When two or more PART-C ISOMERISM

phenomenon is knowncompounds
as having the same
isomerism and such molecular formula differ in
1.Structural compounds are called isomers. physical or chernical properties,
When two or Isomerism
the
mnore
of compounds
different arrangement having
of atoms in
the same molecular
formula possess different chermical
compounds are called structural isomers. Thismoelcules.
their the phenomenon is known as structures on account
is of six types : structural isornerism and the
ISOMERISM

Structural
Isomerism Stereo
Isomerism

Geometrical
Isomerism Optical
Isomerism
Chain Position
Isomerism Functional Meta
Isomerism Isomerism merism Ring-Chain Isomerism Tautomerism
(i) Chain Isomerism
This arises due to the
difference in the carbon skeleton present in the
contain at least four carbon
or skeleton isomerism.
atoms. Chain isomers usually differ in their compound. For hvdrocarbons it must
root word. This is also called as nuclear
(a) CH,CH,CH,CH3 CH-CH-CH3
n-Butane
CH3
2-Methylpropane
CH,
(b) CH,CH,CH,CH,CH3 CH3-CH--CH,-CH CH; -CCH3
n-pentane
CH
2-Methyl butane CH3
2,2-Dimethvll propane
 306 VATSAL ISC HANDBOOK of CHEMISTRY Class XI
(i) Positional Isomerism
This arises due to the difference in position of a
functional group of a multiple bond or a
(a) CH,CH,CH,OH
Propan-1-ol
and CH-CH-CH3 (b) CHCH,CH=CH,
But-Jene
suubstitution
group. eq
and CH;CH = CHCH
But-2-ene
OH
Propan-2-ol
CI
C CI

(c) and and

C CI
ortho-dichlorobenzene meta-dichlorobenzene para-dichlorobenzene
(ii) Functional Isomerism
This type of isomerism arises due to difference in the nature of the functional group present in
(a) C3H0 the compound.t
CH3-0-CH = CH, CH, = CH CH,-OH
Methoxy ethene Prop-2-en-I-ol
HO -CH
CH3C-CH,
H
Propan-2-one H,CCH,
Oxetane H,C CH,
Cyciopropanol
(b) CzHgN
CH,CH,CH,NH,
Propanamine
H3C. H;C
(1°amine) NH
N-CH3
CGHs H,C
NMethvl ethanamine NN-Dimethvl
(2° amine)
methanamine(3amine)
(c) RC = N and R-NCare functional isomers.
Alkvi cyanide Alkyl isocyanide

ADDITIONAL INFORMATION
Double Bond Equivalence (DBE)
DBE = (No. of carbon atoms + 1) - (No. of monovalent atomns - No. of trivalent atoms)
2
or
DBE
i- (C+19-(")
Double bond equÍvalence of a
of rings present on a sum of r compound tells about the number of bonds present in the compound or the nun
bonds and rings present in the
e.g., CgHgN compound.
9
DBE =(3 +1)-4-4 =0
2
Case 1. If the compound contains only
hydrogen and carbon, and
DBE = (3 + 1) -
() = 4-3 =1

DBE = 0 ’ alkane
DBE = 1 ’ alkene or
cycloalkane
DBE = 2’ alkyne, diene,
Case 2. If the compound contains cycloalkene or 2 rings.
DBE = 0 ’ ether or alcoholcarbon, hydrogen and oxygen and
DBE =1 ’ aldehyde, ketone,
unsaturated alcohol or ether, epoxy, cyclicalcohol or cyclic ether.
 307
ORGANIC CHEMISTAY::SOME BASIC PRINCIPLES ANDTECHNIOUES

re 3. If the compound contains, carbon, hydrogen, two orygen atorns and

DBE = 0 ’ Diol

DBE = 1 ’ CarbOxylic acid,ester, hydroxy aldehyde, hydroxy ketone, cyclic diol.

Case 4. If the compound contains carbon, hydrogen, nitrogen and
DBE = 0 ’ Amine (1", 2° or 3*)
DBE = 2’ Cyanide or isocyanide
nitrogen, oxygen and
Case 5. If the compound contains carbon, hydrogen,
DBE =1’ Amide (Simple or Substituted)

functional groups.
(iv)Metamerism
alkyl groups present across a polyvalent
of
isomerism arises due to different type
This type of

and
CH,C-OCH3
C,H,0CzHs (b) HC-0C,H; Methy acetate
(a) CHg0CgH7 and
Ethoxy ethane Ethyl formate
Methoxy propane

CzHs
(c) CH3 and CNH
SNH CzHs
N-Ethyl ethanamine
CH3
N-Methyl propanamine

Note reported.
isomerism cO-exist, metamerism is isomerism, For
functional or positionbutan-2-one and
If metamerism and compounds. but not chain
1.
include the same
class of metamerism is reported 3-methyl
2. Metamers functional group, only position isomers. Similarly
samne polyvalent metamers but not
3. For the Pentan-2-one and pentan-3-one are isomers.
example: chain
metamers but not
pentan-2-one are
compound, then the
open chain
Isomerism compound and one is an
(v) Ring Chain of the isomeric forms is acyclic and H,C-CH-CI
When at least one isomerism. (b) CHzCH,CH=CH-CI
chain
known as ring
1Somerism is
H,C-CH,and
|-chlorobut-l-ene
(a) CHCH=CH-CH3 H,C-CH;
1-chlorocvlobutane
But-2-ene H,C-CH,
Cyclobutane

forms with different functional

interconversion of two isomeric equilibrium. The above
(vi) Tautomerism spontaneous
tautomers. Tautomers exist in dynanmic
to
isomerism is due called
This type of each other. These isomers are desmotropism.
groups into tautomerism or
Phenomenonis termed as
types :
These are mainly of two
(i) Nitro-Aci Tautomerism eg.,
compounds having a-hydrogen.OH
2° nitro
It is only shown by 1° and CH,CH = N
CH3CH,--N Isonitro ethane
(aci form)
Nitroethane
(nitro form)
 308 VATSAL ISC HANDBOOK of CHEMISTAY Class X1
(ii) Keto-enol Tautomerism
In this type of isomerism, a compound exists in two interconvertible forms, one containing a Keto group (know
ds Keto torm) and the othercontaiing an alcoholic goup (known as enolic torm):
T-eleCtrons.
Ihese tvo torms continuously change intoech other through the oscillation of a proton and
For exanmple: (a) Acetoacetic Ester:
0 H O OH

CHËC(C0C,H, CHCÇC0CgH;
H H
(Ketoform) (Enolic forn)

(b) Phenol :
OH

(Enolic form) (Keto form)

(c) Acetaldehvde :

CH-C-H CH,=CHOH
(Keto fom) (Enol form)
Generally 1. 2 or 1,3-migration of H-atom takes place.
Diad System
When the migration of H-atom from Ist to2nd element takes place. e.g.
2
(a) H-C=N H-N2C (b) H-0-N =0 H-N:
(Nitrite form) (Nitro formO
Triad System
When the migration of proton takes place from first to third element. Generally it takes place in keto-en
tautomerism, eg.,
30 H OH

-C-C--H
2 C=CH
Conditions for Tautomerism
1. X= Y-Z-H[at least one H on Z atom]
2. In X, Y, Zthere should be at least one atom which
If both the conditions are satisfied then has electronegativity greater than carbon.
Y
tautomerism exists in a molecule.
e, (a) CH, -CH-Ú
Only seCond condition is satisfied, it will not
Y exhibit tautomerism.
(h) CH,-(CH-H,
As only first condition is
Conditions for Keto-enol Tautomerism satisfied, it will not exhibit tautomerism.
1. Presence of u-hydrogen w.rt. Carbonyl group.
2. a-carbon atom must be sp' hybridised. eg.,
(a) CH,=C-CH, CH--C-CH
OH
(Enol fom) (Keto form)
 ORGANICCHEMISTRY : SOME BASIC
OH
PAINCIPLES ANO TECHNIGUES 309
(-CH3 C-CH,
(b)
(Keto form) (Enol form)
Exception:

(c) It does not show keto-enol tautomerism as the a-carbon atom is sp hybridised

(Benzoquinone)
Characteristics of Tautomerism
intramolecular change.
1. It is a reversible
forms is difficult.
2. Separation of tautomeric
tautomeric form is known as labile form.
3. The less stable
greater resonance stabilisation of carbonyl group as
Stability due to
is generally more stable than enol
1. Keto form double bond. highlvsubstituted double
compared with a carbon-carbon form is more stable but the enol with more
unsymmetricalketones, keto
2. With OH
bond is more stable. e.g.,
OH CH--C= CHCH,
CH3-C-CH,CH: (Enol form)
CH,=C-CH,CH, (Keto form)
(Enol form)

is more stable.
IIform of enol carbon-carbondouble
not have its
OH negligible amount because it does
CH,C-CH, also exists in
CH,= -
group.
conjugated with carbonyl
stable than keto
form due to:
bond enol is more
cases, aromatic ring.
3. In
some forming an
Stabilisationgained by OH
(a)

(Enol form)
H-bond, e&., B-diketones.
(Keto form)
of intramolecular
formation
Conjugationand H
(b)

C-CH;
CH--C
CH3
1
HC H) H
(Keto form) (Enol form)
 310 VATSAL ISC HANDBOOK of CHEMISTAY Class XI
Differences between Tautomerism and Resonance
canonical forms of aresonance hybrid are hypothetical.
I: lautomers are the existing compounds but involve achange in position of t electrone
2. lautomers differ in atomic arrangement but resonating structures molectler
3. lautomerism may occur in planar or non-planar molecules
while resonance occurs only in planar
structures have same functional group.
. lautomers have different functional groups but resonating
involves the change in the bond
). Tautomerism does not involve any change in bond lengths but resonance
length.