Ti III和Bu t OOH在流动系统中的反应在水溶液中生成了叔丁氧基。提出的证据表明,尽管在这些条件下(k > 10 6 dm 3 mol –1 s –1),Bu t O·向Me·和丙酮的裂解迅速,但竞争的加成反应(如对乙烯基醚,呋喃的竞争))和提取反应(使用醇类)可以进行表征。卜ŤO·在反应中显示出亲电性,与·OH相似,但与丙-2-烯-1-醇反应时,与·OH不同,它经历了抽象而不是加成反应。在非常低的pH值下,叔丁氧基行为的变化归因于质子化的对应物Bu t OH + the的形成和反应。
Reaction of vinyl- and propenyl-ethers with tert-butoxyl radicals - an ESR study
作者:Hans-Gert Korth、Reiner Sustmann
DOI:10.1016/s0040-4039(00)98834-8
日期:1985.1
Photolytically generated tert-butoxyl radicals react with vinyl- and propenyl ethers by hydrogen abstraction and addition to the double bond; the abstraction/addition ratio and the regioselectivity of addition are interpreted in terms of predominant steric interactions.