CN104488930A - Compound composition containing methanesulphonyl myclobutanil and zhongshengmycin and preparation - Google Patents
Compound composition containing methanesulphonyl myclobutanil and zhongshengmycin and preparation Download PDFInfo
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Abstract
The invention discloses a compound composition containing methanesulphonyl myclobutanil and zhongshengmycin. The compound composition comprises two active ingredients, wherein the first active ingredient is the methanesulphonyl myclobutanil and the second active ingredient is the zhongshengmycin; the weight ratio of the first active ingredient to the second active ingredient is (40:1)-(1:20); the chemical name of the methanesulphonyl myclobutanil is 2-(p-fluorophenyl)-5-methylsulfonyl-1,3,4-oxadiazole. The compound composition is used for controlling the plant diseases, especially the plant bacterial diseases. After being compounded, the two active ingredients are remarkable in synergetic interaction effect, high in control efficiency, less in dosage and long in lasting period so as to achieve the aim of effectively controlling various crop bacterial diseases, delaying or resisting the drug resistance and prolonging the service life of the product.
Description
Technical field
The present invention relates to technical field of pesticide, be specifically related to the composite composition of two fungicide active ingredients and preparation thereof.
Background technology
Zhongshengmycin is known and a kind of bactericide be disclosed, but again and again uses due to it, and disease produces certain pesticide resistance to it, and biologically active declines, and preventive effect is not ideal, limits its use.The resistance problem of agricultural disease is a global problem.Along with continuity and the not scientifical use agricultural chemicals of disease chemical control, the pesticide species that disease develops immunity to drugs increases, and peasant uses these pesticide species controlling disease to strengthen dosage, but still can not obtain good preventive effect.Therefore, need to research and develop efficient, wide spectrum, low toxicity bactericidal pesticide composition.
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.
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.A kind of novel bactericide methylsulfonyl bacterium azoles of disease development that applicant occurs for Different Crop.But because a kind of new bactericide is used alone, also easily develop immunity to drugs.Through a large amount of tests, find methylsulfonyl bacterium azoles and Zhongshengmycin composite remarkably productive.
In view of this, for the deficiency that prior art exists, the object of the invention is to a kind of complex composition and the preparation thereof that contain methylsulfonyl bacterium azoles and Zhongshengmycin.This complex composition and preparation have obvious synergistic effect relative to single dose, improve control efficiency, and reduce the using dosage of agricultural chemicals, reduce cost accounting, delay pathogen pesticide resistance simultaneously.
For reaching goal of the invention, the technical solution used in the present invention is:
Contain a complex composition for methylsulfonyl bacterium azoles and Zhongshengmycin, described complex composition is made up of methylsulfonyl bacterium azoles and Zhongshengmycin; Wherein, the chemical name of methylsulfonyl bacterium azoles is 2-(to fluorophenyl)-5-mesyl-1,3,4-oxadiazole.
The above-described complex composition containing methylsulfonyl bacterium azoles and Zhongshengmycin, preferably, described methylsulfonyl bacterium azoles and the weight ratio of Zhongshengmycin are (40 ~ 1): (1 ~ 20).
The above-described complex composition containing methylsulfonyl bacterium azoles and Zhongshengmycin, more preferably, described methylsulfonyl bacterium azoles and Zhongshengmycin weight ratio be (10 ~ 1): (1 ~ 5).
The present invention also provides a kind of preparation containing methylsulfonyl bacterium azoles and Zhongshengmycin, comprises acceptable carrier and auxiliary agent on above-mentioned complex composition and agricultural chemicals, is then prepared into disinfectant use in agriculture.
The above-described preparation containing methylsulfonyl bacterium azoles and Zhongshengmycin, as preferably, the weight percentage that described complex composition accounts for described bactericide is 0.1 ~ 90%.
The above-described preparation containing methylsulfonyl bacterium azoles and Zhongshengmycin, further preferably, the weight percentage that described complex composition accounts for described bactericide is 1 ~ 80%.
In order to meet different user demands, bactericide of the present invention can be multiple formulation.
As preferred mode, in embodiments more provided by the invention, the formulation of described bactericide is wetting powder, suspending agent, aqueous emulsion, water dispersible granules, seed treatment dry powder doses or granule.
Carrier of the present invention can be solid packing, liquid diluent or solvent, and any carrier being generally used for preparing bactericide all can use.
Solid packing is selected from one or more in white carbon, clay, attapulgite, potter's clay, bentonite, kaolin, diatomite, earth powder, montmorillonite, urea, NPK trace element.
Liquid diluent is water.
Solvent is methyl naphthalene.
Auxiliary agent of the present invention can comprise one or more in emulsifier, wetting agent, dispersant, defoamer, thickener, disintegrant and antifreezing agent as required, can also comprise other auxiliary agents that the industry is conventional as required.
Emulsifier is selected from polyoxyethylene sorbitan fatty acid ester, fatty alcohol-polyoxyethylene ether, condensation compound of alkyl phenol and epoxy ethane, polyoxyethylene nonylphenol ether, triphen ethyl phenol APEO, two phenethyl phenol polyethenoxy ether, calcium dodecyl benzene sulfonate.
Wetting agent is selected from EO/PO block polyether, lauryl sodium sulfate, fat alcohol ethoxyl compound, tallow ethyoxyl ammonium salt, alkylnaphthalene sulfonate, fatty alcohol polyoxyethylene ether sulfate, acyl group glutamate.
Dispersant is selected from naphthalene sulfonic acid condensate sodium salt, phenolsulfonic acid condensation product sodium salt, methyl naphthalene sulfonate formaldehyde condensate, sodium lignin sulfonate, sodium metnylene bis-naphthalene sulfonate, acrylate homopolymer sodium salt, polymeric polycarboxylic acid salt, dioctyl sodium sulphosuccinate salt, maleic acid-acrylic acid copolymer sodium salt.
Thickener is selected from xanthans, Magnesiumaluminumsilicate, sodium carboxymethylcellulose, starch phosphate sodium, octenyl succinic acid starch or polyvinyl alcohol.
Antifreezing agent is selected from ethylene glycol, propane diols, glycerine, isopropyl alcohol, urea.
Disintegrant is selected from sodium chloride, ammonium sulfate, sodium sulphate, ammonium chloride, sodium phosphate, starch.
Defoamer is silicone oil, glycerine-polyethers-propane copolymer-glycerine, dimethicone.
Binding agent is polyvinyl alcohol.
The present invention also provides the described purposes of composition pesticide in control crop bacterial disease and fungal disease.
Described bacterial disease can be X. c. pv. oryzicola and bacterial leaf-blight, tobacco bacterial wilt, bacterial wilt of peanut, cucurbit wilt, solanaceous vegetable bacterial wilt, soft rot of cabbage, cucumber bacterial angular leaf spot, citrus bacterial canker disease, canker of tomato, ring rot of apple germ, wheat scab.
Bactericide of the present invention can be used by commonsense method, as being watered the process of spraying cauline leaf, also root filling can execute, can also dress seed or seed pelleting use.Be mainly used in the crops such as paddy rice, tobacco, solanaceous vegetable, melon, Chinese cabbage, oranges and tangerines.
As preferably, described plant disease main bacteria venereal disease evil and fungal disease, wherein bacterial disease is Xanthomonas oryzae, bacterial wilt of tomato bacterium;
Complex composition of the present invention and bactericide have advantage compared to existing technology:
1, methylsulfonyl bacterium azoles and Zhongshengmycin rationally composite in certain proportion after, be not the simple superposition of two compositions, both are composite shows obvious synergistic function, and co-toxicity coefficient is all greater than 120.
2, when the dosage of complex composition of the present invention is less compared with single dose, high to the control efficiency of disease, field efficacy is all more than 75%, and the preventive effect after composite is obviously better than single dose, and preventive effect exceeds single dose at least 19.62%.
3, complex composition of the present invention expands fungicidal spectrum, can prevent and treat bacterial disease, also can prevent and treat fungal disease, can also slow down the pesticide resistance of pathogen to methylsulfonyl bacterium azoles simultaneously.
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 medicament are commercial.Wherein active component (A) is methylsulfonyl bacterium azoles, hereinafter referred to as first sulphur; Active component (B) is Zhongshengmycin.
Embodiment 1:
| 21% first sulphur Zhongshengmycin suspending agent (20:1) | |
| Methylsulfonyl bacterium azoles | 20％ |
| Zhongshengmycin | 1％ |
| Polyoxyethylene nonylphenol ether | 4％ |
| Triphen ethyl phenol APEO | 3％ |
| Octenyl succinic acid starch | 4％ |
| Isopropyl alcohol | 4％ |
| Glycerine-polyethers-propane copolymer-glycerine | 1％ |
| Water | Supply 100% |
By all materials, stir, drop in sand mill, by material ball milling, and control desired flow and temperature, 325 mesh sieves, then mix and blend excessively 20 minutes, obtain product.
Embodiment 2:
By all materials, stir, drop in sand mill, by material ball milling, and control desired flow and temperature, 325 mesh sieves, then mix and blend excessively 20 minutes, obtain product.
Embodiment 3:
By all materials, stir, drop in sand mill, by material ball milling, and control desired flow and temperature, 325 mesh sieves, then mix and blend excessively 20 minutes, obtain product.
Embodiment 4:
By all materials, stir, drop in sand mill, by material ball milling, and control desired flow and temperature, 325 mesh sieves, then mix and blend excessively 20 minutes, obtain product.
Embodiment 5:
By all materials, stir, drop in sand mill, by material ball milling, and control desired flow and temperature, 325 mesh sieves, then mix and blend excessively 20 minutes, obtain product.
Embodiment 6:
By said mixture Homogeneous phase mixing, air-flow crushing, adds suitable quantity of water and mediates, and the mixture pelleting of gained, is drying to obtain product.
Embodiment 7:
By said mixture Homogeneous phase mixing, air-flow crushing, adds suitable quantity of water and mediates, and the mixture pelleting of gained, is drying to obtain product.
Embodiment 8:
By said mixture Homogeneous phase mixing, air-flow crushing, adds suitable quantity of water and mediates, and the mixture pelleting of gained, is drying to obtain product.
Embodiment 9:
By said mixture Homogeneous phase mixing, air-flow crushing, adds suitable quantity of water and mediates, and the mixture pelleting of gained, is drying to obtain product.
Embodiment 10:
By said mixture Homogeneous phase mixing, air-flow crushing, adds suitable quantity of water and mediates, and the mixture pelleting of gained, is drying to obtain product.
Embodiment 11:
First weighing is dropped into well the mixing of various composition mixing and blending machine, then namely obtain product through air-flow crushing by 325 mesh sieves.
Embodiment 12:
First weighing is dropped into well the mixing of various composition mixing and blending machine, then namely obtain product through air-flow crushing by 325 mesh sieves.
Embodiment 13:
First weighing is dropped into well the mixing of various composition mixing and blending machine, then namely obtain product through air-flow crushing by 325 mesh sieves.
Embodiment 14:
First weighing is dropped into well the mixing of various composition mixing and blending machine, then namely obtain product through air-flow crushing by 325 mesh sieves.
Embodiment 15:
First weighing is dropped into well the mixing of various composition mixing and blending machine, then namely obtain product through air-flow crushing by 325 mesh sieves.
Embodiment 16:
First weighing is dropped into well the mixing of various composition mixing and blending machine, then namely obtain product through air-flow crushing by 325 mesh sieves.
Embodiment 17:
Methylsulfonyl bacterium azoles, Zhongshengmycin, condensation compound of alkyl phenol and epoxy ethane, polyoxyethylene sorbitan fatty acid ester, methyl naphthalene are mixed, is dissolved into uniform oil phase; Part water, xanthans, ethylene glycol are mixed uniformly aqueous phase; While high-speed stirred, oil phase is added aqueous phase in a kettle., open clipper and carry out high speed shear, and add silicone oil and remaining water supplies 100%, shear about half an hour, form aqueous emulsion.
Embodiment 18:
First weighing is dropped into well the mixing of various composition mixing and blending machine, then namely obtain product through air-flow crushing by 325 mesh sieves.
Embodiment 19:
First weighing is dropped into well the mixing of various composition mixing and blending machine, then namely obtain product through air-flow crushing by 325 mesh sieves.
Embodiment 20:
By above-mentioned all material Homogeneous phase mixing except montmorillonite, air-flow crushing, adds suitable quantity of water even spraying on montmorillonite, obtains product after mediating drying.
Embodiment 21:
By methylsulfonyl bacterium azoles, Zhongshengmycin, sodium lignin sulfonate and polymeric polycarboxylic acid salt mixture Homogeneous phase mixing, air-flow crushing, then add suitable quantity of water with NPK trace element, polyvinyl alcohol, urea after mixing and mediate, the mixture pelleting of gained, being drying to obtain product.
Indoor bioassay test example:
Complex composition of the present invention, combines between them and has obvious synergistic function to disease, and be not only the simple addition of two kinds of pharmacy effects, is specifically illustrated with following Assays Example.
Below raw test is tested and is adopted Sun Yun abundant method calculating co-toxicity coefficient (CTC) to evaluate 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: (CTC) >=120 show as synergistic effect; CTC≤80 show as antagonism; 80 < CTC < 120 show as summation action.
Indoor bioassay test example 1:
Rice Xanthomonas is the pathogenetic bacteria making paddy rice generation bacterial leaf-blight.
Adopt in vitro Nephelometric Determination, design concentration on the basis of preliminary experiment, each medicament is joined respectively in NA liquid nutrient medium, gradient dilution makes pastille medium, Inoculated Rice bacterial leaf-blight germ is placed on 28 DEG C of about shaken cultivation 24h, its turbidity (turbidity and bacterium amount be changing into positive correlation) is measured with transmissometer, the inhibiting rate that each chemicals treatment breeds bacterial growth is calculated according to the turbidity of blank and the turbidity of process, by the linear regression analysis between the probit value of inhibiting rate and the logarithm value of serial drug concentration, obtain the EC of each medicament
50value, CTC value.
Result of the test sees the following form 1.
The Toxicity Determination result of the table 1 water prevention rice bacterial leaf blight
| Composition | EC 50(μg/ml) | ATI | TTI | CTC |
| First sulphur (A) | 8.24 | 100 | / | / |
| Zhongshengmycin (B) | 56.25 | 14.65 | / | / |
| A:B＝40:1 | 7.01 | 117.55 | 97.92 | 120.05 |
| A:B＝30:1 | 6.72 | 122.62 | 97.25 | 126.09 |
| A:B＝20:1 | 6.25 | 131.84 | 95.94 | 137.43 |
| A:B＝15:1 | 5.8 | 142.07 | 94.67 | 150.07 |
| A:B＝10:1 | 5.56 | 148.2 | 92.24 | 160.67 |
| A:B＝9:1 | 5.31 | 155.18 | 91.46 | 169.66 |
| A:B＝5:1 | 5.16 | 159.69 | 85.77 | 186.17 |
| A:B＝2:1 | 5.34 | 154.31 | 71.55 | 215.66 |
| A:B＝1:1 | 7.55 | 109.14 | 57.32 | 190.39 |
| A:B＝1:2 | 10.12 | 81.42 | 43.1 | 188.92 |
| A:B＝1:5 | 17.54 | 46.98 | 28.87 | 162.7 |
| A:B＝1:9 | 22.69 | 36.32 | 23.18 | 156.64 |
| A:B＝1:10 | 25.82 | 31.91 | 22.41 | 142.42 |
| A:B＝1:15 | 29.66 | 27.78 | 19.98 | 139.02 |
| A:B＝1:20 | 35.91 | 22.95 | 18.71 | 122.62 |
| A:B＝1:25 | 40.67 | 20.26 | 17.93 | 112.99 |
From measurement result table 1: methylsulfonyl bacterium azoles and Zhongshengmycin are all greater than 120 by weight the co-toxicity coefficient of water prevention rice bacterial leaf spot pathogenic bacteria time composite between 40:1 ~ 1:20, show as synergistic effect.Especially when weight ratio is within the scope of 10:1 ~ 1:5, the co-toxicity coefficient of each process is all greater than 160, shows that synergistic effect is very remarkable.
Indoor bioassay test example 2:
Pseudomonas solanacearum is the pathogenetic bacteria making tomato, eggplant, capsicum, potatoes and other crops generation bacterial wilt.
After being activated on NA medium by bacterial wilt of tomato pathogen, be made into bacterium stoste with sterile water, the clump count grown after bacterium stoste is diluted to coated plate 100ul is the bacteria suspension of about 100, for subsequent use.
Get 400ul bacteria suspension and equivalent agricultural chemicals single dose mixes, 100ul is got with liquid-transfering gun, be placed on ready-made NA flat board, with sterilized " L " shape glass bar by even for bacteria suspension coating, cultivate 48h for 28 DEG C, counting clump count, and press formulae discovery bacteriostasis rate, bacterium colony inhibiting rate (%)=(contrast clump count-process clump count)/contrast clump count × 100, often process repetition 4 times, replace pesticide-treated for contrast with sterile water, the result of gained adopts Excel software analysis, calculates the EC of each medicament
50, and calculate co-toxicity coefficient according to the abundant method of Sun Yun.
Result of the test sees the following form 2
The Toxicity Determination result of table 2 control of plant bacterial wilt
| Composition | EC 50(μg/ml) | ATI | TTI | CTC |
| First sulphur (A) | 16.89 | 100 | / | / |
| Zhongshengmycin (B) | 22.72 | 74.34 | / | / |
| A:B＝40:1 | 14.14 | 119.45 | 99.37 | 120.2 |
| A:B＝30:1 | 13.44 | 125.67 | 99.17 | 126.72 |
| A:B＝20:1 | 12.73 | 132.68 | 98.78 | 134.32 |
| A:B＝19:1 | 11.56 | 146.11 | 98.72 | 148.01 |
| A:B＝14:1 | 11.3 | 149.47 | 98.29 | 152.07 |
| A:B＝10:1 | 10.68 | 158.15 | 97.67 | 161.92 |
| A:B＝8:1 | 10.06 | 167.89 | 97.15 | 172.82 |
| A:B＝4:1 | 8.96 | 188.50 | 94.87 | 198.70 |
| A:B＝3:1 | 7.87 | 214.61 | 93.58 | 229.32 |
| A:B＝1:1 | 10.34 | 163.35 | 87.17 | 187.39 |
| A:B＝1:3 | 11.94 | 141.46 | 80.75 | 175.17 |
| A:B＝1:4 | 13.12 | 128.73 | 79.47 | 161.99 |
| A:B＝1:5 | 12.95 | 130.42 | 78.62 | 165.90 |
| A:B＝1:8 | 14.56 | 116 | 77.19 | 150.28 |
| A:B＝1:10 | 15.67 | 107.79 | 76.67 | 140.58 |
| A:B＝1:14 | 17.39 | 97.12 | 76.05 | 127.71 |
| A:B＝1:19 | 17.81 | 94.83 | 75.62 | 125.40 |
| A:B＝1:20 | 18.55 | 91.05 | 75.56 | 120.5 |
| A:B＝1:25 | 19.33 | 87.38 | 75.33 | 116 |
From measurement result table 2: methylsulfonyl bacterium azoles and Zhongshengmycin are all greater than 120 by weight the co-toxicity coefficient of control of plant bacterial wilt bacterium time composite between 20:1 ~ 1:40, show as synergistic effect.Especially when weight ratio is within the scope of 10:1 ~ 1:5, the co-toxicity coefficient of each process is all greater than 160, shows that synergistic effect is very remarkable.
Indoor bioassay test example 3:
Carrot soft rot pathological form carrot soft rot Erwinia is the pathogenetic bacteria making soft rot of Chinese cabbage.
Bacterial classification cultured in test tube is extracted test tube tampon near alcolhol burner place, pour 10ml sterile water into, with disinfection inoculation pin, germ on inclined-plane is scraped gently, make spore suspension, being poured into by this spore suspension is equipped with in the sterilizing triangular flask of several glass marbles in advance again, cross bacteriological filtration liquid with sterile gauze after shake 5min, put in another sterilizing triangular flask, namely make required bacterium liquid.
By beef extract-peptone agar medium melt, to be cooled to 45 DEG C ~ 50 DEG C time, aseptically pour into rapidly in sterilizing culture dish together with 0.2ml bacterial suspension, every ware 15ml medium, shakes up rear cooled and solidified.With card punch (aperture 4mm) punching after sterilizing, 1ml liquid is dripped in circular hole, be placed in after 28 DEG C of insulating boxs cultivate 2d, measure 2 diameters of inhibition zone by right-angled intersection method with slide measure, average, calculate inhibiting rate, obtain virulence curve and EC
50, and press Sun Yun abundant method calculating co-toxicity coefficient.
Result of the test sees the following form 3
The Toxicity Determination result of soft rot of Chinese cabbage prevented and treated by table 3
| Composition | EC 50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 19.12 | 100 | / | / |
| Zhongshengmycin (B) | 21.63 | 88.4 | / | / |
| A:B＝40:1 | 15.39 | 124.24 | 99.72 | 124.59 |
| A:B＝30:1 | 14.82 | 129.01 | 99.63 | 129.5 |
| A:B＝20:1 | 13.75 | 139.05 | 99.45 | 139.83 |
| A:B＝15:1 | 12.69 | 150.67 | 99.27 | 151.77 |
| A:B＝10:1 | 11.73 | 163 | 98.95 | 164.74 |
| A:B＝9:1 | 11.22 | 170.41 | 98.84 | 172.41 |
| A:B＝6:1 | 10.61 | 180.21 | 98.34 | 183.25 |
| A:B＝3:1 | 9.97 | 191.78 | 97.1 | 197.51 |
| A:B＝1:1 | 9.42 | 202.97 | 94.2 | 215.47 |
| A:B＝1:2 | 10.75 | 177.86 | 92.26 | 192.77 |
| A:B＝1:5 | 12.19 | 156.85 | 90.33 | 173.64 |
| A:B＝1:8 | 13.95 | 137.06 | 89.69 | 152.82 |
| A:B＝1:10 | 14.89 | 128.41 | 89.45 | 143.55 |
| A:B＝1:15 | 16.28 | 117.44 | 89.12 | 131.78 |
| A:B＝1:20 | 17.3 | 110.52 | 88.95 | 124.25 |
| A:B＝1:25 | 19.05 | 100.37 | 88.84 | 112.97 |
From measurement result table 3: methylsulfonyl bacterium azoles and Zhongshengmycin are all greater than 120 by weight the co-toxicity coefficient preventing and treating soft rot of cabbage time composite between 40:1 ~ 1:20, show as synergistic effect.Especially when weight ratio is within the scope of 10:1 ~ 1:5, the co-toxicity coefficient of each process is all greater than 160, shows that synergistic effect is very remarkable.
Field medicine effect test embodiment:
In order to clear and definite methylsulfonyl bacterium azoles and the composite use of Zhongshengmycin are to the control efficiency of crop bacterial disease, and under verifying the preferably proportioning of Toxicity Determination also whether synergy is obvious in field, present inventor has performed a large amount of field trials, result show that indoor result is suitable in field, and built agent is effective, the lasting period is long.Be illustrated with several embodiment below.Following methylsulfonyl bacterium azoles is referred to as first sulphur.
Contrast medicament 1:3% Zhongshengmycin wetting powder, registration card number: PD20130210, Shenzhen Nuopuxin Agricultural Chemical Co., Ltd, commercial;
Contrast medicament 2:20% methylsulfonyl bacterium azole suspending agent (self-control)
Methylsulfonyl bacterium azoles 20%, triphen ethyl phenol APEO 9.0%, xanthans 0.1%, ethylene glycol 3.0%, silicone defoaming agent 0.1%, deionized water are mended to 100%, put into high shear homogeneous emulsifying machine high speed and shear 30 minutes, transport in sand mill, namely circulation sand milling obtains 20% methylsulfonyl bacterium azole suspending agent for 1-3 time again.
Field medicine effect test embodiment:
One, the field trial embodiment of the water prevention rice bacterial leaf blight:
Test method: be the rice bacterial leaf blight according to " GB/T17980.19-2000 pesticide field efficacy medicine test criterion () " application method controlling object.
Spray first time spray pesticide in bacterial blight of rice initial stage of origination, after 7d, carry out second time spray pesticide.Dispenser twice altogether, 20 square metres, each community, repeats 4 times.According to Chinese agricultural chemicals Information Network, dosage is 350 grams/ha, 400 grams/ha, 450 grams/ha, 500 grams/ha.
Investigation method: according to " GB/T17980.19-2000 pesticide field efficacy medicine test criterion () " investigation method, the sampling of 5, every community, gets 50 strains at often, every strain investigation boot leaf and the following two panels leaf of boot leaf.
0 grade: anosis;
1 grade: lesion area is leaf area less than 10%;
3 grades: lesion area is leaf area 11% ~ 25%;
5 grades: lesion area is leaf area 26% ~ 45%;
7 grades: lesion area is leaf area 46% ~ 65%:
9 grades: lesion area is leaf area
The field test results of the table 4 water prevention rice bacterial leaf blight
As can be known from Table 4, the successful of methylsulfonyl bacterium azoles and the composite water prevention rice bacterial leaf blight of Zhongshengmycin is better than single dose.After the two compound medicine, the preventive effect of 14d is 75.43% ~ 79.57%, and the lasting period is long.The two composite preventive effect synergy used than single dose obviously, illustrates that the synergistic results field that indoor virulence is tested is suitable for.
Two, the field trial embodiment of control of plant bacterial wilt:
Test method: according to " pesticide field efficacy medicine test criterion two (NY/T 1464.32-2010) " regulation application method, beginning to carry out the dispenser of first time filling root when seeing scab, carrying out second time and filling with root dispenser after 7d.Dispenser twice altogether, 20 square metres, each community, repeats 4 times.According to Chinese agricultural chemicals Information Network, dosage is 400 grams/ha, 500 grams/ha, 600 grams/ha, 700 grams/ha.
Investigation method: according to " pesticide field efficacy medicine test criterion nine (NY/T 1464.32-2010) " regulation investigation method, whole plant is investigated in every community, records total strain number, diseased plant number.7d, 14d investigation respectively after second time dispenser, the record total strain number of investigation and diseased plant number, calculate diseased plant rate and prevent and treat preventive effect.
The field test results of table 5 control of plant bacterial wilt
Result of the test shows, the successful of methylsulfonyl bacterium azoles and the composite control of plant bacterial wilt of Zhongshengmycin is better than single dose.After the two compound medicine, the preventive effect of 14d is 75.23% ~ 78.03%, and the lasting period is long.The composite preventive effect synergy than single dose use of both explanations is obvious.
Three, soft rot of Chinese cabbage field trial embodiment is prevented and treated:
Test method: with reference to " GB/T 17980.114-2004 pesticide field efficacy medicine test criterion (two) " regulation application method.
Carry out first time when disease onset and fill with root dispenser, carry out second time after 7d and fill with root dispenser.Dispenser twice altogether, 15 square metres, each community, repeats 4 times.According to Chinese agricultural chemicals Information Network, dosage is 300 grams/ha, 350 grams/ha, 400 grams/ha, 450 grams/ha.
Investigation method: with reference to " GB/T 17980.114-2004 pesticide field efficacy medicine test criterion (two) " regulation investigation method.Whole dish strain is investigated in every community, records total strain number, diseased plant number.7d, 14d investigation respectively after second time dispenser, the record total strain number of investigation and diseased plant number, calculate diseased plant rate and prevent and treat preventive effect.
The field test results of soft rot of Chinese cabbage prevented and treated by table 6
Result of the test shows, the successful of methylsulfonyl bacterium azoles and the composite control soft rot of Chinese cabbage of Zhongshengmycin is better than single dose.After the two compound medicine, the preventive effect of 14d is 75.33% ~ 83.14%, and the lasting period is long.The composite preventive effect synergy than single dose use of both explanations is obvious.
Claims (9)
1. contain a complex composition for methylsulfonyl bacterium azoles and Zhongshengmycin, it is characterized in that, described complex composition is made up of methylsulfonyl bacterium azoles and Zhongshengmycin; 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 Zhongshengmycin according to claim 1, it is characterized in that, the weight ratio of described methylsulfonyl bacterium azoles and Zhongshengmycin is (40 ~ 1): (1 ~ 20).
3. the complex composition containing methylsulfonyl bacterium azoles and Zhongshengmycin according to claim 2, it is characterized in that, the weight ratio of described methylsulfonyl bacterium azoles and Zhongshengmycin is (10 ~ 1): (1 ~ 5).
4. contain a preparation for methylsulfonyl bacterium azoles and Zhongshengmycin, it is characterized in that, comprise acceptable carrier and auxiliary agent on the arbitrary described complex composition of claims 1 to 3 and agricultural chemicals, be then prepared into disinfectant use in agriculture.
5. the preparation containing methylsulfonyl bacterium azoles and Zhongshengmycin according to claim 4, it is characterized in that, the weight percentage that described complex composition accounts for described disinfectant use in agriculture is 0.1% ~ 90%.
6. the preparation containing methylsulfonyl bacterium azoles and Zhongshengmycin according to claim 5, it is characterized in that, the weight percentage that described complex composition accounts for described disinfectant use in agriculture is 1% ~ 80%.
7. the preparation containing methylsulfonyl bacterium azoles and Zhongshengmycin according to claim 4, it is characterized in that, the formulation of described disinfectant use in agriculture is wetting powder, suspending agent, water dispersible granules, aqueous emulsion, seed treatment dry powder doses or granule.
8. the application of complex composition in controlling plant diseases as described in as arbitrary in claim 1-3.
9. complex composition as claimed in claim 8 is in the application in controlling plant diseases, it is characterized in that, the application of described complex composition in control bacterial diseases of plants and fungal disease.
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Cited By (2)
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| CN105794843A (en) * | 2016-04-08 | 2016-07-27 | 广西南宁益土生物科技有限责任公司 | Composition containing lactose high-temperature treated product and Zhongshengmycin |
| CN114521566A (en) * | 2022-02-21 | 2022-05-24 | 广西壮族自治区农业科学院 | Synergistic composition for preventing and treating soft rot of taro |
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Cited By (2)
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| CN105794843A (en) * | 2016-04-08 | 2016-07-27 | 广西南宁益土生物科技有限责任公司 | Composition containing lactose high-temperature treated product and Zhongshengmycin |
| CN114521566A (en) * | 2022-02-21 | 2022-05-24 | 广西壮族自治区农业科学院 | Synergistic composition for preventing and treating soft rot of taro |
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