Potassium Carbonate → 4-Ethylamino-3-nitro-6-(3-trifluoromethyl-phenyl)-pyridine-2-carbonitrile

HRID 2246455Notes

Reaction equation

HRID 2246455 reaction equation
Cl[C:2]1[N:7]=[C:6]([C:8]#[N:9])[C:5]([N+:10]([O-:12])=[O:11])=[C:4]([NH:13][CH2:14][CH3:15])[CH:3]=1.[F:16][C:17]([F:28])([F:27])[C:18]1[CH:23]=[CH:22][C:21](B(O)O)=[CH:20][CH:19]=1.C(=O)([O-])[O-].[K+].[K+]>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:14]([NH:13][C:4]1[CH:3]=[C:2]([C:20]2[CH:21]=[CH:22][CH:23]=[C:18]([C:17]([F:28])([F:27])[F:16])[CH:19]=2)[N:7]=[C:6]([C:8]#[N:9])[C:5]=1[N+:10]([O-:12])=[O:11])[CH3:15]

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 27343894-(Trifluoromethyl)phenylboronic acidHCID 866138696-Chloro-4-ethylamino-3-nitro-pyridine-2-carbonitrile

Product 1

HCID 685163964-Ethylamino-3-nitro-6-(3-trifluoromethyl-phenyl)-pyridine-2-carbonitrileYield 64.3%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

Tetrakis(triphenylphosphine)palladium (2.78 g) was added under a nitrogen atmosphere to a mixture of 6-chloro-4-ethylamino-3-nitro-pyridine-2-carbonitrile (10.9 g), 4-trifluoromethyl-phenylboronic acid (10.0 g) in degassed dioxane (500 mL) and a 2M aqueous solution of potassium carbonate (60 mL). The mixture was refluxed for 4 hours then concentrated under reduced pressure. The residue was partitioned between ethyl acetate (300 mL) and water (300 mL). The aqueous layer was extracted with ethyl acetate (2×300 mL). The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was chromatographed over silica gel (eluent: DCM then DCM/acetone 95/5) to afford the title compound (10.4 g, 64%). 1H NMR (DMSO-d6) δ: 8.59 (br. s, 1H); 8.50-8.40 (m, 2H); 7.91 (d, J=8 Hz, 1H); 7.79 (t, J=7 Hz, 1H); 7.74 (s, 1H); 3.65 (q, J=7 Hz, 2H); 1.24 (t, J=7 Hz, 3H). MS m/z: 337 (M+1).

Workup

  1. temperatureThe mixture was refluxed for 4 hours
  2. concentrationthen concentrated under reduced pressure
  3. customThe residue was partitioned between ethyl acetate (300 mL) and water (300 mL)
  4. extractionThe aqueous layer was extracted with ethyl acetate (2×300 mL)
  5. washThe combined organic layers were washed with brine
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was chromatographed over silica gel (eluent

Sources & evidence

ORD record
ord-6c0d64a9bf2b44c8ad8e7e82ef15cdda
Source dataset
uspto-grants-2010_03
Patent number
US07687515B2

Reaction notes

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