CN104521988A - Compound composition containing 2-(p-fluorophenyl)-5-methanesulfonyl-1,3,4-oxadiazole and Copper(succinate+glutarate+adipate) and preparation - Google Patents
Compound composition containing 2-(p-fluorophenyl)-5-methanesulfonyl-1,3,4-oxadiazole and Copper(succinate+glutarate+adipate) and preparation Download PDFInfo
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- CN104521988A CN104521988A CN201410788175.3A CN201410788175A CN104521988A CN 104521988 A CN104521988 A CN 104521988A CN 201410788175 A CN201410788175 A CN 201410788175A CN 104521988 A CN104521988 A CN 104521988A
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- bacterium azoles
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Abstract
The invention discloses a compound composition containing 2-(p-fluorophenyl)-5-methanesulfonyl-1,3,4-oxadiazole and Copper(succinate+glutarate+adipate) and a preparation. The compound composition is composed of 2-(p-fluorophenyl)-5-methanesulfonyl-1,3,4-oxadiazole and Copper(succinate+glutarate+adipate), wherein the weight ratio of 2-(p-fluorophenyl)-5-methanesulfonyl-1,3,4-oxadiazole to Copper(succinate+glutarate+adipate) is (20-1):(1-40). The compound composition disclosed by the invention accounts for 0.1-90% of the weight percentage of a bactericide and can be used for effectively preventing and controlling various bacterial diseases such as citrus canker and cucumber bacterial angular leaf spot disease and fungous diseases such as plasmopara viticola. The compound composition has a remarkable synergistic effect and is high in preventing effect and capable of reducing the dosage of a pesticide as well as preventing and treating costs and also delaying the pesticide resistance.
Description
Technical field
The present invention relates to technical field of pesticide, the composition that particularly two kinds of pesticide activity components are composite and preparation.
Background technology
In recent years various crop bacterial disease present the trend increased the weight of year by year, occurring area increases year by year, brings significant damage to agricultural production, in the market for preventing and treating thin venereal disease evil good medicament shortcoming.Bacterial disease has the disease caused by bacterium infection process, and the pathology types that plant infects rear generation 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 also seriously caused harm the growth of crop.The medicament simultaneously preventing and treating two kinds of diseases in the market lacks, and peasant household adopts two medicaments of control bacterial disease and fungal disease to carry out scene arbitrarily mixture usually, and in order to improve control efficiency, peasant household generally strengthens dosage.Due to the not Scientific Usage of Drugs of peasant household, not only do not reach synergistic effect, also likely produce antagonism, control efficiency declines on the contrary.
For this reason, Guizhou University's independent research also has the new type bactericide " one class preventing and control crop bacteriosis oxadiazole sulfone compound (patent No. is ZL201110314246.2) " of independent intellectual property rights, and its structural formula is:
The step of preparation process of this compound and condition:
(1) the different preparation replacing sour methyl ester intermediate: with different organic acids and absolute methanol for raw material, back flow reaction 6-10 hour under sulphuric acid catalysis, decompression separating methanol, after saturated sodium bicarbonate aqueous solution adjusts ph=7, separatory obtains different methyl formates;
(2) preparation of the different formylhydrazine intermediate replaced: be dissolved in methyl alcohol with different methyl formates, then slowly add 40%-80% hydrazine hydrate, till back flow reaction is complete, separates out the formylhydrazine of different replacement after cooling;
(3) 2-sulfydryl-5-replaces the preparation of-1,3,4-oxadiazole intermediate: with the formylhydrazine of above-mentioned preparation and KOH, carbon disulphide for raw material, ethanol is solvent, and back flow reaction is complete, de-ethanol, adjusts PH=5 to obtain 2-sulfydryl-5-and replaces-1,3,4-oxadiazole;
(4) 2-thioether-5-replaces-1,3, the preparation of 4-oxadiazole intermediate: replace-1 with above-mentioned 2-sulfydryl-5-, 3,4-oxadiazole is raw material, after the water-soluble solution of hydro-oxidation sodium, be obtained by reacting corresponding sulfide compound with 1-2 by the dimethyl sulfate of mole (second) ester or halogenated hydrocarbons etc.;
(5) 2-methyl (ethyl) sulfonyl-5-replaces the preparation of-1,3,4-oxadiazole.
With corresponding thioether for raw material, be dissolved in glacial acetic acid, 2%-7% potassium permanganate solution or 30% hydrogen peroxide oxidation obtain corresponding sulfone compound.
Tiger glue adipic acid copper, chemical name is succinic acid copper, glutaric acid copper, adipic acid copper, and be the mixture of succinic acid, glutaric acid and adipic acid complex copper, molecular formula is [(CH
2)
17(COO)
2]
ncu is known and published pesticide species.
Summary of the invention
Dui Yu oxadiazole sulfone compound, applicant researches and develops further, is selected from the fluorine in halogen atom, R as Rn
2select the methyl of C1-C5 alkyl and get the structural formula of oxadiazole sulfone compound:
Its chemical name is 2-(to fluorophenyl)-5-mesyl-1,3,4-oxadiazole, is called for short methylsulfonyl bacterium azoles.
The concrete syntheti c route of compound methylsulfonyl bacterium azoles is as follows:
(1) to the synthesis of fluorobenzoyl hydrazine
(2) 2-sulfydryl-5-is to the synthesis of fluorophenyl-1,3,4-oxadiazole
(3) 2-Dimethyl sulfide-5-is to the synthesis of fluorophenyl-1,3,4-oxadiazole
(4) 2-(to fluorophenyl)-5-mesyl-1,3,4-oxadiazole target compound is prepared
Applicant studies discovery further, and methylsulfonyl bacterium azoles is the control bacterial disease medicament of novel structure, by suppressing the synthesis of pathogene energy, the growth of anti-bacteria and breeding.Methylsulfonyl bacterium azoles has the feature of interior suction, conduction, and after infiltration blade epidermis, energy transporting is to other positions of same blade.A large amount of isolated tests shows, methylsulfonyl bacterium azoles has good inhibitory action to causing the various pathogenetic bacterias of phytobacterial disease, and namely directly anti-bacteria is bred.Through repeatedly pot experiment and field control effectiveness test checking, show that methylsulfonyl bacterium azoles all has good control efficiency to crop bacterial disease, especially good control effect is all had to bacterial blight of rice, slice disease, tobacco bacterial wilt, bacterial wilt of tomato, citrus bacterial canker disease etc., and plant growth can be stimulated to a certain extent healthy and strong, improve the resistance of crop.This compound has efficiently, the feature of wide spectrum, use safety, is a bactericide having much exploitation potential quality.
Tiger glue adipic acid copper, chemical name is succinic acid copper, glutaric acid copper, adipic acid copper, and be the mixture of succinic acid, glutaric acid and adipic acid complex copper, molecular formula is [(CH
2)
17(COO)
2]
ncu is known and published pesticide species.
In view of this, for the deficiency that prior art exists, the object of the present invention is to provide containing methylsulfonyl bacterium azoles and amber and the complex composition of glue adipic acid copper and preparation.Contrast with single dose; this complex composition has obvious synergistic effect; can effectively prevent and treat crop bacterial disease and fungal disease; and reduce the using dosage of agricultural chemicals; save drug cost; fungicidal spectrum is more extensive, delays the pesticide resistance of pathogen, is conducive to the comprehensive regulation of environmental protection and agricultural disease.
In order to reach object of the present invention, the technical solution used in the present invention is:
Contain a complex composition for methylsulfonyl bacterium azoles and tiger glue adipic acid copper, this complex composition is made up of methylsulfonyl bacterium azoles and tiger glue adipic acid copper; The chemical name of described methylsulfonyl bacterium azoles is 2-(to fluorophenyl)-5-mesyl-1,3,4-oxadiazole.
In order to ensure that complex composition has better preventive effect and synergistic effect, the above-described complex composition containing methylsulfonyl bacterium azoles and tiger 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 better preventive effect and synergistic effect, the above-described complex composition containing methylsulfonyl bacterium azoles and tiger 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 a kind of preparation containing methylsulfonyl bacterium azoles and tiger glue adipic acid copper, and said preparation book, by adjuvant acceptable on above-described complex composition and agricultural chemicals, is prepared into the bactericide preventing and treating crop pest.
In order to ensure that bactericide has better preventive effect, the above is containing the preparation of methylsulfonyl bacterium azoles and tiger glue adipic acid copper, and as preferably, the weight percentage that described complex composition accounts for above-mentioned bactericide is 0.1%-90%.
The above contains the preparation of methylsulfonyl bacterium azoles and tiger glue adipic acid copper, and preferably, the weight percentage that described complex composition accounts for above-mentioned bactericide is 1%-80%.
The above contains the preparation of methylsulfonyl bacterium azoles and tiger glue adipic acid copper, and more preferably, the weight percentage that described complex composition accounts for above-mentioned bactericide is 5%-60%.
In order to the demand that satisfied difference uses, bactericide of the present invention can be made into multiple formulation, as preferably, provides in embodiment of the present invention, and the formulation of bactericide is suspending agent, wetting powder, water dispersible granules, suspension seed-coating agent or granule.Be not limited only to formulation provided by the invention.
In order to play the bactericidal effect of complex composition better, described bactericide, except comprising compounded combination beyond the region of objective existence, also comprises acceptable adjuvant on agricultural chemicals.Wherein adjuvant is the mixture of a kind of and auxiliary agent in filler and solvent.
Described auxiliary agent is surfactant, wetting dispersing agent, thickener, binding agent, disintegrant, film forming agent.Add other conventional functionality auxiliary agents such as antifreezing agent, thickener, stabilizing agent, defoamer if desired.
Filler is one or more in white carbon, potter's clay, bentonite, kaolin, diatomite, earth powder, montmorillonite, humic acid, urea.
Solvent is water.
Surfactant used is selected from polyoxyethylene sorbitan fatty acid ester series and comprises T-60, T-80, T-85; Fatty alcohol-polyoxyethylene ether JFC; OP series comprises OP-10, OP-15, OP-18, OP-20 for condensation compound of alkyl phenol and epoxy ethane; Polyoxyethylene nonylphenol ether series comprises NP-10, NP-15, NP-18, NP-20; Styrylphenol formaldehyde polyether series comprises 33#, 34#, 36#, 37#; Triphen ethyl phenol APEO 601#, 604#, 605#; Two phenethyl phenol polyethenoxy ether 606#.
Wetting dispersing agent is selected from diisobutyl sodium naphthalene sulfonate (abbreviation pulls open powder), lauryl sodium sulfate (K12), di-2-ethylhexylphosphine oxide bitter edible plant sodium sulfonate (being called for short NNO), acrylic acid and propionamide copolymer (being called for short DA), dispersing agent MF (being called for short MF), Sodium Polyacrylate (being called for short DC), desugar the sodium lignin sulfonate of classification (being called for short M-9), the sodium lignin sulfonate (being called for short M-10) of desugar condensation and modification, poly carboxylic acid derivative's (being called for short CF), sodium lignin sulfonate (being called for short M-14).
Thickener comprises xanthans, aluminium-magnesium silicate, gum Arabic, pectin.
Binding agent is selected from the one in ethyl cellulose, methylcellulose, starch.
Disintegrant comprises sodium phosphate, sodium chloride, potassium sulfate, potassium chloride, potassium phosphate, sodium carbonate, ammonium chloride, ammonium sulfate, potash, sodium sulphate, potassium dihydrogen phosphate.
Film forming agent comprises Sodium Polyacrylate, pectin, polyvinylpyrrolidone, methylcellulose, animal glue.
Antifreezing agent comprises ethylene glycol, isopropyl alcohol, glycerine, propane diols, urea.
Complex composition provided by the invention, is applicable to control crop bacterial disease and/or bacterial disease.
Crop bacterial disease is as the bacterial wilt such as bacterial angular leaf spot, tomato peanut, canker of tomato, bacterial wilt of ginger etc. such as bacterial leaf streak of rice and bacterial leaf spot, soft rot of cabbage, citrus bacterial canker disease, peach bacterial shot hole, cucumber watermelons.
Crop fungal disease is as downy mildew of garpe, downy mildew of cucurbits, mango anthracnose, pepper anthracnose, cucurbits fusarium wilt, citrus scab, Chinese cabbage downy mildew, black leg of beet, melon damping off, leaf spot of peanut, Roots of Peanut maize ear rot, black shank etc.
Complex composition provided by the invention also can prevent and treat crop part Disease, as tomato virus disease, watermelon virus disease, pepper virus disease, tobacco mosaic etc.
Bactericide of the present invention can be used by commonsense method, as added the process of water spray cauline leaf, also root filling can execute, can also dress seed or seed pelleting use.
Complex composition of the present invention and preparation have the following advantages and good effect:
1, complex composition of the present invention and preparation thereof have obvious synergistic function relative to single dose.
2, fungicidal spectrum is wide, all has good control efficiency to multiple diseases.
3, the lasting period is long.After second time medicine, 14 days control efficiency reach more than 77%.
4, delay the service life of new medicament methylsulfonyl bacterium azoles, reduce the development cost of new medicament.
5, dosage is few, residual low, meets the trace standard of pesticide, ecological, environmental protective.
Embodiment
The present invention's the following example is described, but does not limit the scope of the invention.The former medicine of methylsulfonyl bacterium azoles used in the present invention 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 abbreviation of embodiment or commercial disignation.
One, the preparation of suspending agent
By surfactant, antifreezing agent, thickener, surfactant, water mixing, mix through high speed shear, add methylsulfonyl bacterium azoles, tiger glue adipic acid copper successively, abrading-ball 2 ~ 3 hours in ball crusher, the suspending agent of obtained bactericide of the present invention.
Two, the preparation of wetting powder
Methylsulfonyl bacterium azoles, tiger glue adipic acid copper, wetting dispersing agent, white carbon, filler are mixed, after airslide disintegrating mill is pulverized, stirs 30min, obtain the wetting powder of bactericide of the present invention.
| Embodiment | Methylsulfonyl bacterium azoles | Tiger glue adipic acid copper | Wetting dispersing agent | White carbon | Filler |
| 7 | 2g | 40g | DC is 6g, K12 is 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 | Diatomite 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
Methylsulfonyl bacterium azoles, tiger glue adipic acid copper, wetting dispersing agent, white carbon, disintegrant, binding agent, filler are mixed, after airslide disintegrating mill is pulverized, stir 30min, through mediating, after add in fluidized-bed granulation dryer and carry out granulation, drying, obtain the water dispersible granules of bactericide of the present invention.
Four, the preparation of suspension seed-coating agent
By methylsulfonyl bacterium azoles and tiger glue adipic acid copper through air-flow crushing, adding surfactant, film forming agent, thickener, antifreezing agent and water mixes rear completely, drop into sand mill in proportion and grind 2 times, until it is 2-3 μm that the grain fineness of suspension reaches D50, D90 < 8 μm, obtains the suspension seed-coating agent of bactericide of the present invention.
Five, the preparation of granule
By the component Homogeneous phase mixing of each embodiment in table, air-flow crushing, adds suitable quantity of water and then mediates, and the mixture pelleting of gained, is drying to obtain the granule of bactericide of the present invention.
toxicity Determination:
Following indoor biometrics test adopts the abundant method of Sun Yun to calculate co-toxicity coefficient (CTC) and evaluates mixed effect.
Toxicity index TI (B)=(EC of standard agent A
50the EC of ÷ B agent
50× 100
Actual toxicity index ATI (AB)=(EC of A
50the EC of ÷ AB
50) × 100
Theoretical toxicity index TTI (AB)=TI (the A) × A percentage+TI (B) in the mixture × percentage of B in mixture
Actual measurement toxicity index (ATI)=(standard agent EC
50÷ reagent agent EC
50) × 100
In theoretical toxicity index (TTI)=A medicament toxicity index × mixture A percentage composition+B medicament toxicity index × mixture in the percentage composition of B
Co-toxicity coefficient (CTC)=[the theoretical toxicity index (TTI) of mixture actual measurement toxicity index (ATI) ÷ mixture] × 100
Evaluation criterion is: co-toxicity coefficient >=120 show as synergistic effect; Co-toxicity coefficient≤80 show as antagonism; 80< co-toxicity coefficient <120 shows as summation action.
Toxicity Determination embodiment one:
Test is with reference to " pesticide bioassay technology " (old spring chief editor, publishing house of Beijing Agricultural University publishes) and " farm-chemical indoor determination test rule NY/T1156.2-2006 ".This test adopts inhibition zone method.On aseptic operating platform, poured into by NA medium on NA flat board, after drying, the citrus processing bacteria suspension spreading rod getting 0.1ml is applied on NA flat board equably.After drying, punch in dull and stereotyped central authorities with the card punch of diameter 7mm, then get 100 μ l liquids in aperture.Each concentration 5 repetition.To add the process of sterile water in aperture for blank.Be placed on the insulating box aseptic culture of 28 ± 0.5 DEG C after process, take out after 2d.Adopt right-angled intersection method to measure the antibacterial circle diameter (in units of millimeter) of each process respectively, and calculate mean value, the inhibiting rate of antibacterial circle diameter.Carry out statistical analysis with DPS data processing software, calculate the EC of each medicament
50, then press the abundant method of Sun Yun and calculate co-toxicity coefficient (CTC).
Toxicity test is the results detailed in Table 1.
The joint toxicity measuring result of table 1 methylsulfonyl bacterium azoles and the composite control citrus bacterial canker disease of tiger glue adipic acid copper
| Composition | EC 50(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 are by weight in (20 ~ 1): in the scope of (1 ~ 40), the CTC of composite control citrus bacterial canker disease all reaches more than 120, shows obvious synergistic effect.Particularly, weight ratio is in (5 ~ 1): composite in the scope of (1 ~ 20), and the CTC of each process is more than 150, and synergy is particularly remarkable.
Toxicity Determination embodiment two:
Be 10 by bacteria suspension concentration
8cfumL
-1pathogen adds 0.5mL in each diameter 9cm sterilizing culture dish, then pours 15mL into and be cooled in 45 DEG C of gravy peptone medium, fully mixes, solidifies.At the equidistant Angle Position of 3 Ge Ju center 2.5cm of culture dish bottom marker equilateral triangle, prevent Oxford cup (high 10mm, internal diameter 6mm), drip the medicament dilution of equivalent variable concentrations, 7d is cultivated under 28 DEG C of constant temperature aseptic conditions, measure antibacterial circle diameter, and calculate mean value, the inhibiting rate of antibacterial circle diameter.Carry out statistical analysis with DPS data processing software, calculate the EC of each medicament
50, then press the abundant method of Sun Yun and calculate co-toxicity coefficient (CTC).
Toxicity test is the results detailed in Table 2.
The joint toxicity measuring result of table 2 methylsulfonyl bacterium azoles and the composite control cucumber bacterial angular leaf spot of tiger glue adipic acid copper
| Composition | EC 50(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 are by weight in (20 ~ 1): in the scope of (1 ~ 40), the CTC of composite control cucumber bacterial angular leaf spot all reaches more than 120, shows obvious synergistic effect.Particularly, be (5 ~ 1) by weight: composite in the scope of (1 ~ 20), the CTC of each process is more than 150, and synergy is particularly remarkable.
Toxicity Determination embodiment three:
Prepare pathogeny blade, with 4 DEG C of distillation washing lower blade back side Pseudoperonospora cubensis sporangiums, (concentration is every milliliter 1 × 10 to be made into suspension
5~ 1 × 10
7individual sporangium).The medicament mother liquor 0.05% Tween 80 aqueous solution is diluted to corresponding concentration, the plant leaf two sides evenly sprayed in cultivation in advance to 4 ~ 6 leaf periods soaks to whole, often process and repeat for 4 times, if be blank with the process of fresh water spraying, after dispenser 24h, Fresh spores capsule suspension spray is inoculated in vacuum side of blade, the continuous illumination in every day/dark each 12h alternately, temperature is 17 DEG C ~ 22 DEG C, and relative moisture is cultivate under the condition of more than 90%.When the blank incidence of disease reaches more than 50% time stage investigation incidence, calculate disease index and preventive effect, the preventive effect probability value according to each drug concentration logarithm value and correspondence does regression analysis, calculates the EC of lattice medicament
50, and the co-toxicity coefficient of mixture is calculated according to the abundant method of Sun Yun.
Toxicity test is the results detailed in Table 3.
Table 3 methylsulfonyl bacterium azoles and the composite joint toxicity measuring result of preventing and treating downy mildew of garpe of tiger glue adipic acid copper
| Composition | EC 50(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 |
From measurement result table 3 data, methylsulfonyl bacterium azoles and tiger glue adipic acid copper are (20 ~ 1) by weight: in the scope of (1 ~ 40), the composite CTC preventing and treating downy mildew of garpe all reaches more than 120, shows obvious synergistic effect.Particularly, weight ratio is (5 ~ 1): composite in the scope of (1 ~ 20), and the CTC of each process is more than 150, and synergy is particularly remarkable.
land for growing field crops test examples
In order to clear and definite methylsulfonyl bacterium azoles and tiger glue adipic acid copper alone with time mixed to the control efficiency of the bacterial diseases such as citrus bacterial canker disease, cucumber bacterial angular leaf spot and downy mildew of garpe, present invention applicant at home different regions has carried out a large amount of field trials.
| Group | Medicament title | Registration card number | Organization | Medicament is originated |
| CK1 | 20% methylsulfonyl bacterium azoles wetting powder | / | / | Self-control |
| CK2 | 30% tiger glue adipic acid copper wetting powder | PD20096854 | Hainan Zhengye Zhongnong Hi-Tech Industry Co., Ltd | Commercial |
Control citrus bacterial canker disease field efficacy experiment one:
Test method: according to " pesticide field efficacy medicine test criterion (GB/T17980.103-2004) " regulation application method, the beginning see bloom before first time spray pesticide, there is second time spray pesticide after disease.Dispenser twice altogether, each process plot area is for becoming fruit tree 3 strain in age, number of repetition 4 times.Record spraying times and each dispenser date and fruit tree breeding time.
Investigation method: according to " pesticide field efficacy medicine test criterion (GB/T17980.103-2004) " regulation investigation method, 7d after second time dispenser, 14d investigates two strains to each community, every strain is by the sampling of 5, all directions, often whole blades investigated on 10 fruits and 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 is compared with single dose methylsulfonyl bacterium azoles or tiger glue adipic acid copper, when active ingredient dosage identical even less, preventive effect (the active ingredient dosage 20g/667m of the 7d of methylsulfonyl bacterium azoles+tiger glue adipic acid copper control citrus bacterial canker disease
2) all apparently higher than the preventive effect of single dose, exceed single dose more than 24.24% and 47.56% respectively, and the preventive effect of 14d still can reach more than 77.10%, the lasting period is long.
Control cucumber bacterial angular leaf spot field control effectiveness test two:
Test method: according to " pesticide field efficacy medicine test criterion (GB/T17980.110-2004) " regulation application method, when beginning to see scab first time spray pesticide, second time spray pesticide after 10d.Dispenser twice altogether, each process plot area is 20m
2, number of repetition 4 times.
Investigation method: according to " pesticide field efficacy medicine test criterion (GB/T17980.110-2004) " regulation investigation method, 5 samplings of open country every community diagonal, often some investigation 3 strains, investigate whole blade, account for the classification of whole blade area percentage with every leaf spot lesion area.Calculate disease index and preventive effect effect.
Stage division:
0 grade: without scab;
1 grade: lesion area accounts for less than 5% of whole leaf area;
3 grades: lesion area accounts for 6% ~ 10% of whole leaf area;
5 grades: lesion area accounts for 11% ~ 20% of whole leaf area;
7 grades: lesion area accounts for 21% ~ 50% of whole leaf area;
9 grades: lesion area accounts for more than 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: at prevention cucumber bacterial angular leaf spot, methylsulfonyl bacterium azoles+tiger glue adipic acid copper is compared with single dose methylsulfonyl bacterium azoles or tiger glue adipic acid copper, when active ingredient dosage identical even less, 7d preventive effect (the active ingredient dosage 10g/667m of methylsulfonyl bacterium azoles+tiger glue adipic acid copper control cucumber bacterial angular leaf spot
2) all apparently higher than the preventive effect of single dose, exceed single dose more than 27.03% and 49.29% respectively, and the preventive effect of 14d still can reach more than 79.39%, the lasting period is long.
Prevent and treat downy mildew of garpe field control effectiveness test three:
Test method: according to " pesticide field efficacy medicine test criterion (GB/T17980.122-2004) " regulation application method, when blade begins to see morbidity first time spray pesticide, second time spray pesticide after 10d.Dispenser twice altogether, each process plot area is open country 10 strain, number of repetition 4 times.
Investigation method: according to " pesticide field efficacy medicine test criterion (GB/T17980.122-2004) " regulation investigation method, 7d after second time dispenser, pumping is newly climing then to each community random searching 10 for 14d, investigate whole blade from top to bottom, by the following stage division record sick number of sheets at different levels and total number of sheets, calculate disease index and prevent and treat preventive effect.
Stage division:
0 grade: without scab;
1 grade: lesion area accounts for less than 5% of whole leaf area;
3 grades: lesion area accounts for 6% ~ 25% of whole leaf area;
5 grades: lesion area accounts for 26% ~ 50% of whole leaf area;
7 grades: lesion area accounts for 51% ~ 75% of whole leaf area;
9 grades: lesion area accounts for more than 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 is compared with single dose methylsulfonyl bacterium azoles or tiger glue adipic acid copper, when active ingredient dosage identical even less, methylsulfonyl bacterium azoles+tiger glue adipic acid copper prevents and treats preventive effect (the active ingredient dosage 20g/667m of downy mildew of garpe 7d
2) all apparently higher than the preventive effect of single dose, exceed single dose more than 46.74% and 25.66% respectively, and the preventive effect of 14d still can reach more than 78.32%, the lasting period is long.
Claims (10)
1. contain a complex composition for methylsulfonyl bacterium azoles and tiger glue adipic acid copper, it is characterized in that, described 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-oxadiazole.
2. the complex composition containing methylsulfonyl bacterium azoles and tiger glue adipic acid copper according to claim 1, it is characterized in that, the weight ratio of described methylsulfonyl bacterium azoles and tiger glue adipic acid copper is (20 ~ 1): (1 ~ 40).
3. the complex composition containing methylsulfonyl bacterium azoles and tiger glue adipic acid copper according to claim 2, it is characterized in that, the weight ratio of described methylsulfonyl bacterium azoles and tiger glue adipic acid copper is (5 ~ 1): (1 ~ 20).
4. contain a preparation for methylsulfonyl bacterium azoles and tiger glue adipic acid copper, it is characterized in that, by acceptable adjuvant on the complex composition described in any one of claims 1 to 3 and agricultural chemicals, be prepared into the bactericide preventing and treating crop pest.
5. contain the preparation of methylsulfonyl bacterium azoles and tiger glue adipic acid copper according to claim 4, it is characterized in that, the weight percentage that described complex composition accounts for described bactericide is 0.1% ~ 90%.
6. contain the preparation of methylsulfonyl bacterium azoles and tiger glue adipic acid copper according to claim 5, it is characterized in that, the weight percentage that described complex composition accounts for described bactericide is 1% ~ 80%.
7. contain the preparation of methylsulfonyl bacterium azoles and tiger glue adipic acid copper according to claim 6, it is characterized in that, the weight percentage that complex composition accounts for described bactericide is 5% ~ 60%.
8., according to the arbitrary described preparation containing methylsulfonyl bacterium azoles and tiger glue adipic acid copper of claim 4-7, it is characterized in that, the formulation of described bactericide is suspending agent, wetting powder, water dispersible granules, suspension seed-coating agent or granule.
9. according to claim 4 containing the preparation of methylsulfonyl bacterium azoles and tiger glue adipic acid copper, it is characterized in that, on described agricultural chemicals, acceptable adjuvant is the mixture of a kind of and auxiliary agent in filler and solvent.
10. the application of the complex composition according to any one of claims 1 to 3 in control crop bacterial disease and/or fungal disease.
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| CN105941426A (en) * | 2016-07-25 | 2016-09-21 | 李祥英 | Pesticide composition containing oxathiapiprolin and copper succinate |
| CN107810956A (en) * | 2017-10-27 | 2018-03-20 | 中国农业科学院植物保护研究所 | A kind of 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 |
| CN109535097A (en) * | 2019-01-08 | 2019-03-29 | 贵州大学 | The molecular probe and its preparation method and application of one kind detection dihydrolipoic acid succinyltransferase |
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| US5166165A (en) * | 1990-10-20 | 1992-11-24 | Bayer Aktiengesellschaft | Fungicidal agents based on heterocyclically substituted sulphones |
| CN101107932A (en) * | 2007-07-11 | 2008-01-23 | 湖南万家丰科技有限公司 | Bactericial composition containing Difenoconazole and copper fungicide |
| CN102499247A (en) * | 2011-10-17 | 2012-06-20 | 贵州大学 | Oxadiazole sulfone compound for controlling bacterial crop diseases |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5166165A (en) * | 1990-10-20 | 1992-11-24 | Bayer Aktiengesellschaft | Fungicidal agents based on heterocyclically substituted sulphones |
| CN101107932A (en) * | 2007-07-11 | 2008-01-23 | 湖南万家丰科技有限公司 | Bactericial composition containing Difenoconazole and copper fungicide |
| CN102499247A (en) * | 2011-10-17 | 2012-06-20 | 贵州大学 | Oxadiazole sulfone compound for controlling bacterial crop diseases |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105941426A (en) * | 2016-07-25 | 2016-09-21 | 李祥英 | Pesticide composition containing oxathiapiprolin and copper succinate |
| CN107810956A (en) * | 2017-10-27 | 2018-03-20 | 中国农业科学院植物保护研究所 | A kind of bactericidal composition |
| 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 |
| CN109535097A (en) * | 2019-01-08 | 2019-03-29 | 贵州大学 | The molecular probe and its preparation method and application of one kind detection dihydrolipoic acid succinyltransferase |
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