3-(2,2,2-trinitroethoxy)prop-1-ene

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:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of allyl trinitroethyl ether (111 g, 502 mmol) in chloroform (100 ml) was added to the mechanically stirred mixture of m-chloroperoxybenzoic acid (102 g, 590 mmol) and chloroform (450 ml). The mixture was refluxed at 70° C. for 6 h under nitrogen. The mixture was cooled with an ice bath for 30 min and filtered. The filtrate was concentrated and additional precipitate was filtered out. The filtrate was diluted with methylene chloride, washed with 10% sodium thiosulfate, saturated sodium bicarbonate, water and dried. Solvent was removed under vacuum. The golden yellow liquid residue (109 g) was chromatographed in portions using silica gel and methylene chloride to give 72 g (60% yield) of glycidyl trinitroethyl ether: 1HNMR (CDCl3) 2.64 (d of d, 1H), 2.87 (t, 1H), 3.22 (m, 1H), 3.53 (d of d, 1H), 4.15 (d of d, 1H), 4.85 (AB quartet, 2H) ppm; IR (neat): 3067 (w), 3006 (m), 2932 (m), 1591 (br, vs), 1454 (m), 1340 (m), 1305 (s), 1254 (m), 1161 (m), 1138 (s), 1082 (m), 1032 (w), 988 (w), 945 (w), 900 (m), 880 (m), 855 (m), 804 (s), 782 (m) cm−1. The mixture was cooled with an ice bath for 30 min filtered The filtrate was concentrated additional precipitate was filtered out The filtrate was diluted with methylene chloride washed with 10% sodium thiosulfate, saturated sodium bicarbonate, water dried Solvent was removed under vacuum The golden yellow liquid residue (109 g) was chromatographed in portions

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of allyl alcohol (30 g, 520 mmol) and 2-chloropyridine 60 g, 530 mmol) in methylene chloride (100 ml) was added over 60 min to a stirred solution of trifluoromethanesulfonic anhydride (147 g, 520 mmol) in methylene chloride (350 ml) at 0° C. The mixture was stirred at 0° C. for 3 h and then filtered. The brown allyl triflate solution was stored in a freezer for use in the following reaction. A solution of trinitroethanol (58 g, 320 mmol) in methylene chloride (300 ml) was added, with ice bath cooling, over 30 min to a stirred mixture of one-half of the allyl triflate solution and anhydrous sodium sulfate (80 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 24 hrs 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 24 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 chromatographed using silica gel and methylene chloride, followed by distillation to give allyl trinitroethyl ether, bp. 45° C./0.1 mm Hg, yield 60% (42.7 g) based on the trinitroethanol: HNMR (acetone-d6): 4.30 (t of d, 2H), 5.13 (s, 2H), 5.26 (AB quartet of d, 1H), 5.33 (AB quartet of d, 1H), 5.90 (m, 1H) ppm; IR (neat): 2927 (w), 2877 (w), 1597 (br, vs), 1447 (w), 1425 (w), 1347 (w), 1305 (s), 1194 (w), 1123 (br, m), 1029 (w), 995 (w), 938 (m), 879 (w), 856 (w), 804 (m), 783 (m), 732 (w) cm−1. filtered 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 24 hrs of stirring at ambient temperature another 40 g portion of sodium sulfate and the remaining allyl triflate solution were added stirring was continued for 24 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 chromatographed followed by distillation