Hydrochloric Acid → 3-(4-chloro-6-fluoro-2-hydroxy-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione

HRID 1265395Notes

Reaction equation

HRID 1265395 reaction equation
N(OC(C)(C)C)=[O:2].N[C:9]1[C:14]([O:15][CH3:16])=[C:13]([Cl:17])[CH:12]=[C:11]([F:18])[C:10]=1[N:19]1[C:24](=[O:25])[CH:23]=[C:22]([C:26]([F:29])([F:28])[F:27])[N:21]([CH3:30])[C:20]1=[O:31].Cl>S([O-])([O-])(=O)=O.[Cu+2].[Cu-]=O.O.[N+]([O-])([O-])=O.[Cu+2].O.O.O.O.[N+]([O-])([O-])=O.[Cu+2].[N+]([O-])([O-])=O.[N+]([O-])([O-])=O.C(#N)C>[Cl:17][C:13]1[CH:12]=[C:11]([F:18])[C:10]([N:19]2[C:24](=[O:25])[CH:23]=[C:22]([C:26]([F:29])([F:28])[F:27])[N:21]([CH3:30])[C:20]2=[O:31])=[C:9]([OH:2])[C:14]=1[O:15][CH3:16]

Participants

8

Reactant 3

HCID 313Hydrochloric AcidHCID 10906Tert-Butyl nitriteHCID 183145373-(2-Amino-4-chloro-6fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)pyrimidinedione

Product 1

HCID 572512883-(4-chloro-6-fluoro-2-hydroxy-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione

Reagents, catalysts & solvents 4

HCID 24462Copper SulfateCatalystHCID 167780Copper(II) nitrate hemipentahydrateCatalystHCID 178419072HCID 178419072, compoundCatalystHCID 6342AcetonitrileSolvent2×

Procedure

An acetonitrile (10 ml) solution of copper (II) sulfate (0.52 g, 3.26 mmol), copper (I) oxide (0.47 g, 3.26 mmol) and copper (II) nitrate hemipentahydrate (0.76 g, 3.26 mmol) was stirred at −30° C., and added with tert-butyl nitrite (0.41 g, 3.97 mmol) and then an acetonitrile (3 ml) solution of 3-(2-amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (0.94 g, 2.56 mmol). After stirred for 16 hr (−30° C. to room temperature), the mixture was poured into cold 5% hydrochloric acid (30 ml) and then extracted with ethyl acetate (20 ml×3). The organic phase was washed with brine and dried over Na2SO4. Preparative TLC was used for purification (silica gel plates, 2000 microns, ether). Yield: 0.16 g, 0.44 mmol.

Workup

  1. extractionextracted with ethyl acetate (20 ml×3)
  2. washThe organic phase was washed with brine
  3. dry with materialdried over Na2SO4
  4. customPreparative TLC was used for purification (silica gel plates, 2000 microns, ether)

Sources & evidence

ORD record
ord-ec7d152c0822478d82aa2e1e417b4901
Source dataset
uspto-grants-2003_04
Patent number
US06545161B2

Reaction notes

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