Isoamyl Nitrite → HCID 90408508, compound

HRID 2177629Notes

Reaction equation

HRID 2177629 reaction equation
Cl[C:2]1[C:7]([N+:8]([O-])=O)=[C:6]([NH:11][C:12]2[N:17]=[CH:16][C:15]([F:18])=[CH:14][N:13]=2)[CH:5]=[C:4]([CH3:19])[N:3]=1.[N:20](OCCC(C)C)=O.[H+].[B-](F)(F)(F)F>C(O)C.[Pd]>[F:18][C:15]1[CH:14]=[N:13][C:12]([N:11]2[C:6]3[CH:5]=[C:4]([CH3:19])[N:3]=[CH:2][C:7]=3[N:8]=[N:20]2)=[N:17][CH:16]=1

Participants

6

Reactant 3

HCID 8053Isoamyl NitriteHCID 28118Tetrafluoroboric acidHCID 90408828HCID 90408828, compound

Product 1

HCID 90408508HCID 90408508, compoundYield 48%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Conditions

Temperature
0 °C

Procedure

To a slurry of N-(2-chloro-6-methyl-3-nitropyridin-4-yl)-5-fluoropyrimidin-2-amine (13 g, 45.8 mmol) in ethanol (300 mL) was added 10% Pd/C (100 mg). The reaction was stirred for 10 h under a hydrogen atmosphere after which time the reaction was filtered and the filtrate was concentrated. The residue was diluted with ethanol (200 mL) and cooled to 0° C. Isoamyl nitrite (4.0 g, 34.0 mmol) and HBF4 (5.5 g, 34.0 mmol) were added and the reaction was stirred for 30 min at 0° C. followed by rt for 10 h. Evaporation of the solvents followed by recrystallization afforded the product as a white solid (3.2 g, 48%). MS (ESI) mass calcd. C10H7FN6, 230.07. m/z found, 231.2 [M+H]+. 1H NMR (400 MHz, DMSO-d6) δ 9.44 (s, 1H), 9.17 (s, 2H), 8.14 (s, 1H), 2.70 (s, 3H).

Workup

  1. filtrationwas filtered
  2. concentrationthe filtrate was concentrated
  3. additionThe residue was diluted with ethanol (200 mL)
  4. stirringthe reaction was stirred for 30 min at 0° C.
  5. waitfollowed by rt for 10 h
  6. customEvaporation of the solvents
  7. customfollowed by recrystallization

Sources & evidence

ORD record
ord-d033aa049f384275b76f45d8287601ec
Source dataset
uspto-grants-2015_06
Patent number
US09066946B2

Reaction notes

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