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 2209303노트

반응식

HRID 2209303 반응식
[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

참가 물질

7

반응물 3

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

생성물 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]pyridine수율 65.1%

시약·촉매·용매 3

HCID 962Water용매HCID 6344Dichloromethane용매HCID 8857Ethyl Acetate용매

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-9ccaa660e1cb46f7a5bfca0b91336d4c
출처 데이터셋
uspto-grants-2016_06
특허 번호
US09376441B2

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