Chemistry of Organo Halogenic Molecules. 140. Role of the Reagent Structure on the Transformations of Hydroxy Substituted Organic Molecules with the N-Fluoro Class of Fluorinating Reagents

Abstract Hydroxy-substituted organic molecules were used as target molecules in investigations of the role of the reagent structure on the reactivity of three types of N–F class fluorinating reagents: 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) F-TEDA (1a), N-fluorobis(phenylsulfonyl)amine NSF (1b), and N-fluoropyridinium heptafluorodiborate–pyridine (1/1) NFP (1c). Methanol is stable, but hydroquinone is very quickly transformed in acetonitrile to quinone with F-TEDA at room temperature; on the other hand, NSF is less reactive, while oxidation with NFP is achieved only at an elevated temperature; a structure variation of the hydroquinone derivatives did not influence oxidation. Fluorination was achieved with monohydroxy-substituted aromatic compounds; a similar trend concerning the reactivity of N–F reagent (1) was also observed in reactions with 1- and 2-naphthol, while 9-phenanthrol gave 10,10-difluoro-9-(10H)-phenanthrenone with F-TEDA in acetonitrile and 9,10-phenanthrenequinone with NSF. Dealkylation was observed in a reaction with 4-methoxyphenol; although the thio analogue gave bis(4-methoxyphenyl) disulfide, the reactivity was changed and NSF was more reactive than F-TEDA and NFP.