Potassium Carbonate → 3-tert-butyl-1-(2-methoxy-6-methylphenyl)-4-methyl-1H-pyrazol-5-amine

HRID 2109930Notes

Reaction equation

Br[C:2]1[C:3]([C:17]([CH3:20])([CH3:19])[CH3:18])=[N:4][N:5]([C:8]2[C:13]([CH3:14])=[CH:12][CH:11]=[CH:10][C:9]=2[O:15][CH3:16])[C:6]=1[NH2:7].[CH3:21]B1OBOBO1.C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C.O>[C:17]([C:3]1[C:2]([CH3:21])=[C:6]([NH2:7])[N:5]([C:8]2[C:13]([CH3:14])=[CH:12][CH:11]=[CH:10][C:9]=2[O:15][CH3:16])[N:4]=1)([CH3:20])([CH3:19])[CH3:18]

Participants

Conditions

Temperature: 155 °C

Procedure

To a solution of 4-bromo-3-tert-butyl-1-(2-methoxy-6-methylphenyl)-1H-pyrazol-5-amine (2.6 g, 7.68 mmol) in DMF (15 mL) was added methylboroxine (6.66 mL, 46.08 mmol), [1,1′-bis(diphenylphosphino)-butane]palladium (II) dichloride (481.97 mg, 0.80 mmol), and potassium carbonate (3.3 g, 23.04 mmol). The reaction mixture was stirred for 18 h at 155° C. The reaction was diluted with water (100 mL) and extracted with EtOAc (3×25 mL). The combined organic extracts were washed with brine, dried (Na2SO4), and concentrated under reduced pressure. The residue was purified by silica gel chromatography using 90% hexane/EtOAc, to afford the product (1.7 g, 77%) as a pure white solid. 1H NMR (300 MHz, DMSO-d6) δ 1.24 (s, 9H), 1.96 (s, 3H), 1.99 (s, 3H), 3.71 (s, 3H), 4.25 (s, 2H), 6.85 (d, 1H), 6.94 (d, 1H), 7.23-7.29 (m, 1H). ES-MS m/z 274.2 (MH+); HPLC RT (min.) 1.78.

Workup

extractionextracted with EtOAc (3×25 mL)
washThe combined organic extracts were washed with brine
dry with materialdried (Na2SO4)
concentrationconcentrated under reduced pressure
customThe residue was purified by silica gel chromatography

Sources & evidence

ORD record: ord-85ef39d8436a47d4ae1d742bc37e4d7f
Source dataset: uspto-grants-2009_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07517878B2

Reaction notes

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