Ethyl 4-chloroacetoacetate → HCID 86708160, compound

Participants

Reaction Conditions

Reaction Steps

To a solution of 2-bromo-4-fluoroaniline (10 g, 52.6 mmol, 1.0 eq.) in DCM/HOAc (1/1, 160 mL, 0.3M) at 0° C. was added dropwise a precooled solution of sodium nitrite (4.1 g, 57.9 mmol, 1.1 eq.) in conc. sulfuric acid (20 mL). After stirring for 30 min at 0° C. a mixture of ethyl 4-chloroacetoacetate (14.6 mL, 17.8 g, 108 mmol, 1.2 eq.) in HOAc (40 mL) and H2O (80 mL) was added within 5 min. After further 15 min at 0° C. a solution of sodium acetate (72 g, 0.878 mol, 16.7 eq.) in H2O (140 mL) was added slowly. The mixture stirred for 30 min at 0° C. and than 12 h at RT. DCM (200 mL) was added and the organic phase was separated. The aq. phase was extracted with DCM (3×100 mL). The combined organic phase was washed with water, phosphate buffer and subsequent with brine. The organic layer was dried over Na2SO4 and concentrated under reduced pressure to give the product ethyl 2-(2-bromo-4-fluoro-phenyl)azo-4-chloro-3-oxo-butanoate as a red solid. MS (ES) C12H11BrClFN2O3 requires: 365. Found: 365/367 (M+H)+.

Provenance & Evidence