反应详情

To a 250 ml flask fitted with a reflux condenser, nitrogen inlet and thermometer were added 4(3-bromophenoxy)benzil (11.08 g, 29.08 mmol), 1-(3-ethynylphenoxy)-3-phenoxybenzene (21.64 g, 75.66 mmol), triethylamine (150 ml), and triphenylphosphine (0.40 g). After stirring at room temperature under a nitrogen atmosphere for 10 minutes, cuprous iodide (Alfa 98%, 0.20 g) and dichlorobis(triphenylphosphine)palladium (II) (0.20 g) were added. The flask was heated to an internal temperature of 90° C. and maintained by oil bath heating under nitrogen until TLC indicated reaction completion (4 hr). The triethylamine was distilled from the residue and the residue was suspended in toluene. The toluene was washed with 15% HCl (560 ml) twice and separated. The organic layer was washed with ethylenediamine (20 ml) by adding the ethylenediamine at room temperature, heating to 60° C. for 0.5 h and cooling. Water (250 ml) was added and the toluene was separated from the aqueous layer. The ethylenediamine wash was repeated once more. After washing with water (3×500 ml), the organic layer was dried over anhydrous magnesium sulfate (3.00 g) and the toluene distilled by rotary evaporation at reduced pressure to give a dark brown oil. The oil was dissolved in 4:1 hexane:methylene chloride and chromatographed on a silica gel column (Woelm DCC, 230 g, 5 cm dia×25 cm H) using 4:1 hexane:methylene chloride as the eluent. The product was dried in a 70° C. oven under reduced pressure to afford a light brown tacky oil (7.52 g, 44%).

1. customTo a 250 ml flask fitted with a reflux condenser, nitrogen inlet
2. temperatureThe flask was heated to an internal temperature of 90° C.
3. temperaturemaintained by oil bath
4. temperatureheating under nitrogen until TLC
5. customreaction completion (4 hr)
6. distillationThe triethylamine was distilled from the residue
7. washThe toluene was washed with 15% HCl (560 ml) twice
8. customseparated
9. washThe organic layer was washed with ethylenediamine (20 ml)
10. additionby adding the ethylenediamine at room temperature
11. temperatureheating to 60° C. for 0.5 h
12. temperaturecooling
13. additionWater (250 ml) was added
14. customthe toluene was separated from the aqueous layer
15. washThe ethylenediamine wash
16. washAfter washing with water (3×500 ml)
17. dry with materialthe organic layer was dried over anhydrous magnesium sulfate (3.00 g)
18. distillationthe toluene distilled by rotary evaporation at reduced pressure
19. customto give a dark brown oil
20. custommethylene chloride and chromatographed on a silica gel column (Woelm DCC, 230 g, 5 cm dia×25 cm H)
21. customThe product was dried in a 70° C. oven under reduced pressure