α-chloroethyl radical | 16520-13-1

• 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: α-chloroethyl radical
• 英文别名: 1-chloroethyl radical；chloroethane；1-Chloroethane
• CAS: 16520-13-1
• 化学式: C₂H₄Cl
• 分子量: 63.5068
• InChiKey: JSICDMRDIHNAKT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  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：

  α-chloroethyl radical 在 氢溴酸 作用下， 生成 氯乙烷
  参考文献：
  名称：

  R + HBr⇌RH + Br（R = CH 2 Cl，CHCl 2，CH 3 CHCl或CH 3 CCl 2）平衡的动力学和热化学

  摘要：

  CH 2 Cl，CHCl 2，CH 3 CHCl和CH 3 CCl 2与HBr的反应动力学已在与光电离质谱仪耦合的可加热管式反应器中进行了研究。自由基R通过脉冲248 nm激基复合物激光光解在反应器中均匀产生。在伪一阶条件下，监测R的衰减与HBr浓度的关系，以确定速率常数与温度和压力范围的关系。在较宽的温度范围内分别研究了反应，并在这些温度范围内将确定的速率常数与Arrhenius表达式拟合（规定的误差极限为1σ +学生的t值，单位为cm 3分子–1 s –1）：k（CH 2 Cl）=（6.6±1.7）×10 –13 exp [-（4.1±0.2）kJ mol –1 / RT ]，k（CHCl 2）=（4.1±1.0）×10 –13 exp [–（9.8±1.0）kJ mol –1 / RT ]，k（CH 3 CHCl）=（3.0±0.9）×10 –13 exp [+（3.0±0.2） ）kJ

  DOI：

  10.1039/ft9969203069
• 作为产物：
  描述：

  氯乙烯 生成 α-chloroethyl radical
  参考文献：
  名称：

  羰基化合物反应中羰基和烷基自由基的反应性

  摘要：

  双分子自由基反应的抛物线模型用于分析羰基自由基的氢转移反应：>C·OH+R1COR2→>C=O+R1R2C·OH。描述试剂反应性的参数由实验数据计算。得到表征作为氢供体的羰基和烷基自由基与烯烃和羰基化合物反应的参数：>C·OH+R1CH=CH2→>C=O+R1C·HCH3；>R1CH=CH2+R2C·HCH2R3→R2C·HCH3+R2CH=CHR3。这些参数用于计算这些转换的活化能。比较了自由基和分子（醛、酮和醌）从 C-H 和 O-H 键夺氢反应的动力学参数。

  DOI：

  10.1007/bf02494263

文献信息

• Temperature dependence of the kinetic isotopic effect of the reaction of Cl atoms with C2H5Cl between 298 and 550K
  作者：Dariusz Sarzyński、Agnieszka A. Gola、Katarzyna Brudnik、Ryszard Berkowski、Jerzy T. Jodkowski

  DOI：10.1016/j.cplett.2012.09.072

  日期：2012.12

  gas-phase reactions of chlorine atoms with chloroethane and chloroethane-d5 was studied experimentally. The relative rate method was applied using Cl + CH3Cl as the reference reaction. The overall rate constants for H-abstraction from C2H5Cl (kH), D-abstraction from C2D5Cl (kD), the site-specific rate constants for H-abstraction from α-carbon (kH,α) and β-carbon (kH,β) atoms of C2H5Cl were measured in the

  实验研究了氯原子与氯乙烷和氯乙烷-d 5的气相反应动力学。使用Cl + CH 3 Cl作为参考反应，采用相对速率法。从C 2 H 5 Cl（k H）吸氢的总速率常数，从C 2 D 5 Cl（k D）吸氢的总速率常数，从α碳（k H C 2 H 5的（α）和β-碳（k H，β）原子在总压力为100 Torr的情况下，在298–550 K的温度范围内测量了Cl。速率常数的温度相关性由下式给出：k H  =（2.41±0.21）×10 -11  ×exp（-316±11 / T），k H，α  =（1.36±0.09）×10 -11  ×exp （-202±8 / T），k H，β  =（1.14±0.11）×10 -11  ×exp（-592±16 / T）和k D  =（1.58±0.14）×10 -11  ×exp（- 474±13 / T）cm 3 分子-1  s -1。还估算了动力学同位素效应的值k
• Gas-Phase Carbene Radical Anions: New Mechanistic Insights
  作者：Stephanie M. Villano、Nicole Eyet、W. Carl Lineberger、Veronica M. Bierbaum

  DOI：10.1021/ja801819b

  日期：2008.6.1

  The gas-phase reactivity of the CHCl*- anion has been investigated with a series of halomethanes (CCl4, CHCl3, CH2Cl2, and CH3Cl) using a FA-SIFT instrument. Results show that this anion primarily reacts via substitution and by proton transfer. In addition, the reactions of CHCl*- with CHCl3 and CH2Cl2 form minor amounts of Cl2*- and Cl-. The isotopic distribution of these two products is consistent

  已使用 FA-SIFT 仪器研究了 CHCl*- 阴离子与一系列卤代甲烷（CCl4、CHCl3、CH2Cl2 和 CH3Cl）的气相反应性。结果表明，该阴离子主要通过取代和质子转移进行反应。此外，CHCl*- 与 CHCl3 和 CH2Cl2 的反应会形成少量的 Cl2*- 和 Cl-。这两种产物的同位素分布与插入消除机制一致，其中阴离子插入 C-Cl 键形成不稳定的中间体，从而消除 Cl2*- 或 Cl- 和 Cl*。已知中性和阳离子卡宾插入单键；然而，这是对卡宾阴离子的这种反应性的首次观察。
• Kinetics of the Reactions of CH₂Cl, CH₃CHCl, and CH₃CCl₂ Radicals with Cl₂ in the Temperature Range 191−363 K
  作者：Matti P. Rissanen、Arkke J. Eskola、Raimo S. Timonen

  DOI：10.1021/jp909419v

  日期：2010.4.15

  The kinetics of three chlorinated free radical reactions with Cl-2 have been studied in direct time-resolved measurements. Radicals were produced in low initial concentrations by pulsed laser photolysis at 193 nm, and the subsequent decays of the radical concentrations were measured under pseudo-first-order conditions using photoionization mass spectrometer (PIMS). The bimolecular rate coefficients of the CH3CHCl + Cl-2 reaction obtained from the current measurements exhibit negative temperature dependence and can be expressed by the equation k(CH3CHCl + Cl-2) = ((3.02 +/- 0.14) x 10(-12))(T/300 K)(-1.8 +/- 0.19) cm(3) molecule(-1) s(-1) (1.7-5.4 Torr, 191-363 K). For the CH3CCl2 + Cl-2 reaction the current results could be fitted with the equation k(CH3CCl2 + Cl-2) = ((1.23 +/- 0.02) x 10(-13))(T/300 K)(-0.26 +/- 0.10) cm(3) molecule(-1) s(-1) (3.9-5.1 Torr, 240-363 K). The measured rate coefficients for the CH,CI + CI, reaction plotted as a function of temperature show a minimum at about T = 240 K: first decreasing with increasing temperature and then, above the limit, increasing with temperature. The determined reaction rate coefficients can be expressed as k(CH2Cl + Cl-2) = ((2.11 +/- 1.29) x 10(-14)) exp(773 +/- 183 K/T)(T/300 K)(3.26 +/- 0.67) cm(3) molecule(-1) s(-1) (4.0-5.6 Torr, 201-363 K). The rate coefficients for the CH3CCl2 + Cl-2 and CH2Cl + CI, reactions can be combined with previous results to obtain: k(combined)(CH3CCl2 + Cl-2 ) = ((4.72 +/- 1.66) x exp(971 +/- 106 K/T)(T/300 K)(3.07 +/- 0.23) cm(3) molecule(-1) s(-1) (3.1-7.4 Torr, 240-873 K) and k(comhined)(CH2Cl + Cl-2) = ((5.18 +/- 1.06) x 10(-14)) exp(525 +/- 63 K/T)(T/300 K)(2.52 +/- 0.13) cm(3) molecule(-1) s(-1) (1.8-5.6 Torr, 201-873 K). All the uncertainties given refer only to the la statistical uncertainties obtained from the fitting, and the estimated overall uncertainty in the determined bimolecular rate coefficients is about +/- 15%.
• Evidence for the three-center elimination of hydrogen chloride from 1-chloroethoxy
  作者：M. Matti Maricq、Jichun Shi、Joseph J. Szente、L. Rimai、E. W. Kaiser

  DOI：10.1021/j100140a027

  日期：1993.9

  Time-resolved IR spectral photography and transient diode laser absorption measurements reveal a yield of HCl from the photolysis of Cl2 in the presence of C2H5Cl and O2 which is 78% larger than expected from Cl + C2H5Cl. The HCl formation occurs in two steps: a rapid rise to [HCl] = [Cl]0, followed by a secondary rise to [HCl] = 1.78[Cl]0 with a rate constant of k3 = (5.2 +/- 1.3) X 10(-12) cm3 S-1. In the presence of NO, the rate of secondary HCl formation is greatly enhanced, but its yield (84%) is comparable to that in the absence of NO. The secondary HCl is explained as an elimination product from the CH3CHClO, which can be generated by the reaction of CH3CHClO2 with itself or with NO. The fact that the secondary HCl yield increases by 12% when using CD3CH2Cl shows that the secondary HCl is formed mainly by three-center elimination from the 1-chloroethoxy radical. We also report UV absorption cross sections for CH3CHClO2, which has a broad maximum of sigma(max) = 0.029 angstrom2 from 215 to 248 nm, and CH2ClCH2O2, with sigma(max) = 0.045 angstrom2 at 240 nm. The self-reaction rate constants are (5.2+/-1.3) X 10(-12) cm3 s-l and (6.04-0.8) X 10(-12) cm3 s-1, respectively. Finally, the rate constant for the reaction Cl + C2H5Cl = C2H4Cl + HCl (1) is determined to be k1 = (7.3 +/- 0.9) X 10(-12) cm3 s-1.
• Kinetics of Reactions of Cl Atoms with Ethane, Chloroethane, and 1,1-Dichloroethane
  作者：Mikhail G. Bryukov、Irene R. Slagle、Vadim D. Knyazev

  DOI：10.1021/jp0275138

  日期：2003.8.1

  Reactions of Cl atoms with ethane (1), chloroethane (2), and 1,1-dichloroethane (3) were studied experimentally with the discharge flow/resonance fluorescence technique over wide ranges of temperatures and at pressures between 2.3 and 9.2 Torr. Results of earlier investigations of the reactions of Cl atoms with ethane and chloroethanes are analyzed and compared with the results of the current work. The rate constants of the reaction of Cl atoms with ethane obtained in the current study (k(1) = (4.91 x 10(-12))T-0.47 exp(-82 K/T) cm(3) molecule(-1) s(-1), 299-1002 K) agree with the results of earlier determinations. Combination of the temperature dependence of k(1) obtained in the current work with the existing (mostly at lower temperatures) literature data results in the expression k(1) = (7.23 x 10(-13))T-0.70 exp(+117 K/T) cm(3) molecule(-1) s(-1) (203-1400 K). Rate constants of the reactions of Cl atoms with chloroethane and 1,1-dichloroethane demonstrate different temperature dependences in the low-temperature (room temperature to 378 K) and the high-temperature (4848 10 K) regions. The differences are due to the regeneration of Cl atoms at higher temperatures as a consequence of the fast thermal decomposition of radical products with a chlorine atom in the beta position. This information enables quantitative differentiation between the site-specific reaction channels. The results of the current study, combined with those of earlier relative-rate experiments, were used to derive expressions for the temperature dependences of the rates of the site-specific abstraction channels: k(2a)(T) = (2.76 +/- 0.28) x 10(-11) exp(-455 +/- 44 K/T) (296-810 K), k(2b)(T) = (1.92 +/- 0.47) x 10(-11) exp(-789 +/- 84 K/T) (296-378 K), k(3a)(T) = (1.46 +/- 0.21) x 10(-11) exp(-733 +/- 58 K/T) (293-810 K), and k(3b)(T) = (2.98 +/- 1.42) x 10(-11) exp(-1686 +/- 160 K/T) (293-378 K) cm(3) molecule(-1) s(-1), where channels a and b signify abstraction of hydrogen atoms in the alpha and beta positions, respectively.