| 65082-31-7

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机含氧阴离子化合物
• CAS: 65082-31-7
• 化学式: C₁₆H₃₆OP
• 分子量: 275.435
• InChiKey: ASDHAYIHGPFJTB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.13
• 重原子数：
  18.0
• 可旋转键数：
  10.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  叔-丁氧基自由基 、 三丁基膦 生成
  参考文献：
  名称：

  Rate constants and Arrhenius parameters for the reactions of primary, secondary, and tertiary alkyl radicals with tri-n-butyltin hydride

  摘要：

  DOI：

  10.1021/ja00416a008

文献信息

• Kinetic study on the reaction of tributylphosphine with methylviologen. Reactivity of the phosphine radical cation intermediate towards nucleophiles
  作者：Shinro Yasui、Kosei Shioji、Munekazu Tsujimoto、Atsuyoshi Ohno

  DOI：10.1039/a807722c

  日期：——

  Tributylphosphine, Bun3P (BP), was reacted with 1,1′-dimethyl-4,4′-bipyridinium (methylviologen; MV2+) in the presence of an alcohol or thiol (RXH; X = O, S) in acetonitrile under an argon atmosphere at 50 °C, which resulted in the gradual formation of the one-electron reduced form of the MV2+, MV+. Meanwhile, BP was oxidized to tributylphosphine oxide (BP-O). The increase in the amount of MV+, which was followed spectrophotometrically with BP and RXH being in large excess, did not obey first-order kinetics. The observation, along with the results from product analysis, shows that single-electron transfer (SET) takes place from BP to MV2+ to generate tributylphosphine radical cation BP˙+, as well as MV+, and the resulting BP˙+ undergoes ionic reaction with RXH and back electron transfer from MV+ in comparable efficiency. A regression analysis of the kinetic data gave the relative value of the second-order rate constant, kNurel, for the ionic reaction of BP˙+ with RXH. Comparison of the kNurel values thus obtained for reactions with various RXH’s shows that the reaction of BP˙+ with nucleophile RXH is governed by both steric and electronic factors of RXH. The activation energy Ea of the reaction was found to be significantly large, which is in contrast to previous observations that ionic reactions of carbon radical cations with nucleophiles usually have very small values of Ea.

  三丁基膦，Bun3P (BP)，与 1,1'-二甲基-4,4'-联吡啶鎓（甲基紫精；MV2+）在乙醇或硫醇（RXH；X = O, S）存在下在乙腈中在氩气下反应在 50°C 的大气中，逐渐形成单电子还原形式的 MV2+、MV+。同时，BP被氧化为三丁基氧化膦(BP-O)。分光光度法跟踪的 MV+ 量的增加，其中 BP 和 RXH 大大过量，但不符合一级动力学。观察结果以及产物分析结果表明，从 BP 到 MV2+ 发生单电子转移（SET），生成三丁基膦自由基阳离子 BP˙+ 和 MV+，所得的 BP˙+ 与RXH 和来自 MV+ 的反电子转移效率相当。动力学数据的回归分析给出了 BP˙+ 与 RXH 离子反应的二阶速率常数 kNurel 的相对值。比较由此获得的与各种 RXH 的反应的 kNurel 值表明，BP˙+ 与亲核试剂 RXH 的反应受 RXH 的空间和电子因素控制。发现该反应的活化能Ea非常大，这与之前观察到的碳自由基阳离子与亲核试剂的离子反应通常具有非常小的Ea值相反。