Water → 3-chloro-N-(diphenylmethylene)-4-(2-fluoro-4-nitrophenoxy)pyridin-2-amine

HRID 408044Notes

Reaction equation

HRID 408044 reaction equation
[Cl:1][C:2]1[C:7](=[O:8])[CH:6]=[CH:5][NH:4][C:3]=1[N:9]=[C:10]([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.C(=O)([O-])[O-].[Cs+].[Cs+].[F:29][C:30]1[CH:31]=[C:32]([N+:37]([O-:39])=[O:38])[CH:33]=[CH:34][C:35]=1F.O>CN(C=O)C.CCO>[Cl:1][C:2]1[C:3]([N:9]=[C:10]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)=[N:4][CH:5]=[CH:6][C:7]=1[O:8][C:35]1[CH:34]=[CH:33][C:32]([N+:37]([O-:39])=[O:38])=[CH:31][C:30]=1[F:29]

Participants

7

Reactant 4

HCID 962WaterHCID 10796Cesium carbonateHCID 1230531,2-Difluoro-4-nitrobenzeneHCID 581336003-chloro-2-((diphenylmethylene)amino)pyridin-4(1H)-one

Product 1

HCID 581336033-chloro-N-(diphenylmethylene)-4-(2-fluoro-4-nitrophenoxy)pyridin-2-amineYield 32.73%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

To a 2-L Chem-Glass reactor was added the crude 3-chloro-2-(diphenylmethyleneamino)pyridin-4(1H)-one (from above, now in DMF) and cesium carbonate (300.52 g, 923 mmol) followed by the addition of 3,4-difluoronitrobenzene (118.15 mL, 1065 mmol). The mixture was heated to approximately 90° C. with stirring for 2 h. The mixture was cooled to 25° C. with stirring for 10 min. To this solution was added water (1 L). The mixture was extracted with EtOAc (1 L) and the aqueous phase was discarded. The organics were concentrated to afford an oil. The oil was dissolved into EtOH (200 mL) (heating sometimes required). After the solution was allowed to stand at 25° C. for 4 h, a solid was collected by filtration to afford 3-chloro-N-(diphenylmethylene)-4-(2-fluoro-4-nitrophenoxy)pyridin-2-amine (104.00 g; 32.73% yield) as a yellow solid. 1H NMR (CDCl3) δ 6.52 (d, 1 H, J=5.6 Hz), 6.80 (dd, 1 H, J=8.1, 9.1 Hz), 7.21-7.60 (m, 8 H), 7.78-7.95 (m, 2 H), 8.00 (m, 1 H), 8.11 (dd, 1 H, J=2.5, 9.6 Hz), 8.17 (d, 1 H, J=5.6 Hz); MS (ESI+) m/z 448.01 (M+H)+.

Workup

  1. temperatureThe mixture was cooled to 25° C.
  2. stirringwith stirring for 10 min
  3. extractionThe mixture was extracted with EtOAc (1 L)
  4. concentrationThe organics were concentrated
  5. customto afford an oil
  6. temperatureheating sometimes
  7. waitto stand at 25° C. for 4 h
  8. filtrationa solid was collected by filtration

Sources & evidence

ORD record
ord-ffe941c8ad9e4aecabdb1ce851b38d55
Source dataset
uspto-grants-2014_06
Patent number
US08754230B2

Reaction notes

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