三甲基烯丙基矽烷

三甲基烯丙基矽烷
別名	烯丙基三甲基矽烷
識別
CAS編號	762-72-1
PubChem	69808
ChemSpider	63007
SMILES	C[Si](C)(C)CC=C;
EINECS	212-104-5
性質
化學式	C6H14Si
摩爾質量	114.26 g·mol−1
外觀	無色液體
密度	0.7193 g/cm3
沸點	85—86 °C（358—359 K）
溶解性（水）	難溶於水
危險性
	GHS危險性符號;
GHS提示詞	警告
H-術語	H225, H315, H319, H335
P-術語	P210, P233, P240, P241, P242, P243, P261, P264, P271, P280, P302+352, P303+361+353, P304+340, P305+351+338
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

三甲基烯丙基矽烷是一種有機矽化合物，化學式為(CH₃)₃SiCH₂CH=CH₂。它是難溶於水的無色液體，它在有機合成中可用於酰氯、醛、酮、亞銨鹽和烯酮的烯丙基引入，以及與其它碳親電體的交叉偶聯中。它也可用於細見-櫻井反應。^[1]

合成

三甲基烯丙基矽烷可由烯丙基氯和三甲基氯矽烷在萘鈉-四氫呋喃體系中反應得到，反應結束後會由萘鈉的綠色變為烯丙基鈉的紫色。^[4]烯丙基溴和三甲基氯矽烷在二甲基甲酰胺中和金屬銦反應，也能得到該產物。^[5]

性質

三甲基烯丙基矽烷和α,α,α-三氟甲苯的衍生物在五氯化鈮催化下於室溫反應，可以得到相應的α,α,α-三烯丙基甲苯。^[6]

它和苄醇、苄溴或苄氯在三氯化鐵催化下反應，其羥基或鹵原子可以被烯丙基取代，如它和二苯甲醇反應，可以得到烯丙基二苯甲烷。^[7]在四氯化鈦存在下，它和酮發生櫻井反應，得到烯丙基甲醇。^[8]

其它路易斯酸如[Co(TPP)]SbF₆^[9]、InCl₃-(CH₃)₃SiCl^[10]等也能催化這一反應。

參考文獻

^ ^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. （原始內容存檔於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. （原始內容存檔於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. （原始內容存檔於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. （原始內容存檔於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. （原始內容存檔於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. （原始內容存檔於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. （原始內容存檔於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. （原始內容存檔於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.

[Sommer-1] 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. （原始內容存檔於2022-07-10）.

[2] 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. （原始內容存檔於2022-07-12）.

[3] David R. Lide. 1998 Freshman Achievement Award. CRC Press. 2006-06-26: 655– [2022-07-12]. ISBN 978-0-8493-0594-8. （原始內容存檔於2022-07-12）.

[4] 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. （原始內容存檔於2022-07-12）.

[5] 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.

[6] 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. （原始內容存檔於2022-07-12）.

[7] 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. （原始內容存檔於2022-07-12）.

[8] 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. （原始內容存檔於2022-07-12）.

[9] 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. （原始內容存檔於2022-07-12）.

[10] 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.

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