Cesium carbonate → 1-(3-Bromo-phenoxy)-4-chloro-2-phenoxy-benzene

HRID 1822250Notes

Reaction equation

HRID 1822250 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[C:4]([O:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH:3]=1.[Br:16][C:17]1[CH:22]=[CH:21][CH:20]=[C:19](I)[CH:18]=1.CC(C)(C(=O)CC(=O)C(C)(C)C)C.C(=O)([O-])[O-].[Cs+].[Cs+]>CN1C(=O)CCC1.[Cu]Cl>[Br:16][C:17]1[CH:18]=[C:19]([CH:20]=[CH:21][CH:22]=1)[O:8][C:5]1[CH:6]=[CH:7][C:2]([Cl:1])=[CH:3][C:4]=1[O:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 11561Benzene, 1-bromo-3-iodo-HCID 707002,2,6,6-Tetramethyl-3,5-heptanedioneHCID 127742954-Chloro-2-phenoxyphenol

Product 1

HCID 578942271-(3-Bromo-phenoxy)-4-chloro-2-phenoxy-benzeneYield 40.1%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 13387N-methyl-2-pyrrolidoneSolvent

Procedure

A solution of 4-chloro-2-phenoxy-phenol (1.65 g, 7.5 mmol), 1-bromo-3-iodobenzene (6.35 g, 22.4 mmol), copper(I) chloride (0.37 g, 3.74 mmol), 2,2,6,6-tetramethyl-3,5-heptanedione (0.345 g, 1.87 mmol), and cesium carbonate (2.93 g, 9 mmol) in NMP (20 mL) is heated to 120° C. The reaction is stirred overnight and cooled to rt. The reaction is quenched with 1N aqueous HCL and extracted with ethyl ether. The organic is washed with brine, dried over sodium sulfate, filtered, and the solvent is removed. The crude is purified by silica gel column chromatography using 5/1 hexanes/ethyl acetate to elute the pure product. The solvent is removed to afford 1.13 g (40%) of the desired product. 1H NMR (400 MHz, CDCl3); MS (ES+) m/z mass calculated for C18H12BrClO2 374, found 375 and 377 (M+1 and M+3, 100%).

Workup

  1. customThe reaction is quenched with 1N aqueous HCL
  2. extractionextracted with ethyl ether
  3. washThe organic is washed with brine
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. customthe solvent is removed
  7. customThe crude is purified by silica gel column chromatography
  8. washto elute the pure product
  9. customThe solvent is removed

Sources & evidence

ORD record
ord-1c85522644d042b78eaa5e86f3f6c207
Source dataset
uspto-grants-2009_10
Patent number
US07608639B2

Reaction notes

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