CN107673996A - A kind of method that low activity fenvalerate isomers converts to high activity fenvalerate isomers - Google Patents
A kind of method that low activity fenvalerate isomers converts to high activity fenvalerate isomers Download PDFInfo
- Publication number
- CN107673996A CN107673996A CN201710896270.9A CN201710896270A CN107673996A CN 107673996 A CN107673996 A CN 107673996A CN 201710896270 A CN201710896270 A CN 201710896270A CN 107673996 A CN107673996 A CN 107673996A
- Authority
- CN
- China
- Prior art keywords
- fenvalerate
- isomers
- hexane
- activity
- fenvalerates
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method that low activity fenvalerate isomers converts to high activity fenvalerate isomers：Low activity fenvalerate isomers shown in formula I or formula III is dissolved in organic solvent, the product containing the high activity fenvalerate isomers shown in formula II or formula IV is respectively obtained after reacting 12 192h, realizes that low activity fenvalerate isomers converts to high activity fenvalerate isomers；Described organic solvent is n-hexane and the mixed liquor or n-hexane of ethanol and the mixed liquor of isopropanol；Described n-hexane and the volume ratio of ethanol are 1.5 9:1；Described n-hexane and the volume ratio of isopropanol are 1.5 9:1；
Description
(1) technical field
The present invention relates to agriculture field, and in particular to the low activity mapping in a kind of pyrethroid insectide fenvalerate
The method that isomers converts to high activity enantiomter.
(2) background technology
Agricultural chemicals refers in agricultural production, to ensure, promoting the growth of plant and crops, the desinsection applied, sterilization,
A kind of medicine for killing harmful animal (or weeds) is referred to as.Refer in particular to be agriculturally used to preventing and treating disease pest and coordinate plant growth,
The medicaments such as weeding.Agricultural chemicals is to the facilitation of modern agriculture it will be apparent that pest and disease damage is effectively prevented and treated, for human survival work
Major contribution is gone out.But because agricultural chemicals is a kind of toxic chemical substance, long-term substantial amounts of use can be to Environment Ecological Safe and people
Body health produces certain influence.Pollution of the use of agricultural chemicals to air is on the rise, and pollution of the agricultural chemicals to water body is even more not allow
Ignore, the agricultural chemicals that people's daily life takes in low dosage for a long time also causes many chronic harmful effects, such as carcinogenic, teratogenesis and cause
Mutation, nervous system disorder and sex distortion etc..In addition, agricultural chemicals soil pollution is one of most typical example of pollution by pesticides, residual
Agricultural chemicals in soil generates serious poisoning to crops.Agricultural chemicals will not only promote the development of agricultural, it is necessary to meet ring
The requirement of border protection.Therefore, it is increasingly urgent that efficient, low toxicity, less-persistent pesticide kind are developed.Due to the drug effect of single chiral agricultural chemicals
Height, dosage is few, the three wastes are few, safer to crop and environmental ecology, relative cost is low, the market competitiveness is strong, causes section of various countries
The attention of scholar, turn into one of Main way of 21 century Agrochemicals.
The agricultural chemicals (Chiral pesticide) with chiral structure accounts for 40% in the agricultural chemicals used at present, special in chiral environment
When not being chipal compounds interaction, chiral enantiomer often shows different characteristics, even shows completely phase sometimes
Anti- property, to be said from molecular level angle, when agricultural chemical compound interacts with organism, what agricultural chemicals participated in is biochemical reaction,
Organism is to the matching sexual intercourse with chiral structure so that different bioactivity is shown between chiral isomer, this is just
It is that some chiral body surfaces reveal high desinsection, mite killing, sterilization and activity of weeding, and its enantiomer activity is low or shows poisoning
Basic reason.Therefore, the development of single high activity chirality body or the Chiral pesticide without invalid chiral body seems extremely important, no
Input of the agricultural chemicals to nature is only reduced, while poisoning is avoided, the raw material of more than half is also saved, in addition, single
The transition problem of high activity Chiral pesticide in the environment is also the significant problem for being worth us further to further investigate, to subtract as far as possible
Few pesticide residual contamination problem.
Fenvalerate (fenvalerate), is commonly called as Belmark, is that SUMITOMO CHEMICAL chemical industry Co., Ltd. develops,
Synthetic pyrethroid insecticide with compared with the non-three-membered ring structures of high bioactivity, chemical name are (RS)-alpha-cyano -3- benzene
Oxy-benzyl (RS) -2- (4- chlorphenyls) -3 Methylbutanoic acid ester.Active compound be yellow to brown viscous shape liquid, have portion at room temperature
Point crystallization separates out, and decomposes during distillation.It is relatively stable in acid medium to heat, moist stabilization, hydrolyzed rapidly in alkaline medium.Should
Product are broad-spectrum highly efficient insecticide, and effect is rapid, and it is strong to knock down power, killed with angle based on, a variety of cotton-plant pest-insects, such as bollworm can be prevented and treated,
Cotten aphid etc., preventing and treating tobacco, soybean, corn, fruit tree, the insect of vegetables are widely used in, can also be used for preventing and treating the side such as domestic animal and storage
The insect in face.Fenvalerate category moderate toxicity insecticide, active compound rat acute LD50 are 451mg/kg, and rat acute is percutaneous
LD50>5000mg/kg, rat acute suction LC50>101mg/m3, there is slight stimulation to rabbit skin, there is moderate thorn to eyes
Swash.There is no mutagenesis, teratogenesis and carcinogenesis.It is high to toxicity such as honeybee, fishes and shrimps, poultry.
Pyrethroid pesticide structure is more complicated, and used in everyday is typically all racemic modification, wherein only several
Isomers has a good bioactivity, and other isomers or poorly efficient or invalid, as Fenpropathrin has two kinds of isomers, S
The insecticidal activity of body is 50 times of R bodies.It was found from the chemical constitution of fenvalerate, fenvalerate has 2 asymmetric carbon atoms, therefore
There are 4 kinds of optical isomers, have the ester insecticidal activity of S acid structures strong, ester sour R has S alcohol structures almost without insecticidal activity
Ester insecticidal activity be better than the ester of R alcohol, wherein insecticidal activity is followed successively by S acid-S alcohol>S acid-R alcohol>R acid-S alcohol>R acid-R alcohol, its
Other isomers of the biological activity ratio of middle SS isomers are high 2~4 times, and poorly efficient or invalid isomers can not only reduce drug effect, and
And also pollute the environment, or even crops can be made to produce poisoning or the resistance to the action of a drug.
The method obtained of the chipal compounds of single enantiomer has chiral source synthetic method and dissymmetric synthesis, and chiral source is closed
It is the single enantiomer using the chipal compounds of single enantiomer as the other chipal compounds of Material synthesis into method, but due to day
The limitednumber of right chiral material, is very restricted the diversified purpose product of synthesis.Dissymmetric synthesis be
In the presence of catalyst or enzyme, excessive single enantiomer chipal compounds are can obtain, this method is obtaining very in the past 20 years
Big development, some reactions have started to be used for industrialized production, but to reach the reaction of high rotary light yield, still have many tired
Difficulty, biological asymmetric syntheses has very high enantio-selectivity, but the requirement to substrate is high, and reaction is slow, and product separation is difficult.
The common formulation of fenvalerate commercially is 20% fenvalerate missible oil, is that yield is maximum in Pesticidal products
A kind of formulation, it is the transparent true solution generated in organic solvent by the auxiliary agent such as oil-soluble pesticide active compound and emulsifying agent, adds water
In after can form the emulsion of missible oil liquid, pesticide active ingredient dissolving is dispersed in water in imperceptible oil droplet in a solvent
In.But most of existing missible oil product is processed with aromatic hydrocarbons organic solvent, from it is most be mixing diformazan
Benzene, because it is fine to the dissolubility of most of pesticide original medicines, and penetrating power of the medicament to living thing's skins can be strengthened, so as to
Improve drug effect.Progressively it is eliminated and by it because aromatic hydrocarbon solvent has been listed in environmental monitoring material and missible oil formulation is being faced
The situation of his formulation substitution.
(3) content of the invention
In order to reduce the usage amount of fenvalerate, and poorly efficient or invalid isomery body pollution environment is prevented, or even agriculture can be made
Crop produces poisoning or the resistance to the action of a drug, and it is an object of the present invention to provide a kind of low activity fenvalerate isomers to high activity fenvalerate
The method of isomers conversion.
The technical solution adopted by the present invention is：
A kind of method that low activity fenvalerate isomers converts to high activity isomers, it is characterised in that：Described side
Method is specifically carried out in accordance with the following steps：
Low activity fenvalerate isomers shown in formula I or formula III is dissolved in organic solvent, divided after reacting 12~192h
The product containing the high activity fenvalerate isomers shown in formula II or formula IV is not obtained, realizes low activity fenvalerate isomers
Converted to high activity fenvalerate isomers；Described organic solvent is the mixed liquor or n-hexane and isopropyl of n-hexane and ethanol
The mixed liquor of alcohol；Described n-hexane and the volume ratio of ethanol are 1.5-9:1；Described n-hexane and the volume ratio of isopropanol are
1.5-9:1；
Further, the concentration of the single low activity fenvalerate isomers shown in the formula I or formula III is 10mg/L-
1000mg/L。
Further, the volume ratio of described n-hexane and ethanol is 6:4.
Further, the volume ratio of described n-hexane and isopropanol is 6:4.
Further, present invention gained reaction product is detected by high performance liquid chromatography, the high-efficient liquid phase color
Spectrometry uses forward chromatographic column CHIRALCEL OJ-H posts, and mobile phase is n-hexane：Ethanol=90:10, flow rate of mobile phase is
0.6ml/min, sample size 20ul, Detection wavelength 230nm, containing for same solution Chinese style I and formula II is drawn according to chromatographic peak
The content of amount or formula III and IV.
Compared with prior art, the beneficial effects of the present invention are：
Method of the present invention, easy to operate, cost is low, can effectively reduce racemic compound fenvalerate
Usage amount, Chiral pesticide can reach higher drug effect with relatively low dosage, reduce input of the agricultural chemicals to field, and prevent low
Effect or invalid isomery body pollution environment, can effectively improve insecticide efficiency, avoid crops and produce poisoning or the resistance to the action of a drug, together
When save substantial amounts of raw material, improve economic benefit and social benefit.
(4) illustrate
N-hexanes of the Fig. 1 in different proportion：In ethanol, 100% low activity α R-2R- fenvalerates are to high activity α S-2R-
Fenvalerate conversion figure.
N-hexanes of the Fig. 2 in different proportion：In isopropanol, 100% low activity α R-2R- fenvalerates are to high activity α S-
2R- fenvalerates conversion figure.
N-hexanes of the Fig. 3 in different proportion：In ethanol, 100% low activity α S-2R- fenvalerates are to high activity α S-2S-
Fenvalerate conversion figure.
N-hexanes of the Fig. 4 in different proportion：In isopropanol, 100% low activity α S-2R- fenvalerates are to high activity α S-
2S- fenvalerates conversion figure.
Four isomers α R-2R, α R-2S, α S-2R, α S-2S of Fig. 5-Fig. 8 fenvalerates CD spectrograms.
(5) embodiment
With reference to instantiation, the present invention is expanded on further.It should be understood that these embodiments are only used for carrying out the present invention
Illustrate, and be not construed as limiting the scope of claims limitation, it may occur to persons skilled in the art that other alternative means, this
In invention right.
Embodiment 1：5mg α R-2R- fenvalerates are weighed, are dissolved in 500ml n-hexanes：Ethanol is 9:In 1 solvent,
10mg/L α R-2R- fenvalerate solution is obtained, 4 DEG C of refrigerators is put into and preserves, efficient liquid phase is utilized in 12,24,48,96,192h
Chromatogram detects solution, according to chromatographic peak appearance time, compares CD spectrograms, judges the isomers and its content corresponding to chromatographic peak.
As a result Fig. 2 is seen, the results showed that in n-hexane：Ethanol is 9:In 1 solvent, 100% α R-2R- fenvalerates are over time
Passage, the α S-2R- fenvalerates of high activity can be partly converted into, time more long conversion is more more more tends towards stability, in 192h, α
The content of R-2R- fenvalerates is that 57%, α S-2R- fenvalerates are 43%.Fenvalerate contains four isomers, and activity is big
Small is SS>SR>RS>The insecticidal activity of RR, RR type is extremely low, even without activity, is converted into the SR types of high activity, reduces agricultural chemicals
Usage amount.
Embodiment 2：5mg α R-2R- fenvalerates are weighed, are dissolved in 500ml n-hexanes：Ethanol is 8:In 2 solvent,
10mg/L α R-2R- fenvalerate solution is obtained, 4 DEG C of refrigerators is put into and preserves, efficient liquid phase is utilized in 12,24,48,96,192h
Chromatogram detects solution, according to chromatographic peak appearance time, compares CD spectrograms, judges the isomers and its content corresponding to chromatographic peak.
As a result Fig. 2 is seen, the results showed that in n-hexane：Ethanol is 8:In 2 solvent, 100% α R-2R- fenvalerates are over time
Passage, the α S-2R- fenvalerates of high activity can be partly converted into, time more long conversion is more more more tends towards stability, in 192h, α
The content of R-2R- fenvalerates is that 52%, α S-2R- fenvalerates are 48%.
Embodiment 3：5mg α R-2R- fenvalerates are weighed, are dissolved in 500ml n-hexanes：Ethanol is 6:In 4 solvent,
10mg/L α R-2R- fenvalerate solution is obtained, 4 DEG C of refrigerators is put into and preserves, efficient liquid phase is utilized in 12,24,48,96,192h
Chromatogram detects solution, according to chromatographic peak appearance time, compares CD spectrograms, judges the isomers and its content corresponding to chromatographic peak.
As a result Fig. 2 is seen, the results showed that in n-hexane：Ethanol is 6:In 4 solvent, 100% α R-2R- fenvalerates are over time
Passage, can partly be converted into the α S-2R- fenvalerates of high activity, and the time is more long more tends towards stability, in 192h, α R-2R- cyanogen
The content of valerate is that 50%, α S-2R- fenvalerates are 50%.Fig. 2 shows that ethanol content is higher in solvent, α R-2R- cyanogen penta
The conversion ratio of chrysanthemum ester is higher and conversion rate is faster.
Embodiment 4：5mg α R-2R- fenvalerates are weighed, are dissolved in 500ml n-hexanes：Isopropanol is 9:1 solvent
In, 10mg/L α R-2R- fenvalerate solution is obtained, 4 DEG C of refrigerators is put into and preserves, in 12,24,48,96,192h using efficiently
Liquid chromatographic detection solution, according to chromatographic peak appearance time, CD spectrograms are compareed, the isomers corresponding to chromatographic peak is judged and its contains
Amount.As a result Fig. 3 is seen, the results showed that in n-hexane：Isopropanol is 9:In 1 solvent, 100% α R-2R- fenvalerates with when
Between passage, can partly be converted into the α S-2R- fenvalerates of high activity, in 192h, the content of α R-2R- fenvalerates is
58%, α S-2R- fenvalerates are 42%.
Embodiment 5：5mg α R-2R- fenvalerates are weighed, are dissolved in 500ml n-hexanes：Isopropanol is 6:4 solvent
In, 10mg/L α R-2R- fenvalerate solution is obtained, 4 DEG C of refrigerators is put into and preserves, in 12,24,48,96,192h using efficiently
Liquid chromatographic detection solution, according to chromatographic peak appearance time, CD spectrograms are compareed, the isomers corresponding to chromatographic peak is judged and its contains
Amount.As a result Fig. 3 is seen, the results showed that in n-hexane：Isopropanol is 6:In 4 solvent, 100% α R-2R- fenvalerates with when
Between passage, can partly be converted into the α S-2R- fenvalerates of high activity, in 192h, the content of α R-2R- fenvalerates is
58%, α S-2R- fenvalerates are 42%.Fig. 3 shows that conversion of the change of isopropanol content on α R-2R- fenvalerates influences simultaneously
Not significantly, final conversion ratio is similar with conversion rate.
Embodiment 6：5mg α R-2R- fenvalerates are weighed, are dissolved in 500ml n-hexanes：Ethanol is 9:In 1 solvent,
10mg/L α R-2R- fenvalerate solution is obtained, 4 DEG C of refrigerators is put into and preserves, efficient liquid phase is utilized in 12,24,48,96,192h
Chromatogram detects solution, according to chromatographic peak appearance time, compares CD spectrograms, judges the isomers and its content corresponding to chromatographic peak.
As a result Fig. 4 is seen, the results showed that in n-hexane：Ethanol is 9:In 1 solvent, 100% α S-2R- fenvalerates are over time
Passage, can partly be converted into the α S-2S- fenvalerates of high activity, and the time is more long more tends towards stability, in 192h, α R-2R- cyanogen
The content of valerate is that 53%, α S-2R- fenvalerates are 47%.Four isomers activity highests of fenvalerate are SS, i.e., suitable
Formula fenvalerate, cis fenvalerate is higher than fenvalerate to the virulence of Fen-S sensitive strains to ester 8.7 times, to indoor cyanogen
The two resistant strain Fen-R and Shandong Yanggu S6, the virulence of cis fenvalerate of valerate seed selection are higher than fenvalerate respectively
113.1 with 28.5 times.For resistant multiple, the resistant strain of indoor seed selection and the resistant population in cotton field is picked up to fenvalerate
Resistance be 81.8~2142.8 times, be 22.1~164.6 times to the resistance of cis fenvalerate, resistance is bigger, fenvalerate
Bigger with the Difference In Toxicity of cis fenvalerate, the insecticidal activity of cis fenvalerate is significantly larger than fenvalerate.
Embodiment 7：5mg α R-2R- fenvalerates are weighed, are dissolved in 500ml n-hexanes：Ethanol is 8:In 2 solvent,
10mg/L α R-2R- fenvalerate solution is obtained, 4 DEG C of refrigerators is put into and preserves, efficient liquid phase is utilized in 12,24,48,96,192h
Chromatogram detects solution, according to chromatographic peak appearance time, compares CD spectrograms, judges the isomers and its content corresponding to chromatographic peak.
As a result Fig. 4 is seen, the results showed that in n-hexane：Ethanol is 8:In 2 solvent, 100% α S-2R- fenvalerates are over time
Passage, can partly be converted into the α S-2S- fenvalerates of high activity, and the time is more long more tends towards stability, in 192h, α R-2R- cyanogen
The content of valerate is that 53%, α S-2R- fenvalerates are 47%.
Embodiment 8：5mg α R-2R- fenvalerates are weighed, are dissolved in 500ml n-hexanes：Ethanol is 6:In 4 solvent,
10mg/L α R-2R- fenvalerate solution is obtained, 4 DEG C of refrigerators is put into and preserves, efficient liquid phase is utilized in 12,24,48,96,192h
Chromatogram detects solution, according to chromatographic peak appearance time, compares CD spectrograms, judges the isomers and its content corresponding to chromatographic peak.
As a result Fig. 4 is seen, the results showed that in n-hexane：Ethanol is 6:In 4 solvent, 100% α S-2R- fenvalerates are over time
Passage, can partly be converted into the α S-2S- fenvalerates of high activity, and the time is more long more tends towards stability, in 192h, α R-2R- cyanogen
The content of valerate is that 50%, α S-2R- fenvalerates are 50%.
Embodiment 9：5mg α R-2R- fenvalerates are weighed, are dissolved in 500ml n-hexanes：Isopropanol is 6:4 solvent
In, 10mg/L α R-2R- fenvalerate solution is obtained, 4 DEG C of refrigerators is put into and preserves, in 12,24,48,96,192h using efficiently
Liquid chromatographic detection solution, according to chromatographic peak appearance time, CD spectrograms are compareed, the isomers corresponding to chromatographic peak is judged and its contains
Amount.As a result Fig. 5 is seen, the results showed that in n-hexane：Isopropanol is 9:In 1 solvent, 100% α S-2R- fenvalerates with when
Between passage, can partly be converted into the α S-2S- fenvalerates of high activity, the time is more long more tends towards stability, in 192h, α S-
The content of 2R- fenvalerates is that 68%, α S-2S- fenvalerates are 32%.
Embodiment 10：5mg α R-2R- fenvalerates are weighed, are dissolved in 500ml n-hexanes：Isopropanol is 6:4 solvent
In, 10mg/L α R-2R- fenvalerate solution is obtained, 4 DEG C of refrigerators is put into and preserves, in 12,24,48,96,192h using efficiently
Liquid chromatographic detection solution, according to chromatographic peak appearance time, CD spectrograms are compareed, the isomers corresponding to chromatographic peak is judged and its contains
Amount.As a result Fig. 5 is seen, the results showed that in n-hexane：Isopropanol is 6:In 4 solvent, 100% α S-2R- fenvalerates with when
Between passage, can partly be converted into the α S-2S- fenvalerates of high activity, the time is more long more tends towards stability, in 192h, α S-
The content of 2R- fenvalerates is that 58%, α S-2S- fenvalerates are 42%.
Claims (4)
1. a kind of method that low activity fenvalerate isomers converts to high activity fenvalerate isomers, it is characterised in that：Institute
The method stated specifically is carried out in accordance with the following steps：
Low activity fenvalerate isomers shown in formula I or formula III is dissolved in organic solvent, respectively obtained after reacting 12-192h
Product containing the high activity fenvalerate isomers shown in formula II or formula IV, realize that low activity fenvalerate isomers is living to height
Property the conversion of fenvalerate isomers；Described organic solvent is the mixed liquor or n-hexane of n-hexane and ethanol and mixing for isopropanol
Close liquid；Described n-hexane and the volume ratio of ethanol are 1.5-9:1；Described n-hexane and the volume ratio of isopropanol are 1.5-9:
1。
2. the method as described in claim 1, it is characterised in that：Low activity fenvalerate isomery shown in the formula I or formula III
The concentration of body is respectively 10-1000mg/L organic solvents.
3. the method as described in claim 1, it is characterised in that：Described n-hexane and the volume ratio of ethanol are 6:4.
4. the method as described in claim 1, it is characterised in that：Described n-hexane and the volume ratio of isopropanol are 6:4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710896270.9A CN107673996A (en) | 2017-09-28 | 2017-09-28 | A kind of method that low activity fenvalerate isomers converts to high activity fenvalerate isomers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710896270.9A CN107673996A (en) | 2017-09-28 | 2017-09-28 | A kind of method that low activity fenvalerate isomers converts to high activity fenvalerate isomers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107673996A true CN107673996A (en) | 2018-02-09 |
Family
ID=61138162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710896270.9A Withdrawn CN107673996A (en) | 2017-09-28 | 2017-09-28 | A kind of method that low activity fenvalerate isomers converts to high activity fenvalerate isomers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107673996A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5334744A (en) * | 1991-12-24 | 1994-08-02 | Zeneca Ltd. | Isomerisation process |
-
2017
- 2017-09-28 CN CN201710896270.9A patent/CN107673996A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5334744A (en) * | 1991-12-24 | 1994-08-02 | Zeneca Ltd. | Isomerisation process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102524319B (en) | Multiple-effect nanoscale biopesticide water aqua and use thereof | |
| CN101601382B (en) | Thymol mite-killing microemulsion and preparation method thereof | |
| CN100397994C (en) | Insect and mite killer with vegetable oil as base | |
| CN104322572B (en) | A kind of plant insecticide | |
| CN101829074A (en) | Standardized recombinant tea tree oil and preparing method thereof | |
| CN1775026A (en) | Disinsection emulsion in water containing avermectin | |
| CN102626079B (en) | Ultralow-volume liquid containing bifenazate | |
| CN106508991A (en) | Biological pesticide and preparation method thereof | |
| CN1304660A (en) | Liquid insecticide as agricultural chemical prepared from natural plant and its preparing process | |
| Khambay | Pyrethroid insecticides | |
| CN101278683A (en) | Pollution-free plant source pesticide rotenone emulsifiable solution formulation and method of preparing the same | |
| CN108935465A (en) | A kind of application of opopanax alkane type sesquiterpene compound in prevention and treatment powdery mildew | |
| CN109717216A (en) | It is a kind of to utilize garlic, capsicum, Chinese prickly ash, the sterilization and disinfestation agent of ginger extract | |
| CN107673996A (en) | A kind of method that low activity fenvalerate isomers converts to high activity fenvalerate isomers | |
| CN102511477B (en) | Pyrethrin hot fogging agent and preparation method and application thereof | |
| AU2009210746B2 (en) | Compositions and methods for arachnid control | |
| CN103478146A (en) | Aqueous iturin A as well as preparation method and application thereof | |
| Williamson et al. | A comparative analysis of the acute toxicity of technical-grade pyrethroid insecticides and their commercial formulations | |
| CN1611115A (en) | Lamda-cyhalothrin micro emulsion and its production method | |
| CN1299579C (en) | 0.3% matrine insecticide and its preparation method | |
| CN100391337C (en) | Effect-promoting pesticide and its preparing method | |
| CN109221181A (en) | Contain loose mite shark and acaricidal complex composition and its application | |
| CN109315398A (en) | A kind of pheromones analogue improving Xestia c nigrum gyplure attractant effect | |
| CN100553457C (en) | A kind of Horsetail P.E and new purposes thereof | |
| CN106508997A (en) | Microorganism wettable powder for preventing pine caterpillars and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180209 |
|
| WW01 | Invention patent application withdrawn after publication |