IIT JEE

Organic
Chemistry

Structural and
Stereo Isomerism

1.

 Degree of Unsaturation (DU) / Double Bond
Equivalent (DBE) / Index of H-deficiency (IHD)

Introduction :
The main objective of an organic chemist is the determination of the
structure of a new organic compound which has been obtained in pure
state either from a natural source or synthesised in the laboratory.
In order to establish the correct structure of an organic compound, it
is necessary to detect skeleton of compound, elements and functional
groups present in the organic compound.

y Deficiency of hydrogen generates unsaturation in the compound to

compute this unsaturation is called DU.
y How many bond cleavage give open chain saturated compound is DU of
that compound.
y Open chain saturated compound having DU = 0.
y In compound unsaturation is observed in the form of p-bonds & rings.
DU = 1 → Ring’ or Double bond’
DU = 2 → ‘=’ bond + ‘=’ bond
→ ‘≡’ bond
→ ‘=’ bond + ring
→ Ring + Ring

Case-I :
If molecular formula is given.
H + X − N
DU = (C + 1) −  
 2
(Where C = carbon, H = hydrogen, N = nitrogen)

(i) C4H8
8
( 4 + 1) − = 5 – 1 ⇒ DU = 1
2
(ii) C4H6
6
( 4 + 1) − =5–3=2
2
(iii) C6H6
6
( 6 + 1) − =7–3=4
2

2.

(iv) C6H6O
6
( 6 + 1) − =7–3=4
2

(v) C8H8
8
( 8 + 1) − =9–4=5
2

(vi) C8H8O
8
( 8 + 1) − =9–4=5
2

(vii) C8H4BrFClI

4 + 4
(8 + 1) −   =9–4=5
 2 

(xii) C5H9N
9 − 1
(5 + 1) −   = 6 – 4 =2
 2 

(xiii) C3H9N
9 − 1
( 3 + 1) −   =4–4=0
 2 

(xiv) C8H3BrFNO

3 + 2 − 1
(8 + 1) −   =9–2=7
 2 

Case-II :
If molecular structure is given :
DU = Number of π -bond + number of rings

(i) Toulene (4)

(ii) o-xylene (4)

3.

 (iii) p-xylene (4)

(iv) o-cresol (4)

(v) Resorcinol (4)

NH2

(vi) p-toluidine (4)

CH3

(vii) o-salicyaldehyde (5)

(viii) Anisol (4)

(ix) Aspirin (6)

4.

(x) Piperidine (1)

(xi) Tropolone (5)

(xii) Azulene (7)

(xiii) Acetone (1)

(xiv) Benzo phenone (9)

(xv) Mestiylene (4)

(xvi) Triphenyl methane (12)

(xvii) (8)

(xviii) (7)

5.

 Case-III :
If molecular structure is given in 3-D
DU = number of faces – number of box

C8H8
(i) DU = 6 − 1 = 5

C12H8
(ii) DU = 11 − 2 = 9

C6H6
(iii) DU = 5 − 1 = 4

(iv) 2

(v) 3

Note :
In case of salt DU is fractional.

6.

 Introduction of Isomerism and
Structural Isomers

Iso → same

mers → unit

* Two or more different compounds having same molecular formula are

known as isomers.
CH 3CH2OH
 & CH3OCH3

Example : C2H6O Isomers

Characteristic of isomers :
y They have same molecular formula.
y They have same molecular weight.
y They have same emperical formula.
y Emperical formula : Formula in simplest ratio or in condense form.
Eg. MF ⇒ EF
C6H6 ⇒ CH
C6H12O6 ⇒ CH2O

y They have same emperical weight

y They have same vapour density
2 × vapour density = Molecular weight
y They have same DU.
y Atleast one physical or chemical property must be different.

Structural Isomers :
Two or more different compound having same molecular formula but have
difference in connectivity of atoms or groups.

7.

 Stereoisomers :
Two or more different compound having same molecular formula as well as
structural formula but have difference in orientation of atoms & groups in
space or 3-D.

Eg.

(A, B) ⇒ Structural, (A, C) ⇒ Structural, (B, C) ⇒ Stereoisomers

Boiling point µ Dipole moment

Dipole moment of B ⇒ µ ≠ 0
Dipole moment of C ⇒ µ =0
Dipole moment and boiling point are physical property. So here B & C have
different physical properties.

Structural Isomers
(1) Chain Isomers:
Two or more different compound having same molecular formula but
different in parent carbon chain or side chain.
Eg.

(i) Chain isomers

(ii) Chain isomers

(iii) Chain isomers

(iv) CH3 − CH2 − CH2 − CN Chain isomers
C

(v) C–C–C–CC C C CC C C Chain isomers

C C

(vi) Chain isomers

* Chain isomers must have same functional group.

8.

 (2) Positional Isomers :
* Two or more different compound having same molecular formulae but
difference in position of substituent, multiple bond & functional group are
known as positional isomers.
* For positional isomers, parent carbon chain must be same.
* For positional isomers, functional group remain same.

Examples (Solved)
(i) Positional isomers 

(ii) Chain isomers 

They are chain isomers because
PCC is not same
(iii) Positional isomers 

(iv) Positional isomers 

(v) Positional isomers 

(vi) Positional isomers 

(3) Functional Isomers :

* Two or more different compound having same molecular formula but
different functional groups.

Examples (Solved) :
y Alcohol – ether
Eg. CH3 − CH2 − OH & CH3 − O − CH3
y Aldehyde – ketone

9.

 y Alkyne – diene
Eg. CH ≡ C – CH3 CH2 = C = CH2

y 1°, 2°, 3° amine are different functional group.

Eg. CH3 – CH2 – CH2 –CH2 – NH2, CH3 – CH2 – NH– CH2 – CH3, CH3 – N – CH2 – CH3

CH3

y Nitrile & isonitrile

Eg. CH3 – C ≡ N or CH3 − N ≡ C

y 1°, 2°, 3° amide are different functional group

O O O
CH3
Eg. H C CH CH2 C NH2 ,  H3C CH2 C NH CH3  H3C C N
3 2
1° 2° CH3
3°

10.

 Structural Isomerism

Ring chain isomers :

Two or more different compound having same molecular formula but one is
chain & another one is close chain with same DU.

Examples :

(1) Ring chain isomers or functional isomers

(2) Ring chain isomers or functional isomers

(3) Find relations in (a & b), (a & d), (a & f), (b & c), (b & e), (b & g), (c & e),
(c & g), (d & f) and (e & g) :

(a) (b) 

(c) (d)

 

(e) (f)
 

(g)

Ans.
(a) & (b) - chain isomer
(a) & (d) - ring chain
(a) & (f) - ring chain & functional isomer
(b) & (c) -ring chain & functional isomer
(b) & (e) - ring chain
(b) & (g) - ring chain
(c) & (e) - functional isomer
(c) & (g) - functional isomer
(d) & (f) - functional isomer
(e) & (g) - chain isomer

11.

 Metamerism :
y If alkyl or aryl group changes around polyvalent functional group then these
isomers are known as metamers.
Monovalent functional groups :
1. –OH 2.  –NH2 3. 

4.
5. 
6. 

7.

Polyvalent functional groups :

Those group which have more than one free valency are known as polyvalent
functional groups.
1. – O – 2.  – S – 3. 

4. 5.  6.  – NH –

7. 8. 

Examples (Solved) :
Find relation between given isomers :
(i) Metamers

(ii) Identical

(iii) Positional isomers

(iv) Metamers

(v) Metamers

12.

 (vi) Metamers

* Functional group remain same for metamerism.

Tautomerism :
y Protonotropy / cationotropy / desmotropism / keto enol tautomerism
y Those functional isomers which are present in dynamic equilibrium are called
tautomers. This process is known as Tautomerism.
y As in tautomerism, proton migrates, therefore it is also known as protonotropy.
y In tautomerism bonds also migrate, therefore it is also known as desmotropism.
y For tautomerism atleast one a-hydrogen is required.

Examples :

(i)

(ii) Tautomers & functional isomers

(iii) Functional isomer only

Priority order :
R>C>T>F>M>C>P
Radio city top FM near Carrer point

Examples (Solved) :
Among the following compounds how many will show tautomerism ?

(a) Yes (b) No

 

13.

 (c) Yes (d) No

 
(e) 2-pentanone Yes (f)  Acetone Yes

(g) Yes

Examples (Solved) :
Define relation between the following:
1. Chain isomers

2. Different compound
3. Different compound

4. Functional isomer
5. Identical

6. Identical

7. Positional isomer

8. Positional isomer

9. Chain isomers

10. Functional isomer

14.

11. Chain isomers

12. Functional isomer

13. Functional isomer

14. Identical

15. Functional isomer

16. Metamers & positional isomer

17. Functional isomer

18. Chain isomer

O
19. CH3 – CH2 – N
O
CH3 – CH2 – O – N = O Functional isomer

20.

Metamers

15.

 Projection Formulas in Organic Chemistry

1. Wedge-Dash formula :
The configuration of organic molecules can be visualised by three-
dimensional (3D) structures, which may be depicted by any of the following
representations :

(I)

The thick solid (solid wedge) line indicates the bonds lying above the plane of
paper (projecting towards the viewer).
Thin lines indicate the bonds lying within the plane of paper.
The dotted lines indicate the bonds lying below the plane of paper. Such a
representation is called Wedge-Dash formula.

2. Fischer projection formula :

The horizontal lines represent the bonds directed towards the viewer and the
vertical lines away from the viewer. For example, (–CHO) group in glyceraldehyde,
(–COOH) group in lactic acid etc. The C atoms are then numbered according to
the IUPAC nomenclature.

16.

Interconversion of Wedge-Dash Formula to Fischer Formula :
For example,

(i)

(ii)

(iii)

(iv)

Interconversion of Fischer Formula to Wedge-Dash Formula :

Interconversion of fischer formula Wedge–Dash formula :

CHO CHO
HO H HO
H2C OH H CH2 OH
Fischer formula Wedge – Dash formula

17.

 The following rules must be observed :
(i) A fischer projection should not taken out of the plane of paper and turned
over. It would lead to the Fischer projection of the enantiomer, since it
changes the configuration at the chiral centre.
a a
Forbidden
d c turnover
c d
b b
Enantiomer

(ii) Even number of interchanges clockwise or anti-clockwise leads to

the same stereoisomer, while odd umber of interchanges results in an
enantiomer.
CHO CHO CHO
HO H HO CH2OH H CH2OH
One Second
interchange interchange
H2C OH H OH
(I) (II) (III)

(I) and (III) are equivalent Fischer projections.

(iii) Rotation of Fischer projection by 180º on the plane of paper results in the
equivalent Fischer projection.
CHO CH2OH
Rotate by 180°
HO H H OH
one the plane
of paper
H2C OH CHO
(I) (II)

(I) and (II) are equivalent Fischer projections.

Sawhorse and Newman Projection Formulae

Sawhorse projection formula :

(i) (ii) 

(iii) (iv) 

18.

 Newman Projection Formula :
These projection formulae are obtained by viewing the molecule along the
bond joining two carbon atoms.

a a
f d
f d

b c b c
Fron C atom e
e Rear
(back C atom)

Newman Projection :
y Front carbon as dot (.)
y Back carbon as circle ‘O’
Most of compound could be represented in newman projection formula if
particular atoms about which projection has to made is mentioned.

Examples :

(A)

(B)

(C)

19.

 Conversion of Sawhorse and Newman Projection formulae in Fischer and Vice
Versa :
CH3 COOH
H OH COOH
H OH
CH3 HO HO
CH3 H H
(i) HO H
COOH
HO
180°
180° CH3
rotation about
COOH HO H C–C bond
rotation about
(Newman) HO H C–C bond
H
(Sawhorse)
(2OH; same side)

CH3 COOH
HO H COOH
HO H
CH3 H H
OH
(ii) COOH CH3
H
OH
HO H 180°
180° OH
rotation about
COOH HO H C–C bond
rotation about
(Newman) HO H C–C bond
CH3
(Sawhorse)

COOH COOH
H OH
HO H
(iii) H
HO H OH
COOH
COOH
(Newman)
(Sawhorse)

Draw Fischer projection formulae for the following molecules :

CHO
H
H3C H
(a) CH2OH (b) 
HOH 2C
OH
H3CH2C
COOH
H CH3
(c) H3C H (d) 
HO C C OH
NH2 OHC CH2OH
Solution :
CH2OH CHO

(a) H CH3 (b) 

HO H

CH2CH3 CH2OH
CHO

COOH HO H

(c) H2N H (d) 

H3C OH
CH2OH
CH3

20.

Convert wedge formula to Fischer formula :
CHO
H3C COOH H
(a) (b)
H2N H CH2OH
HO
Solution :
COOH CHO

(a) H2N H (b) H OH

CH3 CH2OH
Convert Fischer formula to wedge formula :
COOH Br
(a) H OH (b) H C
3 CHO
C2H5 H
Solution :
COOH Br Br
Vertical Vertical
H line CHO line
(or) H3C
HO C2H5 H CH3 OHC H
(1) (2)

Convert Sawhorse formula to Fischer formula :

Br COOH

Me H
Me H Me Me
(a) H (b) H

COOH Br

Solution :
Br Rotate by
180°
H Me Br COOH
Me Me
Me H H Me Rotate the molecule to 180° H Me
H H Br
(a) Me H on the plane of paper to keep
the (–COOH) group on the top
Me H
COOH COOH
COOH Br
(Fischer projection)

HOOC Rotate by
180° Me H COOH
H Me Me H
Me Me
H H COOH
Me H
(b) Br Br
Br
(Fischer projection)

21.

 Conformer and Conformation

Conformer :
y Isomers formed by rotation across s bond are called conformers.
y There are ∞ conformers across given s bond.
y Energy needed for C-C bond rotation is 3 Kcal per mole in ethane.
y Conformers are freely interconvertable into each other and not seperable, they
are not true isomers.
y Conformers are present in dynamic equilibrium.
y During conformational isomerism bond angle, bond length and configuration
of molecule are not changed.
Q. Which of the following show conformational isomerism :
H H
O
C C H O
(1) H H (2)  H H (3)  H H
H
H H H H H
O O
(4) H H (5)  C C H (6) 
H C C C H
H H
H H H H

Bond Angle (q):

It is an angle between two valency of same atom.
H

Example: Methane molecule (CH4) C has bond angle between 2 C-H

H
H
H
bonds is 109°28 ' .

Dihedral angle (f) :

y The angle between two valency at different atom obtained in sigma bond
rotation, is called dihedral ring.
y Dihedral angle is not fixed, it keep on changing at room temperature, that’s
why it is called rotational angle of conformer during conformation.

∠F − C − C − I= 180°
∠F − C − C − Cl = 60°

22.

Eclipsed form :
When value of f = 0°, 120°, 240°, 360° then, that form is known as eclipsed
form in eclipsed form, valencies of one central atom completely overlapped by
valencies of adjacent atoms.

Staggered form :
When value of φ= 60°, 180°, 300° then that form is known as staggered form.
In staggered form, two biggest sized valencies attached at central atom must
be opposite to each other.

23.

 Skew form :

Infinite forms which are present in between eclipsed & staggered are known
as skew forms.
0° < φ < 60°

Analysis of conformation :

y Interelectronic Repulsion EC > ST

y Interelectronic Distance ST > EC
y Stability ST > EC
y Energy EC > ST
y Mole Fraction ST > EC

Major factors to be considered when dealing with conformational isomerism :

Torsional energy (strain) :

y Bond Pair-Bond Pair electronic repulsion.
y It is only considered in eclipsed conformer.
Vanderwaal strain :
y Steric strain or strain due to their size is Van der Waals repulsion.
y It is maximum in eclipsed conformer.
Rotation Barrier :
y Energy difference between most stable conformer & least stable conformer is
known as rotation barrier.

24.

Examples : Draw most stable structure.
1. Propane
Sol.
6.

Sol. (H-bonding) Gauche > Anti

7. 2-methyl pentane (C2 − C3 )

2. n-hexane (C2 − C3 )
Sol.
Sol.

3. 2-3 dimethyl butane (C2 − C3 )

Sol.

8.

C
H H
H
4.
Sol.

Sol. Stability: Gauche > Anti

5. 3-hydroxy propane (C2 − C3 )

Sol.

25.

 9.

Sol.

Case-(b)
High pH ⇒ Solution (Basic)

Gauche > Anti COOH → H⊕ ↑→ COOΘ

10.

Sol.
(a) Low pH (most stable)
(b) High pH (stable)
Case-(a)
Low pH ⇒ Solution (Acidic)

Q. Among the given compound/s which having zero dipole moment in any of
coformation ?
OH

(A) (B) 

HO

(C) (D)  None of these

Sol.
H H
O O

(A)

µ =0 µ≠0
O O
H H

26.

(B)

(C) Always same µ =0 ∴ Only (C)

27.

 Conformational Analysis in Cyclic Compound

Baeyer Angle Strain Theory :

According to Baeyer cyclic compounds are less stable then corresponding
open chain compunds because in cyclic compound angle strain is present.

1
Angle strain ∝ ∝ Re activity
Stabilbity

Stability order of ring (cycloalkane)

6 > 5 7 > 4 > 3

COMPOUND EXPECTED B.A. REAL B.A. ANGLE STRAINS

109°28° 60° 49°28°

109°28° 90° 19°28°

109°28° 108° 1°28°

109°28° 109° ≈0

Cyclopropane :
y Present in forced eclipsed confirmation.
y Highly reactive due to its high angle strain.
y Highly reactive, therefore gives test of unsaturation.

28.

 Cyclobutane :

It undergo jelly flipping.

Cyclopentane :

Envelop flipping

Cyclohexane :
y In real sense, cyclohexane is non-planar structure with negligible angle strain
so that it is less reactive in nature & highly stable in nature.
y It’s negligible angle strain also releases by various confirmation.

Conformer of cyclohexane :

a || b
1. e || f
c || d

2. a → axial

3. e → equatorial

29.

 4. a & e → axial & equatorial

5.

Possible conformer of cyclohexane :

y Half chair form is very unstable due to eclipsing of hydrogen.

y Boat form is unstable due to flag pole repulsion.

y Twist boat is relatively less stable than chair form due to strain.

Twist boat

30.

y Chair form has negligible angle strain.
Therefore most stable conformer of cyclohexane

y Rigid form does not exist because of eclipsing of twelve hydrogen.

Flipping :

During flipping, all equitorial bond will convert into axial & all axial bond will
convert into equitorial bonds.

31.

 Newman Projection of Cyclohexane Conformer (chair)

H H
6
H CH2 H
1 5
2 4

H CH2 H
H H
Newmann projection of the pair
conformer

Q. Which conformer of methyl cyclohexane is more stable?

(a) (b) 

Sol.

Note :
y Equitorial is more stable than axial.
y Bulky group must occupy equitorial position.
y A is unstable because in (a), 1,3 diaxial repulsion is present

32.

Q. Compare relative stability :

(A) (B) 

(C) (D) 

Sol.

* Chair

* Twist boat
* Boat Stability

* Half chair

* Rigid

Q. Find the direction of equilibrium and also identify Keq.

(1) forward, Keq > 1

(2) forward, Keq > 1

(3) backward, Keq < 1

(4) backward, Keq < 1

33.

 Q.

Explain why substitution at equatorial position changes Keq value

drastically up.
Sol. –R Keq
–H 1
–CH3 18
35

4000

Bulky group is more stable at equitorial as bulkiness increases stability at

equtorial position increases.

Q.

–R Keq
–F 1.5
–Cl 2.4
–Br 2.2
–I 2.2
Explain ?

Sol.
y In case of F and Cl, size factor dominates therefore more bulky group at
equatorial is more stable.
y But in case of Cl, Br and I bond length factor dominates.

34.

 Geometrical Isomerism

Geometrical Isomerism:
Those stereoisomers which are not interconvertable in each other at normal
temperature are called configrational isomers.
Configurational isomers which are not interconvertable in each other at normal
temperatire due to restricted rotation are called geometrical isomers.
OR
Those stereoisomers which have different geometry around restricted rotation
unit.

Three Condition for Geometrical Isomers :

y Restricted rotation
y Axial distance different
y Different unit at terminal (terminal valency should be different)

Free Rotation System :

(free rotation)

For example
Butane molecule about C2 − C3 sigma bond shows rotation.

1. Restricted Rotatory System :

35.

 y In a molecule restricted rotation arises due to
(a) Due to presence of double and triple bond

Note :
Triple bond never show G.I.

Example :

(b) Around single bond in cyclic compounds (σ bond pure)

DU = 1 Example :

act like double bond

(c) Polyphenyl having Steric Hindrance
Example :

H H BG BG

H H BG BG

Free rotation BG = Bulky group

Small group Bulky group

Steric hindrance decreases Steric hindrance increases
Rotation (free) Rotation (restricted)

This is because of stric

hindrance rings become
Perpendicular so they
don't come back

36.

(d) Cyclic alkene

H H H

(e) Allene System

(f) Spirane System
x x x x

y y y y
We will study this d, e, f cases in next lecture.

2. Aerial distance different :

Here  1 ≠  2

3. Different Terminal Valency at same atom :

(a) (b) 

RR    RR
TVD × TVD ×
 1 ≠  2 ×   
1 ≠ 2 ×
GI × GI ×

(c) (d) 

RR
TVD 
1 ≠ 2 
GI 

(e)

37.

 Special point to learn :
Geometrical isomerism have different physical & chemical properties
Example : Dipole moment and Boiling Point :

(A)             (B)

BP µ m (Dipole moment)
BPA > BPB

Example : Melting Point

          

MPA < MPB

Geometrical isomerism in cyclic alkane compound :.

In cycloalkane, two different sp3 hybridised atom contains different groups
then molecule show Geometrical isomerism.

Examples :
Select among the given compounds, capable to show geometrical isomerism.
x
x x
1. No 2.  Yes

38.

 a x
x
x a
3. Yes 4.  No
H
x x

x
5. Yes 6.  Yes
x
x

a b
7. Yes 8.  No
X

x
x
x a
9. No 10.  Yes

x
x + 0H

11. Yes 12.  Yes

a 1

y +
H
N
13. Yes

N
H
1. Which of the following double bond will not exhibit geometrical isomerism.
Me Ph Me
(A)  C C (B)  C O
H3C C6H5 Ph
Me
(C)  C N Me (D)  Me – N = N – Me
Ph

39.

 2. Which of following will not show geometrical isomerism ?
H3C Cl Cl Br
(A)  C C (B) C C
H Br Br I

H3C CH3 Br Cl
(C)  C C (D) C C
H H Ph Cl
CH3 CH3
CH3 CH3
3. CH3
CH3 CH3
(III) CH3
(I) CH3
(II)
Which among these are isomers ?
(A)  I and II (B)  I and III
(C)  II and III (D)  all of these

4. Which of the following compound can show geometrical isomerism.

Br Cl CH3

(A)  C C (B)  C
I Cl CH3

CH3
F Et H3C
C
(C)  C C (D)  CH3
Cl Et
H3C
5. The geometrical isomerism is shown by
CH2 CH2

(A)  (B) 

CHCl
(C)  (D) 

CHCl
Ans.
1.  AB 2.  D 3.  A 4.  D 5.  D

40.

 Poly Alkene

(i) Cumulated alkene : CH2= C= C= C= C= CH2

(ii) Conjugated alkene : CH2 =CH − CH =C − CH =CH2
(iii) Isolated alkene : CH2 = CH − CH2 − CH = CH − CH2 − CH = CH2

y Stereochemistry in even p-bond allene:

y Stereochemistry in Odd p-bond allene :

H H
C C C C
H H

Both terminal sides valencies are in same plane

y Condition for cumulated alkene :

(i) Even cumulated alkene here show geometrical isomerism
(ii) Odd cumulated alkene can show geometrical isomerism if terminal
valencies are different.
H
(i) (ii) 
C C C C C C
H Br

H H
(iii) (iv)  C C C C
C C C C
H H

H Br F
(v) C C C C (vi) 
C C C
Me Et H Cl

41.

 1. GI in cyclo alkene :

They can not show geometrical isomerism about alkene due to angle strain
in trans form.

y Baeyer angle strain theory :

   →   

    H H H
   cis-cyclooctene   trans cyclooctene
  stability
8 to 11 cis > trans
≥ 11 trans > cis

Example :

H
H

H
H
   cis-decene      trans-decene

42.

 Q. Minimum number of carbon required for cycloalkene to show geometrical
isomerism
Ans. 6

Sol.

Q. Minimum number of carbon required to show geometrical isomerism.

Ans. 0

Sol. N N
H H

Q. Minimum number of carbon required for alkene to show geometrical

isomerism
Ans. 4
H3C CH3
Sol. C C
H H

Q. Minimum number of carbon required for cycloalkane to show geometrical

isomerism
Ans. 5
CH3

Sol.
CH3

y geometrical isomerism in Spirane :

By replacing ring from π -bond or π -bond from ring basic geometry remain
same.

   

C
 
Above all have same geometry.

43.

 H H H H
1. 2. 
Cl H D D
H H H
3. 4.  H
Cl Cl H

Cl

H
5. H 6. 
Cl

Cl
Cl
H
7. 8. 
Cl
H
9. 10. 
Cl
Cl

11.

44.

Geometrical isomerism in polyphenyl

  

G1 − G2 ⇒ bulky groups at ortho position

Small groups : −H, −D, −T, –OH, −NH2 , −F, −CI, −CH−, −C ≡ C−, −C ≡ Netc.

3.

Restricted rotation unit 

Terminal valency different 
geometrical isomerism 

Note :
Even phenyl system never show geometrical isomerism
Odd phenyl system can show geometrical isomerism If terminal valencies are
different at ortho position.

4.

Atropisomers :
Stereoisomers arises due to bulky group or stereo repulsion are called
atropisomers.

45.

 Isomerism

y Types of configuration in Geometrical Isomerism

(i) Cis trans
(ii) E – Z
(iii) Syn – Anti

1. Cis-trans :
Same group oriented same side at terminal valencies- CIS
Same group oriented different side at terminal valencies- TRANS

Example :

(A) (B) 

(C) (D)  ( φ =Ph group)

(E) (F) 

(Cis) (Trans)

(G) (H) 

2. E-Z system :
E = Entgegen & Z = Zusamman

Note :
There is no relationship between E-Z & cis-trans means a molecule having E-Z
(i) 
configuration, may be cis or trans & vice versa.

(ii) Same priority group are on same side ⇒ Z

Same priority group are on opposite side ⇒ E

46.

y Priority order or rule : (Cahn, Ingold & Prelog ,CIP rule)
Rule-1 :
Assign priority on the basis of atomic number, higher is the atomic number of
connecting atom from Geometrical Isomer unit higher will be its priority.

Priority order : –I > –Br > –Cl > –F > –OH > –NH > –CH
2 3

Example:

Sol.

Rule-2 :
If first atom attached with terminal valencies is same consider second atom
and if it is also same then see till first point of different is not found.
Examples :
(i) –CH2 – Cl > –CH2 – CH2 – I

(ii)

(iii)

Rule-3 :
If connecting valencies having multiple bonds then duplicate the double bond
& triplicate the triple bond then check priority.
Duplicate Triplicate
–A=B –A ≡ B

47.

 Example:
1. –CH=O –C ≡ N

Sol.   > 

2.

Sol.

Rule-4 :
If cyclic groups are present then priority will be decided by breaking single
bond to obtain open chain compound.

Examples :

1.

Sol.

2.

Sol.

48.

3.

Sol.

Rule-5 :
If real group is exactly identical to hypothetical (imaginary) group then priority
will be given to real group.
Real > Imaginary

Example :

1.

Sol.

Rule-6 :
If lone pair is present then it will considered as least priority group as lone pair
atomic number is zero.

49.

 Example:

5. (E)
1. ⇒Z

2. ⇒E 6. (Z)

Rule-7 : 7. (E)
In case of isotope, priorities will be decided
according to atomic mass, higher will be
atomic mass, higher is the priority.

8. (E)
Examples :
1. −T >, −D > −H

2. −OH < −O18H

3. (trans) / (Z)
9. (E)

1. (Z)

10. (Z)
2. (Z)

3. (Z)
11. (E)

4. (E) 12. (E)

50.

 H CH2–CH2–Br
13. (Z) 18. (E)
Br CH2–CH2–Cl

O
14. (Z) H
19. (E)
Cl

O
O
15. (E)
Br OCH3
20. (Z)
O H CH3

16. (Z)

21.   (EEE)

17. (E)

3. Syn - Anti :
 Applicable only for nitrogen containing compound where geometrical
isomerism is possible.

– N = N – (Azo compound)

Examples :

(1) (2)  (3) 

(4) (5)  (6) 

51.

 (7) (8)  (9) 

(10) (11)  (12) 

(13) (14)  (15) 

(16) (17)  (18) 

52.

 Isomerism

y Calculation of geometrical isomer :

Case I ⇒ If both the ends are different
2n when n is number of stereogenic area or p bond which can
show G.I.
Case II ⇒ If both the ends are same
2n–1 + 2p–1
If n = even ; P = n/2
n+1
If n = odd ; P =
2
y Hint Rules for cyclic system :
(i) 3 member to 7 member cyclo alkene exist in only cis form.
(ii) 8 to 11 member can form cis & trans but cis is more stable
(iii) from 12 member trans is more stable.

Case-1 : Unsymmetrical compounds :

1. CH3 – CH = CH – CH = CH – CH2 – CH3
Ans. 4

2.

Ans. 4

Case-2 : Symmetrical compounds :

3. CH3 – CH2 – CH = CH – CH = CH – CH2 – Me
Ans. 3

4.

Ans. 6

Case-3 : In case of cyclic compound draw and check.

5.

Ans. 2

Sol.

53.

 6.

Ans. 3

Sol.

7.

Ans. 4
Sol.

a a a

b c b c b c

a a

b c b c

Case-4

26.

Ans. 4

27.

Ans. 3

54.

Q.I. Calculate total number of only geometrical isomers in following compounds
(Theoritical).

(1) Total G.I. = 2

(2) Total G.I. = 8

(3) Total G.I. = 8

(4) Total G.I. = 8

(5) Total G.I. = 4

(6) Total G.I. = 3

(7) Total G.I. = 8

(8) Total G.I. = 6

(9) Me Me Total G.I. = 2

H H
H
H
(10) Total G.I. = 2

H H

(11) Total G.I. = 2

Me Me
Me
(12) Total G.I. = 2
Me

(13) Total G.I. = 2

55.

 (14) Total G.I. = 2

(15) Total G.I. = 4

(16) CH3–CH=CH–CH=CH–CH=CH–CH3 Total G.I. = 6

(17) H2C CH CH2 CH Me Total G.I. = 8

(18) Me–CH=C=CH–CH2–CH=C=C=CH–Me Total G.I. = 2

(19) Br – CH = C = C = CH – CH = CH – Br Total G.I. = 4

(20) Total G.I. = 2

56.

 Isomerism

Chiral Centre & | C.C. |

Or Asymmetric - centre
or Stereogenic - centre
* Those sp3 atom which is having four different valancy
To identify chiral centre consider C.I.P. rule (E and Z)

Rule :-
(i) Consider atomic number for preference.
(ii) If lone pair then consider is zero atomic number.
(iii) If isotope then consider atomic mass for preference.
(iv) If first valaney is same then consider second and so on.
(v) If p-bond then consider (s) sigma bond by adding hypothetical atom.
(vi) If cyclic system then consider as open chain system.

Que. Calculation of chiral centre in below mention organic compound :

(A) (1)

(B) (1)

(C) (2)

(D) (2)

H
CH2 CH2
H2C CH2
(E) (0)
H2C CH2
CH2 CH2

57.

 CH
CH CH3
C HC
(F) CH CH CH3 (9)
CH CH
CH
HO
Cholestrol

(G) H3C HC CH2 (1)

O
CH3
CH
(H) (1)

Cl
CH
(I) (1)

(J) H3C CH CH CH3 (2)

OH OH

(K) (2)

Cl

CH
(L) (4)
CH

Cl

(M) (4)

58.

 O

(S) H3C S PH2 (1)

O
(N) (4)

(T) (1)

H
Cl
(U) N (1)
Cl
CH3
(O) (4)
O
Br H
(V) H3C C N (1)
Br CH3
O
H
(W) H3C S (1)
(P) H3C D (1)
T

(X) (1)
(Q) (1)

AS
(R) D CH3 (1)
H

Stereo- Centre / S.C

The specific centre in which one interchange give a new stereo isomer
or
by interchange any two valancy and we get new stereo isomer.

(A)

59.

 (B)

Compound C.C. S.C.

1. H3C CH CH CH3 (2) (2)
OH OH
2. H3C CH CH CH CH3 (1) 1+2=3
OH
3. CH3–CH=CH–CH=CH–CH3 0 4
4. H3C HC CH CH2 (1) (1)
OH
Br
5. H3C (2) (2)

60.

 Isomerism

POS (Plane of symmetry )

(σ)
COS (Centre of symmetry or centre of inversion)
SYMMETRY (C i)
A OS (Axis of symmetry)
(Cn)
AAOS (Alternative axis of symmetry)
(Sn)

Plane of Symmetry (POS) (s) :

y It is an imaginary plane which bisect the molecule in exact two equal half and
they are mirror images of each other.
y In compound POS may or may not be present.
y In a molecule more then one POS may be present.
y While imaging POS thickness of molecule is also consider.
y Those molecule which are planar, they may cut along their thickness which is
known as molecular plane (slice cut).

Example:
Bread

Following alphabetical letters may be used for elementry understanding of

P.O.S. :

axe

A A
axe

S SS Not plane of symmetry

61.

 A B C D E F G
H I J K L M N
O P Q R S T U
V W X Y Z
Q. Identify POS in given molecules :
H Br
1. POS ; Molecular Plane
Br H
H H
2. C C C C POS ; V, H, M.P.
D D
CH3

3. POS ; H ; Vû ; M.P. û

CH3

4. POS ; Hû ; V

5. POS û
O

6. POS; Perpendicular plane mid bisect

7. POS; diagonal bisector

62.

 Centre of Symmetry (COS) :
A imaginary point in the plane from if we draw two lines in opposite direction
meets like atom/group at equal distance, called COS.
y COS is absent in eclipsed conformer.
y COS is absent in fischer projection.
y COS may present in staggered conformer.
H –C ≡ C – H O= C= O
1. COS  2.  COS 
H H H H
3. C=C COS  4.  C=C COS û
H H Me Me
0H + ) %U
5. & & COS  6.  & & COS û
+ 0 H &O ,

H H + '
7. C=C=C COS  8.  & & & COS û
H H + '

9. COS û 10.  COS û

11. COS  12.  COS 

13. COS û
14.  COS û

15. COS û 16.  COS 

17. COS û
18.  COS û

Axis of symmetry (AOS) (Cn) :

n = 360°
y If a compound is rotated by 360° by n, about an imaginary axis and if we get
in-distinguishable compound (configuration repeat itself) then it is called axis
of symmetry.

63.

 y At 360° molecule repeat itself and that axis is called natural axis and it is not
considerable.
y Linear molecule has infinite AOS.

Example :

     

y Axis where value of n is maximum are known as Principle axis or Main axis.

   
n = 2        n = 3

y If q = 180° then n = 2 C2
y If q = 120° then n = 3 C3
y If q = 90° then n = 4 C4
y If q = 72° then n = 5 C5
y If q = 60° then n = 6 C6

Q. Find out A.O.S. in following molecules :

1. O = C = O

2.

3.

4.

5.

6.

64.

Alternate axis of symmetry (AAOS) (Cn)
Example :

Example:
Q. Comment about POS, COS and AOS in 5.
following molecules :
Ans. POS (s) → 
1. CH4
C2 → 
Ans. POS (s) → 
C3 → û
C2 → 
Ci → û
C3 → 
Ci → û
6.
2.
Ans. POS (s) → 
Ans. POS (s) →  C2 → 
C2 →  C3 → û
C3 →  Ci → 
Ci → 

7.

3. Ans. POS (s) → û

C2 → 
Ans. POS (s) →  C3 → û
C2 →  Ci → û
C3 → û
Ci → û

8.
4.

Ans. POS (s) →  Ans. POS (s) → û

C2 →  C2 → 
C3 → û C3 → û
Ci → û Ci → û

65.

 Dpp-23
Q. Answer about following molecules in 5.
below pattern :
Chiral Carbon   → _ _ _ (/û)
POS   → _ _ _ (/û)
COS   → _ _ _ (/û) Ans.
Geometrical isomerism → _ _ _ (/û) Chiral Carbon → û
POS → 
COS → û
Geometrical isomerism → û
1.

6.
Ans.
Chiral Carbon → û
POS → 
COS → û Ans.
Geometrical isomerism → û Chiral Carbon → û
POS → û
COS → û
Geometrical isomerism → û
2.

7.
Ans.
Chiral Carbon → û
POS → û
COS → û
Geometrical isomerism → û Ans.
Chiral Carbon → 
3.
POS → û
Ans.
COS → û
Chiral Carbon → û
Geometrical isomerism → 
POS → 
COS → û
Geometrical isomerism → û
8.

4.

Ans. Ans.
Chiral Carbon → û Chiral Carbon → 
POS →  POS → û
COS → û COS → û
Geometrical isomerism →  Geometrical isomerism → 

66.

9. 13.

Ans.
Chiral Carbon → û Ans.
POS →  Chiral Carbon → û
COS → û POS → 
Geometrical isomerism → û COS → û
Geometrical isomerism → û
10.

Ans. 14.
Chiral Carbon → û
POS → û
COS → û
Geometrical isomerism → û Ans.
Chiral Carbon → û
11. POS → û
COS → û
Geometrical isomerism → û
Ans.
Chiral Carbon → û
POS → 
15.
COS → û
Geometrical isomerism → û

Ans.
12. Chiral Carbon → û
POS → û
Ans. COS → û
Chiral Carbon → û Geometrical isomerism → û
POS → 
COS → û
Geometrical isomerism → 

67.

 Isomerism

y R–S system (Absolute configuration)

R → Rectus (Right)
S → Sinister (Left)
R-S nomenclature is assigned as follow :
Step-I :- By the set of sequence rule, we give the priority order of atom or
group connected through the chiral carbon.
Step-II :- If atom/group of minimum priority present on the vertical line, then
Movement of eyes in clockwise direction = R
Movement of eyes in anticlockwise = S
Movement of eyes taken from 1 → 2 → 3 through low molecular weight group
(if needed)

  

Step III :- If minimum proirity group present on the horizontal line, then
clockwise rotation ⇒ S
anticlockwise rotation ⇒ R

  

Example:

1. 2. 

68.

Q. Indicate whether each of the following structure has the R-configuration or
the S-configuration :

1. → S
11. → 3S–3R

2. → R

12. → 2S–3S
3. → R

13. → S

4. → S

14. → R

5. → 2R–3S
15. → R

6. → 2S–3S

16. → 2S–3R
7. → 2R–3R

17. → R

8. → 2S–3S

18. → 1R–3R

9. → R

10. → R 19. → 1S–2S

69.

 Isomerism

Diastereomer / Dia
Those stereoisomers which are not mirror image of each other.

Example :

cis-trans ,

Erythro-threo

Two chiral centre + one interchange

Three chiral centre + two interchange

y Diastereomer having different physical properties melting, boiling point,

solubility.
y Diastereomer are having different chemical properties.
y If only one chiral centre then diastereomer is not possible but if there is chiral
centre with p bond then diasteromer possible.
y Same function group on same side in two chiral centres

70.

 Enantiomer

Identical:
Those compounds which superimposed on its mirror image are known as
identical.
y To differentiate between identical and enantiomer the following Symmetry
element are required which are:
(i) COS / centre of symmetry / Ci
(ii) POS / plane of symmetry / s
(iii) AOS / axis of symmetry / Cn
(iv) AAOS/ Alternate axis of symmetry / Sn
Meso = two or more C.C. + POS / COS / AAOS
y Those compounds which are having chiral centre even though optically inactive.
y Meso compound are optically inactive because half compound rotates PPL in
clockwise direction and remaining half part in anticlockwise direction.

71.

  or 

Meso compound are optically inactive but consider in optical isomer because it
rotates PPL light but the net result is zero.

Q. Identify meso :

1. 2.  3. 

4. 5.  6. 

7.

Solutions :
1. Meso
2. Optically active
3. Meso
4. Meso
5. Optically active
6. Geometrical Isomer, Optically inactive
7. Optically active
Note : Meso compounds are identical or diastereoisomer but never enantiomer.
Questions : Identify following meso or diastereoisomer

1.  and  2.   and 

72.

 3.

4.  

Answer :
1. Identical
2. diastereoisomers
3. Identical
4. Identical

Enantiomer / Ena
Those stereoisomers which are mirror image of each other but do not
superimpose on each other are known as enantiomer.

Superimpose

Non super impose

Anti    Clockwise

y Enantiomers are having same physical properties like melting point, boiling
point, solubility except rotation towards plane polarised light.
y Enantiomers are having same chemical properties except reaction with enzyme.
y Equimolar mixture of enantiomer is known as
Racemic mixture = 50% d + 50 l
Optically inactive

73.

 Isomerism

Polarimeter
Chiral-Achiral Molecule
Electromagnetic wave of light :

Optical Isomerism :
Substances which can rotate the plane-polarised light are called optically
active substances and the property of a substance to rotate the plane-
polarised light is called optical activity.

 
Normal light     Basic understanding of PPL using slit

The instrument used for measuring the optical rotation called a polarimeter.
It consists of two Nicol prisms, one called the polariser (near the light source)
and the other called the analyser, a glass tube containing the solution of an
optically active compound is placed.

74.

Optical Isomerism :
A substance which rotates the plane-polarised light towards right (in the
clockwise direction) is called dextrorotatory (Latin : dexter = right) and is
usually represented by the prefix d or (+). On the other hand, a substance
which rotates the plane-polarised light towards the left (in the anticlockwise
direction) is called laevorotatory (Latin : leaves = left) and is usually represented
by the prefix ‘l’ or (–).
Behaviour of Optical Active and Inactive Molecules towards PPL

75.

 Chirality of molecules and objects :
An inspection of the molecular structures of optically active compounds
indicates that all these compounds have Chiral* (or dissymmetric) molecules.
A molecule (or an object) is said to be chiral or dissymmetric, if it is not
superimposable on its mirror image, and the property of non-superimposability
is called chirality.
On the other hand, a molecule (or an object) which is superimposable on its
mirror image is called achiral (non-dissymmetric or symmetric).

Specific rotation :
θ
[a]Dt = , where q is the optical rotation, l is the length of the tube in
 ×C
decimetre, C is the concentration of the solution in g ml–1, D is the wavelength
of sodium light, and t is the temperature.

Racemic forms and Enantiomeric Excess :

A sample of an optically active substance that consists of a single enantiomer
is said to be enantiomerically pure or to have an enantiomeric excess of 100%.
An enantiomerically pure sample of (S)-(+)-2-butanol shows a specific rotation
of +13.52°. On the other hand, a sample of (S)-(+)-2-butanol that contains less
than an equimolar amount of (R)-(–)-2-butanol will show a specific rotation
that is less than +13.52° but greater than 0°. Such a sample is said to have an
enantiomeric excess less than 100%. The enantiomeric excess (ee) is defined
as follows :
% Enatiomeric excess
moles of one enantiomer − moles of other enantiomer
= × 100
total moles of both enantiomers

observed specific rotation

% Enantiomeric excess = × 100
specifice rotation of the enantiomer

Example :
A mixture of the 2-butanol enantiomers showed a specific rotation of +6.76°.
We would then say that the enantiomeric excess of the (S)-(+)-2-butanol
is 50%.

Solution :
+6.76°
Enantiomeric excess = × 100 =
50%
+13.52°

76.

 Conditions for optical activity :
y It must have an assymmetric C atom or the chiral C atom. C atom which is
attached to four different atoms or groups is called an assymmetric C atom or
the chiral centre or stereogenic or stereocentre.

For example :

y It must have non-superimposable mirror image.

y It should not contain any element of symmetry, i.e.,
(i) Plane of symmetry or (mirror plane or s-plane).
(ii) Centre of symmetry or centre of inversion.
(iii) Alternating axis of symmetry.
y Chiral, optically active then POS as well as COS should be absent.
y Achiral, optically inactive then POS and COS both absent.
y Compound to be achiral it should have POS or COS or both.
y There is no relationship between AOS and optically activity of molecule.

Example: Reason :
P.O.S 
C.O.S 
1.  
3.

Optically active →  Optically active → 

Chiral molecule →  Chiral molecule → 
Achiral molecule →  Achiral molecule → 
Optically inactive →  Optically inactive → 
Reason : Reason :
P.O.S  P.O.S 
C.O.S 
4.

2.
Optically active → 
Chiral molecule → 
Achiral molecule → 
Optically active →  Optically inactive → 
Chiral molecule →  Reason :
Achiral molecule →  P.O.S 
Optically inactive →  C.O.S 

77.

 Reason :
P.O.S 
5.
C.O.S 

Optically active → 
Chiral molecule →  9.
Achiral molecule → 
Optically inactive → 
Reason : Optically active → 
P.O.S  Chiral molecule → 
C.O.S  Achiral molecule → 
Me Optically inactive → 
Reason :
P.O.S 
6.
10. Hockey shaped molecule
Me Optically active → 
Optically active →  Chiral molecule → 
Chiral molecule →  Achiral molecule → 
Achiral molecule →  Optically inactive → 
Optically inactive →  Reason :
Reason : P.O.S 
P.O.S 
C.O.S  11.

7.

Optically active →  Optically active → 

Chiral molecule →  Chiral molecule → 
Achiral molecule →  Achiral molecule → 
Optically inactive →  Optically inactive → 
Reason : Reason :
P.O.S  P.O.S 
C.O.S  C.O.S 

12.
8.

Optically active → 
Chiral molecule → 
Optically active →  Achiral molecule → 
Chiral molecule →  Optically inactive → 
Achiral molecule →  Reason :
Optically inactive →  P.O.S 

78.

13.

15.

Optically active → 
Chiral molecule → 
Achiral molecule →  Optically active → O
Optically inactive →  Chiral molecule → O
Reason : Achiral molecule → 
P.O.S  Optically inactive → 
C.O.S  Reason :
P.O.S 
14.

Optically active → 
Chiral molecule → 
Achiral molecule → 
Optically inactive → 
Reason :
C.O.S 

79.

 Isomerism

D/L, Epimer, Anomer / Erythro-Threo / Amine flipping

D/L nomenclature :

Rule :
(i) This nomenclature is only applicable for fischer projection of carbohydrate
and amino acid.
(ii) Carbohydrate means optically active polyhydroxy carbonyl compound.
(iii) Amino acid is the monomer of protein.
(iv) For D-L nomenclature, fischer must be correct.

Condition :
(a) Carbon containing main functional group at top
(b) Maximum carbon on vertical line.
(c) For one chiral centre if OH/NH2 group on right side then D and if on left side
then L.

CHO CHO
H OH/NH 2 NH2/HO H
CH2OH CH2OH

D           L

(d) If two or more chiral centre then in amino acid consider first chiral centre
and in carbohydrate consider last chiral centre for D, L configuration.

Q. Identify the D / L configuration CHO

COOH H OH
H NH2 2. HO H
1. HO H CH2OH
CH3
CHO
COOH
H OH
H NH2 Sol. HO H L-Carbohydrate
Sol. HO H Right; D-Amino
CH2OH
CH3

80.

 CHO CHO
H OH 5. HO CH2OH
3. H OH H
CH2OH
CHO

CHO Sol. H OH D-Carbohydrate

H OH CH2OH
Sol. H OH D-Carbohydrate
CH2OH
CH2OH 6. H OH
CHO
CHO
H OH CH2OH CHO

4. HO H Sol. H OH   HO H
CHO CH2OH
H OH
H OH L-Carbohydrate
CH2OH

CHO
H OH
Sol. HO H D-Glucose

H OH
H OH
CH2OH

Erythro and Threo Designation

y Compound with two adjacent chiral (stereogenic) C atoms are sometimes
designated by prefix ‘erythro or threo’.
y The stereoisomers in which the same groups are present on the same side
of the Fischer projection are called erythro isomers while the stereoisomers
in which these groups are present on the opposite sides are known as threo
isomers.

81.

 Example-1 :

CHO CHO
H OH HO H
H OH HO H
CH2OH CH2OH
D–Erythrose Enantiomer
(OH) on the same side

Example-2 :

CHO CHO
HO H H OH
H OH HO H
CH2OH CH2OH
D–Threose Enantiomer
(OH) on different sides

Example-3 :

COOH COOH
H Br Br H
and
H Br H Br
CH3 CH3
Erythro Threo
2,3-Dibromo butanoic acid

Optical activity of tert-Amines and tert-Carbanion of the type (R1R2R3N:) and

(R1R2R3:C¯)
Such an amine and carbanion with a lone pair of electrons (being considered
a fourth different group) are chiral because of their pyramidal geometry, but
they are optically inactive. A rapid ‘umbrella’ type inversion converts either of
the enantiomers to a racemic mixture. The energy required for this inversion
is very low at room temperature, since this inversion does not involve bond
breaking and bond formation. Thus racemisation occurs and enantiomers
cannot be isolated.

82.

 R1 R1 R1 R1
R2 N N R2 R2 C C R2
Nitrogen C inversion
R3 inversion R3 R3 R3
 

But amine salts are optically active. Nitrogen inversion in not possible,
e.g., [R1R2R3N+H]Cl¯.

Amine Flipping (Umbrella Inversion / Amine Inversion)

D
N H T
H T N
D

Q. Why compound (B) has rapid inversion tendency compare to compound (A)

Sol. Bulky group

  (A)       (B)
Bulky valencies at sp3 hybridised nitrogen atom tends more flipping.
DG (A) > (B)

83.

 Some more examples of optically active N-containing compounds :
Me
(i) Me N Me Me N
Me Me
(+) form (–) form
1,2,2-Trimethyl aziridine

(ii) 1-Chloro-2-methyl aziridine shows four stereoisomers.

Cl Cl Cl Cl

Me N N Me H N N H

H H Me Me
(+) form (–) form (+) form (–) form

cis trans

Racemic Mixture :
y When equal amounts of two enantiomers are mixed together, it gives an
optically inactive form called racemic mixture or modification.
y It is denoted by using the prefix ± or dl before the same of compound.
y The optical activity of a racemic mixture is due to external compensation, i.e.,
the rotation caused by molecules of one enantiomer is exactly cancelled by an
equal and opposite rotation caused by the same number of molecules of the
other enantiomer.
y A racemic mixture can also be obtained chemically. The process by which
one enantiomer (+ or –) of an optically active compound is converted into a
racemic mixture is called racemisation. Racemisation can be carried out by
heat, light or chemical reagents.

Example :
Lactic acid and Tartaric acid

Resolution of Racemic Mixture :

y The process of separation of racemic mixture into its (+) and (–) enantiomers
is called resolution.
y Enantiomers have identical physical and chemical properties except towards
optically active reagents, they cannot be separated by the usual techniques
such as fractional crystallisation, fractional distillation, chromatography, etc.
Therefore, special methods are used to achieve their separation. Some of
these are listed below :
(i) Mechanical method
(ii) Biological method
(iii) Chemical methods (by making their diastereomers)
(iv) Chromatographic separation by using special adsorbents.

84.

Diastereomeric method
One of the most common method is to allow a racemic mixture to react
with an enantiomer of some other compound. This changes a racemic form
into a mixture of diastereomers which have different solubilities and melting
and boiling points. These can be separated from one another by conventional
methods of separation of compounds. The separated diastereoisomer is then
broken down to give pure enantiomers.
Chemically we can seperate enantiomer via diastereomerism
(i) d + l + d or l d–d+l–l
(Racemic mixtur) (Diastereomer)
(ii) (+) + (–) + (+) or (–) (+, +) + (+, –)
(Diastereomer)
Example-1 :

85.

 Example-2 :

O O O
18 18 18
R C OH + R OH R C O R + R C O R
+ ++ +–

 
(Racemic Mixture, + –)

The importance of stereochemistry :

Chiral molecules can show their handeness in many ways, including the way they
affects human being. One enantiomeric form of a compound called limonene
is primarily responsible for the odor of oranges and the other enantiomer for
the odor of lemons.

y All naturally occurring sugars, including the sugars that occur in DNA, are of
D-configuration. the yeast enzymes can specifically ferment D-glucose and
not its L-enantiomer.

y Stereochemistry also plays an important role in deciding the physiological

properties of compounds.

(–)-Nicotine is much more toxic than (+)-Nicotine, (+)-adrenaline is very active

in construction of blood vessels than (–)-adrenaline.

y Chirality is crucial for the effect of drugs as well. In majority of cases, only one
enantiomer is found to have the desired effect while the other isomer may be
totally inactive or has an opposite effect.

86.

Example :
It is the (S)-enantiomer of ibuprofen that has the pain-relieving action.
(–)-Thyroxine, an amino acid of thyroid gland, speeds up metabolic processes
and causes nervousness and loss of weight. Its enantiomer, (+)-thyroxine, has
none of these effects but is used to lower the cholesterol levels.

Ring Flipping
Br

Br
Cl

Cl
Non resolvable

87.

 Isomerism

Calculation of Optical Isomer (O.I.) :

Case-I : For unsymmetrical molecules :

For calculation of optical isomers, in unsymmetrical molecule always apply
Total Number of Optical Isomers = 2n
where, n = Number of Chiral Centre / Number of even allene system / spiro /
biphenyl

Q. Calculate number of optical isomer (if CH3

possible) :
5. H OH
OH
H Br
1. H3C CH CH2 CH3
CH3
Sol. n = 1 chiral centre
21 = 2 Sol. n = 2 chiral centre
HO 22 = 4
H HO H
Br
/ R /S

6.
2. CH3 – CH = C = CH – CH3
Sol. n = 1 chiral centre
21 = 2 Cl
Sol. n = 2 chiral centre
22 = 4
H OH H OH
7.
CHO CH2OH
Br Br Sol. n = 2 chiral centre
22 = 4
3.
8. Cl
Br
Cl Cl
Sol. n = 1 chiral centre Sol. n = 2 chiral centre
21 = 2 22 = 4

Br Br

4. 9.

Cl OH
Sol. n = 2 chiral centre Sol. n = 2 chiral centre
22 = 4 22 = 4

88.

 O

13.
10.

Sol. n = 0 chiral centre

No optical isomerism possible Sol. n = 1 chiral centre
O 21 = 2

11.

Sol. n = 2 chiral centre

22 = 4
O O
Q. Number of possible optical isomers for
following molecules :

  
O O
1.

Sol. n = 8 chiral centre

  
Optical isomer = 256
Cl 2. 2,4-dichloropentane
12. Sol. n = 2 chiral centre
Optical isomer = 4
Br
Sol. n = 2 chiral centre
22 = 4
3.
Cl Cl

Sol. n = 2 chiral centre

Br Br Optical isomer = 4
2 2
4.
If optical isomer and geometrical isomer
same centre then consider optical isomer
here geometrical isomer included. Sol. n = 1, spirane system
Optical isomer = 2

89.

 5.
2.
Sol. n = 2 chiral centre
Optical isomer = 4
Sol. n = 2 chiral centre
6. Optical isomer = 3

Sol. n = 1 chiral centre

Optical isomer = 2
3.
Case-II :
Calculation of optical isomers in Sol. n = 2
Symmetrical molecule : Optical isomer = 3
Condition : POS or / and COS present
y n = Even
4.
meso + optically active = optical isomer
n 
 −1
2 2 
+ 2n − 1 = Total Optical Isomers
y n = Odd Sol. n = 2
We suggest to draw optical isomer / Optical isomer = 3
stereoisomer in case of n = odd number

Q. Calculate all possible optical isomers 5.

for following molecules :

1.
Sol. n = 2
Optical isomer = 3
Sol. n = 2
Optical isomer = 3

Tips and Tricks :

Symmetrical molecule → POS / COS
n Meso Optically active Optically isomer
2 1 2 3
3 2 2 4
4 2 8 10
5 4 12 16

90.

7. 2.

Sol. n = 3 (one pseudo)

Sol. n = 4 Optical isomer = 4
4
−1
4−1
⇒ 2 +2
2

⇒ 8 + 2 = 10 3.
Q. Draw all possible optical isomers
(consider pseudo chiral centre) :

1.
Sol.

Sol.

Meso       Meso

Optical isomer = 4

91.

 Isomerism

How to calculate stereo isomer (S.I.)

In unsymmetrical then
Stereo Isomer = 2n
OI → Number of chiral centres
→ Even allene system / spiro / biphenyl
GI → p-bond
→ Ring
→ Odd system allene / spiro / phenyl

Q. Calculate stereo isomer :

1. CH3–CH = CH – Br
Sol. 21 = 2

Cis Trans

2.

Sol. 21 = 2

Cis Trans

3. CH3 – CH = C = C = CH – CH3
Sol. 21 = 2

Cis Trans

92.

4.

Sol. 21 = 2

R    S 

5.

Sol. 22 = 4
Br Br Br Br

Cl Cl Cl Cl

Cl
6.

Br
Sol. 22 = 4
CH CH CH3
7.

Br
Sol. 23 = 8

Cis      

Cis

Trans Trans Trans Trans

93.

 8. H3C CH CH CH CH CH2
CH3
Sol. 2 = 2 1

Cl
9. H3C CH CH CH CH CH CH3
Sol. Stereo Isomer = 4
Cl Cl Cl Cl
cis cis trans trans cis trans trans cis
H H H H
POS POS

enantiomeric pair

10.

Sol.

Cl
Cl Cl
11.

Cl Cl
Cl

Cl Cl Cl Cl

Cl Cl Cl
1 1
Sol. 2
3
Cl Cl Cl

Cl Cl Cl Cl
Cl
Cl
Cl Cl
Cl 1 1
1 1 2
2
5 2
3 4
Cl Cl
4 Cl
Cl Cl
Cl

94.

 G.I. = 8 CH3
S.I. / O.I. = 9 6. H Cl
Cl H
7 meso + 2 enantiomer
CH3
S → 3
Subjective : M → 1
Find : O.A. → 2
Total number of stereoisomers
7. 2,4-dichloropentane
Number of meso compound
S → 3
Number of optically active isomers
M → 1
1. O.A. → 2
8. 2,3-dichloropentane
S → 2 S → 4
M → 0 M → 0
O.A. → 0 O.A. → 4
9. 1,2-dichloropentane
2. S → 2
M → 0
S → 4 O.A. → 2
M → 0
O.A. → 4
3. CH3 – CH = C = CH – CH3 10.
S → 2
M → 0
S → 3
O.A. → 2
M → 1
F O.A. → 2
4. Cl Br
11.
I
S → 2
M → 0 S → 4
O.A. → 2 M → 0
O.A. → 4
CH3
5. H Cl
H Br
CH3
S → 4
M → 0
O.A. → 4

95.