cyclopentyl radical | 3889-74-5

• 分子结构分类: 有机化合物 - 碳氢化合物 - 饱和烃
• 英文名称: cyclopentyl radical
• 英文别名: Cyclopentyl-Radikal；cyclopentyl
• CAS: 3889-74-5
• 化学式: C₅H₉
• 分子量: 69.1265
• InChiKey: BQOWUDKEXDCGQS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 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：

  cyclopentyl radical 在 2-碘代丙烷 、 三苯胂 作用下， 以 异辛烷 为溶剂， 生成 碘代环戊烷
  参考文献：
  名称：

  Heats of formation of some simple alkyl radicals

  摘要：

  DOI：

  10.1021/ja00377a018
• 作为产物：
  描述：

  碘代环戊烷 在 异丙基自由基 、 三苯胂 作用下， 以 异辛烷 为溶剂， 生成 cyclopentyl radical
  参考文献：
  名称：

  Heats of formation of some simple alkyl radicals

  摘要：

  DOI：

  10.1021/ja00377a018

文献信息

• Kinetic applications of electron paramagnetic resonance spectroscopy. 42. Some reactions of the bis(trifluoromethyl)aminoxyl radical
  作者：T. Doba、K. U. Ingold

  DOI：10.1021/ja00326a012

  日期：1984.7

  Determination des constantes de vitesse, dans des freons, de l'enlevement d'hydrogene par (CF 3 ) 2 NO . d'un certain nombre de substrats et de l'addition de ce radical a CH 2 =CCl 2

  Determination des constantes de vitesse, dans des freons, de l'enlevement d'hydrogene par (CF 3 ) 2 NO。d'un 某些 nombre de substrats et de l'addition de ce 自由基 a CH 2 =CCl 2
• Absolute Rate Constants for the β-Scission and Hydrogen Abstraction Reactions of the <i>tert</i>-Butoxyl Radical and for Several Radical Rearrangements:  Evaluating Delayed Radical Formations by Time-Resolved Electron Spin Resonance
  作者：Matthias Weber、Hanns Fischer

  DOI：10.1021/ja990837y

  日期：1999.8.1

  An analysis is presented for the determination of absolute rate constants for radical transformation reactions in complex reaction systems by time-resolved ESR during intermittent photochemical radical production. The technique is applied to obtain absolute rate constants in large temperature ranges for the β-scission of the tert-butoxyl radical in various solvents and its hydrogen abstraction from

  分析了在间歇性光化学自由基产生过程中通过时间分辨 ESR 确定复杂反应系统中自由基转化反应的绝对速率常数。该技术用于获得大温度范围内叔丁氧基自由基在各种溶剂中的 β 断裂及其从环己烷、环戊烷、叔丁基苯和苯甲醚中夺氢的绝对速率常数。Neophyl 和 2-methyloxiran-2-yl 重排和叔丁氧基羰基脱羧的动力学研究也证明了该方法的多功能性。此外，还给出了将甲基加入苯和氟苯的速率数据，以及从二叔丁基过氧化物中夺取甲基的氢的速率数据。
• Alkanethioimidoyl Radicals:  Evaluation of β-Scission Rates and of Cyclization onto <i>S</i>-Alkenyl Substituents
  作者：Matteo Minozzi、Daniele Nanni、John C. Walton

  DOI：10.1021/jo0353637

  日期：2004.3.1

  Thioimidoyl radicals were generated by addition of alkylsulfanyl radicals to alkyl isonitriles and were characterized by electron paramagnetic resonance (EPR) spectroscopy. The β-scissions of their C•S−C bonds were studied by variable-temperature EPR spectroscopy and the fragmentation rate constants and activation energies were calculated. The scission rates depend on the stability of the released alkyl radicals

  硫代亚氨基基团是通过将烷基硫基基团加到烷基异腈中而生成的，并通过电子顺磁共振（EPR）光谱进行了表征。通过变温EPR光谱研究了它们的C • S–C键的β断裂，并计算了断裂速率常数和活化能。断裂速率取决于所释放的烷基的稳定性，但是在任何情况下，在室温下，该过程都是快速的。收集到的类似氧基亚酰亚胺基的数据表明，与类似的硫代酰亚胺基相比，它们的裂解略慢。EPR无法研究硒代亚酰胺的断裂速率，而无法通过理论计算进行评估。EPR实验还启用了β分裂和5-exo待测定的两个S-丁-3-烯基取代的亚甲基酰基的闭环速率常数，表明环化仅在低温下盛行。密度泛函理论（DFT）理论计算预测，断裂过程优先发生在亚氨基的s-顺式旋转异构体（X-C键）上。硫代和硒代亚氨基（而不是氧亚氨基）更喜欢s-反式构象，因此它们的断裂涉及事先围绕X-C键的旋转。
• 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。
• An electron spin resonance study of the regioselectivity of the cyclization of protonated and unprotonated pent-4-en-1-oxyl and pent-4-en-1-peroxyl radicals
  作者：A. J. Bloodworth、Alwyn G. Davies、Robyn S. Hay-Motherwell

  DOI：10.1039/p29880000575

  日期：——

  The regioselectivity of the ring closure of protonated and unprotonated pent-4-en-1-oxyl radicals has been determined by monitoring by e.s.r. spectroscopy the radicals which are formed when the corresponding pent-4-enyl peroxides (2; R = H or Me) are photolysed in solution. [graphic omitted]

  质子化和未质子化的戊-4-烯-1-氧基的闭环的区域选择性已通过电子能谱法监测了相应的戊-4-烯基过氧化物形成的自由基（2； R = H或Me ）在溶液中被光解。[图形省略]