O. A. Luk'yanov

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

N,N-Dinitro derivatives of alkylurethanes, benzamide, andp-toluenesulfamide were synthesized for the first time. Their reactions with ammonia afforded the ammonium salt of dinitramide in 44–85% yields.

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.

PALLADIUM-CATALYZED REACTION OF BROMINE- AND IODINE-CONTAINING ISOTHIAZOLES WITH OLEFINS

Abstract3-Bromo-4-alkenylisothiazoles were synthesized by the reaction of 3-bromo-4-iodoisothiazole with olefins in the presence of palladium acetate

N′-(α-acetoximinoalkyl)diazene-N-oxides and some of their transformations

Nitroso compounds of the aromatic and aliphatic series react with O-acetylalkanoylamidoximes in the presence of dibromoisocyanurate, forming the previously unknown N′-(α-acetoximinoalkyl)diazene-N-oxides, which under gaseous NH3 or oxalic acid in methanol lose the acetyl group and as a result are transformed into the previously unknown N′-(α-hydroximinoalkyl)diazene-N-oxides.

Reaction ofN,N-bis(chloromethyl)amides withN,N′-diacylated alkene(arylene)diamines

Reactions ofN,N-bis(chloromethyl)amides withN,N′-diacyl derivatives of ethylenediamine (oro-phenylenediamine) result in formation of the corresponding 1,3,5-triacylated perhydro-1,3,5-triazepines (or their benzoanalogs) or 1,3-diacylated imidazolidines (or their benzoanalogs). Reactions ofN,N-bis(chloromethyl)amides withN,N′-ditosylated trimethylenediamine occur in a similar way. The direction of the reactions depends on the type of the acyl substituents and the strength of the bases.

New method for the synthesis of 2-substitutedN, N′-diacylimidazolidines

A method for the synthesis of 2-substitutedN, N′-diacylimidazolidines was developed. The method is based on the reactions of acylating reagents (carboxylic acid chlorides and anhydrides, sulfonic acid chlorides, a carbamic acid chloride, and ethyl chlorocarbonate) with Schiffs bases prepared by the reaction ofN-acylethylenediamines with aldehydes.

New regiospecific methods for the synthesis of N′-cyanodiazene N-oxides

New regiospecific methods have been developed for the synthesis of aliphatic, aromatic, and heterocyclic N′-cyanodiazene N-oxides based on the reactions of nitroso compounds with a system containing the sodium salt of cyanamide and tert-butyl hypochlorite and with a system containing cyanamide and dibromoisocyanurate.

Synthesis of bromine-and iodine-containing perhaloisothiazoles

A method was developed for the synthesis of bromine- and iodine-containing perhaloisothiazoles by bromination and iodination of 3-bromoisothiazole prepared from the available 3-hydroxyisothiazole.

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.