CN-121990879-A - Novel process for efficiently preparing pyrogallic acid

Abstract

The invention belongs to the field of new fine chemical materials, and realizes the efficient preparation of pyrogallic acid under the action of carboxylate by taking tetrahalogen cyclohexanone as a raw material.

Inventors

• ZHANG DONGJING
• Xing Xiangyou
• JIN MINGYU
• YANG PENGZHI
• WANG ZHIGANG

Assignees

• 深圳有为技术控股集团有限公司
• 南方科技大学

Dates

Publication Date

20260508

Application Date

20241106

Claims (5)

1. 1. A preparation process technology of pyrogallic acid is disclosed, which is shown in a reaction formula (I), wherein tetrahalo cyclohexanone A is used as a raw material, and a carboxylate environment is reacted under Conditions to obtain pyrogallic acid C. Wherein X is halogen atom, namely one of F, cl, br and I, R is hydrogen atom or alkyl, alkenyl, alkynyl or aromatic group with 1-24 carbon atoms, M is alkaline earth metal ion or alkaline group with alkaline property, n is charge number of metal ion or alkaline group, and the reaction condition conditions are at least one of solvent, additive, temperature and pressure (or vacuum).
2. 2. According to claim (1), the carboxylate system B is a mixed system of single or multiple carboxylates including, but not limited to, sodium carboxylate, potassium carboxylate, calcium carboxylate, zinc carboxylate, magnesium carboxylate, cesium carboxylate, lithium carboxylate, ammonium carboxylate, and the feed ratio of carboxylate B to tetrahalo cyclohexanone a is 0.01:1-1000:1.
3. 3. According to the method (1), the reaction yield shown in the formula (I) can be effectively improved by adding an acidic additive into the reaction system to prepare a buffer system, wherein the acidic additive is inorganic acid or saturated or unsaturated carboxylic acid with 1-24 carbon atoms, including but not limited to formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, adipic acid, hydrochloric acid, sulfuric acid and phosphoric acid, and the feeding ratio of the acidic additive to the tetrachlorocyclohexanone A is 0.01:1-1000:1.
4. 4. According to claim (1), the solvent is water, substituted or unsubstituted aromatic hydrocarbon, straight-chain or branched aliphatic hydrocarbon, (sub) sulfone, amide, ether, alcohol, ester, ketone, carboxylic acid, amine, carbonate, ionic liquid, supercritical fluid or a mixed system of the solvent and water, wherein the solvent is used in an amount of 1-1000 times (mass ratio) that of tetrahalo cyclohexanone.
5. 5. According to claim (1), the temperature of the reaction condition conditions is 40 ℃ to 400 ℃.

Description

Novel process for efficiently preparing pyrogallic acid [ Field of technology ] The invention belongs to the field of new fine chemical materials, and realizes the efficient preparation of pyrogallic acid by taking tetrahalo cyclohexanone as a raw material in the buffer system environment such as carboxylate and the like. [ Background Art ] Pyrogallic acid (Pyrogallic Acid), also known as pyrogallol, has the appearance of white light-colored crystalline powder. The method is widely applied to industries such as fine chemical engineering, novel photosensitive materials, food fresh-keeping, new drugs for treating cardiovascular and cerebrovascular diseases, new drugs for resisting tumors, drugs for treating senile dementia, drugs for treating mental disorder, textile printing and dyeing, light industrial daily chemicals, color printing plate making, microelectronic industry, rare metal analysis, gas analysis, photographic development and the like. The existing preparation process of pyrogallic acid mainly comprises (1) decarboxylation of gallic acid obtained from gallnut tannin or tara tannin by chemical processing of forest products under heating to generate pyrogallic acid, and the decarboxylation methods commonly adopted in industry at present are biological decarboxylation, normal pressure catalytic decarboxylation and reduced pressure catalytic decarboxylation. The method comprises the steps of (1) preparing pyrogallic acid from natural gallnut serving as a raw material by using glutarate (complicated steps, dangerous processes, corrosion equipment and the like), tetrachlorocyclohexanone (sulfur dioxide environmental pollution, corrosion equipment, a large amount of solid wastes, difficult catalyst recovery and the like), cyclohexene (heavy metal participation and difficult separation), resorcinol (low yield, more byproducts and difficult separation) and p-tert-butylphenol (bromine process and longer route) serving as raw materials, wherein the pyrogallic acid is prepared only in a laboratory research and development stage, has obvious amplification effect and is high in cost. At present, the two main technological methods cannot realize mass production. Aiming at the problems, the method has the advantages that tetrahalo cyclohexanone is used as a raw material, the process is changed in a buffer system environment, the high-efficiency preparation of pyrogallic acid is realized in one step, the method has mild conditions, less solid waste, low cost and high product purity, the test result is matched with the published result, and a foundation is laid for subsequent large-scale production. [ Invention ] The application has now surprisingly found that the efficient preparation of pyrogallic acid C can be achieved with tetrahalo cyclohexanone a and carboxylate B under Conditions as shown in reaction formula (i): Wherein X is halogen atom, namely one of F, cl, br and I, R is hydrogen atom or alkyl, alkenyl, alkynyl or aromatic group with 1-24 carbon atoms, M is alkaline earth metal ion or alkaline group with alkaline property, n is charge number of metal ion or alkaline group, and the reaction condition conditions are at least one of solvent, additive, temperature and pressure (or vacuum). Carboxylate B is a mixed system of single or multiple carboxylates, including but not limited to sodium carboxylate, potassium carboxylate, calcium carboxylate, zinc carboxylate, cesium carboxylate, lithium carboxylate, ammonium carboxylate, and the feeding ratio of carboxylate B to tetrahalo cyclohexanone A is 0.01:1-1000:1, preferably 4:1-30:1. The reaction yield shown in the formula (I) can be effectively improved by adding an acidic additive into a reaction system to prepare a buffer system, wherein the acidic additive is inorganic acid or saturated or unsaturated carboxylic acid with 1-24 carbon atoms, including but not limited to formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, adipic acid, hydrochloric acid, sulfuric acid and phosphoric acid, and the feeding ratio of the acidic additive to the tetrachlorocyclohexanone A is 0.01:1-1000:1, preferably 1:1-20:1. In some preferred embodiments of the present invention, the solvent is selected from at least one of water, acetonitrile, methanol, ethanol, butanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, dimethyl sulfone, benzyl sulfoxide, benzyl sulfone, cyclobutylsulfoxide, sulfolane, trichlorosilane, methylene chloride, chloroform, dichloroethane, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, chloroform, carbon tetrachloride, benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, acetonitrile, ethylbenzene, diethylbenzene, chlorobenzene, dichlorobenzene, anisole, nitrobenzene, heptane, hexane, petroleum ether, dioxane, tetrahydrofuran, methyltetrahydrofuran, methyl tert-butyl ether, ethylene glycol dimethyl ether, propylene glycol methyl ether acetate, triethylamine, tribu