Organic Electrode Reactions - Fundamentals and Applications of Organic Electrochemistry - page 156

in anhydrous liquid HF as a solvent with a
nickel anode. This process is called
electrochemical perfluorination and has already
been commercialized (see Chapter 8 ) [66-69].
Electrochemical perfluorination in KF-2HF
melts at a carbon anode has also been
developed for the preparation of perfluorinated
low-molecular-weight organic compounds [69].
Electrochemical partial fluorination, or
selective electrochemical fluorination, is a new
method [69-72]. Since the discharge potential
of the fluoride ion is extremely high (>+2.9 V
vs. SCE at Pt anode in MeCN), the fluorination
proceeds via a (radical) cation intermediate, as
shown in Eq. 5.19 , which is the general pathway
for anodic nucleophilic substitutions.
(5.19)
In this method, fluorine gas is not generated
and no hazardous reagents are required,
therefore this electrochemical fluorination is
much safer than the conventional chemical
method, which often requires hazardous and/or
difficult-to-handle reagents.
Selective electrochemical fluorination can
commonly be achieved in aprotic solvents such
as acetonitrile (MeCN), dichloromethane,