Preparation and application background and overview of tri-tert-butylphosphine tetrafluoroborate
Tri-tert-butylphosphine tetrafluoroborate, also called tri-tert-butylphosphine tetrafluoroborate, is an organic intermediate that can be obtained by the reaction of tert-butyl chloride and phosphorus tribromide. There are literature reports that it can be used to prepare α-aryl vinyl phosphonate, sensitized materials and a sensitized material.
Preparation and application of tri-tert-butylphosphine tetrafluoroborate
Under nitrogen protection, add 7.28g (1.05eq) magnesium chips and 15.2g (one-eighth of the total weight) chlorotert-butane THF solution (26.7g chlorocyclohexane dissolved in 135mL of THF), heat to 55~60°C, add 2 grains of iodine to initiate successfully, add the remaining 105.5g (total 1.0eq) of chlorotert-butane tetrahydrofuran solution dropwise, while maintaining boiling reflux, after the dropwise addition is completed, heat to Reflux sodium bicarbonate for 2 hours, cool to room temperature and set aside. Analyze and measure the concentration to be 1.82±0.3mmol/g (approximately 154g). In a 500mL four-neck flask, under argon protection, add 7.5g (0.182eq) phosphorus tribromide and 70mLTHF, stir at room temperature, add 988mg (0.0182eq) cuprous iodide and 898mg (0.0364eq) lithium bromide, and cool down – At 15°C, at ‑10～‑5°C, add 154g of Grignard reagent dropwise, stir at low temperature for 2 hours, then naturally raise the temperature and stir for 4 hours. Use GC to monitor that di-tert-butylphosphorus chloride is less than 1%, the main content is 80-85%, and the impurities are 10- 20%, the reaction is completed, add 50.6g (0.946eq) 45.9% fluoboric acid, 9.3g (0.092eq) 15% ammonium chloride aqueous solution and 45g water into another reaction bottle, layer the oil, and wash it once with 50mL water. Combine the aqueous layers and extract once more with 50 mL of methylene chloride. Combine the dichloromethane layers, add 20g of sodium sulfate and dry. At this time, there is a small amount of water layer below. Separate the organic layer and add 20g of sodium sulfate to dry. Filter, wash with 10mL of dichloromethane, and concentrate at 35-50°C to obtain 24g of solid oil. , add 20mL ethanol (1 times the volume) and heat to 78°C to dissolve, cool down to 45°C and add 60mL MBTE (3 times the volume of ethanol) to cool down the temperature for crystallization for 1 hour. After filtration, 6.7 g of white solid was obtained, washed with 10 mL of MTBE, and dried to obtain 7.5 g of white solid, with a yield of 55% and a melting point of >260°C. The NMR spectrum was consistent with the literature.
Preparation and application of tri-tert-butylphosphine tetrafluoroborate
Preparation and application of tri-tert-butylphosphine tetrafluoroborate Application 1.
CN201410658785.1 discloses a method for Pd-catalyzed synthesis of α-arylvinylphosphonate. The specific steps are as follows: add α-bromovinylphosphonate, arylboronic acid, and palladium acetate to the reactor. Potassium carbonate, tri-tert-butylphosphine tetrafluoroborate; after vacuuming, add N2 to remove oxygen; under N2 gas protection, add anhydrous toluene and stir at room temperature for 12~16h; after the reaction is completed, the reaction mixture is treated with ethyl acetate As an eluent, pass through a short silica gel column to remove inorganic salts to obtain an eluate. The eluate is distilled to remove ethyl acetate and toluene, and then a mixture of petroleum ether and ethyl acetate is used as an eluent and separated by column chromatography. α-aryl vinyl phosphonate is obtained by distillation; the invention has the advantages of good substrate universality, strong functional group compatibility, mild reaction conditions, high reaction efficiency, low catalyst dosage and reaction amplification performance.
Preparation and application of tri-tert-butylphosphine tetrafluoroborate Application 2.
CN201410658785.1 provides a preparation method of a sensitized material and an organic light-emitting diode. The preparation method of the sensitized material includes: adding C24H16Br2P2 and dichloromethane into a hydrogen peroxide aqueous solution to react, to obtain a first reaction solution, and Filter to obtain a solid; dissolve the solid in dichloromethane and purify with the first silica gel column chromatography to obtain an intermediate; combine the intermediate, preset electron donor material, palladium acetate and tri-tert-butyltetrafluoroborate The base phosphine is mixed to obtain a mixed liquid; and the mixed liquid is put into a potassium trifluoroborate glove box containing sodium tert-butoxide and toluene to react to obtain a second reaction liquid; the second reaction liquid is added with dichloro Extract with methane and purify with a second silica gel column chromatography to obtain the sensitized material. The preparation method of the sensitized material and the organic light-emitting diode of the present invention can improve the internal quantum efficiency and service life of the organic light-emitting diode and expand the color gamut.
Preparation and application of tri-tert-butylphosphine tetrafluoroborate Application 3.
CN201410280753.2 provides a high-yield, low-cost synthesis process of di(tri-tert-butylphosphine)palladium(O), using tri-tert-butylphosphine tetrafluoroborate and tris(dibenzylideneacetone) ) dipalladium(O) chloroform adduct and (1,5-cyclooctadiene)palladium dibromide react with each other to form di(tri-tert-butylphosphine)palladium(O) in an alkaline environment ), which solves the problems of expensive raw materials, low yield, and demanding reaction conditions in the current production of this product using existing technologies. The reaction yield of this method is more than 50%. It has good promotion potential and application prospects.
References
[1]CN201811415628.2 Preparation method of sensitized material and organic light-emitting diode
[2] CN201410658785.1Pd-catalyzed method for synthesis of α-arylvinylphosphonate
[3]CN201410280753.2 A synthetic method for preparing di(tri-tert-butylphosphine)palladium (O)
[4][Chinese invention] CN201210505525.1 A method for preparing trialkylphosphine fluoroborate
