反应详情

To a dry 2-L three-necked flask previously purged with nitrogen was charged 3-bromoquinoline (118.77 g, 570 mmol), propargyl alcohol (71.9 g, 1.28 mol, 2.25 equiv), triethylamine (1500 mL), copper(I) iodide (3.62, 19 mmol, 0.033 equiv) and dichlorobis(triphenyl-phosphine) palladium(II) (6.67 g, 9.5 mmol). The mixture which resulted was mechanically stirred and heated to reflux for 3 hours. Upon cooling the triethylamine solution was mechanically stirred and heated to reflux for 3 hours. Upon cooling, the triethylamine solution was filtered and washed with triethylamine (300 mL). The filtrate was then concentrated under reduced pressure to provide solids which were suspended in 5% aq. NaHCO3 (600 mL) and extracted with ethyl acetate (1×600 mL). The solids which were left after filtration were treated in the same manner. The combined ethyl acetate extracts were stirred with silica gel (15 g) and decolorizing carbon (3 g) before being filtered through a bed of celite. The filtrate was concentrated under reduced pressure to provide a tan colored solid which was vacuum oven dried at 45° C. overnight. The 3-(3-quinolyl)-2-propyn-1-ol was isolated in 92.14 g (88.3% yield). MS(CI): (M+H)+ at 184; 1H NMR (300 MHz CDCl3) δ4.56 (s, 2H), 4.70 (s, broad, 1H), 7.57 (m, 1H), 7.70 (m, 1H), 7.77 (d, 1H), 8.10 (d, 1H), 8.10 (s, 1H), 9.05 (s, 1H).

1. customTo a dry 2-L three-necked flask previously purged with nitrogen
2. customThe mixture which resulted
3. temperatureheated
4. temperatureto reflux for 3 hours
5. stirringwas mechanically stirred
6. temperatureheated
7. temperatureto reflux for 3 hours
8. temperatureUpon cooling
9. filtrationthe triethylamine solution was filtered
10. washwashed with triethylamine (300 mL)
11. concentrationThe filtrate was then concentrated under reduced pressure
12. customto provide solids which
13. extractionextracted with ethyl acetate (1×600 mL)
14. waitThe solids which were left
15. filtrationafter filtration
16. additionwere treated in the same manner
17. stirringThe combined ethyl acetate extracts were stirred with silica gel (15 g)
18. filtrationbefore being filtered through a bed of celite
19. concentrationThe filtrate was concentrated under reduced pressure
20. customto provide a tan colored solid which
21. customdried at 45° C. overnight