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Method for synthesizing novel fluoride-free organic phosphine ligand modified by carbonate ester

A synthesis method and carbonate technology are applied in the field of synthesis of novel carbonate-modified fluorine-free organic phosphine ligands, which can solve environmental problems, expensive fluorocarbons and other problems, and achieve the effects of improving solubility and realizing recovery and reuse.

Inactive Publication Date: 2018-01-12
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, phosphine ligands modified with fluoroalkyl groups have great disadvantages. Fluorocarbons and corresponding fluorine-containing ligands are not only very expensive, but also cause serious environmental problems when a large amount of fluorine-containing compounds are used.

Method used

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  • Method for synthesizing novel fluoride-free organic phosphine ligand modified by carbonate ester
  • Method for synthesizing novel fluoride-free organic phosphine ligand modified by carbonate ester
  • Method for synthesizing novel fluoride-free organic phosphine ligand modified by carbonate ester

Examples

Experimental program
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Effect test

Embodiment 1

[0028] Example 1 Synthesis of (4-carbonate phenyl) diphenylphosphine compound

[0029] The first step, the synthesis of compound 2a ((4-vinylphenyl) diphenylphosphine)

[0030] Wash the magnesium powder with hydrochloric acid and acetone respectively, and drain it for later use. THF was refluxed with metal Na until the benzophenone turned dark purple, and then evaporated for later use. Add the newly prepared 1.5g Mg powder (1.1eq) into the sealed reaction device with the function of dripping reflux, and use N 2 Replace 3 times. in N 2 Under protection, sequentially add a small amount of I 2 Granules, 5mg of HQ (hydroquinone) and refined THF (about 10ml), the dried compound 1 (4-bromostyrene) (10g) was transferred to the dropping funnel, diluted with refined THF (10ml) . The reaction is initiated by heating, and after initiation, the THF solution of 4-bromostyrene is slowly added dropwise, and the rate of addition is controlled so that the temperature of the solution does...

Embodiment 2

[0041] Example 2 Synthesis of (4-carbonate phenyl) diphenylphosphine compound

[0042] The first step, the synthesis of compound 2a ((4-vinylphenyl) diphenylphosphine)

[0043] Add the newly prepared Mg powder (2.0g) into the reaction device, and use N 2 Replace 3 times. in N 2 Under protection, add I in turn 2 Granules, 10 mg of HQ and 15 ml of refined THF, the dried compound 1 (4-bromostyrene) (10 g) was transferred to a dropping funnel, and diluted with refined THF. The reaction was initiated by heating, and after the initiation, a THF solution of 4-bromostyrene (10 g) was slowly added dropwise, and the rate of addition was controlled so that the temperature of the solution did not exceed 30° C. After the dropwise addition was completed, the mixture was stirred at room temperature for 2 h to obtain a gray mixture. After the Grignard reagent was prepared, the reaction apparatus was transferred to an ice-salt bath (-30° C.) and cooled and stirred for 15 minutes, and the ...

Embodiment 3

[0052] Example 3 Synthesis of (4-carbonate phenyl) diphenylphosphine compound

[0053] The first step, the synthesis of compound 2a ((4-vinylphenyl) diphenylphosphine)

[0054] The newly made Mg powder (1.8g) is added to the reaction device, and the 2 Replace 3 times. in N 2 Under protection, add I in turn 2 Granules, 15mg of HQ and 15ml of refined THF, the dried compound 1 (4-bromostyrene) (10g) was transferred to the dropping funnel, and diluted with refined THF. The reaction is initiated by heating, and after the initiation, THF solution of 4-bromostyrene (10 g) is slowly added dropwise, and the rate of addition is controlled so that the solution temperature does not exceed 30°C. After the dropwise addition was completed, the mixture was stirred at room temperature for 2 h to obtain a gray mixture. After the Grignard reagent was prepared, the reaction apparatus was transferred to an ice-salt bath (-30° C.) and cooled and stirred for 15 minutes, and the THF solution of ...

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Abstract

The invention relates to the field of organic synthesis, and provides a method for synthesizing a novel fluoride-free organic phosphine ligand modified by carbonate ester. According the synthesis method, p-bromostyrene or derivatives of the p-bromostyrene are adopted as raw materials for preparing a Grignard reagent which reacts with a phosphorus source to produce a skeleton-structure molecule with triphenylphosphine, and after oxidation, epoxidation, cycloaddition, reduction are conducted, the target molecular structure can be obtained. The synthesis method has the advantages that by synthesizing the novel organic CO2-soluable phosphine ligand, the solubility of the phosphine ligand in supercritical CO2 is improved, so that the application of fluoride-free phosphine ligand- organo-metallic catalysts in the supercritical CO2 is realized; besides, due to the property that the organic carbonate ester compound is insoluble in weak or non-polar organic solvent, such as an alkane compound,the fluorine-free phosphine ligand modified by the carbonate group is provided with a function of phase separation in a reaction system so that the recovery and reuse of the catalysts can be achieved.

Description

technical field [0001] The invention relates to the field of organic chemistry and organic synthesis, and provides a method for synthesizing a novel carbonate-modified fluorine-free organic phosphine ligand. Background technique [0002] With the development of science and technology and the in-depth study of transition metal chemistry by researchers, the field of organometallic catalysis has been greatly developed. Among them, the development and application of organophosphine ligands play an important role in organometallic catalytic reactions. This is because the phosphine ligand is very tailorable, and its electronic and steric effects can be changed by introducing appropriate groups, so that it can achieve the required function in the catalytic process. [0003] Supercritical CO 2 It is an environmentally friendly solvent that is being vigorously developed at present, but the organic phosphine ligand is in the supercritical CO 2 Poor solubility in medium, thus limiti...

Claims

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Application Information

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IPC IPC(8): C07F9/655
CPCY02P20/54
Inventor 姜文凤范玲霞袁宵张天保王慧龙
Owner DALIAN UNIV OF TECH
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