研究了三氯乙酸钠与各种有机硅氢化物在1,2-二甲氧基乙烷中的反应,形成了α-三有机甲硅烷基二氯甲烷,产率为20%至50%。通过竞争反应确定在这些二氯卡宾的插入反应中这些氢硅烷的相对速率常数。一系列烷基取代的氢硅烷的相对反应性与硅上取代基的Taftσ*常数高度相关,ϱ *值为-1.07,一系列芳基取代的氢硅烷也显示出log k rel良好的线性相关性值具有Taftσ*常数,giving *值为-1.18。反应中的氢同位素效应k H / k D1.26±0.02。基于观察到的结果,可以得出结论,Cy 2插入SiH键中是通过三中心协同过程进行的,该过程中过渡态的电荷分离不大,正如塞弗特(Seyferth)对相关的PhHgCCl 2提出的那样。 Br / XC 6 H 4 SiMe 2 H反应。
The present invention provides multi-thiol mercaptoalkoxysilane compositions and methods of making multi-thiol mercaptoalkoxysilane compositions having the formula:
wherein the R
3
group, and the R
4
group are independently an alkoxy, a halogen, an alkyl, an aryl, a heteroaryl, a heterocycle or derivatives thereof and n is an integer between 1 and 30.
The present invention provides multi-thiol mercaptoalkoxysilane compositions and methods of making multi-thiol mercaptoalkoxysilane compositions having the formula:
wherein the R3 group, and the R4 group are independently an alkoxy, a halogen, an alkyl, an aryl, a heteroaryl, a heterocycle or derivatives thereof and n is an integer between 1 and 30.
The reaction of sodium trichloroacetate with various organosiliconhydrides in 1,2-dimethoxyethane was investigated and the products, α-triorganosilyldichloromethanes, were formed in yields of 20–50%. The relative rate constants of these hydrosilanes in such insertion reactions of dichlorocarbene were determined by means of competition reactions. The relative reactivities of a series of alkyl substituted
研究了三氯乙酸钠与各种有机硅氢化物在1,2-二甲氧基乙烷中的反应,形成了α-三有机甲硅烷基二氯甲烷,产率为20%至50%。通过竞争反应确定在这些二氯卡宾的插入反应中这些氢硅烷的相对速率常数。一系列烷基取代的氢硅烷的相对反应性与硅上取代基的Taftσ*常数高度相关,ϱ *值为-1.07,一系列芳基取代的氢硅烷也显示出log k rel良好的线性相关性值具有Taftσ*常数,giving *值为-1.18。反应中的氢同位素效应k H / k D1.26±0.02。基于观察到的结果,可以得出结论,Cy 2插入SiH键中是通过三中心协同过程进行的,该过程中过渡态的电荷分离不大,正如塞弗特(Seyferth)对相关的PhHgCCl 2提出的那样。 Br / XC 6 H 4 SiMe 2 H反应。
Si–N Heterodehydrocoupling with a Lanthanide Compound
作者:Michael P. Cibuzar、Rory Waterman
DOI:10.1021/acs.organomet.8b00372
日期:2018.12.10
[LaN(SiMe3)2}3THF2] (1) is an effective precatalyst for the heterodehydrocoupling of silanes and amines. Coupling of primary and secondary amines with aryl silanes was achieved with a loading of 0.8 mol % of [LaN(SiMe3)2}3THF2]. With primary amines, generation of tertiary and sometimes quaternary silamines was facile, often requiring only a few hours to reach completion, including new silamines Ph3Si(nPrNH)