Hydrochloric Acid → 4-(4-Aminopyrazolo[4,3-c]pyridin-2-yl)-3,5-dichlorobenzonitrile

HRID 626697Notes

Reaction equation

HRID 626697 reaction equation
C(OC(=O)[NH:7][C:8]1[C:13]2=[CH:14][N:15]([C:17]3[C:22]([Cl:23])=[CH:21][C:20]([C:24]#[N:25])=[CH:19][C:18]=3[Cl:26])[N:16]=[C:12]2[CH:11]=[CH:10][N:9]=1)(C)(C)C.Cl>>[NH2:7][C:8]1[C:13]2=[CH:14][N:15]([C:17]3[C:22]([Cl:23])=[CH:21][C:20]([C:24]#[N:25])=[CH:19][C:18]=3[Cl:26])[N:16]=[C:12]2[CH:11]=[CH:10][N:9]=1

Participants

3

Reactant 2

HCID 313Hydrochloric AcidHCID 69674840[2-(2,6-Dichloro-4-cyanophenyl)-2H-pyrazolo[4,3-c]pyridin-4-yl]carbamic acid tert-butyl ester

Product 1

HCID 696717024-(4-Aminopyrazolo[4,3-c]pyridin-2-yl)-3,5-dichlorobenzonitrileYield 39%

Conditions

Temperature
50 °C

Procedure

A mixture of [2-(2,6-dichloro-4-cyano-phenyl)-2H-pyrazolo[4,3-c]pyridin-4-yl]carbamic acid tert-butyl ester (5.0 g, contaminated with residual tert-butyl carbamate) and HCl (4 N in dioxane, 40 mL, 160 mmol) was stirred at 50° C. for 6 h then concentrated to dryness under reduced pressure. The resultant residue was partitioned between ethyl acetate and sodium bicarbonate (sat. aq.). The organic layer was separated, washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated to dryness under reduced pressure to afford the title compound as a yellow solid (1.17 g, 39% yield over 2 steps). 1H NMR (400 MHz, CDCl3): δ 8.95 (s, 1H), 8.48 (s, 2H), 7.58 (d, J=6.9 Hz, 1H), 7.27-7.22 (m, 1H), 7.19-7.14 (m, 1H), 6.91-6.88 (m, 1H). LCMS (Method D): RT=1.95 min, m/z: 304 [M+H+].

Workup

  1. concentrationthen concentrated to dryness under reduced pressure
  2. customThe resultant residue was partitioned between ethyl acetate and sodium bicarbonate (sat. aq.)
  3. customThe organic layer was separated
  4. washwashed with brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated to dryness under reduced pressure

Sources & evidence

ORD record
ord-0381937e961049588687be48021fa17f
Source dataset
uspto-grants-2016_04
Patent number
US09309240B2

Reaction notes

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