富勒烯稠合噁唑啉衍生物的合成已建立多种方法,但绝大多数方法仅限于芳香族类底物.发展了一种N,N-二甲基甲酰胺(DMF)促进富勒烯C60与酰胺类底物在碱性条件下合成富勒烯稠合噁唑啉的方法,该方法对脂肪族和芳香族酰胺均具有较好的兼容性,能以27％～62％的收率成功合成了一系列富勒烯稠合噁唑啉衍生物.实验结果表明N,N-二甲基甲酰胺(DMF)在此反应中作为共溶剂,可以显著提高目标化合物的收率.现场可见近红外吸收光谱和对照实验研究表明,富勒烯稠合噁唑啉二负离子是反应的关键中间体,DMF有利于此二负离子的生成并对此二负离子起到稳定作用.电化学性质研究显示,富勒烯稠合噁唑啉产物的噁唑啉环上不含取代基和含芳基取代基的衍生物,其起始还原电位相对于C60无明显变化,但噁唑啉环上含脂肪烷基的衍生物的起始还原电位有较大负移,达到0.1 V.
N,N-Dimethylformamide-Promoted Synthesis of Fullerene-Fused Oxazoline Derivatives
Fullerene-fused oxazoline derivatives have been synthesized by many methods,however,the range of substrates is mainly limited to the aromatic substrates.Herein,a method for the synthesis of fullerene-fused oxazoline derivatives has been developed through the N,N-dimethylformamide(DMF)-promoted reaction of C60 with amides under basic conditions.The method was viable for both aliphatic and aromatic amides,providing the corresponding products in 27％～62％yields.It was found that DMF as a cosolvent could significantly improve the yield of the products.Mechanistic studies indicate that dianionic[60]fullero-oxazoline is key intermediate,and DMF plays a role in stabilizing dianion as demonstrated by in situ visible near infrared spectroscopy and control experiments.The electrochemical property study showed that,to compare with C60,fullerene-fused oxazoline derivatives of unsubstituted or substituted with an aryl group on oxazoline ring displayed only a slightly changed onset reduction potential,however,that for the derivatives decorated by an alkyl group such as Et on the oxa-zoline ring was apparently negatively shifted of up to 0.1 V.
fullerene-fused oxazoline derivativesnucleophilic reactionN,N-dimethylformamidein situ visible near infrared spectroscopyelectrochemical property
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