1,10-Phenanthroline → HCID 25239477, compound

HRID 2170601Notes

Reaction equation

HRID 2170601 reaction equation
[Br:1][C:2]1[CH:3]=[N:4][CH:5]=[C:6]([CH:10]=1)[C:7](Cl)=[O:8].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:10]=[C:6]([C:7]2[O:8][C:12]3[CH:18]=[CH:17][CH:16]=[CH:15][C:13]=3[N:14]=2)[CH:5]=[N:4][CH:3]=1

Participants

7

Reactant 4

HCID 13181,10-PhenanthrolineHCID 10796Cesium carbonateHCID 119922-BromoanilineHCID 27812235-Bromonicotinoyl chloride

Product 1

HCID 25239477HCID 25239477, compoundYield 46%

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 5-bromonicotinoyl chloride (13.46 g, 61.04 mmol), 2-bromoaniline (10.00 g, 58.13 mmol), Cs2CO3 (37.88 g, 116.3 mmol), CuI (0.554 g, 2.907 mmol), 1,10-phenanthroline (1.048 g, 5.813 mmol) and anhydrous 1,4-dioxane (110 mL) was degassed with argon for 1 h while stirring. The reaction mixture was then maintained under argon at 120° C. while stirring until TLC (SiO2, 1:1 hexanes-dichloromethane) confirmed consumption of the starting material (48 h). Upon cooling to RT, dichloromethane (ca. 200 mL) was added to the reaction, the mixture filtered, the filtrant washed copiously with dichloromethane (ca. 200 mL) and ethyl acetate (ca. 200 mL) and the filtrate concentrated in vacuo. Purification of the crude product via flash chromatography (SiO2, 100% dichloromethane to 29:1-dichloromethane:acetone) afforded 2-(5-bromopyridin-3-yl)benzo[d]oxazole (7.32 g, 46%) as a light brown crystalline solid.

Workup

  1. customwas degassed with argon for 1 h
  2. stirringwhile stirring until TLC (SiO2, 1:1 hexanes-dichloromethane)
  3. customconsumption of the starting material (48 h)
  4. temperatureUpon cooling to RT
  5. additiondichloromethane (ca. 200 mL) was added to the reaction
  6. filtrationthe mixture filtered
  7. washthe filtrant washed copiously with dichloromethane (ca. 200 mL) and ethyl acetate (ca. 200 mL)
  8. concentrationthe filtrate concentrated in vacuo
  9. customPurification of the crude product via flash chromatography (SiO2, 100% dichloromethane to 29:1-dichloromethane:acetone)

Sources & evidence

ORD record
ord-fd86f32f8dd546d1a2b9f80e56b2dab4
Source dataset
uspto-grants-2015_06
Patent number
US09051284B2

Reaction notes

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