Thermal hydrosilylation of olefin with hydrosilane. Preparative and mechanistic aspects
作者:Dong Euy Jung、Joon Soo Han、Bok Ryul Yoo
DOI:10.1016/j.jorganchem.2011.08.019
日期:2011.11
The reaction of trichlorosilane (1a) at 250 °C with cycloalkenes, such as cyclopentene (2a), cyclohexene (2b), cycloheptene (2c), and cyclooctene (2d), gave cycloalkyltrichlorosilanes [CnH2n−1SiCl3: n = 5 (3a), 6 (3b), 7 (3c), 8 (3d)] within 6 h in excellent yields (97–98%), but the similar reactions using methyldichlorosilane (1b) instead of 1a required a longer reaction time of 40 h and afforded
三氯硅烷(1a)在250°C下与环烯烃如环戊烯(2a),环己烯(2b),环庚烯(2c)和环辛烯(2d)反应,得到环烷基三氯硅烷[C n H 2 n -1 SiCl 3:n = 5(3a),6(3b),7(3c),8(3d)]在6小时内以优异的产率(97-98%),但是使用甲基二氯硅烷(1b)代替1a的类似反应需要更长的40小时反应时间,并在88中获得环烷基(甲基)二氯硅烷[C n H 2 n -1 SiMeCl 2:n = 5(3e),6(3f),7(3g),8(3h)] -92%的产率可回收4-8%的反应物2。在大的(2,0.29摩尔)进制制剂,的反应图2a和图2b与图1A(0.58摩尔)在相同条件下,得到图3a和图3b中分别为95%和94个%分离产率,。四种氢硅烷[HSiCl的相对反应性3− m Me m:m = 0–3]与2a的反应表明,随着硅上氯代数的增加,反应速率按以下顺序降低:n