vinyloxyl | 4400-01-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: vinyloxyl
• 英文别名: vinoxy radical；Acetaldehydradikal；Formyl-methyl-Radikal；Formylmethyl
• CAS: 4400-01-5
• 化学式: C₂H₃O
• 分子量: 43.0452
• InChiKey: FATAVLOOLIRUNA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 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：
  1
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  vinyloxyl 在 氧气 作用下， 21.9~199.9 ℃ 、13.33 kPa 条件下， 生成
  参考文献：
  名称：

  乙烯基氧基与氧气和一氧化氮的气相反应

  摘要：

  DOI：

  10.1021/j100243a023
• 作为产物：
  描述：

  乙烯 在 O 作用下， 生成 vinyloxyl
  参考文献：
  名称：

  Fonderie, V.; Maes, D.; Peeters, J., Bulletin des Societes Chimiques Belges, 1983, vol. 92, # 6-7, p. 641 - 642

  摘要：

  DOI：
• 作为试剂：
  描述：

  对苯二胺 在 氢氧化钾 、 vinyloxyl 作用下， 以 水 、 乙二醇 为溶剂， 生成 4-氨基苯胺基
  参考文献：
  名称：

  酚的单电子氧化还原电位。具有生物学意义的羟基和氨基酚及相关化合物

  摘要：

  DOI：

  10.1021/j100215a033

文献信息

• Formation of HO2 from OH and C2H2 in the presence of O2
  作者：Birger Bohn、Cornelius Zetzsch

  DOI：10.1039/a708536b

  日期：——

  Pulsed production of OH in a gas-phase system containing acetylene, O2 and NO resulted in biexponential OH-decay curves, indicating formation of HO2 in secondary reactions. Production and detection of OH were performed by 248 nm photolysis of H2O2 and cw-laser long-path absorption at 308 nm, respectively. Measurements were made at room temperature in O2 or N2–O2 mixtures containing 5% O2 at total pressures between 10 and 100 kPa. Analysis of the decay curves resulted in effective rate constants for the removal of OH and the formation of HO2 by acetylene in the presence of O2 in the range (1.4–3.5)×10-13 cm3 s-1, dependent on total pressure and O2 concentration. HO2 is thought to be formed from HCO and O2, with HCO originating in a reaction of an intermediate acetylene–OH adduct with O2. HO2 yields were found to vary between 1.13 and 1.01 and tending to higher values at lower total pressures. These yields are higher than the expected value of 1, which can be explained by a dissociation of a small fraction of vibrationally excited glyoxal formed, together with OH in a second channel of the acetylene–OH adduct+O2 reaction. In order to check whether the increased HO2 yields are real, CO was used instead of acetylene. In this case, an HO2 yield of 0.99 was found, in good agreement with expectations, and a rate constant of (1.66±0.25)×10-13 cm3 s-1 for the OH+CO reaction in 20 kPa O2 was determined. In addition, a rate constant for the HO2+NO reaction of (9.5±1.5)×10-12 cm3 s-1, rate constants for the OH+NO reaction in the range (1.3–7.4)×10-12 cm3 s-1, depending on total pressure, and upper limits for the rate constants of possible reactions HO2+C2H2 (k⩽5×10-15 cm3 s-1) and HO2+CO (k⩽3×10-15 cm3 s-1) were derived. Error limits include statistical (2σ) and possible systematic errors.

  在含有乙炔、O2和NO的气相系统中，OH的脉冲产生导致了双指数OH衰减曲线，表明在次级反应中形成了HO2。通过248 nm光解H2O2产生OH，通过连续波激光长路径吸收在308 nm检测OH。在室温下，在总压力介于10至100 kPa之间，含有5% O2的O2或N2-O2混合物中进行测量。衰减曲线的分析得到了在O2存在下，乙炔移除OH和形成HO2的有效速率常数在(1.4-3.5)×10-13 cm3 s-1范围内，这取决于总压力和O2浓度。HO2被认为是从HCO和O2中形成的，HCO源自于乙炔-OH中间体与O2的反应。HO2的产率在1.13和1.01之间变化，并向较低的总压力下趋向更高值。这些产率高于预期的1，这可以通过一小部分振动激发态的乙二醛在乙炔-OH中间体+O2反应的第二通道中与OH一起形成后解离来解释。为了检验增加的HO2产率是否真实，使用了CO代替乙炔。在这种情况下，发现HO2产率为0.99，与预期相符，并在20 kPa O2中确定了OH+CO反应的速率常数为(1.66±0.25)×10-13 cm3 s-1。此外，得到了HO2+NO反应的速率常数为(9.5±1.5)×10-12 cm3 s-1，OH+NO反应的速率常数在(1.3-7.4)×10-12 cm3 s-1范围内，取决于总压力，以及可能反应HO2+C2H2（k⩽5×10-15 cm3 s-1）和HO2+CO（k⩽3×10-15 cm3 s-1）的速率常数的上限。误差限包括统计误差（2σ）和可能的系统误差。
• Reaction of atomic oxygen with some simple alkenes. Part 2.—Reaction pathways involving ethene, propene and (E)-but-2-ene at atmospheric pressure
  作者：Christopher Anastasi、Michael G. Sanderson、Palle Pagsberg、Alfred Sillesen

  DOI：10.1039/ft9949003625

  日期：——

  Results from a study of the reaction of atomic oxygen with ethene and propene at atmospheric pressure are reported. Pulse radiolysis of CO2 has been used to generate ground-state atomic oxygen in the presence of the alkenes. The yield of methyl radicals from the reaction of O with ethene, propene and (E)-but-2-ene was measured as 0.70 ± 0.05, 0.15 ± 0.01 and 0.25 ± 0.08, respectively. The yield of the vinyloxyl radical, CH2CHO, from the reaction of O atoms with propene was found to be 0.12 ± 0.03, in good agreement with the methyl radical yield. An upper limit for other radical-producing channels for this reaction of 0.21 ± 0.07 was derived. The formyl radical (HCO) was also searched for in the ethene and propene systems but was not detected in either, which placed an upper limit on its yield of 0.03 in both systems.

  报道了一项关于原子氧与乙烯和丙烯在大气压下反应的研究结果。通过脉冲辐解CO2在烯烃存在下生成基态原子氧。测量了O与乙烯、丙烯和（E）-2-丁烯反应生成甲基自由基的产率，分别为0.70 ± 0.05、0.15 ± 0.01和0.25 ± 0.08。发现O原子与丙烯反应生成乙烯氧自由基CH2CHO的产率为0.12 ± 0.03，与甲基自由基产率吻合良好。推导出该反应其他自由基产生途径的上限为0.21 ± 0.07。在乙烯和丙烯体系中搜索了甲酰自由基（HCO），但在两者中均未检测到，从而在两个体系中对其产率设定了0.03的上限。
• Experimental and theoretical studies of gas phase NO3 and OH radical reactions with formaldehyde, acetaldehyde and their isotopomersElectronic supplementary information (ESI) available: program package FACSIMILE for simulation of the complex set of reactions and the kinetics of the reactor system. Kinetic data from the acetaldehyde studies, the spectral ranges and the compounds included in the subtraction procedures, and a full report of the statistical analyses. Calculated energies of the reactants, intermediate stationary points of the potential energy surface, and the products. Calculated vibrational wavenumbers of the reactants and transition states. See http://www.rsc.org/suppdata/cp/b2/b211234p/
  作者：Barbara D'Anna、Vebjørn Bakken、Jon Are Beukes、Claus J. Nielsen、Katarzyna Brudnik、Jerzy T. Jodkowski

  DOI：10.1039/b211234p

  日期：2003.4.16

  The vapour phase reactions of formaldehyde, formaldehyde-d2, 13C-formaldehyde, acetaldehyde, acetaldehyde-1-d1, acetaldehyde-2,2,2-d3, and acetaldehyde-d4 with NO3 and OH radicals were studied at 298 ± 2 K and 1013 ± 10 mbar using long-path FTIR detection. The values of the kinetic isotope effects at 298 K, as determined by the relative rate method, were: kNO3+HCHO/kNO3+DCDO = 2.97 ± 0.14, kNO3+HCHO/kNO3+H13CHO = 0

  在 298 ± 2 K 和使用长路径 FTIR 检测时为 1013 ± 10 mbar。由相对速率法测定的 298 K 时的动力学同位素效应值为：kNO3+HCHO/kNO3+DCDO = 2.97 ± 0.14，kNO3+HCHO/kNO3+H13CHO = 0.97 ± 0.02，kOH+HCHO/kOH +DCDO = 1.62 ± 0.08，kOH+H13CHO/kOH+DCDO = 1.64 ± 0.12，kOH+HCHO/kOH+H13CHO = 0.97 ± 0.11，kNO3+CH3CHO/kNO3+CD3CHO = 1.19 ± 0.11，kNO3+CH3CHO/kNO3+ CD3CDO = 2.51 ± 0.09，kOH+CH3CHO/kOH+CH3CDO = 1.42 ± 0.10，kOH+CH3CHO/kOH+CD3CHO = 1.13 ± 0.04，并且 kOH+CH3CHO/kOH+CD3CDO
• The rapid hydration of the acetyl radical. A pulse radiolysis study of acetaldehyde in aqueous solution.
  作者：Man Nien. Schuchmann、Clemens. Von Sonntag

  DOI：10.1021/ja00225a019

  日期：1988.8

  are in a 0.8:1 equilibrium. Hydroxyl radicals generated by the pulse radiolysis of N/sub 2/O-saturated water react with this mixture with an overall rate constant of k = 2.4 x 10/sup 9/ dm/sup 3/ mol/sup -1/ s/sup -1/, the rate of reaction with acetaldehyde being about 3 times faster than with the hydrate. The predominant radicals formed are the acetyl radical and its hydrated form, H-abstraction at

  在水溶液中，乙醛及其水合物处于 0.8:1 的平衡状态。N/sub 2/O 饱和水的脉冲辐射分解产生的羟基自由基与该混合物反应，总速率常数 k = 2.4 x 10/sup 9/dm/sup 3/mol/sup -1/s/sup -1/，与乙醛的反应速度比与水合物的反应速度快约 3 倍。形成的主要自由基是乙酰基及其水合形式，甲基上的 H-抽象仅发生约 5-10%。乙酰基快速水合，其水合速率比母体化合物乙醛快 2 x 10/sup 6/ 倍。水合乙酰基自由基通过四硝基甲烷的快速还原、/sub 2//sup .-/ 在氧气存在下的形成以及在 pH 11 (pK/sub a/ /<=/ 9.5) 下的去质子化来监测。乙酰基在脉冲辐解时间尺度上不会氧化 N,N,N',N'-四甲基-对苯二胺 (TMPD)，但乙酰过氧自由基（在氧气存在下形成）与 TMPD、抗坏血酸、和 O/sub 2//sup .-
• Pulse radiolysis and election spin resonance studies of the dehydration of radicals from 1,2-diols and related compounds
  作者：Steen Steenken、Michael J. Davies、Bruce C. Gilbert

  DOI：10.1039/p29860001003

  日期：——

  The complementary techniques of pulse-radiolysis and e.s.r. spectroscopy have been employed in a kinetic study of the dehydration of a variety of α,β-dihydroxyalkyl radicals [˙CR1(OH)CR2R3OH] into the appropriate carbonyl-conjugated radicals [˙CR2R3C(O)R1]. The overall rates of proton-catalysed dehydration, as revealed by steady-state (e.s.r.) and time-resolved (pulse-radiolysis) experiments, indicate

  脉冲辐解和ESR光谱的互补技术已经在各种α，β二羟基烷基的基团的[CR脱水的动力学研究已经采用1（OH）CR 2 - [R 3 OH]到相应的羰基共轭的基团[CR 2 - [R 3 C（O）R 1 ]。稳态（esr）和时间分辨（脉冲辐射分解）实验揭示的质子催化脱水的总速率表明了取代基的电子效应的重要性（对比度值为1.2×10 9和9.8×10 8 dm 3摩尔–1 s –1分别来自环己烷-1,2-二醇和丁烷-2,3-二醇的自由基，而赤藓糖醇的自由基分别为4.2×10 6 dm 3 mol –1 s –1）。时间分辨实验允许获得有关质子化物种[speciesCR 1（OH）CR 2 R 3 OH 2 + ]的生成以及该中间体中水分损失的信息。