Iodine → 2-Boc-Amino-3-iodo-4-chloropyridine

HRID 871070ノート

反応式

HRID 871070 の反応式
[Cl:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])[CH:3]=1.CN(C)CCN(C)C.C([Li])CCC.CCCCCC.[I:35]I.S([O-])(O)=O.[Na+]>O1CCCC1>[Cl:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:12])([CH3:14])[CH3:13])[C:3]=1[I:35]

参加物

8

反応物 6

HCID 807IodineHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 8058HexaneHCID 1516418tert-butyl N-(4-chloropyridin-2-yl)carbamateHCID 23665763Sodium BisulfiteHCID 178418339Butyllithium

生成物 1

HCID 598528862-Boc-Amino-3-iodo-4-chloropyridine

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-70 °C

実験手順

To a solution of tert-butyl (4-chloropyridin-2-yl)carbamate (10 g, 43.7 mmol) and tetramethylethylenediamine (12 mL) in tetrahydrofuran (200 mL) at −70° C. was added 2.5M n-butyl lithium in hexane (52 mL, 131 mmol) over 30 minutes. The mixture was stirred at −70° C. for 1 hour and treated with a solution of iodine (27 g, 109 mmol) in 100 mL tetrahydrofuran at −70° C. The mixture was stirred at −70° C. for 30 minutes and warmed to room temperature. Saturated aqueous sodium hydrogen sulfite (200 mL) was added and the mixture stirred for 30 minutes. The mixture was extracted with ethyl acetate and the organic layers were washed with water and brine, dried over sodium sulfate, filtered, concentrated and precipitated from ethyl acetate/hexane to afford the title compound. LCMS: 298.9 (M+H—NCOOH)+.

後処理

  1. stirringThe mixture was stirred at −70° C. for 30 minutes
  2. temperaturewarmed to room temperature
  3. stirringthe mixture stirred for 30 minutes
  4. extractionThe mixture was extracted with ethyl acetate
  5. washthe organic layers were washed with water and brine
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customprecipitated from ethyl acetate/hexane

出典と根拠

ORDレコード
ord-ffebef3bcbd444cb998b12782f57c523
出典データセット
uspto-grants-2015_03
特許番号
US08969375B2

反応ノート

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