Studies On The Synthesis Of Special Windows Acid And Amine Derivatives Of Special Windows

?-Oxo ketene dithioacetals 1 are a kind of versatile intermediates in organic synthesis. It can be widely used as 1,3-electrophile or nucleophilic reagent to form aromatic and heterocyclic compounds. Tetronic acid, tetronic amine and their derivatives are five-membered heterocyclic compounds along with bio- and pharmacological activities. The scientific and practical demands for such compounds are increasing. Therefore, the combination of ?-oxo ketene dithioacetals and the synthesis of tetronic acid/amine deserves investigation. In this thesis, tetronic acid 4 : 5-pyridinyl-methyl-3-(bis-alkylthio) methylene-furan-2,4-diones was selected for the studies of its reacting orientation firstly.Pyridine carboxaldehydes were selected as electrophiles and their reactions with 4 were investigated.Several Grignard reagents were prepared and used as nuleophilic reagents for the investigation of their reaction with 4 .We found that: (1) The ?-methine-H in tetronic acid is more active than the methylene-H connected with pyridine ring. The electronic effect seems more important than steric effect. (2) The ?-carbonyl carbon is more active than the ester carbonyl carbon and liable to the attack from nucleophilic reagents. Alkylthio groups of tetronic acids have effect,at least to some extent,on their reactivity.??-(Bis-alkylthio)methylene-?-(1-hydroxy-1-?pyridinyl)methylene-?'-pyrinyl methyl-tetronic acid 5,?-(bis-alkylthio) methylene-?-alkyl/aromatic -?-pyrinylmethyl-tetronic acid 7, and some carboxylic acid derivatives 6 were prepared. Next, a range of bis-2-(bis-alkylthio)-methylene-3-carbonyl-5- pyridin yl-4-petene-amide 8 were prepared.from2-(bis-alkylthio)methylene-3- carbonyl-5-pyridinyl/aromatic-4-pentenic acids. Then, tetronic acid derivatives 9 were synthesized via the intramolecular pyridinylethylation of 8. A number of carboxyls, pyridinyls and the unit of ketene dithioacetale were introduced integrally, two tetronic amine(pyrridiones) were connected by an alkyl chain. Due to their tetronic amine framework, these compounds have the potential of bio- and pharmacological activities. Associated with some synthetic advantages such as few preparation steps, mild conditions, simple procedure, these resulting compounds were highly functionized which lead them good candidates to serve as precursors for further synthetic transformations of tetronic amine. The mechanisms for the related reactions and the optimization of reaction conditions were discussed. Further investigation and potential application of these kinds of tetronic acids and amines were prospected in the light of our results and literatures as well. In this paper 24 new compounds were prepared and were characterized by IR and 1H NMR.