Hydrochloric Acid → HCID 54010044, compound

HRID 2372403Notes

Reaction equation

HRID 2372403 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH2:8][C:9]([NH:11][NH2:12])=O.[CH2:13]([O:15][C:16](=[O:21])[C:17](Cl)=[N:18][CH3:19])[CH3:14].Cl>ClCCl>[CH2:13]([O:15][C:16]([C:17]1[N:18]([CH3:19])[C:9]([CH2:8][C:3]2[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=2[Cl:1])=[N:11][N:12]=1)=[O:21])[CH3:14]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 27329592-(2-chlorophenyl)acetohydrazideHCID 12531477HCID 12531477, compound

Product 1

HCID 54010044HCID 54010044, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

14.8 g (80 mmol) of o-chlorophenylacetic acid hydrazide are suspended in 230 ml of dichloromethane. At 5°, 12 g (80 mmol) of 2-chloro-2-(N-methylimino)-acetic acid ethyl ester [Tetrahedron Lett. 30, 2827 (1979)] are added dropwise thereto. The whole is then stirred for 2 hours while cooling with ice and then overnight at room temperature. The reaction mixture is then poured onto ice, 50 ml of 2N hydrochloric acid are added thereto and the whole is extracted twice with dichloromethane. The combined dichloromethane phases are washed twice with water. All the acidic aqueous phases are combined, rendered alkaline with solid sodium carbonate and extracted three times by shaking with dichloromethane. These three organic phases are combined, washed in succession with water and saturated sodium chloride solution, dried over magnesium sulphate and concentrated by evaporation. The residue is taken up in 150 ml of xylene and stirred under reflux for 44 hours. The reaction mixture is then concentrated and chromatographed over silica gel using ethyl acetate as eluant. The eluate is concentrated by evaporation and recrystallised from ether. 5-(o-chlorobenzyl)-4-methyl-4H-1,2,4-triazole-3-carboxylic acid ethyl ester of m.p. 87-88° is obtained in a yield of 12.4 g (55% of the theoretical yield).

Workup

  1. temperaturewhile cooling with ice
  2. customovernight
  3. customat room temperature
  4. additionare added
  5. extractionthe whole is extracted twice with dichloromethane
  6. washThe combined dichloromethane phases are washed twice with water
  7. extractionextracted three times
  8. stirringby shaking with dichloromethane
  9. washwashed in succession with water and saturated sodium chloride solution
  10. dry with materialdried over magnesium sulphate
  11. concentrationconcentrated by evaporation
  12. stirringstirred
  13. temperatureunder reflux for 44 hours
  14. concentrationThe reaction mixture is then concentrated
  15. customchromatographed over silica gel
  16. concentrationThe eluate is concentrated by evaporation
  17. customrecrystallised from ether

Sources & evidence

ORD record
ord-b19f6edb36c94627ae0a27302388b52c
Source dataset
uspto-grants-1992_03
Patent number
US05098922

Reaction notes

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