Preparation of ethynylsilanes from polychloroethylenes
作者:Robert West、Laverne C. Quass
DOI:10.1016/s0022-328x(00)80233-8
日期:1969.7
chloroethylenes are described. Symmetrical bis(trialkylsilyl)acetylenes are obtained in good yield from tetrachloroethylene, lithium and trialkylhalosilanes at −80° in tetrahydrofuran. When lithium and tetrachloroethylene are similarly allowed to react at −80° and then quenched with organosilicon halides, (chloroethynyl)triorganosilanes, R3SiCCCl, are produced. These can be coupled with lithium and chlorosilanes
描述了由氯乙烯制备有机甲硅烷基乙炔的一般方法。对称的双(三烷基甲硅烷基)乙炔可以在-80°C下于四氢呋喃中从四氯乙烯,锂和三烷基卤代硅烷获得高收率。当锂和四氯乙烯被类似地在-80至反应°,然后与有机硅卤化物,(氯乙炔基)三有机硅烷,R猝灭3 SiCCCl,生产。这些可以与锂和氯硅烷偶联以得到不对称取代的双(有机甲硅烷基)乙炔。三氯乙烯,锂和三烷基氯硅烷可得到适当的乙炔基三烷基硅烷R 3 SiC fairCH。对称的双(有机甲硅烷基)乙炔也可以由顺式或反式制备-1,2-二氯乙烯,烷基锂化合物和氯硅烷。
Dehydrocondensation of trialkylsilanes with acetylene and monosubstituted acetylenes
Trialkylsilanes readily undergo dehydrocondensation with acetylene and substituted acetylenes in the presence of the catalytic systems, H2PtCl6/iodine, lithium iodide or /trialkyliodosilanes, and so the monosubstitutedacetylenes HCCR (R = C4H9, C(CH3)3, CH2Cl, C6H5) smoothly afford the corresponding trialkyl(organylethynyl)silanes. In hexane or benzene the yield of the dehydrocondensation products
在催化体系,H 2 PtCl 6 /碘,碘化锂或/三烷基碘硅烷的存在下,三烷基硅烷很容易与乙炔和取代的乙炔进行脱氢缩合反应,因此单取代的乙炔HCCR(R = C 4 H 9,C(CH 3)3,CH 2 Cl,C 6 H 5)平稳地得到相应的三烷基(有机基乙炔基)硅烷。在己烷或苯中,脱氢缩合产物的产率为90%。三乙基硅烷与乙炔的脱氢产物为双(三乙基磺酰基)乙炔和1,2-双(三乙基甲硅烷基)乙烷。讨论了反应机理。
Reaction of the Heteronuclear Cluster [Cp*IrRu
<sub>3</sub>
(μ‐H)
<sub>2</sub>
(CO)
<sub>10</sub>
] with Alkynes: Stereoselective Binding
作者:Padmamalini Srinivasan、Weng Kee Leong
DOI:10.1002/ejic.200500830
日期:2006.1
The reaction of the heteronuclear cluster [Cp*IrRu3(μ-H)2(CO)10] (1) with the symmetrical alkynes RCCR (R = Ph, Et) afforded the butterfly clusters [Cp*IrRu3(CO)9(RCCR)] (2) and the trinuclear clusters [Cp*IrRu2(CO)7(RCCR)] (3) and [Ru3(CO)8(C4R4)] (4). The clusters 2 and 3 have the alkyne aligned parallel to an Ru–Ir bond. The reaction of 1 with unsymmetrical alkynes also afforded stereoselective