Sulfuric Acid → 139422-31-4

Participants

Reaction Steps

To a solution of methyl, 3-methyl furanoate (10 g, 67.6 mmol) in dry tetrahydrofuran (200 ml) under a nitrogen atmosphere at 0° C. was added lithium aluminium hydride (101 ml of a 1M solution in THF, 101 mmol) dropwise over 30 mins. The mixture was heated at reflux for 1 hour, and cooled to room temperature. To this solution was added methanol (70 ml) dropwise, followed by water (3.83 ml), 15% NaOH (3.83 ml), and water (3.83 ml). The mixture was filtered through celite and the solvent was removed under reduced pressure to afford the product (5.43 g) as a pale yellow oil. To a solution of this compound (4.5 g, 40 mmol) in dry dichloromethane (200 ml) under a nitrogen atmosphere was added manganese dioxide (13.98 g, 160 mmol). The mixture was heated to reflux for 1 hour and further manganese dioxide (13.,98 g, 160 mmol) added, and the mixture heated for a further 2 hours. The mixture was cooled to room temperature and filtered through celite. The mixture was washed with saturated sodium hydrogen carbonate (150 ml), saturated sodium chloride (150 ml), dried over MgSO4, filtered and the solvent was removed under reduced pressure to give the product (3.35 g) as a pale yellow oil. To a solution of sodium carbonate (12.9 g, 122 mmol), and potassium cyanide (3.97 g, 61 mmol), in water (150 ml) was added in rapid succession glyoxal bisulphite addition compound (12.12 g, 42.6 mmol), the above product (3.45 g, 30.5 mmol), 1,4-dioxane (7 ml), and water (50 ml). The mixture was stirred at room temperature for 2 hours, then acidified to pH=2 with c.H2SO4. The mixture was stirred for a further 1 hour then extracted into chloroform (3×100 ml) and the combined organics were extracted with 1N NaOH (200 ml). The aqueous NaOH was washed with chloroform (150 ml), then acidified with c.HCl, and extracted with chloroform (3×100 ml), dried over MgSO4, filtered and the solvent was removed under reduced pressure to give 3-methyl-2-furanacetic acid (2.45 g) as a brown solid.

Provenance & Evidence