氟甲基自由基 | 3744-29-4

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氟化物
• 中文名称: 氟甲基自由基
• 英文名称: fluoromethyl
• 英文别名: Fluormethyl；Fluormethylradikal；fluoromethyl radical
• CAS: 3744-29-4
• 化学式: CH₂F
• 分子量: 33.0253
• InChiKey: VUWZPRWSIVNGKG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  2
• 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：
  1

反应信息

• 作为反应物：
  描述：

  氟甲基自由基 生成 氢氟酸
  参考文献：
  名称：

  Sirkin, E. R.; Berry, M. J., IEEE Journal of Quantum Electronics, 1974, vol. 10, p. 701 - 702

  摘要：

  DOI：
• 作为产物：
  描述：

  氟甲烷 以 solid matrix 为溶剂， 生成 氟甲基自由基
  参考文献：
  名称：

  Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: C: MVol.D2, 3.16.1, page 83 - 83

  摘要：

  DOI：

文献信息

• An Experimental and Modelling Study of Ignition Delays in Shock-Heated Ethane-Oxygen-Argon Mixtures Inhibited by 2H-Heptafluoropropane
  作者：K. Ikeda、J.C. Mackie

  DOI：10.1524/zpch.2001.215.8.997

  日期：2001.1.1

  Ignition delay times have been measured behind reflected shock waves in ethane-oxygen-argon mixtures at temperatures between 1150 and 1500 K and pre-ignition pressures between 10 and 14 atm. Delay times have been measured both by pressure rise and OH absorption at 307 nm. Kinetic modelling of the ignition delays has been made using the GRIMech 3.0 mechanism which with addition of several reactions involving HO

  点火延迟时间已在反射激波后的乙烷-氧气-氩混合物中测量，在1150至1500K的温度和10至14大气压的预点火压力下。延迟时间已通过压力升高和307纳米处OH吸收来测量。使用GRIMech 3.0机制进行了点火延迟的动力学建模，其中包括涉及HO的几个反应。
• Gas-Phase Kinetics of the Reactions of the CH₂F Radicals with the Radicals CHF₂, CH₃, and C₂H₅
  作者：T. Beiderhase、Karlheinz Hoyermann、Jörg Nothdurft、Matthias Olzmann

  DOI：10.1524/zpch.218.4.493.29203

  日期：2004.4.1

  The mechanisms and the rates of the reactions of the fluorinated hydrocarbon radical CH₂F with the fluorinated and pure hydrocarbon radicals CHF₂, CH₃, and C₂H₅, respectively, have been studied at low pressure (around 2 mbar) and room temperature using the discharge-flow reactor technique. Mass spectrometry either with electron impact or laser induced multiphoton ionization was applied for the detection of labile and stable species.

  The cross combination of the radicals is mainly followed by HF elimination from the chemically activated adduct. The overall rate coefficients at 298K for

  CH₂F + CHF₂ → C₂H₂F₂ + HF (1)

  CH₂F + CH₃ → C₂H₄ + HF (2)

  CH₂F + C₂H₅ → C₃H₆ + HF (3)

  were derived from the analysis of the radical-time profiles by fit procedures; the following values were obtained:

  CH₂F + CHF₂ → C₂H₂F₂ + HF (1)

  CH₂F + CH₃ → C₂H₄ + HF (2)

  CH₂F + C₂H₅ → C₃H₆ + HF (3)

  k ₁ = (3.0 + 1.5/ − 0.7) × 10¹²cm³mol⁻¹s⁻¹

  k ₂ = (4.0 ± 1.5) × 10¹³cm³mol⁻¹s⁻¹

  k ₃ = (9.0 ± 3) × 10¹²cm³mol⁻¹s⁻¹.

  The results are discussed in terms of chemical activation mechanisms.

  摘要：研究了氟化碳氢自由基CH2F与氟化和纯碳氢自由基CHF2、CH3和C2H5在低压（约2 mbar）和室温下使用放电流动反应器技术进行的反应机制和速率。质谱法（电子轰击或激光诱导多光子电离）被应用于检测不稳定和稳定物种。 自由基的交叉组合主要通过化学活化加合物中的HF消除而进行。在298K下的总速率系数为： 1. CH2F + CHF2 → C2H2F2 + HF (1) 2. CH2F + CH3 → C2H4 + HF (2) 3. CH2F + C2H5 → C3H6 + HF (3) 通过拟合程序从自由基-时间曲线的分析中得出了以下数值： 1. CH2F + CHF2 → C2H2F2 + HF (1) 2. CH2F + CH3 → C2H4 + HF (2) 3. CH2F + C2H5 → C3H6 + HF (3) 得到的数值如下： - k1 = (3.0 + 1.5/ − 0.7) × 10^12 cm^3 mol^−1 s^−1 - k2 = (4.0 ± 1.5) × 10^13 cm^3 mol^−1 s^−1 - k3 = (9.0 ± 3) × 10^12 cm^3 mol^−1 s^−1。 结果从化学活化机制的角度进行了讨论。
• Reaction of photogenerated fluorine atoms with dopant molecules in solid argon
  作者：E. Ya. Misochko、V. A. Benderskii、A. U. Goldshleger、A. V. Akimov、A. V. Benderskii、C. A. Wight

  DOI：10.1007/bf02495195

  日期：1997.4

  The·CH3−HF complexes are characterized by the IR band of HF stetching vibration at 3764 cm−1. Two additional splittings on the H (aH·=2 G) and F(aF=16G) nuclei of the HF molecule appeal in the ESR spectrum of the complex. The latter splitting is retained in the·CD3−DF complex, whereAD· <0.3G The rate constant of the reaction CH4+F→·CH3+HF is equal to −10−25 cm3s−1 at 20 K. Its activation energy (1

  掺杂剂 CH4 分子与 F 原子在 20-30 K 的固体氩气中扩散的反应产物通过 ESR 和 FTIR 光谱进行鉴定。稳定在基体中的 F 原子是通过 Ar-CH4(CD4)-F (1000∶1∶1) 样品在 13 K 下的紫外光解产生的。随后加热到 20 K 以上导致 F 原子的扩散解冻并形成它们与 CH4 反应的产物：自由基-分子复合物·CH3-HF (·CD3-DF) 和自由基·CH3 (·CD3)。自由基的 ESR 谱与观察到的基质分离·CH3 的谱相似。·CH3-HF 复合物的特征在于 3764 cm-1 处的 HF 拉伸振动的 IR 带。HF 分子的 H (aH·=2 G) 和 F(aF=16G) 核上的两个额外分裂在复合物的 ESR 光谱中很有吸引力。后者的分裂保留在·CD3-DF 复合物中，其中AD·<0。3G CH4+F→·CH3+HF 反应的速率常数在 20 K 时等于
• Reactions of fluoromethyl radicals
  作者：Philip Cadman、Howell L. Owen

  DOI：10.1039/f19817703087

  日期：——

  1,3-difluoroacetone was photolysed by itself and in the presence of either diethylketone or di-isopropylketone and the rates of the following reactions of fluoromethyl radicals were measured: (i) CH2F + CH2FCOCH2F, log10(k/cm3 mol–1 s–1)= 11.10–40000//2.303RT, (ii) CH2F + C2H5COC2H5, log10(k/cm3 mol–1 s–1)= 10.71–34050//2.303RT, (iii) CH2F + i-C3H7CO-i-C3H7, log10(k/cm3 mol–1 s–1)= 11.18–31550//2.303RT

  1,3-二氟丙酮本身在二乙基酮或二异丙基酮存在下被光解，并测量以下氟甲基自由基反应的速率：（i）CH 2 F + CH 2 FCOCH 2 F，log 10（k / cm 3 mol –1 s –1）= 11.10–40000 // 2.303 ř Ť，（ii）CH 2 F + C 2 H 5 COC 2 H 5，log 10（k / cm 3 mol –1 s –1）= 10.71–34050 // 2.303 ř Ť，（iii）CH 2 F + iC 3 H 7 CO-iC 3 H 7，log 10（k / cm 3 mol –1 s –1）= 11.18–31550 // 2.303 ř Ť其中R = 8.314 J mol –1 K –1。
• Reactions of fluoroalkyl radicals. Part 6.—Addition of fluoromethyl radicals to ethylene
  作者：J. M. Sangster、J. C. J. Thynne

  DOI：10.1039/tf9696502110

  日期：——

  The addition of fluoromethyl radicals to ethylene in the gas phase has been studied over the temperature range 17–182°C, using the abstraction of a hydrogen atom from hydrogen sulphide as the competing reaction: [graphic omitted] Values of 0.91 ± 0.18 and –1.32 ± 0.29 kcal mole–1 have been determined for log (A2/A1) and E2—E1 respectively. Fluoromethyl radicals add readily to ethylene, their reactivity being intermediate between those of methyl and trifluoromethyl.

  以从硫化氢中抽取一个氢原子作为竞争反应，研究了气相中乙烯与氟甲基自由基的加成反应，温度范围为 17-182°C：[省略]对数（A2/A1）和 E2âE1 的值分别为 0.91 ± 0.18 千卡摩尔 1 和 1.32 ± 0.29 千卡摩尔 1。氟甲基自由基很容易加入乙烯，其反应活性介于甲基和三氟甲基自由基之间。