The synthesis and chemistry of N-chlorosulfenylaziridines [report]

Michael Hare
2000 unpublished
Thiazyl chloride, the monomer of trichlorotrithiazene, reacts with fluorinated olefins to form N-chlorosulfenylaziridines. Four members of this new class of compounds, CF 3 CFCF 2 NSC1, SF 5 CFCF 2 NSC1, C 4 F 9 0CFCF 2 NSC1, and CF 3 CFCF (CF 3 ) NSCl have been prepared. Fluorine NMR, carbon-13 NMR, mass spectrometry, infrared spectroscopy, and elemental analysis analysis have been used to characterize these compounds. The mechanism proposed for the formation of the aziridines involves an
more » ... es involves an attack on the double bond of the olefin by the thiazyl chloride, which acts as a sulfenylnitrene. This mechanism is consistent with previously reported reactions of aziridine formation by sulfenylnitrenes. 2 Thiazyl chloride does not react with the cyclic olefins perfluorocyclopentene and perfluorocyclobutene. A f luoroolef in with a proton in the allylic position was found to react rapidly in the presence of thiazyl chloride, apparently polymerizing by radical mechanism. The disulfide derivative of CF 3 CFCF 2 NSC1 was prepared by dechlorination in the presence of mercury. Other attempts to form derivatives of N-chlorosulfenylaziridines are described. The dimer of trifluorovinylsulfur pentafluoride, formed by a low-temperature reaction catalyzed by (Me 2 N) 3 S+Me 3 SiF 2 -(TASF), has been analyzed by fluorine and carbon NMR, infrared spectroscopy, and mass spectrometry. The structure of the dimer has now been assigned. A computer program written to assist in the analysis of mass spectra is presented and described.
doi:10.15760/etd.6203 fatcat:bkd74xzqpbawrga6wknr6cly3a