π-Electronic structure of the nitrofuran system

Anion radicals of 2-vinylene derivatives of 5-nitrofuran were obtained by electrochemical generation. The hyperfine structure (hfs) of the ESR spectra of these anion radicals indicates delocalization of the unpaired electron over their entire π-electron system. The effect of the vinylene grouping on the distribution of the unpaired electron in the anion radicals and on the distribution of the unpaired electron in the vinylene grouping itself was examined on the basis of the hfs constants. It was found that the vinylene grouping by localizing more than 10% of the density of the unpaired electron on itself reduces, by a factor of 1.4, the effect of substituents in the 2 position of 5-nitrofuran on the distribution of the spin of the unpaired electron in the nitrofuran framework.     

Chemical instabilities during oxidation of 1,4-naphthalenediol in a homogeneous medium: II. Thermodynamic analysis and mathematical modeling

A possible mechanism of 1,4-naphthalenediol oxidation in the oscillatory regime has been considered, and a mathematical model describing the kinetics has been developed. Based on a thermodynamic Lyapunov function, it has been shown that the source of chemical instabilities is in the existence of autocatalytic steps and dynamic feedbacks. Qualitative analysis and numerical solution of the set of differential equations that model the reaction kinetics have been performed. The character of the stationary state and the possibility of bifurcations have been determined. The mathematical model satisfactorily describes the processes occurring in the system.     

Thermal rearrangement of 2,5-diaryl-3,3,4,4-tetracyanopyrrolidines

It was shown that briefly boiling solutions of 2,5-diaryl-3,3,4,4-tetracyanopyrrolidines in DMF caused rearrangement into 5-aryl-2-(N-arylidenamino)-3,4-dicyanopyrroles, which are methylated with diazomethane both at the NH bond and at the carbon atom of the azomethine fragment.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 42–46, January, 1995.     

Cyanoethylation of azafluorenes and syntheses of alcohols containing an azafluorene fragment

Isomeric (with respect to the position of the nitrogen atom) azafluorenes were cyanoethylated. The resulting 9,9-bis(-cyanoethyl) derivatives were converted to the corresponding dibasic acids and their diesters. The latter were subjected to the Dieckmann reaction to obtain spiro compounds with azafluorene and cyclohexene fragments. The analogous spirans with 1,3-dioxalane and 1,3-dioxane rings were obtained from 3-methyl-2-azafluorenone.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1668–1672, December, 1982.     

Reactions of aromatic acetylenic ethers with triethylgermane

Conclusions The addition of Et₃GeH to the phenoxy- and phenylthioacetylenes under the influence of (Ph₃P)₃RhCl is both nonstereo- and nonregiospecific. The analogous reaction with 3-aroxy-1-propynes is stereospecific but nonregioselective.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2618–2620, November, 1982.