The Application Of Sulfinatodehalogenation In Synthesis And Transformation Of Fluoroalkylated Porphyrins

The dissertation focused on the development of new method for the synthesis of fluoroalkylated porphyrins. Fluoroalkyl group was introduced to porphyrins by sulfinatodehalogenation system. We also studied the application of sulfinatodehalogenation on the fluoroalkylated porphyrins. The dissertation consisted of five chapters.ChapterⅠ. Introduction.ChapterⅡ. Fluoroalkylation of 5,10,15-triarylporphyrins. We investigated fluoroalkylation of 5,10,15-triarylporphyrins with fluoroalkyl halides by sulfinatodehalogenation system. Treatment of 5,10,15-triarylporphyrins with perfluoroalkyl iodides RFI in the presence of Na2S2O4/NaHCO3(molar ratio 1:3:4.5:4.5) in DMSO /CH2Cl2(V/V, 1/1) at 65℃for 3h, gave 2-perfluoroalkyl-5,10,15-triarylporphyrins and 5,10,15-triaryl-20-perfluoroalkylporphyrins. The ratio of the products show that the activity of the meso-position of porphyrins is higher than that of theβ-position of porphyrins.ChapterⅢ. Intramolecular cyclizations of 2- and 20-perfluoroalkyl-5,10,15-triarylporphyrin radicals. When 1,3-diiodohexafluoropropane was subjected to react with 5,10,15-triarylporphyrins, in the presence of Na2S2O4/NaHCO3 (reactant ratio = 1:1.5:4.5:4.5) in DMSO/CH2Cl2(v/v=1/1) at 65℃for 8h, 5,10,15-triaryl-2,20-(hexafluoropropanediyl)porphyrins was obtained. It was found that the intermediates of this reaction are 2-(3-iodohexafluoroalkyl)-5,10,15-triarylporphyrin and 20-(3-iodohexafluoroalkyl)-5,10,15-triarylporphyrin. Because the carbon-chlorine bond of perfluoroalkyl chlorides can be activated in sulfinatodehalogenation system in DMSO at higher temperature, the chlorine atoms of 2-(2-Chlorotetrafluoroethyl)-5,10,15-triphenylporphinato zinc(Ⅱ) and 5,10,15-triphenyl-20-(2-Chlorotetrafluoroethyl)porphinato zinc (Ⅱ) could be homogenously cleaved by Na2S2O4/NaHCO3(reactant ratio=1:10:10) in DMSO at 100℃. Both theβ- tetrafluoroethyl and meso- tetrafluoroethyl radicals produced launch their intramolecular cyclization at respective meso- andβ-positions giving a single fluorinated fused porphyrin, ie. 5,10,15-triphenyl-2,20-(tetrafluoroethanediyl)porphinato zinc(Ⅱ). The hydrolysis of CF2 moiety may be simply accomplished by treating 5,10,15-triaryl-2,20-(hexafluoropropanediyl) porphinato zinc (Ⅱ) (or 5,10,15-triphenyl-2,20-(tetrafluoroethanediyl)porphinato zinc(Ⅱ)) with silica gel at room temperature.ChapterⅣ. Generation of 5,15-perfluoroalkyl-10,20-diphenylporphyrin radicals and their intramolecular cyclizations. Heating 5,15-diphenylporphyrin with 1,3-diiodohexafluoropropane in the presence of Na2S2O4/NaHCO3 in the different molar ratios of material in DMSO-CH2Cl2 (v/v, 1/1) at 65℃yielded three different products. They are a mixture of a mono fluoroalkylated porphyrins (the mixture of 2-(3-iodohexafluoropropyl)-5,15-diphenylporphyrin and 5, 15-diphenyl-10-(3-iodohexafluoropropyl)porphyrin), a mono fluoroalkylated meso,β-fused porphyrin (5,15-diphenyl-2,20-(hexafluoropropanediyl)porphyrins)and a double fluoroalkylated meso,β-fused porphyrin(5,15-diphenyl-2,20:10,12-di(hexafluoropropanediyl)porphyrins). In the absence of NaHCO3, the products were the mixture of 5,15-diphenyl-2,20:10,12-di(hexafluoropropanediyl)porphyrins and 5,15-diphenyl-2,20:8,10-di(hexafluoropropanediyl)porphyrins. Using activation method of C-Cl bonds in perfluoroalkyl chlorides, the mono cyclization of 5-(2- Chlorotetrafluoroethyl)-10,20-diphenylporphyrin and the double cyclization of 5, 15-di(2- Chlorotetrafluoroethyl) -10,20- diphenylporphyrin could also take place.ChapterⅤ. Fluoroalkylation of 5, 15-dipropylporphyrin. Using 5, 15-dipropylporphyrin as the starting material instead of 5,15-diphenylporphyrin, the results were quite similar for the mono fluoroalkylated and the mono cyclization reaction. But for the double fluoroalkylated reactions, in the absence of NaHCO3, the product was 5-(1,2,2-trifluorovinyl)-10,20- dipropylporphyrin; in the presence of NaHCO3, the product was meso,meso-linked bis-(5-perfluoroalkyl-5,15-dihydro-10,20-dipropylporphodimethene).