6.

10 Amines
Naming

H H H
Amines H2N O
These end in –amine. H C C C NH2 If there is another
There is, however, rather confusingly CH C
priority functional group
two ways of using this suffix. H H H
as well as the amine H3C O H
The exam board tend to use the propylamine group then the prefix
common version where the name Or propan-1-amine 2-aminopropanoic acid.
amino is used.
stem ends in -yl propylamine.
The IUPAC 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 N-methylpropylamine (common name)
chain is named and the smaller alkyl group N-methylpropan-1-amine (IUPAC name)
is preceded by an –N which plays the same
role as a number in positioning a side alkyl CH2 CH2
chain H3C NH CH3

Diethylamine (common name- does not use N if

In the common naming version if the chains are same length)
chain lengths are the same an –N is N-ethylethanamine (IUPAC name does still use N)
not used

CH3CH2 CH2 N CH3

If a tertiary amine similar rules apply,
and each alkyl side group is given an CH3
N N,N-dimethylpropylamine (common name)
N,N-dimethylpropan-1-amine (IUPAC name)

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

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Properties of Amines
Amines have a characteristic fishy smell H δ+
δ- δ+ δ-
Small amines can form hydrogen bonds with water CH3 N
and therefore can dissolve readily in water.
H O
δ+
δ+ H
Base Properties H
Primary aliphatic amines act as Bronsted-Lowry Bases because the
lone pair of electrons on the nitrogen is readily available for forming a CH3NH2 +H2O  CH3NH3+ +OH-
dative covalent bond with a H+ and so accepting a proton.

Primary aliphatic amines are stronger bases than ammonia as the

alkyl groups are electron releasing and push electrons towards the NH3 (aq) +H2O (l)  NH4+(aq) +OH-(aq)
nitrogen atom and so make it a stronger base.

Secondary amines are stronger bases than primary amines because they have more alkyl groups that are
substituted onto the nitrogen atom in place of hydrogen atoms. Therefore more electron density is pushed onto
the nitrogen atom (as the inductive effect of alkyl groups is greater than that of hydrogen atoms).
One might expect using the same trend that tertiary amine would be the strongest amine base but the trend does
not hold. The tertiary amines and corresponding ammonium salts are less soluble in water and this makes them
less strong bases than the secondary amines.

Base strength of aromatic amines

Primary aromatic amines such as phenylamine do not form basic solutions because the
lone pair of electrons on the nitrogen delocalise with the ring of electrons in the benzene NH2
ring. This means the nitrogen is less able to accept protons.

H H H H phenylamine
H H
H N H N
H H
H H
H H

Overall order of base strength

Aromatic amines < ammonia< primary amines< tertiary amines< secondary amines
Weaker bases Stronger bases

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Formation of amines

1 .Forming a primary amine in a one step reaction of halogenoalkanes with ammonia

Change in functional group: halogenoalkane  amine Ammonia dissolved in ethanol is the initial nucleophile
Reagent: NH3 dissolved in ethanol
CH3CH2Br + 2NH3  CH3CH2NH2 + NH4Br
Conditions: Heating under pressure in a sealed tube
Mechanism: Nucleophilic Substitution
Using an excess of Ammonia can limit the further
Type of reagent: Nucleophile, :NH3 subsequent reactions and will maximise the amount of
primary amine formed

Primary amines can be formed by the nucleophilic substitution reaction between halogenoalkanes and ammonia in
a one step reaction. However, as the lone pair of electrons is still available on the N in the amine formed, the
primary amine can react in the same nucleophilic way in a successive series of reactions forming secondary, tertiary
amines and quaternary ammonium salts.
This is therefore not a good method for making a primary amine because of the further reactions. It would mean the
desired product would have to be separated from the other products.

H H
+ In the first step of the mechanism the nucleophile
H3C C Br H3C C NH3 Br -
attacks the halogenoalkane to form an intermediate
H
H
3HN:
H H
+ In the second step of the mechanism a
H3C C NH2 H3C C NH2 second ammonia removes a proton from the
:NH3 + NH4Br
intermediate (acts as base) to form the
H H H amine

2. Preparing Amines from Nitriles

Using the method above of reacting halogenoalkanes and ammonia is not an efficient method for preparing a
high yield of the primary amine because of the further substitution reactions that occur.

A better method is to use the following 2 step reaction scheme

Step 1. convert halogenoalkane to nitrile by using KCN in ethanol (heat under reflux)

CH3CH2Br + CN-  CH3CH2CN + Br -

Step 2. reduce nitrile to amine by using LiAlH4 in ether or by reducing with H2 using a Ni catalyst

CH3CH2CN + 4[H] CH3CH2CH2NH2 A disadvantage of this method is that it is a two step reaction
that may therefore have a low yield. Also KCN is toxic.

3. Reduction of amides with LiAlH4

Reduce an amide to amine by using the reducing agent LiAlH4 in
O ether
CH3 C + 4[H]  CH3CH2NH2 + H2O
This reaction is then followed by reaction with a dilute
NH2 acid, such as dilute sulfuric or hydrochloric acid.

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4. Reducing nitroarenes to aromatic amines See the benzene chapter for how to
form nitrobenzene from benzene.
The nitro group on an arene can be reduced an amine group as follows

Reagent: Sn and HCl or Fe and HCl NO 2 NH2

Conditions: Heating + 6[H] + 2H2O
Mechanism:reduction

phenylamine
nitrobenzene
As the reaction is carried out in HCl the salt C6H5NH3+Cl- will be formed. Reacting
this salt with NaOH will give phenylamine.

Ionic ½ equation for reduction: C6H5NO2 + 6 e– + 6 H+  C6H5NH2 + 2 H2O

This reduction reaction can also be done with

catalytic hydrogenation ( H2 using a Ni catalyst).

Reactions of amines
Reactions with acids
Amines as bases react with acids to form ammonium salts.
CH3NH2 (aq) +HCl (aq)  CH3NH3+Cl-(aq) Addition of NaOH to an ammonium salt
Methylamine methylammonium chloride will convert it back to the amine
2CH3NH2 (aq) +H2SO4 (aq)  (CH3NH3+)2 SO42- (aq)
These ionic salts will be solid crystals, if
the water is evaporated, because of the
strong ionic interactions.
Phenylamines react with acid

NH2 + H+ 
+
NH3

phenylammonium ion

The ionic salts formed in this reaction means that the compounds are soluble in the acid.
e.g. Phenylamine is not very soluble in water but phenylammonium chloride is soluble

Making a basic buffer from an amine

Basic buffers can be made from combining a weak base with a salt of that weak base
e.g. Ammonia and ammonium chloride
Methylamine and methylammonium chloride
Ethylamine and ethylammonium chloride

Formation of complex ions

The lone pair of electrons on the nitrogen enable amines to act as ligands and form dative covalent bonds
into transition metal ions to form coloured complex ions.

4 CH3CH2NH2 + Cu(H2O)62+ [Cu(CH3CH2NH2)4(H2O)2] 2+ +4H2O

This is a similar ligand exchange reaction to the one where ammonia acts as the ligand

4NH3 + Cu(H2O)62+ [Cu(NH3)4(H2O)2] 2+ + 4H2O

light blue solution deep blue solution

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Reaction of primary Amines with halogenoalkanes forming secondary amines

Amines will react with halogenoalkanes in a similar way to the reaction of ammonia with
halogenoalkanes via a nucleophilic substitution reaction

2CH3CH2NH2+ CH3CH2Br CH3CH2NH2CH2CH3+ CH3CH2NH3Br

H
+
H3C C Br H3C CH2 NH2 CH2 CH3 Br -
H
:

CH3CH2NH2
+
H3C CH2 NH CH2 CH3 H3C CH2 NH CH2 CH3 + CH3CH2NH3Br
:NH2CH2CH3
Diethylamine
H

Reaction secondary amines reacting with halogenoalkanes to form a tertiary amine

The same reaction mechanism occurs with the secondary amine reacting to form a tertiary amine
H CH3
CH2
H3C C Br +
H3C CH2 NH CH2 CH3
H
:

H3C CH2 NH CH2 CH3

CH3
CH2 CH3
+ CH2
H3C CH2 N CH2 CH3
H3C CH2 N CH2 CH3
H triethylamine
:

H3C CH2 NH CH2 CH3

Forming a quaternary ammonium salt

H Using an excess of the halogenoalkane will
promote the formation of the quaternary salt
H3C C Br CH3
CH2 Only the first step of the mechanism
H +
H3C CH2 N CH2 CH3 occurs when forming the quaternary salt
:

H3C CH2 N CH2 CH3 CH2

CH2 CH3 Quaternary ammonium salts are not
CH3 amines
Tetraethylammonium ion

quaternary ammonium salt

Quaternary Salts can be used as cationic surfactants

CH3 + Surfactants reduce the surface tension of liquids

(CH2)11
The positive nitrogen is attracted toward negatively
H3C(CH2)11 N (CH2)11CH3 Cl- charged surfaces such as glass, hair, fibres and plastics.
(CH2)11 This helps in their uses as fabric softeners, hair
conditioners and sewage flocculants
CH3

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 Overall scheme of reactions
Where RX is the haloalkane
H R R
H H
RX RX RX
RX +
R N: R N: R N R
H N: H N:

H R R R R
Using a large excess of Ammonia will maximise the amount of primary amine formed
Using an excess of the haloalkane will promote the formation of the quaternary salt

Some questions will involve substituting an amine onto a halogenoalkane which has a different
length of carbon chain from the amine

CH3
CH3Br
CH3Br CH3CH2 CH2 N CH3 CH3Br +
CH3CH2CH2NH2 CH3CH2 CH2 NH CH3 CH3CH2 CH2 N CH3 Br
-

CH3
CH3
propylamine N-methylpropylamine N,N-dimethylpropylamine
Trimethylpropyl-
ammonium bromide

Using excess bromomethane

would promote the final
quaternary salt
Other reactions of amines

Aliphatic amines and phenylamine can react with acyl chlorides and acid anhydrides to form
amides- see chapter on reactions of acyl chlorides for more detail.

Reaction with primary amines with acyl chlorides

Change in functional group: acyl chloride  secondary amide

Reagent: primary amine
Conditions: room temp.

RCOCl +2CH3NH2  RCONHCH3 + CH3NH3+Cl-

O O
+ -
CH3 C + 2CH3NH2  CH 3 C NH CH 3 + CH3NH3 Cl

Cl N-methylethanamide

Paracetamol is made by the reaction of an aromatic amine with

an acyl chloride to produce an amide
O
CH3 C
Cl O
HO NH2 HO NH C CH3

Paracetamol

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 Reaction of phenylamine with aqueous bromine
The lone pair of electrons on the nitrogen in the amine group delocalise with the ring of
electrons in the benzene ring. This makes the benzene ring more reactive. Phenylamine
reacts with aqueous bromine at room temperature. (Remember Benzene would not do
this)

NH2 NH2

+ 3 Br2 Br Br
+ 3 HBr

phenylamine

Br
2,4,6-tribromophenylamine

Synthesis of azo dyes

Step 1: reaction of an aromatic amine with nitrous acid at Nitrous acid is generated in
<10 °C, forming a diazonium ion, situ from NaNO2/HCl.

NH2 NaNO2 + HCl <10oC Below 0oC the temperature is

+ too low and the reaction would
N N be too slow

diazonium ion If the diazonium ion is allowed to

heat above 10oC it reacts with water
to form phenol and N2 gas
C6H5NH2 + HNO2 + HCl C6H5N2+ Cl− + 2H2O
C6H5N2+ + H2O  C6H5OH + N2 + H+

Step 2: coupling of diazonium ion with a phenol under

alkaline conditions;

NaOH
+
N N + OH N N OH

4-hydroxyazobenzene
C6H5N2+ Cl− +C6H5OH  C6H5N2C6H4OH +HCl

Azo dyes are used for dyes, pigments and colourings

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