CN109956904A - Pyrazol acid amide compounds and its application and fungicide - Google Patents
Pyrazol acid amide compounds and its application and fungicide Download PDFInfo
- Publication number
- CN109956904A CN109956904A CN201811555478.5A CN201811555478A CN109956904A CN 109956904 A CN109956904 A CN 109956904A CN 201811555478 A CN201811555478 A CN 201811555478A CN 109956904 A CN109956904 A CN 109956904A
- Authority
- CN
- China
- Prior art keywords
- compound
- powdery mildew
- preventive effect
- rust
- cucumber
- 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.)
- Granted
Links
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention relates to pesticide fields, disclose pyrazol acid amide compounds and its application and fungicide, which has structure shown in following formula (1).Pyrazol acid amide compounds provided by the invention all have significant preventive effect to soybean rust, corn rust, wheat powdery mildew and powdery mildew of cucumber.
Description
Technical field
The present invention relates to agriculture chemicals fungicide fields, and in particular to a kind of pyrazol acid amide compounds and its application, Yi Jiyi
Fungicide of the kind containing the pyrazol acid amide compounds.
Background technique
It is current most important with the fungicide that succinate dehydrogenase (SDH, succinate dehydrogenase) is target
A kind of fungicide kind, this kind of fungicide be by inhibit pathogen succinate dehydrogenase activity, cause pathogen dead
It dies, achievees the purpose that controlling disease.
Since such fungicide has novel mechanism of action, do not interacted with most of fungicide currently on the market anti-
Property, thus become the hot spot that major pesticide company, the current world is competitively studied.
In this kind of fungicide, pyrazol acid amide compounds are to have listed the most one kind of quantity in kind, due to such
Fungicide fungicidal spectrum is wider, and activity is higher, can prevent and treat the various crop disease in agricultural production, thus is that current research is most wide
General a kind of succinate dehydrogenase inhibitors.
For example, CN1226244A and CN101056858A individually disclose the pyrazol acid amide chemical combination used as fungicide
The general formula of object, and the pyrazol acid amide particular compound of some ether structures containing hexichol is disclosed in embodiment.
Further, CN1226244A discloses 12 He of pyrazol acid amide compounds of following two ether structures containing hexichol
21。
CN101056858A discloses the structure of the pyrazole amide analog derivative of the ether of substituted diphenylamine containing oxime.
For another example, CN104557709A discloses two compounds for having following structure feature.
Soybean rust, corn rust, wheat powdery mildew, powdery mildew of cucumber be endanger the great disease of agricultural production, although
The pyrazol acid amide succinate dehydrogenase inhibitors being commercialized at present have sterilization to one or more of above-mentioned disease
Activity, but it still is able to prevent and treat the pyrazol acid amide succinate dehydrogenase inhibitors of these great diseases at much lower concentrations simultaneously also
It is undiscovered.
For example, being found by biological activity test, disclosed in CN1226244A, CN101056858A and CN104557709A
Compound only have at higher concentrations to soybean rust, corn rust, wheat powdery mildew or powdery mildew of cucumber it is preferable anti-
Effect.When reducing Drug level, compound disclosed in the above-mentioned prior art is bad to the preventive effect of soybean rust or corn rust.
But the medication of high concentration will cause the problem of increased costs first, secondly, drug safety is significantly reduced.
Summary of the invention
The purpose of the invention is to the pyrazol acid amide compounds for the diphenyl ether for overcoming the prior art to provide to become rusty to soybean
The preventive effect difference or very poor to the preventive effect of soybean rust at low concentrations of disease, corn rust, wheat powdery mildew and powdery mildew of cucumber
Defect, provide a kind of new even at low concentrations also to soybean rust, corn rust, wheat powdery mildew and cucumber white powder
Disease all has the pyrazol acid amide compounds of excellent preventive effect.
The present inventor has found under study for action, the pyrazol acid amide compounds containing diphenyl ether, secondly in phenylate structure
Substituent group type and the position of substitution it is living to the sterilization of soybean rust, corn rust, wheat powdery mildew and powdery mildew of cucumber
Property has a major impact.Specifically, when the substituent group on the hexichol ether structure of the pyrazol acid amide compounds of diphenyl ether is respectively bromine
Atom and trifluoromethyl, and bromine atom is located at the ortho position of terminal phenyl rings in hexichol ether structure and trifluoromethyl is located at diphenyl ether knot
The contraposition of terminal phenyl rings in structure, and cooperation pyrazole ring the position 5- without containing fluorine atom substitution when, the compound of formation is (hereinafter
Also referred to as the compound of the present invention) for preventing and treating in soybean rust, corn rust, wheat powdery mildew and powdery mildew of cucumber extremely
When a kind of few disease, even under low Drug level, good control efficiency can be also obtained.
Particularly, benzo alkene fluorine bacterium azoles are the hit products of current treatment Asian Soybean Rust, however, invention of the invention
People is under study for action it was unexpectedly observed that the compound of the present invention is suitable with benzo alkene fluorine bacterium azoles to the preventive effect of soybean rust；Also, mesh
Before, due to a large amount of irrational utilizations of benzo alkene fluorine bacterium azoles, benzo alkene fluorine bacterium azoles resistance bacterium has been had already appeared in areas such as Brazil
Strain, therefore, the medicament of development structure novel and high-efficiency have a very important significance for preventing and treating the diseases such as soybean rust.Based on upper
Discovery is stated, the present inventor completes technical solution of the present invention.
To achieve the goals above, the first aspect of the present invention provides a kind of pyrazol acid amide compounds, compound tool
There is structure shown in following formula (1):
The second aspect of the present invention provides application of the compound described in aforementioned first aspect in prevention and treatment soybean rust.
The third aspect of the present invention provides application of the compound described in aforementioned first aspect in prevention and treatment corn rust.
The fourth aspect of the present invention provides application of the compound described in aforementioned first aspect in prevention and treatment wheat powdery mildew.
The fifth aspect of the present invention provides application of the compound described in aforementioned first aspect in prevention and treatment powdery mildew of cucumber.
The sixth aspect of the present invention provides compound described in aforementioned first aspect in preparation for preventing and treating soybean rust, jade
Application in the pesticide of rice rust, wheat powdery mildew and at least two diseases in powdery mildew of cucumber.
In particularly preferred situation, the present invention provide compound described in aforementioned first aspect prevent and treat at the same time soybean rust,
Application in corn rust, wheat powdery mildew and powdery mildew of cucumber.
The seventh aspect of the present invention provides a kind of fungicide, which is made of active constituent and auxiliary material, the activity
Ingredient includes pyrazol acid amide compounds described in first aspect present invention.
Under preferable case, the content of the active constituent is 1-99.9 weight %.
Preferably, the dosage form of the fungicide be selected from missible oil, suspending agent, wettable powder, pulvis, granula, aqua, poison bait,
At least one of mother liquor and female powder.
The pyrazol acid amide compounds of structure shown in formula (1) provided by the invention are at low concentrations also to soybean rust, jade
Rice rust, wheat powdery mildew and powdery mildew of cucumber have good preventive effect.
Another important research meaning of the invention is, passes through field experiment data confirm that, the compound of the present invention pair
Wheat powdery mildew, powdery mildew of cucumber, soybean rust all have good preventive effect.Those skilled in the art know: new agriculture
What medicine created compound carried out first is greenhouse pot culture screening, by inside authentication be found to have the compound of high activity again into
Enter field experiment.But since the influence factor in field experiment is more complicated (such as temperature, illumination, rainwater, soil etc.), in temperature
The many high-activity compounds found in the screening of room but fail to show excellent effect when entering field experiment.For example, fungicide
When finding to show wheat powdery mildew high activity when alkene oxime amine screens indoors, but entering field experiment, preventive effect
It is very significant with toxicity difference.Therefore, excellent preventive effect still can be shown after lab screening enters field experiment
Compound is fewer and fewer.The discovery that the compound of excellent preventive effect still can be shown in field experiment often needs section
The worker of grinding pays what a large amount of creative work can be found.
Specifically, field experiment data confirm that of the invention, the compound of the present invention is to wheat powdery mildew, cucumber white powder
Disease, the preventive effect of soybean rust are substantially better than at present for the preventive effect or this hair of the staple chemical drug agent of aforementioned crop disease
Bright compound is to wheat powdery mildew, powdery mildew of cucumber, the preventive effect of soybean rust and is directed to the main of aforementioned crop disease at present
The preventive effect that medicament is commercialized is suitable.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
There is no particular limitation for method of the present invention to the pyrazol acid amide compounds of structure shown in preparation formula (1), such as
It can be using the pyrazol acid amide compounds of structure shown in following synthetic route preparation formula (1):
Using structure shown in formula provided by the invention (1) pyrazol acid amide compounds prevention and treatment soybean rust, corn rust,
When wheat powdery mildew or powdery mildew of cucumber, it can will contain the substance conduct of the pyrazol acid amide compounds of structure shown in formula (1)
Active constituent is configured to composition pesticide, is applied to crops to prevent and treat effective quantity.
Auxiliary material in the fungicide of the invention can be to be used to form commonly using for various suitable dosage forms in the art
The substances such as auxiliary material, including but not limited to surfactant.
The present invention will be described in detail by way of examples below.In the case where without specific instruction, implement below
Various reagents described in example are all from commercially available.
Embodiment 1
The pyrazol acid amide compounds of structure shown in synthetic route preparation formula (1) using foregoing description of the present invention are (as
Following compound 1), specifically as follows:
(1) 1-3 compound represented is prepared
By the 1-2 compound represented of 3mmol, the 1-1 compound represented and 3.6mmol potassium carbonate of 3.3mmol is added
Into 50mL round-bottomed flask, the DMF of 20mL is added, is warming up to 100 DEG C, TLC monitoring raw material stops reacting after completion of the reaction, adds
Enter 50mL ethyl acetate, adds anhydrous sodium sulfate dry afterwards twice with the washing of 50mL saturated common salt respectively, solvent rear pillar is removed under reduced pressure
Chromatograph to obtain intermediate 1-3, yield 65%.
Brown liquid,1H NMR (600MHz, DMSO) δ 8.07 (s, 1H), 7.68 (d, J=8.6Hz, 1H), 7.05-7.00
(m, 1H), 6.88 (dd, J=8.1,1.6Hz, 2H), 6.77 (d, J=8.7Hz, 1H), 6.62-6.58 (m, 1H), 5.03 (s,
2H).GC-MS:m/z 331.14[M]+.
(2) 1 compound represented of preparation formula
The 1-3 compound represented of 2mmol is dissolved in 20mL methylene chloride, the triethylamine of 3mmol is added, then in ice bath
Under the conditions of 1-4 compound represented (total 2.4mmol) is slowly added dropwise.30mL bis- will be added after monitoring fully reacting in TLC in system
Chloromethanes adds anhydrous sodium sulfate dry afterwards three times with the washing of 50mL saturated common salt respectively, and column Chromatographic purification obtains chemical combination shown in formula 1
Object, yield 56%.
White powder,1H NMR (600MHz, DMSO) δ 9.67 (s, 1H), 8.36 (s, 1H), 8.07 (d, J=2.0Hz,
1H), 7.73 (ddd, J=10.8,7.9,3.4Hz, 2H), 7.33-7.28 (m, 2H), 7.21 (t, J=54Hz, 1H), 7.10-
7.06 (m, 1H), 7.03 (d, J=8.6Hz, 1H), 3.92 (s, 3H) .HRMS (MALDI) calculated value C19H13BrF5N3O2[M+H]+:
490.01841 measured value 490.01674.
Test case 1: bactericidal activity the selection result
Test method: each compound in table 1 is configured to the missible oil of 5 weight %.Test is all made of living body potting, chemical combination
Object effective concentration is as shown in table 1.
Soybean rust
2 leaf phase soybean potting seedling of selection growth neat and consistent carry out foliar spray processing, separately set the blank of spray clear water
Control, 3 repetitions.Second day inoculation soybean rust spore suspension after processing places phjytotron (temperature: 20 after inoculation
DEG C -25 DEG C, relative humidity: > 95%) moisturizing culture places greenhouse (25 DEG C ± 1 DEG C) normal management after 8-16 hours.7 days backsights
Investigation prevention effect when blank control is sufficiently fallen ill.
Corn rust
The 2-3 leaf phase corn potting seedling of selection growth neat and consistent, carries out foliar spray processing according to design concentration, separately
If spraying the blank control of clear water, 3 repetitions.Second day inoculation corn rust spore suspension after processing is placed artificial after inoculation
Climatic chamber (temperature: 25 DEG C of daytime, 20 DEG C of night, relative humidity: 95~100%) moisturizing culture, after 24 hours place greenhouse (25 DEG C ±
1 DEG C) normal management.Investigation prevention effect when backsight blank control was sufficiently fallen ill in 7 days.
Wheat powdery mildew
The 2 leaf phases wheat potting seedling of selection growth neat and consistent, carries out foliar spray processing according to design concentration, separately sets
Spray the blank control of clear water, 3 repetitions.After processing second day spore shake off method inoculation, the crop after inoculation put greenhouse (25 DEG C ±
1 DEG C) normal management.Investigation prevention effect when backsight blank control was sufficiently fallen ill in 7 days.
Powdery mildew of cucumber
The consistent cucumber seedling of a piece of leaf period, growing way is selected, is dried in the shade for 24 hours after spraying treatment.It washes to take and covers with powdery mildew cucumber leaf
The Fresh spores of on piece, are filtered with double gauze, and the suspension that spore concentration is 100,000/mL or so, spray inoculation is made.It connects
Kind after test material natural air drying, then move under thermostatic chamber light in (21-23 DEG C), 8 days backsight blank control incidences into
Row classification investigation, is referred to by disease and calculates preventive effect %.
Investigation method: grade scale uses " pesticide field efficacy medicine test criterion ", calculates control efficiency % with sick index.
Disease index=∑ (the disease numbers of sheets at different levels × opposite value of series) × 100/ (total number of sheets × 9)；
Control efficiency (the %)=control disease index of (control disease index-processing disease index) × 100/；
Test result is as shown in table 1.
Structural formula difference in table 1 for the compound 2-11 of comparison is as follows:
Table 1
"-" expression is not tested
It can be seen that compound provided by the invention from the result in table 1 at low concentrations to become rusty to corn rust, soybean
Disease, wheat powdery mildew and powdery mildew of cucumber show good preventive effect.Particularly, compound provided by the invention is in low concentration
Under to the preventive effect of wheat powdery mildew and powdery mildew of cucumber be significantly better than the prior art offer compound preventive effect.
The structural formula of control compounds 2 and compound 4 and compound provided by the invention can be seen that aforesaid compound 2
Difference between compound 4 and the structure of compound provided by the invention is only that, the diphenyl ether of compound 2 and compound 4
Free phenyl on ortho-substituent be respectively that (corresponding position of compound provided by the invention is bromine for chlorine atom and iodine atom
Atom) and compound 2 and compound 4 pyrazole ring the position 5- on contain fluorine atom substituent (compound provided by the invention
Corresponding position without fluorine atom replace).It is 25mg/L that compound 2 and compound 4 be can be seen that from the result of table 1 in concentration
It is suitable to preventive effect of the compound of the present invention to corresponding disease to the preventive effect of corn rust and soybean rust when above, but
When concentration is 6.25mg/L, compound 2 and compound 4 have not as good as change of the invention the preventive effect of corn rust and soybean rust
The shortcomings that closing preventive effect of the object to corresponding disease.Further, under same concentrations, compound 2 and compound 4 are to wheat powdery mildew
The compound of the present invention is significantly lower than to the preventive effect of wheat powdery mildew and powdery mildew of cucumber with the preventive effect of powdery mildew of cucumber.Thus may be used
To find out, the fluorine atom on the free phenyl of diphenyl ether on the substitution type of halogen atom and the position 5- of pyrazole ring replaces to pyrazoles
The effect and application range of amides compound have a major impact.
The structural formula of compound 3 and compound provided by the invention can be seen that aforesaid compound 3 with it is provided by the invention
Difference between the structure of compound is only that (present invention mentions containing fluorine atom substituent on the position 5- of the pyrazole ring of compound 3
The corresponding position of the compound of confession replaces without fluorine atom).It is 25mg/L that compound 3 be can be seen that from the result of table 1 in concentration
It is suitable to preventive effect of the compound of the present invention to corresponding disease to the preventive effect of corn rust and soybean rust when above, but
When concentration is 6.25mg/L, compound 3 has too late the compound of the present invention to phase the preventive effect of corn rust and soybean rust
The shortcomings that answering the preventive effect of disease.Further, under same concentrations, compound 3 prevents wheat powdery mildew and powdery mildew of cucumber
Effect is significantly lower than the compound of the present invention to the preventive effect of wheat powdery mildew and powdery mildew of cucumber.It can thus be seen that pyrazole ring
Fluorine atom substitution on the position 5- has a major impact the effect and application range of pyrazol acid amide compounds.
Before the structural formula of control compounds 5, compound 10 and compound 11 and compound provided by the invention can be seen that
The difference stated between compound 5, compound 10 and compound 11 and the structure of compound provided by the invention is only that: compound
Ortho-substituent on the free phenyl of 5 diphenyl ether be iodine atom, compound 11 diphenyl ether free phenyl on ortho position
Substituent group is chlorine atom, and the ortho-substituent and para-orientating group on the free phenyl of the diphenyl ether of compound 10 are chlorine atom
(ortho-substituent of compound provided by the invention is bromine atom, and para-orientating group is trifluoromethyl).It can from the result of table 1
To find out, compound 5, compound 10 and compound 11 are when concentration is 25mg/L or more, to corn rust and soybean rust
Preventive effect is suitable to preventive effect of the compound of the present invention to corresponding disease, but when concentration is 6.25mg/L, compound 5, chemical combination
Object 10 and compound 11 are to the preventive effect of corn rust not as good as the compound of the present invention to the preventive effect of corresponding disease.Further, exist
Under same concentrations, compound 5, compound 10 and compound 11 are to the preventive effect of wheat powdery mildew and powdery mildew of cucumber significantly lower than this
Preventive effect of the compound of invention to wheat powdery mildew and powdery mildew of cucumber.It can thus be seen that on the free phenyl of diphenyl ether
The type of halogen atom substituent has a major impact the effect and application range of pyrazol acid amide compounds.
Control compounds 6, compound 8 and compound provided by the invention structural formula can be seen that aforesaid compound 6,
Difference between compound 8 and the structure of compound provided by the invention is only that: the diphenyl ether of compound 6 and compound 8
2,5- bit substituent on free phenyl is that (the position of substitution of compound provided by the invention is 2,4- to trifluoromethyl, and 2-
Position is that bromine atom replaces, and 4- replace for trifluoromethyl), in addition, also being taken containing fluorine atom on the position 5- of the pyrazole ring of compound 8
Dai Ji.As can be seen that compound 6 and compound 8 are when concentration is 100mg/L or more, to soybean rust from the result of table 1
Preventive effect is suitable to preventive effect of the compound of the present invention to corresponding disease, but when concentration is lower than 100mg/L, compound 6 and change
Object 8 is closed to the preventive effect of soybean rust obviously not as good as the compound of the present invention to the preventive effect of corresponding disease.Further, identical dense
Under degree, compound 6 and compound 8 are to the preventive effect of wheat powdery mildew, soybean rust and powdery mildew of cucumber significantly lower than of the invention
Preventive effect of the compound to wheat powdery mildew, soybean rust and powdery mildew of cucumber.It can thus be seen that on the free phenyl of diphenyl ether
Fluorine atom in the type and the position of substitution of substituent group and the position 5- of pyrazole ring replaces the effect to pyrazol acid amide compounds
And application range has a major impact.
The structural formula of control compounds 7 and compound provided by the invention can be seen that aforesaid compound 7 and mention with the present invention
Difference between the structure of the compound of confession is only that, on the position 5- of the pyrazole ring of compound 7 containing fluorine atom substituent (and this
The compound of invention is in the not no substituent group in corresponding position) and compound 7 diphenyl ether free phenyl on the position 2- replace
Base is trifluoromethyl (and substituent group of the compound of the present invention on corresponding position is bromine atom).It can be with from the result of table 1
Find out, compound 7 is when concentration is 25mg/L or more, to the preventive effect and the compound of the present invention pair of corn rust and soybean rust
The preventive effect of corresponding disease is suitable, but when concentration is 6.25mg/L, compound 7 to the preventive effect of corn rust and soybean rust not
And the compound of the present invention is to the preventive effect of corresponding disease.Further, under same concentrations, compound 7 to wheat powdery mildew and
The preventive effect of powdery mildew of cucumber is substantially less than the compound of the present invention to the preventive effect of wheat powdery mildew and powdery mildew of cucumber.It is possible thereby to
Find out, the type of substituent group is to pyrazol acid amide on the free phenyl of fluorine atom substitution and diphenyl ether on the position 5- of pyrazole ring
The effect and application range of compound have a major impact.
The structural formula of control compounds 9 and compound provided by the invention can be seen that aforesaid compound 9 and mention with the present invention
Difference between the structure of the compound of confession is only that, 2- bit substituent and 4- on the free phenyl of the diphenyl ether of compound 9
Bit substituent is respectively that (and substituent group of the compound of the present invention on corresponding position is respectively bromine original for trifluoromethyl and bromine atom
Son and trifluoromethyl).As can be seen that compound 9 is when concentration is 25mg/L or more from the result of table 1, to corn rust and
The preventive effect of soybean rust is suitable to preventive effect of the compound of the present invention to corresponding disease, but when concentration is 6.25mg/L, changes
The shortcomings that closing the preventive effect that object 9 has too late the compound of the present invention to corresponding disease the preventive effect of corn rust and soybean rust.
Further, under same concentrations, compound 9 is significantly lower than change of the invention to the preventive effect of wheat powdery mildew and powdery mildew of cucumber
Object is closed to the preventive effect of wheat powdery mildew and powdery mildew of cucumber.It can thus be seen that substituent group takes on the free phenyl of diphenyl ether
Subrogate to set and the effect and application range of pyrazol acid amide compounds are had a major impact.
Test case 2: the secondary screening under lower concentration
Using method identical with test case 1 to compound provided by the invention and part for comparison compound into
Row secondary screening, unlike test case 1, the effective concentration of the compound in this test case is as shown in table 2.
The test result of this test case is as shown in table 2.
Table 2
"-" expression is not tested
It is 3.125mg/L or more that compound 5, compound 10 and compound 11 be can be seen that from the result of table 2 in concentration
When, it is suitable to preventive effect of the compound of the present invention to corresponding disease to the preventive effect of soybean rust, but be lower than in concentration
When 3.125mg/L, compound 5, compound 10 and compound 11 are to the preventive effect of soybean rust not as good as the compound of the present invention to phase
Answer the preventive effect of disease.Also, compound 5, compound 10 and compound 11 are equal to the preventive effect of powdery mildew of cucumber at various concentrations
Preventive effect of the obvious too late the compound of the present invention to corresponding disease.It can thus be seen that the substitution on the free phenyl of diphenyl ether
The type of base has a major impact the effect and application range of pyrazol acid amide compounds.
It can also be seen that compound provided by the invention is better than Fluoxastrobin to soybean rust preventive effect by the result in table 2, and
And have and prothioconazoles and the comparable preventive effect of benzo alkene fluorine bacterium azoles.In addition, the compound of the present invention is to powdery mildew of cucumber preventive effect
Better than Fluoxastrobin, prothioconazoles, benzo alkene fluorine bacterium azoles, difenoconazole and ethirimol.
Test case 3
Test method: host plant culture
Soybean is cultivated spare to 1 leaf period in greenhouse.
Test operation step:
Each compound sample is dissolved in dimethyl sulfoxide, it is spare to be configured to mother liquor.When test, by compound sample and
The water for compareing medicinal 0.5 weight % Tween 80 is configured to series of concentrations gradient medical fluid, carries out foliar spray processing to host crop,
Then it dries in the shade naturally, is inoculated with pathogen after 24 hours.With inoculator by soybean rust bacterium spore suspension (5-8 × 106A/mL)
It sparges on host crop, then moves into phjytotron culture (24 ± 2 DEG C, RH > 90, no light), after 16 hours, move into temperature
Room normal management.The bactericidal activity of compound is investigated in test material culture 7-15 days.
Investigation method: result investigation can write " A Manual of Assessment Keys referring to U.S.'s pathology of plants
For Plant Diseases ", according to the occurring degree of control, using visual method, the bactericidal activity of experimental investigation sample is used
100-0 is indicated, represents the occurring degree that disease-free and " 0 " grade represents most serious with " 100 " grade.
It is analyzed and evaluated using DPS evaluation system, calculates linear regression equation, EC50Value and related coefficient (r).
Specific result is as shown in table 3.
Table 3
The EC of compound provided by the invention prevention and treatment soybean rust it can be seen from the result of table 350Value is significantly lower than chemical combination
Object 10 and compound 11 prevent and treat the EC of soybean rust50Value.Therefore, there is compound provided by the invention excellent prevention and treatment soybean to become rusty
The effect of disease.
Test case 4
Test method: host plant culture
Greenhouse is spare to 1 leaf period by corn culture.
Test operation step:
Each compound sample is dissolved in dimethyl sulfoxide, it is spare to be configured to mother liquor.When test, by compound sample and
The water for compareing medicinal 0.5 weight % Tween 80 is configured to series of concentrations gradient medical fluid, carries out foliar spray processing to host crop,
Then it dries in the shade naturally, is inoculated with pathogen after 24 hours.With inoculator by corn rust bacterium spore suspension (5-8 × 106A/mL)
It sparges on host crop, then moves into phjytotron culture (24 ± 2 DEG C, RH > 90, no light), after 16 hours, move into temperature
Room normal management.The bactericidal activity of compound is investigated in test material culture 7-15 days.
Investigation method: result investigation can write " A Manual of Assessment Keys referring to U.S.'s pathology of plants
For Plant Diseases ", according to the occurring degree of control, using visual method, the bactericidal activity of experimental investigation sample is used
100-0 is indicated, represents the occurring degree that disease-free and " 0 " grade represents most serious with " 100 " grade.
It is analyzed and evaluated using DPS evaluation system, calculates linear regression equation, EC90Value and related coefficient (r).
Specific result is as shown in table 4.
Table 4
The EC of compound provided by the invention prevention and treatment corn rust it can be seen from the result of table 490Value is significantly lower than chemical combination
Object 10 and compound 11 prevent and treat the EC of corn rust90Value.Therefore, there is compound provided by the invention excellent prevention and treatment corn to become rusty
The effect of disease.
Test case 5: field trial
I, powdery mildew of cucumber test method:
Application method: cauline leaf is spraying (spraying equipment: prosperous Condar lithium cell electric is spraying).
Trial crops: cucumber (kind: Tian Jiao 7)
This test carries out in Shenyang, is experimental field loam, and content of organics is abundant, and fertilizer and water management is normal, and experimental plot does not make
With other fungicide.
The arrangement mode of experimental plot is the arrangement of random district's groups；Plot area: 15 square metres；Number of repetition: 3 times；Application
It is administered 2 times altogether time and number: on September 28th, 2018 --- on October 11st, 1.Apply liquid volume: 3 weights of each processing
Multiple, 3 repetitions share water 8L.Other pesticides are not applied during test.Test application selects fair weather, after medicine 1 day without rain.
15-20 days investigation preventive effects after 2nd application.
Every cell takes 4 points of investigation at random, and every is looked into 2 plants, and the whole blades of every plant of investigation are accounted for the lesion area on every leaf
The percentage of entire leaf area is classified.
Stage division (as unit of blade):
0 grade: disease-free spot；
1 grade: lesion area accounts for 5% or less entire leaf area；
3 grades: lesion area accounts for the 6%-10% of entire leaf area；
5 grades: lesion area accounts for the 11%-20% of entire leaf area；
7 grades: lesion area accounts for the 21%-40% of entire leaf area；
9 grades: lesion area accounts for 40% or more of entire leaf area.
According to " National Standard of the People's Republic of China's pesticide field trial criterion " related content, the state of an illness is calculated by classification and is referred to
Number is calculated control efficiency according to disease index, is shown using DPS evaluation system (Duncan formula duncan's new multiple range method) to test data
The analysis of work property.
The results are shown in Table 5.
Table 5
As seen from Table 5, in terms of the preventive effect of field trial, the compounds of this invention has powdery mildew of cucumber
Good preventive effect, the compounds of this invention show 50.27% preventive effect under 150 grams/ha of dosage to powdery mildew of cucumber, high
For preventing and treating the preventive effect of the important goods chemical drug agent fluxapyroxad of powdery mildew of cucumber in agricultural production under same dose.?
Under 225 grams/ha of dosage, the compounds of this invention reaches 60% or more to the preventive effect of powdery mildew of cucumber, this is in agricultural production
Preventive effect with practical application value.It should be pointed out that the disease of this test refers to up to 82.74, belong to occurring degree extremely
Serious situation, this absolutely proves that the compounds of this invention to the excellent preventive effect of powdery mildew of cucumber, has apparent practical value.
II, wheat powdery mildew test method:
Application method: cauline leaf is spraying (spraying equipment: prosperous Condar lithium cell electric is spraying).
Trial crops: wheat (kind: distant spring 10)
This test carries out in Shenyang, is experimental field loam, and content of organics is abundant, and fertilizer and water management is normal, and experimental plot does not make
With other fungicide.
The arrangement mode of experimental plot is the arrangement of random district's groups；Plot area: 15 square metres；Number of repetition: 3 times；Application
Time and number: on September 17th, 2018 is administered 1 time altogether.Apply liquid volume: 3 repetitions of each processing, 3 repetitions share water
8L.Other pesticides are not applied during test.Test application selects fair weather, after medicine 1 day without rain.
5 points of every cell diagonal line samplings, every is investigated 20 plants, first blade under the boot leaf of every plant of investigation.
Disease scale standard is as follows:
0 grade: disease-free；
1 grade: lesion area accounts for 5% or less the blade gross area；
3 grades: lesion area accounts for blade gross area 6%-25%；
5 grades: lesion area accounts for blade gross area 26%-50%；
7 grades: lesion area accounts for blade gross area 51%-75%；
9 grades: lesion area accounts for blade gross area 76%-100%.
According to " National Standard of the People's Republic of China's pesticide field trial criterion " related content, the state of an illness is calculated by classification and is referred to
Number is calculated control efficiency according to disease index, is shown using DPS evaluation system (Duncan formula duncan's new multiple range method) to test data
The analysis of work property.
The results are shown in Table 6.
Table 6
As seen from Table 6, in terms of the preventive effect of field trial, the compounds of this invention has wheat powdery mildew
Excellent preventive effect, even under 50 grams/ha of low usage amount, the preventive effect of the compounds of this invention has still reached 92.34%, and
Important goods chemical drug agent fluxapyroxad and triazolone in agricultural production for preventing and treating wheat powdery mildew is under same dose
Preventive effect is substantially less than the compounds of this invention.It should be pointed out that the disease of this test refers to more than 60, belong to occurring degree very
Serious situation, this also absolutely proves the excellent preventive effect of the compounds of this invention, shows that the compounds of this invention has practical value.
III, soybean rust test method:
Application method: cauline leaf is spraying (spraying equipment: prosperous Condar lithium cell electric is spraying).
Trial crops: soybean (kind: distant beans 15)
This test carries out in Shenyang, is experimental field loam, and content of organics is abundant, and fertilizer and water management is normal, and experimental plot does not make
With other fungicide.
The arrangement mode of experimental plot is the arrangement of random district's groups；Plot area: 25 square metres；Number of repetition: 3 times；Application
Time and number: on August 11st, 2018 August 21st, is administered 2 times altogether.Apply liquid volume: 3 repetitions of each processing, 3 repetitions
Share water 8L.Other pesticides are not applied during test.Test application selects fair weather, after medicine 1 day without rain.2nd application
15-20 days investigation preventive effects afterwards.
20 plants of the sampling survey of every cell diagonal method 5,10 leaves of every plant of investigation.Record total leaf number and sick leaf at different levels
Number.
Disease scale standard is as follows:
0 grade: disease-free；
1 grade: lesion area accounts for 5% or less the blade gross area；
3 grades: lesion area accounts for blade gross area 6%-25%；
5 grades: lesion area accounts for blade gross area 26%-50%；
7 grades: lesion area accounts for blade gross area 51%-75%；
9 grades: lesion area accounts for blade gross area 76%-100%.
According to " National Standard of the People's Republic of China's pesticide field trial criterion " related content, the state of an illness is calculated by classification and is referred to
Number is calculated control efficiency according to disease index, is shown using DPS evaluation system (Duncan formula duncan's new multiple range method) to test data
The analysis of work property.
The results are shown in Table 7.
Table 7
The result shows that the compounds of this invention has excellent preventive effect to soybean rust, even in 50 grams/ha of low use
Under amount, the preventive effect of the compounds of this invention still reaches 90% or more, and for preventing and treating the important quotient of soybean rust in agricultural production
Even under 100 grams/ha of dosage, preventive effect is also extremely significant to be lower than the present inventionization for product chemical drug agent fluxapyroxad and Fluoxastrobin
Close object.It should be pointed out that the disease of this test refers to up to 85.48, belong to occurring degree extremely serious situation, this sufficiently says
Bright the compounds of this invention has apparent practical value to the excellent preventive effect of soybean rust.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (9)
1. a kind of pyrazol acid amide compounds, which has structure shown in following formula (1):
2. application of the compound described in claim 1 in prevention and treatment soybean rust.
3. application of the compound described in claim 1 in prevention and treatment corn rust.
4. application of the compound described in claim 1 in prevention and treatment wheat powdery mildew.
5. application of the compound described in claim 1 in prevention and treatment powdery mildew of cucumber.
6. compound described in claim 1 is white for preventing and treating soybean rust, corn rust, wheat powdery mildew and cucumber in preparation
Application in the pesticide of at least two diseases in powder disease.
7. a kind of fungicide, which is made of active constituent and auxiliary material, and the active constituent includes described in claim 1
Pyrazol acid amide compounds.
8. fungicide according to claim 7, wherein the content of the active constituent is 1-99.9 weight %.
9. fungicide according to claim 7 or 8, wherein the dosage form of the fungicide is selected from missible oil, suspending agent, wettable
At least one of pulvis, pulvis, granula, aqua, poison bait, mother liquor and female powder.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2017114028504 | 2017-12-22 | ||
| CN201711402850 | 2017-12-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109956904A true CN109956904A (en) | 2019-07-02 |
| CN109956904B CN109956904B (en) | 2022-03-01 |
Family
ID=66994433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811555478.5A Active CN109956904B (en) | 2017-12-22 | 2018-12-19 | Pyrazole amide compound and application thereof and bactericide |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109956904B (en) |
| WO (1) | WO2019120218A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111187215A (en) * | 2020-01-21 | 2020-05-22 | 西北农林科技大学 | Fluorine-containing pyrazole amide derivative, preparation method and application thereof |
| WO2022042605A1 (en) * | 2020-08-26 | 2022-03-03 | 山东省联合农药工业有限公司 | Bactericidal composition comprising pyrazole amide compound and triazole bactericide |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04316559A (en) * | 1990-11-28 | 1992-11-06 | Nissan Chem Ind Ltd | Pyrazole carboxanilide derivative and fungicide |
| CN1226244A (en) * | 1996-07-24 | 1999-08-18 | 拜尔公司 | Carbanilides used as pesticides |
| JP2004189738A (en) * | 2002-11-29 | 2004-07-08 | Nippon Nohyaku Co Ltd | Substituted anilide derivative, its intermediate, agricultural horticultural chemical and usage of the same |
| CN101056858A (en) * | 2004-09-06 | 2007-10-17 | 巴斯福股份公司 | (hetero)cyclyl(thio) carboxylic acid anilides for controlling pathogenic fungi |
| CN104557709A (en) * | 2013-10-23 | 2015-04-29 | 华中师范大学 | Pyrazole amide compound containing diphenyl ether, and application and pesticide composition of pyrazole amide compound |
| CN106336380A (en) * | 2015-07-07 | 2017-01-18 | 浙江省化工研究院有限公司 | Diphenyl ether structure-containing pyrazolecarboxamide compound and its preparation method and use |
| CN106561667A (en) * | 2016-11-14 | 2017-04-19 | 江西正邦生物化工有限责任公司 | Bactericide composite containing C19H13ClF5N302 |
| CN103391925B (en) * | 2010-11-15 | 2017-06-06 | 拜耳知识产权有限责任公司 | 5 halo-pyrazole formamides |
-
2018
- 2018-12-19 CN CN201811555478.5A patent/CN109956904B/en active Active
- 2018-12-19 WO PCT/CN2018/122050 patent/WO2019120218A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04316559A (en) * | 1990-11-28 | 1992-11-06 | Nissan Chem Ind Ltd | Pyrazole carboxanilide derivative and fungicide |
| CN1226244A (en) * | 1996-07-24 | 1999-08-18 | 拜尔公司 | Carbanilides used as pesticides |
| JP2004189738A (en) * | 2002-11-29 | 2004-07-08 | Nippon Nohyaku Co Ltd | Substituted anilide derivative, its intermediate, agricultural horticultural chemical and usage of the same |
| CN101056858A (en) * | 2004-09-06 | 2007-10-17 | 巴斯福股份公司 | (hetero)cyclyl(thio) carboxylic acid anilides for controlling pathogenic fungi |
| CN103391925B (en) * | 2010-11-15 | 2017-06-06 | 拜耳知识产权有限责任公司 | 5 halo-pyrazole formamides |
| CN104557709A (en) * | 2013-10-23 | 2015-04-29 | 华中师范大学 | Pyrazole amide compound containing diphenyl ether, and application and pesticide composition of pyrazole amide compound |
| CN106336380A (en) * | 2015-07-07 | 2017-01-18 | 浙江省化工研究院有限公司 | Diphenyl ether structure-containing pyrazolecarboxamide compound and its preparation method and use |
| CN106561667A (en) * | 2016-11-14 | 2017-04-19 | 江西正邦生物化工有限责任公司 | Bactericide composite containing C19H13ClF5N302 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111187215A (en) * | 2020-01-21 | 2020-05-22 | 西北农林科技大学 | Fluorine-containing pyrazole amide derivative, preparation method and application thereof |
| CN111187215B (en) * | 2020-01-21 | 2023-02-24 | 西北农林科技大学 | Fluorine-containing pyrazole amide derivative, preparation method and application thereof |
| WO2022042605A1 (en) * | 2020-08-26 | 2022-03-03 | 山东省联合农药工业有限公司 | Bactericidal composition comprising pyrazole amide compound and triazole bactericide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109956904B (en) | 2022-03-01 |
| WO2019120218A1 (en) | 2019-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109928929A (en) | Pyrazol acid amide compounds and its application and fungicide | |
| CN102276596B (en) | Thiadiazole compound as well as preparation and application thereof | |
| WO2006081759A1 (en) | N-(2-substituted phenyl)-n-methoxycarbamates and their preparation as well as use | |
| BR112016007427B1 (en) | pyrazole-amide compounds and uses thereof | |
| BR112017022924B1 (en) | METHODS FOR HYDRAULIC IMPROVEMENT OF CROPS | |
| CN109956904A (en) | Pyrazol acid amide compounds and its application and fungicide | |
| CN104604927A (en) | Seed-treating agent containing clothianidin, pyraclostrobin and metconazole | |
| JPS6034542B2 (en) | New isothiocyanate phenyl esters | |
| CN115594641A (en) | Compound containing benzyl 1,2,3-triazole structure and application of compound as bactericide | |
| JP4558496B2 (en) | Bactericidal composition for controlling rice plant diseases | |
| CN105061412A (en) | Fluorine-containing N-furoamide compound and application thereof | |
| CN111285807A (en) | Pyrazole amide compound and application thereof | |
| CN111285815A (en) | Pyrazinamide compound and application thereof | |
| CN111285801B (en) | Pyridine amide compound and application | |
| CN102067845B (en) | Application of 5-benzyl-4-alkyl-2-arylaminothiazole in preparation of pesticides | |
| CN111285802B (en) | Pyridine amide compound and application | |
| CN108640875B (en) | Pyrazole amide compound and preparation method and application thereof | |
| JPH01117864A (en) | Substituted nicotinic acid derivative, its production and agricultural and horticultural fungicide containing said derivative as active component | |
| JPH0259831B2 (en) | ||
| CN117486866A (en) | Pyrimidine diketone compound and preparation method and application thereof | |
| CN104177310B (en) | Substituted aromatic amines compounds and uses thereof | |
| JPS63198676A (en) | Pyridyltriazine derivative, its production and plant blight controlling agent containing said derivative as active component | |
| JPH0144705B2 (en) | ||
| CN110294751A (en) | Have the imidazoles [4,5-b] of bioactivity and pyridine compounds and their and its preparation method and application | |
| JPS6061572A (en) | Geometric isomer of 2,2-bis-fluoromethyl-5- cyclohexyl-4-(1,2,4-triazol-1-yl)-pentan-3-ol |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |