trans-1-hydroxy-2,5,6-trimethoxydihydrobenzocyclobutene | 143925-87-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: trans-1-hydroxy-2,5,6-trimethoxydihydrobenzocyclobutene
• 英文别名: (7S,8S)-4,5,8-trimethoxybicyclo[4.2.0]octa-1(6),2,4-trien-7-ol
• CAS: 143925-87-5
• 化学式: C₁₁H₁₄O₄
• 分子量: 210.23
• InChiKey: CRBACKSJZVVVLV-UWVGGRQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  3-羟基-2-甲氧基-6-(甲氧基甲基)苯甲醛 在 caesium carbonate 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 生成 trans-1-hydroxy-2,5,6-trimethoxydihydrobenzocyclobutene
  参考文献：
  名称：

  Stereoselective photocyclization of some phenolic, highly congested benzophenones and benzaldehydes. Use of cis-2-arylbenzocyclobutenol methyl ethers for the synthesis of lignans

  摘要：

  Irradiation of some highly congested, phenolic 2-(methoxymethyl)benzophenones provides a rapid, efficient and stereoselective entry to the corresponding 1-aryl-1-hydroxy-2-methoxybenzocyclobutenes in high chemical yield. The analogous photocyclization reaction of phenolic benzaldehydes appears to be more limited in scope. According to semiempirical (AM1) calculations on the thermal ring opening of a large number of benzocyclobutene derivatives, alpha,alpha'-dioxygenated o-quinodimethanes are significantly more stable (5-7 kcal/mol) than the corresponding benzocyclobutene derivatives, thereby suggesting that 1-hydroxy-2-alkoxybenzocyclobutenes are unlikely to be thermally derived from the corresponding o-QDM's during photolysis of o-(methoxymethyl)benzophenones. Hydrogenolysis (H-2, Pd/C) of either the cis or trans isomers of 1-aryl-1-hydroxy-2-methoxybenzocyclobutenes gives rise to cis-trans mixtures of 1-methoxy-2-arylbenzocyclobutenes enriched in the cis isomer. These enriched mixtures undergo thermal isomerization to the desired trans 1-methoxy-2-arylbenzocyclobutenes. The cis-enriched mixture directly derived from the hydrogenolysis step can be used as a precursor of the required (E,E)-alpha-aryl-alpha'-methoxy-o-quinodimethane for the synthesis of lignanes via the intermolecular Diels-Alder approach.

  DOI：

  10.1021/jo00049a033

文献信息

• Stereoselective photocyclization of some phenolic, highly congested benzophenones and benzaldehydes. Use of cis-2-arylbenzocyclobutenol methyl ethers for the synthesis of lignans
  作者：Gloria Coll、Antoni Costa、Pere M. Deya、Francina Flexas、Carmen Rotger、Jose M. Saa

  DOI：10.1021/jo00049a033

  日期：1992.11

  Irradiation of some highly congested, phenolic 2-(methoxymethyl)benzophenones provides a rapid, efficient and stereoselective entry to the corresponding 1-aryl-1-hydroxy-2-methoxybenzocyclobutenes in high chemical yield. The analogous photocyclization reaction of phenolic benzaldehydes appears to be more limited in scope. According to semiempirical (AM1) calculations on the thermal ring opening of a large number of benzocyclobutene derivatives, alpha,alpha'-dioxygenated o-quinodimethanes are significantly more stable (5-7 kcal/mol) than the corresponding benzocyclobutene derivatives, thereby suggesting that 1-hydroxy-2-alkoxybenzocyclobutenes are unlikely to be thermally derived from the corresponding o-QDM's during photolysis of o-(methoxymethyl)benzophenones. Hydrogenolysis (H-2, Pd/C) of either the cis or trans isomers of 1-aryl-1-hydroxy-2-methoxybenzocyclobutenes gives rise to cis-trans mixtures of 1-methoxy-2-arylbenzocyclobutenes enriched in the cis isomer. These enriched mixtures undergo thermal isomerization to the desired trans 1-methoxy-2-arylbenzocyclobutenes. The cis-enriched mixture directly derived from the hydrogenolysis step can be used as a precursor of the required (E,E)-alpha-aryl-alpha'-methoxy-o-quinodimethane for the synthesis of lignanes via the intermolecular Diels-Alder approach.