Annulated benzotetrazine 1,3-dioxides 1. [1,2,5]Oxadiazolo[3,4-f][1,2,3,4]benzotetrazine 2,4,7-and 2,4,9-trioxides

Thermolysis of 6-azido-5-nitro-7-R-benzotetrazine 1,3-dioxides (R = H and Br) gave benzotetrazine 1,3-dioxides annulated with the furoxan ring at the C(5)-C(6) bond. According to the NMR data, these compounds at 297 K are equilibrium mixtures of two isomers with different positions of the N-oxide oxygen atom in the furoxan ring. Full assignment of signals in the ¹³C NMR spectra of the compounds obtained was accomplished. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 133–136, January, 2006.     

Trifluoromethylation and pentafluorophenylation of enamines

A reaction of enamines with Me₃SiCF₃ and Me₃SiC₆F₅ in the presence of carboxylic acids leading to α-CF₃-and α-C₆F₅-substituted amines has been studied. 3-Cyanobenzoic acid was found to be the optimal promoter of these reactions. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1466–1468, August, 2007.     

Synthesis of β-nitroxyalkylnitramines

β-Nitroxyalkylnitramines were obtained by nitration of β-hydroxyalkyl sulfamates, products of the condensation of derivatives of sulfamic acid with alkene oxides, by a mixture of HNO₃ and H₂SO₄. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1061–1062, May, 1997.     

Spectroscopic investigation of 2-nitrodiazenoxides

2-Nitrodiazenoxides have been studied by vibrational spectroscopy methods. The main regularities of the changes in the stretching vibration frequencies of the nitro and diazenoxide groups were studied as functions of different factors.X-ray data for compounds2 and3 will be reported later.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1771–1774, October, 1994.This work was carried out with financial support from the Russian Foundation for Basic Research (Project No 93-03-18461).     

Synthesis of 1,3,5-trisubstituted 1,2,4-triazolio-4-nitroimides

A method for the synthesis of 1,3,5-trisubstituted 1,2,4-triazolio-4-nitroimides was developed. The method is based on the alkylation of the corresponding salts of 3,5-disubstituted 4-nitramino-1,2,4-triazoles.     

Synthesis and structures of pyridoannelated 1,2,3,4-tetrazine 1,3-dioxides

Treatment of 2- and 4-amino-3-(tert-butyl-NNO-azoxy)pyridines with nitrating agents (N₂O₅or NO₂BF₄) afforded the first representatives of pyridoannelated 1,2,3,4-tetrazine di-N-oxides, viz., pyrido[2,3-e][1,2,3,4]tetrazine 1,3-dioxide (9), 7-nitropyrido[2,3-e][1,2,3,4]tetrazine 1,3-dioxide (10), and pyrido[3,4-e][1,2,3,4]tetrazine 2,4-dioxide (11). These compounds were studied by ¹H, ¹³C, and ¹⁴N NMR spectroscopy. The 1:1 complex of compound 10 with benzene was studied by X-ray diffraction analysis.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2471–2477, November, 2004.     

Synthesis of 1-alkyl-1,2,4-triazolium 4-nitroimides by alkylation of 4-nitramino-1,2,4-triazole salts

A method for the synthesis of 1-alkyl-1,2,4-triazolium 4-nitroimides was developed based on alkylation of 4-nitramino-1,2,4-triazole Na and Ag salts with halo- and dihaloalkanes.     

Silylation as a new strategy of the use of aliphatic nitro compounds in organic synthesis

Silylation of aliphatic nitro compounds is considered as a versatile multistage process. Due to activation of the - and -carbon atoms of the initial nitro substrates, these reactions give rise to a series of products untypical of the traditional chemistry of nitro compounds. A new redox process proposed in the present study involves controlled incomplete reduction of the nitro group with simultaneous oxidation of the carbon skeleton of the initial aliphatic nitro compound.     

Synthesis and structures of tris(pentafluorophenyl)silylamines

Tris(pentafluorophenyl)silylamines were synthesized by silylation of amines and imines with (C₆F₅)₃SiCl or (C₆F₅)₃SiOTf in the presence of triethylamine. The crystal structures of the (C₆F₅)₃SiN(H)CH₂Ph and (C₆F₅)₃SiN(CH=CMe₂)CH₂Ph compounds were studied by X-ray diffraction. The crystal packings were analyzed by quantum chemical calculations in terms of the density functional theory (PBE exchange-correlation functional). Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1345–1352, July, 2007.     

Dinitramide and its salts

Nitration of nitramidc to dinitramide with nitryl salts is described.