1,1-dimethyl-1-silacyclopent-2-ene | 18187-50-3

• 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
• 英文名称: 1,1-dimethyl-1-silacyclopent-2-ene
• 英文别名: 1,1-Dimethyl-2-silolene；1,1-dimethyl-2,3-dihydrosilole
• CAS: 18187-50-3
• 化学式: C₆H₁₂Si
• 分子量: 112.247
• InChiKey: XHQZCRYJLMRMKG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.19
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  1,1-dimethyl-1-silacyclopent-2-ene 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 以46%的产率得到6-oxa-2,2-dimethyl-2-silabicyclo<3.1.0>hexane
  参考文献：
  名称：

  The far-UV photochemistry of five- and six-membered-ring monosilacycloalkenes in alcohols: stereospecific .beta.-cleavage to silyl ethers and stereoselective formation of silacycloalkyl ethers

  摘要：

  Photoalcoholysis of 1,1-dimethylsilacyclopent-2-ene (9) at 214 nm in methanol, 2,2,2-trifluoroethanol, and tert-butyl alcohol affords alkoxy(3-butenyl)dimethylsilanes 11 and 3-alkoxy-1,1-dimethylsilacyclopentanes 12. Also formed are alkoxy(cyclopropylmethyl)silanes 13 from apparent 1,3-C migration. In pure, deuterated alcohols (CH3OD and CF3CD2OD) adducts It and 12 become trans deuterated, whereas in dilute solutions of methanol-O-d in pentane, scrambling of deuterium between the trans and cis C-2 positions of 12 is observed without corresponding loss of stereospecificity for formation of silyl ether 11. Silyl ether 11 is thus produced via a pathway which is mechanistically distinct from that giving 12, for which the loss of stereoselectivity in dilute alcohols is ascribed to pseudorotational scrambling of deuterium in a silacyclopentyl cation intermediate. At high concentrations of alcohol the trans-stereoselective deuteration of 12 can be attributed to least hindered anti attack of the alcohol at C-3 of this hyperconjugatively stabilized cation. High cis-stereoselective deuteration of 12 is observed for photolysis in dilute CF3CD2OD in pentane, possibly reflecting the intermediacy of an ion pair or unsymmetrically solvated silacyclopentyl cation. Photoalcoholyses of the silacyclohex-2-ene were conducted for comparison.

  DOI：

  10.1021/jo00037a030
• 作为产物：
  描述：

  2-氯-1,1-二甲基-1-硅杂环戊烷 在 喹啉 作用下， 生成 1,1-dimethyl-1-silacyclopent-2-ene
  参考文献：
  名称：

  The Chlorination of 1,1-Dimethylsilacyclopentane and 1,1-Dimethylsilacyclohexane¹

  摘要：

  DOI：

  10.1021/jo01065a078

文献信息

• Thermally-Induced 1,2-Shifts To Convert Olefins to Carbenes: Does Silicon Do It? If So, Why Not Carbon?
  作者：Thomas J. Barton、Jibing Lin、Sina Ijadi-Maghsoodi、Martin D. Power、Xianping Zhang、Zhongxin Ma、Hideaki Shimizu、Mark S. Gordon

  DOI：10.1021/ja00152a010

  日期：1995.11

  be reported for an olefin-to-carbene rearrangement. The analogous all-carbon system failed to ring expand. Ab initio calculations revealed that this was opposite to any predictions which would be made from ring strain considerations. Calculations showed that for silyl migration the transition state was late and was actually the carbene, while for carbon migration the TS was early and considerably higher

  通过实验和理论研究了通过 1,2-甲硅烷基转移将烯烃热异构化为卡宾。对于无环乙烯基硅烷，没有发现这种重排的证据，也无法在顺式、反式异构化中识别出硅的电子辅助。2,4-二甲基-1, 3-二硅杂环丁烷的偶然合成允许对其气相热环膨胀进行动力学检查，以生成 2-亚甲基-1,3-二硅杂环戊烯。Arrhenius 参数（log A = 12.48，Esub act} = 54.09 kcal/mol）是第一个报告的烯烃到卡宾重排的参数。类似的全碳系统未能环扩。Ab initio 计算表明，这与根据环应变考虑做出的任何预测相反。计算表明，对于甲硅烷基迁移，过渡态较晚，实际上是卡宾，而对于碳迁移，TS 较早且能量比所得卡宾高得多。重新检查了 2-亚甲基-1-硅杂环丁烷重排，发现在低于通过卡宾 TS 扩环所需的温度下发生 1,4-双基的可逆开环。45 个参考文献，5 个图，1 个标签。
• Kinetics and mechanisms of .alpha.- and .beta.-eliminations of alkoxysilanes from saturated and unsaturated carbon frameworks
  作者：Sukhamaya. Bain、Sina. Ijadi-Maghsoodi、Thomas J. Barton

  DOI：10.1021/ja00216a039

  日期：1988.4

  favorable elimination of Me/sub 3/SiOMe from Me/sub 3/SiSiMe/sub 2/CH/sub 2/OMe does not occur. From kinetic studies and trapping experiments, this is found to be due to a more favorable A-factor for three-centered elimination of :CH/sub 2/. Three-centered elimination of Me/sub 3/SiOMe from an sp/sup 2/-hybridized carbon to afford a vinylidene is found to be more facile than the analogous elimination from

  尽管 Me/sub 3/SiCH/sub 2/SiMe/sub 2/OMe 经历了 Me/sub 3/SiOMe 的热诱导 ..beta..-消除以提供二甲基硅烯，但 Me/sub 3/SiOMe 从热力学上有利地消除Me/sub 3/SiSiMe/sub 2/CH/sub 2/OMe 不会发生。从动力学研究和捕获实验中，发现这是由于对三中心消除 :CH/sub 2/ 更有利的 A 因子。发现从 sp/sup 2/-杂化碳中三中心消除 Me/sub 3/SiOMe 以提供亚乙烯基比从 sp/sup 3/-杂化碳中的类似消除更容易，因为两者都更有利活化能和 A 因子。因此，由于 ..cap alpha..-消除到 H/sub 2/C= 的更大便利性，不会发生从 H/sub 2/-C(OMe)SiMe/sub 2/SiMe/sub 3/ 形成硅丙二烯C：。
• Pyrolytic, kinetic, and theoretical studies on the isomerization of Me2HSiCH2.bul. to Me3Si.bul.
  作者：Thomas J. Barton、Anthony. Revis、Iain M. T. Davidson、S. Ijadi-Maghsoodi、Kevin J. Hughes、Mark S. Gordon

  DOI：10.1021/ja00274a028

  日期：1986.7

  4-(dimethylsilyl)-1-butene which decomposes through loss of the allyl radical to produce 'CH2SiHMe2• Rearrangement to Me3Si' was established by product analysis and trapping with methyl chloride. Kinetic analysis afforded a barrier of ca. 41 kcal/mol in excellent agreement with a calculated barrier of 42.6 kcaljmol achieved with fourth-order perturbation theory corrections (MP4) and addition of zero-point vibrational

  通过对 4-(二甲基甲硅烷基)-1-丁烯的热解研究获得了“CH2SiHMe2 通过氢的 1,2-迁移异构化为 Me3Si”的证据，4-(二甲基甲硅烷基)-1-丁烯通过失去烯丙基而分解生成“CH2SiHMe2• 重排为Me3Si' 是通过产物分析和用氯甲烷捕集建立的。动力学分析提供了大约的障碍。41 kcal/mol 与通过四阶微扰理论校正 (MP4) 和零点振动校正实现的 42.6 kcaljmol 计算势垒非常一致。尽管以硅为中心的自由基明显比非共振稳定的以碳为中心的自由基更稳定，1 仅在爱荷华州立大学。t 道康宁博士前少数民族研究员，1981-1983。1 大学。.L 北达科他州立大学。0002-7863/86/1508-4022$01.50/0 已经报道了两个 R3Si-R' 2 重排为 R2Si-CR' 2R 的例子，并且这两个例子都以硅作为迁移基团 R。广泛研究的六甲基乙硅烷 2
• Intramolecular reactions of (alkenyldimethylsilyl)carbenes
  作者：John W. Connolly、Paul F. Fryer

  DOI：10.1016/s0022-328x(00)87515-4

  日期：1971.8

  The reaction between compounds of the type [CH2CH(CH2)n](CH3)2SiCH2Cl and sodium has been studied. Intermediacy of the corresponding carbene (or carbenoid reagent) is proposed and evidence for intramolecular carbene addition to the olefinic linkage is presented in the case where n=0, 2 and 3.

  研究了[CH 2 = CH（CH 2）n ]（CH 3）2 SiCH 2 Cl类型的化合物与钠之间的反应。提出了相应卡宾（或类胡萝卜素试剂）的中间体，并提出了在n = 0、2和3的情况下将分子内卡宾加成至烯烃键的证据。
• Some observations on the thermal interconversion of silanediyls (silylenes) and sila-olefins (silenes)
  作者：Iain M. T. Davidson、Sina Ijadi-Maghsoodi、Thomas J. Barton、Nolan Tillman

  DOI：10.1039/c39840000478

  日期：——

  New experiments on thermally-generated Me2i are interpreted in terms of a reversible silanediyl ⇌ sila-olefin isomerization, as predicted theoretically; earlier apparently conflicting results are shown to be consistent with this explanation.

  如理论上预测的那样，对可热生成的Me 2 i的新实验用可逆的硅烷二基⇌硅烷基-烯烃异构化来解释。早期的明显矛盾的结果表明与该解释是一致的。