CN104151196A - Preparation method of 2,3,4,5,6-pentafluorobenzonitrile - Google Patents
Preparation method of 2,3,4,5,6-pentafluorobenzonitrile Download PDFInfo
- Publication number
- CN104151196A CN104151196A CN201410338985.9A CN201410338985A CN104151196A CN 104151196 A CN104151196 A CN 104151196A CN 201410338985 A CN201410338985 A CN 201410338985A CN 104151196 A CN104151196 A CN 104151196A
- Authority
- CN
- China
- Prior art keywords
- preparation
- fluoro benzene
- penta fluoro
- benzene nitrile
- perchlorobenzonitrile
- 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
Abstract
The invention relates to a preparation method of 2,3,4,5,6-pentafluorobenzonitrile, which mainly solves the problems of high reaction temperature, long reaction time, lower reaction yield and severe pollution in the prior art. The preparation method comprises the following steps: adding 2,3,4,5,6-pentachlorobenzonitrile, a solvent and a dehydrating agent into a reactor, carrying out azeotropic dehydration, adding a N-bis-(N-bis(dimethylamino)methylene)-imine chloride salt catalyst and a fluoride salt, continuing the azeotropic dehydration, reacting at 170-230 DEG C to obtain a reaction solution, filtering out the salts, and sending the filtrate into a rectifying still to perform vacuum distillation, thereby obtaining the 2,3,4,5,6-pentachlorobenzonitrile product. The technical scheme well solves the problems above, and can be used for preparing 2,3,4,5,6-pentachlorobenzonitrile.
Description
Technical field
The present invention relates to a kind of 2,3,4,5, the preparation method of 6-penta fluoro benzene nitrile.
Background technology
Penta fluoro benzene nitrile is a kind of important fluoro-containing intermediate, is mainly used in the synthetic aspect of agricultural chemicals, medicine, liquid crystal, catalyzer and fluorine material.As synthesizing of agricultural chemicals fenfluthrin, medical Sparfloxacin, tetrafluoro phenyl bridging class liquid crystal material, polyolefin catalyst and material monomer pentafluorostyrene etc.Along with continually developing of the product in downstream, its demand will further strengthen, and therefore how efficiently synthetic penta fluoro benzene nitrile gets more and more people's extensive concerning.
Up to now, bibliographical information prepare penta fluoro benzene nitrile mainly contain 3 kinds of synthetic routes [1].(1) five fluorine iodobenzene is raw material and cuprous cyanide reaction; (2) pentabromobenzene formonitrile HCN reacts with Potassium monofluoride; (3) Perchlorobenzonitrile and Potassium monofluoride reaction.Wherein the route of tool economy is that to adopt Perchlorobenzonitrile be raw material, fluoridizes synthetic with Potassium monofluoride.And there is expensive raw material price in route (1) and (2), the shortcoming such as be not easy to obtain, cause penta fluoro benzene nitrile to synthesize high expensive, the market competitiveness is not strong.
Patent JP60184057 has introduced a kind of method of single stage method and the synthetic penta fluoro benzene formonitrile HCN of substep conversion method, pentachlorobenzene formonitrile HCN and dry fine Potassium monofluoride are in cyanobenzene solvent, at 315 ℃, in autoclave pressure, react 18h, mother liquor after cold filtration is with gas-chromatography internal mark method determination, result is containing 3 of 80.5% penta fluoro benzene formonitrile HCN and 1.2%, 5-bis-is chloro-2,4,6-trifluoro-benzene formonitrile HCN.Under simulated condition, add a small amount of dibenzo-18-hat-6 and after 300 ℃ of reaction 7h 66.5% product, 15.4% 3-is chloro-2,4,5,6-tetra fluoro benzene formonitrile HCN and 5.8% 3,5-bis-is chloro-2,4,6-trifluoro-benzene formonitrile HCN.Under condition without crown ether, but temperature of reaction is increased to 350 ℃ of reaction 4h, mother liquor contains 72.5% penta fluoro benzene formonitrile HCN.(the Ge Yali such as Ge Yali, Lin Yuanbin, Su Qiong, etc., the preparation of pentafluorobenzoic acid, Chinese Journal of Pharmaceuticals, 2007,38 (1): 14) report be take tetramethylene sulfone as solvent, polyoxyethylene glycol is catalyzer, temperature is 200～220 ℃ of stirring reaction 36h, and underpressure distillation obtains oily product, and yield is 45.7%.Catalyzer is dibenzo-18-6 or ethylene glycol etc.; Solvent is cyanobenzene or tetramethylene sulfone etc.
Above-mentioned bibliographical information technique exists that temperature of reaction is high, long reaction time, production process energy consumption is high, reaction yield is relatively low, the shortcoming such as seriously polluted.The present invention has solved the problems referred to above targetedly.
Summary of the invention
Technical problem to be solved by this invention be in prior art, have that temperature of reaction is high, long reaction time, lower, the with serious pollution problem of reaction yield, provide a kind of new 2,3,4,5, the preparation method of 6-penta fluoro benzene nitrile.The method, in the preparation of 2,3,4,5,6-penta fluoro benzene nitrile, has advantages of that the temperature of reaction of existence is low, the reaction times is short, reaction yield is higher, it is not serious to pollute.
For addressing the above problem, the technical solution used in the present invention is as follows: a kind of 2,3,4, the preparation method of 5,6-penta fluoro benzene nitrile, comprises 2 to adding in reactor, 3,4,5,6-Perchlorobenzonitrile, solvent, dewatering agent, the material that adds N pair-(two (dimethylin) methylene radical of N-)-chlorimide salt catalyst, fluoride salt after azeotropic dehydration, continuing azeotropic dehydration, is then reaction at 170～230 ℃ in temperature, and the reaction solution obtaining is desalination after filtration, filtrate enters rectifying still and carries out underpressure distillation, obtain 2,3,4,5,6-penta fluoro benzene nitrile product.
In technique scheme, preferably, in temperature, be that at 70～150 ℃, azeotropic dehydration added catalyzer after 2～5 hours, continuing in temperature is azeotropic dehydration 1～3 hour at 70-150 ℃, in temperature, is then at 170～230 ℃, to react 5～20 hours.
In technique scheme, preferably, described solvent is selected from tetramethylene sulfone, DMI, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether or cyanobenzene; Dewatering agent is hexanaphthene or toluene.
In technique scheme, preferably, the weight ratio of described dewatering agent and 2,3,4,5,6-Perchlorobenzonitrile is 0.25～0.5.
In technique scheme, preferably, described fluoride salt is Potassium monofluoride.
In technique scheme, preferably, described 2,3,4,5, the mol ratio of 6-Perchlorobenzonitrile and Potassium monofluoride is 1:6～8, the consumption of catalyzer be 2,3,4,5,6-Perchlorobenzonitrile weight 5～25%, solvent with and 2,3,4,5, the mol ratio of 6-Perchlorobenzonitrile is 5～10:1.
In technique scheme, preferably, described filtrate enters rectifying still and carries out underpressure distillation, collects 66-74 ℃/30mmHg cut, obtains 2,3,4,5,6-penta fluoro benzene nitrile product, and the raffinate after underpressure distillation is delivered in reactor and continued to utilize.
In the present invention, dewatering agent is recycled in reclaiming dehydration, and solvent utilizes by Distillation recovery; Described reactor is the reactor with stirring, reflux water-dividing device, thermometer; Decompress filter after dilution with toluene for described reaction solution, desalination, filter cake toluene wash 1～5 time, filtrate goes in rectifying still carries out rectification under vacuum, and described rectifying still is with stirring.
The present invention adopts, and two-(two (dimethylin) methylene radical of N-)-protochloride amine salt is catalyzer, and catalytic activity is high, can effectively reduce temperature and the reaction time of reaction system, improves the yield of product, and the highest yield can reach 80%.Reaction is carried out at 170～230 ℃, and reaction conditions is gentle.After distillation, raffinate is delivered in reactor and is continued to utilize, and further reduces the few three waste discharge of preparation cost ， Minus, has obtained good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
In the 1000ml reactor of belt stirrer, reflux water-dividing device, thermometer, add 100g2,3,4,5,6-Perchlorobenzonitrile, 240g1,3-dimethyl-2-imidazolinone, 100g hexanaphthene, is warming up to 90 ℃, reflux water-dividing 2 hours, after anhydrous separating in water trap, drop into catalyzer two-(two (dimethylin) methylene radical of N-)-protochloride amine salt 10g, the dry Potassium monofluoride of 140g spraying, is warming up to 90 ℃, reflux water-dividing reaction 1 hour, continue to be warming up to 180 ℃, reaction 15h finishes.By decompress filter after dilution with toluene for the reaction solution obtaining, desalination, toluene wash 3 times for filter cake, filtrate goes to carries out rectification under vacuum in rectifying still, collect the cut 25g of 66-74 ℃/30mmHg, obtain 2,3,4,5,6-penta fluoro benzene nitrile product, GC (gas-chromatography) analyzes its purity 98%, yield 35%.
[embodiment 2]
In the 1000ml reactor of belt stirrer, reflux water-dividing device, thermometer, add 100g2,3,4,5,6-Perchlorobenzonitrile, 240g tetramethylene sulfone, 100g hexanaphthene, is warming up to 90 ℃, reflux water-dividing 2 hours, after anhydrous separating in water trap, drop into catalyzer two-(two (dimethylin) methylene radical of N-)-protochloride amine salt 10g, the dry Potassium monofluoride of 140g spraying, be warming up to 90 ℃, reflux water-dividing reaction 1 hour, continues to be warming up to 180 ℃, and reaction 12h finishes.By decompress filter after dilution with toluene for the reaction solution obtaining, desalination, toluene wash 3 times for filter cake, filtrate goes to carries out rectification under vacuum in rectifying still, collect the cut 42g of 66-74 ℃/30mmHg, obtain 2,3,4,5,6-penta fluoro benzene nitrile product, GC (gas-chromatography) analyzes its purity 99%, yield 60%.
[embodiment 3]
In the 1000ml reactor of belt stirrer, reflux water-dividing device, thermometer, add 100g2,3,4,5,6-Perchlorobenzonitrile, 240g tetramethylene sulfone, 100g hexanaphthene, is warming up to 90 ℃, reflux water-dividing 2 hours, after anhydrous separating in water trap, drop into catalyzer two-(two (dimethylin) methylene radical of N-)-protochloride amine salt 20g, the dry Potassium monofluoride of 140g spraying, be warming up to 90 ℃, reflux water-dividing reaction 1 hour, continues to be warming up to 220 ℃, and reaction 10h finishes.By decompress filter after dilution with toluene for the reaction solution obtaining, desalination, toluene wash 3 times for filter cake, filtrate goes to carries out rectification under vacuum in rectifying still, collect the cut 56g of 66-74 ℃/30mmHg, obtain 2,3,4,5,6-penta fluoro benzene nitrile product, GC (gas-chromatography) analyzes its purity 99%, yield 80%.
[embodiment 4]
In the 1000ml reactor of belt stirrer, reflux water-dividing device, thermometer, add 100g2,3,4,5,6-Perchlorobenzonitrile, 240g tetramethylene sulfone, 100g hexanaphthene, is warming up to 90 ℃, reflux water-dividing 2 hours, after anhydrous separating in water trap, drop into catalyzer two-(two (dimethylin) methylene radical of N-)-protochloride amine salt 15g, the dry Potassium monofluoride of 140g spraying, be warming up to 90 ℃, reflux water-dividing reaction 1 hour, continues to be warming up to 210 ℃, and reaction 10h finishes.By decompress filter after dilution with toluene for the reaction solution obtaining, desalination, toluene wash 3 times for filter cake, filtrate goes to carries out rectification under vacuum in rectifying still, collect the cut 54.7g of 66-74 ℃/30mmHg, obtain 2,3,4,5,6-penta fluoro benzene nitrile product, GC (gas-chromatography) analyzes its purity 99.5%, yield 78%.
[embodiment 5]
In the 1000ml reactor of belt stirrer, reflux water-dividing device, thermometer, add 100g2,3,4,5,6-Perchlorobenzonitrile, 240g tetramethylene sulfone, 100g toluene, is warming up to 130 ℃, reflux water-dividing 2 hours, after anhydrous separating in water trap, drop into catalyzer two-(two (dimethylin) methylene radical of N-)-protochloride amine salt 15g, the dry Potassium monofluoride of 140g spraying, be warming up to 130 ℃, reflux water-dividing reaction 1 hour, continues to be warming up to 200 ℃, and reaction 10h finishes.By decompress filter after dilution with toluene for the reaction solution obtaining, desalination, toluene wash 5 times for filter cake, filtrate goes to carries out rectification under vacuum in rectifying still, collect the cut 57g of 66-74 ℃/30mmHg, obtain 2,3,4,5,6-penta fluoro benzene nitrile product, GC (gas-chromatography) analyzes its purity 99.4%, yield 81.4%.Raffinate after underpressure distillation is delivered in reactor and is continued to utilize.
[embodiment 6]
In the 1000ml reactor of belt stirrer, reflux water-dividing device, thermometer, add 100g2,3,4,5,6-Perchlorobenzonitrile, 240g cyanobenzene, 100g toluene, is warming up to 130 ℃, reflux water-dividing 2 hours, after anhydrous separating in water trap, drop into catalyzer two-(two (dimethylin) methylene radical of N-)-protochloride amine salt 15g, the dry Potassium monofluoride of 140g spraying, be warming up to 130 ℃, reflux water-dividing reaction 1 hour, continues to be warming up to 200 ℃, and reaction 10h finishes.By decompress filter after dilution with toluene for the reaction solution obtaining, desalination, toluene wash 1 time for filter cake, filtrate goes to carries out rectification under vacuum in rectifying still, collect the cut 52.5g of 66-74 ℃/30mmHg, obtain 2,3,4,5,6-penta fluoro benzene nitrile product, GC (gas-chromatography) analyzes its purity 99.3%, yield 75%.Raffinate after underpressure distillation is delivered in reactor and is continued to utilize.
Claims (7)
1. one kind 2,3,4,5, the preparation method of 6-penta fluoro benzene nitrile, comprises 2,3,4 to adding in reactor, 5,6-Perchlorobenzonitrile, solvent, dewatering agent, after azeotropic dehydration, add N two-material of (two (dimethylin) methylene radical of N-)-chlorimide salt catalyst, fluoride salt, continuing azeotropic dehydration, is then reaction at 170～230 ℃ in temperature, and the reaction solution obtaining is desalination after filtration, filtrate enters rectifying still and carries out underpressure distillation, obtains 2,3,4,5,6-penta fluoro benzene nitrile product.
2. according to claim 12,3,4,5, the preparation method of 6-penta fluoro benzene nitrile, it is characterized in that in temperature being that at 70～150 ℃, azeotropic dehydration added catalyzer after 2～5 hours, continuing in temperature is azeotropic dehydration 1～3 hour at 70-150 ℃, in temperature, is then at 170～230 ℃, to react 5～20 hours.
3. according to claim 12,3,4,5, the preparation method of 6-penta fluoro benzene nitrile, is characterized in that described solvent is selected from tetramethylene sulfone, DMI, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether or cyanobenzene; Dewatering agent is hexanaphthene or toluene.
4. according to claim 12,3,4,5, the preparation method of 6-penta fluoro benzene nitrile, the weight ratio that it is characterized in that described dewatering agent and 2,3,4,5,6-Perchlorobenzonitrile is 0.25～0.5.
5. according to claim 12,3,4,5, the preparation method of 6-penta fluoro benzene nitrile, is characterized in that described fluoride salt is Potassium monofluoride.
6. according to claim 12,3,4,5, the preparation method of 6-penta fluoro benzene nitrile, is characterized in that described 2,3,4, the mol ratio of 5,6-Perchlorobenzonitrile and Potassium monofluoride is 1:6～8, and the consumption of catalyzer is 2,3,4,5,5～25% of the weight of 6-Perchlorobenzonitrile, solvent with and 2,3, the mol ratio of 4,5,6-Perchlorobenzonitrile is 5～10:1.
7. according to claim 12,3,4,5, the preparation method of 6-penta fluoro benzene nitrile, it is characterized in that described filtrate enters rectifying still and carries out underpressure distillation, collect 66-74 ℃/30mmHg cut, obtain 2,3,4,5,6-penta fluoro benzene nitrile product, the raffinate after underpressure distillation is delivered in reactor and is continued to utilize.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410338985.9A CN104151196A (en) | 2014-07-16 | 2014-07-16 | Preparation method of 2,3,4,5,6-pentafluorobenzonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410338985.9A CN104151196A (en) | 2014-07-16 | 2014-07-16 | Preparation method of 2,3,4,5,6-pentafluorobenzonitrile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104151196A true CN104151196A (en) | 2014-11-19 |
Family
ID=51876860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410338985.9A Pending CN104151196A (en) | 2014-07-16 | 2014-07-16 | Preparation method of 2,3,4,5,6-pentafluorobenzonitrile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104151196A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105523962A (en) * | 2016-01-06 | 2016-04-27 | 大连奇凯医药科技有限公司 | Fluorobenzonitrile compound preparation method |
| CN106883147A (en) * | 2017-02-13 | 2017-06-23 | 浙江工业大学 | A kind of preparation method of phenyl-pentafluoride formonitrile HCN |
| CN110845414A (en) * | 2019-11-27 | 2020-02-28 | 济宁康盛彩虹生物科技有限公司 | Preparation method and application of N-bis (dimethylamino) -1, 3-dimethylimidazoline |
| CN111004149A (en) * | 2019-12-27 | 2020-04-14 | 大连奇凯医药科技有限公司 | Method for preparing polyfluorobenzonitrile by catalytic fluorination of polychlorinated benzonitrile |
| CN114755332A (en) * | 2022-04-07 | 2022-07-15 | 连云港杰瑞药业有限公司 | Method for detecting isomer impurities in para-fluorobenzonitrile by gas chromatography |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3429935A (en) * | 1964-08-31 | 1969-02-25 | Us Navy | High temperature substitution reactions of hexafluorobenzene |
| US6265627B1 (en) * | 1999-11-23 | 2001-07-24 | Sergei Mikhailovich Igumnov | Process for preparing polyfluoroaromatic compounds |
| JP2005112745A (en) * | 2003-10-06 | 2005-04-28 | Nippon Shokubai Co Ltd | Method for producing aromatic fluorocompound |
| CN103539699A (en) * | 2013-10-30 | 2014-01-29 | 上海华谊（集团）公司 | Process for synthesizing 3,4-difluorobenzonitrile |
-
2014
- 2014-07-16 CN CN201410338985.9A patent/CN104151196A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3429935A (en) * | 1964-08-31 | 1969-02-25 | Us Navy | High temperature substitution reactions of hexafluorobenzene |
| US6265627B1 (en) * | 1999-11-23 | 2001-07-24 | Sergei Mikhailovich Igumnov | Process for preparing polyfluoroaromatic compounds |
| JP2005112745A (en) * | 2003-10-06 | 2005-04-28 | Nippon Shokubai Co Ltd | Method for producing aromatic fluorocompound |
| CN103539699A (en) * | 2013-10-30 | 2014-01-29 | 上海华谊（集团）公司 | Process for synthesizing 3,4-difluorobenzonitrile |
Non-Patent Citations (1)
| Title |
|---|
| 葛雅莉等: "五氟苯甲酸的制备", 《中国医药工业杂志》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105523962A (en) * | 2016-01-06 | 2016-04-27 | 大连奇凯医药科技有限公司 | Fluorobenzonitrile compound preparation method |
| CN106883147A (en) * | 2017-02-13 | 2017-06-23 | 浙江工业大学 | A kind of preparation method of phenyl-pentafluoride formonitrile HCN |
| CN106883147B (en) * | 2017-02-13 | 2018-11-02 | 浙江工业大学 | A kind of preparation method of phenyl-pentafluoride formonitrile HCN |
| CN110845414A (en) * | 2019-11-27 | 2020-02-28 | 济宁康盛彩虹生物科技有限公司 | Preparation method and application of N-bis (dimethylamino) -1, 3-dimethylimidazoline |
| WO2021103614A1 (en) * | 2019-11-27 | 2021-06-03 | 济宁康盛彩虹生物科技有限公司 | Preparation method for and use of n-bis(dimethylamino)-1,3-dimethylimidazoline |
| CN111004149A (en) * | 2019-12-27 | 2020-04-14 | 大连奇凯医药科技有限公司 | Method for preparing polyfluorobenzonitrile by catalytic fluorination of polychlorinated benzonitrile |
| CN111004149B (en) * | 2019-12-27 | 2022-06-07 | 大连奇凯医药科技有限公司 | Method for preparing polyfluorobenzonitrile by catalytic fluorination of polychlorinated benzonitrile |
| CN114755332A (en) * | 2022-04-07 | 2022-07-15 | 连云港杰瑞药业有限公司 | Method for detecting isomer impurities in para-fluorobenzonitrile by gas chromatography |
| CN114755332B (en) * | 2022-04-07 | 2024-04-02 | 连云港杰瑞药业有限公司 | Method for detecting isomer impurities in p-fluorobenzonitrile by gas chromatography |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104151196A (en) | Preparation method of 2,3,4,5,6-pentafluorobenzonitrile | |
| CN102766130A (en) | Preparation method of difluoroethylene carbonate | |
| CN103242197B (en) | Preparation method of ultraviolet absorbent intermediate etocrilene (ETO) | |
| CN103130656B (en) | Prepared method of 2-amino-2-methyl-1-propyl alcohol | |
| CN103539699A (en) | Process for synthesizing 3,4-difluorobenzonitrile | |
| CN106748763B (en) | The method of two kettles joint phase-transfer Wittig reaction methyl benzoate | |
| CN107628967A (en) | A kind of method for synthesizing cyhalofop-butyl | |
| CN103420842B (en) | Preparation method for 2,3,4-trifluoronitrobenzene | |
| CN103012279B (en) | Preparation method of 4,5,6-trifluoro-pyrimidine compound | |
| CN102993226B (en) | Prepare the method for phenyldimethylchlorosilane | |
| CN103524366B (en) | Synthesis process of -p-hydroxyphenylglycine | |
| CN103254074A (en) | Preparation method of ethyl difluoroacetate and intermediate thereof | |
| CN105523529A (en) | Method for preparing bis(fluorosulfonyl)imine | |
| CN106278914B (en) | A kind of synthesis technique of increase production of amines | |
| CN102786427B (en) | Synthetic method of bis-(2-dimethylaminoethyl)ether | |
| CN108530301A (en) | A kind of synthetic method of tri- fluorin benzyl amines of 2,4,6- | |
| CN109320522A (en) | A method of preparing isobide | |
| CN102491901B (en) | Preparation method of 4-bromine-2-nitro trifluoromethyl benzene | |
| CN104387289A (en) | Method for reducing using amount of catalyst in production of difluorobenzonitrile | |
| CN103724213B (en) | A kind of synthetic method of 2,6-di-isopropyl-4-phenoxybenzamine | |
| CN103664833A (en) | Preparation method of trifluoro epoxypropane | |
| CN102964225A (en) | Preparation method of 2, 3-dichloroanisole | |
| CN103288650A (en) | Hydrochloric acid 1-amino-3, 5-dimethyl adamantane preparation method | |
| CN107954878A (en) | A kind of synthetic method of intermediate 3- fluoro-4-nitrophenols | |
| CN107089903B (en) | Preparation method of o-isopropoxyphenol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20141119 |