Reaction of the (Dichloromethyl)oligosilanes R(Me3Si)2Si−CHCl2 (R = Me, Ph, Me3Si) with Organolithium Reagents and the Synthesis of Novel Kinetically Stabilized Silenes
作者:Kathleen Schmohl、Helmut Reinke、Hartmut Oehme
DOI:10.1002/1099-0682(200102)2001:2<481::aid-ejic481>3.0.co;2-6
日期:2001.2
silanols, by the addition of methanol to give methoxysilanes and by formal [2+2] cycloadditions with benzaldehyde to afford stable 1,2-oxasiletanes. 1-Methyl-1-(2,4,6-triisopropylphenyl)-2,2-bis(trimethylsilyl)silene (8a), produced as intermediate from 1a and 2,4,6-triisopropylphenyllithium (1:2), proved to be unstable in the presence of excess aryllithium compound. Thus, only the addition product Me(2
二氯甲基低聚硅烷 R1(Me3Si)2Si-CHCl2 (1a,b) (1a: R1 = Me; 1b: R1 = Ph),分别用氯仿和叔叔钾处理甲基双(三甲基甲硅烷基)硅烷或苯基双(三甲基甲硅烷基)硅烷制备-丁醇盐,用有机锂试剂 R2Li (R2 = Me, Ph) 处理,生成中间体有机锂衍生物 R1R22Si-CLi(SiMe3)2 (10)。在水性后处理期间水解 10 得到 [双(三甲基甲硅烷基)甲基] 硅烷 R1R22Si-CH(SiMe3)2 (2);用氯三甲基硅烷淬灭反应混合物得到[三(三甲基甲硅烷基)甲基]硅烷 R1R22Si-C(SiMe3)3 (11)。讨论 10 的形成是通过一系列显着的异构化过程进行的,这些过程涉及瞬态 silene R1R2Si=C(SiMe3)2 (7),在有效过量的 R2Li 存在下,它立即被捕获,得到 10。通过使用空间拥挤的有机锂衍生物,可以防止