AMINES

AMINES
Amines are derivatives of ammonia with general formula R-NH2
Example- CH3 NH2 Methylamine, C2H5 NH2 Ethylamine etc

Amines are obtained by replacing hydrogen atom of ammonia by alkyl or aryl

group.

CLASSIFICATION:-
They are classified as primary, secondary and tertiary amines based on number of
hydrogen atoms of ammonia replaced by alkyl or aryl group.

Primary amine:-
These are, obtained from ammonia by replacing one hydrogen atom by one alkyl
or aryl group. Its general formula is R-NH2.

Formula Common Name IUPAC Name

CH3 NH2 Methyl amine Methanamine
C2H5 NH2 Ethyl amine Ethanamine
C3H7 NH2 Propyl amine Propanamine
C6H5 NH2 Phenyl amine Amino benzene
(Aniline)

Secondary amine:- These are obtained from ammonia by replacing 2 hydrogen atoms by
2 alkyl or aryl group. General formula is R2-NH

Formula Common Name IUPAC Name

CH3NHCH3 Dimethyl amine N-Methyl Methanamine.
C2H5 NHCH3 Ethyl methyl amine N-Methyl Ethanamine
C3H7 NH CH3 Methyl propyl amine N-Methyl Propanamine
C6H5 NH C6H5 Diphenyl amine N-Phenyl aminobenzene
Tertiary amines:-
It is obtained from ammonia by replacing all the hydrogen atom by alkyl or aryl
group. Its general formula is R3-N.

Formula Common Name IUPAC Name

CH3 Trimethyl amine N,N dimethyl Methanamine.
|
CH3-N-CH3
CH3-N-C2H5 Ethyl dimethyl amine N,N-Dimethyl Ethanamine
|
CH3
C2H5-N-CH3 Ethyl, methyl propyl amine N-Ethyl, N-methyl Propanamine

C6H5 N C6H5 Triphenyl amine N,N-DiPhenyl aminobenzene

|
C6H5

Dept. of Chem. YCM 1 B Sc IV semester

 AMINES

Preparation of amines:
1. Alkylation of ammonia: Alkyl halides on heating with alcoholic ammonia gives 10, 20
and 30 amines . Along with this quaternary salt is also obtained.

CH3Cl +NH3 CH3-NH2 + HCl

Methyl Primary
Chloride amine
CH3-NH2 + CH3 Cl CH3-NH-CH3 + HCl
Secondary amine
CH3-NH-CH3 + CH3 Cl CH3- N- CH3 + HCl
|
CH3
Tertiary amine
CH3
|+ -
CH3-N-CH3 + CH3 Cl CH3-N- CH3Cl
| |
CH3 CH3
Quaternary salt

2. Reduction of amides

Amides will reduced to the amine, by the conversion of the C=O group of amide to -
CH2- in the presence of reducing agent LiAlH4

General reaction

Dept. of Chem. YCM 2 B Sc IV semester

 AMINES
Example:

LiAlH 4
CH3CONH2 CH3CH2NH2
H2O
Acetamide Ethyl amine

3. Reduction of nitrile
The catalytic hydrogenation of nitriles gives amines. The main catalysts used are raney
nickel, palladium black, or platinum dioxide.
R-C≡N + 2 H2 → R-CH2NH2 primary amine
Depending on reaction conditions, we can also get secondary and tertiary amines:
2 R-C≡N + 4 H2 → (R-CH2)2NH + NH3
Secondary amine
3 R-C≡N + 6 H2 → (R-CH2)3N + 2 NH3
Tertiary amine
Example:

Raney Ni
CH3CN CH3CH2NH2
Methyl cyanide Ethyl amine

Separation of amines by Hinsberg’s method:

When an amine is prepared we get mixtures of amines (10, 20, 30) and quaternary
salts. Individual amines are separated by Hinsberg’s method. In this method quaternary
salt is first separated by distillation and Hinsberg’s reagent ( Benzene sulphonyl chloride)
is added to a mixture of 10, 20 and 30 amines. 10 and 20 amines react with Hinsberg’s
reagent and converts into ppt. Where as 30 does not react.

CH3NH2 + ClSO 2 CH3NHSO2- + HCl

Primary amine Precipitate of

primary amine

(CH3)2NH + ClSO 2 (CH3)2NSO2 + HCl

Secondary amine Precipitate of

secondary amine

(CH3)3 N + ClSO 2- No reaction

Dept. of Chem. YCM 3 B Sc IV semester

 AMINES
Tertiary amine

30 amine is separated by filtration and distilled to get pure amine. The ppt of 10
and 2 is treated with NaOH, 10 amine dissolves leaving behind 20 amine as such.
0

10 amine is separated by filtration and distilled to get pure amine. The ppt of 20 amine is
treated with excess of NaOH, the 20 amine dissolves and it is distilled to get its pure
form.

Basicity:
Amines, like ammonia is basic in nature because of the presence of the lone pair of
electron in a nitrogen atom (according to Lewis concept Base is an electron donor)

Aliphatic amines are stronger bases than ammonia and aromatic amines. For example it
easily forms salt with acid
R-NH2 + HCl R-N+H3Cl-
Base Acid Salt

Because of the presence of electron releasing or donating alkyl groups aliphatic

amines are stronger bases than ammonia and aromatic amines. In the presence of the
electron releasing group the density of electron on nitrogen atom increases in other
words, nitrogen atom will be able to donate its pair of electron to proton more easily.
As the number of electron releasing groups increases Basicity of amines also
increases, therefore Basicity of different amines, should be in the order of 30 >20 >10.The
exact order will be 20> 10 > 30 this is because of two reasons they are

1. Steric effect: Addition of proton to amine increases crowding which results in

unstability and it is maximum in 30 amine, as a result the molecules basicity
reduces.
2. Decrease in solvation: Amines after donating lone pair of electrons carry +ve
charge, which gets stabilized due to solvation. The greater the size of the ion the
less will be the solvation. In 30 amine lone pair electrons are available on nitrogen
atom but the size of ion is big therefore it is less solvated. Hence stability of this
ion decreases.
on the other hand aromatic amines are less basic than ammonia & aliphatic
amines for example amino benzene is less basic than NH3, CH3NH2, (CH3)2 NH
NH2 NH2 NH2 NH2

Amino benzene
Because the lone pair of electron on nitrogen atom is involved in resonance i.e
amino group donates its electron to the benzene ring , and hence it cannot donate its
electron to the proton.
If electron releasing group is present in aromatic amine then the Basicity increases.

Dept. of Chem. YCM 4 B Sc IV semester

 AMINES

NH2 NH2 NH2

H3C NO 2
> >

Ex- Methyl amino benzene is more basic than amino benzene due to the presence of
electron releasing methyl group. But in presence of electron withdrawing group NO2,
CO, CHO Basicity decreases.

NH2

NH N
> >

As the number of benzene rings increases Basicity decreases because benzene ring
withdraws electron from amino group.

Identification of 10 , 20 & 30 amines: Hofmann exhaustive methylation

Primary, secondary and tertiary amines react with excess of alkyl halide and form
quaternary ammonium salt. These quaternary ammonium salts react with alkali to give
quaternary ammonium hydroxides. These hydroxides on heating undergo elimination to
form alkene and a tertiary amine.

Primary amine reacts with three molecules of alkyl halide

C2H5NH2 + CH3I C2H5NHCH3 + CH3I C2H5NCH3 + CH3I

-HI -HI
Primary amine CH 3 CH 3 CH 3
Heat
C2H5 NCH3 I AgOH C2H5NCH3 OH CH2=CH2 + (CH3)3N + H2O
-AgI
CH 3 CH 3
quternary salt

Secondary amine reacts with two molecules of alkyl halide

Dept. of Chem. YCM 5 B Sc IV semester

 AMINES
CH 3

C2H5NHCH3 + CH3I C2H5NCH3 + CH3I

C2H5 NCH3 I
-HI
CH 3
secondary amine CH 3

CH 3
Heat quternary salt
AgOH C2H5NCH3 OH CH2=CH2 + (CH3)3N + H2O
-AgI
CH 3

Tertiary amine reacts with one molecule of alkyl halide

CH 3 CH 3

C2H5NCH3 + CH3I AgOH C2H5NCH3 OH

C2H5 NCH3 I
CH 3 -AgI
CH 3 CH 3
Terrtiary amine

Heat quternary salt

CH2=CH2 + (CH3)3N + H2O

DIAZONIUM COMPOUND
Organic compounds with two nitrogen atoms are called diazonium compounds.
The general formula is RN2Cl.

Example: C6H5N2Cl Benzene diazonium chloride

Preparation:
It is prepared by treating an ice cold solution of primary amine in hydrochloric
acid with ice cold solution of sodium nitrite.
O°C
NaNO2 + HCl HNO2 + NaCl
C6H5NH2 + HNO2 + HCl C6H5N2Cl + 2H2O
Aniline Benzene diazonium
(primary amine) chloride

Reaction Synthetic application :

Diazonium compounds are very reactive and give different types of products.
There are two types of synthetic application namely (1) reaction in which nitrogen atoms
are replaced (replacement reaction)
(2) Reactions in which nitrogen atoms are retained.

(1) reaction in which nitrogen atoms are replaced (replacement reaction):

(a) preparation of phenol: It is used in the preparation of phenol. When benzene
diazonium chloride was hydrolyzed we get phenol.

Dept. of Chem. YCM 6 B Sc IV semester

 AMINES

OH H H2O
C6H5 N2 Cl C6H5OH + N2 +
Hydrolysis HCl

(b) Sandmayer’s reaction: (preparation of halo hydrocarbon)

It is used in the preparation of halo hydrocarbons.

CuCl
C6H5 N2 Cl C6H5Cl + N2
HCl Chlro benzene

CuBr
C6H5 N2 Cl C6H5Br + N2
HBr Bromo benzene

(2) Reactions in which nitrogen atoms are retained:

Coupling reaction:
Diazonium compound on coupling with reactive compounds like phenol, aniline etc.,
gives azodye.

N2Cl + OH N2 OH

Benzene diazonium Phenol Para hydroxy azo benzene

chloride (orange colour dye)

N2Cl + NH2 N2 NH2

Benzene diazonium Aniline Para amino azo benzene

chloride (Red colour dye)

Questions

One mark
1. What are amines?
2. Give an example for secondary amine.
3. Arrange the following amines in the decreasing order of basicity
C6H5NH2, CH3NH2, (CH3)3N, (CH3)2NH

4. What are diazonium compounds?

Dept. of Chem. YCM 7 B Sc IV semester

 AMINES
Two marks
1. Write the reactions involved in the alkylation of ammonia.
2. How do you classify amines?
3. What is Hofmann exhaustive methylation? Give an example.
4. How do you convert diazonium compound to phenol?
5. How do you prepare azo compounds?
6. Write the preparation of amines from amide;
7. How do you convert nitrile to amine?

Three/four marks
1. Write a note on identification of primary, secondary and tertiary amines by
Hofmann exhaustive methylation method.
2. Explain Hinsberg’s method.
3. Discuss he basicity of aliphatic amines.
4. Compare the basicity of aliphatic and aromatic amines.
5. Write a note on diazonium compounds

Dept. of Chem. YCM 8 B Sc IV semester