4-Chloroaniline → HCID 54262750, compound

HRID 1461823Notes

Reaction equation

HRID 1461823 reaction equation
[Cl:1][C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][CH:3]=1.[N:9]([O-])=O.[Na+].[CH3:13][O:14][C:15](=[O:30])[CH:16]([NH:21][C:22](=O)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)C(OC)=O.C(=O)([O-])[O-].[K+].[K+].C[O-].[Na+]>C(O)(=O)C.Cl.O.CC(C)=O.CO.C(OCC)(=O)C>[CH3:13][O:14][C:15]([C:16]1[N:21]=[C:22]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[N:6]([C:5]2[CH:7]=[CH:8][C:2]([Cl:1])=[CH:3][CH:4]=2)[N:9]=1)=[O:30]

Participants

12

Reactant 5

HCID 78124-ChloroanilineHCID 11430Potassium CarbonateHCID 569507HCID 569507, compoundHCID 10942334Sodium MethoxideHCID 23668193Sodium Nitrite

Product 1

HCID 54262750HCID 54262750, compound

Reagents, catalysts & solvents 6

HCID 176Acetic AcidSolventHCID 180AcetoneSolventHCID 313Hydrochloric AcidSolventHCID 887MethanolSolvent2×HCID 962WaterSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

6.4 g (0.05 mol) of 4-chloroaniline are dissolved in a mixture of 50 ml of glacial acetic acid and 12.5 ml of concentrated hydrochloric acid, the solution is cooled to 0° C. and a solution of 3.5 g (0.0507 mol) of sodium nitrite in 6.5 ml of water is added dropwise. The reaction mixture is then cooled to -10° C. and a solution of 11.7 g (0.0466 mol) of benzoylaminomalonic acid dimethyl ester in 120 ml of acetone is added dropwise thereto. A solution of 70.2 g (0.509 mol) of potassium carbonate in 70 ml of water is then added dropwise and stirring is then carried out for a further half an hour at from 0° to 5° C. Ethyl acetate is then added to the reaction mixture. The organic phase is separated, washed with water, dried over sodium sulfate, filtered and concentrated by evaporation to produce, in quantitative yield, an intermediate in the form of a red clear oil. 9.75 g (0.025 mol) thereof are dissolved in 50 ml of methanol, and 0.7 g (0.004 mol) of 30% sodium methoxide in methanol is added. The reaction solution is left to stand overnight at room temperature during which the product crystallises out. After filtering off and washing with a small amount of methanol, 3.4 g (43.6% of the theoretical yield) of 1-(4-chlorophenyl)-5-phenyl-1,2,4-triazole-3-carboxylic acid methyl ester having a melting point of 136°-137° C. are obtained.

Workup

  1. temperatureThe reaction mixture is then cooled to -10° C.
  2. waitis then carried out for a further half an hour at from 0° to 5° C
  3. customThe organic phase is separated
  4. washwashed with water
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated by evaporation
  8. customto produce, in quantitative yield
  9. waitThe reaction solution is left
  10. customthe product crystallises out
  11. filtrationAfter filtering off
  12. washwashing with a small amount of methanol, 3.4 g (43.6% of the

Sources & evidence

ORD record
ord-f620951f9d8d4e4eb6f0a67e347a2dcf
Source dataset
uspto-grants-1991_12
Patent number
US05077413

Reaction notes

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