The Michael condensation and the Mannich reaction were employed to prepare a variety of functional polynitro compounds. In general, reactions proceeded smoothly to give the expected products. However, 2,2,i,2'-tetranitrodiethylamine and its N-substituted derivatives did not give the expected Michael adducts with methyl acrylate. Instead, dimethyl 4,4-dinitro-1,7-heptanedioate, the 2: 1 adduct of methyl acrylate and dinitromethane, was formed due to disproportionation of the original nitro compounds. Gradual acidification of the potassium salt of 2,2-dinitroethanol gave the salt of 2,2,4,4-tetranitro-l-butanol, apparently via formation of 1,1-dinitroethylene an an intermediate. The Mannich reaction of polynitro-l,5-pentanediols with amines gave cyclic derivatives, whereas similar reactions of 2,2dinitro-1,3-propanediol gave the linear products in some instances and cyclic derivatives in others; the latter appear to result from iiI situ formation of the anion of 2,2,4,4-tetranitrol-butanol.
As part of a program undertaken to explore various synthetic routes to aliphatic polynitro compounds containing functional groups, a study of the Michael condensation and the Mannich reaction, as applied to nitro aliphatic systems, was undertaken.