Water → Tolpyralate

HRID 1257983Notes

Reaction equation

HRID 1257983 reaction equation
[CH3:1][O:2][CH2:3][CH2:4][O:5][C:6]1[C:7]([CH3:26])=[C:8]([C:16]([C:18]2[CH:19]=[N:20][N:21]([CH2:24][CH3:25])[C:22]=2[OH:23])=[O:17])[CH:9]=[CH:10][C:11]=1[S:12]([CH3:15])(=[O:14])=[O:13].C(=O)([O-])[O-].[K+].[K+].[C:33](=[O:40])([O:38][CH3:39])[O:34][CH:35](Cl)[CH3:36].O>CC(=O)CC.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC>[C:33](=[O:40])([O:38][CH3:39])[O:34][CH:35]([O:23][C:22]1[N:21]([CH2:24][CH3:25])[N:20]=[CH:19][C:18]=1[C:16](=[O:17])[C:8]1[CH:9]=[CH:10][C:11]([S:12]([CH3:15])(=[O:14])=[O:13])=[C:6]([O:5][CH2:4][CH2:3][O:2][CH3:1])[C:7]=1[CH3:26])[CH3:36]

Participants

7

Reactant 4

HCID 962WaterHCID 11430Potassium CarbonateHCID 135066411-Chloroethyl methyl carbonateHCID 178463133HCID 178463133, compound

Product 1

HCID 44473182TolpyralateYield 47.4%

Reagents, catalysts & solvents 2

HCID 74236Tetrabutylammonium BromideCatalystHCID 6569Methyl Ethyl KetoneSolvent

Procedure

5-Hydroxy-1-ethylpyrazol-4-yl 3-(2-methoxyethoxy)-2-methyl-4-(methylsulfonyl)phenyl ketone (300 mg) was dissolved in 2-butanone (10 mL), and potassium carbonate (130 mg) and tetrabutylammonium bromide (15 mg) were added. After stirring at room temperature for 10 minutes, 1-chloroethyl methyl carbonate (purity: 85%, 270 mg) was added at room temperature, followed by heating and refluxing for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and poured into water and then extracted with ethyl acetate. The organic layer was washed with 1N hydrochloric acid and a saturated sodium chloride aqueous solution, followed by drying over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The obtained residue was purified by column chromatography with n-hexane:ethyl acetate=1:1, to obtain the desired product (180 mg) as slightly yellow solid.

Workup

  1. temperatureby heating
  2. temperaturerefluxing for 3 hours
  3. customAfter completion of the reaction
  4. temperaturethe reaction mixture was cooled to room temperature
  5. extractionextracted with ethyl acetate
  6. washThe organic layer was washed with 1N hydrochloric acid
  7. dry with materialby drying over anhydrous sodium sulfate
  8. distillationThe solvent was distilled off under reduced pressure
  9. customThe obtained residue was purified by column chromatography with n-hexane

Sources & evidence

ORD record
ord-8af1bb70ff10485e9b2dd0cf71925a46
Source dataset
uspto-grants-2013_06
Patent number
US08466089B2

Reaction notes

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