Aromatic nitration with bismuth nitrate in ionic liquids and in molecular solvents: a comparative study of Bi(NO3)3·5H2O/[bmim][PF6] and Bi(NO3)3·5H2O/1,2-DCE systems

Abstract

A suspension of bismuth nitrate pentahydrate (BN) in [bmim][PF6] or [bmim][BF4] imidazolium ionic liquid (IL) is an effective reagent for ring nitration of activated aromatics under mild conditions without the need for external promoters. Nitration can also be effected in 1,2-DCE, MeCN, or MeNO2 without additives. Nitration of activated arenes (anisole, toluene, ethylbenzene, cumene, p-xylene, mesitylene, durene, and 1,3-dimethoxybenzene) is considerably faster (time to completion) in BN/[bmim][PF6] relative to BN/1,2-DCE and there are also differences in isomer distributions (for anisole, toluene, and ethylbenzene). With introduction of strongly deactivating substituents (–CHO; –MeCO; –NO2) the BN/IL system is no longer active but reactions still proceed with BN/1,2-DCE in reasonable yields. The ready availability and low cost of BN, simple operation, and absence of promoters, coupled to recycling and reuse of the IL, provide an attractive alternative to classical nitration methods for activated arenes. Switching from Bi(NO3)3·5H2O/[bmim][PF6] to Bi(NO3)3·5H2O/1,2-DCE increases the scope of the substrates that can be nitrated.