Ammonium formate → HCID 178449205, compound

HRID 1507471Notes

Reaction equation

HRID 1507471 reaction equation
C([O:8][C:9]1[CH:14]=[CH:13][C:12]([C:15]2[CH:19]=[C:18]([NH:20][C:21]([NH:35][CH2:36][CH:37]([CH3:39])[CH3:38])=[N:22][C:23]([C:25]3[C:26]([C:31]([F:34])([F:33])[F:32])=[N:27][N:28]([CH3:30])[CH:29]=3)=[O:24])[NH:17][N:16]=2)=[C:11]([F:40])[CH:10]=1)C1C=CC=CC=1.C([O-])=O.[NH4+]>CO.[Pd]>[F:40][C:11]1[CH:10]=[C:9]([OH:8])[CH:14]=[CH:13][C:12]=1[C:15]1[CH:19]=[C:18]([NH:20][C:21]([NH:35][CH2:36][CH:37]([CH3:39])[CH3:38])=[N:22][C:23]([C:25]2[C:26]([C:31]([F:33])([F:34])[F:32])=[N:27][N:28]([CH3:30])[CH:29]=2)=[O:24])[NH:17][N:16]=1

Participants

5

Reactant 2

HCID 2723923Ammonium formateHCID 178449206HCID 178449206, compound

Product 1

HCID 178449205HCID 178449205, compoundYield 33%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Conditions

Temperature
65 °C

Procedure

N-(((3-(4-(Benzyloxy)-2-fluorophenyl)-1H-pyrazol-5-yl)amino)(isobutylamino)methylene)-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide (62 mg, 0.111 mmol) was dissolved in methanol (2 mL), and nitrogen gas was bubbled through briefly. 10% Palladium on carbon (59 mg, 0.5 equivalent) was then added, followed by ammonium formate (70 mg, 10 equivalents). The reaction vessel was sealed and then heated to 65° C. for 1 hour. Then, the crude mixture was cooled, and filtered through a plug of celite. The filtrate was concentrated onto silica gel and the crude product purified by chromatography (gradient: 9:1 hexanes:EtOAc to 1:1 hexanes:EtOAc) to provide the title compound as a white solid (17 mg, 33% yield). 1H NMR (DMSO-d6) δ 12.90 (s, 1H), 12.50 (s, 1H), 10.32 (bs, 1H), 8.83 (t, 1H), 8.28 (s, 1H), 7.55 (t, 1H), 6.65 (m, 2H), 6.35 (s, 1H), 3.89 (s, 3H), 3.39 (m, 2H), 1.83 (m, 1H), 0.94 (d, 6H). MS: calc.=467.42; obs. M+H=468.13. HPLC (Method E): retention time was 4.971 minutes.

Workup

  1. customnitrogen gas was bubbled through briefly
  2. customThe reaction vessel was sealed
  3. filtrationfiltered through a plug of celite
  4. concentrationThe filtrate was concentrated onto silica gel
  5. customthe crude product purified by chromatography (gradient: 9:1 hexanes:EtOAc to 1:1 hexanes:EtOAc)

Sources & evidence

ORD record
ord-8b28c1e71acc42988588151e7995ea78
Source dataset
uspto-grants-2015_12
Patent number
US09221814B2

Reaction notes

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