.3,3 - Dinitro Heterocyclic Butane And Its Salts And Derivatives, Synthesis, Structure, Theoretical Studies And Thermal Properties

3,3-dinitroazetidine(DNAZ),DNAZ salts and DNAZ derivatives was synthesized, nine kinds of chemical compounds of single crystal were cultured,the structure were measured by a four-circle X-ray diffractometer.The nine kinds of chemical compounds are:N-tertiarybutyl-3,3-dinitroazetidine nitrate(BDNAZ·HNO₃),N-acetyl-3,3-dinitroazetidine(ADNAZ),3,3-dinitroazetidine hydrochloride(DNAZ·HCl),N-formyl-3,3-dinitroazetidine(FDNAZ),1-(2',4'-dinitrobenzene)-3,3-dinitroaze tidine(2,4-DNBDNAZ),1,1'-methylene-bis-(3,3-dinitroazetidine)(DNAZ-CH₂-DNAZ),3,3-dinitro azetidine 4-Amino-1,2,4-triazol-5-one salt(DNAZ·NTO),3,3-dinitroazetidine picrate(DNAZ·PA),3,3-dinitroazetidine 3,5-dinitrosalicylate(DNAZ·3,5-DNSA)。The Density-Functional Theory(DFT)method of the Amsterdam density functional(ADF)was used to calculate the geometry and frequency of the compounds. The geometry,Mayer bond orders,Hishfeld charges of atoms,frontier orbital energy and the main atomic orbital percentage were calculated.The thermal behavior of BDNAZ·HNO₃,DNAZ·HCl,DNAZ-CH₂-DNAZ,DNAZ·NTO,DNAZ·PA and DNAZ·3,5-DNSA was studied under a non-isothermal condition by DSC method.The Kissinger method,Ozawa method,the differential method and the integral method were carried out to determine DNAZ·NTO,DNAZ·PA and DNAZ·3,5-DNSA of kinetic parameters,the apparent activation energy (E)and the pre-exponential(A)in the exothermic processes.The thermal decomposition mechanism function were got,entropy of activation(△S^≠),enthalpy of activation(△H^≠),Gibbs free energy of activation(△G^≠)and critical temperature of thermal explosion(T_b)were obtained.The specific heat capacity of ADNAZ,DNAZ·HCl,2,4-DNBDNAZ,DNAZ·NTO,DNAZ·PA and DNAZ·3,5-DNSA were determined with continuous C_p mode of mircocalorimeter.Using the determined relationship of C_p with temperature T,thermodynamic functions(enthalpy,entropy and Gibbs free energy)of compounds between 283.4～354.9K,relative to the standard temperature 298.15K,were derived through thermodynamic relationship.Using the relationship between C_p and T and the thermal decomposition parameters,DNAZ·NTO,DNAZ·PA and DNAZ·3,5-DNSA of adiabatic time-to-explosion were obtained.