2-Butoxy radical | 26397-42-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-Butoxy radical
• 英文别名: 2-butoxyl radical
• CAS: 26397-42-2
• 化学式: C₄H₉O
• 分子量: 73.1149
• InChiKey: HFQYJCVJLPOROO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  5
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  2-Butoxy radical 在 氧化亚氮 作用下， 21.85 ℃ 、39.4 kPa 条件下， 生成 仲丁基亚硝酸酯
  参考文献：
  名称：

  Rate constants for the decomposition of 2-butoxy radicals and their reaction with NO and O2

  摘要：

  利用激光光解/激光诱导荧光技术研究了 2-丁氧基自由基的反应性。研究了三个反应：(i) 在 0.03 < p < 0.4 bar 的氦气总压力和 295-348 K 之间的五个温度下，用同样的技术测量了与 NO 反应的速率常数。(ii) 在室温和 0.131 巴氦气条件下测得 O2 的速率常数：k2 = (9 ± 2) × 10-15 cm3 s-1。由于 O2 对 2-丁氧基荧光有明显的淬灭作用，因此无法在更大的温度范围内进行实验：kq,O2 = (4 ± 1) × 10-11 cm3 s-1。(iii) 在 0.01 < p < 0.8 bar 的氦气总压和 291-348 K 的四种温度下单分子分解的温度和压力依赖性。2 × 10-8 exp(-35.9 kJ mol-1/RT) cm3 s-1，k3,∞ = 1.1 × 1014 exp(-53.6 kJ mol-1/RT) s-1，F3,c = 0.87 - T/870 K。我们预计这些速率常数的不确定性为 ±30%。这些结果与之前的预测（C. Fittschen, H. Hippler and B. Viskolcz, Phys.Chem.Phys., 2000, 2, 1677-1683 (); R. Méreau, M.-T.Rayez, F. Caralp and J.-C.Rayez, Phys.Chem.Phys., 2000, 2, 3765 ()) .

  DOI：

  10.1039/b405134c
• 作为产物：
  描述：

  2-碘丁烷 在 氧气 、 氧化亚氮 作用下， 24.85 ℃ 、100.0 kPa 条件下， 生成 2-Butoxy radical
  参考文献：
  名称：

  Relative-rate study of thermal decomposition of the 2-butoxyl radical in the temperature range 280–313 KElectronic supplementary information (ESI) available: See http://www.rsc.org/suppdata/cp/b1/b111474c/

  摘要：

  在由石英制成的新建210升光反应器中，对2-丁氧基自由基的分解（kdis）与O2反应（kO2）的竞争进行了研究。2-丁氧基自由基是在存在O2和NO的情况下，通过持续的254纳米光解2-丁氧基碘化物产生的，使用N2作为缓冲气体。反应物和产物通过使用傅里叶变换红外光谱仪的长路径（29米）红外吸收进行分析。根据乙醛和丁酮的产品比例，修正了少量副产物的影响，得到了kdis/kO2的比例。在280、298和313 K以及总压力为1巴（M=O2+N2）的条件下，kdis/kO2在O2的分压介于100到1000毫巴之间被确定。在所有温度下，(kdis/kO2)eff≡(Δ[CH3CHO]corr×[O2])/(2×Δ[CH3C(O)CH2CH3])随O2分压的增加有系统性的增加，这可能是由于来自O2独立来源的乙醛的额外贡献（在298 K，1巴的条件下，大约8%的2-丁氧基自由基通过这两种竞争路径中的任何一种反应）。在100到1000毫巴的压力依赖性研究支持了这样一个假设，即额外的乙醛来源于在280到313 K的温度范围内形成的化学激活的2-丁氧基自由基，其比例为6到10%。修正(kdis/kO2)eff对于O2独立产生的乙醛的产率，得到了kdis/kO2=(6.8±1.4)×1017，(2.3±0.5)×1018，和(5.5±1.1)×1018分子cm-3在279.8，298.2，和313.5 K，分别，导致Arrhenius表达式kdis/kO2=(2.0±0.5)×1026exp(-45.4 kJ mol-1/RT)分子cm-3在总压力为1巴。这个kdis/kO2的温度依赖性意味着，取决于温度，在较低对流层的条件下，要么是热分解，要么是与O2反应是2-丁氧基自由基的主要损失过程。使用文献中的kO2值，对于总压力为1巴（M=N2+O2），导出kdis=3.9×1012exp(-47.1 kJ mol-1/RT) s-1，这与Somnitz和Zellner的最近理论估计（从头计算+RRKM）非常吻合。

  DOI：

  10.1039/b111474c

文献信息

• Dispersed fluorescence spectroscopy of primary and secondary alkoxy radicals
  作者：Jin Jin、Ilias Sioutis、György Tarczay、Sandhya Gopalakrishnan、Andrew Bezant、Terry A. Miller

  DOI：10.1063/1.1814104

  日期：2004.12.15

  Dispersed fluorescence (DF) spectra of 1-propoxy, 1-butoxy, 2-propoxy, and 2-butoxy radicals have been observed under supersonic jet cooling conditions by pumping different vibronic bands of the B-X laser induced fluorescence excitation spectrum. The DF spectra were recorded for both conformers of 1-propoxy, three conformers of the possible five of 1-butoxy, the one possible conformer of 2-propoxy

  通过泵送BX激光诱导的荧光激发光谱的不同振动带，在超音速喷射冷却条件下观察到1-丙氧基，1-丁氧基，2-丙氧基和2-丁氧基的分散荧光（DF）光谱。记录了1-丙氧基的两个构象，1-丁氧基的可能的五个构象的三个构象，2-丙氧基的一个可能的构象和2-丁氧基的可能的三个构象的两个构象的DF光谱。频谱分析产生了地面X和低洼A电子态的无振动能级的能量分离，以及它们的振动频率。在所有情况下，DF谱的振动结构都以CO拉伸进程为主，从而产生X态（在大多数情况下为A态）的nuCO拉伸频率。除了实验工作，进行了量子化学计算，以帮助分配X状态的振动能级，对于某些构象异构体，也有助于A状态的能级。对异构体的不同构象异构体进行了几何优化，并确定了它们在基态中的能量差异。提供了不同构象的接近的X和A状态的能量分离的计算结果，以便与实验观察进行比较。
• Fluorescence excitation spectrum of the 2-butoxyl radical and kinetics of its reactions with NO and NO2
  作者：Ch. Lotz、R. Zellner

  DOI：10.1039/b101628h

  日期：——

  The (Ã←) fluorescence excitation spectrum of the 2-C4H9O() (2-butoxyl) radical in the wavelength range 345–390 nm was obtained using a combined laser photolysis/laser-induced fluorescence (LIF) technique following the generation of the radicals by excimer laser photolysis of 2-butylnitrite at λ = 351 nm. The fluorescence excitation spectrum shows 5 vibronic bands, where the dominant progression corresponds to the CO-stretching vibration in the first electronically excited state with CO′ = (560 ± 10) cm−1. The transition origin was assigned at 00 = (26768 ± 10) cm−1 (λ00 = (373.58 ± 0.15) nm). The kinetics of the reactions of the 2-butoxyl radical with NO and NO2 at temperatures between T = 223–305 K and pressures between p = 6.5–104 mbar have been determined. The rate coefficients for both reactions were found to be independent of total pressure with kNO = (3.9 ± 0.3) × 10−11 cm3 s−1 and kNO2 = (3.6 ± 0.3) × 10−11 cm3 s−1 at T = 295 K. The Arrhenius expressions have been determined to be kNO = (9.1 ± 2.7) × 10−12 exp((3.4 ± 0.6) kJ mol−1/RT) cm3 s−1 and kNO2 = (8.6 ± 3.3) × 10−12 exp((3.3 ± 0.8) kJ mol−1/RT) cm3 s−1. In addition, the radiative lifetime of the 2-C4H9O(Ã) radical after excitation at λ = 365.938 nm in the (0,1) band has been determined to be τrad(2-C4H9O(Ã)) = (440 ± 80) ns. Quenching rate constants of the 2-C4H9O(Ã) radical were measured to be kq = (4.7 ± 0.3) × 10−10 cm3 s−1 and kq = (5.0 ± 0.4) × 10−12 cm3 s−1 for 2-butylnitrite and nitrogen, respectively.

  nm的荧光激发光谱。
• Relative-rate study of thermal decomposition of the 2-butoxyl radical in the temperature range 280–313 KElectronic supplementary information (ESI) available: See http://www.rsc.org/suppdata/cp/b1/b111474c/
  作者：H. G. Libuda、O. Shestakov、J. Theloke、F. Zabel

  DOI：10.1039/b111474c

  日期：2002.5.29

  The competition between thermal decomposition (kdis) and reaction with O2 (kO2) has been studied for the 2-butoxyl radical in a newly built 210 L photoreactor constructed of quartz. 2-Butoxyl radicals were generated by continuous 254 nm photolysis of 2-butoxyl iodide in the presence of O2 and NO, using N2 as a buffer gas. Reaction educts and products were analysed by long-path (29 m) IR absorption using an FTIR spectrometer. The ratio kdis/kO2 was derived from the product ratios of acetaldehyde and butanone, corrected for small amounts of side products. At 280, 298, and 313 K and a total pressure of 1 bar (M = O2 + N2), kdis/kO2 was determined at O2 partial pressures between 100 and 1000 mbar. At all temperatures, there was a systematic increase of (kdis/kO2)eff ≡ (Δ[CH3CHO]corr × [O2]) / (2 × Δ[CH3C(O)CH2CH3]) with the partial pressure of O2 which possibly is the result of an additional O2 independent source of acetaldehyde (≈8% of the 2-butoxyl radicals reacting by either of the two competing pathways at 298 K, 1 bar). Pressure-dependence studies between 100 and 1000 mbar support the hypothesis that the additional acetaldehyde originates from the formation of 6–10% chemically activated 2-butoxyl radicals in the temperature range 280–313 K. Correction of (kdis/kO2)eff for the O2 independent yield of acetaldehyde results in kdis/kO2 = (6.8 ± 1.4) × 1017, (2.3 ± 0.5) × 1018, and (5.5 ± 1.1) × 1018 molecule cm−3 at 279.8, 298.2, and 313.5 K, respectively, leading to the Arrhenius expression kdis/kO2 = (2.0 ± 0.5) × 1026exp(−45.4 kJ mol−1/RT) molecule cm−3 at a total pressure of 1 bar. This temperature dependence of kdis/kO2 implies that, depending on temperature, either thermal decomposition or reaction with O2 is the major loss process of 2-butoxyl radicals under the conditions of the lower troposphere. Using literature values for kO2, kdis = 3.9 × 1012 exp(−47.1 kJ mol−1/RT) s−1 is derived for a total pressure of 1 bar (M = N2 + O2), which compares very favourably with a recent theoretical estimate (ab initio + RRKM) by Somnitz and Zellner (H. Somnitz and R. Zellner, Phys. Chem. Chem. Phys., 2000, 2, 1907).

  在由石英制成的新建210升光反应器中，对2-丁氧基自由基的分解（kdis）与O2反应（kO2）的竞争进行了研究。2-丁氧基自由基是在存在O2和NO的情况下，通过持续的254纳米光解2-丁氧基碘化物产生的，使用N2作为缓冲气体。反应物和产物通过使用傅里叶变换红外光谱仪的长路径（29米）红外吸收进行分析。根据乙醛和丁酮的产品比例，修正了少量副产物的影响，得到了kdis/kO2的比例。在280、298和313 K以及总压力为1巴（M=O2+N2）的条件下，kdis/kO2在O2的分压介于100到1000毫巴之间被确定。在所有温度下，(kdis/kO2)eff≡(Δ[CH3CHO]corr×[O2])/(2×Δ[CH3C(O)CH2CH3])随O2分压的增加有系统性的增加，这可能是由于来自O2独立来源的乙醛的额外贡献（在298 K，1巴的条件下，大约8%的2-丁氧基自由基通过这两种竞争路径中的任何一种反应）。在100到1000毫巴的压力依赖性研究支持了这样一个假设，即额外的乙醛来源于在280到313 K的温度范围内形成的化学激活的2-丁氧基自由基，其比例为6到10%。修正(kdis/kO2)eff对于O2独立产生的乙醛的产率，得到了kdis/kO2=(6.8±1.4)×1017，(2.3±0.5)×1018，和(5.5±1.1)×1018分子cm-3在279.8，298.2，和313.5 K，分别，导致Arrhenius表达式kdis/kO2=(2.0±0.5)×1026exp(-45.4 kJ mol-1/RT)分子cm-3在总压力为1巴。这个kdis/kO2的温度依赖性意味着，取决于温度，在较低对流层的条件下，要么是热分解，要么是与O2反应是2-丁氧基自由基的主要损失过程。使用文献中的kO2值，对于总压力为1巴（M=N2+O2），导出kdis=3.9×1012exp(-47.1 kJ mol-1/RT) s-1，这与Somnitz和Zellner的最近理论估计（从头计算+RRKM）非常吻合。
• Rate constants for the decomposition of 2-butoxy radicals and their reaction with NO and O2
  作者：G. Falgayrac、F. Caralp、N. Sokolowski-Gomez、P. Devolder、C. Fittschen

  DOI：10.1039/b405134c

  日期：——

  The reactivity of 2-butoxy radicals has been investigated using the laser photolysis/laser induced fluorescence technique. Three reactions have been studied: (i) The rate constants for the reaction with NO have been measured by the same technique at total pressures between 0.03 < p < 0.4 bar of helium and at five temperatures between 295–348 K. No pressure dependence has been found within the experimental error, and a small negative temperature dependence has been found, in agreement with earlier studies: k1 = (4.4 ± 0.6) × 10−12 exp((4.9 ± 0.3) kJ mol−1/RT) cm3 s−1. (ii) The rate constant with O2 has been measured at room temperature and 0.131 bar of helium: k2 = (9 ± 2) × 10−15 cm3 s−1. Significant quenching of 2-butoxy fluorescence by O2 prevented experiments in a larger temperature range: kq,O2 = (4 ± 1) × 10−11 cm3 s−1. (iii) The temperature and pressure dependence of the unimolecular decomposition at total pressures between 0.01 < p < 0.8 bar of helium and at four temperatures between 291–348 K. The low and the high pressure limiting rate constants as well as the broadening factor Fcent have been extracted from a falloff analysis of the experimental results: k3,0,He = 3.2 × 10−8 exp(−35.9 kJ mol−1/RT) cm3 s−1, k3,∞ = 1.1 × 1014 exp(−53.6 kJ mol−1/RT) s−1, and F3,c = 0.87 − T/870 K. We anticipate an uncertainty of ±30% for these rate constants. These results are in excellent agreement with earlier predictions (C. Fittschen, H. Hippler and B. Viskolcz, Phys. Chem. Chem. Phys., 2000, 2, 1677–1683 (); R. Méreau, M.-T. Rayez, F. Caralp and J.-C. Rayez, Phys. Chem. Chem. Phys., 2000, 2, 3765 ()) .

  利用激光光解/激光诱导荧光技术研究了 2-丁氧基自由基的反应性。研究了三个反应：(i) 在 0.03 < p < 0.4 bar 的氦气总压力和 295-348 K 之间的五个温度下，用同样的技术测量了与 NO 反应的速率常数。(ii) 在室温和 0.131 巴氦气条件下测得 O2 的速率常数：k2 = (9 ± 2) × 10-15 cm3 s-1。由于 O2 对 2-丁氧基荧光有明显的淬灭作用，因此无法在更大的温度范围内进行实验：kq,O2 = (4 ± 1) × 10-11 cm3 s-1。(iii) 在 0.01 < p < 0.8 bar 的氦气总压和 291-348 K 的四种温度下单分子分解的温度和压力依赖性。2 × 10-8 exp(-35.9 kJ mol-1/RT) cm3 s-1，k3,∞ = 1.1 × 1014 exp(-53.6 kJ mol-1/RT) s-1，F3,c = 0.87 - T/870 K。我们预计这些速率常数的不确定性为 ±30%。这些结果与之前的预测（C. Fittschen, H. Hippler and B. Viskolcz, Phys.Chem.Phys., 2000, 2, 1677-1683 (); R. Méreau, M.-T.Rayez, F. Caralp and J.-C.Rayez, Phys.Chem.Phys., 2000, 2, 3765 ()) .