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 2209303ノート

反応式

HRID 2209303 の反応式
[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

参加物

7

反応物 3

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

生成物 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]pyridine収率 65.1%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 6344Dichloromethane溶媒HCID 8857Ethyl Acetate溶媒

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-9ccaa660e1cb46f7a5bfca0b91336d4c
出典データセット
uspto-grants-2016_06
特許番号
US09376441B2

反応ノート

読み込み中…