N-(cyanomethyl)-2-phenylacetamide | 5467-51-6

• 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: N-(cyanomethyl)-2-phenylacetamide
• 英文别名: N-phenylacetyl-glycine nitrile；N-Phenylacetyl-glycin-nitril；Phenacetursaeure-nitril；N-Phenylacetyl-aminoacetonitril；Phenaceturonitrile
• CAS: 5467-51-6
• 化学式: C₁₀H₁₀N₂O
• mdl: MFCD01212306
• 分子量: 174.202
• InChiKey: VTGAHHSISUODFE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  52.9
• 氢给体数：
  1
• 氢受体数：
  2

安全信息

• 海关编码：
  2926909090

反应信息

• 作为反应物：
  描述：

  N-(cyanomethyl)-2-phenylacetamide 在 镍 、 异丙醇 作用下， 125.0 ℃ 、12.75 MPa 条件下， 生成 2-苯甲基咪唑啉
  参考文献：
  名称：

  DE830954

  摘要：

  公开号：
• 作为产物：
  描述：

  2-(2-Phenylacetamido)acetaldehyde oxime 在 2-氯-1-甲基吡啶碘化物 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.17h， 以91%的产率得到N-(cyanomethyl)-2-phenylacetamide
  参考文献：
  名称：

  在温和条件下使用 2-Chloro-1-methylpyridinium Iodide 将醛肟高效转化为腈

  摘要：

  摘要 在温和的条件下，使用 2-氯-1-甲基碘化吡啶鎓（CMPI）作为脱水剂，可以将各种（脂肪族、芳香族和杂环芳香族）醛肟转化为相应的腈类，收率良好。

  DOI：

  10.1081/scc-120034158

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。
• Umpolung reactivity in amide and peptide synthesis
  作者：Bo Shen、Dawn M. Makley、Jeffrey N. Johnston

  DOI：10.1038/nature09125

  日期：2010.6

  which the polarities of the two reactants are reversed (German, umpolung) during carbon–nitrogen bond formation relative to traditional approaches. The use of nitroalkanes as acyl anion equivalents provides a conceptually innovative approach to amide and peptide synthesis, and one that might ultimately provide for efficient peptide synthesis that is fully reliant on enantioselective methods.

  酰胺键是自然界最常见的功能和结构元素之一，因为所有天然肽和蛋白质的骨架都由酰胺键组成。酰胺也存在于许多治疗性小分子中。使用现有方法构建酰胺键主要依赖于脱水方法，尽管氧化和基于自由基的方法是代表性的替代方法。在几乎每个例子中，在碳-氮键形成步骤中，碳和氮分别具有亲电和亲核特性。在这里，我们表明用亲电碘源活化胺和硝基烷烃可以直接产生酰胺产物。初步观察支持两种反应物极性反转的机制（德国，umpolung) 在碳氮键形成过程中相对于传统方法。使用硝基烷烃作为酰基阴离子等价物为酰胺和肽合成提供了一种概念上的创新方法，并且可能最终提供完全依赖对映选择性方法的有效肽合成。
• Studies on Hepatic Agents. I. Synthesis of Aminoacyl (and Hydroxyacyl) Aminoacetonitriles
  作者：SEIGO SUZUE、TUTOMU IRIKURA

  DOI：10.1248/cpb.16.1417

  日期：——

  For the purpose of elucidating the structural relationship between lathyrism and inhibition of necrosis induced by CCl4 in the liver of the rat, many compounds related to aminoacetonitrile were synthesized. N-Aminoacylaminoacetonitriles (VIII, XIV) were synthesized from phthaloylaminoacylaminoacetonitriles. VIII were converted to 2-hydroxyimino-5-oxopiperazine derivatives (XV) and 5-oxo-2-thio-piperazines (XX). Preparations of N-(N-acylaminoacyl) aminoacetonitriles were also described. Further, N-α-hydroxyacylaminoacetonitriles were prepared from chloralides of α-hydroxyacids with aminoacetonitrile. In addition, XV (R=H) was converted to 2-acetamino-5-acetoxypyrazine by treatment with acetic anhydride.

  为了阐明贻贝症与四氯化碳诱导的大鼠肝脏坏死抑制之间的结构关系，合成了许多与氨基乙腈相关的化合物。N-氨基酰氨基乙腈（VIII，XIV）是从邻苯二甲酰氨基酰氨基乙腈合成的。VIII被转化为2-羟基亚胺-5-氧杂哌嗪衍生物（XV）和5-氧-2-硫杂哌嗪（XX）。还描述了N-(N-酰氨基酰)氨基乙腈的制备。此外，N-α-羟基酰氨基乙腈是由α-羟基酸的氯化物与氨基乙腈反应制备的。此外，通过用醋酸无水物处理，XV（R=H）被转化为2-乙酰氨基-5-乙酰氧基吡唑。
• 2-Substituted 4,5-dihydrothiazole-4-carboxylic acids are novel inhibitors of metallo-β-lactamases
  作者：Pinhong Chen、Lori B. Horton、Rose L. Mikulski、Lisheng Deng、Sandeep Sundriyal、Timothy Palzkill、Yongcheng Song

  DOI：10.1016/j.bmcl.2012.08.012

  日期：2012.10

  hospital-acquired, Gram-negative pathogens, poses a significant threat to public health. We report several 2-substituted 4,5-dihydrothiazole-4-carboxylic acids to be novel MBL inhibitors. Structure activity relationship (SAR) and molecular modeling studies were performed and implications for further inhibitor design are discussed.

  由 B 类金属β-内酰胺酶 (MBL) 引起的细菌对 β-内酰胺类抗生素的耐药性，特别是对某些医院获得性革兰氏阴性病原体，对公众健康构成重大威胁。我们报告了几种 2-取代 4,5-dihydrothiazole-4-羧酸是新型 MBL 抑制剂。进行了构效关系 (SAR) 和分子建模研究，并讨论了对进一步抑制剂设计的影响。
• Resonance Raman spectroscopic evidence for an intramolecular interaction involving the amide and dithioester groups of <i>N</i>-acyl glycine ethyl dithioesters
  作者：A. C. Storer、Y. Ozaki、P. R. Carey

  DOI：10.1139/v82-032

  日期：1982.1.15

  The synthesis and resonance Raman spectra of several new N-acyl glycine ethyl dithioesters RC(=O)NH—CH₂—C(=S)SR are reported. The resonance Raman spectra of these compounds contain at least two peaks in the "C=S stretching region" between 1050 and 1200 cm⁻¹. The solvent, concentration, temperature, and excitation wavelength dependencies of these features have been investigated. The results obtained are consistent with two conformations of the dithioesters co-existing in solution with the conformational differences being controlled by rotational isomerism about one or both of the NH—CH₂ and CH₂—CS bonds. Strong support for the existence of more than one conformer in solution comes from the Raman spectrum of a single crystal of N-acetyl glycine ethyl dithioester. In the spectrum of the single crystal several Raman bands are absent compared to the spectrum of the dithioester in solution indicating that only one of the conformers found in the solution phase is retained in the crystal. In one of the conformers found in solution there is evidence for an intramolecular interaction between the amide group and the dithioester group. The exact nature of the intramolecular interaction is uncertain, although simple H-bonding and enethiol tautomerism have been eliminated as possibilities. Possible contributors to the interaction are dipole–dipole forces and amide π-electrons interacting through space with sulfur d_x orbitals. Both of these putative interactions would be modulated by rotational isomerism. Based on deuterium substitution experiments a resonance Raman band is identified in the 1050–1200 cm⁻¹ region which contains a contribution from the motion of the amide proton. The unexpected intensity enhancement of an amide mode is attributed to the amide–dithioester intramolecular interaction. The conformer exhibiting the intramolecular interaction is thought to closely resemble the conformation of the substrate in the active site of certain dithioester enzyme–substrate complexes.

  报道了几种新的N-酰基甘氨酸乙基二硫酯RC(=O)NH—CH₂—C(=S)SR的合成和共振拉曼光谱。这些化合物的共振拉曼光谱在“C=S伸展区”（1050至1200 cm⁻¹）至少包含两个峰。已经研究了这些特征的溶剂、浓度、温度和激发波长的依赖性。所得结果表明，溶液中存在两种二硫酯的构象，其构象差异由NH—CH₂和CH₂—CS键的旋转异构体控制。从N-乙酰基甘氨酸乙基二硫酯的单晶拉曼光谱中得到了溶液中存在多个构象的强有力支持。在单晶的光谱中，与溶液中的二硫酯光谱相比，有几个拉曼带消失，表明晶体中仅保留了溶液相中的一个构象。在溶液中发现的一个构象中，有证据表明酰胺基团与二硫酯基团之间存在分子内相互作用。分子内相互作用的确切性质尚不确定，尽管简单的氢键和烯硫醇互变异构已被排除为可能性。对于相互作用的可能贡献者包括偶极–偶极力和酰胺π-电子通过空间与硫d_x轨道相互作用。这两种假定的相互作用都将受到旋转异构体的调节。基于氘取代实验，确定了在1050–1200 cm⁻¹区域内的一个共振拉曼带，其中包含酰胺质子运动的贡献。对酰胺模式意外强度增强归因于酰胺–二硫酯分子内相互作用。认为展现分子内相互作用的构象与某些二硫酯酶–底物复合物活性位点中的底物构象非常相似。