Chemistry Preparation of Amines

Topics Covered :

● Preparation of Amines
● Reduction of Nitro Compounds
● Ammonolysis of Alkyl Halides
● Reduction of Nitriles
● Reduction of Amides
● Gabriel Phthalimide Synthesis
● Hoffmann Bromamide Degradation Reaction

Preparation of Amines :

There are various methods by which amines are prepared. So the following methods are :

Reduction of nitro compounds :

`=>` Nitro compounds are reduced to amines by passing hydrogen gas in the presence of finely divided nickel, palladium or platinum and also by reduction with metals in acidic medium.

`=>` Nitroalkanes can also be similarly reduced to the corresponding alkanamines.

`=>` Reduction with iron scrap and hydrochloric acid is preferred because `color{red}(FeCl_2)` formed gets hydrolysed to release hydrochloric acid during the reaction. Thus, only a small amount of hydrochloric acid is required to initiate the reaction.


Ammonolysis of alkyl halides

The carbon - halogen bond in alkyl or benzyl halides can be easily cleaved by a nucleophile.

● Hence, an alkyl or benzyl halide on reaction with an ethanolic solution of ammonia undergoes nucleophilic substitution reaction in which the halogen atom is replaced by an amino (`color{red}(–NH_2)`) group.

● This process of cleavage of the `color{red}(C–X)` bond by ammonia molecule is known as ammonolysis.

● The reaction is carried out in a sealed tube at `373 K`.

● 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. See fig.

`color{red}(underset(1^o)(RNH_2) overset(RX)→ underset(2^o)(R_2NH) overset(RX)→ underset(3^o)(R_3N) overset(RX)→ undersettext(Quaternary ammonium salt)(R_4 overset(+)N overset(-)X))`

`=>` The free amine can be obtained from the ammonium salt by treatment with a strong base :

`color{red}(R - overset(+)NH_3overset(-)X+NaOH → R-NH_2+H_2O +overset(+)Na overset(-)X)`

`color{green}(text(Disadvantage ))` : Ammonolysis yields a mixture of primary, secondary and tertiary amines and also a quaternary ammonium salt.

● However, primary amine is obtained as a major product by taking large excess of ammonia.

● The order of reactivity of halides with amines is `color{red}(RI > RBr > RCl)`.
Q 3063201145

Write chemical equations for the following reactions:
(i) Reaction of ethanolic `NH_3` with `C_2H_5Cl`.
(ii) Ammonolysis of benzyl chloride and reaction of amine so formed with two moles of `CH_3Cl`.

Solution:

(i). `undersettext(Chloroethane)(C_2H_5 -Cl) overset(NH_3)→ undersettext(Ethanamine)(C_2H_6-NH_2) overset(C_2H_5-Cl)→ undersettext(N-Ethylethanamine)(C_2H_5 - overset(overset(H)(|))N-C_2H_5) overset(C_2H_5-Cl)→ undersettext(N, N- Diethylethanamine)(C_2H_5 - underset(underset(C_2H_5)(|))N-C_2H_5)`


(ii). `undersettext(Benzylchloride)(C_6H_5-CH_2-Cl) overset(NH_3)→ undersettext(Benzylamine)(C_6H_5-CH_2NH_2) overset(2CH_2Cl)→ undersettext(N, N - Dimethylphenylmethanamine)(C_6H_5-CH_2- underset(underset(CH_3)(|))N-CH_3)`

Reduction of nitriles :

`=>` Nitriles on reduction with lithium aluminium hydride `color{red}(LiAlH_4)` or catalytic hydrogenation produce primary amines.

● This reaction is used for ascent of amine series, i.e., for preparation of amines containing one carbon atom more than the starting amine.

`color{red}(R-C equiv N underset(Na(Hg)//C_2H_5OH) overset(H_2//Ni)→ R- CH_2-NH_2)`

Reduction of amides :

The amides on reduction with lithium aluminium hydride yield amines.

`color{red}(R - overset(overset(O)(||))C-NH_2 underset((ii)H_2O) overset((i) LiAlH_4)→ R-CH_2-NH_2)`

Gabriel phthalimide synthesis :

`=>` Gabriel synthesis is used for the preparation of primary amines.

`=>` Phthalimide on treatment with ethanolic potassium hydroxide forms potassium salt of phthalimide which on heating with alkyl halide followed by alkaline hydrolysis produces the corresponding primary amine.

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

Hoffmann bromamide degradation reaction :

`=>` Hoffmann developed a method for preparation of primary amines by treating an amide with bromine in an aqueous or ethanolic solution of sodium hydroxide.

`=>` In this degradation reaction, migration of an alkyl or aryl group takes place from carbonyl carbon of the amide to the nitrogen atom.

`=>` The amine so formed contains one carbon less than that present in the amide.

`color{red}(R - overset(overset(O)(||))C-NH_2+Br+4NaOH → R-NH_2+Na_2CO_3+2NaBr+2H_2O)`

Q 3063401345

Write chemical equations for the following conversions:
(i) `CH_3–CH_2–Cl` into `CH_3–CH_2–CH_2–NH_2`
(ii) `C_6H_5–CH_2–Cl` into `C_6H_5–CH_2–CH_2–NH_2`

Solution:

(i) `undersettext(Chloroethane)(CH_3-CH_2-Cl) oversettext(Ethanolic NaCN)→ undersettext(propanenitrile)(CH_3-CH_2 - C equiv N) oversettext(reduction)→ undersettext(Propan -1 - amine)(CH_3-CH_2-CH_2-NH_2)`


(ii). `undersettext{ Chlorophenylmethane (benzyl chloride)} (C_6H_5-CH_2-Cl) oversettext(Ethanolic NaCN)→ undersettext{Phenyethanenitrile (Benzyl cyanide)} (C_6H_5-CH_2 - C equiv N) overset(H_2//Ni)→ undersettext(2-phenylethanamine)(C_6H_5-CH_2-CH_2-NH_2)`
Q 3073101946

Write structures and IUPAC names of
(i) the amide which gives propanamine by Hoffmann bromamide reaction.
(ii) the amine produced by the Hoffmann degradation of benzamide.

Solution:

(i) Propanamine contains three carbons. Hence, the amide molecule must contain four carbon atoms. Structure and IUPAC name of the starting amide with four carbon atoms are given below: `CH_3-CH_2-CH_2 - underset ( underset(O)(||))C-NH_2` Butanamide

(ii) Benzamide is an aromatic amide containing seven carbon atoms. Hence, the amine formed from benzamide is aromatic primary amine containing six carbon atoms.

 
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