3.

7 Organic naming and Isomerism continued

See chapter 3.1 for basic naming of organic molecules. This chapter extends the
naming for functional groups met in next few chapters

prefix / suffix
homologous functional group example
(* = usual use)
series
O
suffix -al H O
aldehydes C H
prefix formyl- H C C H ethanal
H

O suffix* -one H O H
ketones prefix oxo-
C H C C C H
Propanone
H H

O
suffix -oic acid H O
carboxylic acids C OH
H C C OH
Ethanoic acid
H

suffix -nitrile H H
nitriles
prefix cyano-
C N H C C C N Propanenitrile
H H
suffix* -amine
amines C NH2 prefix amino- H H H
Propylamine
H C C C NH2
Or propan-1-amine
H H H

H O H
O
esters
C O
-yl –oate H C C O C H methylethanoate
H H
O
O
acyl chloride
C -oyl chloride CH 3 C ethanoylchloride
Cl
Cl

O O
amide
C -amide
CH3 C ethanamide
NH2
NH2

-oic anhydride
acid anhydrides O
O
R C
CH3 C
O
O
Ethanoic anhydride
R C
CH3 C
O
O

When compounds contain more than one functional group, the order of precedence determines which groups are
named with prefix or suffix forms. The highest precedence group takes the suffix (and the lowest number on the carbon
chain), with all others taking the prefix form. However, double and triple C-C bonds only take suffix form.
Order of priority highest first:
Carboxylic acids >carboxylic acid derivative>nitriles>aldehydes>ketones>alcohols>amines>alkenes>halogenoalkanes

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 Aldehydes H
O Ketones H O H
An aldehyde’s name ends in –al
It always has the C=O bond on the Ketones end in -one H C C C H
first carbon of the chain so it does H C C
When ketones have 5C’s or more
not need an extra number. It is by H H
in a chain then it needs a number
default number one on the chain propanone
H
H to show the position of the double
bond. E.g. pentan-2-one
ethanal H O H O H
If two ketone groups then
di is put before –one and H C C C C C H
If two aldehyde groups
an e is added to the stem H H H
then di is put before –al
O O
and an e is added to pentane-2,4-dione
the stem.
pentanedial O
The prefix oxo- should be
used for compounds that H3C C C
contain a ketone group in O OH
addition to a carboxylic acid
or aldehyde 2-oxopropanoic acid
Carboxylic acids
These have the ending -
oic acid but no number is H H
O
If there are carboxylic acid groups on both ends of the
necessary for the acid chain then it is called a - dioic acid
group as it must always be H C C C O O
at the end of the chain. Ethanedioic acid
The numbering always C C
O H
starts from the carboxylic H H
HO OH Note the e in this name
acid end
Propanoic acid

Amines H H H
H2N O
These end in –amine.
There is, however, rather confusingly two H C C C NH2 If there is another priority
CH C
ways of using this suffix. functional group as well
The exam board tend to use the common
H H H as the amine group then
H3C O H
version where the name stem ends in -yl propylamine the prefix amino is used.
propylamine. Or propan-1-amine 2-aminopropanoic acid.
Another version of the same chemical is
propan-1-amine. (This is used in the
same way as naming alcohols)

If the amine is secondary and has two alkyl CH3CH2CH2NHCH3

groups attached to the nitrogen, then each chain N-methylpropylamine (common name)
is named and the smaller alkyl group is preceded N-methylpropan-1-amine (other name)
by an –N which plays the same role as a number
in positioning a side alkyl chain
CH2 CH2
H3C NH CH3
In the common naming version if the diethylamine (common name- does not use N if chains are
chain lengths are the same an –N is not same length)
used N-ethylethanamine (other name does still use N)

If a tertiary amine similar rules apply, and CH3CH2 CH2 N CH3

each alkyl side group is given an N
CH3
N,N-dimethylpropylamine (common name)
N,N-dimethylpropan-1-amine (other name)

If there are two amine groups then name H H

as following N (CH2)6 N It could also be named
1,6-diaminohexane
H H
hexane-1,6-diamine

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 Nitriles
H H H OH
H3C
These end in –nitrile, but the C of the C
H C C C CN
CN group counts as the first carbon of C
the chain. Note the stem of the name is H3C N
H H H
different : butanenitrile and not
2-hydroxy-2-methylpropanenitrile
butannitrile. butanenitrile

Carboxylic acid derivatives

Esters O
Esters have two parts to their names
H 3C CH 2 C O CH 3
The bit ending in –yl comes from the alcohol that has formed it and is
next to the single bonded oxygen. The bit ending in –anoate comes methylpropanoate
from the carboxylic acid. (This is the chain including the C=O bond) O
O
O
O ethylbenzoate
Ethyl 3-methylbutanoate

Acid Anhydrides
O
O
If the alkyl groups are of
This is called ethanoic CH3 C different lengths then CH3 C
anhydride. It is ethanoic
O each one is named
because it is two ethanoate O
e.g. ethanoic propanoic
groups joined together. CH3 C anhydride CH3 CH2 C
.
O
O

Acyl Chlorides O H3C O O O

add –oyl chloride to the stem CH3 C CH C C (CH2)3 C
name H3C Cl Cl
Cl Cl
ethanoyl chloride 2-methylpropanoyl chloride pentanedioyl dichloride

Amides

O Secondary and tertiary amides

Add –amide to the stem are named differently to show the O
name CH3 C
two (or three) carbon chains.
NH2 The smaller alkyl group is
H3C CH2 C NH CH3
preceded by an –N which plays
ethanamide the same role as a number in
N-methylpropanamide
positioning a side alkyl chain

O CH3
CH3 O CH3
H3C CH2 C N CH3
H3C CH C N CH3
N,N-dimethylpropanamide N,N,2-trimethylpropanamide

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 Isomers
Structural isomerism can arise from
Structural isomers: same molecular formula different
structures (or structural formulae)
•Chain isomerism
•Position isomerism
See 3.1 for more on structural isomerism •Functional group isomerism

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

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

Questions often involve functional group isomers of carboxylic acids: including esters etc
H 3C CH2 O O O OH OH OH
CH 2 C H 3C C O CH 2 CH 3 C CH 2 CH 2 H 2C CH CH CH 2
H 3C
OH

Stereoisomerism
Definition: Stereoisomers have the same structural formulae There are two types of stereoisomerism:
but have a different spatial arrangement of atoms geometrical (E- Z isomerism) and optical
isomerism
See 3.1 for EZ isomerism

Optical Isomerism
A carbon atom that has
Optical isomerism occurs in carbon compounds with 4 H H H H
four different groups
different groups of atoms attached to a carbon (called
H C C C C H attached is called a chiral
an asymmetric carbon).
(asymmetric) carbon
H H O H atom
These four groups are arranged H
tetrahedrally around the carbon.

OH OH This causes two

A mixture containing a 50/50 mixture of the
different isomers that
C C two isomers (enantiomers) is described as
are not superimposable
CH3 H3C being a racemate or racemic mixture.
H5 C2 C2 H5 to be formed. They are
H H mirror images
Many naturally occurring molecules
contain chiral C atoms, but are usually
Two compounds that are optical isomers of
found in nature as a pure enantiomer
each other are called enantiomers.

Different systems of nomenclature are is

Optical isomers have similar physical and chemical properties, existence for optical isomers. D/L or +/- are
but they rotate plane polarised light in different directions. commonly used, but both have been
superseded by the more useful and informative
One enantiomer rotates it in one direction and the other enantiomer R/S system (this is not on the syllabus – for
rotates it by the same amount in the opposite direction. information only).

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

dextrorotatory). The other will rotate it anticlockwise(-)(called
laevorotatory).
Racemate
A racemic mixture (a mixture of equal amounts of the two -ve enantiomer +ve enantiomer
no rotation
optical isomers) will not rotate plane-polarised light. Anticlockwise clockwise
rotation rotation

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Chemical Reactions and Optical Isomers
Formation of a racemate
CH3
A racemate will be formed in a reaction
H
mechanism when a reactant or intermediate C
-NC:
has a trigonal planar group in the molecule :CN-
is approached from both sides by 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) O
δ-
O:
- H+ O H
when the trigonal planar carbonyl group
+
is approached equally from both sides by Cδ H3C C C 2H 5 H3C C C 2H 5
the CN- attacking species: results in the H3C C2H5
formation of a racemate (equal amounts
of both enantiomers) :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%

Drug action and optical isomers

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

Thalidomide Ibuprofen
H CH3
H O
C H H H3C HC CH CH CH3
C C H
C
C C H CH2 C C HC
C N
H C C
C C C
H O CH CH C O
C N
H O
O HO
H
Chiral carbon

One enantiomer of thalidomide causes birth defects in

unborn children whilst the other had useful sedative
problems. Unfortunately it was given in a racemic
mixture when first used.

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