CN111747906A - Method for recovering dithiodibenzothiazole - Google Patents
Method for recovering dithiodibenzothiazole Download PDFInfo
- Publication number
- CN111747906A CN111747906A CN202010695008.XA CN202010695008A CN111747906A CN 111747906 A CN111747906 A CN 111747906A CN 202010695008 A CN202010695008 A CN 202010695008A CN 111747906 A CN111747906 A CN 111747906A
- Authority
- CN
- China
- Prior art keywords
- recovering
- active ester
- dithiodibenzothiazyl
- residual liquid
- dithiodibenzothiazole
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
- C07D277/76—Sulfur atoms attached to a second hetero atom
- C07D277/78—Sulfur atoms attached to a second hetero atom to a second sulphur atom
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Abstract
The invention discloses a method for recovering dithiodibenzothiazole from AE crude product mother liquor generated in the production process of AE active ester, which comprises the following steps: and (3) recovering the solvent from the AE crude product mother liquor, adding a benzene solvent, filtering to obtain a 2-mercaptobenzothiazole solution, carrying out catalytic oxidation reaction on the 2-mercaptobenzothiazole solution under the action of a catalyst and a catalytic initiator, filtering, washing and drying to obtain the dithiodibenzothiazole. The method has the advantages of stable process, simple operation, high recovery rate and low production cost, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a method for recovering dithiodibenzothiazyl from AE active ester residual liquid containing 2-mercaptobenzothiazole generated in the production process of AE active ester.
Background
Dithiodibenzothiazole (DM for short in English), with the CAS number of 120-78-5, is a main raw material for producing AE active ester; it is also used as a universal accelerator for natural rubber, synthetic rubber and reclaimed rubber, and is mainly used for manufacturing tires, inner tubes, adhesive tapes, rubber shoes, general industrial products and the like. High purity DM (pharmaceutical grade DM), commonly known as competitive DM, is an important pharmaceutical intermediate in the manufacture of cephalosporin antibiotics. The structural formula is as follows:
AE active ester (MAEM for short) is one of main raw materials of semi-synthetic cephalosporin antibiotic drugs, and is used for synthesizing third and fourth generations of semi-synthetic cephalosporins such as cefmenoxime hydrochloride, cefotaxime sodium, ceftriaxone sodium, cefetamet pivoxil, cefpirome and the like.
The AE active ester is prepared by reacting aminothiazoly loximate with dithiodibenzothiazole under the action of triethyl phosphite serving as a condensing agent, and a byproduct 2-mercaptobenzothiazole is generated in the preparation process, wherein the generated amount is equivalent to about 60 percent of the dithiodibenzothiazole which is not utilized. In order to reduce the production cost of AE active ester and relieve the pressure of three-waste treatment, the invention discloses a method for recovering dithiodibenzothiazyl by oxidizing benzene solution of 2-mercaptobenzothiazole under the action of a catalyst and a catalytic initiator, wherein the quality of the recovered dithiodibenzothiazyl meets the requirement of medicinal standard, and the dithiodibenzothiazyl can be recycled in the production process of the AE active ester.
Disclosure of Invention
The invention aims to provide a method for recovering dithiodibenzothiazole in the production process of AE active ester, so as to overcome the defects in the prior art and meet the requirement of industrial production.
The technical scheme of the invention is as follows: a method for recovering dithiodibenzothiazyl, comprising the steps of:
(1) (1) collecting residues of AE active ester crude mother liquor generated in the production process of AE active ester after a solvent is recovered, and calling the residues as AE active ester residual liquor;
(2) adding a benzene solvent into the AE active ester residual liquid, stirring at room temperature for 30-40 minutes, and performing suction filtration to obtain a filtrate which is a 2-mercaptobenzothiazole solution;
(3) adding a catalyst into the 2-mercaptobenzothiazole, introducing air or oxygen, adding a catalytic initiator at room temperature, carrying out catalytic oxidation reaction under the irradiation of a light source, cooling to 5-10 ℃ after the reaction is finished, stirring for 1-2 hours, carrying out suction filtration, washing a filter cake with a benzene solvent, draining, and drying to obtain the dithiodibenzothiazole.
Further, in the step (2), the benzene solvent is any one of toluene, xylene or chlorobenzene.
Further, the weight ratio of the AE active ester residual liquid to the benzene solvent in the step (2) is 1: 2-6.
Further, the catalyst used in the step (3) is tetrahydrofuran, and the weight ratio of the AE active ester residual liquid to the catalyst is as follows: 1: 0.2-1.
Further, the catalytic initiator in the step (3) is any one of hydrogen peroxide, m-chloroperoxybenzoic acid or peracetic acid, and the weight ratio of the AE active ester residual liquid to the catalytic initiator is 1: 0.05-0.5.
Further, the temperature of the catalytic oxidation reaction in the step (3) is 20-60 ℃.
Further, the catalytic oxidation reaction time in the step (3) is 7 to 24 hours.
Further, the light source in the step (3) is any one of sunlight, incandescent lamp or fluorescent lamp.
The invention has the advantages of stable process, simple operation, high recovery rate of dithiodibenzothiazyl up to 90% and high quality of product. Low production cost and suitability for large-scale industrial production.
Detailed Description
The present invention is described in further detail below by way of examples.
Example 1:
adding 200g of AE active ester residual liquid and 600g of methylbenzene into a 2000ml three-neck round-bottom flask, stirring at room temperature for 30 minutes, and performing suction filtration to obtain a filtrate which is a 2-mercaptobenzothiazole solution;
adding 40g of tetrahydrofuran into 2000ml of three-neck round-bottom flask in a 2-mercaptobenzothiazole solution, introducing oxygen, dropwise adding 20g of hydrogen peroxide at room temperature, carrying out catalytic oxidation reaction under the irradiation of sunlight, controlling the reaction temperature to be 30 ℃, cooling to 6 ℃, stirring for 1.5 hours after reacting for 24 hours, carrying out suction filtration, washing a filter cake with toluene, draining, and drying to obtain 109g of dithiodibenzothiazole. The yield was 91.3%, and the melting point was 179.4-181.6.
Example 2:
adding 200g of AE active ester residual liquid and 800g of chlorobenzene into a 2000ml three-neck round-bottom flask, stirring at room temperature for 35 minutes, and performing suction filtration to obtain a filtrate which is a 2-mercaptobenzothiazole solution;
adding 2-mercaptobenzothiazole solution into a 2000ml four-neck round bottom flask, adding 80g of tetrahydrofuran, introducing oxygen, dropwise adding 50g of m-chloroperoxybenzoic acid at room temperature, carrying out catalytic oxidation reaction under the irradiation of a fluorescent lamp, controlling the reaction temperature to be 40 ℃, reacting for 20 hours, cooling to 8 ℃, stirring for 1 hour, carrying out suction filtration, washing a filter cake with chlorobenzene, pumping, and drying to obtain 112g of dithiodibenzothiazole. The yield was 93.4% and the melting point was 179.5-181.2 ℃.
Example 3:
adding 200g of AE active ester residual liquid and 1000g of dimethylbenzene into a 2000ml three-neck round-bottom flask, stirring at room temperature for 40 minutes, and performing suction filtration to obtain a filtrate which is a 2-mercaptobenzothiazole solution;
adding 2-mercaptobenzothiazole solution into a 2000ml four-neck round bottom flask, adding 200g of tetrahydrofuran, introducing air, dropwise adding 100g of peroxyacetic acid at room temperature, carrying out catalytic oxidation reaction under the irradiation of an incandescent lamp, controlling the reaction temperature to be 50 ℃, reacting for 7 hours, cooling to 7 ℃, stirring for 1.5 hours, carrying out suction filtration, washing a filter cake with dimethylbenzene, draining, and drying to obtain 110g of dithiodibenzothiazole, wherein the yield is 92.4%, and the melting point is 180.1.2-181.6 ℃.
Claims (8)
1. A method for recovering dithiodibenzothiazyl, comprising the steps of:
(1) collecting residues of AE active ester crude mother liquor generated in the production process of the AE active ester after the solvent is recovered, and calling the residues as AE active ester residual liquor;
(2) adding a benzene solvent into the AE active ester residual liquid, stirring at room temperature for 30-40 minutes, and performing suction filtration to obtain a filtrate which is a 2-mercaptobenzothiazole solution;
(3) adding a catalyst into the 2-mercaptobenzothiazole solution, introducing air or oxygen, adding a catalytic initiator at room temperature, carrying out catalytic oxidation reaction under the irradiation of a light source, cooling to 5-10 ℃ after the reaction is finished, stirring for 1-2 hours, carrying out suction filtration, washing a filter cake by using a benzene solvent, draining, and drying to obtain the dithiodibenzothiazole.
2. The method for recovering dithiodibenzothiazyl according to claim 1, wherein: in the step (2), the benzene solvent is any one of toluene, xylene or chlorobenzene.
3. The method for recovering dithiodibenzothiazyl according to claim 2, wherein: the weight ratio of the AE active ester residual liquid to the benzene solvent in the step (2) is 1: 2-6.
4. The process for recovering dithiodibenzothiazyl according to any one of claims 1 to 3, characterized in that: the catalyst used in the step (3) is tetrahydrofuran, and the weight ratio of the AE active ester residual liquid to the catalyst is as follows: 1: 0.2-1.
5. The method for recovering dithiodibenzothiazyl according to claim 4, wherein: the catalytic initiator in the step (3) is any one of hydrogen peroxide, m-chloroperoxybenzoic acid or peracetic acid, and the weight ratio of the AE active ester residual liquid to the catalytic initiator is 1: 0.05-0.5.
6. The method for recovering dithiodibenzothiazyl according to claim 5, wherein: the temperature of the catalytic oxidation reaction in the step (3) is 20-60 ℃.
7. The method for recovering dithiodibenzothiazyl according to claim 6, wherein: the catalytic oxidation reaction time in the step (3) is 7-24 hours.
8. The method for recovering dithiodibenzothiazyl according to claim 7, wherein: the light source in the step (3) is any one of sunlight, incandescent lamps or fluorescent lamps.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010695008.XA CN111747906B (en) | 2020-07-19 | 2020-07-19 | Method for recycling dithiodibenzothiazyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010695008.XA CN111747906B (en) | 2020-07-19 | 2020-07-19 | Method for recycling dithiodibenzothiazyl |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111747906A true CN111747906A (en) | 2020-10-09 |
| CN111747906B CN111747906B (en) | 2023-05-05 |
Family
ID=72711562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010695008.XA Active CN111747906B (en) | 2020-07-19 | 2020-07-19 | Method for recycling dithiodibenzothiazyl |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111747906B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3780038A (en) * | 1971-08-04 | 1973-12-18 | Goodyear Tire & Rubber | Process of preparing an amino thiazolyl disulfide using wet 2-mercaptobenzothiazole |
| CN110330466A (en) * | 2019-07-25 | 2019-10-15 | 山东金城医药化工有限公司 | The method of curing di-mercaptobenzothiazolby is recycled from cephalo active ester production mother liquor |
-
2020
- 2020-07-19 CN CN202010695008.XA patent/CN111747906B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3780038A (en) * | 1971-08-04 | 1973-12-18 | Goodyear Tire & Rubber | Process of preparing an amino thiazolyl disulfide using wet 2-mercaptobenzothiazole |
| CN110330466A (en) * | 2019-07-25 | 2019-10-15 | 山东金城医药化工有限公司 | The method of curing di-mercaptobenzothiazolby is recycled from cephalo active ester production mother liquor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111747906B (en) | 2023-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2012051859A (en) | Method for producing diol compound | |
| CN102143967A (en) | Purification method for adefovir dipivoxil | |
| CN103044402A (en) | Method for synthesizing esomeprazole sodium | |
| CN111747906B (en) | Method for recycling dithiodibenzothiazyl | |
| CN107879995A (en) | The method that the M synthesis DM reclaimed in raffinate is synthesized using cefotaxime acid | |
| CN1863808B (en) | Penam crystal and process for producing the same | |
| KR20230066307A (en) | Method of manufacturing lithium compound | |
| CN111606941A (en) | Novel fluorosilicone rubber auxiliary agent and preparation method and application thereof | |
| CN101613392B (en) | Method for preparing hydrocortisone sodium succinate | |
| CN113845446B (en) | Preparation method of trifluoromethanesulfonic acid | |
| CN115368318A (en) | Synthetic method and application of vortioxetine | |
| CN111269196A (en) | Method for preparing NS by UHP oxidation | |
| CN113842897B (en) | Preparation method of cyclodextrin polymer for adsorbing organic dye | |
| CN109021223A (en) | A kind of preparation method of silane coupler containing sulfur | |
| CN1231475C (en) | Process for producing 2-cyanoimino-1, 3-thiazolidine | |
| CN109354595A (en) | A method of recycling triphenylphosphine oxide from Wittig reactive distillation raffinate | |
| CN113233972B (en) | Synthesis method of (R) -2-benzyloxy propionic acid and intermediate thereof | |
| CN114605494B (en) | Argatroban and preparation method of intermediate thereof | |
| CN115322243B (en) | Method for preparing triamcinolone acetonide key intermediate by one-pot method | |
| CN114539209B (en) | Preparation method of methylene methane disulfonate | |
| CN115716811B (en) | Method for preparing pharmaceutical grade DM by one step by using industrial grade accelerator M | |
| CN111040012B (en) | Preparation method of exemestane spirooxirane impurity | |
| CN111410649B (en) | Preparation method of ceritinib | |
| CN111675676B (en) | Preparation method of vulcanization accelerator 2-mercaptobenzothiazole | |
| CN106188000A (en) | A kind of synthetic method of Dexlansoprazole |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |