CN1266109C - Technique for prepring 3,4,5-trihydroxybenzoic acid methyl ester - Google Patents
Technique for prepring 3,4,5-trihydroxybenzoic acid methyl ester Download PDFInfo
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- CN1266109C CN1266109C CN 02139739 CN02139739A CN1266109C CN 1266109 C CN1266109 C CN 1266109C CN 02139739 CN02139739 CN 02139739 CN 02139739 A CN02139739 A CN 02139739A CN 1266109 C CN1266109 C CN 1266109C
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Abstract
The present invention relates to a preparation technology for 3, 4, 5-trihydroxybenzoic acid methyl ester. Gallic acid, methanol and a catalyst are put in a reaction kettle to be heated and esterified, generated water and a methanol vapour mixture enter a rectifying tower connected with the reaction kettle to be separated, and a refluxing ratio R is controlled to 1 to 4 to keep tower top temperature between 64.5 to 66.5 DEG C; the distilled methanol returns the reaction kettle to continue carrying out a reaction, moisture contents enter a water separator connected to the lower part of the rectifying tower, and after an esterification reaction is carried out for 8 to 14 hours, a reaction material is filtered and cooled to obtain a coarse crystal; the obtained coarse crystal is filtered, washed by water and recrystallized to obtain the 3, 4, 5-trihydroxybenzoic acid methyl ester. The preparation technology of the present invention has the advantages of simple technology, low requirements for equipment and technical conditions, low production cost, low three waste discharge and favorable effects of high quality and high yield.
Description
Technical field
The present invention relates to a kind of 3,4, the preparation technology of 5-trihydroxybenzoic acid methyl esters.
Background technology
3,4,5 trihydroxybenzoic acid methyl esters are also referred to as methyl gallate, it is a kind of important source material in the medicine industry, also be a kind of good oxidation inhibitor simultaneously, in chemical industry, light industry, foodstuffs industry, be widely used, synthetic as the low-carbon-ester of gallic acid is to be catalyzer with sulfuric acid or tosic acid than classic methods, makes gallic acid and corresponding lower alcohol carry out esterification, the water that generates in the reaction process adopts water-retaining agent or azeotropic aqua to get rid of.Methyl gallate is not seen preparation method's report, because the methyl alcohol boiling point is low, can not adopt azeotropic aqua to dewater, but can adopt water-retaining agent, as water-retaining agents such as Calcium Chloride Powder Anhydrous, calcium sulfate or molecular sieves, in dehydration, water-retaining agent also can adsorb a large amount of methyl alcohol, has increased production cost; And methyl alcohol is poisonous Chemicals, must reduce discharging and leakage during production to greatest extent, has therefore increased the difficulty of sorbent treatment.
Summary of the invention
It is easy that purpose of the present invention aims to provide a kind of technology, and equipment and technical qualification are less demanding, can reduce production costs again, reduces three waste discharge, and can obtain 3,4 of good quality and high output effect, the preparation technology of 5-trihydroxybenzoic acid methyl esters.
Processing method of the present invention is for to put into gallic acid, methyl alcohol, catalyzer in the reactor, esterification heats up in reactor, the water that generates and methanol vapor mixture enter in the rectifying tower that reactor links to each other and separate, control reflux ratio R=1-4, make tower top temperature remain on 64.5-66.5 ℃, distilled methyl alcohol returns and continues reaction in the reactor, moisture then enters in the water trap that the rectifying tower bottom is connected with, after esterification 8-14 hour, reaction mass is filtered, and cooling, the filtration of gained coarse-grain, washing, recrystallization get final product.
Described catalyzer is that mixed catalyst can be sulfuric acid, tosic acid, gac or phosphoric acid, tosic acid, gac or phosphoric acid, gac.
Described mixed catalyst consumption is the 6-15% of gallic acid weight, and preferred amounts is 9%.
Sulfuric acid: tosic acid: the weight proportion between the gac is 4-12: 6-17: 1; Tosic acid: phosphoric acid: the weight proportion between the gac is 5-15: 1-5: 1-3; Phosphoric acid: the gac weight proportion is 4-12: 1.
The mixed catalyst preferably combination is phosphoric acid, tosic acid, gac, and the weight proportion scope between the three is 1-1.5: 7-9: 1-1.5.
Used gallic acid is a water gallic acid.
The feed ratio of described gallic acid and methyl alcohol is: weight g: volume ml=1: 2-1: 4, and preferable amount is 1: 3.5.
The temperature of esterification is controlled at 65-80 ℃, preferred 68-76 ℃.
The esterification Best Times is 10-12 hour.
Control water trap liquid level is not wanted too high liquid level and was not played 1/3 of water trap height.
Described rectifying tower has 8-20 theoretical tray.
Because technological process of the present invention need not to use band aqua and water-retaining agent, the gained coarse-grain gets final product highly purifiedly 3,4,5-trihydroxybenzoic acid methyl esters after the simple process.And the distillation that the present invention uses divides the water conservancy project skill, and after esterification finished, after methyl alcohol was reclaimed in the aqueous solution rectifying in the water trap, raffinate discarded, and the discharging of methyl alcohol and spillage are very little, do not have the difficulty of water-retaining agent aftertreatment.
Mixed catalyst used in the present invention, has good catalytic performance, and do not have strong oxidizing property, therefore the colourity of gained coarse-grain after washing is very good, can remove back step bleaching process from, mixed catalyst has good complex ability simultaneously, except that katalysis is arranged, can also effectively remove metal ion in the material.Therefore to have technology easy in the present invention, and equipment and technical qualification are less demanding, but have advantages such as three wastes discharge amount is little simultaneously, and industrial application value is higher.
The catalyzer that the present invention reclaims can not done any processing, directly applies mechanically for next manufacturing processed esterification, and the catalyst attrition part only need be made small amount of supplemental and get final product, and catalyst consumption is very little, and production cost is low; And reduced the quantity discharged of the three wastes.
Finished product after testing, chromatic number＜20
#, fusing point: 200.5-201.5 ℃, content (HPLC):＞99%.
The methyl gallate productive rate reaches 93%.
Rectifying tower of the present invention middle and lower part is by opening for feed, link to each other with reaction kettle of the esterification by pipeline, the bottom of the rectifying tower water trap of ining succession, the top links to each other with condenser, the bottom of condenser links to each other with an end of reflux splitter simultaneously, a shunting of reflux splitter flows to the top of packing tower, and another shunting flows to reaction kettle of the esterification.Have feeding-in solid body mouth and electric mixing device on the reaction kettle of the esterification.
Embodiment:
Embodiment 1:
The liquid starting material that is contained in head tank is imported elevated dosing vessel by transferpump, enters reactor, and solid material is then directly added by the charging opening on the reactor.Get gallic acid 100 grams in the present embodiment, 200 milliliters of methyl alcohol, mixed catalyst are got 15 grams altogether, and it adopts tosic acid, phosphoric acid and gac formulated, and the weight proportion that adopts between the three is 15: 1: 1.After in material drops into reactor, the esterification that promptly heats up, esterification temperature keeps 68 ℃, the steam that comprises water and methyl alcohol component that reaction kettle of the esterification is evaporated, in rectifying tower, separate, control reflux ratio R=1-4 makes tower top temperature remain on 64.5 ℃, overhead vapours through condenser condenses after reflux splitter, a part flows back to rectifying tower, another part flows into reaction kettle of the esterification to be continued to recycle, and moisture is enriched in the water trap after packing tower separates.After the esterification 14 hours, reclaim excessive methyl alcohol by rectifying tower, reaction mass filters, and unnecessary methyl alcohol is reclaimed in distillation, cooling, crystallization, filtration, and catalyzer can be standby for next manufacturing processed esterification, and the catalyst attrition part is replenished by optimizing consumption.Crystallizing and washing gets the methyl gallate crude product.The crude product recrystallization, gained is smart brilliant, and it is dry that finished product 90 restrains to dry final vacuum.
Embodiment 2-9
Reactions steps is with embodiment 1, and following table one is for adopting different ratios of raw materials, mixed catalytic agent content, and under the condition such as reaction times, the amount of gained methyl gallate finished product.Catalyzer all adopts tosic acid: phosphoric acid: gac is formulated, and three's weight proportion of embodiment 2-3 is 15: 1: 1, among the embodiment 4-6 between the three weight proportion be 8: 1: 2, three's weight proportion is 5: 1: 2 among the embodiment 7-9.
| Embodiment | Raw material | Operational condition | Finished product g | ||||
| Gallic acid g | Methyl alcohol ml | Mixed catalyst g | Reaction times h | Esterification temperature ℃ | Filler tower top temperature ℃ | ||
| 2 | 100 | 200 | 6 | 10 | 76 | 66.5 | 89.5 |
| 3 | 100 | 200 | 10.5 | 12 | 72 | 65 | 89.5 |
| 4 | 100 | 350 | 10.5 | 12 | 72 | 65 | 93 |
| 5 | 100 | 350 | 6 | 14 | 68 | 64.5 | 90 |
| 6 | 100 | 350 | 15 | 10 | 76 | 66.5 | 91.5 |
| 7 | 100 | 400 | 15 | 10 | 76 | 66.5 | 93 |
| 8 | 100 | 400 | 10.5 | 12 | 72 | 65 | 93 |
| 9 | 100 | 400 | 6 | 14 | 68 | 64.5 | 89.5 |
Embodiment 10-13
Reactions steps is with embodiment 1, and mixed catalyst is sulfuric acid, tosic acid, gac, and the weight proportion between the three is, embodiment 10 is 12: 17: 1, and embodiment 11 is 4: 6: 1, and embodiment 12,13 is 4: 4: 1.
| Embodiment | Raw material | Operational condition | Finished product g | |||||
| Gallic acid g | Methyl alcohol ml | Mixed catalyst g | Reclaim catalyzer g | Reaction times h | Esterification temperature ℃ | Filler tower top temperature ℃ | ||
| 10 | 200 | 800 | 30 | - | 8 | 72-78 | 64.5-66 | 176 |
| 11 | 200 | 800 | 22 | - | 12 | 72-76 | 64.5-66 | 179 |
| 12 | 200 | 700 | 18 | - | 14 | 72-76 | 65.5-66 | 177.4 |
| 13 | 300 | 1250 | 12 | 14.5 | 12 | 72-76 | 64.5-66 | 270 |
Embodiment 14-18
Reactions steps is with embodiment 1.Mixed catalyst is formulated by phosphoric acid and gac, and the weight proportion of embodiment 14-18 was respectively 6: 1,8: 1,4: 1; 10: 1 and 7: 1.
| Embodiment | Raw material | Operational condition | Finished product g | ||||
| Gallic acid g | Methyl alcohol ml | Mixed catalyst g | Reaction times h | Esterification temperature ℃ | Filler tower top temperature ℃ | ||
| 14 | 100 | 300 | 6 | 8 | 72-78 | 64.5-66 | 82 |
| 15 | 100 | 200 | 10 | 12 | 72-76 | 64.5-66 | 85 |
| 16 | 100 | 400 | 15 | 14 | 72-76 | 65.5-66 | 87 |
| 17 | 100 | 350 | 12 | 14 | 72-78 | 65-66 | 87 |
| 18 | 100 | 350 | 12 | 10 | 72-76 | 64.5-66 | 85 |
Embodiment 19-22
Reactions steps is with embodiment 1.Mixed catalyst adopts tosic acid, phosphoric acid and gac formulated, and its weight proportion is 7: 1: 1.The methyl gallate productive rate reaches 93.2%.
| Embodiment | Raw material | Operational condition | Reclaim | ||||||
| Gallic acid g | Methyl alcohol ml | Mixed catalyst g | Reclaim catalyzer g | Reaction times h | Esterification temperature ℃ | Filler tower top temperature ℃ | Methyl alcohol ml | Finished product g | |
| 19 | 250 | 750 | 26.5 | - | 12 | 72-76 | 64.5-66 | 680 | 232 |
| 20 | 300 | 1050 | 8.5 | 20 | 12 | 72-76 | 64.5-66 | 970 | 281.5 |
| 21 | 300 | 1250 | 12 | 14.5 | 12 | 72-76 | 64.5-66 | 1170 | 277 |
| 22 | 400 | 1200 | 10 | 17 | 12 | 72-76 | 64.5-66 | 1050 | 376 |
Claims (9)
1,3,4,5-trihydroxybenzoic acid methyl esters preparation technology, its processing method is with gallic acid, methyl alcohol, catalyzer is put in the reactor, esterification heats up in reactor, the water that generates and methanol vapor mixture enter in the rectifying tower that reactor links to each other and separate, control reflux ratio R=1-4, make tower top temperature remain on 64.5-66.5 ℃, distilled methyl alcohol returns and continues reaction in the reactor, and moisture then enters in the water trap that the rectifying tower bottom is connected with, after esterification 8-14 hour, reaction mass is filtered cooling, the gained coarse-grain filters, washing, recrystallization gets final product; Described catalyzer is the mixture of the mixture of the mixture of sulfuric acid, tosic acid, gac or phosphoric acid, tosic acid, gac or phosphoric acid, gac, and catalyst levels is the 6-15% of gallic acid weight.
2, according to claim 13,4,5-trihydroxybenzoic acid methyl esters preparation technology, sulfuric acid in the described catalyzer: tosic acid: the weight proportion between the gac is 4-12: 6-17: 1 or tosic acid: phosphoric acid: the weight proportion between the gac is 5-15: 1-5: 1-3 or phosphoric acid: the weight proportion of gac is 4-12: 1.
3, according to claim 1 and 23,4,5-trihydroxybenzoic acid methyl esters preparation technology, catalyzer is phosphoric acid, tosic acid, gac, the weight proportion scope between the three is 1-1.5: 7-9: 1-1.5.
4, according to claim 13,4,5-trihydroxybenzoic acid methyl esters preparation technology, the feed ratio of described gallic acid and methyl alcohol is: weight g: volume ml=1: 2-1: 4.
5, according to claim 13,4,5-trihydroxybenzoic acid methyl esters preparation technology, the feed ratio of described gallic acid and methyl alcohol is: weight g: volume ml=1: 3.5.
6, according to claim 13,4,5-trihydroxybenzoic acid methyl esters preparation technology, the temperature of esterification is controlled at 65-80 ℃.
7, according to claim 13,4,5-trihydroxybenzoic acid methyl esters preparation technology, the temperature of esterification is controlled at 68-76 ℃.
8, according to claim 13,4,5-trihydroxybenzoic acid methyl esters preparation technology, reaction time of esterification is 10-12 hour.
9, according to claim 13,4,5-trihydroxybenzoic acid methyl esters preparation technology, described rectifying tower has 8-20 theoretical tray.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02139739 CN1266109C (en) | 2002-11-05 | 2002-11-05 | Technique for prepring 3,4,5-trihydroxybenzoic acid methyl ester |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02139739 CN1266109C (en) | 2002-11-05 | 2002-11-05 | Technique for prepring 3,4,5-trihydroxybenzoic acid methyl ester |
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| CN1498883A CN1498883A (en) | 2004-05-26 |
| CN1266109C true CN1266109C (en) | 2006-07-26 |
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| CN 02139739 Expired - Lifetime CN1266109C (en) | 2002-11-05 | 2002-11-05 | Technique for prepring 3,4,5-trihydroxybenzoic acid methyl ester |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948387A (en) * | 2010-08-30 | 2011-01-19 | 安徽佳先功能助剂股份有限公司 | Preparation technology of methyl benzoate |
| CN102229533A (en) * | 2011-04-28 | 2011-11-02 | 贵阳单宁科技有限公司 | Method for synthesizing electronic-grade gallicin |
| CN102964252A (en) * | 2012-11-27 | 2013-03-13 | 湖南先伟实业有限公司 | Technology for preparing propyl gallate by utilizing mixed catalyst |
| CN103193651A (en) * | 2013-04-12 | 2013-07-10 | 张家港威胜生物医药有限公司 | Synthesis of medical intermediate 3,5-dihydroxy methyl benzoate and industrial production process |
| CN104086416A (en) * | 2014-07-25 | 2014-10-08 | 遵义林源医药化工有限责任公司 | Synthesis method of ethyl gallate |
| CN107034024A (en) * | 2017-05-11 | 2017-08-11 | 唐山金利海生物柴油股份有限公司 | A kind of production technology of the biodiesel of high oxidation stability |
| CN112745217A (en) * | 2020-12-30 | 2021-05-04 | 湖南先伟实业有限公司 | Propyl gallate preparation process |
| CN115582115B (en) * | 2022-10-18 | 2024-03-01 | 陕西煤业化工技术研究院有限责任公司 | Catalyst, device and method for preparing methyl o-methylbenzoate |
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Effective date of registration: 20170526 Address after: 410000, No. 118, intersection of Huanghua Industrial Park, Changsha, Hunan, Changsha County Patentee after: HUNAN SHINEWAY ENTERPRISE Co.,Ltd. Address before: 410001, Hunan, Changsha agricultural road, No. 378, South Bank branch, four floor office Patentee before: Luo Wei |
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Effective date of registration: 20211201 Address after: 416117 interchange of Changji expressway, Wuxi Town, Luxi County, Xiangxi Tujia and Miao Autonomous Prefecture, Hunan Province (in Wuling Sunshine Biotechnology Co., Ltd.) Patentee after: Hunan Xianwei sunshine Biotechnology Co.,Ltd. Address before: 410000 No. 118, airport intersection, Huanghua Industrial Park, Changsha County, Changsha City, Hunan Province Patentee before: HUNAN SHINEWAY ENTERPRISE Co.,Ltd. |
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