N-<(Trimethylsilyl)methyl>maleimide | 95773-83-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: N-<(Trimethylsilyl)methyl>maleimide
• 英文别名: 1-(Trimethylsilylmethyl)pyrrole-2,5-dione
• CAS: 95773-83-4
• 化学式: C₈H₁₃NO₂Si
• 分子量: 183.282
• InChiKey: FFRDOUPGLNXZJM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.79
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  37.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-<(Trimethylsilyl)methyl>maleimide 以 乙腈 为溶剂， 反应 34.0h， 以92%的产率得到(3aS,8aS,8bR)-2-(trimethylsilylmethyl)-8a-trimethylsilyloxy-4,8b-dihydro-3aH-pyrrolo[3,4-a]pyrrolizine-1,3,6-trione
  参考文献：
  名称：

  Investigations of Novel Azomethine Ylide-Forming Photoreactions of N-Silylmethylimides

  摘要：

  The scope of a recently discovered (Yoon, E. C. et al. J. Am. Chem. Sec. 1995, 117, 2698), azomethine ylide-forming photoreaction has been explored by probing the excited state chemistry of several N-trimethylsilylmethyl substituted cyclic and acyclic imides and amide analogs. Photolysis of N-[(trimethylsilyl)methyl]maleimide (4) in acetonitrile leads to efficient production of the tricyclic product 16, formed by trapping of the photogenerated azomethine ylide intermediate 15 through cydoaddition with 4. Irradiation 4 in solutions containing high concentrations of the dipolarophiles, acrylonitrile or fumaronitrile, results in production of the products (19-21 and 23-24, respectively) arising by cycloaddition of the ylide 15 with the added dipolarophiles. In contrast, photolysis of the nonconjugated cyclic imide, N-[(trimethylsilyl)methyl]succinimide (5), brings about N-acyl migration resulting in the exclusive production of the unstable, iminolactone 30. On the other hand, acyclic, N-trimethylsilylmethyl aroyl imides 6-8 undergo the excited state C to O silyl migration reaction to produce azomethine ylide intermediates 35. Both in the presence or absence of added dipolarophiles, these ylides undergo electrocyclization to form transient aziridine intermediates 36 which react further by ring opening to generate N-phenacylamide products 32-34. In contrast, the nonconjugated imide, N-[(trimethylsilyl)methyl]-N-acetylacetamide (9), is unreactive upon irradiation. Similarly, simple N-[(trimethylsilyl)methyl] amides 10-13, while being photochemically labile, do not react to form ''trappable'' ylide intermediates upon irradiation. The results outlined above are presented and discussed in terms of the scope and limitations of the new, azomethine ylide-forming photoreaction of silylmethyl imides.

  DOI：

  10.1021/jo00113a012
• 作为产物：
  描述：

  马来酰亚胺 、 三甲基硅基甲醇 在 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 以71%的产率得到N-<(Trimethylsilyl)methyl>maleimide
  参考文献：
  名称：

  Investigations of Novel Azomethine Ylide-Forming Photoreactions of N-Silylmethylimides

  摘要：

  The scope of a recently discovered (Yoon, E. C. et al. J. Am. Chem. Sec. 1995, 117, 2698), azomethine ylide-forming photoreaction has been explored by probing the excited state chemistry of several N-trimethylsilylmethyl substituted cyclic and acyclic imides and amide analogs. Photolysis of N-[(trimethylsilyl)methyl]maleimide (4) in acetonitrile leads to efficient production of the tricyclic product 16, formed by trapping of the photogenerated azomethine ylide intermediate 15 through cydoaddition with 4. Irradiation 4 in solutions containing high concentrations of the dipolarophiles, acrylonitrile or fumaronitrile, results in production of the products (19-21 and 23-24, respectively) arising by cycloaddition of the ylide 15 with the added dipolarophiles. In contrast, photolysis of the nonconjugated cyclic imide, N-[(trimethylsilyl)methyl]succinimide (5), brings about N-acyl migration resulting in the exclusive production of the unstable, iminolactone 30. On the other hand, acyclic, N-trimethylsilylmethyl aroyl imides 6-8 undergo the excited state C to O silyl migration reaction to produce azomethine ylide intermediates 35. Both in the presence or absence of added dipolarophiles, these ylides undergo electrocyclization to form transient aziridine intermediates 36 which react further by ring opening to generate N-phenacylamide products 32-34. In contrast, the nonconjugated imide, N-[(trimethylsilyl)methyl]-N-acetylacetamide (9), is unreactive upon irradiation. Similarly, simple N-[(trimethylsilyl)methyl] amides 10-13, while being photochemically labile, do not react to form ''trappable'' ylide intermediates upon irradiation. The results outlined above are presented and discussed in terms of the scope and limitations of the new, azomethine ylide-forming photoreaction of silylmethyl imides.

  DOI：

  10.1021/jo00113a012

文献信息

• Investigations of Novel Azomethine Ylide-Forming Photoreactions of N-Silylmethylimides
  作者：Ung Chan Yoon、Sung Ju Cho、Yean-Jang Lee、Maria J. Mancheno、Patrick S. Mariano

  DOI：10.1021/jo00113a012

  日期：1995.4

  The scope of a recently discovered (Yoon, E. C. et al. J. Am. Chem. Sec. 1995, 117, 2698), azomethine ylide-forming photoreaction has been explored by probing the excited state chemistry of several N-trimethylsilylmethyl substituted cyclic and acyclic imides and amide analogs. Photolysis of N-[(trimethylsilyl)methyl]maleimide (4) in acetonitrile leads to efficient production of the tricyclic product 16, formed by trapping of the photogenerated azomethine ylide intermediate 15 through cydoaddition with 4. Irradiation 4 in solutions containing high concentrations of the dipolarophiles, acrylonitrile or fumaronitrile, results in production of the products (19-21 and 23-24, respectively) arising by cycloaddition of the ylide 15 with the added dipolarophiles. In contrast, photolysis of the nonconjugated cyclic imide, N-[(trimethylsilyl)methyl]succinimide (5), brings about N-acyl migration resulting in the exclusive production of the unstable, iminolactone 30. On the other hand, acyclic, N-trimethylsilylmethyl aroyl imides 6-8 undergo the excited state C to O silyl migration reaction to produce azomethine ylide intermediates 35. Both in the presence or absence of added dipolarophiles, these ylides undergo electrocyclization to form transient aziridine intermediates 36 which react further by ring opening to generate N-phenacylamide products 32-34. In contrast, the nonconjugated imide, N-[(trimethylsilyl)methyl]-N-acetylacetamide (9), is unreactive upon irradiation. Similarly, simple N-[(trimethylsilyl)methyl] amides 10-13, while being photochemically labile, do not react to form ''trappable'' ylide intermediates upon irradiation. The results outlined above are presented and discussed in terms of the scope and limitations of the new, azomethine ylide-forming photoreaction of silylmethyl imides.