[(3,5-Dinitrobenzylidene)(oxido)-lambda~5~-azanyl]oxidanide | 70136-14-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(3,5-Dinitrobenzylidene)(oxido)-lambda~5~-azanyl]oxidanide
• 英文别名: (3,5-dinitrophenyl)methylidene-dioxidoazanium
• CAS: 70136-14-0
• 化学式: C₇H₄N₃O₆
• 分子量: 226.125
• InChiKey: RIDLXVTZZQEXAP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  138
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  [(3,5-Dinitrobenzylidene)(oxido)-lambda~5~-azanyl]oxidanide 在 苯甲酸 作用下， 以 甲醇 为溶剂， 生成 2,4-二硝基-1-(硝基甲基)苯 、 alkaline earth salt of/the/ methylsulfuric acid
  参考文献：
  名称：

  Solvent Effects on Proton Transfer Reactions:  Benzoate Ion Promoted Deprotonation Reactions of Arylnitromethanes in Methanol Solution

  摘要：

  Second-order rate constants and equilibrium constants have been determined for the benzoate ion promoted deprotonation reactions of (m-nitrophenyl)nitromethane, (p-nitrophenyl)nitromethane, and (3,5-dinitrophenyl)nitromethane in methanol solution. The pK(a) values for the arylnitromethanes in methanol are the following: pK(a) = 10.9, 10.5, and 9.86 for (m-nitrophenyl)-nitromethane, (p-nitrophenyl)nitromethane, and (3,5-dinitrophenyl)nitromethane, respectively, relative to benzoic acid (pK(a) = 9.4). A Bronsted beta(B) value of 0.50 and alpha(CH) value of 1.31 have been calculated for the 3,4-dimethylbenzoate, benzoate, m-bromobenzoate, and 3,4-dichlorobenzoate ion promoted reactions of(3,5-dinitrophenyl)nitromethane, and for the benzoate ion promoted reactions of (m-nitrophenyl)nitromethane, (p-nitrophenyl)nitromethane, and (3,5-dinitrophenyl)nitromethane, respectively. The log of the intrinsic rate constants for benzoate ion promoted deprotonations of (m-nitrophenyl)nitromethane, (p-nitrophenyl)nitromethane, and (3,5-dinitrophenyl)nitromethane are 0.0212, 0.270, and 0.877, respectively. These values are 6.3 x 10(4), 2.0 x 10(4), and 2.5 x 10(4) times lower than for the same reactions in acetonitrile solution. The transfer activity coefficient from methanol to acetonitrile solution, log (M) gamma(AN), for (m-nitrophenyl)nitromethyl anion (3.6) and (m-nitrophenyl)nitromethane (-1.0) have been calculated. The solvent effect on these reactions in methanol and acetonitrile, two solvents with similar dielectric constants, are analyzed within the framework of the Principal of Nonperfect Synchronization. The results suggest that the observed solvent effect is a result of an imbalanced transition state (i.e., PNS effects), and a stronger transition state hydrogen bond between the carbon acid and benzoate ion in acetonitrile than in methanol solution.

  DOI：

  10.1021/jo970409f
• 作为产物：
  描述：

  2,4-二硝基-1-(硝基甲基)苯 在 苯甲酸阴离子 作用下， 以 甲醇 为溶剂， 生成 [(3,5-Dinitrobenzylidene)(oxido)-lambda~5~-azanyl]oxidanide 、 alkaline earth salt of/the/ methylsulfuric acid
  参考文献：
  名称：

  Solvent Effects on Proton Transfer Reactions:  Benzoate Ion Promoted Deprotonation Reactions of Arylnitromethanes in Methanol Solution

  摘要：

  Second-order rate constants and equilibrium constants have been determined for the benzoate ion promoted deprotonation reactions of (m-nitrophenyl)nitromethane, (p-nitrophenyl)nitromethane, and (3,5-dinitrophenyl)nitromethane in methanol solution. The pK(a) values for the arylnitromethanes in methanol are the following: pK(a) = 10.9, 10.5, and 9.86 for (m-nitrophenyl)-nitromethane, (p-nitrophenyl)nitromethane, and (3,5-dinitrophenyl)nitromethane, respectively, relative to benzoic acid (pK(a) = 9.4). A Bronsted beta(B) value of 0.50 and alpha(CH) value of 1.31 have been calculated for the 3,4-dimethylbenzoate, benzoate, m-bromobenzoate, and 3,4-dichlorobenzoate ion promoted reactions of(3,5-dinitrophenyl)nitromethane, and for the benzoate ion promoted reactions of (m-nitrophenyl)nitromethane, (p-nitrophenyl)nitromethane, and (3,5-dinitrophenyl)nitromethane, respectively. The log of the intrinsic rate constants for benzoate ion promoted deprotonations of (m-nitrophenyl)nitromethane, (p-nitrophenyl)nitromethane, and (3,5-dinitrophenyl)nitromethane are 0.0212, 0.270, and 0.877, respectively. These values are 6.3 x 10(4), 2.0 x 10(4), and 2.5 x 10(4) times lower than for the same reactions in acetonitrile solution. The transfer activity coefficient from methanol to acetonitrile solution, log (M) gamma(AN), for (m-nitrophenyl)nitromethyl anion (3.6) and (m-nitrophenyl)nitromethane (-1.0) have been calculated. The solvent effect on these reactions in methanol and acetonitrile, two solvents with similar dielectric constants, are analyzed within the framework of the Principal of Nonperfect Synchronization. The results suggest that the observed solvent effect is a result of an imbalanced transition state (i.e., PNS effects), and a stronger transition state hydrogen bond between the carbon acid and benzoate ion in acetonitrile than in methanol solution.

  DOI：

  10.1021/jo970409f

文献信息

• Kinetics of deprotonation of arylnitromethanes by benzoate ions in acetonitrile solution. Effect of equilibrium and nonequilibrium transition state solvation on intrinsic rate constants of proton transfers
  作者：Joseph R. Gandler、Claude F. Bernasconi

  DOI：10.1021/ja00028a032

  日期：1992.1

  Second-order rate constants for benzoate ion promoted deprotonation reactions of (3-nitrophenyl)nitromethane, (4-nitrophenyl)nitromethane, and (3,5-dinitrophenyl)nitromethane have been determined in acetonitrile solution at 25-degrees-C. These data were obtained at low benzoate buffer concentrations (< 0.01 M), utilizing tetraethylammonium benzoate salts, and benzoate ion concentrations corrected for homoconjugation with data previously reported by Kolthoff and Chantooni. Acidity constants in acetonitrile have also been determined: (3-nitrophenyl)nitromethane, pK(a) = 21.7; (4-nitromethyl)nitromethane, pk(a) = 20.6; and (3,5-dinitrophenyl)nitromethane, pK(a) = 19.8. A Bronsted beta(B) value of 0.56 and an alpha(CH) value of 0.79 have been calculated for the benzoate, 3-bromobenzoate, and 4-nitrobenzoate ion promoted reactions of (3,5-dinitrophenyl)nitromethane and for the benzoate ion promoted reactions of (3-nitrophenyl)nitromethane and (3,5-dinitrophenyl)nitromethane, respectively; (4-nitrophenyl)nitromethane deviates negatively from the Bronsted plot due to the resonance effect of the 4-nitro group. The logarithms of the intrinsic rate constants for benzoate promoted deprotonations of (3-nitrophenyl)nitromethane, (4-nitrophenyl)nitromethane, and (3,5-dinitrophenyl)nitromethane are 4.81, 4.58, and 5.27, respectively, and these values are 1.43, 1.70, and 1.30 log units, respectively, higher in acetonitrile than in dimethyl sulfoxide. Transfer activity coefficients from dimethyl sulfoxide (D) to acetonitrile (A) solution, log D(gamma)A for (3-nitrophenyl)nitromethyl anion (0.28), (4-nitrophenyl)nitromethyl anion (0.56), (3-nitrophenyl)nitromethane (0.18), and (4-nitrophenyl)nitromethane (0.16) have been calculated, and log D(gamma) A for benzoic acid (approximately 1.9) and the benzoate ion (approximately 0.25) have been estimated. The solvent effects on the intrinsic rate constants are analyzed within the framework of the Principle of Nonperfect Synchronization (PNS) in terms of contributions by late solvation of the arylnitromethyl anion, late solvation of the benzoic acid (produced as a product of the reaction), early desolvation of the benzoate ion and the arylnitromethane, and by a classical solvent effect. The results are also compared with predictions by a theoretical model recently proposed by Kurz. For the comparison of intrinsic rate constants in water and dimethyl sulfoxide there is good agreement between the Kurz model and the experimental results as well as the PNS analysis, but there is a discrepancy between the results and the predictions of the Kurz model for the comparison of intrinsic rate constants in dimethyl sulfoxide and acetonitrile solutions.
• Solvent Effects on Proton Transfer Reactions:  Benzoate Ion Promoted Deprotonation Reactions of Arylnitromethanes in Methanol Solution
  作者：Joseph R. Gandler、Oliver L. Saunders、Ronald Barbosa

  DOI：10.1021/jo970409f

  日期：1997.7.1

  Second-order rate constants and equilibrium constants have been determined for the benzoate ion promoted deprotonation reactions of (m-nitrophenyl)nitromethane, (p-nitrophenyl)nitromethane, and (3,5-dinitrophenyl)nitromethane in methanol solution. The pK(a) values for the arylnitromethanes in methanol are the following: pK(a) = 10.9, 10.5, and 9.86 for (m-nitrophenyl)-nitromethane, (p-nitrophenyl)nitromethane, and (3,5-dinitrophenyl)nitromethane, respectively, relative to benzoic acid (pK(a) = 9.4). A Bronsted beta(B) value of 0.50 and alpha(CH) value of 1.31 have been calculated for the 3,4-dimethylbenzoate, benzoate, m-bromobenzoate, and 3,4-dichlorobenzoate ion promoted reactions of(3,5-dinitrophenyl)nitromethane, and for the benzoate ion promoted reactions of (m-nitrophenyl)nitromethane, (p-nitrophenyl)nitromethane, and (3,5-dinitrophenyl)nitromethane, respectively. The log of the intrinsic rate constants for benzoate ion promoted deprotonations of (m-nitrophenyl)nitromethane, (p-nitrophenyl)nitromethane, and (3,5-dinitrophenyl)nitromethane are 0.0212, 0.270, and 0.877, respectively. These values are 6.3 x 10(4), 2.0 x 10(4), and 2.5 x 10(4) times lower than for the same reactions in acetonitrile solution. The transfer activity coefficient from methanol to acetonitrile solution, log (M) gamma(AN), for (m-nitrophenyl)nitromethyl anion (3.6) and (m-nitrophenyl)nitromethane (-1.0) have been calculated. The solvent effect on these reactions in methanol and acetonitrile, two solvents with similar dielectric constants, are analyzed within the framework of the Principal of Nonperfect Synchronization. The results suggest that the observed solvent effect is a result of an imbalanced transition state (i.e., PNS effects), and a stronger transition state hydrogen bond between the carbon acid and benzoate ion in acetonitrile than in methanol solution.