Isomerism Theory 1-27

ISOMERISM
ISOMERISM
DEFINATION OF ISOMERISM :
When two or more compounds have same molecular formula but they differ in their physical properties or
chemical properties or both then they are called isomers & the phenomena is called isomerism. Isomers
are also sometimes called as isomerides.
Classification of Isomerism
STRUCTURAL ISOMERISM :
When two or more organic compounds have same molecular formula but different structural formula,
(i.e., they differ in connectivity of atoms) then they are called structural isomers and the phenomena is
called structural isomerism
Structural isomers have always different IUPAC name
Ex. : CH3  CH  CH  CH3 , CH3CH2CH  CH2 
But  2  ene But  1  ene  structural Isomers
CH3
|
CH3  CH  CH2CH3 
Ex. : CH  CH2  CH3 , |  Identical compounds
| CH3  (not isomers)
CH3 
2  Methylbutane 
2  Methyl bu tan e
Isomers Characteristics Conditions

They have different size of They have same nature of
(1) Chain Isomers
main chain or side chain locants
They should have same size of
They have different position of
(2) Positional Isomers main chain and side chain and
locants
same nature of locant
Chain and positional isomerism is
(3) Functional Isomers Different nature of locant
not considered
Different nature of alkyl group They should have same nature of
(4) Metamerism along a polyvalent functional functional groups chain &
group positional isomer is ignored
The two functional isomers

Different position of hydrogen
(5) Tautomerism remains in dynamic equilibrium
atoms
to each other
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ISOMERISM
Chain Isomerism or nuclear isomerism or skeletal isomerism
Chain isomers have the same molecular formula but differ in the order in which carbon atoms are bonded
to each other.This type of isomerism is due to difference in the arrangement of carbon atoms i.e. straight or
branched chain of carbon atoms. It is also known as nuclear or skeletal isomerism
Condition : – 1. Size of main chain or side chain or both should be different.
2. Nature of functional group, multiple bond or substituent should not change.
Ex. : (A) CH3 – CH2CH2 – CH3
Butane 2–Methylpropane
Size of main chain = 4 Size of main chain = 3
Size of side chain = 0 Size of side chain = 1
Isomeric pair :
When more than one structure can be written with a given molecular formula, each of the structure with
respect to any other structure is called an isomeric pair.
Isomerism between two structures 'a1' & 'a2' can also be seen as a relation a1Ra2 between them.
CH3
|
Ex. : CH3  CH2  CH 2  CH2  CH3 , CH3  CH2  CH  CH3 , CH3  C  CH3
| |
( a1 ) CH3
CH3
(a 3 )
(a 2 )
a1 R a2  CI (chain isomers)
a1 R a3  CI
a2 R a3  CI
Ex. : Find all 1º, 2º and 3º amides for C3H7NO(Only structural)

Sol. : For 1º amides
O
||
C2H5  C  NH2 (1 form) total 1º amide = 1
for 2º amide
O O
|| ||
H  C  NH  CH2CH3 CH3  C  NH  CH3 = 2 form
for 3º amide
O
CH3
H–C–N total 3º amide = 1
CH3
total amides (1º + 2º + 3º) = 1 + 2 + 1 = 4
ISOMERISM
Ex. : Find the total no. of acid and esters from C4H8O2(Only structural)
Sol. : For acid, (– COOH) C3H7 – COOH (2 form)
O
for ester, R1 – C – O – R1  alcohol part

acid part
O
||
CH3  C  O C2H5 CH3COOH + C2H5OH
O O O
|| || ||
for ester, H  C  O C3H7 (2 form) CH3  C  O C2H5 C2H5  C  OCH3
total esters = 4
Ring chain isomers :

When two or more organic compounds have same molecular formula but they differ in their structures due
to one being a cyclic compound & the other one an open chain compound, then they are called ring chain
isomers & the phenomena is called ring-chain isomerism or functional isomerisum.
Ex. : Write all isomers of C4H8 and indicate relationship between them :
C4H 8
(1) R(2)  R.C.I. (2) R(3)  R.C.I (3) R(5)  CI

(1) R(3)  P.I. (2) R(4)  C.I. (4) R(5)  RCI
(1) R(4)  R.C.I. (2) R(5)  RCI
(1) R(5)  C.I. (3) R(4)  R.C.I
Ex. : Compound CH3 – CH2 – CH2 – C  CH and show..

(A) Position isomers (B) Chain isomers
(C) Ring chain isomers (D) All of these
Sol. : C
Ex. : 1, 2–Epoxy propane and prop–2–en–1–ol (Allyl alcohol) are

(A) Position isomers (B) Functional isomers
(C) Ring chain isomers (D) Both B and C
Sol. : (D)
METAMERISM
This type of isomerism is found in those types of compounds which have polyvalent atoms or polyvalent
functional group, e.g. ether, 2º amine, ester etc.
Compound having same molecular formula but differ form the nature of alkyl group directly attached with
polyvalent atom or polyvalent functional group
ISOMERISM
CH3O CH2 CH2CH3 
metamers
CH3CH2OCH2CH3 
* (a) CH3  CH2  CH  NH  CH3 (b) CH3 – CH2 – CH2 – NH – CH2 – CH3 a & b are metamers
|
CH3
TAUTOMERISM
Compound having same molecular formula but different due to ascillation of an atom (usually H+) are known
as tautomers.
O O
|| OH
||

CH3  C  CH3  CH2  C  CH3
as after removal of H+, the anion formed is resonance stabilised.
KETO ENOL TAUTOMERISM

O OH
||  |
OH
CH3  C  CH3 CH2  C  CH3
keto enol
Ex. : C2H5 – O – C2H5 C3H7 – O – CH3
Diethyl ether Methyl propyl ether
Hydrocarbon groups – C2H5 , – C2H5 Hydrocarbon groups – C3H7, – CH3
Ex. :
Hydrocarbon groups – CH3 , –C3H7 Hydrocarbon groups

– CH3, – C2H5 , – C2H5
Ex. :
Hydrocarbon groups – C2H5 , – CH3 Hydrocarbon groups – CH3, – C2H5
O O
CH3 – C – NH – CH3 H – C – NH – CH2CH3

Ex. :
N–Methylethanamide N–Ethylmethanamide
Hydrocarbon groups – CH3, – CH3 Hydrogen groups – H, – CH2CH3
Ex. :
Groups – CH3, – CH3 Groups – H, – CH2 – CH3

ISOMERISM
O O
|| ||
Ex. : Compound CH3  CH2  C  NH  CH3 and CH3  C  NH  CH2  CH3 are
(I) (II)
(A) Functional isomers (B) Position isomers

(C) Metamers (D) All of these
Sol. : C
Ex. : Metamer of the compound P is

O
P= C–O
O
(A) (B) O–C
O
(C) O–C (D) All of these
Sol. : C
Tautomerism
Two compounds have different functional groups due to shiffting of H-atom. The two isomers remain in
dynamic equilibrium. These two can be isolated.
Tautomerism is the phenomenon in which two structural isomers differ in the relative positions of their
atoms and are spontaneously interconvertable and can exist in dynamic equilibrium. The two forms in
tautomeric equilibrium are called tautomers of each other. The interconvertibility of tautomers is a chemical
reaction which involves making and breaking of bonds.
O OH
|| |
e.g. CH3  C  CH3 CH2  C  CH3
( I) (II)
Tautomers (I) and (II) are structural isomers that are formaly related only by the shift of a hydrogen atom
and one or more pi bonds. Tautomerism, thus in a single way, can also be defined as follows type of
isomerism occuring by the migration of atom (generally acidic hydrogen from carbon to electronegative
atom and vice-versa) and the movement of a double bond is called tautomerism. Tautomers are true
isomers and either of the individual tautomeric forms may be isolated.
Structural Requirement for tautomerism

(i) Compound should have electron withdrawing groups such as – CO, – NO2 and – C  N.
(ii) Compound should have atleast one acidic hydrogen on  –carbon of the molecule.

O O CH3  C H  C  N
+
e.g.  ||  , CH3 – CH2 – N |
C H3  C  C H3 O- CH3
ISOMERISM
(iii) If compound has active methylene group than tautomerism is shown by hydrogen of this group
O O
e.g. ||  ||
CH3  C  C H2  C  CH3
Types of tautomerism
(1) Diad System
In this system the hydrogen (or the group) migrates from atom number – 1 (i.e. Carbon atom having acidic
hydrogen to electronegative atom – 2 (i.e., oxygen or nitrogen bonded with multiple bond.)
  
e.g. (i) H  C1  N
2 C  N H
 
(ii) R  C  N C  N R
Alkyl cyanide
(2) Triad System
In this system the acidic hydrogen migrates from atom number – 1 to atom number – 3
O OH
e.g. || |
CH3  C  CH3 CH 2  C  CH3
99.99 % 0.01 %
O OH
99.98 % 0.02 %
O OH
|| |
CH3  C  H CH2  C  H
99.90 % 0.10 %
The reason is that the C = O double bond of a carbonyl group is a stronger bond than the C = C of the
enol.
However, some enols are more stable than the corresponding carbonyl compounds.
Ex. : Compare the enol percent.

O O O O O
|| || || || ||
(a) CH3CHO (b) CH3 – C – CH3 (c) CH3 – C – CH2 – C – CH3 (d) CH3 – C – CH2 – C – H
O O O O O O
|| || || || || ||
(e) H  C  CH2  C  H (f) Ph – C – CH2 – C – CH3 (g) Ph – C – CH2 – C – Ph
Sol. : g > f > e > d > c > b > a
* Incase of a and b
After forming enol form
CH2 = CH – OH (no  H)
ISOMERISM
OH
|
CH2  C – CH3 (3  H) more stable = higher %
OH
O
* (enol)
(keto) (99.99%)
O OH
* + +
(keto) (aromatic) (enol)
enol > keto
O OH
*  enol % > keto %
(Aromatic)
O O O HO
* (Keto < enol due to Intramolecular H-bond)
– – –
O O O O
exist 
* CH3 – C – C – CH3 CH3 – C – C – CH3 CH3 – C – C = CH2
  as
O (stable) OH
 keto > enol
NITRO AND ACINITRO FORM
 H2O
CH2  N  O  CH2  N  OH (acinitro)

CH3NO 2  CH2 – N = O
(nitro )  
O O O
CH3 CH2NO 2 CH3  CH  N  OH NO2 OH  N  O

(nitro ) 
O
(acinitr
(nitro) (acinitro)
* (CH3)3 C – NO2 will not show nitro and acinitro form it has no  H w.r.t to NO2 group.
ISOMERISM
IMINE AND ENAMINE

CH3 – CH = N – H CH2  CH  NH
(imine)
acidic 
hydrogen CH2  CH  NH
H2O
CH2 = CH – NH2
* For this type of tautomerism, there must  H w.r.t. (–CH = NH) group.
AMIDE AND IMIDOL
O OH
|
R – C – NH2 R  C  NH
NITROSO AND OXIME FORM

Ph – CH2 – N = O Ph – CH = N – OH
(nitroso) (oxime)
(I) (II)
II > I (stability)
due to extended conjugation in (II)
HYDRAZONE AND AZOFORM

NH2 NH2 (Hydrazine)
C = O + H2N – NH2 C = N – NH2
CH3  CH  N  NH2 CH3 – CH2 – N = NH

(Azo)
CH3 – CH = N – NH – Ph CH3 – CH2N = N – Ph

(extended conjugation)
Azo > Hydrazone (stability)
Stereoisomerism
(I) The particular kind of isomers that are different from each other only in the way the atoms are oriented in
space are called stereoisomers.
(II) These isomers have same connectivity of atoms and groups.
(III) Stereoisomers have remarkably different physical, chemical and biological properties. e.g. The two
stereoisomers of butenedioic acid are maleic acid and fumaric acid. Fumaric acid is an essential metabolic
intermediate in both plants and animals, but maleic acid is toxic and irritating to tissues.
ISOMERISM
Classification of Stereoisomers :
Configurational Isomers :
(I) These isomers differ in the configuration (The spatial arrangement of atoms that characterises a particular
stereoisomer is called its configuration).
(II) Configurational isomerism arises due to noninterconvertibility at room temperature. Since they are non
interconvertible they can be separated by physical or chemical methods.
Geometrical isomerism :
Isomers which possess the same molecular and structural formula but differ in the arrangement of
atoms or groups in space due to restricted rotation are known as geometrical isomers and the phenomenon
is known as geometrical isomerism.
Conditions of geometrical isomerism :

(I) Geometrical isomerism arises due to the presence of a double bond or a ring structure
(i.e. , – N = N – or ring structure)
Due to the rigidity of double bond or the ring structure to rotate at the room temperature the molecules
exist in two or more orientations. This rigidity to rotation is described as restricted rotation / hindered
rotation / no rotation.
ISOMERISM
e.g.
(a) (Restricted Rotation)
(b) (Restricted Rotation)
(II) Different groups should be attached at each doubly bonded atom. For example
and are identical but not geometrical isomers.
On the other hand, following types of compounds can exist as geometrical isomers :
a a a a a d
C=C , C=C or C=C
b b b d b e
Examples of Geometrical isomers :
(I) Along C=C bond
CH3 Br CH3 H
C=C and C=C
H H H Br
CH3 CH3
CH3 H
C and C
H CH3
(II) Along C = N – bond
CH3 .. CH 3 OH
C=N and C=N.
.
H OH H
CH3 .. CH3 OH
C=N and C=N.
.
C2H5 OH C2H5
CH3 CH3
.. OH
N and N.
.
OH
CH3 .. CH3 NH2

C N C N.
and .
C2H5 NH2 C2H5
ISOMERISM
(III) Along – N = N – bond
.. .. .. CH3
N N and N N.
.
CH3 CH3 CH3
.. .. .. Ph
N=N and N = N ..
Ph Ph Ph
(IV) Along  bond of cycloalkane

CH3 CH3 CH3 H
and
H H H CH3
CH3 CH3 H CH3
and
H H CH3 H
CH3 CH3
H H
H3C H
and
H CH3
Me Me H Me
and
H H Me H
(V) Along C=C in ring structures :

Usually in cycloalkenes double bond has cis configuration. Their trans isomers do not exist due to large
angle strain. But if the ring is large enough a trans stereoisomer is also possible. The smallest trans
cycloalkene that is stable enough to be isolated & stored is trans-cyclooctene.
 
ISOMERISM
Configurational nomenclature in geometrical isomerism
Configuration Criteria Remarks

If the two similar groups are on same side of restricted
cis / trans Similarity of groups
bond the configuration is cis otherwise trans.
If the two senior groups are on same side of restricted
E/Z Seniority of groups bond the configuration is Z (Z = zusammen = together)
otherwise E (E = entgegen = opposite).
Sequence rules : (cahn - ingold - prelog sequence rules) (CIP)

For deciding the seniority of groups following rules are applied :
Rule I : The group with the first atom having higher atomic number is senior. According to this rule the
seniority of atoms is :
I > Br > Cl > S > F > O > N > C > H
Rule II : The higher mass isotope is senior.

Thus (a) – T > – D > – H. (b) – C14H3 > – C12 H3
Rule III : If the first atom of group is identical then second atom is observed for seniority.
e.g.
(a) – CH2Cl > – CH2OH > – CH2NH2 > – CH2CH3 > – CH3
F F
| |
(b)  C  Cl >  C  Cl
| |
OH NH2
Rule IV : Groups containing double or triple bonds are assigned seniority as if both atoms were duplicated
or triplicated that
(Y) (C)
C–Y | |
>C=Y as if it were | | & – C  Y as if it were C–Y
(Y) (C) | |
(Y) (C)
e.g. for deciding seniority among – C  CH, – CH = CH2, their hypothetical equivalents are compared.
C C C C
| | | |
 CC H > C CH
| |
C C | |
( for  C  C  H) H H
( for  CH  CH2 )
Rule V : Bond pair is senior to lone pair.

Examples :
Rule VI : Z > E & R > S.
ISOMERISM
Ex. : In which compound, Cis-trans nomenclature cannot be used

(A) CH3 – CH = CH – CH3
(B) CH3 – CH = CH – COOH
Cl CH 3
(C) C=C
Br C 2 H5
(D) C6H5 – CH = CH – CHO
Sol. : C
Ex. : Which among the following will show geometrical isomerism
CH3 CH3
H OH
(A) (B) H CH3
H D
(C) C6H5 – CH = N – OH (D) all of these
Sol. : D
Ex. : Which of the following structures will display geometrical isomerism ?

(A) CH3 CH = CCl2 (B) CH3 CCl = CBr CH3
(C) CH3CH = CHBr (D) All of these
ISOMERISM
Sol. : (B) and (C)
CH3 H H CH3 CH3 Cl CH3 Cl

C C C C
(A) C or C (B) C or C
Cl Cl Cl Cl H3C Br Br H3C
Both are identical Non – identical

H CH3 H CH3
C C
(C) C
or C
H Br Br H
Non – identical
Number of Geometrical isomers :

Number of geometrical isomers can be found by calculating the number of stereocentres in the compound.
(stereocentre is defined as an atom or bond bearing groups of such nature that an interchange of any two
group will produce a stereoisomer).
ISOMERISM
Physical Properties of Geometrical Isomers :
ISOMERISM
Optical Isomers :
Introduction and Definitions :
(I) Optical activity & plane-polarised light : Ordinary light is an electromagnetic wave, which has
oscillation in all the directions perpendicular to the path of propagation. When ordinary light is passed
through Nicol prism it has all its oscillations in the same plane and is called plane-polarised light.
Certain compounds rotate the plane of polarised light in a characteristic way when it is passed through their
solutions. These compounds are referred to as optically active compounds. The angle of rotation can be
measured by an instrument called polarimeter.
(II) dextrorotatory compounds : If the substance rotates plane-polarised light to the right i.e. in clockwise
direction it is called dextrorotatory & indicated by 'd' or (+).
(III) laevorotatory compounds : If light is rotated towards left i.e. in anticlockwise direction the substance
is said to be laevorotatory and indicated by 'l ' or (–).
Optically
active
substance
Ordinary Nicol Plane

light prism polarised
light
(IV) Specific rotation []. Specific rotation is the number of degrees of rotation observed if a
1-dm (10-cm) tube is used and the compound has concentration 1 gm/mL. Thus specific rotation [] is

[ ]t =
C
[] = Specific rotation
 = observed angle of rotation (degree)
 = Pathlength (dm)
c = concentration (gm/ml)
 = wavelength (nm)
t = temperature (25°C)
Cause of optical activity :

The foundation of modern theory of stereochemistry was laid by Louis Pasteur when he observed two
different kind of crystals, which were mirror images of each other. In aqueous solutions of both types of
crystals showed optical rotation that was equal in magnitude but opposite in direction. Pasteur believed
that this difference in optical activity was associated with the three dimensional arrangement of atoms in the
two types of crystals.
Later van't Hoff and LeBel proposed that all the four valencies of carbon are directed towards the four
corners of regular tetrahedron, and if all the four substituent attached to such a carbon are different the
resulting molecule lack symmetry and such a molecule is referred to as asymmetric molecule and asymmetry
of the molecule is responsible for optical activity in such organic compounds.
ISOMERISM
Element of symmetry and concept of molecular dissymmetry/asymmetry and chirality.
(I) Plane of symmetry :
It is an imaginary plane which bisects the molecule in two equal halves in such a way that each half of the
molecule is the mirror image of the other half.
(II) Centre of symmetry :

The centre of symmetry is defined as the point in a molecule through which if a straight line is drawn from
any part of the molecule this line encounters identical groups at equal distances in opposite direction.
(III) Asymmetric and dissymmetric compounds :

A molecule which does not possess any element of symmetry (there are all 23 elements of symmetry) is
called asymmetric. A molecule which does not possess plane of symmetry and centre of symmetry is called
dissymmetric.
(IV) Condition for optical activity :

The minimum condition for a compound to show optical activity is molecular dissymmetry i.e. absence of
plane of symmetry and centre of symmetry.
(V) Chirality :
A compound which is non-superimposable to its mirror image is called chiral while a compound which is
superimposable to its mirror image is called achiral. All dissymmetric (or asymmetric) compounds are
chiral & vice-versa.
(VI) Chiral centre :

A compound in which a carbon is atttached with four different groups lacks symmetry and is called chiral
carbon or asymmetric carbon. It is represented by C*. e.g.
(a) CH 3  CH  CH3 (2-chloropropane) :
|
Cl
I has no chiral centre since two groups (a & b) are identical. Its is superimposable on its mirror image
II ( III).
ISOMERISM
*
CH3  C H  C 2H5
(b) (2-chlorobutane) :
|
Cl
I has one chiral centre it is asymmetric & it is not superimposable to its mirror image II ( III).
The necessary condition for chirality is not just the presence of asymmetric carbon atoms but the asymmetry
of the molecule as a whole.
Ex. : Which of the following compounds has chiral carbon ?

(A) CH3 – CH = CH – CH3 (B) CH3 – CHOH – CH2 – CH3
CH3
(C) C = N – OH (D) All of these
H
Sol. : The starred carbon is chiral carbon because all the four substituents are different
CH3 – C* HOH – CH2 – CH3
Ex. : Mark the asymmetric carbon atoms in the following compounds

(A) CH3 – (CHOH)2 – COOH (B) HOCH2 – (CHOH)4 – CHO
H H H H H H H H H
| | | | | | | |
Ans. : (A) CH3  C *  C *  COOH (B) HO  C  C*  C*  C*  C*  C*  O
| | | | | | |
OH OH H OH OH OH OH
Projection formula in optical isomerism :

(I) Wedge-dash projection formula :
It is a convenient way of depicting three dimensional structure in two dimension. In this projection four
bonds of a tetrahedral molecule is shown by two lines (in the plane) one wedge (up the plane) one dash
(down the plane)
(II) Fischer projection formula :

It is also a convenient way of depicting three dimensional structure in two dimension.
Rules for writing Fischer projection formula :
(i) The molecule is drawn in the form of cross (+) with the chiral carbon at the intersection of horizontal &
vertical lines.
(ii) On vertical line, main chain is taken with first carbon at the top.
(iii) The horizontal lines represent the bonds directed towards the viewer and vertical lines away from the
viewer e.g.
ISOMERISM
*
CH2  C H  CHO
(a) | | (glyceraldehyde)
OH OH
can be represented in two different Fischer projection as
* H  COOH (Alanine)
(b) CH3  C
|
NH2
can be represented in two different Fisher projections as
Ex. : Draw the wedge–dash projection formula of

CF3 NHMe
(A) Cl H (B) Me OH
CH3 Ph
CF3 NHMe
Sol. : C H (B) C OH
Cl CH3 Me Ph
Configurational nomenclature in optical isomers :

Relative configuration : the experimentally determined relationship between the configurations of two
molecules, even though we may not know the absolute configuration of either. Relative configuration is
expressed by D-L system.
Absolute configuration : The detailed stereochemical picture of a molecule, including how the atoms are
arranged in space. Alternatively the (R) or (S) configuration at each chirality centre.
(I) D - L System (Relative configuration) :
This method is used to relate the configuration of sugars and amino acids by the help of enantiomers of
glyceraldehyde. The configuration of (+)-glyceraldenyde has been assigned as D and the compounds with the
same relative configuration are also assigned as D, & those with (-) glyceraldehyde are assigned as L.
ISOMERISM
Examples :
Sugars have several asymmetric carbons. A sugar whose highest numbered chiral centre (the penultimase
carbon) has the same configuration as D-(+)-glyceraldehyde (– OH group on right side) is designated as
a D-sugar, one whose highest numbered chiral centre has the same configuration as L-glyceraldehyde is
designated as an L-sugar.
e.g.
(II) R and S configurations in Fischer projection : (absolute configuration)

Rule I : The priorities of groups which are attached with the asymmetric C-atom are assigned by sequence
rule.
Rule II : The lowest priority group is brought to the bottom of Fischer projection by two or even simultaneous
exchanges.
Rule III : Then an arrow is drawn from first priority group to second priority group to third priority group.
If the arrow is clockwise the configuration assigned to the projection is R & If it is anticlockwise the
configuration assigned is S.
Ex. : (i) (ii) 
ISOMERISM
(iii) 
(iv) 
Ex. : Assign Ror S configuration to each of the following compounds
CHO Cl OH
(A) H C OH (B) Br C COOH (C) H5C2 C H
CH2OH H CH3
Sol. : (A) R (B) R (C) R
Enantiomers :
Stereoisomers which are non-superimposable mirror images of each other are called enantiomers.
e.g. in all the following molecules there is no centre of symmetry or plane of symmetry. Therefore their two
mirror image isomers are non-superimposable and hence enantiomers.
Ex. : 2-Chlorobutane :
Ex. : Chloroiodomethanesulfonic acid : I I
SO3 H SO3 H
Enantiomers
Ex. : Lactic acid :
ISOMERISM
Ex. : Alanine :
Ex. :
RACEMIC MIXTURE
It is an equimolar mixture of R and S or d and l.Racemic mixture is optically inactive

A compound is optically active due to
(1) Absence of plane of symmetry (POS) (2) Absence of centre of symmetry (COS)
COOH
H OH
POS
H OH
COOH
(meso form )

POS is an imaginary plane where if we place a mirror, mirror image will exactly overlap the other half.

For meso form, there must be at least two identical chiral carbon.
Identical carbon Chiral carbons having identical group attached.

If compound has POS then it will be certainly optically inactive and will be called meso form.

After finding two identical carbons. We assign them as R or S. If first part is R and other is S then they will
rotate the light in opposite direction but to equal extent the compound will be optically inactive
(meso form)
COOH COOH
H OH HO H
H COOH HOOC H
OH OH
Enantiomers
ISOMERISM
 If a compound have 'n' different chiral carbon then total no. of optically active isomers = 2n
No. of meso form = 0
COOH
H Br
H Br
H Br
e.g.
H Br
OH
no. of different chiral carbon = 4
total optical isomer = 2n = 24 = 16
 There will be no meso as the compound does not have identical chiral carbon.
 If a compound has n identical chiral centre (symmetrical)  There must be symmetry from some where.
(i) If n is even
optical isomer (a) = 2n–1
mesoform (m) = 2n/2–1
total optical isomer = a + m
(ii) If n is odd
n1
n1
a= 2 2 2
n 1
m= 2 2
n1 n 1
n1
Total optical isomer = 2 2 2 2 2
= 2n1
OH
Pseudo Chiral
H Br
H Br POS
 H Br
OH

When there is odd no. of identical carbon atom (i.e. symmetrical) then this compound will certainly
contain pseudo chiral w.r.t. to which compound be symmetrical (i.e. POS)

Other meso compound of the above compound will form by changing the place Br and H around
Pseudo Chiral carbon.
OH
H Br
Br H POS
H Br
OH
Total meso = 2
ISOMERISM
n 1
optical = 2n 1  2 2
3 1
= 23 1  2 2
= 22 – 2
=4–2=2
OH OH
H Br Br H
H Br Br H
Br H H Br
OH OH
Enantiomers

CHO
H OH
H OH
H OH
H OH
CH2OH
(Glucose)
Total no. of different chiral carbon = 4
Total optical isomer = 24 = 16

CHO
H OH
H OH
POS
H OH
H OH
CHO
Total no. of even chiral = 4

a = 2n1 = 241 = 23 = 8
n 4
1 1
m = 2 2 = 2 2 = 22-1 = 21 = 2
Total isomer = 8 + 2 = 10
ISOMERISM
Diastereo Isomers

For single chiral centre, there is no diastereoisomer. The stereoisomer which are not related as
object and mirror image. They may be optically active or optically inactive.
COOH COOH
H OH H OH
H OH OH H
COOH COOH
(Inactive) (active)
Diastereo isomer
COOH COOH
H OH OH H
H OH H OH
fix
COOC2H5 COOC2H5
(active) (active)
Diastereo isomer

Fix one chiral carbon
After one inter change
If (R, R)  (R, S)
For compound having 3 chiral carbon to get diastereoisomer, fix two chiral carbon and one interchange
with left carbon or fix one chiral carbon and inter change with other two,
OH OH
H Br Br H
H Br Br H
H Br Br H
COOH COOH
(I) (II)
Total isomer = 23 = 8
OH OH
Br H H Br
H Br Br H
H Br Br H
COOH COOH
(III) (IV)
ISOMERISM
(I) and (III), I and (IV), (II) and (III), (II) and (IV) are diastereoisomers.
COOH COOC2H5 OH O OH
R R S R
H OH H OH H COOH C2H5O–C H
R R R
Ex. : HO H HO H HO H HO COOH
S
COOC2H5 COOH COOC2H5 H
(I) (II) (III) (IV)
What are the relation among the above compounds?
Sol. I and II are identical III and IV are identical
II and III are diastereo isomer I and IV are diastereo isomer
Optical activity without asymmetric carbon :
(I) Case of allene :
(a) Allenes with even  bonds : e.g.
the orbital diagram of this structure will be
Since the groups at the end of allene are in perpendicular plane, it will not show geometrical isomerism. The
molecule lacks centre of symmetry as well as plane of symmetry. Overall the structure has molecular
dissymmetry which is the sufficient condition for optical activity. The molecule will exist in two enantiomeric
forms.
(b) Allenes with odd  bonds : e.g.
the orbital diagram of this structure will be -
The groups at the end of allene structure lie in same plane (ZX plane). Therefore it will have a plane of
symmetry (ZX plane). The molecules lacks molecular dissymmetry & it will not show optical activity hence
optical isomerism. But the compound will exist in two geometrical diastereomeric forms.
ISOMERISM
(II) Case of spiranes : A similar case like allenes is observed in spiranes. The spiranes with even rings
and different groups at terminal carbons show optical activity & optical isomerism, while the spiranes with
odd rings shows geometrical isomerism.
(a) spiranes with even rings :
shows optical isomerism.
(b) spiranes with odd rings :
shows geometrical isomerism.
(III) Case of cycloalkylidene :
(IV) Case of ortho-ortho-tetrasubstituted biphenyls :
becomes non-planar at room temperature in order to have minimum electronic

repulsion among the substituent. In this orientation (phenyl planes perpendicular to each other) the free
rotation of C – C single bond is restricted and molecule shows optical activity due to molecular disymmetry. e.g.
Compounds having chiral centres other than carbon :

The tetrahedral atom with four different groups attached to it is a stereocentre (chiral centres). Thus when
atom like nitrogen, phosphorous, sulphur, silicon, germanium has four different groups attached with them
they are chiral and show optical activity & hence optical isomerism. e.g.
ISOMERISM
Asymmetric nitrogen : Amine inversion
Amines with all different groups attached to N-atom have chiral centres (R1R2R3 ) as nitrogen atom.
Since the geometry of the molecule is tetrahedral it has molecular dissymmetry. It will exist as two enantiomers
but the two enantiomers of amines cannot be separated because they rapidly interconvert to each other.
Therefore they always exist as racemic mixture.
..
e.g. Ethylmethyl amines CH3 NHC 2H5 .
Interconvertible ethylmethylamine enantiomers (non resolvable)
Conformational isomerism
Free rotation : For defining free rotation let us consider the bonding in ethane.
We find that the -bond joining the carbon atoms is cylinderically symmetrical about the line joining the two
carbon nuclei ; if the energy does not differ much in different arrangements the molecule can rotate about
this carbon-carbon  bond, we describe this freedom to change by saying that there is free rotation about
the carbon-carbon single bond.
Conformations :
Different arrangements of atoms that can be converted into one another by rotation about single bonds are
called conformations.
Conformational isomers : There are infinite arrangement (conformations) which arise due free rotation around
carbon-carbon  bond, different conformations corresponding to energy minima are called conformational
isomers. The conformational isomerism arises due to free rotation along a bond.
Newman projection : For conformational analysis, a special type of structural formula is convenient to use which
is called newman projection formula and another type is a sawhorse formula.
To write newman projection formula we imagine ourselves taking a view from one carbon atom directly
along the selected bond axis to the next atom. The front carbon and its other bonds are represented as
and those of the back carbon as
ISOMERISM
Dihedral angle :
The angle between C – X and C – Y in X – C – C – Y when it is visualised along C – C bond.
Staggered, eclipsed and skew conformations :

(I) The staggered conformation of a molecule is that conformation where the dihedral angle between the
bonds at each atom of carbon-carbon bond is 180°.
(II) In then eclipsed conformation the atoms bonded to carbons at each end of carbon-carbon bond are
directly opposite to one another. The dihedral angle between them is 0°.
e.g.
(III) Skew conformation : All conformations other than staggered or eclipsed are skew conformations.
Factors affecting stability of conformations :

(I) Angle strain : Any atom tends to have bond angles that match those of its bonding orbitals. For
example 109°.28 for sp3-hybridized carbon. Any deviation from "normal" bond angles are accompanied
by angle strain.
(II) Torsional strain : Any pair of tetrahedral carbons attached to each other tend to have their bonds
staggered for minimum repulsion between their bonds. Any deviation from the staggered conformation are
accompanied by torsional strain.
(III) van der Waals strain : Non bonded atoms or groups that just touch each other i.e. they are about
as far apart as the sum of their van der Waals raddii, attract each other. If brought any closer together they
repel each other. Such crowding together is accompanied by van der Waals strain.
Conformational analysis of ethane :

Ethane molecule contains a carbon-carbon  bond and each carbon is further attached to 3 H-atoms. It
exists in two extreme conformations i.e.
(i) eclipsed conformation
(ii) staggered conformation
The potential energy barrier between the two conformations of ethane is about 12.5 kJ/mol.
The potential energy of ethane molecule is at a minimum for the staggered conformation, increase with
rotation and reaches a maximum at the eclipsed conformation most ethane molecules,
naturally exist in the most stable. staggered conformation. There are only three energy minima, that is
ethane has only three conformers. Since they are indistinguishable they are degenerate.
ISOMERISM
Energy profile of Eclipsed and Staggered forms of ethane
Conformational analysis of butane :

If we consider rotation about the C2 - C3 bond of butane, we find that there are six important conformations
shown as I - VI below :
Energy profile of conforminations of butane :
ISOMERISM
Strains and stability in n-butane
Conformation dihedral Torsional
vander Waal strain Stability
of n-butane angle () strain
I : Anti 180° Absent Absent Maximum
Present (between
II : Partially eclipsed 120° Maximum
– CH3 & – H grps)
Intermediate - 1
Present (between Intermediate - 2

III : Gauche 60° Absent
two – CH3 grps) (> Intermediate1)
Maximum (between
IV : Fully eclipsed 0° Maximum
two – CH3 grps)
Minimum
The stability order will be :

Anti > Gauche > Partially eclipsed > Fully eclipsed.
n-Butane exists as three conformational isomers one anti (I) and two gauche (III & V). The gauche
conformers III and V are mirror images of each other and hence are (conformation) enantiomers. Gauche
conformations (III & V) and anti conformation (I) are not mirror images of each other and hence are
conformational diastereomer n-butane spends the greater part of its time as the anti conformer, and divides
the smaller part equally between the two gauche conformers. As a result of the rapid inter conversion these
isomers can't be separated.
Case of intramolecular hydrogen bonding :

In case of G – CH2 – CH2 – OH, where G = – OH, – NH2 , – F, – NR2, – NO2, – COOH, – CHO the
Gauche form is more stable than the anti form due to intramolecular hydrogen bonding i.e.
stability : Gauche form > anti form.
Ex. : has :
(A) plane of symmetry.

(B) centre of symmetry.
(C) C3 axis of symmetry.
(D) C4 axis of symmetry.
ISOMERISM
Sol. : Centre of symmetry
COS found.
Ex. : How many optically active cycloalkanone are possible with molecular formula C5H8O.
Sol. : 6
Ex. : and
is / are :
(A) Geometrical isomer (B) Diastereomers

(C) Configurational isomer (D) Enantiomers
Sol. : and
are geometrical isomers and they are not mirror image of each other, so they are also known as diastereomers
and they are interconvertable into each other.

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ISOMERISM

Isomers Characteristics Conditions

The two functional isomers

Ex. : (A) CH3 – CH2CH2 – CH3

Ex. : Find all 1º, 2º and 3º amides for C3H7NO(Only structural)

for ester, R1 – C – O – R1  alcohol part

Ring chain isomers :

(1) R(2)  R.C.I. (2) R(3)  R.C.I (3) R(5)  CI

Ex. : Compound CH3 – CH2 – CH2 – C  CH and show..

Ex. : 1, 2–Epoxy propane and prop–2–en–1–ol (Allyl alcohol) are

KETO ENOL TAUTOMERISM

Hydrocarbon groups – CH3 , –C3H7 Hydrocarbon groups

Hydrocarbon groups – C2H5 , – CH3 Hydrocarbon groups – CH3, – C2H5

CH3 – C – NH – CH3 H – C – NH – CH2CH3

Groups – CH3, – CH3 Groups – H, – CH2 – CH3

(A) Functional isomers (B) Position isomers

Ex. : Metamer of the compound P is

Structural Requirement for tautomerism

Ex. : Compare the enol percent.

*  enol % > keto %

* (Keto < enol due to Intramolecular H-bond)

NITRO AND ACINITRO FORM

CH3 CH2NO 2 CH3  CH  N  OH NO2 OH  N  O

AMIDE AND IMIDOL

NITROSO AND OXIME FORM

HYDRAZONE AND AZOFORM

C = O + H2N – NH2 C = N – NH2

CH3  CH  N  NH2 CH3 – CH2 – N = NH

CH3 – CH = N – NH – Ph CH3 – CH2N = N – Ph

Conditions of geometrical isomerism :

(a) (Restricted Rotation)

(b) (Restricted Rotation)

and are identical but not geometrical isomers.

Examples of Geometrical isomers :

(I) Along C=C bond

(II) Along C = N – bond

CH3 .. CH3 NH2

(IV) Along  bond of cycloalkane

CH3 CH3 H CH3

(V) Along C=C in ring structures :

Configuration Criteria Remarks

Sequence rules : (cahn - ingold - prelog sequence rules) (CIP)

Rule II : The higher mass isotope is senior.

Rule V : Bond pair is senior to lone pair.

Ex. : In which compound, Cis-trans nomenclature cannot be used

Ex. : Which of the following structures will display geometrical isomerism ?

CH3 H H CH3 CH3 Cl CH3 Cl

Both are identical Non – identical

Number of Geometrical isomers :

Ordinary Nicol Plane

Cause of optical activity :

(II) Centre of symmetry :

(III) Asymmetric and dissymmetric compounds :

(IV) Condition for optical activity :

(VI) Chiral centre :

Ex. : Which of the following compounds has chiral carbon ?

CH3 – C* HOH – CH2 – CH3

Ex. : Mark the asymmetric carbon atoms in the following compounds