Hydrogen Bromide → Methyl 8-bromo-2-naphthalenecarboxylate

Participants

Reaction Conditions

Reaction Steps

To a cooled (10° C.) stirred solution of NaNO2 (2.18 g, 31.5 mmol) in concentrated H2SO4 (28.3 mL) and glacial acetic acid (26.1 mL) (prepared by adding NaNO2 to cooled [10° C.] H2SO4, heating to dissolve, re-cooling and adding HOAc) was added a solution of 8-amino-2-naphthoic, methyl ester (VII) (5.72 g, 26.36 mmoles) in glacial acetic acid (88.7 mL) over 10 minutes. The resulting solution was then added slowly (over 10 minutes) to a heated (60° C.), stirred solution of CuBr (16.59 g, 43.31 mmoles) in concentrated HBr (160 mL). The mixture was warmed to 90° C. for 10 minutes, cooled, diluted with H2O (350 mL), and filtered to give 5.8 g (yield: 83%) of 8-bromo-2-naphthoic acid, methyl ester; 1H-NMR: δ9.00 (s, 1H), 8.10 (dd, J=7.5, 1.0 Hz, 1H), 7.90 (d, J=8.5 Hz, 1H), 7.85 (d, J=6.5 Hz, 2H), 7.40 (dd, J=8.2, 7.5 Hz, 1H), 4.05 (s, 3H).

Provenance & Evidence