T. Ono et al., LIQUID-PHASE PHOTOFLUORINATION WITH ELEMENTAL FLUORINE .3. SYNTHESIS OF PERFLUOROCYCLOALKYL ETHERS WITH WITHOUT A CHLORINE SUBSTITUENT, Journal of fluorine chemistry, 75(2), 1995, pp. 197-204
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.