Bromine → 5-Bromo-1,3-difluoro-2-(methylsulfanyl)benzene

HRID 732809Notes

Reaction equation

HRID 732809 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([F:8])[C:3]=1[S:9][CH3:10].[Br:11]Br.[Cl-].[Al+3].[Cl-].[Cl-].S([O-])([O-])(=O)=S.[Na+].[Na+]>[Fe].C(OCC)C.ClCCl>[Br:11][C:6]1[CH:7]=[C:2]([F:1])[C:3]([S:9][CH3:10])=[C:4]([F:8])[CH:5]=1

Participants

8

Reactant 4

HCID 24408BromineHCID 24477Sodium ThiosulfateHCID 6451240Aluminum(III) ChlorideHCID 132502621,3-Difluoro-2-(methylsulfanyl)benzene

Product 1

HCID 235966125-Bromo-1,3-difluoro-2-(methylsulfanyl)benzeneYield 17%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent

Procedure

Combine 1,3-difluoro-2-methylsulfanyl-benzene (4.3 g, 27 mmol), iron (300 mg, 5.4 mmol), bromine (1.4 mL, 27 mmol), aluminium chloride (400 mg, 3.0 mmol) and dichloromethane (100 mL), at 0° C. Stir the reaction mixture at room temperature for 2 hours. Add saturated sodium thiosulfate solution (20 mL) and diethyl ether (100 mL). Separate the layers and wash the organic layer with brine (20 mL). Dry with MgSO4, filter and concentrate in vacuo. Chromatograph the residue on a column eluting the material with diethyl ether in hexane (0 to 5%) to give 1.1 g of 5-bromo-1,3-difluoro-2-methylsulfanyl-benzene (17%).

Workup

  1. customat 0° C
  2. customSeparate the layers
  3. washwash the organic layer with brine (20 mL)
  4. dry with materialDry with MgSO4
  5. filtrationfilter
  6. concentrationconcentrate in vacuo
  7. washChromatograph the residue on a column eluting the material with diethyl ether in hexane (0 to 5%)

Sources & evidence

ORD record
ord-26601702e79c46caac2d00bb9b4862b2
Source dataset
uspto-grants-2009_09
Patent number
US07585977B2

Reaction notes

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