O. V. Anikin

Synthesis of Tetrazino‐tetrazine 1,3,6,8‐Tetraoxide (TTTO)

This study presents the first synthesis and characterization of a new high energy compound [1,2,3,4]tetrazino[5,6-e][1,2,3,4]tetrazine 1,3,6,8-tetraoxide (TTTO). It was synthesized in ten steps from 2,2-bis(tert-butyl-NNO-azoxy)acetonitrile. The synthetic strategy was based on the sequential closure of two 1,2,3,4-tetrazine 1,3-dioxide rings by the generation of oxodiazonium ions and their intramolecular coupling with tert-butyl-NNO-azoxy groups. The TTTO structure was confirmed by single-crystal X-ray.

On the structure and spectra of dinitramide salts

Abstract The preparation for the isotopically substituted dinitramide salts has been proposed. The 14 N and 15 N NMR spectra of the 15 N-enriched dinitramide anion in solution are measured and interpreted for the first time. New experimental IR and Raman spectra are obtained for the NH 4 + and K + salts of dinitramide in the solid state and in solution. The assignments are made with the help of quantum-mechanical force field calculations and normal-coordinate analysis. The harmonic vibrational spectrum of the dinitramide anion calculated at the B3LYP/6-31+G(d) level in the presence of solvent correlates best with the experimental data. The structure and spectra of the M + CH(NO 2 ) 2 − and M + N(NO 2 ) 2 − (M denotes a counterion) are compared and discussed. Topology of the electron charge density in the dinitramide anion is analyzed within the framework of Baders theory of atoms in molecules.

DINITRAMIDE AND ITS SALTS. VII: SPECTRA AND STRUCTURE OF DINITRAMIDE SALTS

The vibrational and electronic spectra of dinitramide salts MN(NO2)2 (M=K, Na, Li, NH4, Fe, Ag, Mn, Mg, Rb, C(NH2)3) have been studied. The IR and Raman spectra of solutions and melts of the salts have been satisfactorily interpreted on the basis of the anion model withC2v symmetry. The complication of the spectra in the crystalline phase has been explained by restructurization of the anion that reduces its symmetry and makes the nitro groups nonequivalent.

Stabilization of ammonium dinitramide in the liquid phase

The kinetics of accumulation of the main products of thermal decomposition of ammonium dinitramide in the melt was investigated. The isotope composition of nitrogen-containing gases evolved by the decomposition of 15NH4N(NO2)2 and NH415N(NO2)2 was found. Easily oxidized salts, amines, amides, iodides, and other compounds soluble in the melt interfere with the liquid-phase decomposition of ammonium dinitramide.

Oxidative nitration of the amino group: synthesis of dinitramide and cyanonitramide salts*

A convenient preparative method for the synthesis of potassium dinitramide and cyanonitramide salts was developed. The method involves reactions of nitramide or cyanamide with KNO2 and PhI(OAc)2 or PhIO in methanol.

DINITRAMIDE AND ITS SALTS. 9. MERCURY(II) DINITRAMIDATE, A NEW REAGENT IN CHEMISTRY OF ORGANOMERCURY COMPOUNDS

The potentialities of synthesis on the basis of mercury(II) dinitramidate Hg(N3O4)2 in mercuration, addition to the double carbon-carbon bond, alkylation, and complexation are shown.

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.

A novel heterocyclic system — dihydro-2H-1,5,2,4-dioxadiazine. 2,4-Dimethyldihydro-2H-1,5,2,4-dioxadiazine hydrochloride: synthesis and NMR study

The first representative of a novel heterocyclic system, namely, 2,4-dimethyldihydro-2H-1,5,2,4-dioxadiazine hydrochloride, was synthesized.

N-nitroimidoyl chlorides: synthesis and structure

A new method was developed for the synthesis of N-nitroimidoyl chlorides O2N—N=C(R)Cl (R = SMe, Phth; Phth is phthalimide) by the reaction of O2N—N=C(R)SMe with SO2Cl2. The reaction of O2N—N=C(SMe)Cl with potassium phthalimide leads to the replacement of the Cl atom by the phthalimide moiety. The compounds O2N—N=C(Phth)Cl and O2N—N=C(Phth)SMe were studied by X-ray diffraction and quantum chemical methods. The C=N—N and NO2 groups in the O2N—N=C(Phth)Cl molecule were found to be completely orthogonal to each other. The explanation of this fact was proposed.

Alkylation of salts ofN-nitrohydroxylamines with chloromethylnitramines

The reactions of Ag-salts ofN-nitmhydroxyumines withN-methyl-N-chloromethylnitramine afford mainly products ofO-alkylation, whereas the reactions of the corresponding Li-, Na-, K-, Mg-, and NH4-sals in the presence of tetrabutylammonium (TBAB) give mainly products ofN-alkylation. The reactions of the corresponding. NH4-salts with bis-(chloromethyl)nitramine in the presence of TBAB lead solely to products ofO-alkylation. Increasing in the amount of TBAB results in the appearance of theN-isomer.