二苯基甲基[(对甲氧基苯基)磺酰基]甲基亚砜 | 132102-78-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 二苯基甲基[(对甲氧基苯基)磺酰基]甲基亚砜
• 英文名称: diphenylmethyl <(p-methoxyphenyl)sulfonyl>methyl sulfoxide
• 英文别名: 1-(Benzhydrylsulfinylmethylsulfonyl)-4-methoxybenzene
• CAS: 132102-78-4
• 化学式: C₂₁H₂₀O₄S₂
• 分子量: 400.519
• InChiKey: UXIZXXOXRLTXDW-UHFFFAOYSA-N

物化性质

• 熔点：
  152-154 °C(Solv: chloroform (67-66-3); hexane (110-54-3))
• 沸点：
  657.4±55.0 °C(Predicted)
• 密度：
  1.309±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  27
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  88
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  二苯基甲基[(对甲氧基苯基)磺酰基]甲基亚砜 在 methanolate 作用下， 以 甲醇 、 二甲基亚砜 为溶剂， 生成 [苯基(亚磺酰基)甲基]苯 、 4-甲氧基苯甲砜
  参考文献：
  名称：

  Study of reactions leading to sulfine formation. 5. Methoxide-catalyzed decomposition of diarylmethyl(arylsulfonyl)methyl sulfoxides: a sulfine-forming elimination on the E1cBrev/(E1cB)irrev borderline

  摘要：

  In 7:3 CH3OH-DMSO (v/v) in the presence of methoxide ion, diarylmethyl (arylsulfonyl)methyl sulfoxides (Ar2CHS(O)CH2SO2Ar') 4, undergo elimination remarkably easily to afford the diarylsulfine and the aryl methyl sulfone (eq 4). Comparison of the rate of cleavage of 4 (k(elim)) and the rate of disappearance of the H-1 NMR signal (k(CHSO)) for the Ar2CHS(O) proton in CD3OD-DMSO shows that the mechanism for the elimination is on the (E1cB)rev/(E1cB)irrev borderline, (k(CHSO)/k(elim)) ranging from 1.2 to 5.2, depending on the nature of the Ar and Ar' groups in 4. Slight changes in structure can shift the mechanism from (E1cB)rev to (E1cB)irrev as a result of their effect on the partitioning of the alpha-sulfinyl carbanion intermediate (Ar2CBARS(O)CH2SO2Ar') 5, between cleavage to diarylsulfine plus ArSO2CH2- (step k(ii), eq 8) and protonation to regenerate 4 (step k(-i). Structural changes that make Ar'SO2CH2 a better leaving group increase k(ii)/k(-i)[MeOD] and shift the mechanism toward (E1cB)irrev as does also an increase in the percentage of DMSO in the solvent. Structural changes in Ar that enhance the stability of 5 decrease k(ii)/k(-i)[MeOD] and shift the mechanism toward (E1cB)rev. It is also shown that for 4 in general k(ii) appears larger than would be expected for a leaving group of the basicity of Ar'SO2CH2-. Repulsion between the dipoles of the S(O) and SO2 groups in 5 is thought to be responsible.

  DOI：

  10.1021/jo00004a017
• 作为产物：
  描述：

  sodium 4-methoxybenzenesulfinate 在 正丁基锂 、 间氯过氧苯甲酸 作用下， 以 氯仿 、 二甲基亚砜 为溶剂， 反应 3.0h， 生成 二苯基甲基[(对甲氧基苯基)磺酰基]甲基亚砜
  参考文献：
  名称：

  Study of reactions leading to sulfine formation. 5. Methoxide-catalyzed decomposition of diarylmethyl(arylsulfonyl)methyl sulfoxides: a sulfine-forming elimination on the E1cBrev/(E1cB)irrev borderline

  摘要：

  In 7:3 CH3OH-DMSO (v/v) in the presence of methoxide ion, diarylmethyl (arylsulfonyl)methyl sulfoxides (Ar2CHS(O)CH2SO2Ar') 4, undergo elimination remarkably easily to afford the diarylsulfine and the aryl methyl sulfone (eq 4). Comparison of the rate of cleavage of 4 (k(elim)) and the rate of disappearance of the H-1 NMR signal (k(CHSO)) for the Ar2CHS(O) proton in CD3OD-DMSO shows that the mechanism for the elimination is on the (E1cB)rev/(E1cB)irrev borderline, (k(CHSO)/k(elim)) ranging from 1.2 to 5.2, depending on the nature of the Ar and Ar' groups in 4. Slight changes in structure can shift the mechanism from (E1cB)rev to (E1cB)irrev as a result of their effect on the partitioning of the alpha-sulfinyl carbanion intermediate (Ar2CBARS(O)CH2SO2Ar') 5, between cleavage to diarylsulfine plus ArSO2CH2- (step k(ii), eq 8) and protonation to regenerate 4 (step k(-i). Structural changes that make Ar'SO2CH2 a better leaving group increase k(ii)/k(-i)[MeOD] and shift the mechanism toward (E1cB)irrev as does also an increase in the percentage of DMSO in the solvent. Structural changes in Ar that enhance the stability of 5 decrease k(ii)/k(-i)[MeOD] and shift the mechanism toward (E1cB)rev. It is also shown that for 4 in general k(ii) appears larger than would be expected for a leaving group of the basicity of Ar'SO2CH2-. Repulsion between the dipoles of the S(O) and SO2 groups in 5 is thought to be responsible.

  DOI：

  10.1021/jo00004a017

文献信息

• KICE, JOHN L.;KUPCZYK-SUBOTKOWSKA, LIDIA, J. ORG. CHEM., 56,(1991) N, C. 1424-1430
  作者：KICE, JOHN L.、KUPCZYK-SUBOTKOWSKA, LIDIA

  DOI：——

  日期：——