Isomerism

It is possible for organic molecules with the same molecular formula to have different structures

Definition- Structural isomers: same molecular formula different structures (or structural formulae)

There are three types of structural isomerism

•Chain isomerism
•Position isomerism
•Functional group isomerism

Chain isomerism: Compounds with the same molecular formula but different structures of the carbon skeleton

These isomers arise because of the carbon chains can be branched. For example, there are two isomers
of butane, C4H10. In one of them, the carbon atoms lie in a "straight chain" whereas in the other the chain
is branched
H H H
H H H H
H C C C H
H C C C C H
H H
H C H
H H H H

H
butane
methyl propane
There are three isomers of pentane C5H12
H

H H H H H H H H H H C H
H H
H C C C C H
H C C C C C H
H C C C H
H H H
H H H H H H C H H H
H C H
H
pentane H
2-methylbutane 2,2-dimethylpropane

False isomers

Do not draw "false" isomers which are just twisted versions of the original molecule. Twisting
the molecule into a different shape does not make a different isomer. Isomers are only formed
if a bond would have to be broken and reassembled into the different structure

H H H H H
H H H
H C C C C H H C HH
H C C C H

H H H H
H H H C C H
H C H

H H
H C H

These are all exactly the same compound. H

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Number of Possible Chain Isomers for Selected Alkanes

Molecular Formula Number of possible isomers

C4H10 2
C5H12 3
C6H14 5
C7H16 9
C8H18 18
C9H20 35
C10H22 75
C15H32 4,347
C20H42 336,319
C30H62 4,111,846,763

Position isomers: Compounds with the same molecular formula but different structures due to
different positions of the same functional group on the same carbon skeleton

H H H H H H

H C C C H 1-bromopropane H C C C H 2-bromopropane

Br H H H Br H

Functional group isomers: Compounds with the same molecular formula but with atoms arranges to give different
functional groups

H H
H H

H C O C H Methoxymethane: an ether
H C C O H ethanol: an alcohol
H H
H H
H H
H H
C
H C C H

Cyclohexane- cyclo alkane CH3CH2CH2CH2CH=CH2 hexene- alkene

H C C H
C
H H
H H

Aldehydes and ketones of the same chain length would be classed as functional
group isomers- e.g. Propanal and propanone (both C3H6O)

H H O H O H

H C C C H C C C H

H H H
H H

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Structural Isomer Questions

1) a) Define what a structural isomer is.

b) Define what a molecular formula is.

2) Draw all the structural isomers of hexane and name them. What type of structural isomers are these isomers?

3) a) Draw the displayed formulae and name all the straight-chain isomers with the molecular formula C4H8Br2
b) Name the type of structural isomerism that these isomers show and explain why

4) a) Name and draw the displayed and skeletal formulae of a functional group isomer of pent -1-ene
b) Name and draw the displayed and skeletal formulae of a positional isomer of pent -1-ene
c) Name and draw the displayed and skeletal formulae of a chain isomer of pent -1-ene

5) The following is the structure of methoxyethane

H H H
H C C O C H
H H H
a) Draw the displayed formulae and name a functional group isomer of methoxyethane
b) Draw the displayed formulae and name a positional isomer of the compound you have
drawn in part 5a

6) Draw the skeletal formulas of the structural isomers of the different alcohols with the molecular formula
C4H10O. Name the isomers.
7) Deduce the number of structural isomers for Hexane C6H14

8) Name the compound on the right and draw its skeletal

formula. Deduce how many other position isomers of the
compound on the right can be formed.

9) Compound Y is shown below. It is a member of a homologous series of hydrocarbons.

H H H

H C C C C H
H H H
(a) Write the general formula of the homologous series that contains Y.
(b) Name a process used to obtain a sample of Y from a mixture containing other members of the same
homologous series.
(c) Name and draw the skeletal formula of a position isomer of Y.
(d) Name and draw the skeletal formula of a functional group isomer of Y.

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Stereoisomerism
There are two types of stereoisomerism:
Definition: Stereoisomers have the same structural formulae geometrical (E- Z isomerism) and optical
but have a different spatial arrangement of atoms isomerism

Isomerism

Structural isomerism Stereoisomerism

E-Z stereoisomerism Optical isomerism

E-Z stereoisomerism
Alkenes can exhibit a type of isomerism called E-Z stereoisomerism. This occurs because of
restricted rotation that occurs around a double bond

Single carbon-carbon covalent bonds can easily rotate

Cl Cl Cl H Cl H

H C C H H C C Cl H C C H

H H H H H Cl

All three of these structures are the same

C=C double bonds have restricted rotation, due to position

of the pi bond, so the groups on either end of the bond are
fixed in one position. It is not easy to flip between the two.

Cl H Cl Cl
C C C C
H Cl H H C-C
C-C pi
sigma
This produces two possibilities. The two structures cannot bond
bond
interchange easily so the atoms in the two molecules occupy
different positions in space.

E-Z stereoisomers arise when:

(a) There is restricted rotation around the C=C double bond.
(b) There are two different groups/atoms attached both ends of the restricted double bond

H H E-Z stereoisomers: Same structure NOT E-

H H H H H H
two different groups Z stereoisomers : two
C C C C
attached either end of C C C C identical groups attached
H H H H
the restricted double H H H H to one end of the
bond restricted double bond.

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 H H
two different groups H H
H C C H attached either end of
the restricted double H C C H But-1-ene
C C
bond- leads to EZ C C
H H H H isomers H H
H H
two identical groups attached to
Z- but-2-ene
H one end of the restricted double
H These are two bond – no E-Z isomers
C H isomers as the lack
H of rotation around But-1-ene is a structural isomer of But-2-
C C the double bonds
H ene but does not show E-Z isomerism
H C
means one cannot
H be switched to the
H other
E -but-2-ene

Naming E-Z stereoisomers

Cahn–Ingold–Prelog (CIP) priority rules.
On both sides of the double bond determine the priority group

1. Compare the atomic number (Ar) of the atoms

directly attached to each side of the double bond; the
priority
group having the atom of higher atomic number priority Cl Br
receives higher priority.

C C

H Cl

Priority Priority Cl H
group Cl Cl group
side 1 side 2 C C
C C
Z-1,2-dichloroethene
H H H Cl E-1,2-dichloroethene
If the priority atom is on the same side of the If the priority atom is on the opposite side of
double bond it is labelled Z from the german the double bond it is labelled E from the
zusammen (The Zame Zide!) german entgegen (The Epposite side!)

2. If there is are groups of atoms instead of

single atoms attached to the carbon of the
double bond then consider the sum of the H3C
atomic numbers of the entire group. The
CH3 priority
bigger group is the priority
C C
priority H
CH2
H3C
The CH3CH2 group is bigger
than the CH3 so it is the
priority group

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cis-trans isomerism

In some text books you will find this type of E-Z isomerism referred to as geometric isomerism and cis-
trans isomerism.
cis-trans isomerism can be considered as a special case of EIZ isomerism in which two of the substituent
groups are the same. It has been superseded by E/Z isomerism because the Cahn–Ingold–Prelog (CIP)
priority rules allow all alkenes to be considered and not just the ones where the groups are the same .

H
H H
H
H C C H C H
H
C C C C
H
H H H H H C
H
H
Z- but-2-ene E- but-2-ene
Can also be called Can also be called
Cis- but-2-ene trans- but-2-ene

Cis means “on this side of” in latin trans means “across” in latin

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 E-Z Isomerism Questions

1. State the meaning of the term stereoisomers

2. Identify the feature of the double bond in but-2-ene that causes it to form two EZ stereoisomers

3. Draw stuctural formulae of the E-Z isomers of the following compounds

a) 3-methylpent-2-ene.

b) but-2-ene

c) 3-methylpent-2-ene

d) pent-3-en-2-ol

e) hex-3-ene

f) pent-2-ene

4. Name the following including the correct E-Z letter at the start of the name

H3C CH3
C C
CH2 H
H3C

5. Compound A has the molecular formula C5H10O. It has a branched carbon chain and exists as a
pair of E-Z Stereoisomers. Draw the structures and name the two Isomers.

H H

6 Using the carbon skeleton like it is drawn on the right, H C C

Draw the 3 stereoisomers of 1,4-dichlorobuta-1,3-diene. C C H
H H

7. Draw the two E-Z stereoisomers of hex-4-en-2-one.

8. Explain why the following weak unsaturated acid CH3(CH)4COOH shows EZ isomerism. Draw the
structures of each of the E-Z isomers of this acid.

9. How many E-Z stereoisomers are there of the molecule shown below, including the molecule shown?

OH

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Optical Isomerism

Optical isomerism occurs in carbon compounds with 4 different groups of atoms attached to a carbon
(called an asymmetric carbon).

H H H H
A carbon atom that has four different groups attached is
H C C C C H called a chiral (asymmetric) carbon atom
H H O H

This causes two different isomers that are not superimposable to be formed. They are mirror images

H
H H

H
H H
H H H
H
H
H
H
H H
mirror
H
Mirror images
Non superimposable

H H

If the compound does not have 4 different

groups then when it is rotated it will be
H H H H superimposable
H H
not isomers (same compound)

Butan-2-ol has four different groups around a carbon and so forms optical isomers

OH OH

C C
H5 C2 CH3 H3C C 2 H5
H H

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

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Optical isomers have similar physical and chemical properties, but they rotate plane polarised light in different
directions.

One enantiomer rotates it in one direction and the other enantiomer

rotates it by the same amount in the opposite direction.

One optical isomer will rotate light clockwise (+)(called dextrorotatory).

-ve enantiomer +ve enantiomer
The other will rotate it anticlockwise(-)(called laevorotatory). clockwise
Anticlockwise
rotation rotation

Polarimeter
The rotation of light by a chiral compound can be observed by using a polarimeter.
The light source will produce unpolarised light which is light travelling in all planes. If this light is passed
through a polarising filter then plane polarised light will be formed, which is light that only travels in one plane.
When this passes through the sample of the chiral substance the plane polarised light will rotated in to a
different plane.

Polarising
Light filter
source Angle of rotation
of plane
polarised light

Unpolarised
light Plane
polarised
light Sample
solution of
chiral Plane
substance polarised light Analysing
after rotation filter

Method for using a polarimeter

•first put water in sample tube and rotate analysing filter to block out light
•replace water with sample. If the sample is chiral light will be seen
•rotate analysing filter again to block out light. The amount the analyser is rotated is the amount the light
has been rotated.

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

H4
1) Using the Cahn–Ingold–Prelog (CIP) priority rules, used in
EZ isomerism, assign a priority number for each of the four
groups. The ones with the higher atomic number Ar have 2
C
the higher priority. HOOC CH33
OH
1 (highest priority
O biggest Ar )

OH1
2) Redraw the molecule with the atom with the lowest H
priority pointing into the plane of the page (in this case H)
2 C 3
HOOC CH3

3) Imagine moving from substituent 1 to 2 to 3. If moving OH1

in a clockwise direction then assign the compound the R H
letter. If moving anticlockwise the assign the compound the
2 C 3 This is an S
S letter
CH3 enantiomer
HOOC

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Racemic mixtures

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

A racemic mixture (a mixture of equal amounts of the two optical isomers)

will not rotate plane-polarised light.
Racemate
no rotation

Chemical Reactions and Optical Isomers

Formation of a racemate
CH3
A racemate will be formed in a reaction
H
mechanism when a trigonal planar reactant or C
intermediate is approached from both sides by NC:
:CN
an attacking species
O

H
H H 3C CN
NC CH3

C There is an equal chance of C

either enantiomer forming so
a racemate forms. No OH
OH
optical activity is seen

Mechanism for the reaction (drawn the same for both enantiomers)
Nucleophilic addition of HCN to aldehydes
and ketones (unsymmetrical) when the O
δ-
O:
- H+ O H
trigonal planar carbonyl is approached from
+
both sides by the HCN attacking species: Cδ H3C C C 2H 5 H3C C C 2H 5
results in the formation of a racemate H 3C C2H5
:CN- CN CN

A racemate can also be formed in the reaction of the electrophilic addition of HBr to an unsymmetrical alkene

H
H :Br - The bromide can H
+ attack this planar
C CH2 C
δ+ δ- carbocation from C
H Br both sides leading to CH2 Br CH2
H3C CH3 H3C Br
a racemate CH3 CH3
CH3
H2C CH CH2 CH3
:Br - Major product s 90%
If the alkene is H H
unsymmetrical, addition of +
C C CH2 CH3
hydrogen bromide can CH2 CH2 CH2 CH3 Minor
lead to isomeric products. H H product
Br 10%

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Nucleophilic substitution reactions and optical activity

In the topic of reactions of halogenoalkanes we look at the nucleophilic substitution reactions of

halogenoalkanes with aqueous hydroxide ions to form alcohols. The reaction can occur via two different
mechanisms called SN1 and SN2. Primary halogenoalkanes tend to undergo the SN2 mechanism and
tertiary halogenoalkanes undergo the SN1 mechanism. Secondary halogenoalkanes can undergo either
mechanism. The two different mechanisms have a different effect on optical activity of chiral reactants. By
observing the differing effects it can give us evidence for which mechanism is occurring.

Nucleophilic substitution mechanism, SN1

H H
The OH- ion can then
δ+ δ- attack from either side
H3C C Br C + resulting in different
:OH- enantiomers and a
racemate forms
CH2CH3 CH3 C2H5
The Br breaks off leaving a
planar carbocation intermediate H H

C
C
H3C C 2H 5 H 5 C2 CH3
OH or HO

Nucleophilic substitution mechanism, SN2

H - H
δ+ δ- CH3 H

H3C C Br HO C Br HO C CH3
-HO:
CH 2CH3
CH2CH3 CH2CH3
In the SN2 mechanism no intermediates are formed and the reaction occurs via a transition state
If the reactant was chiral then during the reaction the opposite enantiomer would form
through inversion as shown below. H

H
HO C Br
H
HO C Br CH3
H3C H3CH2C
HO C Br
H3CH2C
H CH3 CH CH
2 3
H
H3C C Br
-HO: HO C
CH3
H3CH2C
CH2CH3

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 Drug action and optical isomers
Drug action may be determined by the stereochemistry of the molecule.
Different optical isomers may have very different effects

Ibuprofen
CH3
H3C HC CH CH CH3
CH2 C C HC
CH CH C O
HO

Thalidomide
H H O O H
H O
C H H H C C N
C C H C
C C C
C C H N C C O
C N
H C C C C H
C C C H C C C C
H C O H H
H N O H H
O H
O H
Chiral carbon
S thalidomide (effective
R thalidomide (dangerous drug) drug)

One enantiomer of thalidomide causes birth defects in unborn children whilst the other had useful
sedative problems. It was used as a drug for treat pregnant women with morning sickness. At the
time the side effect was not know. Unfortunately it was given in a racemic mixture when first used
and many babies were born with birth defects

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