Synthesis Of Trifluoromethyl-substituted Aza-heterocyclic Compounds

Fluorine-containing compounds are widely used in industry, agriculture and medicine. This thesis is mainly focused on preparation ofα-oxo ketene dithioacetals and their applications to synthesis of trifluoromethyl-substituted heterocyclic compounds. Fluorine-containingα-oxo ketene dithioacetals were prepared from trifluoroacetone and were used to react with hydrazine, guanidine and o-phenylenediamine compounds to synthesis tirfluoromethyl-containing aza-heterocycles. The structures of the new compounds were characterized by 1H NMR, 13C NMR, 1 F NMR, MS and IR spectra. Possible mechanisms of the reactions were proposed. This dissertation mainly contains the following aspects:1. Synthesis and structural characterization of fluorine-containingα-oxo ketene dithioacetals as building blocks.1,1,1-Trifluoroacetone was used to react with carbon disulfide and alkyl halide under a basic condition. Two fluorine-containingα-oxo ketene dithioacetal compounds, namely, 1,1,1-trifluoro-4-thiopropionacetal-3-buten-2-one and 1,1,1-trifluoro-4-thiodibenzylacetal-3-buten-2-one, were obtained.2. Synthesis and structural characterization of trifluoromethyl-containing pyrazoles and their derivatives. The prepared 1,1,1-trifluoro-4-thiopropionacetal-3-buten-2-one as a building block was used to react with hydrazines under acidic conditions and three trifluoromethyl-substitued pyrazole compounds were obtained. Then, they were used to react with acyl chlorides in the presence of zinc oxide as catalyst to afford six new derivatives.3. Synthesis and structural characterization of trifluoromethyl-containing diazepines. The prepared 1,1,1-trifluoro-4-thiopropionacetal-3-buten-2-one as a building block was used to react with o-phenylenediamine compounds under heating and microwave conditions, respectively to obtain a diazepine compound 2-trifluoromethyl-4-(3'-mercaptopropylthio)-1,5-benzosdiazepine.4. Synthesis and structural characterization of trifluoromethyl-containing pyrimidines. The prepared 1,1,1-trifluoro-4-thiopropionacetal-3-buten-2-one as a building block was used to react with guanidine in various solvents to obtain three trifluoromethyl-substitued pyrimidine compounds. 5. Synthesis and structural characterization of trifluoromethyl-containing pyridines. The prepared 1,1,1-trifluoro-4-thiodibenzylacetal-3-buten-2-one as a building block was used to react with n-butyl lithium and acetonitrile at low temperature and an intermediate of trifluoromethyl-substituted pyridine, namely,3-hydroxy-3-trifluoromethyl-5-thiodibenzyl-acetal-4-butenenitrile, was obtained.