三甲基-(1-乙烯基-2-丙烯基)硅烷 | 77213-08-2

• 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: 三甲基-(1-乙烯基-2-丙烯基)硅烷
• 英文名称: trimethyl-(1-vinyl-2-propenyl)silane
• 英文别名: 3-Trimethylsilyl-1,4-pentadiene；trimethyl(penta-1,4-dien-3-yl)silane
• CAS: 77213-08-2
• 化学式: C₈H₁₆Si
• 分子量: 140.301
• InChiKey: HSSXPJZXSIGYIX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.07
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  反-1,3-戊二烯 、 三甲基氯硅烷 以23%的产率得到
  参考文献：
  名称：

  HOSOMI AKIRA; SAITO MASAKI; SAKURAI HIDEKI, TETRAHEDRON LETT., 1980, 21, NO 39, 3783-3786

  摘要：

  DOI：

文献信息

• Pentadienyl Type Lithium and Potassium Species: The Regioselectivity of their Reactions with Electrophiles
  作者：Manfred Schlosser、Armin Zellner、Frédéric Leroux

  DOI：10.1055/s-2001-17521

  日期：——

  Seven structurally distinct pentadienyl type lithium and potassium compounds were screened against a variety of electrophiles in order to assess the regioselectivity of the trapping reactions. Organoborates and analogs thereof (fluorodimethoxyborane) proved to be perfectly regioreliable attacking only unsubstituted terminal positions and thus providing, after oxidation, exclusively primary allylic alcohols. 2,4-Pentadienyllithiums or -potassiums, that carry a methyl group at the 1- or 3-position, exhibit the same extreme regioselectivity towards halotrialkylsilanes or carbon dioxide. Although the unsubstituted parent compounds combine with such electrophiles still preferentially at the terminal position, considerable proportions of branched products are concomitantly formed as well (1/3-attack ratios ranging from 2:1 to > 20:1). Hydroxyalkylating and alkylating reagents such as formaldehyde, oxirane or butyl iodide invariably afford regioisomeric mixtures generally varying in composition between 3:1 and 1:3. The condensation reaction with halotrialkylsilanes appears to follow a concerted (SN2-like) rather than an addition/elimination (ate complex-mediated) mechanism.

  进行了七种结构不同的戊二烯基型锂和钾化合物的筛选，以评估它们与各种亲电试剂反应的区域选择性。有机硼酸盐及其类似物（氟二甲氧基硼烷）显示了非常可靠的区域选择性，仅攻击未取代的末端位置，因此氧化后只得到完全的一级烯丙基醇。带有甲基的2,4-戊二烯基锂或钾在1-或3-位置上，对卤代三烷基硅烷或二氧化碳显示出相同的极端区域选择性。尽管未取代的母体化合物仍优先在末端位置与这些亲电试剂反应，但同时也会生成相当比例的支链产物（1/3-攻击比例从2:1到超过20:1）。羟烷基化和烷基化试剂，如甲醛、环氧乙烷或丁基碘，总是得到区域异构体的混合物，其组成通常在3:1和1:3之间变化。与卤代三烷基硅烷的缩合反应似乎遵循协同（类似SN2）而非加成/消除（通过ate复合体介导）的机制。
• Pentadienylsilanes as new reagents of the siteselective dienylmethylation of electrophiles promoted by a Lewis acid
  作者：Akira Hosomi、Masaki Saito、Hideki Sakurai

  DOI：10.1016/0040-4039(80)80177-8

  日期：1980.1

  (2,4-Pentadienyl)- and (2,4-hexadienyl)trimethylsilanes, prepared from the corresponding pentadienylpotassiums and trimethylchlorosilane, react smoothly with various electrophiles such as acetals, aldehydes and acid halides to give pentadienylation products, with regiospecific transposition of the pentadienyl group.

  由相应的戊二烯基钾和三甲基氯硅烷制得的（2,4-戊二烯基）-和（2,4-己二烯基）三甲基硅烷与各种亲电子试剂（如乙缩醛，醛和酰卤）平稳反应，生成戊二烯化产物，并通过戊二烯基的区域特异性转位团体。
• Chemistry of Dienyl Anions. IV. Geometry of Pentadienyl Anions in Solution and in the Solid State Determined by Regioselective Trimethylsilylation and NMR
  作者：Hajime Yasuda、Michihide Yamauchi、Yasuo Ohnuma、Akira Nakamura

  DOI：10.1246/bcsj.54.1481

  日期：1981.5

  series of alkyl substituted pentadienyl anions in THF was examined by trimethylsilylation and from the variable temperature 1H- and 13C-NMR spectra. Potassium pentadienide, -2-methylpentadienide or -2,4-dimethylpentadienide produced preferentially (Z)-2,4-pentadienyltrimethylsilane or its methyl substituted analogues to indicate that these compounds have the “U”-shaped structure in solution. By contrast

  THF 中一系列烷基取代的戊二烯基阴离子的构型分析通过三甲基甲硅烷基化和变温 1H-和 13C-NMR 谱进行检查。戊二烯钾、-2-甲基戊二烯或-2,4-二甲基戊二烯优先产生(Z)-2,4-戊二烯基三甲基硅烷或其甲基取代的类似物，表明这些化合物在溶液中具有“U”形结构。相比之下，结晶状态的戊二烯化钾和 -2-甲基戊二烯化钾的三甲基甲硅烷基化分别产生 (E)- 和 (E),(Z)-异构体，表明几何结构急剧变化为“W”-或“S”形受介质影响。3-甲基戊二烯化钾在 THF 和固态中的 W 形结构是特殊的。