cis-1,2,2a,8a-tetrahydro-2a,5,8a-trimethyl-8H-benzocyclobutapyran-8-one | 138629-60-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 英文名称: cis-1,2,2a,8a-tetrahydro-2a,5,8a-trimethyl-8H-benzocyclobutapyran-8-one
• 英文别名: cis-1,2,2a,8a-tetrahydro-2a,5,8a-trimethyl-8H-benzo[b]cyclobuta[e]pyran-8-one；(2aR,8aS)-2a,5,8a-trimethyl-1,2-dihydrocyclobuta[b]chromen-8-one
• CAS: 138629-60-4
• 化学式: C₁₄H₁₆O₂
• 分子量: 216.28
• InChiKey: CMRLNOGBCYKQKO-ZIAGYGMSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.13
• 重原子数：
  16.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  cis-1,2,2a,8a-tetrahydro-2a,5,8a-trimethyl-8H-benzocyclobutapyran-8-one 在 三氟化硼乙醚 作用下， 以 乙醚 、 苯 为溶剂， 反应 1.0h， 生成 (3aR,8bR)-8b-ethyl-1,3a,6-trimethyl-3H-cyclopenta[b][1]benzofuran
  参考文献：
  名称：

  Rapid, high-yield synthesis of the marine sesquiterpenes debromoaplysin and aplysin via the acid-catalyzed rearrangement of a cyclobutachromanol

  摘要：

  A short, stereocontrolled, high-yield synthesis of debromoaplysin (1) and aplysin (2) from the chromone 13 is described. The cycloaddition of ethylene to 13, followed by the addition of methylmagnesium iodide to the cycloadduct, furnished the cyclobutachromanol 15. Treatment of 15 in benzene with BF3.Et2O furnished a mixture of the alkenes 16 and 17, which can be visualized as arising by way of the initial 1,2-migration of the external and internal bonds, respectively, of the cyclobutane ring of 15. Similar rearrangement of 18, an ethyl analogue of 15, yielded 19 and 20. Rearrangement of 15 on treatment with sulfuric acid in petroleum ether at -78-degrees-C furnished, almost exclusively, 17. In contrast, when performed in nitroethane at -78-degrees-C, the same reaction afforded 16 exclusively. Thus, the solvent exerted a remarkable effect on the outcome of the rearrangement. Since alkene 16 had previously been converted to 1 and 2, this work represents an improved synthesis of the two sesquiterpenes.

  DOI：

  10.1021/jo00031a026
• 作为产物：
  描述：

  1-(2-羟基-4-甲基苯基)丙烷-1-酮 在 sodium acetate 作用下， 以 苯 为溶剂， 反应 10.0h， 生成 cis-1,2,2a,8a-tetrahydro-2a,5,8a-trimethyl-8H-benzocyclobutapyran-8-one
  参考文献：
  名称：

  Rapid, high-yield synthesis of the marine sesquiterpenes debromoaplysin and aplysin via the acid-catalyzed rearrangement of a cyclobutachromanol

  摘要：

  A short, stereocontrolled, high-yield synthesis of debromoaplysin (1) and aplysin (2) from the chromone 13 is described. The cycloaddition of ethylene to 13, followed by the addition of methylmagnesium iodide to the cycloadduct, furnished the cyclobutachromanol 15. Treatment of 15 in benzene with BF3.Et2O furnished a mixture of the alkenes 16 and 17, which can be visualized as arising by way of the initial 1,2-migration of the external and internal bonds, respectively, of the cyclobutane ring of 15. Similar rearrangement of 18, an ethyl analogue of 15, yielded 19 and 20. Rearrangement of 15 on treatment with sulfuric acid in petroleum ether at -78-degrees-C furnished, almost exclusively, 17. In contrast, when performed in nitroethane at -78-degrees-C, the same reaction afforded 16 exclusively. Thus, the solvent exerted a remarkable effect on the outcome of the rearrangement. Since alkene 16 had previously been converted to 1 and 2, this work represents an improved synthesis of the two sesquiterpenes.

  DOI：

  10.1021/jo00031a026

文献信息

• Unusual Rearrangement of Some Cyclobutachromanols. Facile Formation of Benzo-1,3-dioxane Ring System of Averufin
  作者：Jayati Mal、Asok Nath、Ramanathapuram V. Venkateswaran

  DOI：10.1021/jo961053v

  日期：1996.1.1

  Acid-catalyzed rearrangement of cyclobutachromanol (9) furnished the benzo-1,3-dioxane 13, arising from a de Mayo-type rearrangement. The structure of 13 was also proved by synthesis. Similarly, rearrangement of cyclobutachromanol 10 resulted in the benzo-1,3-dioxane compound 14. The benzo-1,3-dioxane ring system is the characteristic structural feature of averufin, an intermediate in the biosynthesis of aflatoxins.