m-Chloroperbenzoic acid → 3-Dichloromethylsulfinyl-7-fluoro-1-methyl-4-quinolone

HRID 1823818Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1823818
[Cl:1][CH:2]([Cl:17])[S:3][C:4]1[C:13](=[O:14])[C:12]2[C:7](=[CH:8][C:9]([F:15])=[CH:10][CH:11]=2)[N:6]([CH3:16])[CH:5]=1.ClC1C=CC=C(C(OO)=[O:26])C=1>C(Cl)Cl.ClC1C=CC=C(C(OO)=O)C=1>[Cl:17][CH:2]([Cl:1])[S:3]([C:4]1[C:13](=[O:14])[C:12]2[C:7](=[CH:8][C:9]([F:15])=[CH:10][CH:11]=2)[N:6]([CH3:16])[CH:5]=1)=[O:26]

Komponenten

5

Edukt 2

HCID 70297m-Chloroperbenzoic acidHCID 113237793-Dichloromethylthio-7-fluoro-1-methyl-4-quinolone2×

Produkt 1

HCID 103805373-Dichloromethylsulfinyl-7-fluoro-1-methyl-4-quinoloneAusbeute 50 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 70297m-Chloroperbenzoic acidKatalysatorHCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

The crude product (2) was used in the second stage. To a stirred solution of 673 mg (2.873 mmol) of compound (2) in 80 ml DCM, ˜80%, m-chloroperbenzoic acid (MCPBA) (620 mg, 2.873 mmol) was added in a few portions over a period of 1 minute at 0° C. The stirred mixture was allowed to warm to room temperature, was stirred for one hour and then an additional 18 mg of MCPBA was added to complete the transformation. After 30 minutes stirring at room temperature the reaction solution was washed with 15 ml of 5% aqueous sodium carbonate. The aqueous layer was extracted two times with 60 ml of DCM each and the combined DCM solutions were dried over sodium sulfate and concentrated. The residue 660 mg was chromatographed on silica gel with hexane-ethyl acetate (gradient 1:1, 2:3, 1:2) to give 358 mg (50% yield) of racemic 7-fluoro-3-fluoromethylsulfinyl-1-methyl-4-quinolone (3) (monofluoroflosequinan) as a white solid. 1H NMR, CDCl3; δ=3.93 s, 3H, N—CH3; 5.75, 5.73, 5.59, 5.56, 5.46, 5.43, 5.30, 5.27 (8 lines, AB part of ABX), 2H, CH2; 7.18-7.30 m, 2H, H at C8 & C6; 7.98 s, 1H, H at C2; 8.44 dd, 1H, J=9.0 & 6.3 Hz, H at C5.

Aufarbeitung

  1. stirringAfter 30 minutes stirring at room temperature the reaction solution
  2. washwas washed with 15 ml of 5% aqueous sodium carbonate
  3. extractionThe aqueous layer was extracted two times with 60 ml of DCM each and the combined DCM solutions
  4. dry with materialwere dried over sodium sulfate
  5. concentrationconcentrated
  6. customThe residue 660 mg was chromatographed on silica gel with hexane-ethyl acetate (gradient 1:1, 2:3, 1:2)

Quellen und Nachweise

ORD-Eintrag
ord-39f1d3e0c9a6427b93996405c4f2f09d
Quelldatensatz
uspto-grants-2006_05
Patentnummer
US07041677B2

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