Six-Membered Cyanuric-Thiazyl and Cyanuric-Sulfanuric Ring Systems: Thermal Isomerization of (CF3CH2O)3C2N3S(O) to (CF3CH2O)2(CF3CH2)C2N3S(O)2

13 C NMR spectra of the reaction of Cl 3 C 2 N 3 S ( 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 C 2 N 3 S cleanly. The monosubstituted derivative Cl 2 C 2 N 3 S(OC 6 H 4 Ph-2) was prepared from 7 and NaOC 6 H 4 C 6 H 5 -2 in a 1:1 molar ratio in dioxane. The reaction of 7 with 3 equiv of NaOR (R = CH 3, C 2 H 5, CH 2 CF 3 ) in diethyl ether produces the trisubstituted derivatives (RO) 3 C 2 N 3 S as colorless liquids, which were characterized by IR, 13 C NMR, and mass spectra. The thermolysis of 7 at 220 °C for 4 h gives a viscous, transparent orange gum with the loss of sulfur chlorides. The oxidation of 7 with a mixture of KMnO 4 and CuSO 4 · x H 2 O ( x = 4−6) in CH 2 Cl 2 yields the new hybrid cyanuric−sulfanuric system Cl 3 C 2 N 3 S(O) ( 8 ) as a low melting solid, which was characterized by IR, 13 C NMR, and mass spectra. The thermolysis of (CF 3 CH 2 O) 3 C 2 N 3 S(O), prepared by the reaction of 8 with 3 equiv of NaOCH 2 CF 3 in CH 2 Cl 2, at 175 °C for 5 days results in an O → N migration of a CH 2 CF 3 group to give (CF 3 CH 2 O) 2 (CF 3 CH 2 )C 2 N 3 S(O) 2 ( 14 ). The X-ray structure of 14 shows that this CH 2 CF 3 group is attached to the unique nitrogen atom of a planar C 2 N 3 S ring. Crystals of 14 are triclinic, space group P with a = 11.931(2) Å, b = 10.949(2) Å, c = 22.063(6) Å, α = 89.97(2)°, β = 90.36(2)°, γ = 90.04(1)°, V = 2882.1(9) Å 3, and Z = 8.