Trimethylsilyldiazomethane → Methyl 5-fluoro-2-(trifluoromethyl)benzoate

To a solution of 5-fluoro-2-(trifluoromethyl)benzoic acid (2.0 g, 9.62 mmol, Aldrich) in a mixture of chloroform and methanol (1:1, 40 ml) was added a 2 M solution of TMS-diazomethane in ether (approximately 8 ml) dropwise, in portions over about 1 h, allowing the solution to cool down between additions. The solution was evaporated in vacuo. To the residue was added chloroform (approximately 40 ml) and the solvent removed in vacuo to give methyl 5-fluoro-2-(trifluoromethyl)benzoate as a colourless slightly cloudy oil (2.09 g). To a stirred solution of phenol (1.06 g, 11.3 mmol, Aldrich) in DMSO (8 ml) under nitrogen was added potassium t-butoxide (1.27 g, 11.3 mmol) and the mixture stirred to dissolve. To the mixture was added methyl 5-fluoro-2-(trifluoromethyl)benzoate (2.09 g, 9.41 mmol) in DMSO (2 ml) and the mixture allowed to stand for one week. To the dark coloured mixture was added dilute aqueous sodium bicarbonate and the mixture extracted with ether four times. The combined organic extracts were dried (Na2SO4), filtered and the solvent removed in vacuo to leave a yellow oil (approximately 2 g). The residue was purified on silica 50 g using 0-100% DCM-cyclohexane. The appropriate fractions were combined and evaporated in vacuo to give methyl 5-(phenyloxy)-2-(trifluoromethyl)benzoate as a colourless oil (0.516 g).