Ethylvanillin → 4-(3-Ethoxy-4-hydroxy-phenyl)-1-(2-ethyl-phenyl)-1,4,5,7-tetrahydro-pyrazolo[3,4-b]pyridin-6-one

HRID 1801564Notes

Reaction equation

HRID 1801564 reaction equation
[CH2:1]([C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[N:9]1[C:13]([NH2:14])=[CH:12][CH:11]=[N:10]1)[CH3:2].[CH2:15]([O:17][C:18]1[CH:19]=[C:20]([CH:23]=[CH:24][C:25]=1[OH:26])[CH:21]=O)[CH3:16].[CH3:27][C:28]1(C)OC(=O)CC(=O)[O:29]1>CCO>[CH2:15]([O:17][C:18]1[CH:19]=[C:20]([CH:21]2[CH2:27][C:28](=[O:29])[NH:14][C:13]3[N:9]([C:4]4[CH:5]=[CH:6][CH:7]=[CH:8][C:3]=4[CH2:1][CH3:2])[N:10]=[CH:11][C:12]2=3)[CH:23]=[CH:24][C:25]=1[OH:26])[CH3:16]

Participants

5

Reactant 3

HCID 8467EthylvanillinHCID 162492,2-Dimethyl-1,3-dioxane-4,6-dioneHCID 675133942-(2-Ethyl-phenyl)-2H-pyrazol-3-ylamine

Product 1

HCID 1363723454-(3-Ethoxy-4-hydroxy-phenyl)-1-(2-ethyl-phenyl)-1,4,5,7-tetrahydro-pyrazolo[3,4-b]pyridin-6-oneYield 42.5%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
75 °C

Procedure

To 2-(2-Ethyl-phenyl)-2H-pyrazol-3-ylamine 3 (25.9 mmol) in EtOH (150 mL) was added 3-Ethoxy-4-hydroxy-benzaldehyde 5 (28.5 mmol), followed by Meldrum's Acid 4 (28.5 mmol). The reaction mixture was heated to 75° C., then after 2 hours, the reaction mixture was cooled to room temperature, and concentrated under reduced pressure. The residue was treated with water (100 mL) and the product was extracted with dichloromethane (200 mL). The organic extract was dried over anhydrous magnesium sulfate and the solvent was removed at reduced pressure. The residue was purified by column chromatography t to provide (11 mmol) of 4-(3-Ethoxy-4-hydroxy-phenyl)-1-(2-ethyl-phenyl)-1,4,5,7-tetrahydro-pyrazolo[3,4-b]pyridin-6-one 6. 1H NMR (300 MHz, CDCl3/TMS) δ 7.44-7.35 (m, 3H), 7.30-7.25 (m, 2H), 5.57 (d, J=2.1 Hz, 1H), 3.57 (br s, 2H), 2.49 (q, J=7.6 Hz, 2H), 1.10 (t, J=7.6 Hz, 3H); 13C NMR (75 MHz, CDCl3/TMS) δ 145.20, 142.60, 139.62, 135.93, 129.47, 129.41, 127.88, 126.55, 88.70, 24.04, 14.34.

Workup

  1. temperaturethe reaction mixture was cooled to room temperature
  2. concentrationconcentrated under reduced pressure
  3. additionThe residue was treated with water (100 mL)
  4. extractionthe product was extracted with dichloromethane (200 mL)
  5. extractionThe organic extract
  6. dry with materialwas dried over anhydrous magnesium sulfate
  7. customthe solvent was removed at reduced pressure
  8. customThe residue was purified by column chromatography t

Sources & evidence

ORD record
ord-3955c232b5a6456d8238e0e5d265bcc7
Source dataset
uspto-grants-2013_01
Patent number
US08349833B2

Reaction notes

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