Potassium Formate → 6-(2-Dodecylsulfonylbutyryl)amino-5-fluoro-benzoxazol-2-one

HRID 1058212

Reaktionsgleichung

Reaktionsgleichung von HRID 1058212
[F:1][C:2]1[C:3]([N+:12]([O-])=O)=[CH:4][C:5]2[O:9][C:8](=[O:10])[NH:7][C:6]=2[CH:11]=1.C([O-])=O.[K+].NC1C(F)=CC2NC(=O)OC=2C=1.[CH2:31]([S:43]([CH:46]([CH2:50][CH3:51])[C:47](Cl)=[O:48])(=[O:45])=[O:44])[CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH3:42]>O.C(OCCC)(=O)C.[Pd].C(O)(C)C>[CH2:31]([S:43]([CH:46]([CH2:50][CH3:51])[C:47]([NH:12][C:3]1[C:2]([F:1])=[CH:11][C:6]2[NH:7][C:8](=[O:10])[O:9][C:5]=2[CH:4]=1)=[O:48])(=[O:45])=[O:44])[CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH3:42]

Komponenten

9

Edukt 4

HCID 2735122Potassium FormateHCID 112178355-Fluoro-6-nitro-2,3-dihydro-1,3-benzoxazol-2-oneHCID 114732302-Dodecylsulfonyl-butyryl chlorideHCID 156759596-Amino-5-fluoro-2,3-dihydro-1,3-benzoxazol-2-one

Produkt 1

HCID 112599646-(2-Dodecylsulfonylbutyryl)amino-5-fluoro-benzoxazol-2-oneAusbeute 79,1 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 23938PalladiumKatalysatorHCID 962WaterLösungsmittel3×HCID 3776IsopropanolLösungsmittelHCID 7997Propyl AcetateLösungsmittel3×

Versuchsvorschrift

In a 250-ml flask, place 9.9 g (0.05 m) of 5-fluoro-6-nitro-benzoxazol-2-one (2a), 40 ml of isopropyl alcohol and 20 ml of propyl acetate, and 0.4 g 5% Pd/C with 1.5 ml of water. Add 16.8 g (0.2 m) of potassium formate in 20 ml of water, and stir the mixture vigorously at 55°-60° C. for 4 hrs. Keep strictly inert nitrogen atmosphere throughout the reaction. Take a TLC to confirm completeness of reaction. Cool the reaction mixture containing 6-amino-5-fluoro-benzoxazol-2-one (3a, X=F) to 40° C. under nitrogen, and add 40 ml of propyl acetate and a solution of 18.8 g (0.05 m×1.05 @95%) of 2-dodecylsulfonyl-butyryl chloride (R′COZ; R′=1-dodecylsulfonylpropyl and Z=Cl) in 60 ml of propyl acetate keeping the temperature at 40°-45° C. over 15 min. Stir the reaction mixture at 40° C. for 30 min. Add 60 ml of water and filter off catalyst and wash it with 60 ml of propyl acetate and 60 ml of water. Separate propyl acetate solution, wash with 120 ml of 1N HCl, and concentrate under a reduced pressure to a thick slurry. Cool the slurry in an ice-water bath for 2 hrs. Collect solid, wash with chilled propyl acetate and heptane, and dry in a vacuum oven to give 18.6 g (79%) of 6-(2-dodecylsulfonylbutyryl)amino-5-fluoro-benzoxazol-2-one (Formula I, Y=X=F and R′=1-dodecylsulfonylpropyl) as off-white solids.

Aufarbeitung

  1. customthroughout the reaction
  2. customcompleteness of reaction
  3. temperatureCool the reaction mixture
  4. stirringStir the reaction mixture at 40° C. for 30 min
  5. filtrationfilter off catalyst
  6. washwash it with 60 ml of propyl acetate and 60 ml of water
  7. washSeparate propyl acetate solution, wash with 120 ml of 1N HCl
  8. concentrationconcentrate under a reduced pressure to a thick slurry
  9. temperatureCool the slurry in an ice-water bath for 2 hrs
  10. customCollect solid
  11. washwash with chilled propyl acetate and heptane
  12. customdry in a vacuum oven

Quellen und Nachweise

ORD-Eintrag
ord-65ad409e92064a2d9b86d2bdfa7ae3a8
Quelldatensatz
uspto-grants-2003_02
Patentnummer
US06515176B1

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