m-Chloroperbenzoic acid → 3-cyano-1-(3,3,4,4,4-pentafluorobutyl)-1H-pyrazolo[3,4-b]pyridine 7-oxide

HRID 2203367Notes

Reaction equation

HRID 2203367 reaction equation
[F:1][C:2]([F:20])([C:16]([F:19])([F:18])[F:17])[CH2:3][CH2:4][N:5]1[C:9]2=[N:10][CH:11]=[CH:12][CH:13]=[C:8]2[C:7]([C:14]#[N:15])=[N:6]1.ClC1C=CC=C(C(OO)=[O:29])C=1>C(O)(=O)C>[C:14]([C:7]1[C:8]2[C:9](=[N+:10]([O-:29])[CH:11]=[CH:12][CH:13]=2)[N:5]([CH2:4][CH2:3][C:2]([F:1])([F:20])[C:16]([F:17])([F:18])[F:19])[N:6]=1)#[N:15]

Participants

4

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 866789821-(3,3,4,4,4-pentafluorobutyl)-1H-pyrazolo[3,4-b]pyridine-3-carbonitrile

Product 1

HCID 1186591253-cyano-1-(3,3,4,4,4-pentafluorobutyl)-1H-pyrazolo[3,4-b]pyridine 7-oxide

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
75 °C

Procedure

1-(3,3,4,4,4-pentafluorobutyl)-1H-pyrazolo[3,4-b]pyridine-3-carbonitrile, as described in Step D of Example 158 (1.818 g, 6.26 mmol) and 3-chloroperbenzoic acid (7.1 g, 31.68 mmol, 77%) in acetic acid (20 mL) were stirred at 75° C. for 6 hours. The reaction was then evaporated under reduced pressure to remove acetic acid. To the residue was added a mixture of hexane/ethyl acetate (2/1, 200 mL total) and the pH adjusted to 7.0˜7.5 with aq. K2CO3 at 0° C. The water layer was extracted with hexane/ethyl acetate (2/1, 2×60 mL). The combined organic layer was dried over MgSO4 and evaporated under reduced pressure. The residue was purified by silica gel column chromatography using hexanes/ethyl acetate eluent to give the desired product as a white solid. 1H NMR (500 MHz, CDCl3): δ 2.86 (m, 2H); 5.44 (t, J=7.3 Hz, 2H); 7.31 (t, J=8.2 Hz, 1H); 7.80 (d, J=8.4 Hz, 1H); 8.38 (d, J=5.1 Hz, 1H). m/z=307.02 (M+H).

Workup

  1. customThe reaction was then evaporated under reduced pressure
  2. customto remove acetic acid
  3. additionTo the residue was added
  4. additiona mixture of hexane/ethyl acetate (2/1, 200 mL total)
  5. customadjusted to 7.0˜7.5 with aq. K2CO3 at 0° C
  6. extractionThe water layer was extracted with hexane/ethyl acetate (2/1, 2×60 mL)
  7. dry with materialThe combined organic layer was dried over MgSO4
  8. customevaporated under reduced pressure
  9. customThe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-b2d6305a26284632bf1e5b84e2161785
Source dataset
uspto-grants-2016_06
Patent number
US09365574B2

Reaction notes

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