ORGANIC CHEMISTRY CHM 207

CHAPTER 9: AMINES
NOR AKMALAZURA JANI

 Amines:
- organic derivatives of ammonia with one or more alkyl or aryl groups bonded to the nitrogen atom. Functional group:

Classification of amines:
Primary amine Secondary amine Tertiary amine

 Primary (1o) amine: one alkyl or aryl group attached to the nitrogen atom. Secondary (2o) amine: two alkyl or aryl group attached to the nitrogen atom. Tertiary (3o) amine: three alkyl or aryl group attached to the nitrogen atom. Quaternary (4o) amine: an ion in which nitrogen is bonded to four alkyl or aryl groups and bears a positive charge
CH3 H3C N CH3 CH3

NAMING AMINES
Common names: - formed from the names of the alkyl groups bonded to nitrogen, followed by the suffix amine. - the prefixes di-, tri-, and tetra- are used to decribe two, three or four identical substituents.

CH3 CH2 NH2

ethylamine

CH3 CH2

CH3 N CH3

(CH3CH2CH2CH2)4N+ -CI tetrabutylammonium chloride

ethyldimethylamine

CH3 N CH3
cyclohexyldimethylamine

 IUPAC names: - similar to that alcohols. - the longest continuous chain of carbon atoms determine the root name. - the e in alkane name is changed to amine, and a number shows the position of the amino group along the chain. - other substituents on the carbon chain are given numbers, and the prefix N- is used for each substituent on nitrogen.
CH3
4 3 2

CH3 CH2
4 3

NH2 CH CH3
2 1

NH2
1

CH3 CH CH2 CH2

3-methyl-1-butanamine

2-butanamine

NHCH3 CH3 CH2 CH CH3

4 3 2 1

CH3 CH3 CH3 CH2 CH CH CH CH3 N CH3 CH3

2,4, N, N-tetramethyl-3-hexanamine

N-methyl-2-butanamine

 The prefix amino is used to indicate the presence of an NH2 group in a molecule containing than one functional group.
For example,
NH2CH2COOH
aminoethanoic acid

H2NCH2CH2OH
2-aminoethanol

OH NH2 COH

NH2
2,4-diaminophenol

NH2
3-aminobenzaldehyde

NAMING AROMATIC PRIMARY AMINES

Aromatic amines have an amine group (-NH2) attached directly to the aromatic ring. Aromatic amines known as arylamines. Examples,
NH2
1

NH2
3 4

CH3
2 1 6 5

NH2

6 5 4

2 3

phenylamine (aniline)

NO2
4-nitrophenylamine (4-nitroaniline)

2-methylphenylamine (2-methylaniline)

 Compounds with two NH2 groups are named by adding the suffix diamine to the name of the corresponding alkane or aromatic compounds.

H2N

(CH2)6 NH2

H2N

NH2

hexane-1,6-diamine (1,6-hexanediamine)

benzene-1,4-diamine (1,4-benzenediamine)

PHYSICAL PROPERTIES OF AMINES

i) Boiling points: - the boiling points of amines is increase with increasing relative molecular mass. - the lower aliphatic amines are gases or low-boiling liquids. - amines are polar compounds and both primary and secondary amines associate by intermolecular hydrogen bonding.

H H R N H R N H

Hydrogen bonding

R H N H

* Comparing the boiling points of 1o, 2o and 3o amines - for isomeric amines, the boiling points decreases in the order, 1 amine > 2 amine > 3 amine - reason: decrease in intermolecular hydrogen bonding. - example,
CH3 CH3CH2CH2NH2
1-propanamine (1o amine) boiling point: 48.6 C
o

CH3 CH3 N CH3

N, N-dimethylmethanamine (3o amine) 3.5oC

CH3CH2N H
N-methylethanamine (2o amine) 37.0 C
o

molecular formula: C3H9N molecular mass: 59

* Comparing the boiling points of amines with other organic compounds - the boiling points of aliphatic amines are higher than those of alkanes or haloalkanes of similar relative molecular mass due to intermolecular hydrogen bonding. - the N-H bond is more polar than the C-H bond but less polar than O-H bond. Hydrogen bonding in amines are weaker than that of alcohols or carboxylic acids. Boiling points of amines are lower than those corresponding alcohols or carboxylic acids.

Comparison of boiling points of some organic compounds with similar molecular weight
alkane < ether < alkyl halide < amine < ketone, aldehyde < alcohol < acid

ii)

Solubilities of 1o, 2o and 3o amines:

- all three classes of aliphatic amines are capable of forming hydrogen bonds with water molecules. - the lower amines (with chain length up to four carbon atoms per molecule) are very soluble in water because they can form hydrogen bonds with water molecules. - the solubilities of amines is decrease with increasing number of carbon atoms in the chain. - amines are soluble in organic solvents.

THE BASICITY OF AMINES

Amines can act as: - a nucleophile (a Lewis base) because its lone pair none bonding electrons can form a bond with an electrophile. - a Brnsted-Lowry base because it can accept a proton from a proton acid.
Reaction of an amine as a nucleophile

H R N H
nucleophile electrophile

H CH3 I R N H
new N-C bond formed

CH3

Reaction of an amine as a proton base

H R N H
base proton acid

H H X R N H H
protonated

 Amines are fairly strong base and their aqueous solutions are basic. An amine can abstract a proton from water, giving an ammonium ion and a hydroxide ion. The equilibrium constant for this reaction is called base-dissociation constant, symbolized by Kb.
H R N H
Kb = [RNH3+] [-OH] [RNH2] Stronger base have smaller values of pKb

Kb

H R N H H OH

H O H

pKb = - log 10 Kb

 The basicity of the amines depends on the ability of the lone pair none bonding electrons at nitrogen atom to form bond with an acid.
The more easier the lone pair electrons formed bond with the acid, will make the amines a stronger base.

Factors that effect the basicity of the amines:

i) substitution by alkyl groups - the presence of alkyl groups (electron-donating group) such as (CH3) and (CH3CH2-) will make the amine become more basic. - for example, methylamine is more basic than ammonia. ii) substitution by electron-withdrawing groups - the presence of electron-withdrawing groups or atom will decrease the basicity. - for example, nitroaniline is less basic than aniline

Basicity of aromatic amines

* Aromatic amines is less basic than aliphatic amines and ammonia. * Reason: - the lone pair of electrons on the nitrogen atom is delocalised into the benzene ring. - As a result, the lone pair of electrons is less available for donation to an acid. - The reaction is shifted toward the left and makes aniline a weaker base than ammonia or aliphatic amines.

REACTIONS OF AMINES
Salt formation Reaction with nitrous acid Amide formation Ring halogenation of phenylamine

Salt formation
Reaction of amines and acid will give amine salt. Amine salt: - composed of two types of ions: i) the protonated amine cation (an ammonium ion) ii) anion derived from the acid Amine salts are ionic, have higher melting points, nonvolatile solids, more soluble in water than the parent amines and slightly soluble in nonpolar organic solvents.

NH2

HCl

RNH3Cl
alkylammonium chloride

primary amine

R2 NH

HCl

R2NH2Cl
dialkylammonium chloride

secondary amine

R3N
tertiary amine

HCl

R3NHCl
trialkylammonium chloride

EXAMPLES:
CH3CH2CH2 NH2
n-propylamine

HCl

CH3CH2CH2 NH3Cl
n-propylammonium chloride

(CH3CH2)3 N
triethylamine

HCl

(CH3CH2)3 NH Cl
triethylammonium chloride

Reaction with nitrous acid

Nitrous acid (HNO2) is unstable and is prepared in situ by the reaction of dilute HCl or dilute H2SO4 with sodium nitrite in the absence of heat. NaNO2 (s) + HCl (aq) NaCl (aq) + O=N-OH (aq)
nitrous acid

Nitrous acid can be used to differentiate primary, secondary and tertiary aliphatic amines.

Primary aliphatic amines

When aliphatic primary amines react with HNO2, nitrogen is evolved rapidly and an alcohol is produced. RNH2 + O=N-OH R-OH + H2O + N2 (g) For example, ethylamine gives nitrogen and a mixture of ethanol (60%), ethene and other products.
C2H5NH2 + O=N-OH C2H5-OH + H2O + N2 (g) + other products

The reaction of propylamine with HNO2 produces nitrogen and a mixture of 1-propanol (7%), 2-propanol (32%) and propene (28%).
The reaction of methylamine with HNO2 produces only a little methanol, and the main products are methoxymethane and nitrogen.

Secondary aliphatic and aromatic amines

Aliphatic secondary amines react with HNO2 at room temperature to form nitrosoamines / nitrosamines (yellow oils). R2N-H + HO-N=O R2N-N=O + H2O nitrosoamine Example,

CH3 CH3

N H

HO N=O

CH3 CH3

N N=O

H2O

dimethylamine

N-nitroso-N,N-dimethylamine

Tertiary aliphatic amines

A tertiary aliphatic amines react with HNO2 will produced ammonium salts which is dissolve readily in water as a clear solution. R3N + HNO2 [R3NH]+NO2- (aq)

Primary aromatic amines

A primary aromatic amines react with cold HNO2 and dissolved in dilute HCl at 0-5oC will produced diazonium salt. When this cold salts heated at room temperature, nitrogen gas will evolved.
NH2 HNO2 HCl
5 C
o

N2 Cl

2H2O

RT

N2

mixture products

benzenediazonium chloride RT = room temperature

Tertiary aromatic amines

Tertiary aromatic amines reacts with nitrous acid by undergoing substitution at the para position of the benzene ring to form nitrosoaniline which is a yellow precipitate.

R N R HNO2
< 5oC

R ON N R

a nitosoamiline compound (yellow precipitate)

Amide formation
i) Reaction with acyl chlorides

Primary and secondary amines are acylated at room temperature by acyl chlorides to form N-substituted amides. RNH2 + CH3COCl RNHCOCH3 + HCl R2NH + CH3COCl R2NCOCH3 + HCl
Tertiary amines are NOT acylated because they do not have hydrogen atom attached to the nitrogen atom.

Examples:
H CH3N H H N H O CH3C Cl
ethanoyl chloride

H O CH3N C CH3
N-methylethanamide

HCl

O CH3C Cl
ethanoyl chloride

H O N C CH3
N-phenylbenzamide

HCl

ii)

Reaction with acid anhydrides Primary and secondary amines are readily acylated by acid anhydrides to yield the corresponding N-alkyl or N-aryl amides. For example,
O O H O CH3CH2CH2N C CH3
N-propylethanamide

H CH3CH2CH2N H
propylamine

O HO C CH3 O HO C CH3

CH3 C O C CH3
ethanoic anhydride

H CH3CH2N CH2CH3
diethylamine

O CH3CH2N C CH3 CH2CH3

N, N-diethylethanamide

CH3 C O C CH3
ethanoic anhydride

Ring halogenation of phenylamine

When bromine water is added to phenylamine (aniline) at room temperature, decolorisation of the bromine water occurs and a white precipitate of 2,4-6-tribromoaniline (C6H4Br3N) is obtained. This reaction is used as a test for aniline.
NH2 3Br2 (aq)
room temperature

NH2 Br Br 3HBr Br
2,4,6-tribromoaniline (white precipitate)

USES OF AMINES SYNTHESIS OF NYLON

Nylons are condensation copolymers formed by reacting equal parts of a diamine and a dicarboxylic acids, so that peptide bonds form at both ends of each monomer in a process analogous to polypeptides biopolymers.

General reactions:

Dicarboxylic acids

Diamines

Nylon

Basic concepts of nylon production

The first approach: - combining molecules with an acid (COOH) group on each end are reacted with two chemicals that contain amine (NH2) groups on each end. - Form nylon 6,6, made of hexamethylene diamine with six carbon atoms and acidipic acid, as well as six carbon atoms. The second approach: - a compound has an acid at one end and an amine at the other and is polymerized to form a chain with repeating units of (-NH-[CH2]n-CO-)x. - Form nylon 6, made from a single six-carbon substance called caprolactam.

SYNTHESIS OF DYE
Primary aromatic amines are used as a starting material for the manufacture of azo dyes. Azo compounds: - compounds bearing the functional group R-N=N-R', in which R and R' can be either aryl or alkyl. - N=N group is called an azo group - HNNH is called diimide Aryl azo compounds have vivid colors, especially reds, oranges, and yellows

Yellow azo dye

 Amines react with nitric(III) acid to form diazonium salt, which can undergo coupling reaction to form azo compound. Azo-compounds are highly coloured, they are widely used in dyeing industries, such as: i) Methyl orange ii) Direct brown 138 iii)Sunset yellow FCF iv)Ponceau

Uses and important of azo dye

Methyl orange - used as acid-base indicators due to the different colors of their acid and salt forms Artists paints clays, yellow to red range Dye in food and textiles

E102: Tartrazine

E107 : Yellow 2G
EXAMPLES OF AZO DYES USED IN FOOD

E110 : Sunset Yellow

E122 : Azorubine

E123 : Amaranth

E124 : Ponceau 4R

E129 : Allura Red

E151 : Brilliant Black