benzophenone-4-carboxylic acid radical anion | 79802-46-3

• 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: benzophenone-4-carboxylic acid radical anion
• 英文别名: 4-carboxybenzophenone anion radical；4-carboxybenzophenone radical anion
• CAS: 79802-46-3
• 化学式: C₁₄H₁₀O₃
• 分子量: 226.232
• InChiKey: JQBTVKKLJCTEHG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.67
• 重原子数：
  17.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  60.36
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  benzophenone-4-carboxylic acid radical anion 在 methonine 作用下， 以 水 为溶剂， 生成 4-羧基二苯甲酮自由基
  参考文献：
  名称：

  含硫氨基酸的 4-羧基二苯甲酮敏化光氧化。纳秒激光闪光光解和脉冲辐解研究

  摘要：

  中性水溶液中的 4-羧基二苯甲酮 (CB) 通过光敏作用氧化含硫氨基酸。用闪光光解和脉冲辐解技术研究了该反应的机理。确定了 12 个氨基酸（相对于硫原子具有可变的相对位置和末端官能团 COOH 和 NH 2 的数量）猝灭 CB 三重态的速率常数，发现为 1.8×10 8 -2.9× 10 9 M -1 秒 -1

  DOI：

  10.1021/ja00052a025
• 作为产物：
  描述：

  4-苯甲酰苯甲酸 在 三氧化硫 作用下， 以 水 、 乙腈 为溶剂， 生成 benzophenone-4-carboxylic acid radical anion
  参考文献：
  名称：

  Interactions of nitrite and sulfite with organic triplets: charge transfer versus energy transfer: the role of reorganization energy in triplet-anion interactions and spectroscopic methods for its evaluation

  摘要：

  Charge-transfer (CT) and energy-transfer (NT) interactions of simple anions with organic triplets are reviewed and discussed in connection with new quenching rate constant (k(q)) and radical yield measurements for SO32- and NO2-. In the latter case, both processes may occur at high organic triplet energies. Reorganization energies for one-electron oxidations are obtained for several anions, using data on charge-transfer-to-solvent (CTTS) spectra and photoelectron emission thresholds, which, like thc kinetic parameters of Marcus-Hush theory, also reflect Franck-Condon strains. These results, combined with thermodynamic free energies, give vertical redox potentials which correlate better than do equilibrium potentials with quenching rates. The theoretical basis for correlation between k(q) and h-nu(CTTS) is discussed in the framework of Marcus rate theory. Assigning the total reorganization energy in the CT quenching reaction to the small anion component of the D-A pair gives reasonable agreement with data on quenching of dye triplets but too slow rates for aryl carbonyl triplets where exciplex formation may possibly occur. The optical reorganization energy for NO2- leads to values of the thermal self-exchange mte agreeing with those computed from the Marcus-Hush cross-relations, which also neglect bonding effects. The mechanism of NO2- interaction with triplets is discussed in detail, including indirect kinetic evidence for quenching of a short-lived exciplex by NO2- without radical formation. The possibility of reduction by triplet NO2- formed by initial NT from the organic triplet is also considered. Finally, a scheme is presented involving an equilibrium between CT and NT states and relating the free energy difference between these states to radical yields.

  DOI：

  10.1021/j100192a018

文献信息

• Quenching, radical formation, and disproportionation in the photoreduction of 4-carboxybenzophenone by 4-carboxybenzhydrol, hydrazine, and hydrazinium ion
  作者：Shai Inbar、Henry Linschitz、Saul G. Cohen

  DOI：10.1021/ja00414a047

  日期：1981.12

  = 6600 M/sup -1/ cm/sup -1/), for CBH, lambda/sub max/ = 570 nm (epsilon = 5500), and for the radical anion CB/sup -/, lambda/sub max/ = 660 nm (epsilon = 8100). The pKa ofCBH was determined, 8.2. Rate constants were determined: for combination of CBH to pinacol, 2k/sub 6/ = 1.8 x 10/sup 9/ M/sup -1/s/sup -1/; for reactions of CBH with CB/sup -/, k/sub 7/ = 1.1 x 10/sup 9/ M/sup -1/s/sup -1/; for disproportionation

  已对 4-羧基二苯甲酮 (CB)-4-羧基-二苯甲醇 (CBH/sub 2/) 和 CB-肼系统在 pH 5.8 至 12 范围内进行了激光闪光和稳定照射研究。 与 CBH/sub 反应2/，CB 三重态部分被羧酸盐淬灭，k/sub q/ 约。= 4 x 10/sup 6/ M/sup -1/s/sup -1/；总反应，k/sub 4/ = 3.0 x 10/sup 7/ M/sup -1/s/sup -1/ 导致羰基自由基 CBH，phi = 1.7。记录 CB 三重峰的吸收光谱，λ/sub max/ = 535 nm (epsilon = 6600 M/sup -1/cm/sup -1/)，对于 CBH，λ/sub max/ = 570 nm (epsilon = 5500) ，对于自由基阴离子 CB/sup -/，λ/sub max/ = 660 nm (epsilon = 8100)。CBH的pKa被确定为8
• Mechanism of 4-carboxybenzophenone-sensitized photooxidation of methionine-containing dipeptides and tripeptides in aqueous solution
  作者：Bronislaw Marciniak、Gordon L. Hug、Krzysztof Bobrowski、Halina Kozubek

  DOI：10.1021/j100036a037

  日期：1995.9

  The mechanism of 4-carboxybenzophenone (CB)-sensitized photooxidation of methionine-containing dipeptides (Met-Gly and Gly-Met) and tripeptides (Met-Gly-Gly, Gly-Met-Gly, and Gly-Gly-Met) was investigated using nanosecond flash photolysis and steady-state photolysis. The rate constants for quenching of the CB triplet by sulfur-containing peptides were determined to be in the range (1.8-2.3) x 10(9) M(-1) s-(1) for neutral and alkaline solutions. The presence of the various electron-transfer intermediates accompanying the CB triplet quenching events was identified through the use of a multiple-regression procedure that was used to resolve the experimental transient spectra into components. The intermediates identified were the CB ketyl radical anion, the CB ketyl radical, intermolecularly (S therefore S)-bonded radical cations, and intramolecularly (S therefore N)-bonded radical cations derived from peptides. The spectra of appropriate (S therefore S)(+) and (S therefore N)(+) intermediates for the peptides were determined from complementary pulse radiolysis studies in acidified aqueous solutions of the peptides. The types of intermediates were found to depend on the pH of the solution and on the location of the methionine unit with respect to the terminal functions. The quantum yields of all the transients and the kinetics of their formation and decay were measured by flash photolysis, and quantum yields of CO2 formation were measured by steady-state photolysis. These results were based on the resolution of the spectral components in the transient absorption spectra at various delays after the flash. A detailed mechanism of the CB-sensitized photooxidation of methionine-containing peptides was discussed and compared to that for methionine.