Diisopropylethylamine → 6-chloro-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrazolo[3,4-b]pyridine 6-chloro-2-((2-(trimethylsilyl)ethoxy)methyl)-2H-pyrazolo[3,4-b]pyridine

HRID 2209303Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2209303
[Cl:1][C:2]1[N:7]=[C:6]2[NH:8][N:9]=[CH:10][C:5]2=[CH:4][CH:3]=1.C(N(CC)C(C)C)(C)C.[CH3:20][Si:21]([CH3:28])([CH3:27])[CH2:22][CH2:23][O:24][CH2:25]Cl>C(Cl)Cl.CCOC(C)=O.O>[Cl:1][C:2]1[N:7]=[C:6]2[N:8]([CH2:25][O:24][CH2:23][CH2:22][Si:21]([CH3:28])([CH3:27])[CH3:20])[N:9]=[CH:10][C:5]2=[CH:4][CH:3]=1.[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[C:6](=[N:8][N:9]([CH2:25][O:24][CH2:23][CH2:22][Si:21]([CH3:28])([CH3:27])[CH3:20])[CH:10]=2)[N:7]=1

Komponenten

7

Edukt 3

HCID 81531DiisopropylethylamineHCID 27242712-Chloromethyl 2-(trimethylsilyl)ethyl etherHCID 454802836-Chloro-1h-pyrazolo[3,4-b]pyridine

Produkt 1

HCID 1317359876-chloro-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrazolo[3,4-b]pyridine 6-chloro-2-((2-(trimethylsilyl)ethoxy)methyl)-2H-pyrazolo[3,4-b]pyridineAusbeute 65,1 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 962WaterLösungsmittelHCID 6344DichloromethaneLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

6-chloro-1H-pyrazolo[3,4-b]pyridine (500 mg, 3.3 mmol) was suspended in DCM (10 mL) and N,N-diisopropylethylamine (1.7 mL, 9.8 mmol) was added followed by 2-(trimethylsilyl)ethoxymethyl chloride (1.2 mL, 6.78 mmol). After stifling 3.5 h, the reaction mixture was diluted with EtOAc and water. The organic phase was dried over Na2SO4, filtered, and concentrated to afford a crude residue that was purified by silica gel chromatography (5-50% EtOAc in hexanes) to provide 610 mg of the first-eluting isomer 6-chloro-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrazolo[3,4-b]pyridine (or 6-chloro-2-((2-(trimethylsilyl)ethoxy)methyl)-2H-pyrazolo[3,4-b]pyridine, regiochemistry not determined) 7.54. Uncertainty in this assignment is implicit in other depictions of Intermediate 7.54. LCMS-ESI+ (m/z): [M+H]+ calcd for C12H19ClN3OSi: 284.10; found: 283.79.

Aufarbeitung

  1. dry with materialThe organic phase was dried over Na2SO4
  2. filtrationfiltered
  3. concentrationconcentrated
  4. customto afford a crude residue that
  5. customwas purified by silica gel chromatography (5-50% EtOAc in hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-9ccaa660e1cb46f7a5bfca0b91336d4c
Quelldatensatz
uspto-grants-2016_06
Patentnummer
US09376441B2

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