phenyl 4-ethylbenzoate

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 缩酚酸和缩酚酸环醚类
• 英文名称: phenyl 4-ethylbenzoate
• 英文别名: 4-Ethylbenzoic acid, phenyl ester
• 化学式: C₁₅H₁₄O₂
• 分子量: 226.275
• InChiKey: SWEBJXGMDBTYKX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  4-氯苯甲酸苯酯 、 乙基氯化镁 在 1,3-二甲基-2-咪唑啉酮 、 iron(III)-acetylacetonate 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以63%的产率得到phenyl 4-ethylbenzoate
  参考文献：
  名称：

  氯苯甲酸芳基酯与烷基格氏试剂的铁催化 C(sp2)–C(sp3) 交叉偶联

  摘要：

  苯甲酸芳基酯是有机合成中非常重要的化合物。在此，我们报告了铁催化的氯苯甲酸芳基酯与烷基格氏试剂的 C(sp2)–C(sp3) Kumada 交叉偶联。该方法的特点是使用环境友好且可持续的铁盐在催化系统中进行交叉偶联，使用良性尿素配体代替生殖毒性 NMP（NMP = N-甲基-2-吡咯烷酮）。值得注意的是，在存在水解不稳定且易于亲核加成酚酯 C(酰基)-O 键的情况下实现了交叉偶联的高选择性。该反应提供了获得烷基官能化苯甲酸芳基酯的途径。对各种 O 配位配体的检查表明，尿素配体在促进交叉偶联与酯 C（酰基）-O 键的亲核加成方面具有高活性。

  DOI：

  10.3390/molecules25010230

文献信息

• Transition‐Metal‐Free DMAP‐Mediated Aromatic Esterification of Amides with Organoboronic Acids
  作者：Tao Wang、Yanqing Wang、Kai Xu、Yuheng Zhang、Jiarui Guo、Lantao Liu

  DOI：10.1002/ejoc.202100478

  日期：2021.6.14

  A new, transition-metal-free, effective method for aromatic esterification of amides with organoboronic acids has been developed, leading to a wide range of benzoate derivatives with yields ranging from moderate to good. The catalytic reaction shows broad substrate scope and excellent functional group tolerance.

  已经开发出一种新的、不含过渡金属的、有效的酰胺与有机硼酸的芳族酯化方法，产生了范围广泛的苯甲酸酯衍生物，产率从中等到良好。该催化反应显示出广泛的底物范围和优异的官能团耐受性。
• N-Heterocyclic carbene catalysed aerobic oxidation of aromatic aldehydes to aryl esters using boronic acids
  作者：Panjab Arde、B. T. Ramanjaneyulu、Virsinha Reddy、Apurv Saxena、R. Vijaya Anand

  DOI：10.1039/c1ob06566a

  日期：——

  The organocatalytic behavior of N-heterocyclic carbenes in the aerobic oxidation of aromatic aldehydes to esters with boronic acids has been explored. This transition metal-free protocol allows access to a wide variety of aromatic esters in good to excellent yields under mild reaction conditions.

  研究了N-杂环卡宾在芳香醛与硼酸的好氧氧化为酯反应中的有机催化行为。这种无过渡金属的方法可以在温和的反应条件下以良好的产率获得各种芳族酯。
• Direct Esterification of Aromatic Aldehydes with Tetraphenylphosphonium Bromide under Oxidative N-Heterocyclic Carbene Catalysis
  作者：Bandaru T. Ramanjaneyulu、Manish Pareek、Virsinha Reddy、R. Vijaya Anand

  DOI：10.1002/hlca.201300369

  日期：2014.3

  An unconventional reagent, tetraphenylphosphonium bromide, was employed as a phenyl source in the direct transformation of aromatic aldehydes to the corresponding phenyl esters under oxidative N‐heterocyclic carbene (NHC) catalysis. The phenyl esters were obtained in moderate yields under mild and organocatalytic conditions.

  在氧化N-杂环卡宾（NHC）催化下，芳香族醛直接转化为相应的苯基酯时，使用了非常规试剂溴化四苯基phosph作为苯基源。在温和的有机催化条件下，以中等收率获得了苯基酯。
• Palladium-catalyzed alkoxycarbonylation of aryl halides with phenols employing formic acid as the CO source
  作者：Xinxin Qi、Chong-Liang Li、Li-Bing Jiang、Wan-Quan Zhang、Xiao-Feng Wu

  DOI：10.1039/c5cy01957e

  日期：——

  An efficient palladium-catalyzed alkoxycarbonylation of aryl halides with phenols has been developed. Various aryl benzoates have been isolated in good to excellent yields with formic acid as the CO source.

  已开发出一种高效的钯催化的醚羰基化反应，用苯酚与芳基卤化物反应。在以甲酸为CO源的条件下，得到了各种芳基苯甲酸酯，收率良好至优异。
• Substituent Effects on the Base-Catalysed Hydrolysis of Phenyl Esters of para-Substituted Benzoic Acids
  作者：Ingrid Bauerová、Miroslav Ludwig

  DOI：10.1135/cccc20001777

  日期：——

  Seventeen model phenyl esters of 4-substituted benzoic acids were synthesised by the reaction of substituted benzoyl chlorides with phenol in aqueous alkaline solutions (Schotten-Baumann reaction), in pyridine (Einhorn reaction), or by the reaction of substituted benzoic acids with phosphorus oxychloride. Structures and purity of the model compounds were confirmed by ¹H NMR and ¹³C NMR spectroscopy as well as by HPLC and elemental analysis. Phenyl 4-aminobenzoate was synthesised by reduction of phenyl 4-nitrobenzoate in methanol on palladium. Kinetics of base-catalysed hydrolysis of model phenyl esters occurring by the B_Ac2 mechanism were measured by UV spectrophotometry in 50% (v/v) aqueous dimethyl sulfoxide solutions at 25 °C under pseudo-first-order conditions, (c[NaOH] = 0.001-1.0 mol l^-1). The addition of OH^- to phenyl benzoates was used to establish the kinetic J_-^E acidity scale. Linear relation between J_-^E and log k_obs with the slope near unity was found for all the model compounds. The kinetic constants of hydrolysis of phenyl esters of 4-substituted benzoic acids precisely obey the Hammett relationship (σ_p) with ρ = 2.44. Quantitatively comparable results have been obtained by application of Alternative Interpretation of Substituent Effects theory (AISE) using the σⁱ set of substituent constants.

  4-取代苯甲酸的17种模型苯酯通过取代苯甲酰氯与酚在水性碱性溶液中（Schotten-Baumann反应），在吡啶中（Einhorn反应），或通过取代苯甲酸与氯化亚磷酸反应合成。模型化合物的结构和纯度通过¹H NMR和¹³C NMR光谱以及HPLC和元素分析得到确认。苯基4-氨基苯甲酸是通过在钯上在甲醇中还原苯基4-硝基苯甲酸合成的。在25°C下，通过伪一级条件（c[NaOH] = 0.001-1.0 mol l^-1）在50%（体积比）水性二甲基亚砜溶液中，利用UV分光光度法测量了发生B_Ac2机制的模型苯酯的碱催化水解动力学。将OH^-加入苯基苯甲酸酯以建立动力学J_-^E酸度标度。对于所有模型化合物，发现了J_-^E与log k_obs之间的线性关系，斜率接近于单位。4-取代苯甲酸酯的水解动力学常数精确遵守Hammett关系（σ_p），ρ = 2.44。使用σⁱ取代基常数集合，通过应用替代取代基效应理论（AISE），获得了定量可比较的结果。