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Unformatted text preview: 644 AMINES Reduce nitro group to amine:
CH3 CH3 1. Fe, HCl
2. HO NO2 NH2 1-Bromo-2-methyl4-nitronaphthalene 4-Bromo-3-methyl1-naphthylamine Replace amino group by ﬂuorine:
CH3 CH3 1. NaNO2, HCl,
H2O, 0–5 C
3. heat F NH2
4-Bromo-3-methyl1-naphthylamine (e) 1-Bromo-4-ﬂuoro-2methylnaphthalene
(64%) Bromination of the starting material will introduce the bromine substituent at the correct
position, that is, ortho to the tert-butyl group.
Br2, Fe NO2 NO2 p -tert -Butylnitrobenzene 2-Bromo-1-tert butyl-4-nitrobenzene The desired product will be obtained if the nitro group can be removed. This is achieved by its
conversion to the corresponding amine, followed by reductive deamination.
Br H2, Ni 1. NaNO2, H
2. H3PO2 (or other appropriate
reducing agent) NO2 NH2 2-Bromo-1-tert butyl-4-nitrobenzene (f) C(CH3)3
Br 3-Bromo-4-tert butylaniline o-Bromo-tertbutylbenzene The proper orientation of the chlorine substituent can be achieved only if it is introduced after
the nitro group is reduced.
C(CH3)3 C(CH3)3 Cl Cl
NH2 C(CH3)3 C(CH3)3 NH2 NO2 The correct sequence of reactions to carry out this synthesis is shown. Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website ...
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