4-(硝基-15N)苯酚 | 103427-15-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 中文名称: 4-(硝基-15N)苯酚
• 英文名称: [(15)N]-p-nitrophenol
• 英文别名: (15)N-p-nitrophenol；4-[¹⁵N]nitro-phenol；4-Nitrophenol-15N；4-[oxido(oxo)(15N)(15N)azaniumyl]phenol
• CAS: 103427-15-2
• 化学式: C₆H₅NO₃
• 分子量: 140.104
• InChiKey: BTJIUGUIPKRLHP-CDYZYAPPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  66
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  双二异丙基氨基氯化磷 、 4-(硝基-15N)苯酚 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以85%的产率得到bis(N,N-diisopropylamino)<15N>-p-nitrophenoxyphosphate
  参考文献：
  名称：

  Studies of Transition-State Structures in Phosphoryl Transfer Reactions of Phosphodiesters of p-Nitrophenol

  摘要：

  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.

  DOI：

  10.1021/ja00127a003
• 作为产物：
  描述：

  4-[(4-chlorophenyl)methoxy]-N-(3,4-dichlorophenyl)-3-methoxybenzamide 在 sodium hydroxide 作用下， 以 水 、 二甲基亚砜 为溶剂， 反应 0.33h， 生成 4-(硝基-15N)苯酚
  参考文献：
  名称：

  15 N核极化中的硝化作用及相关反应。第2部分。对硝基苯酚

  摘要：

  亚硝酸催化三氟乙酸水溶液中H 15 NO 3催化的对硝基苯酚硝化反应在形成的2,4-二硝基苯酚的15 N nmr光谱中的2- 15 NO 2基团反应期间产生强发射信号：最多可提高600倍。反应伴随着原始4-硝基向11位的11％迁移，并在4位被标记的硝基取代。在15使用相关反应在n个核磁共振谱15 Ñ标记p硝基苯酚和未标记的硝酸表明4-迁移15 NO2位到2位引起在形成的2,4-二硝基苯酚中2-15 NO 2基团的吸收信号大大增强。对于在叠氮化钠存在下对硝基苯酚与H 15 NO 3的反应，也发现该组的吸收信号大大增强。当通过扩散或单重态前体形成自由基对时，核对极化的反应就可以解释完整的结果。对硝基苯酚催化了hydr酸与硝酸之间的反应。

  DOI：

  10.1039/p29840001667

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
• Isotope Effects on Enzyme-Catalyzed Acyl Transfer from <i>p</i>-Nitrophenyl Acetate:  Concerted Mechanisms and Increased Hyperconjugation in the Transition State
  作者：Robert A. Hess、Alvan C. Hengge、W. W. Cleland

  DOI：10.1021/ja973413h

  日期：1998.4.1

  0002. Uncatalyzed acyl transfer from PNPA to oxygen and sulfur nucleophiles proceeds by a concerted mechanism. All of the enzymatic reactions showed isotope effects consistent with a concerted mechanism like that seen in uncatalyzed aqueous reactions, but exhibited smaller inverse β-deuterium isotope effects than seen in the nonenzymatic aqueous reac...

  为了检查对硝基苯乙酸酯 (PNPA) 的酶促酰基转移机制，测量了 PNPA 与胰凝乳蛋白酶、碳酸酐酶、木瓜蛋白酶和曲霉酸蛋白酶反应的同位素效应。在 β-氘 (Dk)、羰基碳 (13k)、羰基氧 (18kcarbonyl)、离去基团酚氧 (18klg) 和离去基团氮 (15k) 位置测量同位素效应。Dk 范围从 0.982 ± 0.002 到 0.999 ± 0.002。13k 的范围从 1.028 ± 0.002 到 1.036 ± 0.002。18k羰基的范围从 1.0064 ± 0.0003 到 1.007 ± 0.001。18klg 的范围从 1.141 ± 0.0002 到 1.330 ± 0.0007。15k 的范围从 0.9997 ± 0.0007 到 1.0011 ± 0.0002。从 PNPA 到氧和硫亲核试剂的未催化酰基转移是通过协同机制进行的。
• The mechanism of nitration by 4-methyl-4-nitro-2,3,5,6-tetrabromocyclohexa-2,5-dienone
  作者：Robert G. Coombes、John H. Ridd

  DOI：10.1039/c39920000174

  日期：——

  Nitration of phenol by 4-methyl-4-nitro-2,3,5,6-tetrabromocyclohexa-2,5-dienone in diethyl ether is a radical process involving reaction between the phenoxyl radical and NO2˙ that has escaped from a radical pair in which it was formed by homolytic fission of the C–N bond.

  在二乙醚中，4-甲基-4-硝基-2,3,5,6-四溴环己-2,5-二烯酮对苯酚的硝化作用是一个自由基反应过程，涉及苯氧自由基和 NO2˙之间的反应。
• 15N-CIDNP during Photonitration of Phenol with Tetranitromethane and Reactions with Nitric and Nitrous Acid
  作者：Manfred Lehnig、Klaus Schürmann

  DOI：10.1002/(sici)1099-0690(199805)1998:5<913::aid-ejoc913>3.0.co;2-r

  日期：1998.5

  and during the reaction of 1 with 15N-enriched nitric acid and nitrous acid, emission due to the nitration products o- and p-nitrophenol (2a, 2b) is observed in the 15N-NMR spectra. The CIDNP effects are built up by radical pairs formed by the encounters of the radicals NO2· and 1+· or PhO·. During the reaction of 1 with nitrous acid, 2b is formed, in part due to a non-radical reaction, via oxidation

  在苯酚（1）中用15 N富集的四硝基甲烷在乙腈中辐照期间以及在1与15 N富集的硝酸和亚硝酸反应期间，由于硝化产物邻硝基和对硝基苯酚（2a，2b）的排放在15 N-NMR光谱中观察到）。CIDNP效应是由自由基NO 2 ·和1 +·或PhO ·的相遇形成的自由基对建立的。1与亚硝酸2b反应期间通过对-亚硝基苯酚（3）的氧化，部分地由于非自由基反应而形成α-β-环糊精。
• Morrow, Janet R.; Richard, John P.; et al., Journal of the American Chemical Society, 2008, vol. 130, p. 17858 - 17866
  作者：Morrow, Janet R.、Richard, John P.、et al.、Humphry, Tim、Iyer, Subashree、Iranzo, Olga

  DOI：——

  日期：——