Research on The Novel Photo-rearrangement And Photo-fragmentation of Arylated Cyclic Peroxides

1)采用改进的电子转移光氧化方法制备了多种芳基化的1，2-二氧杂环己烷和1，2-二氧六环。结果，建立了上述环状过氧化氢的未知衍生物的新的合成方法，同时改进了已知衍生物的产率。2)发现在直接光照射下，上述环状过氧化氢的O-O键裂解的双自由基中间体发生了重排和裂解。研究还发现，对甲氧基苯基等具有给电子取代基的底物一般会发生芳基移动。3)在环状过氧化氢的热反应中，双氧基-双自由基中间体机理和类配位键断裂机理同时进行。4)在吡咯盐敏化的光电子转移反应中，C-O键断裂的阳离子自由基中间体发生重排和芳香反应。5)Fe(II)和Fe(III)溴诱导的环状过氧化物单电子转移还原反应。结果发现，O-O键断裂的单氧基中间体发生了重排和断裂。

1) Variety of arylated 1,2-dioxolanes and 1,2-dioxanes were prepared by using original modified methods of electron transfer photo-oxygenation. As a result, new synthetic methods were established for the unknown derivatives of above cyclic peroxides while improvements of the yields for the known derivatives were performed.2) It was found that O-O bond cleaved diradical intermediates of above cyclic peroxides in the direct photo-irradiation occurred rearrangements and fragmentations. It was also found that aryl shift generally proceeded for the substrates possessing electron donating aromatic substituents such as p-methoxyphenyl group.3) It was found that the dioxyl-diradical intermediate mechanism and the concerted-like bond cleavage mechanism were simultaneously operated in the thermal reaction of the cyclic peroxides.4) It was found that C-O bond cleaved cation radical intermediates occurred rearrangements and fragrnentations in the pyrylium salt sensitized photo-electron transfer reactions.5) Non-photochemical single electron transfer reduction of the cyclic peroxides induced by Fe(II)and Fe(III) bromides were performed. As a result, it was found that O-O bond cleaved mono-oxyl-radical intermediates underwent rearrangements and fragmentations.