1014 General Organic Chemistry

Chapter

23
General Organic Chemistry

Carbon is an essential element of organic compounds, it has four 3 2

electrons in its outer most shell.

According to the ground state electronic configuration of carbon, it :
is divalent. Tetravalency of carbon can be explained by promoting one of
O
the 2s 2 - electrons to the unocupied 2 p z 1 atomic orbital. ||
(i) CH 3 CH CH C CH 3
The four valencies of carbon atom are similar and they are
symmetrically arranged around the carbon atom. According to Le Bell and sp 2
sp 2 sp 2 sp 3
the four valencies of carbon do not lie in one plane. They are sp 3
directed towards the corners of a regular tetrahedron with carbon atom at
(ii) CH 2 C CH 2
the centre and the angle between any two valencies is 109 28 . o

sp sp 2
Hybridisation in Organic Compounds sp 2
(1) The process of mixing atomic orbitals to form a set of new (iii) CH 3 CH CH CH 2 C N
equivalent orbitals is termed as . There are of
hybridisation, sp3 sp 2 sp 2 sp3 sp sp
3
(i) sp (involved in saturated organic compounds
containing only single covalent bonds), (iv) HC C CH CH 2
2
(ii) sp (involved in organic compounds having sp sp sp 2
sp 2
carbon atoms linked by double bonds) and
(iii) sp (involved in organic compounds having In diamond carbon is 3
hybridised and in graphite carbon is
carbon atoms linked by a triple bonds). 2
sp hybridised.
Table : 23.1
Type of hybridisation 3 2 (ii) : (Electron pair method)
Number of orbitals used 1 and 3 1 and 2 1 and 1
= + where = electron pair present in hybrid orbitals , =
Number of unused Nil One Two
-orbitals bond pair present in hybrid orbitals
Bond Four - Three - Two - Number of = Number of atoms attached to the central atom
One - Two -
Bond angle
of the species
109.5 120 180
Geometry Tetrahedral Trigonal planar Linear Central atom
% -character 25 or 1/4 33.33 or 1/3 50 or 1/2 First atom
(2) Determination of hybridisation at different carbon atoms : It can
=
be done by two methods,
(i) : In this method hybridisation can be know by the Second atom
number of bonds present on that particular atom. Third atom
0 1 2 Central atom
1 2
H C C H 1
2

bp 2
3
=3
 General Organic Chemistry 1015

s sp sp 2 sp 3 p
% s - character and electronegativityin decreasing order.
(iii)
Number of
(a) If carbon has - bonds or positive charge or odd electron, than % of orbital character
on carbon will be zero. 1 1
(b) If carbon has negative charge, then will be equal to one. C C bond length C H bond length
Number of electron pairs ( ) tells us the type of hybridisation as
follows, Table : 23.2
2 3 4 5 6 Bond type ( Bond length Bond type (C Bond length
sp sp 2 sp 3 sp 3 d sp 3 d 2 ) C)

sp 3 s 1.112Å sp 3 sp 3 (alk 1.54 Å

(alkanes) anes)
(i) CH 2 CH (ii) CH 2 CH
sp 2 s 1.103Å sp 2 sp 2 (alk 1.34Å
bp 2 bp 2 (alkenes) enes)
lp 0 lp 1
sp s 1.08Å sp sp (alkyn 1.20Å
ep 2, sp ep 3, sp 2
(alkynes) es)
(iii) CH 2 C CH 3 (iv) CH C
(iv) :
|
bp 1
CH 3 lp 1
bp 3 ep 2, sp Table : 23.3
lp 0
ep 3, sp 2 Bond type ( Bond type ( Bond energy
) ( ) ) ( )
(v) CH 3 CH CH 3 104 80 90
sp 3 s sp 3 sp 3
bp 3 (in alkanes) (in alkanes)
lp 1
ep 4 , sp 3 sp 2
s 106 sp 2 sp 2 122 164
(3) Applications of hybridisation (in alkenes) (in alkenes)
(i) : Since s - orbitals are closer to the sp s 121 sp sp 123 199
nucleus than p - orbitals, it is reasonable to expect that s
. Thus the decreasing order of the (in alkynes) (in alkynes)
size of the three hybrid orbitals is opposite to that of the decreasing order
of s orbital character in the three hybrid orbitals. (v)
sp3 sp2 sp (a) Hydrogen present on electronegative carbon is acidic in nature.
(ii) (b) Acidity of hydrogen is directly proportional to the
(a) Electronegativity of -orbital is maximum. electronegativity of the atom on which hydrogen is present.
(b) Electronegativity of hybrid orbital % character in hybrid
orbitals Thus
H O H NH3 CH CH
Orbital sp sp 2 sp 3 Electronegativityof the atoms
% s - character 50 33. 33 25 Acidityof compounds in decreasing order
s-character in decreasing order and electronegativityin decreasing order
Thus -hybrid carbon is always electronegative in character and (c) Acidity of hydrocarbon % of
3 2
sp - hybrid carbon is electropositive in character. sp -hybrid carbon can CH CH CH 2 CH 2 CH 3 CH 3
behave as electropositive (in carbocation) as well as electronegative (in % -character 50 33.33 25
carbanion) in character.
pKa 25 44 50
CH 3 CH 2 CH 2 CH - character and acidity in decreasing order
1
Acidity and Acidity (pKa log Ka)
sp 2 pKa
Order of acidic nature of alkynes is,
Electronegative carbon
Electropositive carbon having positive charge HC CH HC C CH 3
(c) Electronegativities of different hybrid and unhybrid orbitals in
decreasing order is as follows The relative acidic character follows the order;
 1016 General Organic Chemistry

H 2O ROH HC CH NH 3 CH 2 CH 2 CH 3 CH 3 Inductive effect or Transmission effect

Obviously, the basic character of their conjugate bases follows the (1) When an electron withdrawing ( ) or electron-releasing ( )
reverse order, , group is attached to a carbon chain, polarity is induced on the carbon atom
and on the substituent attached to it. This permanent polarity is due to
CH 3 CH 2 CH 2 CH NH 2 HC C RO HO displacement of shared electron of a covalent bond towards a more
electronegative atom. This is called
Steric effect
C C C C
On account of the presence of bulkier groups at the reaction centre,
they cause mechanical interference and with the result the attacking reagent C C C C X
finds it difficult to reach the reaction site and thus slows down the reaction.
This phenomenon is called steric hinderance or steric effect. C C C C Y
(1) Tertiary alkyl halides having bulky groups form tertiary (2) Carbon-hydrogen bond is taken as a standard of inductive effect.
carbocation readily when hydrolysed because of the presence of the three Zero effect is assumed for this bond. Atoms or groups which have a greater
bulky groups on the carbon having halogen. electron withdrawing capacity than hydrogen are said to have I effect
Steric strain around this carbon Steric strain is released whereas atoms or groups which have a greater electron releasing power are
CH
3 (More strained species) (less strained species) said to have +I effect.
|
H3C C Cl H 3 C C CH 3
| |
N H3 NO 2 CN SO 3 H CHO CO COOH COCl COOR
CH CH 3 > CONH F Cl Br I OH OR NH 2 C6 H 5 H
3 2

I power of groups in decreasing order with respect to the reference

(2) Primary alkyl halide having quaternary -carbon does not form
alkyl > alkyl > alkyl > CH 3 H
transition state because of the steric strain around -carbon by the -
carbon. To release the strain it converts into carbocation. + I power in decreasing order with respect to the reference
Bulky group
CH + I power number of carbon in the same type of alkyl groups
3
| CH 3 CH 2 CH 2 CH 2 CH 3 CH 2 CH 2
CH 3 C CH 2 Cl
|
CH 3 CH 2
CH Strained carbon due to
3
bulky group present + power in decreasing order in same type of alkyl groups
around this carbon.
(3) Applications of Inductive effect
(3) Steric strain inhibits the resonance. This phenomenon is known
(i) : Magnitude of +
as steric inhibitions of resonance.
charge on cations and magnitude of charge on anions can be
compared by + or groups present in it.
Electronic displacement in covalent bonds
1
It is observed that most of the attacking reagents always possess Magnitude of ve charge I
either a positive or a negative charge, therefore for a reaction to take place I power of the group
on the covalent bond the latter must possess oppositely charged centres. power of the group.
This is made possible by displacement (partial or complete) of the bonding 1
electrons. The electronic displacement in turn may be due to certain effects, Magnitude of ve charge I
I power of the group
some of which are permanent and others are temporary. The former effects
power of the group.
are permanently operating in the molecule and are known as polarisation
effects, while the latter are brought into play by the attacking reagent and (ii) : + effect of methyl group enhances
as soon as the attacking reagent is removed, the electronic displacement effect of the halogen atom by repelling the electron towards tertiary
disappears; such effects are known as the polarisability effects. carbon atom.
CH 3 CH 3
Electronic displacement
H 3C C X H3C CH X
CH 3
Polarisation effect Polarisability effect CH 3 CH 2 X CH 3 X
(permanent) (temporary)
Tertiary > Secondary > Primary > Methyl
(iii) Relative strength of the acids :
Inductive Mesomeric Hyperconjugative Inductomeric Electromeric (a) Any group or atom showing + effect decreases the acid strength
effect effect effect effect effect as it increases the negative charge on the carboxylate ion which holds the
hydrogen firmly. Alkyl groups have + effect.
 General Organic Chemistry 1017

Thus, acidic nature is, R2 NH RNH 2 NH 3 R3 N

C2 H 5
HCOOH CH 3 COOH C 2 H 5 COOH C3 H 7 COOH C4 H 9 COOH
(CH 3 )2 CH RNH 2 NH 3 R2 NH R3 N
+ effect increases, so acid strength decreases
(CH 3 )3 C NH 3 RNH 2 R2 NH R3 N
Formic acid, having no alkyl group, is the most acidic among these
acids.
The relative basic character of amines is not in total accordance
(b) The group or atom having effect increases the acid strength with inductive effect (t s p) but it is in the following order: Secondary
as it decreases the negative charge on the carboxylate ion. Greater is the
> Primary > Tertiary. The reason is the steric hindrance existing in the -
number of such atoms or groups (having effect), greater is the acid
strength. amines.

Thus, acidic nature is, In gas phase or in aqueous solvents such as chlorobenzene etc,
the solvation effect, , the stabilization of the conjugate acid due to H -
CCl 3 COOH CHCl 2 COOH CH 2 ClCOOH CH 3 COOH bonding are absent and hence in these media the basicity of amines
Trichloro Dichloro Monochloro Acetic acid
acetic acid acetic acid acetic acid depends only on the + effect of the alkyl group thus the basicity of amines

( Inductive effect increases, so acid strength increases)

follows the order : 3 o 2o 1o NH 3 .

(c) Strength of aliphatic carboxylic acids and benzoic acid (vii) : The decreasing order of base strength in
alcohols is due to + effect of alkyl groups.
R COOH C6 H 5 COOH
(CH 3 )3 COH (CH 3 )2 CHOH CH 3 CH 2 OH CH 3 OH
I group I group (3 o ) (2 o ) (1o )

(viii) :+ effect tends to decrease the (+ )

charge and effect tends to increases the + charge on carbocation.
Hence benzoic acid is stronger acid than aliphatic carboxylic acids
but exception is formic acid. Thus, (CH 3 )3 C (CH 3 )2 CH CH 3 CH 2 CH 3
HCOOH > C 6 H 5 COOH > RCOOH
(ix) Stability of carbanion : Stability of carbanion increases with
Acid strength in decreasing order increasing effect.
Decreasing order of acids :
CH 3 CH 3 CH 2 (CH 3 )2 CH (CH 3 )3 C
NO 2CH 2COOH FCH2COOH ClCH 2COOH BrCH2COOH .
Resonance effect or mesomeric effect
F3C COOH Cl3C COOH Br3C COOH I3C COOH .
(1) The effect in which electrons are transferred from a multiple
CH 3 OH CH 3 CH 2 OH (CH 3 ) 2 CHOH (CH 3 ) 3 COH bond to an atom, or from a multiple bond to a single covalent bond or lone
Methyl Ethyl Iso propyl Tert butyl pair ( ) of electrons from an atom to the adjacent single covalent bond is
alcohol Alcohol alcohol alcohol called or simply as In case of the compound with
As compared to water, phenol is more acidic ( effect) but methyl conjugated system of double bonds, the mesomeric effect is transmitted
through whole of the conjugated system and thus the effect may better be
alcohol is less acidic (+ effect).
known as conjugative effect
OH H OH > CH 3 OH (2) Groups which have the capacity to increase the electron density
Phenol Water Methyl alcohol
of the rest of the molecule are said to have M effect. Such groups
(vi) (Basic nature of NH 2 ) possess lone pairs of electrons. Groups which decrease the electron density
of the rest of the molecule by withdrawing electron pairs are said to have
The difference in base strength in various amines can be explained
M effect, e.g.,
on the basis of inductive effect. The + effect increases the electron density
(a) The groups which donate electrons to the double bond or to a
while effect decreases it. The amines are stronger bases than NH 3 as
conjugated system are said to have M R .
the alkyl groups increase electron density on nitrogen due to + effect while
ClNH 2 is less basic due to M :
electron pair for coordination with proton, the more is basic nature, .. ..
more is the negative charge on nitrogen atom (due to + effect of alkyl Cl, Br, I, N H 2 , NR 2 , OH, OR, SH , OCH 3 , S R
..

Thus, the basic nature decreases in the order; (b) The groups which withdraw electrons from the double bond or
from a conjugated system towards itself due to resonance are said to have
(C 2 H 5 )2 NH CH 3 CH 2 NH 2 CH 3 NH 2 NH 3 ClNH 2
Diethyl Ethyl Methyl Ammonia Chloro M effect or R effect.
amine amine amine amine
M effect groups :
The order of basicity is as given below;
O
Alkyl groups ( ) Relative base strength ||
R2 NH RNH 2 R3 N NH 3
NO 2 , C N , C , CHO, COOH , SO 3 H
CH 3
 1018 General Organic Chemistry
(3) The inductive and mesomeric effects, when present together, (iv) Resonating structures due to hyperconjugation may be written
may act in the same direction or oppose each other. The mesomeric effect is
more powerful than the former. For example, in vinyl chloride due to
effect the chlorine atom should develop a negative charge but on account of H H
mesomeric effect it has positive charge. |
H C CH CH 2 H C CH C H2
.. .. | |
: Cl CH CH 2 : Cl CH CH 2 H H
.. ..
H H
Application of mesomeric effect : It explains, | |
(1) Low reactivity of aryl and vinyl halides, HC CH C H2 H C CH C H2
|
(2) The acidic nature of carboxylic acids, H H
(3) Basic character comparison of ethylamine and aniline,
(4) The stability of some free radicals, carbocations and carbanions. (v) Number of resonating structures due to the hyperconjugation =
Number of -hydrogens + 1.
Difference between Resonance and Mesomerism : Although both
resonance and mesomerism represent the same phenomenon, they differ in Applications of hyperconjugation
the following respect : Resonance involves all types of electron (1) Stability of alkenes : Hyperconjugation explains the stability of
displacements while mesomerism is noticeable only in those cases where a certain alkenes over other alkenes.
multiple bond is in conjugation with a multiple bond or lone pair of
Stability of alkenes Number of alpha hydrogens Number of
electron.
resonating structures
Example :
CH 3 CH CH 2 CH 3 CH 2 CH CH 2 CH 3 CH CH CH 2
|
.. CH 3
(i) H 2 C CH CH CH 2 H 2 C CH CH C H2 Stability in decreasing order

.. (2) Carbon-carbon double bond length in alkenes : As we know that

..
:O :O: the more is the number of resonating structures, the more will be single
|| .. || bond character in carbon-carbon double bond.
(ii) R C O H R C O H
. .
.. (3) Stability of alkyl carbocations : Stability of alkyl carbocations
Both (i) and (ii) are the examples of mesomerism and resonance number of resonating structures number of alpha hydrogens.
.. (4) Stability of alkyl free radicals : Stability of alkyl free radicals can
effect. Let us consider the following example H Cl : H Cl . be explained by hyperconjugation. Stability depends on the number of
.. resonating structures.
Such an electron displacement is the example of resonance only (not the
(5) Electron releasing (or donating) power of R in alkyl benzene :
mesomerism).
CH 3 (or alkyl group) is R group, ortho-para directing group and
Hyperconjugative effect activating group for electrophilic aromatic substitution reaction because of
(1) When a H C bond is attached to an unsaturated system such the hyperconjugation.
as double bond or a benzene ring, the sigma ( ) electrons of the H C The electron donating power of alkyl group will depends on the
bond interact or enter into conjugation with the unsaturated system. number of resonating structures, this depends on the number of hydrogens
present on -carbon. The electron releasing power of some groups are as
H C follows,
. The concept of
hyperconjugation was developed by Baker and Nathan and is also known as CH 3
. CH 3 |
CH 3 CH 3 CH 2 CH CH 3 C
In fact hyperconjugation effect is similar to resonance effect. Since |
there is no bond between the -carbon atom and one of the hydrogen CH 3
CH
atoms, the hyperconjugation is also called . 3
(2) Structural requirements for hyperconjugation Increasing inductive effect
Electron donating power in decreasing order due to the
(i) Compound should have at least one sp 2 -hybrid carbon of hyperconjugation.
either alkene alkyl carbocation or alkyl free radical. (6) Heat of hydrogenation : Hyperconjugation decreases the heat of
hydrogenation.
(ii) -carbon with respect to sp 2 hybrid carbon should have at
least one hydrogen. (7) Dipole moment : Since hyperconjugation causes the
development of charges, it also affects the dipole moment in the molecule.
If both these conditions are fulfilled then hyperconjugation will take
place in the molecule.
(iii) Hyperconjugation is of three types
 General Organic Chemistry 1019

The increase in dipole moment, when hydrogen of formaldehyde Electromeric effect

( 2.27 D) is replaced by methyl group, ., acetaldehyde ( 2 .72 D)
can be referred to hyperconjugation, which leads to development of charges. (1) The phenomenon of movement of electrons from one atom to
another in multibonded atoms at the demand of attacking reagent is called
H H electromeric effect. It is denoted as E-effect and represented by a curved
H
| | arrow ( ) showing the shifting of electron pair.
H C O ,H C CH O H C CH O
( 2 . 27 D) | | E
H H A B A B:
( 2 .72 D) Reagent

(8) Orienting influence of alkyl group in o, p -positions and of

(2) (i)When the transfer of electrons take place towards the
CCl 3 group in m -position : Ortho-para directing property of methyl
attacking reagent, the effect is called E effect. The addition of acids to
group in toluene is partly due to I effect and partly due to alkenes.
hyperconjugation.
Reverse Hyperconjugation : The phenomenon of hyperconjugation is C C H C C
also observed in the system given below, |
H
X
| CH 3 CH CH 2 H CH 3 CH CH 3
C C C ; where X halogen Propene
|
Since, CH 3 group is electron donating, the electrons are
In such system the effect operates in the reverse direction. Hence transferred in the direction shown.
the hyperconjugation in such system is known as reverse hyperconjugation.
The attacking reagent is attached to that atom on which electrons
Cl have been transferred.
Cl
| (ii) When the transfer of electrons takes place away from the
Cl C CH CH 2 Cl C CH CH attacking reagent, the effect is called E effect. Example, The addition of
| | 2
Cl Cl cyanide ion to carbonyl compounds.

Cl Cl
| | C O CN C O
Cl C CH CH 2 Cl C CH CH |
| 2 CN
Cl Cl
The attacking reagent is not attached to that atom on which
electrons have been transferred.
The directing influence and the deactivating effect of CX 3
(3) Direction of the shift of electron pair : The direction of the shift
group in electrophilic aromatic substitution reaction can be explained by of electron pair can be decided on the basis of following points.
this effect.
(i) When the groups linked to a multiple bond are similar, the shift
X X X X can occur in either direction.
| | | |
X C X X C X X C X X C X (ii) When the dissimilar groups are linked on the two ends of the
| || || || double bond, the shift is decided by the direction of inductive effect.
+
In the case of carbonyl group, the shift is always towards oxygen,
more electronegative atom.

Inductomeric effect C O C O:
Inductomeric effect is the temporary effect which enhances the In cases where inductive effect and electromeric effect
inductive effect and it accounts only in the presence of an attacking reagent. simultaneously operate, usually electrometric effect predominates.
Example,
H Cleavage (fission or breaking) of covalent bonds
H Breaking of covalent bond of the compound is known as bond
HO H C Cl HO....... ..... C..... ....... Cl fission. A bond can be broken by two ways,
H (1) Homolytic bond fission or Homolysis
H H (i) In homolysis, the covalent bond is broken in such a way that
H each resulting species gets its own electron. This leads to the formation of
Cl
HO C H odd electron species known as free radical.
H . .
A : B A B
In methyl chloride the effect of Cl group is further increased Free radical
temporarily by the approach of hydroxyl ion.
 1020 General Organic Chemistry
(ii) The factor which favours homolysis is that the difference in is termed as carbocation. If negative charge is present on the carbon then
electronegativity between A and B is less or zero. anion is termed as carbanion.
(iii) Homolysis takes place in gaseous phase or in the presence of (ii) The factor which favours heterolysis is greater difference of
non polar solvents (CCl 4 , CS 2 ) , peroxide, UV light, heat ( 500 C) , o electronegativities between A and B .
electricity and free radical. (iii) Mechanism of the reaction in which heterolysis takes place is
(iv) Mechanism of the reaction in which homolysis takes place is known as heterolytic mechanism or ionic mechanism.
known as homolytic mechanism or free radical mechanism. (iv) The energy required for heterolysis is always greater than that
(2) Heterolytic bond fission or heterolysis for homolysis due to electrostatic forces of attraction between ions.

(i) In heterolysis, the covalent bond is broken in such a way that Reaction Intermediates
one species ( , less electronegative) is deprived of its own electron, while
the other species gains both the electrons. Short lived fragments called reaction intermediates result from
homolytic and heterolytic bond fission. The important reaction
intermediates are free radicals, carbocations, carbanions, carbenes, benzyne
A : B A: B and nitrenes.
carbanion carbocation

Thus formation of opposite charged species takes place. In case of

organic compounds, if positive charge is present on the carbon then cation
Table : 23.4
Characteristic Free radical Carbocation Carbanion Carbene
Nature Neutral having odd electron Positive charge on Negative charge on Neutral, divalent with 2
unshared electrons
2 2 3
Hybridisation (non-conjugated) (i) 2 (singlet)
2
(Conjugated) (ii) (triplet)
Structure Planar Planar Pyramidal/Planar (i) Planar (singlet)
(ii) Linear (triplet)
Magnetism Paramagnetic Diamagnetic Diamagnetic (i) Diamagnetic
(ii) Paramagnetic
Stability order . . . Triplet > singlet
Ph3 C Ph2 CH Ph CH 2 Ph3 C Ph2 CH PhCH 2 Ph3 C Ph2 CH
.
CH 2 CH CH 2 PhCH 2 Allyl
CH 2 CH CH 2 3o 2o
. . 3o 2o 1o CH 3 CH 2 1o 2o 3o
1o CH 2 CH 2 CH

Benzyne (ii) It reacts with strong nucleophile like NH 2

(1) 1, 2-Didehydrobenzene, C6 H 4 and its derivatives are called
2
2

benzyne or arynes and the simplest member is benzyne. N H2

H
(2) It is neutral reaction intermediate derived from benzene ring by
removing two substituents, of positions, one in the form of
electrophile and other in the from of nucleophile leaving behind two ..
electrons to be distributed between two orbitals. Nitrenes (R N:)
(1) The nitrogen analogous of carbenes are called nitrenes.
Abnormal bond (2) There is possibility of two spin states for nitrenes depending on
whether the two non-bonding electrons (the normal nitrogen lone pair
remains paired) have their spins paired or parallel.
Two sp -orbitals ouside
2

the ring ..
R .N. These two are lone pair of electrons
(3) Benzyne intermediate is aromatic in character.
(4) When halobenzene is heated with sodamide formation of These two may be paired or unpaired
benzyne takes place. (3) In general nitrenes obey Hunds rule and the ground state triplet
with two degenerate sp -orbitals containing a single electron each.

NaNH 2
R N

(5) (i) It behaves as dienophile and gives Diels-Alder reaction with -Triplet nitrene
diene. (4) Nitrenes can be generated, in situ, by the following methods,
 General Organic Chemistry 1021

(i) Br2 1o (2) Nucleophiles : Electron rich species or electron donors are called
nucleophiles. Nucleophiles can be classified into three categories :
(Hofmann-bromamide reaction),
(i) : Negatively charged species are called
O O O charged nucleophiles.
|| || || . .
Br2 / NaOH OH
R C NH 2 R C NHBr R C N Br
1 o Amide
H2O .. H, O H , R O, C H 3 , X , S H, R S
(ii) : It can be classified into two categories :
(a) Neutral covalent compound, in which central atom has complete
O octet, has at least one lone pair of electrons and all atoms present on
|| . . central atom should not be electronegative, is neutral nucleophile.
Rearrangem ent
R C N O C N R
Br . . Isocyanate .. .. .. .. .. ..
N H 3, R N H 2 , R2 N H, R3 N , N H 2 N H 2 (Nitrogen nucleophile)
KOH
R NH 2 K 2 CO 3
(Hydrolysis) 1 o Amine .. .. ..
H O H , R O H, R O R (Oxygen nucleophiles)
(ii) .. .. ..
.. .. .. .. .. ..
or h
R N N N: R N: N N H S H , R S H, R S R (Sulphur nucleophiles)
Alkylazide Alkylnitrene .. .. ..
.. .. .. .. ..
(iii) Unsubstituted nitrene (H N :) can be obtained by photolysis P H 3 , R P H 2 , R 2 P H , R3 P (Phosphorus nucleophiles)
of (or by passing electric discharge through) NH 3 , N 2 H 4 or N 3 H . (b) Organic compound containing carbon, carbon multiple bond/
bonds behaves as nucleophile.
Attacking reagents
Alkenes, Alkynes, Benzene,
The fission of the substrate molecule to create centres of high or
low electron density is influenced by attacking reagents. Most of the CH 2 CH CH CH 2 , CH 2 CH C CH
attacking reagents can be classified into two main groups. (iii) : Species having two nucleophilic
Electrophiles or electrophilic reagents and Nucleophiles or centres out of which, one is neutral (complete octet and has at least one
nucleophilic reagents. lone pair of electrons) and the other is charged (negative charge) behaves as
(1) Electrophiles : Electron deficient species or electron acceptor is ambident nucleophile
an electrophile.
O
It can be classified into two categories : .. ..
(i) : Positively charged species in which C N, O N O, O S OH
central atom has incomplete octet is called charged electrophile.
O
O
H ,X ,R ,N ,N O, S O3 H Organometallic compounds are nucleophiles.
O .. Nucleophiles are Lewis bases.
All cations are charged electrophiles except cations of IA, IIA group Organic compounds which behave as an electrophile as well as a
nucleophile : Organic compound in which carbon is bonded with
elements, Al and NH 4 electronegative atom ( , , ) by multiple bond/bonds behaves as
(ii) : It can be classified into three categories, electrophile as well as nucleophile :
(a) Neutral covalent compound in which central atom has O O O O
|| || || ||
incomplete octet is neutral electrophile,
R C H, R C R, R C OH, R C Cl ,
. .. ..
BeCl 2 , BH 3 , ZnCl 2 , AlX3, FeX 3 , CH 3 , CH 2 , CX 2 O O
|| ||
(b) Neutral covalent compound in which central atom has complete R C OR, R C NH 2 , R C N, R N C
or expended octet and central atom has unfilled sub-shell is neutral During the course of chemical reaction electrophile reacts with
electrophile,
nucleophile.
SnCl 4 , SiCl4 , PCl5 , SF6 , IF7 Strong Lewis acid is stronger electrophile
(c) Neutral covalent compound in which central atom is bonded
only with two or more than two electronegative atoms is called neutral CO 2 N O2 S O 3 H . Stronger is an acid, weaker is its conjugated
electrophile. base or weaker is the nucleophile.
BeCl 2 , BX 3 , AlX3 , FeX 3 , SnCl 4 , PCl3 ; : HF H2O NH 3 CH 4
..
PCl5 , NF3 , C X 2 , CO 2 , SO 3 , CS 2 , F OH NH 2 CH 3
Increasing order of nucleophilicity.
Cl 2 , Br2 and I2 also behave as neutral electrophiles.
Electrophiles are Lewis acids. Types of organic reactions
 1022 General Organic Chemistry
It is convenient to classify the numerous reactions of the various (iii) The leaving power of some nucleophilic groups are given below
classes of organic compound into four types, in decreasing order,
Substitution reactions, Addition reaction, O
O O
Elimination reactions, Rearrangement reactions, || || ||
CF3 S O Br S O CH 3 S O
Substitution reactions || || ||
Replacement of an atom or group of the substrate by any other O O O
atom or group is known as substitution reactions. O O
Substituting or || ||
Leaving group attacking group C6 H 5 S O CH 3 S O
|| ||
O O
CH 3 CH 2 Br NaOH CH 3 CH 2 OH NaBr O O
Ethyl bromide Ethyl alcohol
|| ||
(Bromine atom is replaced by hydroxyl group) I Br CF3 C O H O Cl F CH 3 C O
(iv) In these reactions leaving group of the substrate is replaced by
Types of substitution reactions : On the basis of the nature of another nucleophile. If reagent is neutral then leaving group is replaced by
attacking species substitution reactions are classified into following three negative part of the reagent. Negative part of the reagent is always
categories, nucleophilic in character.
(1) Nucleophilic substitution reactions
R L E Nu R Nu L ; R L Nu R Nu L
(2) Electrophilic substitution reactions (v) In S N reactions basicity of leaving group should be less than
(3) Free radical substitution reactions the basicity of incoming nucleophilic group. Thus strongly basic nucleophilic
(1) Nucleophilic substitution reactions group replaces weakly basic nucleophilic group of the substrate.
OH
(i) Many substitution reactions, especially at the saturated carbon R Cl R OH Cl .....(A)
( NaOH )
atom in aliphatic compounds such as alkyl halides, are brought about by
nucleophilic reagents or nucleophiles. Basicity of OH is more than Cl hence OH replaces as Cl .
R X OH R OH X R OH Cl
R Cl OH ......(B)
Substrate Nucleophile Leaving group
( HCl )

Such substitution reactions are called nucleophilic substitution

Basicity of Cl is less than OH , hence Cl will not replace as
reactions, S N reactions ( stands for substitution and for
nucleophile). OH hence reaction (B) will not occur.
(vi) Unlike aliphatic compounds having nucleophilic group as
(ii) The weaker the basicity of a group of the substrate, the better leaving group, aromatic compounds having same group bonded directly
is its leaving ability. with aromatic ring do not undergo nucleophilic substitution reaction under
ordinary conditions.
1
Leaving power of the group The reason for this unusual reactivity is the presence of lone pair of
Basicityof the group
electron or bond on the key atom of the functional group. Another factor
for the low reactivity is nucleophilic character of aromatic ring.
HI HBr HCl HF
(vii) The S N reactions are divided into two classes, S N 2 and S N 1
Decreasing acidity
reactions.

I Br Cl F
Increasing basicity

Decreasing leaving ability

Table : 23.5 2 1

Factors 2 Reactions 1 Reactions

Number of steps Slow
One: R : L : Nu R : Nu : L Two: (i) R:L R :L
Fast
(ii) R : Nu R : Nu
Reaction rate and order Second order: First order:
Rate [Substrate] [Nucleophile] or Rate Rate [Substrate] or Rate = K1 [RL]
= K 2 [RL][: Nu ]
Molecularity Bimolecular Unimolecular
TS of slow step
: Nu C :L : Nu C L Nu :
Reacting nucleophile The nucleophile attacks the carbon of the substrate The nucleophile can attack the carbon of the substrate both
exclusively from the back side. from the back and front sides although the back side attack
 General Organic Chemistry 1023

predominates.
Stereochemistry Complete inversion of configuration takes place. Inversion and retention takes place.
Reactivity order of alkyl halides Methyl>1°>2°>3°halides. (I Br Cl F) 3°>2°>1° > methyl halides. (I Br Cl F)
Rearrangement No rearranged product is formed (except for Rearranged products can be formed.
allylic).
Nature of nucleophiles Favoured by strong and high concentration of Favoured by mild and low concentration of nucleophiles.
nucleophiles.
Polarity Favoured by solvents of low polarity. Favoured by solvents of high polarity.
Reaction rate determining factor By steric hindrance.
By electronic factor (stability of R ).
Catalysis Not catalysed by any catalyst (phase transfer). Catalysed by Lewis and Bronsted acids,

Ag, AlCl3 , ZnCl 2 and strong .

(2) Electrophilic substitutions reactions : Electrophilic substitution written as S E1 (unimolecular)and if the order is 2, it is S E 2
involves the attack by an electrophile. It is represented as ( stands for
(Bimolecular).
substitution and stands for elctrophile). If the order of reaction is 1, it is
1 Reaction mechanism : Electrophilic substitution in aliphatic compounds are very 2 Reaction mechanism : Electrophilic substitution is very

rare; some of the important examples are: common in benzene nucleus (aromatic compounds) in which -
(i) Replacement of the metal atom in an organometallic compound by hydrogen : electrons are highly delocalized and an electrophile can attack this
region of high electron density.
R M H R H M In all electrophilic aromatic substitution reactions, it involves:

CH 3 CH 2 MgBr
MgBr
CH 3 CH 2
H
CH 3 CH 3 The formation of an electrophile, E,

In halogenation; Cl Cl FeCl3 Cl Fe Cl 4
H
CH 3 CH 2 MgBr H Br CH 3 CH 2 CH 3 CH 3 MgBr2
CH 3 CH 2 Na C6 H6 CH 3 CH 3 C6 H 5 Na In nitration; HNO 3 2 H 2 SO 4 NO 2 2 HSO 4 H3 O

(ii) Decarboxylation of silver salt of carboxylic acid by means of bromine: In sulphonation; 2 H 2 SO 4 SO 3 HSO 4 H 3 O

R3 C C OAg Br Br R3 C C O Br Br Ag In Friedel-crafts reaction; R Cl AlCl3 R AlCl4

|| ||
O O RCOCl AlCl3 RCO AlCl4
R3 C Br CO 2 AgBr
The electrophile attacks the aromatic ring to form
(iii) Isotopic exchange of hydrogen for deuterium or tritium: carbonium ion (or arenium ion) which is stabilized by resonance.

R H D R D H
E
R H T R T H Benzene +

Carbonium ion loses the proton to form substitution

product.

The bromination of benzene in the presence of FeBr3 is

a example of electrophilic substitution reaction.
Similarly, Nitration, sulphonation and Friedel-Crafts

electrophilic substitution reactions.

(3) Free radical substitution reactions : Free radical substitution CH 4 Cl 2 UV

CH 3 Cl HCl
reactions involves the attack by a free radical. These reactions occurs by free Methane light Methyl chloride
radical mechanism which involves Initiation, Propagation and Termination
steps. (ii) (Gomberg reaction) : The
(i) : The chlorination of methane in the reaction of benzene diazonium halide with benzene gives diphenyl by a free
presence of ultraviolet light is an examples of free radical substitution. radical substitution reaction.
 1024 General Organic Chemistry

C6 H 5 H C6 H 5 N 2 X Alkali
C6 H 5 C6 H 5 N2 HX CH 3
Benzene diazonium halide Diphenyl
CH 3 CH CH 2 , C CH 2 ,
(iii) : Ethyl bromide on treatment with metallic CH 3
sodium forms butane, ethane and ethylene by involving free radical
C6 H 5
mechanism.
C CH C 6 H 5 , C6 H 5 CH CH 2
(iv) ( -Bromosuccinimide) : NBS is a
C6 H 5
selective brominating agent and it normally brominates the ethylenic
compounds in the allylic (CH 2 CH CH 2 ) position. This type of Following alkenes will not give addition reaction according to
.
reaction involving substitution at the alpha carbon atom with respect to the
double bond is termed Allylic substitution. It is also used for benzylic R R
bromination. Some examples are: CH 2 CH 2 , R CH CH R, C C ,
CH 2 CO R R
CCl 4
CH 3 CH CH 2 N Br C6 H 5 C6 H 5
Propene
CH 2 CO C C
NBS
C6 H 5 C6 H 5
CH 2 CO (vi) Unsymmetrical alkenes having the following general structure
Br CH 2 CH CH 2 NH give addition according to anti .
Allylbromide
CH 2 CO CH 2 CH G , where is a strong group such as
Succinimide

Addition reactions O
||
These reactions are given by those compounds which have at least CX 3 , NO 2, CN , CHO, COR, COOH , C Z
one bond,
(Z Cl, OH, OR, NH 2 )
O
||
( C C , C C , C ,C N ). In such reaction there
Cl
is loss of one bond and gain of two bonds. Thus product of the |
Anti- Markowniko ff's addition
reaction is generally more stable than the reactant. The reaction is a CH 2 CH CHO HCl CH 2 CH 2 CHO
spontaneous reaction.
(vii) Mechanism of electrophilic addition reactions is as follows,
Types of addition reactions : Addition reactions can be classified
|
into three categories on the basis of the nature of initiating species. C C E Slow
C C E
Olefin Electrophile |
(1) Electrophilic additions Carbonium ion
(2) Nucleophilic additions | |
Fast
(3) Free radical additions C C E X C C E
| Nucleophile | |

(1) Electrophilic addition reactions X

Addition product
(i) Such reactions are mainly given by alkenes and alkynes. (2) Nucleophilic addition reactions : When the addition reaction
(ii) Electrophilic addition reactions of alkenes and alkynes are occurs on account of the initial attack of nucleophile, the reaction is said to
generally two step reactions. be a nucleophilic addition reaction. Due to presence of strongly
(iii) Alkenes and alkynes give electrophilic addition with those electronegative oxygen atom, the -electrons of the carbon-oxygen double
reagents which on dissociation gives electrophile as well as nucleophile. bond in carbonyl group ( C O ) get shifted towards the oxygen atom
(iv) If the reagent is a weak acid then electrophilic addition is and thereby such bond is highly polarised. This makes carbon atom of the
carbonyl group electron deficient.
catalysed by strong acids (Generally H 2 SO 4 ).
(v) Unsymmetrical alkenes and alkynes give addition reactions with C O C O C O

The negative part of the addendum adds on that doubly bonded The addition of to acetone is an example of
carbon of the alkene which has least number of hydrogen atom. nucleophilic addition.
This rule can be used only in those alkenes which fulfil the CH 3 CH 3 OH
following conditions: C O HCN C
(a) Alkene should be unsymmetrical. CH 3 CH 3 CN
Acetone Acetone cyanohydri n
(b) Substituent/substituents present on doubly bonded carbon/( )
should only be + group. The mechanism of the reaction involves the following steps:
(c) If phenyl group is present on doubly bonded carbon, then both gives a proton (H ) and a nucleophile, cyanide ion
doubly bonded carbons should be substituted by phenyl groups.
For example, the following alkenes will give addition according to (CN ) .
 General Organic Chemistry 1025

HCN H CN Elimination reactions are generally endothermic and take place on

heating.
The nucleophile (CN ) attacks the positively charged Elimination reactions are classified into two general types,
carbon so as to form an anion [ H does not initiate the negatively (I) - elimination reactions or 1, 1-elimination reactions.
charged oxygen as anion is more stable than cation].
(II) - elimination reaction or 1, 2-elimination reactions.
CH 3 CH 3 CH 3 O
(I) : A reaction in
CN C O CN C O or C which both the groups or atoms are removed from the same carbon of the
CH CH 3 CH 3 CN
3 molecule is called elimination reaction. This reaction is mainly given by
The proton (H ) combines with anion to form the gem dihalides and gem trihalides having at least one hydrogen.
addition product. ..
Alc. KOH /
CH 3 CHX 3 CX 2 X H
CH 3 | CH 3 OH Product of the reaction is halocarbenes or dihalocarbenes. which are
CN C O H NC C OH or C key intermediates in a wide variety of chemical and photochemical reactions.
CH 3 | CH 3 CN
(II) : Consider the
CH 3 following reactions,

In C O compounds, the addition of liquid gives

CH 3 CH 2 CH 2 L CH 3 CH CH 2 H L
cyanohydrin and the addendum is CN ion and not directly
(addition is catalysed by bases or salts of weak acids and retarded by acids A reaction in which functional group ( leaving group) is
or unaffected by neutral compounds). removed from - carbon and other group (Generally hydrogen atom) from
the - carbon is called - elimination reaction. In this reaction there is loss
O OH
H CN CN H of two bonds and gain of one bond. Product of the reaction is generally
C O C O C C
( A.R.) less stable than the reactant.
CN CN

Nucleophilic addition ( ) reactions on carbonyl compounds will be (1) Types of elimination reactions : In analogy with substitution
in order: reactions, - elimination reactions are divided into three types:

H H 3C H 3C (i) (Elimination unimolecular) reaction, (ii)

1
(Elimination 2

bimolecular) reaction and (iii) (Elimination unimolecular conjugate base)

C O C O C O 1cb

reaction
H H H 3C
(i) (Elimination unimolecular) reaction : Consider the following
Decreasing order of nucleophilic addition in some species. 1

reaction,
O O
|| || CH 3
C 6 H 5 CH 2 COCH 3 CH 3 COCH 3 C6 H 5 C CH 3 C6 H 5 C C6 H 5 CHO
|
CH 3
C H O/
CH 3 C Cl 2 5 CH 2 C C 2 H 5 OH Cl
COCH 3 COCl COOCH 3 CONH 2 COOH |
CH 3 CH 3
(3) Free radical addition reactions : Those reactions which involve
the initial attack by a free radical are known as free radical reactions. (a) Reaction velocity depends only on the concentration of the
Addition of hydrogen bromide to alkenes (say, propylene) in the presence of substrate; thus reaction is unimolecular reaction.
peroxide (radical initiator) follows free radical mechanism. Free radical
Rate [Substrate]
reactions generally take place in non-polar solvents such as CCl 4 , high
temperature, in presence of light or a free radical producing substance like (b) Product formation takes place by the formation of carbocation
as reaction intermediate ( ).
O 2 and peroxides.
(c) Since reaction intermediate is carbocation, rearrangement is
Elimination reactions possible in reaction.
1

Elimination reactions are formally the reverse of addition reactions (d) Reaction is carried out in the presence of polar protic solvent.
and involve the removal of the two groups (Generally, one being a proton)
from one or two carbon atoms of a molecule to form an unsaturated (e) The 1
reaction occurs in two steps,
linkage or centre.
Elimination reaction is given by those compounds which have a
nucleophilic group as leaving group, CH 3 CH 3
| |
Slow step
R R CH 3 C Cl CH 3 C - - - - - Cl CH 3 C CH 3 Cl
| | |
, , , N 2 , N 3 , H 3 O, N R, S CH 3 CH 3 CH 3
(TS 1 )
R R ( RI)
 1026 General Organic Chemistry
In 1
reactions, product formation always takes place by Saytzeff
.. rule.
B H CH 2 C CH 3 B - - - - H - - - -CH 2 - - - - C CH 3
| | In 1cb
reactions, product formation always takes place by
CH 3 CH 3 Hofmann rule.
TS 2

In reactions, product formation takes place by Saytzeff as well

CH 3
2

as Hofmann rule. In almost all reactions product formation take place by

fast
2

BH CH 2 C Saytzeff rule.
CH 3
(ii) (Elimination bimolecular) : Consider the following (3) Examples of - elimination reactions
reaction, (i) is removal of from alkyl halides with
alcoholic or KNH 2 or ter- BuO (Potassium tertiary butoxide) and
Base (B )
CH 3 CH 2 CH 2 Br CH 3 CH CH 2 H Br
an example of - elimination,
(a) Reaction velocity depends only on the concentration of the CH 3 CH 2 X [Link]
H 2C CH 2 ;
substrate and the base used; thus reaction is bimolecular reaction. Rate ( HX ) Ethene
[Substrate] [Base] [Link]
CH 3 CH CH 3 CH 3 CH CH 2
| ( HX )
(b) Since the reaction is a bimolecular reaction, the product Propene

formation will take place by formation of transition state (TS). X

[Link]
(c) Rearrangement does not take place in reaction but in case of CH 3 CH 2 CH CH 3 CH 3 CH CH CH 3
2
| ( HX ) 2 - Butene (Major)
allylic compound rearrangement is possible. X
(d) Reaction is carried out in the presence of polar aprotic solvent. CH 3 CH 2 CH CH 2
1- Butene (Minor)
(e) The 2
reaction occurs in one step,
.. (ii) of alcohol is another example of elimination
B H H B ---- H H reaction. When acids like conc. H 2 SO 4 or H 3 PO4 are used as
| | |
Slow step
CH 3 C C H CH 3 C C H dehydrating agents, the mechanism is . The proton given by acid is taken
| | | 1

H Br H Br up by alcohol.
TS
Dehydration is removal of H 2 O from alcohols,
fast
CH 3 CH CH 2 BH Br
Conc. H 2 SO 4 , 170 C
(2) Orientation in - elimination reactions : If substrate is CH 3 CH 2 OH H 2C CH 2
( H 2 O)
unsymmetrical, then this will give more than one product. Major product of
the reaction can be known by two emperical rules. CH 3 CH 2 CH 2 OH Conc. H 2SO 4 , 170 C
CH 3 CH CH 2
Propan -1 - ol ( H 2O ) Propene
(i) : According to this rule, major product is the most
Dehydration of alcohols is in the order:
substituted alkene major product is obtained by elimination of H from
Tertiary Secondary Primary
that - carbon which has the least number of hydrogen. Product of the (3 ) (2 ) (1 )
reaction in this case is known as Saytzeff product.
2° and 3° alcohol by process and 1° alcohol by 1
process. 2

Cl Alcohols leading to conjugated alkenes are more easily dehydrated than the
|
2
Alc. KOH / alcohols leading to non-conjugated alkenes. CH 2 CH CH CH 3 is
CH 3 CH CH CH 3 CH 3 C CH CH 3 |
| HCl |
1 OH
CH 3 CH
3 easily dehydrated than
Saytzeff p roduct
CH 3 CH 2 CH CH 3 and so
(ii) : According to this rule, major product is always |

least substituted alkene , major product is formed from - carbon which OH

has maximum number of hydrogen. Product of the reaction in this case is
known as Hofmann product. > >
CH 3 Br CH 3
| | |
[Link] /
CH 3 C CH 2 CH CH 3 CH 3 C CH 2 CH CH 2
|
2 1
| (iii) : It is removal of halogens,
CH 3 CH 3 in CH 3 OH , heat
Hofmann product CH 2 CH 2 Zn dust H 2C CH 2
| | (-ZnBr2 ) Ethylene
Br Br
Ethylene bromide
 General Organic Chemistry 1027

(iv) : It is removal of hydrogen, (3) Rearrangement or migration to free radical species (Free radical
Cu , 300 C rearrangement) : Those rearrangement reactions in which the migrating
CH 3 CH CH 3 CH 3 C CH 3
| ( H2 ) || group moves to a free radical centre. Free radical rearrangements are
OH O comparatively rare.
Isopropyl alcohol Acetone
(4) Aromatic rearrangement : Those rearrangement reactions in
Rearrangement reactions which the migrating group moves to aromatic nucleus. Aromatic
The reactions, which involve the migration of an atom or group compounds of the type ( ) undergo rearrangements in the manner
mentioned below,
from one site to another within the molecule (nothing is added from
outside and nothing is eliminated) resulting in a new molecular structure,
are known as rearrangement reactions. The new compound is actually the
structural isomer of the original one.
It is convenient to divide rearrangement reactions into following
types: ()
The element from which group migrates may be nitrogen or
(1) Rearrangement or migration to electron deficient atoms oxygen.
(Nucleophilic rearrangement) : Those rearrangement reactions in which
migrating group is nucleophilic and thus migrates to electron deficient Isomerism
centre which may be carbon, nitrogen and oxygen.
Organic compounds having same molecular formula but differing
Y B: B from each other at least in some physical or chemical properties or both are
| |
Y | | | | known as isomers (Berzelius) and the phenomenon is known as isomerism.
C C C C C C
| | | | The difference in properties of isomers is due to the difference in
X: X X the relative arrangements of various atoms or groups present in their
Bridged or molecules. Isomerism can be classified as follows:
non-classical carbocation
= Nucleophilic species, = Electronegative group, = Another
nucleophile.
(2) Rearrangement or migration to electron rich atoms (Electrophilic
rearrangement) : Those rearrangement reactions in which migrating group
is electrophile and thus migrates to electron rich centre.
Isomerism

Constitutional or structural isomerism Configurational or stereo isomerism

Without referring to space, the isomers differ in the The isomerism arises due to different arrangement of atoms or groups
arrangement of atoms within the molecule is called in space. It deals with the structure of molecules in three dimensions.
structural isomerism. Thus structural isomers have:
Thus stereoisomers have:

Chain Position Ring chain Functional Meta Tauto - Geometrical Optical Conformational
isomerism isomerism isomerism isomerism merism merism isomerism isomerism isomerism

Constitutional or structural isomerism CH 3

|
(1) Chain, nuclear or skeleton isomerism : This type of isomerism CH 3 CH CH 2 CH 3 , CH 3 C CH 3
| |
arises due to the difference in the nature of the carbon chain ( straight CH 3 CH 3
or branched) which forms the nucleus of the molecule. Isopentane Neopentane

Except alkynes chain isomerism is observed when the number of

carbon atoms is four or more than four.
(i) 4 10
: CH 3 CH 2 CH 2 CH 3 , CH 3 CH CH 3 Chain isomers differ in the nature of carbon chain, in the
n Butane |
CH 3 length of carbon chain.
Isobutane The isomers showing chain isomerism belong to the same
homologous series, functional group, class of the compound (Cyclic or
(ii) 5 12
: (Three) CH 3 CH 2 CH 2 CH 2 CH 3 , open) remains unchanged.
n Pentane
Chain and position isomerism cannot be possible together
between two isomeric compounds. If two compounds are chain isomers
then these two will not be positional isomers.
 1028 General Organic Chemistry
(2) Position isomerism : It is due to the difference in the position of O
the substiuent atom or group or an unsaturated linkage in the same carbon
chain. 2 5 2
: C2 H 5 N ; C2 H 5 O N O
Ethyl nitrite
(ii) : CH 3 , CH 3 CH 2 CH Cl 2 ,
O
3 6 2
CCl 2 CH 3 Nitro ethane
2, 2 Dichloro propane, 1,1 Dichloro propane
(gemdihalide) (gemdihalide) (vi) (Primary, secondary and tertiary)
CH 3 C H C H 2 , C H 2 CH 2 C H2 3 9
: CH 3 CH 2 CH 2 NH 2 ;
| | | | Propan -1- amine
Cl Cl Cl Cl
1, 2 Dichloro propane 1, 3 Dichloro propane H
( , -dihalide)
(Vicdihalide) CH 3 CH 2 N
Aldehydes, carboxylic acids (and their derivatives) and cyanides CH 3
do not show position isomerism. N Methyl ethanamine

Monosubstituted alicylic compounds and aromatic compounds CH 3

do not show position isomerism. CH 3 CH CH 3 ; CH 3 CH 2 N
|
Structural isomers which differ in the position of the functional NH 2 CH 3
Propan - 2- amine N , N Dimethyl methanamin e
group are called regiomers. For example, (i) CH 3 CH 2 CH 2 OH
(vii)
(ii) CH 3 CH CH 3
| 2

OH
3

(3) Functional isomerism : This type of isomerism is due to 7 8

;
difference in the nature of functional group present in the isomers. The
following pairs of compounds always form functional isomers with each Benzyl alcohol -Cresol
(viii)
other.
O
||
: CH 3 CH NOH ; CH 3 C NH 2
(i) 2 5

Acetaldoxime Acetamide
: CH 3 CH 2 OH ; H 3 C O CH 3
2 6

Ethyl alcohol Dimethyl ether (4) Ring-chain isomerism : This type of isomerism is due to different
modes of linking of carbon atoms, the isomers possess either open chain
3 8
: CH 3 CH 2 CH 2 OH ; C 2 H 5 O CH 3 or closed chain sturctures.
n propyl alcohol Ethyl methyl ether
H2
4 10
: CH 3 CH 2 CH 2 CH 2 OH ; C
n Butyl alcohol

C2 H 5 O C2 H 5 H 2C CH 2
Diethyl ether 6 12
: | | ;
(ii) H 2C CH 2
O C
|| H2
3 6
: CH 3 CH 2 CHO ; CH 3 C CH 3 ; Cyclohexan e
Propionald ehyde Acetone
CH 2 CH 2
CH 2 CH CH 3 ; CH 2 CH CH 2 OH | CHCH 3
Allylalcohol C H2 CH 2 ; CH 3 CH 2CH 2CH 2CH CH 2
O Methyl cyclopentane 1 Hexene
1, 2 Epoxy propane
Ring chain isomers are always functional isomers.
(iii)
(5) Metamerism : This type of isomerism is due to the difference in
2 4 2
: CH 3 COOH ; HCOOCH 3 the nature of alkyl groups attached to the polyvalent atoms or functional
Aceticacid Methyl formate
group. Metamers always belong to the same homologous series. Compounds
3 6 2
: CH 3 CH 2 COOH ; CH 3 COOCH 3 ; like ethers, thio-ethers ketones, secondary amines, show metamerism.
Propionic acid Methyl acetate
CH 3 C2 H 5
O (i) : C3 H 7 N ; C2 H 5 N
CH 3 CH 3
5 13

||
Dimethyl propyl amine Diethyl methyl amine
CH 3 C HCHO ; CH 3 C CH 2 OH
| 1 Hydroxy propan - 2 - one
OH (ii) 6 15
: C3 H 7 NH C3 H 7 ; C2 H 5 NH C4 H 9
2 Hydroxy propanal Dipropyl amine Butyl ethyl amine

(iv)
: CH 3 CH 2 C CH ; H 2C CH CH CH 2 ; If same polyvalent functional group is there in two or more
4 6

1 Butyne 1, 3 Butadiene organic compounds, then chain or position isomerism is not possible, there
CH 3 C C CH 3 ; H 2C C CH CH 3 will be metamerism
2 Butyne 1, 2 Butadiene (a) CH 3 C CH 2 CH 2 CH 3 ;
||
(v) NO 2 and O N O O
(Pentan 2 one)
 General Organic Chemistry 1029

CH 3 CH 2 C CH 2 CH 3 are metamers and not position isomers. O O

|| || ||
O CH 3 C CH 2 R CH 3 C CH R
(Pentan 3 one) Keto form

(b) CH 3 C CH 2 CH 2 CH 3 ;
|| O OH
| |
O H 2O
(Pentan 2 one) CH 3 C CH R CH 3 C CH R
OH (Enol)
CH 3 C C H CH 3 are metamers and not chain isomers. (c) Triad system containing nitrogen : Examples
|| | Nitrous acid exists in 2 forms
O CH 3
(3 - Methylbutan - 2 - one) O
H O N O H N
Alkenes does not show metamerism. nitrite form O
Nitro form
(6) Tautomerism
(i) The type of isomerism in which a substance exist in two readily Nitro acinitro system
interconvertible different structures leading to dynamic equilibrium is
known as tautomerism and the different forms are called tautomers (or O O
CH 3 CH 2 N CH 3 CH N
tautomerides). O OH
nitro form (i) Aci form (ii)
The term tautomerism (Greek: = same; = parts) was
used by Laar in 1885 to describe the phenomenon of a substance reacting (iii)
chemically according to two possible structures. (a) Tautomerism (cationotropy) is caused by the oscillation of
(ii) It is caused by the wandering of hydrogen atom between two hydrogen atom between two polyvalent atoms present in the molecule. The
polyvalent atoms. It is also known as Desmotropism (Desmos = bond and change is accompanied by the necessary rearrangement of single and double
tropos = turn). If the hydrogen atom oscillates between two polyvalent bonds.
atoms linked together, the system is a dyad and if the hydrogen atom (b) It is a reversible intramolecular change.
travels from first to third atom in a chain, the system is a triad. (c) The tautomeric forms remain in dynamic equilibrium. Hence,
their separation is a bit difficult. Although their separation can be done by
(a) : Hydrocyanic acid is an example of dyad system in special methods, yet they form a separate series of stable derivatives.
which hydrogen atom oscillates between carbon and nitrogen (d) The two tautomeric forms differ in their stability. The less
atoms. H C N C N H stable form is called the labile form. The relative proportion of two forms
varies from compound to compound and also with temperature, solvent etc.
(b) The change of one form into another is also catalysed by acids and bases.
: Polyvalent atoms are oxygen and two carbon (e) Tautomers are in dynamic equilibrium with each other and
atoms.
interconvertible ( ).
(f) Two tautomers have different functional groups.
O H OH (g) Tautomerism has no effect on bond length.
|| | | (h) Tautomerism has no contribution in stabilising the molecule
C C C C and does not lower its energy.
| | (i) Tautomerism may occur in planar or nonplanar molecules.
(Keto) (Enol)
Keto=enol tautomerism is exhibited only by such aldehydes and
ketones which contain at least one -hydrogen.
O OH For example
|| |
CH 3 C CH 2 COOC 2 H 5 CH 3 C CHCOOC 2 H 5 CH 3 CHO, CH 3 CH 2 CHO, CH 3 COCH 2 COCH 3 etc,.
Keto form (92.1%) Enol form (7.9%)
Tautomerism is not possible in benzaldehyde (C 6 H 5 CHO) ,
Acetoacetic ester gives certain reactions showing the presence of
keto group (Reactions with HCN , H 2 NOH , H 2 NNHC 6 H 5 , ) and benzophenone (C6 H 5 COC 6 H 5 ) , tri methyl acetaldehyde,
certain reactions showing the presence of enolic group (Reactions with (CH 3 )3 C CHO and chloral CCl 3 CHO as they do not have
Na, CH 3 COCl , NH 3 , PCl5 , Br2 water and colour with neutral FeCl3 , H.
). Number of structural isomers
Enolisation is in order
Molecular formula Number of isomers
CH 3 COCH 3 CH 3 COCH 2 COOC 2 H 5 C 6 H 5 COCH 2 COOC 2 H 5
Alkanes
CH 3 COCH 2 COCH 3 CH 3 COCH 2 CHO C4 H10 Two
O Three
|| C5 H12
Acid catalysed conversion CH 3 C CH 2 R
Keto C6 H14 Five
OH OH C7 H16 Nine
| |
H
CH 3 C CH R CH 3 C CH R C8 H18 Eighteen
| (Enol form)
H C9 H 20 Thirty five
(Intermediate)
Base catalysed conversion
 1030 General Organic Chemistry

C10 H 22 Seventy five The compounds which have same molecular formula but differ in
the relative spatial arrangement of atoms or groups in space are known as
Alkenes and cycloalkanes
geometrical isomers and the phenomenon is known as geometrical
C3 H 6 Two (One alkene + one cycloalkane)
isomerism. The isomer in which same groups or atoms are on the same side
C4 H 8 Six (Four alkene + 2 - cycloalkane) of the double bond is known as form and the isomer in which same
groups or atoms are on the opposite side is called -isomer.
C 5 H 10 Nine (Five alkenes + 4 cycloalkanes)
Alkynes
C3 H 4 Two H C COOH H
C COOH
|| ||
C4 H 6 Six H C COOH HOOC C H
Maleic acid (cis) Fumaric acid (trans)
Monohalides
C3 H 7 X Two H3C C COOH H3C
C COOH
|| ||
C4 H 9 X Four H C COOH HOOC C H
Citraconic acid (cis- isomer) Mesaconic acid (trans isomer)
C5 H11 X Eight
(1) Conditions for geometrical isomerism : Compound will show
Dihalides geometrical isomerism if it fulfils the following two conditions
C2 H 4 X 2 Two (i) There should be frozen rotation about two adjacent atoms in the
molecule.
C3 H 6 X 2 Four
(a) C C frozen rotation about carbon, carbon double
C4 H 8 X 2 Nine bond in alkenes.
C5 H10 X 2 Twenty one

Two (One alcohol and one ether) (b) frozen rotation about carbon, carbon single bond in
C2 H 6O cycloalkanes.
C3 H 8 O Three (Two alcohols and one ether) (c) C N frozen rotation about carbon, nitrogen double
bond in oxime and imine.
C 4 H10 O Seven (Four alcohols and three ethers)
(ii) Both substituents on each carbon should be different about
C 5 H 12 O Fourteen (Eight alcohols and six ethers) which rotation is frozen.
If these two conditions are fulfilled, then compound will show
Aldehydes and ketones geometrical isomerism.
C3 H 6O Two (One aldehyde and one ketone) The compounds of the following type will not show geometrical
isomerism.
C4 H 8 O Three (Two aldehydes and one ketone)
a C a x C aa C a
C5 H10 O Seven (Four aldehydes and three ketone) || || ||
x C y a C a x C x
Monocarboxylic acids
and esters (2) Distinction between - and - isomers
Two (One acid and one ester) (i) : Generally, the -isomer ( maleic
C2 H 4 O2 acid) cyclises on heating to form the corresponding anhydride while the
C 3 H 6 O2 Three (One acid and two esters) -isomer does not form its anhydride.

C 4 H 8 O2 Six (Two acids and four esters) H C COOH H C CO

Heat
Thirteen (Four acids and nine esters) || || O
C5 H10 O2
H C COOH H C CO
Maleicacid(cis) Maleic anhydride
Aliphatic amines
C2 H7 N Two (One 1°-amine and one 2°-amine) Note that the two reacting groups ( are near to each
other.
C3 H 9 N Four (Two 1°-amines, one 2°-amine and one
3°-amine) H
C COOH Heat
Eight (Four 1°-amines, three 2°-amines and || No anhydride
C 4 H 11 N
one 3°-amines) HOOC C H
Fumaric acid (trans)
Aromatic compounds
Four Note that the two reacting groups ( are quite apart
C8 H10 from each other, hence cyclisation is not possible.
C 9 H 12 Nine (ii) (Oxidation by means of KMnO4 ,OsO4 or
C7 H 8 O Five H 2O2 in presence of OsO4 ) : Oxidation (Hydroxylation) of alkenes by
means of these reagents proceeds in the -manner. Thus the two
geometrical isomers of an alkene leads to different products by these
Geometrical or cis-trans isomerism reagents. For example,
 General Organic Chemistry 1031

H C COOH OH
KMnO 4 H COOH
||
H COOH
H C COOH OH
Maleicacid (cis) meso Tartaricacid

OH
H C COOH KMnO 4 H COOH
||
HOOC C H HOOC H
Fumaric acid (trans )
OH
( ) Tartaric acid

OH
HOOC H
H COOH
OH
( ) Tartaric acid

(iii) : The isomer of a

symmetrical alkene (Alkenes in which both the carbon atoms have similar
groups) has a definite dipole moment, while the isomer has either
zero dipole moment or less dipole moment than the isomer. For
example, 1,2-dichloroethylene and butene-2.
H C Cl H C Cl H C CH 3 H C CH 3
|| || || ||
H C Cl Cl C H H C CH 3 CH 3 C H
cis Dichloroethylene trans Dichloroethylene cis Butene 2 trans Butene 2
( 1 .9 D) ( 0 .0 D) ( 0 .0 D)

In isomer of the symmetrical alkenes, the effect produced in

one half of the molecule is cancelled by that in the other half of the
molecule.
In case of unsymmetrical alkenes, the isomer has higher dipole
moment than the corresponding isomer.
 General Organic Chemistry 1033

For Example, The following rules are followed for deciding the precedence order
of the atoms or groups;
H 3C C Cl CH 3 C Cl
|| || (i) Higher priority is assigned to the atoms of higher atomic
CH 3 CH 2 C Cl Cl C CH 2 CH 3 number. For example, the order of preference in the following atoms,
cis 2, 3 Dichloropentene 2 trans 2, 3 Dichloropentene 2 H, Cl, I, Br is : (at. no. 53)> (at. no. 35)> (at. no. 17)> (at. no. 1).
(High dipole moment) ( Less dipolemoment )
(ii) If isotopes of the same element are attached, the isotope with
Similar is the case with hexene-2. higher mass number is given higher order of preference. For example,
2
H3C CH 2 CH 2 CH 3 deuterium 1D is assigned higher priority in comparison to hydrogen
C C
H H 1
cis Hexene 2(more polar) 1H .
(iii) In the groups, the order of preference is also decided on the
H CH 2 CH 2 CH 3 basis of atomic number of first atom of the group. For example, in the
C C
CH 3 H following set,
trans Hexene 2(Less polar)
Cl, OH, COOH , NH CH 3 , SO 3 H .
(iv) : ( ) The isomer of a The order of the precedence is :
compound has higher boiling point due to higher polarity, higher density Cl S O3 H OH N HCH 3 C OOH
and higher refractive index than the corresponding isomer (
( at.no17) ([Link].16) ([Link].8) ([Link].7) ([Link]. 6)
).
When the order of preference of the groups cannot be settled on
CH 3 C H CH 3 C H the first atom, the second atom or the subsequent atoms in the groups are
|| ||
CH 3 C H H C CH 3 considered. For example, in the set CH 2 CH 3 , CH 3 , COOH, the
cis 2 Butene trans 2 Butene
b.p 4 C 1 C order cannot be decided on the basis of first atom as it is same in all the
m.p. 139 C 106 C
groups. However, in CH 2 CH 3 , the second atom is carbon, in
H C Cl H C Cl CH 3 , the second atom is hydrogen while in COOH, the second atom
|| ||
H C Cl Cl C H is oxygen. Hence, the order of preference is :
cis 1, 2 Dichloroethene trans 1, 2 Dichloroethene
60 C
80 C
48 C
50 C
C O OH CH 2 C H 3 C H3
([Link].8) ([Link].6)
(b) The -isomer has higher melting point than the -isomer ([Link].1)
due to symmetrical nature and more close packing of the -isomer. (iv) A doubly or triply bonded atom is considered equivalent to two
(v) : -isomer is more stable than isomer due to or three such atoms. For example,
symmetrical structure.
The group C O is equal to C O and the group C N
|

. O
isomers are configurational isomers but not mirror N
|
images, hence and isomers are always .
is equal to C N .
Non-terminal alkenes with the same atoms or groups either on |

one or both the carbon atoms of the double bond such as 2-methyl-2- N
butene, 2,3-dimethyl 2 butene etc. do not show geometrical isomerism. (4) Number of geometrical isomers in polyenes
(3) and system of nomenclature : (i) When a compound has double bonds and ends of a polyene
cannot be used if four different atoms or groups are attached to the carbon
are different, the number of geometrical isomers 2n
atoms of a double bond.
C6 H5 CH CH CH CH CH CH CH CH Cl
a d
C C The given compound has four double bonds and the two ends are
b e
different (One is C6 H 5 and other is ). Therefore, number of geometrical
In such cases, and system of nomenclature is used. This system
is based on a priority system developed by and . isomers 2n 24 16 .
In this system, the two atoms or groups attached to each of the (ii) When the ends of polyene are same.
doubly bonded carbon are put in order of preference on the basis of Case I : When number of double bonds (= ) is even then the
sequence rules.
number of geometrical isomers 2n 1 2[(n / 2) 1]
The symbol is assigned to an isomer in which the atoms or
groups of higher preference are on the opposite side ( from German word Cl CH CH CH CH CH CH CH CH Cl
n 4 , even
= across or opposite).
Th Number of geometrical isomers 2n 1 2(n / 2) 1
23 21
groups of higher preference are on the same side ( from German word, 8 2 10 .
= together). Case II : When number of double bonds (= ) is odd.
n 1
1 2 1 1 1
C C C C Number of geometrical isomers 2 n 1 2 2
2 1 2 2
E isomer Z isomer C6 H 6 CH CH CH CH CH CH C6 H 5
(n 3, odd )
1 signifies higher preference and 2 signifies lower preference.
Preference Number of geometrical isomers 22 22 1
22 21
form. However, there are many exceptions. 4 2 6.
(5) Geometrical Isomerism in nitrogen compounds
 1034 General Organic Chemistry

(i) Geometrical isomerism due to C N bond. The optical activity was first observed in organic substances like
The important class of compounds exhibiting geometrical isomerism quartz, rock-crystals and crystals of potassium chlorate (KClO3 ) ,
due to C N bond are oximes, nitrones, hydrazones and potassium bromate (KBrO3 ) and sodium periodate (NaIO4 ) .
semicarbazones. But the most common compound is oxime.
Oximes : In aldoxime, when hydrogen and hydroxyl groups are on (2) Measurement of optical activity : The measurement of optical
the same side, the isomer is known as syn. (analogous to ) and when activity is done in terms of
these groups are on the opposite side, the isomer is known as anti
C6 H 5 C H C6 H 5 C H
(analogous to ) || ||
N OH HO N t C obs
Syn - benzaldoxime Anti benzaldoxime Specific rotation, wavelength
l C
In ketoximes the prefixes syn and anti indicate which group of
ketoxime is syn or anti to hydroxyl group. For example: Where obs is the rotation observed, is the length of the solution
CH 3 C C2 H 5 in decimeters and is the number of grams in 1 of solution. The specific
|| this compound will be named as; rotation of the sucrose at 20° using sodium light ( -line, =5893 ) is
N OH
20 C
+66.5° and is denoted as: D 66.5 C(C 0 .02 g / mL water)
(a) Syn-ethyl methyl ketoxime HO and C2 H 5 are syn or
(b) Anti-methyl ethyl ketoxime HO and C 2 H 5 are anti. + sign indicates the rotation in clockwise direction.
Similarly consider the following structure (3) On the basis of the study of optical activity, the various organic
C 2 H 5 C CH 3 compounds were divided into four types :
|| (i) The optical isomer which rotates the plane of the polarised light
N OH to the right (Clockwise) is known as dextrorotatory isomer (Latin: =
Syn methyl ethyl ketoxime
or Anti ethyl methyl ketoxime ) or form or indicated by + sign.
(ii) Geometrical isomerism due to = bond. (ii) The optical isomer which rotates the plane of the polarised light
C6 H 5 N C6 H 5 N to the left (Anticlockwise) is known as laevorotatory isomer (Latin; =
|| ||
) or -form or indicated by sign.
C H N N C6 H 5
6 5
Syn - azobenzene
Anti azobenzene (iii) The optical powers of the above two isomers are equal in
(6) Geometrical isomerism show by cumulatrienes : Cumulatrienes magnitude but opposite in sign. An equimolar mixture of the two forms,
(Trienes with three adjacent double bonds) show only geometric isomerism. therefore, will be optically inactive due to external compensation. This
This is because their molecule is planar, as such the terminal CH 3 mixture is termed as racemic mixture or form or ( ) mixture.
groups and atoms lie in the same plane. Therefore, in this case their (iv) Optical isomer with a plane of symmetry is called form. It
planar structure can exist in two diastereoisomeric forms, and is optically inactive due to internal compensation, the rotation caused by
but no enantiomeric forms are possible. upper half part of molecule is neutralised by lower half part of molecule.
H3C CH 3 (4) Chirality, (i) : A molecule (or an object) is said to be
C C C C chiral or dissymmetric, if it is does not possess any element of symmetry
H H
cis Hexa 2, 3 , 4 triene and not superimposable on its mirror image and this property of the
molecule to show non-superimposability is called chirality.
H3C H
C C C C On the other hand, a molecule (or an object) which is
H CH 3 superimposable on its mirror image is called achiral (non-dissymmetric or
trans Hexa 2 , 3 , 4 triene
symmetric).
(7) Geometrical isomerism in cycloalkanes : Disubstituted
cycloalkanes show geometrical isomerism. To understand the term chiral and achiral let us consider the

Mirror Mirror
3

1,2-cyclohexanediol
1,2-dimethylcyc 1,2-cyclopent
lopropane anediol
Certain compounds show geometrical as well optical isomerism. Non-superimposable Superimposable
Such type of isomerism is known as geometrical enantiomerism. (Chiral or dissymmetric) (Achiral or non-dissymmetric)
(ii) : There are three elements of symmetry,
Optical isomerism
(a) : It may be defined as a plane which divides a
(1) Compounds having similar physical and chemical properties but molecule in two equal parts that are related to each other as an object and
they have the ability to rotate the plane of polarised light either to the right mirror image. e
(Clockwise) or to the left (Anticlockwise) are termed as optically active or
optical isomers and the property is called optical activity or optical
isomerism.
 General Organic Chemistry 1035

COOH a CH 3
| | |

H C OH d C* b HO C* H
| |
| c COOH
Plane of symmetry
H C OH Lacticacid

| Carbons that can be chirality centres are sp 3 -hybridised

COOH
carbons; sp 2 and sp -hybridised carbons cannot be chiral carbons because
(b) : It may be defined as a point in the they cannot have four group attached to them.
molecule through which if a line is drawn in one direction and extended to
Isotopes of an atom behave as different group in
equal distance in opposite direction, it meets another similar group or atom,
stereoisomerism.
Centre of symmetry D H1
CH 3 CH 3 CH 3 H
| |
| NH CO | | NH CO |
H C* T Cl 35 C* Cl 37
C C and C C
| |
| CO NH | | CO NH |
Br H2
H H H CH 3 Lactic acid
cis Dimethyl diketo piperazine Trans Dimethyl diketo piperazine
Carbon of the following groups will not be a chiral carbon
Since form contains a centre of symmetry, it is optically
O
inactive.
||
(c) : A molecule is said to possess an CH 3 , CH 2 OH, CHX 2 , CHO, C Z
alternating axis of symmetry if an oriention indistinguishable from the
Maleic acid (HOOC CH CH COOH ) show
original is obtained when molecule is rotated Q degree around an axis
geometrical isomerism while malic acid
passing through the molecule and the rotated molecule is reflected in a
mirror that is perpendicular to the axis of rotation in step (I). (HOOC CH 2 CHOH COOH ) show optical isomerism.
(5) Calculation of number of optical isomers
(i) If molecule is not divisible into two identical halves and molecule
has n asymmetric carbon atoms then

Number of optically active forms 2n a

Number of enantiomeric pair a/2

(iii) Number of racemic mixture a/2

(a) If any symmetry is present in the Number of form 0

molecule then molecule will be symmetric molecule. (ii) If molecule is divisible into two identical halves, then the
(b) : Molecule will be a dissymmetric number of configurational isomers depends on the number of asymmetric
molecule if it has no plane of symmetry, no centre of symmetry and no carbon atoms.
alternating axis of symmetry. Case I : When compound has even number of carbon atoms, i.e.,
(c) : Dissymmetric molecule having at least n 2, 4, 8, 10, 12, ..... :
one asymmetric carbon is known as asymmetric molecule. All asymmetric
molecules are also dissymmetric molecules but the reverse is not necessarily (i) Number of optically by active forms a 2n 1

true. (ii) Number of enantiomeric pairs a/2

COOH (iii) Number of racemic mixture a/2
| CHO
(iv) Number of forms m 2(n / 2) 1
H C OH |
(v) Total number of configurational isomers a m
| H C OH
Case II : When compound has odd number of carbon atoms,
H C OH | n 3, 5, 7, 9, 11, ...... :
| CH 3
C6 H 5 No plane of symmetry (i) Number of optically active forms a 2n 1
2(n 1) / 2

No plane of symmetry Dissymmetric molecule (ii) Number of enantiomeric pairs a/2

Dissymmetric molecule Asymmetric molecule (iii) Number of racemic mixutre a/2
Asymmetric molecule (iv) Number of forms m 2(n 1) / 2
(iv) : A carbon bonded to four (v) Total number of configurational isomers a m
different groups is called a chiral carbon or a chirality centre. The chirality (6) Optical activity of compounds containing one asymmetric
centre is indicated by asterisk. carbon
Examples :
 1036 General Organic Chemistry

Number of optical isomers a 22 1

2
CH 3 C HOH COOH ; CH 3 C HOH CHO
Lacticacid 0
Number of meso forms m 2 1

CH 2 OH C HOH CHO ; C6 H 5 C HCl CH 3 Total number of configurational isomers 3

Glyceraldehyde 1 - chloro -1 - phenyletha ne
(8) Optical activity in compounds containing no assymmetric carbon
Any molecule having one asymmetric carbon atom exists in two : Although the largest number of known optically active compounds are
configurational isomers which are nonsuperimposible mirror images. optically active due to the presence of chiral carbon atom, some compounds
COOH COOH are also known which do not possess any chiral carbon atom, but on the
whole their molecules are chiral (such molecules were earlierly called
| | dissymmetric); hence they are optically active. Various types of compounds
H C OH HO C H belonging to this group are allenes, alkylidene cycloalkanes, spiro
| | compounds (spirans) and properly substituted biphenyls.
CH 3 CH 3 (i) : Allenes are the organic compounds of the following
(I) (II) general formulae.
(I) and (II) have the same molecular formula, the same structure C C C
but different configurations, hence (I) and (II) are known as configurational
isomers. (I) and (II) are nonsuperimposable mirror images, hence (I) and Allenes exhibit optical isomerism provided the two groups attached
(II) are optical isomers. Configurational isomers which are to each terminal carbon atom are different,
nonsuperimposable mirror images are known as enantiomers. Thus (I) and a a a x
(II) are enantiomers. Pair of (I) and (II) is known as enantiomeric pair.
C C C or C C C
(i) : All chemical and physical properties
b b b y
of enantiomers are same except two physical properties.
: One enantiomer rotates light to the right and the (ii) : When one or
other by an equal magnitude to the left direction. both of the double bonds in allenes are replaced by one and two rings, the
resulting systems are respectively known as alkylidene cycloalkanes and
(ii) : An equimolar mixture of two enantiomers is spirans.
called a racemic mixture (or racemate, form, ( ) form or racemic
H3C H
modification). Such a mixture is optically inactive because the two
enantiomers rotate the plane polarised light equally in opposite directions C
and canc external H COOH
compensation. 1-Methylcyclohexylidene-4- acetic acid
(Alkylidene cycloalkane)
Racemic mixture can be separated into (+) and ( ) forms. The a CH 2 CH 2 a
separation is known as resolution. C C C
The conversion of (+) or ( ) form of the compound into a b CH 2 CH 2 b
racemic mixture is called racemisation. It can be caused by heat, light or by Spirans
chemical reagents.
(iii) : Suitably substituted diphenyl compounds are also
Racemic mixture is designated as being ( ) or ( ). devoid of individual chiral carbon atom, but the molecules are chiral due to
(7) Optical activity of compounds containing two asymmetric restricted rotation around the single bond between the two benzene nuclei
carbon and hence they must exist in two non-superimposable mirror images of
each other.
Case I : When molecule is not divisible into two identical halves. and the
The number of optical isomers possible in this case is four stereoisomers are known and atropisomers. Examples
(a 2 2 4 ) . Further there will be two pairs of enantiomers and two 2

racemic modifications. In practice also it is found to be so.

Configurational isomers which are not mirror images are known as
diastereomers.
Properties of Diastereomers : Diastereomers have different physical The above discussion leads to the conclusion that the
properties, melting and boiling points, refractive indices, solubilities in
different solvents, crystalline structures and specific rotations. Because of and not the mere presence of a chiral centre. However, it may be
differences in solubility they often can be separated from each other by noted that the
fractional crystallisation; because of slight differences in molecular shape
and polarity, they often can be separated by chromatography. (9) Fischer projection formulae : The arrangement of the atoms or
Diastereomers have different chemical properties towards both groups in space that characterises a stereoisomer is called its configuration.
chiral and achiral reagents. Neither any two diastereomers nor their Emil Fischer (1891) provided an easy method to represent the three
transition states are mirror images of each other and so will not necessarily dimensional formulae of various organic molecules on paper.
have the same energies. However, since the diastereomers have the same
functional groups, their chemical properties are not very dissimilar.
Case II : .
 General Organic Chemistry 1037

By convention, the following points are followed in writing the out of six substituents on two asymmetric carbons, at least two
Fischer formula. should be same.
(i) The carbon chain of the compound is arranged vertically, with When two like groups in Fischer projection formula are drawn on
the most oxidised carbon at the top. the same side of the vertical line, the isomer is called form; if these
(ii) The asymmetric carbon atom is in the paper plane and is are placed on the opposite sides, the isomer is said to be form.
represented at the interaction of crossed lines.
R CH 3 CH 3
Asymmetric
Carbon atom | | |
a C b H C Cl H C Cl
| | |
c C b H C Br Br C H
| | |
R C6 H 5 C6 H 5
Erythro form Erythro form Threo form
(iii) Vertical lines are used to represent bonds going away from the
observer, groups attached to the vertical lines are understood to be (c) (Absolute configuration)
present behind the plane of the paper. The order of arrangement of four groups around a chiral carbon
(iv) Horizontal lines represent bonds coming towards the observer, (stereocentre) atom is called the absolute configuration around that atom.
groups attached to the horizontal lines are understood to be present System which indicates the absolute configuration was given by three
above the plane of the paper. chemists R.S. Cahn, C.K. Ingold and V. Prelog. This system is known as (R)
and (S) system or the Cahn-Ingold Prelog system. The letter (R) comes
(10) Name of optical isomers : Following three nomenclatures are from the latin rectus (means right) while (S) comes from the latin sinister
used for optically active compounds, (means left). Any chiral carbon atom has either a (R) configuration or a (S)
(i) : This nomenclature is mainly used configuration. Therefore, one enantiomer is (R) and other is (S). A racemic
in sugar chemistry or optically active polyhydroxy carbonyl compounds. This mixture may be designated (R) (S), meaning a mixture of the two. (R) (S)
nomenclature was given by Emil Fischer to designate the configurations of nomenclature is assigned as follows :
various sugars relative to the enantiomeric (+) and ( ) glucose as reference.
Step I : By a set of sequence rules given below the atoms or groups
All sugars whose Fischer projection formula shows the group connected to the chiral carbon are assigned a priority sequence.
on the chiral carbon atom adjacent to the terminal CH 2 OH group on the Sequence Rules for Order of Priority
right hand side belong to the D -series. Similarly if OH is on the left
Rule 1 : If all four atoms directly attached to the chiral carbon are
hand side, then the sugars belong to the L -series. different, priority depends on their atomic number. The atom having
| | highest atomic number gets the highest priority, (1). The atom with the
H C OH HO C H lowest atomic number is given the lowest priority, (2), the group with
| | next higher atomic number is given the next higher priority (3) and so on.
CH 2 OH CH 2 OH Thus,
D series L series
Cl 3
Examples :
| |
CHO CHO
| | F C I 4 C 1
H C OH HO C H | |
| |
CH 2 OH CH 2 OH Br 2
D(d ) glyceraldehyde
or
L (l ) glyceraldehyde
or
F Cl Br I
D( ) glyceraldehyde L ( ) glyceraldehyde Increasing atomic number
It must be noted that there is no relation between the sign of 4 3 2 1
rotation (+, or ) and the configuration ( and ) of an enantiomer. Increasing priority
Any compound that can be prepared from, or converted into COOH 4
(+) glyceraldehyde will belong to -series and similarly any compound that | |
can be prepared from, or converted into ( ) glyceraldehyde will belong to H2 N C Br 3 C 1
the -series. | |
This nomenclature is also used in -amino acids. OH 2
C N O Br
(ii) : This nomenclature Increasing prioritywith atomic number
is used only in those compounds which have
Rule 2 : If two or more than two isotopes of the same element is
(a) Only two chiral carbons and present, the isotope of higher atomic mass receives the higher
(b) The following structure, R Cab Cbc R priority.
1 2 3
1 H 1H 1H

Increasing priority
3 2 1
 1038 General Organic Chemistry

F 3
| |
Br C H 1 C 4
| |
Cl 2
Rule 3 : If two or more of the atoms directly bonded to the chiral In this Fischer projection the least priority number is not at the
carbon are identical, the atomic number of the next atoms are used for bottom of the plane.
priority assignment. If these atoms also have identical atoms attached to In such cases the Fischer projection formula of the compound is
them, priority is determined at the first point of difference along the chain. converted into another equivalent projection formula in such a manner that
The atom that has attached to it an atom of higher priority has the higher atom or group having the lowest priority is placed vertically downward.
priority. This may be done by two interchanges between four priority numbers. The
first interchange involves the two priority numbers, one is the least priority
I 2 H and Br
|
number and other is the priority number which is present at the bottom of
I H 2C H2 C C C H2 Br the plane. In the above case first interchange will takes place between 2 and
| 4.
2 H and C CH 2 CH 2 CH 3
3 3
| First interchange |
2 H and C
1 C 4 1 C 2
| Between 2 and 4 |
2 4
In this example the atoms connected directly to the chiral carbon
(A) (B)
are iodine and three carbons. Iodine has the highest priority. Connected, to
the three carbons are 2 and , 2 and and 2 and Bromine has the First interchange of two groups at the chiral centre inverts the
configuration and this gives enantiomer of the original compound. Thus ( )
highest atomic number among and and thus CH 2 Br has highest
and ( ) are enantiomer. The second interchange involves the remaining two
priority among these three groups ( priority no. 2).The remaining two groups.
carbons are still identical ( and 2 ) connected to the second carbons of 3 1
these groups are 2 and and 2 and Iodine has highest priority among | Second interchange |
these atoms, so that CH 2 CH 2 I is next in the priority list and 1 C 2 3 C 2
| between remaining |
CH 2 CH 2 CH 3 has the last priority. 4 groups, 1 and 3 4
(B) (A)
I 1 Arrangement of
| 1, 2 and 3 are
I CH 2 CH 2 C CH 2 Br 3 2 clockwise, hence configuration is
|
H O
CHO C
CH 2 CH 2 CH 3 4 | | O
H C OH H C OH
Rule 4 : If a double or a triple bond is linked to chiral centre the | |
involved atoms are duplicated or triplicated respectively. CH 2OH CH 2OH
D-glyceraldehyde
O N O O 2 2
| | || | | First interchange |
C O C O; C N C N; C OH C OH 4 C 1 3 C 1
| | | |
| Between 3 and 4 |
N O 4
3
1
By this rule, we obtained the following priority sequence : Second interchange
3 2
CH CR 2 , CN , CH 2 OH, CHO, CO, COOH Between 1 and 2
4

Increasing priority
Step 2 : The molecule is then visualised so that the group of lowest Clockwise
CHO 2 configuration
priority (4) is directed away from the observes (At this position the lowest | 1
| (i) First interchange between 3 and 4
priority is at the bottom of the plane). The remaining three groups are in a HO C H
| 1 C 4 2 32
plane facing the observer. If the eye travels clockwise as we look from the | (ii) Sec. interchange between 1and 2
CH 2OH
group of highest priority to the groups of second and third priority ( L -Glyceraldehyde
3 4
1 2 3 with respect to 4) the configuration is designated as . If
Anticlockwise
arrangement of groups is in anticlocwise direction, the configuration is
designated as configuration
Glyceraldehyde (For example) has one asymmetric carbon, hence it has
For example:
two configurational isomers (I) and (II).
2 2 CHO CHO
| | | |
1 C 3 3 C 1 H C OH HO C H
| | | |

4 4 CH 2 OH CH 2 OH
( R ) glyceraldehyde (S ) glyceral dehyde
Clockwise arrangement of Anticlockwise arrangement of (I) (II)
1 , 2 and 3 1 , 2 and 3 One can draw a number other configurations for glyceraldehyde but
Let us apply the whole sequence to bromochlorofluoro methane. each of them will be a repetition of either (I) or (II). In this connection it is
 General Organic Chemistry 1039

important to note that if two projection formulae differ by an odd number Conformational isomerism
they are different. But if the two differ by an even number of interchanges (1) Definition : The different arrangement of atoms in a molecule
which can be obtained due to rotation about carbon-carbon single bond are
For example : called conformational isomers (conformers) or rotational isomers
CHO (rotamers). This type of isomerism is found in alkanes and cycloalkanes and
CHO
|
H , CH 2 OH
|
Second interchange
their substituted derivatives.
H C OH CH 2 OH C H
| First interchange | between OH , CHO
It may be noted that rotation around a C C sigma bond is not
CH 2 OH H
(I) ( II) completely free. It is in fact hindered by an energy barrier of 1 to 20 1

OH in different bonds. There is a possibility of weak repulsive interactions

|
Third intrerchange
between the bonds or electron pairs of the bonds on adjacent carbon atoms.
CH 2 OH C CHO Such type of repulsive interaction is known as torsional strain.
| CH 2 OH , OH
H (2) Difference between conformation and configuration : The term
( III) conformation should not be confused with the
CH 2 OH CH 2 OH
| |
Fourth interchange
HO C CHO HO C H
| H , CHO |
H CHO .
( IV ) (V )
(3) Representation of conformations : Conformers can be
Thus ( ), ( ) and ( ) are identical. Similarly ( ) and ( ) are represented in two simple ways. These are : (i) Saw horse representation
identical. and (ii) Newman projection
(11) Resolution of racemic modifications : The separation of racemic (i) : In this projection, the molecule is
mixture into its enantiomers is known as resolution. viewed along the axis of the model from an oblique angle. The central
Group reacts with group to give new group carbon-carbon bond ( C C ) is draw as a straight line slightly tilted to
right for the sake of clarity. The front carbon is shown as the lower left
(12) Asymmetric synthesis and Walden inversion hand carbon and the rear carbon is shown as the upper right hand carbon.
(i) : The synthesis of an optically active The three bonds around each carbon atom (C H in ethane or C C in
compound (asymmetric) from a symmetrical molecule (having no higher alkanes) are shown by three lines.
asymmetric carbon) without resolution to form (+) or ( ) isomer directly is
termed asymmetric synthesis. For example the reduction of pyruvic acid
O Back carbon
||
(CH 3 C COOH ) in presence of nickel catalyst gives ( ) lactic acid
(racemic mixture). On the other hand, pyruvic acid is reduced to ( ) lactic Back carbon
acid only by yeast.
CH 3 CH 3 Front carbon
| | Front carbon
2H
H C OH H C H
' Ni' | |
COOH COOH
CH 3 ( ) Lactic acid ( ) Lactic acid
|
Saw horse
(ii) representation : This is a Newman projection
simple method to represent the
Reduction mixture
C O conformations. In this method, the molecule is viewed from the front along
|
COOH the carbon-carbon bond axis. The two carbon atoms forming the -bond
(Pyruvic acid)
CH 3
(2 - Keto propanoic acid) | are represented by two circles; one behind the other so that only the front
2H
HO C H carbon is seen. The front carbon atom is shown by a point whereas the
Yeast |
carbon further from the eye is represented by the circle. Therefore, the
COOH
( ) Lactic acid C H bonds of the front carbon are depicted from the centre of the
(ii) : The conversion of (+) form into ( ) form and circle while C H bonds of the back carbon are drawn from the
vice-versa is called Walden inversion. When an atom or group directly circumference of the circle at an angle of 120° to each other.
linked to an asymmetric carbon atom is replaced; the configuration of the (4) Conformation in alkanes
new compound may be opposite to (inverse) that of the original, (i) : When one of the carbon atom is kept
CH 3 CH 3 COOH fixed and other is rotated about C C bond an infinite numbers of
|
PCl5
|
AgOH
| isomers are possible. Out of all the conformations for ethane, only two
H C OH Cl C H HO C H
| | | extreme conformations are important and these are:
CH 2 COOH CH 2 COOH CH 2 COOH
( ) Malic acid ( ) Chloro succinic acid ( ) Malic acid
(a) Staggered conformation
(b) Eclipsed conformation
COOH COOH
| | 60°
PCl5 AgOH
H C Cl H C OH
| | 60°
CH 2COOH CH 2 COOH 60°
( ) Chloro succinic acid ( ) Malic acid

60° Eclipsed conformation

Staggered
conformation
 1040 General Organic Chemistry
(i) : Compounds with three and four
membered rings are not as stable as compounds with five or six membered
Staggered conformation of ethane is more stable than eclipsed. rings.
(ii) : The next higher member in alkane The German chemist Baeyer was the first to suggest that the
series, propane (CH 3 CH 2 CH 3 ) also has two extreme instability of these small rings compounds was due to angle strain. This
theory is known as Baeyer-strain theory.
conformations, the energy barrier in propane is14 , which is slightly
1

higher than that in ethane. Baeyer strain theory was based upon the assumption that when an
3
open chain organic compound having the normal bond angle 109.5° is
convert into a cyclic compound, a definite distortion of this normal angle
3

takes place leading to the development of a strain in24.44°

the molecule.
deviation
Staggered propane Eclipsed propane
Newman projection of propane
(iii) : As the alkane molecule becomes 109.5° 60°
larger, the conformation situation becomes more complex. In butane
109.5°
(CH 3 CH 2 CH 2 CH 3 ) , for example, the rotation about the single
24.44°
bond between two inner atoms ( C 2 and C 3 ) is considered. In this case, all deviation
the staggered as well as eclipsed conformations will not have same stability Baeyer assumed that cyclic rings are planar. Assuming that the rings
and energy because of different types of interaction between C C (of are planar, the amount of strain in various cycloalkanes can be expressed in
methyl) and C H bonds. terms of angle of deviation ( ).
The lowest energy conformation will be the one, in which the two 1 2(n 2) 1
methyl groups are as far apart as possible 180° away form each other. d 109.5 90 or d [109.5 ]
2 n 2
This conformation will be maximum staggered, most stable and is
Where = number of carbon-carbon bonds in cycloalkane ring;
called anti or trans conformation (marked I). Other conformations can be
= inner bond angle in the cycloalkane ring.
obtained by rotating one of the C 2 or C 3 carbon atoms through an angle
of 60° as shown ahead. 1 1
Anglestrain d ; Stability inner angle( )
inner angle d
3 3 3

Now let us take the case of three to eight membered cyclic

compounds.
3

3
Cyclopropane Cyclobutane Cyclopentane
I II III = 60° = 90° = 108°
Anti Eclipsed Skew or Gauche = 22.44° = 9.4° = 0.44°

3 3
3

3 3

3
Cyclohexane Cycloheptane Cyclooctane
IV V VI = 120° = 128.6° = 135°
Fully eclipsed Skew or Gauche Eclipsed = 5.16° = 9.33° = 12.46°
As is clear from the (same
aboveasNewman
III) projection(same
the Gauche
as II) or Skew The positive and negative values of ( ) indicate whether the inner
conformations (III and V) are also staggered. However, in these angle is less than or more than the normal tetrahedral value.
conformations, the methyl groups are so close that they repel each other.
Beayer thus predicted that a five membered ring compound would
This repulsion causes gauche conformations, to have about 3.8 more -1

be the most stable. He also predicted that six membered ring compounds
energy than anti conformation. This conformations II and VI are eclipsed
would be less stable and as the cyclic compounds become larger than five
conformations. These are unstable because of repulsions. These are 16
membered ring, then they would become less and less stable.
-1
less stable than anti conformation. Conformation IV is also eclipsed and
it is least stable having energy 19 more than anti conformation. This
-1
Contrary to what Baeyer predicted, however cyclohexane is more
is because of repulsion between methyl-methyl groups which are very closed stable than cyclopentane. Furthermore, cyclic compounds do not become
together. It is called fully eclipsed conformation. less and less stable as the number of sides increase. Thus Baeyer strain
The order of stability of these conformations is, Anti > Skew or theory is applicable only to cyclopropane, cyclobutane and cyclopantane.
Gauche > Eclipsed > Fully eclipsed. The mistake that Baeyer made was to assume that all cyclic
(5) Conformations in cycloalkanes compounds are planar. But only cyclopropane is planar and other
cycloalkanes are not planar. Cyclic compounds twist and bend in order to
 General Organic Chemistry 1041

achieve structure that minimises the three different kinds of strain and that As a result of rotation about carbon-carbon single bonds
can destabilise a cyclic compound. cyclohexane rapidly interconverts between two stable chair conformations.
(a) Angle strain is the strain that results when the bond angle is This interconversion is known as ring flip. When the two chair forms
different from desired tetrahedral bond angle of 109.5°. interconvert, axial bonds become equatorial and equatorial bonds become
axial.
(b) Torsional strain is caused by repulsion of the bonding electrons
of one substituent with bonding electrons of a nearby substituent.
(c) Steric strain is caused by atoms or groups of atoms approaching Flipping
each other too closely.
(ii)
five-membered cyclic compounds would be the most stable, the six
membered cyclic compound is the most stable. Six membered cyclic Cyclohexane can also exist in a boat conformation. Like the
compound are most stable because they can exist in a conformation that is chair conformation, the boat conformation is free of angle strain. However,
almost completely free of strain. This conformation is called the chair the boat conformation is less stable than the chair conformation by 11
conformation. In a chair conformation of cyclohexane all bond angles are Boat conformation is less stable because some of the carbon-
109.38° which is very close to the 109.5° and all the adjacent carbon- hydrogen bonds in boat conformation are eclipsed.
hydrogen bonds are staggered.
The boat conformations is further destabilised by the close proximity
a a of the flagpole hydrogens. These hydrogens are 1.8 apart but the vander
c The flagpole hydrogens are also known as
c c 2 nuclear hydrogens.
a a
The relative stabilities of the four conformations of cyclohexane
c 2

c c decrease in the order:

a a Newmann projection of the Chair > twist boat > boat > half chair.
chair conformation
Chair conformation of
cyclohexane
Each carbon in chair conformation has an axial bond and an
equatorial bond.
Axial bonds are perpendicular to the plane of the ring and
equatorial bonds are in the plane of the ring.
If axial bond on carbon-1 is above the plane of the ring then
axial bond on carbon-2 will be below the plane of the ring. Thus
C 1, C 3 and C 5 axial bonds are above the plane

C 2, C 4 and C 6 axial bonds are below the plane

a a
1
6 5
a a

2 3 4
a a
Thus C 1 axial and C 2 axial are to each other.
Similarly C 1 and C 5 axials are to each other.
If axial bond on carbon-1 will be above the plane then
equatorial bond on this carbon will be below the plane.

(a) Above

(e) Below 1

(e) Above 2

(a) Below

(a) Thus C 1 equatorial and C 2 equatorial bonds are

(b) C 1 axial and C 2 equatorial will be
 General Organic Chemistry 1043
1. In methane molecule, the hydrogen atoms around carbon are arranged
as [DPMT 1980; MNR 1981; MP PET 1997, 99]
(a) Square planar (b) Tetrahedral
(c) Triangular (d) Octahedral
2. In carbon tetrachloride, four valence of carbon are directed to four
corners of [CPMT 1973, 77]
(a) Rectangle (b) Square
Wohler synthesised the first organic compound urea in the (c) Tetrahedron (d) None of these
laboratory.
3. In alkene (ethene) number of sp 2 hybrid carbon atoms are
The number of optical isomers of a compound depends on its (a) 1 (b) 2
structure and number of asymmetric carbon atoms present in its (c) 3 (d) 0
molecule.
4. Each carbon atom in benzene is in the state of hybridization
Stereoisomers that are not mirror images of each other are called [CPMT 1973, 83, 89; MP PMT 1993;
diastereomers. KCET (Med.) 1999; DCE 2001]

Order of priority for both asymmetric carbon atoms using (a) sp 3 (b) sp 2
sequence rules is (c) sp (d) s 3 p
> > ( ) > 5. Which of the following hybridisation has highest percentage of
character [BHU 1986]
The nitration and sulphonation of alkanes involve free radicals.
(a) sp 3 (b) sp 2
Carbenes undergo insertion reactions.
(c) sp (d) None of these
Alkanes usually undergo free radical substitution when hydrogen is
6. The hybridisation present in C 2 H 2 is [EAMCET 1993]
replaced by a halogen. It is catalysed by benzoyl peroxide ( ). 6 5 2

2
The polymerisation of alkenes is free radical addition reaction. (a) sp (b) sp
3
Allyl free radical ( = ) is more stable than -propyl (c) sp (d) dsp 2
2 2

free radical ( 3
).
2 2
7. What hybrid orbitals will form the following compound
H 3 C CH CH CH 2 CH 3 [AFMC 1991]
The stability of free radicals is explained on the basis of
hyperconjugation or conjugation. (a) sp and sp 3 (b) sp 2 and sp 3
Propene is more reactive than ethene towards electrophilic addition (c) sp and sp 2 (d) Only sp 3
reaction due to the formation of more stable 2° carbocation.
8. The compound in which carbon uses only its sp 3 hybrid orbitals
The reactivity of alkyl halides in 1
is 3°> 2°>1°>methyl while 2
is for bond formation is [IIT-JEE 1989]
methyl > 1°> 2°> 3°. (a) HCOOH (b) (NH 2 )2 CO
Polar solvents favour 1
while non polar solvents favour 2

(c) (CH 3 )3 COH (d) (CH 3 )3 CHO

reactions.
9. A straight chain hydrocarbon has the molecular formula C 8 H 10 .
Dipole moment of is less than that of
3
. This is because 2 2
The hybridisation for the carbon atoms from one end of the chain to
in all bond moments reinforce each other while in the bond
the other are respectively sp 3 , sp 2 , sp 2 , sp 3 , sp 2 , sp 2 , sp and
2 2 3

moment of one of the opposes the net moment of the other two.
sp . The structural formula of the hydrocarbon would be[CBSE PMT 1992]
Low concentration of nucleophiles favour 1
while high
(a) CH 3 C C CH 2 CH CH CH CH 2
concentration favour . 2

(b) CH 3 CH 2 CH CH CH 2 C C CH CH 2
In the attack of the nucleophile may be from either side and so
1

recimization takes place. However, in the attack of the nucleophile

2
(c) CH 3 CH CH CH 2 C C CH CH 2
takes place from back side. So it leads to inversion of configuration. (d) CH 3 CH CH CH 2 CH CH C CH
Hunsdieker reaction proceeds via free radical mechanism.
10. Which of the following has a bond formed by overlap of sp sp 3
Propene reacts with chlorine at 673 to form allyl chloride and hybrid orbitals [MNR 1993; UPSEAT 2001, 02]
the intermediate is allyl free radical.
(a) CH 3 C C H
(b) CH 3 CH CH CH 3
(c) CH 2 CH CH CH 2
(d) HC CH
11. The bond between carbon atom (1) and carbon atom (2) in
compound N C CH CH 2 involves the hybridised carbon as[IIT-JEE 198
Bonding and hybridisation in organic
compounds (a) sp 2 and sp 2 (b) sp 3 and sp
(c) sp and sp 2 (d) sp and sp
 1044 General Organic Chemistry
12. Number of bonds in CH 2 CH CH CH C CH is (a) 8 (b) 10
[Kurukshetra CEE 1991; KCET 2000] (c) 11 (d) 12
(a) 2 (b) 3 21. Which of the following statements is false for isopentane
[MP PET 1996]
(c) 4 (d) 5
13. Number of electrons present in naphthalene is (a) It has three CH 3 groups
[AFMC 1991] (b) It has one CH 2 group
(a) 4 (b) 6
(c) It has one group
(c) 10 (d) 14
(d) It has a carbon which is not bonded to hydrogen
2
14. Number of electrons in cyclobutadienyl anion (C 4 H 4 ) is[IIT-JEE 1991]
22. The number of bonds in xylene is [MP PET 1996]
(a) 2 (b) 4 (a) 6 (b) 9
(c) 6 (d) 8 (c) 12 (d) 18
15. Homolytic fission of - bond in ethane gives an intermediate in 23. In benzene the total number of bonds is [MP PMT 1997]
which carbon is [IIT-JEE 1992] (a) 3 (b) 6
(a) sp 3 hybridised (b) sp 2 hybridised (c) 9 (d) 12

(c) sp hybridised (d) sp 2 d hybridised 24. The number of sp 3 hybridized carbon atoms in cyclohexene are[MP PMT 1997
16. In the reaction (a) 2 (b) 3
H2
(c) 4 (d) 6
Br Br
C C BrCH2 CH 2 Br 25. The number of bonds in 3-hexyne-1-ene is
H 1 2 H Catalyst
3 4 [MP PMT 1999]
The hybridisation states of carbon atoms 1, 2, 3, 4 are (a) 1 (b) 2
[MP PET 1994] (c) 3 (d) 4
2 3
(a) 1 and 2 sp ; 3 and 4 sp 26. Example of sp 2 hybridization is [CPMT 1997]
2
(b) 1 and 2 sp ; 3 and 4 sp (a) CH 3 (b) CH 3
(c) 1, 2, 3 and 4 sp
(c) C2 H5 (d) C 2 H 5
(d) 1, 2 sp 3 ; 3, 4 sp 2
27. Select the molecule which has only one bond
17. In which of the compounds given below is there more than one kind [Pb. PMT 1998]
of hybridisation (sp, sp 2 , sp 3 ) for carbon (a) CH CH (b) CH 2 CHCHO
(i) CH 3 CH 2 CH 2 CH 3
(c) CH 3 CH CH 2 (d) CH 3 CH CHCOOH
(ii) CH 3 CH CH CH 3 28. Carbon atoms in the compound (CN )4 C 2 are
(iii) CH 2 CH CH CH 2 [Roorkee 1999]
(iv) H C C H [CBSE PMT 1995]
(a) hybridized
(a) ( ) and ( ) (b) ( ) and ( ) (b) sp 2 hybridized
(c) ( ) and ( ) (d) ( )
(c) and sp 2 hybridized
18. Examine the following common chemical structures to which simple
functional groups are often attached (d) , sp 2 and sp 3 hybridized
29. Acetylene molecules contain [DCE 1999]
(i) (ii) (a) 5 bond
(b) 4 bond and 1 bond
(c) 3 and 2
(iii) (iv) CH 3 CH 2 CH 2 CH 2 (d) 3 and 3
H 30. Number of unhybridised orbitals in vinyl acetylene are
(v) H 2C C [RPMT 1999]
H
(a) 2 (b) 3
Which of these systems have essentially planar geometry
(c) 4 (d) 6
[CBSE PMT 1995]
(a) ( ) and ( ) (b) ( ) and ( ) 31. Maximum bond energy of C H bonds is found in the compound [RPMT 1999]
(c) ( ), ( ) and ( ) (d) ( ) (a) Ethane (b) Ethene
(c) Ethyne (d) Equal in all the three
19. The structure of di-chloromethane is [MP PMT 1995]
32. Ethylene possess [RPET 1999]
(a) Tetrahedral (b) Trigonal
(a) Two sigma and two pi bonds
(c) Linear (d) Hexagonal
(b) Two pi bonds
20. The numbers of sigma ( ) bonds in 1-butene is
(c) Five sigma and one pi bond
[MP PMT 1995]
 General Organic Chemistry 1045
(d) Four sigma and one pi bond (c) 1, 3-pentadiene (d) -butylene
33. The hybridization involved in the six carbon atoms of benzene is [BHU 1999]45. In which of the following species is the underlined carbon having
(a) 3 sp 3 , 3 sp 2 (b) 3 sp 3 , 3 sp sp 3 hybridisation [AIEEE 2002]
2
(c) All 6 sp (d) All 6sp (a) CH 3 COOH (b) CH 3 CH 2 OH
34. 1, 3-butadiene has [JIPMER 2000] (c) CH 3 COCH 3 (d) CH 2 CH CH 3
2
(a) and sp hybridised -atoms 46. The H C H bond angle in CH 4 is [MP PET 2002]
2 3
(b) , sp and sp hybridized -atoms (a) 109 o 28 ' (b) 107 o 28 '
2
(c) Only sp hybridised -atoms (c) 90 o
(d) 180 o
(d) Only hybridised -atoms 47. The hybridisation of carbons of C C single bond of
35. Which of the following C H bond has the lowest bond HC C CH CH 2 is [RPMT 2002]
dissociation energy [CBSE PMT 2000]
(a) sp 3 sp 3 (b) sp sp 2
(a) Primary (1 o ) C H bond
(c) sp 3 sp (d) sp 2 sp 3
(b) Secondary (2 o ) C H bond
48. The shape of ethylene molecule is [AFMC 2002]
(c) Tertiary (3 o ) C H bond (a) Square planar (b) Furan
(d) All of these (c) Trigonal planar (d) Tetrahedral
36. Number of and bonds present in 1- butene-3-yne respectively 49. Acetylene molecule has carbon in [Kerala (Engg.) 2002]
are [RPMT 1999; MP PET 2000; DCE 2000]
(a) sp - hybridisation (b) sp 2 - hybridisation
(a) 7 ,3 (b) 5 , 2
(c) sp 3 - hybridisation (d) sp 3 d - hybridisation
(c) 8 ,3 (d) 6 ,2
50. In the formation of methane molecule, carbon makes use of
37. Which is an acidic hydrocarbon [AMU 2000] [DPMT 2001; MP PMT 2002]
(a) CH 3 CH 2 CH 2 CH 3 (b) CH 3 C CCH 3 (a) sp -hybridised orbitals (b) sp 2 -hybridised orbitals
(c) CH 3 C CH (d) CH 2 CH CH CH 2 (c) sp 3 -hybridised orbitals (d) Unhybridised orbitals
38. A carbon-carbon triple bond in ethyne ( C C ) consists of 51. In graphite atom is in ....state [CPMT 2002]
[AMU 2000] (a) sp 3 (b) sp
(a) All bonds
(c) sp 2 (d) None of these
(b) Two bonds and one -bond
52. How many -bonds are present in naphthalene molecule
(c) One bond and two bonds [RPMT 2002]
(d) All bonds (a) 3 (b) 4
39. Toluene has [MP PMT 2000; Kerala CET 2005] (c) 5 (d) 6
(a) 6 and 3 bond (b) 9 and 3 bond 53. Hybridisation state of in diamond is [RPMT 2002]
(c) 9 and 6 bond (d) 15 and 3 bond (a) sp (b) sp 2
40. In compound , all the bond angles are exactly 109 o 28 ' , is[DPMT 2000] (c) sp 3 (d) sp 3 d
(a) Chloroform (b) Carbon tetrachloride 54. The number of and bonds present in pent-4-ene, 1-yne is[AIIMS 2002; CPM
(c) Chloromethane (d) Iodoform (a) 10, 3 (b) 3, 10
41. Which of the following hybridization is known as trigonal (c) 4, 9 (d) 9, 4
hybridization [MH CET 2000] 55. Which one of the following is more acidic [DPMT 2002]
(a) Butane (b) 1-butene
(a) sp 3 (b)
(c) 1-butyne (d) 2-butyne
2
(c) sp (d) dsp 2 56. Graphite is soft while diamond is hard because [BHU 2003]
42. The types of hybridization present in 1, 2- butadiene are (a) Graphite is in powder form
[MH CET 2000] (b) Diamond has sp 2 hybridization but graphite has
2 3 2 3 3
(a) sp, sp and sp (b) sp and sp sp hybridization
2 3 (c) Graphite is in planar form while diamond is in tetrahedral form
(c) sp and sp (d) sp and sp
(d) Graphite is covalent and diamond is ionic
43. The bond distance is longest in [BHU 2001] 57. Hybridization of 1 and 2 carbon atoms in
(a) C2 H 2 (b) C 2 H 4 1 2
CH 2 C CH 2 [BHU 2003]
(c) C2 H 6 (d) C 6 H 6 2 2
(a) sp, sp (b) sp , sp
44. Conjugated double bond is present in
2
[RPMT 1999; JIPMER 2001] (c) sp , sp (d) sp 3 , sp 2
(a) 1, 2-butadiene (b) 1, 3-butadiene 58. Hydrogen bonding is maximum in [UPSEAT 2003]
 1046 General Organic Chemistry
(a) C 2 H 5 OH (b) CH 3 O CH 3 (a) -2-butene (b) 1, 3-Dimethylbenzene
(c) Acetophenone (d) Ethanol
(c) (CH 3 )2 C O (d) CH 3 CHO
6. Resonance structure of molecule does not have
59. How many methyl group are present in 2, 5-dimethyl-4-ethylheptane[EAMCET 2003] [IIT-JEE 1984]
(a) 2 (b) 3 (a) Identical arrangement of atoms
(c) 4 (d) 5 (b) Nearly the same energy content
60. Which one of the following does not have sp hybridised carbon [AIEEE 2004] (c) The same number of paired electrons
2

(a) Acetonitrile (b) Acetic acid (d) Identical bonding

7. All bonds in benzene are equal due to
(c) Acetone (d) Acetamide
[Roorkee 1990; KCET 1998]
61. Allyl cyanide contain - and -bonds [MP PET 2004] (a) Tautomerism (b) Inductive effect
(a) 9 , 3 (b) 9 , 9 (c) Resonance (d) Isomerism
(c) 3 , 4 (d) 5 ,7 8. Aromatic properties of benzene are proved by
[MP PMT 1994]
62. Strongest acid is [MP PMT 2004]
(a) Aromatic sextet theory (b) Resonance theory
(a) HC CH (b) C 2 H 6
(c) Molecular orbital theory (d) All of these
(c) C6 H 6 (d) CH 3 OH 9. Which of the following will show aromatic behaviour
63. C C bond is found in [BHU 1982; MP PMT 1994] [KCET 1996]
(a) Ethene (b) Butene
(c) Ethyne (d) Glycerine (a) (b)

64. Number of bonds in [CPMT 1994] (c) (d)

(a) 6 (b) 15 10. Which one of the following orders is correct regarding the inductive
effect of the substituents [CBSE PMT 1998]
(c) 10 (d) 12
65. Number of bonds in benzene [DPMT 2005] (a) NR 2 OR F (b) NR 2 OR F
(a) 6 and 3 (b) 12 and 3 (c) NR 2 OR F (d) NR 2 OR F
(c) 3 and 12 (d) 6 and 6 11. Benzene is unreactive because [KCET 1998]
66. Which is most acidic of the following [J & K 2005] (a) It has double bonds
(a) Methane (b) Acetylene (b) It has carbon-carbon single bond
(c) 1-butene (d) Neo-pentane
67. The enolic form of acetone contains [Pb. PMT 2002] (c) Carbon are sp 2 hybridised
(a) 8 bonds, 2 -bonds and 1 lone pairs (d) electrons are delocalised
(b) 9 -bonds, 1 -bond and 2 lone pairs 12. Carboxylic acids are easily ionised. The main reason of this
statement [UPSEAT 1999]
(c) 9 -bonds, 2 -bonds and 1 lone pairs
(d) 10 -bonds, 1 -bonds and 1 lone pairs (a) Absence of -hydrogen
(b) Resonance stabilisation of carboxylate ion
(c) Reactivity of -hydrogen
Dipole moment, resonance and reaction (d) Hydrogen bond
intermediates 13. ' C C' bond length in benzene lies between single and double
bond. The reason is [RPET 1999]
1. Which has zero dipole moment [NCERT 1990; BHU 2001] (a) Resonance (b) Isomerism
(a) -2-butene (b) -2-butene (c) Metamerism (d) Inductive effect
(c) 1-butene (d) 2-methyl-1-propene 14. Credit for the ring structure of benzene goes to
2. Dipole moment is shown by [DCE 1999] [RPET 1999]
(a) 1, 4-dichloro benzene (a) Wholer (b) Faraday
(b) Cis-1, 2-dichloro ethane (c) Kekule (d) Baeyer
(c) Trans-1, 2-dichloro, 2-pentene
15. Polarisation of electrons in acroline may be written as
(d) Trans-1, 2-dichloro ether
[DCE 2000]
3. Which compound shows dipole moment [RPMT 2002]
(a) 1,4-di-chloro benzene (a) CH 2 CH CH O
(b) 1, 2-di-chloro benzene
(b) CH 2 CH CH O
(c) Trans-1, 2-di-chloro ethene
(d) Trans-2-butene (c) CH 2 CH CH O
4. Which of the following is a polar compound
[MH CET 2003] (d) CH 2 CH CH O
(a) C2 H 6 (b) CCl 4 16. In the mixture of conc. H 2 SO 4 and HNO 3 the nitrating species
(c) (d) CH 4 is [MP PMT 2000]
5. The dipole moment is the highest for [AIIMS 2004] (a) N 2 O4 (b) NO 2
 General Organic Chemistry 1047

(c) NO 2 (d) NO 2 (d) CH 2 CH CH CH O CH 3

17. Which of the following are not aromatic [DCE 2001] 26. Which amongst the following is the most stable carbocation
(a) Benzene [CBSE PMT 2005]
(b) Cyclo-octatetrarenyl dianion CH 3
(c) Tropyllium cation |

(d) Cyclopentadienyl cation (a) CH 3 C (b) CH 3 C

| |
18. Arrangement of CH 3 CH 3
(CH 3 )3 C (CH 2 )3 CH CH 3 CH 2 CH 3 when
attached to benzyl or an unsaturated group in increasing order of (c) C H 3 (d) CH 3 CH 3
inductive effect is [AIEEE 2002] 27. Which is the decreasing order of stability
[IIT-JEE (Screening) 1993]
(a) (CH 3 )3 C (CH 3 )2 CH CH 3 CH 2
(b) CH 3 CH 2 (CH 3 )2 CH (CH 3 )3 C (i) CH 3 CH CH 3

(c) (CH 3 )2 CH (CH 3 )3 C CH 3 CH 2 (ii) CH 3 CH O CH 3

(d) (CH 2 )3 C CH 3 CH 2 (CH 3 )2 CH
(iii) CH 3 CH CO CH 3
19. Which of the following is observed in ethylene molecule
(a) (i) (ii) (iii) (b) (i) (ii) (iii)
[MH CET 2002]
(a) Electromeric effect (b) Inductive effect (c) (iii) (ii) (i) (d) (ii) (iii) (i)
(c) Homolytic fission (d) None of these 28. The order of decreasing stability of the carbanions
20. Cyclopentadienyl anion is [Orissa JEE 2003] (1) (CH 3 )3 C (2) (CH 3 )2 C H
(a) Aromatic (b) Non-aromatic
(c) Non-planar (d) Aliphatic (3) CH 3C H 2 (4) C6 H 5 C H 2 is [KCET 1996]
21. Orbital interaction between the sigma bonds of a substitutent group (a) 1 > 2 > 3 > 4 (b) 4 > 3 > 2 > 1
and a neighbouring orbital is known as (c) 4 > 1 > 2 > 3 (d) 1 > 2 > 4 > 3
[Kerala PMT 2004] 29. Choose the chain terminating step
(a) Hyperconjugation (1) H2 H H
(b) Inductive effect
(c) Steric effect (2) Br2 Br Br
(d) Dipole-dipole interactions (3) Br HBr H Br2
(e) Electric quadruple interactions
(4) H Br2 HBr Br
22. Which of the following is the most stable compound
[BHU 2004] (5) Br Br Br2 [RPET 2000]
(a) 1 (b) 3
(a) Ph3 C (b) Ph2 C H
(c) 4 (d) 5
30. The compound, which gives the most stable carbonium on
(c) Ph3 CH 2 (d) PhCH 2 dehydrogenation [UPSEAT 2001]
23. Which of the following will be most easily attacked by an (a) CH 3 CH CH 2 OH
|
electrophile [MP PET 2004]
CH 3
CH 3
|
(a) (b) (b) CH 3 C OH
|

3
CH 3
(c) CH 3 CH 2 CH 2 CH 2 OH
(c) (d)
(d) CH 3 CH CH 2 CH 3
|
24. Reactivity towards nucleophilic addition reaction of (I) , (II)
CH 3
CH 3 CHO , (III) CH 3 COCH 3 is
31. Which of the following requires radical intermediate
[Orissa JEE 2004]
[Orissa JEE 2004]
(a) II > III > I (b) III > II > I
(a) CH 3 CH CH 2 HBr CH 3 CH CH 3
(c) I > II > III (d) I > II < III |
25. Which of the following resonating structures of 1-methoxy-1, 3- Br
butadiene is least stable [IIT Screening 2005] CN
(b) CH 3 CHO HCN CH 3 CH
(a) CH 2 CH CH CH O CH 3 OH
(c) CH 3 CH CH 2 HBr CH 3 CH 2 CH 2 Br
(b) CH 2 CH 2 CH CH O CH 3
H
(d) CH 3 CHO NH 2 OH CH 3 CH N OH
(c) CH 2 CH CH CH O CH 3
 1048 General Organic Chemistry
32. Which of the following species is paramagnetic in nature (c) RCOOH (d) HCl
[NCERT 1984] 45. Which gives monosubstituted product [DPMT 2005]
(a) Free radical (b) Carbonium ion (a) o -dinitrobenzene (b) m -dinitrobenzene
(c) Carbanion (d) All the above
(c) p -dinitrobenzene (d) Nitrobenzene
33. In which of the following species the central -atom is negatively
charged [NCERT 1985] 46. An aromatic compounds among other things should have a -
(a) Carbanion (b) Carbonium ion electron cloud containing electrons where n can't be
(c) Carbocation (d) Free radical [J & K 2005]
34. Which of the following free radicals is most stable (a) 1/2 (b) 3
[NCERT 1982] (c) 2 (d) 1
(a) Primary (b) Methyl 47. Which of the following is an electrophile [J & K 2005]
(c) Secondary (d) Tertiary (a) H 2 O (b) SO 3
35. Which of the following contains three pairs of electrons
[BHU 1985]
(c) NH 3 (d) ROR
(a) Carbocation (b) Carbanion 48. The presence of the chlorine atom on benzene ring makes the
(c) Free radical (d) None of these second substituent enter at a position [J & K 2005]
36. Which of the following carbanion is most stable (a) (b)
[NCERT 1983] (c) (d)
(a) Methyl (b) Primary 49. Which is the most stable carbocation [J & K 2005]
(c) Secondary (d) Tertiary (a) iso-propyl (b) Triphenylmethyl cation
37. Among the given cations, the most stable carbonium ion is (c) Ethyl cation (d) -propyl cation
[IIT-JEE 1981]
(a) -butyl (b) -butyl
(c) -butyl (d) None of these Organic reactions and their mechanism
38. In the compound given below
1. To which of the following four types does this reaction belong
B R A B R A
3 3

( ) ( ) [Manipal MEE 1995]

(a) Unimolecular electrophilic substitution
(b) Bimolecular electrophilic substitution
(c) Unimolecular nucleophilic substitution
( ) of the acidity of the positions ( ), ( ) and ( ) is
The correct order [IIT-JEE Screening 2004] substitution
(d) Bimolecular nucleophilic
(a) ( ) > ( ) > ( ) (b) ( ) > ( ) > ( ) 2. An alkyl halide may be converted into an alcohol by
(c) ( ) > ( ) > ( ) (d) ( ) > ( ) > ( ) [Pb. PMT 2000]
39. bond length in benzene is (a) Elimination (b) Addition
[MP PMT 1987; MP PMT 2001; AIIMS 2001] (c) Substitution (d) Dehydrohalogenation
(a) 1.39 Å 3. CH 3 CH 2 Cl
(b) 1.54 Å
(c) 1.34 Å
(d) Different in different bonds The above reaction proceeds through [AMU 2000]
40. Heterolysis of carbon-chlorine bond produces
(a) Nucleophilic substitution
[MNR 1986; MP PET/PMT 1998]
(b) Electrophilic substitution
(a) Two free radicals
(c) Free radical substitution
(b) Two carbonium ions
(d) More than one of the above processes
(c) Two carbanions
(d) One cation and one anion 4. Geometry of reaction intermediate in SN 1 reaction is
[MH CET 2001]
41. In CH 3 CH 2 OH, the bond that undergoes heterolytic cleavage
(a) Tetrahedral (b) Planar
most readily is [IIT-JEE 1988]
(c) Triangular bipyramidal (d) None of these
(a) (b)
(c) (d) CH 3 CH 3
| |
42. Which of the following intermediate have the complete octet around 5. H3C C Br KOH ( Aq.) H3C C OH KBr
the carbon atom [Orissa JEE 2003] | |
CH 3 CH 3
(a) Carbonium ion (b) Carbanion ion
(c) Free radical (d) Carbene above reaction is [RPMT 2003]
1 2
43. A solution of D (+) - 2-chloro-2-phenylethane in toluene racemises (a) SN (b) SN
slowly in the presence of small amount of SbCl 5 , due to the (c) E1 (d) Both (a) and (b)
formation of [IIT-JEE 1999]
6. In electrophilic substitution reaction nitrobenzene is
(a) Carbanion (b) Carbene [Kerala (Med.) 2003]
(c) Free radical (d) Carbocation (a) Meta-directing
44. The reagent in Friedel Craft's reaction is [DPMT 2005] (b) Ortho-directing
(a) Pyridine (b) RCOCl (c) Para-directing
 General Organic Chemistry 1049
(d) Not reactive and does not undergo any substitution (b) Benzyl bromide hydrolysis
(e) Non-selective (c) Reaction of with dinitrofluorobenzene
7. The most common type of reaction in aromatic compounds is [Orissa JEE 2003] (d) Sulphonation of benzene
(a) Elimination reaction 20. Which is an electrophile [DCE 2000]
(b) Addition reaction (a) AlCl3 (b) CN
(c) Electrophilic substitution reaction (c) NH 3 (d) CH 3 OH
(d) Rearrangement reaction
21. Strongest nucleophile is [BHU 2003]
8. The function of AlCl3 in Friedel- (a) RNH 2 (b) ROH
[KCET 2003]
(a) To absorb (b) To absorb water (c) C6 H 5 O (d) CH 3 O
(c) To produce nucleophile (d) To produce electrophile 22. The major product obtained when Br2 / Fe is treated with
9. [AFMC 2004]
(a) FeCl 3 (b) FeBr2 is
(c) AlCl3 (d) 3 3

[IIT-JEE Screening 2004]

10. The nitration of a compound is due to the [Pb. PMT 2004]
(a) NO 2 (b) NO 3

(c) (d) NO 2 (a)

3 3

(b)
3 3

11. Dehydrohalogenation of an alkyl halide is a/an

[MH CET 2004]
(a) Nucleophilic substitution reaction
(b) Elimination reaction
(c) Both nucleophilic substitution and elimination reaction
(d) Rearrangement (c) (d)
3 3 3 3

12. Addition of to vinyl chloride gives 1, 1-dichloroethane because of[MP PET 2004]
(a) Mesomeric effect of 23. Which one of the following is least reactive in a nucleophilic
(b) Inductive effect of substitution reaction [CBSE PMT 2004]
(c) Restricted rotation around double bond (a) CH 3 CH 2 Cl (b) CH 2 CHCH 2 Cl
(d) None of these (c) (CH 3 )3 C Cl (d) CH 2 CHCl
13. Formation of ethylene from acetylene is an example of 24. Among the following the strongest nucleophile is
(a) Elimination reaction (b) Substitution reaction [AIIMS 2005]
(c) Addition reaction (d) Condensation reaction
(a) C 2 H 5 SH (b) CH 3 COO
14. Conversion of CH 4 to CH 3Cl is an example of which of the
following reaction [Pb. CET 2001] (c) CH 3 NH 2 (d) NCCH 2
(a) Electrophilic substitution 25. The reaction [AIEEE 2005]
(b) Free radical addition O O
(c) Nucleophilic substitution R C Nu R C X , is fastest when X
(d) Free radical substituion
X Nu
15. Following reaction, (CH 3 )3 CBr H 2O (CH 3 )3 COH HBr is
is an example of (a) Cl (b) NH 2
[DCE 2002]
(a) Elimination reaction (b) Free radical substitution (c) OC2 H 5 (d) OCOR
(c) Nucleophilic substitution (d) Electrophilic substitution 26. Elimination of bromine from 2-bromobutane results in the
16. Which is an electrophile [DCE 2002] formation of [AIEEE 2004, 05]
(a) BCl3 (b) CH 3OH (a) Equimolar mixture of 1 and 2-butene
(b) Predominantly 2-butene
(c) NH 3 (d) AlCl4 (c) Predominantly 1-butene
(d) Predominantly 2-butyne
17. The electrophile in the nitration of benzene is
[Orissa JEE 2004] 27. Examine the following statements pertaining to an SN 2 reaction
(1) The rate of reaction is independent of the concentration of the
(a) NO 2 (b) NO 2 nucleophile
(c) NO (d) NO 2 (2) The nucleophile attacks the C atom on the side of the
molecule opposite to the group being displaced
18. The following compound will undergo electrophilic substitution (3) The reaction proceeds with simultaneous bond formation and
more readily than benzene [UPSEAT 2004] bond rupture/cleavage
(a) Nitrobenzene (b) Benzoic acid Amongst the following which of the above were true
(c) Benzaldehyde (d) Phenol [NCERT 1982]
19. Which represents nucleophilic aromatic substitution reaction (a) 1, 2 (b) 1, 3
[Orissa JEE 2004] (c) 1, 2, 3 (d) 2, 3
(a) Reaction of benzene with Cl 2 in sunlight 28. What is the decreasing order of reactivity amongst the following
compounds towards aromatic electrophilic substitution [IIT-JEE 1995]
 1050 General Organic Chemistry
I. Chlorobenzene II. Benzene H H
III. Anilinium chloride IV. Toluene | |
(a) I II III IV (b) IV II I III (a) HO C COOH (b) CH 3 C COOH
(c) II I III IV (d) III I II IV | |
29. Which of the following applies in the reaction, H Cl
CH 3 CHBrCH 2 CH 3 alc. KOH CH 3 CH 3
(i) CH 3 CH CHCH 3 (major product) | |
(c) CH 3 C COOH (d) CH 3 C COOH
(ii) CH 2 CHCH 2 CH 3 (minor product) | |
[Orissa JEE 2005] OH Cl
(a) Markovnikov's rule (b) Saytzeff's rule
(c) Kharasch effect (d) Hofmann's rule 6. In ethane and cyclohexane which one of the following pairs of
30. Bromination of alkanes involves [J & K 2005] conformations are more stable
(a) Carbanions (b) Carbocations (a) Eclipsed and chair conformations
(c) Carbenes (d) Free radicals (b) Staggered and chair conformations
31. Which of the following cannot undergo nucleophilic substitution (c) Staggered and boat conformations
under ordinary conditions [J & K 2005] (d) Eclipsed and boat conformations
(a) Chlorobenzene (b) -butylchloride 7. Which of the following may exist in enantiomorphs
(c) Isopropyl chloride (d) None of these [CBSE PMT 1988]
32. Which of the following alkyl groups has the maximum + effect[KCET 2002]
CH 3
(a) CH 3 (b) (CH 3 )2 CH
|
(c) (CH 3 )3 C (d) CH 3CH 2 (a) CH 3 CH COOH
(b) CH 2 CHCH 2 CH 2 CH 3
Structural and stereo isomerism NH 2
|
1. Only two isomers of monochloro product is possible of (c) CH 3 CH CH 3
[IIT-JEE 1986]
(a) butane (b) 2,4-dimethyl pentane NH 2
(c) Benzene (d) 1-methyl propane |
(d) CH 3 CH 2 CH CH 3
2. Which is the example of branch isomerization
8. Which of the following compounds may not exist as enantiomers[CPMT 1987]
[NCERT 1976]
(a) CH 3 CH (OH)CO 2 H
C C
| | (b) CH 3 CH 2 CH (CH 3 )CH 2 OH
(a) C C C C and C C C (c) C 6 H 5 CH 2 CH 3
|
C (d) C6 H 5 CHClCH 3
C C 9. Number of isomers of molecular formula C 2 H 2 Br2 are
| | [CPMT 1987]
(b) C C C and C C C (a) 1 (b) 2
| |
C C (c) 3 (d) 0
10. Lactic acid shows which type of isomerism
C [CPMT 1987; MP PMT 1987; BHU 2003]
C | (a) Geometrical isomerism (b) Tautomerism
(c) C C C and C C C (c) Optical isomerism (d) Metamerism
C |
C 11. Which one of the following is an optically active compound
[CBSE PMT 1988; DPMT 1983]
(d) C C C C and C C C (a) -propanol (b) 2-chlorobutane
| (c) -butanol (d) 4-hydroxyheptane
C 12. Compounds with same molecular formula but different structural
3. The isomer of diethyl ether is [CPMT 1975] formulae are called [BHU 1979; AFMC 1989]
(a) Isomers (b) Isotopes
(a) (CH 3 )2 CHOH (b) (CH 3 )3 C OH
(c) Isobars (d) Isoelectronic
(c) C 3 H 7 OH (d) (C 2 H 5 )2 CHOH 13. Which one of the following compounds shows optical isomerism[MP PET 1990]
4. Isomers have essentially identical (a) CH 3 CHCl CH 2 CH 3
[CBSE PMT 1988; MP PMT 1983, 86] (b) CH 3 CH 2 CHCl CH 2 CH 3
(a) Structural formula (b) Chemical properties
(c) Molecular formula (d) Physical properties (c) ClCH 2 CH 2 CH 2 CH 3
5. Which one of the following shows optical activity (d) ClCH 2 CH 2 CH 3
[NCERT 1984, 90] 14.
(a) Letter P (b) Letter F
(c) Ball (d) A pair of hand
15. Total number of isomers of a disubstituted benzene compound is
(a) 1 (b) 2
 General Organic Chemistry 1051
(c) 3 (d) 4 H H C2 H H
16. Separating of and enantiomorphs from a racemic mixture is (a) C C (b) C C
called [CBSE PMT 1988; DPMT 1983; H3C CH 3 H H
KCET 2002] CH 3
(a) Resolution (b) Dehydration CH 3 H | H
(c) Rotation (d) Dehydrohalogenation (c) C C (d) H C C C
CH 3 H | | H
17. Number of optical isomers of lactic acid are H H
(a) 1 (b) 2
(c) 3 (d) 4 25. Maximum number of isomers of alkene C 4 H 8 are
18. Which one of the following contains asymmetric carbon atom[IIT-JEE 1989; Roorkee 2000] [IIT-JEE 1982; MP PMT 1985; MADT Bihar 1995;
Kerala (Engg.) 2002]
Cl Br H Cl (a) 2 (b) 3
| | | | (c) 4 (d) 6
(a) H C C H (b) H C C Cl 26. Rotation of plane polarised light is measured by
| | | | [CPMT 1985; DCE 2001]
H H H H (a) Manometer (b) Polarimeter
(c) Viscometer (d) Refractometer
H H H H 27. An alkane forms isomers if the number of least carbon atom is[CPMT 1976; BHU
| | | | (a) 1 (b) 2
(c) H C C H (d) H C C CH 3
(c) 3 (d) 4
| | | |
28. Which is not found in alkenes [AIIMS 1982; RPMT 1999]
H H Br OH
(a) Chain isomerism (b) Geometrical isomerism
19. -butane and isobutane are examples of (c) Metamerism (d) Position isomerism
(a) Chain isomers (b) Geometrical isomers 29. How many isomers of C 5 H 11 OH will be primary alcohols
(c) Position isomers (d) Tautomers [CBSE PMT 1992]
(a) 2 (b) 3
20. Which of the following has chiral structure
(c) 4 (d) 5
CH 3
30. The compound C 4 H 10 O can show
|
(a) CH 3 CH CH 2 COOH [IIT-JEE 1981; MP PET 2000]
(a) Metamerism (b) Functional isomerism
(b) CH 3 CH CH CH 3 (c) Positional isomerism (d) All types
CH 3 31. The number of possible alcoholic isomers for C 4 H 10 O are
| [DPMT 1984; MNR 1986]
(c) CH 3 CH CH 2 OH (a) 4 (b) 2
(d) CH 3 CHOH CH 2 CH 3 (c) 3 (d) 5
21. Which of the following pairs is an example of position isomerism 32. How many isomers are possible for C 4 H 8 O
(a) CH 3 CH 2 CH 2 CH 3 and CH 3 CH CH 3 [MNR 1992; UPSEAT 2001, 02]
| (a) 3 (b) 4
CH 3 (c) 5 (d) 6
(b) CH 3 CH 2 CH CH 2 and CH 3 CH CH CH 3 33. Which of the following can exhibit isomerism
[CBSE PMT 1989]
(c) CH 3 CH 2 OH and CH 3 O CH 3 (a) (b) =
CH 3 (c) CH 3 .CHCl .COOH (d) ClCH 2 CH 2 Cl
| 34. The number of geometrical isomers in case of a compound with the
(d) CH 3 C CH 3 and CH 3 CH 2 CH 2 CH 2 CH 3
structure CH 3 CH CH CH CH C 2 H 5 is
|
CH 3 [NCERT 1980]
(a) 4 (b) 3
22. Geometrical isomerism is shown by
[IIT-JEE 1983; CPMT 1990, 94; CBSE PMT 1992;
(c) 2 (d) 5
MP PET 1997; AMU (Engg.) 1999] 35. The property by virtue of which a compound can turn the plane
polarised light is known as [BHU 1979]
(a) 2-butene (b) 2-butyne
(a) Photolysis (b) Phosphorescence
(c) 2-butanol (d) Butanal
(c) Optical activity (d) Polarization
23. An organic compound exhibits optical isomerism when
36. Meso-tartaric acid is optically inactive due to the presence of
[CPMT 1971, 78, 81; MP PET 1999]
[AIIMS 1982; MP PMT 1987]
(a) Four groups linked to carbon atom are different
(a) Molecular symmetry
(b) Three groups linked to carbon atom are different
(c) Two groups linked to carbon atom are different (b) Molecular asymmetry
(d) All the groups linked to carbon atom are same (c) External compensation
24. Which one of the following exhibits geometrical isomerism (d) Two asymmetric C-atoms
[NCERT 1979; DPMT 1984; CBSE PMT 1990] 37. Which of the following compounds exhibits optical isomerism[BHU 1983; AFMC 1
 1052 General Organic Chemistry
MP PMT 1999, 2000] (b) Butanone and butanal
(a) CH 3 CH 2 COOH (b) CH 3 CHOHCOOH (c) Ethoxy propane and propoxy ethane
(d) Methoxy methane and ethanol
(c) CH 3 CH 2 CH 2 OH (d) CH 3 CHOHCH 3
50. Functional isomerism is exhibited by the following pair of
38. The maximum number of stereoisomers possible for 2-hydroxy-2- compounds
methyl butanoic acid is [Roorkee 1992] (a) Acetone, propionaldehyde
(a) 1 (b) 2 (b) Diethyl ether, methyl propyl ether
(c) 3 (d) 4 (c) Butane, isobutane
39. Which one of the following pairs represents the stereoisomerism[AIIMS 1992] (d) 1-butene, 2-butene
(a) Geometrical isomerism, position isomerism 51. The total number of possible isomeric trimethyl benzene is
(b) Geometrical isomerism, conformational isomerism [MP PET 1997]
(c) Optical isomerism, geometrical isomerism (a) 2 (b) 3
(d) Optical isomerism, metamerism (c) 4 (d) 6
40. Diethyl ether is not associated with which one of these isomers [AFMC 1993]52. Optically active isomers but not mirror images are called
(a) Butanoic acid (b) Methyl propionate [MP PET 1999]
(c) Steroisomerism (d) None of these (a) Enantiomers (b) Mesomers
41. Diethyl ether and methyl propyl ether are (c) Tautomers (d) Diastereoisomers
[MP PET 1994; AFMC 1999; MP PMT 2002] 53. C 7 H 9 N has how many isomeric forms that contain a benzene
(a) Position isomers (b) Functional isomers ring [CPMT 1997, 99; JIPMER 2002; DCE 2003]
(c) Metamers (d) Chain isomers (a) 4 (b) 5
42. propyl alcohol and isopropyl alcohol are examples of (c) 6 (d) 7
[MP PMT 1994]
54. The total number of isomers formed by C 5 H 10 is
(a) Position isomerism (b) Chain isomerism
[Bihar MEE 1996]
(c) Tautomerism (d) Geometrical isomerism
43. It is possible to distinguish between optical isomers by (a) 2 (b) 3
[Manipal MEE 1995; AFMC 1995] (c) 4 (d) 5
(a) Infrared spectroscopy (e) None of these
(b) Mass spectrometry 55. Which of the following contains asymmetric centre
[CPMT 1996]
(c) Melting point determination
(a) 2-butene (b) 2, 2-dimethylpropane
(d) Polarimetry
(c) 2-hexyne (d) Lactic acid
44. The isomerism exhibited by alkyl cyanide and alkyl isocyanide is[AFMC 1995, 97]
56. Which of the following cannot be given to exemplify chiral structure[JIPMER 199
(a) Functional (b) Positional
(a) A shoe (b) A screw
(c) Tautomerism (d) Metamerism
(c) A screw driver (d) All of these
45. The following compound can exhibits
57. Which of the following is expected to be optically active
CH 3 H [JIPMER 1997]
C C H [IIT-JEE 1995; DCE 2000]
CH 3 C (a) (CH 3 )4 C (b) C 2 H 5 CH (CH 3 )C 3 H 7
CH 3 COOH (c) (C 2 H 5 )2 CHCH 3 (d) CH 3 CH CHCH 3
(a) Tautomerism 58. Which compound does not show geometrical isomerism
(b) Optical isomerism [RPMT 1997]
(c) Geometrical isomerism (a) 2-butene (b) 2-pentene
(d) Geometrical and optical isomerisms (c) 2,3-dibromo-2-butene (d) 2-methyl propene
46. Name the compound, that is not isomer with diethyl ether 59. The isomers which can be converted into another forms by rotation
[IIT-JEE 1981; CPMT 1989; MADT Bihar 1995] of the molecules around single bond are
(a) propylmethyl ether [AIIMS 1997]
(b) Butane-1-ol (a) Geometrical isomers (b) Conformers
(c) 2-methylpropane-2-ol (c) Enantiomers (d) Diastereomers
(d) Butanone 60. The number of enantiomers of the compound
47. Which statement is true for cyclohexane [MP PET 1996] CH 3 CHBrCHBrCOOH is [AIIMS 1997]
(a) It has two possible isomers (a) 0 (b) 1
(b) It has three conformations (c) 3 (d) 4
(c) Boat conformation is most stable
61. C6 H 5 C N and C6 H 5 N C exhibit which type of isomerism[CPMT 199
(d) Chair and boat conformations differ in energy by 44
48. Two compounds have the structural formulae (a) Position (b) Functional
CH 3 O CH 2 CH 3 and CH 3 CH 2 CH 2 OH . The (c) Dextro isomerism (d) Metamerism
62. Which of the following compounds is not chiral
above is an example of
[CBSE PMT 1998; DPMT 2002]
(a) Metamerism (b) Functional isomerism
(a) DCH 2 CH 2 CH 2 Cl (b) CH 3 CH 2 CHDCl
(c) Positional isomerism (d) Chain isomerism
49. Which of the following pairs are not isomeric compounds (c) CH 3 CHDCH 2 CH 2 Cl (d) CH 2 CHClCH 2 D
(a) Ethyl ethanoate and methyl propanoate 63. and 2-butene are [BHU 1998; DPMT 2002]
 General Organic Chemistry 1053
(a) Conformational isomers (b) Optical isomers (c) Cis-trans isomers (d) Position isomers
(c) Position isomers (d) Geometrical isomers 79. Geometrical isomerism is not possible in [CPMT 2000]
64. Which one of the following is the chiral molecule (a) Propene (b) 3-hexane
[BHU 1998; 2005] (c) Butenedioic acid (d) Cyclic compound
(a) CH 3 Cl (b) CH 2 Cl 2 80. Only two isomeric monochloro derivatives are possible for
(c) CHBr3 (d) CHClBrI [Pb. PMT 2000]
65. Cyanide and isocyanide are isomers of type [AFMC 1997]
(a) 2-methyl propane (b) -pentane
(a) Positional (b) Functional (c) Benzene (d) 2, 4-dimethyl pentane
(c) Tautomer (d) Structural 81. Lactic acid in which a methyl group, a hydroxyl group, a carboxylic
66. Glucose and fructose are [AMU (Engg.) 1999] acid group and a hydrogen atom are attached to a central carbon
atom, shown optical isomerism due to the molecular geometry at
(a) Optical isomers (b) Functional isomers the [Pb. PMT 2000]
(c) Position isomers (d) Chain isomers
(a) Central carbon atom
67. Which of the following compounds which is an optically active
compound [UPSEAT 1999] (b) Carbon atom of the methyl group
(a) 1-butanol (b) 2-butanol (c) Carbon atom of the carboxylic acid group
(c) 3-butanol (d) 4-heptanol (d) Oxygen of the hydroxyl groups
68. -tartaric acid and -tartaric acid are [MH CET 1999] 82. The number of possible alkynes with molecular formula C 5 H 8 is [MP PMT 2
(a) Enantiomers (b) Tautomers
(a) 2 (b) 3
(c) Diastereoisomers (d) Structural isomers
(c) 4 (d) 5
69. Minimum resistance in bond rotation will be observed in the
compound [RPMT 1999] 83. Which of the following will not lose asymmetry on reduction with
(a) Hexachloroethane (b) Ethylene LiAlH4 [Roorkee 2000]
(c) Acetylene (d) Ethane CHO
70. Which pair show cis-trans isomerism [RPET 1999]
(a) HOH 2 C CH 2 CH 3
(a) Maleic-fumaric acid (b) Lactic-tartaric acid
(c) Malonic-succinic acid (d) Crotonic-acrylic acid CH CH 2
71. 1, 2-Dichloroethene shows [RPET 1999] CH 3
(a) Geometrical isomerism (b) Optical isomerism
(c) Ring-chain isomerism (d) Resonance (b) H 2C HCO CHO
72. Which compound is optically active [DCE 1999] CH 2 CH 3
(a) 4-chloro, 1 hydroxy butane CH 3
(b) 3 o -butyl alcohol (c) HOH 2 C COOH
(c) Secondary butyl amine
C CH
(d) -butyl alcohol
73. Choose the pair of chain isomer [RPMT 2000] CHO
(a) CH 3 CHBr2 and CH 2 BrCH 2 Br (d) H3C C N
(b) 1-propanol and 2-propanol CH 2 NH 2
(c) Neo-pentane and isopentane 84. Reason for geometrical isomerism by 2-butene is
(d) Diethyl ether and methyl- -propyl ether
[CBSE PMT 2000]
74. Optical isomerism arises due to the presence of
(a) Chiral carbon
[RPMT 2000]
(a) An asymmetric carbon atom (b) Free rotation about single bond
(b) Centre of symmetry (c) Free rotation about double bond
(c) Axis of symmetry (d) Restricted rotation about double bond
(d) Plane of symmetry 85. Stereoisomers which are not the mirror images of one another are
75. Least hindered rotation about carbon-carbon bond is observed in [RPMT 2000] called [RPMT 2000]
(a) Ethane (b) Ethylene (a) Enantiomers (b) Mesomers
(c) Ethyne (d) Hexachloroethane (c) Tautomers (d) Diasteroisomers
76. Which pair represents chain isomer [RPMT 2000] 86. The isomerism shown by -butyl alcohol and isobutyl alcohol is [RPMT 2000]
(a) CH 3 CHCl 2 and ClCH 2 CH 2 Cl (a) Metamerism (b) Chain
(c) Position (d) Stereo
(b) -propyl alcohol and isopropyl alcohol 87. Which is optically active [MH CET 2001]
(c) 2-methy -1 propanol and 2-Methyl-2 propanol
(d) 2-methyl butane and neopentane (a) CH 2 Cl 2
77. Which of the following compounds will exhibit geometrical (b) CHCl 3
isomerism [IIT-JEE Screening 2000]
(c) Meso form of tartaric acid
(a) 1-phenyl-2-butene (b) 3-phenyl-1-butene
(d) Glyceraldehyde
(c) 2-phenyl-1-butene (d) 1, 1-Diphenyl-1-propene
88. Which of the following will show geometrical isomerism
78. On bromination, propionic acid yields two isomeric 2-
bromopropionic acids. This pair is an important example of [BHU 2000] [CPMT 2001; BHU 2005]
(a) Chain isomers (b) Optical isomers (a) CH 3 CH CHCH 3 (b) (CH 3 )2 C C (CH 3 )2
 1054 General Organic Chemistry
(c) (CH 3 )2 C C(CH 3 )2 (d) CH 3 CH C (CH 3 )2 100. If the light waves pass through a nicol prism then all the oscillations
occur only in one plane, such beam of light is called as[Kerala (Med.) 2002]
89. What is the maximum number of open chain structures possible for
(a) Non-polarised light (b) Plane polarised light
C4 H 8 [MP PET 2001]
(c) Polarised light (d) Optical light
(a) 2 (b) 3 101. Racemic mixture is formed by mixing two [AIEEE 2002]
(c) 4 (d) 1 (a) Isomeric compounds (b) Chiral compounds
90. Glucose has optical isomers [DCE 2001]
(c) Meso compounds (d) Optical isomers
(a) 8 (b) 12 102. Which of the following does not show geometrical isomerism [AIEEE 2002]
(c) 16 (d) Cannot be predicted (a) 1, 2 dichloro-1-pentene
91. An organic compound
(b) 1, 3-dichloro-2-pentene
1
CH 3 2 CH 2 3 CH 2 4 CH 2 5 CH 2 6 CH 2 7 CH 3 (c) 1, 1-dichloro-1-pentene
To make it chiral compound the attack should be on which carbon (d) 1, 4-dichloro-2-pentene
atom [DCE 2001]
(a) 1 (b) 3 H3C CH 3 H3C H
(c) 4 (d) 7 103. C C and C C
92. Which of the following statements is not true about enantiomers[DCE 2001] H H H CH 3
(a) They have same physical properties
(b) They have different biological properties exhibit which isomerism [MP PET 2002]
(c) They have same chemical properties towards chiral compounds (a) Position isomerism (b) Geometrical isomerism
(d) None of these (c) Optical isomerism (d) Functional isomerism
93. Meso-tartaric acid is [BHU 2001] 104. Which compound is chiral [RPMT 2002]
(a) Optically inactive (a) butane
(b) Optically active because of molecular symmetry (b) 1-chloro-2-methyl butane
(c) Optically inactive due to external compensation (c) 2-methyl butane
(d) Optically active because of asymmetric carbon atom (d) 2-methyl propane
94. The number of possible isomers of the compound with molecular 105. Methyl acetate and propionic acid are [RPMT 2002]
formula C7 H 8 O is [BHU 2001] (a) Functional isomer (b) Structural isomer
(a) 3 (b) 5 (c) Stereoisomer (d) Geometrical isomer
(c) 7 (d) 9 106. Which compound shows - isomerism [CPMT 2002]
95. The number of isomers for the compound with molecular formula (a) 1-butene (b) 2-propene
C 2 BrClFIis [IIT-JEE (Screening) 2001] (c) 2-butene (d) Benzene
(a) 3 (b) 4 107. Isomers of propionic acid are [MP PMT 2002]
(c) 5 (d) 6 (a) HCOOC 2 H 5 and CH 3 COOCH 3
96. Hydrogenation of the adjoining compound in the presence of (b) HCOOC2 H 5 and C3 H 7 COOCH 3
poisoned palladium catalyst gives
[IIT-JEE (Screening) 2001] (c) CH 3 COOCH 3 and C 3 H 7 OH
Me H (d) C 3 H 7 OH and CH 3 COCH 3
108. The functional isomer of ethyl alcohol is [MP PMT 2002]
Me H (a) CH 3 OCH 3 (b) CH 3 COCH 3
(a) An optically active compound (c) CH 3 COOH (d) CH 3 CH 2 CHO
(b) An optically inactive compound 109. Disymmetric object is one which is [Kerala (Engg.) 2002]
(c) A racemic mixture (a) Superimposable on its mirror image
(d) A diastereomeric mixture (b) Non-superimposible on its mirror image
97. The number of possible structural isomers for a compound with the (c) Optically inactive
molecular formula C7 H16 is [DCE 2001]
(d) Achiral
110. Geometrical isomers differ in [CBSE PMT 2002]
(a) 8 (b) 9 (a) Position of atoms
(c) 10 (d) 12 (b) Length of carbon
98. Which of the following molecule contains asymmetric carbon atom[JIPMER 2002] (c) Spatial arrangement of atoms
(a) CH 3 CHClCOOH (b) CH 3 CH 2 COOH (d) Position of functional group
111. Which of the following hydride is capable of showing conformations[JIPMER 200
(c) ClCH 2 CH 2 COOH (d) Cl 2 CHCOOH
(a) NH 2 NH 2 (b) B2 H 6
99. A similarity between optical and geometrical isomerism is that[AIEEE 2002]
(a) Each forms equal number of isomers for a given compound (c) CH 4 (d) None of these
(b) If in a compound one is present then so is the other 112. Which of the following is an chiral compound
(c) Both are included in stereoisomerism [AIIMS 2002]
(d) They have no similarity (a) Hexane (b) Methane
(c) -butane (d) 2,3,4-trimethyl hexane
 General Organic Chemistry 1055
113. What is the possible number of optical isomers for a compound H 3C Cl H 3C Cl
containing 2-dissimilar asymmetric carbon atom
(a) C C (b) C C
[CPMT 1999; UPSEAT 1999, 2000, 02]
(a) 2 (b) 4 H Br H 3C Br
(c) 6 (d) 8 H Cl Cl Cl
114. Which of the following compounds is optically active (c) C C (d) C C
[Pb. PMT 2001; AMU 2002; Kerala (Med.) 2003]
D Br Br Br
(a) (CH 3 )2 CHCH 2 OH (b) CH 3 CH 2 OH
122. Isomerism shown by
(c) CCl 2 F2 (d) CH 3 CHOHC2 H 5 CH 3 (CH 2 )3 O CH 3
115. Optically active compound is [UPSEAT 2002] CH 3 CH 2 O CH 2 CH 2 CH 3
(a) 3-chloropentane (b) 2-chlorobutane CH 3
CH O CH 2 CH 3 is [RPMT 2003]
(c) 2-chloropropane (d) None of these |
116. If a carbon atom is attached to H, OH, COOH and CH 3
OCOC 2 H 5 number of chiral atoms in compound is (a) Position isomerism (b) Chain isomerism
(c) Metamerism (d) Optical isomerism
[RPMT 2003] 123. A compound whose molecules are superimposable on their mirror
(a) 1 (b) 2 images even through they contain an asymmetric carbon atom is
(c) 3 (d) 4 called [Kerala (Med.) 2003]
(a) A meso compound (b) An erythro isomer
117. Isomerism due to rotation round single bond of carbon-carbon is [UPSEAT 2003] (c) A threo isomer (d) a glycol
(a) Conformation (b) Enantiomerism 124. Of the following, the compound possessing optical isomerism [Kerala (Med.)
(c) Diasterio isomerism (d) Position isomerism (a) CH 3 CH 2 OH (b) CH 3 CHClBr
118. Which of the following pairs of compounds are enantiomers (c) CCl BrF (d) CCl F
2 2 2
[CBSE PMT 2003]
125. Which of the following statement is wrong [EAMCET 2003]
CH 3 CH 3 (a) Diethyl ketone and methyl propyl ketone are position isomers
HO H HO H (b) 2-chloro pentane and 1-chloro pentane are position isomers
(a) and (c) -butane and 2-methyl propane are chain isomers
H OH HO H (d) Acetone and propinaldehyde are functional isomers
CH 3 CH 3 126. Dimethyl ether and ethyl alcohol are
[MH CET 2004; Pb. CET 2002]
CH 3 CH 3 (a) Metamers (b) Homologues
H OH HO H (c) Functional isomers (d) Position isomers
(b) and 127. The correct statement about the compounds and is
HO H H OH
[DCE 2002; UPSEAT 2004; IIT-JEE 1997; DPMT 2005]
CH 3 CH 3
COOCH 3 COOH
CH 3 CH 3 H OH H OH
H OH HO H H OH H OH
(c) and
HO H HO H COOH COOCH 3
CH 3 CH 3 (A) (B)
(a) and are identical
CH 3 CH 3 (b) and are diastereomers
H OH H OH (c) and are enantiomers
(d) and (d) None of these
HO H H OH
128. Ethyl acetoacetate shows, which type of isomerism
CH 3 CH 3 [Pb. CET 2003]
CH 3 (a) Chain (b) Optical
H Br2 .CCl 4
(c) Metamerism (d) Tautomerism
119. [ F] C 4 H 8 Br2 129. Which of the following will have a mesoisomer also
H 2O
H 3C OH [AIEEE 2004]
5 such products
are possible (a) 2, 3-Dichloropentane
(b) 2, 3-Dichlorobutane
How many structures of is possible
(c) 2-Chlorobutane
[IIT-JEE (Screening) 2003] (d) 2-Hydroxypropanoic acid
(a) 2 (b) 5 130. For which of the following parameters the structural isomers
C2 H 5 OH and CH 3OCH 3 would be expected to have the same
(c) 6 (d) 3
values ? (Assume ideal behaviour) [AIEEE 2004]
120. An enantiomerically pure acid is treated with racemic mixture of an (a) Boiling points
alcohol having one chiral carbon. The ester formed will be[IIT-JEE (Screening) 2003] (b) Vapour pressure at the same temperature
(a) Optically active mixture (b) Pure enantiomer (c) Heat of vaporization
(d) Gaseous densities at the same temperature and pressure
(c) Meso compound (d) Racemic mixture
131. The geometrical isomerism is shown by [AIIMS 2004]
121. Which one of the following will not show geometrical isomerism [MP PMT 2003]
2 2
 1056 General Organic Chemistry
(c) Optical isomers (d) Geometrical mesomers
(a) (b) 143. CH 3 CH 2 CH CH 2 and CH 3 CH CH CH 3 show
(a) Chain isomerism (b) Position isomerism
(c) Functional isomerism (d) Metamerism
(c) (d) 144. The number of possible isomers of butene are
[Kerala (Engg.) 2002]
132. Which of the following compounds will exhibit (a) 3
isomerism[Kerala PMT 2004] (b) 2
(a) 2-butene (b) 2-butyne (c) 4 (d) 5
(c) 2-butanol (d) Butanone (e) 6
(e) Butanol 145. Which of the following show geometrical isomerism
[BCECE 2005]
133. Which of the following compounds exhibit stereoisomerism
[MP PMT 2004] (a) C 2 H 5 Br (b) (CH 2 )(COOH )2

(a) 2-methyl-butane I (b) 3-methyl-butanoic acid (c) (CH )2 (COOH )2 (d) C 2 H 6

(c) 3-methyl-butyne I (d) 2-methyl butanoic acid 146. Among the following the most stable compound is
134. The chirality of the compound [CBSE PMT 2005] [AIIMS 2005]
Br (a) cis 1,2 cyclohexanediol
|
C H (b) trans 1,2 cyclohexanediol
(c) cis 1,3 cyclohexanediol
H 3C Cl
(d) trans 1,3 cyclohexanediol
(a) (b) 147. Chirality of carbon compound is because of its
(c) (d) [Kerala (Med.) 2002]
135. Which of the following is most likely to show optical isomerism[UPSEAT 2004] (a) Tetrahedral nature of carbon
H H (b) Monovalent nature of carbon
| | (c) Divalent nature of carbon
(a) HC C C C CH (b) HC C C CH 3 (d) Trivalent nature of carbon
| |
Cl Cl 148. Which kind of isomerism is possible for 1-chloro-2-nitroethene[J & K 2005]
(a) Functional group isomerism
H Cl
| | (b) Position isomerism
(c) HC C C H (d) HC C C CH 2 (c) E / Z isomerism
|
Cl (d) Optical isomerism
136. Nitroethane can exhibit one of the following kind of isomerism[DCE 2004] 149. Which will give chiral molecule [DPMT 2005]
(a) Metamerism (b) Optical activity (a) CH 3 COCl
LiAlH4
(c) Tautomerism (d) Position isomerism
CH 3 MgBr
137. CH 3CH (OH ).COOH shows [BVP 2004] (b) C2 H 5 CHO
H / H 2O
(a) Geometrical isomerism (b) Optical isomerism
Cu
(c) Both (d) None (c) (CH 3 )2 CHC 2 H 5
138. Which will have enantiomer [BVP 2004]
H CH 3
(a) CH 3 CH 2 CH CH 3 (b) CH 2CH 2CH 2CH 2Cl Cl 2
| (d) C C
Cl CH 3 CH 3
(c) CH 3CH 2CH 2CHCl 2 (d) None 150. Which of the following will be chiral
139. The total number of acylic isomers including the stereoisomers with [J & K 2005]
the molecular formula C4 H 7 Cl (a) CH 3 CHCl 2 (b) CH 3CHBrCl
[Pb. CET 2004]
(c) CD2 Cl 2 (d) CH 2 ClBr
(a) 11 (b) 12
(c) 9 (d) 10 151. Which of the following fischer projection formula is same as D -
140. The number of possible enantiomeric pairs that can be produced Glyceraldehyde [Kerala CET 2005]
during mono-chlorination of 2-methylbutane is CH 2 OH
[Pb. CET 2004]
(a) OH CHO
(a) 3 (b) 4
(c) 1 (d) 2 H
141. Which one of the following pairs represents stereoisomerism CH 2 OH
[CBSE PMT 2005]
(b) H OH
(a) Chain isomerism and rotational isomerism
(b) Structural isomerism and geometric isomerism CHO
(c) Linkage isomerism and geometric isomerism CHO
(d) Optical isomerism and geometric isomerism (c) OH CH 2 OH
142. When isomers have the same structural formula but differ in relative
arrangement of atoms or groups are called H
[CPMT 2000; KCET (Med.) 2000]
(a) Mesomers (b) Stereoisomers
 General Organic Chemistry 1057

CHO (d) CH 3 CH 2 CH CH 2 CH 2 OH
|
(d) H CH 2 OH CH 3
HO 6. Which of the following statements is not characteristic of free
H radical chain reaction [JIPMER 1997]
(a) It gives major product derived from most stable free radical
(e) OH CH 2 OH
(b) It is usually sensitive to change in solvent polarity
CHO (c) It proceeds in three main steps like initiation, propagation and
termination
(d) It may be initiated by U.V. light
7. Most stable carbanion is [BHU 2003]
(a) CH 3 (b) CH 3 CH 2
(c) CH 2 (d) CH 2
1. In the given conformation C 2 is rotated about C2 C3 bond
anticlockwise by an angle of 120° then the conformation obtained is[AIIMS 2004]
NO 2 CH 3
4

3
8. Among the following the dissociation constant is highest for
[AIIMS 2004]
3 (a) C6 H 5 OH (b) C6 H 5 CH 2OH
2

(c) CH 3C CH (d) CH 3 NH 3 Cl
(a) Fully eclipsed conformation
9. Which one of the following compounds is most acidic
(b) Partially eclipsed conformation
1
3

[CBSE PMT 2005]

(c) Gauche conformation
(d) Staggered conformation
2. The molecular formula of diphenyl methane, (a) Cl CH 2 CH 2 OH (b)

2
, is C13 H12
How many structural isomers are possible when one of the (c) (d)
hydrogens is replaced by a chlorine atom [CBSE PMT 2004]
(a) 8 (b) 7 3

(c) 6 (d) 4 10. Which one is electrophilic addition [AMU (Engg.) 1999]
3. SN 1 reaction is faster in [Orissa JEE 2004] (a) CH 3 CH 3 Cl 2 C 2 H 5 Cl HCl
CH 3 (b) CH 3 CH O HCN (CH 3 )2 C(OH)CN
(a) CH 3 CH 2Cl (b) CH Cl
CH 3 (c) (CH 3 )2 C O HCN CH 3 CH (OH)CN
CH 3 (d) CH 2 CH 2 Br2 CH 2 BrCH 2 Br
|
(c) CH 3 C Cl (d) CH 3 CH Cl 11. A compound has 3 chiral carbon atoms. The number of possible
| |
CH 3 CH 2 optical isomers it can have [DCE 2004]
|
CH 3 (a) 3 (b) 2
4. How many enantiomer pairs are obtained by monochlorination of 2, (c) 8 (d) 4
3-dimethylbutane [Kerala PMT 2004] 12. How many chiral isomers can be drawn from 2-bromo, 3-chloro
(a) Nil (b) Four butane [DCE 2003]
(c) Two (d) Three (a) 2 (b) 3
(e) One (c) 4 (d) 5
5. Among the following compounds which can be dehydrated very
easily is [AIEEE 2004] 13. Number of isomers of C 4 H 10 is
CH 3 [CBSE PMT 1996; AFMC 1997; RPMT 2002; MP PMT 1997]
|
(a) CH 3 CH 2 C CH 2 CH 3 (a) 2 (b) 3
|
OH (c) 4 (d) Isomerism not exist

OH 14. The number of possible isomers for compound C 2 H 3 Cl 2 Br is[MP PMT 1999]
|
(b) CH 3 CH 2 CH 2 CH CH 3 (a) 2 (b) 3
(c) 4 (d) 5
(c) CH 3 CH 2 CH 2 CH 2 CH 2 OH
15. The optically active tartaric acid is named as (+)- tartaric acid
because it has a positive [IIT-JEE 1999]
 1058 General Organic Chemistry
(a) Optical rotation and is derived from -glucose (c)
(b) in organic solvent
(c) Optical rotation and is derived from (+) glyceraldehyde
(d)
(d) Optical rotation only when substituted by deuterium
16. Among the following compounds (I-III) the correct order of reaction 22. The following reaction is described as [CBSE PMT 1997]
with electrophilic reagent is [CBSE PMT 1997]
CH 3 (CH 2 )5 (CH 2 )5 CH 3
3 2

C Br OH HO C
H 3C | | CH 3
H H

I II III (a) SE 2 (b) SN 1

2
(a) II > III > I (b) III < I < II (c) SN (d) SN 0
(c) I > II > III (d) I = II > III 23. Which one of the following represents eclipsed form of ethane

17. Carbocation which is most stable [BHU 2003]

(a) (b)
(a) CH 3 CH 2 (b) CH 3

(c) C6 H 5 CH 2 (d) CH 3 CH 2 CH 2
18. Tautomerism is exhibited by
(c) (d) None of these
[CBSE PMT 1997; KCET 2002]

(a) (CH 3 )3 CNO (b) (CH 3 ) 2 NH

24. Which are the staggered forms of ethane
(c) R 3 CNO 2 (d) RCH 2 NO 2
19. Which of the following will have geometrical isomers
[MP PET 1996; MP PMT 1997; AFMC 1997]
(a) 2-methylpropene (b) 2-butene
1 2
(c) 1-butene (d) Propene
20. Examine the following three pairs of possible isomers

3 3 4
(a) 1 and 4 (b) 3 and 4
(c) 2 and 4 (d) 1 and 3
25. Which of the following is the most stable cation
[CBSE PMT 1988; MNR 1988; AIIMS 1985]
3

(ia) (iia) (iiia)

(a) CH 3 CH 2 C HCH 3 (b) CH 3 C CH 3

3 3
|
CH 3

(ib) (iib) (iiib) (c) CH 3 CH 2 CH 2 C H 2 (d) CH 3

Now state whether the pairs represent identical compounds or 26. In a reaction of C 6 H 5 Y , the major product (> 60%) is -isomer,
different isomers
so the group is [AIIMS 1997; UPSEAT 2003]
(a) All three pairs represent different compounds
(a) COOH (b) NH 2
(b) ( ) and ( ) are identical; ( ) and ( ) are identical; and ( )
and ( ) are identical (c) OH (d) Cl

(c) ( ) and ( ) are isomers; ( ) and ( ) are identical; and ( ) 27. Dehydrohalogenation in presence of OH is correctly represented
and ( ) are isomers by [Orissa JEE 2004]

(d) ( ) and ( ) are identical; ( ) and ( ) are identical, and ( )

(a) (b)
and ( ) are isomers
21. Tautomerism is exhibited by [IIT-JEE 1998]

(a) =
(c) (d)
(b)
28. Number of structural isomers of C 4 H 10 O are
 General Organic Chemistry 1059
[CPMT 1983, 84, 89, 91; MADT Bihar 1984; 38. How many carbon atoms in the molecule
MNR 1984; MP PET 1997; Pb. PMT 1999; MH CET 2003] HCOO (CHOH )2 COOH are asymmetric
(a) 3 (b) 6
[MP PET 2001]
(c) 7 (d) 10 (a) 1 (b) 2
29. Among the following the aromatic compound is (c) 3 (d) None of these
[AIIMS 2004] 39. Which of the following act as nucleophiles [Roorkee 1999]
(a) (b)
(a) CH 3 NH 2 (b) RO
+ + (c) AlCl3 (d) CH 3 MgBr
(c) (d) 40. Which of the following has the highest nucleophilicity
[IIT-JEE Screening 2000]
30. Which of the following compounds are not arranged in order of (a) F (b) OH
decreasing reactivity towards electrophilic substitution [DCE 2003]
(c) CH 3 (d) NH 2
(a) Fluoro benzene > chloro benzene > bromo benzene
(b) Phenol > -propyl benzene > benzoic acid 41. Keto-enol tautomerism is found in
(c) Chloro toluene > para-nitro toluene > 2-chloro-4-nitro toluene [IIT-JEE 1988; MADT Bihar 1995]
(d) Benzoic acid > phenol > -propyl benzene O
31. Most stable carbonium ion is [Pb. CET 2004] ||
(a) C2H5 (b) (CH 3 )3 C (a) H 5 C6 C H
O
(c) (C6 H 5 )3 C (d) C6 H 5 CH 2 ||
32. Which one of the following species is most stable (b) H 5 C6 C C6 H 5
[IIT-JEE 1995]
O
(a) p O2 N C6 H 4 C H2 ||
(c) H 5 C6 C CH 3
(b) p CH 3 O C6 H 4 C H2
O O
(c) p Cl C6 H 4 C H2 || ||
(d) H 5 C 6 C CH 2 C CH 3
(d) C 6 H 5 C H 2 42. Which of the following compounds will show geometrical isomerism[IIT-JEE 199
33. Which of the following gives most stable carbocation by dehydration [RPMT 2002]
(a) 2-butene (b) Propene
(a) (CH 3 ) 2 CH OH
(c) 1-phenylpropene (d) 2-methyl-2-butene
(b) (CH 3 )3 C OH
43. Which behaves both as a nucleophile and electrophile
(c) CH 3 CH 2 OH [IIT-JEE Screening 1991; Pb. CET 1985]
(d) CH 3 CH 2 O CH 2 CH 3 (a) CH 3 NH 2 (b) CH 3 Cl
34. Which of the following orders regarding relative stability of free
radicals is correct [UPSEAT 2004] (c) CH 3 CN (d) CH 3 OH
(a) 3° < 2° < 1° (b) 3° > 2° > 1°
(c) 1° < 2° > 3° (d) 3° > 2° < 1° 44. The number of optical isomers of an organic compound having
35. The + effect of alkyl groups is in the order [DCE 2002] asymmetric carbon atoms will be [MP PET 1994]
(a) 2° > 3° > 1° (b) 1° > 2° > 3° (a) 2n 1
(b) n 2
(c) 3° > 2° > 1° (d) None of these
36. Which one has asymmetric -atom [Roorkee 1995] (c) 2n (d) 2n 1

(a) CH 3 CH 2 CH 2
45. Total number of isomers of C 6 H 14 are
|
Br [IIT-JEE 1987; DPMT 1983; CPMT 1991;
(b) CH 3 CH CH CH 3 MNR 1990; MP PET 1995; UPSEAT 2001]
| | (a) 4 (b) 5
Br CH 3
(c) 6 (d) 7
(c) CH 3 CH 2 CH CH 3
| 46. With a change in hybridisation of the carbon bearing the charge, the
stability of a carbanion increase in the order
Br
[DCE 2003]
CH 3
| (a) sp sp 2
sp 3
(b) sp sp 3
sp 2

(d) CH 3 C CH 2 CH 2 CH 3
| (c) sp 3 sp 2 sp (d) sp 2 sp sp 3
Br
47. The bond length of the following molecules is in the order[IIT-JEE 1991]
37. Which of the following compounds will show metamerism
[KCET 1996] (a) C2 H 6 C2 H 4 C6 H 6 C2 H 2
(a) CH 3 COOC 2 H 5 (b) C 2 H 5 S C2 H 5
(b) C 2 H 2 C2 H 4 C6 H 6 C2 H 6
(c) CH 3 O CH 3 (d) CH 3 O C2 H 5
(c) C2 H 6 C2 H 2 C6 H 6 C2 H 4
 1060 General Organic Chemistry
(d) C2 H 4 C2 H 6 C2 H 2 C6 H 6 Reason : All isomeric paraffins have same parent name.
10. Assertion : A mixture of glucose and -dinitrobenzene can be
48. In the reaction CH 3 CHO HCN CH 3 CH (OH)CN a chiral separated by shaking it with ether.
centre is produced. This product would be Reason : Glucose is soluble in water.
[CBSE PMT 1995] 11. Assertion : Tertiary carbonium ions are generally formed more
easily than primary carbonium ions.
(a) Laevorotatory (b) Meso compound Reason : Hyperconjugative as well as inductive effect due to
(c) Dextrorotatory (d) Racemic mixture additional alkyl groups stabilize tertiary carbonium
49. ions.
a single plane. All the carbon-carbon bonds are of same length less 12. Assertion : Heterolytic fission involves the breaking of a
than 1.54 , but more than 1.34 . The C C bond angle will be [BVP 2003] covalent bond in such a way that both the electrons
of the shared pair are carried away by one of the
(a) 109 o 2 8 (b) 100 o atoms.
(c) 180 o (d) 120 o Reason : Heterolytic fission occurs readily in polar covalent
bonds.
50. How many structural isomers are possible for a compound with 13. Assertion : The order of reactivity of carbonium ions is
molecular formula C 3 H 7 Cl [CBSE PMT 2001] 2 3 1 .
(a) 2 (b) 5 Reason : Carbon atom in carbonium ions is in sp 3 state of
(c) 7 (d) 9 hybridisation.
14. Assertion : Free radicals are short lived and highly reactive.
Reason : Free radicals are highly unstable.
15. Assertion : Each carbon in ethylene molecule is sp 2
hybridised.
Reason : The H C H bond angle in ethylene molecule
is 120°.
Read the assertion and reason carefully to mark the correct option out of 16. Assertion : Cyclohexanone exhibits keto-enol tautomerism.
the options given below: Reason : In cyclohexanone, one form contains the keto group
( = ) while other contains enolic group
( C C OH) .
17. Assertion : Staggered form is less stable than the eclipsed form.
Reason : The conformation in which the bond pairs of two
central atoms are very far from one another is
called staggered form.
18. Assertion : isomers are more stable than isomer.
1. Assertion : Aniline is better nucleophile than anilium ion. Reason : The isomer is the one in which two similar
Reason : Anilium ion have + charge. [AIIMS 1996] groups are on the same side of double bond.
2. Assertion : Neopentane forms one mono substituted 19. Assertion : Propadiene is optically active.
compound. Reason : Propadiene has a plane of symmetry.
Reason : Neopentane is isomer of pentane. 20. Assertion : Lactic acid is optically active.
[AIIMS 2001] Reason : A symmetry in the inner structure of the organic
3. Assertion : -2-butene on reaction with Br2 gives - compound causes optical activity.
2, 3-dibromobutane. 21. Assertion : Same number of electron pairs are present in
Reason : The reaction involves syn-addition of bromine.[AIIMS 2003] resonance structures.
4. Assertion : Cis-1, 3-dihydroxy cyclohexane exists in boat Reason : Resonance structures differ in the location of
conformation. electrons around the constituent atoms.
Reason : In the chair form, there will not be hydrogen 22. Assertion : Carbon-oxygen bonds are of equal length in
bonding between the two hydroxyl groups. carbonate ion.
[AIIMS 2003] Reason : Bond length decreases with the multiplicity of bond
5. Assertion : Hydroxyketones are not directly used in Grignard between two atoms.
reaction.
Reason : Grignard reagents react with hydroxyl group.
[AIIMS 2003]
6. Assertion : Benzyl bromide when kept in acetone water it
produces benzyl alcohol.
Reason : The reaction follows mechanism.
2

[AIIMS 2003]
7. Assertion : Carbon possesses property of catenation.
Reason : Carbon atoms form double as well as triple bonds
during catenation.
8. Assertion : Olefins have the general formula C n H 2n 1 .
Reason : There is one double bond between two carbon
atoms in their molecules.
9. Assertion : Saturated hydrocarbons are chemically less reactive.
 General Organic Chemistry 1063

Structural and stereo isomerism

1 a 2 a 3 b 4 c 5 b
6 b 7 d 8 c 9 c 10 c
11 b 12 a 13 a 14 c 15 c
Bonding and hybridisation in organic compounds 16 a 17 b 18 d 19 a 20 d
21 b 22 a 23 a 24 a 25 d
1 b 2 c 3 b 4 b 5 c
26 b 27 d 28 c 29 c 30 d
6 a 7 b 8 c 9 d 10 a 31 a 32 d 33 b 34 a 35 c
11 c 12 c 13 c 14 d 15 b 36 a 37 b 38 b 39 c 40 d
16 a 17 d 18 a 19 a 20 c 41 c 42 a 43 d 44 a 45 b
21 d 22 d 23 d 24 c 25 c 46 d 47 d 48 b 49 c 50 a
26 ac 27 c 28 c 29 c 30 d 51 b 52 d 53 b 54 d 55 d
31 c 32 c 33 d 34 c 35 c 56 d 57 b 58 d 59 b 60 d

36 a 37 c 38 c 39 d 40 b 61 b 62 a 63 d 64 d 65 b

41 c 42 a 43 c 44 b 45 b 66 b 67 b 68 a 69 d 70 a

46 a 47 b 48 c 49 a 50 c 71 a 72 c 73 c 74 a 75 a
76 d 77 a 78 b 79 a 80 a
51 c 52 c 53 c 54 a 55 d
81 a 82 b 83 b 84 d 85 d
56 c 57 c 58 a 59 d 60 a
86 b 87 d 88 a 89 b 90 c
61 a 62 d 63 c 64 b 65 b
91 b 92 a 93 a 94 d 95 d
66 b 67 b
96 b 97 b 98 a 99 c 100 b

Dipole moment, resonance and reaction 101 b 102 c 103 b 104 b 105 a

intermediates 106 c 107 a 108 a 109 b 110 c

111 a 112 d 113 b 114 d 115 b
1 b 2 b 3 b 4 c 5 c 116 a 117 a 118 b 119 a 120 d
6 d 7 c 8 d 9 b 10 c 121 b 122 c 123 a 124 b 125 a
11 d 12 b 13 a 14 c 15 d 126 c 127 c 128 d 129 b 130 d
16 b 17 d 18 b 19 a 20 a 131 d 132 a 133 d 134 a 135 b
21 a 22 a 23 b 24 c 25 c 136 c 137 b 138 a 139 b 140 d
26 b 27 b 28 b 29 d 30 b 141 d 142 b 143 b 144 a 145 c

31 c 32 c 33 a 34 d 35 a 146 d 147 a 148 c 149 b 150 b

36 a 37 b 38 b 39 a 40 d 151 c

41 d 42 b 43 d 44 b 45 b
Critical Thinking Questions
46 a 47 b 48 d 49 b

1 c 2 d 3 c 4 e 5 a
Organic reactions and their mechanism
6 b 7 c 8 d 9 b 10 d

1 d 2 c 3 c 4 b 5 a 11 c 12 c 13 a 14 b 15 c

6 c 7 c 8 d 9 d 10 d 16 c 17 c 18 d 19 b 20 d
21 acd 22 c 23 b 24 c 25 b
11 b 12 d 13 c 14 d 15 c
26 a 27 a 28 c 29 a 30 d
16 a 17 a 18 d 19 b,c 20 a
31 c 32 b 33 b 34 b 35 c
21 d 22 a 23 d 24 a 25 a
36 bc 37 b 38 b 39 abd 40 c
26 b 27 d 28 b 29 b 30 d
41 cd 42 ac 43 c 44 c 45 b
31 d 32 c
46 c 47 b 48 d 49 d 50 a
 1064 General Organic Chemistry
Assertion & Reason bonds =5
hence electrons are double
1 a 2 b 3 c 4 d 5 a 14. (d) Cyclobutadienyl anion (C 4 H 4 )2
2
6 a 7 b 8 e 9 b 10 b HC CH
11 a 12 b 13 d 14 b 15 b electrons = 8.
16 a 17 e 18 b 19 e 20 b HC CH
Homolytic
21 e 22 b 15. (b) CH 3 CH 3 CH 3 CH 3
bond fission Methyl free radicals

free radical is formed which is sp 2 -hybridized.

one odd electron

H
C H
H
1 2 3 4
H2
16. (a) Br CH CH Br Br CH 2 CH 2 Br
2 2 Catalyst
sp sp sp 3 sp 3
Bonding and hybridisation in organic compounds
sp 3 sp 3 sp 3 sp 3
17. (d) (i) CH 3 CH 2 CH 2 CH 3
H
only sp 3 hybridized carbon
1. (b) (CH 4 ) sp 3 sp 2 sp 2 sp 3
C (ii) CH 3 CH CH CH 3
H H
H Both sp 2 and sp 3 hybridized carbon.
Tetrahedra l
sp 2 sp 2 sp 2 sp 2
3. (b) CH 2 CH 2 both the carbon atoms are sp 2 hybridised. (iii) CH 2 CH CH CH 2
5. (c) Type -character Only sp 2 hybridized carbon.
sp 3 25%
(iv) H C C H
sp sp
sp 2 33.33%
Only hybridized carbon.
50% 18. (a) (i) Benzene and its derivatives are always
sp sp
planar because all the carbon in benzene are sp 2 hybridized.
6. (a) CH CH
H
7. (b) sp 2 and sp 3 (v) CH 2 C
H
CH 3 CH2 CH2 CH 2 CH 3
sp 3 sp sp sp 3 sp 3 Both the carbon are sp 2 hybridized. Therefore planar.
sp 3 H
CH 3 |
3 | 19. (a) C Tetrahedral structure
sp 3
8. (c) CH 3 C sp OH Cl | Cl
| H
CH 3
sp 3 hybridization
sp 3

H H
All the carbon atoms are sp 3 hybridized. | |
20. (c) H C C C C H ; 11 bonds and 1 bond.
sp 2
sp 3
sp 2 | | | |
9. (d) CH 3 CH CH2 CH 2 CH2 CH C CH H H H H
sp sp sp sp
sp 3
21. (d) CH 3 CH CH 2 CH 3
|
10. (a) CH 3 C C H CH 3
sp sp
sp 3
It has 3 CH 3 groups, one CH 2 group and one group.
11. (c) and sp 2
sp sp 2
N C CH CH 2
1 2 3

13. (c) electrons = 10.

 General Organic Chemistry 1065

H H
|
| H
22. (d) H C H | 39. (d) H C H
| |
C H C
|
H

H
O dimethyl benzene
or
O xylene
15 and 3 .
It has 18 bonds and 3 bonds.
H 40. (b) In CCl 4 all bond angles are same . of 109 o 2 8 the carbon
is hybridised.
3

23. (d) 41. (c) Geometry in sp 2 -hybridisation is trigonal.

42. (a) CH2 C CH2 CH 3
H sp sp sp sp 3
C C bonds = 6
43. (c) Single bond has longest distance of bonds so C 2 H 6 ethane is
C H bonds 6 correct answer.
3
12
2 3 47. (b) HC C CH CH 2
24. (c) 2
sp sp
2 3

3 48. (c) In ethylene molecule carbons are 2

hybridised so its structure
is trigonal planar
Cyclo hexene
Two carbon atoms are sp 2 -hybridized while remaining 4 are 49. (a) CH CH
3 sp sp
sp hybridized.
1 2 3 4 5 6
25. (c) CH 2 CH C C CH 2 CH 3 52. (c) 5 bonds are present in naphthalene.
3-hexyne -1-ene
Three bonds.
26. (a, c) Carbonium ions an 2
hybridized species. H H H H
| | | |
54. (a) H C C C C C
H CH 3 |
C H C H
H H H
(CH 3 ) (C 2 H 5 ) 10 3

27. (c) (a) H C C H (b) CH 2 CH C O 1 2

2 bonds |
57. (c) CH 2 C CH 2
H sp 2
sp
2 bonds
(c) CH 3 CH CH 2 (d) CH 3 CH CH C OH
1 bond 2 bonds || H H H CH 2 CH 3 H CH 3 H
O | | | | | | |

sp
59. (d) H C C C C C C C H
|7 |6 |5 1|
N C C N |4 |3 |2
sp H H CH 3 H H H H
28. (c) C2 C2 2, 5 d; methyl 4 - ethylheptane (5 Methyl group)
sp sp
N C C N
sp sp sp 3 sp 2 sp 3 sp 3 sp 2
60. (a) CH 3 CO CH 3 CH 3 COOH
29. (c) H C C H 3 and 2 bonds are present. Acetone Acetic acid

30. (d) Vinyl acetylene there are 6 unhybridised orbitals. sp 3 sp sp 3 sp 2

CH 3 C N CH 3 CONH 2
CH 2 CH2 C CH Acetonitrile Acetamide
sp sp sp
sp 2
1 2 2
1
(no. of unhybridis ed orbitals) 2 2
31. (c) Bond energy is maximum for triple bond. 61. (a) CH 2 C H C H 2 C N
32. (c) CH 2 CH 2 Allylcyanide
5 ,1

33. (d) In benzene all 6 carbons are sp 2 hybridised. Total 9 bond and 3 bond.
34. (c) CH 2 CH2 CH2 CH 2 62. (d) Because hydrogen is attached with high electronegative
sp 2 sp sp sp 2 element.
36. (a) CH 2 CH C CH
7 ,3
63. (c) CH CH
37. (c) Propyne has one acidic hydrogen. Ethyne

3
 1066 General Organic Chemistry

64. (b) has 15 bonds. 19. (a) C C

21. (a) It is hyperconjugation process.
22. (a) Triphenyl methyl cation has three benzene resonating ring so it
is most stable compound.
65. (b) 23. (b) Due to mesomeric effect (+) of group the electron
density on benzene ring increase. So the electrophile easily
attacked on these electron rich center.
24. (c) Carbonyl carbon become more reactive toward nucleophilic
addition by increasing the + effect of alkyl group so the
12 and 3 bonds reactivity order is as
66. (b) The s -character of C H bond of acetylene is higher in
comparison to C H bond of ethene and ethane. The HCHO CH 3 CHO CH 3 COCH 3
I II IIII
electrons of the C H bond in acetylene are strongly held by
carbon nuclei. This facilitates the removal of hydrogen as H CH 3 CH 3
proton. C O C O C O
H H CH 3
. .
: OH 25. (c) The octet of all atoms are complete in structures (a) and (b).
| In structure (d) electron deficiency of positively charged carbon
67. (b) CH 3 C CH 2 is duly compensated by lone pair electrons of adjacent oxygen
9 1 & 2 L.p atom while such neighbour group support is not available in
structure (c).
Dipole moment, resonance and reaction CH 3
|
intermediates 26. (b) CH 3 C Due to (+ ) effect of three methyl group 3°
|
CH 3
CH 3
carbocation is more stable.
1. (b) CH CH
H3C 27. (b) CH 3 CH CH 3 CH CH 3 CH
| | |
0 symmetrical structure. CH 3 OCH 3 COCH 3
2. (b) Due to presence of two chlorine atom on the same side of
carbon atom produces dipole moment in molecule. 28. (b) C 6 H 5 CH 2 CH 3 CH 2
4. (c) We know that there is more difference in the electronegativities Benzyl carbanion Ethyl carbanion
of hydrogen and chlorine. Therefore is a polar compound. (CH 3 )2 CH (CH 3 )3 C
3
Isopropyl carbanion Tert- butyl
Carbanion
+
| | | | 30. (b) 3° alcohol on dehydrogenation gives most stable carbonium ion.
5. (c) (i) C C C C (ii) 32. (c) Without intermediate reaction take place as under
| |
Trans - 2 butene
(u 0 ) 3
Br
+ |
CH 3 CH CH 2 HBr CH 3 CH CH 3
3

(iii) (iv) C 2 H 5 OH (According to markownikoff rule)

I But the halogen bonded with terminal carbon so it take place
The dipole moment is the highest for Acetophenone. in presence of peroxide by free radical mechanism.
6. (d) Resonance structure of molecule does not have identical . .
bonding. R O OR 2 R O ; HBr RO ROH Br.
peroxide
.
7. (c) CH 3 CH CH 2 Br. CH 3 C H CH 2 Br
.
All the bonds (C C) are equal in benzene. The C C bond CH 3 CH CH 2 Br HBr
length is 1 .39 Å which is in between C C bond (1.54 Å) CH 3 CH 2 CH 2 Br Br.
and C C (1 .34 Å) . 33. (a) Species Valence Magnetic
electrons behaviour
1. Free radical 7 Paramagnetic
9. (b) (1) Molecule is planar. 2. Carbonium ion 6 Diamagnetic
(2) 6 electrons are present. 3. Carbanion 8 Diamagnetic
11. (d) Benzene is unreactive instead of having 3 bonds because of 4. Carbene 6 Diamagnetic
5. Nitrene 6 Diamagnetic
resonance -electrons are delocalized.
12. (b) Carboxylic acids are easily ionized because there is resonance in CH 3 CH 3
| | o
carboxylate ion due to electron shifting so H get ionised o
34. (d) CH 3 C CH 3 CH CH 3 CH 2
very easily. | o
3o CH 3 2o 1o
O O
C O H C H Greater the no. of alkyl groups attached to the carbon atom
.. O carrying the odd electrons, greater is the delocalization of odd
electron and hence more stable is the free radical.
13. (a) Due to delocalisation of electrons benzene has resonance.
 General Organic Chemistry 1067
Dispersal of positive charge increases with the increase in the
C number of benzene ring.
35. (a) R R
R Organic reactions and their mechanism
R
|
1. (d) It is SN 2 type of reaction.
36. (a) CH 3 R CH 2 R CH R C
| | Light
Methyl 3. (c) Cl 2 2Cl
carbanion
o
R R
1 2 3
3 2

CH 3 Cl
| H (Freeradical substitution)
37. (b) CH 3 C CH 3 CH CH 3 CH 2 CH 3
| |
5. (a) It is nucleophilic substitution reaction which is in first order.
CH 3 CH 3 Methyl
9. (d) All cations are expected to act as Lewis acid since they are
1o
3o 2 carbocation
electron deficient in nature. However cation such as Na , K
Greater the no. of alkyl groups, greater would be the dispersal etc. (Inert gas configuration) have a very little tendency to
of the charge and hence more stable will be the carbonium ion. accept electrons. Therefore they do not acts as lewis acids in
39. (a) C C bond length in benzene is 1.39Å which is in between
C C (1.54 Å) and C C (1.34 Å) because of resonance. 10. (d) The process of nitration takes place as below
Heterolytic HONO2 2 H 2 SO 4 H3 O 2 HSO 4 NO 2
40. (d) C Cl C Cl (nitronium ion)
bond fission Cation Anion

41. (d) CH 3 CH 2OH

Heterolytic cleavage
CH 3 CH 2 OH The electrophile responsible for nitration is NO 2 ion.
11. (b) Dehydrohalogenation of an alkyl halide on presence of alcoholic
H H H potash is an example of elimination reaction.
| | |
SbCl 5
43. (d) CH 3 C Cl Cl C CH 3 CH 3 C Cl R CH 2CH 2 Cl KOH
alc.

RCH CH 2 KCl H2 O
CH 2
( ) form ( ) form || CH 3
44. (b) The reaction of an alkyl halide or aryl halide with benzene in 12. (d) CH HCl |
| CH
the presence of a Lewis acid, generally AlCl3 is known as Cl
Friedel Craft's reaction. (1, 1 dichloroethane )
It is addition reaction.
2
Which is according to Markownikoff rule.
45. (b) gives only monosubstitution product as 13. (c) CH CH H 2 CH 2 CH 2
NO 2 group is meta directing and only one That is called addition reaction.
m -position is possible in m -dinitrobenzene.
2
14. (d) When methane gas is treated with chlorine in the presence of
46. (a) According to Huckel ruel, all aromatic compounds must have sunlight, one hydrogen of methane replaced by the chlorine
(4 n 2) electrons where n is an integer, , atom and forms methyl chloride. The mechanism involved in
this reaction is free radical mechanism. So it is an example of
n 0, 1, 2, 3, ... and possesses unusual stability due to the
free radical substitution reaction.
complete delocalisation of -electrons.
15. (c) Due to OH attack it is nucleophilic substitution.
47. (b) H O H , : NH 3 , R O R - nucleophiles SO 3 has 16. (a) Electron deficient species (in complete octet) acts as an
electrophile BCl 3 .
electron deficient centre (a reagent which can accept an
electron pair in a reaction, is called an electrophile) 17. (a) NO 2 is produced when conc. HNO 3 reacts with
48. (d) Chlorine atom is directing group. conc. H 2 SO 4 .
49. (b) Stability of carbonium ions.
tertiary alkyl > secondary alkyl > primary alkyl > methyl. HNO 3 H 2 SO 4 HSO 4 NO 2 H 2 O
More the number of alkyl groups, the greater the dispersal of 18. (d) Phenol will undergo electrophilic substitution more readily than
positive charge and therefore, more the stability of carbonium benzene.
ion is observed.
2 2

19. (b,c) +
+

2 2

Di nitro fluoro benzene Di nitro phenol

20. (a) AlCl3 is lewis acid , electron deficient compound. So it is
electrophile.
triphenylmethyl cation 21. (d) CH 3 O is the strongest nucleophile which is capable of
acting as donar of electon pair.
 1068 General Organic Chemistry
22. (a) The phenyl ring having < group is activated while Structural and stereo isomerism
another one is deactivated due to C , so electrophilic
||
O H
|*
aromatic bromination will occur at para position with respect
to < group inactivated ring. 5. (b) CH 3 C COOH
|
23. (d) The non reactivity of the chlorine atom in vinyl chloride may Cl
be explained from the molecular orbital point of view as In this structure chiral carbon atom is present since it is optical
follows. If the chlorine atom has sp 2 hybridization the active.
6. (b) In ethane staggard form and in cyclohexane chair form is more
bond will be a -bond and the two lone pairs of electron stable.
would occupy the other two sp 2 orbitals. This would leave a
-orbital containing a lone pair and this orbital could not
conjugate with the bond of the ethylenic link. Thus two
M.O.S. will be required to accommodate these four electrons.
Further more since chlorine is more electronegative than Chair form
carbon, the electron will tend to be found in the chlorine atom NH 2
has now lost full control of the one pair and so, is less negative |
than it would have been had there been no conjugation. Since 7. (d) CH 3 CH 2 C CH 3
two carbon atoms have acquired a share in the lone pair, each |
atom acquires a small negative charge. Hence, owing to H
delocalisation of bonds (through conjugation), the vinyl
chloride molecule has an increased stability. Before the chlorine Chiral centre is present. Hence, it exists as optical isomers or
atom can be displaced by some other group the lone pair must enantiomorphs.
be localised again on the chlorine atom. This requires energy 8. (c) In C6 H 5 CH 2 CH 3 chiral centre is absent.
and so the chlorine is more firmly bound than has no 9. (c) C 2 H 2 Br2 has three isomers.
conjugation occurred.
Br
|
2 2
(1) H C C H (2) CH CH
| | |

Br Br Br
24. (a) Nucleophiles are those substances which can donate a pair of
(Trans)
electrons. These can be neutral or negative. The nucleophilic (cis)
1, 2- dibromoeth ene
1, 2 -dibromoeth ene
power depends on the tendency of species to donate electrons.
This is more, when an electron pushing group (+ group) is (3) CH 2 C Br
present. Among the alkyl groups, those having higher number Br
1, 1 dibromoeth ene
of -atoms will push more, hence ethyl > methyl.
10. (c) Lactic acid shows optical isomerism
O
|| H H
2
>> 5 3
>> C , 3
>> 2
, | |
(+I) (+I) (+I)
C C
+
CH 3 | OH HO | CH 3
5 2

( I)
COOH COOH
25. (a) Conjugated acid of Cl is a stronger acid i.e., HCl .
26. (b) Saytzeffs product. H
|
29. (b) If the dehydrohalogenation of an alkyl halide can yield more than
one alkene, then according to the saytzeff rule, the main product is 11. (b) CH 3 C CH 2 CH 3
|
the most highly substituted alkene. Cl
2 - Chlorobuta ne
HO OH
because they contain chiral carbon atom.
H H H H 12. (a)
| | | | H 2C CHCH 2 CH 3 H
H C C C C H 1- butene (20%) |
CH 3 CH CHCH 3
| | | | 2 - butene(80% ) 13. (a) CH 3 C * CH 2 CH 3
H Br H H |
30. (d) Halogenation of alkanes takes place in presence of light Cl
(sunlight or UV) or at elevated temperature via free radical. In other compounds chiral carbon is absent.
31. (d) All the given species undergo nucleophilic substitution reaction. 14. (c) Ball is achiral where other objects are chiral because objects and
This reactivity can be explained in terms of the nature of C X their mirror images are non-super imposable
bond which is highly polarised covalent bond due to large
difference in the electronegativities of carbon and halogen atoms.

C X
32. (c) Increasing + I effect (a) (b) (d)
(CH 3 )3 C (CH 3 )2 CH CH 3 CH 2 CH 3
 General Organic Chemistry 1069

X 26. (b) Polarimeter is an instrument used for measuring the optical

X X rotation. It consists of two Nicol prisms, one called the
polarizer (near the light source) and the other called the
15. (c) analyser (near the eye). In between the polarizer and analyser,
a glass tube containing the solution of an optically active
X compound is placed.
ortho1, 2 X Meta 1, 3
or 1, 6 Para 1, 4 or 1, 5 Second
Polariser Glass Eye
H Nicolprism
tube
|
17. (b) CH 3 C* COOH Plane
| Analyser
Light Ordinary polarized
OH source light light
Only one chiral centre. Hence two optical isomers are possible.
CH 3 CH 3 Ray diagram of polarimeter
27. (d) CH 3 CH 2 CH 2 CH 3 and CH 3 CH CH 3
n butane |
C C CH 3
Iso butane
HO H H OH
28. (c) Metamerism is a special types of isomerism shown by
COOH COOH secondary amines, ethers and ketones.
No. of optical isomer = 2 n (where = no. of chiral carbon) = 29. (c) CH 3 CH 2 CH 2 CH 2 CH 2 OH
1 Pentan -1-ol
2 = 2. 4 3 2 1
19. (a) CH 3 CH 2 CH 2 CH 3 and CH 3 CH CH 3 CH 3 CH CH 2 CH 2 OH
n butane | |
CH 3 CH 3
Iso butane 3 Methylbutan 1 ol
4 3 2 1
H
| CH 3 CH 2 CH CH 2 OH
|
20. (d) CH 3 C CH 2 CH 3 Chiral structure is that in which CH 3
|
2 Methyl butan l ol
OH
one carbon atom is attached to 4 different atoms or groups. CH 3
|
3 2 1
21. (b) CH 3 CH 2 CH CH 2 & CH 3 CH CH CH 3 CH 3 C CH 2 OH
1 butane 2 butane
|
CH 3 CH 3
| 2 , 2 Dimethyl propan l ol
22. (a) HC CH and HC CH 30. (d) Position isomers :
| | |
CH 3 CH 2 CH 2 CH 2 OH and
CH 3 CH 3 CH 3 Butan -1- ol
(Cis) (Trans)
2 - butene 2 - butene CH 3 CH 2 CH CH 3
|
23. (a) Four groups linked to carbon atom are different OH
Butan 2 ol
X Functional isomers:
| CH 3CH 2CH 2 CH 2 OH and C2 H 5 O C2 H 5
Butanol Diethyl ether
C
Metamers: C2 H 5 O C2 H 5 and CH 3 O C3 H 7
| Diethyl ether Methyl propyl ether
Z 31. (a) 1. CH 3 CH 2 CH 2 CH 2 OH
Butan -1-ol
25. (d) Five isomers of C4 H8
2. CH 3 CH 2 CH CH 3
|
CH 3 OH
| Butan - 2 - ol
1. CH 3 C CH 2 2. CH 3 CH 2 CH CH 2
Isobutene 1 butene
3. CH 3 CH CH 2 OH
|

CH 3 H CH 3
H 2C CH 2 2 methyl propan -1 - ol
3. | | 4. C C CH 3
H 2C CH 2 H CH 3 |
Cyclobutane 4. CH 3
Trans - 2 - butene C CH 3
|

CH 3 CH 3 CH 3 OH
2 - Methyl propan - 2 - ol
5. C C 6. 32. (d) C4 H10 O have six isomers are possible
H CH 3 CH 2 CH 2
cis- 2 - butene 1. CH 3CH 2CH 2CH 2 OH
Methyl cyclopropane Butan -1-ol
 1070 General Organic Chemistry
2. CH 3 CH 2 CH CH 3 Diethyl ether C2 H 5 O C2 H 5 is position isomer and not
|
stereoisomer.
OH
Butan - 2 - ol 41. (c) C2 H 5 O C2 H 5 and CH 3 O C3 H 7
3. CH 3 CH CH 2 OH
| are metamers.
CH 3 42. (a) CH 3 CH 2 CH 2 OH and CH 3 CH CH 3
2 - Methyl propan -1 - ol n propyl alcohol |

CH 3 OH
Iso propyl alcohol
|
4. CH 3 C CH 3 are position isomers of each other.
|
44. (a) R N C and R C N are functional isomers.
OH
2 Methyl- propan - 2 - ol 45. (b) Optical isomerism because chiral centre is present
5. CH 3 O C3 H7 H
Methyl propyl ether |

6. C2 H 5 O C2 H 5 (CH 3 )2 C CH C COOH .
Diethyl ether |
CH 3
Cl
33. (b) CH CH CH CH 46. (d) Butanone CH 3 C CH 2 CH 3 (C 4 H 8 O) is not an
||
Cl Cl Cl O
(cis) (trans )
1 2 3 4 5 6,7
isomer of C2 H 5 O C2 H 5 (C4 H10 O)
34. (a) CH 3 CH CH CH CH C2 H 5
47. (d) Chair and boat form differ in energy by 44 /
1. CH CH
H 3C CH CH C2 H5
(cis)

CH CH C2 H 5 Chair form Boat form

2. CH CH
48. (b) CH 3 O CH 2 CH 3 and CH 3 CH 2 CH 2 OH
H 3C
(trans ) ethylmethyl ether and propylalcohol are functional isomers.
49. (c) CH 3 CH 2 CH 2 O C2 H 5
3. CH CH Ethoxy propane

CH 3 CH HC C2 H 5
(cis) CH 3 CH 2 CH 2 O C2 H 5
Propoxy ethane
C2 H 5
Both are same compounds.
4. CH HC
CH 3 CH HC 50. (a) CH 3 CO CH 3 and CH 3 CH 2 CHO are
(trans )
functional isomers.
36. (a) Molecular symmetry
COOH 51. (b) Three isomers are possible
|
H C CH 3 CH 3 CH 3
| Plane of Symmetry 3

H C
3

|
COOH 3

Mesotartaric acid is optically inactive due to internal 1, 2, 3 - Trimethyl

benzene
CH 3 3
3

compensation the effect one half of the molecule is 1, 2, 4 - Trimethyl 1, 3, 5 - Trimethyl

benzene benzene
neutralized by other.
52. (d) Diastereoisomers Optical isomers which are not mirror
H images of each other.
|
37. (b) CH 3 C COOH * chiral centre is present. . .
|
OH COOH COOH
| |
CH 3 H C OH and H C OH
| | |
38. (b) COOH C CH 2 CH 3 H C OH HO C H
| |
|
COOH COOH
OH
Diastereoisomers
One chiral centre. Therefore two forms are possible.
39. (c) Optical isomerism and geometrical isomerism. 53. (b) C 7 H 9 N has 5 isomers
40. (d) (a) CH 3 CH 2 CH 2 COOH (C4 H 8 O2 )
(b) CH 3 CH 2 COOCH 3 (C4 H8 O2 )
 General Organic Chemistry 1071

CH 3 CH 3
CH 2 NH 2 CH 3 CH 3 |
NH 2 CH CH and CH CH
| | |
CH 3 CH 3 CH 3
NH 2 H
Benzyl amine O Methyl aniline m methyl NH 2 |*
aniline
64. (d) I C Br
p methyl |
aniline
Cl
NH CH 3 A carbon atom which is attached to four different atoms or
groups is called a chiral or asymmetric carbon atom. such a
carbon atom is often marked by an asterisk.
65. (b) R C N and R N C are functional isomers.
Cyanide Isocyanide

n methyl 66. (b) Glucose and fructose have similar molecular formula with
aniline difference of functional group, so they are functional isomers.
54. (d) (1) CH 3 CH 2 CH 2 CH CH 2 67. (b) 2-butanol (CH 3 CH CH 2 CH 3 ) is optically active
Pent -1 - ene |
OH
(2) CH 3 CH 2 CH CH CH 3
Pent - 2 - ene
because it has asymmetric carbon atom.
69. (d) Ethane has all single ( ) bonds so there is minimum
(3) CH 3 CH 2 C CH 2
| resistance in bond rotation.
CH 3
2 Methyl 1 butene 70. (a)
(4) CH 3 CH C CH 3 C C C C
|
CH 3 Maleic acid
2 Methyl 2 butene (cis isomer) Fumaric acid
(trans-isomer)
71. (a) ClHC CHCl two structures are possible
2

(5) 2
2
C C C C
2 2
Cyclopentane
Geometrical isomerism
H asymmetric centre H
|
|
55. (d) CH 3 C COOH 2 hydroxy propanoic acid 72. (c) CH 3 C CH 2 CH 3
| (lactic acid) |
OH NH 2
58. (d) CH 3 C CH 2
|
CH 3 Secondary butyl amine is optically active.
2-methyl propene does not show geometrical isomerism. 73. (c) Neopentane and isopentane are chain isomers.
59. (b) Conformers - Conformation arises because of free rotation
CH 3
around C C bond axis. |
H H CH 3 C CH 3 and CH 3 CH 2 CH CH 3
| | | |
60. (d) CH 3 C C COOH CH 3 CH 3
| |
Br Br 75. (a) Due to single bond there is no hindrance
Number of enantiomers = 2 n ( = asymmetric Carbon atom) = 77. (a) Only 1-phenyl-2-butene will exhibit isomerism.
2 2 = 4. 79. (a) Geometrical isomerism is not possible in propene.
61. (b) C6 H5 C N and C 6 H 5 N C are functional isomers. 80. (a) Two isomeric forms are possible for 2-methyl propane.
62. (a) DCH 2 CH 2 CH 2 Cl Others are chiral CH 3 CH 2 CH 2 CH 3 & CH 3 CH CH 3
|
H H CH 3
| |
n butane 2 methyl propane
CH 3 CH 2 C D; CH 3 C CH 2 CH 2 Cl
| | 84. (d) Restricted rotation is essential condition for geometrical
Cl D isomerism.
H
| H 3C
88. (a) and C C
CH 3 C CH 2 D C C
| CH 3
Cl 3
cis isomer
3
Trans isomer
63. (d) Cis and trans 2-butene are geometrical isomers. 89. (b) Three isomeric structures are possible for C 4 H 8
H 2C CH CH 2 CH 3
 1072 General Organic Chemistry
CH 3 CH CH CH 3 O OH
|| |
CH 3 C CH 2 CH 3 C O CH 2 CH 3 CH 2 C OC 2 H 5
|
CH 3 CH 3 CH 3
| |
92. (a) Enantiomers have same chemical properties but different 129. (b) H C Cl H C Cl
| |
physical properties. H C H H C Cl
93. (a) Meso isomer have two achiral carbon with opposite spin so it | |
becomes optically inactive CH 3 CH 3
2 chlorobuta ne 2, 3 dichlorobu tane

CH 3
|
H C Cl OH
| |
H C Cl H3C C COOH
| |
H C H H
| 2 hydroxy propanoic acid
Meso tartaric acid CH 3
2, 3 dichlorope ntane

130. (d) Gaseous density of both ethanol and dimethyl ether would be
C C C C same under identical condition of temperature and pressure
95. (d) C C while the rest of these three properties vapour pressure, boiling
point and heat of vaporization will differ as ethanol has
(Z & E) (Z & E) (Z & E) hydrogen bonding where as ether does not.
96. (b) Due to formation of the plane of symmetry by the syn addition CH 3 CH 3 CH 3 H
of hydrogen in the triple bond, the compound formed is 132. (a) C C C C
H H H CH 3
optically inactive. cis 2 butene Trans 2 butene
101. (b) Racemic mixture is combination of and isomers. Cis-trans isomerism shown by compound which have double or
102. (c) Cl 2 C CH CH 2 CH 2 CH 2 triple bond by which they restrict their rotation, since 2 butyne
have no hydrogen on triple bonded carbon.
geometrical isomerism due to unsymmetrical alkene.
103. (b) Geometrical isomerism. CH 3 C C CH 3 [It does not show cis-trans]
2 butyne
104. (b) CH 3 CH 2 CH CH 2 Cl 133. (d) Because it contain asymmetric carbon atom.
*|
CH 3 CH 3 CH 2 CH COOH
|
105. (a) Functional isomerism CH 3
109. (b) Non superimposible on its mirror image.
H
CH 3 CH 3 CH 3 |
| | | 135. (b) HC C C CH 3 shows optical isomerism because of
112. (d) CH 3 CH 2 CH CH CH CH 3 , it is a chiral |
Cl
compound.
molecule is unsymmetrical. That is called chiral.
OH
|* 136. (c) Nitroalkanes exhibit tautomerism. In it, H atom is
114. (d) CH 3 C H labile and form nitrolic acid.
| O OH
C2 H 5 H 3 C CH 2 N H 3 C CH N
O O
In this structure chiral carbon is present that is why it is
optically active. CH 3
|
115. (b) 2-chloro butane will be optically active. 137. (b) H C COOH shows optical isomerism due to presence of
118. (b) Structures are mirror images of each other which are non |
super impossible so they are enantiomers. OH
120. (d) Both have one chiral carbon atom hence racemic mixture will asymmetric carbon atom.
be obtain 138. (a) 2-chloro butane has a chiral carbon atom, hence only it will
121. (b) Structure have 3-different atoms and group so it is unable to show optical activity and will possess two enantiomers (one
show geometrical isomerism chiral carbon atom).
122. (c) Metamerism is shown by the different arrangement of alkyl H
group about functional group. |
H CH 3 CH 2 C CH 3
| |
124. (b) CH 3 C Cl , it is a chiral compound. Cl
*|
Br 139. (b) C4 H7 Cl is a monochloro derivative of C4 H 8 which itself
126. (c) CH 3 O CH 3 and C2 H 5 OH are functional isomers. exists in three isomeric forms.
127. (c) Both are enantiomer. (i) CH 3 CH 2 CH CH 2 : Its possible mono-chloro
128. (d) CH 3COOC 2 H5 shows tautomeric isomerism. derivatives are :
CH 3 CH 2 CH CH Cl
 General Organic Chemistry 1073
2 isomers : cis and trans forms types (i) Geometrical isomerism (ii) Optical isomerism (iii)
Conformational isomerism.
CH 3 CH CH CH 2 144. (a) CH 3 CH CH 2 CH 3 ; CH 3 CH CH CH 3 ;
|
Cl CH 3 C CH 2
|
optically active (exists in two forms) CH 3
ClCH 2 CH 2 CH CH 2 (one form)
H COOH H COOH
Cl
| C C
H 3 C CH 2 C CH 2 (one form) 145. (c) || and ||
C C
(ii) CH 3 CH CH CH 3 : Its possible monochloro
H COOH HOOC H
derivatives are :
146. (d) configuration is more stable than configuration
CH 3 CH C CH 3 because in -configuration the groups are thrown closely
|
Cl enough together to cause crowding or repulsion. Again
Exists in two geometrical forms between 1,2-and 1,3-configurations, in 1-3, the groups are
placed further apart to minimise the repulsion. Hence, more
CH 3 CH CH CH 2Cl stable is 1,3-configuration.
Exists in two geometrical forms 147. (a) Chirality of carbon compound is because of its tetrahedral
(iii) CH 3 C CH 2 : Its possible monochloro derivatives nature of carbon.
|
148. (c) O2 NHC CHCl
CH 3 1- chloro- 2 - nitroethene
are For highly substituted alkenes E and Z system of
CH 3 C CH Cl nomenclature is used, which is based on a priority system
| developed by Cahn, Ingold and Prelog.
CH 3
H
Only one form |
CH 3 MgBr
ClCH 2 C CH 2 149. (b) C 2 H 5 CHO C2 H 5 C* OH
| H / H 2O |
CH 3 CH 3
Only one form *
C -chiral carbon as all the four valencies are attached with
Thus, the total acylic isomers forms of C4 H 7 Cl are 12. different substituents or groups.
1 2 3 4 CH 3
140. (d) CH 3 CH CH 2 CH 3 |
|
CH 3 150. (b) Br C* Cl * asymmetric or chiral carbon
|
Its monochloro derivatives are as follows : H
All the four valencies of carbon are satisfied with different
(i) ClCH 2 C H CH 2 CH 3 atoms/substituents.
|
CH 3 151. (c) The configuration in which, OH group are on right side, H -
atom are on left side, CHO group are on upper side &
or CH 3 CH CH 2 CH 3 CH 2OH are on lower side found in fischer projection known
| as D -configuration.
CH 2Cl
CHO
It will exist as enantiomeric pair ( and -forms)
H OH
Cl
| CH 2 OH
(ii) CH 3 C CH 2 CH 3 D- glyceraldehyde
|
CH 3 (2 ) (2 )
CHO CHO
no asymmetric atom (4 ) (1) (3 ) (1)
Intrachange
Cl H OH CH 2 OH OH
| H and CH 2 OH
(3 ) (4 )
(iii) CH 3 CH C H CH 3 CH 2 OH H
|
CH 3 CHO
It will exist as enantiomeric pair ( - and -forms) or H OH
(iv) CH 3 CH CH 2 CH 2 Cl CH 2 OH
|
CH 3
No asymmetric carbon atom Critical Thinking Questions
Hence, only two enantiomeric pairs will be obtained by the
monochlorination of 2-methylbutane. 4

141. (d) When isomers have the structural formula but differ in the 3

relative arrangement of atoms or groups in space with in the

molecule, these are known as sterioisomers and the 1. (c) 3
60° 3
60°
3
4
3

phenomenon as sterio isomerism. Stereoisomerism is of three

2
2 2

3 3 3

1 1 1

Gauche conformation
 1074 General Organic Chemistry

11. (c) The number of possible optical isomers 2n

2. (d) Only four structural isomers are possible for diphenyl methane. -atoms) 2 3 8
12. (c) 2-bromo, 3-chloro-butane has 2 chiral carbon atoms, hence has
2 2 4 optical isomers.

2 2
Br Cl
| |

(i) (ii)
CH 3 C C CH 3
| |
H H
|
13. (a) CH 3 CH 2 CH 2 CH 3 , CH 3 CH CH 3
n Butane |
SN 1 mechanism proceeds through carbocation intermediate.
2

3. (c) CH 3
CH 3 (iii) (iv) Iso butane
|
CH 3 C Cl provides stable carbocation intermediate 14. (b) C2 H 3 Cl 2 Br three isomers are possible
| because it has tertiary carbon.
CH 3 Cl
4. (e) CH 3 CH CH CH 3 Cl 2 CH 3 C Cl 1-bromo-1, 1-dichloroethane
| |
CH 3 CH 3 Br
2, 3 - dimethyl butane
Cl
CH 3 CH CH CH 2 Cl Br CH 2 CH 1-bromo-2,2-di-chloroethane
| |
CH 3 CH 3 Br
2, 3 - dimethyl chloro butane
Due to the presence of chiral carbon it shows the optical Br
activity and its mirror image are non superimposable so it Cl CH 2 CH 1-bromo-1, 2-dichloroethane
shows one enantiomer pair.
Cl
CH 3 CH CH CH 2 Cl ClCH 2 CH CH CH 3
| | | |
15. (c) (+)-tartaric acid has positive optical rotation and is derived
CH 3 CH 3 CH 3 CH 3 from (+) glyceraldehyde.
(I) (II)
16. (c) I > II > III
CH 3
| OCH 3 NO 2
H
5. (a) CH 3 CH 2 C CH 2 CH 3
|
OH
CH 3
| Methoxy group is electron releasing it increases electron
CH 3 CH 2 C CH 2 CH 3 density of benzene nucleus while NO 2 decreases electron
density of benzene.
The more stable carbocation is generated thus more easily it
will be dehydrated. 17. (c) Due to resistance benzyl carbonium ion is most stable.
6. (b) This option is not characteristics of free radical chain reaction. OH
18. (d) R CH 2 N R CH N
7. (c) Due to NO 2 group in benzene ring, (Nitro form ) O ( Aci form ) O
2
CH 3
is most stable carbanion. CH CH CH CH
19. (b)
CH 3 CH 3
(cis) CH 3
2 (Trans)

8. (d) Dissociation of proton from CH 3 N H 3Cl is very difficult Cl

due to effect of Cl and N while in C6 H 5 OH due to 20. (d) Both 1, 2-dichloro benzene
resonance stabilization of phenoxide ion proton eliminate easily
similarly due to -bonding in C6 H5 CH 2OH it can be (i a) (i b)
eliminate and CH 3C CH show acidic character by triple Hence, identical compounds.
bond by which proton can be dissociate.
CH 3 3
3

Both, 1, 3-dimethyl benzene

2

9. (b)
(iia) (iib)
Electron withdrawing group increases acidic character due to
and effect of NO 2 hence orthonitrophenol is most acidic. Hence, identical compounds.
10. (d) Halogenation on alkene occurs by electrophilic addition.
 General Organic Chemistry 1075

COOH 3. CH 3 CH CH 2 OH
|
CH 3
Isobutyl alcohol

( iiia) (iiib) CH 3
|
(iiia) and (iiib) are position isomers. 4. CH 3 C CH 3
|
OH
Ter buty alcohol
21. (a,c,d) (a) CH CH OH
(enol)
5. CH 3 CH 2 O CH 2 CH 3
Diethyl ether
CH 2 C O
|
H 6. CH 3 O CH 2 CH 2 CH 3
(Keto) Methyl propyl ether

(c) O OH CH 3
(keto) (enol) 7. CH 3 O CH
CH 3
Methyl isopropyl ether

29. (a) According to Huckel rule for aromaticity the molecule must be
(d) O OH planar, cyclic system having delocalised (4 + 2) electron
(Keto) (enol)
where is an integer equal to 0, 1, 2, 3, thus the aromatic
comp. have delocalised electron cloud of
CH 3 (CH 2 )5 (CH 2 )5 CH 3 +
22. (c) C Br OH
HO C
| Optical inversion 2, 6, 10 or 14 electron cyclopropenyl cation have the 2
CH 3 H H CH 3
electron ( = 0) so it is aromatic.
In this reaction inversion of configuration takes place this is
30. (d) group is a deactivating group, hence benzoic acid is
called optical inversion. It is an example of SN 2 reaction
(Bimolecular Nucleophillic Substitution). less reactive towards electrophilic substitution than phenol.
23. (b) This option shows eclipsed form of ethane. 31. (c) In the triphenyl methyl carbonium ion the electrons of all the
24. (c) 2 and 4 forms of ethane are staggered.
nd th
three benzene rings are delocalised with the vacant -orbital of
central carbon atom. So, it is resonance stabilised. It is the
25. (b) (CH 3 )3 C 3 carbonium ion is most stable. most stable of all the carbonium ions given
Y Y CH 3
|
X
26. (a) The ion CH 3 C is stabilised by hyperconjugation, a
|

X CH 3
second order resonance.
m isomer
( 60%)

Y COOH because it is meta directing group while CH 2

NH 2 . OH and Cl are and directing groups.
32. (b)

27. (a)
NO 2

CH 3 Br CH 3 Nitro-group is electron withdrawing therefore decreases

| | | stability.
Br
H C C H H C C H Br H 2O
| | H |
H CH 3 CH 3 CH 2
OH
28. (c) C4 H10 O have 7 isomers out of which 4 are alcohols and 3
are ethers.
O
1. CH 3 CH 2 CH 2 CH 2 OH , |
n butyl alcohol CH 3
2. CH 3 CH 2 CH CH 3 Methoxy group is electron releasing.
|
OH Therefore increases stability by donating electron.
Sec butyl alcohol
 1076 General Organic Chemistry
CH 3
CH 2 CH CH CH CH
and
CH 3 CH 3 CH 3
(cis) (trans )

CH 3 CH CH
Cl
Chlorine is also electron withdrawing but its effect is less than
NO 2 group.
1 - phenyl pro pene
Hence, correct order of stability.
H
/
CH 2 CH 2 CH 2 CH 2 CH 3 C C C 6 H 5 and CH C C C6 H 5
| | 3
/
H H H
(cis) (Trans)

43. (c) CH 3CN behaves both as nucleophile and electrophile.

O Cl NO 2
| Least 44. (c) 2n , = no. of asymmetric carbon atoms.
CH 3 stable
Most stable 45. (b) 1. CH 3 CH 2 CH 2 CH 2 CH 2 CH 3
n hexane
Me
| 2. CH 3 CH CH 2 CH 2 CH 3
33. (b) 3° alcohols Me C Me is most stable carbocation |
CH 3
34. (b) Due to the increasing no. of hyperconjugative structures free 2 methyl pentane

radical stabilise following as 3 2 1 . 3. CH 3 CH 2 CH CH 2 CH 3

|
35. (c) 3 2 1 CH 3
3 methyl pentane
CH 3 CH 3 H
4. CH 3 CH CH CH 3
| |
CH 3 C H C CH 3 C CH 3 CH 3
2,3 Dimethyl butane
CH 3 CH 3 H CH 3
|
H H 5. CH 3 C CH 2 CH 3
| |
|
36. (b,c) CH 3 C CH CH 3 and CH 3 CH 2 C CH 3 CH 3
| | |
2 , 2 , dimethyl butane
Br CH 3 Br
46. (c) Stability of carbanions increase with increase in -character of
37. (b) C2 H 5 S C2 H 5 and CH 3 S C3 H7 hybrid orbitals of carbon bearing charge, hence correct order is
Methyl propyl
Diethyl thioether
thioether : sp3 sp 2 sp .
are metamers. 47. (b) C2 H 2 C2 H 4 C6 H 6 C2 H 6
OH OH 1.20 Å 1.34 Å 1. 39 Å 1.54 Å
| |
38. (b) HCOO C H CH COOH
* * 48. (d) CH 3 CHO HCN CH 3 CH CN
(1) ( 2) |
OH
Two carbon atoms in the molecule are asymmetric.
(Both and forms are obtained) Hence, product will be a
39. (a,b,d) CH 3 N H 2 , R O , CH 3 Mg Br : are nucleophiles racemic mixture.
49. (d)
due to presence of lone pairs. between single and double bond.
40. (c) CH 3 has the highest nucleophilicity. 50. (a) Two isomers CH 3 CH CH 3 and
|
O OH Cl
|| |
41. (c,d) C6 H5 C CH 3 and C6 H 5 C CH 2 CH 3 CH 2 CH 2Cl are possible for C3 H 7 Cl .
(Keto form) (enol form)

O O
C6 H 5
||
C CH 2
||
C CH 3 and
Assertion & Reason
(Keto form)

C6 H 5 C CH C CH 3 1. (a) It is fact that aniline is better nucleophile than anilium ion.

|| | Anilium ion contain + charge, which reduces the tendency to
O OH
(enol form) donate lone pair of electron C6 H5 NH 3 .
Anilium ion
42. (a,c) 2-butene
Therefore, both assertion and reason are true.
 General Organic Chemistry 1077
2. (b) Neopentane is isomer of pentane and neopentane forms only 16. (a) In cyclohexanone keto enol tautomerism is as follows
one substitution product. Both assertion and reason are true 3
but reason is not a correct explaination of assertion. 3
1
Neopentane forms mono substituted product due to presence 2
2
1
of four identical methyl groups present on carbon atom.
3. (c) The assertion that butene reacts with Br2 to product
meso-2, 3-dibromobutane is correct but it does not involve - Keto form Enol form
addition of Br2 .
4. (d) Here both assertion and reason are incorrect because -1, 3-
dihydroxy cyclohexane exist in chair conformation and in chair
conformation hydrogen bonding is present.
5. (a) Hydroxy ketones are not directly used in Grignard reagent.
Grignard reagents are very reactive. Therefore, they react with
hydroxyl group. Here both are correct.
6. (a) The assertion that on keeping benzyl bromide in acetone water
it produces benzyl alcohol is correct. Because C6 H5 CH 2 Br
hydrolysed to produce C6 H5 CH 2OH . This conversion is of
SN 2 mechanism.
7. (b) Catenation property of carbon is primarily due to its small size. 17. (e) The staggered form is more stable than the eclipsed form
Electronic configuration and unique strength of carbon-carbon because the potential energy of staggered form in which the
bonds. bond pairs of two carbons are far away from each other is
8. (e) Olefins are unsaturated hydrocarbons containing two hydrogen minimum. Also the -atoms are as far apart as possible and
atoms less than the corresponding paraffin there is one non bonded interaction between them is maximum. In occupied
double bond between two carbon atoms in their molecules and form, the -atom are very close and so the increased overlap
they have the general formula Cn H 2n . between them non-bonded orbitals is repulsive. That is why
9. (b) Less reactivity of saturated hydrocarbons are due to presence staggered form is more stable than eclipsed form.
of single bonds between carbon atoms. 18. (b) Trans isomer is more stable than cis isomer because in cis
10. (b) Glucose is insoluble in ether. isomer, the bulky groups are on the same side of the double
11. (a) An alkyl group attached to the positively charged carbon of a bond. The steric repulsion of the groups makes the cis isomer
carbonium ion tends to release electrons towards that carbon; less stable than the trans isomer in which the bulky groups are
thus the positive charges gets dispersed as the alkyl group far apart. (They are on the opposite side of the double bond).
becomes some what positively charged itself. More the number
of alkyl groups, the greater is the dispersal of positive charge 19. (e) 1, 2-propadiene is not optically active because the terminal
and therefore more easily it will be formed. sp2 -hybridised carbons have the same atoms -atoms. As
12. (b) Heterolytic fission occurs when the two atoms differ a result, it has a plane of symmetry passing through the three
considerably in their electronegativities and shared pair of carbon atoms and hence the molecule is optically inactive.
electrons is carried by more electronegative atom.
20. (b) Lactic acid is a chiral molecule because it has a chiral carbon
13. (d) The order of reactivity of carbonium ions is 1 2 3 .
atom or asymmetric carbon atom and is therefore optically
Carbon atom in carbonium ion is in sp 2 state of active.
hybridisation. The three hybridized orbitals lie in the same 21. (e) Resonance structures contain the same number of unpaired
plane and are involved in the formation of three bonds with electrons.
three atoms or groups while the unhybridised -orbital remains
vacant. 22. (b) CO 32 shows resonance and thus all the three bonds are of
14. (b) Since free radicals contain odd electrons, so they are short lived identical bond length.
and they readily try to pair up the odd electrons to form
neutral molecules, that is why they are highly reactive. O C O O C O O C O
| | ||
15. (b) Each carbon atom in ethylene is attached to two hydrogen O O O
atoms by single covalent bonds and to another carbon atoms
by a double bond. Since each carbon is attached to three other
atoms, it uses sp 2 hybrid orbitals and an unhybridised p Z
orbital to form its bond. Each C H bond is a bond
resulting from the overlap of 1 s orbital of hydrogen atom and
sp 2 orbital of a carbon atom. One C C bond results from
2
the linear overlap of sp orbitals one from each carbon atom.
One bond results from the lateral overlap of two
unhybridised p Z orbitals, one from each carbon atom.
 General Organic Chemistry 1079

1. The most stable conformation of -butane is 12. On monochlorination of 2-methyl butane, the total number of chiral
[CBSE PMT 1997] compounds is [IIT-JEE Screening 2004]
(a) Skew boat (b) Eclipsed (a) 2 (b) 4
(c) Gauche (d) Staggered (c) 6 (d) 8
13. An isomer of ethanol is
2. Which of the following undergoes nucleophilic substitution by SN 1 [DPMT 1982, 88; CPMT 1973, 75, 78, 84; IIT-JEE 1986;
mechanism [CBSE PMT 2005] BHU 1984, 85; EAMCET 1993; MP PET 1995;
(a) Benzyl chloride (b) Ethyl chloride RPET 1999; BHU 2000; AFMC 2002]
(c) Chlorobenzene (d) Isopropyl chloride (a) Methanol (b) Dimethyl ether
3. Which type of isomerism is shown by propanal and propanone[CPMT 2004] (c) Diethyl ether (d) Ethylene glycol
(a) Functional group (b) Metamerism 14. Due to the presence of an unpaired electron, free radicals are
(c) Tautomerism (d) Chain isomerism (a) Chemically reactive (b) Chemically inactive
4. Which of the following exhibits optical isomerism (c) Anions (d) Cations
[BHU 1980; NCERT 1983; AIIMS 1992; 15. Tertiary alkyl halides are practically inert to substitution by S N 2
MNR 1993; MP PMT 1990, 94]
mechanism because of [AIEEE 2005]
(a) Butanol-1 (b) Butanol-2
(a) Insolubility (b) Instability
(c) Butene-1 (d) Butene-2 (c) Inductive effect (d) Steric hindrance
5. In carbonium ion the carbon bearing the positive charge in the [Pb. PMT 1999;
16. MH CET
The 2002]
decreasing order of nucleophilicity among the nucleophiles
(a) sp 2 -hybridized state (b) sp 3 d -hybridized state (i) CH 3 C O (ii) CH 3 O
||
3
(c) sp -hybridized state (d) sp -hybridized state O
6. Which of the following is not an electrophile O
[CBSE PMT 2001] ||
(iii) CN (iv) H 3 C S O
(a) Cl (b) Na ||
O
(c) H (d) BF3
is [AIEEE 2005]
7. Heterolytic bond dissociation energy of alkyl halides follows the (a) (i), (ii), (iii), (iv) (b) (iv), (iii), (ii), (i)
sequence [AMU 2000]
(c) (ii), (iii), (i), (iv) (d) (iii), (ii), (i), (iv)
(a) R F R Cl R Br R I 17. Which of the following is optically active [BHU 2005]
(b) R I R Br R Cl R F (a) Butane (b) 4-methylheptane
(c) R I R F R Br R Cl (c) 3-methylheptane (d) 2-methylheptane
(d) R Cl R Br R I R F 18. Correct configuration of the following is
8. The shape of carbonium is [AMU (Engg.) 1999] CH 3
(a) Planar (b) Pyramidal
H OH
(c) Linear (d) None of these [AIIMS 2005]
9. Which of the following compounds shows tautomerism CH 3 OH
[MP PET 2001] H
(a) HCHO (b) CH 3 CHO (a) 1S, 2S (b) 1S, 2R
(c) CH 3 COCH 3 (d) HCOOH (c) 1R, 2S (d) 1R, 2R
10. In which bond angle is the highest [CBSE PMT 1991]
19. Which types of isomerism is shown by 2, 3-dichlorobutane
[AIEEE 2005]
(a) sp 3 (b) sp 2 (a) Distereo (b) Optical
(c) sp (d) sp 3 d (c) Geometric (d) Structural
20. Who synthesised the first organic compound urea in the laboratory[RPMT 2000
11. How many primary amines are possible for the formula C 4 H 11 N [MNR 1995]
(a) Kolbe (b) Wohler
(a) 1 (b) 2 (c) Fraizer (d) Berzilius
(c) 3 (d) 4

(SET -23)

3
 1080 General Organic Chemistry
1. (d) Anti or completely staggard
Therefore, a total of four chiral compounds are obtained.
13. (b) Dimethyl ether is an isomer of ethanol.
14. (a) Free radicals are very reactive due to the presence of free e .
Staggard form is most stable because of minimum repulsion 15. (d) Due to steric hinderance
between bulky methyl groups. 16. (c) (ii) > (iii) > (i) > (iv)
2. (a) Due to more stable carbocation. CH 3
3. (a) When two compounds have similar molecular formula but |
differ in the functional group then the isomerism is called 17. (c) CH 3 CH 2* CHCH 2 CH 2 CH 3 has a chiral carbon atom and
functional group isomerism CH 3CH 2CHO and hence is optically active.
O 18. (a)
|| 3

CH 3 . C CH 3 .
H
|
4. (b) CH 3 C CH 2 CH 3
| 3

OH
Because it has chiral carbon atom.
Following the procedure outlined under 'Golden Rule' the
5. (a) The central carbon atom in carbonium ion is sp 2 hybridised absolute configuration is 1 , 2 .
and it has three sp 2 hybrid orbitals for single bonding to
three substituents. CH 3 CH 3
6. (b) Na is not an electrophile. 19. (b) H Cl , H Cl ,
7. (b) R I R Br R Cl R F H Cl Cl H
8. (a) Carbonium ion is planar species CH 3 CH 3
9. (c) Ketones show tautomerism. They form keto and enol form
O OH CH 3
|| Tautomerism |
CH 3 C CH 3 CH 3 C CH 2 Cl H
10. (c) Type Bond angle H Cl
sp 3 CH 3
109.5 o
20. (b) Wohler synthesised the first organic compound urea in the
sp 2 120 o laboratory.
sp 3 d 90 o and 120 o
180 o
11. (d) CH 3 CH 2 CH 2 CH 2 NH 2
(1- aminobutan e)

CH 3 CH 2 CH CH 3
|
NH 2
(2 - aminobutan e)

CH 3
|
CH 3 C CH 3
|
NH 2
(2 -Methyl- 2 - aminopropa ne)

3
CH 3 CH
2 1
CH 2 NH 2
***
|
CH 3
(2 - Methyl -1 - aminopropa ne)

12. (b) The possible monochlorinated products of 2-methyl butane are

(+) and ( ) forms

(+) and ( ) forms