反应详情

温度

-10 °C

27.15 ml (13.75 g, 0.103 mol) of a 3.8N solution of ethylmagnesium bromide in ether was added dropwise under argon to a cold solution of 15.3g (0.085 mol) of 3-(p-methylthiophenoxy)-1-propyne in 80 ml of anhydrous tetrahydrofuran, at such a rate to maintain the temperature at -10°C. The resulting mixture was stirred for 1 hour and then treated with 677.2mg of cuprous cyanide. After stirring 20 minutes more, a solution of 10.8 g(0.0687 mol) of 1-bromo-2,5-hexadiyne in 25 ml of anhydrous tetrahydrofuranwas added dropwise, maintaining the temperature between 0°-5°C. The reaction mixture was stirred at room temperature for 3 additional hours, and then poured into 150 ml of 1N sulfuric acid and ice. After extraction with ether (3×150 ml) the combined organic extracts were concentrated in vacuo to a small volume, and washed several times with EDTA and then with water, dried over sodium sulfate and evaporated. The crude material was purified by column chromatography on 200 g of silica gel, using hexane:ethyl acetate (95:5) as eluant, and the product crystallized from methylene-chloride-hexane, to yield 9-(p-methylthiophenoxy)-1,4,7-nonatriyne, as an oil. The product was stored in dry ice.

1. stirringAfter stirring 20 minutes more
2. temperaturemaintaining the temperature between 0°-5°C
3. stirringThe reaction mixture was stirred at room temperature for 3 additional hours
4. extractionAfter extraction with ether (3×150 ml) the combined organic extracts
5. concentrationwere concentrated in vacuo to a small volume
6. washwashed several times with EDTA
7. dry with materialwith water, dried over sodium sulfate
8. customevaporated
9. customThe crude material was purified by column chromatography on 200 g of silica gel
10. customthe product crystallized from methylene-chloride-hexane