关键词: 3,3’-偶氮双(6-氨基-1,2,4,5-四嗪), 键级, 合成, 几何构型, 理论计算, 热力学性质

A novel synthetic approach of 3,3’-azobis(6-amino-1,2,4,5-tetrazine) (DAAT) was firstly devised. Taking 3,6-bis(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine (BDT) as a primary material, DAAT was synthesized by high pressure ammonolysis and potassium permanganate oxidation. Compared with the four-step reaction in the literature, this new approach was reduced to two steps with a yield of 58.1%. The intermediate and DAAT were characterized by elemental analysis, IR and NMR spectra. In order to investigate properties of DAAT at a molecular level, the structure of DAAT was optimized and its properties were calculated by a B3LYP method on 6-31G(d,p) basis set. The steady geometric configuration and bond order were obtained. The vibrational frequencies, IR spectra and thermodynamics properties at different temperatures were obtained on the basis of vibrational analysis, and the relationship between temperature and thermodynamics properties was deduced. The conclusion was drawn that the tetrazine ring and amino group in the DAAT structure were in a plane and were able to build a conjugated π-bond, the calculated fre-quency and intensity were consistent with the experimental values in IR spectra, all thermal energy ( ), thermal capacity ( ) and entropy ( ) would increase with the increase of temperature.

Key words: synthesis, theoretical calculation, geometric configuration, bond order, thermodynamics property, 3,3’-azobis(6-amino-1,2,4,5-tetrazine)