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

HRID 408030Notes

Reaction equation

HRID 408030 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[C:31](F)=[C:32]([N+:36]([O-:38])=[O:37])[CH:33]=[CH:34][CH:35]=1>CN(C=O)C>[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+:36]([O-:38])=[O:37])=[CH:31][C:30]=1[F:29]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 813351,2-Difluoro-3-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 67%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
95 °C

Procedure

To a reactor was added 24 g of 3-chloro-2-(diphenylmethyleneamino) pyridin-4(1H)-one, DMF (100 mL), cesium carbonate (12.7 g; 0.5 eq) and difluoronitrobenzene (9.3 mL; 1.1 eq). The reaction mixture was heated to 95° C. and stirred for three hours. After the reaction was complete, the reaction mixture was poured onto crushed ice and the solids were filtered off and washed with water. The crude solids were charged back to the reactor and dissolved in THF (200 mL). Methanol was added and the mixture was distilled at a constant volume of 350 mL, until THF had been azeotropically removed. Additional methanol (100 mL) was added and the suspension was cooled to room temperature. The solids were filtered and dried under vacuum to yield 3-Chloro-N-(diphenylmethylene)-4-(2-fluoro-4-nitrophenoxy) pyridin-2-amine (23.3 g; 67% yield).

Workup

  1. additionthe reaction mixture was poured
  2. customonto crushed ice
  3. filtrationthe solids were filtered off
  4. washwashed with water
  5. additionThe crude solids were charged back to the reactor
  6. dissolutiondissolved in THF (200 mL)
  7. additionMethanol was added
  8. distillationthe mixture was distilled at a constant volume of 350 mL, until THF
  9. customhad been azeotropically removed
  10. additionAdditional methanol (100 mL) was added
  11. temperaturethe suspension was cooled to room temperature
  12. filtrationThe solids were filtered
  13. customdried under vacuum

Sources & evidence

ORD record
ord-0f0ab96fab124703940c5e8d09aee41c
Source dataset
uspto-grants-2014_06
Patent number
US08754230B2

Reaction notes

Loading…