3,6-位不对称二取代咔唑衍生物的合成研究

摘要

以咔唑为主要合成原料,通过N-烷基化、付克酰基化、硝化以及付克烷基化等反应合成了两个结构新颖的3,6-位不对称二取代咔唑衍生物.探讨了原料摩尔比、催化剂用量、反应温度及反应时间等因素对反应的影响,得到最佳反应条件:(1)傅克酰基化反应:n(N-乙基咔唑):n(三氯化铝):n(乙酰氯)=1:1.2:1.5,反应温度室温,反应时间4h,产品收率82％;(2)硝化反应:n(N-乙基咔唑):n(65％硝酸)=1:1.15,反应温度5～10℃,反应时间2h,产品收率89％；(3)傅克烷基化反应:n(3-乙酰基-N-乙基咔唑):n(氯化锌):n(叔丁基氯)=1:1.5:1.5,反应温度室温,反应时间12 h,产品收率64％.所得产品结构经FTIR、1 H NMR、13C NMR、及MS表征.%With carbazole as mainly synthetic material,two novel compounds of 3,6-disubstituted asymmetric carbazole derivatives were prepared by a serious of reactions, such as N- alkylation,Friedel-Crafts acyla-tion, nitration and Friedel-Crafts alkylation. The factors affected the reactions,such as the mol ratio of substrates, the quantity of catalyst,reaction temperature and reaction time were explored and the optimum reaction conditions are as follows; (1) For the reaction of Friedel-Crafts acylation,with the mol ratio 1 : 1. 2 ':1. 5 of N-ethylcarbazole,anhydrous aluminum chloride and acetyl chloride,82% yield of the product was obtained at room temperature for 4 h;(2) For the reaction of nitration, with the mol ratio 1:1. 15 of the N-ethylcarbazole and 65% nitric,89% yield of the object product was obtained at 5 - 10 °C for 2 h;(3) For the reaction of Friedel-Crafts alkylation, with the mol ratio 1 : 1. 5 : 1. 5 of 3-acetyl-N-ethylcarbazol,anhydrous zinc chloride and tert. -butyl chloride,64% yield of the product was obtained at room temperature for 12 h. The structures of object products were characterized by FTIR、1H NMR、13C NMR and MS.