Related Fields of Organic Electrochemistry - Fundamentals and Applications of Organic Electrochemistry - page 328

8.2.4 Electrochemical Perfluorination
Electrochemical perfluorination is a process in
which all the hydrogen atoms in a starting
organic molecule are substituted with fluorine
atoms without elementary fluorine generation
during electrolysis. J.H. Simons at 3M achieved
the electrochemical perfluorination of organic
compounds in anhydrous liquid HF using
nickel electrodes to provide perfluorinated
products for the first time in 1941 [6,7]. He is a
pioneer of electrochemical perfluorination and
this method is called Simons' process. The
process uses an undivided cell at low
temperature to keep HF as a liquid (the boiling
point of HF is 19.5 °C). Electrochemical
perfluorination of organic compounds
containing oxygen, nitrogen or sulfur atoms
forms salts with anhydrous HF, which provide
good conductivity for the anhydrous liquid HF
solution. On the other hand, in the case of
hydrocarbon, salts such as KF and NaF must be
added to impart conductivity and allow the
electrochemical perfluorination process. From
carboxylic acids (its chlorides), sulfonic acids
(its chlorides) and trialkylamines, the
perfluorinated products are obtained in good
yields, as shown in Eqs. 8.5 - 8.7 [8]. However,
in many cases the yield for electrochemical
perfluorination is rather low because of
carbon-carbon bond cleavage during
electrolysis [8]. The products, perfluoroalkyl