Hydrochloric Acid → 4-[1-(3-Methylthiophen-2-yl)-meth-(e)-ylidene]-2-(2,4,6-trimethylphenyl)cyclopentane-1,3-dione

HRID 336090Notes

Reaction equation

HRID 336090 reaction equation
CC(C)([O-])C.[K+].C[O:8][C:9]1[CH2:13][CH2:12][C:11](=[O:14])[C:10]=1[C:15]1[C:20]([CH3:21])=[CH:19][C:18]([CH3:22])=[CH:17][C:16]=1[CH3:23].[CH3:24][C:25]1[CH:29]=[CH:28][S:27][C:26]=1[CH:30]=O.Cl>O1CCCC1.CC(C)=O.O>[CH3:24][C:25]1[CH:29]=[CH:28][S:27][C:26]=1/[CH:30]=[C:12]1/[C:11](=[O:14])[CH:10]([C:15]2[C:20]([CH3:21])=[CH:19][C:18]([CH3:22])=[CH:17][C:16]=2[CH3:23])[C:9](=[O:8])[CH2:13]/1

Participants

8

Reactant 4

HCID 313Hydrochloric Acid2×HCID 799113-Methyl-2-thiophenecarboxaldehydeHCID 155776462-(2,4,6-Trimethylphenyl)-3-methoxy-cyclopent-2-enoneHCID 23665647Potassium tert-butoxide

Product 1

HCID 666838844-[1-(3-Methylthiophen-2-yl)-meth-(e)-ylidene]-2-(2,4,6-trimethylphenyl)cyclopentane-1,3-dioneYield 16.9%

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

Potassium tertiary butoxide (0.53 g, 4.72 mmol) is added to a cold solution of mixture of 3-Methoxy-2-(2,4,6-trimethylphenyl)cyclopent-2-enone (0.5 g, 2.16 mmol) in tetrahydrofuran (5 ml). The reaction mixture is stirred for 30 minutes at 0° C. and to this mixture is added a solution of 3-methyl-2-thiophene carboxaldehyde (0.23 g, 1.82 mmol) in tetrahydrofuran (1 ml). The reaction mixture is stirred at 0° C. for 2 hours, acidified to pH 1 with 2N aqueous hydrochloric acid and the aqueous phase is extracted with ethyl acetate (3×25 ml), the organic phases are combined, washed with water, and dried over anhydrous sodium sulphate. The mixture is filtered, and the filtrate is evaporated under reduced pressure to give a crude residue. The crude residue is dissolved in acetone (6 ml), added concentrated hydrochloric acid (3 ml) and the resulting solution is heated to 60° C. for 8 hrs. The reaction mixture is diluted with water and extracted with ethyl acetate (3×25 ml). The combined organics are washed with brine, dried over sodium sulphate, filtered and concentrated in vacuum to give a residue. This residue is then purified using silica gel column chromatography to give 4-[1-(3-methylthiophen-2-yl)-meth-(E)-ylidene]-2-(2,4,6-trimethylphenyl)cyclopentane-1,3-dione (100 mg).

Workup

  1. stirringThe reaction mixture is stirred at 0° C. for 2 hours
  2. extractionthe aqueous phase is extracted with ethyl acetate (3×25 ml)
  3. washwashed with water
  4. dry with materialdried over anhydrous sodium sulphate
  5. filtrationThe mixture is filtered
  6. customthe filtrate is evaporated under reduced pressure
  7. customto give a crude residue
  8. temperaturethe resulting solution is heated to 60° C. for 8 hrs
  9. extractionextracted with ethyl acetate (3×25 ml)
  10. washThe combined organics are washed with brine
  11. dry with materialdried over sodium sulphate
  12. filtrationfiltered
  13. concentrationconcentrated in vacuum
  14. customto give a residue
  15. customThis residue is then purified

Sources & evidence

ORD record
ord-5fdbfc5a5cfe4b9583bf15c44f214310
Source dataset
uspto-grants-2014_11
Patent number
US08889595B2

Reaction notes

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