Bromine → 4-Bromo-2-(p-chlorophenyl)-5-[(trifluoromethyl)thio]pyrrole-3-carbonitrile

HRID 375211Notes

Reaction equation

HRID 375211 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[NH:9][C:10]([S:15][C:16]([F:19])([F:18])[F:17])=[CH:11][C:12]=2[C:13]#[N:14])=[CH:4][CH:3]=1.[Br:20]N1C(=O)CCC1=O.C([O-])(=O)C.[Na+].BrBr>O1CCCC1.CCOCC.O.C(O)(=O)C>[Br:20][C:11]1[C:12]([C:13]#[N:14])=[C:8]([C:5]2[CH:6]=[CH:7][C:2]([Cl:1])=[CH:3][CH:4]=2)[NH:9][C:10]=1[S:15][C:16]([F:17])([F:19])[F:18]

Participants

9

Reactant 4

HCID 24408BromineHCID 67184N-bromobutanimideHCID 517045Sodium AcetateHCID 189303922-(p-Chlorophenyl)-5-[(trifluoromethyl)thio]pyrrole-3-carbonitrile

Product 1

HCID 189304244-Bromo-2-(p-chlorophenyl)-5-[(trifluoromethyl)thio]pyrrole-3-carbonitrile

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

Under a nitrogen purge, a solution of 2-(p-chlorophenyl)-5-[(trifluoromethyl)thio]pyrrole-3-carbonitrile (0.6 g, 0.002 mol) in tetrahydrofuran is treated with N-bromosuccinimide (0.36 g, 0,002 mol), stirred for 16 hours at room temperature and concentrated in vacuo to obtain a residue. The residue is dissolved in ether and diluted with water. The organic phase is separated, washed with water and brine, dried over anhydrous magnesium sulfate and concentrated in vacuo to obtain a solid. High performance liquid chromatography indicates that the solid contains 20% starting material. A solution of the mixture and sodium acetate (0.05 g, 0.006 mol) in acetic acid is treated with bromine (0.03 mL, 0.0006 mol), stirred for 16 hours at 60° C., cooled and concentrated in vacuo to obtain a semi-solid. The semi-solid is partitioned between ethyl acetate and water. The organic phase is separated, washed with water and brine, dried over anhydrous magnesium sulfate and concentrated in vacuo to obtain a solid. The solid is recrystallized from ethylene dichloride to give the title product as an off-white solid (mp 241°-243° C.) which is identified by 1 HNMR and 13CNMR spectral analyses.

Workup

  1. customUnder a nitrogen purge
  2. concentrationconcentrated in vacuo
  3. customto obtain a residue
  4. customThe organic phase is separated
  5. washwashed with water and brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. concentrationconcentrated in vacuo
  8. customto obtain a solid
  9. stirringstirred for 16 hours at 60° C.
  10. temperaturecooled
  11. concentrationconcentrated in vacuo
  12. customto obtain a semi-solid
  13. customThe semi-solid is partitioned between ethyl acetate and water
  14. customThe organic phase is separated
  15. washwashed with water and brine
  16. dry with materialdried over anhydrous magnesium sulfate
  17. concentrationconcentrated in vacuo
  18. customto obtain a solid
  19. customThe solid is recrystallized from ethylene dichloride

Sources & evidence

ORD record
ord-44dc02ce35624e8ea44e4b50699d6640
Source dataset
uspto-grants-1996_01
Patent number
US05484807

Reaction notes

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