Triphenylphosphine → HCID 67072065, compound

HRID 2246079Notes

Reaction equation

HRID 2246079 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[N:7]=[C:8](I)[S:9][CH:10]=1)=[O:5])[CH3:2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:31]([Si:33]([CH3:36])([CH3:35])[CH3:34])#[CH:32]>C(N(CC)CC)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:34][Si:33]([CH3:36])([CH3:35])[C:31]#[C:32][C:8]1[S:9][CH:10]=[C:6]([C:4]([O:3][CH2:1][CH3:2])=[O:5])[N:7]=1

Participants

6

Reactant 3

HCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 684727782-Iodo-thiazole-4-carboxylic acid ethyl ester

Product 1

HCID 67072065HCID 67072065, compound

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 8471TriethylamineSolvent

Conditions

Temperature
80 °C

Procedure

4-Ethoxycarbonyl-2-iodothiazole (6.39 g) was suspended in 60 ml of triethylamine, and 253 mg of palladium acetate and 592 mg of triphenylphosphine, and 6.37 ml of ethynyltrimethylsilane were added to the suspension under an argon atmosphere, followed by stirring at 80° C. for 2 hr. The reaction solution was concentrated under the reduced pressure, ethyl acetate and brine were added to the concentrate, and the mixture was adjusted to pH 3.0 by the addition of 1 N aqueous hydrochloric acid. The mixture was extracted twice with ethyl acetate and was washed with brine. The organic layer was dried over anhydrous magnesium sulfate, was filtered, and was concentrated under the reduced pressure. The residue was purified by column chromatography on silica gel (hexane:ethyl acetate=5:1) to give 3.97 g of 2-(2-trimethylsilylethynyl)-4-ethoxycarbonylthiazole. This compound was dissolved in 30 ml of methanol, and the solution was cooled in ice. Potassium carbonate (220 mg) was added to the cooled solution, and the mixture was stirred at room temperature for 30 min. Brine was added to the reaction solution, and the mixture was extracted twice with ethyl acetate and was washed with brine. The organic layer was dried over anhydrous magnesium sulfate, was filtered, and was concentrated under the reduced pressure to give 2.50 g of 2-ethynyl-4-methoxycarbonylthiazole.

Workup

  1. concentrationThe reaction solution was concentrated under the reduced pressure, ethyl acetate and brine
  2. additionwere added to the concentrate
  3. additionthe mixture was adjusted to pH 3.0 by the addition of 1 N aqueous hydrochloric acid
  4. extractionThe mixture was extracted twice with ethyl acetate
  5. washwas washed with brine
  6. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  7. filtrationwas filtered
  8. concentrationwas concentrated under the reduced pressure
  9. customThe residue was purified by column chromatography on silica gel (hexane:ethyl acetate=5:1)

Sources & evidence

ORD record
ord-32b1e535903b4e3396fbf2f2ff442f03
Source dataset
uspto-grants-2010_03
Patent number
US07687490B2

Reaction notes

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