有机硅活性中间体的研究 II. 一些含环丙基的有机硅化合物的合成及其结构

用锂有机物的方法合成了四种含有环丙基有机硅化合物,对上述每种化合物中可能存在着的立体异构进行了分离和和构型测定。     

Phenylene-containing organosilicon compounds

Summary By condensation of sodium triphenylsilanolate with 1,4-bis(dimethylchlorosilyl)benzene, we synthesized for the first time 1,4-bis[dimethyl(triphenylsiloxy)silyl]benzene, which is a crystalline substance with m.p, 237–238°, distilling at 465–475° without decomposition.     

Nitrogen-containing organosilicon compounds

By the reaction of trialkylsilanes and dialkoxy- or di(chloroalkyl)alkylsilanes with morpholine, thiamorpholine, N-methylpiperazine, and hexamethyleneimine, 14 new organosilicon derivatives of these heterocycles have been synthesized. The addition of perhydroazepine to diethylmethylvinylsilane has been performed.For part XIII, see [1].     

Nitrogen-containing organosilicon compounds

The dipole moments of 1-ethoxy-2-carbasilatrane (1-ethoxy-2,8-dioxa-5-aza-1-silabicyclo [3,3,3]undecane (II)), and of 1,1-dimethyl-2,8-dioxa-5-aza-1-silacyclooctane (III) have been investigated. The presence of a transannular Si N coordination bond (weaker than in the 1-ethoxysilatrane 1) in II and its absence from III has been established.For part X, see [1].     

Nitrogen-containing organosilicon compounds

Fifteen previously unknown piperidinosilanes of the type R_4–m Si[(CH₂) _n NC₅H₁₀] _m (m=1–3; n=0–3). have been synthesized by the reaction of piperidine with diethylaminotrimethylsilane, bis(diethylamino)dimethylsilane, chlorobis(dimethylamino)methylsilane, trichloro(methyl)silane, trialkyl(chloromethyl)silanes, dialkoxy(alkyl)(chloromethyl)silanes, trialkylvinylsilanes, trialkyl(3-chloropropyl)silanes, and 3-chloropropyl(diethoxy)methylsilane. The piperidinosilanes (n>0) have been converted into the corresponding hydrochlorides and methiodides.For part VIII, see [1].     

Furan organosilicon compounds

A series of 2-furyl- and 5-methyl-2-furylorganylhydrosilanes are synthesized by reacting 2-furyllithium and 5-methyl-2-furyllithium with organylchlorohydrosilanes. Furylorganylhydrosilanes reduce HgCl₂ in pyridine to free mercury; while in the presence of H₂PtCl₆ water converts them to the corresponding silanols, with alcohols they undergo dehydrocondensation, and with unsaturated compounds there is hydrosilanation.For Part XI see [1].     

Infrared spectra of unsaturated organosilicon compounds with a pent a methyldisilyl group

Summary Consideration of the IR spectra of a number of alkenylsilanes with a pentamethyldistlyl group shows that substitution of a methyl radical in the trimethylsilyl group of the alkenylsilane for the (CH₃)₃Si group results in a noticeable lowering of the intensity of the absorption band for the double bond of the alkenylsilane.     

Furan series organosilicon compounds

Six new organosilicon esters of pyromucic, 3-(2-furyl)acrylic, and cinnamic acids were synthesized by reacting these acids with chloromethylalkylsilanes and chloromethylalkoxysilanes in the presence of triethylamine.For Part X see [1].     

有机硅化合物的不对称合成反应

介绍了“碳中心”手性有机硅化合物的合成,以及在烯丙基硅烷与醛的Hosomi-Sakurai反应和α-烯丙基硅碳负离子与醛的反应中的应用。提出并实践了两条提高对映选择性的途径。烯基硅醇的不对称环氧化反应扩展了Sharpless反应的适用范围,为合成光活性的具简单结构的环氧化合物提供了一条简易的途径。     

Disproportionation of unsaturated organosilicon compounds

Russian Chemical Bulletin -     

Electrochemical synthesis of organosilicon compounds

Electrochemical reduction of allyl, vinyl, and aryl halides in the presence of a silylating agent (Me₃SiCl, HMe₂SiCl, or PhMe₂SiCl) afforded the corresponding organosilicon compounds offering a valuable method for introduction of a silyl group into organic molecules.     

Structure of radical anions of organosilicon compounds. INDO calculations of the radical anions of some organosilicon compounds

M. V. Lomonosov Moscow Institute of Fine Chemical Engineering. Translated from Zhurnal Strukturnoi Khimii, Vol. 29, No. 2, pp. 24–30, March–April, 1988.     

有机硅化合物在α-D-葡二糖合成上的应用

三苯基硅基作为葡萄糖1-C位羟基保护基, 在对硝基苯甲酰基存在下形成和脱保护基反应均易进行, 而且有产率高、在反应过程中保持1-C构型不变等特点, 并研究了三苯基硅基保护基在葡二糖上的应用。