Studies on sulfinatodehalogenation XXI. A new and convenient syntheses of 2-(F-alkyl) aldehydes, alcohols, acids and ketones

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 corresponding 2-(F-alkyl) propanals (5a–e) and butanals (6c, d) very readily in high yield, which were converted to 2,4-dinitrophenylhydrazones (7a–e, 8c, d) and characterized. The reaction products 5 and 6 were oxidized with Jone's reagent and reduced with NaBH₄ 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 the dehydrofluorination products 13 and 14. Under the same condition, perfluoroalkyl iodide reacted with 2-ethoxy-1-propene (4) only to form R_FSO₂Na and R_FH as the major products, but in aqueuous DMF (DMF: H₂O = 5:1) to give the perfluoroalkylacetone (15) in good yield. Thus, the reaction provides a convenient, effective new method for syntheses of these useful organofluorine intermediates.