Photolysis of α-Azidoacetophenones: Direct Detection of Triplet Alkyl Nitrenes in Solution
作者:Pradeep N. D. Singh、Sarah M. Mandel、Rachel M. Robinson、Zhendong Zhu、Roberto Franz、Bruce S. Ault、Anna D. Gudmundsdóttir
DOI:10.1021/jo034674e
日期:2003.10.1
of triplet alkyl nitrenes in fluid solution by laser flash photolysis of alpha-azido acetophenone derivatives, 1. Alphazides 1 contain an intramolecular triplet sensitizer, which ensures formation of the triplet alkyl nitrene by bypassing the singlet nitrene intermediate. At room temperature, azides 1 cleave to form benzoyl and methyl azide radicals in competition with triplet energy transfer to form
我们报告了通过α-叠氮基苯乙酮衍生物的激光闪光光解法对液体溶液中的三重态烷基氮的首次检测。1。叠氮化物1包含分子内三重态敏化剂,可通过绕过单重态氮烯中间体确保三重态烷基氮的形成。在室温下,叠氮化物1裂解形成苯甲酰基和叠氮化物自由基,与三重态能量转移竞争形成三重态烷基氮。主要的光产物3是由于三重烷基亚硝基被苯甲酰基所拦截而产生的。三线态烷基腈中间体也被分子氧捕获,得到相应的2-硝基苯基乙酮。1的激光闪光光解表明,三线态烷基腈具有约300 nm的吸收。通过在氩气基质中获得它们的UV和IR光谱,进一步表征了三线态烷基氮烯。(13)C和(15)N同位素标记研究使我们能够表征1201 cm(-)(1)处的丁腈中间体的CN延伸。