p-nitrophenyl cyclohexanecarboxylate | 13551-17-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚酯
• 英文名称: p-nitrophenyl cyclohexanecarboxylate
• 英文别名: (4-nitrophenyl) cyclohexanecarboxylate
• CAS: 13551-17-2
• 化学式: C₁₃H₁₅NO₄
• 分子量: 249.266
• InChiKey: UCQFTYKBLBJWIO-UHFFFAOYSA-N

物化性质

• 沸点：
  384.7±25.0 °C(Predicted)
• 密度：
  1.237±0.06 g/cm3(Predicted)
• 保留指数：
  2023

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  72.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  p-nitrophenyl cyclohexanecarboxylate 在 4-二甲氨基吡啶 、 Bacillus subtilis 168 SrfAD esterase 、 N,N'-二环己基碳二亚胺 作用下， 以 二甲基亚砜 为溶剂， 反应 16.1h， 生成 4-硝基苯基乙酸酯
  参考文献：
  名称：

  Fingerprint lipolytic enzymes with chromogenic p-nitrophenyl esters of structurally diverse carboxylic acids

  摘要：

  A series of structurally diverse chromogenic esters, including a new compound (4-nitrophenyl 2-methylpentanoate), has been synthesized, constituting an array of 17 substrates which could be applied to rapidly fingerprint the activity of lipases or esterases to reveal their substrates specificity and functional characteristics. Combined with genetic technology such as "data mining" and directed evolution, such fingerprints might be a promising platform for discovery of potentially useful enzymes in industrial application. The fingerprint of commercially available Lipase-B from Candida antarctica as a model enzyme was first measured to confirm the reliability of this method. Then three new enzymes mined from genomic libraries were successfully fingerprinted, revealing the functional characteristics of those enzymes. Among them, the enzyme SrfAD was founded with specific substrate preference towards cycloalkyl carboxylic esters and aromatic esters, making it more promising in synthetic utilities than other tested enzymes. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcatb.2011.07.010
• 作为产物：
  描述：

  4-硝基苯基硬脂酸酯 在 4-二甲氨基吡啶 、 Candida antarctica lipase B 、 Bacillus subtilis 168 SrfAD esterase 、 N,N'-二环己基碳二亚胺 作用下， 以 二甲基亚砜 为溶剂， 反应 72.45h， 生成 p-nitrophenyl cyclohexanecarboxylate
  参考文献：
  名称：

  Fingerprint lipolytic enzymes with chromogenic p-nitrophenyl esters of structurally diverse carboxylic acids

  摘要：

  A series of structurally diverse chromogenic esters, including a new compound (4-nitrophenyl 2-methylpentanoate), has been synthesized, constituting an array of 17 substrates which could be applied to rapidly fingerprint the activity of lipases or esterases to reveal their substrates specificity and functional characteristics. Combined with genetic technology such as "data mining" and directed evolution, such fingerprints might be a promising platform for discovery of potentially useful enzymes in industrial application. The fingerprint of commercially available Lipase-B from Candida antarctica as a model enzyme was first measured to confirm the reliability of this method. Then three new enzymes mined from genomic libraries were successfully fingerprinted, revealing the functional characteristics of those enzymes. Among them, the enzyme SrfAD was founded with specific substrate preference towards cycloalkyl carboxylic esters and aromatic esters, making it more promising in synthetic utilities than other tested enzymes. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcatb.2011.07.010

文献信息

• Visible‐Light Catalyzed [1+2+2] Cycloaddition Reactions Enabled by the Formation of Methylene Nitrones
  作者：Jing Guo、Ying Xie、Wen‐Tian Zeng、Qiao‐Lei Wu、Jiang Weng、Gui Lu

  DOI：10.1002/adsc.202000858

  日期：2020.12.8

  Nitrones are key intermediates in organic synthesis. Herein, we report the first photo‐redox synthesis of methylene nitrone intermediates from nitroarenes and arylamines. The highly reactive methylene nitrones are in situ trapped by alkenes to afford various isoxazolidines. This three‐component reaction features the use of N,N‐dimethylanilines or N‐aryl glycines as C1 building blocks, which allow for

  硝基是有机合成中的关键中间体。本文中，我们报道了由硝基芳烃和芳基胺进行的光催化还原亚甲基中间体中间体。高反应性的亚甲基硝基酮被烯烃原位捕获，得到各种异恶唑烷。此三组分反应的特征是使用N，N-二甲基苯胺或N-芳基甘氨酸作为C1结构单元，可从简单的起始原料进行一锅形式的正式[1 + 2 + 2]环加成。在温和的条件下，可以以中等至良好的收率获得各种有用的异恶唑烷。机理研究支持通过选择性的N-CH 3键裂解和亚甲基转移形成亚甲基硝酮。
• An Efficient Catalytic Amidation of Esters Promoted by N-Heterocyclic Carbenes
  作者：Ling-Yan Chen、Mei-Fang Wu

  DOI：10.1055/s-0037-1610355

  日期：2019.4

  amidation between esters and amines or hydrazines is described. This strategy was tolerant for a wide scope of substrates, affording a series of amides (or hydrazides) in good to excellent yields (60–96%) under simple conditions. The approach was also used to synthesize the pharmaceutically relevant antidepressant moclobemide in 85% yield. An efficient NHC-catalyzed amidation between esters and amines or

  摘要 描述了酯和胺或肼之间的有效的NHC催化的酰胺化。该策略可耐受多种底物，在简单条件下可提供一系列酰胺（或酰肼），收率好至极好（60-96％）。该方法还用于以85％的产率合成药学上相关的抗抑郁药莫氯贝米。 描述了酯和胺或肼之间的有效的NHC催化的酰胺化。该策略可耐受多种底物，在简单条件下可提供一系列酰胺（或酰肼），收率好至极好（60-96％）。该方法还用于以85％的产率合成药学上相关的抗抑郁药莫氯贝米。
• A Macrocyclic Enzyme Model System. Deacylation of<i>p</i>-Nitrophenyl Carboxylates as Effected by a [20]Paracyclophane Bearing an Imidazole Group
  作者：Yukito Murakami、Yasuhiro Aoyama、Masaaki Kida、Akio Nakano

  DOI：10.1246/bcsj.50.3365

  日期：1977.12

  The kinetic effect of a [20]paracyclophane bearing an imidazole moiety (1) on the deacylation of various p-nitrophenyl carboxylates was investigated in 10.9% (v/v) ethanol-1.0%(v/v) dioxane-water of μ 0.10 (KCl) at 40.0±0.1 °C. The facile reaction of 1 with a hydrophobic ester resulted in the accumulation of the NIm-acyl derivative of 1 along the progress of reaction, and the rate of regeneration of

  在 μ 0.10 的 10.9% (v/v) 乙醇-1.0%(v/v) 二恶烷-水中研究了带有咪唑部分 (1) 的 [20] 对环烷对各种对硝基苯基羧酸盐脱酰的动力学影响(KCl) 在 40.0±0.1 °C。1 与疏水酯的轻松反应导致 1 的 NIm-酰基衍生物随着反应的进行而积累，并且与相应的酰化速率相比，在当前实验条件下 1 的再生速率（转化率）可以忽略不计. 在 1 存在下带有疏水酰基部分的对硝基苯基羧酸酯的脱酰基反应的总体特征与涉及 1 的单体和聚集形式与底物酯反应的反应方案一致。
• Catalytic Efficiency of Synthetic Micellar Catalysts Bearing a Mercapto Group as the Reaction Center
  作者：Yukito Murakami、Akio Nakano、Kiyoshi Matsumoto

  DOI：10.1246/bcsj.52.2996

  日期：1979.10

  In order to obtain a clue to understanding the micro-environmental effect on the reactivity of a mercapto group placed in a reaction center of enzymes, micellar surfactants bearing a mercapto group were synthesized and their catalytic activity in the degradation of p-nitrophenyl carboxylates was studied. N-Hexadecyl-Nα-glutaryl-l-cysteinamide (AM·Cys-1) has an ability to form anionic micelles in aqueous media. The catalytic activity of AM·-Cys-1 was compared with that of another synthetic surfactant, N-hexadecanoyl-l-cysteine (AM·Cys-2). These surfactants below their critical micelle concentrations markedly accelerated the degradation of several p-nitrophenyl carboxylates. On the contrary, the concentration - rate profiles for the degradation of p-nitrophenyl dodecanoate (PNPL) as catalyzed by the surfactants indicate that the reactivity of the mercapto group is reduced upon formation of the anionic micelles. The large rate retardation is primarily due to the decrease in concentration of the active thiolate anion. This was supported by the fact that the pKa values for mercapto groups of the anionic micelles, for which the carboxyl group acts as an anionic head, were increased by 0.8–1.6 pKa unit over those of the corresponding monomeric surfactants in the bulk phase. These surfactants showed profound reactivity even in a neutral pH region when mixed with cationic CTAB micelle. The electrostatic field effect provided by the cationic head of CTAB micelle seems to enhance the nucleophilicity of the mercapto group in the mixed micelles.

  为了获得线索以理解微环境对放置在酶反应中心的巯基反应性的影响，合成了带有巯基的胶束表面活性剂，并研究了它们在降解对硝基苯基羧酸酯中的催化活性。N-十六烷基-Nα-谷酰基-L-半胱氨酸酰胺（AM·Cys-1）具有在水相介质中形成阴离子胶束的能力。将AM·Cys-1的催化活性与另一种合成表面活性剂N-十六酰基-L-半胱氨酸（AM·Cys-2）进行了比较。这些表面活性剂在其临界胶束浓度以下显著加速了几种对硝基苯基羧酸酯的降解。相反，由表面活性剂催化的对硝基苯基十二酸酯（PNPL）降解的浓度-速率关系显示，巯基反应性在形成阴离子胶束后减弱。速率显著减缓主要是由于活性硫酰阴离子浓度的降低。这一点得到了支持，因阴离子胶束的巯基的pKa值（羧基作为阴离子头）比相应的单体表面活性剂在体相中的pKa值增加了0.8-1.6个pKa单位。这些表面活性剂在与阳离子CTAB胶束混合时，即使在中性pH区间也表现出了显著的反应性。CTAB胶束的阳离子头所提供的静电场效应似乎增强了混合胶束中巯基的亲核性。
• Macrocyclic Enzyme Model Systems. Catalytic Activity of Cyclic Peptides Involving Hydrophobic Segments
  作者：Yukito Murakami、Akio Nakano、Kiyoshi Matsumoto、Kiyoshi Iwamoto

  DOI：10.1246/bcsj.51.2690

  日期：1978.9

  In order to develop an effective hydrolase model, BCP-1 was synthesized and its kinetic behavior investigated. The corresponding linear hexapeptide was prepared by the solid phase method and subjected to cyclization by the azide method. BCP-1 enhanced the hydrolysis of p-nitrophenyl carboxylates bearing a long alkyl chain. The pH-rate profile for the hydrolysis of p-nitrophenyl hexadecanoate (PNPP)

  为了开发有效的水解酶模型，合成了 BCP-1 并研究了其动力学行为。通过固相法制备相应的线性六肽并通过叠氮化物法进行环化。BCP-1 增强了带有长烷基链的对硝基苯基羧酸盐的水解。受 BCP-1 影响的十六酸对硝基苯酯 (PNPP) 水解的 pH 速率曲线不是钟形而是 sigmoid，由此估计动力学 pKa 值为 12.3。发现初始反应速率在一定范围的底物浓度（饱和型动力学）后趋于平稳，动力学数据基于 Michaelis-Menten 方案进行分析。BCP-1 对 PNPP (Km(app) \simeq10−6M) 的大疏水结合能力归因于其双层双环结构。取代的十六烷酸苯基酯水解的哈米特图给出了令人满意的线性相关性。因此，从绑定的酰基转移...