CN110117256A - A kind of synthetic method of biphenyl pyrrole bacterium amine - Google Patents
A kind of synthetic method of biphenyl pyrrole bacterium amine Download PDFInfo
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- CN110117256A CN110117256A CN201910551960.XA CN201910551960A CN110117256A CN 110117256 A CN110117256 A CN 110117256A CN 201910551960 A CN201910551960 A CN 201910551960A CN 110117256 A CN110117256 A CN 110117256A
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- C07—ORGANIC CHEMISTRY
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- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The present invention relates to a kind of synthetic methods of biphenyl pyrrole bacterium amine, first by 3,4- dichloroaniline is prepared into 3 using reducing agent, 4- dichloride phenyl hydrazine hydrochloric acid salt, again by 3,4- dichloride phenyl hydrazine hydrochloric acid salt is passed through air under alkaline environment and para-fluoroaniline oxidative coupling obtains intermediate 3`, and the fluoro- 2- benzidine of the chloro- 5- of 4`- bis- finally occurs amidation process with 1- methyl -3- difluoromethyl -4- pyrazol formyl chloride and biphenyl pyrrole bacterium amine is prepared.The mild reaction condition that the present invention uses is easily-controllable, easy to operate, and product purification is easy, and can directly be recrystallized to give product.Wherein each to walk intermediate body controlling means simply, accurately, product yield is higher, and Atom economy is preferable, avoids the cumbersome post-processing of aging method, has very big competitive advantage and industrial production utility value.Meanwhile avoiding and being generated using the solid waste of the higher raw material of the risk such as butyl lithium and a large amount of tarry matters, the three wastes are extremely low, meet the theory of Green Chemistry.
Description
Technical field
The invention belongs to the synthetic method of biphenyl pyrrole bacterium amine, it is related to a kind of pyrazol acid amide class fungicide biphenyl pyrrole bacterium amine
A kind of preparation method
Background technique
Biphenyl pyrrole bacterium amine, English name Bixafen are a kind of pyrazole amide succinic acid dehydrogenation matchmaker suppressions that Beyer Co., Ltd develops
Preparation is a kind of novel cereal fungicide, and the mechanism of action is mitochondrial inhibitors, upsets Complex II in respiration
Electron transfer function, the prevention and treatment of its main function leaf rust and leaf spot, and it is expected to the important product as fungicide resistance management
Kind, the mixture of it and prothioconazoles has " unrivaled ", long-acting, wide spectrum disease-controlling effect.For winter wheat, rye and
Triticale, the mixture play the role of plant physiology positive, can enhance resistance, improve yield, and the mixture combines one
A patent emulsion formulations blade face protection, to improve its vegetation rate and rain fastness.
At present there are mainly two types of the preparation methods of biphenyl pyrrole bacterium amine, one is with elder generation with the bromo- 4- fluoroaniline of 2- and 3,4- bis-
Chlorophenylboronic acid is that raw material carries out Suzuki coupling reaction obtained intermediate 3` in the presence of palladium catalyst, and the chloro- 5- of 4`- bis- is fluoro-
2- benzidine.Then benzidine intermediate carries out acylation reaction with 1- methyl -3- difluoromethyl -4- pyrazol formyl chloride again and mesh is made
Mark product.The total recovery of this route is about 63%, and European patent WO2008145740 describes such method, but uses this
The bromo- 4- fluoroaniline of the raw material 2- of one route and 3, all costly, and Suzuki reaction is needed using expensive 4- dichloro phenyl boric acid
Palladium catalyst be unfavorable for industrialized production so that such technical solution is at high cost, hinder pushing away for this highly effective pesticide kind
Broad-spectrum and.
Another kind is the method construct benzidine being coupled again with para-fluoroaniline using 3,4-DCA as raw material elder generation diazotising
Intermediate, then with 1- methyl -3- difluoromethyl -4- pyrazol formyl chloride is acylated generates target product, total recovery be 55.8% (such as
Chemistry-A European Journal, 2012,18 (37): 11555-11559), but such method is in diazo reagent
It is not easy to control that the extremely low reaction process of not only conversion ratio is reacted with the coupling of para-fluoroaniline, but also is generated during the reaction a large amount of
Tar class by-product, is introduced into subsequent process and causes purification difficult, is unfavorable for the serious problems of industrialized production more than solid waste etc..And
(Journal of Organic Chemistry, 2014, vol.79, #5,2314-2320) further improves such side afterwards
Method carries out oxidative coupling using adding after Reduction with Stannous Chloride diazonium salt formation biphenyl hydrazine hydrochloride solid in reaction system,
But lower the method yield is 44%, and the stannous chloride of use is not only expensive, easy to maintain, and in actual application
New tin metal oxychloride pollution is introduced to nature, is unfavorable for realizing the economy in industrialized production, environmental protection two is big former
Then.
Summary of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes a kind of synthetic method of biphenyl pyrrole bacterium amine, provide
A kind of economic, environmentally protective biphenyl pyrrole bacterium amine preparation method suitable for industrialized production.
Technical solution
A kind of synthetic method of biphenyl pyrrole bacterium amine, it is characterised in that steps are as follows:
Step 1: by compound 3,4-DCA, acid and solvent mixed dissolution, be added sodium nitrite -20~
0.5h-2h is reacted after the reaction was completed under the conditions of 10 DEG C, and clear liquid is obtained by filtration；Molar ratio with clear liquid and reducing agent is 1:1~1:4
Mixing reacts 1h~8h under the conditions of 40~80 DEG C and generates 3,4- dichloro phenyl hydrazine；It is anti-under the conditions of 40~80 DEG C to add hydrochloric acid
Answer 30min~1.5h that 3,4- dichloride phenyl hydrazine hydrochloric acid salt white solid is obtained by filtration；The compound 3,4-DCA and acids
The molar ratio of substance is 1:2.5~1:5, and the molar ratio with sodium nitrite is 1:1~1:2 and the quality of solvent and volume ratio are
1g:0.5ml~1g:10ml；The molar ratio of the 3,4- dichloro phenyl hydrazine and hydrochloric acid is 1:1~1:4；
Step 2: the mixing of 3,4- dichloride phenyl hydrazine hydrochloric acid salt, solvent, base catalyst and para-fluoroaniline is passed through again under stirring
Air, temperature be 30~90 DEG C reaction, the reaction time be 8h~48h after be cooled to room temperature washed reaction liquid, separate organic phase,
Dry, revolving obtains intermediate 3`, the fluoro- 2- benzidine of the chloro- 5- of 4`- bis-；The quality of the 3,4- dichloride phenyl hydrazine hydrochloric acid salt with it is molten
The volume ratio of agent is 1g:0.5ml~1g:10ml, is 1:1~1:3 with base catalyst molar ratio, and the molar ratio with para-fluoroaniline is
1:1~1:15；
Step 3: by intermediate 3`, the fluoro- 2- benzidine of the chloro- 5- of 4`- bis-, 1- methyl -3- difluoromethyl -4- pyrazoles formyl
Chlorine, solvent and catalyst react 1~5h under the conditions of 30~90 DEG C, washed reaction liquid are cooled to room temperature after reaction, is separated organic
Phase, dry, concentrated by rotary evaporation is recrystallized to give biphenyl pyrrole bacterium amine；The fluoro- 2- benzidine of the chloro- 5- of the intermediate 3`, 4`- bis- and 1-
Methyl -3- difluoromethyl -4- pyrazol formyl chloride molar ratio is 1:1~1:0.8, with the quality and volume ratio of solvent be 1g:4ml~
1g:15ml, the molar ratio with catalyst are 1:0.3 to 1:2.
The acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid.
The solvent of the step 1~step 3 are as follows: ethyl acetate, Ethyl formate, acetonitrile, water, ether, methyl tertiary butyl ether(MTBE),
Tetrahydrofuran, dimethyl-tetrahydrofuran, benzene,toluene,xylene, methylene chloride, dichloroethanes, chloroform, one in carbon tetrachloride
Kind is a variety of.
The reducing agent zinc powder, iron powder, potassium borohydride, sodium borohydride, sodium hydrogensulfite, sodium sulfite, ferrous sulfate, second
One or more of alcohol.
The base catalyst include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, sodium methoxide, sodium ethoxide,
One of sodium tert-butoxide, sodium borohydride are a variety of.
The catalyst includes triethylamine, pyridine, N, N- diisopropylethylamine, sodium hydroxide, cesium carbonate, potassium carbonate, carbon
One of sour sodium, sodium bicarbonate, ammonium carbonate, tetrabutylammonium bromide are a variety of.
Beneficial effect
3,4-DCA, is first prepared by a kind of synthetic method of biphenyl pyrrole bacterium amine proposed by the present invention using reducing agent
For 3,4- dichloride phenyl hydrazine hydrochloric acid salt, then 3,4- dichloride phenyl hydrazine hydrochloric acid salt is passed through air under alkaline environment and para-fluoroaniline aoxidizes
Coupling obtains intermediate 3`, and the fluoro- 2- benzidine of the chloro- 5- of 4`- bis- is finally sent out with 1- methyl -3- difluoromethyl -4- pyrazol formyl chloride
Biphenyl pyrrole bacterium amine is prepared in raw amidation process.Synthesis conversion of the present invention and selectivity are high, are cheaply easy to using raw material
It arrives, greatly reduces the production cost of product.Also, the mild reaction condition that the present invention uses is easily-controllable, easy to operate, produces
Product purification is easy, and can directly be recrystallized to give product.It is wherein each that walk intermediate body controlling means simple, accurate, product yield compared with
Height, Atom economy is preferable, avoids the cumbersome post-processing of aging method, has very big competitive advantage and industrial production exploitation value
Value.Meanwhile avoiding and being generated using the solid waste of the higher raw material of the risk such as butyl lithium and a large amount of tarry matters, three wastes pole
It is low, meet the theory of Green Chemistry.
The present invention has the advantage that the reaction condition of the invention for preparing biphenyl pyrrole bacterium amine is more warm compared with prior art
With prepare that raw material is cheap and easy to get, and step is easier, select reagent and the cleaning of reaction process green, greatly reduce the three wastes
It generates, is suitable for industrialized production, and the yield and content that finally produce are higher.
Intermediate 3` is prepared by 3,4-DCA in the present invention, when the fluoro- 2- benzidine of the chloro- 5- of 4`- bis-, is not only made wherein
Mesosome 3,4- dichloride phenyl hydrazine hydrochloric acid salt is more stable, and reduces the use of the amount of reagent, simplifies operating procedure, avoids pair
The generation of reaction improves reaction efficiency, and three-waste pollution is few, and record colour circle is protected, and is suitable for industrialized production.In addition, of the invention
It is cheap and easy to get to prepare raw material, and the yield of the bis- fluoro- 2- benzidine of chloro- 5- of compound 3`, 4`- and content are higher.
Detailed description of the invention
The synthetic method principle schematic diagram of Fig. 1 biphenyl pyrrole bacterium amine of the present invention
Specific embodiment
Now in conjunction with embodiment, attached drawing, the invention will be further described:
Embodiment 1
The preparation method of the biphenyl pyrrole bacterium amine of the present embodiment has follow steps:
Compound 3,4-DCA (38.88g, 0.2399mol) is dissolved in dichloroethanes (30ml) by step (1), with
The concentrated hydrochloric acid (70ml, 0.84mol) of 12mol/L is added afterwards, sodium nitrite (18.06g, 0.261mol) is added, reaction solution is at 5 DEG C
Under be stirred to react 30min after, filter out supernatant liquid, be added dropwise to 140ml containing (90.71g, 0.7197mol) sodium sulfite solution
In, 80 DEG C are reacted about 3 hours, and reaction is generated as 3,4- dichloro phenyl hydrazine, and it is anti-to add about (60ml, 0.72mol) concentrated hydrochloric acid heat preservation
After answering 1h, stirring at normal temperature is overnight, and 3,4- dichloride phenyl hydrazine hydrochloric acid salt white solid 46.1g, yield: 90% is obtained by filtration.
Step 2: water (30ml) and chloroform is added portionwise in 3,4- dichloride phenyl hydrazine hydrochloric acid salt (46.1g, 0.2159mol)
The mixed system of (30ml) mixed solvent and potassium carbonate (59.68g, 0.4318mol), para-fluoroaniline (26.66g, 0.2399mol)
In, it is passed through air into system for 24 hours under 70 DEG C of stirrings, washed reaction liquid is cooled to room temperature after reaction, separates organic phase, it is dry,
Revolving obtains intermediate 3`, the fluoro- 2- benzidine 48.65g of the chloro- 5- of 4`- bis-, yield: 88%.
Step 3: by (48.65g, 0.19mol) intermediate 3`, the fluoro- 2- benzidine of the chloro- 5- of 4`- bis- is in solvent dichloroethanes
It dissolves completely, is added catalyst sodium hydroxide (7.6g, 0.19mol), 60 DEG C are added with stirring 1- methyl -3- difluoro in 300ml
Methyl -4- pyrazol formyl chloride (36.96g, 0.19mol) reacts 4h under the conditions of 60 DEG C, is cooled to room temperature washed reaction after reaction
Liquid separates organic phase, dry, and concentrated by rotary evaporation is recrystallized to give the biphenyl pyrrole bacterium amine 77.13g, yield: 98%
Embodiment 2
The preparation method of the biphenyl pyrrole bacterium amine of the present embodiment has follow steps:
Compound 3,4-DCA (38.88g, 0.2399mol) is dissolved in ethyl acetate (15ml) by step (1), with
The concentrated hydrochloric acid (70ml, 0.84mol) of 18.4mol/L is added afterwards, sodium nitrite (18.06g, 0.261mol) is added, reaction solution is 5
After being stirred to react 30min at DEG C, supernatant liquid is filtered out, is added dropwise to 140ml containing (200g, 0.7197mol) ferrous sulfate solution
In, 80 DEG C are reacted about 3 hours, and reaction is generated as 3,4- dichloro phenyl hydrazine, and it is anti-to add about (60ml, 0.72mol) concentrated hydrochloric acid heat preservation
After answering 1h, stirring at normal temperature is overnight, and 3,4- dichloride phenyl hydrazine hydrochloric acid salt white solid 45g, yield: 87.8% is obtained by filtration.
Step 2: water (30ml) and ethyl acetate is added portionwise in 3,4- dichloride phenyl hydrazine hydrochloric acid salt (46.1g, 0.2159mol)
The mixture of (30ml) mixed solvent and potassium hydroxide (24.22g, 0.4318mol), para-fluoroaniline (26.66g, 0.2399mol)
In system, it is passed through air into system for 24 hours under 60 DEG C of stirrings, washed reaction liquid is cooled to room temperature after reaction, separates organic phase, does
Dry, revolving obtains intermediate 3`, the fluoro- 2- benzidine 44.22g of the chloro- 5- of 4`- bis-, yield: 80%.
Step 3: by (48.65g, 0.19mol) intermediate 3`, the fluoro- 2- benzidine of the chloro- 5- of 4`- bis- is in solvents tetrahydrofurane
It dissolves completely, is added catalyst pyridine (15g, 0.19mol), 40 DEG C are added with stirring 1- methyl -3- difluoromethyl-in 280ml
4- pyrazol formyl chloride (36.96g, 0.19mol) reacts 4h under the conditions of 40 DEG C, washed reaction liquid is cooled to room temperature after reaction, point
Organic phase out, dry, concentrated by rotary evaporation is recrystallized to give the biphenyl pyrrole bacterium amine 75.55g, yield: 96%
Embodiment 3
The preparation method of the biphenyl pyrrole bacterium amine of the present embodiment has follow steps:
Compound 3,4-DCA (38.88g, 0.2399mol) is dissolved in tetrahydrofuran (30ml) by step (1), with
The concentrated hydrochloric acid (70ml, 0.84mol) of 12mol/L is added afterwards, sodium nitrite (18.06g, 0.261mol) is added, reaction solution is at 5 DEG C
Under be stirred to react 30min after, filter out supernatant liquid, be added dropwise to 140ml containing (74.89g, 0.7197mol) sodium hydrogensulfite it is molten
In liquid, 70 DEG C are reacted about 3 hours, and reaction is generated as 3,4- dichloro phenyl hydrazine, add about (60ml, 0.72mol) concentrated hydrochloric acid heat preservation
After reacting 1h, stirring at normal temperature is overnight, and 3,4- dichloride phenyl hydrazine hydrochloric acid salt white solid 47.12g, yield: 92% is obtained by filtration.
Step 2: water (30ml) and tetrahydrofuran is added portionwise in 3,4- dichloride phenyl hydrazine hydrochloric acid salt (46.1g, 0.2159mol)
The mixed system of (30ml) mixed solvent and cesium carbonate (70.34g, 0.2159mol), para-fluoroaniline (26.66g, 0.2399mol)
In, it is passed through air into system for 24 hours under 70 DEG C of stirrings, washed reaction liquid is cooled to room temperature after reaction, separates organic phase, it is dry,
Revolving obtains intermediate 3`, the fluoro- 2- benzidine 49.2g of the chloro- 5- of 4`- bis-, yield: 89%.
Step 3: by (48.65g, 0.19mol) intermediate 3`, the fluoro- 2- benzidine of the chloro- 5- of 4`- bis- is in solvent toluene 500ml
Completely, catalyst n is added, N- diisopropylethylamine (24.55g, 0.19mol), 60 DEG C are added with stirring 1- methyl -3- in middle dissolution
Difluoromethyl -4- pyrazol formyl chloride (36.96g, 0.19mol) reacts 4h under the conditions of 60 DEG C, washing is cooled to room temperature after reaction
Reaction solution separates organic phase, dry, and concentrated by rotary evaporation is recrystallized to give the biphenyl pyrrole bacterium amine 77.91g, yield: 99%.
Claims (6)
1. a kind of synthetic method of biphenyl pyrrole bacterium amine, it is characterised in that steps are as follows:
Step 1: by compound 3,4-DCA, acid and solvent mixed dissolution, sodium nitrite is added at -20~10 DEG C
Under the conditions of reaction 0.5h-2h after the reaction was completed, clear liquid is obtained by filtration；It is mixed for 1:1~1:4 with the molar ratio of clear liquid and reducing agent
It closes, 1h~8h is reacted under the conditions of 40~80 DEG C and generates 3,4- dichloro phenyl hydrazine；Hydrochloric acid is added to react under the conditions of 40~80 DEG C
3,4- dichloride phenyl hydrazine hydrochloric acid salt white solid is obtained by filtration in 30min~1.5h；The compound 3,4-DCA and acids object
The molar ratio of matter is 1:2.5~1:5, and the molar ratio with sodium nitrite is 1:1~1:2 and the quality of solvent and volume ratio are 1g:
0.5ml~1g:10ml；The molar ratio of the 3,4- dichloro phenyl hydrazine and hydrochloric acid is 1:1~1:4；
Step 2: by the mixing of 3,4- dichloride phenyl hydrazine hydrochloric acid salt, solvent, base catalyst and para-fluoroaniline, being passed through sky under stirring again
Gas is 30~90 DEG C of reactions in temperature, and the reaction time to be cooled to room temperature washed reaction liquid after 8h~48h, separates organic phase, does
Dry, revolving obtains intermediate 3`, the fluoro- 2- benzidine of the chloro- 5- of 4`- bis-；The quality and solvent of the 3,4- dichloride phenyl hydrazine hydrochloric acid salt
Volume ratio be 1g:0.5ml~1g:10ml, be 1:1~1:3 with base catalyst molar ratio, be 1 with the molar ratio of para-fluoroaniline:
1~1:15；
Step 3: the fluoro- 2- benzidine of the chloro- 5- of 4`- bis-, 1- methyl -3- difluoromethyl -4- pyrazol formyl chloride, molten by intermediate 3`
Agent and catalyst react 1~5h under the conditions of 30~90 DEG C, washed reaction liquid are cooled to room temperature after reaction, separates organic phase, do
Dry, concentrated by rotary evaporation is recrystallized to give biphenyl pyrrole bacterium amine；The fluoro- 2- benzidine of the chloro- 5- of the intermediate 3`, 4`- bis- and 1- methyl-
3- difluoromethyl -4- pyrazol formyl chloride molar ratio is 1:1~1:0.8, and the quality and volume ratio with solvent are 1g:4ml~1g:
15ml, the molar ratio with catalyst are 1:0.3 to 1:2.
2. the synthetic method of biphenyl pyrrole bacterium amine according to claim 1, it is characterised in that: the acid is hydrochloric acid, sulphur
One or more of acid, nitric acid, acetic acid.
3. the synthetic method of biphenyl pyrrole bacterium amine according to claim 1, it is characterised in that: the solvent of the step 1~step 3
Are as follows: ethyl acetate, Ethyl formate, acetonitrile, water, ether, methyl tertiary butyl ether(MTBE), tetrahydrofuran, dimethyl-tetrahydrofuran, benzene, first
One of benzene, dimethylbenzene, methylene chloride, dichloroethanes, chloroform, carbon tetrachloride are a variety of.
4. the synthetic method of biphenyl pyrrole bacterium amine according to claim 1, it is characterised in that: the reducing agent zinc powder, iron powder, boron
One or more of hydrofining, sodium borohydride, sodium hydrogensulfite, sodium sulfite, ferrous sulfate, ethyl alcohol.
5. the synthetic method of biphenyl pyrrole bacterium amine according to claim 1, it is characterised in that: the base catalyst includes hydroxide
One of sodium, potassium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, sodium borohydride are more
Kind.
6. the synthetic method of biphenyl pyrrole bacterium amine according to claim 1, it is characterised in that: the catalyst include triethylamine,
Pyridine, N, N- diisopropylethylamine, sodium hydroxide, cesium carbonate, potassium carbonate, sodium carbonate, sodium bicarbonate, ammonium carbonate, tetrabutyl bromine
Change one of ammonium or a variety of.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111072492A (en) * | 2019-11-29 | 2020-04-28 | 浙江工业大学 | Method for synthesizing 3,4-dichloro-2-amino-5-fluorobiphenyl |
| CN115160226A (en) * | 2022-07-19 | 2022-10-11 | 欧阳建峰 | Method for preparing bixafen by one-step condensation method |
| WO2023031959A1 (en) * | 2021-08-31 | 2023-03-09 | Upl Limited | A process for preparation of bixafen |
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| CN103517893A (en) * | 2011-03-07 | 2014-01-15 | 巴斯夫欧洲公司 | Process for the synthesis of aminobiphenylene |
| CN104220417A (en) * | 2012-03-07 | 2014-12-17 | 巴斯夫欧洲公司 | Method for synthesising aminobiphenyls using aryl hydrazines |
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| CN103517893A (en) * | 2011-03-07 | 2014-01-15 | 巴斯夫欧洲公司 | Process for the synthesis of aminobiphenylene |
| CN104220417A (en) * | 2012-03-07 | 2014-12-17 | 巴斯夫欧洲公司 | Method for synthesising aminobiphenyls using aryl hydrazines |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111072492A (en) * | 2019-11-29 | 2020-04-28 | 浙江工业大学 | Method for synthesizing 3,4-dichloro-2-amino-5-fluorobiphenyl |
| WO2023031959A1 (en) * | 2021-08-31 | 2023-03-09 | Upl Limited | A process for preparation of bixafen |
| CN115160226A (en) * | 2022-07-19 | 2022-10-11 | 欧阳建峰 | Method for preparing bixafen by one-step condensation method |
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| SE01 | Entry into force of request for substantive examination | ||
| CI02 | Correction of invention patent application |
Correction item: Applicant|Address Correct: RUICHENG COUNTY SIPULUNDI BIOLOGICAL ENGINEERING CO.,LTD.|044600 Caicun, Yongle Town, Ruicheng County, Yuncheng City, Shanxi Province False: Qicheng County Splendy Bioengineering Co.,Ltd.|044600 Caicun, Yongle Town, Ruicheng County, Yuncheng City, Shanxi Province Number: 33-01 Page: The title page Volume: 35 Correction item: Applicant|Address Correct: RUICHENG COUNTY SIPULUNDI BIOLOGICAL ENGINEERING CO.,LTD.|044600 Caicun, Yongle Town, Ruicheng County, Yuncheng City, Shanxi Province False: Qicheng County Splendy Bioengineering Co.,Ltd.|044600 Caicun, Yongle Town, Ruicheng County, Yuncheng City, Shanxi Province Number: 33-01 Volume: 35 |
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| CI02 | Correction of invention patent application | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 044600 Cai Cun, Yongle Town, Ruicheng County, Yuncheng City, Shanxi Province Patentee after: Shanxi Sprundi Bioengineering Co.,Ltd. Address before: 044600 Cai Cun, Yongle Town, Ruicheng County, Yuncheng City, Shanxi Province Patentee before: RUICHENG COUNTY SIPULUNDI BIOLOGICAL ENGINEERING CO.,LTD. |
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| CP01 | Change in the name or title of a patent holder |