反应详情

温度

37 °C

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%.

1. customA 250 ml, three-necked, round bottom flask was fitted with mechanical stirrer, addition funnel
2. temperaturereflux condenser
3. customfor providing nitrogen atmosphere
4. stirringAfter stirring
5. temperatureheating at 50° to 55° C. for an additional 75 min
6. temperaturethe reaction mixture was cooled to room temperature
7. extractionThe resulting mixture was extracted four times with 100 ml portions of ether
8. washThe combined ethereal layers were washed ten times with 50 ml portions of 0.6 N HCl
9. dry with materialtwice with 50 ml portions of sodium bicarbonate, dried
10. concentrationconcentrated
11. customresulting in 28.0 g (96% yield), of yellow powder, m.p. 53°-58° C
12. customRecrystallization once from methanol
13. customgave colorless long needle crystals, m.p. 71°-72° C