p-Methoxy-benzyl-dimethylsulfoniumchlorid | 14181-51-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: p-Methoxy-benzyl-dimethylsulfoniumchlorid
• 英文别名: (4-Methoxyphenyl)methyl-dimethylsulfanium;chloride
• CAS: 14181-51-2
• 化学式: C₁₀H₁₅OS*Cl
• 分子量: 218.748
• InChiKey: SLQRMFQHKGWVTM-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -0.92
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  10.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  p-Methoxy-benzyl-dimethylsulfoniumchlorid 以 水 为溶剂， 生成 二甲基硫 、 4-甲氧基苄醇
  参考文献：
  名称：

  Reactions of Charged Substrates. 3. The Hydrolysis of (4-Methoxybenzyl)dimethylsulfonium Chloride

  摘要：

  At low concentrations (ca. 10(-4) M), the hydrolysis of (4-methoxybenzyl)dimethyl sulfonium chloride (1) proceeds smoothly to completion in H2O or D2O at 80 degrees C. The rate constants measured directly by UV or NMR methods match the rate constants obtained as the ordinate intercepts of plots of k(obsd) vs [NaN3] or [pyridine-d(5)]. As expected, the rate constants decrease with increasing ionic strength (NaCl or NaClO4, mu = 0-2). There is a small solvent deuterium isotope effect, k(H)/k(D) = 1.1 at mu = 0 and 1.7, and the alpha-deuterium secondary isotope effect is k(H)/k(D) = 1.26 per deuterium. At higher concentrations (10 mM), the hydrolysis does not go to completion, with the fraction of 1 remaining reaching plateau values that are stable. Plots of the fraction of 1 remaining vs the initial concentration of 1 extrapolate to zero. Running the reaction in the presence of either Hg+2 or Zn+2 drives the reaction to completion by removing SMe(2) as the Lewis complex. While these results are consistent with common leaving group suppression of hydrolysis, they are also consistent with the establishment of an equilibrium among the starting material and the product alcohol, SMe(2), and hydronium ion. The suppression data are fitted to the equation for the equilibrium, and running the reaction in reverse gives the amount of I predicted by the equation. Reinterpretation of older data in light of the equilibrium, the results reported here, and results for the nucleophilic substitution reaction suggests that the mechanism of hydrolysis is S(N)1 with no ion-dipole complex intermediate.

  DOI：

  10.1021/jo00098a033
• 作为产物：
  描述：

  二甲基硫 、 4-甲氧基氯苄 以 氯仿 为溶剂， 生成 p-Methoxy-benzyl-dimethylsulfoniumchlorid
  参考文献：
  名称：

  Reactions of Charged Substrates. 3. The Hydrolysis of (4-Methoxybenzyl)dimethylsulfonium Chloride

  摘要：

  At low concentrations (ca. 10(-4) M), the hydrolysis of (4-methoxybenzyl)dimethyl sulfonium chloride (1) proceeds smoothly to completion in H2O or D2O at 80 degrees C. The rate constants measured directly by UV or NMR methods match the rate constants obtained as the ordinate intercepts of plots of k(obsd) vs [NaN3] or [pyridine-d(5)]. As expected, the rate constants decrease with increasing ionic strength (NaCl or NaClO4, mu = 0-2). There is a small solvent deuterium isotope effect, k(H)/k(D) = 1.1 at mu = 0 and 1.7, and the alpha-deuterium secondary isotope effect is k(H)/k(D) = 1.26 per deuterium. At higher concentrations (10 mM), the hydrolysis does not go to completion, with the fraction of 1 remaining reaching plateau values that are stable. Plots of the fraction of 1 remaining vs the initial concentration of 1 extrapolate to zero. Running the reaction in the presence of either Hg+2 or Zn+2 drives the reaction to completion by removing SMe(2) as the Lewis complex. While these results are consistent with common leaving group suppression of hydrolysis, they are also consistent with the establishment of an equilibrium among the starting material and the product alcohol, SMe(2), and hydronium ion. The suppression data are fitted to the equation for the equilibrium, and running the reaction in reverse gives the amount of I predicted by the equation. Reinterpretation of older data in light of the equilibrium, the results reported here, and results for the nucleophilic substitution reaction suggests that the mechanism of hydrolysis is S(N)1 with no ion-dipole complex intermediate.

  DOI：

  10.1021/jo00098a033
• 作为试剂：
  描述：

  (E)-3-(3,5-Dimethoxyphenyl)-6-methoxy-2-(4-methoxyphenyl)-4-<2-(4-methoxyphenyl)ethenyl>benzofuran 在 sodium hydride 、 p-Methoxy-benzyl-dimethylsulfoniumchlorid 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 以93%的产率得到3-(3,5-dimethoxyphenyl)-6-methoxy-2-(4-methoxyphenyl)-4-((2RS,3RS)-3-(4-methoxyphenyl)oxiran-2-yl)benzofuran
  参考文献：
  名称：

  寡麦角类天然产物的一种通用方法–合成长春藤呋喃，马里巴托A和肖塔酚的全甲基化类似物†

  摘要：

  本文描述了一种高度实用的方法来制备低聚类胡萝卜素天然产物。区域选择性的Bi（OTf）3催化的环脱水提供了3-芳基苯并呋喃的制备方法。Pd催化的C–H直接活化苯并呋喃 并成功地与卤代芳烃进行了交叉偶联，从而在C1的C2位置引入了芳基。 苯并呋喃。2,3-二芳基苯并呋喃的进一步操作导致长春藤呋喃的全甲基化类似物的有效全合成，麦立醇A和肖塔酚。

  DOI：

  10.1039/b901911a

文献信息

• 924. Reaction of some substituted methylthiomethyl-benzenes and -naphthalenes with methyl iodide
  作者：P. Mamalis

  DOI：10.1039/jr9600004747

  日期：——
• Synthetic Approach to Malibatol  A
  作者：George A. Kraus、Ikyon Kim

  DOI：10.1021/ol027574o

  日期：2003.4.1

  A synthetic approach to malibatol A featuring a novel benzofuran synthesis is described.
• Reactions of charged substrates. 1. The effect of product isomerization on kinetics in the reaction of thiocyanate with (4-methoxybenzyl)dimethylsulfonium chloride
  作者：Neil Buckley、Norman J. Oppenheimer

  DOI：10.1021/jo00080a043

  日期：1994.1
• Reactions of Charged Substrates. 3. The Hydrolysis of (4-Methoxybenzyl)dimethylsulfonium Chloride
  作者：Neil Buckley、Norman J. Oppenheimer

  DOI：10.1021/jo00098a033

  日期：1994.9

  At low concentrations (ca. 10(-4) M), the hydrolysis of (4-methoxybenzyl)dimethyl sulfonium chloride (1) proceeds smoothly to completion in H2O or D2O at 80 degrees C. The rate constants measured directly by UV or NMR methods match the rate constants obtained as the ordinate intercepts of plots of k(obsd) vs [NaN3] or [pyridine-d(5)]. As expected, the rate constants decrease with increasing ionic strength (NaCl or NaClO4, mu = 0-2). There is a small solvent deuterium isotope effect, k(H)/k(D) = 1.1 at mu = 0 and 1.7, and the alpha-deuterium secondary isotope effect is k(H)/k(D) = 1.26 per deuterium. At higher concentrations (10 mM), the hydrolysis does not go to completion, with the fraction of 1 remaining reaching plateau values that are stable. Plots of the fraction of 1 remaining vs the initial concentration of 1 extrapolate to zero. Running the reaction in the presence of either Hg+2 or Zn+2 drives the reaction to completion by removing SMe(2) as the Lewis complex. While these results are consistent with common leaving group suppression of hydrolysis, they are also consistent with the establishment of an equilibrium among the starting material and the product alcohol, SMe(2), and hydronium ion. The suppression data are fitted to the equation for the equilibrium, and running the reaction in reverse gives the amount of I predicted by the equation. Reinterpretation of older data in light of the equilibrium, the results reported here, and results for the nucleophilic substitution reaction suggests that the mechanism of hydrolysis is S(N)1 with no ion-dipole complex intermediate.