Synthesis of Thiocyameluric Acid C N S H , Its Reaction to Alkali Metal Thiocyamelurates and Organic Tris(dithio)cyamelurates

Overview

Journal Chemistry

Specialty Chemistry

Date 2019 Sep 25

PMID 31550389

Citations 1

Authors

Christian Posern

Carl-Christoph Hohne

Uwe Bohme

Claudia Vogt

Edwin Kroke

Affiliations

Soon will be listed here.

Abstract

Thiocyameluric acid C N S H , 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 C N (SSR) are reported as well as transformation to alkali metal thiocyamelurates M [C N S ], M=Na, K. These compounds were characterised by FTIR, Raman, solution C and 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 pK values, it could be postulated that the acid strength probably increases in the following order: cyanuric acid (C N O H ) < thiocyanuric acid (C N S H ) < cyameluric acid (C N O H ) < thiocyameluric acid (C N S H ). Single crystals of Na [C N S ]⋅10 H O and K [C N S ]⋅6 H 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.

Citing Articles

Synthesis of Thiocyameluric Acid C N S H , Its Reaction to Alkali Metal Thiocyamelurates and Organic Tris(dithio)cyamelurates.

Posern C, Hohne C, Bohme U, Vogt C, Kroke E Chemistry. 2019; 25(68):15555-15564.

PMID: 31550389 PMC: 6916348. DOI: 10.1002/chem.201903400.

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