Robert J. Schmitt

A New Synthesis of Alkyl-N,N-dinitramines by Direct Nitration of Isocyanates

Abstract A facile conversion of aliphatic isocyanates to N,N-dinitramines has been developed. An aliphatic isocyanate is treated with a mixture of nitronium fluoroborate and nitric acid in acetonitrile giving fair yields and simplifing the existing synthesis.

Expedient Synthesis of t-Butyl Azide

Abstract A simple, economical synthesis of bulk (1 to 10,000 moles) quantities of t-butyl azide is described, utilizing only t-butyl alcohol, water, sodium azide, and sulfuric acid.

Gas phase chemistry of dinitramide and nitroacetylide ions

Abstract Using the tandem flowing afterglow-selected-ion flow tube, we have examined the basicity, reactivity, electron binding energy and collision-induced dissociation of two novel nitro species, the dinitramide ion (N(NO 2 ) − 2 ) and the nitroacetylide ion (O 2 NCC − ). Dinitraminic acid is among the strongest known gas phase acids with Δ H ° acid ⩽ 310 kcal mol −1 . The conjugate base, dinitramide anion, has a high electron binding energy, is extremely unreactive and is a very poor nucleophile. Collision-induced dissociation of dinitramide anion generates the O 2 NN − anion. Nitroacetylene is a moderately strong acid with Δ H ° acid = 354 ± 4 kcal mol −1 ; this value is similar to those of other nitro compounds and substituted acetylenes. The nitroacetylide ion is generally unreactive but exhibits a rich chemistry upon reaction with hydrogen sulfide. The anion has a high electron binding energy and generates four ions upon collision-induced dissociation, ONC − , C − 2 , C 2 O − , and CN − .

Synthesis of polynaphthoquinone

Abstract The synthesis of polynaphthoquinone in nitric acid was found to require N(III) catalysis.