Pyrazole → 2-Amino-6-(1H-pyrazol-1-yl)pyridine

HRID 1396444

Reaction equation

C([N:8](C(OC(C)(C)C)=O)[C:9]1[N:14]=[C:13](Br)[CH:12]=[CH:11][CH:10]=1)(OC(C)(C)C)=O.[OH-].[K+].[NH:25]1[CH:29]=[CH:28][CH:27]=[N:26]1>CCOC(C)=O.[Cu]>[N:25]1([C:13]2[N:14]=[C:9]([NH2:8])[CH:10]=[CH:11][CH:12]=2)[CH:29]=[CH:28][CH:27]=[N:26]1

Participants

Conditions

Temperature: 160 °C

Procedure

6-(Di-Boc-amino)-2-bromopyridine (1.0 g, 2.68 mmol, ChronTech), copper (341 mg, 5.36 mmol), potassium hydroxide (301 mg, 5.36 mmol), and 1H-pyrazole (1.82 g, 26.8 mmol, Eq: 10) were combined and stirred at 160° C. for 18 h. The reaction mixture was cooled, diluted with EtOAc (50 mL) and the solids removed by filtration. The dark blue filtrate was washed with saturated aqueous NaHCO3 and brine then concentrated onto silica gel and purified by chromatography (40 g RediSep column, 20 to 100% ethyl acetate in hexanes, 20 min) to give 6-(1H-pyrazol-1-yl)pyridin-2-amine (365 mg, 2.28 mmol, 85%) as a white solid. MS (EI/CI) m/z: 161.2 [M+H].

Workup

temperatureThe reaction mixture was cooled
customthe solids removed by filtration
washThe dark blue filtrate was washed with saturated aqueous NaHCO3 and brine
concentrationthen concentrated onto silica gel
custompurified by chromatography (40 g RediSep column, 20 to 100% ethyl acetate in hexanes, 20 min)

Sources & evidence

ORD record: ord-a3cd4cc96feb4bd681392ab239d08faa
Source dataset: uspto-grants-2014_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08901124B2

Linked notes

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