Water → 1-(3-Methylbutyl)-4-(4-methylphenyl)-1H-pyrazole

HRID 250513Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 250513
Br[C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][CH:3]=1.[CH3:9][CH:10]([CH3:27])[CH2:11][CH2:12][N:13]1[CH:17]=[C:16](B2OC(C)(C)C(C)(C)O2)[CH:15]=[N:14]1.C(=O)([O-])[O-].[K+].[K+].O>O1CCCC1.C1C=CC(P([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.C1C=CC(P([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.[Fe]>[CH3:9][CH:10]([CH3:27])[CH2:11][CH2:12][N:13]1[CH:17]=[C:16]([C:2]2[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][CH:3]=2)[CH:15]=[N:14]1

Komponenten

7

Edukt 4

HCID 962Water2×HCID 78054-BromotolueneHCID 11430Potassium CarbonateHCID 27598311-(3-Methylbutyl)-1H-pyrazole-4-boronic acid pinacol ester

Produkt 1

HCID 98594051-(3-Methylbutyl)-4-(4-methylphenyl)-1H-pyrazoleAusbeute 158,2 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178477754HCID 178477754, VerbindungKatalysatorHCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

To a solution of p-bromotoluene (0.66 g, 3.86 mmol) in tetrahydrofuran (20 ml) was added a solution of 1-(3-methylbutyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (0.41 g, 1.55 mmol) in tetrahydrofuran (10 ml), potassium carbonate (0.42 g, 3.0 mmol), [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium (II) (40 mg, 0.077 mmol) and water (40 μl) and the mixture refluxed under nitrogen for 43 h. Water (50 ml) was added to the reaction mixture and stirring continued at RT for 10 min followed by extraction with ether (2×50 ml). The ether extract was then dried (MgSO4) and evaporated to give a brown oil (0.56 g) that solidified on standing. Purification by column chromatography (silica gel, 100% chloroform) afforded 1-(3-methylbutyl)-4-(4-methylphenyl)-1H-pyrazole (13) as a waxy pale yellow solid (0.216 g, 53%). 1H nmr (CDCl3, 300 MHz) 0.97, d (6.3 Hz), 2×Me; 1.62, m, H3″; 1.80, dt (7.3 Hz), H2″; 2.35, s, 4′-Me; 4.16, t (7.5 Hz), H1″; 7.16, d (8.1 Hz), H3′,5′; 7.37, d (8.1 Hz), H2′,6′; 7.59, s, H3 or H5; 7.74, s, H5 or H3. ESI (+ve) MS m/z 229 (M+H, 100%).

Aufarbeitung

  1. temperaturethe mixture refluxed under nitrogen for 43 h
  2. extractionfollowed by extraction with ether (2×50 ml)
  3. extractionThe ether extract
  4. dry with materialwas then dried (MgSO4)
  5. customevaporated

Quellen und Nachweise

ORD-Eintrag
ord-4a59c65fee634f4ca424bbab4286b2b4
Quelldatensatz
uspto-grants-2011_01
Patentnummer
US07863313B2

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