ISOMERISM OVERVIEW

Structural isomers = Molecules with the same molecular formula but a different structural formula

Stereoisomers = Molecules with the same molecular and structural formulae but a different arrangement of the
atoms in space

Structural isomerism

a) Chain isomerism The carbon chain of molecules with the same molecular formulae can vary causing
isomerism:
CH3
e.g. C4H10 CH3 CH2 CH2 CH3 CH3 CH CH3

butane methylpropane

b) Position isomerism Functional groups can be in different positions on the carbon chain resulting in
isomers:
OH OH
e.g. C3H7OH CH3 CH2 CH2 CH3 CH CH3

propan-1-ol propan-2-ol

c) Functional group isomerism Some compounds with the same molecular formulae can contain different functional
groups.
O O
Aldehydes & ketones
CH3 CH2 C H CH3 C CH3
e.g. C3H6O
propanal propanone

O O O
Carboxylic acids & esters
CH3 CH2 C OH CH3 C O CH3 H C O CH2 CH3
e.g. C3H6O2
propanoic acid methyl ethanoate ethyl methanoate

Stereoisomerism

Stereoisomerism – E/Z isomerism

• Would have to break the C=C double bond to rotate around it.
CH3 H • If both C of the C=C have two different groups attached, the molecule has E-Z
X isomers.
C C • E = entgegan (highest priority opposite)

• Z = zusammen (highest priority together)

H CH3
CANNOT ROTATE AROUND C=C • Cahn-Ingold Prority (CIP) rules assigned priority of groups attached to C=C – the
higher the atomic number of the group attached to the C’s, the higher the priority (if
they are the same, look at the atoms attached to those atoms)

6 H 3C CH3 6 1 H CH2CH3 6 (6,12

12, 1, 1)
C C Z C C E
9 F Br 35 6 6 (1, 1, 1)
12 CH3 CH3 12

© www.CHEMSHEETS.co.uk 04-June-2021 Chemsheets AS 1047

TASK 1 - Decide which of the following alkenes exhibit E-Z isomerism. For those that do, sketch the Z stereoisomer.

E-Z
Name Structure isomers Z isomer if stereoisomers exist
(üû)

methylpropene

1-chloropropene

2-methylpent-2-ene

2-ethylpent-1-ene

3-methylpent-2-ene

but-1-ene

3,4-dimethylhex-3-ene

2-bromo-3-chlorobut-2-ene

© www.CHEMSHEETS.co.uk 04-June-2021 Chemsheets AS 1047

 Stereoisomerism – optical isomerism

• All molecules have a mirror image but often the mirror image is the same molecule. However, sometimes the mirror
image is a different molecule. Molecules have optical isomers if their mirror images are non-superimposable.

• Molecules containing a C with four different groups attached to it exhibit optical isomerism. A carbon atom that has four
different groups attached is called a chiral (asymmetric) carbon atom.

a a e.g. OH OH

C C C C
b b COOH HOOC
d c c d H H
CH3 CH3

(-)-lactic acid (+)-lactic acid

• Two compounds that are optical isomers of each other are called enantiomers.

• A mixture containing a 50/50 mixture of the two isomers (enantiomers) is described as being a racemate or racemic
mixture.

• Many naturally occurring molecules contain chiral C atoms, but are usually found in nature as a pure enantiomer.

• Optical isomers have the same chemical and physical properties as each other, except for their effect on plane polarised
light (and how they react with other chiral compounds).

• Light is a form of electromagnetic radiation and so consists of waves that vibrate in many directions perpendicular to the
direction of travel. Some substances have the ability to remove from normal light all the light waves except those
vibrating in a single plane - producing plane-polarised light (in the diagrams below, the arrows show the plane in which
the light waves are vibrating, with the light waves coming out of the plane of the paper).

normal light plane-polarised light plane-polarised light after

(waves vibrate in all directions) (vibrates in only one direction) clockwise rotation

• Optical isomers can rotate the plane of polarised light (and so these compounds are said to optically active).

• One enantiomer rotates it in one direction and the other enantiomer rotates it by the same amount in the opposite
direction.

• Different systems of nomenclature are is existence for optical isomers. D/L or +/- are commonly used, but both have
been superseded by the more useful and informative R/S system.

• A racemate will have no effect on the plane of the light - it is optically inactive (each enantiomer cancels out the effect of
the other).

(-)-enantiomer (+)-enantiomer (±)-racemate

(anticlockwise rotation) (clockwise rotation) (no overall effect)

• Many naturally occurring compounds contain chiral C atoms and occur as one pure enantiomer only.

• Many drugs contain chiral C atoms and occur as enantiomers. Often, only one of the enantiomers has the desired effect
(in the same way a left hand only fits a left handed glove). With some drugs, the opposite enantiomer can have an
unwanted effect and so the drug must be produced as one enantiomer only.

© www.CHEMSHEETS.co.uk 04-June-2021 Chemsheets AS 1047

TASK 2 - Decide which of the following compounds exhibit optical isomerism. For those that do, draw 3D diagrams to
show both stereoisomers.

optical
3D diagrams to show both stereoisomers if stereoisomers
Name Structure isomers
exist
(üû)

propan-2-ol

2-chlorobutane

1-chlorobutane

3-methylhexane

butanone

2-methylbutanoic
acid

butan-2-ol

1-chloro-3-
methylpentane

© www.CHEMSHEETS.co.uk 04-June-2021 Chemsheets AS 1047