methyl cyanodiazoacetate | 22979-38-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: methyl cyanodiazoacetate
• 英文别名: methyl diazocyanoacetate；methyl 2-cyano-2-diazoacetate；Methylcyanodiazoacetat；methyl (2Z)-2-cyano-2-diazoacetate
• CAS: 22979-38-0
• 化学式: C₄H₃N₃O₂
• 分子量: 125.087
• InChiKey: CBULTUWLDZNVNK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  52.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl cyanodiazoacetate 、 乙烯基三甲基硅烷 反应 1.5h， 以53%的产率得到
  参考文献：
  名称：

  环丙基羰基途径生成γ-甲硅烷基碳阳离子

  摘要：

  已经制备了顺-1-羟甲基-2-三甲基甲硅烷基环丙烷的甲磺酸酯衍生物，以及许多相关的甲磺酸酯和在1-位带有取代基的三氟甲磺酸酯。这些底物全部在CD 3 CO 2 D中溶剂溶解，得到衍生自环丙基羰基阳离子的产物，该产物经过进一步重排得到3-三甲基甲硅烷基环丁基阳离子。这些3-三甲基甲硅烷基环丁基阳离子通过与γ-三甲基甲硅烷基的长距离后叶相互作用而稳定化。当取代基是吸电子的（CF 3，CN或CO 2 CH 3），形成大量的双环丁烷产物。双环丁烷是从阳离子中间体中消除了γ-三甲基甲硅烷基的结果，该中间体具有异常长的Si-C键。反式-1-羟甲基-2-三甲基甲硅烷基环丙烷的甲磺酸酯和三氟甲磺酸酯衍生物和1-取代的类似物的溶剂化化学性质可能完全不同，因为这些底物通常不会导致3-三甲基甲硅烷基环丁基阳离子。

  DOI：

  10.3762/bjoc.15.170
• 作为产物：
  描述：

  氰乙酸甲酯 在 sodium azide 、 2-chloro-1-ethylpyridinium tetrafluoroborate 、 potassium carbonate 作用下， 以 水 、 乙腈 为溶剂， 反应 0.25h， 以62%的产率得到methyl cyanodiazoacetate
  参考文献：
  名称：

  The rhodium carbenoid route to oxazoles. Synthesis of 4-functionalised oxazoles; Three step preparation of a bis-oxazole

  摘要：

  Oxazole-4-sulfones, -phosphonates, and -nitriles are prepared by rhodium(II) catalysed addition of nitriles to the corresponding diazo compound, The effect of the ligand on rhodium was briefly investigated, with rhodium(II) trifluoroacetamide generally proving the most effective catalyst. The 4-cyanooxazole 9 is readily converted into the bis-oxazoles 10-12.

  DOI：

  10.1016/s0040-4020(01)90396-5

文献信息

• Rhodium(<scp>iii</scp>)-catalyzed formal oxidative [4 + 1] cycloaddition of benzohydroxamic acids and α-diazoesters. A facile synthesis of functionalized benzolactams
  作者：Hon-Wah Lam、Ka-Yi Man、Wai-Wing Chan、Zhongyuan Zhou、Wing-Yiu Yu

  DOI：10.1039/c4ob00512k

  日期：——

  A Rh(III)-catalyzed oxidative [4 + 1] cycloaddition of benzohydroxamic acids and α-diazoesters is achieved to afford benzolactams in up to 93% yields. With the N-OAc amido moiety as a directing group, the ortho-C–H is selectively functionalized and the catalytic reaction exhibits excellent tolerance to different functional substituents. A notable rhodacyclic complex is isolated and structurally characterized

  可实现Rh（III）催化的苯并异羟肟酸和α-重氮酸酯的氧化[4 +1]环加成反应，从而以最高93％的收率得到苯并内酰胺。以N -OAc酰胺基部分为导向基团，邻位-C-H被选择性官能化，并且催化反应对不同的官能取代基表现出优异的耐受性。分离出了显着的铑环配合物并对其结构进行了表征，这表明CH / NH环金属化是催化循环的关键步骤。
• Diazo-sulfones and -nitriles in oxazole synthesis; three step preparation of a bis-oxazole
  作者：Kevin J. Doyle、Christopher J. Moody

  DOI：10.1016/0040-4039(93)88041-g

  日期：1992.12

  Oxazole-4-sulfones and -nitriles are prepared by rhodium(II) catalysed addition of nitriles to the corresponding diazo compound: the 4-cyarkooxazole 3 is readily converted into the bis-oxazoles 4 and S.
• A practical system to synthesize the multiple-substituted 2,5-dihydrofuran by the intermolecular dipolar cycloaddition reactions involving acceptor/acceptor-substituted diazo reagents
  作者：Shifa Zhu、Lijuan Chen、Chao Wang、Renxiao Liang、Xiujun Wang、Yanwei Ren、Huanfeng Jiang

  DOI：10.1016/j.tet.2011.05.028

  日期：2011.7

  A practical system for synthesizing the multiple-substituted 2,5-dihydrofuran through intermolecular dipolar cycloaddition reactions of acceptor/acceptor diazo reagents, aldehydes, and acetylenedicarboxylate was developed. The reactions proceeded effectively under ambient temperature with low reactant ratios. The control reactions revealed that there are two competitive paths: one forms 1,3-dioxolane and the other forms 2,5-dihydrofuran. These two paths could be controlled by modifying the steric hindrance of the diazo reagents. (C) 2011 Elsevier Ltd. All rights reserved.
• A ketenimine from the addition of a carbene to an isocyanide
  作者：Engelbert Ciganek

  DOI：10.1021/jo00828a085

  日期：1970.3
• Attempts of arsirane synthesis by addition of diazocompounds with arsaalkenes
  作者：Souad Himdi- Kabbab、Jack Hamelin

  DOI：10.1016/0040-4039(91)85077-i

  日期：1991.6

  The reaction of ethyl diazoacetate with arsaalkenes 8 and 9, leads to diazaarsole 3 and diazocompounds 10 and 11. Diphenyldiazomethane addition follows a different course leading to alkenes 23 and 24, possibly through a transient arsirane.