Benzenepropanoic acid, 4-methoxy-beta-oxo-, ethyl ester → HCID 86721217, compound

HRID 1750377Notes

Reaction equation

HRID 1750377 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9](=O)[CH2:10][C:11]([O:13][CH2:14][CH3:15])=[O:12])=[CH:5][CH:4]=1.COC(OC)[N:20]([CH3:22])C.Cl.[C:26]([NH:30]N)([CH3:29])([CH3:28])[CH3:27]>C1(C)C=CC=CC=1>[C:26]([N:30]1[C:9]([C:6]2[CH:7]=[CH:8][C:3]([O:2][CH3:1])=[CH:4][CH:5]=2)=[C:10]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH:22]=[N:20]1)([CH3:29])([CH3:28])[CH3:27]

Participants

5

Reactant 3

HCID 76150Benzenepropanoic acid, 4-methoxy-beta-oxo-, ethyl esterHCID 78373Dimethylformamide dimethyl acetalHCID 81889tert-Butylhydrazine monohydrochloride

Product 1

HCID 86721217HCID 86721217, compoundYield 70.1%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

A solution of ethyl 3-(4-methoxyphenyl)-3-oxopropanoate (3 g, 13.5 mmol) and 1,1-dimethoxy-N,N-dimethylmethanamine (2.152 mL, 16.20 mmol) in toluene (10 ml) was stirred at 90° C. for 14 hr. The reaction mixture was concentrated under reduced pressure, and ethanol (15 mL) was added thereto. To the residue were added tert-butylhydrazine monohydrochloride (1.85 g, 14.85 mmol) and TEA (2.07 mL, 14.85 mmol), and the mixture was stirred at 80° C. for 20 hr. The reaction mixture was concentrated under reduced pressure, and ethyl acetate was added thereto. The organic layer was washed with water and saturated brine and dried, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent gradient; 3→60% ethyl acetate/hexane) to give ethyl 1-tert-butyl-5-(4-methoxyphenyl)-1H-pyrazole-4-carboxylate (2.86 g, 9.46 mmol, 70.1%) as a pale-yellow powder.

Workup

  1. concentrationThe reaction mixture was concentrated under reduced pressure, and ethanol (15 mL)
  2. additionwas added
  3. concentrationThe reaction mixture was concentrated under reduced pressure, and ethyl acetate
  4. additionwas added
  5. washThe organic layer was washed with water and saturated brine
  6. customdried
  7. customthe solvent was evaporated under reduced pressure
  8. customThe obtained residue was purified by silica gel column chromatography (solvent gradient; 3→60% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-02d56d09a76c448e911e519a7b9f2f6e
Source dataset
uspto-grants-2015_10
Patent number
US09156837B2

Reaction notes

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