Isomerism Allen

Read More at www.puucho.
com
JEE – MAIN
ISOMERISM
The name was given by Berzilius. Two or more than two organic compounds having the same molecular
formula and molecular weight but different physical and chemical properties are called isomers and the
phenomenon is called isomerism.
ISOMERISM
Structural Isomerism Stereoisomerism
Chain Position Ring Chain Functional Metamerism Tautomerism
Structural Isomerism :
S .No . Is o mers Cha ra cte ris tics Co nditio ns
They have differe nt size of They have same na ture of

1 Cha in Isomers
main cha in or side chain loca nt
They should have same size of
They have differe nt p osition
2 Positional Isomers main cha in and side cha in and
of locant
same nature of loca nt
Cha in and p ositiona l

3 Functional Isomers Diffe rent nature of locant
isomerism is not conside red
Diffe rent nature of a lkyl They should have same nature

4 Metamerism group along a p olyvalent of functiona l group chain &
functiona l group p ositional isomer is ignored
The two functiona l isomers

\\NODE6\E_NODE6 (E)\DATA\2014\KOTA\JEE-MAIN\SMP\CHEMISTRY\NOMENCLATURE, ISOMERISM & GOC\ENG\01-THEORY PART\02-ISOMERISM.P65
Diffe rent p osition of hydroge n

5 Tautomerism remains in dynamics
atoms
equilibrium with each other
1. Chain Isomerism (CI) : The compounds which have same molecular formula, same functional group, same
position of functional group or multiple bond or substituent but different arrangement of carbon chain
(different parent name of compound) shows chain isomerism.
Example : CH3 CH2 CH2 CH3 CH3 CH CH3
Butane(4C) CH3
2-Methyl propane (3C)
Example : CH3 CH2 CH CH2 CH2 C CH3

CH3
1–Butene(4C)
2-Methyl-1-propene(3C)
Example : CH3 CH2 CH2 CH2 OH CH3 CH CH2 OH
1-Butanol (4C) CH3

2-Methyl-1-propanol (3C)
E 35
Chemistry
O O
Example : CH3 CH2 CH2 CH2 C OH CH3 CH CH2 C OH
CH3
Pentanoic acid
3-Methyl butanoic acid
CH3 O
CH3 C C OH
CH3
2,2-Dimethyl propanoic acid
2. Position Isomerism (PI) : 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.
Example : CH2 CH CH2 CH3 CH3 CH CH CH3
But–1–ene But–2–ene
Example : CH3 CH2 CH2 CH2 OH CH3 CH2 CH CH3

OH
1–Butanol 2–Butanol
Example : CH3 CH2 CH2 CH2 Cl CH3 CH2 CH CH3

Cl
1–Chlorobutane 2–Chlorobutane
Example of CI and PI :
(i) C4H10 have two isomers : Both butane and isobutane are chain isomers.
Example : CH3 CH2 CH2 CH3 CH3 CH CH3
CH3
Butane Isobutane
(ii) C5H12 have three isomers : All of three structures are chain isomers because only carbon chain (parent)
isdifferent.
CH3

CH3 CH2 CH CH3 CH3 C CH3
CH3 CH2 CH2 CH2 CH3
CH3 CH3
Pentane 2–Methyl butane 2,2–Dimethylpropane
(iii) C6H14 has 5 isomers
(a) CH 3 CH 2 C H 2 CH 2 CH 2 C H 3 (b) CH3 CH2 CH2 CH CH3
CH3
Hexane 2–Methyl pentane
(c) CH3 CH2 CH CH2 CH3 (d) CH3 CH CH CH3
CH3 CH3 CH3

3–Methyl pentane 2,3–Dimethyl butane
CH3
(e) H3C C CH2 CH3  a–b, b–d, a–c, c–d  Chain Isomers
CH3
2,2–Dimethyl butane  b–c, d–e       Position Isomers
36 E
JEE – MAIN
(iv) C7H16 has 9 isomers
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–Dimethyl pentane

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
CH3 CH3
(v) C3H6Cl2 has 4 isomers : Position of chlorine atom is different in all the structure, so these are position
Isomers.
Cl Cl
1. H3C CH2 CH Cl 2. H2C CH2 CH2 Cl
1,1–Dichloropropane 1,3–Dichloropropane
Cl Cl
3. H3C C CH3 4. H2C CH CH3
Cl Cl
2,2–Dichloropropane 1,2–Dichloropropane
(vi) C5H11Cl has 8 isomers
E 37
Chemistry
(vii) C8H10 has 4 aromotic isomers
CH3 CH2 CH3

CH3
(o,m,p)
(viii) C 6 H 4 X 2  3 Aromatic isomers

C 6 H 4 X Y  3 Aromatic isomers
C 6 H 3 X 3  3 Aromatic isomers
C 6 H 3 XYZ  10 Aromatic isomers
Question : Structures CH3—CH2—CH CH2 and CH3 C CH2 are :–
CH3
Ans. Chain Isomers
Molecular formula No. of Isomers Molecular formula No. of Isomers

C 4H 10 2 C 8H 18 18
C 5H 12 3 C 9H 20 35
C 6H 14 5 C 10 H 2 2 75
C 7H 16 9
3. Ring chain isomerism (RCI) : Same molecular formula but different mode of linking (open chain or closed
chain) of carbon atoms.
CH3 CH CH2 [open chain]
C3H6
CH2
[closed chain or ring]
CH2 CH2
They have same molecular formula so they are Ring chain isomers.
(a)
Question : Relate a,b and c:– H3C C CH
(b)
C3H4 CH2 C CH2
(c) CH

CH2 CH
Ans. a–b  Functional Isomers

a–c , b–c  Ring-chain Isomers, Functional Isomers
Special points : Alkenes with cycloalkane and alkynes (Alkadienes) with cycloalkenes show Ring-chain Isomerism.
Ring-chain Isomers are also Functional Isomers.
Question : Relate structures a,b,c and d. (a) CH3—CH 2—C CH (b) CH2 C CH—CH3
CH3
(c) (d)
a, b  Functional Isomers

a, c.  Ring-chain Isomers and Functional Isomers
b, c  Ring-chain Isomers and Functional Isomers
a, d.  Ring-chain Isomers and Functional Isomers
c, d.  Chain Isomers
b, d.  Ring-chain Isomers and Functional Isomers
38 E
JEE – MAIN
5 4 3 2 4 3 2
Question : CH3 CH2 CH2 CH2 and CH3 CH2 CH CH3 are ?
1CN 1CN
Pentanenitrile 2–Methyl butanenitrile
Ans. Molecular formula same, Functional group same, position of Functional group same but different
parent carbon atom chain so both are Chain isomers
Question : How many minimum carbons required for Chain isomerism and Position isomerism in alkanes ?
Ans. 4, 6
Question : How many minimum carbons required for Chain isomerism and Position isomerism in alkenes ?
Ans. 4, 4
Question : How many minimum carbons required for Chain isomerism and Position isomerism in alkynes ?
Ans. 5, 4
4. Functional Isomerism :- Same molecular formula but different functional groups.

Following compounds show Functional isomerism, as they have same molecular formula and different functional
group.
(
i
) Alcohol and ether  C H 3— C H 2— O H and C H 3— O — C H 3
(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  C H 3— C H 2— C H 2— C N and C H 3— C H 2— C H 2— N C
O
(v) Nitro and Nitrite  CH3 CH2 N and C H 3— C H 2— O — N O
O
O
CH2 C CH3
(vi) Keto and enol  CH3 C CH3 and
OH
(vii) Amide and Oxime  CH3 C NH2 and C H 3— C H NOH
O
(viii) 1°, 2°, 3° amines
CH3
(i) CH 3—CH 2—CH 2—NH 2 (ii) CH3—NH—CH2—CH3 (iii)
CH3 N CH3
OH
CH2OH CH3
(ix) Alcoholic and phenolic compounds : and
(x) Alkyl halides do not show Functional isomerism.
E 39
Chemistry
5. Metamerism: Same molecular formula, same polyvalent Functional group but different alkyl groups attached
to polyvalent Functional group.
Polyvalent Functional group [More than one valency] are :
—O— , —S—, C
C , C O , C NH , —NH—, N , O, C N
C
O O O O
O
Example : C H 3— O — C H 2— C H 2— C H 3 ; CH3–CH2–O–CH2–CH3
Both are metamers.
Example : C H 3— C H 2— N H — C H 2— C H 3 C H 3— N H — C H 2— C H 2— C H 3
N–Ethyl ethanamine N–Methyl propanamine
They are only metamers not CI
Example : CH3 C CH2 CH2 CH2 CH3 CH3 CH2 C CH2 CH2 CH3
O O
2–Hexanone 3–Hexanone
Both are metamers and Position isomer
CH3 CH2 C CH2 CH2 CH3 CH3 CH2 C CH CH3

Example :
O O CH3
3–Hexanone 2–Methyl–3–pentanone
Both are Metamers
O O
Question : Structures and are
CH3 C O C6H5 C6H5 C O CH3

Ans. Both are metamers.
6. Tautomerism or Desmotropism : Tautomerism was introduced by "Laar". It's also called desmotropism.
Desmotroism means bond turning. [Desmos = Bond ; Tropos = Turn]
Tautomers have same molecular formula but different structural formula due to wandering nature of active
hydrogen between two atoms.

The tautomerism is also called kryptomerism or allotropism or desmotropism or dynamic isomerism.
CH2 C H
–H attached to carbonyl compound is active H
H O
–Hydrogen or active H
H
H
Example : H C C H
H C C H
O H
H O
40 E
JEE – MAIN
Example : CH3 C CH2 CH3 C CH2

O H O H
keto ene + ol = enol
Note : (1) Tautomers are also F. I. and exist in dynamic equilibrium is used to show tautomerism]
(2) By shifting of H–atom bond also change its position.
(3) Tautomers always exist in dynamic equilibrium.
(4) Number of electrons and lone pairs in both tautomers always remain the same.
(5) It is a chemical phenomenon which takes place only in liquids and gaseous phase only. It never
takes place in solid state.
(6) The process can be catalyzed by the acid as well a bases.
Condition for Tautomerism :
(a) For carbonyl compounds :- Carbonyl compounds having atleast one–H show tautomerism
(
i
) CH3 C H 3 H, show tautomerism.
O
(ii
) CH3 C CH3 6 H, show tautomerism
O
CH3 CH C H
(iii) 1 H, show tautomerism
CH3 O
(iv) H C H No H, No tautomerism
O
O
(v) C H No H, No Tautomerism

O
(vi) 3 H, shows tautomerism (Aceto phenone)
C CH3
(vii) Ph C Ph No H, No tautomerism (Benzophenone)

O
(viii) Ph C CH2 C Ph 2 H, shows tautomerism
O O
O
H H
(ix) 4 H, shows tautomerism
H H
O
H H
(x) H, attached sp2 carbon does not take part in tautomerism
H H
O
E 41
Chemistry
Question : Which of the following show keto enol tautomerism.
O
O H
CH CH OH
(1) (2) H (3) (4)
O O
Ans. (1), (2) and (4)
(b) For nitro compounds : Nitro compounds having atleast one – H show tautomerism
O
O
CH2 N
O CH2 N
H OH
Nitro form Aci nitro form

(acidic form so soluble in base)
Note : Nitro compounds with at least one –H are soluble in NaOH.
Question : Which of the following show tautomerism.
(1) CH3CH2—NO2 (2) (CH3)2CH—NO2 (3) (CH3)3C—NO2 (4) Ph—CH2—NO2
Ans. 1, 2 and 4
Question : Which of the following do not soluble in NaOH.
(1) CH3CH2—NO2 (2) (CH3)2CH—NO2 (3) (CH3)3C—NO2 (4) Ph—CH2—NO2
Ans. Only 3
(c) H—C N and H—N C are tautomers [also Functional isomers] while R—C N and R—N C are
only Functional isomers.
H—C N C N—H
Active H

O
(d) H N and H—O—N O are tautomers.
O
Enol Content :
1. CH2 C H CH2 C H
H O OH
"keto" (  99%) "enol" (  1%)
2. CH3 C CH2 CH3 C CH2 Less stable or unstable
O H OH
 99%  1%
O OH
H sp
2
3.
"keto" (  1%) "enol" (stable by resonance and aromatic nature) (  99%)
42 E
JEE – MAIN
4. CH3 C CH2 C OC2H5 CH3 C CH C OC2H5

O O OH O
Aceto acetic ester (AAE)

aqueous solution
keto : enol = 93 : 7
AAE
liquid state
keto : enol = 25 : 75
In aqueous solution
CH3 C CH2 C O C2H5

O O
Keto from is stablised by intermolecular H–Bonding.
H O H H O H
In liquid state
CH3 C CH C OC2H5
Enol form is stabilised by intramolecular H–Bonding.
O H O
(1) Enol content number of >C O group.

(2) If number of >C O groups are equal then proportional to number of –H.
(3) Group —OH attached to sp2 carbon or double bond is less stable or unstable.
(4) More active H, more take part in tautomerism.
(5) Stability of enol form depnds on (i) Resonance and (ii) H – Bond.
Question : Arrange the following in correct order of enol content.
1. CH3 C H 2. CH3 C CH3

O O
3. CH3 C CH2 C H 4. CH3 C CH2 C CH3

O O O O
Ans. 1 < 2 < 3 < 4
Question : Which have maximum stable enol form
O OH O OH
H H
(1) (2)
H
O OH
OH
O
(3) (4)
O OH
Ans. 4. Stable by Resonance and is Aromatic
E 43
Chemistry
OTHER EXAMPLES
(1) 7 Isomers of C4H10O [4 Alcohol and 3 ethers].

Alcohol : C H 3— C H 2— C H 2— C H 2— O H CH3 CH2 CH CH3
OH
CH3
CH3 CH CH2 OH and CH3 C OH
CH3 CH3
Ethers : C H 3— O — C H 2— C H 2— C H 3, C 2H 5— O — C 2H 5, CH3 O CH CH3

CH3
(2) 14–isomers of C5H12O [8 alcohols and 6 ethers]
(i) CH 3 —O—CH 2 —CH 2 —CH 2 —CH 3 (ii)CH3 O CH CH2 CH3 (iv) C2H5—O—C3H7
CH3
CH3
(iii)CH3 O CH2 CH CH3 (v) CH3 O C CH3 (vi) CH3 CH2 O CH CH3
CH3 CH3 CH3
(3) C4H8O (2 aldehyde and 1 ketone) total 3 isomers are possible.
O O O
(i)CH3 CH2 CH2 C H (ii)CH3 CH C H (iii)CH3 C CH2 CH3
CH3
(4) C4H8O2 (2 acids and 4 esters) total 6 isomers are possible.

O O

(
i
) CH3 CH2 CH2 C OH (
ii
) CH3 C OC2H5
O O
(iii) CH3 CH C OH (iv) C2H5 C OCH3
CH3
O O
(v) H C OC3H7 (vi) H C O CH CH3
CH3
(5) Aromatic isomers of C7H8O.
CH2 OH CH3 CH3 CH3 O CH3

OH
(a) (b) (c) (d) (e)
OH
OH
a, b – Functional isomers  b, c  – Position isomers
 c, d
 – Position isomers  a, d  – Functional isomers
 a, e
 – Functional isomers
Note : Alcoholic and phenolic groups are Functional isomers.
44 E
JEE – MAIN
O O
Question : CH3 CH2 CH2 C OH and CH3 CH2 CH C H are
OH
(a) Position isomers (b) Functional isomers (c) Geometrical isomers (d) Chain isomers
Ans. (b) Functional group different so Functional isomers.
Note : If Functional group is changed then they will be never Chain, Position isomer and metamers.
Question : C H 3 — S — C H 2 — C H 3 and CH 3—CH 2—S—CH 3 are –

Ans. Identical
O O O O
Question : CH3 C O C C6H5 and C6H5 C O C CH3 are –
Ans. Identical
STEREO ISOMERISM
Stereoisomers
Configurational Conformational
(non-interconvertible (Interconvertible
resolvable) non-resolvable)
Geometrical diastereomers Optical Isomers

(non-mirror image
Geo. isomers)
Enantiomers Diastereomers
(Mirror-image (non-mirror image
stereoisomers) optical isomers)
Two or more than two compounds having same molecular formula, same structural formula but different
`arrangements of atoms or groups in space.
(A) CONFIGURATIONAL ISOMERISM : Stereo isomers which have following characteristics.
1. Stereo isomer which cannot interconvert to each other at room temperature due to restricted rotation known
as Geometrical isomerism.
2. Stereo isomer which cannot super impose on each other due to chirality know as optical isomerism.
E 45
Chemistry
GEOMETRICAL ISOMERISM (G. I) : Alkenes ( >C C<), oximes (>C N—) and azo compounds
[—N N—], show Geometrical Isomers due to restricted rotation about double bond while cycloalkanes show
Geometrical Isomers due to restricted rotation about single bond.
GEOMETRICAL ISOMERS IN ALKENES :
Reason :- Restricted rotation about double bond : It is due to overlapping of p–orbital.
Restricted Rotation Free Rotation
CH3 CH CH CH3
2 2
sp sp
CH3 CH3
H H
CH3 CH3 CH3 H

Example : C C C C
H H H CH3
cis–2–butene trans–2–butene
Note : cis trans is possible only when  bond break.

Condition for Geometrical isomerism :
1. 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 isomers Geometrical isomers
p p
a y C
C C
a y C
q q
Not Geometrical isomers Not Geometrical isomers
Question : Which of the following show Geometrical isomerism –

(1) 1,1–diphenyl–1–butene (2) 1,1–diphenyl–2–butene
(3) 2,3–dimethyl–2–butene (4) 3-phenyl–1–butene
Ans. (2)
46 E
JEE – MAIN
NOMENCLATURE SYSTEMS OF GEOMETRICAL ISOMERS :
(a) Cis–Trans System : If same groups at same side then cis and if same groups 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
Example : C C C C
x y x y
cis cis
Cl Cl
CH3 H C
Example : C C
H CH2 CH3 C
Br Br
trans-2–pentene It does not show Geometrical isomers So no cis–trans
Physical Properties of Cis–Trans Isomers :
P h ys ic a l
S .N o . C o m p a ris o n R e m a rk s
p ro p e rtie s
cis-isom e r ha s re sulta nt of dip ole s while in tra ns isom e r dip ole
1 D ip ole m om e nt cis > tra ns
m om e nts ca nce l out
Mole cule s ha ving highe r dip ole m om e nt ha ve highe r boiling p oint

2 Boiling p oint cis > tra ns
due to la rge r inte rm ole cula r force of a ttra ction
3 S olubility (in H 2 O ) cis > tra ns More p ola r m ole cule s a re m ore soluble in H 2 O
More sym m e tric isom e rs ha ve highe r m e lting p oints due to be tte r

4 Me lting p oint tra ns > cis p a cking in cra sta lline la ttice & tra ns isom e rs a re m ore sym m e tric
tha n cis.
The m ole cule ha ving m ore va nde r wa ll stra in a re le ss sta ble . In

5 S ta bility tra ns > cis cis isom e r the bulky group a re close r the y ha ve la rge r va nde r
wa a l stra in.
Dipole moment [] :


Example : CH3 C H H C CH3

 
CH3 C H CH3 C H
cis  0 trans  = Zero
 
CH3 C H CH3 C H
Example :  
H C CH2 CH3 Cl C H
trans  0 cis  0

CH3 C H
Example :  trans  0
H C Cl
E 47
Chemistry
Cl
Question : If dipole moment of chlorobenzene is , then dipole moment of is –

Cl Cl
Ans. Zero
(b) E – Z System:
E (Entgegen) : When high priority groups are opposite side.
Z (Zussaman) : When high priority groups are 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 :
Rule I : Priority is proportional to atomic number of atom which is directly attached to sp2 carbon.
Br F [HP] Cl CH3
C C C C
[HP] I Cl [HP]
Cl C N H2 [HP]
'Z' Cl Cl 'E'
Rule II : If rule-I is failed then consider next atom
CH3
CH3 [C, C, C]
CH3
[HP] F C [HP]
C C CH3 decreasing order of atomic number
[LP] CH3H2C C CH [C, C, H]
3
[LP]
H
'Z'
Rule III :– If multiple bond is present then consider them as :-
C C
C C  C C C C  C C
C C C C

O N
C O  C C N  C N
O N
O
[O, O, H]
N C C H
H C C
[HP] N C OH
H [O, O, O]
O [HP]
'Z'
Prioity order for some groups is :

Br > Cl > OH>NH2 >COOH>CHO>CH2OH>CN>C6H5 >C CH>C(CH3)3 >CH CH2 >CH(CH3)2
Rule IV : If isotopes are present then consider atomic weight.
H CH3
C C
[HP] D CH2 CH3 [HP]
'Z'
48 E
JEE – MAIN
CH3 H CH3 CH3

Example : C C Example : C C
[HP] Cl CH3 [HP] H Cl
'Z' 'E'
N C CBr3 [Br, Br, Br]

CH3 CH2 CH2Cl [Cl, H, H] [HP] C C
Example : C C Example : CH3 C CH2I
CH C COOH [O, O, O] [LP] [I, H, H]
CH3 CH
3
'E' 'E'
GEOMETRICAL ISOMERS IN OXIMES [>C = N–OH] :
 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 + H2N—OH]  CH3—CH N—OH (oxime)
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
Example : Ph—CH N—OH Ph C H
Benzaldoxime N OH [syn.]
Ph C H
HO N [Anti]

(1) CH 3 —CH 2 —CH N—OH (2) H2C N—OH
(3) CH3 C CH3 (4) CH3 C CH2CH3

N OH N OH
Ans. (1), (4)
.. ..
GEOMETRICAL ISOMERS IN AZO COMPOUNDS : ( N N )
Ph Ph
N N
N N
Ph Ph
(syn) (Anti)
Ph—N N—Ph (Azo benzene)
E 49
Chemistry
GEOMETRICAL ISOMERS IN CYCLOALKANES : Cycloalkanes show Geometrical isomers due to restricted

rotation about single bond. Only those cyclo alkanes show Geometrical isomers in which atleast two different
carbons have two different groups.
Two Geometrical isomers

Me Me Me Me cis
H H H H
Me H trans
H Me
H Me
H Cl
H Me
(1) H H (2) Cl (3) Cl Br (4) Me
Cl
Cl Cl
H H Cl Br Me
Ans. (1), (2) and (4)
NUMBER OF GEOMETRICAL ISOMERS IN POLYENES :
R1—CH CH—CH CH .................................. CH CH—R2

(a) If R1 R2 then number of Geometrical isomers = 2n [n = number of double bonds.]
Example : C H 3 — C H CH—CH CH—CH C H — C H 2C H 3

As n = 3  number of Geometrical isomers = 23 = 8
(b) If R1 = R2 then number of Geometrical isomers = 2n – 1 + 2p – 1
n n 1

where p (when n is even) and p (n is odd)
2 2
Example : C H 3 — C H CH—CH CH—CH CH—CH3 [n = 3]

3 1
Number of Geometrical isomers = 2n – 1 + 2p – 1 [p= ]
2
= 2 2 + 21
= 4 + 2 = 6
Special Point : CH2 CH—CH CH2 [1,3–butadiene] show Geometrical isomerism due to resonance.
 
CH2 CH CH CH2
  
CH2 CH—CH CH2  CH2 CH2 H CH2
C C  C C
H H CH2 H
cis trans.
50 E
JEE – MAIN
OPTICAL ISOMERISM :
Optical isomers : Two or more than two compound have same molecular formula, same structural formula but
different direction of rotation of PPL (plane polarised light).
Non polarised Nicol prism Polarised light
Optical activity : Tendancy to rotate plane of PPL in a particular direction. If a compound rotates plane of PPL
in clockwise direction then it will be dexterorotatory or d or (+) and if a compound rotates plane of PPL
in anticlockwise direction then it will be Laevorotatory or  or (–).
Optically active  or d
compound
 or 
PPL
Condition for optical activity : "Molecule should be chiral".

Chiral object : Chiral=unsymmetrical  which cannot divided into two equal parts.
Symmetrical or achiral Mirror image of an achiral

Plane of symmetry object can superimpose on that object
Unsymmetrical or chiral Mirror image of a chiral object

does not superimpose on that object
Chiral carbon : Carbon which is bonded to four different atoms or groups.
COOH
C*
CH3 H Chiral carbon or asymmetric carbon.
OH
Chiral molecule : (i) A molecule has only one chiral carbon then it will be always chiral.
COOH
Chiral carbon
H OH
CH3 Chiral molecule
E 51
Chemistry
(ii) A molecule has atleast two chiral carbons and no plane of symmetry then it will be chiral molecule.
COOH COOH
H OH H OH
H OH HO H
COOH COOH
plane of symmtery No plane of symmetry
Essential and sufficient condition for optical activity is :

"Molecule should be chiral"
or
"Molecule should be unsymmetrical"
or
"Nonsuperimposable mirror images"
Enantiomers : Stereoisomers which are mirror image to each other and not superimpose to each other.
Nonsuperimposable mirror image are called as enantiomers.
COOH COOH
H OH HO H
CH3 CH3
object(I) mirror image (II)

I and II are nonsuperimposable mirror images, so I and II are enantiomers.
(
i
) Enantiomers have chiral structures.
(ii
) Enantiomers have identical physical properties such as melting point, boiling point, density, refractive index etc.
(iii) Enantiomers are optically active substances. They rotate the plane of polarized light in opposite directions

but to the equal extent.
(iv) Enantiomers have identical chemical properties. This means that they form same products as a result of
chemical combination. However, their reactivity, i.e. rates of reaction with other optically active substances
are different.
Diastereomers : Stereoisomers which are not mirror images to each others.
cis–2 butene trans–2–butene

(I) (II)
I and II are not mirror images, so I and II are diastereomers.
COOH COOH
Example : (1) H OH (2) H OH
H OH HO H
COOH COOH
(1) and (2) are diastereomers.
52 E
JEE – MAIN
(
i
) The diastereomers have different physical properties such as melting points, boiling points, densities, solubilities
and values of specific rotation.
(ii
) They can be separated from one another by physical means like fractional distillation, fractional
crystallization, chromatography, etc.
(iii) They are generaly optically active. However, geometrical isomers are exceptions.
(iv) They exhibit similar but not identical chemical behavior.
Identical : Stereo isomers which are superimposable mirror images.
Example :
CH3 CH3 CH3 CH3
H Cl Cl H H Cl Cl H
H Cl Cl H Cl H H Cl
CH2CH3 CH2CH3 CH2CH3 CH2CH3
(I) (II) (III) (IV)
I,II = Enantiomers, III,IV = Enantiomers
I,III = Diastereomers, II,IV = Diastereomers
II,III = Diastereomers, I,IV = Diastereomers
COOH COOH
H OH HO H
H OH HO H
Example :
COOH (I) COOH (II)
Achiral
I and II are identical
Meso compounds : Compounds having atleast two chiral carbons and one plane of symmetry is called meso
compounds.
COOH COOH
H OH H OH
H OH H OH
COOH COOH
Plane of symmetry Achiral molecule

optically inactive
Let one chiral C rotates PPL from OH to COOH,
then net rotation zero. (due to internal compensation)
Racemic mixture : Equimolar mixture of d and  enantiomers is called as racemic mixture. (d or  ).
d +  Net rotation zero

equimolar [External compensation]
"Racemic mixture is optically inactive due to external compensation.
Resolution (Separation) : Separation of racemic mixture into d and  enantiomers can be done by following
methods
1. Chemical method 2. Mechanical method 3. Biological method 4. Chromatography.
E 53
Chemistry
Properties of enantiomers :
S .N o . P ro p e rtie s R e m a rk s
1 Mole cula r form ula Sa m e
2 S tructura l form ula Sa m e
S te re oche m ica l form ula (structura l Form ula with

3 D iffe re nt
orie nta tion)
P hysica l p rop e rtie s (m .p ., b.p . de nsity, solubility),

4 Sa m e
re fra ctive inde x e tc.
Che m ica l p rop e tie s
5 (a ) with op tica lly ina ctive com p ound Sa m e
(b) with op tica lly a ctive com p ound D iffe re nt
Number of stereoisomers :
S.N. Nature of No. of optical active No. of meso Total no. of

compounds isomers (a) compounds (m) Stereoisomer (a + m)
1 Compounds having 2n 0 (2n + 0)

dissimilar ends (n = No. of chiral centre)
2 Compounds having
n
n 1
similar ends with 2n–1
1 ( 2 n 1  22 )
2 2
even chiral centres
3 Compounds having
n 1 n 1
similar ends with 2 n 1  2 2
2 2
2 n 1
odd chiral centres

Question : CHO CH CH CH CH CH2OH , find the number of optical isomers.
OH OH OH OH
Ans. n = 4
a = 2n = 24 = 16, m = 0
a 16
and R  , [R] = =8 where R (Racemic) = a/2
2 2
(a + m) = 16 + 0 = 16
Question : CH CH CH CH3 , find the number of optical isomers.
3
OH OH
Ans. n =2 a = 22–1 = 2,
2
1
2
m = = 2° = 1, [R] = =1 (a + m) = 2 + 1 = 3
22 2
54 E
JEE – MAIN
Three isomers are :
CH3 CH3 CH3

H OH HO H H OH
HO H H OH H OH
CH3 CH3 CH3
Question : *
CH3 CH CH CH CH3 find the number of optical isomers.
OH OH OH
Prochiral carbon
3 –1
Ans. n = 3 ; a = 23–1 –2 2 = 22 – 21 = 2
3 1
m = 2 2
2
(a + m) = 2 + 2 = 4
Question : CH3 CH CH CH CH CH CH3

OH Br CH3 Br OH
Ans. n = 5 a = 12,
m = 4, R = 6 (a + m) = 12 + 4 = 16
H Cl
C
Optical Isomerism in cyclic compounds :
CH2 CH2
Me H
(
i
) (
ii
)
C
CH2 CH2 CH2 CH2
No chiral carbon, No chiral carbon,

Molecule is achiral molecule is achiral
Molecule is optical inactive optical inactive
CH3 Cl Cl Br
(iii) (iv)
Chiral carbon, Chiral molecule No chiral carbon,

Optically active Optically inactive, Molecule achiral
Example : Structure Me Me has two isomers

H H
Me H Me Me
(
i
) (
ii
)
H Me H H
trans cis
No plane of symmetry 2 chiral C and plane of symmetry
No centre of symmetry chiral molecule meso
(opticallyactive) (inactive)
E 55
Chemistry
Absolute Configuration (R, S configuration) :
The actual three dimensional arrangement of groups in a molecule containing asymmetric carbon is termed
absolute configuration.
System which indicates the absolute configurastion was given by three chemists R.S. Cahn, C.K. Ingold and V.
Prelog. This system is known as (R) and (S) system or the Cahn–Ingold system. The letter (R) comes from the latin
rectus (means right) while (S) comes from the latin sinister (means left).
It is better system because in manycases configuration to a compound cannot be assigned by D, L method.
(R) (S) nomenclature is assigned as follows :
1. Each group attached to stereocentre is assigned a priority on the basis of atomic number. The group with the
directly attached atom with highest atomic number out of the four groups gets top priority while the group with
the atom of least atomic number gets the least priority.
F Cl Br I
Cl 3 
Increa sing At.No.
Example : F C I 4 C 1 4 3 2 1

Increa sin g Pr iority
Br 2
2. If out of the four attached atoms in consideration, two are isotopic (like H and D), then priority goes to higher
atomic mass i.e. D.
3. If out of the four attached atoms in consideration, two or more are same, then priority is decided on the basis
of the atom attached next to it in its group. e.g. out of CH3 and COOH, COOH gets priority.
4. While deciding the priority, if the atom in consideration is attached is further to an atom through a double bond
then it is treated as if it is attached to two such atoms. For example :
C C N C
O C
C C C C C N C N
C O C O
C C N C

CH
 In this way, the phenyl group i.e., is treated as if it is is treated as if it is C C
CH
Thus, out of – CH2CH3 and – CH = CH2, the – CH = CH2 gets priority. Consider following examples
lowest Stereocentre with there
priority Carbons attached to it
H H H Cl H carbon atom bonded twice to

O oxygen and once to hydrogen;
Br C C C C C group has the highest priority
H H
C
H H H C HH highest priority
lowest H C OH
priority
two hydrogen H C HH one chlorine atom and two stereocentre
H C OH
atoms and carbon atoms on this carbon
one carbon H atom; the chlorine atom has H
atom on this only hydrogen a higher atomic number than
carbon atom, any of the atoms on the other carbon atom bonded one to
atoms on this oxygen and twice to hydrogen
group of second carbon atom; two carbon atoms, thus this
group has the highest priority group of third priority
priority group on third
priority
56 E
JEE – MAIN
5. After assigning priorties, the lest priority group is written at remotest valency (going away), while the top priority
group is written at the top directed valency (towards viewer). Remaining two groups now have two possibilities,
giving two configuration. Thus, in the above compound (i.e. bromochlorofluoriodo methane) we have
I
1
C
Note that priority order is : I > Br > Cl > F
2
3 Br
Cl 4
F
 Now the order from top priority to the one of second priority and then to the one of third priority is deter-
mined. If this gives a clockwise direction then it is termed R configuration and if the anticlockwise direction is
obtained then it is assigned S configuration. For example. OH
OH
I I
C
C
C C HOOC
COOH CH3
H3C
H
F Br Br F H
Cl Cl
R–configuration S–configuration R–configuration S–configuration
(clockwise from top priority) (clockwise from top priority) (clockwise from top priority) (clockwise from top priority)
6. If we have to assign the configuration to a given structure and in that the lowest priority group is not on the
remotest valency, then we have to first bring this lowest priority group at the valency by exchange rule. One
mutual interchanging of the groups lead to reverse configuration and therefore to retain the given configuration
the double exchange is to be performed.
COOH COOH
COOH
C C
C
H3C H H CH3
H OH HO
CH3 OH (single exchange) (double exchange) R–configuration
Thus, the give structure has R configuration. Note that the top priority group is not to be necessarily on top
valency. We have to simply start the direction form top priority group.
Important : Note that the designation of a compound as R or S has nothing to do with the sign of rotation. the
Cahn-Ingold rule can be applied to any three dimensional representation of a chiral compound to determine
whether it is R or S only. For example in above case (i.e. lactic acid), R configuration is laevo rotatory is
designated as R-(–)-lactic acid. Now the other configuration of it will have opposite sign of rotation i.e. S-(+)-
lacticacid.
7. For the compounds containing more than one asymmetric carbon, again the same rules apply. Configuration
to each asymmetric carbon is assigned separately. Thus, to assign configuration to first asymmetric carbon in (+)-
tartaric acid, we have
COOH COOH COOH
H *C OH
H C OH HO C CH(OH)COOH
HO *C H
HO CH COOH H
COOH R – configuration
E 57
Chemistry
Special Point :
1. Chiral nitrogen containing tetra alkyl ammonium ion show optical isomerism.
R1 R1
N N
R4 R2 R2 R4
R3 R3
(I) (II)
I and II enatiomers
2. Chiral nitrogen containig tertiary amine do not show optical isomerism
Reason :- Rapid umbrella inversion.
N N
Room temperature
R1 R3 R3 R1
R2 R2
(I) (II)
Energy required for this interconversion is available at room temperature so I and II are identical
3. Chiral C containing carbanion do not show optical isomerism.
Reason :- Rapid umbrella inversion.
C C
Room temperature
R1 R3 R3 R1
R2 R2
(I) (II)
Energy required for this interconversion is available at room temperature.So, I and II are identical.
4. Substituted Allenes do not have chiral carbons but molecule is chiral, so show optical isomerism.

CH2 C CH2  X X
C C C
Allene Y Y
No chiral C but molecule is chiral
–bond
–bond
Ha
–bond –bond
Hc
C C C
Hb Hd
–bond
–bond
Only those substituted allenes will be optically active in which "each sp2 C have different atoms or group".
Question : Which of the following is optically active –
(1) CH3 — C H C CH—CH3 (2) CH 2 C CH 2
Cl Cl Me Cl
(3) C C C (4) C C C
Br Br Et Br
Ans. (1), (3) and (4)
58 E
JEE – MAIN
5. Ortho substituted biphenyl compounds do not have any chiral carbon but due to chiral molecule, they are
optically active.
NO2 HOOC
SO3H H3C
COOHO2N
CH3 HO3S
Horizontal Vertical
plane plane Optically active
CONFORMATIONAL ISOMERISM : The different arrangement of atoms in space that result from the free rotation
arround C—C bond axis are called conformations. The phenomenon is called conformational isomerism
H H H
H H
C C
C C
H H H
H H H
H
Here (60°) is dihedral angle, angle between two planes.
Question : Which of the following show conformational isomerism.
H
H
O O
C
(1) (2) C (3)
H H H H
H H
H H
H H H H H
O O C C H C C C
(4) (5) (6)
H H H H H H H
H H H
Ans. 2, 4, 5, 6 [Hint : Condition to show conformational isomerism There should be at least three continuous
sigma bonds.]
Conformers of ethane [CH3—CH3] :
H H H H H
H
C C H H
H 60° H
H H H
H H H H H
(
I
) (
II)
(Saw horse projection)
HH
H
H H
60°
H H
H H
H H
H
(III) (IV)
(Newman projection)
E 59
Chemistry
I = III (Eclipsed form) in this form distance between 2C–H bonds is minimum so maximum repulsion or minimum
stable.
II = IV (Staggered form) in this form distance between 2C–H bonds is maximum so minimum repulsion so
maximum stable.
There are infinite conformers between eclipsed and staggered forms which are called as skew forms
Stability order : Staggered > Skew > Eclipsed.
Dihedral Angle : Dihedral angle in eclipsed form of ethane is 0°.

Dihedral angle in staggered form of ethane is 60°.
The variation of energy with rotation about the C–C bond in ethane has been shown in figure below :
HH
H H
H H
Eclipsed
Potential Energy
–1
12.5 kJ mol
H H
H H H H
H H H H
H H
Staggered Staggered
Rotation
Changes in energy during rotation about C–C bond in ethane

The difference in the energy of various conformers constitutes an energy barrier to rotation. The energy required
to rotate the ethane molecule about carbon-carbon single bond is called torsional energy. But this energy
barrier is not large enough to prevent the rotation. Even at ordinary temperature the molecules possess
sufficient thermal and kinetic energy to overcome the energy barrier through molecular collisions. Thus,

conformations keep on changing form one form to another very rapidly and cannot be isolated as separate
conformers.
 Torsional energy :
The energy required to rotate the ethane molecule about ‘C–C’ bond is called torsional energy .
1 4
CH3 CH3
2 3
Conformation of Butane [CH3—CH2—CH2—CH3] C C
H H H H
Me Me
60° 60° 60°
H
Me
(I) (II) (III) (IV)
60 E
JEE – MAIN
I (Fully eclipsed form) : In this form distance between 2 methyl groups is minimum so maximum repulsion
or minimum stable.
IV (Anti or antistaggered) : In this form distance between 2 methyl groups is maximum so minimum repulsion
or maximum stable.
Stability order : IV > II > III > I
Dihedral angle : Angle between two planes.

Angle of rotation to get minimum stable to maximum stable form in butane is 180°.
Angle of rotation to get maximum stable to maximum stable form in butane is 360°.
The energy profile diagram for the conformation of butane is given below along with the difference of
energy between various conformation of butane.
H3C CH3
H CH3 H CH3
H H
H H
H H Eclipsed IV H H
H3C H H3C CH3
Eclipsed II Eclipsed VI
–1
19 kJ mol
Potential Energy
–1
16 kJ mol–1 16 kJ mol
–1 –1
3.8 kJ mol 3.8 kJ mol
CH3 CH3 CH3 CH3

H H H3C H H CH3 H H
H H H H H H H H
CH3 H H CH3
Anti I Gauche III Gauche V Anti I
0° 60° 120° 180° 240° 300° 360°

Rotation
Energy changes that arises from rotation about the C2–C3 bond of butane.
Baeyer strain theory : Cyclo alkanes with planar structures do not show conformational isomerism,
10 9 0 2 8 ' Bond Angle

Angle strain = 2
< < <
Bond angle 60° 90° 108° 109°.5'

Angle strain Maximum – – Minimum
Stability Minimum – – Maximum
Note : Cyclohexane is maximum stable due to minimum strain cyclohexane is nonplanar so it show conformations.
Two extreme conformers of cyclohexane are –
Chair form Boat form

Here, Chair form is more stable than boat form.
E 61
Chemistry
Sawhorse & Newmann projection of cyclo hexane :
H
H
H H
H
H
H
H
H H H
H
Sawhorse projection (Chair from) Newmann projection
Half Chair Twist–boat
The relative stabilities of the four conformations of cyclohexane decrease in the order :
Chair > twist boat > boat > half chair
 Difference between conformation and configuration
S .N . C o n fo rm a tio n C o n fig u ra tio n
It re fe rs to diffe re nt a rra nge m e nt of a tom s or

It re fe rs to diffe re nt a rra nge m e nt of a tom s or
1. group s re la tive to e a ch othe r a nd ra ise d due to
group s in sp a ce a bout a ce ntra l a tom .
fre e rota tion round a sigm a bond
The e ne rgy diffe re nt be twe e n two conform e rs is The e ne rgy diffe re nce be twe e n two configura tion
2.
lowe r form s is la rge

Conform e rs a re not isom e rs a nd the y ca n not be The se a re op tica l isom e rs a nd ca n be se p a ra te d
3.
se p a ra te d from e a ch othe r. form e a ch othe r.
The se a re not e a sily inte r conve rte d to one

4. The se a re e a sily inte r conve rte d to one a nothe r.
a nothe r.
62 E

Isomerism Allen

Transféré par

Informations du document

Description originale:

Copyright

Formats disponibles

Partager ce document

Partager ou intégrer le document

Options de partage

Avez-vous trouvé ce document utile ?

Ce contenu est-il inapproprié ?

Droits d'auteur :

Formats disponibles

Isomerism Allen

Transféré par

Droits d'auteur :

Formats disponibles

Read More at www.puucho.

Structural Isomerism Stereoisomerism

Chain Position Ring Chain Functional Metamerism Tautomerism

S .No . Is o mers Cha ra cte ris tics Co nditio ns

They have differe nt size of They have same na ture of

Cha in and p ositiona l

Diffe rent nature of a lkyl They should have same nature

The two functiona l isomers

Diffe rent p osition of hydroge n

Example : CH3 CH2 CH2 CH3 CH3 CH CH3

Example : CH3 CH2 CH CH2 CH2 C CH3

Example : CH3 CH2 CH2 CH2 OH CH3 CH CH2 OH

1-Butanol (4C) CH3

Example : CH3 CH2 CH2 CH2 C OH CH3 CH CH2 C OH

Example : CH3 CH2 CH2 CH2 OH CH3 CH2 CH CH3

Example : CH3 CH2 CH2 CH2 Cl CH3 CH2 CH CH3

\\NODE6\E_NODE6 (E)\DATA\2014\KOTA\JEE-MAIN\SMP\CHEMISTRY\NOMENCLATURE, ISOMERISM & GOC\ENG\01-THEORY PART\02-ISOMERISM.P65

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

CH3 CH3 CH3

(iv) C7H16 has 9 isomers

1. CH3 CH2 CH2 CH2 CH2 CH2 CH3 Heptane

4. CH3 CH2 CH2 C CH3 2,2–Dimethyl pentane

5. CH3 CH2 C CH2 CH3 3,3-Dimethylpentane

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

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

8. CH3 CH2 CH CH2 CH3 3–Ethylpentane

1. H3C CH2 CH Cl 2. H2C CH2 CH2 Cl

(vi) C5H11Cl has 8 isomers

CH3 CH2 CH3

(viii) C 6 H 4 X 2  3 Aromatic isomers

Molecular formula No. of Isomers Molecular formula No. of Isomers

\\NODE6\E_NODE6 (E)\DATA\2014\KOTA\JEE-MAIN\SMP\CHEMISTRY\NOMENCLATURE, ISOMERISM & GOC\ENG\01-THEORY PART\02-ISOMERISM.P65

Ans. a–b  Functional Isomers

a, b  Functional Isomers

4. Functional Isomerism :- Same molecular formula but different functional groups.

(iii) Acids and ester  CH3 C OH and H C O CH3

(vii) Amide and Oxime  CH3 C NH2 and C H 3— C H NOH

(x) Alkyl halides do not show Functional isomerism.

CH3 CH2 C CH2 CH2 CH3 CH3 CH2 C CH CH3

\\NODE6\E_NODE6 (E)\DATA\2014\KOTA\JEE-MAIN\SMP\CHEMISTRY\NOMENCLATURE, ISOMERISM & GOC\ENG\01-THEORY PART\02-ISOMERISM.P65

hydrogen between two atoms.

Example : CH3 C CH2 CH3 C CH2

Condition for Tautomerism :

(iv) H C H No H, No tautomerism

(v) C H No H, No Tautomerism

(vii) Ph C Ph No H, No tautomerism (Benzophenone)

Ans. (1), (2) and (4)

Nitro form Aci nitro form

\\NODE6\E_NODE6 (E)\DATA\2014\KOTA\JEE-MAIN\SMP\CHEMISTRY\NOMENCLATURE, ISOMERISM & GOC\ENG\01-THEORY PART\02-ISOMERISM.P65

"keto" (  99%) "enol" (  1%)

2. CH3 C CH2 CH3 C CH2 Less stable or unstable

"keto" (  1%) "enol" (stable by resonance and aromatic nature) (  99%)

4. CH3 C CH2 C OC2H5 CH3 C CH C OC2H5

Aceto acetic ester (AAE)

CH3 C CH2 C O C2H5

(1) Enol content number of >C O group.

Question : Arrange the following in correct order of enol content.

1. CH3 C H 2. CH3 C CH3

3. CH3 C CH2 C H 4. CH3 C CH2 C CH3

Ans. 4. Stable by Resonance and is Aromatic

(1) 7 Isomers of C4H10O [4 Alcohol and 3 ethers].

CH3 CH CH2 OH and CH3 C OH

Ethers : C H 3— O — C H 2— C H 2— C H 3, C 2H 5— O — C 2H 5, CH3 O CH CH3