CN104098464A - Preparation method for 4-fluorobenzoyl chloride - Google Patents
Preparation method for 4-fluorobenzoyl chloride Download PDFInfo
- Publication number
- CN104098464A CN104098464A CN201310128451.9A CN201310128451A CN104098464A CN 104098464 A CN104098464 A CN 104098464A CN 201310128451 A CN201310128451 A CN 201310128451A CN 104098464 A CN104098464 A CN 104098464A
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- CN
- China
- Prior art keywords
- fluorobenzoyl chloride
- preparation
- reaction
- fluorine
- under
- 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.)
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Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- CZKLEJHVLCMVQR-UHFFFAOYSA-N 4-fluorobenzoyl chloride Chemical compound FC1=CC=C(C(Cl)=O)C=C1 CZKLEJHVLCMVQR-UHFFFAOYSA-N 0.000 title abstract 3
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 10
- WRWPPGUCZBJXKX-UHFFFAOYSA-N 1-fluoro-4-methylbenzene Chemical compound CC1=CC=C(F)C=C1 WRWPPGUCZBJXKX-UHFFFAOYSA-N 0.000 claims abstract description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 4
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 4
- 239000011592 zinc chloride Substances 0.000 claims abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 239000000460 chlorine Substances 0.000 claims abstract description 3
- RAAGZOYMEQDCTD-UHFFFAOYSA-N 2-fluorobenzoyl chloride Chemical compound FC1=CC=CC=C1C(Cl)=O RAAGZOYMEQDCTD-UHFFFAOYSA-N 0.000 claims description 20
- UGSQSHVLROBERZ-UHFFFAOYSA-N [F].ClC(C1=CC=CC=C1)(Cl)Cl Chemical compound [F].ClC(C1=CC=CC=C1)(Cl)Cl UGSQSHVLROBERZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- XOJYLEJZALFLLW-UHFFFAOYSA-N 1-fluoro-4-(trichloromethyl)benzene Chemical compound FC1=CC=C(C(Cl)(Cl)Cl)C=C1 XOJYLEJZALFLLW-UHFFFAOYSA-N 0.000 abstract 2
- 230000007062 hydrolysis Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- BBYDXOIZLAWGSL-UHFFFAOYSA-N 4-fluorobenzoic acid Chemical compound OC(=O)C1=CC=C(F)C=C1 BBYDXOIZLAWGSL-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- BKBSMMUEEAWFRX-NBVRZTHBSA-N (E)-flumorph Chemical compound C1=C(OC)C(OC)=CC=C1C(\C=1C=CC(F)=CC=1)=C\C(=O)N1CCOCC1 BKBSMMUEEAWFRX-NBVRZTHBSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 210000003792 cranial nerve Anatomy 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000000055 hyoplipidemic effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 1
- NAUWTFJOPJWYOT-UHFFFAOYSA-N vanoxerine Chemical compound C1=CC(F)=CC=C1C(C=1C=CC(F)=CC=1)OCCN1CCN(CCCC=2C=CC=CC=2)CC1 NAUWTFJOPJWYOT-UHFFFAOYSA-N 0.000 description 1
- 229950007136 vanoxerine Drugs 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/14—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the side-chain of aromatic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- B01J35/19—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
Abstract
A provided preparation method for 4-fluorobenzoyl chloride comprises the following steps: (a) under irradiation of an ultraviolet lamp, enabling 4-fluorotoluene and chlorine to perform a chlorination reaction at 70-85 DEG C, so as to prepare 4-fluorotrichlorotoluene; and (b) performing a hydrolysis reaction on 4-fluorotrichlorotoluene prepared in the step (a) and water under the effect of a composite catalyst of ferric trichloride and zinc chloride, so as to prepare 4-fluorobenzoyl chloride. The method is short in reaction route and time, simple and convenient for operation, and friendly to environment, and has wide application prospect.
Description
Technical field
The present invention relates to the field of chemical synthesis, relate more specifically to the preparation method to fluorobenzoyl chloride.
Background technology
To fluorobenzoyl chloride, be the important intermediate of the fine chemical products such as synthetic medicine, agricultural chemicals, can be used for synthesizing fungicide flumorph, hypolipidemic superstatin, treatment cranial nerve medicine vanoxerine etc.Thereby thering is very important using value, traditional preparation is mainly to be made or through chlorination, hydrolysis, make as starting raw material by take p-fluorotoluene through chloride by parafluorobenzoic acid to the method for fluorobenzoyl chloride.
Yet these two class methods all exist many shortcomings, the operational path that wherein adopts parafluorobenzoic acid is to take parafluorobenzoic acid as starting raw material, through chloride (or with phosgene effect, or with sulfur oxychloride effect) make fluorobenzoyl chloride; It is high that this kind of method exists preparation cost, the more difficult recovery comprehensive utilization of waste gas of generation and the shortcomings such as pollute more seriously.The cardinal principle reaction scheme of the method is as follows:
The another kind of operational path that adopts p-fluorotoluene, is to take p-fluorotoluene as starting raw material, through chlorination (illumination), obtains fluorine trichlorotoluene zotrichloride, and then, under catalyst action, controlled hydrolysis must be to fluorobenzoyl chloride; There is long reaction time in this kind of method, complicated operation, quality product and yield thereof be difficult to control and by product HCl more than etc. shortcoming.The cardinal principle reaction scheme of the method is as follows:
Summary of the invention
For overcoming the problems referred to above of the prior art, the invention provides a kind of preparation method to fluorobenzoyl chloride, its reaction times is short, and quality product and yield are all higher.
The technical solution used in the present invention is: a kind of preparation method to fluorobenzoyl chloride, comprises the following steps:
(a) under ultra violet lamp, make p-fluorotoluene and chlorine, at 70-85 ℃, chlorination reaction occur, make fluorine trichlorotoluene zotrichloride;
(b) by step (a) prepared to fluorine trichlorotoluene zotrichloride under the effect of the composite catalyst of iron trichloride and zinc chloride with water generation hydrolysis reaction, make fluorobenzoyl chloride.
Further, in step (a), chlorination reaction is carried out under the katalysis of catalyzer.
Preferably, in step (a), the catalyzer using is azo catalyst.
Further, in step (b), the temperature of hydrolysis reaction is 120 ℃.
Preferably, in step (b), the temperature of hydrolysis reaction is 130 ℃.
Compared with prior art, the present invention has following advantages: the invention provides a kind of preparation method to fluorobenzoyl chloride, it adopts p-fluorotoluene is raw material, makes fluorine trichlorotoluene zotrichloride after ultraviolet lighting catalytic chlorination, then through hydrolysis, makes fluorobenzoyl chloride, in hydrolytic process, adopt the composite catalyst of iron trichloride and zinc chloride, can improve well productive rate, simple to operate, be easy to suitability for industrialized production, and safety and environmental protection.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, thereby so that advantages and features of the invention are easier to be it will be appreciated by those skilled in the art that protection scope of the present invention is made and more removed clear and definite defining.
Embodiment 1
preparation is to fluorine trichlorotoluene zotrichloride
Under the condition of ultra violet lamp, outside 500mL there-necked flask, add p-fluorotoluene 110.5g (1.0mol), be warmed up to 80-85 ℃, then add 0.5g Diisopropyl azodicarboxylate in batches, pass into 198gCl
2(2.8mol), this reaction is thermopositive reaction, and reaction is used circulating cooling water for cooling after causing, and keeps temperature of reaction at 70-80 ℃.GC tracking reaction process, waits after raw material complete reaction, and insulation 1h is cooling, obtains intermediate to fluorine trichlorotoluene zotrichloride 212.3g (being ready to use in next step reaction), yield 99.5%, purity 99.5%.
Embodiment 2
preparation is to fluorobenzoyl chloride
Prepared to fluorine trichlorotoluene zotrichloride 211.4g (1mol) to adding in embodiment 1 in 500mL there-necked flask, stir, then drip 1.7mL water (0.09mol), temperature is risen to 130 ℃, GC follows the tracks of, and adds subsequently water, then adds composite catalyst FeCl
3: ZnCl
2=1: 1 (6.4g), follows the tracks of by GC, controls the content of fluorine trichlorotoluene zotrichloride at 0.02-0.03%.Under 2kPa, underpressure distillation, 120 ℃ steam product, to fluorobenzoyl chloride.Yield 99.3%, purity 99.5%.
Preparation method to fluorobenzoyl chloride provided by the present invention, adopt ultraviolet lighting catalytic chlorination, and in hydrolysis reaction, use composite catalyst, greatly shortened the time of chlorination reaction and hydrolysis reaction, by the change of catalysts, the single catalyst FeCl using in traditional method
3change into and use FeCl
3+ ZnCl
2composite catalyst, improved to a great extent the efficiency of hydrolysis, the productive rate of hydrolysis is improved, and end product quality and yield all obtained significantly improving, applicable to industrialized production.
Above specific embodiment of the present invention is illustrated; but protection content of the present invention is not only limited to above embodiment; under of the present invention, in technical field, the common knowledge of a GPRS just can be carried out diversified change within the scope of its technology main idea.
Claims (5)
1. the preparation method to fluorobenzoyl chloride, is characterized in that, comprises the following steps:
(a) under ultra violet lamp, make p-fluorotoluene and chlorine, at 70-85 ℃, chlorination reaction occur, make fluorine trichlorotoluene zotrichloride;
(b) by step (a) prepared to fluorine trichlorotoluene zotrichloride under the effect of the composite catalyst of iron trichloride and zinc chloride with water generation hydrolysis reaction, make fluorobenzoyl chloride.
2. the preparation method to fluorobenzoyl chloride according to claim 1, is characterized in that: in step (a), described chlorination reaction is carried out under the katalysis of catalyzer.
3. the preparation method to fluorobenzoyl chloride according to claim 2, is characterized in that: in step (a), described catalyzer is azo catalyst.
4. the preparation method to fluorobenzoyl chloride according to claim 1, is characterized in that: in step (b), the temperature of described hydrolysis reaction is 120 ℃.
5. the preparation method to fluorobenzoyl chloride according to claim 4, is characterized in that: in step (b), the temperature of described hydrolysis reaction is 130 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310128451.9A CN104098464A (en) | 2013-04-15 | 2013-04-15 | Preparation method for 4-fluorobenzoyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310128451.9A CN104098464A (en) | 2013-04-15 | 2013-04-15 | Preparation method for 4-fluorobenzoyl chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104098464A true CN104098464A (en) | 2014-10-15 |
Family
ID=51667050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310128451.9A Pending CN104098464A (en) | 2013-04-15 | 2013-04-15 | Preparation method for 4-fluorobenzoyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104098464A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008197A (en) * | 2016-06-06 | 2016-10-12 | 山东福尔有限公司 | Preparation method for o-fluorobenzoyl chloride |
| CN108610245A (en) * | 2018-05-22 | 2018-10-02 | 江苏万隆化学有限公司 | A kind of preparation method of high-purity difluoro benzophenone |
| CN115108898A (en) * | 2022-07-02 | 2022-09-27 | 浙江三美化工股份有限公司 | Preparation method and reaction device for synthesizing 4,4' -difluorobenzophenone by fluorobenzene |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4163753A (en) * | 1977-02-14 | 1979-08-07 | Diaz Chemical Corporation | Process for the simultaneous preparation of aromatic acid chlorides and aliphatic acid chlorides |
| US4276231A (en) * | 1978-09-23 | 1981-06-30 | Bayer Aktiengesellschaft | Process for the preparation of optionally substituted benzoyl chloride |
| US5840975A (en) * | 1995-02-03 | 1998-11-24 | Bayer Aktiengesellschaft | Process for preparing nucleus-halogenated benzoyl chlorides |
| CN1835904A (en) * | 2003-07-17 | 2006-09-20 | 巴斯福股份公司 | Method for producing substituted arylcarboxylic acid chlorides |
| WO2007138075A1 (en) * | 2006-05-31 | 2007-12-06 | Calaire Chimie Sas | Method for preparing lamotrigine and its intermediate 2,3-dichlorobenzoyl chloride |
| JP2010013388A (en) * | 2008-07-03 | 2010-01-21 | Central Glass Co Ltd | Method for producing 3-chloro-4-fluorobenzotrifluoride |
| CN102531872A (en) * | 2011-12-31 | 2012-07-04 | 金坛市春风化工有限公司 | Method for preparing high purity (99.9 percent) 4,4'-difluorobenzophenone |
-
2013
- 2013-04-15 CN CN201310128451.9A patent/CN104098464A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4163753A (en) * | 1977-02-14 | 1979-08-07 | Diaz Chemical Corporation | Process for the simultaneous preparation of aromatic acid chlorides and aliphatic acid chlorides |
| US4276231A (en) * | 1978-09-23 | 1981-06-30 | Bayer Aktiengesellschaft | Process for the preparation of optionally substituted benzoyl chloride |
| US5840975A (en) * | 1995-02-03 | 1998-11-24 | Bayer Aktiengesellschaft | Process for preparing nucleus-halogenated benzoyl chlorides |
| CN1835904A (en) * | 2003-07-17 | 2006-09-20 | 巴斯福股份公司 | Method for producing substituted arylcarboxylic acid chlorides |
| WO2007138075A1 (en) * | 2006-05-31 | 2007-12-06 | Calaire Chimie Sas | Method for preparing lamotrigine and its intermediate 2,3-dichlorobenzoyl chloride |
| JP2010013388A (en) * | 2008-07-03 | 2010-01-21 | Central Glass Co Ltd | Method for producing 3-chloro-4-fluorobenzotrifluoride |
| CN102531872A (en) * | 2011-12-31 | 2012-07-04 | 金坛市春风化工有限公司 | Method for preparing high purity (99.9 percent) 4,4'-difluorobenzophenone |
Non-Patent Citations (1)
| Title |
|---|
| 张军: "对氟苯甲酰氯的合成", 《有机氟工业》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008197A (en) * | 2016-06-06 | 2016-10-12 | 山东福尔有限公司 | Preparation method for o-fluorobenzoyl chloride |
| CN108610245A (en) * | 2018-05-22 | 2018-10-02 | 江苏万隆化学有限公司 | A kind of preparation method of high-purity difluoro benzophenone |
| CN115108898A (en) * | 2022-07-02 | 2022-09-27 | 浙江三美化工股份有限公司 | Preparation method and reaction device for synthesizing 4,4' -difluorobenzophenone by fluorobenzene |
| CN115108898B (en) * | 2022-07-02 | 2023-10-10 | 浙江三美化工股份有限公司 | Preparation method of fluorobenzene synthesized 4,4' -difluorobenzophenone and reaction device thereof |
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Application publication date: 20141015 |