1-溴-4,5-苯并-1,4-环庚二烯 | 150545-63-4

• 分子结构分类: 有机化合物 - 苯类化合物
• 中文名称: 1-溴-4,5-苯并-1,4-环庚二烯
• 英文名称: 1-Bromo-4,5-benzo-1,4-cycloheptadiene
• 英文别名: 7-bromo-8,9-dihydro-5H-benzo[7]annulene
• CAS: 150545-63-4
• 化学式: C₁₁H₁₁Br
• 分子量: 223.112
• InChiKey: SDSHMQNAYACUOS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  1-溴-4,5-苯并-1,4-环庚二烯 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以74%的产率得到benzocycloheptatrien
  参考文献：
  名称：

  A seven-membered-ring allene dimer: synthesis of 1,2-benzo-1,3,4-cycloheptatriene and attempted synthesis of 1,2-benzo-1,4,5-cycloheptatriene

  摘要：

  7,7-Dibromo-3,4-benzobicyclo[4.1.0]heptane (6) and 7,7-dibromo-2,3-benzobicyclo[4.1.0]heptane (14) have been synthesized and their silver ion-catalyzed reactions studied. Hydroxy alcohol 7a was converted to the corresponding vinyl bromide 10. Reaction of 10 with base gave the hydrocarbon 12, instead of the expected allene 4. Hydroxy alcohol 15a was converted to the corresponding mesylate 20, but all attempts to reduce 20 to the expected vinyl bromide 23 failed. Instead, unexpected ether 21 was obtained. Therefore, 15a was treated with PBr3 to give 22, which upon treatment with LiAlH4 gave the vinyl bromide 23. Reaction of 23 'with potassium tert-butoxide produced strained bicyclic allene 5, which underwent a dimerization to give 24. Addition of tetracyanoethylene to dimer 24 resulted in the formation of 26, whose structure was investigated by X-ray crystallography.

  DOI：

  10.1021/jo00072a016
• 作为产物：
  描述：

  1-Bromo-4,5-benzo-1,4-cycloheptadienyl 7-mesylate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 2.0h， 以74%的产率得到1-溴-4,5-苯并-1,4-环庚二烯
  参考文献：
  名称：

  A seven-membered-ring allene dimer: synthesis of 1,2-benzo-1,3,4-cycloheptatriene and attempted synthesis of 1,2-benzo-1,4,5-cycloheptatriene

  摘要：

  7,7-Dibromo-3,4-benzobicyclo[4.1.0]heptane (6) and 7,7-dibromo-2,3-benzobicyclo[4.1.0]heptane (14) have been synthesized and their silver ion-catalyzed reactions studied. Hydroxy alcohol 7a was converted to the corresponding vinyl bromide 10. Reaction of 10 with base gave the hydrocarbon 12, instead of the expected allene 4. Hydroxy alcohol 15a was converted to the corresponding mesylate 20, but all attempts to reduce 20 to the expected vinyl bromide 23 failed. Instead, unexpected ether 21 was obtained. Therefore, 15a was treated with PBr3 to give 22, which upon treatment with LiAlH4 gave the vinyl bromide 23. Reaction of 23 'with potassium tert-butoxide produced strained bicyclic allene 5, which underwent a dimerization to give 24. Addition of tetracyanoethylene to dimer 24 resulted in the formation of 26, whose structure was investigated by X-ray crystallography.

  DOI：

  10.1021/jo00072a016

文献信息

• Nickel‐Catalyzed Conversion of Enol Triflates into Alkenyl Halides
  作者：Julie L. Hofstra、Kelsey E. Poremba、Alex M. Shimozono、Sarah E. Reisman

  DOI：10.1002/anie.201906815

  日期：2019.10.14

  A Ni-catalyzed halogenation of enol triflates was developed and it enables the synthesis of a broad range of alkenyl iodides, bromides, and chlorides under mild reaction conditions. The reaction utilizes inexpensive, bench-stable Ni(OAc)2 ⋅4 H2 O as a precatalyst and proceeds at room temperature in the presence of sub-stoichiometric Zn and either 1,5-cyclooctadiene or 4-(N,N-dimethylamino)pyridine

  开发了镍催化的烯醇三氟甲磺酸酯卤化反应，能够在温和的反应条件下合成多种烯基碘化物、溴化物和氯化物。该反应使用廉价、实验室稳定的 Ni(OAc)2·4 H2 O 作为预催化剂，并在亚化学计量的 Zn 和 1,5-环辛二烯或 4-(N,N-二甲基氨基) 存在下在室温下进行吡啶。
• Unusual triethylamine catalyzed rearrangement of bicyclic endoperoxides derived from substituted cycloheptatrienes
  作者：M.Emin Sengül、Zeynep Ceylan、Metin Balci

  DOI：10.1016/s0040-4020(97)00630-3

  日期：1997.7

  Triethylamine catalyzed rearrangement of the substituted bicyclic cycloheptatriene endoperoxides 9, 10,12, 13, 20, 21, 22 and 30 underwent different reaction modes and resulted in the formation of ring contraction products in the case of 9, 10, 12 and 13. However, 20, 21, and 30 provided rearranged diketones 23, 24 and 32 almost in quantitative yield. The mechanism of these reactions was discussed

  三乙胺催化的取代双环环庚三烯内过氧化物9、10、12、13、20、21、22和30的重排经历不同的反应模式，并在9、10、12和13的情况下导致形成环收缩产物。然而，20，21，和30提供重新排列二酮23，24和32几乎以定量产率。讨论了这些反应的机理。