Potassium Carbonate → HCID 66876696, Verbindung

HRID 871710Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 871710
[F:1][C:2]([C:5]1[CH:9]=[C:8]([NH2:10])[N:7]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[N:6]=1)([F:4])[CH3:3].C(=O)([O-])[O-].[K+].[K+].Cl[C:24]([O:26][C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)=[O:25]>ClCCl>[F:1][C:2]([C:5]1[CH:9]=[C:8]([NH:10][C:24](=[O:25])[O:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[N:7]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[N:6]=1)([F:4])[CH3:3]

Komponenten

5

Edukt 3

HCID 11430Potassium Carbonate2×HCID 15891Phenyl chloroformate2×HCID 668761373-(1,1-difluoroethyl)-1-phenyl-1H-pyrazol-5-amine

Produkt 1

HCID 66876696HCID 66876696, VerbindungAusbeute 49,2 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

A mixture of 3-(1,1-difluoroethyl)-1-phenyl-1H-pyrazol-5-amine (528 mg, 2.37 mmol), potassium carbonate (979 mg, 7.10 mmol) and phenyl chloroformate (556 mg, 3.55 mmol) in anhydrous dichloromethane (20 mL) was stirred at rt for 15 h. Additional phenyl chloroformate (556 mg, 3.55 mmol) and potassium carbonate (979 mg, 7.10 mmol) was added and the mixture stirred for a further 4 h. The mixture was concentrated under reduced pressure and the residue partitioned between ethyl acetate and saturated aqueous sodium hydrogen carbonate solution. The organic layer was separated, washed with water, saturated aqueous sodium hydrogen carbonate solution, then dried over magnesium sulfate and filtered. Concentration under reduced pressure gave an oil which was purified via silica gel column chromatography (eluting with a gradient of 12% ethyl acetate in hexanes to 100% ethyl acetate) to afford phenyl 3-(1,1-difluoroethyl)-1-phenyl-1H-pyrazol-5-ylcarbamate (400 mg, 49%) as an oil. 1H NMR (300 MHz, CDCl3) δ 7.51-7.58 (m, 5H), 7.35-7.41 (m, 2H), 7.26 (m, 1H), 7.15 (m, 2H), 7.00 (brs, 1H), 6.80 (s, 1H), 2.04 (t, J=18 Hz, 3H); LC-MS (ESI) m/z 344 (M+H)+.

Aufarbeitung

  1. stirringthe mixture stirred for a further 4 h
  2. concentrationThe mixture was concentrated under reduced pressure
  3. customthe residue partitioned between ethyl acetate and saturated aqueous sodium hydrogen carbonate solution
  4. customThe organic layer was separated
  5. washwashed with water, saturated aqueous sodium hydrogen carbonate solution
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationConcentration under reduced pressure
  9. customgave an oil which
  10. customwas purified via silica gel column chromatography (
  11. washeluting with a gradient of 12% ethyl acetate in hexanes to 100% ethyl acetate)

Quellen und Nachweise

ORD-Eintrag
ord-6daae5e08ce04d5daf5c8f4af134c820
Quelldatensatz
uspto-grants-2015_03
Patentnummer
US08969587B2

Notizen zur Reaktion

Wird geladen…