AMINES

Amines: They are derivatives of ammonia formed by replacing one or more hydrogen atoms with alkyl or aryl groups. Classification of Amines: I. Amines are classified as primary, secondary or tertiary depending on the number of hydrogen atoms of ammonia which have been replaced. 1. Primary amines (10): Primary amines are obtained by replacing one hydrogen atom of ammonia by an alkyl or aryl group. They possess the general formula RNH2. e.g. CH3NH2 C2H5NH2 C6H5NH2
Methyl amine Ethyl amine Aniline

2. Secondary amines (20): Secondary amines are obtained by replacing two hydrogen atoms of ammonia by an alkyl or aryl group. They possess the general formula R2NH. e.g. (CH3)2NH (C2H5)2NH (C6H5)2NH
Dimethyl amine Diethyl amine Diphenyl amine

3. Tertiary amines (30): Tertiary amines are obtained by replacing all the three hydrogen atoms of ammonia by an alkyl or aryl group. They possess the general formula R3N. e.g. (CH3)3N (C2H5)3N (C6H5)3N
Triimethyl amine Triethyl amine Triphenyl amine

II. Amines are said to be simple when all the alkyl or aryl groups are the same, and mixed when they are different. 1. Simple amines: When all the alkyl groups or aryl groups are same it is called simple amines. e.g. C2H5NHC2H5
Diethyl amine

2. Mixed amines: When the alkyl groups or aryl groups are different it is called mixed amines. e.g. C2H5NHCH3
Ethylmethylamine

III. Based on the nature of the groups attached to nitrogen atom, the amines are classified as aliphatic, aromatic and aralkyl amines. 1. Aliphatic amines: These are the derivatives of ammonia in which one or more hydrogen atoms are replaced by alkyl groups. e.g. CH3NH2 C2H5NH2
Methyl amine Ethyl amine

2. Aromatic amines: Aromatic amines are of two types. (a) Aryl amines: Amines in which the nitrogen atom is directly linked to one or more aryl groups are called aryl amides. They may be primary, secondary or tertiary.

RBDR

Amines e.g. NH2

NH
0 o

N
0

Aniline (1 amine)

Diphenyl amine (2 amine)

Triphenyl amine (3 amine)

(b) Aralkyl amines: Amines in which the nitrogen atom is attached to the side chain by one or more aralkyl groups are called aralkyl amines. They may be primary, secondary or tertiary. e.g.

CH2 NH2 H CH2NCH2

Benzyl amine (1 amine)
0

CH2 CH2 NCH2

o

Dibenzyl amine (2 amine)

Tribenzyl amine (3 amine)

Separation of Amine mixture by Hinsbergs method: This involves the treatment of the mixture of amines with p-Toluenesulphonyl chloride or benzenesulphonyl chloride (Hinsbergs reagent) followed by the addition of some alkali and ether. Primary amines form sulphonamides which dissolve in alkali forming their soluble sodium salts and form the lower aqueous layer. C2H5NH2 + CH3-C6H4-SO2Cl C2H5NH-SO2-C6H4-CH3 + HCl
Ethylamine

(1 amine)

p- Toluenesulphonylchloride

Sulphonamide

(Hinsbergs reagent) Alkali

C2H5NNa-SO2-C6H4-CH3
(Soluble in water)

Secondary amines form sulphonamides which constitute the upper ethereal layer which also contains the tertiary amine which does not react with Hinsbergs reagent. The two layers are separated and the tertiary amine from the ether layer is separated by fractional distillation. (C2H5)2NH + CH3-C6H4-SO2Cl (C2H5)2N-SO2-C6H4-CH3 + HCl
Ethylamine

(1 amine)

p- Toluenesulphonylchloride

Sulphonamide

(Hinsbergs reagent)

(Insoluble in alkali)

The other fraction of ether layer containing the sulphanamide of the secondary amine is treated with con.HCl when

Amines

(i) The primary amine gives N-alkylbenzenesulphonamide. This forms salt with NaOH, which is soluble in water. H CH3-SO2Cl + H N R 10 Amine H -SO2 N R N-Alkylsulphonamide + HCl

NaOH Na+ -SO2 N R Soluble salt (ii) The secondary amine gives N,N-dialkylbenzenesulphonamide. This does not form salt with NaOH (No acidic hydrogen) and is insoluble in alkali solution. R -SO2Cl + H N R 20 Amine R -SO2 N R + HCl

N,N-dialkylbenzenesulphonamide (Insoluble)

NaOH No reaction (iii) The tertiary amine does not react. The resulting alkaline solution is distilled when the tertiary amine passes over and the remaining mixture is filtered. The filtrate on acidification gives the sulphonamide of the primary amine, while the solid residue is the sulphonamide of the secondary amine. The two sulphonamides thus isolated are hydrolysed with con.HCl and distilled over NaOH to yield the respective amines.

Amines H -SO2 N R + HCl H2O -SO2OH + RNH3+ClBenzenesulphonic acid NaOH / RNH2 + NaCl + H2O 10 Amine R -SO2 N R + HCl H2O -SO2OH + R2NH2+ClBenzenesulphonic acid NaOH /

N-Alkylbenznesulphonamide

N,N-dialkylbenzenesulphonamide

R2NH2 + NaCl + H2O 20 Amine Nowadays benzenesulphonyl chloride has been replaced by p-toluene sulphonyl chloride, CH3-C6H4-SO2Cl, since the substituted sulphonamides thus formed are stable solids which can be easily recrystallised. Reaction with Nitrous acid: All the three types of amines (10, 20 and 30) react with nitrous acid but they form different products. Since nitrous acid (HNO2) is unstable, it is always prepared in situ by the action of dil. HCl on sodium nitrite. a) Primary aliphatic amines: Primary aliphatic amines react with nitrous acid in cold to form primary alcohol with the evolution of nitrogen gas. RNH2 + HONO 273-278K R-OH + N2 + H2O e.g. Ethyl amine when treated with nitrous acid forms ethyl alcohol. C2H5NH2 + HONO 273-278K C2H5-OH + N2 + H2O

b) Primary aromatic amine: Primary aromatic amines react with nitrous acid under ice-cold condition to form diazonium salt. This reaction is called diazotization reaction. e.g. When aniline is treated with nitrous acid in ice-cold condition gives benzene diazonium chloride. HCl + NaNO2 HNO2 + H2O NH2 N2Cl ONHO + HCl 273-278K + 2H2O Benzene chloride c) Secondary aliphatic and aromatic amines: Both, secondary aliphatic and aromatic amines react nitrous acid to form nitroso amines, which separate out as yellow oily liquid. R N H + HONO R N N=O + H2O R 20 amine R Nitrous acid N-nitrosoamine diazonium

Amines e.g. (1) When diethyl amine reacts nitrous acid, N-Nitrosodiethylamine is formed. C2H5 N H + HONO C2H5 N N=O + H2O C2H5 Diethyl amine Nitrous acid C2H5 N-Nitrosodiethylamine

(2) When N-Methyl aniline is treated with Nitrous acid, N-Nitroso-N-methylaniline is formed. CH3 N H CH3 N N = O

+ HONO N-Methyaniline

+ H2O N-Nitroso-N-methylaniline

d) Tertiary aliphatic amines: Tertiary aliphatic amines dissolve in a cold solution of nitrous acid to form nitrite salts which when heated decomposes to give nitrosoamine and alcohol. R3N + HNO2 30 amine (R3NH)+NO2Heat Trialkyl ammonium nitrate R2N-N=O + ROH N-nitrosoamine

e.g. Triethyl amine when treated with cod nitrous acid forms triethyl ammonium nitrite. This on heating gives N-nitrosodiethylamine.
+ -

(C2H5)3N + HONO cold [(C2H5)3NH]NO2 amine Triethyl ammonium nitrite

Warm (C2H5)2N-N=O + C2H5OH N-nitrosodiethylamine

Triethyl

e) Tertiary aromatic amines: Tertiary aromatic amines react with nitrous acid to give a coloured nitroso derivative. This reaction is called nitrosation and as a result, a hydrogen atom in the para position gets replaced by a nitroso (-NO) group. e.g. N, N-Dimethylaniline on treatment with nitrous acid gives p-Nitroso-N,N-Dimethylaniline N(CH3)2 + HONO N(CH3)2 + H2O

N, N-Dimethylaniline

N=O p-Nitoso-N,N-Dimethylaniline

Basic nature of amines: Amines act as Lewis bases due to the presence of a lone pair on the nitrogen atom. Amines are more basic than water and get protonated by it. When dissolved in water they accept a proton from water and form alkyl substituted ammonium ion and hydroxide ions. RNH2 + H2O = RNH3 + OHDue to the formation of hydroxide ions, the aqueous solutions of amines are basic in nature. The equilibrium constant for the above reaction is given as: + Kb = [RNH3] [OH-] [RNH2] Where Kb is known as dissociation constant of the base. Larger the value of Kb, stronger is the base. Smaller the value of pKb, stronger is the base.
+

Amines Relative basic strengths: 1. Ammonia and Methyl amine: Methyl amine is more basic than ammonia. This is because, the methyl groups in the aliphatic amines have +I (inductive) effect i.e. it is electron releasing in nature.
.. ..

CH3 N H H

HNH H

The methyl group tends to increase the electron density on the nitrogen atom whereby the electron releasing tendency of amine becomes more than that of ammonia where no such group with +I effect is present. Moreover, the electron releasing methyl group stabilizes the methyl ammonium ion. Hence the equilibrium shifts to the forward reaction making methyl amine is more basic than ammonia.
..

CH3NH2 + H2O = CH3NH3 + OH-

The greater the number of electron-releasing alkyl groups, the greater the availability of nitrogens lone pair and stronger the base. CH3 CH3 NH3 CH3 - NH2 CH3 NH CH3 N CH3 Ammonia Methyl amine Dimethyl amine Trimethyl amine Kb 1.8 10-5 37 10-5 54 10-5 6.7 10-5 Dimethyl amine is stronger than methyl amine. However, trimethyl amine is a weaker base than both dimethyl amine and methyl amine. Although trimethyl amine the electron-density is further increased, the steric crowding of three methyl groups makes the approach and bonding by a proton relatively difficult. 2. Ammonia and Aniline: Aniline is a weaker base than ammonia. In aniline, the electron pair on the nitrogen atom is involved in conjugation with the electron pairs of the benzene ring.
+

:NH2 ..

NH2

NH2

NH2 ..

NH2

..

Hence the availability of the lone pair on the nitrogen decreases. In addition, the anilinium ion formed is less stable than aniline. Hence the basic nature of aniline is less than ammonia. C6H5NH2 + H2O = CH3NH3 + OHHence the relative basic strength of methyl amine, ammonia and aniline is: Methyl amine > Ammonia > Aniline Hoffmann-Martius rearrangement: When N,N-dialkylanilines are heated at 4000C in strong acidic medium, intermolecular migration occurs. This is known a s Hofmann-Martius Rearrangement.
.. +

CH3 H3C N.HCl

H H3C N.HCl 3000C

H H N.HCl CH3 NaOH NH2 CH3

Amines N,N-Dimethyl aniline Hydrochloride CH3 CH3 CH3 2,4-Dimethylaniline