(E)-2,2,4,4-tetraphenylbut-3-enal oxime | 132716-09-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: (E)-2,2,4,4-tetraphenylbut-3-enal oxime
• 英文别名: 2,2,4,4-tetraphenylbut-3-enal oxime；(NE)-N-(2,2,4,4-tetraphenylbut-3-enylidene)hydroxylamine
• CAS: 132716-09-7
• 化学式: C₂₈H₂₃NO
• 分子量: 389.497
• InChiKey: CYDHDEIEAZMNHU-QUPMIFSKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  32.6
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-2,2,4,4-tetraphenylbut-3-enal oxime 反应 0.5h， 以74%的产率得到2,2,3,3-Tetraphenyl-cyclopropanecarbaldehyde oxime
  参考文献：
  名称：

  β-γ-不饱和肟的氮杂-二-π-甲烷重排

  摘要：

  尽管先前的研究表明，无环的β，γ-不饱和肟和肟醚不会发生氮杂-二-π-甲烷（ADPM）重排，但2-甲基-4,4-二苯基-2-乙烯基丁-3-烯醛肟5a，其甲基醚5b和2,2,4,4-四苯基丁-3-烯肟14通过ADPM途径生成相应的环丙基衍生物8a，8b和15，该反应受聚合物的稳定性控制。中间体1,3-双基。

  DOI：

  10.1016/s0040-4039(00)73099-1
• 作为产物：
  描述：

  2,2,4,4-四苯基-3-丁烯醛 在 吡啶 、 盐酸羟胺 作用下， 以 乙醇 为溶剂， 反应 1.5h， 以83%的产率得到(E)-2,2,4,4-tetraphenylbut-3-enal oxime
  参考文献：
  名称：

  Armesto, Diego; Horspool, William M.; Langa, Fernando, Journal of the Chemical Society. Perkin transactions I, 1991, # 1, p. 223 - 228

  摘要：

  DOI：

文献信息

• A Study of the Competition between the Di-.pi.-methane and the Azadi-.pi.-methane Processes in 2-Vinyl-.beta.,.gamma.-unsaturated Oxime Derivatives. The Novel Azadi-.pi.-methane Reactivity of .beta.,.gamma.-Unsaturated Oximes
  作者：Diego Armesto、Maria J. Ortiz、Ana Ramos、William M. Horspool、Elena P. Mayoral

  DOI：10.1021/jo00105a031

  日期：1994.12

  A study aimed at detecting intramolecular competition between the di-pi-methane (DPM) rear-rangement and the azadi-pi-methane (ADPM) process has been carried out. The results show that direct or acetophenone-sensitized irradiation of 2-(2,2-diphenylvinyl)-2-methyl-4,4-diphenyl-3- butenal oxime acetate 3 and the corresponding oxime trifluoroacetate 11 undergo only the DPM process to yield cyclopropanes. Similar DPM rearrangement was observed for 2-methyl-4,4-diphenyl-2-vinyl-3-butenonitrile 22. These are examples of triplet DPM reactivity in acyclic substrates where the central carbon has only one electron-withdrawing group. There is only one case of such reactivity in the aryl di-pi-methane process. However, 2-methyl-4,4-diphenyl-2-vinyl-2-vinyl-3-butenal oxime acetate 26 and the corresponding trifluoroacetate 15 undergo the ADPM rearrangement exclusively on direct or acetophenone-sensitized irradiation. The selectivity observed is interpreted as being dependent on the relative stabilities of the 1,4-bridged biradical intermediates. Based on previous failures to observe the ADPM reactions of beta,gamma-unsaturated oximes, an attempt to suppress the ADPM reactivity in compounds with a substitution pattern such as that present in 15 and 26 was made using the parent oxime 21. Surprisingly this compound reacts efficiently by the ADPM process and affords cyclopropane 30. This is the first example of ADPM reactivity of an acyclic beta,gamma-unsaturated oxime. Ah the rearrangements described are stereoselective. This reaction was extended to other oximes 45, 47a and 47b and also to the oxime ether 36. The photoreaction of 47b shows that the ADPM rearrangement of oximes can be extended to ketone derivatives. Previous studies have shown that such reactivity is uncommon. beta,gamma-Unsaturated oximes are usually considered to be photochemically inert but these results have shown that changes in substitution can promote efficient ADPM reactivity.
• Armesto Diego, Ramos Ana, Mayoral Elena P., Tetrahedron Lett, 35 (1994) N 22, S 3785-3788
  作者：Armesto Diego, Ramos Ana, Mayoral Elena P.

  DOI：——

  日期：——
• Armesto, Diego; Horspool, William M.; Langa, Fernando, Journal of the Chemical Society. Perkin transactions I, 1991, # 1, p. 223 - 228
  作者：Armesto, Diego、Horspool, William M.、Langa, Fernando、Ramos, Ana

  DOI：——

  日期：——
• The aza-di-π-methane rearrangement of β-γ-unsaturated oximes
  作者：Diego Armesto、Ana Ramos、Elena P. Mayoral

  DOI：10.1016/s0040-4039(00)73099-1

  日期：1994.5

  Although previous studies have shown that acyclic β,γ-unsaturated oximes and oxime ethers do not undergo the aza-di-π-methane (ADPM) rearrangement, the 2-methyl-4,4-diphenyl-2-vinylbut-3-enal oxime 5a, its methyl ether 5b and the 2,2,4,4-tetraphenylbut-3-enal oxime 14 give the corresponding cyclopropyl derivatives 8a, 8b and 15 by the ADPM path, in a reaction that is controlled by the stability of

  尽管先前的研究表明，无环的β，γ-不饱和肟和肟醚不会发生氮杂-二-π-甲烷（ADPM）重排，但2-甲基-4,4-二苯基-2-乙烯基丁-3-烯醛肟5a，其甲基醚5b和2,2,4,4-四苯基丁-3-烯肟14通过ADPM途径生成相应的环丙基衍生物8a，8b和15，该反应受聚合物的稳定性控制。中间体1,3-双基。