反应详情

A solution of 2-bromo-4-thiophenecarboxaldehyde (45.3 g), 1-dodecyne (43.4 g), and triethylamine (99 ml), in dry tetrahydrofuran (250 ml) was chilled to 5° C. and degassed under nitrogen. bis(Triphenylphosphine)palladium(II)chloride (1.66 g) and copper(I)iodide (0.23 g) were added to the reaction mixture. The mixture was degassed and stirred overnight, under nitrogen, as it was allowed to warm to room temperature. The precipitate was filtered off, washed with ethyl acetate, and the filtrate was evaporated. Ethyl acetate was added to the residue. The solution was washed with brine, dried over magnesium sulfate, filtered, and the filtrate was concentrated. The residue was chromatographed through a silica gel pad eluting with heptane/1% ethyl acetate. The appropriate fractions were collected and evaporated. The residue and that from a similar reaction on a 0.05 mole scale were combined and distilled to give 30.7 g (79.5%), bp 181°-185° C. @0.35 mm Hg.

1. customdegassed under nitrogen
2. additionbis(Triphenylphosphine)palladium(II)chloride (1.66 g) and copper(I)iodide (0.23 g) were added to the reaction mixture
3. customThe mixture was degassed
4. filtrationThe precipitate was filtered off
5. washwashed with ethyl acetate
6. customthe filtrate was evaporated
7. additionEthyl acetate was added to the residue
8. washThe solution was washed with brine
9. dry with materialdried over magnesium sulfate
10. filtrationfiltered
11. concentrationthe filtrate was concentrated
12. customThe residue was chromatographed through a silica gel pad
13. washeluting with heptane/1% ethyl acetate
14. customThe appropriate fractions were collected
15. customevaporated
16. customThe residue and that from a similar reaction on a 0.05 mole scale
17. distillationdistilled
18. customto give 30.7 g (79.5%), bp 181°-185° C.