Pyridine → STK396635

HRID 1903276Notes

Reaction equation

HRID 1903276 reaction equation
[NH2:1][C:2]1[CH2:6][C:5](=[O:7])[N:4]([C:8]2[C:13]([Cl:14])=[CH:12][C:11]([Cl:15])=[CH:10][C:9]=2[Cl:16])[N:3]=1.N1C=CC=CC=1.[N+](C1C=CC=CC=1)([O-])=O.[C:32](Cl)(=[O:35])[CH:33]=[CH2:34]>O1CCCC1.O>[Cl:14][C:13]1[CH:12]=[C:11]([Cl:15])[CH:10]=[C:9]([Cl:16])[C:8]=1[N:4]1[C:5](=[O:7])[CH2:6][C:2]([NH:1][C:32](=[O:35])[CH:33]=[CH2:34])=[N:3]1

Participants

7

Reactant 4

HCID 1049PyridineHCID 7416NitrobenzeneHCID 13140Acryloyl chlorideHCID 2707463H-Pyrazol-3-one, 5-amino-2,4-dihydro-2-(2,4,6-trichlorophenyl)-

Product 1

HCID 3580774STK396635Yield 32%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

224 g (0.8 mole) of 3-amino-1-(2,4,6-trichlorophenyl)-2-pyrazolin-5-one was dissolved in 3.5 l of tetrahydrofuran to which were added 144 ml (1.76 mol) of pyridine and 12 ml of nitrobenzene. To the mixture was gradually added dropwise 160 g (1.76 mol) of acryloyl chloride while cooling with ice and the mixture was stirred for about 2 hours. After adding 1 l of water, the mixture was extracted with 1.5 l of ethyl acetate, and the extract was dried with anhydrous sodium sulfate. After distilling off the solvent at fro 20° C. to 30° C. under reduced pressure, the residual oily product was dissolved in a mixture of 500 ml of water and 500 ml of ethanol, to which was then added 50 ml of an aqueous ammonia solution at room temperature. After stirring for 30 minutes, acetic acid was added to the mixture for neutralization and the crystals thus deposited were collected by filtration. By recrystallization from acetonitrile, 83 g (32% yield) of Coupler Monomer (5) was obtained.

Workup

  1. temperaturewhile cooling with ice
  2. extractionthe mixture was extracted with 1.5 l of ethyl acetate
  3. dry with materialthe extract was dried with anhydrous sodium sulfate
  4. distillationAfter distilling off the solvent at fro 20° C. to 30° C. under reduced pressure
  5. dissolutionthe residual oily product was dissolved in a mixture of 500 ml of water and 500 ml of ethanol, to which
  6. additionwas then added 50 ml of an aqueous ammonia solution at room temperature
  7. stirringAfter stirring for 30 minutes
  8. additionacetic acid was added to the mixture for neutralization
  9. filtrationthe crystals thus deposited were collected by filtration
  10. customBy recrystallization from acetonitrile, 83 g (32% yield) of Coupler Monomer (5)
  11. customwas obtained

Sources & evidence

ORD record
ord-32a64723c9384978bc15c5f40f020643
Source dataset
uspto-grants-1984_03
Patent number
US04435503

Reaction notes

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