Ethyl 6-methyl-2-oxocyclohepta[b]furan-3-carboxylate | 201737-57-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 环七呋喃
• 英文名称: Ethyl 6-methyl-2-oxocyclohepta[b]furan-3-carboxylate
• CAS: 201737-57-7
• 化学式: C₁₃H₁₂O₄
• 分子量: 232.236
• InChiKey: ORLVBPJVFKPCAB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Ethyl 6-methyl-2-oxocyclohepta[b]furan-3-carboxylate 在 磷酸 、 水 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 乙醇 、 丙酮 为溶剂， 反应 19.92h， 生成 6-Methyl-1,2-dihydro-cyclopenta[a]azulen-3-one
  参考文献：
  名称：

  通过快速真空热解法合成含有 Azulene 单元的多环 π 共轭体系。二、3H-Cyclopent[a]azulen-3-one及其甲基衍生物的合成及对向性质

  摘要：

  以9-甲氧基羰基-1,2-二氢-3H-环戊[a]azulen-3-为原料合成了具有新三环π-共轭体系的3H-Cyclopent[a]azulen-3-one和2甲基衍生物一种方法是在最后一步应用闪蒸真空热解。在比参考 1,2-二氢化合物更高的场中观察到这些化合物的所有质子信号，但 3H-环戊[a]azulen-3-ones 和参考化合物的碳磁共振之间没有显着差异. 1H NMR 上的这些高场位移在由该分子外围的 12-π 电子系统的贡献引起的感应顺磁环电流方面受到赞赏。3H-cyclopent[a]azulen-3-one在结晶状态下是稳定的，但在溶液中通过脱羰二聚作用逐渐变成六环化合物，而 2-甲基衍生物在结晶态和溶液中都非常稳定。尽管 3H-cyclopent[a]azulen-3-one 与 cyclope...

  DOI：

  10.1246/bcsj.65.2131
• 作为产物：
  描述：

  4-methyl-2-(toluene-4-sulfonyloxy)-cycloheptatrienone 、 丙二酸二乙酯 在 sodium ethanolate 作用下， 以 乙醇 为溶剂， 以88%的产率得到ethyl 8-hydroxy-6-methyl-2-oxo-2H-cyclohepta[b]furan-3-carboxylate
  参考文献：
  名称：

  A Novel Synthetic Method of the (±)-(3aα,8aα)-Ethyl 8β-Hydroxy-6β-methyl-2-oxooctahydro-2H-cyclohepta[b]furan-3α- carboxylate and Its Chemical Transformation to (±)-(3aα,8aα)-3α,6β-Dimethyl-3,3a,4,5,6,8a-hexahydro-2H- cyclohepta[b]furan-2-one, (+)- and (−)-7β-(2-Acetoxy-1α-methylethyl)-4β-methyl-2-cyclohepten-1β-ol, and (+)- and (−)-7β-(2-Acetoxy-1α-methylethyl)-4β-methyl-2-cyclohepten-1-one. Possible Common Synthetic Intermediates for Pseudoguaianolides, 4,5-Secopseudoguaianolides, Guaianolides, 4,5-Secoguaianolides, and Octalactins

  摘要：

  The catalytic hydrogenation of ethyl 8-hydroxy-6-methyl-2-oxo-2H-cyclohepta[b] (6), which was derived regioselectively from 4-methyltropolone (1) in four steps in 62% overall yield, gave (3a alpha,8a alpha)-ethyl 8 beta-hydroxy-6 beta-methyl-2-oxooctahydro-2H-cyclohepta[b]furan-3 alpha-carboxylate (8b) in 45% yield. It is noteworthy that four asymmetric centers newly introduced on the seven-membered ring of 8b were controlled to be syn-oriented by the single operation. The latter was transformed to (3a alpha,8a alpha)-3 alpha,6 beta-dimethyl-3,3a,4,5,6,8a-hexahydro-2H-cyclohepta[b]furan-2-one (17a) in 77% overall yield in five steps, Reduction of 17a with LiAlH4 gave (+/-)-7 beta-(2-hydroxy-1 alpha-methylethyl)-4 beta-methyl-2-cyclohepten-1 beta-ol (22), whose enantioselective acetylation was achieved by vinyl acetate in the presence of Lipase PS to give (+)-7 beta-(2-acetoxy-1 alpha-methylethyl)-4 beta-methyl-2-cyclohepten-1 beta-ol (24) in 48% yield (93% ee) or in 52% yield (77% ee) and (-)-22 in 52% yield (70% ee) or 44% yield (89% ee). Oxidation of (+)-24 with MnO2 gave (-)-7 beta-(2-acetoxy-1 alpha-methyl ethyl)-4 beta-methyl-2-cyclohepten-1-one (-)-(25). Similarly, acetylation of (-)-22 followed by oxidation of resulting (-)-24 gave (+)-25.

  DOI：

  10.1021/jo971529q

文献信息

• Synthesis of a Polycyclic π-Conjugated System Containing an Azulene Unit by the Flash Vacuum Pyrolytic Method. II. Synthesis and Paratropic Properties of 3<i>H</i>-Cyclopent[<i>a</i>]azulen-3-one and Its Methyl Derivatives
  作者：Yoichiro Kitamori、Masafumi Yasunami、Takanori Hioki、Ikue Kikuchi、Kahei Takase

  DOI：10.1246/bcsj.65.2131

  日期：1992.8

  3H-Cyclopent[a]azulen-3-one and two methyl derivalives, which have a new tricyclic π-conjugated system, were synthesized starting from 9-methoxycarbonyl-1,2-dihydro-3H-cyclopent[a]azulen-3-one by the application of flash vacuum pyrolysis in the final step. All proton signals of these compounds were observed at higher fields than those of the referenced 1,2-dihydro compound, but there are no significant

  以9-甲氧基羰基-1,2-二氢-3H-环戊[a]azulen-3-为原料合成了具有新三环π-共轭体系的3H-Cyclopent[a]azulen-3-one和2甲基衍生物一种方法是在最后一步应用闪蒸真空热解。在比参考 1,2-二氢化合物更高的场中观察到这些化合物的所有质子信号，但 3H-环戊[a]azulen-3-ones 和参考化合物的碳磁共振之间没有显着差异. 1H NMR 上的这些高场位移在由该分子外围的 12-π 电子系统的贡献引起的感应顺磁环电流方面受到赞赏。3H-cyclopent[a]azulen-3-one在结晶状态下是稳定的，但在溶液中通过脱羰二聚作用逐渐变成六环化合物，而 2-甲基衍生物在结晶态和溶液中都非常稳定。尽管 3H-cyclopent[a]azulen-3-one 与 cyclope...
• A Novel Synthetic Method of the (±)-(3aα,8aα)-Ethyl 8β-Hydroxy-6β-methyl-2-oxooctahydro-2<i>H</i>-cyclohepta[<i>b</i>]furan-3α- carboxylate and Its Chemical Transformation to (±)-(3aα,8aα)-3α,6β-Dimethyl-3,3a,4,5,6,8a-hexahydro-2<i>H</i>- cyclohepta[<i>b</i>]furan-2-one, (+)- and (−)-7β-(2-Acetoxy-1α-methylethyl)-4β-methyl-2-cyclohepten-1β-ol, and (+)- and (−)-7β-(2-Acetoxy-1α-methylethyl)-4β-methyl-2-cyclohepten-1-one. Possible Common Synthetic Intermediates for Pseudoguaianolides, 4,5-Secopseudoguaianolides, Guaianolides, 4,5-Secoguaianolides, and Octalactins
  作者：Fumito Shimoma、Haruhiko Kusaka、Katsuaki Wada、Hidenori Azami、Masafumi Yasunami、Toshio Suzuki、Hisahiro Hagiwara、Masayoshi Ando

  DOI：10.1021/jo971529q

  日期：1998.2.1

  The catalytic hydrogenation of ethyl 8-hydroxy-6-methyl-2-oxo-2H-cyclohepta[b] (6), which was derived regioselectively from 4-methyltropolone (1) in four steps in 62% overall yield, gave (3a alpha,8a alpha)-ethyl 8 beta-hydroxy-6 beta-methyl-2-oxooctahydro-2H-cyclohepta[b]furan-3 alpha-carboxylate (8b) in 45% yield. It is noteworthy that four asymmetric centers newly introduced on the seven-membered ring of 8b were controlled to be syn-oriented by the single operation. The latter was transformed to (3a alpha,8a alpha)-3 alpha,6 beta-dimethyl-3,3a,4,5,6,8a-hexahydro-2H-cyclohepta[b]furan-2-one (17a) in 77% overall yield in five steps, Reduction of 17a with LiAlH4 gave (+/-)-7 beta-(2-hydroxy-1 alpha-methylethyl)-4 beta-methyl-2-cyclohepten-1 beta-ol (22), whose enantioselective acetylation was achieved by vinyl acetate in the presence of Lipase PS to give (+)-7 beta-(2-acetoxy-1 alpha-methylethyl)-4 beta-methyl-2-cyclohepten-1 beta-ol (24) in 48% yield (93% ee) or in 52% yield (77% ee) and (-)-22 in 52% yield (70% ee) or 44% yield (89% ee). Oxidation of (+)-24 with MnO2 gave (-)-7 beta-(2-acetoxy-1 alpha-methyl ethyl)-4 beta-methyl-2-cyclohepten-1-one (-)-(25). Similarly, acetylation of (-)-22 followed by oxidation of resulting (-)-24 gave (+)-25.