The effect of heteroatoms on the reactions of organic molecules with caesium fluoroxysulphate

Article abstract of DOI:10.1016/S0040-4020(01)90179-6

CsSO₄F reacted at room temperature, or at 35°C in acetonitrile with various heteroatom-containing organic molecules, and three types of transformations have been observed. Fluoro substitution process took place with triphenylmethane, triphenylsilane, triphenylchlorosilane, 4-tert-butylphenol, benzaldehyde, and octanol, thus forming fluorotriphenylmethane, fluorotriphenylsilane, 2-fluoro-4-tert-butylphenol, benzoyl fluoride, or octanoyl fluoride in high yields. Substitution reaction was accompanied by fluoroaddition process in the case of 2-fluoro-4-tert-butylphenol, where 2,2-difluoro-4-tert-butylcyclohexadienon-4,6- was isolated. CsSO₄F easily oxidised secondary alcohols to ketones, and 1,2-dihydro-4-tert-butylbenzene to quinone derivate. Oxygenation process was observed in the case of triphenylphosphine, and dibenzothiophene, while ethyl iodide was transformed to ethyliodo(III) difluoride. Solvent plays an important role in these reactions, being successfully performed in CH₃CN, and completely inhibited in CH₂Cl₂, while different shapes of the effect on fluorination of various organic molecules were observed by altering solvent nature by successive mixing of CH₃CN with CH₂Cl₂.