反应详情

温度

0 °C

1.61 ml (751 mg, 5.6 mmol) of 3.6N ethylmagnesium bromide in ether was added dropwise, under argon to a solution of 1.34 g (6 mmol) of 9-(m-methylphenoxy)-1,4,7-nonatriyne in 20 ml of anhydrous tetrahydrofuran. The temperature was maintained at 0° C. The reaction mixture was stirred for one hour further at 0° C., then allowed to warm to room temperature, and then 50 mg of cuprous cyanide wasadded. The mixture was stirred for 20 minutes, heated to 40° C. and then 1 g (3.75 mmol) of 7-iodo-5-heptynoic acid methyl ester was added. The resulting mixture was stirred during 4 hours at 40° C. The reaction mixture was then poured into 60 ml of 1N sulfuric acid and ice and the product extracted with ether (3×100 ml). The combined organic extract was concentrated to about 1/5 its original volume and washed several times with EDTA and water, dried over sodium sulfate and evaporated in vacuo. The crude material was purified by column chromatography on 75 g of silica gel, using hexane:ethyl acetate (85:15) as eluant, to obtain 16-(m-methylphenoxy)hexadeca-5,8,11,14-tetraynoic acid methyl ester, as an oil. The product was stored in dry ice.

1. temperatureto warm to room temperature
2. stirringThe mixture was stirred for 20 minutes
3. temperatureheated to 40° C.
4. stirringThe resulting mixture was stirred during 4 hours at 40° C
5. extractionthe product extracted with ether (3×100 ml)
6. extractionThe combined organic extract
7. concentrationwas concentrated to about 1/5 its original volume
8. washwashed several times with EDTA and water
9. dry with materialdried over sodium sulfate
10. customevaporated in vacuo
11. customThe crude material was purified by column chromatography on 75 g of silica gel