(E)-5-<2-(2-Naphthalenylthio)-3-oxo-1-cyclohexen-1-yl>-2-pentenoic acid, ethyl ester | 130520-34-2

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: (E)-5-<2-(2-Naphthalenylthio)-3-oxo-1-cyclohexen-1-yl>-2-pentenoic acid, ethyl ester
• 英文别名: ethyl (E)-5-(2-naphthalen-2-ylsulfanyl-3-oxocyclohexen-1-yl)pent-2-enoate
• CAS: 130520-34-2
• 化学式: C₂₃H₂₄O₃S
• 分子量: 380.508
• InChiKey: JJOVSYXXJQOBDQ-AWNIVKPZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  68.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (E)-5-<2-(2-Naphthalenylthio)-3-oxo-1-cyclohexen-1-yl>-2-pentenoic acid, ethyl ester 生成 ethyl 15-oxo-21-thiahexacyclo[11.5.2.111,14.01,14.02,11.03,8]henicosa-3,5,7,9-tetraene-12-carboxylate
  参考文献：
  名称：

  DITTAMI, JAMES P.;NIE, XIAO-YI;BUNTEL, CHRISTOPHER J.;RIGATTI, STEVEN, TETRAHEDRON. LETT., 31,(1990) N7, C. 3821-3824

  摘要：

  DOI：
• 作为产物：
  描述：

  6-<2-(1,3-Dioxan-2-yl)ethyl>-7-oxabicyclo<4.1.0>heptan-2-one 在 溶剂黄146 作用下， 生成 (E)-5-<2-(2-Naphthalenylthio)-3-oxo-1-cyclohexen-1-yl>-2-pentenoic acid, ethyl ester
  参考文献：
  名称：

  光引发的分子内yyl-烯烃环加成反应

  摘要：

  研究了光瞬态物质的分子内烯烃加成反应。掺入丁烯酸乙酯官能团的芳基乙烯基硫醚的光解提供了类似烯的产物和/或（3 + 2）加合物。产物的形成受结构特征和反应条件的支配。

  DOI：

  10.1016/s0040-4039(00)97478-1

文献信息

• Photochemistry of Aryl Vinyl Sulfides and Aryl Vinyl Ethers:  Evidence for the Formation of Thiocarbonyl and Carbonyl Ylides
  作者：James P. Dittami、Yalin Luo、David Moss、W. Grant McGimpsey

  DOI：10.1021/jo9604649

  日期：1996.1.1

  Aryl vinyl thioethers 5a and 9a and aryl vinyl ethers 5b and 9b form ylide intermediates following laser irradiation at 308 nm. In benzene, the ylides possess long-lived absorption bands in the 600-800 nm region with a second weaker band at approximately 460 nm. In methanol, a known quencher of zwitterionic species, the lifetimes are reduced significantly. The decay kinetics measured within the long

  芳基乙烯基硫醚5a和9a以及芳基乙烯基醚5b和9b在308nm激光照射后形成ylide中间体。在苯中，乙炔化物在600-800 nm区域具有长寿命的吸收带，在约460 nm处具有第二弱的吸收带。在已知的两性离子物质淬灭剂甲醇中，寿命会大大缩短。在长波吸收包络线内测得的衰减动力学随波长变化，表明存在一种以上的叶立德物质。在芳基乙烯基醚的情况下，经由类似萘的三重态发生酰基化物的形成，而对于硫醚，则该前驱体的多样性可以是单重态或三重态。苯中5a和5b的产物形成涉及叶立德的闭环反应，生成二氢噻吩和二氢呋喃产物，分别。对于短时间的照射（无论是灯还是激光），观察到顺式和反式融合产物的混合物，而对于长时间的照射，仅检测到了顺式融合的化合物，这表明了将反式转化为顺式的光烯化机理。除了衍生自闭环的产物外，9a还提供分子内加成产物12。相反，衍生自9b的叶立德产生[3 + 2]环加成产物13。
• Tandem photocyclization-intramolecular addition reactions of aryl vinyl sulfides. Observation of a novel [2 + 2] cycloaddition-allylic sulfide rearrangement
  作者：James P. Dittami、Xiao Yi Nie、Hong Nie、H. Ramanathan、C. Buntel、S. Rigatti、Jon Bordner、Debra L. Decosta、Paul Williard

  DOI：10.1021/jo00030a022

  日期：1992.2

  Photocyclization of aryl vinyl sulfides reportedly proceeds via thiocarbonyl ylide intermediates. The photochemical behavior of several aryl vinyl sulfides, which incorporate a pendant alkene side chain, was explored. In general, naphthyl and phenyl vinyl thioethers provided products which are consistent with photocyclization to a thiocarbonyl ylide intermediate followed by either intramolecular hydrogen shift or subsequent intramolecular ylide-alkene addition. Product distribution is influenced by solvent and temperature effects. Novel secondary photoprocesses were also observed during some reactions. Thus, irradiation of naphthyl vinyl sulfide 20 gave dihydrothiophene 22 which underwent subsequent intramolecular [2 + 2] cycloaddition to provide 24. Upon prolonged irradiation 24 undergoes a novel allylic sulfide rearrangement to provide 25.