N-<2-(trimethylsilyl)ethyl>phthalimide | 119340-68-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: N-<2-(trimethylsilyl)ethyl>phthalimide
• 英文别名: N-(2-trimethylsilylethyl)phthalimide；1H-Isoindole-1,3(2H)-dione, 2-[2-(trimethylsilyl)ethyl]-；2-(2-trimethylsilylethyl)isoindole-1,3-dione
• CAS: 119340-68-0
• 化学式: C₁₃H₁₇NO₂Si
• 分子量: 247.369
• InChiKey: ICXYACHRXUEOOD-UHFFFAOYSA-N

物化性质

• 沸点：
  327.8±25.0 °C(Predicted)
• 密度：
  1.097±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.62
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 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-<2-(trimethylsilyl)ethyl>phthalimide 以 乙腈 为溶剂， 反应 7.5h， 以68%的产率得到3,4-二氢-2H-苯并[C]氮杂卓-1,5-二酮
  参考文献：
  名称：

  Exploratory Studies of H-Atom Abstraction and Silyl-Transfer Photoreactions of Silylalkyl Ketones and (Silylalkyl)phthalimides

  摘要：

  Exploratory studies have been conducted to probe competitive H-atom abstraction and SET-promoted, silyl-transfer reactions of excited states of silylalkyl ketones and (silylalkyl)phthalimides. Photochemical investigations with the (silylalkyl)phthalimides have demonstrated that typical gamma-H atom abstraction reactions occur upon irradiation in less polar and less silophilic solvents. In contrast, irradiation of these substances in polar-protic-silophilic solvents results in product formation via pathways involving SET-induced desilylation. Photoreactions of silylamido-aryl ketones in either nonsilophilic or silophilic solvents take place almost exclusively by sequential SET silyl-transfer routes to produce azetidine products. Finally, the chemical selectivities of photochemical reactions of silylpropyl-aryl ketones appear to depend on medium polarity and silophilicity. Irradiation of these substrates in less polar-nonsilophilic solvents leads to almost exclusive formation of acetophenone and vinyltrimethylsilane in essentially equal yields by a reaction pathway initiated by gamma-H atom abstraction and 1,4-biradical fragmentation. However, irradiation of these substances in polar-silophilic solvents produces acetophenone and vinyltrimethylsilane in an ca. 1.7:1 ratio reflecting the fact that a silyl-transfer pathway competes with H-atom abstraction under these conditions.

  DOI：

  10.1021/jo9522623
• 作为产物：
  描述：

  2-(三甲硅基)乙醇 在 氯化亚砜 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 7.0h， 生成 N-<2-(trimethylsilyl)ethyl>phthalimide
  参考文献：
  名称：

  Exploratory Studies of H-Atom Abstraction and Silyl-Transfer Photoreactions of Silylalkyl Ketones and (Silylalkyl)phthalimides

  摘要：

  Exploratory studies have been conducted to probe competitive H-atom abstraction and SET-promoted, silyl-transfer reactions of excited states of silylalkyl ketones and (silylalkyl)phthalimides. Photochemical investigations with the (silylalkyl)phthalimides have demonstrated that typical gamma-H atom abstraction reactions occur upon irradiation in less polar and less silophilic solvents. In contrast, irradiation of these substances in polar-protic-silophilic solvents results in product formation via pathways involving SET-induced desilylation. Photoreactions of silylamido-aryl ketones in either nonsilophilic or silophilic solvents take place almost exclusively by sequential SET silyl-transfer routes to produce azetidine products. Finally, the chemical selectivities of photochemical reactions of silylpropyl-aryl ketones appear to depend on medium polarity and silophilicity. Irradiation of these substrates in less polar-nonsilophilic solvents leads to almost exclusive formation of acetophenone and vinyltrimethylsilane in essentially equal yields by a reaction pathway initiated by gamma-H atom abstraction and 1,4-biradical fragmentation. However, irradiation of these substances in polar-silophilic solvents produces acetophenone and vinyltrimethylsilane in an ca. 1.7:1 ratio reflecting the fact that a silyl-transfer pathway competes with H-atom abstraction under these conditions.

  DOI：

  10.1021/jo9522623

文献信息

• Intermolecular Radical Mediated Anti-Markovnikov Alkene Hydroamination Using<i>N</i>-Hydroxyphthalimide
  作者：Samuel W. Lardy、Valerie A. Schmidt

  DOI：10.1021/jacs.8b06881

  日期：2018.10.3

  An intermolecular anti-Markovnikov hydroamination of alkenes has been developed using triethyl phosphite and N-hydroxyphthalimide. The process tolerates a wide range of alkenes, including vinyl ethers, silanes, and sulfides as well as electronically unbiased terminal and internal alkenes. The resultant N-alkylphthalimides can readily be transformed to the corresponding primary amines. Mechanistic probes

  使用亚磷酸三乙酯和 N-羟基邻苯二甲酰亚胺开发了烯烃的分子间反马尔科夫尼科夫加氢胺化反应。该工艺可耐受多种烯烃，包括乙烯基醚、硅烷和硫化物以及电子无偏的末端和内部烯烃。所得的 N-烷基邻苯二甲酰亚胺可以很容易地转化为相应的伯胺。机理探针表明，该过程是通过亚磷酸酯促进的 N-羟基邻苯二甲酰亚胺的自由基脱氧来获得邻苯二甲酰亚胺自由基介导的。
• Regioselective Radical Alkene Amination Strategies by Using Phosphite-Mediated Deoxygenation
  作者：Samuel W. Lardy、Valerie A. Schmidt

  DOI：10.1055/s-0037-1611911

  日期：2019.11

  frameworks is a highly sought-after goal. Presented here is a summary of recent efforts conducted by our group to develop radical-mediated amination strategies for the formal synthesis of primary amines from alkenes with exclusive anti-Markovnikov regioselectivity. We have found that N-hydroxyphthalimide is an effective reagent capable of supplying both the N and H atoms for alkene hydroamination in

  含氮化合物是所有化学学科的基本主题，这些框架的有效合成是一个备受追捧的目标。这里介绍的是我们小组最近为开发自由基介导的胺化策略而进行的工作的总结，该策略用于从具有独家抗马尔科夫尼科夫区域选择性的烯烃正式合成伯胺。我们发现 N-羟基邻苯二甲酰亚胺是一种有效的试剂，能够在基团转移自由基加成型机制中为烯烃加氢胺化提供 N 和 H 原子。此外，烯丙基氧邻苯二甲酰亚胺衍生物同样能够进行自由基基团转移并允许外部烯烃的氨基烯丙基化。
• 一种抑制激酶化合物及其在医学上的用途
  申请人：上海喆邺生物科技有限公司

  公开号：CN108341837A

  公开（公告）日：2018-07-31

  一种抑制激酶化合物及其在医学上的用途。本发明提供式(I)化合物，其立体异构体、互变异构体或药学上可接受的盐，其作为FGFR4激酶选择性抑制剂及其在制备治疗由FGFR4或FGF19所致疾病的药物或药物组合物中的应用，本发明公开的化合物对FGFR4具有选择性的显著抑制活性，在肿瘤治疗领域具有广泛的应用前景。
• The operation of H-atom and TMS-group transfer processes in the photochemistry of silylamidoalkyl- and silylalkyl-ketones and -phthalimides
  作者：Yean Jang Lee、Chao Pin Lee、Yoon Tag Jeon、Patrick S. Mariano、Ung Chan Yoon、Dong Uk Kim、Jack C. Kim、Jong Gun Lee

  DOI：10.1016/s0040-4039(00)73797-x

  日期：1993.9
• Exploratory Studies of H-Atom Abstraction and Silyl-Transfer Photoreactions of Silylalkyl Ketones and (Silylalkyl)phthalimides
  作者：Yean Jang Lee、Rong Ling、Patrick S. Mariano、Ung Chan Yoon、Dong Uk Kim、Sun Wha Oh

  DOI：10.1021/jo9522623

  日期：1996.1.1

  Exploratory studies have been conducted to probe competitive H-atom abstraction and SET-promoted, silyl-transfer reactions of excited states of silylalkyl ketones and (silylalkyl)phthalimides. Photochemical investigations with the (silylalkyl)phthalimides have demonstrated that typical gamma-H atom abstraction reactions occur upon irradiation in less polar and less silophilic solvents. In contrast, irradiation of these substances in polar-protic-silophilic solvents results in product formation via pathways involving SET-induced desilylation. Photoreactions of silylamido-aryl ketones in either nonsilophilic or silophilic solvents take place almost exclusively by sequential SET silyl-transfer routes to produce azetidine products. Finally, the chemical selectivities of photochemical reactions of silylpropyl-aryl ketones appear to depend on medium polarity and silophilicity. Irradiation of these substrates in less polar-nonsilophilic solvents leads to almost exclusive formation of acetophenone and vinyltrimethylsilane in essentially equal yields by a reaction pathway initiated by gamma-H atom abstraction and 1,4-biradical fragmentation. However, irradiation of these substances in polar-silophilic solvents produces acetophenone and vinyltrimethylsilane in an ca. 1.7:1 ratio reflecting the fact that a silyl-transfer pathway competes with H-atom abstraction under these conditions.