Class-XII

Amines

Preparation

[1] Reduction Method

The primary amines may be prepared by the reduction of nitro compounds,nitriles,amides and oximes. or
H2/Pd

NO 2 NO 2

H2 / Pt

Zn / HCl

or

or

H2 / Ni

Sn/ HCl

or Fe / HCl

or

LiAlH 4

NH 2 NH 2

Sn/ HCl

or

Fe / HCl

Nitro compounds

[Fe/HCl is preferred ,because FeCl2 formed gets hydrolysed to release hydrochloric acid,thus a small amount of HCl is required to initiate the reaction.]
LiAlH 4

C N Nitrile R

or
LiAlH 4

H2 / Ni

or Na(Hg) / C 2H5OH

CH 2 NH2

O / H 2O C Amide NH2 R CH 2 NH2 Amines

[2]Hoffmann Bromamide Degradation Reaction

O R C NH2

Br 2

4 NaOH

NH2

Na 2CO 3

2 NaBr

2 H 2O

In this reaction ,the amine formed contain one carbon less than those of amide. [3] Gabriel phthalimide synthesis
O C N C O Phthalimide H KOH O C N K C O N-Alkylphthalimide COO Na COO Na

O C N C O
+

NaOH

Aromatic primary amines can not be prepared by this method because aryl halides do not undergo nucleophilic substitution with the anion formed by phthalimide.

+
+

NH2

[4] Ammonolysis of alkyl halides The process of cleavage of the C-X bond by ammonia molecule is known as ammonolysis.
RX NH3 R NH2 RX R2NH RX R3N RX R4N X
+

The primary amine thus obtained behaves as a nucleophile and can further react with alkyl halide to form secondary and tertiary amines, and finally quaternary ammonium salt.
NH3
xx

Primary amine is obtained as a major product by taking large excess of ammonia. The order of reactivity of halides with amines is RI > RBr > RCl

NH 3 X

NaOH

NH2

H2O

NaX

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Class-XII

Amines

Properties
R NH2

[1] Salt formation

HX

R NH 3 X Substituted ammonium salt HCl

NaOH

NH2

H2O

+
NH2

NaX

NH2

NH 3 Cl Anilinium chloride

NaOH

H2O

NaCl

[2] Alkylation
R NH2 RX R2NH RX R3N RX
+

R4N X

[3] Acylation The replacement of hydrogen atom of -NH 2 group by acyl group is known as acylation.
O H3C C Cl H O C2H5 Base H3C C H N C2H5

N-Ethylethanamide
O C2H5 N C2H5 O H3C C H N

The base stronger than amine, like pyridine is used to removes HCl so formed.
O H3C C Cl C2H5

+
O C

C 2H 5 H

Base

H3C

Ethanoyl chloride
O H3C C O CH3

N,N-Diethylethanamide

Ethanoic anhydride O C Benzoyl chloride Cl

Aniline
H

N-Phenylethanamide [ acetanilide ]
O H C N CH3 N- methylbenzamide

CH 3

Methanamine

[4] Carbylamine reaction

NH2

CHCl

3 KOH

Heat

NC

3 H 2O

3 KCl

NH2

CHCl

3 KOH

Heat

NC

3 H 2O

Primary amine

[5] Reaction with Nitrous acid [ Nitrous acid is prepared in situ from mineral acid and sodium nitrite.] H2O NaNO 2 + HCl + R NH2

Isocyanide / Carbylamine [ Foul smell ]

3 KCl

HNO 2

N2 Cl

OH

Aliphatic diazonium salt

NH2

Alcohol

N2

HCl

HNO 2

NaNO 2 + HCl

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 R N H S O

Cl

S O

KOH

K
R

O S O

amine

Acidic hydrogen N-alkylbenzenesulphonamide

O O R N R S O

Water soluble potassium salt of sulfonamide

KOH

N R

Cl

S O O

Water insoluble precipitate

2o amine
R N R

N,N-Dialkylbenzenesulphonamide
S

Cl

No reaction

3o amine
K
R
+

O S O

HCl

N H

S O

H2O KOH

N H

Cl

S O O

1o amine
H2O KOH R N H

O R N R S O

Cl

S O

amine
NH2 Br

These days benzenesulphonyl chloride is replaced by p-toluenesulphonyl chloride. [7] Electrophilic substitution
Br 2 / H 2O Br

Br NH2 HNO 3 , H 2SO 4 . 288 K NH2 NH2 NH2 NO 2

+
NO 2 ( 51 % ) ( 47 % )

+
NO 2 (2%)

Aniline
+

NH 3 HSO 4 H2SO 4 453 - 473 K

NH2

NH 3

Aniliniumhydrogensulphate

SO 3H Sulphanilic acid

SO 3 Zw itter ion

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Class-XII
NH2

Amines
O
xx

Controlled Bromination
H ( CH 3CO ) 2O Pyridine

O CH3 Br 2 CH 3COOH H N C CH3 OH / H NH2

+

N-Phenylethanamide ( Acetanilide )

Br

Br

Controlled Nitration
NH2 ( CH 3CO ) 2O Pyridine
xx

O C CH3 HNO 3 , H 2SO 4 , 288 K

H N

O C CH3

NH2
+

OH / H

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. 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

Explanations

[ Base ]

[ Conjugate acid ]
R R HN
+

The stability of substituted ammonium ion: The positive charge get neutralised by the +I effect of alkyl groups.

NH 2 R

NH 3

NH 4

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. So the basicity of methyl substituted amines in aqueous phase: When alkyl group is bigger methyl 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:
H3C NH
CH3 H3C NH2 H3C N CH3 NH3

2o

CH3

1o
C2 H 5

3o

H5C2 NH

H 5 C2 N

H5C2 NH2

NH3

2o

C2 H5

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

xx

NH2 Aniline

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.
H3C 2 Fe
3+
xx

NH2

+
6 OH

OH 2 Fe(OH)

H3C
3

NH 3

OH

or Fe 2O 3. 3H2O

( Brown ppt )

Basicity of
NH2 NH2 NH2 NO 2

NO 2 m-Nitroaniline

Incase of aromatic amines, the basicity depends upon: [i] Inductive effect o- > m- > p[ii] Resonance effect, observed at o- & p- positions.

NO 2 p- Nitroaniline

o-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
+ N2 Cl + NaCl Diazotisation Benzenediazonium chloride Benzenediazonium chloride is stable due to resonance.

NH2

HNO 2

NaNO 2 + HCl

H2O

Diazonium ion being a weak electrophile,can couple with a strongly activated aromatic system.

Coupling do not occur in strong acidic medium

NH2 NH3
+

H3PO 2 H2O CH 3CH 2OH

+ +

N2

+ +

H3PO 3

+ +

HCl

N2

CH 3CHO

HCl

OH

Less activated aromatic system

OH O

CuCl / HCl

Cl

+ + +

N2

CuBr / HBr

Br

N2

OH H
+

CuCN / KCN

CN

N2

N Cl Cu / HCl Cl

+ +

N2

+ + + +

CuCl

-+
In strongly alkaline medium, the concentration of diazonium ion ( act as electrophile ) decreases and coupling reaction does not occur.
N N

O Na

KI

N2

KCl

HBF 4
NaOH

N2 BF 4

N2

BF 3

OH N N

H2O

OH

N2

HCl

HBF 4
NaOH

N2 BF 4

NaNO 2 Cu

NO 2

+ N2 + NaBF 4

N N
+

OH

HO

OH

( Orange dye )

Coupling reaction
H NH2 N N NH2

( Yellow dye )

HO

Coupling reaction

p-Aminoazobenzene

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Class-XII

Amines

Predict the products

NH2

+
-

CHCl

alc. KOH

? ? ? ? ? ? ? ? ?
PhNH 2 Et 2 NH H3C
Br Br

NC

3 KCl

+ 3 H 2O +
HCl

N2 Cl

+ +

H3PO 2

H2O

+ N2 +
HO 3S

H3PO 3

NH2

Conc. H 2SO 4

NH2

N2 Cl

C2H5OH

N2
Br

CH 3CHO

HCl

NH2

aq. Br 2

NH2

3 HBr

O NH C CH3

NH2

+
-

( CH 3CO) 2O

+ CH 3COOH +

N2 Cl

(i) HBF 4 (ii) NaNO

2

NO 2

/ Cu

+
+

NaBF 4

N2

H3C

CH 2 CH 2 NH2 CH3

+ +

HCl

CH 2 CH 2 NH 3 CH3

Cl

H3C

CH3

HCl

H3C

NH Cl

CH3

PKb value Basic strength Basic strength Basic strength in gaseous phase Boiling point Solubility Basic strength +
N
+

> PhNHCH

> Et NH 2 > Et 2 NH
2

> CH 3NH 2 > Ph N Me

Aniline

> PhNH 2

p-Toluidine > Et 3N Et OH Et NH
2

> p-Nitroaniline
2

> >

Et 2 NH > Et NH Et NH
2

> NH3

> Et 2 NH > PhNH 2 >

NH3

> Et 2 NH
Et NH
2

Et 2 NH >
+

> PhNH 2
N
+

Resonating structures of diazonium ion.

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Class-XII

Amines

Jayanta kumar sahu PGT : Chemistry Kendriya Vidyalaya Sangathan

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Class-XII

Amines

Jayanta kumar sahu PGT : Chemistry Kendriya Vidyalaya Sangathan

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