10.

0 ORGANIC NITROGEN
 OBJECTIVES

By the end of the subtopic, you should be able to:

• Describe the formation of ethylamine by reduction of nitrile and of phenyl amine by
reduction of nitrobenzene.
• Explain the relative basicity of ammonia, alkyl-amines and phenyl amines in terms of
their structures.
• Describe the reaction of phenyl amine with aqueous bromine and nitrous acid.
• Describe the coupling of benzene-diazonium chloride and phenol and the use of
similar reactions in the formation of dyestuff.
 10.1 AMINES
• By definition an amine is a molecule of ammonia that has one or more of its hydrogen
molecules replaced by an alkyl or aryl group.
• Amines can be classified into three classes:
• Primary, (10 )
• Secondary, (20 )
• Tertiary amines, (30 )

• Below are structures of primary, secondary and tertiary amines respectively:

H H R

N N N
R H R R R R
Primary amine Secondary amine Tertiary amine
Fig 10.1.2: General structure of amines
• In primary amines, only one hydrogen atom of the ammonia molecule is replaced by an
alkyl or aryl group.
• For secondary amines, two hydrogen atoms are replaced while in tertiary amines all the
three hydrogen atoms are replaced by an alkyl or aryl group.
Nomenclature
• Amines are named the same way as other organic compounds.
• If two or three alkyl groups are attached to the to the nitrogen atom then they are listed
alphabetically with the suffix name -amine.
• The name of an amine is written as one word for example:
CH3 C2H5 C2H5

N N N
CH3 CH3 CH3 H C2H5 H
Trimethylamine Ethylmethylamine Diethylamine
Fig 10.1.3: Examples of amines and their names.
 PREPARATION AND OCCURRENCE
Preparation of Amines
• There are many methods of preparing amines which include:
• Reduction of nitriles (also known as alkyl cyanides)
• Reduction of nitro compounds
• Reaction of haloalkanes with ammonia
• Reaction of alcohols with ammonia.
• At industrial level, either reduction of nitriles or reduction of nitro compounds is used.
Reduction of nitriles
• The reduction of nitriles is an important method in amine preparation as there is addition
of an extra carbon atom from the parent reagent.
• Below is an example using bromomethane:
𝐾𝐶𝑁 𝑖𝑛 𝑎𝑙𝑐𝑜ℎ𝑜𝑙
−
𝐶𝐻3 𝐵𝑟 + 𝐶𝑁 𝐶𝐻3 𝐶𝑁 + 𝐵𝑟 −
• The bromomethane is first refluxed with potassium cyanide in alcohol according to
the equation in the previous slide.
• The nitrile is then refluxed with Lithium aluminium tetrahydride (LiAlH4) in dry ether
according to the equation below.
𝐿𝑖𝐴𝑙𝐻4 𝑖𝑛 𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟
𝐶𝐻3 𝐶𝑁 𝐶𝐻3 𝐶𝐻2 𝑁𝐻2

• Reduction of nitriles can also be extended to the formation of aryl amines.

Reduction of nitro-compounds
• Recall the nitration of benzene.
• Below is the summarised synthesis of phenylamine from nitro benzene:
 NO2 NH2

+ 2H2O

• This is an example of a nucleophilic substitution reaction.

• The phenylamine produced by the reaction is a base and will start to react with the
HCl to form phenylammonium chloride according to the equation:
𝐶6 𝐻5 𝑁𝐻2 𝑙 + 𝐻𝐶𝑙 𝑎𝑞 → 𝐶6 𝐻5 𝑁 + 𝐻3 𝐶𝑙 − (𝑎𝑞)
• Phenylamine can be obtained from phenylammonium chloride by reacting it with
sodium hydroxide according to the equation:
𝐶6 𝐻5 𝑁 + 𝐻3 𝐶𝑙 − 𝑎𝑞 + 𝑂𝐻− 𝑎𝑞 → 𝐶6 𝐻5 𝑁𝐻2 𝑙 + 𝐻2 𝑂 𝑙 + 𝐶𝑙 −
• The above explained methods are the most used methods of synthesising amines.
 BASICITY OF AMINES
• Recall the molecule of ammonia:
H

:
H H
Fig 10.1.8:Structure of ammonia with its lone pair.
• Ammonia acts as a Lewis base because the nitrogen atom is able to donate a lone
pair of electrons to form a dative bond with a lewis acid.
• Consider the reaction below
H H +

+ H+ H N H
N
:

H H H

Fig 10.1.9: Dative bond formation of the ammonium ion

• By the same method, amines can also accept a proton (the H+) ion.
• Two main factors mainly contribute to the basicity of nitrogen containing compounds:
• Ability of the nitrogen atom to donate its lone pair of electrons.
• Stability of cation formed after accepting a proton.

Basic strength of ammonia and alkyl (aliphatic) amines.

• The basicity of alkyl amines is dependent on three factors
• The inductive effect.

The Inductive effect

• Straight chain amines are stronger bases than ammonia because of the electron
inductive effect.
• The alkyl groups of smaller carbon chains tend to push electrons towards the
nitrogen atom (positive inductive effect) thus increasing the electron density on the
nitrogen atom.
• The nitrogen on the amines then easily donates its lone pair of electrons easily
according to the sequence:
(30 )amine >(20 ) amine> (10 ) amine > NH3
• The higher the number of alkyl groups attached to nitrogen the more basic amine.

Basicity of aryl amines

• Aromatic amines are far less basic than ammonia.
• Aromatic amines are resonance stabilized as a result of which lone pair of electrons
on nitrogen atom gets delocalized over benzene and hence less easily available for
protonation.
• The delocalised electrons in the benzene ring draws electrons onto it and form a
cloud that make the aryl amines less basic as the nitrogen lone pair is not readily
available for dative bond formation.
Reactions of Phenylamine, 𝑪𝟔 𝑯𝟓 𝑵𝑯𝟐
• Below is the structure of phenylamine:
NO2 NH2

+ 2H2O

Fig 10.1.10: Structure of phenylamine

• From figure 19.1.7, phenylamine is made of two functional groups, the benzene ring
and the −𝑁𝐻2 group.
• The chemical properties of phenylamine are therefore dependent on what the
chemical is attacking, the benzene ring or the −𝑁𝐻2 group.
 REACTIONS OF THE −𝑵𝑯𝟐 GROUP
Reaction of aliphatic amines with nitrous acid
Amine Observation

Primary amine Effervescence of nitrogen

(an alcohol, nitrogen and water are the products)

Secondary amine Yellow oil of nitrosoamine is given off.

(Nitrosoamine and water are the products)

Tertiary amine No visible change, although an acid base

reaction occurs and a soluble salt is obtained
Reaction of aromatic amine with nitrous acid
• Nitrous acid is unstable and is made in situ from sodium nitrite and in the reaction below nitrous acid and
the proton can be replace by sodium nitrite and HCl.
N
NH2 N+

+ HNO2 + H+ + 2H2O

Fig 10.1.11: Reaction of phenylamine and nitrous acid

• The compound formed are benzene diazonium salts/ions.
• The reaction is carried out at temperatures below 10℃.
• The temperature is below 10℃ because nitrous acid is unstable above 10 ℃ and would decompose into
nitric oxide, nitrogen dioxide and water:
2𝐻𝑁𝑂2 → 𝑁𝑂 + 𝑁𝑂2 + 𝐻2 𝑂
• The diazonium ion is unstable above 10 ℃ and in the presence of water, it would decompose into phenol and
nitrogen and a proton.
Reactions of diazonium ion
• Diazonium ion reacts with
• Warm water (temp above 10℃) to give phenol and nitrogen gas.
• Conc HCl in the presence of copper chloride catalyst to yield Chloro benzene
and nitrogen gas.
• Conc HBr in the presence of copper bromide catalyst to yield Bromo benzene
and nitrogen gas.
• KI to yield Iodo benzene and nitrogen gas
• NaCN and CuCN in natural solution to give Benzonitrile and nitrogen gas.
• All the reactions above have a common observation (Effervescence) because of the
nitrogen gas being given off.
 COUPLING REACTIONS
• The diazonium ion is a poor electrophile: it reacts with activated benzene rings such
as phenol in sodium hydroxide to form brightly coloured compounds called azo-
dyes.
OH
N N

Yellow

N NH2
N+ +
NH2
N N
Phenylamine
Red

OH
OH

N N
Orange
• The diazonium ion attaches to position 4 or to position 2 (if position 4 is occupied).
• Azo dyes are very bright because of the high electronic delocalisation. Azo dyes are very stable
and do not lose their colour easily.
• An examples of azo dyes are phenolphthalein, methyl orange and tartrazine.
• Phenolphthalein and methyl orange are used as indicators in titration while tartrazine is used in
colouring in beverages, sweets and chips.

• Tartrazine doesn’t even sound appetizing when you learn what it’s made from! As with most
artificial colours, it is manufactured from coal tar.
• Tartrazine has been linked to asthma, migraines, thyroid cancer, anxiety, clinical depression,
blurred vision, purple spots on skin and unexplainable itchy skin.
• Tartrazine is still used because it’s cheap. Beta Carotene could be used to achieve the same colour
results as Tartrazine, but it’s more expensive.
 REACTION OF THE BENZENE RING
• Phenylamine reacts with bromine to give 2, 4, 6 tribromo phenylamine.
• This is because the amine group is ring activating due to the lone pairs of electrons
on nitrogen atom.
• Therefore the amine group is otho, para directing.
• The observation made on this reaction is immediate white precipitate formed, white
fumes of HBr and bromine water is decolourised.
• This reaction is used to test for phenylamine.
 AMIDES
An amide is a derivative of ammonia or amines and a carboxylic acid or acyl chloride.
Recall a carboxylic acid contains the -COOH group and acyl chloride the –COCl.
Amines contain the -NH2 group.
When amines/ ammonia reacts with carboxylic acid/ acyl chloride it results in the
formation of an amide and water or hydrochloric acid.
The type of reaction is a nucleophilic substitution reaction.

O CH3

CH3 C N

Amide group H
Fig 10.1.12: Structure of N-methyl ethanamide
Reaction of 𝑹𝑵𝑯𝟐 and 𝑹′𝑪𝑶𝑪𝒍 to form an amide
• Now that we have a generalized idea of what an amide is and how it is formed, let us
looks at an exemplified mechanism of how an amide group is formed.
• Consider the simplest acyl chloride (ethanoyl chloride) and simplest primary amine
(methanamine) below:

O CH3

CH3 C :N H

Cl H

Fig 10.1.15: Structure of ethanoyl chloride and methanamine

• The formation of amide happens in two stages:
• The addition stage.
• The elimination stage.
The addition stage
• The two reagents can be used to synthesize the simplest substituted amide as follows:
O
O- CH3
CH3 C
+
Cl CH3 CH3 C N H

:N H Cl H

H
O- CH3 O CH3
+ +
CH3 C N H CH3 C N H

Cl H H

Cl
-
Fig 10.1.16: Addition of amine and acyl chloride
• Recall that the nitrogen element in amines and ammonia has a lone pair of electrons and that chlorine and oxygen have
high electro negativities.
• The oxygen and chlorine atoms in the acyl chloride draw electrons towards themselves thus making the carbon attached
to them relatively positive.
• The lone pair of the nitrogen then attacks the relatively positive carbon.
The Elimination Stage
• The overall molecule to be removed in this second stage is an HCl molecule.
• The process happens in two stages the first being the elimination of a chloride ion.

O CH3 O CH3
+
CH3 C N H CH3 C N + HCl

H H

Cl
-

Fig 10.1.17: Elimination of the chloride ion

• Note that the carbon-oxygen double bond resurfaces as the chloride ion is knocked off.
• The second stage is the removal of the hydrogen ion on the amine molecule
• The general equation for the reaction of acyl chlorides and primary amines is
𝑅′ 𝐶𝑂𝐶𝑙 + 𝑅"𝑁𝐻2 → 𝑅′𝐶𝑂𝑁𝐻𝑅" + 𝐻𝐶𝑙
• Ethanoyl chloride also reacts violently with ammonia to form amides.
Hydrolysis of amides
• Amides are the least reactive of all carboxylic acid derivatives.
• Because of their less reactive nature, they can only undergo hydrolysis to return to
their parent carboxylic acid and amine.
• The hydrolysis require strong acids (e.g. 𝐻2 𝑆𝑂4 ) or strong bases (e.g. 𝑁𝑎𝑂𝐻).
• The general reaction of hydrolysis reaction is given below:
O R O R

R C N H2O, Heat R C + N H

R OH R
Figure 10.1.19: Hydrolysis of amides
• When an acid is used to hydrolyse an amide, the acid works as a catalyst and the
products are an amine and carboxylic acid.
• If NaOH is used, the alkali works as a reagent meaning its used up in the reaction and
the products are amine and sodium carboxylate.
 ASSESSMENT EXERCISE 10.1 ORGANIC NITROGEN
1. Place the following organic compounds in order of basic strength, starting with the strongest base.
[5]

2. Ethylamine can be prepared from the reaction between bromoethane and ammonia.
a. Name the type of reaction taking place. [1]
b. Give the structures of three other organic substitution products which can be obtained from the reaction
between bromoethane and ammonia. [3]
c. Write an equation for the conversion of ethanenitrile into ethylamine and give one reason why this method
of synthesis is superior to that in part (b). [2]
3. Write down the structures of:
a. 2, 4-hexanediamine. [1]
b. 1, 4-butanediamine. [1]
4. This question is about basicity
a. Explain why ethylamine is a Bronsted-Lowry base. [2]
b. Why is phenylamine a weaker base than ethylamine? [2]