Hydrochloric Acid → 4-Bromo-chloro-3-methylbenzaldoxime

HRID 1096140Notes

Reaction equation

HRID 1096140 reaction equation
[Br:1][C:2]1[CH:10]=[CH:9][C:5]([CH:6]=[N:7][OH:8])=[CH:4][C:3]=1[CH3:11].[ClH:12].Cl[O-].[Na+]>O1CCCC1>[Br:1][C:2]1[CH:10]=[CH:9][C:5]([CH:6]=[N:7][OH:8])=[C:4]([Cl:12])[C:3]=1[CH3:11]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 23665760Sodium HypochloriteHCID 738479544-Bromo-3-methylbenzaldehyde oxime

Product 1

HCID 866584614-Bromo-chloro-3-methylbenzaldoximeYield 98.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

In a solution of 82.0 g of 4-bromo-3-methylbenzaldoxime in 450 ml of tetrahydrofuran, 120.0 g of concentrated hydrochloric acid was added a dropwise with stirring under ice cooling over 45 minutes. Then, 220 ml of 8% sodium hypochlorite aqueous solution was carefully added dropwise over 75 minutes so that the temperature of the reaction mixture would not exceed 5° C., after the completion of the addition, continued to stir at 10° C. or less further for 90 minutes. After the completion of the reaction, nitrogen gas was blown through the reaction mixture for 45 minutes and precipitated insoluble material was filtered off, and tetrahydrofuran was distilled off under reduced pressure. The remaining aqueous solution was extracted with 240.0 g of ethyl acetate. The organic phase was washed with water (240 ml×2) and then insoluble material was filtered off, the solvent was distilled off under reduced pressure to obtain 93.5 g of the aimed product as pale yellow crystal.

Workup

  1. customexceed 5° C.
  2. additionafter the completion of the addition
  3. stirringto stir at 10° C. or less further for 90 minutes
  4. customAfter the completion of the reaction, nitrogen gas
  5. waitwas blown through the reaction mixture for 45 minutes
  6. customprecipitated insoluble material
  7. filtrationwas filtered off
  8. distillationtetrahydrofuran was distilled off under reduced pressure
  9. extractionThe remaining aqueous solution was extracted with 240.0 g of ethyl acetate
  10. washThe organic phase was washed with water (240 ml×2)
  11. filtrationinsoluble material was filtered off
  12. distillationthe solvent was distilled off under reduced pressure

Sources & evidence

ORD record
ord-fb9f8b31081f4026b1a90ad033208025
Source dataset
uspto-grants-2012_03
Patent number
US08138213B2

Reaction notes

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