CN110937983A - Method for producing trichloromethoxybenzene by using hexafluorobenzene as solvent - Google Patents
Method for producing trichloromethoxybenzene by using hexafluorobenzene as solvent Download PDFInfo
- Publication number
- CN110937983A CN110937983A CN201911379877.5A CN201911379877A CN110937983A CN 110937983 A CN110937983 A CN 110937983A CN 201911379877 A CN201911379877 A CN 201911379877A CN 110937983 A CN110937983 A CN 110937983A
- Authority
- CN
- China
- Prior art keywords
- hexafluorobenzene
- trichloromethoxybenzene
- solvent
- producing
- photochlorination
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for producing trichloromethoxybenzene by using hexafluorobenzene as a solvent, belonging to the technical field of chemical processes. Anisole is used as a starting material, hexafluorobenzene is used as a solvent to carry out a photochlorination reaction, and trichloromethoxybenzene is prepared after the hexafluorobenzene is recovered. The method adopts hexafluorobenzene as an organic solvent, can be better applied to the photochlorination, has higher recovery rate, can better prepare the trichloromethoxybenzene by the photochlorination with the raw material anisole in the presence of a proper catalyst, and is suitable for industrial large-scale production.
Description
Technical Field
The invention relates to a method for producing aromatic compounds, in particular to a method for producing trichloromethoxybenzene by using hexafluorobenzene as a solvent.
Background
The photochlorination can be carried out without using a solvent, but in most cases, it is carried out in the presence of an organic solvent. Examples of the solvent used in the photochlorination reaction for producing trichloromethoxybenzene include carbon tetrachloride, trifluoromethylbenzene, o-chlorotrifluoromethylbenzene, m-chlorotrifluoromethylbenzene, p-chlorotrifluoromethylbenzene, trichloromethylbenzene, and chlorobenzene.
1. The trichloromethoxybenzene can be prepared well by using carbon tetrachloride as a solvent (CN 1390820A). Although the production process using carbon tetrachloride as a solvent can be smoothly carried out and a product of high yield and high quality can be obtained. However, in order to fulfill the Montreal protocol on ozone layer depletion substances, the use of carbon tetrachloride solvent in the photo-chlorination process is limited according to the bulletin on strict limitation of carbon tetrachloride production, purchase and use, which is made and issued by the relevant regulations of the national scheme of Chinese gradual elimination of ozone layer depletion substances and the elimination plan of Chinese carbon tetrachloride production and processing aid industry.
2. When trichloromethylbenzene is used as a solvent (U.S. Pat. No. 4, 005773668A), and anisole undergoes a photochlorination reaction at a reflux temperature, the reaction system becomes black.
3. When the trifluoromethyl benzene is used as a solvent (US005773668A), and the anisole is subjected to photochlorination reaction at the reflux temperature, gas chromatographic analysis shows that the anisole raw material can be completely reacted, but a small amount of ring chlorination byproducts are generated, a small amount of side chain dichloro products are generated, and the yield is 83.9%.
4. When p-chlorotrifluoromethylbenzene is used as a solvent (US005773668A), and anisole is subjected to photochlorination at a reflux temperature, gas chromatography analysis shows that the anisole serving as a raw material can be completely reacted, a small amount of ring chlorination byproducts are generated, and the trichloromethoxybenzene serving as an intermediate can be obtained at a high yield.
5. The method is characterized in that trifluoromethylbenzene, p-chlorotrifluoromethoxybenzene or chlorobenzene is used as a solvent, and photochlorination is carried out in the presence of a proper catalyst and under proper reaction conditions, so that trichloromethoxybenzene with higher quality can be obtained. However, the reaction still has a large amount of residue, the yield cannot achieve the expected effect, and the recovered solvent contains a small amount of intermediate products, so that the number of times of the solvent is limited, the prices of the trifluoromethylbenzene, the p-chlorotrifluoromethoxybenzene and the p-chlorotrifluoromethoxybenzene are relatively high, and the production cost is increased.
Therefore, on the basis of the reaction method, a reaction solvent needs to be reasonably selected, so that the solvent is not influenced in the reaction process, new impurities are not introduced in the photochlorination process, black tar-like substances in kettle residues are reduced, and the method is favorable for recycling for multiple times.
Disclosure of Invention
The invention aims to overcome the technical defects and provide a method for producing trichloromethoxybenzene by using hexafluorobenzene as a solvent. Anisole is used as a starting material, hexafluorobenzene is used as a solvent to carry out a photochlorination reaction, and trichloromethoxybenzene is prepared after the hexafluorobenzene is recovered. The method adopts hexafluorobenzene as an organic solvent, can be better applied to the photochlorination, has higher recovery rate, and can better prepare the trichloromethoxybenzene by carrying out the photochlorination with the raw material anisole in the presence of a proper catalyst.
The technical scheme adopted by the invention for solving the technical problem is as follows: the method for producing trichloromethoxybenzene by using hexafluorobenzene as a solvent is characterized in that anisole is used as an initial raw material, hexafluorobenzene is used as a solvent for a photochlorination reaction, and after the hexafluorobenzene is recovered, trichloromethoxybenzene is prepared, wherein the chemical reaction formula is as follows:
further, in the above technical scheme, the molar ratio of anisole to hexafluorobenzene in the reaction charge ratio is 1: 2-6, preferably in a molar ratio of 1: 3.
further, in the technical scheme, the raw material anisole is added in a dropwise manner, and the dropwise adding time is controlled to be longer than 6 hours.
Further, in the technical scheme, when the photochlorination reaction is carried out, the anisole is dropwise added at 70-75 ℃ with a good effect, and when the reaction temperature is 70-75 ℃, the photochlorination reaction can be ensured to be carried out under the condition of hexafluorobenzene reflux, so that the reaction control is easy, the side chain substitution is favorably inhibited, and the yield of the trichloromethoxybenzene is up to 95%.
In experiments, a large amount of kettle residues are generated by using trifluoromethyl benzene, p-chlorotrifluoromethylbenzene, p-chlorotrifluoromethoxybenzene or chlorobenzene as a solvent, and the yield cannot achieve the expected effect.
Further, in the above technical solution, the photochlorination of the present invention is performed in the presence of a catalyst, and the catalyst used is azobisisobutyronitrile and phosphorus trichloride.
Further, in the above technical scheme, after the photochlorination reaction is finished, hexafluorobenzene is recovered, and the method for recovering hexafluorobenzene includes: and (3) distilling at normal pressure and reduced pressure, namely distilling at normal pressure and then distilling at reduced pressure. Because the boiling point difference between hexafluorobenzene and trichloromethoxybenzene is large, the recovery rate can reach 98%, and the recovery effect is good.
The invention has the advantages of
The method adopts hexafluorobenzene as the photochlorination solvent for preparing trichloromethoxybenzene, has mild reaction conditions and lower temperature, ensures that hexafluorobenzene has no impurities substituted by chlorine in the reaction process, has better recycling effect, performs photochlorination with raw anisole in a proper molar ratio in the presence of a proper catalyst and under proper reaction conditions, and can better prepare the trichloromethoxybenzene, thereby being suitable for industrial large-scale production.
Detailed Description
Example 1
1. Photo-chlorination reaction
In a 1000mL reactor, a high-pressure mercury lamp, a thermometer, a stirrer, a condenser and a bottom-inserted vent pipe are arranged, and 1000g of hexafluorobenzene, 5g of phosphorus trichloride and 3g of azobisisobutyronitrile are respectively added; starting illumination (320-340nm, 125W light source), raising the temperature to 70 ℃ under stirring, introducing chlorine gas, beginning to dropwise add 200g of anisole, and dropwise adding at 70-75 ℃ for 6 h; 1.5g of azobisisobutyronitrile is added after the dropwise addition is finished; and (4) after the chlorine is continuously introduced for 1 hour after the addition is finished, stopping chlorine sampling analysis, taking the dichlorobenzyl of less than 1.0 percent as a reaction end point, turning off the lamp after the analysis is qualified, and cooling.
2. Recovery of hexafluorobenzene
Distilling the chlorinated material which is obtained in the photochlorination procedure and is qualified in analysis under normal pressure, then distilling under reduced pressure to recover hexafluorobenzene, and adjusting the vacuum degree to 0.07MPa-0.1MPa during the distillation under reduced pressure; the temperature of the kettle is ensured to be lower than 120 ℃ in the whole process, qualified hexafluorobenzene is obtained when the content of the produced hexafluorobenzene is more than 98 percent, and qualified trichloromethoxybenzene is obtained when the content of the hexafluorobenzene in the trichloromethoxybenzene is less than 1 percent; and cooling and stopping vacuum after the analysis is qualified. 990g of hexafluorobenzene is obtained, and the recovery rate of hexafluorobenzene is 98 percent; 379g of trichloromethoxybenzene is obtained, the external standard content is 98%, and the yield of the photochlorination reaction is 95%.
Example 2
1. Photo-chlorination reaction
In a 1000mL reactor, equipped with a high-pressure mercury lamp, a thermometer, a stirrer, a condenser and a plugged-in vent pipe, 1376g of hexafluorobenzene, 5g of phosphorus trichloride and 3g of azobisisobutyronitrile recovered in example 1 were added, respectively; starting illumination, heating to 70 ℃ while stirring, introducing chlorine, beginning to dropwise add 200g of anisole, and dropwise adding at 70-75 ℃ for 7 hours; 1.5g of azobisisobutyronitrile is added after the dropwise addition is finished; and (4) after the chlorine is continuously introduced for 1 hour after the addition is finished, stopping chlorine sampling analysis, taking the dichlorobenzyl of less than 1.0 percent as a reaction end point, turning off the lamp after the analysis is qualified, and cooling.
2. Recovery of hexafluorobenzene
Carrying out atmospheric distillation and then reduced pressure distillation on the chlorinated material which is obtained in the photochlorination procedure and is qualified in analysis to recover hexafluorobenzene, and adjusting the vacuum degree to 0.07MPa-0.1MPa during reduced pressure distillation; the temperature of the kettle is ensured to be lower than 120 ℃ in the whole process, qualified hexafluorobenzene is obtained when the content of the produced hexafluorobenzene is more than 98 percent, and qualified trichloromethoxybenzene is obtained when the content of the hexafluorobenzene in the trichloromethoxybenzene is less than 1 percent; and cooling and stopping vacuum after the analysis is qualified. 1362g of hexafluorobenzene is obtained, and the recovery rate of hexafluorobenzene is 98%; 379g of trichloromethoxybenzene is obtained, the external standard content is 98%, and the yield of the photochlorination reaction is 95%.
Example 3
1. Photo-chlorination reaction
In a 1000mL reactor, equipped with a high-pressure mercury lamp, a thermometer, a stirrer, a condenser and a bottom-inserted vent pipe, 1376g of hexafluorobenzene, 5g of phosphorus trichloride and 3g of azobisisobutyronitrile are added respectively; starting illumination, heating to 70 ℃ while stirring, introducing chlorine, beginning to dropwise add 200g of anisole, and dropwise adding at 70-75 ℃ for 3 h; 1.5g of azobisisobutyronitrile is added after the dropwise addition is finished; and (4) after the chlorine is continuously introduced for 1h after the addition is finished, stopping chlorine sampling and analyzing, taking the dichlorobenzyl content of less than 1 percent as a reaction end point, and turning off the lamp and cooling after the analysis is qualified.
2. Recovery of hexafluorobenzene
Carrying out atmospheric distillation and then reduced pressure distillation on the chlorinated material which is obtained in the photochlorination procedure and is qualified in analysis to recover hexafluorobenzene, and adjusting the vacuum degree to 0.07MPa-0.1MPa during reduced pressure distillation; the temperature of the kettle is ensured to be lower than 120 ℃ in the whole process, qualified hexafluorobenzene is obtained when the content of the produced hexafluorobenzene is more than 98 percent, and qualified trichloromethoxybenzene is obtained when the content of the hexafluorobenzene in the trichloromethoxybenzene is less than 1 percent; and cooling and stopping vacuum after the analysis is qualified. 1362g of hexafluorobenzene is obtained, and the recovery rate of hexafluorobenzene is 98%; 382g of trichloromethoxybenzene is obtained, the external standard content is 90%, and the yield of the photochlorination reaction is 88%.
Example 4
1. Photo-chlorination reaction
In a 1000mL reactor, equipped with a high-pressure mercury lamp, a thermometer, a stirrer, a condenser and a bottom-inserted vent pipe, 1376g of hexafluorobenzene, 5g of phosphorus trichloride and 3g of azobisisobutyronitrile are added respectively; after illumination is started, heating to 70 ℃ under stirring, introducing chlorine gas, beginning to dropwise add 200g of anisole, and dropwise adding at 60-65 ℃ for 7 h; 1.5g of azobisisobutyronitrile is added after the dropwise addition is finished; and (4) after the chlorine is continuously introduced for 1h after the addition is finished, stopping chlorine sampling and analyzing, taking the dichlorobenzyl content of less than 1 percent as a reaction end point, and turning off the lamp and cooling after the analysis is qualified.
2. Recovery of hexafluorobenzene
Carrying out atmospheric distillation and then reduced pressure distillation on the chlorinated material which is obtained in the photochlorination procedure and is qualified in analysis to recover hexafluorobenzene, and adjusting the vacuum degree to 0.07MPa-0.1MPa during reduced pressure distillation; the whole process ensures that the kettle temperature is not higher than 120 ℃, and qualified hexafluorobenzene is obtained when the content of the produced hexafluorobenzene is more than 98 percent, and qualified trichloromethoxybenzene is obtained when the content of the hexafluorobenzene in the trichloromethoxybenzene is less than 1 percent; and cooling and stopping vacuum after the analysis is qualified. 1362g of hexafluorobenzene is obtained, and the recovery rate of hexafluorobenzene is 98%; 365g of trichloromethoxybenzene is obtained, the external standard content is 91 percent, and the yield of the photochlorination reaction is 84 percent.
Example 5
1. Photo-chlorination reaction
In a 1000mL reactor, a high-pressure mercury lamp, a thermometer, a stirrer, a condenser and a bottom-inserted vent pipe are arranged, and 1000g of hexafluorobenzene, 5g of phosphorus trichloride and 3g of azobisisobutyronitrile are respectively added; starting illumination (320-340nm, 125W light source), raising the temperature to 70 ℃ under stirring, introducing chlorine gas, beginning to dropwise add 200g of anisole, and dropwise adding at 70-75 ℃ for 15 h; 1.5g of azobisisobutyronitrile is added after the dropwise addition is finished; and (4) after the chlorine is continuously introduced for 1 hour after the addition is finished, stopping chlorine sampling analysis, taking the dichlorobenzyl of less than 1.0 percent as a reaction end point, turning off the lamp after the analysis is qualified, and cooling.
2. Recovery of hexafluorobenzene
Distilling the chlorinated material which is obtained in the photochlorination procedure and is qualified in analysis under normal pressure, then distilling under reduced pressure to recover hexafluorobenzene, and adjusting the vacuum degree to 0.07MPa-0.1MPa during the distillation under reduced pressure; the temperature of the kettle is ensured to be lower than 120 ℃ in the whole process, qualified hexafluorobenzene is obtained when the content of the produced hexafluorobenzene is more than 98 percent, and qualified trichloromethoxybenzene is obtained when the content of the hexafluorobenzene in the trichloromethoxybenzene is less than 1 percent; and cooling and stopping vacuum after the analysis is qualified. 990g of hexafluorobenzene is obtained, and the recovery rate of hexafluorobenzene is 98 percent; 379g of trichloromethoxybenzene is obtained, the external standard content is 98%, and the yield of the photochlorination reaction is 95%.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the preferred embodiments of the present invention are described in the above embodiments and the description, and are not intended to limit the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. The method for producing trichloromethoxybenzene by using hexafluorobenzene as a solvent is characterized by comprising the following steps of: anisole is used as a starting material, hexafluorobenzene is used as a solvent to carry out a photochlorination reaction, and trichloromethoxybenzene is prepared after the hexafluorobenzene is recovered.
2. The method for producing trichloromethoxybenzene using hexafluorobenzene as a solvent according to claim 1, wherein: the molar ratio of anisole to hexafluorobenzene is 1: 2-6.
3. The method for producing trichloromethoxybenzene using hexafluorobenzene as a solvent according to claim 2, wherein: the molar ratio of anisole to hexafluorobenzene is 1: 3.
4. the method for producing trichloromethoxybenzene using hexafluorobenzene as a solvent according to claim 1, wherein: the reaction temperature is 70-75 ℃; the raw material anisole is added in a dropwise manner, and the dropwise adding time is controlled to be longer than 6 hours.
5. The method for producing trichloromethoxybenzene using hexafluorobenzene as a solvent according to claim 1, wherein: the catalyst is azodiisobutyronitrile and phosphorus trichloride.
6. The method for producing trichloromethoxybenzene using hexafluorobenzene as a solvent according to claim 1, wherein: after the photochlorination reaction is finished, hexafluorobenzene is recovered for recycling.
7. The method for producing trichloromethoxybenzene using hexafluorobenzene as a solvent according to claim 6, wherein: the method comprises the steps of firstly distilling at normal pressure and then distilling at reduced pressure to recover hexafluorobenzene, and then distilling to obtain trichloromethoxybenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911379877.5A CN110937983A (en) | 2019-12-27 | 2019-12-27 | Method for producing trichloromethoxybenzene by using hexafluorobenzene as solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911379877.5A CN110937983A (en) | 2019-12-27 | 2019-12-27 | Method for producing trichloromethoxybenzene by using hexafluorobenzene as solvent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110937983A true CN110937983A (en) | 2020-03-31 |
Family
ID=69913487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911379877.5A Pending CN110937983A (en) | 2019-12-27 | 2019-12-27 | Method for producing trichloromethoxybenzene by using hexafluorobenzene as solvent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110937983A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5773668A (en) * | 1997-02-24 | 1998-06-30 | Occidental Chemical Corporation | Method of making trichloromethoxybenzene |
| CN102120717A (en) * | 2010-12-16 | 2011-07-13 | 金凯(辽宁)化工有限公司 | Method for producing trichloromethoxybenzene by using chlorobenzene as solvent |
| CN102648170A (en) * | 2009-06-18 | 2012-08-22 | 艾尼纳制药公司 | Processes for the preparation of 5-HT2C receptor agonists |
| CN105085202A (en) * | 2014-05-22 | 2015-11-25 | 刘世伟 | Synthetic method for trichloromethoxybenzene |
| CN106008175A (en) * | 2016-05-19 | 2016-10-12 | 山东道可化学有限公司 | Production method of trifluoromethoxybenzene |
| CN107530327A (en) * | 2015-03-31 | 2018-01-02 | 孟山都技术公司 | The method for preparing 2 thiophene chlorides |
| RU2697581C1 (en) * | 2011-06-27 | 2019-08-15 | Релипса, Инк. | Fluoridation of esters of acrylic acid and derivatives thereof |
-
2019
- 2019-12-27 CN CN201911379877.5A patent/CN110937983A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5773668A (en) * | 1997-02-24 | 1998-06-30 | Occidental Chemical Corporation | Method of making trichloromethoxybenzene |
| CN102648170A (en) * | 2009-06-18 | 2012-08-22 | 艾尼纳制药公司 | Processes for the preparation of 5-HT2C receptor agonists |
| CN102120717A (en) * | 2010-12-16 | 2011-07-13 | 金凯(辽宁)化工有限公司 | Method for producing trichloromethoxybenzene by using chlorobenzene as solvent |
| RU2697581C1 (en) * | 2011-06-27 | 2019-08-15 | Релипса, Инк. | Fluoridation of esters of acrylic acid and derivatives thereof |
| CN105085202A (en) * | 2014-05-22 | 2015-11-25 | 刘世伟 | Synthetic method for trichloromethoxybenzene |
| CN107530327A (en) * | 2015-03-31 | 2018-01-02 | 孟山都技术公司 | The method for preparing 2 thiophene chlorides |
| CN106008175A (en) * | 2016-05-19 | 2016-10-12 | 山东道可化学有限公司 | Production method of trifluoromethoxybenzene |
Non-Patent Citations (1)
| Title |
|---|
| JAMES M. TANKO ET AL.: "Competitive Cage Kinetics. Relative Rates of Complexation of Chlorine Atom by Various Arenes", 《J. AM. CHEM. SOC.》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107778181B (en) | Novel synthesis process of o-nitrobenzyl bromide | |
| CN111153765A (en) | Vitamin K with different cis-trans isomer ratios1Preparation method of halogenated plant alcohol as intermediate thereof | |
| KR20070004990A (en) | Preparation of halo-olefin | |
| CN110002948B (en) | Process for preparing halogenated cycloolefins | |
| EP0296517B1 (en) | Process for preparing monohalogenated benzocyclobutene | |
| CN111499506A (en) | Green production process of 2, 4-dichloro-5-fluorobenzoyl chloride | |
| CN102120717B (en) | Method for producing trichloromethoxybenzene by using chlorobenzene as solvent | |
| CN110937983A (en) | Method for producing trichloromethoxybenzene by using hexafluorobenzene as solvent | |
| EP3941902B1 (en) | A process for preparation of trifluoromethanesulfinyl chloride | |
| CN110845414A (en) | Preparation method and application of N-bis (dimethylamino) -1, 3-dimethylimidazoline | |
| CN110698352A (en) | Synthetic method of 3-bromo-5-aminocatechol dimethyl ether | |
| CN111004131A (en) | Method for recovering sucralose by-product salt | |
| CN111004174A (en) | Method for preparing 5-bromomethyl-2, 3-pyridine dimethyl dicarboxylate by ultraviolet light catalysis | |
| CN114988982A (en) | Method for isomerizing and synthesizing 3, 5-dichlorotoluene | |
| CN111170846A (en) | Method for preparing 3, 3-dimethyl-2-oxo-butyric acid | |
| CN112174878B (en) | Method and device for preparing 2, 6-dichloropyridine by fractional photochlorination of pyridine | |
| CN112479824A (en) | Method for recovering crystallization mother liquor in production process of 4-chloro-3, 5-dimethylphenol | |
| US4277421A (en) | Process for the manufacture of para-tert.butylbenzaldehyde and its derivatives which are halogen-substituted at the nucleus | |
| CN111499486B (en) | Safe and environment-friendly preparation method of cyclopropylacetylene | |
| US5516934A (en) | Process for producing mono-P-nitrobenzyl malonate | |
| JPH0665130A (en) | Production of catechols | |
| CN103420938B (en) | A kind of method preparing contracting piperazine reaction rear recovery piperazine in quinolone medicine | |
| EP0417720B1 (en) | Process for preparing 2-chloro-4-fluorophenol | |
| JP3804085B2 (en) | Method for producing high quality β-bromoethylbenzene | |
| CN101318974A (en) | Process for synthesizing methyl tin chloride |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200331 |
|
| RJ01 | Rejection of invention patent application after publication |