胡椒基类化合物与苯醌光反应的CIDNP研究

Investigation of photochemical reaction of benzodioxoles and benzoquinone(BQ) by CIDNP

光照的1H化学诱导动态核极化 (CIDNP)技术用于研究胡椒基类化合物与苯醌的光化反应。Photo CIDNP谱上胡椒基的亚甲基质子 (—O—CH2 —O— )在氘乙腈中产生发射极化信号 ,在氘苯中产生增强吸收信号 ,证实了在乙腈和苯中分别形成“溶剂分离离子化自由基对 (SSIP)”和中性的半醌 苯并间二氧杂环戊烯自由基对 (RP)。在氘苯中 ,产物三苯基原甲酸酯衍生物的次甲基质子的异常增强吸收 ,表明该产物由中性自由基对 (RP)形成。

Photochemical reactions of benzodioxoles with benzoquinone (BQ) was investigated by photo CIDNP technique. Photo CIDNP measurements showed that solvent separated ion radical pairs (SSIP) were formed in acetonitrile and neural semiquinone benzodioxolyl radical pairs (RP) were formed in benzene as evidenced by the emissive and abnormally enhanced absorptive polarizations of methylenedioxy protons (-O-CH 2-O-)in the regenerated benzodioxoles in CD 3CN and C 6D 6, respectively. Abnormally enhanced absorptions for the methine proton in products of triaryl orthoformate derivatives were also observed in C 6D 6, indicating the formation of the product resulted in radical pair (RP) intermediate.