Cesium carbonate → HCID 59560028, compound

HRID 1177275Notes

Reaction equation

HRID 1177275 reaction equation
[OH:1][C:2]1[C:7]2[CH:8]=[C:9]([CH3:11])[O:10][C:6]=2[CH:5]=[C:4]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH:3]=1.Br[C:18]1[CH:23]=[CH:22][C:21]([S:24]([CH3:27])(=[O:26])=[O:25])=[CH:20][N:19]=1.C([O-])([O-])=O.[Cs+].[Cs+]>CN(C=O)C.[Cu]I>[CH3:11][C:9]1[O:10][C:6]2[CH:5]=[C:4]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH:3]=[C:2]([O:1][C:18]3[CH:23]=[CH:22][C:21]([S:24]([CH3:27])(=[O:26])=[O:25])=[CH:20][N:19]=3)[C:7]=2[CH:8]=1

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 98994832-Bromo-5-(methylsulfonyl)pyridineHCID 11514065Ethyl 4-hydroxy-2-methylbenzofuran-6-carboxylate

Product 1

HCID 59560028HCID 59560028, compoundYield 97.4%

Reagents, catalysts & solvents 2

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

Conditions

Temperature
100 °C

Procedure

A mixture of ethyl 4-hydroxy-2-methyl-1-benzofuran-6-carboxylate (500 mg, 2.27 mmol), 2-bromo-5-methanesulfonyl pyridine (590 mg, 2.57 mmol), Cs2CO3 (1.1 g, 4.12 mmol) and CuI (100 mg, 1 mmol) in DMF (20 mL) was heated to 100° C. for 4 hours. The solvent was removed under reduced pressure. The residue was poured into water (20 mL) and extracted with EtOAc (50 mL×2). The combined organic layer was washed with brine (20 mL×2), dried over Na2SO4 and concentrated. The product was purified via gradient silica gel chromatography on silica gel using EtOAc/Hex (10/90 to 30/70) to afford the title compound (830 mg, 88%) as a white solid. 1H NMR (300 MHz, CHLOROFORM-d) δ ppm 1.42 (t, J=7.16 Hz, 3 H) 2.48 (s, 3 H) 3.01-3.19 (m, 3 H) 4.41 (q, J=7.16 Hz, 2 H) 6.23 (d, J=0.94 Hz, 1 H) 7.02-7.18 (m, 2 H) 7.64 (d, J=1.13 Hz, 1 H) 7.85-7.96 (m, 1 H) 8.02-8.10 (m, 1 H); (ESI, pos): 376.

Workup

  1. customThe solvent was removed under reduced pressure
  2. additionThe residue was poured into water (20 mL)
  3. extractionextracted with EtOAc (50 mL×2)
  4. washThe combined organic layer was washed with brine (20 mL×2)
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated
  7. customThe product was purified via gradient silica gel chromatography on silica gel

Sources & evidence

ORD record
ord-801b68dddd25488689f48b7080f40475
Source dataset
uspto-grants-2010_11
Patent number
US07842713B2

Reaction notes

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