CN104488903B - A kind of containing methylsulfonyl bacterium azoles with the complex composition of the gloomy copper of thiophene - Google Patents
A kind of containing methylsulfonyl bacterium azoles with the complex composition of the gloomy copper of thiophene Download PDFInfo
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Abstract
The present invention discloses a kind of containing methylsulfonyl bacterium azoles with the complex composition of the gloomy copper of thiophene, and the active component of this complex composition includes methylsulfonyl bacterium azoles and the gloomy copper of thiophene；Wherein the chemical name of methylsulfonyl bacterium azoles is 2 (to fluorophenyl) 5 mesyl 1,3,4 diazole；The weight ratio of methylsulfonyl bacterium azoles and the gloomy copper of thiophene is (20～1): (1～40), and two kinds of active component account for 0.1% the 90% of said composition gross weight.Described complex composition can be made into the dosage forms such as suspending agent, seed coat agent, wettable powder, water dispersible granules, granule.Two active component methylsulfonyl bacterium azoles of the complex composition of the present invention and thiophene gloomy copper mixture have obvious synergistic function, can reach potentiation, delay Drug resistance, reduce medicament usage amount, reduce cost, the effect such as save labor.Complex composition is mainly used in preventing and treating various crop bacterial disease, such as bacterial blight of rice, bacterial stripe, soft rot of cabbage, bacterial wilt of tomato etc..
Description
Technical field
The present invention relates to technical field of pesticide, particularly to the compositions of two kinds of pesticide activity component mixtures.
Background technology
The most various crop bacterial diseases present the trend increased the weight of year by year, and occurring area increases year by year, give agricultural
Production brings significant damage, is used in the market preventing and treating thin sexually transmitted disease (STD) evil preferable medicament shortcoming.
Bacterial disease is that what the whole world was on the books has kind more than 500 by the class plant disease caused by pathogenetic bacteria, its
Middle bacterial wilt, soft rot, slice are sick, the important disease of bad maize ear rot and the bacterial leaf-blight Deng Doushi world.Recently as weather
The joint effect of the factors such as the fast development of change, the change of crop varieties and industrialized agriculture, crops bacteriosis causes
Loss increase the weight of year by year, simultaneously as lack effective chemical prevention medicament, cause crops bacteriosis to be sent out the most on a large scale
It is born with and is difficult to be effectively controlled at short notice.Crops bacteriosis caused rot, deformity, withered, speckle,
Variable colors etc., the normal growth having a strong impact on crops and quality, cause production loss, even large stretch of total crop failure, therefore controls also
The extension of pre-disease prevention, has extremely important meaning to agricultural production.
To this end, Guizhou University's independent research have new type bactericide " the one class preventing and control crop bacteriosis of independent intellectual property rights
Diazole sulfone compound (Patent No. ZL201110314246.2) ", its structural formula is:
The step of preparation process of this compound and condition:
(1) preparation of different replacing acid methyl ester intermediate: with different organic acid and absolute methanol as raw material, urge at concentrated sulphuric acid
Changing lower back flow reaction 6 10 hours, reduce pressure separating methanol, and after saturated sodium bicarbonate aqueous solution adjusts ph=7, separatory obtains different
Methyl formate；
(2) preparation of different substituted formylhydrazine intermediate: be dissolved in methanol with different methyl formates, the most slowly add 40%
80% hydrazine hydrate, till back flow reaction is complete, separates out different substituted formylhydrazine after cooling；
The preparation of (3) 2 sulfydryl 5 replacement 1,3,4 diazole intermediate: with the formylhydrazine of above-mentioned preparation and KOH,
Carbon bisulfide is raw material, and ethanol is solvent, and back flow reaction is complete, de-ethanol, adjusts PH=5 to obtain 2 sulfydryls 5 and takes
Generation 1,3,4 diazole；
The preparation of (4) 2 thioether 5 replacement 1,3,4 diazole intermediate: with above-mentioned 2 sulfydryl 5 replacements
1,3,4 diazole is raw material, after hydro-oxidation sodium water dissolution, with 12 by dimethyl sulfate (second) ester of mole or halogen
Corresponding sulfide compound is obtained for reactions such as hydrocarbon；
The preparation of (5) 2 methyl (ethyl) sulfonyl 5 replacement 1,3,4 diazole.
With corresponding thioether as raw material, it is dissolved in glacial acetic acid, 2%7% potassium permanganate solution or 30% hydrogen peroxide oxygen
Change and obtain corresponding sulfone compound.
Summary of the invention
For diazole sulfone compound, applicant researches and develops further, as Rn fluorine in halogen atom, R2Select C1-C5 alkane
The methyl of base i.e. obtains the structural formula of diazole sulfone compound:
Its chemical name is 2-(to fluorophenyl)-5-mesyl-1,3,4-diazole, is called for short methylsulfonyl bacterium azoles.
The concrete syntheti c route of compound methylsulfonyl bacterium azoles is as follows:
(1) synthesis to fluorobenzoyl hydrazine
(2) the 2-sulfydryl-5-synthesis to fluorophenyl-1,3,4-diazole
(3) the 2-Dimethyl sulfide-5-synthesis to fluorophenyl-1,3,4-diazole
(4) 2-(to fluorophenyl)-5-mesyl-1,3,4-diazole target compound is prepared
Applicant further study show that, methylsulfonyl bacterium azoles is the preventing and treating bacterial disease medicament of novel structure, can be by suppression
Pathogen energy synthesizes, the growth of suppression antibacterial and breeding.Methylsulfonyl bacterium azoles has the feature of interior suction, conduction, penetrates into blade
After epidermis, energy transporting is to other positions of same blade.Substantial amounts of isolated test shows, methylsulfonyl bacterium azoles is to causing vegetative bacteria
The various pathogenetic bacterias of disease have good inhibiting effect, the most directly suppress bacterial multiplication.Through repeatedly pot experiment and field
The test of pesticide effectiveness is verified, show that methylsulfonyl bacterium azoles is respectively provided with preferable prevention effect to crop bacterial disease, especially white to Oryza sativa L.
Leaf blight, slice disease, tobacco bacterial wilt, bacterial wilt of tomato, citrus bacterial canker disease etc. all have good control effect, and energy
Stimulate plant growth healthy and strong to a certain extent, improve the resistance of crop.This compound has efficiently, wide spectrum, use safety
Feature, be one have much exploitation potential quality antibacterial.But the alone Drug resistance that is easily generated of this medicament, drug effect declines.Applicant
Test finds that itself and the gloomy copper of thiophene are compounding and has good potentiation.
The gloomy copper of thiophene, chemical name is N, N '-methylene-bis-(2-amino-5-sulfydryl 1,3,4 thiadiazoles) copper, and chemical formula is
C5H4N6S4Cu, molecular weight is 339.5.The gloomy copper of thiophene is also a kind of thiazoles organic copper antibacterial, the registered white leaf of preventing and treating Oryza sativa L.
Rot, bacterial stripe, soft rot of cabbage and bacterial wilt of tomato.High-efficiency broad spectrum, hypotoxicity, safety and environmental protection, nuisanceless,
To bacterial disease specially good effect, efficient to fungal disease.The complex composition of methylsulfonyl bacterium azoles and the gloomy copper of thiophene is not found through retrieval
Report.
In view of this, the present invention is directed to the deficiency that prior art exists, it is provided that a kind of compounding containing methylsulfonyl bacterium azoles and the gloomy copper of thiophene
Compositions, said composition has obvious potentiation relative to single dose, can effectively prevent and treat crop bacterial disease or suppression is planted
Thing bacterial disease, reduces the using dosage of pesticide, has saved drug cost, and fungicidal spectrum is the most extensive, delays cause of disease thin
Bacterium is to methylsulfonyl bacterium azoles and the comprehensive control of the Drug resistance of Fungicidal compounds II, beneficially environmental conservation and agricultural disease.
For realizing above-mentioned purpose, the technical scheme is that
A kind of containing methylsulfonyl bacterium azoles with the complex composition of the gloomy copper of thiophene, described complex composition with methylsulfonyl bacterium azoles and the gloomy copper of thiophene is
Main active, wherein the chemical name of methylsulfonyl bacterium azoles is: 2-(to fluorophenyl)-5-mesyl-1,3,4-diazole.
In above-described complex composition, wherein the weight ratio of methylsulfonyl bacterium azoles and the gloomy copper of thiophene is (20～1): (1～40), first
Sulphonyl bacterium azoles and the gloomy copper of thiophene account for the 0.1%-90% of described complex composition gross weight.
In above-described complex composition, as preferably, the weight ratio of methylsulfonyl bacterium azoles and the gloomy copper of thiophene is (5～1): (1～10),
Methylsulfonyl bacterium azoles and the gloomy copper of thiophene account for the 1%-80% of described complex composition gross weight.
In order to preferably play the bactericidal effect of active component in complex composition, described complex composition also includes on pesticide
One or more in acceptable auxiliary agent, solvent or filler.
In some embodiments that the present invention provides, described auxiliary agent includes surfactant, wetting dispersing agent, if desired also
Other conventional functionality auxiliary agents such as antifreezing agent, thickening agent, stabilizer, defoamer, disintegrating agent, film former can be added.
As the further optimization of technical solution of the present invention, acceptable auxiliary agent, solvent or filler on above-described pesticide
Optimized choice is as follows:
Described surfactant includes T-60, T-80, T-85 selected from polyoxyethylene sorbitan fatty acid ester series, fat
Polyoxyethylenated alcohol series include AEO-9, JFC, condensation compound of alkyl phenol and epoxy ethane series include OP-10, OP-18,
OP-20, NPE series includes NP-10, NP-15, NP-20, styrylphenol formaldehyde resin polyoxy second
Alkene-oxypropylene block type polyether series include 33#, 37#, triphen ethyl phenol polyoxyethylene ether series includes 601#, 602#,
Double phenethyl phenol polyethenoxy ether series include 604#, in anion surfactant calcium dodecyl benzene sulfonate (500#)
Plant or several.
Described wetting dispersing agent is selected from sodium lauryl sulphate (K12), diisobutyl LOMAR PWA EINECS 246-676-2 (abbreviation pulls open powder), methylene
The double bitter edible plant sulfonic acid of base (being called for short NNO), acrylic acid and propionic acid amide. copolymer (being called for short DA), (letter of di-2-ethylhexylphosphine oxide methyl naphthalene sulfonic acid
Claim MF) polyacrylic acid (be called for short DC), desaccharide the lignin sulfonic acid (being called for short M-9) of classification, the wood of desaccharide condensation and modification
Quality sulfonic acid (being called for short M-10), lignosulfonates (being called for short M-11), poly carboxylic acid derivative's (being called for short CF), lignin
In sulfonic acid (be called for short M-14) one or more.
The described thickening agent any one or two kinds in xanthan gum, the aluminium-magnesium silicate.
Described antifreezing agent is selected from any one or a few in glycerol, propylene glycol, ethylene glycol, isopropanol, carbamide.
Described disintegrating agent is selected from: in sodium chloride, sodium phosphate, ammonium phosphate, ammonium sulfate, sodium sulfate, potassium carbonate, potassium chloride
Any one or a few
Described film former is selected from: hydroxypropyl cellulose, methylcellulose, animal glue, polyvinylpyrrolidone, polyacrylic acid
Any one or a few in sodium
One or more in white carbon, Kaolin, potter's clay, bentonite, kieselguhr, earth powder of described filler.
Described aqueous solvent.
According to different use demands, the complex composition that the present invention provides can be made into multiple dosage form, such as wettable powder, water
Dispersible granule, microemulsion, aqueous emulsion, ultra low volume liquids, suspending agent, suspension emulsion, soluble liquid, soluble powder,
Seed dressing, suspension seed-coating agent, dry suspending agent, granule or slow releasing agent.It is not limited only to the dosage form that the present invention provides.
As preferably, in some embodiments that the present invention provides, the dosage form suspending agent of complex composition, wettable powder,
Water dispersible granules, suspension seed-coating agent.
The present invention also provides for described complex composition purposes in terms of preventing and treating crop bacterial disease, is mainly used in preventing and treating such as
Soft rot of Chinese cabbage, X. c. pv. oryzicola, bacterial leaf-blight, cucumber bacterial angular leaf spot, citrus bacterial canker disease, Nicotiana tabacum L., melon with
And the bacterial wilt of solanaceous vegetable, Fructus Lycopersici esculenti bacterial disease macule disease, Peptic Ulcers and shot hole etc..
Complex composition of the present invention can be used by commonsense method, processes as being watered spraying stem and leaf, it is also possible to root fills and executes,
Can also dress seed or seed pelleting uses.It is mainly used in Oryza sativa L., Fructus Lycopersici esculenti, Chinese cabbage etc. crops, prevents and control bacterial disease
Evil, to guarantee crop yield.
The complex composition of the present invention compared with prior art has the advantages that
1, methylsulfonyl bacterium azoles and two kinds of bactericide agricultural chemicals of the gloomy copper of thiophene compound, and have obvious synergistic function, permissible
Carry out from multiple sites suppressing growth of pathogenic bacteria, and be prevented from pathogen and develop immunity to drugs, it is thus possible to reach efficient anti-disease-control
The effect of former bacterium.Methylsulfonyl bacterium azoles and the gloomy copper of thiophene are by (20～1): (1～40) compound, to soft rot of cabbage, paddy bacterial bar
Pinta, bacterial wilt of tomato show obvious synergistic function, and co-toxicity coefficient is more than 120.
2, fungicidal spectrum is wide, strong adaptability.Bacterial blight of rice, bacterial stripe, tobacco bacterial wilt, bacterial wilt of tomato
All have etc. equal bacterial disease and well control effect.
3, preventive effect is good, the complex composition of the present invention its dosage comparison 10g/667m fewer than single dose effective ingredient consumption2, but
Preventive effect exceeds single dose more than 20%.
Detailed description of the invention
Present invention the following example illustrates, but does not limits the scope of the invention.Methylsulfonyl bacterium azoles used in the present invention
Former medicine is provided by Guizhou University, and other former medicines used and preparation are commercial.Wherein active component (A) is methylsulfonyl bacterium
Azoles；Active component (B) is the gloomy copper of thiophene.
Hereinafter prepare embodiment, wetting dispersing agent and surfactant and all use abbreviation or commercial disignation.
Embodiment prepared by preparation:
One, the processing of suspending agent and embodiment
By surfactant and dispersant, antifreezing agent, thickening agent, moisture content mixing, through high speed shear mix homogeneously, add successively
Enter methylsulfonyl bacterium azoles, the gloomy copper of thiophene, abrading-ball 2～3 hours in ball crusher, prepare the outstanding of complex composition of the present invention
Floating agent.
Two, the processing of wettable powder and embodiment
By methylsulfonyl bacterium azoles, the gloomy copper of thiophene, sodium lauryl sulphate, dispersant, white carbon, filler mix homogeneously, through air-flow
After pulverizer is pulverized, stir 30min, obtain the wettable powder of complex composition of the present invention.
Three, the preparation of water dispersible granules
By methylsulfonyl bacterium azoles, the gloomy copper of thiophene, sodium lauryl sulphate, dispersant, white carbon, disintegrating agent filler mix homogeneously,
After jet mill is pulverized, stir 30min, through mediating, rear add fluidized-bed granulation dryer is carried out pelletize, be dried,
Obtain the water dispersible granules of complex composition of the present invention.
Four, suspension seed-coating agent
By methylsulfonyl bacterium azoles and the gloomy copper of thiophene through comminution by gas stream, add surfactant and dispersant, film former, thickening agent, anti-
After freezing after agent is thoroughly mixed with water, put into sand mill in proportion and grind 2 times, until the fineness of the particles of suspension reaches D50 be
2-3 μm, D90 ＜ 8 μm, obtain the suspension seed-coating agent of complex composition of the present invention.
The present composition is in addition to can being made into above dosage form, in conjunction with the common knowledge of those of ordinary skill in the art, adds phase
Answer the adjuvant of dosage form, it is also possible to make microemulsion, aqueous emulsion, ultra low volume liquids, soluble liquid, soluble powder,
The multiple dosage forms such as seed dressing, dry suspending agent, granule or slow releasing agent.
Toxicity Determination:
The test of following indoor biometrics uses the abundant method of Sun Yun to calculate co-toxicity coefficient (CTC) and evaluates mixed effect.
Toxicity index TI (B)=(EC of standard agent A50The EC of ÷ B agent50)×100
Actual toxicity index ATI (AB)=(EC of A50The EC of ÷ AB50)×100
Theoretical toxicity index TTI (AB)=TI (A) × A percent+TI (B) × B percent in mixture in mixture
Actual measurement toxicity index (ATI)=(standard agent EC50÷ reagent agent EC50)×100
Percentage composition+B medicament toxicity index × the mixture of A in theoretical toxicity index (TTI)=A medicament toxicity index × mixture
The percentage composition of middle B
Co-toxicity coefficient (CTC)=[mixture actual measurement toxicity index (ATI) ÷ mixture theory toxicity index (TTI)] × 100
Evaluation criterion is: co-toxicity coefficient >=120 show as potentiation；Co-toxicity coefficient≤80 show as antagonism；80 < altogether
< 120 show as summation action to poison coefficient.
Toxicity Determination embodiment one:
Strain cultured in test tube is extracted test tube tampon at alcohol burner, pours 10ml sterilized water into, use disinfection inoculation
Pin scrapes pathogenic bacteria on inclined-plane gently, makes spore suspension, then this spore suspension is poured into going out equipped with several glass beads in advance
In bacterium triangular flask, filter bacterium solution with sterile gauze after shake 5min, put in another sterilizing triangular flask, i.e. make required bacterium solution.
By beef extract-peptone agar culture medium melt, when being cooled to 45 DEG C～50 DEG C, aseptically together with
0.2ml bacterial suspension is poured into the most rapidly in sterilizing culture dish, every ware 15ml culture medium, shakes up rear cooled and solidified.
Punch with the card punch (aperture 4mm) after sterilizing, 1ml medicinal liquid is dripped in circular hole, is placed in 28 DEG C of calorstats training
After supporting 2d, press decussation method with slide gauge and measure 2 diameters of inhibition zone, average, calculate suppression ratio,
Obtain virulence curve and EC50, and press Sun Yun abundant method calculating co-toxicity coefficient, measurement result is shown in Table 1.
Table 1 methylsulfonyl bacterium azoles and the gloomy copper of thiophene compound the joint toxicity measuring result preventing and treating soft rot of cabbage
| Composition | EC50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 15.63 | 100.00 | / | / |
| The gloomy copper of thiophene (B) | 125.57 | 12.45 | / | / |
| A:B=20:1 | 13.56 | 115.27 | 95.83 | 120.28 |
| A:B=15:1 | 13.08 | 119.50 | 94.53 | 126.41 |
| A:B=10:1 | 12.94 | 120.79 | 92.04 | 131.23 |
| A:B=8:1 | 12.21 | 128.01 | 90.27 | 141.80 |
| A:B=5:1 | 12.06 | 129.60 | 85.41 | 151.74 |
| A:B=3:1 | 11.92 | 131.12 | 78.11 | 167.87 |
| A:B=2:1 | 12.55 | 124.54 | 70.82 | 175.87 |
| A:B=1:1 | 14.49 | 107.87 | 56.22 | 191.85 |
| A:B=1:2 | 17.98 | 86.93 | 41.63 | 208.81 |
| A:B=1:4 | 26.56 | 58.85 | 29.96 | 196.44 |
| A:B=1:6 | 36.79 | 42.48 | 24.95 | 170.25 |
| A:B=1:10 | 50.44 | 30.99 | 20.41 | 151.85 |
| A:B=1:15 | 60.52 | 25.83 | 17.92 | 144.12 |
| A:B=1:20 | 72.16 | 21.66 | 16.62 | 130.35 |
| A:B=1:30 | 80.24 | 19.48 | 15.27 | 127.55 |
| A:B=1:40 | 88.67 | 17.63 | 14.58 | 120.88 |
| A:B=1:50 | 94.16 | 16.60 | 14.16 | 117.19 |
From measurement result table 1: methylsulfonyl bacterium azoles and the gloomy copper of thiophene are (20～1) by weight: in the range of (1～40)
The compounding co-toxicity coefficient preventing and treating soft rot of cabbage all reaches more than 120, illustrates that two composite reagents are to preventing and treating soft rot of cabbage
There is potentiation.Being wherein (5～1) when weight ratio: in the range of (1～10), each co-toxicity coefficient processed is 150
Above, potentiation is especially pronounced.
Toxicity Determination embodiment two:
Use in vitro Nephelometric Determination, design concentration on the basis of pilot study, each medicament is added separately to NA
In fluid medium, gradient dilution makes pastille culture medium, and Inoculated Rice Xanthomonas campestris PV.oryzicola is placed on 28 DEG C and shakes
Swing cultivation about 24h, measure its turbidity (turbidity is changing into positive correlation with bacterium amount) with transmissometer, right according to blank
According to turbidity and the turbidity of process calculate each chemicals treatment suppression ratio that bacterial growth is bred, by the probability of suppression ratio
Linear regression analysis between the logarithm value of value and series drug concentration, obtains the EC of each medicament50Value, CTC value,
Measurement result is shown in Table 2.
Table 2 methylsulfonyl bacterium azoles and the gloomy copper of thiophene compound the joint toxicity measuring result of preventing and treating bacterial leaf streak of rice
| Composition | EC50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 7.63 | 100.00 | / | / |
| The gloomy copper of thiophene (B) | 109.48 | 6.97 | / | / |
| A:B=20:1 | 6.64 | 114.91 | 95.57 | 120.24 |
| A:B=15:1 | 6.46 | 118.11 | 94.19 | 125.40 |
| A:B=11:1 | 6.4 | 119.22 | 92.25 | 129.24 |
| A:B=9:1 | 6.34 | 120.35 | 90.70 | 132.69 |
| A:B=7:1 | 6.12 | 124.67 | 88.37 | 141.08 |
| A:B=5:1 | 6.01 | 126.96 | 84.49 | 150.25 |
| A:B=3:1 | 6.05 | 126.12 | 76.74 | 164.34 |
| A:B=1:1 | 8.07 | 94.55 | 53.48 | 176.78 |
| A:B=1:2 | 10.91 | 69.94 | 37.98 | 184.14 |
| A:B=1:3 | 13.22 | 57.72 | 30.23 | 190.94 |
| A:B=1:5 | 19.38 | 39.37 | 22.47 | 175.18 |
| A:B=1:7 | 25.44 | 29.99 | 18.60 | 161.26 |
| A:B=1:10 | 32.01 | 23.84 | 15.43 | 154.51 |
| A:B=1:16 | 43.27 | 17.63 | 12.44 | 141.73 |
| A:B=1:22 | 51.44 | 14.83 | 11.01 | 134.67 |
| A:B=1:31 | 60.48 | 12.62 | 9.88 | 127.73 |
| A:B=1:40 | 68.56 | 11.13 | 9.24 | 120.46 |
| A:B=1:50 | 73.42 | 10.39 | 8.79 | 118.18 |
From measurement result table 2: methylsulfonyl bacterium azoles and the gloomy copper of thiophene are (20～1) by weight: in the range of (1～40)
The compounding co-toxicity coefficient to X. c. pv. oryzicola all reaches more than 120, illustrates that two composite reagents are to preventing and treating X. c. pv. oryzicola tool
There is potentiation.Being wherein (5～1) when weight ratio: compounding in the range of (1～10), each co-toxicity coefficient processed is 150
Above, potentiation is especially pronounced.
Toxicity Determination embodiment three:
After being activated in NA culture medium by bacterial wilt of tomato pathogen, it is made into bacterium stock solution with sterilized water, bacterium stock solution is diluted to
The clump count grown after coated plate 100ul is the bacteria suspension of about 100, standby.
Take 400ul bacteria suspension to mix with equivalent pesticide single dose, take 100ul with liquid-transfering gun, be placed in the NA being ready for and put down
On plate, with sterilized " L " shape Glass rod by bacteria suspension coating uniformly, cultivate 48h for 28 DEG C, count clump count, and by public affairs
Formula calculates bacteriostasis rate, bacterium colony suppression ratio (%)=(comparison clump count-process clump count)/comparison clump count × 100, often locates
Reason is repeated 4 times, and replaces pesticide-treated for comparison with sterilized water, and the result of gained uses Excel software analysis, calculates each medicine
The EC of agent50, and calculating co-toxicity coefficient according to the abundant method of Sun Yun, measurement result is shown in Table 3.
Table 3 methylsulfonyl bacterium azoles and the gloomy copper of thiophene compound the joint toxicity measuring result of control of plant bacterial wilt
| Composition | EC50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 12.63 | 100.00 | / | / |
| The gloomy copper of thiophene (B) | 153.48 | 8.23 | / | / |
| A:B=20:1 | 10.99 | 114.92 | 95.63 | 120.17 |
| A:B=19:1 | 10.73 | 117.71 | 95.41 | 123.37 |
| A:B=17:1 | 10.49 | 120.40 | 94.90 | 126.87 |
| A:B=14:1 | 10.25 | 123.22 | 93.88 | 131.25 |
| A:B=12:1 | 10.02 | 126.05 | 92.94 | 135.62 |
| A:B=9:1 | 9.86 | 128.09 | 90.82 | 141.04 |
| A:B=5:1 | 9.58 | 131.84 | 84.70 | 155.64 |
| A:B=3:1 | 9.39 | 134.50 | 77.06 | 174.55 |
| A:B=1:1 | 12.61 | 100.16 | 54.11 | 185.09 |
| A:B=1:2 | 17.10 | 73.86 | 38.82 | 190.26 |
| A:B=1:4 | 26.84 | 47.06 | 26.58 | 177.02 |
| A:B=1:8 | 41.33 | 30.56 | 18.43 | 165.85 |
| A:B=1:10 | 49.88 | 25.32 | 16.57 | 152.79 |
| A:B=1:13 | 58.72 | 21.51 | 14.78 | 145.49 |
| A:B=1:24 | 75.68 | 16.69 | 11.90 | 140.24 |
| A:B=1:33 | 89.50 | 14.11 | 10.93 | 129.13 |
| A:B=1:40 | 100.55 | 12.56 | 10.47 | 120.00 |
| A:B=1:50 | 108.64 | 11.63 | 10.03 | 115.92 |
From measurement result table 3: methylsulfonyl bacterium azoles and the gloomy copper of thiophene are in (20～1) by weight: compounding of (1～40)
In the range of the co-toxicity coefficient of water bacterial wilt of tomato is all reached more than 120, show obvious synergistic function.Wherein
When weight ratio is (5～1): compounding in the range of (1～10), each co-toxicity coefficient processed is more than 150, and potentiation is the most aobvious
Write.
Land for growing field crops test examples
In order to clear and definite methylsulfonyl bacterium azoles copper gloomy with thiophene alone with time mixed to the preventing and treating of bacterial disease on Oryza sativa L., Chinese cabbage and Fructus Lycopersici esculenti
Effect, present invention applicant different regions at home have carried out substantial amounts of field test.
Comparison medicament: 20% thiophene gloomy copper suspending agent registration card: PD20110274, Zhejiang east wind Chemical Co., Ltd., commercial.
Soft rot of cabbage field control effectiveness test one:
Test method: according to " GB/T17980.114-2004 pesticide field efficacy medicine test criterion (two) the 114th
Point: the bactericidal agent for preventing and treating soft rot of Chinese cabbage test of pesticide effectiveness ", when disease onset, spray dispenser for the first time, carries out second after 5d
Secondary spray dispenser.Dispenser twice altogether, each process plot area is 10m2, number of repetition 4 times.
Investigation method: the investigation method specified according to above-mentioned " GB/T17980.114-2004 ", for the second time after dispenser respectively
Whole plant are investigated in every community by 7d, 14d, and record is investigated total strain number and diseased plant number, calculated diseased plant rate and prevent and treat preventive effect.
Result of the test refers to table 4.
Soft rot of cabbage field control effectiveness test result prevented and treated by table 4
As shown in Table 4, soft rot of cabbage, methylsulfonyl bacterium azoles+gloomy copper of thiophene and single dose methylsulfonyl bacterium azoles are prevented at the vegetable fields initial stage
Or the gloomy copper of thiophene compares, effective ingredient dosage identical even less in the case of, methylsulfonyl bacterium azoles+thiophene gloomy copper preventing and treating Chinese cabbage
7d prevention effect (effective ingredient dosage 20g/667m of soft rot2) respectively higher than single dose (50.77-60.04) % and
(27.85-37.12) %；And remaining to reach the preventive effect of more than 76.08% at 14d, the lasting period is long.
Bacterial leaf streak of rice field control effectiveness test two:
Test method: specify application method according to " pesticide field efficacy medicine test criterion one (GB/T17980.19-2000) ",
Before disease occurs or early period of origination for the first time spray dispenser, second time spray dispenser after 5d.Dispenser twice, each place altogether
Reason plot area is 20m2, number of repetition 4 times.
Investigation method: specify investigation method according to " pesticide field efficacy medicine test criterion one (GB/T17980.19-2000) ",
Every 5, community sampling, every takes 50 strains, every strain investigation boot leaf and boot leaf following two panels leaf.
X. c. pv. oryzicola Seriousness gradation standard:
0 grade: anosis；
1 grade: lesion area accounts for less than the 1% of one-piece blade area, scab length is less than 0.3cm；
3 grades: lesion area accounts for the 2%～5% of one-piece blade area, scab length is more than 0.3cm；
5 grades: lesion area accounts for the 6%～25% of one-piece blade area, and part scab connecting length is more than 1cm；
7 grades: lesion area accounts for the 26%～50% of one-piece blade area, a large amount of scabs connect, and length is more than 1cm；
9 grades: lesion area accounts for more than the 50% of one-piece blade area, scab connects, and large area is withered.
Result of the test is shown in Table 5.
Oryza sativa L. thin property cecospora spot field control effectiveness test result prevented and treated by table 5
As shown in Table 5, bacterial leaf streak of rice, methylsulfonyl bacterium azoles+gloomy copper of thiophene and single dose methylsulfonyl are prevented at the land for growing field crops initial stage
Bacterium azoles or the gloomy copper of thiophene are compared, in the case of effective ingredient dosage is identical even less, and methylsulfonyl bacterium azoles+thiophene gloomy copper preventing and treating
7d prevention effect (effective ingredient dosage 20g/667m of Oryza sativa L. thin property cecospora spot2) it is respectively higher than single dose (55.19-66.12)
% and (23.06-33.99) %；And remaining to reach the preventive effect of more than 74.88% at 14d, the lasting period is long.
Bacterial wilt of tomato field efficacy experiment three:
Test method: specify application method according to " pesticide field efficacy medicine test criterion (NY/T1464.32-2010) ", is beginning
Pouring root or spray dispenser for the first time when seeing diseased plant, second time pouring root or spray dispenser after 5d.Dispenser twice altogether, each process is little
District's area is 20m2, number of repetition 4 times.
Investigation method: according to " pesticide field efficacy medicine test criterion (NY/T1464.32-2010) " specify investigation method, second
After secondary dispenser, whole plant are investigated in each community by 7d, 14d, record total strain number and diseased plant number, calculate diseased plant rate and preventing and treating is anti-
Effect.
Result of the test is shown in Table 6.
Table 6 control of plant bacterial wilt field control effectiveness test result
As shown in Table 6, bacterial wilt of tomato, methylsulfonyl bacterium azoles+gloomy copper of thiophene and single dose methylsulfonyl bacterium azoles are prevented at the vegetable fields initial stage
Or the gloomy copper of thiophene compares, effective ingredient dosage identical even less in the case of, methylsulfonyl bacterium azoles+thiophene gloomy copper preventing and treating Fructus Lycopersici esculenti
7d prevention effect (effective ingredient dosage 20g/667m of bacterial wilt2) respectively higher than single dose (51.86-63.61) % and
(21.36-34.11) %；And remaining to reach the preventive effect of more than 69.60% at 14d, the lasting period is long.
Claims (9)
1. one kind contains methylsulfonyl bacterium azoles and the complex composition of the gloomy copper of thiophene; it is characterized in that: described complex composition is with methylsulfonyl bacterium azoles and the gloomy copper of thiophene as main active; wherein the chemical name of methylsulfonyl bacterium azoles is 2-(to fluorophenyl)-5-mesyl-1,3,4-diazole；Described methylsulfonyl bacterium azoles and the weight ratio of the gloomy copper of thiophene are (20 ~ 1): (1 ~ 40), methylsulfonyl bacterium azoles and the gloomy copper of thiophene account for the 0.1%-90% of described complex composition gross weight.
Complex composition the most according to claim 1, it is characterised in that described methylsulfonyl bacterium azoles and the weight ratio of the gloomy copper of thiophene are (5 ~ 1): (1 ~ 10), methylsulfonyl bacterium azoles and the gloomy copper of thiophene account for the 1%-80% of described complex composition gross weight.
3. according to the arbitrary described complex composition of claim 1-2, it is characterised in that described complex composition is possibly together with one or more in auxiliary agent acceptable on pesticide.
4. according to the arbitrary described complex composition of claim 1-2, it is characterised in that described complex composition is possibly together with one or more in solvent acceptable on pesticide.
5. according to the arbitrary described complex composition of claim 1-2, it is characterised in that described complex composition is possibly together with one or more in filler acceptable on pesticide.
Complex composition the most according to claim 3, it is characterised in that described complex composition is configured to wettable powder, water dispersible granules, suspending agent, suspension seed-coating agent.
Complex composition the most according to claim 4, it is characterised in that described complex composition is configured to wettable powder, water dispersible granules, suspending agent, suspension seed-coating agent.
Complex composition the most according to claim 5, it is characterised in that described complex composition is configured to wettable powder, water dispersible granules, suspending agent, suspension seed-coating agent.
9. the purposes in terms of preventing and treating crop bacterial disease of the complex composition as described in claim 1-8 is arbitrary.
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