Nitric Acid → (S)-2-amino-6-(2-fluoro-5-nitro-phenyl)-3,5,5,6-tetramethyl-5,6-dihydro-3H-pyrimidin-4-one

HRID 2409124Notes

Reaction equation

HRID 2409124 reaction equation
C(OC(=O)[NH:7][C:8]1[N:9]([CH3:25])[C:10](=[O:24])[C:11]([CH3:23])([CH3:22])[C@:12]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=2[F:21])([CH3:14])[N:13]=1)(C)(C)C.[N+:27]([O-])([OH:29])=[O:28].[OH-].[Na+]>S(=O)(=O)(O)O>[NH2:7][C:8]1[N:9]([CH3:25])[C:10](=[O:24])[C:11]([CH3:23])([CH3:22])[C@:12]([C:15]2[CH:20]=[C:19]([N+:27]([O-:29])=[O:28])[CH:18]=[CH:17][C:16]=2[F:21])([CH3:14])[N:13]=1

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 14798Sodium HydroxideHCID 57497153[(S)-4-(2-fluoro-phenyl)-1,4,5,5-tetramethyl-6-oxo-1,4,5,6-tetrahydro-pyrimidin-2-yl]-carbamic acid tert-butyl ester2×

Product 1

HCID 57497156(S)-2-amino-6-(2-fluoro-5-nitro-phenyl)-3,5,5,6-tetramethyl-5,6-dihydro-3H-pyrimidin-4-one

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Procedure

To a solution of [(S)-4-(2-fluoro-phenyl)-1,4,5,5-tetramethyl-6-oxo-1,4,5,6-tetrahydro-pyrimidin-2-yl]-carbamic acid tert-butyl ester (intermediate E7, 0.27 g) in sulfuric acid (98%, 3.1 ml) was added at 0° C. fuming nitric acid (0.05 ml) and the reaction mixture was allowed to warm to 22° over 30 min. The mixture was slowly added to 20 ml ice cold water, the pH was adjusted to 7 using aqueous 4N NaOH and extracted with ethyl acetate. The organic layer was washed with water, dried and evaporated to give crude (S)-2-amino-6-(2-fluoro-5-nitro-phenyl)-3,5,5,6-tetramethyl-5,6-dihydro-3H-pyrimidin-4-one (0.19 g) as a pale orange amorphous solid. MS (ESI): m/z=309.2 [M+H]+.

Workup

  1. temperatureto warm to 22° over 30 min
  2. extractionextracted with ethyl acetate
  3. washThe organic layer was washed with water
  4. customdried
  5. customevaporated

Sources & evidence

ORD record
ord-46d78f83703f4f849ba8e6977e0c4093
Source dataset
uspto-grants-2014_08
Patent number
US08815881B2

Reaction notes

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