CYI101

Common CHEMISTRY(Organic)

24th Dec 2020/Sec G & H

CYI 101 CHEMISTRY-THEORY (Common) (3-0-0)

UNIT –II

Aromaticity [2L]
Aromatic, non-aromatic and anti-aromatic compounds

Stereochemistry [4L]
Concept of chirality, Axial chirality, enantiomers and diastereomers, specific rotation,
optical purity, Racemic modification and resolution, R/S, D/L and E/Z nomenclature

Pericyclic reactions [4L]

Definitions, Classifications, photochemical [2+2] and thermal [4+2] cycloaddition,
Sigmatropic rearrangement

Macromolecules [4L]
Introduction to peptides and proteins. Basics of Polymer Chemistry, Polymerization
techniques, natural and synthetic polymer
Recommended Books:
1. Organic Chemistry, J. CLayden, N. Greeves, S. Warren, P. Wother, Oxford
University Press, 2000.
2. Principles of polymerization, George G. Odian, 4th Edn, John Wiley & Sons, Inc.,
Publication, 2004.
3. Advanced Organic Chemsitry, Smith & March, 5th Edn, Wiley & Sons
 Physical Properties of Stereoisomers—Optical Activity
• The chemical and physical properties of two enantiomers are
identical except in their interaction with chiral substances. They
have identical physical properties, except for how they interact
with plane-polarized light.
• Plane-polarized (polarized) light is light that has an electric
vector that oscillates in a single plane. Plane-polarized light
arises from passing ordinary light through a polarizer.
• A polarimeter is an instrument that allows polarized light to
travel through a sample tube containing an organic compound.
It permits the measurement of the degree to which an organic
compound rotates plane-polarized light.
• With achiral compounds, the light that exits the sample tube
remains unchanged. A compound that does not change the
plane of polarized light is said to be optically inactive.
• With chiral compounds, the plane of the polarized light is rotated
through an angle . The angle  is measured in degrees (°), and is
called the observed rotation. A compound that rotates polarized
light is said to be optically active.
• The rotation of polarized light can be clockwise or
anticlockwise.
• If the rotation is clockwise (to the right of the noon position),
the compound is called dextrorotatory. The rotation is labeled d
or (+).
• If the rotation is counterclockwise, (to the left of noon), the
compound is called levorotatory. The rotation is labeled l or (-).
• Two enantiomers rotate plane-polarized light to an equal extent
but in opposite directions. Thus, if enantiomer A rotates
polarized light +5°, the same concentration of enantiomer B
rotates it –5°.
• No relationship exists between R and S prefixes and the (+) and
(-) designations that indicate optical rotation.
Specific Rotation []D : a standardized value for the optical rotation

 = observed rotation in degrees

[]obs l = path length in dm
[]T = c = concentration of sample in g/mL
lxc
T = temperature in °C
 = wavelength of light, usually D for the
D-line of a sodium lamp (589 nm)

The specific rotation is a physical constant of a chiral molecule

The []D may also depend upon solvent, therefore the solvent is
usually specified.
H NH2

for alanine: HO2C

[]20
D = +14.5° (c 10, 6N HCl)
• Enantiomeric excess (optical purity) is a measurement of how
much one enantiomer is present in excess of the racemic
mixture. It is denoted by the symbol ee.

ee = % of one enantiomer - % of the other enantiomer.

• Consider the following example—If a mixture contains 75% of

one enantiomer and 25% of the other, the enantiomeric excess
is 75% - 25% = 50%. Thus, there is a 50% excess of one
enantiomer over the racemic mixture.
• The enantiomeric excess can also be calculated if the specific
rotation [] of a mixture and the specific rotation [] of a pure
enantiomer are known.
ee = ([] mixture/[] pure enantiomer) x 100.
What is the ee of the following racemic mixture?
95% A and 5% B

ee = % of A - % of B
= 95 – 5 = 90 ee

Given the ee value, what percent is there of each isomer, 60%

ee

60% excess A, then 40% racemic mixture( so 20% A and

20% B)

So, 60% + 20% = 80% A and leaves 20% B

A pure compound has a specific rotation of +24, a solution of
this compound has a rotation of +10, what is the ee?

ee = [] of mixture / [] of pure x 100

=+10/+24 x 100 = 42%
 Racemic Mixtures
H H
H
HBr H3C
H3C
CH3 CH3 But do we get (R) or (S)?
addition reaction Br
H H

(E)-2-butene 2-bromobutane
achiral chiral

We get both!

CH3 CH3
H3C H3C
H Br Br H

50% (S)-2-bromobutane 50% (R)-2-bromobutane

A 50:50 mixture of 2 enantiomers is called a racemic mixture or a racemate.

 Resolution of Enantiomers
mixture of 2
diastereomers

react or somehow associate with: (R)-compound X (R)-compound Y

(R)-compound X

(S)-compound X (R)-compound Y (S)-compound X (R)-compound Y

Separate by some technique (chromatography,

Single crystallization, distillation, etc.)
racemic mixture enantiomer
of enantiomers

(S)-compound X (R)-compound Y (R)-compound X (R)-compound Y

single single
diastereomer diastereomer
somehow remove compound Y

(S)-compound X (R)-compound X

single single
enantiomer enantiomer
 Resolution of Enantiomers
Reaction Using Diastereomers to Separate Enantiomers
this nitrogen lone
pair is basic
Me
(R)--methylbenzylamine

this hydrogen H2N O Me

O is acidic
Me
(S)-2-chloroproprionic acid Me O H3N
OH
Cl
Cl
The R,S-diastereomer of the salt
this nitrogen lone
pair is basic
Me
(R)--methylbenzylamine
this hydrogen O Me
is acidic H2N
O Me
O H3N
(R)-2-chloroproprionic acid Me
OH Cl

Cl
The R,R-diastereomer of the salt
separate

O O Me
O Me
acidify
Me Me
Me
OH O H3N
O H3N
Cl Cl
Cl
(R)-2-chloroproprionic acid
O
acidify
Me
OH

Cl (S)-2-chloroproprionic acid
Resolution of (+/-) Alcohol

(-) Brucine
Resolution of (+/-) Amino Acid
Enantiomer

Diastereomer
• Compound C contains a plane of symmetry, and is achiral.
• Meso compounds generally contain a plane of symmetry so that
they possess two identical halves.

Meso-Tataric acid

• Because one stereoisomer of 2,3-dibromobutane is

superimposable on its mirror image, there are only three
stereoisomers, not four.
Active/Inactive Isomer

Case I

Case II

Case III
Case IV

General formulae
If 'n' is even (here n is the number of chiral centres):

Number of Optically active isomers 2n-1

Number of Meso Compounds 2n-2/2

If 'n' is odd (here n is the number of chiral centres):

Number of Optically active isomers 2n-1-2n-1/2

Number of Meso Compounds 2n-1/2
Case IV

Active Meso