2-phenyl-6,6-diacetoxyhexa-2,4-dienone

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-phenyl-6,6-diacetoxyhexa-2,4-dienone
• 英文别名: (1-Acetyloxy-6-oxo-5-phenylcyclohexa-2,4-dien-1-yl) acetate
• 化学式: C₁₆H₁₄O₅
• 分子量: 286.284
• InChiKey: WDQJULNYGMKKRB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  lead(IV) tetraacetate 、 邻苯基苯酚 以 溶剂黄146 为溶剂， 反应 2.0h， 以29%的产率得到6-acetoxy-6-phenylcyclohexa-2,4-dienone
  参考文献：
  名称：

  A Solvolytic C−C Cleavage Reaction of 6-Acetoxycyclohexa-2,4-dienones:  Mechanistic Implications for the Intradiol Catechol Dioxygenases

  摘要：

  6-Acetoxycyclohexa-2,4-dienones are found to undergo a rapid reaction in methanol/water under mildly basic conditions to give an acyclic ketoester as the major product for 6-phenyl and 6-methyl substrates. Reaction monitoring by UV spectroscopy indicates the formation of an unsaturated ketone reaction intermediate (lambda (max) 275 nm, R = Ph) and the transient appearance of a highly conjugated species. Reaction of the 6-phenyl substrate (4.95 x 10(-6) s(-1)) is 2-fold faster than the 6-methyl substrate (2.47 x 10(-6) s(-1)). The reaction rate is first order with respect to substrate concentration, and the final step in the reaction is ps-dependent. No cleavage was observed for a substrate lacking an acetyl substituent. A reaction mechanism for C-C cleavage is proposed involving a benzene oxide-oxepin interconversion. The possible relevance to the catalytic mechanism of the intradiol catechol dioxygenases is discussed.

  DOI：

  10.1021/jo001669r

文献信息

• A Solvolytic C−C Cleavage Reaction of 6-Acetoxycyclohexa-2,4-dienones:  Mechanistic Implications for the Intradiol Catechol Dioxygenases
  作者：Kirstin L. Eley、Patrick J. Crowley、Timothy D. H. Bugg

  DOI：10.1021/jo001669r

  日期：2001.3.1

  6-Acetoxycyclohexa-2,4-dienones are found to undergo a rapid reaction in methanol/water under mildly basic conditions to give an acyclic ketoester as the major product for 6-phenyl and 6-methyl substrates. Reaction monitoring by UV spectroscopy indicates the formation of an unsaturated ketone reaction intermediate (lambda (max) 275 nm, R = Ph) and the transient appearance of a highly conjugated species. Reaction of the 6-phenyl substrate (4.95 x 10(-6) s(-1)) is 2-fold faster than the 6-methyl substrate (2.47 x 10(-6) s(-1)). The reaction rate is first order with respect to substrate concentration, and the final step in the reaction is ps-dependent. No cleavage was observed for a substrate lacking an acetyl substituent. A reaction mechanism for C-C cleavage is proposed involving a benzene oxide-oxepin interconversion. The possible relevance to the catalytic mechanism of the intradiol catechol dioxygenases is discussed.