1,10-Phenanthroline → 2-(3-Bromophenyl)benzoxazole

HRID 2170602Notes

Reaction equation

HRID 2170602 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][CH:10]=1)[C:5](Cl)=[O:6].Br[C:12]1[CH:18]=[CH:17][CH:16]=[CH:15][C:13]=1[NH2:14].C([O-])([O-])=O.[Cs+].[Cs+].N1C2C(=CC=C3C=2N=CC=C3)C=CC=1>[Cu]I.O1CCOCC1>[Br:1][C:2]1[CH:3]=[C:4]([C:5]2[O:6][C:12]3[CH:18]=[CH:17][CH:16]=[CH:15][C:13]=3[N:14]=2)[CH:8]=[CH:9][CH:10]=1

Participants

7

Reactant 4

HCID 13181,10-PhenanthrolineHCID 10796Cesium carbonateHCID 119922-BromoanilineHCID 74377Benzoyl chloride, 3-bromo-

Product 1

HCID 8705202-(3-Bromophenyl)benzoxazoleYield 100%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of 3-bromobenzoyl chloride (6.005 g, 27.36 mmol), 2-bromoaniline (4.707 g, 27.36 mmol), Cs2CO3 (17.83 g, 54.73 mmol), CuI (0.261 g, 1.37 mmol), 1,10-phenanthroline (0.493 g, 2.74 mmol) and anhydrous 1,4-dioxane (50 mL) was degassed with argon at 40° C. for 30 min while stirring. The reaction mixture was then maintained under argon at 120° C. while stirring until TLC (SiO2, 4:1 hexanes-ethyl acetate) confirmed consumption of the starting material (24 h). Upon cooling to RT, the mixture was filtered and the filtrant washed copiously with ethyl acetate (ca. 350 mL). The filtrate was then washed with sat. NaHCO3, H2O and brine, dried over MgSO4, filter and concentrated in vacuo. Purification of the crude product via flash chromatography (SiO2, 4:1-hexanes:ethyl acetate) afforded 2-(3-bromophenyl)benzo[d]oxazole (7.50 g, 100%) as an off-white solid.

Workup

  1. customwas degassed with argon at 40° C. for 30 min
  2. stirringwhile stirring until TLC (SiO2, 4:1 hexanes-ethyl acetate)
  3. customconsumption of the starting material (24 h)
  4. temperatureUpon cooling to RT
  5. filtrationthe mixture was filtered
  6. washthe filtrant washed copiously with ethyl acetate (ca. 350 mL)
  7. washThe filtrate was then washed with sat. NaHCO3, H2O and brine
  8. dry with materialdried over MgSO4
  9. filtrationfilter
  10. concentrationconcentrated in vacuo
  11. customPurification of the crude product via flash chromatography (SiO2, 4:1-hexanes:ethyl acetate)

Sources & evidence

ORD record
ord-40eeae8cc7ee4c2b9c8cc49a4cfbd4d1
Source dataset
uspto-grants-2015_06
Patent number
US09051284B2

Reaction notes

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