CN105732747B - A kind of deep processing processing method of abamectin ointment - Google Patents
A kind of deep processing processing method of abamectin ointment Download PDFInfo
- Publication number
- CN105732747B CN105732747B CN201610156129.0A CN201610156129A CN105732747B CN 105732747 B CN105732747 B CN 105732747B CN 201610156129 A CN201610156129 A CN 201610156129A CN 105732747 B CN105732747 B CN 105732747B
- Authority
- CN
- China
- Prior art keywords
- reaction
- ointment
- abamectin
- abamectin ointment
- avermectin
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Saccharide Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
Abstract
A kind of deep processing processing method of abamectin ointment; belong to the organic chemical synthesis in the field of chemical synthesis, which is that abamectin ointment is obtained avermectin avermectin B by the pretreatment protection reaction oxidation reaction amination reduction reaction deprotection reaction salt-forming reaction of abamectin ointment2The amido derivative salt and avermectin B of a1The mixture of a amido derivative salt;The present invention changes the utilization ways of existing abamectin ointment, provides a kind of deep processing processing method of new abamectin ointment, so that synthesis processing is reduced refining crystallization processing step, keeps further preparation processing simpler, conveniently;It is more safe and environment-friendly;More reduce the processing cost of unnecessary farmland pollution and follow-up preparation.
Description
Technical field
The invention belongs to the organic chemical synthesis in the field of chemical synthesis, specifically a kind of leftover bits and pieces of avermectin
The deep processing processing method of abamectin ointment.
Background technology
Avermectin is to belong to streptomyces griseus produced by Sterptomyces avermitills.80 years last century
Generation, by the Japanese villages North university scientific Jia great intelligence etc. and United States Merck company joint development, fermented extraction process production.The U.S.
Merck & Co., Inc. therefrom extracts one group of mixture being made of the similar homologue of eight structures, and is named as Avermectin
Element.
Avermectin is a kind of ten hexa-atomic macrolide antibiotics, in structure, sixteen-ring lactone and a disaccharides
Oleandrose forms glucosides, and is connected with hexa-atomic Spiroketals system and hexahydro benzofuran system.Avermectin is natural fermented component
Mixture, share A1a、A2a、B1a、B2a、A1b、A2b、B1b、B2Eight kinds of groups of b are grouped as;A1a、A2a、B1a、B2Tetra- kinds of a is main
Ingredient total content >=80%, corresponding four kinds of ingredient A1b、A2b、B1b、B2B contents are less, total content≤20%.
Avermectin is a kind of never poison, and mechanism acts on insect neuron cynapse or neuromuscular synapse
The information of GABA receptors, interference insect nerves within the body tip is transmitted, i.e., the non-tip of excitation nerve releases neurotransmission inhibitor Y-- ammonia
Base butyric acid (GABA) promotes the chloride channel that GABA is gated to extend and opens, has activation, a large amount of chlorine to chloride channel
Ion, which pours in, causes neural membrane potentials hyperpolarization, and neu is caused to be in holddown, to the non-tip of block nerves and muscle
Contact, makes insect paralysis, food refusal, death.Because of its mechanism of action uniqueness, so with common medicament no interactions resistance.To insect
Have with snail class and tag and stomach poison function, but be unable to ovicidal, there is broad-spectrum high efficacy, resist long resistance, lasting period, is low toxicity, low residual
It stays, is degradable, the features such as small, safe is influenced on natural enemy.
Avermectin is present in the mycelium of zymotic fluid, discards filtrate by filtering, filter cake passes through de- after being extracted with ethyl alcohol
Sugar, concentration, crystallization can be obtained avermectin fine work and (contain AbamectinB195%), the mother liquor after crystallization is concentrated through being evaporated under reduced pressure
Abamectin ointment is obtained after being formulated into specified viscosity to the solvent-free rear organic solvent that toluene or dimethylbenzene etc is added, wherein
Avermectin B1The content of a (contains AbamectinB generally between 3~9%13%~9%).
Call of the world today with people to pollution-free food, biological pesticide and semi-synthetic biological pesticide increasingly show it
Importance;Artificial semi-synthetic biological pesticide is increasingly valued by people.Deep processing is carried out to avermectin, it is artificial semi-synthetic
Avermectins pesticide has obtained the common recognition of people.However in published patent or non-patent literature, no matter to Avermectin
Plain B1The deep processing of a is still to avermectin B2The deep processing of a none be not using avermectin series fine powder be parent through row study
With exploitation, to the deep processing of abamectin ointment processing no matter external or domestic still belong to blank field;The present invention is quasi- logical
It crosses to the main component B in abamectin ointment2A and B1A performs the derivatization synthesis and carries out deep add to abamectin ointment at salt
Work processing.
Invention content:
The present invention changes the utilization ways of existing abamectin ointment, provides a kind of depth of new abamectin ointment
Processing and treating method makes synthesis processing reduce refining crystallization processing step, keeps further preparation processing simpler, square
Just;It is more safe and environment-friendly;More reduce the processing cost of unnecessary farmland pollution and follow-up preparation.
A kind of deep processing processing method of abamectin ointment of the present invention, through the following steps that carry out:
One, the pretreatment of abamectin ointment
(1) avermectin commodity ointment and water are evaporated under reduced pressure after mixing in the ratio of quality 20~22: 1,
Contained solvent is removed, the paste of abamectin ointment is obtained;
(2) it in mass ratio 1: 1 petroleum ether and stirring is added dissolves paste, static layering, except deoiling into gained paste
Contained grease in cream;
(3) again thereto be added quality be above-mentioned petroleum ether quality 20% mass percent concentration be 10% trichlorine
Acetic acid solution stirs evenly, static layering, except protein contained in oil removing cream;
(4) surplus solution is evaporated under reduced pressure again, removes contained solvent, obtains paste;
Two, protection reaction
Dichloromethane is added by avermectin paste and dichloromethane mass volume ratio 1: 2 and dissolves paste, waits for paste
After object is completely dissolved, cooling system temperature to -20 DEG C~-15 DEG C, be added dropwise the bright ester of chloro-carbonic acid alkene and tetramethylethylenediamine solution into
Row protection reaction, reaction time 2h notice that system temperature must not be higher than -15 DEG C, by B in ointment2A and B1The C of a5Position hydroxyl carries out
Protection;
Three, oxidation reaction
After the completion of protection reaction, with isopropyl acetate dissolving abamectin ointment B2A and B1The C of a5Position hydroxyl protection object, is pressed
Abamectin ointment B is added in mass ratio 1: 10: 3: 32A and B1The C of a5Position hydroxyl protection object, dimethyl sulfoxide (DMSO), four Shen base second two
Amine, phenyl phosphate carry out oxidation reaction, keep -20 DEG C~-15 DEG C, reaction time 2h of system temperature, Ah is obtained after the completion of reaction
Tie up the B of rhzomorph ointment2A and B1The positions a 4 " keto compounds;
Four, amination reduction reaction
(1) after the completion of oxidation reaction, by the B of abamectin ointment2A and B1The positions a 4 " ketone group oxide is dissolved in acetic acid isopropyl
In ester, in mass ratio 2: 5: 1 are added the B of abamectin ointment2A and B1The positions a 4 " ketone group oxide, heptamethyldisilazane, three
Fluoroacetic acid zinc carries out aminating reaction, heats up and keeps 40 DEG C~60 DEG C, reaction time 2h of system temperature, amine is obtained after the completion of reaction
The C of change5The B of position hydroxyl protection2A and B1The positions a 4 " imines radical derivative;
(2) after the completion of aminating reaction, system temperature is reduced to -10 DEG C~-15 DEG C, absolute ethyl alcohol and reducing agent boron hydrogen is added
Change sodium, reaction time 1h obtains the B of abamectin ointment after the completion of reaction2A and B1a C5The methylamine radical derivative of position protection;
Five, deprotection reaction
By the B of abamectin ointment2A and B1a C5The methylamine radical derivative of position protection is dissolved in absolute ethyl alcohol, keeps reaction
Reacting liquid temperature after reaction time 1h, is warming up to 30 DEG C, keeps 1h by -5 DEG C of liquid temperature, is extracted with ethyl alcohol after the completion of reaction anti-
Object, precipitation is answered to obtain the B of abamectin ointment2A and B1The methylamine radical derivative of a.
Six, salt-forming reaction
(1) B of abamectin ointment is pressed2A and B1The methylamine radical derivative and benzoic acid Mass of a carries out anti-than 2: 1 ratios
It answers, reaction time 1h, avermectin B is obtained after the completion of reaction2The amido derivative salt and avermectin B of a1A amido derivative salt
Mixture;
(2) it after reaction is fully completed, is evaporated under reduced pressure to obtaining solution, after waiting for evaporation of the solvent, addition obtains
40% toluene of paste quality and 0.3%BHT are to get to avermectin avermectin B2The amido derivative salt and Avermectin of a
Plain B1The mixture of a amido derivative salt.
Advantageous effect
The present invention changes the utilization ways of existing abamectin ointment, provides a kind of depth of new abamectin ointment
Processing and treating method makes synthesis processing reduce refining crystallization processing step, keeps further preparation processing simpler, square
Just;It is more safe and environment-friendly;More reduce the processing cost of unnecessary farmland pollution and follow-up preparation.
Specific implementation mode
It is described in detail below by way of specific embodiment, but the scope of the present invention is not limited to following lift in fact
Apply example.
Embodiment 1:The deep processing processing method of abamectin ointment of present embodiment a kind of through the following steps that into
Capable:
One, the pretreatment of abamectin ointment
(1) avermectin commodity ointment 120g (B1a contents 8.6%) is added in 500ml flasks, adds water 6g mixing laggard
Row is evaporated under reduced pressure, and removes contained solvent, obtains pasta abamectin ointment 70g;
(2) the pasta Avermectin of petroleum ether 70g stirring and dissolvings is added in the pasta abamectin ointment 70g of gained thereto
Vegetable oil cream, static layering, except contained grease in oil removing cream;
(3) solution of trichloroacetic acid that the mass percent concentration that addition quality is 14g thereto again is 10%, stirring are equal
It is even, static layering, except protein contained in oil removing cream;
(4) surplus solution is evaporated under reduced pressure again, removes contained solvent, obtains paste;
Two, protection reaction
After dichloromethane 130g stirring and dissolvings being added in the avermectin paste 68g after precipitation again, -20 are cooled to
DEG C, allyl chlorocarbonate 3g, tetramethylethylenediamine 2.5g is added dropwise, after reacting 2h, terminates reaction, precipitation obtains abamectin ointment
B2A and B1The C of a5Position hydroxyl protection intermediate;
Three, oxidation reaction
Abamectin ointment B2A and B1The C of a5Position hydroxyl protection intermediate 60g is dissolved in isopropyl acetate solution, is added two
The different diamines 5g of first sulfoxide 4g, tetramethyl, cools to -20 DEG C, and phenyl phosphate 4g is added dropwise, with acid solution adjust the pH of solution to
2.0~3.0, reaction time 2h terminate reaction, collect dichloromethane phase, and pH to 7.0 is adjusted with alkaline solution, and then decompression is gone
Except dichloromethane, Simultaneous Oxidation product Intermediate is obtained;
Four, amination reduction reaction
(1) obtained Simultaneous Oxidation product 57g and isopropyl acetate 200g is stirred, adds trifluoroacetic acid zinc 1g
It is uniformly mixed with heptamethyldisilazane 4g, is then warming up to 50 DEG C, reacted 3h, obtain aminate;
(2) after aminating reaction, reaction system is cooled to -10 DEG C, is added into obtained aminate anhydrous
Ethyl alcohol 100g adds reducing agent sodium borohydride 2g, obtains mixed solution, reacts 1h, adjusts the pH to 3.0 of mixed solution, terminates
Reaction, then mixed solution pH to 7.0 is adjusted with alkaline solution, isopropyl acetate extraction reaction solution is obtained, precipitation is depressurized, obtains C5
The abamectin ointment B of position hydroxyl protection2A and B1The methylamino product of a;
Five, deprotection reaction
To obtained C5The abamectin ointment B of position hydroxyl protection2A and B1Absolute ethyl alcohol is added in the methylamino product of a,
- 5 DEG C are cooled to, triphenylphosphine 0.001g, sodium borohydride 0.01g is added, reacts 1h, hydrochloric acid tune PH to 3 is added, is then warming up to
30 DEG C, 1h is reacted, after reaction, up to abamectin ointment B after decompression precipitation2A and B1A methylamino derivative salts 46g.
Six, salt-forming reaction
In obtained 46g abamectin ointments B2A and B1In a methylamino derivative salts be added quality 18g toluene and
0.13gBHT is to get to avermectin avermectin B2The amido derivative salt and avermectin B of a1A amido derivative salt mixes
Close object.
Embodiment 2:The deep processing processing method of abamectin ointment of present embodiment a kind of through the following steps that into
Capable:
One, the pretreatment of abamectin ointment
(1) avermectin commodity ointment 1200g (B1a contents 8.6%) is added in 5L reaction kettles, adds water 60g stirrings mixed
It is evaporated under reduced pressure after closing uniformly, removes contained solvent, obtain pasta abamectin ointment;
(2) the pasta AVM hereinafter of petroleum ether 700g stirring and dissolvings is added in the pasta abamectin ointment 700g of gained thereto
Rhzomorph ointment, static layering, except contained grease in oil removing cream;
(3) solution of trichloroacetic acid that the mass percent concentration that addition quality is 140g thereto again is 10%, stirring are equal
It is even, static layering, except protein contained in oil removing cream;
(4) surplus solution is evaporated under reduced pressure again, removes contained solvent, obtains paste;
Two, protection reaction
After dichloromethane 130g stirring and dissolvings being added in the avermectin paste 680g after precipitation again, -20 are cooled to
DEG C, allyl chlorocarbonate 30g, tetramethylethylenediamine 25g is added dropwise, after reacting 2h, terminates reaction, precipitation obtains abamectin ointment
B2A and B1The C of a5Position hydroxyl protection intermediate;
Three, oxidation reaction
Abamectin ointment B2A and B1The C of a5Position hydroxyl protection intermediate 600g is dissolved in isopropyl acetate solution, is added
The different diamines 50g of dimethyl sulfoxide 40g, tetramethyl cools to -20 DEG C, and phenyl phosphate 40g is added dropwise, and solution is adjusted with acid solution
PH to 2.0~3.0, reaction time 2h terminate reaction, collect dichloromethane phase, adjust pH to 7.0 with alkaline solution, then subtract
Pressure removal dichloromethane, obtains Simultaneous Oxidation product Intermediate;
Four, amination reduction reaction
(1) obtained Simultaneous Oxidation product 570g and isopropyl acetate 2000g is stirred, adds trifluoroacetic acid zinc
10g and heptamethyldisilazane 40g is uniformly mixed, and is then warming up to 50 DEG C, is reacted 3h, is obtained aminate;
(2) after aminating reaction, reaction system is cooled to -10 DEG C, is added into obtained aminate anhydrous
Ethyl alcohol 1000g adds reducing agent sodium borohydride 20g, obtains mixed solution, reacts 1h, adjusts the pH to 3.0 of mixed solution, eventually
It only reacts, then mixed solution pH to 7.0 is adjusted with alkaline solution, obtain isopropyl acetate extraction reaction solution, depressurize precipitation, obtain
C5The abamectin ointment B of position hydroxyl protection2A and B1The methylamino product of a;
Five, deprotection reaction
To obtained C5The abamectin ointment B of position hydroxyl protection2A and B1Absolute ethyl alcohol is added in the methylamino product of a,
- 5 DEG C are cooled to, triphenylphosphine 0.01g, sodium borohydride 0.1g is added, reacts 1h, hydrochloric acid tune PH to 3 is added, is then warming up to 30
DEG C, 1h is reacted, after reaction, up to abamectin ointment B after decompression precipitation2A and B1aMethylamino derivative salt 460g;
Six, salt-forming reaction
In obtained 460g abamectin ointments B2A and B1In a methylamino derivative salts be added quality 180g toluene and
1.3gBHT is to get to avermectin avermectin B2The amido derivative salt and avermectin B of a1The mixing of a amido derivative salt
Object.
Claims (1)
1. a kind of deep processing processing method of abamectin ointment, it is characterised in that:Include the following steps:
One, the pretreatment of abamectin ointment:
(1) ratio of avermectin commodity ointment and water in mass ratio 20~22: 1 is evaporated under reduced pressure after mixing, is removed
Contained solvent is removed, paste abamectin ointment is obtained;
(2) into gained paste abamectin ointment, in mass ratio 1: 1 addition petroleum ether and stirring dissolves paste abamectin ointment,
Static layering removes contained grease in paste abamectin ointment;
(3) mass percent that quality is the petroleum ether quality 20% described in step (2) is added into the product of step (2) again
A concentration of 10% solution of trichloroacetic acid, stirs evenly, static layering, except protein contained in oil removing cream;
(4) surplus solution is evaporated under reduced pressure again, removes contained solvent, obtains paste;
Two, protection reaction:Dichloromethane is added by avermectin paste and dichloromethane mass volume ratio 1: 2 and dissolves paste
Object, after paste is completely dissolved, allyl chlorocarbonate and tetramethyl second two is added dropwise to -20 DEG C~-15 DEG C in cooling system temperature
Amine aqueous solution carries out protection reaction, and reaction time 2h notices that system temperature must not be higher than -15 DEG C, by B in ointment2A and B1The C of a5Position
Hydroxyl is protected;
Three, oxidation reaction:After protection is reacted, with isopropyl acetate dissolving abamectin ointment B2A and B1The C of a5Position hydroxyl is protected
Object is protected, in mass ratio 1: 10: 3: 3 are added abamectin ointment B2A and B1The C of a5Position hydroxyl protection object, dimethyl sulfoxide (DMSO), tetramethyl
Base ethylenediamine, phenyl phosphate carry out oxidation reaction, keep -20 DEG C~-15 DEG C of system temperature, reaction time 2h, after the completion of reaction
Obtain the B of abamectin ointment2A and B1The positions a 4 " keto compounds;
Four, amination reduction reaction:
(1) after the completion of oxidation reaction, by the B of abamectin ointment2A and B1The positions a 4 " ketone group oxide is dissolved in isopropyl acetate,
In mass ratio 2: 5: 1 are added the B of abamectin ointment2A and B1The positions a 4 " ketone group oxide, heptamethyldisilazane, trifluoroacetic acid
Zinc carries out aminating reaction, heats up and keeps 40 DEG C~60 DEG C, reaction time 2h of system temperature, the C of amination is obtained after the completion of reaction5
The B of position hydroxyl protection2A and B1The positions a 4 " imines radical derivative;
(2) after the completion of aminating reaction, system temperature is reduced to -1 DEG C~-15 DEG C, absolute ethyl alcohol and reducing agent sodium borohydride is added,
Reaction time 1h obtains the B of abamectin ointment after the completion of reaction2A and B1a C5The methylamine radical derivative of position protection;
Five, deprotection reaction:By the B of abamectin ointment2A and B1a C5The methylamine radical derivative of position protection is dissolved in absolute ethyl alcohol
In, -5 DEG C of reacting liquid temperature is kept, is added triphenylphosphine and sodium borohydride, after reaction time 1h, hydrochloric acid tune p H to 3 are added, it will
Reacting liquid temperature is warming up to 30 DEG C, keeps 1h, and reactant is extracted with ethyl alcohol after the completion of reaction, and precipitation obtains abamectin ointment
B2A and B1The methylamine radical derivative of a;
Six, salt-forming reaction:
(1) B of abamectin ointment is pressed2A and B1The methylamine radical derivative and benzoic acid Mass of a is reacted than 2: 1 ratios, instead
1h between seasonable obtains avermectin B after the completion of reaction2The amido derivative salt and avermectin B of a1A amido derivative salt mixes
Close object;
(2) it after reaction is fully completed, is evaporated under reduced pressure to obtaining solution, after waiting for evaporation of the solvent, addition obtains paste
40% toluene of amount of substance and 0.3%BHT are to get to avermectin B2The amido derivative salt and avermectin B of a1A amidos derive
The mixture of object salt.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610156129.0A CN105732747B (en) | 2016-03-11 | 2016-03-11 | A kind of deep processing processing method of abamectin ointment |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610156129.0A CN105732747B (en) | 2016-03-11 | 2016-03-11 | A kind of deep processing processing method of abamectin ointment |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105732747A CN105732747A (en) | 2016-07-06 |
CN105732747B true CN105732747B (en) | 2018-09-18 |
Family
ID=56250830
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610156129.0A Active CN105732747B (en) | 2016-03-11 | 2016-03-11 | A kind of deep processing processing method of abamectin ointment |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105732747B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116237084A (en) * | 2022-12-10 | 2023-06-09 | 河北兴柏农业科技股份有限公司 | Supported zinc trifluoroacetate, preparation method and application |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103030675A (en) * | 2012-11-19 | 2013-04-10 | 河北威远生物化工股份有限公司 | Process of extracting abamectin components B1 and B2 step by step by utilizing crystallization method |
CN103214532A (en) * | 2013-02-28 | 2013-07-24 | 河北威远生物化工股份有限公司 | Avermectin B2a/2b amine derivatives, derivative salts thereof, and preparation method and application of avermectin B2a/2b amine derivative salt |
CN103421065A (en) * | 2013-07-03 | 2013-12-04 | 大庆志飞生物化工有限公司 | Novel Avermectin derivative and preparation method thereof |
CN104497081A (en) * | 2014-05-14 | 2015-04-08 | 孟水强 | Macrolide benzoate compound and application thereof |
-
2016
- 2016-03-11 CN CN201610156129.0A patent/CN105732747B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103030675A (en) * | 2012-11-19 | 2013-04-10 | 河北威远生物化工股份有限公司 | Process of extracting abamectin components B1 and B2 step by step by utilizing crystallization method |
CN103214532A (en) * | 2013-02-28 | 2013-07-24 | 河北威远生物化工股份有限公司 | Avermectin B2a/2b amine derivatives, derivative salts thereof, and preparation method and application of avermectin B2a/2b amine derivative salt |
CN103421065A (en) * | 2013-07-03 | 2013-12-04 | 大庆志飞生物化工有限公司 | Novel Avermectin derivative and preparation method thereof |
CN104497081A (en) * | 2014-05-14 | 2015-04-08 | 孟水强 | Macrolide benzoate compound and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN105732747A (en) | 2016-07-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103214532B (en) | Avermectin B2a/2bAmido derivative, derivative salt and avermectin B2a/2bThe Preparation method and use of amido derivative salt | |
BE530983A (en) | ||
CN104497081A (en) | Macrolide benzoate compound and application thereof | |
CN105732747B (en) | A kind of deep processing processing method of abamectin ointment | |
CN104904721B (en) | A kind of microbicide compositions and preparation and its application | |
CN114982763B (en) | New application of geldanamycin and analogues thereof | |
CN113615700A (en) | Application of parthenolide derivative in prevention and treatment of bacterial blight of rice | |
CN100515200C (en) | Neodymium nitrate berberine complex pesticides sterilizing emulsion agent and preparation method thereof | |
CN110128301B (en) | Blue-green algae remover and green preparation method thereof | |
CN110204538A (en) | Aryl thiazole-tryptamines class marine red tide algae algicide and its preparation method and application | |
CN102060895A (en) | Method for desugaring abamectin | |
CN105837543A (en) | Method for extracting refined kojic acid from fermentation broth | |
CN100515201C (en) | Samarium nitrate berberine complex pesticides sterilizing emulsion agent and preparation method thereof | |
CN107624767A (en) | A kind of application of dipeptide compounds | |
DE3048421A1 (en) | ANTIBIOTIC SUBSTANCE AND METHOD FOR THE PRODUCTION THEREOF | |
CN106135234B (en) | Application of (substituted-amino formyl the methylthiol) -1,3,4- thiadiazole compounds of 2,5- bis- in inhibiting blue algae growth | |
CN103214053B (en) | Method for treating wastewater from gallic acid production | |
CN105917793A (en) | Electrolyzed functional water-based rice seed soaking, germination accelerating and sprout cultivating method | |
CN109438356A (en) | A kind of purification process of Prochloraz raw medicine | |
CN111685126A (en) | Plant growth regulator with oryzanol as effective component | |
CN106520850A (en) | Preparation method of modified natural food coloring agent emulsion | |
CN108558764A (en) | N- [(6- halogen -1H- indazole -1- bases) alkyl] -2- amino acids and the preparation method and application thereof | |
CN105454263A (en) | Wettable carbaryl powder | |
CN100403904C (en) | Application of emulsion of natural Pyrethrum cinerariifolium | |
CN1471820A (en) | Insecticide producing method by cartap pesticide devil liquor and its products and use method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |