Isomerism

Part-01

Isomerism
Two or more than two compounds having the same molecular formula but different physical/chemical
properties or both properties are different are called isomers and this phenomenon is known as isomerism.

Isomerism

Structural isomerism Stereoisomerism

Chain Position Functional Metamerism Tautomerism

Configurational Conformational

Geometrical Optical

Structural Isomerism
Compounds which have same molecular formula, but have different structures are called structural isomers.

Chain Isomerism (C.I.)

The compounds which have same molecular formula, same functional group but length of carbon chain is
different, show chain isomerism.

Illustration 1.
1 2 3 4 1 2 3
(I) CH3—CH2—CH2—CH3 and CH3—CH—CH3

CH3
Butane (4C) 2–Methyl propane (3C)

4 3 2 1 3 2 1
(II) CH3—CH2—CH2—CH2—OH and CH3—CH—CH2—OH

CH3
1–Butanol (4C) 2–Methyl–1–propanol (3C)

1
3 2
5 2

4 1
(III) and 4 3

Methylcyclobutane (4C) Cyclopentane (5C)

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 Isomerism
Part-02

Position Isomerism (P.I.)

The compounds which have same molecular formula, same functional group, same parent carbon chain but
different position of functional group or multiple bond or substituents, shows position isomerism.

Illustration 2.
1 2 3 4 1 2 3 4
(I) CH2=CH–CH2–CH3 and CH3–CH=CH–CH3
But–1–ene But–2–ene

4 3 2 1 4 3 2 1
(II) CH3–CH2–CH2–CH2–OH and CH3—CH2—CH—CH3

OH
1–Butanol 2–Butanol

Cl 2
2
1 Br
(III) and 3
3 1
Br Cl

1-Bromo-2-chlorocyclopropane 1-Bromo-1-chlorocyclopropane

Degree of Unsaturation / Double Bond Equivalent/ Index of Hydrogen Deficiency

D.U/D.B.E./I.H.D. = No. of π bond + No. of rings

If D.U. = 0 (No π bond/ring)
D.U. = 1 (1 π bond/1 ring)
D.U. = 2 (2 π bonds/2 rings/1 π bond + 1 ring/1 triple bond)

Formula
(H + X – N)
D.U. = (C +1) –
2

C  Number of carbon atomsw H  Number of hydrogen atoms

X  Number of halogen atoms N  Number of nitrogen atoms

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Isomerism Part-02

Illustration 1.
(I) CH3–CH3 has D.U. = ____
(II) CH2=CH2 has D.U. = ____
(III) CH≡CH has D.U. = ____
Solution:
(I) CH3–CH3 has D.U. = 0
(II) CH2=CH2 has D.U. = 1
(III) CH≡CH has D.U. = 2

Illustration 2.
Find degree of unsaturation (D.U.) in-
(i) C4H8
(ii) Benzene

Benzene = C6H6
(iii) C2H5Cl
CH3 − CH2 – Cl

Solution:
(8+0-0)
(i) D.U. =(4+1)-
2
D.U. = 5 – 4 = 1
(6+0-0)
(ii) D.U. =(6+1)-
2
D.U. = 7 – 3 = 4
(5+1-0)
(iii) D.U. =(2+1)-
2
D.U. = 3 – 3 = 0

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 Isomerism
Part-03

Functional Isomerism
Compounds which have same molecular formula but different functional group, are functional group isomers.
Following compounds show Functional isomerism, as they have same molecular formula and different functional
group.

(i) Alcohol and Ether ⎯⎯→ CH3—CH2—OH and CH3—O—CH3

(ii) Aldehydes and Ketones ⎯⎯→ CH3—CH2—C—H and CH3—C—CH3

O O

(iii) Acids and Ester ⎯⎯→ CH3—C—OH and H—C—O—CH3

O O

(iv) Cyanide and Isocyanide ⎯⎯→ CH3—CH2—CH2—CN and CH3—CH2—CH2—NC

(v) Nitro and Nitrite ⎯⎯→ CH3—CH2—N O and CH3—CH2—O—N=O

O

(vi) 1°, 2°, 3° Amines

(i) CH3—CH2—CH2—NH2

(ii) CH3—NH—CH2—CH3

CH3
(iii) CH3—N—CH3

(vii) Alcoholic and Phenolic compounds (different chemical properties)

OH
CH2OH CH3
and

(viii) Alkyl halides do not show Functional isomerism due to different molecular formula.

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Isomerism Part-03

Metamerism
Compounds which have same molecular formula, same functional group but different alkyl groups attached to
polyvalent functional group.
Polyvalent functional group [Which have more than one valency] are :

O
–C
–O–, –S–, –C–, –C–O–, –C–NH–, –C–N– –NH–, –N–, O
–C
O O O O
O
ester 2° amide 3° amide 2° amine 3° amine

Illustration
(I) CH3—O—CH2—CH2—CH3 and CH3–CH2–O–CH2–CH3 are metamers

(II) CH3—CH2—NH—CH2—CH3 and CH3—NH—CH2—CH2—CH3 are metamers

(III) CH3—NH—CH2—CH2—CH2—CH3 and CH3–CH2–NH–CH2–CH2–CH3 are metamers

(IV) CH3–C–CH2–CH2–CH2–CH3 and CH3–CH2–C–CH2–CH2–CH3 are metamers

O O

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 Isomerism
Part-04

Number of structural isomers

(i) C5H12 has three structural isomers:

CH3
CH3–CH2–CH2–CH2–CH3 CH3–CH2–CH–CH3 CH3–C–CH3

CH3 CH3
Pentane 2–Methylbutane 2,2–Dimethylpropane

(ii) C6H14 has 5 structural isomers:

(a) CH3CH2CH2CH2CH2CH3 (b) CH3–CH2–CH2–CH–CH3
CH3

Hexane 2–Methylpentane

(c) CH3–CH2–CH–CH2–CH3 (d) CH3–CH–CH–CH3

CH3 CH3 CH3
3–Methylpentane 2,3–Dimethylbutane

CH3
(e) H3C–C–CH2–CH3   ⚫ (a–b), (a–c), (a–d), (a–e) ⎯→ Chain isomers
(b–d), (b–e), (c–d), (c–e)
CH3
2,2–Dimethylbutane   ⚫ b–c, d–e ⎯→ Position isomers

(iii) C3H6Cl2 has 4 isomers:

Cl Cl

a) H3C–CH2–CH–Cl b) H2C–CH2–CH2–Cl

Cl Cl
c) H3C–C–CH3 d) H2C–CH–CH3
Cl Cl

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Isomerism Part-04

(IV) Structural isomers of C7H16 are 9.

1. CH3–CH2–CH2–CH2–CH2–CH2–CH3 Heptane

2. CH3–CH2–CH2–CH2–CH–CH3 2-Methylhexane
CH3
3. CH3–CH2–CH2–CH–CH2–CH3 3-Methylhexane
CH3

CH3
4. CH3–CH2–CH2–C–CH3 2,2-Dimethylpentane
CH3
CH3
5. CH3–CH2–C–CH2–CH3 3,3-Dimethylpentane

CH3
CH3
6. CH3–CH–CH–CH2–CH3 2,3-Dimethylpentane

CH3
CH3 CH3
7. CH3–CH–CH2–CH–CH3 2,4-Dimethylpentane

CH2–CH3
8. CH3–CH2–CH–CH2–CH3 3-Ethylpentane

CH3
9. CH3–CH–C–CH3 2,2,3-Trimethylbutane
(Triptane)
CH3 CH3

(V) Number of structural isomers possible for the C4H10O are 7.

C4H10O → D.U = 0 (no  bond), so only alcohols and ethers are formed.
Alcohol : CH3—CH2—CH2—CH2—OH CH3–CH2–CH–CH3
OH

CH3
CH3–CH–CH2–OH CH3–C–OH
CH3 CH3

Ethers : CH3—O—CH2—CH2—CH3, C2H5—O—C2H5, CH3–O–CH–CH3

CH3

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Isomerism Part-04

Illustration 1.
Determine number of Benzenoid isomers possible for the C7H8O
Solution:
Benzenoid isomers of C7H8O = 5
D.U. for C7H8O = 4 (1 ring + 3 bonds).
CH2–OH CH3 CH3 CH3 O–CH3
OH
(a) (b) (c) (d) (e)
OH
OH
⚫ a-b, a-e – Functional isomers ⚫ b,c,d – Position isomers

Note : Alcoholic and phenolic groups are Functional isomers.

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 Isomerism
Part-06

Stereoisomerism:

Stereoisomerism

Conformational isomerism Configurational isomerism

Geometrical Isomerism Optical Isomerism

Compounds having same molecular formula, same structural formula but different arrangement / configuration
of atoms or groups in space are known as stereoisomers.

(A) Configurational Isomerism:

Stereoisomers which have following characteristics.
(a) Stereoisomer which cannot interconvert at room temperature due to restricted rotation known as
Geometrical isomerism.
(b) Stereoisomers which have different behaviour towards plane polarised light are known as optical isomers.

Geometrical isomerism (G.I.):

(i) Alkenes ( >C=C<), oximes (>C=N—) and azo compounds [—N=N—] etc., show G.I. due to restricted rotation
about double bond and (ii) cycloalkanes show G.I. due to restricted rotation about single bond in ring.

Restricted rotatory systems

(1) Along -bond in acyclic molecules
(2) In cycloalkane (along single bond)

(1) Geometrical isomerism condition for -bond in acyclic molecules

(a) Only those alkenes show G. I. in which "Each sp2 carbon have different atoms or groups"
a a a x
C=C C=C
b b b y

Geometrical isomerism possible Geometrical isomerism possible

same
p p
a y C
same C=C C
a y
q q
Geometrical isomerism not possible Geometrical isomerism not possible

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Isomerism Part-06

••
(b) Oximes C=N–

a a
same C=N C=N
a OH b OH
Geometrical isomerism not possible Geometrical isomerism possible

•• ••
(c) Azo compounds –N=N–

N N N N
a a a b
Geometrical isomerism possible Geometrical isomerism possible

(2) Geometrical Isomerism in Cycloalkane

(a) Restricted rotation about single bond
(b) In cycloalkane system; atleast two sp 3 hybrid atom of ring individually must have different atoms / groups
attached to it.
H H H Cl

Cl Cl
Cl Cl Cl H

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 Isomerism
Part-07

Nomenclature Systems of Geometrical isomers with configuration

(a) Cis–Trans configuration

If same groups are at same side then cis and if same groups are at different side then trans.
a a b a
C=C C=C
b b a b
[Same groups, same side] [Same groups different side]
cis trans

a a z z
Ex. C=C
C=C
x y x y
cis cis

Cl Cl
C
CH3 H
Ex. C=C C
H CH2–CH3 Br Br
trans-2–Pentene It does not show Geometrical isomerism
So no cis–trans
(b) E – Z configuration
E (Entgegen) : When high priority groups are at opposite side.
Z (Zusammen) : When high priority groups are at same side.

LP HP HP HP
C=C C=C
HP LP LP LP
'E' 'Z'
HP – High priority and LP – Low priority

Priority Rules - Cahn-Ingold-Prelog [CIP Sequence Rules]:

Rule I : The atom with the greater atomic number has the higher priority.

Br F
C=C
[HP] I Cl [HP]
'Z'

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Isomerism Part-07

Rule II : If directly attached atom is same then see atomic number of next atom.
[C,C,C]
CH3 [HP]
CH3
[HP] F C CH3
C=C CH3
[LP] CH3H2C C [C,C,H]
CH3
[LP]
H
'Z'

Rule III : If multiple bond is present then consider them as :-

–CH=CH2 –CH–CH2 –CH=O –CH–O
C C O C

C C N C
–CCH –C—CH –CN –C—N
C C N C
Example
O
[O,O,H]
NC C–H
C=C
H
[HP] N C–OH
H [O,O,O]
O [HP]
'Z'

Rule IV : If two isotopes are being compared the one with the greater atomic mass has the higher priority.
H CH3
C=C
[HP] D CH2–CH3 [HP]

'Z'

(c) Syn-anti configuration:

Geometrical Isomers in Oximes [>C = N–] :
• Oximes show G. I. due to restricted rotation about double bond.

• Only those oximes show Geometrical isomerism in which sp2 carbon have two different groups.
CH3—CH=O + H2 N—OH → CH3—CH=N—OH (oxime)
Acetaldehyde Acetaldoximes

Example Acetaldoximes has two Geometrical isomers –

CH3–C–H CH3–C–H

N–OH HO–N
Syn Anti
When H and OH are on the same side. When H and OH are on the opposite side

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Isomerism Part-07

Example Benzaldoxime (formed from Benzaldehyde)

Ph–C–H Ph–C–H

N–OH HO–N
Syn Anti

• Acetoneoxime does not show geometrical isomerism.

CH3 OH
Example same C=N
CH3

•• ••
Geometrical Isomers in Azo compounds: (–N=N–)

Ph Ph
N N
 Ph—N=N—Ph 
N N
Ph Ph

Syn Anti

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 Isomerism
Part-09

1. Physical Properties of cis and trans alkenes

(i) Dipole moments ():

Dipole moment arises due to difference in EN and shape of the molecule.

Example: But-2-ene

H3C CH3 H3C H

C=C C=C
H H H CH3

cis-But-2-ene trans-But-2-ene
(  0) ( = 0)
Therefore, cis > trans

(ii) Polarity  µ (Dipole moment)

Generally, cis > trans

(iii) Boiling Point (B.P.) :

Boiling point depends on dipole-dipole interaction
Generally, cis molecule has higher boiling point than trans molecule due to more polarity.
Boiling Point  polarity  dipole moment (µ)

(iv) Melting point :

Melting point depends on packing efficiency.
Trans molecule has higher melting point than cis molecule as trans molecule is more symmetrical and shows
high packing efficiency compared to cis form which has low packing efficiency.

Example:

More voids less voids

(less packing efficiency) (more packing efficiency)
Melting point order: trans > cis

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Isomerism Part-09

Note: Generally trans alkene is more stable then cis alkene because there is repulsion between the group present on
same side of restricted rotatory system.

Example
H3C CH3 H3C H
C=C C=C
H H H CH3
more repulsion less repulsion

2. Calculation of total number of geometrical isomerism

When compound is unsymmetrical – No. of G.I. = 2n
When compound is symmetrical – No. of G.I. = 2n–1 + 2p–1
n n +1
where p = (when n is even) and p = (when n is odd)
2 2
where n = no. of restricted rotatory system about which G.I. is possible

Illustration 1.
CH3–CH=CH–CH=CH–C2H5
Solution:
n=2
No. of geometrical isomers = 2n = 22 = 4

Illustration 2.
CH3–CH=CH–CH=CH–CH3
Solution:
n = 2 (even)
𝐧 𝟐
𝐏= = =𝟏
𝟐 𝟐
No. of geometrical isomers (symmetrical compound) = 2n–1 + 2p–1 = 22–1 + 21–1 = 3

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 Isomerism
Part-10

Conformational isomerism / Rotational isomerism / Conformations :

• The different arrangement of atoms in space that result from the rotation around single bond are called
conformations. The phenomenon is called conformational isomerism.
• They cannot be isolated at room temperature from each other as they are interconvertible at room
temperature.
• Bond length, bond angle are same in all the conformers.
• These are interconvertible forms of single compound so there is no change in boiling point, melting point,
dipole moment.
• There are infinite conformations of a compound
• If there are three continuous single bond present in a compound then it can show conformation.

Representations of tetrahedral carbon

1. Sawhorse projection 2. Newman projection
3. Wedge-dash projection 4. Fischer projection

Wedge-Dash Formula (3D)

Out of 4 units, 2 units including tetrahedral carbon is maintained in the plane and remaining two units in and
out of the plane.
Example: CH3—CH(OH)—COOH
CH3

C
H
HO2C
OH

Fischer Projection (2D)

Groups at horizontal line towards observer.
Groups at vertical line away from observer.
COOH COOH

HO H HO H

CH3 CH3

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Isomerism Part-10

Saw horse projection

H H H
H H
C C
C H C
H
H
H H H H
Eclipsed Staggered
Saw horse projection

Newman projection
H H
H H H
60º

H
H H H H H
H
Eclipsed Staggered
Newman projection

Some important terms:

1. Types of Strain:

Van der waal Strain / Steric strain Torsional Strain

• When 2 non bonded atoms or groups are brought • Repulsion between bond pair-bond pair
close together then they repel each other. This electrons.
type of repulsion is called van der waal strain/
steric hinderance.

Eclipsed Eclipsed

• Minimum in staggered form and maximum in • Maximum in eclipsed form and almost zero in
eclipsed form. staggered form.

2. Dihedral Angle/ Torsional Angle ():

Angle between two bonds of adjacent atoms.
Example: In ethane, angle between the front carbon-hydrogen bonds and back carbon-hydrogen bonds.

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Isomerism Part-10

Angle of rotation or angle

of tortion or Dihedral angle Stability Order:
H H Staggered>Eclipsed
H H H
• In ethane, staggered form is
more stable than eclipsed
H H form by 12.5 kJ/ mol due to
H
H H H H torsional strain in eclipsed
(Eclipsed) (Staggered) form.
 = 0º  = 60º

Newman's projections of ethane

Skew Form: There are infinite conformations between eclipsed and staggered forms known as skew form.

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 Isomerism
Part-11

Conformations of ethane [CH3—CH3] :

H H H
H H
C C
Saw horse projection C C
H H
H
H H H H
Eclipsed Staggered

H H
H H H
Newman projection 60º

H
H H H H H
H
Eclipsed Staggered

Stability order : Staggered > Eclipsed

Dihedral Angle : Dihedral angle in eclipsed form of ethane is 0°.

Dihedral angle in staggered form of ethane is 60°.

Potential Energy Diagram :

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Isomerism Part-11

Conformation of Butane:
CH3—CH2—CH2—CH3

Me Me Me Me
Me Me H H H
H 60º 60º
60º

H H
H H H H H
H H H Me H Me
H
Fully eclipsed Gauche Partially eclipsed Anti / Staggered

(I) (II) (III) (IV)

I (Fully eclipsed form): In this form distance between two methyl groups is minimum so maximum repulsion or
minimum stable.
IV (Anti or staggered): In this form distance between two methyl groups is maximum so minimum repulsion or
maximum stable.
III (Gauche form): In this form the angle between two methyl groups is 60º
Stability order : IV > II > III > I
Energy order : I > III > II > IV

Note: If staggered form is at 60º (in ethane) then it is not gauche form.

Special Cases:
It is not necessary that anti conformation is always more stable than gauche conformation.
CH2—CH2
Here Z= (-F, -COOH, -NH2, -OH, -NO2, -OCH3 etc.)
OH Z
CH2—CH2
Example: Ethylene glycol
OH OH
OH OH
(Stability Order)
H OH H H
>
H H H H
OH OH
Gauche Anti
(Intra molecular H-bonding)

Conformations of cyclohexane:

Boat Half Chair Chair Twisted boat

• Chair form is most stable conformation of cyclohexane.
• Stability Order: Chair > Twist Boat > Boat > half chair

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