1-溴乙烯基(三苯基)硅烷 | 18676-45-4

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 中文名称: 1-溴乙烯基(三苯基)硅烷
• 英文名称: α-bromovinyltriphenylsilane
• 英文别名: 1-bromo-1-(triphenylsilyl)ethene；(1-bromovinyl)triphenylsilane；Triphenyl-<1-brom-vinyl>-silan；α-Bromovinyltriphenylsilan；α-Bromvinyltriphenylsilan；(1-Bromoethenyl)(triphenyl)silane；1-bromoethenyl(triphenyl)silane
• CAS: 18676-45-4
• 化学式: C₂₀H₁₇BrSi
• 分子量: 365.344
• InChiKey: SHWWADNDSHZGOI-UHFFFAOYSA-N

物化性质

• 熔点：
  132-134 °C
• 沸点：
  409.3±37.0 °C(Predicted)
• 密度：
  1.27±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-溴乙烯基(三苯基)硅烷 以 吡啶 为溶剂， 生成 2-Triphenylsilyl-3-acetoxy-3,3-diphenyl-1-propen
  参考文献：
  名称：

  Synthesis of alkenes from carbonyl compounds and carbanions .alpha. to silicon. 6. Synthesis of terminal allenes and allyl chlorides

  摘要：

  DOI：

  10.1021/jo00402a008
• 作为产物：
  描述：

  乙烯基三苯基硅烷 在 溴 、 二乙胺 作用下， 生成 1-溴乙烯基(三苯基)硅烷
  参考文献：
  名称：

  Palladium-Catalyzed Regio- and Stereoselective Aryldesilylation of α-Silylstyrenes with Arenediazonium Salts

  摘要：

  α-三烷基硅基苯乙烯[Ph(R3Si)C=CH2：R=Me(1)、Et(2)和 Ph (3)]在钯(0)催化下很容易与四氟硼酸别硝基苯铵[ArN2+BF4- (4)]反应，生成 (E)-PhCH=CHAr 。硅上的大取代基具有更好的立体选择性。

  DOI：

  10.1246/cl.1988.873

文献信息

• Copper(I)<b> <i>tert</i> </b>-Butoxide-Promoted Allylation of β-Triphenylsilyl Allylic Alcohols­ via 1,3 C^<b>sp²</b>-to-O Silyl Migration
  作者：Takeshi Takeda、Akira Tsubouchi、Miki Itoh、Kotaro Onishi

  DOI：10.1055/s-2004-822404

  日期：——

  The substitution of the silyl group in vinylsilanes by an allylic group proceeded when β-triphenylsilylallyl alcohols were treated with copper(I) tert-butoxide and allylic halides. This reaction is the first synthetic application of 1,3 Csp2-to-O silyl migration which provides a useful method for generation of vinyl anion equivalents.

  在β-三苯基甲硅烷基烯丙醇与叔丁醇铜(I)和烯丙基卤化物的反应中，烯丙基取代了乙烯基硅烷中的硅基。该反应是首次应用于1,3 Csp2-到-O硅基迁移的合成应用，提供了一种生成乙烯基阴离子等效物的有用方法。
• A New General Route to Acceptor-Substituted Vinyloxiranes via Siloxyoxiranes - Novel Promising Synthetic Building-Blocks
  作者：Ernst Schaumann、Frank Tries

  DOI：10.1055/s-2002-19796

  日期：——

  Epoxidation of silyl enol ethers 2a,b with dimethyldioxirane yields siloxyoxiranes 3a,b. Anions 4a-d lead to nucleophilic ring-opening in the acetal position C-1 of 3 to give diols 5a-d. Monotosylation and cyclisation provide acceptor-substituted vinyloxiranes 6a-d.

  用二甲基二环氧乙烷环氧化甲硅烷基烯醇醚 2a,b 得到硅氧烷环氧乙烷 3a,b。阴离子 4a-d 导致 3 的缩醛位置 C-1 发生亲核开环，得到二醇 5a-d。单甲苯基化和环化提供受体取代的乙烯基环氧乙烷 6a-d。
• Synthesis of 1,3-Difunctionalized Cyclopentenes and 1,3,5-Trifunctionalized Cyclohexanes by Silicon-Induced Domino Reactions
  作者：Frank Tries、Ernst Schaumann

  DOI：10.1002/ejoc.200390160

  日期：2003.3

  domino process based on a 1,4-C⇄O shift of a silyl group (4 ⇄ 3) and a Michael-induced ring-closure reaction (3 ⇄ 2) is investigated. Specifically, attack of carbanions 5 on vinyloxiranes 6 usually occurs on the oxirane unit to give the desired silyl shift. When starting from vinyloxiranes 6a and 6b, however, the reaction stops at this stage to give silyl ethers 7. Sulfur (6c) or silicon activation (6d−f)

  研究了一种基于甲硅烷基 (4 ⇄ 3) 的 1,4-C⇄O 位移和迈克尔诱导的闭环反应 (3 ⇄ 2) 的新型多米诺过程。具体而言，碳负离子 5 对乙烯基环氧乙烷 6 的攻击通常发生在环氧乙烷单元上以产生所需的甲硅烷基位移。然而，当从乙烯基环氧乙烷 6a 和 6b 开始时，反应在此阶段停止以产生甲硅烷基醚 7。C=C 单元的硫 (6c) 或硅活化 (6d-f) 需要产生环戊烯 1a-d。类似地，碳负离子 5a 和烯丙环氧乙烷 15 产生环化产物 19-22，特别是如果闭环步骤由硅取代支持。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• Preparation and reactions of triarylsilylmethylmetallic reagents
  作者：A. G. Brook、J. M. Duff、D. G. Anderson

  DOI：10.1139/v70-093

  日期：1970.2.15

  Triarylsilylmethylmetallic reagents have been prepared by several routes: metalation; addition of phenyllithium to vinyltriphenylsilane; direct synthesis; and by halogen–metal exchange. The latter method is highly superior as regards both generality of application and yields. Dibromomethylsilanes undergo halogen-metal exchange at −78°, and reaction of the product with hydrogen bromide serves as a valuable way of converting geminal dibromides to monobromides. The organometallic reagents have been characterized in several ways, in particular by carbonation to give the related carboxylic acid.

  三芳基硅甲基金属试剂已通过几种途径制备：金属化；苯基锂与乙烯三苯基硅烷的加成；直接合成；以及卤素金属交换。后一种方法在适用性和产率方面都具有极高的优势。二溴甲基硅烷在-78°下发生卤素金属交换，产物与氢溴酸的反应可作为将伪二溴化物转化为单溴化物的有价值途径。这些有机金属试剂已通过多种方式进行表征，特别是通过碳酸化得到相关的羧酸。
• Silyl-substituted α,β-Unsaturated Ketones from the Reaction of Silylvinylmetallic Reagents with Acid Anhydrides
  作者：A. G. Brook、J. M. Duff

  DOI：10.1139/v73-302

  日期：1973.6.15

  The reactions of a series of silyl-substituted vinylmetallic reagents with acetic and benzoic anhydride have been investigated as a general route to α,β-unsaturated ketones having a silyl group attached to the carbon–carbon double bond. The reaction has been found to be generally applicable for acetyl derivatives provided low temperatures are used but the reaction with benzoic anhydride gives poorer results. The i.r. and u.v. spectra of the ketones are discussed. The characterization of novel 1,4-dienes obtained as by-products in the syntheses is also described.

  一系列含硅基取代的乙烯金属试剂与乙酸酐和苯甲酸酐的反应已被研究，作为合成α，β-不饱和酮的一般途径，其中硅基附着在碳-碳双键上。发现该反应通常适用于乙酰衍生物，只要使用低温，但与苯甲酸酐的反应结果较差。讨论了酮的红外和紫外光谱。还描述了在合成中得到的新型1,4-二烯的表征。