N-(hydroxymethyl)-N-methylnitramide

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 1-Hydroxy-2-nitro-2-azapropane (0.52 g, 4.9 mmol) and acetonitrile (0.5 ml) were stirred under nitrogen at -20° C. as 2-nitro-2-azapropyl trifluoroacetate (1.09 g, 5.4 mmol) was added in one portion. The reaction flask was immediately connected to a vacuum pump and brought to 1-2 mm during several minutes. The reaction temperature was allowed to warm to ambient during 21/2 hours, a precipitate forming at about 10° C. After stirring an additional 11/2 hours, the vacuum was removed and cold ether (5 ml) was stirred with the solid mass 5 minutes before filtering bis(2-nitro-2-azapropyl) ether; yield: 0.83 g (87%); m.p. 30°-38.5° C. Recrystallization from ether gave bis(2-nitro-2-azapropyl) ether; yield: 0.55 g (58%); m.p. 38°-41° C. The analytical sample melted at 40.6°-42° C. was added in one portion brought to 1-2 mm during several minutes to warm 2 hours a precipitate forming at about 10° C the vacuum was removed cold ether (5 ml) was stirred with the solid mass 5 minutes before filtering bis(2-nitro-2-azapropyl) ether Recrystallization from ether

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Trifluoroacetic anhydride (80 ml, 118.4 g, 0.56 moles) was added to a stirred solution of 1-hydroxy-2-nitro-2-azapropane (40.0 g, 0.38 moles) in dichloromethane (60 ml) at -5° to 0° C. during 11/2 hours. The resulting solution was then distilled without warming at 20 mm, then to 3 mm. The product was distilled at 1.5 mm, 65° C., to give 2-nitro-2-azapropyl trifluoroacetate; yield: 48 g (63%). The resulting solution was then distilled without warming at 20 mm The product was distilled at 1.5 mm, 65° C.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a stirred mixture of 10.6 g of 2-nitro-2-aza-1-propanol and 25 ml of dichloromethane under a nitrogen atmosphere was added dropwise and with ice-cooling 12 g of acetyl chloride. The cooling bath was removed and the mixture was slowly heated to reflux. After 3 hours the solution was allowed to cool and was then triturated with 50 ml of ice water. The organic phase was separated, dried (MgSO4), and distilled. The product 2-nitro-2-azapropyl acetate had b.p. 56°-57° C. at 0.07 mm Hg. was added dropwise and with ice- The cooling bath was removed the mixture was slowly heated to reflux to cool was then triturated with 50 ml of ice water The organic phase was separated dried (MgSO4) distilled

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The solution of 2-nitro-2-aza-1-propanol in methylene chloride produced in Example 2 was combined with an additional 56 grams of methylnitramine. This mixture was slowly added to 300 ml of stirred concentrated sulfuric acid which had previously been cooled to -5° C. to -10° C. The temperature of the reaction mixture was kept at from 0° C. to -5° C. throughout the controlled addition. After the addition was completed, the mixture was poured into a large excess of ice water. Following the separation of the methylene chloride phase, the water phase was repeatedly extracted with methylene chloride. All the methylene chloride fractions were then combined, twice washed with water, and then dried with magnesium sulfate. The magnesium sulfate was filtered out and then the methylene chloride was removed by evaporation under vacuum, leaving an oily liquid. The oily liquid was converted into solid white crystals of 2,4-dinitro-2,4-diazapentane (m.p. 56° C., 65 grams pure) by precipitation from a chloroform/hexane solvent misture. This mixture was slowly added to 300 ml had previously been cooled to -5° C. to -10° C The temperature of the reaction mixture was kept at from 0° C. to -5° C. throughout the controlled addition After the addition the separation of the methylene chloride phase the water phase was repeatedly extracted with methylene chloride twice washed with water dried with magnesium sulfate The magnesium sulfate was filtered out the methylene chloride was removed by evaporation under vacuum leaving an oily liquid The oily liquid was converted into solid white crystals of 2,4-dinitro-2,4-diazapentane (m.p. 56° C., 65 grams pure) by precipitation from a chloroform/hexane solvent misture

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: An additional mole of methylnitramine is reacted with the 2-nitro-2-aza-1-propanol to produce 2,4-dinitro-2,4-diazapentane. The reactants (in approximately a 1:1 molar ratio) are dissolved in a suitable organic solvent and the resulting solution is added to concentrated sulfuric acid at a controlled rate. The reaction temperature is maintained at a temperature above the freezing point of the concentrated sulfuric acid up to 5° C., but preferably from -5° C. to 0° C. The product 2,4-dinitro-2,4-diazapentane is then isolated by extraction using a suitable organic solvent, washing to remove traces of the acid, evaporating off the solvent, and then recrystallizing the resulting solid. A suitable organic solvent is one that (1) is capable of holding the methylnitramine and 2-nitro-2-aza-1-propanol starting materials and the 2,4-dinitro-2,4-diazapentane product in solution, (2) chemically inert to concentrated sulfuric acid, and (3) essentially immiscible with concentrated sulfuric acid. Suitable solvents include methylene chloride, chloroform, 1,2-dichloroethane, and 1,1,2-trichloroethane. Methylene chloride is the most preferred solvent.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The solution of 2-nitro-2-aza-1-propanol in methylene chloride produced in Example 2 was combined with an additional 56 grams of methylnitramine. This mixture was slowly added to 300 ml of stirred concentrated sulfuric acid which had previously been cooled to -5° C. to -10° C. The temperature of the reaction mixture was kept at from 0° C. to -5° C. throughout the controlled addition. After the addition was completed, the mixture was poured into a large excess of ice water. Following the separation of the methylene chloride phase, the water phase was repeatedly extracted with methylene chloride. All the methylene chloride fractions were then combined, twice washed with water, and then dried with magnesium sulfate. The magnesium sulfate was filtered out and then the methylene chloride was removed by evaporation under vacuum, leaving an oily liquid. The oily liquid was converted into solid white crystals of 2,4-dinitro-2,4-diazapentane (m.p. 56° C., 65 grams pure) by precipitation from a chloroform/hexane solvent mixture. This mixture was slowly added to 300 ml had previously been cooled to -5° C. to -10° C The temperature of the reaction mixture was kept at from 0° C. to -5° C. throughout the controlled addition After the addition the separation of the methylene chloride phase the water phase was repeatedly extracted with methylene chloride twice washed with water dried with magnesium sulfate The magnesium sulfate was filtered out the methylene chloride was removed by evaporation under vacuum leaving an oily liquid The oily liquid was converted into solid white crystals of 2,4-dinitro-2,4-diazapentane (m.p. 56° C., 65 grams pure) by precipitation from a chloroform/hexane solvent mixture

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: An additional mole of methylnitramine is reacted with the 2-nitro-2-aza-1-propanol to produce 2,4-dinitro-2,4-diazapentane. The reactants (in approximately 1:1 molar ratio) are dissolved in a suitable organic solvent and the resulting solution is added to concentrated sulfuric acid at a controlled rate. The reaction temperature is maintained at a temperature above the freezing point of the concentrated sulfuric acid up to 5° C., but preferably from -5° C. to 0° C. The product 2,4-dinitro-2,4-diazapentane is then isolated by extraction using a suitable organic solvent, washing to remove traces of the acid, evaporating off the solvent, and then recrystallizing the resulting solid. A suitable organic solvent is one that (1) is capable of holding the methylnitramine and 2-nitro-2-aza-1-propanol starting materials and the 2,4-dinitro-2,4-diazapentane product in solution, (2) chemically inert to concentrated sulfuric acid, and (3) essentially immiscible with concentrated sulfuric acid. Suitable solvents include methylene chloride, chloroform, 1,2-dichloroethane, and 1,1,2-trichloroethane. Methylene chloride is the most preferred solvent.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Trifluoroacetic anhydride (20 ml, 103.6 g, 0.49 moles) was added to a stirred solution of 1-hydroxy-2-nitro-2-azapropane (40.0 g, 0.38 moles) in dichloromethane (60 ml) at -5° to 0° C. during 11/2 hours. The resulting solution was then distilled without warming at 20 mm, then to 3 mm. The product was distilled at 1.5 mm, 65° C. to give 2-nitro-2-azapropyl trifluoroacetate; yield: 48 g (63%). The resulting solution was then distilled without warming at 20 mm The product was distilled at 1.5 mm, 65° C.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a stirred mixture of 10.6 g of 2-nitro-2-azapropanol and 25 ml of dichloromethane under a nitrogen atmosphere was added dropwise and with ice-cooling 12 g of acetyl chloride. The cooling bath was removed and the mixture was slowly heated to reflux. After 3 hours the solution was allowed to cool and was then triturated with 50 ml of ice water. The organic phase was separated, dried (MG SO4), and distilled. The product 2-nitro-2-azapropyl acetate had b.p. 56°-57° C. at 0.07 mm Hg. was added dropwise and with ice- The cooling bath was removed the mixture was slowly heated to reflux to cool was then triturated with 50 ml of ice water The organic phase was separated dried (MG SO4) distilled