Chlorotrimethylsilane → 4-Chloro-2-methoxyimino-3-oxobutanoic acid

Participants

Reaction Conditions

Reaction Steps

In 15 ml of acetonitrile was dissolved 725 mg of 2-methoxyimino-3-oxobutyric acid, followed by addition of 2.8 ml of triethylamine. Then, 2.5 ml of chlorotrimethylsilane was added dropwise with ice-cooling and the mixture was stirred at 20°-25° C. for 2 hours. After addition of 10 ml of xylene, the reaction mixture was concentrated under reduced pressure and the residue was suspended in 15 ml of tetrahydrofuran. The suspension was filtered in a nitrogen gas stream to remove insolubles. This filtrate containing trimethylsilyl 2-ethoxyimino-3-oxobutyrate trimethylsilyl enol ether (i.e. trimethylsilyl 2-methoxyimino-3-trimethylsilyloxy-3-butenoate) was cooled to -30° C. and 0.45 ml of sulfuryl chloride was added dropwise thereto. After the temperature of the mixture was increased to 20° C., the reaction mixture was concentrated under reduced pressure and the residue was diluted with 20 ml of water and stirred for 10 minutes for hydrolyzing the trimethylsilyl ester. Then, 2N aqueous sodium hydroxide solution was added dropwise to adjust the reaction mixture to pH 9.0. The reaction mixture was washed twice with 20 ml portions of methylene chloride and the aqueous layer was adjusted to pH 0.5 by dropwise addition of concentrated hydrochloric acid. The aqueous layer was saturated with sodium chloride and extracted 3 times with 20 ml portions of ether. The organic layers were combined, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The above procedure gave 4-chloro-2-methoxyimino-3-oxobutyric acid.

Provenance & Evidence