Ethyl Acetate → HCID 24751760, compound

HRID 922065Notes

Reaction equation

HRID 922065 reaction equation
[CH3:1][C:2]1([CH3:20])[CH2:11][CH2:10][C:9]2[C:4](=[C:5]([CH3:19])[C:6]([CH3:18])=[C:7]([OH:17])[C:8]=2[CH2:12][CH:13]=[C:14]([CH3:16])[CH3:15])[O:3]1.C(OCC)(=[O:23])C>[Pd]>[OH:3][C:2]([CH3:20])([CH3:1])[CH2:11][CH2:10][C:9]1[C:4](=[O:23])[C:5]([CH3:19])=[C:6]([CH3:18])[C:7](=[O:17])[C:8]=1[CH2:12][CH2:13][CH:14]([CH3:16])[CH3:15]

Participants

4

Reactant 2

HCID 8857Ethyl AcetateHCID 11288837HCID 11288837, compound

Product 1

HCID 24751760HCID 24751760, compound

Reagents, catalysts & solvents 1

HCID 23938PalladiumCatalyst

Conditions

Temperature
5 °C

Procedure

To a solution of 2,2,7,8-tetramethyl-5-(3-methyl-but-2-enyl)-chroman-6-ol (68 mg) in ethyl acetate (2.4 mL) was added Pd/C (26 mg, 5% w/w). The resulting suspension was flushed with hydrogen gas, the container sealed, and the contents stirred under 1 atm of hydrogen gas for 30 min. The mixture was then filtered and concentrated in vacuo. The resulting residue was dissolved in acetonitrile-water (5:1, 2.6 mL) and the solution cooled to 5° C. in an ice-water bath. Into the reaction mixture was added a solution of cerium(IV) ammonium nitrate (287 mg) in acetonitrile-water (1:4, 1.6 mL) over a period of 5 minutes. The reaction mixture was allowed to stir for an additional 5 minutes, after which it was poured into a separatory funnel containing dichloromethane (30 mL) and water (30 mL). The aqueous layer was removed and the remaining organics were washed once with 1.0 M sodium chloride solution (30 mL). The organics were subsequently dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. Silica gel chromatography (18% ethyl acetate-82% hexanes) provided 29 mg of 2-(3-hydroxy-3-methyl-butyl)-5,6-dimethyl-3-(3-methyl-butyl)-[1,4]benzoquinone. 1H NMR (CDCl3, 400 MHz) 2.53 (m, 2H), 2.43 (m, 2H), 1.99 (s, 3H), 1.62 (m, 1H), 1.53 (m, 2H), 1.24 (m, 8H), 0.94 (s, 3H), 0.92 (s, 3H).

Workup

  1. customThe resulting suspension was flushed with hydrogen gas
  2. customthe container sealed
  3. filtrationThe mixture was then filtered
  4. concentrationconcentrated in vacuo
  5. dissolutionThe resulting residue was dissolved in acetonitrile-water (5:1, 2.6 mL)
  6. additionInto the reaction mixture was added a solution of cerium(IV) ammonium nitrate (287 mg) in acetonitrile-water (1:4, 1.6 mL) over a period of 5 minutes
  7. stirringto stir for an additional 5 minutes
  8. additionafter which it was poured into a separatory funnel
  9. additioncontaining dichloromethane (30 mL) and water (30 mL)
  10. customThe aqueous layer was removed
  11. washthe remaining organics were washed once with 1.0 M sodium chloride solution (30 mL)
  12. dry with materialThe organics were subsequently dried over anhydrous sodium sulfate
  13. filtrationfiltered
  14. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-400196ad5ba544e29c10b5c6afc23575
Source dataset
uspto-grants-2016_03
Patent number
US09278085B2

Reaction notes

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