Syntheses based on (N,N-difluoroamino)dinitroacetonitrile

High reactivity of the nitrite group in (NN-difluoroamino)dinitroacetonitrile was demonstrated. Based on its reaction with HN₃, a new preparative method for the synthesis of 5-[(N,N-difluoroamino)dinitromethylltetrazole was developed; some derivatives of the latter compound have been obtained.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8. pp. 2056–2058, August, 1996.     

Preparation ofN-nitrohydroxylamines by the substituting nitration method

N-Nitro-N-methyl-O-substituted hydroxylamines were synthesized in high yields by nitration of appropriateN-acetylhydroxylamines with nitrogen pentoxide.Translated fromIzvestiya Akademioi Nauk. Seriya Khimicheskaya, No. 3, pp767–769, March, 1996.     

Dinitramide and its salts

The dinitramide anion shows ambident properties. Its reactions with alkylating reagents give rise toN- orO-alkylated products or their mixtures. The reactions of alkylated products with bases were studied.For the previous communication, see V. A. Shlyapochnikov, G. I. Oleneva, N. O. Cherskaya, O. A. Luk'yanov, V. P. Gorelik, O. V. Anikin, and V. A. Tartakovsky,Izv. Akad. Nauk, Ser. Khim., 1994, 1610 [Russ. Chem. Bull., 1994,43, No. 11 (Engl. Transl.)].Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1775–1778, October, 1994.     

A new method for the synthesis of aziridine derivatives

The photoinduced reaction ofN-trialkylstannyl-N-triorganylsilyl-substituted allylamines with perfluorocarbonyl iodides results in the formation of 1-triorganylsilyl-2-(,a-dihydroperfluoroalkyl)aziridines.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya. No. 3, pp 759–760, March, 1996.     

Preparation ofN-nitrohydroxylamines by substitutive nitration

Interaction of Na- or K-salts ofN-acetyl-N-methylhydroxylamines with aryl or aryl halides results in correspondingO-substitutedN-acetyl-N-methylhydroxylamines. Nitration of these compounds by nitronium salts or dinitrogen pentoxide results inO-substitutedN-methyl-N-nitrohydroxylamines.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 239–241, January, 1996.     

Reactions ofN,N-dibromo-tert-butylamine with ketoximes

Reactions of acetone, cyclohexanone, and adamantanone oximes withN,N-dibromo-tert-butylamine result in the correspondingC-bromo-diazene-N-oxides. In the case of benzophenone oxime,O, O'-(diphenylmethylene)-bis-benzophenone oxime has been obtained.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 176–177, January, 1994.     

Synthesis of ammonium salts ofO-substitutedN-nitrohydroxylamines

Ammonium salts ofO-substitutedN-nitrohydroxylamines were synthesized by nitration ofO-substitutedN-benzoyl- orp-nitrobenzoy1hydroxylamines followed by treatment of the reaction products with an alcohol solution of ammonia.Translated fromIzvestiya Akadernii Nauk. Seriya Khimicheskaya, No. 1, pp. 132–134, January, 1996.     

O,N-Dimethylation of 5,6-dihydroxynicotinic acid

AnO,N-dialkylation product, 1-methyl-5-metlioxy-6-oxo-1,6-diliydropyridine-3 carboxylic acid, is formed in the reaction of 5,6-dihydroxynicotinic acid with dimethylsulfate.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1554–1555, June, 1996.     

Nitrodeiodination of 4-iodo-l-methylpyrazoles

4-iodo-l-methylpyrazoles react with a nitrating mixture at 55 °C to give the corresponding 4-nitro-I-methylpyrazoles. The qualitative dependence of the nitrodeiodination rate on the structure of the heterocycles and the reaction conditions was considered.Translated fromlzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2722–2725, November, 1996.     

Complexation equilibrium in a substrate- MgCl2(CaCl2)-Pd/C catalytic system and the influence of its position on asymmetric induction in hydrogenation ofN-acetyl-dehydrophenylalanyl-S-proline

The role of Ca and Mg salts as promoters of asymmetric induction in hydrogenation ofN-acetyl-dehydrophenylalanyl-S-proline in a substrate— MX₂—Pd/C catalytic system was studied. The data of potentiometric titration,¹H NMR spectroscopy, and the value of diastereomeric excess (de) of the resultingN-acetyl-R-phenylalanyl-S-proline indicate the complexation of the substrate with calcium and magnesium chlorides in an alcoholic solution. Ionization and equilibrium constants of the complex were determined. Excess salt shifts the equilibrium toward the complex formation, which increasesde up to 70 %.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1964–1967, August, 1996.     

(N-methyl-N-alkoxymethylaminomethyl)dialkoxysilanes and bis[N-methyl-N-(dialkoxysilylmethyl)amino]methanes

(N-methyl-N-alkoxymethylaminomethyl)-dialkoxysilanes and bis[N-methyl-N-(dialkoxymethyl)amino]methanes were first obtained by the interaction of (N-methylaminomethyl) dialkoxy-R-silanes with chloromethyl alkyl ethers in yields of 40–67% and 10–25 %, respectively.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 382–383, February, 1995.     

Dinitramide and its salts

Dinitramide readily adds to acrolein, methyl vinyl ketone, and phenyl vinyl ketone, but not to acrylonitrile or methyl acrylate. Treatment of dinitro compounds (O₂N)₂NCH₂CH₂COR (R = H, Me, Ph, OMe) with bases results in dinitramide salts in 66–83 % yields.For part 1, see Ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1264–1266, July, 1994.     

Phosphorylation ofN-trimethylsilyllactams

Treatment ofN-trimethylsilyllactams with phosphoryl chlorides results in mixtures of products, whose formation can be explained by competition betweenN- andO-phosphorylation.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1644–1648, September, 1994.     

Solvent effect on catalytic properties of the HCI-DMF-1,1,2,2-tetrachloroethane system

Ionization of 2- and 3-nitroanilines was studied in HCl-DMF-1,1,2,2-tetrachloro-ethane (TCE) solutions at 25 °C. The ionization capability of the medium and basicity constants pK _i of indicators change depending on the ratio of the components. The numerical values of pK _i are found to depend on the analytical composition of the DMF-TCE solvent. The solvent effect on pK _i is associated with a change in the solvation of the nonionized form of the indicators.Translanted fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1446–1449, June, 1996.     

Synthesis and structure of 2-amino- 5-azolyl-3-cyano-4H-pyrans

Previously unknown 5-azolylpyrans were obtained by reactions ofN-acetonyl- andN-phenacylimidazoles, -triazoles, and -tetrazoles with arylmethylenemalononitriles. The structure of 2-amino-3-cyano-6-methyl-5-(5-nitrotetrazol-2-yl)-4-phenyl-4H-pyran was established by X-ray structural analysis.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2050–2055, August, 1996.     

Vibrational spectra and structure ofN,N-dinitromethylamine

The vibrational (IR and Raman) spectra ofN,N-dinitromethylamine were studied. The assignments of the bands were carried out using a comparison of spectra obtained in different aggregate states, invoking the results of normal coordinate analysis. The most probable symmetry of the molecule was shown to beC _s with a planar configuration of the N(NO₂)₂ moiety.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1503–1507, August, 1995.     

Reaction of vinyloxyalkylamines with mercaptoacetic acid

N-[2(3)-Hydroxyalkylj-4-thiazolidinones have been synthesized by the reaction of 2(3)-vinyloxyalkylamines with mercaptoacetic acid in 24–69 % yield. The structure of the compounds obtained was supported by (R and¹H NMR spectroscopic data.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 677–679, March, 1996.     

Synthesis of thermostable aliphatic alkylene-bis(N-phenyl aldonitrones)

A general method for the synthesis of alkylene-bis(N-phenyl aldonitrones) (bisnitrones) by reaction of dianions ofN,N-bisnitroacetyldiamines with nitrobenzene in DMF was proposed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2588–2590, October, 1996.     

Crystal and molecular structure ofN-phenyl-4-nitrobenzamidoxime

N-Phenyl-4-nitrobenzamidoxime has been studied by X-ray structural analysis. In two crystallographically independent molecules1A and1B, amidoxime groups adopt a planarZ configuration, and these fragments are in ans-trans conformation with respect to the =N-O and C-N(H) bonds; an intramolecular NH...O bond occurs. The nitrophenyl and phenyl groups are rotated with respect to the amidoxime plane [ONCN] by –57 and –32° in1A and –38 and –22° in1B, respectively. The rotation of the fragments about the C(1)-N(2) bond is –28 (1A) and –35° (1B). In crystals, molecules1A and1B are linked in oxime dimers through two intermolecular =N...(HO) hydrogen bonds; dimers form double chains through two NH...(O₂N) hydrogen bonds.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1516–1519, August, 1995.The work was supported by the Russian Foundation for Basic Research (Project No. 93-03-05069).     

Interaction ofZ-1,2-borylphosphinoalkene with ketenimine

N-Phenyl-C,C-diphenylketenimine adds toZ-1-butyl-I-dibutylboryl-2-diphenylphosphino-2-phenylethene to give 2,2,3-tributyl-6-diphenylmethylideno-1,4,5,5-tetraphenyl-1-aza-5-phosphonia-2-borataeyclohex-3-ene, which rearranges into 4,6-dibutyl-2-diphenylphosphino-1,1,3,5-tetraplienyl-3-aza-4-boradeca-1,5-diene upon heating. Its crystal structure has been established by X-ray analysis.Deceased in 1995.Translated from IIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. l, pp. 183–187, January, 1996.