THE MICHAEL REACTION IN NON-ALKALINE MEDIA. VIII. THE C9-PRECURSOR, POTASSIUM METHYL 4,4DINITRO-2-HYDROXYBUTYRATE

From the examination of the changes in the ultraviolet spectra with time of the nitroformmethyl acrylate system and methyl 4,4,4-trinitrobutyrate decomposition in aqueous dioxan (pH = 5), it was shown that potassium methyl 4,4-dinitro-2-hydroxybutyrate is the precursor of dimethyl 4,4-dinitro-2-hydroxypimelate (C9). The only path for the formation of potassium methyl 4,4-dinitrobut-2-enoate was found to be the elimination of the elements of nitrous acid from methyl 4,4,4-trinitrobutyrate. The isolation and characterization of potassium methyl 4,4-dinitro-2-hydroxybutyrate and the potassium salt of 5,5-dinitro-3-hydroxypentan-2-one, the methyl vinyl ketone analog, are described. With acrylonitrile as the augend, spectral evidence for the presence in solution of the potassium salt of 3,3-dinitropropionaldehyde was obtained. (Author)