反应详情

温度

-78 °C

This known compound was synthesized according to the procedure of Acheson et al. in J. Chem. Reso; (Miniprint), 1986, 3001-3019 with some modifications. In a 100-mL round bottom flask equipped with a magnetic stir bar, trimethylsilylacetylene (2.9 mL, 21 mmol) was dissolved in dry THF (40 mL) at room temperature under argon atmosphere. The mixture was cooled to −78° C. and n-butyllithium (14 mL of 1.6M in hexane, 22 mmol) was added dropwise over 3 min In a separate round-bottom flask, diethyl chlorophosphate (10 mL) was dissolved in dry THF (10 mL) and was added to the solution of lithium trimethylsilylacetylide dropwise over 25 min via a cannula. The mixture was stirred at −78° C. for 1 h until trimethylsilylacetylene was consumed, as observed by TLC. Two new spots appeared on TLC (Rf=0.8 and 0.6 eluted with ethyl acetate, visualized with KMnO4 stain). The reaction mixture was warmed up to room temperature and saturated aqueous Na2CO3 (100 mL) was added. The mixture was extracted with ethyl acetate (3×50 mL) and concentrated under reduced pressure to give dark brown syrup. This crude material was dissolved in methanol (20 mL) and Na2CO3 (500 mg) was added. Aqueous 1 N NaOH was then added dropwise until the pH the solution was 10 (by a pH paper). Within 30 min, the two spots on TLC converged into the lower Rf spot (Rf=0.6, eluted with ethyl acetate, visualized with KMnO4 stain). The reaction mixture was diluted with water and extracted with ethyl acetate (3×30 mL). The combined aqueous phases were dried over MgSO4 (s), filtered, and concentrated in vacuo. The crude product (pale yellow syrup) was purified by silica gel flash chromatography (30% ethyl acetate in hexane) to give 1.45 g of colorless syrup (yield=45%). The analytical data are identical with those reported by Acheson et al.

1. customThis known compound was synthesized
2. customIn a 100-mL round bottom flask equipped with a magnetic stir bar
3. customwas consumed
4. washTwo new spots appeared on TLC (Rf=0.8 and 0.6 eluted with ethyl acetate, visualized with KMnO4 stain)
5. temperatureThe reaction mixture was warmed up to room temperature
6. additionsaturated aqueous Na2CO3 (100 mL) was added
7. extractionThe mixture was extracted with ethyl acetate (3×50 mL)
8. concentrationconcentrated under reduced pressure
9. customto give dark brown syrup
10. washthe two spots on TLC converged into the lower Rf spot (Rf=0.6, eluted with ethyl acetate, visualized with KMnO4 stain)
11. additionThe reaction mixture was diluted with water
12. extractionextracted with ethyl acetate (3×30 mL)
13. dry with materialThe combined aqueous phases were dried over MgSO4 (s)
14. filtrationfiltered
15. concentrationconcentrated in vacuo
16. customThe crude product (pale yellow syrup) was purified by silica gel flash chromatography (30% ethyl acetate in hexane)