Bromide ion → HCID 10778347, compound

HRID 495607Notes

Reaction equation

HRID 495607 reaction equation
Br[C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5](=[O:12])[C:4](=[O:13])[CH:3]=1.[Cl:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=1B(O)O.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C([O-])([O-])=O.[K+].[K+].[Br-]>C1COCC1.O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C(OCC)(=O)C>[Cl:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=1[C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5](=[O:12])[C:4](=[O:13])[CH:3]=1

Participants

10

Reactant 5

HCID 259Bromide ionHCID 11430Potassium CarbonateHCID 80271Tri-o-tolylphosphineHCID 27343222-Chlorophenylboronic acidHCID 12346155HCID 12346155, compound

Product 1

HCID 10778347HCID 10778347, compound

Reagents, catalysts & solvents 4

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 4-bromo-[1,2]naphthoquinone (350 mg, 1.48 mmol) in THF (20 mL) and H2O (5 mL) was added 2-chlorophenylboronic acid (231 mg. 1.48 mmol). followed by tri-o-tolylphosphine (45 mg, 148 μmol) and K2CO3 (614 mg, 4.44 mmol). The mixture was deoxygenated with bubbling N2 for about ten minutes, at which time the N3 line was removed and tris(dibenzylideneacetone)dipalladium(0) (68 mg, 74 μmol) was added. The resultant mixture was heated to reflux for 2 hours under N2, at which point no starting bromide was detectable by TLC (hexanes:ethyl acetate, 1:1, v/v). The mixture was cooled to room temperature and the THF evaporated under reduced pressure. The dried material was dissolved in ethyl acetate, washed sequentially with saturated aqueous ammonium chloride, H2O and brine, dried over Na2SO4, filtered, and evaporated under reduced pressure. The isolated material was chromatographed on silica gel (hexanes-ethyl acetate, 4:1, v/v) and dried to yield the product, 4-(2-chloro-phenyl)-[1,2]naphthoquinone, as an orange solid. 1H NMR (300 MHz, CDCl3) δ 8.21 (1H, dd, J=6.9, 2.1 Hz), 7.56-7.52 (3H, m), 7.48-7.44(2H, m), 7.44 (1H, m), 6.91 (1H, dd, J=2, 6 Hz), 6.39 (1H, s); HPLC: 7.45 min.

Workup

  1. customThe mixture was deoxygenated with bubbling N2 for about ten minutes, at which time the N3 line
  2. customwas removed
  3. customthe THF evaporated under reduced pressure
  4. dissolutionThe dried material was dissolved in ethyl acetate
  5. washwashed sequentially with saturated aqueous ammonium chloride, H2O and brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. customevaporated under reduced pressure
  9. customThe isolated material was chromatographed on silica gel (hexanes-ethyl acetate, 4:1
  10. customv/v) and dried

Sources & evidence

ORD record
ord-c160593f17fa439994b509f9af8840f1
Source dataset
uspto-grants-2005_09
Patent number
US06939896B2

Reaction notes

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