Bromine → HCID 50994279, compound

HRID 1518125Notes

Reaction equation

HRID 1518125 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=2[C:17]([F:20])([F:19])[F:18])[CH:7]=[CH:8][C:9]=1[NH2:10])([O-:3])=[O:2].[Br:21]Br>C(O)(=O)C>[Br:21][C:8]1[CH:7]=[C:6]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=2[C:17]([F:18])([F:19])[F:20])[CH:5]=[C:4]([N+:1]([O-:3])=[O:2])[C:9]=1[NH2:10]

Participants

4

Reactant 2

HCID 24408BromineHCID 509940363-Nitro-2'-trifluoromethyl-biphenyl-4-ylamine

Product 1

HCID 50994279HCID 50994279, compoundYield 88.3%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

The method of Siegel, J. S. et al. (Org. Lett., 2006, 8, 4989-4992) was used. 3-Nitro-2′-trifluoromethyl-biphenyl-4-ylamine (302 mg, 1.07 mmol, as prepared in Example 6, step A) was placed in an 8 mL vial equipped with a magnetic stir bar, and glacial acetic acid (2 mL) was added via pipette. The solid was allowed to dissolve, and bromine (1.07 eq., 59.0 μL, 1.14 mmol) was added dropwise via microsyringe. The reaction was tightly capped and stirred at RT for 30 min, during which time a precipitate formed. The reaction was poured into crushed ice, and the precipitate was isolated by filtration. The precipitate was washed with water (50 mL), dissolved in DCM (40 mL), dried over anhydrous MgSO4, filtered, and the solvent removed under reduced pressure. The crude material was chromatographed on a 24-g SiO2 pre-packed column eluting with EtOAc/hexanes, 0:1 to 1:4, v/v over 20 min, yielding 341 mg (88%) of the title compound. 1H-NMR (400 MHz, CDCl3) δ: 8.14 (d, J=2.0 Hz, 1H), 7.76 (d, J=7.8 Hz, 1H), 7.72 (d, J=2.0 Hz, 1H), 7.59 (t, J=7.5 Hz, 1H), 7.51 (t, J=7.7 Hz, 1H), 7.32 (d, J=7.6 Hz, 1H), 6.70 (br. s., 2H).

Workup

  1. customvial equipped with a magnetic stir bar
  2. dissolutionto dissolve
  3. customThe reaction was tightly capped
  4. customformed
  5. additionThe reaction was poured
  6. custominto crushed ice
  7. customthe precipitate was isolated by filtration
  8. washThe precipitate was washed with water (50 mL)
  9. dissolutiondissolved in DCM (40 mL)
  10. dry with materialdried over anhydrous MgSO4
  11. filtrationfiltered
  12. customthe solvent removed under reduced pressure
  13. customThe crude material was chromatographed on a 24-g SiO2 pre-packed column
  14. washeluting with EtOAc/hexanes, 0:1 to 1:4, v/v over 20 min

Sources & evidence

ORD record
ord-186eec3fbabd46dca228840f24334e38
Source dataset
uspto-grants-2012_07
Patent number
US08232409B2

Reaction notes

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