Dimethylformamide → 3-Tert-butyl 6-methyl 4-chloro-7-(3-fluorophenyl)pyrazolo[1,5-a]pyridine-3,6-dicarboxylate

HRID 717855

Reaktionsgleichung

Reaktionsgleichung von HRID 717855
[Cl:1][C:2]1[CH:3]=[N:4][C:5]([C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([F:18])[CH:13]=2)=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].[NH2:19]OS(C1C(C)=CC(C)=CC=1C)(=O)=O.[C:33]([O:37][C:38]([CH3:41])([CH3:40])[CH3:39])(=[O:36])[C:34]#[CH:35].CN(C)C=O.C(=O)([O-])[O-].[K+].[K+]>C(#N)C.C(OCC)(=O)C>[Cl:1][C:2]1[C:3]2[N:4]([N:19]=[CH:35][C:34]=2[C:33]([O:37][C:38]([CH3:41])([CH3:40])[CH3:39])=[O:36])[C:5]([C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([F:18])[CH:13]=2)=[C:6]([C:7]([O:9][CH3:10])=[O:8])[CH:11]=1

Komponenten

8

Edukt 5

HCID 6228DimethylformamideHCID 11430Potassium CarbonateHCID 543038tert-Butyl propiolateHCID 11830845O-(2,4,6-Trimethylbenzenesulfonyl)hydroxylamineHCID 58515983Methyl 5-chloro-2-(3-fluorophenyl)nicotinate

Produkt 1

HCID 585159563-Tert-butyl 6-methyl 4-chloro-7-(3-fluorophenyl)pyrazolo[1,5-a]pyridine-3,6-dicarboxylateAusbeute 30,2 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6342AcetonitrileLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

The methyl 5-chloro-2-(3-fluorophenyl)nicotinate (1.00 g, 3.76 mmol) was combined with freshly prepared 2-[(aminooxy)sulfonyl]-1,3,5-trimethylbenzene (0.972 g, 4.52 mmol) ether solution in acetonitrile (20.0 mL) at room temperature. The reaction was stirred for 24 hours and became a tan colored slurry. The slurry was added portion wise to a vigorously stirring suspension of tert-butyl propiolate (1.55 mL, 11.3 mmol), N,N-dimethylformamide (20.0 mL, 258 mmol) and potassium carbonate (2.60 g, 18.8 mmol) open to the air. After stirring for 15 minutes, the reaction was a dark red brown suspension. This was allowed to stir for 5 hours at room temperature. The reaction was taken up in ethyl acetate and decanted from the solids. The organic layer was washed with water, brine, dried over magnesium sulfate and concentrated to give the crude product as a reddish brown oil. The product was purified on silica gel eluting hexane:ethyl acetate gradient to give 3-tert-butyl 6-methyl 4-chloro-7-(3-fluorophenyl)pyrazolo[1,5-a]pyridine-3,6-dicarboxylate (0.46 g, 30%) as a semi-solid residue. LCMS calculated for C20H19ClFN2O4 (M+H)+: m/z=405.1. found: 404.9.

Aufarbeitung

  1. additionThe slurry was added portion wise to
  2. stirringa vigorously stirring
  3. stirringAfter stirring for 15 minutes
  4. stirringto stir for 5 hours at room temperature
  5. customdecanted from the solids
  6. washThe organic layer was washed with water, brine
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated
  9. customto give the crude product as a reddish brown oil
  10. customThe product was purified on silica gel
  11. washeluting hexane

Quellen und Nachweise

ORD-Eintrag
ord-aff6d0b51c2548fd9183c0ac89b78443
Quelldatensatz
uspto-grants-2015_11
Patentnummer
US09193721B2

Verknüpfte Notizen

Wird geladen…