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Class-XII Amines

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Class-XII Amines

Properties
[1] Salt formation
+ - NaOH
R NH2 + HX R NH 3 X R NH2 + H2O + NaX
Substituted ammonium salt

- NaOH
NH2 + HCl +
NH 3 Cl NH2 + H2O + NaCl

Anilinium chloride
[2] Alkylation
RX RX RX + -
R NH2 R2NH R3N R 4N X

[3] Acylation
The replacement of hydrogen atom of -NH 2 group by acyl group is known as acylation.
O H O H
Base
H3C C Cl + H N C2H5 H3C C N C2H5
N-Ethylethanamide
The base stronger than amine, like pyridine is used to removes HCl so formed.
O C2H5 O C2H5
Base
H3C C Cl + H N C2H5 H3C C N C2H5
Ethanoyl chloride N,N-Diethylethanamide
O O H O H

H3C C O C CH3 + H N H3C C N


Ethanoic anhydride N-Phenylethanamide
Aniline
[ acetanilide ]
O
H O H
C Cl + H N CH 3 C N CH3
Methanamine N- methylbenzamide
Benzoyl chloride
[4] Carbylamine reaction
Heat
NH2 + CHCl 3
+ 3 KOH NC + 3 H2O
+ 3 KCl

Heat
R NH2 + CHCl 3 + 3 KOH R NC + 3 H2O + 3 KCl

Primary amine Isocyanide


/ Carbylamine
[ Foul smell ]
[5] Reaction with Nitrous acid
[ Nitrous acid is prepared in situ from mineral acid and sodium nitrite.]
NaNO 2 + HCl + - H2O
R NH2 + HNO 2 R N2 Cl R OH + N2 + HCl
Alcohol
Aliphatic diazonium salt

NH2 NaNO 2 + HCl + -


+ HNO 2 N2 Cl + NaCl + H2O

Benzenediazonium chloride
Benzenediazonium chloride is stable due to resonance.

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Class-XII Amines
[6] Reaction with Hinsberg's reagent
Benzenesulphonyl chloride is known as Hinsberg's reagent.
O O + O
KOH K
R N H + Cl S R N S R N
-
S

H O O O
H
o Water soluble
1 amine
Acidic hydrogen potassium salt
N-alkylbenzenesulphonamide of sulfonamide
O O
KOH Water insoluble
R N H + Cl S R N S
precipitate
O R O
R
o N,N-Dialkylbenzenesulphonamide
2 amine
O
R N R + Cl S No reaction
R O
3o amine
O
+ O O
K H2O
R N S
HCl
R N S
R N H + Cl S
- KOH H O
O O
H
1o amine
O O
H2O
R N S
KOH
R N H + Cl S

O R O
R
2o amine
These days benzenesulphonyl chloride is replaced by p-toluenesulphonyl chloride.
NH2
[7] Electrophilic substitution
Br Br
Br2 / H2O

Br

NH2 NH2 NH2 NH2

NO 2
HNO 3 , H2SO 4 . 288 K
+ +
NO 2
Aniline NO 2 ( 47 % ) (2%)
( 51 % )

+ - +
NH 3 HSO 4 NH2 NH 3

H2SO 4 453 - 473 K

Aniliniumhydrogensulphate -
SO 3H SO3
Sulphanilic acid Zwitter ion

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Class-XII Amines
Controlled Bromination O O
xx
NH2 H N C CH3 H N C CH3 NH2
( CH 3CO ) 2O Br2 - +
OH / H
Pyridine CH 3COOH

N-Phenylethanamide Br Br
( Acetanilide )

Controlled Nitration O
O
NH2
xx
H N C CH3 NH2
H N C CH3
( CH 3CO ) 2O
HNO 3 , H2SO 4 , 288 K - +
OH / H
Pyridine

NO 2 NO 2
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.
Explanations
Aniline and other aryl amines are colourless but get coloured on storage due to
atmospheric oxidation.
Alcohols are more soluble than amine in water because, alcohols are more polar than
amines and form strong intermolecular hydrogen bonds than amine.
The intermolecular association is more in primary amine than in secondary amines as there
are two hydrogen atoms avilable for hydrogen bond formation in primary. Tertiary amines
do not have intermolecular association due to absence of hydrogen atom available for
hydrogen bond formation. Therefore, the order of boiling points of isomeric amines :
Primary > Secondary > Tertiary
The basicity of amines in gaseous phase : 3o amine > 2o amine >1o amine > NH3
H
xx +
+
N + H N

[ Base ] [ Conjugate acid ]


R
The stability of substituted ammonium ion:
+ + +
+
The positive charge get neutralised by R HN R NH 2 R NH 3 NH 4
the +I effect of alkyl groups. R R

In aqueous phase the stability of substituted ammonium cation depend upon both the +I
effect of alkyl group and solvation by water molecules. The greater the size of the ion
lesser will be the solvation and less stabilised is the ion.
CH3
So the basicity of methyl substituted H3C NH H3C NH2 NH3
H3C N
amines in aqueous phase: CH3
When alkyl group is bigger methyl group, 2o 1o 3o CH3
there will be steric hindrance to
H-bonding with water, so the stability C2 H 5
H5C2 NH2 NH3
of substituted ammonium ion decreases. H5C2 NH H5 C2 N
So the basicity of ethyl substituted
amines in aqueous phase: 2o C 2 H 5 3o C 2 H 5 1o

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Class-XII Amines
Aniline does not undergo Friedel-Crafts reaction (alkylation / acetylation) due to salt
formation with aluminium chloride, the Lewis acid, which is used as a catalyst.Due to this
, nitrogen of aniline acquires positive charge and hence acts as a strong deactivating
group for further reaction.
Besides the ortho and para derivatives, significant amount of meta derivative is also formed
during nitration of aniline.Because, in the presence of mineral acids,the aniline readily
forms anilinium ions. The anilinium ion is a strong electron withdrawing group, which
directs the electrophile towards meta position.
+ -
NH2 NH 3 NO 3 NH2
Ring deactivator
HNO 3

NO 2

Aniline is less basic than ammonia, because the availability of electron on


nitrogen atom of aniline decreases due to delocalisation of electron by xx
NH2
resonance
In case of aliphatic amine due to +I effect of alkyl group, the xx Aniline
electron density on nitrogen atom increases, as a result basic R > NH2
strength increases. Aliphatic amine

Amines are less acidic than alcohols, because N-H bond is less polar than O-H bond. Therefore, amine
releases H+ ion with more difficulty.
Aromatic amines are insoluble in water because, the phenyl group is bulky in size and has
-I effect. As a result, its hydrogen bonding with water is negligible.

Methylamine forms a soluble hydroxide on reacting with water. The OH- ions released by
the hydroxide combine with Fe3+ ions of ferric chloride to give ferric hydroxide or
hydrated ferric oxide which is brown in colour.
xx
+ -
H3C NH2
+ H OH H3C NH 3
+ OH
3+ -
2 Fe + 6 OH 2 Fe(OH) 3 or Fe 2O 3. 3H2O ( Brown ppt )

Basicity of
NH2 Incase of aromatic amines, the basicity
NH2 NH2
depends upon:
NO 2 [i] Inductive effect o- > m- > p-
[ii] Resonance effect, observed
at o- & p- positions.
NO 2
NO 2 o-Nitroaniline
m-Nitroaniline
p- Nitroaniline
The electron withdrawing substituents on aromatic ring reduce the basicity of substituted
anilines. The -R effect of nitro group is observed maximum at ortho and para positions.Thus,
m-nitroaniline is relatively more basic compared to ortho and para isomers as it withdraws
electrons through inductive effect(-I effect) only. Out of o-nitroaniline and p-nitroaniline, -I
effect is found to be stronger in ortho isomers as compared to para. Thus,o-nitroaniline
experiences a strong -R and -I effect and is least basic.

So PKb of o-nitroaniline > p-nitroaniline > m-nitroaniline

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Class-XII Amines

Benzenediazonium Chloride
+ - NaNO 2 + HCl
Diazotisation
NH2
N2 Cl + NaCl + HNO 2
+ H2O

Benzenediazonium chloride
Benzenediazonium chloride is stable due to resonance.

Coupling do not H3PO2


Diazonium ion being a weak electrophile,can couple

occur in strong H2O


H + N2 + H3PO 3 + HCl

acidic medium
with a strongly activated aromatic system.

+
NH2 NH 3 CH 3CH 2OH
+
H + N2 + CH 3CHO
+ HCl
H
-
OH

CuCl / HCl
Less Cl + N2
activated
aromatic
system
CuBr / HBr N2
OH O
- Br +
-
OH
+
H CuCN / KCN CN + N2

+ -
N N Cl Cu / HCl
Cl + N2 + CuCl

-+
O Na
In strongly alkaline medium, the concentration of

N
KI
diazonium ion ( act as electrophile ) decreases

N
I + N2 + KCl
and coupling reaction does not occur.

HBF 4 -
+

NaOH N2 BF 4 F + N2 + BF 3

OH

N H2O
N
OH + N2
+ HCl

HBF 4 + - NaNO 2
NaOH
N2 BF 4
Cu 
NO 2 + N2 + NaBF 4
N H OH
+
N -
N N OH ( Orange dye )
HO Coupling reaction

H NH2 N N NH2 ( Yellow dye )


-
HO Coupling reaction p-Aminoazobenzene

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Class-XII Amines

Predict the products


+ + 3 H2O
?
NC 3 KCl
NH2 + CHCl 3 + alc. KOH

- + N2 + H3PO 3 +
?
+ HCl
N2 Cl + H3PO 2
+ H2O

NH2
+ Conc. H 2SO 4
? HO 3S NH2

-
?
+
N2 Cl + C2H5OH + N2 + CH 3CHO + HCl

Br

NH2 + aq. Br 2 ? Br NH2 + 3 HBr

Br

O
NH2 + ( CH 3CO) 2O ? NH C CH3 + CH 3COOH

- + +
?
+ (i) HBF 4 NO 2 NaBF 4 N2
N2 Cl
(ii) NaNO 2 / Cu 

+ -
?
H3C CH 2 CH 2 NH 3
H3C CH 2 CH 2 NH2 + HCl Cl

CH3 CH3

?
+
H3C N CH3 + HCl H3C NH
Cl
CH3
-

PKb value PhNH 2 > PhNHCH 3 > Et NH 2 > Et2 NH


Basic strength Et 2 NH > CH 3NH 2 > Ph N Me 2 > PhNH 2

Basic strength p-Toluidine > Aniline > p-Nitroaniline

Basic strength in gaseous phase Et 3N > Et 2 NH > Et NH 2 > NH3

Boiling point Et OH > Et NH 2 > Et2 NH

Solubility Et NH 2 > Et2 NH > PhNH 2

Basic strength Et 2 NH > Et NH 2 > NH3 > PhNH 2


+
+ + - + N
+
N
- + -
N N N N N N

+
Resonating structures of diazonium ion.

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Class-XII Amines

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