The synthetic process for 2,2-dimethyl-5-nitro-5-nitroso-1,3-dioxane(DMNNDO) was improved by using tri(hydroxymethyl)nitromethane and acetone as starting materials through a "one-pot" method combined with alkali...The synthetic process for 2,2-dimethyl-5-nitro-5-nitroso-1,3-dioxane(DMNNDO) was improved by using tri(hydroxymethyl)nitromethane and acetone as starting materials through a "one-pot" method combined with alkaline hydrolysis and nitrosation reactions. The yield of DMNNDO was increased from 37% to 45%. The structure of DMNNDO was characterized by IR,^1H NMR,^13 C NMR,and elemental analysis. Also the thermal decomposition of DMNNDO was studied by using DSC and TG-DTG to find that there are primarily two exothermic decomposition processes between 90 and 300 oC. The crystal structure of DMNNDO was studied by X-ray single-crystal diffraction for the first time. The molecular structure exists as a dimeric form due to the presence of nitroso group. The crystal belongs to monoclinic system,space group C2/c with a = 14.515(3),b = 9.955(2),c = 11.897(2) °,β = 98.500(3)°,V = 1.6998(2) nm^3,Z = 8,D_c = 1.486 g×cm^-3,μ = 0.128 mm^-1,F(000) = 800,S = 1.055,R = 0.0358 and wR = 0.0917. In particular,DMNNDO could be easily hydrolyzed in hydrous systems and the hydrolysis mechanism in CDCl_3 was revealed by means of NMR monitoring.展开更多
文摘The synthetic process for 2,2-dimethyl-5-nitro-5-nitroso-1,3-dioxane(DMNNDO) was improved by using tri(hydroxymethyl)nitromethane and acetone as starting materials through a "one-pot" method combined with alkaline hydrolysis and nitrosation reactions. The yield of DMNNDO was increased from 37% to 45%. The structure of DMNNDO was characterized by IR,^1H NMR,^13 C NMR,and elemental analysis. Also the thermal decomposition of DMNNDO was studied by using DSC and TG-DTG to find that there are primarily two exothermic decomposition processes between 90 and 300 oC. The crystal structure of DMNNDO was studied by X-ray single-crystal diffraction for the first time. The molecular structure exists as a dimeric form due to the presence of nitroso group. The crystal belongs to monoclinic system,space group C2/c with a = 14.515(3),b = 9.955(2),c = 11.897(2) °,β = 98.500(3)°,V = 1.6998(2) nm^3,Z = 8,D_c = 1.486 g×cm^-3,μ = 0.128 mm^-1,F(000) = 800,S = 1.055,R = 0.0358 and wR = 0.0917. In particular,DMNNDO could be easily hydrolyzed in hydrous systems and the hydrolysis mechanism in CDCl_3 was revealed by means of NMR monitoring.