阅读说明：本技术 一种9-蒽甲酸的合成方法 (Synthesis method of 9-anthracenecarboxylic acid ) 是由 于景喜 郑丽敏 刘扬 于 2021-08-02 设计创作，主要内容包括：本发明涉及染料中间体及电子荧光材料的合成技术领域,提供了一种新型9-蒽甲酸的合成方法,包括以下步骤：以9-蒽甲醛为原料,在氧化剂和助剂及pH缓冲剂的作用下进行反应,反应完成后蒸除溶剂,调节pH＝1-5,萃取有机物,然后蒸除有机相,即可制备得到9-蒽甲酸。本发明解决了现有技术合成9-蒽甲酸副产物较多,收率低等问题,合成中以9-蒽甲醛为原料,在氧化剂和助剂以及pH缓冲剂的作用下进行反应,将制备得到的黄色固体进行核磁氢谱鉴定及液相色谱检测,结果显示,所制备得到的产品结构为9-蒽甲酸,纯度可达99％以上,由此说明本发明的合成方法副产物较少,易提纯,反应条件温和,操作简单,产品质量稳定,适合工业化生产。(The invention relates to the technical field of synthesis of dye intermediates and electronic fluorescent materials, and provides a synthesis method of novel 9-anthracenecarboxylic acid, which comprises the following steps: the 9-anthracene formaldehyde is used as a raw material, the reaction is carried out under the action of an oxidant, an auxiliary agent and a pH buffering agent, after the reaction is finished, a solvent is evaporated, the pH value is adjusted to be 1-5, an organic matter is extracted, and then an organic phase is evaporated to obtain the 9-anthracene formic acid. The invention solves the problems of more by-products, low yield and the like of 9-anthracenecarboxylic acid synthesized by the prior art, the 9-anthracenecarboxylic acid is used as a raw material in the synthesis, the reaction is carried out under the action of an oxidant, an auxiliary agent and a pH buffering agent, and the prepared yellow solid is subjected to nuclear magnetic hydrogen spectrum identification and liquid chromatography detection, and the result shows that the prepared product has the structure of 9-anthracenecarboxylic acid and the purity can reach more than 99 percent.)

1. A synthesis method of 9-anthracenecarboxylic acid is characterized in that 9-anthraceneformaldehyde is used as a raw material, the reaction is carried out under the action of an oxidant, an auxiliary agent and a pH buffering agent, after the reaction is finished, a solvent is evaporated, the pH value is adjusted to 1-5, organic matters are extracted, and then an organic phase is evaporated, so that the 9-anthracenecarboxylic acid can be prepared.

2. The method for synthesizing 9-anthracenecarboxylic acid according to claim 1, wherein the oxidant is sodium chlorite, calcium chlorite or potassium chlorite.

3. The method for synthesizing 9-anthracenecarboxylic acid according to claim 2, wherein the molar ratio of 9-anthraceneformaldehyde to chlorite ion is 1: 0.9-3.0.

4. The method for synthesizing 9-anthracenecarboxylic acid according to claim 1, wherein the auxiliary agent is 2-methyl-2-butene, 2-methyl-1-butene, resorcinol or sulfamic acid.

5. The method for synthesizing 9-anthracenecarboxylic acid according to claim 4, wherein the auxiliary agent is 2-methyl-2-butene, and the molar ratio of 9-anthracenealdehyde to 2-methyl-2-butene is 1: 1.0-3.0.

6. The method for synthesizing 9-anthracenecarboxylic acid according to claim 1, wherein the pH buffer is sodium dihydrogen phosphate or potassium dihydrogen phosphate.

7. The method for synthesizing 9-anthracenecarboxylic acid according to claim 6, wherein the molar ratio of the 9-anthracenecarboxylic acid to the pH buffering agent is 1: 1.0-3.0.

8. The method for synthesizing 9-anthracenecarboxylic acid according to claim 1, wherein the solvent used in the reaction is tert-butanol, isopropanol, acetone, tetrahydrofuran, acetonitrile, dioxane or N, N-dimethylformamide.

9. The method for synthesizing 9-anthracenecarboxylic acid according to claim 8, wherein the solvent used in the reaction is isopropanol, and the mass ratio of 9-anthracenealdehyde to isopropanol is 1: 10-20.

10. The method for synthesizing 9-anthracenecarboxylic acid according to claim 1, wherein the reaction is carried out under the conditions of temperature control of 20-30 ℃ and reaction time of 2-3 hours.

Technical Field

The invention relates to the technical field of synthesis of dye intermediates and electronic fluorescent materials, in particular to a synthesis method of 9-anthracenecarboxylic acid.

Background

The 9-anthracene formic acid is used as a dye intermediate and an electronic fluorescent material, and has the following structural formula:

the current method for synthesizing 9-anthracenecarboxylic acid is reported as follows:

GB2523811A reports that 9-anthracenecarboxylic acid is obtained by taking 9, 10-dibromoanthracene as a raw material, forming lithium salt by butyl lithium at the temperature of-78 ℃, and then treating with dry ice. The literature [ Tetrahedron Letters,2014, vol.55, #41, p.5671-5675] reports a process for the synthesis of 9-anthracenecarboxylic acid by reaction of 9-anthraceneboronic acid and ethyl acetoacetate in a yield of 87%. The 9-anthracene boric acid is not easy to obtain and has higher price. CN110577457 reports that the yield of 9-anthracenecarboxylic acid synthesized by using 9-anthraceneboronic acid and carbon dioxide as raw materials is 82%. However, the catalyst used and 9-anthraceneboronic acid are not readily available.

The document [ Transition Metal Chemistry,2019, vol.44, #2, p.167-173] reports that 9-anthracene formaldehyde is used as a raw material, the catalyst is catalyzed by a cobalt composite catalyst, LED lamp irradiates for 150 hours, the yield is 100%, and the catalyst is not easy to obtain in the process and is not suitable for industrial production.

The literature [ Chemistry Letters,2012, vol.41, #9, p.913-914,2] reports that 9-anthracenecarboxylic acid is synthesized with a yield of only 47% by using carbon dioxide and anthracene as raw materials.

Disclosure of Invention

Aiming at the problems of the prior art, the invention provides a novel synthesis method of 9-anthracenecarboxylic acid, which has the advantages of mild reaction conditions, simple operation and stable product quality and is suitable for industrial production.

The invention adopts the following technical scheme:

a synthesis method of 9-anthracene formic acid comprises the steps of taking 9-anthracene formaldehyde as a raw material, reacting under the action of an oxidant, an auxiliary agent and a pH buffering agent, evaporating to remove a solvent after the reaction is finished, adjusting the pH value to be 1-5, extracting an organic matter, and then evaporating to remove an organic phase to obtain the 9-anthracene formic acid.

Further, the oxidant is sodium chlorite, calcium chlorite or potassium chlorite.

Further, the molar ratio of the 9-anthracene formaldehyde to the chlorite ion is 1: 0.9-3.0.

Further, the auxiliary agent is 2-methyl-2-butene, 2-methyl-1-butene, resorcinol or sulfamic acid.

Further, the auxiliary agent is 2-methyl-2-butene, and the molar ratio of the 9-anthracene formaldehyde to the 2-methyl-2-butene is 1: 1.0-3.0.

In the technical scheme, the 2-methyl-2-butene is low in price and is easier to remove.

Further, the pH buffer is sodium dihydrogen phosphate or potassium dihydrogen phosphate.

Further, the molar ratio of the 9-anthracene formaldehyde to the pH buffering agent is 1: 1.0-3.0.

Further, the solvent used in the reaction is tert-butyl alcohol, isopropanol, acetone, tetrahydrofuran, acetonitrile, dioxane or N, N-dimethylformamide.

Furthermore, the solvent used in the reaction is isopropanol, and the mass ratio of the 9-anthracene formaldehyde to the isopropanol is 1: 10-20.

In the technical scheme, the isopropanol is low in price and has good solubility to the substrate 9-anthracene formaldehyde.

Further, the reaction condition is controlled by 10-50 ℃.

Further, the reaction condition is that the temperature is controlled to be 20-30 ℃ and the reaction lasts for 2-3 hours.

Further, the solvent used for extraction is a water-immiscible solvent, including but not limited to ethyl acetate, dichloromethane, chloroform, dichloroethane, tetrachloroethane, toluene, xylene.

Further, the acid used for adjusting the pH is hydrochloric acid, sulfuric acid, nitric acid or acetic acid.

The invention has the beneficial effects that:

the synthesis method comprises the steps of taking 9-anthracene formaldehyde as a raw material, reacting under the action of an oxidant, an auxiliary agent and a pH buffering agent, evaporating a solvent after the reaction is finished, adjusting pH, extracting an organic matter, and evaporating an organic phase to obtain the 9-anthracene formic acid. The method has the advantages of fewer byproducts, easy purification, mild reaction conditions, simple operation and stable product quality, and is suitable for industrial production.

Drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum identification map;

FIG. 2 is a liquid quality detection map;

FIG. 3 is a liquid phase detection profile.

Detailed Description

The present invention will be described in detail with reference to the following specific examples:

example 1

100g of 9-anthracenealdehyde, 1000g of isopropanol and 50g of 2-methyl-2-butene are added into a reaction bottle, 113.5g of sodium dihydrogen phosphate and 300g of aqueous solution are added into the reaction bottle while stirring, 68.6g of sodium chlorite and 300g of aqueous solution are added dropwise, and the temperature is controlled to be 20-30 ℃. After the dropwise addition, the reaction is stirred at room temperature for 2 hours. After the reaction was completed, the reaction solution was distilled off under reduced pressure, the solvent was distilled off, 50g of concentrated hydrochloric acid was used to adjust the pH to 2-3, a large amount of solid was precipitated, 1000g of ethyl acetate was added and stirred to dissolve the solid, filtration was performed, the filter cake was rinsed with 200g of ethyl acetate, liquid separation was performed, the organic phase was washed twice with 300g × 2 water, and the organic phase was distilled off to obtain 74.1g of yellow solid, yield: 69.32 percent.

The prepared yellow solid is subjected to nuclear magnetic hydrogen spectrum identification, and the result is shown in figure 1, and the structure of the yellow solid is 9-anthracenecarboxylic acid.

The yellow solid obtained by the preparation was subjected to liquid quality detection, as shown in FIG. 2, and it was found that the molecular weight thereof was 222.1, which was consistent with that of 9-anthracenecarboxylic acid.

And then, liquid chromatography detection is carried out, and the result is shown in figure 3, and the purity of the 9-anthracenecarboxylic acid prepared by the method can reach more than 99%.

Example 2

100g of 9-anthracenealdehyde, 1500g of isopropanol and 68g of 2-methyl-2-butene are added into a reaction bottle, 151g of sodium dihydrogen phosphate and 300g of aqueous solution are added into the reaction bottle while stirring, 87g of sodium chlorite and 300g of aqueous solution are added dropwise, and the temperature is controlled to be 20-30 ℃. After the dropwise addition, the reaction is carried out for 2 hours under room temperature stirring, reduced pressure distillation is carried out, the solvent is evaporated, 50g of concentrated hydrochloric acid is used for adjusting the pH value to be 2-3, a large amount of solid is separated out, 1000g of ethyl acetate is added, the solid is dissolved by stirring, filtration is carried out, a filter cake is rinsed by 200g of ethyl acetate, liquid separation is carried out, an organic phase is washed twice by 300g of multiplied by 2 water, and the organic phase is evaporated, so that 72g of yellow solid is obtained, and the yield: 67.29 percent.

Example 3

100g of 9-anthracenealdehyde, 1000g of isopropanol and 34.02g of 2-methyl-2-butene are added into a reaction bottle, 151g of sodium dihydrogen phosphate and 300g of aqueous solution are added into the reaction bottle while stirring, 39.47g of sodium chlorite and 300g of aqueous solution are added dropwise, and the temperature is controlled to be 20-30 ℃. After the dropwise addition, the reaction is carried out for 2 hours under room temperature stirring, reduced pressure distillation is carried out, the solvent is evaporated, 50g of concentrated hydrochloric acid is used for adjusting the pH value to be 2-3, a large amount of solid is separated out, 1000g of ethyl acetate is added, the solid is dissolved by stirring, the filtration is carried out, a filter cake is rinsed by 200g of ethyl acetate, liquid separation is carried out, an organic phase is washed twice by 300g of multiplied by 2 water, and the organic phase is evaporated, so that 75g of yellow solid is obtained, and the yield is: 69.65 percent.

Example 4

100g of 9-anthracenealdehyde, 2000g of isopropanol and 102.05g of 2-methyl-2-butene are added into a reaction flask, 151g of sodium dihydrogen phosphate and 300g of aqueous solution are added into the reaction flask under stirring, 131.59g of sodium chlorite and 300g of aqueous solution are added dropwise, and the temperature is controlled to be 20-30 ℃. After the dropwise addition, the reaction is carried out for 2 hours under room temperature stirring, reduced pressure distillation is carried out, the solvent is evaporated, 50g of concentrated hydrochloric acid is used for adjusting the pH value to be 2-3, a large amount of solid is separated out, 1000g of ethyl acetate is added, the solid is dissolved by stirring, filtration is carried out, a filter cake is rinsed by 200g of ethyl acetate, liquid separation is carried out, an organic phase is washed twice by 300g of multiplied by 2 water, and the organic phase is evaporated, so that 70.5g of yellow solid is obtained, and the yield is: 65.47 percent.

It is to be understood that the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and those skilled in the art may make modifications, alterations, additions or substitutions within the spirit and scope of the present invention.