3-(2,4,5-trimethoxyphenyl)-3-cyclobutene-1,2-dione

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 3-(2,4,5-trimethoxyphenyl)-3-cyclobutene-1,2-dione
• 英文别名: 3-(2,4,5-Trimethoxyphenyl)cyclobut-3-ene-1,2-dione
• 化学式: C₁₃H₁₂O₅
• 分子量: 248.235
• InChiKey: JRVBXTYRWNUSSI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  1,2,4-三甲氧基苯 、 Semisquaric chloride 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以21%的产率得到3-(2,4,5-trimethoxyphenyl)-3-cyclobutene-1,2-dione
  参考文献：
  名称：

  Selective 1,4-Addition of Arenes to 3-Chloro-3-cyclobutene-1,2-dione under Friedel−Crafts Conditions. Synthesis and Reactivity of 4-Aryl-3-chloro-2-hydroxy-2-cyclobuten-1-ones¹

  摘要：

  The reaction of semisquaric chloride (7) with arenes 2 has been investigated. In the presence of 1.1 equiv of AlCl3 and in the temperature range of -15 degrees C to rt the arenes 2a-q afford the 4-aryl-3-chloro-2-hydroxy-2-cyclobuten-1-ones (chloroenols) 8a-q in good yield. By contrast, 7 reacts with 1,4-dimethoxybenzene (21) in boiling CH2Cl2 to give a mixture of (2,5-dimethoxyphenyl)cyclobutenedione (9a) (27% yield) and bis(2,5-dimethoxyphenyl)cyclobutenedione (10a) (8% yield). With 1,2,4-trimethoxybenzene (2r) in the presence of trifluoroacetic acid is generated (2,4,5-trimethoxyphenyl)cyclobutenedione (9b) in 21% yield. The chloroenols 8 allow a series of valuable transformation reactions: with diazomethane the chloroenol methyl ethers 11 are generated, with chlorine the 3-aryl-4-chlorocyclobutenediones 12, and with bromine in MeOH the 3-aryl-4-methoxycyclobutenediones 13. In DMSO or in acetone/H2O the chloroenols 8 eliminate HCl, furnishing the arylcyclobutenediones 14. In a mixture of acetone -d(6)/D2O/DCl are obtained 4-aryl-cyclobutenediones-3-d 15. For the latter two processes the corresponding 3-aryl-4-chlorocyclobutane-1,2-diones 16 are postulated as intermediates. Thermolysis of the chloroenols 8 and the chloroenol methyl ethers 11 in refluxing m-xylene afforded the 3-chloro-1,2-dihydroxynaphthalenes 17 and the 3-chlorol-hydroxy-2-methoxynaphthalenes 18, respectively.

  DOI：

  10.1021/jo952062r

文献信息

• Selective 1,4-Addition of Arenes to 3-Chloro-3-cyclobutene-1,2-dione under Friedel−Crafts Conditions. Synthesis and Reactivity of 4-Aryl-3-chloro-2-hydroxy-2-cyclobuten-1-ones¹
  作者：Arthur H. Schmidt、Gunnar Kircher、Stephan Maus、Heinz Bach

  DOI：10.1021/jo952062r

  日期：1996.1.1

  The reaction of semisquaric chloride (7) with arenes 2 has been investigated. In the presence of 1.1 equiv of AlCl3 and in the temperature range of -15 degrees C to rt the arenes 2a-q afford the 4-aryl-3-chloro-2-hydroxy-2-cyclobuten-1-ones (chloroenols) 8a-q in good yield. By contrast, 7 reacts with 1,4-dimethoxybenzene (21) in boiling CH2Cl2 to give a mixture of (2,5-dimethoxyphenyl)cyclobutenedione (9a) (27% yield) and bis(2,5-dimethoxyphenyl)cyclobutenedione (10a) (8% yield). With 1,2,4-trimethoxybenzene (2r) in the presence of trifluoroacetic acid is generated (2,4,5-trimethoxyphenyl)cyclobutenedione (9b) in 21% yield. The chloroenols 8 allow a series of valuable transformation reactions: with diazomethane the chloroenol methyl ethers 11 are generated, with chlorine the 3-aryl-4-chlorocyclobutenediones 12, and with bromine in MeOH the 3-aryl-4-methoxycyclobutenediones 13. In DMSO or in acetone/H2O the chloroenols 8 eliminate HCl, furnishing the arylcyclobutenediones 14. In a mixture of acetone -d(6)/D2O/DCl are obtained 4-aryl-cyclobutenediones-3-d 15. For the latter two processes the corresponding 3-aryl-4-chlorocyclobutane-1,2-diones 16 are postulated as intermediates. Thermolysis of the chloroenols 8 and the chloroenol methyl ethers 11 in refluxing m-xylene afforded the 3-chloro-1,2-dihydroxynaphthalenes 17 and the 3-chlorol-hydroxy-2-methoxynaphthalenes 18, respectively.