2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → Methyl [1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazolo[3,4-b]pyridin-3-yl]acetate

HRID 1952356Notes

Reaction equation

[NH:1]1[C:5]2=[N:6][CH:7]=[CH:8][CH:9]=[C:4]2[C:3]([CH2:10][C:11]([O:13][CH3:14])=[O:12])=[N:2]1.[CH2:15]1[CH2:20][O:19][CH:18]=[CH:17][CH2:16]1.C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N>C(#N)C>[O:19]1[CH2:20][CH2:15][CH2:16][CH2:17][CH:18]1[N:1]1[C:5]2=[N:6][CH:7]=[CH:8][CH:9]=[C:4]2[C:3]([CH2:10][C:11]([O:13][CH3:14])=[O:12])=[N:2]1

Participants

Conditions

Temperature: 75 °C

Procedure

To a solution of methyl 1H-pyrazolo[3,4-b]pyridin-3-ylacetate (84 mg, 0.439 mmol) in acetonitrile (3 mL) was added DHP (37 mg, 0.439 mmol) and DDQ (10 mg, 0.044 mmol). This mixture was heated to 75° C. for 20 minutes. After this time, additional DHP (37 μL, 0.44 mmol) was added and the reaction mixture heated to 85° C. for 1.5 hours. The reaction mixture was partitioned between water (10 mL) and ethyl acetate (2×20 mL). The combined organic extracts were washed with brine, dried over MgSO4, filtered and evaporated in vacuo. This residue was purified by chromatography using RediSep column (12 g) and eluting with gradient of 0-20% EtOAc/CH2Cl2. The desired fractions were combined and the solvent evaporated in vacuo to give the title compound. LRMS (M+1): 276.1.

Workup

temperaturethe reaction mixture heated to 85° C. for 1.5 hours
customThe reaction mixture was partitioned between water (10 mL) and ethyl acetate (2×20 mL)
washThe combined organic extracts were washed with brine
dry with materialdried over MgSO4
filtrationfiltered
customevaporated in vacuo
customThis residue was purified by chromatography
washeluting with gradient of 0-20% EtOAc/CH2Cl2
customthe solvent evaporated in vacuo

Sources & evidence

ORD record: ord-2195b8d89fb34522bc7ebaf36583a4b3
Source dataset: uspto-grants-2013_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08404856B2

Reaction notes

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