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ORGANIC LECTURE NOTES

(LECTURE No. 5 TO 14

TOPIC : ISOMERISM

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Contents

Lecture 5 & 6
Structural Isomerism
(a) Classification of Isomers (b) Definition of
Chain isomers
(a) Alkanes, Alkenes, Alkynes
(b) R OH, RNH2 (c) With terminal F.G.
(d) Aromatic side chains
Position isomers
(a) C C, C = C, C C, (b) OH, NH2,
SO3H

Metamers
(a) R O R

(b) R NH R, R N R
|
R

(c) R C OR , R C NH R , R C O C R
||
||
||
||
O
O
O
O

(c) Disubstituted, Trisubstituted


Aromatic Compound
Functional Isomers
(a) G.F. = CnH2n+2 O

( OH, O )

(b) G.F. = CnH2nO

(R2C = O, RCHO)

(c) G.F. = CnH2nO2

(RCOOH, R C OR )
||
O

(d) G.F. = CnH2n+3 N

(1, 2, 3 Amines)

(e) Amides

1, 2, 3

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Contents
Lecture 7

Lecture 8

1. Ozonolysis:
1. Structure
2. Applications:
Indentification
(a) Monochlorination
(b) Catalytic Hydrogenation
of C = C; C C

Lecture 9

Lecture 10

1. Stereoisomers
(Classification)
2. Configurational isomers
3. Conformational
isomers
4. Geometrical Isomerism

Lecture 11

Lecture 12

1. Configuration
1. Optical Isomerism
nomenclature
2. Symmetry of elements
in Optical
3. Chirality (Dissymmetry)
Isomers
and Optical Isomers
2.
R/S
Configura4. Optically Active Cartion
in Fisher
bon Compounds
Projection
5. Projection Formula of
Formula
Chiral Molecules
3. Compounds
with 2 Asymmetric Carbons
of Similar
Nature

1. Number of geometrical
isomers
2. E/Z Nomenclature :
3. Physical properties of
Geometrical isomers
(i) Dipole moment ()
(ii) Boiling Point
(iii) Melting Point:
(iv) Water Solubility

Lecture 13
1. Meso isomers
2. Properties of
Optical Diastereomers
3. Chemical method
of separation
(resolution) by
using optically
active reagent

4. Optically active compounds without a


chiral carbon:5. Optical activity without
asymmetric carbon
(I) Case of allene
(II) Case of spiranes :
(III)Case of cycloalkylidene
(IV) Case of ortho-orthotetrasubstituted biphenyls

Lecture 14
1. Conformations/conformers
2. Conformational isomers
3. Conformational energy
4. Dihedral angle of rotation
5. Strains
6. Ethane, propane, n-Butane
7. X-CH2CH2X type
(Saw horse Newman projection formula, stability, P.E. curves)

Phase Coordinator (F Batch)


CDS Sir

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Isomerism Lecture Notes


Isomers:
Compounds with same general formula or molecular formula but different physical and chemical property.
Ex:-

CH3 CH2 OH and CH3 O CH3

Ex:-

CH3COOH and HCOOCH3

Homologs:
Compounds with same general formula differing by same structural unit CH2 or molecular weight by 14
unit.
Ex:- CH3 OH and CH3 CH2 OH
Difference between isomers and homologs:-

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Structural isomers:
When two or more number of organic compounds have same molecular formula but different structural
formula these are called structural isomers.

Stereo isomers:
When two or more compounds have same Molecular Formual (M.F.) and same Structural Formula (S.F.) but
have different stereochemical formula (S.C.F.), these are called stereoisomers.

Stereo Chemical Formula (S.C.F) :


It indicates different arrangements of atoms or groups in space around a stereo centre or it indicates different
spatial orientations of atoms or groups around a stereo centre.
C4H8
CH3
(iii) CH 3 C = CH 2

M.F.

S.F.
(i) CH3 CH2 CH = CH2
These are structural isomers.
For (ii), S.C.F. are
H3C
H

CH3
C=C

H3C

and

(ii) CH3 CH = CH CH3

C=C

H
CH3
Stereocentre
These are stereoisomers.
H

Structural isomers are also known as:(i) Skeletal isomers


(ii) Linkage isomers

(iii) Constitutional isomers

Chain isomers :
They have different size of main carbon chain or side chain (of C atoms)
(i) The two chain isomers should have same nature of F.G./multiple bonds/substituents (except R group)
(ii) The position of F.G./M.B./substituent (locants) is not. considered here.
Note : (i) In almost all functional group chain isomer starts from four carbon atoms except in alkene, alkanone,
ether, ester, 2 amine and 3 amine.
Ex:-

Alkanes:(a) C1 C3

chain isomers not possible

(b) C4H10

H3C CH2 CH2 CH3 and CH3

(c) C5H12

CH3 CH2 CH2 CH2 CH3 , CH3 CH2

(d) C6H14

(i) CH3 CH2 CH2 CH2 CH2 CH3, (ii) CH3 CH CH2
(iii) CH3 CH2

(v) CH3 CH2

CH3

CH2 CH3, (iv) CH3

CH3 ,

CH3

CH3

CH3,

CH3,

CH3

(i) and (ii) Chain isomers


(i) and (iii) Chain isomers
(i), (iv) Chain isomers
(i), (v) Chain isomers
(ii), (v) Chain isomers
(ii), (iii) Position isomers
(iv), (v) Position isomers
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(iii) C C C C C C
C
C

(ii) C C C C C C,
C C

(i) C C C C C C
CC

Ex.

(i), (ii) Chain


(ii), (iii) Position
(i), (iii) Chain

C6H12 (Cycloalkanes):-

(10)

Ans.

(4)

C
CC

CCC

(7)

(11)

(8)

CC

(9)

(6)

(3)

(2)

(5)

(1)

Ex.

CC

(3) and (4) Positional isomer


(3) and (6) Positional isomer
(4) and (6) Positional isomer
(5) and (10) Positional isomer
(All are chain isomers of 1)
Remaining are chain isomers

Ex.

and

shows which types of isomerism ?

Ans.

Chain Isomers

Q.

Write chain isomers of N-alkanamine (1) containing 4 carbon atoms ?

C
C C C NH2

Ans.

C C C C NH2,

Positional isomers:
They have different position of locants Functional group (F.G.) or Multiple Bond (M.B.) or substituents in
the same skeleton of C-atoms.
Nature of F.G. or M.B. should not change.
The skeleton of C-atom should not change.
CC C CC
C

(2) C = C C C ,

CC=CC

(3) C C C C C ,

CCCCC

(1) C C C C C ,
C

Ex.

Page-6

(4) C C C C ,
C C C C OH
OH
Write all Positional isomers of Dichlorobenzene ?

Cl

Ans.

Q.

Cl

Cl

Cl
,

Q.

Cl

Cl

Write all Positional isomers of Dichlorocyclopropane ?


Cl

Cl Cl

Ans.

Cl

Write all Positional isomers of Dichlorocyclobutane ?


Cl Cl

Q.

Cl Cl
,

Cl

Ans.

,
Cl

Write all Positional isomers of Dichlorocyclopentane ?


Cl

Cl

Ans.

Cl Cl

Cl

Q.

Cl

Functional isomers:
They have different nature of functional group (F.G.). The chain and positional isomerism is ignored (not
considered).
Compound
Functional isomer
CCCC

Nil

CCC=C
Ex.
(1)

(Ring-chain isomers are Functional isomers)

Compound
CCCC

Isomer Functional
(a) C = C C = C Alkadiene

Remarks
(a), (b) are not functional isomers

Alkyne

(b)

Cycloalkene

among themselve

(c)

Bicyclo

(2)

C C C OH
Alcohol

CCOC
Ethers

(3)

C C CH = O

C C C
O
Ketones

(4)

C C COOH
Carboxylic acids

(5)

C C C NH2
1 amine

C C OC
O
Esters
..
(a) C C NH C
2 amine
..
(b) C N C
C
3 amine

1, 2, 3 amines are functional isomers

Aldehydes

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(6)

CCCN
Cyanide
(Propanenitrile)

C C NC
Isocyanide
(Ethane isocyanide)

Peroxy bond (unstable)


O
does not exist at room temperature.
C = C O C OH
R O CH2 OH

Hemiacetal
Unstable

Conclusion:- Following compounds dont exist at room temperature:(ii) C C OH

(iii) C OH

(i) C = C OH

OH

(v) C O C = C

OR

Q.

(vi) Any peroxy compound

(iv) C OH

OH

Write acyclic isomers of C5H12O

C
C C C C OH,

C C C C C,
OH
C
C C C OH
C

(7 alcohols)

C
C C O C,
C

C C C O C,
C

C C C O C C,

C
C C OCC

(6 ethers).

G.F.
CnH2n + 3N

n
(1) 3

M.F.
C3H9N

2 Amine (R NH R)

3 Amine R N R
R

G.F.
CnH2n + 1N
2

n
(1) 2

M.F.
C2H5N

1 Amine
(1) C = C NH2
Ethenamine

2 Amine
3 Amine
CC=N
CN=C
Ethanimine
N-Methylene methanamine
(Unstable at room temperature)

C C C O C,
C

C C C C O C,

C
C C C C OH,

C C C C C,
OH
C
C C C OH,
C

(i) C C C C C OH,

Ans.

1 Amine (R NH2)
Q

Q.

H2C CH2 Azine

N
H

Q.

G.F.
CnH2n 1N

n
2

M.F.
C2H3N

Ans.

Cyanides and isocyanides


H3C C N

CH2 = C = NH

HC C NH2

H3C N

C
Page-8

Metamers:
When two isomers have same functional group (containing a hetero atom O, N, S) but have different nature
of alkyl or aryl (aromatic radical) group attached to hetero atom, then these are called metamers.
(a) Same functional group
(b) Chain or position isomerism is not considered.
Following functional groups show metamerism
Ethers (All isomeric ethers are metamers)

(b) R NH R

2 Amines

(c) R N R
R''
(d) R S R

3 Amines

(e) R C O R
O

Esters

(a) R O R

Thioethers

(f) R C O C R Anhydrides
O

O
(g) R S O R

Sulphonate esters

O
Q.

How many esters are possible for C3H6O2 ?

Ans.

C C O C H and C C O C are metamers


||
||
O
O

Q.

3 Amines of M.F. C5H13N (All metamers)

Ans.

CC NCC
C
CCC NC

OCC

Q.

C C
C C NC

and

OC

Show which type of isomerism ?


C

Q.

Acyclic compound (A) contains 18 1 H atoms, two types of C atoms. All H are identical. Identify (A).

Ans.

C C
C C C C C8H18
C C

Q.

Cyclic compound (P) contains 18 1 H atoms, two types of C atoms. All H are identical. Identify (P).

Metamerism

Ans.

Ans.

or

Page-9

Q.

Write structure of smallest cyclic ester (S.F.)


O

Cyclic esters are known as lactones.

O
Q.

Write structure of smallest cyclic amide ?

NH
C

Ans.

CH2 is amide. C

CH is imide

O
O
Compound X is an ether. It has 12 1 H atoms. It has 2 types of H-atoms and 3 types of C-atoms. Write it
Structural formula ?
CH3
H3C O C CH3

Q.

CH3

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STRUCTURE INDENTIFICATION
(1) Calculation of Degree of Unsaturation (DU):(a) It is the hydrogen deficiency index (HDI) or Double Bond Equivalence (DBE)
2H
(b) H3 C H2C CH3
(DU O)

2H
CH3 C CH or CH2 = C = CH2 or

That means Deficieny of 2H is equivalent to 1 DU


(c)

(i) 1DU = Presence of 1 Double Bond or Presence of 1 Ring closure


(ii) 2DU = Presence of 2 Double bond or 1 Triple bond or two ring closure or 1 double bond + 1 ring.

(d)

G.F.

D.U.

(i) CxHy

y
(x + 1)
2

(ii) CxHyOz

yo

(x + 1)
2

(iii) CxHyXs

ys

(x + 1)
2

(iv) CxHyNw

yw

(x + 1)
2

(v) CxHyOzXsNw

ys w

(x + 1)
2

Ex

Calculate DU of following compounds


(a) C6H6O

DU = 4

(b) C6H5Cl

DU = 4

(c) C6Br6

DU = 4

(d) C5H11OCl

DU = 0

(e) C9H12N2

DU = 5

(f) C6N6

DU = 10

(g) C10H8SO5 N4Cl2


E.g.
M.F.

DU = 8
DU

S.F.
H

1.

C4H6

CC=C=C

H
H

H H

CCCC
CCCC
C=CC=C

Page-11

C
CH2

2.

C2H2Cl2

=1

Total isomers = 3

Cl
3. C6H6ClNO (Aromatic)

NHOH
OH

=4

Cl

NH2
Note : If the aromatic Compounds have minimum D.E. 4. That means at least 1 Benzene ring is present.
Q.

C16H16 is symmetrical aromatic alkene. Draw all possible structure.

ANS.

DU = 9
or

or

CC=CC

Page-12

Structure Identification of Organic Compounds by Chemical Reactions:

Monochlorination:(a)

Cl / h
CH3Cl + HCl
(i) CH4 2
Cl / Sunlight
(ii) CH3 CH3 2 CH3 CH2Cl + HCl

Cl

Cl / h
2

(iii)

+ HCl

C
C
Cl / h
C C C Cl + HCl
(iv) C C C 2
C
C
Cl / h
2

(v)

Cl

+ HCl

Remarks:- When an alkane or a cycloalkane is treated with halogen (Cl2, Br2, F2, I2), a photochemical reaction takes
place and a C H bond cleaves and a C Cl bond is formed. So, on H-atom is substituted by one halogen
atom. This is known as monohalogenation reaction.
Application:- If a molecule has more than one type of H-atom, then on monochlorination, it forms a mixture of
monochloroisomers. All these isomers are position isomers.
Conclusion:- Hence, it can be concluded that the total no. of position isomers (structural) of monochloro compounds
is equal to the number of different types of H-atoms present in the reactant. The different type of H-atoms are
also known as non-identical Hydrogens or non-equivalent Hydrogens or chemically different Hydrogens.
Ex.

Monochlori nation
(a) C C C 2
Monochlori nation
(b) C C C C 2

(c) C C C C C

Monochlori nation
3

Monochlori nation
(d) C C C C 4
C
CH3
Monochlori nation
5
(e)

Q.

Cl / h
only one monochloro isomer..
X(C5H12) 2

Ans.

X = Neopentane

Q.

Cl / h
Two monochloro
P(C6H14) 2

How many isomers of P will give two monochloro compounds ?


Ans.

C C
C C C C only one isomers

Remark : In aromatic hydrocarbons, the hydrogen atoms of the side-chain are chlorinated, but H-atoms of Benzene
ring are stable. In pure benzene, no monochlorination

Page-13

CH3
Cl / h
2

Ex.
Q.

CH2Cl

Cl / h
Two mohochloro
X(C8H10) (Aromatic) 2
Cl / h
One monochloro
Y(C8H10) (Aromatic) 2

Ans.

(X)

(Y)

Catalytic Hydrogenation of C = C; C C
General reaction:Ni
R CH2 CH2 R
(a) R CH = CH R + H2
Ni / Pt / Pd
R CH2 CH2 R
(b) R C C R + 2H2
H2

H2
R CH2 CH2 R
R CH CH R
(Not isolated)
2H2 / Ni

CH3 CH2 CH2 CH3


(c) CH2 = CH CH CH3
3H2 / Ni

H2 / Ni


room temperature

H 2/Ni
(100 150C)

(f)

CH2 CH3

CH = CH2

(e)

CH2 CH3

(d)

[Reaction cannot be stopped at any intermediate stage]

Remarks:(a) Alkenes, Alkynes, polyenes or polyynes can be hydrogenated by using catalysts Ni/Pt/Pd at room temperature.
(b) All C C bonds(C = C, C C) are hydrogenated. The reaction cant be stopped at any intermediate stage.

Exceptions:Aromatic bonds which are stable at room temperature but can be hydrogenated at high temperature.

The no. of moles of H2 consumed by 1 mole of compounds is equal to the no. of bonds presents.

All positional isomers of alkenes or alkynes (due to multiple bond) always give same product on hydrogenation.
Page-14

During catalytic hydrogenation, all monochlorination and no rearrangement in carbon skeleton takes place.

Ex:- C = C C = C + Cl2 X

Ex.

C CC
C Cl

2H2 / Ni

(1)

C Cl

Y =

Cl / h
2
Y + Z

(X)

Z =
Cl

CH3

CH3
H / Ni
2

(2)

CH3

CH3
H / Ni
2

(3)

Q.

Cl / h
2
5 Monochloro product

5 Monochloro product

H / Ni
Cl / h
Z(only one monochloro product)
X(C4H6) 2 Y 2

Identify X, Y, Z
Ans.

DU = 2

Cl

Identify the lowest molecular weight alkane which gives four structural isomeric monochloro products ?
C C CC

Q.
Ans.

C5H12

= 72g

Identify the structure of hexane which gives 3 monochloro products ?

Ans.

C
C C C C,
C

Q.

Find the no. of monochloro products of a fully saturated isomer of C4H6.

Ans.

DU = 2

Q.

CCCCCC

2 monochloro product
Find the structural isomers of
product?

fully saturated cycloalkane of M.F. C6H12 which gives two monochloro

Q.

Q.

Ans.

Cl / h
2

A
C8H17 Cl
(C8H18 )
(Only one type)

Identify A ?

Page-15

Q.

Ans.

C C
C C C C
C C

Write all isomeric alkynes which produce an isomer of heptane which on further monochlorination gives
(a) three monochloro products.
CC
(i) C C C C C

(b)
Ans.

two monochloro
Nil

Q.

Find the structure of lowest molecular weight hydrocarbon and maximum unsaturation which on hydrogenation produce such an alkane which gives two monochloro products ?

Ans.

C = C = C or C C C

Q.

Determine the M.W. of maximum unsaturated hydrocarbon which on hydrogenation gives C6H12 which on
further chlorination gives two monochloro.

C
(ii) C C C C C
C

Ans.

CH2

Ans.
CH2

CH2

C6H6 = 78g

Ozonolysis :
It tells about position of unsaturation.
Remarks:(1)

Alkene and polyalkene on ozonolysis undergo oxidative cleavage.

(2)

(a) The reagent of reductive ozonolysis is


(i) O3 (ozone)
(ii) Zn and H2O or Zn and CH3COOH or (CH3)2 S
(b) The reagent of oxidative ozonolysis is O3 and H2O2.

(3)

The products are carbonyl compounds (aldehydes or ketones). This type of ozonolysis is known as reductive
ozonolysis.

(4)

Ozonolysis does not interfere with other F.G.s.

(1) O3
General Reaction:- R CH = CH R
R CH = O + O = CH R + ZnO + H2O
(2) Zn/H O
2

Ex:-

(1) CH2 = CH2

(1) O3
CH2 = O + CH2 = O
(2) Zn/H2O

(2) CH3 CH2 CH = CH2

(1) O3
CH3 CH2 CH = O + O = CH2
(2) Zn/H2O

(3) CH2 = CH CH2 CH = CH CH3

O3 / Zn

CH2 = O + O = CH CH2 CH = O + O = CH CH3


(4)

O / Zn
3 + OHC CH2 CHO (Propandial)
Page-16

Applications:
The process is used to determine the position of C = C in a molecule.
If the products are rejoined, the position of C = C can be determined in the reactant molecule. All C = C (except

aromatic ones) undergo oxidative cleavage under normal conditions.


At higher temperature, the aromatic double bonds can also undergo ozonolysis.

O3

O = C C C C C = O + O = CH2

(1)

Zn

O ()
3

(2)

(4)

Q.

CH = CH CH3

low temperatur e

(3)

Zn

CH = O

O3 / Zn

CH = CH

+ O = CH CH3

O3

C6H5 CH = O
Zn

H / Ni
Cl / h
2 CnH2n 2 2
CnH2n1Cl
(P)
CnH2n 2
( Q)
(m products )
Single Compound
m3
(no isomer )

H2O2 O3(oxidative)

CH3
HCOOH + CH3 C COOH
CH3

Identify P ?

Ans.

P=

Q.

An unsaturated hydrocarbon on ozonolysis produces 1 mole of

Ans.

Find the structure of the hydrocarbon and the no. of monochloro products formed by hydrogenation.
,
5 monochloro product

, 1 mol CO2, 1 mol

X
H / Ni
2
(Unsat. hydrocarbon)

Q.

Cl2

m products
h
(m 3 )

O 3 (Zn/H2O)

identify structure of X ?
O

Ans.

X =
Page-17

Q.

H / Ni
2
X
(Unsat. H.C.)

Cl / h
2
m products
(m 7 )

O 3 (Zn/H2O)

HCHO + 4(1-oxoethyl) Cyclohexan-1-one.


Identify X ?

C
X

Ans.

C=CC

Q.

Identify structure of X ?

Ans.

X is

Q.

H2
CCCCCC
X

O3 (Zn)

CH3CHO + CHO CHO


Identify structure of X ?
Ans.

X is C C = C C = C C

Q.

CH3

CH
3

Q.

CH3

Q.

O3

Zn, H2O

O3

Zn, H2O

CH3

CH3
C C
+2

CH
3

Q.

O O

Methyl glyoxal + Formaldehyde


Page-18

Stereoisomers (Classification)

Steriosomers :
The stereoisomers has different orientation of groups along a stereo centre. A stereocentre can be C = C
(any double bond), a ring structure, asymmetric carbon atom (*Cabcd). These isomer has same general
formula, structural formula and molecular formula but different stereochemical formula.
E.g.

CH3

C=C

H
CH3

(I)

CH3
H
H

(II)

C=C
H
CH3
CH3CH2CH=CH2
I, III
II, III
I, II

(III)

Positional
Positional
Stereoisomer

Configurational isomers :
Configurational isomerism arises due to different orientations along a stereocentre and these isomers can
be seperated and these isomers do not convert into one-another at room temperature. Therefore, they are
true isomers. They can separated by physical and chemical method.
E.g.
Cis2Butene
Trans-2-Butene

Conformational isomers :
When different optical orientations arise due to the free-rotation along a sigma covalent bond. Such isomers
are called conformational isomers.
E.g.
eclipsed ethane and
staggered ethane
These change into each other at room temperature and can never be isolated. So these are not considered
as true isomers.

Geometrical Isomerism
1.

Cause of Geometrical isomerism :


Geometrical isomerism arises due to the presence of a double bond or a ring structure
C = C, C = N, N = N, or Ring structure (Stereo centres)
Due to the rigidity of double bond or the ring structure to rotate at the room temperature the molecule exist
in two or more orientations.
This rigidity to rotation is described as restricted rotation/hindered Rotation/No rotation.
E.g.

C=C
(I) b

The root form of geometrical isomers lie in restricted rotation.

a
b

(I)

a
(II)

b
Page-19

Condition
(i) The two groups at each end of restricted bond must be different.
1
3
C=C
2
4
Caa Caa
X
Caa Cbd
X
Cae Cb2
X
Cab Cab

Cab . Cbd
Cab Cde

(ii) In two geometrical isomer the distance between two particular groups one the ends of the restricted bond
must be changed.

Q.

Which of the following compounds show G.I.


(1) Ethene

(2) Propene

(3) 2-Methylbut-2-ene CH 3 C CH CH3


|
CH3

(4) But-2-ene CH3 CH = CH CH3

(5) Penta-1, 3-diene C = C C = C C

(6) 1, 2-Dideuteroethene

H2C = CH

(7) Phenyle thene


Ans.

(8) Buta-1, 3-Diene C = C C = C

4, 5, 6

1. Geometrical isomerism across

Nil

and

By E / Z

2. Geometrical isomerism across


(a) Imine (
)
Imine compounds are produced from carbonyl compounds on reaction with ammonia.

(Syn and anti)


Imines prepared from unsymmetrical addehydes and ketones, always show geometrical isomerism.
Page-20

Q.

Which of the following compounds show geometrical isomerism after reaction with NH3.
O
||
(a) CH3 C CH3

O
||
(d) CH3 C H

(g)

Ans.

O
||
(b) H C H

O
||
(c) H C D

(e) Ph C CH3
||
O

(f) Ph C Ph
||
O

(h)

(i)

c, d, e, g, i
(b) Oximes

C = N OH :

They are prepared by reacting carbonyl compuond with hydroxyl amine (NH2 OH)
R
H

C = NOH
H
(Aldoxime)
OH

C=N
H

H2O
+ H2 NOH

C=O

(I)
(syn)

OH

C=N

and

(II)
(anti)

Syn and anti in aldehyde only not for ketones.


* Except formaldehyde (CH2O) All other aldehyde form two oximes.
* Unsymmetrical ketoes form two oximes.
Eg.

Which of the following ketones will form two oximes.


(1) Propanone
CCC=O
(2) Butanone

CCCC=O
H

(3) 3-Pentanone

CCCCC
O

(4) Acetophenone

C 6H 5CCH 3
O

(5) Benzophenone

C 6H 5CC 6H 5
O

O
(6) Cyclo hexane
O
Me
(7)
Methyl Cyclohexanone
Ans.

1, 2, 4, 7

Page-21

Q.
Ans.

The lowest molecular weight of acyclic ketone and its next homologue are mixed with excess of NH2 OH
to react. How many oximes are formed after the reaction ?
3
(c) Hydrazones

C = N NH2 :

H2O
C = O + H2N.NH2

H
hydrazine

C = NNH2
H
R

NH2

R
+

C=N
H

(I)

NH2

C=N
H

(II)

(Geo. diastereomers)

Q.

Ans.

Two chain isomer of a cycloalkanone which are next higher homologue of lowest molecular weight,
cycloalkanone reacted with hydrazine. Identify the structure and number of isomer of hydrazones prepared ?
..
..
N
NH2
NH2
N
N ..
O +
+ H2N NH2
+
+
NH2
CH 3
CH3
O
CH
3

Number of isomer = 3
(3) Geometrical isomerism across azo compounds ( N = N )
(i) H N = N H (H2N2)

(ii) Ph2 N2 (Azobenzene)

..

..
N=N
Ph

syn

Ph

..

Ph
..

N=N
anti

Ph

(4) Geometrical isomerism across ring structure

(i)

Restricted rotation

(ii)

(iii)
Page-22

(5) Geometrical isomerism in cycloalkenes across double bonds :


In cycloalkenes, G.I. exists across double bonds with ring size equal to or greater then 8 carbon atoms (due
to ring strain)

Stereocentre
An atom or bond across which stereoisomerism exists (either G.I. or optical isomerism)

These compounds which are not mirror images of each other are diastereomers. These compounds which
are non-superimponsible mirror-images of each other are enantiomers

are enantiomers

Number of geometrical isomers


Case I : Compounds having dissimilar ends
No. of G.I. = 2n
where n = number of stereocentre
Ex.
Ans.

Stereocentre = 2
Geometrical isomerism = 4

(a)

(b)

(c)

(d)

Case II : Compounds with similar ends even no. of stereocentre.


n

Ex.1
Ans.

No. of Geometrical isomerism = 2n1 + 2 2


CH3 CH = CH CH = CH CH3
Stereocentre = 2
Geometrical isomerism = 21 + 20 = 3

Page-23

Ex.2

Cl CH CH

CH CH

Ans.

Stereocentre = 4
Geometrical isomerism = 23 + 21 = 10.

Case III : Compounds with similar ends but odd number of stereocentre.
No. of Geometrical isomerism = 2n1 + 2
Ex.1
Ans.

n 1
2

CH CH = CH CH = CH CH = CH CH3
Stereocentre = 3
Geometrical isomerism = 6

E/Z Nomenclature :
Z (Zussamen = together) a > b and e > d

E (Entagegen = opposite) a > b and e > d


Rules :(i) The group with the first atom having higher atomic number is senior.
Thus F > CH > NH2 > CH3
(ii) If the first atom is identical, then second atom is observed for deciding the seniority of the group.

(a)

(b)

<

(c)

<

(d)

>

Ex.

Ex.

E
(iii) If the first atom has same atomic number but different atomic mass, that is isotopes. Then heavier
isotope has higher seniority.
Page-24

(iv) If the group has unsaturation, then a hypothetical hypothetical equivalent in drawn for it and it is compared with other group for seniority.

(1)
(2) CH = CH2 < C CH

Remark : Bond pair is always senior to lone pair.


CH 2 = CH

Ex.

(1)

HC

C == C

C(CH3)3

E
CH CH = CH2

(2)

N
(3)

CH2 C(CH3)3

H2C = C = CH

C == C

CH

(3)

(4)

(5)

Page-25

Physical properties of Geometrical isomers :


The physical properties of organic compounds can be compared through the knowledge of their molecular
formula, structural formula and stereochemical formula (S.C.F.)

(1) Dipole moment () : Polarity of an organic molecule.


The organic molecules are composed of covalent bonds, every covalent bond has its own dipole moment
which is known as bond moment.
It is expressed by given formula :
=qd
Where q is partial charge on individual atoms A and B whose value increases with increase in E.N. difference
between A and B. and d is the internuclear separation.
If = zero, E.N. difference is zero or very less and bond is non-polar.
Ex.

(1) H F > H Cl > H Br > H I

()

(2) C C < C N > C O < C F

()

Dipole moment of the molecule :


It is the vector sum of the individual bond moments.
If the vector sum of individual bond moments becomes zero, then the molecule as a whole is said to be nonpolar.
Ex.

(i) O = C = O

Non-Polar

(ii) S = C = S

Non-Polar

(iii)

Polar

(iv)

Polar

(v)

Polar

Note. CH3 Cl > CH3 F > CH3 Br > CH3 I


because M = q d
qCH Cl qCH
3

3 F

but

Thus,

CH3 Cl > CH3 F

But,

H F > H Cl.

dCH3 Cl dCH3 F

Dipole moment of some Functional Groups : (order)


> COX > COOH > OH > NH2 > R X
(2.8 3 D)

> ROR

(X = Cl, Br, I)

> R C C H > R CH = CH2 > R CH2 CH3


(non polar)
(non polar)
Page-26

Dipole moment for Geometrical isomerism :

(A)

(cis)

(trans)

Thus Alkene Cab = Cab type,


= cis> trans (= O)
(B)

Unsymmetrical Alkene (Cab = Cad )

(i)

<

(ii)

<

(iii)

CH3 CH = CH COOH (Trans > Cis)

(iv)

>

Ortho > Meta > Para


If two isomers have different dipole moments then their all physical properties are different. (melting point,
boiling point, solubility, refractive index, density)
All structural isomers have different , and thus different physical properties.
In case of stereoisomers, all diastereoisomers have different dipole moments and thus different physical
properties.
All geometrical isomers are diastereoisomers and thus posses different diople moment and Physical properties.
Separation of isomers : The isomers having different physical properties can be separated by normal
physical methods of separation.

(2) Boiling Point :


Intermolecular forces of attraction :
H bond > Dipole Dipole interaction > Vander-wall force.
The boiling point of a compound depends on the intermolecular forces of attraction existing between two
molecule. If a compound has strong forces of attraction, then the B.P. is high.
Among homologs, molecular weight increases, Vander Wall force increases, Boiling point also increases
Ex.

(a) CH4 < C2H6 < C3H8


(b) CH3OH < CH3 CH2 OH < C C C OH
(c) H CHO < CH3 CHO < C2H5CHO

Page-27

Among structural isomers


(1) Functional isomers (H-bond > Dipole Dipole > Vander Wall force)
COOH > OH > NH2 >

> R X > ROR > R C CH > R CH = CH2 > R CH2 CH3

(a) Among COOH, OH, NH2 H-bond

(b) C = O, R X, R OR, R C CH Dipole Dipole


(c) R CH = CH2, R CH2 CH3 Vander Wall force
In acids, there is dimer formation

O ------ H O

CR

RC

dimer

O H ------ O

In isomeric ketones and aldehydes, BPKetone > B.P..Aldehyde


In chain isomers, as branching , surface area of molecule VDW forces Boiling Point
Thus, BP 1 > 2 > 3 (OH, NH2)

(i) C3H8O

C C C OH

> C C C

Eg:-

OH

C C C C OH > C C C OH > C C C C > C C C


OH
C
OH

(ii) C4H10O

Among stereoisomers:-In geometrical isomer, the dipole moment of geometrical isomer is always different.
More polar geometrical isomer has higher B.P.
(a) Cab = Cab
B.P.cis > B.P.trans
(b) R CH = CH X

B.P.trans > B.P.cis

COOH
H
H
>
C=C
C=C
H
COOH HOOC
COOH
Fumaric acid (trans)
Maleic acid (Cis)
H

(c)

CH3

CH3

H
C=C

(d)

+CHO

CH3

(e)
H

NH2

CH3

C=C

>

C=C

CHO
C=C

>

NH2

Among Disubstituted Aromatic Compounds:(i) C6H4Cl2


ortho B.P. > meta B.P. > para B.P.
(ii) C6H4(OH)2
ortho B.P. < meta B.P. < para B.P. (due to H-bonding)
OH

OH

OH
Less
Intermolecular
H-bonding

Ortho
5-membered
Intramolecular
H-bonding

OH

OH

OH
More
Intermolecular
H-bonding
Page-28

(3) Melting Point:


The melting point of an organic compound depends upon its packing in solid state. The packing depends on
following factors:(i) Intermolecular forces of attraction:- (H-bond > Dipole Dipole > Vander Wall force) in structural
isomer.
(ii) Symmetry of the molecule:- More symmetrical molecules are more closely packed.
In geometrical isomers the trans isomers are more symmetrical than cis isomers (Cab = Cab type of alkenes)
So trans form have higher M.P. than cis isomers.
Eg:- (I) (a) CH2 = CH2 < CH3 CH = CH2 < CH3 CH2 CH = CH2
Homologues: Molecular weight increases vander wall force increases melting point increases.
(b) CH2 = O < CH3 CH = O < CH3 CH2 CH = O

<

Et

(c)

CH3
<

<

(II) Structural isomers:(a) Functional isomers:(i) R COOH

>

H C OR
O
(No H-bonding)

(H-bonding)
H-attached to O
(ii) CH3 CH2 CH2 CH2 OH
(H-bond)

H with R
CH3 CH2 O CH2 CH3
(No H-bond)

>

(iii) CH3 CH2 CH2 CH2 NH2 >


(1)

CH3 CH2 CH2 NH CH3


(2)

> CH3 CH2 N(CH3)2


(3)

(b) Chain isomers:

C
(i) C C C C > C C C
CH3
|
**Exception :- (ii) CH3 C CH3 > CH3 CH2 CH2 CH2 CH3 > CH3 CH CH2 CH3 (M.P.)
.)
|
|
CH3
CH3

Neopentane (spherical) (Close-packing)


For B.P.:- n > iso > neo
For M.P.:- neo > n > iso
(III) Geometrical isomers:Cab = Cab type
a
b

.C
C=
*
a

a
C=C
b

Elements of symmetry:- 2 Planes of Symmetry


1 Plane of Symmetry
It has a centre of symmetry ().
No centre of symmetry.
The symmetry of a molecule can be described by observing symmetry elements.
Plane of Symmetry (P.S.) :- It is defined as any plane in the molecule which bisect the molecule into 2
equal halves, which should be mirror images of each other. A molecule can have more than one P.S.

Page-29

Centre of Symmetry (C.S.) :- If we start from one point of the molecule, reach to centre and then go to
equal and opposite distance (in same direction), then if similar point is obtained, then the molecule has a
C.S.
(It should be applicable to all the points of the molecule).
The trans isomers has more no, of symmetry elements than cis isomer; so it is more closely packed in solid
state and has higher M.P.

Melting point in geometrical isomers :


Cl
H
H
H
C=C
C=C
Ex.:- (1)
>
H
Cl
Cl
Cl
H

Me
(2)

>

C=C
Cl

Cl

(3) Maleic acid < Fumaric acid


(4) Stilbene (Ph CH = CH Ph) E > Z
(IV) ortho, meta, para isomers

Cl

Cl

Cl

Cl

Cl
Cl
(m)
(o)
(p)
less polar
more polar
Most symmetric
para > ortho > meta (we see polarity now, if H-bonding doesnt exist)
(1)

OH

OH

OH

OH

OH
(p)
(2)
Symmetrical
H-bond
(intermolecular)

OH
(m)
Intermolecular
H-bond

(o)
Intramolecular
H-bond

Thus, para > meta > ortho (if H-bonding)

(4) Water Solubility :


Criteria:- H-bond > Dipole dipole > Vander Wall forces (insoluble) between solute and solvent
Homologs: Hydrophilic water loving H-bond
Hydrophobic water repelling Hydrocarbon
As M.W.. , solubility .

Ex:-

(i) CH3OH > C2H5OH > C3H7OH > C4H9OH


OH
OH
(ii)

(I)

>

Me >

(iii) Formic acid > Acetic acid > Propanoic Acid > Butanoic acid
(II)

Structural isomers:(1) Functional isomers:(a) COOH > NH2 > OH >


H-bond
> R CH = CH2 > R CH2 CH3
insoluble (VDW)
Page-30

(b)
(c)

R COOH > HCOOR

(d)

R CHO > R2C = O

(2) Chain isomers (Effect of Branching):As branching (in Hydrocarbon) , Surface Area of hydrocarbon so, water solubility (as area repelling
water decreases)
Degree:- 3 > 2 > 1 (OH)
C C C OH < C C C.........Solubility
OH
C C C OH > C C C.........B.P..
OH

(i) M.F. = C3H8O

Ex:-

(ii) C4H10O

C
C
C C C C OH < C C C OH < C C C C < C C C
OH
OH

(iii) C4H8O2 (acid)

CH3 CH2 CH2 C O H


O
(III)

CH3
|
CH3 CH CH C O H
O

<

Geometrical Isomers:- More Polar geometrical isomer is more soluble in water.


(i)

>

(ii)

Cis > Trans

<

COOH

COOH
C=C

(iii)
H

Trans > Cis

COOH

H
C=C

>
COOH

Cis > Trans


H

Optical Isomerism
Some organic compounds can rotate the plane of plane-polarised light. Such compounds are called
optically active compounds.
The optically active compound can show optical isomerism.
Measurement of optical activity
It is measured by an instrument called polarimeter.

=
(1)

(3)

(5)

(6)

Recorder
(8)

Page-31

(1) Source of light


(2) Polychromatic Non-polarised light
(3) Slit (Monochromator)
(4) Monochromatic Non-polarised light
(5) Polariser (Prism-setting)
(6) Monochromatic plane-polarised light
(7) Sample tube ( = path length)
(8) Recorder for measurement of optical rotation
Observations:- When plane polarised light is passed through sample tube, then following changes can be observed
in the recorder:Angle of rotation ()
(1) = 0
(2) = +x (clockwise rotation)
(3) = x (anticlockwise rotation)

Inference
Compound is optically inactive.
Optically active, dextrorotatory or d or (+).
Optically active, laevorotatory or l or ().

Specific Rotation:- The specific rotation of a compound indicates the optical rotation of unit concentration (1 g/mL)
present in a sample tube of 1 dm of path-length at given temperature and given wavelength of light. It is
represented as follows:-

t 25 C

[ ] 580 nm
where

= observed angle of rotation


c = concentration in g/mL (or density)
= Path length of Sample tube in dm

Q.

Compound X has = +70 for 2 g/mL solution in sample tube of = 1 dm. Calculate ?

Ans.

(1)
(2)

70
= +35
2
Its concentration is made twice, the observed rotation() will be 140 but = 35
If = +70, it will be a
(i) d compound or (ii) compound of = (360 70) = 290
It can be decided by changing the concentration or by changing the length of the tube (c or ).
If concentration is reduced to half, d will have +35 and will have 145 (not distinguish) still halfed, it will
give +17.5 and 72.5 to distinguish.

(I)
(II)
With symmetrical
With asymmetric
molecule
molecule
[] = 0
[] 0
Optically inactive compounds:These compounds have symmetrical molecule, so the optical rotation observed after interaction of light is
zero.
But in case of optically active compounds. The molecules are asymmetric in nature and show non-zero
optical rotation.

Symmetry of elements :(1) Centre of symmetry (C.S.)


(2) Plane of symmetry (P.S.)

Cl
H

R
C=C

Ex:-

H
R
Centre of symmetry

Cl
Centre of symmetry

Page-32

Dissymmetry:- The molecules or objects in which minimum two elements of symmetry (Centre of symmetry and
Plane of symmetry) are absent are called dissymetric molecules/objects.
Asymmetry:- When all the elements of symmetry (23 including Centre of symmetry and Plane of symmetry are
absent) the molecule is said to be asymmetry.
So, all asymmetric molecules are always dissymmetry, but the reverse is not true.
Dissymmetry and chirality:- All dissymmetric molecules are chiral and are optically active.
Dissymmetry, Chirality and Optical Activity:- Dissymmetry/Chirality is the minimum and sufficient condition for a
molecule to be optically active. So, if in a molecule, a C.S. and P.S. are absent, the molecule will be optically
active. All asymmetric molecules are also optically active.
Chirality (Hand-like property or Handedness):- The human hand does not have Centre of symmetry and Plane
of symmetry , so it is dissymmetry. It does not have any element of symmetry, so it can be called
asymmetry. Any molecule which has this property is called chiral.
Note : All dissymmetric compounds are chiral.

Optical Isomers:Enantiomers:- The mirror-image stereoisomers are called enantiomers.


Two types:(a) Dextrorotatory
(b) Laevorotatory

Enantiomers are always mirror image isomers.


They have same molecular formula, structural formula but have different orientation in space.
They have dissymmetry/chirality.
Every enantiomer is optically active.
The two enantiomers can rotate the plane-polarised light with equal magnitude and opposite signs.
They have similar physical properties except the sign of optical rotation.
These are the isomers which have maximum resemblance with each other.
These can be distinguished only by polarimeter.

Chirality (Dissymmetry) and Optical Isomers:(a)


(b)
(c)
(d)
(e)

The dissymmetric molecules have two orientations in space. These two orientations are called
stereoisomers, optical isomers, enantiomers.
These are mirror images (enantiomers).
Non-superimposability of enantiomers:- The dissymmetric molecules are always non-superimposable
on their mirror-image orientations.
The non-superimposable orientations are non-identical orientations, so are called isomers.
Because of dissymmetry, these two isomers are capable of rotating plane-polarised light. So, these are
called optical isomers.

Optically Active Carbon Compounds:If a carbon-atom is attached with four different group, then if does not have any element of symmetry. It is
known as asymmetric carbon atom, which is represented as *Cabde.
a
C*
e
d
If a molecule contains only one asymmetric carbon atom, then the molecule as a whole becomes chiral and
optically active and show optical isomers.
b

Centre of symmetric

Plane of symmetric

Optical active

H
C

(1)
H

Absent

Yes

No

Absent

Yes

No

H
C

(2)
H

Cl

Page-33

H
C

(3)
Br

Cl

Absent

Yes

No

Absent

No

Yes

H
C

(4)
Br

Cl

Ex.1:- Mark the chiral objects:(i) Cup


(ii) Plate
(vii) Shoe
(viii) Glove
Ans.

(iii) Letter A

(iv) Letter G

(v) Fan

(vi) Door

IV, VII VIII

Projection Formula of Chiral Molecules:(i) Wedge-Dash Projection formulae


down
up

Ex:-

(i) Butan-2-ol
CH3
C
H

OH
C2H5

(ii) Fisher Projection formula


(i) Butan-2-ol

(CH3 CH2 CH CH3)

Ex:-

OH

CH3
H

OH
CH2CH3

Ex:-

///////////////////////

Rules of writing Fisher Projection formula :(i) It is represented by a cross (+).


(ii) Groups at Vertical line are away from observer.
(iii) Groups at Horizontal line are towards the observer.
(iv) Centrol C atom of the cross is chiral.
(v) High priority group lies at the top of vertical line (Numbering starts from top).

Draw Fisher Projection formula of following molecules:-

(1) 2-chlorobutane

(2) Pentan-2-ol

Page-34

*
(3) CH2 CH CH
OH OH O

*
*
(4) CH3 CH CH CH2 CH3
OH OH

(I, II), (III, IV) Enantiomers.


All other diastereomers.
They are true isomers (not superimposable)

CHO
CHOH
CHOH
CHOH
CHOH
CH2 OH

(5) Glucose

Mark:- (i) No. of C* 4


(ii) Draw one Fisher Projection Formula
CH = O
H

OH

OH

OH

OH

Configuration 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) : Application on correct Fisher Projection Formula
This method is used to relate the configuration of sugars and amino acids to the 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.

Page-35

Examples :

Sugars have several asymmetric carbons. A sugar whose highest numbered chiral centre (the penultimate
carbon) has the same configuration as D-(+)-glyceraldehyde ( OH group on right side) is designated as a Dsugar, one whose highest numbered chiral centre has the same configuration as L-glyceraldehyde is designated as an L-sugar.

e.g.

(I) R/S Configuration :


R Rectus

S Sinister

Examples :
a
b

(1) Seniority order a > b > c > d


(2) Put junior most group at dotted line
b

(3)

Q.

c
a
d
Now go from a to b, b to c.
(i) If it follows clockwise route, it is (R).
(ii) If it follows anticlockwise route, its configuration is (S).
Br
Br

Cl

Cl
F
(S)

(R)

R/S Configuration in Fisher Projection Formula :(c)

Me(c)

Ex:-

H(d)

Et(b) (d)
Pr
(a)

(b)

abc

Clock wise

(a)

Page-36

If the juniormost group is at horizontal line clockwise S


anticlockwise R
If juniormost at vertical line, then
clockwise R
anticlockwise S

Q.

(1)

Ans. R

(2)

Ans. R

(3)

Ans. S

Properties of enantiomers :One chiral carbon :


(i) Number of optical isomer = 2 (d or )
(ii) Number of Racemic Mixture Equimolar mixture of d and . [] = 0 due to external compensation of
optical rotation.

Properties:(i) Dipole moment


(ii) Boiling Point
(iii) Melting Point
(iv) Solubility
(v) Specific rotation []

same
same
same
same
different

Molecules with more than one chiral carbons:(I) Calculation of No. of optical isomer :Case I:- When all Chiral carbon atoms are differently substituted (all are dissimilar C*)
optical isomer = (2)n
Case II:- When all the Chiral carbon atoms are similar at ends.
n

(i) n = even
x = 2n 1 + 2 2
(ii) n = odd
x = 2n 1
Molecules with two Asymmetric Carbon Atoms of Dissimilar Nature:(i) Structural formula
CH3 CH CH CH2 CH3
Cl
Cl
n
2
(ii) Optical isomer = 2 = 2 = 4

Page-37

(iii) Stereochemical Formula:-

CH3

CH3

CH3

Cl

Cl

H H

Cl

Cl

H; Cl

C2H5

C2H5

I
[] = +x

CH3
Cl

Cl

C2H5

II
x

Cl
C2H5

III
+y

Analysis:(a)
I, II Enantiomers
I, III Diasteromers
II, III Diasteromers

IV
y

III, IV Enantiomers
I, IV Diasteromers
II, IV Diasteromers

(b) No. of Racemic Mixture Two (I + II, III + IV).

n = 3,
x = 23 = 8 (4 d- pairs)

Ans.

CH3 CH CH CH CH2 CH3


Cl
Cl
Cl
Calculate total number of optical isomer.

Q.

(i)

(ii)

(ii)

(iii)

(iv)

and their mirror images.


4 Racemic Mixtures (4 different boiling point on fractional distillation)

Compounds with 2 Asymmetric Carbons of Similar Nature:Ex:CH3 CH CH CH3


OH OH
(i) n = 2
n

(ii) x = 2n 1 + 2 2 = 3 (Optical stereoisomers).


(iii) Stereo chemical formula :Me
H

OH

OH
Me
(I)
(II)

In (I and II)
Plane of symmetry present.
Superimposable on its mirror image.
Thus, I and II are identical.
[] = 0, optically inactive.
Meso isomer

In (III) Specific rotation [] = +x


In (IV) Specific rotation [] = x
No. of d pairs = 1 (III + IV) = No. of Racemic mixtures

(III)

In (I) and (II) : [] = 0 due to internal compensation and Non-Resolvable


In (III) and (IV) : Resolvable [can be separated into two isomers (enantiomers)]

(IV)

Page-38

Meso isomers: The optical stereoisomers which have more than one no. of asymmetric carbon atoms but have a plane of

symmetry are called meso isomers.


They are achiral (optical rotation = 0).
They have [] = 0 due to internal compensation of optical rotation.
They are diastereomer of d pair. So, it has different physical properties than d -pair..
Presence of more than one asymmetric C atoms.
They are non resolvable.

Q.

Mark meso isomers among following


H

COOH
OH

(1)

(2)
H

Ans.

OH
COOH

Cl
Me

Cl

(3)

(4)

Me

OH
H

(5)

*
OH

(1) (2) (4) and (5)

Molecules with three similar chiral carbon:


Ex:CH3 CH CH CH CH3 M.F..
Cl
Cl
Cl
n=3
x = 2n 1 = 4 stereoisomers.
Stereo Chemical Formula :-

\\\\\\\\\\\\\\\\\\\\

(I)
2S
3S
4R

(II)
2S
3R
4R

(III)
2S
3 achiral
4S

(IV)
2R
3 achiral
4R
Optically active

(i) Achiral due to Plane of symmetric. (Optically inactive).


(ii) Achiral due to Plane of symmetric. (Optically inactive).

Properties of Optical Diastereomers:The optical isomer which are neither mirror image nor superimpossible to each other are called optical
diastereomers.

Conclusion:- Optical Diastereomers have different physical properties, so these can be separated by normal
physical methods of separation.
(i) By fractional distillation (different B.P.)
(ii) By fractional crystallization (different solubility)
(iii) Chromatography (different solubility)
(iv) Differential Melting (M.P. diff.)
Page-39

Assertion:- All diastereomers have different polarities (Both Geometrical and Optical) True
Assertion:- Geometrical isomer are always diastereomers True

Resolution of d mixture (Racemic Mixture):- The enantiomers in a d pair have identical physical properties, so these cannot be separated by using normal physical methods of separation. The special methods
used for separation of d pair is known as resolution.

Chemical method of separation (resolution) by using optically active reagent: General scheme of resolution:-

d+
+ d'
Racemic Optically
mixture
active
Reagent

Hydrolysis

Hydrolysis

d + d'

(I) Resolution (by using Esterification) of RCOOH and R'OH

Example:-

Esterifica tion

General Reaction:- R C O H + H O R ' R* C O R'


(H2 SO 4 )
O
O
H2O
Me
H

COOH
(d)

Me

Et
Et

+ OH

H
D
(d')

COOH
( )

H + H
(dd')

CO
O

(d')

O
D
( d ')

(dd')

Me

H
( d' )

CO
Me

Et

Me

Et

Me

Me

Pair of Diastereomers
Ester upon still hydrolysis will give back the carboxylic acid and alcohol.
(II) Separation of (d ) pair of alcohol by using optically active acid:D

Ph
+

H
(dd')

OC
O
Me

Me

Ph

Me

CO
O
( d' )

Me

(III) By salt formation (RCOOH + RNH2)

R COOH + R' NH2


(d )
(d' )

R COO R' NH3


( dd' d' ) salt

Page-40

Optical Purity or Enantiomeric Excess (O.P. or E.E.):Ex:Compound X has [] = 70


We have mixture of enantiomers in different percentage. %E.E.

(obs)
100%
[]specific

Optically active compounds without a chiral carbon:Rapid


R
R
Inversion

Asymmetric N:R' N
N R'
R''
R''
A nitrogen atom attached with 3 different groups (sp3) is chiral, asymmetric.
In case of acyclic compounds, the Nitrogen, having trigonal pyramidal shape undergoes rapid inversion of shape
at room temperature. So at room temperature, everytime a racemic mixture of d and forms exists.
This racemic mixture can never be resolved at room temperature.
Nitrogen converts into its enantiomer..

So, acyclic molecules with chiral nitrogen are chiral but optically inactive ([] = 0) and are non-resolvable.
If asymmetric Nitrogen atom is present in ring structure, then inversion does not take place and such molecules are
optically active [] 0 . (otherwise ring will break)

Ex:-

Me
N

[ ] 0

Optical activity without asymmetric carbon :


CCCCC
(Cumulated double bond)

One after another

CCC CC
(Conjugated double bond)

Alternate

C CCC C
(Isolated double bond)

Separated

(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.

Page-41

(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.

(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.

Page-42

Lecture # 14
CONFORMATIONAL ISOMERISM :
1.

Free Rotation : A sigma covalent bond undergoes free rotation at room temperature.
(CC, C O, CN, NN, OO)

2.

Conformers / Rotamers or conformations : The infinite number of spatial oreintation of molecule is arise
due to free rotation along a sigma covalent bond or rotamers.

3.

Conformational Isomers : The conformations of extreme energy different are called conformational isomers but these are not true isomers and can never be isolated.

4.

Conformational energy : The potential energy different b/w 2 conformational isomer is called conformational energy. It has very low value i.e. (1020 kJ/ mole) which is available at room temperature.
Projection formula
(a) Saw horse Projection formula
Ex.

CH3 CH3

rotation

Eclipsed

Staggered

(b) Newmann Projection formula

1
12.5 kJ / mol

Energy - Level Diagram

Page-43

Ex.

CH3CH2CH3

Saw horse Projection formula

Eclipsed

Staggered

Newman Projection Formula


CH3
H

CH3
H

60

H
H
II
Staggered

Eclipsed

120

HH

H
III
Eclipsed

CH3
H
H
H

H
H
IV
Staggered

Propane :

Butane :
Ex.

Ethyl-hydrogen repulsion is less than methyl-methyl repulsion.


CH3

CH3
CH3

60

H
H

HH
(I)

CH3
CH3

120

H
(II)

180

CH3
H
H
240

CH3

(IV)

H CH3 H H
(V)
Page-44

300

360

I/VII = Fully eclipsed


II/IV = Gauche form or skew form
III/V = Partially eclipsed
IV = Anti form
Stability Order : IV > II > III > I
P.E. Order : IV < II < III < I
Potential Energy Diagram :

Conformational Isomers : Due to free rotation from 0 to 360 those conformations which are most stable
and have minimum P.E. are defined as conformational isomers. They maay have same energy and such
isomers are called degenerate isomers or equienergic isomers.
The conformational isomers with different energies are called non-degenerate isomers.
The conformational isomes lie at the P.E. minima in the P.E. diagram with respect to rotational angle.
Conformational Energy (C.E.)
The rotational energy barrier is known as conformational energy. It is the P.E. difference between conformational at potential energy minima and maxima.
Angle of rotation/Dihedral Angle (D.H.A.)/Torsion Angle :
The interfacial angle between the groups attach at two -bonded atoms is defined as dihedral angle.

Strains :
(i) Torsional Stran (eclipsing strain) :
It is defined as the electronic repulsion between the bond-pairs of two adjacent eclipsed bonds. It is active at
torsional angles 0, 120, 240 which the molecule has eclipsed conformation. It is considered almost zero
in the staggered conformation. (D.H.A. = 60, 180, 300)
(ii) Vander Wall strain :
It is the repulsion between the group attached at adjacent bonds. The vander wall strain is maximum in
eclipsed conformation, and minimum in anti conformation, while intermediate in gauche (skew) conformations.
It is almost zero for H-atom since the sum of vander wall radii is less than internuclear distance between two
H atom.
(iii) Angle Strain :
It arises due to distortion in normal bond-angles. In acyclic compounds, there is no distortion of bond-angle
due to free rotation. So, all conformational have angle strain zero.
Page-45

Page-46

Ques. Draw conformation isomers of following compound (a) CH3 CH CH3

(b) CH3 (CH2)3 CH3

CH3
Ques. Draw conformation isomers of following compound CH3 CH CH CH3 with respect to C2 and C3 carbon
CH3 CH3

atoms.
H
H

H
60

180

CH
CH3 CH3 3
Eclipsed

CH3

CH3

H3CCH

CH3

CH3

CH3

120

H3C

H3C

CH3

H3C

CH3

H
Staggered

CH3

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.


Example 1.

CH2OH (Glycol).
CH2OH
OH
OH

H
H
(II) Gauche

Hydrogen Bonding : (II)


OH
H

OH

H
H
Gauche form most stable due to hydrogen bonding.
Stability Order : II > IV > III > I
H

Example 2.

O2N CH2 CH2 OH

Page-47

Example 3.

Tartaric Acid :
COOH CHOH CHOH COOH

Sterioisomers : 3
1. Meso

COOH
H

OH

OH
COOH

2. d/

COOH

COOH
H

Meso

COOH
H

OH

OH
COOH

OH

OH

H
H

COOH OH

COOH

COOH
COOH

H H

COOH
OH

OH

COOH

OH

OH

OH

d/
COOH

COOH
COOH
OH
H

OH

COOH

H OH

OH

COOH

COOH
OH

HH

COOH H
OH

COOH
COOH

OH

OH
COOH

COOH

OH
H
COOH OH
OH
Conformation isomers of cyclohexane : Superficial idea of chair & boat form (This is discuss in orientation class)
Page-48
H

OH