4-羧基二苯甲酮自由基 | 128884-32-2

• 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: 4-羧基二苯甲酮自由基
• 英文名称: 4-carboxybenzophenone radical
• CAS: 128884-32-2
• 化学式: C₁₄H₁₁O₃
• 分子量: 227.24
• InChiKey: QTFFLMJCCUAQPF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.69
• 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：
  57.53
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  4-羧基二苯甲酮自由基 在 azomethine-H monosodium salt 作用下， 以 甲苯 为溶剂， 生成 4-苯甲酰苯甲酸
  参考文献：
  名称：

  Study of the mechanism of the photoreduction of azomethine dyes sensitized by carbonyl compounds

  摘要：

  DOI：

  10.1007/bf00961974
• 作为产物：
  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

文献信息

• Mechanism of Sulfoxide Formation through Reaction of Sulfur Radical Cation Complexes with Superoxide or Hydroxide Ion in Oxygenated Aqueous Solution
  作者：Brian L. Miller、Todd D. Williams、Christian Schöneich

  DOI：10.1021/ja962032l

  日期：1996.11.13

  We have characterized and quantified several pathways which transform aliphatic sulfur radical cations into sulfoxides in aqueous solution. Sulfur radical cations were produced photochemically via one-electron photooxidation through triplet 4-carboxybenzophenone. Sulfur radical cations and superoxide yield sulfoxide, confirmed by oxygen product isotope effects and an inhibitory role of superoxide dismutase

  我们已经表征和量化了几种将脂肪族硫自由基阳离子在水溶液中转化为亚砜的途径。硫自由基阳离子是通过三线态 4-羧基二苯甲酮的单电子光氧化以光化学方式产生的。硫自由基阳离子和超氧化物产生亚砜，通过氧产物同位素效应和超氧化物歧化酶的抑制作用证实。在超氧化物歧化酶竞争实验的基础上，二甲硫醚自由基阳离子与超氧化物反应的速率常数为（2.3±1.2）×1011 M-1 s-1。超氧化物歧化酶的脱金属变体不抑制超氧化物介导的亚砜形成，证实了酶活性位点对于抑制的重要性。
• Hydrogen transfer from ketyl radicals to nitroxyl radicals
  作者：A. S. Tatikolov、V. I. Sklyarenko、V. A. Kuz'min

  DOI：10.1007/bf00961676

  日期：1990.5

  The transfer of an H atom from a ketyl radical (KR) to a nitroxyl radical is the sole reaction occurring between benzophenone or acetone KR and nitroxyl radicals (NR). The rate constants (k(H)) of the reaction of the KR of substituted benzophenones with the NR - 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl and 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl in various solvents were measured by the pulse photolysis method. In low-viscosity solvents (up to 1-2 cP), the values of k(H) are not limited by the diffusion of the reagents. The k(H) values decrease with increase in the Hammet's sigma-constants of the substituents in the KR and with decrease in the reduction potential of the NR, which indicates a charge transfer from the KR to NR in the transition state of the reaction. A cyclic structure was proposed for the transition state. The reaction is characterized by a low isotopic effect (k(H)/k(D) = 1.4-1.5). The dependence of log k(H) on the solvation parameter of the solvent E(t)(30) is V-shaped in character.
• 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.