反应详情

A solution of 4-bromo-2-thiazolecarboxaldehyde (14.8 g), 1-dodecyne (14.1 g), and triethylamine (23.5 g) in dry tetrahydrofuran (85 m) was chilled to 5° C. and degassed under nitrogen. bis(Triphenylphosphine)palladium (II) chloride (0.54 g) and copper (I) iodide (0.07 g) were added to the mixture, which was degassed, and stirred, under nitrogen, at room temperature for 2.5 hrs. The reaction mixture was heated at 40° C. for 7 hrs, during which time additional amounts of 1-dodecyne (3.9 g), bis(triphenylphosphine)palladium (II) chloride (0.11 g), and copper (I) iodide (0.02 g) were added. The mixture was cooled to room temperature, the precipitate was collected, and the filter cake was washed with ethyl acetate. The filtrate was diluted with ethyl acetate (300 ml). Water was added in portions, and the organic layer was washed with brine, dried over magnesium sulfate, filtered, and the filtrate was concentrated. The residue was chromatographed on silica gel, eluting with heptane to heptane: 1% ethyl acetate. A portion (1.05 g) of the residue was rechromatographed, eluting with hexane:(0.3 to 1%) ethyl acetate. The appropriate fractions were collected and evaporated to yield 0.79 g (76.5% yield) of product, mp 25.5°-26° C.

1. customdegassed under nitrogen
2. additionbis(Triphenylphosphine)palladium (II) chloride (0.54 g) and copper (I) iodide (0.07 g) were added to the mixture, which
3. customwas degassed
4. temperatureThe reaction mixture was heated at 40° C. for 7 hrs, during which time additional amounts of 1-dodecyne (3.9 g), bis(triphenylphosphine)palladium (II) chloride (0.11 g), and copper (I) iodide (0.02 g)
5. additionwere added
6. temperatureThe mixture was cooled to room temperature
7. customthe precipitate was collected
8. washthe filter cake was washed with ethyl acetate
9. additionThe filtrate was diluted with ethyl acetate (300 ml)
10. additionWater was added in portions
11. washthe organic layer was washed with brine
12. dry with materialdried over magnesium sulfate
13. filtrationfiltered
14. concentrationthe filtrate was concentrated
15. customThe residue was chromatographed on silica gel
16. washeluting with heptane to heptane
17. customA portion (1.05 g) of the residue was rechromatographed
18. washeluting with hexane
19. customThe appropriate fractions were collected
20. customevaporated