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

HRID 1941144

反応式

HRID 1941144 の反応式
[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

参加物

8

反応物 5

HCID 313Hydrochloric AcidHCID 6497Dimethyl SulfateHCID 11430Potassium CarbonateHCID 14797Potassium HydroxideHCID 178439162HCID 178439162、化合物

生成物 1

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

試薬・触媒・溶媒 2

HCID 712Formaldehyde触媒HCID 962Water溶媒

反応条件

温度
100 °C

実験手順

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. 1H NMR (CDCl3) δ(ppm) 1.29 (d, 6H, 6.9 Hz), 2.89 (qui, 1H, J=6.9 Hz), 3.97 (s, 3H), 4.67 (s, 2H), 6.77 (s, 1H), 6.84 (d, 1H, J=9.2 Hz), 7.44 (d, 1H, J=9.2 Hz).

後処理

  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

出典と根拠

ORDレコード
ord-e42e5e0d4d47478d8e0183702540a37a
出典データセット
uspto-grants-1997_12
特許番号
US05703071

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