Hydrogen Peroxide → HCID 56619791, compound

HRID 1789612Notes

Reaction equation

HRID 1789612 reaction equation
[CH3:1][CH:2]([CH2:21][CH2:22][CH:23]=[C:24]([CH3:26])[CH3:25])[CH2:3][CH2:4][CH:5]1[C:9](=[CH:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][C:16]([O:18][CH3:19])=[O:17])[C:8](=[O:20])[CH:7]=[CH:6]1.OO.[OH-].[Na+].[Cl-:31].[NH4+]>CO>[Cl:31][C:7]1[C:8](=[O:20])[C:9](=[CH:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][C:16]([O:18][CH3:19])=[O:17])[CH:5]([CH2:4][CH2:3][CH:2]([CH3:1])[CH2:21][CH2:22][CH:23]=[C:24]([CH3:25])[CH3:26])[CH:6]=1.[CH3:19][O:18][C:16]([CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][CH:10]=[C:9]1[C:8](=[O:20])[CH:7]=[CH:6][CH2:5]1)=[O:17].[Cl:31][C:7]1[C:8](=[O:20])[C:9](=[CH:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][C:16]([OH:18])=[O:17])[CH:5]([CH2:4][CH2:3][CH:2]([CH3:1])[CH2:21][CH2:22][CH:23]=[C:24]([CH3:26])[CH3:25])[CH:6]=1

Participants

8

Reactant 4

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 25517Ammonium ChlorideHCID 70403049HCID 70403049, compound

Product 3

HCID 56610153HCID 56610153, compoundHCID 56619791HCID 56619791, compoundYield 8%HCID 86741758HCID 86741758, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

422 mg (1.17 mmol) of 4-(3,7-dimethyl-6-octen-1-yl)-5-(6-methoxycarbonylhexylidene)-2-cyclopentenone was dissolved in 4 ml of methanol. With ice cooling and stirring, 600 μl (5.85 mmol) of 30% aqueous hydrogen peroxide and further 40 μl (40 mmol) of an aqueous solution of 1N sodium hydroxide were added thereto. After the mixture was stirred at 0° C. for 45 minutes, a saturated aqueous solution of ammonium chloride was added to the reaction mixture, the mixture was extracted with hexane, dried over anhydrous sodium sulfate, filtrated, and concentrated. 408 mg of the thus obtained oily product was dissolved in 4 ml of acetone. With ice cooling and stirring, 800 μm of concentrated hydrochloric acid was added to the solution and the mixture was stirred at 0° C. for 10 minutes and then at room temperature for 2 hours. A saturated saline solution was added thereto and the pH of the mixture was adjusted to 4 with an aqueous solution of 5N sodium hydroxide and extracted with ethyl acetate. The collected organic layer was washed with a saturated saline solution, dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to silica gel column chromatography (silica gel, 45 g; eluent, cyclohexane:ethyl acetate=30:1→1:2) to obtain 28 mg (yield 6%) of a low polar isomer (Z-form) of 2-chloro-4-(3,7-dimethyl-6-octenyl)-5-(6-methoxycarbonylhexylidene)-2-cyclopentenone, 168 mg (yield 36%) of its high polyer isomer (E-form), 46 mg (yield 9%) of 2-chloro-4-)6-chloro-3,7-dimethyloctyl)-5-(6-methoxycarbonylhexylidene)-2-cyclopentenone, and 34 mg (yield 8%) of 2-chloro-4-(3,7-dimethyl-6-octenyl)-5-(6-carboxyhexylidene)-2-cyclopentenone.

Workup

  1. stirringAfter the mixture was stirred at 0° C. for 45 minutes
  2. extractionthe mixture was extracted with hexane
  3. dry with materialdried over anhydrous sodium sulfate
  4. filtrationfiltrated
  5. concentrationconcentrated
  6. dissolution408 mg of the thus obtained oily product was dissolved in 4 ml of acetone
  7. stirringWith ice cooling and stirring
  8. addition800 μm of concentrated hydrochloric acid was added to the solution
  9. stirringthe mixture was stirred at 0° C. for 10 minutes
  10. additionA saturated saline solution was added
  11. extractionextracted with ethyl acetate
  12. washThe collected organic layer was washed with a saturated saline solution
  13. dry with materialdried over anhydrous sodium sulfate
  14. filtrationfiltered
  15. concentrationconcentrated

Sources & evidence

ORD record
ord-75cc88c9f3e8425b88b8b37838a6f11c
Source dataset
uspto-grants-1987_08
Patent number
US04689426

Reaction notes

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