Ethyl Acetate → HCID 24824482, compound

HRID 2220409Notes

Reaction equation

HRID 2220409 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([O:12][CH2:13][CH:14]([CH3:16])[CH3:15])[CH:3]=1.[B:17]1(B2OC(C)(C)C(C)(C)O2)[O:21]C(C)(C)C(C)(C)[O:18]1.C([O-])(=O)C.[K+].C(OCC)(=O)C>O1CCOCC1.Cl[Pd]Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O>[CH2:13]([O:12][C:4]1[CH:3]=[C:2]([B:17]([OH:21])[OH:18])[CH:11]=[CH:10][C:5]=1[C:6]([O:8][CH3:9])=[O:7])[CH:14]([CH3:16])[CH3:15]

Participants

8

Reactant 4

HCID 8857Ethyl AcetateHCID 517044Potassium AcetateHCID 2733548Bis(pinacolato)diboraneHCID 24824347Methyl 4-bromo-2-(2-methylpropoxy)benzoate

Product 1

HCID 24824482HCID 24824482, compoundYield 72%

Reagents, catalysts & solvents 3

HCID 13169693Triphenylphosphine palladium dichlorideCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of methyl 4-bromo-2-isobutoxybenzoate (12.0 g), bis(pinacolato)diboron (12.2 g), dichloropalladium-triphenylphosphine (1:2, 2.05 g) and potassium acetate (12.3 g) in 1,4-dioxane (120 ml) was stirred at 90° C. for 1.5 hours. After cooling to room temperature, the reaction mixture was poured into ethyl acetate (500 ml) and water (500 ml) and the mixture was filtered through a Celite cake. The organic layer was separated and washed with water (500 ml) and brine (500 ml). The separated organic layer was concentrated under reduced pressure to ca. 150 ml. To the solution were added water (150 ml), acetic acid ammoniate (14.4 g) and sodium periodate (31.2 g) and the reaction mixture was stirred at room temperature for 3.5 hours. The reaction mixture was filtered and washed with ethyl acetate. The filtrate was extracted with ethyl acetate (twice) and the combined organic layer was washed with water and brine and dried over magnesium sulfate. Filtration followed by evaporation under reduced pressure gave a crude product followed by purification by column chromatography on silica gel (eluent: chloroform/methanol=98/2) to give [3-isobutoxy-4-(methoxycarbonyl)phenyl]boronic acid (7.58 g) as a purple solid.

Workup

  1. temperatureAfter cooling to room temperature
  2. filtrationthe mixture was filtered through a Celite cake
  3. customThe organic layer was separated
  4. washwashed with water (500 ml) and brine (500 ml)
  5. concentrationThe separated organic layer was concentrated under reduced pressure to ca. 150 ml
  6. additionTo the solution were added water (150 ml), acetic acid ammoniate (14.4 g) and sodium periodate (31.2 g)
  7. stirringthe reaction mixture was stirred at room temperature for 3.5 hours
  8. filtrationThe reaction mixture was filtered
  9. washwashed with ethyl acetate
  10. extractionThe filtrate was extracted with ethyl acetate (twice) and the combined organic layer
  11. washwas washed with water and brine
  12. dry with materialdried over magnesium sulfate
  13. filtrationFiltration
  14. customfollowed by evaporation under reduced pressure
  15. customgave a crude product
  16. customfollowed by purification by column chromatography on silica gel (eluent: chloroform/methanol=98/2)

Sources & evidence

ORD record
ord-82c5880a8c6d4530b6a5fb3f5fb4c0dc
Source dataset
uspto-grants-2008_08
Patent number
US07417060B2

Reaction notes

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