cyclohexylperoxy radical | 2143-59-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: cyclohexylperoxy radical
• 英文别名: Cyclohexylperoxy-Radikal
• CAS: 2143-59-1
• 化学式: C₆H₁₁O₂
• 分子量: 115.152
• InChiKey: PCXXFAKDWJPSSA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  10.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  cyclohexylperoxy radical 在 hydroperoxyl radical 作用下， 以99%的产率得到环己基过氧化氢化物
  参考文献：
  名称：

  Kinetic and mechanistic studies of the reactions of cyclopentylperoxy and cyclohexylperoxy radicals with hydroperoxy radical

  摘要：

  The kinetics and mechanism of the reactions c-C5H9O2 + HO2 --> c-C5H9OOH + O2 (1) and c-C6H11O2 + HO2 --> c-C6H11OOH + O2 (2) have been studied using both the flash photolysis/UV absorption and continuous photolysis/FTIR product analysis techniques. End product analysis experiments at 295 +/- 2 K demonstrated that the yield of hydroperoxide was (96 +/- 3) % and (99 +/- 3)% for reactions 1 and 2, respectively, although systematic errors could add an additional 15% uncertainty. Experiments between 248 and 364 K showed that k1 and k2 demonstrated virtually indistinguishable kinetic behavior at all temperatures, with k1/cm3 molecule-1 s-1 = (2.1 +/- 1.3) x 10(-13) exp((1323 +/- 185) K/T) and k2/cm3 molecule-1 s-1 = (2.6 +/- 1.2) x 10(-13) exp((1245 +/- 124) K/T). Absolute uncertainties on kl and k2, including experimental scatter and uncertainties in the analysis parameters, are estimated to be 18%. No dependence of k1 or k2 on pressure between 200 and 760 Torr was found. The room temperature rate constants for reactions 1 and 2 are significantly greater than those measured for other alkylperoxy radicals to date. The reactions of Cl atoms with cyclopentane, Cl + c-C5H 10 --> HCl + c-C5H9 (6) and cyclohexane, Cl + c-C6H12 --> HCl + c-C6H11 (8) were measured relative to that with methanol, Cl + CH3OH --> HCl + CH2OH (4). Neither k6 nor k8 varied significantly with temperature over the range 248-364 K, with k6/cm3 molecule-1 s-1 = (2.3 +/- 0.2) x 10(-10) and k8/cm3 molecule-1 s-1 = (2.4 +/- 0.3) x 10(-10), using k4/cm3 molecules-1 s-1 = 5.7 x 10(-11). Errors are 1-sigma and represent experimental scatter only, unless stated otherwise.

  DOI：

  10.1021/j100191a031
• 作为产物：
  描述：

  cyclohexyl radical 在 氧气 、 六氟化硫 作用下， 生成 cyclohexylperoxy radical
  参考文献：
  名称：

  Atmospheric Chemistry of Cyclohexane:  UV Spectra of c-C₆H₁₁^• and (c-C₆H₁₁)O₂^• Radicals, Kinetics of the Reactions of (c-C₆H₁₁)O₂^• Radicals with NO and NO₂, and the Fate of the Alkoxy Radical (c-C₆H₁₁)O^•

  摘要：

  A pulse radiolysis technique was used to measure the UV absorption spectra of c-C6H11. and (c-C6H11)O-2(.) radicals over the ranges 230-290 and 220-300 nm, sigma(c-C6H11.)(250 nm), = (7.0 +/- 0.8) x 10(-18) and sigma((c-C6H11)O-2(.))(250 nm) = (5.7 +/- 0.6) x 10(-18) cm(2) molecule(-1). The rate constant for the self-reaction of c-C6H11. radicals was k(3) = (3.0 +/- 0.4) x 10(-11) cm(3) molecule(-1) s(-1). The addition reaction of c-C6H11. radicals with O-2 proceeds with a rate constant k(2) = (1.3 +/- 0.2) x 10(-11) cm(3) molecule(-1) s(-1). Rate constants for reactions of (c-C6H11)O-2(.) radicals with NO and NO2 were k(4) = (6.7 +/- 0.9) x 10(-12) and k(5) = (9.5 +/- 1.5) x 10(-12) cm(3) molecule(-1) s(-1), respectively. FTIR-smog chamber techniques were used to record the IR spectrum of the peroxynitrate (c-C6H11)O2NO2, determine that the reaction between (c-C6H11)O-2(.) radicals and NO produces a (16 +/- 4)% yield of the nitrate (c-C6H11)ONO2, and study the atmospheric fate of cyclohexoxy radicals. Decomposition via C-C bond scission and reaction with O-2 are competing fates of the cyclohexoxy radical. In 700-750 Torr total pressure at 296 +/- 2K, the rate constant ratio k(decomp)/k(O2) = (8.1 +/- 1.5) x 10(18) molecule cm(-3). At 296 K in 1 atm of air, 61% of cyclohexoxy radicals:decompose and 39% react with O-2. These results are discussed with respect to the literature data concerning the atmospheric chemistry of cyclohexane and analogous compounds.

  DOI：

  10.1021/jp984195x

文献信息

• METHOD FOR PRODUCING TRIARYLORGANOBORATES
  申请人：Covestro Deutschland AG

  公开号：US20190263838A1

  公开（公告）日：2019-08-29

  The invention relates to a process for preparing triaryl organoborates proceeding from organoboronic esters in the presence of an n-valent cation 1/n K n+ , comprising the anhydrous workup of the reaction mixture and the use of the triaryl organoborates obtained as co-initiator in photopolymer formulations, holographic media and holograms.

  该发明涉及一种从有机硼酸酯出发制备三芳基有机硼酸酯的方法，该方法在n价阳离子1/n Kn+存在下进行，包括对反应混合物进行无水处理和使用所得的三芳基有机硼酸酯作为光聚合物配方、全息介质和全息图中的共同引发剂。
• UV absorption spectrum and self-reaction of cyclohexylperoxy radicals
  作者：David M. Rowley、Phillip D. Lightfoot、Robert Lesclaux、Timothy J. Wallington

  DOI：10.1039/ft9918703221

  日期：——

  cyclohexyloxy radical formed in channel (1a): c-C6H11O + M → CH2(CH2)4CHO + M (4) competes with the reaction with oxygen: c-C6H11O + O2→ c-C6H10O + HO2(2) under atmospheric conditions. Flash photolysis–UV absorption experiments were used to obtain the UV spectrum of the cyclohexylperoxy radical and the kinetics of reaction (1). The spectrum of c-C6H11O2 is similar to those of other alkylperoxy radicals, with

  环己基过氧自由基自反应的动力学和机理：2c-C 6 H 11 O 2 →2c-C 6 H 11 O + O 2（1 a），→cC 6 H 10 O + cC 6 H 11 OH + O 2（1 b）已使用时间分辨和最终产品分析技术进行了研究。Cl 2 –cC 6 H 12 –O 2 –N 2的光氧化作用测定产物的产率使用FTIR光谱法的混合物表明，用于产生自由基的通道（1点分支比一）为295 K.另外，在氧分压示出了产物的产率的依赖性0.29±0.02，在所形成的环己基基团的开环通道（1 a）：cC 6 H 11 O + M→CH 2（CH 2）4 CHO + M（4）与氧气竞争反应：cC 6 H 11 O + O 2 →cC 6 H 10 O + HO 2个（2）在大气条件下。闪光光解-紫外吸收实验用于获得环己基过氧自由基的紫外光谱和反应动力学（1）。CC的光谱6 ħ 11 ö 2是类似于那些其他烷基过氧自由基，具有的（4
• Metal-free oxygenation of cyclohexane with oxygen catalyzed by 9-mesityl-10-methylacridinium and hydrogen chloride under visible light irradiation
  作者：Kei Ohkubo、Atsushi Fujimoto、Shunichi Fukuzumi

  DOI：10.1039/c1cc12534f

  日期：——

  Photooxygenation of cyclohexane by O(2) occurs efficiently under visible-light irradiation of an O(2)-saturated acetonitrile solution containing 9-mesityl-10-methylacridinium ions (Acr(+)-Mes) and HCl to yield cyclohexanone, cyclohexanol and hydrogen peroxide. The photocatalytic reaction is initiated by electron transfer from Cl(-) to the mesitylene radical cation moiety.

  O（2）对环己烷的光氧化有效发生在O-（2）-饱和的乙腈溶液的可见光辐射下，该溶液含有9-甲磺基-10-甲基ac离子（Acr（+）-Mes）和HCl，产生环己酮，环己醇和过氧化氢。光催化反应是通过电子从Cl（-）转移至均三甲苯基阳离子部分而引发的。
• Ultraviolet absorption spectrum and self-reaction of cyclopentylperoxy radicals
  作者：David M. Rowley、Phillip D. Lightfoot、Robert Lesclaux、Timothy J. Wallington

  DOI：10.1039/ft9928801369

  日期：——

  The kinetics and mechanism of the self-reaction of cyclopentylperoxy radicals: 2 c-C5H9O2→ 2 c-C5H9O + O2(1a), → c-C5H9OH + c-C5H8O + O2(1b), have been studied using both time-resolved and end-product-analysis techniques. Determination of the product yields from the photolysis of Cl2–c-C5H10–O2–N2 mixtures using FTIR spectroscopy demonstrates that ring-opening of the cyclopentoxy radical formed in channel (1a): c-C5H9O + M → CH2(CH2)3CHO + M (3) dominates over reaction with oxygen: c-C5H9O + O2→ c-C5H8O + HO2(2), under atmospheric conditions. Flash photolysis-UV absorption experiments were used to obtain the UV spectrum of the cyclopentylperoxy radical and the kinetics of reaction (1). The spectrum of c-C5H9O2 is similar to those of other alkylperoxy radicals, with a maximum cross-section of (5.22 ± 0.20)× 10–18 cm2 molecule–1 at 250 nm, measured relative to a value of 4.55 × 10–18 cm2 molecule–1 for CH3O2 at 240 nm. The observed second-order rate constant, kobs(–d[c-C5H9O2]/dt= 2kobs[c-C5H9O2]2), for removal of cyclopentylperoxy radicals was dependent on the oxygen partial pressure. Experiments as a function of temperature from 243 to 373 K gave limiting minimum and maximum values of kobs at low (<1 Torr) and high (>50 Torr) oxygen partial pressures, respectively: kmin/cm3 molecule–1 s–1=(1.3 ± 0.4)× 10–14 exp[(188 ± 83)K/T] and kmax/cm3 molecule–1 s–1=(2.9 ± 0.8)× 10–13 exp[–(555 ± 77)K/T]. At low oxygen partial pressures, the only effective removal channel for cyclopentylperoxy radicals is the molecular channel (1b) and kmin can be equated to k1b. Simulations suggest that kmax represents an upper limit on k1 and is at most 25% greater. In light of the present results on the cyclopentylperoxy radical, further experiments were performed on the cyclohexylperoxy radical self-reaction: 2 c-C6H11O2→ 2 c-C6H11O + O2(16a), → c-C6H11OH + c-C6H10O + O2(16b) at low oxygen partial pressures, giving k16b/cm3 molecule–1 s–1=(1.3 ± 0.3)× 10–14 exp[(185 ± 15) K/T] and an estimated k16/cm3 molecule–1 s–1= 7.7 × 10–14 exp(–184 K/T). The above errors are 1σ and represent experimental uncertainty only.

  使用时间分辨模型研究了环戊基过氧自由基自反应的动力学和机理：2 c-C5H9O2→ 2 c-C5H9O + O2(1a), → c-C5H9OH + c-C5H8O + O2(1b)和最终产品分析技术。使用 FTIR 光谱测定 Cl2–c-C5H10–O2–N2 混合物光解的产物产率表明，通道 (1a) 中形成环戊氧基自由基的开环：c-C5H9O + M → CH2(CH2)3CHO +在大气条件下，M (3) 主导与氧的反应：c-C5H9O + O2→ c-C5H8O + HO2(2)。采用闪光光解-紫外吸收实验获得了环戊基过氧自由基的紫外光谱和反应动力学(1)。 c-C5H9O2 的光谱与其他烷基过氧自由基的光谱相似，在 250 nm 处最大横截面为 (5.22 ± 0.20)× 10–18 cm2 molecular–1，相对于 4.55 × 10–18 的值测量cm2 分子–1（CH3O2），240 nm。观察到的去除环戊基过氧自由基的二阶速率常数 kobs(–d[c-C5H9O2]/dt= 2kobs[c-C5H9O2]2) 取决于氧分压。作为 243 至 373 K 温度函数的实验分别给出了低氧分压 (<1 Torr) 和高氧分压 (>50 Torr) 下 kobs 的限制最小值和最大值：kmin/cm3 分子–1 s–1=( 1.3±0.4)×10–14exp[(188±83)K/T]和kmax/cm3分子–1s–1=(2.9±0.8)×10–13exp[–(555±77)K/T ]。在低氧分压下，环戊基过氧自由基唯一有效的去除通道是分子通道（1b），kmin 可等于 k1b。模拟表明 kmax 代表 k1 的上限，最多大 25%。根据环戊基过氧自由基的现有结果，对环己基过氧自由基自反应进行了进一步的实验： 2 c-C6H11O2→ 2 c-C6H11O + O2(16a), → c-C6H11OH + c-C6H10O + O2(16b) ）在低氧分压下，给出 k16b/cm3 分子–1 s–1=(1.3 ± 0.3)× 10–14 exp[(185 ± 15) K/T] 和估计的 k16/cm3 分子–1 s–1 = 7.7 × 10–14 exp(–184 K/T)。上述误差为 1σ，仅代表实验不确定性。
• Kinetics of the Cross Reactions of CH₃O₂ and C₂H₅O₂ Radicals with Selected Peroxy Radicals
  作者：Eric Villenave、Robert Lesclaux

  DOI：10.1021/jp960765m

  日期：1996.1.1

  be between the rate constants for the self-reactions of RO2 and CH3O2 (or C2H5O2). However, when the RO2 self-reaction is fast, the cross reaction with CH3O2 (or C2H5O2) is also fast, with similar rate constants for both reactions, suggesting that these particular peroxy radical cross reactions can play a significant role in the chemistry of hydrocarbon oxidation processes in the troposphere and in

  使用两种技术研究了选定的过氧自由基（RO 2）与CH 3 O 2和与C 2 H 5 O 2的反应动力学：准分子激光光解法和常规闪速光解法，均与紫外吸收光谱法结合。在适当的烃存在下，通过分子氯的光解或通过适当的烷基氯的光解，产生自由基。除烯丙基过氧自由基与CH 3 O 2的反应外，所有此类交叉反应动力学均在760 Torr总压力和室温下进行。，对于将其291和423之间所确定的速率常数K，从而产生以下速率表达式：  ķ 15 =（2.8±0.7）×10 -13 EXP [（515±75）/ Ť ]厘米3分子-1小号- 1。（2.0±0.5）×10 -13，（1.5±0.5）×10 -12，（9.0±0.15）×10 -14，<2.0×10 -12，（2.5±0.5）×10 -12，和CH 3 O 2的反应获得了（8.2±0.6）×10 -12（cm 3分子-1 s -1的单位）。具有C 2 H