Hydrochloric Acid → HCID 69103710, compound

HRID 2220416Notes

Reaction equation

HRID 2220416 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10])=[C:4]([O:14][CH:15]2[CH2:20][CH2:19][CH2:18][CH2:17][CH2:16]2)[CH:3]=1.CC1(C)C(C)(C)[O:25][B:24](B2OC(C)(C)C(C)(C)O2)[O:23]1.C([O-])(=O)C.[K+].Cl>O1CCOCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH:15]1([O:14][C:4]2[CH:3]=[C:2]([B:24]([OH:25])[OH:23])[CH:7]=[CH:6][C:5]=2[CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH2:20][CH2:19][CH2:18][CH2:17][CH2:16]1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 517044Potassium AcetateHCID 2733548Bis(pinacolato)diboraneHCID 86056548HCID 86056548, compound

Product 1

HCID 69103710HCID 69103710, compoundYield 65.2%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
95 °C

Procedure

To a solution of ethyl (4-bromo-2-cyclohexyloxyphenyl)acetate (1.23 g) in 1,4-dioxane (14.6 ml) were added 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi-1,3,2-dioxaborolane (1.01 g), dichlorobis(triphenyphosphine)palladium(II) (126 mg) and potassium acetate (1.06 g) at room temperature under nitrogen, and the mixture was stirred at 95° C. for 2 hours. The resulting mixture was poured into 1N hydrochloric acid and the aqueous layer was extracted with a mixture of hexane and ethyl acetate (1:1). The organic layer was washed successively with water and brine, dried over anhydrous magnesium sulfate, evaporated and dried in vacuo. To a suspension of the above obtained residue in a mixture of ethyl acetate (14.6 ml) and water (24.6 ml) were added ammonium acetate (1.75 g) and sodium periodate (4.86 g) at room temperature, and the mixture was stirred at the same temperature for 24 hours. The resulting mixture was poured into dilute hydrochloric acid and the aqueous layer was extracted with ethyl acetate. The organic layer was washed successively with water and brine, dried over anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel (hexane/ethyl acetate=2:1 to 1:1) to give [3-cyclohexyloxy-4-(ethoxycarbonylmethyl)phenyl]boronic acid (719 mg).

Workup

  1. extractionthe aqueous layer was extracted with a mixture of hexane and ethyl acetate (1:1)
  2. washThe organic layer was washed successively with water and brine
  3. dry with materialdried over anhydrous magnesium sulfate
  4. customevaporated
  5. customdried in vacuo
  6. additionTo a suspension of the above obtained residue
  7. additionin a mixture of ethyl acetate (14.6 ml) and water (24.6 ml)
  8. additionwere added ammonium acetate (1.75 g) and sodium periodate (4.86 g) at room temperature
  9. stirringthe mixture was stirred at the same temperature for 24 hours
  10. additionThe resulting mixture was poured into dilute hydrochloric acid
  11. extractionthe aqueous layer was extracted with ethyl acetate
  12. washThe organic layer was washed successively with water and brine
  13. dry with materialdried over anhydrous magnesium sulfate
  14. customevaporated under reduced pressure
  15. customThe residue was purified by column chromatography on silica gel (hexane/ethyl acetate=2:1 to 1:1)

Sources & evidence

ORD record
ord-99c66e29591b4748b011ec8984557ec9
Source dataset
uspto-grants-2008_08
Patent number
US07417060B2

Reaction notes

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