1-苄基-3-氰基-1,4-二氢喹啉 | 73184-18-6

• 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
• 中文名称: 1-苄基-3-氰基-1,4-二氢喹啉
• 英文名称: 1-benzyl-3-cyano-1,4-dihydroquinoline
• 英文别名: 1-benzyl-4H-quinoline-3-carbonitrile
• CAS: 73184-18-6
• 化学式: C₁₇H₁₄N₂
• 分子量: 246.312
• InChiKey: OEIDFKCTDXKQQD-UHFFFAOYSA-N

物化性质

• 熔点：
  130 °C (decomp)
• 沸点：
  415.1±45.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  27
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-苄基-3-氰基-1,4-二氢喹啉 在 2-氟吡啶 作用下， 以 乙腈 为溶剂， 生成 C₁₇H₁₃N₂
  参考文献：
  名称：

  Anne, Agnès; Hapiot, Philippe; Moiroux, Jacques, Journal of the American Chemical Society, 1992, vol. 114, # 12, p. 4694 - 4701

  摘要：

  DOI：
• 作为产物：
  描述：

  4,4'-Oxydi-(1-benzyl-1,4-dihydro-3-chinolincarbonitril) 在 zinc(II) chloride 作用下， 以 甲苯 为溶剂， 反应 48.0h， 生成 1-苄基-3-氰基-1,4-二氢喹啉
  参考文献：
  名称：

  Guendel, Wolf-H.; Berenbold, Helmut, Zeitschrift fur Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, 1981, vol. 36, # 6, p. 745 - 749

  摘要：

  DOI：
• 作为试剂：
  描述：

  N-甲基吖啶 在 1-苄基-3-氰基-1,4-二氢喹啉 作用下， 以 乙腈 为溶剂， 生成 9,10-dihydro-10-methylacridine
  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

• Intramolecular kinetic isotope effect in hydride transfer from dihydroacridine to a quinolinium ion. Rejection of a proposed two-step mechanism with a kinetically significant intermediate
  作者：Charles L. Perrin、Chen Zhao

  DOI：10.1039/b806869k

  日期：——

  The intramolecular kinetic isotope effect (KIE) for hydride transfer from 10-methyl-9,10-dihydroacridine to 1-benzyl-3-cyanoquinolinium ion has been found to be 5-6 by both (1)H NMR and mass spectrometry. This KIE is consistent with other hydride transfers. It is inconsistent with the high intermolecular KIEs derived by fitting to a two-step mechanism with a kinetically significant intermediate complex

  通过（1）H NMR和质谱法，发现氢化物从10-甲基-9,10-二氢ac啶转移至1-苄基-3-氰基喹啉鎓离子的分子内动力学同位素效应（KIE）为5-6。该KIE与其他氢化物转移相一致。这与通过具有动力学上显着的中间配合物的两步机制拟合而得到的高分子间KIE不一致，并且与那些KIE的强温度依赖性不一致。因此，我们拒绝这种反应的两步机制，并且我们建议采用这种机制的其他情况是错误的。
• Nonconventional versus conventional application of pseudo-first-order kinetics to fundamental organic reactions
  作者：Vernon D. Parker、Weifang Hao、Zhao Li、Russell Scow

  DOI：10.1002/kin.20609

  日期：2012.1

  Three new analysis procedures for pseudo‐first‐order kinetics are introduced and applied to eight different fundamental organic reactions. The reactions belong to the following classes: nitroalkane proton transfer, formal hydride ion transfers from NADH model compounds, and SN2 reactions of alkyl halides with ionic and neutral nucleophiles. The three methods consist of (1) half‐life dependence of kapp

  引入了三种针对拟一阶动力学的新分析程序，并将其应用于八个不同的基本有机反应。反应属于以下几类：硝基烷烃质子转移，来自NADH模型化合物的形式氢化物离子转移以及烷基卤化物与离子和中性亲核试剂的S N 2反应。这三种方法包括（1）k app的半衰期依赖性，（2）顺序线性伪一阶相关，以及（3）修正的瞬时速率常数分析。这三个过程中的每一个都能够区分单步机制和多步机制，并且这三个过程的组合为区分这两种机制可能性提供了强有力的策略。从作为示例选择的八个反应中获得的数据清楚地表明了程序在实践中的工作方式。©2011 Wiley Periodicals，Inc.国际化学杂志Kinet 44：2–12，2012
• Structure sensitivity of the Marcus .lambda. for hydride transfer between NAD+ analogs
  作者：Maurice M. Kreevoy、Drazen. Ostovic、In Sook Han. Lee、David A. Binder、Gary W. King

  DOI：10.1021/ja00210a036

  日期：1988.1

  Constantes de vitesse et d'equilibre du transfert d'hydrure entre divers pyridinium, quinoleinium, acridinium et phenanthridinium

  Constantes de vitesse et d'equilibre du transfert d'hydrure entre divers pyridinium, quinoleinium, acridinium et phenanthridinium
• 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.