2-Methoxybenzene-1,4-diol → 2-Methoxy-1,4-benzoquinone

Participants

Reaction Steps

To a vigorously stirred solution of NaIO4 (33.5 g, 157 mmol, Baker) in H2O (1500 mL), there was added solid 2-methoxyhydroquinone (11.00 g, 50.0 mmol) in portions. The reaction immediately became dark orange. The reaction was allowed to stir for 1 h at rt and was extracted with CH2Cl2 (3×150 mL). The extract was washed with half saturated brine (1×150 mL), filtered through cotton and the solvent removed in vacuo to yield 2-methoxybenzoquinone as an orange solid (10.5 g) which was of sufficient purity (TLC analysis, 10% EtOAc/90% CHCl3) for further reaction. The crude quinone was combined with toluene (150 mL) and hydroquinone (1.0 g, Mallinkrodt). Neat 2,3-dimethyl-1,3-butadiene (8.3 g, 101 mmol, Aldrich) was added. The reaction was allowed to stir overnight at 65° C. under N2. TLC (10% EtOAc/90% CHCl3) indicated total consumption of the dienophile. The solvent was removed in vacuo to yield a dark solid. This was triturated with MeOH (100 mL) at rt to give a beige solid. Crystallization from MeOH (dissolved in 140 mL, allowed to cool to rt) yielded a fluffy colorless solid (10.2 g, 64%, >95% pure by 1H NMR analysis); mp 133°-134° C. (MeOH); 1H NMR (CDCl3) δ1.62 (s, 6H), 2.12 (m, 2H), 2.42 (m, 2H), 3.09 (m, 1H), 3.20 (m, 1H), 3.78 (s, 3H), 5.88 (s, 1H).

Provenance & Evidence