Syntheses by Free-Radical Reactions. XII. Reactions of Fluoroacyl Radicals

Aromatic Trifluoromethylation with Metal Complexes

“…Radical perfluoroalkylation of aromatic compounds has been known for a long time . However, as was demonstrated as early as 1960, the formation of diperfluoroalkylated side products is hard to avoid, even if the arene substrate is used in a large excess. Furthermore, radical perfluoroalkylation reactions, as expected, usually exhibit poor positional selectivity, − although a limited number of exceptions exist. ,,− …”

A Preparation of Primary Aliphatic Nitramines

“…The only presently known examples of fluorinated open-chain a,@-diketones are those in which R of R-CO-CO-R is perfluoropropyl,6 perfluoroi~opropyl,~ and octafluorobutyl. 6 The cyclic diketone, perfluorocyclobutane-1,2-dione, has also been described.s The straight-chain compounds were prepared by the condensation of polyfluoroacyl chlorides in the presence of nickel carbonyl to give enediol diesters which pyrolyzed to the a,@-diketones,6 the perfluoroisopropyl compound was made by the addition of oxalyl fluoride to perfluoropropene catalyzed by fluoride and the cyclic member of this series was made by the hydrolysis of 1,2-dimethoxyhexafluorocyclobutane. 8 We have now synthesized the first and simplest member of the series by a new and relatively simple method.…”

“…This procedure appears to complement the method of Emmons and Freeman4 since it is not possible to convert second- 2:1:1 " The aqueous layer was continuously extracted with ether for 20 hr. 6 Phenyllithium in ether was used in place of the ro-butyllithium reagent. c The reactants were added to the reaction mixture in one step.…”