Tetrabutylammonium Fluoride → HCID 136016222、化合物

HRID 2078719ノート

反応式

HRID 2078719 の反応式
[C:1]([O:5][C:6]([N:8]1[C:16]2[C:11](=[CH:12][CH:13]=[C:14]([O:17][Si](C(C)(C)C)(C)C)[CH:15]=2)[CH:10]=[C:9]1[C:25]1[C:26]2[S:39][C:38]([C:40]3[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=3)=[CH:37][C:27]=2[N:28]([C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])[N:29]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[F-].C([N+](CCCC)(CCCC)CCCC)CCC>O1CCCC1>[C:1]([O:5][C:6]([N:8]1[C:16]2[C:11](=[CH:12][CH:13]=[C:14]([OH:17])[CH:15]=2)[CH:10]=[C:9]1[C:25]1[C:26]2[S:39][C:38]([C:40]3[CH:41]=[CH:42][CH:43]=[CH:44][CH:45]=3)=[CH:37][C:27]=2[N:28]([C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])[N:29]=1)=[O:7])([CH3:2])([CH3:3])[CH3:4]

参加物

4

反応物 2

HCID 2724141Tetrabutylammonium FluorideHCID 57637385HCID 57637385、化合物2 回

生成物 1

HCID 136016222HCID 136016222、化合物収率 99%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

To a solution of 2-(1-tert-butoxycarbonyl-5-phenyl-1H-thieno[3,2-c]pyrazol-3-yl)-6-(tert-butyl-dimethyl-silanyloxy)-indole-1-carboxylic acid tert-butyl ester [2.44 g, 3.78 mmol, Intermediate (48)] in tetrahydrofuran (25 mL) at 0° C. was added tetrabutylammonium fluoride (4.20 mL of a 1M THF solution, 4.20 mmol) in one portion with stirring. After 40 minutes, the reaction was partitioned between ethyl acetate (75 mL) and 10% aqueous ammonium chloride (50 mL) and the layers separated. The organics were washed with water (50 mL) and brine (50 mL) successively, dried over magnesium sulfate, and the solvent removed under reduced pressure to give an amber foam. The crude product was chromatographed on silica, eluting with 10% ethyl acetate/dichloromethane, to yield 2-(1-tert-butoxycarbonyl-5-phenyl-1H-thieno[3,2-c]pyrazol-3-yl)-6-hydroxy-indole-1-carboxylic acid tert-butyl ester [1.99 g, 99%, Intermediate (49)] as a tan foam. TLC Rf 0.31 (silica, 10% ethyl acetate/dichloromethane); LC/MS: 532.2 (M+H), RT=4.31 minutes; 1H NMR [300 Mhz, (CD3)2SO]: δ 9.73 (s, 1H), 7.84-7.81 (m, 2H), 7.76 (s, 1H), 7.61 (d, J=2 Hz, 1H), 7.56-7.44 (m, 4H), 7.07 (s, 1H), 6.84 (dd, J=2, 8 Hz, 1H), 1.71 (s, 9H), 1.40 (s, 9H).

後処理

  1. customthe reaction was partitioned between ethyl acetate (75 mL) and 10% aqueous ammonium chloride (50 mL)
  2. customthe layers separated
  3. washThe organics were washed with water (50 mL) and brine (50 mL) successively
  4. dry with materialdried over magnesium sulfate
  5. customthe solvent removed under reduced pressure
  6. customto give an amber foam
  7. customThe crude product was chromatographed on silica
  8. washeluting with 10% ethyl acetate/dichloromethane

出典と根拠

ORDレコード
ord-855ae489a02e471ca427756915c1fe58
出典データセット
uspto-grants-2011_04
特許番号
US07928231B2

反応ノート

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