CN113582841A - Preparation method and product of 3,4, 5-trimethoxybenzoic acid methyl ester - Google Patents
Preparation method and product of 3,4, 5-trimethoxybenzoic acid methyl ester Download PDFInfo
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- CN113582841A CN113582841A CN202110977204.0A CN202110977204A CN113582841A CN 113582841 A CN113582841 A CN 113582841A CN 202110977204 A CN202110977204 A CN 202110977204A CN 113582841 A CN113582841 A CN 113582841A
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- dimethyl carbonate
- hydrolysate
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- caustic soda
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- KACHFMOHOPLTNX-UHFFFAOYSA-N Methyl EudesMate Chemical compound COC(=O)C1=CC(OC)=C(OC)C(OC)=C1 KACHFMOHOPLTNX-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 72
- 239000000047 product Substances 0.000 claims abstract description 36
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 24
- 239000000413 hydrolysate Substances 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 19
- 235000017399 Caesalpinia tinctoria Nutrition 0.000 claims abstract description 17
- 241000388430 Tara Species 0.000 claims abstract description 17
- 230000007062 hydrolysis Effects 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 12
- 238000005886 esterification reaction Methods 0.000 claims abstract description 11
- 230000032050 esterification Effects 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 108010009736 Protein Hydrolysates Proteins 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 238000007069 methylation reaction Methods 0.000 claims description 12
- 230000011987 methylation Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- YJWGKXIQTRYZSH-UHFFFAOYSA-N 2,4-diiodoaniline Chemical compound NC1=CC=C(I)C=C1I YJWGKXIQTRYZSH-UHFFFAOYSA-N 0.000 claims description 7
- UEOFNBCUGJADBM-UHFFFAOYSA-N Trimethylaethergallussaeure-aethylester Natural products CCOC(=O)C1=CC(OC)=C(OC)C(OC)=C1 UEOFNBCUGJADBM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- SJSOFNCYXJUNBT-UHFFFAOYSA-N 3,4,5-trimethoxybenzoic acid Chemical compound COC1=CC(C(O)=O)=CC(OC)=C1OC SJSOFNCYXJUNBT-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 abstract description 8
- 208000005374 Poisoning Diseases 0.000 abstract description 2
- 231100000572 poisoning Toxicity 0.000 abstract description 2
- 230000000607 poisoning effect Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 description 18
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 235000004515 gallic acid Nutrition 0.000 description 5
- 229940074391 gallic acid Drugs 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 235000007627 Caesalpinia Nutrition 0.000 description 2
- 241000522234 Caesalpinia Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- ABUKTBFSGLUCCG-YGKCYCOQSA-N (3r)-4-[3-[3,4-dihydroxy-5-(3,4,5-trihydroxybenzoyl)oxybenzoyl]oxy-4,5-dihydroxybenzoyl]oxy-1-hydroxy-3,5-bis[(3,4,5-trihydroxybenzoyl)oxy]cyclohexane-1-carboxylic acid Chemical compound C([C@H](C1OC(=O)C=2C=C(OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)C(O)=C(O)C=2)OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(C(=O)O)(O)CC1OC(=O)C1=CC(O)=C(O)C(O)=C1 ABUKTBFSGLUCCG-YGKCYCOQSA-N 0.000 description 1
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- IWPZKOJSYQZABD-UHFFFAOYSA-N 3,4,5-trimethoxybenzoic acid Natural products COC1=CC(OC)=CC(C(O)=O)=C1 IWPZKOJSYQZABD-UHFFFAOYSA-N 0.000 description 1
- LORDFXWUHHSAQU-UHFFFAOYSA-N 3,4,5-trimethoxybenzoic acid [2-(dimethylamino)-2-phenylbutyl] ester Chemical compound C=1C=CC=CC=1C(CC)(N(C)C)COC(=O)C1=CC(OC)=C(OC)C(OC)=C1 LORDFXWUHHSAQU-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- UHWVSEOVJBQKBE-UHFFFAOYSA-N Trimetazidine Chemical compound COC1=C(OC)C(OC)=CC=C1CN1CCNCC1 UHWVSEOVJBQKBE-UHFFFAOYSA-N 0.000 description 1
- 239000002249 anxiolytic agent Substances 0.000 description 1
- 230000000949 anxiolytic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 229960005345 trimebutine Drugs 0.000 description 1
- 229960001177 trimetazidine Drugs 0.000 description 1
- IEDVJHCEMCRBQM-UHFFFAOYSA-N trimethoprim Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(N)=NC=2)N)=C1 IEDVJHCEMCRBQM-UHFFFAOYSA-N 0.000 description 1
- 229960001082 trimethoprim Drugs 0.000 description 1
- FBGCNHGVKQWUHV-UHFFFAOYSA-N trimethoxymethyl benzoate Chemical compound COC(OC)(OC)OC(=O)C1=CC=CC=C1 FBGCNHGVKQWUHV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
- C07C69/92—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with etherified hydroxyl groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method for directly producing 3,4, 5-trimethoxybenzoic acid methyl ester by using tara powder hydrolysate, which comprises the following steps of (1) adding dimethyl carbonate into the tara hydrolysate; adding liquid caustic soda for hydrolysis; and step two, adding dimethyl carbonate for esterification to obtain the product. The invention uses dimethyl carbonate to replace dimethyl sulfate, reduces the risk of poisoning in production and lays a foundation for safe production.
Description
Technical Field
The invention relates to the field of chemistry, in particular to a preparation method and a product for directly producing 3,4, 5-trimethoxybenzoic acid methyl ester by using tara powder hydrolysate.
Background
Methyl 3,4, 5-trimethoxybenzoate is used as the main material of antibiotic synergist trimethoprim as medicine intermediate, anxiolytic trimetazidine, and gastrointestinal maleic trimebutine.
The prior art in the industry is prepared by the methylation reaction of gallic acid and dimethyl sulfate. Adding water, gallic acid and dimethyl sulfate into a reaction kettle, dripping sodium hydroxide solution at 15-35 deg.C, and stirring at about 40 deg.C for half an hour. Then adding a second batch of dimethyl sulfate, and dropwise adding a sodium hydroxide solution at about 40 ℃ until the pH value is 8-9. And (3) continuously reacting for 1h, cooling, filtering, washing and drying to obtain the trimethoxy methyl benzoate with the yield of over 90 percent. The methylation and esterification reaction can also adopt tannic acid as a raw material or be prepared by esterifying 3,4, 5-trimethoxybenzoic acid and methanol.
In the prior art, raw materials such as dimethyl sulfate and the like are adopted, wherein the dimethyl sulfate belongs to high toxicity. Has strong irritation and corrosiveness and has delayed biological effect. Can be burnt by heat, open fire or oxidant. The existing preparation method is not environment-friendly, has high cost, is difficult to produce in a large scale and can not meet the ever-increasing market demand of medical intermediates.
Disclosure of Invention
The invention mainly solves the technical problems that the production method of methyl 3,4, 5-trimethoxybenzoate in the prior art is unsafe, not environment-friendly, has high cost, is difficult to produce in a large scale and cannot meet the increasing market demand.
In order to solve the technical problem, the technical scheme is as follows: the preparation method for directly producing 3,4, 5-trimethoxybenzoate from tara powder hydrolysate comprises the following steps:
adding dimethyl carbonate into the tower-pulling hydrolysate;
adding liquid caustic soda for hydrolysis;
and step two, adding dimethyl carbonate for esterification to obtain the product.
Introduction of a main raw material tara powder; tara also called spine caesalpinia, spine bean, is an evergreen shrub with thorns or small arbor of caesalpinia family, and is a precious economic plant distributed in south america peru, chile, bolivia, ecuador and other countries; the plants are planted in China in Yunnan, Guangxi, Guizhou, Sichuan and other places in large scale. Tara tannin belongs to hydrolyzed tannin and is widely used in chemical industry, medical raw materials, animal feed and the like.
Further, the preparation method comprises the following steps:
adding tara powder into liquid caustic soda for hydrolysis to obtain hydrolysate;
adding dimethyl carbonate into the hydrolysate;
adding liquid caustic soda for hydrolysis after the step two;
fourthly, adding dimethyl carbonate to esterify after the third step.
Further, the steps further include: dissolving the esterified methanol, adding active carbon, filtering, crystallizing and centrifuging.
Further, the steps further include: drying and sieving.
In the invention, in the step (i), the mass-to-volume ratio of the tala powder to the liquid caustic soda is 1:1, and the liquid caustic soda and the tala powder are added, wherein in one specific embodiment of the invention, the ratio of the tala powder to the liquid caustic soda is 1: 1.
in the invention, in the step I, the volume is L; the mass is kg.
In the second step of the invention, the volume ratio of the hydrolysate to the dimethyl carbonate is 550:300, and in one specific embodiment of the invention, the volume ratio is 550: 300.
according to the invention, the content of the alkali liquor is 30-32wt%, preferably 32 wt%.
In the invention, the step II comprises the step of regulating the PH, wherein the PH is 7.5-9: in one embodiment of the invention, the pH is 8.5 to 9; and/or the step (iv) comprises adjusting the pH value to be 7.5-9: in one embodiment of the invention the pH is from 8.5 to 9.
The invention comprises the following steps:
adding 550L of liquid caustic soda, adding 550kg of Tara powder, heating to 110-115 ℃, preserving heat for 1 hour, and filtering to obtain 550L of hydrolysate;
adding 300L dimethyl carbonate into the hydrolysate, controlling the temperature at 80-85 ℃ and the pH value at 8.5-9 for methylation, keeping the pH value unchanged, and keeping the temperature for 20-30 minutes, preferably 30 minutes;
adding 200L of liquid caustic soda after the step II, controlling the temperature at 102 ℃ and 105 ℃ for hydrolysis for 1-1.5 hours, preferably for 1.5 hours;
fourthly, adding 200L of dimethyl carbonate after the third step, controlling the temperature at 40-50 ℃ and the PH value at 8.5-9, and carrying out esterification to obtain the product.
The invention further comprises the following steps:
adding 550kg of Tara powder into 550L of liquid caustic soda, heating to 110-115 ℃, preserving heat for 1 hour, and filtering to obtain 550L of hydrolysate;
adding 300L dimethyl carbonate into the hydrolysate, controlling the temperature at 80-85 ℃ and the pH value at 8.5-9 for methylation, keeping the pH value unchanged, and keeping the temperature for 20-30 minutes, preferably 30 minutes;
adding 200L of liquid caustic soda after the step II, controlling the temperature at 102 ℃ and 105 ℃ for hydrolysis for 1-1.5 hours, preferably for 1.5 hours;
fourthly, adding 200L of dimethyl carbonate after the third step, controlling the temperature at 40-50 ℃ and the PH value at 8.5-9 for esterification;
dissolving the esterified product in methanol, adding 20-30kg of activated carbon, preferably 20kg of activated carbon, keeping the temperature for preferably 40 minutes, filtering, crystallizing and centrifuging;
sixthly, drying the product obtained in the fifth step to obtain the product.
The technical scheme of the invention prepares the finished product of the 3,4, 5-trimethoxybenzoate, the product yield can reach 99 percent, the content can reach 99.97 percent according to the forestry industry standard LY/T3153-2019 through HPLC detection, and the melting point can be 83.7-84.7 ℃.
In the invention, the process flow of the methyl 3,4, 5-trimethoxybenzoate is as follows:
tara powder-alkali hydrolysis-methylation-hydrolysis-esterification-decolouring-drying-product
The main synthetic route of the methyl 3,4, 5-trimethoxybenzoate is as follows:
on the basis of researching the preparation method of methyl 3,4, 5-trimethoxybenzoate, the invention provides a product of methyl 3,4, 5-trimethoxybenzoate prepared by the preparation method.
The invention has the beneficial effects that:
1. the invention uses tara powder hydrolysate to directly produce 3,4, 5-trimethoxy methyl benzoate products, compared with the production of gallic acid in LY/T1301-2005, the invention reduces the waste water, and reduces 25 cubic production waste water (200 yuan cost for each cubic treatment waste water, 5000 yuan waste water treatment cost for each ton product)
2. By adopting the technical scheme of the invention to produce each ton of products, the hydrochloric acid amount is saved by 5 tons. (500 yuan/ton hydrochloric acid, saving 2500 yuan per ton product)
3. By adopting the technical scheme of the invention to produce each ton of products, 30kg of active carbon for acidification, decoloration and refining decoloration of gallic acid is reduced, and the cost is 3000 yuan; 3000 yuan is saved for each ton.
4. By adopting the technical scheme of the invention to produce each ton of products, the labor cost of acidification, decoloration, drying and the like of gallic acid is reduced by 2000 yuan.
1-4, compared with the prior art, the technical scheme of the invention makes great progress in cost saving, and the cost for producing each ton of 3,4, 5-trimethoxybenzoic acid methyl ester product is saved as follows:
| item | Cost of wastewater treatment | The consumption of hydrochloric acid is saved | For saving decolourationThe amount of activated carbon used | Reduce labor cost of acidification, decoloration, drying and the like | In total |
| Save money | 5000 yuan | 2500 yuan | 3000 yuan | 2000 yuan | 12500 yuan |
5. Dimethyl carbonate is used to replace dimethyl sulfate (dimethyl sulfate is used in the methylation of the traditional process), so that the risk of poisoning in production is reduced, and a foundation is laid for safe production.
Detailed Description
Example 1
1. Adding 550L of liquid caustic soda (with the content of 32%) into a 3000L reaction tank, stirring, adding 550kg of tala powder, starting steam, heating to 110-;
2. pumping 550L of hydrolysate into a 2000L reaction tank by vacuum, adding 300L of dimethyl carbonate, controlling the temperature at 80-85 ℃ and the pH value at 7.5-8.0, and carrying out methylation. Keeping the pH value unchanged and keeping the temperature for 30 minutes;
3. adding 200L of liquid alkali (the content is 32%), controlling the temperature at 102 ℃ and 105 ℃ and hydrolyzing for 1.5 hours;
4. adding 200L dimethyl carbonate, controlling the temperature at 40-50 deg.C and pH at 7.5-8.0, and esterifying. Centrifuging the solution to obtain a crude product without changing the pH value;
5. dissolving the crude product in methanol, adding 20kg of active carbon, keeping the temperature for 40 minutes, filtering, crystallizing and centrifuging to obtain refined crystals;
6. drying at low temperature, and controlling the water content to be below 0.5%, thus obtaining the product: 135kg of 3,4, 5-trimethoxybenzoic acid methyl ester finished product, the product yield is 67.5 percent, the content is 99.00 percent according to the forestry industry standard LY/T3153-201 by HPLC detection, and the melting point is 82.0-83.9 ℃.
Example 2
1. Adding 550L of liquid caustic soda (with the content of 32%) into a 3000L reaction tank, stirring, adding 550kg of tala powder, starting steam, heating to 110-;
2. pumping 550L of hydrolysate into a 2000L reaction tank by vacuum, adding 300L of dimethyl carbonate, controlling the temperature at 80-85 ℃ and the pH value at 8.0-8.5 for methylation. Keeping the pH value unchanged and keeping the temperature for 30 minutes;
3. adding 200L of liquid alkali (the content is 32%), controlling the temperature at 102 ℃ and 105 ℃ and hydrolyzing for 1.5 hours;
4. adding 200L dimethyl carbonate, controlling the temperature at 40-50 deg.C and pH at 8.0-8.5, and esterifying. Centrifuging the solution to obtain a crude product without changing the pH value;
5. dissolving the crude product in methanol, adding 20kg of active carbon, keeping the temperature for 40 minutes, filtering, crystallizing and centrifuging to obtain refined crystals;
6. drying at low temperature, and controlling the water content to be below 0.5%, thus obtaining the product: 190kg3, 4, 5-trimethoxybenzoate finished product, the product yield is 95%, the content is 99.79% according to forestry industry standard LY/T3153-201 by HPLC detection, and the melting point is 82.7-83.7 ℃.
Example 3
1. Adding 550L of liquid caustic soda (with the content of 32%) into a 3000L reaction tank, stirring, adding 550kg of tala powder, starting steam, heating to 110-;
2. pumping 550L of hydrolysate into a 2000L reaction tank by vacuum, adding 300L of dimethyl carbonate, controlling the temperature at 80-85 ℃ and the pH value at 8.5-9.0, and carrying out methylation. Keeping the pH value unchanged and keeping the temperature for 30 minutes;
3. adding 200L of liquid alkali (the content is 32%), controlling the temperature at 102 ℃ and 105 ℃ and hydrolyzing for 1.5 hours;
4. adding 200L dimethyl carbonate, controlling the temperature at 40-50 deg.C and pH at 8.5-9.0, and esterifying. Centrifuging the solution to obtain a crude product without changing the pH value;
5. dissolving the crude product in methanol, adding 20kg of active carbon, keeping the temperature for 40 minutes, filtering, crystallizing and centrifuging to obtain refined crystals;
6. drying at low temperature, and controlling the water content to be below 0.5%, thus obtaining the product: 198kg of 3,4, 5-trimethoxybenzoate finished product, the product yield is 99 percent, the content is 99.97 percent according to the forestry industry standard LY/T3153-201 by HPLC detection, and the melting point is 83.7.00-84.7 ℃.
Experiment of influence of pH value on product yield and product quality in methylation and esterification
In conclusion, the optimal scheme is that the pH value is controlled to be 8.5-9.0 during methylation and esterification.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A preparation method for directly producing 3,4, 5-trimethoxybenzoate from tara hydrolysate is characterized by comprising the following steps:
adding dimethyl carbonate into the tower-pulling hydrolysate;
adding liquid caustic soda for hydrolysis;
and step two, adding dimethyl carbonate for esterification to obtain the product.
2. The method of manufacturing according to claim 1, comprising the steps of:
adding tara powder into liquid caustic soda for hydrolysis to obtain hydrolysate;
adding dimethyl carbonate into the hydrolysate;
adding liquid caustic soda for hydrolysis after the step two;
fourthly, adding dimethyl carbonate to esterify after the third step.
3. The method of claim 2, wherein the steps further comprise:
dissolving the esterified methanol, adding active carbon, filtering, crystallizing and centrifuging; or/and the steps further comprise: drying and sieving.
4. The preparation method according to claim 2, wherein in the step (r), the mass-to-volume ratio of the tara powder to the liquid alkali is 1:0.95-1.05, preferably 1: 1; adding liquid caustic soda and tara powder, and further, the volume is L; the mass is kg.
5. The preparation method according to claim 2, wherein dimethyl carbonate is added in the step (iv) for esterification, and the ratio of the volume of dimethyl carbonate added to the volume of liquid-base hydrolysis added in the step (iii) is 200: 200.
6. the preparation method according to claim 2, wherein in the second step, the volume ratio of the hydrolysate to the dimethyl carbonate is 550: 300.
7. the process of claim 2, wherein step (ii) comprises adjusting the PH to a PH of 7.5 to 9, preferably 8.5 to 9; and/or step (iv) comprises adjusting the pH to a pH of 7.5 to 9, preferably 8.5 to 9.
8. The method of manufacturing according to claim 1 or 2, comprising the steps of:
adding 550L of liquid caustic soda, adding 550kg of Tara powder, heating to 110-115 ℃, preserving heat for 1 hour, and filtering to obtain 550L of hydrolysate;
adding 300L dimethyl carbonate into the hydrolysate, controlling the temperature at 80-85 ℃ and the pH value at 8.5-9 for methylation, keeping the pH value unchanged, and keeping the temperature for 30 minutes;
adding 200L of liquid caustic soda after the step II, controlling the temperature at 102 ℃ and 105 ℃ for hydrolysis for 1-1.5 hours, preferably for 1.5 hours;
fourthly, adding 200L of dimethyl carbonate after the third step, controlling the temperature at 40-50 ℃ and the PH value at 8.5-9, and carrying out esterification to obtain the product.
9. The method of manufacturing according to claim 1 or 2, comprising the steps of:
adding 550kg of Tara powder into 550L of liquid caustic soda, heating to 110-115 ℃, preserving heat for 1 hour, and filtering to obtain 550L of hydrolysate;
adding 300L dimethyl carbonate into the hydrolysate, controlling the temperature at 80-85 ℃ and the pH value at 8.5-9 for methylation, keeping the pH value unchanged, and keeping the temperature for 20-30 minutes, preferably 30 minutes;
adding 200L of liquid caustic soda after the step II, controlling the temperature at 102 ℃ and 105 ℃ for hydrolysis for 1-1.5 hours, preferably for 1.5 hours;
fourthly, adding 200L of dimethyl carbonate after the third step, controlling the temperature at 40-50 ℃ and the PH value at 8.5-9 for esterification;
dissolving the esterified product in methanol, adding 10-20 kg, preferably 20kg of active carbon, preserving the temperature for 30-40 minutes, preferably 40 minutes, filtering, crystallizing and centrifuging;
sixthly, drying the product obtained in the fifth step to obtain the product.
10. A methyl 3,4, 5-trimethoxybenzoate product prepared by the process of any one of claims 1 to 8.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051353A (en) * | 1990-10-13 | 1991-05-15 | 上海大众制药厂 | Direct method preparation 3,4, the 5-tri-methoxybenzoate |
| CN106977397A (en) * | 2017-04-11 | 2017-07-25 | 五峰赤诚生物科技股份有限公司 | A kind of synthetic method of 3,4,5 trimethoxybenzoic acid |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051353A (en) * | 1990-10-13 | 1991-05-15 | 上海大众制药厂 | Direct method preparation 3,4, the 5-tri-methoxybenzoate |
| CN106977397A (en) * | 2017-04-11 | 2017-07-25 | 五峰赤诚生物科技股份有限公司 | A kind of synthetic method of 3,4,5 trimethoxybenzoic acid |
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