氰基甲基自由基 | 2932-82-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: 氰基甲基自由基
• 英文名称: cyanomethyl
• 英文别名: cyanomethylene radical；cyanomethyl radical
• CAS: 2932-82-3
• 化学式: C₂H₂N
• 分子量: 40.0446
• InChiKey: XSTKDMFTWATIQP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  氰基甲基自由基 在 PF6 、 氧气 作用下， 以 乙腈 为溶剂， 生成
  参考文献：
  名称：

  Radiolytic studies of ruthenium oxo-acetato trinuclear complexes in acetonitrile

  摘要：

  Redox reactions of the ruthenium(III,III,III) and ruthenium(III,III,II) trinuclear cluster complexes, [Ru3(mu3-O)-(mu-CH3COO)6(py)3]PF6 and Ru3(mu3-O)(mu-CH3COO)6(py)3, (Ru(333) and Ru(332), respectively) in acetonitrile were studied by pulse radiolysis. Irradiation of deaerated Ru(333) acetonitrile solutions induced one-electron reduction of the trinuclear Ru(333) center by the acetonitrile radical anion, CH3CN.-, to Ru(332). When Ru(332) was used as a parent complex, irradiation afforded Ru(322). The yield of CH3CN.- was evaluated to be 0.21 mumol J-1. In aerated solutions, Ru(333) was competitively reduced by CH3CN.- with a rate constant of 6.1 x 10(10) m-1 s-1 and the superoxide ion, O2-, with a rate constant of 3.5 x 10(9) m-1 s-1 at 14-degrees-C. Ru(332) once produced decayed to regenerate Ru(333) in 100-300 mus after the electron-pulse irradiation. Oxidation of Ru(332) by the peroxyl radical, O2CH2CN, to Ru(333) with a rate constant of 2.7 x 10(9) m-1 s-1 was confirmed. The whole reaction scheme for the radiation-induced processes is discussed.

  DOI：

  10.1021/j100131a058
• 作为产物：
  描述：

  溴乙腈 在 N,N'-bis(2'-(dimethylamino)ethyl)-N,N'-dimethylpropane-1,3-diamine 、 copper(I) bromide 作用下， 以 乙腈 为溶剂， 生成 氰基甲基自由基
  参考文献：
  名称：

  了解原子转移自由基聚合：配体和引发剂结构对平衡常数的影响

  摘要：

  铜基原子转移自由基聚合 (ATRP) 中的平衡常数是在 22 摄氏度的乙腈中确定的范围广泛的配体和引发剂。获得的 ATRP 平衡常数变化超过 7 个数量级，并且强烈依赖于配体和引发剂结构. Cu(I)/配体配合物的活性对于四齿配体最高，对于三齿配体较低，对于双齿配体最低。具有三足和桥连配体（Me6TREN 和桥连环链球菌）的复合物往往比具有相应线性配体的复合物更具活性。叔烷基卤化物的平衡常数最大，而伯烷基卤化物的平衡常数最小。烷基溴的活性比类似的烷基氯的活性大几倍。腈衍生物的平衡常数最大，其次是苄基衍生物和相应酯的平衡常数。其他不容易测量的平衡常数是从参考配体和引发剂的值推断出来的。观察到平衡常数与 Cu(II/I) 氧化还原电位和碳 - 卤素键解离能的极好相关性。

  DOI：

  10.1021/ja802290a

文献信息

• Homolytic dissociation of 1-substituted cyclohexa-2,5-diene-1-carboxylic acids: an EPR spectroscopic study of chain propagation†
  作者：Leon V. Jackson、John C. Walton

  DOI：10.1039/b104859g

  日期：——

  Hydrogen abstraction from 1-substituted cyclohexa-2,5-diene-1-carboxylic acids containing linear, branched and cyclic alkyl substituents, as well as allyl, propargyl (prop-2-ynyl), cyanomethyl and benzyl substituents, has been studied by EPR spectroscopy. For each carboxylic acid, EPR spectra of the corresponding cyclohexadienyl radicals were observed at lower temperatures, followed by spectra due to ejected carbon-centred radicals at higher temperatures. Rate constants, for release of the carbon-centred radicals from the cyclohexadienyl radicals, were determined from radical concentration measurements for the above range of substituents. The rate of cyclohexadienyl radical dissociation increased with branching in the 1-alkyl substituent and with electron delocalisation in the ejected carbon-centred radical; 3,5- and 2,6-dimethyl-substitution of the cyclohexadienyl ring led to reductions in the dissociation rate constants. Rate data for abstraction of bisallylic hydrogens from the cyclohexadienyl acids were also obtained for ethyl, n-propyl and isopropyl radicals. These results indicated a sharp drop in the rate of hydrogen abstraction as the degree of branching in the attacking radical increased. Small decreases in the hydrogen abstraction rate constants were observed for cyclohexadienes containing CO2R substituents.

  通过电子顺磁共振（EPR）光谱研究了从含有线性、支化、环状烷基取代基以及烯丙基、炔丙基（丙-2-炔基）、氰基甲基和苄基取代基的1-取代环己-2,5-二烯-1-羧酸中提取氢的反应。对于每种羧酸，在较低温度下观察到相应的环己二烯基自由基的EPR谱，随后在较高温度下观察到由喷出的碳中心自由基引起的谱。通过对于上述范围的取代基的自由基浓度测量，确定了从环己二烯基自由基释放碳中心自由基的速率常数。环己二烯基自由基解离速率随着1-烷基取代基的分支增加和喷出的碳中心自由基的电子离域程度增加而加快；环己二烯环的3,5-和2,6-二甲基取代导致解离速率常数降低。还获得了从环己二烯羧酸中提取双烯丙基氢的速率数据，涉及乙基、正丙基和异丙基自由基。这些结果表明，随着攻击自由基的分支程度增加，氢提取速率急剧下降。环己二烯中含有CO2R取代基时，氢提取速率常数略有下降。
• Solvent effects on the thermochemistry of free-radical reactions
  作者：J. M. Kanabus-Kaminska、B. C. Gilbert、D. Griller

  DOI：10.1021/ja00191a030

  日期：1989.4

  were the same and their contributions to the measured heats of reaction therefore canceled. The results suggest that solution data, measured in extremely polar solvents, can be converted to their gas-phase equivalents (and vice versa) by considering only the heats of solvation of very small, polar molecules that participate in a given reaction. Moderately large organic molecules and their corresponding

  通过使用光声量热法测量各种有机底物在水中的反应热 Hsub 2}O + 2RH 产量} 2H sub 2}O + 2R sup sm bullet}。获得的值大大低于从气相数据计算的值，差异完全是由于与 1 当量过氧化氢转化为 2 当量水相关的溶剂化能的变化。Rsm bullet}} 和RH 的溶剂化能相同，因此它们对测量的反应热的贡献被抵消。结果表明，通过仅考虑参与给定反应的极小极性分子的溶剂化热，可以将在极极性溶剂中测量的溶液数据转换为其气相当量（反之亦然）。
• FTIR and computational studies of gas-phase hydrogen atom abstraction kinetics by t-butoxy radical
  作者：Shuping Li、Wai Yip Fan

  DOI：10.1016/j.cplett.2006.06.100

  日期：2006.8

  for the hydrogen atom abstraction reactions of several substrates including halogenated organic compounds and amines by t-butoxy radical generated from the uv photolysis of t-butyl nitrite in the gas phase. Arrhenius parameters for selected reactions have been measured in the temperature range 299–318 K. Transition states and activation barriers for such reactions have been computed with the help of

  通过使用傅立叶变换红外（FTIR）吸收光谱法，已确定了包括卤代有机化合物和氢氧烷在内的几种底物的氢原子提取反应的速率系数在10 -16至10 -14  cm 3 分子-1  s -1范围内。通过叔丁氧基自由基在气相中亚硝酸叔丁酯的紫外光解而生成胺。在299–318 K的温度范围内测量了所选反应的Arrhenius参数。借助Gaussian 03软件计算了此类反应的过渡态和激活势垒，发现与实验值非常吻合。
• Absolute Rate Constants for the Addition of Cyanomethyl (·CH₂CN) and (<i>tert</i>-Butoxy)carbonylmethyl (·CH₂CO₂C(CH₃)₃) radicals to alkenes in solution
  作者：Jie Qiang Wu、Ivan Beranek、Hanns Fischer

  DOI：10.1002/hlca.19950780118

  日期：1995.2.8

  Absolute rate constants and their temperature dependence were determined by time-resolved electron spin resonance for the addition of the radicals ·CH2CN and ·CH2CO2C(CH3)3 to a variety of mono- and 1,1-disubstituted and to selected 1,2- and trisubstituted alkenes in acetonitrile solution. To alkenes CH2CXY, ·CH2CN adds at the unsubstituted C-atom with rate constants ranging from 3.3·103M−1S−1 (ethene)

  通过时间分辨电子自旋共振确定绝对速率常数及其温度依赖性，方法是将自由基·CH 2 CN和·CH 2 CO 2 C（CH 3）3添加到各种单取代和1,1-二取代基中并在乙腈溶液中选择1,2-和三取代的烯烃。·CH 2 CN在烯烃CH 2 CXY处以未取代的C原子加成，其速率常数范围为3.3·10 3 M -1 S -1（乙烯）至2.4·10 6 M -1 S -1（1，1-二苯基乙烯）在278 K，并且频率因子在log的窄范围内（A / M -1 S -1）= 8.7±0.3。·CH 2 CO 2 C（CH 3）3具有非常相似的反应性，在296 K时的速率常数为1.1·10 4 M -1 S -1（乙烯）至10 7 M -1 S -1（1,1 -二苯乙烯）和频率因子log（A / M -1 S -1）= 8.4±0.1。对于两个自由基，速率常数和添加到CH 2中的活化能CXY与总反应焓密切相
• Photo-oxidation of alcohols by hexachlorometalate(IV) ions (M = Pt, Pd, or Ir): spin trapping and matrix isolation electron spin resonance studies
  作者：Anand G. Fadnis、Terence J. Kemp

  DOI：10.1039/dt9890001237

  日期：——

  Spin-trapping studies reveal that whereas the mild (λ > 380 nm) photolysis of ions [MCl6]2–(M = Pd, Pt, or Ir) in alcohol (RCH2OH)-water mixtures leads invariably to RĊHOH, in pure alcoholic media many of the oxidations lead to RCH2[graphic omitted]. Prolonged, wide-band photolysis leads to the production of H atoms. At 77 K, wide-band photolysis leads to the production of platinum(III) and palladium(III)

  自旋捕集研究表明，尽管酒精（RCH 2 OH）-水混合物中的离子[MCl 6 ] 2–（M = Pd，Pt或Ir）的轻度（λ> 380 nm）光解作用总是导致RĊHOH，在纯酒精介质中，许多氧化反应会生成RCH 2 [未显示图形]。长时间的宽带光解导致产生H原子。在77K，宽波段光解导致产生铂（III）和钯（III）中心，可以通过鉴定克⊥特征，除了预期的Ç -centred有机基团。