LIQUID-PHASE PHOTOFLUORINATION WITH ELEMENTAL FLUORINE .3. SYNTHESIS OF PERFLUOROCYCLOALKYL ETHERS WITH WITHOUT A CHLORINE SUBSTITUENT

Liquid-phase photofluorination (LPPF) of 2-phenyl-2-methoxyhexafluorop ropane 1 gave the desired F-2-cyclohexyl-2-methoxypropane, 2, in 21% y ield. An unusual re arranged product, F-2-cyclohexylmethyl isopropyl e ther, 4, and a degradation product, F-2-cyclohexyl propane, 3, were al so produced in 10 and 20% yields, respectively, A plausible reaction m echanism for the formation of the rearranged product 4 was presented. The Cl-containing ethers with cyclic structures, 2-chlorohexafluorocyc lopentenyl cyclopentyl ether, and 2-chlorohexafluorocyclopentenyl 2,2, 3,3,4,4,5,5-octafluoro-n-pentyl ether were also perfluorinated by the LPPF method to give the corresponding Cl-containing F-ethers in fair y ields. The total retention of the chlorine atom through perfluorinatio n and the ability to have a benzene substituent on the substrate are b enificial features of this novel perfluorinating method.