JEE

COURSE MATERIAL
CHEMISTRY
MATHEMATICS
MODULE- 4

Contents
Sr. No. Topics Page No.
1. HYDROCARBONS
Straight Line 2 to 69
1-143
2. ALKYL& Circle
ARYL HALIDE 70 to 118
144-210
3. LCD
ALCOHOL & MOD ETHERS 119
PHENOL& to 236
211-293
HYDROCARBONS
H

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Physical Properties
1. The first four members are colourless gases. The next 13 members (C5 to C17) are colourless liquids and the
higher ones are colourless solids.
2. The boiling points of the straight chain alkanes increases regularly with increase in molecular mass. On the
average boiling point increases by 20-30K, for the addition of each carbon atom ( –CH2– group). Among the
isomeric alkanes the boiling point of straight chain isomer is greater than branched chain isomers
H H H H H
e.g. n-pentane H – C – C – C – C – C – H [Link]. 309 K
H H H H H

CH3
isopentane CH – CH2 – CH3 [Link]. 301 K
CH3

CH3
Neopentane CH3 – C – CH3 [Link]. 282.5 K.
CH3

Boiling point order is n-pentane > isopentane > neo-pentane.

However melting point order is Neopentane > Isopentane > n-pentane.
This is because as branching takes place the molecule assumes a spherical form that leads to a much more
closed packing.
3. Alkanes are non-polar and hence are soluble in non-polar solvents and other organic solvents but insoluble in
solvents such as water.

Preparations
A. REDUCTION METHODS
1. Hydrogenation of Alkenes and Alkynes :
When unsaturated hydrocarbons are catalytically hydrogenated we get alkane.
H2 + Pt, Pd or Ni
CnH2n CnH2n+2
200 – 300ºC

2H2
CnH2n–2 CnH2n+2
Ni, Pt or Pd
200 – 300ºC

2 H /Ni
e.g. CH2 = CH2 300ºC CH3 – CH3

Ni
CH  CH + 2H2 CH3 – CH3.
200 – 300ºC

In the above reactions, Raney nickel is often used as an effective catalyst. It is obtained by boiling
Ni-Al along with NaOH, when Aluminium dissolves leaving nickel in finely divided state, it is then filtered and
dried. When palladium or platinum is used , the reactions can be carried even at room temperature.
2. Reduction of Alkyl Halides
Zn – Cu
(a) R – X  C H OH R – H.
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Mechanism :
Zn – Zn2+ + 2e–
. . . – . –
R – X – R + X , R + e– – R , X + e– – X
– –
R + H – OC2H5 – R – H + C2H5O
Zn/HCl
(b) R – X  R – H.

Zn/CH3COOH
(c) R – X 
R–H

Zn/NaOH
(d) R – X  R–H
[Mechanisms for the reaction (b), (c) and (d) are the same as that of (a)]
LiAlH4
(e) R – X 
R–H

[primary and secondary- alkyl halides give alkanes but tertiary halide- gives alkenes]

(f) R–X NaBH4 R–H

[Here secondary- and tertiary-halides are converted to alkanes but not p-halides]
Ph3SnH
(g) R – X 
R–H

[All types of alkyl halides undergo this reaction.]

HI/Red P
R–X  R – H.
3. Reduction of Alcohols

Red P
(a) R – OH + HI 150ºC R–H

Red P
CH3CH2 – OH + HI CH3 – CH3 + I2 + H2O

150ºC

4. Reduction of Carbonyl Compounds (Aldehydes and Ketones)

(a) Using HI / Red P
Red P
C = O + 4HI > CH2+ H2O + 2 I2


CH3 – C – H + 4HI Red P

CH3 - CH3 + H2O + 2I2

O

CH3 – C – CH3 + 4HI Red P

CH3 – CH2 – CH3 +2 I2 + H2O

O
(b) Clemmensen’s Reduction: The reduction of carbonyl compounds to alkanes by using Zn-Hg/HCl is
called Clemmensen’s reduction.

R – C = O + 4[H]
Zn - Hg/HCl
R – CH3 + H2O

H

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CH3 – C = O + 4[H] Zn - Hg/HCl CH3 – CH3 + H2O.

H
Note: Clemmensen’s reduction should not be used if the molecule contains acid sensitive groups and - NO2
group because it also get reduced to - NH2 group

(c) Wolff Kishner Reduction: It is the reduction of carbonyl compounds to alkanes using hydrazine in
the presence of alcoholic KOH. This method is not used if the molecule contains base sensitive groups
group apart from the carbonyl functional group.

alcoholic KOH
R – C = O + NH2 – NH2 — R – C = N – NH2 + H2O R – CH3
473 K
H H

NH2 - NH2
+
CH3 – C – CH3 alcoholic KOH CH3CH2CH3.
O 473 K

O NH2 - NH2
NH2
NH2
alcoholic KOH

5. Reduction of Carboxylic Acids

HI/Red P
RCOOH  150ºC R – CH3

HI/Red P
CH3COOH  150ºC CH3 – CH3.

B. DECARBOXYLATION METHODS

1. Soda Lime Decarboxylation

RCOOH + NaOH — RCOONa + H2O
CaO
RCOONa + NaOH 630 K R – H + Na2CO3

CaO
CH3COONa + NaOH 630 K CH4 + Na2CO3

2. Kolbe’s Electrolytic Decarboxylation

The electrolysis of aqueous salt solutions of carboxylic acids give alkane at anode
Electrolysis
2RCOONa + 2H2O R – R + 2NaOH + 2CO2 + H2.
Electrolysis
2CH3COONa (aq) CH3 – CH3 + 2NaOH + 2CO2 + H2.
Mechanism
R – C – ONa — RCOO– + Na+
O
H2O — H + OH–
Reaction at cathode

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1
Na+ + e– — Na (Not possible) H+ + e– — H (Possible)
2 2
(Because the discharge potential of H+ is less than the discharge potential of Na+)
Reaction at anode
–
2R – C – O
– –
4OH — 2H2O + O2 + 4e (Not possible) — R – R + 2CO2 + 2e– (Possible)
O
– –
(Because discharge potential of RCOO < OH )
Detailed reaction at anode Side Reaction
.. – . – . .
. .: — R – C – O R–C–O–R
R–C–O . .: + e R + RCOO
O O O

–
. . OH
R – C – O — R + CO2 R–C–O–R RCOONa + ROH
O O

. .
R +R — R – R Here ROH is side product:
.
Also disproportionation of R leads to the formation of alkene at smaller alkane as side products
. .
(a) CH3CH2 + CH3CH2COO CH3CH2COOCH2CH3

NaOH
CH3CH2COO CH2CH3 CH3CH2COONa + C2H5OH (side product)
. .
(b) CH3CH2 CH2 = CH2 + H
. .
CH3CH2 + H CH3 – CH3
Hence side products are CH2 = CH2 + CH3CH3 also
Limitation :
1. Methane cannot be perpared by this method
2. Only symmetrical alkanes are prepared by this method

C. THROUGH FORMATION OF ORGANOMETALLIC COMPOUNDS

1. Wurtz reaction
When alkyl halides are reacted with Na in the presence ether we get alkane.
Dry
2R – X + 2Na ether R – R + 2NaX.
Other metals in a finely divided state may also be used in place of Na e.g. Cu or Ag.
Dry
2CH3Cl + Na ether
CH3CH3 + NaCl

Limitations :
1. Methane cannot be prepared.
2. This reaction is not suitable for preparing unsymmetrical alkanes e.g. propane or pentane etc.
1. Mechanism
Ionic
. .
R–X R +X
Na Na+ + e–
. –
R + e– R
. –
X + e– X
R + Na
–
RNa
X + Na
–
NaX
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RNa + R – X R – R + NaX + side products

Note : Side Products are possible due to elemination reaction on R–X by RNa giving a mixture of alkene and
alkane.
Free radical Mechanism
. .
R–X R +X
Na Na + e–
. – –
X +e X
. .
R +R R–R + other side products
The side products are formed due to disproportionation of free radicals.
2. From Grignard’s Reagent
When Grignard’s reagent is made to react with any compound containing H-atom attached to
highly electronegative atom like O, N or F will give alkane corresponding the alkyl part of Grignard’s
Reagent.
RMg X + H – OH R – H + MgX (OH)
R Mg X + H – OR R – H + MgX (OR)
R Mg X + H – NH2 R – H + MgX (NH2)
R Mg X + H – NHR R – H + MgX (NHR)
R Mg X + H – O – C – R Mg ( R 'COO ) (X)
O
3. Frankland Reaction
RX + Zn R ZnX
The alkyl zinc halide or dialkyl zinc may be isolated and made to react with different alkyl halide
or same alkyl halide.
RZnX + RX R – R + ZnX2
(unsymmetrical alkane)
e.g. CH3ZnCl + CH3CH2Cl CH3CH2CH3 + ZnCl2
RZnX + R – X R – R + ZnX2
(symmetrical alkane)
e.g. CH3ZnCl + CH3Cl CH3CH3 + ZnCl2
Hence Frankland reaction is useful for preparing both hydrocarbons containing odd number of C atoms as
well as even number of carbon atom. i.e. for preparing symmetrical as well as unsymmetrical alkanes.
4. Corey House Synthesis
This reaction is very much useful in the preparations of unsymmetrical alkane.
ether
R2CuLi + R – X R – R + R Cu + LiX.
(unsymmetrical)
ether
R2CuLi + R – X R – R + RCu + LiX
(symmetrical)
2Li
CH3CH2 – Br Dry ether CH3CH2Li + LiBr.
2CH3CH2Li + CuI (CH3CH2)2CuLi + LiI
CH3 – Cl
(CH3CH2)2CuLi CH3CH2– CH3 + CH3CH2Cu + LiCl.
CH3CH2 – Cl
(CH3CH2)2CuLi CH3CH2– CH2CH3 + CH3CH2Cu + LiCl.

5. From Carbides :
Al4C3 + 12H2O 4Al(OH)3 + 3CH4.

Be2C + 4H2O 2Be(OH)2 + CH4.

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Chemical Properties
The alkanes are referred as paraffins. Much of the chemistry of alkanes involves free-radical chain reactions,
which takes place under vigorous conditions and usually yield mixtures of products.
The reactions of alkanes can be classified under the following headings.
(A) Substitution reactions (B) Combustion reactions (C) Miscellaneous reactions.

A. SUBSTITUTION REACTIONS

1. Halogenation
250 - 400ºC
– C – H + X2 – C – X + HX.
or light

CH4 + X2 U.V. CH3 – X + HX.

(excess)

CH4 + X2 U.V. CH3 – X CH2X2 CHX3 CX4

(excess)

diffused
CH3 – CH3 + Cl CH3CH2 – Cl + HCl.
(excess)
2 sunlight
diffused
CH3 – CH3 + Cl2 CH3CH2Cl + mixture of products obtained by polychlorination
(excess) sunlight
diffused
i.e. CH3 CH3 + Cl2 CH 3 – CH 2 – Cl + CH 3 CHCl 2 + CH2 – CH2 + CH 3 CCl 3 +
(excess) sunlight
Cl Cl
CH2 – CHCl2 + CH2 – CCl3 + CHCl2 – CCl3 + CCl3 – CCl3.
Cl Cl
Mono halogenation of propane and Butane
CH3CH2CH2 – Cl 45%
hv
CH3CH2CH3 + Cl2
CH3 – CH – CH3 55%
Cl

hv CH3CH2CH2 – Cl 28%
CH3CH2CH2CH3 + Cl2 hv
CH3CH2 – CH – CH3 72%
Cl

CH3CH2CH3 + Br2 hv CH3 – CH – CH3 (major) (96.5%)

hv Br
CH3 – CH2 – CH2 – Br (minor) (3.5%)

Hence these reactions show that the reaction depends upon the abstracting power of the halogen atoms as well
as the number of H-atoms present in the organic molecule.

The abstracting power of the halogen atoms refers to the selectivity factor which includes the HX bond
energy as well as bond dissociation energy of the C–H bond.

Mechanism of Halogenation of CH4 (monohalogenation)

diffused
CH4 + X2 sunlight CH3X + HX
.
Initiation Step - I X2 2X .....(i)
. hv .
Propogation Step - II X + CH3 – H CH3 + HX .....(ii)
. .
CH3 + X – X CH3X + X .....(iii)

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. .
X + CH3 – H CH3 + HX .....(iv)
.
In this whole reaction the reactive species is CH3 . The formation depends upon the abstracting power of
halogen which in turn depends upon the bond strength of HX formed. Which is HF > HCl > HBr > HI and also
bond dissociation energy of X2 which is Cl2 > Br2 > F2 > I2.

Reactivity of halogen is
Reaction reversible and highly endothermic, so moves more
F2 > Cl2 > Br2 > I2 in backward direction

(reacts explosively)
. .
Termination Step-III The free Radicals present in the reactions are CH3 and X . The different
ways in which they can combine for terminating the reaction is
. .
CH3 + X CH3 – X
. .
CH3 + CH3 CH3 – CH3
. .
X +X X2
Reactivity of different H-atom :
The general order of reactivity of different H-atoms is tertiary -H > secondary-H > primary-H because the
stabilities of the corresponding free radicals are tertiary free radical > secondary free radical > primary free
[Link] basic reactivity of H-atom is tertiary > secondary > primary but their reactivity ratio with chlorine
or bromine differs.
p:s :t
The reactivity order with chlorine 1 : 3.8 : 5
The reactivity order with Bromine 1 : 82 : 1600
The reaction of alkane with I2 can be performed by addition of oxidising agents like HNO3 or HIO3.
CH4 + I2 CH3 – I + HI
This reaction is highly reversible with reactions proceeding more in backward direction. But on adding HNO3
or HIO3 the HI gets oxidised to I2 thereby preventing the reduction of CH3-I to CH4.
Laboratory Chlorination
The laboratory chlorinations are usually done using SO2Cl2 (sulphuryl chloride) in the presence of alkyl peroxides
as initiator.
R – H + SO2Cl2 R–O–O–R
R – Cl + SO2 + HCl.
.
Initiation Step - I R–O–O–R 2R – O
. .
Step - II R – O + R – H R – OH + [R
. .
Propogation Step - III [R + SO2Cl2 RCl + S O2Cl
. .
Step - IV SO 2Cl SO2 + Cl
. .
Step - V Cl + R – H [R + HCl.

Then there is repeatation of step III, IV and V.

Termination :
. . . .
The different free radicals are R , S O2Cl and Cl , R – O which can combine in many ways.

Evidence in support of free radical mechanism

(i) Effect of U.V. light :
The reaction does not take place at room temperature. This is because energy is needed to cleave chlorine
molecule homolytically into chlorine free radical.

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(ii) Effect of number of photon :

For each photon or quantumn of light used, several thousand molecules of alkylhalide are formed.
(iii) Effect of Adding Inhibitors :Inhibitors are substances which slow down the rate of reaction
It has been observed that when oxygen is added in the reaction mixture, halogenation
of alkanes slows down due to the formation of less reactive peroxy alkyl free radical.
. .
R + O = O — R–O–O
Peroxyalkyl free radical

2. Nitration : The reaction in which H atom of an alkane is substituted by nitro group (–NO2) is called nitration.

High
R — H + HO NO2 R – NO2 + H2O
Temp. Nitroalkane
Alkane

Normally hexane and higher alkanes can be Nitrated very easily but will give many side products
H3C – (CH2)4 – CH3 + HNO3  H2O + H3C – (CH2)4 – CH2 – NO2
Hexane Nitrohexane

Recently, developed technique of vapour phase nitration, has made nitration of lower alkanes
possible. But the vapour phase nitration also causes cleavage of C–C bond and results in the
formation of more than one nitro compounds,

V.P.
H3C – CH3 + HNO3 H3C – CH2 – NO2 + H3C – NO2
500ºC
Ethane Nitroethane Nitromethane

V.P.
H3C – CH2 – CH3 + HNO3 H3C – CH2 – CH2 – NO2 + H3C – CH – CH3
Propane 500ºC 1-Nitropropane
NO2
2-Nitropropane

+ H3C – CH2 – NO2 + H3C – NO2

Nitroethane Nitromethane
3. Sulphonation : The reaction in which H atoms of alkanes are replaced by sulphonic acid group (–SO3H) is
called sulphonation.

H3C – (CH2)4 – CH2 — H + HO SO2OH 400ºC H3C – (CH2 )4 – CH2 – SO3H + H2O
Hexane
SO3 Hexanesulphonic acid
(conc.)
The mixture of H2SO4 + SO3 =H2S2O7 is called as oleum or Fuming sulphuric acid.

4. Oxidation of alkanes :
(a) Combustion (complete oxidation).
Like other organic compounds alkanes on complete combustion form CO2 and H2O.
CH4 + 2O2 —CO2 + 2H2O
Methane

7
C2H6 + 2 O2 — 2CO2 + 3H2O
Ethane

(b) Chemical oxidation :

Alkanes are usually not affected by oxidising agents like KMnO4 or K2Cr 2O7, but, alkanes
having 3º H atoms are oxidised on heating by these oxidising agents to alcohols.

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H3 C H3 C
H3 C C – H + [O] 
KMnO4
 H3 C C – OH

H3 C H3 C
Isobutane tert. butyl alcohol

Miscellaneouse Reactions :

(i) Isomerisation :
The process of conversion of one isomer into an other is called [Link] are converted to
branched isomers when heated with AlCl3
CH3
AlCl3 + HCl
H3C – CH2 – CH2 – CH3 H3C – CH – CH3
Butane 200ºC, 35 atm. Isobutane

(ii) Aromatisation :
The conversion of aliphatic compounds into aromatic compounds is known as aromatisation.
CH3
H2 C CH3 Cr2O3/Al2O3
+ 4H2
H2 C CH3 600ºC/15 atm.
CH2 Benzene (C
6 H6 )
Hexane (C6H14 )

(iii) Action of steam :

CH4 + H2O Ni/Al2O3

(steam) 800ºC
CO + 3H2

(iv) Insertion of methylene.

Methylene can be inserted into any C–H bonds of alkanes yielding higher alkanes.
Sunlight
CH3CH2CH2CH3 + CH2N2 CH3CH2CH2 CH2CH3 + CH3 – CH – CH2 – CH3
Diazomethane –N2 n-pentane
CH3
Isopentane

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ALKENE
Introduction :

(1) Alkenes are unsaturated hydrocarbons having at least one double bond.

(2) They are represented by the general formula CnH2n (one double bond)

(3) In ethene C = C bond length is 1.34 Å

(4) Its bond energy is 146 [Link]-1

(5) The hybridization of (C = C) alkenic carbon is sp2

(6) The  e¯ cloud is present above and below the plane of - bonded skeleton.

(7) They are also known as olefins since ethene, the first member of the homologous series forms oily liquid
substance when treated with halogens.

(8) Compounds may have more than one double bond in conjugation or isolated or cumulated
forms. Some examples of alkenes and alkadienes are :

(CH3)2C = CH2

Isobutylene Farnesene
(used in the production (present in the waxy coating found on apple skins)
of synthetic rubber)

CH3 – CH = CH – CH2 – CH = CH2 Isolated diene

CH2 = CH – CH = CH2 Conjugated diene
CH3 – CH = C = CH – CH3 Cumulated diene

Note that hybridization of middle double bonded carbon is sp in cumulated [Link] dienes are less
stable than isolated diene which are less stable than conjugated diene.

Structure and bonding in Alkenes:

134pm

117.2°
110pm
()
121.4°
()

(1) Note that bond angle  >  since repulsion due to  electrons (double bond - single bond repulsion > single
bond - single bond repulsion

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Laboratory test of alkene

1. Bayer’s reagent test

cold, dilute alkaline KMnO4 solution is Bayer’s reagent. It is pink in colour.
Bayer 's reagent
CH2  CH2     CH2  CH2
| |
OH OH
Pink colour disappears & brown ppt appears
2. Bromine water test
Br2 / H2O is reddish brown
Br
|
CH2  CH2
Br2  CH2  CH2 
|
Br
colourless solution
& Red colour disappears

Table : I Structural Isomerism in alkenes :

CH3
|
Chain isomerism : 1. CH3 – CH = CH – CH3 & CH3  C  CH2

2. &

Positional Isomerism 1. CH2 = CH – CH2 – CH3 & CH3 – CH = CH – CH3

CH3 CH3
| |
2. CH3  C  CH  CH3 & CH3  CH  CH  CH 2

3. &

Functional Isomerism 1. & CH3 – CH = CH – CH3

2. CH2 = CH – CH = CH2 & CH3 – C  C – CH3

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Table II : Stereoisomerism in alkenes :

(a) Geometrical Isomerism : 1.

(b) Optical Isomerism : 1.

2.

Stability of alkenes

The way of measuring the stability of an alkene is the determination of its heat of hydrogenation or the
heats of combustion. Both are exothermic reactions. (H = – ive)
1
H 
stability

Heat of Hydrogenation of Alkenes :

Heat of
Heat of hydrogenation, Alkene combustion
Alkene
kcal/mol kJ / mol
1-Butene 2719
Ethene 32.8 Isobutene 2703
Propene 30.1 2712
cis-2-Butene
1-Butene 30.3
trans-2-Butene 2707
Isobutene 27.2
cis-2-Butene 28.6
trans-2-Butene 27.6
2-Methyl-2-butene 26.9
2,3-Dimethyl-2-butene 26.6

In general, the order of stability of alkenes is :

R2C = CR2 > R2C = CHR > R2C = CH2 > RCH = CHR (trans > cis) > RCH = CH2 > CH2 = CH2

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TABLE III : PHYSICAL PROPERTIES OF ALKENES

Physical properties Homologus series Isomers

1. Physical state C1 – C3 gases
C4 – C20 liquids
C20 < solid
2. Dipolemoment () cis > trans ( for straight chain alkene)
3. Polarity – cis > trans (for Cab=Cab type of alkenes)
4. Melting point increases trans > cis
(due to more packing capacity)
5. Boiling point increases cis > trans
# branching decreases bp

<C–C=C–C
Polarity increases boiling point
increases

6. Solubility Practically insoluble cis > trans ( due to more polar nature )
in water but fairly Polarity increases solubility in polar
soluble in nonpolar solvents
solvents like benzene
petroleum ether, etc. or other
organic solvents
7. Stability trans > cis
(due to less repulsion
force between two similar group)

Methods of preparation of alkenes:

1. BY PARTIAL REDUCTION OF ALKYNES

(i) A Syn Addition of Hydrogen: Synthesis of cis-Alkenes : This is performed by : -

(a) Lindlar’s catalyst : Metallic palladium deposited on calcium carbonate conditioned with lead acetate
and quinoline.
(b) P-2 catalyst (Ni2B nickel boride)
H2 ,Pd / CaCO 3
(Lindlar 's catalyst )
R – C  C – R       
quinoline

H2 / Ni2B(P 2)
or H / Pd / CaCO 3
CH3 CH2C  CCH2 CH3  2     
(syn addition )

3  Hexyne

Mechanism of hydrogenation :

(1) H H –C=C– H H

 | | | | | | 

( 2)

adsorption

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Steps : The reactant alkyne molecules and hydrogen molecules get adsorbed at the surface of metal cata-
lyst. It is chemical adsorption (chemisorption).
In this state the reactant lie very close to each other and so the hydrogen atoms start forming bond with
carbon. Two hydrogen atoms are added to two triply bonded carbon atoms f rom the
same side of  bond and a cis or syn addition product is formed. The product alkene now escapes away
from the surface of the catalyst. Quinoline occupies the metal surface inhibiting further reduction to alkanes.
Quinoline therefore is called catalyst poison and such palladium is called deactivated catalyst or poisoned
catalyst.
(ii) Anti Addition of Hydrogen: Synthesis of trans-Alkenes
Mechanism : Reagents Na(or Li,K) + liq NH3  Na+ + e¯ (solvated electron)

NaNH2 +

Na / NH (  )
Example : CH3 – CH2 – C  C – CH2 – CH3   3

Note # This process of reduction is not eligible when terminal alkynes are taken.(Ex. CH3–CCH)
because terminal alkynes form sodium salt with Na metal.
CH3 – C  CH + Na / NH3  CH3 – C  C¯ Na+ + NH4+

2. BY DEHALOGENATION OF VICINAL DIHALIDES :

There are two types of dihalides namely gem (or geminal) dihalides in which the two halogen atoms are
attached to the same carbon atom and vicinal dihalides in which the two halogen atoms are attached to the
adjacent carbon atoms.
Dehalogenation of vicinal dihalides can be effected either by heating with NaI in acetone or zinc.
CH3 – CHBr – CH2Br 
Zn dust
 CH3 – CH = CH2
NaI
CH3 – CHBr – CHBr – CH3    CH3 – CH = CH – CH3
Acetone
# It involves an anti - elimination of halogen atoms

3. DEHYDROHALOGENATION OF ALKYL HALIDES

Alkyl halides when treated with a strong base like

(i) Hot alcoholic solution of KOH (ii) NaNH2 /KNH2 (iii) tBuO¯K+ in t-BuOH
Undergo elimination of hydrogen halide (HX) leading to the formation of alkenes.
alc. KOH
R – CH2 – CH2 – X   R – CH = CH2 + KX + H2O

CH3
|
Heat
CH3  C  Br + alc. KOH  CH3  C  CH2  KBr  H2 O
| |
CH3 CH3

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CH3
|
Heat
CH3  C  Br + alc. KOH  CH3  C  CH2  KBr  H2 O
| |
CH3 CH3

Here  – H is eliminated by base hence called  elimination following saytzeff rule.

i.e. (Highly substituted alkene is major product). It also involves an anti elimination of HX.
For example

4. DEHYDRATION OF ALCOHOLS

Alcohols when heated in presence of following reagents undergo loss of water molecule and form alkenes.
The elimination is  elimination.
(i) H2SO4 / 160°C (ii) H3PO4 / 
(iii) P2O5 / 
(iv) Al2O3 / 350°C undergoes loss of water molecule and form alkenes

Dehydration of alcohols may involve rearrangement

5. BY PYROLYSIS OF ESTERS
Thermal cleavage of an ester involves formations of a six membered ring in the transition state leading to the
elimination of an acid leaving behind an alkene.

500C +
  

As a direct consequence of cyclic transition state, both the leaving groups namely proton and carboxylate ion
are eliminated from the cis position. This is an example of cis elimination.

6. BY HOFMANN ELIMINATION METHOD

Alkenes can be prepared by heating quaternary ammonium hydroxide under reduced pressure at a tempera-
ture between 100°C and 200°C.
Less subsituted alkenes are formed as major product in this case, which are defined as Hofmann alkenes.


 (CH3)3N + CH2 = CH2 + H2O

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¯ OH




7. BY WITTIG REACTION
The aldehydes and ketones are converted into alkenes by using a special class of compounds called phos-
phorus ylides, also called Wittig reagents.
The Triphenyl group of phosphorane has a strong tendency to pull oxygen atom of the aldehyde or ketone via
a cyclic transition state forming an alkene.

R’
C=O
R R’ R’ R
C–O C = C
- +  R  + Ph3P = O
R – C – PPh3 R R 
| Phosphorous ylide R – C – PPh3
|
R R
(R, R, R and R may be hydrogen or any alkyl group)

Reactions at the carbon–carbon double bond

Addition Reaction : The double bond consists of a strong  bond and a weak  bond; we expect,
therefore, that reaction would involve breaking of this weaker bond. This expectation is correct; the typical
reactions of the double bond are of the sort where the bond is broken and two strong bonds are formed
in its place.

–C=C– + EZ –C–C–
E Z
A reaction in which two molecules combine to yield a single molecule or product is called as an addition
reaction. The reagent is simply added to the substrate, in contrast to a substitution reaction where part of the
reagent is substituted for a part of the substrate. Addition reactions are necessarily limited to compounds that
contain atoms sharing more than one pair of electrons that is, to compounds that contain multiply bonded
atoms. Formally, addition is the opposite of elimination; just as elimination generates a multiple bond, addition
destroys it. In the structure of the bond there is a cloud of electrons above and below the plane of the
atoms. These electrons are less involved than the electrons in holding together the carbon nuclei.

C—C


As a result, they are themselves held less tightly. These loosely held electrons are particularly available to a
reagent that is seeking electrons. It is not surprising, then, that in many of its reactions the carbon–carbon
double bond serves as a source of electrons : that is, it acts as a base. The compounds with which it reacts
are those that are deficient in electrons. These acidic reagents that are seeking a pair of electrons are called
electrophilic reagents. The typical reaction of an alkene is electrophilic addition, or, in other words, addition
of acidic [Link] of another kind i.e., free radicals also seek electrons–or, rather, seek an electron.
And so we find that alkenes also undergo free-radical addition.

Electrophilic Addition Reaction – Mechanism

Addition of the acidic reagent, HZ, involves two steps : (Z may be –Cl, –Br, –I, –CN, –OH, –OSO3H etc.)
Step (1) the first step involves the addition of H leading to the formation of carbocation.
Step (2) is the combination of the carbocation with the base : Z.

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The evidence for this mechanism includes.
(a) The rate of reaction depends upon the concentration of both the alkene and the reagent HZ.
(b) Where the structure permits, reaction is accompanied by rearrangements.
(c) orientation of addition
(d) Relative reactivities of alkenes.

Rearrangements in Electrophillic Addition Reaction: Where the structure permits, the reaction is accompanied
by rearrangements. The product sometimes contains the group Z attached to a carbon that was not doubly
bonded in the substrate; sometimes the product even has a carbon skeleton different from that of the substrate.
These “unexpected”: products, are readily accounted for by rearrangements of the carbocations proposed as
intermediates.
For example, addition of hydrogen iodide to 3,3-dimethyl-1butene yields not only the expected 2-iodo-3, 3-
dimethylbutane, but also 2-iodo-2, 3-dimethylbutane:

CH3 CH3 CH3

–
HI I
CH3 – C – CH = CH2 CH3 – C – CH – CH3 CH3 – C – CH – CH3

CH3 CH3 CH3 I
Methyl shift CH3
CH3 – C – CH – CH3
 I–
CH3
(CH3)2C(I) CH(CH3)2
Since a 1,2-shift of a methyl group can convert the initially formed secondary cation into a more stable tertiary
cation, such a rearrangement does occur, and much of the product is derived from this new ion and hence the
product obtained is 2-Iodo –2, 3– dimethyl butane.

Electrophilic Addition : Orientation and Reactivity

The mechanism is consistent with the orientation of addition of acidic reagents, and the effect of structure on
the relative reactivities of alkenes.
Addition of hydrogen chloride to two of the typical alkenes is outlined below, with the two steps of the mechanism
shown. In accordance with Markovnikov’s rule, propylene yields isopropyl chloride, isobutylene yields tert-
butyl chloride, and 2-methyl-2-butene yields tert-pentyl chloride.

Cl
CH3 – CH 2 – CH2 (gives minor products ) CH3 – CH – CH3
CH3 – CH = CH2 HCl CH3 – CH– CH3 (gives major products) Cl
(major product)

According to the mechanism, hydrogen from the reagent adds to one or the other of the two doubly bonded
carbons to give one or the other of two possible carbocations. For example, if hydrogen goes to C–2 of
propylene, we get the n-propyl cation; if it goes to C–1, we get isopropyl cation. Once formed, the carbocation
rapidly reacts to yield product. Which halide is obtained, then depends upon, which carbocation is formed in the
first step. The fact that propylene yields isopropyl chloride rather than n-propyl chloride shows that the isopropyl
cation is formed, faster than the n-propyl cation. Thus, orientation in electrophilic addition is determined by the
relative rates of two competing reactions : formation of one carbocation or the other.

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CH3
CH3
CH3 – C – CH3
CH3 CH3 – C – CH3 –
HCl  Cl
CH3 – C = CH2 Cl
tertiary carbocation (major product)

CH3

HCl CH3 – C – CH2
H
(give minor product)

In each of the examples given above, the product obtained shows that in the initial step a secondary cation is
formed faster than a primary, or a tertiary cation is formed faster than a primary, or a tertiary tertiary cation is
formed faster than secondary. Examination of the orientation in many cases shows that this is a general rule :
in electrophilic addition the rate of formation of carbocations follow the sequence
Rate of formation of carbocations 3º > 2º > 1º Stability of carbocations 3º > 2º > 1º > CH3+
Reactivity of alkenes towards acids is

CH3
C = CH2 > CH3CH = CHCH3 > CH3 CH = CH2 > CH2 = CH2 > CH2 = CH
CH3
Cl

Chemical Reactions :

1. Hydrogenation Reaction
H2 / Ni
– C = C – + H2 Pt, Pd
–C– C– CH3 – CH = CH2 CH3 – CH2 CH3
or 
Ni
H H
2. Addition of Halogens

–C= C– + X2 –C– C– Here X2 = Cl2 or Br2

CClX
4
X
e.g. CH3CH = CH2 + Br2 CH3 – CH – CH2
Br Br
Vicynal dihalide
The reaction is carried out simply by mixing together the two reactants, usually in the solvents like carbon
tetrachloride. The addition proceeds rapidly at room temperatures and does not require exposure to ultraviolet
light.
Note : If high temperature or exposure of light is there,then substitution may
become an important side reaction.

Mechanism: The additions of halogens to alkenes involves two steps.

Step - 1: Halogen transfer loosing a pair of electron.

H H H H H  H
+ X
C—C C — C C — C
– +X–X + X–
H H H
H H H  – T.S.
Halonium complex
 – Complex

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Step - 2:

H X H X H
C — C
H– C – C – H
H – H
X H X
Anti Addition

The second step involves the attack of X– ion on the halonium complex to form the dihalogen derivatives.
This mechanism is proposed based upon the fact that the reaction depends upon
(i)effect of the structure of alkene.
(ii) effect of added nucleophile on the product obtained.

(a) Effect of Structure of Alkene: Alkenes show the same order of reactivity towards halogens as towards acid.
CH3
C = CH2 >CH –CH=CH–CH >CH –CH=CH >CH =CH > CH = CH – Cl
CH3 3 3 3 2 2 2 2

(b) Effect of Nucleophiles on Products Formed: If a holomium ion is the intermediate and capable of reacting
with halide ion, then we might expect it to react with almost any negative ion or basic molecule.
CH2 = CH2 + Br2 
CCl4
 CH2 – CH2
Br Br

CH2 – CH2 CH2 – CH2

CH2 = CH2 + Br2 NaCl +
Br Br Br Cl

CH2 – CH2
CH2 = CH2 + Br2 NaI + CH2 – CH2
Br Br Br I
But also CH2 = CH2 + NaCl No reaction
H2 O
CH2 = CH2 + Br2 CH2 – CH2
Br OH

Stereo Chemistry of Addition:

The stereochemistry of the reaction can be used understood by the mechanisms.

Br
Br — Br C= C C= C


Br Br
C= C –C– C–

Br – Br

When cis But-2-ene is brominated a racemic mixture of 2,3-Dibromo butane is obtained this could be
explained by the mechanism as proposed above.

H H H Br H
C=C C=C
Br2 + Br–
Me Me Me Me

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Br
Br
Br
H Me H
Attack (a) C Me Me H
C
 I
H Br H H Me
Br
C=C H Br
Br Me
Br
Me Br – Me C C
Attack (b)
(Attack a) (Attack b)
H Me Br Me
H H Me
II

Compounds I and II are mirror images of each other. Also attack of Br anti to Brcan be by 50% attack a
and 50% attack b thus leading to racemization.
However, Bromination of trans but-2-ene leads to meso compound formation.

H Me H Br
Me
C=C C–C –
+ Br2 + Br
Me H Me H

Br
Br Br
H Me
C C III
 H
H Br (a) Me
Me Br Me H H Me
C–C
Me H Br
Br Br
Me (a) Br – (b) H (b)
C C IV
H
H Me Br Me
H Me

Compound III and IV are identical and possess a plane of symmetry and hence are meso Form
3. Addition of Hydrogen Halides
An alkene is converted to alkyl halide by addition reaction of HCl or HBr or HI.

(a) – C = C – + HX –C– C–
H X
Here HX = HCl, HBr, HI
CH3 – CH = CH2 + HI CH3 – CH – CH3
I
CH2 = CH2 + HI CH3 – CH2 – I
The reaction is frequently carried out by passing dry gaseous hydrogen chloride into alkene. Sometimes it is
carrried out in moderately polar solvents like CH3 COOH, which dissolves both the polar HX and the non polar
alkene.
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When the alkene is symmetrical like CH2 = CH2 or CH3–CH=CH–CH3 etc. then the addition of HX may
go to any C-atom carrying a double bond.
CH2 = CH2 + HBr CH3–CH2–Br
CH3–CH = CH–CH3 + HBr  CH3 – CH – CH2 – CH3
Br

But if the alkene is not symmetrical, like CH3–CH=CH2, C2H5–CH=CH2 then addition of HX takes place
according to Markownikov’s rule.
“In addition of an acid to carbon-carbon double bond of an alkene, the hydrogen atom of the HX attaches
itself to the carbon atoms that has greater number of hydrogen.”
e.g. CH3 – CH = CH2 + HI CH3 – CH – CH3
I
CH3 CH3
CH3 – C = CH2 + HI CH3 – C – CH3
I
I
CH3 – CH – CH = CH2 + HI CH3 – C – CH2 – CH3
CH3 CH3

(b) Peroxide Effect: Addition of HCl and HI to alkenes follows Markownikov’s rule. But HBr addition was
reported to be a mixture of both Markawnikov’s Rule and Anti Markownikov’s rule.. Until in 1933 M.S.
Kharasch and Mayo solved this confusion by discovering the orientations of addition of HBr solely in
presence or absence of peroxides.

CH3 – CH – CH2
CH3 – CH = CH2 HBr
Br
Markownikov's Rule

HBr
CH3 – CH = CH2 CH3 CH2 – CH2 – Br
Peroxide

CH3
Peroxide
CH3 CH3 – CH – CH2 – Br
HBr Anti Markownikov's Rule
CH3 – C = CH2
CH3
No Peroxide
CH3 – C – CH3
Br
Markownikov's Rule

4. Addition of H2 SO4: Alkenes react with cold concentrated sulphuric acid to form compounds of general
formula ROSO3 H. known as alkyl hydrogen sulphates. The reactions are again highly regeioselective and
follow the Markownikov’s Rule.
98% H2SO4
CH2 = CH2 CH3 CH2OSO3H
Ethyl hydrogen Sulfate

CH3 CH – CH3
80% H2SO4 OSO3 H
CH3 CH = CH2
Isopropyl Hydrogen sulphate

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The alkyl hydrogen sulphates are deliquiscent solids and are difficult to isolate.
When such an alkyl hydrogen sulphate is diluted with water and heated, we get an alcohol bearing the same
alkyl group. The ester of the sulphuric acid is cleaved to get an alcohol and sulfuric acid.
98% H2O
CH2 = CH2 H2SO4 CH3 CH2 OSO3H 
CH3CH2 – OH + H2SO4

80% H2O
CH3 – CH = CH2 CH3 – CH– CH3 CH3 – CH– CH3 + H2SO4
H2SO4 
OSO3H OH

CH3 OH
63% H2O
CH3C CH2 CH3 – C– CH3 CH3 – C– CH3 + H2SO4
H2SO4 
CH3 OSO3H CH3

This sequence of the reaction provides a good route for preparing alcohols.

5. Addition of H2O: Water may be added to alkenes in the presence of acids to yield alcohols. This reaction
also follows Markownikov’s rule.
+
CH2 = CH2 + H2O H 3 O CH3 – CH2 – OH
OH
CH3 – C = CH2 + H2O H3O + CH3 – C – CH3
CH3 CH3

6. Addition of Hypohalous Acids: The addition of Cl2 or Br2 in the presence of water can yield compounds
containing halogen and OH on adjacent C-atoms such compounds are called halohydrins.
H2O
CH2 = CH2 + Br2 CH2 – CH2
Br OH
H2O
CH3 – CH = CH2 + Cl2 CH3 – CH – CH2
OH Cl
These compounds are not formed due to the formation of HOX but by reactions of alkene with halogen and

X
–C– C– X
H2O
water. X2 + C= C –C– C–
OH2

OH
These reactions follow anti stereospecific mechanism.
Though these reactions proceed to form products which are in accordance with Markownikov’s rule, the
stereochemistry suggests that the reaction proceed via halomium ion formation and not via formation of
classical carbocation
7. Addition of Alkene, Dimerization: When Isobutene is reacted with catalytic amount of H2SO4 or H3PO4
(a protic acid) then we get a mixture of two alkenes with molecular formula C8H16
CH3 CH3 CH3 CH3 CH3
H2SO4
CH3 – C = CH2 CH2 = C – CH2 – C – CH3 + CH3 – C = CH – C – CH3 H2/ Ni
80ºC 
CH3 CH3

( Major (CH3)2CHCH2 – C(CH3)3

product) Isooctene
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Mechanism
CH3 CH3
–
CH3 – C = CH2 + H2SO4 CH3 – C – CH3 + HSO4

CH3 CH3 CH3 CH3
CH3 – C = CH2 + CH3 – C – CH3 CH3 – C – CH2 – C – CH3


CH3
CH3 CH3
CH2 = C– CH2 – C – CH3 Me Me
CH3 CH3 (a)
CH3 Me – CH – CH2 – C – CH3
CH2 – C – CH – C – CH3 CH3 CH3 H2 / Ni
 (b) Me
H H CH3 CH3 – C= CH – C – CH3
(Isooctene)
CH3
–
HSO4

8. Addition of Alkanes (Alkylation): When alkenes are reacted with alkanes in the presence of H2 SO4 or HF
at 0ºC then we get a higher homologue of alkane.
CH3 CH3 Me Me
H2SO4
e.g. CH3 – C = CH2 + H – C – CH3 Me – C– CH2 – C – Me
or HF
CH3 0º C H Me
Mechanism
Me Me
–
Me – C= CH2 + HF Me – C – CH3 + F


Me Me Me Me
Me – C = CH2 + Me – C – Me Me – C – CH2 – C – Me
 
Me
Me Me Me Me
Me – C – CH2 – C – Me Me – CH – CH2 – C – Me + Me3 C+
 Me
Me Me
H – C– Me
Me
9. Oxymercuration - Demercuration : Alkenes react with mercuric acetate in the presence of water to give
hydroxy mercurial compounds which on reduction yields alcohols.
Step - 1 Oxymercuration

C= C + H2O + Hg (OAC)2 – C – C–
Step - 2 Demercuration OH Hg (OAC)

NaBH4
– C – C– – C – C–
OH Hg (OAC) OH H

Oxy mercuration-Demercuration is highly regeioselective and gives alcohols corresponding to

Markownikov’s Rule.
(i) Hg (OAC)2 / H2O
CH3 CH2 CH2 CH2 CH = CH2 Me CH2CH2CH2 – CH – CH3
(ii) NaBH4
OH

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Me Me
(i) Hg (OAC)2 / H2O
Me – C= CH2 + Me – C – Me
(ii) NaBH4
OH
Me Me
(i) Hg (OAC)2
Me – C – CH = CH2 Me – C – CH – Me
(ii) NaBH4
Me Me OH
Oxymercuration involves electrophilic addition to carbon-carbon double bond with the mercuric ion acting as
electrophile.
Me Me Me Me
Since Me – C – CH = CH2 gives only Me – C – CH – Me and not Me – C – CH – Me so it indicates that the
Me Me OH OH
mechanism does not involve any rearrangement, thus carbocations is not formed. But it proceeds via a
cyclic mercurinium ion.

2+
2+ H2 O NaBH4
– C = C– + Hg – C – C– – C – C– – C – C–
Hg OH Hg (OAC) OH H
Mercuration can be carried out in different solvents to yield products other than alcohol.

10. Hydroboration–Oxidation: When alkenes are reacted with dibroranes (B2H6), alkenes undergo hydroboration
to yield alkyl boranes (R3B) which on oxidation give alcohols.
CH2 = CH2 + B2H6 — (CH3 CH2)3B
–
(CH3CH2)3B + 3H2O2 OH CH3CH2 – OH + B(OH)3
All Hydroboration - oxidation, reactions are highly regeioselective, however here the product formed is according
to Anti Markownikov’s Rule.
H2 O2
CH3 – CH = CH2 + B2H6 — (CH3CH2CH2)3B – CH3CH2CH2 – OH + H3BO3
OH
H2 O2
CH3 CH2CH = CH2 + B2H6 — (CH3CH2CH2CH2)3B – CH3CH2CH2CH2 – OH + H3BO3
OH
CH3 CH3
(i) B2H6
CH3 – CH = C – CH3 CH3 – CH – CH – CH3
–
(ii) H2O2 / OH
OH
Thus rearrangement does not occur in Hydroboration.

Oxidation Reactions in Alkene

1. Hydroxylation (Using Baeyer’s Reagent): When an alkene react with dilute alkaline KMnO4 solution in cold
condition then the alkene gets converted to vicinal diol.

alkaline KMnO4
(Cold) CH2 – CH2 + MnO2
CH2 = CH2 (Pink)
OH OH
(Colourless)
alk KMnO4
CH3 – CH = CH2 CH2 – CH – CH2
(Cold)
OH OH

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Mechanism
–
O
C C–O
1. + MnO –
4
Mn
C C–O
O

–
O
C–O C – OH
Mn –
C–O OH + MnO2
O C – OH

This reaction on alkene generates vicinal diol and is a SYN–ADDITION reaction.

This is supported by the mechanism that the oxygen atoms of OH group in the diol formed are from the
permanganate ions which add to the alkene molecule from the same side.

2. With OsO4 (Osmium tetraoxide)

R H
R – CH – O O
C R – CH – OH
Os NaHSO3
+ OsO4 R – CH – O
C O R – CH – OH
R H
This is again a SYN–ADDITION reaction.

3. With HOT KMnO4: Alkenes on reaction with hot alkaline KMnO4 give a mixture of carboxylic acid and
ketones or only ketones or carboxylic acids.
O 
CH2 = CH2 
  O 
Hot KMnO4 2 HCOOH  
2CO2 + 2H2O
(O)
CH3 – CH = CH2 CH3COOH + CO2 + H2O
Hot KMmO4

CH3 CH3
O 
CH3 – C = CH2 
Hot KMnO4 CH3 – C = O + CO2 + H2O

4. Ozonolysis Reaction: All alkenes react with Ozone to form an Ozonide.

O
C=C + O3 C C
O—O
Such Ozonides may be cleaved in 3-ways

Hydrolytic/ Reductive
Zn / H2O or Zn / HCl C=O+O=C
(Removing H2O2 formed)
Oxidative
O Carboxylic acid + Ketones
(without Removing H2O2 formed)
C C
O O Strong Reductive primary alcohol + secondary alcohol
Li AlH4 or H2 /Ni
or H2 /Pt or H2 /Pd

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(i) Ozonolysis of Propene

O
O3
CH3 – CH = CH2 CH3 – CH CH2
O O

Zn/H2O LiAlH4
(Removing H2O2 (Without Removing
H2O2 formed)
formed)

CH3 CHO + HCHO CH3 COOH CH3 CH2 – OH

+ +
HCOOH CH3OH

(ii) Ozonolysis of 2-Methyl but-2-ene

CH3 O CH3
O3
CH3 – CH = C CH3 – CH C
CH3 CH3
O O

LiAlH4
Zn/H2O (Without Removing
(Removing H2O2 H2O2 formed)
formed)
CH3 CH3 COOH CH3 CH2 – OH
CH3 CHO + C=O
CH3 + CH3 CH – CH3
CH3
C=O OH
CH3
Note Only
CH3CHO gets converted to acid
i.e. aldehydic part gets converted to
carboxylic acid

Ozonolysis reactions help to locate the terminal position of double bond in alkene by estimation of CO2 formed
by oxidation of terminal alkene.
5. Addition of Oxygen: Alkenes on addition with oxygen in the presence of silver as catalyst at 570K forms
epoxide.

1 Ag CH2 – CH2
CH2 = CH2 + O
2 2 570K O
Ethylene oxide

1 Ag R – CH– CH2
R – CH = CH2 + O
2 2 570K O

6. Substitution Reactions: Most alkenes contain not only the carbon-carbon double bond but also alkyl groups
which have essentially alkane character. Hence besides the addition reactions which are characterstics of
carbon-carbon double bonds, Alkenes may undergo the free radical substitution also which is a characteristic
of alkanes.

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(a) Halogenation, Allylic Substitution

H–C–C–C– + X2 X– C–C=C–

Low concentration

Cl2
CH3 – CH = CH2 Cl – CH2 – CH = CH2
700º C

Br
+ N- Bromo succinimide

When we consider the molecule of propene

H
H – C – CH = CH2 Site - I
H

Site - II
The Site-I is the alkene site where due to the presence of reactive -bonds the reaction can take place at low
temperature, in the absence of light and generally in liquid state. While site-II is the alkane site which requires
high temperatures or U.V light. If we try to make the reaction possible at site-II, we must take the necessary
condition of high temperature or U.V. radiations.

Cl2 lower temp

CH3 – CH – CH2
CCl4 solution (By polar mechanism)
Cl Cl
CH3 – CH = CH2
Cl2 500 – 600º C Cl – CH2 – CH = CH2 (By radical mechanism)
Gas phase

Mechanism

high temp. .
Inilation X2 2X
U .V .
Propogations.
. 
X + CH3 – CH = CH2 HX + CH 2 – CH = CH2

 .
CH2 – CH = CH2 + X
CH 2 – CH = CH2 + X – X
X

Also CH3 – CH = CH2 + SO2 Cl2 CH2 – CH = CH2 + HCl + SO2

Cl
CH3 – CH = CH2 + Me3 COCl CH2 – CH = CH2 + HCl
Cl
7. Addition of Carbenes: Alkenes react with diazomethane to form cyclic compounds.
CH3 – CH = CH2 + CH2N2 CH3 – CH – CH2

CH2

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Mechanism

..
–  hv CH2 + N2
CH2 – N  N :
Carbene

..
CH3 – CH = CH2 + CH2 CH3 – CH – CH2

CH2

Also

– C–C–
– C–C–
C=C + ICH2ZnI + ZnI2
CH2
CH2
I – Zn I

8. Addition of Free Radicals: Analogous to free radical addition of HBr to alkenes, even CCl4 or CBr Cl3, or
CBr2 Cl2 can be added on to alkenes by using certain conditions favourable for free radical addition reaction
R – CH = CH2 + CCl4 Peroxide R – CH – CH2 – CCl3
Cl
Mechanism
Peroxide Radical
.
Radical + CCl4 Radical : Cl + CCl3
. .
CCl3 + RCH = CH2 R – CH – CH2 – CCl3

. .
R – CH – CH2 CCl3 + Cl R – CH – CH2
Cl CCl3

uv
Me3C – CH = CH2 + ICF3 Me3C – CH – CH2 – CF3
I
9. Isomerization
CH3 CH2 CH2 CH = CH2 770-870 ºC CH3 – CH2 – CH = CH – CH3
or
AlCl3 at 470-510ºC
10. Polymerization

nCH2 = CH2
 / Pressure   CH 2  CH 2  n  polyethene
O2

nCH2 = CH – Cl Traces of O2 (CH 2 - CH) n polyvinylchloride (PVC)

Cl

nCF2 = CF2 ( F2C – CF2 )n polytetrafluoro ethylene (PTFE)



11. Diels Alder reaction :

+

Diene Dienophile

Presence of electron donating groups on diene and electron withdrawing groups on dienophile favours the
reaction.

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ALKYNES
Introduction :
(1) Alkynes are hydrocarbons that contain carbon-carbon triple bond.

(2) The general formula is : CnH2n–2. (one triple bond)

(3) The hybridization of carbon (C  C) in alkynes is carbon sp

(4) Overlapping of these sp hybrid orbitals with each other and with the hydrogen s orbitals gives the sigma
bond framework which is linear (180°) structure.

(5) Two pi bonds result from overlap of the two remaining unhybridized p orbitals on each carbon atom. These
orbitals overlap at right angles (90°) to each other, forming one pi bond with electron density above and below
the C – C sigma bond, and the other with electron density in front and in back of the sigma bond. This result
in a cylindrical  electron cloud around  bonded structure

Note : Any type of stereoisomerism does not arise in acetylenic bond due to linearity of C  C bond.

Laboratory test of alkynes

1. Bayer’s reagent test
cold, dilute alkaline KMnO4 solution is Bayer’s reagent. It is pink in colour.
Bayer 's reagent
CH  CH  4O   
 HOOC – COOH
Pink colour disappears
2. Bromine water test
Br2 / H2O is reddish brown
Br Br
| |
CH  CH + 2Br2  H  C  C  H
| |
Br Br
white ppt.
& Red colour disappears

Laboratory test of terminal alkynes

When triple bond comes at the end of a carbon chain. The alkyne is called a terminal alkyne.

1. Ammoniacal silver nitrate test

HC  CH + 2AgNO3 + 2NH4OH  Ag – C  C – Ag + 2NH4NO3 + 2H2O
(white ppt)

2. Ammonical Cu2Cl2 test

HC  CH + Cu2Cl2 + 2NH4OH  Cu – C  C – Cu + 2NH4Cl + 2H2O

(red ppt)

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3. Na in ether test
HC  CH + 2Na  Na – C  C – Na + H2
(colourless gas)

Acidity of Terminal Alkynes

Terminal alkynes are much more acidic than other hydrocarbons due to more electronegative sp hybridized
carbon. The polarity (acidity) of a C – H bond varies with its hybridization, increasing with the increase in % s
character of the orbitals : sp3 < sp2 < sp.

Weakest
Compound Conjugate Base Hybridization of carbon % s character pKa
acid

sp3 25% 50

sp 3 33% 44

sp 50% 25

R - OH R-O- 16 -18
Stronger
acid

Nomenclature :

CH  CH Ethyne
CH3 – C  CH Propyne
CH  C  CH2  CH3 But-1-yne
CH  C  C  CH3 But  2  yne

6-Bromo-2-methylpent-3-yne

But-3-yn-2-ol

Isomerism
(i) Chain isomerism : CH3 – CH2 – CH2 – C  CH & CH3 – CH – C  CH
|
CH3
(ii) Position isomerism : CH3 – CH2 – CH2 – C  CH & CH3 – CH2 – C  C – CH3

(iii) Functional group isomerism

CH3 – CH2 – C  C – CH3 & CH3 – CH = C = CH – CH3

etc.

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Physical Properties of Alkynes
(1) Alkynes are relatively nonpolar (w.r.t. alkyl halides and alcohols) and are nearly insoluble in water (but they
are more polar than alkenes and alkynes). They are quite soluble in most organic solvents, (acetone, ether,
methylene chloride, chloroform and alcohols).

(2) Acetylene, propyne, and the butynes are gases at room temperature, just like the corresponding alkanes
and alkenes. In fact, the boiling points of alkynes are nearly the same as those of alkanes and alkenes with
same number of carbon atoms.

TABLE : COMPARATIVE STUDY OF ALKANES, ALKENES, ALKYNES

Properties Alkanes Alkenes Alkynes

1. bond length 1.54 (C – C) 1.34 (C = C) 1.20 (C  C)

2. bond energy(KJmol-1) 415 (C – C) 615 (C = C) 835 (C  C)

3. Hybridization sp3 sp2 sp

4. % s charecter 25% 33% 50%

5. PKa 50 44 25

6. Electronegativity of ‘C’ Increases

7. Polarity Increases

8. Rate of hydrogenation – less more

9. Rate of electrophilic
addition reaction – more less

10. Heat of combustion C2H6 (– 373) C2H4 (– 337 kcal) C2H2 (– 317 kcal)

11. Density (g/cm3) C3H8 (0.50) C3H6 (0.52) C3H4 (0.67)

12. Structure

13. Shape Tetrahedral Planar Linear

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General methods of preparation :

1. By dehydrohalogenetion of geminal and vicinal dihalide :

(Anti elimination reaction)

R – C  C – R

R – C  C – R

mechanism :

 R – C  C – R

2. By dehalogenetion of tetrahaloalkane :

R – C  C – R + 2Zn X2

3. By alkylation of terminal alkynes :

(a)

Example
2 eq 2 moles ( CH3 X )
H–CC–H    Na+ C–  C– Na+      
NaNH2
 CH3 – C  C – CH3

R Mg X RX
(b) R – C  C – H    R – C  C Mg X  R – C  C – R
+ R H

4. By Kolbes electrolylic synthesis :

CH
Electrolysis
+ H2O   ||| + 2CO2 + 2KOH + H2
CH

5. By hydrolysis of carbides
CaC2 + 2HOH  C2H2 + Ca(OH)2
MgC2 + 2HOH  C2H2 + Mg(OH)2

Mg2C3 + 4HOH  CH3 – C  CH + 2Mg(OH)2

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Chemical reactions :
(i) Reduction to alkanes
H H
| |
Pt. Pd, or Ni
R – C  C – R + 2H2     R  C  C  R
| |
H H
Example
Pt / H
CH3 CH2  C  C  CH2  OH + 2H2  
2
 CH3 CH2  CH2  CH2  CH2  OH
2  Pentyn  1  ol Pen tan– 1 – ol

(ii) Reduction to alkenes

Pd / BaSO4, quinoline
R – C  C - R         (syn addtion)

Na  NH
R – C C – R’   
3
 (anti addtion)

Example

CH3 CH2  C  C  CH2 CH3 

H2 , Pd / BaSO 4
  
3  Hexyne quinoline

(iii) Addition of halogens (X2 = Cl2, Br2)

X X
X2 X2
| |
R – C  C – R 
 R – CX = CX – R 
 R  C  C  R
| |
X X

(iv) Addition of hydrogen halides (where HX = HCl, HBr, or HI)

H X
| |
HX HX
R – C  C – R  R  CH  CX  R  R  C  C  R
(Markovnikov addition) | |
H X
Example

Cl
HCl HCl |
CH3 CH 2  C  C  H   CH3 CH2  C  CH3
|
1  Butyne Cl
2, 2  Dichlorobu tan e

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(v) Addition of water
(a) Catalyzed by HgSO4 / H2SO4

H
|
R  C  C  H  H2O RCCH
|| |
Markovnik ov rule) O H
(

ketone
( stable)

O
||
Example CH3  C  C  H  H2 O CH3  C  CH3
propyne Pr opanone (acetone )

(b) Hydroboration-oxidation

H
|
R C  C  H R C CH
| ||
 M a rk o v n ik o v ru le
H O
a n ti
Ketone or Aldehyde
(

(stable )

O
||
Example CH3  C  C  H CH3  CH2  C  H
Propyne Pr opanal

(vi) Formation of alkylide anions (alkynides)

Sodium, lithium, and magnesium alkynide
R – C  C – H + NaNH2  R – C  C:¯ +Na + NH3
R – C  C – H + R Li  R – C  CLi + R H
R – C  C – H + R MgX  R – C  CMgX + RH
Alkylation of alkylide ions
R – C  C:¯ + R – X  R – C  C – R
(R – X must be an unhindered primary halide or tosylate)
Example

CH3 CH2  C  CH :¯  Na + CH3 CH2CH2  Br  CH3 CH2  C  C  CH2CH2 CH3

Sodium butynide 1  Bromopropane Hept  3  yne
Reactions with carbonyl groups

R – C  C:¯ + 

Example

CH3  C  C :¯Na 
sodium propynide

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ix) Oxidation to -diketones
O O
|| ||
KMnO 4 , (netural)
R – C  C – R       
 R  C  C  R
(or O3 & Zn / H2O)
Example
O O
KMnO 4 , (netural) || ||
CH3  C  C  CH2 CH3       C H 3  C  C C H 2 C H 3
(or O & Zn / H O)
2  Pentyne 3 2
P en tan e  2, 3  dione

(x) Oxidative cleavage

O O
|| ||
R – C  C – R R  C  OH + HO  C  R

Example
O
(1) KMnO4 , NaOH O
( 2) H
|| ||
CH3 – C  C – CH2CH3        CH3  C  OH + HO  C  CH2CH3

(1) KMnO 4 , NaOH O

( 2) H ||
CH3CH2CH2 – C  CH        CH3 CH2 CH2  C  OH + CO2

Solved Exa mples

Example 1 :What happens when an alkane is reacted with tertiary butyl hypochlorite, (t-BuOCl) in presence of
sunlight. Explain
Solution : When an alkane is reacted with t-Bu OCl an alkyl chloride is obtained
R – H + (CH3)3 COCl R – Cl + (CH3)3 COH

Mechanism
CH3 CH3
. .
CH3 – C – O – Cl CH3 – C – O + Cl
CH3 CH3

CH3 CH3
. .
CH3 – C – O + R – H CH3 – C – O – H + R
CH3 CH3

CH3 CH3
. .
R + CH3 – C – O – Cl R – Cl + CH3 – C – O
CH3 CH3

Example 2: A certain compound “A” has a molecular formula C6H13Br. When reacts with Mg metal in anhydrous
ether, a Gringnard’s reagent is formed which upon hydrolysis with acid produces the compound n-
hexane as a product. When the compound A reacts with sodium metal in a Wurtz reaction, the product
obtained is 4, 5-diethyl octane. What is A ? Draw its structure and give its IUPAC name.
Mg H2O
Solution : 1. C6H13Br Dry ether
C6H13MgBr C6H14
H+
n-hexane

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[Link] reaction involves coupling of 2 moles of an alkyl halide to give an alkane. Since the
alkane is 4, 5-diethyloctane,
CH3 – CH2 – CH2 – CH – CH – CH2 – CH2– CH3
C2H5 C2H5

 The alkyl halide must be CH3CH2CH2CHBr C2H5 (3-Bromohexane). Thus :

Dry ether
CH3 – CH2 – CH2 – CH Br + 2Na + Br – CH – CH2 – CH2– CH3
C2H5 C2H5

CH3 – CH2– CH2 – CH – CH – CH2 – CH2 CH3

C2H5 C2H5

Example 3: a) Arrange the following compounds in order of their increasing boiling points ? n-pentane,
2-methyl pentane, n-hexane, 2,2-dimethyl pentane, ethane.
b) An unknown alkyl halide, C 4H9Br, reacts with sodium to give a hydrocarbon C 8H18. The
hydrocarbon is shown to be identical to that produced by the Kolbe’s electrolysis of the
sodium salt of the acid CH3 – CH – CH2 – COOH
CH3

What are the structures of the hydrocarbon and the alkyl halide ?
c) Give the structural formulae and names for all dibromo derivatives of propane.
Solution : a) Ethane < Pentane < 2-Methyl pentane < n-Hexane < 2, 2-Dimethyl pentane
This is because the boiling point is directly propotinal to molecular forces of attraction
which in turn being Vander Waal’s force is directly proportional to surface area.
Dry ether
b) RI + 2Na + IR R – R + 2NaI (Wurtz reaction)
Electrolysis
2RCOONa + 2H2O R – R + CO2 + 2NaOH + H2

The sodium salt of the acid, CH3 – CH – CH2 – COOH should give alkane
CH3

2H3C – CH – CH2 – COONa + 2H2O Electrolysis H3C – CH – CH2 – CH2 – CH – CH3 + 2CO2 + 2NaOH + H2
CH3 CH3 CH3

This alkane with molecular formula C 8H 18 (2, 5-dimethylhexane) can be obtained by

Wurtz synthesis by coupling 2 moles of CH3 – CH – CH2 Br (Isobutylbromide)
CH3

2CH3 – CH – CH2 Br + 2Na Dry ether CH3 – CH – CH2 – CH2 – CH – CH3 + 2NaBr
CH3 CH3 CH3
Thus the alkyl bromide C4H9Br is Isobutyl bromide (1-Bromo-2-methylpropane).
c) The two Br’s are placed first on the same carbon and then on different carbons.
Propane : CH3–CH2–CH3

(i) (ii)

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(iii) (iv)

Example 4: A 1.37 g sample of n-butyl bromide was converted to the Grignard’s reagent. What volume of butane,
measured over water at 20ºC and at 750 mm pressure will be produced on addition of water to the
Gringnard’s reagent ? Aqueous tension at 20ºC is 17.4 mm.

C4 H9Br + Mg Dry ether

Solution : C4 H9 MgBr
n-Butyl bromide Butyl magnesium bromide
1 mole

C4 H9 Mg Br + HOH C4 H10 + Mg (OH)Br

H OH Butane
1 mole (22.4 L at NTP)

Given weight of n-butyl bromide = 1.37 g

Molecular weight of n-butyl bromide = 12  4 + 1  9 + 80 = 48 + 9 + 80 = 137
m 1.37
No. of moles of n-butyl bromide = = = 0.01 mole
M 137

1 mole of n-butyl bromide gives butane = 0.01 mole

Hence volume of 0.01 mole of butane at 750 mm pressure and temperature 293 K = PV = nRT
nRT
 V=
P
732 .6
n = 0.01, R = 0.082, P = (750 – 17.4) = 732.6 mm = 760 atm., 293K

0.01  0.082  293  760

 = 0.24934 litre = 249.24 ml.
732.6
Example 5: Suggest a mechanism for the dehydration of CH3CHOHCH3 that proceeds through a carbenium ion
intermediate. Assign a catalytic role to the acid and keep in mind that the O in ROH is a basic site
like O in H2O. H3C CH CH3 CH3 - CH - CH3
Solution : OH
.. + OH 2
O
H - O - S - OH
O

Slow 
CH3 - CH - CH 3 CH3 - CH - CH 3
Carbocation
 OH2


CH3 - CH - CH2 CH3 - CH = CH 2

H
_
..
HSO4

H2SO4 act as an acid in first step and base in third step. Since it is regenerated back it is acting as a catalyst.
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Example 6:List the possible products, in order of decreasing yield, from the reaction of 3-bromo –2,3 –
dimethyl pentane with alcoholic KOH.

CH3 CH 3
alc. KOH 
CH 3––CH2––C–––CH––CH3
Solution : –HBr
Br

CH3 CH 3
CH3 ––CH 2––C = C––CH3 (A) CH2
Tetra alkyl substituted CH3
CH3 ––CH 2––C––CH (C)
CH3
CH 3 CH3 Dialkyl substituted
CH3 ––CH = C––CH––CH3 (B) yield A > B > C
trialkyl substituted

According to saytzeff rule, more substituted alkene is more stable.

Example 7 : Account for the formation of both 3 – bromo –2,2– dimethyl butane and 2–bromo –2,3
dimethyl butane from the reaction of HBr with 2,3–dimethyl –1- butene.

Solution :
CH3 CH3
Markonikov addition
CH 3––C––CH = CH2 + HBr H 3C — C — CH — CH 3

CH 3 CH3 Br

3 – bromo –2,2 – dimethyl butane.

The reaction step are
CH 3 CH 3

CH 3C — C — CH = CH2 + H + + methanide
H3 C — C — CH — CH3 migration

CH 3 CH 3

CH3 CH 3 CH3
CH 3 +
C–– CH –– CH3 + Br– H3C –– C –– CH –– CH3
H 3C
Br
2- bromo –2,3 - dimethylbutane

The addition of HBr to some alkene gives a mixture of expected alkyl bromide and an isomer
formed by rearrangement of carbocation

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Examples 8 : One mole of a hydrocarbon (A) reacts with one mole of bromine giving a dibromo compound
C5H10Br2 (B). Substance (A) on treatment with cold, dilute alkaline KMnO4 solution forms a
compound C5H12O2(C). On ozonolysis (A) gives equimolar quantities of propanone and
ethanal. Deduce the structural formula of (A), (B) & (C)
A 
i ) O3
 Propanone + ethanal
ii ) H 2

So A is
H 3C

H 3C CH3
2-methylbut-2-ene

H3C Br CH3

+ Br2 H 3C
H3C CH3 Br (B)
CH3
2-methylbut-2-ene
2,3-dibromo-2-methylbutane

H3C OH OH

+ alk. KMnO4 H3 C

H3C CH3 CH3 CH3 (C)

2-methylbutane-2,3-diol

Examples 9 : An unsaturated hydrocarbon A (C6H10) readily gives B on treatment with NaNH2 in liquid
NH3. When B is allowed to react with 1-chloropropane a compound C is obtained. On partial
hydrocarbon in the presence of Lindlar catalyst, compound C gives D (C9H18). On ozonolysis
D gives 2, 2-dimethyl propanal and 1-butanal. With proper reasoning give the structures of A,
B, C and D.
CH3 CH3
H3C
- +
H3 C C Na
Solution : A= H C B=
3
CH3
H

CH3 CH3
H3C
H3C
C= D= CH3
CH3 CH3 H3C

since A readily reacts with NaNH2 and has got 2o unsaturation so it can be a terminal alkyne.
D is an alkene obtained by controlled reduction.

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Examples # 10: There are six different alkenes A, B, C, D, E and F. Each on addition of one mole of
hydrogen gives G which is the lowest molecular wt. hydrocarbon containing only one
asymmetric carbon atom. None of the above alkene give acetone as a product on
ozonolysis. Give the structures of A to F. Identity the alkenes that is likely to give a
ketone containing more than five carbon atoms on treatment with a warm
concentrated solution of alkaline KMnO4. Show various configurations of G in fisher
projection.

Solution : The 6 different alkenes (A) to (F) are :

C H3
CH 3

A= B=
C H3 CH 3
H2 C H3C

CH 3
CH2

C= D=
CH 3 CH3
H 3C H3C

CH3 CH 3

E= F=
CH3 CH2
H3C H3C

H3C

H
G=
H3C
CH3

Alkene A will give ketone ( with 6 carbon) on treatment with hot. conc. alkaline KMnO4

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REACTION CHART FOR ALKANES

H , Ni
(1) R–C  CH 2  (1) X , h or UV light or 400 C
200300C 2         
 RX

or
R–CH=CH2 Sabatier senderens
reaction (2)  R-N
Nitration

ZnCu  HCl
(2) R–X   
Re d P HI , LiAlH4 (3) Sulphonation H S O
227  Alkyl Sulphonic acid
       

(3) R–Mg–X 

HOH or ROH
  
SO2 + Cl2   RSO Cl
or NH3 or RNH 2
(4) h 2

(4) RX Na
,dry ether

Wurtz reaction
AlCl / HCl
(5) 3  branched alkanes
(5) RX  Zn
 Isomerisation
Frankland's reaction R–H
or
R  C  H or RO H Pyrolysis
(6) || 
Re d P / HI
 R–R (6)  Alkenes + CH4 or C2H6
500 700 C
O
or
CnH2n+2
or Cr or Mo or V oxide
       
R CR or RCHO (7)  Al 2O3 500C Aromatic compound
||
O
CH N
22
(8)    Higher alkane
R CR step up reaction
Zn  Hg / Conc. HCl
(7) ||     

O Clemension 's reduction
O
2
(9) 
 CO2 + H2O
R C  O 
H 2 N  NH 2
(8) |   
 Combustion
R Wolf / Kishner reduction

or
(RCH2CH2)3B H O
 2

(9) RCOONa NaOH  CaO

  

(10) RCOONa Kolbe

's
electrolytic synthesis
 

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REACTION CHART FOR ALKENES

conc . H SO
(1) R–CH2–CH2–OH  24  H Ni
(1) 2, R–CH2–CH3
H2O
200300 C

(2) R–CH2–CH2–X alc

. KOH
 (2) X
2 R–CHX–CH2X
 HX
(3) HX
 R–CHX–CH3

X    R–CH=CH2
Zn dust
(3) R–CH2–CH or (4) HBr , Peroxide
X
for higher alkene
X2    R–CH2–CH2Br
C n H 2n
(5) HOCl
 R–CH(OH)–CH2Cl
R  CH  CH 2 Zn dust
(4) | |  
 dil. H SO
(6)  HO R–CH2(OH)–CH3
2 4

X X 2
1 / 2 O2
(7) Ag 
(5) R–C  CH 

Ni2B,H2 300C
200300C

RCH  COOK (8) 

CH 2 N 2

(6) | Kolbe's electrolytic synthesis
    
RCH  COOK
(9) BH
3  (RCH2CH2)3B
(7) (C2H5)4N+OH  O
 (10) 
2
CO2 + H2O

R  C  O  CH 2  CH 2  R Pyrolysis
(8) ||
 R  CH  CH 2
O (11) OS O4  | |
(9) R–H Pyrolysis OH OH


Bayer reagent R  CH  CH 2
(12)    
1% alkalineKM nO | |
4
OH OH

(13) strong R  C  OH + CO + H O
 oxidant
 || 2 2

O
Per acid
(14) Pr iles  
chalev 's reaction

O3 H 2 O , Zn
  
(15) +
Ozonolysis

Cl
(16) 
2 Substitution product
500 C

Al (SO )
(17) 200
2    Isomerisation
4 3
300 C
(18) acetic
 anhydride
 R–CH2=CH–COCH3
Methyl alkenyl ketone
(19) Alkane
  Higher alkane

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REACTION CHART FOR ALKYNESREACTION CHART FOR ALKYNES

(1) CH2Br–CH2Br alc . KOH or NaNH 2 (1) 

H2
 C2H4, C2H6
     Catalyst

(2) CH3–CHBr2 alc. KOH , NaNH (2) X

2 C2H2X4
    2 
HBr
Ag powder (3)  CH BrCH Br
(3) CHCl3    C2 H 2 3
Peroxide 2

HBr
Zn dust 
(4) No  CH –CHBr
(4) CHBr2–CHBr2  
 Peroxide 3 2

(5) HOCl
 Cl2CHCHO
CHBr
(5) || Zn (6) HCN , Ba ( CN ) 2
  2  CH2=CHCN

CHBr (7) 3    CH3CH(OCOCH3)2
CH COOH , Hg

(6) CH2=CH–Cl alc. KOH , NaNH Hg 2 , 80C , dil. H SO

    2  (8)     2 4  CH CHO
( Kucherov 's reaction ) 3
HC  COONa Kolbe's electroly tic synthesis
(7) ||        (9) Conc
 
. H 2SO 4
 CH3CH(HSO4)2
HC  COONa
AsCl
H 2O (10) Ca det 3  CHCl=CHAsCl2
(8) CaC2 
 & Bunsen reaction

electric arc,1200C C 2 H 5OH / H 2O

(9) 2C + H2     

Berthelot 's process
(11)   
HgSO
 CH CHO
3
4

i ) Na ( ii ) R X CO  HOH
(10) CH3–CCH (    (12)    CH =CH–COOH
Ni( CO ) 2
(10) CH3–CCH (i ) CH MgI (ii ) R X 4
 3   
CO  EtOH
(13)    CH =CH–COOEt
Ni ,160C 2

(14) NaNH
 2  Na–CC–Na
AgNO3  NH 4OH
(15) (     Ag–CC–Ag
Tollen 's Re agent )
(16) Cu Cl  NH OH
22 4  Cu–CC–Cu
Combustion
(17)     O2
 CO2 + H2O
CHO
(18) Bayer
 Reagent
 |  HCOOH
CHO
O
 3
(19) Ozonolysis H O

2
 HCOOH
Trimerisat ion
(20)    benzene
(Re d hot iron tube)

(21) Trimerisat
  ion  C8H8or 1,3,5,7-cyclo octa tetraene
[ Ni( CN ) 2 ]
Dimerisati on
(22)    butenyne
[ Cu ( NH 3 ) 2 ]

(23)  S


CH OH
(24)  3 
( BF  HgO )
methylal
3

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Home Assignment- 1

1. 
R
 , Regent R can be

(A) LiAlH4 (B) H2 / Ni (C) NaBH4 (D) H2 / Pd / CaCO3

2. The hydrogen attached to C-1 of Methylcyclohexane is:

(a) Primary (b) Secondary
(c) Tertiary (d) Quaternary

3. The heat of combustion per CH2 group is higher for cyclopropane than for cyclohexane
because:
(a) Angle strain and torsional strain are greater in cyclopropane than in cyclohexane.
(b) Only angle strain is greater in cyclopropane than in cyclohexane.
(c) Only torsional strain is greater in cyclopropane than in cyclohexane.
(d) The C―H bonds in cyclopropane are fully staggered but those in cyclohexane are eclipsed.

4. The number of different substitution products possible when bromine and ethane are allowed
to react is:
(a) 9 (b) 8
(c) 7 (d) 6

5. A hydrocarbon with molecular formula C8H18 gives one monochloro derivative.

The hydrocarbon is:
(a) n-octane (b) 2-Methylheptane
(c) 2,2,4-Trimethylpentane (d) 2,2,3,3-Tetramethylbutane

6. In the complete combustion of CnH2n+2, the number of moles of oxygen required per mole of
hydrocarbon is:
(a) n/2 (b) (n + 1)/2
(c) (3n + 1)/2 (d) n + 1/2

7. Bromination of an alkane as compared to chlorination proceeds

(a) at a slower rate.
(b) at a faster rate.
(c) at equal or different rate depending on the nature of alkane.
(d) with equal rate.

8. Which one of the following compounds will react with CH3MgBr in the molar ratio 1 : 2?
(a) H2O (b) CH3CCCH3
(c) HCCCH2OH (d) CH3CH2OH

9. Which of the following alkane can be obtained in good yield by the Wurtz reaction?
CH3CHCH2CH3
(a) (b) CH3CH2CH2CH3
CH3
CH3
CH3CHCH3
(c) CH3CHCH2CHCH3 (d)
CH3
CH3

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10. Which of the following reagent is used for the aromatization of nhexane?
(a) AlCl3 (b) Na in liquid NH3
(c) Cr2O3/Al2O3 with heat (d) Wilkinson’s catalyst

11. Ph3SnH can be used to reduce

CH3CH2CHCl
(a) CH3CH2CH2CH2Cl (b)
CH3
CH3

(c) CH3CCl (d) All of them

CH3

Br

12. When isobutane is brominated, the percentage of CH3CCH3 would be approximately

CH3
(a) 0% (b) 83%
(c) 10% (d) 100%

13. On heating CH3COONa with sodalime the gas evolved will be

(A) C2H 2 (B) CH4
(C) C2H 6 (D) C2H 4

14. Which of the following will have least hindered rotation about carbon-carbon bond?
(A) Ethane (B) Ethylene
(C) Acetylene (D) Hexachloro ethane

15. What is the Major product obtained when n–butane is treated with bromine in the presence of light at
130°C?
(A) CH3 – CH2 – CH2 – CH2 – Br (B) CH3 – CH2 – CH – Br
|
CH3

CH3
(C) CH3 – CH – CH2 – Br |
| (D) H3C – C – CH2Br
CH3 |
CH3

16. The product obtained on heating n-heptane with Cr2O3– Al2O3 at 600°C is
(A) Cyalohexane (B) Cyclohexane
(C) Benzene (D) Toluene

17. The treatment of C2H5MgI with water produces

(A) Methane (B) Ethane
(C) Ethanal (D) Ethanol

18. The order of reactivity of halogens towards halogenation of alkanes is

(A) F2 > Br2 > Cl2 > I2 (B) F2 > Cl2 > Br2 > I2
(C) Cl2 > F2 > Br2 > I2 (D) Cl2 > Br2 > F2 > I2

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19. The chlorination of alkane involves

(A) Cl free radicals (B) Cl+ species

(C) Cl– species (D) C H 3 carbocation

20. When n-butane is heated in the presence of AlCl3/HCl it will be converted into –
(A) Ethane (B) Propane (C) Butene (D) Isobutane

21. In the free radical chlorination of methane and tetradeuteromethane, the rate of the reaction
(A) is faster for CH4 than for CD4 (B) is faster for CD4 than for CH4
(C) is equal for both (D) for CD4 is zero

22. The catalytic hydrogenation product of which of the following would be optically active?
CH3 CH3
(A) HCCCCH2CH3 (B) H2C=CHCCH2CH3
H H
CH3 CH3
(C) CH3CH2CH2CCCCH3 (D) CH2=CHCCD=CD2
H H

23. The treatment of CH3OH with excess CH3Mgl releases 1.04 ml of a gas at STP. The mass of CH3OH
added is
(A)1.485 mg (B) 2.98 mg
(C) 3.71 mg (D) 4.47 mg

24. An unknown carboxylic acid salt on Kolbe’s electrolysis forms cyclobutane. The carboxylic acid is
(A) hexanedionic acid (B) hexanoic acid (C)butanoic acid (D) transbutenedioic acid

25. Which member of each of the following pairs would you expect to have the larger heat of combustion
(1) cis- or trans-1, 2-dimethylcyclohexane
(2) cis- or trans-1, 3-dimethylcyclohexane
(3) cis- or trans-1, 4-dimethylcyclohexane.
(a) (1) cis-isomer > trans-isomer, (2) cis-isomer < trans-isomer, (3) cis-isomer > trans-isomer
(b) (1) cis-isomer < trans-isomer, (2) cis-isomer < trans-isomer, (3) cis-isomer > trans-isomer
(c) (1) cis-isomer > trans-isomer, (2) cis-isomer > trans-isomer, (3) cis-isomer > trans-isomer
(d) (1) cis-isomer < trans-isomer, (2) cis-isomer > trans-isomer, (3) cis-isomer > trans-isomer

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Home Assignment- 2

1. Reaction of Br2 with ethylene in presence of NaCl will mainly give:

(a) BrCH2CH2Br (b) ClCH2CH2Br
(c) ClCH2CH2Cl (d) NaCH = CHNa

2. When propylene is treated with chlorine at 500C, allyl chloride is formed as the main product.
Mechanism of the reaction is:
(a) Free radical addition. (b) Free radical substitution.
(c) Electrophilic substitution. (d) Nucleophilic substitution.

3. Ethene can be prepared by dehydration of ethanol. Which of the following conditions will not
favour the formation of ethene?
(a) Large amount of ethanol (b) Large amount of H2SO4
(c) High temperature (d) none of these

4. A hydrocarbon (C5H8) can not have

(a) two double bonds. (b) one double bond.
(c) one triple bond. (d) double as well as triple bond.

5. Identify the product formed on addition of excess HOCl to propyne.

(a) CH3COCHCl2 (b) CH3COCH2Cl
(c) CH3CH(OH)CHCl2 (d) CH3C(OH)2CHCl2

6. Longest carbon carbon single bond will be in:

(a) CH3CH=CH2 (b) CH2=CHCH=CH2
(c) CH3CH2CH3 (d) equal in all

7. The order of stability of three alkenes R2C=CR2, R2C=CHR and RHC=CHR is

(a) RCH=CHR > R2C=CHR > R2C=CR2 (b) RCH=CHR < R2C=CHR > R2C=CR2
(c) RHC=CHR > R2C=CHR < R2C=CR2 (d) RHC=CHR < R2C=CHR < R2C=CR2

8. The dehydrohalogenation of 2bromobutane with alcoholic KOH gives

(a) only 2butene (b) only 1butene
(c) 2butene as the major product (d) 1butene as the major product

Catalyst
9. 2 - butene Optical isomers for the product formed will be
H2

(a) 2 (b) 4
(c) Zero (d) 3

10. The compound (CH3)2CHCH(Cl)CH3 reacts with alcoholic KOH to give the alkene
(a) (CH3)2CHCH=CH2 (b) CH3CH=C=CH2
(c) CH3CH2CH=CHCH3 (d) (CH3)2C=CHCH3

11. Which of the following alkene will react fastest with H2 under catalytic hydrogenation conditions?

R H R H

(a) (b)
H H R H

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R R R R

(c) (d)
R H R R

12. Which of the following compound on ozonolysis followed by oxidative hydrolysis yields propane
1, 3dioic acid (malonic acid) as the only product?
(a) CH2=CHCH2CH=CH2 (b) CH2=CHCH=CH2

(c) CH3 (d)

13. Propene can be converted into 1propanol by oxidation. Which set of the reagents is used to
effect the conversion?
(a) OsO4CHCl3 (b) O3 / ZnH2O
(c) Alkaline and cold KMnO4 (d) B2H6 and alkaline H2O2

H3C CH2OH
14. The major product obtained in the acid catalysed dehydration of would be H2SO4

is

CH3 CH3 CH2

CH3
CH3 CH2
(a) (b) (c) (d)

15. What is (B) in the following sequence of reactions?

O
P(Ph)3 nC4H9Li
CH3CCH2CH2CH2CH2Br (A) (B)

CH3 CH2

(a) (b)

O
(c) CH3CH=CHCH2CH2CH3 (d)
CH3CCH2CH2CH2C4H9

16. Of the following compounds, which one will have zero dipole moment?
(a) 1, 1dichloroethylene (b) cis1, 2dichloroethylene
(c) trans1, 2dichloroethylene (d) none of these

17. 1Chlorobutane on heating with alcoholic potash gives

(a) 1butene (b) 1butanol
(c) 2butene (d) 2butanol

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CH2 OH

18. When is heated with conc. H2SO4 at 443 K , the alkene formed is mainly

(A) (B) (C) (D)

19. Rate of hydrogenation of the following alkenes is in the order :-

(A) II > IV > III > I (B) IV > II > III > I (C) IV > II > I > III (D) IV > I > II > III

20. Reactivity order towards electrophilic addition of the following alkenes is

(A) IV < III < I > II (B) IV > III > I > II (C) IV > I > III > II (D) IV > I > II > III

21. Rate of hydration of the following alkenes is

(A) I > II > III > IV (B) I < II < III < IV (C) I > IV > III > II (D) I > IV > II > III

22. Rate of hydrohalogenation of the following alkenes is

(A) I > III > II > IV (B) II > I > III > IV
(C) II > I > IV > III (D) I > II > IV > III

23. Match the relative reactivity of the following alkenes towards bromine in methanol solution.

Compound Rela tive Rate

I . (CH3)2C = CH2 a. 6.0 × 103

II. CH2 = CH2 b. 1.0

III. (CH3)2 C = CHCH3 c. 3.0 × 101

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I II III
(A) a b c
(B) b a c
(C) c b a
(D) b c a

24. Which is the major product in the following?

CH2Br

..
Et3N

CH2

(a) (b) (c) (d)

25. Dehydration takes place to a maximum extent in:

O O

OH
(a) (b)
OH

O
CHO

(c) (d)
OH
OH

26. Major product of the dehydration of the following is

 CH 3 3 CCHCH 3
OH

 CH 3 2 CHC  CH 2
(a) (CH3)3CCH=CH2 (b)
CH 3

(c)  CH 3 2 C  C  CH 3 2 (d) CH 3CH 2CH  CHCH 2CH 3

27. In the following reaction A is.

CH3
H Br NaI/acetone


H Br Major product , major product is :
CH3

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H CH3 H CH3

( a) (b)
H CH3 H3C H

(c) both of these (d) none of these

28. p-2 catalyst consists of :

(a) nickel boride (b) palladium/carbon
(c) both of these (d) none of these

29. Reagent used to carry out following alkyne to alkene is:

?


CH 2C  CCH 3 H
CH2
C C
H CH3

(a) Pd-C/H2 (b) Na/NH3

(c) P-2/H2 (d) Ni/H2

A
30. 

A can be –
(A) Conc. H2SO4 (B) alcoholic KOH (C) Et3N (D) t-BuOK

Home Assignment- 3

1. An alkene of molecular formula C4H8, having zero dipole moment, on treatment with cold
aqueous KMnO4 gives :
(a) optically inactive non resolable solution
(b) optically inactive resolvable solution.
(c) optically active non resolvable solution.
(d) optically active resolvable solution.

2. The addition of Br2 to cis2butene produces

(a) (+)2, 3dibromobutane only (b) ()2, 3dibromobutane only
(c) (  ) 2, 3dibromobutane (d) meso2, 3dibromobutane

3. The addition of HI in the presence of peroxide does not follow antiMarkovnikov’s rule because
(a) HI bond is too strong to be broken homolytically.
(b) reaction of I radical with alkene is endothermic in nature.
(c) I combines with H to give back HI.
(d) HI is a reducing agent

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CH3C=CHCH3
4. The treatment of with hot acidic KMnO4 produces
CH3
(a) CH3COCH3 + CH2O (b) CH3COCH3 + CH3COOH
(c) CH3CHO + CO2 (d) CH3COCH3 only

5. An optically active carboxylic acid, (X) has the molecular formula C6H10O2 and can be shown
by chemical and physical tests to contain the group CH=CH2 and at least one alkyl group.
When (X) is reduced with hydrogen over platinum, the product formed is optically inactive.
Which of the following best represents the structure of (X)?
(a) CH2=CHCH(CH3)CH2COOH (b) CH2=CHCH(CH2CH3)COOH
(c) CH2=CHCH2CH(CH3)COOH (d) CH2=CHC(CH3)2COOH

6. The order of reactivity of the following alkenes towards electrophilic attack is

H3C
(i) CH3CH=CH2 (ii) CH2=CHCOOH (iii) CH2=CH2 (iv) CH2
H3C
(a) (i) > (iii) > (iv) > (ii) (b) (i) > (iii) > (ii) > (iv)
(c) (iv) > (i) > (iii) > (ii) (d) (i) > (iv) > (iii) > (ii)

7. The major product of reaction of pure HBr with pure propene is

(a) 1bromopropane (b) 2bromopropane
(c) 3bromopropane (d) none of these

8. The reaction of 2methylpropene with hypochlorous acid gives

(CH3)2C CH2
(a) (CH3)2C(Cl)CH2OH (b) CH2

(c) (CH3)2C(OH)CH2Cl (d) (CH3)2C(OH)CH2OH

9. In the reaction of Br2 in the presence of sodium iodide with ethylene, what products would be
found in the reaction mixture?
(a) 1,2dibromoethane only
(b) 1,2dibromoethane and 1,2diiodoethane
(c) 1bromo2iodoethane and 1,2dibromoethane
(d) 1,2diiodoethane

10. The compound most likely to decolourize a solution of potassium permanganate is

(a) CH3CH3 (b)

CH3

(c) CH3CH=CHCH2CH3 (d) CH3CCH3

CH3
11. At low temperatures, the slow addition of molecular bromine to CH2=CHCH2CCH gives
(a) CH2=CHCH2CBr=CHBr (b) BrCH2CHBrCH2CCH
(c) CH2=CHCH2CH2CBr3 (d) CH3CBr2CH2CCH

12. CH2=CHCl reacts with HCl to form

(a) CH2ClCH2Cl (b) CH3CHCl2
(c) CH2=[Link] (d) None of these

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13. The predominant product formed, when 3methyl2pentene reacts with HOCl, is
Cl OH Cl Cl

(a) CH3CH2C CHCH3 (b) CH3CH2C CHCH3

CH3 CH3

OH CH3 OH

(c) CH3CH2C CHCH3 (d) CH3C CHCH3

CH3 Cl CH3

14. The product of following reaction is

CH3
(i) Hg(OAc)2 ; H2O
CH3CCH=CH2
(ii) NaBH4
CH3

CH3 CH3

(a) CH3C CHCH3 (b) CH3CCH2CH2OH

CH3 OH CH3

OH CH3 CH3

(c) CH3C CHCH3 (d) HOCH2CCH2CH3

CH3 CH3
15. Addition of HI on the double bond of propene yields isopropyl iodide and not npropyl iodide as
the major product. This is because the major product formation proceeds through
(a) more stable carbocation.
(b) more stable carbanion.
(c) more stable free radical.
(d) none of the above being a concerted reaction.

16. The product of acid catalyzed hydration of 2phenyl propene is

(a) 3phenyl -2propanol (b) 1phenyl2propanol
(c) 2phenyl2propanol (d) 2phenyl1propanol

17. 3Phenylpropene on reaction with HBr gives (as a major product)

(a) C6H5CH2CH(Br)CH3 (b) C6H5CH(Br)CH2CH3
(c) C6H5CH2CH2CH2Br (d) C6H5CH(Br)CH=CH2

18. Cyclohexene on reaction with OsO4 followed by reaction with NaHSO3 gives
(a) cisdiol (b) transdiol
(c) epoxide (d) alcohol

19. A hydrocarbon of formula C6H10 absorbs only one molecule of H2 upon catalytic hydrogenation.
Upon ozonolysis, the hydrocarbon yields
H H
O=CCH2CH2CH2CH2C=O
The hydrocarbon is
(a) cyclohexane (b) benzene
(c) cyclohexene (d) cyclobutane

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20. In methanol solution, bromine reacts with ethylene to yield BrCH2CH2OCH3 and
1, 2dibromoethane because
(a) intermediate bromonium ion may react with Br or CH3OH.
(b) methyl alcohol solvates bromine.
(c) reaction follows Markownikoff’s rule.
(d) this is a free radical mechanism.

21. In the addition of HBr to propene in the absence of peroxides, the first step involves the addition of
(a) H+ (b) Br
(c) H° (d) Br+

22. The olefin, which on ozonolysis gives CH3CH2CHO and CH3CHO?

(a) But1ene (b) But2ene
(c) Pent1ene (d) Pent2ene

23. Rate of addition of halogen acid (HX) is least in

(a) CH2=CHCl (b) CH2=CH2
(c) CH3CH=CH2 (d) (CH3)2C=CH2

24. The product formed by the action of chlorine on ethene in saturated solution of KBr is/are
(a) ClCH2CH2Cl + ClCH2CH2CH2Br (b) ClCH2CH2Cl
(c) ClCH2CH2Cl + BrCH2CH2Cl (d) ClCH2CH2Cl + BrCH2CH2Br

25. The reaction of propene with HOCl proceeds via the addition of
(a) H+ in the first step (b) Cl+ in the first step

(c) OH in the first step (d) Cl and OH in a single step

26. Major product of the reaction,

CH3
D2O/D+
CH3CCH=CH2
CH3
would be
CH3 CH3 CH3
(a) CH3  C  CH  CH2D (b) CH3  C  CH  CH2D
H3C OD OD

CH3 H CH3

(c) CH3  C  C  CH3 (d) H3C  C  CH  CH2

OD D H 3C D OD
27. AntiMarkownikoff’s addition of HBr is not observed in
(a) propene (b) 1butene
(c) 2butene (d) 2pentene

28. Addition of one equivalent of bromine to 1, 3–pentadiene produces

(A) 1, 3–pentadiene (B) 4, 5–dibromo–2–pentene
(C) 3, 4–dibromopentene (D) 1, 4–dibromo–2–pentene

29. The ozonolysis of an olefin gives only propanone. The olefin is

(A) propene (B) but–1–ene
(C) but–2–ene (D) 2, 3–dimethylbut–2–ene

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30. The treatment of CH3C = CH2
|
CH3
with boiling KMnO4 produces
(A) CH3COCH3 + CH2O (B) CH3CHO + CH3CHO
(C) CH3COCH3 + CO2 (D) CH3COCH3 + HCOOH

31. Point out (A) in the given reaction sequence:


( A) 
O3 / H 2O
( B)   2CH 3COOH  2CO2

(A) (B)

(C) (D)

Ozonolysis of will give

32.

O
(A) 2 (B) O

O
O

(C) (D)
2

33.
CH3 – CH – CH = CH2 + HBr  A (predominant), A is
|
CH3
CH3 – CH – CH – CH3 CH3 – CH – CH2 – CH2Br
(A) | | (B) |
CH3 Br CH3

Br
|
CH3 – C – CH2 – CH3
(C) | (D) None is correct
CH3

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CH3
|
H–C
|| alkaline KMnO 4
  A
34. H–C
|
CH3
(cis)
Which is true about this reaction?
(A) A is meso 2, 3-butan-di-ol formed by syn addition
(B) A is meso 1, 2-butan-di-ol fomred by anti addition
(C) A is a racemic mixture of 1, 2-butan-di-ol formed by anti addition
(D) A is a racemic mixture of 1, 2-butan-di-ol formed by syn addition

CH3
2-butene + Br2  H Br and enantiomer. 2-butene is
Br H
35. CH3
(by anti addition)

(A) cis (B) trans (C) both (D) none

36. (A) cis-2-butene 

HCO3 H ( aq ) I
(B) trans-2-butene 
HCO3 H ( aq ) II
Correct statements are
(A) is racemic mixture by anti addition
(B) II is meso compound by anti addition & I is recemic mixture by Syn addition
(C) I is meso compound by syn addition & II is recemic mixture by anti addition
(D) II is racemic compound by anti addition

37. dil. H SO
 2 4  A, structure of A is :-

(A) (B)

(C) (D)

38. HBr / R O
  2 
2
 A, structure of A is :-

(A) (B) (C) (D)

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39.

(A) (B)

(C) (D)

40. Arrange in decreasing order of reactivity with HCl

(A) I < III < II (B) III > II > I

(C) III > I > II (D) none of the above

Home Assignment- 4

Re d hot
1. 3CH3 – C  CH  
 A , Structure of A is
Cu tube

(A) (B) (C) (D)

NaNH 2 / NH3 (liq.) CH3 CH2 Br Li, NH (liq)

2. CH3CH2C  CH          3
(A) CH3CH2CH = CHCH3 (B) CH3CH2CH = CH2

(C) (D)

Na / liq. NH
3. CH3CH2CH2CHO + CH3C  CH    
3
 A , Structure of A is

(A) CH3 CH2 CH2CHC  CCH3 (B) CH3 CH2 CH  CH2 C  C CH3
| |
OH OH

(C) CH2  CH2 CH2CH  CCH3 (D) CH 3CH 2 CH 2C H 2 C  CHCH 3

| |
OH OH

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1. excess NaNH , NH
BrCH 2CHCH2 CH2CHCH2Br          A , Structure of A is
2 3
4.
2. H2O
| |
Br Br

(A) H – C  C – CH2 – CH2 – C  C – H (B) H – C  C – C  C – H

(C) H – C  C – CH2 – C  C – H (D) H – C  C – H

5. Which of the following pair can not be distinguished by quantitative catalytic hydrogenation.
(A) But-1-ene, But-1-yne (B) Cyclohexane, Cyclohexene
(C) But-1-yne, Buta 1, 3-diene (D) But-1-ene, But-2-yne

O
||
(i) CF3  COOH (1eq.)
6.    

 
 A , Structure of A is
(ii) H3O

(A) (B)

(C) (D)

BH , THF H O / OH ¯
3
7. CH3CH2CH2C  CH   2 2  
 A , Structure of A is
(A) CH3CH2CH2CH2 – CHO (B) C H 3 C H 2 C H 2 C C H 3
||
O

(C) CH3CH2CH2CHO (D) CH3 CH2C  CH2CH3

||
O

Cl / H O 18
NaO H
8. 2 
2
 W   
 X.
( excess )

(A) W is (B) W is

(C) X is (D)

9. Which is the most suitable reagent among the following to distinguish compound (3) from rest of the com-
pounds ?
1. CH3 – C  C – CH3 2. CH3 – CH2 – CH2 – CH3
3. CH3 – CH2 – C  CH 4. CH3 – CH = CH2
(A) Bromine in carbon tetrachloride (B) Bromine in acetic acid
(C) Alk. KMnO4 (D) Amoniacal silver nitrate

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BuLi CH I Hg2 / H O
12. CH3CH2CH2-C  CH  X  

3 
Y  
3
 Z + W
Which is incorrect about products :
(A) X is (B) Y is CH3 – (CH2)2 – C  C – CH3
(C) Z is CH3  (CH2 )2  C  CH2  CH3 (D) X is CH3  (CH2 )2  C  CH3
|| ||
O O

n  C H Br
13. n – C13H27C  CH + n – C4H9Li  (A) (C15H27Li)  817 (B) (C23H44)

(C) C23H46
Which is incorrect about products :

(A) C is (B) C is

(C) B is n-C13H27C  C – C8H17 (D) A is n-C13H27C  CLi

1. NaNH H
CH3C  CH    (A)   2 (B) .Which is correct about product?
2
14.
2. CH3CH2Br Lindlar 's catalyst

(A) A is H – C  C – CH2 – CH2 – CH3 (B) A is C H 3 - C C CH3

Et
CH3
(C) B is (D) B is C C
H H

15. S T. Which is correct about product?

C C.. Na+
(A) S is (B) S is

(C) T is (D) T is

H O, H SO / HgSO [O]
16. CH  CH 2 2 
4
  4
 (A)  (B), Which correct about product?
(A) A is CH3COOH (B) A is CH3CH2OH (C) B is CH3CHO (D) B is CH3COOH

CC
17. B 
Na / NH 3

  H2
Lindlar ' s catalyst
A. A and B are:

(a) in both cases (b) in both cases

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(c) A is I, B is II (d) A is II, B is I

Li / NH 3
18. C  C C  C A ; A is:

(a)

(b)

(c) both are correct (d) none is correct

19. The product of reaction between one mole of acetylene and two mole of HCHO in the presence of
Cu2Cl2 will be -
(A) HOCH2 – C  C – CH2OH (B) H2C = CH – C  C – CH2OH
(C) HC  C – CH2OH (D) None of these

B   R–CC–R Na

Lindlar / NH
20. catalyst  3  A
A and B are geometrical isomers (R–CH=CH–R) –
(A) A is trans, B is cis (B) A and B both are cis
(C) A and B both are trans (D) A is cis, B is trans

21. An alkyne C7H12 on reaction with alk. KMnO4 and subsequent acidification with HCl yields a mixture of
CH 3  CHCOOH
| + CH3CH2COOH. The alkyne is –
CH 3
(A) 3–Hexyne (B) 2–Methyl–3–hexyne
(C) 2–Methyl–2–hexyne (D) 2–Methyl–2–hexene

22. A compound (C5H8) reacts with ammonical AgNO3 to give a white precipitate and reacts with excess of
KMnO4 solution to give (CH3)2CH–COOH. The compound is –
(A) CH2=CH–CH=CH–CH3 (B) (CH3)2CH–CCH
(C) CH3(CH2)2CCH (D) (CH3)2C=C=CH2

23. Which of the following reagents cannot be used to locate the position of triple bond in CH3–CC–CH3
(A) Br2 (B) O3 (C) Cu 22 (D) KMnO4

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24. CH3–CH2–CCH CH3CC–CH3

A and B are –
(A) alcoholic KOH and NaNH2 (B) NaNH2 and alcoholic KOH
(C) NaNH2 and Lindlar (D) Lindlar and NaNH2

BH THF
25. B  3
 CH3–CCH HgSO / H SO
 4 24  A
H O OH 
2 2,

A and B are –
O O
|| ||
(A) CH 3CH 2CHO, CH 3  C  CH 3 (B) CH 3  C  CH 3 CH 3CH 2CHO

(C) CH3CH2CHO (both) (D) CH 3  C  CH 3 (both)

||
O
NH Cl
26. CHCH Cu
 4 product
Cl 2 2

Product is –
(A) Cu–CC–Cu (B) CH2=CH–CCH (C) CHC–Cu (D) Cu–CC–NH4

27. Which reagent is the most useful for distinguishing compound I from the rest of the compounds
CH3CH2CCH CH3CCCH3 CH3CH2 CH2CH3 CH3CH=CH2
I II III IV
(A) alk. KMnO4 (B) Br2/CCl4 (C) Br2/CH3COOH (D) Ammonical AgNO3
28. Ammonical AgNO3 reacts with acetylene to form:
(A) Silver acetate (B) Silver acetylide
(C) Silver formate (D) Silver metal

29. The product obtained via oxymercuration (HgSO4 + H2SO4) of 1-butyne would be
H3C
CH 3
(a) (b) H C O
3
O

O
H3 C
+ HCO2 H
O
(c) H C + CH2O (d)
3
OH

30. A mixture of methane, ethylene, ethyne gases is passed through a Woulfe’s bottle containing ammoniacal
AgNO3. The gas not coming out from bottle is
(A) Methane (B) Ethyne
(C) Ethelene (D) All

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M iscella neous Exer cise

Objective Type questions ( Single choice)

1. F3C – CH = CH2 + HCl 

H
|
(A) F3 C  C  CH3 (B) F3C – CH2 – CH3 (C) F3 C  CH  CH2 (D) F3CCH2CH2Cl
| | |
Cl Cl Cl

2. CH3  CH  CH  CH2
|
Br
(A )
(1, 2  addition)
Both the major product Aand B are
(A) Kinetically controlled product (B) Thermodynamically controlled product
(C) Both (D) A is kinetically, B is thermodynamically controlled

(1) HBr (2moles ) ( 2) Zn

3.  A   B
     
R 2O 2 Ether

(A) A is (B) A is (C) B is (D) B is

Br

Bayer 's reagent

4.        A, Structure of A is
dil (cold KMnO )
4

CH3
CH3
OH
OH
(A) (B) (C) H
(D)
CH3
OH H

5. A, Structure of A is

(A) (B) (C) (D)

6. A, Structure of A is

(A) (B) (C) (D)

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7. CH N A, Structure of A is
 
2 2

(A) (B) (C) (D)

(1) BH
8.  
3
 A, Structure of A is
( 2 ) H2O 2 , OH ¯

(A) (B) (C) (D)

(1) BH , THF
9.  3
 A, Structure of A is
(2) H O , OH¯
2 2

(A) (B)

(C) (D)

(i) Hg(OAc)2/H 2O
10. CH3 – CH – CH = CH2 (ii) NaBH4 /  A, Structure of A is
|
CH3

OH H OH
| | |
(A) CH3  C  CH2  CH3 (B) CH3  C  C  CH3
| | |
CH3 CH3H

H H H
| | |
(C) CH3  C  CH2  CH2  OH (D) HOCH2  C  C  CH3
| | |
CH3 CH3H

(1) Hg(OAc) / THF  H O

11. 
2 2
 A, Structure of A is
( 2 ) NaBH4 / 

(A) (B) (C) (D) all of these

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12. A, Structure of A is

(A) (B) (C) (D)

CHBr
13.  
3

 A, Structure of A is
t BuO ¯ K

(A) (B) (C) (D)

14. The product of the following reaction would be :

(A) (B)

(C) (D)

15. Rate of addition of Cl2 / H2O of the following alkenes is

(A) IV > III > I > II (B) IV > III > II > I (C) I > II > III > IV (D) I > II > IV > III

16. Which of the following can give H2 on reaction with Na

(A) 1 - butyne (B) 2 - butyne (C) 1 ,3- butadiene (D) butene

17. An unknown compound decolorizes bromine in carbon tetrachloride, and it undergoes catalytic reduction to
give deccalin. When treated with warm, connected potassium permangate, this compound give cis–cyclohex-
ane–1,2–dicaboxylic acid and oxalic acid. Propose a structure for the unknown.

(A) (B) (C) (D)

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18. Write the products of the following reaction :

(A) A = (B) A is (C) B is (D) B is

19. Product formed in the following reaction:

CH3 H
+ Br2
CH3 H

(A) is a racemic mixture (B) is a meso compound

(C) is a achiral compound (D) none is correct.

20. Which is the incorrect reaction?

OH


KMaO4 / KOH
  
1) HCO3 H

. . 2) H O 
(a) (b) 3

HO
OH OH

OH
H3C H CH3
H OH


1)OSO4
2) NaHSO3 

KMnO4 / OH

(c) (d) H OH
H3C H CH3
OH

21. Consider following reaction:

CHO
A  (CH 3 )2 CO  HCHO 
O3 / Zn . H2 O

CHO
Thus, A is:
(a) (CH3)2CHCH = CHCH = CH2 (b) (CH3)2C = CHCH = CH2
(c) CH3CH = CHCH = CHCH = CH2 (d) none of the above

22. Consider following reaction:

O OH

Alkene (A)  .

KMnO4
 A is:
. O

(a) (b)

(c) (d)

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OH
CH 2Cl2
23.  Br2 A , A is:

Br Br
OH
Br
OH
OH O
(a) Br (b) (c) (d)

Br

24. Limonene (A) is a naturally occurring C10H16 hydrocarbon that causes the odour of lemons
(a “citrus” smell). When treated with excess hydrogen in the presence of platinum catalyst, it
takes up two equivalents of hydrogen. When treated with ozone, followed by zinc in acetic
acid, it forms one mole of formaldehyde (C) and one mole of tricarbonyl compound (B) .shown below.

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O O

1. O3  HCHO
Limonene
(C )
( A) 2. Zn, AcOH H

O
( B)

Propose a suitable structure for limonene if it has one six membered ring:

(a) (b)

(c) (d)

H H

BH / THF H O
B HO/ OH

3
25.  
3
 A
2 2

A and B are –

CH3
(A) Both (B) Both OH

CH 2 OH CH3 CH3 CH 2 OH
(C) OH
(D) OH

26. Dehydration of 2, 2, 3, 4, 4–pentamethyl–3–pentanol gave two alkenes Xand Y. The ozonolysis products
of X and Y are -
O
||
(A) X gives (CH 3 )3 C  C  CH 2  C(CH 3 )3 and HCHO

O
||
Y gives CH 3  C  CH 2  C(CH 3 )3 and HCHO

O
||
(B) X gives (CH 3 )3 C  C  C(CH 3 )3 and HCHO

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O CH 3
Y gives || | and HCHO
CH 3  C  C  C(CH 3 )3
|
CH 3

O
||
(C) X gives (CH 3 )3 C  C  CH (CH 3 ) 2 and HCHO

O
||
Y gives (CH 3 )  CH 2  C  C(CH 3 )3 and CH3CH2CHO
(D) None of these

O
||
27. Alkene A O
3 / H2O
 CH 3  C  CH 3 + CH3COOH + CH 3  C  COOH
||
O
A can be –
C(CH 3 ) 2
||
(A) (B) CH 3  C  CH  HC  CH 3
(C) Both correct (D) None is correct

reagent R reagent R
28.   2  1 

R1 and R2 are –
(A) Cold alkaline KMnO4, OsO4/H2O2 (B) Cold alkaline KMnO4, HCO3H + H3O+
(C) Cold alkaline KMnO4, CH3–O–O–CH3 (D) C6H5CO3H, HCO3H

SUBJECTI VE TYPE

1. (a) How many structural isomers can be drawn for C7H16? Draw the structures and give their IUPAC
names.
(b) C6H12(X) does not give Br2/CCl4 test. How many cyclic isomers (only structural ) can be drawn for
the compound? Draw their structures and give their IUPAC names.

2. (a) An alkane with the formula C6H14 can be synthesized by treating (in separate reactions) five different
alkyl halides (C6H13X) with TPH (triphenyl tin hydride). Give the structure of the alkane and the
structures of the alkyl halides.
(b) An alkane with the formula C6H14 can be prepared by reduction (with Zn and HCl) of only two alkyl
chlorides (C6H13Cl) and by the hydrogenation of only two alkenes (C6H12). Write the structure of this
alkane, give its IUPAC name, and show the reactions.

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3. A hydrocarbon (A) was found to have vapour density 36. It forms only a single monochloro substitution
product. Suggest the structure of (A)?

4. h
Write mechanism for the halogenation of methane depicted as CH4 + X2  CH3X + HX.

5. Calculate the relative amounts of 1 and 2bromopropane obtained from bromination of propane. The
reactivity of 1°, 2° and 3° hydrogen in bromination is 1 : 82 : 1600.
6. Hydrocarbon (A) reacts with Br2 by substitution to give an alkyl bromide (B). By the
Wurtz reaction (B) yields a gaseous hydrocarbon (C), which has a specific gravity of 0.94
compared to oxygen. Identify compounds (A), (B) and (C).

7. Identify (A) and (B) in the following reactions.

h (i) Mg/Ether
CH 3CH 2CH2CH3 + Br2 (A) (B)
(ii) D2O

8. Complete the reaction sequence

t  BuOK PhC CPh AgNO
(a) PhCHCl 2   A    B  
3C

H / Lindar's CH l
(b) C 2 H 5  C  C  CH 3 2Catalyst
  E  22  F
Zn (Cu )

9. A hydrocarbon (A) having molecular formula C8H14 exists in three diastereoisomeric forms, of which
one is optically active while other two are optically inactive. All the three forms of (A) absorbs two
moles of H2 to produce (B) of molecular formula C8H18, which is optically inactive. All the three forms
of (A)has the same length of carbon chain and position of multiple bonds. None of the form of (A)
either gives white ppt with Ammonical AgNO3 or reacts with H2 in the presence of Lindlar’s catalyst.
Identify the three forms of (A) and also (B).

GET EQUI PPED FOR I I T JEE


Con . H SO O 3 / H 2O / Zn
1. + CH3MgBr H A  24  B 
3O   C
A, B and C are –
A B C

CH3

(A) O
CHO

(B) HCHO

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(C)

CH3

(D) O
COOH

x
2. CH3–CH=CH–CH3   product is Y (non–resolvable) then X can be –
cis
(A) Br2 water (B) HCO3H followed by H3O+
(C) Cold alkaline KMnO4 (D) all of the above

3. Electrophilic addition reaction is not shown by

(A) CH 2  C  CH 3 and Br2 (B) CHCH and HO–Cl
|
CH 3

(C) CH3–CCH and CH3MgBr (D) HC  CH and Cl2

4. CH3CH=CH2 1)B
2D6
 product X
2)H2O2 /OH

X is –
(A) CH 3  CH  CH 2 D (B) CH 3  CH  CH 2OH
| |
OH D

(C) CH 3  CH  CH 3 (D) none is correct

|
OD

5. (CH3)3CCl 
[Link]

 A 
CF3CO 3H
 B identify B -
O
CH3
(A) CH2 = CH - CH2 OH (B) C CH2
CH3
(B) CH3COCH2CH3 (D) (CH3)2CHCH2OH

6. Acetylene may be prepared by electrolysis of:

(a) potassium maleate (b) potassium fumarate
(c) both (a) and (b) (d) potassium acetate

7. A metallic carbide on treatment with water gives a colourless gas, which burns readily in air and
gives a precipitate with ammoniacal silver nitrate solution. The gas evolved is:
(a) CH4 (b) C2H6
(c) C2H4 (d) C2H2

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8. Which of these will not react with acetylene?

(a) NaOH (b) Na
(c) Ammoniacal AgNO3 (d) HCl

9. From the following reactions

HCCH + LiNH2  NH3 + HCCLi
HCCLi + H2O  HCCH + LiOH
predict which of the following order of basic strength is correct?
(a) HCC¯ < OH¯ < NH2 (b) HCC¯ < NH2 < OH¯
(c) OH¯ < NH2 < HCC¯ (d) OH¯ < HCC¯ < NH2

10. The reagent which is used to distinguish between propene and propyne is
(a) Bromine (b) Alkaline KMnO4
(c) Ammoniacal AgNO3 (d) Ozone

11. To synthesize the unsymmetrical alkyne CH3CCCH2CH3 the reagents needed

would be
(a) ethene, iodoethane, iodomethane and potassium hydroxide.
(b) acetaldehyde, 1bromopropane and conc. H2SO4.
(c) 1, 2dichloroethane, 1propanol and alcoholic potassium hydroxide.
(d) ethyne, iodomethane, iodoethane and sodamide.

H2 O
12. What is the end product of the following sequence of operations CaC2  (A)
dil. H SO Ni
 
2

4
 (B)  (C)?
Hg  H 2

(a) Methyl alcohol (b) Acetaldehyde

(c) C2H5OH (d) C2H4

13. 2Butyne when treated with lithium in presence of liquid ammonia gives
(a) cis2butene (b) trans2butene
(c) nbutane (d) 1butyne

14. Identify (B) in the following sequence of reactions.

Cu 2Cl2 NH 4Cl
CHCH     (A)  (B)
HCl (1mole )

(a) CH3CH2Cl (b) CH2=CHCH2CH2Cl

HCCCHCH3 Cl
(c) (d)
Cl CH2=CHC=CH2
15. Number of isomers which can be theoretically obtained on mono chlorination of 2- methyl butane is
(a) 6 (b) 2 (c) 3 (d) 4
16. A hydrocarbon with molecular formula C8H18 gives only one monochloro derivative. The hydrocarbon is
(a) n-octane (b) Methylcyclohexane
(c) 2,2,4-trimethyl pentane (d) 2,2,3,3 - tetramethylbutane
17. Ozonolysis of 2,3-dimethyl-1-butene followed by reduction with Zn-dust + H2O gives
(a) Methanoic acid and 3-methyl-2-butanone (b) Methanal and 2-methyl-butan-2-one
(c) Methanal and 3 methyl butan-2-one (d) Methanoic acid and 2-methyl-butan-2-one

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18. 2.8 g of pure alkene containing only one double bond per molecule, reacts completely with 8 g of Br2
what is the molecular formula of the Alkene.
(a) C2H4 (b) C4H8 (c) C3H4 (d) C6H12

19. What is the decreasing order of strength of bases HO- , NH2 - , HC  C - and C H 3 C H 2
(a) CH 3  CH 2   NH 2  HC  C   OH  (b) HC  C   CH 3  CH 2   NH 2  OH 
(c) OH   NH 2  HC  C   CH 3  CH 2 (d) NH 2  HC  C   OH   CH 3  CH 2

20. During electrolysis which anion migrates towards anode so as to produce 2,3-dimethyl butane.

COO– CH3 – CHCOO–

(a) CH3 – CH2 – COO– (b) (c) CH3 (d) CH3COO–
CH3 – CH
COO–
C  CH

21. Hydration of in presence of H2SO4/HgSO4 gives

COCH3 CH2CHO COCH3 CH2CHO

(a) (b) (c) (d)

22. An alkyne C7H12 on reaction with alk. KMnO4 and subsequent acidification with HCl yields a mixture
of (CH3)2CHCOOH + CH3CH2COOH. The alkyne is
(a) 3-Hexyne (b) 2-Methyl-3-hexyne
(c) 2-Methyl-2-hexyne (d) 2-Methyl-2-hexene

23. A compound (C5H8) reacts with ammonical AgNO3 to give a white ppt. and reacts with excess of
KMnO4 solution to give (CH3)2CH–COOH. The compound is
(a) CH2 = CH – CH = CH – CH­3 (b) (CH3)2CH – C  CH
(c) CH3(CH2)2C  CH (d) (CH3)2C = C = CH2

CHCOOH
24. CH 2  CH  CH  CH 2  || 
  product (X) by reaction (R). (X) and (R) are
CHCOOH

COOH COOH

(a) ; Diels Alder (b) free radical addition

COOH COOH

COOH COOH

; Diels Alder Aromatization

(c) (d)
COOH COOH

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25. CH 2  CH  CH  CH2 

CCl 3 Br
Product
CH 2  CH  CH  CH2  CCl 3
(a) Br – CH2 – CH = CH – CH2 – CCl3 (b) |
Br
CH 2  CH  CH  CH 2  Br
(c) | (d) none is correct
CCl 3

26.  Br2 
(A)

A will have configuration

Br Br

(a) (b) + Enantiomer (c) both true (d) none is true

Br Br

27. 
OsO4
(A) . The product (A) is
H2 O 2

(a) meso diol (b) racemic diol (c) both correct (d) none is correct

28. Which one is the correct statement

(a) meso-2, 3-dibromobutane on reaction with NaI/acetone gives trans-2-butene
(b) (d) or (l) of 2, 3-dibromobutane on reaction with NaI/CH3COCH3 gives trans-2-butene
(c) meso-2, 3-dibromobutane one reaction with NaI/acetone gives cis-2-butene
(d) none of these

One or More than one option may be correct.

C 4 H 6 
H 2 / Pt
1 eq
 C 4 H 8 
O3 / H 2 O
 CH 3COOH
29.
(A) (B)
Hence (A) and (B) are
(a) CH3 – C  C – CH3, CH3 – CH = CH – CH3
(b) CH2 = CH – CH = CH2, CH3 – CH = CH – CH3
(c) ; CH3 – CH = CH – CH3 (d) none of these

30. Hydroboration oxidation and acid hydration will yield the same product in case of

(a) (b)

(c) CH2 = CH2 (d) CH3 –CH = CH –CH3

CH3
31.
Br
t  BuOK
  Product. Choose the correct statement

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(a) CH3 is an endocyclic saytzeff product

(b) CH2 is an exocyclic saytzeff product

(c) CH3 is an endocyclic Hoffmann product

(d) CH2 is an exocyclic Hoffmann product

Br
CH3
CH3  Product. The product
Aq . KOH
32. 
can be

CH3
CH3 CH3
CH3 CH3
(a) CH3 (b) CH3 (c) (d)
CH3

33. O 
reagent
The reagent can be
(a) NH2 –NH2/ alcohalic KOH /  (b) Zn-Hg/HCl
(c) HI/ Red phosphurus (d) NH3/LiAlH4

34. A mixture of an aqueous solution of sodium acetate and sodium propanoate on kolbe’s electrolysis gives
(a) C2H6 (b) C3H8 (c) C4H10 (d) CH2=CH – CH3

35. (A) + HCl 

 2-chloro-2,3-dimethyl butane. Hence (A) is
CH3
CH3 CH3
CH3 C CH CH3 H3C CH3
(a) CH3 – C – CH = CH2 (b) (c) CH3 –CH2 – C – CH = CH2 (d) CH3 – C = C – CH3
CH3 CH3 OH CH3

36. Which of the following statements are correct?

(a) 1,1-Dichloroethane exhibits geometrical isomerism
(b) 1,2-Dichloroethene shows geometrical isomerism
(c) 1-Butene exhibits geometrical isomerism.
(d) Isobutylene does not show geometrical isomerism.
37. Which of the following have chiral carbon?
H H H H

(a) C2H5 – C – CH2OH (b) C2H5 – C – CH3 (c) C6H5 – C – CH3 (d) C6H5 – C – C2H5
CH3 Cl H H

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38. Which of the following structures can exist as cis-trans isomers?

(a) CH3CH2CH2CH = CHCH2CH3 (b) CH3CH2CH2CH2CH2CH2CH = CH2
(c) CH3CH2CH = CHCH2CH2CH2CH3 (d) CH2 = CHCH2CH2CH2CH2CH3

39. Which of the following reactions are expected to give (CH3)3CCH = CH2 in yields of more than 50%?
H3C H3C
 

H 2 SO4

(CH 3 )3 CO K

(a) CH3 – C – CH – CH3  (b) CH3 – C – CH – CH3 

H3C OH H3C Br

H3C

 
(d) (CH3 )3 CCH 2 CH 2 Br 
Zn
(c) CH3 – C – CH – CH3 
EtOH / EtO

H3C Br
40. Which of the following can be used for preparation of propane?
(a) CH 3 CH  CH2   (b) CH 3 CH 2 CH2 Cl 
1. Br H 2 6 [Link] / ether
2. CH COOH
3 2.H O 2

NaOH(CaO) / 
 (d) CH 3 CH2 CH2 COONa 
HI /  / 150 o C
(c) CH 3 CH2 CH2 I 
41. The nitration of propane with concentrated HNO3 gives
CH3 CH CH3
(a) CH3CH2CH2NO2 (b) (c) CH3CH2NO2 (d) CH3NO2
NO2

H3C
42. The reaction of isobutylene CH2 = C – CH3 with dil. H2SO4 gives

H3C H 3C CH2 H 3C CH3

H3C
CH3 – C – CH3 CH3 – C – CH2 – C CH 3 – C – CH = C
(a) (b) HOCH2 – CH – CH3 (c) (d)
HO H 3C CH3 H3C CH3

43. CH4 can be prepared by the reaction of H2O with:

(a) Mg 2C3 (b) CaC2 (c) Be2C (d) Al4C3

COMPREHENSI ON TYPE
Passage # 1
An alkane (A) molecular formula C6H14 reacts with chlorine in the presence of ultra violet light to yield
three isomeric monochloro derivatives (B) , (C) and (D) . Of these only (C) and (D) undergo
dehydrohalogenation with sodium ethoxide in ethanol to produce an alkene . Moreover (C) and (D) yields the
same alkene (E) (C6H12) . Hydrogenation of (E) produces (A) . Treating (E) with HCl produces a compound
(F) that is an isomer of (B) , (C) and (D) . Treating (F) with Zn and acetic acid gives a compound (G) , which
is isomeric with (A). Propose structures for (A) to (G) .
44. The structure of A is
CH3

(A) CH3–CH2–CH2–CH2–CH2–CH3 (B) CH3–CH–CH 2–CH2–CH3

CH3 CH3 CH3
(C) CH3–C–CH2–CH3 (D) CH3–CH–CH–CH3
CH3

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45. The structure of G is
CH3 CH3 CH3

(A) CH3–CH2–CH–CH2–CH3 (B) CH3–CH––CH–CH3

CH3 CH3
(C) CH3–CH–CH 2–CH2–CH3 (D) CH3–C–CH2 –CH3

CH3

46. The compound (F) on treatment with alcoholic KOH, the major product obtained is
(A) 1-hexene (B) 2,3-dimethyl-2-butene
(C) 2,3-dimethyl-1-butene (D) 3-hexene

Passage # 2
Alkanes are the saturated hydrocarbons. They are represented by a general formula CnH2n + 2
(n = 1, 2.......). They can be synthesized by different methods. One of the important method of
formation is Corey-House synthesis. In this process when alkyl halide is treated with lithium, it forms
alkyl lithium. Alkyl lithium on treatment with cuprous halide give lithium dialkyl cuprate. When it is
treated with another alkyl halide or same alkyl halide, an alkane formation takes place. The reactions
are as follows :
R–X + Li  RLi + LiX
2RLi + CuX  R2CuLi + LiX
R2CuLi + R'X  R–R' + RCu + LiX
Alkane
And in case of Wurtz reaction, when alkyl halide (RX) is treated with sodium in presence of dry
ether, alkane is formed again :
Dry
2RX + Na 
 R–R + 2NaX.
Ether
47. In Corey house reaction the yield of R–R' by reaction of R'–X with R2CuLi is in the following order
(A) Primary > Secondary > Tertiary (B) Tertiary > Secondary > Primary
(C) Secondary > Primary > Tertiary (D) Secondary > Tertiary > Primary

48. In case of Wurtz reaction which alkyl halide gives maximum yield of alkane?
(A) Isopropyl bromide (B) Methyl bromide
(C) Tert-butyl bromide (D) Ethyl bromide
49. To form the isopentane which of the following alkyl halides should be used in Corey house synthesis
(RX) and (R'X) respectively as shown above :
(A) Both CH3– CH– Br (B) CH3Br and CH3CH2CH2CH2Br
CH3
(C) CH3– CH– Br and CH3Br (D) CH3– CH– CH2Br and CH3Br
CH3 CH3

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Passage # 3

An alkene (A) on oxidation with K2Cr2O7/H2SO4 gives only two moles of gas (X), which turns lime
water milky.
50. The ‘A’ can be:
(A) H2C=CH2 (B) CH2=CH–CH=CH2

(C) (D) CH2=CH–CH2–CH=CH2

51. ‘B’ that is next homologous of ‘A’. The product/s on oxidation of ‘B’ are:
(A) Acetic acid (B) Acetic acid and formic acid
(C) Acetone and acetic acid (D) Acetic acid and CO2
52. The compound ‘C’ is the just higher homologous of ‘B’ but on oxidation does not evolve CO2. The
‘C’ is
CH3

(A) H3C–CH=CH–CH3 (B) H2C=C–CH3

(C) H2C=CH–CH2–CH3 (D) None of these

Passage–4
An unsaturated hydrocarbon A (C7H12) absorbs 2 molecule of hydrogen when hydrogenated. On
oxidation it gives one molecule each of acetic acid and acetoacetic acid and on reduction give 2-
methylhexane :
53. The structure of A:
CH2 CH3
(A) CH3—CH2— C— CH2—CH=CH2 (B) CH3—CH= C— CH2—CH=CH2
CH2 CH3
(C) CH3— C— CH2—CH=CH—CH3 (D) CH3—CH= C— CH=CH—CH3

54. The compound A on heating produces a more stable compound:

CH3 CH3
(A) CH3—CH2— C=CH —CH=CH2 (B) CH3—CH= C— CH=CH—CH3
CH2 CH3
(C) CH3–C–CH=CH–CH2–CH3 (D) CH3–C=CH–CH=CH–CH3

55. A on Reduction with 1 equivalent of H2/ Ni gives:

CH3 CH3
(A) CH3—CH2— CH— CH2—CH=CH2 (B) CH3—CH= C— CH2—CH2—CH3
CH3 CH3
(C) CH3— CH— CH2—CH=CH—CH3 (D) CH3—CH2— CH —CH2—CH2—CH3

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Passage–5

Dehydrobromination of (A) & (B) gives same alkene (C). Alkene (C) can be converted (A) & (B) by
addition of HBr in presence & absence of peroxide respectively. 1, 1 – diphenyl ethane is obtained on
reaction of (C) with benzene in the presence of H+ ions.

56. Compound ‘A’ & ‘B’ are

(A) H H
C  C  CH 3 CH 2  CH  Br  CH 3
A: B:
Br H

Br
( B) Br
A: B:

Br
( C)
CH 2  CH 2  Br CH  CH 3
A: B:

(D) None

57. Hydrolysis of (A) & (B) gives isomeric products (D) & (E). Which of the following statement for D & E is
not true ?
(A) Both D & E are isomers
(B) Both D & E gives same alkene upon dehydration
(C) Both D & E do not react with NaOH
(D) None of these

58. A when treated with NBS & then with excess NaNH2 gives (X), when (X) is reacted with HgSO4 + dil.
H2SO4 then it gives :-
(A) Phenol (B) Acetophenone (C) Benzoic acid (D) None of these

I nteger Type

59. C10H 12 after hydrogenation with excess of hydrogen gives compound of molecular
formula C10H 16 . If sum of total number of rings and  bonds possible for organic
compound C10H 12 is x, then find the value of x.

60. What is the sum of oxidation state of carbon in ethylene ozonide and its total number of
oxygen atoms.

61. How many moles of methane gas is released if 1 mole of (A) reacts with excess Me MgBr.

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(c) BrCH 2 CH 2 CH 2CH 3 and CH 3C  CH

(d) BrCH 2 CH 2CH 2CH 3 and CH 3CH 2C  CH [2010]

Q.31. In the reaction CH 3 - CH = CH 2 

NOCl
 A, the compound A is
(a) CH 3CH  NO  CH 2Cl (b) CH 3CHClCH 2 NO

(c) CH 2  NO  CH 2CH 2Cl (d) CH 3CH  Cl  CH 2CH  Cl  CH 3

X
H 3C CH 3

Q.32 In the Newman projection for 2,2 -dimethylbutane

H H
Y
X and Y can respectively be
(a) H and H (b) H and C2H5 (c) C2H5 and H (d) CH3 and CH3 [2010]

Answer Key
Home Assignment # 1

1.B 2.C 3.A 4.A 5.D 6.C 7.A

8.C 9.B 10.C 11.D 12.D 13.B 14.A
15.B 16.D 17.B 18.B 19.A 20.D 21.A
22.D 23.A 24.A 25.A
Home Assignment # 2

1.B 2.B 3.A 4.D 5.A 6.C 7.D

8.C 9.C 10.D 11.A 12.A 13.D 14.C
15.A 16.C 17.A 18.C 19.A 20.B 21.C
22.D 23.C 24.A 25.B 26.C 27.B 28.A
29.B 30.A
Home Assignment # 3

1.B 2.C 3.B 4.B 5.B 6.C 7.B

8.C 9.C 10.C 11.B 12.B 13.C 14.A
15.A 16.C 17.B 18.A 19.C 20.A 21.A
22.D 23.A 24.C 25.B 26.B 27.C 28.D
29.D 30.C 31.C 32.B 33.C 34.A 35.A
36.C 37.C 38.A 39.B 40.B

Home Assignment # 4

1.C 2.C 3.A 4.A 5.C 6.A 7.A

[Link] 9.D 10.C 11.B 12.D 13.B 14.D
15.C 16.D 17.D 18.B 19.A 20.A 21.B
22.B 23.A 24.A 25.B 26.B 27.D 28.B
29.A 30.B

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Miscellaneouse exercise

1.D 2.D 3.A 4.A 5.C 6.A 7.D

8.B 9.C 10.B 11.A 12.D 13.A 14.C
15.A 16.A 17.D 18.A 19.A 20.C 21.B
22.A 23.B 24..D 25.D 26.B 27.C 28.B

SUBJECTI VE TYPE

1. (a) 9
(b) 12
2. (a) The alkane is 2-methylpentane. The five alkyl halides are
C
C |
| C  C  CC  C
(i) X  C C  C  C  C (ii) | (2)
(1)
X

C C
| |
CC  CC C CC C C C
(iii) | (iv) |
( 3) (4)
X X

C
|
(v) CC CC C
( 5) |
X

CH 3  CH  C H  CH 3
(b) | |
CH 3 CH 3

3. V. D. = 36 ;  Molecular weight = 2  36 = 72
An examination of molecular weight suggests it to be alkane i.e. CnH2n+2.
 12n + 2n + 2 = 72 ;  n = 5
 Alkane (A) is C5H12.
(A) gives only one product on substitution, thus (A) is

CH3 CH3
CH3CCH2Cl
Cl2
CH3CCH3
CH3 CH3
(A)
h
4. Chain initiation: X2  2X  .

Chain propagation: CH3H + X  

.
C H3 + HX
.
C H 3 + X  X  CH3  X + X 
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Chain termination: X + X  X2
. .
C H 3 + C H 3  C2H6 etc.

5. The ratio of 1° to 2° Hs is 6 : 2 or 3 : 1. 1bromopropane: 3 H’s  1 = 3; 2bromopropane:

1 H  82 = 82. The percentages are: 3/85 = 3.5% of 1bromopropane and 82/85 = 96.5% of 2
bromopropane. Bromination gives mostly 2bromopropane.

6. (A):CH4 (B): CH3Br (C): CH3CH3

7. Secondary hydrogen is much more reactive than primary hydrogen towards bromination. Therefore, (A) is
mainly 2bromobutane. The subsequent reaction involves formation of Grignard reagent which picks up D+
from D2O to give CH3-CHD -CH2 - CH3.

8. (a)

(A) Ph  C  Cl

Ph Ph

(B)
Ph Cl

Ph Ph


(C) NO3– + AgCl
Ph
(aromatically stable)

C2H5 CH3 C2H5 CH3

C=C C–C
H H H H
(b) CH2
(E) (F)

CH3

CH3 C CH3
9. (A) First form C=C C=C optically inactive
H H H
H H

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CH3

H C H
(A) Second form C=C C=C optically inactive
CH3 H CH3
H H

CH3

CH3 C H
(A) Third form C=C C=C optically active
H H CH3
H H

CH3
|
CH 3  CH 2CH 2  C  CH 2CH 2CH 3
(B) | optically inactive
CH3

GET EQUI PPED FOR I I T - JEE

SI NGLE CHOI CE

1.A 2.C 3.C 4.B 5.B 6.C 7.D

8.A 9.D 10.C 11.D 12.C 13.B 14.D
15.A 16.D 17.C 18.B 19.A 20.C 21.C
22.B 23.B 24.A 25.A 26.B 27.A 28.A

ONE OR MORE THAN ONE MAY BE CORRECT

[Link] [Link] [Link] [Link] [Link] [Link]

[Link] [Link] [Link] [Link] [Link] [Link]
[Link] [Link] [Link]

PASSAGE

44.C 45.B 46.B 47.A 48.B 49.D 50.A

51.D 52.A 53.C 54.D 55.C 56.C 57.A
58.B

I NTEGER TYPE

59. (5) 60.(3) 61.(3) 62.(4) 63.(6) 64.(4) 65.(3)

66.(5) 67.(9) 68.(7)

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I I T- ia n’s PACE [Link]. AROMATIC HYDROCARBON Rg - AH - 13

1. IIT-JEE SYLLABUS
Electrophilic substitution reactions, bromination, nitration, sulfonation, friedel crafts alkylation
and acylation. Effect of o, m, p directing groups in mono substituted benzenes.

2. Electrophilic Aromatic Substitution Reactions

Aromatic hydrocarbons are known generally as arenes. An aryl group is one derived from an
arene by removal of a hydrogen atom and its symbol is Ar –. Thus, arenes are designated ArH just as
alkanes are designated RH.
The most characteristic reactions of benzenoid arenes are the substitution reactions that occur when they
react with electrophilic reagents. These reactions are of the general type shown below.

ArH + E+ –– Ar – E + H+ or

E
+ +
+ E + H

The electrophiles are either a positive ion (E+) or some other electron-deficient species with a large partial
positive charge. For example, benzene can be brominated when it reacts with bromine in the presence of
FeBr3. Bromine and FeBr3 reacts to produce positive bromonium ions, Br+. These positive bromonium ions
act as electrophiles and attack the benzene ring replacing one of the hydrogen atoms in a reaction that is
called an electrophilic aromatic substitution (EAS).
Electrophilic aromatic substitutions allow the direct introduction of a wide variety of groups into an aromatic
ring and because of this they provide synthetic routes to many important compounds. The five electrophilic
aromatic substitutions that we shall study in this package are outlined in fig. All of these reactions involve
the attack on the benzene ring by an electron-deficient species – (by an electrophile). Later we shall learn
what the electrophile is in each instance.
NO 2
HONO2
+ H2O Nitration
H2SO4

X
X2, FeX3 + H2O Halogenation
(X = Cl, Br)

SO 3H
Sulfonation
SO3
H2SO4

R
RCl, AlCl3
+ HCl Friedel-Crafts Alkylation

(R can rearrange)
O
O C
R-C AlCl 3
R
Cl + HCl Friedel-Crafts Acylation

Electrophilic Aromatic Substitution Reactions

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3. Mechanism for Electrophilic Aromatic Substitution

 and  complexes: It might be expected that the first phase of reaction would be interaction
between the approaching electrophile and delocalised  orbitals leading to  complexes (a weakly bonded
charge-transfer complex which exists in solution only and is formed by the association of an electrophilic
species (E+) and one electron-donating species) e.g. toluene form a 1:1 complex with HCl at –78°C, the
reaction being readily reversible. DCl also forms  complex with toluene. This complex on decomposition
does not form deuterium substituted toluene. Formation of complex leads to a solution that is a non-
conductor of electricity.

When an electrophile reacts with an arene usually in presence of a catalyst, a salt is formed. This
salt is composed of an anioin and a complex, resonance stabilized carbenium ion (arenium ion) in which
only two of the total  electrons of arene are utilized to form a  bond between a particular C atom of the
ring and the electrophile, known as  complex (also called Wheland intermediate).
H D H D H D
H + + H
-
+ DCl + AlCl 3 AlCl 4

+
H
H D

 + AlCl 4
-

 complex
Of course one may assume that an aromatic substitution reaction consists of four stpes involving two  and
one  complexes as shown below.
1. Formation of a -complex
+
E

+
+ E

2. Conversion of  complex to a  complex

+
E

E
+
H

3. Conversion of a  complex into  complex

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4. Decomposition of  complex to products

+
H

+
E E + H

However the most widely accepted mechanism for aromatic electrophilic substitution reaction is the
two step mechanism.
i)  complex formation ii) Loss of proton from the  complex

Of the following two steps, step 1, the formation of the arenium ion, is the rate-determining step in
electrophilic aromatic substitution.

+ E+ + Slow , rate determining

Step 1:

E H

+
+ + H Fast
Step 2:

H E E

Step 2, the loss of a proton, occurs rapidly relative to step 1 and generally has no effect on the
overall rate of reaction.
TS I

TS II

Energy
 complex
Substrate

Product

Progress of the reaction

Energy profile of an aromatic electrophilic substitution without formation of  complex.

The evidence for the two step mechanism are :

i) Detection and isolation of  complex: A large number of  complexes as intermediates have

been detected, some of them have also been isolated.

ii) Displacement of an H (or D) atom of C6H6 (or C6D6) by a nitronium ion NO2+ (formed by the
action of concentrated H2SO4 on concentrated HNO3) is an aromatic electrophilic substitution
reaction. If the C – H bond breaking is the rate determining step, then the reaction will exhibit a
primary kinetic isotope effect. By contrast C6H6 and C6D6 are found to undergo nitration at
essentially the same rate, thus C – H bond breaking cannot be involved in the rate determining
step, that means  complex formation is the rate determining step.

4. Effect of Substituents on Reactivity & Orientation

When substituted benzenes undergo electrophilic attack, groups already on the ring affect both, the rate of
the reaction and the site of attack. We say, therefore, that substituent groups affect both reactivity and
orientation in electrophilic aromatic substitutions.

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We can divide substituent groups into two classes according to their influence on the reactivity of the ring.
Those that cause the ring to be more reactive than benzene itself are called activating groups. Those that
cause the ring to be less reactive than benzene are called deactivating groups.

We also find that we can divide substituent groups into two classes according to the way they influence the
orientation of attack by the incoming electrophile. Substituents in one class tend to bring about electrophilic
substitution primarily at the positions ortho and para to themselves. We call these groups ortho - para
directors because they tend to direct the incoming group into the ortho and para positions. Substituents in
the second category tend to direct the incoming electrophile to the meta position. We call these groups
meta directors.

Several examples will illustrate more clearly what we mean by these terms.

4.1 Activating Groups: Ortho - Para Directors

The methyl group is an activating group and is an ortho - para director. Toluene reacts considerably
faster than benzene in all electrophilic substitutions.

CH3

An activating group

More reactive than benzene

toward electrophilic substitution

We observe the greater reactivity of toluene in several ways. We find, for example, that with toluene, milder
conditions (lower temperatures and lower concentrations of the electrophile ) can be used in electrophilic
substitutions than with benzene. We also find that under the same conditions, toluene reacts faster than
benzene. In nitration, for example, toluene reacts 25 times as fast as benzene.

We find, moreover, that when toluene undergoes electrophilic substitution, most of the substitution takes
place at its ortho and para positions. When we nitrate toluene with nitric and sulfuric acids, we get
mononitrotoluenes in the following relative proportions.

ortho para meta

CH3 CH3 CH3 CH3

NO 2

 
HNO3 + +
H2SO 4

o-nitrotoluene (59%) NO 2

NO 2 m-nitrotoluene (4%)
p-nitrotoluene (37%)
Of the mononitrotoluenes obtained from the reaction, 96% (59% + 37%) has the nitro group at ortho or para
position. Only 4% has the nitro group at meta [Link] substitution at the ortho and para
positions of toluene is not restricted to nitration reactions. The same behavior is observed in halogenation,
sulfonation, and so [Link] alkyl groups are activating groups, and they are also ortho – para directors.
The methoxy group, CH3O–, and the acetamido group, CH3CONH–, are strong activating groups and both
are ortho – para [Link] hydroxyl group and the amino group are very powerful activating groups and
are also powerful ortho- para directors. Phenol and aniline react with bromine in water (no catalyst is
required) to produce products in which both of the ortho positions and the para position are substituted.
These tribromo products are obtained in nearly quantitative yield.
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OH OH
Br Br



Br2
H2O

Br
2,4,6-tribromophenol

NH2 NH2

Br Br


 
Br
2

H2O

Br
2,4,6-tribromoaniline

4.2 Deactivating Groups: Meta Directors

The nitro group is a very strong deactivating group. Nitrobenzene undergoes nitration at a rate only 10-4
times that of benzene. The nitro group is a meta director. When nitrobenzene is nitrated with nitric acid and
sulfuric acids, 93% of the substitution occurs at the meta position.
NO2 NO2 NO2 NO2

NO2

 
HNO 2
+ +
H2SO 4

NO2
(6%)
NO2 (93%)
(1%)
The carboxyl group (–CO2H), the sulfo group (–SO3H), and the trifluoromethyl group (–CF3) are also
deactivating groups; they are also meta directors.

4.3 Halo Substituents: Deactivating Ortho – Para Directors

The chloro and bromo groups are weak deactivating groups. Chlorobenzene and bromobenzene undergo
nitration at rates that are, respectively, 33 and 30 times slower than for benzene. The chloro and bromo
groups are ortho - para directors, however. The relative percentages of monosubstituted products that are
obtained when chlorobenzene is chlorinated, brominated, nitrated, and sulfonated are shown in Table 1.
TABLE 1 Electrophilic Substitution Of Chlorobenzene
Para Product Total Ortho and Para Meta Product
Reaction Ortho Product (%)
(%) (%) (%)
6
Chlorination 39 55 94
2
Bromination 11 87 98
Negligible
Nitration 30 70 100
Negligible
Sulfonation Negligible 100 100

Similar results are obtained from electrophilic substitutions of bromobenzene.

5. Reactivity: the effect of electron-releasing and electron-withdrawing groups

We have now seen that certain groups activate the benzene ring towards electrophilic substitution,
while other groups deactivate the ring. When we say that a group activates the ring, what we mean, of
course, is that the group increases the relative rate of the reaction. We mean that an aromatic compound
with an activating group reacts faster in electrophilic substitutions than benzene. When we say that a group
deactivates the ring, we mean that an aromatic compound with a deactivating group reacts slower than
benzene.
We have also seen that we can account for relative reaction rates by examining the intermediate
state for the rate-determining steps. We know that any factor that increases the energy of the intermediate
state relative to that of the reactants decreases the relative rate of the reaction. It does this because it
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increases the free energy of activation of the reaction. In the same way, any factor that decreases the
energy of the intermediate state relative to that of the reactants lowers the free energy of activation and
increases the relative rate of the reaction.
The rate-determining step in electrophilic substitutions of substituted benzenes is the step that results in the
formation of arenium ion. We can write the formula for a substituted benzene in a generalized way if we
use the letter S to represent any ring substituent including hydrogen. (If S is hydrogen the compound is
benzene itself). We can also write the structure for the arenium ion in the way shown here. By this formula
we mean that S can be at any position – ortho, meta, or para – relative to the electrophile, E+. Using these
conventions, then, we are able to write the rate-determing step for electrophilic aromatic substitution in the
following general way.
When we examine this step for a large number of reactions, we find that the relative rates of the reactions
depend on whether S withdraws or release electrons. If S is an an electron - releasing group (relative to
hydrogen), the reaction occurs faster than the corresponding reaction of benzene. If S is an electron
withdrawing group, the reaction occurs slower than that of benzene.

S
S (electron releasing group)
+ Reaction is
+ E + faster

S releases
electrons H H
Arenium ion
is stabilized

S S (electron withdrawing group)

+ Reaction is
+ E + slower

S withdraws
electrons H H
Arenium ion is
destabilized

It appears, then, that the substituent (S) must affect stability of the transition state relative to that of the
reactants. Electron - releasing groups apparently make the transition state more stable, while electron
withdrawing groups make it less table. That is entirely reasonable, because the transition state resembles
the arenium ion, and the arenium ion is a delocalized carbocation.

5.1 Inductive and Resonance effect: Theory of orientation

We can account for the electron-withdrawing and electron - releasing properties of a group on the basis of
two factors: inductive effect and resonance effects. We shall also see that these two factors determine
orientation in aromatic substitution reactions.

The inductive effect of a substituent S arises from the electrostatic interaction of the polarized S to ring
bond with the developing positive charge in the ring as it is attacked by an electrophile. If, for example, S is
a more electronegative atom (or group) than carbon, then the ring will be at the end of the dipole:


-
S (e.g. S = F, Cl or Br)

Attack by an electrophile will be retarded because this will lead to an additional full positive charge on the
ring. The halogens are all more electronegative than carbon and exert an electron - withdrawing inductive

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effect. Other groups have an electron - withdrawing inductive effect because the atom directly attached to
the ring bears a full or partial positive charge. Examples are the following:

X+ O–
O–
O
+
NR3 +
C X +
N S+—OH C+—G
+
(R-alkyl or H)
O– O
X+
( G = H , R , OH , or OR)

Then resonance effect of a substituent S refers to the possibility that the presence of S may increase or
decrease the resonance stabilization of the intermediate arenium ion. The S substituent may, for example
cause one of the three contributors to the resonance hybrid for the arenium ion to be stabilized or
destabilized than the case when S is hydrogen. Moreover, when S is an atom bearing one or more
nonbonding electron pairs, it may lend extra stability to the arenium ion by providing a fourth resonance
contributor in which the positive charge resides on S.

E E +
+ S S
H H

This electron-donating resonance effect applies with decreasing strength in the following order:

Most electron –– NH2 ,–– NR2  –– OH, – OR  –– X Least electron

This is also the order of the activating ability of these groups. Amino groups are highly activating, hydroxyl
and alkoxyl groups are somewhat less activating, and halogen substituents are weakly deactivating. When
X = F, this order can be related to the electronegativity of the atoms with the nonbonding pair. The more
electronegative the atom is the less able it is to accept the positive charge (fluorine is the most
electronegative, nitrogen the least). When X = Cl, Br, or I, the relatively poor electron-donating ability of the
halogens by resonance is understandable on a different basis. These atoms (Cl, Br, and I) are all larger
than carbon and, therefore, the orbitals that contain the nonbonding pairs are further from the nucleus and
do not overlap well with the 2p orbital of carbon. (This is a general phenomenon: resonance effects are not
transmitted well between atoms of different rows in the periodic table.)

5.2 Meta-Directing Groups

All meta-directing groups have either a partial positive charge or a full positive charge on the atom directly
attached to the ring. As a typical example let us consider the trifluoromethyl group.

The trifluoromethyl group, because of the three highly electronegative fluorine atoms, is strongly electron
withdrawing. It is a strong deactivating group and a powerful meta director in electrophilic aromatic
substitution reactions. We can account for both of these characteristics of the trifluoromethyl group in the
following way.

The trifluoromethyl group affects reactivity by causing the transition state leading to the arenium ion to be
highly unstable. It does this by withdrawing electrons from the developing carbocation thus increasing the
positive charge in the ring.

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We can understand how the trifluoromethyl group affects orientation in electrophilic aromatic substitution if
we examine the resonance structures for the arenium ion that would be formed when an electrophile
attacks the ortho, meta, and para positions of (trifluoromethyl) benzene.
Ortho Attack
CF3 CF3 CF3 CF3
E E E
H H
+ H

+ +
+ Highly unstable
E contributor
Meta Attack
CF3 CF3 CF3 CF3

+ +
E E E
+ H
+ H H
E
Para Attack
CF3 CF 3 CF 3 CF 3
+

+ +
+
E H E H E
H E
Highly unstable
contributor

We see in the resonance structures for the arenium ion arising from ortho and para attack that one
contributing structure is highly unstable relative to all the others because the positive charge is located on
the ring carbon that bears the electron-withdrawing group. We see no such highly unstable resonance
structure in the arenium ion arising from meta attack. This means that the arenium ion formed by meta
attack should be the most stable of the three. By the usual reasoning we would also expect the transition
state leading to the meta - substituted arenium ion to be the most stable and, therefore, that meta attack
would be favoured. This is exactly what we find experimentally. The trifluoromethyl group is a powerful
meta director.

CF 3 CF 3

+ HNO3  

H2SO 4

NO 2
(Trifluoromethyl)benzene
(~100%)
We bear in mind, however, that meta substitution is favoured only in the sense that it is the least
unfavorable of three unfavourable pathways. The free energy of activation for substitution at the meta
position of (trifluoromethyl) benzene is less than that for attack at an ortho or para position, but it is still far
greater than that for an attack on benzene. Substitution occurs at the meta position of (trifluoromethyl)
benzene faster than substitution takes place at the ortho and para positions, but it occurs much more
slowly than it does with benzene.
The nitro group, the carboxyl group, and other meta-directing groups are all powerful electron-withdrawing
groups and all act in similar way.
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5.3 Ortho - Para - Directing Groups

Except for the alkyl and phenyl substituents, most of the ortho-para-directing groups in Table 2 are of the
following general type:
H H H
SH N O Cl

Non-bonding electrons as in

aniline phenol chlorobenzene

All of these ortho-para directors have at least one lone pair of electrons on the atom attached to the
benzene ring. This structural feature - an unshared electron pair on the atom attached to the ring -
determines the orientation and influence reactivity in electrophilic substitution reactions.
The directive effect of these groups with an unshared pair is predominantly caused by an electron -
releasing resonance effect. The resonance effect, moreover, operates primarily in the arenium ion and,
consequently, in the transition state leading to it.
Except for the halogens, the primary effect on reactivity of these groups is also caused by an electron-
releasing resonance effect. And, again, this effect also operates in the transition state leading to the
arenium ion.
In order to understand these resonance effects let us begin by recalling the effect of the amino group on
electrophilic aromatic substitution reactions. The amino group is not only a powerful activating group, it is
also a powerful ortho–para director. Aniline reacts with bromine in aqueous solution at room temperature
and in the absence of a catalyst to yield a product in which both ortho positions and the para position are
substituted.
The inductive effect of the amino group makes it slightly electron withdrawing. Nitrogen, as we know, is
more electronegative than carbon. The difference between the electronegativities of nitrogen and carbon in
aniline is not large, however, the carbon of the benzene ring is sp2 hybridized and thus is somewhat more
electronegative than it would be if it were sp3 hybridized.

Exercise1: Classify the following substituents as activating or deactivating groups and write the
structural formula of mono-substitution products.
a) C6H5CF3, Mono bromination b) C6H5CH(CH3)CH2CH3, mono sulfonation
c) Mononitration, C6H5COOCH3

6. Theory of Substituent Effects on Electrophilic Aromatic Substitution

Ortho attack
: NH2
: NH2 : NH2 +
E+ : NH2 NH2
E
E E E
H
+
H H H
+ +

Relatively stable contributor

Meta Attack
NH2 NH2 NH2 NH 2

+ +
E E E
+ H
+ H H
E
Para Attack
NH2 NH2 NH2 NH2 NH2

+ +
+
E H E H E H E H E
Relatively stable
contributor

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We see that four reasonable resonance structures can be written for the arenium ions resulting from ortho
and para attack, whereas only three can be written for the arenium ion that results from meta attack. This,
in itself, suggests that the ortho- and para-substituted arenium ions should be more stable. Of greater
importance, however, are the relatively stable structures that contribute to the hybrid for the ortho- and
para-substituted arenium ions. In these structures, nonbonding pairs of electron from nitrogen form an extra
bond to the carbon of the ring. This extra bond and the fact that every atom in each of these structures has
a complete outer octet of electrons makes these structures the most stable of all of the contributors.
Because these structures are unusually stable, they make a large and stabilizing contribution to the hybrid.
This means, of course, that the ortho- and para-substituted arenium ions themselves are considerably
more stable than the arenium ion, that results from the meta attack.

Phenol reacts with acetic anhydride, in the presence of sodium acetate, to produce the ester, phenyl
acetate.

OH   
( CH3CO )2 O
O
CH3CO2Na
CH3
phenol O
phenyl acetate
Phenyl acetate, like phenol is an ortho - para director. Try to find out :
(a) What structural feature of phenyl acetate explains this ? (b) Phenyl acetate, although an ortho - para
director, is less reactive toward electrophilic aromatic substitution than phenol. (Use resonance theory to
explain why this is so). (c) Aniline is often so highly reactive toward electrophilic substitution that
undesirable reactions take place. One way to avoid these undesirable reactions is to convert aniline to
acetanilide (below), by treating aniline with acetyl chloride or acetic anhydride.

NH2  
( CH3CO )2 O
NH
CH3
aniline O
N-phenylacetamide
What kind of directive effect would you expect the acetamido group (CH3CONH–) to have ? (d) Explain
why it is much less activating than the amino group, –NH2.
The directive and reactivity effects of halo substituents may, at first, seem to be contradictory. The halo
groups are the ortho - para directors (in Table 2) that are deactivating groups. Most of other deactivating
groups are meta directors. We can readily account for the behavior of halo substituents, if we assume that
their electron-withdrawing inductive effect influences reactivity and their electron-donating
resonance effect governs orientation.
Let us apply these assumptions specifically to chlorobenzene. The chloro atom is highly electronegative.
Thus, we would expect a chloro atom to withdraw electrons from the benzene ring and thereby deactivate
it.
Cl

Inductive effect of chloro group

deactivates ring

On the other hand, when electrophilic attack does take place, the chloro group stabilizes the arenium ions
resulting from ortho and para attack relative to that from meta attack. The chloro group does this in the same
way as amino groups and hydroxyl group do – by donating an unshared pair of electron. These electrons
give rise to relatively stable resonance structures contributing to the hybrids for the ortho- para-substituted
arenium ions.

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Ortho Attack
+
Cl + Cl Cl Cl Cl
E E E E E
H H + H H

+ +
Relatively stable
contributor
Meta Attack
Cl Cl Cl Cl

+ +

E E E
+ H
+ H H
E
Para Attack
+
Cl Cl Cl Cl Cl
+

+ + +
+
E H E H E H E H E
Relatively stable
contributor
We see that four reasonable resonance structures can be written for the arenium ions resulting from ortho
and para attack, whereas only three can be written for the arenium ion that results from meta attack. This,
in itself, suggests that the ortho- and para-substituted arenium ions are more stable than meta substituted
arenium [Link] we have said about chlorobenzene is, of course, true of bromobenzene. We can
summarize the inductive and resonance effects of halo substituents in the following way. Through their
electron-withdrawing inductive effect make the ring more positive than that
of benzene. This causes the free energy of activation for any electrophilic aromatic substitution reaction to
be greater than that for benzene, and, therefore, halo groups are deactivating. Through their electron
donating resonance effect, however, halo substituents cause the free energies of activation leading to ortho
and para substitution to be lower than the free energy of activation leading to meta substitution. This makes
halo substituents ortho-para directors.

7. Classification of Substituents
Studies like the ones that we have presented in this section have been done for a number of
other substituted benzenes. The effects of these substituents on reactivity and orientation are included
in Table 2.
TABLE 2

Effect of substituents on electrophilic aromatic substitution

ORTHO - PARA DIRECTORS META DIRECTORS
( Class – I ) (Class – II)
Strongly Activating Moderately Deactivating
–NH
. . 2, –NHR, –NR2, –C N
-
–OH,
.. –O: –SO3H
–CO2H, –CO2R
Moderately Activating –CHO, –COR
–NHCOCH3, –NHCOR, 
–OCH3, –OR - CH2- N R 3
Strongly Deactivating
Weakly Activating –NO2
– CH3, C2H5, – R, – CH2X, –NR3+
– C6H5 –CF3, –CCl3
O
Weakly
.. .. Deactivating
.. .. ||
–F:, –Cl:, –Br:, –I:, –CHX2, –NO, –S– OH,
.. .. .. .. 
–CH = CH – W, - CH2- CH2- N R 3
W represents electron withdrawing group

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8. Introduction of a 3rd group into the benzene ring

The position taken up by a third electrophile entering the ring depends on the nature of the two groups
already present. It is often possible in such cases to predict the correct isomer; but remember following
generalizations in order to do so.

1. When the two groups direct differently, i.e. they belong to the classes I and II, then class I group
takes precedence.

In the following examples, the number of arrowheads indicates (qualitatively) the amount of
substitution and the encircled number below indicates the possible number of isomers.
For example,
Cl OH
NO2

NO2

4 4

2. When both groups belong to class I, then introduction of third group is very easy and the group
enters in accordance with higher activating group. For this purpose, we can arrange the groups in
the following order: O , NH2, OH, NR2, OR > OCOR, NHCOR > R, Ar > halogen. For example,
OH

Cl
2

3. When both groups belong to class II, then it is difficult to introduce a third group and the deactivating
power of groups is in the order:

Me3N+ > NO2 > CN > SO3H > CHO > COMe > CO2H

The most deactivating group controls the orientation. For example,

NO2 NO2
CHO

CHO
2 4

4. All other things being equal, a third group is least likely to enter between two groups in the meta
position. This is the result of steric hindrance and increases in importance with the size of the groups
on the ring and with the size of the attacking electrophile. For example,

Most favoured
OCH3 Least favoured
attack attack

SO3H
4

5. When a metadirecting group is meta to an ortho/paradirecting group, the incoming group primarily
goes ortho to the meta-directing group rather than para. For example, chlorination of
mchloronitrobenzene (I) mostly gives (II) and small amounts of (III) but (IV) is formed in very small
amount.
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NO2 NO2 NO2 NO2

1
6 2 Cl Cl
Cl2/Fe
3 +
5 Cl
Cl Cl Cl
4
Cl
(I) (II) (III) (IV)

It is interesting that chlorination of (I) illustrates three rules. Of the four positions available to
electrophile, the position-5 violates rule 1, position-2 violates rule 4 and position-4 disregards rule 5.
Thus, principal attack of Cl is taking place at position-6 giving (II) as the major product.

Exercise 2: Write the major product in each of the following reaction

(a) Cl (b) Br


Sulphoration
A 
Chlorination
B

O C CH3
CH3 C CH3
O
CH3

9. Substitution of other aromatic system

9.1 Naphthalene And Anthracene Rings

The delocalization of the positive charge in the intermediate states of electrophilic substitutions is increased
by the fusion of two or more benzene rings and the polycyclic hydrocarbons are therefore all more reactive
than benzene.

Substitution in naphthalene is illustrative. The intermediatestates for the reaction at 1 and 2positions may
be represented as follows:
H E H E H E
 
1substitution: * *

H E H E


 H H H
E E E
2substitution: *
 

H  H
E E


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In each of the two intermediate states, the positive charge is more extensively delocalized than in reaction
with benzene, leading to lower activation energies. Further, the three starred structures are of benzenoid
type and therefore of lower energy content than the remainder in which the benzenoid nature of the second
ring has been destroyed. Since there are two such low energy contributors for 1substitution as compared
with one for 2substitution, it is understandable that the 1position should be the more reactive than
2position.

The presence of an electronattracting group in naphthalene reduces the reactivity and causes substitution
to occur in the unsubstituted ring, mainly at the 5 and 8positions (i.e. the two 1positions of that ring). An
electronreleasing group activates the molecule further and reaction occurs in the substituted ring. If the
group is in the 1position, substitution occurs at the 2 and 4positions (i.e. ortho and para to the
electronreleasing group), but a 2substituent directs almost entirely to the 1position, although the
3position is also an ortho position. The reason is that the stabilization of the transition state which is
provided by the substituent is more effective when the appropriate resonance structure is benzenoid
(1substitution) than when it is not (3substitution). For instance,

H E
 
OH
.. OH
..
*
H
(Benzenoid) (Nonbenzenoid) E

In anthracene, the electrophile attacks preferentially at the 9 or 10 positions since the arenium ion formed
by the electrophilic attack at any of these positions can have two intact benzene rings in its canonical forms,
while attack of electrophile at any other position (1 or 2) would give arenium ion having a naphthalene ring
in its canonical forms. The resonance energy of 2 benzene rings is more than the resonance energy of a
naphthalene ring.
1 9 8
2 7

3 6
4 10 5

(Position 1,4,5 and 8 are identical, positions 2,3,6 and

7 are also identical and positions 9 and 10 are same)

9.2 Five–Membered Heterocyclic Rings

The principles that govern the electrophilic substitutions of this group of heterocyclic aromatic compounds
will be illustrated by reference to pyrrole.
Pyrrole is highly reactive at both the 2and 3positions. The reason is that the transition state for
substitution at each position is strongly stabilized by the accommodation of the positive charge by nitrogen,
in just the way that aniline owes its reactivity to the exocyclic nitrogen. 2substitution predominates
because the positive charge in the transition state is delocalized over a total of three atoms, compared with
two for 3substitution.

The similarity of pyrrole and aniline is particularly apparent in their reactions with aqueous bromine: each
reacts at all its activated carbon atoms, pyrrole giving tetrabromopyrrole and aniline giving
2,4,6tribromoaniline. In fact, pyrrole is even more strongly activated than aniline and should perhaps be
compared with the phenoxide ion: each undergoes the ReimerTiemann reaction, unlike other benzenoid
compounds. In addition, pyrrole undergoes FriedelCrafts acylation in the absence of a catalyst.

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2substitution: .. H .. H  H

N N N
E E E
H H H
(Stable contributoroctet of
every atom is complete)

H H
E E
3substitution: 
.. 
N N
H H
(Stable contributoroctet of
every atom is complete)

Furan and thiophen are also activated towards electrophiles and react predominantly at the 2position. The
underlying theory is similar to that for pyrrole, namely, that the heteroatom is able to delocalize the positive
charge on the transition state. Since oxygen accommodates a positive charge less readily than nitrogen,
furan is less reactive than pyrrole, just as phenol is less reactive than aniline. The +M effect of sulphur is
smaller than that of oxygen because the overlap of the differently sized porbitals of carbon and sulphur is
less than in the case of carbon and oxygen so that, understandably, thiophene is less reactive than furan.
Thus, the reactivity order of 5membered heterocyclics towards electrophilic substitution would be

pyrrole > furan > thiophene.

9.3 Six–Membered Heterocyclic Rings

The principles governing the reactivity of these compounds are illustrated by reference to pyridine. The
transition states for substitution at the 3 and 4positions can be represented as the hybrids.
H H  H
E E E
3substitution:
 
N N N
H E H E H E
 
4substitution:

N N N

In each case, the positive charge is less well accommodated than in reactions on benzene because
nitrogen is more electronegative than carbon. Hence, both the 3 and 4positions are deactivated, the
latter more strongly because of the high energy of the contributing structure which contains divalent
positive nitrogen. The 2position resembles the 4position, as reference to the appropriate resonance
structures will show.
Quinoline and isoquinoline are also deactivated, though less so than pyridine and reaction normally occurs
in the homocyclic ring at the 5 and 8positions.

5 4 5 4
6 3 6 3
2
7 2 7 N
8 N1 8 1

Quinoline Isoquinoline

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10 Examples of Electrophilic Substititution

10.1 Nitration of Benzene

Benzene reacts slowly with hot concentrated nitric acid to yield nitrobenzene. The reaction is much faster if
it is carried out by heating benzene with a mixture of concentrated nitric acid and concentrated sulfuric acid.
NO2
50  55  C
 HNO3  H2 SO 4    H3 O   HSO 4

Concentrated sulfuric acid increases the rate of the reaction by increasing the concentration of the
electrophile –– the nitronium ion (NO2+).

H + NO2 -
O + HSO4
+ HOSO3H O
H NO2 (H 2SO4)
Step 1:
H

Step 2: H + NO 2
+
O NO 2 + H2O
Nitronium ion
H

In step 1 nitric acid acts as a base and accepts a proton from the stronger acid, sulfuric acid. In step 2 the
protonated nitric acid dissociates and produces a nitronium ion. In step 3, the nitronium ion reacts with
benzene by attacking the  cloud and forming an arenium ion.


NO2 H H 
H
slow NO2 NO 2
NO2
Step3:  

Arenium ion

In step 4, the arenium ion then transfers a proton to some base in the mixture such as HSO4- and becomes
nitrobenzene.

H
NO2
NO2 HSO4
H2SO 4

Nitration of arene can also be achieved by using N2O5 and nitronium salts like NO2BF4 ,
NO2PF6 etc.
Step 4:
 
 N O2
N 2 O5   N O3
electrophile
 
NO 2 BF4  N O 2  B F4

NO 2 PF6  N O 2  PF6

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10.2 Halogenation of Benzene

Cl
+ Cl2  
FeCl 3
+ HCl

25 C

chlorobenzene
Br
+ Br2 + HBr
 
FeCl3

25 C
bromobenzene

Benzene does not react with bromine or chlorine unless a Lewis acid is present in the mixture, (as a
consequence, benzene does not decolorize a solution of bromine in carbon tetrachloride). When Lewis
acids are present, however, benzene reacts readily with bromine or chlorine, and the reactions give
bromobenzene and chlorobenzene in good yields.

The Lewis acids most commonly used to perform chlorination and bromination reactions are FeCl3, FeBr3,
and AlCl3 all in the anhydrous form. Ferric chloride and ferric bromide may also be generated in the
reaction mixture by adding iron to it. The iron reacts with halogen to produce the ferric halide which then
acts as catalyst : 2Fe + 3X2 –– 2FeX3

The mechanism for aromatic bromination is as follows :

Step 1: + -
Br Br + FeBr3 Br + FeBr4

H H
+ Br Br
+ Br  
slow
etc
Step 2: + +

Arenium Ion

H
Br
Br
Step 3: -
Br FeBr3 
 fast
+ H Br + FeBr3
+

The function of the Lewis acid can be seen in step 1. The ferric bromide reacts with bromine to produce a
positive bromonium ion, Br+ (and FeBr4-). In step 2 this Br+ ion attacks the benzene ring to produce an
arenium ion. Then finally in step 3 the arenium ion transfers a proton to FeBr4-. This results in the formation
of bromobenzene and hydrogen bromide, the products of the reaction. At the same time this step
regenerates the catalyst FeBr3.

The mechanism of the chlorination of benzene in the presence of ferric chloride is analogous to the one for
bromination. Ferric chloride serves the same purpose in aromatic chlorination as ferric bromide does in
aromatic bromination. It assists in the generation and transfer of a positive halonium ion. The rate of
reaction is often of the form, Rate = K [Ar – H] [X2] [Lewis acid]

Hypo-halous acids (HO – X) in presence of strong acid also become a very powerful halogenating agent.

HO X H+ H2O X H2O X
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Fluorine reacts so rapidly with benzene that aromatic fluorination requires special conditions and special
types of apparatus. Even then, it is difficult to limit the reaction to monofluorination. Fluorobenzene can be
made, however, by an indirect method.

Iodine, on the other hand, is so unreactive that a special technique has to be used to affect direct
iodination; the reaction has to be carried out in the presence of an oxidizing agent ( to destroy strong
reducing agent HI ) such as nitric acid.

I

L.A.
+ I2  + HI
Strong reducing agent

+ I2  
HNO 3

Iodination can also be performed using inter halogen compound like I – Cl that leads to the formation of
HCl instead of HI.

I
+ ICl 
L.A.
 + HCl
not a Strong reducing agent

Kinetic isotope effects have not been observed for chlorination and rarely for bromination, but iodination
shows kinetic isotope effect.

10.3 Sulfonation of Benzene

Benzene reacts with fuming sulfuric acid at room temperature to produce benzenesulfonic acid. Fuming
sulfuric acid is sulfuric acid that contains added sulfur trioxide (SO3). Sulfonation also takes place in
concentrated sulfuric acid alone, but more slowly.
O
O
O S H
25  C
+ O S  O
conc . H2SO 4

O
Suffer trioxide Benzenesulfonic acid

In either reaction, the electrophile appears to be sulfur trioxide. In concentrated sulfuric acid, sulfur trioxide
is produced in the following equilibrium in which H2SO4 acts as both an acid and a base.

Step 1: 2H2SO4 SO3 + H3O+ + HSO4-

When sulfur trioxide reacts with benzene the following steps occur.

O H H + H
- - -
slow SO 3 SO 3 SO 3
S O
Step2: + +
O

Arenium Ion

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H
- SO 3
Step 3: SO 3 -
+ HSO 4 + H2SO 4 Fast
+

SO 3 SO 3H
+ H2O
Step 4: + H3O + Fast

All of the steps are reversible, including step 1 in which sulfur trioxide is formed from sulfuric acid. This
means that the overall reaction is an equilibrium as well. In concentrated sulfuric acid, the overall
equilibrium is the sum of steps 1 - 4.
SO3 H

+ H2SO 4 + H2 O

In fuming sulfuric acid, step 1 is unimportant because the dissolved sulfur trioxide reacts directly.

Because all of the steps are reversible, the position of equilibrium can be influenced by the conditions we
employ. If we want to sulfonate benzene we use concentrated sulfuric acid (or better fuming sulfuric acid).
Under these conditions the position of equilibrium lies appreciably to the right and we obtain
benzenesulfonic acid in good yield.

On the other hand, we may want to remove a sulfonic acid group from a benzene ring. To do this we
employ dilute sulfuric acid and usually pass steam through the mixture. Under these conditions with a high
concentration of water the equilibrium lies appreciably to the left and desulfonation occurs. The equilibrium
is shifted even further to the left with volatile aromatic compounds because the aromatic compounds distill
with the steam.

We shall see later that sulfonation and desulfonation reactions are often used in synthetic work. We may,
for example, introduce a sulfonic acid group into a benzene ring to influence the course of some further
reaction. Later, we may remove the sulfonic acid group by desulfonation. Like iodination, sulfonation
exhibits a kinetic isotopic effect.

10.4 Friedel - Crafts Alkylation

In 1877 a French chemist, Charles Friedel, and his American collaborator James M. Crafts, discovered new
methods for the preparation of alkylbenzenes (ArR) and acylbenzenes (ArCOR). These reactions are now
called the Friedel - Crafts alkylation and acylation reactions. We shall study the Friedel - Crafts alkylation
reaction here and then take up the Friedel - Crafts acylation reaction. A general equation for a Friedel -
Crafts alkylation reaction is the following :

+ R X  
AlCl3
+ HX

The mechanism for the reaction (shown in following steps with isopropyl chloride as R –– X) starts with the
formation of a carbocation (step 1). The carbocation then acts as an electrophile (step 2) and attacks the
benzene ring to form an arenium ion. The arenium ion (step 3) then loses a proton to generate
isopropylbenzene.
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H3C H3C
+
CH Cl + AlCl 3 CH + AlCl 3
Step 1:
H3C H3C
Isopropyl chloride Carbocation

CH3 H CH3
+ CH
+ CH +
Step 2: CH3
H3C
Arenium ion

CH3
H CH3
CH
CH - CH3 + HCl + AlCl 3
Step 3: + + AlCl 4
CH3

Isopropylbenzene

When R –– X is a primary halide, a simple carbocation probably does not form. Rather, the aluminum
chloride forms a complex with the alkyl halide and this complex acts as the electrophile. The complex is
one in which the carbon - halogen bond is nearly broken and the carbon atom has a considerable positive
charge.

+ –
RCH2 ---- Cl : AlCl3

Even though this complex is not a simple carbocation, it acts as if it were and it transfers a positive alkyl
groups to the aromatic ring. These complexes are so carbocation like that they also undergo typical
carbocation rearrangements.

Factors Determining mechanism of alkylation:

(i) Nature of alkyl groups

If the alkyl group is simple CH3 or CH3CH2, then a complex between alkyl halide and Lewis
acid is the electrophile as shown in second mechanism. But because of the relative stability of
sand t carbonium ions, the adducts with s and t alkyl halides ionise and it is now the
carbonium ion that is predominantly the active species. e.g.
Me3CCl + AlCl3  Me3C + AlCl 4

(ii) Nature of Lewis acid as catalyst

The order of effectiveness of Lewis acid catalysts has been shown to be
AlCl3 > FeCl3 > BF3 > TiCl3 > ZnCl2 > SnCl4
The action of Me3CCH2Cl/AlCl3 on benzene is found to yield almost completely the rearranged
product, PhCMe2CH2Me, which can be explained on the basis of the initial electrophilic complex
being polarized enough to allow the rearrangement of [Me3CCH2]+ClAlCl3 to the more
stable [Me2CCH2Me]+ ClAlCl3. By contrast Me3CCH2Cl/FeCl3 on benzene is found to
yield almost completely the unrearranged product, Me3CCH2Ph. This is due to the fact that the
complex with the weaker Lewis acid, FeCl3, is not polarized enough to allow the rearrangement.

(iii) Temperature
Not only nature of the alkyl group, but also temperature determines the nature of electrophile. e.g.
nalkyl group can be introduced to a fair extent without rearrangement at low temperatures, because
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ionisation of the adduct is retarded. But at higher temperatures, carbonium ion is formed which
rearranges and the product is rearranged alkyl benzene. Thus npropylchloride gives isopropyl
benzene.

H
..  +
CH3CH2CH2Cl:
.. + AlCl 3 (ii) CH3CHCH2 + AlCl4
(i)
rearranged
+ 
CH3CH2CH2 Cl AlCl3 +
CH3CHCH3
2° Carbocation (more stable)

CH2CH2CH3 + AlCl3 + HCl

CH3
CH
CH3 + HCl + AlCl3
npropyl benzene

Isopropyl benzene
In the same way, isobutyl chloride gives tbutyl benzene.

Friedel - Crafts alkylations are not restricted to the use of alkyl halides and aluminum chloride. Many other
pairs of reagents that form carbocations (or carbocation like species) may be used as well. These
possibilities include the use of a mixture of an alkene and an acid.

A mixture of an alcohol and an acid may also be used

60oC
+ HO
BF3

10.5 Friedel - Crafts Acylation

O
||
The R C  group is called an acyl group, and a reaction whereby an acyl group is introduced into a
compound is called an acylation reaction. Two common acyl groups are the acetyl group and the benzoyl
group.
O

O C

CH3C
Acetyl group Benzoyl group

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Mechanism:

Friedel crafts acylation is found to follow the same general rate law as alkylation
Rate  [Substrate] [RCOCl] [AlX3]
In case of acylation, the nature of electrophile will be as follows:

O
.. 
i) R  C  Cl:
.. + AlCl3 R  C = O + AlCl4


O O AlCl3
ii) R  C  Cl + AlCl3 R  C  Cl
+

O O
.. 
iii) R  C  Cl:
.. + AlCl3 R  C  Cl AlCl3
+

Due to the presence of lone pair of electron on both chlorine and oxygen two intermediates are
possible and both are capable of electrophilic attack on benzene.
Acylium ions have been detected in a number of solid complexes, in the liquid complex between
CH3COCl and AlCl3 (by spectroscopy), in solution in polar solvents and in a number of cases
+ 
where R is very bulky. In less polar solvents the polarized complex R C O AlCl3 has been
Cl
detected to act as the electrophile. Direct chemical evidence clearly indicates that both can be
involved depending upon the circumstances.
Mechanism may be represented as follows:

O
+
i) R  C  Cl + AlCl3 R  C = O + AlCl 4
or 
O O AlCl3
+
R  C  Cl + AlCl3 RC
Cl

O AlCl3
+ 
H C R
R C O AlCl3 
Cl + Cl

ii) O

H C R

R C O +

COR AlCl4

+ AlCl3 + HCl

Product

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The Friedel - Crafts acylation reaction is an effective means of introducing an acyl group into an aromatic
ring. The reaction is often carried out by treating the aromatic compound with an acyl halide. Unless the
aromatic compound is one that is highly reactive, the reaction requires the addition of at least one
equivalent of a Lewis acid (such as AlCl3) as well. The product of the reaction is an aryl ketone.

O C
+ H3 C C AlCl3 CH3
o
Cl excess benzene 80 C

Acetyl chloride Acetophenone ( methyl phenyl ketone )

Acyl chlorides, also called acid chlorides, are easily prepared by treating carboxylic acids with thionyl
chloride (SOCl2) or phosphorus pentachloride (PCl5).

O O
80  C
H3C C + SOCl 2  H3C + SO 2 + HCl
OH Thionyl chloride Cl
acetic acid acetyl chloride
O O
+ PCl5 + POCl3 + HCl
OH Cl
Phosphorus
benzoic acid pentachloride benzoyl chloride

Friedel - Crafts acylations can also be carried out using carboxylic acid anhydrides. For example :
O O
H3C C C O
CH3
+ O 
AlCl3
+ H3C
excess benzene

H3C C OH
Acetophenone
O
acetic anhydride

In the last step aluminum chloride (a Lewis acid) forms a complex with the ketone (a Lewis base). After the
reaction is over, treating the complex with water liberates the ketone.

H3C R

C O AlCl3 + 3H2 O C O + Al(OH)3 + 3HCl

H5C6 H5C6

Several important synthetic applications of the Friedel - Crafts reaction are later in the package.

Limitations of Friedel - Crafts Reactions: Several restrictions limit the usefulness of Friedel -
Crafts reactions.

1. When the carbocation formed from an alkyl halide, alkene, or alcohol can rearrange to a more
stable carbocation, it usually does so and the major product obtained from the reaction is usually the
one from the more stable carbocation. When benzene is alkylated with butyl bromide, for example,
some of the developing butyl cations rearrange by a hydride shift some developing 1o carbocations
(see following reactions) become more stable 2o carbocations. Then benzene reacts with both kinds
of carbocations to form both butylbenzene and sec-butyl-benzene :

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+
 
AlCl3 CH2 CH3
H3C Br H3C H3C
+

CH3
H3C
H3C

butylbenzene
sec-butylbenzene
This rearrangement can be minimized if we do the reaction at low temperature and in presence of
weaker Lewis acid like FeX3 , SnX4 etc.

2. Friedel - Crafts reactions do not occur when powerful electron-withdrawing groups are present on
the aromatic ring or when the ring bears an –NH2, –NHR, or –NR2 group. This applies to
alkylations and acylations.
+ O OH O R +
NO2 N(CH3)3 C C CF3 SO3H NH3

These do not undergo Friedel-Crafts reactions

We know that groups present on an aromatic ring can have large effect on the reactivity of the ring
towards electrophilic aromatic substitution, Electron - withdrawing groups make the ring less reactive
by making it electron deficient. Any substituent more electron withdrawing (or deactivating) than a
halogen, that is, any meta-directing group, makes an aromatic ring too electron deficient to undergo
a Friedel - Crafts reaction. The amino groups, –NH2, –NHR, and –NR2, are changed into powerful
electron - withdrawing groups by the Lewis acids used to catalyze Friedel - Crafts reactions. For
example :
H
H H
N H +N AlCl 3

+ AlCl 3

Does not undego a Friedel-Crafts reaction

3. Aryl and vinylic halides cannot be used as the halide component because they do not form
carbocations readily.
Cl

No Friedel-Crafts reaction

AlCl3

No Friedel-Crafts reaction
CH3

Cl
H3C

CH3

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4. Polyalkylations often occur because Alkyl groups are electron - releasing groups, and once one is
introduced into the benzene ring it activates the ring toward further substitution.
C 3H 7 C3 H7
H3C

+ CH2OH 
BF3

 +
60 C

H3C
Isopropyl benzene (24%)
C3 H7
p-diisopropylbenzene (14%)

Polyacylations are not a problem in Friedel - Crafts acylations, because the acyl group (RCO–) by
itself is an electron - withdrawing group, and when it forms a complex with AlCl3 in the last step of
the reaction, it is made even more electron withdrawing. This strongly inhibits further substitution
and makes monoacylation easy.

Synthetic Applications of Friedel - Crafts Acylations

Rearrangements of carbon chain do not occur in Friedel - Crafts acylations. The acylium ion,
because it is stabilized by resonance, is more stable than most other carbocations. Thus, there is
no driving force for a rearrangement. Because rearrangements do not occur, Friedel - Crafts
acylations often give us much better routes to unbranched alkylbenzenes than do Friedel - Crafts
alkylations.

As an example, let us consider the problem of synthesizing propylbenzene. If we attempt this

synthesis through a Friedel - Crafts alkylation, a rearrangement occurs and the major product is
isopropylbenzene.
CH(CH3)2

Br  
AlCl3
+ HBr
+ H3C

isopropylbenzene

By contrast, the Friedel - Crafts acylation of benzene with propanoyl chloride produces a ketone
with an unrearranged carbon chain in excellent yield.
O
Cl
H3C + HCl
+  
AlCl 3

CH3
O
propanoyl chloride Ethyl phenyl ketone

The resultant ketone can be then reduced to alkyl benzene when refluxed with zinc [Caution : As we
shall discuss later zinc and hydrochloric acid will also reduce nitro groups to amino groups] in
presence of HCl.
O

CH3
  
Zn( Hg)
HCl reflux
CH3

Ethyl phenyl ketone propylbenzene

or
O

  
Zn( Hg ) Ar
HCl, reflux
Ar R R
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When cyclic anhydrides are used as one component, the Friedel - Crafts acylation provides a means of
adding a new ring to an aromatic compound.

Comparison between alkylation and acylation

i) A comparison of the electrophilic nature of both alkyl and acyl group indicates that
acyl group is a better electrophile on account of two electron withdrawing atoms attached to Carbon.

H O
+ 
R C Cl R C Cl


H
alkyl halide Effective +ve charge density
on carbonyl carbon is greater.

ii) Acylation requires more catalyst than alkylation because much of the catalyst is consumed in the
formation of a complex with the product (ketone)
 
H3C C O AlCl3
COCH3

+ AlCl3

and is prevented from further participation in the reaction.

iii) Unlike polyalkylation, polyacylation does not take place as the product ketone is much less reactive
than the original hydrocarbon.
iv) Rearrangement of acyl cation does not take place, as in alkylation, but decarbonylation can take
place, particularly where R would form a stable carbonium ion, so that the end result is then
alkylation rather than the expected acylation.

Me3C  C = O  CO + Me3C

CMe3
+ Me3C+

Exercise 3: Convert benzene to -tetralone

Exercise 4: Nitrobenzene, but not benzene, is used as a solvent for the Friedel-Craft alkylation of bromo-
benzene. Explain.

11. Reactions of Alkyl Benzenes

11.1 Halogenation of the side chain

The side chain halogenation of alkyl benzene takes place in the presence of light or high temperature. Side
chain bromination is many times carried out by using the reagent N-bromosuccinimide (NBS) in the
presence of light.
CH3 O
CH2Br
C
H 2C h
+ NBr 
CCl 4
H 2C
C
O

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An alkyl benzene with side chain other than methyl may lead to the formation of more than one products.
Br
CH3
CH3
(I)
Br2
Heat, light
Br

(II)

Product (I) is the only product obtained, and formation of such product can be attributed to mechanism
governing this reaction. Side chain halogenation has a similar mechanism as that of alkanes. It involves the
formation of free radical intermediates. Now if we observe the free radicals formed by attack of Bromine
free radical on Ethyl benzene, we will find that product (I) involves formation of Benzyl free radical and (II)
involves formation of Primary free radical.
CH3 Br CH3
HC

h 

Br2
CH3

Br

CH2

h 

Br2

The benzyl free radical is more stable than primary free radical because its bond dissociation energy is 19
kcal/mole less than that of primary free radical.

Order of stability of free-radicals. Benzyl > Allyl > 3° > 2° > 1° (from bond dissociation energy data).

11.2 Oxidation of side chain

Although benzene itself is not susceptible to oxidation but side chain attached to the benzene ring
undergoes oxidation and converts itself into a –COOH group. Oxidation of side chain takes place after
substance is heated for a long time with KMnO4.
R COOH

 
KMnO 4

The above reaction can be used for identifying substitution pattern in aromatic compound. If any compound
gives phthalic acid on heating with KMnO4, then we can infer that it is ortho disubstituted benzene.
CH3
R COOH H3C CH3
R COOH
 

KMnO 4
 
4
 No reaction
KMnO

Tertiary alkyl benzene is resistance to oxidation because of the absence of a benzylic hydrogen.
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12. Solution to Exercises

Br
Solution 1: a)
deactivating, F3C

b) CH3

activating, HO3S
CH3
c) NO2
O
deactivating,
H3C O

Solution 2: Cl CH3

HO3S Cl

A=
B=

O C CH3

O CH3 C CH3

CH3

O
Solution 3:
O
 
3 AlCl
+ O

O OH
excess Succinic anhydride O
3-benzoylpropanoic acid

4 – keto – 4 – phenylbutanoic acid Cl

OH
 
SOCl 2

80 C
O O

4-phenylbutanoic acid 4-phenylbutanoyl chloride

AlCl3-CS2

O
-Tetralone

Solution 4: Benzene is more reactive than bromobenzene and hence would preferentially undergo
alkylation. On the other hand, nitrobenzene is very much less reactive than bromobenzene
(due to deactivating effect on the –NO2 group) and hence will not undergo Friedel - Craft
reaction.

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13. Solved Problems

Problem 1: Phenol undergoes electrophilic substitution at a faster rate in alkaline medium. Why?

Solution: Phenol is 0-,p-directing due to the +M effect of its  O H group.

+ +
OH OH OH


Also  O H has –I effect.

But in alkaline medium, phenol is converted to phenoxide ion which has both +M and +I
effect. Hence ring is more activated and hence electrophilic substitution occurs more
readily.

Problem 2: How will you synthesize

CH3

from benzene?

O
Solution:
Cl CH3
+ H3C 
ACl3

O
Zn(Hg)/HCl
(Clemmensen reduction)

CH3

If we would have tried to synthesize it using CH3CH2CH2Br then we would have got
iso-propylbenzene due to rearrangement of carbocation.

Problem 3: When toluene is treated with DCl at – 78°C no deuterium is exchanged and the solution
does not conduct electricity. What is the structure of the complex?

Solution: Under the given condition, either a  complex or a  complex usually forms. DCl

Since no D is exchanged and since the solution does not conduct electricity,
the formation of  complex is ruled out. Hence the product is a -complex. CH3

Problem 4: Phenyl group is known to exert – I effect. But each phenyl ring in biphenyl (C6H5 – C6H5) is
more reactive than benzene towards electrophilic substitution. Why?

Solution: In biphenyl, one of the phenyl groups acts as electron donor and the other electron
acceptor. This makes the phenyl ring more reactive than benzene towards electrophilic
substitution.

Problem 5: The alkylation of phenol and aniline with alkyl halide in presence of AlCl3 gives poor
yields. Explain.

Solution: In presence of Lewis acid (e.g. AlCl3), the group (–NH2 or –OH) becomes electron
withdrawing due to formation of Lewis acid base adduct.
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Problem 6: Predict the product

O
(CH3)3C - C
Cl
   ?
AlCl 3

Solution: O O

C AlCl 3 C + AlCl 3
(CH3)3C Cl (CH3)3C Cl
CMe3

(CH3)C + O
+
C CO + Me 3 C

In R  C  Cl , if R is capable to form a stable carbocation, decarbonylation can take

||
O
place. So the end result is then alkylation rather than the expected acylation.
Problem 7: The rates of bromination (FeBr3 catalyst) of C6H6 and C6D6 are the same. Discuss.

Solution: All the evidence favours a bimolecular mechanism for bromination; this may be written:
Br2 + FeBr3 fast
Br+ + FeBr4

H Br
+ 1 
+ Br FeBr 4
  + HBr + FeBr3
+ 2

Steps 1 and 2 are bimolecular and so either could be the r/d step. Since no kinetic isotope
effect is observed when H is replaced by D, C–H or C–D bond fission cannot be involved in
rate determining step. Hence, 1 is the rate determining and so the rate of bromination is the
same for C6H6 and C6D6.
Problem 8: Complete the equations
CHO

i)

+ HNO 3  ?
Ac 2O
AcOH

Solution:
CHO CHO CHO

i)
NO2
+ Ac 2O
+ HNO 3  
AcOH

NO2

Although the side-chain is electron - withdrawing, substitution occurs at the o and

p position. In this case, the correct orientation is obtained from a consideration of the
stabilities of the various carbonium ions. The major product is the o compound. This is often
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the case when acetyl nitrate (HNO3, Ac2O) is the nitrating agent. The explanation is
uncertain.
The aldehyde group, although sensitive to oxidation, remains unchanged. The OMe groups
are o/p - directing and the CHO group is m-directing; the former take [Link]
product is the 2-nitro-derivative (p to one OMe group). However, since the 3-position is
'assisted' by the CHO group and OMe group (0 to 3), it might have been expected that the 3-
nitro-derivative would be the major product. One possible explanation could be steric effects
at the 3-position arising from the orientation of the Me groups due to resonance ( thetwo Me
groups will be as far apart as possible).

CH O
CHO

OMe Me
O
OMe MeO

Problem 9: Cinnamic acid is ortho-para directing. Explain

Solution: It is easier to explain this orientation by consideration of the stabilities of the various
carbonium ions.
For p-attack
+
E
CH 
 E CH
CH CO2H CH CO2H

E + CH E CH
+
CH CO2H CH CO2H
m-attack
E


CH 

E
+ CH
CH CO 2H CH C2H
E E
+
CH CH
CH CO 2H CH CO 2H
+

Only for o and p-attack spreading of positive charge to the side chain is possible, thereby
stabilizing these more than m-attack.
Problem 10: Complete the series of reaction
o-HOOC—C6H4—CH2—C6H5  SOCl Anhydrous
 ?  ZnHg
   ? 
2
 
AlCl 3 HCl

Solution:
 
SOCl
  
anhydrous
AlCl 3
int ramolecula r
COOH COCl F.C. reaction

ZnHg
 
HCl

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H OME ASSI GNMENT – 1

PART – A (OBJECTI VE )
Only one option is correct :
1. Among the following, the compound that can be most readily sulphonated is
(a) benzene (b) nitrobenzene
(c) toluene (d) chlorobenzene

2. The presence of which one of the following groups on benzene nucleus activates it towards
electrophilic substitution?
(a) CN (b) CHO
(c) COOR (d) OCOR

3. Which species will undergo electrophilic substitution reaction most easily?

(a) Ph–OH (b) PhSH
(c) Ph – O– (d) Ph – S–

4. The relative reactivities of benzene, aniline, nitrobenzene and toluene are

(a) benzene > toluene > aniline > nitrobenzene
(b) nitrobenzene > aniline > toluene > benzene
(c) toluene > aniline > nitrobenzene > benzene
(d) aniline > toluene > benzene > nitrobenzene

5. Which of the following is electrophilic substitution reactions:

OH OH
CuCl Br Br
(1) C6H5N2Cl  C6H5Cl (2) Br2
HCl
HOH

Br
Cl NO2

Cl2 HNO3
(3) (4)
Fe H2SO4

Select the correct answer from the codes given below:

(a) only (1) (b) (2), (3) and (4)
(c) (1) and (3) (d) (1), (2), (3) and (4)

6. Which of the following species is expected to have maximum enthalpy in an electrophilic aromatic
substitution reaction?
H E+ H E +
H E E
+ +
+ E+ + H+

(I) (II) (III) (IV) (V)

(a) species (II) (b) species (III)
(c) species (IV) (d) species (V)

7. Electrophile NO 2 attacks the following aromatic species.


CCl3 NO2 NR3 O

(I) (II) (III) (IV)

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In which cases NO 2 will be at meta position?

(a) (II) and (IV) (b) (I), (II) and (III)
(c) (II) and (III) only (d) (I) only

8. Which of the following aromatic compound will undergo nitration most easily?
CH3 CMe3

(a) (b)
CH2OH CN

(c) (d)
9. Which of the following is meta directing group?
(a) COOH (b) OH
(c) NH2 (d) Cl

10. Identify the correct order of reactivity in electrophilic substitution reaction of the following
compounds
NO2 Cl OH

1 2 3 4
(a) 1 > 2 > 3 > 4 (b) 4 > 1 > 2 > 3
(c) 4 > 3 > 2 > 1 (d) 4 > 1 > 3 > 2

11. When cinnamic acid ( 3- phenylpropenoic acid ) is nitrated, the incoming electrophile ( NO 2 ) goes
at
(a) ortho position only (b) para position only
(c) meta position only (d) both ortho and para positions

12. Which of the following substituted benzenes would furnish three isomeric compounds when one
more substituent is introduced?
Cl Cl
Cl
(1) (2)

Cl Cl

(3) (4)
Cl

Cl
Select the correct answer using the codes given below:
(a) (1), (2) and (3) (b) only (1)
(c) (2) and (4) (d) (1) and (3)

13. Which one of the following will undergo meta substitution on mono chlorination?
(a) chloro benzene (b) phenol
(c) ethyl benzoate (d) ethoxybenzene

14. The following groups when attached to benzene increase the electron density of the benzene. In
which case the increase in electron density is maximum?
(a) OH (b) NH2
(c) CH3 (d) X (Halogen)
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15. Which of the following triad of group activates the benzene ring and directs the electrophile to o
and pposition for substitution
(a) NO2, CHO, COOH (b) OH, O, CH3
(c) OH, SO2OH, NO2 (d) NH2, CHO, SO2OH

16. A particular form of tribromobenzene (A) melts at 44°C. On nitration it forms one possible mononitro
tribromo benzene. The structure of compound (A) is
Br Br
Br
(a) (b)
Br Br
Br
Br
Br
(c) (d) Both (a) and (b)
Br

17. The order of reactivity of following compounds

CH3 CH2CH3 CH(CH3)2 C(CH3)3
(I) (II) (III) (IV)
towards electrophilic substitution will be-[where φ = C6H5]
(a) (I) > (II) > (III) > (IV) (b) (IV) > (III) > (II) > (I)
(c) (II) > (I) > (III) > (IV) (d) (III) > (II) > (I) > (IV)

18. Halogen shows overall deactivation effect for electrophilic aromatic substitution because
(a) it is meta directing.
(b) it has higher (I) inductive effect than (+R) resonance effect.
(c) it has higher (+R) resonance effect than (I) inductive effect.
(d) it is orthopara directing.

19. How many  electron are there in the following species :

(a) 2 (b) 4 (c) 6 (d) 8

20. Number of ฀ electrons present in naphthalene is:

(a) 2 (b) 4 (c) 10 (d) 14

21. Which order is correct for the decreasing reactivity to ring monobromination of the following
compounds:

(I) C6H5CH3 (II) C6H5COOH (III) C6H6 (IV) C6H5NO2

(a) I > II > III > IV (b) I > III > II > IV (c) II > III > IV > I (d) III > I > II > IV

22. Number of benzene derivatives of C7H7Cl is:

(a) 2 (b) 4 (c) 5 (d) 6

23. The number of benzene derivatives of the formula C7H8O is:

(a) 2 (b) 3 (c) 4 (d) 5

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24. Reaction of SO3 is easier in:
(a) Benzene (b) Toluene (c) Nitrobenzene (d) chlorobenzene

25. Which of the following is the strongest o,p-directing group?

(a) OH (b) Cl (c) Br (d) C6H5

26. The highest yield of m-product is possible by the electrophilic substitution of the following:
(a) C6H5CH3 (b) C6H5CH2COOC2H5
(c) C6H5CH(COOC2H5)2 (d) C6H5C(COOC2H5)3

27. Which of the following is not an aromatic compound:

(a) (b) (c) (d)

28. Which of the following undergoes chlorination at fastest rate?

(a) (b) (c) (d)

29. Which of the following is most reactive towards sulphonation?

(a) m-Xylene (b) o-Xylene (c) Toluene (d) p-Xylene

30. Which of the following carbocations is expected to be most stable?

(a) (b) (c) (d)

31. C 6 H 4 Cl 2  Cl 2 
Fe
C 6 H 3Cl
(x) (y)
Only one isomer of ‘y’ is formed. Hence ‘x’ is
(a) o-isomer (b) m-isomer
(c) p-isomer (d) either o or pisomer

(SUBJECTI VE)

32. Using resonance contributors, answer the following. Which is a more stable carbocation
intermediate?
OH CH3

or
+ +
H NO2 H NO2

33. Which is a more stable carbanion intermediate?

NO2 NO2

or Cl

HO Cl OH
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34. A phenyl group has an electronwithdrawing inductive effect. However, each ring of the biphenyl is
more reactive than benzene towards electrophilic substitution and the chief products are ortho and
paraisomers. Show how reactivity and orientation can be accounted for on the basis of resonance.

35. Compare the rate of nitration under similar conditions of PhOMe and PhSMe. Explain.

36. Explain the following percentages of meta product when these compounds undergo electrophilic
substitutions:
(a) ArCH3, ArCH2Cl, ArCHCl2, ArCCl3
4.4% 15.5% 33.8% 64.6%

(b) ArN+Me3, ArCH2N+Me3, ArCH2CH2N+Me3

100% 88% 19%

H OME ASSI GNMENT – 2

1. p-Nitrotoluene on further nitration gives
CH3
CH 3
NO2
(a) (b)

NO2 NO 2 NO 2
CH3 CH3
NO2
(c) (d)
NO2 O2N
NO2

2. Naphthalene undergoes electrophilic substitution reaction at C1 forming naphthalinium ion as

intermediate. Some of the structures of naphthalinium ion are given below. Choose the most stable
structure.
H E H E H E H E
 

(a) (b) (c) (d)


8 9 1
7 2
3. AlCl3
6
+ CH3Cl major product
3
5 10 4
In this reaction the electrophile will attack at the position.
(a) 6 or 7 (b) 1 or 2 (c) 9 or 10 (d) 5 or 8

4. In the following reaction, the major product will be

HNO3
H2SO4
(major product)
N
NO2
NO2
(a) (b) (c) (d)
N N N NO2 N
NO2
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+
5. O2N + NO2
Product of this reaction by single electrophilic substitution is
NO2
(a) O2N (b) O2N NO2
NO2 O 2N
(c) O2N (d) O2N

6. The major product expected from the monobromination of phenyl benzoate is

Br Br

(a) —COO—C6H5 (b) C6H5COO—

(c) Br— —COO—C6H5 (d) C6H5COO— —Br

7. During electophilic substitution the major product in the following reaction will be
FeCl3
+ Cl2 ?
N
H
Cl

Cl
N N
(a) (b)
H H

(c) (d) both (a) & (b)

N
Cl

8. Ring nitration of dimethyl benzene results in the formation of only one nitro dimethyl benzene. The
dimethyl benzene is:

(a) (b) (c) (d) None of these

9. If p-methoxy toluene is nitrated, the major product is:

(a) (b) (c) (d) No reaction

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10. If meta-nitroaniline is chlorinated, the major product is:

(a) (b)

(c) (d)

11. An aromatic compound of molecular formula C6H4Br2 was nitrated when three isomers of formula
C6H3Br2NO2 were obtained. The original compound is:
(a) o-dibromobenzene (b) m-dibromobenzene
(c) p-dibromobenzene (d) None of these

12. Which of the following is the effective electrophile in the sulphonation of benzene?
  

(a) H S O 4 (b)
H S O3 (c)
S O3 (d) SO3

13. Among the following statements on the nitration of aromatic compounds, the false one is
(a) The rate of nitration of benzene is almost the same as that of hexadeuterobenzene.
(b) The rate of nitration of toluene is greater than that of benzene.
(c) The rate of nitration of benzene is greater than that of hexadeuterobenzene.
(d) Nitration is an electrophilic substitution reaction.

14. Which of the following will have fastest rate of reaction with Br2/FeBr3.
NO2 CH3 OCH3

(a) (b) (c) (d)

15. The conversion

CH2CH2CH3 CH2CH2CH3

Br
can be effected using
(a) Br2/CCl4 (b) Br2/OH-
(c) Br2/Fe (d) Br2/benzoyl peroxide

16. In the halogenation of aromatic nucleus, the halogen carrier, is used to generate the species
(a) Cl  (b) Cl+

(c) Cl (d) Cl

17. In the presence of iron catalyst, benzene reacts with chlorine to form
(a) chlorobenzene (b) benzene hexachloride
(c) hexachloro benzene (d) none of these

18. Phenol reacts with bromine in carbon disulphide at low temperature to give
(a) mbromophenol (b) o and pbromophenol
(c) pbromophenol (d) 2,4,6tribromophenol

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19. The direct iodination of benzene is not recommended because
(a) I2 is an oxidising agent. (b) resulting C6H5I is reduced to C6H6 by HI
(c) HI is unstable (d) the ring gets deactivated

CCl3

Cl2, Fe
20. X. What is X as a main product?

CCl3 CCl3
CCl3 Cl Cl
CCl3
Cl

(a) (b) Cl (c) Cl (d) Cl

21. The species responsible for nitration and sulphonation by concentrated nitric acid + concentrated
H2SO4 and fuming H2SO4 respectively, are
(a) NO2 and SO3 (b) NO2+ and SO3
+
(c) NO and SO2 (d) NO2 and SO2

22.  HOCl CH

3COOH
 A. A is

OH Cl OCOCH3 OCl

(a) (b) (c) (d)

23. The major product obtained in the reaction

O
Br2
—C—CH2— FeBr

3

is expected to be
O O
(a) Br— —C—CH2— (b) —C—CH2— —Br

O O

(c) —C—CH — (d) —C—CH2— —Br

Br
Br

24. Which of the following sequence regarding the rate of reaction is true for the electrophilic
substitution involving sulphonation?
(a) k C6 H 6  k C6 D 6  k C6 T6 (b) k C 6 H 6  k C 6 D 6  k C6 T6
(c) k C6 H 6  k C6 D 6  k C6 T6 (d) k C6 H 6  k C6 T6  k C 6 D 6

25. Which of the following reagents and conditions convert benzene to chloro-benzene:
(a) Cl2, sunlight, heat (b) HCl, heat
(c) HCl, sunlight, heat (d) Cl2, AlCl3, cold

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(SUBJECTI VE)

26. For each of the following compounds, indicate the ring carbon that would be mononitrated if the
compound were treated with HNO3/H2SO4.
NO2 O
NHCCH3
(a) (b)
COOH
OCH3 OH

(c) (d)

Cl COOH
O
O
CCH3 OCCH3
(e) (f)
Br CH3OC
O
CH3 Cl

(g) (h)
Cl
NO2

OCOCH3
OH
(i) (j)
CH3

CH3 NO2 SO3H

(k) (l)

27. Give the product(s) obtained from the reaction of each of the following compounds with Br2/FeCl3.
O
(a) OC

(b) CH2O

O O
(c) H3C C COCH3

NO2

(d)
CH3O

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H OME ASSI GNMENT – 3

1. Which of the following statement made on FriedelCrafts reaction is false?
(a) Friedel Crafts alkylation and acylation leads to new carboncarbon bond formation.
(b) Alcohol/acid combination can be used as reagent for FriedelCrafts alkylation.
(c) When benzene and nitrobenzene, both liquids, are mixed and treated with CH3COCl/AlCl3 under
proper reaction conditions, the products obtained are macetyl nitrobenzene and acetophenone.

(d) npropylbenzene can be made in good yield from benzene using npropyl chloride and
anhydrous AlCl3 combination as reagent at low temperature.

2. The halide that will not react with benzene in the presence of anhydrous AlCl3 is
(a) CH3CHClCH3 (b) C6H5CH2Cl
(c) C6H5Cl (d) CH3CH2CH2Cl

3. Which one of the following aromatic compounds fails to undergo FriedelCrafts reactions?
(a) C6H5CH3 (b) C6D6
(c) C6H5NO2 (d) C6H5Cl

4. In the Friedel-Crafts acylation, the electrophile is

 
(a) C 6 H 5 (b) AlCl 3

(c) CH3CO+ (d) C 6 H 5 CH 2

5. The major product obtained by the Friedel-Craft’s reaction of n-butylbromide with benzene in the
presence of anhydrous AlCl3 is
CH2CH2CH2CH3 CH3–CH2–CH–CH3

(a) (b)

CH3
CH3–C–CH3
(c) (d) none of these

6. Benzene reacts with acetyl chloride in presence of anhydrous aluminium chloride to form
(a) acetophenone (b) phenyl acetate
(c) chlorobenzene (d) benzoic acid

7. The function of anhydrous aluminium chloride in the FriedelCrafts reaction is

(a) to absorb water. (b) to absorb hydrochloric acid.
(c) to produce an electrophile. (d) to produce nucleophile.

8. Benzene reacts with npropyl chloride in the presence of anhydrous AlCl3 to give predominantly
(a) npropyl benzene (b) isopropyl benzene
(c) 3propyl1chloro benzene (d) no reaction

9. Which of the following is wrong?

CH3
Anhydrous
AlCl3
(a) + CH3Cl

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CH2CH2CH3
Anhydrous
AlCl3
(b) + CH3CH2CH2Cl
Room
Temperature

CH(CH3)2
Anhydrous
AlCl3
(c) + CH3CH2CH2Cl Room
Temperature

O
CH3C
Anhydrous
AlCl3
(d) + CH3COCl
Room
Temperature

O Anhydrous

10. + CH3CH2CCl AlCl3

X. Identify X.

O
C
(a) (b)

O
OH
(c) (d)
O

11. For preparing monoalkyl benzene, acylation process is preferred than direct alkylation because
(a) In alkylation, a poisonous gas is evolved
(b) In alkylation, large amount of heat is evolved
(c) In alkylation, polyalkylated product is formed
(d) Alkylation is very costly

12. In which of the following reaction tbutylbenzene is formed?

(a) Benzene + t-butyl chloride, AlCl3 (b) Benzene + (CH3)2C=CH2 BF
3 .
HF

H SO
(c) Benzene + t-butyl alcohol 2 
4
 (d) All of these

13. Isopropylbenezene can be obtained by

AlCl3 AlCl 3
(a) + CH3–CH=CH2 (b) + CH3 CH2CH2Cl
Δ

CH3 AlCl3
(c) + CHCl (d) all of these
CH3

14. Product (X) of the following reaction is

SnCl4
(X).

OH

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(a) (b) (c) (d)

15. An aromatic compound 'A' C7H6Cl2, gives AgCl on boiling with alcoholic AgNO3 solution, and
yields C7H7OCl on treatment with sodium hydroxide. 'A' on oxidation gives a mono chlorobenzoic
acid which affords only one mononitro derivative. The compound A is:

(a) (b) (c) (d)

16. m-Bromotoluene is prepared by:

(a) Bromination of toluene
(b) Friedel Craft's reaction of bromobenzene with CH3Cl
(c) Bromination of nitrobenzene and subsequent reduction of –NO2 group.
(d) Bromination of aceto-p-toluidine followed by hydrolysis and deamination.

17. C6H6 + A   C6H5CONH2

A in the above reaction is:

(a) NH2CONH2 (b) ClCONH2 (c) CH3CONH2 (d) CH2(Cl)CONH2

18. C6H6 CH 3COCl A Zn  Hg B

   

AlCl3 HCl
The end product in the above sequence is:
(a) Toluene (b) Ethyl benzene (c) Both the above (d) None

19. The mixture of the following four aromatic compounds on oxidation by strong oxidising agent gives:

, , and

(a) Mixture of C6H5CH2OH + C6H5COOH (b) Mixture of C6H5CHO + C6H5COOH

(c) Only C6H5COOH (d) None of the above

Br2 KMnO4
20. A      B
Compound A and B respectively are:
(a) o-Bromostyrene, benzoic acid (b) p-Bromostyrene, benzaldehyde
(c) m-Bromostyrene, benzaldehyde (d) Styrene dibromide, benzoic acid

21. The number of benzylic hydrogen atoms in ethylbenzene is:

(a) 3 (b) 5 (c) 2 (d) 7

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22. Benzene on reaction with 'A' forms which on reaction with 'B' forms
'A' and 'B' are:

(a) Zn(Hg) + conc. HCl, (b) , LiAlH4

(c) , NaBH4 (d) , Zn(Hg) + conc. HCl

23. Reaction of toluene with CO and HCl in presence of AlCl3/Cu2Cl2 yields

(a) benzoyl chloride (b) p–tolualdehyde
(c) p–chlorotoluene (d) benzyl chloride

24. Which of the following structure corresponds to the product expected, when excess of C6H6 reacts
with CH2Cl2 in presence of anhydrous AlCl3?
(a) Ph2CHCl (b) PhCHCl2
(c) Ph2CCl2 (d) Ph2CH2

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Get Equipped for I I T-JEE

SINGLE CHOICE

1. Chlorination of toluene in the presence of light and heat followed by treatment with aqueous NaOH
gives
(a) ocresol (b) pcresol
(c) 2, 4dihydroxytoluene (d) benzoic acid

2. For the electrophilic substitution reaction involving nitration, which of the following sequence
regarding the rate of reaction is true?
(a) k C6H6  k C6D6  k C6T6 (b) k C6H6  k C6D6  k C6T6
(c) k C6H6  k C6D6  k C6T6 (d) k C6H6  k C6D6  k C6 T6

CH3 CH2 – Cl

3. X 
Which of the following is the correct structure of reagent ‘X’?
(a) PCl3 in the presence of U.V. light (b) SOCl2/ROOR
(c) SO2Cl2/ROOR (d) SO2Cl2 under cold conditions
4. Benzene on reaction with conc. HNO3 in presence of conc. H2SO4 followed by the treatment of Cl2
in presence of FeCl3, gives
(a) 1chloro2nitrobenzene
(b) 1chloro3nitrobenzene
(c) 1chloro4nitrobenzene
(d) a mixture of 2chloro and 4chloro1nitro benzene

5. Sulphonation of benzene differs from most of the electrophilic aromatic substitution reactions. Which
one of the following statement is correct?
(a) is reversible.
(b) requires the presence of Lewis acid as catalyst.
(c) takes place with explosive violence.
(d) requires elevated temperature.

6. Which does not show substitution in benzene ring?

(a) CISO3H (b) conc. H2SO4 on heating
(c) conc. HCl (d) CH3Cl/AlCl3

7. To prevent the formation of carbocation in Friedal craft alkylation the best possible condition is:
(a) AlCl3 + high temperature (b) SnCl4 + high temperature
(c) AlCl3 + low temperature (d) SnCl4 + low temperature

8. A compound reacts reversibly with another to give two products that are isomeric. Isomer (X) is
thermodynamically more stable than isomer (Y) but (Y) is formed much faster. What would the
reaction product consist of after reaction times that were (1) short and (2) very long?
(a) (1) mainly (X) (2) mainly (X) (b) (1) mainly (Y) (2) mainly (Y)
(c) (1) mainly (X) (2) mainly (Y) (d) (1) mainly (Y) (2) mainly (X)

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O
C
CH2 CH3 +
H
9. (X). What is (X)?
C
NH O
OH CH OH
3
C CH2 CH2CCH3
(a) (b) +
N C=O NH=C O

CH3 CH 3

(c) (d)
NH O N OH

COCl Anhydrous
10. AlCl3 (X). The major product is
+
COCl
H O O
C=O C C
(a) (b)
C=O
H
O O
C C

(c) (d) all of these

11. Product obtained when benzoyl acetic acid is heated with soda-lime is:

(a) (b) (c) (d)

12. Benzene, on ozonolysis, followed by reaction with Zn/H2O gives

(a) Hexane–1, 6–dial (b) Glyoxal (3 moles)
(c) Methylglyoxal (2 moles) (d) Oxalic acid (3 mole)

13. The reaction of toluene with chlorine in the presence of light gives
CH3 CH3
Cl
(a) (b)

Cl
CH2Cl CH2Cl
Cl
(c) (d)

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14. Which of the following reactions is not an example of electrophilic substitution
(a) C 6 H 6  CH2 CH CH3   C6H5CH(CH3)2
AlCl3

(b) C 6 H 6  CH2 Cl 2   C 6 H5  CH2 Cl

AlCl3

(c) C 6 H 6  3 Cl 2   C 6 H6 Cl 6
UV light

OH

AlCl
(d) C 6 H5 OH  CO  HCl 3 

CHO
15. Identify the product (X) formed in the following reaction
AlCl
C 6H 6 + CCl4 
3
 (X)
( excess ) Heat

(a) C6H5CCl3 (b) C6H5CCl2C6H5

(c) (C6H5)3CCl (d) (C6H5)4C

16. To transform into , initial steps could be

O2 N

(a) Nitration followed by FriedelCrafts alkylation.

(b) FriedelCrafts alkylation followed by nitration.
(c) Nitration followed by FriedelCrafts acylation.
(d) FriedelCrafts acylation followed by Clemmensen’s reduction followed by nitration.

17. For the given reaction

CH3

CH2 C CH3
+S
CH3

(S) may be
CH3 CH3
|
(a) CH3 C CH2 OH/BF3 (b)
CH3 — C — CH2 — X / AlX3

CH3 |
CH3

CH3

(c) CH3 C C—Cl/AlCl3 (d) All of these

CH3 O
followed by NH2NH2 base

18. The reaction least likely to occur is

H SO
(a) C6H6 + HNO3 2 
4
 C6H5NO2 (b) C6H6 + H2SO4  C6H5SO3H
UV
(c) C6H6 + Br2 
 C6H5Br  C6H5Cl
(d) C6H6 + Cl2 
Fe
light

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19. Anhydrous AlCl3 is used in FriedelCrafts reaction because it is

(a) soluble in ether (b) ionisable to Al and Cl ions
(c) electron rich (d) electron deficient molecule

CH3 CH3 CH3

COPh
Me3CCl PhCOCl
20. AlCl3
C6H6/AlCl3
(A)
AlCl3

CMe3 CMe3
The compound (A) is
CH3 CH3 COPh CH3
COPh
(a) (b) (c) (d)
CMe3
CMe3

21. Identify the major product (X) formed in the following reaction
AlBr3
+ 3CH3Br (X).
Heat

CH3 CH3
CH3 H3C CH3
(a) (b)

CH3
CH3

(c) (d) None of these

H3C CH3

NH2
Br2/H2O NaNO2/HCl (i) HBF4
22. (X) (Y) (Z). Identify the product (Z).
0°5°C (ii) Heat

(a) pBromoflourobenzene (b) p-Bromoaniline

(c) 1, 3, 5Tribromobenzene (d) 2, 4, 6Tribromo1fluorobenzene

+ –
NO2 BF4
23. CH2 (X). What is the product (X) formed in the reaction.

NO2
NO2 NO2

(a) CH2 (b) CH2

NO2 NO2

(c) CH2 NO2 (d) both (b) and (c)

NO2
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O
C Br2/Fe(1eq)
24. N

Br O O
Br

(a) N (b) N

O O Br
C
(c) N Br (d) NH +

ONE OR MORE MAY BE CORRECT

1. Which of the following will show aromatic character:

(a) (b) (c) (d)

2. Benzoic acid may be prepared by the oxidation of:

(a) (b) (c) (d)

3. In which of the following reaction t-butylbenzene is formed:

BF . HF
(a) Benzene + iso-butyl chloride, AlCl3 (b) Benzene + (CH3)2C = CH2 3 

H SO AlCl
(c) Benzene + t-butyl alcohol 2 
4  (d) Benzene + (CH3)2 C= CH2 3 

4. The reaction of replacement of a hydrogen atom in benzene by alkyl group can be brought about
with the following reagents:
(a) Alkyl chloride and AlCl3 (b) Alkene and AlCl3
(c) Alkanol and alkali (d) Alkanol and acid
5. Which of the following statements is correct:
(a) Bromination of toluene occurs faster than that of benzene
(b) Nitration of toluene is faster than that of ethylbenzene
(c) The bromonium ion is a good nucleophile
(d) Effective nitrating agent is nitrate ion

6. Electrophilic substitution in cinnamic acid will take place at :

(a) Ortho-position (b) Para-position
(c) Meta-position (d) On side chain

7. Which of the following gives Friedel Crafts reaction?

(a) (b) (c) (d)

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8. Which of the following can be used in Friedel Crafts reaction of benzene?

(a) (b) CH2=CH–Cl

(c) CH3CH2Cl (d) CH2=CH–CH2–Cl

9. Which of the following will undergo nitration faster than benzene?

(a) (b) (c) (d)

10. Which of the following is ortho-para directing group?

(a) CF3 (b) CCl3
(c) –CH=CH–COOH

(d) – N  C

11. Which of the following statements is true?

(a) Ortho-and para-directing groups generally increase electron density at ortho-and para-positions
(b) Meta-directing groups increase electron density at meta-position
(c) Meta-directing groups decrease electron density at meta-position
(d) Ortho-and para-directing groups decrease electron density at meta-position

12. Which of the following compounds can be classified as aromatic?

(a) 1, 2, 3-Triphenylcyclopropenium cation (b) Cyclooctatetraenyl dianion
(c) Azulene (d) 10-Annulene

13. The structure of the compound that gives a tribromo derivative on treatment with bromine water is:

(a) (b) (c) (d)

14. False statement is / are :

(a) Although benzene contains three double bonds, normally it does not undergo addition reaction.
(b) m-chlorobromobenzene is an isomer of m-bromochlorobenzene.
(c) In benzene, carbon uses all the three p orbitals for hybridization.
(d) An electron donating substitutent in benzene orients the incoming electrophilic group to the
meta position.

15. The possible product(s) of the following bromination reaction is/are

Br2, h
CH2CH3
400600°C

Br
(a) Br CH2CH3 (b) CH2CH3

(c) CH2CH2Br (d) CHCH3

Br

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Passage Type

PASSAGE-1
The Lewis acid usually reacts with the acyl halide to form an acylium ion. The acylium ion is
stabilized by resonance. The acylium ion acts as an electrophile attacking the benzene ring to form an
arenium ion. The arenium ion then loses a proton to generate the final product. Powerful electron
withdrawing groups on the benzene ring such as another acyl group will retard this reaction.
Naphthalene is the simplest and most important of the fused ring hydrocarbons. Five percent of all
constituents of coal tar are naphthalene. Naphthalene can be manufactured using the Friedel-Crafts
reaction via the reaction pathway shown below:
O
O O
C
H2C AlCl3 Zn(Hg), HCl HF
O +
Step 1 Step 2 Step 3
H2C C C C
O OH O OH
O
Zn(Hg), HCl Pd, heat
Step 4 Step 5

Naphthalene
O
1. The Friedel-Crafts reaction occurs twice in the given sequence of reactions. Which two steps
represent Friedel-Crafts reactions?
(a) Steps 1 and 3 (b) Steps 1 and 5
(c) Steps 2 and 4 (d) Steps 3 and 5

2. What type of reaction occurs in step 2?

(a) An oxidation reaction. (b) A reduction reaction.
(c) An elimination reaction. (d) A Friedel-Crafts reaction.

3. What are the most likely products of the following reaction?

O
H3C–C
AlCl3
O +
H3C–C
O
O
O CCH3
O
(a) C2H6 + (b) CH3COH +
C
O OH
O O
O O
COCH3 OCCH3
(c) CH3C-OH + (d) CH3CH +

PASSAGE-2

Benzene and other aromatic rings have tendency to undergo electrophilic aromatic substitution
reactions and do not undergo electrophilic addition reactions like alkenes and alkynes.

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Monosubstituted benzenes undergo substitution reactions either faster or slower than benzene
depending on the fact that whether the group is electron donating or electron withdrawing,
respectively. The directive influence of a group is determined by the fact that the arenium ion formed
by the attack of electrophile on a particular position is more stable than the arenium ion formed by
attacking other [Link] chain oxidation of alkyl benzene generally gives benzoic acid
irrespective of the length or nature of the side chain.

4. Rank the following compounds in the decreasing order of their reactivity towards electrophilic
substitution.

NHCOCH3 ONa NH3 CHCl2

(1) (2) (3) (4)

(a) (1) > (2) > (4) > (3) (b) (2) > (1) > (4) > (3)
(c) (2) > (1) > (3) > (4) (d) (4) > (1) > (2) > (3)

5. In the given reaction,

Conc. HNO3
+
NHC CH3 ?
Conc. H2SO4
O
the probable product would be

(a) NHC CH3 (b) NHC CH3

O O
NO2 NO2

(c) NHC CH3 (d) O2N NHC CH3

O O
NO2

6. In the given compound,

5 4
6 3

7 2
8
N1
H
the electrophile (E) would mainly attack on
(a) position 4 (b) position 5
(c) position 6 (d) position 7

7. Compound (A) having molecular formula C10H10 is chiral, decolourises Br2 in CCl4 and is oxidised by
acidified KMnO4 to give phthalic acid (benzene1,2dicarboxylic acid). The probable structure of (A)
would be

(a) CH3 (b)

CH3
(c) (d)

CH3
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PASSAGE-3

Electrophilic aromatic substitution reactions involve the formation of arenium ion as

intermediate. In this mechanism formation of C—E bond is rate determining step. The second step is
the breaking of C—H bond which is fast step. Most electrophilic reactions are irreversible except
sulphonation, iodination etc. Electrophilic substitution reactions are carried out in the presence of
proton acid or Lewis acid as a catalyst.

8. Which of the following reactions are carried out in the presence of proton acid?
(1) Nitration (2) Sulphonation
(3) Halogenation (4) Friedel-Crafts reaction
Select the correct answer from the codes given below :
(a) only (1) (b) only (2)
(c) (1) and (2) (d) (1), (2), (3) and (4)

9. Consider the following statements for nitration of benzene.

(1) reaction velocity of C6H6 and C6D6 for nitration reaction is different.
(2) reaction velocity of C6H6 and C6D6 is same.

(3) The reacting species of the reaction is N O 2
(4) Sulphuric acid works as catalyst in this reaction.
of these the correct statements are:
(a) only (1) (b) (2) and (3)
(c) (2), (3) and (4) (d) (1), (3) and (4)

10. Nitrating agent for aromatic compound may be

(a) N2O5 (b) HNO3 + H2SO4
(c) CF3SO3NO2 (d) all of these

Assertion & Reason

1. Assertion : Alkylation of benzene by Friedel-crafts reaction gives polyalkylated benzene.

Reason : The ring gets activated for further substitution after introduction of one alkyl group.
(a) A (b) B (c) C (d) D

2. Assertion : In strongly acidic solutions, aniline becomes more reactive towards electrophilic
reagents.
Reason : The amino group being completely protonated in strongly acidic solution, the lone pair of
electrons on the nitrogen is no longer available for resonance.
(a) A (b) B (c) C (d) D

3. Assertion : Acylation of aniline increases the reactivity of benzene ring.

Reason : Acylation of aniline results in decrease of electron density at the benzene ring.
(a) A (b) B (c) C (d) D

4. Assertion : Sulphanilic acid cannot be acylated by treating with acetic anhydride, but its salts with
base can be acylated.
Reason : Sulphanilic acid exists as a zwitter ion.
(a) A (b) B (c) C (d) D
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5. Assertion : Rate of general electrophilic substitution follows the order: C6H6 ≈ C6D6 ≈ C6T6
Reason : CH, CD and CT bonds are not equally strong.
(a) A (b) B (c) C (d) D

6. Assertion : OCOCH3 group when attached to benzene is orthopara directing in the electrophilic
aromatic substitution reactions.
Reason : OCOCH3 group is an activating group because it increases the electron density of
benzene ring by resonance.
(a) A (b) B (c) C (d) D

7. Assertion : Increasing order of acidic strength is BBr3 < BCl3 < BF3.
Reason : Electronegativity increases in the order Br < Cl < F.
(a) A (b) B (c) C (d) D

8. Assertion : The reactivity of thiophene is less than that of furan towards the electrophilic aromatic
substitution.
Reason : Thiophene and furan are both aromatic compounds.
(a) A (b) B (c) C (d) D

Matrix Match
1. Match the following

Column I (Reactions) Column II (Products)

OH COOH

— COOH
(A) Br
2 / 
water
1.
Br
COOH CH2
2. O
C
(B) Br
2 /  
AlCl3

CH2Br 3. 2, 4, 6-tribromophenol

(C) NaOH


COOH

COOH 4. Benzene

5. Decarboxylation
/
(D) NaOH
  
CaO

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2. Match the following

Column I Column II
(A) C6H6 + conc. H2SO4  C6H5SO3H + H2O 1. C6H6 > C6D6 > C6T6
(B) C6H6 + conc. HNO3  C6H5NO2 + H2O 2. C6H3D3 > C6H3T3 > C6T6
HNO
(C) C6H6 + I2 3  C6H5I + HI 3.  C6H2D2T2 ~ C6HT5
C6H6 ~

(D) C6H6 + Cl2  C6H5Cl + HCl

Fe 4. C6H2D2T2 > C6HDT4 > C6T6

3. Match the functional groups attached to benzene given in column I with their effect towards
electrophilic aromatic substitution given in column II.

Column I Column II
(A) –OH 1. deactivating
(B) –Br 2. activating
(C) –NO2 3. ortho–para directing
(D) –CH=CH–CHO 4. meta directing

4. Match the Column (I) with the observations given in Column (II) w.r.t. EAS

Column I Column II
O
NH–C–CH3 CH3
1. Order of reactivity I > II.
(A) (I) (II)

OH Cl
2. The substituents in (I) and (II) are both
(B) (I) (II) o, p– directors.

CH3 CH2CH3
3. One of the substituents is activating
(I) and while the other is deactivating.
(C) (II)

NO2 OH
4. One of the substituents is o, p director
(D) (I) and (II) while the other is a meta director.

Subjective Type Questions

1. Give the products of the following reactions.
O CH3
OCCH3 1. Mg/Et2O
(a) + HNO3 H2SO4
? (b) 2. D2O ?
Br

OCH3 O N

AlCl3 Fe
(c) + O ? (d) + Br2 ?


O
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CH3 CF3
1. NBS/
2. Mg/Et2O FeCl3
(e) 3. ethylene oxide
? (f) + Cl2 ?
+
4. H

2. What products would be obtained from the reaction of the following compounds with hot and
acidified KMnO4?
CH2CH3 CH3 CH2CH2CH2CH3

(a) (b) (c)

CH3 CHCH3
C(CH3)3
CH3

3. Propose a mechanism for each of the following reactions.

CH2CH2CHCH=CH2
CH3 H
+
(a)

H3C CH2CH3
CH=CH2
CH3
+
(b) H

4. Show how the following compounds could be prepared from benzene.

O
CH3
CH3C SO3H
(a) (b)
CH2CH(CH3)2
CH3C=CH2

5. Determine the major product for each of the following reactions.

CH3
Anhydrous Cl2/Fe
(a) AlCl3 (b) O ?
+ O ?
N
H
OEt
(c)
Conc. HNO 3 CH2O
? ?
HCl
ZnCl2
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ANSWERS KEY

Home Assignment -1 (Objective)

Part – A

1.C 2.D 3.C 4.D 5.B 6.A 7.B

8.A 9.A 10.D 11.D 12.D 13.C 14.B

15.B 16.A 17.A 18.B 19.C 20.C 21.B

22.B 23.D 24.B 25.A 26.D 27.B 28.D

29.A 30.B 31.C

(Subjective)

OH
32.

H  
N O
O

is the most stable Intermediate.


OH OH OH OH

 etc

H NO2 H NO2 H NO2 H NO2
Here OH stabilises adjacent carbocation by + R effect but in the other one methyl stabilizes the adjacent
carbocation only by + I effect.
NO2
33. is more stable carbanion because of several resonating structures.

HO Cl
   
O 
O O O O 
O

NO2 N N N
..

 
HO Cl HO Cl HO Cl HO Cl


 E E
34. + E 
H H


E E E

H H H


When the attack occurs at ortho or para position; the positive charge is most delocalized in the other
benzene ring.

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35. PhOMe > PhSMe. The bond from O (which uses a 2porbital) to the ring C is shorter and stronger
than the comparable bond from S (which uses a 3porbital) to the ring C. Therefore, + R effect of –OMe
group will be more than that of –SMe group.

36. (a) Successive replacement of H’s in electronreleasing CH 3 by electronegative Cl’s makes the group
increasingly electronattracting and morienting.
(b) The + charge on N in + NMe3 makes the substituent electronattracting and mdirecting by an
inductive effect. Its influence wanes with increasing CH 2’s between + N and Ar. With two CH 2’s, the
electronreleasing effect of the alkyl group is more significant and o,porientation dominates.

Home Assignment -2

1.A 2.A 3.C 4.B 5.B 6.D 7.A

8.C 9.B 10.B 11.B 12.D 13.C 14.D

15.C 16.A 17.B 18.A 19.B 20.B 11.B

22.B 23.B 24.B 25.A

Subjective

NO2 OCH3
26. (a) (b) NHCOCH3 (c)
CO2H
Cl
OH OCOCH3
COCH3
(d) (e) (f) CH3OC
Br O
CO2H
CH3 Cl OCOCH3
(g) (h) (i)
Cl CH3
NO2
SO3H
CH3 NO2
OH
(j) (k) (l)

O
27. (a) Br O C (b) CH2 O Br

O O NO2
(c) CH3 C COCH3 (d) Br
Br OCH3

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Home Assignment -3

1.C 2.C 3.C 4.C 5.B 6.A 7.C

8.B 9. C 10.A 11.C 12.D 13.D 14.A
15.A 16.D 17.B 18.B 19.C 20.D 21.C
22.D 23.B 24.D

Get Equipped for I I T - JEE

Single choice

1.D 2.C 3.C 4.B 5.A 6.C 7.D

8.D 9. D 10.C 11.A 12.B 13.D 14.C
15.C 16.D 17.C 18.D 19.D 20.A 21.C
22.D 23.C 24.C

Multiple Choice

[Link] [Link] [Link] [Link] [Link] [Link] 7.A

[Link] 9. ABD 10.C [Link] [Link] [Link] [Link]
[Link]

PASSAGE

1.A 2.B 3.B 4.B 5.B 6.C 7.C

8.C 9. C 10.D

ASSERTI ON & REASON

1.A 2.D 3.D 4.A 5.C 6.A 7.D

8.B

MATRI X MATCH

1.A- 3,5 , B – 1 , C- 2 , D – 4,5 2.A – 1,2,4 , B – 3 , C- 1,2,4 , D – 3

3.A – 2 ,3 , B- 1,3 , C-1,4 , D- 1,3 4.A- 1,2 , B- 1,2,3, C – 1,2 , D – 3,4

SUBJECTI VE

OCOCH3 OCOCH3 CH3 CH3

+ NO2 (1) Mg/Et2O
1. (a) (b)
(2) D2O
Br D
NO2
(Major) (Minor)

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OCH3 OCH3
CO(CH2)2COOH N N
(c) + (d) Br
+
C=O (Minor)

CH2CH2COOH (Minor) Br
(Major)
(Major)

CH2CH2CH2OH CF3
(e) (f)
Cl

COOH COOH COOH

2. (a) (b) (c)

COOH COOH
C(CH3)3
CH3 CH3 CH3

(CH2)2CHCH=CH2 (CH2)2CHCH CH3 (CH2)2CCH2CH3

H 1, 2 hydride shift
(a)
3.


H
H


CH=CH2 CHCH3
H
(b)


CH=CH2 CHCH3


CH3
CH3 CH3


H
H

CH3 CH3 CH3

CH3Cl, CH3CH=CH2 1 eqv. Cl2 + h alc KOH,
4. (a)  Heat
AlCl3, H
Heat CH3 CH3
CH3
CH CH3 CCl
(4)

COCH3 COCH3
(CH3)2CHCH2Cl + AlCl3 CH3COCl, Conc. H2SO4
(b) Cold AlCl3 + 
(No rearrangement) SO3H
CH2CHMe2 CH2CH(CH3)2 CH2CH(CH3)2
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 I I T- ia n’s PACE Edu. Pvt. Ltd. ALKYL & ARYL
ALKYL HALIDE Rg -
HALI DES ALH - 1 3

ELIMINATION REACTION

In an elimination reaction, groups are eliminated from the reactant. For example, when an
alkly halide undergoes an elimination reaction, the halogen (X) is removed from the carbon to
which it is attached, and a proton is removed from an adjacent carbon. As a result, a double bond
is formed between the two carbons from which the atoms are eliminated. Therefore, the product
of an elimination reaction is an alkene.
substitution
CH3 CH2 CH2 Y + X–

CH3 CH2 CH2 X + Y–

elimination
CH3 CH CH2 + HY + X–

In this chapter we will first discuss the elimination reactions. of alkyl halides. Then we will
examine the factors that determine whether a given alkyl halide will undergo a substitution reac-
tion, an elimination reaction, or both substituion and elimination reactions.

THE E2 REACTION

There are two important mechanisms for an elimination reaction. The reaction of ethyl bromide
with hydroxide ion is an example of an E2 reaction, where E stands for elimination and 2 stands
for bimolecular. It is a second-order reaction because the rate of ther reaction depends on the
concentrations of both ethyl bromide and hydroxide ion

CH 3 CH 2 Br + HO– CH2 = CH2 +H2 O + Br –

ethyl bromide
rate=k [alkyl halide][base]

The rate law tells us that both ethyl bromide and hydroxide ion are involved in the transition
state of the rate-determining step of the reaction. The following mechanism agrees with the ob-
served second-order kinetics. We see that the E2 reaction is a concerted, one-step reaction. The
proton and the bromide ion are removed in the same step, so no intermediate is formed.

mechanism of the E2
HO

CH2 — CH2   CH2 CH2 + H2 O + Br –

Br

In an E2 reaction of an alkyl halide, a base removes a proton from a carbon adjacent to the
carbon bonded to the halogen. As the proton is removed, the electrons that the hydrogen shared
with carbon move toward the carbon bonded to the halogen. As these electrons move towards the
carbon, the halogens leaves taking its bonding electrons with it. The eloctrons that were bonded to
the hydrogen in the reactant have formed the  bond of the double bond in the product. Removal
of a proton and a halide ion is called dehydrohalogenation.

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The carbon to which the halogen is attached is called the -carbon. A carbon adjacent to an
-carbon is called a -carbon. Because the elimination reaction is initiated by removing a proton
from a -carbon, an E2 reaction is sometimes called a -elimination reaction. It is also called a
1,2-elimination reaction because the atoms being removed are on adjacent carbons.
(B: – is any base.)
B H –carbon
..
RCH — CHR   R — CH CH — R + B —H + Br

–carbon Br

2-Bromopropane has two -carbons from which a proton can be removed in an E2 reaction.
Because the two -carbons are identical, the proton can be removed equally easily from either
one. The product of this elimination reaction is propene.

CH3 CHCH3 + CH3 O–   CH3 CH CH2 + CH3 OH +Br –

propane
Br
2-bromopropane

2-Bromopropane has two structurally different -carbons from which a proton can be
removed. So when 2-bromobutane reacts with a base, two elimination products are formed, 2-
butene and 1-butene.

–carbon

CH3CHCH2CH3 + CH 3O–  CH 3CH CHCH 3 + CH 2 CHCH 2CH3 +CH 3OH + Br–
CH3OH
2-butene 1-butene
Br 80% 20%
2-bromobutane (mixture of E and Z)

How do you know which of the two elimination products will be formed in greater yield? To
answer this question, you must determine which of the alkenes is formed more easily–that is,
which is formed faster. The reaction coordinate diagram for the reaction is shown in the figure.
Free energy

2-bromobutane + CH 3O– 1-butene + CH3 OH

2-butene + CH3 OH

Progress of the reaction

You know that alkene stability depends on the number of alkyl substituents bonded to the sp2
carbons–the greater that number, the more stable the alkene. For example,2-butene, with a total
of two methyl substituent bonded to its sp2 carbons, is more stable than 1-butene, with one ethyl
substituent. In the transition state leading to an alkene, the C–H and C–Br bonds are partially

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broken and the double bond is partially formed, giving the transition state an “alkene-like” struc-
ture. Because the transition state has an alkene-like structure, the one leading to 2-butene is more
stable than the one leading to 1-butene for the same reason that 2- butene is more stable than 1-
butene. The more stable transition state allows 2-butene to from faster than 1-butene.
– OCH
3

CH3 CH CHCH3
–
Br
transition state leading to
2-butene
more stable

The difference in the rate of formation of the two alkenes is not very great. Consequently, both
products are formed, but 2-butene (the more stable of the two alkenes) is the major product of
the elimination reaction. Thus, an E2 reaction is regioselective because more of one constitutional
isomer is formed than the other.
The reaction of 2-bromo-2-methylbutane with hydroxide ion produces both 2-methyl-2-
butene and 2-methyl-1-butene. Because 2-methyl-2-butene is the more substituted alkene (it has
a greater number of alkyl substituents bonded to its sp2 carbons), it is the more stable of the two
alkenes and, therefore, is the major product of the elimination reaction.
CH 3 CH 3 CH 3

CH3 CCH2 CH3 + HO-   CH3 C CHCH3 + CH2 CCH2 CH3 +H2 O + Br –
H2 O
2-methyl-2-butene 2-methyl-1-butene
Br 70% 30%
2-bromo-2-methylbutane

ZAITSEV’S RULE ( SAYTZEFF’S RULE )

In the previous examples we saw that the major product of an elimination reaction is the more
substituted alkene because it is the more easily formed product. Alexander M. Zaitsev, a
nineteenth century Russia chemist, devised a shortcut to predict the more substituted alkene
product. He pointed out that the more substituted alkene product is obtained when a proton is
removed from the -carbon that is bonded to the fewest hydrogens. This is called Zaitsev’s
rule. In 2-chloropentane, for example, there are three hydrogens bonded to one -carbon and
two hydrogens bonded to the other -carbon. According to Zaitsev’s rule, the more substituted
alkene will be the one formed by removing a proton from the -carbon that is bonded to two
hydrogens rather than from the -carbon that is bonded to three hydrogens. Keep in mind,
though, that Zaitsev’s rule is just a shortcut to determine which of the possible alkene products is
the more substituted alkene.
Cl

CH 3 CH 2 CH 2 CHCH 3 + HO –   CH3 CH2 CH CHCH3 + CH3 CH2 CH2 CH CH2

2-pentene 1-pentene
2 -hydrogens 3 -hydrogens 67% 33%
(mixture of E and Z)

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Alkyl halides have the following relative reactivities in an E2 reaction because elimination
from a tertiary alkyl halide typically leads to a more substituted alkene than elimination from a
secondary alkyl halide, and elimination from a secondary alkyl halide generally leads to a more
substituted alkene than elimination from a primary alkyl halide.

relative reactivities of alkyl halides in an E2 reaction

tertiary alkyl halide > secondary alkyl halide > primary alkyl halide

CH 3

CH 3 CH 2 CCH 3 CH 3 CH 2 CHCH 3 CH3 CH2 CH2 CH2 Br

Br Br

CH 3

CH3 CH CCH3 CH3 CH CHCH3 CH3 CH2 CH CH2

three two one

alkyl substituents alkyl substituents alkyl substituents

In most elimination reactions, the more substituted alkene is the major product of the reaction
because it is the more easily formed product. There are some elimination reactions, however, in
which the more substituted alkene is not the more easily formed product.
For example, if the base in an E2 reaction is sterically bulky, it will preferentially remove
the most accessible hydrogen. In the following reaction, it is easier for the bulky tert -butoxide ion
to remove one of the more exposed terminal hydrogens,which leads to the less substituted alkene.
Because the less substituted alkene is the one that is more easily formed, it is the major product of
the reaction.
CH 3 CH 3 CH 3 CH 3 CH 3

CH3CCH2CH3 + CH 3CO–   CH C CHCH + CH CCH 2CH3 + CH3COH + Br –

3 3 2
(CH3)3COH
2-methyl-2-butene 2-methyl-1-butene
Br CH 3 28% 72% CH 3
2-bromo-2-methylbutane tert-butoxide ion

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The data in Table 10.1show that when an alkyl halide undergoes an E2 reaction with a variety
of alkoxide ions, the percent of the less substituted alkene increases as the size of the base in-
creases.

Table 10.1 Effect of the steric properties of the Base on

CH 3 CH 3 CH 3

CH3 CH – CCH3 + RO–  CH3 C CCH3 + CH3 CHC CH2

CH 3 Br CH 3 CH 3
2-bromo-2,3-dimethyl- 2,3-dimethyl- 2,3-dimethyl-

B as e More substituted Less substituted

CH 3 CH 2 O– 79% 21%

CH 3

CH 3 CO – 27% 73%

CH 3
CH 3

CH 3 CO – 19% 81%

CH 2 CH 3

CH 2 CH 3

CH 3 CH 2 CO –

CH 2 CH 3

Although the major product of the E2 dehydrohalogenation of alkyl chlorides, alkyl bromides,
and alkyl iodides is normally the more substituted alkene, the major product of the E2
dehydrohalogenation of alkyl fluorides is the less substituted alkene (Table 10.2).

F CH2CH3

CH3CHCH2 + CH3O–   CH 3CH CHCH 2CH3 + CH 2 CHCH 2CH2CH3 + CH 3OH + F–

CH3OH 2-pentene
2-fluoropentane methoxide 1-pentene
ion 30% 70%
(mixture of E and Z)

You have seen that when a hydrogen and a chlorine, bromine, or iodine are eliminated from
an alkyl halide, the halogen starts to leave as soon as the base begins to remove the proton.
Because the halogen begins to depart with its bonding electrons as soon as the proton begins to
leave, there is no buildup of any negative charge on the carbon that is losing the proton. Thus, the
transition state resembles an alkene

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Table 10.2 Products Obtained from the E2 Reaction of CH 3 O – and 2-Halohexanes

More substituted product Less substitutedproduct

X

CH3CHCH 2CH2CH2CH3 + CH3O–  CH3CH CHCH2CH2CH3 + CH2 CHCH 2CH2CH2CH3

2-hexene 1-hexene
(mixture of E and Z)

Leaving group Cojugate acid pK a

X=1 HI –10 81% 19%
X=Br HBr –9 72% 28%
X=Cl HCl –7 67% 33%
X=F HF 3.2 30% 70%

rather than a carbanion (Section 10.1). Of the halogen ions, the fluoride ion is the strongest base
and, therefore, the poorest leaving group. So when a base begins to remove a proton from an
alkyl fluoride, the fluoride ion has less tendency to leave than the other halide ions. As a result,
negative charge develops on the carbon that is losing the proton, causing the transition state to
resemble a carbanion rather than an alkene. To determine which of the carbanion-like transition
states is more stable, we must determine which carbanion would be more stable.
– – OCH
OCH 3 3

H H
–
CH CHCH2 CH2 CH3 CH 3 CHCHCH 2 CH 3
– 2
– –
F F
transition state leading to transition state leading to
2-pentene 2-pentene
more stable less stable
We have seen that carbocations, because they are positively charged are stabilized by elec-
tron-donating groups. Because alkyl groups are more electron donating than a hydrogen, alkyl
groups stabilize carbocations, so tertiary carbocations are the most stable and methyl cations are
the least stable

relative stabilities of carbocations

R R H H

R — C+ > R — C+ > R — C + > H—C +

R H H H
teritary secondary primary methyl
cabocation corbocation carbocation cation

Increasing stability

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Carbanions, on the other hand, are negatively charged, so they are destabilized by alkyl groups.
Therefore, methyl anions are the most stable and tertiary carbanions are the least stable.
R R H H

R—C < R—C < R — C < H— C

R H H H
te ritary secondary primary methyl
carbonanions carbonanion carbonanion anions

Increasing stability

The transition state leading to 1- pentene has the developing negative charge on a primary
carbon. This is more stable than the transition state leading to 2-pentene, which has the develop-
ing negative charge on a secondary carbon. Because the transition state leading to 1-pentene is
more stable, 1-pentene is formed more rapidly and is the major product of the elimination reac-
tion.
The data in Table 10.2 show that, as the halide ion increases in basisity (decreases in leaving
ability), there is a decrease in the amount of the more substituted alkene product. However, the
more substituted alkene remains the major elimination product in all cases except when the halo-
gen is fluorine.
In the following reactions, Zaitsev’s rule does not lead to the more stable alkene because the
rule does not take into account the fact that conjugated double bonds are more stable than iso-
lated double bonds. Because the conjugated alkene is the more stable alkene, it is the one that is
more easily formed and is, therefore, the major product of the reaction. So, if there is a double
bond or a benzene ring in the alkyl halide, do not use Zaitsev’s rule to predict the major product
of the elimination reaction.
CH3 CH3 CH3
HO –
CH2 CHCH 2CHCHCH 3   CH2 CHCH CHCHCH 3 + CH2 CHCH 2CH CCH 3 + H2O + Cl–
5-methyl-1,3-hexadiene 5-methyl-1,4-hexadiene
Cl a conjugated diene an isolated diene
4-chloro-5-methyl-hexene major product minor product

CH3 CH3 CH3

HO –
CH 2CHCHCH 3   CH CHCHCH 3 + CH 2CH CCH 3 + H2O + Br –

Br
2-bromo-3-methyl- 3-methyl-1-phenly-1-butene 3-methyl-1-phenly-2-butene
1-phenylbutane the double bond is the double bond is not
conjugated with the conjugated with the
benzene ring benzene ring
major product minor product

We can summarize by saying that the major product of an E2 elimination reaction is the more
substituted alkene unless one of the following applies:
 the base is large; + + + +
 the alkyl halide is an alkyl fluoride; ( as well as containing - NR3 , -OR2 , - SR2 , - PR3
 the alkyl halide contains one or more double bonds.

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Because Zaitsev’s rule leads to the more substituted alkene, the rule cannot be used to predict the
major product of an elimination reaction in these three [Link] will see that Zaitsev’s rule
also cannot be used with certain cyclic compounds.

THE E1 REACTION

The reactionof tert-butyl bromide with water to form 2-methylpropene is a first-order elimination
reaction because the rate of the reaction depends only on the concentration of the alkyl halide. It
is called an E1 reaction, where E stands for elimination and 1 stands for unimolecular.
CH3 CH3

CH3— C — Br + H 2O  CH 3 — C CH 2 + H 3O + + Br –
2-methylpropene
CH3
tert-butyl bromide

rate=k[alkly halide]
We know, then, that only the alkyl halide is involved in the transition state of the rate-determining
step of the reaction. Therefore, there must be at least two steps in the reaction. The following
mechanism agrees with the observed first-order kinetics.

mechanism of the E1 reaction

CH 3 CH 3
slow
CH3 — C — Br CH3 — C + + Br –

CH 3 CH 3

CH 3 CH 3
fast
CH3 — C+   CH3 — C + H3 O+

CH 2 CH 2

H2 O H

An E1 reaction is two-step reaction. In the first step, the alkyl halide dissociates
heterolytically. This is the rate-determining step. In the second step of the reaction, the base forms
an elimination product by removing a proton from a carbon adjacent to the positively charged
carbon. Because the first step of the reaction is the rate-determining step, increasing the concen-
tration of the base–which comes into play only in the second step of the reaction–has no effect on
the rate of the reaction.
When two elimination products can be formed, the major product is generally the more
substituted alkene.
CH 3 CH 3 CH 3

CH3 CH2 CCH3 + H2 O  CH3 CH CCH3 +CH3 CH2 C CH2 + H3 O+ + Cl–
2-methyl-2-butene 2-methyl-1-butene
Cl major product minor product
2-chloro-2-methylbutane

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You can see why by looking at the reaction coordinate diagram in Figure 10.2. The more substi-
tuted alkene is the more stable of the two alkenes and, therefore, has the more stable transition
state. Because it has the more stable transition state, it is formed more rapidly. To obtain the more
substituted alkene, the hydrogen is removed from the -carbon bonded to the fewest hydrogens–
following Zaitsev’s rule.

CH3
Free reaction

CH3 CH2 C CH3

+ CH3

CH3CH2C CH2 + H+
CH3

CH3CH CCH3 + H+

Progress of the reaction

Because the first step is the rate-determining step, the rate of an E1 reaction depends on both
the ease with which the leaving group leaves and the stability of the carbocation that is formed.
Thus, the relative reactivities of a series of alkyl halides with the same leaving group parallel the
relative stabilities of the carbocations. A tertiary benzylic halide is the most reactive alkyl halide
because a tertiary benzylic cation–the most stable carbocation–is the easiest to form

relative reactivities of alkyl halides in an E1 reaction = relative stabilities of carbocations

30 benzylic > 30 allylic > 20 benzylic > 20 allylic > 30 > 10 benzylic 1 allylic  20 > 10 > vinyl

Increasing reactivity and stability

Because the E1 reaction involves the formation of a carbocation intermediate, rearrangement

of the carbon skeleton can occur before the proton is lost. For example, the secondary
carbocation that is formed when a chloride ion dissociates from 3-chloro-2-methyl-2-
phenylbutane undergoes a 1,2-methyl shift to form a more stable tertiary benzylic cation.

CH3 CH3 CH3 CH3

1,2-methyl
CH 3 OH –H +
C— CHCH3    C — CHCH 3 shift
 C — CHCH 3   C CCH 3
+ +
CH3 Cl CH3 CH3 CH3
3-chloro-2-methyl- 2-methyl-3-phenyl-
secondary carbocation tertiary benzylic cation
2-phenylbutane 2-butene

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In the following example, the secondary carbocation undergoes a 1,2-hydride shift to form a more
stable secondary allylic cation.
Br
CH3OH +
CH3 CH CHCH2 CHCH2 CH3 CH3 CH CHCH2 CHCH2 CH3
5-bromo-2-heptene
secondary carbocation

1,2-hydride
shift
–H + +
CH3 CH CHCH CHCH2 CH3 CH3 CH CHCHCH2 CH2 CH3
2,4-heptadiene
secondary allylic cation

COMPETITION BETWEEN E2 AND E1 REACTIONS

Primary alkyl halides undergo onyl E2 elimination reactions. They cannot undergo E1 reactions
because of the difficulty encontered in forming carbocations. Secondary and tertiary alkyl halides
undergo both E2 and E1 reactions (Table 10.3).

Table 10.3 Summary of the Reactivity of Alkyl Halides in Elimination Reactions

Primary alkyl halide E2 only

secondary alkyl halide E1 and E2
tertiary alkyl halide E1 and E2

For those alkyl halides that can undergo both E2 and E1 reactions, the E2 reaction is favored
by the same factors that favor an SN2 reaction, and the E1 reaction is favored by the same factors
that favor an SN1 reaction. An E2 reaction is favoured by a high concentration of a strong
base and an aprotic polar solvent (e.g., DMSO or DMF).An E1 reaction, on the other hand,
is favoured by a weak base and a protic polar solvent (e.g., H2O or ROH).

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EXERCI SE # I

(Choose the correct option. Only one is correct)

1. Which of the alkyl halides will undergo SN1 reaction at a fastest rate?
(A) Cl–CH2–CN (B) Cl–CH2 –NO 2 (C) Cl–CH2–OMe (D) Cl–CH2–CH3
Cl

2. OEt The major product is

O

Cl Cl Cl OEt

(A) (B) (C) (D)

OH OEt EtO OH O
O

[Link]
CH3 –CH2 –CH–CH3 
3.    (X) (Major)
|
Br

CH3 CH2 CH CH3

EtOna
(Y) (Major)

NMe3

Product (X)&(Y) respectively is

(A) 1-butene, trans–2–butene (B) 1-butene, cis-2-butene
(C) cis-2-butene, 1–butene (D) trans–2–butene , 1 - butene
Cl
1 equivalent Mg D2O
4. X Y;Y is
ether
Br

Cl D D

(A) (B) (C) (D) none of these

D Br D
5. How many number of optically active isomers are possible for 2,3-dibromo butane 1,4-dioic
acid?
(A) 2 (B) 3 (C) 4 (D) 1
O

. (i) NaCN
6. CH3 Products
(ii) H2SO4
.
Products of above reaction are
(A) Racemic mixture (B) Diastereomer (C) Meso
(D) Mixture of meso compound & optically active compound.

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7. In which of the following molecule all the effect namely inductive, mesomeric & hyperconjugation
operate

CH3 COCH3

(A) Cl (B) (C) (D)

CH3 CH3

8. From each of the following pairs select the compound that will react faster with sodium iodide in
acetone.
(a) 2-Chloropropane or 2-bromopropane
I II
(b) 1-Bromobutane or 2-bromobutane
I II
(A) (a)-I, (b)-I (B) (a)-I, (b)-II (C) (a)-II, (b)-I (D) (a)-II, (b)-II

9. Arrange decreasing order of reactivity of these compounds for nucleophilic substitution

biomolecular reaction
O

(I) CH3 CH2 O S CF3 (II) CH3–CH2–O–Ts

O
(III) CH3–CH–CH 3 (IV) CH3 CH–OCH 3
| |
OH C 6H 5

(A) III, IV, I, II (B) III< IV, II, I (C) I, II, III, IV (D) I, II, IV, III

10. Among the following pairs in which case the second compound has higher heat of hydrogenation.

(A) , (B) Cis-2-butene, trans-2-butene

(C) , (D) 1-butene, 2butene

11. The resonance energy of following heterocycles is in the order

(A) pyrole > furan > pyridine (B) furan > pyrole > pyridine
(C) pyridine > pyrole > furan (D) pyridine > furan > pyrole

12. HBr reacts fastest with

(A) 2-methyl butane-2-ol (B) 3-methyl butane-2-ol
(C) Butane-1-ol (D) 2-methyl butane-1-ol

13. Which of the following alcohol shows fastest reaction with HI?
OH

OH OH
OH
(A) (B) (C) H C (D)
2

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Br CH3
S 2
14. +OH N A ,A is
H H

HO CH3 H CH3

(A) (B)
H H OH H

(C) Both are correct (D) None is correct

15. Arrange the following in order of C–Br bond strength in polar solvent.
Br Br Br Br

(I) (II) (III) (IV)

CH3 H CH3 H

(A) I < II < III < IV (B) III < IV < I < II (C) IV < III < II < I (D) II < I < II < IV

Cl
16. EtOH OEt Rate R1

CH3 CH 3

Cl
EtOH OEt Rate R2

C H3 CH 3
EtOH OEt Rate R3
Cl

Which of following is correct:

(A) R1>R2>R3 (B) R3>R2>R1 (C) R2>R1>R3 (D) R2>R3>R1

17. (I) Br , which is correct about (I)

(A) I is more soluble than bromocyclopropane

(B) I gives pale yellow ppt. on addition with AgNO3
(C) I is having lower dipole moment than bromocyclo propane
Br
(D) I have more ionic character than

18. The reaction of 4-bromobenzy chloride with sodium cyanide in ethanol leads to
(A) 4-bromobenzylcyanide (B) 4-cyanobenzlychloride
(C) 4-cyanobenzyl cyanide (D) 4-bromo-2-cyanobenzyl chloride

19. Which of the following statement about the reactivity of 1-chloro apocamphane
towards AgNO3 is true.

(A) React by SN1 mechanism (B) React by SN2 mechanism

(C) React by SNi mechanism (D) Does not react Cl

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20. Arrange the following halide in decreasing order fo SN1 reactivity.
(I) CH3CH 2CH2Cl (II) CH2=CHCHCH3 (III) CH3CH 2CHCH 3
| |
Cl Cl

(A) I>II>III (B) II>I>III (C) II>III>I (D) III>II>I

OH
21. H+


(A) (B) (C) (D)

OH

H+
22. P. The product P is:

OH
(A) (B) (C) (D)

23. Among the given compounds, the correct dehydration order is:

OH OH OH
(I) (II) (III) OH (IV)

(A) I < II < III < IV (B) II < III < IV < I
(C) I < III < IV < II (D) I < II < III = IV

24. Identify Z in the following series of reaction:

OH conc.H2SO4 Br2 [Link]
H3C X Y
o
170 C CCl4 

OH

H3C CH2
H3C H3C
(A) (B) H3C (C) (D) CH2
CH
OH
HO

CF 2Cl F
1eq. OEt 
25. C C     A (major product),A is
Ph F

OEt
CF 2Cl CF 2 Cl F F 2C CF2 Cl F
OEt
(A) C C (B) C C (C) C C F (D) C C
Ph F Ph Ph OEt F
OEt F

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OH

O
CH3 H+
26. CH3 major product is

CH3 CH3
O CH3 CH3
CH3
O OH
(A) (B) CH3 (C) (D) CH3

CH3 HO

27. Which one of the following alcohol will undergo acid catalysed dehydration with greatest ease by
E1 mechanism ?

(A) CH2 =CH–OH (B) (C) (D) Me2CHOH

OH OH

NaCN
28. (A) C3H6O cyanohydrin of (A). If the cyanohydrin is optically active, then the
2SO4

possible structure of (A) is

H
O O
.
(A) (B) (C) OH (D)
O

29. Which of the following has minimum reactivity towards nucleophiles?

(A) CH 2 O (B) CH 3 CHO
O O

(C) CH3 C CH3 (D) CH3 C CH2 CH3

ROH / H+
30. anhydrous P (major org. product)
O

The product P is
OR
OR R

(A) (B) (C) (D)

O OR O O
O

3 2 1 3 2 1
31. Cl 3C CH CH2 H3C CH CH2
(I) (II)

In addition of HOBr to (I) and (II)

(A) Br is at C2 in both cases (B) Br is at C2 in II and C1 in I
(C) Br is at C1 in II and C2 in I (D) Br is at C1 in both cases

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32. Which of following is correctly matched.
OH
|
(A) CH3 – C – CH3, Ei reaction (B) CH3 – CH2 – CH2OH, E1 cb reaction
|
CH3
OH
CH3
CH3 C CH3
(C) E 1cb reaction (D) CH3 CH2 CH2 N O , cyclic elimination
CH3 CH3

33. Major product obtained in reaction of 1-phenyl-2bromo butane with NaOMe.

(A) (E)-1-phenyl but-1-ene (B) (E)-1-phenyl but-2-ene
(C) 1-phenyl-1-ethoxy butane (D) (Z)-1-phenyl but-2-ene

EXERCISE # I I

1. In the given reaction:

H

N Br2
[X]

[X] is:
H
H
Br N
N
N
Br N Br
(A) (B) (C) (D)
Br Br Br

CHCOOH
2. (maleic acid) can form:
CHCOOH
(A) stereoisomer (B) geometrical isomer (C) chain isomer (D) functional isomer

3. Which can show tautomerism ?

CH2
O
O

(A) (B) CH3 –CN (C) C CH3 (D)

N

4. Which are incorrect statements:

(A) O and O are enantiomers

O O

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Cl CH 3
| |
(B) CH3–C–CH2CH3 and Cl–C–H are enantiomers
| |
H CH 2 CH 3

(C) Argol (sodium potassium tartarate) will show optical isomerism.

(D) CH3CHO on reaction with HCN gives racemic mixture.

5. Which is/are less acidic than Benzoic acid?

(A) CH 3COOH (B) COOH (C) COOH (D) H2O

CH3 NO2

6. Which have active methylene group?

O O

(A) CH3 C CH2 C CH3 (B) CH3– CH2–NO2

O O O

(C) CH3 C CH2 C O Et (D) C CH2 CN

7. Which of the following are not resonating structures of each other:

O O
(A) (B)

O O
(C) (D)

8. Which of the following compounds yield most stable carbonion after rupture of (C1–C2) bond:
O O O

(A) CH3 C CCl 3 (B) CH3 C CBr3 (C) CH3 CH2 C Cl 3 (D) none of these
1 2 1 2 1 2

9. N

H N NH2

pyrrole(I) pyridine(II) aniline(III)

which is/are correct statements?
(A) I is more basic than II (B) II is more basic than I and III
(C) III is more basic than II (D) all are aromatic bases

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10. Which is/are true statement(s)?
(A) Protonation increases electrophilic nature of carbonyl group
(B) CF3SO 3 is better leaving group than CH 3SO 3
(C) Benzyl carbonium ion is stabilised by resonance
OH

(D) CCl3CH is unstable

OH

11. Identify the correct statement(s).

I II III IV

(A) I & III are antiaromatic (B) III & IV are non-aromatic
(C) II alone is aromatic (D) II & IV are non-aromatic
12. Which have acidic hydrogen ?

OH
(A) CH 3COOH (B)

(C) CH3 C CH2 CN (D) NaNH2

13. Which of the following may be classed as an electrophilic reagent?

(A) BCl3 (B) NH4 (C) CH3 (D) AlCl 4

14. The acid strength of substituted carboxylic acids is know to be dependent on the nature and
position of the substituent. In the following examples, an attempt has been made to arrange the
acids in order of acid strength, the strongest first. One of the series is incorrect-which one?
(A) CH3.CH2CH(Cl) .COOH > [Link](Cl).CH2COOH>CH3.CH2.CH2COOH
(B) [Link] > [Link] > [Link]
(C) [Link] > [Link] > [Link]
(D) [Link] > [Link] > (CH3)[Link]

15. Whcih of the following would not have a dipole moment?

OH

(A) CCl4 (B) CH 2Cl2 (C) trans-1,2-dichloroethene (D)

OH

16. Which of the following structures represent the less stable tautomeric form?
OH O

C C
(A) CH3CH2 O C OCH2 .CH3 (B) N CH2

H H

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O
HO H
H
C C
(C) H (D) H3C C CH3
O

17. Which of the following compounds cannot exhibit keto-enol tautomerism?

O
O O
H3C
H3C CH3 H3C CH3
H3C C CH3
C O
(A) (B) (C) (D) H3C CH3

CH3 CH3
H3C

18. In tautomerism
(A) a proton is moved around the molecule (B) electrons are moved around the molecule
(C) no actual movement occurs (D) shift of double bond occurs

19. Which species is not aromatic?

NH
(A) (B) (C) (D)
N
N

20. Which reacts with AgNO3 to give ppt. ?

(A) Br (B) CH CH CH2Br

Br
(C) (D) Br

21. In which of following compound chiral center is not affected on heating.

(A) CH3 CH COOH (B) O

OH CH3
HOOC

(C) CH3– CH – CH2 – COOH (D) CH3 – CHCOOH

| |
OH CH2COOH
22. Which are correct statements?

(A) methyl malonic acid is converted into propanoic acid on heating

(B) succinic acid forms succinic anhydride on heating
(C) 3-hydroxy propanoic acid forms Lactide on heating
O

(D) CH3 C CH2COOH forms acetone on heating

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23. Select incorrect statements:

(A) OH and OH both give colour with FeCl3 solution

(B) 2-pentanone and 3-pentanone are metamers

(C) product formed when benzaldehyde reacts with hydroxylamine shows optical isomerism
(D) 1,2-dibromocyclohexane shows geometrical and optical isomerism.


24. C5H8O4(A)  C4H8O2 (B) 
soda lime

 (C)

C is hydrocarbon occupying 0.509 litre per a approximately. Hence A and B are:

(A) methyl malonic acid, propanoic acid
(B) succinic acid, succinic anhydride
(C) Dimethyl malonic acid, 2-Methyl propanoic acid
(D) Ethyl Malonic acid, Butanoic acid
O

O C

25. CH3 CH CH CH3

product can be: (Both stable & unstable form)

(A) CH3CH(OH)2, CH3CH(OH)COOH
(B) CH3CHO,CH3CH(OH)COOH
(C) CH3CH2COOH, CH3CH2OH
(D) CH3CH(OH)COOH, CH3CH2OH

26. Products formed when HCl adds to 2,4-hexadiene is:

(A) 4-chloro-2-hexene (B) 2-chloro-3-hexene
(C) 2-chloro-4-hexene (D) 1-chloro-2-hexene

27. Match the List I (reaction) with List II (reaction intermediate) and select the correct answer using
the codes given below the Lists. (More than one)
List I List II
[Link] /
(A) F3C–CHCl2     CF2=CCl2 (1) Transition state
CH3
H
(B) CH3 C OH CH3 C CH2 (2) Carbocation

CH3 CH3

alc. KOH
(C) CH3– CH2–Br CH2=CH2 (3) Carbanion


Br

alc. KOH
(D) CH3 C CH3 CH3 C CH2 (4)Free radical

CH3 CH3

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28. Column A Column B
O

N3H
(A) Caprolactum formation take place in (P)
H2SO4

N OH

H+
(B) Beckmann rearrangement is (Q)


OH

(i) CHCl3/HO
(C) Schmidt reaction is (R)
(ii) H+

Ph
CH3
PCl5
C N
(D) Reaction in which number of carbon increases (S)
CH3 OH

29. Match List I with List II and select the correct answer from the codes given below:
List I List II
(A) CH 3–O–SO 2 CH 3+C 2H 5 O- (1) CH3–CH2–PH2

(B) CH3–CH2–I+PH3 (2) CH3–O–C 2H 5

- 
(C) HCC Na + CH3–CH2–Br (3) CH 3 –O–CH 3

(D) CH3–Cl+CH 3–O - (4) CH  C–CH2–CH3

30. Match List-I with List-II for relative rates of given SN2 reaction & select the correct answer from
the codes given below
Z  CH 2 Br  CH 3O  
 Z  CH 2  OCH 3  Br -

List – I Lsit – II
(A) H– (P) 0.1
(B) CH 3 – (Q) 3
(C) C2H5– (R) 1
CH3
CH
(D) (S) 100
CH3

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31. Match List–I & List–II and select correct answer
List – I List – II
(A) R–MgX+HCHO   Adduct (P) Ketone
n-carbon
(B) R–MgX+(CH2)2O   Adduct (Q) 10Alcohol (n+1) carbon
n-carbon
(C) R–MgX+CO2   Adduct (R) Acid (n + 1) carbon
n-carbon
(D) R–MgX+Ph–C  N   Adduct (S) 10 Alcohol (n+2) carbon

EXERCISE # I I I

1. Arrange the following compounds in decreasing order of Keq for hydrate formation.
O

C6H5COCH 3 Cl C CH3

(1) (2)
O O

NO2 C CH3 CH3 C CH3

2. Arrange the following compounds in order of:

Decreasing SN1 reaction rate:

Ph Ph

Ph
Cl Cl
Cl Cl
(II) (III)
(I) (IV)

3. (a) Decreasing SN2 reaction rate:

(I) Cl (II) Cl

(III) Cl (IV)
Cl

4. Which compound is more stable explain

O

(a) CH3 C CH N N (b) CH 3 CH N N

5. Arrange the isomers of molecular formula C4H9Cl in order of decreasing rate of reaction with
sodium iodine in acetone.

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6. Select the member of each pair that shows faster rate of SN2 reaction with KI in acetone.
(a) CH3–CH2–CH2–CH2–Cl or CH3–CH–CH2–Cl
|
CH3
(I) (II)

(b) CH3 – CH2 – CH2 – Cl or CH3 – CH2 – CH2 –Br

(I) (II)

CH3
|
(c) CH3 – CH – CH2 – CH2 – Cl or CH3 – C – CH2Cl
| |
CH3 CH3
(I) (II)

Br Br
| |
(d) CH3–CH2–CH2–CH–CH3 or CH3–CH–CH2–CH–CH3
|
CH3
(I) (II)
7. Select the number of each pair the undergoes SN1 solvoysis in aqueous ethanol more rapidly.
CH3
|
(a) CH3–CH2–CH2–CH2–Cl or CH3 – C –Cl
|
CH3

(b) CH2 = CH – CH2 – Cl or CH3– CH2 – CH2 Cl

CH 3 CH3
| |
(c) CH3 – C – Cl or CH3–C–Br
| |
CH3 CH3
Br Br

(d) or

8. Classify each of the following species as electrophile or nucleophile & explain your choice.

(a) CH 3CO 2 (b) CH 3 O – (c) BF3 (c) Cl (e) CMe 3

(f) :CCl2 (g) SiF4 (h) Br– (i) :P(CH3)3 (j) Me2CH
(k) CH2 = CH2 (I) HCl

9. Of the following statements, which are true for SN2 reaction.

(a) Tertiary alkyl halides reacts faster than secondary.
(b) The absolute configuration of product is opposite to that of the reactant when an optical
active substrate is used.
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(c) The reaction shows first order kinetics.
(d) The rate of the reaction depends markedly on the nucleophilicity of the attacking reagent.
(e) The mechanism is one step.
(f) Carbocations are intermediate.
(g) Rate  [Alkyl halides]
(h) The rate of the reaction depends on the nature of the leaving group.
10. Explain why Cl–CH2–O–CH2–CH3 is hydrolysed more rapidly than CH3–O–CH2–CH2–Cl
11. The dichlorocarbene reacts with electron rich species like phenol where as it doesn’t reacts with
benzene explain.
12. Why is elimination preferred to hemiacetal formation in the acid catalysed cyclisation of this
ketone?
O O
O

Ph
H

OH
O Ph

13. Draw mechanisms for these reactions, explaining why these particular products are formed.
Cl
Cl
MeOH

O Cl
O OMe

14. The reaction of 2,2-dimethyl-1-propanol with HBr is very slow and gives 2-bromo-2-methyl-
propane as the major product.
CH 3 CH 3
| |
CH3CCH2OH CH 3CCH 2CH 3
| |
CH 3 Br
Give a mechanistic explanation for these observations.

15. 1-Bromobicyclo [2.2.1] heptane (the structure of which is shown) is exceedingly unreactive
towards nucleophilic substitution by either the SN1 or SN2 mechanism.

Br
1-Bromobicyclo [2.2.1] heptane

16. Give a mechanism to explain the two products formed in the following reaction.
H CH 3 CH 3
H CH 3
C C H
C CH 3
H NBS, hv H
CH 3 CH 3 Br C C
C C C C H
H
H H H H

3-methyl-1-butene not rearranged rearranged

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17. Comment on the selectivity, (that is, say what else might have happened & why it didn’t) shown in
this grignard addition reaction used in the manufacture of an antihistamine drug, A.
Cl
(i) Mg, Et2O
(ii)

Br N
CHO

18. Select the alkyl halide and a nucleophile that will give each of the following products.
(a) CH3–CH2–CH2 – NH2 (b) CH3 – CH2 –O –CH2 –CH3
(c) CH  C – CH2 –CH2 –CH3 (d) (CH3)2CHS(CH3)2
(e) C6H5 – O –CH2 –CH3

19. Identify the product in each of the following reactions:

NaI (1 mole)
(a) ClCH2CH2 CHCH2CH3 C5H10CII
acetone
Cl
(b) BrCH2CH2Br + NaSCH2CH2SNa   C4H8S2
(c) ClCH2CH2CH2CH2Cl+Na2S   C4H8S

20. Write the structure of the principal organic product to be expected from the reaction of 1-
bromopropane with each of the following:
(a) Sodium iodide in acetone.
O
(
(b) Sodium acetate (CH3CONa in acetic acid.
(c) Sodium ethoxide in ethanol.
(d) Sodium cyanide in dimethyl sulfoxide.
(e) Sodium azide in aqueous ethanol
(f) Sodium hydrogen sulfide in ethanol
(g) Sodium methanethiolate (NaSCH3) in ethanol.

21. Predict the products of the following SN2 reaction:

NaSCH3
(a) C6H5 – CH2 – CH2 – Br NaCN (b) Cl

NaI
(c) CH3 – (CH2)8 – CH2 – Cl acetone (d) N CH3I

(e) HO – CH2–CH2–CH2–CH2–Cl NaOH

22. Draw each of the following reaction in a way that clearly show the stereoisomerism of the prod-
ucts.
H CH3
| |
(a) CH3 – C – Br + CH3ONa (b) CH3 – CH2 – C–Br + CH3OH
| |
CH 2–CH 3 C 3H 7

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Br NaSH
(c) SNI
H3C

23. Complete the following reactions. Give all possible products in each. Give mechanism of the
reactions.

CH3
Moist Ag2O
HOH / 
(a) (b) CH2 Cl
CH2Cl

24. What products would be formed in these reactions ?

Cl
(i) EtMgBr (i) PhLi
(a) Ph – C  CH (ii) Ph2CO
A (b) B
(ii) CO2, (iii) H / H2O
(iii) NH4Cl

CCl 3 C OH + Na   A 
25. B. Find out A & B.
CH2 = CH2

26. Give product and suggest mechanism for these reactions.

MeOCH2Cl CHBr 3 N2 (1) 

(i) ? ? (ii) CO2Et ?
BuLi tBuOK (2) Ph CH = CH2

27. Explain in which solvents these reactions are faster:

CH3 Br

(a) + KOH in CH3OH or CH3CH2OH

I
|
(b) CH3CH2CH2CH2 + OH in CH3OH or 50% CH3OH, 50% H2O
Cl
|
(c) CH3CH2CH2 + CN in CH3CH2OH or DMSO.

28. In each of the following indicate which reaction will occur fatser. Explain your reasoning.
(a) CH3CH2CH2CH2Br or CH3CH2CH2CH2I with sodium cyanide in dimethyl sulfoxide.
(b) 1-chloro-2-methylbutane or 1-chloropentane with sodium iodide in acetone.
(c) Hexyl chloride or cyclohexyl chloride with sodium azide in DMF.
(d) Solvolysis of 1-bromo-2,2-dimethyl propane or tert-butyl bromide in ethanol.
(e) Reaction of 1-chlorobutane with sodium acetate in acetic acid or with sodium methoxide in
methanol.
(f) Reaction of 1-chlorobutane with sodium azide or sodium p-toluenesulfonate in aqueous
ethanol.
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29. CHCl2F is found to react more slowly than CHCl3 in alkaline hydrolysis with plausible mechanism.
Illustrate this phenomenon.

30. Dr. Don T. Doit wanted to sythesize the anesthetic 2-ethoxy-2-methypropane. He used ethoxide
ion and 2-chloro-2-methylpropane for this synthesis and ended up with very little enter. What was
the predominant product of this synthesis? What reagent should he have used?

31. When ethyl bromide is added to potassium t-butoxide, the product is ethyl t-butyl ether.
CH3CH2–Br + (CH3)3C –O– +K   (CH3)3 C– O – CH2CH3
ethly bromide potassium t-butoxide ethyl t-butyl ether
(a) What happens to the reaction rate if the concentration of ethyl bromide is doubled?
(b) What happens to the rate if the concentration of potassium t-butoxide id tripled and the
concentration of ethyl bromide is double ?
(c) What happens to the rate if the temperature is raised?

32. Solution A was prepared by dissolving potassium acetate in methanol solution B was prepared by
adding potassium methoxide to acetic acid. Reaction of methyl iodide either with solution A or
with solution B gave the same major product. Why? What was this product?

33. Select the combination of alkyl bromide and potassium alkoxide that would be the most effective
in the synthesis of the following ethers:

(a) CH3 OC(CH3) 3 (b) OCH3 (c) (CH3 )3CCH2OCH2CH 3

34. (i) Choose the member of the following pairs of unsaturated hydrocarbons that is more reactive
towards acid-catalysed hydration and predict the regiochemistry of the alcohols formed from
this compound.

(a) or
(b) or

(I) (II) (I) (II)

or
(c)
(I) (II)

(ii) Predict on the basic of cabocation stability, which member of each of the following pairs
hydrolyses at the faster rate.
Br Br
Br

(a) or (b) or
Br

(I) (II)

Br
Br
(c) or

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35. Assuming that cation stability governs the barrier for protonation in H — X additions, predict
which compound in each of the pairs in parts (a) to (b) will be more rapidly hydrochlorinated in a
polar solvent.
(I) (II)
(a) CH2 = CH2 or

(b) or

36. If the temperature is not kept below 250C during the reaction of primary alcohols with
p-toluenesulfonyl chloride in pyridine, it is sometimes observed that the isolated product is not the
desired alkyl p-toluenesulfonate but is instead the corresponding alkyl chloride. Suggest a mecha-
nistic explanation for this observation.

37. With the help of following data show HBr exhibits the peroxide effect.
H 1 0 H 2 0
H–X X CH2 X CH2 CH2 XCH2 C H2 H X XCH2CH3 X

HCl –67 +12.6

HBr –25.1 –50.2
HI + 17 –117
All are in kJ mole–1.

38. Formulate the reactions between but-1-ene in presence of small amount of benzoyl peroxide &
(i) CCl4 (ii) CBrCl3
Give your reasons.

39. p-Amino benzaldehyde behaves like an amide as is evident by the fact that it is not readily at-
tacked by the nucleophile at the carbonyl carbon. Explain
40. Explain the following :
(a) 3-pentanol reacts with HBr to give a mixture of 2&3- bromopentane. The exact composition
of the mixture depends upon whether gaseous HBr is used.
(b) Hydration of 3-phenyl-1-butene in dil H2SO4 is not a satisfactory method for preparing
3-phenyl-2-butanol
O
Br2
Br O
41. CH2 CH CH2CH2 C OH
NaHCO3 O
(Cyclic easter lactone)

This type of reaction is called “bromolactonisation”. Suggest a mechanism.

42. Write a reasonable and detailed mechanism for the following transformation.

conc.
H2SO4 H2O

OH

43. We saw that acid-catalyzed dehydration of 2,2-dimethyl-cyclohexanol afforded 1,2-

dimethylcyclohexene. To explain this product we must write a mechanism for the reaction in which

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a methyl shift transforms a secondary carbocation to a tertiary one. Another product of the dehy-
dration of 2,2-dimethylcyclohexanol is isopropylidencyclopentane. Write a mechanism to rational-
ize its formation.
H
CH3
+
CH3
OH H
heat C
CH3
CH3
CH3
CH3

2,2-Dimethylcyclohexanol 1,2-Dimethylcyclohexene Isopropylidenecyclopentane

44. When 2-bromo-2,2-dimethylbutane reacts with a base under E2 conditions, two alkenes (2,2-
dimethyl-1-butane and 2,3-dimethyl-2-butane) are formed.
(a) Which of the following bases would give the highest percentage of the 1-alkene?
(b) Which would give the highest percentage of the 2-alkene
CH3 CH3 CH3
| | |
CH 3 CO – CH 3CH 2CO – CH 3CH 2CO –
| | CH 3 CH 2 O – |
CH3 CH2CH3 CH 3

45. The following reaction takes place under second-order conditions (strong nucleophile), yet the
structure of the product shows rearrangement. Also, the rate of this reaction is several thousand
times faster than the rate of substitution of hydroxide ion on 2-chlorobutane under similar condi-
tions. Propose a mechanism to explain the enhanced rate and rearragement observed in this
unusual reaction.(“Et” is the abbreviation for ethyl.)
Et2N NEt2

H2C CH CH2CH3 OH H2C CH CH2CH3 Cl

Cl OH

46. Give the structures of all possible products when 2-chloro-2-methylbutane reacts by the E1
mechanism.

47. Solvolysis of 1,2-dimethylpropyl p-toluenesulfonate in acetic acid (750C) yields five different
products: three are alkenes and two are substitution products. Suggest reasonable structures for
these five product.

48. Solvolysis of 2-bromo2-methylbutane in acetic acid containing potassium acetate gave three
products. Identify them.

49. (a) Write the structures or build molecular models of all the isomeric alkyl bromides having the
molecular formula C5H11Br.
(b) Which one undergoes E1 elimination at the fastest rate?
(c) Which one is incapable of reacting by the E2 mechanism?
(d) Which one can yield only a single alkene on E2 elimination?
(e) For which isomers does E2 elimination give two alkenes that are not constitutionnal isomers?
(f) Which one yields the most complex mixture of alkenes on E2 elimination?

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50. Evidence has been reported in the chemical literature that the reaction
(CH3CH2)2CHCH2Br+KNH2   (CH3CH2)2C=CH2+NH3+KBr
proceeds by the E2 mechanism. Use curved arrow notation to represent the flow of electrons for
this process.

51. The given compound give mixture of six products on treatment with CH3OH. Write structures of
all five products and give mechanism of the reaction.
CH 2 Br

CH3OH
A+B+C+D+E+F

52. Outline an efficient synthesis of each of the following compounds from the indicated starting
material and any necessary organic or inorganic reagents:
(a) Cyclopentyl cyanide from cyclopentane. (b) Cyclopentyl cyanide from cyclopentene.
(c) Cyclopentyl cyanide from cyclopentanol. (d) Isobutyl iodide from isobutyl chloride.
(e) Isobutyl iodide from tert-butyl chloride. (f) Isobutyl azide from isopropyl alcohol
53. Indicate the major alkene produced by each of the following
Br
CH3 OK / 
(a) CH3 CH2 CH2 C CH3

CH3

CH3

[CH3 
(b) CH2 CH2 C N (CH3)3 OH
[

CH3

CH3

(c) [(CH3)3 N C CH2 CH3 OH
[

CH3

F
(CH 3)3COK
(d) CH3 CH2 CH2 CH CH3

54. Choose the compound of molecular formula C7H13Br that gives each alkene shown as the exclu-
sive product of E2 elimination.

(a) (b) CH2 (c) CH3

CH3 CH(CH3)2

(d) (e) CH CH2 (f)

CH3

(g) C(CH3)3

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55. What will be the products (A,B,C) in the following reaction in presence of peroxide?
RSH
RCH CH2 A
hv
CCl 4 hv BrCCl 3
B
hv
C
Give a mechanism for each of the reactions.

56. Identify (A) to (D) in the given reaction sequence.

Br2 / hv alc KOH HBr LiF
CH3 — CH2 — CH3 (A) (B) (C) (D)
 Peroxide DMF

57. Complete the following reactions

Cl
C6H5 CH   
[Link]

Cl

58. (i) What are the products of the following reactions?

(a) PhCH=CHCH3 + HBr   A
H3C CH3
(b) C C + HI   B
H3C H

CH3

(c) +HBr    C
Peroxide

CH3

(d) +HCl   D

CH2CH3

(ii) What are the products of the following reactions ?

Cl2
(a) PhC  CH + Br2   (b) CH3CH2CH = CH2
H2O

H3C
Br2 NaOH
C CH2
(c) H2O H2O
H3C

59. CH3CH2CH2Cl [Link] A SO2Cl2 B Mg/Et2O C (i) CH3 C CH3

D H2SO4 /  E.
(ii) aq.NH4Cl

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1. REACTIVITY CONSIDERATIONS Nucleophilic Substitution

A halogen is more electronegative than carbon. Consequently, the two atoms do not share their bonding
electrons equally. Because the more electronegative halogen has a larger share of the electrons, it has a
partial negative charge and the carbon to which it is bonded has a partial positive charge.
+ –
RCH2 – X
X = F, Cl, Br, I
The polar carbon-halogen bond causes alkyl halides to undergo substitution and elimination reactions.
There are two important mechanisms for the substitution reaction :
1. A nucleophile is attracted to the positively charged carbon. As the nucleophile approaches the carbon,
it causes the carbon-halogen bond to break heterolytically (the halogen keeps both of the boding electrons).

+ -
Nu + C X C Nu + X-

2. The carbon-halogen bond breaks heterolytically without any assistance from the nucleophile, forming
a carbocation. The carbocation then reacts with the nucleophile to form the substitution product.

+ 
-
C X C+ + X

C+ + Nu C Nu

Regardless of the mechanism by which a substitution reaction occurs, it is called a nucleophilic substitution
reaction because a nucleophile is substituted for the halogen. The mechanism that predominates depends
on the following:
* The structure of the alkyl halide,
* The reactivity and structure of the nucleophile,
* The concentration of the nuccleophile, and
* The solvent in which the reaction is carried out.

2. THE MECHANISM OF SN2 REACTIONS

The rate of a nucleophilic substitution reaction such as the reaction of methyl bromide with dydroxide ion
depends on the concentrations of both regents. If the concentration of methyl bromide in the reaction
mixture is doubled , the rate of the nucleophilic substitution reaction doubles. If the concentration of hydroxide
ion is doubled, the rate of thereaction also doubles. If the concentrations of both reactants are doubled , the
rate of the reaction quadruples .

CH3Br + HO   CH3OH + Br 

methyl bromide methyl alcohol

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When you know the relationship between the rate of a reaction and the concentration of the concentration
of the reactants, you can write a rate law for the reaction.
rate  [ alkyl halide] [ nucleophile ]
Recall from section 3.7 that the “proportional to” sign (  ) can be replaced by an “equal” sing and a
proportionality constant (k).
rate = k [ alkyl halide ] [ nucleophile ]
because the rate of reaction depends on the concentration of two reactants, it is a second  order
reaction ( section 3.7 )
The rate law tells us what molecules are involved in the transition state of the rate  determining step of the
reaction. from the rate law of the reaction of methyl bromide with hydroxide ion, we know that both methyl
bromide and hydroxide ion are involved in the rate  determining transition state. The transition state, there-
fore , is bimolecular because it involves tow molecules. As we saw in section 3.7, the proportionality
constant (k) is called the rate constant. the rate constant describes how difficult it is to overcome the energy
barrier of the reaction ( how hard it is to reach the transition state ). The larger the rate constant , the easier
it is to reach the transition state.
The reaction of methyl bromide with hydroxide ion is an example of an SN2 reaction where S stands for
substitution, N stands nucleophilic , and 2 stands for bimolecular. In 1937 , Edward Hughes and Christopher
Ingold proposed a mechanism for an SN2 reaction. Recall that a mechanism describes the step  by  step
process by which reactants are converted into products. It is a theory that fits the experimental evidence that
has been accumulated concerning the reaction. Hughes and Ingold based their mechanism for an SN2 reaction
on the following three pices of experiment evidence.
1. The rate of the reaction depends on the concentration of the alkyl halide and in the concentration of the
nucleophilic. This means that both reactants are involved in the transition state of the rate  determined step.
2. When the hydrogen’s of methyl bromide are successively replaced with methyl groups, the rate of the
reaction with a given nucleophile becomes progressively slower. ( Table 9.1 )
3. The reaction of an alkyl halide in which the halogen is bonded to a chirality centre leads to the formation of
only one stereoisomer , and its configuration is inverted relative to the configuration of the reacting alkyl
halide.

Relative rate of SN2 reaction of several Alkyl Bromides

R – Br + Cl-  
SN 2
 R – Cl + Br-
Alkyl bromide Class Relative rate

CH3 – Br Methyl 1200

CH3CH2  Br Primary 40
CH3CH2CH2Br Primary 16
CH3CH  Br Secondary 1

CH3
CH3

CH3C Br tertiary too slow to measure

CH3

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The mechanism proposed by Hughes and Ingold for an SN2 reaction is a concerted reaction the reaction
takes place in a single step so no intermediates are formed. The nucleophilic attacks the carbon bearing the
leaving group and displaces the leaving group. Because the nucleophilic hits the carbon on the side opposite
to the side bonded to the leaving group, the carbon is said to undergo back side attack. Back side attack
occurs because the orbital of the nucleophile that contains its nonbonding electrons interacts with the empty
 * molecules orbital associated with the C  Br bond. This orbital has its larger lobe on the side of the
carbon directed away from the C  Br bond. Consequently, the best overlap of the interacting orbital is
achieved through back side. Attack. An SN2 reaction is also called a direct displacement reaction
because the nucleophilic displaces the leaving group in a single step.

mechanism of the SN2 reaction

HO + CH3 — Br   CH3 – OH + Br

How does this mechanism account for the three observed pieces of experimental evidence ? The mechanism
shows the alkyl halide and the nucleophilic coming together in the transition state on the one  step reaction.
Therefore, increasing the concentration of either of them makes their coming together more probable. Thus,
the reaction will follow second  order kinetic , exactly as observed.
Because the nucleophilic attacks the back side of the carbon that is bonded to the halogen, bulky substituents
attached to this carbon will make it harder for the nucleophilic to get to the back side and, therefore , will
decreases the rate of the reaction. this explains why substituting methyl groups for the hydrogen in methyl
bromide progressively shows the of the substitution reaction.

Effects due to group occupying a certain volume of space are called steric effects. A steric effect that
decreases reactivity is called steric hindrance. Results from groups getting in the way at the reaction site.
Because of steric hindrance, alkyl halides have the following relative reactivates iis an SN2 reaction. the
steric crowding in tertiary alkyl halides is so great that they are unable to undergo SN2 reactions.

relative reactivates of alkyl halides in an SN2 reaction.

methyl halide > 1° alkyl halide > 2° alkyl halide > 3° alkyl halide

Increasing reactivity in an S N2 reaction

It is not just the number of alkyl groups attached to the carbon undergoing nucleophilic attack that
determines the rate of an SN2 reaction  the size of alkyl groups is also important. For example, ethyl
bromide and propyl bromide are both primary alkyl halides, but ethyl bromide is more than twice as reactive
in an SN2 reaction because the methyl group of ethyl bromide provides less steric hindrance to back side
attack than does the ethyl group of propyl bromide ( table 9.1 ). Reaction coordinate diagrams for an SN2
reaction with methyl bromide and with a sterically hindered alkyl halide are shown in figure.
As the nucleophilic approaches the back side of the carbon of methyl bromide, the carbon  hydrogen
bonds begin to move away from the nucleophilic and its attacking electrons. By the time the transition state
is reached, the carbon  hydrogen.

  

HO – + C — Br  H O - - - C - - - B r   HO — C + Br –
 

transition state

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R R
– –
HO ----- C ----- Br
H H
– –
HO ----- C ----- Br H
Free energy

Free energy
H

G+
G+
R R
–
CH3Br + HO– CH3OH + Br R–CHBr + HO – R–CHOH + Br –

Progress of the reaction Progress of the reaction

Figure 9.2
Reaction coordinate diagrams for :
(a) the SN2 reaction of methyl bromide with hydroxide ion.
(b) an SN2 reaction of a sterically hindered alkyl bromide with hydroxide ion.

bonds are all in the same plane and the carbon is pentacoordinate ( fully bonded to three atoms and
partially bonded to two ) rather then tetrahedral. As the nucleophile gets closer to the carbon and the
bromine moves farther away from it, the carbon hydrogen bonds continue to move in the same direction.
Eventually, the bond between the carbon and the nucleophile is fully formed and the bond between the
carbon and bromine is completely broken  the carbon is once again tetrahedral.
One way to visualize movement of the groups bonded to the carbon at which substitution occurs is to
picture an umbrella that turns inside out. This called inversion of configuration. The carbon at which
substitution occurs has inverted its configuration during the course of the reaction just as an umbrellas has
tendency to invert to a windstorm. The inversion is known as a Walden inversion, since Pual Walden was
the first to discover that compounds could invert their configuration as a result of substitution reactions.
Because an SN2 reaction takes place with inversion of configuration , only one substation product is
formed when an alkyl halide  that has the halogen leaving group bonded to a chirality centre  undergoes
an SN2 reaction. the configuration of that product of the reaction of hydroxide ion with (R)  2  bromopentane
is (S)  2  pentanol. Therefore, the proposed mechanism accounts for the observed configuration of the
product.
R R

C + HO–  
C + Br –
H H
R R
Br HO

R R
R Br HO R
H H

the configuration of the product is inverted to the configuration of the reactant.

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3. THE SN2 REACTION

The leaving group

If an alkyl iodide, an alkyl bromide, an alkyl chloride, and an alkyl fluoride ( all with the same alkyl same
alkyl group ) were allowed to reach with the same nucleophile under the same conditions, we would find
that the alkyl iodide is the most reactive and the alkyl fluoride is the least reactive.

relative rates of reaction

HO– + RCH2I   RCH2OH + I– 30,000

HO– + RCH2Br   RCH2OH + Br– 10,000
HO– + RCH2Cl   RCH2OH + Cl– 200
HO– + RCH2F   RCH2OH + F– 1

The only difference among these four reactions is the nature of the leaving group. Apparently, the iodide
ion is the best leaving group and the fluoride ion is the worst. This brings us to an important rule in organic
chemistry that will keep coming up in this text  the weaker the basicity of a group, the better its leaving
ability. Leaving ability depends on basicity because a weak base does not share its electrons as well as a
strong base does. Consequently , a weak base is not bonded as strongly to the carbon as a strong base
would be, and a weaker bond is more easily broken.
We have seen that the hydrogen halides have the following relative acidities ( see section 1.18 )

relative acidities of the hydrogen halides

HI > HBr > HCl .> HF

Increasing acidity

Because we know that the stronger the acid, the weaker its conjugate base, we know that the halide ions
have the following relative basicities.
relative basicities of halide ions
I < Br < Cl < F

Increasing basicity

Furthermore, because weaker bases are better leaving groups, the halide ions have the following relative
leaving abilities.

relative leaving abilities of the halide ions

I > Br > Cl > F

Increasing leaving ability

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As a consequence of the relative leaving abilities of the halide ions, alkyl halides have the following relative
reactivities in an SN2 reaction. (Recall from section 1.13 that the bond formed by a halogen becomes longer
and weaker as the atomic weight of the halogen increases )
relative reactivities of alkyl halides in an SN2 reaction
RI > RBr > RCl > RF

Increasing reactivity

The nucleophile

When we talk atoms or molecules that have nonbonding electrons, sometimes we call them bases and
sometimes we call then nucleophiles . What is the difference between a base and a nucleophile ?

A base shares its nonbonding electrons with a proton. Basicity is a measure of how well the base shares
those electrons with a proton. The stronger the base, the better it shares its electrons. Basicity is measured
by an equilibrium constant ( the acid dissociation constant , Ka ) that indicates the tendency of the conjugate
acid of the base to lose a proton. ( section 1.17 )

A nucleophile uses its nonbonding electrons to attack an electron  deficient atom other than a proton.
Nucleophilicity is a measure of how readily the nucleophile is able to attack such an atom. It is measured
by a rate constant (k). In the case of the an SN2 reaction, nueclephilicity is a measure of how readily the
nucleophile attacks an sp3 hybridized carbon bonded to a leaving group. Thus , a base forms a new bond
with a proton, whereas a nucleophile forms a new bond with an atom other than a proton.
When comparing molecules with the same attacking atom, there is a direct relationship between basicity
and nucleophilicity. Stronger bases are better nuecleophlies. For example , a species with a negative charge
is a stronger base and a better nuecleophile than a species with the same attacking atom that is neutral. Thus
HO is a stronger base and a better nucleophile than H2O.

stronger base, weaker base

better nucleophile poorer nucleophile

HO– > H 2O
CH3O – > CH3OH
–
NH2 > NH3
CH3CH2NH– > CH3CH2NH2

When comparing molecules with attacking atoms of approximately the same size, the stronger bases are
again the better nucleophiles. The atoms across the second row of the periodic table have approximately the
same size. If hydrogens are attached to the second  row elements, the resulting compounds have the
following relative acidities ( section 1.18 )
relative acid strengths
CH4 < NH3 < H2O < HF

Increasing acidity

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consequently , the conjugate bases have the following relative base strengths and nucleophilicities. For
example. The methyl anion is the strongest base as well as the best nucleophile.

relative base strengths and relative nucleophilicities


CH3 > NH2 > HO > F

Increasing basicity and nucleophilicity

when comparing molecules with attacking atoms that are very different in size, the direct relationship
between basicity and nucleophilicity is maintained if the reaction occurs in the gas phase. If however the
reaction occurs in a solvent  as most organic reactions do  the relationship between basicity and nucleophilicity
depends on the solvent.
If the solvent is protic ( ie. it has a hydrogen bonded to an oxygen or to a nitrogen, making it a hydrogen
bond donor ) , the relationship between basicity and nucleophilicity becomes inverted. In other words, as
basicity decreases, nucleophilicity increases. Iodide ion, therefore, which is the weakest base of the
halogen family, is the best nucleophlie in a protic solvent.
increasing
nucleophilicity
increasing in a polar
size solvent
F–

Cl–

Br–

I–
increasing
basicity

Why, in a protic solvent, is the largest atom the best nucleophile even though it is the weakest base ? First
of all, the larger the atom, the farther away the electrons are from the nucleus, and the more polarizable it is.
( Recall from section 2.9 that polarizability indicates how easily an atom’s electron cloud can be distorted ).
Because the electrons are farther away, they are not held as tightly and can, therefore, move more freely
toward a positive charge. As a result, the electrons are able to overlap from farther away with the orbital of
carbon, as shown in figure 9.3. This results in a greater degree of bonding in the transition state, making it
more stable. Secondly, the protic solvent makes the larger atoms better nucleophiles by making the smaller
atoms less nucleophlic.
more bonding


H  H 
 –

C—X   C ------- X 

 
H  H 
I– H  H 
 
trantisition state

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little bonding


H  H 
 – 
 
C—X   C ------- X 
 
F– H  H H 
H  
 
trantisition state

The effect of the solvent of Nucleophilicity

How does a protic solvent make the smaller atom less nucleophilic ? When a negatively charged species
is placed in a protic solvent, the ion becomes solvated ( section 2.9 ). The solvent molecules arrange
themselves so that their partially positively charged hydrogens point toward the negatively charged species.
The interaction between the ion and the dipole of the protic solvent is called an ion  dipole interaction. At
least one of the ion  dipole interactions must be broken before the nucleophile can participate in an SN2
reaction. Weak bases interact weakly with protic solvents, whereas strong bases interact more strongly
because they are better at sharing their electrons. It is easier , therefore , to break the ion  dipole interactions
between an iodide ion ( a weak base ) and the solvent than between a fluoride ion ( a stronger base ) and the
solvent. As a result , iodide ion is a better nucleophile than fluoride ion in a protic solvent ( Table 9.2 )
+
H
O –
H
+ +
+ + H
– O H
Y– H O
–
H +
+ H
– O

H
+
ion-dipole interaction between
anucleophile and water

TABLE 9.2 Relative Nucleophicity toward CH3l in Methanol

RS–
I–
–
CN
increasing nucleophilicity

CH3O –
Br–
NH3
Cl–
F–
CH3OH

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The nucleophilicity of a small species like a fluoride ion would increase in a nonpolar solvent because
there are no ion-dipole no ion-dipole interactions between the ion and the solvent. However, ions are
insoluble in most nonpolar solvents but they can dissolve in aprotic polar solvents such as dimethylformamide
(DMF) or dimethylsulfoxide (DMSO). An aprotic polar solvent is not a hydrogen bond donar because it
does not have a hydrogen attached to an oxygen or to a nitrogen, so there are no positively charged
hydrogens to form iondipole intersection. Aprotic polar solvents have a partial negative charge on the
surface of their molecules that can solvate cations, but the partial positive charge is on the inside of the
molecule, which makes it less accessible. Therefore, the relatively “naked” anion can become a powerful
nucleophile in an aprotic polar solvent. Thus fluoride ion is a better nucleophile in DMSO than it is in water.

O CH3 O
|| | ||
H — C — N — CH3 CH3 — S — CH3
N, N dimethyl formamide dimethyl sulfoxide
DMF DMSO

Nucleophilicity Is Affected by Steric Effects

Because a base removes a relatively unhindered proton, base strength is relatively unaffected by steric
effects. The strength of a base depends only on how well the base shares its electrons with a proton. For
example, tert  butoxide ion is a stronger base than ethoxiode ion because tert  butaxide ion is a stronger
base than ethoxide ion because tert-butanol ( pKa = 18 ) is a weaker acid than ethanol ( pKa = 15.9 ).

CH3
|
CH3CH2O– CH3CO –
|
CH3
ethoxide ion tert-butoxide ion
better nucleophile stronger bae

Steric effects, on the other hand, do affect nucleophilicity. A bulky nucleophile cannot approach the back
side of a carbon as easily as a less sterically hindered nucleophile can. Thus, the bulky tert  butoxide ion,
with its three methyl groups, is a poorer nucleophile can. Thus, the bulky tert-butoxide ion, with its three
methly groups, is a poorer nucleophile than ethoxide ion even though tert  butoxide ion is a stronger base.
Therefore, if you want a species to act as base, you should choose one that is bulky because it will be less
apt to act as a nucleophile. On the other hand, if you want a species to act as a nucleophile, you should use
a non  sterically hindered reagent.

4 THE REVERSIBILITY OF AN SN2 REACTION

Because there are many different kinds of nucleophiles, a wide variety of organic compounds can be
synthesized by means of SN2 reactions. The following reactions show just a few of the many kinds of
organic compounds that can be synthesized in this way.

CH3CH2Cl + HO–   CH3CH2OH + Cl–

an alcohol

CH3CH2Br + HS–   CH3CH2SH + Br–

a thiol

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CH3CH2I + RO–   CH3CH2OR + I–

an ether

CH3CH2Br + RS–   CH3CH2SR + Br–

a thioether

CH3CH2Cl + NH2   CH3CH2NH2 +Cl–

a primary amine

CH3CH2Br + –C  CR   CH3CH2C  CR + Br–

an alkyne

CH3CH2I + –C  N   CH3CH2C  N + I–

a nitrile

CH3CH2CH2Br + NH3   CH3CH2CH2 Ν H3Br– CH3CH2CH2NH2 + HBr
a primary amine

CH3I + CH3CH2NH   CH3CH2 Ν HCH3 I– CH3CH2NCH3 + HI
| | |
CH3 CH3 CH3
a tertiary amine

The reverse of each of these reactions can also be visualized as a nucleophilic substitution reaction. In the
first reaction, for example , ethyl chloride reacts with hydroxide ion to from ethyl alcohol and a chloride ion.
The reverse reaction appears to satisfy the requirements for a nucleophilic substitution reaction because the
chloride ion is a nucleophile and ethyl alcohol has an HO leaving group. But ethyl alcohol and chloride ion
do not react.
Why does a nucleophilic substitution reaction take place in one direction but not in the other? We can
answer this question by comparing the leaving tendency of Cl in the forward direction and the leaving
tendency of HO in the reverse direction. In order to compare leaving tendencies, we must compare basicities.
Most people find it easier to compare the acid strengths of the conjugates acids ( table ), so that is what we
will do. HCl is a much stronger acid than H2O, which means that Cl is a much weaker base than HO
( remember that the stronger the acid, the weaker its conjugate base ). Because it is a weaker base, Cl is
a better leaving group. Consequently , HO can displace Cl– is the forward reaction, but Cl cannot displace
HO in the reverse reaction. The reaction proceeds in the direction that allows the stronger base to displace
the weaker base ( the best leaving group )

If the different between the basicities of the nucleophile and the leaving group is not very larger, the
reaction will reversible . For example , in the reaction of ethyl bromide with iodide ion, Br is the leaving
group in one direction and I is the leaving group in the other direction. Because the pKa values of the
conjugate acid is of the two leaving groups are similar ( pKa of HBr =  9 ; pKa of HI =  10 ) , the reaction
is reversible.
TABLE 9.3 The Acidities of the Conjugate Acids of Some Leaving Groups

Acid pKa Conjugate base (leaving group)

HI –10.0 I–
HBr –9.0 Br–

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HCl –7.0 Cl–
–
H2SO4 –5.0 OSO3H

CH3 O H2 –2.5 CH3OH
+
H3O –1.7 H 2O

SO3H –0.6 SO 3–

HF 3.2 F–
O O

CH3COH 4.8 CH3CO –

H2S 7.0 HS–
HC  N 9.1 –
CN

N H4 9.4 NH3
CH3CH2SH 10.5 CH3CH2S–

(CH3)3 N H 10.8 (CH3)3N
CH3OH 15.5 CH3O –
H 2O 15.7 HO–
HC  CH 25 HC  C–
–
NH3 36 NH2
H2 very large H–

CH3CH2Br + I– CH3CH2I + Br

You can drive a reversible reaction toward the desired products be removing one of the products as it is
formed. Le Chatelier’s principle states that if an equilibrium is disturbed, the system will adjust to
offset the disturbance. In other words, if the concentration of product C is decreased. A and B will react
to from more C and D so that the value of equilibrium constant does not change.
A+B C+D
[C][D]
Keq = [A][B]
For example, the reaction of ethyl chloride with methanol is reversible because the difference between the
basicities of the nucleophile and the leaving group is not very large. If the reaction is carried out in a neutral
solution, the protonated product will lose a proton ( section 1.20 ). This disturbs the equilibrium and drives
the reaction toward the product.
 
CH3CH2Cl + CH3OH CH3CH2 O CH3 

H
 CH3CH2OCH3
fast

H + Cl–

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5. THE MECHANISM OF SN1 REACTIONS

Given our understanding of the SN2 reaction, we would expect the rate of reaction of tert  butyl bromide
with water to be relatively slow because water is a poor nucleophile and tert – butyl bromide is sterically
hindered to attack by a nucleophile. It turns out, however , that the reaction is surprisingly fast. In fact, it is
over one million times faster than the reaction methyl bromide  a compound with no steric hindrance  with
water ( table 9.4 ). Clearly , the reaction must be taking place by a mechanism different from that of an SN2
reaction.
CH3 CH3
| |
CH3 — C— Br + H2O  CH3 — C — OH + HBr
| |
CH3 CH3
tert-butyl bromide tert-butyl alcohol

As we have seen, a study of the kinetics of a reaction is one of the first steps undertaken when investigating
the mechanism of reaction. If we are to investigate the kinetic of the reaction of tert – butyl bromide with
water, we would find that doubling the concentration of the nucleophile has no effect on the rate of the
reaction. Knowing that the rate of this nucleophilic substitution reaction depends only on the concentration
of the alkyl halide, we can write the following rate law for the reaction.

rate = k[alkyl halide]

Because the rate of the reaction depends on the concentration of only one reactant, it is a first-order
reaction.

The rate law for the reaction of tert-butyl bromide with water differs from the rate law for the reaction of
methyl bromide with hydroxide ion, so the two reactions must follow different mechanisms. We have seen
that the reaction between methyl bromide and hydroxide ion is an SN2 reaction (Section 9.2). The reaction
between tert-butyl bromide and water is an SN1 reaction where S stands for substitution, N stands for
nucleophilic, and 1 stands for unimolecular. The mechanism of an SN1 reaction is based on the following
experimental evidence:

1. The rate law shows that the rate of the reaction depends only on the concentration of the alkyl
[Link] means that we must be observing a reaction whose rate-determining transition state
involves only the alkyl halide. The rate only one molecule.
2. When the methyl groups of tert-butyl bromide are successively replaced by hydrogen’s, the rate of
the SN1 reaction decreases progressively (Table 9.4). This is opposite to the order of reactivity
exhibited by alkyl halides in SN2 reactions (Table 9.1).
3. The reaction of an alkyl halide in which the halogen is bonded to a chirality centre forms two
stereoisomers: one with the same relative configuration as the reacting alkyl halide, and the other
with the inverted configuration.

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Table 9.4 Relative Rates of SN1 Reactions for Several Alkyl Bromides
(Solvet Is H2O, Nucleophile is H2O)

Alkyl bromide Class Ralative rate

CH3
|
CH3C — Br tertiary 1,200,000
|
CH3

CH3CH — Br secondary 11.6

|
CH

CH3CH2 — Br primary 1.00*

CH3 — Br methyl 1.05*

* Although the rate of the SN1 reaction of this compound with water is 0, a small rate is observed as a
result of an SN2 reaction.

An SN1 reaction has two steps. In the first step, the carbon-halogen bond breaks hetrolytically, with the
halogen retaining the previously shared pair of electrons. In the second step, the nucleophile reacts rapidly
with the carbocation formed in the first step.
mechanism of the SN1 reaction

CH3 CH3
| slow |
CH3 — C — Br CH3 — C+ + Br–
| |
CH3 CH3

CH3 CH 3 CH 3
| | |
+ +
CH3 — C+ + H2 O fast
 
CH3 — C — O H CH3 — C — O H + H3 O
| | | |
CH3 CH3 H CH 3

O —H
|
H

Because the rate of SN1 reaction depends only on the concentration of the alkyl halide, the first step must
be the slow and rate-determining step. The nucleophile, therefore, is not involved in the rate-determining
step, so its concentration has no effects on the rate of the second step will not make an SN1 reaction go any
faster.

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carbocation
intermediate

Free energy G + R + + X–
+ – Nu

R—X

R — Nu

Progress of the reaction

How does the mechanism for an SN1 reaction account for the three pieces of experimental evidence?
First, because the alkyl halide is the only species that participates in the rate-limiting step, the mechanism
agrees with the observation that the rate of the reaction depends on the concentration of the alkyl halide and
does not depend on the concentration of the nucleophile.
Second, a carbocation is formed in the slow step of an SN1 reaction. Because a tertiary carbocation is
more stable and is therefore easier to form than a secondary carbocation, which in turn is more stable and
easier to form than a primary carbocation (Section 3.10), tertiary alkyl halides are more reactive than
secondary alkyl halides, which are more reactive than primary alkyl halides in an SN1 reaction. Thus, the
reactivity order agrees with the observation that the rate of an SN1 reaction decreases as the methyl groups
of tert-butyl bromide are successively replaced by hydrogen as the methyl groups to tert-butyl bromide are
successively replaced by hydrogen (Table 9.4).

relative reactive of alkyl halides in an SN1 reaction

30 alkyl halide >20 alkyl halide > 10 alkyl halide

Increasing reactivity

Actually, primary carbocations and methyl cations are so unstable that primary alkyl halides and methyl
halides do not undergo SN1 reactions. (The very slow reactions reported for ethyl bromide and methyl
bromide in Table 9.4 are SN2 reactions.)
The positively charged carbon of the carbocation intermediate is sp2 hybridized, and the three bonds
connected to an sp2 hybridized carbon are in the same plane. In the second step of the SN1 reaction, the
nucleophile can approach the carbocation from either side of the plane.

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C — Br

Br – –Br –

+
a C b

H2 O O H2

a b

–H + + + –H +
HO — C HO — C C — OH C — OH
H+ H H+
inverted configuration same configuration as
relative to the configuration the alkyl halide
of the alkyl halide

If the nucleophile attacks the side of the carbon from which the leaving group departed, the product will
have the same relative configuration as the reacting alkyl halide. If, however the nucleophile attacks the
opposite side of the carbon, the product will have the inverted configuration relative to the configuration of
the alkyl halide. We can now understand the third piece of experimental evidence for the mechanism of the
SN1 reaction. The SN1 reaction of an akyl halide, in the which the leaving group is attached to a chirality
center, forms two stereoisomers because attack of the nucleophile on one side of the planar carbocation
forms one stereoisomer, and attack on the other side produces the other stereoisomer.
R R R

C + H2 O  
C + C + HBr
H H H
R R R
Br HO OH

R R R
R Br HO R + HO R
H H H
if the leaving group in an SN1 reaction is attached to a chirality center,
a pair of enantiomers will be formed as products

THE SN1 REACTION

THE LEAVING GROUP

Because the rate-determining step of an SN1 reaction is the dissociation of the alkyl halide to form a
carbocation, two factors affect the rate of an SN1 reaction-the ease with which the leaving group dissociates
from the carbon and the stability of the carbocation that is formed. In the preceding section, we saw that
tertiary alkyl halides are more reactive than secondary alkyl halides, which are more reactive than primary

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alkyl halides. This is because the more substituted the carbocation is, the more stable it is and therefore the
easier it is form. But what about a series of alkyl halides with different leaving groups that dissociate to form
the same carbocation? The answer is the same for the SN1 reaction as for the SN2 reaction. That is, the
weaker the base, the less tightly it is bonded to the carbon and the easier it is to break the carbon-halogen
bond. As a result, an alkyl iodide is the most reactive and an alkyl fluoride is the least reactive of the alkyl
halides in both SN1 and SN2 reactions.

relative reactivates of alkyl halides in an SN1 reaction

RI > RBr > RCl > RF

Increasing reactivity

THE NUCLEOPHILE

The nucleophile traps the carbocation that is formed in the rate-determining step of an SN1 reaction.
Because the nucleophile has no effect on the rate of the SN1 reaction.
In some SN1 reactions, the solvent is the nucleophile. For example, the relative rates given in Table 9.4 are
for the reactions of alkyl halides with water. Water serves as both the nucleophile and the solvent. When the
solvent is the nucleophile, the reaction is called as solvolysis reaction. Thus, the relative rates in Table 9.4
are for the solvolysis reactions of the indicated alkyl bromides in water.

CARBOCATION REARRANGEMENTS

A carbocation intermediate is formed in an SN1 reaction. In section 3.14 we saw that a carbocation will
rearrange if it becomes more stable in the process. If the carbocation formed in an SN1 reaction can rearrange,
SN1 and SN2 reactions of the same alkyl halide can produce different constitutional isomers as products
because carbocations are not formed in an SN2 reaction and, therefore rearrangement of the carbon skeleton
cannot occur. For example, the product obtained when 2-bromo-3-methylbutane undergoes an SN1 reaction
is different from the product obtained when it undergoes an SN2 reaction. When the reaction is carried out
under conditions that favor an SN1 reaction, the initially formed secondary carbocation undergoes a 1,2-
hybride shift, rearranging to a more stable tertiary carbocation.
CH 3 CH 3 CH 3
SN1 1,2-hydride shift H2 O
CH 3 CHCHCH 3    CH 3 CCH 2 CH 3   CH3 CCH2 CH3
+ +
CH 3 +OH
secondary tertiary H
CH 3 CHCHCH 3 carbocation carbocation
H + –H +
Br
CH 3 CH 3
2-bromo-
3-methylbutane SN2
CH 3 CHCHCH 3 CH 3 CCH 2 CH 3
HO –
OH OH
3-methyl-2-butanol 2-methyl-2-butanol

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The product obtained from the reaction of 3-bromo-2, 2-dimethylbutane with a nucleophile also depends
on the conditions under which the reaction is carried out. The carbocation formed under conditions that
favor an SN1 reaction undergoes a 1, 2-methyl shift. Because a carbocation is not formed under conditions
that favor an SN2 reaction, the carbon skeleton does not rearrange.
CH 3 CH 3 CH 3
SN1 1,2-methyl shift H2 O
CH 3 C–CHCH 3    CH 3 C–CHCH 3   CH3 C—CHCH3
+ +
CH 3 +OH
CH 3 CH 3
H
CH3 C — CHCH3 secondary tertiary
carbocation carbocation H + –H +
CH3 Br
CH 3 CH 3
3-bromo-2,2
dimethylbutane SN2
CH3 C — CHCH3 CH 3 C—CHCH 3
HO –
CH 3 OH OH CH 3
3,3-dimethyl-2-butanol 2,3-dimethyl-2-butanol

We will see in Sections 9.9 and 9.10 that we can exercise some control over whether an SN1 and SN2
reaction takes place by choosing appropriate reaction conditions.

BENZYLIC HALIDES, ALLYLIC HALIDES,

VINYLIC HALIDES, AND ARYL HALIDES

To this point, we have limited our discussion of substitution reactions to methyl halides and primary,
secondary, and tertiary alkyl halides. But what about benzylic, allylic, vinylic, and aryl halides? Let’s first
consider benzylic and allylic halides. Benzylic and allylic halides readily undergo SN2 reactions unless they
are tertiary. Tertiary benzylic and tertiary allylic halides, like other tertiary halides, are unreactive in SN2
reactions because of steric hindrance.
SN2 conditions
CH2 Cl + CH3 O–    CH2 OCH3 + Cl–

benzyl chloride benzyl methyl ether

SN2 conditions
CH3 CH = CHCH2 Br + HO–    CH3 CH = CHCH2 OH + Br –
1-bromo-2-butane 2-butane-1-ol
an allylic halide
Benzylic and allylic halides also undergo SN1 reactions because they from relatively stable carbocations.
While primary alkyl halides (such as CH3CH2Br and CH3CH2CH2Br) cannot undergo SN1 reactions because
their carbocations are too unstable, primary benzylic and primary allylic halides readily undergo SN1 reactions
because their carbocations are stabilized by electron delocalization (Section 6.7).
SN1 + CH 3 OH
CH2 Cl CH2    CH3 OCH3 + H+
+ Cl–
SN1 + H2 O
CH2 = CHCH2 Br CH2 = CHCH2   CH2 = CHCH2 OH + H+
+ Br –

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If the resonance contributors of the allylic carbocation intermediate do not have the same groups bonded
to their sp2 carbons, two substitution products will be obtained.
SN1 + +
CH3 CH— CHCH 2 Br CH3 CH — CHCH2 CH3 CHCH — CH2

H2 O H2 O

CH3 CH = CHCH2 OH CH3 CHCH = CH2

+ H+ OH + H+

Vinylic halides and aryl halides do not undergo SN2 or SN1 reactions. They do not undergo SN2 reactions
because as the nucleophile approaches the back side of the sp2 carbon, it is repelled by the  electron cloud
of the double bond or the aromatic ring.

a nucleophile is repelled
by the  electron cloud

R Cl
C=C Br
H H
nucleophile nucleophile

a vinylic halide an aryl halide

There are two reasons why vinlic halides and aryl halides do not undergo SN1 reactions First, vinylic and
aryl cations are even more unstable than primary carbocations, and we saw that primary alkyl halides do not
undergo SN1 reactions because of the instability of their carbocations (Section 9.5). The instability of vinylic
and aryl cations is the result of the positive charge on an sp carbon. Because sp carbons are more electronegative
than the sp2 carbons that carry the positive charge of alkyl carbocations, sp carbons are more resistant to
becoming positively charged. Second, we have seen that sp2 carbons form stronger bonds that sp2 carbons
do (Section 1.14). As a result, it is harder to break the carbon-halogen bond when the halogen is bonded to
an sp2 carbon.

sp hybridized

+
RCH = CHCl   RCH = CH + Cl–
vinyl cation
too unstable to be formed

sp hybridized

Br   + + Br –
aryl cation
too unstable to be formed

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6. COMPETITION BETWEEN SN2 AND SN1 REACTIONS

The characteristics of the SN2 and SN1 reactions are summarized in Table 9.5. It is important to remember
that the “2” in SN2 and the “1” in SN1 refer to the molecularity of the rate-determining step. Thus, the rate-
determining step of an SN2 reaction is bimolecular. whereas the rate-determining step of an SN1 reaction is
unimolecular. These numbers do not refer to the number of steps in the mechanism. In fact, just the opposite
is true-an SN2 reaction proceeds by a one-step concerted mechanism whereas an SN1 reaction proceeds
by a two-step mechanism with a carbocation intermediate.

Table 9.5 Comparison of the SN2 and SN1 Reactions

SN 2 SN 1

A one-step mechanism A two-step mecahnism

A bimolecular rate-determining A unimolecular rate-determining
transition state transition state
No carbocation rearrangements Carbocation rearrangements
Products has inverted configuration Products have both identical and inverted
compared with reactant configurations compared with reacant
Reactivity order: Reactivity order:
methyl > 10 > 20 > 30 30 > 20 > 10> methyl

We have seen that methyl halides and primary alkyl halides undergo only SN2 reactions because methyl
cations and primary carbocations, which would be formed in an SN1 reactions are too unstable to be
formed. Tertiary alkyl halides undergo only SN1 reactions because steric hindrance makes them very unreactive
in an SN2 reaction. Secondary alkyl halides as well as benzylic and allylic halides (unless they aretertiary)
can undergo both SN1 and SN2 reaction because they form relatively stable carbocations and the amount of
steric hindrance associated with these alkyl halides is generally not very great. Vinylic and aryl halides do not
undergo either SN1 or SN2 reactions. These results are summarized in Table 9.6

TABLE 9.6 Summary of the Reactivity of Alkyl of Alkyl Halides in Nucleophilic Substitution Reactions

methyl and 10 alkyl halides SN2 only vinylic and aryl halides neither SN1 nor SN2
20 alkyl halides SN1 and SN2 10 and 20 benzylic and 10 and 20 allylic halides SN1 and SN2
30 alkyl halides SN1 only 30 benzylic and 30 allylic halides SN1 only

When an alkyl halide can undergo both SN1 and SN2 reactions, both reactions take place simultaneously.
The conditions under which the reaction is carried out determine which of the reactions predominates.
Therefore, we have some experimental control over which reaction takes place.
What conditions favor an SN1 reaction? What conditions favor an SN2 reaction? These are important
questions to synthetic chemists because an SN2 reaction results in the formation of a single substitution
product whereas an SN1 reaction can form two substitution products if the leaving group is bonded to a

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chirality center. An SN1 reaction is further complicated by carbocation rearrangements. In other words, an
SN2 reaction is a synthetic chemist’s friend, but an SN1 reaction can be a synthetic chemist’s nightmare.
The conditions that determine whether the predominat reaction will be an SN2 reaction or an SN1 reaction
are the concentration of the nucleophile, the reactivity of the nucleophile, and the solvent in which the
reaction is carried out. To understand how the concentration of the nucleophile and the reactivity of the
nucleophile affect whether an SN2 or an SN1 reaction predominates, we must first examine the rate laws for
the two reactions. The rate constants have been given subscripts that indicate the reaction order.

Rate law for the SN2 reaction : rate = k2 [alkyl halide][nucleophile]

Rate law for the SN1 reaction : rate=k1 [alkyl halide]

The rate law for the reaction of an alkyl halide that can undergo both SN2 and SN1 reactions simultaneously
is the sum of the individual rate laws.

rate =k2[alkyl halide][nucleophile] + k1[alkyl halide]

contribution to the rate contribution to the rate

by an S N2 reaction by an S N1 reaction

From the rate law you can see that an increase in the concentration of the nucleophile increases the rate of
an SN2 reaction but has no effect on the rate of an SN1 reaction. Therefore, when both reactions occur
simultaneously, increasing the concentration of the nucleophile increases the fraction of the reaction that
takes place by an SN2 pathway. On the other hand, decreasing the concentration of the nucleophile decreases
the fraction of the reaction that takes place by an SN2 pathway.
The slow (and only) step of an SN2 reaction is attack of the nucleophile on the alkyl halide. Increasing the
reactivity of the nucleophile increases the rate of an SN2 reaction by increasing the value of the constant
(k2), because more reactive nucleophiles are better able to displace the leaving group. The slow step of an
SN1 reaction is the dissociation of the alkyl halide. The carbocation formed in the slow step rapidly reacts in
a second step with any nucleophile present in the reaction mixture. Increasing the rate of the fast step does
not affect the rate of the prior slow, carbocation -forming step. This means that increasing the reactivity of
the nucleophile has no effect on the rate of an SN1 reaction. A good nucleophile, therefore, favors an SN2
reaction over an SN1 reaction. A poor nucleophile favors an SN1 reaction, not by increasing the rate of the
SN1 reaction itself, but by decreasing the rate of the competing SN2 reaction.

 An SN2 reaction is favored by high concentration of a good nucleophile.

 An SN1 reaction is favored by a low concentration ofa nucleophile or by a poor nucleophile.

Notice in the previous sections that SN1 reactions are described, poor nucleophiles (H2O, CH3OH) are
used, and when SN2 reactions ae described, good nucleophiles (HO– , CH3O–) are used. In other words, a
poor nucleophile is used to encourage an SN1 reaction, and a good nucleophile is used to encourage an SN2
reaction

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7 THE ROLE OF THE SOLVENT IN SN2 AND SN1 REACTIONS

The solvent in which the nucleophilic substitution reaction is carried out also influences whether an SN2 or
an SN1 reaction will predominate. Before we can understand how a particular solvent favors one reaction
over another, however, we must understand how solvents stabilize organic molecules.
The dielectric constant of a solvent is a measure of how well the solvent can insulate opposite charges
from one another. Solvent molecules insulate charges by clustering around a charge so that the positive
poles of the solvent molecules surround negative charges while the negative poles of the solvent molecules
surround positive charges. Recall that the interaction between a solvent and an ion or molecule dissolved in
that solvent is called solvation (Section 2.9). When an ion interacts with a polar solvent, the charge is no
longer localized solely on the ion but is spread out to the surrounding solvent molecules. Spreading out the
charge stabilizes the charged species.

+
H
O – + H H +
O
H +
+ + – +
+ + H H H
– O H O– – O
Y– H O Y+
– H H
H + +
+
+ H –
– O O
+ H H +
H
+
ion-dipole interactions ion-dipole interactions
between a negatively between a positively
charged species and water charged species and water

Polar solvents have high dielectric constants and thus are very good at insulating (solvating) charges.
Nonpolar solvents have low dielectric constants and are poor insulators. The dielectric constants of some
common solvents are listed in Table 9.7. In this table, solvents are divided into two groups: protic solvents
and aprotic solvents. Recall that protic solvents contain a hydrogen bonded to an oxygen or a nitrogen, so
protic solvents are hydrogen bond donors. Aprotic solvents, on the other hand, do not have a hydrogen
bonded to an oxygen or a nitrogen, so they are not hydrohen bond donors.
Stabilization of charges by solvent interaction plays an important role in organic reactions. For example,
the first step in an SN1 reaction is dissociation of the carbon – halogen bond of the alkly halide to form a
carbocation and a halide ion. Energy is required to break the bond but, with no bonds being formed, where
does this energy come from? If the reaction is carried out in a polar solvent, the ions that are produced as
products are solveted. The energy associated with a single ion-dipole interaction is small, but the additive
effect of all the ion-dipole interactions involved in stabilizing a charged species by the solvent represents a
great deal. of energy. These ion-dipole interactions provide much of the energy nessary for dissociation of
the carbon-halogen bond. So in an SN1 reaction, the alkyl halide does not fall apart spontaneously, solvent
molecules pull it apart. An SN1 reaction, therfore, can take place in a polar solvent but not in a nonpolar
solvent. An SN1 reaction also cannot take place in the gas phase where there are no solvent molecules and
consequently no solvation effects.

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8. TABLE 9.7 The Dielectric Constants of Some Common Solvents

Solvent Structure Dielectric constant (, at 250C)

Protic solvents
Water H 2O 79
Formic acid HCOOH 59
Methanol CH3OH 33
Ethanol CH3CH2OH 25
tert-Butyl alcohol (CH3)3 COH 11
Acetic acid CH3COOH 6
Aprotic solvents
Dimethyl sulfoxide (CH3)2SO 47
Acetonitrile CH3CN 38
Dimethyl formamide (CH3)2NCHO 37
Hexamethyl phosphoramide [(CH3)2N]3PO 30
Acetone (CH3)2CO 21
Dichloromethane CH2Cl2 9.1
Ethyl acetate CH3COOCH2CH3 6
Diethyl ether CH3CH2OCH2CH3 4.3

Benzene 2.3

Hexane CH3(CH2)4CH3 1.9

The Effect of the Solvent on the Rate of a Reaction

One simple rule describes how a change in solvent will affect the rate of most chemical reactions–increasing
the polarity of the solvent will decrease the rate of the reaction if one or more reactants in the rate-limiting
step are charged and will increase the rate of the reaction if none of the reactants in the rate-limiting step is
charged.
Now let’s see why this rule is true. The rate of a reaction depends on the difference between the energy
of the reactants and the energy of the transition state in the rate-limiting step of the reaction. We can therfore
predict how changing the polarity of the solvent will affect the rate of a reaction. We do this simply by
looking at the charge on the reactant(s) and the charge on the transition state of the rate-limiting step to
determine which of these species will be more stabilized by a polar solvent. The greater the charge on the
solvated molecule, the stronger it will interact with a polar solvent and the more the charge will be stabilized.
Therfore, if the charge on the reactants is greater that the charge on the rate-determining transition state, a
polar solvent will interact more strongly with the reactants that with the transition state. As a result, a poar

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solvent will stabilize the reactants more than it will stabilize the transition stae, increasing the difference in

energy ( G  ) between the reactants and the transition state. Therfore, increasing the polarity of the solvent
will decrease the rate of the reaction, as shown in Figure 9.5.
transition state is less highly charged

Free energy
G
nonpolar
G solvent
polar
solvent

reactants are more highly charged

Progress of the reaction

On the other hand, if the charge on the rate-determinig transition state is greater than the charge on the
reactants, a polar solvent will interact more strongly with the transition state than with the reactants, stabilizing
the transition state more than it stabilizes the reactants. Therfore increasing the polarity of the solvent will

decrease the difference in energy ( G  ) between the reactants and the transition state, which will increase
the rate of the reaction, as shown in Figure 9.6
transition state is more highly charged
Free energy

G
nonpolar
G solvent
polar
solvent

reactants are less highly charged

Progress of the reaction

The Effect of the Solvent on the Rate of an SN1 Reaction

Now let’s see how increasing the polarity of the solvent affects the rate an SN1 reaction of an alkyl halide.
The alkyl halide is the only reactant in the rate-determining step. It is a neutral molecule with a small dipole
moment. The rate-determining transition state has a greater charge because as the carbon-halogen bond
breaks, the carbon becomes more positive and the halogen becomes more negative. Since the charge is
greater in the rate-determining transition state, increasing the polarity of the solvent will increase the rate of
the SN1 reaction (Figure 9.6 and Table 9.8).

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rate-determining step of an SN1 reaction



+ –  + – 
C—X  C ----- X  —C + X–
 
 
reactant transition state products

TABLE 9.8 The Effect of the Polarity of the Solvent on the Rate of Reaction of tert-Butyl
Bromide in an SN1 Reaction
Solvent Relative rate
100% water 1200
80% water / 20 % ethanol 400
50% water / 50 % ethanol 60
20% water / 80 % ethanol 10
100% ethanol 1

In chapter 11 we will see that compounds other than alkyl halides undergo SN1 reactions. As long as the
compound undergoing an SN1 reaction is neutral, increasing the polarity of the solvent will increase the rate
of the SN1 reaction beacuse the polar solvent will stabilize the dispersed charges on the transition state more
than it will stabilize the relatively neutral reactant (Figure 9.6). If, however, the compound undergoing an
SN1 reaction is charged, increasing the polarity of the solvent will decrease the rate of the reaction because
the more polar solvent will stabilize the full charge on the reactant to a greater extent than it will stabilize the
dispersed charge on the transition state (Figure 9.5)

The Effect of the Solvent on the Rate of SN2 Reaction

The way in which a change in the polarity of the solvent affects the rate of an SN2 reaction depends on
whether the reactants are charged or neutral, just as in an SN1 reaction.
Most SN2 reactions of alkyl halides involve a neutral alkyl halide and a charged nucleophile. Increasing
the polarity of a solvent will have a strong stabilizing effect on the negatively charged nucleopahile. The
transition state also has a negative charge, but the charge is dispersed over two atoms. Consequently, the
interactions between the solvent and the transition state are not as strong as the interactions between the
solvent and the fully charged nucleophile. Therefore, a polar solvent stabilizes the nucleophile more than it
stabilizes the transition state, so increasing the polarity of the solvent will decrease the rate of the reaction
(Figure 9.5).
If, however, the SN2 reaction involves an alkyl halide and a neutral nucleophile, the charge on the transition
state will be larger than the charge on the neutral reactants, so increasing the polarity of the solvent will
increase the rate of the substitution reaction (Figure 96.)
In summary, the way in which a change in solvent affects the rate of a a substitution reaction does not
depend on the mechanism of the reaction. It depends only on whether or not the reactants are charged. If a
reactant in the rate-limiting step is charged, increasing the polarity of the solvent will decrease the
rate of the reaction. If none of the reactants in the rate-limiting step is charged, increasing the
polarity of the solvent will increase the rate of the reaction.

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In considering the solvation of charged species by a polar solvent, we have been discussing polar solvents,
such as water or alcohols, that are hydrogen bond donors (protic polar solvents). There are also polar
solvents (Table 9.7) such as N, N-dimethlyformamide (DMF), dimethyl sulfoxide (DMSO), and
hexamethylphosporamide (HMPA) that are not hydrogen bond donors (aprotic polar solvents).
Ideally, one would like to carry out an SN2 reaction with a negatively charged nucleophile in a nonpolar
solvent because the charge on the reactants in such a reaction is greater than the charge on the transition
state. However, a negatively charged nucleophile generally will not dissolve in a nonpolar solvent. Therefore,
an aprotic polar solvents is used. Because aprotic polar solvents are not hydrogen bond donors, they are
less effective than polar protic solvents in stabilizing negative charges. Thus, the rate of an SN2 reaction
involving a negatively charged nucleophile will be greater in an aprotic polar solvent than in a protic polar
solvent. Consequently, an aprotic polar solvent is the solvent of choice for an SN2 reaction in which the
nucleophile is negatively charged, wheras a protic polar solvent is used if the nucleophile is a neutral molecule.
We have now seen that when an alkyl halide can undergo both SN2 and SN1 reactions, the SN2
reaction will be favored by a high concentration of a good (negatively charged) nucleophile in an
aprotic polar solvent, whereas the SN1 reaction will be favored by a poor (neutral) nucleophile in a
protic poalr solvent.

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EXERCISE # I V (A)

1. Which one of the following has the smallest heat of hydrogenation per mole ? [JEE 1993]
(A) 1-Butene (B) trans-2-Butene
(C) cis-2-Butene (D) 1,3-Butadiene

2. In the following compounds: [JEE 1996]

OH
OH
OH OH

NO 2
CH3 NO2

(I) (II) (III) (IV)

The order of acidity is:
(A) III > IV > I > II (B) I > IV > III > II (C) II > I > III > IV (D) IV > III > I > II

3. The reaction of CH3–CH = CH OH with HBr gives: [JEE 1998]

(A) CH3CHBrCH2 OH (B) CH3CH2CHBr OH

(C) CH3CHBrCH2 Br (D) CH3CH2CHBr Br

4. A solution of (+) 1-chloro-1-phenylethane in tolune in tolune racemizes slowly in the presence of

small amount of SbCl5 due formation of: [JEE 1999]
(A) carbanion (B) carbene (C) free radical (D) carbocation

5. An aromatic molecule will: [JEE 1999]

(A) have 4n  electrons (B) have (4n+2)  electrons
(C) be planar (D) be cyclic

6. The enol form of acetone, after Prolonged treatment with D2O, gives: [JEE 1999]

OD OH OD
| | |
(A) CH3–C = CH2 (B) CH3 – C –CH3 (C) CH2 = C – CH2D (D) CD2 = C –CD3
7. Amongst the following, the most basic compound is: [JEE 2000]
(A) C6H 5NH 2 (B) p-NO 2–C 6 H 4NH 2
(C) m-NO 2–C 6 H4NH 2 (D) C6H 5CH 2NH 2

8. An SN2 reaction at an assymetrical carbon of a compound always gives: [JEE 2001]

(A) enatiomer of the substrate (B) a product with opposite optical rotation
(C) a mixture of diastereomers (d) a single stero isomers

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9. The correct order of basicities of the following compounds is: [JEE 2001]
NH
O
CH3 C
CH 3 CH 2 NH 2 (CH3)2NH
NH2 CH3CNH2
(1) (2) (3) (4)
(A) 2>1>3>4 (B) 1>3>2>4 (C) 3>1>2>4 (D) 1
10. Identify the correct order of reactivity in electrophilic substitution reaction of the following com-
pounds: [JEE 2002]
CH3 Cl NO2

(1) (2) (3) (4)

(A) 1>2>3>4 (B) 4>3>2>1 (C) 2>1>3>4 (D) 2>3>1>4
11. Left to right sp2, sp2, sp, sp hybridization present in: [JEE 2003]
(A) H2C = CH–C  N (B) H2C = C=CH–CH3
(C) HC  C–C  CH (D) HC  C – CH = CH2
12. Maximum dipole moment will be of: [JEE 2003]
(A) CCl4 (B) CHCl3 (C) CH 2Cl2 (D) CH3Cl

OH

COOH
13.

OH

O 2N

when X is made to react with 2eq. of NaNH2 the product formed will be: [JEE 2003]

OH
O
OOC
OOC

H H
(A) (B)
OH OH

O2 N O2N

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OH O

OOC HOOC

H H
(C) (D)
O OH

O2N O 2N

14. Order of rate reaction of following compound with phenyl magnesium bromide is: [JEE 2004]
Ph C Ph Me C H Me C Me

O O O
(I). (II) (III)
(A) I > II > III (B) II > III > I (C) III > I > II (D) II > I >II

(Z) (Y)
. NH3

15. H3N [JEE 2004]

(X) COOH

Correct order of acidic strength is:

(A) x > y > z (B) z > y > x (C) y > z > x (D) x > z > y

16. 1-Bromo-3-chloro cyclobutane on reaction with 2- equivalent of sodium in ether gives

[JEE 2005]

Br Cl

(A) (B) (C) (D)

SO3H

CH3COONa(excess)
(aq. solution)
17. [JEE 2005]

Me

SO3Na
COONa
SO2COOCH 3

(A) (B) (C) + CH3COOH (D) +H2SO3

Me
Me Me

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18. Conversion of cyclohexanol into cyclohexene is most effective in [JEE 2005]
(A) concentrated H3PO4 (B) concentrated HCl
(C) concentrated HCl / ZnCl2 (D) concentrated HBr

CH 3
|
19. Ph – MgBr + CH3 – C– OH   A [JEE 2005]
|
CH 3
OH H
CH3
CH3
CH3 C OPh
(A) (B) (C) (D) CH3 C Ph
CH3
CH3

20. For 1-methoxy-1,3-butadiene, which of the following resonating structure is the least stable?
(A) H2C CH CH CH O CH3 (B) H 2C CH CH CH O CH3

(C) H2C CH CH CH O CH3 (D) H2C CH CH CH O CH3

[JEE 2005]
CH3 H CH3

21. MeO NO2 [JEE 2005]

H Cl CH3

on hydrolysis in presence of acetone

CH3 H CH3 CH3 H CH3

(K) MeO NO2 (L) MeO NO2

H OH CH3 OH H CH3

CH3 H CH3

(M) MeO NO2

H CH3 OH

(A) K & L (B) only (C) M only (D) K & M

22. When benzene sulfonic acid and p-nitrophenol are treated with NaHCO3, the gases released
repsectively are [JEE 2006]
(A) SO2, NO2 (B) SO2, NO (C) SO2, CO2 (D) CO2, CO2

23. CH3NH2 + CHCl3 + KOH  Nitrogen containing compound + KCl + H2O. Nitrogen containing
compound is [JEE 2006]
 
(A) CH3–C  N (B) CH3–NH–CH 3 (C) CH3– N  C (D) CH3 N  C

24. (I) 1,2-dihydroxy benzene (II) 1,3-dihydroxy benzene [JEE 2006]

(III) 1,4-dihydroxy benzene (IV) Hydroxy benzene

The increasing order of boiling points of above mentioned alcohols is

(A) I < II < III < IV (B) I < II < IV < III
(C) IV < I < II < III (D) IV < II < I < III
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EXERCISE # I V (B)

[Link]
Q.1 CH3CH 2CHCl2    ? [JEE 1991]

AlCl
Q.2 C6H6 + (CH3)2CHCH2Cl   
3  ? [JEE 1992]

HNO 3 / H 2SO 4
COO
Q.3 mononitration ? [JEE 1993]

Q.4 Draw the stereochemical structure of the products in the following reaction: [JEE 1994]
C2H5
NaOH
Br H ?
SN2
CH3

Q.5 Complete the following, giving the structures of the principal organic products: [JEE 1997]
Ph H

(a) + KNH2   A

Ph Br

(b) + CHBr3 + t – BuOK   B

(c) ClCH2CH2CH2COPh + KOH + MeOH   C

Q.6 Write the intermediate steps for each of the following reaction. [JEE 1998]
O
H O
(i) C6H5CH(OH)C  CH  
3

 C6H5 CH CH CH

.
H
(ii)
OH O CH3

Q.7 Each of the following reaction gives two products. Write the structure of the products.
[JEE 1998]
[Link] , 
(a) C6H5CH2CHClC6H5   

(b) CH3CONHC6H5   A  B   C ‘N’ containing compound.

di / H 2SO 4 Br2
H2O

Q.8 Out of anhydrous AlCl3 and hydrous AlCl3 which is more soluble in diethyl ether? Explain with
reason. [JEE 2003]

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Q.9 Match Ka values with suitable acid: [JEE 2003]

Ka Acid

(i) 3.3  10–5 (a) COOH

(ii) 4.2  10–5 (b) Me COOH

(iii) 6.3  10–5 (c) Cl COOH

(iv) 6.4  10–5 (d) MeO COOH

(v) 30.6  10–5 (e) NO 2 COOH

Q.10 Give resonating structures of following compound. [JEE 2003]

OH

Q.11 Which of the following is more acidic and why? [JEE 2004]

NH3 NH3

Q.12 Predict whether the following molecules are iso structural or not. Justify your answer.
[JEE 2005]
(i) NMe 3 (ii) N(SiMe3)3

Q.13 Give reasons: [JEE 2005]

H3C Br

CH3
C H OH(aq.)
(a) (i) 25   acidic solution

CH3
Br C H OH(aq.)
(ii) 25   neutral
CH3

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(b) (i) NaOH(aq.)

O2N     F(liberated)
CH3

NaOH(aq.)
(ii) H3C     F is not liberated
CH2 NO2

O O O
N N N

NO2
Conc. HNO3
Conc. H2SO 4
(c) (i)

NO2

NO2 NO2

Conc. HNO3
(ii)
Conc. H2SO4
NO2

ANSWER KEY

EXERCISE # I

1. C 2. D 3. D 4. D 5. A 6. B 7. C
8. C 9. C 10. C 11. C 12. A 13. B 14. B
15. A 16. C 17. ABD 18. A 19. D 20. C 21. D
22. B 23. A 24. C 25. C 26. C 27. C 28. A
29. D 30. A 31. C 32. D 33. A

EXERCISE # I I

1. D 2. AB 3. ABC 4. AB 5. AD 6. ACD 7. C

8. A 9. BD 10. ABC 11. AC 12. ABC 13. AC 14. C

15. AC 16. BCD 17. D 18. AD 19. B 20. BD

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21. ABD 22. ABD 23. C 24. CD 25. AB 26. B

27. A 3 , B  2, C  1, D1

28. (A) P, Q (B) Q, S (C) P, (D) R

29. A  2, B  1, C  4, D3

30. (A) – S (B) – Q (C) – R (D) – P

31. (A) – Q (B) – S (C) – R (D) – P

EXERCISE # I I I

1. 3 > 2 > 1 > 4 2. IV > I > II > III 3. (a) II > I > III > IV (b) (ii)
C
|
4. (a) 5. C–C–C–C–Cl > C–C–C–Cl > C– C–C–Cl > C–C–Cl
| | |
C C C
6. a) I b) II c) I d) II
7. a) II b) I c) II d) II
9. b, d, e, g, h

18. (a) CH3 CH2 CH2 Cl + NH3 ; (b) CH3 CH2 ONa + CH3 CH2 Cl ;

(c) HC C Na + CH3CH2CH2 Cl (d) Me2 CH–Cl + Me2 S ;

(e) C6 H5 ONa + CH3 CH2 – Cl

S

19. (a) ICH2 CH2 CH CH2 CH3 ; (b) ; (c)

Cl S S

O
20. (a) I ; (b) ; (c) O
O

(d) CN ; (e) N3 ; (f) SH ;

(e) S

21. (a) C6 H5 –CH2 –CH3 – CN, (b) SCH3 , (c) CH3 – (CH2 )9 – I,

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(d) N CH3I , (e)

H Me Me
| | |
22. (a) CH3O–C–CH3 ; (b) Et – C– OMe + MeO – C – Et,
| | |
CH2CH3 Pr Pr

SH
(c) CH3 + CH3

SH

Ph
Ph
COOH

23. (a) Ph C C C Ph ; (b)

OH

25. A: CCl2 B:
Cl Cl

Br
26. (i) & OMe ; (ii) Ph COOEt
Br

27. (a) II , (b) I, (c) II

28. (a) II ; (b) II ; (c) I ; (d) II ; (e) II ; (f) I

32.. MeCOOMe

34. (i) (a) II, (b) I, (c) II ; (ii) (a) II, (b) II, (c) I

35. (a) II , (b) I 44. (a) Et3 CO ; (b) EtO

OAC
|
48. C=C–C–C,C–C=C–C,C–C–C–C
| | |
C C C

C C
| |
49.. (b) C – C – C – Br ; (c) Br – C– C – C ; (d) C – C – C– C – C – Br
| |
C C

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(e) C – C – C – C – C (f) C–C–C–C–C

| |
Br Br

C C
| |
53. (a) C – C – C = C – C ; (b) C – C – C – =C ; (c) C = C – C – C
|
C

(d) C – C – C – C = C

CH2Br
Br

54. (a) ; (b) ; (c) Br CH3 ; (d) ;

Br

Br

(e) CH2 CH2 Br ; (f) , (g) CMe3

Br

55. (A) RCH2 CH2 SR (B) RCHBrCH2 CCl3 (C) RCHClCH2 CCl3

56. CH3 – CH2 – CH2 –F

57. PhCHO

Cl
58. (i) (a) Ph CH Et , (b) Me2 C(I) – Et, (c) , (d)
Br Et
Br

Ph Br
Et CH CH3 Cl
(ii) (a) C C , (b) , (c)
Br H OH O

59. Me2 C =CH – CH = CH2

EXERCISE # I V (A)
1. D 2. D 3. B 4. D 5. B 6. D 7. D

8. D 9. B 10. C 11. A 12. D 13. C 14. B

15. D 16. C 17. C 18. A 19. C 20. C 21. A

22. D 23. D 24. C

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EXERCISE # I V (B)
C(CH 3) 3

1. CH3 CH2 CHO 2.

C2H5

3. COO NO 2 4. H OH

CH2

Br

5. (A) PhC  CPh, (B) ,

O CH 2

(C) Ph C CH CH 2

C 6H 5 H C 6H 5 C 6H 5
C C C C
Q.7 (a) H C 6H 5 H H
(trans) (cis)

O
(b) A Ph C OH
B Ph NH 2

NH2

Br Br

Br

Q.9 (i) d (ii) b (iii) a (iv) c (v) e

NH3 NH3

Q.11 in due to +R r + m effect. p position contain -ve charge

CH3

C OCH2 CH3 HBr

Q. 13 (a) (i) (ii) No reaction
CH3

(b) P’ position contain NO2 group

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 ALCOHOLS PHENOL AND ETHER
II T- i a n’ s PACE [Link].L td. ALCOH OL PH ENOL & ETH ER Rg - APE - 1 3

1. IIT-JEE Syllabus
Alcohol (esterification, dehydration and oxidation) Reaction of alcohols with sodium,
phosphorus halides, ZnCl2/Conc. HCl. Phenol, Acidity of phenols, halogenation nitration,
sulfonation and Riemer – Tiemann reaction

2. Alcohols
2.1 Introduction
The organic compounds containing one or more than one hydroxyl group(s) attached to
sp3 hybridised carbon atom(s) are called alcohols. Alcohols are bent shaped molecules.
In alcohols, the carbon atom linked with ‘O’ atom of OH group is sp3 hybridised. The central ‘O’ atom is
also sp3 hybridised and the COH bond angle is 105°.
O
105°
H3C H
Some examples of alcohols are:

CH3 OH
CH3COH H2C=CHCH2OH
Allyl alcohol
CH3
tertButyl alcohol Cyclohexanol

CH2CH2 CH2CHCH2
CH2OH
Cl OH OH OH OH
Benzyl alcohol Ethylene chlorohydrin Glycerol
(Chloroethyl alcohol)

Compounds in which the hydroxyl group is attached directly to a sp2 hybridised carbon atom are
known as enols or phenols (in case of aromatic compounds).
For example,
OH
CH3CH2CH=CHOH
But1en1ol
(enol)
(Phenol)

2.2 Structure

Alcohols can be represented by the general formula ROH, where R is any alkyl or substituted alkyl
group. The group may be primary, secondary, or tertiary; it may be open-chain or cyclic; it may
contain a double bond, a halogen atom, or an aromatic ring. For example

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CH3
H3C OH
H2C

OH
H3C
prop-2-en-1-ol
OH
2,2-dimethylpropan-1-ol cyclohexanol

OH

OH
OH Br OH OH
phenylmethanol 2-bromoethanol glycerol

All alcohol contains the hydroxyl (-OH) group, which, as the functional group, determines the
properties characteristic of this family. Variations in structure of the R group may affect the rate at
which the alcohol undergoes certain reactions, and even, in a few cases, may affect the kind of
reaction.

When the hydroxyl group is attached directly to an aromatic ring they are phenols, and differ so
markedly from the alcohols that we shall consider them separately.

2.3 Classification

Alcohols are classified as mono, di and trihydric alcohols depending upon the number of OH groups
present in them. Alcohols with one, two and three OH groups are called mono,
di and trihydric alcohols respectively. Alcohols, which contain four or more hydroxyl groups attached to the
sp3 hybridised carbon atoms are called polyhydric alcohols.
CH3 OH CH 2OH CH 2OH CH2OH
Methyl alcohol
CH 2OH CHOH (CHOH)4
Ethan1, 2diol
(Dihyd ri c alcohol) CH 2OH CH2 OH
Propan1,2,3triol Sor bitol or Manni tol
(Trihydric alcohol) (Polyhydric alcohol)

The monohydric alcohols can further be classified according to the type of carbon that bears the
OH group. An alcohol in which OH group is attached to carbon atom, which in turn is linked to only one
carbon atom, is called primary (1°) alcohol. Similarly, an alcohol in which OH group is attached a carbon
atom which is linked to two carbon atoms is called secondary (2°) alcohol and an alcohol in which the
carbon atom bearing OH group is attached to three carbon atoms is called tertiary (3°) alcohol. For
example,
H R R
R  C  OH R  C  OH R  C  OH
H H R
Primary Secondary Tertiary
(1°) (2°) (3°)

2.4 Nomenclature

For the simpler alcohols the common names, are most often used. These consist simply of the
name of the alkyl group followed by the word alcohol. For example :

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OH
OH
H3C
OH OH
H3C CH3 H3C
propan-1-ol propan-2-ol propylene glycol

CH3 
CH3
H3C 
OH
OH CH3 H3C OH
2-methylbutan-2-ol (3-methylphenyl)methanol 1-phenylethanol

We should notice that similar names do not always mean the same classification; for example,
isopropyl alcohol is a secondary alcohol, whereas isobutyl alcohol is a primary alcohol.

Finally, there is the most versatile system, the IUPAC. The rules are:

1. Select as the parent structure the longest continuous carbon chain that contains the
-OH group; then consider the compound to have been derived from this structure
by replacement of hydrogen by various groups. The parent structure is known
as ethanol, propanol, butanol, etc., depending upon the number of carbon
atoms; each name is derived by replacing the terminal -e of the corresponding alkane name by -
ol.

2. Indicate by a number the position of the -OH group in the parent chain, generally using the
lowest possible number for this purpose.

3. Indicate by numbers the positions of other groups attached to the parent chain.

H3C OH

H3C OH CH3 OH
ethanol 2-methylbutan-1-ol phenylmethanol

OH

H3C CH3
CH3 OH
H3C
H3C OH CH2
OH CH3 Cl H3C
2-methylbutan-2-ol 3-methylbutan-2-ol 2-chloroethanol but-3-en-2-ol

Alcohols containing two hydroxyl groups are called glycols. They have both common names and
IUPAC names.
CH3
OH
H3C
CH3
H3C
H
OH
HO OH
HO OH H
ethylene glycol propylene glycol 3,4,5-trimethylcyclopentane-1,2-diol

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Alcohols containing two hydroxyl groups are called glycols. They have both common name and IUPAC
names. Common names are given in parenthesis.
H
H H
H
CH2–CH2 CH3–CHCH2 CH2CH2CH2 HH HH
OH OH OH OH OH OH
1, 2ethanediol 1, 2propanediol 1, 3propanediol HO OH
(Ethylene glycol) (Propylene glycol) (Trimethylene glycol) cis1, 2cyclopentanediol

2.5 Preparation of Alcohols

1. By hydrolysis of haloalkanes: in presence of aqueous sodium or potassium hydroxide or

moist silver oxide.

R – X + KOH(aq)  R – OH + KX
Reaction will follow either SN1 or SN2 mechanism.

2. By reduction of Aldehydes, ketones and esters: in presence of reducing agents like H2 in

Ni/Pt/Pd or [H] or LiAlH4 or NaBH4. Esters can however only be reduced by LiAlH4 or [H].
R  CHO  RCH2OH(1O alcohol)
O OH

R
R R R
O
||
R  C  OR   R  CH2OH  ROH
4[ H]

REDUCTION OF CARBONYL COMPOUNDS

Aldehydes can be reduced to primary alcohols and ketones to secondary alcohols, either
by catalytic hydrogenation or by the use of chemical reducing agents like lithium
aluminium hydride (LiAlH4), H2/Ni, B2H6/THF etc.

REDUCTION BY LiAlH4 OR NaBH4

The commonly used reagent for the reduction of aldehydes and ketones are LiAlH4 or NaBH4. The
reaction proceeds by successive transfer of hydride ions (H) from boron or aluminium to four different
carbonyl carbons. As all four of the hydrides are transferred, there are distinct reducing agent used in every
step of reduction. In the first step, the reducing agent is AlH4 (I), while in the second step, the reducing
agent is RCH2OAlH3 (II).
In the same manner, species [RCH2O]2AlH2 (species III) and [RCH2O]3AlH (species IV) will be
obtained. Reduction with NaBH4 is usually done in water or in alcohol which are used as the solvent. The
solvent destroys the intermediate alkoxide ion and yields alcohol. If water or an alcohol is not used as the
solvent, aqueous acid can be added after the reduction to convert the alkoxide to alcohol.
The mechanism for reduction with lithium aluminium hydride is very similar to that of NaBH4. As
LiAlH4 violently reacts with water and other polar protic solvents to give molecular hydrogen, reduction
with LiAlH4 are done in aprotic solvents like anhydrous ether. Ethyl acetate is added to decompose the
aluminium complex. But reduction with NaBH4 can be carried out in water or ethanol solution.

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Mechanism of reduction by LiAlH4:

H
H AlH3 RCH=O R CH=O
RCH ether RCOAlH3 [RCH2O] 2AlH2
O H
OCH2R
CH3 CO2 Et RCH=O
4RCH2OH + Al(OH)3 RCH2OAlOCH2R [RCH2O]3AlH
OCH2R
Aldehydes are reduced to primary alcohols by both LiAlH4 and NaBH4 while these reducing agents
reduce ketones to secondary alcohols.

LiAlH4 H
(i) O
OH
O
LiAlD4
 PhCDOH.
(ii) Ph H 3O
CH3

NaBH4 H
(iii) O
OH
O O OH OH
2NaBH4
(iv)
H H
LiAlH4 can reduce all functional groups of column ‘A’ into Column ‘B’. Generally, it is unable to reduce
double bond, which are in conjugation with C=O group the double bond is reduced when a phenyl
group is attached to the carbon.
For example,
LiAlH
C6H5CH=CHCHO  
4
 C6H5CH2CH2CH2–OH

“A” “B”

CHO CH2OH

C=O CHOH
COOH CH2OH
COOR CH2OH + ROH
COCl CH2OH
(RCO)2O RCH2OH
lactone diol
epoxide alcohol

can reduce all the above groups of column ‘A’ into groups of column ‘B’ except, COOH and COOR.
NaBH4 is able to reduce the double bonds, which are in conjugation with C=O group.

REDUCTION BY H2/Ni
It can reduce all the above groups of column ‘A’ into groups of column ‘B’. It can also reduce double
and triple bond present in carbonyl compounds irrespective of the position in carbon chain whether
it is in conjugation with carbonyl group or not.

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H / Ni
CH3CH=CHCHO 2 
 CH3CH2CH2CH2 –OH
H / Ni
CH2=CHCH2CHO 2 
 CH3CH2CH2CH2–OH

REDUCTION BY B2H6/THF
It can reduce all above groups of column ‘A’ into groups of column ‘B’ except, COCl.

REDUCTION OF CARBOXYLIC ACID

Lithium aluminum hydride, LiAlH4, is one of the few reagents that can reduce an acid to an alcohol;
the initial product is an alkoxide from which the alcohol is liberated by hydrolysis:

4RCOOH + 3LiAlH4  4RCH2OH.......... 1oalcohol

Because of the excellent yield it gives, LiAlH4 is widely used in the laboratory for the reduction of not
only acids but many other classes of compounds.

REDUCTION OF ESTER

Like many organic compounds, esters can be reduced in two ways: (a) by catalytic hydrogenation
using molecular hydrogen, or (b) chemical reduction. In either case, the ester is cleaved to yield (in
addition to the alcohol or phenol from which it was derived) a primary alcohol corresponding to the
acid portion of the ester.
RCOOR'   RCH2OH + R'OH
reduction

3. By the action of Grignard’s Reagent on aldehydes, ketones and esters:

When a solution of an alkyl halide in dry ethyl ether, (C2H5)2O, is allowed to stand over turnings of
metallic magnesium, a vigorous reaction takes place. The solution turns cloudy, begins to boil and the
magnesium metal gradually disappears. The resulting solution is known as Grignard reagent. It is one of
the most useful and versatile reagents known to the organic chemists.
Dry ether
RX + Mg   
 RMgX
Alkyl halide Alkyl magnesium halide

The Grignard reagent has the general formula RMgX, and the general name
alkyl magnesium halide. The carbonmagnesium bond is covalent but highly polar, with carbon pulling
away electrons from electropositive magnesium but the magnesiumhalogen bond is essentially ionic,

R MgX.
Since magnesium becomes bonded to the same carbon that previously held halogen, the alkyl
group remains intact during the preparation of the reagent. Thus, npropyl chloride yields npropyl
magnesium chloride and isopropyl chloride yields isopropyl magnesium chloride.
Dry ether
CH3CH2CH2Cl + Mg   
 CH3CH2CH2MgCl
nPropyl chloride nPropyl magnesium chloride

Dry ether
(CH3)2CHCl + Mg   
 (CH3)2CHMgCl
Isopropyl chloride Isopropyl magnesium chloride

The Grignard reagent belongs to a class of compounds called organometallic compounds, in which
carbon is bonded to a metal like lithium, potassium, sodium, zinc, mercury, lead, thallium or to almost any
metal known. Each kind of organometallic compound has its own set of properties and its particular uses
depend on these. But whatever the metal, it is less electronegative than carbon and the carbonmetal bond

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is always highly polar. Although the organic group is not a fullfledged carbanion but has considerable
carbanionic characters. Thus, organometallic compounds can serve as a source of carbon bearing negative
charge.

The Grignard reagent has the formula RMgX and is prepared by the reaction of metallic magnesium
with the appropriate organic halide. This halide can be alkyl (1°, 2°, 3°), allylic, aryl alkyl (e.g. benzyl), or
aryl (phenyl) or substituted phenyl. The halogen may be Cl, Br or I, (Aryl magnesium chlorides must be
made in the cyclic ether tetrahydrofuran instead of ethyl ether). Aldehydes and ketones resemble each
other closely in most of their reactions. The carbonyl group is also unsaturated and like the carboncarbon
bond, it also undergoes addition. One of the typical reaction is cis addition of the Grignard reagent.

The electrons of the carbonyl double bond hold together atoms of different electronegativity, thus,
the electrons are not equally shared, the mobile cloud is pulled strongly towards the more
electronegative atom, oxygen. The addition of an unsymmetrical reagent happens such that the
nucleophilic (basic) portion attaches itself to carbon and the electrophilic (acidic) portion attaches itself to
oxygen.

The carbonmagnesium bond of the Grignard reagent is a highly polar bond, carbon being negative
relative to electropositive magnesium. When Grignard reagent is added to carbonyl compounds, the
organic group attaches to carbon and magnesium to oxygen.
+   +
C=O + R: MgX COMgX H2O COH + Mg(OH)X
R R H
+
An alcohol

Mg2+ + X + H2O
The product is a magnesium salt of the weakly acidic alcohol and is easily converted into the alcohol
by the addition of the stronger acid, water. The Mg(OH)X thus formed is a gelatinous material, which forms
coating over carbonyl compound, thus dilute mineral acid (HCl, H2SO4) is commonly used instead of water,
so that watersoluble magnesium salts are formed.
PRODUCTS OF THE GRIGNARD SYNTHESIS:
The type of alcohol that is obtained from a Grignard synthesis depends upon the type of carbonyl
compound used. Formaldehyde (HCHO) yields primary alcohols, other aldehydes (RCHO) yield secondary
alcohols and ketones (R2CO) yield tertiary alcohols. The number of hydrogens attached to the carbonyl
carbon defines the carbonyl compound as formaldehyde, higher aldehydes or ketone. The carbonyl carbon
is the one that finally bears the OH group in the product and the number of hydrogen defines the alcohol
as primary, secondary, or tertiary.
For example,
H CH3 CH3
H2O
CH3CH2CHCH3 + HC=O CH3CH2CHCH2OMgBr CH3CH2CHCH2OH
Formaldehyde secButyl carbinol
MgBr
(1°alcohol)
secbutyl magnesium
bromide

H CH3 CH3
H2O
MgBr + CH3C=O CHOMgBr CHOH
Acetaldehyde
Phenyl magnesium Phenylmethylcarbinol
bromide (1Phenylethanol)
(1° alcohol)

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CH3 CH3 CH3

H2O
nC4H9MgBr + CH3C=O nC4H9COMgBr nC4H9COH
Acetone
CH3 CH3
nButyl magnesium nButyldimethyl carbinol
bromide (3°alcohol)

C=O + RMgX COMgX H2O COH + Mg++ + X

R R

H H H
H2O
HC=O + RMgX HCOMgX HCOH (1°alcohol)
Formaldehyde R R

H H H
H2O
RC=O + RMgX RCOMgX RCOH (2°alcohol)
Other aldehydes R R

R R R
H2O
RC=O + RMgX RCOMgX RCOH (3°alcohol)
Ketone R R
Reactivity order of the substrates with a Grignard reagent is

Active H compounds > –CHO > C=O > –COCl > –CO2R > –CH2X.

EXCEPTIONAL BEHAVIOUR OF GRIGNARD REAGENT:

Sometimes, Grignard reagent does not react with compounds containing functional group normally
capable of undergoing reaction. Generally, branching of the carbon chain near the functional group
prevents the reaction. For example, methyl magnesium bromide or iodide does not react with hexamethyl
acetone (CH3)3CCOC(CH3)3. It has also been found that if Grignard reagent contains large alkyl groups,
reaction may be prevented. For example, isopropyl methyl acetone reacts with methyl magnesium iodide
but not with tbutyl magnesium iodide. In other cases, abnormal reaction may take place. For example,
when isopropyl magnesium bromide is added to diisopropyl ketone, the expected tertiary alcohol is not
formed, instead the secondary alcohol, diisopropyl carbinol is obtained resulting from the reduction of the
ketone.
( CH ) CHMgBr
(CH3)2CHCOCH(CH3)2   
3 2
 (CH3)2CHCH(OH)CH(CH3)2 + CH3CH=CH2
, unsaturated carbonyl compounds adds on Grignard reagents at the 1, 2 or
1, 4positions.
1, 2addition:
R3
3
R MgX
R1CH=CHC=O R1CH=CHCOMgX
R2 +
R2
H3O
R3
R1CH=CHCOH
R2

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1, 4addition:
R MgX
3

R1CH=CHC=O R1CHCH=COMgX
R2 R3 R2
+
H3O

tautomerizes
R1CH=CH2CR2 R1CHCH=COH
R3 O R3 R2
[enol]

The reaction of dihalides of the type Br(CH2)nBr with magnesium depends on the value of n. For n =
1, no Grignard reagent is formed. For example,

Mg Mg
CH2CH2 ether
CH2=CH2, CH2CH2CH2 ether
Br Br Br Br
When n  4, the Grignard reagent can be possibly made with dibromo compound i.e, Br(CH2)nBr.

ORGANOLITHIUM COMPOUNDS:
Alkyl lithium compounds can be prepared by direct displacement, the chlorides give best yields. For
example,
N
Bu–Cl + 2Li 
2
 Bu–Li + LiCl
hexane

Other organolithium compounds can be prepared by the halogenmetal exchange with the butyl
lithium compound.
BuLi + RX  RLi + BuX
Organolithium compounds behave like the Grignard reagent but the lithium compounds are usually
more reactive and the yield of the product is often better. Because of their sensitivity to oxygen and to
water, reaction with lithium alkyls is best carried out in an atmosphere of dry nitrogen. Alkyl lithium reacts
with CO2 to give carboxylate salt.
O
RLi + CO2 RC
OLi+
4. By Aliphatic Primary Amines: on treatment with nitrous acid give primary alcohols.

RCH2NH2 + HNO2  RCH2OH + N2 + H2O

5. Hydration of alkenes

Boil
CH2  CHR  H2SO4  CH3  CH(R )OH
Concentrat ed H 2O

6. Oxo Process
R = R + CO + H2    RRCHO 2 
 RRCH2OH
[ Co( CO ) 4 ] 2 H / Ni
high temperatur e

7. Fermentation of Carbohydrates

C12H22 O11  H2 O   C 6H12 O 6  C 6H12 O 6 

Invertase
 2C 2H5 OH  2CO 2
Zymase ,

Sucrose Glu cos e Fructose

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8. Oxymercuration-demercuration

H3C
H3C
  
Hg( OAc )2 / NaBH4
CH3
CH2
HO
Markonikov's Addition

Examples:
CH3 CH3

H3C   
Hg( OAc )2 / NaBH4
H3C

CH2 CH3

HO

No Rearrangement

9. Hydroboration-oxidation

H3C
   H3C
B2H6 / THF / H2O 2
OH
CH2
Anti Markonikov's Addition
CH3

H3C    H3C

B2H6 / THF / H2O 2
OH
CH2
CH3

No Rearrangement

10. Hydroxylation of alkenes.

OH
  
[Link] 4 or OsO 4

OH
syn-Hydroxylation

OH
RCO 3H / H

OH
anti-Hydroxylation

2.6 Physical Properties

1. Physical State: Lower alcohols are liquid at room temperature while higher ones are solid. They
have distinct smell and burning taste.

2. Boiling Point: The lower members like methanol, ethanol, 1propanol have higher boiling points.
The boiling point rises as the molecular weights of the alcohol increases. It is quite evident that within the
homologous series, the alcohols of normal chain show a rise in the boiling points with the increase in
molecular weights. Like alkanes, the branched chain isomers of alcohol have lower boiling points. Thus
among the four isomeric butyl alcohols, tbutyl has the lowest boiling points (80°C).

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The order of boiling points of isomeric butyl alcohols is

nButyl alcohol, CH3(CH2)3OH > isobutyl alcohol, (CH3)2CHCH2OH > secbutyl alcohol,
CH3CH(OH)CH2CH3 > tbutyl alcohol, (CH3)3COH

Compactness of tbutyl alcohol reduces the surface area and hence lowers the boiling point. The
boiling point of alcohols are much higher than alkanes of comparable molecular weights. The high boiling
point of the alcohols is due to hydrogen bonding by which the alcohol molecules remain associated in the
liquid state.
HO HO HO HO
R R R R
The hydrogen of one (OH) group forms a loose bond with the oxygen of OH group of another
molecule i.e. they remain in the molecular association through intermolecular hydrogen bonding, which
accounts for their high boiling points. But the hydrogen bonding is not so extensive as in water molecules.
So, water boils at a higher temperature than methyl and ethyl alcohols.

3. Solubility: The lower members of alcohols are highly soluble in water but as the size of the alkyl group
increases, the solubility decreases. This phenomenon is common with other organic compounds having
atleast one electronegative atom or group like ethers, aldehydes, ketones, acids, amides, sugars etc. and
they all are soluble in water. The solubility of alcohols is attributed to its ability to form hydrogen bonds with
water.
 +
RO HO
H H
But as the molecular weight increases, the solubility decreases. For example, methanol is infinitely
soluble but only 0.6 g of nhexyl alcohol dissolves in 100 ml of water. In general, organic compounds
having atleast one electronegative element become gradually insoluble in water as the hydrocarbon chain
increases. However, branching of the alcohol increases the solubility.
Thus, tbutyl alcohol is infinitely soluble but 1butanol is slightly soluble in water. This is again due to the
compactness of the molecule. Better and easy surrounding by water increases the
solubility. Increase in the number of OH groups increases the solubility. For example, glycol
(two OH groups) and glycerol (three OH groups) are more soluble in water than methanol and ethanol.

2.7 Chemical Properties

Chemical reactions are mainly based on OH group of alcohol. The oxygen atom of OH group polarize
both the CO bond and the OH bond of any alcohol. Polarization of the OH bond makes the hydrogen
partially positive and explain why alcohols are weak acids. Polarization of the CO bond makes the carbon
atoms partially positive. The polarization of CO bond is responsible for the weak basic character of
alcohols.

On the basis of the above explanation of polarization of CO and OH bonds, we can classify the
reaction of alcohols into two parts, first due to breaking of the CO bond, with removal of OH group and
second due to the breaking of OH bond, with removal of ‘H’. Except these reactions, alcohols show some
other reactions like oxidation, reduction, elimination etc. Alkyl group of alcohols is also responsible for some
chemical reactions.

5.1 REACTION DUE TO OH BOND CLEAVAGE

5.1.1 REACTION WITH ALKALI METALS:
Active metals (Na, K, Mg, Al etc) when treated with alcohols give hydrogen gas. In this reaction,
order of reactivity of alcohols is CH3OH > 1° > 2° > 3°. This reaction exhibits acidic character of
alcohols.

ROH + Na  RONa+ + ½ H2

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In OH group of alcohols, oxygen is more electronegative than hydrogen, this results in polarization
of OH bond due to which acidic nature arises in alcohols. Reaction of active metals with alcohols
shows that alcohols are acidic in nature.
RONa+ + HOH  NaOH + ROH
Stronger Stronger Weaker Weaker
base acid base acid

The order of acidity for some compounds is

H2O > ROH > HCCH > NH3 > RH
The order of basicity is
R > NH 2 > HCC > OR > OH
The above order is based on the reactions of alcohols with other species.

C2H5OH + Na C2H5O Na + ½ H2
HCCNa+ + ROH  HCCH + RONa+
5.1.2 ESTERIFICATION:
A direct reaction between a carboxylic acid and alcohol under the catalytic effect
of sulphuric acid yields an ester. This is a reversible reaction and is known as the
”Fischer esterification”.
 ..
.. OH OH OH
O: + Fast 
RC +H RC RC RC
OH
OH :OH OH
..
Ia
.
. .. 
OH :OH .OH
. 2
.. Slow  H IMPE
RC + :OH RC O
.. RCOR
R
OH R OH OH
Ib
H2O

H
+

RCOR RCOR RCOR
Fast
O  OH
.. : OH
..

5.2 REACTIONS DUE TO CO BOND CLEAVAGE

Polarization of the CO bond makes the carbon atom partially positive, so this carbon would be
susceptible to the nucleophilic attack and if it were not for the fact that OH is a strong base and
they are very poor leaving group. Protonation of the alcohol converts a poor leaving group (OH)
into a good one. It also make the carbon atom even more positive (because  OH 2 is more electron
withdrawing than OH) and therefore, even more susceptible to nucleophilic attack. Now,
nucleophilic substitution reactions are possible in alcohols according to the given mechanism.

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5.2.1 REACTION WITH HX:

For example,
Conc. HBr
CH3CHCH3 CH3CHCH3
or (NaBr + H2SO4)
OH Br
Isopropyl alcohol Isopropyl bromide
Conc. HCl / ZnCl2
CH3CH 2CH2CH2CH2OH 
CH3CH2CH2CH2CH2Cl
npentyl alcohol npentyl chloride

CH3 CH3
Conc. HCl
CH3CCH3 CH3CCH3
OH Cl
tertButyl alcohol tertButyl chloride

In SN1 reactions of alcohol (when R group is 3°), R may rearrange. Primary alcohols and methanol
apparently react through a mechanism that we recognize as an SN2 type.

With HBr, alcohols produce alkyl bromide.

  Slow
ROH
.. +H ROH2 BrR+ H2O
SN2
..
Br

or for stable carbocation R , racemic mixture will be obtained for optically active alcohol by SN1
mechanism.
But 3pentanol reacts with HBr to produce 2 and 3bromopentane derivatives.

H
CH3CHCHCH2CH3 CH3CHCHCH2CH3
H OH H OH2

Br
Br 
CH3CH2CHCH2CH3 CH3CHCHCH2CH3
(II a) I (More +I groups
H +
attached to C )
Br
 Br
CH3CHCH2CH2CH3 CH3CHCH2CH2CH3
II (More members of (II b)
hyperconjugation structure)
In SNi reaction, retention of configuration is observed & mechanism operates through intimate
ionpair formation.
With PBr3, PBr5 also alkyl bromide results with no rearrangement. Sometimes alcoholic OH is made
good leaving group by converting OH into OTs group.
ClSO2 CH3
TsCl
ROH HCl
ROSO2 CH3

(Pyridine) R + 
OS CH3
Solvent Br
O
RBr More resonance
(Rearranged as well stabilization
as unrearranged product)

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For the compound like CH3CHCH=CH2, double bond shifts and resultant bromide is a mixture as
OH
shown below.
H
  
CH3CHCH=CH2 H2O CH3CHCH=CH2 CH3CH=CHCH2
(allylic carbocation) ..
OH .. Br
Br

CH3CHCH=CH2 CH3CH=CHCH2
Br Br

5.2.2 REACTION WITH PX3 AND PX5:

Alcohols react with PX3 and PX5 to yield alkyl halides (PX3 = PBr3, PI3)
3ROH + PBr3  3RBr + H3PO3
(1° or 2°)
ROH + PCl5  RCl + POCl3 + HCl
For example,
CH3 CH3
PBr3
3CH3CH2CHCH2OH 3CH3CH2CHCH2Br + H3PO3

PBr3
3C6H5CHCH3 3C6H5CHCH3 + H3PO3
OH Br

5.2.3 REACTION WITH SOCl2:

Alcohols react with thionyl chloride in presence of pyridine to give alkyl chloride with inverted
configuration, while in absence of pyridine, an alkyl chloride with retention of configuration is obtained
via SNi mechanism.
ROH + SOCl2  RCl + SO2 + HCl
5.2.4 ACID CATALYSED DEHYDRATION OF ALCOHOLS:
Alcohols in presence of dilute acid undergo dehydration forming alkenes. The reaction proceeds by
E1 mechanism.

 
H H
..   H
CH2OH CH2OH2 CH2
Dehydration of cyclic alcohol is accompanied by expansion in the above reaction. Stability of the
ring is given by Baeyer strain theory, according to which the stability order of the rings is 6 > 7, 5 > 8, 9
>> 4 > 3 .

5.3 OXIDATION OF 1°, 2°, 3° ALCOHOLS WITH CrO3 OR K2Cr2O7 IN ACID

Alcohols with atleast one hydrogen atom on 1° and 2° carbinol are oxidised to carbonyl
compounds (aldehydes and ketones). PCC (Mixture of pyridine, HCl and CrO3) oxidises 1° alcohol
to aldehydes but K2Cr2O7 or KMnO4 in acid converts 1° alcohol directly to carboxylic acids. Under
mild conditions, 3° alcohols are not oxidised.
Jone’s reagent (chromic acid in aqueous acetone solution). This is a sufficiently mild oxidising
agent, so that it oxidises alcohols without oxidising or rearranging double bonds. MnO2 can oxidise
1° allylic or 1° benzylic alcohols selectively into aldehydes.
For example,

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H2CrO 4
CH3–CH=CH–CH2OH   CH3–CH=CH–CH=O
in acetone

H MnO2
O
OH

MnO2
CH2OH CH=O

CHROMIC ACID (JONES REAGENT)

The most convenient reagent for the oxidation of alcohols is 8N chromic acid in sulphuric
acid (Jones reagent). Two millimoles of this reagent oxidizes 3 millimoles of monohydric alcohol
according to the equation:
3R2CHOH + 2H2CrO4  3R2C=O + 2Cr(OH)3 + 2H2O
The function of sulphuric acid is to prevent complex formation of Cr(VI) with its reduced form
Cr (III) to a salt having much less oxidation potential. This ensures that all the Cr(VI) is used in
oxidation, which thus becomes rapid and complete. Acetone is the usual solvent used at ice bath
temperature. Alcohols having double or triple bonds in the molecule can be selectively oxidized to
ketones in good yields. For example,
OH O
CH3(CH2)3CCCH–CH3  CH3(CH2)3CCC–CH3

The most likely mechanism for the oxidation of alcohols by Jones reagents has been shown
to be
R2CHOH + Cr6+  R2C=O + Cr4+ + 2H+
Cr4+ + Cr6+  2Cr5+
3Cr5+ + 2R2CHOH  2R2C=O + 2Cr3+ + 4H+
3R2CHOH + 2Cr6+  3R2C=O + 2Cr3+ + 4H+

Thus, apparently, 3 moles of alcohols react with 2 moles of Cr(VI) to give 3 moles of ketone
and 2 moles of Cr(III). It is clear, however, that only one mole of the alcohol is oxidized directly by
Cr(VI) and the other two part in the oxidation with Cr (V).

5.4 CLEAVAGE OF 1, 2GLYCOLS

Lead tetraacetate or periodic acid are commonly used for the cleavage of 1, 2glycols.
The former reagent is used in anhydrous solvent, whereas the later in organic solvent. Periodic acid
is more selective and readily cleaves 1, 2glycols at room temperature. But cleavage of an
hydroxy ketone or acid by this reagent even at higher temperature is slow. Lead tetraacetate,
however, oxidizes hydroxyketone or acid as well as 1, 2glycols more easily. This is explained on
the basis of a fivemembered cyclic intermediate.

C O O C O
I OH Pb(OAc)2
C O O C O

C O + C O C O + C O
A 1, 2glycol need not necessarily be cis to undergo cleavage with lead tetraacetate.
For instance, trans9, 10decalindiol undergoes cleavage to cyclodecane1, 6dione.

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OH
Pb(OAc)4
O O

OH

Upon treatment with periodic acid, HIO4, compounds containing two or more–OH or C=O groups
attached to adjacent carbon atoms undergo oxidation with cleavage of carbon-carbon bonds.

For example:
OH

R' + HIO 4 RCHO + R'CHO

R

OH
O

R' + HIO 4 RCOOH + R'COOH

R

O
OH

R' + HIO 4 RCHO + R'COOH

R

O
OH OH

+ 2HIO 4 RCHO + HCOOH + R'CHO

R R'

OH
OH
R
R' + HIO 4 R2CO+R'CHO
R

OH
OH OH

R R' + HIO 4 No reaction

(as it is not a vicinal diol)

The oxidation is particularly useful in determination of structure. Qualitatively, oxidation by HIO4 is

indicated by formation of a white precipitate (AgIO3) upon addition of silver nitrate. Since the
reaction is usually quantitative, valuable information is given by the nature and amounts of the
products, and by the quantity of periodic acid consumed.

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5.5 HALOFORM REACTION

The general reaction is represented as


RCHCH3 + X2 + NaOH RCO Na + CHX3 + NaX + H2O
OH O
The CH3 carbon is lost as CHX3 and the remaining part exists as acid salt, which can be acidified to
liberate free acid.
The structural feature essential in the compound to show haloform reaction is that any of the
following moieties should be present in the molecule attached to some electronwithdrawing group or
electron donating group by +I only.

CH3CH or XCH2CH or X2CHCH or X3CCH

OH OH OH OH

CH3C or XCH2C or X2CHC or X3CC

O O O O

or any other grouping that can be converted to any of the above moieties.
The mechanism of the reaction can be outlined as:
The reaction has 3 important steps. Step I is the oxidation, caused by mild oxidizing agent (hypo
halite ion). The second step is basepromoted halogenation and the third step is cleavage of C–C bond.
I2 + 2OH– I– + OI– + H2O RCHCH2I
OH
OI
+ 
 OH ..
OI I I
RCHCH3 RCCH3
H2O
RCCH2 
RCCH2I
(Oxidising I
OH agent) O O O
Carbanion I
OH
(Resonance stabilized)
OH + 
OH I2/OH ..
I I
RCCI3 RCCI3 RCCHI2 RCCHI
I
O O O O
Carbanion II
 
OI OI (more resonance stabilized
.. due to I effect of iodine)
RCOH + CI3 RCHCI3 RCHCHI2
O Proton OH OH
exchange

RCO + CHI3
Yellow crystalline ppt.
O (M.P = 119°C)

Some of the compounds which responds positively to iodoform test are

CH3CH2OH (only primary alcohol)

CH3CHCH3 CH3CHCH2CH3 PhCHCH3 (secondary alcohols)

, ,
OH OH OH

CH3CH CH3CCH3 CH3CCH2CH3 PhCCH3 (ketones)

(only aldehyde) , , ,
O O O O

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X
CH3CHCH3 CH3CCH3 CH3CCH2CCH3 CH3COEt (after heating with OH–)
X , X , O O , O

O
CH3CCH
 2
CO2H (after heating)


The compounds that respond negatively to iodoform test are

CH3COH CH3CCl CH3CNH2 CH3COR CH3COCCH3

, , , ,
O O O O O O

CH3CCH2COH CH3CCH2COEt
,
O O O O

The chemical properties of an alcohol, ROH, are determined by its functional group, –OH, the
hydroxyl group. Reactions of an alcohol can involve the breaking of either of two bonds: the C--OH
bond, with removal of the –OH group; or the O--H bond, with removal of –H. Either kind of reaction
can involve substitution, in which a group replaces the –OH or –H, or elimination, in which a double
bond is formed.

Differences in the structure of R cause differences in reactivity, and in a few cases even profoundly
alter the course of the reaction. We shall see what some of these effects of structure on reactivity
are, and how they can be accounted for.

5. Test Distinguishing 1, 2 & 3 alcohols

1. Lucas Test: Alcohols + ZnCl2 + HCl

RCH2OH  
  No reaction at room temperature
ZnCl
i) Alcohol : 2

HCl

ii) Alcohol : R 2CHOH   R 2CH  Cl White turbidity after 5-10 min.

ZnCl 2
HCl

R3C  OH  
  R3 C  Cl white turbidity instaneously
ZnCl
iii) Alcohol : 2

or HI

2. DICHROMATE TEST (OXIDATION TEST)

This test is based on the fact that three types of monohydric alcohols give different oxidation
products on oxidation.
The unknown alcohol is treated with sodium dichromate in dilute sulphuric acid
(orange solution) at room temperature. Then the oxidation products are identified.
(i) A carboxylic acid with same number of carbon atoms as in the alcohol, if formed confirms the
primary alcohol. The colour of the solution changes from orange to green.
(ii) A ketone with same number of carbon atoms as in the alcohol if formed confirms the secondary
alcohol. The colour of the solution also changes from orange to green.
(iii) In case the colour of the solution does not change, i.e. it remains same, then it is
3° alcohol.

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3. Victor Meyer Test

1° alcohol: RCH2OH   RCH2I 

P / I2
 RCH 2NO 2 
AgNO 2

 R – C – NO2
HNO 2

NOH
(nitrolic acid)
NaOH

CH3CNO2
Sodium salt of nitrolic acid
NONa
Red colour

Nitrolic acid on treatment with alkali gives colouration

2° alcohol: R R R
CHOH  
P / I2
CHI  
AgNO 2
CHNO2
R R R HNO2

Pseudonitrol on treatment with alkali gives

R
Blue colouration C – NO2
R N=O
(Pseudonitrol)
3° alcohol: R3C – OH   R3C – I 
P / I2
 R3C – NO2
AgNO 2

HNO2

No reaction
(colour less)

7. Ethers
Ethers are compounds in which oxygen is bonded to two alkyl substituents. If the alkyl substituents are
identical, the ether is symmetrical or simple ether and if they are different, the ether is unsymmetrical
ether.

R O R R O R
A symmetrical or simple ether An unsymmetrical or mixed ether.

The groups R and R can be alkyl or aryl. When both the R groups are alkyl, they are called alkyl
ether and when at least one of the R group is an aryl, they are called aryl ethers.

7.1 Structure and Nomenclature of Ethers

General formula :R—O—R are the same or different alkyl, aryl, alkeny, vinyl, alkynl groups.

1. i) simple / symmetrical ethers : R & R are the same group

e.g. CH3—O—CH3 Dimethyl ether

ii) Mixed / Unsymmetrical ethers: R & R are different group

e.g. C6H5—O—CH2C6H5 Benzyl phenyl ether

2. i) aliphatic ethers : R & R are alkyl groups

e.g. CH3—O—CH2CH3 Ethyl methyl ether

ii) Aromatic ethers : Either are both R & R are aryl groups

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e.g. C6H5—O—C6H5 Diphenyl ethers

Aromatic ethers are further subdivided into :

a) Phenolic ethers: One of the groups are aryl while other is alkyl or Alkyl aryl ethers

e.g. C6H5—O—CH3 Methyl phenyl ether

b) Diaryl ethers: both groups are aryl

e.g. C6H5—O—C6H5 Diphenyl ether

3. There are various types of cyclic ethers also.

i) Cyclic ethers consisting of 2 C's in a 3 member ether are called as oxirane or Epoxides

ii) 3 C's in a 4 member ether are called oxetanes

iii) 4C's in a 5 member ether are called tetrahydrofurans.

O O

O O O
Oxirane Oxetane Tetrahydraofuran 1,4 - dionane
(epoxide) (oxacyclobutane) (Oxacyclopentane) (1,2 - dioxacyclohexane)

7.2 Physical Properties

1. Physical state, colour and odour: Dimethyl and ethyl methyl ethers are gases at ordinary
temperature while the other lower homologues of ethers are colourless liquid with
characteristic 'ether smell'.

2. Dipole nature: Ethers have a tetrahedral geometry i.e., oxygen is sp3 hybridized. The C—
O—C angle in ethers is 110°. Because of the greater electronegativity of oxygen than
carbon, the C—O bonds are slightly polar and are inclined to each other at an angle of 110°,
resulting in a net dipole moment.
lone pairs
3
sp
R
pairs
3
sp
O
Net dipole moment
R
R 110° R

3. Bond angle of ether is greater than that of tetrahedral bond angle of 109°28. This is due to
the fact that internal repulsion by the hydrocarbon part is greater than the external repulsion
of the lone pair on oxygen. If the size of the hydrocarbon part increases, then the bond angle
also increases slightly and
vice - versa.

4. Solubility and boiling point: Due to the formation of less degree of hydrogen bonding, ethers
have lower boiling point than their corresponding isomeric alcohols and are slightly soluble in
water. Upto C4 (on both side of —O—) ether is soluble in water being polar. Moreover,
others are fairly soluble in common organic solvents like alcohols, benzene chloroform,
acetone etc.
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R
– +
 
O----H—O + –
R
 
R H--------O
R

5. Ethers are polar as well as non polar. Alkyl groups in an ether act as a hydrophobic part
whereas oxygen acts as a hydrophilic part. If the hydrophilic part is dominant over the
hydrophobic part, then ether will be polar. As the size of the hydrophobic part increases, the
ether becomes non polar.

7.3 Preparation of Ethers

1. From alcohols

Ethers may be prepared by dehydration of alcohols either in the presence of acid or heated
alumina.

Acid - catalysed dehydration

The yield of alcohol however depends on the nature of alcohols (1,2° or 3°) 2° alcohol mainly
gives alkenes with low yields of ethers whereas 3° exclusively gives alkenes.

 Order of dehydration of alcohol leading to formation of ethers: 1°  2°  3°

H SO
CH3CH2OH 2
4
 CH3CH2  O  CH2CH3
140o C Ether

Mechanism of SN2

H

CH3CH2— O —H + H+ HSO 4  CH3—CH2—O+—H + H 2 SO 4
 oxonium ion

H H

CH3CH2— O H + CH3CH2—O+—H  CH3CH2—O +—CH2CH3


H

CH3CH2—O+—CH2CH3 + H  O —H  CH3—CH2—O—CH2CH3 + H3 O 


Catalytic dehydration: Dehydration of alcohols to ethers can also be achieved by passing the
vapours of an alcohol over heated alumnia at 523 K.

Al O
e.g.: CH3CH2—OH + H—OCH2CH3 2
3
 CH3CH2—O—CH2CH3 + H2O
523 K

2. By the action of diazomethane on alcohols - Methyl ethers can also be prepared by action of
CH2N2 on alcohols in presence of fluoroboric acid (HBF4) as catalyst.

HBF4
CH3CH2OH + CH2N2   CH3CH2—O—CH3 + N2

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(2) Williamson's synthesis: It is the most important method for formation of ethers. It is a
nucleophilic substitution reaction. Nucleophile (SN2) attack by alkoxide ion on an alkyl
halide/alkyl sulphate / alkyl sulphonato which are known as substrates.

a) Substrates should have good leaving group like X–, —OSO2, —OSO2R.
b) Substrates must have a primary alkyl group for good yield.
c) In case of tertiary substrate elimination occurs giving alkenes
d) With a secondary alkyl halide, both elimination and substitution products are obtained.
RX + Na+ -OR'  ROR' + Na+ X-

For example:
CH3 CH3

 CH3OCCH3
+ -
CH3Br + Na OCCH3

CH3 CH3
Sodium tert-Butyl methyl ether
tert-butoxide

Reaction involves nucleophilic substitution of alkoxide ion for halide ion; it is strictly analogous to the
formation of alcohols by treatment of alkyl halides with aqueous hydroxide.

R  X  R'OR
- -
R'O + + X

Nucleophile Substrate Leaving group

Since alkoxides and alkyl halides are both prepared from alcohols, the Williamson method ultimately
involves the synthesis of an ether from two alcohols.

If we wish to make an unsymmetrical dialkyl ether, we have a choice of two combinations of

reagents; one of these is nearly always better than the other. In the preparation of tert-butyl ethyl
ether, for example, the following combinations are conceivable :
-
H3C CH3 CH3CH2Br + t-BuO

O CH3

CH3 t-BuCl + EtO - (not feasible)

Which do we choose ? Alkoxides are not only nucleophiles, but also strong bases which tend to
react with alkyl halides by elimination, to yield alkenes. Whenever we are trying to carry out
nucleophilic substitution, one must be aware of the danger of a competing elimination reaction. The
tendency of alkyl halides to undergo elimination is 30 > 20 > 10.

In the above example, the use of the tertiary halide is rejected as it would be expected to yield
mostly or all elimination product; hence the other combination is used. Aromatic ethers are formed
when phenoxides react with alkyl sulphates following SN2 mechanism.

C6H5O–Na+ + CH3—OSO2O—CH3  C6H5OCH3 + NaSO2OCH3

3. From alkenes: Ethers can also be prepared by the addition of alcohols to alkenes in presence
of acids as catalyst.

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CH3 CH3
H2SO4
CH3—C=CH2 + H—OCH3   CH3—C—OCH3

CH3

4. From Grignard reagent: Higher ethers can be prepared by treating  - halo ethers with
suitable Grignard reagents.
CI
Dry
CH3—O—CH2Cl + CH3MgI  CH3—O—CH2CH3 + Mg
ether
I

Stability of Ethers

On standing in contact with air, most aliphatic ethers are converted slowly into unstable peroxides.
Although present in only low, these peroxides are very dangerous, since they can cause violent
explosions during the distillation that normally follow extractions with ether.

The presence of peroxides is indicated by formation of a red colour when the ether is shaken with
an aqueous solution of ferrous ammonium sulfate and potassium thiocyanate; the peroxide oxidizes
ferrous ion to ferric ion, which reacts with thiocyanate ion to give the characteristic blood-red colour
of the complex.


SCN ( 3 n ) 
peroxide + Fe2+  Fe3+  Fe(SCN)n (n 1to6 )
Re d

Peroxides can be removed from ethers in a number of ways, including washing with solutions of
ferrous ion (which reduces peroxides), or distillation from concentrated H2SO4 (which oxidizes
peroxides).

For use in the preparation of Grignard reagents, the ether (usually diethyl) must be free of traces of
water and alcohol. This so-called absolute ether can be prepared by distillation of ordinary ether
from concentrated H2SO4 (which removes not only water and alcohol but also peroxides), and
subsequent storing over metallic sodium.

Illustration 8: Explain why sometimes explosion occurs while distilling ethers.

Solution: It is due to formation of peroxide

OOH
h
CH3CH2—O—CH2CH3 + O2  CH3—CH—O—CH2CH3

7.4 Reactions of Ethers. Cleavage by Acids

Ethers are generally less reactive and react only with acids. The reactive sites in ethers are:

i) C—H bond

ii) —O— group of ether bond

Ethers resist the attack of nucleophiles and bases. However, they are very good solvents in many
organic reactions due to their ability to solvate cations by donating the electron pair from oxygen
atom.
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1. Halogenation of ethers: Ethers undergo halogenation in dark to give halogenated ethers. The
hydrogen atom attached to the C atom directly linked to oxygen atom is replaced by halogens.

Cl2 Cl2
CH3CH2—O—CH2CH3  CH3CH2—O—CHCH3  CH3CH—O—CHCH3

Cl Cl Cl

2. Ethers as base: O atom of ethers makes them basic. They react with a proton donor to give
oxonium salts.

H
 |
CH3CH2  O CH2CH3  H  Br  CH3CH2  O CH2CH3Br 
 

3. Reaction with acids:

a) Cold conc. HI/HBr - Ether undergoes cleavage with cold conc. solution of HI/HBr to give a
mixture of alcohol and iodides. The smaller of alkyl groups goes with the halide and larger
group forms alcohols.

R—O—R + HI  R—OH + RI (R R)

cold

b) Hot conc. HI/HBr - On heating ethers with conc. HI / HBr ethers gives two molar equivalents
of halides.

R—O—R + HI  RI + RI + H2O

hot conc.

In the first step, ether is protonated by HX to give protonated ether. In the second step,
halide ion acts as nucleophile and attacks protonated ether to undergo cleavage. This step is favoured
because the leaving group (alcohol) is weakly basic.
H
..
Step I: R O: R + H X R O R + X

protonated ether

H H 
SN2 
Step II: 
R O R + X X R O R R X + ROH
 pathway +
SN1
pathway

R + ROH
+X
R X
Reaction in second step can take the direction of SN1 or SN2 pathway, depending upon the
conditions employed and the structure of ether. When both the alkyl groups are methyl or 1°, it will follow
SN2 reaction and when atleast one of the alkyl group is 3°, the reaction follows SN1 pathway. For all other
cases, it can undergo SN1 or SN2 pathway, depending upon the reaction conditions.

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For example,
H
HI
CH3OC2H5 (One equivalent) C2H5OCH3 + I

S N2
pathway
H 

C2H5 O CH3 I CH3I + C2H5OH
+

Case I: H
HI SN 2
CH3—O—CH—CH3 
 CH3—O—CH—CH3   CH3I +CH3—CH—OH

primary _
CH3 I CH3 CH3
secondary

Case II: CH3 H CH3

HI
CH3—CH—O—C—CH3 
 CH3—CH—O—C—CH3
+

CH3 CH3 CH3 CH3

secondary tertiary –
I ,SN1
CH3

CH3—CH—OH + CH3—C—I

CH3 CH3

Case III: CH3

CH3—O—C—CH3
primary tertiary
CH3

Ether
(i.e., aprotic
HI H2O HI
polar/Non polar
solvent)SN2 Protic polar
SN1
CH3I + (CH3 )3C—OH
CH3

CH3—C—I + CH3OH

CH3

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Case IV: OH

HI (g)
O—CH3 CH3I +
S N2
OH

Conc. HI CH I +
3
S N1

Hint: a) Methyl cation is stable than phenyl cations

b) Hot conc. H2SO4 - secondary and tertiary ethers react with to give a mixture of alcohols
and alkenes.

Conc.H SO
(CH3)3CO—CH3   2 
4
 (CH3)2—C=CH2 + CH3OH
hot

conc.H2SO 4
(CH3)3CO—    (CH3)2—C=CH2 + HO
hot
isobutene
Cyclohexyl tert butyl ether cyclohexanol

Example

CH3CH2  O  CH2CH3 + H2SO4  CH3CH2  OH CH3CH2  OSO2OH

diethyl ether conc. ethyl alcohol ethyl hydrogen sulphate

4. Reaction with acid chlorides and anhydrides: Acid chlorides react with ethers when heated in the
presence of anhyd. ZnCl2 or AlCl3 to form chloride and esters.

[Link]
e.g. C2H5  O  C2H5 + CH3 COCl     

2
 C2H5Cl  CH3COOC2H5
diethyl ether Acetyl chloride  ethyl chloride ethyl acetate

Anhydride react with ethers to give only esters

anhy. AlCl
(C2H5 )2 O + (CH3CO)2 O    
3
 2CH3 COOC2H5
diethyl ether Acetic anhydride  Ethyl acetate

Electrophilic substitution reactions

OCH3 OCH3 OCH3

Br
Br2 / CS2 +
  
Anisole
o-Bromoanisole Br
p-bromoanisole

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OCH3 OCH3 OCH3

NO2
conc.HNO3
   
conc.H2SO 4 +
Anisole
o-Nitroanisole
NO2
p-Nitroanisole

5. Action of air and light - Reaction involving alkyl group leads to the formation of peroxides.

OOH
h
CH3CH2—O—CH2CH3 + O2  CH3—CH—O—CH2CH3

It is a free radical reaction and oxidation occurs at the C atom next to the ethereal oxygen to
form hydroperoxides .

7.5 Oxirane

Cyclic ethers with three membered rings are known as expoxides or oxiranes (IUPAC
nomenclature).

Example
O
O
R R
oxirane
R R
epoxide

Preparation

a) Oxidation of ethylene : In presence of Ag2O

Ag O
H2C=CH2 + O2   
2

300o C H2C—CH2

b) Expoxidation: Most important method of formation. It is the reaction in which an alkene is

reacted with an organic peroxy acid or peracid such as per benzoic acid (C6H5CO—O—OH) or
peracetic acid (CH3CO—O—OH).

O O
|| ||
expoxidation
RHC=CHR + C 6 H5 C O  OH     
 RHC—CHR+ C 6 H5  C OH

Reactions: The epoxy bond angle is lower than that of normal tetrahedral bond angle (109°28).
 There is strain in the ring due to the unstability. Due to this, epoxides are highly reactive
towards nucleophilic substitution reaction (unlike ethers). They undergo ring opening reaction so

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as to release the strain. Epoxides undergo acid catalysed and base catalysed opening of the
ring.

Acid catalysed opening

The acid reacts with epoxides to prooduce a protonated epoxide. The protonated epoxide reacts
with the weak nucleophile (water) to form protonated glycol , which then transfer a proton to a
molecule of water to form the glycol and hydronium ion.

+
—C—C— + H—O—H  —C—C— + OH2
+
O H OH
epoxide Protonated epoxide

OH2
—C—C— + :O—H  —C—C—   —C—C— + H3O+

OH+ H OH OH2 OH OH
Protonated epoxide +
Weak nucleophile glycol

Base Catalysed opening: Epoxides can also undergo base - catalysed ring opening provided the
attacking nucleophile is also a strong base such as an alkoxide or hydroxide ion.

HOR
—C—C—+ –O—R  O–—C—C—OR   HO—C—C—OR + OR–
O
epoxide nucelophile an alkoxide ion

8. Phenols
8.1 Introduction
Compounds having hydroxyl groups directly attached to a benzene ring are called phenols. A phenolic OH
is characterized by the formation of violet, red or green colouration when treated with neutral FeCl3 solution.
Some examples of phenolic compounds are given below.
OH OH OH OH
CH3

CH3
Phenol omethylphenol mmethyl phenol CH3
(Carbolic acid) (ocresol) (mcresol) pmethyl phenol
(pcresol)

OH OH OH OH
OH OH

OH OH
odihydroxybenzene mdihydroxybenzene OH 1, 2, 3trihydroxybenzene
(catechol) (resorcinol) pdihydroxybenzene (pyrogallol)
(Hydroquinone)

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OH
8 1
7 2 OH
6 3
5 4
1naphthol 2naphthol
(naphthol) (naphthol)

8.3 Nomenclature of phenols and phenyl ethers

Compound having a hydroxyl group directly attached to a benzene ring are called phenols. The term
phenol is also used for the parent compound, hydroxybenzene. Hydroxybenzene, may be regarded
as an enol, as implied by the name phenol, from phenyl + enol. However unlike simple ketones,
which are far more stable than their corresponding enols, the analogous equilibrium for phenol lies
far on the side of the enol form. The reason for this difference is the resonance energy of the
aromatic ring, which provides an important stabilization of the enol form.

O OH
H
H

Cyclohexa –2,4 – dien –1 one

Since the functional group occurs as suffix in phenol, many compounds containing hydroxyl group
are named as derivatives of the parent compound phenol, as illustrated by the IUPAC names.

OH OH
NO2

NO2 C(CH3)3
2,4 - dinitrophenol p-t butylphenol

Suffix groups such as sulfonic acid and carboxylic acid take priority, and when these groups are
present the hydroxyl group is used as a modifying prefix.
COOH SO3H
CHO
OH

OH OH
OH
p-hydroxybenzoic acid m – hydroxy 2,4 – dihydroxybenzene
benzaldehyde sulfonic acid

OH

 - naphthol

Phenyl ethers are named in the IUPAC system as alkoxyarenes, although the ether nomenclature is
used for some compounds.
OC(CH3)3

CH3 OCH2

t-butoxybenzene p-benzyloxytoluene

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Phenols and their ethers are widespread in nature, and, as is usual for such compounds, trivial
names abound.

OCH3 OC2H5 CH3

OH

anisole phenetole o-cresol

OH OH
O2N CO2H
NO2
OH
OH
NO2
Salicylic acid resorcinol
Picric acid
OH
OH
OH

OH
catechol
hydroquinone

The methyl phenols are commonly called cresols.

CH3 CH3 CH3

OH OH
OH
(o-cresol) (m-cresol) (p-cresol)

The benzene diols also have common names

OH OH OH

OH HO
OH
(catechol) (resorcinol) (quinol)

 Salts of Phenols

Phenols are fairly acidic compounds, and in this respect, markedly different from alcohols, which
are even more weakly acidic than water. Aqueous hydroxides converts phenols into their salts,
aqueous mineral acid convert the salts back into the free phenols.
–
OH –
ArOH +
ArO
H
A phenol A phenoxide ion
(acid) (salt)
Insoluble in water Soluble in water

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Most phenols have Ka values in the neighbourhood of 10–10 and are thus weaker acids than the
carboxylic acids (Ka values about 10–5). Most phenols are weaker than carbonic acid and hence
unlike carboxylic acids do not dissolve in aqueous bicarbonate solution.

8.4 Preparation

Industrial method: Phenol is a highly important industrial chemical; it serves as the raw material for
a large number of commercial products ranging from asprin to a variety of plastics.

i) Hydrolysis of chlorobenzene: (Dow’s process): When chlorobenzene is heated at 360C and

under high pressure with aqueous sodium hydroxide, it is converted to sodium phenoxide, which
on acidification gives phenol.

Cl ONa OH
H
  
NaOH

360 C; 320 atm

The mechanism for the above reaction involves probably the formation of benzyne.

ii) Alkali fusion of Sodium benzene sulfonate

Sodium benzene sulfonate is melted (fused) with sodium hydroxide (at around 350C) to
produce sodium phenoxide which on acidification yields phenol.

SO3Na ONa OH
H
 
NaOH

 
350 C

SO3Na ONa OH
H
 
NaOH


300  350 C
H3C H3C H3C

iii) From Cummene Hydroperoxide

It is a method for converting two relatively inexpensive organic compounds; benzene and
propene into two more valuable ones - phenol and acetone. The only other substance
consumed in the process is oxygen from air.

CH3

CH
+ CH2 = CH– CH3  
250
CH3
H3PO 4

(Cummene)
CH3
CH3
CH C – O – OH
95 135 
+ O2  
CH3 CH3
(Cummene hydroperoxide)

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CH3
O
C – O – OH 
OH
 
H , H2O

 + CH3 – C – CH3
CH3 50  90 C

The mechanism of the above reactions are,

 
CH2 = CH – CH3 
 CH3 – C H – CH3
H

CH3

CH
CH3 – C H – CH3  CH3

The second reaction is a radical chain reaction. A radical initiator forms a 3 benzylic radical which

then forms cummene hydroperoxide.

CH3 CH3

CH C CH 3
 
R  +RH
CH3 H
CH3 CH3

C –CH3 C – O – O
+ O2 
CH3

CH3 CH3 CH3

CH3
C – O – O C – O – OH C
H–C  +
CH3 CH3 CH3
CH3

The third one, resembles the carbocation rearrangements.

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CH3
CH3 
C – O – OH2
C – O – OH + H+ 
CH3
CH3
CH3 
C–O

CH3
Phenyl anion
migration to oxgen
CH3 CH3

O – C – OH2 O – C
 H2 O

CH3 CH3
CH3
CH3
O – C – OH
O–C–O–H 
CH3
CH3

O OH
OH O–
+ CH3 – C – CH3  + CH3 – C – CH3

Laboratory Methods

a) Alkali Fusion of Aryl Sulphonate Salts

Phenols may be prepared by fusion of sodium arylsulphonates with sodium hydroxide

b) Aromatic Nucleophilic Substitution of Nitro Aryl Halides

Phenols are formed when compounds containing an activated halogen atom are heated with
aqueous sodium hydroxide, e.g.., p-nitrophenol from p-chloronitrobenzene.

Cl ONa

 
NaOH

O 2N O 2N

c) Hydrolysis of diazonium salts

When a diazonium sulphate solution is steam distilled, a phenol is produced

 
Ar N2 H SO4  H2O  ArOH + N2 + H2SO4

d) Distillation of phenolic acids with soda-lime produces phenols, e.g. sodium salicylate
gives phenol.

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Cl ONa
 
NaOH
CaO

CO 2Na

8.2 Physical Properties

 Phenol is a colorless, toxic, corrosive, needle shaped solid.

 Phenol soon liquifies due to high hygroscopic nature.
 Phenol is less soluble in water, but readily soluble in organic solvents.
 Simplest phenols, because of hydrogen bonding have quite high boiling points.
 o-nitrophenol is, steam volatile and also is less soluble in water because of intramolecular
hydrogen bonding.

Illustration 10: Explain the lower boiling point and decreased water solubility of o-nitrophenol and
o-hydroxybenzaldehyde as compared with their m-and p-isomers.
Solution: Intramolecular H–bonding (chelation) in the o-isomers inhibits intermolecular
attraction, lowering the boiling point, and reduces H-bonding with H2O,
decreasing water solubility. Intramolecular chelation cannot occur in m- and p-
isomers.

O O
H H
O O
+ C
N
H
O–
o-Nitrophenol o-Hydroxybenzaldehyde

8.5 Acidity of Phenols

Phenols are weak acids (pKa = 10). They form salts with aqueous NaOH but not with aqueous
NaHCO3.

Acidity of Phenols

Although Phenols are structurally similar to alcohols, they are much stronger acids. But phenol is a
weak acid when compared to a carboxyllic acid, such as acetic acid
(pKa = 4.7447).

The greater acidity of phenol owes itself primarily to an electrical charge distribution in phenols that
causes the –OH oxygen to be more positive; therefore the proton is held less strongly.

The factor influencing the electron distribution may be the contributions to the overall resonance
hybrid of phenol made by the resonance structures shown below. The effect of these structures is to
withdraw electrons from the hydroxyl group and to make the oxygen positive.

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  
O–H OH OH OH
  

OH

The considerably greater acid strength of PhOH (pKa = 10) than that of ROH (pKa = 18) can be
accounted for as the negative charge on the alkoxide anion, RO–, cannot be delocalized, but on
PhO– the negative charge is delocalized to the ortho and para ring positions as indicated by the
starred sites in the resonance hybrid.

PhO– is therefore a weaker base than RO–, and PhOH is a stronger acid the effect of

a) electron – attracting and

b) electron – releasing substituents on the acid strength of phenols

Electron–attracting substituents disperse negative charges and therefore stabilize ArO– and
increase acidity of ArOH. Electron – releasing substituents concentrate the negative charge on O
destabilizes ArO– and decreases acidity of ArOH.

In terms of resonance and inductive effects we can account for the following relative acidities.
a) p-O2NC6H4OH > m–O2NC6H4OH > C6H5OH
b) m–ClC6H4OH > p-ClC6H4OH v > C6H5OH
a) The–NO2 is electron–withdrawing and acid–strengthening. Its resonance effect, which occurs
only from para and ortho positions, predominates over its inductive effect, which occurs also
from the meta position.
b) Cl is electron – withdrawing by inductive. This effect diminishes with increasing distance
between Cl and OH. The meta is closer than the para positions and m-Cl is more acid –
strengthening than the p-Cl. Other substituents in this category are F,Br, I, +NR3.

8.6 Chemical Properties

8.6.1 ACYLATION:
Phenols react with carboxylic acid anhydrides or acid chlorides to yield phenyl esters.
O–H OCOR

(RCO)2O/OH
+ RCOO

O–H OCOR

RCOCl/OH
+ Cl

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8.6.2 FRIES REARRANGEMENT:

The phenyl ester formed from the reaction of phenol and acid anhydride undergoes rearrangement
when treated with anhydrous AlCl3 to yield ortho and parahydroxyketones. The oisomer is
separated from the mixture by steamdistillation.
O
OH OH
OCCH3
AlCl3(CS2) COCH3
 +
pHydroxy
oHydroxy COCH3 acetophenone
acetophenone
Generally low temperature (60°C or less) favours the formation of the pisomer whereas high
temperature (above 160°C) favours the oisomer.
Mechanism:
The reaction proceeds as FriedelCrafts acylation, acylium ion being supplied by the substrate
itself.
Cl2Al  COCH3
OCOCH3 O
Cl
+
AlCl3(CS2) [COCH3]
Cl

O–AlCl2 O–AlCl2 O–AlCl2 OH

H
+  COCH3 COCH3
COCH3
COCH3 Cl H2 O
HCl

Similarly, if the electrophile attacks at pposition, pisomer is formed.

8.6.3 REACTION WITH BENZOYL CHLORIDE:

Alkaline solution of phenol when treated vigorously with benzoyl chloride yields phenylbenzoate.
The reaction is known as SchottenBaumann reaction.
O O
NaOH
C6H5–OH + ClCC6H5 C6H5OCC6H5
Phenol Benzoyl chloride Phenyl benzoate

8.6.4 REACTION WITH ZnDUST:

Phenol yields benzene when heated with Zndust.

C6H5–OH + Zn  C6H6 + ZnO
8.6.5 REACTION WITH AMMONIA:
Phenol is converted into aniline when heated with ammonia under pressure or in presence of ZnCl2.
ZnCl
C6H5–OH + NH3  
2
 C6H5–NH2 + H2O

8.6.6 REACTION WITH PCl5:

Phenol reacts with PCl5 to give chlorobenzene along with POCl3 and HCl. Further with POCl3,
phenol reacts to produce triphenyl phosphate. With PCl3, phenol reacts to give chlorobenzene and
H3PO3.
C6H5–OH + PCl5  C6H5–Cl + + POCl3 + HCl
3C6H5–OH + POCl3  O=P(OC6H5)3 + 3HCl
(Triphenyl phosphate)
3C6H5–OH + PCl3  3C6H5–Cl + H3PO3
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8.6.7 TEST FOR PHENOL:

Phenol and its derivatives give a violet, red, blue or green colouration with ferric chloride solution.
This reaction is characteristics of all compounds containing C(OH)=C group.

8.7.1 BROMINATION:
Phenol on treatment with chlorine or bromine water gives an immediate precipitate of
2,4,6trihalogen derivative. Phenol in aqueous medium is partially ionised and the phenoxide ion
thus obtained is much more reactive than phenol itself towards electrophilic attack. Moreover,
halogen reacts with water forming halogen acid and hypohalous acid. The proton attacks at the OH
group of hypohalous acid to give H2OX, which acts as a stronger electrophile. Therefore,
halogenation takes place at all the ortho and para positions.
OH O

+ H+

H  ( from HBr ) 
Br2 + H2O HBr + HOBr ; HOBr    H2OBr

O O O O
 Br
H
+ BrOH2 H
+
  H

BrOH2 H Br
Br Br

O O O OH
Br  Br Br Br Br Br Br
H
+ +
BrOH2 H
H 

Br Br Br Br
(Yellow ppt.) 2,4,6Tribromophenol
If the halogenation is carried out in nonaqueous medium like CS2 or CCl4, only monosubstitution
takes place. This is because the ionisation of phenol does not occur in nonaqueous medium. The
benzene ring of phenol is less activated than that of phenoxide ion as well as the bromine in Br2

molecule is not as electrophilic as in BrOH2.
OH OH OH
Br
CS2, 0°C
+ BrBr +
HBr

oBromophenol Br
pBromophenol
oBromophenol is also prepared by protecting one ortho and the para positions by sulphonation.
OH OH OH OH
SO3H Br SO3Na Br
H2SO4 Br2 H +

NaOH boil

SO3H SO 3Na

So strong is the activation of benzene ring in aqueous medium that derivatives of phenol containing
COOH group or SO3H group either at the ortho or at the para position are displaced by Br in

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bromination reaction. This is an example of brominative decarboxylation. For example, salicylic acid
when treated with bromine water gives 2,4,6trisubstituted phenol.
OH
COOH
Br2
H2O OH
CO2 Br Br
OH

Br2
H2O
Br
CO2
CO2H
O

.. O
H2O C=O
:O
.. C + BrOH2 O O Br + CO2

O Br

2BrOH2
2H2O
2H
+

Br Br

H
HO Br O Br

Br Br
In case when SO3H group is present at ortho and para positions, desulphonation takes place
liberating SO3 gas.
Trisubstitution of benzene is also observed when aniline is treated with bromine because the
reactivity of aniline is same as that of phenoxide ion towards electrophilic attack.

8.7.2 NITRATION:
When treated with dilute HNO3, phenol gives o and pnitrophenol. When treated with nitrating
mixture, phenol gives 2, 4, 6 trinitrophenol (picric acid) but the yield is poor.
OH OH OH OH
NO2 O2N NO2
dil HNO3 HNO3
20°C
+ H2SO4

NO2 NO2
oNitrophenol pNitrophenol 2,4,6–trinitrophenol
(Picric acid)
Picric acid can be alternatively prepared as follows:
Cl Cl OH OH
NO2 NO2 O 2N
HNO3 aqueous HNO3
NO2
H2SO4 Na2CO3 H2SO4

NO2 NO2 NO2

2,4,6–trinitrophenol
(Picric acid)

Pure pnitrophenol is prepared in good yield when phenol is treated with nitrous acid and the
product, pnitrosophenol is oxidised to pnitrophenol.
+
HON=O + H+  HON=O  H2O + NO
H

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OH OH OH

+ NO Dil. HNO3

NO NO2

8.7.3 SULPHONATION:
When treated with concentrated sulphuric acid, phenol gives either o or p sulphonated derivatives.
Low temperature yields o isomer whereas high temperature yields pisomer in greater yield.
OH
SO3H
H2SO4, 298 K
OH H2O
(ophenol sulphonic acid)

OH

H2SO4, 373 K
H2O (pphenol sulphonic acid)

SO3H
8.7.4 FRIEDELCRAFTS REACTION:
Phenol undergoes alkylation and acylation to form mainly pderivative along with some
oderivative.
OH OH OH
CH3
+ CH3–Cl AlCl3
–HCl
+

CH3
OH OH OH
COR
AlCl3
+ RCO–Cl –HCl
+

COR
The yield is not good as the reactivity of phenol is diminished by the formation of a complex with
Lewis acid AlCl3.

HOAlCl3

8.7.5 KOLBE’S REACTION:

Sodium phenoxide is heated with carbon dioxide at 120140°C under pressure to yield sodium
salicylate, which upon acidification produces salicylic acid.
ONa OH OH
HCl
+ CO2
COONa COOH
Salicylic acid
A small amount of pderivative is also formed. If the temperature rises above 140°C, the pisomer
is the main product.

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Mechanism:
O O O O HO HO
H
H CO2 CO2H
C Tautomerize
CO2
+
: H
O
(isolated) (Salicylic acid)

Salicylic acid is used for the preparation of Aspirin, oil of winter green (methyl salicylate) and salol
(phenyl salicylate).
OH OH OCOCH3
CO2Me CO2H CO2H
MeOH (CH3CO)2O
Conc. H2SO4 NaOH

Methyl salicylate Aspirin

PhOH
Conc. H2SO4

OH
CO2Ph
Phenyl salicylate

8.7.6 REIMERTIEMANN REACTION:

An alkaline solution of phenol is refluxed with chloroform at 60°C, distilling off the excess of
chloroform and acidifying the residual liquid with sulphuric acid. As a result, ohydroxy and
phydroxy benzaldehyde are formed, which are separated by steamdistillation.

OH OH
CHO
AlCl3
+ CHCl3 + 3NaOH + 3NaCl + 2H2O

Mechanism:
Cl Cl
OH or OR Cl
HCCl :CCl ClCCl
H2O
dichloro carbene
Cl or  ROH Cl
O O O
H CCl2 H
: IMPE
CCl2

O O OH
CHCl2 CHO CHO

2OH/–2Cl– H
–H2O

(more stable) (isolated)

If ‘o’ both the opositions are blocked, phydroxy benzaldehyde is the main product. With blocked
pposition, ohydroxy benzaldehyde and cyclohexadienones are formed.

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O O O O HO
H H
CHCl2 CHO
CCl2 IMPE 2OH H+
CCl2 H2O

Me Me Me Me Me
(isolated)

O O O

CCl2 H+

Me Me CCl2 Me CHCl2

Cyclohexadienone derivative remains unhydrolysed as it has a neopentylic system, which involves

lot of steric crowding.

When phenol is refluxed with CCl4 in alkaline medium, salicylic acid is formed.

OH OH
CO2H
+ CCl4 + 4NaOH + 4NaCl + 2H2O

8.7.7 GATTERMANN’S REACTION:

When phenol is treated with liquid HCN and gaseous HCl in the presence of anhydrous AlCl3 and
the product formed is hydrolysed, phydroxy benzaldehyde is formed.
AlCl 
HCl + HCN 
3
 HC=NH Cl–

OH OH OH

– AlCl3/HCl H2O
+ HC=NH Cl NH3

CH=NH CHO
(imine) pHydroxybenzaldehyde

8.7.8 LIEBERMANN TEST:

When phenol is dissolved in concentrated sulphuric acid and a few drops of aqueous sodium nitrite
is added, a red colour is obtained on dilution and turns blue when aqueous sodium hydroxide is
added.

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9. Solved Examples
9.1 Subjective
Example 1:
Compound (X) (C5H8O) does not react appreciably with Lucas reagent at room temperature but gives a
precipitate with ammoniacal silver nitrate. With excess of MeMgBr, 0.42 g of (X) gives 224 ml CH4 at
STP. Treatment of (X) with H2 in presence of Pt catalyst followed by boiling with excess HI gives
npentane. Suggest structure for (X) and write the equations involved.
Solution:
(1) (X), (C5H8O) does not react with Lucas reagent appreciably at room temperature but gives precipitate with
ammoniacal AgNO3 and thus, (X) has terminal alkyne linkage as well as primary alcoholic group.
(2) (X) on hydrogenation and then reacting with HI gives pentane and thus, (X) is straight chain compound.
(3) Keeping in view of the above facts (X) may be
CH2.CH2.CH2.CCH*
(x)
OH* Pent4yn1ol
(4) Its reaction with MeMgBr gives CH4. (It has two acidic or active H* atoms) and thus, 1 mole of (X) will give
two mole of CH4.
CH2.CH2.CH2.CCH+2CH3MgBr  2CH4
(X )
OH
 84 g (X) gives 2  22.4 litre CH4
2  22.4  0.42
 0.42 g (X) will give = 224 ml CH4
84
Given fact is confirmed.

Example 2:
10 g of a mixture of hexane and ethanol are reacted with sodium to give 200 ml hydrogen at 27°C and
760 mm pressure. What is the percentage of ethanol into the mixture?
Solution:
Given, Hexene + ethanol = 10 g
Therefore, C2H5OH + Na  C2H5ONa + ½ H2
PV 760  200
Now, Mole of H2 formed = =
RT 760  100  0.0821  300
= 8.13  103 mole
( 200 ml H2 is formed at 27°C and 760 mm pressure)

1
Now, mole H2 is formed by = 46 g C2H5OH
2
 8.13  103 is formed by = 46  8.13  103  2 g C2H5OH
= 0.748 g
0.748  100
 % of ethanol in mixture = = 7.48%
10

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Example 3:
3, 3Dimethylbutan2ol loses a molecule of water in the presence of concentrated sulphuric acid to
give tetramethylethylene as a major product. Suggest a suitable mechanism.
Solution:
+
(i) H + CH3
(CH3)[Link].CH3 (CH3)[Link] .CH3 shift
(ii) H2O

H+
(CH3)2C=C(CH3)2 (CH3)2C+CH(CH3)2

Example 4:
Give the structure of the major organic products formed 3ethyl2pentene under each of the
following reaction conditions.
(a) HBr in the presence of peroxide
(b) Br2 / H2O
(c) Hg(OAc)2 /H2O; NaBH4.
Solution:
Br
HBr
(a) (CH3CH2)2C=CHCH3 (CH3CH2)2CHCHCH3
H2O2
OH
Br2/H2O
(b) (CH3.CH2)2C=CHCH3 (CH3.CH2)2CCHCH3
Br
Hg(OAc)2/H2O
(c) (CH3.CH2)2C=CHCH3 (C2H5)[Link]
NaBH4

Example 5:
Identify the ethers that are cleaved with excess conc. HI to yield (a) (CH3)3Cl and CH3CH2CH2I, (b)
cyclohexyl and methyl iodides and (c) I(CH2)5I.
Solution:
Place an O atom between the C’s bonded to I’s. (a) (CH3)3COCH3CH2CH3 (b) cyclohexyl and methyl iodides
and (c) The presence of two I‘s in the same product indicates a cyclic ether, i.e., tetrahydropyran.

Example 6:
A compound (A), C10H12O2, is soluble in aqueous NaOH, but does not dissolve in aqueous NaHCO3.
When (A) is treated with dimethyl sulphate and aqueous NaOH, compound (B), C11H14O2, is formed
with hot HI (A) gives methyl iodide and with hot and concentrated base, compound (C) C10H12O2 is
obtained. Compound (B) is insoluble in aqueous NaOH but readily decolourises KMnO4 solution.
When treated with hot and concentrated base, compound (B) produces (D), C11H14O2. Ozonolysis of C
produces a compound, which is isomeric with 4hydroxy3methoxybenzaldehyde. Ozonolysis of (D)
gives a compound, which is also obtained by treating 4hydroxy3methoxybenzaldehyde with
dimethyl sulphate. Deduce the structure of A with proper reasoning.
Solution:
Since (A) is soluble in aqueous NaOH, it is phenolic compound. Methylation with (CH3)2SO4/NaOH introduces
CH3 group.
 (B) is C11H14O2
(A) is C10H12O2
A difference of CH2 also indicates phenolic group in (A). (A) is cleaved with hot HI to produce CH3I, indicating
the presence of second oxygen.
That ozonolysis yields 4hydroxy3methoxybenzaldehyde, indicates that (A) is trisubstituted benzene ring.

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C10H12O2(A) C10H11O C9H8

OH OCH3 C6H3 (Trisubstituted aromatic ring)
C10H11O C9H8 C3H5
The residual group, C3H5 corresponds to an unsaturated side chain.
Treatment of (A) with strong and hot base results into isomerisation to C.
HO OH
HO
C6H3CH2CH=CH2 C6H3CH=CHCH3

CH3O CH3O
(A) (C)
C10H12O2 C10H12O2

The same isomerisation occurs when (B) is treated with hot and concentrated base.

CH3O OH
CH3O
C6H3CH2CH=CH2 C6H3CH=CHCH3

CH3O CH3O
(B) (D)
C11H14O2 C11H14O2

Orientation in the compounds can be worked out as follows:

CHO CHO

O3 (CH3)2SO4
(D)
OCH3 OH OCH3

OCH3 OH

CH2CH=CH2

OCH3

OH
CH2CH=CH2 CH2=CHCH3 CHO
(A)
(CH3)2SO4 OH O3
(or)
OH  OCH3  OCH3 OCH3
CH2CH=CH2
OCH3 OCH3 OCH3

(B) (D)
OH

OCH3
(A)

(C) has the same orientation of groups as (D). Hence the only possible isomer of
4hydroxy3methoxybenzaldehyde that can be formed by cleavage of (C) is the one in which the
OH and OCH3 groups are reversed.
CHO

O3
(C) (isomer of 4hydroxy3methoxybenzaldehyde)
OH

OCH3

Thus, A is

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CH2CH=CH2 CH=CHCH3 CHO

OH O3
OH  OH OH

OCH3 OCH3 OCH3

(A) (C)

Example 7:
Compound (A), C9H13O3N shows optical isomerism when 1,2dihydroxybenzene is treated with
chloroethanoyl chloride in the presence of POCl3, compound (B), C8H7O3Cl, is obtained which upon
treatment with methyl amine gives compound (C), C9H11O3N. Reduction of (C) with Pd/H2 yields (A).
Compound (B) when heated with NaOI and subsequent treatment of the product formed with dilute
acid solution yields 3,4dihydroxybenzoic acid. Deduce the structure of (A).
Solution:
O
OH OH OH OH
OH OH OH OCCH2Cl
ClCH2COCl
or or
POCl3

CCH2Cl CH2COCl
O (I) (II) (III)

1,2dihydroxybenzene may undergo ring acylation or ring alkylation or esterification to form compound (B).
Since (B) gives haloform test, the only possibility is (I).
OH OH OH
OH OH +
OH
NaOI H
CHClI2 +

CCH2Cl COONa COOH

O (B) 3,4dihydroxybenzoic acid

OH OH OH
OH OH OH
CH3NH2 H2/Pd

CCH2Cl CCH2NHCH3 * CH(OH)CH2NHCH3

O O (C) (A)

Example 8:
(a) Isomers (G) and (H), C10H12O, are isolated from the oil of bay leaf. They are insoluble in aq. NaOH
+
and decolorize Br2/CCl4 and KMnO4/H . Each is vigorously oxidized to panisic acid,
pMeOC6H4COOH. Ozonolysis of (G) and (H) give the same products. (a) Identify (G) and (H). (b) Give
the structure of a third isomer (I) that is also oxidized to panisic acid and that give the same product
on hydrogenation as does (G) and (H). (d) Suggest a chemical reaction that can distinguish it from (G)
and (H).

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Solution:
(a) Both (G) and (H) have 5° of unsaturation, four owing to a benzene ring and one to a C = C bond as
+
evidenced by positive tests with Br2 and KMnO4/H for unsaturation. They are not phenolic since they are
not acidic. Isolation of pMeOC6H4COOH shows that (G) and (H) are methyl ethers with a para
substituted alkenyl side chain. They do not differ in the position of C=C but rather are cistrans isomers
because they give the same ozonolysis products. Since seven C’s are accounted for by the ring and the C
of OCH3, the alkenyl side chain has three C’s. In order to exhibit stereoisomerism, the side chain is
CH=CHCH3. (G) and (H) are cis and transpMeOC6H4CH=CHCH3 (anethole).
(b) The structural isomer (I) is pMeOC6H4CH2CH=CH2 which also gives anisic acid on oxidation and is
reduced to pMeOC6H4CH2CH2CH3, as are (G) and (H). (d) Reductive ozonolysis of (G) and (H) gives
CH3CHO which gives a positive test with NaOI. (I) is reductively ozonized to H2C = O, which gives a
negative test with NaOI.

Example 9:
(a) Synthesize tetrahydrofuran using the Williamson synthesis. (b) Through which conformation does
the substrate react? (c) What byproduct might one expect in this synthesis? (d) Why is very little of
this byproduct formed?
Solution:
(a) The SN2 reaction to prepare cyclic ethers must be intramolecular. The number of C’s separating X and OH
in the chain is the number in the ring. In this case enough alkoxide ion can be formed by adding NaOH to
the alcohol.

OH O
OH O
Cl Cl + Cl
4Chlorobutanol an alkoxide intermediate Tetrahydrofuran

The alkoxide intermediate may not be completely formed. The incipient anion can begin to displace Cl as it
forms, a one step reaction. (b) As shown in the equation in (a), the substrate must be in the highest
energyeclipsed conformation (c) HOCH2CH2CH2CH2OH. (d) Formation of the diol is a bimolecular
displacement, which is slower than the intramolecular ring closure.

Example 10:
(a) Why are ethers such as Et2O used as solvents for (i) BF3 and (ii) RMgBr? (b) Compare the Lewis
basicities of tetrahydrofuran, diethyl ether and diisopropyl ether and give your reasoning.
Solution:
(a) Because of their unshared e’s, ethers are also Lewis bases capable of reacting with Lewis acids such as
BF3 and RMgBr to form coordinate covalent bonds.
.. ..+ 
(i) Et2O: + BF3  Et2O:BF3

.. R
..
(ii) 2Et2O: + RMgBr  Et2O:Mg:
.. OEt2
Br
2+
Note that two molecules of ether coordinate tetrahedrally with one Mg .
(b) In addition to the amount of electron density on the nucleophilic site, steric affects also influence
basicities. The greater the steric hindrance encountered in the formation of the coordinate bond, the
weaker is the Lewis basicity. In tetrahydrofuran, the R groups (the sides of the ring) are “tied back” leaving
a very exposed O atom free to serve as a basic site. The 2° R groups in diisopropyl ether furnish more
steric hindrance than do the 1° ethyl groups in ethyl ether.
The order of decreasing Lewis basicity is thus tetrahydrofuran > ethyl ether > ipropyl ether.

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9.2 Objective

Example 1:
Which of the following product is formed on acid catalysed hydration of 2phenyl propene?
(a) 1phenyl2propanol (b) 1phenyl1propanol
(c) 1phenyl3propanol (d) 2phenyl2propanol
Solution:
Addition of water to 2phenyl propene follows Markownikoff’s rule.
 (d)

Example 2:
Which of the following is the best reagent to convert cyclohexanol to cyclohexene?
(a) Concentrated H3PO4
(b) Concentrated HCl
(c) Concentrated HBr
(d) Concentrated HCl + anhydrous ZnCl2
Solution:
Cl and Br are better nucleophiles than H2O, so with concentrated HCl and concentrated HBr, the
corresponding chloride and bromide would have been formed. But phosphate is a very poor nucleophile
because of its bulkier size and would be used effectively for causing elimination only.
 (a)

Example 3:
The product of the reaction between

MgBr + (CH3)3COH ?
OH
(a) (b)

CH3 CH3
CCH3 OCCH3
(c) (d)
CH3 CH3
Solution:
Grignard reagent with any compound containing active hydrogen will form a hydrocarbon.
 (a)

Example 4:
H3C H CH3

CH3O NO2 on hydrolysis in presence of aqueous acetone gives

H Cl CH3

H3C H CH3 H3C H CH3

(K): MeO NO2 ; (L): MeO NO2

H OH CH3 HO H CH3

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CH3 H CH3
(M): MeO NO2
H CH3 OH
(a) (K) and (L) (b) (K) only
(c) (K) and (M) (d) (M) only
Solution:
The reaction follows partly SN1 and partly SN2 mechanism in aqueous acetone. In SN1 mechanism, the 2°
carbocation formed due to the loss of Cl undergoes rearrangement forming more stable benzylic carbocation
containing OCH3 group at the pposition. Therefore, products (K) and (L) would be formed.
 (a)

Example 5:
O
Which of these reagents will form npropionic acid from CH3CCH2CH3?
(a) NaOH + I2, H+ (b) Fehling’s solution
+
(c) NaOH + NaI, H (d) Tollen’s reagent
Solution:
O
(i) NaOH
CH3CCH2CH3 + I2 + CHI3 + HOOCCH2CH3
(ii) H
(Iodoform reaction) (npropionic acid)

 (a)

Example 6:
What is the major product of the following reaction?
O

NaBH4
?
CH3OH
CO2H
OH OH

(a) (b)
CH2OH CO2H
O OH

(c) (d)
CH2OH CO2CH3
Solution:
Sodium borohydride is a mild reducing agent. It can reduce only aldehydes and ketones to alcohols but
cannot reduce carboxylic acids.
O OH

NaBH4
CH3OH
CO2H CO2H
 (b)

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Example 7:
Which of the ester shown, after reduction with LiAlH4 and aqueous work up, will yield two molecules
of only a single alcohol?
(a) CH3CH2CO2CHCH3 (b) C6H5CO2C6H5
(c) C6H5CO2CH2C6H5 (d) HCO2C2H5
Solution:
Lithium aluminium hydride reduces an ester (RCOOR’) to a mixture of two alcohols i.e., RCH2OH and ROH.
In the given problem both the alcohols are same. Therefore, the ester must be of the type RCOOCH2R.
O
LiAlH4
C6H5COCH2C6H5 2C6H5CH2OH

 (c)

Example 8:
Heating a particular ether with HBr yielded a single organic product. Which of the following
conclusions may be reached?
(a) The reactant was a methyl ether.
(b) The reactant was a symmetrical ether.
(c) The reactant was a cyclic ether.
(d) Both (b) and (c) may be correct.
Solution:
An unknown ether reacts with excess of HBr to yield a single product. This implies that the ether must be
either symmetrical or cyclic.
(i) ROR + HBr  RBr + ROH
ROH + HBr  RBr + H2O
ROR + 2HBr  2RBr + H2O
O Br Br
(ii) + 2HBr + H 2O  (d)

Example 9:
What reactant gives the product shown on heating with anhydrous AlCl3?
O
H3C C OH

O O
(a) H3C OC (b) H3C CO

O
(c) H3C COH (d) OH

O C CH3
O
Solution:
Phenyl esters of aliphatic or aromatic carboxylic acids when heated with anhydrous AlCl3 undergo Fries
rearrangement. The given product can be obtained from

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OCO CH3 OH
AlCl3


CO CH3

 (b)

Example 10:
What are the products of the following reaction?

1. Excess HBr
OCH2CH2OH ? + ?
2. Heat
(a) pBrC6H4OCH2CH2Br (b) PhBr + BrCH2CH2OH
(c) PhBr + BrCH2CH2Br (d) PhOH + BrCH2CH2Br
Solution:
OCH2CH2OH OH
HBr
 + BrCH2CH2OH

HBr
BrCH2CH2OH  BrCH2CH2Br + H2O
 (d)

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9 Assignments (Objective Problems)

HOME ASSIGNMENT-I

1. Predict the major product in the reaction given below.

CH3
Ag+
CH3–C–CH2Cl H2O
CH3

CH3 CH3
(A) CH3–C–CH2OH (B) CH3–C–CH2CH3
CH3 OH

CH3
(C) HO–CH2–CH–CH2CH3 (D) H3C CH2OH

2. Which of the following compound on reaction with LiAlH4 (in excess) in dry ether and subsequent
hydrolysis will give isobutyl alcohol only?

CH3 CH3 CH3 CH3

(A) CH3CHCH2COCH2CH–CH3 (B) CH3CHCH2OCCHCH3
O O

CH3 CH3 CH3 CH3

(C) CH3CHOCCH2–CH–CH3 (D) CH3CHOCH2O–CH–CH3
O

3. Consider the following sequence of reactions:

C2H5CCH 
CH MgBr
(A) 
1. HCHO
2. H O
3
(B) 3
+

The product (B) is

(A) CH3CH2OH (B) C2H5C=CHCH2OH

CH3

(C) C2H5CC–CH–CH3 (D) C2H5CC–CH2OH

OH

4. The product formed in the reaction

B H 2 6
PhCH=CH2 H O /OH 2 is 2
–

(A) PhCH(OH)CH3 (B) PhCH2CH2OH

(C) PhCOCH3 (D) PhCH2CHO

5. Consider the following sequence of reactions:

Mg
PhBr Et2O, heat (A)
NH4Cl
CH3CH–CH2 + (A) (B) H2O (C)
O

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The major product (C) is

(A) Ph–CH–CH2OH (B) PhCH2CH(OH)CH3

CH3

(C) PhCH2COCH3 (D) none of these

CH3
6. The compound CH3–C–CH2CH2CH2OH may be prepared by the reaction of
OH

(A) CH3COCH2CH2OH with CH3MgI / H+

(B) CH3COOCH2CH2CH2CH2OH with CH3MgI / H+

(C) O with CH3MgI (1 mol) / H+

(D) O with CH3MgI (excess) / H+

NaNO2
7. The reaction CH2NH2 dil. H2SO4 mainly gives

OH
(A) CH2OH (B)
CH3

OH
(C) (D) CH2

8. An alkene (A) on reaction with BD3–THF followed by H2O2 / OH– gives Me3C–CD2CH2OH. (A) on
reaction with H2O / D2SO4 gives:
(A) Me2C(OH)CD(Me)CH2D (B) Me2C(OD)CDMeCH2D
(C) Me3C–CD(OH)CH2D (D) Me2CD–CD(Me)(OH)CH2D

9. Acid catalysed hydration of alkenes except ethene leads to the formation of

(A) Primary alcohol.
(B) Secondary or tertiary alcohol.
(C) Mixture of primary and secondary alcohols.
(D) Mixture of secondary and tertiary alcohols.

10. The end product in the following sequence of reaction is

HCCH   (A)  3

1% HgSO4 CH MgX
20% H2SO4 H2 O

(A) Acetic acid (B) Isopropyl alcohol

(C) Acetone (D) Ethanol

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CH3 CH3
X
11. CH3CCH=CH2 CH3C CHCH3
CH3 CH3 OH

‘X’ can be:

(A) BH3/THF, H2O2/OH (B) H3O+
(C) Hg(CH3COO)2/NaBH4, NaOH (D) All of these

12. The acid derivative which does not give alcohol on reduction
(A) RCX (B) RCNH2
O O

O
RC
(C) RCOR (D) O
RC
O
O

MgBr CH2CH2OH
13. forms on the reaction with

(A) CH3CHO (B) CH2CH2

O

(C) CH3CH2CHO (D)

O

O
(i) CH3MgI excess
14. +
product is
(ii) H
OCH3

OH O OH
(A) (B) (C) (D)
OH
OC2H5 O

O
15. Cl H2/Ni
(A)

LiAlH4

(B)

The product(s) is/are

(A) (A) is an alcohol ; (B) is an aldehyde (B) (A) is an aldehyde ; (B) is an alcohol
(C) (A) and (B) both are alcohols (D) (A) and (B) both are aldehydes

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
(i) H
16. CH2=CH2 (A)
(ii) D2O

The compound (A) is

(A) CH3CH2OH (B) CH3CH2OD

(C) DCH2CH2OH (D) DCH2CH2OD

17. Rate of hydration of

will be in order:
(A) I < II < III (B) I < III < II (C) II < I < III (D) III < II < I

18. Action of HNO2 on CH3NH2 gives following as major product

(A) CH3OH (B) CH3–O–CH3 (C) CH3–O–N=O (D) CH3–NO2

19.

A and B are:

20.

Select schemes A, B, C out of

I acid catalysed hydration II HBO III oxymercuration-demercuration
(A) I in all cases (B) I, II, III (C) II, III, I (D) III, I, II

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21.

E is

(A) (B) (C) (D)

22.

OH
CH2OH CHCH2CH3
23. is changed into

(A) (i) Cu, 300°C (ii) CH3CH2MgCl, H3O+

(B) (i) CrO3, H+ (ii) CH3CH2MgCl, H3O+

(C) (i) KMnO4 (ii) CH3CH2MgCl, H3O+

(D) (i) Na2Cr2O7 + H2SO4 (ii) CH3CH2MgCl, H3O+

24. In the given reaction:

+
CH 3MgBr HOH/H
CH3 — CH — CH2 [X]
O
[X] will be
(A) 1°Alcohol (B) 2°Alcohol
(C) 3°Alcohol (D) Open chain ether

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25 Which of the following is a primary alcohol?

(A) Butan –2-ol (B) Butan –1-ol

(C) Propan -2-ol (D) 2,2-Dimethylhexane-4-ol

HOME ASSIGNMENT-II

1. Which of the following alcohol is the weakest acid in water?

(A) Ethyl alcohol (B) Phenol
(C) Methyl alcohol (D) t-Butyl alcohol

2. The most suitable reagent for converting a primary alcohol into an aldehyde is
(A) K2Cr2O7 and H2SO4 (B) KMnO4 and NaOH

+ –
(C) NHClCrO3 in CH2Cl2 (D) conc. HNO3

3. Which of the following compound, on reaction with excess of RMgX, gives 3 moles of alkane (RH)?
(A) HCC–CH–COOH (B) CH3–CC–CH–COOH
OH OH
(C) HCC–CH–COOH (D) CH2=CH–CH–COOH
OCH3 OH

4. The compound that reacts fastest with Lucas reagent at room temperature is
(A) 1–butanol (B) 2–butanol
(C) 2–methyl–1–propanol (D) benzyl alcohol

OH OH
5. The treatment of CCH3 with concentrated H2SO4 gives
Ph

O O
CH3
C
(A) Ph (B) Ph
CH3

O
C
(C) CH3 (D) None of these
Ph

6. Among the given compounds, which is easily dehydrated?

(A) OH (B) OH

(C) OH (D) OH

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7. Most easily dehydration is possible for

(A) C6H5CH2OH (B) C6H5CH2CH2OH

OH
(C) C6H5CH2CHC6H5 (D) CH2=CHOH

8. An organic compound ‘A’ (liquid) containing C, H & O has a pleasant odour with a boiling point of
70°C. On boiling ‘A’ with concentration H2SO4 a colourless gas is produced, which decolorise
bromine water and alkaline KMnO4. One mole of this gas also takes one mole of H2. The organic
liquid ‘A’ is
(A) C2H5Cl (B) C2H5CHO (C) C2H6 (D) C2H5OH

9. Ethylene glycol reacts with PI3 to give:

(A) CH3ICH2I (B) CH2=CHI (C) CHI=CHI (D) CH2=CH2

H3C CH3 H

H , heat
10. CH3CCHCOH Mixture of Alkenes
CH3 CH3

Major alkene in this reaction is

H CH3 CH3
(A) C=C (B) (CH3)3CC=C
CH3 C(CH3)3 CH3
H

CH3
CH3 CH3
(C) C=C (D) CH3C=CCH(CH3)2
H C(CH3)3
CH3


11. CH2OH H /
(A)

The compound (A) is

OH
(A) CH3 (B) (C) (D)

Keq
12. CH3O + C2H5OH CH3OH + C2H5O
The equilibrium constant, Keq for this reaction would be
(A) Keq > 1 (B) Keq = 1 (C) Keq < 1 (D) none of these

SOCl2
13. CH3CHOH (A)
C2H5
The compound (A) has/is
(A) retention of configuration (B) inversion of configuration
(C) racemic mixture (D) all of these

14. Ethanol on reaction with acetic anhydride gives

(A) Acetic ester (B) Formic ester
(C) Ethanoic acid (D) Acetic ester and Ethanoic acid both

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15. Most acidic alcohol out of following compounds is

(A) (CH3)3C–OH (B) CH3CH2OH (C) CH3OH (D) PhOH

16. A compound ‘X’ with molecular formula C3H8O can be oxidised to a compound ‘Y’ with the
molecular formula C3H6O2, ‘X’ is most likely to be
(A) Primary alcohol (B) Secondary alcohol (C) Aldehyde (D) Ketone

17.

(A) , (B) ,

(C) , (D) no formation of A and B

18.

Hence A 
conc . H 2 SO4
B, B is

CH 2  O  CH 2
| |
(A) (B) (C) OH OH (D) None

19. Dehydration of the alcohols

will be in order
(A) IV > III > II > I (B) I > II > III > IV (C) IV > II > III > I (D) II > IV > I > III

20.

(A) (B) (C) (D)

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21.

(A) OH at C2 is more basic than that of at C5 (B) OH at C2 is more acidic than at C5.
(C) both have same basicity (D) both have same acidic strength

22.

(A) (B) (C) (D)

23.

CH 2  CHCCH 2CH 2OH CH 2  CHCHCH2 CHO

|| |
(A) O (B) OH

O
||
CH 2  CHCCH 2 CHO CH 2  CHCCH 2 COH
|| ||
(C)
O (D)
O

24. Which can be cleaved by HIO4?

O O OH O
|| || | ||
CH 3CH 2CCH 2CCH 3 CH 3CHCCH 2CH 3
(A) (B)

O O
|| ||
CH 3CCH 2CHCH 2CCH 3
|
(C) (D)
OH

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25. Methanol can be distinguished from ethanol by

(A) Heating with I2 and alkali (B) Treating with schiff’s reagent
(C) Treating with CrO3 solution in dil. H2SO4 (D) Treating with Lucas reagent

HOME ASSIGNMENT-III

1. Di–t–butyl ether is prepared best by the reaction,

(B) (CH3)3C–OH  
 
H SO
(A) (CH3)3C–Br + (CH3)3COK  2 4

180C

(C) (CH3 )3 C –OH 

Al 2 O3
(D) (CH3 )2 C  CH 2    
conc.

( CH3 ) 3 COH

vapour 350C H 2 SO 4

2. 2–Butene is allowed to react with CF3CO3H. The product formed (A) is heated with LiAlH4 in dry
ether and finally acidified to give (B).
CH 3 CH  CHCH 3    ( A ) 
CF3CO 3H

1. LiAlH4

 (B )
2. H 3 O

The final product (B) is

(A) CH3CH–CHCH3 (B) CH3CH–CHCH3

O OH OH

(C) CH3CH2CH(OH)CH3 (D) CH3CH2CH2CH3

3. In the given reaction,

H3C
+ HCl (1 equivalent)
H O

the major product formed is

Cl OH Cl
OH Cl Cl
(A) (B) (C) (D)

4. Consider the following reaction,

14
CH2–CH–CH2Cl + CH3O (A)
O

The product (A) is

14 14
(A) CH2–CH–CH2OCH3 (B) CH3OCH2–CH–CH2
O O

14 14
(C) HO–CH2–CH–CH2OCH3 (D) CH3OCH2–CH–CH2OCH3
OCH3 OH

5. In the reaction,
CH3  CH CH2  ( A ) 
NBS
CCl
 (B)
C2H5ONa
4

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the product (B) is

CH3
(A) CH3–CH–OC2H5 (B) CH2=CHCH2OC2H5
(C) CH3CH2CH2OC2H5 (D) C2H5CH2OCH=CH2

6. One mole of t–butyl methyl ether on being heated with 1 mole of concentrated hydroiodic acid gives
(A) CH3OH(1 mole) and (CH3)3CI (1 mole)
(B) CH3I (1 mole) and (CH3)3CCOH (1 mole)
(C) CH3I (1 mole) and (CH3)3CI (1 mole)
(D) CH3OH (1 mole) and (CH3)3COH (1 mole)

7. Diethyl ether on being exposed to air for a long time forms some amount of diethyl ether
hydroperoxide. The presence of this hydroperoxide compound in diethyl ether can be detected by
adding ferrous sulphate into it and then adding
(A) KCNS (B) SnCl2 (C) HgCl2 (D) KI

8. Which of the following reaction will not result in the formation of anisole?
NaOH
(A) OH + (CH3)2SO4 (B) ONa + CH3I

(C) OH + CH2N2 (D) OH + CH3MgI
9. The major product (A) of the reaction,
OH H2SO4
H2O
(A)
is

(A) (B) O
O
O
(C) (D)

10. Consider the following transformation,

conc. HI
CH3CH=CH–O–CH2CH3 heat
(A) CH3CH=CHI and CH3CH2I (B) CH3CH=CHI and CH3CH2OH
(C) CH3CH2CHO and CH3CH2I (D) CH3CH2CH–O–CH2CH3
I

11. The product formed in the given reaction is

CH3
CH3OH
CH3 C CH2 Product
CH3ONa
O
CH3

(A) (CH3)2CCH2OCH3 (B) CH3 C CH2OH

OH OCH3
(C) (CH3)2C=CHOCH3 (D) None of these

12. Glycol on treatment with PI3 mainly gives–

(A) Ethylene (B) Ethylene iodide (C) Ethyl iodide (D) Ethane

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13. Acrolein is formed when glycerol is heated with –

(A) Acidified KMnO4 (B) Br2 water (C) KHSO4 (D) HNO3

14. Glycerol on treatment with oxalic acid at 110°C forms–

(A) Allyl alcohol (B) Formic acid (C) CO2 and CO (D) Glyceric acid

15. If the starting material is 1–methyl–1,2–epoxy cyclopentane, of absolute configuration, decide which
one compound correctly represent the product of its reaction with sodium methoxide in methanol.

(A) (B) (C) (D)

16. Consider the reaction of HI with the following:

I II

Which forms di-iodide on reaction with HI (excess)?

(A) I and II both (B) II only (C) I only (D) none

17. The reaction of CH3OC2H5 with HI gives

(A) CH3I (B) C2H5OH `(C) CH3I + C2H5OH (D) C2H5I + CH3OH

K H SO L iA lH
18. Glycerol   4  A   4  B
A and B are:
(A) Acrolein, allyl alcohol (B) Glyceryl sulphate, acrylic acid
(C) Allyl alcohol, acrolein (D) Only acrolein (B is not formed)

19. An ether is heated with phosphorous penta sulphide to give

(A) Alkanthiol (B) Dialkyl sulphide (C) Hydrogen sulphide (D) Thioester

20.
OH CH 2OH CH 3
CH 2OH

CH 3 CH 3 CH 3
(A) OH , (B) OH (C) CH 3 (D) OH

21.

A and B are

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CH 3 CH 3 CH 3 CH 3
| | | |
CH 3  C  CH 2 CH 3  C  CH 2 CH 3  C — CH 2 CH 3  C  CH 2
| | | | | | | |
OH OH OH OCH3 OH18OH OH OCH3
(A) 18 , (B) ,
CH 3 CH 3 CH 3
CH 3
| | | |
CH 3  C  CH 2 CH 3  C — CH 2 CH 3  C — CH 2 CH 3  C — CH 2
| | | | | | | |
18 18
OH OH 18OH OH 18
OH OH OCH 3 OH
(C) 18 , (D) ,

22.

HOME ASSIGNMENT-IV

1. Picric acid and benzoic acid can be distinguished by

(A) Aqueous NaHCO3 (B) Aqueous NaOH
(C) Aqueous FeCl3 (D) Aqueous Na2CO3

2. Intramolecular rearrangement of phenyl esters to give o and pderivatives in presence of

anhydrous AlCl3 is known as:
(A) FriedelCraft’s reaction (B) Fries rearrangement
(C) Esterification (D) Coupling

3. Phenol is heated with phthalic anhydride in presence of conc. H2SO4. The product gives pink colour
with alkali. The product is
(A) Phenolphthalein (B) Bakelite (C) Salicylic acid (D) Fluorescein

4. Characteristic violet colouration with neutral FeCl3 solution is given by

OH OH
(A) (B) CH3CH2CHCH2CH3

OH

(C) (D) CH3CH2CH2OH

CH3

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5. A crystalline solid C7H8O reacts with sodium to liberate hydrogen. It is insoluble in water but soluble
in dilute aqueous NaOH. Upon treatment with Br2/CCl4, only one monobrominated compound with
the formula C7H7OBr is formed. The original compound has the structure
CH2OH CH3 CH3 CH3
OH
(A) (B) (C) (D)
OH
OH

6. An organic compound with molecular formula, C7H8O dissolves in NaOH and gives a characteristic
colour with FeCl3. On treatment with bromine, it gives tribromoderivative, C7H5OBr3. The compound
is
(A) C6H5CH2OH (B) ocresol (C) mcresol (D) pcresol

7. Which of the following will not be soluble in sodium bicarbonate solution?

OH
O2N NO2 COOH
(A) (B)

OH SO3H

(C) (D)

8. Phenol on exposure to air produces

(A) pbenzoquinone (B) obenzoquinone
(C) o and pbenzoquinone (D) phenoquinone

9. When phenol is treated with CHCl3 and NaOH followed by acidification, salicyldehyde is formed.
The electrophile involved in the process is
(A) Carbocation (B) Carbanion
(C) Carbene (D) None of these

10. Which of the following is true about phenol?

(A) It is acidic in nature and gives effervescence with sodium bicarbonate.
(B) It is basic in nature owing to the presence of OH group.
(C) It gives violet colour with neutral FeCl3 owing to the formation of a soluble complex in which iron
is said to be in hexavalent state.
(D) Phenol as well as ethanol can be reduced to corresponding alkanes by heating with
Zn dust.

11. Which of the following statement regarding phenol is not correct?

(A) oNitrophenol has a much lower boiling point as compared to pnitrophenol.
(B) oNitrophenol has much lower solubility in water as compared to pnitrophenol.
(C) oNitrophenol is stronger acid than pnitrophenol.
(D) oNitrophenol can be steam distilled while pnitrophenol cannot be.

12. (X) is a higher phenol and (Y) is an aromatic carboxylic acid. Separation of a mixture of (X) and (Y)
can be carried out easily by using a solution of
(A) NaOH (B) Na2CO3 (C) Lime water (D) NaHCO3

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13. The most steam volatile compound is

OH OH
OH
OH
(A) (B) (C) (D)
O2N NO2
NO2 O2N NO2
NO2 NO2

14. When phenol is treated with PCl5, the yield of chlorobenzene is generally poor because of the
formation of
(A) Benzoyl chloride (B) p–chorophenol (C) o–chlorophenol (D) Triphenyl phosphate

15. Phenol with Hinsberg’s reagent gives

(A) Sulphone (B) Sulphanilic acid
(C) Sulphonic ester (D) Sulphonal

16.

In this reaction, the end product C is:

(A) salicylaldehyde (B) salicylic acid (C) phenyl acetate (D) aspirin

17.

18.

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19.

20.

21. m-Aminophenol on treatment with NaOH and CO2 gives which of the following as major product?

(A) (B) (C) (D)

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22. Phenol and ethanol are distinguished by the reaction with

(A) Red litmus (B) NaHCO3 (C) FeCl3 (D) NaOH

23. Phenol Zinc

(A) Conc.
 (B) Sn/HCl
HNO 3
–
(C)
distillati on Conc. H 2SO 4 OH
at 60 C
In the above reaction, compounds (A), (B) and (C) are:
(A) benzene, nitrobenzene and aniline
(B) benzene, dinitrobenzene and m-nitroaniline
(C) toluene, m-nitrobenzene and m-toluidine
(D) benzene, nitrobenzene and hydrazobenzene

24. Which one of the following compounds gives aspirin on reaction with acetic anhydride in presence of
H2SO4?
OH CHO
COOH COOH
(A) (B)

CHO OH
OH
(C) (D)

NH2

25. When phenol is treated with excess of bromine water, it gives

(A) m-bromo phenol (B) o- & p-bromophenol
(C) 2, 4-dibromophenol (D) 2, 4, 6-tribromophenol

10. Get Equipped for IIT - JEE

10.3 Only Single Choice Correct
1. A compound with molecular formula C4H10O3 is converted by the action of acetyl chloride to a
compound of molecular mass 190. The original compound (C4H10O3) has
(A) one OH group (B) two OH group (C) three OH group (D) four OH group

2. The treatment of CH3OH with excess of CH3MgI releases 1.04 ml of a gas at STP. The mass of
CH3OH added is
(A) 1.485 mg (B) 2.98 mg (C) 3.71 mg (D) 4.47 mg

3. Buff coloured precipitate is obtained when aqueous FeCl3 solution is treated with
COOH NO2 CONH2
CO
(A) (B) (C) O (D)
CO
OH

4. Which of the following compounds on reaction with CH3MgBr followed by hydrolysis will give a
tertiary alcohol?
(A) C2H5CHO (B) C2H5COCH3 (C) C2H5COOH (D) CH3CH CHCH3
O

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5. The end product (C) in the following sequence of reactions is

CH 3MgX
HCCH  4  (A)   (B)   4  (C)
1% HgSO 2 2 7 2 K Cr O |H SO
20% H 2SO 4 
H |H 2 O
(A) Acetic acid (B) Isopropyl alcohol (C)Acetone (D) Ethanol

6. For the reaction, C 2 H 5 OH  HX ZnX

 2  C 2 H 5 X . The decreasing order of reactivity of halogen
acids is :
(A) HI > HCl > HBr (B) HI > HBr > HCl
(C) HCl > HBr > HI (D) HBr > HI > HCl

7. CH 3OH 
PI3
(A) 
KCN
(B) 
Hydrolysis
(C) , The compound (C) is:
(A) CH3OH (B) HCOOH (C) CH3CHO (D) CH3COOH

8. Which of the following compounds is stable?

(A) CH3CH(OH)2 (B) (CH3)2CH(OH)2 (C) CCl3CH(OH)2 (D) none of these

9. (CH3)3CMgCl on reaction with D2O molecule produces

(A) (CH3)3CD (B) (CH3)3COD (C) (CD3)3CD (D) (CD3)3COD

10. The strength of an acid decreases in the order:

(A) CH3CH2CH2OH > CH3CH2OH > CH3OH > H2O
(B) H2O > CH3OH > CH3CH2OH > CH3CH2CH2OH
(C) CH3OH > CH3CH2OH > CH3CH2CH2OH > H2O
(D) CH3CH2CH2OH > CH3CH2OH > CH3OH > H2O

11. Identify the product (P) in the following reaction


H2O\H (P)
O O

(A) + OH (B) + OH
O OH O CHO

(C) HO–(CH2)4–CHO + OH (D) All of these

H3 C CH2
LiAlH4
(A). ‘A’ is
12.
H3 C O
(A) CH3CHCH2OH (B) CH3CH2CH2CH2OH
CH3

CH3
(C) CH3C–OH (D) No reaction
CH3

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13. The final product of the following reaction sequence is

Ph CH3
| |
CH 3  C  C  CH 3 
HNO2
 ( N2 )
  rearrangement
    ?
| | cold
OH NH2

O O
|| ||
(A) CH 3  C  C(CH 3 ) 2 Ph (B) Ph  C  C(CH 3 ) 3

H O
| ||
(C) CH 3  C  C  CH 2  Ph (D) none of these
|
CH3

14. The decreasing order of ease of dehydration in the following compounds is

H D OH
OH H OH H
OH
(I) (II) (III) (IV)
(A) I > III > IV > II (B) II > I > III > IV
(C) IV > I > III > II (D) III > I > II > IV

15. Which of the following compound is most reactive with HCl in presence of anhydrous ZnCl2 (Lucas
reagent)?
Cl

(A) CH2OH (B) CH2OCH3 (C) CH2OH (D) CH2CH3

16. The major product formed in the following reaction is

••
HCl
CH 3  C  CH  O  CH 3  CH 3OH 

| ••
CH3
OCH3
| OCH3
(A) CH 3  C  CH 2  OCH 3 (B) CH 3  CH  CH
| | OCH3
CH3 CH 3
OCH3
| OCH3
(C) CH 3  CH  CH (D) CH 3  CH  CH O
OCH3 |
CH 3

17. Which of the following ether is not cleaved by HI even at 525K?

(A)C6H5–O–CH3 (B) C6H5–O–C6H5
(C)C6H5–O–C3H7 (D)
O

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18. More stable carbocation is formed during the heating of which one of the following compound with
conc. H2SO4?
(A)(CH3)3COH (B) C6H5CH2OH
(C)(CH3)2CHOH (D) CH3CH(OH)CH2CH3

19. H-Br reacts faster with

(A)propan-1-ol (B) 2-methylpropan-2-ol
(C)propan-2-ol (D) 2-methyl propan-1-ol

20. Which one of the following dyes has a nitro group?

(A) Indigo (B) Phenolphthalein (C) Martius yellow (D) Malachite

21. Which of the following alcohols have highest solubility in water at 25°C?
(A) CH3OH (B) OH
(C) t-butyl alcohol (D) Isobutyl alcohol

22. Identify (A) in the following reaction

CH3ONa
CH3 + CH3OH (A)
O
CH3
(A) CH O CH3 (B)
3
O O OCH3
CH3
(C) CH3O CH3 (D)
HO OH OCH3

23. The product formed in the given reaction is

CH3
CH3OH
CH3 C CH2 CH3ONa
Product
O

CH3

(A) (CH3)2CCH2OCH3 (B) CH3 C CH2OH

OH OCH3

(C) (CH3)2C=CHOCH3 (D) None of these

CH3
24. The product in the reaction + HBr  is

CH3 CH3 CH3 CH3

OH Br Br
(A) (B) (C) (D)
Br OH

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25. Read the following flow chart carefully

CH3

Ph – C H 2 C H O H
(Potassium ) K (I) 1-P henyl-2-pro panol (III) TsC l
S .R . = + 33.02º
CH3 CH3

Ph – C H 2 C H O K + gas Ph – C H 2 – C H O Ts
EtO Ts (II) (IV ) C 2 H 5 O K
CH3 CH3

Ph – C H 2 – C H – O C 2 H 5 P h – C H 2 – C H – O C 2H 5
ethyl-1-phenyl-2-p ropylether ethyl 1-phenyl-2-propyleth er

(A) Both the ethers obtained by the two routes have opposite but equal optical rotation.
(B) One of the ether is obtained as a recemic mixture.
(C) Step (II) and (III) both are SN2 reactions and hence both show inversion of configuration.
(D) Step (II) shows inversion but step (III) shows retention of configuration.

26. Identify the final product in the given reaction

 (1) (2) H  H2 PBr3

1-hexyne + n-BuLi C8H14O Lindlars
C8H16O C8H15Br
catalyst

n-C4H9 CH2 – CH3 n-C4H9 CH2CH2Br

(A) C=C (B) C=C
Br H H H

n-C4H9 H n-C4H9 Br
(C) C=C (D) C=C
H CH2CH2Br H CH2CH3

H+
27. ? Identify the product
OH

(A) (B)
O CH3

(C) C2H5 (D) None of these

O

O H+
28. H2O
‘P’ (Major). Identify the product ‘P’.

O OH O O
OH OH OH
(A) (B) (C) (D)

OH

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OH
CH3
‘A’ Br2 Br2
29. ’B’ ‘A’ and ‘B’ are
H2O CS2

OH OH
CH3 Br CH3
(A)Both are (B) Both are

Br Br
OH OH OH OH
Br CH3 CH3 CH3 Br CH3
(C) and (D) and

Br Br Br Br

( i ) NaOH H / H O Al2O3
30. Phenol  
o
(A)  
2
 (B)  (C)
( ii ) CO 2 / 140 C CH3COOH

In this reaction, the end product (C) is

(A)salicylaldehyde (B) salicylic acid
(C)phenyl acetate (D) aspirin

31. The product of the following reaction is

H H
H+
C=C=C ?
H3 C C(CH3)2CH2OH
CH3 H CH3
(A) H (B)
H3C O CH3
H3 C O CH3

CH3
H CH3
(C) H CH3 (D)
H3C O CH3
H3 C O

32. The reagents used in the following conversion are

H2C=CH2  O O

OH
(A)O3, Zn, H2O, OH OH (B) Br2/CCl4, OH

  
(C) MnO 4 / OH , H ,  (H 2O) (D) HBr, RONa, OH OH

33. An organic compound with molecular formula, C7H8O dissolves in NaOH and gives a characteristic
colour with FeCl3. On treatment with bromine, it gives a tribromoderivative, C7H5OBr3.
The compound is
(A) benzyl alcohol (B) omethyl phenol
(C) mmethyl phenol (D) pmethyl phenol
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34. HBr reacts with CH2=CHOCH3 under anhydrous conditions at room temperature to give
(A)CH3CHO and CH3Br (B) BrCH2CHO and CH3OH
(C)BrCH2CH2OCH3 (D) H3CCHBrOCH3

Cl

35. on treatment with aqueous KOH give

CH3 CH3

Cl CH3 OH
OH CH3
(A) (B) (C) (D)
CH3 CH3
CH3 CH3 CH3 OH CH3 OH CH3

O
OH O OH O OH
36.
OH OH O OH
O O
(I) (II) (III)

Ease of dehydration among these compounds will be in the order as:

(A)(I) > (II) > (III) (B) (III) > (II) > (I)
(C)(I) > (III) > (II) (D) (II) > (III) > (I)

37. Propan-2-ol on reacting with Cl2 produces

(A) Trichloroethanol (B) Trichloroacetone
(C) Acetone (D) None

38. Diethyl ether absorbs oxygen to form

(A) Red coloured sweet smelling compound
(B) CH3CO2H (C) Ether suboxide
(D) Ether peroxide

39. Ethyl alcohol can be industrially prepared from ethylene by

(A) MnO4– oxidation (B) Catalytic reduction
(C) Absorbing in H2SO4 followed by hydrolysis
(D) Fermentation

40. The correct decreasing order of acidic strength is

(A) C6H5OH  C6H5CH2OH  C6H5COOH  C6H5SO3H
(B) C6H5CH2OH  C6H5OH  C6H5SO3H  C6H5COOH
(C) C6H5COOH  C6H5CH2OH  C6H5OH  C6H5SO3H
(D) C6H5SO3H C6H5COOH  C6H5OH  C6H5CH2OH

10.4 One or MORE than one Choice Correct

41. When phenol is treated with chloroform and sodium hydroxide, followed by acidification,
salicylaldehyde is obtained. Which of the following species is/are involved in the above mention
reaction as intermediate(s)?

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CCl3 O O
H
(A)CCl2 (B) O (C) 
(D) CHCl2
CCl2

42. Salicylic acid is prepared from phenol by

(A)ReimerTiemann reaction (B) Kolbe’s electrolytic reaction
(C)Kolbe’s reaction. (D) None of the above

43. Which of the following reactions will give good yield of ether?

OH OC2H5
(i) Na
(A) (ii) C 2H5Br

(i) Na
(B) (CH3)3C—OH (ii) C6H5Br
C6H5—O—C(CH3)3
(i) Na
(C)(CH3)3C—OH (ii) CH3CH 2CH 2Br
(CH3)3C—O—CH2CH2CH3
(i) Na
(D) CH3CH2CH2OH (ii) (CH3)3CBr
(CH3)3C—O—CH2CH2CH3

44. Lucas test of alcohols involves following reaction:

anhydrous
R — OH + HCl ZnCl 2
RCl + H2O
conc. white
turbidity

Select the correct statement(s) for the Lucas test.

(A)ROH behaves as a base.
(B) Lesser is the acidic character of alcohol, greater is its reactivity towards Lucas reagent.
(C) Reactivity of 1°, 2°, 3° alcohol, lies in the following sequence (for Lucas reaction) 3°>2°>1°.
(D) CH3OH gives Lucas test most quickly.

45. Which among the following statement(s) about ethers is/are correct?

(A) Peroxide is obtained in presence of air.

(B) Ethers are weakly acidic.
(C) Ethers form oxonium salt.
(D)Ethers form stable complexes with Lewis acids.

46. Identify the products (A) and (B) formed in the following reaction
OH conc.H2SO4
(A) + (B)

(A) (B) (C) (D)

47. Select wrong statements:

(A) Phenol reacts with Na2CO3 and liberates CO2 gas.
(B) Phenols turn blue litmus to red.
(C) Reactivity of methanol with sodium metal is more than that of isopropyl alcohol.
(D) Methanol gives iodoform test.

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48. Which of the following will result in the formation of an ether:

(A) (CH3)3CONa + CH3CH2Br  (B) (CH3)3CBr + C2H5ONa 
(C)C6H5ONa + CH3Br  (D) C6H5Br + CH3ONa 

49. Which of the following products are formed in the reaction or after hydrolysis?
mcpba
CH = CH2 ? (mcpba = metachloro perbenzoic acid)

O
O
(A) CH – CH2 (B) CH = CH2

(C) CH = CH2 (D) CH = CH2

O HO OH

50. Which of the following on reduction with LiAlH4 will give ethyl alcohol?
(A)(CH3CO)2O (B) CH3COCl
(C)CH3CONH2 (D) CH3COOC2H5

51. In the reaction sequence, CaC2 

H 2O
 A 
dil . H 2 SO4
Hg 2
 B 
H2
Ni
 C , true about the product C is
(A) give yellow ppt. with NaOI
(B) its final oxidation product is carbonyl compound
(C) its final oxidation product is CO2 and H2O
(D) its final oxidation product is CH3COOH

52. HBO, oxymercuration-demercuration and acid catalysed hydration will not give same product in

(A) (B) (C) (D)

10.5 Comprehension Type

PASSAGE- 1

53. Compound 'B' is?

(A) (B) (C) (D)

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54. Organic compound A does not undergo de carboxylation reaction because?

(A) Intermediate does not follow Saytzeff's rule
(B) Intermediate does not follow Hofmann's rule
(C) Intermediate does not follow Bredt's rule
(D) Intermediate does not follow MarkwoniKoffs rule

55. Total No. of stereoisomers of B are?

(A) 2 (B) 4 (C) 3 (D) 6

PASSAGE -2

Two optically active isomeric alcohols (X) and (Y) of molecular formula C9H12O on oxidation by acidified
KMnO4 gives benzoic acid. (X) gives positive iodoform test but (Y) does not. (X) loses optical activity on
oxidation with CrO3/H+ but (Y) does not.

Based on the above passage; answer the following questions:

56. Which one of the following is the correct structure of (X)?

H
CH2–CH–CH3
(A) C–CH2–CH3 (B) OH
OH
O OH
CH2–C–CH3 CH–CH3
(C) (D)
CH3

57. Which one of the following is the correct structure of (Y)?

CH2CH2OH CH3
(A) (B) C–CH3
CH3 OH
CH3 OH
CH–CH2–OH CH–CH2–CH3
(C) (D)

58. When the compounds (X) and (Y) are separately reacted with conc.H2SO4 at 180oC, which of the
following observation(s) is/are correct?

(A)The dehydrated product of (X) shows geometrical isomerism.

(B)The dehydrated product of (Y) shows geometrical isomerism.
(C) Both (A) and (B) are correct.
(D) Both (A) and (B) are incorrect.

PASSAGE -3
A reaction characteristic of vicinal diols is their oxidative cleavage on treatment with periodic acid
(HIO4). The carbon-carbon bond of the vicinal diol unit is broken and two carbonyl groups are
formed. Periodic acid is reduced to iodic acid (HIO3).
R R'
R R'
R — C — C — R '  HIO 4  C  O  C  O  HIO 3  H 2 O
R R'
OH OH
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Cyclic diols react to give dicarbonyl compounds. The reactions are faster when the hydroxyl groups
are cis than when they are trans but both stereoisomers are oxidized by periodic acid. Periodic acid
cleavage of vicinal diols is often used for analytic purposes as an aid in structural determination. By
identifying the carbonyl compounds produced, the constitution of the diol may be deduced.

59. Which of the following compound is obtained when the following compound is oxidized by HIO4?
CH3
— CH — C — CH 3
OH OH
O O O O
(A) — C — OH (B) CH 3 — C — H (C) — C — CH 3 (D) CH 3 — C — CH 3

OH
60. HIO
4  ( X )
H3C OH
The compound (X) in the above reaction is
O O O
(A) (B) HCCH2CH2CH2CH
O
O O O O
(C)HCCH2CH2CH2CCH3 (D) HOCCH2CH2CH2CCH3

 CHO 
 
 HO — C — H 
 
61. When arabinose  H — C — OH  is oxidized by HIO4, then formaldehyde and formic acid are
 
 H — C — OH 
 
 CH2 OH 
 
 
obtained. Molar ratio of formic acid and formaldehyde obtained per mol of arabinose is
(A) 3 : 2 (B) 4 : 1 (C) 1 : 4 (D) 2 : 3

PASSAGE- 4
Vanillin (A) of molecular formula (C8H8O3) is isolated from vanilla Beans. It gives intense violet colour with
neutral FeCl3 and also gives positive Tollen’s Test. One mole of vanillin reacts with conc. HBr to give a
compound (B) and one mole CH3Br. (B), on oxidation followed by heating with sodalime gives catechol,
OH
OH
.

62. Vanillin contains

(A) one –OC2H5 group (B) one –OCH3 group
(C) two –OC2H5 groups (D) two –OCH3 groups

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63. The structure of Vanillin is

CHO CHO CHO CHO

OCH3 OH
(A) (B) (C) (D)
OH OCH3
OH OH OH OH

64. Compound (B) on heating with Zn dust will give

CHO OH CHO OH
CHO
(A) (B) (C) (D)
OH

65. Compound (B) can be prepared by

(A) Gatterman Reaction (B) Benzoin condensation
(C) Perkin Reaction (D) Reformatsky Reaction

PASSAGE -5
Acid strength is measured by the position of equilibrium of ionisation in water i.e. acid strength is a
function of stability of conjugate base of the acid. More is the stability of conjugate base of the acid, more is
the acidic strength. While basicity of nitrogenous compounds are determined by the relative availability of
non–bonding electrons on nitrogen atom to a proton donor or Lewis acid and by the stabilisation of the
positive charged nitrogen atom by solvation or in some cases by resonance.

66. Which one of the following phenols will show highest value of Ka?
CH3 CH3
OH H3C OH H3C OH OH
(A) (B) (C) (D)
CH3 O2N H3 C NO2 H3C
CH3 NO2

67. Which one of the following is least basic in character?

(A) (B) N N–H (C) (D)

..
N N N
H

68. Arrange the following compounds in decreasing order of acidity?

OH Cl Cl
OH Cl
(I) (II) (III) (IV)
OH
OH
Select the correct answer from the codes given below:
(A) (III) > (II) > (IV) > (I) (B) (III) > (II) > (I) > (IV)
(C) (II) > (III) > (I) > (IV) (D) (II) > (III) > (IV) > (I)

69. Consider the basicity of following aromatic amines:

(I) Aniline (II) p–nitroaniline
(III) p–methoxy aniline (IV) p–methylaniline
The correct order of decreasing basicity is
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(A) (III) > (IV) > (I) > (II) (B) (III) > (IV) > (II) > (I)
(C) (I) > (II) > (III) > (IV) (D) (IV) > (III) > (II) > (I)

10.6 Match The Column

70.
Reaction Mechanism
(P) change in number of carbon in cycle
Conc.H SO
(A)   
2
4 
(Q) Pinacol rearrangement
HIO4
(B) 
(R) Oxidative bond cleavage

H

(C) heat
(S) Ketone as product

H O

3

(D) heat

71. Column I Column II

(A) Identification of 1°, 2°& 3° Alcohols (P) Oxymercuration demercuration
(B) Identification of 1°, 2°& 3° Nitro alkanes (Q) Cu/300° heat
(C) Formation of alcohol by anti Markovnikov's (R) Victor Mayer's test
addition of H2O
(D) Formation of alcohol by Markovnikov's (S) Hydroboration oxidation
addition
(T) Lucas test
72.
Column – I Column – II

(A) Oxidation of 1°alcohol in aldehyde (P) KMnO4/OH−

(Q) Collin's reagent

(R) Jone's reagent

(D) Oxidation of alkene into acid (S) P.C.C

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73.
Column – I Column – II

(B) Violet color is obtain by thereaction of

neutral FeCl3 with

(C) Reaction of benzaldehyde with

LiAlH4 / H2O gives

74.
Column I (Alcohol) Column II (Dehydration Products)
OH CH2
(A)
(P)

CH2OH
(Q)
(B)

OH
(R)
(C)
H3C OH CH3

(D) (S)

75.
Column I Column II
OH (P) Single substitution occurs and ortho
concH2SO4, Room temperature product is predominant.
(A)

OH (Q) Single substitution occurs and para

concH2SO4, 100oC product is predominant.
(B)

O OH (R) Tri–substitution occurs.

Br2–Water
(C) HO–C

OH (S) Di–substitution occurs.

CH3 Br2–Water (T) No reaction occurs.
(D)

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76.
Column–I Column–II
(A) neohexyl alcohol (P) highest boiling point
(B) sec-butyl alcohol (Q) positive iodoform test
(C) n-hexyl alcohol (R) highest water solubility
(D) iso-propyl alcohol (S) susceptible to chromate (CrO3/H+) oxidation
77.
Column I Column II
(A) Phenol + neutral FeCl3 (P) No reaction
(B) Phenol + Br2(aq.) (Q) Violet colour
(C) Phenol + NaHCO3 (R) White ppt.
(D) Picric acid + NaHCO3 (S) CO2 gas in evolved
(T) Yellow colour

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9. Answers to Objective Assignments

HOME ASSIGNMENT – I

1. B 2. B 3. D 4. B 5. B 6. D 7. C

8. A 9. B 10. B 11. C 12. B 13. B 14. A

15. C 16. B 17. C 18. A 19. B 20. C 21. D

22. B 23. A 24. B 25. B

HOME ASSIGNMENT – II

1. D 2. C 3. A 4. D 5. B 6. D 7. C

8. D 9. D 10. A 11. C 12. C 13. D 14.D

15. D 16. A 17. A 18. A 19. C 20. A 21. A

22. D 23. A 24. B 25. A

HOME ASSIGNMENT – III

1. D 2. C 3. A 4. B 5. B 6. A 7. A

8.D 9. A 10. C 11. A 12. A 13. C 14. B

15. B 16. C 17. C 18. A 19. B 20. C 21. A

22. B

HOME ASSIGNMENT – IV

1. C 2. B 3. A 4. A 5.C 6. C 7. C

8. A 9. C 10. C 11. C 12. D 13. A 14. D

15. C 16. D 17. A 18. A 19. C 20. C 21. C

22.C 23. A 24. A 25.D

Get Equipped for IIT - JEE

1. B 2. A 3. A 4. B 5. C 6. B 7. D

8. C 9. A 10. B 11. C 12. C 13. A 14. A

15. C 16. B 17. B 18. A 19. B 20. C 21. A

22. C 23. A 24. C 25. A 26. B 27. B 28. D

29. C 30. D 31. D 32. C 33. C 34. D 35. C

36. B 37. B 38. D 39. C 40. D 41. ACD 42. AC

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43. AC 44. ABC 45. ACD 46. AB 47. AD 48. AC 49. CD

50. ABD 51. AC 52. ABD 53. C 54. C 55. A 56. B

57. C 58. A 59. D 60. C 61. B 62. B 63. C

64. A 65. A 66. B 67. A 68. D 69. A

70. (A) – P,Q, S ; (B) – R, S; (C) – P; (D)- S

71. (A) – Q, R, T; (B) – R; (C) - S; (D) – P

72. (A) – Q, R, S; (B) –S; (C)- Q; (D)- P

73. (A)- R, S; (B)- R; (C)- Q; (D)- P

74. (A)  Q, R ; (B)  P, S ; (C)  R ; (D)  P, S

75. (A)  P ; (B)  Q ; (C)  R ; (D)  S

76. (A)  S ; (B)  Q, S ; (C)  P, S ; (D)  Q, S

77. (A)  Q ; (B)  R ; (C)  P ; (D)  S

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