CN105418536B - The method that 2,2 ' dithio-bis-benzothiazoles are prepared by AE active esters production waste residue - Google Patents
The method that 2,2 ' dithio-bis-benzothiazoles are prepared by AE active esters production waste residue Download PDFInfo
- Publication number
- CN105418536B CN105418536B CN201511019667.7A CN201511019667A CN105418536B CN 105418536 B CN105418536 B CN 105418536B CN 201511019667 A CN201511019667 A CN 201511019667A CN 105418536 B CN105418536 B CN 105418536B
- Authority
- CN
- China
- Prior art keywords
- waste residue
- methoxyiminoacetic
- amino
- thiazolyl
- bis
- 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
- 239000002699 waste material Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 29
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical class C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 150000002148 esters Chemical class 0.000 title abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- COFDRZLHVALCDU-LICLKQGHSA-N s-(1,3-benzothiazol-2-yl) (2e)-2-(2-amino-1,3-thiazol-4-yl)-2-methoxyiminoethanethioate Chemical compound N=1C2=CC=CC=C2SC=1SC(=O)/C(=N/OC)C1=CSC(N)=N1 COFDRZLHVALCDU-LICLKQGHSA-N 0.000 claims description 40
- 238000001914 filtration Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000011109 contamination Methods 0.000 abstract description 2
- 239000003814 drug Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 10
- 239000000543 intermediate Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 6
- 229940069744 2,2'-dithiobisbenzothiazole Drugs 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000012267 brine Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229960004755 ceftriaxone Drugs 0.000 description 1
- VAAUVRVFOQPIGI-SPQHTLEESA-N ceftriaxone Chemical compound S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)\C(=N/OC)C=2N=C(N)SC=2)CC=1CSC1=NC(=O)C(=O)NN1C VAAUVRVFOQPIGI-SPQHTLEESA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 thio benzothiazoles Chemical class 0.000 description 1
- 229940041007 third-generation cephalosporins Drugs 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Abstract
The present invention relates to the method that one kind prepares 2,2' dithio-bis-benzothiazoles by AE active esters production waste residue, is that AE active esters production waste residue is dissolved in into methanol, catalyst TBAB is added, ozone, 1~1.5h of stirring reaction are passed through at 40~45 DEG C of temperature, treat that step a reactions are completed, stopping is passed through ozone, continues to stir, and is incubated 1~1.5 hour at the reaction temperatures, after be cooled to 5~10 DEG C, last filtered, vacuum drying treatment, obtains 2,2' dithio-bis-benzothiazoles.Using the inventive method, M that can be in high efficiente callback AE active esters production waste residue is to be prepared high-purity DM, and this method technique is simple, mild condition, safety, easily controllable, the solvent contamination used is small, easily recovery, production cost is low, suitable for large-scale production and application.
Description
Technical field
The present invention relates to the recycling method of pharmaceutical field production waste residue, more particularly to one kind to be given birth to by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester
The method that production waste residue prepares 2,2'- dithio-bis-benzothiazoles.
Background technology
2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester, chemical name 2- methoxyiminos -2- (2- amino -4- thiazolyls)-(z)-thioacetic acid benzo thiophene
Azoles ester, it is production Third generation Cephalosporins antibiotic ceftriaxone, the important intermediate of CTX, is widely used.AE- lives
Property ester by ainothiazoly loximate and 2,2'- dithio-bis-benzothiazoles (abbreviation DM) synthesis obtains, in the synthetic reaction mistake of 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester
Raw material DM can resolve into the thio benzothiazoles (abbreviation M) of 2 2- in journey, and one of M synthesizes AE- activity with ainothiazoly loximate
Ester, another M residuals are produced in waste residue to 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester, and the production waste residue can both cause greatly to pollute to environment, increase back up again
Add production cost, it is therefore desirable to 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue is handled, the M wherein remained is converted into DM, is back to AE-
In the production of active ester.The method that DM is reclaimed in the production waste residue from 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester published at present is a lot, but in big multi-method
Recycling step is cumbersome, complex operation, is unsuitable for large-scale production and application.
The content of the invention
To solve the deficiencies in the prior art, simply, easily to operate lived the invention provides a kind of step by AE-
Property ester production waste residue prepare 2,2'- dithio-bis-benzothiazoles method, be suitable for large-scale production and application.
To achieve the above object, it is of the invention that 2,2'- dithio-bis-benzothiazoles are prepared by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue
Method, comprise the following steps：
A, 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue is dissolved in methanol, catalyst TBAB is added, in 40~45 DEG C of temperature
Under be passed through ozone, 1~1.5h of stirring reaction；The catalyst charge be 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester produce waste residue weight 0.5~
0.6‰；
B, treat that step a reactions are completed, stopping is passed through ozone, continues to stir, and is incubated 1~1.5 hour at the reaction temperatures, after
5~10 DEG C are cooled to, last filtered, vacuum drying treatment, obtains 2,2'- dithio-bis-benzothiazoles.
As the restriction to the above method, the consumption proportion of 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue and methanol is in the step a
1kg:(2~2.2) L.
As the restriction to the above method, ozone intake is that 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester produces waste residue weight in the step a
4%~5%.
As the restriction to the above method, the filtration treatment of the step b uses centrifugal filtration mode.
As the restriction to the above method, the vacuum drying uses double-cone vacuum dryer.
It is of the present invention to be prepared by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue in the method for 2,2'- dithio-bis-benzothiazoles, methanol
On the one hand the solvent as dissolving 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue, the on the other hand reaction as M and ozone catalytic reaction production DM
Solvent, solvent of the another further aspect as dissolved impurity purifying DM, has the function that important.In addition, during DM reaction is prepared by M,
The selection of oxidant and catalyst is most important, and the oxidant and catalyst of selection will can make rapid reaction, efficiently carry out, both
Ensureing to produce the M in waste residue as far as possible more can must be oxidized to DM, improve the rate of recovery, ensure that all kinds of impurity do not influence to aoxidize again
It will not also be introduced in product DM while reaction, to obtain high-purity DM, consider under the influence of all kinds of factors, select
It is oxidant to take ozone, and TBAB is catalyst.Moreover, ozone, TBAB and methanol these three materials
Selection is to influence each other mutually restricting, it is necessary to which considering can just make reaction result meet production requirement.
In summary, using the side that 2,2'- dithio-bis-benzothiazoles are prepared by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue of the present invention
Method, M that can be in high efficiente callback 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue is to be prepared high-purity DM, and this method reaction rate is fast, yield
Height, the DM purity height of acquisition, quality are good, can reach medicine synthesis material standard, can be directly used for 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester or other medicines
The synthetic reaction of product intermediate, medicine.In addition, the inventive method technique is simple, mild condition, safety are easily controllable, use
Solvent contamination is small, easily recovery, and production cost is low, suitable for large-scale production and application.
Embodiment
Embodiment one
The present embodiment is related to the method for preparing 2,2'- dithio-bis-benzothiazoles by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue.Use
2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester produces waste residue, and wherein M contents are about 30%, and the other materials contained include ainothiazoly loximate, triethyl phosphate, AE-
Active ester etc..
Embodiment 1.1
2,2'- dithio-bis-benzothiazoles are prepared by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue, specifically comprised the following steps：
A, 500kg 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole esters production waste residue is dissolved in 1000L methanol, adds catalyst TBAB
0.25kg, after then heating makes reaction system be warming up to 40 DEG C, 20kg ozone is passed through with 9.3 cubic meters/hour, at 90 revs/min
Mixing speed under react 1h；.
B, treat that step a reactions are completed, stopping is passed through ozone, continues to stir, and system material is incubated 1 hour at 40 DEG C
Afterwards, logical cool brine is cooled to 10 DEG C, and the system material after cooling is rotated into capable filtering with per minute 900 by centrifuge, collects
Solid, finally with vacuum 0.09-0.095Mpa in double-cone vacuum dryer, it is small that 80-90 DEG C of temperature dries 4-5 to solid
When, product 2,2'- dithio-bis-benzothiazole 126kg are obtained, reaction yield reaches 96.5%.
The product 2 of acquisition, 2'- dithio-bis-benzothiazoles, fusing point are 180 DEG C -182 DEG C, Chun Du≤99%；The product can
It is directly used in 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester or other medicine intermediates, the synthetic reaction of medicine.
Embodiment 1.2
2,2'- dithio-bis-benzothiazoles are prepared by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue, specifically comprised the following steps：
A, 1000kg 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole esters production waste residue is dissolved in 2100L methanol, adds catalyst TBAB
0.6kg, after then heating makes reaction system be warming up to 42 DEG C, 45kg ozone is passed through with 9.5 cubic meters/hour, at 90 revs/min
1h is reacted under mixing speed；
B, treat that step a reactions are completed, stopping is passed through ozone, continues to stir, and system material is incubated 1.5 hours at 42 DEG C
Afterwards, logical cool brine is cooled to 8 DEG C, and the system material after cooling is rotated into capable filtering with per minute 900 by centrifuge, collected solid
Body, 4-5 hours are finally dried to solid with vacuum 0.09-0.095Mpa, 80-90 DEG C of temperature in double-cone vacuum dryer,
Product 2,2'- dithio-bis-benzothiazole 254kg are obtained, reaction yield reaches 97.2%.
The product 2 of acquisition, 2'- dithio-bis-benzothiazoles, fusing point are 180 DEG C -182 DEG C, Chun Du≤99%；The product can
It is directly used in 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester or other medicine intermediates, the synthetic reaction of medicine.
Embodiment 1.3
2,2'- dithio-bis-benzothiazoles are prepared by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue, specifically comprised the following steps：
A, 1500kg 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole esters production waste residue is dissolved in 3300L methanol, adds catalyst TBAB
0.82kg, after then heating makes reaction system be warming up to 44 DEG C, 75kg ozone is passed through with 9.5 cubic meters/hour, at 90 revs/min
Mixing speed under react 1.5h；
B, treat that step a reactions are completed, stopping is passed through ozone, continues to stir, and system material is incubated 1.5 hours at 44 DEG C
Afterwards, logical cool brine is cooled to 5 DEG C, and the system material after cooling is turned over into filter with per minute 900 by centrifuge, collects solid,
Finally 4-5 hours are dried to solid, obtained with vacuum 0.09-0.095Mpa, 80-90 DEG C of temperature in double-cone vacuum dryer
Product 2,2'- dithio-bis-benzothiazole 382kg, reaction yield reach 97.5%.
The product 2 of acquisition, 2'- dithio-bis-benzothiazoles, fusing point are 180 DEG C -182 DEG C, Chun Du≤99%；The product can
It is directly used in 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester or other medicine intermediates, the synthetic reaction of medicine.
Embodiment two
The present embodiment is related to one group of pair on preparing 2,2'- dithio-bis-benzothiazoles by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue
According to the facts test.
Embodiment 2.1
It is identical with embodiment 1.3, as a result reach 97.5% for reaction yield, product 2,2'- dithio-bis-benzothiazoles
Fusing point is 180 DEG C -182 DEG C, Chun Du≤99%, and it is anti-to can be directly used for 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester or other medicine intermediates, the synthesis of medicine
Should.
Embodiment 2.2
It is essentially identical with embodiment 1.3, catalyst TBAB is added without in difference reaction, reacts 3h, is protected
Warm 3h, obtained result are that reaction yield is less than 90%, product 2, and the fusing points of 2'- dithio-bis-benzothiazoles is less than 176 DEG C, pure
Degree is less than 97%, not directly for 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester or other medicine intermediates, the synthetic reaction of medicine, also needs to be purified
Processing.
Embodiment 2.3
Essentially identical with embodiment 1.3, difference is to substitute ozone with hydrogen peroxide, and is added without catalyst in reacting
TBAB, react 3h, be incubated 3h, obtained result be reaction yield be less than 88%, product 2, bis- thio dibenzo of 2'-
The fusing point of thiazole is less than 173 DEG C, purity is less than 92%, not directly for 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester or other medicine intermediates, medicine
Synthetic reaction, also need to carry out purification processes.
The experimental result of comparative example 2.1,2.2,2.3 is visible, of the present invention to produce waste residue system by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester
The method of standby 2,2'- dithio-bis-benzothiazoles, reaction rate is fast, high income, and the DM purity height of acquisition, quality are good, Neng Gouda
To medicine synthesis material standard, 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester or other medicine intermediates, the synthetic reaction of medicine can be directly used for.
Claims (5)
- A kind of 1. method that 2,2'- dithio-bis-benzothiazoles are prepared by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue, it is characterised in that the party Method comprises the following steps：A, 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue is dissolved in methanol, adds catalyst TBAB, lead at 40~45 DEG C of temperature Enter ozone, 1~1.5h of stirring reaction；The catalyst charge is that 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester produces 0.5~the 0.6 ‰ of waste residue weight；B, treat that step a reactions are completed, stopping is passed through ozone, continues to stir, and is incubated 1~1.5 hour at the reaction temperatures, rear cooling To 5~10 DEG C, last filtered, vacuum drying treatment, 2,2'- dithio-bis-benzothiazoles are obtained.
- 2. the method according to claim 1 that 2,2'- dithio-bis-benzothiazoles are prepared by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue, It is characterized in that：The consumption proportion of 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue and methanol is 1kg in the step a:(2~2.2) L.
- 3. the method according to claim 1 that 2,2'- dithio-bis-benzothiazoles are prepared by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue, It is characterized in that：Ozone intake is that 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester produces the 4%~5% of waste residue weight in the step a.
- 4. bis- thio dibenzo of 2,2'- is prepared by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue according to according to any one of claims 1 to 3 The method of thiazole, it is characterised in that：The filtration treatment of the step b uses centrifugal filtration mode.
- 5. bis- thio dibenzo of 2,2'- is prepared by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue according to according to any one of claims 1 to 3 The method of thiazole, it is characterised in that：The vacuum drying uses double-cone vacuum dryer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511019667.7A CN105418536B (en) | 2015-12-29 | 2015-12-29 | The method that 2,2 ' dithio-bis-benzothiazoles are prepared by AE active esters production waste residue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511019667.7A CN105418536B (en) | 2015-12-29 | 2015-12-29 | The method that 2,2 ' dithio-bis-benzothiazoles are prepared by AE active esters production waste residue |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105418536A CN105418536A (en) | 2016-03-23 |
| CN105418536B true CN105418536B (en) | 2018-02-02 |
Family
ID=55497141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201511019667.7A Active CN105418536B (en) | 2015-12-29 | 2015-12-29 | The method that 2,2 ' dithio-bis-benzothiazoles are prepared by AE active esters production waste residue |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105418536B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330466B (en) * | 2019-07-25 | 2021-02-26 | 山东金城医药化工有限公司 | Method for recovering dibenzothiazyl disulfide from mother liquor of production of cephalosporin active ester |
| CN113968827A (en) * | 2020-07-22 | 2022-01-25 | 东营市晨宏橡胶助剂有限公司 | Regeneration treatment process for waste material in cephalosporin production in pharmaceutical industry |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438224A (en) * | 2003-03-11 | 2003-08-27 | 武汉化工学院 | Method for preparing pure 2-dibenzo-thiazole-sulfide from waste slag of AE-active ester production |
| CN102807533A (en) * | 2012-08-25 | 2012-12-05 | 华北制药河北华民药业有限责任公司 | Method utilizing cefotaxime acid waste-liquor to prepare 2, 2'-dithio-dibenzo thiazole |
| CN103044354A (en) * | 2012-12-04 | 2013-04-17 | 山东鑫泉医药有限公司 | Production method for preparing pharmaceutical grade DM (Dibenzothiazyl Disulfide) with ozone serving as oxidant |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10055219A1 (en) * | 2000-11-08 | 2002-05-29 | Bayer Ag | Process for the preparation of dithiazolyl disulfides |
| CN1876698A (en) * | 2006-05-17 | 2006-12-13 | 濮阳市蔚林化工有限公司 | Production method of dibenzothiazole disulfide as rubber vulcanization accelerator |
| CN101215272A (en) * | 2008-01-16 | 2008-07-09 | 天津市科迈化工有限公司 | Method of producing rubber vulcanization accelerator DM |
-
2015
- 2015-12-29 CN CN201511019667.7A patent/CN105418536B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438224A (en) * | 2003-03-11 | 2003-08-27 | 武汉化工学院 | Method for preparing pure 2-dibenzo-thiazole-sulfide from waste slag of AE-active ester production |
| CN102807533A (en) * | 2012-08-25 | 2012-12-05 | 华北制药河北华民药业有限责任公司 | Method utilizing cefotaxime acid waste-liquor to prepare 2, 2'-dithio-dibenzo thiazole |
| CN103044354A (en) * | 2012-12-04 | 2013-04-17 | 山东鑫泉医药有限公司 | Production method for preparing pharmaceutical grade DM (Dibenzothiazyl Disulfide) with ozone serving as oxidant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105418536A (en) | 2016-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5460283B2 (en) | Method for producing lithium sulfide | |
| CN101830946B (en) | Method for synthesizing clindamycin phosphate | |
| CN103058983B (en) | Method for purifying glycolide | |
| CN104031065A (en) | Preparation method for tazobactam | |
| CN105418536B (en) | The method that 2,2 ' dithio-bis-benzothiazoles are prepared by AE active esters production waste residue | |
| CN103030232A (en) | Method for treating titanium-containing waste liquid produced by polyolefin catalyst | |
| CN101607892B (en) | Method for producing sodium citrate | |
| CN101289464B (en) | Process for recovering triphenyl phosphine oxide and 2-mercaptobenzothiazole from production waste liquid of cephalothin active ester | |
| CN104086439A (en) | Method for recovering pregabalin intermediate resolving agent (R)-(+)-alpha-phenylethylamine | |
| CN106905254B (en) | A kind of preparation method of 5- phenyl -1H- tetrazole | |
| CN106699681B (en) | Synthetic method of ethyl noraminothiazolyloximate | |
| CN104478747B (en) | A kind of method utilizing organic solvent to produce glycine | |
| CN105330545A (en) | Method for recycling oxalic acid from triazine ring cyclization mother liquor dreg with tin chloride as catalyst | |
| CN102992415B (en) | Treatment method of polyolefin catalyst residual liquid | |
| CN111518861B (en) | Novel process for preparing D-calcium pantothenate | |
| CN105524015B (en) | The method for preparing 2,2 ' dithio-bis-benzothiazoles by 2 thio benzothiazoles | |
| CN109942000B (en) | Treatment device and process for slag slurry generated in cold hydrogenation synthesis process | |
| CN109678651B (en) | Preparation method of high-purity alpha, alpha-dichloroethyl cyclopropane | |
| CN109354595B (en) | Method for recovering triphenylphosphine oxide from Wittig reaction rectification residual liquid | |
| CN101928261A (en) | Method for producing 2,2'-dibenzothiazolyl disulfide by nitric acid one-step method | |
| CN102503956A (en) | Preparation method of penicillanic acid sulphoxide diphenylmethyl ester | |
| CN106966901A (en) | A kind of preparation method of 6- hydroxyls -8- Lipase Catalyzed Resolution of Racemic Ethyl | |
| CN108484505B (en) | Preparation method of 2-methylimidazole | |
| CN103028224A (en) | Method for treating titanium tetrachloride-containing waste liquid | |
| CN101792453A (en) | Method for preparing 7-amino-3-sulfotetrazolthiomethylcephalosporanic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 050000 Hainan Road, Shijiazhuang economic and Technological Development Zone, Shijiazhuang, Hebei Province, No. 80 Patentee after: HEBEI HEJIA PHARMATECH GROUP CO.,LTD. Address before: 050000 Hainan Road, Shijiazhuang economic and Technological Development Zone, Shijiazhuang, Hebei Province, No. 80 Patentee before: HEBEI HEJIA MEDICINE TECHNOLOGY GROUP Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder | ||
| PE01 | Entry into force 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: Method for preparing 2,2 '- dithiodibenzothiazole from waste residue of AE active ester production Effective date of registration: 20220629 Granted publication date: 20180202 Pledgee: China CITIC Bank Co.,Ltd. Shijiazhuang Branch Pledgor: HEBEI HEJIA PHARMATECH GROUP CO.,LTD. Registration number: Y2022130000043 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20230831 Granted publication date: 20180202 Pledgee: China CITIC Bank Co.,Ltd. Shijiazhuang Branch Pledgor: HEBEI HEJIA PHARMATECH GROUP CO.,LTD. Registration number: Y2022130000043 |
|
| PE01 | Entry into force 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: Method for preparing 2,2 '- dithiodibenzothiazole from AE active ester production waste residue Effective date of registration: 20230904 Granted publication date: 20180202 Pledgee: China CITIC Bank Co.,Ltd. Shijiazhuang Branch Pledgor: HEBEI HEJIA PHARMATECH GROUP CO.,LTD. Registration number: Y2023980055239 |