Hexane → HCID 11735574, compound

HRID 967745Notes

Reaction equation

HRID 967745 reaction equation
Br[C:2]1[S:3][CH:4]=[CH:5][N:6]=1.C(N(CC)CC)C.[C:14]1([C:20]#[CH:21])[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.CCCCCC>COCCOC.C(OCC)(=O)C.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[C:14]1([C:20]#[C:21][C:2]2[S:3][CH:4]=[CH:5][N:6]=2)[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Participants

9

Reactant 4

HCID 8058HexaneHCID 8471TriethylamineHCID 10821PhenylacetyleneHCID 764302-Bromothiazole2×

Product 1

HCID 11735574HCID 11735574, compoundYield 60%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 80711,2-DimethoxyethaneSolvent2×HCID 8857Ethyl AcetateSolvent2×

Procedure

2-Bromo-1,3-thiazole (2.0 g, 12 mmol) and CuI (460 mg, 2.4 mmol) were combined in DME (40 mL), and argon gas was bubbled through the suspension for several minutes to deoxygenate the mixture. Triethylamine (8.6 mL, 62 mmol) and PdCl2(PPh3)2 (856 mg, 1.22 mmol) were added and then phenylacetylene (3.7g, 36.5 mmol) was added dropwise. The reaction was heated to reflux at which point the reaction mixture solidified. Additional DME (20 mL) was added to dissolve the solids and the reaction mixture was allowed to stir for 16 h at reflux, at which time GC/MS showed no remaining 2-bromothiazole. After cooling, the mixture was diluted with 200 mL ethyl acetate, and filtered through Celite™. The pad was then washed thoroughly with ethyl acetate and the combined filtrates were washed with water (200 mL), brine (200 mL), dried over Na2SO4, and filtered. The filtrate was concentrated in vacuo, and the residue was purified by column chromatography eluting with hexane, then 97:3 hexane:ethyl acetate) to afford 2-(phenylethynyl)-1,3-thiazole (1.3 g, 60% yield) as a yellowish oil. 1H NMR (CDCl3, 300 MHz) δ 7.86 (d, J=3.2 Hz, 1H), 7.61–7.57 (m, 2H), 7.42–7.26 (m, 4H). MS (ESI) 185.2 (M+).

Workup

  1. customargon gas was bubbled through the suspension for several minutes
  2. customto deoxygenate the mixture
  3. temperatureThe reaction was heated
  4. temperatureto reflux at which
  5. dissolutionto dissolve the solids
  6. temperatureat reflux, at which time GC/MS
  7. temperatureAfter cooling
  8. filtrationfiltered through Celite™
  9. washThe pad was then washed thoroughly with ethyl acetate
  10. washthe combined filtrates were washed with water (200 mL), brine (200 mL)
  11. dry with materialdried over Na2SO4
  12. filtrationfiltered
  13. concentrationThe filtrate was concentrated in vacuo
  14. customthe residue was purified by column chromatography
  15. washeluting with hexane

Sources & evidence

ORD record
ord-104e6660a41a4fa1abfa62f34862f442
Source dataset
uspto-grants-2005_10
Patent number
US06956049B1

Reaction notes

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