Potassium vinyltrifluoroborate → methyl 4-(4-(difluoromethyl)-5-vinylthiazol-2-yl)-1-methyl-1H-pyrazole-5-carboxylate

HRID 60143

Reaktionsgleichung

Reaktionsgleichung von HRID 60143
F[C:2](OB([O-])[O-])=[C:3]([F:5])[F:4].[K+].[K+].Br[C:13]1[S:17][C:16]([C:18]2[CH:19]=[N:20][N:21]([CH3:27])[C:22]=2[C:23]([O:25][CH3:26])=[O:24])=[N:15][C:14]=1[CH:28](F)F.[B-](F)(F)(F)C=C.[K+]>[Pd](Cl)Cl.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].C(OCC)(=O)C.C(N(CC)CC)C.C(O)C>[F:4][CH:3]([F:5])[C:2]1[N:15]=[C:16]([C:18]2[CH:19]=[N:20][N:21]([CH3:27])[C:22]=2[C:23]([O:25][CH3:26])=[O:24])[S:17][C:13]=1[CH:14]=[CH2:28]

Komponenten

8

Edukt 3

HCID 23679353Potassium vinyltrifluoroborateHCID 86620274Potassium trifluorovinylborateHCID 90383233methyl 4-(5-bromo-4-(difluoromethyl)thiazol-2-yl)-1-methyl-1H-pyrazole-5-carboxylate

Produkt 1

HCID 117761094methyl 4-(4-(difluoromethyl)-5-vinylthiazol-2-yl)-1-methyl-1H-pyrazole-5-carboxylateAusbeute 58 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)Katalysator2×HCID 702EthanolLösungsmittelHCID 8471TriethylamineLösungsmittel2×HCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

Potassium trifluorovinylborate (172 mg), 1,1′-bis(diphenylphosphino)ferrocene-palladium(II) dichloride (31 mg), and triethylamine (59.4 μl) were added to an ethanol (2.1 ml) solution of the methyl 4-(5-bromo-4-(difluoromethyl)thiazol-2-yl)-1-methyl-1H-pyrazole-5-carboxylate (150 mg) obtained in (Example 1.4) <Step 1>, and the obtained mixture was then stirred in a nitrogen atmosphere at 100° C. for 17 hours. Thereafter, potassium trifluoro(vinyl)borate (342 mg), 1,1′-bis(diphenylphosphino)ferrocene-palladium(II) dichloride (62 mg), and triethylamine (59.4 μl) were added to the reaction solution, and the obtained mixture was stirred again in a nitrogen atmosphere at 100° C. for 2 hours 40 minutes. Thereafter, ethyl acetate (100 ml) and a saturated saline (50 ml) were added to the reaction solution. An organic layer was extracted, and was then dried over anhydrous sodium sulfate. The solvent was distilled away under reduced pressure, and the obtained residue was then purified by silica gel column chromatography (silica gel:eluent; heptane:ethyl acetate=95:5-50:50), so as to obtain the title compound (74 mg) in the form of a colorless solid.

Aufarbeitung

  1. customobtained in (Example 1.4) <Step 1>
  2. stirringthe obtained mixture was stirred again in a nitrogen atmosphere at 100° C. for 2 hours 40 minutes
  3. extractionAn organic layer was extracted
  4. dry with materialwas then dried over anhydrous sodium sulfate
  5. distillationThe solvent was distilled away under reduced pressure
  6. customthe obtained residue was then purified by silica gel column chromatography (silica gel:eluent; heptane:ethyl acetate=95:5-50:50)

Quellen und Nachweise

ORD-Eintrag
ord-f7e2c1a181be472c8a441820e6365940
Quelldatensatz
uspto-grants-2016_09
Patentnummer
US09440970B2

Verknüpfte Notizen

Wird geladen…