CN111518003A - Purification method of dithiodibenzoic acid - Google Patents
Purification method of dithiodibenzoic acid Download PDFInfo
- Publication number
- CN111518003A CN111518003A CN202010452105.6A CN202010452105A CN111518003A CN 111518003 A CN111518003 A CN 111518003A CN 202010452105 A CN202010452105 A CN 202010452105A CN 111518003 A CN111518003 A CN 111518003A
- Authority
- CN
- China
- Prior art keywords
- dithiodibenzoic acid
- dmf
- acid
- water
- dithiodibenzoic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- LBEMXJWGHIEXRA-UHFFFAOYSA-N 2-[(2-carboxyphenyl)disulfanyl]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1SSC1=CC=CC=C1C(O)=O LBEMXJWGHIEXRA-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000000746 purification Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012046 mixed solvent Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000000967 suction filtration Methods 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012043 crude product Substances 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 238000006193 diazotization reaction Methods 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/18—Dithiocarboxylic acids
Abstract
The invention belongs to the field of dithiodibenzoic acid production, and particularly relates to a purification method of dithiodibenzoic acid, which is realized by the following steps: adding the crude dithiodibenzoic acid into a mixed solvent of DMF and water, stirring, heating for dissolving, keeping the temperature, then cooling, carrying out suction filtration to remove the mixed solvent and impurities, and drying to obtain refined dithiodibenzoic acid; the mass ratio of the dithiodibenzoic acid crude product to the DMF to the water is 1: 1-1.5: 1. According to the invention, through a mixed solvent of DMF and water, impurities which are insoluble in water in the crude dithiodibenzoic acid are dissolved in DMF, the DMF is soluble in water, the residual DMF is weak after drying, and the purity of the product is as high as 99%; the method has simple steps and convenient operation, does not need the post-treatment of alkali liquor wastewater and acid liquor wastewater, saves the production cost, and is environment-friendly and low in consumption.
Description
Technical Field
The invention belongs to the field of dithiodibenzoic acid production, and particularly relates to a purification method of dithiodibenzoic acid.
Background
Dithiodibenzoic acids, also known as dithiosalicylic acids, are useful as intermediates for pharmaceuticals, dyes, bactericides, and photoinitiators. At present, the following 3 routes are mainly used for the synthesis process of dithiodibenzoic acid:
(1) diazotization of sodium polysulfide route: taking o-aminobenzoic acid as a raw material, carrying out diazotization reaction with sodium nitrite and hydrochloric acid at low temperature, and then reacting with sodium polysulfide to obtain a target product;
(2) anthranilic acid direct sulfurization route: the method comprises the following steps of (1) directly reacting anthranilic acid serving as a raw material with sodium polysulfide at a high temperature to obtain a target product;
(3) diazotization gas sulfur dioxide route: the o-aminobenzoic acid is used as a raw material, is subjected to diazotization reaction with sodium nitrite and hydrochloric acid at low temperature, and is then reacted with sulfur dioxide gas to obtain a target product.
The existing process mainly adopts water as a solvent, most impurities are soluble in water, but part of impurities are poor in water solubility, so that the product purity of the dithiodibenzoic acid production line is only 96.5% at most. For refining dithiodibenzoic acid, the jade article improves the original refining process, and simplifies the operations of adding materials → boiling → filtering → precipitating → filtering → drying on the basis of 8 steps, namely precipitation → filtering → dissolving → boiling → filtering → precipitating → filtering → drying, and the operation of adding materials → boiling → filtering → precipitating → filtering → drying, and the discharge of acid wastewater still exists in the refining process. CN201810985288A provides a refining process of dithiodibenzoic acid, which adjusts the product purity of pH value to 98% through alkali dissolution, impurity removal and acidification processes, and the use of alkali liquor and acid liquor increases the pollution discharge cost and has complex operation.
Disclosure of Invention
Aiming at the problems of low purity, complex operation and the like of dithiodibenzoic acid in the prior art, the application provides a purification method of dithiodibenzoic acid, which has the advantages of high purity, simple steps and simple and convenient operation.
The technical scheme of the invention is as follows:
a purification method of dithiodibenzoic acid is realized by the following steps:
adding the crude dithiodibenzoic acid into a mixed solvent of DMF and water, stirring, heating for dissolving, keeping the temperature, then cooling, carrying out suction filtration to remove the mixed solvent and impurities, and drying to obtain refined dithiodibenzoic acid; the mass ratio of the dithiodibenzoic acid crude product to the DMF to the water is 1: 1-1.5: 1.
Wherein the content of the first and second substances,
the mass ratio of the crude dithiodibenzoic acid to DMF to water is preferably 1:1.25: 1.
The purity of the crude dithiodibenzoic acid is 95%, and the purity of the product of the dithiodibenzoic acid production line is generally 95-97%.
The stirring time is 0.5-1 h. The dissolution of the crude dithiodiphenic acid in the mixed solvent is promoted by stirring.
Heating to 70-80 ℃. Dithiodibenzoic acid is easily dissolved in a hot DMF solution, and if the temperature is too low, the solubility is low, and if the temperature is too high, the subsequent cooling effect can be influenced.
The heat preservation time is 1-2 h. The reaction was incubated to facilitate dissolution.
Cooling to 5-10 ℃. The dithiodibenzoic acid is insoluble in cold DMF, and the pure dithiodibenzoic acid is separated out by cooling.
The drying mode adopts a flash evaporator for drying.
When the mass ratio of the crude dithiodibenzoic acid to DMF to water is =1:1.25:1, substances contained in the crude dithiodibenzoic acid are all dissolved in a mixed solvent, and because salicylic acid as an impurity, trace anthranilic acid which is not completely reacted and other impurities are easily dissolved in DMF, the dithiodibenzoic acid is easily dissolved in hot DMF and is difficultly dissolved in cold DMF, the purification of the dithiodibenzoic acid is realized by a method of firstly dissolving in heat and then cooling and precipitating.
The beneficial effect of the invention is that,
(1) according to the invention, through a mixed solvent of DMF and water, impurities which are insoluble in water in the crude dithiodibenzoic acid are dissolved in DMF, the DMF is soluble in water, the residual DMF is weak after drying, and the purity of the product is as high as 99%;
(2) the method has simple steps and convenient operation, does not need the post-treatment of the alkali liquor wastewater and the acid liquor wastewater, saves the production cost, and is environment-friendly and low in consumption.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
A purification method of dithiodibenzoic acid is realized by the following steps:
adding 200g of crude dithiodibenzoic acid into a mixed solvent of DMF and water, wherein the mass ratio of the crude dithiodibenzoic acid: DMF: water =1:1.25: 1; stirring for 0.5h, heating to 80 ℃ for dissolution, keeping the temperature for 2h, then cooling to 5 ℃, removing the mixed solvent and impurities by suction filtration, and drying to obtain 180.6g of refined dithiodibenzoic acid. The yield was 90.3%, and the purity by high performance liquid chromatography was 99%.
Example 2
A purification method of dithiodibenzoic acid is realized by the following steps:
adding 200g of crude dithiodibenzoic acid into a mixed solvent of DMF and water, wherein the mass ratio of the crude dithiodibenzoic acid: DMF: water =1:1: 1; stirring for 0.5h, heating to 70 ℃ for dissolution, keeping the temperature for 1h, then cooling to 10 ℃, removing the mixed solvent and impurities by suction filtration, and drying to obtain 170.3g of refined dithiodibenzoic acid. The yield was 85.2%, and the purity by high performance liquid chromatography was 98%.
Example 3
A purification method of dithiodibenzoic acid is realized by the following steps:
adding 200g of crude dithiodibenzoic acid into a mixed solvent of DMF and water, wherein the mass ratio of the crude dithiodibenzoic acid: DMF: water =1:1.5: 1; stirring for 1h, heating to 80 ℃ for dissolution, keeping the temperature for 2h, then cooling to 10 ℃, removing the mixed solvent and impurities by suction filtration, and drying to obtain 186g of refined dithiodibenzoic acid. The yield was 93%, and the purity by high performance liquid chromatography was 99%.
Although the present invention has been described in detail by way of preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. A method for purifying dithiodibenzoic acid is characterized in that the method is realized by the following steps: adding the crude dithiodibenzoic acid into a mixed solvent of DMF and water, stirring, heating for dissolving, keeping the temperature, then cooling, carrying out suction filtration to remove the mixed solvent and impurities, and drying to obtain refined dithiodibenzoic acid; the mass ratio of the dithiodibenzoic acid crude product to the DMF to the water is 1: 1-1.5: 1.
2. The method for purifying dithiodibenzoic acid according to claim 1, wherein the mass ratio of crude dithiodibenzoic acid, DMF and water is preferably 1:1.25: 1.
3. The method as claimed in claim 1, wherein the purity of the crude dithiodibenzoic acid is 95%.
4. The purification method of dithiodibenzoic acid according to claim 1, wherein the stirring time is 0.5-1 h.
5. The method for purifying dithiodibenzoic acid as claimed in claim 1, wherein the temperature is raised to 70-80 ℃.
6. The purification method of dithiodibenzoic acid according to claim 1, wherein the holding time is 1-2 h.
7. The method for purifying dithiodibenzoic acid as claimed in claim 1, wherein the temperature is reduced to 5-10 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010452105.6A CN111518003B (en) | 2020-05-26 | 2020-05-26 | Purification method of dithiodibenzoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010452105.6A CN111518003B (en) | 2020-05-26 | 2020-05-26 | Purification method of dithiodibenzoic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111518003A true CN111518003A (en) | 2020-08-11 |
| CN111518003B CN111518003B (en) | 2021-11-09 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010452105.6A Active CN111518003B (en) | 2020-05-26 | 2020-05-26 | Purification method of dithiodibenzoic acid |
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| Country | Link |
|---|---|
| CN (1) | CN111518003B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181124A (en) * | 2021-12-13 | 2022-03-15 | 大连百傲化学股份有限公司 | Recycling treatment method of 1, 2-benzisothiazolin-3-one chlorination process wastewater |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805277A (en) * | 2010-04-23 | 2010-08-18 | 上虞市洁源环保科技有限公司 | Preparation method of 2,2'-dithio-salicylic acid |
| CN109096165A (en) * | 2018-08-28 | 2018-12-28 | 临沂华毅医药股份有限公司 | A kind of refining plant and technique of dithiodibenzoic acid |
| CN208980616U (en) * | 2018-08-28 | 2019-06-14 | 临沂华毅医药股份有限公司 | A kind of refining plant of dithiodibenzoic acid |
| CN209597201U (en) * | 2019-02-25 | 2019-11-08 | 临沂华毅医药股份有限公司 | A kind of sulfuration process highly effective reaction device of dithiodibenzoic acid |
-
2020
- 2020-05-26 CN CN202010452105.6A patent/CN111518003B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805277A (en) * | 2010-04-23 | 2010-08-18 | 上虞市洁源环保科技有限公司 | Preparation method of 2,2'-dithio-salicylic acid |
| CN109096165A (en) * | 2018-08-28 | 2018-12-28 | 临沂华毅医药股份有限公司 | A kind of refining plant and technique of dithiodibenzoic acid |
| CN208980616U (en) * | 2018-08-28 | 2019-06-14 | 临沂华毅医药股份有限公司 | A kind of refining plant of dithiodibenzoic acid |
| CN209597201U (en) * | 2019-02-25 | 2019-11-08 | 临沂华毅医药股份有限公司 | A kind of sulfuration process highly effective reaction device of dithiodibenzoic acid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181124A (en) * | 2021-12-13 | 2022-03-15 | 大连百傲化学股份有限公司 | Recycling treatment method of 1, 2-benzisothiazolin-3-one chlorination process wastewater |
| CN114181124B (en) * | 2021-12-13 | 2024-01-26 | 大连百傲化学股份有限公司 | Recycling treatment method of 1, 2-benzisothiazolin-3-one chlorination process wastewater |
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| Publication number | Publication date |
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| CN111518003B (en) | 2021-11-09 |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A Purification Method for Dithiodibenzoic Acid Effective date of registration: 20230418 Granted publication date: 20211109 Pledgee: Dongying Rural Commercial Bank Co.,Ltd. Helong Branch Pledgor: DONGYING JINFENGHUANG CHEMICAL Co.,Ltd. Registration number: Y2023980038330 |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
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Granted publication date: 20211109 Pledgee: Dongying Rural Commercial Bank Co.,Ltd. Helong Branch Pledgor: DONGYING JINFENGHUANG CHEMICAL Co.,Ltd. Registration number: Y2023980038330 |
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| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A purification method for dithiodibenzoic acid Granted publication date: 20211109 Pledgee: Dongying Rural Commercial Bank Co.,Ltd. Helong Branch Pledgor: DONGYING JINFENGHUANG CHEMICAL Co.,Ltd. Registration number: Y2024980008438 |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right |