Acid-catalyzed solvolysis of polyenol ethers. III. Effect of the alkoxy moiety
作者:Saskia A.M. Nieuwenhuis、Louis B.J. Vertegaal、Marian C. de Zoete、Arne van der Gen
DOI:10.1016/s0040-4020(01)89330-3
日期:1994.1
The dependence of the solvolysis of polyenol ethers on the nature of the alkoxy moiety has been studied. A new reaction path, leading to the formation of ω-hydroxy (methoxy) substituted aldehydes and -esters, was established. The proposed reaction pathway (scheme 6) is initiated by an electron transfer from the polyenol ether to molecular oxygen, followed by combination of the two radicals to a peroxide
研究了烯醇醚的溶剂分解对烷氧基部分性质的依赖性。建立了导致ω-羟基(甲氧基)取代的醛和酯形成的新反应路径。所提出的反应途径(方案6)是由电子从多烯醇醚转移到分子氧,然后将两个自由基结合成过氧化物两性离子而引发的。质子化后,溶剂加到多烯的ω-碳原子上,得到中间体,该中间体可以使水松散而形成酯,或者使烷氧基部分松散而得到醛。据信这种机理与许多聚烯醇醚,包括天然诱变剂番石榴烯12所表现出的强诱变活性有关。