methylperoxy radical | 2143-58-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methylperoxy radical
• 英文别名: Methyldioxy
• CAS: 2143-58-0
• 化学式: CH₃O₂
• 分子量: 47.0336
• InChiKey: WTFNSXYULBQCQV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• 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：

  methylperoxy radical 在 氧化亚氮 作用下， -70.15~21.85 ℃ 、26.66 kPa 条件下， 生成 硝基甲烷
  参考文献：
  名称：

  Kinetics of the CH₃O₂ + NO Reaction:  Temperature Dependence of the Overall Rate Constant and an Improved Upper Limit for the CH₃ONO₂ Branching Channel

  摘要：

  The overall rate constant and an upper limit for the CH3ONO2 product channel for the CH3O2 + NO reaction have been measured using the turbulent flow technique with high-pressure chemical ionization mass spectrometry for the detection of reactants and products. At room temperature and 100 Torr pressure, the rate constant (and the two standard deviation error limit) was determined to be (7.8 +/- 2.2) x 10(-12) cm(3) molecule(-1) s(-1). The temperature dependence of the rate constant was investigated between 295 and 203 K at pressures of either,100 or 200 Torr, and the data was fit to the following Arrhenius expression: (9.2(-3.9)(+6.0) x -10(-13)) exp[(600 +/- 140)/T] cm(3) molecule(-1) s(-1). Although the room-temperature rate constant value agrees well with the current recommendation for atmospheric modeling, our values for the rate constant at the lowest temperatures accessed in this study (203 K) are about 50% higher than the same recommendation. No CH3ONO2 product was detected from the CH3O2 + NO reaction (using direct CH3ONO2 detection methods for the first time), but an improved upper limit of 0.03 (at 295 K and 100 torr) for this branching channel was determined.

  DOI：

  10.1021/jp990469k
• 作为产物：
  描述：

  过氧硝酸甲酯 以 水 为溶剂， 生成 methylperoxy radical
  参考文献：
  名称：

  水溶液中有机过氧自由基与•NO2 和•NO 的反应：有机过氧硝酸盐和过氧亚硝酸盐的中间体

  摘要：

  在这项工作中，我们使用脉冲辐解技术研究了烷基过氧自由基与•NO2 和•NO 的反应。•NO2 与(CH3)2C(OH)CH2OO•、CH3OO• 和c-C5H9OO• 反应的速率常数在7 × 108 和1.5 × 109 M-1 s-1 之间变化。该反应产生相对长寿命的过氧硝酸烷基酯，它与母体自由基平衡，在 270 nm 以上没有明显的吸收。还表明•NO 迅速加入(CH3)2C(OH)CH2OO• 和CH3OO• 以形成烷基过氧亚硝酸盐。这些反应的速率常数分别确定为 2.8 × 109 和 3.5 × 109 M-1 s-1。然而，与过氧硝酸烷基酯相比，过氧亚硝酸烷基酯不会积累。相反，它们通过沿相对较弱的 O-O 键均裂而迅速分解，最初形成一对。这对中的大部分在笼中坍缩形成硝酸烷基酯RONO2，大约14% 以游离烷氧基和•NO2 自由基的形式扩散出来。热动力学分析预测 CH3 的半衰期..

  DOI：

  10.1021/jp037431z

文献信息

• Investigation into the kinetics and mechanism of the reaction of NO3 with CH3 and CH3O at 298 K between 0.6 and 8.5 Torr: is there a chain decomposition mechanism in operation?
  作者：Peter Biggs、Carlos E. Canosa-Mas、Jean-Marc Fracheboud、Dudley E. Shallcross、Richard P. Wayne

  DOI：10.1039/ft9949001197

  日期：——

  The reactions CH3+ NO3→ products (1), and CH3O + NO3→ products (2), have been studied using a flow system at T= 298 K and at pressures between 0.6 and 8.5 Torr. The laser-induced fluorescence (LIF) technique was used to detect CH3O and multi-pass optical absorption to detect NO3. The chemical systems were studied as a pair of consecutive reactions; however, a simple analytical treatment was not sufficient

  CH 3 + NO 3 →产物（1）和CH 3 O + NO 3 →产物（2）的反应已使用流动系统在T = 298 K且压力介于0.6和8.5 Torr之间进行了研究。激光诱导荧光（LIF）技术用于检测CH 3 O，多道光吸收检测NO 3。化学系统被作为一对连续的反应进行了研究。然而，简单的分析方法不足以描述它们，因为CH 3 O 2作为主要反应通道中的产物之一形成（2）。该物质还与NO 3发生反应，生成CH 3O.使用数值模型校正此再生过程时，允许的速率参数为k 1 =（3.5±1.0）×10 –11 cm 3分子–1 s –1和k 2 =（2.3±0.7）×10 –12 cm 3分子–1 s –1将在2.4 Torr下确定。在1至2.4 Torr之间，未观察到反应（1）的压力依赖性，但是存在对反应（2）的轻微压力依赖性的可能性。使用半经验量子RRK方法检查了这些压力效应。
• Flash photolysis study of the UV spectrum and kinetics of reactions of the acetonylperoxy radical
  作者：Isabelle Bridier、Bernard Veyret、Robert Lesclaux、Michael E. Jenkin

  DOI：10.1039/ft9938902993

  日期：——

  2CH3C(O)CH2O2→ 2CH3C(O)CH2O + O2(7a) and → CH3C(O)CH2OH + CH3C(O)CHO + O2(7b) with k7=(8.0 ± 2.0)× 10–12 cm3 molecule–1 s–1 and k7a/k7=(0.75 ± 0.1). The kinetics of the reactions between CH3C(O)CH2O2 and the CH3C(O)O2, CH3O2 and HO2 radicals were determined by adding acetaldehyde, methane or methanol to the photolysis mixtures: CH3C(O)CH2O2+ CH3C(O)O2→ O2+ CH3C(O)CH2O + CH3+ CO2(11a); → O2+ CH3C(O)OH + CH3C(O)CHO

  通过快速光解-紫外吸收法研究了在氧存在下通过Cl原子与丙酮之间的反应形成的CH 3 C（O）CH 2 O 2自由基的紫外光谱和动力学。根据描述使用最终产品分析的工作的前一篇文章的结果对结果进行了分析。过氧自由基CH 3 C（O）CH 2 O 2在UV中吸收，在约230和290 nm处有两个最大值。该过氧自由基根据以下条件反应：2CH 3 C（O）CH 2 O 2 →2CH 3 C（O）CH 2 O + O 2（7 a）和→CH 3 C（O）CH 2 OH + CH 3 C（O）CHO + O 2（7 b），其中k 7 =（8.0±2.0）×10 –12 cm 3分子–1 s –1和k 7 a / k 7＝（0.75±0.1）。CH 3 C（O）CH 2 O 2与CH 3 C（O）O 2，CH 3 O 2和HO 2之间反应的动力学通过向光解混合物中添加乙醛，甲烷或甲醇来确定自由基：CH 3 C（O）CH
• Kinetics and products of the reactions of CH₃O₂ with Cl and ClO
  作者：V Daële、G Poulet

  DOI：10.1051/jcp/1996931081

  日期：——

  The mechanisms of the reactions CH_{3O2 + Cl → products (1) and CH3O2 + ClO → products (2) have been studied at 298 K using a discharge flow reactor coupled to laser induced fluorescence for the detection of CH3O, observed as a product of both reactions, and mass spectrometry for the detection of other species. In the kinetic study of reaction (1), the channel producing the Criegee radical, CH2O2, has been found to be preponderant compared to the CH3O forming channel ; CH3O2 + Cl → CH3O + ClO (la), k1a = (2.0 ± 0.4) x 10^{-11 cm3 molecule-1 s-1 and CH3O2 + Cl → CH2O2 + HC1 (lb), k1b = (2.0 ± 0.4) x 10-10 cm3 molecule-1 s-1. The study of reaction (2) aimed at identifying the reaction pathways : CH3O2 + ClO → CH3O + ClOO (2a) and CH3O2 + ClO → CH3OCl + O2 (2b). The branching ratio for the first channel has been determined : α2a = 0.3 ± 0.1. These results are compared with other recent literature data and their atmospheric implication is briefly discussed.}}

  在298 K下，使用放电流动反应器结合激光诱导荧光检测甲氧基（CH_{3O），该物质作为两种反应的产物被观测到，并利用质谱法检测其他物种，研究了反应CH3O2 + Cl → 产物（1）和CH3O2 + ClO → 产物（2）的机制。在反应（1）的动力学研究中，发现生成Criegee自由基（CH2O2）的通道相对于生成甲氧基（CH3O）的通道更为主要；CH3O2 + Cl → CH3O + ClO（1a），k1a = (2.0 ± 0.4) x 10^{-11 cm3 molecule-1 s-1 和 CH3O2 + Cl → CH2O2 + HC1（1b），k1b = (2.0 ± 0.4) x 10-10 cm3 molecule-1 s-1。反应（2）的研究旨在确定反应路径：CH3O2 + ClO → CH3O + ClOO（2a）和CH3O2 + ClO → CH3OCl + O2（2b）。第一个通道的分支比已被确定：α2a = 0.3 ± 0.1。这些结果与最近的文献数据进行了比较，并简要讨论了它们对大气的影响。}}
• Reactions of Superoxo and Oxo Metal Complexes with Aldehydes. Radical-Specific Pathways for Cross-Disproportionation of Superoxometal Ions and Acylperoxyl Radicals
  作者：Andreja Bakac

  DOI：10.1021/ja026365w

  日期：2002.8.1

  remote oxygen of Cr(aq)OO(2+), followed by elimination of O(2) and formation of CH(3)COOH and Cr(V)(aq)O(3+). The latter disproportionates and ultimately yields Cr(aq)(3+) and HCrO(4)(-). No CO(2) was detected. The Cr(aq)OO(2+)/C(CH(3))(3)C(O)OO(*) reaction yielded isobutene, CO(2), and Cr(aq)(3+), in addition to chromate. In the suggested mechanism, the transient Cr(aq)OOOO(O)CC(CH(3))(3)(2+) branches into

  aquachromyl(IV) 离子，Cr(aq)O(2+)，通过氢原子提取与乙醛和新戊醛反应，并在 O(2) 存在下产生酰基过氧自由基 RC(O)OO(*)。在下一步中，自由基与 Cr(aq)OO(2+) 反应，Cr(aq)O(2+) 是我们制备中伴随 Cr(aq)O(2+) 的一种物质。Cr(aq)OO(2+)/CH(3)C(O)OO(*) 交叉反应的速率常数，k(Cr) = 1.5 x 10(8) M(-1) s(-1 )，由激光闪光光解测定。证据表明在 Cr(aq)OO(2+) 的远程氧发生自由基耦合，随后消除 O(2) 并形成 CH(3)COOH 和 Cr(V)(aq)O(3+) . 后者不成比例并最终产生 Cr(aq)(3+) 和 HCrO(4)(-)。没有检测到 CO(2)。Cr(aq)OO(2+)/C(CH(3))(3)C(O)OO(*) 反应生成异丁烯、CO(2) 和 C
• The CH₃C(O)O₂ Radical. Its UV Spectrum, Self-Reaction Kinetics, and Reaction with CH₃O₂
  作者：M. Matti Maricq、Joseph J. Szente

  DOI：10.1021/jp9533234

  日期：1996.1.1

  The reactions of CH3C(O)O2 with itself and with CH3O2 are investigated using flash photolysis combined with time-resolved UV spectroscopy and transient infrared absorption. The UV spectrum of CH3C(O)O2 exhibits two bands; the stronger short wavelength component has a maximum cross section of 6.5 × 10-18 cm2 at 206 nm and the weaker one a cross section of 2.9 × 10-18 cm2 at 250 nm. These bands are used

  CH 3 C（O）O 2本身与CH 3 O 2的反应是使用快速光解结合时间分辨紫外光谱和瞬态红外吸收进行研究的。CH 3 C（O）O 2的紫外光谱显示出两个谱带。较强的短波分量在206 nm处的最大横截面为6.5×10 -18 cm 2，而较弱的短波长分量在250 nm处的最大横截面为2.9×10 -18 cm 2。这些频带被用于监测CH消失3 C（O）O 2和次级CH的形成3 ö 2，产生的自反应速率常数为 ×10 -12  e （504±114）/ T cm 3 s -1和交叉反应速率常数为 ×10 -13  e （726±75）/ T cm 3 s -1。对CH 2 O形成的瞬态红外监测显示CH 3 C（O）O 2 + CH 3 O 2 →CH 2 O + CH 3 COOH + O 2是整个209-358 K温度范围内交叉反应的主要通道。这与先前的研究相反，后者的研究表明支化比率对温度的依赖性很强，在高温下通道导致CH