Acetic Acid → 2,4-Dihydroxy-4b,6,7,8,8a,10-hexahydrophenanthren-9(5H)-one

HRID 1283865Notes

Reaction equation

HRID 1283865 reaction equation
[OH-].[K+].[C:3]1([CH:11]=[C:9]([OH:10])[CH:8]=[C:6]([OH:7])[CH:5]=1)O.[C:12]([C:15]1[CH2:20][CH2:19][CH2:18][CH2:17][CH:16]=1)(=[O:14])[CH3:13].C(O)(=O)C>COCCO.C(OCC)(=O)C.O>[OH:7][C:6]1[CH:8]=[C:9]([OH:10])[C:11]2[CH:20]3[CH:15]([CH2:16][CH2:17][CH2:18][CH2:19]3)[C:12](=[O:14])[CH2:13][C:3]=2[CH:5]=1

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 359PhloroglucinolHCID 136121-AcetylcyclohexeneHCID 14797Potassium Hydroxide

Product 1

HCID 203227742,4-Dihydroxy-4b,6,7,8,8a,10-hexahydrophenanthren-9(5H)-one

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 80192-MethoxyethanolSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
50 °C

Procedure

To a flask equipped with a stirrer, dropping funnel, condenser and gas inlet tube maintained under a nitrogen atmosphere, there is added 50 g (0.89) moles of potassium hydroxide in one liter of 2-methoxyethanol. Stirring is initiated and 100 g(0.79mole) of anhydrous phloroglucinol is added in three portions, followed by the addition of 100 g (0.80 mole) of 1-acetyl-cyclohexene while maintaining the temperature at 50°C. The resulting solution is refluxed at 140°C for 4 hours. After cooling there is then added gradually 53.6 g. of acetic acid while obtaining a pH of approximately 7. The solvent is then removed in vacuo, and the residue is further heated in vacuo in a bath at 70°C, to obtain a viscous residue. The resulting residue is dissolved in ethyl acetate and water; washed twice with water, dried over anhydrous sodium sulfate, filtered and evaporated in vacuo to obtain a brown solid. The resulting solid is recrystallized from ethyl acetate/cyclohexane to give 2,4-dihydroxy-4b,5,6,7,8,8a,9,10-octahydro-9 -oxo-phenanthrene. m.p. 220°-223°C.

Workup

  1. customTo a flask equipped with a stirrer
  2. temperaturemaintained under a nitrogen atmosphere
  3. temperatureThe resulting solution is refluxed at 140°C for 4 hours
  4. temperatureAfter cooling there
  5. additionis then added gradually 53.6 g
  6. customThe solvent is then removed in vacuo
  7. temperaturethe residue is further heated in vacuo in a bath at 70°C
  8. customto obtain a viscous residue
  9. washwashed twice with water
  10. dry with materialdried over anhydrous sodium sulfate
  11. filtrationfiltered
  12. customevaporated in vacuo
  13. customto obtain a brown solid
  14. customThe resulting solid is recrystallized from ethyl acetate/cyclohexane

Sources & evidence

ORD record
ord-4f0ee37b7a23466283a09f877121f6af
Source dataset
uspto-grants-1976_08
Patent number
US03976684

Reaction notes

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