methoxymethyl radical | 16520-04-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methoxymethyl radical
• 英文别名: Methoxymethyl-Radikal；Methyl radical, methoxy-
• CAS: 16520-04-0
• 化学式: C₂H₅O
• 分子量: 45.0611
• InChiKey: AFGPRWUFPLEMTF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  methoxymethyl radical 在 氧气 作用下， -53.1 ℃ 、14.8 kPa 条件下， 生成 methoxymethylperoxy radical
  参考文献：
  名称：

  Kinetic Studies of the Oxidation of Dimethyl Ether and Its Chain Reaction with Cl₂

  摘要：

  The reaction between dimethyl ether radicals and molecular oxygen proceeds along two distinct pathways at temperatures between 230 and 350 K. Above about 100 Torr total pressure the peroxy radical, CH3OCH2O2, is predominantly formed. As the pressure is reduced, a channel leading to the formation of OH and two formaldehyde molecules becomes progressively more important. Real time kinetic measurements of these reactions are made using time-resolved UV spectroscopy to monitor CH3OCH2 loss and CH3OCH2O2 formation along with transient IR absorption to probe formaldehyde production. The OH radicals are identified via their UV spectrum. The reaction can be described via a modified Lindemann mechanism using the three parameters k(ro2 infinity), k(ro2,0), and k(prod,0), which represent the high- and low-pressure limits of the O-2 addition reaction and the low-pressure limit of the OH/formaldehyde channel. At 295 K they have values of (1.1 +/- 0.1) x 10(-11) cm(3) s(-1), (2.6 +/- 0.9) x 10(-29) cm(6) s(-1), and (6 +/- 2) x 10(-12) cm(3) s(-1), respectively. At P-tot = similar to 120 Torr the reaction exhibits a negative temperature dependence with k(r+o2) = (3.1(-0.8)(+1.0)) x 10(-12) e((326+/-80)/T) cm(3) s(-1). Experiments in the absence of oxygen were performed to investigate the CH3OCH2-mediated chain reaction between chlorine and dimethyl ether. Analysis of time-resolved UV spectra reveals rate constants of k(r+cl2) = (1.8(-0.5) (+0.7)) x 10(-11) e((360+/-120)/T) cm(3)s(-1) and k(r+r) = (1.8(-0.5)(+0.6)) x 10(-11) e((200+/-100)/T) cm(3)s(-1), respectively, for the chain propagation reaction between CH3OCH2 and molecular chlorine and for the chain-terminating recombination reaction.

  DOI：

  10.1021/jp9709666
• 作为产物：
  描述：

  甲醚 在 大鼠1,25-二羟基维生素D(1,25(OH)2D)试剂盒 作用下， 生成 methoxymethyl radical
  参考文献：
  名称：

  OH自由基与二甲醚反应动力学及机理的实验和理论研究

  摘要：

  OH与二甲醚（CH 3 OCH 3）的反应已在195至850 K范围内使用激光闪光光解法和激光诱导的OH自由基荧光检测进行了研究。这项工作的速率系数可以通过修改后的Arrhenius表达式来参数化k =（1.23±0.46）×10 –12（T / 298）2.05±0.23 exp（（257±107）/ T）cm 3分子–1 s – 1。包括其他最近的文献数据（923–1423 K），得出修正的Arrhenius表达式为k 1 =（1.54±0.48）×10 –12（T / 298 K）在195–1423 K范围内为1.89±0.16 exp（（184±112）/ T）cm 3分子–1 s –1。还研究了反应的各种同分异构组合，对二甲醚进行氘化可导致正常的同位素效应。羟基的氘代导致小的反同位素效应。为了深入了解反应机理并支持实验工作，还进行了理论研究，使用高级从头算方法计算了过渡态和配合物

  DOI：

  10.1021/jp4070278

文献信息

• An Experimental and Theoretical Study of the Long-Lived Radical Cation of CH₃OCH₂CH₂OH
  作者：Jaana M. H. Pakarinen、Rebecca L. Smith、Pirjo Vainiotalo、Tapani A. Pakkanen、Hilkka I. Kenttämaa

  DOI：10.1021/ja952145p

  日期：1996.4.24

  reagents via three main channels in a Fourier-transform ion cyclotron resonance mass spectrometer. CH3OCH2CH2OH•+ abstracts an electron from reagents with ionization energies less than that of CH3OCH2CH2OH. Neutral reagents with higher ionization energies replace CH3OCH2• or CH2O in the ion. Both replacement reactions are probably driven by the formation of a hydrogen bond between the entering nucleophile

  2-甲氧基乙醇的长寿命自由基阳离子 CH3OCH2 H•+ 在气相中对异构化是稳定的。这种自由基阳离子通过傅里叶变换离子回旋共振质谱仪中的三个主要通道与中性试剂反应。CH3OCH2 H•+ 从电离能低于 CH3OCH2 H 的试剂中夺取一个电子。具有较高电离能的中性试剂可替代离子中的 CH3OCH2• 或 CH2O。两种置换反应可能都是由进入的亲核试剂与 CH3OCH2 H•+ 中的羟基之间形成氢键驱动的，这会破坏 CH3OCH2 H•+ 中的 C-C 键。对于强亲核试剂，这个过程是放热的，以致于生成的离子/分子复合物因失去 CH3OCH2• 而解离。然而，弱亲核试剂会产生寿命更长的离子-分子复合物。
• Formation and homolysis of organonickel(III) complexes
  作者：Douglas G. Kelley、Adam Marchaj、Andreja Bakac、James H. Espenson

  DOI：10.1021/ja00020a020

  日期：1991.9

  The reactions of Ni(1,4,8,11-tetraazacyclotetradecane)2+ with alkyl radicals were studied. Data were collected for the R,R,S,S (or beta) and R,R,R,R (or alpha) isomers. The reactions form sigma-bonded organometallic cations, as in the equation NiL2+ + R. + H2O reversible RNiL(H2O)2+. The values of the rate constants for the forward (colligation) and reverse (homolysis) reactions were measured separately by laser flash photolysis techniques with a kinetic probe. The values of k(col) lie in the order CH3 >> primary >> secondary, and just the reverse order applies to k(hom). Thus the equilibrium constants for formation of RNiL(H2O)2+, given by k(col)/k(hom), are most favorable for methyl and least favorable for secondary alkyls. These nickel-alkyl bonds are much weaker than those in corresponding cobalt and chromium complexes. For that reason, values of k(col) vary widely with the nature of R.. Values of k(col) are considerably higher for alpha-Ni(cyclam)2+ than for the beta-isomer, and the reverse order applies to k(hom). Also, the alpha-isomer has the highest equilibrium constant for the formation equilibrium. The kinetic and thermodynamic trends can be rationalized by structural effects.
• Bakac, Andreja; Espenson, James H., Inorganic Chemistry, 1989, vol. 28, # 20, p. 3901 - 3904
  作者：Bakac, Andreja、Espenson, James H.

  DOI：——

  日期：——
• Huston, Patrick; Espenson, James H.; Bakac, Andreja, Inorganic Chemistry, 1991, vol. 30, # 25, p. 4826 - 4830
  作者：Huston, Patrick、Espenson, James H.、Bakac, Andreja

  DOI：——

  日期：——
• Bakac, Andreja; Espenson, James H., Inorganic Chemistry, 1989, vol. 28, # 24, p. 4319 - 4322
  作者：Bakac, Andreja、Espenson, James H.

  DOI：——

  日期：——