ORGANIC CHEMISTRY

CHM 207

CHAPTER 9:
AMINES
 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
CH3 CH2 NH2 CH3 CH2 N (CH3CH2CH2CH2)4N+ -CI
CH3
ethylamine
ethyldimethylamine tetrabutylammonium chloride

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.

NH2 CH3 NH2

CH3 CH2 CH CH3 CH3 CH CH2 CH2
4 3 2 1 4 3 2 1

2-butanamine 3-methyl-1-butanamine

CH3 CH3
NHCH3 CH3 CH2 CH CH CH CH3
CH3 CH2 CH CH3 N CH3
3 2 1
4 CH3
N-methyl-2-butanamine 2,4, N, N-tetramethyl-3-hexanamine
 The prefix ‘amino’ is used to indicate the presence of
an –NH2 group in a molecule containing more than one
functional group.

 For example,

NH2CH2COOH H2NCH2CH2OH
aminoethanoic acid 2-aminoethanol

OH
NH2 COH

NH2 NH2
2,4-diaminophenol 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
NH2 CH3 1
2 2
NH2 6
3 1 5 3
4 6 4
5 NO2
phenylamine 2-methylphenylamine 4-nitrophenylamine
(aniline) (2-methylaniline) (4-nitroaniline)
• 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 benzene-1,4-diamine
(1,6-hexanediamine) (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 Hydrogen bonding

H N
R H R R
N H N
H 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 CH3
CH3CH2CH2NH2 CH3CH2N H CH3 N CH3
1-propanamine N-methylethanamine N, N-dimethylmethanamine
o
(1o amine) (2 amine) (3o amine)

boiling point: 48.6oC 37.0oC 3.5oC

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 Brønsted-Lowry base because it can accept a proton
from a proton acid.
Reaction of an amine as a nucleophile

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

Reaction of an amine as a proton base

H H
R N H X R -
N H X
H
H
base proton acid 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 K b.

H H
Kb
R N -
H O H R N H OH
H
H

Kb = [RNH3+] [-OH] pKb = - log 10 Kb

[RNH2]

Stronger base have smaller values of pKb

 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 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
 i) 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.
 R NH2 HCl RNH3Cl
primary amine alkylammonium chloride

R2 NH HCl R2NH2Cl
secondary amine dialkylammonium chloride

R3N HCl R3NHCl

tertiary amine trialkylammonium chloride

EXAMPLES:

CH3CH2CH2 NH2 HCl CH3CH2CH2 NH3Cl

n-propylamine n-propylammonium chloride

(CH3CH2)3 N HCl (CH3CH2)3 NH Cl

triethylamine triethylammonium chloride
 ii) 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 N N=O H2O
CH3 CH3
dimethylamine N-nitroso-N,N-dimethylamine
 Tertiary aliphatic amines
 A tertiary aliphatic amines react with HNO 2 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 HNO 2 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
5oC + - 2H2O
RT
N2
HNO2 HCl N2 Cl 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 R
N R HNO2
< 5oC ON N R

a nitosoamiline compound (yellow precipitate)

 iii) 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 O H O
CH3N H CH3C Cl CH3N C CH3 HCl
ethanoyl chloride N-methylethanamide

H O H O
N H CH3C Cl N C CH3 HCl
ethanoyl chloride
N-phenylbenzamide
 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 O
H H O
CH3CH2CH2N H CH3 C O C CH3 CH3CH2CH2N C CH3 HO C CH3
propylamine ethanoic anhydride N-propylethanamide

H O O O O
CH3CH2N CH2CH3 CH3 C O C CH3 CH3CH2N C CH3 HO C CH3
diethylamine ethanoic anhydride CH2CH3
N, N-diethylethanamide
 iv) 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 NH2
Br Br
room temperature
3Br2 (aq) 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
 Artist’s 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