Bromide ion → HCID 45138156、化合物

HRID 2198095ノート

反応式

HRID 2198095 の反応式
Br[C:2]1[N:7]=[CH:6][C:5]([CH2:8][NH:9][C:10]([C:12]2[C:13]3[CH:20]=[N:19][N:18]([C:21]4[CH:26]=[CH:25][C:24]([F:27])=[CH:23][CH:22]=4)[C:14]=3[CH:15]=[N:16][CH:17]=2)=[O:11])=[CH:4][CH:3]=1.[CH2:28]([S:30]([O-:32])=[O:31])[CH3:29].[Br-].[Mg+2].C([Mg]Br)C.[Br-]>CS(C)=O.C(=O)([O-])[O-].[K+].[K+].[Cu](I)I.CCOC(C)=O>[CH2:28]([S:30]([C:2]1[N:7]=[CH:6][C:5]([CH2:8][NH:9][C:10]([C:12]2[C:13]3[CH:20]=[N:19][N:18]([C:21]4[CH:26]=[CH:25][C:24]([F:27])=[CH:23][CH:22]=4)[C:14]=3[CH:15]=[N:16][CH:17]=2)=[O:11])=[CH:4][CH:3]=1)(=[O:32])=[O:31])[CH3:29]

参加物

9

反応物 4

HCID 259Bromide ionHCID 451380091-(4-fluorophenyl)-1H-pyrazolo[3,4-c]pyridine-4-carboxylic acid(6-bromopyridin-3-ylmethyl)-amideHCID 86640799Magnesium bromide ethanesulfinate saltHCID 178418443HCID 178418443、化合物

生成物 1

HCID 45138156HCID 45138156、化合物

試薬・触媒・溶媒 4

HCID 83717Copper iodide触媒HCID 679Dimethyl Sulfoxide溶媒HCID 8857Ethyl Acetate溶媒HCID 11430Potassium Carbonate溶媒

反応条件

温度
130 °C

実験手順

To a microwave tube charged with 1-(4-fluorophenyl)-1H-pyrazolo[3,4-c]pyridine-4-carboxylic acid (6-bromopyridin-3-ylmethyl)-amide (80 mg, 0.2 mmol) in DMSO (3 mL) was added magnesium bromide ethanesulfinate salt (122 mg, 0.618 mmol) (prepared by treating the Grignard reagent, ethylmagnesium bromide with SO2) followed by copper iodide (210 mg, 1.1 mmol). The mixture was warmed in a microwave at 130° C. for 1 hour. The reaction was monitored by TLC (EtOAc) indicating a major new more polar product than starting bromide. The reaction was diluted with first saturated aqueous potassium carbonate (5 mL) and then saturated aqueous ammonium chloride (10 mL) and extracted with EtOAc (5×10 mL). The combined organic layers were washed with saturated aqueous ammonium chloride (3×10 mL), brine (3×10 mL), dried over magnesium sulfate, treated with activated carbon, filtered through diatomaceous earth and concentrated. The solid was dissolved in dichloromethane and purified by silica gel chromatography eluting with EtOAc-dichloromethane (25:75, then 1:1, then 66:34, then 75:25). The material from the column was triturated with ether to afford the title compound as a white solid.

後処理

  1. customprepared
  2. extractionsaturated aqueous ammonium chloride (10 mL) and extracted with EtOAc (5×10 mL)
  3. washThe combined organic layers were washed with saturated aqueous ammonium chloride (3×10 mL), brine (3×10 mL)
  4. dry with materialdried over magnesium sulfate
  5. additiontreated with activated carbon
  6. filtrationfiltered through diatomaceous earth
  7. concentrationconcentrated
  8. dissolutionThe solid was dissolved in dichloromethane
  9. custompurified by silica gel chromatography
  10. washeluting with EtOAc-dichloromethane (25:75
  11. customThe material from the column was triturated with ether

出典と根拠

ORDレコード
ord-f63636a851ad4c0fa5e02a18a8692f30
出典データセット
uspto-grants-2012_12
特許番号
US08338610B2

反応ノート

読み込み中…