quinuclidinyl radical | 35942-63-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 奎宁环
• 英文名称: quinuclidinyl radical
• CAS: 35942-63-3；71223-00-2
• 化学式: C₇H₁₂N
• 分子量: 110.179
• InChiKey: ZLPJBUCTICXVHQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.26
• 重原子数：
  8.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  3.24
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  奎宁环 在 tert-butoxyl radical 作用下， 以 苯 为溶剂， 生成 quinuclidinyl radical
  参考文献：
  名称：

  叔丁氧基自由基的化学：大多数从碳中提取氢的证据是熵控制的

  摘要：

  报告了溶液中几种碳氢化合物和叔胺的绝对速率常数和 Arrhenius 参数，用于通过叔丁氧基自由基 ((t) BuO.) 从碳中提取氢。结合文献中已有的数据，对所有可用数据的分析表明，大多数氢提取（从碳中）是由 (t) BuO 提取的。是熵控制的（即，TdeltaS > deltaH，在室温下的溶液中）。对于 CH 键解离能 (BDE) > 92 kcal/mol 的底物，根据 Evans-Polanyi 方程，夺氢的活化能随着 BDE 的降低而降低，α 约为 0.3。对于含有 79 至 92 kcal/mol CH BDE 的底物，活化能不会随 CH BDE 显着变化。这些结果在使用 (t) BuO 的背景下的含义。

  DOI：

  10.1021/ja0493493

文献信息

• Hydrogen Atom Abstraction Reactions from Tertiary Amines by Benzyloxyl and Cumyloxyl Radicals: Influence of Structure on the Rate-Determining Formation of a Hydrogen-Bonded Prereaction Complex
  作者：Michela Salamone、Gino A. DiLabio、Massimo Bietti

  DOI：10.1021/jo201025j

  日期：2011.8.5

  study on the hydrogen atom abstraction reactions from a series of tertiary amines by the cumyloxyl (CumO•) and benzyloxyl (BnO•) radicals was carried out. With the sterically hindered triisobutylamine, comparable hydrogen atom abstraction rate constants (kH) were measured for the two radicals (kH(BnO•)/kH(CumO•) = 2.8), and the reactions were described as direct hydrogen atom abstractions. With the other

  由cumyloxyl（粗磨上从一系列叔胺的氢原子夺取反应时间分辨动力学研究•）和苄氧基（BNO •）自由基进行。在空间位阻的三异丁胺下，测量了两个自由基的相对可比的氢原子抽象速率常数（k H）（k H（BnO •）/ k H（CumO •）= 2.8），并且该反应被描述为直接氢原子抽象。与其他胺类相比，k H（BnO •）/ k H（CumO •）观察到13至2027倍的比率。在BnO之间的反应中，k H接近扩散极限•环胺和无环胺，以及无环胺和受阻环胺1,2,2,6,6-五甲基哌啶的反应性下降。这些结果为我们的假设提供了进一步的支持，即该反应是通过速率决定性地在苄氧基α-C–H与其中发生氢原子抽象的氮孤对之间形成C–H / N氢键预反应复合物而进行的，以及证明了胺结构对整个反应机理的重要作用。支持这一图象的附加机械信息从胺的反应的研究用氘代苄氧基自由基（PhCD得到2 ö •，BNO • -
• N−H and α(C−H) Bond Dissociation Enthalpies of Aliphatic Amines
  作者：Jacques Lalevée、Xavier Allonas、Jean-Pierre Fouassier

  DOI：10.1021/ja0204168

  日期：2002.8.1

  Bond dissociation enthalpies (BIDES) of a large series of aliphatic amines (21) were measured by means of photoacoustic calorimetry. Despite the different structures studied in the primary, secondary, and tertiary amine series, the a(C-H) BIDES were found to be very similar for unconstrained amines with values very close to 91 kcal/mol. alphaC- and N-alkylation or introduction of an hydroxy group only slightly affect the BDEs, a fact in perfect agreement with calculations performed at different CBS levels. This demonstrates the predominance of the two-orbital-three-electron interaction involving the N and alphaC(.) orbitals. On the other hand, the N-H BIDE decreases when going from primary to secondary amines. This result is interpreted in term of a hyperconjugation in sigmaC-C bonds, which leads to a stabilization of the aminyl radical. For cyclized amines, the BIDES depend on the relative geometry of the singly occupied alphaC(.) orbital with respect to that of the N atom, disfavoring the two-orbital-three-electron interaction. However, such structures can exhibit through-bond interaction. For a crowded structure such as triisopropylamine, for which the alphaC(.) orbital is not coplanar with the nitrogen one, the relaxation of a strain energy allows the BIDE to be comparable to flexible structures.
• Absolute rate constants for the reactions of tert-butoxyl, tert-butylperoxyl, and benzophenone triplet with amines: the importance of a stereoelectronic effect
  作者：D. Griller、J. A. Howard、P. R. Marriott、J. C. Scaiano

  DOI：10.1021/ja00393a020

  日期：1981.2
• <i>tert</i>-Butoxyl as a Model for Radicals in Biological Systems:  Caveat Emptor
  作者：J. M. Tanko、Robert Friedline、N. Kamrudin Suleman、Neal Castagnoli

  DOI：10.1021/ja005730l

  日期：2001.6.1