<15N,18O>-p-nitrophenol | 161321-59-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: <15N,18O>-p-nitrophenol
• 英文别名: <18O,15N>-p-nitrophenol；(18)O,(15)N-p-nitrophenol
• CAS: 161321-59-1
• 化学式: C₆H₅NO₃
• 分子量: 142.105
• InChiKey: BTJIUGUIPKRLHP-OVRSYYMNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  10.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  63.37
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  <15N,18O>-p-nitrophenol 在 三氯氧磷 作用下， 生成 <15N,bridge-18O>-p-nitrophenyl phosphate
  参考文献：
  名称：

  Transition-State Structures for Phosphoryl-Transfer Reactions of p-Nitrophenyl Phosphate

  摘要：

  Heavy-atom isotope effects have been used to characterize the transition states for the aqueous hydrolysis reactions of the p-nitrophenyl phosphate dianion and monoanion, for the reaction of the dianion in neat tert-butyl alcohol, and for the reaction catalyzed by alkaline phosphatase. The primary oxygen-18 isotope effect at the phenolic oxygen ((18)k(bridge)), the secondary nitrogen-15 effect ((15)k) in the nitrogen atom of the leaving group, and the secondary oxygen-18 isotope effects in the nonbridge oxygen atoms of the phosphoryl group ((18)k(nonbridge)) have been measured. The isotope effects for the dianion reaction in water at 95 degrees C were (15)k = 1.0028 +/- 0.0002, (18)k(bridge) = 1.0189 +/- 0.0005, and (18)k(nonbridge) = 0.9994 +/- 0.0005. The dianion reaction in tert-butyl alcohol at 30 degrees C gave values of (15)k = 1.0039 +/- 0.0003, (18)k(bridge) = 1.0202 +/- 0.0008, and (18)k(nonbridge) = 0.9997 +/- 0.0016. When corrected for temperature, the results are very similar, indicating similar late transition state structures for the two reactions with little or no change in bond order between the phosphorus and the nonbridge oxygen atoms. The isotope effects on the aqueous reaction of the monoanion were (15)k = 1.0004 +/- 0.0002, (18)k(bridge) = 1.0087 +/- 0.0003, and (18)k(nonbridge) = 1.0184 +/- 0.0005, suggesting both proton transfer and bond cleavage are rate-limiting. The isotope effects on the alkaline phosphatase reaction are all near unity, indicating that a nonchemical step is rate-limiting for the enzymatic reaction.

  DOI：

  10.1021/ja00091a003
• 作为产物：
  描述：

  <15N>-p-nitrophenol sodium salt 在 重氧水 作用下， 生成 <15N,18O>-p-nitrophenol
  参考文献：
  名称：

  Transition-State Structures for Phosphoryl-Transfer Reactions of p-Nitrophenyl Phosphate

  摘要：

  Heavy-atom isotope effects have been used to characterize the transition states for the aqueous hydrolysis reactions of the p-nitrophenyl phosphate dianion and monoanion, for the reaction of the dianion in neat tert-butyl alcohol, and for the reaction catalyzed by alkaline phosphatase. The primary oxygen-18 isotope effect at the phenolic oxygen ((18)k(bridge)), the secondary nitrogen-15 effect ((15)k) in the nitrogen atom of the leaving group, and the secondary oxygen-18 isotope effects in the nonbridge oxygen atoms of the phosphoryl group ((18)k(nonbridge)) have been measured. The isotope effects for the dianion reaction in water at 95 degrees C were (15)k = 1.0028 +/- 0.0002, (18)k(bridge) = 1.0189 +/- 0.0005, and (18)k(nonbridge) = 0.9994 +/- 0.0005. The dianion reaction in tert-butyl alcohol at 30 degrees C gave values of (15)k = 1.0039 +/- 0.0003, (18)k(bridge) = 1.0202 +/- 0.0008, and (18)k(nonbridge) = 0.9997 +/- 0.0016. When corrected for temperature, the results are very similar, indicating similar late transition state structures for the two reactions with little or no change in bond order between the phosphorus and the nonbridge oxygen atoms. The isotope effects on the aqueous reaction of the monoanion were (15)k = 1.0004 +/- 0.0002, (18)k(bridge) = 1.0087 +/- 0.0003, and (18)k(nonbridge) = 1.0184 +/- 0.0005, suggesting both proton transfer and bond cleavage are rate-limiting. The isotope effects on the alkaline phosphatase reaction are all near unity, indicating that a nonchemical step is rate-limiting for the enzymatic reaction.

  DOI：

  10.1021/ja00091a003

文献信息

• Mechanistic Study of Protein Phosphatase-1 (PP1), A Catalytically Promiscuous Enzyme
  作者：Claire McWhirter、Elizabeth A. Lund、Eric A. Tanifum、Guoqiang Feng、Qaiser I. Sheikh、Alvan C. Hengge、Nicholas H. Williams

  DOI：10.1021/ja803612z

  日期：2008.10.15

  the alkaline hydrolysis of 4NPMP that is similar to that of diesters with the same leaving group. For the enzymatic reaction of 4NPMP, the KIEs are indicative of a transition state that is somewhat looser than the alkaline hydrolysis reaction and similar to the PP1-catalyzed monoester reaction. The data cumulatively point to enzymatic transition states for aryl phosphate monoester and aryl methylphosphonate

  由蛋白质磷酸酶-1 (PP1) 催化的反应已通过线性自由能关系和动力学同位素效应进行了检查。对于底物 4-硝基苯基磷酸酯 (4NPP)，反应显示出 kcat/KM 的钟形 pH 速率曲线，表明酸性和碱性残基的催化作用，动力学 pKa 值为 6.0 和 7.2。一系列芳基单酯底物的酶促水解产生 -0.32 的 Brønsted beta(lg)，比单酯双阴离子的未催化水解 (-1.23) 的负值小得多。具有底物 4NPP 的离去基团中的动力学同位素效应为 (18)(V/K) 桥 = 1.0170 和 (15)(V/K) = 1.0010，与其他具有和不具有一般酸催化作用的酶促 KIE 相比，它们是与离去基团部分中和的松散过渡态一致。PP1 还有效地催化 4-硝基苯基甲基膦酸酯 (4NPMP) 的水解。一系列芳基甲基膦酸酯底物的酶促水解产生 -0.30 的 Brønsted beta(lg)，小于碱性水解
• A Mechanistic Study of the Alkaline Hydrolysis of Diaryl Sulfate Diesters
  作者：Jarod M. Younker、Alvan C. Hengge

  DOI：10.1021/jo0488309

  日期：2004.12.1

  alkyl aryl diesters, which undergo reaction by carbon−oxygen bond fission. Sulfuryl transfer reactions of sulfate diesters (RO−SO2−OR‘) proceeding by attack at sulfur have been little explored. When both ester groups are aryl groups the hydrolysis reaction (sulfuryl transfer to water) occurs by way of attack at sulfur. The alkaline hydrolysis of diaryl sulfate diesters was shown to obey first-order kinetics

  几乎所有已报道的关于硫酸二酯反应的研究都是针对二烷基或烷基芳基二酯，它们通过碳-氧键裂变进行反应。很少研究通过攻击硫而进行的硫酸二酯（RO-SO 2 -OR'）的硫酰基转移反应。当两个酯基均为芳基时，水解反应（硫酰基转移至水中）是通过攻击硫而发生的。硫酸二芳基二酯的碱性水解物显示出服从一级动力学相对于[ - OH]，并通过S-O键断裂进行，在最有可能一致的机构。用于4-氯-3-硝基苯基苯基硫酸酯和4-硝基苯基苯基硫酸激活参数给出下列各值：Δ ħ ⧧= 88.0±0.1和84.83±0.06千焦耳摩尔- 1和Δ小号⧧ = -37±1和±-50.2 0.5焦耳摩尔- 1度- 1。二阶速率常数的水解在离开基团P的依赖性ķ一个分析给出β LG -0.7±0.2斜率和0.36莱弗勒α参数值。获得了针对氢氧化物对4-硝基苯基苯基硫酸盐的氢氧化物攻击的15 k动力学同位素效应（KIE）1.0000±0.0005和1
• Studies of Transition-State Structures in Phosphoryl Transfer Reactions of Phosphodiesters of p-Nitrophenol
  作者：Alvan C. Hengge、Aleksandra E. Tobin、W. W. Cleland

  DOI：10.1021/ja00127a003

  日期：1995.6

  Heavy-atom kinetic isotope effects have been used to study the transition states for a number of phosphoryl transfer reactions of the phosphodiesters p-tert-butylphenyl p-nitrophenyl phosphate (1) and 3,3-dimethylbutyl p-nitrophenyl phosphate (2). The alkaline and acid hydrolysis reactions and the reaction with phosphodiesterase I from snake venom were studied with each substrate. In addition, the hydrolysis reactions of 1 catalyzed by bis-(imidazolyl)- and by mono(imidazolyl)-beta-cyclodextrins were studied. The isotope effects measured were the primary O-18 isotope effect in the p-nitrophenyl leaving group, the secondary O-18 isotope effect in the nonbridge oxygen atoms, and the N-15 isotope effect in the leaving group. The data indicate similar early transition-state structures for the aqueous hydrolysis reactions of the two compounds with little bond cleavage to the leaving group. In contrast, significant differences in transition-state structure between the substrates are seen in their reactions with phosphodiesterase I. Compound 1 is a substrate for the imidazolyl-beta-cyclodextrin catalysts, which operate as simple general base catalysts for this substrate. Transition-state bond cleavage to the leaving group is much further advanced in these reactions than in the uncatalyzed aqueous reactions.