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 RFSO2Na and RFH 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.