Chloromethylperoxy radical | 73761-32-7

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氯化物
• 英文名称: Chloromethylperoxy radical
• 英文别名: chloromethylperoxy；Methyldioxy, chloro-
• CAS: 73761-32-7
• 化学式: CH₂ClO₂
• 分子量: 81.4787
• InChiKey: BYEIONXFWDIOGF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  4
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  10.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Chloromethylperoxy radical 在 氯丙嗪 、 水 作用下， 以 二氯甲烷 、 异丙醇 为溶剂， 生成 氯(氢过氧)甲烷
  参考文献：
  名称：

  醇水溶液中过氧自由基氧化有机化合物的速率常数与温度的关系

  摘要：

  Rate constants for reactions of chlorinated methylperoxyl radicals with chlorpromazinc (2-chloro-10-[3-(dimethylamino)-propyl]phenothiazine), trolox (6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxy?? lic acid), and ascorbate in aqueous alcohol solutions have been measured by pulse radiolysis as a function of temperature, generally between 5 and 75-degrees-C. The rate constants varied between 10(6) and 10(9) M-1 s-1, the calculated Arrhenius activation energies ranged from 1 to 30 kJ mol-1, and the preexponential factors also varied considerably, with log A ranging from 7 to 14. In general, room temperature rate constants increase with an increase in the number of chlorine atoms on the radical (increasing its electron affinity and thus the driving force for the reaction) and with an increase in the solvent polarity. The Arrhenius preexponential factor and the activation energy both increased as the proportion of water in the solvent mixture increased; i.e., the increase in rate constant with solvent polarity is a result of two compensating effects. Electron transfer from the organic reductants to the chlorinated methylperoxyl radicals is suggested to take place via an inner-sphere mechanism involving a transient adduct of the peroxyl radical to the reductant.

  DOI：

  10.1021/j100181a045
• 作为产物：
  描述：

  氯甲基自由基 在 氧气 作用下， 24.9 ℃ 、101.32 kPa 条件下， 生成 Chloromethylperoxy radical
  参考文献：
  名称：

  Kinetics of the dichloromethyl and chloromethyl association reactions with molecular oxygen between 298 and 448 K and from 1 to 760 Torr of total pressure

  摘要：

  The rate constants for the recombination reactions between molecular oxygen and the halogenated methyl radicals CHCl2 and CH2Cl were determined over the pressure range of 1 to 760 Torr in nitrogen as a function of temperature. The CHCl2 + O2 reaction (1) was studied over the temperature range 298 < T/K < 383 and the CH2Cl reaction (2) over the range 298 < T/K < 448. The large range in pressure was attained by using two complementary techniques: Low-pressure experiments (1-10 Torr) were concluded using laser photolysis/photoionization mass spectrometry. High-pressure experiments (20-760 Torr) were carried out with the laser photolysis/UV absorption spectroscopy technique. A nonvariational RRKM calculation using previously determined thermodynamic parameters for these two reactions was performed, providing a complete and coherent picture of the kinetics and equilibria for these reactions. In addition, the data were fitted to a simplified and commonly used form of an expression developed by Troe to extrapolate falloff data to obtain high- and low-pressure limiting rate constants. Parameters are provided that allow the calculation of the rate constants of the title reactions as a function of temperature and pressure. The data are well represented by the following limiting rate-constant expressions: reaction 1, k(o)(T) = (1.26 +/- 0.03) X 10(-30)(T/300)-4.0 +/- 0.2 cm6 molecule-2 s-1, k(oo)(T) = (2.8 +/- 0.2) X 10(-12)(T/300)-1.4 +/- 0.3 cm3 Molecule-1 s-1; reaction 2, k(o)(T) = (1.88 +/- 0.05) X 10(-30)(T/300)-3.2 +/- 0.2 cm6 molecule-2 s -1, k(oo)(T) = (2.9 +/- 0.2) X 10(-12)(T/300)-1.2 +/- 0.4 cm3 molecule-1 s-1.

  DOI：

  10.1021/j100120a023

文献信息

• Structure and reactivity of peroxyl and sulphoxyl radicals from measurement of oxygen-17 hyperfine couplings: relationship with taft substituent parameters
  作者：Michael D. Sevilla、David Becker、Mengyao Yan

  DOI：10.1039/ft9908603279

  日期：——

  hyperfine couplings are shown to monitor closely the spin density distribution on the oxygen atoms in the peroxyl radicals. The experimental 17O couplings suggest a value of –5.7 mT for the anisotropic coupling parameter, B, in good agreement with the theoretical value calculated from improved wavefunctions. An increase in the magnitude of the terminal oxygen coupling is shown to correlate with an increase

  用电子顺磁共振波谱研究了一系列具有不同吸电子能力的取代基的过氧自由基（ROO 3）。已经产生，鉴定了十六个基于碳的自由基，并与17 O-标记的分子氧反应以产生相应的过氧自由基。以碳为中心的自由基前体包括烷基，芳族，卤代烃，脂质和醇基。氧17超精细偶合被显示为密切监测过氧自由基中氧原子上的自旋密度分布。实验的17 O耦合建议各向异性耦合参数B的值为–5.7 mT与通过改进的波函数计算出的理论值非常吻合。末端氧偶联的量的增加显示出与过氧自由基的反应性的增加相关。另外，塔夫脱取代基参数（σ *）也与氧17偶合相关。结果允许过氧化自由基的反应性的估计从氧-17联轴器和建议络合的超氧离子可以比自由直径：多个反应性˙- 2。根据基于碳的过氧自由基的结果，讨论了半胱氨酸磺酰基过氧自由基和硫醇过氧自由基。磺酰基过氧自由基被认为是高反应性的，而巯基过氧自由基具有独特的性质，这表明它具有不同的性质。
• Oxidation of Ferrous and Ferrocyanide Ions by Peroxyl Radicals
  作者：G. I. Khaikin、Z. B. Alfassi、R. E. Huie、P. Neta

  DOI：10.1021/jp9533335

  日期：1996.1.1

  Alkylperoxyl and arylperoxyl radicals were produced by pulse radiolysis in aqueous solutions, and their reactions with ferrous and ferrocyanide ions were studied by kinetic spectrophotometry. Oxidation of Fe(CN)64- took place with rate constants that varied from <1 × 105 to 5 × 107 L mol-1 s-1, depending on the electron-withdrawing effects of the substituents on the peroxyl radical and presumably reflecting

  在水溶液中通过脉冲辐射分解产生烷基过氧自由基和芳基过氧自由基，并通过动力学分光光度法研究它们与亚铁和亚铁氰化物离子的反应。Fe（CN）6 4-的氧化速率常数从<1×10 5到5×10 7 L mol -1 s -1变化，这取决于取代基对过氧自由基和电子的吸电子作用。大概反映了过氧自由基还原电位的变化，这是外球电子转移所期望的。Fe aq 2+的氧化另一方面，是通过受水配体的解离交换速率控制的内球机理发生的。所述速率常数分别为几乎相同的所有过氧自由基检查（ķ =（0.5-1.1）×10 6大号摩尔-1小号-1）和所涉及的瞬时中间体的形成，RO 2 -的Fe 3+，后来分解产生Fe aq 3+。H +和Fe 2+促进分解。所提出的机理是对先前提出的反应方案的修改。
• Kinetics of the Cross Reactions of CH₃O₂ and C₂H₅O₂ Radicals with Selected Peroxy Radicals
  作者：Eric Villenave、Robert Lesclaux

  DOI：10.1021/jp960765m

  日期：1996.1.1

  be between the rate constants for the self-reactions of RO2 and CH3O2 (or C2H5O2). However, when the RO2 self-reaction is fast, the cross reaction with CH3O2 (or C2H5O2) is also fast, with similar rate constants for both reactions, suggesting that these particular peroxy radical cross reactions can play a significant role in the chemistry of hydrocarbon oxidation processes in the troposphere and in

  使用两种技术研究了选定的过氧自由基（RO 2）与CH 3 O 2和与C 2 H 5 O 2的反应动力学：准分子激光光解法和常规闪速光解法，均与紫外吸收光谱法结合。在适当的烃存在下，通过分子氯的光解或通过适当的烷基氯的光解，产生自由基。除烯丙基过氧自由基与CH 3 O 2的反应外，所有此类交叉反应动力学均在760 Torr总压力和室温下进行。，对于将其291和423之间所确定的速率常数K，从而产生以下速率表达式：  ķ 15 =（2.8±0.7）×10 -13 EXP [（515±75）/ Ť ]厘米3分子-1小号- 1。（2.0±0.5）×10 -13，（1.5±0.5）×10 -12，（9.0±0.15）×10 -14，<2.0×10 -12，（2.5±0.5）×10 -12，和CH 3 O 2的反应获得了（8.2±0.6）×10 -12（cm 3分子-1 s -1的单位）。具有C 2 H
• Packer, John E.; Willson, Robin L.; Bahnemann, Detlef, Journal of the Chemical Society. Perkin transactions II, 1980, p. 296 - 299
  作者：Packer, John E.、Willson, Robin L.、Bahnemann, Detlef、Asmus, Klaus-Dieter

  DOI：——

  日期：——
• Rate constants for reduction of substituted methylperoxyl radicals by ascorbate ions and N,N,N',N'-tetramethyl-p-phenylenediamine
  作者：P. Neta、R. E. Huie、S. Mosseri、L. V. Shastri、J. P. Mittal、P. Maruthamuthu、S. Steenken

  DOI：10.1021/j100347a045

  日期：1989.5