1,1-二硝基乙烷

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

实验步骤: Dinitroethane (2.4 g, 0.02 mol) and potassium hydroxide (1.2 g, 0.22 mol) were dissolved in 50 mL of water to form a first solution. 50 mL of water was added to the first solution to dissolve a salt remaining in the first solution to form a second solution. Octane-3-yl acrylate (8.3 mL, 0.05 mol) was mixed with 50 mL of methanol, and then the mixture was slowly added to the second solution to form a third solution. The third solution was stirred at room temperature for 5 hours. The reaction product was extracted by diethyl ether, and was then distilled under reduced pressure to obtain yellow liquid octane-3-yl 4,4-dinitropentanoate (4.9 g, yield: 80%). to form a first solution to dissolve a salt to form a second solution the mixture was slowly added to the second solution to form a third solution The reaction product was extracted by diethyl ether was then distilled under reduced pressure

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

实验步骤: Dinitroethane (2.4 g, 0.02 mol) and potassium hydroxide (1.2 g, 0.22 mol) were dissolved in 50 mL of water to form a first solution. 50 mL of water was added to the first solution to dissolve a salt remaining in the first solution to form a second solution. Octane-3-yl acrylate (8.3 mL, 0.05 mol) was mixed with 50 mL of methanol, and then the mixture was slowly added to the second solution to form a third solution. The third solution was stirred at room temperature for 5 hours. The reaction product was extracted by diethyl ether, and was then distilled under reduced pressure to obtain yellow liquid octane-3-yl 4,4-dinitropentanoate (4.9 g, yield: 80%). to form a first solution to dissolve a salt to form a second solution the mixture was slowly added to the second solution to form a third solution The reaction product was extracted by diethyl ether was then distilled under reduced pressure

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

实验步骤: Dinitroethane (2.4 g, 0.02 mol) and potassium hydroxide (1.2 g, 0.22 mol) were dissolved in 50 mL of water to form a first solution. 50 mL of water was added to the first solution to dissolve a salt remaining in the first solution to form a second solution. Octyl acrylate (10.2 mL, 0.05 mol) was mixed with 50 mL of methanol, and then the mixture was slowly added to the second solution to form a third solution. The third solution was stirred at room temperature for 4 hours. The reaction product was extracted by diethyl ether, and was then distilled under reduced pressure to obtain yellow liquid octyl 4,4-dinitropentanoate (5.0 g, yield: 82%). to form a first solution to dissolve a salt to form a second solution the mixture was slowly added to the second solution to form a third solution The reaction product was extracted by diethyl ether was then distilled under reduced pressure

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

实验步骤: Dinitroethane (2.4 g, 0.02 mol) and potassium hydroxide (1.2 g, 0.22 mol) were dissolved in 50 mL of water to form a first solution. 50 mL of water was added to the first solution to dissolve a salt remaining in the first solution to form a second solution. Heptyl acrylate (9.5 mL, 0.05 mol) was mixed with 50 mL of methanol, and then the mixture was slowly added to the second solution to form a third solution. The third solution was stirred at room temperature for 3 hours. The reaction product was extracted by diethyl ether, and was then distilled under reduced pressure to obtain yellow liquid heptyl 4,4-dinitropentanoate (4.8 g, yield: 83%). to form a first solution to dissolve a salt to form a second solution the mixture was slowly added to the second solution to form a third solution The reaction product was extracted by diethyl ether was then distilled under reduced pressure

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

实验步骤: Dinitroethane (2.4 g, 0.02 mol) and potassium hydroxide (1.2 g, 0.022 mol) were dissolved in 50 mL of water to form a first solution. 50 mL of water was added to the first solution to dissolve a salt remaining in the first solution to form a second solution. Hexyl acrylate (8.8 mL, 0.05 mol) was mixed with 50 mL of methanol, and then the mixture was slowly added to the second solution to form a third solution. The third solution was stirred at room temperature for 4 hours. The reaction product was extracted by diethyl ether, and was then distilled under reduced pressure to obtain yellow liquid hexyl 4,4-dinitropentanoate (4.5 g, yield: 81%). to form a first solution to dissolve a salt to form a second solution the mixture was slowly added to the second solution to form a third solution The reaction product was extracted by diethyl ether was then distilled under reduced pressure

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

实验步骤: Dinitroethane (2.4 g, 0.02 mol) and potassium hydroxide (1.2 g, 0.022 mol) were dissolved in 50 mL of water to form a first solution. 50 mL of water was added to the first solution to dissolve a salt remaining in the first solution to form a second solution. Hexyl acrylate (8.8 mL, 0.05 mol) was mixed with 50 mL of methanol, and then the mixture was slowly added to the second solution to form a third solution. The third solution was stirred at room temperature for 4 hours. The reaction product was extracted by diethyl ether, and was then distilled under reduced pressure to obtain yellow liquid hexyl 4,4-dinitropentanoate (4.5 g, yield: 81%). to form a first solution to dissolve a salt to form a second solution the mixture was slowly added to the second solution to form a third solution The reaction product was extracted by diethyl ether was then distilled under reduced pressure

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

实验步骤: Dinitroethane (12 g, 0.10 mol) and potassium hydroxide (6 g, 0.11 mol) were dissolved in 100 mL of water to form a first solution. 500 mL of water was added to the first solution to dissolve a salt remaining in the first solution to form a second solution. Butyl acrylate (36 mL, 0.25 mol) was mixed with 300 mL of methanol, and then the mixture was slowly added to the second solution to form a third solution. The third solution was stirred at room temperature for 3 hours. The reaction product was extracted by diethyl ether, and was then distilled under reduced pressure to obtain yellow liquid butyl 4,4-dinitropentanoate (21.5 g, yield: 87%). to form a first solution to dissolve a salt to form a second solution the mixture was slowly added to the second solution to form a third solution The reaction product was extracted by diethyl ether was then distilled under reduced pressure

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

实验步骤: The reaction sequences for preparing these branched polynitroalkyl diols can be summarized as follows: ##STR6## where Z is --C(NO2)3, --CF(NO2)2, --C(NO2)2CH3, or --N(NO2)CH3. The reaction of one mole of trinitromethane with one mole of gamma-crotonolactone under the reaction conditions of example 1 produces 4-hydroxy-3-(trinitromethyl)butyric acid, gamma-lactone which is reduced by borane-tetrahydrofuran to produce 2-(trinitromethyl)-1,4-butanediol as shown in example 3. Similarly, the reaction of one mole of fluorodinitromethane with gamma-crotonolactone under the reaction conditions of example 2 produces 4-hydroxy-3-(fluorodinitromethyl)butric acid, gamma-lactone which is reduced by borane-tetrahydrofuran to produce 2-(fluorodinitromethyl)-1,4-butanediol as shown in example 4. Using the same procedure, 1,1-dinitroethane and gamma-crotonolactone can be used to produce 2-(1,1-dinitroethyl)-1,4-butanediol and methyl nitramine and gamma-crotonolactone can be used to produce 2-(methylnitraza)-1,4-butanediol.

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

实验步骤: Triethylamine was added dropwise to a solution of 1.4 g (0.010 mol) of dimethyl methylenemalonate and 1.6 g (0.0133 mol) of 1,1-dinitroethane in 15 ml of ether at 0°, until yellow coloration persisted in the solution. The solution was allowed to stand 1 hr at ambient temperature and was then washed with 10% sodium bicarbonate, 1 N hydrochloric acid and water. The solution was dried over sodium sulfate, and the solvent was removed under vacuum. Column chromatography on a 100 g column of silica gel (CCl4 --CH2Cl2) and recrystallization of the product (methylene chloride-hexane, -78°) gave 1.9 g (72%) of dimethyl 2,2-dinitropropylmalonate, a white crystalline solid, mp 44°: NMR (CDCl3) 3.75 (s, 6 H, CH3), 3.1-3.5 (m, 3 H, CHCH2) and 2.13 (s, 3 H, C--CH3); IR (neat) 1730 (C=O) and 1570 cm-1 (NO2). was then washed with 10% sodium bicarbonate, 1 N hydrochloric acid and water The solution was dried over sodium sulfate the solvent was removed under vacuum Column chromatography on a 100 g column of silica gel (CCl4 --CH2Cl2) and recrystallization of the product (methylene chloride-hexane, -78°)

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

实验步骤: Carefully controlled reaction conditions are required because the addition of a nucleophile (nitro- or halonitroalkyl ion) to a methylenemalonate ester gives the salt of an alkylmalonate which is itself capable of undergoing further nucleophilic reactions. Nitroform, a strong acid, reacts with diethyl methylenemalonate in aqueous methanol at ambient temperature, without a base as catalyst, to produce diethyl 2,2,2-trinitroethylmalonate. The same conditions may also be used to produce dimethyl 2,2,2-trinitroethylmalonate. The reaction of 1,1-dinitroethane with methylenemalonates does not take place under these conditions, presumably because the nitro compound is not sufficiently ionized. However, the addition of triethylamine to an ether solution of 1,1-dinitroethane and dimethyl methlenemalonate at 0° C. resulted in a 72% yield of dimethyl 2,2-dinitropropylmalonate. In the same manner, diethyl 2,2-dinitropropylmalonate may be prepared. Finally, the addition fluorodinitromethane to methylenemalonates in ether solution in the presence of catalytic amounts of pyridine produces good yields of dimethyl and diethyl 2-fluoro-2,2-dinitroethylmalonates.

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

实验步骤: Dinitroethane (2.4 g, 0.02 mol) and potassium hydroxide (1.2 g, 0.22 mol) were dissolved in 50 mL of water to form a first solution. 50 mL of water was added to the first solution to dissolve a salt remaining in the first solution to form a second solution. Octane-3-yl acrylate (8.3 mL, 0.05 mol) was mixed with 50 mL of methanol, and then the mixture was slowly added to the second solution to form a third solution. The third solution was stirred at room temperature for 5 hours. The reaction product was extracted by diethyl ether, and was then distilled under reduced pressure to obtain yellow liquid octane-3-yl 4,4-dinitropentanoate (4.9 g, yield: 80%). to form a first solution to dissolve a salt to form a second solution the mixture was slowly added to the second solution to form a third solution The reaction product was extracted by diethyl ether was then distilled under reduced pressure

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

实验步骤: Dinitroethane (2.4 g, 0.02 mol) and potassium hydroxide (1.2 g, 0.22 mol) were dissolved in 50 mL of water to form a first solution. 50 mL of water was added to the first solution to dissolve a salt remaining in the first solution to form a second solution. Octyl acrylate (10.2 mL, 0.05 mol) was mixed with 50 mL of methanol, and then the mixture was slowly added to the second solution to form a third solution. The third solution was stirred at room temperature for 4 hours. The reaction product was extracted by diethyl ether, and was then distilled under reduced pressure to obtain yellow liquid octyl 4,4-dinitropentanoate (5.0 g, yield: 82%). to form a first solution to dissolve a salt to form a second solution the mixture was slowly added to the second solution to form a third solution The reaction product was extracted by diethyl ether was then distilled under reduced pressure