Menadiol → 6-(3-Methyl-1,4-naphthoquinon-2-yl)-6-(4-methoxyphenyl)hexanoic acid

HRID 1646788Notes

Reaction equation

HRID 1646788 reaction equation
[CH3:1][C:2]1[CH:11]=[C:10]([OH:12])[C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[C:3]=1[OH:13].C(O[CH:17]([C:25]1[CH:30]=[CH:29][C:28]([O:31][CH3:32])=[CH:27][CH:26]=1)[CH2:18][CH2:19][CH2:20][CH2:21][C:22]([OH:24])=[O:23])C>CC1(C)C2(CS(O)(=O)=O)C(CC1CC2)=O.C1(C)C=CC=CC=1>[CH3:1][C:2]1[C:3](=[O:13])[C:4]2[C:9](=[CH:8][CH:7]=[CH:6][CH:5]=2)[C:10](=[O:12])[C:11]=1[CH:17]([C:25]1[CH:26]=[CH:27][C:28]([O:31][CH3:32])=[CH:29][CH:30]=1)[CH2:18][CH2:19][CH2:20][CH2:21][C:22]([OH:24])=[O:23]

Participants

5

Reactant 2

HCID 10209MenadiolHCID 190880606-Ethoxy-6-(4-methoxyphenyl)hexanoic acid

Product 1

HCID 152308586-(3-Methyl-1,4-naphthoquinon-2-yl)-6-(4-methoxyphenyl)hexanoic acidYield 45%

Reagents, catalysts & solvents 2

HCID 18462Bicyclo[2.2.1]heptane-1-methanesulfonic acid, 7,7-dimethyl-2-oxo-, (1S)-CatalystHCID 1140TolueneSolvent

Conditions

Temperature
60 °C

Procedure

D-Camphor-10-sulfonic acid (0.1 g) was added to a toluene solution (50 ml) of 2-methyl-1,4-naphthohydroquinone (3.6 g, 0.02 mole) and 6-ethoxy-6-(4-methoxyphenyl)hexanoic acid (5.6 g, 0.021 mole), and the mixture was heated at 60° C. for 18 hours, with stirring. After cooling, the solvent was distilled off under reduced pressure, and then tetrahydrofuran (20 ml) was added to the residue. A 10% aqueous solution of ferric chloride was added to the solution, followed by stirring for 10 minutes, and the reaction product was extracted with ethyl acetate. The organic layer was washed with water, dried and concentrated under reduced pressure. The residue was chromatographed on a silica gel column, and elution was effected with isopropyl ether to give 6-(3-methyl-1,4-naphthoquinon -2-yl)-6-(4-methoxyphenyl)hexanoic acid (3.5 g, 45%). This product was recrystallized from isopropyl ether. Its typical physical properties and nuclear magnetic resonance spectrum data are shown in Table 1. By following the procedure of this Example, the Compound No. 21 was prepared.

Workup

  1. temperatureAfter cooling
  2. distillationthe solvent was distilled off under reduced pressure
  3. additiontetrahydrofuran (20 ml) was added to the residue
  4. additionA 10% aqueous solution of ferric chloride was added to the solution
  5. stirringby stirring for 10 minutes
  6. extractionthe reaction product was extracted with ethyl acetate
  7. washThe organic layer was washed with water
  8. customdried
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was chromatographed on a silica gel column, and elution

Sources & evidence

ORD record
ord-2a4846cc186e4d098fc646fb57bea6a4
Source dataset
uspto-grants-1993_01
Patent number
US05180742

Reaction notes

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