Trimethylhydroquinone → Diisopropyl Ether

HRID 1646803Notes

Reaction equation

HRID 1646803 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[CH:20]=[CH:19][C:18]([CH2:21][C:22]([O:24][CH2:25][CH3:26])=[O:23])=[CH:17][CH:16]=1)[CH3:14].CC1(C)C2(CS(O)(=O)=O)C(CC1CC2)=O>C1(C)C=CC=CC=1>[CH:13]([O:7][CH:6]([CH3:5])[CH3:8])([CH3:15])[CH3:14].[CH3:1][C:2]1[C:3](=[O:11])[C:4]([CH3:10])=[C:5]([CH3:9])[C:6](=[O:7])[C:8]=1[CH:13]([C:15]1[CH:20]=[CH:19][C:18]([CH2:21][C:22]([O:24][CH2:25][CH3:26])=[O:23])=[CH:17][CH:16]=1)[CH3:14]

Participants

6

Reactant 3

HCID 12785TrimethylhydroquinoneHCID 18462Bicyclo[2.2.1]heptane-1-methanesulfonic acid, 7,7-dimethyl-2-oxo-, (1S)-HCID 19088078Ethyl [4-(1-hydroxyethyl)phenyl]acetate

Product 2

HCID 7914Diisopropyl EtherHCID 19088041HCID 19088041, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
60 °C

Procedure

To 100 ml of toluene were added 2.2 g (2 mmole) of trimethylhydroquinone and 3 g (1.5 mmole) of ethyl 4-(1-hydroxyethyl)phenylacetate, and after 0.2 g of D-camphorsulfonic acid was added, the reaction solution was stirred for 18 hours with heating at 60° C., cooled and evaporated under reduced pressure. The residue was dissolved in THF, and an aqueous solution of ferric chloride was added to the solution to carry out oxidation. Isopropyl ether (IPE) was added to the reaction solution, and the mixed solution was washed with water, dried and then evaporated under reduced pressure. The crude product was purified by silica gel column chromatography using solution: IPE to give ethyl 4-[1-(3,5,6-trimethyl-1,4-benzoquinon -2-yl)ethyl]phenylacetate. Hydrolysis of this compound with 6N hydrochloric acid in THF yielded 4-[1-(3,5,6-trimethyl-1,4-benzoquinon-2-yl)ethyl]phenylacetic acid (1 g, uield of 31%). This compound was recrystallized from IPE, m.p. 142°-143° C. δ8.70(1H,COOH), 7.19(4H,s), 4.52(1H,m), 3.58(2H,s), 1.98 (9H,s), 1.57(2H,d,7Hz).

Workup

  1. temperaturecooled
  2. customevaporated under reduced pressure
  3. dissolutionThe residue was dissolved in THF
  4. additionan aqueous solution of ferric chloride was added to the solution
  5. additionIsopropyl ether (IPE) was added to the reaction solution
  6. washthe mixed solution was washed with water
  7. customdried
  8. customevaporated under reduced pressure
  9. customThe crude product was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-5eab9ff7a6bb431f823259a9766131da
Source dataset
uspto-grants-1993_01
Patent number
US05180742

Reaction notes

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