Potassium Carbonate → 1-(4-cyanonaphthalene-2-yl)-1H-pyrazole-3-carboxylic acid ethyl ester

HRID 2383343Notes

Reaction equation

HRID 2383343 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[CH:10]=[CH:9][NH:8][N:7]=1)=[O:5])[CH3:2].Br[C:12]1[CH:13]=[C:14]([C:22]#[N:23])[C:15]2[C:20]([CH:21]=1)=[CH:19][CH:18]=[CH:17][CH:16]=2.CN[C@@H]1CCCC[C@H]1NC.C(=O)([O-])[O-].[K+].[K+]>C1(C)C=CC=CC=1.[Cu](I)I.C(OCC)(=O)C>[CH2:1]([O:3][C:4]([C:6]1[CH:10]=[CH:9][N:8]([C:12]2[CH:13]=[C:14]([C:22]#[N:23])[C:15]3[C:20](=[CH:19][CH:18]=[CH:17][CH:16]=3)[CH:21]=2)[N:7]=1)=[O:5])[CH3:2]

Participants

8

Reactant 4

HCID 11430Potassium CarbonateHCID 2733821trans-N,N'-dimethyl-1,2-cyclohexanediamineHCID 534856703-Bromonaphthalene-1-carbonitrileHCID 178469268HCID 178469268, compound

Product 1

HCID 673092091-(4-cyanonaphthalene-2-yl)-1H-pyrazole-3-carboxylic acid ethyl esterYield 19.2%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

A suspension of 1H-pyrazole-3-carboxylic acid ethyl ester (0.1 g), 3-bromonaphthalene-1-carbonitrile (0.17 g), copper iodide (0.0068 g), (1R,2R)-(−)-N, N′-dimethylcyclohexane-1,2-diamine (0.010 g) and potassium carbonate (0.21 g) in toluene (3 mL) was stirred at 90° C. overnight. After cooling to room temperature, ethyl acetate was added to the reaction mixture. The resulting mixture was filtered through a Celite pad. The residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=100/0-66/34) to give 1-(4-cyanonaphthalene-2-yl)-1H-pyrazole-3-carboxylic acid ethyl ester (0.040 g). To a solution of this compound (0.040 g) in a mixed solvent of tetrahydrofuran (0.2 mL), ethanol (0.08 mL) and water (0.08 mL) was added lithium hydroxide monohydrate (0.017 g), and the mixture was stirred at room temperature overnight. To the reaction mixture was added 2 mol/L hydrochloric acid (0.35 mL). The precipitated solid was collected by filtration, washed with water and n-hexane, and dried under reduced pressure to give the title compound (0.026 g).

Workup

  1. temperatureAfter cooling to room temperature
  2. filtrationThe resulting mixture was filtered through a Celite pad
  3. customThe residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=100/0-66/34)

Sources & evidence

ORD record
ord-2c093670350a4fb7b86a3550d6ea04c7
Source dataset
uspto-grants-2012_09
Patent number
US08263622B2

Reaction notes

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