Synthesis And Characterization Of Tri(Hydroxymethyl)Nitromethane Derivatives

In this thesis, synthesis and thermal analysis of tris(hydroxymethyl)nitromethane derivatives tris(para-nitrophenyloxymethyl)nitromethane and tris(azidoacetoxymethyl)nitro-methane were studied. The structures of intermediate compounds and title compounds were characterized by1H NMR and IR. In order to obtain the optimal process conditions, the principal effect of each unit reaction were discussed based on reaction mechanism.Tris(hydroxymethyl)nitromethane was synthesized by condensation reaction from formaldehyde. The optimal synthetic processes as follows:nitromethane6.1g(0.1mol), formaldehyde solution21mL(0.314mol), calcium hydroxide solution3.3mL(0.425mol·L-1), reaction time5h at37℃, the yield was88.4%.Tris(para-nitrophenyloxymethyl)nitromethane was synthesized via esterification and nucleophilic substitution reaction with tris(hydroxymethyl)nitromethane as the material. The optimal synthetic processes of esterification reaction as follows:tris(hydroxymethyl) nitromethane15.2g(0.1mol), tosylchloride61g(0.32mol), pyridine100mL, reaction time48h at room temperature. The optimal synthetic processes of nucleophilic substitution reaction as follows:tris(para-tolylsulfonylmethyl)nitromethane6.14g(0.01mol), p-nitrophenol4.87g(0.035mol), potassium carbonate5.53g(0.04mol), DMF50mL, reaction time24h at120℃, the total yield was58%.Tris(azidoacetoxymethyl)nitromethane was synthesized via esterification and nucleophilic substitution reaction with tris(hydroxymethyl)nitromethane as the material. The optimal synthetic processes of esterification reaction as follows:tris(hydroxymethyl) nitromethane1.52g(0.01mol), chloroacetic acid3.31g(0.035mol), p-toluenesulfonic acid0.03g(0.2mmol), dimethylbenzene50mL, heated to reflux. The optimal synthetic processes of nucleophilic substitution reaction as follows:tris(chloroacetyloxymethyl)nitromethane3.8g(0.01mol), sodium azide2.6g(0.04mmol), tetrabutyl ammonium bromide0.07g(0.2mmol), DMSO(90%)30mL, reaction time15h at50℃, the total yield was75.7%.DSC analysis shows that the thermal decomposition peak temperature of tris(para-nitrophenyloxymethyl)nitromethane was340.59℃, the decomposition enthalpy was951.26J·g-1; the thermal decomposition peak temperature of tris(azidoacetoxymethyl) nitromethane was234.36℃, the decomposition enthalpy was1470.53J·g-1. TG analysis shows that tris(para-nitrophenyloxymethyl)nitromethane was decomposed at246℃, the mass loss was62%at500℃; the decomposition process of tris(azidoacetoxymethyl)nitromethane was divided into two stages, the total mass loss was42.759%at500℃.