Synthesis and structures of nitroxyalkyl methylphosphonates

The reactions of ethylene glycol mononitrate and glycerol 1,3-dinitrate with methylphosphonic dichloride afforded new nitroxyalkyl methylphosphonates.     

Vicinal N,C-difluorination of secondary polynitroalkylamine Mannich bases

The direct fluorination of Mannich bases containing nitro groups in one or two alkyl substituants in the position relative to the amine nitrogen gives previously unreported vicinal N,C-difluorides.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1692–1693, July, 1991.     

Thermal Transformations of Cubane Derivatives

The thermal degradation of the cubane moiety in 1,4-cubanedicarboxylic acid, its dimethyl ester, and 1,4-dibromocubane in a condensed state were studied by calorimetry. The kinetic parameters and the composition of products, as determined by ¹H and ¹³C NMR spectroscopy, are consistent with a biradical reaction mechanism. The presence of carboxyl groups capable of resonance conjugation stabilizes a biradical and increases the rate of isomerization of the acid and ester by a factor of 20, as compared with that of cubane. Bromine as a substituent has almost no effect on the rate of cubane thermolysis. The primary biradical is rapidly isomerized to corresponding cyclooctatetraene derivatives. A detailed reaction scheme is presented, and the relative rates of individual steps of the process are considered.     

Polynitro-substitutedN-alkylalkaneimidoyl chlorides

The reaction of -fluorosubstituted polynitroalkylaldimines with HCl results in replacement of the fluorine atom by a chlorine atom. The hitherto unknown -chlorosubstituted polynitroalkylaldimines have been obtained, and their X-ray structural investigation has been performed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 440–443, March, 1994.     

Synthesis of esters of 3-fluoro-3-nitroacrylic acid

Conclusions The reaction of 1,3-difluoro-1,1,3,3-tetranitropropane with alkanols was used for the preparation of alkyl esters of 3-fluoro-3-nitroacrylic acid. 1,3-Difluoro-1,3,3-trinitro-1- propene and 1,3-difluoro-1,3-dinitro-2-alkoxy-1-propene were also isolated as intermediates.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 709–711, March, 1989.     

1,1,4,4-Tetranitrobutane-2,3-diol and its derivatives. 5. Reaction of 1,1,4,4-tetranitrobutane-2,3-diol with formaldehyde; synthesis and crystal structure of 4,4-dinitro-2,3-dihydroxytetrahydrofuran

1,1,4,4-Tetranitrobutane-2,3-diol reacts with formaldehyde, forming 2,2-dinitropropane-1,3-diol or a cyclic ether — 4,4-dinitro-2,3-dihydroxytetrahydrofuran — as a function of the reaction conditions.Institute of Chemical Physics, Chernogolovka, Russian Academy of Sciences, 142432 Chernogolovka. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2755–2759, December, 1992.     

Cubane derivatives

New substituted cubane-1,4-dicarboxamides and 4-bromocubanecarboxamides containing the nitroxyl group and amino acid fragments along with the cubane skeleton were synthesized. The cardiac pharmacological activity (both the effect on aorta relaxation and the calcium channel blocking activity) of most of nitroxyalkyl derivatives is equal to or higher than that of N-(2-nitroxyethyl)nicotinamide (nicorandil).     

Kinetics of thermoinitiated oligomerization of 3,3′-(2,4,6-triethyl-1,3-phenylene)bis(5-methyl-1,2,4-oxadiazole)

The crystal structure of 3,3′-(2,4,6-triethyl-1,3-phenylene)bis(5-methyl-1,2,4-oxadiazole), which models the cross-linking fragment of polynitriles by benzodinitrile oxides, was determined by X-ray diffraction analysis. The kinetic regularities of its thermoinitiated oligomerization were studied by isothermal calorimetry and spectrophotometry. The process proceeds with self-acceleration, and the Arrhenius dependences of the initial and maximum reaction rates were determined. The reaction accelaration is determined by an increase in the viscosity of the reaction medium. Possible mechanisms were proposed for oligomerization.     

N-Substituted tetrahydro-1,3-oxazines and oxazolidines. 1. A new version of the Mannich reaction involving amino alcohols

A new version of the Mannich reaction involving amino alcohols (3-aminopropan-1-ol and aminoethanol) was developed. These compounds react with formaldehyde and CH or NH acids to give N-substituted tetrahydro-1,3-oxazines or oxazolidines.