4-nitrophenyl nicotinate | 24690-42-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚酯
• 英文名称: 4-nitrophenyl nicotinate
• 英文别名: p-Nitrophenyl nicotinate；(4-nitrophenyl) pyridine-3-carboxylate
• CAS: 24690-42-4
• 化学式: C₁₂H₈N₂O₄
• mdl: MFCD00434434
• 分子量: 244.207
• InChiKey: BRFXCDOSNZVQAQ-UHFFFAOYSA-N

物化性质

• 保留指数：
  2145

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  85
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4-nitrophenyl nicotinate 在 Zn(II) complex with N,N,N-tris<2-<((3-hydroxyphenyl)methyl)amino>ethyl>amine 作用下， 以 水 、 乙腈 为溶剂， 生成 对硝基苯酚
  参考文献：
  名称：

  Acceleration of p-Nitrophenyl Ester Cleavage by Zn(II)-Organized Molecular Receptors

  摘要：

  Tris(2-aminoethyl)amine (TREN) has been functionalized by introducing phenolic residues in the tripodal ligand side arms. The resulting functionalized ligands 1-5 form stable complexes with Zn(II) ions at pH > 6-6.5. The conformation of the Zn(II) complexes is such to form an ill-defined cavity with the metal ion occupying its bottom and the aromatic residues defining its hydrophobic walls. In these Zn(II) complexes one of the phenolic hydroxyls is, depending on the structure of the ligand, up to 1.3 pK(a) units more acidic than that of phenol itself. This enhanced acidity is attributed to second sphere coordination to the metal center. The complexes, particularly 1 . Zn(II), behave as molecular receptors of p-nitrophenyl esters of carboxylic acids with binding constants greater than or equal to 300 M-1 for those substrates capable of coordination to the Zn(II) ion (p-nitrophenyl nicotinate, PNPN, p-nitrophenyl isonicotinate, PNPIN and p-nitrophenyl urocanoate, PNPU). At pH 8.3 they also accelerate the cleavage of these esters with rate accelerations with respect to the uncatalyzed: hydrolysis of up to 60 times, depending on the structure of the substrate. The kinetic analysis of the process shows that the rate effects are due to two independent mechanisms: a bimolecular process that does not comprise binding of the substrate and a pseudointramolecular process within the supramolecular complex made of ligand, metal ion, and substrate. In both cases the nucleophile is one of the phenolic hydroxyls of the functionalized side arms of the TREN-based complex which, in the first step, is acylated by the substrate and eventually slowly hydrolyzes turning over the catalyst. Determination of second-order rate constants shows that the nucleophilicity of the phenolic hydroxyls is higher than that of a substituted phenol of the same pK(a). Comparison of the metalloreceptor 1 . Zn(II) with cyclodextrins allowed one to highlight similarity and differences between the two receptors.

  DOI：

  10.1021/jo970783f
• 作为产物：
  描述：

  烟酸 、 对硝基苯基氯甲酸酯 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 4-nitrophenyl nicotinate
  参考文献：
  名称：

  Pd-Catalyzed Decarbonylative Olefination of Aryl Esters: Towards a Waste-Free Heck Reaction

  摘要：

  DOI：

  10.1002/1521-3773(20020402)41:7<1237::aid-anie1237>3.0.co;2-f

文献信息

• Polymerization- and Solvent-Triggered Cooperativity Between Copper(II) Ions in the Catalysis of the Hydrolysis of Amino Esters by Pyridine-Based Ligands
  作者：Paolo Scrimin、Paolo Tecilla、Umberto Tonellato

  DOI：10.1002/(sici)1099-0690(199806)1998:6<1143::aid-ejoc1143>3.0.co;2-u

  日期：1998.6

  Polymeric (2) and oligomeric (4, 5) materials made of repeating units of 2,6-diaminomethylpyridine and 4,4′-diphenylmethane have been synthesized with the number of monomeric units (n) ranging from 2 to 29. In 1:1 DMSO/water solutions, these materials are fully soluble and strongly bind CuII ions. The complexes catalyze to different extents the hydrolysis of the p-nitrophenyl esters of α-, β-, and γ-amino acids

  聚合物（2）和低聚（4，5）由2,6- diaminomethylpyridine和4,4'-二苯基甲烷的重复单元的原料已经合成了与单体单元的数量（Ñ范围从2到29。1）： 1 DMSO /水溶液，这些材料是完全可溶的，并与Cu II离子牢固结合。该络合物在不同程度上催化α-，β-和γ-氨基酸的对硝基苯基酯的水解。仅利用Cu II的聚合物络合物2（Ñ ≥10）是更有效的催化剂比游离的Cu II离子在β-氨基酯的裂解中。当与单体配体（N，N'-苄基）-的Cu II配合物进行比较时，这种增强的反应性在β-丙氨酸对硝基苯酯（β-AlaPNP）的情况下几乎达到两个数量级。仅当达到一定聚合度时（6 < n <10），才在1：1（v / v）DMSO / H 2 O中观察到2,6-氨基甲基吡啶（3）。在1：1（v / v）CH 3 CH 2 OH / H 2 O中，聚合物2（n = 10）的配合物的动力学益处在9：1（v
• Transfer of a positively charged acyl group between substituted phenolate ion nucleophiles: the brønsted β for the calibrating equilibrium for N-methylisonicotinyl (4-carbonyl-N-methylpyridinium) transfer
  作者：Matthew J. Colthurst、Matilde Nanni、Andrew Williams

  DOI：10.1039/p29960002285

  日期：——

  measured for the reaction of substituted phenolate ions with aryl acetate esters and with aryl N-methylisonicotinate esters in aqueous solution. A new method is demonstrated for determining βeq for group transfer from 4-nitrophenyl esters; it employs the rate constant for the reaction of 2,6-difluorophenolate ion with substituted phenyl ester as a surrogate for the reactivity of the 4-nitrophenolate ion

  已经测量了在水溶液中取代酚盐离子与乙酸芳基酯和与芳基N-甲基异烟酸酯的反应的速率常数。一种新方法被证明用于确定β当量从4-硝基苯基酯基转移; 它采用的速率常数的反应2,6- difluorophenolate离子取代的苯基酯作为4-硝基苯酚盐离子和产量的反应性的替代β当量= 1.55为Ñ -methylisonicotinyl转移反应。苯甲酸根离子对4-硝基苯基N-甲基异烟酸根酸酯的进攻速率常数的布朗斯台德图在p K a范围内是线性的值从5.5到10，并为该反应的协调位移机制提供了很好的证据。所述的反应性Ñ -methylisonicotinate酯酚离子是比相应的乙酸酯的大约300次，但较大的β NUC值（0.90与0.74比较）提出了一种“后面”过渡结构。所述的校准β与对应的值β当量给出莱弗勒α NUC为= 0.58和0.42 Ñ -methylisonicotinate和乙酸分别，与
• Cosmetic composition
  申请人：UNILEVER PLC

  公开号：EP0489581A2

  公开（公告）日：1992-06-10

  Compositions containing an ester of nicotinic acid and a cosmetically acceptable surfactant are provided. These compositions, when applied topically to the human body produce a response such as a sensory or therapeutic response, for example a tingling or warming sensation or an increase in blood flow, which persists after the composition is rinsed from the body. The compositions are particularly suitable for application to the hair and/or scalp where they may encourage hair growth. Compositions for application to the hair and/or scalp preferably additionally comprise hair benefit agents such as hair growth promoters.

  提供含有烟酸酯和化妆品可接受的表面活性剂的组合物。这些组合物在局部涂抹到人体时会产生一种感官或治疗反应，例如刺痛或温热感觉，或者增加血液流动，这种反应在组合物被冲洗后仍然持续。这些组合物特别适用于涂抹到头发和/或头皮，可以促进头发生长。用于涂抹到头发和/或头皮的组合物最好还包括头发益处剂，如促进头发生长的剂。
• Kinetic Study on Aminolysis of 4-Nitrophenyl Nicotinate and Isonicotinate: Factors Influencing Reactivity and Reaction Mechanism
  作者：Min-Young Kim、Minah Shin、Ik-Hwan Um

  DOI：10.5012/bkcs.2014.35.8.2443

  日期：2014.8.20

  A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl nicotinate (7) and 4nitrophenyl isonicotinate (8) with a series of cyclic secondary amines in H2O containing 20 mol % DMSO at 25.0 o C. The Bronted-type plots for the reactions of 7 and 8 are linear with βnuc = 0.90 and 0.92, respectively, indicating that the reactions proceed through a stepwise mechanism with expulsion

  对 4-硝基苯基烟酸酯 (7) 和 4-硝基苯基异烟酸酯 (8) 与一系列环状仲胺在含有 20 mol % DMSO 的 H2O 中在 25.0 o C 的亲核取代反应进行了动力学研究。反应的 Bronted 型图7 和 8 分别与 βnuc = 0.90 和 0.92 呈线性关系，表明反应通过逐步机制进行，离去基团的排出发生在速率决定步骤中。将 7 和 8 的反应性与苯甲酸 4-硝基苯酯 (2a) 和 4-硝基苯基吡啶甲酸酯 (6) 的反应性进行比较表明，它们对胺的反应性按 2a < 7 < 8 < 6 的顺序增加，尽管这些底物通过相同的机制进行。已经详细讨论了控制反应性和反应机理的因素（例如，
• Carbene-Catalyzed Alkylation of Carboxylic Esters via Direct Photoexcitation of Acyl Azolium Intermediates
  作者：Shi-Chao Ren、Wen-Xin Lv、Xing Yang、Jia-Lei Yan、Jun Xu、Fang-Xin Wang、Lin Hao、Huifang Chai、Zhichao Jin、Yonggui Robin Chi

  DOI：10.1021/acscatal.1c00165

  日期：2021.3.5

  A carbene-catalyzed reductive coupling reaction of carboxylic esters and substituted Hantzsch esters is disclosed. Key steps of this reaction include one-electron reduction of a carbene catalyst-bound acyl azolium intermediate to generate the corresponding radical intermediate for subsequent alkylation reactions. The reaction is promoted by irradiation with visible light without the involvement of

  公开了羧酸酯和取代的汉茨tz酯的卡宾催化的还原偶联反应。该反应的关键步骤包括单电子还原卡宾催化剂所结合的酰基偶氮中间体，以产生相应的自由基中间体用于随后的烷基化反应。在不涉及过渡金属光催化剂的情况下，通过可见光照射可促进反应。机理研究表明，原位形成的酰基偶氮鎓中间体的直接光激发可能是这种光诱导的单电子还原过程的原因。光激发将酰基偶氮中间体转化为单电子氧化剂，从而使Hantzsch酯进行单电子氧化以生成自由基中间体。我们的反应适用于各种芳基羧酸酯和Hantzsch酯底物。可以使用我们的方法，通过非常温和的条件（可以耐受各种官能团）将复杂的结构（包括药物中存在的结构）并入酮分子中。