Triethylamine → 2-(4-Bromo-2,6-dimethylphenyl)-3-methoxy-5-[1-pyridin-2-ylmethylidene]cyclopent-2-enone

HRID 514194Notes

Reaction equation

HRID 514194 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([C:9]2[C:10](=[O:24])[CH:11]([CH:16](O)[C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][N:18]=3)[CH2:12][C:13]=2[O:14][CH3:15])=[C:4]([CH3:25])[CH:3]=1.C(N(CC)CC)C.CS(Cl)(=O)=O.C(=O)([O-])[O-].[K+].[K+]>ClCCl>[Br:1][C:2]1[CH:3]=[C:4]([CH3:25])[C:5]([C:9]2[C:10](=[O:24])[C:11](=[CH:16][C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][N:18]=3)[CH2:12][C:13]=2[O:14][CH3:15])=[C:6]([CH3:8])[CH:7]=1

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 11430Potassium CarbonateHCID 31297Methanesulfonyl chlorideHCID 896011142-(4-Bromo-2,6-dimethylphenyl)-5-(hydroxypyridin-2-ylmethyl)-3-methoxycyclopent-2-enone

Product 1

HCID 896012732-(4-Bromo-2,6-dimethylphenyl)-3-methoxy-5-[1-pyridin-2-ylmethylidene]cyclopent-2-enone

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 2-(4-bromo-2,6-dimethylphenyl)-5-(hydroxypyridin-2-ylmethyl)-3-methoxycyclopent-2-enone (7.2 g, 17.9 mmol) in dichloromethane (200 ml) at 0°C. is added triethylamine (7.0 ml, 53.8 mmol) dropwise, then methanesulfonyl chloride (6 ml, 53.8 mmol). The reaction mixture is allowed to warm to room temperature, then is stirred overnight and quenched with ice cold water. The organic phase is separated and the aqueous phase is extracted with ethyl acetate (100 ml×3). The combined organic fractions are concentrated in vacuo and the residue is re-dissolved in methanol (250 ml) and stirred for 10 minutes. To this suspension is then added potassium carbonate (8.1 g, 58.7 mmol), and the reaction mixture is stirred for 4-5 hours at 25-30°C. Volatile solvents are removed under vacuum and the crude product is diluted with distilled water and extracted with ethyl acetate (150 ml×3). The combined organic fractions are washed with distilled water, brine, then dried over sodium sulfate, filtered and the filtrate is concentrated in vacuo. The crude product is purified by flash column chromatography to afford 2-(4-bromo-2,6-dimethylphenyl)-3-methoxy-5-[1-pyridin-2-ylmethylidene]cyclopent-2-enone.

Workup

  1. customquenched with ice cold water
  2. customThe organic phase is separated
  3. extractionthe aqueous phase is extracted with ethyl acetate (100 ml×3)
  4. concentrationThe combined organic fractions are concentrated in vacuo
  5. dissolutionthe residue is re-dissolved in methanol (250 ml)
  6. stirringstirred for 10 minutes
  7. customVolatile solvents are removed under vacuum
  8. additionthe crude product is diluted with distilled water
  9. extractionextracted with ethyl acetate (150 ml×3)
  10. washThe combined organic fractions are washed with distilled water, brine
  11. dry with materialdried over sodium sulfate
  12. filtrationfiltered
  13. concentrationthe filtrate is concentrated in vacuo
  14. customThe crude product is purified by flash column chromatography

Sources & evidence

ORD record
ord-2cbebe9855084f17b515e38d92a8d31d
Source dataset
uspto-grants-2015_08
Patent number
US09107415B2

Reaction notes

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