Preparation Of 1,5-Ditosyl-1,5-Diazocane-3,7-Dione

1,5-dinitro-1,5-diazocane-3,3,7,7-tetraamine(HNFX)has two important inter-mediates:1,5-ditosyl-1,5-diazocane-3,7-diol(Ts-diol)and 1,5-ditosyl-1,5-diazocane-3,7-dione(Ts-dione).Both of Ts-diol and Ts-dione are nitrogen-containing heter-ocyclic compounds.Nowadays,nitrogen-containing heterocyclic compounds hav-e been widely used as energetic materials,in the field of military and civil in-dustry.Particularly,high-energy nitrogen heterocyclic compounds often used as energetic components of solid propellants in the field of aerospace,which can greatly improve the energy of propellants and play an important role in the de-velopment of military technology in China.In this paper,the main research objective is to synthesize Ts-diol,and to find a suitable oxidation method to synthesize Ts-dione,then try to optimize the process of synthesizing Ts-diol and Ts-dione.The research of this paper aim to make the preparation for HNFX,a high energy oxidant.The main contents and results of this paper are as follows:1.Ts-diol was synthesized by using p-toluene sulfonamide and epichlorohydrin as raw materials and ethanol as reaction solvent,under the catalysis of strong alkali sodium hydroxide.Three important factors,such as ratio of reactive materials,reaction time and solvent concentration in the reaction were determined by single factor experiment.2.Furthermore,the optimal process conditions for the synthesis of Ts-diol were determined by the response surface methodology The results show that through the response surface methodology,the optimal response corresponding to each factor level can be easily and intuitively obtained,which can be indicated by drawing response surface and contours.The optimum experimental conditions were predicted as follows:reaction time was 9.38 h,sodium hydroxide concentration was 6.06 mol/L,molar ratio of epichlorohydrin to p-toluenesulfonamide was 1.38:1.Under the optimum experimental conditions,the experimental yield of Ts-diol are 22.14%;Compared with the predicted yield 22.87%,the relative error is 3.20%.Ts-diol was characterized by means of some analysis and testing,such as MPT,HPLC,FTIR,~1H-NMR,EA.3.The synthesis of Ts-dione was carried out by using PCC oxidation,CAN oxidation and Swern oxidation.The oxidation of Ts-dione was as follows:Ts-diol was used as the raw material;Dichloromethane was used as the reaction solvent;Chlormatte salt intermediate produced by dimethyl sulfoxide(DMSO)and oxaloyl chloride was used as oxidant;Ts-dione was prepared under the condition of using triethylamine alkalinity at low temperature.4.The factors affecting the synthesis were discussed by single factor test:the molar ratio of DMSO to Ts-diol was 4:1,and the oxidation temperature was-75?;The reaction time was 3 h,and the quenching time of triethylamine was 1.5 h.The yield of synthesized Ts-dione was up to 57.3%under the conditions of the best influencing factors.Ts-dione was characterized by means of HPLC,FTIR,~1H-NMR,EA.