2-Diazo-N-(2-hydroxyethyl)-N-phenylmalonamic acid ethyl ester | 156115-86-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2-Diazo-N-(2-hydroxyethyl)-N-phenylmalonamic acid ethyl ester
• 英文别名: ethyl 2-diazo-3-[(2-hydroxyethyl)(phenyl)amino]-3-oxopropanoate；ethyl 2-diazo-3-[N-(2-hydroxyethyl)anilino]-3-oxopropanoate
• CAS: 156115-86-5
• 化学式: C₁₃H₁₅N₃O₄
• 分子量: 277.28
• InChiKey: CVQOOZMEWGTZPU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  68.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-Diazo-N-(2-hydroxyethyl)-N-phenylmalonamic acid ethyl ester 在 Rh₂(NHCOC₃F₇)4 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 1-(2-Hydroxy-ethyl)-2-oxo-2,3-dihydro-1H-indole-3-carboxylic acid ethyl ester
  参考文献：
  名称：

  Ligand Effects in the Rhodium(II)-Catalyzed Reactions of .alpha.-Diazoamides. Oxindole Formation is Promoted by the Use of Rhodium(II) Perfluorocarboxamide Catalysts

  摘要：

  An improved procedure for the preparation of ethyl 2-diazomalonyl chloride ws developed which involves the reaction of ethyl diazoacetate with triphosgene. Using this diazo acid chloride, it was possible to prepare a variety of diazoamides from substituted amines. The rhodium(II)-catalyzed decomposition of these diazoamides was studied in order to probe the chemoselectivity of the carbenoid intermediates in intramolecular insertion reactions. Rhodium(II) acetate decomposition of N-benzyl-2-diazo-N-phenylmalonamic acid ethyl ester resulted in intramolecular C-H insertion to give ethyl 1,4-diphenyl-2-oxoazetidine-3-carboxylate. By changing the catalyst ligand to trifluoroacetamide, beta-lactam formation was completely suppressed in favor of the aromatic C-H insertion which produces an oxindole as the only detectable product. The competition between aliphatic and aromatic carbon-hydrogen insertion of 2-diazo-N-phenylmalonamic acid ethyl ester provides another example of ligand effectiveness in controlling chemoselectivity in dirhodium(II)-catalyzed metal carbene reactions. Thus, treatment of the N-isobutyldiazoanilide with rhodium(II) acetate results in exclusive aliphatic C-H insertion giving 4,4-dimethyl-2-oxo-1-phenylpyrrolidine-3-carboxylic acid ethyl ester, while the perfluorobutyramide ligand promotes oxidinole formation by aromatic C-H insertion. Several other rhodium(II)-catalyzed reactions were studied and were found to be highly catalyst dependent, rhodium(II) perfluorocarboxamides promoting aromatic C-H insertion, and hence oxindole formation, over O-H insertion, cyclization onto adjacent triple bonds, or cyclization to generate 1,3-dipolar intermediates.

  DOI：

  10.1021/jo00088a028
• 作为产物：
  描述：

  N-苯基乙醇胺 在 三乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 39.0h， 生成 2-Diazo-N-(2-hydroxyethyl)-N-phenylmalonamic acid ethyl ester
  参考文献：
  名称：

  Studies towards the Synthesis of AlkylN-(4-Nitrophenyl)-3/2-oxomorpholine-2/3-carboxylates

  摘要：

  AbstractThe syntheses of methyl 4‐(4‐nitrophenyl)‐3‐oxomorpholine‐2‐carboxylate (3a) and ethyl 4‐(4‐nitrophenyl)‐2‐oxomorpholine‐3‐carboxylate (5b), important building blocks for the synthesis of factor Xa inhibitor rivaroxaban analogs with potential dual antithrombotic activity, via Rh2(OAc)4‐catalyzed OH and NH carbene insertion reactions are described.

  DOI：

  10.1002/hlca.201300085

文献信息

• Ethyl 2-diazomalonyl chloride. An efficient diazoacylating reagent
  作者：Joseph P. Marino、Martin H. Osterhout、Alan T. Price、Scott M. Sheehan、Albert Padwa

  DOI：10.1016/s0040-4039(00)75980-6

  日期：1994.1

  Ethyl 2-diazomalonyl chloride readily reacts with aromatic and aliphatic amines, alcohols, thiols, and amides for form a variety of alpha-diazo carbonyl species.