[CH3:1][C:2]1[N:6]=[C:5]([CH3:7])[N:4]([C:8]2[C:12]([CH3:13])=[N:11][NH:10][C:9]=2[O:14][CH:15]([CH3:27])[C:16]([C:18]2[CH:23]=[CH:22][C:21]([O:24][CH3:25])=[CH:20][C:19]=2[CH3:26])=O)[N:3]=1>ClCCCl.CCOCC.CCCC(C)C.[Ti](Cl)(Cl)(Cl)Cl>[CH3:1][C:2]1[N:6]=[C:5]([CH3:7])[N:4]([C:8]2[C:12]([CH3:13])=[N:11][N:10]3[C:16]([C:18]4[CH:23]=[CH:22][C:21]([O:24][CH3:25])=[CH:20][C:19]=4[CH3:26])=[C:15]([CH3:27])[O:14][C:9]=23)[N:3]=1To 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).
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