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

HRID 2170596Notes

Reaction equation

HRID 2170596 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>O1CCOCC1.[Cu]I.O.C(OCC)(=O)C>[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

9

Reactant 4

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

Product 1

HCID 8705202-(3-Bromophenyl)benzoxazoleYield 76.3%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of 3-bromobenzoyl chloride (10.0 g, 45.6 mmol), 2-bromoaniline (7.91 g, 46 mmol), Cs2CO3 (30 g, 92 mmol), CuI (0.437 g, 2.3 mmol) and 1,10-phenanthroline (0.829 g, 4.6 mmol) in anhydrous 1,4-dioxane (110 ml) was heated at 120° C. for 8 h. After cooling to RT, the mixture was poured into ethyl acetate (300 ml), worked up with water (250 ml). The aqueous solution was extracted with dichloromethane (300 ml). The organic phase was collected, combined, and dried over Na2SO4. Purification by a short silica gel column (hexanes/ethyl acetate 3:1) gave a solid which was washed with hexanes to give a light yellow solid 1 (9.54 g, 76% yield).

Workup

  1. temperatureAfter cooling to RT
  2. extractionThe aqueous solution was extracted with dichloromethane (300 ml)
  3. customThe organic phase was collected
  4. dry with materialdried over Na2SO4
  5. customPurification by a short silica gel column (hexanes/ethyl acetate 3:1)
  6. customgave a solid which
  7. washwas washed with hexanes

Sources & evidence

ORD record
ord-716d9ebe65074cc0a5264433d5991cdb
Source dataset
uspto-grants-2015_06
Patent number
US09051284B2

Reaction notes

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