5-isopropylidene-2,6-dimethyl-2-(triethylsiloxy)-3-heptyn-6-ol | 201275-88-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-isopropylidene-2,6-dimethyl-2-(triethylsiloxy)-3-heptyn-6-ol
• 英文别名: 2,6-dimethyl-3-propan-2-ylidene-6-triethylsilyloxyhept-4-yn-2-ol
• CAS: 201275-88-9
• 化学式: C₁₈H₃₄O₂Si
• 分子量: 310.552
• InChiKey: DEXBMMMNFKJFEO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  21.0
• 可旋转键数：
  6.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  29.46
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  5-isopropylidene-2,6-dimethyl-2-(triethylsiloxy)-3-heptyn-6-ol 在 palladium on activated charcoal 氢气 作用下， 以 甲醇 为溶剂， 以90%的产率得到(3Z)-5-isopropylidene-2,6-dimethyl-2-(triethylsiloxy)-3-hepten-6-ol
  参考文献：
  名称：

  Further demonstration of the higher reactivity of the vinyl hydrogen rather than the allyl hydrogen towards singlet oxygen

  摘要：

  在一种新的线性扭曲的1,3-二烯中，观察到乙烯氢相对于仲烯氢对单态氧的异常高反应性。

  DOI：

  10.1039/a705924h
• 作为产物：
  描述：

  2-溴-3-甲基丁烯酸甲酯 在 四(三苯基膦)钯 作用下， 以 四氢呋喃 为溶剂， 生成 5-isopropylidene-2,6-dimethyl-2-(triethylsiloxy)-3-heptyn-6-ol
  参考文献：
  名称：

  Further demonstration of the higher reactivity of the vinyl hydrogen rather than the allyl hydrogen towards singlet oxygen

  摘要：

  在一种新的线性扭曲的1,3-二烯中，观察到乙烯氢相对于仲烯氢对单态氧的异常高反应性。

  DOI：

  10.1039/a705924h

文献信息

• Photosensitized Oxygenation of Twisted 1,3-Dienes:  Abnormally Higher Reactivity of Vinyl Hydrogen Rather than Allyl Hydrogen toward Singlet Oxygen
  作者：Hajime Mori、Keiichi Ikoma、Sachihiko Isoe、Kazuo Kitaura、Shigeo Katsumura

  DOI：10.1021/jo980955o

  日期：1998.11.1

  As one of the novel examples to investigate the characteristic reactivity of significantly twisted 1,3-dienes, the photosensitized oxygenation of two types of significantly twisted 1,3-dienes, cis-beta-ionol derivative 2 and acyclic derivative Il, is investigated. Photosensitized oxygenation of 2a-f and 11a-e revealed that the vinyl hydrogen Ha was more reactive than the allyl hydrogen Hb. Thus, phenyl derivative 2e and tert-butyl-substituted compound lid selectively produced allenes 3e and 13d in 67% and 75% yield resulting from the ene reaction of the vinyl hydrogen Ha rather than allyl alcohols 4e and 14d resulting from the allyl hydrogen abstraction in 24% and 8% yield, respectively. Furthermore, in the case of methyl-substituted compound 11b, the extent of the inherent reactivity of the vinyl hydrogen Ha was similar to that of the allyl hydrogen He. On the basis of X-ray analysis and NIM and MO calculations, the discovered abnormally higher reactivity of the vinyl hydrogen would be rationalized by considering mainly the large sigma*-pi orbital interaction between the vinyl C-H bond and another double bond in significantly twisted 1,3-dienes resulting from calculations of HOMO electron densities.