Bromide ion → N-(4-Formyl-3-methylphenyl)acetamide

HRID 1955373Notes

Reaction equation

HRID 1955373 reaction equation
[OH-:1].[Na+].[S].O.O.O.O.O.O.O.O.O.[S-2].[Na+].[Na+].[N+:16]([C:19]1[CH:20]=[C:21]([CH3:26])[C:22]([CH3:25])=[CH:23][CH:24]=1)([O-])=O.[Br-].[CH:28]([OH:31])(C)[CH3:29]>O>[C:28]([NH:16][C:19]1[CH:24]=[CH:23][C:22]([CH:25]=[O:1])=[C:21]([CH3:26])[CH:20]=1)(=[O:31])[CH3:29]

Participants

8

Reactant 6

HCID 259Bromide ionHCID 3776Isopropanol2×HCID 74404-Nitro-o-xyleneHCID 14798Sodium HydroxideHCID 73972Sodium sulfide nonahydrateHCID 5362487Sulfur

Product 1

HCID 12931765N-(4-Formyl-3-methylphenyl)acetamideYield 68%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

In a 500-ml flask, place 12.0 g (0.3 m) of sodium hydroxide pellets, 6.41 g (0.2 m) of sulfur powder, 18.0 g (0.075 m) of sodium sulfide nonahydrate, and 140 ml of distilled water. Heat the mixture with good stirring to about 70 C. to make an orange-red solution. In a 100-ml beaker, place 22.7 g (0.15 m) of 4-nitro-o-xylene, 2.4 g (5 mole %) of tetrabutlammonium bromide and 30 ml of isopropyl alcohol. Warm it to 50 C. with occasional stirring to make a clear pale-yellow solution. Add the solution in the beaker to the mixture in the 500-ml flask and use 10 ml of isopropyl alcohol to rinse the beaker and add to the reaction mixture. Heat the mixture with vigorous stirring under gentle reflux for 4.5 hours. Distill off isopropyl alcohol till approximately 50 ml of distillate is collected and pot/vapor temperature reaches to 100 C. Cool the reaction mixture to 20 C. Add 100 ml of propyl acetate and stir vigorously at room temperature for 5 minutes, and let layers settle. Separate off bottom water layer. Wash propyl acetate solution with 100 ml of water. Add 27 g (0.45 m) of acetyl anhydride slowly to propyl acetate solution containing 4-amino-2-methylbenzaldehyde. Stir the mixture at 40 C. for 1 hour. Add 100 ml of heptane and cool the mixture to room temperature. Stir slurry in a cold water bath for 1 hour. Collect solid, wash with 1:1 propyl acetate/heptane and dry to give 18.0 g (68%) of 4-acetylamino-2-methylbenzaldehyde.

Workup

  1. temperatureHeat the mixture
  2. temperatureWarm it to 50 C
  3. stirringwith occasional stirring
  4. additionAdd the solution in the beaker to the mixture in the 500-ml flask
  5. washto rinse the beaker
  6. additionadd to the reaction mixture
  7. temperatureHeat the mixture
  8. stirringwith vigorous stirring
  9. temperatureunder gentle reflux for 4.5 hours
  10. distillationDistill off isopropyl alcohol till approximately 50 ml of distillate
  11. customis collected
  12. temperatureCool the reaction mixture to 20 C
  13. additionAdd 100 ml of propyl acetate
  14. stirringstir vigorously at room temperature for 5 minutes
  15. customSeparate off bottom water layer
  16. additionAdd 27 g (0.45 m) of acetyl anhydride slowly to propyl acetate solution
  17. additioncontaining 4-amino-2-methylbenzaldehyde
  18. stirringStir the mixture at 40 C
  19. additionAdd 100 ml of heptane
  20. stirringStir slurry in a cold water bath for 1 hour
  21. customCollect solid
  22. washwash with 1:1 propyl acetate/heptane
  23. customdry

Sources & evidence

ORD record
ord-b6962cd6823a425caf45e163d9eb263d
Source dataset
uspto-grants-2000_09
Patent number
US06124503

Reaction notes

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