5,6,8,9-tetrachloro-2-(4-chlorophenyl)-3-phenyl-1-oxaspiro<3.5>nona-5,8-dien-7-one

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 5,6,8,9-tetrachloro-2-(4-chlorophenyl)-3-phenyl-1-oxaspiro<3.5>nona-5,8-dien-7-one
• 英文别名: 5,6,8,9-tetrachloro-2-phenyl-3-(4-chlorophenyl)-1-oxaspiro<3,5>nona-5,8-dien-7-one；5,6,8,9-tetrachloro-2-(4-chlorophenyl)-3-phenyl-1-oxaspiro[3.5]nona-5,8-dien-7-one；(2S,3R)-5,6,8,9-tetrachloro-2-(4-chlorophenyl)-3-phenyl-1-oxaspiro[3.5]nona-5,8-dien-7-one
• 化学式: C₂₀H₁₁Cl₅O₂
• 分子量: 460.571
• InChiKey: AUIYFROCGGLPQH-CXAGYDPISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  27
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1-(4-氯苯基)-2-苯基乙烯 、 四氯苯醌 以 1,4-二氧六环 为溶剂， 反应 50.0h， 以44%的产率得到5,6,8,9-tetrachloro-2-(4-chlorophenyl)-3-phenyl-1-oxaspiro<3,5>nona-5,8-dien-7-one
  参考文献：
  名称：

  Oxetanes from [2+2] Cycloaddition of Stilbenes to Quinone via Photoinduced Electron Transfer

  摘要：

  The photochemical coupling of various stilbenes (S) and chloranil (Q) is effected by the specific charge-transfer (CT) activation of the precursor electron donor-acceptor (EDA) complex [S, Q], and the [2+2] cycloaddition is established by X-ray structure elucidation of the crystalline trans-oxetanes formed selectively in high yields. Time-resolved (fs/ps) spectroscopy reveals the (singlet) ion-radical pair (1)[S.+, Q(.-)] to be the primary reaction intermediate and thus unambiguously establishes for the first time the electron-transfer pathway for this typical Paterno-Buchi transformation. The alternative cycloaddition via the specific activation of the carbonyl component (as a commonly applied procedure in Paterno-Buchi couplings) leads to the same oxetane regioisomers in identical molar ratios. As such, we conclude that a common electron-transfer mechanism applies via the quenching of the photoactivated quinone acceptor by the stilbene donor to afford triplet ion-radical pairs (3)[S.+, Q(.-)] which appear on the ns/mu s time scale. The spin multiplicities of the critical ion-pair intermediate [S.+, Q(.-)] in the two photoactivation methodologies determine the time scale of the reaction sequences (which are otherwise the same), and thus the efficiency of the relatively slow ion-pair collapses (k(c) similar or equal to 10(8) s(-1)) to the 1,4-biradical that ultimately leads to the oxetane product.

  DOI：

  10.1021/jo981754n

文献信息

• Xu, Jian-Hua; Wang, Long-Cheng; Xu, Jian-Wei, Journal of the Chemical Society. Perkin transactions I, 1994, # 5, p. 571 - 578
  作者：Xu, Jian-Hua、Wang, Long-Cheng、Xu, Jian-Wei、Yan, Bao-Zhen、Yuan, Han-Cheng

  DOI：——

  日期：——
• Oxetanes from [2+2] Cycloaddition of Stilbenes to Quinone via Photoinduced Electron Transfer
  作者：Duoli Sun、Stephan M. Hubig、Jay K. Kochi

  DOI：10.1021/jo981754n

  日期：1999.4.1

  The photochemical coupling of various stilbenes (S) and chloranil (Q) is effected by the specific charge-transfer (CT) activation of the precursor electron donor-acceptor (EDA) complex [S, Q], and the [2+2] cycloaddition is established by X-ray structure elucidation of the crystalline trans-oxetanes formed selectively in high yields. Time-resolved (fs/ps) spectroscopy reveals the (singlet) ion-radical pair (1)[S.+, Q(.-)] to be the primary reaction intermediate and thus unambiguously establishes for the first time the electron-transfer pathway for this typical Paterno-Buchi transformation. The alternative cycloaddition via the specific activation of the carbonyl component (as a commonly applied procedure in Paterno-Buchi couplings) leads to the same oxetane regioisomers in identical molar ratios. As such, we conclude that a common electron-transfer mechanism applies via the quenching of the photoactivated quinone acceptor by the stilbene donor to afford triplet ion-radical pairs (3)[S.+, Q(.-)] which appear on the ns/mu s time scale. The spin multiplicities of the critical ion-pair intermediate [S.+, Q(.-)] in the two photoactivation methodologies determine the time scale of the reaction sequences (which are otherwise the same), and thus the efficiency of the relatively slow ion-pair collapses (k(c) similar or equal to 10(8) s(-1)) to the 1,4-biradical that ultimately leads to the oxetane product.