1,3-Dibromo-5,5-dimethylhydantoin → 1-Benzenesulfonyl-5-chloro-2-bromomethyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid methyl ester

HRID 60230

反応式

HRID 60230 の反応式
[CH3:1][O:2][C:3]([C:5]1[C:13]2[C:8](=[N:9][CH:10]=[C:11]([Cl:14])[CH:12]=2)[N:7]([S:15]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)(=[O:17])=[O:16])[C:6]=1[CH3:24])=[O:4].[Br:25]N1C(C)(C)C(=O)N(Br)C1=O>ClCCCl>[CH3:1][O:2][C:3]([C:5]1[C:13]2[C:8](=[N:9][CH:10]=[C:11]([Cl:14])[CH:12]=2)[N:7]([S:15]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)(=[O:17])=[O:16])[C:6]=1[CH2:24][Br:25])=[O:4]

参加物

4

反応物 2

HCID 64791,3-Dibromo-5,5-dimethylhydantoinHCID 583649861-Benzenesulfonyl-5-chloro-2-methyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid methyl ester

生成物 1

HCID 583651731-Benzenesulfonyl-5-chloro-2-bromomethyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid methyl ester収率 66.8%

試薬・触媒・溶媒 1

HCID 111,2-Dichloroethane溶媒

実験手順

A mixture of 1-benzenesulfonyl-5-chloro-2-methyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid methyl ester (16.9 g, 46.2 mmol), 1,3-dibromo-5,5-dimethylhydantoin (13.21 g, 46.2 mmol) and 1,1-azobis(cyclohexanecarbonitrile) (1.52 g, 9.3 mmol) in 1,2-dichloroethane (200 mL) was heated under reflux for 90 minutes then stirred at ambient temperature for 16 hours. The reaction mixture was washed with saturated aqueous sodium thiosulfate solution. The organic layer was dried (Na2SO4) then filtered. The filtrate was stirred with flash silica gel, filtered and the filtrate evaporated under reduced pressure. The resultant residue was triturated with diethyl ether/pentane (1:1) to afford the title compound as white solid (13.7 g, 61%). LCMS (Method B): RT=4.35 min, M+H+=443/445/447. 1H NMR (400 MHz, CDCl3): 8.46-8.46 (m, 2H), 8.39 (d, J=2.4 Hz, 1H), 8.32 (d, J=2.4 Hz, 1H), 7.64-7.64 (m, 1H), 7.55-7.52 (m, 2H), 5.67 (s, 2H), 4.00 (s, 3H).

後処理

  1. temperaturewas heated
  2. temperatureunder reflux for 90 minutes
  3. washThe reaction mixture was washed with saturated aqueous sodium thiosulfate solution
  4. dry with materialThe organic layer was dried (Na2SO4)
  5. filtrationthen filtered
  6. stirringThe filtrate was stirred with flash silica gel
  7. filtrationfiltered
  8. customthe filtrate evaporated under reduced pressure
  9. customThe resultant residue was triturated with diethyl ether/pentane (1:1)

出典と根拠

ORDレコード
ord-21c54ea8a39c465cb72954c01e742bd1
出典データセット
uspto-grants-2016_09
特許番号
US09440976B2

関連ノート

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