Photochemical generation and lifetimes in water of p-aryloxy- and p-alkoxyphenylnitrenium ions
作者:Pratima Ramlall、Robert A. McClelland
DOI:10.1039/a807567k
日期:——
the para position leads through a hemiacetal (or halohydrin) to the quinone imine, whose hydrolysis results in the final quinone product. Three kinetic processes are observed, the nitrenium hydration on the µs time scale, the hemiacetal breakdown on the ms time scale, and the imine hydrolysis on the minutes time scale. The nitrenium ions have lifetimes in aqueous solution of 50 ns (4-PhO), 70 ns (4-MeOC6H4O)
本文描述了以下4X-C的水溶液照射产品和闪光光解的研究6 ħ 4 Ñ 3 [X =的MeO(12A),环氧乙烷(12B),镨我O(图12C),卜吨O(12D),C 6 H 5 O(12e),4-MeOC 6 H 4 O(12f),F,Cl]和4-甲氧基-1-萘叠氮化物(15)。p苯醌(或1,4-萘),观察到作为产品,与图12a-d,15%,40%与12E,26%,4-F,用4-氯15%的70-90%的产率。醌是通过一种途径产生的,通过溶剂水分子的质子化作用,将最初形成的单线态芳基亚硝烯淬灭,形成亚硝酸根离子。该阳离子在水合处的水合对位通过半缩醛(或卤代醇)到达醌亚胺,后者水解产生最终的醌产物。观察到三个动力学过程,即在µs时间尺度上的nitr水合,在ms时间尺度上的半缩醛分解以及在分钟时间尺度上的亚胺水解。硝酸根离子在水溶液中的寿命为50 ns(4-PhO),70 ns(4-MeOC 6 H