N-bromobutanimide → 2-Bromo-4-fluorobenzaldehyde

HRID 1006906Notes

Reaction equation

HRID 1006906 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[CH3:9].BrN1C(=[O:16])CCC1=O>C(OCC)(=O)C.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[Br:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[CH:9]=[O:16]

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 740162-Bromo-4-fluorotoluene

Product 1

HCID 27733192-Bromo-4-fluorobenzaldehydeYield 41%

Reagents, catalysts & solvents 2

HCID 7187Benzoyl PeroxideCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

2-Bromo-4-fluorotoluene (10.215 g) was dissolved in ethyl acetate (100 ml), N-bromosuccinimide (11.3 g) and 70% benzoyl peroxide (200 mg) were added thereto, and the resulting mixture was stirred under heating at 80° C. for 1 hr. After the reaction solution was cooled, the resulting insoluble matters were filtered off. The resulting filtrate was washed with an aqueous solution of saturated sodium bicarbonate, dried (over MgSO4) and evaporated. The resulting residue was dissolved in acetic acid (30 ml), water (30 ml) and hexamethylene tetramine (15.141 g) were added thereto, and the resulting mixture was heated under stirring at 100° C. for 1 hr. To the mixture was added 38% hydrochloric acid (20 ml), which was then stirred for 1 hr, and then it was cooled as it was, and extracted with ethyl acetate. The resulting organic phase was washed with an aqueous solution of saturated sodium bicarbonate, dried (over MgSO4) and evaporated. The resulting residue was purified by silica gel column chromatography (ethyl acetate/hexane system), to give the title compound as a colorless solid (4.376 g, yield; 41%).

Workup

  1. temperatureAfter the reaction solution was cooled
  2. filtrationthe resulting insoluble matters were filtered off
  3. washThe resulting filtrate was washed with an aqueous solution of saturated sodium bicarbonate
  4. dry with materialdried (over MgSO4)
  5. customevaporated
  6. dissolutionThe resulting residue was dissolved in acetic acid (30 ml)
  7. additionwater (30 ml) and hexamethylene tetramine (15.141 g) were added
  8. temperaturethe resulting mixture was heated
  9. stirringunder stirring at 100° C. for 1 hr
  10. additionTo the mixture was added 38% hydrochloric acid (20 ml), which
  11. stirringwas then stirred for 1 hr
  12. temperatureit was cooled as it
  13. extractionextracted with ethyl acetate
  14. washThe resulting organic phase was washed with an aqueous solution of saturated sodium bicarbonate
  15. dry with materialdried (over MgSO4)
  16. customevaporated
  17. customThe resulting residue was purified by silica gel column chromatography (ethyl acetate/hexane system)

Sources & evidence

ORD record
ord-6b4701cfa96b42bd9e0e81b500d079dc
Source dataset
uspto-grants-2004_09
Patent number
US06790844B2

Reaction notes

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