123740-01-2Relevant academic research and scientific papers
Preparation method of (3, 5-difluorophenyl) diphenylphosphine oxide
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Paragraph 0025-0030, (2021/01/04)
The invention relates to (3, 5-difluorophenyl) diphenylphosphine oxide and a preparation method thereof, the structural formula of the (3, 5-difluorophenyl) diphenylphosphine oxide is shown in the specification, and the preparation method comprises the following steps: firstly, under the protection of inert gas, mixing a solution containing 1-bromine- 3, 5-difluorobenzene and a reaction solution containing Mg powder, and carrying out Grignard reaction; adding a solution containing diphenyl phosphine chloride, mixing, and reacting at the temperature of 0 DEG C to room temperature; then, after purification treatment, obtaining an oily product; and finally, sequentially carrying out oxidation and purification treatment on the oily product to obtain the (3, 5-difluorophenyl) diphenylphosphineoxide. Compared with the prior art, the preparation method has the advantages of simple operation, no need of heating, easily available raw materials, high safety and the like, and the phosphine oxidegroup of the obtained compound has good water absorption and moisture retention and oxidation resistance stability, and can be applied to the fields of fuel cells, ion exchange resin, membrane separation, sensors and other functional materials.
Phosphinodefluorination of polyfluorobenzenes by silylphosphines Ph(R)PSiMe3 (R = Me, Ph): Further experimental and computational evidences for the concerted ANDN mechanism of aromatic nucleophilic substitution
Zhivetyeva,Goryunov,Bagryanskaya,Grobe,Shteingarts,Würthwein
, p. 58 - 69 (2014/07/08)
Trimethylsilylphosphines PhRPSiMe3 (1 R = Me, 2 R = Ph) have been shown to phosphinodefluorinate 1,2,3- (3), 1,3,5- (4) and 1,2,4-trifluorobenzene (5) in benzene solution or without solvent at 150-200 °C to form the respective (difluorophenyl)methylphenyl- and -diphenylphosphines in high NMR yields under harder conditions compared to the previously reported reactions of Me2PSiMe3 with the same substrates. Hexafluorobenzene (6), pentafluorobenzene (7) (at 150 °C), octafluorotoluene (8) and pentafluoropyridine (9) (at 20 °C) react with phosphine 2 without a solvent almost quantitatively under fluorine 1,4-disubstitution (for 6) or monosubstitution (for 7-9) by the Ph2P group to give the corresponding (polyfluoroaryl)diphenylphosphines in 50-60% (for 6-8) and 95% (for 9) isolated yields. The regio and substrate selectivities exhibited by 3-5 in the reactions of the single substrates and in competitive reactions of 3 vs. 4 with 1 or 2 and 4 vs. 5 with 2 indicate relative fluorine substituent rate factors fo-F > fm-F consistent with the concerted ANDN mechanism which is supported by high level quantum chemical DFT-studies for the reactions of the substrates 3 and 4 with 1, 2 and 10 as well as for 6 with 2.
