芳氧基取代的邻苯二腈衍生物的合成研究

Synthesis of Aryloxy-Substituted Phthalonitrile Derivatives

芳氧基取代的邻苯二腈衍生物是制备金属酞菁的重要前体.以硝基取代的邻苯二腈和对叔丁基苯酚的芳香族亲核取代反应为模型反应,研究芳氧基取代的邻苯二腈衍生物的合成方法.重点考察溶剂、碱、温度、反应物物质的量的比和时间对芳香族亲核取代反应的影响,优选条件为:3-硝基邻苯二腈为底物时,DMF为溶剂,K_(2)CO_(3)作碱,n(3-硝基邻苯二腈)∶n(对叔丁基苯酚)∶n(K_(2)CO_(3))=1∶1.1∶2,65℃,反应时间为6 h;4-硝基邻苯二腈为底物时,DMF为溶剂,K_(2)CO_(3)作碱,n(4-硝基邻苯二腈)∶n(对叔丁基苯酚)∶n(K_(2)CO_(3))=1∶1.05∶2,55℃,反应时间为6 h.通过上述优选条件,高收率地合成了6个邻苯二腈衍生物,并通过核磁氢谱进行表征.此外,讨论了芳香族亲核取代反应的机理.

Aryloxy-substituted phthalonitrile derivatives are important precursors for the preparation of metal phthalocyanines.The nucleophilic aromatic substitution of nitro-substituted phthalonitriles and p-tert-butylphenol were employed as a model reaction to study the synthesis of aryloxy-substituted phthalonitrile derivatives.The effects of solvent,base,temperature,mole ratio of reagents and time on aromatic nucleophilic substitution reaction were investigated.The optimal conditions were:when 3-nitrophthalonitrile was used as substrate,DMF was used as solvent,K_(2)CO_(3)was used as base,n(3-nitrophthalonitrile)∶n(p-tert-butylphenol)∶n(K_(2)CO_(3))=1∶1.1∶2,65℃,and the reaction time was 6 h.When 4-nitrophthalonitrile was used as substrate,DMF was used as solvent,K_(2)CO_(3)was used as base,n(4-nitrophthalonitrile):n(p-tert-butylphenol)∶n(K_(2)CO_(3))=1∶1.05∶2,55℃,and the reaction time was 6 h.Six phthalonitrile derivatives were obtained with high yield by the above optimal conditions,and these phthalonitriles were characterized by 1H-NMR.In addition,the mechanism of nucleophilic aromatic substitution was discussed.