Ammonium Chloride → Methyl 5-(hydroxymethyl) furan-2-carboxylate

Participants

Reaction Steps

A solution of 5-formyl-2-furancarboxylic acid methyl ester in 65 ml of tetrahydrofuran was treated with 14 ml of a 3M solution of methyl magnesium bromide in ether at 0°-5° C. The reaction mixture was stirred at the same temperature for 1 hour, poured into a saturated solution of ammonium chloride and extracted with ether. The organic phase was washed with water, dried over anhydrous magnesium sulfate and concentrated giving 6.3 g (87.8%) of 5-(1-hydroxymethyl)-2-furan carboxylic acid methyl ester as a pale yellow oil after chromatographic purification. The oxidation of this secondary alcohol was carried out by using the Swern oxidation conditions. Thus, 6.3 g of 5-(1-hydroxy- methyl) -2-furancarboxylic acid methyl ester in 60 ml of methylene chloride was added to a stirred solution of 5 g of oxalyl chloride, 7.1 g of dimethyl sulfoxide in 80 ml of methylene chloride at -60° C. The reaction mixture was stirred 15 minutes at the same temperature, then 17.5 ml of triethylamine was added. The cooling bath was removed allowing the temperature to rise to 25° C. The reaction mixture was then treated with 25 ml of water, stirred for 10 minutes and extracted with methylene chloride. The organic phase was washed with water, dried over anhydrous magnesium sulfate and concentrated in vacuo to give 6.7 g of a brown oil. Chromatographic purification of this material on a silica gel column followed by crystallization from ethyl acetate-hexane gave 3.5 g (56.2%) of 5-acetyl-2-furancarboxylic acid methyl ester as a white solid, mp 101°-102° C.

Provenance & Evidence