三甲基烯丙基硅烷
化合物
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 | |
|---|---|
| |
| 别名 | 烯丙基三甲基硅烷 |
| 识别 | |
| CAS号 | 762-72-1 
|
| PubChem | 69808 |
| ChemSpider | 63007 |
| SMILES |
|
| 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
编辑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
编辑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
编辑- ^ 1.0 1.1 Sommer, Leo H.; Tyler, Leslie J.; Whitmore, Frank C. Reactions of Allyltrimethylsilane. Journal of the American Chemical Society. September 1948, 70 (9): 2872–2874 [2022-07-12]. ISSN 0002-7863. doi:10.1021/ja01189a010. eISSN 1520-5126. （原始内容存档于2022-07-10）.
- ^ House, Herbert O.; Sayer, Trevor S. B.; Yau, Cheuk-Chung. Chemistry of carbanions. 32. Formation of the perhydroazulene system by intramolecular alkylation. The Journal of Organic Chemistry. May 1978, 43 (11): 2153–2157 [2022-07-12]. ISSN 0022-3263. doi:10.1021/jo00405a014. eISSN 1520-6904. （原始内容存档于2022-07-12）.
- ^ David R. Lide. 1998 Freshman Achievement Award. CRC Press. 2006-06-26: 655– [2022-07-12]. ISBN 978-0-8493-0594-8. （原始内容存档于2022-07-12）.
- ^ 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.