Preparation of Nitroanilines by Ammonolysis of Multinitrobenzenes

Abstract

Highly efficient ammonolysis of several multinitrobenzenes to the corresponding nitroanilines was achieved by aqueous ammonia. o-Dinitrobenzene on reaction with 8 equiv. of ammonia produce the o-nitroaniline in yields of 87%. Similar reactions with p-dinitrobenzene, m-dinitrobenzene, and trinitrobenzene produce p-nitroaniline, m-nitroaniline, and 3,5-dinitroaniline, in yields of 86%, 45%, and 84%, respectively.

Keywords:

• Ammonia
• ammonolysis
• multinitrobenzene
• nitroaniline

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).

Notes

^a Entry 1: ¹H NMR (CDCl₃, 400 MHz): δ6.64 (2H, s), 6.71 (2H, s), 7.97 (2H, s); Entry 2: ¹H NMR (DMSO, 400 MHz): δ6.53 (2H, s), 7.73 (2H, s), 7.88 (1H, s); Entry 3: ¹H NMR (CDCl₃, 400 MHz): δ4.0 (2H, s), 6.95 (1H, t, J = 6.8 Hz), 7.26 (1H, t, J = 7.5 Hz), 7.48 (1H, t, J = 7.0 Hz), 7.54 (1H, t, J = 7.2 Hz).

^b Isolated yield.