Nitroform (trinitromethane) adds readily in a Michael type of addition to ct, ~ unsaturated compounds such as acrylic acid and its esters, hydroxyrnethyl vinyl ketone, and nitroethylene. The synthesis of 2-nitro-3-acetoxy-1-propene and its unique reaction with 1,1dinitroethane and nitroform is described. 4,4,4-Trinitrobutyric acid was converted to 3,3,3trinitropropyl isocyanate and 3,3,3-trinitropropyl amine hydrochloride. Trinitromethyl carbamates were prepared by the addition of 2,2,2-trinitroethanol to various isocyanates and the addition of different alcohols to 3,3,3-trinitropropyl isocyanate. Trinitromethyl amines were prepared by the Mannich condensation of 2,2,2-trinitroethanol with various primary amines and the reaction of 3,3,3-trinitropropyl amine with nitroalcohols. All of these carbamates and secondary amines were converted to the corresponding N-nitro derivatives. The synthesis of trinitromethyl heterocyclic compounds and 2,2,2-trinitroethyl esters is also reported.
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THE preparation of trinitromethyl compounds is based on nitroform (trinitromethane) as the starting material. Severalmethods for the synthesis of nitroform appear in the older literature, but none were too satisfactory. Hantzsch and Rinckenberger-treated tetranitromethane, which was prepared from acetic anhydride and nitric acid, with alcoholic potassium hydroxide to obtain potassium nitroform which was then converted to free nitroform. Orton and Mckie" introduced acetylene into 100%nitric acid with mercuric nitrate catalyst and obtained nitroform. During World War II the method of Orton and McKie was developed to a pilot-plant scale by Schimmelschmidt-in the laboratory of 1.G. Farbenindustrie in Germany. For the first time a practical synthesis of nitroform was available, and it was now feasible to investigate the little known field of trinitromethyl chemistry. Schimmelschmidt conducted research on the addition of nitroform to organic compounds and found that nitroform added to iX, p-unsaturated carbonyl compounds and formaldehyde.
1 The work summarized in this paper was done