Amines

By – A.P.S. Bhadouriya
PGT-Chemistry
KVS
• Alkyl or aryl derivatives of ammonia are
regarded as amines. These are obtained by
replacing one or more hydrogen atoms by alkyl
or aryl groups.

• Amines are classified as primary, secondary or

tertiary depending upon whether one, two or three
atoms of hydrogen have been replaced by alkyl or
aryl grups.
 Nomenclature
• In the trivial system, amines are named as
alkylamine.
• In the IUPAC system, these are named as
alkanamine (replacing ‘e’ of alkane with amine).
 Preparation of Amines:
• 1.Reduction Method-.
• a)Reduction of nitro compounds:

• H2 / Pt or H2/Pd or LiAlH4 may also be used.

• Complete the following reaction-

𝑺𝒏 , 𝑯𝑪𝒍𝒐𝒓 𝑭𝒆, 𝑯𝑪𝒍

→
• (b)Reduction of nitriles:
• (c)Reduction of amides:

• 2.Ammonolysis of alkyl halides:

• The process of cleavage of the C-X bond by
ammonia molecule is known as ammonolysis
 .

If alkyl halide is in excess, the amine formed further

reacts with alkyl halide to form 2°, 3° amines and finally
quaternary ammonium salts.

Primary amine is obtained as a major product by taking

large excess of ammonia
 3.Hoffmann Bromamide Degradation Reaction

• R-CONH2 + Br2 + 4 NaOH  R-NH2 +Na2CO3 +2NaBr + H2O

• In this reaction ,the amine formed contain one
carbon less than those of amide.(R=Alyl or aryl grp.)
• Complete the following reaction

Note – NaOBr may also be used in place of NaOH+Br2

 4.Gabriel phthalimide synthesis

Aromatic amines can not be prepared by this method because aryl halides do
not undergo nucleophilic substitution with the anion formed by phthalimide.
 Practice Questions
• How will you convert:
• (i) Benzene into aniline,
• (ii) Benzene into N,N-dimethylaniline,
• (iii) Cl(CH2)4—Cl into hexan-1,6-diamine
• (iv)Ethanoic acid to methanamine
• (v) Hexanenitrile to 1-aminopentane
 Physical Properties
• The lower members are combustible gases, members
from C3 to C11 are volatile liquids and from C12 onwards
are solids.
• The lower members are readily soluble in water, due
to the formation of hydrogen bond between amine
and water molecules.
• However, in higher amines, the alkyl group
predominates over the amino group with the result
that they have less tendency for forming hydrogen
bond with water that’s why higher amines are
insoluble in water.
• Aromatic amines are insoluble in water. This is because
of the larger hydrocarbon part.
 Chemical Properties
• A)Salt formation :
 • B)Alkylation:

• C) Acylation:
• The replacement of hydrogen atom of -NH2 group by
acyl group is known as acylation

Acid anhydride (R-CO)2O may also be use as acylating agent.

The base stronger than amine, like pyridine is used to removes HCl so formed
• .
• D)Reaction with chloroform (Carbylamine reaction):
• Only primary amine give this reaction
• R-NH2 + CHCl3 + 3KOH R-N≡C + 3H2O + 3 KCl
• Isocyanide / Carbylamine
• (foul smell)
• E) Reaction with Nitrous acid –
• Nitrous acid is prepared in situ from mineral acid and
sodium nitrite
• R NH2 + HNO2 [R-N2+Cl- ] R-OH +N2+HCl
• (Unstable)
• F)Diazotization:

Benzenediazonium chloride is stable due to resonance.

• Electrophilic substitution reactions:
• Due to resonance(+R effect), electron density
increases at ortho and para positions as compared to
meta positions.
• Therefore, —NH2 group directs the incoming group
to ortho and para positions and is ring activator
towards ES reactions.
• Bromination:

The lone pair of electrons on nitrogen is less available for donation to

benzene ring by resonance. Therefore, activating effect of -NHCOCH3 group is
less than that of amino group.
• Nitration:

• In strongly acidic medium, significant amount of meta isomer is

obtained. This is due to the formation of anilinium ion which is
meta directing.
• Friedel–Crafts reaction:
• Due to salt formation, nitrogen of aniline acquires
positive charge and thus acts as a strong deactivating
group and hence does not allow Friedel–Crafts
reaction to occur.
 Test for Amines
• Hinsberg’s test: In this test, the amine is first treated
with Hinsberg’s reagent (benzenesulphonyl chloride) and
then shaken with aqueous KOH solution when the three
amines behave in different ways.
• (i) A 1° amine gives a clear solution
• ii)A 2° amine gives an insoluble N, N-dialkyl benzene
sulphonamide

(iii) A 3° amine does not react at all.

• Isocyanide test (Carbylamine test):
• Primary amines (aliphatic as well as aromatic) react
with chloroform in the presence of alcoholic KOH to
form foul smelling carbylamine.
 Basic Character of Amines:
• Amines have a lone pair of electrons on nitrogen atom due
to which they behave as Lewis base.
• Basic character of amines can be better understood in
terms of Kb and pKb values as explained below.

• Larger the value of Kb or smaller the value of pKb stronger is

the base.
• Basic strength of Alkylamines
• In gas phase, the basic trend in nature is as
• 3o amine > 2o amine > 1o amine > ammonia.
• In aliphatic amines, the electron-releasing alkyl groups
stabilise their ammonium cations by dispersing the
positive charge, and in parent amines make the nitrogen
unshared electrons more available for sharing with a
proton.
• In aqueous solution, the substituted ammonium cations
are stabilised not only by electron-releasing effect of the
alkyl groups but also by solvation with water molecules.
It is a combination of electron-releasing, H-bonding and
steric factors that determine the stability of the
ammonium cations in solution.
• The greater the size of the ion lesser will be the solvation
and less stabilised is the ion.
• So the basicity of methyl substituted amines in aqueous
phase is
• When alkyl group is bigger ethyl group, there will be steric
hindrance to H-bonding with water, so the stability of
substituted ammonium ion decreases. So the basicity of
ethyl substituted amines in aqueous phase:

• Aromatic amines are weaker bases than ammonia and

aliphatic amines because the availability of electron on
nitrogen atom of aniline decreases due to delocalisation
of electron by resonance.
Effect of substituent on the basicity of aromatic amines:
• Incase of aromatic amines, the basicity depends upon:
• a) Inductive effect o- > m- > p-
• b) Resonance effect, observed at o- & p- positions
• Electron-donating groups such as —CH3, —OCH3, –NH2,
etc., increase the basicity.
• Electron-withdrawing substituents such as —NO2, —CN,
halogens, etc., decrease the basicity of amines.
• Among the isomeric toluidines, the basic strength with respect
to aniline decreases as:

• Ortho-substituted anilines are weaker bases than aniline

irrespective of the nature of the substituent. This is called ortho-
effect and it is probably due to a combination of steric and
electronic factors.
 BENZENE
DIAZONIUM
SALT
By- AJAY PRATAP SINGH
PGT-Chemistry
PM SHRI KV BALRAMPUR
PREPARATION
 Benzenediazonium chloride is prepared by the
reaction of aniline with nitrous acid at 273-278K.
Nitrous acid is produced in the reaction mixture by
the reaction of sodium nitrite with hydrochloric acid.
 The conversion of primary aromatic amines into

diazonium salts is known as diazotisation.

 Thediazonium salts have the general formula–
ArN2+X-
 where
Ar stands for an aryl group and –X ion
may be Cl– ,Br– , HSO4− , BF4− , etc
PROPERTIES
 Alkyl diazonium salts are highly unstable .
 Arenediazonium are stable for a short time in

solution at low temperatures (273-278 K) which can

be explained on the basis of resonance.
PHYSICAL PROPERTIES
 Benzenediazonium chloride is a colourless
crystalline solid.

 Solublein water and is stable in cold but

reacts with water when warmed.
CHEMICAL PROPERTIES
 1.Replacement by halide or cyanide ion:
 (a)Sandmeyer Reaction-
 (b)
Gatterman reaction- It is a modification of
Sandmeyer reaction
 2. Replacement by iodide ion:

 3.Replacement by fluoride ion:

 4. Replacement by Hydrogen:

 5. Replacement by hydroxyl group:

 6. Replacement by –NO2 group:
 7.Coupling reactions with phenol and aniline :
 In such reactions benzene diazonium ion acts as an

electrophile and it is an example of electrophilic

substitution reaction.
 Practice Questions
1. Arrange the following in increasing order of their basic
strength: C2H5NH2, C6H5NH2, NH3, C6H5CH2NH2,
(C2H5)2NH
2. (CH3)2NH is more basic than (CH3)3N in an aqueous
solution. Give reason.
3. Write structures of compounds A and B in each of the
following reactions:
4. Write the structures of A, B and C in the following:

5. Write the structures of A, B and C in the following

6. How will you convert the following:

(I) Aniline to chlorobenzene
(ii) Ethanoic acid to methanamine
(iii) Benzene diazonium chloride to phenol
7. Complete the following reactions:
8. How do you convert the following:
(i) N-phenylethanamide to p-bromoaniline
(ii) Benzene diazonium chloride to nitrobenzene
(iii) Benzoic acid to aniline.
9. An aromatic compound ‘A’ of molecular formula C 7H7ON
undergoes a series of reactions as shown below. Write the
structures of A, B, C, D and E in the following reactions:
10. Write the structures of A, B, C, D and E in the following
reactions:

11. How will you bring about the following conversions?

(a) Ethanamine into methanamine
(b) Aniline into 1,3,5-tribromobenzene
(c) Aniline into 4-bromoaniline
12. Account for the following:
(a) Methylamine in water reacts with ferric chloride to
precipitate hydrated ferric oxide.
(b) Diazonium salts of aromatic amines are more stable
than those of aliphatic amines
(c) Acetylation of aniline reduces its activation effect.
(d) CH3NH2 is more basic than C6H5NH2.
(e) Although —NH2 is o/p directing group, yet aniline on
nitration gives a significant amount of m-nitroaniline.

Thank You