methyl sulfite | 44209-66-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl sulfite
• 英文别名: Methanesufonate
• CAS: 44209-66-7
• 化学式: CH₃O₃S
• 分子量: 95.099
• InChiKey: QFUDHWDUKUCCHZ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  68.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  硫酸二甲酯 在 hydroxide 作用下， 24.9 ℃ 、40.0 Pa 条件下， 生成 methyl sulfate 、 methyl sulfite
  参考文献：
  名称：

  Intrinsic reactivity of sulfur esters: site selectivity by anions with dimethyl sulfate and methyl methanesulfonate

  摘要：

  The thermally equilibrated (298 K) gas-phase ion-molecule reactions of a variety of anions with dimethyl sulfate and methyl methanesulfonate have been examined using the flowing afterglow technique. Two competitive pathways are observed for the reactions of dimethyl sulfate: reductive elimination across a C-O bond yielding CH3OSO2- as the ionic product and nucleophilic substitution at carbon yielding CH3OSO3- as the ionic product. Nucleophilic substitution is observed to some extent for every anion examined, while reductive elimination is observed for only the strongest bases (PA > 390 kcal mol-1) examined. For methyl methanesulfonate, the reaction channels observed are nucleophilic substitution at carbon yielding CH3SO3- as the ionic product and proton transfer yielding CH3OSO2CH2- as the ionic product. Proton transfer dominates the reaction of methyl methanesulfonate, while nucleophilic substitution is again observed to some extent for each of the anions studied. For neither dimethyl sulfate nor methyl methanesulfonate are products arising from reaction at sulfur found. The S(N)2 reaction at carbon in both cases is believed to overwhelm the analogous S(N)2-type process at sulfur because the substitution reaction at carbon displaces a much better leaving group.

  DOI：

  10.1021/jo00060a015

文献信息

• Selectivity as a function of anionic base properties in the gas-phase reactions of dimethyl sulfite
  作者：Joseph J. Grabowski、Rachel C. Lum

  DOI：10.1021/ja00158a018

  日期：1990.1
• Substitution competes with elimination in a gas-phase anion-molecule reaction
  作者：Rachel C. Lum、Joseph J. Grabowski

  DOI：10.1021/ja00233a056

  日期：1988.12
• Intrinsic reactivity of sulfur esters: site selectivity by anions with dimethyl sulfate and methyl methanesulfonate
  作者：Rachel C. Lum、Joseph J. Grabowski

  DOI：10.1021/jo00060a015

  日期：1993.4

  The thermally equilibrated (298 K) gas-phase ion-molecule reactions of a variety of anions with dimethyl sulfate and methyl methanesulfonate have been examined using the flowing afterglow technique. Two competitive pathways are observed for the reactions of dimethyl sulfate: reductive elimination across a C-O bond yielding CH3OSO2- as the ionic product and nucleophilic substitution at carbon yielding CH3OSO3- as the ionic product. Nucleophilic substitution is observed to some extent for every anion examined, while reductive elimination is observed for only the strongest bases (PA > 390 kcal mol-1) examined. For methyl methanesulfonate, the reaction channels observed are nucleophilic substitution at carbon yielding CH3SO3- as the ionic product and proton transfer yielding CH3OSO2CH2- as the ionic product. Proton transfer dominates the reaction of methyl methanesulfonate, while nucleophilic substitution is again observed to some extent for each of the anions studied. For neither dimethyl sulfate nor methyl methanesulfonate are products arising from reaction at sulfur found. The S(N)2 reaction at carbon in both cases is believed to overwhelm the analogous S(N)2-type process at sulfur because the substitution reaction at carbon displaces a much better leaving group.