(4-methoxybenzyl)dimethylsulfonium | 46122-80-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (4-methoxybenzyl)dimethylsulfonium
• 英文别名: p-Methoxybenzyldimethylsulfonium；(4-Methoxyphenyl)methyl-dimethylsulfanium
• CAS: 46122-80-9
• 化学式: C₁₀H₁₅OS
• 分子量: 183.294
• InChiKey: RCBWOXMTEAHFGT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  12
• 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：
  1

反应信息

• 作为反应物：
  描述：

  (4-methoxybenzyl)dimethylsulfonium 在 水 、 sodium chloride 作用下， 生成 4-甲氧基苄醇
  参考文献：
  名称：

  带电底物的反应。8.（4-甲氧基苄基）二甲基s氯化物的亲核取代反应。

  摘要：

  仅对于具有中等硬度的亲核试剂，发生在标题化合物（1）上的置换反应。反应的亲核试剂显示出多种机制。1通过混合的S（N）1 / S（N）2机理与中性亲核吡啶-d（5）反应；加入盐以控制离子强度会影响单分子过程的速率，但对双分子速率常数没有影响。N（3）（-）和SO（3）（2）（-）取代的机理取决于是否存在外源盐。在恒定的离子强度下，机理是在[Nu]的大部分范围内混合S（N）1 / S（N）2。仅存在亲核试剂时，k（obsd）对[Nu]的图显示出严重的断裂，这不是盐效应的结果。速率常数和产物比率的分析表明，在低[Nu]反应下，会通过协调的休斯-英戈尔德S（N）2和预先缔合的机制同时发生。在高[Nu]时，位移仅通过预先关联确认的机制发生。将这些结果与苄基二甲基ulf的气相解离数据和苄基吡啶鎓的溶液结果进行比较表明，中间体的内在稳定性不一定决定其机理。

  DOI：

  10.1021/jo9620977
• 作为产物：
  描述：

  二甲基硫 、 4-甲氧基氯苄 以 氯仿 为溶剂， 生成 (4-methoxybenzyl)dimethylsulfonium
  参考文献：
  名称：

  Reactions of Charged Substrates. 4. The Gas-Phase Dissociation of (4-Substituted benzyl)dimethylsulfoniums and -pyridiniums

  摘要：

  The relative rates for the gas-phase dissociation RX(+) --> R(+) + X degrees of five (4-Y-substituted benzyl)-dimethysulfoniums (Y = MeO, Me, H, Cl, and NO2) and 24 (4-Y-substituted benzyl)-3'-Z-pyridiniums (complete series for Z = CN, Cl, CONH2, and H, and 4-methoxy- and 4-nitrobenzyls for Z = F and CH3CO) were measured using liquid secondary ion mass spectrometry. The Hammett plot (vs delta Delta G degrees or sigma(+)) is linear for the sulfoniums, but plots for the four pyridinium series have a drastic break between the 4-Cl and 4-NO2 substrates. Broinsted-like plots for the pyridiniums show a strong leaving group effect only for 4-nitrobenzyls. An analysis of these linear free energy relations with supporting evidence from semiempirical computations suggests that collisionally activated pyridinium substrates dissociate by two pathways, direct dissociation and through an ion-neutral complex intermediate. Comparison of these results with results for the solution reactions of some of these compounds shows that the mechanism is different in the gas and solution phases. Sufficient experimental data are not available to assign a mechanism for dissociation to the sulfonium series, but computational results show characteristics of a direct dissociative mechanism.

  DOI：

  10.1021/jo951257w

文献信息

• Reactions of Charged Substrates. 4. The Gas-Phase Dissociation of (4-Substituted benzyl)dimethylsulfoniums and -pyridiniums
  作者：Neil Buckley、David Maltby、Alma L. Burlingame、Norman J. Oppenheimer

  DOI：10.1021/jo951257w

  日期：1996.1.1

  The relative rates for the gas-phase dissociation RX(+) --> R(+) + X degrees of five (4-Y-substituted benzyl)-dimethysulfoniums (Y = MeO, Me, H, Cl, and NO2) and 24 (4-Y-substituted benzyl)-3'-Z-pyridiniums (complete series for Z = CN, Cl, CONH2, and H, and 4-methoxy- and 4-nitrobenzyls for Z = F and CH3CO) were measured using liquid secondary ion mass spectrometry. The Hammett plot (vs delta Delta G degrees or sigma(+)) is linear for the sulfoniums, but plots for the four pyridinium series have a drastic break between the 4-Cl and 4-NO2 substrates. Broinsted-like plots for the pyridiniums show a strong leaving group effect only for 4-nitrobenzyls. An analysis of these linear free energy relations with supporting evidence from semiempirical computations suggests that collisionally activated pyridinium substrates dissociate by two pathways, direct dissociation and through an ion-neutral complex intermediate. Comparison of these results with results for the solution reactions of some of these compounds shows that the mechanism is different in the gas and solution phases. Sufficient experimental data are not available to assign a mechanism for dissociation to the sulfonium series, but computational results show characteristics of a direct dissociative mechanism.
• Reactions of Charged Substrates. 8. The Nucleophilic Substitution Reactions of (4-Methoxybenzyl)dimethylsulfonium Chloride
  作者：Neil Buckley、Norman J. Oppenheimer

  DOI：10.1021/jo9620977

  日期：1997.2.1

  product ratios suggests that at low [Nu] reaction occurs simultaneously through concerted Hughes-Ingold S(N)2 and preassociation-concerted mechanisms. At high [Nu], displacement occurs only through the preassociation-concerted mechanism. Comparison of these results with data for gas-phase dissociation of benzyl dimethylsulfoniums and with solution results for benzyl pyridiniums suggests that the intrinsic

  仅对于具有中等硬度的亲核试剂，发生在标题化合物（1）上的置换反应。反应的亲核试剂显示出多种机制。1通过混合的S（N）1 / S（N）2机理与中性亲核吡啶-d（5）反应；加入盐以控制离子强度会影响单分子过程的速率，但对双分子速率常数没有影响。N（3）（-）和SO（3）（2）（-）取代的机理取决于是否存在外源盐。在恒定的离子强度下，机理是在[Nu]的大部分范围内混合S（N）1 / S（N）2。仅存在亲核试剂时，k（obsd）对[Nu]的图显示出严重的断裂，这不是盐效应的结果。速率常数和产物比率的分析表明，在低[Nu]反应下，会通过协调的休斯-英戈尔德S（N）2和预先缔合的机制同时发生。在高[Nu]时，位移仅通过预先关联确认的机制发生。将这些结果与苄基二甲基ulf的气相解离数据和苄基吡啶鎓的溶液结果进行比较表明，中间体的内在稳定性不一定决定其机理。