Research On Synthesis Of Novel 4,6-Disubstituted-3,4-Dihydropyrimidin-2(1H)-(Thio) One Derivatives

The 3,4-dihydropyrimidin-2(1H)-(thio)ones were synthesized by Biginelli reaction.This reaction was the simplest and most efficient method of synthesizing 3,4-dihydropyrimidin-2(1H)-(thio)ones.Carbazole compounds were N-containing heterocyclic compounds with a rigid conjugated plane and had a good electron-donating ability.Therefore,they were widely used in the fields of photoelectric materials,medicines and organic pigments.Ferrocene compounds belonged to metal organic compounds and had a wide range of applications in material additives,medicines and catalysts.The main topic of this project was the synthesis of 3,4-dihydropyrimidin-2(1H)-(thio)ones containing carbazolyl and ferrocenyl groups via Biginelli reaction from the three components of aromatic aldehydes,ketones and urea(thiourea)under acidic condition.The synthesized compounds were expected to be applied to medicine and material fields.(1)Eight kinds of 9-alkylcarbazole compounds were synthesized using carbazole as raw material,DMF or DMSO as solvent and NaOH or KOH as catalyst and deacid reagent.The reaction conditions were optimized.The structures of the compounds were characterized by FT-IR,1H NMR and 13C NMR.(2)Eight kinds 3-formyl-9-alkylcarbazole compounds were synthesized using 9-alkylcarbazole,DMF and POCl3 by the Vilsmeier-Haack reaction.Acetylferrocene was synthesized via Friedel-Crafts acylation reaction,using ferrocene as raw material,H3PO4 as catalyst and acetic anhydride as acylating agent and solvent.The synthesized compounds were characterized by FT-IR,1H NMR and 13C NMR.The effects of the molar ratio,catalyst and reaction temperature were explored,and the reaction conditions were optimized.The optimum conditions for the synthesis of 3-formyl-9-alkylcarbazole was as follows:the molar ratio of 9-alkylcarbazole:catalyst was 1:1.1,the catalyst was POCl3,the reaction temperature was 40?,the highest yield can reach 70.1%.The yield of acetylferrocene can reach 89.5%.(3)Using 3-formyl-9-alkylcarbazole,urea(thiourea)and acetylacetone as raw materials,the target products were obtained via Biginelli reaction.These compounds structures were characterized by FT-IR,1H NMR and 13C NMR.The effects of molar ratio,catalyst,solvent and reaction temperature on the yield of the target compounds were explored.and the reaction conditions were optimized.The optimal synthesis conditions were as follows:the molar ratio of 3-formyl-9-alkyl carbazole/urea(thiourea)/acetylacetone/NH2SO3H was 1:1.2:1.2:1,NH2SO3H was used as the catalyst,EtOH was used as the solvent,the reaction temperature was 80?,the reaction time was 2-4 h,the highest yield can reach 84.1%.(4)Using acetyl ferrocene,urea(thiourea)and aromatic aldehyde as raw materials,the target products were obtain via Biginelli reaction.And the compounds structures were characterized by FT-IR,1H NMR and 13C NMR.The effects of molar ratio,catalyst,solvent and reaction temperature on the yield of the compound were explored.And the reaction conditions were optimized.The optimal synthesis conditions were as follows:molar ratio of acetylferrocene/urea(thiourea)/aromatic aldehyde/catalyst was 1:1.2:1.2:0.8,H3BO3 was used as catalyst,the solvent was CH3COOH,the reaction temperature was 100? and reaction time was 1-1.5 h,the highest yield can reach 87.0%.