Professional Documents
Culture Documents
1 STEREOISOMERISM
1.0 INTRODUCTION
2.0 GEOMETRICAL ISOMERISM
2.1 Geometrical Isomerism in Alkenes
2.2 Nomenclature Systems of Geometrical isomers
2.3 Geometrical Isomerism in Oximes [>C = N–OH]
2.4 Geometrical Isomers In Azo Compounds ( N N )
2.5 Geometrical Isomers in Cycloalkanes
2.6 Physical Properties of Cis–Trans Isomers
2.7 Number of Geometrical isomers in polyenes
3.0 OPTICAL ISOMERISM
3.1 Optical activity
3.2 Types of Symmetry
3.3 Chiral Compound
3.4 Asymmetric carbon (or) Chiral Carbon
3.5 Projection Formula of Chiral Molecules
3.6 Enantiomers
3.7 Diastereomerism
3.8 Meso isomers
3.9 Calculation of number of optical isomers
3.10 Pseudo Chiral Centre
3.11 D - L System (Relative configuration) : Application on correct Ficher Projection Formula
3.12 Absolute Configuration (R, S configuration)
3.13 Optically active compounds having no asymmetric carbon
3.14 Optical Purity
EXERCISE-1
EXERCISE-2
EXERCISE-3
EXERCISE-4(A)
EXERCISE-4(B)
EXERCISE-5
sdfsfggg
Stereoisomerism
1.0 INTRODUCTION
SL AL
Stereoisomers
Configurational Conformational
(non-interconvertible (Interconvertible
resolvable) non-resolvable)
Configurational Isomerism
SL AL
Non interconvertable Stereo isomers are known as Configurational Isomers.
Stereo isomer which cannot interconvert in each other at room temperature due to restricted rotation known
as Geometrical isomerism.
2.1 Geometrical Isomerism in Alkenes
SL AL
CH3 CH3
H H
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Enthusiast\Che\Unit-06\Stereoisomerism
CH3 CH CH CH3
sp2 sp 2
CH3 CH 3 CH 3 H
Example : C C C C
H H H CH 3
cis–2–butene trans–2–butene
Note : cis trans is possible only when p bond break.
1
JEE-Chemistr y
a a
b C C a b C C y
x
b
Geometrical isomerism present Geometrical isomerism present
p p
C
a y
C C
a y C
q q
No Geometrical isomerism No Geometrical isomerism
(a) Cis–Trans System : If same groups at same side then cis and if same groups at different side then
trans.
a a b C C a
b C C b a b
[Same groups, same side] [Same groups different side]
cis trans
a a z z
Example : C C C C
x y x y
cis cis
Cl Cl
CH 3 C
H
Example : C C
H CH 2 CH 3 C
Br Br
trans-2–pentene It does not show Geometrical isomers So no cis–trans
(b) E – Z System :
E (Entgegen) : When high priority groups are opposite side.
Z (Zussaman) : When high priority groups are same side.
LP HP
C C HP C C HP
HP LP LP LP
'E' 'Z'
HP – High priority and LP – Low priority
l Priority Rules : (Cahn Ingold Prelog Rule)
Rule I : Priority is proportional to atomic number of atom which is directly attached to sp2 carbon.
[HP] Cl CH 3
Br F C C
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Enthusiast\Che\Unit-06\Stereoisomerism
C C Cl C N H 2 [HP]
[HP] I Cl [HP]
Cl Cl
' Z' 'E'
CH 3
CH 3 [C, C, C]
CH 3
[HP] F C [HP]
C C CH 3 decreasing order of atomic number
[LP] CH3 H2C C CH [C, C, H]
3
[LP]
H
'Z'
2
Stereoisomerism
N C
C O C O C N C N
O C N C
O
[O, O, H]
N C C H
H C C
Example : [HP] N C OH
H [O, O, O]
O [HP]
Z'
Example :
H CH3
(i) C C 'Z'
[HP] D CH2 CH3 [HP]
CH 3 H
(ii) C C 'Z'
[HP] Cl CH3 [HP]
CH3 CH3
(iii) C C 'E'
H Cl
(v) 'E'
[I, H, H]
CH3 CH
3
CH2 = CH C(CH3)3
C == C
(vi) HC C 'E'
CH – CH = CH2
NºC
C=N
(vii) HO – C CH3 'Z'
O
3
JEE-Chemistr y
N C CH2 – C(CH3)3
C == C
(viii) H2C = C = CH 'E'
C CH
O
Cl – C C º CH
(ix) C =C 'Z'
Br – C
Ph
O
O
CH3O – C COOH
C =C
(x) Cl – C 'E'
CHO
O
CH3
CH3 – C – CH2 CºN
(xi) C =C 'E'
HO – CH2
CH = N – OH
E-Z Configuration
1. Assign E & Z configuration?
O O
O
O
(I) (II)
O
Z E
CH2CH2CH3
Ph
(III) CH – CH3 (IV)
| Cl
CH3
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Enthusiast\Che\Unit-06\Stereoisomerism
F
| NC CH = CH2
C–C–C Br
(V) F (VI)
HOOC CHO
C–C–C Cl
Z
C º CH O
HO
CH3 O O
OHC C – CH3 O
(VII) (VIII)
| O
CH3 O
4
Stereoisomerism
18
Me OMe OH
H
(IX) (X) 16
Et O¯ Li
+
D OH
CH3
|
CH – CH2 – CH3
Me F
C º CH
(XI) (XII)
Cl Me CH3
H
Ph C H
Example : Ph—CH N—OH
N OH [syn.]
Ph C H
HO N [Anti]
Benzaldoxime
l Ketoxinme
H3C OH H3C
C=N C=N
H5C2 H5C2 OH
SL AL
Ph Ph
N N
N N
Ph Ph
(syn) (Anti)
5
JEE-Chemistr y
Cycloalkanes show Geometrical isomers due to restricted rotation about single bond. Only those cyclo alkanes
show Geometrical isomers in which atleast two different carbons have two different groups.
Me H trans
H Me
3 Solubility (in H2O) cis > trans More polar molecules are more soluble in H2O
More symmetric isomers have higher melting points due to
4 Melting point trans > cis better packing in crastalline lattice & trans isomers are more
symmetric than cis.
The molecule having more vander wall strain are less stable.
5 Stability trans > cis In cis isomer the bulky group are closer they have larger
vander waal strain.
CH3 C H CH3 C H
Example :
H C CH 2 CH3 Cl C H
trans m ¹ 0 cis m ¹ 0
6
Stereoisomerism
H Me
H Cl
H Me
(A) H H (B) Cl (C) Cl Br (D) Me
Cl
Cl Cl
H H Cl Br Me
Solution (A), (B) and (D)
2.7 Number of Geometrical isomers in polyenes
SL AL
R1 HC CH R2
n
(a) If R1 ¹ R2 then number of Geometrical isomers = 2n [n = number of double bonds.]
Example : CH3—CH=CH—CH=CH—CH=CH—CH2CH3
As n = 3 ® number of Geometrical isomers = 23 = 8
Geometrical Isomerism
1. Calculate the total number of open chain isomeric carbonyl compounds of molecular formula C5H8O which
can't show geometrical isomerism.
7
JEE-Chemistr y
7. Among the following compounds, the one which does not show geometrical isomerism is -
(A) C6H5N = NC6H5 (B) C6H5CH = CHC6H5
(C) C6H5 – C = N – OH (D) C6H5 – C = N – CH3
CH3 C6H5
Compounds which have same molecular and structural formula but have different optical activity are known
as optical isomers.
Certain substances possess the property to rotate the plane of polarized light. Such substances are called optically
active substances and this phenomenon is called optical activity.
Light has vibrations occur in all planes at right angles to the line of propagation. In plane polarized light the
vibrations take place only in one plane. Plane polarized light can be obtained by passing ordinary light through
a Nicol prism.
Certain organic compounds, when their solutions are placed in the path of a plane polarized light, have the
remarkable property of rotating its plane through a certain angle which may be either to the left (or) to the right.
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Enthusiast\Che\Unit-06\Stereoisomerism
This property of a substance of rotating the plane of polarized light is called optical activity and the substance
possessing it is said to be optically active.
The observed rotation of the plane of polarized light [determined with the help of polarimeter] produced by a
solution depends on :
(a) The amount of the substance in tube ;
(b) On the length of the sample tube;
(c) The temperature of the experiment and
(d) the wavelength of the light used.
The instrument used to measure angle of rotation is called polarimeter. The measurement of optical rotation
is expressed in terms of specific rotation [a]Dt ; this is given by the following relation :
8
Stereoisomerism
a obs
[a]Dt = [where a = observed angle of rotation]
l´C
(i) Plane of symmetry (POS) : An imaginary plane which bisects any object or molecule into two equal
parts which are mirror images of each other is known as POS.
H Me
Cl H OH
H H H
H OH
Cl Me Me Me
Plane of symmetry Plane of symmetry Plane of symmetry
(ii) Center of Symmetry (COS): It is a point inside a molecule from which on travelling equal distance
in opposite directions one takes equal time.
CH3 COOH
Cl
H H R H
• C=C H H
H H
H R
Cl
Centre of symmetry Centre of symmetry
COOH CH3
(iii) Axis of Symmetry (AOS) (Cn) : Axis of symmetry is an axis such that if one rotates the molecule
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Enthusiast\Che\Unit-06\Stereoisomerism
360 °
by , the new position of molcule is superimposable with the original one.
n
180°
(iv) Alternate axis of Symmetry (AAOS) : An imaginary plane around which rotation by angle x gives
360
its mirror image is known as AAOS. It is represented by Sn where n =
x
9
JEE-Chemistr y
H3C H H CH3
C C ¾¾® C C
H CH3 CH3 H
180°
H3C H
(viii) (ix)
(x) (xi)
F F F
H H
H H
(xii) (xiii) (xiv) (xv)
F F
F
H F
H
F H
F H C
(xvi) (xvii) H H (xviii)
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Enthusiast\Che\Unit-06\Stereoisomerism
H H
F
Solution POS Þ (i), (ii), (iii), (iv), (vi), (viii), (ix), (xi), (xii), (xiii), (xiv), (xv), (xvi), (xvii), (xviii)
COS Þ (iv), (xi), (xiii), (xiv), (xviii)
Compound which is not super imposable on its mirror image is known as Chiral Compound. All optically active
compounds are Chiral.
10
Stereoisomerism
If all the four bonds of carbon are satisfied by four different atoms/groups, it is chiral. Chiral carbon is designated
by an asterisk (*).
Br
Example : H C* Cl
I
3.5 Projection Formula of Chiral Molecules
SL AL
up
CH3
H OH OH H
CH2CH3 CH2CH3
3.6 Enantiomers
SL AL
Stereoisomers which are mirror-image of each other are called enantiomers (or) enantiomorphs. Thus (i) and
(ii) are enantiomers. All the physical and chemical properties of enantimoers are same except two :
(i) They rotate PPL to the same extent but in opposite direction. One which rotates PPL in clockwise
direction is called dextro-rotatory [dextro is latin word meaning thereby right] and is designated by d (or)
(+). One which rotates PPL in anti-clockwise direction is called laevo rotatory [means towards left] and
designated by l (or) (–).
(ii) They react with optically active compounds with different rates.
3.7 Diastereomerism
SL AL
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Enthusiast\Che\Unit-06\Stereoisomerism
The optical isomer which are not mirror images to each other are called diastereomers.
Me Me
Properties
H Cl H Cl
H Cl Cl H
Et Et
I II
(i) Dipole moment Different
(ii) Melting point Different
(iii) Boiling point Different
(iv) Solubility & Density Different
(v) Specific rotation Different
11
JEE-Chemistr y
Example :
COOH COOH
H OH HO H
Example : H OH HO H
COOH (I) COOH (II)
Achiral
I and II are identical
CO2H
CO2H
CO2H
HO—C—H
H—C—OH
H—C—OH
H—C—OH H—C—OH
OH—C—H
CO2H CO2H
CO2H
(3)
(1) (2)
Meso tartaric acid
(i) Achiral compound which have chiral centers is known meso compound.
(ii) They are achiral (optical rotation = 0).
(iii) They have [a] = 0 due to internal compensation of optical rotation.
(iv) They are diastereomer of d – l pair. So, it has different physical properties than d – l -pair..
(v) Presence of more than one asymmetric ‘C’ atoms.
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Enthusiast\Che\Unit-06\Stereoisomerism
The number of optical isomers of an organic compound depends on its structure and number of asymmetric
carbon atoms. Thus, the number of optical isomers may be determined from the knowledge of the structure
of the compound as follows :
(a) When the molecule is unsymmetrical
No. of optically active isomers, a = 2n
Number of meso forms (m) = 0
Number of racemic mixtures, r = a/2
\ Total no. of optically active isomers = (a + m) = 2n
12
Stereoisomerism
(b) When the molecule is symmetrical and has even no. of asymmetric carbon atoms.
No. of optically active isomers, a = 2(n –1)
n
No. of meso forms, m = -1
22
No. of racemic mixtures, r = a/2
\ Total no. of optically active isomers = a + m
(c) When the molecule is symmetrical and has an odd no. of asymmetrical carbon atoms.
n -1
no. of optically active isomers, a = 2(n–1) – 2 2
n -1
No. of meso forms, m = 2 2
\ Total no. of optically active isomer = (a + m) = 2(n–1)
l Stereochemical Formula
H Cl Cl H; Cl H H Cl
C2H5 C2H5 C2H5 C2H5
I II III IV
[a] = +xº –xº +yº –yº
Analysis
I, II – Enantiomers III, IV – Enantiomers
I, III – Diasteromers I, IV – Diasteromers
II, III – Diasteromers II, IV – Diasteromers
A chiral center which becomes achiral on changing the configuration of one of its substituents and vice versa
CH3
CH OH
Pseudo chiral center ¾® HC Br
HC OH
CH3
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Enthusiast\Che\Unit-06\Stereoisomerism
This method is used to relate the configuration of sugars and amino acids to the enantiomers of glyceraldehyde.
The configuration of (+)-glyceraldenyde has been assigned as D and the compounds with the same relative
configuration are also assigned as D, & those with (-) glyceraldehyde are assigned as L.
CHO CHO
H OH HO H
(S)
(R)
CH2OH CH2OH
D-(+)-glyceraldehyde L-(–)-glyceraldehyde
– OH group on right side – OH group on left side
13
JEE-Chemistr y
Examples :
Sugars have several asymmetric carbons. A sugar whose highest numbered chiral centre (the penultimate car-
bon) has the same configuration as D-(+)-glyceraldehyde (– OH group on right side) is designated as a D-sugar,
one whose highest numbered chiral centre has the same configuration as L-glyceraldehyde is designated as an L-
sugar.
CH2OH
CHO | CHO
H OH C=O HO H
CHO
HO H HO H HO H
HO H
H OH H OH H OH
H OH
e.g. H OH H OH H OH
CH2OH
CH2OH D-(-)-Threose
CH2OH CH2OH
D-(+)-Glucose D-Mannose
D-Fructose
The actual three dimensional arrangement of groups in a molecule containing asymmetric carbon is termed
absolute configuration.
System which indicates the absolute configurastion was given by three chemists R.S. Cahn, C.K. Ingold and V.
Prelog. This system is known as (R) and (S) system or the Cahn–Ingold system. The letter (R) comes from the
latin rectus (means right) while (S) comes from the latin sinister (means left).
(R) (S) nomenclature is assigned as follows :
Step 1 : Assign priority to the groups which are attached with chiral carbon.
Step 2 : Bring the lowest priority group to dash by even simultaneous exchanges.
Step 3 : Draw an arrow from first priority group to second priority group till third priority group.
Step 4 : If the direction of arrow is clockwise the configuration is R and if anticlockwise it is S.
(1)
OH H C2H5
S
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Enthusiast\Che\Unit-06\Stereoisomerism
(2)C2H5 CH3 S
C C CH3 OH
H CH3 OH C2H5
(4) (3) H
l Important
Note that the designation of a compound as R or S has nothing to do with the sign of rotation. the Cahn-Ingold
rule can be applied to any three dimensional representation of a chiral compound to determine whether it is R or
S only. For example in above case (i.e. lactic acid), R configuration is laevo rotatory is designated as R-(–)-lactic
acid. Now the other configuration of it will have opposite sign of rotation i.e. S-(+)-lactic acid.
14
Stereoisomerism
(i) Allenes : An sp-hybridized carbon atom possess one electron in each of two mutually perpendicular
p orbitals. When it is joined to two sp2-hybridized carbon atoms, as in allene, two mutually perpendicualr
p-bonds are formed and consequently the p-bonds to the sp2-carbons are in perpendicular planes. Allenes
of the type abC=C=Cab (a ¹ b) are therefore not superimposable on their mirror images and despite
the absence of any asymmetric atoms, exist as enantiomers and several optically active compounds have
been obtained.
(Ex. a = phenyl, b=1-naphthyl)
b a a b
C C C C C C
a b b a
(ii) Alkylidene cyclo alkanes : The replacement of one double bond in an allene by a ring does not alter
the basic geometry of the system and appropriately substituted compounds exist in optically active forms.
H CO2H
H3C H
Related compounds in which sp2-carbon is replaced by nitrogen have also been obtained as optical
isomers.
H OH
N
CO2H
l Difference between Racemic mixture and Meso compound
A racemic mixture contains equimolar amounts of enantiomers. It is optically inactive due to external
compensation.
l External compensation
If equimolar amounts of d and l-isomers are mixed in a solvent, the solution is inactive. The rotation of each
isomer is balanced (or) compensated by the equal but opposite rotation of the other. Optical inactivity having
this origin is described as due to external compensation. Such mixtures of (+) and (–) isomer (Racemic mixtures)
can be separated into the active components.
A meso compound is optically inactive due to internal compensation
l Internal compensation
In meso tartaric acid the inactivity is due to effects within the molecule and not external. The force of rotation
due to one of the molecule is balanced by the opposite and equal force due to the other half. The optical
inactivity so produced is said to be due to internal compensation. It occurs whenever a compound containing
two (or) more asymmetric carbon atoms has a plane (or) point of symmetry. Since the optical inactivity of such
a compound arises within the molecule, the question of separating into active components does not arise.
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Enthusiast\Che\Unit-06\Stereoisomerism
l Special Point
(i) Chiral nitrogen containing tetra alkyl ammonium ion show optical isomerism.
R1 R1
NÅ NÅ
R4 R2 R2 R4
R3 R3
(I) (II)
I and II enatiomers
15
JEE-Chemistr y
(ii) Chiral nitrogen containig tertiary amine do not show optical isomerism
Reason :- Rapid umbrella inversion.
N N
Room temperature
R1 R3 R3 R1
R2 R2
(I) (II)
(iii) Energy required for this interconversion is available at room temperature so I and II are identical
(iv) Ortho substituted biphenyl compounds do not have any chiral carbon but due to chiral molecule, they
are optically active.
NO2 HOOC
SO3H H3C
COOH O2 N
CH3 HO3 S
Horizontal Vertical
plane plane Optically active
Some times we deal with mixtures that are neither otpically pure nor racemic mixture. In these cases we
specify the optical purity of the mixture. It is defined as the ratio of its rotation to the rotation of pure enantiomer.
observed optical rotation
Þ Optical purity = optical rotation of pure enantiomer × 100
e.g. If we have some 2-butanol with observed rotation of +9.72, we compare this rotation with +13.5 rotation
of the pure (+) enantiomer.
9.72
Optical purity = ´100 = 72%
13.5
That means 72% is pure (+) 2-Butanol and 28% is (± mixture)
Total (+) isomer = 72 + 14 = 86%, (–) isomer = 14%
COOH
H OH
Cl Cl
(1) (2) (3)
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Enthusiast\Che\Unit-06\Stereoisomerism
H OH Me Me
COOH
(4) H
OH
(5)
*
OH
Solution (1), (2), (4) and (5)
16
Stereoisomerism
(v) (vi)
Cl Cl
(vii) (viii)
H
H3C—C=C=C=C
(ix) Cl (x) Me
Cl
(xi) Cl HC CH CH=CH–Cl
Cl
(xii)
Cl Cl
Solution (i) = 3, (ii) = 4, (iii) = 4, (iv) = 3, (v) = 4, (vi) = 8, (vii) = 10, (viii) = 6, (ix) = 32
(x) = 2, (xi) = 6, (xii) = 2
Illustration 9. Give (R), (S) & (E), (Z) configuration of following compounds.
CH3
Br Cl
H3C H Cl Me
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Enthusiast\Che\Unit-06\Stereoisomerism
17
JEE-Chemistr y
Optical Isomerism
CH3
H Cl
1. HO H
C2H5
2. Find out the total number of cyclic isomers of C6H12 which are optically active?
(i) and
18
Stereoisomerism
ANSWERS
BEGINNERS BOX-1
1. (Z) – I, II, III, VI, VII ; (E)– IV, V, VIII, IX, X, XI, XII
BEGINNERS BOX-2
1. (8) 2. (A) 3. (D) 4. (B) 5. (C)
6. (D) 7. (D) 8. (C)
BEGINNERS BOX-3
1. (A) 2. 8 3. 4
4. (i) (ii)
Et
Et
C2H5
H Br
(iii) (iv)
CH3
C3H7 CH3
H Br
Cl Br
(v) (vi) H Br
C2H5 CH3
19
JEE-Chemistr y
H
The value of x and y respectively are :-
(A) 4 and 4 (B) 2 and 2 (C) 2 and 4 (D) 4 and 2
5. In the structure :
CH3
H OH the configurations at the chiral centres are :
H Br
CH3
(A) 2R, 3R (B) 2S, 3R (C) 2R, 3S (D) 2S, 3S
CH3 C2H5 Cl Cl
(A) Cl Br (B) Cl Br (C) CH3 Br (D) C2H5 CH3
C2H5 CH3 C2H5 Br
Which of the following statements is not correct
(A) B and C are identical (B) A and B are enantiomers
(C) A and C are enantiomers (D) B and D are enantiomers
H Br
Br
CH3 C C
(I) (II) H3C H3C H
C CH3 H
C
Br H
Br
(A) confermers (B) enantiomers (C) geometrical isomers (D) diastereoisomers
COOH
CH3 H
H H H
(A) (B)
H CH3
H H
OH H Ph Ph
H COOH
H H H H
H H H H
(C) (D)
HOOC H
H OH COOH COOH
CH2CH3
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Enthusiast\Che\Unit-06\Stereoisomerism
21
JEE-Chemistr y
19. Of the five isomeric hexanes, the isomer which can give two structural monochlorinated compounds is-
(A) 2-methyl pentane (B) 2,2–dimethyl butane
(C) 2,3–dimethyl butane (D) n-hexane
20. Which of the following molecules is expected to rotated the plane of plane-polarised light ?
CHO
(A) HO H (B)
SH
CH2OH
COOH
H2N NH2
H H
(C) (D) H2N H
Ph Ph
H
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Enthusiast\Che\Unit-06\Stereoisomerism
22
Stereoisomerism
H H
(A) C6H5–CH=NOH (B) (C) C6H5–N=N–C6H5 (D)
H3C CH3
5. Observe the following structures and pick up the correct option (s) mentioned below :-
CH3 CH3
H Cl H Cl
H H H H
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Enthusiast\Che\Unit-06\Stereoisomerism
CH2Cl Cl
(A) (B)
(A) The two are position isomers
(B) None of the two shows optical isomerism
(C) Only A shows optical isomerism
(D) The two are not related to each other regarding isomerism
23
JEE-Chemistr y
X Y
(A) X is cis- and Y is trans (B) X is Z and Y is E
(C) X is trans and Y is cis (D) X and Y are diastereomers
10. For which of the following pairs of compounds are the correct notation given :-
Ph Ph Ph
N=N and N=N
(A) Ph
Anti-azobenzene Syn-azobenzene
H3C H3C OH
(B) C=N C=N
H OH and H
Syn-acetaldoxime Anti-acetaldoxime
H H
CO2H H
C=C C=C
H CO2H
(C) and
NH2 NH2
Trans-o-aminocinnamic acid Cis-o-aminocinnamic acid
12. Which of the following will show optical isomerism as well as geometrical isomerism.
H3C H3C CH3
CH3
(A) C (B) C
H CH3
24
Stereoisomerism
CH3 CH3
H———Cl H———Cl
Cl———H H———Cl
13.
CH2CH3 CH2CH3
(I) (II)
(A) I and II are enantiomers (B) I is 2S, 3S; while II is 2S, 3R
(C) I is 2R, 3R; While II is 2R, 3S (D) I and II are diastereomers
14. Which of the following statements are true regarding following structures :-
CH2 CHCl
(A) (B) (C) (D)
Comprehension-2
The optical isomers rotate the plane of plane-polarised light. A sp3-hybridised carbon atom attached to four
different atoms or groups is called an asymmetrical centre or chiral centre. Chiral molecules do not possess any
of the elements of symmetry. A chiral molecule cannot be superimposed on its mirror image. These stereoisomers
are called enantiomers. Molecules having a plane of symmetry or centre of symmetry are superimposable on
their mirror images and are achiral. The stereoisomers that are not mirror images of each other are called
diastereomers. A mesoisomer has a plane of symmetry and is optically inactive due to internal compensation.
25
JEE-Chemistr y
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Enthusiast\Che\Unit-06\Stereoisomerism
26
Stereoisomerism
6. How many cyclic isomers are possible for C5H10 molecular formula including stereoisomers ?
7. How many total isomers are possible for the formula C 2FClBrI.
8. Give number of chiral carbon atoms in the compound X, Y and Z. Give your answer as XYZ.
Me
Me
Me Me
(X) (Y) (Z)
9. For the given reaction how many monochloro products will be obtained (all isomers) ?
Cl / hv
¾¾¾¾
2
® products
(B) (Q) 4
27
JEE-Chemistr y
HO2C CO2H
1. The absolute configuration of is [AIEEE-2008]
HO H H OH
(1) S, S (2) R, R (3) R, S (4) S, R
3. Out of the following, the alkene that exhibits optical isomerism is :- [AIEEE-2010]
(1) 2-methyl-2-pentene (2) 3-methyl-2-pentene
(3) 4-methyl-1-pentene (4) 3-methyl-1-pentene
4. How many chiral compounds are possible on monochlorination of 2–methyl butane ? [AIEEE-2012]
(1) 6 (2) 8 (3) 2 (4) 4
5. Which of the following compounds will exhibit geometrical isomerism? [JEE MAINS - 2015]
(1) 1 - Phenyl - 2 - butene (2) 3 - Phenyl - 1 - butene
(3) 2 - Phenyl - 1 - butene (4) 1, 1 - diphenyl - 1 - propane
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Enthusiast\Che\Unit-06\Stereoisomerism
28
Stereoisomerism
2. Which branched chain isomer of the hydrocarbon with molecular mass 72 u gives only one isomer of mono
substituted alkyl halide ? [AIEEE-2012]
(1) Neohexane (2) Tertiary butyl chloride (3) Neopentane (4) Isohexane
CO2H
H OH
H Cl
CH3
is
(1) (2R, 3S) (2) (2S, 3R) (3) (2S, 3S) (4) (2R, 3R)
2. The number of chiral centres in penicillin is ______ [JEE MAINS - 2020 - ONLINE]
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Enthusiast\Che\Unit-06\Stereoisomerism
29
JEE-Chemistr y
2. The correct statement(s) about the compound given below is (are) :- [IIT-2008]
Cl H
H3C CH3
Cl H
(A) The compound is optically active (B) The compound possesses centre of symmetry
(C) The compound possesses plane of symmetry (D) The compound possesses axis of symmetry
3. The correct statement(s) about the compound H3C(HO)HC – CH = CH – CH(OH)CH3 (X) is (are) :
[IIT-2009]
(A) The total number of stereoisomers possible for X is 6
(B) The total number of diastereomers possible for X is 3
(C) If the stereochemistry about the double bond in X is trans, the number of enantiomers possible for X is
4
(D) If the stereochemistry about the double bond in X is cis, the number of enantiomers possible for X is 2
4. Which of the given statement(s) about N,O,P and Q with respect to M is (are) correct ? [IIT-2012]
HO HO Cl CH3 CH3
H H
H OH H OH HO H
Cl CH3
HO H HO
H OH H
HO H HO H
CH3 Cl CH3 Cl Cl
M N O P Q
(A) M and N are non-mirror image stereoisomers (B) M and O are identical
(C) M and P are enantiomers (D) M and Q are identical
H3C CH3
[JEE ADVANCED-2015]
H3C O
M
6. Total number of isomers, considering both structural and stereoisomers, of cyclic ethers with the molecular
formula C4H8O is ___ [JEE ADVANCED-2019]
30
Stereoisomerism
ANSWERS
EXERCISE-1
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. B C B D B B D B D D D D A D B
Que. 16 17 18 19 20
Ans. B C A C A
EXERCISE-2
l MULTIPLE CHOICE CORRECT QUESTIONS
1. (CD) 2. (ABC) 3. (ABCD) 4. (AB) 5. (CD)
6. (AC) 7. (AB) 8. (AC) 9. (AC) 10. (BC)
11. (BC) 12. (ACD) 13. (BD) 14. (BCD)
EXERCISE-3
l NUMERICAL ANSWER BASED QUESTIONS
1. (4) 2. (3) 3. (2) 4. (4) 5. (6)
6. (7) 7. (6) 8. (021) 9. (6)
EXERCISE-4(A)
1. (2) 2. (1) 3. (4) 4. (4) 5. (1)
EXERCISE-4(B)
l SECTION - 1 : SINGLE CORRECT CHOICE QUESTIONS
1. (1) 2. (3) 3. (3) 4. (2)
EXERCISE-5
1. (BCD) 2. (AD) 3. (AD) 4. (ABC) 5. (2)
6. (10)
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Enthusiast\Che\Unit-06\Stereoisomerism
31
Stereoisomerism
Me Me
(A) (B) (C) Cl (D)
Me
C l Br H Cl H Cl H H
| | | | | | | |
(A) H - C - C - H (B) H - C - C - C l (C) H - C - C - H (D) H - C - C - CH 3
| | | | | | | |
H H H H H H Br OH
7. Meso-tartaric acid and d-tartaric acid are
(A) positional isomers (B) enantiomers (C) diastereomers (D) racemic mixture
CH3
HO H
8. The full name of the compound is
H Cl
C2H5
251
JEE-Chemistr y
10. How many stereoisomers of the following molecule are possible?
HOOC.CH=C=CH.COOH
(A) two optical isomers (B) two geometrical isomers
(C) two optical and two geometrical isomers (D) None
11. The interchange of two groups (Br and CH3) at the chiral centre of the projection formula (A) yields the formula
(B), while the interchange of another set of two groups (C 2H5 and Cl) of (A) yields the projection formula (C)-
CH3 Br CH3
Cl Br Cl CH3 C2H5 Br
C2H5 C2H5 Cl
(A) (B) (C)
Which of the following statements is not correct about the structures (A), (B) and (C) -
(A) B and C are identical (B) A and C are enantiomers
(C) B and C are enantiomers (D) A and B are enantiomers
Br COOH COOH Br
HOOC Br Br COOH
(A) Positional (B) Chain (C) Geometrical (D) Functional
COOH
16. Ordinary light can be converted into plane polarized light with the help of a :
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Nurture\Che\Unit-06\Stereoisomerism
(A) Nickel prism (B) Nicol prism (C) Diffraction grating (D) Quartz cell
252
Stereoisomerism
18. Isomers which can be interconverted through rotation around of single bond are -
(A) Conformers (B) Diastereomers (C) Enantiomers (D) Positional isomers
20. The optically active tartaric acid is named as D–(+) tartaric acid because it has a positive :
(A) optical rotation and is derived from D–glucose
(B) pH in an organic solvent
(C) optical rotation and is derived from D–(+)– glyceraldehyde
(D) optical rotation only when substituted by deuterium
23. Hydrogen of the following compound in the presence of poisoned palladium catalyst gives :
Me H Me
H
Me H
(A) optically active compound (B) an optically inactive compound
(C) a racemic mixture (D) a diastereomeric mixture
HOOC H 3C CH 3
Ph
CH3
Ph
COOH
(C) H 3C CH–CH3 (D)
Ph
COOH
253
JEE-Chemistr y
28. Which of the following are optically active :-
C=C=C
F F Cl
H
H —CO2H
(C) H N (D)
2 NH2
F F
CH3 CH3
CH3 Cl
H OH H Cl
(A) H C 2H 5 (B) HO H (C) (D) H Cl
Cl
CH3 CH3
254
Stereoisomerism
32. Which of the following allene compounds is optically active ?
H 3C CH3 H CH3
C C C C C C C
(A) (B)
H H H 3C H
H 3C CH3 H CH3
C C C C C C C
(C) (D)
H 3C H H CH3
NC
CN CN
(B) & (Q) Diastereomers
CN
CH3 CH3
H OH HO H
(C) & (R) Geometrical isomers
H OH HO H
CH3 CH 3
Me
Me
(T) Stereoisomers
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Nurture\Che\Unit-06\Stereoisomerism
255
JEE-Chemistr y
34. Match the following column :
Column-I Column-II
CH3 H
H CH2OH H3C CH2NH2
(A) and (P) Structural
NH2 OH
CH3 Cl
H Cl H CH3
(B) and (Q) Identical
Et Et
CH3 H
H OH H3C Et
(C) and (R) Enantiomers
Et OH
H3C2 H3C2
(D) and (S) Diastereomers
HO H H OH
36. The number of isomers of dibromoderivative of an alkene (molar mass 186 g mol –1) is
38. How many optically active stereoisomers are possible for butane –2,3–diol :
39. The number of possible enantiomeric pairs that can be produced during monochlorination of 2–methyl butane
is :
40. The number of isomers for the compound with molecular formula C2BrCIFI is :
42. Why does cyclopentene not exhibit geometric isomerism though it has a double bond.
43. Why does 2-butene exhibit cis-trans isomerism but 2-yne does not ?
45. How many pseudo chiral carbon are present in butane–1,2,3–triol and cyclohexane–1,2,3–triol ?
46. (+) 2-butanol has specific rotation of + 13.9° when measured in pure form. A sample of 2-butanol was found
to have an optical rotation of –3°. What is the stereomeric composition of this mixture ?
47. N-methylethenamine as such does not show any stereoisomerism but one of its resonance form exhibit
stereoisomerism. Explain.
256
Stereoisomerism
48. Assign Cahn-ingold prelog priorites to the following sets of substituents :
(i) —H, —Br, —CH2CH3, —CH2CH2OH (ii) —COOH, —COOCH3, —CH2OH, —OH
(iii) —CN, —CH2NH2, —CH2NHCH3, —NH2 (iv) —Br, —CH2Br, —Cl, —CH2Cl
50. Discuss the optical activity of tertiary amines of the type R1R2R3N :
H C
Cl C2H5
CH3 CH3
HO———H H———OH
(i) (ii)
H———OH H———OH
CH3 CH3
(F)
55. Statement-I : All double bond containing compounds show geometrical isomerism.
Because
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Nurture\Che\Unit-06\Stereoisomerism
58. Statement-I : Molecules that are not superimposable on their mirror images are chiral
Because
Statement-II : All chiral molecules have chiral centres.
257
JEE-Chemistr y
ANSWERS
l SINGLE CHOICE CORRECT QUESTIONS
1. (B) 2. (C) 3. (D) 4. (A) 5. (C)
6. (D) 7. (C) 8. (A) 9. (A) 10. (A)
11. (C) 12. (B) 13. (A) 14. (B) 15. (C)
16. (B) 17. (B) 18. (A) 19. (C) 20. (C)
21. (A) 22. (D) 23. (B)
l SUBJECTIVE QUESTIONS
41. Only CHBr = CHCl can exist as geometric isomers :
Br Cl Br H
C C and C C
H H H Cl
In CH2Cl— CH2Cl and CH2Cl—CH2Br, the carbon atoms are connected by a single bond about which the
groups can rotate relatively freely. Thus any conformation of the halogen atoms may be converted into any other
simply by rotation about the single bond. In CH2Cl2, the configuration of the molecule is tetrahedral and all
interchanges of atoms yield exactly equivalent configurations.
H H
42. This is cis form. Two H atoms on the same side. To get trans, ring must be twisted.
Double bond becomes severely twisted-destabilized. Effective overlap of P orbitals is missing, so does not exist.
43. The Pz orbitals forming p-bonds and the empty Pz orbital of the carbon with +ve charge are parallel. So the
electrons may be delocalized. The +ve charge is effectively spread out over two carbons; delocalized.
p-orbital
H empty orbital
C C
C+ H
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Nurture\Che\Unit-06\Stereoisomerism
H
H
+ +
CH2=CH— C H 2 ¬¾® C H 2 —CH= CH
In n-propyl cation, + I effect of R increases the stability.
In allyl + M effect increases the stability. But + M effect in allyl cation is more effective. So allyl > propyl.
A group with + M effect stabilizes cation; destabilizes anion.
258
Stereoisomerism
45. Number of pseudo chiral carbon in butane–1,2,3–triol is 0.
Number of pseudo chiral carbon in cyclohexane–1,2,3–triol is 1.
5=2 2=5
(ii) It has no stereogenic centre.
H OH
Br
(iii) CH 3—C —CH2—CH 2— CH 3 bromine bearing carbon is stereogenic centre.
H Br
(iv) CH3—CH2—CH—CH2—CH3 It has no stereogenic centre.
••
2
sp -hybridized 2
2
R1 sp
R1 sp R1
R2 N N R2
••
N
•
•
••
R3 R3
R2 R3
Planar transition state
Enantiomers
Tertiary amine N-oxide has four group hence nitrogen inversion is not possible, thus tertiary amine -N-oxide can
be resolved.
259
JEE-Chemistr y
CH3
51. Cl C
H C2H5
52. , ,
CH3 CH3
HO—R ——H H——
S
—OH
53. (i) H——R—OH (ii) H——
R
—OH
CH3 CH3
l ASSERTION–REASON QUESTIONS
55. (D) 56. (D) 57. (A) 58. (C)
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Nurture\Che\Unit-06\Stereoisomerism
260