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Structure Optical Activity

• N-atom in amines is sp3-hybridised with tetrahedral • Amines containing different substituents on


structure where one position of the tetrahedral nitrogen are chiral. 2° and 3° amines exhibit
is occupied by a lone pair. Thus, the actual optical activity or enantiomerism. However,
geometry is pyramidal with bond angle little less unlike chiral carbon compounds, most chiral
than 109.5°. amines cannot be resolved as two enantiomeric
Unshared
forms rapidly interconvert into one another by
electron nitrogen inversion or amine inversion. This is
sp3
pair also known as flipping, (resembles an umbrella
turning inside out) which occurs very rapidly
CH3 (rate = 2.3 × 1010 s–1).
CH3
sp2-hybridised sp3-hybridised
3
sp -hybridised N-atom N-atom
N-atom R1
CH3 R1 R1
108° R2 N N N R2
Pyramidal shape of R3 R2 R3 R3
trimethylamine (I) Planar transition state (II)

Preparation
Ammonolysis of alkyl halides Hoffmann bromamide degradation reaction
(Hoffmann’s ammonolysis method) RCONH2 + Br2 + 4KOH R NH2 + K2CO3
NH3 RX R NH2 RX R2NH RX R3N + 2KBr + 2H2O
1° amine 2° amine 3° amine (Migration of alkyl group from carbonyl to nitrogen)
RX +–
R4NX
Quaternary Gabriel phthalimide synthesis
ammonium
salt (4°) CO CO – +
KOH(alc.)
(Reactivity order : R I>R Br > R Cl) NH –H O NK
2
CO CO
Methods of Preparation

Reduction of nitriles –KBr C2H5Br/D

(Mendius reduction) COOH H3O+, CO


H2/Raney Ni + C2H5NH2 D N C2H5
R C N or Na(Hg)/C2H5OH
R CH2 NH2 COOH Ethylamine CO

(Only for preparation of aliphatic primary amines)


Reduction of amides
(i) LiAlH4
R CONH2 (ii) H O R CH2 NH2 Schmidt reaction
2
3 NH
R COOH conc. H R NH2 + CO2 + N2
2SO4
Reduction of nitro compounds
NO2 NH2 Industrial preparation
H2/Pd-C, ethanol/ D 723 K C2H5OH
C2H5OH + NH3 C2H5NH2
D/Sn + HCl or Fe+ HCl Al2O3
C H OH
(Fe/HCl is preferred because FeCl2 formed gets (C2H5)3N 2 5 (C2H5)2NH
hydrolysed to release HCl gas.) (Mixture is separated by fractional distillation)