P. V. Galkin

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.

Preparation and properties of N-fluoro- and N-nitrobis(2,2,2-trinitroethyl)ureas

Fluorination and nitration of bis(2,2,2-trinitroethyl)urea has given the novel N-fluoro-bis(2,2,2-trinitroethyl)urea and N-nitro-bis(2,2,2-trinitroethyl)urea. The thermal decomposition rates and parameters for bis(2,2,2-trinitroethyl)urea and its derivatives have been found, and the standard enthalpies of combustion, and the standard enthalpies of formation of these compounds calculated therefrom, have been determined.

1,1,4,4-Tetranitrobutane-2,3-diol and its derivatives. 3. Synthesis of 1,4-dichloro- and 1,4-dibromo-1,1,4,4-tetranitrobutane-2,3-diol dinitrates and their crystalline structure

Abstract1,4-Dichloro- (1) and 1,4-dibromo-1,1,4,4-tetranitrobutane-2,3-diol dinitrates (2) were synthesized by nitration of the corresponding diols with a mixture of trifluoroacetic anhydride and nitric acid. The x-ray diffraction investigations of 1 and 2 that have been carried out showed the influence of the intramolecular interactions of the nitro and nitrate groups on the packing of the molecules in the crystal.

Preparation and properties of secondary amides of 1,1-dinitroalkanecarboxylic acids

The previously unknown secondary amides of 1,1-dinitroalkanecarboxylic acids were prepared by the reaction of polynitroimidoyl fluorides with water in the presence of mineral acids. They are inert with respect to electrophiles, but react with nucleophiles with the cleavage of the C-C bond between the carbonyl C atom and the C atom of the dinitromethylene group. An X-ray structural study of the amides was carried out and their thermochemical characteristics were determined.

New N-nitrosoamines. 2. Transformations of tetrahydro-1,3-oxazines into nitrates of N-nitrosoamino alcohols

The reactions of HNO3 with tetrahydro-1,3-oxazines 1a—c produced by aminomethylation of diketopiperazine, isatin, and succinimide, respectively, afforded nitrates of amino alcohols [RCH2NH2(CH2)3ONO2]+NO3– (4a—c) whose subsequent N-nitrosation (NaNO2, AcOH) gave nitrates of N-nitrosoamino alcohols RCH2N(NO)(CH2)3ONO2 (5a—c). The structures of compound 5b,c were established by X-ray diffraction analysis.

Transformations of nitrates (nitro esters) of amino alcohols involving both functions. 1. Reaction with alkali metal hydrogen carbonates

The reaction of nitrates (nitro esters) of amino alcohols with alkali metal hydrogen carbonates yielding oxazolidin-2-ones and tetrahydro-1,3-oxazin-2-ones was discovered. A large number of both known and newly synthesized nitrates of amino alcohols with various structures were involved in this reaction, and the optimum reaction conditions were found. New oxazolidin-2-ones and tetrahydro-1,3-oxazin-2-ones were synthesized. Two more transformations were found for a few examples. One of the reactions gives nitramino alcohols, whereas another reaction affords polymers.

Polynitro-substitutedN-alkylalkaneimidoyl chlorides

The reaction of α-fluorosubstituted polynitroalkylaldimines with HCl results in replacement of the fluorine atom by a chlorine atom. The hitherto unknown α-chlorosubstituted polynitroalkylaldimines have been obtained, and their X-ray structural investigation has been performed.

ELIMINATION REACTIONS OF N,C-DIFLUORIDES

Hydrogen fluoride was eliminated from N,C-difluorinated derivatives of bis(polynitroalkyl)amines by the action of alkanols. Previously unreported α-fluoropolynitroalkylaldimines were obtained.

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 theβ position relative to the amine nitrogen gives previously unreported vicinal N,C-difluorides.

BIS(POLYNITROALKYL)-N-CHLORAMINES

A series of previously unreported bis(polynitroalkyl)-N-chloramines was obtained by the chlorination of bis(polynitroalkyl)amines.