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Diisopropylamine → 4,4-Difluoro-5-(2-fluoropyridin-3-yl)-3,4-dihydro-2H-pyrrol-3-yl 4-methylbenzenesulfonate

HRID 869734
ノート
印刷プレビュー

反応式

HRID 869734 の反応式
C(NC(C)C)(C)C.CCCCCC.C([Li])CCC.[F:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][N:21]=1.[F:26][C:27]1([F:51])[CH:31]([O:32][S:33]([C:36]2[CH:41]=[CH:40][C:39]([CH3:42])=[CH:38][CH:37]=2)(=[O:35])=[O:34])[CH2:30][N:29](C(OC(C)(C)C)=O)[C:28]1=O>O1CCCC1.O>[CH3:42][C:39]1[CH:38]=[CH:37][C:36]([S:33]([O:32][CH:31]2[C:27]([F:51])([F:26])[C:28]([C:25]3[C:20]([F:19])=[N:21][CH:22]=[CH:23][CH:24]=3)=[N:29][CH2:30]2)(=[O:35])=[O:34])=[CH:41][CH:40]=1
参加物実験手順後処理出典と根拠反応ノート

参加物

7

反応物 4

HCID 7912DiisopropylamineHCID 97462-FluoropyridineHCID 58349825tert-Butyl 3,3-difluoro-4-{[(4-methylphenyl)sulfonyl]oxy}-2-oxopyrrolidine-1-carboxylateHCID 178418244HCID 178418244、化合物

生成物 1

HCID 583498384,4-Difluoro-5-(2-fluoropyridin-3-yl)-3,4-dihydro-2H-pyrrol-3-yl 4-methylbenzenesulfonate収率 51%

試薬・触媒・溶媒 2

HCID 962Water溶媒
HCID 8028Tetrahydrofuran溶媒2 回

実験手順

To a solution of diisopropylamine (8.76 g) in tetrahydrofuran (230 mL) was added 1.6 mol/L n-butyllithium hexane solution (51 mL) at −78° C., and the mixture was stirred for 1 hr. 2-Fluoropyridine (11.2 g) was added dropwise thereto, and the mixture was stirred for 2 hr. To the resultant pale-yellow suspension was slowly added dropwise a solution of tert-butyl 3,3-difluoro-4-{[(4-methylphenyl)sulfonyl]oxy}-2-oxopyrrolidine-1-carboxylate (22.6 g) in tetrahydrofuran (50 mL), and the mixture was stirred for 1 hr. Water was added to the reaction mixture, and the mixture was heated to room temperature and concentrated under reduced pressure. The residue was diluted with ethyl acetate, and washed with water. The separated aqueous layer was extracted again with ethyl acetate. Combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained mixture was dissolved in dichloromethane (30 mL), trifluoroacetic acid (100 mL) was added dropwise under ice-cooling, and the mixture was stirred for 4 hr while allowing the mixture to warm to room temperature. The reaction mixture was concentrated under reduced pressure, diluted with ethyl acetate, and a saturated aqueous sodium hydrogen carbonate solution was added until the mixture became neutral. The separated aqueous layer was extracted again with ethyl acetate. Combined organic layers were washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent:hexane-ethyl acetate=9:1→3:1) to give the title compound as a colorless solid (yield 10.9 g, 51%).

後処理

  1. stirringthe mixture was stirred for 2 hr
  2. stirringthe mixture was stirred for 1 hr
  3. concentrationconcentrated under reduced pressure
  4. additionThe residue was diluted with ethyl acetate
  5. washwashed with water
  6. extractionThe separated aqueous layer was extracted again with ethyl acetate
  7. washCombined organic layers were washed with saturated brine
  8. dry with materialdried over anhydrous magnesium sulfate
  9. concentrationconcentrated under reduced pressure
  10. dissolutionThe obtained mixture was dissolved in dichloromethane (30 mL)
  11. additiontrifluoroacetic acid (100 mL) was added dropwise under ice-
  12. temperaturecooling
  13. stirringthe mixture was stirred for 4 hr
  14. temperatureto warm to room temperature
  15. concentrationThe reaction mixture was concentrated under reduced pressure
  16. additiondiluted with ethyl acetate
  17. additiona saturated aqueous sodium hydrogen carbonate solution was added until the mixture
  18. extractionThe separated aqueous layer was extracted again with ethyl acetate
  19. washCombined organic layers were washed with saturated brine
  20. dry with materialdried over magnesium sulfate
  21. concentrationconcentrated under reduced pressure
  22. customThe residue was purified by silica gel column chromatography (eluent:hexane-ethyl acetate=9:1→3:1)

出典と根拠

ORDレコード
ord-2405e10b551b4658a9c57c2036d22949
出典データセット
uspto-grants-2015_03
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08969387B2

反応ノート

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