C-13 NMR spectra of the reaction of Cl3C2N3S (7) with NaOPh in THF in various molar ratios show that nucleophilic substitution occurs preferentially at sulfur and, for a 1:3 molar ratio, produces (PhO)(3)C2N3S cleanly. The monosubstituted derivative Cl2C2N3S(OC6H4Ph-2) was prepared from 7 and NaOC6H4C6N5-2 in a 1:1 molar ratio in dioxane. The reaction of 7 with 3 equiv of NaOR (R = CH3, C2H5, CH2CF3) in diethyl ether produces the trisubstituted derivatives (RO)(3)C2N3S as colorless liquids, which were characterized by IR, C-13 NMR, and mass spectra. The thermolysis of 7 at 220 degrees C for 4 h gives a viscous, transparent orange gum with the loss of sulfur chlorides. The oxidation of 7 with a mixture of KMnO4 and CuSO4. xH(2)O (x = 4-6) in CH2Cl2 yields the new hybrid cyanuric-sulfanuric system Cl3C2N3S(O) (8) as a low melting solid, which was characterized by IR, C-13 NMR, and mass spectra. The thermolysis of (CF3CH2O)(3)C2N3S(O), prepared by the reaction of 8 with 3 equiv of NaOCH2CF3 in CH2Cl2, at 175 degrees C for 5 days results in an O --> N migration of a CH2CF3 group to give (CF3CH2O)(2)(CF3CH2)C2N3S(O)(2) (14) The X-ray structure of 13 shows that this CH2CF3 group is attached to the unique nitrogen atom of a planar C2N3S ring. Crystals of 14 an triclinic, space group P with a 11.931(2) ft, b = 10.949(2) Angstrom, c = 22.063(6) Angstrom, alpha = 89.97(2)degrees, beta = 90.36(2)degrees, gamma = 90.04(1)degrees, V = 2882.1(9) Angstrom(3), and Z = 8.