CN105418536A - Method for preparing 2,2'-dithiodibenzothiazole from waste residues generated during process of AE-active ester production - Google Patents
Method for preparing 2,2'-dithiodibenzothiazole from waste residues generated during process of AE-active ester production Download PDFInfo
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- CN105418536A CN105418536A CN201511019667.7A CN201511019667A CN105418536A CN 105418536 A CN105418536 A CN 105418536A CN 201511019667 A CN201511019667 A CN 201511019667A CN 105418536 A CN105418536 A CN 105418536A
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- Prior art keywords
- thiazolyl
- methoxyiminoacetic
- amino
- waste residue
- benzothiazole
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- 239000002699 waste material Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 34
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 150000002148 esters Chemical class 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 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
- 238000003756 stirring Methods 0.000 claims abstract description 12
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 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 45
- 229940069744 2,2'-dithiobisbenzothiazole Drugs 0.000 claims description 21
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000003814 drug Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 238000003786 synthesis reaction Methods 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
- 238000009413 insulation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- ZCXGMSGCBDSEOY-UHFFFAOYSA-N 2-benzothiazolsulfonic acid Chemical class C1=CC=C2SC(S(=O)(=O)O)=NC2=C1 ZCXGMSGCBDSEOY-UHFFFAOYSA-N 0.000 description 1
- -1 2-methoxyimino-2-(2-amino-4-thiazolyl)-(z)-thioacetic acid benzothiazole ester Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229960004261 cefotaxime Drugs 0.000 description 1
- GPRBEKHLDVQUJE-VINNURBNSA-N cefotaxime Chemical compound N([C@@H]1C(N2C(=C(COC(C)=O)CS[C@@H]21)C(O)=O)=O)C(=O)/C(=N/OC)C1=CSC(N)=N1 GPRBEKHLDVQUJE-VINNURBNSA-N 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
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000126 substance Substances 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
Abstract
The invention relates to a method for preparing 2,2'-dithiodibenzothiazole from waste residues generated during the process of AE-active ester production. The method comprises the following steps: dissolving waste residues generated during the process of AE-active ester production into methanol, adding a catalyst (tetrabutyl ammonium bromide), introducing ozone into the reactions system at a temperature of 40 to 45 DEG C, carrying out reactions for 1 to 1.5 hours under stirring, after the reactions (a), stopping introducing ozone, keeping on stirring, maintaining the reaction temperature for 1 to 1.5 hours, then cooling to a temperature of 5 to 10 DEG C, filtering, and drying the reaction product in vacuum to obtain 2,2'-dithiodibenzothiazole. The provided method can high efficiently recover M from the waste residues generated during the process of AE-active ester production so as to produce high purity DM; moreover, the provided method has the advantages of simple technology, mild conditions, safety, and easiness in controlling, the used solvent is easy to recover and generates little pollution, the production cost is low, and the preparation method is suitable for large scale production.
Description
Technical field
The present invention relates to the recycling method that pharmacy field produces waste residue, particularly relate to a kind of method being prepared 2,2'-dithio-bis-benzothiazole by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue.
Background technology
2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester, chemical name 2-methoxyimino-2-(2-amino-4-thiazolyl)-(z)-thioacetic acid benzothiazole ester, be the important intermediate of producing Third generation Cephalosporins microbiotic ceftriaxone, cefotaxime, be widely used.2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester is by ainothiazoly loximate and 2,2'-dithio-bis-benzothiazole (being called for short DM) synthesis obtains, 2 2-sulfo-benzothiazoles (being called for short M) can be resolved at the synthetic reaction process Raw DM of 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester, one of them M and ainothiazoly loximate synthesize 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester, another one M remains 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester and produces in waste residue, this production waste residue both can cause very big pollution to environment, return again increase production cost, therefore need to produce waste residue to 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester to process, wherein residual M is transformed DM, is back in the production of 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester.Published at present to produce waste residue from 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester the method reclaiming DM a lot, but in large multi-method, recycling step is loaded down with trivial details, and complicated operation, is unsuitable for large-scale production and application.
Summary of the invention
For solving the deficiencies in the prior art, the invention provides a kind of method being prepared 2,2'-dithio-bis-benzothiazole by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue that step is simple, easy and simple to handle, to be suitable for large-scale production and application.
For achieving the above object, the method being prepared 2,2'-dithio-bis-benzothiazole by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue of the present invention, comprises the following steps:
A, 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester is produced waste residue be dissolved in methyl alcohol, then add catalyzer Tetrabutyl amonium bromide, at temperature 40 ~ 45 DEG C, pass into ozone, stirring reaction 1 ~ 1.5h; Described catalyst charge is that 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester produces 0.5 ~ 0.6 ‰ of waste residue weight;
B, treat that step a has reacted, stop passing into ozone, continue to stir, be incubated 1 ~ 1.5 hour at the reaction temperatures, after be cooled to 5 ~ 10 DEG C, finally by filtration, vacuum drying treatment, obtain 2,2'-dithio-bis-benzothiazole.
As the restriction to aforesaid method, in described step a, 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester produces the consumption proportion of waste residue and methyl alcohol is 1kg:(2 ~ 2.2) L.
As the restriction to aforesaid method, in described step a, ozone intake is that 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester produces 4% ~ 5% of waste residue weight.
As the restriction to aforesaid method, the filtration treatment of described step b adopts centrifuging mode.
As the restriction to aforesaid method, described vacuum-drying adopts double-cone vacuum dryer.
Of the present invention by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester produce waste residue prepare 2, in the method for 2'-dithio-bis-benzothiazole, methyl alcohol is on the one hand as the solvent dissolving 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue, the reaction solvent producing DM is reacted on the other hand as M and ozone catalytic, again on the one hand as the solvent of dissolved impurity purifying DM, there is important effect.In addition, prepare in the reaction of DM by M, choosing of oxygenant and catalyzer is most important, and the oxygenant chosen and catalyzer are wanted to make reaction carry out fast and efficiently, should ensure that the M produced in waste residue must be oxidized to DM more than try one's best, improve the rate of recovery, ensure that all kinds of impurity also can not be introduced in product D M while not affecting oxidizing reaction again, to obtain high purity DM, consider under the impact of all kinds of factor, choosing ozone is oxygenant, and Tetrabutyl amonium bromide is catalyzer.And the choosing to influence each other of these three kinds of materials of ozone, Tetrabutyl amonium bromide and methyl alcohol restricts mutually, need to consider just to make reaction result meet production requirement.
In sum, adopt of the present invention by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester produce waste residue prepare 2, the method of 2'-dithio-bis-benzothiazole, M in waste residue can be produced to prepare high-purity DM by high efficiente callback 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester, the method speed of reaction is fast, yield is high, the DM purity obtained is high, quality good, can reach medicine synthesis material standard, can be directly used in the building-up reactions of 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester or other medicine intermediate, medicine.In addition, the inventive method technique is simple, mild condition, safety, and be easy to control, the solvent contamination of use is little, easily reclaims, and production cost is low, is suitable for large-scale production and application.
Embodiment
Embodiment one
The present embodiment relates to the method being prepared 2,2'-dithio-bis-benzothiazole by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue.The 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester used produces waste residue, and wherein M content is about 30%, and other material contained comprises ainothiazoly loximate, triethyl phosphate, 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester etc.
Embodiment 1.1
Produce waste residue by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester and prepare 2,2'-dithio-bis-benzothiazole, specifically comprise the steps:
A, by 500kgAE-active ester produce waste residue be dissolved in 1000L methyl alcohol, add catalyzer Tetrabutyl amonium bromide 0.25kg, then, after heating makes reaction system be warming up to 40 DEG C, pass into 20kg ozone with 9.3 cubic meters/hour, under the stirring velocity of 90 revs/min, react 1h; .
B, treat that step a has reacted, stop passing into ozone, continue to stir, after making system material be incubated 1 hour at 40 DEG C, logical cool brine is cooled to 10 DEG C, cooled system material is filtered with per minute 900 turns by whizzer, collect solid, finally in double-cone vacuum dryer with vacuum tightness 0.09-0.095Mpa, temperature 80-90 DEG C to solid drying 4-5 hour, obtain product 2,2'-dithio-bis-benzothiazole 126kg, reaction yield reaches 96.5%.
Product 2, the 2'-dithio-bis-benzothiazole obtained, fusing point is 180 DEG C-182 DEG C, Chun Du≤99%; This product can be directly used in the building-up reactions of 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester or other medicine intermediate, medicine.
Embodiment 1.2
Produce waste residue by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester and prepare 2,2'-dithio-bis-benzothiazole, specifically comprise the steps:
A, by 1000kgAE-active ester produce waste residue be dissolved in 2100L methyl alcohol, add catalyzer Tetrabutyl amonium bromide 0.6kg, then, after heating makes reaction system be warming up to 42 DEG C, pass into 45kg ozone with 9.5 cubic meters/hour, under the stirring velocity of 90 revs/min, react 1h;
B, treat that step a has reacted, stop passing into ozone, continue to stir, after making system material be incubated 1.5 hours at 42 DEG C, logical cool brine is cooled to 8 DEG C, cooled system material is filtered with per minute 900 turns by whizzer, collect solid, finally in double-cone vacuum dryer with vacuum tightness 0.09-0.095Mpa, temperature 80-90 DEG C to solid drying 4-5 hour, obtain product 2,2'-dithio-bis-benzothiazole 254kg, reaction yield reaches 97.2%.
Product 2, the 2'-dithio-bis-benzothiazole obtained, fusing point is 180 DEG C-182 DEG C, Chun Du≤99%; This product can be directly used in the building-up reactions of 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester or other medicine intermediate, medicine.
Embodiment 1.3
Produce waste residue by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester and prepare 2,2'-dithio-bis-benzothiazole, specifically comprise the steps:
A, by 1500kgAE-active ester produce waste residue be dissolved in 3300L methyl alcohol, add catalyzer Tetrabutyl amonium bromide 0.82kg, then, after heating makes reaction system be warming up to 44 DEG C, pass into 75kg ozone with 9.5 cubic meters/hour, under the stirring velocity of 90 revs/min, react 1.5h;
B, treat that step a has reacted, stop passing into ozone, continue to stir, after making system material be incubated 1.5 hours at 44 DEG C, logical cool brine is cooled to 5 DEG C, cooled system material is turned over filter by whizzer with per minute 900, collect solid, finally in double-cone vacuum dryer with vacuum tightness 0.09-0.095Mpa, temperature 80-90 DEG C to solid drying 4-5 hour, obtain product 2,2'-dithio-bis-benzothiazole 382kg, reaction yield reaches 97.5%.
Product 2, the 2'-dithio-bis-benzothiazole obtained, fusing point is 180 DEG C-182 DEG C, Chun Du≤99%; This product can be directly used in the building-up reactions of 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester or other medicine intermediate, medicine.
Embodiment two
The present embodiment relates to one group about the control experiment being prepared 2,2'-dithio-bis-benzothiazole by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue.
Embodiment 2.1
Identical with embodiment 1.3, result is that reaction yield reaches 97.5%, and the fusing point of product 2,2'-dithio-bis-benzothiazole is 180 DEG C-182 DEG C, Chun Du≤99%, can be directly used in the building-up reactions of 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester or other medicine intermediate, medicine.
Embodiment 2.2
Substantially identical with embodiment 1.3, catalyzer Tetrabutyl amonium bromide is not added in difference reaction, reaction 3h, insulation 3h, the result obtained is that reaction yield is less than 90%, product 2, the fusing point of 2'-dithio-bis-benzothiazole is less than 176 DEG C, purity is less than 97%, not directly for the building-up reactions of 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester or other medicine intermediate, medicine, also needs to carry out purification processes.
Embodiment 2.3
Substantially identical with embodiment 1.3, difference is to substitute ozone with hydrogen peroxide, and do not add catalyzer Tetrabutyl amonium bromide in reaction, reaction 3h, insulation 3h, the result obtained is that reaction yield is less than 88%, the fusing point of product 2,2'-dithio-bis-benzothiazole is less than 173 DEG C, and purity is less than 92%, not directly for the building-up reactions of 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester or other medicine intermediate, medicine, 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 by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester produce waste residue prepare 2, the method of 2'-dithio-bis-benzothiazole, speed of reaction is fast, yield is high, the DM purity obtained is high, quality good, medicine synthesis material standard can be reached, the building-up reactions of 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester or other medicine intermediate, medicine can be directly used in.
Claims (5)
1. prepared the method for 2,2'-dithio-bis-benzothiazole by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue for one kind, it is characterized in that, the method comprises the following steps:
A, 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester is produced waste residue be dissolved in methyl alcohol, then add catalyzer Tetrabutyl amonium bromide, at temperature 40 ~ 45 DEG C, pass into ozone, stirring reaction 1 ~ 1.5h; Described catalyst charge is that 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester produces 0.5 ~ 0.6 ‰ of waste residue weight;
B, treat that step a has reacted, stop passing into ozone, continue to stir, be incubated 1 ~ 1.5 hour at the reaction temperatures, after be cooled to 5 ~ 10 DEG C, finally by filtration, vacuum drying treatment, obtain 2,2'-dithio-bis-benzothiazole.
2. the method being prepared 2,2'-dithio-bis-benzothiazole by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue according to claim 1, is characterized in that: in described step a, 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester produces the consumption proportion of waste residue and methyl alcohol is 1kg:(2 ~ 2.2) L.
3. the method being prepared 2,2'-dithio-bis-benzothiazole by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue according to claim 1, is characterized in that: in described step a, ozone intake is that 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester produces 4% ~ 5% of waste residue weight.
4. the method being prepared 2,2'-dithio-bis-benzothiazole by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue according to any one of claims 1 to 3, is characterized in that: the filtration treatment of described step b adopts centrifuging mode.
5. the method being prepared 2,2'-dithio-bis-benzothiazole by 2-(2-Amino-4-thiazolyl)-2-methoxyiminoacetic,thiobenzothiazole ester production waste residue according to any one of claims 1 to 3, is characterized in that: described vacuum-drying adopts double-cone vacuum dryer.
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| 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 |
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|---|---|
| CN105418536B (en) | 2018-02-02 |
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