苄氧基自由基引发的叔胺的扩散控制氢原子摘取。C-H/N 氢键的重要性。
Diffusion controlled hydrogen atom abstraction from tertiary amines by the benzyloxyl radical. The importance of C-H/N hydrogen bonding.
机构信息
Dipartimento di Scienze e Tecnologie Chimiche, Università Tor Vergata, Via della Ricerca Scientifica, 1 I-00133 Rome, Italy.
出版信息
Org Lett. 2011 Jan 21;13(2):260-3. doi: 10.1021/ol102690u. Epub 2010 Dec 9.
The rate constants for H-atom abstraction (k(H)) from 1,4-cyclohexadiene (CHD), triethylamine (TEA), triisobutylamine (TIBA), and DABCO by the cumyloxyl (CumO(•)) and benzyloxyl (BnO(•)) radicals were measured. Comparable k(H) values for the two radicals were obtained in their reactions with CHD and TIBA whereas large increases in k(H) for TEA and DABCO were found on going from CumO(•) to BnO(•). These differences are attributed to the rate-determining formation of BnO(•) C-H/amine N lone-pair H-bonded complexes.
测定了氢原子提取（k（H））的速率常数从 1,4-环己二烯（CHD），三乙胺（TEA），三异丁基胺（TIBA）和 DABCO 由枯基氧基（CumO（•））和苄基氧基（BnO（•））自由基。在它们与 CHD 和 TIBA 的反应中，获得了两个自由基的可比 k（H）值，而在从 CumO（•）到 BnO（•）时，TEA 和 DABCO 的 k（H）值大大增加。这些差异归因于 BnO（•）C-H/胺 N 孤对氢键合复合物的形成速率决定。
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