4-nitrophenyl phosphate | 29314-29-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 英文名称: 4-nitrophenyl phosphate
• 英文别名: p-nitrophenyl phosphate；p-nitrophenylphosphate；pNPP；NPP；phosphoric acid mono-(4-nitro-phenyl ester); deprotonated form；(4-Nitrophenyl) hydrogen phosphate
• CAS: 29314-29-2
• 化学式: C₆H₅NO₆P
• 分子量: 218.083
• InChiKey: XZKIHKMTEMTJQX-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  115
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4-nitrophenyl phosphate 在 erythro-1-phenyl-1,2-dibromopropylphosphonate 、 N,N-二异丙基乙胺 作用下， 以 乙腈 为溶剂， 反应 1.0h， 以35%的产率得到4-nitrophenyl pyrophosphate dianion salt
  参考文献：
  名称：

  Reactions of the monomeric metaphosphate anion generated from different sources

  摘要：

  DOI：

  10.1021/ja00369a033
• 作为产物：
  描述：

  4-硝基苯二氯化磷 以 四氢呋喃 、 水 为溶剂， 反应 0.17h， 生成 4-nitrophenyl phosphate 、 4-nitrophenyl phosphorochloridate anion
  参考文献：
  名称：

  碱性过氧化氢裂解磷酸双 (4-硝基苯基) 和 4-硝基苯基氯代磷酸盐中的意外化学计量

  摘要：

  碱性过氧化氢与双（4-硝基苯基）磷酸根离子的反应同时释放出 ca 2 equiv。每摩尔底物含有 4-硝基苯酚，没有证据表明中间体形成。HO2- 与活性更高的 4-硝基苯基氯代磷酸酯反应得到 4-硝基苯酚，产率高达 40%，一级动力学简单，没有长寿命中间体的迹象。提出了在最初形成的 4-硝基苯基过氧磷酸盐中通过过氧化物对 4-硝基苯酚离子进行快速分子内亲核置换来解释这种行为。版权所有 © 2000 John Wiley & Sons, Ltd.

  DOI：

  10.1002/1099-1395(200009)13:9<505::aid-poc277>3.0.co;2-n

文献信息

• Structural Flexibility Enhances the Reactivity of the Bioremediator Glycerophosphodiesterase by Fine-Tuning Its Mechanism of Hydrolysis
  作者：Kieran S. Hadler、Nataša Mitić、Fernanda Ely、Graeme R. Hanson、Lawrence R Gahan、James A. Larrabee、David L. Ollis、Gerhard Schenk

  DOI：10.1021/ja903534f

  日期：2009.8.26

  recent attention due to its potential in bioremediation. Formation of a catalytically competent binuclear center is promoted by the substrate (Hadler et al. J. Am. Chem. Soc. 2008, 130, 14129). Using the paramagnetic properties of Mn(II), we estimated the K(d) values for the metal ions in the alpha and beta sites to be 29 and 344 microM, respectively, in the absence of a substrate analogue. In its presence

  产气肠杆菌的甘油磷酸二酯酶 (GpdQ) 属于双核金属水解酶家族，由于其在生物修复方面的潜力，最近引起了人们的关注。底物促进催化能力双核中心的形成（Hadler et al. J. Am. Chem. Soc. 2008, 130, 14129）。使用顺磁性的 Mn(II)，我们估计 alpha 和 beta 站点中金属离子的 K(d) 值分别为 29 和 344 microM，在没有基质类似物的情况下。在其存在下，beta 站点的亲和力大大增加（K(d) = 56 microM），而alpha 站点的亲和力并没有受到很大影响（K(d) = 17 microM）。停流荧光测量确定了催化转化的三个不同阶段，与底物与活性位点的初始结合 (k(obs1))、催化活性双核中心的组装 (k(obs2)) 以及随后较慢的结构重排以优化催化作用 (k(obs3)) 相关。这三个阶段取决于底物 ([S])
• A calix[4]arene with acylguanidine units as an efficient catalyst for phosphodiester bond cleavage in RNA and DNA model compounds
  作者：Riccardo Salvio、Stefano Volpi、Tommaso Folcarelli、Alessandro Casnati、Roberta Cacciapaglia

  DOI：10.1039/c9ob01141b

  日期：——

  under neutral pH conditions. The catalyst performance is discussed in terms of acceleration over background hydrolysis and effective molarity (EM). The combination of potentiometric acid-base titrations with pH-rate profiles for HPNP and BNPP cleavage in the presence of 2·2HCl additives points to a marked synergic action of an acylguanidine/acylguanidinium catalytic dyad in 2H+, via general base-electrophilic

  杯[4]芳烃支架，在圆锥构象中被阻塞，并在上部边缘装饰有两个酰基胍单元，在中性pH条件下有效催化HPNP和BNPP的磷酸二酯键的裂解。根据背景水解的加速和有效摩尔浓度（EM）讨论了催化剂的性能。在2·2HCl添加剂存在下，电位计酸碱滴定法与pH速率曲线在HPNP和BNPP裂解作用下的结合表明，通过一般的亲电双功能催化作用，酰基胍/酰基胍盐催化二元体在2H +中具有明显的协同作用。获得超过3个数量级的背景加速因子。通过羰基连接将胍/胍二联体与杯芳烃骨架连接具有双重优势：（i）吸电子羰基增强了胍基部分的酸度，并且在几乎中性的pH值下最大程度地转化为催化活性形式2H +，该pH低于不含羰基的单质子化形式1H +所需的pH; （ii）用2H +进行HPNP裂解的EM值肯定高于使用1H +进行裂解的EM值，表明高度预组织的催化剂完全适合于催化过程中的无应变环形过渡态。DFT计算还提供了对反应机理和过渡态的有用见解。（ii）用2H
• Intra‐ and Intermolecular Cooperativity in the Catalytic Activity of Phosphodiester Cleavage by Self‐Assembled Systems Based on Guanidinylated Calix[4]arenes
  作者：Daniele Lisi、Carlo Alberto Vezzoni、Alessandro Casnati、Francesco Sansone、Riccardo Salvio

  DOI：10.1002/chem.202203213

  日期：2023.2.24

  Self-assembled enzyme mimic. Calix[4]arenes, provided with long alkyl chains and guanidine units, perform spontaneous aggregation driven by hydrophobic effect. A pronounced superiority of the phosphodiesterase activity of the assembled structures compared with the monomers indicates intermolecular cooperation of the active units through a dynamic preorganization.

  自组装酶模拟物。杯 [4] 芳烃具有长烷基链和胍单元，在疏水作用的驱动下进行自发聚集。与单体相比，组装结构的磷酸二酯酶活性的显着优势表明活性单元通过动态预组织进行分子间合作。
• Entropy and Enthalpy Contributions to Solvent Effects on Phosphate Monoester Solvolysis. The Importance of Entropy Effects in the Dissociative Transition State
  作者：Richard H. Hoff、Alvan C. Hengge

  DOI：10.1021/jo981160k

  日期：1998.9.1

  The solvolysis reactions of a series of aryl phosphates in tert-butyl alcohol and in tert-amyl alcohol have been examined. The dianion of p-nitrophenyl phosphate reacts 7500- and 8750-fold faster in these solvents, respectively, than the corresponding aqueous reactions. The monoanion reacts 14- and 16-fold slower respectively in tert-butyl alcohol and in tert-amyl alcohol. Analysis of the activation parameters shows that the rate enhancement for the dianion is due solely to entropic factors, while the slower reaction of the monoanion is due to increased enthalpy of activation. The significantly more positive entropy of activation for the solvolysis of p-nitrophenyl phosphate dianion in tert-butyl alcohol supports the original proposal that racemization at phosphorus in this reaction is caused by a switch to a D-N + A(N) mechanism, rather than subsequently proposed mechanisms which avoid the formation of metaphosphate. Rate enhancements of similar magnitudes are seen for the dianion reactions of all of the aryl phosphates examined; the slope of a plot of the rate constants for solvolysis versus the aqueous pK(a) of the leaving phenols has a slope of -1.1, within experimental error of the value for the aqueous reaction. However, in the reactions in tert-amyl alcohol, para-substituted and meta-substituted aryl phosphates fall on separate but parallel lines with para-substituted compounds reacting faster than meta-substituted reactants with leaving groups of similar pK(a). The pK(a) values for a series of para- and meta-substituted phenols in tert-butyl alcohol and in tert-amyl alcohol were determined and were found to have a linear relationship with the aqueous pK(a) values, with no distinction between para and meta substitution. Thus the different BrOnsted behavior of para- and meta-substituted aryl phosphates in these solvents is not due to differential solvent-induced perturbations of the pK(a) values of the leaving groups. The mechanistic implications of these results and their relevance to enzymatic phosphoryl transfer are discussed.
• Selective Hydrolysis of Phosphate Esters, Nitrophenyl Phosphates and UpU, by Dimeric Zinc Complexes Depends on the Spacer Length
  作者：William H. Chapman、Ronald Breslow

  DOI：10.1021/ja00125a005

  日期：1995.5

  Zn(II) complexes of monomers and dimers derived from 1,4,7-triazacyclododecane and 1,5,9-triazacyclotetradecane were examined as catalysts for the hydrolyses of p-nitrophenyl phosphate and bis(p-nitrophenyl) phosphate and for the cyclizations of p-nitrophenyl 2-hydroxypropyl phosphate and 3',5'-uridyluridine (UpU). The dimers with 1,4-phenyl and 1,3-phenyl linkers were more effective than were monomers or a longer dimer-with a 4,4'-biphenyl linker-in the hydrolysis of p-nitrophenyl phosphate, suggesting that two Zn(II)) ions coordinate to the phosphate group, as in the enzyme alkaline phosphatase. However, for the hydrolysis or cyclization of the phosphate diesters, the longer biphenyl linker was preferred. In this case one Zn(II) coordinates to the phosphate group while the other delivers a nucleophilic oxide anion. Bell-shaped pH vs rate profiles were seen in both cases, but with different pK's related to the specific mechanisms in the two cases.