Synthesis and conformational study of new S-polyfluoroalkyl dithiocarbamates

• New S-polyfluoroalkyl dithiocarbamates were synthesized.
• N- and S-substituent effects were investigated using variable temperature 1H NMR spectroscopy.
• The barriers to rotation around the NCS bond in these dithiocarbamates were in the range 12–16 kcal/mol.

The synthesis of a series of new S-polyfluoroalkyl dithiocarbamates from isothiocyanates and polyfluoroalkyl thiols is reported. The reaction was carried out in the presence of triethylamine and the are produced in moderate to good yields. These compounds were characterized by NMR, FT-IR and MS techniques. In addition, the conformational s-cis/s-trans isomerisation in these dithiocarbamates was investigated using dynamic NMR experiments. The free energies of activation thus obtained were in the range 12–16 kcal/mol. The effects of N- and S-substituents on the barrier to rotation around the NCS bond in these dithiocarbamates are discussed and compared with those in thiocarbamate analogs.

New S-polyfluoroalkyl dithiocarbamates were synthesized by the reaction of isothiocyanates with polyfluoroalkyl thiols. The barriers to rotation around the NCS bond were in the range 12–16 kcal/mol.Figure optionsDownload as PowerPoint slide