9 .

36 | Isomerism

Solved Examples

JEE Main/Boards Example 3: Consider the compound (A) given as:

R R
Example 1: Explain why α –methyl acetone enolises to | |
a smaller extent than acetylacetone. R '− C− HC= CH − C− R '
| |
H H
Sol: (A)
O O OH O
a. Give the total number of stereoisomers possible for
Me C CH2 C Me C C (A).
Acetyl acetone Me CH Me
Enolisation is greater due b. If the stereochemistry about the double bond in (A)
to less strain is cis, give the number of enantiomers possible for (A).
O O OH O
Sol: The compound (A) contains two asymmetric C
Me C CH C Me
 2 C C atoms with the same terminal group.
Me C Me
Me
-Methyl acetyl acetone R R
(keto from)
Me | |
Enolisation is lesser due to R '− C − C =C− C* − R '
*
high strain as a result of the | | | |
presence of two Me groups H H H H

Number of optically active isomers (O.I.A.) = 2n−1 = 22−1 =

(
Example 2: Why is the −CH2 − group in acetyl acetone ) 2 (where, n is the number of asymmetric C atoms).
called active methylene group? Number of meso form = 2(n−2)/2 = 20 = 1
O O Total optical isomers = 2+1=3
Me C CH2 C Me Due to one double bond, the number of geometrical
isomers = 2
Sol: The ( −CH2 − ) group is acidic in nature because
these H atoms can be easily lost as HΘ with base, as the Total number of stereoisomers = 3 × 2 = 6
resulting carbanion is resonance stabilized. If the stereochemistry about (C=C) bond is cis, Then two
( )
The −CH2 − group is acidic in nature because these H pairs of diastereomers (II) and (III) are possible. (II) is meso
atoms can be easily lost as HΘ with base, as the resulting (O.I.A.) due to the presence of plane of symmetry. (III) is
carbanion is resonance stabilised. optically active (O.A) and two enantiomers are possible.
Therefore, in total there are three diastereomers.
O O
OH H H H H H H
Me Me H H H H H H
H H R’ C C R’ R’ C R’ C C R’ C R’
O O O O
R R R R R R
Plane of symmetry (+) (lll) (-) (lll)
Me Me Me Me (meso) (O.I.O.)
(ll) (lll)
(+) or racemate
O O
II and (+) III, II and (–)III are diastereomers, whereas (+)
Me Me III and (–) III are enantiomers.
-
O O -
Example 4: How many geometrical isomers are possible
Me Me for the following?
a. Decalin b. 1–Methyldecalin c. 9–Methyldecalin
 Isomerism | 9.37

Sol: a. Two geometrical isomers: cis and trans

b. Geometrical isomerism is shown by the ( C ≡ C ) only
H H and not by ( C ≡ C ) , so we have an alkene of the type

 
R R
C C
H
H H H
cis trans
(l) (l) In this, one R group should have ( C ≡ C ) and the other
b. Four geometrical isomers R should be a Me group so that the lowest number of C
Me Me atoms is obtained.
8
H 1
H
9 5 2 1 2 1
7 2 H3C 4 3 C CH H 4 3 C CH
C C 5 C C
6 3 H3C H
H H (C)
5
10
4
(B)
H H (Z) (E)
cis-1-Methyl- trans-1-Methyl-
Pent-3-en-1-yne
cis-decalin cis-decalin
(l) (ll) c. In compound (A) given in the solution to part (A),
Me Me put one Me group at C–1 so that it can show both
H H geometrical and optical isomerisms.
H
1 2 3 4 5 H
HC C + Enantiomer
* C C
H H Me
cis-1-Methyl- trans-1-Methyl-
Me H (4E)
trans-decalin trans-decalin
(lll) (lV) H
1 2 4 5 Me
HC C
3
* C C + Enantiomer
c. Two geometrical isomers
Me Me H
8 1 Me H (4E)
9
7 2
(4E and 4Z-3-Methyl hex-4-en-1-yne)
6 3
10
5 4
H H Example 6: Give the structural formula of a cyclic alkyne
cis-9-Methyl decalin trans-9-Methyl decalin
(l) (ll) with the lowest number of C atoms and showing:
a. Both geometrical and optical isomerisms.
b. Geometrical isomerism with two meso stereo–
Example 5: Give the structural formula of an unsaturated isomers.
hydrocarbon with the lowest number of C atoms (or
with lowest molecular mass) which shows: Sol: a. For the lowest number of C atoms, take
a. Optical isomers b. Geometrical isomers disubstituted cyclopropane ring in which one group is
(HC≡C)(ethynyl) and the other is (–Me) group.
c. Both optical and geometrical isomers
3 3

Sol: a. An unsaturated hydrocarbon with the lowest H H H Me

molecular mass should have one ( C ≡ C ) , one ( C = C ) , (A)  * * (B)  * 1 *
1 2 2
one H atom, and finally one Me group.
C Me C H
H and and
2 1 CH CH
5 4 3
HC C C HC CH2 Four different groups Enantiomer Enantiomer

Me 1-Ethynyl-2-methyl cyclopropane
(3-Methyl pent-1-ene)
(A) b. For the lowest number of C atoms, take the
trisubstituted cyclopropane ring with one (HC≡C)
9 .38 | Isomerism

ethyne group and two (–Me) groups, so that meso 1

compound can be obtained to have the plane of NH2 NH2
2
symmetry in the molecule. *
First Second
4 CH2CH3 CH2CH3
interchange interch-
Me Me H 3 CH3
H and CH3
H3C H ange
1 H and
Me Me H (R)-Butan-2-amine NH C2H3
2
H H
(C)  (D)  3 H
H3C 2 CH2CH3
H H H (clockwise)

C
(Meso)
C

(R) -Butan-2-amine
trans-1-Ethynyl-
Linear

CH
CH

cis-2,3-dimethyl
(Meso) portion Priority order:–NH2>–CH2CH3>–CH3>–H
cis-1-Ethynyl- cyclopropane
cis-2,3-dimethyl (B) The lowest priority ligand (H) is on 2
Plane of CHO
cyclopropane
symmetry the dotted line. R and S can be 4
assigned directly from the priority H 3

rule. HO 1 CH2CH3
(clockwise)
Example 7: 2, 2’–Difluoro–6,6’–dimethylbiphenyl is (–OH>–CHO>–CH2OH>–H). (R)
non–resolvable, whereas 2, 2’–dinitro–6,
F Me 6’–disulphonic
acid biphenyl is resolvable. Account for this fact. (C) Lowest priority ligand (–CH3) is in the plane (i.e., not
on the dotted line). So make one interchange so that
Sol: Presence of bulky group at ortho position causes (–CH3) is projected away from the observer. (Priority
ortho repulsion and due to this two ring becomes non order. –Cl>–SH>–CH2CH3>–CH3
Me F
planar and thus becomes resolvable.
1
F Me O2N SO3N CH3 Cl 4
CH3
n

1
ai

Cl
Ch

3 2 3 2
One interchange
Observer SH SH
CH3 and Cl
CH3 CH3
Me F HO3S NO2 (I) (clocwise)
(S configuration)
Steric
O2Ncrowding
SO3N is not large enough to prevent free (R)
rotation about (C–C) single bond, so the energy of But with one interchange,
the configuration changes
separation between various invertomers is low and from R to S.
consequently non–isoable. Due to the bulky group at
ortho
HO3Spositions,
NO2 free rotation is restricted as the two Example 9: Convert Sawhorse formula to Fischer
rings become nearly perpendicular and hence the formula.
energy of separation between the isomers is highly and Br COOH
consequently isolable.
Me H H Me
a. Me H b. Me H
Example 8: Assign the R and S designations to the
COOH Br
following compounds:
Sol:
NH2 Br
CH2CH3 CHO Rotate by
a. H CH3 b. H Me
180o Br
H H Me
Cl SH OH CH2OH H Br H Me
a. Me Me H
c. Me H
COOH COOH COOH
COOH
Sol: (A) The lowest priority ligand (H) is in the plane (i.e., o
H Me Rotate the molecule to 180
not on the dotted line) so it makes two interchanges (Fischer projection)
Me H On the plane of paper o keep
such that H is projected away from the observer. the (-COOH) group on the top
Br
HOOC Rotate by
180o
Me H COOH
H Me
COOH Me H
b. Me H Me
H Me H
Br Br Br
 COOH COOH COOH
COOH
o
H Me Rotate the molecule to 180
(Fischer projection)
Me H On the plane of paper o keep Isomerism | 9.39
the (-COOH) group on the top
Br
HOOC Example 2: Write down the number of asymmetric
Rotate by
carbon atoms in each optically active compound and
180o H COOH
H Me Me report the number of isomers.
COOH Me H
b. Me H Me
H i. CH3(CHOH)2COOH ii. COOH(CHOH)2COOH
Me H
Br Br Br
Fischer projection Sol: Since n is even in both the case,
Number of O.I.A = 2n
Example 10: Convert Fischer formula to Wedge formula.
Number of meso forms=2(n–2)/2
COOH Br
Number of (O.I.A) racemic form=n/2
(1) H OH (2) H3C CHO
C2H5 H Total optical isomers=2n–1 + 2(n–2)/2
i. Number of asymmetric C atoms = 2
Sol: COOH Vertical Br Different terminal groups : (–COOH) and (Me)
(1) H line (2) CHO
Number of O.I.A = 2n=22=4
OH C2H5 H CH3
(or) Number of meso forms =0
Br 4
Vertical Number of (O.I.A) racemic form = =2
line 2
H3O OH
(racemate mixture)
CHO H
∴ Total optical isomers = 4 COOH
Me
Optically inactive forms = 2.
OH
JEE Advanced ii. Number of asymmetric C atoms = 2.
Same terminal groups: (–COOH)
Example 1: Give the decreasing order of net dipole OH
moments of the following:
COOH
Br H Br Br H
HOOC
(I) (II) (III)
H OH
Br H H H Br
n−1 2−t
Number of O.I.A = 2= 2= 2
Br
Sol: Dipole moment is inversely proportional to angle of Number of meso forms = 2
(n−2) /2 = 2° = 1
separation. Thus smaller angle of separation will cause 2
large dipole moment whereas large angle of separation Number of (O.I.A) racemic form = =1
2
causes less dipole moment. I>II>III Total optical isomers = 2+1=3
I. (I) has a smaller angle of separation between two Br
atoms than in (II) and (III), resulting in more net dipole Example 3: Resolute the compounds from enantiometric
moment (µ). mixture
Br H
 Sol: First convert the pair of enantiomers into
H diastereomers by using proper resolving agent. The two
Br
diastereomers have different physical properties like
II. (II) has a large angle of separation between two Br solubility. By using a proper solvent two diastereomers
atoms; therefore, net (µ) is less than (I). can be separated and they are converted back into
Br enantiomer.
H
CH3
HOOC CH3
H Br H
+ C
III. In (III), two Br atoms and two H atoms have equal and NH2
Cl H
opposite bond moments; therefore, the net µ is zero. (+)-1-Phenylethylamine
(an optically pure reagent; (+)-2-Chloropropanoic acid
a resolving agent; it is reacted (racemic mixture)
with the racemic mixture)

CH3 CH3
H H
NH NH
 + C
NH2
(+)-1-Phenylethylamine
Cl H
9(an
.40 | Isomerism (+)-2-Chloropropanoic acid

  
optically pure reagent;
a resolving agent; it is reacted (racemic mixture)
with the racemic mixture)

0.01
CH3 CH3 = = 0.5 ( l is cons tant )
0.02
H H
NH3 NH3 New α  = −125° × 0.5 = −62.5°
D

OOC CH3 OOC CH3 Change in specific rotation = 62.5–(–125)=+ 62.5°

C C
Cl H H Cl
(+) Amine(+) Acid salt (+) Amine(+) Acid salt
Example 5: What is the optical purity of a sample having
 Mixture of diastereomers; Components of the mixture have
different physical properties; hence can be easily separated.
an α 
obs.
=+9.0 if α  =
D
+12°

Sol Optical purity (OP) of sample =

+9°
+12°
× 100 =75%
The mixture has 75% (+) and 25% racemic mixture [i.e.;
12.5%(+) and 12.5%(–) form.
25%
Total percentage of (+) form= 75 % + =87.5%
(+) Amine(+) Acid salt (+) Amine(-) Acid salt 2
Enantiomers(+) and (-) are cleaved Total percentage of (–) form = 12.5%
from respective diastereomers

Example 6: How many optically active and inactive

(+) Amine and (+) Acid (+) Amine and (-) Acid
Resolving agent (+) is separated
and recovered. Pure enantiomers isomers of 1, 2, 3 trimethylcyclohexane are possible?
from the recemate are obtained
HOOC CH3 HOOC CH3 Sol:
Cl Cl
Cl Cl
Cl ClCl
C C Cl 11 22 33 11 22 33 44
C
C C
C C
C CC CC CC CC
Cl H H Cl H H H
(+) Acid (-) Acid H
2 2 H H 2 HH
sp2 sp
sp sp sp2
sp
2 sp
sp2 sp sp2
sp 2

 
sp sp2
sp
C22 is
C is in
in different
different (Allare
areininsame
samepla planne)e)
(All
plane with C C¹¹ aanndd C³
C³
Example 4: An aqueous solution containing 10gm plane with optically
opt icallyin
inact
active
ive
Opt i cally act ive a n d 
and   0  0
of optically pure fructose was diluted to 500 mL with Optically active
  00
aannd d
water and placed in a polarimeter tube 20 cm long. The Me Me
Me Me
measured rotation was −5.0°. To this solution 500 mL Me H
of a solution containing 10 gm of racemic fructose is H Me HH
H H
added. What will be the change in specific rotation? Me Me
Me H Me Me
H Me
Sol: Using the following equation, first calculate the (I) H
(I) H
(II) H
(II) H
(Meso) (Meso)
specific rotation. (Plane (Meso)
of symmetry) (Plane(Meso)
of symmetry)
θ
(Plane of symmetry) (Plane of symmetry)
α  = Me Me
D I×C Me
Me Me
Me
H Me Me H
As we know, 20 cm = 2 dm. H H
H H
θ −5.0° H H HH
α D = = =−125° H H
I × C 2dm × 10gm / 500ml (+)Me Me(-)
(+)Me Me(-)
Total volume of solution = 500+500=1000mL O.l.A.
(III) O.l.A. (IV)
Mass per mL of pure fructose = 10/1000 = 0.01 gm/mL –1 (III) (IV)
Cl Cl
Mass per mL of mixture = (10+10 = 2) = 20/1000 Example 7: Which of the following
I. C C will
C show dipole
= 0.02 gm/mL–1 moment (µ)? Cl Cl
OP (optical purity) Cl Cl Cl Cl
I. C C C II. C C C C
α  of mixture Mass per ml of pure form Cl Cl Cl Cl
obs.
= α
α  of pure form Mass per ml of mixture Cl Cl
D Sol: (i) Will show dipole moment (µ). The terminal C
C C C C
atoms
II. are not in plane with middle C atom.
Cl Cl
 Isomerism | 9.41

Cl Cl Thus, there is no change in the configuration when both

C C C switches (A) and (B) are made.
Cl Cl
2 2 d.
sp sp sp
So they have net resultant dipole moment. CH3 H

 
(ii) Has zero dipole moment. All the C atoms are in one SR 3 1
H Br H3C Br Check the configuration,
plane, so the net resultant bond moment is cancelled. 2
H on vertical line;
C2H5 C2H5 Clockwise and thus (R)
(S) (I) (R)
Cl Cl
Net resultant C C C C Net resultant
Cl Cl vector
e. This type of operation is not allowed in Fischer
sp sp
sp
2
sp
2
projection because any flipping out of the plane of
paper (side to side or top to bottom) would change the
As a general rule, an even number of cumulative double ligands formerly projecting behind the plane of paper to
bonds with all the same four groups will show a dipole projecting towards the observer. Those ligands formerly
moment and an odd number of cumulative double pointing towards the observer would change to behind
bonds with all the same four groups will not show the paper.
dipole moment.
f. This type of operation is also not allowed in Fischer
Similarly, an even number of cumulative double bonds projection. For example,
with two different groups on terminal C atoms will
be optically active and an odd number of cumulative CH3 Br
double bonds with two different groups on terminal C H Br H3C C2H5
atoms will be optically inactive.
C2H5 H
Example 8: Give the effect of the configuration of (S)–2– (I) (I’)
bromo butane on performing the following operations:
(a) Exchanging ligands across the horizontal bond.
Example 9: Some possible structures of a compound A
(b) Exchanging ligands across the vertical bond. (C10H16) are:
(c) Making both switches (A) and (B).
Me Me Et
(d) Exchanging a horizontal and vertical ligand.
(e) A 180o vertical or horizontal rotation outside the
plane of paper. a. b. c.
Me Me
(f) A 90 rotation on the plane of paper.
o

Me Me Et
Sol: 3
CH3 CH3
a.
1
Write the possible stereoisomers of (A), (B) , and (C).
H Br SR Br H
2
C2H5 C2H5 Sol: (A) Representations of geometrical isomers
Enantiomer of (l)
H on horizontal line:
(diastereomers).
Clockwise (R) ;
(B) Three geometrical isomers are shown; out of them
Change (R) to (S);
(S)-2-Bromobutane(l)
one is optically active.
(C) The cis form is optically active.
CH3 C2H5
b.
H Br SR H Br
CH3 Me
C2H3
(S) (R) and
(I) Enantiomer of (I) Me Me Me
c. CH3 CH3 C2H5 (Cis) (Trans)
H Br Br H Br H (I) (II)
SR SR
C2H5 C2H5 CH3
(S) (R) (S)
(I) Same as (I)
 Me Me H H
Plane of
9 .42 | Isomerism (O.l.A.) (O.l.A.)
symmetry
(I) (II)

Et H Me Me
Et H
H Et Et Me H H H
H Me H
Me
Me
(cis) H H
Et H H Me Me
(O.A) (+) (-)
(O.A) (+) (-) H

(III)
H Et
But the trans form is (O.l.A.) due
to the presence of centre Example 10: What is the observed rotation when 0.1 M
of symmetry.
solution of (R)–2 butanol is mixed with an equal volume
of 0.05M solution of racemic 2– butanol and the resulting
H H H H
solution is taken in a cell of 5 cm long tube in a polarimeter?
* * * * The specific rotation of (R)–2–butanol is +13.9o.
Me Me Me Me
Sol: The racemic 2–butanol has no contribution to
Me optical activity . So, the observed rotation will be due
H H Me
to (R)–2 butanol only. Racemic butanol helps in diluting
* * * * after dilution is 0.05M. Molecular weight of 2– butanol
Me Me H H is 74.
Plane of l=5 cm = 0.5 dm
(O.l.A.) (O.l.A.)
symmetry
(I) (II) 74 × 0.05
∴ Concentration = 3.7 × 10−3 gm ml−1
=
1000
H Me Me
H ∴ α   
=α ×l× c =13.9 × 0.5 × 3.7 × 10−3 = 0.26o
obs. pure

Me H H H
Me H
Me
Me
H Me Me
H
JEE Main/Boards
(O.A) (+) (-)

(III)
Exercise 1
Q.1 0.90 gm of an organic compound C4H10O2(A) when
treated with sodium gives 224 mL of hydrogen at NTP.
Compound (A) can be separated into fractions (B)
and (C) , by crystallisation of which the fraction (B) is
resolved into optical isomers (D) and (E). Write down the
structural formula of (A) to (E) with proper reasoning.
Q.2 Write down the structures of close homologues of
heptane having one quaternary C atom in their molecule
and the other having two tertiary carbon atoms.
Q.4 Which alkane, having a molecular weight of 86, will
form only two monobromo alkanes?
Q.5 A hydrocarbon (A) was found to have vapour density
36. It forms only a single monochloro substitution
product. Suggest (A).
Q.6 Which of the following will not be able to show
optical isomerism (enantiomerism)?
(A) 1,2–Propadiene (B) 2,3–Pentadiene
(C) Sec–Butyl alcohol (D) All exhibit enantiomerism

Q.3 An alkaline (A)C5H12 on chlorination at 300°C gives Q.7 If optical rotation produced by the compound (A) is
a mixture of four different monochlorinated derivatives, +52°, the one produced by compound (B) is:
(B), (C), (D), and (E). Two of these derivatives give the same CH3 CH3
stable alkene (F) on dehydrohalogenation. On oxidation
Cl H H Cl
with hot alkaline KMnO4 followed by acidification, (F) H Cl Cl H
gives two products (G) and (H). Give the structures of (A) CH3 CH3
to (H) with porper reasoning. (A) (B)
 Isomerism | 9.43

Q.8 The E–isomer among the following is: (B) 8σ−bonds, 2π−bond, and 2 lone pairs
Cl Br H3C CH CH2 (C) 10σ−bonds, 2π−bond, and 1 lone pairs
(A) C C (C) C C
H3C C2H5 H CH3 (D) 9σ−bonds, 2π−bond, and 2 lone pairs

Cl C2H5 H CHCl2 Q.16 Arrange the following in the increasing order of

(B) C C (D) C C expected enol content.
H3C CHO H3C CHCl2
i. CH3COCH2 CHO ii. CH3COCH3

Q.9 Which of the following will not show geometrical iii. CH3CHO iv. CH3COCH2 COCH3
isomerism? (A) iii<i<ii<iv (B) iii<ii<i<iv
H3C H CH2 CH CH2Cl3
(C) i<iv<ii<iii (D) iv<i<ii<iii
(A) C (C) C
Cl CH CHCH3 H CH CHCl
Q.17 Hydrocarbon with formula C8H18 gives one chloro
ClH2C CH CH3
derivative. The hydrocarbon can be:
(B) C (D) CH3CH CHCH2 CH3
H CH3 (A) n–octane
(B) 2–methylheptane
Q.10 The dihedral angle between the hydrogen atoms
(C) 2,2,4–trimethylpentane
of two methyl groups in staggered conformation of
ethane is: (D) 2,2,3,3–tetramethylbutane

(A) 120o (B) 180o (C) 90o (D) 60o Q.18 The minimum number of carbon atoms an alkane
should contain in order to exhibit optical activity is:

Q.11 Which of the following objects is chiral? (A) 5 (B) 6 (C) 7 (D) 8

(A) Nail (B) Blade

(C) Tennis racket (D) Laced football
Q.12 Predict the number of stereoisomers for 2,5–
heptadiene.
(A) 4 (B) 3 (C) 2 (D) 5
Q.19 A compound whose molecule is superimposable
on its mirror image despite containing chiral carbon
atoms is called:
(A) Threo isomer (B) Meso compound
(C) Enantiomer (D) No special name

Q.13 Symbol D stands for:

Q.20 The IUPAC name of the compound with formula
(A) Dextrorotatory, which rotates P.P.L. towards right. CnH2n+2, having the lowest possible molecular mass and
(B) Dextrorotary , which rotates P.P.L. towards left. capable of showing enantiomerism is:

(C) Relative configuration with respect to lactic acid (A) 3–Methyl hexane (B) 2,3–Dimethyl pentane
taken as standard. (C) Methane (D) Both (A) and (B)
(D) Relative configuration with respect to glyceraldehyde
taken as standard and (OH) group is on the right side.
Exercise 2
Q.14 Which of the following compounds will not show Single Correct Choice Type
geometrical isomerism?
(A) 3–Phenyl–2–propenoic acid Q.1 In which of the following has minimum torsional
(B) 2–Butene strain and minimum Vander waal strain.

(C) 3–Methyl–2–butenoic acid CH3

CH3
CH3
H H
(D) 3–Methyl–2–penteoic acid
CH3
Q.15 The enolic form of acetone contains: H CH3 H CH3
CH3 CH3
(A) 9σ−bonds, 1π−bond, and 2 lone pairs I II
CH3 CH3
CH3 H CH3
 CH3 OH CH3 CH3
CH3
CH3 H CH3 (A) H (B) H
H | Isomerism
9 .44 CH3
OH and CH3 H OH and H C2H5
CH3
I II CH3 CH3 C2H3 CH

CH3 CH3 CH3 Br

CH3 Cl H3C Br
CH3 H CH3 and (D) Cl Br and
(C) C=C C=C
CH3 Br H3C Cl H3C
Cl
H H
CH3 CH3
H CH3 CH3
Q.6 Which statement is correct about the following
III IV
structures
CH3 C2H5 Cl
(A) I (B) II (C) III (D) IV H Br H Br H3CO C2H5
Cl OCH3 H3CO Cl H Br
C2H5 C2H5 CH3
Q.2 The IUPAC name of the compound:
I II III
(A) I and II are structural isomers
(B) I and II, I and III are enantiomers
(A) (2E,4E,6Z)–octa–2,4,6–triene (C) I, III are enantiomers and I, II are structural isomers
(B) (2E,4E,6E)–octa–2,4,6–triene (D) I, II and III are stereoisomers.
(C) (2Z,4E,6Z)–octa–2,4,6–triene Q.7 Which will form geometrical isomers?
(D) (2Z,4Z,6Z)–octa–2,4,6–triene Cl

(A)
(A) (B) CH3CH=NOH
Q.3 How many spatial orientations are possible in the Cl
following compound?

CH=CHCH3
(C)(C) (D) All of these
I

Q.8 If optical rotation produced by (A) is +36o then

CH2 ClCH3Br optical rotation produced by (B) will be ?
CH3 CH3
(A) 2 (B) 4 (C) 6 (D) 8
Cl H Cl H
H Cl Cl H
Q.4 How are compounds I and II are related? CH3 CH3
F Br (A) (B)
Cl H Cl CH3
(I) (II) (A) +36o (B) 0o (C) +26o (D) Unpredictable
Br CH3 l H
l F Q.9 W
 hat is the configuration of the given molecule?
(A) Enantiomers (B) Diastereomers
CH2 OH
(C) Constitutional (D) Identical |
HO − C − H
|
Q.5 The non identical species are:
CHO

CH3 OH CH3 (A)

CH3D (B) L (C) d (D) 1
(A) H OH and CH3 H (B) H OH and H C2H5
Q.10 Which of the following is/are correct matchings?
CH3 CH3 C2H3 CH

OH CH
CH3 3 CH3 CH CH3 O O
CH3 Cl H3C OH Br CH3 3 Br || ||
(D) Cl Br and
3 H ((A)
C) HH
(B) OH
C=C OHand
andand
HCH3 C=CC2HH5 (B) H OH and H (A) CCH 3 − C − OH and H − C − OCH3
2H5 → Metamers
CH3 Br H3C Cl H3C
CH3 CCH
2H33 CH
CH3 C2H3 CH
Cl
(B) CH3 − CH2 − C ≡ CH and → Position isomers
CH3 CH3
C
3 Br CH
(D) Cl 3 Cl
Br and
Br
H3C Br
(D) Cl Br and
Br CH3 − C ≡ C − CH3
C=C (C) C=C and C=C
C Cl CH3 Br HH33CC Cl H3C
Cl Cl
 Isomerism | 9.45

(C) CH3CH2CH2NH2 and CH3 − CH − CH3 → Tautomers Q.5 Which of the following compounds exhibits,
| stereoisomerism?  (2002)
NH2
(A) 2–methylbutene–1 (B) 3–methylbutyne–1
(D) Anisole ando-cresol → Metamers
(C) 3–methylbutanoic acid (D) 2
 –methylbutanoic acid
Q.11 The correct IUPAC name of D–Glucose is:
Q.6 C2 is rotated anti –clockwise 120o about C2–C3
CHO
bond. The resulting conformer is (200)
H OH
HO H (A) Partially eclipsed CH3

H H
H OH
(D-Glucose) (B) Eclipsed 3
H OH 2
(C) Gauche H H
CH2OH
(D) Staggered CH3
(A) (2D,3D,4L,5D) 2,3,4,5,6– penthahydroxyhexanal.
(B) D–2,3,4,5,6–pentahydroxyhexanal Q.7 The number of stereoisomers obtained by
bromination of trans–2–butene is (2007)
(C) 6–oxo–(2D,3L,4D,5D)–2,3,4,5,6–pentahydroxyhexane.
(A) 1 (B) 2 (C) 3 (D) 4
(D) (2D,3L,4D,5D)–2,3,4,5,6–pentahydroxyhexanal.
Q.8 Read the following questions and answer as per the
Q.12 Total number of geometrical isomer of following direction given below:  (2007)
compound.
(A) Statement-I is true; statement-II is true; statement II
is the correct explanation of statement-II.
(B) Statement: I is true; statement-II is true; statement-II
(A) 2 (B) 4 (C) 8 (D) 16 is not the correct explanation of statement-I.
(C) Statement-I is true; statement-II is false
(D) Statement-I is false; statement-II is true
Previous Years’ Questions
Statement-I : Molecules that are non–superimposable
Q.1 How many optically active stereoisomers are on their images are chiral.
possible for butane–2,3–diol? (1997)
Statement-II : All chiral molecules have chiral centres.
(A) 1 (B) 2 (C) 3 (D) 4
Q.9 Isomers which are ………… mirror images are known
Q.2 The optically active tartaric acid is named as D–(+)– as ………..(superimposable, non–superimposable,
tartaric acid because it has a positive (1999) enantiomers, diastereomers, epimers) (1988)
(A) Optical rotation and is derived from D–glucose
(B) pH in organic solvent Q.10 A solution of (–) 1–chloro–1–phenylethane in
toluene racemises slowly in the presence of a small
(C) 
Optical rotation and is derived from D–(+)–
amount of SbCl5, due to the formation of : (2013)
glyceraldehydes
(A) Carbanion (B) Carbene
(D) Optical rotation when substituted by deuterium
(C) Carbocation (D) Free radical
Q.3 Which of the following compounds will exhibit
geometrical isomerism? (2000) Q.11 The absolute configuration of (figure) is (2016)

(A) 1–phenyl–2–butene (B) 3–phenyl–1–butene (A) (2S, 3R)

(B) (2S, 3S)
(C) 2–phenyl–1–butene (D) 1,1–diphenyl–1–propene
(C) (2R, 3R)
Q.4 The number of isomers for the compound with (D) (2R, 3S)
molecular formula C2BrClFI is  (2001)
(A) 3 (B) 4 (C) 5 (D) 6
9 .46 | Isomerism

JEE Advanced/Boards

Exercise 1 (A) C7H16 (B) C7H12 (C) C7H9 Cl

(D) C3H4ClBr (E) C2H2Cl2F2
Q.1 How many benzenoid isomer are possible for cresol?
Q.8 How many cyclopentane structures (excluding
Q.2 Find out the total number of cyclic structural stereo isomer) are possible for C7H14.
isomers of C6H12
Q.9 Find out total number of structures of X.
Q.3 How many pair(s) of geometrical isomers are
possible with C6H12 (with in open chain structures) 2H2
X
Pt
Q.4 Which of the following compounds can be optically
active?
Q.10 Calculate the total number of cyclic isomeric
CH3 CHClBr CH3 CH C
compounds of molecular formula C5H8O which can’t
(A) C=C (B) show geometrical isomerism.
H CH2-Cl CH CH3

SO3H Br
Q.11. Asssign E and Z configuration

Cl Cl O
(C) (D) C=C=C=C O
H H (I)
(II) O
O
Br SO3H O

Cl I Br C2H5 Cl Br Br Cl

CH2CH2CH3
(E) (F)
Ph
(III)
I Cl C2H5 Br CH3 I I H3C CH CH3
(IV) Cl
Br CH3
OHC CH3 H3C
(G) (H) FF
C=C=O
F CN H
CC CC CC BrBr NC CH=CH2
I (V)
(V) FF (VI)
CH3 HOOC CHO
CH3O C C C Cl
(I) C C C C Cl
Br CH2Br
O
HO C CH
HO C CH O
CH3 O
Q.5 Calculate the number of Benzenoid isomers possible (VII) CH3 O
(VII) OHC C CH3 (VIII)
for C6H3ClBrI. OHC C CH3 O
O

Q.6 Calculate the total number of structural isomers of

3°− amines for the molecular formula C6H15N are? Me OMe H OH
(IIX) (X)
16
O- Li
+
Et
D OH
Q.7 Write the number of acyclic, optically active
structural isomers having following molecular formula
and write their structural formula also.
 Isomerism | 9.47

Me (A) Draw the Newman projection of the most stable

F CH3
(XI)
conformer.
CH CH2 CH3
Cl Me (B) Draw the Newman projection of the least stable
(XII)
C CH conformer.
H
CH3
Q.18 Determine whether each of the following
compounds is a cis isomer or a trans isomer.
Br
Q.12 Write the number of all possible acyclic compounds H H
having molecular formula. Give their structural formula H
Cl
(A) Br (B)
also.
CH3
(A) C2H2Cl2F2 (B) C2HClBrlF (C) C2ClBrlF H

H H
Q.13 Mention the specific type of isomerism exhibited
Br
by each of the following pairs (C ) CH3
H (D)
(A) 1,2–dichloro ethane and 1,1–dichloro ethane CH3
Br
(B) Propanoic acid and methyl acetate H
(C) Methyl acetate and ethyl formate
H H
(D) o–Nitrophenol and P–nitrophenol.
CH3
(E) Anisole and o–cresol (F)
(E) Cl CH3
(F) Phenol and Cyelohexa–2,4–dien–1–one. CH3
H
H
Q.14 Draw the two chair conformers of each compound
and indicate which conformer is more stable.
Q.19 Write down all the isomers of formula C7H7O2N .
(A) Cis 1–ethyl–3–methylcyclohexane What type of isomerism they show?
(B) Trans–1–ethyl–3–isopropylcyclohexane
(C) Trans–1–ethyl–2–methylcyclohexane Q.20 Assign the priority order number to the following
atoms or groups.
(D) Trans–1–ethyl–3–methylcyclohexane
(E) Cis 1–ethyl–3– isopropylcyclohexane (A) −CHO, − CH2 OH, − CH3 , − OH
(F) Cis 1–ethyl–4– isopropylcyclohexane (B) −Ph, − CH(Me)2 , − H, − NH2

(C) −COOH, − Ph, − CHO, − CH =

CH2
Q.15 Write stereochemical formula of the following
compounds. (D) −CH(Me)2 , − CH= CH2 , − C ≡ CH3 − Ph
(A) D–2–Hexanol (E) −CH3 , − CH2Br, − CH2 OH, − CH3Cl
(B) L–Lactic acid (CH3 − CHOH − COOH)
(F) −H, − N(Me)2 , − Me, − OMe


(C) D-Glyceric acid CH2 CH COOH
OH OH  (G) −CH= CH2 , − Me, − Ph, − Et

(H) −CH − CH2 − Br, − Cl, − CH2 − CH2


(D) D-Alaninc CH3 CH COOH
NH2  −CH2 − Br,(Me)2 CH −

(I) −Cl, − Br, − I, − NH2

Q.16 Draw the most stable conformer of N–meth-
ylpiperidine. (J) NH2 ,NO2 ,CH2NH2 ,C ≡ N

Q.17 Considering rotation about the C–3–C–4 bond of Q.21 Allot R/S configurations to the following optical
2–methylhexane: isomers.
9 .48 | Isomerism

CH3 COOH Q.25 In each of the following pairs which will have less
enrol content:
(A) H2N H (B) H CH
CH2OH O OCH3 O OCH3
O
C C
COOH CH3 (A) and
(C) H OH (D) H Cl
H OH H H
COOH CH3
(B) N O and N O
Q.22 In each of the following pairs which is more stable: H H
O OH
Q.26 In each of the following sets of compounds write
the decreasing order of % enrol content.
(A) 1
O
N O
N
(II) (A)
H (I) (A) O O
(I) (II) O (III) O
(I) (II) (III)

(B) 1 HO (B)
O N N (B)
O
(II)
H (I) O
O O
O
O
O
O
(I) (II) (III)
O (I) (II) (III)
OH
C
(C) 1H C
H NH2 NH Q.27 Identify the following pairs as enantiomers,
(I) (II) diastereomers or identicals.
O Me H

C OH H Cl Cl Me
(D) 1 CH3 C (A)
CH3 NH2 Me Br
(I) NH H Br
(II)
Me H
O
C OH
CH2OH COOH
(E) CH3 1 CH2 C
OH
OH H OH
(I)
(II) (B) H OH
H OH H OH
Q.23 In each of the following pairs which is more stable: CH2OH
COOH
O O H O
O
CH3 CH3
C C C C
(A) HO H
CH3 CH2 CH3 CH3 CH CH3 H OH
(I) (II) (C) H Cl H Cl

H H OH HO H
Q.24 In
O each Oof the following
O O pairs which will have less
enol content: CH3 CH3

(B) O O O
O
C Q.28 In each of the following sets of compounds write
and
(A) (I) and (II)
(B) the decreasing order of % enrol content.
CH3 CH3 O O O O
O
O O O
H O
CO CH3 OC O N
((C)) CH C and 1CH3 (D) and
C C O
3 (A) (B) (C) (D)
O CH2
(I) (II)

O O
 Isomerism | 9.49

Q.29 In each of the following sets of compounds write Q.4 In which of the following pairs first will have higher
the decreasing order of % enrol content. enol content than second:
O O O
O COOEt
(A) CH2 C
and
N COOEt CH 3 CH3
N O
Cl
COOEt O O
H H
(A) (B) (C) (D) (B) CH2 C C
and
COOEt CH3 CH3 OCH3
Q.30 In each of the following sets of compounds write O O O O
the decreasing order of % enrol content.
(C) C C and C C
O O O CH3 CH2 OCH3
O CH3 CH2 CH3
O H H O O O O
(A) (B) (C ) (D) C C C C
(D) and
CH3 CH2 CH3 Ph CH2 Ph

Exercise 2
Q.5 What statement is correct for Keto – enol
Single Correct Choice Type tautomerism?
(A) Tautomerism is catalysed by acid and base.
Q.1 Identify the position isomer.
(B) Tautomers are present in dynamic equilibrium state.
(C) Generally keto is more stable than enol from in
&
(A) & CN (B) NC mono Ketones
CN NC (D) Atomic arrangements are same in tautomerism.
O

Q.6 What is the relation between (I), (II) and (III)?

(C) & (D)
OCH3 O O OH O-
OCH3 + +
(I) HN NH (II) N N (III) HN NH
+
O N O O N O -O N O-
Q.2 Which compound show tautomerism
H H H
O
(A) I and II are tautomers
(A) Ph–NO (B) (B) III is conjugate base of II
O (C) III is resonance structure of I
(D) No relation exists.
N OH

(C) (D) HCHO Q.7 Which of the following have zero dipole moment?
(A) p–Dichlorobenzene (B) Benzene–1,4–diol
Multiple Correct Choice Type (C) Fumaric acid (D) Maleic acid

Q.3 Which of the following compounds have higher

Q.8 Which of the following statements is/are not correct?
enolic content than Keto content:
O (A) Metamerism belongs to the category of structural
O O isomerism
O
(A) CH3 C C CH3 (B) (B) Tautomeric structures are the resonating structures
of a molecule.
O O (C) Keto form is always more stable than the enol form
(C) O (D) Geometrical isomerism is shown only by alkanes
(D)
 O O
9 .50 | Isomerism
C CH2 C

Q.9 Which compound show tautomerism:

OH O(A) C CH
OH C (B) CH CH2 C
N O OH OH O
(A) (B) (C) (D) None of these

(C) CH CH
N=O CH (D) C CH2 CH

OH OH O OH

Q.10 Tautomeric form of this compound is/are:

Q.13 Which of the following can tautomerise:
OH
HO O O O
OH
(A) CD3, C Ph (B) (C) (D)
N
HO OH O H
OH
O O Q.14 Tautomer of which of the following can show
HO O HO O geometrical isomerism
(A) (B) (A) CH3–CHO (B) CH2CH2–CHO
HO OH O O O O
O OH O O
O (C) (C) (D) (D)
HO O
(C) (D) All of these
Q.15 The Z–isomer among the following are:
HO OH
OH
(A) CH3 − C− H (B) CH3 − C− H
|| ||
C3H7 − C − C2H5 C2H5− C − C3H7
Q.11 Which of the following is not the correct
relationship.
(C) Cl − C− Br (D) Cl − C− Br
|| ||
Me Me Me
H− C −F F − C −H
Me Me

Q.16 Which of the following is correctly matched?
Me Me
OH O-Me OH O-Me (A) CH3 − CH = CH − CH = CH = C2H5 → 4
I II III IV
(A) II and TV are metamer (B) CH3 − ( CH = CH)4 − CH3 → 2
(B) I and II are functional isomer (C) CH3 = CH − CH = CH2 → 23 + 21 = 10
(C) I and III are chain isomer
(D) CH3 ( −CH= CH)5 − CH3 → 24 + 22 = 20
(D) I and IV are positional isomer.[as q 8]

Q.17 Which of the following compounds show

Q.12 Tautomer of following compound is:
tautomerism?
O O O O
O S
C CH2 C C CH2 C || ||
(A) NH2 − C − NH2 (B) NH2 − C− NH2
O
C CH(A) C C CH C(B) (B)2 C
CH CH CH CH2 C ||
OH OH (C)
(C) HO N O (D) CH3 − C − NH2
O OH O OH O O

CH (CH
C) CH CH CH (D)
CH C CH 2 CH
(D) C CH2 CH

OH OH OH OH O OH O OH
 Isomerism | 9.51

Match the Columns (B) OH

O
(q) Structural isomer
Q.18 Match Column I with Column II

Column I Column II
(C) OH OH (r) Positional isomers
O
||
(A) CH3 − C − C3H7 (p) Chain isomer
(D) O CH2 (s) Atleast one of the two
O structures is enol
||
& Et − C − O − Et OH

CH3 Q.21 Match Column I with Column II

CH3
(B) CH3 & (q) Positional
Column I Column II
isomers
(A) (p) Positional isomers
CH3
O OH
(C) (r) Metamers (q) Geometrical
& (B) isomers
O O HO OH
Me OH Me (r) First is E and
(C) C=N C=N second is Z form
(D) CH3 − C − O − CH3
|| (s) Tautomers
OH

CH3
OH (s) Structural isomer
& CH3 − CH2 − CH2 − O − CH3 (D) OH

OH
OH
Q.19 Match Column I with Column II

Column I Column II Q.22 Match Column I with Column II

(p) Geometrical isomers
(A) Column I Column II
Compound Number of geometrical isomers

(q) Structural isomer (p) 2

Br (A)
(B) Br
Br (B) (q) 4
Br
F I (r) Number of Geometrical
(C) (r) 6
isomer of first compound is
(C) Br F
Cl Br even number

I Cl (s) 8
(D)
(s) Number of geometrical
isomer of second compound is
even number

Q.20 Match Column I with Column II

Column I Column II
(A) O OH
(p) Tautomers
9 .52 | Isomerism

Previous Years’ Questions reaction, is

(2008)
(A) (C2H5)2CHCl (B) (CH3)3CCl
Q.1 Which of the following compounds will show (C) (CH3)2CHCl (D) CH3Cl
geometrical isomerism? (1998)
(A) 2–butene (B) Propene Q.8 The absolute configuration of is (2008)
(C) 1–phenyl propene (D) 2–methyl–2–butene HO2C CO2H

Q.2 The correct statement(s) about the compound given

OH
below is (are) (2008) HO H H
Cl H
(A) S, S (B) R, R (C) R, S (D) S, R
CH3
H3C
H
Cl
Q.9 α–D–(+) glucose and β–D (+) – glucose are (2013)
(A) The compound is optically active
(A) Conformers (B) Epimers
(B) The compound possess centre of symmetry
(C) The compound possess plane of symmetry (C) Anomers (D) Enantiomers
(D) The compound possess axis of symmetry
Q.10 Glycerine contain one …………..hydroxy group.
Q.3 The correct statement(s) concerning the structures (2004)
E,F and G is (are) (2008)
Q.11 (A) Draw Newman’s projection for the less stable
H3C O H3C OH H3C CH3
staggered form of butane.
H3C CH3 H3C CH3 H3C OH (B) Relatively less stability of the staggered form is due to
(E) (F) (G)
(i) Torsional strain
(A) E,F and G are resonance structures (ii) van der waals’ strain
(B) E,F and G are tautomers (iii) Combination of the above two (2004)
(C) F and G are geometrical isomers
(D) F and G are diastereomers Q.12 µobs = ∑ µixi Where µi is the dipole moment of
stable conformer and Xi is the mole fraction of that
Q.4 The correct statement(s) about the compound conformer.
H3C − H C − CH = CH − C H − CH3 (X) is (are) (2009) (A) Write stable conformer for Z–CH2– CH2–Z in
| |
OH OH Newman’s projection.
(A) The total number of stereoisomers possible for X is 6. If µsolution =1.0D and mole fraction of anti form = 0.82,
(B) The total number of diastereomers possible for X is 3. find µgauche

(C) If the stereochemistry about the double bond in X (B) Write most stable meso conformer of (CHDY)2 If
is trans, the number of enantiomers possible for X is 4. (i) Y = CH3 about C2–C3 rotation and
(D) If the stereochemistry about the double bond in X is (ii) Y = OH about C1–C2 rotation. (2005)
cis, the number of enantiomers possible for x is 2.

Q.5 M–chlorobromobenzene is an isomer of m–bromo- Q.13 Give the total number of cyclic structural as well
chlorobenzene. (1985) as stereo isomers possible for a compound with the
molecular formula C5H10 (2009)
Q.6 2,3,4–trichloropentane has three asymmetric carbon
atoms. (1990)

Q.7 The organic chloro compound, which shows

complete stereochemical inversion during a SN2
 Isomerism | 9.53

MASTERJEE Essential Questions

JEE Main/Boards JEE Advanced/Boards

Exercise 1 Exercise 1
Q.1 Q.3 Q.11 Q.15 Q.4 Q.5 Q.11 (3,8,12)
Q.13 (E,B) Q.21 (C,D) Q.23 (D,E) Q.27
Exercise 2
Exercise 2
Q.2 Q.7 Q.11
Q.1 Q.3 Q.8 Q.20
Q.18 Q.22 Q.23

Previous Years’ Questions

Previous Years’ Questions
Q.2 Q.4 Q.9
Q.4

Answer Key

JEE Main/Boards
Exercise 1

Q.6 A Q.7 –52o Q.8 B Q.9 B Q.10 D Q.11 D Q.12 B

Q.13 B Q.14 C Q.15 A Q.16 B Q.17 A Q.18 C Q.19 B

Q.20 D

Exercise 2
Single Correct Chioce Type

Q.1 B Q.2 C Q.3 D Q.4 C Q.5 B Q.6 C Q.7 D

Q.8 C Q.9 B Q.10 A Q.11 D Q.12 B

Previous Years’ Questions

Q.1 B Q.2 C Q.3 A Q.4 D Q.5 D Q.6 C Q.7 A

Q.8 C Q.9 Non–superimposable; enantiomers Q.10 C Q.11 A

9 .54 | Isomerism

JEE Advanced/Boards

Exercise 1

Q.1 3 Q.2 6 Q.3 4 Q.4 A,B,C,E,G Q 5. 10 Q 6. 7

CH3 CH3 CH = CH2

Q 7. (A) 2, H CH2 CH3 (B) H CH2 CH3 (C) 1, H CH3

CH2 CH2 CH3 CH CH3 CH2 CH3

CH3

CH = CH2 F
H Cl
(D) 1, H Cl (E) 1, (d ,1)
Cl H
Br
F

Q.8 4 Q.9 7 Q.10 10 Q.11 Z–I,II,III,VI,VII; E–IV,V,VIII,IX,X,XI,XII

Q.12 (A) 6, structural isomers = 4, stereoisomers = 3

H Cl H Cl

H C C F (Optically inactive) H C C Cl (Optically inactive)

Cl F F F
H H H Cl

F C C Cl (d,1, meso) F C C H (Optically inactive)

Cl F F Cl

(B) 10×4=40, structural (positional) isomers =10, stereoisomers = 40

Cl Cl Cl Cl l
F Br F H F D F l F H
l H l Br l H Br H Cl Br
D D Br D D

l l H Cl Br
F D F Br F D F Br F D
Cl Br H Cl Cl Br l Cl H Cl
D D Br D D

(C) 14, structural isomers = 7, Stereoisomers = 14

F Br F F

Cl C C C Br Cl C C C F Cl C C C I Br C C C Cl

l l Br l

F Cl F Cl F Br
C C C C C C C C C
l Br Br l Cl l
 Isomerism | 9.55

Q.13 (A) Positional (B) Functional (C) Metamerism (D) Positional

(E) Functional (F) Tautomerism

Q.14 Stable are : (A) diequatorial

H
i-Pr C2H5 C2H5
(B) (C) (D)

CH3
H5C2 H3C
(trans)

CHMe2 CHMe2
C2H2
(E) (F)
C2H5

CH3 COOH COOH COOH

Q.15 (A) H OH (B) HO H (C) H OH (D) H NH2
C4H9 CH3 CH2OH CH3

H H Et
N
CH3
Q.16 Q.17 (A) (B)
H H H
H H
Et H
Q.18 (A) Cis (B) Cis (C) Cis (D) Trans (E) Trans (F) Trans

Q.19 Position isomers, Functional isomers, Tautomers, Geometrical isomers CH3

NO2

Q.20 (A) 4,1,2,3 (B) 4,1,2,3 (C) 1,3,2,4 (D) 4,3,2,1 (E) 2,4,3,1 (F) 4,2,3,1

(G) 3,1,4,2 (H) 2,4,1,3 (I) 3,2,1,4 (J) 2,1,4,3

Q.21 (A) S (B) R (C) R, S (D) S , S Q.22 (A) 1; (B) 1; (C) 1; (D) 1; (E) 1;

Q.23 (A) 2; (B) 2; (C) 1; (D) 2; (E) 1 Q.24 (A) 2; (B) 1; (C) 2; (D) 1; (E) 2

Q.25 (A) 2; (B) 2 Q.26 (A) 3>1>2 (B) 4>2>1>3

Q.27 (A) Diastereomer, (B) Enantiomer, (C) Diastereomer

Q.28 (D)>(B)>(A)>(C)

Q.29 (C)>(A)>(D)>(B)

Q.30 (C)>(D)>(B)>(A)
9 .56 | Isomerism

Exercise 2

Single Correct Chioce Type

Q.1 C Q.2 C
Multiple Correct Choice Type

Q.3 B, D Q.4 A, C Q.5 A, B, C Q.6 A,C Q.7 A,B Q.8 C,D

Q.9 (A) P,R,S (B) Q (C) Q Q.10 A,B Q.11 A,D Q.12 A,C,D Q.13 A,B,C Q.14 B,C

Q.15 A,C Q.16 A,B Q.17 A,B,C,D

Match the Columns

Q.18 A → r; B → q; C → s; D → q Q.19 A → q, r, s; B → q, r, s; C → p, r, s

Q.20 A → p, q, s; B → q, s, C → s; D → q, s Q.21 A → p, r, s; B → q; C → q, r; D → p, r, s

Q.22 A → p; B → p; C → s; D → p

Previous Years’ Questions

Q.1 A,C Q.2 A,D Q.3 B,C,D Q.4 A,D Q.7 D Q.8 B Q.9 C
OH

OH

Solutions

JEE Main/Boards
CH3 CH3 CH3 CH3

Exercise 1 *CHOH HO C* H HO C* H H C* OH
*COOH HO C* H H C* OH HO C* H
Sol 1: i. (A) reacts with Na to give H2 and thus it
contains (–OH) group. CH3 CH3 CH3 CH3
(A) (c) Meso form (D) ‘l’ form (E) ‘d’ form
ii. The molecular weight of (A) ( C4H10O 2) is 90. If one
(OH) group, then 90 gm (A) with Na gives 11200 mL H2 (B) ‘d’ ‘l’ forms
(i.e., half mole H2). * Represents two
11200 × 0.90 asymmetric C atoms.
0.90 gm of (A) gives = 112 ml of H2 at STP.
90
Sol 2: Heptane is C7 H16.
Since 0.90 Na gives 224 mL H2 at STP, it contains two
The homologues of heptane are C7 H14 and C8 H18.
(–OH) groups.
OH i. Molecule of hexane having one quaternary C atom:
iii. keeping in view the above facts, (A) is C4H8
OH CH3
1 | 3 4

iv. (A) shows optical isomerism of which (B) form is CH3 − C2 − CH2 CH3 (2,2 − Dimethylbutane)
|
optically active having two isomers (D) and (E); (C) being o
C H3
C − 2 is 4 C atom
the inactive form; therefore, (A), (B), (C), and (D) are:
ii. Molecule of octane having one quaternary C atom:
 Isomerism | 9.57

Br2
CH3 CH3.CH.CH.CH3
1 | 3 4 5 6
CH3.CBr.CH.CH3
CH3 − C2 − CH2 CH2CH2 CH3 (2,2 − (2,
Dimethylbutane)
2–Dimethylhexane) CH3 CH3 CH2.CH.CH.CH3
| +
(2,3-Dimrthyl butane) Br CH3 CH3
C H3 CH3 CH3
o
C − 2 is 4 C atom (I) (II)

Note: Other structures with one quaternary may also Sol 5: Vapour density = 36; Molecular weight = 2 × 36
be formed with octane. = 72
ii. Molecule of hexane having two tertiary c atoms: Examination of molecular weight suggests it to be an
alkane, i.e. Cn H2n+2.
Where C–2 and C–3 are 3°C atoms.
1 2 3 4 12n +2n +2=72 ⇒n =5
CH3 − CH − CH − CH3
| | Therefore, alkane (A) is C5 H12.
CH3 CH3
(A) Gives only one product on substitution, thus (A) is:
(2, 3 − Dimethylbutane)
CH3 CH3
Molecule of octane having two tertiary C atoms: |
Cl
|

1 2 3
CH3 − C − CH3 2
→ CH3 − C − CH2 Cl
| |
CH3 − CH − CH − CH2 CH2 CH3 CH3 CH3
| |
CH3 CH3
(A) is (CH3)4C, i.e. 2, 2–dimethyl propane ( neopentane).
(2, 3 − Dimethy hexane)

C–2 and C–3 are 3°C atoms.

Sol 6: H 1
2
3 H Allenes of the type
Sol 3: i. Alkane (A) C5 H12 on chlorination gives four
monochlroro products and thus (A) is isopentane. H H

Sol 7: Since (A) and (B) are enantiomers,

O  so
H specific
Chlorination
CH3 CH CH2 CH3 O H H
  have
rotation of B is –52° (because enantiomers  equal
CH3 (A)
Dehydro
 
CH2 C CH2 CH3 CH2Cl.CH.CH2CH3 and
CH3 opposite
C specific
CH 3 rotation).H  C  C  C H
halogenation
Acetone 
CH3 CH2 (Enol form)
(Keto form) H
(B)
Sol 8: Two higher priority groups (Cl and CHO) on C–1
CH3
CH3 CCl.CH2.CH3 C CH. CH3 and C–2 are in the opposite directions; so the and C–2
CH3 (9,11 , and 2LP -
e s)
CH3
(F) are in the opposite directions; so the configuration is E.
(C) show optical isomerism.
Cl 2
H 1 3 H C2H5
Sol 4: Alkane is Cn H2n+2, Molecular weight =86 a.
C C
2H (Does not show O.I.)
H
H3C 1 CHO
∴12n +2n +2=86 ⇒ n =6
Therefore, alkane is C6H 14. Sol 9: In (B), the two groups (two H atoms) are same
around the
H doubleH bond.
CH3
CH3 CH.CHCl.CH3 C CH.CH3 4 2
3 1
CH3 5 H
CH3 (F) b. Me Me
(Show O.I.)
(D) Sol 10: H H
o
[o] 60
CH3 CH.CH2.CH2.Cl (CH3)2CH CH2 OH
1
CH3 3 H Me
H
CH3 4 *
(E) CO + CH3COOH
Me 2 H
CH3 (G) (H) c. H
Staggered (It has an
conformation asymmetric C atom)

The alkane with this formula on bromination giving

two product may be written as H3C CH3 Sol 11: The mirror image of placed football is non–
| | superimposable.
CH3 . CH. CH. CH3

Sol 12:
 7
Me
6
5
4
3
2
1
Me   R
R’
C C C
R
R’ 
9 .58 | Isomerism

Terminal groups are same. The number of double Sol 2: (C) (2Z,4E,6Z)–octa–2,4,6–triene
bonds is two (even number).
Sol 3: (D) 3– stereo centers and no POS in any
∴ Number of GI= 2n–1 +2 (n–2)/2= 21+20=2+1=3
compound
Where n is the number of double bonds. ∴ Stereo isomers = 23 = 8

Sol 14: Me
1 Sol 4: (C) Compounds are (C) constitutional isomers
3
4 COOH
Me 2
Sol 5: (B)
H
CH3 OH
Two same groups (Me ) on C–3; hence, do not show
(A) H OH CH3 H
G.I.
CH3 CH3
Sol 15: 9σ Bonds, 1 π and 2 lone pairs. Achiral compounds hence
identical
H 
OH
| | CH3 CH3
H − C− C = C− H (B) H OH and H C2H5
| |
H H C2H5 OH

Sol 16: Order of enol content:

Aldehyde < Ketone < Keto–aldehyde < Diketone.
(iii < ii < i < iv)

Sol 17: CH3

H3C − C* − C3H7
|

|
(Total C =
7)
 (C)
CH3

CH3
C=C
Enantiomers

Br
Symmetric compound
(No isomers)

CH3
Cl

H Cl Br Br
(Optically active alkane)

Sol 18: Although the meso compounds contain CH3

asymmetric C atoms, but they are optically inactive due Cl
to superimposable mirror image or due to the presence (Same compound)
of any element of symmetry.

Sol 19: Meso compound Sol 6: (C) I and II are enantiomers as they are non-
superimposable mirror image of each other.

2
5 I, II and are all structural isomer as they have same
C 2H5 C 2 H5CH3 molecular formula.
| |
Sol 20: H3C − 3 C − C36H7 or H3C − C3* − CH2 − CH3 Cl
|
|
2 1
Sol 7: (D)
H CH3 Forms G.I.

2–Methyl hexane 2, 3–Dimethyl pentane Cl

Both (I) and (II) are optically active alkanes. CH3 OH
C=N Forms G.I.
H

Exercise 2
Forms geometric
Single Correct Choice Type
(Trans form)
Sol 1: (B) All groups are as far apart as possible.
As form of ring is also formed. Ans (D)
 Isomerism | 9.59

Sol 8: (C) CH3 CH3 Sol 3: (A)

H Cl Cl H H3C CH2 Ph H CH2 Ph
Cl H Cl H C C C C
H H H3C H
CH3 CH3
cis trans
(A) Meso-isomer
CH2OH (Symmetric) 1-phenyl-2-butene
HO C H represent Sol 4: (D)
∴ Optically inactive optical rotation = 0 Cl
CHO F F I
C C + C C
Sol 9: (B) CHO Br I Br Cl Geometrical isomers
H C OH Represent (D)
F Br F I
CH2OH C C + C C
Cl I Cl Br Geometrical isomers
Since OH is on right side of the carbon chain, molecule
acquires D configuration.
CH3 C2H5 F Cl F Br
(A) C C (2) Z C C + C C
C2H7 C3H5
O O I Br I Cl Geometrical isomers

Sol 10: (A) CH3–C–OH (1)

& H–C–OCH3 Are functional
H C2H7 H
isomers (B) (1) C C E •
CH C H Sol 5: (D) CH3 CH2 C COOH
(B) CH –CH –C≡H and CH –C≡C–CH Are positional
3 2
3 2 5
3 3

(C) Are postional

(1)
isomer
(1) CH3
Br F
(C) 2-methyl butanoic acid
(D) Are funtional isomer
C C Z
Cl H
Has a chiral carbon, optically active.
(1)
Sol 11: (D) Correct
Cl nameBr
(D) C C E Sol 6: (C)
⇒ (2 D 3L 4D 5D) 2, 3, 4, 5, 6 – pentahydroxyhexanal
(1) P Cl CH3
1 CH
3
H H
Sol 12: (B) 2 stereo centres and non symmetry H H 120o
anti-clokwise
3
3 1
∴ 22 = 4 2 H3C
2
H
H H
CH3
CH3 gauche
Previous Years’ Questions
Sol 7: (A)
CH3
Sol 1: (B) I and II are optically active while III is Br

optically inactive (meso form). H

Br2
H
C
H Br
CH3 CCl4
H
H3C Br
C C C H
CH3 M CH3 CH3 CH3 CH3
H3C H
Br meso
H OH HO H H OH

HO H H OH H OH Sol 8: (C) Molecules that are non–super imposable

on its mirror image are optically active and known as
CH3 CH3 CH3 chiral molecule. However, for chirality of molecule,
presence of chiral centre is not essential, eg.
I II III
H3C CH3

Sol 2: (C) The ‘D’ term in name is derived from D– C C C
glyceraldehyde.
H H
Molecule is chiral but does not possesses any chiral
carbon.
9 .60 | Isomerism

Sol 9: Non–superimposable, Enantiomers.

Sol 2:
Sol 10: (C) OH O

enol keto
Sol 3: C6H12 CH3 CH2CH2CH3 Total = 4 pair
Sol 11: (C) C=C
+

SbCl5 (1)
Cl − C H − CH3  → Ph − CH − CH3 + SbCl5−
| Toluene CH3 CH3
↓ C=C
Ph CH2-CH3
Ph − C H − CH3 (2)
| CH3CH3 CH3CH3
Cl C=C
dl − mixture (3)

Sol 12: (A) 1CO H 1 CH3 CH2-CH3

2 CO2H C=C
2
1 (4) CH3
H OH H OH 2S
2
H Cl H Cl 3R Sol 4:
3
4 1 Compound Optical activity
4 CH3 3 CH3
Numbering according
(A) Planar compound but CHClBr Active due to
lUPAC numbering
to ClP rules for (group active) CHCl–Br
R/S naming (B) Non–planar Active
(C) Non–planar Active
(D) Planar non symmetric Inactive
Sol 13: (A) C₆H₅CH₂CH=CHCH₃ has two geometrical
isomers as (E) Non–planar & asymmetric Active
(F) Non–symmetric but planar Inactive
C6H5CH2 H C6H5CH2 CH3 (G) Non–planar (chain form) Active
C=C and C=C (H) Planar Inactive
H CH3 H H
(I) Planar (no–chiral) side groups Inactive
Trans Cis
Cl Cl
Sol 5:
(4) Br Br

JEE Advanced/Boards (3) (1) I
(2)
I
Exercise 1
Cl Cl
Sol 1: Three isomers are possible (4) I

OH OH OH (3)
I Br (1) Br
CH3 (2)
Cl

CH3
CH3
I Br

= 4 + 4 + 1 +2 – 1 = 10 isomers
 Isomerism | 9.61

Sol 6: 7 isomers
C C C Sol 8:

N N
C C C C C C C C C
C

N C
C 4 structure
C C C
N
C C C C C C
C Sol 9:
N C
C
C C C C C N N
C
C C

CH3 CH3
Sol 7: (A) H CH2 CH3 H CH2 CH3
CH2 CH2 CH3 CH2 CH3
CH3 7 isomers
(B) C6H12
CH= CH2 Sol 10: C5H8O
C5H8O
H CH3 C=O
O
CH2 CH3

(C) C5H9Cl
CH3 CH2CH3 CH3
H Cl H Cl CH2 O
O
C= CH2 CH= CH2
CH3 CH2
CH2
CH3 CH2 Cl
H Cl H CH3 O
CH=CN-CH3 CH= CH2 CH2
CH3
H Cl O C=O
CH2
CH2-CH=CH2
5 isomers
C=O C=O
(D) C2H4ClBr
C
H
Br C Cl
Sol 11: (1) (1)
C=C
(e) C2H2Cl2F2
H (I) Confi -Z
(2)
H Cl
Cl H (1)
(2)
F
Optically active
9 .62 | Isomerism

(1) (1)
O O Me F (1)
O (XI) E
(II) Confi = Z (1)
Cl Me
O
(1)
C≡C

CH2–CH2–CH3 (XII)
(III) C C Z
(1) (1) CH
C–CH3 E
CH3 (1)
CH3

(1)
Sol 12: (A) C2H2Cl2F2 (3)

Ph H
H
(IV) E FF Cl
Cl
(1)
(optically active 2)
Cl Cl FF(1)
Cl (1)
H
H

(1) H Cl (2) I Cl (3)

Br
F C C F H C C Cl
(V) C C E
Cl H Cl F H
Cl Cl (2) F H Cl (2)
N–C CH2=CH2 Cl C C H Cl C C H
(VI) C C Z F F F Cl
HOOC C=O (B) C2HClBr IFD
(1) (1)
All isomers all active (no meso)
(1) (1)
HO C≡CH ‫ ؞‬Corresponding to each structural there all 4 stereo isomers
(VII) C C CH3 Z
‫ ؞‬Total number of isomers (structure all)
OHC C–CH3
(1)
CH3
Cl Cl H
O (1)
F Br F H F Br
O(1) I H I Br I Cl
O
(VIII) E D D D

O O
Br Cl I
(1)
O F D F I F H
(1) H Cl Br H Cl Br
Me OMe
I D D
(IX) E
(1)
Et OΘLi H I Cl
18 F D F D F D
H OH (1) Cl Br Cl Br I H
(X) E
(1) I H Br
D OH
16
 Isomerism | 9.63

I OH OCH3
(E)
F Br CH3
10 isomers
H Cl

D
Functional

(C) Trans (2 isomers each) OH O

(F )
Cl (VI) Tautamerism
F––C––C C––Br Chiral
I
Br Sol 14:
Cl––C––C C––F Chiral C2H5 C2H5
553 Me Me
I
(A) or
F
Br––C––C C––I Chiral
More stable (both in equatorial less repulsion)
I
i Br i Br
I Cl
C C C Chiral (B)
F Br >
H5C2
I Cl C2H5
C C C Chiral Both equatorial
Br F
C2H5
F Cl Me
C C C Chiral C2H5
(C)
Br I Me >

Morestable
Sol 13: C2H5
Cl Cl Cl C2H5
(D)
(A) C––C
(I) C––C Positional Me
(1)
Cl CH3
O
More stable
(B) C–C–COOH
(II) CH3–C–OCH3 Et
Functional Et
(E) <
O O

(C) CH3–C–OCH3 H–C–OCH2CH3

(III) i-Br i-Br
Metamerism More stable

OH OH CHMe2
NO2 CHMe2
(D)
(IV) (F)

C2H5
Positional NO2
C2H5
9 .64 | Isomerism

CH3 COOH C–C=C–C=C–C=C

Sol 15: (A) H OH (B) HO H
NO2
C4H9 CH3 ONO–C–C=C–C=C–C=C
Functional
COOH COOH
C=C–C–C
(C) H OH (D) H NH3
C=C C=C
CH2OH CH3 Geometrical
C C
NO2 CH3
Sol 16:
..
N Sol 20: (A) OH > CHO > CH2OH > CH3
CH3 4 > 1 > 2 > 3

(B) NH2 > – Ph > CH (Me ) > H

2
4 > 1 > 2 > 3

Sol 17: i-Bu i-Bu Et (C) COOH > CHO > Ph > C =
CH2

H H 1 > 3 > 2 > 4

(A) (B)
H
H H H H (D) Ph > C ≡ CH > CH= CH2 > CHMe2
H 4 > 3 > 2 > 1
Et

According to hydrogen (E) CH2Br3 > CH3Cl > CH2OH > CH3
2 > 4 > 3 > 1
Sol 18: (A) 1–3 axial–axia cis
(F) OMe > – NMe2 > Me > H
(B) 1–4 axial–equitorial cis 4 > 2 > 3 > 1
(C) 1–3 axial axial cis
(G) Ph > CH = CH2 > Et > Me
(D) 1–2 axial axial trans
3 > 1 > 4 > 2
(E) 1–4 axial axial trans
(F) 1–3 axial equatorial trans (H) Cl > CH (Me )2 > CH2 ( CH2 – Br ) > CH2 – CH2 – CH2 – Br
2 > 4 > 1 > 3
 
Sol 19: C7H7O2N (I) I > Br > Cl > NH2
CH3 CH3 CH3 3 > 2 > 1 > 4

NO2 NO2 (J) NO2 > NH2 > C ≡ N > CH2NH2

2 > 1 > 4 > 3
COO COOH
NO2 CH3 (B) H OH H OH
Positional
Sol 21: (A) H2N H CH2OH H OH

CH3 Cl S R COOH
R1S
COO
COO COOH
COOH CH3
(B) (B)H H OHOH (C)
H H OHOH (D) H Cl
ONO
Functional H H OHOH H Cl
CHCH2OH
2OH
COOH
COOH CH3
R R
R1SR1S S1S

CHCH
3 3

H H Cl Cl
 Isomerism | 9.65

O O O OH

Sol 22: (A) (1) > (2)

(D) <
N N
H
O OH

(B) < Dislulented density but intramolecular attractive H–

bonding
O N HO N
H O
(1) > (2) (E)
C CH2 CH3
O CH2 C >
OH CH3
(C) C > H C
H NH O
NH2
(1) > (2) HO CH3
O C
O
OH
(D) C CH3 C C CH2
CH3 NH2 NH2 CH
CH3
(2) < (1)
(7) membered chelates are very difficult
O O
OH O
(E) C Sol 24: (A)
CH2 C > C CH3
CH3 OH OH CH3
(1) > (2)

Enol for
OH
Sol 23: H
O O O O

(A) C C C C More stable due to resonance

CH
CH3 CH2 CH3 CH3 CH3 O
O
(2) > (1) due to H–O=C attraction and chelate formation (B) <
H
O O O O
enol
(B) (2) > (1) OH

Resonance
O H
O
(C) O O
(C) C CH3 CH3 C CH3
C (1) > (2)
CH3 C
O
(1) > (2) CH2 More stable due to extended resonance in enol–form
More e– density is far on higher electro negative element
only
9 .66 | Isomerism

O CH2OH COOH
O H OH H OH
(D) < (B)
H OH H OH
O
(1) hass by COOH CH2OH
Enol for Enantiomer
OH (180º rotation and OH–H reversed)
CH3 CH3
H OH HO H
OH (C)
Extended H Cl H Cl
Resonance I OH HO H
CH2––CHO < CH3––CHO
CH3 CH3
Cl Enol for Diastereomer
CH2OH
C7H9N NaNO3
CH2––CH A C7H8D
HCN
Stable due to –I effect
Br2/H2O

Sol 25: di-bromo derivative

(A) O OCH3 O OCH3
C C
∆ + Cl2/KOH C +H2O + C8H7N

NaNO2/
Isomers HCl

Less enol content as double bond not in conjugation HCN

(O) +H O (D) Cu(D)
(B) 2

N
O
N O Di-paric acid
..

Aromatis On halogenative forms one molecule direvative

atom (2) < (1) according to the following reactions compounds are
En enol No
formation aromatisation NH2 OH

Sol 26: (A) 3 > 1 > 2 (B) 4 > 2 > 1 > 3 A= B=

Me
Sol 27:
H Cl CH3 CH3
(A)
H Br
NC CN
Me

H Me
C= D=
H Me H Cl
Me Br Br H
CH3 CH3
H Me

Distereomer
 Isomerism | 9.67

COOH Exercise 2
Single Correct Choice Type
E=
Sol 1: (B)
(A) are chain isomers
COOH
(B) position are isomers 1º ard.
Since D gives red colour with (A.N.)
(C) OCH3
∴ D is a pairing alcohol R–CH2–OH
OCH3
∴ C would be a primary amine Positional isomers
C = R–CH2–NH2 (D) O
and A would be a R–CH2–CONH2
Mass of RCH2CONH2 = 135 O
∴ Mass of R = 135 – 2 × 12 – 16 – 14 – 4 Functional isomers
= 135 – 24 – 16 – 18 = 77 O
Sol 2: (C) Ph–NO –No tautamerism No – α –
∴ R–Phenyl group
A = Ph–CH2–CONH2
B = Ph–CH2–COOH N–OH N=O
O
C = Ph–CH2–NH2
H
D = Ph–CH2–OH
O
C
∴ Cr= O Multiple Correct Choice Type
C
OH
O
Sol 3: (B,D) B → enol chelation
COOH O
F=
CH3 OH
(D) O Chelation
CONH2
E= OH

CH3
Sol 4: (A,C)
O
Sol 28: (D) > (B) > (A) > (C) COOEt
(A) CH2 C
Sol 29: (C) > (A) > (D) > (B) COOEt CH3 CH3
(1) > (2)
Sol 30: (C) > (D) > (B) > (A)
O
COOEt
(B) (2) CH2 < C
O
COOt CH2 CH3
C
CH3
9 .68 | Isomerism

Carbanion in enol form more stable due to higher–I O

group.
O O O O (C)
(C) >
C C C C
CH3 CH2 CH3 CH3 CH2 OCH3 N=O
(enol form) tautamers
(D) O O < O O
Sol 10: (A,B)
C C C C
CH3 CH2 CH3 Ph CH2 Ph OH
(B) Cl OH

Sol 5: (A,B,C) Cl OH
(A) Tautomers catalysed by acid/base
OH
(B) Tautamers present in dynamic equilibrium OH
continuous conversion form one form to other
HO OH
(C) Generally mono ketones are more stable than enol.
O O
Sol 6: (A,C) I, II are tautamers and III and I are OH
resonating structure
Cl OH A can also be, but C is not possible

Sol 7: (A,B)
Sol 11: (A,D) (i) 2 and 4– are not metamers, they are
chain isomer
(ii) I and V are not positional, they are structural isomers.
Cl OH
Sol 8: (C,D)
Sol 12: (A,C,D) O O
(D) Keto form is not always more stable than the
O OH C CH2 C is

OH O

C=CH2-C
(D) For geometrical rotation can also be show in cyclic OH O
compound
or C-CH2-C

Similarly D

Similarly D

Sol 9: (A,C) Sol 13: (A,B,C) CD3–C–Ph 3 – α –H can

OH O O
(B) 2 – α – H can tautomerise
(A) (C) 1 – α – H can tautomerise
(D) No – α – H can not tautomerise
(B) No alpha–H
 Isomerism | 9.69

Sol 14: (B,C) 4–α–H will show tautamerism

(A) CH3 CHO No isomers (C) HO H=O

(B) CH3 CH3 CHO No isomerism in keto for O N O

CH3 OH
C=C O
H H
(D) CH3–C–CH2
(C) In enol form 2 geometrical isomers 6–α–H will show tautamerism

Match the Columns

(D) No geometrical isomer
O O
Sol 18: (A) CH3–C–O–C3H7 Et–C–O–Et

Sol 15: (A,C) Metamers

O O CH3 CH3
C C CH3
CH3 CH2 CH3 (B)
enol

H CH3
O O Positional isomers

C C
O OH
CH
CH3 CH3

Resonance and chelate or due to a intramolecular H– (C)

bonds
O O HO OH
Tautomerism
Sol 16: (A,B)
(A) CH3–CH=CH–CH=CH–C2H5 (D) CH3–CH–O–CH3
2–stereo centes ⇒ 2 = 4
CH3
CH2=CH–CH–CH2 (Planar symmetric compound)
CH3–CH2–CH2–O–CH3
Isomer = 0
Chain isomers
CH3– (CH=CH)5–CH3
Total isomers
Sol 19 A → P, R, S B → Q C→Q
(B) CH3– (CH=CH)4–CH3 ; Total isomers = 4

Sol 17: (A,B,C,D)

(A)
O

(A) H2N–C–NH2
(A) Both are structural isomers of each other and both
4–α–H will tautamerism have even number of geometrical isomers.
S

(B) NH2–C–NH2
 9 .70 | Isomerism

Br Br
(B) Sol 22: (A)

Br
Isomer = 21 = 2
Br No. of isomer
(B) Both are structural isomer of each other.
(B) *
F I

Br F 1 chiral 21 = 2
(C)
Cl Br center

I Cl (C)

(C) Both are structural isomer of each other. 23 = 8

S-stereo centre
Sol 20:
O OH (D) 2-stereo isomers

(A)

QPS Previous Years’ Questions

Tautomers and one is enol
Sol 1: (A,C) a and c will show geometrical isomerism
O OH as follow:
(A) H3C CH3 H3C H
(B) C C + C C
H H H CH3
enol
cis-2-butene trans-2-butene
Structural isomers (s)
(C) H H Ph H
OH OH
C C + C C
Ph CH3 H CH3
(C) (S) cis-1-phenylpropene trans-1-phenylpropene

Sol 2: (A,D) The compound is optically active as well

Not isomers as it possesses a two–fold axis of symmetry.
O CH2
Sol 3: (B,C,D) E, F and G are not resonance structures
because movement of hydrogen between E and F are
(D) (Q) (S) involved. E, F and E, G are tautomers in which E is keto
OH form and both F and G are enol form of the same E.

Sol 4: (A,D)
Sol 21: (A) Position isomers P, R, S structure CH3 CH3
CH3 CH3
HO H
(B) GeometricQ C OH C OH
C C
(C) Synand antiQ, R H C C H
HO C C H
(D) Position, structuralP, R, S H H H H
(I) (I+II)
(meso) (enantiomeric)

CH3 CH3
HO HO
C C
H H
H C C H C C
 H C C HO C C
H H
H H H H
(I) (I+II) Isomerism | 9.71
(meso) (enantiomeric)

CH3 CH3 (B) The less stability of above mentioned conformer is

HO HO due to vander Waal’s repulsion between the adjacent
C C
H H methyl groups.
H C C H C C
OH H
H C H C Sol 12: (A) Z Z
CH3 H CH3 OH H H H Z

(IV + V) (VI)
(enantiomeric) (meso)
H H H H
Total six isomers. In both cis and trans forms, there are Z H
two enantiomers each. anti gauche

Sol 5: They are identical. Mole–fraction of anti form = 0.82

Mole–fraction of gauche form = 0.18
Sol 6: It has only two asymmetric carbon, carbon no.3 µobs =
1D
is not asymmetric.

H H H
⇒ 1 = µanti × 0.82 + µgauche × 0.18 ∴ µanti =
0
1 5 1
⇒1=
µgauche × 0.18 ⇒ µgauche = = 5.55D
CH3 C • C • C • CH3 0.18
2 3 4
Cl Cl Cl H
(B)
CH3 O

Sol 7: (D) For SN2 reaction, the C atom is least D H D O

hindered towards the attack of nucleophile in the case H
of CH3Cl
H D D H
Hence, (D) is the correct answer.
CH3 H
Sol 8: (B) HO2C CO2H (i) (ii)
1 2
Structure (ii) is more stable than its anti conformer
OH because of intra molecular H–bonding.
HO H H

Both C1 and C2 have R – configuration.

Sol 13:
CH2 CH3 CH3 CH3
CH3
Sol 9: (C) α –D–(+) glucose and β –D (+) – glucose are
anomers.

Sol 10: HO OH
CH3 CH3 H CH3 CH3 H
OH
glycerine
H H CH3 H H CH3
It contains a secondary (2º) hydroxy group.
meso
pair of enantiomers
CH3  Total seven isomers
Sol 11: (A) CH3 ⇒ Total seven isomers
H

H H
H
less stable staggered form of butane