A. A. Fainzil'berg

α-Azidopolynitroalkanes. Synthesis and vibrational spectra

Methods for the preparation of α-azidopolynitroalkanes by reactions of polynitroalkanes or α-(difluoroamino)polynitroalkanes with NaN3 were developed. In the case of tetranitromethane, one or two nitro groups can be substituted, depending on the reaction conditions. The reaction of 1,1,1-trinitroethane with NaN3 affords nitro-1,2,3-triazole, together with 1-azido-1,1-dinitroethane. The IR spectra of α-azidopolynitroalkanes were studied.

Crystal and molecular structure of 2,5-bis(fluorodinitromethyl)-1,3,4-oxadiazole

An X-ray structural study of 2,5-bis(fluorodinitromethyl)-1,3,4-oxadiazole (1), one of the representatives of azoles with strong electron-withdrawing substituents, has been carried out. It has been found that in the orthorhombic modification of1 the conformations of the fluorodinitromethyl groups are different. Intermolecular contacts in the crystal are realized through the heterocycles arranged at large angles to each other. The presence of strong electron-withdrawing substituents results in shortening of the C-O bonds and in a certain increase in the OCN angle in the 1,3,4-oxadiazole ring.

Synthesis and some properties ofN-polynitromethyl derivatives of fused benzotriazoles

The procedures for the synthesis ofN-polynitromethyl derivatives of benzo[1,2-d;4,5d′]ditriazole-4,8-dione are described. Some chemical properties of the compounds obtained are investigated.

The spectra and structures of halogen derivatives of trinitromethane

1. We have carried out a spectral study of the halogen derivatives of trinitromethane. 2. We have given the relations of the oscillation frequencies to the bonds C-N and C-Hal. 3. The anomalous values of the frequencies and intensities for the bonds C-Hal in the halotrinitromethanes is explained by the presence of the bonds C-Hal and N-O.

Interaction of polynitro compounds with difluoroamine

Difluoroamine does not react with tetranitromethane and fluoro-, chloro-, and bromotrinitromethanes in DMF and in acidic media (CF3COOH, ClSO3H, FSO3H, and oleum), but reacts with α-fluoro- and α-(difluoroamino)-α,α-dinitrotoluenes to give substitution products of the difluoroamino group for both the nitro groups,viz., PhC(NF2)2F and PhC(NF2)3, respectively.

The synthesis of fused benzotriazoles based on hexaaminobenzene derivatives

New methods for synthesis of hexaaminobenzene are proposed and, based on this compound, previously unknown preparative procedures for obtaining fused benzotriazoles are developed.

A polarographic study of aliphatic nitro compounds

1. Study has been made of the behavior of dinitroformoxime, and of methods of determining the concentration of this compound in solution proposed. 2. Study has been made also of the kinetics of the reaction of dinitromethane with nitrous acid in acid solution, the reaction proving to be second-order, first-order in each of the system components. 3. The ionization constant for dinitroformoxime in aqueous solution has been determined.

Synthesis based on electrogenerated carbenes

Conclusions1.The MINDO/3 method has been used to calculate enthalpies in decomposition reactions of the dimethylsulfonium dinitromethylide cation radical in the gas phase; it has been shown that the most probable direction of decomposition leads to the formation of dinitrocarbene.2.The MINDO/3 method has been used to calculate the geometric parameters and electronic structure of dinitrocarbene, and it has been shown that the singlet state is more favorable than the triplet state. It has been found that, in a series of singlet carbenes with electron-acceptor substituents, dinitrocarbene is the strongest electrophile.

POLAROGRAPHIC STUDY OF ALIPHATIC NITRO COMPOUNDS. 13. GENERAL MECHANISM OF ELECTROREDUCTION OF POLYNITRO COMPOUNDS

Summary1.The electroreduction of polynitro compounds that do not have a mobile α-hydrogen atom conforms to certain general relationships: The reduction in the first stage takes place with C-N bond rupture, and then is accompanied by chemical reactions with participation of the nitro-compound anion that has been formed.2.The kinetics of the chemical reactions that accompany electroreduction will depend on the acidity of the medium and the nature of the intermediate anion, and these reaction kinetics determine the type of polarographic behavior of polynitro compounds.

Polarographic study of aliphatic nitro compounds 11. Reduction of nitroalkanes with an electronegative substituent in the α position

1. Reduction of nitroacetonitrile and 2-cyano-2-nitropropane proceeds through attack at the nitrogroup N-O bond. 2. The details of the structure of the anion formed through C-N bond rupture will determine whether nitroalkane reduction, will proceed through the C-N or N-O bonds.