Hydrochloric Acid → Diethyl (4-bromo-2-nitrophenyl)propanedioate

HRID 1386348Notes

Reaction equation

Br[C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].[H-].[Na+].[C:14]([O:22][CH2:23][CH3:24])(=[O:21])[CH2:15][C:16]([O:18][CH2:19][CH3:20])=[O:17].Cl>CN(C=O)C>[CH2:19]([O:18][C:16](=[O:17])[CH:15]([C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10])[C:14]([O:22][CH2:23][CH3:24])=[O:21])[CH3:20]

Participants

Conditions

Temperature: 60 °C

Procedure

2,5-Dibromonitrobenzene (41.5 g, 148 mmol) was dissolved in anhydrous DMF (500 ml) and sodium hydride (17.7 g of a 60% suspension in mineral oil, 443 mmol) was added under argon. Diethyl malonate (49.6 g, 295 mmol) was added dropwise over 10 minutes giving a strong exotherm (mixture rose to 60° C.). The reaction mixture was maintained at 60° C. for 6 hours then left to cool to ambient temperature and stirred for 18 hours. The resulting dark red solution was poured slowly into 2M hydrochloric acid (1500 ml) and extracted with ether (500 ml×4). The organic phases were combined, washed with brine, dried (MgSO4) and the solvent removed by evaporation. The crude oil was purified by flash chromatography eluting with isohexanes/ethyl acetate (100/0, then 95/5 and finally 80/20) to give diethyl(4-bromo-2-nitrophenyl)malonate (51 g, 96%).

Workup

customgiving a strong exotherm (mixture rose to 60° C.)
waitthen left
temperatureto cool to ambient temperature
extractionextracted with ether (500 ml×4)
washwashed with brine
dry with materialdried (MgSO4)
customthe solvent removed by evaporation
customThe crude oil was purified by flash chromatography
washeluting with isohexanes/ethyl acetate (100/0

Sources & evidence

ORD record: ord-f2b1824ea9924d02852c48e2dcb8f86e
Source dataset: uspto-grants-2001_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06265411B1

Reaction notes

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