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With tetrabutyl ammonium fluoride In tetrahydrofuran; chloroform at -30 - 50℃; for 20h; Cooling with liquid nitrogen-acetone bath; |
2.2
2) Synthesis of tetrakis(4-ethynylphenyl)porphyrin (TEPP) (2) A solution of 700 mg (0.7 mmol) of protected TEPP (1) obtained above in 500 ml of a chloroform/tetrahydrofuran (THF) mixture (1/1 v/v) was cooled in a bath of liquid nitrogen and acetone to a temperature of between -30 and -50° C., and then a 1 mol/l solution of tetrabutylammonium fluoride (TBAF) in THF (259 mg, 0.99 mmol in 1 ml) was added to the reaction mixture, which was subsequently stirred for 20 hours. The rise in temperature was not controlled. The solvent was subsequently evaporated off and the deprotected porphyrin (2) was obtained in the form of a purple powder (747 mg, 1.05 mmol). |
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With tetrabutyl ammonium fluoride In tetrahydrofuran at -78℃; for 1.5h; Inert atmosphere; |
Preparation of 5,10,15,20-tetra(4-ethynylphenyl)porphyrin monomer reactant
4.63g (5mmol) p-bromobenzaldehyde was added to the tetrahydrofuran and triethylamine mixed solution (3: 1, v / v), Stirred vigorously for 30 minutes under nitrogen protection. Afterwards, add 190mg(1.0mmol) cuprous iodide and 350mg bistriphenylphosphine palladium dichloride(0.5mmol). After 10 minutes, slowly add dropwise over 1 hour 3.7mL (26.3mmol) of trimethylsilyl acetylene. React for 3 hours. After completion of the reaction, diluted with ethylacetate, washed three times with saturated brine, then dried over anhydrousmagnesium sulfate. Spin-dry product after the oily solvent, and then purifiedby a silica gel column, eluent used petroleum ether: ethyl acetate = 20: 1 togive the pure compound 4-trimethylsilyl ethynylbenzaldehyde. 752 mg 4-trimethylsilyl ethynylbenzaldehyde dissolved in 100mL of chloroform, stirred under nitrogen for 30 minutes uniformly. By using a pipette, 275mg pyrrole was added, then add 116μL boron trifluoride etherate. At room temperature react for1.5 ~ 2 hours, until the 4-trimethylsilyl ethynylbenzaldehyde reacted completely.After addition of 0.64g2,3- dichloro-5,6-dicyano-1,4-benzoquinone and reacting for0.5 hours, the reaction was added 126μL of triethylamine and reacted for 10 minutes.The reaction solution was added directly to a silica gel column with chloroformas an eluent until no red liquid effluent, after which spin dry, dissolved inmethanol and washing, filtration to give a purple solid tetrakis(trimethylsilyl ethynyl) porphyrin. At -78 deg.C, solution containing 43.6 milligrams (mg)(0.066 millimoles (mmol)) 5,10,15,20- tetrakis (trimethylsilyl ethynyl)porphyrin in tetrahydrofuran (THF) was added 0.4ml tetrabutylammonium fluoride(TBAF) (1 mol / l (M) in tetrahydrofuran, 0.4mmol), the reaction mixture wasstirred under nitrogen for 1.5 hours, until the reaction was complete tracking gussets. The reaction was purified by silica gel column, to give removed trimethylsilylacetylenegroup 5,10,15,20-tetra(4-ethynyl-phenyl) porphyrin monomer. |
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