4-Fluoroiodobenzene → HCID 57963782, compound

HRID 1948546Notes

Reaction equation

HRID 1948546 reaction equation
[F:1][C:2]([F:14])([F:13])[C:3]1[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[CH:6][NH:5][N:4]=1.CN[C@@H]1CCCC[C@H]1NC.[F:25][C:26]1[CH:31]=[CH:30][C:29](I)=[CH:28][CH:27]=1.C(=O)([O-])[O-].[K+].[K+]>C1(C)C=CC=CC=1.[Cu]I>[F:25][C:26]1[CH:31]=[CH:30][C:29]([N:5]2[CH:6]=[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[C:3]([C:2]([F:1])([F:13])[F:14])=[N:4]2)=[CH:28][CH:27]=1

Participants

7

Reactant 4

HCID 96054-FluoroiodobenzeneHCID 11430Potassium CarbonateHCID 2733821trans-N,N'-dimethyl-1,2-cyclohexanediamineHCID 178469923HCID 178469923, compound

Product 1

HCID 57963782HCID 57963782, compoundYield 96.5%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 1140TolueneSolvent

Procedure

To a solution of ethyl 3-(trifluoromethyl)-1H-pyrazole-4-carboxylate (100 mg, 0.480 mmol) in toluene (0.5 mL) was added (1R,2R)-N1,N2-dimethylcyclohexane-1,2-diamine (13.67 mg, 0.096 mmol), 1-fluoro-4-iodobenzene (0.166 mL, 1.441 mmol), potassium carbonate (139 mg, 1.009 mmol), and copper(I) iodide (9.00 mg, 0.047 mmol). This reaction was heated to reflux overnight. The next day, the reaction was complete by HPLC so it was filtered through a frit with EtOAc and purified on a SiO2 column using 25-100% EtOAc hexanes gradient to give white crystalline ethyl 1-(4-fluorophenyl)-3-(trifluoromethyl)-1H-pyrazole-4-carboxylate (140 mg, 0.463 mmol, 96% yield). The structure was assigned by small molecule X-ray crystallography. 1H NMR (400 MHz, CDCl3) δ ppm 8.35 (1H, s), 7.62 (2H, m), 7.14 (2H, m), 4.25 (2H, q), 1.37 (3H, t).

Workup

  1. temperatureThis reaction was heated
  2. temperatureto reflux overnight
  3. filtrationwas filtered through a frit with EtOAc
  4. custompurified on a SiO2 column

Sources & evidence

ORD record
ord-046da23f8228405b92a3d44d5f693f28
Source dataset
uspto-grants-2013_03
Patent number
US08399451B2

Reaction notes

Loading…