10-methyltetracyclo[8.4.0.0^1,11.O^2,7]tetradeca-2,4,6,8-tetraen-12-one | 194918-57-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 10-methyltetracyclo[8.4.0.0^1,11.O^2,7]tetradeca-2,4,6,8-tetraen-12-one
• 英文别名: 10-Methyltetracyclo[8.4.0.01,11.02,7]tetradeca-2,4,6,8-tetraen-12-one
• CAS: 194918-57-5
• 化学式: C₁₅H₁₄O
• 分子量: 210.276
• InChiKey: CIFVOBYFLSJQCJ-UHFFFAOYSA-N

物化性质

• 沸点：
  346.4±31.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  10-methyltetracyclo[8.4.0.0^1,11.O^2,7]tetradeca-2,4,6,8-tetraen-12-one 以 二氯甲烷 、 三氟乙酸 为溶剂， 反应 0.17h， 以47%的产率得到10a-Methyl-3,10a-dihydro-1H-phenanthren-2-one
  参考文献：
  名称：

  Rhodium(II)-Catalyzed Decomposition of 1-Diazo-4-(1- or 2-naphthyl)-2-butanones as a New Route to Rearranged Pimarane and Abietane Skeleta. Synthesis of Umbrosone

  摘要：

  The Rh-2(OAc)(4)-catalyzed intramolecular Buchner reaction of 1-diazo-4-(1- or 2-naphthyl)butan-2-ones was examined as a potential route to abietane and rearranged abietane derivatives. Treatment of the alpha-diazo ketone 26 with catalytic amount of dirhodium tetraacetate in CH2Cl2 at 0 degrees C furnished the tetracyclic derivative 27 in good yield. Addition of TFA to 27 (in CH2Cl2) resulted in an acid-induced opening of the cyclopropane ring to give the 4a- and 10a-methyldihydrophenanthrenones 28 and 29 in nearly equal amounts. These compounds and their analogs appear to be suitable intermediates for the synthesis of diterpenoids containing aromatic A or C rings. When the diazo ketone 34 was decomposed under Rh(II) catalysis, a 10-methyldihydroanthracenone (i.e., 36) was obtained as the main product, besides minor amounts of the expected tetracyclic ketone 35. The extension of this result to the preparation of the methoxy-substituted dihydroanthracenone 39 (52% yield) was exploited in a new total synthesis of umbrosone (6), an unusual diterpenoid possessing a rearranged linear skeleton.

  DOI：

  10.1021/jo970631k
• 作为产物：
  描述：

  2-甲氧基-1-萘醛 在 palladium on activated charcoal dirhodium tetraacetate 、 氢氧化钾 、 草酰氯 、 氢气 、 sodium 作用下， 以 乙醚 、 乙醇 、 二氯甲烷 、 乙酸乙酯 为溶剂， 23.0~25.0 ℃ 、101.33 kPa 条件下， 反应 56.5h， 生成 10-methyltetracyclo[8.4.0.0^1,11.O^2,7]tetradeca-2,4,6,8-tetraen-12-one
  参考文献：
  名称：

  Rhodium(II)-Catalyzed Decomposition of 1-Diazo-4-(1- or 2-naphthyl)-2-butanones as a New Route to Rearranged Pimarane and Abietane Skeleta. Synthesis of Umbrosone

  摘要：

  The Rh-2(OAc)(4)-catalyzed intramolecular Buchner reaction of 1-diazo-4-(1- or 2-naphthyl)butan-2-ones was examined as a potential route to abietane and rearranged abietane derivatives. Treatment of the alpha-diazo ketone 26 with catalytic amount of dirhodium tetraacetate in CH2Cl2 at 0 degrees C furnished the tetracyclic derivative 27 in good yield. Addition of TFA to 27 (in CH2Cl2) resulted in an acid-induced opening of the cyclopropane ring to give the 4a- and 10a-methyldihydrophenanthrenones 28 and 29 in nearly equal amounts. These compounds and their analogs appear to be suitable intermediates for the synthesis of diterpenoids containing aromatic A or C rings. When the diazo ketone 34 was decomposed under Rh(II) catalysis, a 10-methyldihydroanthracenone (i.e., 36) was obtained as the main product, besides minor amounts of the expected tetracyclic ketone 35. The extension of this result to the preparation of the methoxy-substituted dihydroanthracenone 39 (52% yield) was exploited in a new total synthesis of umbrosone (6), an unusual diterpenoid possessing a rearranged linear skeleton.

  DOI：

  10.1021/jo970631k

文献信息

• Rhodium(II)-Catalyzed Decomposition of 1-Diazo-4-(1- or 2-naphthyl)-2-butanones as a New Route to Rearranged Pimarane and Abietane Skeleta. Synthesis of Umbrosone
  作者：Paolo Manitto、Diego Monti、Giovanna Speranza

  DOI：10.1021/jo970631k

  日期：1997.9.1

  The Rh-2(OAc)(4)-catalyzed intramolecular Buchner reaction of 1-diazo-4-(1- or 2-naphthyl)butan-2-ones was examined as a potential route to abietane and rearranged abietane derivatives. Treatment of the alpha-diazo ketone 26 with catalytic amount of dirhodium tetraacetate in CH2Cl2 at 0 degrees C furnished the tetracyclic derivative 27 in good yield. Addition of TFA to 27 (in CH2Cl2) resulted in an acid-induced opening of the cyclopropane ring to give the 4a- and 10a-methyldihydrophenanthrenones 28 and 29 in nearly equal amounts. These compounds and their analogs appear to be suitable intermediates for the synthesis of diterpenoids containing aromatic A or C rings. When the diazo ketone 34 was decomposed under Rh(II) catalysis, a 10-methyldihydroanthracenone (i.e., 36) was obtained as the main product, besides minor amounts of the expected tetracyclic ketone 35. The extension of this result to the preparation of the methoxy-substituted dihydroanthracenone 39 (52% yield) was exploited in a new total synthesis of umbrosone (6), an unusual diterpenoid possessing a rearranged linear skeleton.