Benzene, [[(2-bromo-2-propenyl)oxy]methyl]- → HCID 58550929, compound

HRID 1908121Notes

Reaction equation

HRID 1908121 reaction equation
Br[C:2](=[CH2:12])[CH2:3][O:4]CC1C=CC=CC=1.[CH3:13][O:14][C:15]1[CH:16]=[C:17]([CH:28]=[CH:29][C:30]=1B1OC(C)(C)C(C)(C)O1)[C:18]([O:20]CC1C=CC=CC=1)=[O:19]>CN(C=O)C.Cl[Pd](Cl)([P+](C1CCCCC1)(C1CCCCC1)C1C=CC=CC=1)[P+](C(C)(C)C)(C(C)(C)C)C(C)(C)C.[Pd]>[OH:4][CH2:3][CH:2]([C:30]1[CH:29]=[CH:28][C:17]([C:18]([OH:20])=[O:19])=[CH:16][C:15]=1[O:14][CH3:13])[CH3:12]

Participants

6

Reactant 2

HCID 10857167Benzene, [[(2-bromo-2-propenyl)oxy]methyl]-HCID 58551005HCID 58551005, compound

Product 1

HCID 58550929HCID 58550929, compound

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 178454888HCID 178454888, compoundCatalystHCID 6228DimethylformamideSolvent2×

Conditions

Temperature
90 °C

Procedure

Dichloro-[dicyclohexyl(phenyl)phosphaniumyl]-tritert-butylphosphaniumyl-palladium (981 mg, 0.150 mmol) and 2-bromoallyloxymethylbenzene (341 mg, 1.50 mmol) were dissolved in DMF (1 mL). A solution of benzyl 3-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate (1.11 g, 3.00 mmol) in DMF (3 mL) was added the mixture was heated at 90° C. for 3 h. The mixture was then filtered through Celite using ethyl acetate. The filtrate was then washed with brine, dried over sodium sulfate, filtered, and concentrated. The residue from step 1 was taken up in isopropanol (2 mL) and was added to 10% Pd/C (160 mg, 0.150 mmol). The vessel was purged with nitrogen and a balloon of hydrogen was added and the reaction mixture was allowed to stir overnight. The reaction mixture was filtered through Celite and the filtrate was concentrated. The residue was partitioned between aqueous 2M Na2CO3 and ethyl acetate. The layers were separated and the organic phase was discarded. To the aqueous phase was added 1M HCl until the solution was pH 3. The solution was then extracted with EtOAc (3×) and the combined organic layers were dried over sodium sulfate, filtered, and concentrated to provide 4-(1-hydroxypropan-2-yl)-3-methoxybenzoic acid. ESI-MS m/z calc 210.1. found 211.1 (M+1)+. Retention time: 1.19 minutes (3 min run).

Workup

  1. filtrationThe mixture was then filtered through Celite
  2. washThe filtrate was then washed with brine
  3. dry with materialdried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe vessel was purged with nitrogen
  7. additiona balloon of hydrogen was added
  8. filtrationThe reaction mixture was filtered through Celite
  9. concentrationthe filtrate was concentrated
  10. customThe residue was partitioned between aqueous 2M Na2CO3 and ethyl acetate
  11. customThe layers were separated
  12. additionTo the aqueous phase was added 1M HCl until the solution
  13. extractionThe solution was then extracted with EtOAc (3×)
  14. dry with materialthe combined organic layers were dried over sodium sulfate
  15. filtrationfiltered
  16. concentrationconcentrated

Sources & evidence

ORD record
ord-182670de066043bbb8663a90ce6f79b6
Source dataset
uspto-grants-2013_12
Patent number
US08598164B2

Reaction notes

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