反应详情

温度

85 °C

To a dispersion of 2-[4-(3,5-dimethyl-[1,2,4]triazol-1-yl)-5-methyl-2H-pyrazol-3-yloxy]-1-(4-methoxy-2-methyl-phenyl)-propan-1-one (0.905 g, 2.45 mmol) in 1,2-dichloroethane (20 ml) is added titanium tetrachloride (0.675 ml, 6.12 mmol). The reaction mixture is heated to 85° C. for 2.5 hours and then left at RT overnight. The mixture is quenched carefully with sat. NH4Cl (50 ml) and extracted with EtOAc (2×50 ml). The combined organic extracts are washed with NaHCO3 (50 ml), brine, dried over MgSO4 and concentrated in vacuo to afford a dark brown oil. The crude oil is then taken up in 10% Et2O/iso-hexane (50 ml) and the brown solution is sonicated: no precipitation occurred immediately, but after 2 hours large crystals form. The solid is collected and washed with iso-hexane to give a cream coloured solid. Purification of this solid by recrystallisation from hot Et2O (˜40 ml) yields the title compound as tan crystals; MS: m/z=352.1 [M+H]+. 1H NMR (400 MHz, DMSO-d6) δ 7.39 (1H, d), 7.01 (1H, d), 6.94 (1H, dd), 3.83 (3H, s), 2.30 (6H, s), 2.26 (6H, s), 2.11 (3H, s).

1. customThe mixture is quenched carefully with sat. NH4Cl (50 ml)
2. extractionextracted with EtOAc (2×50 ml)
3. washThe combined organic extracts are washed with NaHCO3 (50 ml), brine
4. dry with materialdried over MgSO4
5. concentrationconcentrated in vacuo
6. customto afford a dark brown oil
7. customthe brown solution is sonicated
8. customno precipitation
9. waitafter 2 hours large crystals form
10. customThe solid is collected
11. washwashed with iso-hexane
12. customto give a cream
13. customPurification of this solid
14. customby recrystallisation from hot Et2O (˜40 ml)