Acetic Acid → HCID 86732263, compound

HRID 930423Notes

Reaction equation

HRID 930423 reaction equation
[F:1][C:2]1[C:7]([CH3:8])=[CH:6][C:5]([N+:9]([O-])=O)=[CH:4][C:3]=1[C@:12]1([CH2:23][F:24])[CH2:17][C@@H:16]([C:18]([F:21])([F:20])[F:19])[O:15][C:14]([NH2:22])=[N:13]1.N#N.C(O)(=O)C>CCO.[Pd]>[NH2:9][C:5]1[CH:6]=[C:7]([CH3:8])[C:2]([F:1])=[C:3]([C@:12]2([CH2:23][F:24])[CH2:17][C@@H:16]([C:18]([F:21])([F:19])[F:20])[O:15][C:14]([NH2:22])=[N:13]2)[CH:4]=1

Participants

6

Reactant 3

HCID 176Acetic AcidHCID 947NitrogenHCID 86732262(4S,6S)-4-(2-fluoro-3-methyl-5-nitrophenyl)-4-(fluoromethyl)-6-(trifluoromethyl)-5,6-dihydro-4H-1,3-oxazin-2-amine

Product 1

HCID 86732263HCID 86732263, compoundYield 96.1%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

A solution of (4S,6S)-4-(2-fluoro-3-methyl-5-nitrophenyl)-4-(fluoromethyl)-6-(trifluoromethyl)-5,6-dihydro-4H-1,3-oxazin-2-amine (1.26 g, 3.57 mmol) in EtOH (15 mL) was purged with N2 followed by the addition of acetic acid, glacial (0.412 ml, 7.13 mmol) and palladium, 10% wt. on activated carbon (0.047 ml, 5.35 mmol). The resulting mixture was purged with N2 again and H2 was bubbled through a balloon for 1 h. The mixture was filtered through celite, concentrated, diluted washed with 10% Na2CO3, 1 N NaOH, extracted with DCM and chromatographed on silica gel using 0-5% MeOH/DCM to afford a white solid as (4S,6S)-4-(5-amino-2-fluoro-3-methylphenyl)-4-(fluoromethyl)-6-(trifluoromethyl)-5,6-dihydro-4H-1,3-oxazin-2-amine (1.11 g, 3.43 mmol, 96% yield). MS m/z=323.9 [M+H]+. Calculated for C13H14F5N3O: 323.11.

Workup

  1. customThe resulting mixture was purged with N2 again
  2. customH2 was bubbled through a balloon for 1 h
  3. filtrationThe mixture was filtered through celite
  4. concentrationconcentrated
  5. additiondiluted
  6. washwashed with 10% Na2CO3, 1 N NaOH
  7. extractionextracted with DCM
  8. customchromatographed on silica gel using 0-5% MeOH/DCM

Sources & evidence

ORD record
ord-41bdbfbe8b2644408b2e07f655c5cd23
Source dataset
uspto-grants-2016_03
Patent number
US09296734B2

Reaction notes

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