Reactions of 2-bromo-2,2-dinitroethyl acetate with bases

Abstract

2-Bromo-2,2-dinitroethyl acetate (I) has been found to be extremely reactive towards a variety of bases, including some relatively weak ones. For example, reaction of the ester with absolute methanol gives 1-bromo-1,1-dinitro-2-methoxyethane (VIII) in 72% yield and 2-bromo-2,2-dinitroethanol (IX) in 12% yield. The alcohol IX arises by reaction of VIII with water, the latter compound resulting from the Fischer esterification reaction of acetic acid, another solvolysis product of I, and methanol, the solvent. Furthermore, IX is converted to VIII in 91% yield by treatment with absolute methanol. The rate of this reaction, however, is decidedly slower than that of the methanolysis of I. Reaction of I with the sodium salt of phthalimide in aqueous methanol affords a mixture of 1-bromo-1,1-dinitro-2-phthalimidoethane (VII) and the sodium salt (IV) of 1,1-dinitro-2-phthalimidoethane. Condensation of I with the disodium salt of ethylenedinitramine gives 1,8-dibromo-1,1,3,6,8,8-hexanitro-3,6-diazaoctane (VI) in 72% yield.