cyclohexen-3-yl radical | 7493-04-1

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: cyclohexen-3-yl radical
• 英文别名: cyclohex-1->3-enyl；2-cyclohexen-1-yl radical；cyclohexenyl radical；3-Cyclohexenyl-radikal；Cyclohexenyl；3-cyclohexenyl radical
• CAS: 7493-04-1
• 化学式: C₆H₉
• 分子量: 81.1375
• InChiKey: FHEPZBIUHGLJMP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  1.0
• 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：

  cyclohexen-3-yl radical 生成 1,3-环己二烯
  参考文献：
  名称：

  Homolytic Bond Dissociation Enthalpies of the C−H Bonds Adjacent to Radical Centers

  摘要：

  Homolytic bond dissociation enthalpies (BDEs) at 0 and 298 K of the C-H bonds adjacent to various radical centers have been obtained from ab initio CBS-4 (complete basis set) model calculations and experimental data available in the literature. The BDEs of the C-H bonds adjacent to the radical centers derived from 11 saturated hydrocarbons were found to be 33.5 +/- 3 kcal/mol at 298 K. The BDEs of the C-H bonds adjacent to nine allylic and benzylic radical centers were found to be 48 +/- 3 kcal/mol at 298 K, but the benzylic C-H BDE of the PhCH2CH2. radical was found to be only 29.7 and 30.5 kcal/mol at 0 and 298 K, respectively. The BDEs of the vinylic C-H bonds adjacent to four vinylic radical centers were found to be 35.5 +/- 3.5 kcal/mol at 298 K. The BDEs of the vinylic C-H bonds adjacent to three allylic radical centers were found to be 56.5 +/- 3 kcal/mol at 298 K. These results suggest that the radical centers weaken the adjacent C-H bond strengths by about 50-70 kcal/mol. The calculated BDEs agree within +/-2 kcal/mol with most of the available experimental results. Isomerization enthalpies of butenes and pentenes have been obtained. Substituent effects on BDEs have also been examined.

  DOI：

  10.1021/jo971768d
• 作为产物：
  描述：

  环己烯 在 二叔丁基过氧化物 作用下， 以 苯 为溶剂， 生成 cyclohexen-3-yl radical
  参考文献：
  名称：

  五元和六元环烃之间的能量差异：母体和自由基分子的应变能

  摘要：

  对五元和六元环烷烃，烯烃和二烯的CH键解离焓（BDE）进行了研究，并根据常规应变能（SE）进行了讨论。据报道，通过时间分辨光声热法和量子化学方法对环戊烷和环己烷进行了新的测定。还计算了产生烷基环戊烯-4-基和环己烯-4-基的烯烃的CHBDEs和环戊烯中的α-CHBDE。该小号-homodesmotic模型被用来确定两个亲本分子和原子团的SE。适当的时候选择-homodesmotic模型，所获得的SE与从群可加方案推导的SE非常吻合。标题分子中不同的BDE由母体分子及其基团中的SE计算得出：（1）导致烷基基团的BDE约为ca。环戊烷和环戊烯比环己烷和环己烯低10 kJ mol -1，这是由于五元基团中的相对于母体分子的蚀变较小（六元烃及其基团基本无应变）。（2）环戊烯和环己烯中导致烯丙基自由基的CH BDE相似，这是因为环戊烯-3-基具有近平面构型，几乎具有与其母体相同的应变。（3）1,3-环戊二烯中的CH

  DOI：

  10.1021/jo800690m

文献信息

• Structure and reactivity of perfluorinated branched α-ketoradicals
  作者：B.L. Tumanskii、E.N. Shaposhnikova、E.A. Avetisyan、R.S. Sterlin

  DOI：10.1016/s0022-1139(98)00319-4

  日期：1999.6

  Fluoroaliphatic hydroxyketoradicals prepared by photochemical reduction of the corresponding α-diketones and (i-C3F7)2C⋅C(O)CF3 react with hydrogen abstraction (according to ESR data). The hydroxyketoradicals are shown to dimerize reversibly, and the dimerization rate decreases in the presence of polyfluorinated alcohols due to the formation of radical–alcohol complexes.

  氟脂hydroxyketoradicals制备由相应的α二酮的光化学还原和（我-C 3 ˚F 7）2 Ç ⋅ C（O）CF 3与夺氢反应（根据ESR数据）。羟基酮三醇可逆地二聚，由于存在自由基-醇配合物，在存在多氟醇的情况下，二聚率降低。
• Energetics of the Allyl Group
  作者：Filipe Agapito、Paulo M. Nunes、Benedito J. Costa Cabral、Rui M. Borges dos Santos、José A. Martinho Simões

  DOI：10.1021/jo701397r

  日期：2007.11.1

  reference, we have concluded that one methyl group bonded to C3 in propene (i.e., 1-butene) leads to a decrease of 12 kJ mol-1 and that a second methyl group bonded to C3 (3-methylbut-1-ene) further decreases the BDE by 8 kJ mol-1. When the methyl group is bonded to C2 in propene (isobutene), an increase of 7 kJ mol-1 is observed. Finally, a methyl group bonded to C1 in propene (2-butene) has essentially

  为了增进我们对含有烯丙基部分的自由基的稳定性的理解，丙烯，异丁烯，1-丁烯，（E）-2-丁烯，（3-甲基丁-1-烯）中的碳氢键解离焓（BDE）E）-2-戊烯，（E）-1,3-戊二烯，1,4-戊二烯，环己烯，1,3-环己二烯和1,4-环己二烯已通过量子化学计算确定。环己烯，1，3-环己二烯和1，4-环己二烯中的BDE也已通过时间分辨光声量热法获得。理论研究涉及DFT方法以及从头开始的完整基础集方法，包括复合CBS-Q和CBS-QB3程序，以及基础集外推耦合群集计算（CCSD（T））。通过取C（sp 3）-H BDE在丙烯中作为参考，我们得出的结论是，一个与丙烯中的C3键合的甲基（即1-丁烯）导致减少12 kJ mol -1，另一个与甲基C3键合的甲基（3 -甲基丁-1-烯）进一步将BDE降低8 kJ mol -1。当甲基在丙烯（异丁烯）中与C 2键合时，观察到增加了7 kJ mol -1。最
• Finkel'shtein, E. I.; Gerasimov, G. N., Russian Journal of Physical Chemistry, 1984, vol. 58, # 4, p. 570 - 572
  作者：Finkel'shtein, E. I.、Gerasimov, G. N.

  DOI：——

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• Bromine atom complexes with bromoalkanes: their formation in the pulse radiolysis of di-, tri-, and tetrabromomethane and their reactivity with organic reductants
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• Ring-inversion barriers for the 3- and 4-cyclohexenyl radicals in solution
  作者：J. A. Berson、D. Griller、K. Owens、D. D. M. Wayner

  DOI：10.1021/jo00391a026

  日期：1987.7