Synthesis of Thiocyameluric Acid C6 N7 S3 H3 , Its Reaction to Alkali Metal Thiocyamelurates and Organic Tris(dithio)cyamelurates.

Thiocyameluric acid C6 N7 S3 H3 , the tri-thio analogue of cyameluric acid, is a key compound for the synthesis of new s-heptazine (tri-s-triazine) derivatives. Here, two different routes for the synthesis of thiocyameluric acid and its reaction to tris(aryldithio)- and tris(alkyldithio)cyamelurates C6 N7 (SSR)3 are reported as well as transformation to alkali metal thiocyamelurates M3 [C6 N7 S3 ], M=Na, K. These compounds were characterised by FTIR, Raman, solution 13 C and 1 H NMR spectroscopies, thermal gravimetric analysis (TGA) and elemental analysis. The three (de)protonation steps of thiocyameluric acid were investigated by acid-base titration followed via UV/Vis absorption spectroscopy. While it was not possible to determine the three pKa values, it could be postulated that the acid strength probably increases in the following order: cyanuric acid (C3 N3 O3 H3 ) < thiocyanuric acid (C3 N3 S3 H3 ) < cyameluric acid (C6 N7 O3 H3 ) < thiocyameluric acid (C6 N7 S3 H3 ). Single crystals of Na3 [C6 N7 S3 ]⋅10 H2 O and K3 [C6 N7 S3 ]⋅6 H2 O were obtained and the structures analyzed by single crystal X-ray diffraction. Additionally, quantum chemical calculations were performed to get insights into the electronic structure of thiocyameluric acid and to clarify the thiol-thione tautomerism. Based on a comparison of calculated and measured vibrational spectra it can be concluded that thiocyameluric acid and the di- and mono-protonated anions exist in the thione form.