Isomerism

Compounds having same molecular formula but atleast one

r

difference in their properties. (Physical,Chemical or both)

If D.U is different, molecular formula can’t be same.
r

If D.U is same, MF may/may not be same.

Never count H- atoms, while checking molecular formula.

r

Types

Structural Isomers Stereoisomers

Structural isomers:-
MF same but structure different.
n

Arrangement/Sequence/Connectivity of atoms different.

Two structural isomers can never have same IUPAC.

r

Chain isomers
Position isomers
Types
Functional/group isomers
Metamers
Tautomers
Chain isomers:- have different no. of C-atoms in P.C.C & side
carbon chain.
Eg:-
Determine min. no of C-atoms C are required for an
open chain alkane to show isomerism.
C —C—C—C C—C—C
: C

(1)For a cycloalkane to show chain isomerism

(2)For an alkene

C—C—C—C C—C—C
C
(3) For an alkyne

↳
C—C—C—C—C C—C—C—C
C
Position isomerism:- Have some molecular formula but different
position of functional group/multiple bond/substituents in P.C.C
Eg:-

§
§

§
§.

If
§%

is
Identify pairs of str. C represent position isomers:-

I
É
(1)

£
E.
(2)

se
§
(3)

&
ET
§

(4)
8

8
(5)

:{É
(6)
E

E
(7)

(8)
E

E
(9)

Min. no of c-atoms required

I

(10) E

for an organic compound to

show isomerism:-2
8

8
(11)
8

:
&

(12)
at
B
Minimum no of C-atoms required for an open chain
alkane to show positional isomerism.
6 atoms

B
For a cycloalkane
:

For an alkene
Functional/functional group isomerism:- has different
functional group. O
Eg:- CH3 — CH2 — OH CH3 — CH2 — C — OH
O

CH3 — O — CH3 CH3 — C — O — CH3

:
 É

Z
E

E
E

Amide Monosubstituted unit Disubstituted

unit
All are functional isomers.
r
 E
8

E
8
Alkenes with cycloalkane & alkynes/alkadienes with
>

cyclohexane show ring-chain isomerism.

Min no of C-atoms C are required for an alcohol to

>

show F.I
CH3 — CH2 — OH / CH3 — O — CH3

Min no of C-atoms C are required for an aldehyde to

*

show F.I
 O O
C—H D.U=1 CH3 — C — H

Alcohol C=C
µ
Ether C=C

I
µ

Cyclic compound

Metamerism :- have bivalent/polyvalent functional group but different

nature of units attached c bivalent/polyvalent functional groups.
I

Monovalent Bivalent/Polyvalent
O
OH —O—
COX —C—NH
CHO —C—O— O
NH2
COOH —NH— —C—N
0
CN —N— —S—O—
Eg:-

Functional isomers:-

0-4=0

§
6
É

0=4--0
go
É
0

§
3-
E
&
 :&i
Main no of C-atoms c are required for an ether to show isomerism.

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C—C—O—C—C C—C—O—C
C
For an ester ,
O
E

C—O
0=4
0=01

if
i
É

±
÷
±
 For a 3 amine

o
r

Total no of structural isomers c are responsible for C4H10:-

r

§ .
C5H12
n

C4H9Br
n

:
C5H10 D.U=1

C4H6(excluding open chain) D.U= 2

•
ÉT
Always grp C5H1O—O
0=0

:
Having carboxylic acid (COOH) C5H10–02 D.U=1

0=0
o=É

←
É

É
Having C4H8O(-CHO)

É
¥
:

'
C4H9Br , C4H9CHO , C4H9–COOH 4 isomers

q
C3H7– Z
:{
C2H5 - Z
ii.

CH3–Z
Total no of str. isomers for C4H9OH

④ OH -O-

③
C-C-O-C-C
C-O-C-C-C
C-O-C-C
C4H11N C
D.U=0 8 Structure

C4H9NH2
C-C NH — C — C N
4 isomers C-N—C—C—C
0

E
C—N—C—C
C
E
 Total no of structural isomers having 5- membered ring
C7H14:-
D.U=1

O
CH3-CH2-CH2-C-O-H
in

Chain isomers & functional

O
isomers.
CH3-CH2-C-O-CH3

Chain isomers & positional

isomers.
 Chain isomers/Metamers

Priority order:- R > T > F > M > C > P

Which of the following statements are correct:-

*

(A)2 position isomers can have different no of C-atoms

in their P.C.C
(B)2 functional isomers belong to same homologous
series.
(C)2 Metamers can have different F.G
(D)2 Chain isomers can have different F.G

ALL ARE INCORRECT.

 Stereoisomerism

Compounds having molecular formula, same sequence of atoms but

difference orientation of atoms, groups in space are called
stereoisomerism.

CH3 CH3 CH3 H

C—C C—C
H H
H CH3
But-2-ene

E
E

Et
E
E
E

E
E
I

Butane-2-3diol
E
E
 Two stereoisomers can never be structural isomers of each other &
n

two structural isomers can never be stereoisomers.

Stereoisomers will have same IUPAC excluding configuration.

Have 2 types

Conformational Configurational
Are interconvertable in normal Not interconvertable in normal
conditions. conditions.

Geometrical Optical
stereoisomers stereoisomers
Geometrical stereoisomers :- Compounds having same molecular
formula, same sequence of atoms but different orientations of atoms
& groups about restricted rotation.

Conditions for a compound to show geometrical isomerism:-

±

Restricted rotation:- when Bond is present.

-
-
•
E

E
↳

•
-
-
-
-
Stearic hindrance

Ti
o
Different groups:-
i
in
?
i
÷:& →

§
Ed
o
 Different distance:-;

ones
of !
or
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i
i
'

}
Compounds C can show geometrical isomerism:-
i

(1) Alkene Ist and 3rd conditions are always

£

Toi
%

fulfilled. Only check 2nd.

11£

Which of the following will show geometric isomerism:-

(1) Propene
←

TF
←

✗
u
J
"
It
(2) 1-Bromopropene

"
(3) 2 Chloropropene

'
¥
✗

g-
•

(4) But-1-ene
✗

U
i
y
\
I
(5) But-2-ene

÷
¥ :

.
(6) Pent-2-ene
;
I
%
i

(7) (8)

փ
Ig
•
✗

✗
(9) (10)

✗
-

§
(12)
§

(11)

>
✗
Allenes/Cumulated Polyene:- always have restricted rotation.

÷÷÷÷:&
.÷÷
0
to
:{ %
-
:}
e-
•
%
.

¥
11

¥ got

&
§•
.
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Which of the following are geometric isomers:-

✗
In Ém

¥¥¥¥÷i¥÷;É÷÷¥÷÷
>
£

✗
Ém § §

✗
>
É

s
.
Oximes Restricted rotation & different distance (both conditions
always valid)

¥:

E.EE
É
¥¥
Both C&N are SP2 hybridised.

Ñ
•

E
oh
¥:

Only check different groups

on C-atoms
→

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Which of the following compounds can show geometric
isomerism?
(1) CH3–CH — N—OH (2) Ph—CH — N—OH

>
>

(4)
(3)

>
✗

or
(5) (6)

÷÷:
•

(7) (8)
: Butanone
Propanone
(9) (10)

✗
Pentane-2-one Pentan-3-one

(11) (12)
EE

✗
>

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Benzaldehyde
3-methylcyclobutanone
(13) 2-ethylcyclohexanone (14) Benzophenone

÷÷
.

✗
(15) Acetaldehyde

o=É
Ems
Azo compounds:-

i
Can be substituted Benzene ring too.
i i.i.
i- Restricted rotation
i
§
I

§
•
¥
:}
Azo compounds always show geometric isomerism without any
exception.
 Cyclic structure/ Cycloalkane:- always restricted rotation,
different distance.
If in cyclic structure, SP3 hybridised have different group,
a

geometric isomerism is possible.

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or
8

¥
→

or

: I
•

•
\
Which of the following compounds will show geometric
isomerism?
(1) (2)

>
✗

(4)
(3)

&
:
(5) (6)

↳
.

,
Cycloalkane having 8 or greater than 8 numbers will
show isomerism about double bond.

CH3 — CH — CH — CH3

_jÉ
.
÷
Cyclic compounds having less than 8 carbon, wont show
geometric isomerism about double bond, out of C it
follows all conditions.
 ¥
Which of the following will show G.I?

(1) §
and (2)

>
✗
(3) (4)

&
:
✗
Naming of geometrical isomers:-

Cis:- If same groups are present on same side of restricted

rotation.
Trans:- If same group present on different side of restricted
rotation.
 }
§
§ I
3
•
.
8
§
E-Z Naming:- If no common group is attached to terminals.
ÉE .

É¥É Z= if same priority

E= if different priority
I

Priority — assigned using Rule

Eft
(1) Grp/unit having Ist atom
n
Chain Ingold Prelog

more atomic no. is given priority.

:*:
U
N
÷
N
g
(4)
(2)

;ɵ¥
of B

¥
M
N W
Én

(3)
(1)
(5)

i i÷. ÷ :*: (6)

EEE
"
W
.

(7) Covalent bond

Ionic bond -not considered

Covalent bond is given 1st priority

Syn/Anti compounds:- Azo compounds

Oxime compounds Ph—N—N—Ph

Aldoxime

ego
£30B
Ketoxime

e.
oÉÉ
F
iz
 ⑨
£ 's
£ 's

§É :&
Anti-aldoxime
Syn-aldoxime
Syn-methyl ethyl ketone

§
←
É"§

/ \
¥

→
R

Can be syn or anti depending on £

Anti-ethyl phenylketoxime
our choice but always chose wrt
OH.
Total no of geometric isomers:-

CH3 — CH — CH — CH — CH — Eth

Unsymmetric:- If no. from one side only.

Symmetric:- If no. from any of the sides.

:
¥
E

£
:{
B
Formula to calculate total no of isomers:-
G.I/ Total no of these sites where geometric isomerism is possible.

Unsymmetric- G.I= 2

i.
Symmetric - 2 +
E
Even

§
"
m= n+1 Odd

In
Calculate total no of geometric isomers in given
compounds:-

§
÷ ¥÷É
(1)

E÷
 I
& £
§É÷ É ÷É É
¥ ¥÷ ;¥¥¥
*
É ,
É E

(4)
(2)

(3)
(5)

+
¥

E.
(6)

£
%
Determine total no of chiral atoms present in following
compounds:-

8
(1) (2)

0
-1

8
I
EN

(3) (4)

-
N

Er
N
 I
(5) (6)

N
::
(7)
0
£

(8)
 N= no. of chiral carbon

N=0 N=1 N 2

ni
Polyphenyl Optically Unsymmetric Symmetric
All - ve can be
system[X] active
stereoisomers optically
always
optically active or
active not.

If H POS present - active

÷
If H POS (X) - active
Horizontal plane of symmetry
In ring, check vertical- POS
 OPTICAL ISOMERS
PPL:- plane polarised light

÷
i. i
a

¥1M

:
^
^

Nodal prism Plane polarised light

Optical activity:- Any organic compound

(In glass tube)

Rotated in CW No rotation
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Rotated in ACW

Optically active Optically inactive

/
Factors affecting angle of rotation:-

(1) length :- length of glass tube

(2) Concenteration:- conc. of substance filled in glass tube
(3) Temperature:- m c experiment is conducted
(4) Wavelength:- of light
(5) Nature of solvent

j¥
If temp & wavelength are constant , then :-

E-
÷
E

•
IÉ

Wedge-Dash Method:-

SP3 hybridised C
:&
.
EE
Atoms attached outside plane :- should be represented by Wedge &
Dash.

Towards the viewer

Away from viewer

Fisher-Projection method:- 3D—2D

SP3 hybridised c-atom represented by two straight lines

perpendicular to each other. Conditions for a compound to be
A
optical active:-
o

Away
Only condi. is chirality of its molecule.
:
o

Chiral molecule:- optically active

Towards
Achiral molecule:- optically inactive