Ethyl Acetate → HCID 69203662, compound

HRID 2378239Notes

Reaction equation

HRID 2378239 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:11]=[CH:12][C:13](=[O:15])[CH3:14])[CH:6]=[C:7]([O:9][CH3:10])[CH:8]=1.Br[C:17]1[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[C:19]([O:25][CH3:26])[CH:18]=1.CC([O-])=O.[Na+].CCOC(C)=O>CN(C=O)C.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.CC([O-])=O.CC([O-])=O.[Pd+2].O>[CH3:24][O:23][C:20]1[CH:21]=[C:22]([C:11]([C:5]2[CH:6]=[C:7]([O:9][CH3:10])[CH:8]=[C:3]([O:2][CH3:1])[CH:4]=2)=[CH:12][C:13](=[O:15])[CH3:14])[CH:17]=[CH:18][C:19]=1[O:25][CH3:26]

Participants

9

Reactant 4

HCID 8857Ethyl AcetateHCID 76114Benzene, 4-bromo-1,2-dimethoxy-HCID 517045Sodium AcetateHCID 69204094HCID 69204094, compound

Product 1

HCID 69203662HCID 69203662, compoundYield 15%

Reagents, catalysts & solvents 4

HCID 74236Tetrabutylammonium BromideCatalystHCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent2×

Conditions

Temperature
60 °C

Procedure

A suspension of Pd(OAc)2 (67 mg, 0.30 mmol) in DMF (1 ml) was added to a stirred suspension of 4-(3,5-dimethoxyphenyl)-but-3-en-2-one (2.05 g, 9.96 mmol), 4-bromo-1,2-dimethoxybenzene (2.15 ml, 14.94 mmol), NaOAc (1.39 g, 16.94 mmol), and tetrabutylammonium bromide (3.53 g, 10.96 mmol) in DMF (19 ml). The suspension was heated at ˜60° C. overnight. The mixture was then poured into EtOAc (50 ml) and H2O (150 ml), followed by extraction with EtOAc (2×50 ml), washing with H2O (2×50 ml), brine (50 ml) and drying over MgSO4. The crude was purified flash column chromatography (10% EtOAc in hexane gradient to 25% EtOAc in hexane) to give 4-(3,4-dimethoxy-phenyl)-4-(3,5-dimethoxy-phenyl)-but-3-en-2-one as a gummy oil (0.49 g, 15%): 1HNMR (CDCl3) δ 6.93-6.92 (m, 1H, Ar), 6.82-6.77 (m, 2H, Ar), 6.53-6.51 (m, 2H, Ar and double bond proton), 6.38 (d, J=2 Hz, 2H, Ar), 3.87 (s, 3H, OCH3), 3.85 (s, 3H, OCH3), 3.79 (s, 6H, 2OCH3), 1.91 (s, 3H, CH3); 13C NMR (CDCl3) δ 160.9, 153.8, 150.7, 148.9, 141.1, 132.9, 126.5, 122.4, 113.2, 110.8, 100.9, 56.1, 55.8, 55.6, 55.4, 30.0; Anal. Calcd. For C20H22O5: C, 70.16; H, 6.48. Found: C, 70.26; H, 6.37; N, <0.05.

Workup

  1. extractionfollowed by extraction with EtOAc (2×50 ml)
  2. washwashing with H2O (2×50 ml), brine (50 ml)
  3. dry with materialdrying over MgSO4
  4. customThe crude was purified flash column chromatography (10% EtOAc in hexane gradient to 25% EtOAc in hexane)

Sources & evidence

ORD record
ord-588a310e47434411899e10ae8166191c
Source dataset
uspto-grants-2008_12
Patent number
US07470723B2

Reaction notes

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