9,9a-Dihydro-9-methyl-3H-1,2-dioxino<3,4-b>indole | 62747-54-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 9,9a-Dihydro-9-methyl-3H-1,2-dioxino<3,4-b>indole
• 英文别名: 9-Methyl-3,9a-dihydro-1,2-dioxacarbazol；9-methyl-9,9a-dihydro-3H-[1,2]dioxino[3,4-b]indole；9-Methyl-9,9a-dihydro-3H-[1,2]dioxino[3,4-b]indole；9-methyl-3,9a-dihydro-[1,2]dioxino[3,4-b]indole
• CAS: 62747-54-0
• 化学式: C₁₁H₁₁NO₂
• 分子量: 189.214
• InChiKey: XHEPESYQIIZOAI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  21.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  1-甲基吲哚-3-甲醛 在 正丁基锂 、 polymer-bound Rose Bengal 、 氧气 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 3.83h， 生成 9,9a-Dihydro-9-methyl-3H-1,2-dioxino<3,4-b>indole
  参考文献：
  名称：

  Sensitized photooxygenations of 3-vinylindole derivatives

  摘要：

  A series of 1-methyl- and 1-(phenylsulfonyl)-substituted 3-vinylindoles with different electronic and steric features has been synthesized and their sensitized photooxygenation in aprotic solvents investigated. 1-Methyl-3-vinyl- (1a), 1,2-dimethyl-3-vinyl- (1b), 1-methyl-3-(beta-methoxyvinyl)- (4-Z and 4-E), 1-(phenylsulfonyl)-3-vinyl- (8a), 1-(phenylsulfonyl)-3-(alpha-methylvinyl) (8b), 1-(phenylsulfonyl)-3-(8-methoxyvinyl)- (8c and 8d), and cis-1-(phenylsulfonyl)-3-(alpha-methyl-beta-methoxyvinyl) indoles (15-Z) react with O-1(2) predominantly to give endoperoxides via [4+2] cycloaddition. However, 1,2-dimethyl-3-(beta-methoxyvinyl)indole (1c) gives [2 + 2] cycloaddition with the 3-double bond to give 1,2-dimethyl-3-formylindole (3c); trans-1-(phenylsulfonyl)-3-(alpha-methyl-beta-methoxyvinyl)indole (15-E) gives the 3-indolyl allylic hydroperoxide (17) via ene reaction, along with a small amount of isomerization of the 3-vinyl double bond. A zwitterionic intermediate in the isomerization is proposed. Most of the resulting dioxacarbazole endoperoxides are isolable and inert to reduction by trimethyl phosphite and thiourea except for N-methyldioxacarbazole 5, which undergoes clean rearrangement to indolin-2-one epoxide 7 at -20-degrees-C.

  DOI：

  10.1021/jo00079a032

文献信息

• Sensitized photooxygenation of 1-methyl-3-vinylindoles
  作者：Masakatsu Matsumoto、Kiyosi Kondo

  DOI：10.1021/ja00449a089

  日期：1977.3
• Sensitized photooxygenations of 3-vinylindole derivatives
  作者：Xiaojun Zhang、Saeed I. Khan、Christopher S. Foote

  DOI：10.1021/jo00079a032

  日期：1993.12

  A series of 1-methyl- and 1-(phenylsulfonyl)-substituted 3-vinylindoles with different electronic and steric features has been synthesized and their sensitized photooxygenation in aprotic solvents investigated. 1-Methyl-3-vinyl- (1a), 1,2-dimethyl-3-vinyl- (1b), 1-methyl-3-(beta-methoxyvinyl)- (4-Z and 4-E), 1-(phenylsulfonyl)-3-vinyl- (8a), 1-(phenylsulfonyl)-3-(alpha-methylvinyl) (8b), 1-(phenylsulfonyl)-3-(8-methoxyvinyl)- (8c and 8d), and cis-1-(phenylsulfonyl)-3-(alpha-methyl-beta-methoxyvinyl) indoles (15-Z) react with O-1(2) predominantly to give endoperoxides via [4+2] cycloaddition. However, 1,2-dimethyl-3-(beta-methoxyvinyl)indole (1c) gives [2 + 2] cycloaddition with the 3-double bond to give 1,2-dimethyl-3-formylindole (3c); trans-1-(phenylsulfonyl)-3-(alpha-methyl-beta-methoxyvinyl)indole (15-E) gives the 3-indolyl allylic hydroperoxide (17) via ene reaction, along with a small amount of isomerization of the 3-vinyl double bond. A zwitterionic intermediate in the isomerization is proposed. Most of the resulting dioxacarbazole endoperoxides are isolable and inert to reduction by trimethyl phosphite and thiourea except for N-methyldioxacarbazole 5, which undergoes clean rearrangement to indolin-2-one epoxide 7 at -20-degrees-C.