Methanol → 5-Bromo-2-(1-carboxy-ethoxy)-benzoic acid

HRID 402918Notes

Reaction equation

C[O:2][C:3](=[O:19])[C:4]1[CH:9]=[C:8]([Br:10])[CH:7]=[CH:6][C:5]=1[O:11][CH:12]([C:14]([O:16]CC)=[O:15])[CH3:13].CO.[OH-].[Na+]>C1COCC1>[Br:10][C:8]1[CH:7]=[CH:6][C:5]([O:11][CH:12]([C:14]([OH:16])=[O:15])[CH3:13])=[C:4]([CH:9]=1)[C:3]([OH:19])=[O:2]

Participants

Conditions

Temperature: 85 °C

Procedure

A solution of 5-bromo-2-(1-ethoxycarbonyl-ethoxy)-benzoic acid methyl ester (41.1 g, 124 mmol) in a mixture of THF (250 mL), MeOH (250 mL) and a 5 M aqueous NaOH solution (300 mL) is heated under reflux (85° C.) for 16 h. After cooling to room temperature the resulting suspension is concentrated by rotary evaporation. The residue is dissolved in water and acidified with an aqueous concentrated HCl solution under cooling with ice. The aqueous phase is extracted twice with EtOAc and the combined organic layers are washed with brine, dried over Na2SO4, filtered and concentrated at reduced pressure to afford the title compound as a beige solid (31.5 g, 109 mmol, 88%). 1H NMR (400 MHz, DMSO-d6, 298 K): δ=13.04 (bs, 2H), 7.72 (d, J=2.7 Hz, 1H), 7.63 (dd, J=8.9, 2.7 Hz, 1H), 6.92 (d, J=8.9 Hz, 1H), 4.90 (q, J=6.6 Hz, 1H), 1.49 (d, J=6.6 Hz, 3H). MS (ES+): 289 (M(C10H979BrO5)+H)+.

Workup

temperatureAfter cooling to room temperature the resulting suspension
concentrationis concentrated by rotary evaporation
dissolutionThe residue is dissolved in water
temperatureunder cooling with ice
extractionThe aqueous phase is extracted twice with EtOAc
washthe combined organic layers are washed with brine
dry with materialdried over Na2SO4
filtrationfiltered
concentrationconcentrated at reduced pressure

Sources & evidence

ORD record: ord-6fa0ac3b710f449dbac8da8885b9da4e
Source dataset: uspto-grants-2014_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08742132B2

Reaction notes

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