1,5,8-trimethoxybenzobarrelene | 66731-02-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1,5,8-trimethoxybenzobarrelene
• 英文别名: 1,5,8-Trimethoxybenzobarrelen；1,3,6-Trimethoxytricyclo[6.2.2.0~2,7~]dodeca-2,4,6,9,11-pentaene；1,3,6-trimethoxytricyclo[6.2.2.02,7]dodeca-2,4,6,9,11-pentaene
• CAS: 66731-02-0
• 化学式: C₁₅H₁₆O₃
• 分子量: 244.29
• InChiKey: HFPZDJGGTQYGSO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,5,8-trimethoxybenzobarrelene 在 高氯酸 作用下， 反应 1.5h， 以42%的产率得到3,4-dihydro-5,8-dimethoxy-1,4-ethenonaphthalen-2(1H)-one
  参考文献：
  名称：

  双环系统的重排反应。第五部分。1，4-二氢-1,5,8-三甲氧基-1,4-亚乙基萘的酸催化重排以及芳族甲氧基对反应过程的显著作用

  摘要：

  3,6-Dimethoxyanthranilic acid (2) has been prepared by a procedure that is more reliable than our earlier one and used as a 3,6-dimerhoxybenzyne precursor in a reaction with anisole to give 1,4-dihydro-1,5,8-trimethoxy-1,4-ethenonaphthalenelene (1,5,8-trimethoxybenzobarrelene) (1). Trifluoroacetic acid-catalysed rearrangement of this benzobarrelene (1) gave as precedented products of bicyclo-rearrangement 3,4-dihydro-5,8-dimethoxy-1,4-erhenonaphthalen-2(1H)-one (5,8-dimethoxybenzobarrelenone) (3) and 5,9-dihydro-1,4-dimethoxy-5 9-methanobenzocyclohepten-6-one (7) along with 2,4',5-trimethoxybiphenyl (6), the product of a remarkable retro-Friedel-Crafts protodealkoxyalkylative fragmentation of the bicyclic system. Similar reactions were observed with perchloric acid. The structure of this unexpected biphenyl was confirmed by its preparation by Gomberg-Bachman-Hey arylation of 1,4-dimethoxybenzene.

  DOI：

  10.1016/0040-4020(95)00354-b
• 作为产物：
  描述：

  苯甲醚 、 3,6-dimethoxybenzenediazonium-2-carboxylate 以 1,2-二氯乙烷 为溶剂， 反应 4.0h， 以1.7 g的产率得到1,5,8-trimethoxybenzobarrelene
  参考文献：
  名称：

  双环系统的重排反应。第五部分。1，4-二氢-1,5,8-三甲氧基-1,4-亚乙基萘的酸催化重排以及芳族甲氧基对反应过程的显著作用

  摘要：

  3,6-Dimethoxyanthranilic acid (2) has been prepared by a procedure that is more reliable than our earlier one and used as a 3,6-dimerhoxybenzyne precursor in a reaction with anisole to give 1,4-dihydro-1,5,8-trimethoxy-1,4-ethenonaphthalenelene (1,5,8-trimethoxybenzobarrelene) (1). Trifluoroacetic acid-catalysed rearrangement of this benzobarrelene (1) gave as precedented products of bicyclo-rearrangement 3,4-dihydro-5,8-dimethoxy-1,4-erhenonaphthalen-2(1H)-one (5,8-dimethoxybenzobarrelenone) (3) and 5,9-dihydro-1,4-dimethoxy-5 9-methanobenzocyclohepten-6-one (7) along with 2,4',5-trimethoxybiphenyl (6), the product of a remarkable retro-Friedel-Crafts protodealkoxyalkylative fragmentation of the bicyclic system. Similar reactions were observed with perchloric acid. The structure of this unexpected biphenyl was confirmed by its preparation by Gomberg-Bachman-Hey arylation of 1,4-dimethoxybenzene.

  DOI：

  10.1016/0040-4020(95)00354-b

文献信息

• Rearrangement reactions of bicyclic systems. Part V. 1 Acid-catalysed rearrangements of 1,4-dihydro-1,5,8-trimethoxy-1,4-ethenonaphthalene and the remarkable effect of aromatic methoxy-groups on the course of the reaction
  作者：Neil J. Hales、Harry Heaney、John H. Hollinshead、Ram P. Sharma

  DOI：10.1016/0040-4020(95)00354-b

  日期：1995.7

  3,6-Dimethoxyanthranilic acid (2) has been prepared by a procedure that is more reliable than our earlier one and used as a 3,6-dimerhoxybenzyne precursor in a reaction with anisole to give 1,4-dihydro-1,5,8-trimethoxy-1,4-ethenonaphthalenelene (1,5,8-trimethoxybenzobarrelene) (1). Trifluoroacetic acid-catalysed rearrangement of this benzobarrelene (1) gave as precedented products of bicyclo-rearrangement 3,4-dihydro-5,8-dimethoxy-1,4-erhenonaphthalen-2(1H)-one (5,8-dimethoxybenzobarrelenone) (3) and 5,9-dihydro-1,4-dimethoxy-5 9-methanobenzocyclohepten-6-one (7) along with 2,4',5-trimethoxybiphenyl (6), the product of a remarkable retro-Friedel-Crafts protodealkoxyalkylative fragmentation of the bicyclic system. Similar reactions were observed with perchloric acid. The structure of this unexpected biphenyl was confirmed by its preparation by Gomberg-Bachman-Hey arylation of 1,4-dimethoxybenzene.