Pyridine → ethyl 3-methyl-1-(6-methoxy-2-naphthyl)-1H-pyrazole-5-carboxylate

HRID 2085020Notes

Reaction equation

HRID 2085020 reaction equation
B(O)O.[CH3:4][C:5]1[CH:9]=[C:8]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[NH:7][N:6]=1.[N:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1>C(Cl)Cl.C([O-])(=O)C.[Cu+2].C([O-])(=O)C>[CH3:4][C:5]1[CH:9]=[C:8]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[N:7]([C:16]2[CH:4]=[CH:5][C:9]3[C:18](=[CH:19][CH:20]=[C:10]([O:12][CH3:13])[CH:8]=3)[CH:17]=2)[N:6]=1.[CH3:4][C:5]1[N:15]([C:20]2[CH:4]=[CH:5][C:9]3[C:18](=[CH:17][CH:16]=[C:10]([O:12][CH3:13])[CH:8]=3)[CH:19]=2)[N:7]=[C:8]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[CH:9]=1

Participants

7

Reactant 3

HCID 1049PyridineHCID 61668Boronic AcidHCID 178469061HCID 178469061, compound

Product 2

HCID 22728868ethyl 3-methyl-1-(6-methoxy-2-naphthyl)-1H-pyrazole-5-carboxylateYield 37%HCID 22728899ethyl 5-methyl-1-(6-methoxy-2-naphthyl)-1H-pyrazole-3-carboxylateYield 25%

Reagents, catalysts & solvents 2

HCID 8895Cupric acetateCatalystHCID 6344DichloromethaneSolvent2×

Procedure

To a solution of the above-prepared boronic acid (0.84 g, 3.2 mmol) and ethyl 3-methylpyrazole-5-carboxylate (0.49 g, 3.2 mmol) in 20 mL dry DCM were added pyridine (0.77 mL, 9.5 mmol) and anhydrous powder of copper(II) acetate (1.15 g, 6.3 mmol). Some activated molecular sieve powder was added afterwards. The resulting slurry was stirred for 4 days under argon. The mixture was diluted with DCM. It was filtered through celite. The blue filtrate was washed with water (×2), dried, concentrated and purified by flash column to separately afford ethyl 3-methyl-1-(6-methoxy-2-naphthyl)-1H-pyrazole-5-carboxylate [37% yield. Rf 0.80 (1:1 EtOAc:hexane). ES-MS: (M+H)+ 311] and ethyl 5-methyl-1-(6-methoxy-2-naphthyl)-1H-pyrazole-3-carboxylate [25% yield. Rf 0.69 (1:1 EtOAc:hexane). ES-MS: (M+H)+ 311] in a 1.5:1 ratio.

Workup

  1. additionSome activated molecular sieve powder was added afterwards
  2. filtrationIt was filtered through celite
  3. washThe blue filtrate was washed with water (×2)
  4. customdried
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-00bd7d374c9b41679d2d3c9dbb8b8ff0
Source dataset
uspto-grants-2004_04
Patent number
US06720317B1

Reaction notes

Loading…