ChemInform Abstract: Synthesis and Investigation of Nucleophilic Reaction of Vicinal Bis(fluorosulfonyloxy)perfluoroisononenes.

✍ Scribed by E. A. Avetisyan; V. F. Cherstkov; B. L. Tumanskii; S. R. Sterlin

• Book ID: 101872833
• Publisher: John Wiley and Sons
• Year: 2010
• Weight: 36 KB
• Volume: 30
• Category: Article
• ISSN: 0931-7597
• DOI: 10.1002/chin.199914084

✦ Synopsis

Synthesis and Investigation of Nucleophilic Reaction of Vicinal Bis(fluorosulfonyloxy)perfluoroisononenes.

-Addition of peroxodisulfuryl difluoride to perfluoroisononene (I) under electrolytic conditions affords a stable radical (II) which is transformed to bis(fluorosulfate) (III) at higher temperatures. In contrast, addition of peroxodisulfuryl difluoride to the isomeric perfluoroisononene (VIII) gives no stable radical since its formation proceeds more slowly than the transformation to bis(fluorosulfate) (IX). Bis(fluorosulfates) (III) and (IX) are converted to ketofluorosulfates [cf. (VII)] on reaction with weak nucleophiles. Under the action of CsF they undergo a "haloform" type cleavage to furnish perfluoroalkenyl fluorosulfates (IV) and (X) as well as some secondary products. Addition of peroxodisulfuryl difluoride to the isomeric perfluoroisononene (XII) affords a sterically constrained adduct which subsequently undergoes homolytic cleavage to form perfluoroketone (XIII) and bis(fluorosulfate) (XIV). -(AVETISYAN, E. A.; CHERSTKOV,