John D Anderson

Perfluoroalkyl hypobromites: synthesis and reactivity with some fluoroalkenes

Abstract The first perfluoroalkyl hypobromites have been prepared by the reaction of bromine(I) fluorosulfate with perfluorinated tertiary alkoxides of general formula RfC (CF3)2ONa where RfCF3 or CF3CF2. These hypobromites are of lower thermal stability but they behave similarly to analogous hypochlorites and decompose rapidly above −20 °C to give CF3C(O)CF3 and either CF3Br or CF3CF2Br. New polyfluoroethers generated from the reaction of perfluoroalkyl hypobromites with fluoroalkenes have been characterized by 19F and IH NMR spectroscopy, IR spectroscopy and MS.

Fluorinated diketones from nucleophilic trifluoromethylation of carbonyl compounds and subsequent reactions yielding novel heterocyclic compounds

Abstract Our research has shown that (CH 3 ) 3 SiCF 3 can be employed to generate tertiary alkoxides and alcohols by nucleophilic trifluoromethylation of a variety of fluoroketones and acid fluorides in the presence of metal fluorides. In an effort to extend the usefulness of this chemistry the reaction of (CH 3 ) 3 SiCF 3 with diacyl fluorides was investigated. Our goal was to prepare new fluorinated diols of various chain lengths which would have useful solvent properties; however, we observed the formation of fluorinated diketones, via a cyclic alkoxide intermediate. While the chemistry of highly fluorinated ketones has been reviewed, we have found unusual reactivity with a variety of nucleophiles to give compounds with novel cyclic structures. The preparation, properties and reactivity of these new diketones will be discussed.