Dimethyl malonate → Dimethyl 2-(4-nitrophenyl)malonate

HRID 2356687Notes

Reaction equation

HRID 2356687 reaction equation
[C:1]([O:8][CH3:9])(=[O:7])[CH2:2][C:3]([O:5][CH3:6])=[O:4].Br[C:11]1[CH:16]=[CH:15][C:14]([N+:17]([O-:19])=[O:18])=[CH:13][CH:12]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].CC1(C)C2C=CC=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=2OC2C1=CC=CC=2P(C1C=CC=CC=1)C1C=CC=CC=1>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[N+:17]([C:14]1[CH:15]=[CH:16][C:11]([CH:2]([C:1]([O:8][CH3:9])=[O:7])[C:3]([O:5][CH3:6])=[O:4])=[CH:12][CH:13]=1)([O-:19])=[O:18]

Participants

7

Reactant 4

HCID 7943Dimethyl malonateHCID 114661-Bromo-4-nitrobenzeneHCID 62657Potassium Phosphate, TribasicHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)

Product 1

HCID 2764303Dimethyl 2-(4-nitrophenyl)malonate

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
90 °C

Procedure

2.0 g of dimethyl malonate, 3.36 g of 1-bromo-4-nitrobenzene, 9.64 g of potassium phosphate, 85 mg of palladium(II) acetate and 394 mg of 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene were dissolved under an argon atmosphere in 25 ml of dry dioxane and stirred at 90° C. for 8 h. For workup, the reaction mixture was filtered through a cartridge and the filtrate was concentrated under reduced pressure. The residue was purified by chromatography (silica gel; n-heptane/15-35% ethyl acetate). Dimethyl 2-(4-nitrophenyl)malonate (229.1) was obtained. Molecular weight 253.05 (C11H11NO6); retention time Rt=1.88 min. [B]; MS (ESI): 254.03 (MH+).

Workup

  1. filtrationFor workup, the reaction mixture was filtered through a cartridge
  2. concentrationthe filtrate was concentrated under reduced pressure
  3. customThe residue was purified by chromatography (silica gel; n-heptane/15-35% ethyl acetate)

Sources & evidence

ORD record
ord-d2f29966e54a4f3f917c6a646a1f029d
Source dataset
uspto-grants-2010_07
Patent number
US07759366B2

Reaction notes

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