Oxygen → HCID 14418205, compound

HRID 1516960Notes

Reaction equation

HRID 1516960 reaction equation
CN(C=[O:5])C.O=O.[CH3:8][C:9]1[CH:16]=[CH:15][C:12]([CH:13]=[CH2:14])=[CH:11][CH:10]=1.[C:17]1([Mg]Br)[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1>Cl[Pd]Cl.Cl[Cu].O>[C:17]1([C:13]([C:12]2[CH:15]=[CH:16][C:9]([CH3:8])=[CH:10][CH:11]=2)([OH:5])[CH3:14])[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1

Participants

8

Reactant 4

HCID 977OxygenHCID 6228DimethylformamideHCID 121611-Ethenyl-4-methylbenzeneHCID 178418255HCID 178418255, compound

Product 1

HCID 14418205HCID 14418205, compoundYield 62%

Reagents, catalysts & solvents 3

HCID 24290Palladium ChlorideCatalystHCID 62652Cuprous chlorideCatalystHCID 962WaterSolvent

Procedure

Sequential reaction of a Wacker-Tsuji oxidation followed by Grignard reduction. A PDMS thimble containing PdCl2 (0.100 g, 0.564 mmol) and CuCl (0.564 g, 5.64 mmol) was placed in a 2-necked Schlenk flask with a stir bar. DMF (3.96 mL) and H2O (0.56 mL) were added to the inside of the PDMS thimble and the flask was capped with a rubber septum. A balloon filled with O2 was affixed to the septum and the reaction mixture was stirred at room temperature for 1 hour. p-Methylstyrene (0.742 mL, 5.64 mmol) was added to the reaction mixture and allowed to stir under an O2 atmosphere for 24 hours. The PDMS thimble was swelled with hexanes (30 mL) for 0.5 hours with a stir bar added to the exterior of the PDMS thimble. Phenylmagnesium bromide (3M in Et2O, 18.8 mL, 56.4 mmol) was added to the exterior of the thimble and stirred under N2 for 12 h. The exterior solvent was removed and the PDMS thimble was swelled with Et2O (4×50 mL). The combined solvents were transferred to a separatory funnel and 3N HCl (200 mL) was added. 3N HCl (200 mL) was used two more times to extract from the organic layer then the organic layer was dried over Na2SO4 and filtered. The organic solvents were concentrated in vacuo. 1-Phenyl-1-p-tolyl-ethanol (0.737 g, 62% yield) was isolated by column chromatography using hexanes/EtOAc (95/5). NMR spectra agree with those reported in the literature. 1H NMR (300 MHz, CDCl3, δ): 7.33 (d, J=8.1 Hz, 2H), 7.17 (m, 5H), 7.03 (d, J=8.1 Hz, 2H), 2.62 (s, 1H), 2.25 (s, 3H), 1.81, (s, 3H). 13C NMR (75.48 MHz; CDCl3, δ): 148.1, 145.0, 136.2, 128.6, 127.9, 126.6, 125.7, 125.6, 75.8, 30.6, 20.8.

Workup

  1. customSequential reaction of a Wacker-Tsuji oxidation
  2. customwas placed in a 2-necked Schlenk flask with a stir bar
  3. customthe flask was capped with a rubber septum
  4. stirringto stir under an O2 atmosphere for 24 hours
  5. stirringstirred under N2 for 12 h
  6. customThe exterior solvent was removed
  7. customThe combined solvents were transferred to a separatory funnel
  8. addition3N HCl (200 mL) was added
  9. extractionto extract from the organic layer
  10. dry with materialthe organic layer was dried over Na2SO4
  11. filtrationfiltered
  12. concentrationThe organic solvents were concentrated in vacuo

Sources & evidence

ORD record
ord-f6c3da3aa80548f2bf6316fa9fa5da87
Source dataset
uspto-grants-2012_07
Patent number
US08227635B2

Reaction notes

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