Preparation of Nitroanilines
2785
was carried out by reacting it with ammonia. We found that only the
starting material was recovered. We conclude that the activity of the nitro
group on the aromatic ring increased because of the electrophilic effect of
the other nitro groups. Furthermore, the activity of the remaining nitro
group decreased because of the pushing electron effect of the substituted
amino groups, so there were no multiamino compounds observed.
In conclusion, a new method has been developed for the ammonoly-
sis of multinitrobenzenes. The materials are inexpensive, and the yields
are significantly high. The method described herein compares very favor-
ably with known methods and should be a valuable addition to ammon-
olysis methodology.
ACKNOWLEDGMENTS
We gratefully acknowledge the funding support by grants from the
National Natural Science Foundation of China (No. 20776127), the
National Key Technology R&D Program (No. 2007BA134B07), and
the Opening Foundation of Zhejiang Provincial Top Key Discipline
(
No. 56310101613).
REFERENCES
1
. For example, see (a) Hodgson, H. H.; Ward, E. R. Reactions of aromatic nitro
compounds with alkaline sulfides. II. The three dinitrobenzenes. J. Chem. Soc.
1949, 1316–1317; (b) Rahaim, R. J.; Maleczka, R. E. Palladium-
catalyzed silane=siloxane reductions in the one-pot conversion of nitro
compounds into their amines, hydroxylamines, amides, sulfonamides, and
carbamates. Synthesis 2006, 19, 3316–3340; (c) Dale, J.; Vikersveen, L. The
reaction of nitrobenzenes with sodium borohydride; a novel reductive coupling
to diphenylamine derivatives. Acta Chem. Scand., Ser. B: Org. Chem. and Bio-
chem. 1988, B42, 354–361.
2
3
4
. For example, see Zhao, F. Y.; Fujita, S.; Sun, J. M.; Ikushima, Y.; Arai, M.
Hydrogenation of nitro compounds with supported platinum catalyst in super-
critical carbon dioxide. Catal. Today 2004, 98, 523–528.
. For example, see Chari, M. A.; Prasad, M. S.; Syamasundar, K. Reduction
of nitroaromatics with a new heterogenised MCM-41-1-(benzimidazol-2-yl)-
ethanone. J. Indian Chem. Soc. 2005, 82, 153–154.
. For example, see (a) Selvam, P.; Mohapatra, S. K.; Sonavane, S. U.; Jayaram,
R. V. Chemo- and regioselective reduction of nitroarenes, carbonyls and
azo dyes over nickel-incorporated hexagonal mesoporous aluminophosphate
molecular sieves. Tetrahedron Lett. 2004, 45, 2003–2007; (b) Kulkarni, A. S.;
Jayaram, R. V. Liquid phase catalytic transfer hydrogenation of aromatic
nitro compounds on perovskites prepared by microwave irradiation. Appl.