Dimethyl malonate → Dimethyl (3-fluoro-2-nitrophenyl)propanedioate

HRID 2378953Notes

Reaction equation

F[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([F:8])[C:3]=1[N+:9]([O-:11])=[O:10].C(=O)([O-])[O-].[K+].[K+].[C:18]([O:25][CH3:26])(=[O:24])[CH2:19][C:20]([O:22][CH3:23])=[O:21]>CN(C)C=O>[F:8][C:4]1[C:3]([N+:9]([O-:11])=[O:10])=[C:2]([CH:19]([C:18]([O:25][CH3:26])=[O:24])[C:20]([O:22][CH3:23])=[O:21])[CH:7]=[CH:6][CH:5]=1

Participants

Conditions

Temperature: 65 °C

Procedure

1,3-Difluoro-2-nitrobenzene (2.83 g, 17.79 mmol) was dissolved in N,N-dimethylformamide (25 mL). Potassium carbonate (2.49 g, 18.02 mmol) was added to the mixture followed by dimethyl malonate (2.033 ml, 17.79 mmol). Mixture was warmed to 65° C. and held for 24 hours. Mixture was cooled to room temperature. Reaction was quenched with 1N hydrochloric acid. Material was extracted three times with diethyl ether and the aqueous phase was discarded. Material was washed twice with water and the aqueous phase was discarded. Material was washed with brine and the aqueous phase was discarded. Organics were dried MgSO4, filtered and then concentrated to dryness. Residue was crystallized with hexanes. Solids were filtered off and washed with hexanes. Title compound was obtained as yellow crystals in 52% yield. MS (M−H)−=270.1.

Workup

temperatureMixture was cooled to room temperature
customReaction
customwas quenched with 1N hydrochloric acid
extractionMaterial was extracted three times with diethyl ether
washMaterial was washed twice with water
washMaterial was washed with brine
filtrationfiltered
concentrationconcentrated to dryness
customResidue was crystallized with hexanes
filtrationSolids were filtered off
washwashed with hexanes

Sources & evidence

ORD record: ord-1ae5c379cb244710bc68d44e7da3174a
Source dataset: uspto-grants-2008_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07470680B2

Reaction notes

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