Cesium carbonate → Methyl 3-(3-bromo-4-phenoxyphenyl)propionate

HRID 2378536Notes

Reaction equation

HRID 2378536 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH2:9][CH2:10][C:11]([O:13][CH3:14])=[O:12])[CH:5]=[CH:6][C:7]=1[OH:8].C(=O)([O-])[O-].[Cs+].[Cs+].I[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1.C(CC(=O)C(C)(C)C)(=O)C(C)(C)C>CN1CCCC1=O.[Cu]Cl.COC(C)(C)C>[Br:1][C:2]1[CH:3]=[C:4]([CH2:9][CH2:10][C:11]([O:13][CH3:14])=[O:12])[CH:5]=[CH:6][C:7]=1[O:8][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 11575IodobenzeneHCID 707002,2,6,6-Tetramethyl-3,5-heptanedioneHCID 22558720Methyl 3-(3-bromo-4-hydroxyphenyl)propanoate

Product 1

HCID 68742079Methyl 3-(3-bromo-4-phenoxyphenyl)propionate

Reagents, catalysts & solvents 3

HCID 62652Cuprous chlorideCatalystHCID 13387N-methyl-2-pyrrolidoneSolventHCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
120 °C

Procedure

A solution of Intermediate 5 (3.08 g) in anhydrous N-methylpyrrolidone (9.5 ml, WAKO) was successively added with cesium carbonate (3.58 g, WAKO), iodobenzene (1.4 ml, TCI), dipivaloylmethane (0.12 ml, TCI) and copper(I) chloride (275 mg, WAKO), and stirred 120° C. for 16 hours under argon gas atmosphere. The reaction mixture was added with t-butyl methyl ether (25 ml), and insoluble solids were removed by filtration. The filtrate was washed successively with 2 N aqueous hydrochloric acid and saturated brine and dried, and then the solvent was evaporated under reduced pressure. The residue was purified by flash column chromatography (hexane:ethyl acetate=1:10) to obtain the title compound (Compound No. A-31, 1.00 g).

Workup

  1. customwere removed by filtration
  2. washThe filtrate was washed successively with 2 N aqueous hydrochloric acid and saturated brine
  3. customdried
  4. customthe solvent was evaporated under reduced pressure
  5. customThe residue was purified by flash column chromatography (hexane:ethyl acetate=1:10)

Sources & evidence

ORD record
ord-1766ff505ee64f6e8e9af941fc52e333
Source dataset
uspto-grants-2008_12
Patent number
US07470807B2

Reaction notes

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