Ethyl 4-(4-methoxyphenyl)-2,4-dioxobutanoate → Ethyl 1-(1-methylethyl)-6-[4-(methyloxy)phenyl]-1H-pyrazolo[3,4-b]pyridine-4-carboxylate

HRID 1522473Notes

Reaction equation

[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9](=O)[CH2:10][C:11](=O)[C:12]([O:14][CH2:15][CH3:16])=[O:13])=[CH:5][CH:4]=1.[CH3:19][CH:20]([N:22]1[C:26]([NH2:27])=[CH:25][CH:24]=[N:23]1)[CH3:21]>C1C=CC=CC=1>[CH3:19][CH:20]([N:22]1[C:26]2[N:27]=[C:9]([C:6]3[CH:7]=[CH:8][C:3]([O:2][CH3:1])=[CH:4][CH:5]=3)[CH:10]=[C:11]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[C:25]=2[CH:24]=[N:23]1)[CH3:21]

Participants

Conditions

Temperature: 62 °C

Procedure

To a solution of ethyl 4-[4-(methyloxy)phenyl]-2,4-dioxobutanoate (600 mg, 2.397 mmol) in benzene (5 mL) was added 1-(1-methylethyl)-1H-pyrazol-5-amine (300 mg, 2.397 mmol), and the reaction mixture was stirred at 62° C. overnight. The mixture was concentrated in vacuo and the residue was dissolved into acetic acid (3 mL). The solution was stirred at reflux for 1 h and concentrated in vacuo. The residue was purified using column chromatography (Silica gel, 0 to 100% EtOAc/hexanes) to give 530 mg (65%) of product. LCMS E-S (M+H)=340.1 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.47-1.57 (m, 3 H), 1.61-1.71 (m, 6 H), 3.88-3.96 (s, 3 H), 4.55 (q, J=7.2 Hz, 2 H), 5.46 (m, 1 H), 7.03-7.12 (m, 2 H), 8.13-8.25 (m, 3 H), 8.36-8.43 (m, 1 H).

Workup

concentrationThe mixture was concentrated in vacuo
dissolutionthe residue was dissolved into acetic acid (3 mL)
stirringThe solution was stirred
temperatureat reflux for 1 h
concentrationconcentrated in vacuo
customThe residue was purified

Sources & evidence

ORD record: ord-7209bbdc49914b11b5c86b9388301cc7
Source dataset: uspto-grants-2015_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09073924B2

Reaction notes

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