Polyfluoroalkyl sulfines derived from 1,1-dihydropolyfluoroalkanesulfinyl chlorides: Decomposition and [4+2]-cycloaddition reactions

•1,1-Dihydropolyfluoroalkanesulfinyl chlorides were prepared by the oxidative chlorination of polyfluoroalkyl thioacetates.•The dehydrochlorination of these chlorides produced new polyfluoroalkanethial-S-oxides.•Internal fluorinated alkenes were prepared by the thermal decomposition of sulfines.•Convenient preparation of 2-(polyfluoroalkyl)-3,6-dihydro- 2H-thiopyran-1-oxides was elaborated.

A convenient method for the preparation of 1,1-dihydropolyfluoroalkanesulfinyl chlorides has been developed basing on the oxidative chlorination of 1,1- dihydropolyfluoroalkyl thioacetates. The dehydrochlorination of the sulfinyl chlorides leads to the formation of new polyfluoroalkylsulfines (fluorinated thioaldehyde-S-oxides). The thermal decomposition of the sulfines results in formation of the symmetrical polyfluorinated alkenes, whereas the reactions of the sulfines with 1,3-dienes afford 2 -(polyfluoroalkyl)-3,6-dihydro-2H-thiopyran-1-oxides.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slide1,1-Dihydropolyfluoroalkanesulfinyl chlorides were prepared by the oxidative chlorination of 1,1- dihydropolyfluoroalkyl thioacetates. The dehydrochlorination of the sulfinyl chlorides produced unstable polyfluoroalkanethial-S-oxides. The decomposition of the fluorinated thioaldehyde-S-oxides and their [4+2]- cycloaddition with dienes were studied.