Methanol → (E)-3-[7-Hydroxy-6-methoxy-3-(3,4,5-trimethoxy-benzoyl)-benzofuran-2-yl]-acrylic acid methyl ester

HRID 1191991Notes

Reaction equation

HRID 1191991 reaction equation
Br[C:2]1[O:3][C:4]2[C:24]([O:25]C(=O)C)=[C:23]([O:29][CH3:30])[CH:22]=[CH:21][C:5]=2[C:6]=1[C:7](=[O:20])[C:8]1[CH:13]=[C:12]([O:14][CH3:15])[C:11]([O:16][CH3:17])=[C:10]([O:18][CH3:19])[CH:9]=1.[CH3:31][O:32][C:33](=[O:36])[CH:34]=[CH2:35].CO.C(=O)([O-])[O-].[K+].[K+]>C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:31][O:32][C:33](=[O:36])/[CH:34]=[CH:35]/[C:2]1[O:3][C:4]2[C:24]([OH:25])=[C:23]([O:29][CH3:30])[CH:22]=[CH:21][C:5]=2[C:6]=1[C:7](=[O:20])[C:8]1[CH:9]=[C:10]([O:18][CH3:19])[C:11]([O:16][CH3:17])=[C:12]([O:14][CH3:15])[CH:13]=1

Participants

7

Reactant 4

HCID 887MethanolHCID 7294Methyl AcrylateHCID 11430Potassium CarbonateHCID 247865602-Bromo-7-acetoxy-3-(3,4,5-trimethoxybenzoyl)-6-methoxybenzofuran

Product 1

HCID 24786669(E)-3-[7-Hydroxy-6-methoxy-3-(3,4,5-trimethoxy-benzoyl)-benzofuran-2-yl]-acrylic acid methyl esterYield 37%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6342AcetonitrileSolvent

Procedure

Mixture of 2-bromo-7-acetoxy-3-(3,4,5-trimethoxybenzoyl)-6-methoxy-benzofuran (50 mg, 0.10 mmol) and methylacrylate (0.5 mL, excess) in a mixture of acetonitrile: TEA; 1 mL:0.5 mL was degassed with nitrogen and palladium acetate (10 mg) was added to it. Reaction mixture was stirred for one hour under nitrogen at reflux, more palladium acetate (15 mg) was added and the refluxing was continued for 7 hours (monitored by tlc). Methanol (1 mL) was added followed by the addition of potassium carbonate (70 mg, 0.51 mmol) and stirring was continued for 1 hour. Solvent was distilled and the crude material was purified over silica gel column (eluent Hexane:diethylether; 1:1) to afford the title compound as yellow crystalline solid (17 mg, 37%); 1H NMR (300 MHz, CDCl3) δ 7.61 (d, 1H, J=15.76 Hz), 7.14 (s, 2H, benzoyl Hs), 6.98 (d, 1H, J=8.64 Hz), 6.89 (d, 1H, J=8.69 Hz), 6.81 (d, 1H, J=15.78 Hz), 3.96 (s, 3H, OMe), 3.95 (s, 3H, OMe), 3.81 (s, 6H, 2×OMe), 3.77 (bs, 3H, OMe).

Workup

  1. custom1 mL:0.5 mL was degassed with nitrogen and palladium acetate (10 mg)
  2. additionwas added to it
  3. customReaction mixture
  4. temperatureat reflux
  5. waitthe refluxing was continued for 7 hours
  6. stirringstirring
  7. waitwas continued for 1 hour
  8. distillationSolvent was distilled
  9. customthe crude material was purified over silica gel column (eluent Hexane:diethylether; 1:1)

Sources & evidence

ORD record
ord-f17582a6a32841588f10d34dd1e14fe6
Source dataset
uspto-grants-2014_03
Patent number
US08680135B2

Reaction notes

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