7-(3,4-二氰基苯氧基)-4-甲基香豆素的合成

The synthesis of 7-(3,4-dicyanophenoxy)-4-methylcoumarins

摘要:

以间苯二酚和乙酰乙酸乙酯为原料在浓硫酸的催化下合成7-羟基-4-甲基香豆素。以 4-硝基邻苯二甲酰亚胺为原料通过氨水催化开环，三氯氧磷脱水制得4-硝基邻苯二甲腈。得到的7-羟基-4-甲基香豆素和4-硝基邻苯二甲腈经过亲核取代反应得到7-(3,4-二氰基苯氧基)-4-甲基香豆素。考察了7-羟基-4-甲基香豆素和4-硝基邻苯二甲腈的投料比、缚酸剂用量、反应温度和反应时间对反应的影响，最优反应条件为7-羟基-4-甲基香豆素、4-硝基邻苯二甲腈和无水碳酸钾的物质的量比为1.4：1.0：1.5，反应温度30 ℃，反应时间14 h，收率为63.7%，并通过红外吸收光谱、核磁共振谱和高效液相色谱（纯度为99.30%）对合成的化合物的结构进行了确证。在此条件下适当放大实验条件得到收率基本在83.1%，比文献报道收率68%要高。

Abstract:

7-hydroxy-4-methylcoumarin was synthesized by resorcinol and ethyl acetoacetate under the catalysis of concentrated sulfuric acid. Then 4-nitro-phthalimide as raw materials was first in the open-loop catalytic ammonia and then by the dehydration with phosphorus oxychloride to get 4-nitro-phthalonitrile. The two obtained compounds by nucleophilic substitution reaction were reacted to form 7-(3,4-dicyanophenoxy)-4-methylcoumarin. By investigating the feed ratio, the amount of acid binding agent, the reaction temperature and reaction time, we confirmed the optimal reaction conditions which were 7-hydroxy-4-methylcoumarin,4-nitro-phthalonitrile and anhydrous potassium carbonate whose molar ratio were 1.4:1.0:1.5 , the temperature 30 ℃, reaction time 14 h and the yield 63.7%. And the structures of compounds synthesized have been confirmed by IR, 1H-NMR and high performance liquid chromatography(purity 99.30 %).By enlarging the experimental conditions, we get the yield about 83.1% which is higher than the reported yield 68%.