Amines

Amines

• Derivatives of ammonia

• Obtained by the replacement of one, two or all the three H-atoms of ammonia by alkyl and/or aryl
groups

• Example:

Structure of Amines

• Nitrogen on amines is sp3 hybridised.

• Geometry − Pyramidal

• Example: Pyramidal shapes of trimethylamine

• Bond angle C−N−E (E is C or H) is less than 109.5° due to the presence of unshared pair of
electrons. It is 108° in the case of trimethylamine.

Classification

• Classified as primary (1°), secondary (2°), and tertiary (3°)

• If one H-atom of NH3 is replaced by R or Ar, RNH2 or ArNH2 is obtained (primary amine, 1°).

• If two H-atoms of NH3 or one H-atom of RNH2 are replaced by alkyl or aryl group (R′), R2NH is
obtained (secondary amine, 2°).
• On the replacement of another hydrogen atom by alkyl or aryl group, R3N is obtained (tertiary
amine, 3°).

Nomenclature

Common System

• Aliphatic amine: Named by prefixing alkyl group to amine, i.e., alkylamine.

• Example: Methylamine (CH3NH2)

• Secondary and tertiary amines: Prefix di- or tri- is appended before the name of alkyl group when
two or more groups are the same.

IUPAC System

• Named as alkanamines; derived by replacing the ‘e’ of alkane with the word amine.

• Example:

CH3NH2 − Methanamine

CH3CH2NH2 − Ethanamine

• When more than one amino group is present −

• Suitable prefix such as di-, tri-, etc., is attached to amine.

• ‘e’ of the suffix of hydrocarbon is retained.

• Positions of −NH2 group are specified by giving numbers to the parent chain.

• Example:

Ethane-1, 2-diamine

• For aryl amines −

• −NH2 group is directly attached to the benzene ring

• Simplest arylamine: C6H5NH2 (Common name − aniline, IUPAC name − benzenamine)

• While naming arylbenzenes by IUPAC system, the suffix ‘e’ of arene is replaced by ‘amine’.

• Common and IUPAC names of some alkylamine and arylamines are given in the table.

Amine Common name IUPAC name

CH3−CH2−NH2 Ethylamine Ethanamine

Isopropylamine Propan-2-amine

Ethylmethylamine N-Methylethanamine

Trimethylamine N,N-Dimethylmethanamine

Aniline Aniline or Benzenamine

o-Toluidine 2-Aminotoluene
 N,N-Dimethylaniline N,N-Dimethylbenzenamine

Methods of Preparation of Amines

Reduction of Nitro Compounds

• By passing H2 gas in presence of finely divided Ni, Pd, or Pt

Example:

• By reduction with metals in acidic medium

Ammonolysis of Alkyl Halides

• The carbon−halogen (C−X) bond in alkyl or benzyl halides can be easily cleaved by a nucleophile.

• The process of cleavage of C−X bond by ammonia molecule is called ammonolysis.

• The reaction is carried out in a sealed tube at 373 K.

• An alkyl or benzyl halide reacts with an ethanolic solution of NH3 as follows.

• Primary amine obtained behaves as a nucleophile and further reacts as

• Order of reactivity of halides with amines − RI > RBr > RCl

• Disadvantage − Mixture of primary, secondary, tertiary amines and quaternary ammonium salts is
produced.

Reduction of Nitrites

• Reduction of nitrites with LiAlH4

• Catalytic hydrogenation of nitriles

Reduction of Amides

Gabriel Pthalimide Synthesis

• Used for the preparation of primary amine

• Reactions involved in the preparation of primary amine from phthalimide are as follows:
• Aromatic primary amines cannot be prepared by this process.

• Reason − Aryl halides do not undergo nucleophilic substitution with the anion formed by
phthalimide.

Hoffmann Bromamide Degradation Reaction

• Preparation of primary amines by treating an amide with Br2 in an aqueous or ethanolic solution of
NaOH

• Amine formed contains one carbon less than that present in the amide.

Physical Properties of Amines & Chemical Reaction of Amines - I

• Lower aliphatic amines are gases with fishy odour.

• Primary amines with three or more carbon atoms are liquid.

• Higher ones are solid.

• Aniline and other arylamines are colourless, but get coloured on storage due to atmospheric
oxidation.

• Lower aliphatic amines are soluble in water.

• Reason: Form H-bonds with water molecules

• Solubility decreases with increase in molar mass.

• Higher amines are insoluble in water.

• Amines are soluble in organic solvents like alcohol, ether and benzene.

• Order of boiling points of isomeric amines is

 Primary > Secondary > Tertiary

Chemical Reactions

• Amines are basic in nature.

• Order of basicity of amines in the gaseous phase:

Tertiary amine > Secondary amine > Primary amine > NH3

• Order of basic strength in the case of methyl-substituted and ethyl-substituted amines is as follows:

• In the case of substituted aniline:

• Electron-releasing groups like −OCH3, −CH3 increase basic strength

• Electron-withdrawing groups such as −NO2, −SO3, −COOH, −X decrease basic strength.

Let us go through the given video to see the basicity of the simplest aromatic amine, aniline.

• Alkylation

Amines undergo alkylation on reaction with alkyl halides.

• Sandmeyer’s reaction
 .

• Acylation

• Example:

Benzoylation − Reaction of amines with benzoyl chloride (C6H5COCl)

 Chemical Reactions of Amines - II

Carbylamine Reaction

• Known as carbylamine reaction or isocyanide test

• Used as a test for primary amines

• 2° and 3° amines do not show this test

Reaction with Nitrous Acid

HNO2is prepared in situfrom a mineral acid (HCl) and sodium nitrite (NaNO2).

• Primary aliphatic amines

• Aromatic amines

• Secondary and tertiary amines react differently with HNO2.

Reaction with arylsulphonyl chloride

• Benzenesulphonyl chloride (C6H5SO2Cl) (known as Hinsberg’s reagent) reacts with 1° and 2°

amines to form sulphonamides.
• With primary (1°) amine

• With secondary (2°) amine

• No reaction with tertiary (3°) amines

• This reaction is used for the distinction of 1°, 2° and 3° amines.

Electrophilic Substitution Reactions

• Aniline is a resonance hybrid of five structures.

• −NH2 group is a powerful ortho and para directing group.

• Bromination

• Electrophilic substitution reaction of aromatic amines is of very high reactivity − tends to occur
both at ortho and para positions. To prepare monosubstituted aniline, −NH2 group is protected by
acetylation with acetic anhydride; then the desired substitution is carried out, followed by
hydrolysis.
 Activating effect of −NHCOCH3is less than that of the amino group.

Reason − Lone pair is less available on nitrogen for donation to the benzene ring by resonance.

• Nitration

• In strong acidic medium, anilinium ion is formed, which is meta directing. Hence, significant
amount of meta derivative is also formed along with ortho and para isomers.

• By protecting −NH2 group by acetylation reaction, para isomer can be obtained as the major
product.
• Sulphonation

Diazonium Salts

• General formula =

R → An aryl group

X− ion →
 group → Diazonium group

• Examples:

→ Benzenediazonium chloride

→ Benzenediazonium hydrogen sulphate

• Primary aliphatic amines form unstable alkyldiazonium salts.

Primary aromatic amines form stable arenediazonium salts, which are stable for a short time in
solution (at 273 − 278 K).

Stability of arenediazonium salts can be explained on the basis of resonance.

Preparation

• HNO2 is produced in the reaction by the reaction of NaNO2 and HCl.

• The conversion of primary aromatic amines into diazonium salts is called diazotisation.

Physical properties

• Colourless crystalline solid

• Readily soluble in water

• Stable in cold, but reacts with water when warmed

• Decomposes easily in dry state

• Benzenediazonium fluoroborate is water insoluble and stable at room temperature.

Chemical Reactions

Reaction Involving Displacement of Nitrogen

• group is a good leaving group and escapes from the reaction mixture as a gas.

• Replacement by halide or cyanide ion

• Sandmeyer reaction

• Gatterman reaction

• Replacement by iodide ion

• Replacement by fluoride ion

• Replacement by Hydrogen atom

• Replacement by hydroxyl group

• Replacement by −NO2 group

Reactions Involving Retention of Diazo Group

• Coupling reactions

• Azo products are obtained, which have an extended conjugated system. Both the aromatic rings are
joined through the −N=N− bond.

• It is an example of electrophilic substitution reaction.

Importance of Diazonium Salts in synthesis of aromatic compounds

• Substituted aromatic compounds can easily be prepared by the replacement of diazo group, which
cannot be obtained by direct substitution in benzene or substituted benzene.

• − F, −Cl, −Br, −I, −CN, −OH, −ON2 groups can be introduced into the aromatic ring.