Hydrochloric Acid → 7-Hydroxymethyl-4-isopropyl-2-methoxy-2,4,6-cycloheptatrien-1-one

HRID 234153

Reaction equation

HRID 234153 reaction equation
[CH3:1][CH:2]([C:4]1[CH:11]=[C:10]([OH:12])[C:8](=[O:9])[CH:7]=[CH:6][CH:5]=1)[CH3:3].[OH-].[K+].Cl.[C:16](=[O:19])([O-])[O-].[K+].[K+].S(OC)(O[CH3:26])(=O)=O>O.C=O>[OH:19][CH2:16][C:7]1[C:8](=[O:9])[C:10]([O:12][CH3:26])=[CH:11][C:4]([CH:2]([CH3:1])[CH3:3])=[CH:5][CH:6]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 6497Dimethyl SulfateHCID 11430Potassium CarbonateHCID 14797Potassium HydroxideHCID 178439162HCID 178439162, compound

Product 1

HCID 151426617-Hydroxymethyl-4-isopropyl-2-methoxy-2,4,6-cycloheptatrien-1-oneYield 74%

Reagents, catalysts & solvents 2

HCID 712FormaldehydeCatalystHCID 962WaterSolvent

Conditions

Temperature
100 °C

Procedure

Hinokitiol (20 g, 0.12 mol) and potassium hydroxide (8 g, 0.12 mol) were dissolved in water (80 ml), and 37% Formalin (12 ml, 0.16 mmol) was added thereto. The reaction solution was heated at 100° C. for 5 hours while stirring. The reaction solution was neutralized with 6N HCl, then the reaction product was extracted with dichloromethane. The extract was dried over sodium sulfate, then concentrated under reduced pressure. The residue was dissolved in acetone (200 ml), potassium carbonate (34 g, 0.25 mol) and dimethyl sulfate (16 ml, 0.16 mol) were added thereto, and the solution was heated and refluxed for an hour with stirring. The precipitate was removed by filtration, and filtrate was concentrated under reduced pressure. The filtration residue was washed with dichloromethane. The resultant was washed with water and dried over sodium sulfate. The solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography [(eluent:hexane/ethyl acetate (1:4)] to give 18.5 g of 7-hydroxymethyl-4-isopropyl-2-methyoxy-2,4,6-cycloheptatrien-1-one as a pale yellow oil (yield, 74%). This oil was solidified when allowed to stand at room temperature.

Workup

  1. extractionthe reaction product was extracted with dichloromethane
  2. dry with materialThe extract was dried over sodium sulfate
  3. concentrationconcentrated under reduced pressure
  4. dissolutionThe residue was dissolved in acetone (200 ml)
  5. temperaturethe solution was heated
  6. temperaturerefluxed for an hour
  7. stirringwith stirring
  8. customThe precipitate was removed by filtration, and filtrate
  9. concentrationwas concentrated under reduced pressure
  10. washThe filtration residue was washed with dichloromethane
  11. washThe resultant was washed with water
  12. dry with materialdried over sodium sulfate
  13. distillationThe solvent was distilled off under reduced pressure
  14. customthe residue was purified by silica gel column chromatography [(eluent
  15. customhexane/ethyl acetate (1:4)] to give

Sources & evidence

ORD record
ord-c1febb105e434cd2b70613efeaf5416b
Source dataset
uspto-grants-1997_01
Patent number
US05594144

Linked notes

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