N-methyl-2-pyrrolidone → Ethyl 1-amino-6-cyclopropyl-1H-pyrazolo[3,4-b]pyridine-4-carboxylate

HRID 476039Notes

Reaction equation

HRID 476039 reaction equation
[CH:1]1([C:4]2[CH:5]=[C:6]([C:13]([O:15][CH2:16][CH3:17])=[O:14])[C:7]3[CH:12]=[N:11][NH:10][C:8]=3[N:9]=2)[CH2:3][CH2:2]1.CC(C)([O-])C.[K+].C[N:25]1CCCC1=O>CCOC(C)=O>[NH2:25][N:10]1[C:8]2[N:9]=[C:4]([CH:1]3[CH2:2][CH2:3]3)[CH:5]=[C:6]([C:13]([O:15][CH2:16][CH3:17])=[O:14])[C:7]=2[CH:12]=[N:11]1

Participants

5

Reactant 3

HCID 13387N-methyl-2-pyrrolidoneHCID 23665647Potassium tert-butoxideHCID 67124108ethyl 6-cyclopropyl-1H-pyrazolo[3,4-b]pyridine-4-carboxylate

Product 1

HCID 67124432Ethyl 1-amino-6-cyclopropyl-1H-pyrazolo[3,4-b]pyridine-4-carboxylate

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

Ethyl 6-cyclopropyl-1H-pyrazolo[3,4-b]pyridine-4-carboxylate (200 mg, 0.865 mmol) was dissolved in N-Methyl-2-pyrrolidone (NMP) (8 mL), followed by addition of potassium tert-butoxide (116 mg, 1.038 mmol). After 20 minutes stirring, 0-{[4-(methyloxy)phenyl]carbonyl}hydroxylamine 1-[(aminooxy)carbonyl]-4-(methyloxy)benzene (289 mg, 1.730 mmol) was added and the mixture stirred at room temperature for 16 h. The contents were diluted with EtOAc, and then washed with brine, and saturated NaHCO3. The organic phase was dried over MgSO4, filtered, and concentrated in vacuo. The crude product was purified via silica gel chromatography (eluent: 0 to 50% EtOAc). The final product as collected as 106 mg (50%). LCMS E-S (M+H)=274.4. 1H NMR (400 MHz, DMSO-d6) δ ppm 1.00-1.14 (m, 4H), 1.41 (t, J=7.07 Hz, 3H), 2.34-2.47 (m, 1H), 4.44 (q, J=7.07 Hz, 2H), 6.39 (s, 2H), 7.64 (s, 1H), 8.09 (s, 1H).

Workup

  1. stirringthe mixture stirred at room temperature for 16 h
  2. washwashed with brine, and saturated NaHCO3
  3. dry with materialThe organic phase was dried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe crude product was purified via silica gel chromatography (eluent: 0 to 50% EtOAc)
  7. customThe final product as collected as 106 mg (50%)

Sources & evidence

ORD record
ord-e3d7700c83b04bdda7da85d20b18e65d
Source dataset
uspto-grants-2014_01
Patent number
US08637509B2

Reaction notes

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