CN104488908A - Compound composition and preparation containing methylsulfonyl azole and bismerthiazol - Google Patents
Compound composition and preparation containing methylsulfonyl azole and bismerthiazol Download PDFInfo
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Abstract
The invention discloses a compound composition and a preparation thereof. The compound composition comprises two active ingredients, the first active ingredient is methylsulfonyl azole, and the second active ingredient is bismerthiazol, wherein the weight ratio of the first active ingredient to the second active ingredient is (20-1):(1-40); and the chemical name of methylsulfonyl azole is 2-(4-fluorophenyl)-5-methylsulfonyl-1,3,4-oxadiazole. The compound composition can be used for effectively preventing and controlling bacterial diseases, and has a remarkable synergetic effect relatively to a single agent, the using amount and application times of pesticide can be reduced, the drug resistance of pathogenic bacteria can be retarded, and the prevention and control effect can be improved. Methylsulfonyl azole and bismerthiazol have high safety, and can be used for better guaranteeing safe production of agriculture and protecting the ecological environment.
Description
Technical field
The invention belongs to technical field of compounded pesticide, is a kind of Recompounded pesticide containing methylsulfonyl bacterium azoles and Yekuzuo and preparation thereof, application.
Background technology
Along with the change of pattern of farming, increase the weight of, and the pharmacy variety preventing and treating bacterial disease is limited when previous crop bacteriosis occurs in, Yekuzuo is the leading products of control bacterial disease, and the control of paddy rice bacteriosis is the most conventional recommendation medicament.Yekuzuo is the internal-suction type curative fungicide agent that China independently formulates, and belong to thiazoles new medicament, have another name called bismerthlazol, MBAMT, its molecular formula is: C
5h
6n
6s
4.Yekuzuo has interior suction, treatment and conduction, is mainly used to prevent and treat bacterial diseases of plants, the preventive effect good to bacterial blight of rice, bacterial stripe and citrus bacterial canker disease.But reach nearly 40 years owing to promoting the use of in China, long-time a large amount of use, cause Yekuzuo field efficacy to occur serious resistance, biologically active declines, and the preventive effect of controlling disease is undesirable.Even if develop better new medicament, but as long in service time, and disease is strengthened its resistance, causes preventive effect to decline.Therefore, adopting new varieties of pesticides and old kind rationally composite is the optimum method improving preventive effect.
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 all has good control efficiency and inhibitory action to bacterial disease, especially all has good control effects to bacterial blight of rice, slice disease, tobacco bacterial wilt, bacterial wilt of tomato etc.Methylsulfonyl bacterium azoles has efficiently, the feature of wide spectrum, use safety, is the bactericide with the potential quality being developed as large tonnage product.
Find through test, methylsulfonyl bacterium azoles and Yekuzuo mixture control bacterial disease effect very outstanding.Methylsulfonyl bacterium azoles is different with the mechanism of action of Yekuzuo, and the two composite application decreases every mu of dosage and spraying times that use, can ensure agriculture safety in production better and protect ecotope.
In view of this, for the deficiency that prior art exists, the object of the present invention is to provide a kind of complex composition and the preparation thereof that contain methylsulfonyl bacterium azoles and Yekuzuo, this complex composition and preparation thereof are relative to single dose, there is obvious synergistic function, reduce the dosage of agricultural chemicals, delay pathogen pesticide resistance simultaneously, improve control efficiency.
For reaching goal of the invention, the technical solution used in the present invention is:
Contain a complex composition for methylsulfonyl bacterium azoles and Yekuzuo, described complex composition contains two active components, and the first active component is methylsulfonyl bacterium azoles, and second active ingredient is Yekuzuo; 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 Yekuzuo, in order to ensure that complex composition has better synergistic effect, as preferably, the weight ratio that the first active component and second active ingredient are is (20 ~ 1): (1 ~ 40).
The above-described complex composition containing methylsulfonyl bacterium azoles and Yekuzuo, in order to ensure that complex composition has better synergistic effect, preferably, the weight ratio that the first above-mentioned active component and second active ingredient are is (5 ~ 1): (1 ~ 10).
The present invention also provides a kind of preparation containing methylsulfonyl bacterium azoles and Yekuzuo, and by weight containing 0.1 ~ 90% above-mentioned complex composition, all the other are agriculturally acceptable carrier and auxiliary agent, are then prepared into the bactericide for preventing and treating agricultural disease.
The preparation of above-described methylsulfonyl bacterium azoles and Yekuzuo, preferably, described bactericide is by weight containing 1 ~ 80% above-mentioned complex composition.
Above-described bactericide can be mixed with aqueous emulsion, wetting powder, suspending agent, water dispersible granules, granule or suspension seed-coating agent according to the method that this area is general.
Carrier of the present invention can be solid or liquid, and any carrier being generally used for preparing microbicide compositions all can use.
Liquid-carrier and solvent comprise in methyl alcohol, ethanol, solvent naphtha, castor oil, dimethylbenzene, toluene, dimethyl formamide, methyl-sulfoxide, glycol dimethyl ether or methyl oleate one or more.
Solid carrier comprise clay, diatomite, kaolin, attapulgite, imvite, talcum powder, precipitated calcium carbonate, P trace element or urea in one or more.
Auxiliary agent of the present invention comprises one or more in emulsifier, wetting dispersing agent, defoamer, thickener, suspending agent and antifreezing agent, can also comprise other auxiliary agents that the industry is conventional as required.
Emulsifier is selected from styrylphenol formaldehyde resin PULLRONIC F68 block type polyethers, polyoxyethylene nonylphenol ether, neopelex, xenol APEO, styryl phenol polyethenoxy ether phosphate, Ben-zylphenol Polyoxyethyl Ether phosphate, sorbitan trioleate, anhydrous sorbitol tristearate, polyoxyethylene ether alcohol six stearate, cithrol, polyethylene glycol mono stearate, sorbitan sesquioleate, glyceryl monostearate or phenethyl phenol polyethenoxy ether and agriculture breast 601#.
Wetting dispersing agent comprises sodium lignin sulfonate, calcium lignosulfonate, Negel, two (alkyl) naphthalenesulfonate formaldehyde condensation compound, sodium methylene bis-naphthalene sulfonate, aryl phenol polyoxyethylene succinate sulfonate, succinate sodium sulfonate, sldium lauryl sulfate, octylphenol polyethylene oxyethylene group ether sulfate, alkyl benzene sulfonate calcium salt, polyoxyethylene carboxylate, condensation compound of methyl naphthalene sulfonic acid and formaldehyde sulphate, naphthalene sulfonic acid-formaldehyde condensation product, methanonaphthalene sodium sulfonate or dibutyl naphthalenesulfonic acid formaldehyde condensation products.
Antifreezing agent comprises ethylene glycol, 1,2-PD, glycerine, one or more in urea.
Thickener comprise in xanthans, polyethylene glycol, pectin, polyvinyl alcohol, carboxymethyl cellulose and phenolic resins one or more.
Film forming agent can be ethyl cellulose.
Binding agent comprises starch, polyvinyl alcohol, ethyl cellulose.
Disintegrant is sodium sulphate.
The application of the complex composition that the present invention also provides in control crop bacterial disease.
Described bacterial disease is paddy rice bacterium cecospora spot 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 bacterial disease is Xanthomonas oryzae, bacterial wilt of tomato bacterium, soft rot of cabbage;
Complex composition of the present invention and bactericide have advantage compared to existing technology:
1, methylsulfonyl bacterium azoles and Yekuzuo rationally composite in certain proportion after, both are composite shows obvious synergistic function, and co-toxicity coefficient is all greater than 120, is not the simple superposition of two compositions.
2, complex composition dosage of the present invention is less compared with single dose, and the preventive effect of controlling disease is high, and field efficacy is more than 70%, and the preventive effect after composite is obviously better than single dose, and preventive effect is higher than single dose 17.79% ~ 46.12%.
3, the present invention kills complex composition and 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 Yekuzuo.
The preparation method of suspending agent:
By emulsifier, antifreezing agent, thickener, auxiliary agent, water mixing, mix through high speed shear, add methylsulfonyl bacterium azoles, Yekuzuo successively, abrading-ball 2 ~ 3 hours in ball crusher, the suspending agent of obtained bactericide of the present invention.
The preparation method of wetting powder
Methylsulfonyl bacterium azoles, Yekuzuo, wetting dispersing agent, filler are mixed, after airslide disintegrating mill is pulverized, stirs 30min, obtain the wetting powder of bactericide of the present invention.
The preparation method of suspension seed-coating agent
By methylsulfonyl bacterium azoles and Yekuzuo through air-flow crushing, after after adding assistant, film forming agent, thickener, antifreezing agent and water mix 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.
The preparation method of granule
Methylsulfonyl bacterium azoles, Yekuzuo, auxiliary agent, binding agent, filler are mixed, pulverizes, stir after adding water-wet, then use Squeezinggranulator granulation, sieve after drying, obtain the granule of bactericide of the present invention.
The preparation method of aqueous emulsion
By methylsulfonyl bacterium azoles, Yekuzuo, emulsifier, solvent, be dissolved into uniform oil phase; Part water, antifreezing agent 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 remaining water and supply, shear about half an hour, form aqueous emulsion.The i.e. aqueous emulsion of obtained bactericide of the present invention.
The preparation method of water dispersible granules
Methylsulfonyl bacterium azoles, Yekuzuo, auxiliary agent, binding agent, disintegrant, filler are mixed, pulverizes after stirring, then use Squeezinggranulator granulation, sieve after drying, obtain the water dispersible granules of bactericide of the present invention.
Formulation embodiment:
Embodiment 1:21% first sulphur Yekuzuo aqueous emulsion (1:20)
Methylsulfonyl bacterium azoles 1g, Yekuzuo 20g, styryl phenol polyethenoxy ether phosphate 4g, polyoxyethylene ether alcohol six stearate 3g, dimethyl formamide 8g, dimethylbenzene 20g, ethylene glycol 4g, aluminium-magnesium silicate 1g, phenolic resins 0.2g, water supplies 100g.
Embodiment 2:15% first sulphur Yekuzuo aqueous emulsion (5:10)
Methylsulfonyl bacterium azoles 5g, Yekuzuo 10g, xenol APEO 3g, polyethylene glycol mono stearate 5g, methyl-sulfoxide 8g, toluene 20g, 1,2-PD 5g, xanthans 0.2g, water supplies 100g.
Embodiment 3:10% first sulphur Yekuzuo aqueous emulsion (8:2)
Methylsulfonyl bacterium azoles 8g, Yekuzuo 2g, sorbitan trioleate 7g, anhydrous sorbitol tristearate 2g, glycol dimethyl ether 8g, methyl oleate 12g, glycerine 5g, polyethylene glycol 0.5g, water supplies 100g.
Embodiment 4:1% first sulphur Yekuzuo aqueous emulsion (0.9:0.1)
Methylsulfonyl bacterium azoles 0.9g, Yekuzuo 0.1g, polyoxyethylene nonylphenol ether 6.6g, neopelex 0.4g, ethanol 10g, solvent naphtha 15g, glycerine 5g, polyvinyl alcohol 0.5g, water supplies 100g.
Embodiment 5:21% first sulphur Yekuzuo aqueous emulsion (20:1)
Methylsulfonyl bacterium azoles 20g, Yekuzuo 1g, sorbitan sesquioleate 5g, glyceryl monostearate 3g, methyl alcohol 10g, castor oil 18g, urea 5g, carboxymethyl cellulose 0.3g, water supplies 100g.
Embodiment 6:32% first sulphur Yekuzuo wetting powder (30:2)
Methylsulfonyl bacterium azoles 30g, Yekuzuo 2g, sodium lignin sulfonate 6g, succinate sodium sulfonate 3g, clay supplies 100g.
Embodiment 7:25% first sulphur Yekuzuo wetting powder (1:24)
Methylsulfonyl bacterium azoles 1g, Yekuzuo 24g, calcium lignosulfonate 5g, Negel 4g, kaolin supplies 100g.
Embodiment 8:20% first sulphur Yekuzuo wetting powder (10:10)
Methylsulfonyl bacterium azoles 10g, Yekuzuo 10g, two (alkyl) naphthalenesulfonate formaldehyde condensation compound 7g, sodium methylene bis-naphthalene sulfonate 2g, diatomite supplies 100g.
Embodiment 9:36% first sulphur Yekuzuo wetting powder (30:6)
Methylsulfonyl bacterium azoles 30g, Yekuzuo 6g, aryl phenol polyoxyethylene succinate sulfonate 6g, sldium lauryl sulfate 4g, kaolin supplies 100g.
Embodiment 10:55% first sulphur Yekuzuo wetting powder (50:5)
Methylsulfonyl bacterium azoles 50g, Yekuzuo 5g, octylphenol polyethylene oxyethylene group ether sulfate 3g, naphthalene sulfonic acid-formaldehyde condensation product 5g, attapulgite 6g, kaolin supplies 100g.
Contrast medicament 1:20% methylsulfonyl bacterium azoles wetting powder
Methylsulfonyl bacterium azoles 20g, octylphenol polyethylene oxyethylene group ether sulfate 3g, naphthalene sulfonic acid-formaldehyde condensation product 5g, attapulgite 6g, kaolin supplies 100g.
Embodiment 11:80% first sulphur Yekuzuo wetting powder (5:75)
Methylsulfonyl bacterium azoles 5g, Yekuzuo 75g, alkyl benzene sulfonate calcium salt 3g, polyoxyethylene carboxylate 5g, 100g is supplied in imvite.
Embodiment 12:22% first sulphur Yekuzuo wetting powder (2:20)
Methylsulfonyl bacterium azoles 2g, Yekuzuo 20g, methanonaphthalene sodium sulfonate 3g, dibutyl naphthalenesulfonic acid formaldehyde condensation products 6g, 100g supplied by talcum powder.
Embodiment 13:30% first sulphur Yekuzuo wetting powder (20:10)
Methylsulfonyl bacterium azoles 20g, Yekuzuo 10g, calcium lignosulfonate 2g, condensation compound of methyl naphthalene sulfonic acid and formaldehyde sulphate 5g, precipitated calcium carbonate supplies 100g.
Embodiment 14:20% first sulphur Yekuzuo wetting powder (19:1)
Methylsulfonyl bacterium azoles 19g, Yekuzuo 1g, alkyl benzene sulfonate calcium salt 3g, naphthalene sulfonic acid-formaldehyde condensation product 5g, kaolin supplies 100g.
Embodiment 15:41% first sulphur Yekuzuo wetting powder (1:40)
Methylsulfonyl bacterium azoles 1g, Yekuzuo 40g, condensation compound of methyl naphthalene sulfonic acid and formaldehyde sulphate 5g, naphthalene sulfonic acid-formaldehyde condensation product 4g, clay supplies 100g.
Embodiment 16:6% first sulphur Yekuzuo granule (3:3)
Methylsulfonyl bacterium azoles 3g, Yekuzuo 3g, aryl phenol polyoxyethylene succinate sulfonate 3g, alkyl benzene sulfonate calcium salt 1g, clay supplies 100g.
Embodiment 17:0.5% first sulphur Yekuzuo granule (0.4:0.1)
Methylsulfonyl bacterium azoles 0.4g, Yekuzuo 0.1g, methanonaphthalene sodium sulfonate 2.5g, sldium lauryl sulfate 2g, starch 2g, P trace element 4g, 100g supplied by urea.
Embodiment 18 90% first sulphur Yekuzuo water dispersible granules (84:6)
Methylsulfonyl bacterium azoles 84g, Yekuzuo 6g, methanonaphthalene sodium sulfonate 3g, polyoxyethylene carboxylate 2g, 100g supplied by white carbon.
Embodiment 19 40% first sulphur Yekuzuo water dispersible granules (20:20)
Methylsulfonyl bacterium azoles 20g, Yekuzuo 20g, naphthalene sulfonic acid-formaldehyde condensation product 2g, aryl phenol polyoxyethylene succinate sulfonate 3g, polyvinyl alcohol 2g, sodium sulphate g, bentonite supplies 100g.
Embodiment 20 31% first sulphur Yekuzuo water dispersible granules (1:30)
Methylsulfonyl bacterium azoles 1g, Yekuzuo 30g, polyoxyethylene carboxylate 1g, naphthalene sulfonic acid-formaldehyde condensation product 1g, Negel 3g, ethyl cellulose 2g, sodium sulphate g, bentonite supplies 100g.
Embodiment 21:0.1% first sulphur Yekuzuo suspension seed-coating agent (0.05:0.05)
Methylsulfonyl bacterium azoles 0.05g, Yekuzuo 0.05g, styrylphenol formaldehyde resin PULLRONIC F68 block type polyethers 3.0g, condensation compound of methyl naphthalene sulfonic acid and formaldehyde sulphate 3g, ethyl cellulose 1g, pectin 1g, isopropyl alcohol 5g, water supplies 100g.
Embodiment 22:16% first sulphur Yekuzuo suspending agent (1:15)
Methylsulfonyl bacterium azoles 1g, Yekuzuo 15g, cithrol 5.0g, Negel 3g, xanthans 0.1g, ethylene glycol 5g, water supplies 100g.
Embodiment 23:20% first sulphur Yekuzuo suspending agent (18:2)
Methylsulfonyl bacterium azoles 18g, Yekuzuo 2g, naphthalene sulfonic acid-formaldehyde condensation product 3.5g, Ben-zylphenol Polyoxyethyl Ether phosphate 1g, agriculture breast 601#1.5g, xanthans 0.1g, glycerine 5g, water supplies 100g.
Missible oil, microemulsion and ultra low volume liquids also all adopt composition well known in the art and content, do not repeat them here.
Indoor bioassay is tested:
Bactericidal 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.
Toxicity Determination embodiment:
Toxicity Determination embodiment one
Adopt in vitro nephelometry to carry out Toxicity Determination, select bacterial leaf streak of rice to be target target, repeat 4 times, latter 24 hours check results of investigating.
Concrete grammar: 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 Xanthomonas campestris PV.oryzicola 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.
Measurement result sees the following form 1
The Toxicity Determination result of bacterial leaf streak of rice prevented and treated by table 1
| Composition | EC 50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 8.13 | 100 | / | / |
| Yekuzuo (B) | 46.11 | 17.63 | / | / |
| A:B＝25:1 | 7.28 | 111.68 | 96.83 | 115.33 |
| A:B＝20:1 | 6.96 | 116.81 | 96.08 | 121.58 |
| A:B＝18:1 | 6.85 | 118.69 | 95.66 | 124.06 |
| A:B＝14:1 | 6.21 | 130.92 | 94.51 | 138.52 |
| A:B＝10:1 | 6.14 | 132.41 | 92.51 | 143.13 |
| A:B＝8:1 | 5.94 | 136.87 | 90.85 | 150.66 |
| A:B＝5:1 | 4.56 | 178.29 | 86.27 | 206.66 |
| A:B＝4:1 | 5.05 | 160.99 | 83.53 | 192.74 |
| A:B＝3:1 | 5.38 | 151.12 | 79.41 | 190.30 |
| A:B＝1:1 | 7.19 | 113.07 | 58.82 | 192.25 |
| A:B＝1:3 | 11.84 | 68.67 | 38.22 | 179.64 |
| A:B＝1:6 | 16.25 | 50.03 | 29.4 | 170.18 |
| A:B＝1:8 | 18.12 | 44.87 | 26.78 | 167.52 |
| A:B＝1:10 | 20.07 | 40.51 | 25.12 | 161.26 |
| A:B＝1:14 | 22.73 | 35.77 | 23.12 | 154.68 |
| A:B＝1:20 | 27.19 | 29.9 | 21.55 | 138.72 |
| A:B＝1:30 | 31.15 | 26.1 | 20.29 | 128.64 |
| A:B＝1:40 | 34.43 | 23.61 | 19.64 | 120.23 |
| A:B＝1:50 | 38.15 | 21.31 | 19.25 | 110.72 |
From measurement result table 1: methylsulfonyl bacterium azoles and Yekuzuo are by weight when being composite between 20:1 ~ 1:40, and the co-toxicity coefficient of control bacterial leaf streak of rice is all greater than 120, shows 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 two:
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 |
| Methylsulfonyl bacterium azoles (A) | 16.89 | 100 | / | / |
| Yekuzuo (B) | 30.43 | 55.5 | / | / |
| A:B＝25:1 | 15.49 | 109.04 | 98.29 | 110.94 |
| A:B＝20:1 | 13.83 | 122.13 | 97.88 | 124.77 |
| A:B＝19:1 | 13.08 | 129.13 | 97.78 | 132.07 |
| A:B＝15:1 | 12.72 | 132.78 | 97.22 | 136.58 |
| A:B＝10:1 | 12.34 | 136.87 | 95.95 | 142.64 |
| A:B＝9:1 | 11.75 | 143.74 | 95.55 | 150.44 |
| A:B＝5:1 | 11.6 | 145.6 | 92.58 | 157.27 |
| A:B＝2:1 | 10.62 | 159.04 | 85.17 | 186.74 |
| A:B＝1:1 | 10.92 | 154.67 | 77.75 | 198.93 |
| A:B＝1:2 | 11.6 | 145.60 | 70.34 | 207.01 |
| A:B＝1:5 | 14.25 | 118.53 | 62.92 | 188.38 |
| A:B＝1:9 | 16.83 | 100.36 | 59.95 | 167.39 |
| A:B＝1:10 | 17.57 | 96.13 | 59.55 | 161.43 |
| A:B＝1:15 | 18.92 | 89.27 | 58.29 | 153.16 |
| A:B＝1:19 | 20.13 | 83.90 | 57.73 | 145.34 |
| A:B＝1:24 | 20.71 | 81.55 | 57.28 | 142.37 |
| A:B＝1:30 | 22.49 | 75.1 | 56.94 | 131.89 |
| A:B＝1:35 | 23.17 | 72.90 | 56.74 | 128.47 |
| A:B＝1:40 | 24.61 | 68.63 | 56.59 | 121.28 |
| A:B＝1:50 | 27.42 | 61.6 | 56.38 | 109.26 |
From measurement result table 2: methylsulfonyl bacterium azoles and Yekuzuo are by weight when being composite between 20:1 ~ 1:40, and the co-toxicity coefficient of control of plant bacterial wilt bacterium is all greater than 120, shows as synergistic effect.Especially when weight ratio is within the scope of 1:5 ~ 1:10, synergistic effect highly significant.
Indoor bioassay test example three:
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) | 18.67 | 100 | / | / |
| Yekuzuo (B) | 32.37 | 57.68 | / | / |
| A:B＝25:1 | 16.52 | 113.01 | 98.37 | 114.88 |
| A:B＝20:1 | 15.39 | 121.31 | 97.98 | 123.81 |
| A:B＝18:1 | 15.02 | 124.3 | 97.77 | 127.13 |
| A:B＝12:1 | 13.78 | 135.49 | 96.74 | 140.05 |
| A:B＝10:1 | 13.15 | 141.98 | 96.15 | 147.66 |
| A:B＝8:1 | 12.56 | 148.65 | 95.3 | 155.98 |
| A:B＝5:1 | 11.95 | 156.23 | 92.95 | 168.09 |
| A:B＝2:1 | 11.42 | 163.49 | 85.89 | 190.34 |
| A:B＝1:1 | 10.5 | 177.81 | 78.84 | 225.54 |
| A:B＝1:3 | 13.03 | 143.28 | 68.26 | 209.92 |
| A:B＝1:6 | 15.6 | 119.68 | 63.72 | 187.81 |
| A:B＝1:9 | 17.77 | 105.06 | 61.91 | 169.71 |
| A:B＝1:10 | 18.52 | 100.81 | 61.52 | 163.85 |
| A:B＝1:15 | 20.63 | 90.5 | 60.32 | 150.03 |
| A:B＝1:20 | 21.98 | 84.94 | 59.69 | 142.3 |
| A:B＝1:30 | 24.06 | 77.6 | 59.04 | 131.43 |
| A:B＝1:40 | 26.44 | 70.61 | 58.71 | 120.28 |
| A:B＝1:50 | 28.38 | 65.79 | 58.51 | 112.44 |
From measurement result table 3: methylsulfonyl bacterium azoles and Yekuzuo are by weight when being composite between 20:1 ~ 1:40, and the co-toxicity coefficient preventing and treating soft rot of cabbage is all greater than 120, shows as synergistic effect.Especially when weight ratio is within the scope of 5:1 ~ 1:10, the co-toxicity coefficient of each process is all greater than 160, shows that synergistic effect is very remarkable.
land for growing field crops test examples
In order to clear and definite methylsulfonyl bacterium azoles and Yekuzuo alone with time mixed to the control efficiency of paddy rice, Solanaceae class vegetables, the crop pest such as melon, and composite use whether synergy and synergy whether obvious, present invention applicant at home different regions has carried out a large amount of field trials.Illustrate with several fields embodiment below.
Contrast medicament 1:20% methylsulfonyl bacterium azoles wetting powder, self-control.
Contrast medicament 2:20% Yekuzuo wetting powder, registration card number: PD86153-12, Sichuan Prov. Chemical Industry Research & Design Academy, commercial;
Field trial embodiment one: the field control effectiveness test of control bacterial leaf streak of rice
Test method: according to " pesticide field efficacy medicine test criterion two (GB/T17980.105-2004) " regulation application method, disease occur before or initial stage of origination first time spray pesticide, after 7d second time spray pesticide.Dispenser twice altogether, 20 square metres, each community is repeated four times.
Investigation method: according to " pesticide field efficacy medicine test criterion two (GB/T17980.105-2004) " regulation investigation method, every community adopts 5 diagonal samplings, gets 25 clumps at often, every strain investigation boot leaf and the following two panels leaf of boot leaf.
X. c. pv. oryzicola Seriousness gradation standard:
0 grade: paddy rice is without scab;
1 grade: blade only has half past one transparent water stain shape scab, and lesion area accounts for less than 1% of one-piece blade area;
3 grades: blade has sporadicly short and narrow strip scab, and lesion area accounts for the 1%-5% of one-piece blade area;
5 grades: leaf spot lesion is more, lesion area accounts for the 6%-25% of one-piece blade area;
7 grades: on blade, scab is closeer, lesion area accounts for the 26%-50% of one-piece blade area;
9 grades: on blade, scab gathers, lesion area accounts for more than 51% of one-piece blade area.
Result of the test is in table 4.
The field test results of bacterial leaf streak of rice prevented and treated by table 4
From result of the test table 4, methylsulfonyl bacterium azoles and Yekuzuo composite when dosage is less than single dose, but the successful of control bacterial leaf streak of rice is better than single dose, after the two composite second time medicine, 7 days preventive effects exceed single dose 27.06% ~ 35.66%, and after second time medicine, 14 days control X. c. pv. oryzicola effects still can reach 81.96% ~ 87.76%, and the lasting period is long.
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 diseased plant, carrying out second time and filling with root dispenser after 7d.Dispenser twice altogether, 20 square metres, each community, repeats 4 times.
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
From result of the test table 5, methylsulfonyl bacterium azoles and Yekuzuo composite when dosage is less than single dose, but the successful of control of plant bacterial wilt is better than single dose, after the two composite second time medicine, 7 days preventive effects exceed single dose 28.06% ~ 46.12%, and 14 days preventive effects still can reach 77.61% ~ 86.24% after second time medicine, the lasting period is long.
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, 25 square metres, each community, repeats 4 times.
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
From result of the test table 6, methylsulfonyl bacterium azoles and Zhongshengmycin composite when dosage is less than single dose, but the successful of control soft rot of Chinese cabbage is better than single dose, after the two composite second time medicine, 7 days preventive effects exceed single dose 25.50% ~ 41.71%, and 14 days preventive effects still can reach 79.36% ~ 86.73% after second time medicine, the lasting period is long.
Claims (7)
1. contain a complex composition for methylsulfonyl bacterium azoles and Yekuzuo, it is characterized in that, described complex composition contains two active components, and the first active component is methylsulfonyl bacterium azoles, and second active ingredient is Yekuzuo; Wherein, the chemical name of methylsulfonyl bacterium azoles is 2-(to fluorophenyl)-5-mesyl-1,3,4-oxadiazole.
2., according to the complex composition containing methylsulfonyl bacterium azoles and Yekuzuo described in claim 1, it is characterized in that, the weight ratio that the first active component described and second active ingredient are is (20 ~ 1): (1 ~ 40).
3., according to the complex composition containing methylsulfonyl bacterium azoles and Yekuzuo described in claim 1, it is characterized in that, the weight ratio of the first active component described and second active ingredient is (5 ~ 1): (1 ~ 10).
4. one kind contains the preparation of methylsulfonyl bacterium azoles and Yekuzuo, it is characterized in that, by weight containing the arbitrary described complex composition of 0.1 ~ 90% claim 1-3, all the other are agriculturally acceptable carrier and auxiliary agent, are then prepared into the bactericide for preventing and treating agricultural disease.
5. according to the preparation containing methylsulfonyl bacterium azoles and Yekuzuo described in claim 4, it is characterized in that, described bactericide is by weight containing the arbitrary described complex composition of 1% ~ 80% claim 1-3.
6. the preparation containing methylsulfonyl bacterium azoles and Yekuzuo according to claim 4, it is characterized in that, the formulation of described bactericide is aqueous emulsion, wetting powder, suspending agent, water dispersible granules, granule or suspension seed-coating agent.
7. the application of the complex composition as described in as arbitrary in claim 1-3 in control bacterial diseases of plants.
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| CN101176448A (en) * | 2007-10-26 | 2008-05-14 | 张少武 | Leaf die azoles water decentrality granula bactericide and preparation method thereof |
| CN102499247A (en) * | 2011-10-17 | 2012-06-20 | 贵州大学 | Oxadiazole sulfone compound for controlling bacterial crop diseases |
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| CN102499247A (en) * | 2011-10-17 | 2012-06-20 | 贵州大学 | Oxadiazole sulfone compound for controlling bacterial crop diseases |
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