Water → Methyl 3-methoxy-4-(4-methyl-3-thienyl)benzoate

HRID 400758Notes

Reaction equation

HRID 400758 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[O:12][CH3:13].[CH3:14][C:15]1[C:16](B(O)O)=[CH:17][S:18][CH:19]=1.C(=O)([O-])[O-].[K+].[K+].O>C1(C)C=CC=CC=1.CCOC(C)=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:13][O:12][C:3]1[CH:4]=[C:5]([CH:10]=[CH:11][C:2]=1[C:16]1[C:15]([CH3:14])=[CH:19][S:18][CH:17]=1)[C:6]([O:8][CH3:9])=[O:7]

Participants

8

Reactant 4

HCID 962WaterHCID 11430Potassium CarbonateHCID 50839314-Methyl-3-thiopheneboronic acidHCID 14570117Methyl 4-bromo-3-methoxybenzoate

Product 1

HCID 67400074Methyl 3-methoxy-4-(4-methyl-3-thienyl)benzoate

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

Methyl 4-bromo-3-methoxybenzoate (Combi-Blocks, 2.50 g; 10.20 mmol) and 4-methyl-3-thiopheneboronic acid (1.59 g; 11.22 mmol), potassium carbonate (7.04 g; 51 mmol), tetrakis(triphenylphosphine)palladium(0) (1.17 g; 1.02 mmol) were mixed in toluene (10 mL) and water (10 mL) under N2 atmosphere. The reaction mixture was degassed with N2 for 10 min and was heated under reflux for 3 hours. The reaction mixture was cooled to RT, filtered over a pad of celite and washed with toluene. The filtrate was concentrated under vacuum to afford brown oil. It was taken in EtOAc and the organic layer was washed with a saturated aqueous solution of NaHCO3, water and brine. It was dried over MgSO4, filtered off and concentrated under vacuum giving a brown oil. LC/MS (Method A): 262.8 (M+1-1)+. HPLC (Method A) Rt 4.79 min (Purity: 63.0%).

Workup

  1. customThe reaction mixture was degassed with N2 for 10 min
  2. temperaturewas heated
  3. temperatureunder reflux for 3 hours
  4. filtrationfiltered over a pad of celite
  5. washwashed with toluene
  6. concentrationThe filtrate was concentrated under vacuum
  7. customto afford brown oil
  8. washthe organic layer was washed with a saturated aqueous solution of NaHCO3, water and brine
  9. dry with materialIt was dried over MgSO4
  10. filtrationfiltered off
  11. concentrationconcentrated under vacuum
  12. customgiving a brown oil

Sources & evidence

ORD record
ord-88614171eac04e7c8822deb2fc2f6812
Source dataset
uspto-grants-2014_06
Patent number
US08741923B2

Reaction notes

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