1-<4-Chlor-benzyl>-pyridinium | 71897-27-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-<4-Chlor-benzyl>-pyridinium
• 英文别名: N-(4-Chlorbenzyl)pyridinium；p-Chlorbenzylpyridinium；1-(4-chloro-benzyl)-pyridinium；1-(4-chloro-benzyl)-pyridinium cation；1-[(4-Chlorophenyl)methyl]pyridin-1-ium
• CAS: 71897-27-3
• 化学式: C₁₂H₁₁ClN
• 分子量: 204.679
• InChiKey: GDGNYUXBILMTKL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  3.9
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  吡啶 在 p-chlorobenzyl halide 作用下， 反应 3.0h， 生成 1-<4-Chlor-benzyl>-pyridinium
  参考文献：
  名称：

  Investigations of the fragmentation pathways of benzylpyridinium ions under ESI/MS conditions

  摘要：

  苄基吡啶鎓离子经常被用作 "温度计离子"，以评估在质谱仪源中形成的离子的内部能量分布。然而，这些母离子的详细碎裂途径尚未得到很好的确定。特别是涉及重排（RR）过程的碎片可能会影响模拟分布曲线。在之前的研究中，我们认为在电喷雾电离/质谱（ESI/MS）和快速原子轰击/质谱（FAB/MS）实验中实际发生了这种重排。在此，我们对不同取代的苄基吡啶鎓离子进行了系统研究。理论计算表明，在诸如 ESI 或 FAB 等 "软电离 "条件下，会发生导致取代的托吡啶离子的 RR 断裂。在气相反应条件下获得的实验结果表明，在 ESI/MS 条件下，一些取代的苄基吡啶鎓化合物实际上会发生 RR 断裂。为了了解实际发生的反应途径，还进行了质量分析动力学实验，这些实验结果与理论上提出的反应途径一致。Copyright © 2009 John Wiley & Sons, Ltd. All Rights Reserved.

  DOI：

  10.1002/jms.1672

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.
• US4032596A
  申请人：——

  公开号：US4032596A

  公开（公告）日：1977-06-28
• Investigations of the fragmentation pathways of benzylpyridinium ions under ESI/MS conditions
  作者：Emilie-Laure Zins、David Rondeau、Philippe Karoyan、Céline Fosse、Sophie Rochut、Claude Pepe

  DOI：10.1002/jms.1672

  日期：——

  Benzylpyridinium ions are often used as ‘thermometer ions’ in order to evaluate the internal energy distribution of the ions formed in sources of mass spectrometers. However, the detailed fragmentation pathways of these parent ions were not well established. In particular, fragmentation involving a rearrangement (RR) process may be influencing the simulated distribution curves. In a previous study, we suggested that such RR actually occurred under electrospray ionization/mass spectrometry (ESI/MS) and fast atom bombardment/mass spectrometry (FAB/MS) experiments. Here, we present a systematic study of different substituted benzylpyridinium ions. Theoretical calculations showed that RR fragmentation leading to substituted tropylium ions could occur under ‘soft ionization’ conditions, such as ESI or FAB. Experimental results obtained under gas-phase reactivity conditions showed that some substituted benzylpiridinium compounds actually undergo RR fragmentations under ESI/MS conditions. Mass-analyzed kinetic experiments were also carried out to gain information on the reaction pathways that actually occur, and these experimental results are in agreement with the reaction pathways theoretically proposed. Copyright © 2009 John Wiley & Sons, Ltd.

  苄基吡啶鎓离子经常被用作 "温度计离子"，以评估在质谱仪源中形成的离子的内部能量分布。然而，这些母离子的详细碎裂途径尚未得到很好的确定。特别是涉及重排（RR）过程的碎片可能会影响模拟分布曲线。在之前的研究中，我们认为在电喷雾电离/质谱（ESI/MS）和快速原子轰击/质谱（FAB/MS）实验中实际发生了这种重排。在此，我们对不同取代的苄基吡啶鎓离子进行了系统研究。理论计算表明，在诸如 ESI 或 FAB 等 "软电离 "条件下，会发生导致取代的托吡啶离子的 RR 断裂。在气相反应条件下获得的实验结果表明，在 ESI/MS 条件下，一些取代的苄基吡啶鎓化合物实际上会发生 RR 断裂。为了了解实际发生的反应途径，还进行了质量分析动力学实验，这些实验结果与理论上提出的反应途径一致。Copyright © 2009 John Wiley & Sons, Ltd. All Rights Reserved.