CH 13

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
o 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, R 3N is obtained (tertiary
amine, 3°).
Nomenclature
Common System
 Aliphatic amine: Named by prefixing alkyl group to amine, i.e., alkylamine.
o 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 −
o Suitable prefix such as di-, tri-, etc., is attached to amine.
o ‘e’ of the suffix of hydrocarbon is retained.
o Positions of −NH2 group are specified by giving numbers to the parent chain.
o Example:
Ethane-1, 2-diamine
 For aryl amines −
o −NH2 group is directly attached to the benzene ring
o Simplest arylamine: C6H5NH2 (Common name − aniline, IUPAC name − benzenamine)
o 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 NH 3 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.

o 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
 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.
o Reason: Form H-bonds with water molecules
o 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:

o Electron-releasing groups like −OCH3, −CH3 increase basic strength
o Electron-withdrawing groups such as −NO2, −SO3, −COOH, −X decrease basic
strength.
 Alkylation
Amines undergo alkylation on reaction with alkyl halides.
o Sandmeyer’s reaction
.
 Acylation
o Example:
Benzoylation − Reaction of amines with benzoyl chloride (C 6H5COCl)
Chemical Reactions of Amines : II

Charbylamine 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
HNO2 is prepared in situ from a mineral acid (HCl) and sodium nitrite (NaNO 2).
 Primary aliphatic amines
 Aromatic amines
 Secondary and tertiary amines react differently with HNO 2.
Reaction with arylsulphonyl chloride
 Benzenesulphonyl chloride (C6H5SO2Cl) (known as Hinsberg’s reagent) reacts with 1° and 2°
amines to form sulphonamides.
o With primary (1°) amine
o 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
o Electrophilic substitution reaction of aromatic amines is of very high reactivity − tends

to occur both at ortho and para positions. To prepare monosubstituted aniline, −NH 2
group is protected by acetylation with acetic anhydride; then the desired substitution
is carried out, followed by hydrolysis.
Activating effect of −NHCOCH3 is less than that of the amino group.Reason − Lone
pair is less available on nitrogen for donation to the benzene ring by resonance.
 Nitration
o 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.
o 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 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 NaNO 2 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
o Sandmeyer reaction
o 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
o Azo products are obtained, which have an extended conjugated system. Both the
aromatic rings are joined through the −N=N− bond.
o 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.
o − F, −Cl, −Br, −I, −CN, −OH, −ON2 groups can be introduced into the aromatic ring.
MAZHAR SIR
(M.Sc. ORGANIC CHEMISTRY)
CONTACT NO. 7878114456

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Amines

Amine Common name IUPAC name

CH3−CH2−NH2 Ethylamine Ethanamine

Aniline Aniline or Benzenamine

 By reduction with metals in acidic medium

Ammonolysis of Alkyl Halides

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

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

 Catalytic hydrogenation of nitriles

Gabriel Pthalimide Synthesis

 Aromatic primary amines cannot be prepared by this process.

Physical Properties of Amines & Chemical Reaction of

 Lower aliphatic amines are gases with fishy odour.

 Order of basicity of amines in the gaseous phase:

 In the case of substituted aniline:

Chemical Reactions of Amines : II

 Known as carbylamine reaction or isocyanide test

o With secondary (2°) amine

 No reaction with tertiary (3°) amines

o Electrophilic substitution reaction of aromatic amines is of very high reactivity − tends

group → Diazonium group

 HNO2 is produced in the reaction by the reaction of NaNO 2 and HCl.

 Replacement by iodide ion

 Replacement by Hydrogen atom

 Replacement by hydroxyl group

 Replacement by −NO2 group

Reactions Involving Retention of Diazo Group

o It is an example of electrophilic substitution reaction.

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