(+)-Camphorquinone → (1s,4r)-1,7,7-Trimethyl-3-[2-(5-methyl-1-phenyl-1h-pyrazol-4-yl)-2-oxo-eth-(e)-ylidene]-bicyclo[2.2.1]heptan-2-one

HRID 2243903Notes

Reaction equation

HRID 2243903 reaction equation
COP([CH2:7][C:8]([C:10]1[CH:11]=[N:12][N:13]([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[C:14]=1[CH3:15])=[O:9])(=O)OC.CC(C)([O-])C.[K+].[CH3:28][C@@:29]12[C:35]([CH3:37])([CH3:36])[C@@H:32]([CH2:33][CH2:34]1)[C:31](=O)[C:30]2=[O:39]>C(O)(C)(C)C>[CH3:28][C@@:29]12[C:35]([CH3:37])([CH3:36])[C@@H:32]([CH2:33][CH2:34]1)/[C:31](=[CH:7]\[C:8]([C:10]1[CH:11]=[N:12][N:13]([C:16]3[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=3)[C:14]=1[CH3:15])=[O:9])/[C:30]2=[O:39]

Participants

5

Reactant 3

HCID 1549179(+)-CamphorquinoneHCID 23665647Potassium tert-butoxideHCID 86609911[2-(5-Methyl-1-phenyl-1H-pyrazol-4-yl)-2-oxo-ethyl]-phosphonic acid dimethyl ester

Product 1

HCID 67364601(1s,4r)-1,7,7-Trimethyl-3-[2-(5-methyl-1-phenyl-1h-pyrazol-4-yl)-2-oxo-eth-(e)-ylidene]-bicyclo[2.2.1]heptan-2-oneYield 74.6%

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

[2-(5-Methyl-1-phenyl-1H-pyrazol-4-yl)-2-oxo-ethyl]-phosphonic acid dimethyl ester (1.1 g) in tert-butanol (60 mL) at RT under an argon atmosphere was treated with potassium tert-butoxide (0.412 g) and the mixture was stirred for 30 minutes. Then (1S,4R)-1,7,7-trimethyl-bicyclo[2.2.1]heptane-2,3-dione (0.499 g) was added at RT and the mixture was heated at reflux for 12 h under an argon atmosphere. The reaction mixture was partitioned between water and AcOEt, the layers were separated, the aqueous layer extracted twice with AcOEt. The combined organic layers were washed with water, dried over Na2SO4, filtered and evaporated. The residue was purified by flash chromatography (heptane/AcOEt 100% to 80%) to give (1S,4R)-1,7,7-trimethyl-3-[2-(5-methyl-1-phenyl-1H-pyrazol-4-yl)-2-oxo-eth-(E)-ylidene]-bicyclo[2.2.1]heptan-2-one (0.78 g) as a light yellow solid. MS (EI): 348.2 (M+).

Workup

  1. temperaturethe mixture was heated
  2. temperatureat reflux for 12 h under an argon atmosphere
  3. customThe reaction mixture was partitioned between water and AcOEt
  4. customthe layers were separated
  5. extractionthe aqueous layer extracted twice with AcOEt
  6. washThe combined organic layers were washed with water
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. customevaporated
  10. customThe residue was purified by flash chromatography (heptane/AcOEt 100% to 80%)

Sources & evidence

ORD record
ord-bf72ccea36c641bda136c57407615c01
Source dataset
uspto-grants-2010_03
Patent number
US07678795B2

Reaction notes

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