5,6-(methylenedioxy)benzocyclobutenol | 144493-72-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: 5,6-(methylenedioxy)benzocyclobutenol
• 英文别名: 6,7-Dihydrocyclobuta[g][1,3]benzodioxol-7-ol
• CAS: 144493-72-1
• 化学式: C₉H₈O₃
• 分子量: 164.161
• InChiKey: FEESLXNHKOJNDT-UHFFFAOYSA-N

物化性质

• 沸点：
  298.7±39.0 °C(Predicted)
• 密度：
  1.506±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5,6-(methylenedioxy)benzocyclobutenol 在 盐酸 、 lithium aluminium tetrahydride 、 硫酸 、 2,2,6,6-tetramethylpiperidinyl-lithium 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 氯仿 为溶剂， 反应 10.5h， 生成 Peshawarin
  参考文献：
  名称：

  Reaction of Benzocyclobutene Oxides with Aldehydes: Synthesis of Peshawarine and Other 3,4-Dihydroisocoumarins

  摘要：

  Deprotonation of benzocyclobutenols 6 in the presence of aromatic aldehydes affords benzopyranols 7 in high yield. In the key step of this process, an o-tolualdehyde anion generated by the known ring-opening of benzocyclobutenoxides adds to the aldehyde to give 7 which is easily oxidized to 3-substituted 3,4-dihydroisocoumarins 8 including intermediates in some natural product syntheses. For example, reaction of 6-methoxybenzocyclobutenol (1) with LTMP and p-anisaldehyde gave in 96% yield the benzopyranol 16, which subsequently was converted to (+/-)-hydrangenol (17). Similar treatment of 1 with LDA and isovanillin benzyl ether afforded the benzopyranol 19 (87% yield) which already has been converted to (+/-)-phyllodulcin (21). Finally, reaction of 5,6-(methylenedioxy)-benzocyclobutenol (10) with LTMP and the aldehyde 26 (from treatment of hydrastinine with ClCO2-Me) followed by methanolysis produced the acetal 28 in 96% yield. The overall yield was 65% for the five-step synthesis of the alkaloid (+/-)-peshawawine (24) from 10 and 26. Extension of the process to aliphatic aldehydes was illustrated by the preparation of 32 from benzocyclobutenol and isobutyraldehyde in 69% overall yield after oxidation with PCC.

  DOI：

  10.1021/jo00094a022
• 作为产物：
  描述：

  5,6-(methylenedioxy)benzocyclobutenone 在 sodium tetrahydroborate 作用下， 以 乙醇 为溶剂， 反应 0.5h， 以97%的产率得到5,6-(methylenedioxy)benzocyclobutenol
  参考文献：
  名称：

  Rapid, convergent, and regioselective synthesis of anthracenes

  摘要：

  Anthracenes are obtained in moderate to good yield by the simultaneous treatment of benzocyclobutenols and halobenzenes with LTMP in tetrahydropyran. In the key step of this one-pot process, o-toluoyl anion intermediates from the known ring-opening of benzocyclobutenoxides add to halobenzene derived arynes. Methoxy-substituted benzocyclobutenols which are readily made regiospecifically by known methods also react regiospecifically with the single benzyne generated from either a 2- or 3-haloanisole. For example, the only trimethoxyanthracene isolated (48% yield) from the reaction of 6-methoxybenzocyclobutenol (8) with 5-chloro-1,3-dimethoxybenzene is the 1,3,8-isomer 20. When 1,2-dihydrocyclobuta[l]phenanthren-1-ol (14) and/or halonaphthalenes are the reactants, benzannulated anthracenes are formed; e.g., tribenz[a,c,h]anthracene in 68% yield from 14 and bromonaphthalene. In another extension, pentaphene (31) was made in one pot from o-dichlorobenzene.

  DOI：

  10.1021/jo00052a027

文献信息

• Reaction of benzocyclobutenoxides with nitriles: Synthesis of hypecumine and other 3-substituted isoquinolines
  作者：John J. Fitzgerald、Forrest E. Michael、R.A. Olofson

  DOI：10.1016/0040-4039(94)88462-5

  日期：1994.12

  Treatment of benzocyclobuten-2-ols with MeLi affords o-tolualdehyde anions which in the presence of nitriles cyclize to 3-substituted isoquinolines. Examples include the synthesis of the alkaloid hypecumine from the precursors, 14 and 19 (1:1), in 50% yield.

  用MeLi处理苯并环丁烯-2-醇可得到邻甲苯甲醛阴离子，在腈存在下，它们可环化为3-取代的异喹啉。实例包括从前体14和19（1：1）以50％的收率合成生物碱hypercumine 。
• Rapid, convergent, and regioselective synthesis of anthracenes
  作者：John J. Fitzgerald、Neville E. Drysdale、R. A. Olofson

  DOI：10.1021/jo00052a027

  日期：1992.12

  Anthracenes are obtained in moderate to good yield by the simultaneous treatment of benzocyclobutenols and halobenzenes with LTMP in tetrahydropyran. In the key step of this one-pot process, o-toluoyl anion intermediates from the known ring-opening of benzocyclobutenoxides add to halobenzene derived arynes. Methoxy-substituted benzocyclobutenols which are readily made regiospecifically by known methods also react regiospecifically with the single benzyne generated from either a 2- or 3-haloanisole. For example, the only trimethoxyanthracene isolated (48% yield) from the reaction of 6-methoxybenzocyclobutenol (8) with 5-chloro-1,3-dimethoxybenzene is the 1,3,8-isomer 20. When 1,2-dihydrocyclobuta[l]phenanthren-1-ol (14) and/or halonaphthalenes are the reactants, benzannulated anthracenes are formed; e.g., tribenz[a,c,h]anthracene in 68% yield from 14 and bromonaphthalene. In another extension, pentaphene (31) was made in one pot from o-dichlorobenzene.
• Reaction of Benzocyclobutene Oxides with Aldehydes: Synthesis of Peshawarine and Other 3,4-Dihydroisocoumarins
  作者：John J. Fitzgerald、Alex R. Pagano、Vianne M. Sakoda、R. A. Olofson

  DOI：10.1021/jo00094a022

  日期：1994.7

  Deprotonation of benzocyclobutenols 6 in the presence of aromatic aldehydes affords benzopyranols 7 in high yield. In the key step of this process, an o-tolualdehyde anion generated by the known ring-opening of benzocyclobutenoxides adds to the aldehyde to give 7 which is easily oxidized to 3-substituted 3,4-dihydroisocoumarins 8 including intermediates in some natural product syntheses. For example, reaction of 6-methoxybenzocyclobutenol (1) with LTMP and p-anisaldehyde gave in 96% yield the benzopyranol 16, which subsequently was converted to (+/-)-hydrangenol (17). Similar treatment of 1 with LDA and isovanillin benzyl ether afforded the benzopyranol 19 (87% yield) which already has been converted to (+/-)-phyllodulcin (21). Finally, reaction of 5,6-(methylenedioxy)-benzocyclobutenol (10) with LTMP and the aldehyde 26 (from treatment of hydrastinine with ClCO2-Me) followed by methanolysis produced the acetal 28 in 96% yield. The overall yield was 65% for the five-step synthesis of the alkaloid (+/-)-peshawawine (24) from 10 and 26. Extension of the process to aliphatic aldehydes was illustrated by the preparation of 32 from benzocyclobutenol and isobutyraldehyde in 69% overall yield after oxidation with PCC.