methyl cyanoacetate sodium enolate

• 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: methyl cyanoacetate sodium enolate
• 英文别名: methyl sodiocyanoacetate；sodio methyl cyanoacetate
• 化学式: C₄H₄NNaO₂
• 分子量: 121.071
• InChiKey: KNGTVRSCWJOJBY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.2
• 重原子数：
  8
• 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：
  27.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl cyanoacetate sodium enolate 、 丙酮肟 在 三氟甲磺酸酐 、 三乙胺 作用下， 以 甲苯 为溶剂， 反应 1.08h， 以99%的产率得到2-cyano-3-methylaminobut-2-enoic acid methyl ester
  参考文献：
  名称：

  Facile One-pot Syntheses of Amidines and Enamines from Oximes via Beckmann Rearrangement Using Trifluoromethansulfonic Anhydride

  摘要：

  通过在温和条件下分别利用胺和碳亲核试剂捕获由肟经贝克曼重排形成的碳正离子中间体，实现了酰亚胺和烯胺的简易一锅法合成。

  DOI：

  10.1246/cl.2004.322

文献信息

• Facile One-Pot Syntheses of Amidines and Enamines from Oximes via Beckmann Rearrangement Using Trifluoromethanesulfonic Anhydride
  作者：Tomofumi Takuwa、Tomofumi Minowa、Jim Yoshitaka Onishi、Teruaki Mukaiyama

  DOI：10.1246/bcsj.77.1717

  日期：2004.9

  Iminocarbocation intermediates were in situ-generated by treating various oximes with trifluoromethanesulfonic anhydride (Tf2O) in the presence of triethylamine in toluene and nucleophilic trapping with amines or sodium enolates under mild conditions afforded the corresponding amidines and enamines. Some of the thus-obtained enamines were converted to 2-substituted 4-oxo-3-quinolinecarboxylic acid derivatives by subsequent intramolecular Friedel–Crafts acylation.

  通过将各种肟在甲苯中与三氟甲磺酸酐（Tf2O）和三乙胺反应，原位生成亚胺碳正中间体，并在温和条件下用胺或烯醇钠捕捉，得到相应的脒和烯胺。部分获得的烯胺随后通过分子内 Friedel-Crafts 酰基化反应转化为 2-取代的 4-氧代-3-喹啉羧酸衍生物。
• Synthesis of Novel Bicyclic Nitroxides Using Partial Favorskii Rearrangement
  作者：Andrej Babič、Slavko Pečar

  DOI：10.1055/s-2008-1072715

  日期：2008.5

  1-oxyl was reacted with several C-nucleophiles to give novel bicyclic pyrrolidine nitroxides through partial Favorskii rearrangement. Further reduction with sodium borohydride gave spin probes with free hydroxyl groups and under harsh reduction conditions allowed the Favorskii rearrangement to proceed to completion.

  3-Bromo-2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl 与几种 C-亲核试剂反应，通过部分 Favorskii 重排得到新型双环吡咯烷氮氧化物。用硼氢化钠进一步还原得到带有游离羟基的自旋探针，并且在苛刻的还原条件下允许 Favorskii 重排进行到完成。
• Organoiron complexes in organic synthesis. Part 18. Spiroannelation reactions of some bifunctional tricarbonyl(cyclohexadienyl)iron hexafluorophosphate salts
  作者：Anthony J. Pearson、Peter Ham、David C. Rees

  DOI：10.1039/p19820000489

  日期：——

  The synthesis of tricarbonyl(cyclohexadienylium)iron salts containing tosyloxy-substituents in the lateral chain, and their reactions with nucleophiles to give spirocyclic compounds, is described. The synthesis and spiroannelation reactions of complexes with gem-dinitrile and cyanoester groups in the lateral chain are presented.

  描述了在侧链中含有甲苯磺酰氧基取代基的三羰基（环己二烯基）铁盐的合成，以及它们与亲核试剂反应生成螺环化合物的过程。提出了在侧链中具有宝石-二腈基和氰基酯基的配合物的合成和螺二酰胺化反应。
• The preparation of enantiomerically enriched γ-amino acids (GABAs) using palladium catalysed allylic substitution
  作者：Christopher J. Martin、David J. Rawson、Jonathan M.J. Williams

  DOI：10.1016/s0957-4166(98)00383-8

  日期：1998.10

  Enantioselective palladium catalysed allylic substitution reactions have been employed as the asymmetry-producing step in the synthesis of enantiomerically enriched gamma-amino acids. (C) 1998 Elsevier Science Ltd. All rights reserved.
• New substitution reaction of allylic nitro compounds. Regioselective replacement of nitro group in cyclic α-(nitroalkyl)enones by nucleophiles
  作者：Rui Tamura、Shinobu Tamai、Hitomi Suzuki

  DOI：10.1016/s0040-4039(01)80414-7

  日期：——