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

HRID 2308728Notes

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 to 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 recrystallized 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 recrystallized from ethyl acetate-hexane

Sources & evidence

ORD record: ord-ad15473b8aaa4c238aae6389eb7184a1
Source dataset: uspto-grants-1987_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04690943

Reaction notes

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