反応 #6637

反応方程式

2,2,4,4-tetramethyl-6-bromothiochroman

Compound 72

2,2,4,4-tetramethyl-6-bromothiochroman

trimethylsilylacetylene

trimethylsilylacetylene

→

title compound

2,2,4,4-Tetramethyl-6-trimethylsilylethynyl-thiochroman

溶媒

triethylamine

反応条件

後処理

1. 1
   その他degassed
2. 2
   その他The reaction mixture was degassed again
3. 3
   その他the tube was sealed
4. 4
   温度to cool to room temperature
5. 5
   その他The mixture was then degassed
6. 6
   温度heated in the sealed tube at 100 degrees C
7. 7
   workup.WAITfor 96 h
8. 8
   温度The mixture was cooled to room temperature
9. 9
   抽出extracted with 3×10 ml of ether
10. 10
    洗浄washed successively with 25 ml of water and 25 ml of saturated sodium chloride solution
11. 11
    乾燥dried (MgSO4) The solvent
12. 12
    その他was removed in vacuo
13. 13
    その他the residue purified by flash chromatography (silica; hexanes followed by 3% ethyl acetate in hexanes)

実験手順

A solution of 600 mg (2.11 mmol) of 2,2,4,4-tetramethyl-6-bromothiochroman (Compound 72) in 1.5 ml of triethylamine was placed in a heavy-walled tube and degassed and then treated under argon with 1.4 g (14.3 mmol) of trimethylsilylacetylene and a powdered mixture of 75 mg (0.39 mmol) of cuprous iodide and 150 mg (0.21 mmol) of bis(triphenylphosphine) palladium (II) chloride. The reaction mixture was degassed again, then placed under argon and the tube was sealed. The mixture was heated at 100 degrees C. for 24 h, allowed to cool to room temperature and then treated with a further 1.4 g (14.3 mmol) of trimethylsilylacetylene and a powdered mixture of 75 mg (0.39 mmol) of cuprous iodide and 150 mg (0.21 mmol) of bis(triphenylphosphine) palladium (II) chloride. The mixture was then degassed, placed under argon and then heated in the sealed tube at 100 degrees C. for 96 h. The mixture was cooled to room temperature and extracted with 3×10 ml of ether. The organic extracts were combined, washed successively with 25 ml of water and 25 ml of saturated sodium chloride solution and then dried (MgSO4) The solvent was removed in vacuo and the residue purified by flash chromatography (silica; hexanes followed by 3% ethyl acetate in hexanes) to give the title compound as a yellow, crystalline solid. PMR (CDCl3): δ 0.23 (9H, s), 1.36 (6H, s), 1.39 (6H, s), 1.94 (2H, s), 7.17 (1H, dd, J~8.2 Hz, 1.8 Hz), 7.25 (1H, d, J~1.8 Hz), 7.30 (1H, d, J~8.2 Hz). MS exact mass, m/l 302.1519 (calcd. for C18H26S Si, 382.1524).

出典