Sulfuric Acid → 3-Methoxy-2-MethylBenzoic Acid

Participants

Reaction Conditions

Reaction Steps

3-Amino-2-methylbenzoic acid (140.3 g, 0.93 mol, reacted in four portions) in 5.7 mass equivalents of methanol was treated with 1.5 mole equivalents of concentrated sulfuric acid. The mixture was heated to 55° C. and 1.05 mole equivalent of sodium nitrite dissolved in twice its mass of water was fed to the reaction over 30 to 45 minutes, maintaining the temperature between 55 and 65° C. 4.5 mole equivalents of 25% aqueous sodium hydroxide was added over one-half hour, followed by a half-hour feed of 2 mole equivalents of dimethylsulfate at 50 to 60° C. After one-half hour the batch was assayed by GC. Additional sodium hydroxide and dimethylsulfate were added in portions until complete conversion was obtained, The methanol remaining was removed by vacuum, and the residue was partitioned between ethyl acetate and water made acidic with sulfuric acid. The ethyl acetate was removed under vacuum. The combined residues (152.8 g) dissolved in 350 g warm methanol were poured into a mixture of 278 g concentrated sulfuric acid and 1 liter water. The resulting precipitate was collected by filtration, washed with water, and dried in vacuo, giving 135.8 g (88%) of material which was 96% pure as determined by GC.

Provenance & Evidence