1-benzyl-3-cyanoquinolinium ion | 148761-78-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: 1-benzyl-3-cyanoquinolinium ion
• 英文别名: 1-benzyl-3-cyanoquinolinium cation；1-benzyl-3-cyanoquinolinium；Quinolinium, 3-cyano-1-(phenylmethyl)-；1-benzylquinolin-1-ium-3-carbonitrile
• CAS: 148761-78-8
• 化学式: C₁₇H₁₃N₂
• 分子量: 245.304
• InChiKey: RAWCJBNTWIPXSE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-benzyl-3-cyanoquinolinium ion 以 水 、 异丙醇 为溶剂， 生成 1-benzyl-2-hydroxy-1,2-dihydroquinoline
  参考文献：
  名称：

  马库斯关于 .alpha 垂直效应的理论。用于 NAD+ 类似物之间的氢化物转移

  摘要：

  Une serie d'ions benzyl-1 cyano-3 quinoleinium, substitues sur le groupe benzyl, est preparee。Les constantes de vitesse et d'equilibre sont 确定倾泻反应 avec l'ionmethyl-10 acridinium

  DOI：

  10.1021/ja00321a011
• 作为产物：
  描述：

  1-benzyl-2-hydroxy-1,2-dihydroquinoline 以 水 、 异丙醇 为溶剂， 生成 1-benzyl-3-cyanoquinolinium ion
  参考文献：
  名称：

  马库斯关于 .alpha 垂直效应的理论。用于 NAD+ 类似物之间的氢化物转移

  摘要：

  Une serie d'ions benzyl-1 cyano-3 quinoleinium, substitues sur le groupe benzyl, est preparee。Les constantes de vitesse et d'equilibre sont 确定倾泻反应 avec l'ionmethyl-10 acridinium

  DOI：

  10.1021/ja00321a011
• 作为试剂：
  描述：

  9,10-dihydro-10-methylacridine 在 1-benzyl-3-cyanoquinolinium ion 作用下， 以 乙腈 为溶剂， 生成 N-甲基吖啶
  参考文献：
  名称：

  Solvent modulation of the dynamics of hydride transfer

  摘要：

  A two-coordinate model is used to discuss hydride transfer between substituted acridans and substituted quinolinium ions. Both the donor and the acceptor can be regarded as analogues of the enzymatic cofactor, NAD+. One coordinate is used for solvent and heavy atom motions; the other is used for the hydrogenic motion which produces the covalency change. In hydroxylic solvents the primary kinetic isotope effect is maximized and constant, and the Bronsted a indicates a critical configuration equally resembling reactants and products. However, in certain polar, aprotic solvents, most notably dimethyl sulfoxide (DMSO), the isotope effect is sharply reduced and the Bronsted a indicates a productlike critical configuration. These changes are attributed to a barrier in the solvent coordinate. Solvents like DMSO, which are known to be relatively good Lewis bases, are thought to respond relatively slowly to the relocation of positive charge in the reacting molecules. This shifts the rate-limiting step to the solvent coordinate. Hydroxylic solvents, on the other hand, have a fast component in their dielectric relaxation spectrum, which permits them to respond quickly to the relocation of charge. Thus, the overall bottleneck is in the hydrogenic coordinate.

  DOI：

  10.1021/j100178a021

文献信息

• Hydride-exchange reactions between NADH and NAD+ model compounds under non-steady-state conditions. Apparent and real kinetic isotope effects
  作者：Yun Lu、Yixing Zhao、Kishan L. Handoo、Vernon D. Parker

  DOI：10.1039/b208186e

  日期：2003.12.19

  The profiles for the reactions of MAH deviate significantly from those expected for the simple single-step mechanism with the deviation increasing with increasing temperature. The deviation from simple mechanism behavior is much less pronounced for the reactions of 10-methyl-9,10-dihydroacridine-10,10-d2 (MAD) which gives rise to extent of reaction dependent apparent kinetic isotope effects (KIEapp)

  研究了NADH模型化合物10-甲基-9,10-二氢ac啶（MAH）和1-苄基-3-氰基喹啉鎓（BQCN +）离子在乙腈中的氢化物交换反应的动力学，反应温度范围为291至325 K.将前半衰期的反应时间分布图与理论数据进行比较，以得到简单的单步机制和包括初始供体/受体复合物形成以及随后的单分子氢化物转移的两步机制的理论数据。MAH的反应曲线与简单的单步机理所预期的明显不同，并且随着温度的升高而增加。对于10-甲基-9,10-二氢ac啶-10的反应，其与简单机理行为的偏离远没有那么明显。10-d2（MAD），它引起依赖于反应的表观动力学同位素效应（KIEapp）的程度。在所有稳态下，均观察到反应时间曲线的实验范围与两步机理的理论数据在稳态前时期的极佳拟合。在整个温度范围内将氢化物交换反应的动力学分解为微观速率常数，导致氢化物转移步骤的真正动力学同位素效应为40（291 K）至8.2（325 K
• Thermodynamic Control in Ion Radical Cleavages through Out-of-Cage Diffusion of Products. Dynamics of C−C Fragmentation in Cation Radicals of <i>tert</i>-Butylated NADH Analogues and Other Ion Radicals
  作者：Agnès Anne、Sylvie Fraoua、Jacques Moiroux、Jean-Michel Savéant

  DOI：10.1021/ja9542294

  日期：1996.4.24

  alkyl group, cation radicals of NADH analogues alkylated para to the nitrogen atom (AHR), generated by direct or indirect electrochemical means, may undergo C−C fragmentation or deprotonation. The former reaction is dominant with the tert-butyl substituent and the latter with methyl and phenyl substituents. It is shown that the cleavage reaction produces AH+ and the tert-butyl radical which is then

  根据烷基的性质，通过直接或间接电化学方法产生的在氮原子（AHR）的对位烷基化的 NADH 类似物的阳离子自由基可能会发生 C-C 碎裂或去质子化。前一种反应占主导地位的是叔丁基取代基，后者占主导地位的是甲基和苯基取代基。结果表明，裂解反应产生 AH+ 和叔丁基自由基，然后迅速氧化形成叔丁基阳离子。改变 A 基团允许 C-C 裂解速率常数（由循环伏安法或氧化还原催化确定）变化约。大约变化的六个数量级。反应的标准自由能为 0.4 eV。速率常数的对数与反应的标准自由能呈线性变化，斜率为 1/(60 meV)，表明破碎是由两个碎片从溶剂笼中扩散出来的动力学控制的，而不是由活化控制的。因此，动力学数据允许轻松地...
• The Tightness Contribution to the Brønsted α for Hydride Transfer between NAD⁺ Analogues
  作者：In-Sook Han Lee、Kim-Hung Chow、Maurice M. Kreevoy

  DOI：10.1021/ja011855u

  日期：2002.7.1

  It has been shown that the rate of symmetrical hydride transfer reaction varies with the hydride affinity of the (identical) donor and acceptor. In that case, Marcus theory of atom and group transfer predicts that the Bronsted α depends on the location of the substituent, whether it is in the donor or the acceptor, and the tightness of the critical configuration, as well as the resemblance of the critical

  已经表明对称氢化物转移反应的速率随着（相同）供体和受体的氢化物亲和力而变化。在这种情况下，马库斯原子和基团转移理论预测布朗斯台德 α 取决于取代基的位置，无论是在供体还是受体中，以及临界构型的紧密度，以及临界构型的相似性反应物或产物的配置。现在，这一预测已在杂环含氮阳离子之间的氢化物转移反应中得到证实，可将其视为酶辅因子烟酰胺腺嘌呤二核苷酸 (NAD+) 的类似物。与供体中的取代基发生的一系列反应得到 0.67 ± 0.03 的 Bronsted α 和 0.64 ± 0.06 的紧密度参数 τ。受体中的取代基 α = 0.32 ± 0。03 和 τ = 0.68 ± 0.08。反应都是自发的，平衡常数在 0.4 到 3 × 104 之间，两组跨越大约相同的平衡常数范围。
• Steric and Kinetic Isotope Effects in the Deprotonation of Cation Radicals of NADH Synthetic Analogs
  作者：Agnes Anne、Sylvie Fraoua、Philippe Hapiot、Jacques Moiroux、Jean-Michel Saveant

  DOI：10.1021/ja00133a014

  日期：1995.7

  The deprotonation rate constants and kinetic isotope effects of the cation radicals have been determined by combined use of direct electrochemical techniques at micro- and ultramicroelectrodes, redox catalysis, and laser flash photolysis, over a extended series of opposing bases. Significant steric hindrance to deprotonation results from encumbering of the opposing base and of the functional carbon in the cation radical by alkyl groups. Kinetic isotope effects, ranging from 2 to 12 in terms of k(H)/k(D), appear upon substituting H to D at the functional carbon of the cation radical. The modest magnitude of the kinetic isotope effects and the fact that they are insensitive to steric hindrance show that proton (or H-atom) tunneling does not interfere significantly in the deprotonation reaction. All the cation radicals in the methylacridan series are strong acids, with pK(a)'s ranging from 0.8 to 1.7, as determined from thermodynamic cycles involving measured standard potentials and hydride-transfer equilibrium constants.
• Hydride transfer and oxyanion addition equilibria of NAD+ analogs
  作者：Drazen Ostovic、In Sook Han Lee、Roger M. G. Roberts、Maurice M. Kreevoy

  DOI：10.1021/jo00222a006

  日期：1985.11