Water → 4-(4-Methoxyphenyl)-1-(3-methylbutyl)-1H-pyrazole

HRID 250512

Reaction equation

HRID 250512 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][CH:3]=1.[CH3:10][CH:11]([CH3:28])[CH2:12][CH2:13][N:14]1[CH:18]=[C:17](B2OC(C)(C)C(C)(C)O2)[CH:16]=[N:15]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][O:8][C:5]1[CH:6]=[CH:7][C:2]([C:17]2[CH:16]=[N:15][N:14]([CH2:13][CH2:12][CH:11]([CH3:28])[CH3:10])[CH:18]=2)=[CH:3][CH:4]=1

Participants

7

Reactant 4

HCID 962WaterHCID 77304-BromoanisoleHCID 11430Potassium CarbonateHCID 27598311-(3-Methylbutyl)-1H-pyrazole-4-boronic acid pinacol ester

Product 1

HCID 112880284-(4-Methoxyphenyl)-1-(3-methylbutyl)-1H-pyrazoleYield 127.4%

Reagents, catalysts & solvents 2

HCID 178477754HCID 178477754, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To p-bromoanisole (0.25 g, 1.33 mmol) 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 (0.29 g, 2.1 mmol) and [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium (II) (12 mg, 0.023 mmol) and the mixture refluxed under nitrogen for 17 h. Water (50 ml) was added to the reaction mixture and stirring continued at RT for 15 min followed by extraction with ether (2×50 ml), drying (MgSO4) and evaporation of the ether extract to give a brown oil (0.414 g). Purification by column chromatography (silica gel, 100% chloroform) afforded 4-(4-methoxyphenyl)-1-(3-methylbutyl)-1H-pyrazole (12) as a waxy pale yellow solid (37 mg, 11%). 1H nmr (CDCl3, 300 MHz) 0.97, d (6.6 Hz), 2×Me; 1.64, sept (6.6 Hz), H3″; 1.80, dt (7.2 Hz), H2″; 3.82, s, OMe; 4.15, t (7.5 Hz), H1″; 6.90, d (8.7 Hz), H3′,5′; 7.39, d (8.7 Hz), H2′,6′; 7.54, s, H3 or H5; 7.69, s, H5 or H3. ESI (+ve) MS m/z 245 (M+H, 100%).

Workup

  1. temperaturethe mixture refluxed under nitrogen for 17 h
  2. extractionfollowed by extraction with ether (2×50 ml)
  3. customdrying
  4. custom(MgSO4) and evaporation of the ether
  5. extractionextract

Sources & evidence

ORD record
ord-f08da7ac3fa24a7584799519aa8d4db6
Source dataset
uspto-grants-2011_01
Patent number
US07863313B2

Linked notes

Loading…