2,2-dinitropropan-1-ol

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Using a method similar to example 12, 2,2-dinitropropanol and pentafluorothioacetic acid were reacted to form 2,2-dinitropropyl pentafluorothioacetate (95% yield) mp 22° C.; were reacted

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 7.5 g. (0.1 mole) of glycine, 4.0 g. (0.1 mole) of sodium hydroxide and 50 ml. of water was mixed with 15.0 g. (0.1 mole) of 2,2-dinitropropanol. The temperature rose to 42° and the yellow solution formed was allowed to stand overnight. Upon addition of dilute sulfuric acid a viscous, colorless oil separated and solidified on standing. The product 15.6 g. (92.0%) was collected and recrystallized from methanol-water to give white crystals, m.p. 123°-124°. rose to 42° the yellow solution formed separated (92.0%) was collected recrystallized from methanol-water to give white crystals, m.p. 123°-124°

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 7.5 g. (0.1 mole) of glycine, 4.0 g. (0.1 mole) of sodium hydroxide and 50 ml. of water was mixed with 15.0 g. (0.1 mole) of 2,2-dinitropropanol. The temperature rose to 42° and the yellow solution formed was allowed to stand overnight. Upon addition of dilute sulfuric acid a viscous, colorless oil separated and solidified on standing. The product 15.6 g. (92.0%) was collected and recrystallized from methanol-water to give white crystals, m.p. 123°-124°. rose to 42° the yellow solution formed separated (92.0%) was collected recrystallized from methanol-water to give white crystals, m.p. 123°-124°

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of 2.66 g (66.5 mmoles) of sodium hydroxide in 15 ml of water at 20° was added 5.0 g (66.5 mmoles) of nitroethane. When all the nitroethane dissolved, the solution was cooled to 5°-7° in an ice-water bath and 5.4 g of 37% aqueous formaldehyde (66.5 mmoles) was then added. The cooling bath was removed and the mixture was stirred for 2 hours before the ice-water bath was replaced and 25 ml of ether was added. A solution of 18.3 g of sodium nitrite (0.265 mole) in 30 ml of water was then added followed by solutions of 15.8 g (66.3 mmoles) of sodium persulfate in 30 ml of water and 4.4 g (13.4 mmoles) of potassium ferricyanide in 15 ml of water. The reaction temperature rose from 14° to 35°. The mixture was then stirred at ambient temperature for 1 hour and phases were separated. The aqueous phase was extracted twice with ether and the combined ether extracts were washed with brine and dried. The product was distilled in a short path distillation apparatus to give 6.57 g (65% yield) of 2,2-dinitropropanol. the solution was cooled to 5°-7° in an ice-water bath The cooling bath was removed 25 ml of ether was added rose from 14° to 35° The mixture was then stirred at ambient temperature for 1 hour phases were separated The aqueous phase was extracted twice with ether the combined ether extracts were washed with brine dried The product was distilled in a short path distillation apparatus

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of 2.66 g (66.5 mmoles) of sodium hydroxide in 15 ml of water at 20° was added 5.0 g (66.5 mmoles) of nitroethane. When all the nitroethane dissolved, the solution was cooled to 5°-7° in an ice-water bath and 5.4 g of 37% aqueous formaldehyde (66.5 mmoles) was then added. The cooling bath was removed and the mixture was stirred for 2 hours before the ice-water bath was replaced and 25 ml of ether was added. A solution of 18.3 g of sodium nitrite (0.265 mole) in 30 ml of water was then added followed by solutions of 15.8 g (66.3 mmoles) of sodium persulfate in 30 ml of water and 4.4 g (13.4 mmoles) of potassium ferricyanide in 15 ml of water. The reaction temperature rose from 14° to 35°. The mixture was then stirred at ambient temperature for 1 hour and phases were separated. The aqueous phase was extracted twice with ether and the combined ether extracts were washed with brine and dried. The product was distilled in a short path distillation apparatus to give 6.57 g (65% yield) of 2,2-dinitropropanol. the solution was cooled to 5°-7° in an ice-water bath The cooling bath was removed 25 ml of ether was added rose from 14° to 35° The mixture was then stirred at ambient temperature for 1 hour phases were separated The aqueous phase was extracted twice with ether the combined ether extracts were washed with brine dried The product was distilled in a short path distillation apparatus

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Using a method similar to example 12, 2,2-dinitropropanol and pentafluorothioacetic acid were reacted to form 2,2-dinitropropyl pentafluorothioacetate (95% yield) mp 22° C.; were reacted

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 50 ml single necked, round bottom flask was charged with 20 ml methylene chloride, 0.50 g (7.14 mmole) divinyl ether, 1.07 g (7.14 mmole) 2,2-dinitropropanol (VIII), and 0.1 g red mercuric oxide. The solution was stirred, using a Teflon coated magnetic bar while 100 μl trifluoroacetic acid was added. The reaction flask was then fitted with a water cooled reflux condenser and drying tube filled with Drierite desiccant. The reaction was stirred under reflux (~37° C.) for 16 hours. The methylene chloride solvent was removed in vacuo, leaving a slightly yellow, clear oil. The oil was taken up in 2 ml carbon tetrachloride and placed onto 7.8 g neutral alumina (pH 6.9) packed with carbon tetrachloride into a 15 ml "course" glass sintered funnel. The carbon tetrachloride was removed in vacuo, leaving 0.74 g of crude 2,2-dinitropropyl vinyl ether (IX) which was shown by nuclear resonance spectrometry to be 92 percent pure. was added cooled reflux condenser drying tube filled with Drierite desiccant The reaction was stirred under reflux (~37° C.) for 16 hours The methylene chloride solvent was removed in vacuo leaving a slightly yellow, clear oil The carbon tetrachloride was removed in vacuo

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of 2.66 g (66.5 mmoles) of sodium hydroxide in 15 ml of water at 20° was added 5.0 g (66.5 mmoles) of nitroethane. When all the nitroethane dissolved, the solution was cooled to 5°-7° in an ice-water bath and 5.4 g of 37% aqueous formaldehyde (66.5 mmoles) was then added. The cooling bath was removed and the mixture was stirred for 2 hours before the ice-water bath was replaced and 25 ml of ether was added. A solution of 18.3 g of sodium nitrite (0.265 mole) in 30 ml of water was then added followed by solutions of 15.8 g (66.3 mmoles) of sodium persulfate in 30 ml of water and 4.4 g (13.4 mmoles) of potassium ferricyanide in 15 ml of water. The reaction temperature rose from 14° to 35°. The mixture was then stirred at ambient temperature for 1 hour and phases were separated. The aqueous phase was extracted twice with ether and the combined ether extracts were washed with brine and dried. The product was distilled in a short path distillation apparatus to give 6.57 g (65% yield) of 2,2-dinitropropanol. the solution was cooled to 5°-7° in an ice-water bath The cooling bath was removed 25 ml of ether was added rose from 14° to 35° The mixture was then stirred at ambient temperature for 1 hour phases were separated The aqueous phase was extracted twice with ether the combined ether extracts were washed with brine dried The product was distilled in a short path distillation apparatus

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of allyl alcohol (16 g, 276 mmol) and 2-chloropyridine (32 g, 282 mmol) in methylene chloride (100 ml) was added over 30 min to a stirred solution of trifluoromethanesulfonic anhydride (78 g, 277 mmol) in methylene chloride (200 ml) at 0° C. The mixture was stirred in an ice bath for 3 h, and then filtered cold to remove the salt byproduct. The brown allyl triflate solution was stored in a freezer for use in the following reaction. A solution of 2,2-dinitropropanol (24 g, 160 mmol) in methylene chloride (100 ml) was added, with ice bath cooling, over 15 min to a stirred mixture of one-half of the allyl triflate solution and anhydrous sodium sulfate (50 g). The ice bath was removed. After the mixture was stirred at room temperature for 17 h, sodium sulfate (40 g) and half of the remaining allyl triflate solution were added. After another 8 his of stirring at ambient temperature, another 40 g portion of sodium sulfate and the remaining allyl triflate solution were added, and stirring was continued for 17 h. The mixture was filtered. The solution was washed with saturated sodium bicarbonate solution and with water. The solution was dried over magnesium sulfate and solvent was removed under vacuum. The brown liquid residue was distilled to give 25.7 g of allyl 2,2-dinitropropyl ether, by 50° C./0.1 mm Hg, 84% yield based on dinitropropanol: HNMR (acetone-d6): 2.20 (s, 3H), 4.15 (t of d, 2H), 4.37 (s, 2H), 5.22 (AB quartet, of d, 1H), 5.30 (AB quartet of d, 1H), 5.90 (m, 1H) ppm; IR (neat): 2890 (m), 1573 (br, vs), 1469 (m), 1445 (m), 1424 (m), 1401 (m), 1383 (m), 1349 (m), 1328 (s), 1273 (w), 1230 (w), 1195 (m), 1099 (br, s), 989 (s), 939 (s), 869 (m), 848 (m), 776 (w), 736 (w) cm−1. filtered cold to remove the salt byproduct The brown allyl triflate solution was stored in a freezer for use in the following reaction The ice bath was removed After the mixture was stirred at room temperature for 17 h sodium sulfate (40 g) and half of the remaining allyl triflate solution were added After another 8 his of stirring at ambient temperature another 40 g portion of sodium sulfate and the remaining allyl triflate solution were added stirring was continued for 17 h The mixture was filtered The solution was washed with saturated sodium bicarbonate solution and with water The solution was dried over magnesium sulfate and solvent was removed under vacuum The brown liquid residue was distilled

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of 15 g (0.1 mole) of 2,2-dinitropropanol and 1.5 g (0.05 mole) of s-trioxane in 13 mL of methylene chloride at 0° C., 15 g (98%) of a concentrated sulfuric acid solution was injected with syringe pump over 2 hours. During the reaction, temperature was controlled not to exceed 5° C. After addition was completed, the reaction was stirred for further 30 minutes. Upon completion of the reaction, the reaction solution was quenched with water. The reaction mixture was extracted with 130 mL of methylene chloride, and then, the extract was successively washed with 5% sodium hydroxide aqueous solution (130 mL×4) and saturated sodium chloride aqueous solution (130 mL×2), dried over anhydrous magnesium sulfate, and then filtered. The filtrate was concentrated under reduced pressure. Further evaporation under 60° C., about 10 mmHg for 5 hours gave 12.8 g of BDNPF. During the reaction, temperature to exceed 5° C After addition Upon completion of the reaction the reaction solution was quenched with water The reaction mixture was extracted with 130 mL of methylene chloride the extract was successively washed with 5% sodium hydroxide aqueous solution (130 mL×4) and saturated sodium chloride aqueous solution (130 mL×2) dried over anhydrous magnesium sulfate filtered The filtrate was concentrated under reduced pressure Further evaporation under 60° C.