Hydrogen Bromide → 4-Bromo-2-(methoxyimino)-3-oxobutanoic acid

Participants

Reaction Steps

In 3 liters of methylene chloride was dissolved 460 g of the 2-methoxyimino-3-oxobutyric acid obtained by the procedure of Example 1. To the solution was added 46 ml of a 25% hydrogen bromide solution in acetic acid. To the resultant solution was added dropwise over 2 hours at 7° to 15° C. a solution of 372 g of bromine in 372 ml of methylene chloride. Nitrogen was then blown into the mixture violently at 7° to 8° C. for 30 minutes so as to eliminate the byproduct hydrogen bromide. Silica gel (Kieselgel 60, 70 to 230 mesh, manufactured by Merck; 80 g) and activated carbon (Shirasagi of larger grain A grade, manufactured by Takeda Chemical Industries; 30 g) were added to the supernatant obtained. The mixture was stirred at 10° to 15° C. for 30 minutes and the insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure, the oily residue was dissolved in 685 ml of xylene, and the solution was allowed to stand at 5° C. for 15 hours. The resultant crystalline precipitate was collected by filtration, washed with 100 ml of a 1:1 (v/v) mixture of xylene and n-hexane and then with 200 ml of n-hexane, and dried under reduced pressure to give 434 g of 4-bromo-2-methoxyimino-3-oxobutyric acid. The filtrate (mother liquor) was concentrated under reduced pressure and the oily residue was crystallized by addition of 238 ml of a 100:15 (v/v) mixture of xylene and n-hexane to give 82.3 g of 4-bromo-2-methoxyimino-3-oxobutyric acid as a second crop.

Provenance & Evidence