Dichloromethane → 5-tert-Butylsalicylaldehyde

Participants

Reaction Steps

To an ice-cold stirred mixture of o-anisaldehyde (50 ml, 326 mmol) and tert-butylchloride (80 ml, 735 mmol) was added aluminum chloride (40 g, 300 mmol). The reaction mixture became thick. Dry dichloromethane (100 ml) and aluminum chloride (60 g, 450 mmol) were added carefully with cooling. Once the reaction became less vigorous the reaction mixture was stirred at room temperature for 2.25 h. Ice (50 g) and subsequently ice-cold water (100 ml) were added carefully and the mixture was left to stir for 20 min. water (250 ml) and ether (550 ml) were added. The aqueous layer was removed and the organic layer was washed with water (3×250 ml), dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was purified by distillation under reduced pressure and the fraction (b.p. 80°-86° C., 0.55-0.65 mm Hg) collected to yield (6) as a colourless oil (23.4 g, 40%). Preparation of 2-methoxy-5-tert-butylbenzaldehyde (5) To a solution of (6) (5.01 g, 28.1 mmol) in dry DMF (25 ml) was added a solution of tetra-n-butylammonium hydroxide in methanol (1.0M, 28.5 ml, 28.5 mmol). Methyl iodide (25 ml, 399 mmol) was added and the solution was stirred ac reflux for 1.5 h and then allowed to cool. Ether (250 ml) and water (250 ml) were added. The aqueous layer was removed and the organic layer was washed with water (3×250 ml), brine (250 ml), dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was purified by column chromatography over silica (dichloromethane/petroleum ether [60/80]; 4:1) to yield a colourless oil of (5) (4.36 g, 81%); δH (CDCl3) 1.29 (9 H, s, tert-butyl), 3.88 (3 H, s, OCH3), 6.95 (1 H, d, J=8.8 Hz, H3), 7.56 (1 H, dd, J=8.8, 2,7 Hz, H4), 7.83 (1 H, d, J=2.7 Hz, H6), and 10.44 (1 H, s, CHO).

Provenance & Evidence