Sodium Carbonate → HCID 58691611, Verbindung

HRID 856010Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 856010
CC1(C)C(C)(C)OB([C:9]2[CH:10]=[C:11]([C:14]([O:16][CH3:17])=[O:15])[S:12][CH:13]=2)O1.CC1(C)C(C)(C)OB(B2OC(C)(C)C(C)(C)O2)O1.C([O-])(=O)C.[K+].Br[C:43]1[CH:44]=[N:45][C:46]2[N:47]([N:49]=[CH:50][C:51]=2[C:52]2[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=2)[CH:48]=1.C(=O)([O-])[O-].[Na+].[Na+]>CN(C=O)C.O1CCOCC1.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].Cl[Pd]Cl.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:52]1([C:51]2[CH:50]=[N:49][N:47]3[CH:48]=[C:43]([C:9]4[CH:10]=[C:11]([C:14]([O:16][CH3:17])=[O:15])[S:12][CH:13]=4)[CH:44]=[N:45][C:46]=23)[CH:53]=[CH:54][CH:55]=[CH:56][CH:57]=1

Komponenten

11

Edukt 5

HCID 10340Sodium CarbonateHCID 517044Potassium AcetateHCID 2733548Bis(pinacolato)diboraneHCID 52911233Methyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene-2-carboxylateHCID 586916046-Bromo-3-phenylpyrazolo[1,5-a]pyrimidine

Produkt 1

HCID 58691611HCID 58691611, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 5

HCID 24290Palladium ChlorideKatalysatorHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)KatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 6228DimethylformamideLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

A mixture of methyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene-2-carboxylate (5-1, 3.00 g, 13.6 mmol, 1 equiv), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi-1,3,2-dioxaborolane (3.80 g, 15.0 mmol, 1.10 equiv), potassium acetate (4.10 g, 41.8 mmol, 3.07 equiv), and 1,1′-bis(diphenylphophino)-ferrocene)dichloropalladium (360 mg, 0.44 mmol, 0.032 equiv) in DMF (50 mL) was heated at 80° C. for 4 hours. The reaction mixture was concentrated and the residue was partitioned between aqueous half-saturated sodium bicarbonate solution and ethyl acetate (150 mL). The organic layer was dried over sodium sulfate and concentrated. A solution of this residue, 6-bromo-3-phenylpyrazolo[1,5-a]pyrimidine (1-3, 1.90 g, 6.93 mmol, 0.510 equiv), and tetrakis(triphenylphosphine)palladium (400 mg, 0.350 mmol, 0.025 equiv) in a mixture of dioxane and aqueous sodium carbonate solution (2M, 7 mL, 14 mmol, 1.0 equiv) was heated at reflux for 20 hours. The reaction mixture was partitioned between aqueous saturated sodium bicarbonate solution and ethyl acetate. The organic layer was dried over sodium sulfate and concentrated. The residue was suspended in methanol and filtered to give methyl 4-(3-phenylpyrazolo[1,5-a]pyrimidin-6-yl)thiophene-2-carboxylate (5-2) as a yellow solid. 1H NMR (400 MHz, CDCl3) δ 8.86 (d, 1H, J=2.4 Hz), 8.80 (d, 1H, J=2.2 Hz), 8.46 (s, 1H), 8.07 (d, 1H, J=1.6 Hz), 8.05 (br d, 2H, J=7.8 Hz), 7.75 (d, 1H, J=1.6 Hz), 7.47 (br t, 2H, J=7.7 Hz), 7.30 (t, 1H, J=7.5 Hz), 3.95 (s, 3H).

Aufarbeitung

  1. concentrationThe reaction mixture was concentrated
  2. customthe residue was partitioned between aqueous half-saturated sodium bicarbonate solution and ethyl acetate (150 mL)
  3. dry with materialThe organic layer was dried over sodium sulfate
  4. concentrationconcentrated
  5. temperaturewas heated
  6. temperatureat reflux for 20 hours
  7. customThe reaction mixture was partitioned between aqueous saturated sodium bicarbonate solution and ethyl acetate
  8. dry with materialThe organic layer was dried over sodium sulfate
  9. concentrationconcentrated
  10. filtrationfiltered

Quellen und Nachweise

ORD-Eintrag
ord-4ae62f7073ee4ce290e48f5d6934b08f
Quelldatensatz
uspto-grants-2007_08
Patentnummer
US07262199B2

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