Water → HCID 66813770, compound

HRID 924558Notes

Reaction equation

HRID 924558 reaction equation
[C:1]1(=[O:15])[C:14]2[C:5](=[N:6][CH:7]=[C:8]3[C:13]=2[CH:12]=[CH:11][CH:10]=[CH:9]3)[CH:4]=[CH:3][CH2:2]1.[Br:16]Br.O>C(O)(=O)C>[Br:16][CH:2]1[CH:3]=[CH:4][C:5]2[C:14](=[C:13]3[C:8](=[CH:7][N:6]=2)[CH:9]=[CH:10][CH:11]=[CH:12]3)[C:1]1=[O:15]

Participants

5

Reactant 3

HCID 962WaterHCID 24408Bromine3×HCID 53434997HCID 53434997, compound

Product 1

HCID 66813770HCID 66813770, compoundYield 91.4%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent2×

Procedure

99.8 g (511 mmol) phenanthridinone was added to a 3 L multi-neck flask equipped with a stir arm and condenser. 1.2 L glacial acetic acid was added and the mixture was allowed to stir at 150 rpm and heated to reflux. 90 g (562 mmol) Br2 suspended in 100 ml acetic acid was added to the refluxing solution dropwise over a period of 3 hours. After addition, the mixture was assayed and revealed to be ˜80% complete. Based on this assay, an additional 20 g of Br2 (in 30 mL acetic acid) was added dropwise to the mixture at reflux. After this addition, the assay was >90% complete. A final 20 g Br2 (in 30 mL acetic acid) was added dropwise and the mixture allowed to stir for 1 hour after addition. The final assay was >97%. The mixture was cooled and 1 L of water was added and the mixture filtered. The wet solids were then stirred in aqueous sodium thiosulfate to destroy residual bromine and refiltered. These solids were rinsed with H2O and allowed to dry in vacuo to remove residual water. The solids were then recrystalllized from nitrobenzene (>2 liters) and collected on a funnel to give 128 g 2-bromophenanthridinone (90.8% yield).

Workup

  1. customequipped with a stir arm and condenser
  2. temperatureheated to reflux
  3. additionwas added to the refluxing solution dropwise over a period of 3 hours
  4. additionAfter addition
  5. temperatureat reflux
  6. additionAfter this addition
  7. stirringto stir for 1 hour
  8. additionafter addition
  9. temperatureThe mixture was cooled
  10. filtrationthe mixture filtered
  11. stirringThe wet solids were then stirred in aqueous sodium thiosulfate
  12. customto destroy residual bromine
  13. washThese solids were rinsed with H2O
  14. customto dry in vacuo
  15. customto remove residual water
  16. customcollected on a funnel

Sources & evidence

ORD record
ord-138095ad7d1d429b8059d9041a73967e
Source dataset
uspto-grants-2016_03
Patent number
US09281483B2

Reaction notes

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