Hydrosilylation of aromatic nitriles promoted by solvated rhodium atom-derived catalysts

Rhodium metal particles, isolated as supported or unsupported powder starting from mesitylene solvated rhodium atoms, catalyse the hydrosilylation of aromatic nitriles to N,N-disilylamines in high conversion at 100°C. Different hydrosilanes (HSiMe₃, HSi(OEt)₃) can be employed. In the case of cinnamonitrile, the chemoselectivity of the reaction to 2-trimethylsilyl-3-phenylpropionitrile and (E)- and (Z)-1-di(trimethylsilyl)amino-3-phenyl-1-propene is strongly dependent on the reaction temperature. The commercial rhodium on γ-Al₂O₃ catalyst is considerably less active and selective than the analogous catalyst prepared via Metal Vapour Synthesis (MVS) probably owing to the different dimension and distribution of the metal particles in the two samples as shown by HRTEM analysis.     

Spirocyclohexadienones. 6. Three-component synthesis of 1-R-3,3-dimethyl-2-azaspiro[4.5]deca-1,6,9-trien-8-ones

1-R-3,3-Dimethyl-2-azaspiro[4.5]deca-1,6,9-trien-8-ones were synthesized through three-component condensation of anisole, isobutyraldehyde, and a corresponding nitrile in dichloromethane in the presence of concentrated sulfuric acid.     

等离子体聚合膜的电学性质研究——Ⅱ.腈类单体结构的影响

等离子体聚合膜多为具有高电阻的绝缘体。但是,近年来的研究结果表明,选择合适的单体及采取一些措施,可使等离子体聚合膜从绝缘体至半导体乃至导体的宽范围变化。本文将一些具有不同化学结构的腈类单体进行了等离子体聚合,研究了单体化学结构对所得聚合膜结构及电学性质的影响。聚合方法等同前报。     

Interaction of Alkyl 5,6-Dialkyl-2-amino-3-cyano-4-pyridinecarboxylates with O-Nucleophiles. Synthesis of 6,7-Dialkyl-4-amino-2,3-dihydro-1H-pyrrolo[3,4-c]pyridine-1,3-diones

The reaction of alkyl 5,6-dialkyl-2-amino-3-cyano-4-pyridinecarboxylates with certain O-nucleophiles was investigated, as a result of which 6,7-dialkyl-4-amino-2,3-dihydro-1H-pyrrolo[3,4-c]pyridine-1,3-diones were synthesized.     

Synthesis of 2-amino-5-(5R-1,2,4-oxadiazolyl-3)-1,3,4-oxadiazoles

The interaction of 2-amino-1,3,4-oxadiazole-5-carboxamidoxime with nitriles in the presence of ZnCl₂ and HCl or with trichloroacetic anhydride affords 2-amino-5-(5R-1,2,4-oxadiazolyl-3)-1,3,4-oxadiazoles. Their reactions with N-nucleophiles have been studied.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2100–2103, December, 1993.     

Alkyl Esters of 2-[5-Chloro(bromo)-6-methoxy-4-methylpyrimidinyl-2-oxy]alkanoic Acids

The reaction of a mixture of formaldehyde and sodium cyanide or of lactic acid nitrile with trimethyl(6-methoxy-4-methylpyrimidinyl-2)ammonium chloride give the 2-(6-methoxy-4-methylpyrimidinyl-2-oxy)alkanoic acid nitriles. They were subsequently converted to the corresponding alkyl esters by a Pinner reaction and then to their 2-(5-halo-6-methoxy-4-methylpyrimidinyl-2-oxy) derivatives using N-halosuccinimides.     

15N NMR study of the mechanism of the reaction of amidoximes with nitrites in the presence of ZnCl2 and HCl

The structures of complexes formed during the transformation of amidoximes into 1,2,4-oxadiazoles by the action of nitriles in the presence of zinc chloride and HCl were studied by¹⁵N NMR spectroscopy.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 676–678, April, 1994.     

Peculiarities of interaction of H+, Me3C+, and Me3Si+ ions with multifunctional molecules in the gas phase

Peculiarities of interaction of H⁺, Me₃C⁺, and Me₃Si⁺ ions with functional groups of molecules in the gas phase have been studied. Proton tends to form chelates with virtually all of the functional groups studied, whereas Me₃Si⁺ ions exhibit no capacity for chelation. Using isomeric xylenes as examples it was shown that Me₃Si⁺ ions (unlike Me₃C⁺ ions) experience virtually no steric hindrance when they react with nucleophilic centers. Effects of functional groups present in molecules of nitriles on the generation of [M+Me₃C]⁺ adducts in the gas phase and the Ritter reaction in solution were estimated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1767–1773, September, 1995.This work was carried out with financial support from the International Science Foundation (Grant MA7 000) and the Russian Foundation for Basic Research (Project No. 93-03-18033).