Michael E. Sitzmann

Polynitroaliphatic explosives containing the pentafluorosulfanyl (SF5) group: The selection and study of a model compound

An investigation concerning the effect of the pentafluoro-sulfanyl (SF5) group on the properties of explosive nitro compounds is described. The investigation includes: (a) the preparation of severa...

1,3,4-Oxadiazoles with SF5-containing substituents

Abstract 1,3,4-Oxadiazoles containing a combination of SF 5 -perfluoroalkyl, SF 5 -alkyl, polynitroalkyl and perfluoroalkyl substituents have been synthesized by cyclization (dehydration) of the corresponding diacyl hydrazines. The properties of oxadiazoles with SF 5 -perfluoroalkyl substituents are compared with those of similar oxadiazoles containing the corresponding perfluoroalkyl substituent (CF 3 in place of SF 5 ).

2,5-Dipicryl-1,3,4-oxadiazole: a shock-sensitive explosive with high thermal stability (thermally-stable substitute for PETN)

Abstract The preparation and properties of 2,5-dipicryl-1,3,4-oxadiazole (DPO), a thermally stable substitute for PEIN, are discussed. Results of short pulse shock tests on DPO are also given. (b) Standard exploding foil test parameters were used (0.051 mm thick mylar flyer). 12. The m.p. of high purity DPO after crystallization from acetone-methanol is 335°C.

N-Pentafluorosulfanyl-N-nitro carbamates

Abstract Unlike N-alkyl carbamates, N-pentafluorosulfanyl carbamates (SF 5 NHCO 2 R) did not readily undergo nitration to provide the N-NO 2 derivatives. Although trifluoroacetyl nitrate did provide nitration, work-up yielded a mixture of SF 5 N(NO 2 )CO 2 R and starting material. The ratio of nitration product to starting material was not changed after prolonged reaction times and the N-NO 2 product was stable to the work-up conditions. A rationale for these results as well as the effect of varying R is discussed.

Polynitroalkyl derivatives of SF5NCCl2: nitrations of SF5 imines

Abstract Polynitroalkyl SF5 imines have been synthesized from SF5NCCl2 via nucleophilic substitution and nitration reactions. Only in one instance was the SF5 imino moiety (SF5NC) affected by a nitration reagent; the product was the fluorosulfonyl compound; very similar SF5 materials were not affected by the nitration reagent. The SF5NC moiety, when compared to the carbonyl group (OC), exhibited a strong tendency to lower the melting points of nitro compounds. The crystal structures of three SF5 imines and one fluorosulfonyl imine have been determined.

Facile formation of N-alkyl-oxazolidin-2-ones from N-alkyl-nitroxyethylamines and carbonate anion in biphasic media

Abstract Nitration of N-alkyl ethanolamines ( 1 ) followed by treatment of their corresponding N-alkyl-N-(2-nitroxyethyl)amine salts ( 2 ) in a biphasic CH 2 Cl 2 /aqueous Na 2 CO 3 or NaHCO 3 mixture at 25 °C gives N-alkyl-oxazolidin-2-ones ( 3 ). This represents a new method that allows the preparation of oxazolidinones at ambient temperature with the use of aqueous carbonate.

Improved Synthesis of 2,2,2-Trinitroethyl Ethers

Abstract An improved synthesis of 2,2,2-trinitroethyl ethers (from iodomethyl ethers and trinitromethane) that avoids the use of unstable potassium trinitromethide is described.

Reaction of 1,3,5-trifluorotrinitrobenze with nucleophiles

1,3,5-Trifluorotrinitrobenzene (1) is shown to be a versatile intermediate for the preparation of symmetrical and unsymmetrical 1,3,5-substituted trinitrobenzene derivatives. Its reaction with a number of representative N, O, C, and halogen nucleophiles is described. An unusually large cation effect is reported for its reaction with the ambident anion of dinitromethane.