A method of using black phosphorus to synthesize organic phosphine compounds

A compound and organic phosphine technology, which is applied in the field of synthesis of organic phosphine compounds using black phosphorus, can solve the problems of not meeting the development requirements of green chemistry, harsh reaction conditions, and large substrate limitations, and achieve safe and efficient synthesis with less reaction by-products , good reproducibility

Active Publication Date: 2020-07-03
HUBEI MOPHOS TECH CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, since most of the reaction substrates used in these two methods are sensitive to air, the reaction conditions are relatively harsh, the substrates are limited, and the reaction produces a large number of organic halogenated by-products and organometallic compounds, which do not meet the development requirements of green chemistry.
Moreover, a large amount of pollutants will also be produced during the preparation of phosphorus halides.

Method used

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  • A method of using black phosphorus to synthesize organic phosphine compounds
  • A method of using black phosphorus to synthesize organic phosphine compounds
  • A method of using black phosphorus to synthesize organic phosphine compounds

Examples

Experimental program
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Effect test

Embodiment 1

[0045] Embodiment 1: the synthetic method one of triethyl phosphate

[0046]

[0047] Take 6.2mg of black phosphorus crystals and disperse them in 20mL of ethanol, add 2mL of H 2 o 2 , stirred and reacted for 4h at 40°C, stopped the reaction after the solution was clarified, then removed the solvent by rotary evaporation, and obtained the yellow oily product triethyl phosphate after separation by silica gel column chromatography, and its yield was 75%, and its nuclear magnetic spectrum was determined as follows: figure 1 As shown, NMR spectrum data: 1 H NMR (400MHz, CDCl 3 )δ4.23–4.00(m,6H),1.35(m,9H), the spectrum proves the correctness of its structure.

Embodiment 2

[0048] Embodiment 2: the synthetic method two of triethyl phosphate

[0049]

[0050] Disperse 6.2mg of black phosphorus crystals in 20ml of ethanol, add 20mg of KClO to the system 3 , Stir the reaction at 60°C for 8h, stop the reaction after the solution is clear, then remove the solvent by rotary evaporation, and obtain the yellow oily product triethyl phosphate after separation by silica gel column chromatography, and the correctness of its structure is also confirmed by nuclear magnetic spectrum.

Embodiment 3

[0051] Embodiment 3: the synthetic method three of triethyl phosphate

[0052]

[0053] Disperse 6.2mg of black phosphorus crystals in 20mL of ethanol, add 5mL of concentrated hydrochloric acid dropwise to the system, stir and react at 60°C for 6h, stop the reaction after the solution is clear, then remove the solvent by rotary evaporation, and obtain yellow Oily product triethyl phosphate, its yield is 60%.

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Abstract

The invention discloses a method for compounding organphosphorus by using black phosphorus. The method takes the black phosphorus as a reaction raw material, safely and efficiently compounds organic phosphate, sulpho-phosphite ester, amino phosphite ester, alkylphosphine, alkylphosphine oxide and other organphosphorus with wide usages, a conventional synthsis route by using phosphorus halide and phosphate to compound the organphosphorus is avoided, the synthesis steps are simple and short, the production technology is operated simply and easily, the reproducibility is good, the reaction is simple and green, the use of a phosphorus halide reagent is avoided, the range of the synthetic organphosphorus is wider, the method satisfies the requirements of green chemical development, and the large-scale production can be achieved.

Description

technical field [0001] The invention relates to an organic synthesis method, in particular to a method for synthesizing an organic phosphine compound using black phosphorus. Background technique [0002] Organophosphine compounds are an important class of organic compounds, which have broad application prospects in the fields of flame retardants, rare earth extractants, pesticides, battery electrolytes, organic asymmetric catalysis, functional materials, and biomedicine. Many major breakthroughs in organic synthesis are closely related to the discovery of new organophosphine reagents, phosphine ligands and phosphorus catalysts. For example, German chemist Georg Wttig used phosphonium ylide reagents to react with aldehydes and ketones to form alkenes, which won the 1979 Nobel Prize Chemistry Award; Heck, Negishi and Suzuki who won the Nobel Prize in Chemistry in 2010 also require the participation of organophosphine ligands in the coupling reaction. Organophosphate compounds...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/11C07F9/50C07F9/53C07F9/202C07F9/22C07F9/12
CPCC07F9/11C07F9/12C07F9/202C07F9/22C07F9/50C07F9/5031C07F9/53C07F9/5333
Inventor 喻学锋吴列
Owner HUBEI MOPHOS TECH CO LTD
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