3,4-Dichloroaniline → HCID 22763481, compound

HRID 1973044Notes

Reaction equation

HRID 1973044 reaction equation
[Cl-].[Cl:2][C:3]1[CH:4]=[C:5]([N+:10]#N)[CH:6]=[CH:7][C:8]=1[Cl:9].ClC1C=C(C=CC=1Cl)N.N([O-])=O.[Na+].[OH-].[K+].ClC1C=C(NN=[C:37]([CH2:43][C:44]2[CH:49]=[CH:48][C:47]([Cl:50])=[CH:46][C:45]=2[Cl:51])[C:38]([O:40][CH2:41][CH3:42])=[O:39])C=CC=1Cl>Cl.O.C(O)C.S(=O)(=O)(O)O>[Cl:9][C:8]1[CH:7]=[C:6]2[C:5](=[CH:4][C:3]=1[Cl:2])[NH:10][C:37]([C:38]([O:40][CH2:41][CH3:42])=[O:39])=[C:43]2[C:44]1[CH:49]=[CH:48][C:47]([Cl:50])=[CH:46][C:45]=1[Cl:51]

Participants

10

Reactant 5

HCID 72573,4-DichloroanilineHCID 14797Potassium HydroxideHCID 10262515Benzenediazonium, 3,4-dichloro-, chlorideHCID 23668193Sodium NitriteHCID 86733168HCID 86733168, compound

Product 1

HCID 22763481HCID 22763481, compound

Reagents, catalysts & solvents 4

HCID 313Hydrochloric AcidSolventHCID 702EthanolSolvent2×HCID 962WaterSolvent2×HCID 1118Sulfuric AcidSolvent

Procedure

Prepare a solution of 3,4-dichlorophenyl-diazonium chloride by treating 8.2 g. of 3,4-dichloroaniline in 25 ml of concentrated hydrochloric acid with a solution of 3.5 g. of sodium nitrite in 35 ml of water at -5°. Dissolve ethyl 2-(2,4-dichlorobenzyl) acetoacetate (14.3 g.) in 100 ml of ethanol with 8.3 g. of potassium hydroxide in 8.3 ml of water and cool to -5°. Add the solution of the diazonium salt to the latter solution, keeping the temperature at 0°, and stir for 15 minutes. Extract with ether and wash the ether solution with two 75 ml portions of 5% sodium hydroxide and then with water and dry (MgSo4). Evaporate to yield the intermediate: ethyl 2,4-dichlorophenylpyruvate 3,4-dichlorophenyl hydrazone. The analytical sample is obtained from ethanol; m.p. 160°-161°. Dissolve the hydrazone (125 g.) in 700 ml of 20% ethanolic sulfuric acid and boil under reflux for 2 hours. Cool to room temperature and collect the crystalline product. Wash with 50% aqueous alcohol. Recrystallize from ethanol; m.p. 230°-231°.

Workup

  1. additionby treating 8.2 g
  2. customat -5°
  3. customat 0°
  4. extractionExtract with ether
  5. washwash the ether solution with two 75 ml portions of 5% sodium hydroxide
  6. dry with materialwith water and dry (MgSo4)
  7. customEvaporate
  8. customto yield the intermediate
  9. temperatureunder reflux for 2 hours
  10. customcollect the crystalline product
  11. washWash with 50% aqueous alcohol
  12. customRecrystallize from ethanol

Sources & evidence

ORD record
ord-3aa0f7c9cca744088f10f0926847cfc8
Source dataset
uspto-grants-1976_12
Patent number
US03996159

Reaction notes

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