t-butyl methyl ether radical | 25191-59-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: t-butyl methyl ether radical
• 英文别名: tert.-Butoxy-methyl-radikal；tert-butoxymethyl
• CAS: 25191-59-7
• 化学式: C₅H₁₁O
• 分子量: 87.1417
• InChiKey: HXPQBIAVEXAOSC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  6
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  t-butyl methyl ether radical 在 氧气 作用下， 生成 2-Methoxy-2-methyl-prop-1-yl-hydroperoxide
  参考文献：
  名称：

  气相中甲基叔丁基醚产生的烷基和烷基过氧自由基反应的脉冲辐解研究

  摘要：

  通过脉冲辐射分解-UV吸收技术研究了在1 atm SF 6中来自甲基叔丁基醚（MTBE）的烷基和烷基过氧自由基反应的UV光谱和动力学。自由基混合物的UV光谱在215至340nm之间定量。在240 nm。σ [R =（2.6±0.4）×10 -18厘米2分子-1和σ RO 2 =（4.1±0.6）×10 -18厘米2分子-1（以e为底）。烷基自由基的自反应速率常数为（2.5±1.1）×10 -11 cm 3分子-1 s -1。所述速率常数与分子氧的烷基基团和烷基过氧自由基与NO和NO的反应2是（9.1±1.5）×10 -13，（4.3±1.6）×10 -12和（1.2±0.3）×10 -分别为11 cm 3分子-1 s -1。上面给出的速率常数是指在分子的叔丁基侧的反应。

  DOI：

  10.1016/0009-2614(95)00571-k
• 作为产物：
  描述：

  甲基叔丁基醚 在 tert-butoxyl radical 作用下， 以 various solvent(s) 为溶剂， 生成 t-butyl methyl ether radical
  参考文献：
  名称：

  激光闪光光解-溶液中均相反应的电子自旋共振动力学研究

  摘要：

  激光闪光光解法（308 nm）的产生与自由基中间体的时间分辨esr光谱检测结合已用于获得许多单分子和双分子均解反应的绝对速率系数和活化参数[（A）–（F） ]解决方案。结果符合卜井吨OCO→卜Ť + CO 2（A），（ETO）3 ṖOBu吨→卜Ť +（ETO）3 PO（B），卜吨O +环-C 5 H ^ 10 →环-C 5 H ^ 9 ˙+卜吨OH（C），卜吨O +卜吨OME→卜吨OCH 2 +卜吨OH（d）中，Me 3 SIO +环-C 5 H ^ 10 →环-C 5 H ^ 9 ˙+我3 SiOH基（E）中，Me 3 SIO +卜吨OME→卜吨OCH 2 +我3SiOH（F）先前使用其他技术通过某些反应获得的那些。反应（C）的数据与通过激光闪光光解结合瞬态的光学检测获得的数据非常一致，但是与先前通过闪光光解/ esr技术获得的结果明显不同。氢转移（E）和（F）的动力学结果代表三烷基甲硅

  DOI：

  10.1039/p29860001269

文献信息

• Laser flash photolysis–electron spin resonance kinetic studies of homolytic reactions in solution
  作者：Jehan A. Baban、Jeffrey P. Goddard、Brian P. Roberts

  DOI：10.1039/p29860001269

  日期：——

  agreement with those obtained by laser flash photolysis coupled with optical detection of transients, but differ markedly from results obtained previously by a flash photolysis/e.s.r. technique. The kinetic results for the hydrogen transfers (E) and (F) represent the first absolute rate data for reactions of trialkylsiloxyl radicals. The trimethylsiloxyl radical is more reactive in hydrogen abstraction

  激光闪光光解法（308 nm）的产生与自由基中间体的时间分辨esr光谱检测结合已用于获得许多单分子和双分子均解反应的绝对速率系数和活化参数[（A）–（F） ]解决方案。结果符合卜井吨OCO→卜Ť + CO 2（A），（ETO）3 ṖOBu吨→卜Ť +（ETO）3 PO（B），卜吨O +环-C 5 H ^ 10 →环-C 5 H ^ 9 ˙+卜吨OH（C），卜吨O +卜吨OME→卜吨OCH 2 +卜吨OH（d）中，Me 3 SIO +环-C 5 H ^ 10 →环-C 5 H ^ 9 ˙+我3 SiOH基（E）中，Me 3 SIO +卜吨OME→卜吨OCH 2 +我3SiOH（F）先前使用其他技术通过某些反应获得的那些。反应（C）的数据与通过激光闪光光解结合瞬态的光学检测获得的数据非常一致，但是与先前通过闪光光解/ esr技术获得的结果明显不同。氢转移（E）和（F）的动力学结果代表三烷基甲硅
• A laser flash photolysis kinetic study of reactions of the Cl2? radical anion with oxygenated hydrocarbons in aqueous solution
  作者：H.-W. Jacobi、F. Wicktor、H. Herrmann、R. Zellner

  DOI：10.1002/(sici)1097-4601(1999)31:3<169::aid-kin2>3.0.co;2-k

  日期：——

  A laser photolysis-long path laser absorption (LP-LPLA) experiment has been used to determine the rate constants for H-atom abstraction reactions of the dichloride radical anion (Cl-2(-)) in aqueous solution. From direct measurements of the decay of Cl-2(-) in the presence of different reactants at pH = 4 and I = 0. 1 M the following rate constants at T = 298 K were derived: methanol, (5.1 +/- 0.3) 10(4) M-1 S-1; ethanol, (1.2 +/- 0.2) 10(5) M-1 s(-1); 1-propanol, (1.01 +/- 0.07) 10(5) M-1 s(-1); 2-propanol, (1.9 +/- 0.3) 105 M-1 S-1; tert.-butanol, (2.6 +/- 0.5) 104 M-1 s(-1); formaldehyde, (3.6 +/- 0.5) 10(4) M-1 s(-1); diethylether, (4.0 +/- 0.2) 10(5) M-1 s(-1); methyltert.-butylether, (7 +/- 1) 10(4) M-1 s(-1); tetrahydrofuran, (4.8 +/- 0.6) 105 M-1 s(-1); acetone, (1.41 +/- 0.09) 10(3) M-1 s(-1). For the reactions of Cl-2(-) with formic acid and acetic acid rate constants of (8.0 +/-: 1.4) 10(4) M-1 s(-1) (pH = 0, I = 1.1 M and T= 298 K) and (1.5 +/- 0.8) 10(3) M-1 s(-1) (pH = 0.42, I = 0.48 M and T= 298 K), respectively, were derived.A correlation between the rate constants at T = 298 K for all oxygenated hydrocarbons and the bond dissociation energy (BDE) of the weakest C-H-bond of log k(2nd) = (32.9 +/- 8.9) (0.073 +/- 0.022) BDE/kJ mol(-1) is derived.From temperature-dependent measurements the following Arrhenius expressions were derived:k(Cl-2(-) + HCOOH) = (2.00 +/- 0.05) . 10(10 .) exp(-(4500 +/- 200) K/T) M-1 s(-1),E-a = (37 +/- 2) kJ mol(-1)k(Cl-2(-) + CH3COOH) = (2.7 +/- 0.5) .10(10) . exp(-(4900 +/- 1300) k/T) M-1 s(-1),E-a= (41 +/- 11) kJ mol(-1).
• Pulse radiolysis study of reactions of alkyl and alkylperoxy radicals originating from methyl tert-butyl ether in the gas phase
  作者：Sarka Langer、Evert Ljungström、Thomas Ellermann、Ole J. Nielsen、Jens Sehested

  DOI：10.1016/0009-2614(95)00571-k

  日期：1995.7

  reactions of alkyl and alkylperoxy radicals from methyl tert-butyl ether (MTBE) were studied in 1 atm of SF6 by the pulse radiolysis-UV absorption technique. UV spectra for the radical mixtures were quantified from 215 to 340 nm. At 240 nm. σR = (2.6 ± 0.4) × 10−18 cm2 molecule−1 and σRO2 = (4.1 ± 0.6) × 10−18 cm2 molecule−1 (base e). The rate constant for the self-reaction of the alkyl radicals is

  通过脉冲辐射分解-UV吸收技术研究了在1 atm SF 6中来自甲基叔丁基醚（MTBE）的烷基和烷基过氧自由基反应的UV光谱和动力学。自由基混合物的UV光谱在215至340nm之间定量。在240 nm。σ [R =（2.6±0.4）×10 -18厘米2分子-1和σ RO 2 =（4.1±0.6）×10 -18厘米2分子-1（以e为底）。烷基自由基的自反应速率常数为（2.5±1.1）×10 -11 cm 3分子-1 s -1。所述速率常数与分子氧的烷基基团和烷基过氧自由基与NO和NO的反应2是（9.1±1.5）×10 -13，（4.3±1.6）×10 -12和（1.2±0.3）×10 -分别为11 cm 3分子-1 s -1。上面给出的速率常数是指在分子的叔丁基侧的反应。
• A novel long path photolysis cell—application to the reactivity of selected organic compounds toward the nitrate radical (NO₃)
  作者：Davy Rousse、Christian George

  DOI：10.1039/b400175c

  日期：——

  Bimolecular rate coefficients for the reactions of the nitrate radical, NO3, with methanol, ethanol, acetaldehyde tert-butyl methyl ether, propionic acid, dimethylmalonate, dimethylsuccinate, dimethyl carbonate and diethylcarbonate in aqueous solutions have been measured using a novel experimental approach. This study was performed using laser flash photolysis (LFP) with a capillary made of Teflon AF2400 as a long path capillary photolysis cell. Taking benefit of this new material allowing a long optical path length for a very limited irradiated solution volume, new rate constants were established. All experiments were carried out at room temperature. Measured rate coefficients for the reaction of the NO3 radical with methanol, ethanol, acetaldehyde, dimethylcarbonate, diethylcarbonate, dimethylmalonate, dimethyl succinate, propionic acid and tert-butyl-methyl ether are (units are 105 M−1 s−1): kNO3 + ethanol = 4.8 ± 0.5, kNO3 + ethanol = 19 ± 3, kNO3 + acetaldehyde = 20 ± 3, kNO3 + dimethylcarbonate = 0.15 ± 0.04, kNO3 + diethylcarbonate = 0.84 ± 0.12, kNO3 + dimethylmalonate = 0.26 ± 0.07, kNO3 + dimethylsuccinate = 0.34 ± 0.02, kNO3 + propionic acid = 0.77 ± 0.02, kNO3 + tert-butyl-methyl ether = 3.9 ± 1.3. The uncertainties in the above expressions are ±2σ and represent precision only. The reported rate coefficients for the reactions of NO3 with methanol, ethanol and acetaldehyde agree well with currently recommended values. To date, there is no kinetic data reported in the literature for the NO3 radical reaction with dimethylcarbonate, diethylcarbonate, dimethylmalonate, dimethylsuccinate, propionic acid and tert-butyl-methyl ether. The reaction mechanism is briefly discussed as a function of bond energies

  已使用一种新颖的实验方法测量了硝酸根自由基（NO3）与甲醇、乙醇、乙醛、叔丁基甲基醚、丙酸、二甲基马来酸盐、二甲基丁二酸盐、碳酸二甲酯和碳酸二乙酯在水溶液中的双分子反应速率系数。该研究采用激光闪光光解法（LFP），使用由特氟龙AF2400制成的毛细管作为长光程光解池。得益于这种新材料，它允许在非常有限的辐照溶液体积内实现较长的光学路径长度，建立了新的速率常数。所有实验均在室温下进行。NO3自由基与甲醇、乙醇、乙醛、二甲基碳酸酯、二乙基碳酸酯、二甲基马来酸盐、二甲基丁二酸盐、丙酸和叔丁基甲基醚反应的速率系数（单位为 10⁵ M⁻¹ s⁻¹）为：kNO3 + 乙醇 = 4.8 ± 0.5, kNO3 + 乙醇 = 19 ± 3, kNO3 + 乙醛 = 20 ± 3, kNO3 + 二甲基碳酸酯 = 0.15 ± 0.04, kNO3 + 二乙基碳酸酯 = 0.84 ± 0.12, kNO3 + 二甲基马来酸盐 = 0.26 ± 0.07, kNO3 + 二甲基丁二酸盐 = 0.34 ± 0.02, kNO3 + 丙酸 = 0.77 ± 0.02, kNO3 + 叔丁基甲基醚 = 3.9 ± 1.3。上述表达式中的不确定性为 ±2σ，仅表示精确度。NO3与甲醇、乙醇和乙醛反应的速率系数与目前推荐的值高度一致。到目前为止，文献中尚无NO3自由基与二甲基碳酸酯、二乙基碳酸酯、二甲基马来酸盐、二甲基丁二酸盐、丙酸和叔丁基甲基醚反应的动力学数据。反应机制将简要讨论作为键能的函数。