三甲基烯丙基硅烷
化合物
(重定向自烯丙基三甲基硅烷)
三甲基烯丙基硅烷是一种有机硅化合物,化学式为(CH3)3SiCH2CH=CH2。它是难溶于水的无色液体,它在有机合成中可用于酰氯、醛、酮、亚铵盐和烯酮的烯丙基引入,以及与其它碳亲电体的交叉偶联中。它也可用于细见-樱井反应。[1]
三甲基烯丙基硅烷 | |
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别名 | 烯丙基三甲基硅烷 |
识别 | |
CAS号 | 762-72-1 ![]() |
PubChem | 69808 |
ChemSpider | 63007 |
SMILES |
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EINECS | 212-104-5 |
性质 | |
化学式 | C6H14Si |
摩尔质量 | 114.26 g·mol−1 |
外观 | 无色液体 |
密度 | 0.7193 g/cm3[1] |
沸点 | 85—86 °C(358—359 K)[2] |
溶解性(水) | 难溶于水[3] |
危险性 | |
GHS危险性符号![]() ![]() | |
GHS提示词 | 警告 |
H-术语 | H225, H315, H319, H335 |
P-术语 | P210, P233, P240, P241, P242, P243, P261, P264, P271, P280, P302+352, P303+361+353, P304+340, P305+351+338 |
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。 |
合成
三甲基烯丙基硅烷可由烯丙基氯和三甲基氯硅烷在萘钠-四氢呋喃体系中反应得到,反应结束后会由萘钠的绿色变为烯丙基钠的紫色。[4]烯丙基溴和三甲基氯硅烷在二甲基甲酰胺中和金属铟反应,也能得到该产物。[5]
性质
三甲基烯丙基硅烷和α,α,α-三氟甲苯的衍生物在五氯化铌催化下于室温反应,可以得到相应的α,α,α-三烯丙基甲苯。[6]
它和苄醇、苄溴或苄氯在三氯化铁催化下反应,其羟基或卤原子可以被烯丙基取代,如它和二苯甲醇反应,可以得到烯丙基二苯甲烷。[7]在四氯化钛存在下,它和酮发生樱井反应,得到烯丙基甲醇。[8]
参考文献
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- ^ van den Ancker, Tania R.; Love, Cameron J. Polymer supported naphthalene-catalysed sodium reactions. Organic & Biomolecular Chemistry. 2007, 5 (21): 3520 [2022-07-12]. ISSN 1477-0520. PMID 17943212. doi:10.1039/b710308e. eISSN 1477-0539. (原始内容存档于2022-07-12).
- ^ Li, Zhifang; Yang, Chenjun; Zheng, Hongfang; Qiu, Huayu; Lai, Guoqiao. Selective mono- and di-allylation and allenylation of chlorosilanes using indium. Journal of Organometallic Chemistry. December 2008, 693 (25): 3771–3779. ISSN 0022-328X. doi:10.1016/j.jorganchem.2008.08.028.
- ^ Saito, Kodai; Umi, Taishi; Yamada, Takayuki; Suga, Takuya; Akiyama, Takahiko. Niobium(V)-catalyzed defluorinative triallylation of α,α,α-trifluorotoluene derivatives by triple C–F bond activation. Organic & Biomolecular Chemistry. 2017, 15 (8): 1767–1770 [2022-07-12]. ISSN 1477-0520. PMID 28139811. doi:10.1039/C6OB02825J. eISSN 1477-0539. (原始内容存档于2022-07-12).
- ^ Han, Jie; Cui, Zili; Wang, Jianguo; Liu, Zhongquan. Efficient and Mild Iron-Catalyzed Direct Allylation of Benzyl Alcohols and Benzyl Halides with Allyltrimethylsilane. Synthetic Communications. 2010-06-17, 40 (14): 2042–2046 [2022-07-12]. ISSN 0039-7911. doi:10.1080/00397910903219393. eISSN 1532-2432. (原始内容存档于2022-07-12).
- ^ Hosomi, Akíra; Sakurai, Hideki. Syntheses of γ,δ-unsaturated alcohols from allylsilanes and carbonyl compounds in the presence of titanium tetrachloride. Tetrahedron Letters. April 1976, 17 (16): 1295–1298 [2022-07-12]. ISSN 0040-4039. doi:10.1016/S0040-4039(00)78044-0. (原始内容存档于2022-07-12).
- ^ Tomifuji, Rei; Masuda, Shota; Kurahashi, Takuya; Matsubara, Seijiro. Cationic Cobalt Porphyrin-Catalyzed Allylation of Aldehydes with Allyltrimethylsilanes. Organic Letters. 2019-05-07, 21 (10): 3834–3837 [2022-07-12]. ISSN 1523-7060. PMID 31062985. doi:10.1021/acs.orglett.9b01303. eISSN 1523-7052. (原始内容存档于2022-07-12).
- ^ Onishi, Yoshiyuki; Ito, Takeshi; Yasuda, Makoto; Baba, Akio. Indium(III) Chloride/Chlorotrimethylsilane as a Highly Active Lewis Acid Catalyst System for the Sakurai−Hosomi Reaction. European Journal of Organic Chemistry. May 2002, 2002 (9): 1578–1581. ISSN 1434-193X. doi:10.1002/1099-0690(200205)2002:9<1578::AID-EJOC1578>3.0.CO;2-P. eISSN 1099-0690.