Hydrogen Peroxide → HCID 178504195, compound

HRID 1275540Notes

Reaction equation

HRID 1275540 reaction equation
[OH:1][C:2]1[C:3](=[O:23])[C:4]2[C:9]([C:10](=[O:22])[C:11]=1[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16]C[Si](C)(C)C)=[CH:8][CH:7]=[CH:6][CH:5]=2.C(OC1C(=O)C2C(C(=O)C=1)=CC=CC=2)(=O)C1C=CC=CC=1.[CH3:45][Si:46](C(CCCCC)C(O)=O)([CH3:48])[CH3:47].C(=O)([O-])[O-].[Na+].[Na+].OO>O1CCOCC1.O.S([O-])([O-])(=O)=O.[Cu+2]>[OH:1][C:2]1[C:3](=[O:23])[C:4]2[C:9]([C:10](=[O:22])[C:11]=1[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][Si:46]([CH3:48])([CH3:47])[CH3:45])=[CH:8][CH:7]=[CH:6][CH:5]=2

Participants

9

Reactant 5

HCID 784Hydrogen PeroxideHCID 10340Sodium CarbonateHCID 825051HCID 825051, compoundHCID 22117156HCID 22117156, compoundHCID 178504196HCID 178504196, compound

Product 1

HCID 178504195HCID 178504195, compound

Reagents, catalysts & solvents 3

HCID 24462Copper SulfateCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
70 °C

Procedure

2-Hydroxy-3(6'-trimethylsilylhexyl)-1,4-naphthoquinone (337 mg, 1.02 mmol), prepared from 2-benzoyloxy-1,4-naphthoquinone and trimethylsilylheptanoic acid by the method of Example 1 followed by the method of Example 2, was dissolved in dioxane (2.5 ml) under nitrogen. Sodium carbonate (120 mg) in water (2.5 ml) was added followed by an excess of 30% (w/v) hydrogen peroxide (200 μl). The mixture was heated at 70° C. for 40 minutes during which time the reaction mixture turned from red to colourless. The reaction mixture was allowed to cool and 20% (w/v) copper sulphate solution (100 μl) was added and the solution stirred until bubbling ceased. 25% (w/v) sodium hydroxide solution (2 ml) and 20% (w/v) copper sulphate solution (5 ml) were then added and the reaction mixture heated at 70° C. for 30 minutes. The mixture was allowed to cool and acidified to pH 2 with 1N hydrochloric acid. The product was extracted into diethyl ether and the ether extract was then washed with brine, dried over anhydrous magnesium sulphate and concentrated in vacuo. The crude material was chromatographed using 5% diethyl ether/hexane as eluent to give 2-hydroxy-3(5'-trimethylsilylpentyl)-1,4-naphthoquinone (202 mg) which was recrystallised from hexane, m. pt. 73-75° C. NMR peaks at: 184.6, 181.4, 153.0, 134.8, 132.9, 132.7, 129.4, 126.7, 126.0, 124.8; 33.6, 27.9, 33.7, 23.2, 16.5; -1.7.

Workup

  1. temperatureto cool
  2. customuntil bubbling
  3. addition25% (w/v) sodium hydroxide solution (2 ml) and 20% (w/v) copper sulphate solution (5 ml) were then added
  4. temperaturethe reaction mixture heated at 70° C. for 30 minutes
  5. temperatureto cool
  6. extractionThe product was extracted into diethyl ether
  7. extractionthe ether extract
  8. washwas then washed with brine
  9. dry with materialdried over anhydrous magnesium sulphate
  10. concentrationconcentrated in vacuo
  11. customThe crude material was chromatographed

Sources & evidence

ORD record
ord-85ac3400b43e45179af89ef17936d9b5
Source dataset
uspto-grants-2000_12
Patent number
US06162799

Reaction notes

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