Triethylamine → [4-(3-Bromo-5-hydroxy-phenylsulfanyl)-2-chloro-phenoxy]-acetic Acid Ethyl Acetate

HRID 1969187Notes

Reaction equation

HRID 1969187 reaction equation
[CH2:1]([O:3][C:4](=[O:15])[CH2:5][O:6][C:7]1[CH:12]=[CH:11][C:10]([SH:13])=[CH:9][C:8]=1[Cl:14])[CH3:2].[Br:16][C:17]1[C:18](Br)=[C:19]([OH:23])[CH:20]=[CH:21][CH:22]=1.C(N(CC)CC)C>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CN1C(=O)CCC1>[CH2:1]([O:3][C:4](=[O:15])[CH3:5])[CH3:2].[Br:16][C:17]1[CH:22]=[C:21]([S:13][C:10]2[CH:11]=[CH:12][C:7]([O:6][CH2:5][C:4]([OH:3])=[O:15])=[C:8]([Cl:14])[CH:9]=2)[CH:20]=[C:19]([OH:23])[CH:18]=1

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 342642,3-DibromophenolHCID 57882838Ethyl (2-chloro-4-sulfanylphenoxy)acetate

Product 1

HCID 67024266[4-(3-Bromo-5-hydroxy-phenylsulfanyl)-2-chloro-phenoxy]-acetic Acid Ethyl Acetate

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
100 °C

Procedure

(2-Chloro-4-mercapto-phenoxy)-acetic acid ethyl ester (3 g; 12.16 mmol), dibromophenol (3.67 g; 14.59 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.45 g; 0.49 mmol), and 1,1′-bis-(diphenylphosphineo)ferrocenE (0.40 g; 0.73 mmol) were added to a dry reaction flask under an atmosphere of nitrogen. Triethylamine (6.74 mL, 48.64 mmol) and NMP (10 mL) were added, and the reaction mixture was stirred in a microwave oven for 1 h at 100° C. The reaction mixture was extracted with ethyl acetate, and the ethyl acetate phase was washed twice with a 5% aqueous citric acid solution. The organic phase was dried and evaporated in vacuo. The crude reaction product was purified by flash chromatography (dichloromethane→dichlormethane:ethyl acetate (1:1)). Yield 1.8 g. HPLC-MS: m/z: 441.2 (M+Na); Rt: 2.34 min.

Workup

  1. extractionThe reaction mixture was extracted with ethyl acetate
  2. washthe ethyl acetate phase was washed twice with a 5% aqueous citric acid solution
  3. customThe organic phase was dried
  4. customevaporated in vacuo
  5. customThe crude reaction product
  6. customwas purified by flash chromatography (dichloromethane→dichlormethane:ethyl acetate (1:1))

Sources & evidence

ORD record
ord-04e10d6cb8ff49739e0bb859451d2dbb
Source dataset
uspto-grants-2013_04
Patent number
US08426473B2

Reaction notes

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