| 96% |
With pyridine at 0 - 20℃; for 24.5h; |
Synthesis of 2-oxo-2H-chromen-7yl trifluoromethanesulfonate (1)
Trifluoromethanesulfonic anhydride (20 ml, 119 mmol) was added to a solution of umbelliferon(21.35 g, 132 mmol) in pyridine (500 ml) at 0 °C. The mixture was stirred at 0 °C for5 minutes and then at room temperature for 24 hours. The reaction mixture was poured intowater (400 ml) and extracted with toluene (400 ml). The organic extracts were washed with10%HCl solution (100ml) and then with saturated NaCl solution (100ml). The organic layerwas dried over Na2SO4, filtered and evaporated to dryness to give 33.8 g (96%) in a whitesolid.1H NMR (400 MHz, CDCl3): δ 7.73 - 7.71 (d, 1H), 7.60 - 7.58 (d, 1H), 7.27 - 7.20 (m,2H), 6.48 (d, 1H). Anal. Calcd. for C10H5F3O5S (294.2 g/mol): C, 40.82%; H, 1.71%. Found:C, 40.74%; H, 1.82%. |
| 95% |
With pyridine In dichloromethane at 0℃; for 0.25h; |
|
| 91% |
With pyridine for 4h; ice cooling; |
|
| 91% |
With dmap In dichloromethane at 20℃; |
|
| 88% |
With pyridine In dichloromethane at -10℃; for 1h; Inert atmosphere; |
|
| 88% |
With pyridine at 20℃; for 5h; Inert atmosphere; Cooling with ice; |
1-1 Synthesis of 2-Oxo-2H-chromen-7-yl trifluoromethanesulfonate
Under an argon atmosphere, 4-Methylumbelliferone (100 mg, 617 μmol) of pyridine (6 mL)Ice-Cooled Dissolved.Trifluoromethanesulfonic Anhydride (114 MyuL, 679 Myumol) Was Added DropwiseIt was.The Mixture Was Then Stirred At Room Temperature For 5 Hours.After Completion Of The Reaction, And Extracted With Ethyl Acetate, Washed With Saturated Brinedid.Organic Layer Was The Dried Over Anhydrous Sodium Sulfate And The Solvent Was Distilled Off.Purification Silica Gel Column (SiOTwo. At 20 g), to give a white solid compound (160 mg, 88%) |
| 86.5% |
With 4-methyl-morpholine In dichloromethane at 0 - 20℃; for 16h; Inert atmosphere; |
|
| 85% |
With pyridine at 0 - 20℃; for 2.83333h; |
Synthesis of 2-oxo-2H-chromen-7-yltrifluoromethanesulfonate (9)
A solution of 7-hydroxycoumarin (8) (1.0 g, 6.17 mmol) inpyridine (5 mL) was cooled to 0 °C and treated with triflicanhydride (2.1 mL, 12.34 mmol, 20 min addition). Thereaction mixture was allowed to warm to room temperatureand stirred for an additional 2.5 h. The crude mixture waspartitioned between saturated aqueous CuSO4 and ethylacetate. After separation of the fractions, the organic fractionwas dried (Na2SO4) and concentrated under reducedpressure. The crude product was purified by column chromatographyover silica gel. Elution with a mixture ofhexane-ethyl acetate (8:2 ratio) afforded compound 9 in85% yield (1.54 mg, 85% yield). M.p. 78-80 °C; IR (KBr, cm-1): νmax 1720 (C=O),1421 y 1220 S(=O)2, 1130 (CF3), 1294 (C-O-C), 1110((C=O)-O), 748-979 (C-O-S). 1H NMR (CDCl3,300 MHz): δ 6.53 (H3, d, J = 9.7 Hz), 7.25 (H6, dd, J = 2.3,8.6 Hz), 7.31 (H8, d, J = 2.3 Hz), 7.62 (H5, d, J = 8.6 Hz),7.76 (H4, d, J = 9.7 Hz). 13C NMR (CDCl3, 75MHz): δ110.60 (C8), 117.81 (C3, C6), 118.66 (-SO3CF3, q, JC-F =321 Hz), 118.80 (C4a), 129.48 (C5), 142.18 (C4), 150.84(C7), 154.57 (C8a), 159.35 (C=O). EIMS: m/z 294.9880 [M+ H]+, (calculated for [C10H6F3O5S]+: 294.9884). |
| 82% |
With pyridine at 20℃; for 25h; |
7
To a solution of 7-hydroxy-benzopyran-2-one (3.20 g, 20.0 mmol)Pyridine (30.0 mL)Triflic anhydride (5.00 mL, 30.0 mmol) was added slowly to the solution.After stirring for 5 minutes, the temperature was raised to room temperature and the reaction was stirred for 25 hours.The reaction system was quenched by adding water (10 mL)Extract with ether (20.0 mL).The extract was washed with water (50 mL), 10%Aqueous hydrochloric acid (100 mL), water (50 mL) and saturated brine, the organic phase was dried over anhydrous magnesium sulfate and evaporated under reduced pressureAfter flashing solvent, flash column chromatography (eluent PE: EA = 3: 1, Rf = 0.40)A white solid (5.33 g, 82%) was obtained, |
| 81% |
With pyridine In dichloromethane at 0 - 20℃; |
|
| 80% |
With pyridine In dichloromethane at 20℃; for 2h; |
|
| 64% |
With pyridine In dichloromethane at 0 - 20℃; for 1h; |
|
|
With triethylamine In dichloromethane at 0℃; |
1 2.5 Synthesis of 7-trifluoromethylsulfonyloxycoumarins (5a-c)
General procedure: The coumarins (5a-c) were synthesized by the reaction of 7-hydroxycoumarins (4a-c) (0.56mmol) and trifluoromethanesulfonic anhydride (0.72mmol) in the presence of Et3N (0.74mmol) as reported in the literature [40]. The spectral data of known compounds (5a-b) are found to be in good agreement with the reported data [41,42] whereas the characterization data of unknown compound 5c are given below. |
|
With pyridine In dichloromethane at 0 - 20℃; Inert atmosphere; |
|
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