N-芳基-3-氰基-5-氨基吡唑及其衍生物的合成
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摘要
吡唑类药物因其作用谱广、药效强烈等特点而受到越来越多的关注。论文对吡唑杂环化合物的研究进展、合成、应用等进行了系统的论述,对N-芳基-3-氰基-5-氨基吡唑及其衍生物进行了探索合成。
首先,利用串联法合成了1-(2,6-二氯-4-三氟甲基)苯基-3-氰基-5-氨基吡唑1,体现了串联反应操作简便、无需分离中间体、产率高等优点。探索了氟虫腈即1-(2,6-氯-4-三氟甲基)苯基-3-氰基-4-三氟甲基亚磺酰-5-氨基吡唑的合成。同时,探索合成了1-(2,6-二氯-4-三氟甲基)苯基-3-氰基-5-三氟甲基磺酰氨基吡唑。
其次,由于氨基的活泼性,对化合物1进行了氨基上的修饰：是与醛的缩合反应,二是与酰卤或酸酐的反应,三是与磺酰基化合物的反应。分别进行条件优化,成功合成了三个系列化合物,产率较高。
再次,分别利用氯化亚砜、N-溴代琥珀酰亚胺和N-碘代琥珀酰亚胺与化合物1反应,成功地合成了4-位被氯、溴、碘取代的吡唑化合物,并进行了条件筛选。又进一步分别合成了两个系列的4-氯和4-溴代吡唑的Schiff碱化合物。方法简便,产率也比较高。由于碘离子的逃逸,未能得到4-碘代吡唑的Schiff碱化合物。
Because of their widely using in agriculture and excellent medicinal activity, pyrazole compounds are being more and more noted. This dissertation describes the character, synthesis and application of the N-heterocycle complexes in general. As for N-Aryl-3-cyano-5-amino pyrazole, we explore and search the good methods to synthesize it and its derivatives with higher yield.
Firstly, we synthesized the 1-(2,6-dichloro-4-trifluoromethyl) phenyl-3-cyano-5-aminopyrazole 1 with tandem reaction successfully. The reaction confirms that tandem reaction can react easily with higher yield without distracting the intermediate. Then, we searched the method using trifluoromethyl sulfinyl dichloride or salt of trifluoromethyl sulfinyl to prepare Fipronil in one-step, but without output. At the same time, the paper describes a method for producing the compound named 1-(2,6-dichloro-4-trifluoromethyl)phenyl-3-cyano-5-trifylamino pyrazole.
Secondly, because the amino group is an active group, we made some variation by kinds of methods on the amino group so that could avoid the unnecessary waste of time and materials that should be used to separate different compounds by the amino group. There are three ways: one is to make imines using compound 1 and different aldehydes; the other is to make acylamino pyrazole using acid anhydride, acyl halide; another is to make sulfonyl amino pyrazole using sulfonic halide and so on. We tried to optimize the condition for the synthesis of the above compounds, respectively. Fortunately, the yields of those compounds are satisfying.
Finally, we searched the right reagents and reacting condition to make halogen substituted reaction. Successfully, we made the compound of 4-choro,4-bromo and 4-iodo pyrazole with high yields from sulfur oxychloride, NBS and NIS. Then, taking the good property of Schiff Base into consideration, we attempted to made imine Schiff Base. The reaction of the former two 4-halopyrazole with aldehydes gave excellent yields. The optimized methods by us can not only shorten reaction time but also improve the output of the reaction. Unfortunately, the reaction of 4-iodopyraole with aldehydes were failed because of the escaping of the iodo ion.
首先,利用串联法合成了1-(2,6-二氯-4-三氟甲基)苯基-3-氰基-5-氨基吡唑1,体现了串联反应操作简便、无需分离中间体、产率高等优点。探索了氟虫腈即1-(2,6-氯-4-三氟甲基)苯基-3-氰基-4-三氟甲基亚磺酰-5-氨基吡唑的合成。同时,探索合成了1-(2,6-二氯-4-三氟甲基)苯基-3-氰基-5-三氟甲基磺酰氨基吡唑。
其次,由于氨基的活泼性,对化合物1进行了氨基上的修饰：是与醛的缩合反应,二是与酰卤或酸酐的反应,三是与磺酰基化合物的反应。分别进行条件优化,成功合成了三个系列化合物,产率较高。
再次,分别利用氯化亚砜、N-溴代琥珀酰亚胺和N-碘代琥珀酰亚胺与化合物1反应,成功地合成了4-位被氯、溴、碘取代的吡唑化合物,并进行了条件筛选。又进一步分别合成了两个系列的4-氯和4-溴代吡唑的Schiff碱化合物。方法简便,产率也比较高。由于碘离子的逃逸,未能得到4-碘代吡唑的Schiff碱化合物。
Because of their widely using in agriculture and excellent medicinal activity, pyrazole compounds are being more and more noted. This dissertation describes the character, synthesis and application of the N-heterocycle complexes in general. As for N-Aryl-3-cyano-5-amino pyrazole, we explore and search the good methods to synthesize it and its derivatives with higher yield.
Firstly, we synthesized the 1-(2,6-dichloro-4-trifluoromethyl) phenyl-3-cyano-5-aminopyrazole 1 with tandem reaction successfully. The reaction confirms that tandem reaction can react easily with higher yield without distracting the intermediate. Then, we searched the method using trifluoromethyl sulfinyl dichloride or salt of trifluoromethyl sulfinyl to prepare Fipronil in one-step, but without output. At the same time, the paper describes a method for producing the compound named 1-(2,6-dichloro-4-trifluoromethyl)phenyl-3-cyano-5-trifylamino pyrazole.
Secondly, because the amino group is an active group, we made some variation by kinds of methods on the amino group so that could avoid the unnecessary waste of time and materials that should be used to separate different compounds by the amino group. There are three ways: one is to make imines using compound 1 and different aldehydes; the other is to make acylamino pyrazole using acid anhydride, acyl halide; another is to make sulfonyl amino pyrazole using sulfonic halide and so on. We tried to optimize the condition for the synthesis of the above compounds, respectively. Fortunately, the yields of those compounds are satisfying.
Finally, we searched the right reagents and reacting condition to make halogen substituted reaction. Successfully, we made the compound of 4-choro,4-bromo and 4-iodo pyrazole with high yields from sulfur oxychloride, NBS and NIS. Then, taking the good property of Schiff Base into consideration, we attempted to made imine Schiff Base. The reaction of the former two 4-halopyrazole with aldehydes gave excellent yields. The optimized methods by us can not only shorten reaction time but also improve the output of the reaction. Unfortunately, the reaction of 4-iodopyraole with aldehydes were failed because of the escaping of the iodo ion.
引文
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