38451-14-8

A Novel 2(3H)-thiazolone azines family having RF substituents on the 4,4′-positions were efficiently prepared in good yield. The two-step synthesis involves the preparation of N, N′ -dialkyl-1,2-hydrazinedicarbothioamides and their reaction with bromomethyl perflooroalkyl ketone, resulting in double ring closure. All the members prepared in this new family of compounds form stable radical cations, which enables them to be considered as ideal candidates for electrochemical tuning of light absorption as in electrochromic windows or displays and as redox indicators or mediators.

To extend our previous study aimed at the reactions of chlorodithiophosphoric acid pyridiniumbetaine (py·PS2Cl) with thiosemicarbazide derivatives, we performed the reactions of chlorodithiophosphoric acid pyridiniumbetaine with a new group of polyfunctional nucleophiles – symmetrical and nonsymmetrical derivatives of hydrazine-1,2-bis(thiocarboamide) of general formula R(H)N–C(S)N(H)N(H)C(S)–N(H)R (R?=?methyl, i-propyl, ethyl, t-butyl, phenyl). In analogy to heterocyclic anions obtained with the thiosemicarbazide derivatives, the hydrazine derivatives were expected to form heterobicyclic dianions from the reactions with py·PS2Cl. All the reactions were carried out in acetonitrile in the presence of pyridine to keep the same reaction conditions as with the previous experiments. Four new compounds were prepared and characterized by31P NMR, FTIR, Raman spectroscopy, and single crystal X-ray diffraction. Molecular structures of the products are based on heterobicyclic dianion consisting of two condensed five membered P–N–N–C–N rings, each of them bearing an organic group. Both of the organic groups in heterobicyclic dianion are either identical (Me,iPr) or different (Et/tBu, Et/Ph). The molecular structure of the heterobicyclic dianion with unusual structural features was further examined by quantum chemistry calculations.