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Lecture -11

Stereochemistry of carbon compounds

Introduction:

Stereochemistry, a sub discipline of chemistry, involves the study of the relative spatial arrangement
of atoms that form the structure of molecules and their manipulation. An important branch of
stereochemistry is the study of chiral molecules.

Stereochemistry is also known as 3D chemistry because the prefix "stereo-" means "three-
dimensionality".

The study of stereochemistry focuses on stereoisomers and spans the entire spectrum of organic,
inorganic, biological, physical and chemical properties of molecules.

Isomerism:
The concept of isomerism is an important feature of the study of organic compounds which relates to
the existence of different compounds which have the same molecular formula but different properties.
Such compounds are called isomers. The difference in properties of isomers is due to the difference in
the relative arrangements of atoms in their molecules.

Examples:
1. Pentane (C5H12) has three structural isomers.

2. Isomers of 2-butene

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Classification of isomers:

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Lecture -12

Constitutional Isomers:
Structural isomers are compounds that have same molecular formula but different structural formulas.

- Types of Structural isomers:

(i) Chain isomerism (ii) Position isomerism (iii) Functional isomerism

I. Chain isomerism: It has the same molecular formula but differ in the order in which the carbon
atoms are bonded to each other.

II. Position isomerism: It has the same molecular formula but differ in the position of a functional
group on the carbon chain

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III. Functional isomerism: It has the same molecular formula but different functional groups.
Alcohols - Ethers
Carboxylic acid - Esters
Cyanides - Iso cyanides
10 Amines - 20 Amines

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Lecture -13

Stereo isomers: Isomers with same bond connectivity

Configurational isomers: Two types-

1. If the isomerism is not at double bond –Optical isomers
2. If the isomerism is at double bond - Geometrical isomers

1. Optical isomers:
Isomers resembles one another in chemical reactions and most of physical properties but differ
in their effect on polarized light

Enantiomers:

An enantiomer is one of the two stereoisomers that are mirror images of each other that are non-super
imposable and which rotate the plane polarized light equally but in opposite directions. The
phenomenon of mirror image isomerism is called enantiomerism

The non-super imposability of mirror images invariably arises due to chiral nature of the molecules. A
molecule is termed as chiral if it has no plane or center of symmetry and is therefore, non-super
imposable on its mirror image. Therefore, chirality is the fundamental and only condition of
enantiomerism.

Characteristics:

 They are stable,isolobal compounds that differ from one another in 3dimensional
arrangements of atom or groups
 They have identical physical properties such as melting point, boiling point, densities, solubility,
and refractive index.
 They have identical chemical properties except in reactions with other optically active
compounds
 They have different biological properties.
 Enantiomers will rotate the plane polarized light equally but in opposite directions, the one
which rotates plane polarized light towards right is called as dextro rotatory (+) and which
rotates towards left is called as leavo rotatory (-).
 A mixture of equal amounts of enantiomers is called as racemic mixture
 Enantiomers can be separated by mechanical separation, bio chemical separation etc.

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Examples:

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Diastereomers:
Diastereomers are a type of a stereoisomer. Diastereomerism occurs when two or more
stereoisomers of a compound have different configurations at one or more (but not all) of the
equivalent (related) stereo centers and are not mirror images of each other.

When two diastereomers differ from each other at only one stereo center they are epimers.

Characteristics:

 They show different chemical properties.

 They have different physical properties such as melting point, boiling point, density, solubility,
refractive indices.
 On account of different physical properties, they can be rather easily separated through
fractional crystallization, fractional distillation, chromatography
 Diastereomers are optically inactive

Examples:
The following isomer combinations are diastereomers
I. Cis and Trans
II. Syn and Anti
III. E and Z
IV. Erythrose and Threose
V. Meso and D
VI. Meso and L
VII. Exo and Endo
VIII. Epimers

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I and II – Enantiomers
III and IV – Enantiomers
I and III – Diastereomers
II and III – Diastereomers
I and IV – Diastereomers
II and IV – Diastereomers

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I and II – Enantiomers
I and III – Diastereomers
II and III – Diastereomers

Differences between Enantiomers and Diastereomers

D

Enantiomers Diastereomers
Enantiomer is one of two stereoisomers that are Diastereomers are non-superimposable and
non-superimposable complete mirror images of non-mirror images of each other.
each other.
Molecules must contain at least one chiral Molecules must contain more than one chiral
centers. center.
Enantiomers have identical chemical and Diastereomers can have different physical
physical properties properties and different reactivity.
Enantiomers will rotate plane polarized light by Diastereomers may be optically active or
equal amounts but in opposite directions. inactive
A mixture of equal parts of an optically active Racemic mixture is not possible
isomer and its enantiomer is termed Racemic
and has a net rotation of plane polarized light of
zero.
They always have different R,S-configuration They have the same R,S-configuration at least on
one stereocenter

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Lecture -14

Optical activity: The phenomenon by virtue of which certain substances exhibit remarkable ability
to rotate plane polarized light is known as optical activity and the substances are known as optically
active.
 Chirality is the requirement of optical activity

Chiral:
Molecules that form non superimposable mirror images, and thus exist as enantiomer, are said to be
chiral

 The most common cause of chirality in an organic molecule is a carbon atom with four
different atoms or groups bonded to it. This carbon atom is called a stereogenic, chiral,
or asymmetric center.

Achiral:

Molecules that form superimposable mirror images are said to be achiral.

 A carbon atom which is not having four different groups.

 An object or molecule with internal plane of symmetry is achiral
 An object or compound which has no right hand left hand phenomenon is called achiral.

Example: Isomers of Tartaric acid:

L-tartaric acid D-tartaric acid

 D and L forms of Tartaric acid are chiral with no plane of symmetry,

Non-superimposable mirror images and optically active

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Meso-tartaric acid

 Meso-tartaric acid is achiral due to plane of symmetry, forms superimposable mirror

image and optically inactive

Optical activity:
Optical activity is the phenomenon of rotating plane polarized light.
The instrument with which optically active compounds are studied is a polarimeter, shown in the
figure below

 Ordinary light consists of waves vibrating in all planes perpendicular to line of propagation.
When such light is passed through Nicol prism, its vibrations in all planes cut off except in
one plane which is called as plane polarized light

 The molecule will interact with plane polarized light and rotate either towards right side or
left side.

 Those that rotate the plane to the right (clockwise) are said to be dextrorotatory
(d or +ve) (dexter-right).

e.g., D-Glyceraldehyde [α]D25 = +8.70

D-Tartaric acid [α]D25 = +12.70

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 Those that rotate the plane to the left (counter clock wise) are called levorotatory
(l or -ve) (laevus-left).

e.g., L-Glyceraldehyde [α]D25 = -8.70

L-Tartaric acid [α]D25 = +12.70

Specific rotation: The rotation in degrees observed when a plane polarized light is passed through 1dm
of solution having concentration of 1g/ml at specified temperature and wave length.

[α] = Specific rotation

α = Observed rotation
l = Length of polarimeter tube (dm)
C = Concentration of solution in g/ml
t = Temperature in 0C (250C)
D = D-lines of sodium having 589.3nm

Example problem

1. An optically active compound has specific rotation +500, length of tube is 4dm and its
concentration is 4g/100ml.caluclate optical rotation.

[α] = +500
Concentration = 4/100=0.04g/ml
Length of tube = 4dm
α =?

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Lecture -15

Absolute configuration: (R, S nomenclature)

 R, S nomenclature is applicable for all stereo chemical formulae and all chiral molecules.
 To assign Configurational symbols R, S to an organic compound, sequence rules are proposed
i.e., Cahn Ingold Prelog Rules.
 If the sequence is clockwise the configuration is “R”-(Rectus = right) and if the
sequence is anti-clockwise the configuration is “S”-(Synistrous = left)

Cahn Ingold Prelog Rules:

1. Atomic number rule: Greater atomic number results is higher priority

I> Br>Cl>F

2. Atomic weight rule: In presence of two isotopes of same element, the heavier isotope will have
higher priority
D>H
C14 > C12

3. If the two atoms attached to carbon are same, priority is determined by comparing next atom
in the group

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4. If chiral carbon is attached to doubly or triply bonded atom the atom is considered equivalent
to two or three singly bonded atoms in determining priority. (Triple bond > double bond >
single bond)

5. In the Fischer projection formula, the lowest priority group should be placed at the bottom
position (vertically downwards), if lowest priority group is present on horizontal line, the
configuration becomes opposite.

(Anti-clockwise but R)

Examples:

Alanine L-Glyceraldehyde

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(2R, 3S, 3R) (2R, 3S, 4R, 5R)

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

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Examples of Wedge projection:

 Configuration is opposite,
If highest priority group on dotted line (or)
If least priority group on thick line

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Lecture -16

Geometrical isomerism:

➢ Isomers which possess the same molecular formula but differ in arrangement of atoms or
groups in space due to restricted rotation about a bond are known as geometrical isomers and
phenomenon is known as geometrical isomerism.
➢ The restricted rotation is due to multiple bond(or by ring system)
➢ Molecule must contain different atoms or groups attached to doubly bonded atom
➢ Geometrical isomers are classified in to two type:
I. Cis-Trans isomers
II. E-Z isomers

Cis –Trans isomers:

Cis-Ttrans are stereoisomers that are a pair of molecules which have same molecular formula but
different orientation of atoms or groups about a double bond.

To designate cis-trans isomers there must be

➢ Restricted rotation in a molecule due to double bond or ring system

➢ Non identical atoms or groups on each doubly bonded carbon atom
➢ Molecules with identical atoms attached to doubly bonded carbon will not exhibit isomerism
➢ Isomers with similar groups on same side of doubly bonded atom are known as Cis and those
with similar groups on opposite side are known as Trans isomers
➢ Cis-same side Trans-opposite side

Examples:

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E-Z Nomenclature:

The terms Cis and Trans are used to designate the stereochemistry of disubstituted alkenes only. If,
however, the alkene is tri or tetra substituted these terms cannot be applied at all. To designate tri or
tetra substituted alkenes E-Z system of nomenclature is used.

➢ In the E-Z system two groups attached to each carbon of double bond arranged in order of
priority
➢ If similar priority order groups are located on the same side of double bond the alkene is
designated as Z isomer(German word Zusammen = together)
➢ If similar priority order groups are located on the opposite side of double bond the alkene is
designated as E isomer(German word Entegeggen = opposite)
➢ Cahn Ingold Prelog Convention rules are used to designate priority of groups attached to alkene.

Cahn Ingold Prelog Rules:

1. Atomic number rule: Greater atomic number results is higher priority

I> Br>Cl>F
2. Atomic weight rule: In presence of two isotopes of same element, the heavier isotope will have
higher priority
T>D>H ; H3C14 > H3C12
3. If the two atoms attached to carbon are same, priority is determined by comparing next atom
in the group
4. If chiral carbon is attached to doubly or triply bonded atom the atom is considered equivalent
to two or three singly bonded atoms in determining priority.
(Triple bond > double bond > single bond)

5. Bond gets priority over lone pair electrons

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Examples:

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