Diethyl Malonate → Diethyl (4'-nitrobiphenyl-4-yl)malonate

HRID 1713859Notes

Reaction equation

HRID 1713859 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][C:11]([N+:14]([O-:16])=[O:15])=[CH:10][CH:9]=2)=[CH:4][CH:3]=1.C(=O)([O-])[O-].[Cs+].[Cs+].[C:23]([O:31][CH2:32][CH3:33])(=[O:30])[CH2:24][C:25]([O:27][CH2:28][CH3:29])=[O:26]>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2CCCCC2)C2C=CC=CC=2C2C(C(C)C)=CC(C(C)C)=CC=2C(C)C)CCCCC1>[N+:14]([C:11]1[CH:12]=[CH:13][C:8]([C:5]2[CH:6]=[CH:7][C:2]([CH:24]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[C:23]([O:31][CH2:32][CH3:33])=[O:30])=[CH:3][CH:4]=2)=[CH:9][CH:10]=1)([O-:16])=[O:15]

Participants

7

Reactant 3

HCID 7761Diethyl MalonateHCID 10796Cesium carbonateHCID 2336104-Bromo-4'-nitro-1,1'-biphenyl

Product 1

HCID 59464037Diethyl (4'-nitrobiphenyl-4-yl)malonateYield 101.7%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylCatalystHCID 1140TolueneSolvent

Procedure

A mixture of 4-(4-bromophenyl)nitrobenzene (Journal of Organic Chemistry, 2005, 70(9), 3730) (800 mg, 2.88 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos) (69 mg) and caesium carbonate (2.81 g, 8.63 mmol) in toluene (40 mL) was deoxygenated then palladium(II) acetate (13 mg, 0.06 mmol) and diethyl malonate (0.480 mL, 3.2 mmol) were added. The reaction mixture was heated under reflux for 2 h, cooled and then filtered through diatomaceous earth and the filter washed with EtOAc. The filtrate was concentrated by evaporation and adsorbed onto silica then purified by chromatography, eluting with 0-25% EtOAc in isohexane, to give the title compound (1.047 g) as a solid.

Workup

  1. customwas deoxygenated
  2. temperatureThe reaction mixture was heated
  3. temperatureunder reflux for 2 h
  4. temperaturecooled
  5. filtrationfiltered through diatomaceous earth
  6. washthe filter washed with EtOAc
  7. concentrationThe filtrate was concentrated by evaporation
  8. customthen purified by chromatography
  9. washeluting with 0-25% EtOAc in isohexane

Sources & evidence

ORD record
ord-a552d6c04b8848d1983e7b9454fe2453
Source dataset
uspto-grants-2010_09
Patent number
US07795283B2

Reaction notes

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