Potassium Carbonate → HCID 90460509, compound

HRID 2202109Notes

Reaction equation

HRID 2202109 reaction equation
[NH:1]1[CH:5]=[C:4]([C:6]([O:8][CH2:9][CH3:10])=[O:7])[N:3]=[CH:2]1.C(=O)([O-])[O-].[K+].[K+].I[C:18]1[CH:25]=[CH:24][C:21]([C:22]#[N:23])=[CH:20][CH:19]=1.CN[C@H]1CCCC[C@@H]1NC>O1CCOCC1.[Cu]I>[C:22]([C:21]1[CH:24]=[CH:25][C:18]([N:3]2[C:4]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:5][N:1]=[CH:2]2)=[CH:19][CH:20]=1)#[N:23]

Participants

7

Reactant 4

HCID 11430Potassium CarbonateHCID 764674-IodobenzonitrileHCID 13822957(1S,2S)-(+)-N,N'-Dimethylcyclohexane-1,2-diamineHCID 178469898HCID 178469898, compound

Product 1

HCID 90460509HCID 90460509, compoundYield 3%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
95 °C

Procedure

A mixture of ethyl 1H-imidazole-4-carboxylate (10 g, 71.36 mmol, 1.00 equiv), CuI (2.7 g, 14.18 mmol, 0.20 equiv), potassium carbonate (30 g, 217.06 mmol, 3.02 equiv), 4-iodobenzonitrile (25 g, 109.16 mmol, 1.53 equiv) and (1S,2S)-1-N,2-N-dimethylcyclohexane-1,2-diamine (2.0 g, 14.06 mmol, 0.20 equiv) in 1,4-dioxane (200 mL) was stirred under nitrogen at 95° C. overnight. The reaction was cooled to room temperature and the solid material was removed by filtration. The filtrate was diluted with 800 mL of ethyl acetate then washed with 3×400 mL of brine, dried over anhydrous sodium sulfate and concentrated under vacuum. The residue was purified on a silica gel column eluted with 1-3% of methanol in dichloromethane to give 450 mg (3%) of ethyl 1-(4-cyanophenyl)-1H-imidazole-5-carboxylate as a white solid. 1H-NMR (300 MHz, DMSO-d6): δ 8.19 (d, J=0.9 Hz, 2H), 7.84 (d, J=0.9 Hz, 2H), 4.15 (q, J=5.4 Hz, 2H), 1.16 (t, J=5.1 Hz, 3H) ppm. LCMS (method D, ESI): RT=1.19 min, m/z=242.0 [M+H]+ and 1.2 g (7%) of ethyl 1-(4-cyanophenyl)-1H-imidazole-4-carboxylate as a white solid. 1H-NMR (300 MHz, CDCl3): δ 7.90 (s, 1H), 7.82-7.76 (m, 3H), 7.50-7.47 (m, 2H), 4.24 (q, J=7.2 Hz, 2H), 1.28 (t, J=7.2 Hz, 3H) ppm. LCMS (method D, ESI): RT=1.16 min, m/z=242.0 [M+H]+.

Workup

  1. temperatureThe reaction was cooled to room temperature
  2. customthe solid material was removed by filtration
  3. additionThe filtrate was diluted with 800 mL of ethyl acetate
  4. washthen washed with 3×400 mL of brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated under vacuum
  7. customThe residue was purified on a silica gel column
  8. washeluted with 1-3% of methanol in dichloromethane

Sources & evidence

ORD record
ord-217bcd0c913440d993ef733f262bee21
Source dataset
uspto-grants-2016_06
Patent number
US09365527B2

Reaction notes

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