三氯甲基自由基 | 3170-80-7

• 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: 三氯甲基自由基
• 英文名称: trichloromethyl radical
• CAS: 3170-80-7
• 化学式: CCl₃
• 分子量: 118.37
• InChiKey: ZBZJXHCVGLJWFG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  4
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  三氯甲基自由基 在 氧气 作用下， 253.0 ℃ 、101.32 kPa 条件下， 生成 光气
  参考文献：
  名称：

  三氯甲基+氧+ M.fwdarw反应的动力学研究。三氯甲基过氧离子+ M从1至760托和233至333 K

  摘要：

  The kinetics of reaction 1, CCl3 + O2 + M --> CCl3O2 + M, has been investigated in detail as a function of temperature and over a large pressure range. At low pressure, 0.8-12 Torr, the reaction was investigated by laser photolysis and time-resolved mass spectrometry, while at high pressure (760 Torr), flash photolysis with UV absorption spectrometry was employed. At the low-pressure limit, the rate expression, k1(0) = (1.6 +/- 0.3) x 10(-30)(T/298)-(6.3 +/- 0.5) cm6 molecule-2 s-1 (M = N2), exhibits a quite strong negative temperature coefficient. The obtained strong collision rate expression, 7.0 x 10(-30)(T/298)-4.3 cm6 molecule-2 s-1, using either RRKM calculations or Troe's factorized expression, is unable to reproduce the experimental temperature dependence, unless an unreasonably strong temperature dependence is assigned to the collisional efficiency factor: beta-c = 0.23(T/298)-2.0 (M = N2). Similar results are obtained for other chlorofluoromethyl radicals. The falloff curves were constructed by using RRKM calculations obtained by adjusting beta-c and the transition-state model, in order to reproduce the experimental data. The rate expression at the high-pressure limit was derived from these calculations k1(infinity) = (3.2 +/- 0.7) x 10(-12)(T/298)-(1.2 +/- 0.4) cm3 molecule-1 s-1. All the parameters to be used in Troe's analytical expression for calculating the bimolecular rate constant at any pressure and temperature are given. The rate constant at the low-pressure limit k1(0) is more than an order of magnitude lower than for the CF3 radical. The RRKM calculations show that this arises from a large difference in the C-O bond dissociation energies in the corresponding peroxy radicals: 81.9 kJ mol-1 for CCl3O2 instead of almost-equal-to 145 kJ mol-1 for CF3O2.

  DOI：

  10.1021/j100172a037
• 作为产物：
  描述：

  氯化苦 生成 三氯甲基自由基
  参考文献：
  名称：

  Free Radicals by Mass Spectrometry. IX. Ionization Potentials of CF₃and CCl₃Radicals and Bond Dissociation Energies in Some Derivatives

  摘要：

  The vertical ionization potentials of CF3 and CCl3 radicals, as measured by electron impact, are 10.10±0.05 and 8.78±0.05 v respectively. From the appearance potentials of the CF3+ and CCl3+ ions from derivatives, the heats of formation of CF3 and CCl3 radicals were found to be —117±2 kcal/mole and +13.4±3 kcal/mole respectively, assuming that no excess energy was included in the appearance potentials. From this data and other heats of formation the following bond dissociation energies (in kcal/mole) have been evaluated: D(CCl3−H)=88.9±3D(CCl3−F)=102±7D(CCl3−Cl)=67.9±3D(CCl3−Br)=49.5±3D(CF3−H)=103±4D(CF3−F)=121±4D(CF3−Cl)=83±3

  DOI：

  10.1063/1.1742474
• 作为试剂：
  描述：

  异丙醇 在 三氯甲基自由基 作用下， 以 四氯化碳 为溶剂， 生成 丙酮
  参考文献：
  名称：

  液相中三氯甲基自由基引起的氢辐射的动力学。仲醇

  摘要：

  DOI：

  10.1021/j150621a010

文献信息

• <b>The Effects of Temperature and Various Solutes on the Radiolysis of CCl₄</b>
  作者：Fred P. Abramson、Brenda M. Buckhold、Richard F. Firestone

  DOI：10.1021/ja00871a002

  日期：1962.6

  solutes (Cl/sub 2/, Br/sub 2/ , I/sub 2/, O/sub 2/ and C/sub 2/Cl/sub 4/) on the Co/sup 60/ gamma-ray -induced decomposition of liquid CCl/sub 4/ were investigated. Cl/sub 2/ and C/sub 2/Cl/ sub were the only detectable products in pure, air-free, dry CCl/sub 4/. O/sub 2/ accelerated and C/sub 2/Cl/sub 4/ inhibited the decompositi on. Scavenger studies indicated that an abundance of CCl/sub 3/ radtials

  温度和各种溶质（Cl/sub 2/、Br/sub 2/、I/sub 2/、O/sub 2/ 和 C/sub 2/Cl/sub 4/）对 Co/sup 60 的一些影响研究了γ-射线诱导的液体CCl/sub 4/ 的分解。Cl/sub 2/ 和 C/sub 2/Cl/ sub 是纯净、无空气、干燥的 CCl/sub 4/ 中唯一可检测到的产物。O/sub 2/加速和C/sub 2/Cl/sub 4/抑制分解。清除剂研究表明，形成了大量的 CCl/sub 3/ 辐射，其中大部分在可测量的 Cl/sub 2/ 浓度下发生逆反应形成 CCl/sub 4/。没有检测到其他自由基。在室温以上观察到具有约 3%/摄氏度的温度系数的快速初始反应。该反应受到 Cl/sub 2/ 的强烈抑制，达到与温度无关的最终速率。提出了一种涉及热 CCl/sub 3/-自由基和激发的 CCl/sub 3/-自由基的扩散限制自由基机制，以合理化温度和
• 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。
• Absolute rate constants for some reactions of the triethylamine-boryl radical and the borane radical anion
  作者：Brad Sheeller、Keith U. Ingold

  DOI：10.1039/b009494n

  日期：——

  generated the title radicals which were found to have broad, featureless absorptions in the visible region. Rate constants for H-atom abstraction from Et3N→BH3 by cumyloxyl radicals show a small solvent dependence, e.g. 12 × 107 and 2.2 × 107 dm3 mol−1 s−1 in isooctane and acetonitrile, respectively. Rate constants for halogen atom abstraction by Et3N→BH2˙ and BH3˙− from a number of chlorides and bromides

  激光闪光光解 （LFP） 的 二-叔丁基过氧化 或者 过氧化二枯基在的的Et存在下的环境温度下3 Ñ→BH 3或BH 4 -产生其中发现有广泛的，在可见光区域无特征吸收的标题自由基。枯基自由基从Et 3 N→BH 3提取H原子的速率常数很小溶剂依赖性，例如12×10 7和2.2×10 7 dm 3 mol -1 s -1 in异辛烷 和 乙腈， 分别。的速率常数卤素原子通过抽象的Et 3 Ñ→BH 2 ˙和BH 3 ˙ -从若干氯化物和溴化物的被测定LFP并通过竞争性动力学，例如，用于ET 3 Ñ→BH 2 ˙+ 四氯化碳4/的PhCH 2 CL / CH 3（CH 2）2氯，ķ  = 4.4×10 9 /1.1×10 7 /5.1×10 5分米3摩尔-1小号-1和BH 3 ˙ -  + 四氯化碳4/的PhCH 2氯，ķ  = 2.0×10 9 /3.0×10 7分米3摩尔-1小号-1。加入的Et率3
• Radical adducts of dibenzofulvenes and 9-methylenanthrone - an esr study
  作者：Angelo Alberti、Gian Franco Pedulli、Rino Leardin、Antonio Tundo、Giuseppe Zanardi

  DOI：10.1016/0040-4020(86)80018-7

  日期：1986.1

  R3M. radicals (M=C, Si, Ge, Sn, P, O, S) to give the corresponding paramagnetic adducts. In the case of 9-methylenanthrone radical addition occurred selectively at the exocyclic carbon-carbon double bond even with Group IV B organometallic radicals for which attack at the carbonyl oxygen would give rise to thermodynamically more stable adducts. When irradiating solutions of 9-methylenanthrone a photoinduced

  使标题化合物与一系列R 3 M.基团（M = C，Si，Ge，Sn，P，O，S）反应，得到相应的顺磁性加合物。在9-亚甲基蒽酮基团的情况下，即使在IV B族有机金属基团上，环碳-碳双键选择性地发生加成，其对羰基氧的攻击将产生热力学上更稳定的加合物。辐射9-甲基蒽酮溶液时，发生了光致自反应，导致形成了二聚体。根据测得的ESR光谱参数，讨论了加合物的结构，以及R n M基团对β-质子超细分裂常数的影响。
• Time-Resolved Fluorescence and Transient Spectroscopy in Determining Photochemical and Photophysical Channels in Reacting Systems in Solutions and Microheterogeneous Media
  作者：David G. Whitten、Mohammad S. Farahat、Elizabeth R. Gaillard

  DOI：10.1111/j.1751-1097.1997.tb01873.x

  日期：1997.1

  amphiphiles that readily form bilayer systems in aqueous media has been analyzed using a distribution of lifetimes analysis (DLA). The utility of DLA for quantitative studies was first determined by simulation of artificial decay data. Despite some limitations in DLA, qualitative conclusions as to the nature of the fluorescing species may be drawn when supplementary information such as steady‐state spectroscopic

  摘要：已使用时间分辨光谱技术对均质和微异质系统中的短寿命中间体进行表征。从这些技术中获得的数据已经以一种相对非常规的方式进行了分析，以阐明两个反应系统的复杂瞬态行为。已经使用寿命分布分析 (DLA) 分析了一系列易于在水性介质中形成双层系统的 fraws-芪衍生的两亲物的高度非指数荧光衰减。DLA 用于定量研究的效用首先是通过模拟人工衰减数据来确定的。尽管 DLA 存在一些限制，当还考虑诸如稳态光谱数据之类的补充信息时，可以得出关于荧光物质性质的定性结论。结果表明，观察到的荧光来自不同类型的激发态物质，这些物质由两个或多个反式二苯乙烯单元组成；其中一个排放归因于基态聚集体的激发态，而另一个归因于可能由双层中的“缺陷”引起的准分子。衰变的非指数性质归因于荧光物质所经历的环境分布。已经发现溶液中几种激发的频哪醇和四氯化碳之间的电子转移 (ET) 反应产生的产物的量子产率在氧气存在下高于 1，提