Dimethyl malonate → 1,3-Dimethyl 2-(4-bromo-2-nitrophenyl)propanedioate

HRID 414267

Reaction equation

[H-].[Na+].[C:3]([O:10][CH3:11])(=[O:9])[CH2:4][C:5]([O:7][CH3:8])=[O:6].Br[C:13]1[CH:18]=[CH:17][C:16]([Br:19])=[CH:15][C:14]=1[N+:20]([O-:22])=[O:21].[Cl-].[NH4+]>CS(C)=O>[Br:19][C:16]1[CH:17]=[CH:18][C:13]([CH:4]([C:3]([O:10][CH3:11])=[O:9])[C:5]([O:7][CH3:8])=[O:6])=[C:14]([N+:20]([O-:22])=[O:21])[CH:15]=1

Participants

Conditions

Temperature: 100 °C

Procedure

To 9.4 g of sodium hydride was added 195 ml of dimethyl sulfoxide, followed by the dropwise addition of 22.37 ml of dimethyl malonate. At the end of the addition, the mixture was heated at 100° C. and maintained at that temperature for 40 minutes. At this point, 25 g of 1,4-dibromo-2-nitrobenzene was added all at once. The reaction mixture was maintained at 100° C. for 4 hours and then it was added to 1.0 liter of saturated ammonium chloride solution. The resulting mixture was extracted with ethyl acetate and the extracts were washed with ammonium chloride solution, water and saturated sodium chloride. The dried (MgSO4) solvent was evaporated, and the residue was recrystalized from ethyl acetate-hexane to give 22.45 g of dimethyl 2-(4-bromo-2-nitrophenyl)malonate.

Workup

additionAt the end of the addition
temperaturemaintained at that temperature for 40 minutes
temperatureThe reaction mixture was maintained at 100° C. for 4 hours
extractionThe resulting mixture was extracted with ethyl acetate
washthe extracts were washed with ammonium chloride solution, water and saturated sodium chloride
dry with materialThe dried (MgSO4) solvent
customwas evaporated
customthe residue was recrystalized from ethyl acetate-hexane

Sources & evidence

ORD record: ord-3d5eb43172a14b90bf1cd55080bc599b
Source dataset: uspto-grants-1988_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04791131

Linked notes

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