AMINES

Proteins, vitamins, alkaloids, hormones all of these

are the naturally occurring amino compounds.
Amines are the nitrogen containing organic compounds.
Many drugs and medicines are the complex amines.
Amines are the organic basic compounds.
H R
These occur in plants & animals, ─ 3H
Amines are used as intermediates H─N─H ┼ 3R R─N─R
in synthesis of dyes, synthetic fibres, medicines & agrochemicals.
e.g. trimethylamine in animal tissues & used as an insect attractant.
Nicotine in Quaternary ammonium salts used as surfactants.
tobacco.
Diazonium salts are the intermediates in preparing variety of
Amines are the organiccompounds
derivatives of ammonia & are supposed
formed by replacing H-atom/s of NH3 by alkyl or aryl group/s.
H H H R
─H ─ 2H
H─N─H ┼ R R─N─H H─N─H ┼ 2R R─N─H
 Classification of Amines
Amines are classified on the basis of the nature of the nitrogen atom.
1) The nitrogen atom in amine if is attached to only one singly bonded
carbon atom is said to be the 10-N atom.
2) The nitrogen atom in amine if is attached to the two singly bonded
carbon atoms is said to be the 20-N atom.
3) The nitrogen atom in amine if is attached to the three singly bonded
carbon atoms is said to be the 30-N atom.
1) Primary Amines:- Amines containing 10-N-atom are 10-amines.
10-amines are characterized by their 10-amino, -NH2 group.
Amines those are supposed to be formed by replacing only one H-atom
of ammonia molecule by an alkyl/aryl group are called as 10-amines.
H H 10-Amines are represented by
─H H
H─N─H ┼ R R─N─H R─NH2 Ar─NH2
10-amines. R─N─H, e.g. CH3-NH2 is Methylamine.
C6H5-CH2-NH2 benzylamine.
CH3-CH2-NH2 is ethylamine.
C6H5-NH2 Phenylamine i.e. Aniline
2) Secondary Amines:- Amines containing 20-N-atom are 20-amines.
20-amines are characterized by their 20-amino, imino, >NH group.
Amines those are supposed to be formed by replacing the two H-atoms
of ammonia by the two alkyl/aryl groups are called as 20-amines.
H R 20
-Amines are represented by
─ 2H R
H─N─H ┼ 2R R─N─H R2N ─H Ar2N ─H
R─N─H e.g. (CH3)2NH is dimethylamine.
(C6H5)2NH diphenylamine i.e. N-phenylaniline
(C2H5)2-NH is diethylamine.

3) Tertiary Amines:- Amines containing 30-N-atom are 30-amines.

30-amines are characterized by their 30-amino, nitrile, N, ≡N, group.
Amines those are supposed to be formed by replacing the three H-atoms
of ammonia by the three alkyl/aryl groups are called as 30-amines.
H R 30-Amines are represented by
─ 3H R e.g. (CH3)3N is
H─N─H ┼ 3R R─N─R R 3 N Ar 3 N trimethylamine.
(C6H5)3N is triphethylamine. R─N─R (C2H5)3N is triethylamine.
(C6H5)N(C2H5)2 is diethylphenylamine. C6H5N(C2H5)CH3 is ethylmethylphenylamine.
 Amines are Bases
As in ammonia, the nitrogen of all the amines is sp3-hybridized.
One of the sp3-orbital has lone pair of electrons.
This lone pair of electrons is the cause of their basic nature.
Amines have pyramidal geometry. N-has valence angle of < 109028’ .
Nomenclature of Amines
Common names
The common names of amines are obtained by writing the common
name of hydrocarbon radical/group followed by the term amine.
e.g. CH3-NH2 has methyl group & amine group, thus by common name
it is methyl amine.CH3-CH2-NH2 is ethyl amine.CH3-CH–CH2-CH3
CH3-CH2-CH2-NH2 is n-propyl amine. CH3 NH2 20-butyl amine
CH3-CH -CH3 is iso-propyl amine.CH3-CH–CH2-NH2
CH3 iso-butyl amine
NH2 2 0
-propyl amine.
CH3-C–CH3
CH3-CH2-CH2-CH2-NH2 is n-butyl amine. 3 0
-butyl amine
NH2
 ─ NH2 aniline Types of 20 & 30 amines
phenyl amine,
There are two types of 20 & 30 amines.
─ NH2
1) Simple 20 & 30 amines:
β-naphthyl amine, The amines with all the alkyl or aryl groups on
NH2 the nitrogen same are called as the
simple 20 & 30 amines.
By the common name simple 20 & 30 amines are
called as the dialky amines & trialkyamines.
α-naphthyl amine, e.g. dimethyl amine CH3-NH-CH3,
─CH2-NH2
diethyl amine CH3-CH2-NH-CH2-CH3,
benzyl amine, Di-n-propyl amine
CH3-CH2-CH2-NH-CH2-CH2-CH3,
─NH--
Di-iso-propyl amine (CH3)2CH-NH-CH-(CH3)2,
diphenl amine trimethyl amine (CH3)3NH
C6H5
─N─-- triethyl amine (C2H5)3NH
Tri-n-propyl amine (CH3-CH2-CH2-)3N
triphenl amine Tri-iso-propyl amine ((CH3)2CH-)3N
 2) Mixed 20 & 30 amines:
The amines with all different alkyl or aryl groups on the nitrogen are
called as the mixed 20 & 30 amines.
The common names of mixed 20 & 30 amines are obtained by writing
the common names of alkyl, aryl groups in an alpha betical order
followed by the term amine. e.g. C2H5-NH-CH3 is ethylmethylamine
C2H5-CH2-NH-CH3 is Methyl-n-propylamine --NH-CH3
C2H5-CH2-NH-C2H5 is ethyl-n-propylamine Methyl-β-naphthyl amine
C2H5-CH2-NH-CH(-CH3)2 is iso-propyl-n-propylamine
C2H5-NH-CH(-CH3)2 is Ethyl-iso-propylamine (C2H5-)2N-CH3 is
C2H5-CH2-N-(CH3)2 is dimethyl-n-propylamine diethylmethylamine
(C2H5-)2N(CH3)-CH2-C2H5 is Ethylmethyl-n-propylamine CH3-CH2
C6H5-NH-C2H5 is ethylphenylamine ─N
CH3-CH-CH3 CH3-CH-CH3
CH3-CH2-N-CH2-CH2-CH3 is ethyl-β-naphthylphenyl amine
─N─ ─N-CH3
Ethyl-iso-propyl-n-propylamine
C6H5-NH-CH3 is Methylphenylamine
Diphenyl-iso-propyl amine
methyl-β-naphthylphenyl amine
 IUPAC names
IUPAC system considers that amines are derivatives of parent
hydrocarbons, alkanes, cyclo-alkanes & arenes.
Amines are therefore by IUPAC system, the amino derivatives of parent
Hydrocarbons.
Their IUPAC names are derived from the name of parent hydrocarbon by
replacing their
─ ending
e ‘e’ by amine. ─e
Alkane amine Alkanamine Benzene + amine Benzenamine
┼
Cycloalkane ─e
+ amine cycloalkanamine
─e ─e
methane + amine methanamine Ethane + amine ethanamine
1) Identify the longest carbon chain of parent alkane containing amino
N.
2) Identify the substituents on the main chain.
3) Identify the positions of substituents on the main chain.
For this, number the C-atoms of main chain from the nearest to amino N.
To express the positions of substituents, Prefix the position number so
obtained to the name of corresponding substituents..
If necessary use di, tri, tetra for the 2, 3, 4 same groups if present.
Similarly use separate position numbers correspondingly.
Finally IUPAC name is written by writing names of substituents in a
an alpha betical order with their prefix position numbers followed
by the name of parent alkane with the change of its ending ‘e’ by.
the term amine with of prefix its position number.
In case of 20-& 30-amines, the smaller hydrocarbon groups are taken
as the term substituents on the amino N-atom.
Such groups on N-atom are numbered by prefix N to their name.
e.g. C2H5-NH-CH3 is N-methylethanamine
C2H5-CH2-NH-CH3 is N-Methylpropan-1-amine
C2H5-CH2-NH-C2H5 is N-ethylpropan-1-mine
CH3-CH-CH3
C2H5-CH2-NH-CH(-CH3)2 is
CH3-CH2-N-CH2-CH2-CH2-CH3
N-iso-propylpropan-1-amine N-Ethyl-N-iso-propylbutan-1-amine
 IUPAC Name
By IUPAC system, these are the derivatives of parent alkanes.
The parent alkanes are the unbranched alkanes.
The IUPAC name is derived by writing the name of parent alkane.
parent hydrocarbon by replacing their ending ‘e’ by amine.
To have parent alkane chain, Select longest C-chain containing α-C.
& the compound is supposed to be derived from such parent alkane.
CH -CH-CH -CHNH -CH The longest chain is of 6- C atoms & not
3 2 2 3

CH2CH3 5 -C. Thus parent alkane is hexane & not pentane.

Identify the( substituents) side chains & amine group & enlist them.
The substituents are, methyl & amino groups.
To have the positions of CH3 & NH2 groups,
Number the main chain carbon atoms, from the end nearest to F.G.
3 4 5 6 4 3 2 1
chloro group.
CH3-CH-CH2-CHNH2-CH3 CH3-CH-CH2-CHNH2l-CH3
2 1 5 6
CH2CH3 Is incorrect CH2CH3 is correct
To express the position of substituents in IUPAC name,
Prefix the position number to the name of corresponding
substituent.
If necessary use di, tri, tetra for the 2, 3, 4 same groups if present.
Similarly use separate position numbers correspondingly.
Finally IUPAC name is written by writing names of substituents in a
an alpha betical order with their prefix position numbers followed
by the name of parent alkane by change of its ending ‘e’ by amine.
Thus IUPAC name of 4 3 2 1
CH3-CH-CH2-CHNH2-CH3 is-
5 6
CH3-CH2CH2CH3 CH2CH3 4-methylhexan-2-amine
6 5 4 3 2 1
CH3-C---CH(CH3)-CH(CH3)--CHNH2-CH2-CH3 is-
7 8
CH2CH3 Parent alkane chain is of 8-C atoms, i.e. of octane
Substituents- 2 ethyl grs, 3 methyl grs, amine gr,
positions- 5,6-diethyl 4,5,6- trimethyl 3-amine
Thus IUPAC is 5,6-diethyl- 4,5,6- trimethyl octan- 3-amine
Finally IUPAC name is 5,6-diethyl-4,5,6-tri-methyloctan-3-amine
 Formula Common name IUPAC name
1) CH3-NH2 Methyl amine methanamine
2) CH3-CH2-NH2 Ethyl amine ethanamine
3) CH3-CH2-CH2-NH2 n-propyl amine Propan-1-amine
4) CH3-CHNH2 -CH3 iso-propyl amine Propan-2-amine
5) CH3-CH2-CH2-CH2-NH2 n-butyl bromide Butan-1-amine
6) CH3-CH2-CHNH2-CH3 sec-butyl amine Butan-2-amine
7) (CH3)2CH-CH2-NH2 iso-butyl amine 2-methylpropan-1-amine
8) (CH3)3C-NH2 ter-butyl amine 2-methylpropan-2-amine
9) (CH3)3CCH2-NH2 neo-pentyl amine 2,2-dimethylpropan-1-amine
10) CH3-CH(CH3)-CHNH2-CH3 ---------- 3-methylbutan-2-amine
11) CH3-C(CH3)2-CHNH2-CH3 ---------- 3,3-dimethylbutan-2-amine
12) CH2-= CH-NH2 vinylamine etheneamine
13) CH2-= CH-CH2-NH2 allylamine prop-2-ene-1-amine
14) 3-methylpentan-2-amine is CH3-CH2-CH(CH3)-CHNH2-CH3
15) hexan-3-amine is CH3-CH2-CH(NH2)-CH2-CH2-CH3
16) 4-ethylcyclohexane-1-amine is H N - -CH2-CH
2 3
C2H5-CH2-NH-C2H5 is N-ethylpropan-1-mine
C2H5-CH2-NH-CH(-CH3)2 is N-iso-propylpropan-1-amine
CH3-CH-CH3
CH3-CH2-N-CH2-CH2-CH2-CH3 N-Ethyl-N-iso-propylbutan-1-amine

C6H5-NH-CH3 is N-phenylmethnamine
C6H5-NH-C2H5 is N-phenylethanamine
CH3-CH-CH3
N,N-diphenylpropan-2-amine
─N--

CH3-CH2 N-(2-naphthyl)-N-phenyl ethanamine

─N

─N-CH3
N-(2-naphthyl)-N-phenyl methanamine
 Methods for the Preparation of Amines
Amine from Alkyl halides: by Ammonolysis
The mixture of 10, 20, 30 amines & quaternary ammonium halides
is obtained by heating alkyl halide with alcoholic ammonia in a sealed
copper tube at 373-383K.
H H +
in Cu-sealed tube H H ─
X
H─N─H ┼ X ─ R 373-383K R─N─H ┼ H-X R─N─H
alcoholic 10-amines. R-ammonium salt.
H R
+
R─N─H ┼ X ─ R
in Cu-sealed tube R H ─
373-383K R─N─H ┼ H-X X
10-amines. 20-amines. R─N─H
R R di-R-ammonium salt.
+
in Cu-sealed tube R H ─
R─N─H ┼ X ─ R 373-383K R─N─R ┼ H-X R─N─R X
20-amines. 3 -amines.
0
tri-R-ammonium salt.
R +
R R
in Cu-sealed tube X─
R─N─R ┼ X ─ R 373-383K
R─N─R
30-amines. 40-ammonium salt.
 Ethylamines from ethyl bromide: by Ammonolysis
The mixture of 10, 20, 30 ethylamines & tetraethyl ammonium halides
is obtained by heating ethyl bromide with alco. ammonia in a sealed
copper tube at 373-383K.
H H
in Cu-sealed tube
H─N─H ┼ Br─ C2H5 373-383K
C2H5 ─N─H ┼ H-Br
alcoholic Ethyl bromide ethylamine
H H┼ H-Br
in Cu-sealed tube
C2H5 ─N─H ┼ Br─ C2H5 373-383K
C2H5 ─N─ C2H5
ethylamine diethylamine
C2H5 C2H5
C2H5 ─N─H ┼ Br─ C2H5 in Cu-sealed tube
373-383K
C2H5 ─N─ C2H5 ┼ H-Br
diethylamine triethylamine
C2H5 +
in Cu-sealed tube
C 2 H5 C 2 H5
C2H5 ─N─ C2H5 ┼ Br─ C2H5 Br ─
373-383K C2H5─N─C2H5
tetraethylammoniumbromide
The mixture is neutralized with dil alkali & then distilled to obtain fractions of ethyl,
diethyl & triethyl amines. tetraethylammoniumbromide remains in distillation flask.
By this method as we get the mixture of 10-amine, 20-amine, 30-amine
& tetra-alkylammoniumhalide & the separation of these form the
is not so easy, is very difficult. method is not of practical use.
mixture
By this method mixture of 10-amine, 20-amine, 30-amine forms due to
The stronger nucleophilic nature of amines than ammonia which causes
reactions of amines with alkyl halides resulting even quaternary
ammonium salts. However,
10-amines can be formed in more amount by using NH3 in excess.
30-butylamines does not form by heating 30-butylbromide with alco. NH3
As 30-butylbromide with alco. NH3 undergoes β-elimination & gives
isobutylene.
CH3 CH3
CH3 ─C─ CH2 ┼ NH3 alco. in Cu-sealed tube CH3 ─C ═ CH2 ┼ NH4Br
373-383K
β-elimination isobutylene
Br H
30-butylbromide
Arylamines are not prepared from arylhalides, as the
nucleophilic substitution of arylhalides is very difficult.
 Amine from Alkyl halides:
by Gabriel Phthalimide Synthesis
i) By Alkylation of Phthalimide

10-amines are obtained from phthalimide by the stepwise actions of

Alcoholic KOH, R-X & aq. NaOH
O O
C C
N─H + HO-K N─ K+ + X─R
C ─ HOH
C
O O O
O C─ONa
C + H ─ ONa
N─R C─ONa +
─ KX C + H ─ ONa O
O R ─NH2
N-alkylphthalimide 10-amine
 Ethyl amine from Phthalimide
Ethylamine is obtained from phthalimide by the stepwise actions of
Alcoholic KOH, C2H5-Br & aq. NaOH
O O
C C
N─H + HO-K N─ K+ + Br─C2H5
C ─ HOH
C
O O O
O C─ONa
C + H ─ ONa
N─C2H5 C─ONa +
─ KBr C + H ─ ONa O
O C2H5 ─NH2
N-alkylphthalimide
Ethyl amine
No over alkylation, i.e. no formation of 2 & 3 amines.
0 0

Aryl amines can not be formed, as Aryl halides do not give nucleophilic
substitution with the anion formed from phthalimide.
ii) Primary Amines by Reduction of Alkyl cyanides
10 amines except methyl amine are prepared by reducing alkyl cyanides
(nitriles) by boiling with sodium & ethanol. This is Mendius Reaction.
C H O-H + Na C H O-Na + [H]
R─C ≡ N + 4H
2 5 R─CH2─NH2
2 5

alkyl cyanide boil 0-

1 alkyl amine

Ethyl amine by reducing methyl cyanides by boiling with Na & ethanol.

(C H O-H & Na) CH3-CH2-NH2
CH3-C≡N + [4H]
2 5

alkyl cyanide boil ethyl amine

n-propyl amine by ethyl cyanides by boiling with Na & ethanol.

(C2H5O-H & Na)
CH3-CH2-C≡N + [4H] CH3-CH2-CH2-NH2
ethyl cyanide boil ethyl amine
iso-propyl amine & tertiary butyl amine i.e. 20 & 30 alkyl amines can not
prepared by this method. iso-butyl amine from iso-propyl cyanide.
CH3 CH3
(C H O-H & Na)
CH3-CH-C≡N + [4H]
2 5

boil
CH3-CH-CH2-NH2
isopropyl cyanide isobutyl amine
2-phenyl-1-ethanamine (β-phenyl ethyl amine) from phenyl aceto nitrile.
(C2H5O-H & Na)
─CH2-C≡N+ 4H ─CH2-CH2-NH2
boil
phenyl aceto nitrile Β-phenyl ethyl amine
For the reduction in place of Na & ethanol, we can use H2 & Raney Ni.
iii) Primary Amines by Reduction of Oximes
10 amines are prepared by reducing oximes with Na & ethanol.
R/H R/H H2O
C H O-H + Na C H O-Na + [H]
R─C=N-OH + 4H R─CH-NH2 +
2 5 2 5

Aldo/keto oxime boil

10/20-alkyl 10-amine
e.g. Methamine by boiling formaldoxime with Na & ethanol/ H2& Ni.
H H
(C H O-H & Na)
H─C=N-OH + 4H + H 2O
2 5
H─CH ─ NH2
formaldoxime boil
Methyl-amine
Similarly ethanamine by boiling actaldoxime with Na & ethanol/ H2& Ni.
H H
(C2H5O-H & Na)
CH3─C=N-OH + 4H CH3─CH ─ NH2 + H2O
acetaldoxime boil
Ethyl-amine
Benzyl amine by boiling formaldoxime with Na & ethanol/ H2& Ni.
H H
(C H O-H & Na)
──C=N-OH + 4H ──CH─NH2 + H2O
2 5

boil
benzaldoxime Benzyl-amine
iso-propyl amine by boiling acetoxime with Na & ethanol/ H2& Ni.
CH3 CH3
(C H O-H & Na)
CH3─C=N-OH + 4H 2 5
CH3─CH─NH2 + H 2O
acetoxime boil
iso-propyl-amine
20-butyl amine from ethyl methyl ketoxime.
CH3 CH3
(C H O-H & Na)
CH3-CH2-C=N-OH + 4H CH3-CH2-CH─NH2 + H2O
2 5

Ethyl methyl ketoxime boil

20-butyl-amine
1-phenyl-1-ethanamine by boiling acetophenonoxime with Na & ethanol
CH3 CH3
(C H O-H & Na)
──C=N-OH + 4H
2 5
──CH─NH2 + H2O
boil
1-phenyl-1-ethanamine
Methyl phenyl ketoxime
 iv) Primary Amines by Reduction of Amides
10 amines are prepared by i) reducing amides with LiAlH4 in ether &
then ii) hydrolyzing the complex with dil. Acid.
NH2 NH2
i) LiAlH in ether
R─C = O + 4H 4
R─CH2 + H 2O
Amide ii) di. Acid/ H3O+
10-amine
e.g. Methamine by boiling formamide with i) LiAlH4 in ether & ii) H3O+.
O
H─C ─NH2 + 4H i) LiAlH in ether4
H─CH2 ─ NH2 + H 2O
ii) di. Acid/ H3O+ Methyl-amine
formamide
Ethanamine by boiling acetamide with i) LiAlH4 in ether & ii) H3O+.
O
CH3─C ─NH2 + 4H i) LiAlH in ether 4
CH3─CH2 ─ NH2 + H2O
acetamide ii) di. Acid/ H3O+
Ethyl-amine
n-propyl amine by boiling propanamide with i) LiAlH4 in ether & ii) H3O+.
O
i) LiAlH4 in ether
CH3-CH2-C-NH2 +4H CH3-CH2-CH2-NH2 + H2O
ii) di. Acid/ H3O+ n-propyl-amine
propanamide
Benzyl amine by boiling benzamide with i) LiAlH4 in ether & ii) H3O+.
O
i) LiAlH in ether
─C─NH2 + 4H
─ 4
─ 2 ─ NH2
─CH + H 2O
ii) di. Acid/ H3O+ Benzyl-amine
benzamide
iso-butylamine from iso-butyramide with i) LiAlH4 in ether & ii) H3O+
CH3 O CH3
i) LiAlH in ether
CH3─CH ─C─NH 2
+ 4H 4
CH 3 ─CH─CH 2 ─NH 2
+ H 2O
ii) di. Acid/ H3O
+
iso-butyramide iso-butylamine

vi) By Reduction of Nitroalkanes

1) Reduction:
Aniline is prepared by boiling nitrobenzene with tin or iron & conc. HCl
─NO2 + 6H 4HCl + Sn SnCl4 + 4[H] ─NH2 +
boil 2H2O
Nitro benzene Aniline
Any primary amine is prepared by the reduction of nitroalkanes by
using Fe/Sn & conc. HCl or LiAlH4 in ether.
 vi)By Reduction of Nitroalkanes
1) Reduction:
Nitroalkanes are reduced by i) tin- conc. HCl, ii) Fe- conc. HCl,
iii) Ni & hydrogen (catalytic reduction), iv) LiAlH4 into 10-amines.
R-NO2 + 6[H] R-NH2 + 2H2O
Nitroethane on heating with tin & conc. HCl is reduced into ethylamine.
Tin & conc. HCl
CH3-CH2-NO2 + 6[H] CH3-CH2-NH2 + 2H2O
Similarly 1-nitropropane on heating with Ni-H2 forms propan-1-amine.
CH3-CH2- CH2-NO2 + 3H2 Rani Niickel CH3-CH2– CH2-NH2 + 2H2O
Similarly 2-nitropropane on heating with LiAlH4 forms propan-2-amine.
H 3C H 3C
LiAlH4
H3C-CH- NO2 + 6[H] H3C-CH- NH2 + 2H2O
In neutral medium with metals nitroalkanes form N-alkyl hydroxylamines.
Nitroethane with Zn in NH4Cl forms N-ethyl hydroxyl amine
CH3-CH2-NO2 + 4[H] Zn-NH4Cl CH3-CH2-NH-OH + H 2O
Stannous chloride & HCl also reduce nitroalkanes into N-alkyl hydroxyl amines
CH -CH -NO + 4[H] SnCl2 HCl
3 2 2 CH -CH -NH-OH + H O
3 2 2
 vii)From amides by Hoffmann bromide
degradation
10-amines are prepared by boiling amides with Br2 & alco. NaOH.
O
Alcohol, boiled
R─C─NH2 + 2Br2 +4NaOH R─NH2 + 2NaBr +
Hoffmann degradation
Amide 10-Amine
Na2CO3 + 2H2O
This reaction is also called as Hoffmann’s degradation as during this
alkyl group from carbonyl C-migrates to the amide N-atom.
Thus reaction is also called as Hoffmann’s rearrangement reaction.
e.g. Ethyl amine is obtained by boiling propanamide with Br2 & NaOH
in ethyl alcohol.
O + 2Br2 +4NaOH Alcohol, boiled C2H5─NH2 + 2NaBr +
C2H5─C─NH2 Hoffmann degradation
propanamide Na2CO3 + 2H2O

Aniline by boiling benzamide with alcoholic NaOH & bromine.

 O
Alcohol, boiled
─C─NH2
─ + 2Br2 +4NaOH
Hoffmann degradation
benzamide
─NH2
─ + 2NaBr +
Na2CO3 + 2H2O
Aniline

Intext Questions
Q. 1) How will you effect following two step conversions?
i) Methyl iodide into ethylamine.
Ans: CH3-I to CH3-CN to CH3-CH2-NH2 (C H O-H & Na)
CH3-I + KCN alco boil CH3-CN
2 5

- KI boil
C2H5─NH2
ii) Propionaldehyde into n-propylamine.
H H
CH3-CH2-C=O + NH2-OH CH3-CH2-C=N-OH
- H2 O
H H
(C2H5O-H & Na)
CH3-CH2-C=N-OH + 4H CH3-CH2-CH-NH2 + H2O
boil
Q. 2) Identify ‘A’ & ‘B’ in the following reactions.
i) ‘A’ + Nitrating Mix. ‘B’ Tin & conc. HCl Aniline
+ HO-NO2 ─NO2 Tin & conc. HCl ─NH2
& H2SO4 + 6H +
H2 O
benzene Nitro benzene
‘A’ ‘B’
(C2H5O-H & Na)
ii) C6H5-CH2-Br ‘A’ ‘B’
+ KCN alco boil
(C2H5O-H & Na)
Ans: C6H5-CH2-Br C6H5-CH2-CN
‘B’ boil
+ KCN alco ‘A’
C6H5-CH2-CH2-NH2
Q. 2) Identify ‘A’, B, C, D, E, F & ‘I’ in following series of reactions.
B NH3 C
NaON/Br
(KMnO /H SO
4 2 A PCl5
4 D 2

CH3CH2COOH CH3CH2COCl CH3CH2CONH2 CH3CH2NH2

CH3-CH2-CH2-OH Red P/Br2
E NH3 F
CH3-CH2-CH2-Br CH3-CH2-CH2-NH2
HBr KCN Na/ethanol
G H I
CH3-CH2-CH2-Br CH3-CH2-CH2-CN CH3-CH2-CH2-CH2NH2
 PCl5
B NH3
(KMnO4/H2SO4 NaON/Br2
A C D
CH3CH2COOH CH3CH2COCl CH3CH2CONH2 CH3CH2NH2
CH3-CH2-CH2-OH Red P/Br2 NH3 F
E
CH3-CH2-CH2-Br CH3-CH2-CH2-NH2
HBr KCN Na/ethanol
G H I
CH3-CH2-CH2-Br CH3-CH2-CH2-CN CH3-CH2-CH2-CH2NH2

A CH3CH2COOH
B CH3CH2COCl
C CH3CH2CONH2
D CH3CH2NH2
E CH3-CH2-CH2-Br G CH3-CH2-CH2-Br
F CH3-CH2-CH2-NH2
H CH3-CH2-CH2-CN
I CH3-CH2-CH2-CH2NH2
 Physical Properties of Amines
1) The lower members are colourless with fishy odour.
2) The 10 amines of three or more C-atoms are liquids.
3) The higher members of 10 amines solids.
4) Aniline & other arylamines are colourless liquids when pure.
But after long time get tarnished (coloured) as are air oxidized by air.
5) Arylamines are generally highly toxic.
6) Solubility:- Amines 10, 20, 30 amines form H-bonding with water.
Thus up to hexyl amines are water soluble.
But the solubility decreases with increase of number of C-atoms.
They are soluble in organic solvents like alcohol, ether, benzene etc.
7) Polarity:- Amines are more polar than alkanes but less than alcohols.
As electronegativity of nitrogen is 3.0 and that of oxygen is 3.5.
The polarity causes 10& 20-amines to form intermolecular H-bonding.
And H-bonding is more in 10-amines due to their two amino H-atoms..
30-amines can not form intermolecular H-bonding due to absence of
amino H-atom. Due to H-bonding they boil at temperature than
alkanesand carboxylic acids.
but lower than alcohols
The order of boiling points is Alkane < amine < alcohol
isomeric 10-branched amine < 10-n-amine > 20-amine > 30-amine
It is clear from the boiling points of following examples.
Name Formula type molar mass B.P. K
1) iso-pentane C2H5CH(CH3)2 Alkane 72 27.8K

2) butan-1-ol C2H5CH2CH2OH Alcohol 74 117.3K

3) di-ethylamine C2H5NHC2H5 20-Amine 73 77.8K

4) Ethyl C2H5N(CH3)2 20-Amine 73 56.3K

di-methylamine
5) 30-butyl amine (CH3)3C-NH2 Branched 73 45.0K
10-Amine
 Intext Question
1) Arrange the following in the decreasing order of their water solubility.
i) Ethyl amine Diethyl amine Tri-ethyl amine
Answer is Diethyl amine > Ethyl amine > Tri-ethyl amine
ii) Ethyl amine n-propyl amine n-butyl amine
Answer is n-butyl amine > n-propyl amine > Ethyl amine
iii) n-butane n-butyl alcohol n-butyl amine
Answer is n-butyl alcohol > n-butyl amine > n-butane
2) Arrange the following in the decreasing order of their boiling points.
i) Ethane Ethyl amine Ethyl alcohol
Answer is Ethyl alcohol > Ethyl amine > Ethane
ii) Ethyl amine n-propyl amine n-butyl amine
Answer is n-butyl amine > n-propyl amine > Ethyl amine
iii) n-propyl amine Ethyl methyl amine tri-methyl amine
Answer is n-propyl amine > Ethyl methyl amine > tri-methyl amine
iv) Ethyl alcohol dimethyl amine tri-methyl amine
Answer is Ethyl alcohol > dimethyl amine > tri-methyl amine
 Chemical Reactions Of Amines
Amines are basic & nucleophilic due to their lone pair of electrons on
nitrogen atom.
i) They react with acids & with electrophiles & form salts.
ii) 10, 20 & 30-amines with certain reagents give different products
because of their different number of H-atoms on nitrogen atom.
1) Basic Nature Of Amines
i) Amines are basic & nucleophilic due to their lone pair of electrons
on nitrogen atom.
Thus amines are electron pair donor, i.e. Lewis bases.

+
:

R─NH2 + X +
R─NH2 X
Amine electrophile
ii) Amines are proton acceptors i.e. Bronsted-Lowry bases.
+
:

H + + R─NH2 R─NH3
iii) Amines in water, like ammonia, form alkyl ammonium hydroxide
which dissociate to give hydroxide ion i.e. Arrhenius bases.
+ ̶ + ̶
:

R─NH2 + H 2 O [R─NH 3 ]OH [R─NH 3 ] + OH

Amine Alkyl ammonium Alkyl ammonium ion
hydroxide ion
iv) Amines with acids form alkyl ammonium salts.
+ ̶
:

R─NH2 + HX [R─NH3]OH
Amine acid Alkyl ammonium salt
e.g. Ethyl amines with dil HCl & form alkyl ammonium chloride.
+ ̶
C2H5─NH2 + HCl [C2H5 ─NH3]Cl
Ethyl amine acid ethyl ammonium chloride
These salts, [C2H5 ─NH3]Cl with NaOH & form parent amine, ethyl
+ ̶
amine. [C2H5 ─NH3]Cl + NaOH C2H5─NH2 + NaCl +
Ethyl amine
These salts are soluble in water but insoluble in ether. H2O
This reaction is used to separate amines from water insoluble non-basic
organic compounds
Aniline in dilute HCl forms a solution of anilinium chlorde.
neutralization + ̶
─NH2 HCl dil. ─NH3 Cl
+
Aniline Anilinium chloride
Phenyl ammonium chloride
or +
─NH3 Cl̶

Ethyl amine with H2SO4 forms a di-[ethyl ammonium] sulphate.

+ ̶̶
2C2H5─NH2 + H2SO4 [C2H5 ─NH3]2SO4
Ethyl amine Di-[ethyl ammonium] sulphate
v) Aqueous solutions of amines are basic. Turn blue litmus to red. as
in water form weak acid alkyl ammonium ion & strong base OH- ion.
+ ̶
R─NH2 + H2O [R─NH3] + OH
Amine Alkyl ammonium ion ion
Weak acid Strong base
 Intext Question
Balanced chemical equations for the action of dilute -
i) Nitric acid on ethyl amine.
Balanced chemical equation is-
+ ̶
C2H5─NH2 + HNO3 [C2H5 ─NH3]2NO3
Ethyl amine [Ethyl ammonium] nitrate
ii) Sulphuric acid on di-ethyl amine.
Balanced chemical equation is-
+ ̶̶
2(C2H5)2NH + H2SO4 [(C2H5)2 ─NH2]2SO4
di-ethyl amine Di-[diethyl ammonium] sulphate
iii) Acetic acid on tri-ethyl amine.
Balanced chemical equation is-
+ + ̶
(C2H5)3N CH3COOH [(C2H5)3 ─NH]2 OOC-CH3
di-ethyl amine
tri-ethyl ammonium acetate
 Basic Strength Of Amines
The basic strength or nature is better explained in terms of their
Kb & pKb values.
+ ̶
[R-NH3] [OH]
K =
[R-NH2] [H2O]
+ ̶
[R-NH3] [OH]
K x [H2O] =
[R-NH2]
+ ̶
[R-NH3] [OH]
Kb = K x [H2O] =
[R-NH2]
The negative log of Kb is equal to pKb . pKb = ─ log Kb
Thus, stronger the base higher will be the value of Kb.
and lower will be the value of pKb.
 Basic Strength Of Amines
Kb & pKb values of some amines in aqueous bases (amines)
Sr. No. Amine Kb pKb
1 methylamine 4.5 x 10-4 3.38
2 ethylamine 5.1 x 10-4 3.29
3 iso-propylamine 2.0 x 10-5 4.70

1 N-methylmethanamine 5.4 x 10-4 3.27

2 N-Ethylethanamine 10.0 x 10-4 3.00

1 N,N-dimethylmethanamine 00.6 x 10-4 4.22

2 N,N-diethylethanamine 05.6 x 10-4 3.25
0 Ammonia 1.8 x 10-5 4.75
1 Benzenamine 4.2 x 10-10 9.38
2 N-methylaniline 7.1 x 10-10 9.30
3 N,N-dimethylaniline 11.7 x 10-10 8.92
Consider to compare the stability of ammonia & amines & their ions;
H H A) Alkyl group of R-NH is 2
H─N: + H +
H─N +
H electron releasing group.
H H Increases electron density on
[Ammonium ion] nitrogen atom of amines.
H H Alkyl amines hold proton firmly.
+
R N: + H+ R N: H
H H Alkyl amines are stronger bases
[alkyl ammonium ion] than ammonia.
R R
H H
H─N: R N: R N: R N:
H H H
R
[Ammonia 10-Amine 20-Amine 30-Amine

In gaseous phase, basic strength is as expected, 10 < 20 < 30 > NH3

In aqueous phase, hydration of R-NH+3 ion is decides it.
i) Greater is size of R-NH+3 ion, lesser is solvation, lesser the stability.
i) Greater is size of R-NH+3 ion, lesser is solvation, lesser the stability.
ii) In 20 & 30 amines, due to larger, bulky R-groups, sterric hindrance
decreases the number of water molecules approach closely to solvate it.
Thus the order of basicity of aliphatic amines should be 10 > 20 > 30.
therefore, to compare the basicity of amines,
inductive effect, solvation effect & sterric hindrance must be
considered.
For ethyl amines it is- (C2H5)2NH > (C2H5)3N > (C2H5)NH2 > NH3.
But for methyl amines it is- (CH3)2NH > CH3 NH2 > (CH3)3N > NH3.
B) In aryl amines, -NH2 group is attached to the benzene ring.
The lone pair of electrons of N-atom is in conjugation with benzene ring.
So lone pair of electrons of N-atom is less available for the protonation.
It is delocalized due to resonance effect
e.g. aniline has thus five resonating structures.

+
+

H2N: H2 N

:
H2 N H2 N H2 N

(-) (-)

i ii (-) iii iv v
While anilinium ion has only two resonating structures.

H 3N+ H2N+

i ii
Aniline has five resonating structures is more stable than
anilinium ion as it has only two resonating structures.
More the resonating structures more the stability.
Thus aniline or any other aryl amine accept proton less readily & are
less basic than ammonia.
Aniline substituted with electron releasing groups like –OCH3, -CH3,
-NH2 etc. is more basic than aniline.
Aniline substituted with electron withdrawing groups like –NO2,
-C6H3, -SO3, -COOH, -CN, -X etc. is less basic than aniline.
 Intext Question
1) Arrange the following in decreasing order of their basic nature.
i) aniline, propan-1-amine and N-methylethanamine
Answer is N-methylethanamine > propan-1-amine > aniline.
ii) benzene-1,4-diamine, ammonia and 4-aminobenzoic acid.
Answer is ammonia > benzene-1,4-diamine > 4-aminobenzoic acid.
iii) N-methylaniline, phenyl methylamine, N-phenylaniline.
Answer is N-methylaniline > phenyl methylamine > N-phenylaniline.
2) Arrange the following in increasing order of their pKb values.
i) aniline, N-methylaniline and cyclohexylamine.
Answer is cyclohexylamine > N-methylaniline > aniline.
ii) phenylmethylamine, 2-aminotoulene and 4-fluoroaniline.
Answer is 2-aminotoulene > phenylmethylamine > 4-fluoroaniline.
3) Arrange gaseous bases in decreasing order of their basic strength.
ammonia, N-methylethanamine, propan-1-amine & trimethanamine.
Answer is trimethanamine > N-methylethanamine > propan-1-amine >
ammonia.
 2) Action of Nitrous Acid (HNO2)
1)Nitrous acid is unstable so prepared at the time of reaction, in situ as.
Na-NO2 + H-Cl Na-Cl + HNO2
Na nitrite Nitrous acid
10, 20 and 30-amines react differently with nitrous acid.
i) Primary amines except methyl amine react with cold nitrous acid
and form unstable aliphatic diazonium salt, decomposing into R-OH.
i.e. alcohols & liberate nitrogen gas.
273 -278 K + ̶ + NaCl
R─NH2 Na-NO2 2H-Cl [R─N2] Cl 2H2O
1 -amine
0 + + Alkyl diazonium
+
chloride salt
+ ̶
[R─N2] Cl + H2O R─OH + HCl
alcohol
Ethyl amine with nitrous acid at 273-278K forms ethanol & N2-gas.
Ethanamine
C2H5─N H2 273 -278 K C2H5─OH
+ + H2O + N2
Na-NO2 + HCl Ethyl alcohol
HO-N O
Nitrous acid
Aromatic amines with nitrous acid at 273-278K forms diazonium salts.
273 -278 K + ̶ + NaCl
Ar─NH2 Na-NO2 2H-Cl [Ar─N2] Cl 2H2O
aryl-amine + + Aryl diazonium
+
chloride salt
aniline with nitrous acid at 273-278K forms benzene diazonium salts.
+
─NH2 2H-Cl ─N2 ̶ + NaCl
+ 273 -278 K Cl
+ Na-NO2 + 2H2O
Aniline
Benzene diazoniumchloride
Propan-2-amine with nitrous acid at 273-278K forms propan-2-ol & N2.
Propan-2-amine
(CH3)2C─N H2 273 -278 K (CH3)2C ─OH + H2O + N2
+ Na-NO2 + HCl Propan-2-ol
Nitrous acid HO-N O

Methyl amine with nitrous acid forms dimethyl ether, N-nitroso amine &
Methylammonium nitrite.
CH3─NH2 + HO-N=O CH3─NH─N=O + H2O
CH3─NH2 + H2N─CH3 + HO-N=O CH3─O─CH3 + H2O
+ ̶ + NH3 + N2
CH3─NH2 + HO-N=O [CH 3 ─NH 2 ] NO2
ii) All the (aliphatic & aromatic) secondary amines react with cold
nitrous acid and form yellow oily N-nitroso-amines.
R R
273 -278 K
R─N─ H + HO ─ N ═ O R─N─N ═ O + HO ─H
Na-NO2 + HCl
2 -amine
0 N-nitroso-20-amine
Diethyl amine with nitrous acid at 273-278K forms yellow & oily
N-nitrosodiethylamine.
C2H5 C2H5 + HO ─H
273 -278 K
C2H5─N─ H + HO ─ N ═ O Na-NO + HCl C2H5─N─N ═ O
diethyl-amine
2
N-nitroso-diethyl-amine
N-ethylaniline with nitrous acid at 273-278K forms yellow & oily
N-ethyl-N-nitrosoaniline.
C2H5 C2H5 + HO ─H
273 -278 K
─N ─ H + HO ─ N ═ O ─N ─N ═ O
Na-NO + HCl
2
N-ethyl-aniline N-ethyl-N-nitroso-aniline
dimethylamine with at 273-278K forms yellow & oily N-nitrosodom-
ami 273 -278 K +
(CH3)2N─ H + HO ─ N ═ O (CH3)2N ─N ═ O HO H
Na-NO + HCl
dimethyl-amine 2
N-nitroso-dimethanamine
iii) 30-amines as bases react with nitrous acids & form Nitrite salts.
Actually no visible change is observed. So said as no reaction.
R +
R
273 -278 K R─N─H ̶
R─N─R + HO ─ N ═ O NO 2
30-amine
Na-NO +2HCl R
Tiralkylammonium Nitrite
triethyl amine with nitrous acid forms triethyl ammonium nitrite salt.
273 -278 K
[(C H ) NH] + ̶
NO
(C2H5)3N + HO ─ N ═ O Na-NO2 + HCl
2 5 3 2
Tri-ethyl-amine Tirethylammonium Nitrite
Aromatic ter-amines with nitrous acid give electrophilic substitution on
the ring carbon & form nitroso ter-amines.
e.g. N,N-dimethylaniline with nitrous acid gives 4-nitroso-N,N-dimethyl
aniline. 273 -278 K ─NO
─H + HO─N═O (CH 3 ) 2 N─ +
(CH3)2N─ Na-NO + HCl
2 4-nitroso-N,N-dimethylaniline
N,N-dimethylaniline Electrophilic substitution
HO H
 3) Acetylation of Amines
3) Action of Acid anhydride & Acid chloride
Acetylation:- The process of replacement of amino-H of amines by
the Acetyl, (CH3-CO-) is called acetylation of amines.
Acetylation reaction reaction is the nucleophilic substitution reaction
Acetylating Reagents:- The reagents are O
O O CH3─C
1) acetic anhydride (CH3CO)2O, CH3─C─O─C─CH3. CH ─C O
3

O
O O

O
2) acetyl chloride CH3COCl, . CH3─C─Cl CH3─C─Cl C─CH3
Cl
Acetic anhydride is obtained by dehydrating acetic acid with conc.H2SO4
O

C─CH3 +
2CH3─COOH. ∆,conc H2SO4 O HO H
C─CH3
O

Acetylchloride is obtained by heating acetic acid with PCl5/SOCl2

∆ O
CH3─COOH. + SOCl 2 + SO2
CH3─C
Cl
Acetylation carried out in stronger base than amines. + HCl
 3) Acetylation of 10-Amines
10-amines with acetic anhydride or acetyl chloride in stronger base like
Pyridine (C5H5N) form monoacetyl amines, amides which with excess of
reagent on strong heating form diacetyl amines, diamides.
O
H C─CH3
R─N O ∆, pyridine
H + C─CH acetylation
3 +

O
O

1 -amine
0
C─CH3
R─N HO
H
tion monoacetyl-10-amine C─CH3

O
ty l a
H ace N-alkyl acetamide
O

R─N + C─CH3 OR
H Cl H-Cl

2nd acetylation-

O
C─CH3 HO
O

C─CH3 ∆, pyridine
R─N C─CH3
R─N Strong ∆ C─CH3 +

O
H
O

C─CH3 O
+ O diacetyl-10-amine
C─CH3 N-acetyl-N-alkyl acetamide
O
 Mechanism of Acetylation of amines
10-amines with acetic anhydride or acetyl chloride in stronger base like
̶
H H O

:
O
:

R─N + C─CH3 R─N ─ C ─CH3

H Cl
10-amine Acid chloride H Cl
intermediate

O
+ R─N ─ C ─ CH3
H
HCl
Amide
Ethyl amine with acetic anhydride or acetyl chloride in pyridine 1 st gives
monoacetyl ethyl amines, N-ethylacetamide which with excess of
reagent on strong heating form di-acetyl ethylamine, N-acetyl-N-ethyl-
acetaamide.

H C─CH3 O
C2H5─N O ∆, pyridine
H + C─CH3 acetylation +

O
O

Ethylamine C─CH3
C2H5 ─N HO
H
tion monoacetylethylamine C─CH3

O
ty l a
H ace N-ethyl acetamide
O

C2H5 ─N + C─CH3 OR
H Cl H-Cl

2nd acetylation-

O
C─CH3 HO
O

∆, pyridine
C─CH3 C2H5 ─N C─CH3
C2H5 ─N Strong ∆
C─CH3 +

O
H
O

C─CH3 O
+ O diacetylethylamine
C─CH3 N-acetyl-N-ethyl acetamide
O
Aniline with acetic anhydride or acetyl chloride in pyridine 1st gives
monoacetyl aniline, N-phenylacetamides which with excess of reagent
on strong heating form di-acetyl aniline, N-acetyl-N-phenyl-acetamide.

O
C─CH3
O
H C─CH3 C6H5 ─N +
C6H5─N O ∆, pyridine H
H + C─CH3 acetylation
O
Monoacetyl aniline HO
N-phenyl acetamide C─CH3
Aniline

O
Acetanilide

O
C─CH3 HO
O

∆, pyridine
C─CH3 C6H5 ─N C─CH3
C6H5 ─N Strong ∆
C─CH3

O
H
O

O
C─CH3
+ O diacetylethylamine
C─CH3 N-acetyl-N-ethyl acetamide
O

Ethyl amine with benzyol chloride in pyridine 1st gives N-ethyl benzamide.

O
H C─C6H5 +
O

C2H5 ─N + C─C6H5 ∆, pyridine C2H5 ─N H

H Cl
Benzoyl chloride
acetylation
N-ethyl benzamide HO
C─CH3

O
 3) Acetylation of 20-Amines
20-amines with acetic anhydride or acetyl chloride in stronger base like
Pyridine (C5H5N) form monoacetyl amines, amides only.

O
C─CH3
H
O O
C─CH3
∆, pyridine R ─N
R
+
R─N + HO
R C─CH3 acetylation acetyl 20-amine C─CH3
O
20-amine

O
diethylamine with acetic anhydride or acetyl chloride in pyridine gives
N-acetyldiethylamine.

O
C─CH3
O

C─CH3 C H ─N +
H O ∆, pyridine 2 5
C2H5 HO
C2H5 ─N + C─CH3 acetylation
C2H5 acetyl 20-amine C─CH3
O

O
Ethylphenylamine with acetic anhydride or acetyl chloride in pyridine gives
N-acetyl ethyl phenyl amine.

O
H C─CH3
O

+ O C─CH3 ∆, pyridine C6H5 ─N +

C6H5 ─N C2H5 HO
C2H5 C─CH3 acetylation N-acetyl ethyl phenyl amine. C─CH3
O

O
Reaction is also performed by using acetyl chloride.
 3) Acetylation of 30-Amines
30-amines are without H-atom on amino nitrogen i.e. without amino H.
Thus 30-amines can not be acetylated.
30-amines can not react with any acetylating reagent.
Therefore 10, 20 & 30-amines are distinguished by their acetylation.
As 1) 10-amines undergo double acetylation & form diacetyl amines.
2) 20-amines undergo single acetylation & form monoacetyl amines.
3) 30-amines are not acetylated at all & remain unaffected.
4) Alkylation of Amines
4) Action of Acid Alkyl halides
Hoffmann’s Exhaustive Alkylation
Alkylation:- The process of replacement of amino-H of 10 & 20-amines
by the Alkyl, (R-) is called alkylation of amines.
H alkylation H + X─R R +
R─N + ─ HX R─N alkylation R─N X─R
H X─R R ─ HX R
10-amine 2 -amine
0
3 -amine
0
Exhaustive
alkylation [R4N]+X- tetra-alkyl ammonium salt
Alkylation of amines follow SN2 reaction mechanism.
Alkylation of amines is not feasible 30-alkyl halides.
As it with 30-alkyl halides prefers elimination predominantly .
10-Amines on heating with alkyl halides give the mixture of 20-amines,
30-Amines & tetra-alkyl ammonium halide i.e. quaternary ammonium
halide salts, quaternary ammonium salts.
H Alkylation, ∆ H +Alkylation,
X─R ∆ R +
R─N R─N R─N
H + X─R ─ HX R ─ HX R X─R
1 -amine
0 2 -amine
0
3 -amine
0
∆ Exhaustive
alkylation [R4N]+X- tetra-alkyl ammonium salt
With excess of alkyl halide only tetra-alkyl ammonium halide salts,
quaternary ammonium salts formed.
10-Amines on heating with the three molecules of alkyl halides,
20-Amines on heating with the two molecules of alkyl halides and the,
30-Amines on heating with the one molecules of alkyl halides form
quaternary ammonium salts .
∆ Exhaustive
R─NH2 + 3X─R alkylation [R4 N] X + 2HX
+ -

10-amine tetra-alkyl ammonium salt

 ∆ Exhaustive
R2N─H alkylation [R4N]+X- + HX
+ 2X─R
20-amine tetra-alkyl ammonium salt
∆ Exhaustive
R2N─R alkylation [R4N]+X-
+ X─R
30-amine tetra-alkyl ammonium salt
Exhaustive alkylation is carried out by using weak base Na2CO3 to
to neutralize HX formed.
If reaction is by using methyl iodide then reaction is called as
Exhaustive methylation. to
Methyl amine with methyl iodide forms tetra-methyl ammonium iodide.
CH3─NH2 + 3I─CH ∆ Exhaustive [(CH3)4N]+I- + 2HI
alkylation
methylamine 3 tetra-methyl ammonium iodide
dimethyl amine with methyl iodide forms tetra-methylammonium iodide.
(CH3)2NH + 2I─CH ∆ Exhaustive [(CH3)4N]+I- + HI
alkylation
dimethylamine 3 tetra-methyl ammonium iodide
trimethyl amine with methyl iodide forms tetra-methylammonium
iodide.
(CH3)3N + I─CH ∆ Exhaustive
[(CH3)4N]+I-
alkylation
dimethylamine 3 tetra-methyl ammonium iodide
 Intext Question
Predict the products of exhaustive methylation of-
1) Ethyl amine on exhaustive methylation gives ethyl trimethyl ammonium iodide.
Answer Reaction is-
C2H5─NH2 + 3I─CH ∆ Exhaustive
[(CH3)3N(C2H5)]+I- + 2HI
alkylation
ethylamine 3 Ethyl tri-methyl ammonium iodide
2) diethyl amine on exhaustive methylation gives diethyl dimethyl ammonium
iodide. Answer Reaction is-
(C2H5)2NH + 2I─CH ∆ Exhaustive
[(CH3)2N(C2H5)2]+I- + HI
alkylation
diethylamine 3 Di-ethyl di-methyl ammonium iodide
3) benzyl amine on exhaustive methylation gives benzyl trimethyl ammonium
iodide. Answer Reaction is-
∆ Exhaustive
C6H5─CH2─NH2 alkylation [C6H5─CH2─N(H3)3]+ I- + 2HI
+ 3I─CH benzyl trimethyl ammonium iodide
ethylamine 3
 5) Hoffmann’s β-Elimination
Tetra alkyl ammonoium halide is heated with moist silver oxide, Ag2O
Ag2O + H2O i.e. Ag(OH), give Tetra alkyl ammonium hydroxide.
Ag2O + H2O
[R4N] X
+ -
+ Ag─OH [R4N]+OH- + Ag─I
tetra-alkyl ammonium salt tetra-alkyl ammonium hydroxide
Tetra alkyl ammonium hydroxides are strongly basic like alkali
Tetra alkyl ammonium hydroxides are crystalline & deliquescent solids.
Na/KOH.
Quaternary ammonium hydroxides having β-H atom on strong heating
Give i) least substituted alkene ii) 30-amine & iii) water.
Water is formed by the elimination of β-H atom and hydroxy group.
e.g. Ethyltrimethyl ammonium iodide on strongly heating with moist
Ag2O + H2O i.e. Ag(OH), under goes its hydroxide which under goes
β-elimination and gives i) ethene, ii) trimethyl amine & iii) water.
+ CH +
α CH3
Ag O + H O
β 2
─ Ag-OH
2 β α 3 ─
CH2-CH2-N-CH3 I CH2-CH2-N-CH3 OHβ-elimination
H CH3 + ─Ag-I H CH3 Strong heated
β α
β-elimination CH2═CH2 + (CH3)3N + HOH.
Ethyl-n-propyl dimethyl ammonium iodide on strongly heating with moist Ag 2O gives
i) Ethene ii) dimethyl-n-propylamine iii) water

CH + Ag O + H O CH +
β α 3 ─ Ag-OH
2 2
β α 3 ─
CH2-CH2-N-CH3 I CH2-CH2-N-CH3 OH β-elimination
H CH2 + ─Ag-I H CH2 Strong heated
βC2H5 βC2H5

β CH3
β α α
CH2═CH2 + CH2-CH2-CH2-N-CH3 + HOH.
Here least substituted ethene is formed in preference to
propene, (methyl substituted ethene).
The reaction is called as Hoffmann’s β-elimination.
 6) Action of Arylsulphony Chloride
6) Hinsberg’s Test.
10-amines with benzene sulphonyl chloride form alkyl benzene
sulphonamides (compounds with acidic H attached to the amide N).
sulphonamides are the strongly acidic as N-is attached to the strongly
electron withdrawing sulphonyl, O Group.
O C6H5-S─N─C2H5
H O H
Strongly acidic
C6H5-S─Cl N─R H-atom.
H 0 O
O + 1 -amine
+ H-Cl
Benzene sulphonyl
C6H5-S─N─R
Strongly acidic
chloride O H
H-atom.
Benzene sulphonamide
These benzene sulphonamides being strongly acidic dissolve in aq. KOH.
The solutions of benzene sulphonamides formed with aq. KOH are
Reprecipitated with acid due to reformation of sulphonamides.
e.g. ethyl-amines with benzene sulphonyl chloride form ethyl benzene
-sulphonamide which dissolves in aq. KOH & regenerated with acid.
O O
C H -S─N─C H + H-Cl
─ S─Cl H 6 5 2 5
N─C2H5 O H
Strongly acidic
O +H H-atom.
Ethyl amine
Benzene sulphonyl
2chloride
0
-amines with benzene sulphonyl chloride form N,N-dialkyl benzene
sulphonamides (compounds without acidic H attached to the N).
N,N-dialkyl benzene sulphonamides does not dissolve in aq. KOH.
e.g. di-ethyl-amines with benzene sulphonyl chloride form N,N-diethyl-
benzenesulphonamide which does not dissolve in aq. KOH being neutral
O O
─ S─Cl H─N─C2H5 C6H5-S─N─C2H5
+ H-Cl
O + C2H5 O C2H5
diethyl amine
diethylbenzene sulphonamide
Benzene sulphonyl
chloride has no acidic hydrogen.
is insoluble in aqu. KOH
.:
30-amines react with benzene sulphonyl chloride but differently.
30-aminecompound with C6H5-SO2Cl insoluble in aq. KOH but in acid.
Thus, 10-amines, 20-amines & 30-amines are distinguished by the
action of benzene sulphonyl chloride, Hinsberg’s reagent..
Amine if treated with C6H5-SO2Cl, Hinsberg’s reagent & then KOH if
1) It dissolves & reprecipitates with acid then amine is if 10-amines.
2) It do not dissolve & also not in acid then amine is if 20-amines.
3) It do not dissolve & but dissolves in acid then amine is if 30-amines.
C6H5-SO2-NH-R KOH C6H5-SO2-N-K+-R H
+
1) C6H5-SO2Cl + H2N─R
C6H5-SO2-NH-R
KOH H+ dissolves
2) C6H5-SO2Cl + H─NR2 C6H5-SO2-NR2 C6H5-SO2-NR2
Insoluble in KOH
KOH
3) C6H5-SO2Cl + NR3 C6H5-SO2-N+R3Cl- C6H5-SO2+ + NR3 + Cl-
Insoluble in KOH
However, these days in stead of C6H5-SO2Cl, Hinsberg’s reagent
p-toulene sulphonyl chloride is preferentially used. O
─ S─Cl
p-toulene sulphonyl chloride CH3─
 Intext Question
Predict the products of exhaustive methylation of-
1) C6H5-SO2Cl + HN(CH3)2 Product is C6H5-SO2 -N(CH3)2 + HCl
2) Product is
O
N-H + C─(CH2)4-CH3 + HCl

O
Cl C─(CH2)4-CH3
N
3) CH3
CH3─CH─CH2─NH2 + HNO2 Product isCH3 + H2O + N
2
CH3─CH─CH2─OH
4) C H -CH ─N (CH ) + HNO Product is
6 5 2 3 3 2

O=N─ ─CH2─N (CH3)3

5)
─NO2 + 6H 2HCl + Zn ZnCl2 + 2[H] ─NH2 +
boil Product is 2H2O
Nitro benzene Aniline
6) Explain, why N,N,2,6-tetramethylaniline is a much stronger base then
N,N,-dimethylaniline.
CH3 CH3 CH3
─N─CH3 is more basic than ─N─CH3
─CH3
1) 2)
Answer:-
Both 1 & 2 have i) benzene ring & ii) N,N-dimethyl groups
same.
but 1 is much more basic than 2.
This is due to its two electron repelling methyl groups at is 2 & 6 proper positions.
Which makes N-atom of it highly electron rich, in turns it is very good e - donor.
In turns 1 is much stronger base than 2.
 7) Electrophilic Aromatic Substitution
Aromatic (aryl) amines have two functional groups, i.e. bifunctional.
The two functional groups are i) NH2 group ii) aromatic ring.
Therefore, arylamines give electrophilic substitution at their benzene
The amine -NH2, -NHR & -NR2 groups are ortho & para directing &
ring
And powerful ortho & para activating groups.
e.g. aniline has five resonating structures with high electron density on
ortho & para positions as in structures. ..
.. NH2
NH2 NH
+
2 NH
+
2 NH
+
2
. ̶. . ̶.

i ii iii . ̶ . iv v
1) Bromination: Aniline with bromine water at forms
. . 2,4,6-tribromoaniline.
.. NH2
NH2
Br─ ─Br
+ 3Br - Br HOH + 3HBr
bromination
2,4,6-tribromoaniline.
Br
-NH2 gr. is powerful ortho para directing & actvating group, so bromination is at all positions.
To prepare monosubstituted derivatives of aniline, -NH2 gr is deactivated
by protecting, blocking by acetylation, with acetyl, –CO-CH3group.
after monosubstitution it is resumed by acid hydrolysis.
Blocking of –NH2 gr.

O
H C─CH3

O
C6H5 ─N + C─CH3 ∆, pyridine C6H5 ─NH
aniline H Cl
acetylation
N-acetyl aniline HO
acetyl chloride C─CH3

O
O
Ar─N─ C ─ CH3 is less reactive than -NH2 group.
H It is ortho para deactivating group for electrophilic
Amide Attack due to its electron withdrawing –C=O group.
O O

. ̶.
.. +
─N─ C ─ CH3 ─N═ C ─ CH3
H H
The + ve charge on N-atom makes benzene ring
electron deficient, in turn deactivate it.
in turn favors monosubstitution.
Monobromination: Aniline is heated with acetic anhydride forms acetanilide
acetanilide on treatment with bromine in acetic acid forms p-bromo acetanilide
which on treatment with dil. Acid is hydrolyzed to give p-brominoaniline.
..
. . C─CH

O
NH2
O
+
+ O C─CH3 ∆, pyridine HN 3
HO
O C─CH3 acetylation C─CH3

O
acetanilide

. . C─CH . . C─CH
O

O
HN 3 HN 3

CH3COOH
+ Br - Br +
bromination 3HBr
acetanilide Br 4-bromoacetanilide
. . C─CH ..
O

HN 3 NH2
+
+ H . HOH
+
HO
C─CH3

O
Br Br
2) Nitration: Aniline with nitrating mixture at 288 K forms the mixture of
..
2-nitro aniline, 4,-nitro aniline & 3-nitro. . aniline. NH2 ..
..
NH2 Conc. HNO 3 NH2 NH2
+ HO-NO & H SO 2 4
─NO2
288 K
2
Nitration + + ─NO2
NO2
The formation of 3-nitro aniline is due to formation anilinium ion in
Acidic medium. The –N+H3 group of anilinium ion is meta directing.
4-nitro aniline is the step wise action of acetic anhydride, HNO3 & HCl.
.. . . C─CH
NH2 O . . C─CH . .

O
O

C─CH HN 3
HN 3 NH
+O 3
Conc. HNO 3
2

C─CH3 + & H SO + H . HOH

+
+
O

2 4

- CH3COOH 288 K
Nitration H 2O
acetanilide
NO2 NO2

+
3) Sulphonation: Aniline with conc. H2SO4 forms anilinium hydrogen sulphate
which on heating with sulphuric acid at 43-473 K gives 4-aminobenzene
-sulphonic (sulphanilic) acid with sulphonic acid as a major product..
.. + ─ ..
NH2 NH3 HSO4 Conc. H SO NH2
2 4
+ H SO
+ 2 4
453-473 K + H 2O
H2SO4 + sulphonation

Anilinium H- HO-SO3H
Aniline sulphate SO H
4-Amino benzene 3
sulphonic acid Sulphanilic acid

Sulphanilic acid both acidic –SO3H & basic –NH2 groups.

Thus sulphanilic acid gets self neutralized into a salt called dipolar ion,
Zwitter ion. An ion formed by reaction between acidic & basic groups
.. +
of the same molecule. NH2 NH3

─
SO3H SO3
Sulphanilic acid Zwitter ion
 Intext Question
Aniline does not undergo Friedel Craft’s reaction using aluminium
chloride. Explain.
Aniline has a lone pair of electrons on nitrogen atom i.e. Lewis base.
Aluminium chloride is electron deficient i.e. Lewis acid.
These while Friedel & Craft reaction form a base & reaction of
alkylation, acetylation on benzene ring gets blocked.
.. Cl
NH2 Cl Cl
Al
Al Cl
..
+ Cl
Cl
Aniline NH2
Aluminium chloride
Lewis base
Lewis acid
Electron pair Electron pair
donor acceptor
Once electron pair is donated by aniline to AlCl3,
Benzene ring gets deactivated for electrophilic substitution, Friedel Craft
reaction.
 b) OCH2 OCH3
a) CH3 c) OCH3 d)
─NO2
─NO2
SO3H NO2 NO2

..
NH2