Sodium Carbonate → Methyl 3-bromo-5-[(1E)-3-methoxy-1-propen-1-yl]-4-methylbenzoate

HRID 337648Notes

Reaction equation

HRID 337648 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([Br:13])[C:11]=1[CH3:12])[C:5]([O:7][CH3:8])=[O:6].CC1(C)C(C)(C)OB(/[CH:22]=[CH:23]/[CH2:24][O:25][CH3:26])O1.C([O-])([O-])=O.[Na+].[Na+]>CN(C=O)C.O>[Br:13][C:10]1[CH:9]=[C:4]([CH:3]=[C:2](/[CH:22]=[CH:23]/[CH2:24][O:25][CH3:26])[C:11]=1[CH3:12])[C:5]([O:7][CH3:8])=[O:6]

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 624016Methyl 3,5-dibromo-4-methylbenzoateHCID 162174432-[(1E)-3-methoxyprop-1-en-1-yl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Product 1

HCID 67062162Methyl 3-bromo-5-[(1E)-3-methoxy-1-propen-1-yl]-4-methylbenzoate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of methyl 3,5-dibromo-4-methylbenzoate (1 eq.) and 4,4,5,5-tetramethyl-2-[(1E)-3-(methyloxy)-1-propen-1-yl]-1,3,2-dioxaborolane (1.1 eq.) in DMF (0.1 M) was added trans-bis(triphenylphosphine) palladium(II) bromide (0.02 eq.). The vessel was repeatedly evacuated and back-filled with nitrogen. Finally, 2 M aq. Na2CO3 (3 eq.) was added and the resulting mixture was heated at 100° C. for 2 h. The now black suspension was cooled to RT, diluted with water and extracted with ether. The combined organic extracts were washed further with water and brine, dried over Na2SO4, filtered and the filtrate concentrated in vacuo. Purification of the crude product by way of flash chromatography (SiO2, 9:1 (v/v) Hex:EtOAc→→1:1 (v/v) Hex:EtOAc) afforded the title compound as a colorless oil.

Workup

  1. customThe vessel was repeatedly evacuated
  2. additionback-filled with nitrogen
  3. temperatureThe now black suspension was cooled to RT
  4. extractionextracted with ether
  5. washThe combined organic extracts were washed further with water and brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationthe filtrate concentrated in vacuo
  9. customPurification of the crude product by way of flash chromatography (SiO2, 9:1 (v/v) Hex:EtOAc→→1:1 (v/v) Hex:EtOAc)

Sources & evidence

ORD record
ord-28bfd96c2894402291065b971f24b0f5
Source dataset
uspto-grants-2014_11
Patent number
US08889714B2

Reaction notes

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