AMINES

CLASSIFICATION & NOMENCLATURE

• Classified as 10 (RNH2), 20 (RR’NH) @ 30

(RR’R’’N) depending on the no. of alkyl @ aryl
groups bonded to the N atom
• Compounds with 4 alkyl @ aryl groups
attached to the N atom are called quatenary
ammonium salt
• These compounds are ionic R’

R’’ N+ R X-

R
 CLASSIFICATION & NOMENCLATURE

• Primary Amine (RNH2)

– IUPAC name, alkanamine
– Common name, alkylamine @ arylamine
– If R is phenyl, compound is called aniline
– If –NH2 is considered as a substituent : amino
 CLASSIFICATION & NOMENCLATURE
methanamine CH3CHCH3
CH3NH2 2-propanamine
(methylamine)
NH2 (isopropylamine)

ethanamine
CH3CH2NH2
(ethylamine)

NH2 NH2

4-ethylaniline
4-aminobenzoic
acid ( (4-ethylphenyl)amine )

COOH CH2CH3
CLASSIFICATION & NOMENCLATURE

1-propanamine
CH3CH2CH2-NH2
(propylamine)

H2N NH2

1,2-ethanediamine
 CLASSIFICATION & NOMENCLATURE

• Secondary Amine, (RR’NH)

– The longest chain as parent’s name
– IUPAC name, N-alkylalkanamine

CH3-NH-CH3 CH3CH2-NH-CH3
N-methylmethanamine N-methylethanamine

CH3CH-NH-CH3
N-methyl-2-propanamine
CH3
 CLASSIFICATION & NOMENCLATURE

NH-CH2CH3

N-ethyl-4-methylaniline NH

N-ethylethanamine
CH3

NH

N-isopropylcyclohexanamine
 CLASSIFICATION & NOMENCLATURE

• Tertiary Amine, (RR’R’’N)

– The longest chain as a parent’s name
– IUPAC name, N-alkyl-N-alkylalkanamine

CH3-N-CH3 CH3CH2-N-CH2CH3

CH3 CH3
N,N-dimethylmethanamine N-ethyl-N-methylethanamine
 CLASSIFICATION & NOMENCLATURE

CH3-N-CH2CH3

N
N-ethyl-N-methylaniline

N,N-diethyl-3-methyl-3-pentanamine
N

N-ethyl-N-methylcyclohexanamine
 PHYSICAL PROPERTIES
• Low Mr of amines have a characteristic of
fishy smell
• Amines are polar & form inter-molecular H-
bonds for 10 & 20 amines (not for 30 amines!)
 PHYSICAL PROPERTIES
• BOILING POINT
• The order of boiling point of some organic
compounds

R-COOH > R-OH > R-NH2 > R-X / R-COH>

R-H
 PHYSICAL PROPERTIES
• For isomeric amines, 10 > b.p. compared to 20
& 30 due to the 10 can form more inter-
molecular H-bonds

H bonds

δ+ H H
δ+ δ-
R-N-H N-H 10 AMINE
δ-
R
 PHYSICAL PROPERTIES
R R
δ+ δ-
R-N-H N-H 20 AMINE
δ-
R
H bonds

R R
R-N-R N-R 30 AMINE
R
 PHYSICAL PROPERTIES
• SOLUBILITY
• Low Mr of amines soluble in water molecules
• Solubility in water decreases with Mr
• All amines are completely miscible in R-OH
due to their ability to form H-bonds & Van der
Waals forces
 BASICITY OF AMINES
• The presence of lone pair of e on the N atom,
makes amines both basic & nucleophilic
• Amines react with acids to form salts

R-NH2 + HCl RNH3+Cl-

RR’NH + HCl RR’NH2+Cl-
RR’R’’N + HCl RR’R’’NH+Cl-
 BASICITY OF AMINES
• Aliphatic amines > basic than NH3 because the
alkyl group is the e releasing group
• Aromatic amines (aniline) < basic than
aliphatic amines & NH3
• This is because the lone pair of e on the N
atom are delocalized together with the  e of
the aromatic ring
 PREPARATION OF AMINES
1. Reduction of nitro compounds
• nitro compounds can be reduced to 10
amine by using one of the following
reagents:-
1. H2 with Ni @ Pd @ Pt catalyst
2. Reactive metals & strong acid , Sn @ Fe @ Zn
with HCl
3. ZnCl2 with HCl
4. LiAlH4 followed by hydrolysis
 [H]
R-NO2 R-NH2

Sn/HCl
(a) CH3CH2-NO2 CH3CH2-NH2

(b) Preparation of aromatic amines from benzene

NO2 NH2
Sn/conc
1.
HNO3 HCl reflux
H2SO4 2. NaOH

+ 6 [H]
 PREPARATION OF AMINES
2. Reduction of nitrile compounds
• Nitrile compounds can be reduced to 10
amines:-
1. H2 with Ni @ Pd @ Pt catalyst
2. LiAlH4 followed by hydrolysis
 [H]
R-CN R-CH2NH2

LiAlH4
(a) CH3CH2-CN CH3CH2CH2-NH2
H+
(b) Preparation of amine starting from alcohol

PCl3
(CH3)2CHCH2-OH (CH3)2CHCH2-Cl

NaCN
LiAlH4
(CH3)2CHCH2CH2-NH2 (CH3)2CHCH2-CN
H+
 PREPARATION OF AMINES
3. Alkylation of NH3 @ alkylamines

NaOH
NH3 + R-X RNH3 +X- RNH2 10
NaOH
RNH2 + R-X R2NH2 +X- R2NH 20
NaOH
R2NH + R-X R3 NH+X- R3N 30

R3N + R-X R4N+X- quaternary ammonium salt

 REACTION OF AMINES
Reaction with nitrous acid (HNO2)
• Nitrous acid is always prepared in situ
• HNO2 reacts with different classes of amines yield
different products

HCl + NaNO2 OH-NO(aq) + NaCl(aq)

Reaction with nitrous acid (HNO2)
1. 10 aliphatic amines
– Yields highly unstable aliphatic diazonium salts which
decompose spontaneously to form carbocations by
evolving nitrogen gas
– The carbocations is stabilized by formation of alkenes, R-
X & R-OH

HO-NO
R-NH2 + NaNO2 +2HX [R-N+ N:X-] + NaX + 2H2O
H2O
aliphatic diazonium salt
- N2
R-X + R-OH + C=C R+ + X-
carbocation
Reaction with nitrous acid (HNO2)
1. 10 aliphatic amines
– Example:-

NaNO2,HCl
CH3CH2CH2NH2 CH3CH=CH2 + CH3CH(OH)CH3 +
0- 50C
CH3CH(Cl)CH3 + N2
 Reaction with nitrous acid (HNO2)
2. 10 aromatic amines
– Yield arenediazonium salts which are stable at temp. <
100C

NaNO2, HCl
-NH2 [ -N+ N:X-] + NaX + H2O
<100C
benzenediazonium salt

• Arenediazonium salts as intermediates in the synthesis of other

aromatic compounds
• Arenediazonium salts are unstable at temp. > 100C
• The reagents are added & warmed gently
 H3O+
-OH phenol

CuCl
-Cl chlorobenzene

CuBr
-N+ N:X- -Br bromobenzene

CuC N
-C N benzonitrile

KI
-I iodobenzene
Arenediazonium ions also undergo coupling reaction (<10oC)with
aromatic compound with strong e donating groups, such as –OH &
-NR2 at the para position, to yield azo compounds
Azo compounds are usually intensely coloured & widely used as
dyes

-OH
-N=N- -OH

(orange)
-N+ N:X- CH3

-N-CH3 CH3

-N=N- -N-CH3

(yellow)
 AMIDES
• Preparation of amides
– Reaction with ammonia produces a primary amide
CH3COCl + NH3  CH3CONH2 + HCl
– Reaction with a primary amine produces a
secondary amide
CH3COCl + CH3NH2  CH3CONHCH3 + HCl
AMINO ACIDS,
PROTEINS and
POLYMERS
 INTRODUCTION
• They contain both an amino group ( NH2) and an
acidic carboxylic group ( COOH).
• Amino acids can join together into long chains by
forming amide bonds between the NH2 of one acid
to the COOH of another acid
• Chains less than 50 amino acids are often called
peptides, while those larger chain are termed as
protein.
• Amino acid commonly found in proteins are -amino
acids.
General Structure:
alkyl

R
O
carboxyl
NH2 C C
OH
H
amino
 carbon

Notice that, the amino Different R groups give

group and the carboxyl the unique characteristic
group are bonded to the of the amino acids
same carbon ( Carbon)
Example:
The simplest
The nextacid
amino member
is of
amino acid
glycine is where
(Gly)
HR3
CH
alanine (Ala) where
O R is a hydrogen
Ratom
is the alkyl group
NH2 C C CH3.
OH
H

Other amino acids contain R groups which are

more complex consisting of carbon, hydrogen,
oxygen, nitrogen and sulphur.
 PEPTIDES
• They are amino acid polymers in which the individual
amino acid unit are linked by amide bonds or
peptide bonds.
• Two amino acids linked by a peptide bond form a
dipeptide.
• Three amino acids form a tripeptide.
• Many amino acids form oligopeptide
• 400 – 10,000 amino acids form polypeptide.
 H O O O O O

H H H H H H H H H
H N C C N C C N C C N C C N C C O

H CH CH2 2HC OH CH2 CH2

3HC CH3
C O SH C CH

O H N NH

C
H

This is a pentapeptide.
That is, it is a chain of 5 amino acids that are
connected by peptide bonds.
 H O O O O O

H H H H H H H H H
H N C C N C C N C C N C C N C C O

H CH CH2 2HC OH CH2 CH2

3HC CH3
C O SH C CH

O H N NH

C
H

A peptide bond is the bond made during the

formation of an amide functional group.
.
 PROTEINS

• Proteins are the connective tissue, catalysts, carriers,

guardians of health, storage, regulation that all living
things need to live.
• Proteins determine skin, hair, eye color, whether our
hair is curly or not.
• Proteins are essential to life.
CLASSIFICATION OF 20 AMINO
ACIDS IN PROTEIN

See your textbook for table of 20 amino

acids in proteins
The first three amino acids are shown in
the next slide
Name Structure
Glycine H CH COOH
Gly
G NH2

Alanine H3C CH COOH

Ala
NH2
A

CH3
Valine
Val HC CH COOH
V
CH3 NH2
 NAMING AMINO ACIDS
• Take the carboxyl group as the parent name whereas
amino group as the substituent.

Longest chain contains 3

Alanine (Ala) carbon atoms, therefore
it is a propanoic acid.
H3C CH COOH

NH2 Amino group is at Carbon no 2.

IUPAC name: 2-aminopropanoic acid

 NAMING AMINO ACIDS
CH3CH(OH)CH-COOH
NH2 2-amino-3-hydroxybutanoic acid
Threonine

HOOCCH2CH-COOH
NH2 2-aminobutanedioic acid
Aspartic acid

H2NCH2CH2CH2CH2CH-COOH
NH2 2,6-diaminohexanoic acid
Lysine
 PHYSICAL PROPERTIES

• Zwitterions

• Because of the presence of both acidic and basic

functional groups, amino acid can undergo an
internal acid-base reaction.
• A proton is transferred from the carboxylic acid to
the amino group.
• The product is called zwitterions
 -
COOH COO
+
H2N C H H3 N C H
R R
uncharged structure dipolar ion or zwitterion

• The dipolar nature of amino acid give them unusual

properties such as:
• High melting point
• More soluble in water than other organic solvent
• They are amphoteric or ampholite (amphoteric
electrolytes) which can react as acid or base
depending on the pH of the solution
Isoelectric Point

• In general , zwitterions are electrically neutral and

exist at a specific pH.
• These pH are called isoelectric point.
• Each amino has its own isoelectric point.
• Example Alanine exists in zwitterion form at pH
6.02
• Symbol is pI
 Exercise
1) The isoelectric point of serine (R= -CH2OH) is 5.7. Draw the form of the
molecule in aqueous solutions of pH 3.0, pH 5.7 and pH 10.0.

2) Draw the structure of tripeptide with the sequence alanine-serine-

aspartic acid
(Ala: R= -CH3 ; Asp : R= -CH2COOH)
 Exercise
• The isoelectric point of alanine is 6.0. If most alanine exist in the form of
H
+
H3N C COOH
CH3
What is the possible pH of the solution?
a) 2.5 b) 6.0 c) 9.7

Answer: (a)
 OPTICAL PROPERTIES
• All amino acids except glycine have chirality
centre.
• So they can rotate plain polarized light.
• Which means they can exist as –D and –L isomers
 How to write the configuration for amino acid?

• The configuration is written where the –COOH group is

at the top and the R group at the bottom.
• If the amino group is left, they are L-amino acid.
• If the amino group is right, they are D-amino acid.

COOH COOH
H2N C H H C NH2

CH3 CH3

L-alanine D-alanine
 Formation of Peptide Bond

O H O
H2N-CH-C-O-H H-N-CH-C-O-H
R R’

Removal of H2O

O H O
H2N-CH-C N-CH-C-O-H
R R’
Peptide bond
 Formation of Peptide Bond

• 2 amino acids form 2 dipeptides

• 3 amino acids form 6 tripeptides
• Example: Glysine (Gly) & Alanine (Ala) can form 2
dipeptides: Glysylalanine (Gly.Ala) and Alanylglysine
(Ala.Gly).
 O O O H O
H2N-CH2-C-OH + H2N-CH-C-O-H H2N-CH2-C N-CH-C-OH
CH3 CH3
glysine alanine glysylalanine (Gly.Ala)

N Terminal C Terminal

O O O H O
H2N-CH-C-OH + H2N-CH2-C-OH H2N-CH-C N-CH2-C-OH
CH3 CH3
alanine glysine alanylglysine (Ala.Gly)
POLYMERS
 Addition Polymerization
• Addition polymerization is the addition
reaction in which unsaturated monomers are
joined together by covalent bonds to form
a polymer without elimination of a small
molecule.
Polymers obtained by addition
polymerization are called addition polymers.
Therefore, addition polymer always involves
the polymerization of monomers which have
double bond within the monomers.
Peroxide is used as initiator in addition
polymerization.
52
i. Formation of polyethene

n CH2 CH2 ROOR -CH

( 2-CH2-
)n

ethene polyethene

ii.Formation of polyvinyl chloride

n HC CH2 ROOR (
-HC-CH 2-
)n
Cl Cl
chloroethene polychloroethene
(polyvinyl chloride or PVC)

53
iii.Formation of polystyrene

n HC CH2 ROOR (
-HC-CH 2-
)n

phenylethene Polyphenylethene
(styrene) (polystyrene)

iv.Formation of polyisopropene

n CH 2=C-CH=CH 2 -CH 2-C=CHCH 2-

CH 3 CH 3 n
isoprene polyisoprene 54
Condensation Polymerization
Condensation polymerization is a process that combines the
monomers with elimination of a small molecule such as water,
methanol, hydrogen chloride or ammonia to form a polymer.

The polymers obtained from condensation polymerization are

called condensation polymers.

The monomers involves in this polymerization must have at

least two identical or different functional group in the
molecule.

When a carboxylic acid with two –COOH group reacts with an

amine with two –NH2 groups, a polyamide is formed.

When a carboxylic acid with two –COOH group reacts with an

alcohol with two –OH groups, a polyester is formed.

55
(A). Polyamides
i. Formation of Nylon 6,6
O O
n H2N-(CH2)6-NH2 + n HO-C-(CH2)4-C-OH
hexane-1,6-diamine hexane-1,6-dioic acid

H H O O
(
-N-(CH 2)6-N-C-(CH2)4-C-
)n + n H2O
Nylon 6,6
ii. Formation of Nylon 6

O O
n H2N-(CH2)5-C-OH (
-NH-(CH 2)5-C-
)n + n H2O
6-aminohexanoic acid Nylon 6 56
iii. Formation of Kevlar
H H O O
n H-N- -N-H + n Cl-C- -C-Cl

1,4-diaminobenzene terephthalic acid

H H O O
N- -N-C- -C n + n HCl

Kevlar
(B). Polyester

The repeating functional groups in this polymer chain are

ester.
The most familiar polyester is polyethylene terephthalate
known as Dacron and Terylene.
57
 The polymer is formed by the reaction of ethylene glycol with
methyl ester or terephthalic acid.
In this process, a molecule of methanol is split out for each
new ester group formed.

i. Formation of Dacron

O O
n CH3O-C- -C-OCH3 + n HO-CH2CH2-OH
1,2-ethanediol
dimethyl terephthalate
(ethylene glycol)

O O
(
-O-CH 2CH 2-O-C- -C-
)n + n CH3OH

Dacron or poly(ethylene terephthalate) metanol

58
ii. Formation of Terylene

O O
n HO-CH 2CH 2-OH + n HO-C- -C-OH
ethane-1,2-diol benzene-1,4-dicarboxylic acid

O O
(
-O-CH 2CH 2-O-C- -C-
)n + n H 2O
water
Terylene

59