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3-取代酰基吡啶可由3-氰基吡啶与相应的卤代烷基镁加成,然后酸化水解来制备.我们曾用该法顺利地制备了一系列的3-取代酰基吡啶,另外还得到少量的4-烷基-3-取代酰基吡啶.但当用氯化苄基镁时,只得到少量的3-取代酰基吡啶,而主要产物却是4-苄基-3-氰基吡啶.为了探讨这两种反应中各组分的相对含量,用高压液相色谱分别对3-氰基吡啶与溴化丁基镁、氯化苄基镁的反应产物进行了分析.为了解释反应产物的异常现象,对反应物进行了量子化学计算,用前线轨道理论对以上反应进行了讨论.
3-Substituted acylpyridines can be prepared by the addition of 3-cyanopyridines to the corresponding alkyl halogens and subsequent acid hydrolysis. We have successfully prepared a series of 3-substituted-acyl-pyridines by this method, in addition to small amounts of 4 -alkyl-3-substituted acylpyridines, but only a small amount of 3-substituted acylpyridines were obtained when benzylmagnesium chloride was used, while the major product was 4-benzyl-3-cyanopyridines. To explore these two The reaction products of 3-cyanopyridine, butylmagnesium bromide and benzylmagnesium chloride were respectively analyzed by high pressure liquid chromatography in order to explain the relative content of each component in the reaction.In order to explain the abnormal phenomenon of the reaction products, The reactants were subjected to quantum chemistry calculations and the above reactions were discussed using frontier orbital theory.