TYPES OF ISOMERISM

CHAIN ISOMERISM

STRUCTURAL ISOMERISM POSITION ISOMERISM

Same molecular formula but

different structural formulae FUNCTIONAL GROUP

ISOMERISM
ISOMERISM

GEOMETRICAL ISOMERISM

Occurs due to the restricted

rotation of C=C double bonds...
STEREOISOMERISM
two forms E and Z (CIS and
Same molecular TRANS)
formula but atoms
occupy different
positions in space. OPTICAL ISOMERISM

Occurs when molecules have a

chiral centre. Get two non-
superimposable mirror images.

Note: structural isomerism also known as constitutional isomerism

STRUCTURAL ISOMERISM - INTRODUCTION STRUCTURAL ISOMERISM - CHAIN

COMPOUNDS HAVE THE SAME MOLECULAR FORMULA BUT DIFFERENT
STRUCTURAL FORMULA Two structural isomers of C4H10.

Chain different arrangements of the carbon skeleton

similar chemical properties BUTANE 2-METHYLPROPANE
slightly different physical properties straight chain branched
more branching = lower boiling point

Positional same carbon skeleton

same functional group
functional group is in a different position
similar chemical properties - slightly different physical
properties

Functional Group different functional group

different chemical properties
different physical properties

Sometimes more than one type of isomerism occurs in the same molecule.
The more carbon atoms there are, the greater the number of possible isomers

STRUCTURAL ISOMERISM - CHAIN STRUCTURAL ISOMERISM - POSITIONAL

DIFFERENCES BETWEEN CHAIN ISOMERS
molecule has the same carbon skeleton
Chemical Isomers show similar chemical properties because molecule has the same same functional group... BUT
the same functional group is present. the functional group is in a different position
Physical Properties such as density and boiling point show trends according have similar chemical properties / different physical properties
to the of the degree of branching
Example 1 POSITION OF A DOUBLE BOND IN ALKENES
Boiling Point straight chain isomers have higher values than branched ones
the greater the degree of branching the lower the boiling point
branching decreases the effectiveness of intermolecular forces
1 2 2 3
less energy has to be put in to separate the molecules

- 0.5C - 11.7C greater branching PENT-1-ENE PENT-2-ENE

straight chain branched = lower boiling point double bond between double bond between
carbons 1 and 2 carbons 2 and 3

There are no other isomers with five Cs in the longest chain but there are three
other structural isomers with a chain of four carbons plus one in a branch.

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 STRUCTURAL ISOMERISM - POSITIONAL STRUCTURAL ISOMERISM - POSITIONAL

Example 2 POSITION OF A HALOGEN IN A HALOALKANE Example 3 RELATIVE POSITIONS ON A BENZENE RING

1-CHLOROBUTANE
2-CHLOROBUTANE
halogen on carbon 1
halogen on carbon 2
1 2 2

1,2-DICHLOROBENZENE 1,3-DICHLOROBENZENE
Moving the chlorine along the chain makes new isomers; the position is measured from ortho dichlorobenzene meta dichlorobenzene 1,4-DICHLOROBENZENE
the end nearest the functional group... the third example is 2- NOT 3-chlorobutane. para dichlorobenzene

There are 2 more structural isomers of C4H9Cl but they have a longest chain of 3

STRUCTURAL ISOMERISM FUNCTIONAL GROUP STRUCTURAL ISOMERISM FUNCTIONAL GROUP

molecules have same molecular formula
molecules have different functional groups
ALCOHOLS and ETHERS
molecules have different chemical properties
molecules have different physical properties

ALCOHOLS and ETHERS

Name ETHANOL METHOXYMETHANE

Classification ALCOHOL ETHER

ALDEHYDES and KETONES Functional Group R-OH R-O-R

Physical properties polar O-H bond gives rise No hydrogen bonding

to hydrogen bonding. low boiling point
get higher boiling point insoluble in water
and solubility in water
ACIDS and ESTERS
Chemical properties Lewis base Inert
Wide range of reactions

MORE DETAILS FOLLOW

STRUCTURAL ISOMERISM FUNCTIONAL GROUP STRUCTURAL ISOMERISM FUNCTIONAL GROUP

ALDEHYDES and KETONES CARBOXYLIC ACIDS and ESTERS

Name PROPANAL PROPANONE Name PROPANOIC ACID METHYL ETHANOATE

Classification ALDEHYDE KETONE Classification CARBOXYLIC ACID ESTER

Functional Group R-CHO R-CO-R Functional Group R-COOH R-COOR

Physical properties polar C=O bond gives
dipole-dipole interaction
Chemical properties easily oxidised to acids of
same number of carbons
reduced to 1 alcohols
polar C=O bond gives Physical properties O-H bond gives rise No hydrogen bonding
dipole-dipole interaction to hydrogen bonding. insoluble in water
get higher boiling point
undergo oxidation under and solubility in water
extreme conditions only
Chemical properties acidic fairly unreactive
reduced to 2 alcohols react with alcohols hydrolysed to acids

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 GEOMETRICAL ISOMERISM IN ALKENES
STEREOISOMERISM
Introduction
Molecules have the SAME MOLECULAR FORMULA but the atoms are
joined to each other in a DIFFERENT SPACIAL ARRANGEMENT - they an example of stereoisomerism
occupy a different position in 3-dimensional space. found in some, but not all, alkenes
occurs due to the RESTRICTED ROTATION OF C=C
There are two types... bonds
get two forms...

GEOMETRICAL ISOMERISM

OPTICAL ISOMERISM

CIS (Z) TRANS (E)

Groups/atoms are on the Groups/atoms are on OPPOSITE
SAME SIDE of the double bond SIDES across the double bond

GEOMETRICAL ISOMERISM GEOMETRICAL ISOMERISM

RESTRICTED ROTATION OF C=C BONDS RESTRICTED ROTATION OF C=C BONDS

Single covalent bonds can easily rotate. What appears to be a different structure is C=C bonds have restricted rotation so the groups on either end of the bond are
not. It looks like it but, due to the way structures are written out, they are the same. frozen in one position; it isnt easy to flip between the two.

Animation doesnt
work in old
versions of
Powerpoint

ALL THESE STRUCTURES ARE THE SAME BECAUSE C-C BONDS HAVE FREE ROTATION This produces two possibilities. The two structures cannot interchange easily
so the atoms in the two molecules occupy different positions in space.

Animation doesnt
work in old
versions of
Powerpoint

GEOMETRICAL ISOMERISM IN ALKENES GEOMETRICAL ISOMERISM

CIS-TRANS
Isomerism in butene

CIS / Should only be used when there are two Hs and two non- There are 3 structural isomers of C4H8 that are alkenes*. Of these ONLY
TRANS hydrogen groups attached to each carbon. ONE exhibits geometrical isomerism.

cis non-hydrogen groups / atoms on the

SAME side of C=C bond

trans non-hydrogen groups / atoms on

OPPOSITE sides of C=C bond

* YOU CAN GET ALKANES WITH FORMULA C4H8 IF THE CARBON ATOMS ARE IN A RING

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 OPTICAL ISOMERISM OPTICAL ISOMERISM
- is a form of stereoisomerism that occurs when compounds have
non-superimposable mirror images
Left and right hands are an example
of non-superimposable mirror images.
CHIRAL CENTRES

a a

C* C
d d
b c c b
the two different forms are known as optical isomers or
enantiomers
This usually happens when a molecule contains a C atom with
four(4) different groups attached (chiral / asymmetric carbon [often
shown by an asterisk (*)).
Such molecules are said to be chiral or optically active
Note: superposable and superimposable are identical in
meaning

21 Chiral and Achiral

For chiral molecules the mirror image is
*
a different molecule (the mirror image is
non-superimposable).
chiral molecules (optically active)
OH OH

C C
COOH HOOC
H H3C H
CH3
(-) lactic acid (+) lactic acid
in sour milk in muscles achiral molecules (not optically active)

TASK Some of the following molecules 23 24

are optically active. propan-2-ol CH3 CH CH3

For each one, decide whether it is
optically active or not. OH

NOT OPTICALLY ACTIVE

a) propan-2-ol e) butanone

b) 2-chlorobutane f) 2-methylbutanoic acid

c) 1-chlorobutane g) butan-2-ol

d) 3-methylhexane h) 1-chloro-3-methylpentane

4
2-chlorobutane CH3 CH CH2 CH3 25 26

1-chlorobutane CH2 CH2 CH2 CH3

Cl
Cl
CH2CH3 CH2CH3
NOT OPTICALLY ACTIVE
C C
CH3 H3C
H H
Cl Cl
OPTICALLY ACTIVE

3-methylhexane CH3 CH2 CH CH2 CH2 CH327 O

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butanone
CH3
CH3 C CH2 CH3
CH2CH 2CH3 CH2CH2CH 3

C C
NOT OPTICALLY ACTIVE
CH3 CH3
H H
CH2CH 3 CH3CH2

OPTICALLY ACTIVE

29 2-methylbutanoic acid CH3 O 30

propan-2-ol CH3 CH CH3 CH3 CH2 CH C OH

OH CH2CH3 CH2CH3

NOT OPTICALLY ACTIVE C C

H H
CH3 CH3
COOH HOOC

OPTICALLY ACTIVE

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butan-2-ol OH 31 1-chloro-3-methylpentane CH3 Cl 32

CH3 CH2 CH CH3 CH3 CH2 CH CH2 CH2

CH2CH3 CH2CH3 CH2CH3 CH2CH3

C C C C
H H H H
CH3 CH3 CH3 CH3
OH HO CH2CH2Cl CH2ClCH2

OPTICALLY ACTIVE OPTICALLY ACTIVE

33 OPTICAL ISOMERS - DIFFERENCE

Molecules that are optical isomers are isomers differ in their reaction to plane-polarised light
plane polarised light vibrates in one direction only
called enantiomers. one isomer rotates light to the right, the other to the left
rotation of light is measured using a polarimeter
Enantiomers have identical chemical rotation is measured by observing the polarised light coming out towards
the observer
and physical properties, except:
If the light appears to have turned to the right turned to the left

Their effect on plane polarised light; DEXTROROTATORY

d or + form
LAEVOROTATORY
l or - form
Their reaction with other chiral molecules 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 common in biochemistry and
pharmaceuticals
Most amino acids exhibit optical activity
many drugs must be made of one optical isomer to be
effective
- need smaller doses (safer and cost effective)
- get reduced side effects
- improved pharmacological activity
OPTICAL ISOMERISM
The polarimeter
A B
C D
E
F
A Light source produces light vibrating in all directions
B Polarising filter only allows through light vibrating in one direction
C Plane polarised light passes through sample
D If substance is optically active it rotates the plane polarised light
E Analysing filter is turned so that light reaches a maximum
F Direction of rotation is measured coming towards the observer

If the light appears to have turned to the right turned to the left
DEXTROROTATORY(+) LAEVOROTATORY(-)

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 37 38

Chiral molecules often react differently For example, most amino acids (and
with other chiral molecules. some proteins) are chiral, along with
many other molecules.
This is like the idea that a right hand
does not fit a left handed glove the In nature, only one enantiomer usually
molecule must be the correct shape to occurs (e.g. all natural amino acids
fit the molecule it is reacting with. rotate polarised light to the left).

Many natural molecules are chiral and

most natural reactions are affected by
optical isomerism.

39 In the 1960s thalidomide was given to pregnant 40

women to reduce the effects of morning
Many drugs are optically sickness.
active, with one enantiomer This led to many deformaties in babies and early
only having the beneficial deaths in many cases.

effect.
In the case of some drugs, the
other enantiomer can even be
harmful, e.g. thalidomide.

42

Thalidomide was banned worldwide

O NH O O NH O
O O when the effects were discovered.
H2C C C H2C
CH2 N N CH2
H H

O O

S thalidomide (effective drug) R thalidomide (dangerous drug)

The body racemises each

enantiomer, so even pure S is
dangerous as it converts to R in
the body.

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