On Oxalyl Halide Isothiocyanates Part II: Decarbonylation and Reactivity Studies

The reaction of oxalyl halide isothiocyanate, X (CO) 2 NCS ( X = Cl ( 1 ), Br ( 2 )), with activated carbon proceed via decarbonylation to yield the corresponding carbonyl halide isothiocyanate. Both compounds were isolated as liquids at room temperature and exhibit characteristic resonances in 13 C NMR as well as distinct features in their vibrational spectra. Crystal structures of carbonyl chloride isothiocyanate and carbonyl bromide isothiocyanate are reported, revealing an anti orientation of the isothiocyanate group relative to the carbonyl moiety and distinct intermolecular interactions governing the crystal packing. Furthermore, the reactivity of 1 toward O ‐ and S ‐nucleophiles was investigated, leading to the formation of thiocarbamate derivatives, which were structurally and spectroscopically characterized.