Trifluoroacetic acid → 6,7-dichloro-4H-benzo[1,4]oxazin-3-one

Participants

Reaction Conditions

Reaction Steps

Ethyl[(4,5-dichloro-2-nitrophenyl)oxy]acetate (36.0 g, 0.122 mol) was dissolved in 400 mL of ethanol and treated with SnCl2.2H2O (138.0 g, 0.612 mol). This mixture was magnetically stirred and heated to 85° C. in an oil bath. After 20 hours, HPLC (Eclipse XDB-C18, 4.6×250 mm, 5 micron, 1-99% CH3CN/H2O with 0.1% trifluoroacetic acid) showed that all of the starting material (Rt=7.8 min) was gone and that two new compounds had formed: the desired product (Rt=6.2 min) and the hydroxamic acid of the desired product (Rt=5.9 min). An additional 138.0 g of SnCl2.2H2O (0.612 mol) and 90 mL of concentrated HCl were added and stirred at 85° C. for seven hours, after which time HPLC showed that only the desired product remained. The reaction mixture was poured into 5.5 L of 5% aqueous HCl and stirred for 20 minutes, resulting in precipitation of the product. The solid was filtered off and air-dried on a vacuum funnel for one hour. The solid was transferred to a 1 L round bottom flask and suspended in 500 mL of absolute ethanol. The solvent was removed by rotary evaporation to azeotrope off the last traces of water and the resulting white solid was dried under high vacuum to give 6,7-dichloro-2H-1,4-benzoxazin-3(4H)-one (22.2 g. 0.102 mol, 83%) as a fine white powder. MS (ES) m/e 218 [M+H]+.

Provenance & Evidence