反应详情

温度

-10 °C

12.03 ml (6.077 g, 0.0455 mol) of 3.8N ethylmagnesium bromide in ether was added dropwise to a solution of 9.65 g (0.0379 mol) of 9-(p-methylthiophenoxy)-1,4,7-nonatriyne in 80 ml of anhydrous tetrahydrofuran. The temperature was maintained at -10° C. The reaction mixture was stirred for 1 hour further at 0° C., allowed to warm to room temperature, and then 374 mg of cuprous cyanide were added. The mixture was stirred for 20 additional minutes, heated to 40° C. and then treated with 13.83 g (49.38 mmol) of 7-iodo-5-heptynoic acid ethyl ester in 30 ml of anhydrous tetrahydrofuran.The resulting mixture was stirred for 3 additional hours at 40° C., then poured on to 300 ml of 1N sulfuric acid and ice. After extraction with ether (3×150 ml), the combined extract was concentrated to a small volume and washed several times with Versene solution and water, dried and evaporated in vacuo. The crude material was purified by column chromatography on 125 g of silica gel, using hexane:ethyl acetate (95:5) as eluant, to obtain 16-(p-methylthiophenoxy)-hexadeca-5,8,11,14-tetraynoic acid ethyl ester, as an oil. The product was stored in dry ice.

1. temperatureto warm to room temperature
2. stirringThe mixture was stirred for 20 additional minutes
3. temperatureheated to 40° C.
4. stirringThe resulting mixture was stirred for 3 additional hours at 40° C.
5. extractionAfter extraction with ether (3×150 ml)
6. extractionthe combined extract
7. concentrationwas concentrated to a small volume
8. washwashed several times with Versene solution and water
9. customdried
10. customevaporated in vacuo
11. customThe crude material was purified by column chromatography on 125 g of silica gel