CN104488906A - Compound composition and bactericide containing methylsulfonyl azole and benziothiazolinone - Google Patents
Compound composition and bactericide containing methylsulfonyl azole and benziothiazolinone Download PDFInfo
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- CN104488906A CN104488906A CN201410788262.9A CN201410788262A CN104488906A CN 104488906 A CN104488906 A CN 104488906A CN 201410788262 A CN201410788262 A CN 201410788262A CN 104488906 A CN104488906 A CN 104488906A
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Abstract
The invention discloses a compound composition containing methylsulfonyl azole and benziothiazolinone. The compound composition is prepared from methylsulfonyl azole and benziothiazolinone serving as main active ingredients, wherein the chemical name of methylsulfonyl azole is 2-(4-fluorophenyl)-5-methylsulfonyl-1,3,4-oxadiazole; the weight ratio of methylsulfonyl azole to benziothiazolinone is (100-1):(1-40), and preferably (40-1):(1-10); and the total weight of active ingredients A and B is 0.1-90 percent of total weight of the composition. The compound composition shows a remarkable synergetic effect, can be used for reducing drug resistance of diseases, and can be used for preventing and controlling multiple crop bacterial diseases, such as rice bacterial leaf streak, rice bacterial leaf blight, cucumber bacterial angular leaf spot, tomato bacterial wilt, soft rot of Chinese cabbage, citrus bacterial canker and other bacterial diseases.
Description
Technical field
The present invention relates to technical field of pesticide, particularly relate to the complex composition containing methylsulfonyl bacterium azoles and benziothiazolinone and bactericide.
Background technology
Along with the change of weather, pattern of farming, the generation of bacterial diseases of crops, the loss caused increases the weight of year by year, but the correlative study of bacterial disease does not obtain enough attention, relatively fungal disease is lagged behind to the Prevention Technique of bacterial disease, causes bacterial disease day by day to become the Major Diseases having a strong impact on agricultural production in some areas.Secondly, few to the good pharmacy variety of bacterial disease drug effect at present.
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 a kind of novel bacterial disease pesticide control, can infiltrate plant epidermis, after Uptake and translocation, act on target leaf, is synthesized, the Growth and reproduction of final anti-bacteria by the energy of anti-bacteria.Show that methylsulfonyl bacterium azoles has good control effect to serial diseases such as bacterial blight of rice, cucumber bacterial angular leaf spot, citrus bacterial canker disease, bacterial wilt of peanut, softs rot of cabbage through great many of experiments.This medicament production technology is simple, environmentally friendly, without the discharge of three industrial wastes, production cost is lower, meets the environmental protection theory that modern agricultural production is advocated.And sterilization is extensively general, have good control effect to various bacterial disease, having the feature of high-efficiency low-toxicity, wide spectrum, safety, is a kind ofly have the novel green agricultural chemicals being developed as large tonnage product potential quality.
Benziothiazolinone is a kind of novel, wide-spectrum bactericide, is mainly used in various bacteria, the fungal disease of preventing and treating and treating cucumber downy mildew, pear scab, apple scab, citrus anthracnose, anthracnose of grape etc.Its bactericidal action mechanism, mainly comprises and destroys germ nuclear structures, makes it lose the metabolism of core position and exhaustion death and interference germ cell, makes its physiologic derangement, finally cause dead two aspects.
Through our a large amount of experiment, show that methylsulfonyl bacterium azoles can effectively prevent and delay generation and the expansion of the diseases such as soft rot, canker, bacterial wilt.Methylsulfonyl bacterium azoles is mixed with benziothiazolinone, methylsulfonyl bacterium azoles anti-bacteria on the one hand, induction plant disease resistance, on the other hand, benziothiazolinone was also a kind of broad-spectrum germicide originally, not only can significantly improve the preventive effect of methylsulfonyl bacterium azoles, the control spectrum of complex composition can also be expanded, guarantee output to greatest extent.
In view of this, for above-mentioned defect, the object of the invention is: a kind of complex composition and the bactericide thereof that contain methylsulfonyl bacterium azoles and benziothiazolinone are provided, show obvious synergistic function at control bacterial disease.
In order to reach the order of invention, the technical solution used in the present invention is:
Containing a complex composition for methylsulfonyl bacterium azoles and benziothiazolinone, described complex composition is with methylsulfonyl bacterium azoles and benziothiazolinone for active component, and wherein the chemical name of methylsulfonyl bacterium azoles is 2-(to fluorophenyl)-5-mesyl-1,3,4-oxadiazole; The weight ratio of methylsulfonyl bacterium azoles and benziothiazolinone is (100 ~ 1): (1 ~ 40).
The above-described complex composition containing methylsulfonyl bacterium azoles and benziothiazolinone, the weight ratio of described methylsulfonyl bacterium azoles and benziothiazolinone is preferably (40 ~ 1): (1 ~ 10).
The above-described complex composition containing methylsulfonyl bacterium azoles and benziothiazolinone, the weight ratio of described methylsulfonyl bacterium azoles and benziothiazolinone is preferably (20 ~ 1): (1 ~ 5).
The present invention also provides a kind of preparation containing methylsulfonyl bacterium azoles and benziothiazolinone, and by weight containing more than 0.1 ~ 90% arbitrary described complex composition, all the other are acceptable auxiliary agent and carrier on agricultural chemicals, are then prepared into the bactericide preventing and treating crop pest.
The above-described preparation containing methylsulfonyl bacterium azoles and benziothiazolinone, described bactericide is by weight containing more than 1 ~ 80% arbitrary described complex composition.
The above-described preparation containing methylsulfonyl bacterium azoles and benziothiazolinone, described bactericide is mixed with water dispersible granules, wetting powder, microemulsion, suspending agent, aqueous emulsion, missible oil, suspension seed-coating agent.
Auxiliary agent of the present invention can comprise one or more in surfactant, defoamer, thickener, disintegrant and antifreezing agent as required, can also comprise other auxiliary agents that the industry is conventional as required.
The preferred selfpolyoxyethylene sorbitan fatty acid ester series of surfactant used, fatty alcohol-polyoxyethylene ether series, condensation compound of alkyl phenol and epoxy ethane OP series, polyoxyethylene nonylphenol ether series, styrylphenol formaldehyde resin PULLRONIC F68 block type polyether series, triphen ethyl phenol APEO series, two phenethyl phenol polyethenoxy ether series, in calcium dodecyl benzene sulfonate (i.e. 500#) one or more.
Wetting dispersing agent preferably from lauryl sodium sulfate, diisobutyl naphthalene sulfonic acids (abbreviation pulls open powder), di-2-ethylhexylphosphine oxide bitter edible plant sodium sulfonate (be called for short NNO), acrylic acid and propionamide copolymer, dispersing agent MF (being called for short MF), Sodium Polyacrylate, desugar and in the sodium lignin sulfonate of the sodium lignin sulfonate of classification, desugar, condensation and modification, lignosulfonates, poly carboxylic acid derivative's sodium lignin sulfonate one or more.
Any one or two kind of thickener preferably in xanthans, aluminium-magnesium silicate.
Disintegrant comprises potassium phosphate, potash, potassium sulfate, sodium chloride, sodium sulphate, sodium phosphate, ammonium sulfate.
Antifreezing agent comprises isopropyl alcohol, propane diols, glycerine, ethylene glycol, urea.
Film forming agent comprises animal glue, pectin, polyethylene glycol.
Binding agent comprises ethyl cellulose, starch, polyvinyl alcohol.
Carrier of the present invention can be solid or liquid, and the carrier being generally used for compositions formulated bactericide all can use.
One or more preferably in white carbon, kaolin, water, potter's clay, bentonite, diatomite, earth powder, precipitated calcium carbonate of described solid carrier
During described bactericidal composition obtaining liq formulation, the liquid-carrier used comprises water and organic solvent, organic solvent is toluene, dimethylbenzene, methyl oleate, solvent naphtha, turpentine oil, vegetable oil, carrene, chloroform, methyl alcohol, ethanol, isopropyl alcohol, butanols, isoamyl alcohol, cyclohexanone, isophorone, acetophenone, ethyl acetate, butyl acetate, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), methyl cellosolve, ethyl cellosolve, solvent naphtha 200#, solvent naphtha 150#, methyl naphthalene can be used alone, also can two kinds or more used in combination.
As preferably, organic solvent of the present invention is one or more in ethanol, solvent naphtha 200#, solvent naphtha 150#, methyl naphthalene, N methyl pyrrolidone.
Complex composition of the present invention can be mixed with wetting powder, water dispersible granules, microemulsion, aqueous emulsion, suspending agent, seed coat agent, missible oil according to the method that this area is general.
The bacterial fungus venereal disease evils such as complex composition of the present invention is applicable to control crop bacterial disease and some fungi venereal disease evil, the bacterial wilt of as sick in soft rot of cabbage, watermelon blight, cucumber bacterial angular leaf spot and downy mildew, tobacco bacterial wilt, citrus bacterial canker disease and shot hole, X. c. pv. oryzicola and bacterial leaf-blight, tomato shot hole and canker, downy mildew of garpe, melon and solanaceous vegetable.
Composition of the present invention can be used by commonsense method, as added the process of water spray cauline leaf, also can execute by root, can also dress seed or seed pelleting use.Be mainly used in the crops such as paddy rice, tobacco, cucumber, tomato, oranges and tangerines, prevention and corntrol bacterial disease, guarantees output.
Complex composition of the present invention has following beneficial effect compared to existing technology:
1, methylsulfonyl bacterium azoles and benziothiazolinone composite, within the scope of certain proportion, prevent and treat its co-toxicity coefficient of crop pest be greater than 120, show obvious synergistic function.
2. reduce the usage amount of agricultural chemicals,
3. guarantee output to greatest extent: methylsulfonyl bacterium azoles and benziothiazolinone are all broad-spectrum germicide simultaneously, effective object is mainly plant pathogenetic bacteria, the mechanism of action there is bigger difference, complementary synergistic effect can be played, increase the effect effectiveness to action target each other, thus crop yield can be guaranteed to the full extent.
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 (A) is methylsulfonyl bacterium azoles (being called for short methylsulfonyl in following form); Active component (B) is benziothiazolinone.
In preparation embodiment, wetting dispersing agent used comprises diisobutyl sodium naphthalene sulfonate (abbreviation pulls open powder), 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, lignosulfonates (being called for short M-11), poly carboxylic acid derivative's (being called for short CF), sodium lignin sulfonate (being called for short M-14).
Surfactant is selected from polyoxyethylene sorbitan fatty acid ester series and comprises T-20, T-40, T-60, T-80, T-85, fatty alcohol-polyoxyethylene ether series comprises AEO-9, AEO-15, AEO-20, OS-15, JFC, condensation compound of alkyl phenol and epoxy ethane series comprises OP-10, OP-15, OP-18, OP-20, polyoxyethylene nonylphenol ether series comprises NP-10, NP-15, NP-18, NP-20, styrylphenol formaldehyde resin PULLRONIC F68 block type polyether series comprises 33#, 34#, 36#, 37#, triphen ethyl phenol APEO series comprises 601#, 602#, 603#, two phenethyl phenol polyethenoxy ether series comprises 604#, 605#, 606#, anion surfactant calcium dodecyl benzene sulfonate (500#).
For the purpose of unification, listed preparation embodiment below, dispersant and emulsifier all adopt abbreviation or commercial disignation.
embodiment prepared by preparation:
One, the preparation of water dispersible granules
Methylsulfonyl bacterium azoles, benziothiazolinone, wetting dispersing agent, binding agent, white carbon, disintegrant, carrier are mixed, after airslide disintegrating mill is pulverized, stir 30min, mediate with water, after add in fluidized-bed granulation dryer and carry out granulation, drying, obtain the water dispersible granules of bactericide of the present invention.
Two, the preparation of microemulsion
Methylsulfonyl bacterium azoles and benziothiazolinone are added in organic solvent, after stirring, obtains transparent mixed liquor; In above-mentioned mixed liquor, add surfactant, be stirred to emulsifier and dissolve completely; Under the mixing speed of 50r/min, water is joined and is above-mentionedly dissolved with in the mixed liquor of surfactant, at ambient temperature, stir 30min, obtain the micro emulsion of homogeneous transparent; In above-mentioned micro emulsion, add antifreezing agent, stir, obtain the microemulsion of bactericide of the present invention.Formula composition:
Three, the preparation of suspending agent
By surfactant, antifreezing agent, thickener, moisture content mixing, mix through high speed shear, add methylsulfonyl bacterium azoles, benziothiazolinone successively, abrading-ball 2 ~ 3 hours in ball crusher, obtained bactericide of the present invention suspending agent.
Four, the preparation of aqueous emulsion
By methylsulfonyl bacterium azoles, benziothiazolinone, surfactant, organic solvent mixing, 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.
Five, the preparation of wetting powder
Methylsulfonyl bacterium azoles, benziothiazolinone, wetting dispersing agent, white carbon, carrier are mixed, after airslide disintegrating mill is pulverized, stirs 30min, obtain the wetting powder of bactericide of the present invention.
Comparative examples is 20% methylsulfonyl bacterium azoles wetting powder.
Six, the preparation of missible oil
Methylsulfonyl bacterium azoles and benziothiazolinone are added in organic solvent, then adds after surfactant stirs and obtain transparent mixed liquor, be i.e. the missible oil of obtained bactericide of the present invention
Seven, suspension seed-coating agent
By methylsulfonyl bacterium azoles and benziothiazolinone 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.
The present composition, except can being made into above formulation, can also make the multiple formulations such as micro-capsule suspension, injection drying agent, ultra low volume.
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 criterions are: co-toxicity coefficient >=120 show as synergistic effect; Co-toxicity coefficient≤80 show as antagonism; 80< co-toxicity coefficient <120 shows as summation action.
The Toxicity Determination of control cucumber downy mildew:
Test method: prepare some pathogeny blades, with 4 DEG C of distillation washing lower blade back side Pseudoperonospora cubensis sporangiums, is made into suspension 1 × 107 sporangium/ml.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 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, calculate the EC of lattice medicament according to the preventive effect probability value of each drug concentration logarithm value and correspondence
50and co-toxicity coefficient.
The Toxicity Determination result of table 1 methylsulfonyl bacterium azoles and the composite control cucumber downy mildew of benziothiazolinone
| Composition | EC 50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 27.38 | 100.00 | / | / |
| Benziothiazolinone (B) | 14.92 | 183.51 | / | / |
| A:B＝100:1 | 22.31 | 122.73 | 100.83 | 121.72 |
| A:B＝60:1 | 19.27 | 142.09 | 101.37 | 140.17 |
| A:B＝40:1 | 17.84 | 153.48 | 102.04 | 150.41 |
| A:B＝20:1 | 16.67 | 164.25 | 103.98 | 157.97 |
| A:B＝10:1 | 15.94 | 171.77 | 107.59 | 159.65 |
| A:B＝5:1 | 13.26 | 206.49 | 113.92 | 181.26 |
| A:B＝2:1 | 11.19 | 244.68 | 127.84 | 191.40 |
| A:B＝1:1 | 9.43 | 290.35 | 141.76 | 204.82 |
| A:B＝1:2 | 8.72 | 313.99 | 155.67 | 201.70 |
| A:B＝1:5 | 9.37 | 292.21 | 169.59 | 172.30 |
| A:B＝1:10 | 10.34 | 264.80 | 175.92 | 150.52 |
| A:B＝1:20 | 11.57 | 236.65 | 179.54 | 131.81 |
| A:B＝1:30 | 12.10 | 226.28 | 180.82 | 125.14 |
| A:B＝1:40 | 12.49 | 219.22 | 181.48 | 120.80 |
| A:B＝1:50 | 13.15 | 208.21 | 181.87 | 114.48 |
From table 1, methylsulfonyl bacterium azoles and benziothiazolinone composite in above ratio, in 15 proportionings, except 1:50, all the other proportioning CTC are all greater than 120, therefore in (100 ~ 1): have synergistic effect in varying degrees between (1 ~ 40); When proportioning is in (40 ~ 1): time between (1 ~ 10), synergy is particularly remarkable, and co-toxicity coefficient is more than 150.
The Toxicity Determination of control citrus bacterial canker disease:
Test method: 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).
The Toxicity Determination result of table 2 methylsulfonyl bacterium azoles and the composite control citrus bacterial canker disease of benziothiazolinone
| Composition | EC 50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 7.48 | 100.00 | / | / |
| Benziothiazolinone (B) | 46.37 | 16.13 | / | / |
| A:B＝100:1 | 6.27 | 119.30 | 99.17 | 120.30 |
| A:B＝75:1 | 5.89 | 126.99 | 98.90 | 128.41 |
| A:B＝40:1 | 4.97 | 150.50 | 97.95 | 153.65 |
| A:B＝30:1 | 4.68 | 159.83 | 97.29 | 164.27 |
| A:B＝20:1 | 4.47 | 167.34 | 96.01 | 174.30 |
| A:B＝10:1 | 4.61 | 162.26 | 92.38 | 175.65 |
| A:B＝5:1 | 4.87 | 153.59 | 86.02 | 178.55 |
| A:B＝3:1 | 5.20 | 143.85 | 79.03 | 182.01 |
| A:B＝1:1 | 6.54 | 114.37 | 58.07 | 196.97 |
| A:B＝1:3 | 11.19 | 66.85 | 37.10 | 180.18 |
| A:B＝1:5 | 15.73 | 47.55 | 30.11 | 157.93 |
| A:B＝1:10 | 20.67 | 36.19 | 23.76 | 152.33 |
| A:B＝1:20 | 27.03 | 27.67 | 20.12 | 137.51 |
| A:B＝1:40 | 33.47 | 22.35 | 18.18 | 122.95 |
| A:B＝1:50 | 36.78 | 20.34 | 17.78 | 114.41 |
From table 2, methylsulfonyl bacterium azoles and benziothiazolinone composite in above ratio, in 15 proportionings, except 1:50, all the other proportioning CTC are all greater than 120, therefore in (100 ~ 1): have synergistic effect in varying degrees between (1 ~ 40); When proportioning is in (40 ~ 1): time between (1 ~ 10), synergy is particularly remarkable, and co-toxicity coefficient is greater than 150.
The Toxicity Determination of control cucumber bacterial angular leaf spot:
Test method: be that 108cfumL-1 pathogen adds 0.5mL in each diameter 9cm sterilizing culture dish by bacteria suspension concentration, then pour 15mL into and be cooled in 45 DEG C of gravy peptone medium, fully mix, solidify.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).
The Toxicity Determination result of table 3 methylsulfonyl bacterium azoles and the composite control cucumber bacterial angular leaf spot of benziothiazolinone
| Composition | EC 50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 9.67 | 100.00 | / | / |
| Benziothiazolinone (B) | 57.46 | 16.83 | / | / |
| A:B＝100:1 | 8.02 | 120.57 | 99.18 | 121.57 |
| A:B＝60:1 | 7.28 | 132.83 | 98.64 | 134.67 |
| A:B＝40:1 | 6.46 | 149.69 | 97.97 | 152.79 |
| A:B＝30:1 | 5.58 | 173.30 | 97.32 | 178.08 |
| A:B＝20:1 | 4.74 | 204.01 | 96.04 | 212.42 |
| A:B＝10:1 | 4.39 | 220.27 | 92.44 | 238.29 |
| A:B＝5:1 | 5.37 | 180.07 | 86.14 | 209.05 |
| A:B＝1:1 | 8.84 | 109.39 | 58.41 | 187.26 |
| A:B＝1:2 | 12.19 | 79.33 | 44.55 | 178.05 |
| A:B＝1:5 | 18.71 | 51.68 | 30.69 | 168.40 |
| A:B＝1:10 | 25.67 | 37.67 | 24.39 | 154.45 |
| A:B＝1:20 | 31.95 | 30.27 | 20.79 | 145.58 |
| A:B＝1:30 | 38.77 | 24.94 | 19.51 | 127.83 |
| A:B＝1:40 | 42.49 | 22.76 | 18.86 | 120.68 |
| A:B＝1:50 | 47.82 | 20.22 | 18.46 | 109.54 |
From table 3, methylsulfonyl bacterium azoles and benziothiazolinone composite in above ratio, in 15 proportionings, except 1:50, all the other proportioning CTC are all greater than 120, therefore in (100 ~ 1): have synergistic effect in varying degrees between (1 ~ 40); When proportioning is in (40 ~ 1): time between (1 ~ 10), synergy is particularly remarkable, and co-toxicity coefficient is greater than 150.
The field control effectiveness test of control cucumber downy mildew:
Test method and drug effect computational methods: with reference to GB/T17980.26-2000 pesticide field efficacy medicine test criterion (one): bactericidal agent for preventing and treating cucumber downy mildew; Controlling object: cucumber downy mildew;
Test site: Nanning doube bridge.
Experimental plot: 24 communities are chosen in field, are divided into 6 groups, often organizes 4 repetitions, random number;
Test method: adopt directed spraying method with test medicine process different districts respectively, first time dispenser is spaced apart 7 days apart from second time spraying time.
Investigation method: Yao Qianmei gets community a bit, often 5 strains, every strain 2 leaf (from top to bottom), the sampling of 5, Yao Houmei community, 10 clumps often, every strain 2 leaf (from top to bottom).Within after dispenser 7 days, 14 days, investigate respectively once.
Stage division:
0 grade: blade is 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% ~ 25% of whole leaf area;
7 grades: lesion area accounts for 26% ~ 50% of whole leaf area;
9 grades: lesion area accounts for more than 51% of whole leaf area.
Contrast medicament: 3% benziothiazolinone wetting powder, registration card PD20100161, Shaanxi Xida Huate Science & Technology Industrial Co., Ltd., commercial.
The field control effectiveness test result of cucumber downy mildew prevented and treated by table 4
Result of the test: as shown in Table 4, from the preventive effect of control cucumber downy mildew, methylsulfonyl bacterium azoles+benziothiazolinone is compared with single dose methylsulfonyl bacterium azoles or benziothiazolinone, when effective ingredient consumption identical even less, 14d control efficiency (the active ingredient dosage 15g/667m of methylsulfonyl bacterium azoles+benziothiazolinone control cucumber downy mildew
2) respectively higher than single dose 20% first sulphur sulfonyl bacterium azoles WP (active ingredient dosage 10g/667m
2) and benziothiazolinone WP (active ingredient dosage 20g/667m
2) control efficiency be more than more than 14.95% and 18.38, and still can reach the preventive effect of more than 74% at 14d, the lasting period is long.
The field control effectiveness test of control citrus bacterial canker disease:
Test method: with reference to GB/T17980.103-2004 pesticide field efficacy medicine test criterion (two) the 103rd part: bactericidal agent for preventing and treating citrus bacterial canker disease;
Controlling object: citrus bacterial canker disease
Test site: Nanning Shi Bu
Experimental plot: choose 24 communities, randomized arrangement, each community 3 strain becomes fruit tree in age, each process 4 repetition;
Test method: adopt directed spraying method, first time dispenser is spaced apart 7 days apart from second time spraying time.
Investigation method: two strains are investigated in every community, every strain are got 5 points, choose 10 fruits and two blade tips at often, before dispenser, investigation once, and after first time dispenser, investigation in 20 days once.
Stage division:
0 grade: anosis;
1 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 16-20;
9 grades: every leaf (really) has scab more than 21.
Contrast medicament: 3% benziothiazolinone wetting powder, registration card PD20100161, Shaanxi Xida Huate Science & Technology Industrial Co., Ltd., commercial.
The field control effectiveness test result of citrus bacterial canker disease prevented and treated by table 5
Result of the test: as shown in Table 5, from the preventive effect of control citrus bacterial canker disease, methylsulfonyl bacterium azoles+benziothiazolinone is compared with single dose methylsulfonyl bacterium azoles or benziothiazolinone, when effective ingredient consumption identical even less, 14d control efficiency (the active ingredient dosage 15g/667m of methylsulfonyl bacterium azoles+benziothiazolinone control citrus bacterial canker disease
2) respectively higher than single dose methylsulfonyl bacterium azoles (active ingredient dosage 15g/667m
2) and benziothiazolinone (active ingredient dosage 20g/667m
2) control efficiency be more than 15.56% and 18.4%; And still can reach the preventive effect of more than 69% at 14d, the lasting period is long.
The field control effectiveness test of control cucumber bacterial angular leaf spot:
Test method: with reference to GB/T17980.103-2004 pesticide field efficacy medicine test criterion (two) the 110th part: bactericidal agent for preventing and treating cucumber bacterial angular leaf spot.
Test site: Nanning doube bridge
Experimental plot: choose 24 communities, randomized arrangement, each community 20 ㎡, each process 4 repetition;
Test method: adopt directed spraying method, first time dispenser is spaced apart 7 days apart from second time spraying time.
Investigation method: every community diagonal five-point type sampling, often 3 strains, investigate whole blade, account for the percentage classification of total leaf area with every leaf lesion area; Before dispenser, investigation once, is investigated once for after dispenser 7 days and 14 days respectively.
Stage division:
0 grade: blade is 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% ~ 25% of whole leaf area;
7 grades: lesion area accounts for 26% ~ 50% of whole leaf area;
9 grades: lesion area accounts for more than 51% of whole leaf area.
Contrast medicament: 3% benziothiazolinone wetting powder, registration card PD20100161, Shaanxi Xida Huate Science & Technology Industrial Co., Ltd., commercial.
The field control effectiveness test result of cucumber bacterial angular leaf spot prevented and treated by table 6
Result of the test: as shown in Table 6, from the preventive effect of control cucumber bacterial angular leaf spot, methylsulfonyl bacterium azoles+benziothiazolinone is compared with single dose methylsulfonyl bacterium azoles or benziothiazolinone, when effective ingredient consumption identical even less, 14d control efficiency (the active ingredient dosage 10g/667m of methylsulfonyl bacterium azoles+benziothiazolinone control cucumber bacterial angular leaf spot
2) respectively higher than single dose first sulphur sulfonyl bacterium azoles (active ingredient dosage 15g/667m
2) and benziothiazolinone (active ingredient dosage 20g/667m
2) control efficiency be more than 19.39% and 19.07, and still can reach the preventive effect of more than 70% at 14d, the lasting period is long.
Claims (8)
1. one kind contains the complex composition of methylsulfonyl bacterium azoles and benziothiazolinone, it is characterized in that, described complex composition is with methylsulfonyl bacterium azoles and benziothiazolinone for main active, and wherein the chemical name of methylsulfonyl bacterium azoles is 2-(to fluorophenyl)-5-mesyl-1,3,4-oxadiazole; The weight ratio of methylsulfonyl bacterium azoles and benziothiazolinone is (100 ~ 1): (1 ~ 40).
2. contain the complex composition of methylsulfonyl bacterium azoles and benziothiazolinone according to claim 1, it is characterized in that, the weight ratio of described methylsulfonyl bacterium azoles and benziothiazolinone is (40 ~ 1): (1 ~ 10).
3. contain the complex composition of methylsulfonyl bacterium azoles and benziothiazolinone according to claim 1, it is characterized in that, the weight ratio of described methylsulfonyl bacterium azoles and benziothiazolinone is (20 ~ 1): (1 ~ 5).
4. one kind contains the preparation of methylsulfonyl bacterium azoles and benziothiazolinone, it is characterized in that, by weight containing the arbitrary described complex composition of 0.1 ~ 90% claim 1-3, all the other are acceptable auxiliary agent and carrier on agricultural chemicals, are then prepared into the bactericide preventing and treating crop pest.
5. the preparation containing methylsulfonyl bacterium azoles and benziothiazolinone according to claim 4, 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 benziothiazolinone according to claim 4 or 5, it is characterized in that, described bactericide is mixed with water dispersible granules, wetting powder, microemulsion, suspending agent, aqueous emulsion, missible oil, suspension seed-coating agent.
7. the application of the arbitrary described complex composition of claim 1-3, it is characterized in that, described complex composition is for preventing and treating crop bacterial disease and/or fungal disease.
8. the arbitrary described application containing the preparation of methylsulfonyl bacterium azoles and benziothiazolinone of claim 4-6, it is characterized in that, described bactericide is for preventing and treating crop bacterial disease and/or fungal disease.
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Cited By (2)
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| CN105432606A (en) * | 2015-12-04 | 2016-03-30 | 陕西西大华特科技实业有限公司 | Composition containing benziothiazolinone and preparing method thereof |
| CN105613517A (en) * | 2016-02-29 | 2016-06-01 | 陕西西大华特科技实业有限公司 | Application of benziothiazolinone to prevention and treatment of potato common scab and method for preventing and treating potato common scab |
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| CN105432606A (en) * | 2015-12-04 | 2016-03-30 | 陕西西大华特科技实业有限公司 | Composition containing benziothiazolinone and preparing method thereof |
| CN106818723A (en) * | 2015-12-04 | 2017-06-13 | 陕西西大华特科技实业有限公司 | Composition containing benziothiazolinone and preparation method thereof |
| CN105613517A (en) * | 2016-02-29 | 2016-06-01 | 陕西西大华特科技实业有限公司 | Application of benziothiazolinone to prevention and treatment of potato common scab and method for preventing and treating potato common scab |
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