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Method for preparing pyrogallol and phloroglucinol

A technology of pyrogallol and pyrogallol, applied in the field of marine chemical and pharmaceutical intermediates, can solve the problems of high price, large pollution and many influencing factors, achieve good activity and stability, reduce production costs, and facilitate industrialization Effect

Active Publication Date: 2014-04-30
SHOUGUANG FUKANG PHARMA +2
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0011] Trinitrotoluene (TNT) method is obtained by using trinitrotoluene as raw material through sodium dichromate oxidation (oxidation of methyl to carboxyl), high temperature decarboxylation, nitro reduction, diazotization, and hydrolysis, but due to trinitrotoluene Toluene (TNT) is an explosive, not easy to buy, and has the disadvantages of heavy metal chromium pollution and long steps
[0012] Disadvantages of the prior art: the preparation of pyrogallol by gallic acid is obtained by extracting gallic acid from the plant Galla, the source is scarce, the price is expensive, the market fluctuates greatly, and it also damages the environment, while the reaction temperature is high and the energy consumption is large;
[0013] The aniline method has a long route for the preparation of pyroglucinol, many influencing factors, insufficient production stability, and a large amount of copper sludge will be produced at the same time, causing great pollution
[0014] Trinitrotoluene (TNT) method prepares p-(homo)glucinol, because trinitrotoluene (TNT) is an explosive, it is not easy to buy, and there are heavy metal chromium pollution and long steps.

Method used

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  • Method for preparing pyrogallol and phloroglucinol
  • Method for preparing pyrogallol and phloroglucinol
  • Method for preparing pyrogallol and phloroglucinol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Embodiment 1: the synthesis of pyrogallol

[0032] Add 200g of 3,4,5-trimethoxybenzaldehyde, 300mL of tetrahydrofuran, and 6g of modified framework nickel into a 1L autoclave. After airtight, replace with nitrogen and hydrogen for 3 times respectively, fill with nitrogen to 2MPa, and then raise the temperature to 165 °C, adjust the pressure inside the kettle to 3.5 MPa, maintain this condition for 1.5 hours, and analyze by gas chromatography, the conversion rate of raw materials is 100%, and the selectivity of 1,2,3-trimethoxybenzene is 93%. The solution is extracted from the kettle, the catalyst is left in the kettle and washed with tetrahydrofuran for 2-3 times, the washed tetrahydrofuran is combined with the extracted solution, and the combined solution is rectified to collect 1,2,3-trimethoxybenzene fraction to obtain 155g, Yield 90.6%.

[0033] Add 50 g of 1,2,3-trimethoxybenzene, 220 g of aluminum trichloride, and 200 mL of chloroform into a 1000 mL three-neck fl...

Embodiment 2

[0035] The synthesis of embodiment 2 pyrogallol

[0036] Add 200g of 3,4,5-trimethoxybenzaldehyde, 300mL of cyclohexane, and 4g of modified framework nickel into a 1L autoclave, seal it and replace it with nitrogen and hydrogen for 3 times, fill it with nitrogen to 2MPa, and then raise the temperature To 165°C, adjust the pressure inside the kettle to 3.5 MPa, maintain this condition for 3 hours, sample gas chromatography analysis, the conversion rate of raw materials is 100%, and the selectivity of 1,2,3-trimethoxybenzene is 92%. Extract the solution from the kettle, leave the catalyst in the kettle and wash it with cyclohexane for 2-3 times, combine the washed cyclohexane with the extracted solution, and rectify the combined solution to collect 1,2,3-trimethoxybenzene The fraction was 152g, and the yield was 88.7%.

[0037] Add 50g of 1,2,3-trimethoxybenzene, 250g of aluminum trichloride, and 250mL of dichloromethane into a 1000mL three-neck flask with reflux condenser, dro...

Embodiment 3

[0038] Embodiment 3: the synthesis of pyroglucinol

[0039]Add 200g of 2,4,6-trimethoxybenzaldehyde, 300mL of cyclohexane, and 3g of modified framework nickel into a 1L autoclave, seal it and replace it with nitrogen and hydrogen for 3 times respectively, fill it with nitrogen to 2MPa, and then raise the temperature To 165°C, adjust the pressure inside the kettle to 3.5 MPa, maintain this condition for 4 hours, sample gas chromatography analysis, the conversion rate of raw materials is 100%, and the selectivity of 1,3,5-trimethoxybenzene is 95%. Extract the solution from the kettle, leave the catalyst in the kettle and wash it with cyclohexane for 2-3 times, combine the cyclohexane washing solution with the extracted solution, and rectify the combined solution to collect 1,3,5-trimethoxybenzene The fraction was 156g, and the yield was 90.9%.

[0040] Add 50g of 1,3,5-trimethoxybenzene, 240g of aluminum trichloride, and 300mL of chlorobenzene into a 1000mL three-neck flask equ...

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Abstract

The invention belongs to the field of marine chemical industry medicine intermediates, and particularly relates to a method for preparing pyrogallol and phloroglucinol, wherein the preparation route that trimethoxybenzaldehyde is subjected to catalysis decarbonylation under a hydrogen atmosphere is adopted, the modified raney nickel is adopted as a catalyst to carry out a catalysis decarbonylation reaction in a solvent, the modified raney nickel is subjected to bulk phase and surface modification based on the conventional raney nickel preparation method, the modified component is one or a plurality of materials selected from Mn, Fe, Cr, Mo, Ti and W, and the modified component content (wt) is 0.5-10 wt%. The method has characteristics of environmental protection, easy operation, wide raw material source, short reaction step, simple catalyst preparation and capability of being repeatedly applied multiple times, and is suitable for industrialization.

Description

technical field [0001] The invention belongs to the field of marine chemical pharmaceutical intermediates, and in particular relates to a method for preparing pyrogallol and pyrogallol. Background technique [0002] The method of removing functional groups of organic molecules is extremely important in chemical synthesis, especially in the synthesis of natural products. For a long time, many people engaged in chemical catalysis and organic synthesis have been working on the decarbonylation of aldehyde groups Research in this area, but they are only limited to the selection of noble metal (such as ruthenium, iridium, rhodium, etc.) .Ed.2012,51,8607-8610; A General and Convenient Method for the Rhodium-Catalyzed Decarbonylation of Aldehydes.Adv.Synth.Catal.2006,348,2148-2154, etc.), while British Mark A.Keane used Ni / SiO 2 The hydrogenolysis (decarbonylation) of benzaldehyde to benzene needs to be above 200°C, and the hydrogenolysis (decarbonylation) of methylbenzaldehyde ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C39/10C07C37/055
CPCC07C37/055C07C41/18C07C39/10C07C43/2055
Inventor 朱素圆董良军彼得·普劳克斯林文翰宋伟国杨磊
Owner SHOUGUANG FUKANG PHARMA
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