2-(Phenylmethyl)-10c-hydroxy-6-methyl-3,3a,4,5,6,10c-hexyhydropyrrolo<3,4-c>carbazol-1(2H)-one | 165072-89-9

• 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: 2-(Phenylmethyl)-10c-hydroxy-6-methyl-3,3a,4,5,6,10c-hexyhydropyrrolo<3,4-c>carbazol-1(2H)-one
• 英文别名: 2-Benzyl-10c-hydroxy-6-methyl-3,3a,4,5-tetrahydropyrrolo[3,4-c]carbazol-1-one
• CAS: 165072-89-9
• 化学式: C₂₂H₂₂N₂O₂
• 分子量: 346.429
• InChiKey: RORYZEKEWWNCNF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  45.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(Phenylmethyl)-10c-hydroxy-6-methyl-3,3a,4,5,6,10c-hexyhydropyrrolo<3,4-c>carbazol-1(2H)-one 以7%的产率得到3,6-Dihydro-6-methyl-2-(phenylmethyl)pyrrolo<3,4-c>carbazol-1(2H)-one
  参考文献：
  名称：

  Intramolecular Diels-Alder Reactions. 5. Approaches to the Pyrrolo[3,4-c]carbazole and Pyrido[4,3-c]carbazole Systems1

  摘要：

  Two methods for the preparation of indole-2,3-quinodimethanes are reported. Treatment of 1,2-dimethyl-alpha-oxo-N-(phenylmethyl)-N-2-propenyl-1H-indole-3-acetamide (3) with sodium bis(trimethylsilyl)amide in refluxing THF gave 2-(phenylmethyl)-10c-hydroxy-6-methyl-3,3a,4,5,6,10c-hexahydropyrrolo[3,4-c]-carbazol-1(2H)-one (5) in 18% yield by intramolecular Diels-Alder reaction of the intermediate enolate 4. LiBH4-reduction of amide 3 and thermolysis of the resulting alpha-hydroxyamide 8 at 190 degrees C gave a 63:37 mixture of the cis and trans isomers of 2-(phenylmethyl)-6-methyl-3,3a,4,5,6,10c-hexahydropyrrolo[3,4-c]carbaxol-1(2H)-one (9a and 9b) in 64% yield. The corresponding N-3-butenylamide 10 at 205 degrees C led to a 67:33 mixture of cis- and trans-7-methyl-2,3,4,4a,5,6,7,11c-octahydro-2-(phenylmethyl)-1H-pyrido[4,3-c]carbazol-1-one (11a and 11b) in 53% yield. Thermolysis of 1,2-dimethyl-alpha-hydroxy-N-(phenylmethyl)-N-2-propynyl-1H-indole-3-acetamide (15) gave an equimolar mixture of lactam 9a and the aromatized product, 3,6-dihydro-6-methyl-2-(phenylmethyl)pyrrolo[3,4-c]carbazol-1(2H)-one (17) in 80% yield by disproportionation of the intermediate lactam 16. Reaction of 1,2-dimethyl-1H-indole-3-carboxaldehyde with methyl acrylate and sodium bis(trimethylsilyl)amide produced methyl 1,2-dihydro-9-methyl-9H-carbazole-3-carboxylate (20) in 26% yield, most likely by a sequence of Michael addition to the enolate of the aldehyde and intramolecular aldol condensation.

  DOI：

  10.1021/jo00119a046
• 作为产物：
  描述：

  N-烯丙基苄胺 在 sodium hydroxide 、 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.5h， 生成 2-(Phenylmethyl)-10c-hydroxy-6-methyl-3,3a,4,5,6,10c-hexyhydropyrrolo<3,4-c>carbazol-1(2H)-one
  参考文献：
  名称：

  Intramolecular Diels-Alder Reactions. 5. Approaches to the Pyrrolo[3,4-c]carbazole and Pyrido[4,3-c]carbazole Systems1

  摘要：

  Two methods for the preparation of indole-2,3-quinodimethanes are reported. Treatment of 1,2-dimethyl-alpha-oxo-N-(phenylmethyl)-N-2-propenyl-1H-indole-3-acetamide (3) with sodium bis(trimethylsilyl)amide in refluxing THF gave 2-(phenylmethyl)-10c-hydroxy-6-methyl-3,3a,4,5,6,10c-hexahydropyrrolo[3,4-c]-carbazol-1(2H)-one (5) in 18% yield by intramolecular Diels-Alder reaction of the intermediate enolate 4. LiBH4-reduction of amide 3 and thermolysis of the resulting alpha-hydroxyamide 8 at 190 degrees C gave a 63:37 mixture of the cis and trans isomers of 2-(phenylmethyl)-6-methyl-3,3a,4,5,6,10c-hexahydropyrrolo[3,4-c]carbaxol-1(2H)-one (9a and 9b) in 64% yield. The corresponding N-3-butenylamide 10 at 205 degrees C led to a 67:33 mixture of cis- and trans-7-methyl-2,3,4,4a,5,6,7,11c-octahydro-2-(phenylmethyl)-1H-pyrido[4,3-c]carbazol-1-one (11a and 11b) in 53% yield. Thermolysis of 1,2-dimethyl-alpha-hydroxy-N-(phenylmethyl)-N-2-propynyl-1H-indole-3-acetamide (15) gave an equimolar mixture of lactam 9a and the aromatized product, 3,6-dihydro-6-methyl-2-(phenylmethyl)pyrrolo[3,4-c]carbazol-1(2H)-one (17) in 80% yield by disproportionation of the intermediate lactam 16. Reaction of 1,2-dimethyl-1H-indole-3-carboxaldehyde with methyl acrylate and sodium bis(trimethylsilyl)amide produced methyl 1,2-dihydro-9-methyl-9H-carbazole-3-carboxylate (20) in 26% yield, most likely by a sequence of Michael addition to the enolate of the aldehyde and intramolecular aldol condensation.

  DOI：

  10.1021/jo00119a046

文献信息

• Intramolecular Diels-Alder Reactions. 5. Approaches to the Pyrrolo[3,4-c]carbazole and Pyrido[4,3-c]carbazole Systems1
  作者：Engelbert Ciganek、Ernest M. Schubert

  DOI：10.1021/jo00119a046

  日期：1995.7

  Two methods for the preparation of indole-2,3-quinodimethanes are reported. Treatment of 1,2-dimethyl-alpha-oxo-N-(phenylmethyl)-N-2-propenyl-1H-indole-3-acetamide (3) with sodium bis(trimethylsilyl)amide in refluxing THF gave 2-(phenylmethyl)-10c-hydroxy-6-methyl-3,3a,4,5,6,10c-hexahydropyrrolo[3,4-c]-carbazol-1(2H)-one (5) in 18% yield by intramolecular Diels-Alder reaction of the intermediate enolate 4. LiBH4-reduction of amide 3 and thermolysis of the resulting alpha-hydroxyamide 8 at 190 degrees C gave a 63:37 mixture of the cis and trans isomers of 2-(phenylmethyl)-6-methyl-3,3a,4,5,6,10c-hexahydropyrrolo[3,4-c]carbaxol-1(2H)-one (9a and 9b) in 64% yield. The corresponding N-3-butenylamide 10 at 205 degrees C led to a 67:33 mixture of cis- and trans-7-methyl-2,3,4,4a,5,6,7,11c-octahydro-2-(phenylmethyl)-1H-pyrido[4,3-c]carbazol-1-one (11a and 11b) in 53% yield. Thermolysis of 1,2-dimethyl-alpha-hydroxy-N-(phenylmethyl)-N-2-propynyl-1H-indole-3-acetamide (15) gave an equimolar mixture of lactam 9a and the aromatized product, 3,6-dihydro-6-methyl-2-(phenylmethyl)pyrrolo[3,4-c]carbazol-1(2H)-one (17) in 80% yield by disproportionation of the intermediate lactam 16. Reaction of 1,2-dimethyl-1H-indole-3-carboxaldehyde with methyl acrylate and sodium bis(trimethylsilyl)amide produced methyl 1,2-dihydro-9-methyl-9H-carbazole-3-carboxylate (20) in 26% yield, most likely by a sequence of Michael addition to the enolate of the aldehyde and intramolecular aldol condensation.