Citric Acid → 1,3-Dibromo-5-[3-(trifluoromethyl)phenoxy]benzene

HRID 549556Notes

Reaction equation

HRID 549556 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([OH:9])[CH:5]=[C:6]([Br:8])[CH:7]=1.[F:10][C:11]([F:22])([F:21])[C:12]1[CH:13]=[C:14](B(O)O)[CH:15]=[CH:16][CH:17]=1.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>CC([O-])=O.CC([O-])=O.[Cu+2].ClCCl>[Br:1][C:2]1[CH:3]=[C:4]([O:9][C:16]2[CH:15]=[CH:14][CH:13]=[C:12]([C:11]([F:22])([F:21])[F:10])[CH:17]=2)[CH:5]=[C:6]([Br:8])[CH:7]=1

Participants

6

Reactant 3

HCID 311Citric AcidHCID 122803,5-DibromophenolHCID 27343883-(Trifluoromethyl)phenylboronic acid3×

Product 1

HCID 671714461,3-Dibromo-5-[3-(trifluoromethyl)phenoxy]benzene

Reagents, catalysts & solvents 2

HCID 8895Cupric acetateCatalystHCID 6344DichloromethaneSolvent

Procedure

3,5-Dibromophenol (4.1 g; 16.2 mmol), 3-(trifluoromethyl)-phenylboronic acid (6.2 g; 32.4 mmol), Cu(II) acetate (2.9 g; 16.2 mmol), TEA (5.6 mL; 40.5 mmol) and dichloromethane (150 mL) and molecular sieves (2 ml) was added to a reaction flask the reaction mixture was stirred for 7 days. Further 3-(trifluoromethyl)-phenylboronic acid (6.2 g; 32.4 mmol) was added and the reaction mixture stirred for 1 day. Further 3-(trifluoromethyl)-phenylboronic acid (6.2 g; 32.4 mmol) and TEA (5.6 mL; 40.5 mmol) was added and the reaction mixture stirred for 1 day. 5% Aqueous citric acid (150 mL) was added and the two phases were separated. The aqueous phase was extracted with dichloromethane (50 mL×2) and the organic phases were pooled, dried and evaporated to dryness. The crude product purified by flash chromatography (heptane→ethyl acetate:heptane 1:9). Yield: 1.86 g; HPLC-MS: m/z: 397. (M+H)+; Rt: 2.78 min.

Workup

  1. stirringthe reaction mixture stirred for 1 day
  2. stirringthe reaction mixture stirred for 1 day
  3. customthe two phases were separated
  4. extractionThe aqueous phase was extracted with dichloromethane (50 mL×2)
  5. customdried
  6. customevaporated to dryness
  7. customThe crude product purified by flash chromatography (heptane→ethyl acetate:heptane 1:9)

Sources & evidence

ORD record
ord-0c0078cdfa374a9b97eccc2551e30aa0
Source dataset
uspto-grants-2011_05
Patent number
US07943669B2

Reaction notes

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