α-o-tolyl α-cyanoacetate | 1136-24-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: α-o-tolyl α-cyanoacetate
• 英文别名: ethyl 2-(2-methylphenyl)cyanoacetate；ethyl 2-cyano-2-(o-tolyl)acetate；ethyl 2-(2-tolyl)-cyanoacetate；ethyl o-tolylcyanoacetate；cyano-o-tolyl-acetic acid ethyl ester；Cyan-o-tolyl-essigsaeure-aethylester；ethyl 2-cyano-2-(2-methylphenyl)acetate
• CAS: 1136-24-9
• 化学式: C₁₂H₁₃NO₂
• 分子量: 203.241
• InChiKey: CLVFCYRZVOKCDP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  α-o-tolyl α-cyanoacetate 、 环己胺 以94%的产率得到
  参考文献：
  名称：

  HARRIS R. L. N.; HUPPATZ J. L.; TEITEI T., AUSTRAL. J. CHEM., 1979, 32, NO 3, 669-679

  摘要：

  DOI：
• 作为产物：
  描述：

  邻甲基苯乙腈 在 乙醚 、 sodium amide 作用下， 生成 α-o-tolyl α-cyanoacetate
  参考文献：
  名称：

  Bergel et al., Journal of the Chemical Society, 1944, p. 261,264

  摘要：

  DOI：

文献信息

• An efficient method for the preparation of mono α-aryl derivatives of diethyl malonate and ethyl cyanoacetate using ethyl-1-imidazole carbamate (EImC)
  作者：Manoranjan Behera、R. Venkat Ragavan、M. Sambaiah、Balaiah Erugu、J. Rama Krishna Reddy、K. Mukkanti、Satyanarayana Yennam

  DOI：10.1016/j.tetlet.2011.12.067

  日期：2012.2

  An efficient method for the synthesis of mono α-aryl derivatives of diethyl malonate and ethyl cyanoacetate using ethyl-1-imidazole carbamate (EImC) has been described. Using this method many sterically hindered and highly substituted mono α-aryl derivatives of diethyl malonate and ethyl cyanoacetate were synthesized in high yield.

  已经描述了使用-1-咪唑氨基甲酸乙酯（EImC）合成丙二酸二乙酯和氰基乙酸乙酯的单α-芳基衍生物的有效方法。用这种方法可以高产率地合成许多位阻和高度取代的丙二酸二乙酯和氰基乙酸乙酯的单α-芳基衍生物。
• [EN] ASYMMETRIC MICHAEL AND ALDOL ADDITION USING BIFUNCTIONAL CINCHONA-ALKALOID-BASED CATALYSTS<br/>[FR] ADDITIONS ASYMETRIQUES DE MICHAEL ET D'ALDOL UTILISANT DES CATALYSEURS BIFONCTIONNELS A BASE DE CINCHONINE
  申请人：UNIV BRANDEIS

  公开号：WO2005121137A1

  公开（公告）日：2005-12-22

  One aspect of the present invention relates to quinine-based and quinidine-based catalysts. Another aspect of the invention relates to a method of preparing a derivatized quinine-based or quinidine-based catalyst comprising 1) reacting quinine or quinidine with 5 base and a compound that has a suitable leaving group, and 2) converting the ring methoxy group to a hydroxy group. Another aspect of the present invention relates to a method of preparing a chiral, non-racemic compound from a prochiral electron-deficient alkene or azo compound or prochiral aldehyde or prochiral ketone, comprising the step of: reacting a prochiral electron-deficient alkene or azo compound or prochiral aldehyde or prochiral 10 ketone with a nucleophile in the presence of a catalyst; thereby producing a chiral, non racemic compound; wherein said catalyst is a derivatized quinine or quinidine. Another aspect of the present invention relates to a method of kinetic resolution, comprising the step of reacting racemic chiral alkene with a nucleophile in the presence of a derivatized quinine or quinidine.

  本发明的一个方面涉及基于奎宁和奎宁的催化剂。发明的另一个方面涉及一种制备衍生奎宁或奎宁催化剂的方法，包括1）将奎宁或奎宁与5碱和具有适当离去基团的化合物反应，以及2）将环甲氧基转化为羟基。本发明的另一个方面涉及一种从前手性电子亏缺烯烃或偶氮化合物或前手性醛或前手性酮制备手性、非拉克米化合物的方法，包括以下步骤：在催化剂存在下，将前手性电子亏缺烯烃或偶氮化合物或前手性醛或前手性酮与亲核试剂反应；从而产生手性、非拉克米化合物；其中所述催化剂是衍生奎宁或奎宁。本发明的另一个方面涉及一种动力学分辨的方法，包括在衍生奎宁或奎宁存在下，将拉克米手性烯烃与亲核试剂反应的步骤。
• Synergistic Effect of a Bis(proazaphosphatrane) in Mild Palladium-Catalyzed Direct α-Arylations of Nitriles with Aryl Chlorides
  作者：So Han Kim、Wonseok Jang、Min Kim、John G. Verkade、Youngjo Kim

  DOI：10.1002/ejoc.201402466

  日期：2014.9

  The effect of a bis(proazaphosphatrane) ligand on the palladium-catalyzed direct α-arylation of nitriles with various aryl chlorides under mild conditions is reported. Comparisons of the catalytic properties of this ligand with those of three related mono(proazaphosphatrane)s under the same reaction conditions revealed that bis(proazaphosphatrane) displayed a synergistically enhanced activity. In the

  报道了在温和条件下双（氮杂磷杂环丙烷）配体对腈与各种芳基氯的钯催化直接 α-芳基化的影响。在相同的反应条件下，该配体与三个相关单（原氮杂磷酯）的催化性能的比较表明，双（原氮杂磷酯）显示出协同增强的活性。在双（原氮杂磷酯）配体的存在下，氰基乙酸乙酯和伯腈和仲腈有效地与各种含有富电子、缺电子和电子中性基团的芳基氯化物偶联。
• Palladium-Catalyzed Arylation of Malonates and Cyanoesters Using Sterically Hindered Trialkyl- and Ferrocenyldialkylphosphine Ligands
  作者：Neil A. Beare、John F. Hartwig

  DOI：10.1021/jo016226h

  日期：2002.1.1

  diethyl malonate, di-tert-butyl malonate, diethyl fluoromalonate, ethyl cyanoacetate, and ethyl phenylcyanoacetate. Although alkyl malonates and ethyl alkylcyanoacetates did not react with aryl halides using these catalysts, the same products were formed conveniently in one pot from diethylmalonate by cross-coupling of an aryl halide in the presence of excess base and subsequent alkylation.

  据报道，钯催化的芳基溴化物和氯化物与两种常见的稳定化碳负离子（丙二酸二烷基酯和烷基氰基酸酯的烯醇盐）的反应。对这些反应的范围进行了探索，并且表明该过程以一般方式发生。使用P（t-Bu）（3）（1），五苯基二茂铁基配体（Ph（5）C（5））Fe（C（5）H（4））P（t-Bu）（2）（2） ，或金刚烷基配体（1-Ad）P（t-Bu）（2）（3），表明贫电子和富电子，空间受阻且不受阻碍的芳基溴化物和氯化物与丙二酸二乙酯丙二酸叔丁酯，氟丙二酸二乙酯，氰基乙酸乙酯和苯基氰基乙酸乙酯。尽管使用这些催化剂的丙二酸烷基酯和烷基氰基乙酸乙酯不与芳基卤化物反应，
• An Efficient and Mild CuI/<scp>l</scp>-Proline-Catalyzed Arylation of Acetylacetone or Ethyl Cyanoacetate
  作者：Yongwen Jiang、Nan Wu、Haihong Wu、Mingyuan He

  DOI：10.1055/s-2005-918921

  日期：——

  The coupling reaction of aryl iodides with acetylacetone or ethyl cyanoacetate under catalysis of CuI/l-proline works at ­relatively mild conditions to provide 3-aryl-2, 4-pentanediones and α-aryl cyanoacetates in moderate to good yields.

  在CuI/l-脯氨酸催化下，芳基碘化物与乙酰乙酮或乙基氰乙酸酯的偶联反应在相对温和的条件下进行，能够生成3-芳基-2, 4-戊二酮和α-芳基氰乙酸酯，产率中等至良好。