반응 #1312

반응 방정식

trimethylsilyl acetylene

6-bromo-3,4-dihydro-4,4-dimethylnaphthalen-1(2H)-one

Compound H

6-bromo-3,4-dihydro-4,4-dimethylnaphthalen-1(2H)-one

K2CO3

→

title compound

6-Ethynyl-3,4-dihydro-4,4-dimethylnaphthalen-1(2H)-one

용매

triethylamine

methanol

반응 조건

후처리

1. 1
   기타The solution mixture was flushed with argon for 5 minutes
2. 2
   기타The reaction mixture was sealed in a pressure tube
3. 3
   기타placed in a preheated oil bath
4. 4
   여과The reaction mixture was then filtered through celite
5. 5
   세척washed with Et2O
6. 6
   농축the filtrate concentrated in vacuo
7. 7
   기타to give crude 6-(2-trimethylsilyl)ethynyl-3,4-dihydro-4,4-di-methyl-naphthalen-1(2H)-one
8. 8
   여과filtered
9. 9
   농축The filtrate was concentrated in vacuo
10. 10
    workup.ADDITIONdiluted with Et2O (100 ml)
11. 11
    세척washed with water (10 ml), 10% HCl (10 ml) and brine (10 ml)
12. 12
    건조dried over MgSO4
13. 13
    농축concentrated in vacuo
14. 14
    기타Purification by column chromatography (silica, 10% EtOAc-hexane)

실험 절차

To a solution (flushed for 15 minutes with a stream of argon) of 13.55 g (53.8 mmol) of 6-bromo-3,4-dihydro-4,4-dimethylnaphthalen-1(2H)-one (Compound H) in 280 ml of triethylamine was added 1.87 g (2.66 mmol) of bis(triphenylphosphine)palladium(II) chloride and 0.53 g (2.66 mmol) of cuprous iodide. The solution mixture was flushed with argon for 5 minutes and then 100 ml (938.7 mmol) of trimethylsilyl acetylene was added. The reaction mixture was sealed in a pressure tube and placed in a preheated oil bath (100° C.) for 24 hours. The reaction mixture was then filtered through celite, washed with Et2O and the filtrate concentrated in vacuo to give crude 6-(2-trimethylsilyl)ethynyl-3,4-dihydro-4,4-di-methyl-naphthalen-1(2H)-one. To a solution of this crude TMS-acetylenic compound in 50 ml of methanol was added 2.8 g (20.3 mmol) of K2CO3. The mixture was stirred for 8 hours at ambient temperature and then filtered. The filtrate was concentrated in vacuo, diluted with Et2O (100 ml), washed with water (10 ml), 10% HCl (10 ml) and brine (10 ml), dried over MgSO4 and concentrated in vacuo. Purification by column chromatography (silica, 10% EtOAc-hexane) yielded the title compound as a white solid.

출처