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• W2003128251 abstract "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 cycloalkyl(methyl)dichlorosilanes [CnH2n−1SiMeCl2: n = 5 (3e), 6 (3f), 7 (3g), 8 (3h)] in 88–92% yields with 4–8% recovery of reactant 2. In large (2, 0.29 mol)-scale preparations, the reactions of 2a and 2b with 1a (0.58 mol) under the same condition gave 3a and 3b in 95% and 94% isolated yields, respectively. The relative reactivity of four hydrosilanes [HSiCl3−mMem: m = 0–3] in the reaction with 2a indicates that as the number of chlorine-substituent(s) on the silicon increases the rate of the reaction decreases in the following order: n = 3 > 2 > 1 ≫ 0. In the reaction with 1a, the relative reactivity of four cycloalkenes (ring size = 5–8) decreases in the following order: 2d > 2a > 2c > 2b. Meanwhile linear alkenes like 1-hexene undergo two reactions of self-isomerization and hydrosilylation with hydrosilane to give a mixture of the three isomers (1-, 2-, and 3-silylated hexanes). In this reaction, the reactivity of the terminal 1-hexene is higher than the internal 2- and 3-hexene. The redistribution of hydrosilane 1 and the polymerization of olefin 2 occurred rarely under the thermal reaction condition." @default.
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• W2003128251 date "2011-11-01" @default.
• W2003128251 modified "2023-10-01" @default.
• W2003128251 title "Thermal hydrosilylation of olefin with hydrosilane. Preparative and mechanistic aspects" @default.
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• W2003128251 doi "https://doi.org/10.1016/j.jorganchem.2011.08.019" @default.
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