Synthesis of 4H-pyrans by O-cyclization of 1,5-diketones

Substituted 4H-pyrans were obtained in high preparative yields by the reaction of 1,5-diketones with acetic anhydride and boron trifluoride etherate in diethyl ether. It is assumed that the heterocyclization of 1,5-diketones includes a step involving the formation and transformations of an acyloxy carbonium ion.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 320–322, March, 1992.     

Investigation of metal-containing carbon nanostructures prepared from functional polymers

Metal-containing carbon nanostructures are prepared by heating poly(vinyl alcohol) in mineral media with a lamellar structure at a temperature below 300°C. It is demonstrated that three possible types of nanostructures can be formed, namely, multilayer carbon nanotubes, spherical carbon nanoparticles, and finely crystalline carbon structures. According to the data of transmission electron microscopy, the nanotube size falls in the range from 50 to 300 nm and the nanotubes themselves have a stranded structure.     

Theoretical Study of the Mechanism of the Nitro-Nitrite Rearrangement and Its Role in Gas-Phase Monomolecular Decomposition of C-Nitro Compounds

Semiempirical, ab initio, and density functional theory calculations were used to study the primary act of gas-phase monomolecular decomposition of certain C-nitro compounds and their radical cations, associated with the nitro-nitrile rearrangement. It was shown that the reaction fails to occur with all neutral molecules of aliphatic nitro compounds (except for fluoronitromethane and fluoronitroethene) and has a much lower barrier with the corresponding radical cations. An important role of the nitro-nitrile rearrangement in gas-phase decomposition of aromatic nitro compounds was demonstrated.     

Synthesis of phosphorus (silicon,tin)-containing derivatives of mercaptoketenes and some of their properties

Some newS-phosphorylated,S-silylated, andS-stannylated derivatives of -mercaptoketones were obtained. The reactions of some of these compounds induced by the temperature and by molecular oxygen as well as the phosphorylation of the Si- and Sn-containing derivatives were studied.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 353–357, February, 1995.     

Dialkylamino- and alkoxytrialkylstannanes as reagents for synthesis of organoboryl (trialkylsilyl) ketenes

Dialkylamino- and alkoxytrialkylstannanes have been studied as N- and O-nucleophilic reagents in substitution reactions at the B-Br bond. The previously unknown bis(dialkylamino)- and dialkoxyboryl trialkylsilyl ketenes were synthesized. Some peculiarities of the reactivity of these compounds have been studied.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 911–915, May, 1994.This research was carried out in the framework of the Universities of Russia State Program.     

Homolytic addition of 1,3-oxathiolane to unsaturated hydrocarbons

The homolytic addition of 1,3-oxathiolane to olefins takes place with the formation of 2-substituted 1,3-oxathiolanes and insignificant amounts of functional derivatives of sulfides.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 259–263, February, 1986.     

Transformations of sym-octahydroxanthene-1,8-diones and 1,8-dioxo-sym-octahydroxanthylium salts in recyclization under the influence of amines

The chemical behavior of 9-R-sym-octahydroxanthene-1,8-diones and salts based on them in recyclization reactions under the influence of amines was studied. The effect of the basicity of the amines on the direction of recyclization was established. A method is proposed for the single-stage synthesis of sym-octahydroacridine-1.8-dione oximes based on 1,8-dioxo-sym-octahydroxanthenes. Conditions were worked out for the oxidation of sym-octahydroxanthene-1,8-diones and N-R-decahydroacridinediones to the corresponding salts. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 32–38, January, 2006.     

The influence of perchloric acid on the spectral and luminescent properties of cyclopalladated complexes

The influence of perchloric acid in ethanol on the spectral and luminescent characteristics of cyclopalladated amine complexes with 4-phenylpyrimidine, 1,7-phenanthroline, and coumarin-6 is studied. A protonation mechanism is proposed.     

Electrochemical reduction of 4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one

The properties of 4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-one which contains the trichloromethyl substituent at a quaternary carbon atom have been studied by cyclic voltammetry, rotating disk electrode voltammetry, and preparative electrolysis. Reductive dehalogenation involves initial two-electron reductive elimination of one of the geminal chlorine atoms followed by consecutive addition of proton, simultaneous elimination of the two residual halogen atoms to form carbene, and rearrangement of cyclohexadienone into the corresponding 4-methylcyclohepta-2,4,6-trien-1-one.