tert-Butyl N-(2-bromoethyl)carbamate → Ethyl 6-cyclopropyl-1-[2-({[(1,1-dimethylethyl)oxy]carbonyl}amino)ethyl]-1H-pyrazolo[3,4-b]pyridine-4-carboxylate

HRID 1522440Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1522440
[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+].Br[CH2:25][CH2:26][NH:27][C:28](=[O:34])[O:29][C:30]([CH3:33])([CH3:32])[CH3:31]>CN(C=O)C>[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][N:10]([CH2:25][CH2:26][NH:27][C:28]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:34])[C:8]=3[N:9]=2)[CH2:2][CH2:3]1

Komponenten

5

Edukt 3

HCID 4103526tert-Butyl N-(2-bromoethyl)carbamateHCID 23665647Potassium tert-butoxideHCID 67124108ethyl 6-cyclopropyl-1H-pyrazolo[3,4-b]pyridine-4-carboxylate

Produkt 1

HCID 68078825Ethyl 6-cyclopropyl-1-[2-({[(1,1-dimethylethyl)oxy]carbonyl}amino)ethyl]-1H-pyrazolo[3,4-b]pyridine-4-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6228DimethylformamideLösungsmittel

Versuchsvorschrift

Ethyl 6-cyclopropyl-1H-pyrazolo[3,4-b]pyridine-4-carboxylate (125 mg, 0.541 mmol) was dissolved in DMF(10 mL), followed by addition of potassium tert-butoxide (79 mg, 0.703 mmol). After stirring for 15 minutes, 1,1-dimethylethyl (2-bromoethyl)carbamate (121 mg, 0.541 mmol) was added and the mixture was stirred at room temperature for 16 h. The reaction mixture was concentrated to dryness. The crude residue was diluted with water (50 mL) and acidified with acetic acid. The contents were extracted with DCM (4×50 mL). The combined organic layers were washed with water, brine, dried over MgSO4, filtered, and concentrated in vacuo. The crude residue was purified via silica gel chromatography (eluent: 0 to 50% EtOAc:Hex). The final product was obtained as 0.114 g (56%). LCMS E-S (M+H)=375.1. 1H NMR (400 MHz, DMSO-d6) δ ppm 1.04-1.14 (m, 4 H), 1.15-1.20 (m, 2 H), 1.27 (s, 7 H), 1.41 (t, J=7.07 Hz, 3 H), 2.36-2.45 (m, 1 H), 3.31-3.41 (m, 3 H), 4.36-4.50 (m, 5 H), 6.84 (t, J=5.81 Hz, 1 H), 7.65 (s, 1 H), 8.24 (s, 3 H).

Aufarbeitung

  1. stirringthe mixture was stirred at room temperature for 16 h
  2. concentrationThe reaction mixture was concentrated to dryness
  3. additionThe crude residue was diluted with water (50 mL)
  4. extractionThe contents were extracted with DCM (4×50 mL)
  5. washThe combined organic layers were washed with water, brine
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe crude residue was purified via silica gel chromatography (eluent: 0 to 50% EtOAc:Hex)

Quellen und Nachweise

ORD-Eintrag
ord-39b7e1d00cb34101bc29dd79644cc6a2
Quelldatensatz
uspto-grants-2015_07
Patentnummer
US09073924B2

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