Microwave-assisted Synthesis Of N-Phenylanthranilic Acids And2-(Arylamino)nicotinic Acids By Ullman Type Reaction

Nowadays，most synthetic chemists probably use microwave irradiation techniqueto heat chemical reactions on a laboratory scale. Comparison to conventional heatingmethods, microwave heating has been shown to remarkably accelerate the reaction rate,increase the yields, reduce the by-products and perform the reactions that even notoccur under conventional heating. N-Phenylanthranilic acids and2-(arylamino)nicotinicacids are important nonsteroidal anti-inflammatory drugs (NSAIDs), and crucialintermediates. And their synthesis always induced considerable attention. In thisdissertation, the aim is to develop the novel, simple, efficient and environmentalfriendly method for the synthesis of N-Phenylanthranilic acids and2-(arylamino)nicotinic acids under microwave heating. More specifically, there arethree parts in this dissertation.In the first part, some new N-Phenylanthranilic acids were designed andsynthesized from highly sterically hindered anilines in an efficient and convenientmethod using CuI as catalyst using microwave irradiation and conventional heating,respectively. The high regio-and chemoselectivity was found in the reactions of2,4-dichlorobenzoic acid. What’s more, it was found there was shorter reaction time,fewer by-products under microwave irradiation as compared with conventional heating.In the second part, we have developed a simple, efficient and environmentallyfriendly method for the synthesis of2-arylaminonicotinic acids derivatives by reacting2-chloronicotinic acid with anilines with potassium carbonate as base and water asmedia without any catalyst under microwave irradiation. Several2-arylaminonicotinicacids derivatives were prepared in good yields.In the third part, in hydrothermal reactions at150to180℃,2-(arylamino)nicotinicacids were synthesized by amination of2-chloronictinic acid with aromatic aminesderivatives with potassium carbonate as base. The procedure is an efficient,environmental friendly and practical protocol, and offers a moderate to excellent yieldswith both electron-deficient and electron-rich aromatic amines (up to98%). Moreover,this procedure affords good tolerates to alkylamine and thiophenol.