Pyridine → HCID 13627545, compound

HRID 1903277Notes

Reaction equation

HRID 1903277 reaction equation
[NH2:1][C:2]1[CH2:6][C:5](=[O:7])[N:4]([C:8]2[CH:13]=[C:12]([Cl:14])[CH:11]=[CH:10][C:9]=2[Cl:15])[N:3]=1.N1C=CC=CC=1.[N+](C1C=CC=CC=1)([O-])=O.[C:31](Cl)(=[O:35])[C:32]([CH3:34])=[CH2:33].[OH-].[Na+]>O1CCCC1.O.C(O)(=O)C>[Cl:15][C:9]1[CH:10]=[CH:11][C:12]([Cl:14])=[CH:13][C:8]=1[N:4]1[C:5](=[O:7])[CH2:6][C:2]([NH:1][C:31](=[O:35])[C:32]([CH3:34])=[CH2:33])=[N:3]1

Participants

9

Reactant 5

HCID 1049PyridineHCID 7416NitrobenzeneHCID 13528Methacryloyl chlorideHCID 14798Sodium HydroxideHCID 13853230HCID 13853230, compound

Product 1

HCID 13627545HCID 13627545, compoundYield 52%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

30 g (0.12 mol) of 3-amino-1-(2,5-dichlorophenyl)-2-pyrazolin-5-one was dissolved in 250 ml of tetrahydrofuran to which were added 21 ml (0.27 mol) of pyridine and 2.5 ml of nitrobenzene. To the mixture there was further added dropwise 28.2 g (0.27 mol) of methacryloyl chloride while cooling with ice and the mixture was stirred for about 30 minutes. After adding 250 ml of water, the mixture was extracted with ethyl acetate and the extract was dried with anhydrous sodium sulfate. After distilling off the solvent at from 20° C. to 30° C. under a reduced pressure, the residual oily product was dissolved in a mixture of 360 ml of water and 200 ml of ethanol, to which was then added dropwise an aqueous solution containing 14.8 g (0.37 mol) of sodium hydroxide dissolved in 50 ml of water 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, 19.5 g (52% yield) of Coupler Monomer (8) was obtained.

Workup

  1. temperaturewhile cooling with ice
  2. extractionthe mixture was extracted with ethyl acetate
  3. dry with materialthe extract was dried with anhydrous sodium sulfate
  4. distillationAfter distilling off the solvent at from 20° C. to 30° C. under a reduced pressure
  5. dissolutionthe residual oily product was dissolved in a mixture of 360 ml of water and 200 ml of ethanol, to which
  6. additionwas then added dropwise an aqueous solution
  7. stirringAfter stirring for 30 minutes
  8. filtrationthe crystals thus deposited were collected by filtration
  9. customBy recrystallization from acetonitrile, 19.5 g (52% yield) of Coupler Monomer (8)
  10. customwas obtained

Sources & evidence

ORD record
ord-4a04736455ef4cd18f51380fc254f819
Source dataset
uspto-grants-1984_03
Patent number
US04435503

Reaction notes

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