Cesium carbonate → 5-(4-Methyl-1H-imidazol-1-yl)pyridin-2-amine

HRID 570349

Reaction equation

HRID 570349 reaction equation
C([O-])([O-])=O.[Cs+].[Cs+].[CH3:7][C:8]1[N:9]=[CH:10][NH:11][CH:12]=1.Br[C:14]1[CH:15]=[CH:16][C:17]([NH2:20])=[N:18][CH:19]=1>[Cu]I.CN(C=O)C>[CH3:7][C:8]1[N:9]=[CH:10][N:11]([C:14]2[CH:15]=[CH:16][C:17]([NH2:20])=[N:18][CH:19]=2)[CH:12]=1

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 706222-Amino-5-bromopyridineHCID 178418800HCID 178418800, compound

Product 1

HCID 575128615-(4-Methyl-1H-imidazol-1-yl)pyridin-2-amine

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6228DimethylformamideSolvent

Procedure

To a microwave tube with a magnetic stirring bar was charged CuI (382 mg, 2.0 mmol), Cs2CO3 (6.5 g, 20.0 mmol), 4-methyl-1H-imidazole (1.15 g, 14.0 mmol), 5-bromopyridin-2-amine (1.75 g, 10.0 mmol), and DMF (10 mL) under N2. The system was sealed and then evacuated twice and back filled with N2. The reaction mixture was stirred for 30 min at room temperature, and then heated at 120° C. for 48 h. The reaction mixture was then cooled to ambient temperature, diluted with 30 mL of ethyl acetate, washed with water. The combined organic layers were concentrated, and the resulting residue was purified by column chromatography on silica gel to provide 5-(4-methyl-1H-imidazol-1-yl)pyridin-2-amine (134). 1H NMR (400 MHz, d6-DMSO) δ 8.09 (m, 1H), 7.85 (d, J=1.6 Hz, 1H), 7.56 (dd, J=2.8, 8.8 Hz, 1H), 7.22 (t, J=1.2 Hz, 1H), 6.51 (dd, J=0.8, 8.8 Hz, 1H), 6.15 (s, 2H), 2.14 (d, J=1.2 Hz, 3H). MS m/z 175.1 (M+1)+.

Workup

  1. customThe system was sealed
  2. customevacuated twice
  3. additionback filled with N2
  4. temperatureheated at 120° C. for 48 h
  5. temperatureThe reaction mixture was then cooled to ambient temperature
  6. additiondiluted with 30 mL of ethyl acetate
  7. washwashed with water
  8. concentrationThe combined organic layers were concentrated
  9. customthe resulting residue was purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-d58bc5a7046d4eb493167f9895dbf349
Source dataset
uspto-grants-2015_05
Patent number
US09023839B2

Linked notes

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