2 Isomerism

ISOMERS x = no. of ‘c’ in parent

. k chain
P.S.S tric
Compound having same M.F i c no. P .I y = no. of branches of ‘c’
Mag r CI &
but diff physical & chemical prop. f o
Magic no ⇒ diff ⇒ C.I
XY same ⇒ P.I
Types of Isomerism
2 4 C.I 1 2 21
1. Structural isomerism Mf = same, structure diff, IUPAC name 2 Cl P.I
diff 3 Cl
2. Stereoisomerism Mf = same, diff orientation of groups 1 1 Cl Cl
3
in space, IUPAC name same 40 31 20 20

Types of Structural Isomerism 1

CN
3 1
1. Chain Isomerism CN C.I
2
4 2
Compound having same MF. but different parent 3
chain. 40 31

2 4 3. Metamerism
3 2
1 C.I MF Same but difference in arrangement of atoms
1 or groups from either side of Bridging funcn group
3 (Polyvalent)
*
2. Position Isomerism —O— —NH— O O
MF = same, different position of branch like R or —S— —N —C—O—C—
F.G. like OH, NH2, OR, SH —C— O
O
O —C—O—
3 1 3 1 —C—NH—
2 OH 2 PI —C— O —C—
4 4
OH S —C—N— O

1 2 3
4 4 2
C—C—C—O—C C—C—O—C C—C—O—C—C
2 5 3 PI
5
—

1 ’ C
3 1 3 ‘c al 1‘c’ 1‘c’ 2‘c’ 2‘c’
o r m Branch
n
O 1, 2, 3 are metamers
2
3 4. Functional isomerism
2 PI
1 1 MF same, different F.G.
O
O
keto F.I.
OH

ene alc.
Some examples of F.I. 2 1O 2 OH
O  1, 5-system sp sp
3 2 3
ail
a. Aldehyde & ketone: H 1,3 f a
Jab hog 4 4
l
O 3 5H Pheno
sp
b. Carboxylic acid & ester: CH3COOH, HCOOCH3 2 1 + –
1,2-system H –C≡N H–N≡C
c. Alcohol & ether: OH
O
d. Cyanide & isocyanide: RCN, RNC

e. 1°, 2°, 3° amines:

CALCULATION
 OF NUMBER OF
3°
STRUCTURAL ISOMERS
2°
1° NH N Degree of unsaturation (D.U)
2 NH

or, double bond equivalent (D.B.E)
f. 1°, 2°, 3° amides:
H + X- N
DU=(C + 1) -  
NH2 NH N 2
O
 
 O O    

g. diene, yne: C = no of 'C' atoms DU = 0 ⇒ all single bond

H = no of 'H' atoms DU = 1
5. Ring Chain Isomerism
X = no of 'X' atoms 1π 1 Ring
MF ⇒ same
N = no of 'N' atoms
1st Ring DU = 2
1π + 1 Ring
2nd Chain 2π
2 Ring
6. Tautomerism
Total structural isomers
Keta-enol system 1 3
O H sp O–H
1, 3-system
CH3–C–CH2  10 + 0 - 0 
n
Cond for exhibition
α
2 3 α-H
CH3–C=CH2
1 C5H10 DU = (5 +1) -  
keto ene+ol  2 
of tauto. +
Intramolecular H enol
1 α–c should be sp
3 transfer = 6 – 5 = 1
1, 3 system
2 Presence of α–H 1π 1 Ring

Examples of Tautomerism:
O Total 10
O

O
O O

O  Alkanes No. of structural isomers

O O
C4H10 2

Ph–CH=CH–OH C5H12 3

167
Isomerism
 C6H14 5  Ring: -
C7H16 9 a) Two different group at different positions.
C8H18 18 b) Hybn sp3
C9H20 35 b
a a
C10H22 75
Cis-
TYPES OF STERO ISOMERISM a sp 3
a
H H
Configurational Isomerism b
a H

Trans
IUPAC name same H a b
    

TYPES OF CONFIGURATIONAL TYPES OF G.I

ISOMERISM Case 1: Cis -Trans

1. Geometrical Isomerism similar groups same side cis

otherwise trans
Arises due to restricted rotation around
C=C, C=N, N=N, Ring Me Me Me H
C = C C = C
Condn :- Restricted site must have diff groups
H H H Me
Cis
a X a Y Trans
diff. C = C diff. C= C
b Y b X Case 2:
Z/E

 Example of GI zusammen Entgegen

. same side opp. side
No P.S.S
H
Cis/trans fail hoga toh Z/E Sochna hai
H I
1) Same C = C 5) C 1
H3C Br
H NH2 Cl
(No) C = C
1
HO E NH2
Br ××
diff H
2) diff C=N 6) C
 C.I.P rules
Cl Yes OH Yes Cl
1. Atomic no , priority
H 2. Atomic no of 1st atom same
3) ×× ××
7) C
N=N
azo
Cl go for next atom apply rule 1
Yes
R
Always
R Comp 3. In Isotopes mass no , priority
GI O C
C = O > C – O'
H H
O
4) C 8) C Same N C C
Cl No H
No C N < C = O

N C

168
Organic Chemistry
SPECIAL CASES n +1
P = (n = odd)
Case 1: Odd no. of cumulative double bond 2
Py–Py P –P P –P X CH3–CH=CH–CH=CH–CH=CH–CH3
a z z y y

C C C C n = 3
b
Y 3+1 4
P = = = 2
Br Me 2 2
C=C=C=C
Total G.I. = 23–1 + 22–1
Cl G.I. H
= 22 + 21
Case 2: Odd no. of Rings (spiro) = 4 + 2 = 6

X
a Properties
 of Geometrical
Isomerism
b Y
a. BP: Cis > Trans (BP ∝ DM)
Case 3: Cumulative double bond + Ring = odd Me
Me Me H
a DM
X C=C C=C m=0
H
DM ≠ 0 H Me
b Y m≠0
Case 4: Cycloalkene
8 memb b. MP: Cis < Trans
c. Stability: Cis < Trans
d. Solubility: Cis > Trans

2. Optical Isomerism

Chiral carbon
sp3 'c' attached with 4 diff groups

CALCULATION OF G.I. A
OH
X *C B * H CH3
Case 1: If molecule is Unsymm H *
*
n
Total G.I. = 2 ,   n = sites where G.I. exhibits OH H
Y

CH3–CH=CH–CH=CH–CH=CH–CH2Br
dextrorotatory

n = 3, Total G.I. = 23 = 8. If compound CW 'd' or +

rotates PPL
ACW 'ℓ' or –
Case 2: If molecule is symm. O.A
laevorotatory
Total G.I. = 2n–1 + 2P–1 If compound does not
rotate PPL
n O.I.A
P = (n = even)
2

169
Isomerism
 condn for exhibition of opti Iso: 1
3CH
3
Br
assymetry(chirality). 4 2 3
H OH HO CH3 Enantiomer
pos cos comp 2
4
Br H
OIA 1
x OIA S
x OIA R
.
x x O.A ← P.S.S
Jab Aankhon se na dikhe

POS (plane of symm) Comp 1 Comp 2
COS (center of symm)
(acyclic & cyclic) cyclic comp R S

A
E
P even membered
ring
Me H Me H
S
R
R
R
pos (x) I
pos ( ) S S
CH3 CH3
* Me Me H Me
H OH H OH
diff cos ( )
Et pos (x) CH3 Case 2 If two chiral carbons are present
cos (x)
pos ( ) CH3 CH3
H OH HO H Enan
H OH HO H
 R/S nomenclature  Br Br

In fischer projection formula CH3 CH3

Case 1 if 4 is on vertical then check direction H OH H OH Diastereo
of movement from 1→2→3 HO H H OH
4 H R → Rectus (CW) Br Br
1 3 S S → Sinister (ACW)
 I NH2 Comp 1 Comp 2
Answer
Br D
2 Enan
or R,R R,S
Case 2 if 4 is on horizontal make a switch Iden E
D E D
or
CH3
3
Diastereomer S,R S,S
H
4 1
OH D
2
1) not mirror images
NH2 2) phy & chem prop diff
S
 Relation b/w compounds
Meso Compounds
Case 1 If only 1 chiral carbon is present
Answer : Enantiomer or Identical
atleast 2 chiral carbon c-car( )
Enan: 1) non super imposable mirror images with pos or cos pos( )
c-car(2)
2) phy & chem prop same 2 ) pos( ) meso(X)
a r( ( ) CH3 * meso( )
c.cpos H * OH *
CH3 CH3
H
H OH HO H Enantiomer * OH
meso CH
( ) 3
Br Br

170
Organic Chemistry
Racemic Mixture Epimers
equimolar mix of two enantiomers .
P.S.S
CH3 CH3 A & B are enantiomers Diastereo 1 1

* CHO CHO
H OH HO * H A → OA θ = +30° but 1 chiral 2 2
H OH HO H
Et Et carbon
B → OA θ = –30° 3 3
A B par he HO H HO H
A+B → O.I.A θnet= 0 config 4 4
H OH H OH
change 5 5
due to external H OH H OH
compensation hoga 6 6
CH2OH CH2OH
Glucose C-2 epimer
Resolution
Sep of pure enantiomers from R.M

A+B Rxn A + B
Calculation of Optical Isomers
RM
Case 1 if molecule is unsym
Pseudo Chiral Centres
Total O.I = 2n n = chiral carbon
a) 'c' attached with two diff group n
O.A = 2
b) other two groups are same bsut exhibit G.I or
have chiral carbons meso = 0

*CH(OH)CH OA
CH—
—CH—CH3 3 R.M =
2
— —

**C — OH
— —

**C — OH
H— H—
4
CH3 n = 2 Total OI = 22 = 4 RM = =2
CH(OH)CH3 2
CH—
—CH—CH3 * CH(OH)
OA = 4
meso = 0
* CH(OH)
Special Cases Et
1 even no. of cumulative 2 even no. of spirane rings
Case 2 If molecule is sym
double bonds A X
O.A n
Y P=
iff C —
— C —
— C diff B n = even 2
d O.A (a)
HO NH2 n-1 p-1
HO H
same
Total OI = 2 + 2
C —
— C —
— C O.A H
pos ( )
NH2 OA meso
Br Br
OIA OA
R.M =
2
e nyls
3 Biph
G G diff NO2 NO2 diff
CH3 n=2 P=1
2-1 1-1
* CH(OH) Total OI = 2 + 2
= 2 + 1
G G COOH COOH
* CH(OH) meso
POS ( )
G → bulky group O.A
OA CH3
2
G ‡ H,D,T,CN,F,OH RM = = 1
2

171
Isomerism
(b) n = odd 1 2
Total OI = 2n-1 b) butane CH3—CH2—CH2—CH3
n-1
meso = 2 2
Me
Me Me
OA = OI - meso H 60° Me
θ=60°
OA
R.M = H
2 H H
H H
H H
CH3 n=3
Eclipsed Staggered
* CH(OH) OI = 23-1 = 4
3-1 Fully Eclip Gauche
2
meso = 2 = 2
* CH(OH) Me
O.A = 4-2 = 2 H Me
* CH(OH) H H
2 θ=60°
RM = = 1
CH3 2 θ=60° H H H H
H Me Me
Calculation of Stereo Isomers Eclipsed Staggered
n = chiral carbon + site of GI exhibition Partially Eclip Anti
Total Energy Stability
stereogenic area
S.I = 2n [A < G < PE < FE] [A > G> PE > FE]
* *
CH3—CH——CH—CH—CH3
Gauche Effect
—

OH CH2 CH2 G>A>PE>FE

n=2
2
Total S.I = 2 = 4 F OH [Stability]
CH2 CH2
O H
Conformational Isomerism G G
H
chelate
G → Hydrogen F
1) free rotation around σ bonds Most stable
bonding
2) C—C σ bond conformation
F,O,N H H
H
3) Total Conformers = ∞
Gauche ÷ Stablised by
Hydrogen bonding
Conformers of Alkanes
Conformers of Cyclohexane
a) ethane CH3—CH3 Stability
dihedral Stability C > T.B > B > H.C
H angle
HH
S > Skew > E
chair Energy
H H θ=60° Energy
S < Skew < E C< TB < B < HC
Twist boat
H H
H
H H (Chiral)
H H (OA)
max. stable Skew min. stable Boat
Staggered Eclipsed
Half chair

Jo kahi geere nahi, unhe kha asmaan ki

uchaiyo ka pata hota hai.

172
Organic Chemistry