Sodium Carbonate → HCID 57429418, compound

HRID 2369782Notes

Reaction equation

HRID 2369782 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([C:8]([CH3:11])([CH3:10])[CH3:9])[CH:3]=1.[CH2:12]([OH:16])[CH:13]=[CH:14][CH3:15].C(=O)([O-])[O-].[Na+].[Na+].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.CC(OC)(C)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CN(C=O)C>[C:8]([C:4]1[CH:3]=[C:2]([CH:14]([CH3:15])[CH2:13][CH:12]=[O:16])[CH:7]=[CH:6][CH:5]=1)([CH3:11])([CH3:10])[CH3:9]

Participants

9

Reactant 4

HCID 10340Sodium CarbonateHCID 200242-Buten-1-olHCID 80271Tri-o-tolylphosphineHCID 3437981-Bromo-3-tert-butylbenzene

Product 1

HCID 57429418HCID 57429418, compoundYield 39%

Reagents, catalysts & solvents 4

HCID 74236Tetrabutylammonium BromideCatalystHCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolventHCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
95 °C

Procedure

In a 1 L three-necked round-bottom flask equipped with a mechanical stirrer and a reflux condenser were introduced DMF (200 mL), 1-bromo-3-tert-butylbenzene (54.3 g, 0.25 mol), crotyl alcohol (65 mL, 0.76 mol, 3 eq), sodium carbonate (66.2 g, 0.62 mol, 2.5 eq), tetrabutyl ammonium bromide (69.5 g, 0.25 mol, 1 eq), palladium acetate (5.05 g, 7.5 mmol, 3 mol %) and tri-o-tolyl phosphine (7.6 g, 25 mmol, 0.1 eq). After stirring for 1 h at 90-100° C., the reaction mixture was cooled to ambient temperature. The reaction mixture was filtered over celite. The organic phase thus obtained was diluted with MTBE (500 mL) and washed three times with water (500 mL portions), dried over magnesium sulphate and concentrated. The resulting crude product was distilled with a bulb-to-bulb distillation (3 mBar, 121° C.) to give a colourless oil (34.7 g, gc purity 73%). The crude product was chromatographed on a silica gel column with 5% EtOAc in hexane as elution agent giving 3-(3-tert-butylphenyl)butanal (12.3 g, gc purity 99%; yield 39%).

Workup

  1. customIn a 1 L three-necked round-bottom flask equipped with a mechanical stirrer and a reflux condenser
  2. temperaturethe reaction mixture was cooled to ambient temperature
  3. filtrationThe reaction mixture was filtered over celite
  4. customThe organic phase thus obtained
  5. washwashed three times with water (500 mL portions)
  6. dry with materialdried over magnesium sulphate
  7. concentrationconcentrated
  8. distillationThe resulting crude product was distilled with a bulb-to-bulb distillation (3 mBar, 121° C.)
  9. customto give a colourless oil (34.7 g, gc purity 73%)
  10. customThe crude product was chromatographed on a silica gel column with 5% EtOAc in hexane as elution agent

Sources & evidence

ORD record
ord-3a273973300d4b82afac5a7d64a08adf
Source dataset
uspto-grants-2014_04
Patent number
US08709994B2

Reaction notes

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