(E)-3-Amino-3-methoxy-2-{[1-naphthalen-2-yl-meth-(E)-ylidene]-amino}-acrylonitrile | 126210-94-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (E)-3-Amino-3-methoxy-2-{[1-naphthalen-2-yl-meth-(E)-ylidene]-amino}-acrylonitrile
• CAS: 126210-94-4
• 化学式: C₁₅H₁₃N₃O
• 分子量: 251.288
• InChiKey: JYYWFKHHKHRYDY-AWJFGPGASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.56
• 重原子数：
  19.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  71.4
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  甲醇 、 对苯二磺酸氨基丙二酰丁氰 、 2-萘甲醛 在 sodium acetate 作用下， 反应 24.0h， 以69%的产率得到(E)-3-Amino-3-methoxy-2-{[1-naphthalen-2-yl-meth-(E)-ylidene]-amino}-acrylonitrile
  参考文献：
  名称：

  Reaction of aminopropanedinitrile 4-methylbenzenesulfonate [aminomalononitrile p-toluenesulfonate (tosylate)] with aromatic aldehydes

  摘要：

  Aminopropanedinitrile 4-methylbenzenesulfonate (ammoniopropanedinitrile p-toluenesulfonate, aminomalononitrile p-toluenesulfonate (tosylate), 1) reacts with aromatic aldehydes in methanolic sodium ethanoate to give diastereoselectively (E,E)-4-amino-1-aryl-3-cyano-4-methoxy-2-aza-1,3-butadienes (3) and trans-3,6-diaryl-2,2,5,5-tetracyanopiperazines (4). The product distribution (3:4) depends on the ratio of reactants and the structures of the substrates. Electron-releasing groups on the 4-position of the phenyl ring favor piperazine (4) formation (method B.) The formation of piperazines (4) may involve synthetically useful N-protonated aryl-and cyano-stabilized azomethine ylide (prototropic 1,3-dipoles) intermediates which could have resulted from an imine-azomethine ylide tautomerism of prior formed 1-aryl-3,3-dicyano-2-aza-1-propenes. 1,3-Dipolar cycloaddition [4 + 2] reactions of the highly reactive azomethine ylides with dimethyl 1,2-ethynedicarboxylate (DMAD) give 3,4-dicarbomethoxy-2-cyano-5-aryl-3-pyrrolines, which undergo facile dehydrocyanation to 3,4-dicarbomethoxy-2-cyano-5-arylpyrroles. The possible intermediacy of ketenimines and of aryl- and cyano-stabilized 2-azaallyl anionic intermediates in equilibrium with azomethine ylides is also considered.

  DOI：

  10.1021/jo00002a031

文献信息

• Preparation of (<i>E,E</i>)-4-Amino-1-aryl-3-cyano-4-methoxy-2-azabutadienes
  作者：Fillmore Freeman、Darrick S. H. L. Kim

  DOI：10.1055/s-1989-27364

  日期：——

  Aromatic aldehydes react with ammoniopropanedinitrile p-toluenesulfonate (ammoniomalononitrile tosylate, AMNT) to give (E,E)-4- amino-1-aryl-3-cyano-4-methoxy-2-azabutadienes.

  芳香醛与氨丙二腈对甲苯磺酸盐（氨丙二腈对甲苯磺酸盐，AMNT）反应生成 (E,E)-4-氨基-1-芳基-3-氰基-4-甲氧基-2-氮杂丁二烯。
• FREEMAN, FILLMORE;KIM, DARRICK S. H. L., SYNTHESIS,(1989) N, C. 698-699
  作者：FREEMAN, FILLMORE、KIM, DARRICK S. H. L.

  DOI：——

  日期：——
• FREEMAN, FILLMORE;KIM, DARRICK S. H. L., J. ORG. CHEM., 56,(1991) N, C. 657-663
  作者：FREEMAN, FILLMORE、KIM, DARRICK S. H. L.

  DOI：——

  日期：——
• Reaction of aminopropanedinitrile 4-methylbenzenesulfonate [aminomalononitrile p-toluenesulfonate (tosylate)] with aromatic aldehydes
  作者：Fillmore Freeman、Darrick S. H. L. Kim

  DOI：10.1021/jo00002a031

  日期：1991.1

  Aminopropanedinitrile 4-methylbenzenesulfonate (ammoniopropanedinitrile p-toluenesulfonate, aminomalononitrile p-toluenesulfonate (tosylate), 1) reacts with aromatic aldehydes in methanolic sodium ethanoate to give diastereoselectively (E,E)-4-amino-1-aryl-3-cyano-4-methoxy-2-aza-1,3-butadienes (3) and trans-3,6-diaryl-2,2,5,5-tetracyanopiperazines (4). The product distribution (3:4) depends on the ratio of reactants and the structures of the substrates. Electron-releasing groups on the 4-position of the phenyl ring favor piperazine (4) formation (method B.) The formation of piperazines (4) may involve synthetically useful N-protonated aryl-and cyano-stabilized azomethine ylide (prototropic 1,3-dipoles) intermediates which could have resulted from an imine-azomethine ylide tautomerism of prior formed 1-aryl-3,3-dicyano-2-aza-1-propenes. 1,3-Dipolar cycloaddition [4 + 2] reactions of the highly reactive azomethine ylides with dimethyl 1,2-ethynedicarboxylate (DMAD) give 3,4-dicarbomethoxy-2-cyano-5-aryl-3-pyrrolines, which undergo facile dehydrocyanation to 3,4-dicarbomethoxy-2-cyano-5-arylpyrroles. The possible intermediacy of ketenimines and of aryl- and cyano-stabilized 2-azaallyl anionic intermediates in equilibrium with azomethine ylides is also considered.