RIMARY AMINES These have two hydrogen atoms and one alkyl or aryl group attached to the nitrogen

to form the amine or amino group -NH2.

ALIPHATIC: methylamine (aminomethane), CH5N, ethylamine (aminoethane), molecular formula C2H7N,

, ,

, ,

displayed/graphic structural formula

, skeletal formula

propylamine, (1-aminopropane), C3H9N,

2-aminopropane,

butylamine, (1-aminobutane), C4H11N,

2-aminobutane,

1-aminopentane (pentylamine), C5H13N,

2-aminopentane,

3-aminopentane,

1-aminohexane (hexylamine), C6H15N,

2-aminohexane,

3-aminohexane,

examples of primary diamines:

1,2-diaminoethane, C2H8N2,

1,3-diaminopropane, C3H10N2,

1,4-diaminobutane, C4H12N2,

1,5-diaminopentane, C5H14N2,

2,3-diaminopentane,

2,4-diaminopentane,

1,4-diaminohexane, C6H16N2,

1,6-diaminohexane, examples of primary cyclo-amines: e.g.

cyclopentylamine, aminocyclopentane, C5H11N2,

aminocyclohexane, cyclohexylamine, C 6H13N2,

benzylamine, C7H9N, aliphatic, NOT aromatic, compare with one of its isomers 2-methylphenylamine below.

examples of primary AROMATIC amines where the amino or amine group is directly attached to the aromatic benzene ring ....

e.g. the simplest is , C6H7N, C6H5NH2, phenylamine (aniline)

1,3-diaminobenzene, C6H8N2,

, 3-aminobenzoic acid,

2-methylphenylamine, methyl-2-phenylamine, 1-amino-2-methylbenzene

this is isomeric with phenylmethylamine or benzylamine, which is a primary aliphatic amine because the amine group is NOT directly attached to the benzene ring. (note: that many 'amino acids' are 'primary' amines - see below)

SECONDARY AMINES These have one hydrogen atom and two alkyl or aryl groups attached to the nitrogen

ALIPHATIC: dimethylamine,

ethylmethylamine,

diethylamine,

methylpropylamine,

ethylpropylamine,

dipropylamine, examples of cyclo-secondary amines: e.g.

piperidine, C5H11N,

N-methylcyclopentylamine, C6H13N, examples of secondary AROMATIC amines: e.g.

N-methylphenylamine, C7H9N,

, N-ethylphenylamine, C8H11N,

and diphenylamine, C12H11N,

TERTIARY AMINES These have no hydrogen atom and three alkyl or aryl groups attached to the nitrogen

ALIPHATIC: trimethylamine,

ethyldimethylamine,

diethylmethylamine,

triethylamine,

two examples of cyclo-tertiary amines:

N-methylpyrrolidine,

and N-methylpiperidine,

examples of tertiary AROMATIC amines: e.g.

N,N-dimethylphenylamine

, N,N-diethylphenylamine

and triphenylamine

QUATERNARY AMMONIUM SALTS If all for hydrogens of an ammonium ion are replaced with alkyl or aryl groups then an ionic quaternary salt is formed.

e.g. the simplest is tetramethylammonium chloride, (CH3)4N Cl tetrapropylammonium chloride, (CH3CH2CH2)4N Cl

+ -

and the R groups can be mixed e.g. [(CH3CH2CH2)3NC6H5] Cl

AMINO ACIDS and ZWITTERIONS The primary suffix name for an aliphatic carboxylic acid is based on the "longest carbon chain name *" for the -COOH bond system e.g. ethanoic acid, propanoic acid etc. Theamino group -NH2, with its Catom position number, is added as a prefix. [* without the end 'e'] Many amino-acids in aqueous solution, or in the crystalline state, exist as 'zwitterions' where the proton migrates from the acidic -COOH group to + the basic -NH2 group to form the ionic groups -NH3 and -COO BUT within the same 'molecule'.

aminoethanoic acid, C2H5NO2,

2-aminopropanoic acid, C3H7NO2,

3-aminopropanoic acid ,

PRIMARY ACID AMIDES

The primary suffix name for an aliphatic acid amide is based on the "longest carbon chain name *" + "amide" for the CONH2 bond system at the end of the carbon chain e.g. methanamide, ethanamide etc. [* without the end 'e'] There are two hydrogens on the N of the amide group.

methanamide, CH3NO,

ethanamide, C2H5NO,

propanamide, C3H7NO,

butanamide, C4H9NO,

pentanamide, C5H9NO,

benzamide, C7H7NO, amide)

, (the simplest primary aromatic acid

SECONDARY ACID AMIDES These have one hydrogen and one alkyl or aryl group on the N of the amide group.

N-methylethanamide,

; N-phenylethanamide,

N-methylbenzamide,

; N-

phenylbenzamide,

POLYAMIDES and POLYPEPTIDES are secondary amides formed in a condensation reaction between a carboxylic acid and an amine. Water is eliminated between the two 'monomers' to give the secondary, polyamide (polymer) or polypeptide (if in proteins) linkage ...

-COOH + H2N- ==> -CO-NH- + H2O process.

is the basic condensation 'polymeric'

(1) KEVLAR is formed from benzene-1,4-dicarboxylic acid and 1,4-diaminobenzene

(2) in proteins, amino acids link together in a condensation reaction to form peptides e.g. Alanine (Ala, 2-aminopropanoic acid) links with Glycine (Gly, aminoethanoic acid) to form the dipeptide

AlaGly (in 'biochemical' shorthand!)

displayed graphical formula

or the skeletal formula Proteins are built up in this way to form long chains of amino-acid residues after the elimination of water ... i.e. nH2NCH(R)COOH ==> -(-NH-CH(R)-CO-)n- + n H2O where R is the variable 'side chain' from the original amino acid (3) NYLONS are formed by condensing together a dicarboxylic acid and a diamine (nylon-x,y) OR polymerising an amino carboxylic acid (nylon-y). [x = length carbon atoms in amine, y = length of carbon atoms in carboxylic acid]

nylon-5

nylon-6

nylon-7

nylon-8

nylon-9

nylon 10

nylon-3,7

nylon-4,6

nylon-4,8

nylon-5,7

nylon-6,6

nylon-7,7

nylon-7,9

nylon-7,11

TERTIARY ACID AMIDES These have two alkyl or aryl groups attached to the N of the amide group.

N,N-dimethylethanamide,

N,N-dimethylbenzamide,

DIAZONIUM SALTS and AZO DYES

Diazonium salts are formed when primary aromatic amines reaction with nitrous acid e.g. C6H5NH2(aq) + HNO2(aq) + H
+ (aq)

==> C6H5N2

+ (aq)

+ 2H2O(l)

The diazonium cation has a nitrogen - nitrogen triple bond system directly attached to the benzene ring e.g.

(1)

from phenylamine+

(2)

from 4-methylphenylamine

(3) from 2-aminobenzoic acid. In alkaline solution these diazonium salts couple with phenols and aromatic amines to form azo dyes which have benzene rings linked with an azo -N=N- bond system e.g.

reacting (1) with phenol gives

reacting (1) with phenylamine gives

reacting (2) with phenol gives

reacting (2) with phenylamine gives

NITRO-AROMATICS These have the nitro -NO2 group directly attached to the ring. On reduction they form primary aromatic amines.

nitrobenzene, C6H5NO2,

; 1,3-dinitrobenzene, C6H4N2O4,

methyl-2-nitrobenzene, C7H7NO2,

; 3-nitrobenzoic acid,

NITRILES The nitrile functional group consists of a carbon to nitrogen triple bond. The name is based on the longest carbon chain, including the C of the nitrile group. methanenitrile (methanonitrile, hydrogen cyanide),, CHN , ,

ethanenitrile (ethanonitrile, acetonitrile), C2H3N, , propanenitrile (propanonitrile, ethyl cyanide), C3H5N,

2-hydroxypropanenitrile, CH3CH(OH)CN