Sodium Carbonate → HCID 15354815, compound

HRID 2369777Notes

Reaction equation

HRID 2369777 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH3:8])[CH:5]=C[CH:7]=1.[CH2:9]([OH:13])[CH:10]=[CH:11][CH3:12].[C:14](=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>[CH3:8][C:4]1[CH:5]=[C:12]([CH:11]([CH3:14])[CH2:10][CH:9]=[O:13])[CH:7]=[CH:2][CH:3]=1

Participants

9

Reactant 4

HCID 10340Sodium CarbonateHCID 115603-BromotolueneHCID 200242-Buten-1-olHCID 80271Tri-o-tolylphosphine

Product 1

HCID 15354815HCID 15354815, compoundYield 36%

Reagents, catalysts & solvents 4

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

Conditions

Temperature
102.5 °C

Procedure

In a 1 L three-necked round-bottom flask equipped with a mechanical stirrer and a reflux condenser were introduced DMF (300 mL), 3-bromo toluene (66.3 g, 0.39 mol), of crotyl alcohol (99 mL, 1.16 mol, 3 eq), sodium carbonate (102.5 g, 0.97 mol, 2.5 eq), tetrabutyl-ammonium bromide (107.6 g, 0.39 mol, 1 eq), palladium acetate (7.8 g, 11.6 mmol, 3 mol %) and tri-o-tolyl phosphine (11.8 g, 38.7 mmol, 0.1 eq). After stirring for 1 h at 100-105° 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 (800 mL) and washed three times with water (500 mL portions), dried over magnesium sulphate and concentrated. The resulting crude product was fractionally distilled with a Vigreux column (1 mBar, 70-81° C.) to give a colourless oil (39.6 g, gc purity 90%). The oil was chromatographed on a silica gel column with 7% EtOAc in hexane as elution agent giving 3-(3-methylphenyl)butanal (12.5 g, gc purity>99%; yield 36%).

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 fractionally distilled with a Vigreux column (1 mBar, 70-81° C.)
  9. customto give a colourless oil (39.6 g, gc purity 90%)
  10. customThe oil was chromatographed on a silica gel column with 7% EtOAc in hexane as elution agent

Sources & evidence

ORD record
ord-d4e247a916ed424d9f2196c3586b8831
Source dataset
uspto-grants-2014_04
Patent number
US08709994B2

Reaction notes

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