CN107337599A - A kind of preparation method of 3,4,5 tri-methoxybenzoates - Google Patents
A kind of preparation method of 3,4,5 tri-methoxybenzoates Download PDFInfo
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- CN107337599A CN107337599A CN201710627143.9A CN201710627143A CN107337599A CN 107337599 A CN107337599 A CN 107337599A CN 201710627143 A CN201710627143 A CN 201710627143A CN 107337599 A CN107337599 A CN 107337599A
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- tri
- methoxybenzoates
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- sodium hydroxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
- C07C67/11—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond being mineral ester groups
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- 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
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- 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
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- 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
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
- C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
- C07H13/08—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals directly attached to carbocyclic rings
Abstract
The invention provides a kind of preparation method of 3,4,5 tri-methoxybenzoates, using tannic acid as raw material, 3,4,5 tri-methoxybenzoates are prepared by techniques such as methylation reaction, hydrolysis, esterification, refinery decolorization, dryings.The present invention changes traditional " tannic acid → 3,4,5 trimethoxybenzoic acids → 3,4,5 tri-methoxybenzoates " technological process, directly prepares 3,4,5 tri-methoxybenzoates.3,4,5 tri-methoxybenzoates are prepared by the present invention, shorten for 33% process time, reduce 28% material and energy resource consumption, reduce 50% water consumption, quantity of wastewater effluent is greatly decreased, and cost reduces at least 22%, is adapted to industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of chemicals, and in particular to one kind uses tannic acid to prepare 3,4,5- for raw material
The method of tri-methoxybenzoate.
Background technology
3,4,5- tri-methoxybenzoates are important organic synthesis and drug synthesis intermediate, classical synthesis side
Method is using gallic acid as raw material, methylates obtained 3 in the basic conditions, 4,5- trimethoxybenzoic acids, then methanol esterification
Obtain.It is existing to be by the tri-methoxybenzoate technique of Material synthesis 3,4,5- of tannic acid：Tannic acid → methylation reaction
→ hydrolysis → methylation reaction → acidifying → dehydration → 3,4 again, 5- trimethoxybenzoic acids crude product → decolouring → 3,4,5- front threes
P-methoxybenzoic acid fine work → esterification → 3,4,5- tri-methoxybenzoates crude product → refined → 3,4,5- trimethoxies
Methyl benzoate fine work → drying → 3,4,5- tri-methoxybenzoate finished products.This method is multiple by methylation reaction etc.
Step obtains, and because step is more, process route length, causes the long production cycle, raw and auxiliary material and energy resource consumption are big, produce wastewater flow rate
Handle greatly costly, production cost can be in any more.
The content of the invention
In order to solve the above problems, the present invention provides a kind of production method of 3,4,5- tri-methoxybenzoates.
For this technical scheme is that：The preparation method of one kind 3,4,5- tri-methoxybenzoates, its feature
It is, comprises the following steps：
A. methylation reaction：400 liters of water are added in a kettle, put into 200 kilograms of tannic acid, add mass percent concentration
For 38.5%-39.5% 200 liters of sodium hydroxide solution, stirring ensures tannic acid dissolving；Temperature is controlled to add sulphur at 30-35 DEG C
300 liters of dimethyl phthalate, while the sodium hydroxide solution for being 38.5%-39.5% with mass percent concentration adjusts pH value to 8.1-
8.4, then heated up in 80-85 DEG C of insulation reaction half an hour 30-34 minute；
B. hydrolyze：The sodium hydroxide solution 150 that mass percent concentration is 38.5%-39.5% is added on the basis of step A
Rise, hydrolyze 2 hours, cooled to 40-45 DEG C at a temperature of 100-105 DEG C；
C. esterification：300 liters of dimethyl ester is added on the basis of step B, while pH value is adjusted to 8.4-8.7 with liquid caustic soda,
Insulation reaction 1.5 hours at a temperature of 40-45 DEG C；
D. decolourize：50 kilograms of activated carbons are added on the basis of step C, are warming up to 70-75 DEG C, are incubated decolouring 1-1.5 hours；
40-45 DEG C, and centrifugal dehydration are subsequently cooled to, produces 3,4,5- tri-methoxybenzoate crystal；
E. dry, crush：3 that step D is obtained, 4,5- tri-methoxybenzoate crystal are dry, crush, and produce 3,4,
5- tri-methoxybenzoate finished products.
Preferably, the method for dropwise addition is taken to add dimethyl suflfate in the methylation reaction described in step A.
Preferably, the method for dropwise addition is taken to add dimethyl ester in the esterification described in step C.
Beneficial effect：
The present invention changes traditional " tannic acid → 3,4,5- trimethoxybenzoic acids → 3,4,5- trimethoxybenzoic acid first
The pilot process of ester ", 3,4,5- tri-methoxybenzoates are directly produced, shorten for 33% process time, reduce 28%
Material and energy resource consumption, reduce 50% water consumption, quantity of wastewater effluent is greatly decreased, and cost reduces at least 22%, is adapted to work
Industry metaplasia is produced；Dimethyl suflfate, dimethyl ester, rather than disposable addition are added using dropwise addition mode in the esterification reaction, so
The yield of product can be effectively improved；The core of the present invention be to change it is traditional decolourized at a temperature of 95-100 DEG C, using 70-
75 DEG C of relative low temperature decolourizes, and ensures to decolourize thoroughly by the time of 1-1.5 hours, and inhibits the trend of oxidation reaction,
The generation of accessory substance is prevented, ensures product purity and yield.
Embodiment
Embodiment 1：
The preparation method of one kind 3,4,5- tri-methoxybenzoates, it is characterised in that comprise the following steps：
A. methylation reaction：400 liters of water are added in a kettle, put into 200 kilograms of tannic acid, add mass percent concentration
For 38.5%-39.5% 200 liters of sodium hydroxide solution, stirring ensures tannic acid dissolving；Control temperature that sulphur is added dropwise at 30-35 DEG C
300 liters of dimethyl phthalate, while the sodium hydroxide solution for being 38.5%-39.5% with mass percent concentration adjusts pH value to 8.1-
8.4, then heated up in 80-85 DEG C of insulation reaction half an hour 30-34 minute.
B. hydrolyze：The sodium hydroxide solution that mass percent concentration is 38.5%-39.5% is added on the basis of step A
150 liters, hydrolyze 2 hours, cooled to 40-45 DEG C at a temperature of 100-105 DEG C.
C. esterification：300 liters of dimethyl ester is added dropwise on the basis of step B, while pH value is adjusted to 8.4- with liquid caustic soda
8.7, insulation reaction 1.5 hours at a temperature of 40-45 DEG C.
D. decolourize：50 kilograms of activated carbons are added on the basis of step C, are warming up to 70-75 DEG C, insulation decolouring 1-1.5 is small
When；40-45 DEG C, and centrifugal dehydration are subsequently cooled to, produces 3,4,5- tri-methoxybenzoate crystal.
E. dry, crush：3 that step D is obtained, 4,5- tri-methoxybenzoate crystal are dry, crush, and produce
3,4,5- tri-methoxybenzoate finished products.
The mechanism and innovative point explanation of the present invention：
1st, the present invention changes traditional " tannic acid → 3,4,5- trimethoxybenzoic acids → 3,4,5- trimethoxybenzoic acid first
The pilot process of ester ", directly prepare 3,4,5- tri-methoxybenzoates with tannic acid.
2nd, carried out when the dimethyl suflfate described in step A is methylated, it is necessary under alkaline medium, to increase oxygen original
The reactivity of negative charge on son, dimethyl suflfate reactivity is big, and temperature is too high easily to decompose, and is preferably reacted at low temperature, together
When tannic acid be polyatomic phenol, it is unstable in alkaline high temperature, oxidation reaction easily occurs, therefore the temperature that methylates is unsuitable too high, control
At 80-85 DEG C, pH value controls in 8.1-8.4 system.
3rd, it is one of key link in the hydrolysis described in step C, hydrolysis is to disconnect macromolecular, forms small molecule,
If hydrolysis is not thorough, as a result the disconnected key is not disconnected, and big molecular impurity is more in product, product color depth and tacky, to make hydrolysis
Reaction is thorough, it is necessary to assure the dosage of liquid caustic soda, but can not be excessive, it is otherwise unfavorable to the esterification after hydrolysis, reduce yield；
In the control in reaction time, short reaction excessively is incomplete, the long more power of consumption, while influences product quality.
4th, in the decolouring described in step D, temperature control is selected to be incubated 1-1.5 hours at 70-75 DEG C, first, considering to live
Property charcoal optimal use temperature；Two allow in the case of a high temperature, and ester hydrolyzes in the basic conditions, are unfavorable for balance to generation ester
Direction movement, cause the generation of side reaction, it is impossible to ensure the purity and yield of product.
Claims (3)
1. one kind 3,4, the preparation method of 5- tri-methoxybenzoates, it is characterised in that comprise the following steps：
A. methylation reaction：400 liters of water are added in a kettle, put into 200 kilograms of tannic acid, add mass percent concentration
For 38.5%-39.5% 200 liters of sodium hydroxide solution, stirring ensures tannic acid dissolving；Temperature is controlled to add sulphur at 30-35 DEG C
300 liters of dimethyl phthalate, while the sodium hydroxide solution for being 38.5%-39.5% with mass percent concentration adjusts pH value to 8.1-
8.4, then heated up in 80-85 DEG C of insulation reaction half an hour 30-34 minute；
B. hydrolyze：The sodium hydroxide solution 150 that mass percent concentration is 38.5%-39.5% is added on the basis of step A
Rise, hydrolyze 2 hours, cooled to 40-45 DEG C at a temperature of 100-105 DEG C；
C. esterification：On the basis of step B add 300 liters of dimethyl ester, while with sodium hydroxide solution adjust pH value to
8.4-8.7, insulation reaction 1.5 hours at a temperature of 40-45 DEG C；
D. decolourize：50 kilograms of activated carbons are added on the basis of step C, are warming up to 70-75 DEG C, are incubated decolouring 1-1.5 hours；
40-45 DEG C, and centrifugal dehydration are subsequently cooled to, produces 3,4,5- tri-methoxybenzoate crystal；
E. dry, crush：3 that step D is obtained, 4,5- tri-methoxybenzoate crystal are dry, crush, and produce 3,4,
5- tri-methoxybenzoate finished products.
A kind of 2. preparation method of 3,4,5- tri-methoxybenzoates according to claim 1, it is characterised in that：In step
The method of dropwise addition is taken to add dimethyl suflfate in methylation reaction described in rapid A.
A kind of 3. preparation method of 3,4,5- tri-methoxybenzoates according to claim 1, it is characterised in that：In step
The method of dropwise addition is taken to add dimethyl ester in esterification described in rapid C.
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| CN201710627143.9A CN107337599A (en) | 2017-07-28 | 2017-07-28 | A kind of preparation method of 3,4,5 tri-methoxybenzoates |
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| CN201710627143.9A CN107337599A (en) | 2017-07-28 | 2017-07-28 | A kind of preparation method of 3,4,5 tri-methoxybenzoates |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4471134A (en) * | 1982-09-29 | 1984-09-11 | Mallinckrodt, Inc. | Preparation of trimethoxybenzoate esters and trimethoxybenzoic acid |
| CN1057254A (en) * | 1991-04-10 | 1991-12-25 | 湖北省竹山县林产化工厂 | Chinese gall Beihua tannin is synthetic produces 3,4, the 5-TMB |
| CN102690196A (en) * | 2011-04-15 | 2012-09-26 | 竹山县天新医药化工有限责任公司 | Preparation and purification method of 3,4,5-trimethoxybenzoic acid |
-
2017
- 2017-07-28 CN CN201710627143.9A patent/CN107337599A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4471134A (en) * | 1982-09-29 | 1984-09-11 | Mallinckrodt, Inc. | Preparation of trimethoxybenzoate esters and trimethoxybenzoic acid |
| CN1057254A (en) * | 1991-04-10 | 1991-12-25 | 湖北省竹山县林产化工厂 | Chinese gall Beihua tannin is synthetic produces 3,4, the 5-TMB |
| CN102690196A (en) * | 2011-04-15 | 2012-09-26 | 竹山县天新医药化工有限责任公司 | Preparation and purification method of 3,4,5-trimethoxybenzoic acid |
Non-Patent Citations (2)
| Title |
|---|
| 武斌等: "塔拉单宁酸制取3,4,5-三甲氧基苯甲酸甲酯的研究", 《贵州化工》 * |
| 毕良武等: "塔拉粉直接法制备3,4,5-三甲氧基苯甲酸甲酯的研究", 《林产化学与工业》 * |
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