2-硝基苯基磷酸甲酯 | 29307-56-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2-硝基苯基磷酸甲酯
• 英文名称: methyl 2-nitrophenyl phosphate
• 英文别名: Methyl-2-Nitro-phenyl-phosphat；Methyl-2-nitrophenyl-phosphat；Methyl (2-nitrophenyl) hydrogen phosphate；methyl (2-nitrophenyl) hydrogen phosphate
• CAS: 29307-56-0
• 化学式: C₇H₈NO₆P
• 分子量: 233.117
• InChiKey: QPYNHEJPOVAIQK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  102
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  甲醇 、 2-硝基苯基磷酸甲酯 在 1,3-bis-N₁-(1,5,9-triazacyclododecyl)propane*Zn(II)*MeOH tert-butylammonium hydroxide 作用下， 生成 磷酸二甲酯 、 硝苯酚
  参考文献：
  名称：

  A Simple DNase Model System Comprising a Dinuclear Zn(II) Complex in Methanol Accelerates the Cleavage of a Series of Methyl Aryl Phosphate Diesters by 10¹¹−10¹³

  摘要：

  The di-Zn(II) complex of 1,3-bis[N-1,N-1'-(1,5,9-triazacyclododecyl)] propane with an associated methoxide (3:Zn(II)(2):-OCH3) was prepared and its catalysis of the methanolysis of a series of fourteen methyl aryl phosphate diesters (6) was studied at (s)(s)pH 9.8 in methanol at 25.0 +/- 0.1 degrees C. Plots of k(obs) VS [3:Zn(II)(2):-OCH3](free) for all members of 6 show saturation behavior from which K-M and k(cat)(max) were determined. The second order rate constants for the catalyzed reactions (k(cat)(max)/K-M) for each substrate are larger than the corresponding methoxide catalyzed reaction (k(2)(-OMe)) by 1.4 x 10(8) to 3 x 10(9)-fold. The values of kcatmax for all members of 6 are between 4 x 10(11) and 3 x 10(13) times larger than the solution reaction at (s)(s)pH 9.8, with the largest accelerations being given for substrates where the departing aryloxy unit contains ortho-NO2 or C(= O)OCH3 groups. Based on the linear Bronsted plots of k(cat)(max) VS (s)(s)pK(a)of the phenol, beta(Ig) values of -0.57 and -0.34 are determined respectively for the catalyzed methanolysis of "regular' substrates that do not contain the ortho-NO2 or C(= O)OCH3 groups, and those substrates that do. The data are consistent with a two step mechanism for the catalyzed reaction with rate limiting formation of a catalyst-coordinated phosphorane intermediate, followed by fast loss of the aryloxy leaving group. A detailed energetics calculation indicates that the catalyst binds the transition state comprising [CH3O-:6]double dagger, giving a hypothetical [3:Zn(II)(2):CH3O-:6]double dagger complex, by -21.4 to -24.5 kcal/mol, with the strongest binding being for those substrates having the ortho-NO2 or C(= O)OCH3 groups.

  DOI：

  10.1021/ja8006963
• 作为产物：
  描述：

  sodium o-nitrophenate 、 氯磷酸二甲酯 生成 2-硝基苯基磷酸甲酯
  参考文献：
  名称：

  磷酸酯的反应性。二酯与亲核试剂的反应

  摘要：

  多种亲核试剂与一系列芳基甲基磷酸酯阴离子的反应涉及在磷处的协同亲核取代。中性亲核试剂的进攻要比三酯和单酯单阴离子的相应反应慢。观察到涉及阴离子对磷酸二酯阴离子的攻击的S N 2（P）反应，并且显示出受阻约两倍。速率为100倍，这归因于不良的静电作用。对亲核试剂和离去基团的敏感性都很高，并且对反应性有一定的依赖性：它们显然也受到静电作用的影响。

  DOI：

  10.1039/j29700001165

文献信息

• The reactivity of phosphate esters. Reactions of diesters with nucleophiles
  作者：A. J. Kirby、M. Younas

  DOI：10.1039/j29700001165

  日期：——

  The reactions of a wide range of nucleophiles with a series of aryl methyl phosphate ester anions involve concerted nucleophilic displacement at phosphorus. The attack of neutral nucleophiles is slower than the corresponding reactions of both triesters and monoester monoanions. SN2(P) reactions involving the attack of anions on phosphate diester anions are observed, and are shown to be retarded by

  多种亲核试剂与一系列芳基甲基磷酸酯阴离子的反应涉及在磷处的协同亲核取代。中性亲核试剂的进攻要比三酯和单酯单阴离子的相应反应慢。观察到涉及阴离子对磷酸二酯阴离子的攻击的S N 2（P）反应，并且显示出受阻约两倍。速率为100倍，这归因于不良的静电作用。对亲核试剂和离去基团的敏感性都很高，并且对反应性有一定的依赖性：它们显然也受到静电作用的影响。
• A Simple DNase Model System Comprising a Dinuclear Zn(II) Complex in Methanol Accelerates the Cleavage of a Series of Methyl Aryl Phosphate Diesters by 10¹¹−10¹³
  作者：Alexei A. Neverov、C. Tony Liu、Shannon E. Bunn、David Edwards、Christopher J. White、Stephanie A. Melnychuk、R. Stan Brown

  DOI：10.1021/ja8006963

  日期：2008.5.1

  The di-Zn(II) complex of 1,3-bis[N-1,N-1'-(1,5,9-triazacyclododecyl)] propane with an associated methoxide (3:Zn(II)(2):-OCH3) was prepared and its catalysis of the methanolysis of a series of fourteen methyl aryl phosphate diesters (6) was studied at (s)(s)pH 9.8 in methanol at 25.0 +/- 0.1 degrees C. Plots of k(obs) VS [3:Zn(II)(2):-OCH3](free) for all members of 6 show saturation behavior from which K-M and k(cat)(max) were determined. The second order rate constants for the catalyzed reactions (k(cat)(max)/K-M) for each substrate are larger than the corresponding methoxide catalyzed reaction (k(2)(-OMe)) by 1.4 x 10(8) to 3 x 10(9)-fold. The values of kcatmax for all members of 6 are between 4 x 10(11) and 3 x 10(13) times larger than the solution reaction at (s)(s)pH 9.8, with the largest accelerations being given for substrates where the departing aryloxy unit contains ortho-NO2 or C(= O)OCH3 groups. Based on the linear Bronsted plots of k(cat)(max) VS (s)(s)pK(a)of the phenol, beta(Ig) values of -0.57 and -0.34 are determined respectively for the catalyzed methanolysis of "regular' substrates that do not contain the ortho-NO2 or C(= O)OCH3 groups, and those substrates that do. The data are consistent with a two step mechanism for the catalyzed reaction with rate limiting formation of a catalyst-coordinated phosphorane intermediate, followed by fast loss of the aryloxy leaving group. A detailed energetics calculation indicates that the catalyst binds the transition state comprising [CH3O-:6]double dagger, giving a hypothetical [3:Zn(II)(2):CH3O-:6]double dagger complex, by -21.4 to -24.5 kcal/mol, with the strongest binding being for those substrates having the ortho-NO2 or C(= O)OCH3 groups.