phenylmalonitrile | 86489-57-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: phenylmalonitrile
• 英文别名: 2-mesitylmalononitrile；mesitylmalononitrile；2-(2,4,6-trimethylphenyl)propanedinitrile
• CAS: 86489-57-8
• 化学式: C₁₂H₁₂N₂
• 分子量: 184.241
• InChiKey: AWBARRZDWMPKEU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  47.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  phenylmalonitrile 、 苯甲醇 在 氧气 、 caesium carbonate 作用下， 以 乙腈 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 43.5h， 以74%的产率得到benzyl 2,4,6-trimethylbenzoate
  参考文献：
  名称：

  使用分子氧的氧化法由α取代的丙二腈和醇形成的立体拥挤酯

  摘要：

  通过在分子氧气氛下在碱的存在下，简单地将α-取代的丙二腈与醇或硫醇混合，已开发出了易于获得的取代的丙二腈与醇或硫醇的无金属氧化酯化或硫代酯化方法。

  DOI：

  10.1002/ejoc.201800984
• 作为产物：
  描述：

  2,4,6-三甲基氟苯 、 丙二腈 在 (η5-ethyltetramethylcyclopentadienyl)(η6-benzene)rhodium(III) tetrafluoroborate 、 sodium carbonate 作用下， 以 硝基甲烷 、 氘代丙酮 为溶剂， 100.0~220.0 ℃ 、8.67 Pa 条件下， 反应 7.0h， 以0.014 g的产率得到phenylmalonitrile
  参考文献：
  名称：

  Arene complexes of transition metals in reactions with nucleophilic reagents: XXX. Reaction of π-halomesitylene [Tetramethyl(ethyl)cyclopentadienyl]rhodium(II) complexes with anions derived from CH acids

  摘要：

  Reactions of fluoro- and chloromesitylene pi-complexes [(eta(6)-1-Hlg-2,4,6-Me3C6H2)(eta(5) -C5EtMe4)Rh]-(BF4)(2) (Hlg = F, Cl) with diethyl malonate anion in THF or acetone-d(6) at 20 degrees C initially (within the first 530 min) involve nucleophile addition at unsubstituted carbon atom in the arene ligand with formation of pi-cyclohexadienyl complexes {[eta(5)-1-(EtOCO)(2)CH-1-H-3-Hlg-2,4,6-Me3C6H2](eta(5)-C5EtMe4)Rhj(BF4)(2), The subsequent replacement of the halogen atom yields {[eta(6)-1-(EtOCO)(2)CH-2,4,6-Me3C6H2](eta(5) -C5EtMe4)Rh}(BF4)(2), where the arene ligand is readily withdrawn from pi-coordination by the action of chloride ion or the solvent. Dimethyl mesitylmalonate was isolated in 76% yield. Likewise, the reactions with anions derived from malononitrile and ethyl cyanoacetate gave 25-38% of the corresponding derivatives 1-R-2,4,6-Me3C6H2 where R = (NC)(2)CH or EtOCO(NC)CH.

  DOI：

  10.1134/s1070428007120056

文献信息

• Sterically Demanding Oxidative Amidation of α-Substituted Malononitriles with Amines Using O₂
  作者：Jing Li、Martin J. Lear、Yujiro Hayashi

  DOI：10.1002/anie.201603399

  日期：2016.7.25

  An efficient amidation method between readily available 1,1-dicyanoalkanes and either chiral or nonchiral amines was realized simply with molecular oxygen and a carbonate base. This oxidative protocol can be applied to both sterically and electronically challenging substrates in a highly chemoselective, practical, and rapid manner. The use of cyclopropyl and thioether substrates support the radical

  简单地使用分子氧和碳酸盐碱即可实现易于获得的1,1-二氰基烷烃与手性或非手性胺之间的高效酰胺化方法。该氧化方案可以高度化学选择性，实用和快速的方式应用于空间和电子挑战性底物。环丙基和硫醚底物的使用可支持α-过氧丙二腈物种的自由基形成，后者可以环化成二恶英，后者可以单价氧化丙二腈α-碳二酮以提供能够与胺亲核试剂反应的活化的酰基氰化物。
• A FACILE SYNTHETIC ROUTE TO SOME ARYLMALONONITRILES
  作者：Hitomi Suzuki、Tsutomu Kobayashi、Atsuhiro Osuka

  DOI：10.1246/cl.1983.589

  日期：1983.4.5

  Copper(I) iodide-assisted reaction of aryl iodides with malononitrile anion provides a convenient route to some arylmalononitriles.

  碘化铜 (I) 辅助芳基碘化物与丙二腈阴离子的反应为某些芳基丙二腈提供了一条便捷的途径。
• A Convenient Protocol for the Synthesis of Hindered Aryl Malononitriles
  作者：Anita Schnyder、Adriano Indolese、Thomas Maetzke、Jean Wenger、Hans-Ulrich Blaser

  DOI：10.1055/s-2006-944215

  日期：2006.11

  A technically feasible method has been developed for the synthesis of variety of aryl malononitriles in high yields (70-95%) using the palladium-catalyzed coupling reaction of malononitrile with aryl bromides and chlorides, respectively. The influence a ­several reaction parameters such as base, ligand, solvent or tem­perature were investigated in some detail.

  利用钯催化的丙二腈与芳基溴化物和氯化物的偶联反应，开发出了一种技术上可行的方法，可以高产率（70%-95%）合成各种芳基丙二腈。研究人员对碱基、配体、溶剂或温度等反应参数的影响进行了深入研究。
• Industrial R&D on Catalytic CC and CN Coupling Reactions: A Personal Account on Goals, Approaches and Results
  作者：Hans-Ulrich Blaser、Adriano Indolese、Frédéric Naud、Ulrike Nettekoven、Anita Schnyder

  DOI：10.1002/adsc.200404156

  日期：2004.12

  AbstractR&D issues for the application of Pd‐ and Ni‐catalyzed CC and CN coupling reactions in the fine chemicals industry are discussed. In a first part, some background is given on industrial R&D and the role of CC and CN coupling for preparative applications is described. The following principal approaches to industrial research are illustrated with relevant examples from the literature and from our own laboratories: i) development of catalysts and catalytic methodologies with industrial potential; ii) finding shorter routes to target molecules using catalytic methods; iii) development of industrial catalytic processes in multi‐step syntheses.
• SUZUKI, HITOMI;KOBAYASHI, TSUTOMU;OSUKA, ATSUHIRO, CHEM. LETT., 1983, N 4, 589-590
  作者：SUZUKI, HITOMI、KOBAYASHI, TSUTOMU、OSUKA, ATSUHIRO

  DOI：——

  日期：——