(Z)-dodeca-4,8-diyn-6-ene | 78071-49-5

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: (Z)-dodeca-4,8-diyn-6-ene
• 英文别名: (Z)-dodeca-6-en-4,8-diyne；(Z)-dodeca-4,8-diyn-6-en；(z)-Dodec-6-ene-4,8-diyne；(Z)-dodec-6-en-4,8-diyne
• CAS: 78071-49-5
• 化学式: C₁₂H₁₆
• 分子量: 160.259
• InChiKey: FKHXRPLVKFJQLL-QXMHVHEDSA-N

物化性质

• 沸点：
  228.1±23.0 °C(Predicted)
• 密度：
  0.857±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (Z)-dodeca-4,8-diyn-6-ene 在 [Cp*Fe(η6-o-dipropylbenzene)]PF6 、 γ-松油烯 作用下， 以 丙酮 为溶剂， 反应 144.0h， 以91%的产率得到1,2-dipropylbenzene
  参考文献：
  名称：

  A Transition-Metal-Catalyzed Enediyne Cycloaromatization

  摘要：

  The pentamethylcyclopentadienyl iron cation, generated from [(eta5-C5Me5)Fe(NCMe)3]PF6, triggers the room temperature cycloaromatization of acyclic and alicyclic enediynes, in the presence of either 1,4-cyclohexadiene or terpinene as the hydrogen-atom donor, to give metal-arene products in good to excellent yields. Photolysis of the metal-arene complexes liberates the arene from the metal in excellent yield. The first demonstration of a transition-metal-catalyzed cycloaromatization of conjugated enediynes has been achieved under photochemical conditions utilizing either [(eta5-C5Me5)Fe(NCMe)3]PF6 or [(eta5-C5Me5)Fe(eta6-1,2-(Prn)2C6H4)]PF6 as the catalyst precursor. The use of a metal and light has led to a convenient method for cycloaromatization of a trans-enediyne.

  DOI：

  10.1021/ja050060a
• 作为产物：
  描述：

  (E)-dodeca-4,8-diyn-6-ene 生成 (Z)-dodeca-4,8-diyn-6-ene
  参考文献：
  名称：

  形成离散 1,4-脱氢苯中间体的动力学证据。分子间和分子内氢原子转移的捕获和高温 CIDNP 的观察

  摘要：

  LBL-11696 预印本已提交至美国化学学会杂志 离散 1,4-脱氢苯中间体形成的动力学证据。通过分子间和分子内氢原子转移的捕获和高温 CIDNP 的观察。托马斯·P·洛克哈特。Paul B. Comita 和 Robert C. Bergman 1980 年 9 月 两周借阅本 这是一本图书馆的流通本，可借阅两周。个人保留副本）> 致电技术人员。信息。Division )> 根据合同 W-7405-ENG-48 为美国能源部准备

  DOI：

  10.1021/ja00404a018

文献信息

• 2,3-Di-propyl-1,4-dehydrobenzene
  作者：Thomas P. Lockhart、Charles B. Mallon、Robert G. Bergman

  DOI：10.1021/ja00538a078

  日期：1980.8

  detailed study of the thermolysis of (Z)-4,5-diethynyl-4-octene (4) is presented. This reaction gives high yields of products formed by rearrangement and intramolecular and intermolecular trapping of the intermediate 1,4-dehydrobenzene 5. The kinetics of the solution pyrolysis of 4 in the presence and absence of trapping agent establish that the 1,4-dehydrobenzene is a discrete intermediate on the pathway

  在本文中，详细研究了 (Z)-4,5-二乙炔基-4-辛烯 (4) 的热解。该反应通过重排和分子内和分子间捕获中间体 1,4-脱氢苯 5 产生高产率的产物。 存在和不存在捕获剂时 4 的溶液热解动力学表明 1,4-脱氢苯是通向产品的途径上的离散中间体。通过在高温核磁共振光谱仪的探针中跟踪该反应，首次观察到 1,4-脱氢苯反应中的 CIDNP。这一观察结果以及动力学和化学捕获证据表明，随后在通往产品的途径上形成了两种额外的中间体。CIDNP的观察，
• A Synthetic and Mechanistic Investigation of the Chromium Tricarbonyl-Mediated Masamune–Bergman Cyclization. Direct Observation of a Ground-State Triplet<i>p</i>-Benzyne Biradical
  作者：Kai E. O. Ylijoki、Séverine Lavy、Angelika Fretzen、E. Peter Kündig、Théo Berclaz、Gérald Bernardinelli、Céline Besnard

  DOI：10.1021/om300427j

  日期：2012.8.13

  bond formation from an η6-enediyne complex is the lowest-energy path, forming a metal-bound p-benzyne biradical. NMR spectroscopy suggests that enediyne alkene coordination occurs in preference to alkyne coordination, forming a THF-stabilized olefin intermediate; subsequent alkyne coordination leads to cyclization. While biradical quenching occurs rapidly and primarily via the singlet biradical, the

  报道了一种新的室温下三羰基铬介导的苯二炔环芳香化反应。发生反应以在存在环状和非环状烯二炔[CR（CO）3（η 6 -萘）]和两个配位溶剂和氢原子源，提供铬-芳烃在合理产率和良好的diastereocontrol络合物。反应的机理已通过DFT计算和光谱方法进行了探讨。这些研究表明由该η直接C1-C6键形成6 -enediyne络合物具有最低能量的路径，形成金属结合的p-双苄基。NMR光谱表明，烯炔炔的配位优先于炔配位，形成了THF稳定的烯烃中间体。随后的炔烃配位导致环化。虽然双自由基淬灭迅速且主要通过单线态双自由基发生，但三重态双自由基可通过EPR光谱检测到，表明系统间交叉为三重态基态。
• Transition-Metal Hydrides as Hydrogen Atom Donors: Stronger Metal−Hydrogen Bonds Can Be Advantageous
  作者：Joseph M. O’Connor、Seth J. Friese

  DOI：10.1021/om800551d

  日期：2008.9.1

  The tungsten hydride complex (eta(5)-C5H5)W(CO)(3)H (1-W) functions as a hydrogen atom donor in the [(eta(5)- C5Me5)Ru(NCMe)(3)]PF6-mediated Bergman cycloaromatization reaction of (Z)-dodeca-4,8-diyn-6-ene. The strong M-H bond in 1-W does not react with the enediyne substrate but does react with the diradical arising from cyclization, thereby demonstrating the advantages of strong metal-hydrogen bonds in the hydrogen atom transfer reactions of metal hydrides with substrates involving alkenes and alkynes.
• Lott, William B.; Evans, Tom J.; Grissom, Charles B., Journal of the Chemical Society. Perkin transactions II, 1994, # 12, p. 2583 - 2586
  作者：Lott, William B.、Evans, Tom J.、Grissom, Charles B.

  DOI：——

  日期：——
• A Transition-Metal-Catalyzed Enediyne Cycloaromatization
  作者：Joseph M. O'Connor、Seth J. Friese、Betsy L. Rodgers

  DOI：10.1021/ja050060a

  日期：2005.11.30

  The pentamethylcyclopentadienyl iron cation, generated from [(eta5-C5Me5)Fe(NCMe)3]PF6, triggers the room temperature cycloaromatization of acyclic and alicyclic enediynes, in the presence of either 1,4-cyclohexadiene or terpinene as the hydrogen-atom donor, to give metal-arene products in good to excellent yields. Photolysis of the metal-arene complexes liberates the arene from the metal in excellent yield. The first demonstration of a transition-metal-catalyzed cycloaromatization of conjugated enediynes has been achieved under photochemical conditions utilizing either [(eta5-C5Me5)Fe(NCMe)3]PF6 or [(eta5-C5Me5)Fe(eta6-1,2-(Prn)2C6H4)]PF6 as the catalyst precursor. The use of a metal and light has led to a convenient method for cycloaromatization of a trans-enediyne.