Synthesis, structures and reactions of cyanuric-sulfanuric heterocycles.

摘要

This thesis focuses on the synthesis, structural characterization, and reactions of cyanuric-sulfanuric (C-N-SVI-N) heterocycles involving eight or sixteen atoms. Oxidation of the corresponding S(IV) ring systems with meta-chloroperoxybenzoic acid, converts S(IV) to S(VI). Characterization of these novel heterocycles is carried out by mass spectrometry, elemental analysis, IR, 1H and 13C NMR Single crystal X-ray crystallography is also used to determine the solid state structures of the rings and the bond lengths, bond angles, and torsion angles are compared to those of the corresponding C-N-SIV-N heterocycles. Several reactions of the eight-membered cyanuric-sulfanuric rings are investigated including thermolysis, photolysis, and reactions with electrophiles.; X-ray crystallography revealed that oxidation results in replacement of the lone pair of electrons on each sulfur by an oxygen atom without significant change in the conformations of the eight- and sixteen-membered rings. In all the systems the sulfur-nitrogen bond lengths are shorter in the oxidized systems, but C-N distances are unaffected.; Thermolysis of the eight-membered rings at approximately 220°C produces a ring contraction with loss of a sulfanuric group to give a six-membered C2N3S ring which is characterized by mass spectrometry, elemental analysis, IR, 1H and 13C NMR.