Nitric Acid → Pyridazine, 4-nitro-, 1-oxide

HRID 648425Notes

Reaction equation

HRID 648425 reaction equation
[N+:1]1([O-:7])[CH:6]=[CH:5][CH:4]=[CH:3][N:2]=1.[N+:8]([O-])([OH:10])=[O:9].C(=O)(O)[O-].[Na+]>S(=O)(=O)(O)O>[N+:8]([C:4]1[CH:5]=[CH:6][N+:1]([O-:7])=[N:2][CH:3]=1)([O-:10])=[O:9]

Participants

5

Reactant 3

HCID 944Nitric Acid3×HCID 137016Pyridazine 1-oxideHCID 516892Sodium Bicarbonate

Product 1

HCID 147196Pyridazine, 4-nitro-, 1-oxide

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Procedure

With cooling and stirring, 5.1 grams (0.053 mole) of pyridazine-1-oxide was dissolved in 50 ml of fuming sulfuric acid. To this was added 8.83 ml of fuming nitric acid. Upon completion of addition the reaction mixture was warmed to 130°-135° C. where it stirred for two hours. Analysis of the reaction mixture by thin layer chromatography (TLC) indicated the reaction was not complete. The reaction mixture was allowed to cool to ambient temperature where it stood for 16 hours. An additional 1.3 ml of fuming nitric acid was added and the reaction mixture was heated to 130°-135° C. where it stirred for 4 hours. Analysis of the reaction mixture by TLC indicated the reaction still had not gone to completion. An additional 1.3 ml of fuming nitric acid was added to the reaction mixture, which was stirred an additional 4 hours at 130°-135° C. The reaction mixture was poured into ice-water where it stood for several hours. The pH of the mixture was adjusted to near 7 with sodium bicarbonate, then the mixture was extracted with methylene chloride using a continuous extractor. The extract was dried with sodium sulfate and filtered. The filtrate was subjected to column chromatography on silica gel using 10% acetone in methylene chloride as eluent. The appropriate fractions were combined and concentrated under reduced pressure to give 1.1 grams of 4-nitropyridazine-1-oxide, m.p. 149°-151.5° C.

Workup

  1. temperatureWith cooling
  2. additionUpon completion of addition the reaction mixture
  3. temperaturewas warmed to 130°-135° C. where it
  4. stirringstirred for two hours
  5. temperaturethe reaction mixture was heated to 130°-135° C. where it
  6. stirringstirred for 4 hours
  7. customthe reaction
  8. stirringwas stirred an additional 4 hours at 130°-135° C
  9. waitstood for several hours
  10. extractionthe mixture was extracted with methylene chloride using a continuous extractor
  11. dry with materialThe extract was dried with sodium sulfate
  12. filtrationfiltered
  13. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-379e5fcee414491e87462a014e57a405
Source dataset
uspto-grants-1988_04
Patent number
US04735650

Reaction notes

Loading…