CN111747906B - Method for recycling dithiodibenzothiazyl - Google Patents
Method for recycling dithiodibenzothiazyl Download PDFInfo
- Publication number
- CN111747906B CN111747906B CN202010695008.XA CN202010695008A CN111747906B CN 111747906 B CN111747906 B CN 111747906B CN 202010695008 A CN202010695008 A CN 202010695008A CN 111747906 B CN111747906 B CN 111747906B
- Authority
- CN
- China
- Prior art keywords
- active ester
- dithiodibenzothiazyl
- raffinate
- recovering
- carrying
- 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.)
- Active
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 dithiodibenzothiazyl from AE crude mother liquor generated in an AE active ester production process, 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, and filtering, washing and drying to obtain the dithiodibenzothiazole. The invention 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 raffinate containing 2-mercaptobenzothiazole produced in an AE active ester production process.
Background
Dithiodibenzothiazyl (DM for short in English), with CAS number 120-78-5, is the main raw material for producing AE active ester; the catalyst is also used as a general 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 is commonly referred to as fine DM) is an important pharmaceutical intermediate in the manufacture of cephalosporin antibiotics. The structural formula is as follows:
AE active ester (MAEM for short in english) is one of the main raw materials of semisynthetic cephalosporin antibiotics, and is used for synthesizing cefmenoxime hydrochloride, cefotaxime sodium, ceftriaxone sodium, cefetamet pivoxil and cefpirate Luo Dengdi three-and four-generation semisynthetic cephalosporins.
The AE active ester is prepared by reacting aminothioxime acid with dithiodibenzothiazyl under the action of condensing agent triethyl phosphite, wherein the byproduct 2-mercaptobenzothiazole is produced in the preparation process, and the produced amount is equivalent to about 60 percent of dithiodibenzothiazyl which is not utilized. In order to reduce the production cost of the AE active ester and relieve the pressure of three-waste treatment, the invention discloses a method for oxidizing and recovering dithiodibenzothiazyl by using a 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 pharmaceutical grade standard, and the recovered 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 dithiodibenzothiazyl in the AE active ester production process, so as to overcome the defects in the prior art and meet the requirements 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 generated in the AE active ester production process after the AE active ester crude product mother liquor is subjected to solvent recovery, which are called AE active ester residual liquid;
(2) Adding benzene solvent into AE active ester raffinate, stirring for 30-40 minutes at room temperature, and carrying out suction filtration to obtain a filtrate which is 2-mercaptobenzothiazole solution;
(3) Adding a catalyst into 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, pumping, and drying to obtain dithiodibenzothiazole.
Further, the benzene solvent in the step (2) is any one of toluene, xylene or chlorobenzene.
Further, in the step (2), the weight ratio of AE active ester raffinate to benzene solvent is 1:2-6.
Further, the catalyst used in the step (3) is tetrahydrofuran, and the weight ratio of AE active ester raffinate to the catalyst is: 1:0.2-1.
Further, in the step (3), the catalytic initiator is any one of hydrogen peroxide, m-chloroperoxybenzoic acid or peroxyacetic acid, and the weight ratio of AE active ester raffinate to the catalytic initiator is 1:0.05-0.5.
Further, the catalytic oxidation reaction temperature in the step (3) is 20-60 ℃.
Further, the catalytic oxidation reaction time in the step (3) is 7-24 hours.
Further, the light source in the step (3) is any one of sunlight, an incandescent lamp or a fluorescent lamp.
The invention has the advantages of stable process, simple operation, and the recovery rate of the dithiodibenzothiazyl reaching more than 90 percent, and the yield and the quality reaching the medical grade. Low production cost and is suitable for large-scale industrial production.
Detailed Description
The present invention will be described in further detail by way of examples.
Example 1:
200g of AE active ester raffinate and 600g of toluene are added into a 2000ml three-necked round bottom flask, stirred for 30 minutes at room temperature, and then filtered by suction, and the filtrate is 2-mercaptobenzothiazole solution;
adding 40g of tetrahydrofuran into a 2000ml three-necked round bottom flask of a 2-mercaptobenzothiazole solution, introducing oxygen, dropwise adding 20g of hydrogen peroxide at room temperature, carrying out catalytic oxidation reaction under sunlight irradiation, controlling the reaction temperature to be 30 ℃, cooling to 6 ℃ after 24 hours of reaction, stirring for 1.5 hours, carrying out suction filtration, washing a filter cake with toluene, pumping, and drying to obtain 109g of dithiodibenzothiazole. The yield was 91.3% and the melting point was 179.4-181.6.
Example 2:
200g of AE active ester raffinate and 800g of chlorobenzene are added into a 2000ml three-necked round bottom flask, stirred for 35 minutes at room temperature, and then filtered by suction, and the filtrate is 2-mercaptobenzothiazole solution;
adding 2-mercaptobenzothiazole solution into a 2000ml four-port 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:
200g of AE active ester raffinate and 1000g of dimethylbenzene are added into a 2000ml three-necked round bottom flask, stirred for 40 minutes at room temperature, and then filtered by suction, wherein the filtrate is 2-mercaptobenzothiazole solution;
adding 2-mercaptobenzothiazole solution into a 2000ml four-port round bottom flask, adding 200g of tetrahydrofuran, introducing air, dropwise adding 100g of peracetic 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, pumping, and drying to obtain 110g of dithiodibenzothiazole, wherein the yield is 92.4%, and the melting point is 180.1.2-181.6 ℃.
Claims (4)
1. A method for recovering dithiodibenzothiazyl comprising the steps of:
(1) Collecting residues generated in the AE active ester production process after the AE active ester crude product mother liquor is subjected to solvent recovery, wherein the residues are called AE active ester residual liquid;
(2) Adding benzene solvent into AE active ester raffinate, stirring for 30-40 minutes at room temperature, and carrying out suction filtration to obtain filtrate which is 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 with a benzene solvent, pumping, and drying to obtain dithiodibenzothiazole;
the benzene solvent in the step (2) is any one of toluene, xylene or chlorobenzene, and the weight ratio of AE active ester raffinate to the benzene solvent is 1:2-6;
the catalyst used in the step (3) is tetrahydrofuran, and the weight ratio of AE active ester raffinate to the catalyst is: 1:0.2-1, wherein the catalytic initiator is any one of hydrogen peroxide, m-chloroperoxybenzoic acid or peroxyacetic acid, and the weight ratio of AE active ester raffinate to the catalytic initiator is 1:0.05-0.5.
2. The method for recovering dithiodibenzothiazyl according to claim 1, wherein: the catalytic oxidation reaction temperature in the step (3) is 20-60 ℃.
3. The method for recovering dithiodibenzothiazyl according to claim 2, wherein: the catalytic oxidation reaction time in the step (3) is 7-24 hours.
4. A process for the recovery of dithiodibenzothiazyl according to claim 3, wherein: the light source in the step (3) is any one of sunlight, an incandescent lamp or a fluorescent lamp.
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 CN111747906A (en) | 2020-10-09 |
| CN111747906B true 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| 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 |
-
2020
- 2020-07-19 CN CN202010695008.XA patent/CN111747906B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|---|
| CN111747906A (en) | 2020-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111747906B (en) | Method for recycling dithiodibenzothiazyl | |
| CN116496159A (en) | Preparation method of ethyl 6,8-dichloro octoate | |
| CN107879995A (en) | The method that the M synthesis DM reclaimed in raffinate is synthesized using cefotaxime acid | |
| CN115557927A (en) | Preparation method of vinyl sulfate | |
| CN113845446B (en) | Preparation method of trifluoromethanesulfonic acid | |
| KR20230066307A (en) | Method of manufacturing lithium compound | |
| CN101613392B (en) | Method for preparing hydrocortisone sodium succinate | |
| CN101805327A (en) | Rabeprazole sodium compound and novel preparation method thereof | |
| CN109400600A (en) | The novel preparation method of 10 α-methoxyl group -9,10- dihydro lysergol | |
| CN108516944B (en) | Preparation method of methane disulfonic acid | |
| CN115368318A (en) | Synthetic method and application of vortioxetine | |
| CN111269196A (en) | Method for preparing NS by UHP oxidation | |
| CN109589998B (en) | Novel ZnO/Se/SiO2Preparation method of composite material and application of composite material in preparation of phthalide | |
| CN107365281B (en) | Synthesis method of dibenzothiazole disulfide | |
| CN111170894A (en) | Method for circularly producing urea phosphate by using wet-process phosphoric acid and urea phosphate mother liquor | |
| CN118164832B (en) | Preparation method of 1, 6-hexanedialdehyde | |
| CN115716811B (en) | Method for preparing pharmaceutical grade DM by one step by using industrial grade accelerator M | |
| CN1231475C (en) | Process for producing 2-cyanoimino-1, 3-thiazolidine | |
| CN115322243B (en) | Method for preparing triamcinolone acetonide key intermediate by one-pot method | |
| CN114539209B (en) | Preparation method of methylene methane disulfonate | |
| CN113233972B (en) | Synthesis method of (R) -2-benzyloxy propionic acid and intermediate thereof | |
| CN113321648B (en) | Synthetic method of atropine sulfate | |
| CN113842897B (en) | Preparation method of cyclodextrin polymer for adsorbing organic dye | |
| CN114605494B (en) | Argatroban and preparation method of intermediate thereof | |
| CN109836398B (en) | Preparation method of special biological buffer-piperazine-diethylsulfonic acid 1.5Na salt |
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 |