Trimethylhydroquinone → HCID 19088055, compound

HRID 1646802Notes

Reaction equation

HRID 1646802 reaction equation
[CH3:1][C:2]1[C:3]([OH:11])=[C:4]([CH3:10])[C:5]([CH3:9])=[C:6]([CH:8]=1)[OH:7].O[CH:13]([C:15]1[S:19][C:18]([CH2:20][C:21]([OH:23])=[O:22])=[CH:17][CH:16]=1)[CH3:14].[CH3:24][C:25]1(C)C2(CS(O)(=O)=O)C(CC1CC2)=O>C1(C)C=CC=CC=1>[CH2:24]([O:23][C:21](=[O:22])[CH2:20][C:18]1[S:19][C:15]([CH:13]([C:8]2[C:6](=[O:7])[C:5]([CH3:9])=[C:4]([CH3:10])[C:3](=[O:11])[C:2]=2[CH3:1])[CH3:14])=[CH:16][CH:17]=1)[CH3:25]

Participants

5

Reactant 3

HCID 12785TrimethylhydroquinoneHCID 18462Bicyclo[2.2.1]heptane-1-methanesulfonic acid, 7,7-dimethyl-2-oxo-, (1S)-HCID 19088043HCID 19088043, compound

Product 1

HCID 19088055HCID 19088055, compoundYield 804.6%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
50 °C

Procedure

Trimethylhydroquinone (1.5 g, 10 mmole) and 5-(1-hydroxyethyl)-2-thienylacetic acid (2.5 g, 8.5 mmole) were added to 50 ml of toluene, and D-camphorsulfonic acid (0.2 g) was added to the mixture, followed by heating at 50° C. for 6 hours with stirring. After cooling, the reaction solution was concentrated under reduced pressure, and the residue was dissolved in THF. An aqueous solution of ferric chloride was added to the solution, followed by stirring at room temperature for 10 minutes. The reaction solution was extracted with isopropyl ether, and the organic layer was washed with water, dried and evaporated under reduced pressure. The crude product was purified by silica gel column chromatography using IPE:hexane(1:1) to give ethyl-5-[1-(3,5,6-trimethyl-1, 4-benzoquinon -2-yl)ethyl]-2-thienylacetate (2.4 g, 72%). Hydrolysis of this compound with 6N hydrochloric acid in THF yielded 5-[1-(3,5,6-trimethyl-1,4-benzoquinon-2-yl)ethyl]-2-thienylacetic acid (2.1 g, 90 %). δ6.69(2H,m), 4.61(1H,m), 3.73(2H,s), 1.98(9H,s), 1.61(3H,d, 7Hz).

Workup

  1. additionwas added to the mixture
  2. temperatureAfter cooling
  3. concentrationthe reaction solution was concentrated under reduced pressure
  4. dissolutionthe residue was dissolved in THF
  5. additionAn aqueous solution of ferric chloride was added to the solution
  6. stirringby stirring at room temperature for 10 minutes
  7. extractionThe reaction solution was extracted with isopropyl ether
  8. washthe organic layer was washed with water
  9. customdried
  10. customevaporated under reduced pressure
  11. customThe crude product was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-3ae4f79301884849b9139bce896abcdb
Source dataset
uspto-grants-1993_01
Patent number
US05180742

Reaction notes

Loading…