1-Bromo-4,5-benzo-1,4-cycloheptadienyl 7-mesylate | 150545-62-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1-Bromo-4,5-benzo-1,4-cycloheptadienyl 7-mesylate
• 英文别名: (7-bromo-6,9-dihydro-5H-benzo[7]annulen-6-yl) methanesulfonate
• CAS: 150545-62-3
• 化学式: C₁₂H₁₃BrO₃S
• 分子量: 317.203
• InChiKey: AOBYAGOSQOCQKE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.41
• 重原子数：
  17.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  1-Bromo-4,5-benzo-1,4-cycloheptadienyl 7-mesylate 在 lithium aluminium tetrahydride 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 4.0h， 生成 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：

  1,1-dibromo-1a,2,7,7a-tetrahydro-1H-cyclopropanaphthalene 在 水 、 silver nitrate 、 三乙胺 作用下， 以 二氯甲烷 、 丙酮 为溶剂， -4.0~126.0 ℃ 、911.92 kPa 条件下， 反应 2.5h， 生成 1-Bromo-4,5-benzo-1,4-cycloheptadienyl 7-mesylate
  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