We review and systematize experimental evidence concerning the extreme high-pressure kinetics of condensed phase nitroalkanes and nitroaromatics. This systematization suggests that enolate aci anions of the nitroalkanes and enolate aci-quinone anions of the nitroaromatics are important in the initial high-pressure kinetics of such systems. Kinetic data from experiments which observed the effect of: (1) small amounts of chemical additives, (2) substitution for protons, (3) difference in chemical isomer, (4) exposure to ultra-violet light, and (5) application of very high pressure can all be rationalized within the framework of our hypothesis. We suggest a static high-pressure ultra-violet absorption spectroscopy experiment on nitromethane that would test the proposed hypothesis.

Importance of enolate anions in the high-pressure kinetics of nitroalkanes and nitroaromatics

The kinetics of the reaction of di- and triethylamine with 1,8-dimethyl-2,4,5-trinitronaphthalene (245 TND) have been studied in dimethylsulfoxide and dimethylsulfoxide-methanol solvent systems and comparison made with data for corresponding reactions involving 1,5-dimethyl-2,4,8-trinitronaphthalene (248 TND). Analysis of the results shows that the formation of a benzyl-type anion is more facile with 245 TND than with 248 TND. Thus, the former compound has the greater potential for base-induced coupling to give thermally stable explosive material.

T. F. Houiellebecq

Papers

Substituent Pattern Effect in the reaction of dimethyltrinitronaphthalenes with Di‐ and triethylamine