2-methyl-2-trimethylsilyloxy-4-pentyne | 132789-33-4

• 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
• 英文名称: 2-methyl-2-trimethylsilyloxy-4-pentyne
• 英文别名: Silane, [(1,1-dimethyl-3-butynyl)oxy]trimethyl-；trimethyl(2-methylpent-4-yn-2-yloxy)silane
• CAS: 132789-33-4
• 化学式: C₉H₁₈OSi
• 分子量: 170.327
• InChiKey: ANVMNPNQZIVXKR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.64
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-methyl-2-trimethylsilyloxy-4-pentyne 在 Lindlar's catalyst N-溴代丁二酰亚胺(NBS) 、 正丁基锂 、 Amberlite resin 、 氢气 、 4-甲基苯磺酸吡啶 、 potassium carbonate 作用下， 以 四氯化碳 为溶剂， 反应 12.5h， 生成 5-bromo-2,2-dimethyl-1,7-dioxaspiro<5.5>undec-3-ene
  参考文献：
  名称：

  Allylic oxidation of unsaturated spiroketals.

  摘要：

  Allylic bromination of the bicyclic spiroketals (4a-c) gave predominantly the axial bromides (6), (9) and (12) which underwent S(N)2 displacement to the equatorial alcohols (7), (11) and (14) respectively using KO2/18-crown-6 in THF/DMSO (10:1).

  DOI：

  10.1016/s0040-4039(00)88531-7
• 作为产物：
  描述：

  三甲基氯硅烷 、 2-甲基-4-戊炔-2-醇 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 以55%的产率得到2-methyl-2-trimethylsilyloxy-4-pentyne
  参考文献：
  名称：

  Allylic functionalization of the 1,7-dioxaspiro[5.5]-undec-4-ene and d1,6,8-trioxadispiro[4.1.5.3]-pentadec-13-ene ring systems.

  摘要：

  Allylic bromination of the bicyclic spiroacetals 5, 6 and 7 gave predominantly the axial bromides 15, 21 and 23 which underwent S(N)2 displacement to the equatorial alcohols 17, 22 and 25 respectively, using potassium superoxide and 18-crown-6 in THF/DMSO (10:1). Allylic bromination of the cis-bis-spiroacetal 26 gave predominantly the rearranged allylic bromide 29 which afforded alcohols 30 and 31 resulting from both S(N)2' and S(N)2 displacement upon treatment with potassium superoxide. Bromination of the trans-bis-spiroacetal 27 afforded a complex mixture from which only the non-rearranged bromide 34 could be isolated. This bromide 34 afforded the axial alcohol 37 upon treatment with potassium superoxide.

  DOI：

  10.1016/s0040-4020(01)88235-1

文献信息

• Efficient and practical protocol for silylation of hydroxyl groups using reusable lithium perchlorate dispread in silica gel under neutral condition
  作者：Najmedin Azizi、Rozbeh Yousefi、Mohammad R. Saidi

  DOI：10.1016/j.jorganchem.2005.11.005

  日期：2006.2

  for the trimethylsilylation of a wide variety of alcohols, including primary, allylic, benzylic, secondary, hindered secondary, tertiary, and phenols with hexamethyldisilazane on the surface of silica gel dispersed with LiClO4 in room temperature at few minutes in excellent yields under neutral conditions is reported. This procedure also allows the excellent selectivity under LP-SiO2 system for silylation

  在室温下几分钟内，用六甲基二硅氮烷在六氯二硅氮烷上分散含有LiClO 4的硅胶表面上的多种醇，包括伯，烯丙基，苄基，仲，受阻仲，叔和苯酚的三甲基甲硅烷基化反应，非常高效，温和据报道在中性条件下产量极高。该方法还允许在存在胺和酚羟基的情况下在LP-SiO 2系统下对醇进行甲硅烷基化具有优异的选择性。
• BRIMBLE, MARGARET A.;EDMONDS, MICHAEL K.;WILLIAMS, GEOFFREY M., TETRAHEDRON LETT., 31,(1990) N1, C. 7509-7512
  作者：BRIMBLE, MARGARET A.、EDMONDS, MICHAEL K.、WILLIAMS, GEOFFREY M.

  DOI：——

  日期：——
• Allylic functionalization of the 1,7-dioxaspiro[5.5]-undec-4-ene and d1,6,8-trioxadispiro[4.1.5.3]-pentadec-13-ene ring systems.
  作者：Margaret A. Brimble、Michael K. Edmonds、Geoffrey M. Williams

  DOI：10.1016/s0040-4020(01)88235-1

  日期：1992.1

  Allylic bromination of the bicyclic spiroacetals 5, 6 and 7 gave predominantly the axial bromides 15, 21 and 23 which underwent S(N)2 displacement to the equatorial alcohols 17, 22 and 25 respectively, using potassium superoxide and 18-crown-6 in THF/DMSO (10:1). Allylic bromination of the cis-bis-spiroacetal 26 gave predominantly the rearranged allylic bromide 29 which afforded alcohols 30 and 31 resulting from both S(N)2' and S(N)2 displacement upon treatment with potassium superoxide. Bromination of the trans-bis-spiroacetal 27 afforded a complex mixture from which only the non-rearranged bromide 34 could be isolated. This bromide 34 afforded the axial alcohol 37 upon treatment with potassium superoxide.
• Allylic oxidation of unsaturated spiroketals.
  作者：Margaret A Brimble、Michael K Edmonds、Geoffrey M Williams

  DOI：10.1016/s0040-4039(00)88531-7

  日期：1990.1

  Allylic bromination of the bicyclic spiroketals (4a-c) gave predominantly the axial bromides (6), (9) and (12) which underwent S(N)2 displacement to the equatorial alcohols (7), (11) and (14) respectively using KO2/18-crown-6 in THF/DMSO (10:1).