1,1,1-三氯乙基自由基 | 23273-89-4

• 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: 1,1,1-三氯乙基自由基
• 英文名称: 1,1,1-trichloroethyl radical
• 英文别名: 2,2,2-trichloroethyl radical；1,1,1-trichloroethylene
• CAS: 23273-89-4
• 化学式: C₂H₂Cl₃
• 分子量: 132.397
• InChiKey: CZWMFYUHOQKUFL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1,1,1-三氯乙基自由基 在 hydroxide 作用下， 以 gas 为溶剂， 24.9 ℃ 、98.66 kPa 条件下， 生成 2,2,2-三氯乙醇
  参考文献：
  名称：

  Laser photolysis/laser-induced fluorescence studies of the reaction of hydroxyl with 1,1,1-trichloroethane over an extended temperature range

  摘要：

  Absolute rate coefficients are determined for the gas-phase reaction of OH radicals with 1,1,1-trichloroethane over an extended temperature range. Employing a laser photolysis/laser-induced fluorescence technique, experiments were conducted with a flow system at a total pressure of 740 +/- 10 Torr using He as diluent and carrier gas. The rate coefficients, obtained over the temperature range 298-761 K, exhibited pronounced non-Arrhenius behavior and were best described by the modified Arrhenius equation k(T) = (3.95 +/- 0.78) X 10(-13)(T/300)2.08 exp{(-1068 +/- 108)/T} CM3 Molecule-1 s-1. Comparison of the data with numerous lower temperature measurements is presented. The temperature dependence of the data is compared with empirical and transition-state model calculations. The reactivity of this compound with OH compared to other chlorinated ethanes at both lower and higher reaction temperatures is presented and discussed.

  DOI：

  10.1021/j100201a048
• 作为产物：
  描述：

  三氯乙烷 在 氯 作用下， 7.0 ℃ 、2.8 kPa 条件下， 生成 1,1,1-三氯乙基自由基
  参考文献：
  名称：

  从 C2H6、C2D6、CH3CHCl2、CD3CHCl2、CH3CCl3 和 CD3CCl3 中的甲基中提取氢/氘的竞争性光氯化和动力学同位素效应

  摘要：

  已经使用甲烷在 7-95 °C 的温度范围内研究了通过光化学产生的基态氯原子从乙烷、1,1-二氯乙烷、1,1,1-三氯乙烷及其一些氘代类似物中提取氢和氘作为竞争对手。报告了以下反应的速率常数及其温度系数： 在所有情况下均观察到阿伦尼乌斯定律温度相关性。混合初级和 α-次级动力学同位素效应为 k1/k2 = 2.79 ± 0.27、k4/k6 = 4.13 ± 0.32、k7/k8 = 1.46 ± 0.12 在 298 K 并降低至 k1/k2 = 2.53 ± 0.26、k = 4.06 ± 0.28，k7/k8 = 1.45 ± 0.09 在 370 K，显示“正常”温度依赖性。从甲基中提取 H/D 的动力学同位素效应随着相邻氯甲基中氯取代基数量的增加而降低。β-二次同位素效应 k3/k5 接近于 1，并显示出轻微的逆温度依赖性。

  DOI：

  10.1139/v85-185

文献信息

• Kinetics of the gas-phase reactions of chlorine atoms with CH₂F₂, CH₃CCl₃, and CF₃CFH₂over the temperature range 253-553 K
  作者：E. J. K. Nilsson、M. S. Johnson、O. J. Nielsen、E. W. Kaiser、T. J. Wallington

  DOI：10.1002/kin.20398

  日期：2009.6

  to study the title reactions in 930–1200 mbar of N2 diluent. The reaction rate coefficients measured in the present work are summarized by the expressions k(Cl + CH2F2) = 1.19 × 10−17 T2 exp(−1023/T) cm3 molecule−1 s−1 (253–553 K), k(Cl + CH3CCl3) = 2.41 × 10−12 exp(−1630/T) cm3 molecule−1 s−1 (253–313 K), and k(Cl + CF3CFH2) = 1.27 × 10−12 exp(−2019/T) cm3 molecule−1 s−1 (253–313 K). Results are discussed

  相对速率技术用于研究930–1200 mbar N 2稀释剂中的标题反应。本工作中测得的反应速率系数由表达式k（Cl + CH 2 F 2）= 1.19×10 -17 T 2 exp（-1023 / T）cm 3分子-1 s -1（253-553）总结。 K），k（Cl + CH 3 CCl 3）= 2.41×10 -12 exp（−1630 / T）cm 3分子-1 s -1（253–313 K）和k（Cl + CF 3 CFH 2）= 1.27×10 -12 exp（-2019 / T）cm 3分子-1 s -1（253-313 K）。关于文献数据讨论了结果。©2009 Wiley Periodicals，Inc.国际化学杂志Kinet 41：401–406，2009
• Atmospheric Chemistry of 1,1,1-Trichloroethane: UV Spectra and Self-Reaction Kinetics of CCl3CH2 and CCl3CH2O2 Radicals, Kinetics of the Reactions of the CCl3CH2O2 Radical with NO and NO2, and the Fate of the Alkoxy Radical CCl3CH2O
  作者：Jesper Platz、Ole J. Nielsen、Jens Sehested、Timothy J. Wallington

  DOI：10.1021/j100017a044

  日期：1995.4

  A pulse radiolysis technique was used to measure the UV absorption spectra of CCl3CH2 and CCl3CH2O2 radicals over the range 220-300 nm. At 220 nm, sigma(CCl3CH2) = (9.4 +/- 1.1) x 10(-18) cm(2) molecule(-1); at 250 nm, sigma(CCl3CH2O2) = (2.9 +/- 0.3) x 10(-18) cm(2) molecule(-1). The observed self-reaction rate constants, defined as -d[CCl3CH2]/dt = 2k(4)[CCl3CH2] and -d[CCl3CH2O2]/dt = 2k(5obs)[CCl3CH2O2](2), were k(4) = (9.1 +/- 1.1) x 10(-12) and k(5obs) = (4.7 +/- 1.6) x 10(-12) cm(3) molecule(-1) s(-1). The reaction of CCl3CH2O2 radicals with NO gives CCl2CH2O radicals. In the atmosphere, >96% of the CCl3CH2O radicals react with O-2 to give CCl3CHO. The rate constants for the reactions of CCl3CH2O2 radicals with NO and NO2 were determined to be k(6) greater than or equal to 6.1 x 10(-12) cm(3) molecule(-1) s(-1) and k(7) = (6.5 +/- 0.4) x 10(-12) cm(3) molecule(-1) s(-1), respectively. As a part of this work, the rate constant for the reaction between F atoms and CCl3CH3 was determined to be k(3) = (6.8 +/- 1.5) x 10(-12) cm(3) molecule(-1) s(-1). A relative rate technique was used to measure rate constants for the reactions of Cl atoms with: CCl3CH3, (9.9 +/- 2.0) x 10(-15); CCl3CHO, (6.0 +/- 1.3) x 10(-12); and CCl3CH2OH (3.0 +/- 0.6) x 10(-12) (units of cm(3) molecule(-1) s(-1)) at 296 K. Results are discussed in the context of the atmospheric chemistry of 1,1,1-trichloroethane.
• Rate constants for isomerization of polychloroalkyl radicals with 1,2-migration of chlorine atom, as determined by means of ESR
  作者：R. G. Gasanov

  DOI：10.1007/bf00951218

  日期：1980.10
• Competitive photochlorination and kinetic isotope effects for hydrogen/deuterium abstraction from the methyl group in C₂H₆, C₂D₆, CH₃CHCl₂, CD₃CHCl₂, CH₃CCl₃, and CD₃CCl₃
  作者：E. Tschuikow-Roux、Jan Niedzielski、F. Faraji

  DOI：10.1139/v85-185

  日期：1985.5.1

  α-secondary kinetic isotope effects are k1/k2 = 2.79 ± 0.27, k4/k6 = 4.13 ± 0.32, k7/k8 = 1.46 ± 0.12 at 298 K and decrease to k1/k2 = 2.53 ± 0.22, k4/k6 = 4.06 ± 0.28, k7/k8 = 1.45 ± 0.09 at 370 K, showing a "normal" temperature dependence. The kinetic isotope effect for H/D abstraction from the methyl group decreases with increasing number of chlorine substituents in the adjacent chloromethyl group. The

  已经使用甲烷在 7-95 °C 的温度范围内研究了通过光化学产生的基态氯原子从乙烷、1,1-二氯乙烷、1,1,1-三氯乙烷及其一些氘代类似物中提取氢和氘作为竞争对手。报告了以下反应的速率常数及其温度系数： 在所有情况下均观察到阿伦尼乌斯定律温度相关性。混合初级和 α-次级动力学同位素效应为 k1/k2 = 2.79 ± 0.27、k4/k6 = 4.13 ± 0.32、k7/k8 = 1.46 ± 0.12 在 298 K 并降低至 k1/k2 = 2.53 ± 0.26、k = 4.06 ± 0.28，k7/k8 = 1.45 ± 0.09 在 370 K，显示“正常”温度依赖性。从甲基中提取 H/D 的动力学同位素效应随着相邻氯甲基中氯取代基数量的增加而降低。β-二次同位素效应 k3/k5 接近于 1，并显示出轻微的逆温度依赖性。
• Laser photolysis/laser-induced fluorescence studies of the reaction of hydroxyl with 1,1,1-trichloroethane over an extended temperature range
  作者：Zhen Jiang、Philip H. Taylor、Barry Dellinger

  DOI：10.1021/j100201a048

  日期：1992.10

  Absolute rate coefficients are determined for the gas-phase reaction of OH radicals with 1,1,1-trichloroethane over an extended temperature range. Employing a laser photolysis/laser-induced fluorescence technique, experiments were conducted with a flow system at a total pressure of 740 +/- 10 Torr using He as diluent and carrier gas. The rate coefficients, obtained over the temperature range 298-761 K, exhibited pronounced non-Arrhenius behavior and were best described by the modified Arrhenius equation k(T) = (3.95 +/- 0.78) X 10(-13)(T/300)2.08 exp(-1068 +/- 108)/T} CM3 Molecule-1 s-1. Comparison of the data with numerous lower temperature measurements is presented. The temperature dependence of the data is compared with empirical and transition-state model calculations. The reactivity of this compound with OH compared to other chlorinated ethanes at both lower and higher reaction temperatures is presented and discussed.