CN104788341B - A kind of method preparing 2,6-difluorobenzonilyile - Google Patents
A kind of method preparing 2,6-difluorobenzonilyile Download PDFInfo
- Publication number
- CN104788341B CN104788341B CN201410023012.6A CN201410023012A CN104788341B CN 104788341 B CN104788341 B CN 104788341B CN 201410023012 A CN201410023012 A CN 201410023012A CN 104788341 B CN104788341 B CN 104788341B
- Authority
- CN
- China
- Prior art keywords
- difluorobenzonilyile
- reaction vessel
- temperature
- reaction
- dichlorobenzonitrile
- 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
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to one and prepare 2, the method for 6 difluorobenzonilyiles, add non-proton intensive polar solvent, toluene, 2,6 dichlorobenzonitrile and catalyst, controlling temperature is 110～150 DEG C, reflux dewatering, piptonychia benzene；It is cooled to 90～100 DEG C, in reaction vessel, adds potassium fluoride；Controlling reaction temperature is 150～250 DEG C, reacts 15～20h；Reaction vessel temperature is down to less than 50 DEG C, and the filtrate that sucking filtration obtains forwards in rectification bottle, opens vacuum pump, and vacuum is 0.1MPa, collects 105～108 DEG C of fractions, obtains finished product 2,6 difluorobenzonilyiles.Compared with prior art, reaction condition of the present invention is gentle, and preparation technology is simple, and reaction yield can be up to 98%.
Description
Technical field
The present invention relates to the preparation method of a kind of pesticide, especially relate to one and prepare 2, the method for 6-difluorobenzonilyile.
Background technology
2,6-difluorobenzonilyile is specificity insect growth regulator, IGR: the benzoyl area kind pesticide such as diflubenzuron, UC 62644 must
Standby intermediate, is the most also applicable as the synthesis of medicine, liquid crystal material, has market prospect widely.The most efficient
Synthesis 2,6-difluorobenzonilyile gets more and more people's extensive concerning, and the synthetic method of 2,6-difluorobenzonilyiles mainly has following several:
1, before 1980, the synthesis of 2,6-difluorobenzonilyiles mainly takes chlorinated aromatic hydrocarbons and anhydrous potassium fluoride various molten
Agent carries out the method (seeing GC, Fing, et al., chem.commn, 1965, (18), 430～431) of fluorination reaction.
2, phase transfer catalyst method: phase transfer catalysis process is to develop a kind of synthetic method quickly in organic synthesis, because of it
There is the features such as yield is high, reaction condition is gentle and be widely used.Usual phase transfer catalyst is quaternary ammonium salt, season phosphine
Salt, polyethers, crown ether etc. (beautiful see such as family industry, Wang Xianyi, Zeng Ying. pesticide, 1998,37 (7): 14～15 and patent
CN101456827)。
3, solventless method: German patent DE 3322936 reports 2,6-dichlorobenzonitrile and potassium fluoride under nitrogen atmosphere in 350 DEG C
Reacting 3 hours, pressure is maintained at 1.43MPa, yield 83%, purity 99%.
4,2,3,6-trichloro-benzenes nitrile synthesis: day JP 58189151(1983) patent mentions by 2,3,6-trichlorine cyanophenyl
Synthesize 3-chloro-2,6-difluoro cyanophenyl, then catalytic hydrogenation and dechlorination obtains 2,6-difluorobenzonilyile.
These synthesis techniques above-mentioned, technique 1 and 2 yield is relatively low, and technique 3 high-temperature and high-pressure conditions to be used, technique 4 technique is numerous
Trivial, post processing is complicated；Therefore industrial quarters is the most urgent to mild condition and the efficient method demand preparing 2,6-difluorobenzonilyile
's.
The invention provides that a kind of technique is simple, reaction time is short, it is gentle to react, the system of yield is high 2,6-difluorobenzonilyile
Preparation Method.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and provide a kind of reaction condition gentle,
Preparation technology is simple, and reaction yield reaches the preparation 2 of 98%, the method for 6-difluorobenzonilyile.
The purpose of the present invention can be achieved through the following technical solutions:
One prepares 2, the method for 6-difluorobenzonilyile, uses following steps:
(1) in reaction vessel, it is sequentially added into non-proton intensive polar solvent, toluene, 2,6-dichlorobenzonitrile and catalyst；
(2) opening heating system, controlling reaction vessel temperature is 110～150 DEG C, reflux dewatering, piptonychia benzene；
(3) utilize cooling system that reaction vessel temperature is down to 90～100 DEG C, in reaction vessel, add potassium fluoride；
(4) opening heating system, controlling reaction vessel temperature is 150～250 DEG C, reacts 15～20h；
(5) utilize cooling system that reaction vessel temperature is down to less than 50 DEG C, sucking filtration；
(6) during the filtrate that sucking filtration obtains forwards rectification bottle to, opening vacuum pump, vacuum is-0.1MPa, collects 105～108
DEG C fraction, obtains finished product 2,6-difluorobenzonilyile.
The molar equivalent ratio of 2,6-difluorobenzonilyiles and potassium fluoride is 1:2.2～5,
The consumption of catalyst is 2, the 3%～10% of 6-difluorobenzonilyile quality,
The mass ratio of non-proton intensive polar solvent and 2,6-difluorobenzonilyile is 1.0～5:1.
As preferred embodiment, the molar equivalent ratio of 2,6-difluorobenzonilyiles and potassium fluoride is 1:2.4, catalyst
Consumption is 2, the 6% of 6-difluorobenzonilyile quality, reaction dissolvent and 2, and the mass ratio of 6-difluorobenzonilyile is 3.
Non-proton intensive polar solvent described in step (1) is DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, N-methyl pyrrole
Pyrrolidone, 1,3-dimethyl-2-imidazolinone or sulfolane.
Catalyst described in step (1) is N-alkyl pyridine quaternary ammonium salt, and structural formula is:
Wherein, R be carbon chain lengths be the alkyl group of C1～C4, X is halogen, including chlorine, bromine or iodine.
The preferred N-ethylpyridinium chloride of described catalyst or chlorination N-propyIpyridine.
Temperature is risen to 110 DEG C by step (2), reflux dewatering 2h, then proceed to be warming up to 150 DEG C of removing toluene.
Compared with prior art, the present invention uses N-alkyl pyridine quaternary ammonium salt to be catalyst, adds potassium fluoride at solvent
In dissolubility, add the nucleophilicity of fluorion, beneficially fluorination reaction simultaneously and carry out and improve fluorination reaction yield, N-alkane
The fusing point of yl pyridines quaternary ammonium salt is high, and catalyst is high temperature resistant, Heat stability is good, excellent catalytic effect, and yield can reach 98%, compares it
He is less than 90% by quaternary ammonium salt catalyst yield, and heat stability is poor, and reaction temperature not can exceed that 180 DEG C, improves reaction and receives
Rate, reduces preparation cost；150～250 DEG C of reactions, without High Temperature High Pressure, reaction condition is gentle, and preparation technology is simple, suitableeer
Close industrialized production；The solvent of reaction can repeat to apply mechanically, and reduces preparation cost further；The yield additionally reacted is up to 98%,
Product purity is up to 99.5%, and the three wastes are little, are more suitable for industrialization.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1:
At 1000ml equipped with in the mechanic whirl-nett reaction bottle of condenser and water knockout drum, it is sequentially added into 1,3-dimethyl-2-miaow
Oxazoline ketone 450g, toluene 100g, 2,6-dichlorobenzonitrile 150g(content 99.5%, 0.868mol), N-ethylpyridinium chloride 9g, stir
Mix and be warmed up to 110 DEG C, reflux water-dividing 2 hours, then proceed to intensification piptonychia benzene, reclaim toluene 99g.
Close heating, reaction temperature lowered the temperature 90 DEG C, in reaction bulb, add anhydrous potassium fluoride 122g(content 99%,
2.08mol), heating is raised to 150 DEG C reaction temperature, insulation reaction 15 hours, closes heating.
Reaction temperature is dropped to 40 DEG C, and sucking filtration, filtrate forwards to, in rectification bottle, open vacuum, and vacuum is-0.1MPa, collects
105～108 DEG C of fractions, obtain finished product 2,6-difluorobenzonilyile 118.8g(content 99.5%, 0.85mol), yield 98%.Distillation residual liquid returns
Receipts are applied mechanically.
Embodiment 2:
At 1000ml equipped with in the mechanic whirl-nett reaction bottle of condenser and water knockout drum, it is sequentially added into 1,3-dimethyl-2-miaow
Oxazoline ketone 450g, toluene 100g, 2,6-dichlorobenzonitrile 150g(content 99.5%, 0.868mol), chlorination N-propyIpyridine 9g, stir
Mix and be warmed up to 110 DEG C, reflux water-dividing 2 hours, then proceed to intensification piptonychia benzene, reclaim toluene 99g.
Close heating, reaction temperature lowered the temperature 90 DEG C, in reaction bulb, add anhydrous potassium fluoride 122g(content 99%,
2.08mol), heating is raised to 150 DEG C reaction temperature, insulation reaction 15 hours, closes heating.
Reaction temperature is dropped to 40 DEG C, and sucking filtration, filtrate forwards to, in rectification bottle, open vacuum, and vacuum is-0.1MPa, collects
105～108 DEG C of fractions, obtain finished product 2,6-difluorobenzonilyile 119g(content 99.5%, 0.852mol), yield 98.17%.Distillation residual liquid
Recovery.
Embodiment 3:
At 1000ml equipped with in the mechanic whirl-nett reaction bottle of condenser and water knockout drum, it is sequentially added into dimethyl sulfoxide, toluene
100g, 2,6-dichlorobenzonitrile 150g(content 99.5%, 0.868mol), N-ethylpyridinium chloride 9g, stirring is warmed up to 110 DEG C, returns
Flow point water 2 hours, then proceedes to intensification piptonychia benzene, reclaims toluene 99g.
Close heating, reaction temperature lowered the temperature 90 DEG C, in reaction bulb, add anhydrous potassium fluoride 122g(content 99%,
2.08mol), heating is raised to 150 DEG C reaction temperature, insulation reaction 15 hours, closes heating.
Reaction temperature is dropped to 40 DEG C, and sucking filtration, filtrate forwards to, in rectification bottle, open vacuum, and vacuum is-0.1MPa, collects
105～108 DEG C of fractions, obtain finished product 2,6-difluorobenzonilyile 119.2g(content 99.5%, 0.853mol), yield 98.34%.Rectification is residual
Liquid recovery.
Embodiment 4:
At 1000ml equipped with in the mechanic whirl-nett reaction bottle of condenser and water knockout drum, it is sequentially added into sulfolane 450g, toluene
100g, 2,6-dichlorobenzonitrile 150g(content 99.5%, 0.868mol), N-ethylpyridinium chloride 9g, stirring is warmed up to 110 DEG C, returns
Flow point water 2 hours, then proceedes to intensification piptonychia benzene, reclaims toluene 99g.
Close heating, reaction temperature lowered the temperature 90 DEG C, in reaction bulb, add anhydrous potassium fluoride 122g(content 99%,
2.08mol), heating is raised to 190 DEG C reaction temperature, insulation reaction 15 hours, closes heating.
Reaction temperature is dropped to 40 DEG C, and sucking filtration, filtrate forwards to, in rectification bottle, open vacuum, and vacuum is-0.1MPa, collects
105～108 DEG C of fractions, obtain finished product 2,6-difluorobenzonilyile 118.8g(content 99.5%, 0.85mol), yield 98%.Distillation residual liquid returns
Receipts are applied mechanically.
Embodiment 6
One prepares 2, the method for 6-difluorobenzonilyile, uses following steps:
(1) in reaction vessel, it is sequentially added into 1,3-dimethyl-2-imidazolinone, toluene, 2,6-dichlorobenzonitrile and catalysis
Agent bromination N-ethylpyridine, wherein, the consumption of catalyst is 2, the 3% of 6-difluorobenzonilyile quality, 1,3-dimethyl-2-imidazoline
The mass ratio of ketone and 2,6-difluorobenzonilyile is 1:1；
(2) opening heating system, controlling reaction vessel temperature is 110 DEG C, and reflux dewatering 2h then proceedes to be warming up to 150
DEG C removing toluene；
(3) utilize cooling system that reaction vessel temperature is down to 90 DEG C, in reaction vessel, add potassium fluoride, 2,6-difluoros
The molar equivalent ratio of cyanophenyl and potassium fluoride is 1:2.2；
(4) opening heating system, controlling reaction vessel temperature is 150 DEG C, reacts 20h；
(5) utilize cooling system that reaction vessel temperature is down to less than 50 DEG C, sucking filtration；
(6) during the filtrate that sucking filtration obtains forwards rectification bottle to, opening vacuum pump, vacuum is-0.1MPa, collects 105～108
DEG C fraction, obtains finished product 2,6-difluorobenzonilyile.
Embodiment 7
One prepares 2, the method for 6-difluorobenzonilyile, uses following steps:
(1) in reaction vessel, it is sequentially added into sulfolane, toluene, 2,6-dichlorobenzonitrile and catalyst bromination N-isobutyl group pyrrole
Pyridine, wherein, the consumption of catalyst is 2, the 6% of 6-difluorobenzonilyile quality, sulfolane and 2, and the mass ratio of 6-difluorobenzonilyile is 3:1；
(2) opening heating system, controlling reaction vessel temperature is 110 DEG C, and reflux dewatering 2h then proceedes to be warming up to 150
DEG C removing toluene；
(3) utilize cooling system that reaction vessel temperature is down to 90 DEG C, in reaction vessel, add potassium fluoride, 2,6-difluoros
The molar equivalent ratio of cyanophenyl and potassium fluoride is 1:2.4；
(4) opening heating system, controlling reaction vessel temperature is 200 DEG C, reacts 18h；
(5) utilize cooling system that reaction vessel temperature is down to less than 50 DEG C, sucking filtration；
(6) during the filtrate that sucking filtration obtains forwards rectification bottle to, opening vacuum pump, vacuum is-0.1MPa, collects 105～108
DEG C fraction, obtains finished product 2,6-difluorobenzonilyile.
Embodiment 8
One prepares 2, the method for 6-difluorobenzonilyile, uses following steps:
(1) in reaction vessel, it is sequentially added into sulfolane, toluene, 2,6-dichlorobenzonitrile and catalyst iodate N-propyl group pyrrole
Pyridine, wherein, the consumption of catalyst is 2, the 10% of 6-difluorobenzonilyile quality, sulfolane and 2, and the mass ratio of 6-difluorobenzonilyile is 5:
1；
(2) opening heating system, controlling reaction vessel temperature is 110 DEG C, and reflux dewatering 2h then proceedes to be warming up to 150
DEG C removing toluene；
(3) utilize cooling system that reaction vessel temperature is down to 100 DEG C, addition potassium fluoride in reaction vessel, 2,6-bis-
The molar equivalent ratio of fluorobenzonitrile and potassium fluoride is 1:5；
(4) opening heating system, controlling reaction vessel temperature is 250 DEG C, reacts 15h；
(5) utilize cooling system that reaction vessel temperature is down to less than 50 DEG C, sucking filtration；
(6) during the filtrate that sucking filtration obtains forwards rectification bottle to, opening vacuum pump, vacuum is-0.1MPa, collects 105～108
DEG C fraction, obtains finished product 2,6-difluorobenzonilyile.
Claims (5)
1. prepare 2 for one kind, the method for 6-difluorobenzonilyile, it is characterised in that the method employing following steps:
(1) be sequentially added in reaction vessel non-proton intensive polar solvent, toluene, 2,6-dichlorobenzonitrile and catalyst, wherein, urge
Agent is N-alkyl pyridine quaternary ammonium salt, and structural formula is:
R be carbon chain lengths be the alkyl group of C1～C4, X is halogen；
(2) opening heating system, controlling reaction vessel temperature is 110～150 DEG C, reflux dewatering, piptonychia benzene；
(3) utilize cooling system that reaction vessel temperature is down to 90～100 DEG C, in reaction vessel, add potassium fluoride；
(4) opening heating system, controlling reaction vessel temperature is 150～250 DEG C, reacts 15～20h；
(5) utilize cooling system that reaction vessel temperature is down to less than 50 DEG C, sucking filtration；
(6) during the filtrate that sucking filtration obtains forwards rectification bottle to, opening vacuum pump, vacuum is-0.1MPa, collects 105～108 DEG C and evaporates
Point, obtain finished product 2,6-difluorobenzonilyile；
The molar equivalent ratio of 2,6-dichlorobenzonitriles and potassium fluoride is 1:2.2～5,
The consumption of catalyst is 2, the 3%～10% of 6-dichlorobenzonitrile quality,
The mass ratio of non-proton intensive polar solvent and 2,6-dichlorobenzonitrile is 1.0～5:1；
Non-proton intensive polar solvent described in step (1) is DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, N-crassitude
Ketone, 1,3-dimethyl-2-imidazolinone or sulfolane.
One the most according to claim 1 prepares 2, the method for 6-difluorobenzonilyile, it is characterised in that
The molar equivalent ratio of 2,6-dichlorobenzonitriles and potassium fluoride is 1:2.4,
The consumption of catalyst is 2, the 6% of 6-dichlorobenzonitrile quality,
The mass ratio of reaction dissolvent and 2,6-dichlorobenzonitrile is 3.
One the most according to claim 1 prepares 2, the method for 6-difluorobenzonilyile, it is characterised in that described catalyst is excellent
Select N-ethylpyridinium chloride or chlorination N-propyIpyridine.
One the most according to claim 1 prepares 2, the method for 6-difluorobenzonilyile, it is characterised in that N-alkane in step (1)
X in the structural formula of yl pyridines quaternary ammonium salt includes chlorine, bromine or iodine.
One the most according to claim 1 prepares 2, the method for 6-difluorobenzonilyile, it is characterised in that by temperature in step (2)
Degree rises to 110 DEG C, reflux dewatering 2h, then proceedes to be warming up to 150 DEG C of removing toluene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410023012.6A CN104788341B (en) | 2014-01-17 | 2014-01-17 | A kind of method preparing 2,6-difluorobenzonilyile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410023012.6A CN104788341B (en) | 2014-01-17 | 2014-01-17 | A kind of method preparing 2,6-difluorobenzonilyile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104788341A CN104788341A (en) | 2015-07-22 |
| CN104788341B true CN104788341B (en) | 2017-01-04 |
Family
ID=53553583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410023012.6A Active CN104788341B (en) | 2014-01-17 | 2014-01-17 | A kind of method preparing 2,6-difluorobenzonilyile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104788341B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111454174A (en) * | 2019-01-18 | 2020-07-28 | 南通泰禾化工股份有限公司 | Method for preparing fluorobenzonitrile |
| CN113024414A (en) * | 2021-03-23 | 2021-06-25 | 江苏合泰新材料科技有限公司 | Method for efficiently synthesizing fluorine-containing compound |
| CN113620841A (en) * | 2021-08-03 | 2021-11-09 | 南京硕达生物科技有限公司 | Method for preparing 2, 6-difluorobenzonitrile |
| CN113929595A (en) * | 2021-11-12 | 2022-01-14 | 江苏新河农用化工有限公司 | Preparation method of 2, 6-difluorobenzonitrile |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1433420A (en) * | 2000-04-26 | 2003-07-30 | 阿托菲纳公司 | Ion liquids derived from lewis acid based on titanium, niobium, tantalum, tin or antimony and uses thereof |
| CN1580042A (en) * | 2003-08-15 | 2005-02-16 | 中国科学院动物研究所 | Substituted benzoyl urea insect growth regulator synthesizing method |
| CN101456827A (en) * | 2009-01-05 | 2009-06-17 | 扬州天辰精细化工有限公司 | Industrial production method of 2,6-difluorobenzene nitrile |
-
2014
- 2014-01-17 CN CN201410023012.6A patent/CN104788341B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1433420A (en) * | 2000-04-26 | 2003-07-30 | 阿托菲纳公司 | Ion liquids derived from lewis acid based on titanium, niobium, tantalum, tin or antimony and uses thereof |
| CN1580042A (en) * | 2003-08-15 | 2005-02-16 | 中国科学院动物研究所 | Substituted benzoyl urea insect growth regulator synthesizing method |
| CN101456827A (en) * | 2009-01-05 | 2009-06-17 | 扬州天辰精细化工有限公司 | Industrial production method of 2,6-difluorobenzene nitrile |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104788341A (en) | 2015-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104788341B (en) | A kind of method preparing 2,6-difluorobenzonilyile | |
| CN104402780B (en) | 4, the synthesis technique of 4 '-dichloro diphenyl sulfone | |
| CN102516060B (en) | Preparation method of m-phthaloyl chloride | |
| CN103739500B (en) | A kind of synthesis of cinacalcet hydrochloride and process for purification | |
| CN107473949B (en) | Synthesis process of 3, 5-dichloro-2-pentanone | |
| CN109574877B (en) | Preparation method of 2-cyano-3-fluorobenzotrifluoride | |
| CN105693507B (en) | The synthetic method of 3,4,5,6 ptfe phthalates | |
| US10183903B2 (en) | Method for preparing 2,3,3,3-tetrafluoropropene using methyl magnesium chloride | |
| CN111039771B (en) | Preparation method of 3,3, 3-trifluoropropionic acid | |
| JP2004161768A (en) | Method for production of polyhaloalkylaryl compounds | |
| JPS623087B2 (en) | ||
| CN105408293A (en) | Method for manufacturing methyl fluoride | |
| CN105646261B (en) | A kind of method for preparing totokaine | |
| CN108017574B (en) | A kind of method of the chloro- 2,4,6- trifluoromethyl pyridine continuous production of fluroxypramide intermediate 3,5- bis- | |
| CN106478464A (en) | A kind of preparation method of 2 fluorine, 6 trifluoromethyl benzene sulfonyl chloride | |
| JPH0565250A (en) | Production of 3,5-difluoroaniline | |
| CN110283043A (en) | A method of preparing the chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2- | |
| CN106631886B (en) | The preparation method of 2- nitro-4-trifluoromethyl Benzonitriles | |
| CN108997203A (en) | A kind of process for effectively purifying of bis- chloro-5-trifluoromethylpyridine of 2,3- | |
| JP7482125B2 (en) | Process for the preparation of 2,6-dichlorobenzonitrile | |
| CN108191628B (en) | Method for preparing bis- (heptafluoroisopropyl) -ketone by oxalyl chloride fluorination | |
| WO2020119507A1 (en) | Method for continuously preparing 5-citalopram diol | |
| CN115010694B (en) | Fluoroethylene carbonate and preparation method thereof | |
| CN104030906A (en) | Method for preparing 9-fluorenone by liquid-phase oxidation | |
| CN108358797A (en) | A kind of synthetic method of alkyl glycine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 200335 Shanghai city Changning District North Zhai Road No. 785 Applicant after: SHANGHAI TAIHE INTERNATIONAL TRADE CO., LTD. Applicant after: Nantong Taihe Chemical Co., Ltd. Address before: 200335 Shanghai city Changning District North Zhai Road No. 785 Applicant before: Shanghai CAC Chemical Co.,Ltd. Applicant before: Nantong Taihe Chemical Co., Ltd. |
|
| COR | Change of bibliographic data | ||
| CB02 | Change of applicant information |
Address after: 200335 Shanghai city Changning District North Zhai Road No. 785 Applicant after: SHANGHAI TAIHE INTERNATIONAL TRADE CO., LTD. Applicant after: Nantong Taihe chemical Limited by Share Ltd Address before: 200335 Shanghai city Changning District North Zhai Road No. 785 Applicant before: SHANGHAI TAIHE INTERNATIONAL TRADE CO., LTD. Applicant before: Nantong Taihe Chemical Co., Ltd. |
|
| COR | Change of bibliographic data | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Yang Binglian Inventor after: Zhou Qingjiang Inventor after: Wu Yong Inventor after: Xie Simian Inventor after: Tian Xiaohong Inventor before: Zhou Qingjiang Inventor before: Wu Yong Inventor before: Xie Simian Inventor before: Tian Xiaohong |