Ethyl Acetate → 8-Bromo-6-nitroquinoline

HRID 402958Notes

Reaction equation

HRID 402958 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]2[C:11](=[CH:12][CH:13]=1)[N:10]=[CH:9][CH:8]=[CH:7]2)([O-:3])=[O:2].[Br:14]N1C(=O)CCC1=O.C(=O)(O)[O-].[Na+].C(OCC)(=O)C>S(=O)(=O)(O)O>[Br:14][C:12]1[CH:13]=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=[C:6]2[C:11]=1[N:10]=[CH:9][CH:8]=[CH:7]2

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 119456-NitroquinolineHCID 67184N-bromobutanimideHCID 516892Sodium Bicarbonate2×

Product 1

HCID 141173628-Bromo-6-nitroquinolineYield 35.2%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Conditions

Temperature
60 °C

Procedure

To a flask containing 6-nitroquinoline (4 g, 23 mmol) in sulfuric acid (20 ml) was added N-bromo-succinimide (5.31 g, 29.9 mmol). The mixture was heated to 60° C. (oil bath) for 6 hours and then stored in a freezer overnight. The crude reaction mixture was poured into a beaker containing ice (250 ml). The material was basified by adding first solid sodium bicarbonate and then a saturated solution of sodium bicarbonate (to a pH of about 10). During this procedure ethyl acetate (60 ml) was also added. The material was filtered to remove insoluble material and the filtrate transferred to a reparatory funnel. Ethyl acetate (100 ml) was added and the biphasic material shaken. The organic phase was collected and shaken with an equal volume of brine solution. The ethyl acetate phase was collected and the aqueous phases were back extracted with ethyl acetate (2×100 ml). The combined organic phase was stripped to provide a solid. The solid from the above filtration was taken up in hot ethyl acetate (60 ml). The material was cooled to ambient, dried over magnesium sulfate and filtered. The solvent was stripped and the crude solid product was combined with the material obtained from aqueous work up. This material was crystallized from hot ethyl acetate/hexane to provide the desired product as a yellow powder (2.05 g).

Workup

  1. customThe crude reaction mixture
  2. additionwas poured into a beaker
  3. filtrationThe material was filtered
  4. customto remove insoluble material
  5. customthe filtrate transferred to a reparatory funnel
  6. additionEthyl acetate (100 ml) was added
  7. customThe organic phase was collected
  8. stirringshaken with an equal volume of brine solution
  9. customThe ethyl acetate phase was collected
  10. extractionthe aqueous phases were back extracted with ethyl acetate (2×100 ml)
  11. customto provide a solid
  12. filtrationThe solid from the above filtration
  13. temperatureThe material was cooled to ambient,
  14. dry with materialdried over magnesium sulfate
  15. filtrationfiltered
  16. customobtained from aqueous work up
  17. customThis material was crystallized from hot ethyl acetate/hexane

Sources & evidence

ORD record
ord-b35adc5c76ec41d6ad0d45c7d737153a
Source dataset
uspto-grants-2014_06
Patent number
US08742098B2

Reaction notes

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