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Arylmethyl phosphonate preparation method

A technology of arylmethyl phosphonate and arylmethyl alcohol, applied in the field of organic synthesis, can solve the problems of high cost, environmental pollution, high toxicity of reagents and the like, and achieves the effects of simple operation, high product quality and reduction of reaction cost.

Active Publication Date: 2016-01-13
HEBEI UNIV OF TECH
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  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] The purpose of the present invention is to solve the problems of high toxicity, environmental pollution and high cost of the reagents used in the preparation process of the above-mentioned arylmethyl phosphonate. We have developed a method for preparing arylmethyl phosphonate with simple process and easy industrial production.

Method used

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  • Arylmethyl phosphonate preparation method

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Effect test

Embodiment 1

[0021] With 6.40g (0.02mol) 3,5-dibenzyloxybenzyl alcohol, 9.96g (0.06mol) triethyl phosphite, 1.09g (3.0mmol) cetyltrimethylammonium bromide and 0.07g ( 0.4mmol) KI was added to the three-necked flask, stirred thoroughly and reacted at 140°C for 6h, then depressurized (pressure 10mmHg, the same as the following examples) to distill off excess triethyl phosphite, and continued to react at 140°C for 4h. After cooling down to room temperature, extract with a mixed solvent of ethyl acetate and petroleum ether (boiling range: 60-90°C, the same as the following examples) with a volume ratio of 1:3, and concentrate under reduced pressure to obtain 7.95 g of the product, of which 3,5-di The yield of diethyl benzyloxybenzylphosphonate was 60.3%. 1 H-NMR (CDCl 3 ,400MHz)δ:1.23~1.26(t,J=7.0Hz,6H,Ar-P-O-CH 2 -CH 3 ), 1.32~1.35 (t, J=7.2Hz, 9H, P-O-CH 2 -CH 3 ), 3.09 (d, 2H, J=21.6Hz, Ar-CH 2 -P),3.96~4.05(m,4H,Ar-P-O-CH 2 ),4.08~4.15(m,6H,P-O-CH 2 ),5.04(s,4H,PhCH 2 ),6.52~6.57(...

Embodiment 2

[0024] With 12.80g (0.04mol) 3,5-dibenzyloxybenzyl alcohol, 33.20g (0.20mol) triethyl phosphite, 1.92g (6.0mmol) cetyltrimethylammonium chloride and 0.13g ( 0.8mmol) KI was added into the three-necked flask, stirred thoroughly and reacted at 185°C for 5.5h, distilled off excess triethyl phosphite, and continued to react at 185°C for 4h. After cooling down to room temperature, it was extracted with a mixed solvent of ethyl acetate and petroleum ether with a volume ratio of 1:3, and concentrated under reduced pressure to obtain 20.03 g of the product, of which the yield of diethyl 3,5-dibenzyloxybenzylphosphonate was was 75.8%.

Embodiment 3

[0026] With 6.40g (0.02mol) 3,5-dibenzyloxybenzyl alcohol, 26.56g (0.16mol) triethyl phosphite, 0.32g (1.0mmol) tetrabutylammonium bromide and 0.06g (0.4mmol) NaI Add it into a three-necked flask, stir it well, and react it at 162°C for 6h, steam off excess triethyl phosphite, and continue to react at 162°C for 4h. After cooling down to room temperature, it was extracted with a mixed solvent of ethyl acetate and petroleum ether with a volume ratio of 1:3, and concentrated under reduced pressure to obtain 11.25 g of the product, of which the yield of diethyl 3,5-dibenzyloxybenzylphosphonate was was 85.3%.

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Abstract

The invention provides an arylmethyl phosphonate preparation method. The method includes the following steps that arylmethyl ester, triethyl phosphate and a catalyst are sequentially added into a reactor and reacted for 5-8 h at the temperature of 100-200 DEG C after full stirring, and after excessive triethyl phosphate is distilled off through decompression, the mixture continues to be reacted for 3-7 h at the temperature of 100-200 DEG C; then, the mixture is cooled to the room temperature, a product is extracted through a mixed solvent, and arylmethyl phosphonate is obtained after the mixed solvent is removed. The catalyst is one or more of tetramethyl ammonium bromide, tetraethylammonium bromide, tetrabutyl ammonium bromide, benzyltrimethyl ammonium bromide, cetyl trimethyl ammonium bromide, cetyltrimethyl ammonium chloride, ammonium chloride, sodium iodide and potassium iodide. Arylmethyl phosphonate is synthesized through a one-step method, other solvents are not added, operation is easy, and the product yield is high and can be 85.3% at maximum.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and relates to the preparation of a pharmaceutical intermediate, in particular to a preparation method of arylmethyl phosphonate. Background technique [0002] Arylmethylphosphonate is an important pharmaceutical intermediate, which can undergo Wittig-Horner reaction with aromatic aldehyde to form a stilbene skeleton, and is widely used in the synthesis and conjugation of pharmaceutical intermediates such as resveratrol and its derivatives Preparation of functional materials such as macromolecules. [0003] At present, arylmethyl phosphonate is mainly obtained by the reaction of arylmethyl halide and triethyl phosphite, and aryl methyl halide is prepared by the halogenation reaction of alcohol. Halogenating reagents are mainly phosphorus tribromide (Chinese Journal of Synthetic Chemistry, 2008, 16 (2): 170-172), thionyl chloride (Fine Chemical Intermediates, 2011, 41 (6): 37-40), hydro...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/40
Inventor 王家喜张明明周宏勇李云庆
Owner HEBEI UNIV OF TECH
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