Bromine → 3'-Bromo-4'-methyl-1,1'-biphenyl-2-carbonitrile

HRID 1591498Notes

Reaction equation

HRID 1591498 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:9]([C:14]#[N:15])=[CH:10][CH:11]=[CH:12][CH:13]=2)=[CH:4][CH:3]=1.[Br:16]Br>C(Cl)Cl.FC(F)(F)C([O-])=O.[Ag+]>[Br:16][C:7]1[CH:6]=[C:5]([C:8]2[C:9]([C:14]#[N:15])=[CH:10][CH:11]=[CH:12][CH:13]=2)[CH:4]=[CH:3][C:2]=1[CH3:1]

Participants

5

Reactant 2

HCID 24408BromineHCID 1455122-Cyano-4'-methylbiphenyl

Product 1

HCID 218403383'-Bromo-4'-methyl-1,1'-biphenyl-2-carbonitrileYield 41%

Reagents, catalysts & solvents 2

HCID 76299Silver trifluoroacetateCatalyst2×HCID 6344DichloromethaneSolvent

Procedure

A solution of 5.2 g (27 mmol) of 4'-methyl-1,1'-biphenyl-2-nitrile (Example 69, Step B) in 60 mL of methylene chloride at 0° C. was treated with 6.7 g of silver trifluoroacetate (30 mmol). When all the silver trifluoroacetate was dissolved, 1.6 mL of bromine was added dropwise (4.95 g, 31 mmol) with vigorous stirring. After two hours, the reaction mixture was filtered and the solid washed with methylene chloride. The combined organic layers were washed once with dilute (<1N) aqueous sodium hydroxide and once with brine. The organic layer was removed, dried over magnesium sulfate, filtered and concentrated under vacuum. The residue was purified by preparative high pressure liquid chromatography on silica, eluting with 10% ether/hexane to give 3 g (41%) of product. 1H NMR (200 MHz,CDCl3): 2.46 (s,3H), 7.2-7.8 (m,7H).

Workup

  1. filtrationthe reaction mixture was filtered
  2. washthe solid washed with methylene chloride
  3. washThe combined organic layers were washed once
  4. additionwith dilute (<1N) aqueous sodium hydroxide
  5. customThe organic layer was removed
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under vacuum
  9. customThe residue was purified by preparative high pressure liquid chromatography on silica
  10. washeluting with 10% ether/hexane

Sources & evidence

ORD record
ord-bdbd54521e7447a18c875fa64cf6d5ba
Source dataset
uspto-grants-1993_04
Patent number
US05206235

Reaction notes

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