ethyl α-cyano-α-hydroxyphenylacetate | 147506-75-0

• 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: ethyl α-cyano-α-hydroxyphenylacetate
• 英文别名: ethyl 2-cyano-2-hydroxy-2-phenylacetate；Carbethoxymandelonitrile
• CAS: 147506-75-0；131221-75-5
• 化学式: C₁₁H₁₁NO₃
• 分子量: 205.213
• InChiKey: BBRGQMMBDKYDDJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  70.3
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl α-cyano-α-hydroxyphenylacetate 在 2,6-二甲基吡啶 、 silver nitrate 作用下， 以 乙醇 为溶剂， 反应 0.67h， 生成 苯甲酰甲酸乙酯
  参考文献：
  名称：

  Babler, James H.; Marcuccilli, Charles J.; Oblong, John E., Synthetic Communications, 1990, vol. 20, # 12, p. 1831 - 1836

  摘要：

  DOI：
• 作为产物：
  描述：

  苯甲酰甲酸 在 硫酸 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 生成 ethyl α-cyano-α-hydroxyphenylacetate
  参考文献：
  名称：

  Chemistry of novel compounds with multifunctional carbon structure. 9. Molecular design, synthetic studies, and NMR investigation of several efficient chiral derivatizing reagents which give very large 19F NMR .DELTA..delta. values in enantiomeric excess determination

  摘要：

  In order to develop efficient ee-determining reagents potentially superior to MTPA (1), some multifunctional compounds 2-5 were rationally designed. From NMR investigations of the analogous diastereomeric derivatives it was found that the chemical shift differences for each pair of diastereomers (DELTAdelta values) for CFPA derivatives 5d-f were approximately five times greater in F-19 NMR spectra and two times greater in H-1 NMR spectra than those of 1d-f. Synthesis of the optically pure CFPA, (-)-5a and (+)-5a, was achieved by nitrosation of each diastereomer of the optically active N-(1-phenylethyl)amides, 5f(M) and 5f(L), followed by thermal decomposition. Various derivatives were prepared by the condensation of 5b and lb with alcohol and amine nucleophiles, and both DELTAdelta(F) and DELTAdelta(H) Values were obtained for each compound. The CFPA derivatives 5d-m have proven to be significantly superior for ee determinations when compared to the corresponding MTPA derivatives 1d-m, particularly in compounds having remotely disposed chiral centers.

  DOI：

  10.1021/jo00059a036

文献信息

• “On Water” Nucleophilic Addition of Formaldehyde N,N-Dialkylhydrazones to α-Keto Esters
  作者：Ana Crespo-Peña、Eloísa Martín-Zamora、Rosario Fernández、José M. Lassaletta

  DOI：10.1002/asia.201100174

  日期：2011.9.5

  Water solves the problem: The use of pure water as the reaction mixture is key for the nucleophilic addition of formaldehyde hydrazones to α‐keto esters, leading to highly functionalized carbinols in high yields and short reaction times. The need for heterogeneous conditions and the observed solvent kinetic isotope effect are in agreement with the proposed “on water” activation.

  水解决了问题：使用纯水作为反应混合物是甲醛与α-酮酯进行亲核加成反应的关键，从而可以以高收率和较短的反应时间生产高度官能化的甲醇。对非均质条件的需求和观察到的溶剂动力学同位素效应与提议的“水上”活化相一致。
• BABLER, JAMES H.;MARCUCCILLI, CHARLES J.;OBLONG, JOHN E., SYNTH. COMMUN., 20,(1990) N2, C. 1831-1836
  作者：BABLER, JAMES H.、MARCUCCILLI, CHARLES J.、OBLONG, JOHN E.

  DOI：——

  日期：——