Isomerism PP 4

Stereochemistry
Stereo talks about arrangement in space, therefore Stereochemistry means the study
of spatial arrangement of atoms in a molecule. The spatial arrangement of atoms
affects the structural properties of the molecule resulting in different isomers.
Isomerism is a phenomenon whereby a chemical compound have the same
molecular formula but different structural formulae.
Chain Length Isomerism- deals with compounds of same molecular formula but are different
in their own length. E.g
Positional Isomerism- deals with position of functional group or branch group. E.g
Functional group Isomerism- deals with 2 different compounds with same molecular formula
but different functional groups.
Cyclic/Acyclic Isomerism- deals with isomers of unsaturated compounds (double/triple
bond) in which a double bond = a ring structure irrespective of the size of the ring; a triple
bond = 2 double bonds etc. E.g:
Rules for IUPAC Naming Organic Compounds
i. Locate the longest chain, this determines the parent name for the compound.
ii. Number the longest chain beginning with the end nearest to the substituent group or number
so as to give least summation of numbers.
It will be incorrect to name the above as: 2,4,4,5-

tetramethylhexane becos summation of numbers (15) is
higher than 2,3,3,5- which is 13.
Rules for IUPAC Naming Organic Compound Contd
iii.Use of the number obtained in 2 above to designate the location of the substituent groups.
iv.When 2 substitute groups are present on the same carbon atom, use the number twice.
CH3 CH3
H2 2,2,3,5,5-pentamethylhexane
H
H 3C C C C C CH3
NOT 2,2,4,5,5-pentamethylhexane
CH3 CH3 CH3
v. When two or more chains are of equal length, choose the chain with greater number of
substituent group
2,3,5- trimethyl-4-propyl heptane

NOT
3,5,6-trimethyl-4-propyl heptane
vi. If the substituent group in a branched alkyl group, note the position of the branching and
write the name of the branch group in bracket and note that the carbon that is directly attached
to the main chain is referred to as carbon number 1 in the substituent group.
Stereo-Isomerism
Geometrical Isomerism- This is known as cis/trans isomerism. This is as a result of
the double bond in the structure. The double bond confers rigidity on the molecule
thereby restricting free rotation.
H Y H H
H C C H H C C H
X H X Y
H Y H H
C C X C C
X H X Y
Double bond confers rigidity
Identical groups on the opposite side of the double bond =Trans; Identical groups on the side of
the double bond = Cis
Geometrical Isomerism: Z and E notation
Z means Zusamen; E means entgene
Z and E notation is resolved by a set of rule called: Cahn Ingold- Prelog Rule. It depends on
the mass number (atomic mass) of atoms attached to the alkene (olefinic) center.
If two bulky atoms are on the same side. It is Z- isomer; whereas if two bulky groups are on
opposite side of the double bond it is E-isomer.
Cahn Ingold- Prelog Rule

1. Consider and arrange the atoms directly attached to the Olefinic center in order of their
mass numbers Br CH3

C C
Z- Isomer
Cl H
2. If you cannot distinguish priority based on the 1st set of atoms (1o consideration), then move
to the next set of atoms.
Optical Isomerism
When two or more organic compounds are alike in every aspect, but differ in their action on
plane-polarized light, they are known as ‘Optical Isomers’.
Polarimeter - instrument used to measure the observed rotation of optical isomers.
Any compound that affects the plane polarised light is said to be optically active. If it turns
the plane of polarised light clockwise it is termed Dextro- rotatory compound and
designated as positive (+ve) isomer but if it turns the plane anti-clockwise, it is termed
Levo-rotatory, designated as negative (-ve) isomer. If a compound did not affect the plane
of polarised light, then it is not optically active.

The degree of activity of an optically active compound is measured by its observed rotation
(α) expressed as either + or - in degree. Mathematically observed rotation α is:
Where:

is the specific rotation of the the compound. The specific rotation of a pure
organic compound is a characteristic of the compound. It is expressed as either + or –
in degree.
C = concentration of the organic compound (g/ml), while l = path length (length of
sample cell in dm); 25 = average room temp and D = Sodium D-line.
e.g:

Calculate the observed rotation of an organic compound containing 0.35 g/ml of it a
5.0 cm cell , if it’s specific rotation is +16o.

α = cxl x

= [ 0.35 x 0.5 x 16 ] o
(5.0 cm = 0.5 dm)
= + 2.8 o.
Chiral Carbon
For a particular compound to be optically active, it must possess asymmetric center or
chiral center or stereogonic center all of this indicate the presence of chiral carbon atom(s).
A chiral carbon is one that does not possess any element of symmetry, it is attached to four
different atoms or group of atoms. Such C-atom is said to be non symmetrical
(asymmetrical, possesses no element of symmetry)
A and B above are mirror images becos of presence of asymmetric carbon center (a C-atom
connected to 4 different groups), they are none super-impossable mirror images. The none
super impossability of mirror images of a compound is a feature of optically active
compound.
Compounds C & D possess element of symmetry becos at least 2 of the 4 atoms bonded to
the center C-atom are identical.
Identify chiral C-atom(s) in the following compounds:
Stereogenic C-atoms & Number of Optical Isomers:

A compound with 1 chiral C-atom will have 2 isomers, which are mirror images; with 2
chiral C-atoms, 4 isomers will be obtained. The number of optical isomers of a compound
with n chiral C-atoms is given by:
2n .
2-hydroxyl-2-methylpentane, a molecule with 2 chiral C-atoms hence 4 optical isomers as

shown above.
Assignment
Draw the structure of glucose
How many chiral carbon atom does it have
How many optically active isomers does the glucose possess
Draw the structures of the isomers
Some important terminologies in Optical Isomerism

(i). Racemic Mixture (Racemate)
This is equimolar amounts of enantiomers i:e a mixiture of equal amount of +ve
& -ve isomers, the resultant optical activity is zero. This implies that a racemate
has zero optical activity i:e it is not optically active. Compounds a & b above are
enantiomers therefore a mixture of equal amounts of a & b will constitute a
racemate

(ii) Diastereomers
These are optically active compounds which are not mirror images e.g:
compounds a & c; b & d; a & d; b & c above are diastereomers

(iii) Meso compounds
These are compounds that contain chiral C-atoms but are not optically active due
to internal compensation i:e presence of element of symmetry within the
molecule itself.
2,3-dihydroxyl butane has 2 chiral centres so should have 4 isomers. Compounds e & f above
are optically active but g is not becos of presence of element of symmetry (axis and plane of
symmetry). Compound g therefore is a meso compound.

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Stereochemistry

Rules for IUPAC Naming Organic Compounds

It will be incorrect to name the above as: 2,4,4,5-

2,3,5- trimethyl-4-propyl heptane

Double bond confers rigidity

Cahn Ingold- Prelog Rule

Stereogenic C-atoms & Number of Optical Isomers:

2-hydroxyl-2-methylpentane, a molecule with 2 chiral C-atoms hence 4 optical isomers as

Some important terminologies in Optical Isomerism

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