Organosilicon compounds containing the furan ring

Hydrolysis of organosilicon esters of 3-(2furyl)acrylic or cinnamic acids, and cohydrolysis with organyltrialkoxysilanes gives organosilicon resins, which solidify when illuminated with UV light.For Part XIII see [1].     

Organic compounds containing a pentafluorothio group

The addition of sulfur chloride pentafluoride to various terminal olefins, including those containing functional substituents, was studied. Possible side processes in these reactions are oligomerization and fluorination of the starting olefin.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2952–2954, December, 1996.     

Organosilicon hypersilylchalcogenolates and related compounds

Reaction of potassium hypersilylchalcogenolates (Me₃Si)₃SiEK (E = S, Se, Te) with organochlorosilanes R_4 − xSiCl_x (R = Me, Ph; x = 1-4) and methylchlorodisilanes (Si₂Me₅Cl, 1,2-Si₂Me₄Cl₂) yields organosilicon hypersilylchalcogenolates [(Me₃Si)₃SiE]_xSiR_4 − x (x = 1-4) and [(Me₃Si)₃SiE]_xSi₂Me_6 − x (x = 1, 2). A partial substitution product, [(Me₃Si)₃SiSe]₂SiPhCl (2) has been obtained by reaction of PhSiCl₃ with 1.5 equivalents (Me₃Si)₃SiSeK. Besides characterization by ¹H, ¹³C, ²⁹Si, ⁷⁷Se and ¹²⁵Te NMR spectroscopy the compounds [(Me₃Si)₃SiTe]₂SiPh₂ (1), [(Me₃Si)₃SiSe]₂SiPhCl (2) and [(Me₃Si)₃SiSe]₂Si₂Me₄(3) have also been analyzed by crystal structure analyses.Starting from (Me₃Si)₅Si₂K treatment with sulfur gave the highly branched potassium heptasilanylthiolate (Me₃Si)₅Si₂SK. Reactions with methylchlorosilanes Me_4 − xSiCl_x (x = 1, 2, 3) yielded organosilicon heptasilanylthiolates [(Me₃Si)₃Si-(Me₃Si)₂Si-S]_xSiMe_3 − x.     

Reactivity of compounds containing the ferrocenylmethyl group

Summary The reactions of ferrocenylmethyllithium with formaldehyde, benzaldehyde, and carbon dioxide were studied. These reactions go without rearrangement.     

Organosilicon compounds of the furan series

2-Vinylfuran is hydrosilylated by trichlorosilane, alkyldichlorosilanes, triethoxysilane, alkyldialkoxysilanes, trialkylsilanes, and tetraethyldisoloxane, in the presence of H₂PtCl₆ · 6H₂O, 1% Pt/C, and 1% Pd/C. The structures of the products are shown by PMR, and IR spectra, and proved by reverse synthesis. It is shown that in the majority of cases hydrosilylation is in accordance with Farmer's rule. New views on the mechanism of hydrosilylation are put forward.For Part IX see [1].Thanks are due to A. Grinvald and O. Neiland for the IR spectra, and to R. Gavar for the EPR work.     

Organometallic synthesis of compounds containing a perfluoroisobutenyl group

Conclusions Perfluoroisobutenyllithium and perfluoroisobutenylmagnesium bromide were obtained, and it was shown that these reagents can be used in the synthesis of compounds containing a perfluoroisobutenyl group.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, Np. 12, pp. 2826–2828, December, 1982.     

Synthesis of unsaturated compounds containing the nitrodifluoromethyl group

Conclusions We synthesized a number of saturated and unsaturated compounds containing the nitrodifluoromethyl group.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2742–2744, December, 1972.     

Organosilicon and organophosphorus compounds with pseudohalide groups

The reactions of alkoxydimethylsilyl cyanides with some tetracoordinated phosphorus chlorides and fluorides were investigated. It was shown that the investigated reactions are realized primarily with the replacement of two halogen atoms by functional groups. The transformations of the phosphorus acid cyanides obtained with metal fluorides were studied.For previous communication, see [1].Institute of Physiologically Active Substances, Russian Academy of Sciences, 142432 Chernogolovka. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 187–191, January, 1992.     

Synthesis of pentacoordinated germanium compounds containing a phosphonyl group

The title compounds were prepared by the reaction of germanium sesquioxides with diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonate in good yields (72–94%). The X-ray analyses showed that the geometry about the germanium atom was a distorted trigonal bipyramid. © John Wiley & Sons, Inc.     

Synthesis of new spiro compounds containing a carbamate group

1,3-Dipolar cycloaddition to methyl 4-[2-(2-oxo-2,3-dihydro-1H-indol-3-ylidene)-1-oxoethyl]-phenylcarbamate of diazomethane in chloroform-diethyl ether and of 3,4-dimethoxybenzonitrile oxide generated from the corresponding aldehyde oxime by the action of N-chlorobenzenesulfonamide sodium salt (Chloramine B) in boiling ethanol gave, respectively, methyl 4-(2-oxo-1′,5′-dihydro-1H-spiro[indole-3,4′-pyrazol]-3′-ylcarbonyl)phenylcarbamate and methyl 4-[3′-(3,4-dimethoxyphenyl)-2-oxo-1H,4′H-spiro[indole-3,5′-isoxazol]-4′-ylcarbonyl]phenylcarbamate. The condensation of methyl 4-[2-(2-oxo-2,3-dihydro-1H-indol-3-ylidene)-1-oxoethyl]phenylcarbamate with hydrazine hydrate in ethanol afforded methyl 4-(2-oxo-1,2,2′,4′-tetrahydrospiro[indole-3,3′-pyrazol]-5′-yl)phenylcarbamate.     

Vibrational spectra of polyfluoroaromatic compounds containing the azomethine group

Conclusions The replacement of hydrogen atoms of the benzene rings in aromatic azomethines is accompanied by changes in the state of the nitrogen atom and the C=N bond. This is expressed in a shift of the signals in the NMR spectra and in a change in band intensities for the stretching vibrations of multiple bonds in the Raman spectra, but it does not affect the positions of these bands.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 568–575, March, 1984.