Methane → HCID 15753023, compound

HRID 1085617Notes

Reaction equation

HRID 1085617 reaction equation
[C:1]1([C:7]2[NH:8][CH:9]=[C:10]([C:14]#[N:15])[C:11]=2[C:12]#[N:13])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Br:16]Br.C>C(Cl)(Cl)Cl>[Br:16][C:9]1[NH:8][C:7]([C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)=[C:11]([C:12]#[N:13])[C:10]=1[C:14]#[N:15]

Participants

5

Reactant 3

HCID 297MethaneHCID 24408Bromine3×HCID 15753022HCID 15753022, compound

Product 1

HCID 15753023HCID 15753023, compound

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent2×

Conditions

Temperature
-10 °C

Procedure

Under a nitrogen purge, 2-phenyl-pyrrole-3,4-dicarbonitrile (1.4 g; 0.0075 mol) is added to CHCl3 (35 mL), much of the solid dissolving. A solution of bromine (0.4 mL; 0.008 mol) in CHCl3 (5 mL) is added dropwise over 20 minutes. Initially the color is discharged rapidly, but as a new, gummy solid begins to precipitate, the color remains. After stirring 30 minutes at ambient, the mixture is brought to reflux, resulting in a much more discreet solid. After refluxing 90 minutes, the reaction mixture is cooled and an aliquot is removed and analyzed (HPLC), showing ca. 60% starting material still remaining. In a single portion fresh bromine (0.2 mL; 0.004 mol) is added, and refluxing continued another 45 minutes whereupon an aliquot shows 10% starting material remaining. Another fresh portion of bromine (0.2 mL; 0.004 mol) is added to the refluxing suspension and refluxing is continued another 30 minutes. The suspension is cooled and stirred 18 hours at room temperature. Solvent is removed under reduced pressure to yield a greenish solid which is extracted with hot CHCl3, leaving behind a dark residue. The extract is treated with DARCO and filtered hot. The clear yellow filtrate quickly began to deposit a white precipitate. After cooling to -10° C., the white solid is collected by filtration.

Workup

  1. customUnder a nitrogen purge
  2. dissolutiondissolving
  3. customto precipitate
  4. temperatureto reflux
  5. customresulting in a much more discreet solid
  6. temperatureAfter refluxing 90 minutes
  7. temperaturethe reaction mixture is cooled
  8. customan aliquot is removed
  9. temperaturerefluxing
  10. waitcontinued another 45 minutes whereupon an aliquot
  11. temperaturerefluxing
  12. waitis continued another 30 minutes
  13. temperatureThe suspension is cooled
  14. stirringstirred 18 hours at room temperature
  15. customSolvent is removed under reduced pressure
  16. customto yield a greenish solid which
  17. extractionis extracted with hot CHCl3
  18. customleaving behind a dark residue
  19. filtrationfiltered hot
  20. filtrationthe white solid is collected by filtration

Sources & evidence

ORD record
ord-3074677dc5e64835ac45111d4f9053dd
Source dataset
uspto-grants-1991_04
Patent number
US05010098

Reaction notes

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