1,10-Phenanthroline → 4-Pyridinamine, 5-methoxy-2-phenyl-

HRID 917459Notes

Reaction equation

HRID 917459 reaction equation
I[C:2]1[C:3]([NH2:14])=[CH:4][C:5]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)=[N:6][CH:7]=1.N1C2C(=CC=C3C=2N=CC=C3)C=CC=1.[C:29](=O)([O-])[O-:30].[Cs+].[Cs+]>CO.[Cu]I>[CH3:29][O:30][C:2]1[C:3]([NH2:14])=[CH:4][C:5]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)=[N:6][CH:7]=1

Participants

6

Reactant 3

HCID 13181,10-PhenanthrolineHCID 10796Cesium carbonateHCID 534263614-Amino-5-iodo-2-phenylpyridine

Product 1

HCID 451164384-Pyridinamine, 5-methoxy-2-phenyl-Yield 45%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 887MethanolSolvent

Conditions

Temperature
130 °C

Procedure

A stirred suspension of 6.20 g (20.9 mmol) 5-iodo-2-phenyl-pyridin-4-ylamine, 319 mg (1.68 mmol) copper(I) iodide, 453 mg (2.51 mmol) 1,10-phenanthroline and 13.6 g (41.9 mmol) cesium carbonate in 40 ml methanol was heated at 130° C. for 20 min in a microwave oven. The resulting mixture was then cooled to room temperature and concentrated in vacuo. The residue was resuspended in 500 ml dichloromethane and extracted three times with 200 ml portions of 1 M aq. hydrochloric acid. The combined acid extracts were then made basic by addition of 5 N aq. sodium hydroxide solution and extracted three times with dichloromethane. The combined organic phases were dried over sodium sulfate and concentrated in vacuo. Flash chromatography (methanol/dichloromethane 3/97-5/95) afforded 1.87 g (45%) 5-methoxy-2-phenyl-pyridin-4-ylamine as a dark red oil. ES-MS m/e (%): 201 (M+H+, 100).

Workup

  1. temperatureThe resulting mixture was then cooled to room temperature
  2. concentrationconcentrated in vacuo
  3. extractionextracted three times with 200 ml portions of 1 M aq. hydrochloric acid
  4. additionThe combined acid extracts were then made basic by addition of 5 N aq. sodium hydroxide solution
  5. extractionextracted three times with dichloromethane
  6. dry with materialThe combined organic phases were dried over sodium sulfate
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-7baf200770214701aac515f959b1517f
Source dataset
uspto-grants-2007_09
Patent number
US07273865B2

Reaction notes

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