3,5-Dimethyl-7-phenyl-bicyclo[4.2.0]octa-1(6),2,4-trien-7-ol | 33574-14-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3,5-Dimethyl-7-phenyl-bicyclo[4.2.0]octa-1(6),2,4-trien-7-ol
• 英文别名: 3,5-Dimethyl-7-phenylbicyclo[4.2.0]octa-1,3,5-trien-7-ol
• CAS: 33574-14-0
• 化学式: C₁₆H₁₆O
• 分子量: 224.302
• InChiKey: KZPFIEUJPULFRY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3,5-Dimethyl-7-phenyl-bicyclo[4.2.0]octa-1(6),2,4-trien-7-ol 在 2,6,9,10-tetracyanoanthracene 作用下， 以 二氯甲烷 为溶剂， 反应 0.33h， 以99%的产率得到2,4,6-三甲基苯甲酮
  参考文献：
  名称：

  光诱导电子转移促进苯并环丁烯醇的电环还原

  摘要：

  苯并环丁烯醇1经历电子转移诱导的电环还原，生成邻喹啉甲烷中间体E - 4和Z - 4，然后互变异构为二苯甲酮2。捕集实验和激光闪光光解实验提供了有关中间体的证据。

  DOI：

  10.1016/0040-4039(96)01152-5
• 作为产物：
  描述：

  2,4,6-三甲基苯甲酮 生成 3,5-Dimethyl-7-phenyl-bicyclo[4.2.0]octa-1(6),2,4-trien-7-ol
  参考文献：
  名称：

  光致反应—XLVIII：立体和取代基对2,4,6-三烷基苯基酮的光反应的影响

  摘要：

  研究了立体和取代基对2,4,6-三烷基苯基酮的光化学反应的影响。在2,4,6-三烷基二苯甲酮的光反应中观察到惊人的空间效应。羰基越受阻，越容易发生光致烯化，导致分子内环化，导致苯并环丁烯醇衍生物。具有2,4,6-三烷基苯乙酮。在环化和光烯化反应中未观察到这种空间效应。这些反应已根据引起这些反应的激发态性质进行了解释。

  DOI：

  10.1016/s0040-4020(01)98025-1

文献信息

• Photoinduced reactions—XLVIII
  作者：Y. Kitaura、T. Matsuura

  DOI：10.1016/s0040-4020(01)98025-1

  日期：1971.1

  Steric and substituent effects on the photochemical reaction of 2,4,6-trialkylphenyl ketones has been investigated. A striking steric effect was observed in the photoreaction of 2,4,6-trialkylbenzophenones. The more hindered the carbonyl group, the more readily photoenolization occurs resulting in intramolecular cyclization leading to benzocyclobutenol derivatives. With 2,4,6-trialkylacetophenones

  研究了立体和取代基对2,4,6-三烷基苯基酮的光化学反应的影响。在2,4,6-三烷基二苯甲酮的光反应中观察到惊人的空间效应。羰基越受阻，越容易发生光致烯化，导致分子内环化，导致苯并环丁烯醇衍生物。具有2,4,6-三烷基苯乙酮。在环化和光烯化反应中未观察到这种空间效应。这些反应已根据引起这些反应的激发态性质进行了解释。
• Photoinduced reaction. 142. Intramolecular hydrogen abstraction from triplet states of 2,4,6-triisopropylbenzophenones: importance of hindered rotation in excited states
  作者：Yoshikatsu Ito、Hiroaki Nishimura、Yasutoshi Umehara、Yutaka Yamada、Mutsuto Tone、Teruo Matsuura

  DOI：10.1021/ja00344a029

  日期：1983.3
• Sterically promoted benzocyclobutenol formation from 2,4,6-triisopropylbenzophenone photolysis
  作者：Yoshikatsu Ito、Yasutoshi Umehara、Toyoto Hijiya、Yutaka Yamada、Teruo Matsuura

  DOI：10.1021/ja00538a041

  日期：1980.8
• Electrocycloreversion of benzocyclobutenols promoted by photoinduced electron transfer
  作者：Yasutake Takahashi、Kazuya Miyamoto、Kazuhiro Sakai、Hiroshi Ikeda、Tsutomu Miyashi、Yoshikatsu Ito、Ken Tabohashi

  DOI：10.1016/0040-4039(96)01152-5

  日期：1996.7

  Benzocyclobutenols 1 undergo electron-transfer induced electrocycloreversion to generate o-quinodimethane intermediates E-4 and Z-4, which then tautomerize to benzophenones 2. Evidence for the intermediates is provided by the trapping experiments and the laser flash photolysis experiments.

  苯并环丁烯醇1经历电子转移诱导的电环还原，生成邻喹啉甲烷中间体E - 4和Z - 4，然后互变异构为二苯甲酮2。捕集实验和激光闪光光解实验提供了有关中间体的证据。
• Photocyclization of 2,4,6-triethylbenzophenones in the solid state
  作者：Yoshikatsu Ito、Hiroki Takahashi、Jun-ya Hasegawa、Nicholas J. Turro

  DOI：10.1016/j.tet.2008.10.105

  日期：2009.1

  Photocyclization of 2,4,6-triethylbenzophenones (TEBPs) into (E)- or (Z)-benzocyclobutenols ((E)- or (Z)-CBs) is E-selective in solution. By contrast, upon solid-state photolysis, TEBP-3,4-diCl and especially TEBP-4-t-Bu gave (Z)-CB relative to (E)-CB with a Much higher proportion than that in solution. For TEBP-4-t-Bu, the most major product in the solid state is an indanol derivative (Inol) (E/Z/Inol=1:3.9:10.3 at 9% conversion). On the basis of the X-ray crystallographic analysis, Inol and (Z)-CB are both topochemical products. Notably, the relative proportion of (E)-CB increased with increased conversion, namely with increased disruption of the crystal lattice. The DFT calculation of highly hindered 2,6-diisopropylbenzophenone (DIBP) was also conducted. These results in conjunction with the previous results on 2,4,6-triisopropylbenzophenones (TIBPs) indicate that CB is formed either via trans-enol followed by its conrotatory ring-closure (paths a and d) or through direct cyclization of biradical (BR) (path b) as shown in Scheme 1. Normally the former route is faster. However, in the crystalline state or in the case of sterically hindered phenyl ketones, path b tends to be adopted. (c) 2008 Elsevier Ltd. All rights reserved.