4-(N-甲基苯胺基)-4-氧代丁酸 | 33684-12-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 4-(N-甲基苯胺基)-4-氧代丁酸
• 英文名称: 4-oxo-4-(N-methylphenylamino)butanoic acid
• 英文别名: N-methyl-N-phenylsuccinimic acid；N-methyl-N-phenyl-succinamic acid；N-Methyl-N-phenyl-succinamidsaeure；Bernsteinsaeure-mono-methylanilid；N-Methyl-succinanilsaeure；N-methyl-N-phenyl-butanedioic acid amide；4-[Methyl(phenyl)amino]-4-oxobutanoic acid；4-(N-methylanilino)-4-oxobutanoic acid
• CAS: 33684-12-7
• 化学式: C₁₁H₁₃NO₃
• mdl: MFCD08059162
• 分子量: 207.229
• InChiKey: ZBTZGOKOGQVOPH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.272
• 拓扑面积：
  57.6
• 氢给体数：
  1
• 氢受体数：
  3

安全信息

• 海关编码：
  2922509090

反应信息

• 作为反应物：
  描述：

  4-(N-甲基苯胺基)-4-氧代丁酸 在 rhodium(II) acetate dimer 、 三乙胺 、 氯甲酸甲酯 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 4-carbomethoxy-6-trans-(N-methyl-N-phenylcarbamyl)-1-oxaspiro<2.4>hept-4-ene
  参考文献：
  名称：

  A Novel Cycloaddition Reaction of α-Diazo-γ-amido Ketones Catalyzed by Rhodium(II) Acetate. Scope and Mechanistic Details of the Process

  摘要：

  alpha-Diazo ketones containing an amido group in the gamma-position have been found to undergo a novel rhodium(II)-catalyzed cycloaddition reaction. Intramolecular cyclization of the keto carbenoid onto the oxygen atom of the amide group generates a carbonyl ylide dipole as a transient species. This highly stabilized dipole does not readily undergo 1,3-dipolar cycloaddition but rather transfers a proton to produce a cyclic ketene N,O-acetal. The ketene acetal is unstable to moisture and upon standing is readily hydrolyzed to a gamma-keto delta-lactone and an amine. In the absence of any significant amount of water, the ketene N,O-acetal undergoes conjugate addition with the activated st-bond of the dipolarophile to give a zwitterion intermediate. The anionic portion of the zwitterion adds to the neighboring carbonyl group. This is followed by epoxide ring formation with charge dissipation leading to an amido-substituted spiro cyclopentyl epoxide. In certain cases a hydroxy lactone was also isolated and its formation can be attributed to the competitive hydrolysis of the zwitterionic intermediate. The Rh(II)-catalyzed reaction of the diazo ketoamide derived from N-benzylpiperidone with DMAD afforded two different types of cycloadducts. In addition to the spiro cyclopentyl epoxide, a product derived from trapping of the carbonyl ylide dipole was also obtained, thereby providing additional support for the proposed mechanism.

  DOI：

  10.1021/jo952078h
• 作为产物：
  描述：

  丁二酸酐 、 N-甲基苯胺 以 四氢呋喃 为溶剂， 反应 4.0h， 以85%的产率得到4-(N-甲基苯胺基)-4-氧代丁酸
  参考文献：
  名称：

  A Novel Cycloaddition Reaction of α-Diazo-γ-amido Ketones Catalyzed by Rhodium(II) Acetate. Scope and Mechanistic Details of the Process

  摘要：

  alpha-Diazo ketones containing an amido group in the gamma-position have been found to undergo a novel rhodium(II)-catalyzed cycloaddition reaction. Intramolecular cyclization of the keto carbenoid onto the oxygen atom of the amide group generates a carbonyl ylide dipole as a transient species. This highly stabilized dipole does not readily undergo 1,3-dipolar cycloaddition but rather transfers a proton to produce a cyclic ketene N,O-acetal. The ketene acetal is unstable to moisture and upon standing is readily hydrolyzed to a gamma-keto delta-lactone and an amine. In the absence of any significant amount of water, the ketene N,O-acetal undergoes conjugate addition with the activated st-bond of the dipolarophile to give a zwitterion intermediate. The anionic portion of the zwitterion adds to the neighboring carbonyl group. This is followed by epoxide ring formation with charge dissipation leading to an amido-substituted spiro cyclopentyl epoxide. In certain cases a hydroxy lactone was also isolated and its formation can be attributed to the competitive hydrolysis of the zwitterionic intermediate. The Rh(II)-catalyzed reaction of the diazo ketoamide derived from N-benzylpiperidone with DMAD afforded two different types of cycloadducts. In addition to the spiro cyclopentyl epoxide, a product derived from trapping of the carbonyl ylide dipole was also obtained, thereby providing additional support for the proposed mechanism.

  DOI：

  10.1021/jo952078h

文献信息

• Boyd,G.V.; Monteil,R.L., Journal of the Chemical Society. Perkin transactions I, 1978, p. 1338 - 1350
  作者：Boyd,G.V.、Monteil,R.L.

  DOI：——

  日期：——
• Rhodium(II) Catalyzed Cyclization of Diazo Thiocarbonyl Compounds for Heterocycloic Synthesis
  作者：Albert Padwa、Frederic R. Kinder、William R. Nadler、Lin Zhi

  DOI：10.3987/com-92-s29

  日期：——

  The mesoionic thioisomunchnone system was prepared from the rhodium(II) acetate catalyzed cyclization of a diazothioamide and was found to undergo smooth 1,3-dipolar cycloaddition with N-phenylmaleimide. In contrast to this system, the rhodium(II) reaction of an alpha-diazo-beta-oxo ester containing a thiocarbonyl group produced a cyclic thiocarbonyl ylide which extruded sulfur from a transient episulfide intermediate.
• Auwers, Justus Liebigs Annalen der Chemie, 1896, vol. 292, p. 185
  作者：Auwers

  DOI：——

  日期：——
• Peptide derivatives
  申请人：ICI AMERICAS INC.

  公开号：EP0189305B1

  公开（公告）日：1992-07-29
• US4910190A
  申请人：——

  公开号：US4910190A

  公开（公告）日：1990-03-20