Phenylacetylene → [4-(3-hydroxy-5-phenylethynyl-phenylsulfanyl)-2-methyl-phenoxy]-acetic Acid Ethyl Ester

HRID 1969192Notes

Reaction equation

HRID 1969192 reaction equation
[CH2:1]([O:3][C:4](=[O:6])[CH3:5])[CH3:2].Br[C:8]1[CH:9]=[C:10]([S:15][C:16]2[CH:26]=[CH:25][C:19]([O:20]CC(O)=O)=[C:18]([CH3:27])[CH:17]=2)[CH:11]=[C:12]([OH:14])[CH:13]=1.[C:28]1([C:34]#[CH:35])[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1>C(N(CC)CC)C.CN(C=O)C.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.[Cu](I)I>[CH2:1]([O:3][C:4](=[O:6])[CH2:5][O:20][C:19]1[CH:25]=[CH:26][C:16]([S:15][C:10]2[CH:9]=[C:8]([C:35]#[C:34][C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=3)[CH:13]=[C:12]([OH:14])[CH:11]=2)=[CH:17][C:18]=1[CH3:27])[CH3:2]

Participants

7

Reactant 2

HCID 10821PhenylacetyleneHCID 67024264[4-(3-Bromo-5-hydroxy-phenylsulfanyl)-2-methyl-phenoxy]-acetic Acid Ethyl Acetate

Product 1

HCID 57791909[4-(3-hydroxy-5-phenylethynyl-phenylsulfanyl)-2-methyl-phenoxy]-acetic Acid Ethyl Ester

Reagents, catalysts & solvents 4

HCID 83717Copper iodideCatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 6228DimethylformamideSolventHCID 8471TriethylamineSolvent

Procedure

[4-(3-Bromo-5-hydroxy-phenylsulfanyl)-2-methyl-phenoxy]-acetic acid ethyl acetate (2.3 g; 5.79 mmol), phenylacetylene (1.9 mL; 17.4 mmol), bis(triphenylphosphine)palladium (II) chloride (0.33 g; 0.46 mmol) and copper iodide (0.07 g; 0.35 mmol) were dissolved in a mixture of triethylamine (7 mL) and DMF (8 mL) under an atmosphere of nitrogen. The reaction mixture was reacted in a microwave oven at 100° C. for 1 h. The reaction mixture was evaporated to dryness, and 5% aqueous citric acid and ethyl acetate was added. The organic phase was separated, dried and evaporated to dryness. The crude product was purified by flash chromatography (ethyl acetate:heptane 1:10→1:3). Yield: 1.2 g. HPLC-MS: m/z: 419 (M+); Rt: 2.52 min.

Workup

  1. customThe reaction mixture was reacted in a microwave oven at 100° C. for 1 h
  2. customThe reaction mixture was evaporated to dryness, and 5% aqueous citric acid and ethyl acetate
  3. additionwas added
  4. customThe organic phase was separated
  5. customdried
  6. customevaporated to dryness
  7. customThe crude product was purified by flash chromatography (ethyl acetate:heptane 1:10→1:3)

Sources & evidence

ORD record
ord-dd35925598c84c8281b9ade3316a7474
Source dataset
uspto-grants-2013_04
Patent number
US08426473B2

Reaction notes

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