Addition reactions of pentafluorosulfur bromide with unsaturated substrates were studied and four new compounds containing the pentafluorosulfur group have been prepared. The mechanism for these reactions seems to involve a radical addition pathway. In reaction with CH2=CFC1, CF3C≡CH and CH3C≡CH the SF5 radical attacks the carbon atoms carrying the most hydrogens. The reaction with CF2=CHCl is interesting, as by analogy with other fluoroolefins, the SF5 primary attack should occur.at the CHCl group, however, SF5CF2CHC1Br was found as the only product for this reaction. The reaction of SF5Br with CF3C≡CH produced two isomers but with CH3C≡CH only one isomer was forrmed. Analytical data, infrared, nmr .and mass spectra are presented supporting the proposed structures for these new compounds.

Addition reactions of pentafluorosulfur bromide (SF5Br) with fluoroolefins were studied. Three new adducts were prepared, SF5CHFCHC1Br, SF5CH2CH(CF3)Br, SF5CHFCFC1Br. SF5Br and CFC1=CHC1 yielded a small amount of product but attempts to add SF5Br to CF2=FCOF were unsuccessful. The mechanism for these addition reactions seems to involve a free radical addition pathway. Steric factors seem to be important in determining whether SF5Br will add to fluoroolefins. The new compounds, SF5CF(CF3)COF and SF5CF(CF3 )CONH2 have been produced from SF5CF=CF2. Analytical data, infrared, Raman, nmr and mass spectra are presented supporting the proposed structures for these new compounds.