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New Synthetic Route of Nitroform (NF) from Acetylacetone and Study of the Reaction Mechanism

Yan, Chao, Ding, Peng, Yang, Hongwei, Lu, Chunxu, Cheng, Guangbin
Industrial & Engineering Chemistry Research 2016 v.55 no.41 pp. 11029-11034
acetic anhydride, additives, carbonyl compounds, engineering, nitric acid, nuclear magnetic resonance spectroscopy, raw materials, reaction mechanisms, temperature
A new synthetic route of nitroform (NF), the crucial raw material of hydrazinium nitroformate (HNF), was presented in this paper. Preparation of NF with a series of α-methyl carbonyl compounds as substrates was investigated by utilizing fuming HNO₃ (98%, white) as the nitrating system. The results indicated that acetylacetone showed a good efficiency for the further studied reaction. The influence of various factors, such as additives, reaction temperature, time, and the molar ratio of fuming nitric acid to acetic anhydride, on the yield of the NF was demonstrated. NF was obtained under optimized conditions with a good yield of 40.8%. The reaction mechanism, which involved nitration–hydrolysis–nitration–hydrolysis, was proposed and verified by the ¹³C NMR tracking. Acetylacetone displays excellent prospects for industrial production of NF, because of the use of inexpensive raw materials, mild conditions, and a satisfactory yield of NF.