Ethanol → ethyl 3-(5-amino-3-tert-butyl-1H-pyrazol-1-yl)benzoate

HRID 2284973Notes

Reaction equation

HRID 2284973 reaction equation
[NH:1]([C:3]1[CH:4]=[C:5]([CH:9]=[CH:10][CH:11]=1)[C:6]([OH:8])=[O:7])[NH2:2].[CH3:12][C:13]([CH3:20])([CH3:19])[C:14](=O)[CH2:15][C:16]#[N:17].S(=O)(=O)(O)O.[CH3:26][CH2:27]O>>[CH2:26]([O:7][C:6](=[O:8])[C:5]1[CH:9]=[CH:10][CH:11]=[C:3]([N:1]2[C:16]([NH2:17])=[CH:15][C:14]([C:13]([CH3:20])([CH3:19])[CH3:12])=[N:2]2)[CH:4]=1)[CH3:27]

Participants

5

Reactant 4

HCID 702EthanolHCID 1118Sulfuric AcidHCID 108871Pentanenitrile, 4,4-dimethyl-3-oxo-HCID 27365213-Hydrazinobenzoic acid

Product 1

HCID 21867322ethyl 3-(5-amino-3-tert-butyl-1H-pyrazol-1-yl)benzoateYield 56%

Procedure

A solution of 3-hydrazino benzoic acid (5.53 g, 36.4 mmol) and 4,4-dimethyl-3-oxo pentanenitrile (5.00 g, 40.0 mmol) and concentrated sulfuric acid (2 mL) in EtOH (72 mL) was stirred at reflux for 19 h. The cooled mixture was concentrated in vacuo, was diluted with 1N NaOH solution (15 mL) and extracted with EtOAc. The combined organics were dried and concentrated in vacuo. The residue was purified by FCC, using 0-40% EtOAc in cyclohexane, to give the title compound as an off-white powder (5.92 g, 56%). LCMS (Method 3): Rt 3.04 min, m/z 288 [MH+].

Workup

  1. temperatureat reflux for 19 h
  2. concentrationThe cooled mixture was concentrated in vacuo
  3. additionwas diluted with 1N NaOH solution (15 mL)
  4. extractionextracted with EtOAc
  5. customThe combined organics were dried
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by FCC

Sources & evidence

ORD record
ord-0142d5376c7b447d82fcf9711c32baf2
Source dataset
uspto-grants-2015_09
Patent number
US09145413B2

Reaction notes

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