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

HRID 235185Notes

Reaction equation

HRID 235185 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)palladium (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 washed 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)palladium (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. washthe filter cake was washed with ethyl acetate
  9. additionThe filtrate was diluted with ethyl acetate (300 ml)
  10. additionWater was added in portions
  11. washthe organic layer was washed with brine
  12. dry with materialdried over magnesium sulfate
  13. filtrationfiltered
  14. concentrationthe filtrate was concentrated
  15. customThe residue was chromatographed on silica gel
  16. washeluting with heptane to heptane
  17. customA portion (1.05 g) of the residue was rechromatographed
  18. washeluting with hexane
  19. customThe appropriate fractions were collected
  20. customevaporated

Sources & evidence

ORD record
ord-e6cac698ec964c44be5247b8f53f00e5
Source dataset
uspto-grants-1997_01
Patent number
US05597838

Reaction notes

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