INSTA LEARN

PLUS TWO

AMINES
CHEMISTRY
 CH3-N-CH2-CH2-CH3
-----------------------
AMINES C H2-CH3

CH3-N-CH3
CH3 ------------------------------
Amines constitute an important class of or-
ganic compounds derived by replacing one or
more hydrogen atoms of ammonia molecule
by alkyl/aryl group. Preparation of Amines
01. REDUCTION OF NITRO COMPOUNDS

Depending upon the number of hydrogen at- Nitro compounds are reduced to amines by
oms replaced by alkyl or aryl groups in ammo- passing hydrogen gas in the presence of
nia molecule, amines are classified as; finely divide nickel, palladium or platinum and
also by reduction with metals in acidic medi-
 Primary amines (1˚ Amine): um.
Nitrogen is attached to one carbon NH2
 Secondary amines (2˚ Amine):
Nitrogen is attached to two carbon
 Tertiary amines (3˚ Amine):
Nitrogen is attached to three carbon
NH2

Structure of amine
02. REDUCTION OF NITRILES

Nitriles on reduction with lithium aluminium

hydride (LiAlH4) or catalytic hydrogenation
produce primary amines.
1˚1 Amine
Amine 2˚2Amine
Amine 3˚ Amine
0 0

3 Amine
0

H2/ Pd
R - CH2 - NH2
OR

Nomenclature LiAlH4

03. REDUCTION OF AMIDES

1 Amine
0
Alkanamine

2 Amine
0
N-Alkyl Alkanamine

04. AMMONOLYSIS OF ALKYL HALIDES

3 Amine 0
N-Alkyl N-Alkyl Alkanamine
 Alkyl or benzyl halide on reaction with an
alcoholic solution of ammonia undergoes
nucleophilic substitution reaction in which
CH3 - NH2--------------------------------- the halogen atom is replaced by an amino
(–NH2 ) group.
CH3 - CH2 - CH2 - NH2-----------------------
 This process of cleavage of the C–X bond
CH3-NH-CH2-CH3------------------------- by ammonia molecule is known as ammo-
CH3-CH2-CH2-NH-CH2-CH3 ----------------- nolysis.

JOIN AGNI +1 & +2 ONLINE TUITION BATCH CALL NOW 9995 400 800 3
 05. GABRIEL PHTHALIMIDE SYNTHESIS Chemical Reactions
=O O BASIC CHARACTER OF AMINES

=
C C
KOH R-X Amines, being basic in nature, react with acids
NH NK to form salts.
-H2O
C C
In amine, there is an unshared pair of elec-
=

=
O O
trons on nitrogen atom and hence it can
O donate this electron pair. So it acts as a Lewis
base. Basic character of amines can be ex-
=

C COOH
HYDROLYSIS pressed in terms of Kb and pKb.
NR + R - NH2 (pKb = - log Kb)
BAISC MEDIUM COOH
C Greater the value of Kb, smaller will be the pKb
=

O value and stronger will be the base

 Phthalimide on treatment with ethanolic
potassium hydroxide forms potassium salt
of phthalimide which on heating with alkyl
Aliphatic amine vs Ammonia
halide followed by alkaline hydrolysis pro-
duces the corresponding primary amine.  Aliphatic amines are stronger bases than
ammonia. This is due to the +I effect of alkyl
 Aromatic primary amines cannot be pre- groups leading to greater electron density
pared by this method. because aryl halides on the nitrogen atom. But aromatic amines
do not undergo nucleophilic substitution are weaker bases than ammonia. This is
with the anion formed by phthalimide. due to the electron withdrawing nature of
06. HOFFMANN BROMAMIDE DEGRADATION the aryl group
REACTION  Besides inductive effect, there are some
Hoffmann developed a method for prepara- other effects like solvation effect, steric
tion of primary amines by treating an amide hindrance etc. affect the basic strength of
with bromine in an aqueous or ethanolic amines.
solution of sodium hydroxide.

BASIC STRENGTH OF ALIPHATIC AMINE IN

R-NH2+Na2CO3+2NaBr.
GASEOUS STATE
30 > 20 > 10 > NH3

Physical Properties BASIC STRENGTH OF ALIPHATIC AMINE IN

AQUEOUS STATE
1 The order of basic strength in case of meth-
Solubility ∝ yl substituted amines and ethyl substituted
No.of Carbon atoms
amines in aqueous solution is as follows:
R-OH>R-NH2
(C2H5)2 NH >(C2H5)3N >C2H5NH2> NH3
20 30 10
Boiling point
(CH3)2 NH >CH3NH2> (CH3)3 N>H3
R-OH>R-NH2>R-NH-R > R-N-R>R-H 20 30
10
-

Space for Keynotes

JOIN AGNI +1 & +2 ONLINE TUITION BATCH CALL NOW 9995 400 800 4
Arylamine vs Ammonia 05. REACTION WITH NITROUS ACID
+ - H2O
R-NH2 + NaNO2 + HCl R-N2 Cl R-OH + N2 + HCl
Aryl amine is less basic than ammonia
0-5 0
C

CH3-CH2-NH2 + NaNO2 + HCl CH3-CH2-N2 Cl

Reason 0-5 0 C
H2O

The lone pair of electron on nitrogen atom to CH3-CH2-OH + N2 + HCl

be in conjugation with the benzene ring and
thus making it less available for protonation.
Diazotisation
Aromatic primary amines react with nitrous
acid at 0 to 50C (273-278 K) to form aromatic
diazonium salts [Diazotisation].

On the other hand, anilinium ion obtained by

accepting a proton can have only two reso- NH2 N2 Cl
nating structures NaNO2 + HCl

2. ACYLATION 0-5 C 0

Primary and secondary amine are acylated

when treated with acid chloride or acid an-
hydride . Tertiary amines are not acylated
as they do not contain a hydrogen atom on
06. REACTION WITH ARYL SULPHONYL CHLO-
nitrogen.
RIDE - HINSBERG TEST
When acetyl group introduced into the mole-
cule the process is called acetylation Benzenesulphonyl chloride (C6H5SO2Cl) is
known as Hinsberg’s reagent. It is used to
O O
distinguish primary, secondary and tertiary
=
—

Py ridene
C2 H5 - NH2 + CH3 - C - Cl
-HCI
C2H5 - NH - C - CH3 amines and also for the separation of a mix-
O O ture of amines
=
—

Py ridene
C2 H5 - NH- C2 H5 + CH3 - C - Cl
-HCI
C2H5 - N - C - CH3
-

C2H5
O
—
—

Py ridene
C2 H5 - N - C2 H5 + CH3 - C - Cl NO REACTIONS
-

-HCI
C2 H5
soluble in alkail

Benzoylation of amine
O O
=

Pyridene
—

insoluble in alkali.
CH3 - NH2 + Ph - C - Cl CH3 - NH - C - PH
N - METHYL BEZAMIDE
TERTIARY AMINES DO NOT REACT WITH BEN-
ZENESULPHONYL CHLORIDE
04. CARBYLAMINE REACTION
Aliphatic and aromatic primary amine when
warmed with chloroform and alcoholic KOH
solution produce foul smelling Isocynides or Space for Keynotes
Carbylamines.

This is used as a test for primary Amine

R - NC + 3kCl + 3H2O

JOIN AGNI +1 & +2 ONLINE TUITION BATCH CALL NOW 9995 400 800 5
 7. ELECTROPHILIC SUBSTITUTION OF ANILINE Although -NH2 is o/p directing group, yet ani-
line on nitration gives a significant amount of
Due to resonance, electron density increases
m-nitro aniline . Give reason
at ortho and para positions as compared to
meta positions.
Therefore —NH2 group directs the incoming
group to ortho and para positions.

aniline is protonated to form the anilinium ion

which is meta directing. That is why besides
the ortho and para derivatives, significant
(1) BROMINATION OF ANILINE amount of meta derivative is also formed.
Aniline reacts with bromine water at room
temperature to give a white precipitate of
2,4,6-tribromoaniline.
For the preparation of p-nitroaniline, the –NH2
group is first deactivated by acetylation. The
acetanilide thus formed is nitrated followed by
hydrolysed
NHCOCH3 NHCOCH3 NH2

For the preparation of p-bromoaniline, the – NO2 NO2

NH2 group is first deactivated by acetylation.

The acetanilide thus formed is brominated
followed by hydrolysed

03. SULPHONATION

2) NITRATION OF ANILINE Sulphanilic acid contains both acidic and ba-

sic groups and so it forms internal salts called
Direct nitration of aniline with conc. HNO3 and zwitter ions.
conc. H2SO4 gives a mixture of ortho, meta and
para nitroanilines
Why aniline does not undergo Friedal-Crafts
reaction?
Since the catalyst, AlCI3, used in Friedel craft's
reaction is a Lewis acid and Aniline is a Lewis
base, they combine together to form salt. So
the catalyst is not available for the reaction.

JOIN AGNI +1 & +2 ONLINE TUITION BATCH CALL NOW 9995 400 800 6
Diazonium Salt 3. GATTERMANN REACTION

The diazonium salts have the general formula

RN2 X where R stands for an aryl group and x- ion
may be Cl- Br- -HSO4-, BF4-, etc. They are

Preparation of Diazonium salt

4. REACTION WITH HBF4

Chemical reactions
1. SANDMEYER REACTION

5. REACTION WITH MILD REDUCING AGENTS

C2H5OH

2. REACTION WITH Kl

6. REACTION WITH WATER

JOIN AGNI +1 & +2 ONLINE TUITION BATCH CALL NOW 9995 400 800 7
Reaction involving Retention of
Diazonium group (Coupling Reaction)

JOIN AGNI +1 & +2 ONLINE TUITION BATCH CALL NOW 9995 400 800 8