Phenylhydrazine → 3-Methyl-1-phenyl-4,5-dihydro-1H-1,2,4-triazol-5-one

HRID 2399542Notes

Reaction equation

HRID 2399542 reaction equation
C1(NN)C=CC=CC=1.C(OC)(OC)(OC)C.[C:17]1([NH:23][N:24]=[C:25](OC)[CH3:26])[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.[O-:29][C:30]#[N:31].[Na+]>CO.O.C(O)(=O)C>[CH3:26][C:25]1[NH:31][C:30](=[O:29])[N:23]([C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)[N:24]=1

Participants

8

Reactant 4

HCID 7516PhenylhydrazineHCID 15050Trimethyl orthoacetateHCID 517096Sodium CyanateHCID 54154372N-phenyl-N'-(1-methoxyethylidene)hydrazine

Product 1

HCID 1355376213-Methyl-1-phenyl-4,5-dihydro-1H-1,2,4-triazol-5-oneYield 75.9%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolvent2×HCID 887MethanolSolventHCID 962WaterSolvent2×

Procedure

A stirred solution of 2.0 grams (0.019 mole) of phenylhydrazine and 11.1 grams (0.092 mole-5 eq.) of trimethyl orthoacetate (TMOA) in 20 mL of methanol was heated at reflux for about six hours. The reaction mixture was then allowed to cool to ambient temperature where it stirred for about 18 hours. The reaction mixture was again warmed to reflux where it stirred for another six hours, until the reaction to the intermediate N-phenyl-N'-(1-methoxyethylidene)hydrazine was complete. The progress of the reaction was monitored by gas chromatograph (GC). After this time, the reaction mixture was cooled in an ice-water bath (0° C.), and 1.5 grams (0.023 mole- 1.2 eq.) of sodium cyanate was added. Upon completion of addition, 1.6 grams (0.026 mole-1.4 eq.) of acetic acid was added dropwise. The reaction mixture was then stirred at the ice-water bath temperature for about 10 minutes and then was allowed to warm to ambient temperature. After this time, two mL of water was added to the reaction mixture. Analysis of the reaction mixture by GC showed formation of the targeted compound. One mL of acetic acid was then added to the reaction mixture, followed by the addition of two mL of water. Upon completion of addition, the reaction mixture was stirred at ambient temperature for about 18 hours. The reaction mixture was concentrated under reduced pressure, yielding 2.5 grams (75.9% yield) of 4,5-dihydro-3-methyl-1-phenyl-1,2,4-triazol-5(1H)-one.

Workup

  1. temperatureat reflux for about six hours
  2. temperatureThe reaction mixture was again warmed
  3. temperatureto reflux where it
  4. additionwas added
  5. additionwas added dropwise
  6. temperatureto warm to ambient temperature
  7. additionUpon completion of addition
  8. stirringthe reaction mixture was stirred at ambient temperature for about 18 hours
  9. concentrationThe reaction mixture was concentrated under reduced pressure

Sources & evidence

ORD record
ord-43c93709f4184747ac1c15d21b2d11fb
Source dataset
uspto-grants-1995_09
Patent number
US05449784

Reaction notes

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