ISOMERISM

Isomers are molecules which have the same

molecular formula but different structures.

There are a number of different types of isomerism in

organic compounds, we will consider structural isomerism and stereoisomerism

Structural Isomerism
Structural isomers are molecules which have the

same molecular formula but a different arrangement of covalent bonds. The different arrangement of covalent bonds can result from: 1. The functional group being in different positions (positional isomerism) 2. A different arrangement of the carbon skeleton (chain isomerism) 3. A different functional group (functional isomerism)

Positional isomerism
Positional isomers are molecules with the same

molecular formula but which have the functional group on different positions in the molecule.
Alkanes do not show functional isomerism as they have no

functional group.
Alkenes with four or more carbon atoms show positional

isomerism:
Eg but-1-ene and but-2-ene
H H C H H H C C C H H H

H H C H C H C H

H C H H

Positional isomerism
Haloalkanes with three or more carbon atoms show

positional isomerism Eg 1-chloromethylpropane and 2-chloromethylpropane

CH3 CH CH3 CH2 Cl
CH3 Cl C CH3 CH3

True for most other functional groups

Chain isomerism
The arrangement of carbon atoms in an organic

molecule is known as the carbon skeleton.

Carbon skeletons containing up to three carbon atoms

can only be arranged in one way i.e. a straight chain with no branching:

Carbon skeletons containing four carbon atoms can be

arranged in two ways: C C C C

C C

Chain isomerism
Carbon skeletons containing five carbon atoms can be

arranged in three ways:

C C C C C
C

C C C C

Carbon skeletons containing six carbon atoms can be

arranged in five ways:

C C C C C
C

C C C C C C
C C

C
C

C C

C
C

C C All molecules containing four or more carbon atoms

can thus show chain isomerism:

Chain isomerism
Eg butane and methylpropane
H H C H H C H H C H H C H H
H H C H H H H C C H C H H H

Eg pent-1-ene and 2-methylbut-1-ene

H H C H H H H
H H H

H C

H C

H
H

H
H C

C C

H H C

H C H

Functional isomerism
Functional isomers are molecules with the same

molecular formula but different functional groups. Alkanes which have a ring rather than a straight chain arrangement are known as cycloalkanes. They have the general formula CnH2n, which is the same as alkenes. Cycloalkanes and alkenes can thus show functional isomerism.
Eg cyclohexane and hex-1-ene
H H H H H H H C C C H C H C C H

H H
H H

H C H

H C H

H C H

H C H H

C H

Functional group isomerism

Eg 1-propanol, 2-ppropanol, and methyl-ethyl ether

Stereoisomerism
Molecules with the same atoms, and functional

groups, with the same connectivity, but different orientation in space.

Includes geometrical (cis/trans) isomerism, and

optical isomerism.

Geometrical isomerism
In a double bound molecules are not free to rotate in

space

H2C

CH2

or

In a double bond, the second bond is a -bond. This is

caused by the side-on overlap of two p-orbitals: The result is an overlap in two places. This means that the bond cannot be twisted and as a result there is restricted rotation about the -bond. This is why the cis and trans isomers cannot be interconverted and are therefore different

Geometrical isomerism
In a double bound molecules are not free to rotate in

space

H2C

CH2

or

Because of this substituents s are held in place on a

fixed side the double bond. When similar substituents are on the same side of the double bond, the molecules is in the cis- conformation, while if the are across from each other they are in the trans configuration

Geometrical isomerism
Cl C HO C CH3 Cl

H C Cl C

Cl

CH3

Cis

Trans

Questions
Name the following compounds:
a)
H H C H H C H CH3 H C C H
Br C H C H C H C H

b)

CH3 H

c)
H

H C H C H C H

H C H H

d)
Cl

H H H
C C C

H H
C

H H

C H H

Questions
Name the following compounds:
e) CH3CH(CH3)CH3

f) CH3CHBrCH2Br

g) CH2=CHCH2CH3

h) CH3CH=C(CH3)CH3

Questions
Draw the structures of the following compounds:
a) methylbutane c) but-1-ene b) cyclohexane

d) 3-ethyl,2-methylhex-1-ene ene f) 1,1-dichloropropane h) pent-2-ene

e) 3-chlorobut-1-

g) 2,2,4-trimethylheptane

Questions
Draw the four structural isomers of C4H9Cl and name

them.

Draw the three isomers of C4H8 containing a C=C bond and

name them.

Draw the five structural isomers with the formula C6H14

and name them. Then arrange them in order of increasing boiling point, starting with the lowest.

Questions
Given two molecular formulae C4H10 and C4H8;
Select a compound which could be: an alkane

a cycloalkane
an alkene In each case, draw one possible structure to show how

your choice is correct.