tripropylamine radical | 90265-29-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: tripropylamine radical
• 英文别名: tripropylamine
• CAS: 90265-29-5
• 化学式: C₉H₂₀N
• 分子量: 142.264
• InChiKey: PWXQYNWETQRRLN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.68
• 重原子数：
  10.0
• 可旋转键数：
  6.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 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：

  三正丙胺 在 二苯甲酮 作用下， 以 乙腈 为溶剂， 生成 tripropylamine radical
  参考文献：
  名称：

  N−H and α(C−H) Bond Dissociation Enthalpies of Aliphatic Amines

  摘要：

  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.

  DOI：

  10.1021/ja0204168

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 • -