Hydrogen Peroxide → HCID 22287194, compound

HRID 2257425Notes

Reaction equation

HRID 2257425 reaction equation
[OH:1][C:2]([CH3:14])([CH3:13])[C:3]#[C:4][C:5]1[CH:10]=[CH:9][C:8](Br)=[CH:7][C:6]=1[F:12].[OH-].[Na+].CN1[CH2:22][CH2:21][CH2:20][C:19]1=O.OO.O1CCC[CH2:27]1>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>[OH:1][C:2]([CH3:14])([CH3:13])[C:3]#[C:4][C:5]1[CH:10]=[CH:9][C:8](/[CH:19]=[CH:20]/[CH2:21][CH2:22][CH3:27])=[CH:7][C:6]=1[F:12]

Participants

7

Reactant 5

HCID 784Hydrogen PeroxideHCID 8028Tetrahydrofuran2×HCID 13387N-methyl-2-pyrrolidoneHCID 14798Sodium HydroxideHCID 22287527HCID 22287527, compound

Product 1

HCID 22287194HCID 22287194, compoundYield 84%

Reagents, catalysts & solvents 1

HCID 178418476HCID 178418476, compoundCatalyst

Procedure

In a four necked flask equipped with a stirrer, a reflux condenser and a thermometer which had been replaced by a nitrogen atmosphere, 4-(3-hydroxy-3,3-dimethyl-1-propynyl)-3-fluoro-1-bromobenzene (3.9 g, 15 mmol), bis(triphenylphosphine)palladium chloride (0.07 g, 0.1 mmol), sodium hydroxide (1.2 g, 30 mmol), tetrahydrofuran (40 ml) and N-methylpyrrolidone (5 ml) were charged. Then, to the mixture, a solution of E-1-pentenylcatecholborane prepared in Reference Example 1 (20 mmol) in tetrahydrofuran (50 ml) was dropwise added at room temperature, followed by heat refluxing for 6 hours while stirring. After cooling the reaction mixture to room temperature, 30% aqueous hydrogen peroxide (2 ml) was added to the mixture, followed by stirring for 1 hour. The mixture was extracted with toluene and water. The organic layer was washed with water twice and dried over anhydrous magnesium sulfate. After evaporating the solvent off, the residue was purified by silica gel column chromatography to obtain 4-(3-hydroxy-3,3-dimethyl-1-propynyl)-1-(1-trans-pentenyl)-3-fluorobenzene (3.1 g). Yield: 84%. Melting point: 62° C.

Workup

  1. customIn a four necked flask equipped with a stirrer, a reflux condenser
  2. additionwere charged
  3. additionwas dropwise added at room temperature
  4. temperatureby heat
  5. temperaturerefluxing for 6 hours
  6. stirringby stirring for 1 hour
  7. extractionThe mixture was extracted with toluene and water
  8. washThe organic layer was washed with water twice
  9. dry with materialdried over anhydrous magnesium sulfate
  10. customAfter evaporating the solvent off, the residue
  11. customwas purified by silica gel column chromatography

Sources & evidence

ORD record
ord-e771eb0c592844349a21fa84f0e1c29b
Source dataset
uspto-grants-1997_08
Patent number
US05658489

Reaction notes

Loading…