(E)-2,2-dimethyl-1-phenylpent-3-en-1-one | 74175-88-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-2,2-dimethyl-1-phenylpent-3-en-1-one
• CAS: 74175-88-5
• 化学式: C₁₃H₁₆O
• 分子量: 188.269
• InChiKey: YWRKCTVAAFALFD-ONNFQVAWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (E)-2,2-dimethyl-1-phenylpent-3-en-1-one 在 sodium hydroxide 、 sodium tetrahydroborate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 4.5h， 生成 4,4-dimethyl-5-methoxy-5-phenyl-(E)-2-pentene
  参考文献：
  名称：

  Stereochemistry of Carbenic 1,2-Vinyl Shifts

  摘要：

  Various 1-phenylbut-3-enylidenes, (Ph)CCR2CH=CHR', were generated thermally and photolytically from tosylhydrazone (diazo) precursors. 1,2-Vinyl shifts, leading to 1,3-dienes, R'CH=CHC(Ph)=CR2, were found to predominate over gamma-C-H insertion (R = Me) and to compete with 1,2-H shifts (R = H). Intramolecular addition to the double bond was detected in the case of R = R' = Me. The resulting bicyclobutane is thermally stable and does not mediate the vinyl shift. Stereospecific migration of 1-propenyl groups (R' = Me), with retention of configuration, was observed on thermolysis and direct photolysis of appropriate substrates. These data exclude the intervention of a triplet diradical and point, to vinyl migration in the singlet manifold. Benzophenone-sensitized generation of the carbenes led to partial stereomutation but did not provide conclusive evidence for a triplet rearrangement (isomerization of the diene products could not be avoided under these conditions).

  DOI：

  10.1021/jo971691t

文献信息

• Weerdt, Anton J. A. van der; Cerfontain, Hans, Journal of the Chemical Society. Perkin transactions II, 1980, p. 592 - 597
  作者：Weerdt, Anton J. A. van der、Cerfontain, Hans

  DOI：——

  日期：——
• Stereochemistry of Carbenic 1,2-Vinyl Shifts
  作者：Wolfgang Kirmse、Siegfried Kopannia

  DOI：10.1021/jo971691t

  日期：1998.2.1

  Various 1-phenylbut-3-enylidenes, (Ph)CCR2CH=CHR', were generated thermally and photolytically from tosylhydrazone (diazo) precursors. 1,2-Vinyl shifts, leading to 1,3-dienes, R'CH=CHC(Ph)=CR2, were found to predominate over gamma-C-H insertion (R = Me) and to compete with 1,2-H shifts (R = H). Intramolecular addition to the double bond was detected in the case of R = R' = Me. The resulting bicyclobutane is thermally stable and does not mediate the vinyl shift. Stereospecific migration of 1-propenyl groups (R' = Me), with retention of configuration, was observed on thermolysis and direct photolysis of appropriate substrates. These data exclude the intervention of a triplet diradical and point, to vinyl migration in the singlet manifold. Benzophenone-sensitized generation of the carbenes led to partial stereomutation but did not provide conclusive evidence for a triplet rearrangement (isomerization of the diene products could not be avoided under these conditions).