The Electrochemical Fluorination of Aliphatic Primary Monohydric Alcohols and Aldehydes

Abstract

The perfluorocyclic ethers as well as the perfluoroalkanoyl fluorides were obtained by the electrochemical fluorination of primary monohydric alcohols and aldehydes containing 4–8 carbon atoms. The five-membered rather than the six-membered perfluorocyclic ethers were formed as the cyclic products. The over-all yields of the perfluorocyclic ethers and the perfluoroalkanoyl fluorides from the alcohols were in the range of 10–20%, and 3–12% respectively. Those from the aldehydes were poor because of the formation of a considerable amount of tarry by-products. The physical properties of the perfluorocyclic ethers obtained are also described.

Effect of alkyl chain length on the electrochemical perfluorination of n-alkane (C6–C10) carboxylic acid chlorides

“…Some controversy regarding product distribution is also noticed in the literature [1,3,12]. For example while perfluoro oxolanes are reported to be the predominant cyclic ethers [12], some reports suggest perfluoro oxane as the predominant product [3,4].…”

“…For example while perfluoro oxolanes are reported to be the predominant cyclic ethers [12], some reports suggest perfluoro oxane as the predominant product [3,4]. Abe et al have studied the structure of cyclic ethers formed from ECPF of alcohols and aldehydes [12], a-alkyl substituted carboxylic acids [13] and cyclic ethers [14], with a view to resolving this issue.…”

On the mechanisms of the reactions between some perfluorinated compounds and CH5+-experimental and theoretical approaches

“…Compounds 1-5 (for more details, see Table 1) have been synthesized and purified following the method used by Abe's et al [21,22]…”

The Chemistry of Highly Fluorinated Carbocations

“…Perfluorinated alkanes are very stable toward the action of strong Lewis acids, but fluorine atoms are activated by an α-heteroatom, for example oxygen, and can be exchanged with AlCl 3 among other reagents. −

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