Reaction of perfluoroalkyl iodides(1a—e)with the unsaturated ethers such as 1-ethoxy-1-propene(2),1-methoxy-1-butene(3)under the sulfinatodehalogenation condition gave the correspon-ding 2-(F-alkyl)propanals(5a—e)and butanals(6c,d)very readily in high yield,which were convertedto 2,4-dinitrophenylhydrazones(7a—e,8c,d)and characterized.The reaction products 5 and 6were oxidized with Jone’s reagent and reduced with NaBH_4 in ethanol to give the corresponding acids(9,10)and alcohols(11,12)in good yield.Treatment of compounds 5 and 6 with pyridine gave thedehydrofluorination products 13 and 14.Under the same condition,perfluoroalkyl iodide reactedwith 2-ethoxy-1-propene(4)only to form R_FSO_2Na and R_FH as the major products,but in aqueu-ous DMF(DMF:H_2O=5:1)to give the perfluoroalkylacetone(15)in good yield.Thus,the reac-tion provides a convenient,effective new method for syntheses of these useful organofluorine inter-mediates.