Triethylamine → 4-(1-Dodecynyl)-2-thiazolecarboxaldehyde

HRID 1734814Notes

Reaction equation

HRID 1734814 reaction equation
Br[C:2]1[N:3]=[C:4]([CH:7]=[O:8])[S:5][CH:6]=1.[CH:9]#[C:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20].C(N(CC)CC)C>O1CCCC1>[C:9]([C:2]1[N:3]=[C:4]([CH:7]=[O:8])[S:5][CH:6]=1)#[C:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 698211-DodecyneHCID 27631874-Bromothiazole-2-carboxaldehyde

Product 1

HCID 183729404-(1-Dodecynyl)-2-thiazolecarboxaldehydeYield 76.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of 4-bromo-2-thiazolecarboxaldehyde (14.8 g), 1-dodecyne (14.1 g), and triethylamine (23.5 g) in dry tetrahydrofuran (85 m) was chilled to 5° C. and degassed under nitrogen. bis(Triphenylphosphine)paIladium (II) chloride (0.54 g) and copper (I) iodide (0.07 g) were added to the mixture, which was degassed, and stirred, under nitrogen, at room temperature for 2.5 hrs. The reaction mixture was heated at 40° C. for 7 hrs, during which time additional amounts of 1-dodecyne (3.9 g), bis(triphenylphosphine)palladium (II) chloride (0.11 g), and copper (I) iodide (0.02 g) were added. The mixture was cooled to room temperature, the precipitate was collected, and the filter cake was wasted with ethyl acetate. The filtrate was diluted with ethyl acetate (300 ml). Water was added in portions, and the organic layer was washed with brine, dried over magnesium sulfate, filtered, and the filtrate was concentrated. The residue was chromatographed on silica gel, eluting with heptane to heptane: 1% ethyl acetate. A portion (1.05 g) of the residue was rechromatographed, eluting with hexane:(0.3 to 1%) ethyl acetate. The appropriate fractions were collected and evaporated to yield 0.79 g (76.5% yield) of product, mp 25.5°-26° C.

Workup

  1. customdegassed under nitrogen
  2. additionbis(Triphenylphosphine)paIladium (II) chloride (0.54 g) and copper (I) iodide (0.07 g) were added to the mixture, which
  3. customwas degassed
  4. temperatureThe reaction mixture was heated at 40° C. for 7 hrs, during which time additional amounts of 1-dodecyne (3.9 g), bis(triphenylphosphine)palladium (II) chloride (0.11 g), and copper (I) iodide (0.02 g)
  5. additionwere added
  6. temperatureThe mixture was cooled to room temperature
  7. customthe precipitate was collected
  8. additionThe filtrate was diluted with ethyl acetate (300 ml)
  9. additionWater was added in portions
  10. washthe organic layer was washed with brine
  11. dry with materialdried over magnesium sulfate
  12. filtrationfiltered
  13. concentrationthe filtrate was concentrated
  14. customThe residue was chromatographed on silica gel
  15. washeluting with heptane to heptane
  16. customA portion (1.05 g) of the residue was rechromatographed
  17. washeluting with hexane
  18. customThe appropriate fractions were collected
  19. customevaporated

Sources & evidence

ORD record
ord-b89b233de8174dd79f34bd8abb6f2cc2
Source dataset
uspto-grants-1996_07
Patent number
US05534636

Reaction notes

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