Nitrogen → 1-(6-Bromo-4-chloro-5-methylbiphenyl-2-yl)ethanone

HRID 510855Notes

Reaction equation

HRID 510855 reaction equation
FC(F)(F)S(O[C:7]1[C:12]([C:13](=[O:15])[CH3:14])=[CH:11][C:10]([Cl:16])=[C:9]([CH3:17])[C:8]=1[Br:18])(=O)=O.[C:21]1(B(O)O)[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.N#N>C1(C)C=CC=CC=1.C(=O)(O)[O-].[Na+].O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Br:18][C:8]1[C:7]([C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)=[C:12]([C:13](=[O:15])[CH3:14])[CH:11]=[C:10]([Cl:16])[C:9]=1[CH3:17]

Participants

8

Reactant 3

HCID 947NitrogenHCID 66827Phenylboronic AcidHCID 866667866-Acetyl-2-bromo-4-chloro-3-methylphenyl trifluoromethanesulfonate

Product 1

HCID 866667871-(6-Bromo-4-chloro-5-methylbiphenyl-2-yl)ethanoneYield 93.1%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 516892Sodium BicarbonateSolvent

Conditions

Temperature
80 °C

Procedure

A biphasic solution of 6-acetyl-2-bromo-4-chloro-3-methylphenyl trifluoromethanesulfonate (3.3 g, 8.3 mmol) and phenylboronic acid (1.2 g, 10 mmol) in toluene (30 mL) and saturated sodium bicarbonate in water (30 mL) was bubbled with N2 to degas. After tetrakis(triphenylphosphine)palladium(0) (0.385 g, 0.333 mmol) was added, the mixture was bubbled with N2 for 5 min. more and heated at 80° C. for 2 hours. After cooling to r.t., the mixture was diluted with ethyl acetate. The layers were separated and the aq. layer was extracted with more ethyl acetate. The combined extracts were washed with brine, dried over Na2SO4, filtered, and concentrated. The residue was purified on silica gel column, eluting with 0-20% of ethyl acetate in hexane, to give the desired product (2.5 g, 93%). LCMS calculated for C15H13BrClO (M+H)+: m/z=323.0. found: 323.0.

Workup

  1. customto degas
  2. customthe mixture was bubbled with N2 for 5 min. more
  3. temperatureAfter cooling to r.t.
  4. additionthe mixture was diluted with ethyl acetate
  5. customThe layers were separated
  6. extractionthe aq. layer was extracted with more ethyl acetate
  7. washThe combined extracts were washed with brine
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe residue was purified on silica gel column
  12. washeluting with 0-20% of ethyl acetate in hexane

Sources & evidence

ORD record
ord-7a08fc72b71d4260ab77c88d1f5e3a76
Source dataset
uspto-grants-2015_08
Patent number
US09096600B2

Reaction notes

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