Dimethylformamide → Methyl 3-(benzyloxy)-4-bromo-2-nitrobenzoate

HRID 928542Notes

Reaction equation

[Br:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([N+:12]([O-:14])=[O:13])[C:3]=1[OH:15].C(=O)([O-])[O-].[K+].[K+].CN(C)C=O.[CH2:27](Br)[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1>O>[CH2:27]([O:15][C:3]1[C:4]([N+:12]([O-:14])=[O:13])=[C:5]([CH:10]=[CH:11][C:2]=1[Br:1])[C:6]([O:8][CH3:9])=[O:7])[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1

Participants

Conditions

Temperature: 60 °C

Procedure

A solution of methyl 4-bromo-3-hydroxy-2-nitrobenzoate (5.41 g, 19.6 mmol) and potassium carbonate (5.42 g, 39.2 mmol) in N,N-dimethylformamide (30 mL, 387 mmol) was treated with benzyl bromide (3.26 mL, 27.4 mmol) and stirred at 60° C. for 1 h. The reaction mixture was diluted with water (250 mL) and extracted with ethyl acetate (2×150 mL). The combined organic extracts were washed with brine, dried over sodium sulfate, filtered, and concentrated to give a crude tan oil. Purification by flash column chromatography (100% hexanes to 50% EtOAc/hexanes) gave the desired product (6.99 g, 97%) as a yellow solid. LCMS calculated for C15H16BrN2O5 (M+NH4)+: m/z=383.0, 385.0. found: 383.0, 385.0.

Workup

extractionextracted with ethyl acetate (2×150 mL)
washThe combined organic extracts were washed with brine
dry with materialdried over sodium sulfate
filtrationfiltered
concentrationconcentrated
customto give a crude tan oil
customPurification by flash column chromatography (100% hexanes to 50% EtOAc/hexanes)

Sources & evidence

ORD record: ord-2c0ecb4e5543412c93c153abad1936c2
Source dataset: uspto-grants-2016_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09290514B2

Reaction notes

Loading…