N-<(trimethylsilyl)methyl>-1,8-naphthalimide | 153489-40-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异喹啉及其衍生物
• 英文名称: N-<(trimethylsilyl)methyl>-1,8-naphthalimide
• 英文别名: N-trimethylsilylmethyl-1,8-naphthalimide；2-(Trimethylsilylmethyl)benzo[de]isoquinoline-1,3-dione
• CAS: 153489-40-8
• 化学式: C₁₆H₁₇NO₂Si
• 分子量: 283.402
• InChiKey: UHHWMQRVVSNHKL-UHFFFAOYSA-N

物化性质

• 沸点：
  406.7±28.0 °C(Predicted)
• 密度：
  1.166±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.31
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 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>-1,8-naphthalimide 以 甲醇 为溶剂， 反应 4.5h， 以75%的产率得到2-甲基-1H-苯并(去)异喹啉-1,3(2H)-二酮
  参考文献：
  名称：

  Novel and Efficient Azomethine Ylide Forming Photoreactions of N-(Silylmethyl)phthalimides and Related Acid and Alcohol Derivatives

  摘要：

  An investigation of the photochemistry of N-(silylmethyl)phthalimides and related alpha-phthaloylacetic acids and 2-phenylethanol derivatives has uncovered new excited state processes resulting in the formation of azomethine ylide intermediates. Irradiation of N-[(trimethylsilyl)methyl]phthalimide in MeCN promotes C to O silyl transfer to generate the corresponding azomethine ylide which is efficiently trapped by reaction with water to yield the N-methylphthalimide or by dipolar cycloaddition with acetone, methyl acrylate, or acrylonitrile. Cycloadditions with the latter two dipolarophiles are both regioselective and endo-stereoselective. These processes can be triplet photosensitized by use of acetophenone. The related N-[(trimethylsilyl)methyl]-1,8-naphthalimide reacts in a similar manner upon irradiation in MeCN solutions containing the dipolarophiles methyl acrylate and acrylonitrile to produce cycloadducts which undergo spontaneous elimination of TMSOH, yielding alpha,beta-unsaturated ester or nitrile products. The ylide formed by irradiation of the (silylmethyl)phthalimide is trapped in a stereospecific (retention) manner by the dipolarophiles trans-hex-4-en-3-one, dimethyl maleate, and dimethyl fumarate. The effect of aryl ring substitution on the regiochemical course of the photoinduced C to O silyl migration process was probed by use of the 4-methoxy- and 4-carbomethoxyl-N-(silylmethyl)phthalimides. Irradiation of the former substance in an MeCN solution containing acrylonitrile gives rise to a single adduct whose structure suggests that silyl migration to oxygen of the carbonyl meta to the OMe substituent is highly favored. In contrast, the 4-carbomethoxyphthalimide is converted under these conditions to a mixture of regioisomeric adducts. Thus, silyl migration in the excited state of this substance is nonselective. In accord with hints found in earlier observations made by Kanaoka (Chem. Pharm. Bull. 1982, 30, 1263), N-phthalimide derivatives of the alpha-amino acids glycine, alanine, and phenylalanine undergo similar ylide forming photoreactions upon irradiation in MeCN solutions. The azomethine ylides produced by photodecarboxylation of these substances are efficiently trapped by dipolarophiles, and the overall photoreactions starting with the alanine and phenylalanine derivatives are highly stereoselective. Finally, the N-phthalimide derivative of 2-amino-1-phenylethanol also is transformed to a related ylide upon irradiation in MeCN. The nature, regiochemical and stereochemical course, and mechanistic interpretation of these new azomethine ylide forming photoreactions are discussed in this publication.

  DOI：

  10.1021/ja00115a004
• 作为产物：
  描述：

  萘亚胺 、 氯甲基三甲基硅烷 在 sodium hydride 作用下， 生成 N-<(trimethylsilyl)methyl>-1,8-naphthalimide
  参考文献：
  名称：

  Novel and Efficient Azomethine Ylide Forming Photoreactions of N-(Silylmethyl)phthalimides and Related Acid and Alcohol Derivatives

  摘要：

  An investigation of the photochemistry of N-(silylmethyl)phthalimides and related alpha-phthaloylacetic acids and 2-phenylethanol derivatives has uncovered new excited state processes resulting in the formation of azomethine ylide intermediates. Irradiation of N-[(trimethylsilyl)methyl]phthalimide in MeCN promotes C to O silyl transfer to generate the corresponding azomethine ylide which is efficiently trapped by reaction with water to yield the N-methylphthalimide or by dipolar cycloaddition with acetone, methyl acrylate, or acrylonitrile. Cycloadditions with the latter two dipolarophiles are both regioselective and endo-stereoselective. These processes can be triplet photosensitized by use of acetophenone. The related N-[(trimethylsilyl)methyl]-1,8-naphthalimide reacts in a similar manner upon irradiation in MeCN solutions containing the dipolarophiles methyl acrylate and acrylonitrile to produce cycloadducts which undergo spontaneous elimination of TMSOH, yielding alpha,beta-unsaturated ester or nitrile products. The ylide formed by irradiation of the (silylmethyl)phthalimide is trapped in a stereospecific (retention) manner by the dipolarophiles trans-hex-4-en-3-one, dimethyl maleate, and dimethyl fumarate. The effect of aryl ring substitution on the regiochemical course of the photoinduced C to O silyl migration process was probed by use of the 4-methoxy- and 4-carbomethoxyl-N-(silylmethyl)phthalimides. Irradiation of the former substance in an MeCN solution containing acrylonitrile gives rise to a single adduct whose structure suggests that silyl migration to oxygen of the carbonyl meta to the OMe substituent is highly favored. In contrast, the 4-carbomethoxyphthalimide is converted under these conditions to a mixture of regioisomeric adducts. Thus, silyl migration in the excited state of this substance is nonselective. In accord with hints found in earlier observations made by Kanaoka (Chem. Pharm. Bull. 1982, 30, 1263), N-phthalimide derivatives of the alpha-amino acids glycine, alanine, and phenylalanine undergo similar ylide forming photoreactions upon irradiation in MeCN solutions. The azomethine ylides produced by photodecarboxylation of these substances are efficiently trapped by dipolarophiles, and the overall photoreactions starting with the alanine and phenylalanine derivatives are highly stereoselective. Finally, the N-phthalimide derivative of 2-amino-1-phenylethanol also is transformed to a related ylide upon irradiation in MeCN. The nature, regiochemical and stereochemical course, and mechanistic interpretation of these new azomethine ylide forming photoreactions are discussed in this publication.

  DOI：

  10.1021/ja00115a004

文献信息

• Mechanistic Studies of the Azomethine Ylide-Forming Photoreactions of <i>N</i>-(Silylmethyl)phthalimides and <i>N</i>-Phthaloylglycine
  作者：Yasutake Takahashi、Tsutomu Miyashi、Ung Chan Yoon、Sun Wha Oh、Maria Mancheno、Zhuoyi Su、Daniel F. Falvey、Patrick S. Mariano

  DOI：10.1021/ja9841862

  日期：1999.4.1

  spectroscopy have now been employed to investigate the mechanistic details of these novel excited-state processes. The results of this effort show that azomethine ylides are the key reactive intermediates in these processes. In addition, the investigations provide information about the dynamics of several ylide decay pathways and the nature of the excited states responsible for the ylide-forming silyl-migration

  在早期的研究中，我们已经表明，在缺电子烯烃（例如丙烯酸甲酯）存在的情况下，对 N-[（三甲基甲硅烷基）甲基] 邻苯二甲酰亚胺和 N-邻苯二甲酰甘氨酸的 MeCN 溶液进行辐照会产生环加合物。此外，这些物质在 MeCN 水溶液中的辐照会导致 N-甲基邻苯二甲酰亚胺的形成。现在已采用激光闪光光解和荧光光谱来研究这些新型激发态过程的机械细节。这项工作的结果表明，偶氮甲碱叶立德是这些过程中的关键反应中间体。此外，这些研究提供了有关几种内立德衰变途径的动力学以及负责形成内立德的甲硅烷基迁移（单线态和三线态）和脱羧（三线态）反应的激发态性质的信息。N-[(三甲基甲硅烷基)甲基]邻苯二甲酰亚胺 (1) 和 N-邻苯二甲酰甘氨酸 (2) 的 MeCN 溶液的脉冲照射会产生瞬变，其吸收和...
• A novel azomethine ylid forming photoreaction of N-trimethylsilylmethylphthalimides
  作者：Chan Yoon Ung、Uk Kim Dong、Jack C. Kim、Gun Lee Jong、Patrick S. Mariano、Jang Lee Yean、Herman L. Ammon

  DOI：10.1016/s0040-4039(00)73798-1

  日期：1993.9
• Novel and Efficient Azomethine Ylide Forming Photoreactions of N-(Silylmethyl)phthalimides and Related Acid and Alcohol Derivatives
  作者：Ung Chan Yoon、Dong Uk Kim、Chan Woo Lee、Young Sun Choi、Yean-Jang Lee、Herman L. Ammon、Patrick S. Mariano

  DOI：10.1021/ja00115a004

  日期：1995.3

  An investigation of the photochemistry of N-(silylmethyl)phthalimides and related alpha-phthaloylacetic acids and 2-phenylethanol derivatives has uncovered new excited state processes resulting in the formation of azomethine ylide intermediates. Irradiation of N-[(trimethylsilyl)methyl]phthalimide in MeCN promotes C to O silyl transfer to generate the corresponding azomethine ylide which is efficiently trapped by reaction with water to yield the N-methylphthalimide or by dipolar cycloaddition with acetone, methyl acrylate, or acrylonitrile. Cycloadditions with the latter two dipolarophiles are both regioselective and endo-stereoselective. These processes can be triplet photosensitized by use of acetophenone. The related N-[(trimethylsilyl)methyl]-1,8-naphthalimide reacts in a similar manner upon irradiation in MeCN solutions containing the dipolarophiles methyl acrylate and acrylonitrile to produce cycloadducts which undergo spontaneous elimination of TMSOH, yielding alpha,beta-unsaturated ester or nitrile products. The ylide formed by irradiation of the (silylmethyl)phthalimide is trapped in a stereospecific (retention) manner by the dipolarophiles trans-hex-4-en-3-one, dimethyl maleate, and dimethyl fumarate. The effect of aryl ring substitution on the regiochemical course of the photoinduced C to O silyl migration process was probed by use of the 4-methoxy- and 4-carbomethoxyl-N-(silylmethyl)phthalimides. Irradiation of the former substance in an MeCN solution containing acrylonitrile gives rise to a single adduct whose structure suggests that silyl migration to oxygen of the carbonyl meta to the OMe substituent is highly favored. In contrast, the 4-carbomethoxyphthalimide is converted under these conditions to a mixture of regioisomeric adducts. Thus, silyl migration in the excited state of this substance is nonselective. In accord with hints found in earlier observations made by Kanaoka (Chem. Pharm. Bull. 1982, 30, 1263), N-phthalimide derivatives of the alpha-amino acids glycine, alanine, and phenylalanine undergo similar ylide forming photoreactions upon irradiation in MeCN solutions. The azomethine ylides produced by photodecarboxylation of these substances are efficiently trapped by dipolarophiles, and the overall photoreactions starting with the alanine and phenylalanine derivatives are highly stereoselective. Finally, the N-phthalimide derivative of 2-amino-1-phenylethanol also is transformed to a related ylide upon irradiation in MeCN. The nature, regiochemical and stereochemical course, and mechanistic interpretation of these new azomethine ylide forming photoreactions are discussed in this publication.