1014 General Organic Chemistry

Chapter

23
General Organic Chemistry

Carbon is an essential element of organic Bond Four - Three - Two -

compounds, it has four electrons in its outer most shell. One - Two -
Bond angle 109.5 120 180
According to the ground state electronic
Geometry Tetrahedra Trigonal Linear
configuration of carbon, it is divalent. Tetravalency of
l planar
carbon can be explained by promoting one of the 2s 2 - % s-character 25 or 1/4 33.33 or 50 or 1/2
electrons to the unocupied 2 p z 1 atomic orbital. 1/3

The four valencies of carbon atom are similar and (2) Determination of hybridisation at different
they are symmetrically arranged around the carbon
carbon atoms : It can be done by two methods,
atom. According to Le Bell and Van’t Hoff the four
valencies of carbon do not lie in one plane. They are (i) First method : In this method hybridisation
directed towards the corners of a regular tetrahedron can be know by the number of   bonds present on
with carbon atom at the centre and the angle between that particular atom.
any two valencies is 109o28.
Number of – bond/s 0 1 2
Hybridisation in Organic Compounds
3 2
Type of hybridisation sp sp sp
(1) The process of mixing atomic orbitals to form
Examples :
a set of new equivalent orbitals is termed as
hybridisation. There are three types of hybridisation, O
3 ||
(i) sp hybridisation (involved in saturated
(i) CH 3  CH  CH  C  CH 3
organic compounds containing only single covalent     
bonds), sp 3 sp 2 sp 2 sp 2 sp 3
(ii) sp 2 hybridisation (involved in organic
(ii) CH 2  C  CH 2
compounds having carbon atoms linked by double   
sp sp 2
bonds) and sp 2
(iii) sp hybridisation (involved in organic
(iii) CH 3  CH  CH  CH 2  C  N
compounds having carbon atoms linked by a triple    
 
bonds). sp 3 sp 2
sp 2
sp 3 sp sp
Table : 23.1
Type of sp3 sp2 sp (iv) HC  C  CH  CH 2
hybridisation    
Number of 1s and 3p 1s and 2p 1s and 1p
sp sp sp 2 sp 2
orbitals used
Number of Nil One Two  In diamond carbon is sp3 hybridised and in
unused
graphite carbon is sp 2 hybridised.
p-orbitals
 General Organic Chemistry 1015

(ii) Second method : (Electron pair method) of the decreasing order of s orbital character in the
three hybrid orbitals.
ep = bp + lp; where ep = electron pair present in
sp 3  sp 2  sp
hybrid orbitals , bp = bond pair present in hybrid orbitals
(ii) Electronegativity of different orbitals
Number of bp = Number of atoms attached to (a) Electronegativity of s-orbital is maximum.
the central atom of the species (b) Electronegativity of hybrid orbital  % s-
character in hybrid orbitals
Central atom
First atom H
H Orbital sp sp 2 sp 3
C=C % s - character 50 33 . 33 25

s-character in decreasing order and electroneg ativity in decreasing order
Second atom H H
Thus sp-hybrid carbon is always electronegative
bp = 3
Third atom in character and sp 3 - hybrid carbon is electropositive
in character. sp 2 -hybrid carbon can behave as
Central atom
1 2 electropositive (in carbocation) as well as
H  C  C H 2
1 electronegative (in carbanion) in character.
 H
 
bp  2 CH 3  CH 2 CH 2  CH
3
bp = 3
sp 2 sp
Number of lp’s can be determined as follows,
(a) If carbon has  - bonds or positive charge or
odd electron, than lp on carbon will be zero. Electronegative
Electropositive
(b) If carbon has negative charge, then lp will be carbon having
carbon positive charge
equal to one.
(c) Electronegativities of different hybrid and
Number of electron pairs (ep) tells us the type of
unhybrid orbitals in decreasing order is as follows
hybridisation as follows,
s  sp  sp 2  sp 3  p

ep 2 3 4 5 6 % s - character and electroneg ativity in decreasing order.
Type of sp sp 2 sp 3 sp 3 d sp 3 d 2
hybridisation (iii) Bond length variation in hydrocarbons
% of s orbital character
Example :
  1 1
(i) CH 2  CH (ii) CH 2  CH  
  C  C bond length C  H bond length
bp  2 bp  2 Table : 23.2
lp  0 lp  1
ep  2, sp ep  3, sp 2 Bond type Bond Bond type Bond
  (C – H) length (C – C) length
(iii) CH 2  C  CH 3 (iv) CH  C
|  sp 3  s 1.112Å sp 3  sp 3 (al 1.54 Å
bp 1
CH 3 lp  1 (alkanes) kanes)
bp  3 ep  2, sp
lp  0 sp 2  s 1.103Å sp 2  sp 2 (al 1.34Å
ep  3, sp 2 (alkenes) kenes)

(v) CH 3  CH  CH 3 sp  s 1.08Å sp  sp (alk 1.20Å
 (alkynes)
bp  3 ynes)
lp  1
ep  4 , sp 3 (iv) Bond strength in hydrocarbons : The shorter
is the bond length, the greater is the compression
(3) Applications of hybridisation
between atomic nuclei and hence greater is the strength
(i) Size of the hybrid orbitals : Since s - orbitals
of that bond.
are closer to the nucleus than p - orbitals, it is
reasonable to expect that greater the s character of an Table : 23.3
orbital the smaller it is. Thus the decreasing order of Bond Bond Bond type Bond
the size of the three hybrid orbitals is opposite to that
type (C – energy (C – C) energy
 1016 General Organic Chemistry
H) (kcal/mole) (kcal/mole) (1) Tertiary alkyl halides having bulky groups
form tertiary carbocation readily when hydrolysed
sp 3  s 104 sp 3  sp 3 80 – 90
because of the presence of the three bulky groups on
(in (in the carbon having halogen.
alkanes) alkanes) Steric strain around this Steric strain is
CH
2 2 2 3 carbon released
sp  s 106 sp  sp 122 – 164
| 
(More strained species) (less strained
(in (in H 3 C  C  Cl  H 3 C  C  CHspecies)
3
| |
alkenes) alkenes) CH CH
3
3
sp  s 121 sp  sp 123 – 199
(in (in (2) Primary alkyl halide having quaternary  -
alkynes) alkynes) carbon does not form transition state because of the
steric strain around  -carbon by the  -carbon. To
(v) Acidity of hydrocarbons
release the strain it converts into carbocation.
(a) Hydrogen present on electronegative carbon Bulky
CH group
3
is acidic in nature. |
(b) Acidity of hydrogen is directly proportional to CH 3  C CH 2  Cl
|
the electronegativity of the atom on which hydrogen is CH
3 Strained carbon
present. due to bulky group
present around this
Thus
carbon.
H O  H  NH 3  CH  CH
   (3) Steric strain inhibits the resonance. This
phenomenon is known as steric inhibitions of
Electronegativity of the atoms
Acidity of compounds in decreasing order resonance.
(c) Acidity of hydrocarbon  % of s-character Electronic displacement in covalent bonds
CH  CH CH 2  CH 2 CH 3  CH 3
It is observed that most of the attacking reagents
% s-character 50 33.33
always possess either a positive or a negative charge,
25
therefore for a reaction to take place on the covalent
pKa 25 44 50
bond the latter must possess oppositely charged
s- character and acidity in decreasing order centres. This is made possible by displacement (partial
1 or complete) of the bonding electrons. The electronic
Acidity  Ka and Acidity  (pKa   log Ka)
pKa displacement in turn may be due to certain effects,
Order of acidic nature of alkynes is, some of which are permanent and others are
temporary. The former effects are permanently
HC  CH  HC  C  CH 3
operating in the molecule and are known as
The relative acidic character follows the order; polarisation effects, while the latter are brought into
H2O  ROH  HC  CH  NH 3  CH 2  CH 2  CH 3  CH 3 play by the attacking reagent and as soon as the
attacking reagent is removed, the electronic
Obviously, the basic character of their conjugate displacement disappears; such effects are known as the
bases follows the reverse order, i.e., polarisability effects.
CH 3 CH 2  CH 2  CH 
 NH 2  HC  C 
 RO 
 HO 
Electronic
displacement
Steric effect
On account of the presence of bulkier groups at
Polarisation Polarisability
the reaction centre, they cause mechanical interference effect effect
and with the result the attacking reagent finds it (permanent) (temporary)
difficult to reach the reaction site and thus slows down
the reaction. This phenomenon is called steric Inductiv Mesomeri Hyperconjugati Inductomer Electromeri
hinderance or steric effect. e effect c effect ve effect ic effect c effect
 General Organic Chemistry 1017

Inductive effect or Transmission effect (ii) Reactivity of alkyl halide : + I effect of

methyl group enhances – I effect of the halogen atom
(1) When an electron withdrawing (X) or
by repelling the electron towards tertiary carbon atom.
electron-releasing (Y) group is attached to a carbon
CH 3 CH 3
chain, polarity is induced on the carbon atom and on
the substituent attached to it. This permanent polarity H3C C X  H3C CH X
is due to displacement of shared electron of a covalent CH 3
bond towards a more electronegative atom. This is
 CH 3 CH 2 X  CH 3 X
called inductive effect or simply as I – effect.
Tertiary > Secondary > Primary > Methyl
C  C  C  C Non polar
     (iii) Relative strength of the acids :
C  C  C  C X
(a) Any group or atom showing +I effect
    
C  C  C  C Y decreases the acid strength as it increases the negative
charge on the carboxylate ion which holds the hydrogen
(2) Carbon-hydrogen bond is taken as a standard firmly. Alkyl groups have + I effect.
of inductive effect. Zero effect is assumed for this bond.
Thus, acidic nature is,
Atoms or groups which have a greater electron
withdrawing capacity than hydrogen are said to have–I HCOOH  CH 3 COOH  C 2 H 5 COOH  C3 H 7 COOH  C4 H 9 COOH
effect whereas atoms or groups which have a greater +I effect increases, so acid strength decreases
electron releasing power are said to have +I effect.
Formic acid, having no alkyl group, is the most

N H 3  NO 2  CN  SO 3 H  CHO  CO  COOH  COCl  COOR acidic among these acids.
> CONH 2  F  Cl  Br  I  OH  OR  NH 2  C 6 H 5  H (b) The group or atom having – I effect increases
–I power of groups in decreasing order with respect to the the acid strength as it decreases the negative charge on
reference H the carboxylate ion. Greater is the number of such
atoms or groups (having – I effect), greater is the acid
ter. alkyl > sec. alkyl > pri. alkyl > CH 3  H strength.
+ I power in decreasing order with respect to the Thus, acidic nature is,
reference H
CCl 3 COOH  CHCl 2 COOH  CH 2 ClCOOH  CH 3 COOH
+ I power  number of carbon in the same type of Trichloro
acetic acid
Dichloro
acetic acid
Monochloro
acetic acid
Acetic acid

alkyl groups
(– Inductive effect increases, so acid strength increases)
CH 3  CH 2  CH 2  CH 2   CH 3  CH 2  CH 2  
(c) Strength of aliphatic carboxylic acids and
CH 3  CH 2  benzoic acid

+ I power in decreasing order in same type of R COOH C6 H 5 COOH

alkyl groups  
 I group  I group
(3) Applications of Inductive effect

(i) Magnitude of positive and negative charges :

Hence benzoic acid is stronger acid than aliphatic
Magnitude of +ve charge on cations and magnitude of
carboxylic acids but exception is formic acid. Thus,
–ve charge on anions can be compared by + I or – I
groups present in it. HCOOH > C6 H 5 COOH > RCOOH

ve Acid strength in decreasing order

 Magnitude of charge
1  Decreasing order of acids :
   I power of the group.
 I power of the group NO2CH 2COOH  FCH 2COOH  ClCH 2COOH  BrCH 2COOH .
 Magnitude of ve charge F3C  COOH  Cl3C  COOH  Br3C  COOH  I3C  COOH .
1
   I power of the group.
 I power of the group CH 3 OH  CH 3 CH 2 OH  (CH 3 ) 2 CHOH  (CH 3 )3 COH
Methyl Ethyl Iso propyl Tert butyl
alcohol Alcohol alcohol alcohol
 1018 General Organic Chemistry
As compared to water, phenol is more acidic (–I (viii) Stability of carbonium ion :+I effect tends
effect) but methyl alcohol is less acidic (+I effect). to decrease the (+ve) charge and –I effect tends to
OH  H  OH > CH 3 OH increases the +ve charge on carbocation.
Phenol Water Methyl alcohol
(CH 3 )3 C   (CH 3 )2 CH   CH 3 CH 2  CH 3
(vi) Relative strength of the bases (Basic nature
of  NH 2 ) (ix) Stability of carbanion : Stability of
carbanion increases with increasing – I effect.
The difference in base strength in various amines
can be explained on the basis of inductive effect. The +I CH 3  CH 3 CH 2  (CH 3 )2 CH   (CH 3 )3 C 
effect increases the electron density while –I effect
Resonance effect or mesomeric effect
decreases it. The amines are stronger bases than NH 3
(1) The effect in which  electrons are
as the alkyl groups increase electron density on
transferred from a multiple bond to an atom, or from a
nitrogen due to + I effect while ClNH 2 is less basic due
multiple bond to a single covalent bond or lone pair (s)
to –I effect. “So more is the tendency to donate electron of electrons from an atom to the adjacent single
pair for coordination with proton, the more is basic covalent bond is called mesomeric effect or simply as
nature, i.e., more is the negative charge on nitrogen M-effect. In case of the compound with conjugated
atom (due to +I effect of alkyl group), the more is basic system of double bonds, the mesomeric effect is
nature”. transmitted through whole of the conjugated system
and thus the effect may better be known as conjugative
Thus, the basic nature decreases in the order; effect.
(C 2 H 5 )2 NH  CH 3 CH 2 NH 2  CH 3 NH 2  NH 3  ClNH 2 (2) Groups which have the capacity to increase
Diethy l Ethy l Methy l Ammonia Chloro
amine amine amine amine the electron density of the rest of the molecule are said
to have  M effect. Such groups possess lone pairs of
The order of basicity is as given below;
electrons. Groups which decrease the electron density
Alkyl groups (R– Relative base strength of the rest of the molecule by withdrawing electron
) pairs are said to have M effect, e.g.,
CH 3 R2 NH  RNH 2  R3 N  NH 3 (a) The groups which donate electrons to the
double bond or to a conjugated system are said to have
C2 H 5 R2 NH  RNH 2  NH 3  R3 N  M effect or R effect.
(CH 3 )2 CH RNH 2  NH 3  R2 NH  R3 N  M effect groups :
.. ..
(CH 3 )3 C NH 3  RNH 2  R2 NH  R3 N
 Cl,  Br ,  I,  N H 2 ,  NR 2 ,OH ,OR,SH ,OCH 3 , S R
..
 The relative basic character of amines is not in
total accordance with inductive effect (t  s  p) but it is (b) The groups which withdraw electrons from
the double bond or from a conjugated system towards
in the following order: Secondary > Primary > Tertiary.
itself due to resonance are said to have M effect or
The reason is the steric hindrance existing in the t-
R effect.
amines.
M effect groups :
 In gas phase or in aqueous solvents such as
chlorobenzene etc, the solvation effect, i.e., the O
||
stabilization of the conjugate acid due to H -bonding
 NO 2 ,C  N ,  C ,CHO ,COOH ,SO 3 H
are absent and hence in these media the basicity of
amines depends only on the +I effect of the alkyl group (3) The inductive and mesomeric effects, when
thus the basicity of amines follows the order : present together, may act in the same direction or
3 o  2 o  1 o  NH 3 . oppose each other. The mesomeric effect is more
powerful than the former. For example, in vinyl
(vii) Basicity of alcohols : The decreasing order chloride due to – I effect the chlorine atom should
of base strength in alcohols is due to +I effect of alkyl develop a negative charge but on account of mesomeric
groups. effect it has positive charge.
(CH 3 )3 COH  (CH 3 )2 CHOH  CH 3 CH 2 OH  CH 3 OH
(3 o ) (2 o ) (1 o )
 General Organic Chemistry 1019

..  .. (2) Structural requirements for

: Cl  CH  CH 2  : Cl  CH  CH 2 hyperconjugation
.. ..
(i) Compound should have at least one sp 2 -
Application of mesomeric effect : It explains,
hybrid carbon of either alkene alkyl carbocation or
(1) Low reactivity of aryl and vinyl halides,
alkyl free radical.
(2) The acidic nature of carboxylic acids,
(ii)  -carbon with respect to sp 2 hybrid carbon
(3) Basic character comparison of ethylamine and
aniline, should have at least one hydrogen.
(4) The stability of some free radicals, If both these conditions are fulfilled then
carbocations and carbanions. hyperconjugation will take place in the molecule.
Difference between Resonance and
(iii) Hyperconjugation is of three types
Mesomerism : Although both resonance and
mesomerism represent the same phenomenon, they (iv) Resonating structures due to
differ in the following respect : Resonance involves all hyperconjugation may be written involving “no bond”
types of electron displacements while mesomerism is between the alpha carbon and hydrogen atoms.
noticeable only in those cases where a multiple bond is 
in conjugation with a multiple bond or lone pair of H H
| 
electron. H  C  CH  CH 2  H  C  CH  C H 2 
| |
Example : H H
(i) H H
  |  | 
..  H C  CH  C H 2  H  C  CH  C H 2
H 2 C  CH  CH  CH 2  H 2 C  CH  CH  C H 2 |
H H

.. ..
:O :O: (v) Number of resonating structures due to the
.. 
|| ||
hyperconjugation = Number of  -hydrogens + 1.
(ii) R  C  O  H  R  C  O  H
..
.. Applications of hyperconjugation
Both (i) and (ii) are the examples of mesomerism (1) Stability of alkenes : Hyperconjugation
and resonance effect. Let us consider the following explains the stability of certain alkenes over other
..  
alkenes.
example H Cl :  H Cl . Such an electron Stability of alkenes  Number of alpha hydrogens
..
 Number of resonating structures
displacement is the example of resonance only (not the
CH 3  CH  CH 2  CH 3  CH 2  CH  CH 2  CH 3  CH  CH  CH 2
mesomerism). |
CH 3
Hyperconjugative effect
Stability in decreasing order
(1) When a H  C bond is attached to an
(2) Carbon-carbon double bond length in
unsaturated system such as double bond or a benzene
alkenes : As we know that the more is the number of
ring, the sigma () electrons of the H  C bond interact
resonating structures, the more will be single bond
or enter into conjugation with the unsaturated system.
The interactions between the electrons of  systems character in carbon-carbon double bond.
(multiple bonds) and the adjacent  bonds (single (3) Stability of alkyl carbocations : Stability of
H  C bonds) of the substituent groups in organic alkyl carbocations  number of resonating structures 
compounds is called hyperconjugation. The concept of number of alpha hydrogens.
hyperconjugation was developed by Baker and Nathan
and is also known as Baker and Nathan effect. (4) Stability of alkyl free radicals : Stability of
alkyl free radicals can be explained by
In fact hyperconjugation effect is similar to
hyperconjugation. Stability depends on the number of
resonance effect. Since there is no bond between the
resonating structures.
 -carbon atom and one of the hydrogen atoms, the
hyperconjugation is also called no-bond resonance. (5) Electron releasing (or donating) power of R
in alkyl benzene : CH 3  (or alkyl group) is R group,
 1020 General Organic Chemistry
ortho-para directing group and activating group for 
Cl Cl
electrophilic aromatic substitution reaction because of | 
Cl  C  CH  CH 2  Cl  C  CH  CH 2 
the hyperconjugation. | |
Cl Cl
The electron donating power of alkyl group will
depends on the number of resonating structures, this Cl Cl
 |  | 
depends on the number of hydrogens present on - Cl C  CH  CH 2  Cl  C  CH  CH
2
carbon. The electron releasing power of some groups |
Cl Cl

are as follows,
The meta directing influence and the deactivating
CH 3
CH 3 | effect of CX 3 group in electrophilic aromatic
CH 3   CH 3  CH 2   CH   CH 3  C  substitution reaction can be explained by this effect.
CH 3 |
CH X X X X
3
| |  |  | 
Increasing inductive effect X  C X X C X X C X X C X
| || || ||
Electron donating power in decreasing order due  +
to the hyperconjugation.

(6) Heat of hydrogenation : Hyperconjugation
decreases the heat of hydrogenation. Inductomeric effect
(7) Dipole moment : Since hyperconjugation Inductomeric effect is the temporary effect which
causes the development of charges, it also affects the enhances the inductive effect and it accounts only in
dipole moment in the molecule. the presence of an attacking reagent.
The increase in dipole moment, when hydrogen of Example,
formaldehyde (  2 .27 D) is replaced by methyl group, H
i.e., acetaldehyde (  2 . 72 D) can be referred to H
hyperconjugation, which leads to development of HO  H  C  Cl  HO....... ..... C..... ....... Cl
charges. H
H H H H
H
| | 
H
H  C  O , H  C  CH  O  H  C  CH  O Cl 
(  2.27 D) | |  HO  C  H
H H
(  2 . 72 D) H

(8) Orienting influence of alkyl group in o, p - In methyl chloride the –I effect of Cl group is
further increased temporarily by the approach of
positions and of CCl 3 group in m -position : Ortho-
hydroxyl ion.
para directing property of methyl group in toluene is
partly due to I effect and partly due to
Electromeric effect
hyperconjugation. (1) The phenomenon of movement of electrons
from one atom to another in multibonded atoms at the
Reverse Hyperconjugation : The phenomenon of
demand of attacking reagent is called electromeric
hyperconjugation is also observed in the system given effect. It is denoted as E-effect and represented by a
below, curved arrow ( ) showing the shifting of electron
X pair.
| E
 
 C  C  C ; where X  halogen A  B  A B :
Reagent
|

In such system the effect operates in the reverse

direction. Hence the hyperconjugation in such system is (2) (i)When the transfer of electrons take place
known as reverse hyperconjugation. towards the attacking reagent, the effect is called  E
effect. The addition of acids to alkenes.
 General Organic Chemistry 1021

C C  H   C  C . .
| A : B  A  B
H Free radical


(ii) The factor which favours homolysis is that
CH 3 CH  CH 2  H   CH 3  C H  CH 3
Propene the difference in electronegativity between A and B is
Since, CH 3 group is electron donating, the less or zero.
electrons are transferred in the direction shown. (iii) Homolysis takes place in gaseous phase or in
The attacking reagent is attached to that atom on the presence of non polar solvents (CCl 4 , CS 2 ) , peroxide,
which electrons have been transferred. UV light, heat ( 500 o C) , electricity and free radical.
(ii) When the transfer of electrons takes place (iv) Mechanism of the reaction in which
away from the attacking reagent, the effect is called homolysis takes place is known as homolytic
 E effect. Example, The addition of cyanide ion to
mechanism or free radical mechanism.
carbonyl compounds.
(2) Heterolytic bond fission or heterolysis

C  O  CN   C  O (i) In heterolysis, the covalent bond is broken in

| such a way that one species (i.e., less electronegative)
CN
is deprived of its own electron, while the other species
The attacking reagent is not attached to that
gains both the electrons.
atom on which electrons have been transferred.
 
(3) Direction of the shift of electron pair : The A : B  A:  B
carbanion carbocation
direction of the shift of electron pair can be decided on
Thus formation of opposite charged species takes
the basis of following points.
place. In case of organic compounds, if positive charge
(i) When the groups linked to a multiple bond are
is present on the carbon then cation is termed as
similar, the shift can occur in either direction.
carbocation. If negative charge is present on the
(ii) When the dissimilar groups are linked on the carbon then anion is termed as carbanion.
two ends of the double bond, the shift is decided by the
(ii) The factor which favours heterolysis is
direction of inductive effect.
greater difference of electronegativities between A
In the case of carbonyl group, the shift is always and B .
towards oxygen, i.e., more electronegative atom.
(iii) Mechanism of the reaction in which
 
C  O  C O : heterolysis takes place is known as heterolytic
mechanism or ionic mechanism.
In cases where inductive effect and electromeric
effect simultaneously operate, usually electrometric (iv) The energy required for heterolysis is always
effect predominates. greater than that for homolysis due to electrostatic
forces of attraction between ions.
Cleavage (fission or breaking) of covalent bonds
Reaction Intermediates
Breaking of covalent bond of the compound is
known as bond fission. A bond can be broken by two Short lived fragments called reaction
intermediates result from homolytic and heterolytic
ways,
bond fission. The important reaction intermediates are
(1) Homolytic bond fission or Homolysis free radicals, carbocations, carbanions, carbenes,
(i) In homolysis, the covalent bond is broken in benzyne and nitrenes.
such a way that each resulting species gets its own
electron. This leads to the formation of odd electron
species known as free radical.
Table : 23.4

Characteristi Free radical Carbocation Carbanion Carbene

c
 1022 General Organic Chemistry
Nature Neutral having odd electron Positive charge on C Negative charge on Neutral, divalent
C with 2 unshared
electrons
Hybridisation sp2 sp2 sp3 (non- (i) sp2 (singlet)
conjugated) (ii) sp (triplet)
sp2 (Conjugated)
Structure Planar Planar Pyramidal/Planar (i) Planar (singlet)
(ii) Linear (triplet)
Magnetism Paramagnetic Diamagnetic Diamagnetic (i) Diamagnetic
(ii) Paramagnetic
Stability . . .      Triplet > singlet
order 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  3 o  2 o 
 
. . 3 o  2 o  1o  CH 3 CH 2  1o  2 o  3 o
o
1  CH 2  CH 2  CH

Benzyne (2) There is possibility of two spin states for

nitrenes depending on whether the two non-bonding
(1) 1, 2-Didehydrobenzene, C6 H 4 and its
electrons (the normal nitrogen lone pair remains
derivatives are called benzyne or arynes and the paired) have their spins paired or parallel.
simplest member is benzyne. ..
(2) It is neutral reaction intermediate derived R –. N
. These two are lone pair of
from benzene ring by removing two substituents, of  electrons
ortho positions, one in the form of electrophile and These two may be paired or
other in the from of nucleophile leaving behind two unpaired
electrons to be distributed between two orbitals. (3) In general nitrenes obey Hunds rule and the
ground state triplet with two degenerate sp -orbitals
Abnormal  bond containing a single electron each.

R–N
2
Two sp -orbitals
ouside the ring
sp-Triplet
nitrene
(4) Nitrenes can be generated, in situ, by the
(3) Benzyne intermediate is aromatic in
following methods,
character.
(4) When halobenzene is heated with sodamide (i) By action of Br2 in presence of a base on a 1 o
formation of benzyne takes place. amide (Hofmann-bromamide reaction),
Cl O  O O
||  || 
|| . .
R  C  NH 2  R  C  NHBr  R  C  N  Br
Br2 / NaOH OH
NaNH 2
  1 o Amide  H 2O ..


(5) (i) It behaves as dienophile and gives Diels-
Alder reaction with diene. O
|| . .
O  C  N  R 

Rearrangement
(ii) It reacts with strong nucleophile like NH 2    R  C  N  
 Br . . Isocy anate 
NH2 NH2 KOH

H
 
 R  NH 2  K 2 CO 3
 N H 2   (Hydrolysis) 1 o Amine

(ii) By decomposition of azides in presence of
.. heat or light.
Nitrenes (R – N : ) ..  .. ..
 or h ν
R  N  N  N :  R  N :  N  N
(1) The nitrogen analogous of carbenes are called Alkylazide Alkylnitrene
nitrenes.
 General Organic Chemistry 1023

.. (ii) Neutral nucleophiles : It can be classified

(iii) Unsubstituted nitrene (H  N :) can be into two categories :
obtained by photolysis of (or by passing electric
(a) Neutral covalent compound, in which central
discharge through) NH 3 , N 2 H4 or N 3 H . atom has complete octet, has at least one lone pair of
electrons and all atoms present on central atom should
Attacking reagents
not be electronegative, is neutral nucleophile.
The fission of the substrate molecule to create .. .. .. .. .. ..
centres of high or low electron density is influenced by N H 3, R  N H 2 , R2 N H , R3 N , N H 2  N H 2 (Nitrogen
attacking reagents. Most of the attacking reagents can
nucleophile)
be classified into two main groups.
.. .. ..
Electrophiles or electrophilic reagents and H  O H, R  O H, R  O R (Oxygen
Nucleophiles or nucleophilic reagents. .. .. ..

(1) Electrophiles : Electron deficient species or nucleophiles)

electron acceptor is an electrophile. .. .. ..
H  S  H , R  S  H , R  S  R (Sulphur nucleophiles)
It can be classified into two categories : .. .. ..
(i) Charged electrophiles : Positively charged .. .. .. ..
species in which central atom has incomplete octet is P H 3 , R P H 2 , R2 P H , R3 P (Phosphorus
called charged electrophile.
nucleophiles)
 O  
H , X , R, N , N  O, S O3 H (b) Organic compound containing carbon, carbon
O .. multiple bond/ bonds behaves as nucleophile.
All cations are charged electrophiles except Alkenes, Alkynes, Benzene,

cations of IA, IIA group elements, Al    and NH 4 CH 2  CH  CH  CH 2 , CH 2  CH  C  CH

(ii) Neutral electrophiles : It can be classified (iii) Ambident nucleophiles : Species having two
into three categories, nucleophilic centres out of which, one is neutral
(a) Neutral covalent compound in which central (complete octet and has at least one lone pair of
atom has incomplete octet is neutral electrophile, electrons) and the other is charged (negative charge)
. .. .. behaves as ambident nucleophile
BeCl 2 , BH 3 , ZnCl 2 , AlX 3, FeX 3 , CH 3 , CH 2 , CX 2
O
 ..  ..  
(b) Neutral covalent compound in which central C  N , O  N  O, O  S  OH
atom has complete or expended octet and central atom 
O
has unfilled –d-sub-shell is neutral electrophile,
SnCl 4 , SiCl 4 , PCl 5 , SF6 , IF7  Organometallic compounds are nucleophiles.
 Nucleophiles are Lewis bases.
(c) Neutral covalent compound in which central
atom is bonded only with two or more than two Organic compounds which behave as an
electronegative atoms is called neutral electrophile. electrophile as well as a nucleophile : Organic
BeCl 2 , BX 3 , AlX 3 , FeX 3 , SnCl 4 , PCl 3 ; compound in which carbon is bonded with
electronegative atom (O, N, S) by multiple bond/bonds
..
PCl 5 , NF3 , C X 2 , CO 2 , SO 3 , CS 2 , behaves as electrophile as well as nucleophile :
O O O O
Cl 2 , Br2 and I2 also behave as neutral || || || ||
R  C  H , R  C  R, R  C  OH , R  C  Cl ,
electrophiles.
O O
Electrophiles are Lewis acids. || ||  
R  C  OR, R  C  NH 2 , R  C  N , R  N  C
(2) Nucleophiles : Electron rich species or
electron donors are called nucleophiles. Nucleophiles  During the course of chemical reaction
can be classified into three categories : electrophile reacts with nucleophile.
(i) Charged nucleophiles : Negatively charged  Strong Lewis acid is stronger electrophile
species are called charged nucleophiles.  
CO 2  N O 2  S O 3 H . Stronger is an acid, weaker is its
     
H , O H , R  O, C H 3 , X , S H , R  S conjugated base or weaker is the nucleophile.
 1024 General Organic Chemistry
Examples : HF  H 2 O  NH 3  CH 4    
I Br Cl F
        
F   OH   NH 2  CH 3 Increasing basicity

Increasing order of nucleophilicity. Decreasing leaving ability
Types of organic reactions (iii) The leaving power of some nucleophilic
It is convenient to classify the numerous groups are given below in decreasing order,
reactions of the various classes of organic compound
O O O
into four types, ||  ||  || 
 Substitution reactions,  Addition reaction, CF3  S  O  Br S  O  CH 3 SO 
|| || ||
 Elimination reactions,  Rearrangement O O O
reactions, O O
||  || 
Substitution reactions C 6 H 5  S  O  CH 3  S  O
|| ||
Replacement of an atom or group of the substrate
O O
by any other atom or group is known as substitution
O O
reactions.   ||     || 
Substituting or  I  Br  CF3  C  O  H O  Cl  F  CH 3  C  O
Examples : Leaving group attacking (iv) In these reactions leaving group of the
group substrate is replaced by another nucleophile. If reagent
CH 3  CH 2  Br  NaOH  CH 3  CH 2 OH  NaBr is neutral then leaving group is replaced by negative
Ethyl bromide Ethyl alcohol
part of the reagent. Negative part of the reagent is
(Bromine atom is replaced by hydroxyl group) always nucleophilic in character.
    
E  Nu
Types of substitution reactions : On the basis of R  L    R  Nu  L ; R  L  Nu  R  Nu  L
the nature of attacking species substitution reactions (v) In S N reactions basicity of leaving group
are classified into following three categories, should be less than the basicity of incoming
(1) Nucleophilic substitution reactions nucleophilic group. Thus strongly basic nucleophilic
group replaces weakly basic nucleophilic group of the
(2) Electrophilic substitution reactions substrate.

(3) Free radical substitution reactions OH 
Example : R  Cl   R  OH  Cl .....(A)
( NaOH )
(1) Nucleophilic substitution reactions
 
Basicity of OH is more than Cl hence OH replaces
(i) Many substitution reactions, especially at the

saturated carbon atom in aliphatic compounds such as Cl as Cl .
alkyl halides, are brought about by nucleophilic 
Cl

R  OH 
 R  Cl  OH ......(B)
reagents or nucleophiles. ( HCl )
  
R  X  OH   R  OH  X Basicity of Cl is less than OH , hence Cl will not
Substrate Nucleophil e Leaving group

replace OH as OH hence reaction (B) will not occur.
Such substitution reactions are called
(vi) Unlike aliphatic compounds having
nucleophilic substitution reactions, i.e., S N reactions (S
nucleophilic group as leaving group, aromatic
stands for substitution and N for nucleophile). compounds having same group bonded directly with
(ii) The weaker the basicity of a group of the aromatic ring do not undergo nucleophilic substitution
reaction under ordinary conditions.
substrate, the better is its leaving ability.
The reason for this unusual reactivity is the
Leaving power of the group 
1 presence of lone pair of electron or  bond on the key
Basicity of the group atom of the functional group. Another factor for the
low reactivity is nucleophilic character of aromatic
HI  HBr  HCl  HF
Example :          ring.
Decreasing acidity (vii) The S N reactions are divided into two
classes, S N 2 and S N 1 reactions.

Table : 23.5 Distinction between SN2 and SN1 reactions

 General Organic Chemistry 1025

Factors SN2 Reactions SN1 Reactions

 
R : L  R   : L
Number of steps Slow
One: R : L  : Nu  R : Nu  : L Two: (i)
(ii) R   : Nu  
Fast
 R : Nu
Reaction rate and order Second order: First order:
Rate  [Substrate] [Nucleophile] or Rate  [Substrate] or Rate = K1 [RL]
Rate = 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 nucleophile can attack the carbon of the
the substrate exclusively from the substrate both from the back and front sides
back side. although the back side attack predominates.
Stereochemistry Complete inversion of configuration Inversion and retention takes place.
takes place.
Reactivity order of alkyl Methyl>1°>2°>3°halides. 3°>2°>1° > methyl halides. (I  Br  Cl  F)
halides (I  Br  Cl  F)

Rearrangement No rearranged product is formed Rearranged products can be formed.

(except for allylic).
Nature of nucleophiles Favoured by strong and high Favoured by mild and low concentration of
concentration of nucleophiles. nucleophiles.
Polarity Favoured by solvents of low polarity. Favoured by solvents of high polarity.
Reaction rate determining By steric hindrance. 
By electronic factor (stability of R ).
factor
Catalysis Not catalysed by any catalyst (phase Catalysed by Lewis and Bronsted acids, e.g.,
transfer). 
Ag , AlCl 3 , ZnCl 2 and strong HA.

(2) Electrophilic substitutions reactions : of reaction is 1, it is written as S E 1 (unimolecular)and

Electrophilic substitution involves the attack by an if the order is 2, it is S E 2 (Bimolecular).
electrophile. It is represented as SE (S stands for
substitution and E stands for elctrophile). If the order
SE1 Reaction mechanism : Electrophilic substitution in SE2 Reaction mechanism : Electrophilic
aliphatic compounds are very rare; some of the important substitution is very common in benzene nucleus
examples are: (aromatic compounds) in which -electrons are
(i) Replacement of the metal atom in an organometallic highly delocalized and an electrophile can attack
  this region of high electron density.
compound by hydrogen : R  M  H  R  H  M In all electrophilic aromatic substitution
 reactions, it involves:

 MgBr H
e.g., CH 3  CH 2  MgBr   CH 3  CH 2  CH 3  CH 3 

Step 1. The formation of an electrophile, E, i.e.,

H  
CH 3  CH 2  MgBr  H  Br  CH 3  CH 2  CH 3  CH 3  MgBr2
In halogenation; Cl  Cl  FeCl 3  Cl  Fe Cl 4
CH 3  CH 2 Na  C6 H6  CH 3  CH 3  C6 H5 Na
In nitration;
(ii) Decarboxylation of silver salt of carboxylic acid by means   
HNO 3  2 H 2 SO 4  NO 2  2 HSO 4  H 3 O
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;
O O  
R  Cl  AlCl 3  R  AlCl 4
 R3C  Br  CO2  AgBr
 
(iii) Isotopic exchange of hydrogen for deuterium or tritium: RCOCl  AlCl 3  RCO  AlCl 4
H E
Step 2. The electrophile H E theHaromatic
attacks E
  
E

Benzene +

H E
E
 1026 General Organic Chemistry
  ring to form carbonium ion (or arenium ion)
RH D⇋ RDH which is stabilized by resonance.
 
R  H T ⇋ R T H

Step 3. Carbonium ion loses the proton to form

substitution product.

The bromination of benzene in the

presence of FeBr 3 is a example of electrophilic
substitution reaction.
Similarly, Nitration, sulphonation and
Friedel-Crafts reaction…..etc., in benzene
nucleus are the other examples of electrophilic
substitution reactions.

(3) Free radical substitution reactions : Free CH 2  CO

radical substitution reactions involves the attack by a CH 3  CH  CH 2  CCl 4
N  Br  
free radical. These reactions occurs by free radical Propene
CH 2  CO
mechanism which involves Initiation, Propagation and NBS
Termination steps. Examples,
CH 2  CO
(i) Chlorination of methane : The chlorination of
Br  CH 2  CH  CH 2  NH
methane in the presence of ultraviolet light is an Ally lbromide
CH 2  CO
examples of free radical substitution. Succinimide

CH 4  UV
Cl 2  CH 3 Cl  HCl Addition reactions
Methane light Methylchloride
These reactions are given by those compounds
(ii) Arylation of aromatic compounds (Gomberg which have at least one  bond,
reaction) : The reaction of benzene diazonium halide O
||
with benzene gives diphenyl by a free radical i.e., ( C  C ,C  C , C , C  N ). In such
substitution reaction.
reaction there is loss of one  bond and gain of two 
C6 H 5  H  C6 H 5 N 2 X Alkali
  C6 H 5  C6 H 5  N 2  HX bonds. Thus product of the reaction is generally more
Benzene diazonium halide Diphenyl stable than the reactant. The reaction is a spontaneous
reaction.
(iii) Wurtz reaction : Ethyl bromide on treatment
Types of addition reactions : Addition reactions
with metallic sodium forms butane, ethane and
can be classified into three categories on the basis of
ethylene by involving free radical mechanism.
the nature of initiating species.
(iv) Allylic bromination by NBS (N-
(1) Electrophilic additions
Bromosuccinimide) : NBS is a selective brominating
(2) Nucleophilic additions
agent and it normally brominates the ethylenic
compounds in the allylic (CH 2  CH  CH 2 ) position. (3) Free radical additions

This type of reaction involving substitution at the alpha (1) Electrophilic addition reactions
carbon atom with respect to the double bond is termed (i) Such reactions are mainly given by alkenes
Allylic substitution. It is also used for benzylic and alkynes.
bromination. Some examples are: (ii) Electrophilic addition reactions of alkenes
and alkynes are generally two step reactions.
 General Organic Chemistry 1027

(iii) Alkenes and alkynes give electrophilic Cl

|
addition with those reagents which on dissociation Anti- Markowniko ff's addition
CH 2  CH  CHO  HCl    CH 2  CH 2  CHO
gives electrophile as well as nucleophile.
(vii) Mechanism of electrophilic addition
(iv) If the reagent is a weak acid then
reactions is as follows,
electrophilic addition is catalysed by strong acids
  |
(Generally H 2 SO 4 ). CC  E Slow
  C C E
Olefin Electrophile |
(v) Unsymmetrical alkenes and alkynes give Carbonium ion

addition reactions with unsymmetrical reagents  | 

Fast
|

according to Markownikoff’s rule. C C E  X  C  C E

| Nucleophile | |

The negative part of the addendum adds on that X

Addition product
doubly bonded carbon of the alkene which has least
(2) Nucleophilic addition reactions : When the
number of hydrogen atom.
addition reaction occurs on account of the initial attack
This rule can be used only in those alkenes which of nucleophile, the reaction is said to be a nucleophilic
fulfil the following conditions: addition reaction. Due to presence of strongly
(a) Alkene should be unsymmetrical. electronegative oxygen atom, the  -electrons of the
(b) Substituent/substituents present on doubly carbon-oxygen double bond in carbonyl group ( C  O )
bonded carbon/(s) should only be +I group. get shifted towards the oxygen atom and thereby such
bond is highly polarised. This makes carbon atom of the
(c) If phenyl group is present on doubly bonded
carbonyl group electron deficient.
carbon, then both doubly bonded carbons should be
   
substituted by phenyl groups. CO  C O  C O
For example, the following alkenes will give
addition according to the Markownikoff’s rule. Example : The addition of HCN to acetone is an
example of nucleophilic addition.
CH 3
CH 3 CH 3 OH
CH 3  CH  CH 2 , C  CH 2 ,
C  O  HCN  C
CH 3
CH 3 CH 3 CN
C6 H 5 Acetone Acetone cy anohy drin

C  CH  C6 H 5, C6 H 5  CH  CH 2 The mechanism of the reaction involves the

following steps:
C6 H 5


Following alkenes will not give addition reaction Step 1. HCN gives a proton (H ) and a nucleophile,

according to Markownikoff’s rule. cyanide ion (CN ) .
R R HCN  H   CN 
CH 2  CH 2 , R  CH  CH  R, CC , Step 2. The nucleophile (CN ) attacks the
R R
positively charged carbon so as to form an anion [ H 
C6 H 5 C6 H 5 does not initiate the negatively charged oxygen as
CC anion is more stable than cation].

C6 H 5 C6 H 5 CH 3 CH 3 O
 CH 3 
(vi) Unsymmetrical alkenes having the following CN C  O  CN C  O or C
general structure give addition according to anti CH CH CH CN
3 3 3
Markownikoff’s rule.
CH 2  CH  G , where G is a strong –I group such Step 3. The proton (H  ) combines with anion to
as form the addition product.
O CH 3
||
 CX 3 , NO 2,  CN ,CHO ,COR ,COOH , C  Z CH 3 | CH 3 OH

CN C  O  H  NC  C  OH or C
(Z  Cl, OH, OR, NH 2 ) CH 3 | CH 3 CN
Example: CH 3
 1028 General Organic Chemistry
(I) -elimination reactions or 1,1-elimination
In C  O compounds, the addition of liquid HCN
reactions: A reaction in which both the groups or atoms
gives cyanohydrin and the addendum is CN  ion and are removed from the same carbon of the molecule is
not HCN directly (addition is catalysed by bases or salts called - elimination reaction. This reaction is mainly
of weak acids and retarded by acids or unaffected by given by gem dihalides and gem trihalides having at
neutral compounds). least one - hydrogen.
 ..
   O  OH Alc. KOH /

H CN   CN H CHX 3   CX 2  X  H
C  O    C  O  C 
 C
( A. R.) CN CN Product of the reaction is halocarbenes or
Nucleophilic addition (AN) reactions on carbonyl dihalocarbenes. which are key intermediates in a wide
compounds will be in order: variety of chemical and photochemical reactions.

H H 3C H 3C (II) -elimination reactions or 1, 2-elimination

C O  C O  C O reactions: Consider the following reactions,
H H H 3C  
CH 3  CH 2  CH 2  L  CH 3  CH  CH 2  H  L
Decreasing order of nucleophilic addition in some  

species.
A reaction in which functional group (i.e., leaving
O O
|| || group) is removed from - carbon and other group
C 6 H 5 CH 2 COCH 3  CH 3 COCH 3  C 6 H 5  C  CH 3  C 6 H 5  C  C 6 H 5  CHO  (Generally hydrogen atom) from the - carbon is called
COCH 3  COCl  COOCH 3  CONH 2  COOH - elimination reaction. In this reaction there is loss of
two  bonds and gain of one  bond. Product of the
(3) Free radical addition reactions : Those
reaction is generally less stable than the reactant.
reactions which involve the initial attack by a free
radical are known as free radical reactions. Addition of (1) Types of - elimination reactions : In
hydrogen bromide to alkenes (say, propylene) in the analogy with substitution reactions, - elimination
presence of peroxide (radical initiator) follows free reactions are divided into three types:
radical mechanism. Free radical reactions generally
(i) E1 (Elimination unimolecular) reaction, (ii) E2
take place in non-polar solvents such as CCl 4 , high
(Elimination bimolecular) reaction and (iii) E1cb
temperature, in presence of light or a free radical (Elimination unimolecular conjugate base) reaction
producing substance like O 2 and peroxides.
(i) E1 (Elimination unimolecular) reaction :
Elimination reactions Consider the following reaction,
Elimination reactions are formally the reverse of CH 3  CH 3
addition reactions and involve the removal of the two | C H O/  
CH 3  C  Cl 2 5
  CH C  C 2 H 5 OH  Cl
groups (Generally, one being a proton) from one or two 2
|
carbon atoms of a molecule to form an unsaturated CH 3 CH 3
linkage or centre.
(a) Reaction velocity depends only on the
Elimination reaction is given by those compounds
concentration of the substrate; thus reaction is
which have a nucleophilic group as leaving group,
unimolecular reaction.
  R R
  Rate  [Substrate]
i.e., X, OH, OR, N 2 , N 3 , H 3 O, N R, S
R R (b) Product formation takes place by the
Elimination reactions are generally endothermic formation of carbocation as reaction intermediate (RI).
and take place on heating. (c) Since reaction intermediate is carbocation,
Elimination reactions are classified into two rearrangement is possible in E1 reaction.
general types,
(d) Reaction is carried out in the presence of
(I) - elimination reactions or 1, 1-elimination polar protic solvent.
reactions.
(e) The E1 reaction occurs in two steps,
(II) - elimination reaction or 1, 2-elimination
reactions. Step 1.
 General Organic Chemistry 1029

CH 3 CH 3 Cl
| | 
   2 |
[Link] / 
CH 3  C  Cl  CH 3 Slow step
 C - - - - - Cl    CH 3  C  CH 3  Cl CH 3  CH  CH  CH 3 
 CH 3  C  CH  CH 3
| | | |  1  HCl |
CH 3 CH 3 CH 3 CH 3 CH
(TS 1 ) ( RI )
3
Saytzeff p roduct

Step 2.
(ii) Hofmann rule : According to this rule, major
  product is always least substituted alkene i.e., major
..  
   product is formed from - carbon which has maximum
B  H  CH 2  C  CH 3   B - - - - H - - - -CH 2 - - - - C  CH 3 
|

|
 number of hydrogen. Product of the reaction in this
CH 3 CH 3
  case is known as Hofmann product.
 TS 2 

CH 3 CH 3 Br CH 3
 | |
[Link] / 
|
fast
 B H  CH 2  C CH 3  C  CH 2  CH  CH 3  CH 3  C  CH 2  CH  CH 2
| 2  1 |
CH 3 CH 3 CH 3
Hofmann product
(ii) E2 (Elimination bimolecular) reaction :
Consider the following reaction,  In E1 reactions, product formation always takes
place by Saytzeff rule.
Base ( B)
 
CH 3  CH 2  CH 2  Br   CH 3  CH  CH 2  H  Br
  In E1cb reactions, product formation always
(a) Reaction velocity depends only on the takes place by Hofmann rule.
concentration of the substrate and the base used; thus  In E2 reactions, product formation takes place
reaction is bimolecular reaction. Rate [Substrate] by Saytzeff as well as Hofmann rule. In almost all E2
[Base]
reactions product formation take place by Saytzeff rule.
(b) Since the reaction is a bimolecular reaction,
the product formation will take place by formation of (3) Examples of  - elimination reactions
transition state (TS). (i) Dehydrohalogenation is removal of HX from
(c) Rearrangement does not take place in E2 alkyl halides with alcoholic KOH or KNH 2 or ter- BuOK
reaction but in case of allylic compound rearrangement (Potassium tertiary butoxide) and an example of -
is possible. elimination,
[Link]
(d) Reaction is carried out in the presence of e.g., CH 3  CH 2 X   H 2 C  CH 2 ;
( HX ) Ethene
polar aprotic solvent.
[Link]
CH 3  CH  CH 3   CH 3 CH  CH 2
(e) The E2 reaction occurs in one step, | ( HX ) Propene
.. X
B H H  B  - - - - H   H  [Link]
| |   |  CH 3  CH 2  CH  CH 3   CH 3  CH  CH  CH 3 
CH 3  C  C  H    CH 3  C
Slow step
C  H | ( HX ) 2 - Butene (Major)
| |  |   X
H Br  H Br 
 TS  CH 3  CH 2  CH  CH 2
1- Butene (Minor)
fast

 CH 3  CH  CH 2  BH  Br
(ii) Dehydration of alcohol is another example of
(2) Orientation in  - elimination reactions : If elimination reaction. When acids like conc. H 2 SO 4 or
substrate is unsymmetrical, then this will give more
H 3 PO 4 are used as dehydrating agents, the mechanism
than one product. Major product of the reaction can be
is E1 . The proton given by acid is taken up by alcohol.
known by two emperical rules.
Dehydration is removal of H 2 O from alcohols,
(i) Saytzeff rule : According to this rule, major
product is the most substituted alkene i.e., major e.g.,
 Conc. H 2 SO 4 , 170 C
CH 3  CH 2  OH    H 2 C  CH 2
product is obtained by elimination of H from that - ( H 2 O )

carbon which has the least number of hydrogen.

Conc. H 2SO 4 , 170 C
Product of the reaction in this case is known as Saytzeff CH 3  CH 2  CH 2  OH    CH 3  CH  CH 2
Propan -1 - ol ( H 2 O ) Propene
product.
 1030 General Organic Chemistry
 Dehydration of alcohols is in the order: Y  B
Tertiary  Secondary  Primary
| |
Y | | | |
 C  C    C  C    C  C 
(3) (2) (1) | | | |
X: X
 2° and 3° alcohol by E1 process and 1° alcohol
Bridged or
by E2 process. Alcohols leading to conjugated alkenes
non-classical carbocation
are more easily dehydrated than the alcohols leading to X= Nucleophilic species, Y = Electronegative
non-conjugated alkenes. CH 2  CH  CH  CH 3 is easily group, B = Another nucleophile.
|
OH (2) Rearrangement or migration to electron
dehydrated than rich atoms (Electrophilic rearrangement) : Those
CH 3  CH 2  CH  CH 3 and so rearrangement reactions in which migrating group is
|
electrophile and thus migrates to electron rich centre.
OH
OH OH OH
(3) Rearrangement or migration to free radical
>
species (Free radical rearrangement) : Those
>
rearrangement reactions in which the migrating group
moves to a free radical centre. Free radical
rearrangements are comparatively rare.
(iii) Dehalogenation : It is removal of halogens,
in CH 3 OH , heat (4) Aromatic rearrangement : Those
e.g., CH 2  CH 2  Zn dust   H 2 C  CH 2
| | (-ZnBr2 ) Ethy lene rearrangement reactions in which the migrating group
Br Br moves to aromatic nucleus. Aromatic compounds of the
Ethy lene bromide
type (I) undergo rearrangements in the manner
X–Y X–H X–H
(iv) Dehydrogenation : It is removal of hydrogen, mentioned below,
Y
Cu , 300 C
e.g., CH 3  CH  CH 3    CH 3  C  CH 3  +
| ( H 2 ) ||
OH O +
Isopropy l alcohol Acetone
(I) Y
Rearrangement reactions
The reactions, which involve the migration of an The element X from which group Y migrates may
atom or group from one site to another within the be nitrogen or oxygen.
molecule (nothing is added from outside and nothing is Isomerism
eliminated) resulting in a new molecular structure, are
known as rearrangement reactions. The new compound Organic compounds having same molecular
is actually the structural isomer of the original one. formula but differing from each other at least in some
physical or chemical properties or both are known as
It is convenient to divide rearrangement
isomers (Berzelius) and the phenomenon is known as
reactions into following types:
isomerism.
(1) Rearrangement or migration to electron
The difference in properties of isomers is due to
deficient atoms (Nucleophilic rearrangement) : Those
the difference in the relative arrangements of various
rearrangement reactions in which migrating group is
atoms or groups present in their molecules. Isomerism
nucleophilic and thus migrates to electron deficient
can be classified as follows:
centre which may be carbon, nitrogen and oxygen.
B:
Isomerism

X
Constitutional or structural Configurational or stereo isomerism
isomerism The isomerism arises due to different arrangement
Without referring to space, the isomers
of atoms or groups in space. It deals with the
differ in the arrangement of atoms within
the molecule is called structural structure of molecules in three dimensions. Thus
isomerism. Thus structural isomers have: stereoisomers have:

Chain Position Ring Functiona Meta Tauto - Geometric Optical Conformation

isomeris isomeris chain l merism merism al isomeris al
m m isomeris isomeris isomerism m isomerism
m m
 General Organic Chemistry 1031

Constitutional or structural isomerism  Structural isomers which differ in the position

of the functional group are called regiomers. For
(1) Chain, nuclear or skeleton isomerism : This example, (i) CH 3  CH 2  CH 2  OH (ii) CH 3  CH  CH 3
type of isomerism arises due to the difference in the |
OH
nature of the carbon chain (i.e., straight or branched)
which forms the nucleus of the molecule. (3) Functional isomerism : This type of
isomerism is due to difference in the nature of
Examples :
functional group present in the isomers. The following
(i) C4H10 : CH 3  CH 2  CH 2  CH 3 , pairs of compounds always form functional isomers
n Butane
with each other.
CH 3  CH  CH 3
| Examples :
CH 3
Isobutane (i) Alcohols and ethers (Cn H2n+2O)
(ii) C5H12 : (Three) CH 3  CH 2  CH 2  CH 2  CH 3 , C2H6O : CH 3  CH 2  OH ; H 3 C  O  CH 3
n  Pentane Ethy l alcohol Dimethy lether

CH 3 C3H8O : CH 3  CH 2  CH 2  OH ; C 2 H 5  O  CH 3
n  propy l alcohol Ethy l methy lether
|
CH 3  C H  CH 2  CH 3 , CH 3  C  CH 3 C4H10O : CH 3  CH 2  CH 2  CH 2  OH ;
| | n Buty l alcohol
CH 3 CH 3
Isopentane Neopentane C2 H 5  O  C2 H 5
Diethy l ether
 Except alkynes chain isomerism is observed (ii) Aldehydes, ketones and unsaturated
when the number of carbon atoms is four or more than alcohols …etc. (Cn H2nO)
four.
O
 Chain isomers differ in the nature of carbon ||
C3H6O : CH 3  CH 2  CHO ; CH 3  C  CH 3 ;
chain, i.e., in the length of carbon chain. Propionald ehy de Acetone

 The isomers showing chain isomerism belong CH 2  CH  CH 3 ; CH 2  CH  CH 2 OH

to the same homologous series, i.e., functional group, Ally lalcohol
O
class of the compound (Cyclic or open) remains 1, 2  Epoxy propane
unchanged.
(iii) Acids, esters and hydroxy carbonyl
 Chain and position isomerism cannot be compounds …etc. (Cn H2nO2)
possible together between two isomeric compounds. If C2H4O2 : CH 3 COOH ; HCOOCH 3
two compounds are chain isomers then these two will Acetic acid Methy l formate

not be positional isomers. C3H6O2 : CH 3  CH 2  COOH ; CH 3 COOCH 3 ;

Propionic acid Methy l acetate
(2) Position isomerism : It is due to the
difference in the position of the substiuent atom or O
||
group or an unsaturated linkage in the same carbon CH 3 C HCHO ; CH 3  C  CH 2  OH
chain. | 1  Hy droxy propan - 2 - one
OH
(ii) C3 H6 Cl2 : 2  Hy droxy propanal
CH 3  CCl 2  CH 3 , CH 3  CH 2  CH  Cl 2 ,
2, 2 Dichloro propane, 1,1Dichloro propane (iv) Alkynes and alkadienes (Cn H2n-2)
(gemdihalide) (gemdihalide)
C4H6 : CH 3  CH 2  C  CH ; H 2C  CH  CH  CH 2 ;
1  Buty ne 1, 3  Butadiene
CH 3  C H  C H 2 , C H 2  CH 2  C H 2
| | | |
Cl Cl CH 3  C  C  CH 3 ; H 2C  C  CH  CH 3
Cl Cl 2  Buty ne 1, 2  Butadiene
1, 2  Dichloro propane 1, 3  Dichloro propane
( , - dihalide)
(Vicdihalide) (v) Nitro alkanes and alkyl nitrites (  NO 2 and
 Aldehydes, carboxylic acids (and their O  N  O )
derivatives) and cyanides do not show position O
isomerism. C2H5NO2 : C 2 H 5  N ; C2 H 5  O  N  O
Ethy l nitrite
O
 Monosubstituted alicylic compounds and Nitro ethane
aromatic compounds do not show position isomerism. (vi) Amines (Primary, secondary and tertiary)
 1032 General Organic Chemistry
C3H9N : CH 3  CH 2  CH 2  NH 2 ; isomerism is not possible, there will be metamerism
Propan -1 - amine
e.g.,
H (a) CH 3  C  CH 2  CH 2  CH 3 ;
||
CH 3  CH 2  N O
(Pentan  2  one)
CH 3
N  Methy l ethanamine
CH 3 CH 2  C  CH 2 CH 3 are metamers and not position
||
CH 3 O
(Pentan  3  one)
CH 3  C H  CH 3 ; CH 3  CH 2  N
| isomers.
NH 2 CH 3
Propan - 2- amine N , N  Dimethy l methanamin e
(b) CH 3  C  CH 2 CH 2 CH 3 ;
||
(vii) Alcohols and phenols O
(Pentan  2  one)
CH2OH OH CH 3  C  C H  CH 3 are metamers and not chain isomers.
CH3 || |
C7 H8 O ; O CH 3
(3- Methy lbuta n - 2 - one)

Benzyl alcohol o-Cresol  Alkenes does not show metamerism.

(viii) Oximes and amides (6) Tautomerism
(i) The type of isomerism in which a substance
O
|| exist in two readily interconvertible different
C2H5NO : CH 3  CH  NOH ; CH 3  C  NH 2
Acetaldoxime Acetamide
structures leading to dynamic equilibrium is known as
tautomerism and the different forms are called
(4) Ring-chain isomerism : This type of tautomers (or tautomerides).
isomerism is due to different modes of linking of
The term tautomerism (Greek: tauto = same;
carbon atoms, i.e., the isomers possess either open
chain or closed chain sturctures. meros = parts) was used by Laar in 1885 to describe
H2 the phenomenon of a substance reacting chemically
C according to two possible structures.
(ii) It is caused by the wandering of hydrogen
H 2C CH 2
C6H12 : | | ; atom between two polyvalent atoms. It is also known
H 2C CH 2 as Desmotropism (Desmos = bond and tropos = turn).
C If the hydrogen atom oscillates between two polyvalent
H2 atoms linked together, the system is a dyad and if the
Cy clohexane
hydrogen atom travels from first to third atom in a
CH 2  CH 2 chain, the system is a triad.
| CHCH 3
C H 2  CH 2 ; CH 3 CH 2CH 2CH 2CH  CH 2 (a) Dyad system : Hydrocyanic acid is an example
Methy l cy clopentane 1 Hexene
of dyad system in which hydrogen atom oscillates
 Ring – chain isomers are always functional
between carbon and nitrogen atoms. H  C  N ⇌
isomers. 
C  N H
(5) Metamerism : This type of isomerism is due (b) Triad system
to the difference in the nature of alkyl groups attached Keto-enol system : Polyvalent atoms are oxygen
to the polyvalent atoms or functional group. Metamers
and two carbon atoms.
always belong to the same homologous series.
Compounds like ethers, thio-ethers ketones, secondary Examples :
amines, etc. show metamerism. O H OH
CH 3 C2 H 5 || | |
(i) C5H13N : C3 H7  N ; C2 H 5  N  C C ⇌  C  C 
CH 3 CH 3 | |
Dimethy l propy l amine Diethy l methy l amine
(Keto) (Enol)

(ii) C6H15N : C 3 H 7  NH  C 3 H 7 ; Acetoacetic ester (Ethyl acetoacetate) :

Dipropy l amine

C 2 H 5  NH  C4 H 9 O OH
Buty l ethy l amine || |
CH 3  C  CH 2 COOC 2 H 5 ⇌ CH 3  C  CHCOOC 2 H 5
Keto form (92.1%) Enol form (7.9%)

 If same polyvalent functional group is there in Acetoacetic ester gives certain reactions showing
two or more organic compounds, then chain or position
the presence of keto group (Reactions with HCN ,
 General Organic Chemistry 1033

H 2 NOH , H 2 NNHC 6 H5 , etc.) and certain reactions (g) Tautomerism has no effect on bond length.
showing the presence of enolic group (Reactions with (h) Tautomerism has no contribution in
stabilising the molecule and does not lower its energy.
Na, CH 3COCl , NH 3 , PCl5 , Br2 water and colour with neutral
(i) Tautomerism may occur in planar or
FeCl 3 , etc.). nonplanar molecules.
Enolisation is in order  Keto=enol tautomerism is exhibited only by
CH 3 COCH 3  CH 3 COCH 2 COOC 2 H 5  C6 H 5 COCH 2 COOC 2 H 5 such aldehydes and ketones which contain at least one
 -hydrogen.
 CH 3 COCH 2 COCH 3  CH 3 COCH 2 CHO
O For example
|| H
Acid catalysed conversion CH 3  C  CH 2 R CH 3 CHO, CH 3 CH 2 CHO, CH 3 COCH 2 COCH 3 etc,.
Keto

OH OH  Tautomerism is not possible in benzaldehyde

| |
H  (C6 H 5 CHO ) , benzophenone (C6 H 5 COC 6 H 5 ) , tri methyl
CH 3  C  C H  R  CH 3  C  CH  R
 | (Enol form) acetaldehyde, (CH 3 )3 C  CHO and chloral CCl 3  CHO as
H
(Intermediate)
they do not have   H .
Base catalysed conversion
Number of structural isomers
O O
|| OH ||
Molecular
CH 3  C  CH 2  R CH 3  C  C H  R Number of isomers
– H2 O  formula
Keto form

 Alkanes
O OH C4 H10 Two
| |
H 2O
 CH 3  C  CH  R   CH 3  C  CH  R
OH  (Enol)
C5 H12 Three
(c) Triad system containing nitrogen : Examples C6 H14 Five
Nitrous acid exists in 2 forms
C7 H16 Nine
O
H O  N  O HN C8 H18 Eighteen
nitrite form O
Nitro form
C9 H 20 Thirty five
Nitro acinitro system C10 H 22 Seventy five

O O Alkenes and
CH 3  CH 2  N CH 3  CH  N cycloalkanes
O OH
nitro form (i) Aciform (ii) C3 H6 Two (One alkene + one
(iii) Characteristics of tautomerism cycloalkane)
(a) Tautomerism (cationotropy) is caused by the C4 H8 Six (Four alkene + 2 -
oscillation of hydrogen atom between two polyvalent cycloalkane)
atoms present in the molecule. The change is C5 H10 Nine (Five alkenes + 4 –
accompanied by the necessary rearrangement of single cycloalkanes)
and double bonds.
Alkynes
(b) It is a reversible intramolecular change.
(c) The tautomeric forms remain in dynamic C3 H4 Two
equilibrium. Hence, their separation is a bit difficult. C4 H 6 Six
Although their separation can be done by special
Monohalides
methods, yet they form a separate series of stable
derivatives. C3 H 7 X Two
(d) The two tautomeric forms differ in their C4 H 9 X Four
stability. The less stable form is called the labile form.
The relative proportion of two forms varies from C5 H11 X Eight
compound to compound and also with temperature, Dihalides
solvent etc. The change of one form into another is also C2 H 4 X 2 Two
catalysed by acids and bases.
(e) Tautomers are in dynamic equilibrium with C3 H 6 X 2 Four
each other and interconvertible (⇌). C4 H 8 X 2 Nine
(f) Two tautomers have different functional C5 H10 X 2 Twenty one
groups.
 1034 General Organic Chemistry
Alcohols and H  C  COOH H  C  COOH
ethers || ||
H  C  COOH HOOC  C  H
C2 H 6 O Two (One alcohol and one ether) Maleic acid (cis) Fumaric acid (trans)

C3 H 8 O Three (Two alcohols and one H 3 C  C  COOH H 3 C  C  COOH

|| ||
ether) H  C  COOH HOOC  C  H
Citraconic acid (cis- isomer) Mesaconic acid (trans  isomer)
C4 H10 O Seven (Four alcohols and three
ethers) (1) Conditions for geometrical isomerism :
Compound will show geometrical isomerism if it fulfils
C5 H12 O Fourteen (Eight alcohols and six
the following two conditions
ethers)
(i) There should be frozen rotation about two
Aldehydes and
adjacent atoms in the molecule.
ketones
(a) CC frozen rotation about carbon,
C3 H 6 O Two (One aldehyde and one
carbon double bond in alkenes.
ketone)
C4 H 8 O Three (Two aldehydes and one
ketone)
(b) frozen rotation about carbon, carbon
C5 H10 O Seven (Four aldehydes and three single bond in cycloalkanes.
ketone) (c) C  N  frozen rotation about carbon,
Monocarboxylic nitrogen double bond in oxime and imine.
acids and esters (ii) Both substituents on each carbon should be
C 2 H 4 O2 Two (One acid and one ester) different about which rotation is frozen.
If these two conditions are fulfilled, then
C 3 H 6 O2 Three (One acid and two esters)
compound will show geometrical isomerism.
C 4 H 8 O2 Six (Two acids and four esters)  The compounds of the following type will not
C5 H10 O2 Thirteen (Four acids and nine show geometrical isomerism.
esters) a  C a x  C a a  C a
|| || ||
Aliphatic amines x C y aC a x C  x
C2 H7 N Two (One 1°-amine and one 2°-
amine) (2) Distinction between cis- and trans- isomers
C3 H 9 N Four (Two 1°-amines, one 2°- (i) By cyclization method : Generally, the cis-
amine and one 3°-amine) isomer (e.g. maleic acid) cyclises on heating to form the
corresponding anhydride while the trans-isomer does
C4 H11 N Eight (Four 1°-amines, three 2°-
not form its anhydride.
amines and one 3°-amines)
Aromatic H  C  COOH Heat H  C  CO
||   || O
compounds
H  C  COOH H  C  CO
C8 H10 Four Maleic acid(cis) Maleic anhy dride

C9 H12 Nine  Note that the two reacting groups (–COOH) are
near to each other.
C7 H 8 O Five
H  C  COOH Heat
||   No anhydride
Geometrical or cis-trans isomerism
HOOC  C  H
Fumaric acid (trans)
The compounds which have same molecular
 Note that the two reacting groups (–COOH) are
formula but differ in the relative spatial arrangement
quite apart from each other, hence cyclisation is not
of atoms or groups in space are known as geometrical
possible.
isomers and the phenomenon is known as geometrical
(ii) By hydroxylation (Oxidation by means of
isomerism. The isomer in which same groups or atoms
KMnO 4 ,OsO4 or H 2O2 in presence of OsO4 ) : Oxidation
are on the same side of the double bond is known as cis
(Hydroxylation) of alkenes by means of these reagents
form and the isomer in which same groups or atoms
proceeds in the cis-manner. Thus the two geometrical
are on the opposite side is called trans-isomer.
Examples :
 General Organic Chemistry 1035

isomers of an alkene leads to different products by

these reagents. For example,
H  C  COOH OH
KMnO 4 H COOH
||  
H COOH
H  C  COOH OH
Maleic acid (cis) meso  Tartaric acid

OH
H  C  COOH H
KMnO 4 COOH
|| 
HOOC  C  H HOOC H
Fumaric acid (trans )
OH
() Tartaric acid

OH
HOOC H

H COOH
OH
() Tartaric acid

(iii) By studying their dipole moments : The cis-

isomer of a symmetrical alkene (Alkenes in which both
the carbon atoms have similar groups) has a definite
dipole moment, while the trans-isomer has either zero
dipole moment or less dipole moment than the cis-
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 Dichloroethy lene trans  Dichloroethy lene cis Butene  2 trans  Butene  2
( 1 .9 D) ( 0 .0 D) (   0 . 0 D)

In trans-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 cis-isomer
has higher dipole moment than the corresponding
trans-isomer.
 General Organic Chemistry 1033
For Example, The symbol ‘E’ is assigned to an isomer in which
H 3 C  C  Cl CH 3  C  Cl the atoms or groups of higher preference are on the
|| || opposite side (E from German word Entgegen = across
CH 3  CH 2  C  Cl Cl  C  CH 2 CH 3 or opposite).
cis  2, 3  Dichloropentene  2 trans 2, 3  Dichloropentene  2
(High dipole moment) ( Less dipole moment ) The symbol ‘Z’ is assigned to an isomer in which
the atoms or groups of higher preference are on the
Similar is the case with hexene-2.
same side (Z from German word, Zusammen =
H3C CH 2 CH 2  CH 3
CC together).
H H
cisHexene  2(more polar) 1 2 1 1
CC CC
H CH 2 CH 2  CH 3 2 E  isom er
1 2 Z  isom er 2
C C
CH 3 H  1 signifies higher preference and 2 signifies
trans  Hexene  2(Less polar)
lower preference. Preference in most of the cases ‘Z’
(iv) By studying other physical properties: (a) corresponds to cis-form and ‘E’ to trans-form. However,
The cis-isomer of a compound has higher boiling point there are many exceptions.
due to higher polarity, higher density and higher The following rules are followed for deciding the
refractive index than the corresponding trans-isomer precedence order of the atoms or groups;
(Auwers-skita rule). (i) Higher priority is assigned to the atoms of
CH 3  C  H CH 3  C  H higher atomic number. For example, the order of
|| ||
CH 3  C  H H  C  CH 3 preference in the following atoms, H , Cl , I, Br is : I (at.
cis 2 Butene trans  2 Butene
b.p 4 C 1C no. 53)> Br (at. no. 35)>Cl (at. no. 17)>H (at. no. 1).
m.p. 139 C 106 C
(ii) If isotopes of the same element are attached,
H  C  Cl H  C  Cl the isotope with higher mass number is given higher
||
H  C  Cl
||
Cl  C  H order of preference. For example, deuterium  D
2
1 is
cis 1, 2  Dichloroethene trans 1, 2  Dichloroethene
60 C 48 C assigned higher priority in comparison to hydrogen
 80 C

(b) The trans-isomer has higher melting point

 50 C
 H .
1
1

than the cis-isomer due to symmetrical nature and (iii) In the groups, the order of preference is also
more close packing of the trans-isomer. decided on the basis of atomic number of first atom of
(v) Stability : Trans-isomer is more stable than the group. For example, in the following set,
cis-isomer due to symmetrical structure. Cl,OH,COOH , NH  CH 3 ,SO 3 H .
 Terminal alkenes such as propene, 1-butene and The order of the precedence is :
2-methyl propene do not show geometrical isomerism.  Cl   S O3 H   O H   N HCH 3   C OOH
    
( at.no17) ([Link].16) ([Link].8) ([Link].7) ([Link]. 6)
 Cis-trans isomers are configurational isomers
but not mirror images, hence cis and trans isomers are When the order of preference of the groups
always diastereomers. cannot be settled on the first atom, the second atom or
 Non-terminal alkenes with the same atoms or the subsequent atoms in the groups are considered. For
groups either on one or both the carbon atoms of the example, in the set CH 2  CH 3 ,CH 3 ,COOH , the order
double bond such as 2-methyl-2-butene, 2,3-dimethyl – cannot be decided on the basis of first atom as it is
2 – butene etc. do not show geometrical isomerism. same in all the groups. However, in CH 2  CH 3 , the
(3) E and Z system of nomenclature : ‘Cis’ and second atom is carbon, in CH 3 , the second atom is
‘Trans’ designations cannot be used if four different
hydrogen while in COOH , the second atom is oxygen.
atoms or groups are attached to the carbon atoms of a
Hence, the order of preference is :
double bond.
C O OH  CH 2  C H 3  C H 3
a d   
CC ([Link].8) ([Link].6) ([Link].1)
b e
In such cases, E and Z system of nomenclature is (iv) A doubly or triply bonded atom is considered
used. This system is based on a priority system equivalent to two or three such atoms. For example,
developed by Cahn, Ingold and Prelog. The group C  O is equal to C O and the group
|
In this system, the two atoms or groups attached O
to each of the doubly bonded carbon are put in order of N
preference on the basis of sequence rules. |
C  N is equal to  C N .
|
N
 1034 General Organic Chemistry
(4) Number of geometrical isomers in polyenes Similarly consider the following structure
(i) When a compound has n double bonds and C 2 H 5 C CH 3
||
ends of a polyene are different, the number of N OH
geometrical isomers  2 n Sy n  m ethy lethy l ketoxim e
or Anti  ethy l m ethy l ketoxim e
C6 H5  CH  CH  CH  CH  CH  CH  CH  CH  Cl (ii) Geometrical isomerism due to N = N bond.
The given compound has four double bonds and C6 H 5  N C6 H 5  N
|| ||
the two ends are different (One is C6 H5 and other is C H N N  C6 H 5
6 5 Anti azobenzene
Cl). Therefore, number of geometrical isomers Sy n - azobenzene

 2n  2 4  16 . (6) Geometrical isomerism show by

(ii) When the ends of polyene are same. cumulatrienes : Cumulatrienes (Trienes with three
Case I : When number of double bonds (=n) is adjacent double bonds) show only geometric
even then the number of geometrical isomers isomerism. This is because their molecule is planar, as
such the terminal CH 3 groups and H- atoms lie in the
 2 n 1  2[(n / 2)1]
Cl  CH  CH  CH  CH  CH  CH  CH  CH  Cl same plane. Therefore, in this case their planar
n  4 , even
structure can exist in two diastereoisomeric forms, cis-
Number of geometrical isomers  2n 1  2(n / 2)1 and trans- but no enantiomeric forms are possible.
3 1
 2  2  8  2  10 . H 3C CH 3
CCCC
Case II : When number of double bonds (=n) is H H
odd. cis Hexa  2, 3 , 4  triene

 n 1  H 3C H
 2  1
Number of geometrical isomers  2 n 1  2   CCCC
H CH 3
C6 H 6  CH  CH  CH  CH  CH  CH  C6 H 5 trans  Hexa  2, 3 , 4  triene
(n  3 , odd )
(7) Geometrical isomerism in cycloalkanes :
Number of geometrical isomers  2 2  2 2 1 Disubstituted cycloalkanes show geometrical
 2 2  21  4  2  6 . isomerism.
(5) Geometrical Isomerism in nitrogen CH3
OH
compounds H OH H
(i) Geometrical isomerism due to C  N  bond. H CH3
H OH HO
The important class of compounds exhibiting H
geometrical isomerism due to C  N  bond are oximes, H Cis-1,2-
Cis-1,2-dimethylcyc cyclohexanediol Trans-1,2-
nitrones, hydrazones and semicarbazones. But the most lopropane cyclopent anediol
common compound is oxime.
 Certain compounds show geometrical as well
Oximes : In aldoxime, when hydrogen and
optical isomerism. Such type of isomerism is known as
hydroxyl groups are on the same side, the isomer is
geometrical enantiomerism.
known as syn. (analogous to cis) and when these
groups are on the opposite side, the isomer is known as Optical isomerism
C6 H 5  C  H (1) Compounds having similar physical and
anti (analogous to trans) ||
chemical properties but they have the ability to rotate
N  OH
Sy n - benzaldoxi me the plane of polarised light either to the right
C6 H 5  C  H (Clockwise) or to the left (Anticlockwise) are termed as
|| optically active or optical isomers and the property is
HO  N called optical activity or optical isomerism.
Anti benzaldoxi m e

In ketoximes the prefixes syn and anti indicate The optical activity was first observed in organic
which group of ketoxime is syn or anti to hydroxyl substances like quartz, rock-crystals and crystals of
group. For example: potassium chlorate (KClO 3 ) , potassium bromate
CH 3  C  C2 H 5 (KBrO 3 ) and sodium periodate (NaIO4 ) .
|| this compound will be named as;
N OH (2) Measurement of optical activity : The
(a) Syn-ethyl methyl ketoxime  HO and C2 H5 measurement of optical activity is done in terms of
are syn or specific rotation which is defined as the rotation
(b) Anti-methyl ethyl ketoxime  HO and C 2 H 5 produced by a solution of length of 10 centimetres (One

are anti.
 General Organic Chemistry 1035
decimetre) and unit concentration (1 g/mL) for the given
wavelength of the light at the given temperature.
 obs
Specific rotation,  twavelength
C

lC
(ii) Elements of symmetry : There are three
Where obs is the rotation observed, l is the elements of symmetry,
length of the solution in decimeters and C is the (a) Plane of symmetry : It may be defined as a
number of grams in 1mL of solution. The specific plane which divides a molecule in two equal parts that
rotation of the sucrose at 20°C using sodium light (D- are related to each other as an object and mirror image.
line, =5893Å) is +66.5°C and is denoted as: e.g.,
 20D C  66 .5C(C  0.02 g / mL water) COOH
+ sign indicates the rotation in clockwise |
H  C  OH
direction. | Plane of
(3) On the basis of the study of optical activity, H  C  OH symmetry
the various organic compounds were divided into four |
COOH
types :
(i) The optical isomer which rotates the plane of (b) Centre of symmetry : It may be defined as a
the polarised light to the right (Clockwise) is known as point in the molecule through which if a line is drawn
dextrorotatory isomer (Latin: dextro = right) or d-form in one direction and extended to equal distance in
or indicated by +ve sign. opposite direction, it meets another similar
Centregroup or
of symmetry
atom, eg.
(ii) The optical isomer which rotates the plane of
CH 3 CH 3 CH 3 H
the polarised light to the left (Anticlockwise) is known
as laevorotatory isomer (Latin; laevo = left) or l-form | NH  CO | | NH  CO |
or indicated by –ve sign. C C and C  C
| CO  NH | | CO  NH |
(iii) The optical powers of the above two isomers
H H H CH 3
are equal in magnitude but opposite in sign. An cis  Dimethy ldiketo piperazine Trans  Dimethy ldiketo piperazine
equimolar mixture of the two forms, therefore, will be
Since trans form contains a centre of symmetry, it
optically inactive due to external compensation. This
mixture is termed as racemic mixture or dl-form or () is optically inactive.
mixture. (c) Alternating axis of symmetry : A molecule is
said to possess an alternating axis of symmetry if an
(iv) Optical isomer with a plane of symmetry is
oriention indistinguishable from the original is
called meso form. It is optically inactive due to internal
obtained when molecule is rotated Q degree around an
compensation, i.e., the rotation caused by upper half
part of molecule is neutralised by lower half part of axis passing through the molecule and the rotated
molecule. molecule is reflected in a mirror that is perpendicular
to the axis of rotation in step (I).
(4) Chirality, (i) Definition : A molecule (or an
Reflection
object) is said to be chiral or dissymmetric, if it is does perpendicular to
not possess any element of symmetry and not axis rotation
Cl H H F H
Cl
superimposable on its mirror image and this property H F 180o Cl H H F
of the molecule to show non-superimposability is called F H rotation
Cl
around axis H F
H
chirality. H Cl F H H Cl
On the other hand, a molecule (or an object)
which is superimposable on its mirror image is called
achiral (non-dissymmetric or symmetric). (iii) Symmetric, Asymmetric and Dissymmetric
molecules
To understand the term chiral and achiral let us
consider the alphabet letters ‘P’ and ‘A’ whereas ‘P’ is (a) Symmetric molecules : If any symmetry is
chiral, ‘A’ is achiral as shown in fig. present in the molecule then molecule will be
symmetric molecule.
Mirror Mirror
(b) Dissymmetric molecules : Molecule will be a
dissymmetric molecule if it has no plane of symmetry,

Non-superimposable Superimposable
(Chiral or (Achiral or non-
dissymmetric) dissymmetric)
 1036 General Organic Chemistry
no centre of symmetry and no alternating axis of Number of enantiomeric pair  a/2
symmetry. Number of racemic mixture  a/2
(c) Asymmetric molecules : Dissymmetric Number of meso form 0
molecule having at least one asymmetric carbon is
(ii) If molecule is divisible into two identical
known as asymmetric molecule. All asymmetric
halves, then the number of configurational isomers
molecules are also dissymmetric molecules but the
depends on the number of asymmetric carbon atoms.
reverse is not necessarily true.
Case I : When compound has even number of
COOH
carbon atoms, i.e., n  2, 4, 8, 10, 12, ..... :
| CHO
H — C  — OH | (i) Number of optically by active forms  a  2 n 1
| H — C  — OH (ii) Number of enantiomeric pairs  a / 2
H — C  — OH | (iii) Number of racemic mixture  a / 2
| CH 3
No plane of symmetry (iv) Number of meso forms  m  2 (n / 2)1
C6 H 5
No plane of symmetry  (v) Total number of configurational isomers
Dissymmetric molecule
 am
Dissymmetric molecule 
Asymmetric molecule
 Case II : When compound has odd number of
Asymmetric molecule
carbon atoms, i.e., n  3, 5, 7, 9, 11, ...... :
(iv) Chiral or asymmetric carbon atom : A
(i) Number of optically active forms
carbon bonded to four different groups is called a chiral
 a  2 n 1  2(n 1) / 2
carbon or a chirality centre. The chirality centre is
indicated by asterisk. e.g., (ii) Number of enantiomeric pairs  a / 2
a CH 3 (iii) Number of racemic mixutre  a / 2
| |
* *
d C b HO  C  H (iv) Number of meso forms  m  2 (n 1) / 2
| |
c COOH (v) Total number of configurational isomers
Lactic acid
am
 Carbons that can be chirality centres are sp 3 -
(6) Optical activity of compounds containing
hybridised carbons; sp 2 and sp -hybridised carbons
one asymmetric carbon
cannot be chiral carbons because they cannot have four
Examples :
group attached to them.
 
 Isotopes of an atom behave as different group CH 3  C HOH  COOH ; CH 3  C HOH  CHO
in stereoisomerism. Lactic acid

D H1  
CH 2 OH  C HOH  CHO ; C6 H 5  C HCl  CH 3
| | Gly ceraldehy de 1 - chloro -1 - pheny letha ne
H — C* — T Cl 35 — C * — Cl 37
Any molecule having one asymmetric carbon
| |
atom exists in two configurational isomers which are
Br H2 nonsuperimposible mirror images.
Lactic acid
COOH COOH
 Carbon of the following groups will not be a
| |
chiral carbon
H — C — OH HO — C — H
O
|| | |
 CH 3 ,  CH 2 OH ,  CHX 2 ,  CHO ,  C  Z CH 3 CH 3
(I) (II)
 Maleic acid (HOOC  CH  CH  COOH ) show
(I) and (II) have the same molecular formula, the
geometrical isomerism while malic acid
same structure but different configurations, hence (I)
(HOOC  CH 2  CHOH  COOH ) show optical isomerism. and (II) are known as configurational isomers. (I) and
(5) Calculation of number of optical isomers (II) are nonsuperimposable mirror images, hence (I)
(i) If molecule is not divisible into two identical and (II) are optical isomers. Configurational isomers
halves and molecule has n asymmetric carbon atoms which are nonsuperimposable mirror images are
known as enantiomers. Thus (I) and (II) are
then
Number of optically active forms  2 n  a
 General Organic Chemistry 1037
enantiomers. Pair of (I) and (II) is known as diastereomers have the same functional groups, their
enantiomeric pair. chemical properties are not very dissimilar.
(i) Properties of Enantiomers : All chemical and Case II : When molecule is divisible into two
physical properties of enantiomers are same except two identical halves.
physical properties.
Number of optical isomers  a  2 2 1  2
Mode of rotation : One enantiomer rotates light to
the right and the other by an equal magnitude to the Number of meso forms  m  2 0  1
left direction. Total number of configurational isomers  3
(ii) Racemic Mixture : An equimolar mixture of (8) Optical activity in compounds containing no
two enantiomers is called a racemic mixture (or assymmetric carbon : Although the largest number of
racemate,  form, (dl) form or racemic modification). known optically active compounds are optically active
Such a mixture is optically inactive because the two due to the presence of chiral carbon atom, some
enantiomers rotate the plane polarised light equally in compounds are also known which do not possess any
opposite directions and cancel each other’s rotation. chiral carbon atom, but on the whole their molecules
are chiral (such molecules were earlierly called
This phenomenon is called external compensation.
dissymmetric); hence they are optically active. Various
 Racemic mixture can be separated into (+) and types of compounds belonging to this group are allenes,
(–) forms. The separation is known as resolution. alkylidene cycloalkanes, spiro compounds (spirans) and
 The conversion of (+) or (–) form of the properly substituted biphenyls.
compound into a racemic mixture is called (i) Allenes : Allenes are the organic compounds of
racemisation. It can be caused by heat, light or by the following general formulae.
chemical reagents. C C C
 Racemic mixture is designated as being (  ) or Allenes exhibit optical isomerism provided the
(dl). two groups attached to each terminal carbon atom are
(7) Optical activity of compounds containing different, i.e.,
two asymmetric carbon a a a x
Case I : When molecule is not divisible into two CCC or C C C
identical halves. b b b y
The number of optical isomers possible in this (ii) Alkylidene cycloalkanes and spiro
2 compounds : When one or both of the double bonds in
case is four (a  2  4 ) . Further there will be two pairs
allenes are replaced by one and two rings, the resulting
of enantiomers and two racemic modifications. In
systems are respectively known as alkylidene
practice also it is found to be so.
cycloalkanes and spirans.
Configurational isomers which are not mirror
H 3C H
images are known as diastereomers.
C
Properties of Diastereomers : Diastereomers H COOH
have different physical properties, e.g., melting and 1-Methylcyclohexylidene-4-
boiling points, refractive indices, solubilities in acetic acid (Alkylidene
a CH 2 cycloalkane)
CH 2 a
different solvents, crystalline structures and specific
C C C
rotations. Because of differences in solubility they
b CH 2 CH 2 b
often can be separated from each other by fractional
Spirans
crystallisation; because of slight differences in
molecular shape and polarity, they often can be (iii) Biphenyls : Suitably substituted diphenyl
separated by chromatography. compounds are also devoid of individual chiral carbon
atom, but the molecules are chiral due to restricted
Diastereomers have different chemical properties
rotation around the single bond between the two
towards both chiral and achiral reagents. Neither any
benzene nuclei and hence they must exist in two non-
two diastereomers nor their transition states are superimposable mirror images of each other. Such
mirror images of each other and so will not necessarily types of stereoisomerism which is due to restricted
have the same energies. However, since the rotation about single bond, is known as atropisomerism
 1038 General Organic Chemistry
and the stereoisomers are known and atropisomers. nomenclature was given by Emil Fischer to designate
Examples the configurations of various sugars relative to the
COOH O2N F HOOC enantiomeric (+) and (–) glucose as reference.
All sugars whose Fischer projection formula
shows the OH group on the chiral carbon atom adjacent
NO2 HOOC COOH F to the terminal CH 2 OH group on the right hand side
The above discussion leads to the conclusion that belong to the D -series. Similarly if OH is on the left
the essential condition for optical isomerism is the hand side, then the sugars belong to the L -series.
molecular disymmetry or molecular chirality and not the
| |
mere presence of a chiral centre. However, it may be H — C — OH HO — C — H
noted that the molecules having only one chiral centre | |
CH 2 OH CH 2 OH
are always chiral and exhibit optical isomerism. D  series L  series
(9) Fischer projection formulae : The Examples :
arrangement of the atoms or groups in space that CHO CHO
characterises a stereoisomer is called its configuration. | |
H — C — OH HO — C — H
| |
Emil Fischer (1891) provided an easy method to
CH 2 OH CH 2 OH
represent the three dimensional formulae of various D(d ) gly ceraldehy de L (l ) gly ceraldehy de
or or
organic molecules on paper. Fischer projection is, thus, D( ) gly ceraldehy de L () gly ceraldehy de
a planar representation of the three dimensional
 It must be noted that there is no relation
structure.
between the sign of rotation (+, – or d, l) and the
By convention, the following points are followed
configuration (D and L) of an enantiomer.
in writing the Fischer formula.
 Any compound that can be prepared from, or
(i) The carbon chain of the compound is arranged
vertically, with the most oxidised carbon at the top. converted into D(+) glyceraldehyde will belong to D-
series and similarly any compound that can be
(ii) The asymmetric carbon atom is in the paper
prepared from, or converted into L(–) glyceraldehyde
plane and is represented at the interaction of crossed
will belong to the L-series.
lines.
Asymmetric  This nomenclature is also used in  -amino
Carbon atom acids.

(ii) Erythro and Threo system of nomenclature :

This nomenclature is used only in those compounds
which have
C
(a) Only two chiral carbons and

(b) The following structure, R  Cab  Cbc  R

(iii) Vertical lines are used to represent bonds i.e., out of six substituents on two asymmetric
going away from the observer, i.e., groups attached to carbons, at least two should be same.
the vertical lines are understood to be present behind
When two like groups in Fischer projection
the plane of the paper.
formula are drawn on the same side of the vertical line,
(iv) Horizontal lines represent bonds coming the isomer is called erythro form; if these are placed on
towards the observer, i.e., groups attached to the the opposite sides, the isomer is said to be threo form.
horizontal lines are understood to be present above the
plane of the paper.
(10) Name of optical isomers : Following three
nomenclatures are used for optically active compounds,
(i) D,L. System of nomenclature : This
nomenclature is mainly used in sugar chemistry or
optically active polyhydroxy carbonyl compounds. This
 General Organic Chemistry 1039
R CH 3 CH 3 COOH 4
| | | | |
a—C—b H — C — Cl H — C — Cl H 2 N — C — Br  3 —C —1
| | | | |
c—C—b H — C — Br Br — C — H OH 2
| |
C N O Br
| 
Increasing priority with atomic number
R  C6 H 5 C6 H 5
Erythro form Erythro form Threo form
Rule 2 : If two or more than two isotopes of the
(c) R,S Nomenclature (Absolute configuration) same element is present, the isotope of higher

The order of arrangement of four groups around

atomic mass receives the higher priority.
1 2 3
1 H 1H 1H
a chiral carbon (stereocentre) atom is called the
absolute configuration around that atom. System which Increasing
priority
indicates the absolute configuration was given by three 3 2 1
chemists R.S. Cahn, C.K. Ingold and V. Prelog. This
system is known as (R) and (S) system or the Cahn- Rule 3 : If two or more of the atoms directly
Ingold Prelog system. The letter (R) comes from the bonded to the chiral carbon are identical, the atomic
latin rectus (means right) while (S) comes from the number of the next atoms are used for priority
latin sinister (means left). Any chiral carbon atom has assignment. If these atoms also have identical atoms
either a (R) configuration or a (S) configuration. attached to them, priority is determined at the first
Therefore, one enantiomer is (R) and other is (S). A point of difference along the chain. The atom that has
racemic mixture may be designated (R) (S), meaning a attached to it an atom of higher priority has the higher
mixture of the two. (R) (S) nomenclature is assigned as priority.
follows : I 2 H and Br
| 
Step I : By a set of sequence rules given below I  H 2 C  H 2 C  C  C H 2  Br
 |
the atoms or groups connected to the chiral carbon are 2 H and C CH 2  CH 2  CH 3
assigned a priority sequence. 
2 H and C
Sequence Rules for Order of Priority

Rule 1 : If all four atoms directly attached to the In this example the atoms connected directly to
chiral carbon are different, priority depends on their the chiral carbon are iodine and three carbons. Iodine
atomic number. The atom having highest atomic has the highest priority. Connected, to the three
number gets the highest priority, i.e., (1). The atom carbons are 2H and Br, 2H and C and 2H and C.
with the lowest atomic number is given the lowest Bromine has the highest atomic number among C,H and
priority, i.e., (2), the group with next higher atomic Br and thus CH 2 Br has highest priority among these
number is given the next higher priority (3) and so on. three groups (i.e., priority no. 2).The remaining two
Thus, carbons are still identical (C and 2H) connected to the
Cl 3 second carbons of these groups are 2H and I and 2H
| | and C. Iodine has highest priority among these atoms,
F — C — I  4 — C —1 so that CH 2  CH 2  I is next in the priority list and
| | CH 2  CH 2  CH 3 has the last priority.
Br 2
F Cl Br I

I 1
|
Increasing atomic number
I  CH 2  CH 2  C  CH 2  Br  3 2
|
4 3 2 1 CH 2 CH 2 CH 3 4
Increasing priority
Rule 4 : If a double or a triple bond is linked to
chiral centre the involved atoms are duplicated or
triplicated respectively.
 1040 General Organic Chemistry
O N O O First interchange of two groups at the chiral
| | || |
 C  O   C  O ;  C  N   C  N ;  C  OH   C  OH centre inverts the configuration and this gives
| | | | enantiomer of the original compound. Thus (A) and (B)
N O
are enantiomer. The second interchange involves the
By this rule, we obtained the following priority remaining two groups.
sequence
CH:  CR 2 , CN , CH 2 OH , CHO, CO, COOH 3 1
| Second |
1 C  2 interchange 3 C  2
| |
Increasing between remaining
priority 4 groups, i.e., 1 and3 4
(B) (A)
Step 2 : The molecule is then visualised so that Arrangement of1 2, and
3
the group of lowest priority (4) is directed away from Example : are clockwise, hence
configuration is R
the observes (At this position the lowest priority is at H O
the bottom of the plane). The remaining three groups CHO C
| | O
are in a plane facing the observer. If the eye travels H  C  OH  H  C  OH 
| |
clockwise as we look from the group of highest priority CH 2OH CH 2OH
to the groups of second and third priority (i.e., D-gly ceraldehy de
2 2
1  2  3 with respect to 4) the configuration is | First |
designated as R. If arrangement of groups is in 4 C 1 interchange 3 C 1
| Between3 and4 |
anticlocwise direction, the configuration is designated
3 4
as S. 1
Second
For example: interchange 3 2
Between1 and2
2 2 4
| |

1 C
|
 3 3 C 1
| Clockwise
4 4 R-
Clockwise Anticlockwise
CHO 2
configuration
| 1
arrangement | (i) First interchange between 4
1 2 3of arrangement
1 2 3of HO  C  H 
3
| 1  C  4 and
3
, and R , and S |
2
(ii) Sec. interchange between
CH 2OH 1 2 2
3 and
Let us apply the whole sequence to L-Gly ceraldehy de 4
bromochlorofluoro methane. Anticlockwise

F 3
| | S-configuration
Br  C  H  1 C 4 Glyceraldehyde (For example) has one asymmetric
| |
Cl carbon, hence it has two configurational isomers (I) and
2
(II).
In this Fischer projection the least priority
CHO CHO
number is not at the bottom of the plane. | |
H  C  OH HO  C  H
In such cases the Fischer projection formula of | |

the compound is converted into another equivalent CH 2 OH CH 2 OH

( R ) gly ceraldehy de (S ) gly ceraldehy de
projection formula in such a manner that atom or group (I) (II)
having the lowest priority is placed vertically One can draw a number other configurations for
downward. This may be done by two interchanges glyceraldehyde but each of them will be a repetition of
between four priority numbers. The first interchange either (I) or (II). In this connection it is important to
involves the two priority numbers, one is the least note that if two projection formulae differ by an odd
priority number and other is the priority number which number of interchanges (1, 3, 5, 7, …..) of positions of
is present at the bottom of the plane. In the above case groups on the chiral carbon, they are different. But if
first interchange will takes place between 2 and 4. the two differ by an even number of interchanges (2, 4,
3 3 6, …..) they are identical.
| First |
For example :
1 C  4 interchange 1 C  2
| | CHO
Between2 and 4 CHO
2 4 | |
H , CH 2OH Second interchang e
H  C  OH   CH 2 OH  C  H  
(A) (B) | First interchang e | between OH , CHO
CH 2 OH H
( I) ( II)
 General Organic Chemistry 1041
OH Conformational isomerism
|
Third intrerchange
CH 2 OH  C  CHO 
 (1) Definition : The different arrangement of
| CH 2OH , OH
H atoms in a molecule which can be obtained due to
( III)
rotation about carbon-carbon single bond are called
CH 2 OH CH 2 OH
| | conformational isomers (conformers) or rotational
Fourth interchang e
HO  C  CHO   HO  C  H isomers (rotamers). This type of isomerism is found in
| H , CHO |
H CHO alkanes and cycloalkanes and their substituted
( IV) (V )
derivatives.
Thus (I), (III) and (V) are identical. Similarly (II)
It may be noted that rotation around a C  C
and (IV) are identical.
sigma bond is not completely free. It is in fact hindered
(11) Resolution of racemic modifications : The
by an energy barrier of 1 to 20 kJ mol–1 in different
separation of racemic mixture into its enantiomers is
bonds. There is a possibility of weak repulsive
known as resolution.
interactions between the bonds or electron pairs of the
 Group X reacts with group O to give new group
bonds on adjacent carbon atoms. Such type of repulsive
W.
interaction is known as torsional strain.
(12) Asymmetric synthesis and Walden
(2) Difference between conformation and
inversion
configuration : The term conformation should not be
(i) Asymmetric synthesis : The synthesis of an confused with the configuration which relates to those
optically active compound (asymmetric) from a spatial arrangements of the atoms of a molecule that can
symmetrical molecule (having no asymmetric carbon) be changed only by the breaking and making of bonds
without resolution to form (+) or (–) isomer directly is whereas the spatial arrangements in conformation are
termed asymmetric synthesis. For example the changed simply by rotation about a single bond.
O
|| (3) Representation of conformations :
reduction of pyruvic acid (CH 3  C  COOH ) in presence Conformers can be represented in two simple ways.
of nickel catalyst gives () lactic acid (racemic These are : (i) Saw horse representation and (ii)
mixture). On the other hand, pyruvic acid is reduced to Newman projection
(–) lactic acid only by yeast. (i) Saw horse representation : In this projection,
CH 3 CH 3 the molecule is viewed along the axis of the model from
| |
2H an oblique angle. The central carbon-carbon bond

 H  C  OH  H  C  H
' Ni ' | | ( C  C ) is draw as a straight line slightly tilted to right
COOH COOH
CH 3 for the sake of clarity. The front carbon is shown as the
|
( (
) Lactic acid ) Lactic acid

Reduction mixture lower left hand carbon and the rear carbon is shown as
CO   
| the upper right hand carbon. The three bonds around
COOH CH 3 each carbon atom (C  H in ethane or C  C in higher
(Pyruvic acid)
(2 -Keto propanoic acid) |
2H

 HO  C  H alkanes) are shown by three lines.
Yeast |
COOH H
() Lactic acid
Back
(ii) Walden inversion: The conversion of (+) carbon
C
form into (–) form and vice-versa is called Walden H
H H Back
inversion. When an atom or group directly linked to an H carbon
H
asymmetric carbon atom is replaced; the configuration H H
of the new compound may be opposite to (inverse) that C Front Front
of the original, i.e., carbon H Hcarbon

CH 3 CH 3 COOH H H
|
PCl 5
|
AgOH
| Saw horse Newman
H  C  OH  Cl  C  H 
 HO  C  H representation projection
| | |
CH 2 COOH CH 2 COOH CH 2 COOH (ii) Newman projection : This is a simple method
() Malic acid () Chloro succinic acid () Malic acid
to represent the conformations. In this method, the
COOH COOH molecule is viewed from the front along the carbon-
| |
PCl 5
 H  C  Cl   AgOH
 H  C  OH carbon bond axis. The two carbon atoms forming the -
| |
CH 2COOH CH 2 COOH bond are represented by two circles; one behind the
( ) Chloro succinic acid ( ) Malic acid other so that only the front carbon is seen. The front
 1042 General Organic Chemistry
carbon atom is shown by a point whereas the carbon This conformation will be maximum staggered,
further from the eye is represented by the circle. most stable and is called anti or trans conformation
Therefore, the C  H bonds of the front carbon are (marked I). Other conformations can be obtained by
depicted from the centre of the circle while C  H rotating one of the C 2 or C 3 carbon atoms through an
bonds of the back carbon are drawn from the
angle of 60° as shown ahead.
circumference of the circle at an angle of 120° to each
other. CH3 CH3 CH3
(4) Conformation in alkanes H H H CH3 H
(i) Conformations of ethane : When one of the H3C H
H H H H
carbon atom is kept fixed and other is rotated about H H
CH3 H
C  C bond an infinite numbers of isomers are possible.
I II III
Out of all the conformations for ethane, only two
Anti Eclipsed Skew or Gauche
extreme conformations are important and these are:
(a) Staggered conformation CH3 CH3 CH3
(b) Eclipsed conformation CH3 H CH3 H
60° H H H H
H H H H
H
H H H CH3
H H 60°
H
60° IV V VI
H H
H H Fully eclipsed Skew or Gauche Eclipsed
H H
H (same as III) (same as II)
60 Eclipsed
conformation
° Staggered As is clear from the above Newman projection the
conformation
Gauche or Skew conformations (III and V) are also
Staggered conformation of ethane is more stable staggered. However, in these conformations, the
than eclipsed. methyl groups are so close that they repel each other.
This repulsion causes gauche conformations, to have
(ii) Conformations of propane : The next higher
about 3.8 kJ mol-1 more energy than anti conformation.
member in alkane series, propane (CH 3  CH 2  CH 3 )
This conformations II and VI are eclipsed
also has two extreme conformations, the energy barrier
conformations. These are unstable because of
in propane is14kJmol–1, which is slightly higher than
repulsions. These are 16 kJ mol-1 less stable than anti
CH3
that in ethane. CH3 conformation. Conformation IV is also eclipsed and it is
H H H
least stable having energy 19 kJ mol-1 more than anti
H H H H conformation. This is because of repulsion between
H H H
methyl-methyl groups which are very closed together.
Staggered Eclipsed propane
propane It is called fully eclipsed conformation.
Newman projection of propane
The order of stability of these conformations is,
Anti > Skew or Gauche > Eclipsed > Fully eclipsed.
(iii) Conformations of butane : As the alkane
molecule becomes larger, the conformation situation (5) Conformations in cycloalkanes
becomes more complex. In butane (i) Stability of cycloalkanes : Compounds with
(CH 3  CH 2  CH 2  CH 3 ) , for example, the rotation three and four membered rings are not as stable as
about the single bond between two inner atoms ( C 2 compounds with five or six membered rings.

and C 3 ) is considered. In this case, all the staggered as The German chemist Baeyer was the first to
suggest that the instability of these small rings
well as eclipsed conformations will not have same
compounds was due to angle strain. This theory is
stability and energy because of different types of
known as Baeyer-strain theory.
interaction between C  C (of methyl) and C  H bonds.
Baeyer strain theory was based upon the
The lowest energy conformation will be the one,
assumption that when an open chain organic compound
in which the two methyl groups are as far apart as
having the normal bond angle 109.5° is convert into a
possible i.e., 180° away form each other.
cyclic compound, a definite distortion of this normal

24.44°
deviation

109.5° 60
°
109.5°
 General Organic Chemistry 1043
angle takes place leading to the development of a strain strain theory is applicable only to cyclopropane,
in the molecule. cyclobutane and cyclopantane.

The mistake that Baeyer made was to assume

that all cyclic compounds are planar. But only
cyclopropane is planar and other cycloalkanes are not
planar. Cyclic compounds twist and bend in order to
achieve structure that minimises the three different
kinds of strain and that can destabilise a cyclic
compound.

(a) Angle strain is the strain that results when

Baeyer assumed that cyclic rings are planar.
the bond angle is different from desired tetrahedral
Assuming that the rings are planar, the amount of
bond angle of 109.5°.
strain in various cycloalkanes can be expressed in
terms of angle of deviation (d). (b) Torsional strain is caused by repulsion of the
bonding electrons of one substituent with bonding
1 2(n  2)  1
d 109 .5   90  or d [109 .5   ] electrons of a nearby substituent.
2  n  2
(c) Steric strain is caused by atoms or groups of
Where n = number of carbon-carbon bonds in
atoms approaching each other too closely.
cycloalkane ring;  = inner bond angle in the
cycloalkane ring. (ii) Conformation of cyclohexane : Despite
Baeyer’s prediction that five-membered cyclic
1 1
Angle strain  d  ; Stability   inner angle(  ) compounds would be the most stable, the six membered
inner angle d
cyclic compound is the most stable. Six membered
Now let us take the case of three to eight cyclic compound are most stable because they can exist
membered cyclic compounds. in a conformation that is almost completely free of
  
strain. This conformation is called the chair
conformation. In a chair conformation of cyclohexane
Cyclopropane Cyclobutane Cyclopentane all bond angles are 109.38° which is very close to the
 = 60°  = 90°  = 108°
109.5° and all the adjacent carbon-hydrogen bonds are
d = 22.44° d = 9.4° d = 0.44°
staggered.
  a a
H H
 c
c c H CH2 H
Cyclohexane Cycloheptane Cyclooctane a a
H CH2 H
 = 120°  = 128.6°  = 135° c
c c H H
d = –5.16° d = –9.33° d = –12.46°
a a Newmann projection
of the chair
The positive and negative values of (d) indicate Chair conformation
of cyclohexane conformation
whether the inner angle is less than or more than the
normal tetrahedral value.
 Each carbon in chair conformation has an
Beayer thus predicted that a five membered ring axial bond and an equatorial bond.
compound would be the most stable. He also predicted  Axial bonds are perpendicular to the plane of
that six membered ring compounds would be less stable the ring and equatorial bonds are in the plane of the
and as the cyclic compounds become larger than five ring.
membered ring, then they would become less and less  If axial bond on carbon-1 is above the plane of
stable. the ring then axial bond on carbon-2 will be below the
plane of the ring. Thus
Contrary to what Baeyer predicted, however
C  1, C  3 and C  5 axial bonds are above the
cyclohexane is more stable than cyclopentane.
Furthermore, cyclic compounds do not become less and plane
less stable as the number of sides increase. Thus Baeyer
 1044 General Organic Chemistry
C  2, C  4 and C  6 axial bonds are below the 2.4 Å. The flagpole hydrogens are also known as trans
plane nuclear hydrogens.
a a
1  The relative stabilities of the four
6 5
conformations of cyclohexane decrease in the order:
a a
Chair > twist boat > boat > half chair.
2 3 4
a a

 Thus C  1 axial and C  2 axial are trans to

each other. Similarly C  1 and C  5 axials are cis 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 trans.
(b) C  1 axial and C  2 equatorial will be cis.
 As a result of rotation about carbon-carbon
single bonds cyclohexane rapidly interconverts
between two stable chair conformations. This
interconversion is known as ring –flip. When the two
chair forms interconvert, axial bonds become
equatorial and equatorial bonds become axial.

Flipping

 Cyclohexane can also exist in a boat

conformation. Like the chair conformation, the boat
conformation is free of angle strain. However, the boat
conformation is less stable than the chair conformation
by 11 kcal/mole. Boat conformation is less stable
because some of the carbon-hydrogen bonds in boat
conformation are eclipsed.
The boat conformations is further destabilised by
the close proximity of the flagpole hydrogens. These
hydrogens are 1.8 Å apart but the vander Waal’s radii is