Chapter 2

Isomerism

Isomerism
Compounds having same molecular formula but which differ in atleast some physical or chemical properties is known as

ck
isomers and the phenomena is said to be isomerism.

Isomerism

a
Structural isomerism Stereo isomerism
(Constitutional isomerism) cr
Chain isomerism
Conformational Configurational
Position isomerism
Functional group isomerism
e_
Geometrical Optical
Ring chain isomerism isomerism isomerism
Metamerism
Tautomerism
Je

Structural isomerism
It is due to different molecular structural arrangement having same molecular formula so that properties will be
different.
The structural isomerism may be classified into six categories. These are:
@

(i) Chain Isomerism: It is due to arrangement of carbon atom so that size of parent chain or size of side chain must
be different.
(ii) Position of isomerism: It is due to different locant number of functional group or multiple bond or side chain
along the same parent chain.
(iii) Functional group isomerism: It is due to presence of different functional group.
(iv) Ring Chain Isomerism: It is due to mode of linking of carbon atom so that same molecular formula correspond
to both open and cyclic skeleton is known ring chain isomerism.
• For ring chain isomerism double bond equivalent (D.B.E) π 0.
• All ring chain isomers are always functional group isomers.
(v) Metamerism: It is due to different size of alkyl group along the same divalent functional group.
Condition: Polyvalent functional group containing substances will show metamerism.These are:

O O
O NH S N C C O S O C NH etc.
O O O
2.2 | Organic Chemistry Module I
(vi) Tautomerism:
• Tautomerism is a special type of functional group isomerism which arises due to the oscillation of atom, mostly
H-atom as proton between polyvalent atoms.
• Such isomers are directly and readily interconvertible under ordinary conditions, and the isomers are called
tautomers.
• Tautomerism is chemical process and catalysed by acid or base.
• Tautomers exist in dynamic equilibrium.
• They have no separate existence under ordinary conditions.
• The other names of tautomerism are ‘desmotroprism’ or ‘prototropy’ etc.

Classification in Tautomerism
• On the basis of migrated atom
Cation migrate Æ Cationotropy

ck
Proton migrate Æ Prototropy
Anion migrate Æ Anionotropy
• On the basis of system
shiftting between 1, 2 atom – dyad system

a
shiftting between 1, 3 atom – triad system
shiftting between 1, 4 atom – tetrad system
shiftting between 1, 5 atom – pentad system
cr
Keto enol tautomerism
e_
Condition: Carbonyl compound must have atleast one a-H or acidic-H
It is Triad system because shiffing of proton occured between 1, 3 position.
• When the tautomers exist in the two forms keto and enol then, such type of tautomerism is called keto-enol
tautomerism.
Je

H O OH
C C C C
(Keto form) (Enol form)
Base catalysed tautomerism mechanism
@

O OH
H 3C C H H2C C H

• It is important to recognise that the enol is a real substance capable of independent existence it is not a resonance
from of the carbonyl compound.
• Following compound cannot show keto-enol tautomerism
(i) Carbonyl compounds do not have a-H can’t show keto-enol tautomerism.
(ii) Carboxylic acid and acid derivative except acid amide can’t show keto-enol tautomerism.
 Isomerism |   2.3
(iii) For keto-enol tautomerism, the tautomeric form must be geometrically favourable.
• Para tautomerism
When double-bond is present between a and b position (between C3 and C4) of cyclic ketone then ‘H’ of C5 takes
part in tautomerism, known as 1, 5 or para tautomerism.
–
O O O O OH
– –
Base B BH
–BH
–
H H

• % of enol in different compound

Enol content µ number of acidic H
µ stability of enolate ion

ck

µ stability of enol (due to intramolecular-H/aromatic character)

Comparison of Stability of Keto and Enol Forms

a
(i) In simple aldehydes and ketones, keto form is more stable than enol form because C=O bond is stronger than C=C
bond. cr
(ii) In complex structures like 1,3-diketo compounds, enol form is more stable because it is stabilized by resonance as
well as intramolecular hydrogen bonding.

O O H
O O
e_
H3C CH3 H 3C CH3
keto
H
enol
Je

Percentage composition of tautomeric mixture

Percentage of enol content of some compounds is given below in the table.
Compounds Enol percentage Compound Enol percentage
O O
@

O
H3C 0.00025 31.0
H3C CH3
CH3 CH3

O
O O
CH3 0.0056 80.3
H3C
H3C CH3
O
O O O O
4.8 89.00
H5C6 O–CH3 H5C6 CH3

O
O O
7.7 99.00
H5C6 O–C6H5
2.4 | Organic Chemistry Module I
Calculation of number of structural Isomers
Profile-1: Isomers of Alkane
Molecular formula CH4 C2H6 C3H8 C4H10 C5H12 C6H14 C7H16 C8H18 C9H20 C10H22
of alkane
number of isomer 1 1 1 2 3 5 9 18 35 69

Trick: Number of isomer in alkane = (2n – 1), where n = number of isomer in previous alkane (except C8H18)

Profile-2: Isomers of Alkyl Radical

Type of alkyl –CH3 –C2H5 –C3H7 –C4H9 –C5H11 –C6H13
Number of isomer 1 1 2 4 8 17

Profile-3: Isomers in different molecular formula

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Step-1: Find D.B.E for given molecular formula.
H+X–N
Degree of unsaturated (DU)/Double bond equivalent (DBE) = (C + 1) – ​ ​ _________
2
 ​  ​ ( )
Step-II: Select nature of bonding between C-C

a
D.B.E Possible bonding between C–C
cr
0 (–) single bond
1 (=) double bond/ Í ring
2 1 (∫) triple bond Í2 (=) double bond Í1 (=) double bond + 1 ring Í2 ring
4 Benzene ring (3(=) double bond + 1 ring)
e_

Step-III: Select the possible functional group

• If Molecular formula (M.F.) contains C, H only or C, H and (halogen), then draw and find out number of isomers
(for alkane refer above table).
Je

• If M.F. contains C, H, N, O, etc. then select possible functional group as follows:

M.F. D.B.E Possible functional group

CnH2n+2O 0 Alcohol/ether
CnH2nO 1 Aldehyde/ketone
@

CnH2nO2 1 Carboxylic acid/ester/ hydroxy carbonyl

CnH2n+3N 0 1°/2°/3° amine
CnH2n–1N 2 Cyanide/isocyanide

Step-IV: Separate possible functional groups and radical parts then number of isomers of radical is equal to number struc-
taur of some of corresponding functional group.

Stereo or space isomerism

Compound having same molecular formula and structural formula but differ due to spatial orientations of groups or atoms
is known as stereo isomers and phenomenon is termed as stereo isomerism.
(1) Geometrical isomerism
• Compound having same molecular formula but differ in their properties due to the difference in the orientations of
attachment of same atoms or group in their molecule.
• It is caused due to the restricted rotation about double bond in open chain and about single bond in cyclo alkane.
 Isomerism |   2.5
Condition of Geometrical isomerism
1. Rotation must be restricted.
2. Each blocked atom must have pair of different groups/atoms.
Geometrical isomerism is exhibited by following type of compounds.
(a) Compounds containing C = C, C = N, N = N, etc.
(b) Compounds containing cyclic structure.
1. Geometrical isomerism in alkene:
• Generally alkene show Geometrical isomerism because by the overlapping of two unhybridised carbon, formation
of p−bond takes place which produce restricted rotation.
p

ck
• All alkenes do not show Geometrical isomerism but not those in which both the double bonded carbon attach with
different group or atoms.

a
a a a a a a
C C C C C C
b b b cr b a a
Configuration of Geometrical isomer
1, cis/trans configuration:
• Cis form: Such isomer in which atleast one pair of similar groups/atoms attaches on the same side of double
e_
bonded carbon.
• Trans form: Such isomer in which atleast one pair of similar groups/atoms attaches on the opposite side of double
bonded carbon.
CH3 CH3 CH3 CH3
C C & C C
ex. H H H H
Je

(cis-2-Butene) (trans-2-Butene)
Comparison of properties of cis or trans-isomers: (With respect to 2-Butene)
S.No. Properties Answer Reason
1. Stability Trans > cis Trans have less mutual repulsion between the groups
@

2. Dipole moment Cis > trans Trans have zero dipole moment
3. Polarity Cis > trans Cis have more dipole moment so more polar
4. Solubility in water Cis > trans Cis is more polar so more soluble in water
5. Boiling Point (BP) Cis > trans Cis is more polar so more BP
6. Melting Point (MP) trans > cis Trans is symmetrical molecule therefore better packing in crystal lattice, so it has more MP

E-Z Configuration:
E Æ Entgegen (opposite), Z Æ Zusammen (same)
• E-form: when two same priority groups attach on the opposite side of double bonded carbon, then it is called as
E-form.
• Z-form: when two same priority groups attach on the same side of double bonded carbon, then it is called as
Z-form
1 1 1 2
C C C C
2 2 2 1
Z-form E-form
2.6 | Organic Chemistry Module I
• Priority rule: Chan, Ingold and Prelong proposed a sequence rule (CIP Rule)
Rule-1 When atom or group of atoms which are directly attached to the stereogenic centre have higher atomic number
will have higher priority.
Rule-2 When the atomic number is same, then higher atomic weight group or atom have higher priority
Rule-3 When both atomic number and atomic weight are same then priority will be decided by the next joining atom.
If one of the atom from next joining atoms have higher atomic number then it corresponds to higher priority and
so on.
Rule-4 If multiple bonded groups attach to the double bonded carbon, then they are considered in following manner.

N C

C O C O C C N C N
O C N C

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2. Geometrical isomerism in oxime: Oxime of aldehyde and oxime of unsymmetrical ketone also show geometrical
isomerism except Oxime of formaldehyde.
• In aldoximes
Syn isomer: When –OH group and H atom is on same side.

a
Anti isomer: When –OH group and H atom is on opposite side.
H
CH3 H CH3
C
cr and
C
N N
HO
OH
e_
Syn-Acetaldoxime Anti-Acetaldoxime

• In unsymmetrical ketoxime
Syn isomer: When –OH group and the alphabetically preferred alkyl are present on the same side of double bond,
then it is called as syn form.
Je

Anti isomer: When –OH group and the alphabetically preferred alkyl are present on the opposite side of double
bond, then it is called as Anti form.

CH3 CH2 CH3 CH3 CH2 CH3

@

C C
and
N N
OH OH
Syn-ethylmethyl ketoxime Anti-ethylmethyl ketoxime

3. Geometrical isomerism in azo compounds: All azo compounds show geometrical isomerism
ex. Ph–N = N–Ph
Ph Ph
N N
and
N N
Ph Ph
Syn-Azobenzene Anti-Azobenzene

4. Geometrical isomerism in cycloalkane: In cyclic compound the rotation about C–C single bond is restricted because
of the rigidity caused by the presence of other carbon of the ring which keep them tightly held, thus a disubstituted
cyclic compound (having the two substitution at the separate carbon) will also show Geometrical isomerism.
 Isomerism |   2.7
H H Cl H

and

Cl Cl H Cl
(cis form) (trans form)
Optical Isomerism: It is due to behaviour of plane of polarised light. Certain organic compounds, have the ability to rotate
plane of polarised light in either of the directions through certain angle when their solution is placed in the path of plane
of polarised light known as optical active compounds. This property of substances is termed as optical activity.

q q
or &

ck
Monochamotic light Nicol prism Plane polarised Solution of For optically
For optically
light compound inactive
acitive
Specific rotation: Optical rotation caused by 1 gm/ml solution in 1 dm length polarimeter tube at specific temp and source
of the light.

a
observed rotation µ concentration × length
q = [a]TD × concertration × length
q
cr
[a]TD = ​ __________________
     ​
concertration × length
q
[a]TD = ​ ____  ​
e_
c× l
d Optical Rotation
• Enantiomeric axis = ​  ​ 100 = ​ ______________
  
    ​ × 100
d Specific Rotation
q = The observed rotation (Optical rotation)
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a = Thereotical rotation (Specific rotation)

The magnitude of observed rotation (q) depends upon following factors.
(1) Nature of substance.
(2) Nature of solvent.
(3) The concentration of the substance in tube. (C gm/mol)
@

(4) The length of the solution column. (l dm) [1 dm = 10 cm]

(5) The temperature of the experiment (t°C)
(6) The wavelength of the light used. (lÅ)

Optical isomers
All these substances are known to exist in two stages.
(1) Optically active isomer:
(a) One rotating the plane of polarised light to the right is named dextrorotatory
(Latin, Dexter-right) or direction (+) form.
(b) One rotating the plane of polarised light to the left this form is named laevorotatory
(Latin, laevous = left) or direction (–) form.
(2) Optically inactive isomer:
(a) Meso compound:
• Compound having two or more chiral carbons as well as POS, COS and AAOS is known as meso compounds.
• Meso compounds are optically inactive due to internal compensation.
2.8 | Organic Chemistry Module I
• Meso are optically inactive, even though considered in optical isomer.
• Two different meso are diastereomers of each other.
(b) Racemic mixture:
• An equimolar mixture of d and l isomer which does not rotate the plane polarised light hence it is optical inactive
named (±)- mixture or Racemic mixture.
• Racemic mixture are optically inactive due to external compensation.
• Racemic mixture are optically inactive, and not considered in optical isomer.
Theoretical Condition for optical activity:
• Compound must be chiral.
• Compound is non-superimposable on their mirror image.
Type-1: Optically active compound with chiral ‘C’.
Chiral ‘C’: Carbon (sp3) having all four different groups is called as chiral ‘C’.
• Chirality is defined only at sp3 hybridised atom not at sp or sp2 atom.

ck
b Chiral ‘C’
Asymmetric ‘C’
a C d Dissymmdric ‘C’
c Stereogenic ‘C’

a
a π b π d π c
• Compound having only one chiral C, their molecule must be chiral.
cr
• Compound having more than one chiral C, their molecule may be or may not be chiral depending upon symmetry
elements.
Symmetry elements:
e_
(1) Plane of symmetry (POS) (s)
(2) Centre of symmetry (COS) (i)
(3) Axis of symmetry (AOS) (Cn)
(4) Alternative symmetry(AAOS) (Sn)
POS: An imaginary plane which bisects the molecule into two equal half and equal half must be mirror image of each
Je

other is known as plane of symmetry.

COS: An imaginary point within a molecule through which draws a line in opposite directions and gets same atom at
same distance is known as centre of symmetry. This rule is applicable for each atom.
AOS: An imaginary axis through which rotates a molecule by minimum angle that molecule again reappears is known
as axis of symmetry
@

360
n = ​ ____​
q
q 360° 180° 120° 90° 72° 60°
Cn C1 C2 C3 C4 C5 C6

• C1 is not included in axis of symmetry.

AAOS: An imaginary symmetry element in which, first consider imaginary axis of symmetry after that consider imaginary
POS ^ with AOS and again it’s molecule reappears then it is known as alternative axis of symmetry.
Organic compound

Symmetrical Unsymmetrical
(Optically inactive) (Optically active)
(achiral) (chiral)
(POS/COS/AOS/AAOS)
are present Asymmetrical disymmetrical
no POS no POS
no COS no COS
no AOS AOS Present
no AAOS no AAOS
 Isomerism |   2.9
Type-2 Optically active compound without chiral ‘C’
Continuous p-bond/ Even Odd
Ring/both • non planer • Planner
• optically active When • Always inactives
G1 π G2 , G3 π G4 • Can show G.I. When
G1 π G2 , G3 π G4

G1 G3 G1 G3
(1) Allenes C C C C C C C
G2 G4 G2 G4

G1 G3 G1 G3
(2) Cyclo-alkylidenes C C C C C C C
G2 G4 G2 G4

G1 G3 G1 G3
(3) Spiranes C C C C C C
G2 G4 G2 G4

ck
Configuration of optical isomer
(1) D, L-SYSTEM (RELATIVE CONFIGURATION):
• It is applicable for only proper Fischer projection formula

a
• It is mostly used for assigning D/L configuration of carbohydrate (Poly hydroxy carbonyl compound) and protein
(a-amino acid). cr
• It represents relative configuration with respect to glyceraldehydes.
• Following configuration of glyceraldehydes is considered as standard configuration.
e_
Je

• In carbohydrate, group of only last chiral carbon compares with D/L glyceraldehydes
(2) R–S SYSTEM (ABSOLUTE CONFIGURATION):
• R Æ Rectus (Right) S Æ Sinister (Left)
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• R–S nomenclature is assigned as follow:

Rules of R-S configuration in Fischer formula
Step-I: By the set of sequence rule, we give the priority order of atom or group connected though the chiral carbon.
Step-II: If atom/group of minimum priority is present on the vertical line, then put arrow 1 Æ 2 Æ 3.
If it is clockwise fi R but Anti clockwise fi S

Step-III: If minimum priority group present on the horizontal line, then put arrow 1 Æ 2 Æ 3
If it is clockwise fi S but anticlockwise fi R
2.10 | Organic Chemistry Module I

Rule of R-S configuration in wedge dash formula

Step-I: By the set of sequence rule, we give the priority order of atom or group connected though the chiral carbon.
Step-II: If atom/group of minimum priority is present on upward the plane (broken line), then put arrow 1 Æ 2 Æ 3.
If it is clockwise fi R but Anti clockwise fi S
Step-III: Step-II must be satisfied first by golden rule as given below.
By interchanging odd pair of groups across the chiral carbon, its R–S configuration will be opposite.

ck
By interchanging even pair of groups across the chiral carbon, its R–S configuration will remain same
Enantiomers
• d and form of any compound is called enantiomer.
• Non-superimposable mirror image are called enantiomers.

a
• Opposite configuration of any compound are called enantiomers.
Properties of enantiomers cr
(1) Enantiomers have chiral molecule (optically active).
(2) Enantiomers have identical physical properties like BP, MP, refractive index, density, etc.
(3) They rotate PPL in opposite direction but to the equal extent of optical rotation.
(4) They have identical chemical properties, however their rate of reaction will differ if they combine with other opti-
e_
cally active reagents.

{
​ ​R + x
​S + x
k1

k2
P​
}
P ​  ​ X is optically inactive, then K = K
1 2
Je

​ ​
{
R +y

​S + y
k3

k4
P

P​
}
​  ​ Y optically active, then K3 π K4
@

Diastereomers: Such configurational isomers which are neither mirror images nor superimposable on each other are called
as diastereomers.
Properties of diastereomers
(1) They are generally optically active, however geometrical isomers are exceptions.
(2) They have different physical properties like MP, BP, density, solubilities and value of specific rotation.
(3) they are separated by fractional distillation, fractional crystallisation and chromatography, etc.
(4) They exhibit similar but not identical chemical behaviour.
Pseudo chiral carbon: Those achiral carbon converted into chiral carbon whenever stereochemistryof one of the valency
will change.
Prochiral carbon: Those achiral carbon converted into chiral carbon if one of the valency changes by different group.
Calculation of stereo isomer
Type-1: Compound showing only geometrical isomers
Case-1 If R1 π R2 (Unsymmetrical Compound)
(R1–CH=CH–CH=CH–R2)
 Isomerism |   2.11

Number of Geometrical isomers = 2n

n Æ number of stereogenic (double bond) centre
Case-2 If R1 = R2 (Symmetrical Compound)
(R1–CH = CH–CH=CH–R2)

Number of Geometrical isomers = 2n–1 + 2p–1

n
If n is even number then, p = ​ __ ​;
2
n+1
_____
if n is odd number then, p = ​   ​
2
Type-2: Compound showing only Optical isomers
Compound Optically active isomer (a) Number of Total num-
or meso ber of optical

ck
isomer isomer
(m) (a + m)

(1) Unsymmetrical 2n 0 2n
n–1 n/2–1 n –1
(2) Symmetrical 2 2 2 + 2n/2 –1

a
n = even number
(3) Symmetrical
n = odd number

n = number of chiral carbon

cr n –1
​ ____
2n–1 – ​2​ 2 ​
 ​
n –1
​ ____
​2​ 2 ​
 ​
2n –1

Type-3: Compound showing both Optical isomers and Geometrical isomers

e_
(1) Compound Unsymmetrical
Number of stereo isomer = 2n
n = Number of chiral carbon and Number of p-bonds which showing geometrical isomersism
(2) Compound symmetrical – draw and check
Je

Conformational isomerism: Such non-identical arrangements of atoms or group in a molecule obtained by the free
rotation about a single bond that can easily be reconverted at room temperature are known as conformational isomers or
conformers.
Condition: Molecule must have at least only 3 continuous s bonds.
Projection of Tetrahedral Carbon Atom:
@

1. Newman projection: The two s bonded carbon atoms represented by circle by one behind the other so that only the
front carbons are depicted from the centre of the circle while C–H bonds of back carbon are drawn from the circumfer-
ence of circle as
2.12 | Organic Chemistry Module I
2. Sawhorse Projection: The two s bonded e expressed by slanted and elongated line

&

Conformation of ethane:

HH H HH
H H
H

ck
H H H H H
H H H H
H
q = 0° q = 60° q = 120°
(i) (ii) (iii)

a
H HH H
H H cr H H
H H H H
H H H
H
H H
q = 180° q = 240° q = 300°
e_
(iv) (v) (vi)

• Ethane molecule contains infinite number of conformers

• The extreme conformation of ethane molecules is staggered and eclipsed
Je

• All other conformer erist in between 0° + 60° known as skew form.

• The energy of staggered conformation is lower than eclipsed conformation by 2.8 kcal/mole (11.7 kJ/mole).
• Staggered conformation is more stable than the eclipsed conformation
• The mixture contains 99% staggered conformation and 1% eclipsed conformation.
• Eclipsed and staggered conformations are not isolated from the mixture.
@

Order of Stability Staggered > Skew > Eclipsed

Energy Level Comparison of Conformations of Ethane

I I I I

E
II II II

0 60 120 180 240 300 360

Degree of Rotation q
 Isomerism |   2.13
Conformations of Butane (CH5–CH2–CH2–CH3):

ck
(i) = Fully eclipsed form (CH3 group eclipsed by CH3 group)

a
(ii) = (vi) = partial staggered form
(iv) = anti or trans (Staggered) cr
(iii) = (v) = partial eclipsed form (CH3 group eclipsed by H)
Stability order: iv > ii > iii > i
Order of Stability Anti > Gauche > Partially Eclipsed > Fully Eclipsed
e_
Energy Level Comparison of Conformations of n-butane

I I
III III
Je

E II V
IV

0 60 120 180 240 300 360

@

Degree of Rotation q

Cycloalkanes
In cyclopropane and cyclobutane (both planar), C–C–C angle are 60° and 90° respectively. Cyclopentane and cyclohexane
(considered planar though non-planar) with C–C–C angles 180° and 120° respectively.

Baeyer or angle strain Cyclopropane Cyclobutane Cyclopentane Cyclohexane

1
__
​   ​ [109°28¢ – angle] 24°44¢ 9°44¢ 0°44¢ –5°16¢
2

Conformations of Cyclohexane: A cyclohexane ring can assume many shapes and any single cyclohexane molecule is in
a continuous state of flexing or flipping into different shapes which are illustrated as follows:

Chair (more stable) Half-chair Twist-boat Boat (less stable)

(optically active)
2.14 | Organic Chemistry Module I
Interconversion of chair forms is known as conformational inversion and occurs by rotation about carbon-carbon
bonds.
The most stable conformation of cyclohexane is the chair form.
Relative energies of the conformation of cyclohexane molecule
Half chair Half chair
Twist boat

potential energy
Boat

11 kcal/mol 7.1 kcal mol

5.5 kcal mol
Chair Chair
Degree of Rotation q

ck
Actual conformers of cyclohexane with relative energy are as follows :

Conformer Chair Twist boat Boat Half chair

Relative energy 0.000 kJ mol–1 22.2 kJ mol–1 28.9 kJ mol–1 44 kJ mol–1 (approx.)

a
The relative stability of conformations of cyclohexane decreases in the order:
cr
Chair Ò Twist boat Ò Boat Ò Half chair
The potential energy barrier for transformation of chair form to other forms is about 37.8-46.0 kJ mol–1

Solved Example
e_
1. Which are not position isomers? I. They are functional group isomers with molecular
formula C2H4O2.
II. They belong to same homologous series.
(1) III. They have different chemical properties.
Je

(1) I and II (2) I and III

(3) II and III (4) I, II and III
(2) Sol. [2]
@

(3)
Æ m.f. = C2H4O2
Æ functional group differ, So belong different
homologous series and also have different chemical
Properties.
(4) 3. Organic compound with molecular formula C4H8O2
cannot have the functional group
Sol. [2] (1) carboxylic acid (2) ester
(3) dialdehyde (4) cyclic diol
Sol. [3]
H+X–N
D.B.E = (C + 1) – ​ __________  ​
  
Functional group isomer 12

2. Which of the following statements regarding ethanoic ()

8
= (4 + 1) – ​ __
​   ​  ​ = 1
2
acid and methyl methanoate are correct? In dialdehyde, D.B.E = 2 (not possible)
 Isomerism |   2.15
4. Which of the following Compounds are structural 7. How many structural isomers are possible for com-
isomers of C5H10O? pounds containing C, H and O atoms only with their
molar masses 100 as well as the isomers are simul-
I. 2-methyl butanal
taneously ketones?
II. Propyl ethanoate
(1) 3 (2) 4
III. Pentanal
(3) 5 (4) 6
(1) I and II (2) I and III
Sol. [4]
(3) II and III (4) I, II and III
General formula of ketone CnH2nO
Sol. [2]
12n + 2n + 16 = 100
CH3
14n = 84
(In I & III)
CH3–CH2–CH–CH = O C5H10O Size of Parent n=6
chain differ C6H12O
CH3– C –O–CH2–CH2–CH3 C5H10O2
chain isomer

ck
O C4H9 – C–CH3 C3H7 – C–C2H5
CH3–CH2–CH2–CH = O C5H10O
4 O 2 O
5. Select pair of chain isomers from the following
8. An organic compound has three ether isomers and it is

a
the smallest ether which satisfy this condition. Which
(I) (II) cr of the following is true regarding this compound?
(1) Only one alcohol isomer exist
(III) (IV) (2) Four alcohol isomers exist and they are all con-
stitutional isomers
(1) I and II (2) II and IV
(3) Five alcohol isomers exist and they are positional
e_
(3) I and IV (4) II and III isomers of each other
Sol. [4] (4) Molecular formula of the compound is C5H12O
4 3
2
2 1 P.C differ so Sol. [2]
3
1 5
4 they becomes
Chain isomer
Je

(II) (III)
6. An alkyne has molar mass 96. How many different
isomer (excluding stereochemical designation) are
possible considering all of them to be internal
alkynes?
@

(1) 3 (2) 4
(3) 6 (4) 8
Sol. [3]
CnH2n–2 = 96
12n + 2n–2 = 96

14n = 98 9. How many alkene isomers are possible for compound

n=7 with molecular formula C5H10?
m.f. = C7H12 (1) 3 (2) 4
(3) 5 (4) 6
Sol. [4]

number of possible alkyne = 4 + 2 = 6
2.16 | Organic Chemistry Module I
CH3
CH3–CH–CH = CH2 (7)

CH3

CH3–C = CH–CH3 (8)

CH3

CH2 = C–CH2–CH3 2° halide isomer = 3

alkene isomer = 6 12. Which of the following compound will not undergo
10. How many structural isomer are possible with the tautomerism?
molecular formula C8H10
(1) 3 (2) 4

ck
(3) 5 (4) 6
(1) (2)
Sol. [2]
10
D.U = (8 + 1) – ​ ___ ​ = 4
2

a
cr (3) (4)

Sol. [4]
11. How many different secondary halide names can be
assigned to the compounds with molecular formula
e_
C5H11Cl (excluding stereoisomers)?
(1) 3 (2) 4

(3) 5 (4) 7
Sol. [1] 13. Which of the following compound has highest enol
content?
Je

C5H11 –C1
(1) (2)
8
(1) C–C–C–C–C–Cl (1°)
@

(2) (3) (4)

Sol. [3]
(3)

(4)
Æ Stabilised by intramolecular H-bond
Æ Phenyl group, further stabilised via Resonance
(5) 14. Which of the following compounds will not show
geometrical isomerism?
(1) 3-Phenyl-2-propenoic acid
(2) 2-Butene
(6) (3) 3-Methyl-2-butenoic acid
(4) 3-Methyl-2-pentenoic acid
 Isomerism |   2.17
Sol. [3] (3) 3-Methylbutanoic acid
3 2 1 (4) 2-Methylbutanoic acid
C6H5–CH = CH–COOH
Sol. [4]
CH3–CH = CH–CH3
CH3
2 methyl at same double
bonded carbon sop that
CH3–C = CH–COOH
4 3 2 1 no G.I 18. Which of the following is a meso compound:

CH3
(1) (2)
CH3–CH = C–CH–COOH
4 3 2 1

15. Which of the following will have zero dipole

moment?

ck
(1) cis-1, 2-Dichloroethene (3) (4)
(2) trans-1, 2-Dichloroethene
(3) trans-1, 2-Dichloropropene
(4) 2-Pentyne Sol. [1]

a
Sol. [2] CH3 CH3 CH3 CH3
H C1 H Cl H * Cl H * Cl
cr H
*
*

CH3
C1 H
*
*

CH3
H H H
CH2CH3
Cl * H
CH2
2C chiral 1C chiral 1C chiral 2C chiral
POS Present No POS No POS No POS
e_
Meso

Optically active

19.
Je

16. What is the IUPAC name of the following
compound?
@

Relation between (a) and (b) is:

(1) Enantiomer (2) Diastereomer
(3) Identical (4) Structural isomer
(1) hepta-(2E, 4Z) diene (2) hepta (2E, 4E) diene Sol. [2]
(3) hepta-(2Z, 4E) diene (4) hepta-(2Z, 4Z)diene Stereoisomer not mirror image
Sol. [3] Diastereomer
20. The pair of molecules shown are

17. Which of the following compounds exhibits (1) enantiomers
stereioisomerism? (2) diastereomers
(1) 2-Mehylbutene (3) constitutional isomers
(2) 3-Methylbutyne (4) two conformations of the same molecule
2.18 | Organic Chemistry Module I
Sol. [2] 24. An optically pure compound x gave an [a]25
D = + 20.0°.
For comparison of Fischer projection, like groups A mixture of X and its enantiomer Y gave [a]25 D =
should be present on vertical and horizontal lines. + 10°. The ratio of X to Y in the mixture is:
(1) 2 : 1 (2) 1 : 3
21. (3) 3 : 1 (4) 1 : 2

Sol. [3]
Total number of stereoisomers are–
(1) 4 (2) 6 10 1
Enantiomeric axis of d = ​ ___ ​ = ​ __ ​ × 100 = 50%
(3) 8 (4) 12 20 2
Sol. [1] Racemic mix = 50%
n=2
number of streoisomer = 22 = 4 d = 25%, 25
22. Which of the following representations have an R Total d = 50 + 25 = 25%

ck
configuration?
75
​  ​ ​ ___ ​ = 3 : 1
25
(1) (2)

a
CH2Cl
+
cr * *
Cl
(3) (4)
In each one chiral Carbon
present, chiral molecule
Sol. [1]
e_
Br Br +
2 cw Acw 2 Cl
1 C 3 3 C 1 Cl
I Cl Cl I
4 4 No chiral Carbon present,
H H achiral molecule
Je

(R) (S)
25. The most stable conformer of 2-methyl propane is
COOH 3
CH3
Acw 2 Acw
3 C 1 1 C 2
CH3 OH HO CH2–CH3
@

4 4
H H
(S) (S) (1) (2)
23. How many chiral compounds are possible on mono-
chlorination of 2-methyl butane?
(1) 8 (2) 2
(3) 4 (4) 6
Sol. [3]
(3) (4)

Sol. [2]
Only option (2) belongs 2-methyl propane and also
it is more stable

 Isomerism |   2.19

Exercise 1
1. Which of the following statements are correct? (1) 4 (2) 8
I. A pair of positional isomers differs in the position (3) 12 (4) 16
of the same functional group. 9. How many amide isomers are possible for
II. A pair of structural isomers have the same C4H9ON?
relative molar mass (1) 4 (2) 5
III. A pair of functional group isomers belongs to (3) 6 (4) 8
different homologous series.
10. Which of the following compounds will undergo
(1) I and II (2) I and III tautomerism?
(3) II and III (4) I, II and III
2. Assuming a hydrocarbon C5H10 without any double
bond, how many different structures exist that contain (1) (2)
only one alkyl group?

ck
(1) 1 (2) 2
(3) 3 (4) 5
3. Which name is not possible with molecular formula
C6H10?

a
(1) 2-hexyne (2) 3-hexyne
(3) 4-methyl-2-pentyne (4) 3-cyclopropylpropyne
4. Given compound shows which type of isomerism?
cr (3) (4)

11. Which of the following compounds cannot show

e_
tautomerism?

(1) (2)
(1) Chain isomerism
Je

(2) Positional isomerism

(3) Functional group isomerism
(4) Metamerism
5. How many structural isomers of molecular formula
C3H6BrCl? (3) (4)
@

(1) 4 (2) 5
(3) 6 (4) 7
6. The total number of stable acyclic compounds having 12. Order of stability of enol content:
the molecular formula C4H8O is: O O O
(1) 4 (2) 7
(a) CH3–C–CH3 (b) CH3–C–CH2–C–CH3
(3) 11 (4) 14
7. Which of the following statements concerning 3,
4-dibromo-1-pentene and 3, 5-dibromo-2-pentene are O O
correct?
I. They have same molecular formula C5H8Br2 (c) CH3–C–CH2–C–O–Et
II. They are positional isomers
(1) a > b > c (2) b > a > c
III. They have similar chemical properties.
(3) b > c > a (4) a > b > c
(1) I and II (2) I and III
13. Which of the following compounds does not have
(3) II and III (4) I, II and III any geometrical isomer?
8. Number of structural isomers of compound having
molecular formula C4H7Cl is:
2.20 | Organic Chemistry Module I
17. Consider the following compounds,

(1) (2)

(3) (4) The correct E/Z configurational notations for the
compounds I to II are respectively-
(1) Z, Z (2) E, Z
14. Which of the following will show optical isomerism (3) E, Z (4) E, E
as well as geometrical isomerism?
18. A cyclic dichloride has a total five constitutional plus
geometrical isomers. Which of the following satisfy
(1) this condition without altering the carbon skeleton?

ck
(1) Dichloromethyl cyclopropane
(2) Dichlorocyclobutane
(3) Dichlorocyclopentane
(2) (4) Dichlorocyclohexane

a
19. How many cyclic isomers exists (structural and
cr geometrical only) for C3H3Cl3?
(1) 2 (2) 3
(3)
(3) 4 (4) 5
20. Which of the following compounds is a meso
compound?
e_

(4) (1) (2)

Je

15. The correct order of the substituent in each of the

following set in order of priority according to CIP (3) (4)
rule
(1) –Cl > –OH > –SH > H
(2) –CH2–Br > –CH2–Cl > –CH2–OH > –CH3 21. Which of following is not capable of existing
@

enantiomers
(3) –CH = O > –OH > –CH3 > –H
(1) 1, 3-dichloro butane
(4) –OCH3 > –N(CH3)2 > –CH3 > –CD3
(2) 1, 2-dibromo propane
16. The E-isomer among the following is
(3) 1, 4-dichloro pentane
(4) 3-ethyl pentane
(1)
22. Which of the following is not correct representation
of L-amino acids

(2)
(1) (2)

(3)

(3) (4)
(4)
 Isomerism |   2.21
23. Which isomer below has a stable intramoecular
H-bond?
(1) trans-3-fluoro propenoic acid

(2) Cis-3-fluoro propenoic acid
(3) 2-fluoro propenoic acid (1) Enantiomer (2) Diastereomers
(4) 4-fluoro-3-methyl-3-pentenoic acid (3) Identical (4) Structural isomer
24. If solution of a compound (30 g/100 mL of solution) 28. Which compound does not possess a plane of
has measured rotation of +15° in a 2 dm log sample symmetry?
tube, the specific rotation of this compound is
(1) +50° (2) +25° (I) (II)
(3) +15° (4) +7.5°
25. What is true regarding a meso form of a
compound?

ck
(1) A meso form is achiral due ot the presence of (III) (IV)
an axis of symmetry
(2) A meso form does not contain any chiral
carbon
(V)

a
(3) A meso form cannot be isolated from its optically
active stereoisomer by fractional crystallisation
(4) A meso form is achiral due to internal
compensation of optical rotation
cr
26. Which structures represent(s) diastereomers of l?
(1) I, II and V
(3) II, III and IV
(2) I, III and IV
(4) III and IV
29. Dextrorotatory a-pinene has a specific rotation n
[a]20
D = + 51.3°. A sample of a-pinene containing
e_
both the enantiomers was found to have a specific
(I) (II) rotation value [a]20
D = + 30.8°. The percentages of
the (+) and (–) enantiomers present in the sample
are, respectively:
Je

(1) 70% and 30% (2) 80% and 20%

(3) 20% and 80% (4) 60% and 40%
30. What is wrong about enantiomers of 2-chloropro-
panoic acid?
(1) Have same solubility in water
@

(III) (IV) (2) Have same pKa value

(3) Have same refractive Index
(4) Have same rate of reactions with (+)-2-butanol
31. How many stereoisomers exist for the compound
4-(1-propenyl) cyclohexene?
(1) 2 (2) 3
(3) 4 (4) 5
(V) 32. Calculate the number of stereoisomerism for

(1) Only II (2) II and III

(3) II and IV (4) III and IV
27. Relation between given pair is:
(1) 2 (2) 4
(3) 8 (4) 6
2.22 | Organic Chemistry Module I
33. The number of stereoisomers possible for the
compound is-
(3) (4)

37. Which is true about conformers of 1, 1, 2,
(1) 2 (2) 4 2-tetrachloroethane?
(3) 6 (4) 8 (1) The most stable conformer has dihedral angle of
60° between all adjacent chlorine atoms
(2) In the least stable conformer, two Cl-atoms are
eclipsing one another while other two Cl-atoms
34. are eclipsed to hydrogen atoms
(3) In the most stable conformer, dihedral angle
between hydrogen atoms is 60°

ck
(4) The most stable conformer is non-polar
38. Consider the following structure

a
a and b are stereoismers sum of (a + b = ?) O
(1) 4 (2) 6 cr
(3) 8 (4) 12
35. Which of the following represents the staggered con-
formation of ethane?
Its IUPAC name is
e_
(1) (Z)-3, 4-diethyl-1-methoxy-5-methyl-3-hexene
(2) (E)-3, 4-diethyl-1-methoxy-5-methyl-3-hexene
(3) (E)-3, 4-diethyl-6-methoxy-2-methyl-3-hexene
(4) (Z)-3, 4-diethyl-6-methoxy-2-methyl-3-hexene
39. Which of the following statements is incorrect about
Je

cis and trans isomers ?

(1) I and II (2) I, II and III (1) cis-2-butene can be converted into trans-2-butene
(3) I and III (4) II, III and IV by irradiation
36. Consider the following Newman projection. (2) In general trans isomers have zero dipole
@

moment
(3) On heating, fumaric acid (a trans acid) gives an
anhydride
(4) On heating, maleic acid (a cis acid) gives an
anhydride
40. The in correct statement concerning various conform-
ers of 2-fluoroethanol is/are
Which of the following is the correct representation (1) Anti-conformer is the most stable conformer
of the same compound in Fischer projection formula
(2) There is intramolecular H-bonding in its most
(ignore conformational aspect)?
stable conformer
(3) The most stable conformer has greater steric
strain than 2nd most stable conformer
(1) (2) (4) Dissolving in water lower the percentage of most
stable conformer
 Isomerism |   2.23

Exercise 2
1. How many different isomer can be given to
bromodichlorobenzene?
(1) 3 (2) 4
(3) 6 (4) 7

2. How many cycloalkene isomers exist for C5H8 which
(1) It is having two stereocentres
contain at least one methyl locant directly present on
the ring? (2) Its configuration at double bond is E
(3) It shows optical isomerism
(1) 2 (2) 4
(4) It shows geometrical isomerism
(3) 5 (4) 6
9. Which of the following compound is chiral?
3. How many structural isomers exist for C4H8O which
are simultaneously ether? Also there is no atom sp2-
hybridised. (1) (2)

ck
(1) 3 (2) 4
(3) 6 (4) 7
4. A hydrocarbon has molecular formula X(C6H6). Also,
X has triple bonds as the only type of unsatura-

a
tion, i.e., it has neither double bonds nor any ring (3) (4)
structure. How many different IUPAC name can be
cr
assigned to X?
(1) 3 (2) 4
(3) 5 (4) 7 CH3 CH3
10.
e_
O O

ƒ
5. H
Number of chiral center present in above compounds
are:
Number of positional isomer are:
Je

(1) 1, 1 (2) 1, 2
(1) 4 (2) 5 (3) 2, 1 (4) 2, 3
(3) 6 (4) 7 11. Which of the following molecule is chiral?
6. Which of following compound will not show geo-
metrical isomerism?
(1) (2)
@

(1) (2)

(3) (4)
(3) (4)

7. Among the configurations 12. Consider the following structures,

Which one of the following statements is correct
The meso pair is-
about the structures (X) and (Y)?
(1) I and II (2) I and IV
(1) Both (X) and (Y) exhibit enantiomerism
(3) III and IV (4) II and III
(2) Both (X) and (Y) exhibit distereomerism
8. False statement about the following compound is–
2.24 | Organic Chemistry Module I
(3) (X) exhibits enantiomerism while (Y) exhibits
distereomerism
(4) (X) exhibits distereomerism while (Y) exhibits (3)
enantiomerism
13. Which two of the following compounds are
identical?

(4)

ck
17.

Which of the following statements is correct?

a
(1) I and II are conformational isomers while II and
III are functional isomers
(1) I & II
(3) III & IV
(2) II & IV
(4) I & III
cr (2) I and II are functional isomers while II and III
are conformational isomers
14. How many stereo isomers are possible for the fol-
lowing molecule? (3) I and II are functional isomers while I and III
are conformational isomers
e_
(4) I and II are functional isomers while I and III
are metamer isomers
18. The total number of dimethylphenols having the
(1) 4 (2) 8 molecular formula C8H10O is:
Je

(3) 16 (4) 32 (1) 3 (2) 4

15. The structures shown here are related as being: (3) 6 (4) 8
19. Which of the following structures represents a chiral
compound?
@

(1) (2)

(1) Conformers (2) Enantiomorphs
(3) Geometrical isomers (4) Diastereoisomers
16. Which of following pair is Diastereomers? (3) (4)

(1) 20. (+)-mandelic acid has a specific rotation of 158°.

What would be the observed specific rotation of a
mixture of 25% (–)-mandelic acid and 75% (+)-man-
delic acid?
(1) +118.5° (2) –118.5°
(3) –79° (4) +79°
(2)
21. Which species exhibits a plane of symmetry?
 Isomerism |   2.25
(1) CH3–CH=C=CH–CH3
(2) CH3–CH=C=C=CH–CH3
(1) (2)

(3)

(3) (4)

(4)
22. Which of the following represents Z-3-chloro-3-
heptene?
25. How many geometrical isomers exist for the mol-
ecule shown below?
(1)

ck
(2)

a

(1) 2 (2) 3
(3)
cr (3) 5 (4) 6
26. If chlorocyclohexane is subjected to further
chlorination, how many different isomers (geomet-
rical plus structural only) of dichlorocyclohexane
e_
(4) would be produced?
(1) 3 (2) 5
23. Which compound below can show geometrical (3) 6 (4) 7
isomerism?
27. The correct statement regarding elements of sym-
Je

metry and chirality of compound is

(1)
(1) Presence of an axis of symmetry destroy chiral-
ity
(2) Centre of symmetry has no role to play in chiral-
ity of a compound
@

(2) (3) A compound with either plane or centre of sym-

metry is always achiral
(4) A compound with an axis of symmetry simulta-
neously contain centre of symmetry
28. Consider the following set of molecules

(3)
(I) (II)

(III) (IV)
(4)

(V)
24. Which compound below is capable of showing geo-
metrical isomerism?
2.26 | Organic Chemistry Module I
The pairs of enantiomers are The configurations at the chiral centre and the double
(1) I, II, III and IV (2) I and II bond are respectively,
(3) III and IV (4) IV and V (1) R and E (2) R and Z
29. How many stereoisomers are possible for the com- (3) S and Z (4) S and E
pound 2, 5-heptadiene-4-ol? 36. If a hydrogen of 1, 3-pentadiene is substituted by
(1) 2 (2) 3 chlorine, how many different isomer (excluding ste-
(3) 4 (4) 5 reochemical designation) can be assigned to the chlo-
30. A stereoisomer of cyclobutane-1,2-diol has lower rinated dienes?
solubility in water than its other stereoisomer, which (1) 2 (2) 3
is this isomer and why? (3) 4 (4) 5
(1) Trans, lower dipole moment 37. How many different structural isomers exist for C5H8
(2) Cis, higher dipole moment that have only sp3-hybridised carbon atoms?
(3) Cis, intramolecular H-bonding (1) 3 (2) 4
(4) Trans, intramolecular H-bonding

ck
(3) 5 (4) 7
31. Which of the following correctly ranks the cycloal- 38. Which compound below has four stereoisomers?
kanes in order of increasing ring strain per methylene
group? (1)
(1) Cyclopropane < Cyclobutane < Cyclopentane < (2) H – N = N – N = N – H

a
Cyclohexane
(2) Cyclohexane < Cyclopentane < Cyclobutane <
cr (3)
Cyclopropane (4)
(3) Cyclohexane < Cyclobutane < Cyclopentane <
Cyclopropane
(4) Cyclopropane < Cyclopentane < Cyclobutane < 39.
e_
Cyclohexane
32. The correct statement concerning conformers of
1, 2-dichloroethane is Incorrect statement about this compound is:
(1) It’s gauche conformer has higher potential en- (1) It shows geometrical isomerism
ergy than an eclipsed conformer in which H–Cl (2) It possess centre of symmetry
Je

aoms are eclipsing (3) It possess plane of symmetry

(2) Syn-periplanar conformer is most stable (4) It shows optical isomerism
(3) Increasing temperature decreases dipole moment Sol. [2]
of 1, 2-dichloroethane
(4) The two gauche conformers are enantiomers
@

33. Which of the following is achiral

(1) 2-bromo bicyclo [1, 1, 0] butane
(2) 2-fluoro bicyclo [2, 2, 2] octane
(3) 2-chloro bicyclo [2, 1, 1] hexane
(4) 5-chloro bicyclo [2, 1, 1] hexane
34. In the compound POS present
COS absent
C* present
G.I. present
The configurations at the chiral centre and the double 40. The absolute configuration of the below figure is:
bond are respectively,
(1) R and E (2) R and Z
(3) S and Z (4) S and E
(1) 2R, 3S (2) 3R, 4S
35. (3) 2S, 3R (4) 3S, 4R
 Isomerism |   2.27

Exercise 3
One and More Than One Option Correct (2) A meso compound has no chiral centres and thus
Type Question are optically inactive
(3) Meso compounds are superimposable on their
1. The correct statement(s) regarding the isomers of
mirror images even though they contain chiral
compound N-ethyl-N-methyl-1-propanamine is/are
centres
(1) A pair of enantiomers remain in dynamic
(4) Meso compounds do not show optical activity due
equilibrium
to external compensation of optical rotation
(2) Addition of HCl results in the formation of
5. Which of the following will show optical isomerism
enantiomeric hydrochloride salts
as well as geometrical isomerism?
(3) Addition of a pure enantiomer of 2-methyl
butanoic acid to the solution of amine results in
formation of a pair of diastereomeric salts
(1)

ck
(4) Its enantiomers can be separated by gas
chromatography
2. Consider the following molecule

a
(2)

cr
The correct statement/s concerning above molecule
is / are (3)
(1) It has a total of six stereoisomers
e_
(2) It’s meso form upon ozonolysis followed by Zn-
hydrolysis gives racemic mixture
(3) It’s optically active isomers, each upon ozonol-
ysis followed by Zn-hydrolysis given a single (4)
Je

enantiomer
(4) It has only two optically active isomers
3. The correct statement(s) concerning the following 6. The correct statement (s) concerning aldehydes of
Newmann’s projections is/are general formula C5H10O is/are
(1) It has total five aldehyde isomers
@

(2) Two of the aldehydes are chiral

(3) Two of the aldehyde isomers have no enol
(4) All enols of aldehyde isomers are
diastereomeric
7. Which compound below can have a non-polar
stereoisomers?
(1) I and II correspond to conformers of enantiomers
of 2, 3-dichlorobutane
(2) I and III are two conformers of the same (1) (2)
enantiomer of 2, 3-dichlorobutane
(3) III is the most stable conformer of meso-2, 3-di-
chlorobutane
(4) I and II are conformers of a pair of diastereomers
(3) (4)
of 2, 3-dichlorobutane
4. Which of the following statements is/are correct ?
(1) A meso compound has chiral centres but exhibits 8. The correct statement(s) concerning the following
no optical activity structures is/are
2.28 | Organic Chemistry Module I
(1) Statement-1 is true, statement-II is true and state-
ment-II is correct explanation for statement-I
(2) Statement-1 is true, statement-II is true and
statement-II is NOT the correct explanation for
statement-I
(3) Statement-I is true, statement-II is false
(1) P and Q are enantiomers (4) Statement-I is false, statement-II is true
(2) P and Q are diastereomers 12. Statement-I: Fluoroethanal has two stereomeric enols
(3) Both are optically active in which cis enol predominates at equilibrium.
(4) P is optically inactive while Q is optically active Statement-II: Intramolecular H-bonding increases
the stability of a stereomer.
9. Which of the following compounds can show
geometrical & optical isomerism. 13. Statement-I: The compound shown below is opti-
cally inactive.

ck
(1) (2)

a

(3) (4)
cr Statement-II: Compound shown above possesses
axis of rotation.
Statement type Question
14. Statement-I: Enantiomers differ in their chemical
(1) If both Statement-I and Statement-II are correct action with other enantiomer.
and Statement-II is the correct explanation for Statement-II: A pair of enantiomers have differ-
e_
Statement-I ent orientation of collision with another enantiomer
(2) If both Statement-I and Statement-II are correct forming different transition state.
and Statement-II is not the correct explanation
for Statement-I Comprehension type question
(3) If Statement-I is correct and Statement-II is
Je

Passage (Q. 15–17)

incorrect
Organic compound with molecular formula C3H6O has one
(4) If Statement-I is incorrect and Statement-II is
degree of unsaturation. One degree of unsaturation can be
correct
present in the form of a pi-bond or a ring structure. Pi-bond
10. Statement-I: Molecules that are non-superimposable can be formed between carbon atoms or between carbon and
on their mirror images are chiral
@

oxygen atom.
Statement-II: All chiral molecules have chiral 15. How many isomers exist for this compound that have
centres. a ring structure?
(1) If both statement-I and statement-II are true but (1) 1 (2) 2
statement-II is not a correct explanation of the (3) 3 (4) 4
statement-I
16. If only carbonyl isomers (aldehyde and ketone) are
(2) If both statement-I & statement-II are true & considered, how many corresponding enol isomers
the statement-II is a correct explanation of the would be possible?
statement-I
(1) 1 (2) 2
(3) If statement-I is true and statement-II is false
(3) 3 (4) 4
(4) If statement-I is false and statement-II is true
17. How many isomers of this compound exist that have
no stereoisomer?
11. Statement-I: Percentage enol content for is (1) 2 (2) 4
(3) 6 (4) 7
almost 100%. Passage (Q. 18–20)
Statement-II: Due to aromaticity, stability of The two major contributors of conformers of 1,2-dichlo-
enol increases, hence percentage enol content also roethane are anti and gauche. At 32°C in gas phase, the
increases. measured dipole moment of 1,2-dichloroethane is 1.12 D.
 Isomerism |   2.29
The dipole moment of a mixture of X and Y is given by (2) There is only one gauche conformer in about
the relationship 64%
m2 = Nxm2x + Ng u2g (3) There is racemic mixture, although inseparable,
Here, N = mole fraction of each kind of molecule. From bond of gauche conformers, about 12%
moment measurement, it has been estimated that gauche con- (4) There is racemic mixture, although inseparable,
former of 1, 2-dichloroethane should have a dipole moment of gauche conformers, about 64%
of about 3.2 D. 20. What happens if temperature if increased to 52°C?
18. What per cent of conformers of 1,2-dichloroethane (1) Percentage of gauche conformers decreases and
is anti, at 32°C? that of anti-conformers
(1) 12% (2) 36% (2) Percentage of both gauche and anti conformers
(3) 60% (4) 89% increases
19. What is true about percentage of gauche (3) No change in percentage of anti and gauche
conformer? conformers occur
(1) There is only one gauche conformer is about (4) Percentage of both anti and gauche conformers

ck
12% decreases

Column matching type question

21. Match list I with List II and select the correct answer from the codes given below the lists:

a
List-I List-II

(A) and
cr (P) Enantiomer
e_

(B) (Q) Position isomers

Je
@

(C) (R) Metamers

(D) (S) Tautomers

Codes:
A B C D
(1) R Q S P
(2) R Q P S
(3) P Q R S
(4) Q R S P
22. Match the quantity from Column I with the types of isomerism from Column II.
2.30 | Organic Chemistry Module I
Column I Column II
(i) Pentene (p) Has two positional isomers.
(ii) 1-methoxypropene (q) Has two geometrical isomers.
(iii) Dichlorocyclopropane (r) Has six geometrical isomers.
(iv) 2, 4, 6-octatriene (s) Has more than four cyclic isomers.
Codes
(i) (ii) (iii) (iv)
(1) p, q, s p, s p, r, s p, s
(2) p q r s
(3) p, s p, q, r s, p, q p
(4) q, r p, s r, s q
23. Consider the molecules in Column I and match them with their stereochemical properties from Column II.
Column I Column II

ck
(i) (p) Have only three stereoisomers

(ii) (q) Have four stereoisomers

a
(iii) cr (r) Have only two optically active isomers.

(iv) CH3–CH–CH = CH–Cl (s) Have more than two pairs of diastereomers.

OH
e_
Codes
(i) (ii) (iii) (iv)
(1) q, r, s p, r q, s q, s
(2) p q r s
Je

(3) p, q q, s r q
(4) p, q, r r, s q, r p, q
24. Match the structures on the left Column I with the properties on the right Column II.
Column I Column II
@

(i) (p) Has plane of symmetry

(ii) (q) Has axis of symmetry

(iii) (r) Has centre of symmetry

(iv) (s) Rotate plane polarised light

 Isomerism |   2.31
Codes
(i) (ii) (iii) (iv)
(1) r,s p,q q,r p,s
(2) p,q,r,s r,s p q
(3) p,r q,s p,q,r p,q
(4) p q r s
25.
Column I Column II

(A) (P) Structural isomers

ck
(B) (Q) Enantiomers

a
(C)
cr
(R) Compounds which are geometrical isomer and
diastereoisomers
e_

(D) (S) Compound are geometrical isomers and enantiomers

Je

(1) (A)Æ(R); (B)Æ(Q); (C)Æ(P); (D)Æ(S)

@

(2) (A)Æ(Q); (B)Æ(R); (C)Æ(P); (D)Æ(Q)

(3) (A)Æ(R); (B)Æ(Q); (C)Æ(S); (D)Æ(P)
(4) (A)Æ(R); (B)Æ(S); (C)Æ(Q); (D)Æ(S)

26. Column-I Column-II

(Compound) (Number of isomer)

(A) (P) 2

(B) (Q) 3

(C) (R) 4

(D) (S) 6
2.32 | Organic Chemistry Module I
(1) (A)Æ(Q); (B)Æ(R); (C)Æ(P); (D)Æ(P)
(2) (A)Æ(R); (B)Æ(P); (C)Æ(Q); (D)Æ(P)
(3) (A)Æ(R); (B)Æ(Q); (C)Æ(P); (D)Æ(P)
(4) (A)Æ(R); (B)Æ(Q); (C)Æ(Q); (D)Æ(P)

Single digit integer type question

27. How many isomers, each containing a phenyl ring, 31. How many pairs of diastereomers can be made for
are possible for C9H12? the compound shown below?
28. How many different isomers of alkene with molecu-
lar formula C7H14, on catalytic hydrogenation, can
give 3-methyl hexane?
29. Total number of chiral centers in amoxicillin, which
belongs to the family of semisynthetic penicillins.

ck
32. Find out the total number of stereoisomers of the
given following compound.

a


cr 33. How many different structural isomers exist for
C3H6O in which no atom is sp2 or sp-hybridised?
30. Total number of plane of symmetry present in given 34. Consider the following reaction
compound is
e_
H2 Cl2
(X) C6H12 C6H14 C6H13Cl (Y)
Ni hn
(4 positional isomers)

How many different isomers of X satisfy the above

Je

condition?

Exercise 4
1. Stereo-Isomerism includes [AIEEE-2002] (3) Meso compounds
@

(1) Geometrical isomerism only (4) Enanitiomers with chiral carbon

(2) Optical isomerism only 4. Geometrical isomerism is not shown by
(3) Both geometrical & optical isomerism [AIEEE-2002]
(1) 1, 1-dichloro-1-pentene
(4) Position & Functional isomerism
(2) 1, 2-dichloro-1-pentene
2. Which of the following does not show geometrical
(3) 1, 3-dichloro-2-pentene
isomerism– [AIEEE-2002]
(4) 1, 4-dichloro-2-pentene
(1) CH3–CH=CH–CH3
5. Racemic mixture is– [AIEEE-2002]
(2) CH3–CH2–CH=CH2
(1) A mixture of chiral carbons
(3) (2) A mixture of isomers
(3) A mixture of aldehydes and ketones
(4) CIHC=CH–CH2–CH3 (4) A mixture of alcohols and ethers
3. Racemic mixture is formed by mixing two– 6. Following types of compounds (as I and II)
[AIEEE-2002] (i) CH3CH=CHCH3
(1) Isomeric compounds
(ii) [AIEEE-2002]
(2) Chiral compounds
 Isomerism |   2.33
Are studied in terms of isomerism in (1) Gauche, Eclipse, Anti
(1) chain isomerism (2) Eclipse, Anti, Gauche
(2) position isomerism (3) Anti, Gauche, Eclipse
(3) conformers (4) Eclipse, Gauche, Anti
(4) stereoisomerism 13. Which one of the following conformation of cyclo-
7. Among the following four structures i to iv hexane is chiral? [AIEEE-2007]
[AIEEE-2003] (1) Twist boat (2) Rigid
(3) Chair (4) Boat
14. Which of the following molecules is expected to
(I) (II) rotate the plane of plane-polarised light?
[AIEEE-2007]

(III) (IV)
(1) (2)

ck
It is true that–
(1) Only (III) is a chiral compound

a
(2) Only (II) and (IV) are chiral compounds (3) (4)
(3) All four are chiral compounds cr
(4) Only (I) and (II) are chiral compounds
8. Which of the following compounds is not chiral? 15. The absolute configuration of the compound is
[AIEEE-2004] [AIEEE-2008]
(1) 1-chloropentane
e_
(2) 2-chloropentane is
(3) 1-chloro-2-methyl pentane
(4) 3-chloro-2-methyl pentane
(1) R, R (2) R, S
9. Which of the following will have a meso isomer
(3) S, R (4) S, S
Je

also [AIEEE-2004]
16. The alkene that exhibits geometrical isomerism is
(1) 2-Chlorobutane [AIEEE-2009]
(2) 2, 3-Dichlorobutane (1) Propene (2) 2-methyl propene
(3) 2, 3-Dichloropentane (3) 2-butene (4) 2-methyl-2-butane
(4) 2-Hudroxypropanoic acid
@

17. The number of stereoisomers possible for a compound

10. For which of the following parameters, the structural of the molecular formula CH3–CH=CH–CH(OH)–Me
isomers C2H5OH and CH3OCH3 would be expected is [AIEEE-2009]
to have the same values? (Assume ideal behaviour) (1) 3 (2) 2
[AIEEE-2004] (3) 4 (4) 6
(1) Heat of vaporisation 18. Out of the following the alkene that exhibits optical
(2) Vapour pressure at the same temperature isomerism is– [AIEEE-2010]
(3) Boiling points (1) 2-methyl-2-pentene (2) 3-methyl-2-pentene
(4) Gaseous densities at the same temperature and (3) 4-methyl-1-pentene (4) 3-methyl-1-pentene
pressure 19. Identify the compound that exhibits tautomerism
11. Which type of isomerism is shown by 2,3-dichlorob- [AIEEE-2011]
utane [AIEEE-2005] (1) 2-Butene (2) Lactic acid
(1) Optical (2) Diastereo isomerism (3) 2-Pentanone (4) Phenol
(3) Structural (4) Geometric 20. How many chiral compounds are possible on mono-
12. Increasing order of stability among the three main chlorination of 2-methyl butane? [AIEEE-2012]
conformations (i.e., Eclipse, Anti, Gauche) of 2-flu- (1) 2 (2) 4
oroethanol is [AIEEE-2006] (3) 6 (4) 8
2.34 | Organic Chemistry Module I
21. Maleic acid and fumaric acids are: [AIEEE-2012] 27. The number of structural isomers for C6H14 is–
(1) Tautomers [JEE Main Online-2015]
(2) Chain isomers (1) 6 (2) 4
(3) Geometrical isomers (3) 3 (4) 5
(4) Functional isomers 28. The optically inactive compound from the following
22. The IUPAC name of the following compounds is is– [JEE Main Online-2015]
[JEE Main Online-2012] (1) 2-chloropropanal
(2) 2-chlorobutane
(3) 2-chloro-2-methylbutane
(4) 2-chloropentane
(1) (Z) – 5 – heptene – 3 – yne 29. Which of the following pairs of compounds are
positional isomers– [JEE Main Online-2015]
(2) (Z) – 2 – heptene – 4 – yne
(3) (E) – 5 – heptene – 3 – yne

ck
(1)
(4) (E) – 2 – heptene – 4 – yne
23. Monocarboxylic acids are functional isomers
[JEE Main Online-2013]
(2)

a
(1) Ethers (2) Amines
(3) Esters (4) Alcohols
24. Arrange in the correct order of stability (decreasing
order) for the following molecules–
cr (3)

[JEE Main Online-2013]

(4)
e_

30. The absolute configuration of is

Je

[JEE-main-2016]
(1) (2S, 3R) (2) (2S, 3S)
@

(3) (2R, 3R) (4) (2R, 3S)

31. If C2­ in above compound is rotated by 120° angle
in anticlockwise direction along C2–C3, which of the
(1) I > II > III > IV (2) IV > III > II ª I following form will be produced
(3) III > I ª II > IV (4) I > II ª III > IV [IIT-2004]
25. Which one of the following acids does not exhibit
optical isomerism– [JEE Main Online-2014]
(1) Lactic acid (2) Tartaric acid
(3) Maleic acid (4) a-amino acid
26. Which of the following compounds will exhibit
geometrical isomerism? [JEE-Main-2015]
(1) 1-Phenyl-2-butene (1) Partial eclipsed
(2) 3-Phenyl-1-butene (2) Perfectly eclipsed
(3) 2-Phenyl-1-butene (3) Perfectly staggered
(4) 1, 1-Diphenyl-1-propane (4) Gauche conformation
 Isomerism |   2.35
32. mobs = SmiXi where mI is the dipole moment of
stable conformer and Xi is the mole fraction of that
conformer. [IIT-2005, Subjective type]
(a) Write stable conformer for Z–CH2–CHs–Z in
Newman’s projection.
If µsolution = 1.0 D and mole fraction of anti
form
= 0.82, find µgauche
(b) Write most stable meso conformer of (CHDY)2
If (i) Y = CH3 about C2-C3 rotation and
(1) E, F and G are resonance structures
(ii) Y = OH about C1-C2 rotation
(2) E, F and E, G are tautomers
Cl2/hv (3) F and G are geometrical isomers
33. N (no. of isomers)
(4) F and G are diastereomers

ck
Fractuional distillation
(F), (N) and (F) are: [IIT-2006] 38. Give the total number of cyclic structural as well
(1) 6, 4 (2) 4, 4 as stereo isomers possible for a compound with the
molecular formula C5H10. [IIT-2009, Integer type]
(3) 6, 6 (4) 3, 3
39. The correct statement about the compound H3C(HO)

a
34. The number of structural isomers for C6H14 is
[IIT-2007] HC–CH=CH–CH(OH)CH3(X) is [IIT-2010]
(1) The total number of stereo isomers possible for
(1) 3
(3) 5
(2) 4
(4) 6
cr X is 6
(2) The total number of distereomers possible for X
35. Statement-I: Molecule that are non superimposable
is 3
on their mirror images are chiral.
(3) If the stereochemistry about the double bond in
e_
Statement-II: All chiral molecules have chiral
X is trans, the number of enantiomers possible
centres. [IIT-2007]
for X is 4
(1) If both Statement-I and Statement-II are correct
(4) If the stereochemistry about the double bond in
and Statement-II is the correct explanation for
X is cis, the number of enantiomers possible for
Statement-I.
X is 2
Je

(2) If both Statement-I and Statement-II are correct

40. In the Newman projection for 2, 2-dimethylbutane
and Statement-II is not the correct explanation
[IIT-2010]
for Statement-I.
(3) If Statement-I is correct and Statement-II is
incorrect.
@

(4) If Statement-I is incorrect and Statement-II is

correct.
36. The correct statement about the compound given
below is [IIT-2008]
X and Y can respectively be
(1) H and H (2) H and C2H5
(3) C2H5 and H (4) CH3 and CH3

41. The total number of cyclic isomers possible for a
(1) The compound is optically active hydrocarbon with the molecular formula C4H6 is
(2) The compound possesses center of symmetry [IIT-2010]
(3) The compound possesses plane of symmetry
(4) The compound possesses axis of symmetry (1) 5 (2) 4
37. Which is correct statement concerning the structures (3) 2 (4) 3
E, F and G is [IIT-2008] 42. The maximum number of isomers (including
stereoisomers) that are possible on monochlorination
of the following compound, is– [IIT-2011]
2.36 | Organic Chemistry Module I

(1) 5 (2) 6
(3) 5 (4) 8

43. Which of the given statement(s) about N, O, P and
Q with respect to M is (are) correct? [IIT-2012] 46. The Structure of D-(+)-glucose is
[JEE-Adv-2015, Integer type]

a ck

cr The structure of L-(–)-glucose is
e_

(1) M and N are non-mirror image Stereoisomers

(2) M and Q are identical (1) (2)
(3) M and P are enantomers
Je

(4) M and Q are identical

44. The correct combination of names for isomeric
alcohols with molecular formula C4H10O is/are
[JEE-Adv-2014]
(1) tert-butanol and 2-methylpropan-2-ol
@

(2) tert-butanol and 1, 1-dimethylethan-1-ol

(3) n-butanol and butan-1-ol
(4) isobutyl alcohol and 2-methylpropan-1-ol
45. The total number of stereoisomers that can exist for (3) (4)
M is [JEE-Adv-2015, Integer type]

Answer Key

Exercise # 1 16. (2) 17. (1) 18. (2) 19. (2) 20. (3)
1. (1) 2. (2) 3. (4) 4. (2) 5. (2) 21. (4) 22. (2) 23. (2) 24. (2) 25. (4)
6. (4) 7. (4) 8. (3) 9. (4) 10. (4) 26. (2) 27. (1) 28. (4) 29. (2) 30. (4)
11. (4) 12. (3) 13. (4) 14. (1) 15. (2) 31. (3) 32. (2) 33. (3) 34. (2) 35. (1)
36. (1) 37. (4) 38. (2) 39. (3) 40. (1)
 Isomerism |   2.37

Exercise # 2 3. [4]
CH3–CH2–CH2–C∫C–CH3
1. (3) 2. (4) 3. (3) 4. (3) 5. (3)
2-hexyne (C6H10)
6. (3) 7. (3) 8. (1) 9. (2) 10. (2)
CH3–CH2–C∫C–CH2–CH3
11. (2) 12. (3) 13. (2) 14. (3) 15. (4)
3-hexyne (C6H10)
16. (2) 17. (4) 18. (3) 19. (4) 20. (4)
21. (4) 22. (4) 23. (4) 24. (2) 25. (2)
26. (4) 27. (3) 28. (3) 29. (3) 30. (3)

31. (2) 32. (4) 33. (1) 34. (2) 35. (3)
2-methyl 2-pentyne (C6H10)
36. (4) 37. (3) 38. (3) 39. (2) 40. (3)

Exercise # 3
1. (1, 2, 3) 2. (1, 2, 3) 3. (1, 3, 4) 4. (1, 3) 3-cyclo propyl propyne (C6H8) hence it is not

ck
5. (1, 3, 4) 6. (1, 2, 4) 7. (2, 3, 4) 8. (2, 4) possible.
9. (1, 2) 10. (3) 11. (1) 12. (1) 13. (4) 4. [2]
14. (1) 15. (4) 16. (3) 17. (4) 18. (4)
19. (3) 20. (3) 21. (1) 22. (3) 23. (1)

a
24. (3) 25. (2) 26. (3) 27. (8) 28. (9)
29. (4) 30. (3) 31. (5) 32. (4) 33. (2)
34. (3)

Exercise # 4
cr
Locant position (3, 4, 5) & (2, 4, 5) differ along same
parent chain
1. (3) 2. (2) 3. (4) 4. (1) 5. (1)
5. [2]
e_
6. (4) 7. (4) 8. (1) 9. (2) 10. (4)
11. (1) 12. (2) 13. (1) 14. (1) 15. (1) H+X–N
___________ 6+2
D.B.E = (C + 1) – ​     3 + 1 – ​ _____
 ​ =  ​ = 0
16. (3) 17. (3) 18. (4) 19. (3, 4) 20. (2) 2 2
21. (3) 22. (4) 23. (3) 24. (3) 25. (3)
26. (1) 27. (4) 28. (3) 29. (1) 30. (1)
Je

31. (4) 32. (1) 33. (1) 34. (3) 35. (3)
36. (1, 4) 37. (2, 3, 4) 38. (7) 39. (1, 4) 40. (2, 4)
6. [4]
41. (1) 42. (4) 43. (1,2,3) 44. (1,3,4) 45. (2)
46. (1) Molecular formula C4H8O correspond to CnH2nO so
that isomers are
@

Hint and Solution Aldehyde / ketone / unsaturated alcohol / unsaturated

ether
Exercise # 1
1. [1]
As per definition
2. [2]
• Given molecular formula C5H10 corresponds to
CnH2n so that isomers should be alkene and cyclo
alkane.
• C5H10 do not have double bond so it must be cyclo
alkane.
• Alkyl containing cyclo alkane are
CH3
CH2–C=CH2 fi 1
OH
2.38 | Organic Chemistry Module I
CH2=CH–O–CH2–CH3 fi 1
CH2=CH–CH2–O–CH3 fi 1
CH3–CH=CH–O–CH3 fi 2
(GI)
CH3
CH2=C–O–CH3 fi 1
CH3
CH2–CH=CH–CH3 fi 2
(GI)
OH
Total isomer = 14
No unsaturation.
7. [4]

ck
10. [4]
Br Br
5 4 3 2 1
M.F = C5H8Br2
CH3–CH–CH–CH=CH2 Position isomer
Br Br functional group fi

a
same so chemical
CH2–CH2–C=CH–CH3 properties are same
cr
8. [3]
M.P. = C9H7Cl

(H+X–N
D.B.E. = (C + 1) – ​ __________
​ 
2
 ​ )
   ​
e_
7+1–0
= (4 + 1) – ​ ________
 ​ = 1
2
fi
Je

fi
@

O Carbonyl group
fi
CH3 a – H
Show tautomerism

11. [4]
number of isomer = 12
9. [4]

 Isomerism |   2.39
19. [2]

Cl
Cl Cl

Cl Cl Cl

Total isomer = 3
12. [3] 20. [3]
O O O O O Cl Cl
2 C chiral

ck
CH3–C–CH3 CH3–C–CH2–C–CH3 CH3–C–CH2–C–O–Et POS present
* *
(a) (b) (c) Achiral molecule
(Monocarbonyl) (b–dicarbonyl) (b–ketoester) Meso isomer
H H

a
(b > c > a) (refer key concept) 21. [4]
13. [4] * *
Same substituents at same Carbon
14. [1]
cr CH3–CH–CH2–CH2–Cl CH3–CH–CH2
Cl Br Br
CH3 GF CH3 *
e_
O.I * CH2–CH2–CH2–CH–CH3
C
H
Cl Cl
Each blocked atom consist of pair of different groups,
so that it shows G.I. CH3
15. [2]
Je

CH2
Use sequence rule or CIP rule
16. [2] CH3–CH2–CH–CH2–CH3 (no chiral C)

22. [2]
(1) (2)
@

(1)

C=C Same
(3) (4)
(No G.I) group
17. [1]

(2)

18. [2]
Cl Cl Cl
(3)
Cl

Cl Cl
Cis and trans Cis and trans
2.40 | Organic Chemistry Module I
4-(1–propenyl) cyclohexene n = 2 (stereogenic centre)
number of stereo isomer = 22 = 4
(4) 32. [2]

23. [2]
Chiral carbon = 2, number of S.I. = 22 = 4
H–O
33. [2]
F C=O Stable, six membered ring due to
C=C intra molecular H-bonding
=CH–CH=CH–C∫CH
H H *
n=2
24. [2] 2
number of S.I. = 2
30 g =4
C = ​ _______ ​ = 0.3 g/mL

ck
100 mL 34. [2]
a 15
{a}lT = ​ ___ ​ = ​ ______  ​ = + 25°
.C 0.3 × 2
25. [4]

A meso form, although containing chiral carbons is n
__

a
​   ​ – 1
optically inactive due to the presence of plane of a = 2n–1 + ​2​2 ​
2
symmetry. Optical activity of one half of the mol- __
​   ​ – 1
= 22–1 + ​2​2 ​
compensated.
cr
ecule is exactly cancelled by other half, i.e., internally
=2+1=3
26. [2]
II and III are meso form of hence diastereomers
e_
27. [1]
Hint: Calculating R-S Configration of both chiral
carbon & compare with R-S configration of other 35. [1]
combound.
By viewing structure properly
Æ Opposite configulation bf some locant carbon
Je

36. [1]
shows enantiomerism.
CH2OH
28. [4]
CH2OH CH2OH
III and IV are enantiomeric so that they do not have H HO H
HO H
plane of symmetry.
@

29. [2] HO H HO H
HO CH=O HO CH=O
CH=O
30.8
Enantionmeric axis (d) = ​ ____ ​ × 100 = 60% H
51.3
Racemic mix = 40%
d = 20% = 20%
CH2OH
Total d = 60 + 20 = 80% = 20
30. [4] HO H
Pair of enantiomers react differently with a pure
enantiomer of other compound.
H OH
31. [3]
Chiral carbon (OI) CH=O
1¢ 2¢ Only eclipsed form will convert into fisher
2 3
4 CH = CH—CH2 projection.
G.I 37. [4]
5
1 The most stable conformer is
6
 Isomerism |   2.41
3. [3]

4. [3]

38. [2]

Numbering of parent chain takes place according to
Number of alkyne isomer = 5

ck
locant number rule.
5. [3]
39. [3]
refer Key Concept
40. [2]

a
H
O OH
H F H H cr
H H H H
H F
nd
Most stable 2 most stable
I II
e_
Conformer II has less steric strain than I.

Exercise # 2

1. [3] 6. [3]
Je

Condition for G.I.

Each double bonded atom consist of pair of different
group.
7. [3]
(I), (II) POS absent (optically active compound)
@

(III), (IV) POS present (Meso compound)

8. [1]

Number of isomer = 6
2. [4]

Number of isomer = 6
9. [2]

2.42 | Organic Chemistry Module I
1 C chiral so molecule chiral 15. [4]
10. [2] Eclipsed form of show Sawhorse be change into
Fischer form.
* CH3 * CH3

O O+
ƒ
Chiral centre = 1 Chiral centre = 2

11. [2]
O

Chiral carbon = 1
molecule chiral
* CH3

ck
H
16. [2]
12. [3]
X Æ Show optical isomerism because (ring + double

a
bond = even number)
Æ Exhibits enantiomerism. cr
Y Æ Show geometrical isomerism

Æ Exhibits distereomerism.
Æ Diastereomers
13. [2]
17. [4]
(II) and (IV) are identical CH3
e_
OH OH CH3 CH2 NH C CH3 I
OH
O CH3
OH O CH3CH3
Je

OH OH
CH3 N CH CH2 CH3 II
(I) (II)
POS absent POS present CH3
Optically active Meso
CH3 CH2 C NH CH3 III
@

OH CH3
HO OH
OH
OH I & II – Functional Group will be differ.
I & III – Alkyl groups will differ along same func-
O
O tional group. Hence they are metamers.
OH 18. [3]
(III) (IV)
POS absent POS present
Optically active Meso

14. [3]

n=4

Number of Stereo isomer = 24 = 16 Number of isomer=6
 Isomerism |   2.43
19. [4] 26. [4]

• 1 carbon is chiral so that molecule is always
chiral.
• In rest 1, 2, 3 potion no chiral carbon is present.

20. [4]
27. [3]
Observed rotation
Enantiomeric axis = ​  = ​ _______________
  
   ​ Presence of either plane of symmetry or centre of
Specific rotation
symmetry makes a molecule superimposable its mirror
75 – 25 Observed rotation image, Presence or absence of axis of symmetry has
fi ​ _______ ​ = ​ _______________
 ​
    
75 + 25 +158 no role to play in optical activity.

ck
158 28. [3]
Observed rotation = ​ ____ ​ = + 79°
2 III and IV both are chiral and mirror images of one
21. [4] another.
Ph 29. [3]
Ph

a
H H
H H
cr
COOH COOH
Equal half have mirror image of one another so that 30. [3]
e_
POS is present.
22. [4]
Je

31. [2]

Cyclohexane has least angle strain. Cyclopropane
In rest other option, either E-form or double bond at has highest angle strain and angle strain decreases
2nd carbon of parent chain with increase in ring size reaches minimum in
@

23. [4] cyclohexane

32. [4]

24. [2]
When there is three consecutive double bonds,
terminals lie in the same plane giving geometrical 33. [1]
isomerism
25. [2] Br F Cl
Æ Cis-cis Cl
Æ trans-trans
Æ cis-trans No chiral C Have Chiral C
2.44 | Organic Chemistry Module I
34. [2] • Least proirity group always takes at inward the
3
plane.
CH3 1 1 1
COOH • By even exchange between the groups about chiral
H C carbon then configuration remains same.
4cw
(Z) CH OH • Locant number of chiral carbon decided by IUPAC
(R)2 2 2
2 rule
35. [3]
1 Exercise # 3
1 Z
Br Cl By interchanging One and more than one option correct type
C C 1 2 the groups about 2
H C C 1 question
chiral carbon
CH3 Acw 1. [1, 2, 3]
3 H 1Æ2,3Æ4 (even exchange)
4 3
4 So that configuration
S It show fluxional inversion at nitrogen and the two
remains same
enantiomers remain in dynamic equilibrium
36. [4]

ck

Type of C = 5

a
Type of H = 5
Number of monochloro product = type of H = 5
37. [3]
cr 2. [1, 2, 3]
CH3 CH3 CH3 CH3
H H H F
C C C C
e_
F C=C F F C=C H
H H H H
38. [3] (I) (II)
Meso Chiral (d + l)

It is unsymmetrical compound having 2-stereogenic CH3 CH3
Je

double bond H H
H C H C
Number of S.I = 22 = 4 H C=C F H C=C F
C H C H
39. [2] F F
Me CH3 CH3
(III) (III)
@

*
Me Meso Chiral (d + l)
H
* Total six isomers, two optically incactive and four
optically active. Both I and III upon ozonolysis
H followed by Zn-hydrolysis produces racemic mix-

ture. II and IV on similar treatment yields a single
POS present
optically active product in each case.
COS absent
C* present 3. [1, 3, 4]
G.I. present I and II conformers of enantiomers.
III is most stable due to largest groups at maximum
40. [3] distance.
I is enantiomeric while III is meso, hence I and II
are diastereomers.
4. [1, 3]
Meso form is optically inactive as it is superimposable
on its mirror image. In meso form, optical activity
of one half is compensated by other half of the
molecule, i.e., internally compensated.
 Isomerism |   2.45
5. [1, 3, 4]
Option 2 has a chiral carbon, show optical isomerism
but cannot show geometrical isomerism.
6. [1, 2, 4]

CH3—CH2—CH2—CH2—CHO
CHO 13. [4]
CHO Compound is optically active inspite of possessing
CH3—CH2—CH—CH3 axis of symmetry.
(d + I)
CH3—C—CH3
14. [1]
CH3 Enantiomers have opposite orientation of groups at
CH3—CH—CH2CHO
chiral carbon.
CH3
Comprehension type question
Total five aldehyde isomers. Out of five above shown

ck
Passage (15 to 17):
aldehydes, two are chiral. All of the above aldehydes
are capable of showing keto-enol tautomerism have 15. [4]
diastereomeric enols.
7. [2, 3, 4]

a
All these have functional groups are in same plane
can be non-polar. In (1), the two rings are in different
cr
plane, always polar.
8. [2,4] 16. [3]
e_

Br H
Je

Cl H Br Cl
Br H Cl Br 17. [4]
Cl (Q) H (Optically oetive)
@

9. [1,2]
10. [3]
Statement-I is true but II is false. Because allene type
substance do not have chiral centre even that they
have chiral molecule.
11. [1]
enol content µ stability of enol

none of the above isomer has any stereocentre
12. [1]
2.46 | Organic Chemistry Module I
Passage (Q. 18 to 20): Size of alkyl differ along same bivalent functional
18. [4] group

Cl Cl
H Cl H H
H H H H (B)
H Cl
Mgauche π 0 m=0

(Q) Position isomers
1.12 D = (3.2)2x + 0(1 – x)
Locant number will be differ along same parent
x = 0.11 chain
Mole fraction of anti = 1 – x = 0.89
% anti-conformer = 89%

ck
19. [3] (C)
The two gauche conformers are enatiomers, com-
bined they are 11%
20. [3] (S) Tautomers

a
Increasing temperature will decrease percentage of Functional group will be differ due to migration
both anti and gauche conformers as it will increase
cr of proton
percentages of less stable eclipsed conformers.

(D)
e_

(P) Enantiomer
Je

22. [3]
(i) Pentene has several cyclic isomers.

Hence, (i) Æ (p, q, s)

(ii) CH3–CH=CH–OCH3, shows cis-trans isomerism

I and II are here same isomers.

Column matching type question

21. [1]

(A)

Hence, (ii) Æ (q, s)
(iii) Dichlorocyclopropane
(R) metamers
 Isomerism |   2.47

(ii)

It has C-2 axis of symmetry passing through centre

of C2–C3 bond. However, this compound is optically

active.
(ii) Æ (q, s)
(iii) Compound is achiral, has all three types of
symmetry.
(iii) Æ (p, q, r)
Hence, (iii) Æ (p, q)
(iv) It ahs both plane and axis of symmetry.
(iv) Æ (p, q)

ck
(iv)
25.
Sol. (A)Æ(Q); (B)Æ(R); (C)Æ(P); (D)Æ(Q)
It has several positional isomers and six geo-
metrical isomers, i.e., 26.

a
cis-cis-cis Sol. (A)Æ(R); (B)Æ(Q); (C)Æ(P); (D)Æ(P)
trans-trans-trans cr
cis-trans-cis Single digit integer type question
trans-cis-trans 27. [8]
cis-cis-trans
trans-trans-cis
e_
It has several ring isomers.
\ (iv) Æ (r, s)
23. [1]
(i) Æ (q, r, s); (ii) Æ (p, r);
Je

(iii) Æ (q, s); (iv) Æ (q, s)

(i) cis-cis and trans-trans are achiral while cis-trans
is chiral giving total four stereoisomers.

(ii) Diastereomers can be both optically active, inac-
tive can be separated meso form consist of plane 28. [9]
@

of symmetry.
(iii) Meso form is optically inactive, usually consists Single
of plane of symmetry. isomers
(iv) Racemic mixture consists of equal amount of
enantiomers, hence optically inactive. However,
it can be resolved into enantiomers. All have pair
of geometrical
24. [3] isomers

29. [4]
30. [3]
(i)

(i) Æ (p, r)
2.48 | Organic Chemistry Module I
31. [5] 4. [1]
Ph Ph

H CH3 H CH3
H CH3 H 3C H two groups or atoms attached to doubly bonded car-
bon atoms should be different for G.I.
H CH3 H CH3
5. [1]
Ph Ph Racemic mixture is mixture of chiral carbons
(I) (II) 6. [4]
Ph Ph
H CH3 H3C H
H CH3 H3C H
H 3C H H CH3

ck
Ph Ph
(III) (IV)

Enantiomers

a

Pair of diastereomers are cr Geometrical isomers and enantiomers both are
I + III, I + IV, II + III, II + IV and I + II. stereoisomers.
32. [4] 7. [4]
Chiral compounds are those which have one chiral
centre, i.e., all four atoms or groups attached to same
e_
carbon are different. Here, I and II are chiral but III
and IV are achiral compounds.
8. [1]
33. [2] Chiral carbon has all the four different groups
Given condition (no sp & sp2 atom) satisfied only attached to it.
Je

when ring isomer exist (1) CH3CH2CH2CH2CH2Cl (no chiral carbon atom)
*
(2) CH3CHCH2CH2CH3 (one chiral carbon atom)
Cl

@

(3) (one chiral carbon atom)

34. [3]

(4) (two chiral carbon atoms)

9. [2]
Exercise # 4
(1)
1. [3]
Geometrical & Optical isomerism are different type
of Stereo-Isomerism. One asymmetric carbon atom, forms d-and
2. [2] l-optical isomers.
two groups or atoms attached to doubly bonded car-
bon atoms should be different for G.I. (2)
CH3–CH2–CH=CH2
3. [4]
Racemic mixture is an equimolar mixture of
enantiomers.
 Isomerism |   2.49
Two asymmetric carbon atoms, forms d-, l-and 14. [1]
meso forms. The molecule, which is optically active, has chiral cen-
tre, is expected to rotate the plane of polarised light.
(3)

Two asymmetric carbon atoms but does not have

symmetry. Hence, meso form is not formed.

(4)
One chiral centre hence, optically active

One asymmetric carbon atom, meso form is not

fomed
10. [4] Two chiral centres, but plane of symmetry within

ck
In CH3CH2OH, there is intermolecular H-bonding molecule hence, optically inactive.
while it is absent in isomeric ether CH3OCH3. 15. [1]
Larger heat is required to vaporise CH3CH2OH, as
compared to CH3OCH3, thus (1) is incorrect.

a
CH3CH2OH is less volatile than CH3OCH3, thus
vapour pressures are different, thus (2) is incorrect.
cr
Boiling point of CH3CH2OH > CH3OCH3, thus (3)
is incorrect.
16. [3]
mass
Density = ​ _______ ​, due to ideal behaviour at a given Geometrical isomerism is shown by those alkenes
volume
only in which atoms or groups attached to each car-
e_
temperature and pressure, volume and molar mass
bon atom are different. Thus,
are same. Hence, they have same vapour density.
11. [1] CH3 H CH3 H
C=C C=C
H H H3C H
Propene 2-methyl propene
Je

(three-atoms H linked to doubly (no geometrical isomerism)

bonded C-atoms are same, thus
There are two chiral C-atom (*) no geometrical isomerism)
Thus, it shows optical isomerism. H3C CH3 H3C H
12. [2] C=C C=C
H H H CH3
@

HO–CH2–CH2–F
cis-2-butene Trans-2-butene
(methyl group and H-atom H-atom lie on opposite side
linked to doubly bonded to one another, hence, trans
C-atom lie on same side, isomer
hence, cis isomer)

H3C CH3
C=C
H CH3
Gauche-conformation is comparatively more sta-
2-methyl-2-butene
ble due to hydrogen linkage in between F and H (no geometrical isomerism)
(at O-atom), hence increasing order of stability is
17. [3]
eclipsed, anti (staggered), gauche.
There are four stereoisomers
13. [1]
cis (R), cis (S), trans (R), trans (S)
18. [4]
Optical isomerism is shown by the carbon compounds
which possess atleast one chiral carbon.
Chair form is unsymmetrical and has absence of any Thus, 3-methyl-1-pentene possess a chiral carbon,
element of symmetry. hence it shows optical isomerism
2.50 | Organic Chemistry Module I
H 22. [4]
*
CH3–CH2–C–CH=CH2
CH3
3-methyl-1-pentence
(It has one chiral centre)
19. [3, 4]
Tautomerism is due to spontaneous interconver-
sion of two isomeric forms with different functional 23. [3]
groups into one another. The term tautomer means
constitutional isomers that undergo such rapid
interconversion that cannot be independently
isolated Carboxylic acid and ester have same M.F
• Hence mono carboxylic acid in functional group

ck
isomer of ester.
24. [3]
25. [3]
All other have at least one chiral C so they will show

a
optical isomerism only maleic acid have no chiral
cr carbon, thus it do not show optical isomerism
26. [1]
Thus, (3) 2-pentanone and (4) Phenol exhibit For G.I. each double bonded carbons have pair of
tautomerism. different group/atom
20. [2]
e_
Je

27. [4]
CH3–CH2–CH2–CH2–CH2–CH3
@

CH3
CH3–CH–CH2–CH2–CH3
CH3

CH3–CH2–CH–CH2–CH3
*
• Each chiral carbon (C) cantaining substance have CH3 CH3
two chiral molecule
CH3–CH–CH–CH3
• Total chiral molecule
21. [3] CH3
CH3–C–CH2–CH3
CH3
Total structural. isomer = 5
28. [3]

 Isomerism |   2.51
32. [1]

Mole-fractin of anti form = 0.82

Mole-fraction of gauche form = 0.18
29. [1] µobs = 1 D fi 1 = µanti × 0.82 + µgauche × 0.18

µanti = 0 fi 1 = µgauche × 0.8

1
Same MF, but locant number of functional group will µgauche = ​ ____ ​ = 5.55 D

ck
0.18
differ along same parcent carbon chain so it is pair
of position isomer
30. [1]

a
(b)
cr
Structure (ii) is more stable than its anti-conformer
For C-2, order of priority of substituents is because of intramolecular H-bonding
e_
OH > CH(Cl)(CH3) > COOH (According to CIP 33. [1]
rules)
For C-3, order of priority of substituents is
Cl > CH(OH)(COOH) > CH3 (According to CIP
Je

rules)
Hence
@

31. [4]
Here, when C2 is rotated anticlockwise 120° about
C2–C3 bond the resulting conformer is gauche

conformer.

Hence
• Total number of structural isomers (N) = 6
34. [3]

2.52 | Organic Chemistry Module I
39. [1, 4]

ck
Total structural isomer = 5
35. [3] Total six isomers, in both cis and trans forms, there
Molecules that are non-superimposable on its are two enantiomers each.

a
mirror image are optically active and known as
chiral molecule. However, for chirality of molecule,
presence of chiral centre is not essential
cr
e.g.,
e_
Molecule is chiral but does not possesses any chiral
carbon 40. [2, 4]
36. [1, 4]
The compound is optically active as well as it
possesses a two-fold axis of symmetry
Je

37. [2, 3, 4]

E, F and G are not resonance structures because
Conformation projection along C1–C2
movement of hydrogen between E and F are
involved. C1 contains all three Hs
E, F and E, G are tautomers in which E is keto form So, X = H
@

and both F and G are enol form of the same E.

F and G are geometrical isomers.
F and G are diastereomers as they are stereoisomers
but not related by mirror image relationship.
38. [7]

C2 contains two methyl and one ethyl group
So, Y = C2H5
Conformational projection along C2–C3
C2 contains three methyl groups (C2 from the back
carbon in the given structure)
So, Y = CH3

Total seven isomers.
 Isomerism |   2.53
C3 contains two Hs and one methyl group Since, M and N have –OH on same side and opposite
[C3 form front carbon in the given structure] side respectively, they cannot be mirror image, they
are diastereomers.
So, X = CH3
C3 contains two Hs and one methyl group
(C3 form front carbon in the given structure)
So, X = CH3
Isomerism (Stereochemistry)
Conceptual (Structural visualisation) III
41. [1]
C4H6 can have five cyclic isomers
M and O are identical.
Note: Fischer projection represents eclipsed form of

Sawhorse projection.

ck
Isomerism (organic)
For comparison purpose, similar types of eclipsed
Structural manipulation
conformers must be drawn, i.e., both vertically up
III or both vertically down.
42. [4]

a
cr
e_

I has one chiral carbon = two isomers
II has two chiral carbons and no symmetry = four
Je

isomers.
III and IV have not chiral carbon, no stereoisomers.
43. [1, 2, 3] M and P are non-superimposable mirror images,
Converting all of them into Fischer projection. hence, enantiomers.
Cl
@

HO
H
HO H
HO Cl
H HO H
CH3 CH3
(M) (M)
CH3
HO
H HO H
H CH3
OH H OH

Cl Cl

(N) (N)
M and Q are non-identical they are diastereomers.
2.54 | Organic Chemistry Module I
44. [1, 3,4] Hence, choices (1), (3) and (4) are correct
Plan this problem is based on structure and nomen- 45. [2]
clature of organic compound. Although the compound has two chiral carbons (indi-
Draw structure of each compound and write IUPAC cated by stars), it does not has four optically active
name of the given compound. isomers as expected. It is due to its existence in cis-
Match the molecular formula of given compound with form only
molecular formula of compound given in choices.
The combination of names for possible isomeric H 3C CH3 H 3C CH3
*
alcohols with molecular formula C4H10O is/are
*
H 3C H 3C
Formula Names O O
cis-form Trans-form
CH3CH2CH2CH2OH n-butyl alcohol/n-butanol/butan-1-ol (only hypothetical)
Isobutyl alcohol/2-methyl propan-
The above shown transformation does not exist due

ck
1-ol
to restricted rotation about the bridge head carbons,
hence only cis-form and its mirror image exist.
Secondary butyl alcohol/butan-2-ol 46. [1]
L-(–)-glucose is enantiomer of D-(+)-glucose

a
with hydroxyl group on left of vertical at C-5
Tertiary butyl alcohol/2-methyl
cr (L-configuration).
propan-2-ol
e_
Je
@