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Optical Isomerism
Part-01
Optical Isomerism
Two or more than two compounds have same molecular formula, same structural formula but different
behaviour towards PPL (plane polarised light).
+ (+) or d [Optically active]
– (-) or [Optically active]
Polarimeter
Nicol Plane
tube [Optically inactive]
Prism polarised =
Source light
of light (PPL) Angle of rotation
1. Optical activity : Tendancy to rotate plane of PPL in a particular direction. If a compound rotates plane of PPL
in clockwise direction then it will be dextrorotatory or d or (+) and if a compound rotates plane of PPL in
anticlockwise direction then it will be laevorotatory or or (–).
• Clockwise rotation = dextrorotatory = 'd' or (+)
• Anticlockwise rotation = laevorotatory = 'l' or (-)
• Angle of rotation () depends on –
(a) Concentration of solution (in gm/ml) (b) Length of polarimeter tube (in dm)
(c) Wavelength of light used (in Å) (d) Temperature (°C), etc.
2. Chiral Centre: sp3 hybridised atom [C,N,O,P,S] having four different valencies.
I
C* centre
Cl Br
F
3. Chiral carbon / asymmetric carbon: sp3 carbon atom attached with four different atoms or groups is known
as chiral or asymmetric carbon.
CH3
Me Cl
Ex. (1) (2)
H3C—CH—CH—CH2—CH3
* *
CH3
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Optical Isomerism
Part-02
Representations of tetrahedral carbon
1. Wedge-dash projection
2. Fischer projection
3. Sawhorse projection
4. Newman projection
Wedge-Dash Formula (3D)
Out of 4 units, 2 units including tetrahedral carbon is maintained in the plane and remaining two units below
and above the plane.
Example: CH3—CH(OH)—COOH
CH3
C
H
HO2C
OH
Fischer Projection (2D)
Groups at horizontal line towards observer.
Groups at vertical line away from observer.
COOH COOH
HO H HO H
CH3 CH3
Saw horse projection
H H H
H H
C C
C H C
H
H
H H H H
Eclipsed Staggered
Saw horse projection
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Optical Isomerism Part-02
Newman projection
H H
H H H
60º
H H
H H
H H H
Eclipsed Staggered
Newman projection
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Optical Isomerism
Part-03
Condition for Optical activity:
Presence of chirality (unsymmetry) is essential condition for optical activity that is the molecule must be chiral
/ It should not have any symmetry element.
Chiral Molecule:
Optically active molecule. (Non-superimposable mirror images)
Symmetry Elements
Presence or absence of chiral carbon not a necessary condition for optical activity.
The necessary condition for optical activity is absence of elements of symmetry.
The elements of symmetry are
(a) Plane of symmetry (POS)
(b) Centre of symmetry (COS)
(a) Plane of symmetry:
A plane which divides molecule in two equal halves is known as plane of symmetry.
COOH
H
H OH
C Cl POS
H OH
F
Br
No POS COOH
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Optical Isomerism
Part-04
(b) Centre of symmetry
It is an imaginary point in the centre of a molecule such that if a line is drawn from any group of the molecule
to this point and then extended to an equal distance beyond the point, it meets the mirror images of the original
group.
Cl H Cl H
(1) (2)
H Cl H Cl
NOTE: How to find optically active compound?
Chiral Carbon
CC = 0 CC = 1 CC > 1
Generally optically inactive Generally optically active May or may not be
Except:- Substituted allene, Except:- Umbrella optically active
biphenyl, spiro compounds flipping/inversion (check POS/COS)
(optically inactive)
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Optical Isomerism
Part-05
Types of Configuration
1. R-S configuration (Absolute configuration)
2. D-L configuration (Relative configuration)
3. Erythro and Threo
(1) R-S configuration / Absolute configuration
R = Rectus (clockwise rotation)
S = Sinister (anticlockwise rotation)
(a) R-S configuration in Fischer Projection.
Rule I — Priority between the different groups attached on chiral carbon is determined by CIP rules.
Rule II — When 4th priority group is present at vertical line of Fischer projection, then we move
1→ 2 → 3
If clockwise ( ) R
Anti-clockwise ( ) S
4
or
Rule III — When 4th priority group is present at horizontal line of Fischer projection.
Now,
1→2→3
If clockwise ( ) S
Anti-clockwise ( ) R
4 or 4
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Optical Isomerism
Part-06
(1) R-S configuration / Absolute configuration
(b) R-S configuration in wedge dash
Rule I – When 4th priority group is on dash line.
1→2→3
C If clockwise ( ) R
4 anti-clockwise ( ) S
Rule II – If 4th priority is not on dash position then by even interchange using 4th priority to dash position and
then find R-S configuration.
I1
Br 2
even
C 4
interchange C 3
Br F
2 I Cl
1
Cl
3 F4
R-configuration R-configuration
Rule of odd/even interchange
• When any two groups around a chiral carbon are exchanged odd number of times, then configuration of
molecule get reversed.
F Cl
S Exchanges R
I Cl I F
F Cl
Br Br
• When any two groups around a chiral carbon are exchanged even number of times, then configuration of
molecule remains same.
F Cl
S Exchanges S
I Cl Br F
F Cl
Br Br l I
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Optical Isomerism Part-06
• When complete molecules rotate 180° [in the plane] then configuration remain same.
COOCH3 COOH
H OH HO H
180º
H OH HO H
COOH COOCH3
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Optical Isomerism
Part-07
Types of Configuration
2. D-L configuration (Relative configuration):
• D or L is applied for amino acids and carbohydrates.
• The basic unit for D-L configuration is glyceraldehyde and -Amino acid.
OHC—CH—CH2OH R—CH—COOH
OH NH2
Glyceraldehyde -Amino acid
Rules for D-L configuration :-
(a) Most oxidised group should be present at the top of vertical line in Fischer projection.
(b) –CH2OH or -R should be present at the bottom of vertical line in Fischer projection.
(c) At last chiral centre, the relative position of –OH in carbohydrates and –NH2 in amino acid defines D-L
i.e. right side = D and left side = L.
Example:
* *
OHC—CH—CH2OH R—CH—COOH
OH NH2
Glyceraldehyde -Amino acid
RHS
D-form
-OH group
At last chiral
or
-NH2 group centre
LHS
L-form
CHO CHO
H OH HO H
(1)
CH2OH CH2OH
D-Glyceraldehyde L-Glyceraldehyde
COOH COOH
H NH2 H2N H
(2)
R R
D-Amino acid L-Amino acid
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Optical Isomerism Part-07
3. Erythro and Threo
If same groups comes on the same side on two horizontal lines, then it is called erythro.
If same groups comes on the opposite side on two horizontal lines, then it is called threo.
R R
H OH HO H
H OH H OH
R’ R’
Erythro Threo
Note: Erythro and threo are pair of diastereomers.
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Optical Isomerism
Part-08
Enantiomers
(i) Some stereoisomers are mirror images of each other but do not superimpose on each other.
Non-superimposable mirror images are called as enantiomers.
COOH COOH
H OH HO H
CH3 CH3
Object (I) mirror Object (II)
I and II are non superimposable mirror images, so I and II are enantiomers.
(ii) Enantiomers are optically active substances. They rotate the plane polarized light in opposite directions but to
the equal extent.
Diastereomers
(i) Stereoisomers which are not mirror image of one another.
(ii) They have different physical and chemical properties and hence can be separated by fractional distillation, etc.
(iii) May or may not be optically active.
(iv) Generally cis-trans isomers are also diastereomers of each other.
1. But-2-ene
H3C CH3 H3C H
C=C C=C
H H H CH3
cis-But-2-ene trans-But-2-ene
Illustration 1.
COOH COOH
H OH H OH
(1) (2)
H OH HO H
COOH COOH
Solution: (1) and (2) are diastereomers.
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Optical Isomerism Part-08
Illustration 2.
CH3 CH3 CH3 CH3
H Cl Cl H H Cl Cl H
H Cl Cl H Cl H H Cl
CH2CH3 CH2CH3 CH2CH3 CH2CH3
(I) (II) (III) (IV)
Solution: I, II = Enantiomers, III, IV = Enantiomers
I, III = Diastereomers, II, IV = Diastereomers
II, III = Diastereomers, I, IV = Diastereomers
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Optical Isomerism
Part-09
Meso compounds
Compounds having atleast two chiral carbons and element of symmetry is called meso compounds. It is optically
inactive due to internal compensation.
COOH
H OH Plane of symmetry
H OH (achiral molecule, optically inactive)
COOH
Illustration 1.
COOH COOH
H OH HO H
H OH HO H
COOH COOH
(I) (II)
Solution: I and II are identical (mirror image of meso compound is identical)
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Optical Isomerism
Part-10
Racemic mixture
Equimolar mixture of d and enantiomers is called as racemic mixture. (d or (±)).
d+ Net rotation zero
equimolar [External compensation]
"Racemic mixture is optically inactive due to external compensation.
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Optical Isomerism
Part-11
Special cases:
Presence or absence of chiral center is not a necessary condition for optical activity. The necessary condition is
absence of element of symmetry.
1. Substituted Allenes:
Substituted allenes (cumulenes)
CH3 1 2 CH3 CH3 1 2 3 CH3
C=C=C C=C=C=C
H H H H
Even number of double bonds Odd number of double bonds
Terminal groups not present in same plane. Terminal groups present in same plane.
CH3 CH3 CH3 CH3
C=C=C C=C=C=C
H H H H
• Substituted allenes do not have chiral carbons but molecule is chiral, so show optical isomerism.
X X
XYC=C=CXY C=C=C
Y Y
Allene
(No chiral carbon but molecule is chiral)
Only those substituted allenes will be optically active in which "each sp2 carbon have different atoms or group".
2. Biphenyl system:
Free rotation possible (optically inactive)
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Optical Isomerism Part-11
Ortho ortho' substituted Biphenyl:
(i) If all four ortho positions are occupied by bulky groups, then to minimise repulsion rings become perpendicular
to each other.
a b
a' b
Bulky groups: –R, –Cl, –Br, –I, –CHO, –COOH, –COOR, –CONH2, –SO3H, -NR2 etc.
Condition for GI/Ol
• No GI in Biphenyl
• If a = a' or b = b’, No optical isomerism
a a' and b b', optical isomerism is possible.
(ii) They do not have any chiral carbon but they are optically active.
NO2 HOOC
COOH O2N
Horizontal Vertical
Plane Plane
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Optical Isomerism
Part-12
Number of stereoisomers:
Calculation of Optical Isomers:
No. of optically No. of meso Total no. of optical
S.N. Nature of compounds
active isomers (a) compounds (m) isomers (a + m)
Compounds having
2n
more than one chiral
1 (n = No. of chiral 0 (2n+0)
centre with dissimilar
centre)
ends.
Compounds having
even number of chiral n n
2 2n-1 −1 −1
centres with similar 22 2n−1 + 2 2
ends
Compounds having odd
number of chiral n−1 n−1
3 2n−1 − 2 2 22 2n-1
centres with similar
ends
Total number of stereo isomer (TSI):
(A) If molecule is unsymmetrical
T.S.I. = 2n
where n = No. of G.I. sites + O.I. sites
(B) If molecule is symmetrical
n = odd
T.S.I. = 2n-1+2p-1
n = even
(C) In case of ring system when G.I. center and O.I. center same then
Stereoisomers = Optical isomers
Ex. S.I. = O.I.
Me Me
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Optical Isomerism Part-12
Illustration 1. CH3—CH—CH—CH—CH3
OH Cl Br
Solution:
no. of optically active isomers = 8
no. of meso = 0
total no. of optical isomers = 8
no. of racemic mixtures =4
Illustration 2. CH3—CH—CH—CH3
OH OH
Solution:
no. of optically active isomers = 2
no. of meso = 1
total no. of optical isomers = 3
no. of racemic mixtures =1
Amine Flipping
N and N
Me H Et R1 R2 R3
It has one chiral centre but even then it is optically inactive. Why?
In all open chain amines, in which lone pair of nitrogen present in sp3 orbital is amine inversion takes place.
Me Me
H N N H
Et Et
• Keq = 1
• Equal stability
• Both are enantiomers
• Behaves as 50% 'd' and 50% '' form (Racemic mixture) so optically inactive
• cannot be separated (non-resolvable)
• Barrier to inversion is low enough (about 6 Kcal/mol) for inversion to occur at an observable rate at room temp.
• Conditions → 2nd period element and 1 lone pair
• Chiral nitrogen containing tertiary amine does not show optical isomerism
Reason :- Rapid umbrella inversion.
R3 R2 R 1
Room temperature
N N
R1 R2 R3
(I) (II)
Energy required for this interconversion is available at room temperature. So I and II are interconvertible.
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