苯甲酸,3-溴-,离子(1-) | 16887-61-9

• 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: 苯甲酸,3-溴-,离子(1-)
• 英文名称: 3-bromobenzoate
• 英文别名: O2CC6H4Br-m(1-)；3-bromo-benzoic acid; deprotonated form；3-Brom-benzoesaeure-Anion
• CAS: 16887-61-9
• 化学式: C₇H₄BrO₂
• 分子量: 200.012
• InChiKey: VOIZNVUXCQLQHS-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 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：
  40.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  苯甲酸,3-溴-,离子(1-) 以 甲醇 为溶剂， 生成 间溴苯甲酸
  参考文献：
  名称：

  Ka Values of Weak Organic Acids in Protic Solvents Obtained from Their First Hyperpolarizabilities in Solution

  摘要：

  The first hyperpolarizabilities (beta) of some weak aromatic organic acids have been measured in protic solvents by the hyper-Rayleigh scattering (HRS) technique at low concentrations. The measured hyperpolarizability (beta(m)) varies between the two extreme limits: the hyperpolarizability of the acid form (beta(HA)) at the lower side and that of the basic form (beta(A-)) at the higher side. The degree of dissociation (alpha) of the acid in a solvent is related to the measured hyperpolarizability, beta(m), by the following relationship: beta(m)(2)=(1-alpha)beta(HA)(2)+alpha beta(A-)(2). The calculated beta's including solvent effects in terms of an Onsager field do not reproduce the experimentally measured hyperpolarizabilities. Other solvent-induced effects like hydrogen bonding and van der Waals interactions seem to influence the first hyperpolarizability and, thus, indirectly the extent of dissociation of these weak acids in these protic solvents.

  DOI：

  10.1021/j100051a014
• 作为产物：
  描述：

  间溴苯甲酸 以 甲醇 为溶剂， 生成 苯甲酸,3-溴-,离子(1-)
  参考文献：
  名称：

  Ka Values of Weak Organic Acids in Protic Solvents Obtained from Their First Hyperpolarizabilities in Solution

  摘要：

  The first hyperpolarizabilities (beta) of some weak aromatic organic acids have been measured in protic solvents by the hyper-Rayleigh scattering (HRS) technique at low concentrations. The measured hyperpolarizability (beta(m)) varies between the two extreme limits: the hyperpolarizability of the acid form (beta(HA)) at the lower side and that of the basic form (beta(A-)) at the higher side. The degree of dissociation (alpha) of the acid in a solvent is related to the measured hyperpolarizability, beta(m), by the following relationship: beta(m)(2)=(1-alpha)beta(HA)(2)+alpha beta(A-)(2). The calculated beta's including solvent effects in terms of an Onsager field do not reproduce the experimentally measured hyperpolarizabilities. Other solvent-induced effects like hydrogen bonding and van der Waals interactions seem to influence the first hyperpolarizability and, thus, indirectly the extent of dissociation of these weak acids in these protic solvents.

  DOI：

  10.1021/j100051a014

文献信息

• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Cr: Org.Verb., 1.6.2.1.2, page 331 - 347
  作者：

  DOI：——

  日期：——
• Elimination Reactions of (<i>Z</i>)-Thiophene- and (<i>Z</i>)-Furan-2-carbaldehyde <i>O</i>-Benzoyloximes. Effect of β-Aryl Group upon the Nitrile-Forming Anti Transition State
  作者：Bong Rae Cho、Nam Soon Cho、Sang Hun Song、Sang Kook Lee

  DOI：10.1021/jo981169m

  日期：1998.11.1

  Elimination reactions of(Z)-thiophene- and (Z)-furan-2-carbaldehyde O-benzoyloximes 1 and 2 with DBU in MeCN have been investigated kinetically. The reactions are second order and exhibit substantial values of Hammett rho and k(H)/k(D) values, and an E2 mechanism is evident. The relative rates of elimination from (Z)-ArCH=NOC(O)C6H4Y are 1/1.1/0.6 for Ar = phenyl/thienyl/furyl, respectively. For reactions of 1 with DBU in MeCN, k(H)/k(D) = 8.2 +/- 0.1, Hammett rho = 1.22 +/- 0.19, beta(1g) = -0.43 +/- 0.01, Delta H-double dagger = 5.9 +/- 0.1 kcal/mol, and Delta S-double dagger = -28.5 +/- 0.3 eu have been determined. The corresponding values for 2 are k(H)/k(D) = 8.8 +/- 0.2, rho = 1.87 +/- 0.05, beta(1g) = -0.55 +/- 0.10, Delta H-double dagger = 6.5 +/- 0.1 kcal/mol, and Delta S-double dagger = -29.0 +/- 1.5 eu. The k(H)/k(D), Hammett rho, and \beta(1g)\ values increase as the beta-aryl group is changed in the order phenyl < thienyl < furyl. The results indicate that the transition state structure for the nitrile-forming elimination changes slightly toward product-like with the change of the beta-aryl group.
• Hein, F.; Schwartzkopff, O.; Hoyer, K., Berichte der Deutschen Chemischen Gesellschaft, 1928, vol. 61, p. 730 - 753
  作者：Hein, F.、Schwartzkopff, O.、Hoyer, K.、Klar, K.、Eissner, W.、Clauss, W.

  DOI：——

  日期：——
• 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.