Thiobenzoic Acid → (2S,4S)-4-benzoylthio-2-(difluoromethyl)thiomethyl-1-(4-nitrobenzyloxycarbonyl)pyrrolidine

HRID 346341ノート

反応式

HRID 346341 の反応式
[F:1][CH:2]([F:24])[S:3][CH2:4][C@@H:5]1[CH2:9][C@@H:8](O)[CH2:7][N:6]1[C:11]([O:13][CH2:14][C:15]1[CH:20]=[CH:19][C:18]([N+:21]([O-:23])=[O:22])=[CH:17][CH:16]=1)=[O:12].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O.[C:56]([SH:64])(=[O:63])[C:57]1[CH:62]=[CH:61][CH:60]=[CH:59][CH:58]=1>O1CCCC1>[C:56]([S:64][C@@H:8]1[CH2:7][N:6]([C:11]([O:13][CH2:14][C:15]2[CH:20]=[CH:19][C:18]([N+:21]([O-:23])=[O:22])=[CH:17][CH:16]=2)=[O:12])[C@H:5]([CH2:4][S:3][CH:2]([F:24])[F:1])[CH2:9]1)(=[O:63])[C:57]1[CH:62]=[CH:61][CH:60]=[CH:59][CH:58]=1

参加物

6

反応物 4

HCID 7414Thiobenzoic AcidHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 56991440(2S,4R)-2-(difluoromethyl)thiomethyl-4-hydroxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidine

生成物 1

HCID 57295496(2S,4S)-4-benzoylthio-2-(difluoromethyl)thiomethyl-1-(4-nitrobenzyloxycarbonyl)pyrrolidine

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

To a solution of (2S,4R)-2-(difluoromethyl)thiomethyl-4-hydroxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidine (1.01 g) and triphenylphosphine (1.1 g) in tetrahydrofuran (20 ml) was added dropwise a solution of diethyl azodicarboxylate (0.66 ml) in tetrahydrofuran (3 ml) at -10° C. to -5° C. with stirring. The mixture was stirred at the same temperature for 30 minutes. To the solution was added thiobenzoic S-acid (0.49 ml) at the same temperature and the mixture was stirred under ice-cooling for 2 hours. The reaction mixture was concentrated under reduced pressure. The resulting residue was dissolved in ethyl acetate (60 ml). The solution was washed with saturated aqueous sodium hydrogen carbonate and saturated aqueous sodium chloride successively, dried over anhydrous magnesium sulfate, and evaporated in vacuo. The resulting residue was chromatographed on silica gel (100 g) eluting with a mixture of n-hexane and ethyl acetate (3.1 , V/V). The fractions containing the desired compound were collected and evaporated in vacuo to give (2S,4S)-4-benzoylthio-2-(difluoromethyl)thiomethyl-1-(4-nitrobenzyloxycarbonyl)pyrrolidine (1.01 g).

後処理

  1. stirringThe mixture was stirred at the same temperature for 30 minutes
  2. stirringthe mixture was stirred under ice-
  3. temperaturecooling for 2 hours
  4. concentrationThe reaction mixture was concentrated under reduced pressure
  5. dissolutionThe resulting residue was dissolved in ethyl acetate (60 ml)
  6. washThe solution was washed with saturated aqueous sodium hydrogen carbonate and saturated aqueous sodium chloride successively
  7. dry with materialdried over anhydrous magnesium sulfate
  8. customevaporated in vacuo
  9. customThe resulting residue was chromatographed on silica gel (100 g)
  10. washeluting with a mixture of n-hexane and ethyl acetate (3.1 , V/V)
  11. additionThe fractions containing the desired compound
  12. customwere collected
  13. customevaporated in vacuo

出典と根拠

ORDレコード
ord-96a28df3efe841ef9cad377bd77154b9
出典データセット
uspto-grants-1991_10
特許番号
US05061804

反応ノート

読み込み中…