Alkynyl thiofuran compound and its prepn and application
A technology of alkynyl thiophene and compounds, which is applied in the field of alkynyl thiophene compounds, and can solve problems such as failure to promote application, limited application value, and low activity
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Embodiment 1
[0051] Embodiment 1: the preparation of 2,5-bis (thiophen-2-ylethynyl) thiophene
[0052] Weigh 10.8g (0.1mol) of 2-ethynylthiophene and 12.1g (0.05mol) of 2,5-dibromothiophene, add 100ml of anhydrous diethylamine, stir under nitrogen protection, add 0.0325g (0.0001mol) of palladium acetate ), cuprous iodide 0.038g (0.0002mol) and triphenylphosphine 0.0786g (0.0003mol). Heated and refluxed for 4h, a large amount of salt was produced. Cool to room temperature, filter, and wash the residual solid with benzene; combine the filtered solution, distill off the solvent under reduced pressure, and recrystallize with ethanol to obtain 13.26 g of 2,5-bis(thiophen-2-ylethynyl) in light yellow flaky crystals Thiophene has a melting point of 113.8-114.3°C. 1 HNMR (500MHz): δ7.3410(d, J=5.05Hz, 2H, thiophene-H), 7.3135(d, J=3.45Hz, 2H, thiophene-H), 7.305(d, J=8.8Hz, 2H, thiophene-H), 7.1578 (s, 2H, thiophene-H). 13 C NMR: δ85.84, 87.51, 122.65, 124.65, 127.24, 128.04, 131.99, 13253. EI...
Embodiment 2
[0053] Embodiment 2: the preparation of 2,5-diphenylethynylthiophene
[0054] -40℃, 16gNaNH 2 Add to 200mL liquid ammonia, add 20.4kg of phenylacetylene, pass through N2 protection, add 24.2g of dibromothiophene in ether solution, stir, heat up to -30°C, stop stirring after 1h, let stand overnight, add NH 4 Cl, heat up to recover ammonia, filter, wash with ether, remove ether, and dry to obtain a yellow solid, recrystallized from ethanol, 22.5 g of light yellow flake solid, yield 80%. mp 75.8-76.7°C. 1 H NMR (500MHz): δ7.1539 (s, 2H, thiophene-H), 7.32-7.53 (m, 10H, Ph-H). 13 C NMR: δ82.34, 94.12, 122.73, 124.78, 128.44, 128.69, 131.55, 131.83. EIMS m / z (%): 284 (M + , 100), 158(3), 142.05(21).
[0055] To synthesize asymmetric 2,5-diynylthiophenes, the reaction formula is as follows:
[0056]
Embodiment 3
[0057] Example 3: Preparation of 2-pyridine-3-ethynyl-5-p-methoxyphenylethynylthiophene:
[0058] Weigh 10g (0.097mol) of m-ethynylpyridine and 24.2g (0.1mol) of 2,5-dibromothiophene, add 100ml of anhydrous triethylamine, stir under nitrogen protection, add 0.065g (0.0002mol) of palladium acetate, Cuprous iodide 0.076g (0.0004mol) and triphenylphosphine 0.1572g (0.0006mol). Heated and refluxed for 4h, a large amount of salt was produced. Cool to room temperature, filter, and wash the residual solid with benzene; combine the filtered solution, and distill off the solvent under reduced pressure to obtain 21 g of 1-pyridin-3-yl-2-(5-bromothiophen-2-yl)acetylene with a melting point of 128°C.
[0059] Weigh 6.6g (0.05mol) of p-methoxyphenylacetylene and 13.2g (0.05mol) of 1-pyridin-3-yl-2-(5-bromothiophen-2-yl)acetylene, and add 100ml of anhydrous triethylamine , stirred under the protection of nitrogen, and added 0.0325 g (0.0001 mol) of palladium acetate, 0.038 g (0.0002 mol)...
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