4-carbomethoxy-3-methoxy-4-(1'-oxa-3'-butenyl)-2,5-cyclohexadien-1-one | 136213-38-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 乙烯酯类
• 英文名称: 4-carbomethoxy-3-methoxy-4-(1'-oxa-3'-butenyl)-2,5-cyclohexadien-1-one
• 英文别名: Methyl 2-methoxy-4-oxo-1-prop-2-enoxycyclohexa-2,5-diene-1-carboxylate
• CAS: 136213-38-2
• 化学式: C₁₂H₁₄O₅
• 分子量: 238.24
• InChiKey: GOHCVYYZCFMPQS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4-carbomethoxy-3-methoxy-4-(1'-oxa-3'-butenyl)-2,5-cyclohexadien-1-one 以 苯 为溶剂， 反应 8.0h， 以58%的产率得到(2R^*,6S^*,9S^*,10S^*)-6-carbomethoxy-5-methoxy-7-oxatricyclo<5.2.1.0^2,10>dec-4-en-3-one
  参考文献：
  名称：

  Substituent effects on the photorearrangements of 4-alkoxy-4-carbomethoxy-3-methoxy-2,5-cyclohexadien-1-ones

  摘要：

  Enantiomerically enriched 4-carbomethoxy-3,4-dimethoxy-2,5-cyclohexadien-1-one (1) undergoes a completely diastereoselective (but not enantiospecific) type A photorearrangement at 366 nm to give 6-carbomethoxy-4,6-dimethoxybicyclo[3.1.0(1,5)]hex-3-en-2-one (2) in 81% isolated yield. A chiral NMR shift study indicates that 1 undergoes partial loss of absolute configuration at C(4) during irradiation. Bicyclohexenone 2 is photostable at 366 nm but rearranges to its diastereoisomer 3 and phenols 4 and 5 at > 300 nm. It is proposed that ground-state conformational effects control the type A photoreactivity of 1 and that rearrangement to 2 occurs in accord with the principle of least motion in the transition states for rearrangements to diastereomerically related zwitterions 1a and 1b (Scheme III). The intramolecular 2 + 2 photocycloaddition of 4-carbomethoxy-3-methoxy-4-(1'-oxa-3'-butenyl)-2,5-cyclohexadien-1-one (9) gives a mixture of 7-oxatricyclodecenones 10 (58%) and 11 (18%), without interference from type A photoreactivity.

  DOI：

  10.1021/jo00022a033
• 作为产物：
  描述：

  6-carbomethoxy-1-methoxy-6-(1'-oxa-3'-butenyl)-1,4-cyclohexadiene 在 叔丁基过氧化氢 、 重铬酸吡啶 、 Celite 作用下， 以 苯 为溶剂， 反应 2.0h， 以31%的产率得到4-carbomethoxy-3-methoxy-4-(1'-oxa-3'-butenyl)-2,5-cyclohexadien-1-one
  参考文献：
  名称：

  Substituent effects on the photorearrangements of 4-alkoxy-4-carbomethoxy-3-methoxy-2,5-cyclohexadien-1-ones

  摘要：

  Enantiomerically enriched 4-carbomethoxy-3,4-dimethoxy-2,5-cyclohexadien-1-one (1) undergoes a completely diastereoselective (but not enantiospecific) type A photorearrangement at 366 nm to give 6-carbomethoxy-4,6-dimethoxybicyclo[3.1.0(1,5)]hex-3-en-2-one (2) in 81% isolated yield. A chiral NMR shift study indicates that 1 undergoes partial loss of absolute configuration at C(4) during irradiation. Bicyclohexenone 2 is photostable at 366 nm but rearranges to its diastereoisomer 3 and phenols 4 and 5 at > 300 nm. It is proposed that ground-state conformational effects control the type A photoreactivity of 1 and that rearrangement to 2 occurs in accord with the principle of least motion in the transition states for rearrangements to diastereomerically related zwitterions 1a and 1b (Scheme III). The intramolecular 2 + 2 photocycloaddition of 4-carbomethoxy-3-methoxy-4-(1'-oxa-3'-butenyl)-2,5-cyclohexadien-1-one (9) gives a mixture of 7-oxatricyclodecenones 10 (58%) and 11 (18%), without interference from type A photoreactivity.

  DOI：

  10.1021/jo00022a033

文献信息

• Substituent effects on the photorearrangements of 4-alkoxy-4-carbomethoxy-3-methoxy-2,5-cyclohexadien-1-ones
  作者：Arthur G. Schultz、Roger E. Harrington

  DOI：10.1021/jo00022a033

  日期：1991.10

  Enantiomerically enriched 4-carbomethoxy-3,4-dimethoxy-2,5-cyclohexadien-1-one (1) undergoes a completely diastereoselective (but not enantiospecific) type A photorearrangement at 366 nm to give 6-carbomethoxy-4,6-dimethoxybicyclo[3.1.0(1,5)]hex-3-en-2-one (2) in 81% isolated yield. A chiral NMR shift study indicates that 1 undergoes partial loss of absolute configuration at C(4) during irradiation. Bicyclohexenone 2 is photostable at 366 nm but rearranges to its diastereoisomer 3 and phenols 4 and 5 at > 300 nm. It is proposed that ground-state conformational effects control the type A photoreactivity of 1 and that rearrangement to 2 occurs in accord with the principle of least motion in the transition states for rearrangements to diastereomerically related zwitterions 1a and 1b (Scheme III). The intramolecular 2 + 2 photocycloaddition of 4-carbomethoxy-3-methoxy-4-(1'-oxa-3'-butenyl)-2,5-cyclohexadien-1-one (9) gives a mixture of 7-oxatricyclodecenones 10 (58%) and 11 (18%), without interference from type A photoreactivity.