ORGANOPHOSPHINE INITIATED REACTION OF PERFLUOROALKYL IODIDES WITH ALKENES

perfluoroalkyl iodides reacted with alkenes in acetonitrile solu- tion containing catalytic amount of organophosphine under mild condition to give the corresponding adducts in moderate to good yields.Reaction was shown to involve a free radical mechanism.

Studies on sulfinatodehalogenation——XVIII. The reaction of perfluoroalkyl iodides with α-methylene cyclic ethers

Perfluoroalkyl iodides reacted with various a-methylene oxacycloalkanes in the presence of sodium dithionite to give ring opening adducts. The reaction provided an efficient method for the syntheses of polyfunctional organofluorine compounds.

Studies on sulfinatodehalogenation——ⅪⅩ.The reaction of perfluoroalkyl iodides and perfluoroalkane-sulfonyl bromides with conjugated dienes

The reaction of TbCl_3 with K[2,4-(CH_2)_2C_5H_5] at 0℃ in THF followed by crystalliza- tion at -90℃ led to a pale yellow hexagonal prismatic crystalline product [2,4-[CH_3)_2-η~5-C_5H_5]_(2-) Tb·1/2THF, which is highly sensitive to air and water and rapidly efflorescent at ambient temper- ature. The single Crystal X-ray diffraction data of the compound have been collected at low tem- perature (-60℃) and the crystal structure has been solved by heavy atom method. It belongs to triclinic system, space group Pl with lattice parameters a=8.477 (?),b=12.583 (?),c=12.858 (?), a=118.08°,β=91.38°,γ=108.75°,V=1120.36 (?)~ 3 and Z=2. Least-squares refinement converged to a final value R=0.043. The compound possesses an idealized G_(2h) symmetry、with three 2,4- dimethylpentadienyl ligands bound to the central terbium atom in a pentahapto mode (η~5). Each unit cell contains two molecules of[2,4-(CH_3)_2-η~5-C_5H_5]_3Tb and one molecule of solvent THF, of which the role in the lattice has been discussed in detail.

Studies on sulfinatodehalogenation XVI.Sodium dithionite-initiated addition of perfluoroalkyl iodides to terminal alkynes

Reaction of perfluoroalkyl iodides with a series of alkynes under sulfinatodehalogenation condition gave a mixture of E/Z adducts very readily in high yield, thus constituted a mild, convenient and effective new method for the addition of perfluoroalkyl iodides to alkynes. Under the same con- dition, in the presence of 1-hexyne perfluoroalkyl bromide and 1,1,1-trichlorotrifluoroethane reacted only to give sulfinates as the major products. A radical mechanism was proposed for the addition reaction.

Rongalite-initiated addition of perfluoroalkyl iodides to olefins

Perfluoroalkyl iodides reacted with olefins in aqueous acetonitrile in the presence of Rongalite- sodium bicarbonate under mild conditions to give the corresponding 1:1 adducts in moderate to high yields. The formation of these products and the orientation of the addition seemed to show that radicals took part in the reaction. This provides a convenient method for perfluoroalkylation.

Studies on the reactions of silyl enol ether with perfluoroorganic compounds——I. The reaction of silyl enol ether with perfluoroalkyl iodide

The reaction of silyl enol ethers (la-le) with perfluoroalkyl iodides (2f-2k) initiated with sodium dithionite was studied, α-Perfluoroalkyl ketones (3) were synthesized in excellent yield by this method, α,β-Unsaturated fluorinated ketones (4) were obtained easily by dehydrofluorination of the α-perfluoroalkyl ketones. A radical mechanism was proposed.

Factors Influencing Sulfinatodehalogenation Reactions of Perhalocarbons

The study on the factors influencing sulfinatodehalogenation of perfluorohexyl chloride plus octene-1 by using Na2S2O4/NaHCO3 discovered that among the various solvents tested (e.g. Me2SO, NMP, DMAc, CH3CN, CH3CN/H2O) at different temperatures, Me2SO was found to be the most suitable solvent and the conversion of the chloride was very dependent on the reaction temperature. When Me2SO was used in the reaction of perfluoroalkyl iodides, the reaction temperature could be decreased by 20 ℃ as compared with that carried out in CH3CN/H2O to reach the comparable yields.