Formaldehyde → 5-amino-2,4-dihydro-4-methyl-2-[4-(methylsulphonyl)phenyl]-3H-pyrazol-3-one

HRID 1974045Notes

Reaction equation

HRID 1974045 reaction equation
[CH3:1][S:2]([C:5]1[CH:10]=[CH:9][C:8]([N:11]2[C:15](=[O:16])[CH2:14][C:13]([NH2:17])=[N:12]2)=[CH:7][CH:6]=1)(=[O:4])=[O:3].C=O.[C:20]([O-])(=O)C.[NH4+].[H][H]>[Ni].CO>[CH3:1][S:2]([C:5]1[CH:10]=[CH:9][C:8]([N:11]2[C:15](=[O:16])[CH:14]([CH3:20])[C:13]([NH2:17])=[N:12]2)=[CH:7][CH:6]=1)(=[O:3])=[O:4]

Participants

7

Reactant 4

HCID 712FormaldehydeHCID 517165Ammonium AcetateHCID 21488696HCID 21488696, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 30155745-amino-2,4-dihydro-4-methyl-2-[4-(methylsulphonyl)phenyl]-3H-pyrazol-3-one

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 887MethanolSolvent

Procedure

In a 3 liter autoclave were placed: 151.8 g (0.6 mole) of 1-(p-methylsulphonylphenyl)-3-amino-2-pyrazolin-5-one, 27 g (0.9 mole) of paraformaldehyde, 115.5 g (1.5 mole) of ammonium acetate, 60 g of Raney nickel and 1735 ml of methanol. The autoclave was charged with hydrogen to a pressure of 1500 psi. After reduction for 2 h at 100° C the catalyst was filtered off and the filtrate was neutralized by addition of 100 ml of concentrated hydrochloric acid. The filtrate was concentrated by evaporation and the residue was diluted by addition of 300 ml of water. The precipitate was separated and treated with boiling acetonitrile. Yield: 65 g (40%). Melting Point: 239°-240° C.

Workup

  1. filtrationAfter reduction for 2 h at 100° C the catalyst was filtered off
  2. additionthe filtrate was neutralized by addition of 100 ml of concentrated hydrochloric acid
  3. concentrationThe filtrate was concentrated by evaporation
  4. additionthe residue was diluted by addition of 300 ml of water
  5. customThe precipitate was separated
  6. additiontreated with boiling acetonitrile

Sources & evidence

ORD record
ord-61185ecde5184b03940bfb5b69db01fb
Source dataset
uspto-grants-1976_12
Patent number
US04000156

Reaction notes

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