p-nitrophenyl 3-(dimethylphosphono)propionate | 78939-55-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚酯
• 英文名称: p-nitrophenyl 3-(dimethylphosphono)propionate
• 英文别名: (4-Nitrophenyl) 3-dimethoxyphosphorylpropanoate；(4-nitrophenyl) 3-dimethoxyphosphorylpropanoate
• CAS: 78939-55-6
• 化学式: C₁₁H₁₄NO₇P
• 分子量: 303.208
• InChiKey: OIALNEFTVLVAKA-UHFFFAOYSA-N

物化性质

• 沸点：
  453.5±30.0 °C(Predicted)
• 密度：
  1.345±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  108
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  p-nitrophenyl 3-(dimethylphosphono)propionate 在 sodium molybdate 盐酸 、 buffer solution (0.01 M HEPES) 作用下， 以 乙腈 为溶剂， 生成 4-硝基苯酚阴离子
  参考文献：
  名称：

  Nucleophilic reactions of molybdate

  摘要：

  Although molybdate (MoO42-) is over 1000 times less basic than the phosphate dianion it is 35 times more nucleophilic toward p-nitrophenyl acetate (pNPA) and p-nitrophenyl thioacetate (pNPTA) at 27-degrees-C (Wikjord, B.; Byers, L. D. J. Am. Chem. Soc. 1992,114,5553). Based on Bronsted relationships for the reaction of a series of phosphonate dianions with these esters (beta(nuc) = 0.3 at 37-degrees-C), molybdate (pK(a2) = 3.9) is as reactive as a phosphonate with pK(a2) = 12. The activation parameters are DELTAH(double dagger) = 15.8 (+/-0.1) kcal/mol and DELTAS(double dagger) = -17.4 (+/-0.4) eu for the reaction with pNPA and DELTAH(double dagger) = 16.0 (+/-0.2) kcal/mol and DELTAS(double dagger) = -15.0 (+/-0.6) eu for the reaction with pNPTA. The second-order rate constant for the reaction of MoO42- with a series of 13 acyl-substituted p-nitrophenyl esters at 27-degrees-C shows nearly identical sensitivity to substituent effects (rho* = 2.8) as does the rate of alkaline hydrolysis or the equilibrium addition of hydroxide to aldehydes (Shames, S. L.; Byers, L. D. J. Am. Chem. Soc. 1981, 103, 6170), suggesting that the transition state for the molybdenolysis reaction closely resembles the tetrahedral intermediate. In addition to the reaction with activated carboxylic esters, molybdate catalyzes the hydrolysis of a variety of electrophiles. The second-order rate constants (M-1 min-1, 27-degrees-C, mu = 1.5 M) for the reactions of molybdate are 0.25 (+/-0.01) with ethyl pyruvate, (2.10+/-0.08) x 10(-2) with 2,4-dinitrofluorobenzene, and (7.2 +/-0.4) x 10(-5) with methyl iodide.

  DOI：

  10.1021/jo00051a026
• 作为产物：
  描述：

  对硝基苯酚 、 alkaline earth salt of/the/ methylsulfuric acid 在 N,N'-二环己基碳二亚胺 作用下， 以 乙酸乙酯 为溶剂， 反应 6.0h， 生成 p-nitrophenyl 3-(dimethylphosphono)propionate
  参考文献：
  名称：

  Acyl substituent effects on rates of acyl transfer to thiolate, hydroxide, and oxy dianions

  摘要：

  DOI：

  10.1021/ja00410a032

文献信息

• Effect of phosphono substituents on acyl transfer reactions
  作者：Spencer L. Shames、Larry D. Byers

  DOI：10.1021/ja00410a033

  日期：1981.10
• Acyl substituent effects on rates of acyl transfer to thiolate, hydroxide, and oxy dianions
  作者：Spencer L. Shames、Larry D. Byers

  DOI：10.1021/ja00410a032

  日期：1981.10
• Nucleophilic reactions of molybdate
  作者：Brenda R. Wikjord、Larry D. Byers

  DOI：10.1021/jo00051a026

  日期：1992.12

  Although molybdate (MoO42-) is over 1000 times less basic than the phosphate dianion it is 35 times more nucleophilic toward p-nitrophenyl acetate (pNPA) and p-nitrophenyl thioacetate (pNPTA) at 27-degrees-C (Wikjord, B.; Byers, L. D. J. Am. Chem. Soc. 1992,114,5553). Based on Bronsted relationships for the reaction of a series of phosphonate dianions with these esters (beta(nuc) = 0.3 at 37-degrees-C), molybdate (pK(a2) = 3.9) is as reactive as a phosphonate with pK(a2) = 12. The activation parameters are DELTAH(double dagger) = 15.8 (+/-0.1) kcal/mol and DELTAS(double dagger) = -17.4 (+/-0.4) eu for the reaction with pNPA and DELTAH(double dagger) = 16.0 (+/-0.2) kcal/mol and DELTAS(double dagger) = -15.0 (+/-0.6) eu for the reaction with pNPTA. The second-order rate constant for the reaction of MoO42- with a series of 13 acyl-substituted p-nitrophenyl esters at 27-degrees-C shows nearly identical sensitivity to substituent effects (rho* = 2.8) as does the rate of alkaline hydrolysis or the equilibrium addition of hydroxide to aldehydes (Shames, S. L.; Byers, L. D. J. Am. Chem. Soc. 1981, 103, 6170), suggesting that the transition state for the molybdenolysis reaction closely resembles the tetrahedral intermediate. In addition to the reaction with activated carboxylic esters, molybdate catalyzes the hydrolysis of a variety of electrophiles. The second-order rate constants (M-1 min-1, 27-degrees-C, mu = 1.5 M) for the reactions of molybdate are 0.25 (+/-0.01) with ethyl pyruvate, (2.10+/-0.08) x 10(-2) with 2,4-dinitrofluorobenzene, and (7.2 +/-0.4) x 10(-5) with methyl iodide.