Synthesis, Crystal structure and Properties of 2,3-Bis(hydroxymethyl)-2,3-dinitro-1,4-butanediol Tetranitrate

Starting from nitromethane, 2,3-bis(hydroxymethyl)-2,3-dinitro-1,4-butanediol tetranitrate (BHDBT) was synthesized by the condensation, cyclization, oxidative dimerization, deketalization and nitration in total yield of 36.1%. The structures of BHDBT and its intermediates were characterized by means of H-1 NMR, C-13 NMR, FT-IR and elemental analysis. The synthetic process for 2,3-bis(hydroxymethyl)-2,3-dinitro-1,4-butanediol (BHDB) was improved by using concentrated hydrochloric acid instead of HCl gas. It was found that the optimum conditions for the synthesis of BHDB were as follows: the molar ratio of concentrated hydrochloric acid to BDND is 1.1 : 1, the reaction temperature is 55 degrees C, the reaction time is 4 h, and the yield is up to 94.8%. It was experimentally first found that the protons in BHDB and BHDBT are magnetic nonequivalent. The crystal structure of BHDBT was determined by X-ray single crystal diffractometer. It was shown that the crystal is monoclinic and P2(1)/n space group with unit cell dimensions of a= 0.81944(11) nm, b=2.3365(3) nm, c=0.85838(11) nm, alpha=90 degrees, beta=113.501(2)degrees, gamma=90 degrees, V=1.5072(3) nm(3), Z=4, D-c = 1.852 g.cm(-3), mu=0.189 mm(-1), F(000)=856. Furthermore, the thermal decomposition performance of BHDBT was tested by DSC and TG, and its sensitive properties such as friction sensitivity and impact sensitivity were also investigated. The results showed that the melting point and decomposition peak of BHDBT, which can be used for castable explosive componets and high energy plasticizer for the propellants, are 86.37 and 185.79 degrees C, respectively. The friction sensitivity and impact sensitivity (H-50) of BHDBT are 100% (3.92 MPa, 90 degrees) and 10.0 cm (5 kg), respectively.