CN105198835B - The synthesis technique of the formic acid of benzothiazole 2 - Google Patents
The synthesis technique of the formic acid of benzothiazole 2 Download PDFInfo
- Publication number
- CN105198835B CN105198835B CN201510613067.7A CN201510613067A CN105198835B CN 105198835 B CN105198835 B CN 105198835B CN 201510613067 A CN201510613067 A CN 201510613067A CN 105198835 B CN105198835 B CN 105198835B
- Authority
- CN
- China
- Prior art keywords
- benzothiazole
- formic acid
- dimethylacetal
- acid
- phosphorus
- 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
Abstract
The present invention relates to a kind of synthesis technique of the formic acid of benzothiazole 2, comprise the following steps：Step one, benzothiazole, methanol, oxidant, phosphorus-containing catalyst are heated in closed reaction vessel, is incubated and stirs and reacted, obtain 2 benzothiazole dimethylacetals；Step 2, the 2 benzothiazole dimethylacetal is added in organic solvent DMF, is added acid catalyst reaction, is obtained the formaldehyde of benzothiazole 2；Step 3, under the catalysis of manganese acetate and potassium permanganate, carries out oxidation reaction by the formaldehyde of benzothiazole 2 and the oxygen being passed through, obtains the formic acid of benzothiazole 2.The present invention has effectively facilitated the combined coefficient of the benzothiazole dimethylacetal of intermediate 2 using phosphorus-containing catalyst, and raw material is easy to get, cost is low, step is simple, it is easy to operate, the later stage is conducive to further to synthesize the formaldehyde of benzothiazole 2 and the formic acid of benzothiazole 2, it is adaptable to the industrial extensive synthesis formic acid of benzothiazole 2.
Description
Technical field
The present invention relates to a kind of synthesis technique of benzothiazole analog derivative, and in particular to a kind of benzothiazole -2- formic acid
Synthesis technique.
Background technology
Benzothiazole is the extremely important heterocyclic compound of a class, is had extensively in fields such as medicine, agricultural chemicals, material engineering
Purposes.For example, pharmaceutically, benzothiazole compound can be also used for anti-parasitism as bactericide, fungicidal agent etc.
Worm, antituberculosis, wind resistance diseases caused by dampness and anticancer etc.；Agriculturally, benzothiazole compound have resist agricultural fungi, desinsection, weeding,
Plant growth regulating isoreactivity；In material engineering field, benzothiazole compound may be used as thiofide, plastics
Ultraviolet absorber, liquid crystal display material, electroluminescent material and fluorescence probe material in coloring agent, cosmetics and sunglasses
Deng.2- replaces benzo thiazole derivative as a kind of nitrogen-containing heterocycle compound, with extensive bioactivity and pharmacological activity,
Replaced benzothiazole compound as 2- as important pharmaceutical synthesis construction unit, especially benzothiazole -2- formic acid, be
A kind of important organic medicinal intermediate, anticancer, anti-inflammatory, it is antiviral in terms of play an important role, so research benzene
And thiazole -2- formic acid synthesis technique is significant and application value.
At present, the synthetic method of benzothiazole 2- formic acid, mainly including CO2Carboxylation method, Hydrolyze method, potassium permanganate oxidation method
With Phillips synthetic methods；Wherein CO2Carboxylation method includes catalysis synthesis process and catalyst-free synthesis method, but these methods are present
Process is more, complex operation, the shortcoming and defect that yield is low and cost is high, is unfavorable for industrial large-scale promotion application.
Therefore, there is further improvement and optimization demand in the synthetic method for benzothiazole 2- formic acid, and this is exactly originally
Invent the power being accomplished and starting point place.
The content of the invention
In order to overcome the above-mentioned technical problem that prior art is present, after substantial amounts of further investigation, so as to provide
A kind of synthesis technique of new benzothiazole -2- formic acid, with process is few, simple to operate, high income and cost are low
Advantage.
The present invention is achieved through the following technical solutions, a kind of synthesis technique of new benzothiazole -2- formic acid, including such as
Lower step：
Step one, benzothiazole, methanol, oxidant, phosphorus-containing catalyst are heated to 80~120 in closed reaction vessel
DEG C, be incubated and stir 1~18 hour and reacted, the oxidant be potassium peroxydisulfate or sodium peroxydisulfate or the mixture of the two,
Filtering, filtrate decompression concentration, with acetone recrystallization, obtains solid 2-[4-morpholinodithio dimethylacetal；
Step 2, the 2-[4-morpholinodithio dimethylacetal is added in organic solvent DMF, is contracted according to 2-[4-morpholinodithio diformazan
The ratio between amount of material of aldehyde and acid catalyst is 1:(1~10) adds acid catalyst hydrochloric acid or sulfuric acid, 30~100 DEG C of temperature
Under the conditions of react 1~20 hour, be concentrated under reduced pressure, recrystallisation from isopropanol obtains white solid benzothiazole -2- formaldehyde；
Step 3, using glacial acetic acid as solvent, under the catalysis of manganese acetate and potassium permanganate, by the benzothiazole -2-
Formaldehyde and the oxygen being passed through carry out oxidation reaction, and reaction temperature is 5-10 DEG C, and the reaction time is 48-72 hours, is concentrated under reduced pressure, mistake
Filter, recrystallisation from isopropanol obtains white solid benzothiazole 2- formic acid.
It is preferred that, in step one, the phosphorus-containing catalyst is hydroxyapatite powder.
It is preferred that, in step one, the benzothiazole, methanol, oxidant, the mol ratio of phosphorus-containing catalyst are 1:(3~
8):(1~8):(0.01~0.6), it is further preferred that mole of the benzothiazole, methanol, oxidant, phosphorus-containing catalyst
Than for 1:5:3:0.1.
It is preferred that, in step one, reaction temperature is 90 DEG C.
It is preferred that, in step one, reaction mixing time is 10 hours.
The reaction equation of the present invention is as follows：
Compared with prior art, the present invention has the advantages that:The present invention is effectively facilitated using phosphorus-containing catalyst
Benzothiazole and methanol react the efficiency that 2-[4-morpholinodithio dimethylacetal is made, and phosphorus-containing catalyst in the presence of oxidant
It is easy to get Deng raw material, cost is low, process is few, simple to operate, the high income of 2-[4-morpholinodithio dimethylacetal has up to 80% or so
Benzothiazole -2- formaldehyde and benzothiazole -2- formic acid are further synthesized beneficial to the later stage, it is adaptable to industrial extensive synthesis benzo
Thiazole -2- formic acid.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the ordinary skill of this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the present invention
Protection domain.
Embodiment 1
The present embodiment is related to a kind of synthesis technique of benzothiazole -2- formic acid, comprises the steps of：
Step one, it is 0.1mol benzothiazoles, 0.5mol methanol, 0.3mol oxidants potassium peroxydisulfate and 0.01mol is phosphorous
Catalyst (hydroxyapatite powder), is heated to 90 DEG C in closed reaction vessel, is incubated and stirs 10 hours and is reacted, mistake
Filter, filtrate decompression concentration, uses 50mL acetone recrystallizations, obtains solid 2-[4-morpholinodithio dimethylacetal 17g, yield 81%, purity
99.3%, MS:M/z=209 (M+)；
Step 2, above-mentioned 2-[4-morpholinodithio dimethylacetal is added in organic solvent DMF, is contracted according to 2-[4-morpholinodithio diformazan
The ratio between amount of material of aldehyde and acid catalyst is 1:5 add reaction 10 hours under acid catalyst hydrochloric acid, 50 DEG C of temperature conditionss,
It is concentrated under reduced pressure, 50mL recrystallisation from isopropanol obtains white solid benzothiazole -2- formaldehyde 11.4g, yield 86%, purity 99.6%,
MS:M/z=163 (M+),1H NMR(CDCl3,500MHz)δ:10.18 (s, 1H), 8.25 (d, J=8.5Hz, 1H), 8.02 (d, J
=8.5Hz, 1H), 7.63-7.59 (m, 2H)；
Step 3, using 100mL glacial acetic acid as solvent, in manganese acetate and the potassium permanganate (weight of manganese acetate and potassium permanganate
Amount compares 0.1:100) as under the catalytic action of catalyst, above-mentioned benzothiazole -2- formaldehyde and the oxygen being passed through are aoxidized
React (weight consumption of catalyst accounts for the 1% of benzothiazole -2- formaldehyde), reaction temperature is 7 DEG C, the reaction time is 60 hours,
It is concentrated under reduced pressure, filters, recrystallisation from isopropanol obtains white solid benzothiazole 2- formic acid 10.1g, yield 80.3%, purity
98.7%, MS:M/z=179 (M+),1H NMR(CDCl3,500MHz)δ:11.02 (s, 1H), 8.31 (d, J=8.5Hz, 1H),
8.09 (d, J=8.5Hz, 1H), 7.73-7.68 (m, 2H).
Embodiment 2
The present embodiment is related to a kind of synthesis technique of benzothiazole -2- formic acid, comprises the steps of：
Step one, it is 0.1mol benzothiazoles, 0.3mol methanol, 0.8mol oxidants sodium peroxydisulfate and 0.001mol is phosphorous
Catalyst (hydroxyapatite powder), is heated to 80 DEG C in closed reaction vessel, is incubated and stirs 18 hours and is reacted, mistake
Filter, filtrate decompression concentration, uses 50mL acetone recrystallizations, obtains solid 2-[4-morpholinodithio dimethylacetal 16.5g, yield 78% is pure
Spend 99.1%, MS:M/z=209 (M+)；
Step 2, above-mentioned 2-[4-morpholinodithio dimethylacetal is added in organic solvent DMF, is contracted according to 2-[4-morpholinodithio diformazan
The ratio between amount of material of aldehyde and acid catalyst is 1:1 adds reaction 1 hour under acid catalyst sulfuric acid, 100 DEG C of temperature conditionss,
It is concentrated under reduced pressure, 50mL recrystallisation from isopropanol obtains white solid benzothiazole -2- formaldehyde 10.7g, yield 84%, purity 99.4%,
MS:M/z=163 (M+),1H NMR(CDCl3,500MHz)δ:10.19 (s, 1H), 8.27 (d, J=8.5Hz, 1H), 8.04 (d, J
=8.5Hz, 1H), 7.64-7.60 (m, 2H)；
Step 3, using glacial acetic acid as solvent, under the catalysis of manganese acetate and potassium permanganate, by the benzothiazole -2-
Formaldehyde and the oxygen being passed through carry out oxidation reaction, and reaction temperature is 5 DEG C, and the reaction time is 72 hours, is concentrated under reduced pressure, and is filtered, different
Propyl alcohol is recrystallized, and obtains white solid benzothiazole 2- formic acid 9.5g, yield 79.9%, purity 99.1%, MS:M/z=179 (M+),1H NMR(CDCl3,500MHz)δ:11.01 (s, 1H), 8.30 (d, J=8.5Hz, 1H), 8.10 (d, J=8.5Hz, 1H),
7.72-7.68(m,2H)。
Embodiment 3
The present embodiment is related to a kind of synthesis technique of benzothiazole -2- formic acid, comprises the steps of：
Step one, by 0.1mol benzothiazoles, 0.8mol methanol, 0.1mol oxidants, (potassium peroxydisulfate and sodium peroxydisulfate are each
Half) and 0.06mol phosphorus-containing catalysts (hydroxyapatite powder), 120 DEG C are heated in closed reaction vessel, is incubated and stirs
Mix 1 hour and reacted, filtered, filtrate decompression concentration uses 50mL acetone recrystallizations, obtains solid 2-[4-morpholinodithio dimethylacetal
16.6g, yield 79%, purity 99.2%, MS:M/z=209 (M+)；
Step 2, above-mentioned 2-[4-morpholinodithio dimethylacetal is added in organic solvent DMF, is contracted according to 2-[4-morpholinodithio diformazan
The ratio between amount of material of aldehyde and acid catalyst is 1:10 to add under acid catalyst hydrochloric acid, 30 DEG C of temperature conditionss reaction 20 small
When, it is concentrated under reduced pressure, 50mL recrystallisation from isopropanol obtains white solid benzothiazole -2- formaldehyde 11g, yield 85%, purity
99.3%, MS:M/z=163 (M+),1H NMR(CDCl3,500MHz)δ:10.18 (s, 1H), 8.25 (d, J=8.5Hz, 1H),
8.02 (d, J=8.5Hz, 1H), 7.66-7.59 (m, 2H)；
Step 3, using glacial acetic acid as solvent, under the catalysis of manganese acetate and potassium permanganate, by the benzothiazole -2-
Formaldehyde and the oxygen being passed through carry out oxidation reaction, and reaction temperature is 10 DEG C, and the reaction time is 48 hours, is concentrated under reduced pressure, and is filtered, different
Propyl alcohol is recrystallized, and obtains white solid benzothiazole 2- formic acid 9.7g, yield 80%, purity 98.9%, MS:M/z=179 (M+),1H
NMR(CDCl3,500MHz)δ:11.02 (s, 1H), 8.32 (d, J=8.5Hz, 1H), 8.09 (d, J=8.5Hz, 1H), 7.74-
7.67(m,2H)。
Comparative example 1
The difference of this comparative example and embodiment 1 is：In step one, phosphorus-containing catalyst (hydroxylapatite powder is added without
End), obtain solid 2-[4-morpholinodithio dimethylacetal 13.1g, yield 62%, purity 99.1%, MS:M/z=209 (M+)。
Comparative example 2
The difference of this comparative example and embodiment 2 is：In step one, phosphorus-containing catalyst (hydroxylapatite powder is added without
End), obtain solid 2-[4-morpholinodithio dimethylacetal 7.4g, yield 35%, purity 99.2%, MS:M/z=209 (M+)。
Comparative example 3
The difference of this comparative example and embodiment 3 is：In step one, phosphorus-containing catalyst (hydroxylapatite powder is added without
End), obtain solid 2-[4-morpholinodithio dimethylacetal 10.4g, yield 49%, purity 98.7%, MS:M/z=209 (M+)。
Analysis of conclusion
Implement above-described embodiment 1-3 and comparative example 1-3 respectively, and count 2-[4-morpholinodithio dimethylacetal and benzothiazole-
The yield and purity of 2- formic acid.Embodiment 1-3 obtains the yield of 2-[4-morpholinodithio dimethylacetal between 78-81%, and right
Ratio 1-3 is after omit phosphorus-containing catalyst (hydroxyapatite powder), and 2-[4-morpholinodithio dimethylacetal drops to 35-62%,
Fall is beyond expectation, illustrates that hydroxyapatite powder has as catalyst to the generation for generating 2-[4-morpholinodithio dimethylacetal
Vital influence, especially benzothiazole, methanol, oxidant, phosphorus-containing catalyst mol ratio be 1:(3~8):(1~
8):Influence is more protruded when (0.01~0.6), and benzothiazole, methanol, oxidant, the mol ratio of phosphorus-containing catalyst are 1:5:3:
Better when 0.1, the high efficiency synthesis of 2-[4-morpholinodithio dimethylacetal is conducive to the later stage further to synthesize benzothiazole -2- first
Aldehyde and benzothiazole -2- formic acid, therefore, it is adaptable to industrial extensive synthesis benzothiazole -2- formic acid.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (1)
1. a kind of synthesis technique of benzothiazole -2- formic acid, it is characterised in that comprise the following steps：
Step one, benzothiazole, methanol, oxidant, phosphorus-containing catalyst are heated to 90 DEG C in closed reaction vessel, insulation is simultaneously
Stirring is reacted for 10 hours, and the oxidant is potassium peroxydisulfate or sodium peroxydisulfate or the mixture of the two, filtering, filtrate decompression
Concentration, with acetone recrystallization, obtains solid 2-[4-morpholinodithio dimethylacetal, the phosphorus-containing catalyst is hydroxyapatite powder,
The benzothiazole, methanol, oxidant, the mol ratio of phosphorus-containing catalyst are 1:5:3:0.1；
Step 2, the 2-[4-morpholinodithio dimethylacetal is added in organic solvent DMF, according to 2-[4-morpholinodithio dimethylacetal with
The ratio between amount of material of acid catalyst is 1:(1~10) adds acid catalyst hydrochloric acid or sulfuric acid, 30~100 DEG C of temperature conditionss
Lower reaction 1~20 hour, is concentrated under reduced pressure, recrystallisation from isopropanol obtains white solid benzothiazole -2- formaldehyde；
Step 3, using glacial acetic acid as solvent, under the catalytic action of manganese acetate and potassium permanganate, by the benzothiazole -2-
Formaldehyde and the oxygen being passed through carry out oxidation reaction, and reaction temperature is 5-10 DEG C, and the reaction time is 48-72 hours, is concentrated under reduced pressure, mistake
Filter, recrystallisation from isopropanol obtains white solid benzothiazole 2- formic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510613067.7A CN105198835B (en) | 2015-09-23 | 2015-09-23 | The synthesis technique of the formic acid of benzothiazole 2 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510613067.7A CN105198835B (en) | 2015-09-23 | 2015-09-23 | The synthesis technique of the formic acid of benzothiazole 2 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105198835A CN105198835A (en) | 2015-12-30 |
| CN105198835B true CN105198835B (en) | 2017-09-29 |
Family
ID=54946833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510613067.7A Active CN105198835B (en) | 2015-09-23 | 2015-09-23 | The synthesis technique of the formic acid of benzothiazole 2 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105198835B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467585B (en) * | 2019-08-26 | 2021-11-23 | 浙江工业大学 | Mild preparation method of substituted benzothiazole C2 hydroxyalkylated derivative |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977050A (en) * | 2012-11-20 | 2013-03-20 | 浙江工业大学 | Method for synthesizing 2-benzothiazolyl dimethylacetal and 2-benzothiazol formaldehyde |
-
2015
- 2015-09-23 CN CN201510613067.7A patent/CN105198835B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977050A (en) * | 2012-11-20 | 2013-03-20 | 浙江工业大学 | Method for synthesizing 2-benzothiazolyl dimethylacetal and 2-benzothiazol formaldehyde |
Non-Patent Citations (3)
| Title |
|---|
| A General, Selective, and Convenient Procedure of Homolytic Formylation of Heteroaromatic;Claudio Giordano;《J. Org. Chem》;19861231;第51卷;536-537 * |
| Cu-Catalyzed Cross-Dehydrogenative Coupling Reactions of (Benzo)thiazoles with Cyclic Ethers;Zengyang Xie et al.;《Org. Lett.》;20130822;第15卷;4600-4603 * |
| Multifold Bond Cleavage and Formation between MeOH and Quinoxalines (or Benzothiazoles): Synthesis of Carbaldehyde Dimethyl Acetals;Yunkui Liu et al.;《J. Org. Chem.》;20130107;第78卷;966-980 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105198835A (en) | 2015-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103304512A (en) | Preparation method for febuxostat | |
| CN105198835B (en) | The synthesis technique of the formic acid of benzothiazole 2 | |
| CN103613568B (en) | The preparation method of a kind of Naphtonone and analogue thereof | |
| CN103848783B (en) | The method of the synthetic 2-chlorine apellagrin of a kind of oxidation step | |
| CN102977050A (en) | Method for synthesizing 2-benzothiazolyl dimethylacetal and 2-benzothiazol formaldehyde | |
| CN103012313A (en) | Synthetic method of aminothiazoly loximate | |
| CN102827015B (en) | Preparation method of 5-aminolevulinic acid (ALA) hydrochloride | |
| CN105198833B (en) | The synthesis technique of the formaldehyde of benzothiazole 2 | |
| CN106631885A (en) | 4-formaldoxime benzoate derivative preparation method | |
| CN103772189B (en) | Synthesis method of diethylstilbestrol compound methyl pigeon pea ketonic acid A | |
| CN101293832A (en) | Process for synthesizing chlorogenic acid and its derivative | |
| CN110330450A (en) | A kind of preparation method of asymmetry thiourea | |
| CN101575301B (en) | Preparation method of 2-amino-5-chlorobenzamide | |
| CN101391988B (en) | Method for preparing 2-(4-hydroxyl phenyl)-4-methyl-1,3-thiazole-5-carboxylic acid ethyl ester by one pot method | |
| CH433378A (en) | Process for the production of new anthranilic acid derivatives | |
| CN101475541B (en) | Preparation of 4-methyl thiazole-5-carboxyl acid | |
| CN104945312A (en) | Preparation method of 2,6-dichlorine methyl pyridine hydrochloride | |
| CN105198834B (en) | The synthesis technique of 2,6 dibromo benzothiazoles | |
| CN114591176B (en) | Preparation method of 3-nitrophthalic acid | |
| CN111039768B (en) | Synthesis method of targeting antioxidant SKQ1 intermediate 2, 3-dimethyl-p-benzoquinone | |
| CN112480016B (en) | (E) -1-acyl-1- (3-quinoxalinone) methyl ketoxime and synthesis method thereof | |
| CN103224494B (en) | One prepares the method for 2-amino-5-(N-phenothiazinyl) methylene radical-1,3,4-thiadiazoles | |
| CN110862311B (en) | Synthesis method of 1-hydroxycyclopropanecarboxylic acid and carboxylate | |
| CN117105779A (en) | Preparation method of 5-bromo-2-formylbenzoic acid methyl ester | |
| KR20240019353A (en) | Intermediates of eldoxaban tosylate and methods for their preparation |
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 | ||
| 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: Synthesis of benzothiazole-2-carboxylic acid Effective date of registration: 20220615 Granted publication date: 20170929 Pledgee: The Bank of Shanghai branch Caohejing Limited by Share Ltd. Pledgor: SHANGHAI TITAN TECHNOLOGY Co.,Ltd. Registration number: Y2022310000059 |
|
| 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: 20230802 Granted publication date: 20170929 Pledgee: The Bank of Shanghai branch Caohejing Limited by Share Ltd. Pledgor: SHANGHAI TITAN TECHNOLOGY Co.,Ltd. Registration number: Y2022310000059 |
|
| 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: Synthesis process of benzothiazol-2-carboxylic acid Effective date of registration: 20230829 Granted publication date: 20170929 Pledgee: The Bank of Shanghai branch Caohejing Limited by Share Ltd. Pledgor: SHANGHAI TITAN TECHNOLOGY Co.,Ltd. Registration number: Y2023310000500 |