Hydrochloric Acid → 1-(N-carbazolyl)-2,4-heptadecadiyne

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Reaction Conditions

Reaction Steps

A 250 ml, three-necked, round bottom flask was fitted with mechanical stirrer, addition funnel, reflux condenser, thermometer and means for providing nitrogen atmosphere. To the flask was added 0.5 g of hydroxylamine hydrochloride, 0.25 g of cuprous chloride, 15.0 g (0.073 mole) of 3-(N-carbazolyl) propyne (prepared as in Example 2A), 75 ml of dimethylformamide, 12 ml of water, and 12 ml of 70% ethylamine. The resulting mixture was stirred and heated to 37° C., and 21.9 g (0.080 mole) of 1-bromo-1-tetradecyne (from Example 17A) was added dropwise over a period of 30 min at a temperature of 37° to 52° C. After stirring and heating at 50° to 55° C. for an additional 75 min, the reaction mixture was cooled to room temperature and poured into an aqueous solution of 150 ml of sodium chloride containing 5 ml of concentrated HCl. The resulting mixture was extracted four times with 100 ml portions of ether. The combined ethereal layers were washed ten times with 50 ml portions of 0.6 N HCl, twice with 50 ml portions of sodium bicarbonate, dried and concentrated, resulting in 28.0 g (96% yield), of yellow powder, m.p. 53°-58° C. Recrystallization once from methanol gave colorless long needle crystals, m.p. 71°-72° C. I.R. (KBr Pellet) in cm-1 : 3060 (Ar--H), 2920+2850 (CH), 2260 (C≡C), 1620+1600 (C=C), 1480 (CH2), 1460+1330 (CN), 750+720 (Ar H). Anal: Calculated for C29H35N: C, 87.60%; H, 8.87%; N, 3.52%; found: C, 88.32%; H, 8.72%; N, 3.45%.

Provenance & Evidence