Isomerism 1

ISOMERISM - A general survey

STRUCTURAL
ISOMERS have the same molecular formula but different structural formulae
They occur due to variations in . . .

CH3
the carbon skeleton
CH3 CH 2 CH2 CH3 CH3 CH CH3
CHAIN ISOMERISM

positions of a functional CH3CH2CH2Cl CH3CHClCH3

group on a chain
CH3 CH3
POSITION ISOMERISM H CH2 CH3
C C C C
H H H H

Cl Cl Cl
Cl
relative positions
on a benzene ring
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Cl
Cl

H H H H
functional group
FUNCTIONAL GROUP H C C OH H C O C H
ISOMERISM
H H H H

Differences between isomers

Boiling
Point • “straight” chain isomers have higher boiling points than branched chain isomers
• the greater the degree of branching the lower the boiling point
• branching decreases the effectiveness of intermolecular attractive forces
• less energy has to be put in to separate the molecules
• boiling points also vary between isomers containing different functional groups
e.g alcohols and ethers - due to permanent dipole-dipole interactions
or hydrogen bonding.

Chemical
properties Most isomers show similar chemical properties if the same functional group is
present. However, it is best to have a look at each structure and apply any
knowledge of the chemical reactions of the compounds in question.

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2 Isomerism

E/Z ISOMERISM

Occurrence • a form of stereoisomerism.

• found in alkenes, it occurs due to the restricted rotation of C=C double bonds
• certain forms are known as CIS and TRANS
• to occur, there must be two different groups/atoms on one end of the C=C
and two different groups/atoms on the other end

CH3 CH3
2 different groups 2 different groups
on this end C C on this end
H H

Cis-trans • if there are two H’s and two non-hydrogen groups attached to each carbon
CH3 CH 3
CIS groups on the same side of the double bond C C

H H

CH3 H
TRANS groups are across the double bond C C

H CH3

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Both molecules have the double bond in the same position but the atoms occupy
different positions within space.

Quick
check • are two similar atoms, or groups of atoms attached to the same end of the C=C ?
• if so you will not get E/Z isomers

CH3 Br CH3 H CH 3 H

C C C C C C

H H H Br Br H

A B C

A and B are E/Z isomers, C isn’t. It is a structural isomer of the other two.

E/Z • a newer system based on the masses of groups/atoms attached to the C=C
• CIP rules are used to allocate priority
• the heavier the atom / group attached to the C=C bond, the higher its priority...

higher mass I > Br > Cl > F > H lower mass =

= higher priority C3H7 > C2H5 > CH3 > H lower priority

Z ZUSAMMEN Higher priority groups are on the same side of C=C

E ENTGEGEN Higher priority groups are on opposite sides of C=C

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 Isomerism 3

CIP RULES • they work out if a geometrical isomer is E or Z

• named after the people who developed the system... Cahn-Ingold-Prelog
• groups/atoms either side of the C=C are prioritised according to their mass
• higher mass number = higher priority

4-methylheptane

(15) (1) (29)

higher priorities are on the CH3 CH3 higher priorities are on the
H C2H 5
same side of the C=C same side of the C=C
C C C C
C3H C2H C3H H
(Z) isomer 7 5 7 (E) isomer
(43) (29) (43)

Properties E/Z isomers have different physical properties (e.g. boiling point) and sometimes
react differently in certain chemical reactions.

Q.1 Work out all the possible structural isomers of pentene C5H10 and
hexene C6H12 . How many exhibit E/Z isomerism?
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OPTICAL ISOMERISM D D

Occurrence • another form of stereoisomerism

C C
• occurs when compounds have ... B A A B
non-superimposable mirror images

Existence • the two different forms are known as OPTICAL ISOMERS or ENANTIOMERS
and occur when molecules have a CHIRAL centre.

• to find such a centre, look for an ASYMMETRIC CARBON ATOM ...

one with four different atoms, or arranged tetrahedrally around it.
CH3
example C2H5 C OH
Br

• two forms exist which are non-superimposable mirror images of each other;
i.e. you can’t stack one form exactly on top of the other.

Difference • isomers differ in their reaction to plane-polarised light

• one isomer rotates light to the right, the other to the left
• rotation of light is measured using a polarimeter

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4 Isomerism

A POLARIMETER

Polarising filter produces

plane polarised light
Light
source Filter is rotated until the
light appears brightest

Sample under
examination

• rotation is measured by observing the polarised light as it emerges towards

the observer. If the light appears to have...

turned to the right turned to the left

DEXTROROTATORY LAEVOROTATORY
d or + form l or - form

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Racemate • a 50-50 mixture of the two enantiomers (dl) or (±) is a racemic mixture
• the opposite optical effects of each isomer cancel each other out

Examples Optical activity is widespread in nature, biochemistry and pharmaceuticals.

e.g. COOH COOH

H C CH3 H C CH3
NH2 OH
2-aminopropanoic acid 2-hydroxypropanoic acid
(alanine) (lactic acid)

The drug thalidomide is optically active but only one of the optical isomers is
effective. Many years ago women gave birth to babies with abnormalities caused
by taking thalidomide tablets which contained some of the ‘wrong’ enantiomer.

Practical
problems • laboratory reactions are more likely to make mixtures than those in the body
• a larger dose will be needed if a drug contains a mixture of enantiomers
• the non-reactive isomer may be dangerous (as in thalidomide)

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 Isomerism 5

Q.2 How many structural isomers of C6H14 are optically active?

How many structural isomers of butanol, C4H9OH, are optically active?

Q.3 Which of the following can exist as enantiomers?

a) 2-bromopropane b) 2-bromobutane
c) 2-bromopentane d) 3-bromopentane
e) CH3CH(OH)C2H5 f) CH3CH(OH)CH3

Q.4 Why is there the possibility of enantiomers being formed when butanone
undergoes nucleophilic addition with HCN? Do all carbonyl compounds
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produce a mixture of products with HCN? If not, why not?

ISOMERISM

STRUCTURAL ISOMERS STEREOISOMERS

Same molecular formula - Same structural formula, different
different structural formula arrangement of groups in space.

E/Z (cis-trans) ISOMERS OPTICAL ISOMERS

Groups fixed in different space as Groups fixed in different space as a
a result of the restricted rotation result of the asymmetry of the structure.
of double bonds etc. Non-superimposable mirror images of each other.

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