氯甲氧基 | 114282-89-2

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氯化物
• 中文名称: 氯甲氧基
• 英文名称: chloromethoxy radical
• CAS: 114282-89-2
• 化学式: CH₂ClO
• 分子量: 65.4793
• InChiKey: ZDOLPVWPBVTPNA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  3
• 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：
  1
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  氯甲氧基 在 氧气 作用下， -8.15 ℃ 、666.61 Pa 条件下， 生成 甲酰氯
  参考文献：
  名称：

  Kinetics of CH₂ClO Radical Reactions with O₂ and NO, and the Unimolecular Elimination of HCl

  摘要：

  The kinetics of the title reactions were investigated at 5-35 Torr total pressure and 265-306 K by UV flash photolysis and time-resolved mass spectrometry. The CH2ClO radical was generated by photolysis of NOCl in the presence of CH3Cl, O-2, and NO. Atomic chlorine from NOCl photodissociation abstracted H from CH3Cl acid initiated oxidation of CH2Cl radicals, leading to formation of CH2ClO. The CH2ClO radical reacted with both O-2 and NO, or underwent unimolecular elimination of HCl. The kinetics were determined from growth rates of HC(O)Cl and HCl. The rate coefficient of the CH2ClO + O-2 reaction was found to be independent of pressure, The temperature dependence can be expressed as: k(CH2ClO + O-2) = (2.0 +/- 0.7) x 10(-12) exp[-(934 +/- 128)/T] cm(3) molecule(-1) s(-1). The rate coefficients for the CH2ClO + NO reaction were found to be independent of both pressure and temperature, with the value k(CH2ClO + NO) = (2.7 +/- 0.6) x 10(-12) cm(3) molecule(-1) s(-1), obtained by averaging all rate coefficients determined over the experimental range of pressure and temperature. The rate coefficient for unimolecular elimination of HCl from CH2ClO was found to be pressure dependent, and well into the falloff. The unimolecular rate coefficient at 10 Torr can be expressed as (7.7 +/- 2.3) x 10(9) exp[-(4803 +/- 722)/T]s(-1).

  DOI：

  10.1021/jp001953m
• 作为产物：
  描述：

  Chloromethylperoxy radical 生成 氯甲氧基 、 alkaline earth salt of/the/ methylsulfuric acid
  参考文献：
  名称：

  Kinetic Study of the Reactions of CH2ClO2 with Itself and with HO2, and Theoretical Study of the Reactions of CH2ClO, between 251 and 600 K

  摘要：

  The UV absorption spectrum, self-reaction (2CH2ClO2 --> 2CH2ClO + O2 (1)) kinetics and the kinetics of the reaction with HO2 (CH2ClO2 + HO2 --> products (3)) of the chloromethylperoxy radical, CH2ClO2, have been studied between 251 and 600 K and at 760 Torr total pressure. Chloromethylperoxy radicals were produced by the flash photolysis of Cl2/CH3Cl/O2/N2 mixtures; for the study of reaction 3, chloromethylperoxy and hydroperoxy radicals were produced simultaneously by the flash photolysis Of Cl2/CH3Cl/CH3OH/O2/N2 mixtures. Radical concentrations were monitored by UV absorption spectrometry from 205 to 290 nm. The chloromethoxy radicals formed in reaction 1 produce hydroperoxy radicals via reaction with molecular oxygen (CH2ClO + O2 --> HO2 + CHClO (2)). These hydroperoxy radicals are removed via reaction 3 and by their self-reaction (HO2 + HO2 --> H2O2 + O2 (4)). Unlike the majority of systems studied to date, the rate constant for the RO2 + HO2 reaction is not significantly faster than that for the RO2 + RO2 reaction and significant transient concentrations of HO2 are produced. Consequently, the observed second-order rate constant for radical disappearance depends strongly on the monitoring wavelength, and UV absorption cross-section and values of k1 and k3 could only be obtained by an iterative process. Sensitivity analyses with respect to all model parameters on fitted rate constants were performed. Arrhenius fits to the data on k1 and k3 gave k1 = (1.95 +/- 0.16) X 10(-13) exp[(874 +/- 26)K/7]cm3 molecule-1 s-1 and k3 = (3.26 +/- 0.61) X 10(-13) exp[(822 +/- 63)K/T] cm3 molecule-1 s-1. Average absolute uncertainties in k1 and k3 over the temperature range studied, including experimental scatter and uncertainties in the analysis parameters, were estimated to be 31 and 33%, respectively. The UV absorption spectrum of the chloromethylperoxy radical is typical of the spectra of alkylperoxy radicals, peaking at 230 nm, where sigma = (4.06 +/- 0.53) X 10(-18) cm2 molecule-1. In sharp contrast to the behavior of fully halogenated methylperoxy radicals, there was no evidence for the elimination of a chlorine atom from the chloromethoxy radical, CH2ClO, even at the highest temperature employed in this study. Semiempirical MNDO calculations and RRKM calculations were performed which suggest that unimolecular elimination of HCl from CH2ClO is important at high temperatures.

  DOI：

  10.1021/j100062a027

文献信息

• 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
• The chloromethoxy radical: kinetics of the reaction with O2 and the unimolecular elimination of HCl at 306 K
  作者：Fuxiang Wu、Robert W Carr

  DOI：10.1016/s0009-2614(99)00350-4

  日期：1999.5

  The gas-phase kinetics of the CH2ClO radical, formed by flash photolysis of Cl-2 in CH3Cl/O-2/N-2 mixtures, was investigated at 306 K and at total pressures from 5 to 35 Tori by time-resolved mass spectrometry. Reaction of CH2ClO with O-2 to form HC(O)Cl and HO2, and unimolecular dissociation to HCl and HCO were both observed. The absolute rate coefficient for reaction of CH2ClO with O-2 is (2.8 +/- 1.2) X 10(-13) cm(3) molecule(-1) s(-1). The unimolecular dissociation is well into the fall-off, the rate coefficient increasing from 6 X 10(2) s(-1) to 4 X 10(3) s(-1) between 5 and 35 Torr. (C) 1999 Elsevier Science B.V. All rights reserved.