Aerosol direct fluorination of esters and ethers

A series of esters and ethers were perfluorinated utilizing the direct aerosol fluorination technique. All final compounds were perfluorinated starting from their hydrocarbon analog. The following compounds were synthesized: -tetraethylene glycol dimethyl ether, -pentaethylene glycol dimethyl ether, -hexaethylene glycol dimethyl ether, -tertiary butyl methyl ether, -tertiary butyl ethyl ether, -methyl 2-methoxypropanoate and -2-methoxypropanoyl fluoride. The purpose of studying the glyme ethers was to increase the range of molecular weights of compounds that can be perfluorinated with little or no effect on the ether linkage. The glyme ethers were also used to determine fixed mechanical system losses in the reactor. The tertiary butyl system was studied to investigate the probability of rearrangement within the tertiary butyl group during fluorination. No evidence of a rearrangement was observed. The purpose for the fluorination of methyl 2-methoxypropanoate was to test the modifications made on the new one inch vertical reactor system and the effect the modifactions had on formation of acid fluorides from ester cleavage. Continuous modifications were made to the aerosol fluorination system to improve yields and to increase the amount of hydrocarbon injected per hour. The reactor rate was successfully increased and all parameters maximized to 1.5 milliliters per hour, three times the previous rate. All compounds were characterized by infrared spectroscopy, electron impact and chemical ionization mass spectroscopy, ¹⁹F and ¹H nuclear magnetic resonance spectroscopy.