Abstract:

Oxidation of fluoroalkanesulfonyl fluoride/hydrogen peroxide/base/acetone system with six benzyl alcohol derivative substrates was reported. Fluoroalkanesulfonyl fluorides(R_fSO₂F) include 5-H-3-oxa-1,1,2,2,4,4,5,5-octafluoropentanesulfonyl fluoride(HCF₂CF₂OCF₂CF₂SO₂F), perfluorobutanesulfonyl fluoride(n-C₄F₉SO₂F) and perfluorooctanesulfonyl fluoride(n-C₈F₁₇SO₂F). The optimized reaction condition was n(Substrate): n(R_fSO₂F): n(H₂O₂): n(NaOH)=1: 4: 8: 8, solvent was acetone, reaction temperature was 20℃ and reaction time was 24 h. Yield of product ketones was 23%-92%. A plausible mechanism was proposed. Experimental results showed that in-situ generated fluorinatedalkano persulfonic acid intermediate could efficiently oxidize acetone and resulted dimethyl dioxirane could oxidize benzyl alcohol derivatives yiel-ding corresponding ketones. The oxidizing ability of fluoroalkanesulfonyl fluoride/hydrogen peroxide/base/acetone system for the oxidation of benzyl alcohol derivatives is similar to that of the traditional Oxone/CH₃COCH₃ system. A novel method for the in-situ generation of dimethyl dioxirane was developed.

Key words: Fluoroalkanesulfonyl fluoride, Dimethyl dioxirane, Oxidation, Benzyl alcohol derivatives, Ketone