Glyoxylic Acid → 6-(2-Hydroxyphenyl)-3(2H)-pyridazinone

HRID 370751Notes

Reaction equation

HRID 370751 reaction equation
[OH-:1].[K+].[C:3]([OH:7])(=O)[CH:4]=O.O[CH2:9][C:10]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)=O.C(O)(=O)C=O.[OH-].[K+].S(=O)(=O)(O)O.O.[NH2:31][NH2:32]>O>[OH:1][C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][C:12]=1[C:10]1[CH:9]=[CH:4][C:3](=[O:7])[NH:31][N:32]=1

Participants

8

Reactant 6

HCID 760Glyoxylic AcidHCID 1118Sulfuric AcidHCID 14797Potassium Hydroxide2×HCID 24654Hydrazine hydrate (1:1)HCID 68490alpha-HydroxyacetophenoneHCID 23702009HCID 23702009, compound

Product 1

HCID 30173466-(2-Hydroxyphenyl)-3(2H)-pyridazinoneYield 54%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A 20% w/v solution of potassium hydroxide cooled to 5° was added slowly to a cooled (5°) 50% aqueous solution of glyoxylic acid (1184 g, 8 mol) until the mixture had pH 9, with external cooling to maintain the temperature below 25°. 2-Hydroxyacetophenone (1089 g, 8 mol) was poured into a solution of potassium hydroxide (783 g) in water (2580 ml), this mixture was added to the glyoxylic acid-potassium hydroxide solution and the resultant mixture was stirred at room temperature for 4 hours. The pH was adjusted to pH 8, with external cooling, by the addition of concentrated sulphuric acid (330 ml). An inorganic sediment was removed by filtration, the filtrate was extracted with dichloromethane (3000 ml) and concentrated sulphuric acid (100 ml) was added with external cooling to the aqueous phase to give a mixture with pH 4.5. A solid precipitated out during this process. Concentrated aqueous ammonia (28% w/w) was added with external cooling until the mixture had pH 8. The precipitate dissolved during this addition. Aqueous hydrazine hydrate (64% w/w, 402.4 g, 8 mol) was added, the mixture was heated under reflux for 3 hours and allowed to cool to room temperature. The solid was filtered off, washed with water and 2-propanol and dried to give 6-(2-hydroxyphenyl)-3(2H)-pyridazinone (811 g, 54%) m.p. 294°.

Workup

  1. temperaturecooled to 5°
  2. additionwas added slowly to
  3. temperaturewith external cooling
  4. temperatureto maintain the temperature below 25°
  5. customAn inorganic sediment was removed by filtration
  6. extractionthe filtrate was extracted with dichloromethane (3000 ml) and concentrated sulphuric acid (100 ml)
  7. additionwas added
  8. temperaturewith external cooling to the aqueous phase
  9. customto give a mixture with pH 4.5
  10. customA solid precipitated out during this process
  11. additionConcentrated aqueous ammonia (28% w/w) was added
  12. temperaturewith external cooling until the mixture
  13. dissolutionThe precipitate dissolved during this addition
  14. temperaturethe mixture was heated
  15. temperatureunder reflux for 3 hours
  16. filtrationThe solid was filtered off
  17. washwashed with water and 2-propanol
  18. customdried

Sources & evidence

ORD record
ord-3ebb164c0b9b4290a1aa577447123a02
Source dataset
uspto-grants-1985_07
Patent number
US04528371

Reaction notes

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