Allyl Alcohol → HCID 15103101, compound

Participants

Reaction Conditions

Reaction Steps

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.

Provenance & Evidence