Synthesis of perfluoropolyether diacyl peroxides in a fluorous biphasic system

摘要

The reduction of peroxidic PFPEs of formula T-O(CF2CF2O)_x(CF2O)_y(CF2CF2-O-O)_p(UCF2-O-O)_qT' with an average MW = 10~4, and with T and 1= -CF3, -CF2Cl, -COF, -CF2COF, gives rise to PFPE diacyl fluorides. PFPE diacyl (poly)peroxides are obtained by the peroxidation reaction of a diacyl halide in a basic aqueous medium in the presence of H2O2. In this paper, we demonstrate that the oxidation reaction performed using a modified version of the Fluorous Biphase System (mFBS) increases by as much as 3 fold the yield of the corresponding PFPE diacyl peroxide with respect to the same oxidative reaction performed in homogeneous conditions. The hydrolysis rate of the PFPE diacyl halide decreases by as much as a factor of 5. Yields as high as 70 mol% of PFPE diacyl peroxide can be obtained with mFBS.