Dimethylformamide → HCID 86745422, compound

HRID 1090998Notes

Reaction equation

HRID 1090998 reaction equation
[H-].[Na+].N[C:4]1[C:5]([Cl:21])=[CH:6][C:7]([Cl:20])=[C:8]([N:10]2[C:14](=[O:15])[N:13]([CH:16]([F:18])[F:17])[C:12]([CH3:19])=[N:11]2)[CH:9]=1.F[C:23]1[CH:28]=[CH:27][C:26]([N+:29]([O-:31])=[O:30])=[CH:25][CH:24]=1.C[N:33](C)C=O>>[Cl:20][C:7]1[C:6]([NH2:33])=[C:5]([Cl:21])[C:4]([C:23]2[CH:28]=[CH:27][C:26]([N+:29]([O-:31])=[O:30])=[CH:25][CH:24]=2)=[CH:9][C:8]=1[N:10]1[C:14](=[O:15])[N:13]([CH:16]([F:18])[F:17])[C:12]([CH3:19])=[N:11]1

Participants

5

Reactant 4

HCID 6228DimethylformamideHCID 9590p-Fluoronitrobenzene2×HCID 24758Sodium hydrideHCID 110559662-(5-Amino-2,4-dichlorophenyl)-4-(difluoromethyl)-2,4-dihydro-5-methyl-3H-1,2,4-triazol-3-one

Product 1

HCID 86745422HCID 86745422, compound

Procedure

To a stirred, cold (0° C.) mixture of 0.085 gram (0.00355 mole) of sodium hydride in 10 mL of N,N-dimethylformamide was added 1.0 gram (0.00323 mole) of 1-(5-amino-2,4-dichlorophenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one. After stirring for a brief period of time, 0.455 gram (0.00323 mole) of 4-fluoronitrobenzene was added. The resultant mixture was allowed to warm to room temperature and was stirred for one hour. The reaction mixture was heated at 60° C. for three hours and an additional 0.455 gram of 4-fluoronitrobenzene was added. This mixture was heated at 50° C. for approximately 18 hours. After cooling to room temperature, the mixture was poured into ice water. The aqueous mixture was extracted with three portions of ethyl acetate. The extracts were combined and washed in succession with 1N hydrochloric acid, an aqueous saturated sodium bicarbonate solution, water, and an aqueous sodium chloride solution. The washed organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure to yield a solid. This solid was purified by recrystallization from ethyl acetate and n-heptane to yield 0.25 gram of 1-[2,4-dichloro-5-(4-nitrophenyl)-aminophenyl]-4-difluoromethyl-4,5-dihydro -3-methyl-1,2,4-triazol-5(1H)-one, m.p. 249°-251° C. The mother liquor from the recrystallization process was evaporated under reduced presure leaving 1.0 gram of an orange oil. Analysis of this oil by thin layer chromatography indicated it contained a substantial amount of the desired product.

Workup

  1. additionwas added
  2. temperatureThe reaction mixture was heated at 60° C. for three hours
  3. temperatureThis mixture was heated at 50° C. for approximately 18 hours
  4. temperatureAfter cooling to room temperature
  5. extractionThe aqueous mixture was extracted with three portions of ethyl acetate
  6. washwashed in succession with 1N hydrochloric acid
  7. dry with materialThe washed organic phase was dried over anhydrous magnesium sulfate
  8. filtrationwas filtered
  9. customThe filtrate was evaporated under reduced pressure
  10. customto yield a solid
  11. customThis solid was purified by recrystallization from ethyl acetate and n-heptane

Sources & evidence

ORD record
ord-278d68b58e7147a18b2bf38cf94db421
Source dataset
uspto-grants-1992_01
Patent number
US05084085

Reaction notes

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