2-乙酰氧基-2-苯基乙酸乙酯 | 74327-04-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2-乙酰氧基-2-苯基乙酸乙酯
• 英文名称: ethyl (+/-)-O-acetylmandelate
• 英文别名: ethyl 2-acetoxy-2-phenylacetate；Ethyl (acetyloxy)(phenyl)acetate；ethyl 2-acetyloxy-2-phenylacetate
• CAS: 74327-04-1
• 化学式: C₁₂H₁₄O₄
• 分子量: 222.241
• InChiKey: VTVRQPAFUYRQQH-UHFFFAOYSA-N

物化性质

• 沸点：
  146-147 °C(Press: 13 Torr)
• 密度：
  1.133±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-乙酰氧基-2-苯基乙酸乙酯 在 盐酸 作用下， 反应 76.0h， 生成 D-扁桃酸
  参考文献：
  名称：

  通过相应乙酸盐的微生物不对称水解合成旋光炔醇和α-羟基酯

  摘要：

  枯草芽孢杆菌变种对消旋炔醇和α-羟基酯的乙酸酯的不对称水解。尼日尔提供了7–90％的光学纯度的旋光乙酸酯和醇。通过该微生物方法制备光学纯的扁桃酸的两种对映体。

  DOI：

  10.1016/0040-4020(80)85030-7
• 作为产物：
  描述：

  扁桃腈 在 吡啶 、 盐酸 、 4-二甲氨基吡啶 、 水 、 对甲苯磺酸 作用下， 以 1,4-二氧六环 、 二氯甲烷 、 甲苯 为溶剂， 反应 10.0h， 生成 2-乙酰氧基-2-苯基乙酸乙酯
  参考文献：
  名称：

  脂肪酶PS-30催化的立体选择性酰化反应对扁桃酸酯的动力学拆分

  摘要：

  通过使用脂肪酶PS-30作为催化剂，已通过立体选择性酰化反应实现了一系列外消旋扁桃酸酯的动力学拆分。动力学对映体比率（E）的值达到197.5。简要讨论了取代基的作用。

  DOI：

  10.1016/j.tetlet.2014.02.095

文献信息

• Synthesis of chiral α-aryl-α-hydroxyacetic acids: Substituent effects in pig liver acetone powder (PLAP) induced enantioselective hydrolysis
  作者：Deevi Basavaiah、Peddinti Rama Krishna

  DOI：10.1016/0040-4020(94)01105-9

  日期：1995.2

  Pig liver acetone powder (PLAP) catalyzed hydrolysis of alkyl α-acetoxy-α-arylacetates produces alkyl (S)-α-aryl-α-hydroxyacetates in 23–80% enantiomeric purities. Enantioselectivity is dependent on the ester group of O-acetylmandelates. Substitution on the aromatic ring results in inferior selectivities. Only acetate group is hydrolyzed by PLAP while the ester functionality is found to be completely

  猪肝脏丙酮粉（PLAP）烷基α乙酰氧基α-arylacetates的催化的水解产生烷基（小号） - α -芳基- α -hydroxyacetates在23-80％对映体纯度。对映选择性取决于O-乙酰扁桃酸酯的酯基。芳环上的取代导致较差的选择性。PLAP仅水解乙酸酯基团，而发现酯官能团是完全完整的。
• Urea-Induced Acid Amplification: A New Approach for Metal-Free Insertion Chemistry
  作者：Erica D. Couch、Tyler J. Auvil、Anita E. Mattson

  DOI：10.1002/chem.201403283

  日期：2014.7.1

  α‐aryldiazoacetates in high yield. This methodology was found to be generally applicable to a broad substrate scope and presents a conceptually new approach for organocatalytic diazo insertion reactions. Mechanistic investigations suggest that the reaction pathway involves a urea‐induced protonation of the α‐aryldiazoester.

  事实证明，增强二氟硼酸脲的催化活性对于提高酸度α-芳基重氮乙酸酯的无金属OH和SH插入反应而言是必不可少的。发现该方法通常适用于广泛的底物范围，并且提出了用于有机催化重氮插入反应的概念上新的方法。机理研究表明，该反应途径涉及尿素诱导的α-芳基重氮酯的质子化。
• Photochemical Reactions of Alkyl Phenylglyoxylates¹
  作者：Shengkui Hu、Douglas C. Neckers

  DOI：10.1021/jo960685e

  日期：1996.1.1

  isolated and identified in the reactions of ethyl phenylglyoxylate (1a) in benzene. Quantum yields and initial rate constants of product formation are shown to be concentration dependent. For the formation of carbonyl product 3 at lower starting material concentrations (<0.01 M), quantum yields greater than 1 are observed. Variations in the quantum yields as a function of reaction time are due to the accumulation

  在苯乙醛酸乙酯（1a）在苯中的反应中，分离并鉴定了三种新的光产物，O-苯甲酰扁桃酸乙酯（5a），O-乙酰扁桃酸乙酯（6a）和联苯三酮（7a）。量子产率和产物形成的初始速率常数显示为浓度依赖性。为了在较低的起始原料浓度（<0.01 M）下形成羰基产物3，观察到量子产率大于1。量子产率随反应时间的变化是由于α-羟苯基烯酮（D）的积累。比较了苯乙醛酸酯1和苯酮的三重激发态的相对反应性。提出了涉及分子内γ-H抽象和分子间H抽象的机制，其导致自由基链反应。
• INSECT REPELLENTS. I. ESTERS OF MANDELIC AND SUBSTITUTED MANDELIC ACIDS¹
  作者：W. F. BARTHEL、JOSE LEON、S. A. HALL

  DOI：10.1021/jo01369a001

  日期：1954.4
• Lipase activity of Lecitase® Ultra: characterization and applications in enantioselective reactions
  作者：Mithilesh Kumar Mishra、Thenkrishnan Kumaraguru、Gurrala Sheelu、Nitin W. Fadnavis

  DOI：10.1016/j.tetasy.2009.11.012

  日期：2009.12

  The general properties of Lecitase (R) Ultra, a phospholipase manufactured and marketed by Novozymes, Denmark, have been studied after purification by ultrafiltration. The enzyme has a molecular mass of 35 KD, pH-optimum of 8.5, and appears to possess a single active site which exhibits both the lipase and phospholipase activities that increase in the presence of Ca2+ and Mg2+ ions. The enzyme is inhibited by heavy metal ions and surfactants, and does not accept p-nitrophenyl acetate and glycerol triacetate. Substrates, such as glycerol tributyrate and p-nitrophenyl palmitate, esters of N-acetyl-alpha-amino acids and alpha-hydroxy acids are readily accepted. Amino acids with aliphatic residues, such as alanine, isoleucine, and methionine, are hydrolyzed with high enantioselectivity for the L-enantiomer (E > 100), but amino acids with aromatic residues such as phenylalanine and phenylglycine, and esters of alpha-hydroxy acids are hydrolyzed with low enantioselectivity (E = 1-5). Immobilization of the enzyme in a gelatin matrix (gelozyme) leads to a marginal improvement in the enantioselectivity for these substrates. However, a dramatic improvement in enantioselectivity is observed for ethyl 2-hydroxy-4-oxo-4-phenylbutyrate (E value increases from 4.5 to 19.5 with S-selectivity). Similarly, glycidate esters, such as ethyl trans-(+/-)-3-phenyl glycidate and methyl trans-(+/-)-3-(4-methoxyphenyl) glycidate, are selectively hydrolyzed with a remarkable selectivity towards the (2S,3R)-enantiomer providing unreacted (2R,3S)-glycidate esters (ee >99%, conversion 52-55%) by the immobilized enzyme. (C) 2009 Elsevier Ltd. All rights reserved.