2-((二苯基亚甲基)氨基)环丁烯羧酸甲酯 | 152530-75-1

• 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: 2-((二苯基亚甲基)氨基)环丁烯羧酸甲酯
• 英文名称: Methyl 2-<(diphenylmethylene)amino>cyclobutenecarboxylate
• 英文别名: 2-(Benzhydrylideneamino)-cyclobutene-1-carboxylic acid methyl ester；methyl 2-(benzhydrylideneamino)cyclobutene-1-carboxylate
• CAS: 152530-75-1
• 化学式: C₁₉H₁₇NO₂
• 分子量: 291.349
• InChiKey: AXKYWADMOGXBQJ-UHFFFAOYSA-N

物化性质

• 沸点：
  403.5±45.0 °C(Predicted)
• 密度：
  1.11±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-((二苯基亚甲基)氨基)环丁烯羧酸甲酯 500.0 ℃ 、0.13 Pa 条件下， 以68%的产率得到3,4-Dihydro-3-<1'-(methoxycarbonyl)vinyl>-1-phenyisoquinoline
  参考文献：
  名称：

  Cyclopropyl building blocks for organic synthesis. Part 22. Facile synthesis of stable analogs of 2-oxocyclobutanecarboxylates: 2-[(diphenylmethylene)amino]cyclobutenecarboxylates, derivatives and reactions

  摘要：

  An efficient two-step synthesis of 2-[(diphenylmethylene)amino]cyclobutenecarboxylate (4a) and some analogous derivatives from 2-chloro-2-cyclopropylideneacetates 2, 17, 22, and 25 and nonenolizable ketimines, especially diphenylmethyleneamine (DPMA-H), is described. A likely mechanism for the formation of 4a from the primary Michael adduct 3 of DPMA-H to 2 and its substituted analogues is presented. The unique neighboring group effect of the DPMA moiety to allow formation of an azaspiropentane intermediate and its regioselective rearrangement to cyclobutenamine derivatives is discussed and further exemplified by an extremely facile SET alpha-chlorination. Compound 4a and derivatives undergo a thermal ring-opening reaction to the corresponding butadienes with subsequent formation of 1,3-disubstituted 3,4-dihydroisoquinolines 39. Further transformations of 4a and some derivatives include transesterification, hydrolysis to methyl 2-oxocyclobutanecarboxylates, and addition of N-phenyltriazolinedione.

  DOI：

  10.1021/jo00075a047
• 作为产物：
  描述：

  Methyl 2-<1-(diphenylmethylene)aminocyclopropyl>-2-chloroacetate 在 三乙胺 、 lithium iodide 作用下， 以 异丙醇 为溶剂， 反应 168.0h， 以73%的产率得到2-((二苯基亚甲基)氨基)环丁烯羧酸甲酯
  参考文献：
  名称：

  Cyclopropyl building blocks for organic synthesis. Part 22. Facile synthesis of stable analogs of 2-oxocyclobutanecarboxylates: 2-[(diphenylmethylene)amino]cyclobutenecarboxylates, derivatives and reactions

  摘要：

  An efficient two-step synthesis of 2-[(diphenylmethylene)amino]cyclobutenecarboxylate (4a) and some analogous derivatives from 2-chloro-2-cyclopropylideneacetates 2, 17, 22, and 25 and nonenolizable ketimines, especially diphenylmethyleneamine (DPMA-H), is described. A likely mechanism for the formation of 4a from the primary Michael adduct 3 of DPMA-H to 2 and its substituted analogues is presented. The unique neighboring group effect of the DPMA moiety to allow formation of an azaspiropentane intermediate and its regioselective rearrangement to cyclobutenamine derivatives is discussed and further exemplified by an extremely facile SET alpha-chlorination. Compound 4a and derivatives undergo a thermal ring-opening reaction to the corresponding butadienes with subsequent formation of 1,3-disubstituted 3,4-dihydroisoquinolines 39. Further transformations of 4a and some derivatives include transesterification, hydrolysis to methyl 2-oxocyclobutanecarboxylates, and addition of N-phenyltriazolinedione.

  DOI：

  10.1021/jo00075a047

文献信息

• Cyclopropyl building blocks for organic synthesis. Part 22. Facile synthesis of stable analogs of 2-oxocyclobutanecarboxylates: 2-[(diphenylmethylene)amino]cyclobutenecarboxylates, derivatives and reactions
  作者：Ludger Wessjohann、Karsten Giller、Bernd Zuck、Lars Skatteboel、Armin de Meijere

  DOI：10.1021/jo00075a047

  日期：1993.11

  An efficient two-step synthesis of 2-[(diphenylmethylene)amino]cyclobutenecarboxylate (4a) and some analogous derivatives from 2-chloro-2-cyclopropylideneacetates 2, 17, 22, and 25 and nonenolizable ketimines, especially diphenylmethyleneamine (DPMA-H), is described. A likely mechanism for the formation of 4a from the primary Michael adduct 3 of DPMA-H to 2 and its substituted analogues is presented. The unique neighboring group effect of the DPMA moiety to allow formation of an azaspiropentane intermediate and its regioselective rearrangement to cyclobutenamine derivatives is discussed and further exemplified by an extremely facile SET alpha-chlorination. Compound 4a and derivatives undergo a thermal ring-opening reaction to the corresponding butadienes with subsequent formation of 1,3-disubstituted 3,4-dihydroisoquinolines 39. Further transformations of 4a and some derivatives include transesterification, hydrolysis to methyl 2-oxocyclobutanecarboxylates, and addition of N-phenyltriazolinedione.