CHEMISTRY OF ORGANO HALOGENIC MOLECULES .140. ROLE OF THE REAGENT STRUCTURE ON THE TRANSFORMATIONS OF HYDROXY-SUBSTITUTED ORGANIC-MOLECULESWITH THE N-FLUORO CLASS OF FLUORINATING REAGENTS

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: romethyl-4-fluoro- 1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) F-TEDA (1a), N -fluorobis(phenylsulfonyl)amine NSF (1b), and N-fluoropyridinium hepta fluorodiborate-pyridine (1/1) NFP (1c). Methanol is stable, but hydroq uinone is very quickly transformed in acetonitrile to quinone with F-T EDA at room temperature; on the other hand, NSF is less reactive, whil e oxidation with NFP is achieved only at an elevated temperature; a st ructure variation of the hydroquinone derivatives did not influence ox idation. Fluorination was achieved with monohydroxy-substituted aromat ic compounds; a similar trend concerning the reactivity of N-F reagent (1) was also observed in reactions with 1- and 2-naphthol, while 9-ph enanthrol gave 10,10-difluoro-9-(10H)-phenanthrenone with F-TEDA in ac etonitrile and 9,10-phenanthrenequinone with NSF. Dealkylation was obs erved in a reaction with 4-methoxyphenol; although the thio analogue g ave bis(4-methoxyphenyl) disulfide, the reactivity was changed and NSF was more reactive than F-TEDA and NFP.