CN104521988B - A kind of containing methylsulfonyl bacterium azoles and the complex composition of tiger glue adipic acid copper and preparation - Google Patents
A kind of containing methylsulfonyl bacterium azoles and the complex composition of tiger glue adipic acid copper and preparation Download PDFInfo
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- CN104521988B CN104521988B CN201410788175.3A CN201410788175A CN104521988B CN 104521988 B CN104521988 B CN 104521988B CN 201410788175 A CN201410788175 A CN 201410788175A CN 104521988 B CN104521988 B CN 104521988B
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Abstract
The present invention discloses a kind of containing methylsulfonyl bacterium azoles and the complex composition of tiger glue adipic acid copper and preparation.This complex composition is made up of methylsulfonyl bacterium azoles and tiger glue adipic acid copper；Wherein, the chemical name of methylsulfonyl bacterium azoles is 2 (to fluorophenyl) 5 mesyl 1; 3; 4 diazole; the weight ratio of methylsulfonyl bacterium and tiger glue adipic acid copper is (20～1): (1～40), and it is 0.1% 90% that the complex composition of the present invention accounts for the weight percentage of antibacterial.The complex composition of the present invention can effectively prevent and treat various bacterial disease such as citrus bacterial canker disease, cucumber bacterial angular leaf spot etc., can prevent and treat fungal disease such as downy mildew of garpe simultaneously.The complex composition of the present invention has obvious synergistic function, and preventive effect is high, reduce the usage amount of medicament, reduce cost accounting, delays Drug resistance simultaneously.
Description
Technical field
The present invention relates to technical field of pesticide, the compositions compounding particularly to two kinds of pesticide activity components and preparation.
Background technology
The most various crop bacterial diseases present the trend increased the weight of year by year, and occurring area increases year by year, gives
Agricultural production brings significant damage, is used in the market preventing and treating thin sexually transmitted disease (STD) evil preferable medicament shortcoming.Bacterial disease is to have
Disease caused by antibacterial infection process, the pathology types that plant produces after being infected by bacterial disease has: the withered type of spotted type, leaf,
Blue or green withered type, ulcer type, rot type, deformity.But while bacterial disease occurs, fungal disease is the most seriously caused harm crop
Growth.The medicament that can simultaneously prevent and treat two kinds of diseases in the market lacks, and peasant household generally uses preventing and treating bacterial disease and fungus
Two medicaments of sexually transmitted disease (STD) evil carry out on-the-spot arbitrarily mixture, and in order to improve prevention effect, peasant household typically strengthens dosage.Due to peasant household
Not Scientific Usage of Drugs, not only do not reach potentiation, it is also possible to produce antagonism, prevention effect declines on the contrary.
To this end, Guizhou University's independent research have new type bactericide " the one class preventing and control crop antibacterial of independent intellectual property rights
The diazole sulfone compound (Patent No. ZL201110314246.2) of disease ", its structural formula is:
The step of preparation process of this compound and condition:
(1) preparation of different replacing acid methyl ester intermediate: with different organic acid and absolute methanol as raw material, at concentrated sulphuric acid
Lower back flow reaction 6-10 hour of catalysis, reduce pressure separating methanol, and after saturated sodium bicarbonate aqueous solution adjusts ph=7, separatory obtains different first
Acid methyl ester；
(2) preparation of different substituted formylhydrazine intermediate: be dissolved in methanol with different methyl formates, the most slowly add
40%-80% hydrazine hydrate, till back flow reaction is complete, separates out different substituted formylhydrazine after cooling；
(3) 2-sulfydryl-5-replaces the preparation of-1,3,4-diazole intermediate: with the formylhydrazine of above-mentioned preparation and KOH, two
Nitric sulfid is raw material, and ethanol is solvent, and back flow reaction is complete, de-ethanol, adjusts PH=5 to obtain 2-sulfydryl-5-and replaces-1,3,4-
Diazole；
(4) 2-thioether-5-replaces the preparation of-1,3,4-diazole intermediate: replace-1,3,4-with above-mentioned 2-sulfydryl-5-
Diazole is raw material, after hydro-oxidation sodium water dissolution, is reacted by dimethyl sulfate (second) ester or the halogenated hydrocarbons etc. of mole with 1-2
To corresponding sulfide compound；
(5) 2-methyl (ethyl) sulfonyl-5-replaces the preparation of-1,3,4-diazole.
With corresponding thioether as raw material, it is dissolved in glacial acetic acid, 2%-7% potassium permanganate solution or 30% hydrogen peroxide
Oxidation obtains corresponding sulfone compound.
Tiger glue adipic acid copper, chemical name is succinic acid copper, 1,3-propanedicarboxylic acid copper, adipic acid copper, be succinic acid, 1,3-propanedicarboxylic acid and oneself two
The mixture of acid complex copper, molecular formula is [(CH2)17(COO)2]nCu, for known and published pesticide species.
Summary of the invention
For diazole sulfone compound, applicant researches and develops further, as Rn fluorine in halogen atom, R2Select C1-C5
The methyl of alkyl i.e. obtains the structural formula of diazole sulfone compound:
Its chemical name is 2-(to fluorophenyl)-5-mesyl-1,3,4-diazole, is called for short methylsulfonyl bacterium azoles.
The concrete syntheti c route of compound methylsulfonyl bacterium azoles is as follows:
(1) synthesis to fluorobenzoyl hydrazine
(2) the 2-sulfydryl-5-synthesis to fluorophenyl-1,3,4-diazole
(3) the 2-Dimethyl sulfide-5-synthesis to fluorophenyl-1,3,4-diazole
(4) 2-(to fluorophenyl)-5-mesyl-1,3,4-diazole target compound is prepared
Applicant further study show that, methylsulfonyl bacterium azoles is the preventing and treating bacterial disease medicament of novel structure, can pass through
Suppression pathogen energy synthesis, the growth of suppression antibacterial and breeding.Methylsulfonyl bacterium azoles has the feature of interior suction, conduction, penetrates into leaf
After sheet epidermis, energy transporting is to other positions of same blade.Substantial amounts of isolated test shows, methylsulfonyl bacterium azoles is thin to causing plant
The various pathogenetic bacterias of fungus diseases have good inhibiting effect, the most directly suppress bacterial multiplication.Through repeatedly pot experiment and field
Between the test of pesticide effectiveness checking, show that methylsulfonyl bacterium azoles is respectively provided with preferable prevention effect to crop bacterial disease, especially to Oryza sativa L.
Bacterial leaf-blight, slice disease, tobacco bacterial wilt, bacterial wilt of tomato, citrus bacterial canker disease etc. all have good control effect, and energy one
Determine in degree, to stimulate plant growth healthy and strong, improve the resistance of crop.This compound has efficiently, wide spectrum, use safety spy
Point, is an antibacterial having much exploitation potential quality.
Tiger glue adipic acid copper, chemical name is succinic acid copper, 1,3-propanedicarboxylic acid copper, adipic acid copper, be succinic acid, 1,3-propanedicarboxylic acid and oneself two
The mixture of acid complex copper, molecular formula is [(CH2)17(COO)2]nCu, for known and published pesticide species.
In view of this, the deficiency existed for prior art, it is an object of the invention to provide containing methylsulfonyl bacterium azoles and amber
And the complex composition of glue adipic acid copper and preparation.Contrasting with single dose, this complex composition has obvious potentiation, can be effective
Preventing and treating crop bacterial disease and fungal disease, and reduce the using dosage of pesticide, save drug cost, fungicidal spectrum
The most extensive, delay the comprehensive control of the Drug resistance of pathogen, beneficially environmental conservation and agricultural disease.
In order to reach the purpose of the present invention, the technical solution used in the present invention is:
A kind of containing methylsulfonyl bacterium azoles and the complex composition of tiger glue adipic acid copper, this complex composition is by methylsulfonyl bacterium azoles and amber
Glue adipic acid copper forms；The chemical name of described methylsulfonyl bacterium azoles is 2-(to fluorophenyl)-5-mesyl-1,3,4-diazole.
In order to ensure that complex composition has more preferable preventive effect and potentiation, above-described containing methylsulfonyl bacterium azoles and amber
The complex composition of glue adipic acid copper, as preferably, described methylsulfonyl bacterium azoles and the weight ratio of tiger glue adipic acid copper are (20～1):
(1～40).
In order to ensure that complex composition has more preferable preventive effect and potentiation, above-described containing methylsulfonyl bacterium azoles and amber
The complex composition of glue adipic acid copper, as preferably, described methylsulfonyl bacterium azoles and the weight ratio of tiger glue adipic acid copper are (5～1): (1
～20).
The present invention also provides for a kind of containing methylsulfonyl bacterium azoles and the preparation of tiger glue adipic acid copper, and said preparation book is by above-described multiple
Acceptable adjuvant on combo compound and pesticide, is prepared as preventing and treating the antibacterial of crop pest.
In order to ensure that antibacterial has more preferable preventive effect, the above contains methylsulfonyl bacterium azoles and the preparation of tiger glue adipic acid copper,
As preferably, it is 0.1%-90% that described complex composition accounts for the weight percentage of above-mentioned antibacterial.
The above contains methylsulfonyl bacterium azoles and the preparation of tiger glue adipic acid copper, it is preferable that described complex composition accounts for above-mentioned killing
The weight percentage of microbial inoculum is 1%-80%.
The above contains methylsulfonyl bacterium azoles and the preparation of tiger glue adipic acid copper, it is highly preferred that described complex composition accounts for above-mentioned
The weight percentage of antibacterial is 5%-60%.
In order to meet the demand of different use, antibacterial of the present invention can be made into multiple dosage form, as preferably, at this
Invention offer embodiment in, the dosage form of antibacterial be suspending agent, wettable powder, water dispersible granules, suspension seed-coating agent or
Granule.It is not limited only to the dosage form that the present invention provides.
In order to preferably play the bactericidal effect of complex composition, described antibacterial is except including compounded combination beyond the region of objective existence, also
Including adjuvant acceptable on pesticide.The mixture of a kind of and auxiliary agent during wherein adjuvant is filler and solvent.
Described auxiliary agent is surfactant, wetting dispersing agent, thickening agent, binding agent, disintegrating agent, film former.Add if desired
Enter other conventional functionality auxiliary agents such as antifreezing agent, thickening agent, stabilizer, defoamer.
Filler is in white carbon, potter's clay, bentonite, Kaolin, kieselguhr, earth powder, montmorillonite, humic acids, carbamide
One or more.
Solvent is water.
Surfactant used includes T-60, T-80, T-85 selected from polyoxyethylene sorbitan fatty acid ester series；Fat
Fat polyoxyethylenated alcohol JFC；OP series is that condensation compound of alkyl phenol and epoxy ethane includes OP-10, OP-15, OP-18, OP-20；
NPE series includes NP-10, NP-15, NP-18, NP-20；Styrylphenol formaldehyde polyether series includes
33#、34#、36#、37#；Triphen ethyl phenol polyoxyethylene ether 601#, 604#, 605#；Double phenethyl phenol polyethenoxy ether 606#.
Wetting dispersing agent is selected from diisobutyl sodium naphthalene sulfonate (abbreviation pulls open powder), sodium lauryl sulphate (K12), methylene
Double bitter edible plant sodium sulfonates (being called for short NNO), acrylic acid (are called for short with propionic acid amide. copolymer (being called for short DA), dispersing agent MF
MF), the sodium lignin sulfonate (being called for short M-9) of sodium polyacrylate (being called for short DC), desaccharide classification, the lignin of desaccharide condensation and modification
Sodium sulfonate (being called for short M-10), poly carboxylic acid derivative's (being called for short CF), sodium lignin sulfonate (being called for short M-14).
Thickening agent includes xanthan gum, aluminium-magnesium silicate, arabic gum, pectin.
Binding agent one in ethyl cellulose, methylcellulose, starch.
Disintegrating agent includes sodium phosphate, sodium chloride, potassium sulfate, potassium chloride, potassium phosphate, sodium carbonate, ammonium chloride, ammonium sulfate, carbon
Acid potassium, sodium sulfate, potassium dihydrogen phosphate.
Film former includes sodium polyacrylate, pectin, polyvinylpyrrolidone, methylcellulose, animal glue.
Antifreezing agent includes ethylene glycol, isopropanol, glycerol, propylene glycol, carbamide.
The complex composition that the present invention provides, it is adaptable to preventing and treating crop bacterial disease and/or bacterial disease.
Crop bacterial disease such as bacterial leaf streak of rice and bacterial leaf spot, soft rot of cabbage, citrus bacterial canker disease, Fructus Persicae antibacterial
Property bacterial wilt, canker of tomato, the bacterial wilt of ginger etc. such as the bacterial angular leaf spot such as shothole disease, Fructus Cucumidis sativi Citrullus vulgaris, Fructus Lycopersici esculenti Semen arachidis hypogaeae.
Crop fungal disease such as downy mildew of garpe, downy mildew of cucurbits, mango anthracnose, pepper anthracnose, melon withered
Disease, citrus scab, Chinese cabbage downy mildew, black leg of beet, melon damping off, leaf spot of peanut, Roots of Peanut maize ear rot, the black shin of Nicotiana tabacum L.
Sick etc..
The complex composition that the present invention provides also can prevent and treat crop part Disease, such as tomato virus disease, Citrullus vulgaris disease
Viral disease, pepper virus disease, tobacco mosaic disease etc..
Antibacterial of the present invention can be used by commonsense method, processes as added water spray stem and leaf, it is also possible to root
Portion fills and executes, it is also possible to seed dressing or seed pelleting use.
Complex composition and the preparation of the present invention have the advantages that:
1, complex composition and the preparation thereof of the present invention has obvious synergistic function relative to single dose.
2, fungicidal spectrum is wide, and multiple diseases is respectively provided with good prevention effect.
3, the lasting period is long.After medicine, 14 days prevention effects reach more than 77% for the second time.
4, delay the service life of new medicament methylsulfonyl bacterium azoles, reduce the development cost of new medicament.
5, dosage is few, remains low, meets the trace standard of pesticide, ecological, environmental protective.
Detailed description of the invention
Present invention the following example illustrates, but does not limits the scope of the invention.Methylsulfonyl used in the present invention
The former medicine of bacterium azoles is provided by Guizhou University, and other former medicines used and preparation are commercial.Wherein active component methylsulfonyl bacterium azoles and
Tiger glue adipic acid copper.
Preparation embodiment:
For unification, below prepare the adjuvant used whole use abbreviations of embodiment or commercial disignation.
One, the preparation of suspending agent
By surfactant, antifreezing agent, thickening agent, surfactant, water mixing, through high speed shear mix homogeneously, successively
Add methylsulfonyl bacterium azoles, tiger glue adipic acid copper, abrading-ball 2～3 hours in ball crusher, prepare the suspending agent of antibacterial of the present invention.
Two, the preparation of wettable powder
By methylsulfonyl bacterium azoles, tiger glue adipic acid copper, wetting dispersing agent, white carbon, filler mix homogeneously, through jet mill powder
After broken, stir 30min, obtain the wettable powder of antibacterial of the present invention.
| Embodiment | Methylsulfonyl bacterium azoles | Tiger glue adipic acid copper | Wetting dispersing agent | White carbon | Filler |
| 7 | 2g | 40g | DC be 6g, K12 be 2g | 6g | Earth powder supplies 100g |
| 8 | 60g | 20g | M-14 is 7g | 4g | Kaolin supplies 100g |
| 9 | 20g | 10g | NNO is 7g | 10g | Potter's clay supplies 100g |
| 10 | 12.5g | 12.5g | M-9 is 8g | 3g | Kieselguhr supplies 100g |
| 11 | 16g | 4g | NNO is 6g | 0 | Earth powder supplies 100g |
| 12 | 18g | 2g | DC is 7g | 6g | Kaolin supplies 100g |
| 13 | 25g | 5g | M-10 is 8g | 9g | Bentonite supplies 100g |
| 14 | 10g | 40g | MF is 6g | 10g | Potter's clay supplies 100g |
| CK1 | 20g | 0 | DC is 7g | 6g | Kaolin supplies 100g |
Three, the preparation of water dispersible granules
By methylsulfonyl bacterium azoles, tiger glue adipic acid copper, wetting dispersing agent, white carbon, disintegrating agent, binding agent, filler mix homogeneously,
After jet mill is pulverized, stir 30min, through mediating, rear add fluidized-bed granulation dryer is carried out pelletize, be dried,
Water dispersible granules to antibacterial of the present invention.
Four, the preparation of suspension seed-coating agent
By methylsulfonyl bacterium azoles and tiger glue adipic acid copper through comminution by gas stream, add surfactant, film former, thickening agent, antifreeze
Agent and water are thoroughly mixed rear, put into sand mill in proportion and grind 2 times, until it is 2-3 μ that the fineness of the particles of suspension reaches D50
M, D90 ＜ 8 μm, obtains the suspension seed-coating agent of antibacterial of the present invention.
Five, the preparation of granule
The component of embodiment each in table is uniformly mixed, comminution by gas stream, add suitable quantity of water and then mediate, the mixture of gained
Pelletize, it is drying to obtain the granule of antibacterial of the present invention.
Toxicity Determination:
The test of following indoor biometrics uses the abundant method of Sun Yun to calculate co-toxicity coefficient (CTC) and evaluates mixed effect.
Toxicity index TI (B)=(EC of standard agent A50The EC of ÷ B agent50×100
Actual toxicity index ATI (AB)=(EC of A50The EC of ÷ AB50)×100
Theoretical toxicity index TTI (AB)=TI (A) × A percent+TI (B) × B percentage in mixture in mixture
Number
Actual measurement toxicity index (ATI)=(standard agent EC50÷ reagent agent EC50)×100
Percentage composition+B medicament the toxicity index of A in theoretical toxicity index (TTI)=A medicament toxicity index × mixture × mixed
The percentage composition of B in agent
Co-toxicity coefficient (CTC)=[mixture actual measurement toxicity index (ATI) ÷ mixture theory toxicity index (TTI)] × 100
Evaluation criterion is: co-toxicity coefficient >=120 show as potentiation；Co-toxicity coefficient≤80 show as antagonism；80<
< 120 show as summation action to co-toxicity coefficient.
Toxicity Determination embodiment one:
Test is with reference to " pesticide bioassay technology " (the old spring edits, and publishing house of Beijing Agricultural University publishes) and " agriculture
Bioassay test criterion NY/T1156.2-2006 in coyote hole ".This test uses inhibition zone method.On aseptic operating platform, by NA
Culture medium is poured on NA flat board, and after drying, the citrus processing bacteria suspension spreading rod taking 0.1ml is applied to NA flat board equably
On.After drying, punch in flat board central authorities with the card punch of diameter 7mm, then take 100 μ l medicinal liquids in aperture.Each concentration 5
Repeat.The process of sterilized water is added as blank in aperture.The calorstat aseptic culture of 28 ± 0.5 DEG C it is placed on after process,
Take out after 2d.Use decussation method to measure the antibacterial circle diameter (in units of millimeter) of each process respectively, and calculate inhibition zone
The meansigma methods of diameter, suppression ratio.Carry out statistical analysis with DPS data processing software, calculate the EC of each medicament50, then press Sun Yun
Abundant method calculates co-toxicity coefficient (CTC).
Toxicity test is the results detailed in Table 1.
Table 1 methylsulfonyl bacterium azoles and tiger glue adipic acid copper compound the joint toxicity measuring result of preventing and treating citrus bacterial canker disease
| Composition | EC50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 7.53 | 100.00 | / | / |
| Tiger glue adipic acid copper (B) | 75.64 | 9.96 | / | / |
| A:B=20:1 | 6.53 | 115.31 | 95.71 | 120.48 |
| A:B=15:1 | 6.11 | 123.24 | 94.37 | 130.59 |
| A:B=10:1 | 5.74 | 131.18 | 91.81 | 142.88 |
| A:B=5:1 | 5.62 | 133.99 | 84.99 | 157.64 |
| A:B=4:1 | 5.52 | 136.41 | 81.99 | 166.38 |
| A:B=2:1 | 6.28 | 119.90 | 69.99 | 171.33 |
| A:B=1:1 | 7.23 | 104.15 | 54.98 | 189.44 |
| A:B=1:2 | 9.85 | 76.45 | 39.97 | 191.26 |
| A:B=1:4 | 12.95 | 58.15 | 27.96 | 207.93 |
| A:B=1:5 | 16.73 | 45.01 | 24.96 | 180.31 |
| A:B=1:10 | 24.24 | 31.06 | 18.14 | 171.24 |
| A:B=1:15 | 29.71 | 25.35 | 15.58 | 162.65 |
| A:B=1:20 | 35.09 | 21.46 | 14.24 | 150.67 |
| A:B=1:30 | 42.72 | 17.63 | 12.86 | 137.07 |
| A:B=1:40 | 51.37 | 14.66 | 12.15 | 120.63 |
| A:B=1:50 | 54.82 | 13.74 | 11.72 | 117.19 |
From measurement result table 1 data, methylsulfonyl bacterium azoles and tiger glue adipic acid copper by weight in (20～1): (1～40)
In the range of the CTC of compounding preventing and treating citrus bacterial canker disease all reach more than 120, show obvious potentiation.Particularly, weight
Ratio is in (5～1): compounding in the range of (1～20), and each CTC processed is more than 150, and potentiation is especially pronounced.
Toxicity Determination embodiment two:
It is 10 by bacteria suspension concentration8cfu·mL-1Pathogen adds 0.5mL in each diameter 9cm sterilizing culture dish, then
Pour 15mL into be cooled in 45 DEG C of gravy peptone culture medium, fully mix, solidification.At culture dish bottom marker equilateral triangle 3
Away from the equidistant Angle Position of center 2.5cm, preventing Oxford cup (high 10mm, internal diameter 6mm), the medicament of dropping equivalent variable concentrations is dilute
Release liquid, under 28 DEG C of constant temperature aseptic conditions, cultivate 7d, measure antibacterial circle diameter, and calculate the meansigma methods of antibacterial circle diameter, suppression
Rate.Carry out statistical analysis with DPS data processing software, calculate the EC of each medicament50, then press the abundant method of Sun Yun and calculate co-toxicity coefficient
(CTC)。
Toxicity test is the results detailed in Table 2.
Table 2 methylsulfonyl bacterium azoles and tiger glue adipic acid copper compound the joint toxicity measuring result of preventing and treating cucumber bacterial angular leaf spot
| Composition | EC50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 6.31 | 100.00 | / | / |
| Tiger glue adipic acid copper (B) | 76.19 | 8.28 | / | / |
| A:B=20:1 | 5.47 | 115.36 | 95.63 | 120.62 |
| A:B=13:1 | 5.30 | 119.06 | 93.45 | 127.40 |
| A:B=7:1 | 5.03 | 125.45 | 88.54 | 141.69 |
| A:B=5:1 | 4.93 | 127.99 | 84.71 | 151.09 |
| A:B=3:1 | 4.77 | 132.29 | 77.07 | 171.64 |
| A:B=1:1 | 5.92 | 106.59 | 54.14 | 196.87 |
| A:B=1:3 | 10.66 | 59.19 | 31.21 | 189.65 |
| A:B=1:6 | 16.87 | 37.40 | 21.38 | 174.91 |
| A:B=1:8 | 20.54 | 30.72 | 18.47 | 166.30 |
| A:B=1:13 | 27.08 | 23.30 | 14.83 | 157.09 |
| A:B=1:20 | 33.25 | 18.98 | 12.65 | 150.03 |
| A:B=1:33 | 42.95 | 14.69 | 10.98 | 133.81 |
| A:B=1:40 | 49.20 | 12.83 | 10.52 | 121.92 |
| A:B=1:45 | 52.43 | 12.04 | 10.28 | 117.12 |
From measurement result table 2 data, methylsulfonyl bacterium azoles and tiger glue adipic acid copper by weight in (20～1): (1～40)
In the range of the CTC of compounding preventing and treating cucumber bacterial angular leaf spot all reach more than 120, show obvious potentiation.Especially
Being to be (5～1) by weight: compounding in the range of (1～20), each CTC processed is more than 150, and potentiation is especially pronounced.
Toxicity Determination embodiment three:
Preparing source of disease blade, with 4 DEG C of distillation washing lower blade back side Pseudoperonospora cubensis Sporangiums, (concentration is to be made into suspension
Every milliliter 1 × 105～1 × 107Individual Sporangium).Medicament mother solution is diluted to corresponding concentration with 0.05% Tween 80 aqueous solution,
Uniformly spray in the plant leaf two sides of cultivation in advance to 4～6 leaf periods to whole moistenings, often process 4 times and repeat, if with clear
The process that water sprays is blank, after dispenser 24h, Fresh spores capsule suspension spray is inoculated in vacuum side of blade, in every day
Alternately, temperature is 17 DEG C～22 DEG C to continuous illumination/dark each 12h, and relative humidity is cultivation under conditions of more than 90%.Work as blank
Comparison sickness rate reaches more than 50% time stage investigation incidence, calculates disease index and preventive effect, according to each drug concentration pair
The preventive effect probability value of numerical value and correspondence makees regression analysis, calculates the EC of lattice medicament50, and the common poison of mixture is calculated according to the abundant method of Sun Yun
Coefficient.
Toxicity test is the results detailed in Table 3.
Table 3 methylsulfonyl bacterium azoles and tiger glue adipic acid copper compound the joint toxicity measuring result preventing and treating downy mildew of garpe
| Composition | EC50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 35.55 | 100.00 | / | / |
| Tiger glue adipic acid copper (B) | 15.34 | 231.75 | / | / |
| A:B=20:1 | 27.76 | 128.06 | 106.27 | 120.50 |
| A:B=14:1 | 23.91 | 148.68 | 108.78 | 136.68 |
| A:B=9:1 | 21.52 | 165.20 | 113.17 | 145.96 |
| A:B=5:1 | 18.37 | 193.52 | 121.96 | 158.68 |
| A:B=2:1 | 14.53 | 244.67 | 143.92 | 170.01 |
| A:B=1:1 | 12.30 | 289.02 | 165.87 | 174.24 |
| A:B=1:4 | 9.26 | 383.91 | 205.40 | 186.91 |
| A:B=1:7 | 9.22 | 385.57 | 215.28 | 179.10 |
| A:B=1:9 | 9.48 | 375.00 | 218.57 | 171.57 |
| A:B=1:14 | 9.91 | 358.73 | 222.96 | 160.89 |
| A:B=1:20 | 10.48 | 339.22 | 225.47 | 150.45 |
| A:B=1:27 | 11.84 | 300.25 | 227.04 | 132.25 |
| A:B=1:40 | 12.88 | 276.01 | 228.53 | 120.77 |
| A:B=1:43 | 13.17 | 269.93 | 228.75 | 118.00 |
It is (20～1) by weight from measurement result table 3 data, methylsulfonyl bacterium azoles and tiger glue adipic acid copper: (1～40)
In the range of the compounding CTC preventing and treating downy mildew of garpe all reach more than 120, show obvious potentiation.Particularly, weight
Than for (5～1): compound in the range of (1～20), each CTC processed is more than 150, and potentiation is especially pronounced.
Land for growing field crops test examples
In order to clear and definite methylsulfonyl bacterium azoles alone with tiger glue adipic acid copper with time mixed to citrus bacterial canker disease, Fructus Cucumidis sativi bacillary angle speckle
The prevention effect of the bacterial diseases such as disease and downy mildew of garpe, present invention applicant different regions at home have carried out substantial amounts of field
Between test.
| Group | Medicament title | Registration card number | Organization | Medicament is originated |
| CK1 | 20% methylsulfonyl bacterium azoles wettable powder | / | / | Self-control |
| CK2 | 30% tiger glue adipic acid copper wettable powder | PD20096854 | Hainan Zhengye Zhongnong Hi-Tech Industry Co., Ltd | Commercial |
Preventing and treating citrus bacterial canker disease field efficacy experiment one:
Test method: specify application method according to " pesticide field efficacy medicine test criterion (GB/T17980.103-2004) ",
Begin to see bloom before for the first time spray pesticide, second time spray pesticide after disease occurs.Dispenser twice, each process community altogether
Area for becoming fruit tree in age 3 strain, number of repetition 4 times.Record spraying times and each dispenser date and fruit tree period of duration.
Investigation method: specify investigation method according to " pesticide field efficacy medicine test criterion (GB/T17980.103-2004) ",
Two strains are investigated in each community by 7d after dispenser for the second time, 14d, and the sampling of 5, all directions, 10 fruits of every some investigation are pressed in every strain
And the whole blades on two tips, calculate and prevent and treat preventive effect.
Leaf (really) stage division:
0 grade: every leaf (really) has scab 1～5；
3 grades: every leaf (really) has scab 6～10；
5 grades: every leaf (really) has scab 11～15；
7 grades: every leaf (really) has scab 15～20；
9 grades: every leaf (really) has scab more than 21；
Field control effectiveness test is the results detailed in Table 4.
The field control effectiveness test result of citrus bacterial canker disease prevented and treated by table 4
From test of pesticide effectiveness result table 4: when preventing citrus bacterial canker disease, methylsulfonyl bacterium azoles+tiger glue adipic acid copper and single dose
Methylsulfonyl bacterium azoles or tiger glue adipic acid copper are compared, in the case of effective ingredient dosage is identical even less, and methylsulfonyl bacterium azoles+amber
Preventive effect (effective ingredient dosage 20g/667m of the 7d of glue adipic acid copper preventing and treating citrus bacterial canker disease2) preventing obviously higher than single dose
Effect, exceeds single dose 24.24% and more than 47.56% respectively, and the preventive effect of 14d remains to reach more than 77.10%, the lasting period
Long.
Preventing and treating cucumber bacterial angular leaf spot field control effectiveness test two:
Test method: specify application method according to " pesticide field efficacy medicine test criterion (GB/T17980.110-2004) ",
First time spray pesticide when beginning to see scab, second time spray pesticide after 10d.Dispenser twice altogether, each process plot area is
20m2, number of repetition 4 times.
Investigation method: specify investigation method according to " pesticide field efficacy medicine test criterion (GB/T17980.110-2004) ",
5 samplings of open country every community diagonal, every some investigation 3 strains, investigate whole blade, account for whole blade with every leaf spot lesion area
Area percentage classification.Calculate disease index and preventive effect effect.
Stage division:
0 grade: without scab；
1 grade: lesion area accounts for less than the 5% of whole leaf area；
3 grades: lesion area accounts for the 6%～10% of whole leaf area；
5 grades: lesion area accounts for the 11%～20% of whole leaf area；
7 grades: lesion area accounts for the 21%～50% of whole leaf area；
9 grades: lesion area accounts for more than the 51% of whole leaf area.
Field control effectiveness test is the results detailed in Table 5.
The field control effectiveness test result of cucumber bacterial angular leaf spot prevented and treated by table 5
From test of pesticide effectiveness result table 5: prevention cucumber bacterial angular leaf spot, methylsulfonyl bacterium azoles+tiger glue adipic acid copper with
Single dose methylsulfonyl bacterium azoles or tiger glue adipic acid copper are compared, in the case of effective ingredient dosage is identical even less, and methylsulfonyl bacterium
7d preventive effect (effective ingredient dosage 10g/667m of azoles+tiger glue adipic acid copper preventing and treating cucumber bacterial angular leaf spot2) obviously higher than
The preventive effect of single dose, exceeds single dose 27.03% and more than 49.29% respectively, and the preventive effect of 14d remains to reach more than 79.39%,
Lasting period is long.
Prevent and treat downy mildew of garpe field control effectiveness test three:
Test method: specify application method according to " pesticide field efficacy medicine test criterion (GB/T17980.122-2004) ",
The first time spray pesticide when blade begins to see morbidity, second time spray pesticide after 10d.Dispenser twice, face, each process community altogether
Amass as open country 10 strain, number of repetition 4 times.
Investigation method: specify investigation method according to " pesticide field efficacy medicine test criterion (GB/T17980.122-2004) ",
7d after dispenser for the second time, 14d are the most climing to each community random searching 10 pumping then, investigate whole blade from top to bottom, press
Following stage division records the sick numbers of sheets at different levels and total number of sheets, calculates disease index and prevents and treats preventive effect.
Stage division:
0 grade: without scab；
1 grade: lesion area accounts for less than the 5% of whole leaf area；
3 grades: lesion area accounts for the 6%～25% of whole leaf area；
5 grades: lesion area accounts for the 26%～50% of whole leaf area；
7 grades: lesion area accounts for the 51%～75% of whole leaf area；
9 grades: lesion area accounts for more than the 76% of whole leaf area.
Field control effectiveness test is the results detailed in Table 6.
The field control effectiveness test result of downy mildew of garpe prevented and treated by table 6
From test of pesticide effectiveness result table 6: in prevention downy mildew of garpe, methylsulfonyl bacterium azoles+tiger glue adipic acid copper and single dose first
Sulphonyl bacterium azoles or tiger glue adipic acid copper are compared, in the case of effective ingredient dosage is identical even less, and methylsulfonyl bacterium azoles+amber glue
Adipic acid copper prevents and treats preventive effect (effective ingredient dosage 20g/667m of downy mildew of garpe 7d2) obviously higher than the preventive effect of single dose, point
Not exceeding single dose 46.74% and more than 25.66%, and the preventive effect of 14d remains to reach more than 78.32%, the lasting period is long.
Claims (9)
1. one kind contains methylsulfonyl bacterium azoles and the complex composition of tiger glue adipic acid copper, it is characterised in that described complex composition is by first
Sulphonyl bacterium azoles and tiger glue adipic acid copper composition；Wherein, the chemical name of methylsulfonyl bacterium azoles be 2-(to fluorophenyl)-5-mesyl-
1,3,4-diazole；The weight ratio of described methylsulfonyl bacterium azoles and tiger glue adipic acid copper is (20 ~ 1): (1 ~ 40).
The most according to claim 1 containing methylsulfonyl bacterium azoles and the complex composition of tiger glue adipic acid copper, it is characterised in that described
The weight ratio of methylsulfonyl bacterium azoles and tiger glue adipic acid copper is (5 ~ 1): (1 ~ 20).
3. one kind contains methylsulfonyl bacterium azoles and the preparation of tiger glue adipic acid copper, it is characterised in that described in any one of claim 1 ~ 2
Acceptable adjuvant on complex composition and pesticide, is prepared as preventing and treating the antibacterial of crop pest.
The most according to claim 3 containing methylsulfonyl bacterium azoles and the preparation of tiger glue adipic acid copper, it is characterised in that described compounding group
It is 0.1% ~ 90% that compound accounts for the weight percentage of described antibacterial.
The most according to claim 4 containing methylsulfonyl bacterium azoles and the preparation of tiger glue adipic acid copper, it is characterised in that described compounding group
It is 1% ~ 80% that compound accounts for the weight percentage of described antibacterial.
The most according to claim 5 containing methylsulfonyl bacterium azoles and the preparation of tiger glue adipic acid copper, it is characterised in that complex composition accounts for
The weight percentage of described antibacterial is 5% ~ 60%.
7. arbitrary described containing methylsulfonyl bacterium azoles and the preparation of tiger glue adipic acid copper according to claim 3-6, it is characterised in that described in kill
The dosage form of microbial inoculum is suspending agent, wettable powder, water dispersible granules, suspension seed-coating agent or granule.
The most according to claim 3 containing methylsulfonyl bacterium azoles and the preparation of tiger glue adipic acid copper, it is characterised in that on described pesticide
Acceptable adjuvant is the mixture of a kind of and auxiliary agent in filler and solvent.
9. the complex composition as according to any one of claim 1 ~ 2 is at preventing and treating crop bacterial disease and/or fungoid disease
Application in terms of Hai.
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| CN107810956B (en) * | 2017-10-27 | 2020-05-05 | 中国农业科学院植物保护研究所 | Bactericidal composition |
| CN107897189A (en) * | 2017-11-28 | 2018-04-13 | 谭贵友 | A kind of complex composition and preparation of the lactams of ketoxime containing isolonglifolene and tiger glue adipic acid copper |
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