Dimethylsulfoxid-Radikal | 25087-46-1

• 分子结构分类: 有机化合物 - 有机硫化合物
• 英文名称: Dimethylsulfoxid-Radikal
• 英文别名: methanesulfinyl-methyl
• CAS: 25087-46-1
• 化学式: C₂H₅OS
• 分子量: 77.1271
• InChiKey: OXBCXTCTKBRUPI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  4
• 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：
  20.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  二甲基亚砜 在 potassium methanolate 作用下， 以 甲醇 为溶剂， 反应 0.03h， 生成 Dimethylsulfoxid-Radikal
  参考文献：
  名称：

  Formation of DMSO and DMF radicals with minute amounts of base

  摘要：

  So far overlooked DMSO and DMF form long-lived radicals in the presence of small amounts of bases. DMF radicals being less stable than DMSO radicals. In solvent mixtures, the presence of DMSO prolonged the lifetime of DMF radicals. The occurrence of radicals may explain previously reported unexpected outcomes of reactions performed in these solvents. The commonly accepted inertness of these solvents towards minor quantities of alkali seems not to be warranted. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2009.06.109

文献信息

• Electron spin resonance. Part 67. Oxidation of aliphatic sulphides and sulphoxides by the sulphate radical anion (SO₄^–˙) and of aliphatic radicals by the peroxydisulphate anion (S₂O₈^2–)
  作者：Michael J. Davies、Bruce C. Gilbert、Richard O. C. Norman

  DOI：10.1039/p29840000503

  日期：——

  E.s.r. experiments employing in situ photolytic decomposition of the peroxydisulphate anion (S2O82–) have been carried out to study the reaction of SO4–˙ with aliphatic sulphides and sulphoxides. For the former, ‘dimer’ radical cations (R2SSR2+˙) are detected; these are evidently generated via direct one-electron oxidation of the sulphide (to give firstly R2S+˙). The more complex behaviour of the latter

  采用ESR实验原位的过二阴离子的光解分解（S 2 ö 8 2-）已经进行了研究SO的反应4 -与脂族硫化物和亚砜˙。对于前者，检测到“二聚体”自由基阳离子（R 2 SSR 2 + ˙）。这些显然是通过硫化物的直接单电子氧化生成的（首先是R 2 S + generated）。后者[涉及的更复杂的行为，例如，我的反应2 S（O），得到CH 2 S（O）我（在低pH），ME，和内消旋2·]是根据（未检测到的）自由基阳离子R 2 S（O）+ initial的初始形成来解释的，其后的竞争反应包括去质子化和水合（随后发生碎裂）。
• Reactions of the Cumyloxyl and Benzyloxyl Radicals with Strong Hydrogen Bond Acceptors. Large Enhancements in Hydrogen Abstraction Reactivity Determined by Substrate/Radical Hydrogen Bonding
  作者：Michela Salamone、Gino A. DiLabio、Massimo Bietti

  DOI：10.1021/jo3019889

  日期：2012.12.7

  α-C–H and the oxygen atom of the substrates followed by hydrogen abstraction. This is supported by theoretical calculations that show the formation of relatively strong prereaction complexes. These observations confirm that in alkoxyl radical reactions specific hydrogen bond interactions can dramatically influence the hydrogen abstraction reactivity, pointing toward the important role played by structural

  从强氢键受体如DMSO，HMPA，和三丁基膦氧化物（TBPO）由cumyloxyl（粗磨上夺氢的动力学研究•）和苄氧基（BNO •）自由基是在乙腈中进行。与CumO •的反应是根据直接氢提取机理描述的，与动力学氘同位素效应k H / k D的2.0和3.1相符，该自由基与DMSO / DMSO- d 6和HMPA的反应测得/ HMPA- d 18。从CumO •到BnO •的反应性观察到非常大的提高，如与HMPA，TBPO和DMSO反应的k H（BnO •）/ k H（CumO •）比率分别为86、4.8 ×10 3和1.6×10 4。所述ķ ħ / ķ d为BNO的反应测得的0.91和1.0 •用DMSO / DMSO- d 6和HMPA / HMPA- d 18与，一起ķ ħ（BNO •）/ ķ ħ（粗磨•）的比率，是根据苄氧基α-C–H与底物的氧原子之间形成氢键合的预反应配合物，然后
• Formation of DMSO and DMF radicals with minute amounts of base
  作者：Christer L. Øpstad、Thor-Bernt Melø、Hans-Richard Sliwka、Vassilia Partali

  DOI：10.1016/j.tet.2009.06.109

  日期：2009.9

  So far overlooked DMSO and DMF form long-lived radicals in the presence of small amounts of bases. DMF radicals being less stable than DMSO radicals. In solvent mixtures, the presence of DMSO prolonged the lifetime of DMF radicals. The occurrence of radicals may explain previously reported unexpected outcomes of reactions performed in these solvents. The commonly accepted inertness of these solvents towards minor quantities of alkali seems not to be warranted. (C) 2009 Elsevier Ltd. All rights reserved.