AMINES

Amines are the derivatives of ammonia in which one, two or all the three hydrogen atoms are replaced by alkyl and/or aryl groups. They constitute an important class of organic chemistry. The three classes of amines are primary, secondary and tertiary amines which are obtained by replacing one, two and three hydrogen atoms of ammonia by alkyl or aryl groups. So, we can represent different types of amines as follows:

In natures, amines are found among proteins, vitamins, alkaloids and hormones. Synthetic polymers, dyestuffs and drugs also contain different types of amines as their constituent parts. For example, adrenaline and ephedrine (that are used to increase blood pressure), both contain secondary amino group while Benadryl, a popular antihistaminic drug contains tertiary amino group. Quaternary ammonium salts are used as surfactants while Diazonium salts act as intermediate in the preparation of variety of aromatic compounds and dyes.

Structure of amines
Nitrogen orbitals of all amines are Each of the three hybridised and the geometry of amines is pyramidal.

hybridised orbitals of nitrogen overlaps with the orbital of hydrogen or carbon orbital contains an unshared pair (lone pair) of

depending upon the composition of amines. The fourth electrons. According to VSEPR theory

Therefore, the bond angle between any two adjacent H-atoms or alkyl groups decreases from the tetrahedral angle of 109.5 to 107 in primary (1) and secondary (2) amines and ammonia. In case of tertiary (3) amines, the bond angle may increase from 107 due to steric hindrance between the three bulky alky groups. For example, it is 108 in case of trymethylamine as shown in following figure.

Pyramidal shape of trimethylamine

Nomenclature
Nomenclature: Following rules are adopted in nomenclature of amines: (i) Aliphatic amines are commonly named by naming alkyl groups attached to the nitrogen atom followed by the suffix-amine. The names are written in one word.

In IUPAC system, amines are named as alkanamines. Hence the IUPAC names of the above two compounds are methanamine and propane-1-amine respectively. (ii) When more than one amino group is present at different positions in the parent chain, their positions are specified as follows:

(iii) In case of aromatic amines (arylamines),

group is directly attached to the benzene ring. In (aniline) is is

IUPAC nomenclature, suffix e of arene is replaced by amine. For example, named as benzenamine.

(iv) In case of complex amine, only IUPAC nomenclature is used in which amino group considered as a substituent and its position on the chain is indicated by the lowest possible number. For example,

Table: Nomenclature of Some Alkylamines and Arylamines Amine Common Name IUPAC Name Ethylamine n-Propylamine Ethanamine Propan-1-amine

Isopropylamine

Propan-2-amine

Ethylmethylamine

N-Methylethanamine

Trimethylamine

N, N-Dimethyl-methanamine

N, N-Diethylbutylamine N, N-Diethylbutan-1-amine

Allylamine

Prop-2-en-1-amine

Hexa-methylenediamine Hexane-1, 6-diamine Aniline Aniline or Benzenamine

o-Toluidine

2-Aminotoluene

p-Bromoaniline

4-Bromo-benzenamine Or 4-Bromoaniline

N, N-Dimethylaniline

N, N-Dimethylbenzenamine

Preparation of amines
Amines are prepared by the following methods: (i) Reduction of nitro compounds:

(ii) Ammonolysis of alkyl halides:

If alkyl halide is in excess, the amine formed further reacts with akyl halide to form 2, 3 amines and finally quaternary ammonium salts.

(iii) Reduction of nitriles:

(iv) Reduction of amides:

(v) Hoffmann bromide degradation reaction:

(vi) Gabriel phthalimide synthesis:

Aromatic amines cannot be prepared by this method because aryl halides do not undergo nucleophilic substitution with the anion formed by phthalimide. (vii) Preparation of Aniline: (i) From nitrobenzene

(ii) By Hoffmann bromamide degradation reaction

Physical Properties of Amines

(i) The lower amines are gases (or low-boiling liquids) with ammonia-like smell (fishy odour). Primary amines with more than two carbon atoms are liquid and still higher ones are solid. Aniline and other aromatic amines are usually colourless but get coloured on oxidation. (ii) In general, amines have higher boiling points than non-polar compounds of similar molecular weights. This is because amines are polar compounds and form intermolecular hydrogen bonds. For example, ethylamine respectively. and propane having almost similar molar masses boil at +17C and 42C

(iii) Amines are soluble in water because they form hydrogen bonds in water. However, solubility decreases in higher amines due to increase in size of the hydrophobic alkyl group. Amines are also soluble in organic solvents like alcohol, ether and benzene.

Basicity of amines
Amines are basic in nature because they have an unshared pair (lone pair) of electrons on nitrogen atom. This lone pair of electrons is available for the formation of a new bond with a proton or lewis acid. The reaction of amines with mineral acids to form ammonium salts shows the basic nature of amines.

Basic strength of amines: Amines are weak bases because they are partially ionised in aqueous solution and an equilibrium exists between the ionised and non-ionised forms. The extent of ionisation is described by an equilibrium constant , known as basicity constant.

Larger the value of stronger is the base. Why amines are more basic than ammonia? The alkyl groups of amines show +I effect and thus they release electrons towards the nitrogen atom. Due to this, the electron density around nitrogen atom increases which increases the availability of lone pair of electrons.

The greater the number of electron-releasing alkyl groups (R), greater the availability of lone pair of electrons on nitrogen and stronger the base.

Here, we should notice that the less basicity of trimethylamine is due to steric crowding of three methyl groups which prevent the bonding of lone pair electrons with the protons.

Chemical Properties of Amines

(i) Alkylation:

(ii) Acylation:

(iii) Reaction with chloroform (carbylamines reaction)

(iv) Reaction with nitrous acid Reaction with nitrous acid helps in distinguishing between amines. Primary amines react with nitrous acid to form alcohols.

Amines react with nitrous acid to form a yellow green oily layer of N-nitrosoamines. N-Nitroamines on warming with a crystal of phenol and a few drops of conc. form green solution which when treated with aqueous NaOH, turns deep blue and then red on dilution. This reaction is called Libermans nitroso reaction.

ter-Amines readily dissolve in nitrous acid forming crystalline trialkyl ammonium nitrite.

(v) Diazotisation:

(vi) Electrophilic substitution reaction: Due to resonance electron density increases at ortho and para positions as compared to meta positions. Therefore group directs the incoming group to ortho and para positions.

A. Bromination:

B. Nitration:

In strongly acidic medium significant amount of meta isomer is obtained. This is due to the formation of anilinium ion which is meta directing.

C. Sulphonation:

D. Friedel-Craft reaction:

Due to salt formation nitrogen of aniline acquires positive charge and thus acts as a strong deactivating group and hence does not allow Friedel-Craft reaction to occur.

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Diazonium Salts
(i) Diazonium Salts: General Formula : where R stands for an aryl group and ion may be , etc. The is called the diazonium group. Stability of Diazonium salts: Arene diazonium salts are much more stable than alkyl diazonium salts. The stability of arene diazonium salt is due to the dispersal of the positive charge over the benzene ring as show below:

(ii) Preparation of Diazonium salts

This process of conversion of a primary aromatic amine into its diazonium salt is called diazotisation. (iii) Chemical Properties of Diazonium Salts: The reactions of diazonium salts can be divided into two categories, namely A. Reactions involving displacement of nitrogen B. Reactions involving retention of diazo group. A. Reactions involving displacement of nitrogen (a) Replacement by halide or cyanide ion.

(b) Replacement by iodide ion

(c) Replacement by fluoride ion

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(d) Replacement by H

Replacement by hydroxyl group:

Replacement by

group:

B. Reactions involving retention of diazo group (coupling reactions): Diazonium salts react with aromatic amines in weakly acidic medium and phenols in weakly alkaline medium to form coloured compounds called azo dyes by coupling at p- or o- position of amines or phenol. The mechanism is basically that of electrophilic aromatic substitutions where the diazonium salt is electrophile.

Test for amines

(i) Hinsbergs Test: In this test, the amine is treated with Hinsbergs reagent [benzene sulphonyl chloride] and shaken with aqueous KOH solution when the three amines behave in different ways.

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A. 1 amine gives a clear solution which on acidification gives an insoluble N-alkyl benzene sulphonamide.

B. 2 amine gives an insoluble N, N dialkyl benzene-sulphonamide which remains unaffected on addition of acid.

C. 3 amine does not react at all. Therefore, it remains insoluble in KOH solution but dissolves on acidification to give a clear solution.

(ii) Isocyanide test (carbylamine test): Primary amines (aliphatic as well as aromatic) react with chloroform in the presence of alcoholic KOH to form foul smelling carbylamines.

Secondary and tertiary amines (aliphatic as well as aromatic) do not give this test.

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Summary

Amines are alkyl or aryl derivatives of ammonia Amines can be prepared by:

Reduction of intro compounds. Ammonolysis of alkyl halides. Reduction of cyanides, amides and oximes. Reduction amination of aldehyde/ketones. Gabriel phthalamide synthesis (for only 1 amine) Hoffmann bromamide degradation reaction.

Hoffmann bromamide reaction also gives only 1 amine but it has one carbon less than the parent amide. Boiling points of amines are higher than alkanes but lower than those of carboxylic acids and alcohols of similar molecular mass. Aliphatic amines are soluble in water because they form hydrogen bonds with water molecules. However, arylamines are insoluble in water. Aliphatic amines are stronger bases than ammonia and their order of basicity is as follows:

Aromatic amines are weaker bases than ammonia. The substituents like R (alkyl),

, etc.,

increase the basic strength (due +I effect) while the substituents like decrease the basic strength (due to I effect). The effect of these substituents are maximum at p (para) position and minimum at O (ortho) position.

The basic strength of amines are expressed in

The amines react with

Alkyl halides (Alkylation) Acid chlorides and acid anhydrides (acylation) Benzoil chlorides (Benzoylation) Heavy metal ions such as to form coordination complexes.

Aldehydes/ketones to form schiffs bases. differently. , where

The 1, 2 and 3 amines react with The general formula of diazonium salts is

R = an aryl group and

Hinsbergs reagent is benzene sulphonyl chloride. Hinsbergs test is used to distinguish 1, 2 and 3 aliphatic amines.

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