Synthesis method of 9-anthracene carboxylic acid

Abstract

The invention relates to the technical field of synthesis of dye intermediates and electronic fluorescent materials, and provides a novel synthesis method of 9-anthracene carboxylic acid. The synthesis method comprises the following steps of: taking 9-anthracene formaldehyde as a raw material, reacting under the action of an oxidizing agent, an auxiliary agent and a pH buffer agent, evaporating to remove a solvent after the reaction is completed, adjusting the pH to 1-5, extracting organic matters, and then evaporating to remove an organic phase, thereby obtaining 9-anthracene carboxylic acid. The problems of more by-products, low yield and the like in synthesis of 9-anthracene carboxylic acid in the prior art are solved. In synthesis, 9-anthracene formaldehyde is taken as a raw material, and reaction is performed under the action of an oxidizing agent, an auxiliary agent and a pH buffer agent. The prepared yellow solid is subjected to nuclear magnetic hydrogen spectrum identification and liquid chromatography detection, and results show that the structure of the prepared product is 9-anthracene carboxylic acid, and the purity can reach 99% or above, so that the synthesis method has the advantages of fewer by-products, easiness in purification, mild reaction conditions, simplicity in operation, stable product quality and suitability for industrial production.

Description

technical field

[0001] 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 technique

[0002] 9-Anthracenecarboxylic acid is used as a dye intermediate and electronic fluorescent material, and its structural formula is as follows:

[0003]

[0004] The current method of synthesizing 9-anthracene formic acid has the following reports:

[0005] GB2523811A reported that 9,10-dibromoanthracene was used as raw material, butyllithium was formed into lithium salt at -78°C, and then treated with dry ice to obtain 9-anthracenecarboxylic acid. This method is harsh and unsuitable for industrial production. The literature [Tetrahedron Letters, 2014, vol.55, #41, p.5671-5675] reported a method of synthesizing 9-anthracenecarboxylic acid by reacting 9-anthracenboronic acid and ethyl acetoacetate, with a yield of 87%. The method 9-anthracene b...

Examples

Embodiment 1

[0032] In the reaction flask, add 100g 9-anthracene formaldehyde, 1000g isopropanol, 50g 2-methyl-2-butene, add 113.5g sodium dihydrogen phosphate and 300g aqueous solution under stirring, add dropwise 68.6g sodium chlorite and 300g aqueous solution, temperature control 20-30°C. After the dropwise addition was completed, the reaction was stirred at room temperature for 2 h. After the reaction is completed, distill under reduced pressure, distill off the solvent, adjust the pH to 2-3 with 50g of concentrated hydrochloric acid, and precipitate a large amount of solids, add 1000g of ethyl acetate to stir to dissolve the solids, filter, rinse the filter cake with 200g of ethyl acetate, and separate the liquids , the organic phase was washed twice with 300 g×2 water, and the organic phase was evaporated to obtain 74.1 g of yellow solid, yield: 69.32%.

[0033] The prepared yellow solid was identified by proton nuclear magnetic spectrum, see figure 1 As shown, the results show tha...

Embodiment 2

[0037] In the reaction flask, add 100g 9-anthracene formaldehyde, 1500g isopropanol, 68g 2-methyl-2-butene, add 151g sodium dihydrogen phosphate and 300g aqueous solution under stirring, add dropwise 87g sodium chlorite and 300g aqueous solution , temperature control 20-30 ℃. After the dropwise addition, stir the reaction at room temperature for 2 hours, distill under reduced pressure, distill off the solvent, adjust the pH to 2-3 with 50 g of concentrated hydrochloric acid, and precipitate a large amount of solid, add 1000 g of ethyl acetate and stir to dissolve the solid, filter, and filter the cake with 200 g of ethyl acetate Rinse, separate liquid, wash the organic phase twice with 300 g×2 water, evaporate the organic phase to obtain 72 g of yellow solid, yield: 67.29%.

Embodiment 3

[0039] In the reaction flask, add 100g 9-anthracene formaldehyde, 1000g isopropanol, 34.02g 2-methyl-2-butene, add 151g sodium dihydrogen phosphate and 300g aqueous solution under stirring, add dropwise 39.47g sodium chlorite and 300g aqueous solution, temperature control 20-30°C. After the dropwise addition, stir the reaction at room temperature for 2 hours, distill under reduced pressure, distill off the solvent, adjust the pH to 2-3 with 50 g of concentrated hydrochloric acid, and precipitate a large amount of solid, add 1000 g of ethyl acetate and stir to dissolve the solid, filter, and filter the cake with 200 g of ethyl acetate Rinse, separate liquid, wash the organic phase twice with 300 g×2 water, evaporate the organic phase to obtain 75 g of yellow solid, yield: 69.65%.

technical field

[0001] 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 technique

[0002] 9-Anthracenecarboxylic acid is used as a dye intermediate and electronic fluorescent material, and its structural formula is as follows:

[0003]

[0004] The current method of synthesizing 9-anthracene formic acid has the following reports:

[0005] GB2523811A reported that 9,10-dibromoanthracene was used as raw material, butyllithium was formed into lithium salt at -78°C, and then treated with dry ice to obtain 9-anthracenecarboxylic acid. This method is harsh and unsuitable for industrial production. The literature [Tetrahedron Letters, 2014, vol.55, #41, p.5671-5675] reported a method of synthesizing 9-anthracenecarboxylic acid by reacting 9-anthracenboronic acid and ethyl acetoacetate, with a yield of 87%. The method 9-anthracene b...

Examples

Embodiment 1

[0032] In the reaction flask, add 100g 9-anthracene formaldehyde, 1000g isopropanol, 50g 2-methyl-2-butene, add 113.5g sodium dihydrogen phosphate and 300g aqueous solution under stirring, add dropwise 68.6g sodium chlorite and 300g aqueous solution, temperature control 20-30°C. After the dropwise addition was completed, the reaction was stirred at room temperature for 2 h. After the reaction is completed, distill under reduced pressure, distill off the solvent, adjust the pH to 2-3 with 50g of concentrated hydrochloric acid, and precipitate a large amount of solids, add 1000g of ethyl acetate to stir to dissolve the solids, filter, rinse the filter cake with 200g of ethyl acetate, and separate the liquids , the organic phase was washed twice with 300 g×2 water, and the organic phase was evaporated to obtain 74.1 g of yellow solid, yield: 69.32%.

[0033] The prepared yellow solid was identified by proton nuclear magnetic spectrum, see figure 1 As shown, the results show tha...

Embodiment 2

[0037] In the reaction flask, add 100g 9-anthracene formaldehyde, 1500g isopropanol, 68g 2-methyl-2-butene, add 151g sodium dihydrogen phosphate and 300g aqueous solution under stirring, add dropwise 87g sodium chlorite and 300g aqueous solution , temperature control 20-30 ℃. After the dropwise addition, stir the reaction at room temperature for 2 hours, distill under reduced pressure, distill off the solvent, adjust the pH to 2-3 with 50 g of concentrated hydrochloric acid, and precipitate a large amount of solid, add 1000 g of ethyl acetate and stir to dissolve the solid, filter, and filter the cake with 200 g of ethyl acetate Rinse, separate liquid, wash the organic phase twice with 300 g×2 water, evaporate the organic phase to obtain 72 g of yellow solid, yield: 67.29%.

Embodiment 3

[0039] In the reaction flask, add 100g 9-anthracene formaldehyde, 1000g isopropanol, 34.02g 2-methyl-2-butene, add 151g sodium dihydrogen phosphate and 300g aqueous solution under stirring, add dropwise 39.47g sodium chlorite and 300g aqueous solution, temperature control 20-30°C. After the dropwise addition, stir the reaction at room temperature for 2 hours, distill under reduced pressure, distill off the solvent, adjust the pH to 2-3 with 50 g of concentrated hydrochloric acid, and precipitate a large amount of solid, add 1000 g of ethyl acetate and stir to dissolve the solid, filter, and filter the cake with 200 g of ethyl acetate Rinse, separate liquid, wash the organic phase twice with 300 g×2 water, evaporate the organic phase to obtain 75 g of yellow solid, yield: 69.65%.

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