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Method for preparing 2,5-furandicarboxylicacid (FDCA) by catalytic carbonylation

A technology of furandicarboxylic acid and palladium catalyst, applied in the direction of organic chemistry and the like, can solve problems such as consumption of human food resources, and achieve the effects of great application value and prospect, mild reaction conditions and high reaction efficiency

Active Publication Date: 2018-06-12
HUAZHONG UNIV OF SCI & TECH
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  • Abstract
  • Description
  • Claims
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AI Technical Summary

Problems solved by technology

[0005] In view of the defects that most of the current methods of preparing FDCA use food-based C6 sugars as raw materials to compete with humans for the already tight food resources, the purpose of the present invention is to provide a method for preparing 2,5-furandicarboxylic acid by catalytic carbonylation , wherein by using 5-bromo-2-furoic acid as a raw material, and improving the overall process flow design of the preparation method, as well as the reaction conditions and parameters of each step (including the type and proportion of reaction raw materials, reaction temperature and time, etc.) Compared with the prior art, it can effectively solve the problem that the preparation of FDCA needs to consume human food resources. The present invention uses furfural derivative 5-bromo-2-furoic acid as raw material, and the C5 sugar for synthesizing the raw material originally comes from abundant and Renewable agricultural and forestry waste such as straw, sawdust, etc., so the present invention can effectively achieve "not competing with people for food or land with food" by changing the source of FDCA synthesis route, and also broadens the biomass of furfural-based C5 platform The molecular market makes its downstream products more diversified; and, the present invention ensures high reaction parameters by optimizing reaction parameter conditions (such as the type and proportion of reaction raw materials, reaction temperature and time, carbon monoxide initial pressure value, etc.). Efficiency and product selectivity, mild reaction conditions, easy operation, great application value and prospects

Method used

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  • Method for preparing 2,5-furandicarboxylicacid (FDCA) by catalytic carbonylation

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Palladium chloride (50.0 mg, 0.28 mmol) and 4,5-bisdiphenylphosphine-9,9-dimethylxanthene (161.8 mg, 0.28 mmol) were sequentially charged into a pressure-resistant Schlenk test tube. , potassium carbonate (1.52 g, 11 mmol), water (4.96 g, 275 mmol), 5-bromo-2-furoic acid (1.04 g, 5.5 mmol) and 10 ml of 1,4-dioxane, The system is evacuated and replaced three times with carbon monoxide (in the sealed atmosphere formed by the last replacement, the pressure of carbon monoxide is 1 standard atmospheric pressure), and the temperature is maintained at 90 degrees Celsius for 6 hours. After cooling down to room temperature, the raw material is converted by liquid phase analysis. The yield is 100%, the FDCA yield is 99%, and the selectivity is 99%. The pH of the reaction solution was adjusted to 1 with hydrochloric acid solution, and then filtered, washed with ice water, and dried to obtain 2,5-furandicarboxylic acid (0.79 g, 5.06 mmol), with a yield of 92%.

Embodiment 2

[0033] Palladium chloride (50.0 mg, 0.28 mmol), 1,3-bis(diphenylphosphine) propane (115.5 mg, 0.28 mmol), potassium bicarbonate (1.65 g, 16.5 mmol), water (2.48 g, 137.5 mmol), 5-bromo-2-furoic acid (1.04 g, 5.5 mmol) and 10 milliliters of DMSO, the system was evacuated and replaced three times with carbon monoxide (the last replacement In the formed sealed atmosphere environment, the pressure of carbon monoxide is 1 standard atmospheric pressure), and the temperature is maintained at 90 degrees Celsius for 12 hours. After cooling down to room temperature, the conversion rate of raw materials is 95%, the FDCA yield is 90%, and the selectivity is 95%. . The pH of the reaction solution was adjusted to 2 with sulfuric acid solution, and then filtered, washed with ice water, and dried to obtain 2,5-furandicarboxylic acid (0.70 g, 4.51 mmol), with a yield of 82%.

Embodiment 3

[0035] [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (140.0 mg, 0.28 mmol), potassium bicarbonate (1.65 g, 16.5 mmol), water (2.48 g, 137.5 millimol) and 5-bromo-2-furoic acid (1.04 g, 5.5 mmol) were added successively in 10 milliliters of ethylene glycol diethyl ether, and the reaction system was placed in a stainless steel autoclave with a polytetrafluoroethylene lining inside. Introduce carbon monoxide at 30 standard atmospheric pressure, keep the temperature at 110 degrees centigrade and react for 6 hours. After cooling down to room temperature, the conversion rate of raw materials is 100%, the yield of FDCA is 97%, and the selectivity is 97%. The pH of the reaction solution was adjusted to 2 with sulfuric acid solution, and then filtered, washed with ice water, and dried to obtain 2,5-furandicarboxylic acid (0.81 g, 5.17 mmol), with a yield of 94%.

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Abstract

The invention discloses a method for preparing 2,5-furandicarboxylicacid (FDCA) by catalytic carbonylation. The method comprises the following steps: taking 5-bromo-2-furoic acid as a raw material, carrying out stirring reaction on a reaction system which simultaneously contains 5-bromo-2-furoic acid, solvent, alkali and palladium catalyst under the atmosphere of carbonic oxide at the temperatureof 50-120 DEG C for 4-20h; then, removing the solvent, adding acidified reagent to regulate a pH (Potential of Hydrogen) value to acidity, and separating a target product FDCA, wherein the palladium catalyst contains a palladium element, the solvent is water or a mixture of water and organic solvent. According to the method, the 5-bromo-2-furoic acid is taken as the raw material, and the whole technical process design of the preparation method and the reaction condition and parameter (including the category and the ratio of reaction raw materials, reaction temperature, time and the like) of each step can be improved. Compared with the prior art, the method disclosed by the invention solves the problem that human grain resources which need to be consumed for preparing FDCA is solved.

Description

technical field [0001] The invention belongs to the field of organic catalysis, and more specifically relates to a method for preparing 2,5-furandicarboxylic acid by catalytic carbonylation, which provides a new way for the preparation of 2,5-furandicarboxylic acid. Background technique [0002] The gradual depletion of petroleum resources has caused a huge impact on the petroleum-based chemical industry and even affected the development of the national economy. Terephthalic acid (PTA) has always been a bulk chemical with great market demand. Domestic PTA production capacity has soared from about 15 million tons in 2010 to nearly 46 million tons in 2015, accounting for about half of the global production capacity, of which 90% The above PTAs are all used in the production of polyester. In order to solve the crisis caused by the depletion of petroleum resources, the search for petroleum substitutes has attracted much attention, and biomass resources, which have the advantage...

Claims

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Application Information

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IPC IPC(8): C07D307/68
CPCC07D307/68
Inventor 尹国川张思成申冠飞雷宇
Owner HUAZHONG UNIV OF SCI & TECH
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