Method for preparing phosphate ester derivatives from white phosphorus

A technology of phosphate esters and derivatives, applied in the chemical industry, can solve the problems of poor atom economy, unfriendly environment, violent reaction, etc., and achieve the effects of low reaction cost, no white phosphorus residue, and high yield

Active Publication Date: 2021-06-22
XIAMEN UNIV
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  • Abstract
  • Description
  • Claims
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AI Technical Summary

Problems solved by technology

The traditional industrial method for synthesizing organophosphorus compounds is to chlorinate white phosphorus (P 4 ) generate PCl 3 , and then through the multi-step reaction of nucleophilic substitution and equalization, this type of method has disadvantages such as poor atom economy, high energy consumption, violent reaction, etc., and is not environmentally friendly

Method used

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  • Method for preparing phosphate ester derivatives from white phosphorus
  • Method for preparing phosphate ester derivatives from white phosphorus
  • Method for preparing phosphate ester derivatives from white phosphorus

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Embodiment 1: the preparation of tri-p-methoxyphenyl phosphite

[0028]

[0029] In the 10mL reaction bottle, first add K 3 PO 4 (0.045mmol, 9.6mg), diphenyl diselenide (0.045mmol, 14.1mg), white phosphorus toluene solution (white phosphorus 5.6mg, toluene 0.5mL), p-methoxyphenol (0.9mmol, 112.0mg), di Methyl sulfoxide (0.5 mL) was heated up to 60° C. under argon atmosphere, and reacted for about 4 hours. The reaction was detected by phosphospectrum and the reaction was stopped. The reaction solution was cooled to room temperature, and the reaction solution was separated by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 10:1, v / v) to obtain 61.3 mg of the product tri-p-methoxyphenyl phosphite. rate of 85%. 1 H NMR (400MHz, CDCl 3 ):δ7.07(d, J=7.4Hz, 6H), 6.86(d, J=7.5Hz, 6H), 3.80(s, 9H). 13 C NMR (100MHz, CDCl 3 ): δ156.2, 145.1 (d, J=3.3Hz), 121.7 (d, J=6.3Hz), 114.7, 55.6. 31 P NMR (162MHz, CDCl 3 ):δ123.83.

Embodiment 2～7

[0030] Embodiment 2~7: the preparation of tri-p-methoxyphenyl phosphite

[0031]

[0032] In addition to the change of the type of alkali, the amount of other substances and the reaction conditions have no change, the results are shown in Table 1:

[0033] Table 1

[0034] Example alkali Yield Example alkali Yield 2 KOH 76％ 5 Na 2 CO 3

Embodiment 8

[0035] Embodiment 8: the preparation of triphenyl phosphite

[0036]

[0037] In the 10mL reaction bottle, first add K 3 PO 4 (0.045mmol, 9.6mg), diphenyldiselenide (0.045mmol, 14.1mg), white phosphorus toluene solution (white phosphorus 5.6mg, toluene 0.5mL), phenol (1.1mmol, 101.0mg), dimethyl sulfoxide ( 0.5mL), under the condition of argon, the temperature was raised to 60°C, and the reaction was carried out for about 6 hours. When the reaction was detected by phosphospectrum, the reaction was stopped. The reaction solution was cooled to room temperature, and the reaction solution was separated by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 10:1, v / v) to obtain 49.1 mg of the product triphenyl phosphite, with a yield of 88%. 1 H NMR (400MHz, CDCl 3 ):δ7.45-7.30(m,6H),7.25-7.21(m,3H),7.21-7.13(m,6H). 13 C NMR (100MHz, CDCl 3 ): δ151.6(d, J=2.7Hz), 129.7, 124.3, 120.8(d, J=6.9Hz). 31 P NMR (162MHz, CDCl 3 ):δ127.84.

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Abstract

A method for preparing phosphate ester derivatives from white phosphorus relates to the field of chemical engineering, and comprises the following steps: adding alkali, a catalyst, a white phosphorus solution, ROH or RSH (R represents alkyl or aromatic group) into a reaction container in an inert atmosphere, and heating and stirring the mixture in a mixed solvent of toluene and DMSO (dimethyl sulfoxide) to react for a certain time, so as to obtain three-coordinated phosphate ester derivatives; and 2) continuing to add H2O2, air or sulfur powder until the oxidation is completed, thereby obtaining the tetra-coordinated phosphate ester derivative. According to the method, chlorine, phosphorus trichloride and halogen are not needed, phosphite ester is directly prepared from elementary white phosphorus in an efficient, green and environment-friendly manner, and phosphate and thiophosphate can be directly prepared after oxidation. High pollution and high corrosivity of a traditional method are avoided in the whole process; meanwhile, white phosphorus is completely converted in the whole process, white phosphorus residues are avoided, and the post-reaction treatment process is safe.

Description

technical field [0001] The invention relates to the field of chemical industry, in particular to a method for preparing phosphate derivatives from white phosphorus. Background technique [0002] As important compounds in organic synthesis, flame retardants and biochemistry, organophosphates have been attracting much attention. The traditional industrial method for synthesizing organophosphorus compounds is to chlorinate white phosphorus (P 4 ) generate PCl 3 , and then through the multi-step reaction of nucleophilic substitution and equalization, this type of method has disadvantages such as poor atom economy, high energy consumption, violent reaction, etc., and is not environmentally friendly. Organophosphorus compounds with C-O-P bonds have attracted increasing attention due to their favorable properties in the fields of antioxidants, flame retardants, antistress agents, and medicine. Their application in organic synthesis is also well developed. These compounds are tr...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/145C07F9/202C07F9/205
CPCC07F9/145C07F9/205C07F9/202
Inventor 唐果张粤迟杨洋曾祥哲陈双慧赵玉芬
Owner XIAMEN UNIV
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