1,1-dichloroethyl radical | 19468-97-4

• 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: 1,1-dichloroethyl radical
• 英文别名: α,α-dichloroethyl radical；α,α-Dichlorethyl；1,1-dichloro-ethyl
• CAS: 19468-97-4
• 化学式: C₂H₃Cl₂
• 分子量: 97.9518
• InChiKey: JJBQYDJSNVBLLE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  4
• 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-dichloroethyl radical 在 氢溴酸 作用下， 生成 1,1-二氯乙烷
  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：

  1,1-二氯乙烷 在 氯 作用下， 7.0 ℃ 、2.8 kPa 条件下， 生成 1,1-dichloroethyl radical
  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 R+Cl2 (R=CH2Cl, CHBrCl, CCl3 and CH3CCl2) reactions. An ab initio study of the transition states
  作者：Jorma A. Seetula

  DOI：10.1039/a804223c

  日期：——

  The kinetics of the reactions of CH2Cl, CHBrCl, CCl3 and CH3CCl2 radicals with molecular chlorine were investigated in a heatable tubular reactor coupled to a photoionization mass spectrometer. The reactions were studied under pseudo-first-order conditions. The radicals were photogenerated at 248 nm. The pressure-independent rate constants determined were fitted to the following Kooij and Arrhenius expressions (units in cm3 molecule-1 s-1): k(CH2Cl)=7.56×10-17(T)1.45 exp(-350 J mol-1/RT), k(CHBrCl)=5.83×10-20(T)2.3 exp(-300 J mol-1/RT), k(CCl3)=(8.4±2.9)×10-13 exp[-(25±9) kJ mol-1/RT] and k(CH3CCl2)=1.10×10-26(T)4.3 exp(+15000 J mol-1/RT). The Arrhenius rate expression for the Cl+CCl4 reaction was determined to be k(Cl+CCl4)=(3.9±3.2)×10-13 exp[-(71±9) kJ mol-1/RT] using the kinetics measured and the thermochemistry of the CCl3 radical. Errors for the Kooij expressions were estimated to be 25% overall, and for the Arrhenius expressions they were calculated to be 1σ+Student's t values. The transition states of the measured R+Cl2 and four other similar reactions were localized and fully optimized at the MP2/6-31G(d,p) level of theory by abinitio methods. The energetics of the reactions were considered by determining thermochemical and activation parameters of the reactions. The reactivity differences of the radicals studied were explained by a free-energy correlation using an electronegativity difference scale.

  在可加热的管式反应器中，结合光电离质谱仪，研究了CH₂Cl、CHBrCl、CCl₃和CH₃CCl₂自由基与分子氯的反应动力学。这些反应在准一级条件下进行了研究，自由基在248 nm下光生。测得的与压力无关的速率常数拟合为以下Kooij和Arrhenius表达式（单位为cm³ molecule⁻¹ s⁻¹）： k(CH₂Cl) = 7.56×10⁻¹⁷(T)¹.⁴⁵ exp(-350 J mol⁻¹/RT) k(CHBrCl) = 5.83×10⁻²⁰(T)².³ exp(-300 J mol⁻¹/RT) k(CCl₃) = (8.4±2.9)×10⁻¹³ exp[-(25±9) kJ mol⁻¹/RT] k(CH₃CCl₂) = 1.10×10⁻²⁶(T)⁴.³ exp(+15000 J mol⁻¹/RT) 利用测得的反应动力学和CCl₃自由基的热化学数据，确定了Cl+CCl₄反应的Arrhenius速率表达式为： k(Cl+CCl₄) = (3.9±3.2)×10⁻¹³ exp[-(71±9) kJ mol⁻¹/RT] Kooij表达式的误差估计为总体25%，而Arrhenius表达式的误差计算为1σ加上学生的t值。通过从头计算方法，在MP2/6-31G(d,p)理论水平上，定域并完全优化了所测量的R+Cl₂反应和其他四个类似反应的过渡态。通过确定反应的热化学和活化参数，考虑了反应的能量学。通过使用电负性差异尺度进行自由能相关，解释了所研究自由基的反应性差异。
• Kinetics of the Photobromination of Dichloro- and Dibromoethane. Estimate of the C–H Bond Dissociation Energies and the Heats of Formation of the CH₃CCl₂and CH₃CBr₂Radicals
  作者：Kikuo Miyokawa、Eugene Tschuikow-Roux

  DOI：10.1246/bcsj.72.1

  日期：1999.1

  8(σ)] × 1011exp[(−7300 ± 360 cal mol−1)/RT] and k2 = [2.2 ± 1.2(σ)] × 1011exp[(−7110 ± 360 cal mol−1)/RT]. Using a justifiable approximation concerning the magnitude of the activation energies for the reverse reaction, the following thermochemical quantities (kcal mol−1) were derived: ΔH°f(CH3CCl2) = 11.9 ± 1.2, D°(CH3CCl2-H) = 95.1 ± 1.2, ΔH°f(CH3CBr2) = 33.5 ± 1.3, D°(CH3CBr2-H) = 94.9 ± 1.2. The relation

  使用氯乙烷和乙烷在 308-368 K 的温度范围内研究了 α-H 提取反应 RH + Br → R + HBr、RH = 1,1-二氯 (1) 和 1,1-二溴乙烷 (2) 的动力学分别作为外部竞争对手。将相对速率与氯乙烷和乙烷的已知速率参数相结合以获得绝对速率常数 (cm3 mol−1 s−1)： k1 = [6.9 ± 3.8(σ)] × 1011exp[(−7300 ± 360 cal mol −1)/RT] 和 k2 = [2.2 ± 1.2(σ)] × 1011exp[(−7110 ± 360 cal mol−1)/RT]。使用关于逆反应活化能大小的合理近似，推导出以下热化学量 (kcal mol−1)：ΔH°f(CH3CCl2) = 11.9 ± 1.2, D°(CH3CCl2-H) = 95.1 ± 1.2, ΔH°f(CH3CBr2) = 33.5 ± 1.3, D°(CH3CBr2-H)
• 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%.
• Thoelmann, Detlef; Flottmann, Dirk; Gruetzmacher, Hans-Friedrich, Chemische Berichte, 1991, vol. 124, # 10, p. 2349 - 2356
  作者：Thoelmann, Detlef、Flottmann, Dirk、Gruetzmacher, Hans-Friedrich

  DOI：——

  日期：——
• 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.