CN104488963B - Compound composition with methanesulphonyl myclobutanil and organic copper bactericide and preparation - Google Patents
Compound composition with methanesulphonyl myclobutanil and organic copper bactericide and preparation Download PDFInfo
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Abstract
The invention relates to a compound composition with methanesulphonyl myclobutanil and an organic copper bactericide and a preparation. The compound composition consists of methanesulphonyl myclobutanil and the organic copper bactericide, wherein the organic copper bactericide is selected from any one of cuaminosulfate, oxine-copper, copper nitrohumic acid, mixed amino acid copper, copper resinate, copper citrate, copper succinate, cupric nonyl phenolsulfonate and copper acetate; the weight ratio of the methanesulphonyl myclobutanil to the organic copper bactericide is (10:1)-(1:50). The invention also relates to an agricultural bactericide; the agricultural bactericide contains 0.1-90wt% of the compound composition. The compound composition and the preparation thereof have a remarkable synergetic interaction effect in comparison with single dosage and have the advantages of improving the bactericidal effect, reducing the dosage, reducing the control cost, bringing benefit to delay or resist the bacterial drug resistance and decreasing the environmental pollution and the pesticide residue at the same time.
Description
Technical field
The invention belongs to technical field of pesticide combination, is related to a kind of complex composition, more particularly, to a kind of methylsulfonyl is contained
The disinfectant use in agriculture of bacterium azoles and organic copper series bactericidal agent.
Background technology
In actual agricultural production, generation fungal disease is also accompanied by while there is bacterial disease.Peasant is in order to save
About man-hour operation, also adds the medicament of preventing and treating fungal disease, but this random mixture, no while bacterial disease is prevented and treated
Synergistic effect is not only reached, it is also possible to a series of problems, such as producing antagonism, waste medicament, remain exceeded or poisoning.
Currently used for the organic copper series bactericidal agent of corps diseases is prevented and treated because use time is long, pathogen is to which creating one
The fixed resistance to the action of a drug, the prevention effect of its preventing and treating agricultural disease is not ideal, and organic copper preventing and treating spectrum is narrow, limits its use.
Organic copper series bactericidal agent is exactly the copper agent containing carbon (C) element in structure；Existing protective effect, there is prevention effect again, and simultaneous
The certain treatment of tool and eradicant action.The current organic copper agent developed has：It is network ammonia copper, copper 8-hydroxyquinolinate, nitro humus acid copper, mixed
Close amino acid copper, copper rosinate, copper citrate, butanedioic acid copper, nonylphenolsulfonate copper, copper acetate.The organic copper class that the present invention is referred to is sterilized
Agent is known and published pesticide species.
Network ammonia copper (cuaminosulfate)：CAS 7646-79-9, chemical formula Cu (NH3)4SO4, mainly by copper ion
Bactericidal action is played, the network ammonia copper facilitation certain to the growth tool of cotton seedling, watermelon etc. plays certain disease-resistant and volume increase and make
With.
Copper 8-hydroxyquinolinate (oxine-copper)：CAS 10380-28-6, chemical formula C18H12CuN2O2, it is a kind of wide spectrum, height
Effect, organic copper chelate of low-residual, have good preventive and therapeutic action to the virus such as fungi, bacillary.In crop surface
One layer of tight diaphragm is formed, suppresses germ to sprout and invade, so as to reach the purpose prevented and cured diseases.
Nitro humus acid copper (nitrohumic acid+copper sulfate)：Chemical formula NO2R(COO)4Cu2, this product
For broad spectrum protection type bactericide, Main Function mechanism is the protein coagulating that copper ion makes on pathogen cell membrane, while part
Copper ion penetrates into that pathogeny bacterium is intracellular, and poisoning the enzyme containing sulfydryl makes the biochemical activity of thalline stop and kill germ, right
Crop fungal disease and bacterial disease have good prevention effect.
Kilnitamin copper：Complex compound is produced by several amino acids and copper effect.Its bactericidal action is mainly copper ion
The enzyme containing-SH bases is poisoned, the biochemical activity of these enzyme controls is stopped and is killed germ.
Copper rosinate：CAS 10248-55-2, chemical name is 1,2,3,4,4a, 9,10,10a- octahydros-Isosorbide-5-Nitrae a- bis-
Methyl -7- (1- Methylethyls) -1- phenanthrene carboxylic acid copper, this product is compounded by copper rosinate active compound, solvent and emulsifying agent
Planting can replace the bactericide of Bordeaux mixture, have good prevention effect to downy mildew of garpe etc..
Copper citrate (copper citrate)：Chemical name is copper citrate complex compound, twists lemon acid copper complex and ammonia
Close copper sulphate, ammino zinc sulfate composition bactericide anti-wither chemical.
Butanedioic acid copper (Cupric tartrate trihydrate)：CAS 815-82-7, chemical formula C4H4CuO6·
3H2O, succinic acid copper, penta succinic acid copper, the mixture of adipic acid copper are to generate butanedioic acid copper using butanedioic acid and mantoquita reaction.
Nonylphenolsulfonate copper (cuppric nonyl phenolsulfonate)：Nonylphenolsulfonate copper is a kind of stronger organic copper of permeability
Bactericide, in recent years, because the prevention effect of nonylphenolsulfonate copper is notable, is widely used by friends peasant.
Copper acetate (copper acetate)：Chemical formula Cu (CH3COO)2·H2O, disinfectant use in agriculture, typically with hydrochloric acid
Quinoline guanidine compounding use, prevents and treats crop pest.
For this purpose, Guizhou University's independent research and possessing new type bactericide " the one class preventing and control crop bacterium of independent intellectual property rights
Disease oxadiazole sulfone compound (Patent No. ZL201110314246.2) ", its structural formula is：
The step of preparation process and condition of the compound：
(1) preparation of the sour methyl ester intermediate of different replacements：With different organic acid and absolute methanol as raw material, in the concentrated sulfuric acid
The lower back flow reaction 6-10 hour of catalysis, reduce pressure separating methanol, and saturated sodium bicarbonate aqueous solution adjusts point liquid after ph=7 to obtain different first
Sour methyl esters；
(2) preparation of the different formylhydrazine intermediates for replacing：Methyl alcohol is dissolved in different methyl formates, is then slowly added
40%-80% hydrazine hydrates, till back flow reaction is complete, separate out the different formylhydrazines for replacing after cooling；
(3) 2- sulfydryls -5- replaces the preparation of -1,3,4- oxadiazole intermediates：With the formylhydrazine and KOH of above-mentioned preparation, two
Nitric sulfid is raw material, and ethanol is solvent, and back flow reaction completely, takes off ethanol, adjusts PH=5 to obtain 2- sulfydryls -5- and replaces -1,3,4- Evil
Diazole；
(4) 2- thioethers -5- replaces the preparation of -1,3,4- oxadiazole intermediates：Replace -1,3,4- with above-mentioned 2- sulfydryls -5-
Oxadiazole is raw material, after hydro-oxidation sodium water dissolves, is reacted by dimethyl sulfate (second) ester or halogenated hydrocarbons of mole etc. with 1-2
To corresponding sulfide compound；
(5) 2- methyl (ethyl) sulfonyl -5- replaces the preparation of -1,3,4- oxadiazoles.
With corresponding thioether as raw material, in being dissolved in glacial acetic acid, 2%-7% potassium permanganate solutions or 30% hydrogen peroxide
Oxidation obtains corresponding sulfone compound.
The content of the invention
Dui Yu oxadiazole sulfone compounds, applicant further researches and develops, when Rn is selected from the fluorine in halogen atom, R2Select C1-C5
The methyl of alkyl is Jied and get s the structural formula of oxadiazole sulfone compound：
Its chemical name be 2- (p-fluorophenyl) -5- mesyl -1,3,4- oxadiazoles, abbreviation methylsulfonyl bacterium azoles.
The concrete syntheti c route of compound methylsulfonyl bacterium azoles is as follows：
(1) to the synthesis of fluorobenzoyl hydrazine
(2) synthesis of 2- sulfydryls -5- p-fluorophenyls -1,3,4- oxadiazoles
(3) synthesis of 2- Dimethyl sulfides -5- p-fluorophenyls -1,3,4- oxadiazoles
(4) 2- (p-fluorophenyl) -5- mesyl -1,3,4- oxadiazole target compounds are prepared
Applicant further study show that methylsulfonyl bacterium azoles is the novel preventing and treating bacterial disease medicament of structure, can be passed through
Suppress the synthesis of pathogen energy, suppress the growth and breeding of bacterium.Methylsulfonyl bacterium azoles has the characteristics of interior suction, conduction, penetrates into leaf
Other positions of energy transporting to same blade after piece epidermis.Substantial amounts of isolated test shows that methylsulfonyl bacterium azoles is thin to causing plant
The various pathogenetic bacterias of fungus diseases have good inhibiting effect, i.e., directly suppress bacterial multiplication.Through multiple pot experiment and field
Between the test of pesticide effectiveness checking, draw methylsulfonyl bacterium azoles to crop bacterium venereal disease evil be respectively provided with preferable prevention effect, especially to paddy rice
Bacterial leaf-blight, slice disease, tobacco bacterial wilt, bacterial wilt of tomato, citrus bacterial canker disease etc. have good control effect, and energy one
Determine to stimulate plant growth healthy and strong in degree, improve the resistance of crop.The compound has efficient, wide spectrum, uses the spy of safety
Point, is a bactericide for having much exploitation potential quality.
Jing tests find that methylsulfonyl bacterium azoles and organic copper series bactericidal agent mixture preventing and treating corps diseases effect are projected very much.
Methylsulfonyl bacterium azoles is different with the mechanism of action of Yekuzuo, and the application of the two compounding reduces per mu of dosage for using and dispenser
Number of times, can preferably ensure the safety in production of agricultural and protect ecological environment.
In view of this, in view of the shortcomings of the prior art, present invention aim at provide a kind of azoles of bacterium containing methylsulfonyl with
The complex composition and its preparation of organic copper series bactericidal agent, the complex composition and its preparation compared with single dose, with obvious
Synergistic function, improves the effect of controlling disease, reduces the usage amount of agricultural chemicals, reduces cost accounting, and expanding prevention spectrum is prolonged
The slow resistance to the action of a drug, also reduces environmental pollution and residues of pesticides.
In order to realize the purpose of the present invention, employ the following technical solutions：
The present invention provides the complex composition of a kind of azoles of bacterium containing methylsulfonyl and organic copper series bactericidal agent, the complex composition
It is made up of methylsulfonyl bacterium azoles and organic copper series bactericidal agent, wherein the chemical name of methylsulfonyl bacterium azoles is 2- (p-fluorophenyl) -5- first
Sulfonyl -1,3,4- oxadiazoles.
The complex composition of the above-described azoles of bacterium containing methylsulfonyl and organic copper series bactericidal agent, the organic copper series bactericidal agent
Selected from network ammonia copper, copper 8-hydroxyquinolinate, nitro humus acid copper, kilnitamin copper, copper rosinate, copper citrate, butanedioic acid copper, nonyl bacterium
Any one in copper, copper acetate.
The complex composition of the azoles of bacterium containing methylsulfonyl and organic copper series bactericidal agent described in any of the above,：The methylsulfonyl bacterium
The weight ratio of azoles and organic copper series bactericidal agent is 10:1～1:50.
The complex composition of the above-described azoles of bacterium containing methylsulfonyl and organic copper series bactericidal agent, the methylsulfonyl bacterium azoles and has
The weight ratio of machine copper series bactericidal agent is 5:1～1:20.
The present invention also provides the preparation of a kind of azoles of bacterium containing methylsulfonyl and organic copper series bactericidal agent, by weight, contains 0.1%
Complex composition described in～90% any of the above, remaining is acceptable auxiliary material on agricultural chemicals, is then prepared into disinfectant use in agriculture.
The preparation of the above-described azoles of bacterium containing methylsulfonyl and organic copper series bactericidal agent, by weight, described pesticide sterilizing
Agent contains the complex composition described in 1%～80% any of the above.
The preparation of the above-described azoles of bacterium containing methylsulfonyl and organic copper series bactericidal agent, the formulation that the disinfectant use in agriculture is prepared
For wettable powder, water dispersible granules, suspending agent or granule.
The preparation of the above-described azoles of bacterium containing methylsulfonyl and organic copper series bactericidal agent, acceptable auxiliary material is solvent on agricultural chemicals
With a kind of mixture of the and auxiliary agent in filler.
Auxiliary agent include emulsifying agent, wetting dispersing agent, can also add if necessary antifreezing agent, thickener, stabilizer, defoamer,
Other conventional functionality auxiliary agents such as disintegrant, film forming agent.
The bactericide of the present invention can be configured to wettable powder, suspending agent, microemulsion, aqueous emulsion, water dispersible granules, particle
The preparation of agent, seed coat agent, soluble powder, soluble liquid, suspension emulsion, dry suspending agent, ultra low volume liquids or other formulations.
The type of dosage form of present invention offer is provided.
In some embodiments that the present invention is provided, the formulation of bactericide is preferably wettable powder, water dispersible granules, hangs
Floating agent, granule.
In some embodiments that the present invention is provided, wetting dispersing agent is alkyl benzene sulfonate calcium salt, naphthalenesulfonateformaldehyde formaldehyde condensation
Thing sodium salt, polyoxyethylene carboxylate, condensation compound of methyl naphthalene sulfonic acid and formaldehyde sulfate, naphthalene sulfonic acid-formaldehyde condensation product, methanonaphthalene
Sodium sulfonate, dibutyl naphthalenesulfonic acid formaldehyde condensation products, N- Methyl fatty acyl taurines sodium, APES formaldehyde condensation
Thing sulfate, APES phosphate, tea seed cake powder, saponin, lignosulfite, aliphatic alcohol sulfate, 12
Sodium alkyl sulfonate, fatty acid amide-N methyl taurine sodium salt, sodium sulfate of polyethenoxy ether of fatty alcohol, pull open powder.They can be independent
Use, also can compound use.Above-mentioned surfactant is material well known in the art, can be obtained by various commercial channel.
At least one of the described thickener in xanthans, Arabic gum, aluminium-magnesium silicate, pectin, animal glue.
Described filler is kaolin, bentonite, talcum powder, soil powder, precipitated calcium carbonate, diatomite, potter's clay, concave convex rod
Soil, atlapulgite, gypsum, clay.
Solvent is water.
Disintegrant includes potassium phosphate, potassium carbonate, potassium sulfate, sodium chloride, sodium sulphate, sodium phosphate, ammonium sulfate, ammonium chloride, urine
Element, potassium nitrate.
Antifreezing agent is selected from any one or a few in urea, isopropanol, ethylene glycol, glycerine.
The complex composition of the present invention can be applied by commonsense method, cauline leaf process of such as spraying, also can soil treatment, such as
Solid root spreads fertilizer over the fields or liquid pouring root.
Above-mentioned complex composition can be used to prevent and treat crop bacterium venereal disease evil and fungal disease.
Described bacterial disease can be spotted type bacteriosis, the withered type bacteriosis of leaf, blue or green withered type bacteriosis, withered
The type that withers bacteriosis, ulcer type bacteriosis, type bacteriosis of rotting or deformity bacteriosis.
Above-mentioned spotted type bacteriosis is paddy bacterial brown spot, bacterial leaf streak of rice, the bacillary angle spot of cucumber
Disease, cotton bacterial angular leaf spot, tomato macula disease, Chinese cabbage leaf spot, watermelon bacterial angular leaf spot, cucumber bacterial angular leaf spot,
Pepper bacterial leaf spot, Chinese cabbage bacterial angular leaf spot, mango bacterial black spot, common bacterial blight of bean or corn bacterium
Property leaf blight.
The withered type bacteriosis of above-mentioned leaf be bacterial blight of rice, cucumber Bacterial Leaf Blight, konjaku Bacterial Leaf Blight or
Cucumber leaf blight.
Above-mentioned blue or green withered type bacteriosis is tobacco bacterial wilt, bacterial wilt of tomato, potato bacterial wilt, leather certain kind of berries bacterial wilt, peppery
Green pepper bacterial wilt or eggplant bacterial wilt.
Above-mentioned withered type bacteriosis is potato wilt.
Above-mentioned ulcer type bacteriosis is citrus ulcer, bacterial pustule of soybean, canker of tomato, tomato scab
Disease, bacterial speck or bacterial spot of pepper.
Above-mentioned rotten type bacteriosis is that the bacterial soft rot of Solanaceae and ground family crop, paddy rice basal stem rot, Chinese cabbage are soft
Maize ear rot, capsicum soft rot, wild cabbage soft rot, cabbage black rot, bacterial ring rot o potato or bacterial soft rot of potato.
Described fungal disease can be rice sheath blight disease, melon, brassicaceous vegetable, solanaceous vegetable downy mildew, eggplant
Section's vegetables early blight, late blight, pulse family, Solanaceae and melon damping-off and samping off, melon, solanaceous vegetable droop, peanut,
Cucumber, Fusarium solani and base rot disease, peanut sclerotium rolfsii, black shank, crucifer club root.
In some embodiments of the present invention, the bacterial disease be bacterial wilt of tomato, citrus bacterial canker disease, the fungoid
Disease is Muskmelon Fusarium wilt.
The complex composition and bactericide of the present invention has the advantage that relative to prior art：
The complex composition and bactericide that the present invention is provided has significantly increasing in the range of certain proportion relative to single dose
Effect is acted on, hence it is evident that improve prevention effect, reduces the usage amount of agricultural chemicals, reduces cost accounting, while being made using different type, difference
With the component mixture of mechanism, also delay or resist the resistance to the action of a drug generation of pathogen.
Specific embodiment
Below by embodiment, the invention will be further described.It should be noted that the embodiment of the present invention is only used
It is of the invention in explanation, rather than limitation of the present invention.Methylsulfonyl bacterium azoles active compound used in the present invention is provided by Guizhou University,
Other active compounds for using and preparation are commercial.Abbreviation first sulphur in the preparation embodiment of the following preparation of methylsulfonyl bacterium azoles.
The preparation embodiment of preparation：
Application Example one
The wettable powder of embodiment 1～44
By methylsulfonyl bacterium azoles, organic copper fungicide, Ricinate, filler mixing, it is well mixed in mixing kettle, Jing gas
Stream pulverizer remixes uniform after crushing, you can make the wettable powder of bactericide of the present invention.Specifically see the table below.
Application Example two
The water dispersible granules of embodiment 46～80
By methylsulfonyl bacterium azoles, organic copper series bactericidal agent, wetting dispersing agent, disintegrant, filler together Jing air-flow crushings, then
Into entering in fluidized bed granulating dryer after granulation and drying, the water dispersible granules of bactericide of the present invention are obtained.Tool
Body see the table below：
Application Example three
The suspending agent of example 81～89
Antifreezing agent, thickener, wetting dispersing agent, water mixing, Jing high speed shears are well mixed, methylsulfonyl bacterium is sequentially added
Azoles, organic copper series bactericidal agent, abrading-ball 2～3 hours in ball crusher are obtained the suspending agent of bactericide of the present invention.
Specifically see the table below
The granule of embodiment 90～99
Methylsulfonyl bacterium azoles, organic copper series bactericidal agent, wetting dispersing agent, disintegrant, filler are well mixed, are crushed, added water
Stir after wetting, then granulated with screw extruder pelletizer, sieve after being dried, i.e., the particle of bactericide of the present invention
Agent.
Specifically see the table below
Biological activity determination embodiment
In order to clear and definite methylsulfonyl bacterium azoles and organic copper series bactericidal agent compounding compares whether single dose has synergistic effect, if can be with
Reach it is efficient, simultaneous control, reduce dosage, environmental protection purpose, We conducted Toxicity Determination and field control effectiveness test.
Toxicity Determination：
Following indoor biometricses test calculates co-toxicity coefficient (CTC) to evaluate mixed effect using the abundant methods of Sun Yun.
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
Percentage+TI (B) × B percentages in mixture of theoretical toxicity index TTI (AB)=TI (the A) × A in mixture
Number
Actual measurement toxicity index (ATI)=(standard agent EC50÷ reagent agents EC50)×100
Percentage composition+B the medicament toxicity index of A in theoretical toxicity index (TTI)=A medicament toxicity index × mixture × mixed
The percentage composition of B in agent
Co-toxicity coefficient (CTC)=[mixture actual measurement toxicity index (ATI) ÷ mixture theoretical toxicity index (TTI)] × 100
Evaluation criterion is：Co-toxicity coefficient >=120 show as synergistic effect；Co-toxicity coefficient≤80 show as antagonism；80<
Co-toxicity coefficient<120 show as summation action.
Toxicity Determination embodiment one：The Toxicity Determination test of control of plant bacterial wilt
The following is methylsulfonyl bacterium azoles respectively with network ammonia copper, copper 8-hydroxyquinolinate, nitro humus acid copper, kilnitamin copper, resin acid
The Toxicity Determination test of copper, butanedioic acid copper compounding control of plant bacterial wilt.
With reference to the Toxicity Determination method of tobacco bacterial wilt, bacterial wilt of tomato pathogen is activated on NA culture mediums
Afterwards, bacterium stoste is made into sterilized water, bacterium stoste is diluted to the bacterium that the clump count grown after coated plate 100ul is 100 or so and is hanged
Liquid, it is standby.
Take 400ul bacteria suspensions to mix with equivalent agricultural chemicals single dose, with liquid-transfering gun 100ul is taken, be placed in the NA flat boards being ready for
On, with sterilized " L " shape glass bar that bacteria suspension coating is uniform, 28 DEG C of culture 48h count clump count, and calculate by formula
Bacteriostasis rate, bacterium colony inhibiting rate (g)=(control clump count-process clump count)/control clump count × 100, often processes and is repeated 4 times,
Replace pesticide-treated as control with sterilized water, the result of gained adopts Excel software analysis, calculates the EC of each medicament50, and according to
The abundant methods of Sun Yun calculate co-toxicity coefficient.The results are shown in Table 1～table 3.
The methylsulfonyl bacterium azoles of table 1 respectively with network ammonia copper, the Toxicity Determination result of oxine-copper composite control of plant bacterial wilt
| Composition | EC50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 14.36 | 100.00 | / | / |
| Network ammonia copper (B) | 23.25 | 61.76 | / | / |
| Copper 8-hydroxyquinolinate (C) | 26.54 | 54.11 | / | / |
| A:B=10:1 | 12.05 | 119.17 | 96.52 | 123.46 |
| A:B=8:1 | 11.53 | 124.54 | 95.75 | 130.07 |
| A:B=5:1 | 9.96 | 144.18 | 93.63 | 153.99 |
| A:B=2:1 | 8.98 | 159.91 | 87.25 | 183.27 |
| A:B=1:1 | 8.23 | 174.48 | 80.88 | 215.73 |
| A:B=1:2 | 7.60 | 188.95 | 74.51 | 253.59 |
| A:B=1:5 | 8.58 | 167.37 | 68.14 | 245.63 |
| A:B=1:7 | 10.16 | 141.34 | 66.54 | 212.40 |
| A:B=1:10 | 12.37 | 116.09 | 65.24 | 177.94 |
| A:B=1:20 | 14.85 | 96.70 | 63.58 | 152.08 |
| A:B=1:40 | 15.63 | 91.87 | 62.70 | 146.54 |
| A:B=1:50 | 18.27 | 78.60 | 62.51 | 125.73 |
| A:B=1:60 | 20.15 | 71.27 | 62.39 | 114.23 |
| A:C=10:1 | 12.19 | 117.80 | 95.83 | 122.93 |
| A:C=8:1 | 11.64 | 123.37 | 94.90 | 130.00 |
| A:C=5:1 | 9.84 | 145.93 | 92.35 | 158.02 |
| A:C=2:1 | 8.12 | 176.85 | 84.70 | 208.79 |
| A:C=1:1 | 8.23 | 174.48 | 77.05 | 226.44 |
| A:C=1:2 | 8.57 | 167.56 | 69.40 | 241.43 |
| A:C=1:5 | 11.28 | 127.30 | 61.76 | 206.14 |
| A:C=1:8 | 13.01 | 110.38 | 59.21 | 186.43 |
| A:C=1:15 | 15.12 | 94.97 | 56.98 | 166.69 |
| A:C=1:20 | 16.57 | 86.66 | 56.29 | 153.95 |
| A:C=1:35 | 18.45 | 77.83 | 55.38 | 140.54 |
| A:C=1:50 | 20.28 | 70.81 | 55.01 | 128.73 |
| A:C=1:60 | 22.15 | 64.83 | 54.86 | 118.18 |
The methylsulfonyl bacterium azoles of table 2 compounds respectively the interior of control of plant bacterial wilt with nitro humus acid copper, kilnitamin copper
Toxicity test result
| Composition | EC50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 18.14 | 100.00 | / | / |
| Nitro humus acid copper (D) | 48.56 | 37.36 | / | / |
| Kilnitamin copper (E) | 55.54 | 32.66 | / | / |
| A:D=10:1 | 15.23 | 119.11 | 94.31 | 126.30 |
| A:D=8:1 | 14.20 | 127.75 | 93.04 | 137.30 |
| A:D=5:1 | 13.46 | 134.77 | 89.56 | 150.48 |
| A:D=2:1 | 12.28 | 147.72 | 79.12 | 186.71 |
| A:D=1:1 | 11.32 | 160.25 | 68.68 | 233.33 |
| A:D=1:2 | 12.14 | 149.42 | 58.24 | 256.58 |
| A:D=1:5 | 16.53 | 109.74 | 47.80 | 229.60 |
| A:D=1:10 | 20.27 | 89.49 | 43.05 | 207.88 |
| A:D=1:15 | 24.89 | 72.88 | 41.27 | 176.59 |
| A:D=1:20 | 29.64 | 61.20 | 40.34 | 151.72 |
| A:D=1:40 | 33.26 | 54.54 | 38.88 | 140.26 |
| A:D=1:50 | 37.71 | 48.10 | 38.58 | 124.67 |
| A:D=1:60 | 39.89 | 45.48 | 38.38 | 118.48 |
| A:E=10:1 | 15.73 | 115.32 | 93.88 | 122.84 |
| A:E=8:1 | 14.51 | 125.02 | 92.52 | 135.13 |
| A:E=5:1 | 13.58 | 133.58 | 88.78 | 150.47 |
| A:E=2:1 | 13.14 | 138.05 | 77.55 | 178.01 |
| A:E=1:1 | 12.89 | 140.73 | 66.33 | 212.17 |
| A:E=1:2 | 14.14 | 128.29 | 55.11 | 232.80 |
| A:E=1:5 | 19.69 | 92.13 | 43.88 | 209.94 |
| A:E=1:10 | 23.17 | 78.29 | 38.78 | 201.88 |
| A:E=1:15 | 28.66 | 63.29 | 36.87 | 171.68 |
| A:E=1:20 | 33.21 | 54.62 | 35.87 | 152.30 |
| A:E=1:35 | 39.64 | 45.76 | 34.53 | 132.53 |
| A:E=1:50 | 42.53 | 42.65 | 33.98 | 125.52 |
| A:E=1:60 | 46.25 | 39.22 | 33.76 | 116.17 |
The methylsulfonyl bacterium azoles of table 3 is tied respectively with the Toxicity Determination of copper rosinate, copper acetate compounding control of plant bacterial wilt
Really
| Composition | EC50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 13.33 | 100.00 | / | / |
| Copper rosinate (F) | 35.24 | 37.83 | / | / |
| Copper acetate (J) | 36.12 | 36.90 | / | / |
| A:F=20:1 | 12.46 | 106.98 | 97.04 | 110.25 |
| A:F=10:1 | 11.24 | 118.59 | 94.35 | 125.70 |
| A:F=8:1 | 10.47 | 127.32 | 93.09 | 136.76 |
| A:F=5:1 | 9.51 | 140.17 | 89.64 | 156.37 |
| A:F=3:1 | 9.65 | 138.13 | 84.46 | 163.56 |
| A:F=1:1 | 9.72 | 137.14 | 68.91 | 199.00 |
| A:F=1:2 | 9.86 | 135.19 | 58.55 | 230.90 |
| A:F=1:5 | 13.18 | 101.14 | 48.19 | 209.88 |
| A:F=1:10 | 16.36 | 81.48 | 43.48 | 187.40 |
| A:F=1:15 | 19.35 | 68.89 | 41.71 | 165.15 |
| A:F=1:20 | 21.71 | 61.40 | 40.79 | 150.54 |
| A:F=1:30 | 24.56 | 54.28 | 39.83 | 136.26 |
| A:F=1:50 | 26.51 | 50.28 | 39.05 | 128.78 |
| A:F=20:1 | 12.18 | 109.44 | 97.00 | 112.83 |
| A:J=10:1 | 11.32 | 117.76 | 94.26 | 124.92 |
| A:J=8:1 | 10.03 | 132.90 | 92.99 | 142.92 |
| A:J=5:1 | 9.53 | 139.87 | 89.48 | 156.31 |
| A:J=2:1 | 9.61 | 138.71 | 78.97 | 175.65 |
| A:J=1:1 | 9.72 | 137.14 | 68.45 | 200.34 |
| A:J=1:2 | 9.89 | 134.78 | 57.94 | 232.64 |
| A:J=1:5 | 13.89 | 95.97 | 47.42 | 202.38 |
| A:J=1:10 | 16.92 | 78.78 | 42.64 | 184.76 |
| A:J=1:15 | 19.86 | 67.12 | 40.85 | 164.32 |
| A:J=1:20 | 21.54 | 61.88 | 39.91 | 155.06 |
| A:J=1:35 | 25.49 | 52.30 | 38.66 | 135.28 |
| A:J=1:50 | 28.41 | 46.92 | 38.14 | 123.01 |
From test result table 1-3, methylsulfonyl bacterium azoles respectively with the organic copper class such as network ammonia copper, copper rosinate, copper acetate
Bactericide is (10：1)～(1：50) compound in the range of, the CTC values of control of plant bacterial wilt are all higher than 120, with significantly association
Same synergistic effect.(5：1)～(1：20) compound in the range of, the CTC of control of plant bacterial wilt is all higher than 150, and synergy shows very much
Write.
Toxicity Determination embodiment two：The Toxicity Determination test of preventing and treating citrus bacterial canker disease ulcer disease
The following is methylsulfonyl bacterium azoles respectively with network ammonia copper, copper 8-hydroxyquinolinate, nitro humus acid copper, kilnitamin copper, resin acid
Copper, copper citrate, butanedioic acid copper, the Toxicity Determination test of nonylphenolsulfonate copper compounding preventing and treating citrus bacterial canker disease.
Test reference《Pesticide bioassay technology》(old spring chief editor, publishing house of Beijing Agricultural University publishes) and《Agriculture
Bioassay test criterion NY/T1156.2-2006 in coyote hole》.This test adopts inhibition zone method.On aseptic operating platform, by NA
Culture medium is poured on NA flat boards, and after drying, the citrus processing bacteria suspension spreading rod for taking 0.1ml is equably applied to NA flat boards
On.After drying, punched in flat board central authorities with the card punch of diameter 7mm, then take 100 μ l liquids in aperture.Each concentration 5
Repeat.The process of sterilized water is added with aperture as blank.28 ± 0.5 DEG C of insulating box sterile culture is placed on after process,
Take out after 2d.Adopt crossing method to measure the antibacterial circle diameter (in units of millimeter) of each process respectively, and calculate inhibition zone
The mean value of diameter, inhibiting rate.Statistical analysis is carried out with DPS data processing softwares, the EC of each medicament is calculated50, then by Sun Yun
Abundant method calculates co-toxicity coefficient (CTC).The results are shown in Table 4～table 7.
The methylsulfonyl bacterium azoles of table 4 prevents and treats respectively the Toxicity Determination result of citrus bacterial canker disease with network ammonia copper, oxine-copper composite
| Composition | EC50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 6.35 | 100.00 | / | / |
| Network ammonia copper (B) | 22.54 | 28.17 | / | / |
| Copper 8-hydroxyquinolinate (C) | 27.01 | 23.51 | / | / |
| A:B=20:1 | 6.07 | 104.61 | 96.58 | 108.32 |
| A:B=10:1 | 5.58 | 113.80 | 93.47 | 121.75 |
| A:B=8:1 | 5.02 | 126.49 | 92.02 | 137.46 |
| A:B=5:1 | 4.68 | 135.68 | 88.03 | 154.14 |
| A:B=3:1 | 4.15 | 153.01 | 82.04 | 186.50 |
| A:B=2:1 | 3.72 | 170.70 | 76.06 | 224.43 |
| A:B=1:1 | 4.19 | 151.55 | 64.09 | 236.48 |
| A:B=1:2 | 4.86 | 130.66 | 52.11 | 250.71 |
| A:B=1:5 | 7.67 | 82.79 | 40.14 | 206.24 |
| A:B=1:10 | 10.26 | 61.89 | 34.70 | 178.35 |
| A:B=1:20 | 13.26 | 47.89 | 31.59 | 151.58 |
| A:B=1:40 | 15.33 | 41.42 | 29.92 | 138.42 |
| A:B=1:50 | 17.54 | 36.20 | 29.58 | 122.39 |
| A:B=20:1 | 6.17 | 102.92 | 96.36 | 106.81 |
| A:C=10:1 | 5.62 | 112.99 | 93.05 | 121.43 |
| A:C=5:1 | 4.73 | 134.25 | 87.25 | 153.86 |
| A:C=2:1 | 4.80 | 132.29 | 74.50 | 177.56 |
| A:C=1:1 | 4.92 | 129.07 | 61.75 | 209.00 |
| A:C=1:2 | 5.09 | 124.75 | 49.01 | 254.57 |
| A:C=1:5 | 8.28 | 76.69 | 36.26 | 211.51 |
| A:C=1:10 | 11.76 | 54.00 | 30.46 | 177.25 |
| A:C=1:15 | 13.51 | 47.00 | 28.29 | 166.14 |
| A:C=1:20 | 15.38 | 41.29 | 27.15 | 152.06 |
| A:C=1:30 | 17.21 | 36.90 | 25.98 | 142.04 |
| A:C=1:40 | 19.65 | 32.32 | 25.38 | 127.35 |
| A:C=1:50 | 20.22 | 31.40 | 25.01 | 125.57 |
The methylsulfonyl bacterium azoles of table 5 prevents and treats respectively the interior of citrus bacterial canker disease with nitro humus acid copper, kilnitamin copper compounding
Toxicity test result
| Composition | EC50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 8.62 | 100.00 | / | / |
| Nitro humus acid copper (D) | 34.77 | 24.79 | / | / |
| Kilnitamin copper (E) | 45.69 | 18.87 | / | / |
| A:D=20:1 | 8.16 | 105.64 | 96.42 | 109.56 |
| A:D=10:1 | 7.37 | 116.96 | 93.16 | 125.54 |
| A:D=8:1 | 6.92 | 124.57 | 91.64 | 135.93 |
| A:D=5:1 | 6.42 | 134.27 | 87.47 | 153.51 |
| A:D=2:1 | 6.51 | 132.41 | 74.93 | 176.71 |
| A:D=1:1 | 6.68 | 129.04 | 62.40 | 206.81 |
| A:D=1:2 | 6.75 | 127.70 | 49.86 | 256.12 |
| A:D=1:5 | 11.72 | 73.55 | 37.33 | 197.05 |
| A:D=1:10 | 16.28 | 52.95 | 31.63 | 167.41 |
| A:D=1:20 | 20.16 | 42.76 | 28.37 | 150.70 |
| A:D=1:30 | 23.27 | 37.04 | 27.22 | 136.10 |
| A:D=1:40 | 25.16 | 34.26 | 26.63 | 128.67 |
| A:D=1:50 | 26.64 | 32.36 | 26.27 | 123.19 |
| A:D=20:1 | 8.11 | 106.29 | 96.14 | 110.56 |
| A:E=10:1 | 7.59 | 113.57 | 92.62 | 122.61 |
| A:E=8:1 | 6.94 | 124.21 | 90.99 | 136.51 |
| A:E=5:1 | 6.49 | 132.82 | 86.48 | 153.59 |
| A:E=2:1 | 6.62 | 130.21 | 72.96 | 178.48 |
| A:E=1:1 | 7.13 | 120.90 | 59.43 | 203.42 |
| A:E=1:2 | 8.88 | 97.07 | 45.91 | 211.44 |
| A:E=1:5 | 12.35 | 69.80 | 32.39 | 215.50 |
| A:E=1:10 | 19.27 | 44.73 | 26.24 | 170.46 |
| A:E=1:20 | 24.97 | 34.52 | 22.73 | 151.88 |
| A:E=1:30 | 27.64 | 31.19 | 21.48 | 145.17 |
| A:E=1:40 | 31.85 | 27.06 | 20.85 | 129.84 |
| A:E=1:50 | 34.86 | 24.73 | 20.46 | 120.87 |
The methylsulfonyl bacterium azoles of table 6 prevents and treats respectively the Toxicity Determination of citrus bacterial canker disease with copper rosinate, copper citrate compounding
As a result
| Composition | EC50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 6.71 | 100.00 | / | / |
| Copper rosinate (F) | 34.62 | 19.38 | / | / |
| Copper citrate (G) | 54.79 | 12.25 | / | / |
| A:F=10:1 | 5.86 | 114.51 | 92.67 | 123.56 |
| A:F=8:1 | 5.52 | 121.56 | 91.04 | 133.52 |
| A:F=5:1 | 5.01 | 133.93 | 86.56 | 154.72 |
| A:F=2:1 | 5.57 | 120.47 | 73.13 | 164.74 |
| A:F=1:1 | 5.73 | 117.10 | 59.69 | 196.18 |
| A:F=1:2 | 5.88 | 114.12 | 46.25 | 246.71 |
| A:F=1:5 | 10.42 | 64.40 | 32.82 | 196.22 |
| A:F=1:10 | 14.09 | 47.62 | 26.71 | 178.29 |
| A:F=1:20 | 18.30 | 36.67 | 23.22 | 157.90 |
| A:F=1:30 | 21.64 | 31.01 | 21.98 | 141.06 |
| A:F=1:40 | 24.69 | 27.18 | 21.35 | 127.30 |
| A:F=1:50 | 26.51 | 25.31 | 20.96 | 120.74 |
| A:F=1:60 | 28.13 | 23.85 | 20.70 | 115.22 |
| A:G=10:1 | 6.03 | 111.28 | 92.02 | 120.92 |
| A:G=8:1 | 5.63 | 119.18 | 90.25 | 132.06 |
| A:G=5:1 | 5.20 | 129.04 | 85.37 | 151.14 |
| A:G=3:1 | 5.31 | 126.37 | 78.06 | 161.88 |
| A:G=2:1 | 5.78 | 116.09 | 70.75 | 164.09 |
| A:G=1:1 | 6.03 | 111.28 | 56.12 | 198.27 |
| A:G=1:2 | 6.42 | 104.52 | 41.50 | 251.86 |
| A:G=1:5 | 12.57 | 53.38 | 26.87 | 198.65 |
| A:G=1:10 | 20.13 | 33.33 | 20.22 | 164.82 |
| A:G=1:20 | 26.71 | 25.12 | 16.43 | 152.94 |
| A:G=1:35 | 33.82 | 19.84 | 14.68 | 135.11 |
| A:G=1:50 | 39.14 | 17.14 | 13.97 | 122.74 |
| A:G=1:65 | 43.86 | 15.30 | 13.58 | 112.69 |
The methylsulfonyl bacterium azoles of table 7 is tied respectively with the Toxicity Determination of butanedioic acid copper, nonylphenolsulfonate copper compounding preventing and treating citrus bacterial canker disease
Really
| Composition | EC50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 7.91 | 100.00 | / | / |
| Butanedioic acid copper (H) | 36.19 | 21.86 | / | / |
| Nonylphenolsulfonate copper (I) | 54.76 | 14.44 | / | / |
| A:H=10:1 | 6.82 | 115.98 | 92.90 | 124.85 |
| A:H=7:1 | 6.27 | 126.16 | 90.23 | 139.81 |
| A:H=5:1 | 5.71 | 138.53 | 86.98 | 159.27 |
| A:H=2:1 | 5.91 | 133.84 | 73.95 | 180.98 |
| A:H=1:1 | 6.27 | 126.16 | 60.93 | 207.06 |
| A:H=1:2 | 6.54 | 120.95 | 47.90 | 252.48 |
| A:H=1:5 | 11.75 | 67.32 | 34.88 | 193.00 |
| A:H=1:10 | 16.14 | 49.01 | 28.96 | 169.22 |
| A:H=1:20 | 20.34 | 38.89 | 25.58 | 152.04 |
| A:H=1:30 | 22.57 | 35.05 | 24.38 | 143.77 |
| A:H=1:40 | 25.49 | 31.03 | 23.76 | 130.59 |
| A:H=1:50 | 27.48 | 28.78 | 23.39 | 123.07 |
| A:H=1:60 | 28.81 | 27.46 | 23.14 | 118.66 |
| A:I=10:1 | 6.95 | 113.81 | 92.22 | 123.41 |
| A:I=8:1 | 6.27 | 126.16 | 90.49 | 139.41 |
| A:I=5:1 | 5.84 | 135.45 | 85.74 | 157.97 |
| A:I=2:1 | 6.31 | 125.36 | 71.48 | 175.37 |
| A:I=1:1 | 6.84 | 115.64 | 57.22 | 202.09 |
| A:I=1:2 | 7.26 | 108.95 | 42.96 | 253.60 |
| A:I=1:5 | 13.79 | 57.36 | 28.70 | 199.83 |
| A:I=1:10 | 19.72 | 40.11 | 22.22 | 180.50 |
| A:I=1:15 | 25.53 | 30.98 | 19.79 | 156.54 |
| A:I=1:20 | 28.10 | 28.15 | 18.52 | 152.00 |
| A:I=1:35 | 34.89 | 22.67 | 16.82 | 134.78 |
| A:I=1:50 | 40.27 | 19.64 | 16.12 | 121.83 |
| A:I=1:65 | 45.38 | 17.43 | 15.74 | 110.73 |
From test result table 4-7, sulphonyl bacterium azoles respectively with network ammonia copper, copper 8-hydroxyquinolinate, nitro humus acid copper, mixed amino
The organic copper series bactericidal agent such as sour copper is (10：1)～(1：50) compound in the range of, the CTC values for preventing and treating citrus bacterial canker disease are all higher than
120, with obvious synergistic function.(5：1)～(1：20) compound in the range of, the CTC for preventing and treating citrus bacterial canker disease is big
In 150, synergy highly significant.
Toxicity Determination embodiment three：The Toxicity Determination test of preventing and treating Muskmelon Fusarium wilt
The following is methylsulfonyl bacterium azoles respectively with network ammonia copper, copper 8-hydroxyquinolinate, nitro humus acid copper, kilnitamin copper, resin acid
Copper, copper citrate, butanedioic acid copper, nonylphenolsulfonate copper, the Toxicity Determination test of copper acetate compounding preventing and treating Muskmelon Fusarium wilt.
Under aseptic technique, the sterilising medium 36ml for being melted in advance with pipette, extract in aseptic conical flask,
The liquid 4ml diluted with the 0.1g Tween 80s aqueous solution is added, is fully shaken up, then equivalent pours the culture of 4 a diameter of 9cm into
In ware, pastille flat board is made, if the process without medicament is blank.By cultured pathogen, aseptically use
The sterilization punchers of diameter 5mm are beaten and take bacteria cake, and with transfer needle by pure culture biscuits involvng inoculation in pastille flat board central authorities, mycelia faces down, covers
Ware lid, is placed in moisturizing culture in 26 DEG C of insulating boxs.When the colony diameter of blank accounts for more than half of ware footpath, slide calliper rule are used
Measurement colony diameter, each bacterium colony is once averaged with crossing method vertical survey diameter is each, is calculated mycelial growth and is suppressed
Rate, according to each drug concentration logarithm value and corresponding mycelial growth inhibition rate niqueMin regression analysis is made, and calculates each medicament
EC50, and the co-toxicity coefficient of mixture is calculated according to the abundant methods of Sun Yun.The results are shown in Table 8～table 11.
The methylsulfonyl bacterium azoles of table 8 prevents and treats respectively the Toxicity Determination result of Muskmelon Fusarium wilt with network ammonia copper, oxine-copper composite
| Composition | EC50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 23.42 | 100.00 | / | / |
| Network ammonia copper (B) | 25.63 | 91.38 | / | / |
| Copper 8-hydroxyquinolinate (C) | 27.84 | 84.12 | / | / |
| A:B=10:1 | 18.72 | 125.11 | 99.22 | 126.10 |
| A:B=8:1 | 17.49 | 133.91 | 99.04 | 135.20 |
| A:B=5:1 | 15.81 | 148.13 | 98.56 | 150.29 |
| A:B=2:1 | 13.85 | 169.10 | 97.13 | 174.10 |
| A:B=1:1 | 11.47 | 204.18 | 95.69 | 213.38 |
| A:B=1:2 | 9.68 | 241.94 | 94.25 | 256.70 |
| A:B=1:5 | 11.53 | 203.12 | 92.81 | 218.85 |
| A:B=1:8 | 13.69 | 171.07 | 92.34 | 185.27 |
| A:B=1:10 | 15.17 | 154.38 | 92.16 | 167.51 |
| A:B=1:20 | 16.84 | 139.07 | 91.79 | 151.52 |
| A:B=1:40 | 18.82 | 124.44 | 91.59 | 135.87 |
| A:B=1:50 | 21.04 | 111.31 | 91.55 | 121.59 |
| A:B=1:70 | 23.27 | 100.64 | 91.50 | 110.00 |
| A:C=10:1 | 18.93 | 123.72 | 98.56 | 125.53 |
| A:C=8:1 | 17.25 | 135.77 | 98.24 | 138.21 |
| A:C=5:1 | 15.74 | 148.79 | 97.35 | 152.84 |
| A:C=2:1 | 13.62 | 171.95 | 94.71 | 181.56 |
| A:C=1:1 | 11.81 | 198.31 | 92.06 | 215.41 |
| A:C=1:2 | 10.36 | 226.06 | 89.42 | 252.82 |
| A:C=1:5 | 13.09 | 178.92 | 86.77 | 206.20 |
| A:C=1:10 | 15.28 | 153.27 | 85.57 | 179.13 |
| A:C=1:20 | 17.71 | 132.24 | 84.88 | 155.80 |
| A:C=1:30 | 19.30 | 121.35 | 84.64 | 143.38 |
| A:C=1:40 | 21.08 | 111.10 | 84.51 | 131.46 |
| A:C=1:50 | 22.24 | 105.31 | 84.43 | 124.72 |
| A:C=1:60 | 23.46 | 99.83 | 84.38 | 118.30 |
The methylsulfonyl bacterium azoles of table 9 prevents and treats respectively the interior of Muskmelon Fusarium wilt with nitro humus acid copper, kilnitamin copper compounding
Toxicity test result
| Composition | EC50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 23.72 | 100.00 | / | / |
| Nitro humus acid copper (D) | 34.68 | 68.40 | / | / |
| Kilnitamin copper (E) | 44.75 | 53.01 | / | / |
| A:D=20:1 | 22.76 | 104.22 | 98.50 | 105.81 |
| A:D=10:1 | 20.24 | 117.19 | 97.13 | 120.66 |
| A:D=7:1 | 17.33 | 136.87 | 96.05 | 142.50 |
| A:D=5:1 | 15.93 | 148.90 | 94.73 | 157.18 |
| A:D=2:1 | 13.61 | 174.28 | 89.47 | 194.81 |
| A:D=1:1 | 12.42 | 190.98 | 84.20 | 226.82 |
| A:D=1:2 | 11.76 | 201.70 | 78.93 | 255.54 |
| A:D=1:5 | 16.54 | 143.41 | 73.66 | 194.68 |
| A:D=1:10 | 19.57 | 121.21 | 71.27 | 170.07 |
| A:D=1:20 | 22.17 | 106.99 | 69.90 | 153.06 |
| A:D=1:30 | 24.64 | 96.27 | 69.42 | 138.68 |
| A:D=1:40 | 26.93 | 88.08 | 69.17 | 127.34 |
| A:D=1:50 | 28.17 | 84.20 | 69.02 | 122.00 |
| A:D=20:1 | 21.52 | 110.22 | 97.76 | 112.75 |
| A:E=10:1 | 19.76 | 120.04 | 95.73 | 125.40 |
| A:E=8:1 | 17.69 | 134.09 | 94.78 | 141.47 |
| A:E=5:1 | 16.84 | 140.86 | 92.17 | 152.82 |
| A:E=2:1 | 15.19 | 156.16 | 84.34 | 185.16 |
| A:E=1:1 | 14.86 | 159.62 | 76.50 | 208.65 |
| A:E=1:2 | 13.67 | 173.52 | 68.67 | 252.68 |
| A:E=1:5 | 19.32 | 122.77 | 60.84 | 201.81 |
| A:E=1:10 | 24.16 | 98.18 | 57.28 | 171.41 |
| A:E=1:20 | 28.37 | 83.61 | 55.24 | 151.35 |
| A:E=1:30 | 32.27 | 73.50 | 54.52 | 134.82 |
| A:E=1:40 | 34.16 | 69.44 | 54.15 | 128.23 |
| A:E=1:50 | 35.82 | 66.22 | 53.93 | 122.80 |
The methylsulfonyl bacterium azoles of table 10 prevents and treats respectively the Toxicity Determination of Muskmelon Fusarium wilt with copper rosinate, copper citrate compounding
As a result
| Composition | EC50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 23.17 | 100.00 | / | / |
| Copper rosinate (F) | 33.42 | 69.33 | / | / |
| Copper citrate (G) | 57.61 | 40.22 | / | / |
| A:F=10:1 | 19.76 | 117.26 | 97.21 | 120.62 |
| A:F=8:1 | 17.61 | 131.57 | 96.59 | 136.21 |
| A:F=5:1 | 15.49 | 149.58 | 94.89 | 157.64 |
| A:F=3:1 | 12.58 | 184.18 | 92.33 | 199.48 |
| A:F=2:1 | 12.41 | 186.70 | 89.78 | 207.97 |
| A:F=1:1 | 12.26 | 188.99 | 84.66 | 223.22 |
| A:F=1:2 | 11.59 | 199.91 | 79.55 | 251.30 |
| A:F=1:5 | 15.19 | 152.53 | 74.44 | 204.91 |
| A:F=1:10 | 18.37 | 126.13 | 72.12 | 174.89 |
| A:F=1:20 | 21.17 | 109.45 | 70.79 | 154.61 |
| A:F=1:35 | 24.36 | 95.11 | 70.18 | 135.53 |
| A:F=1:50 | 27.59 | 83.98 | 69.93 | 120.09 |
| A:F=1:65 | 29.45 | 78.68 | 69.79 | 112.72 |
| A:G=10:1 | 19.62 | 118.09 | 94.57 | 124.88 |
| A:G=8:1 | 16.88 | 137.26 | 93.36 | 147.03 |
| A:G=5:1 | 16.94 | 136.78 | 90.04 | 151.91 |
| A:G=2:1 | 16.28 | 142.32 | 80.07 | 177.74 |
| A:G=1:1 | 15.37 | 150.75 | 70.11 | 215.02 |
| A:G=1:2 | 14.96 | 154.88 | 60.15 | 257.51 |
| A:G=1:5 | 21.45 | 108.02 | 50.18 | 215.25 |
| A:G=1:10 | 27.86 | 83.17 | 45.65 | 182.17 |
| A:G=1:20 | 34.69 | 66.79 | 43.07 | 155.09 |
| A:G=1:30 | 39.19 | 59.12 | 42.15 | 140.28 |
| A:G=1:40 | 42.83 | 54.10 | 41.68 | 129.80 |
| A:G=1:50 | 45.37 | 51.07 | 41.39 | 123.38 |
| A:G=1:60 | 47.64 | 48.64 | 41.20 | 118.05 |
The methylsulfonyl bacterium azoles of table 11 is tied respectively with the Toxicity Determination of butanedioic acid copper, nonylphenolsulfonate copper compounding preventing and treating Muskmelon Fusarium wilt
Really
| Composition | EC50(μg/ml) | ATI | TTI | CTC |
| Methylsulfonyl bacterium azoles (A) | 24.71 | 100.00 | / | / |
| Butanedioic acid copper (H) | 35.59 | 69.43 | / | / |
| Nonylphenolsulfonate copper (I) | 43.96 | 56.21 | / | / |
| A:H=20:1 | 22.62 | 109.24 | 98.54 | 110.85 |
| A:H=10:1 | 20.24 | 122.08 | 97.22 | 125.57 |
| A:H=7:1 | 18.91 | 130.67 | 96.18 | 135.86 |
| A:H=5:1 | 16.72 | 147.79 | 94.90 | 155.72 |
| A:H=2:1 | 14.39 | 171.72 | 89.81 | 191.20 |
| A:H=1:1 | 13.62 | 181.42 | 84.71 | 214.16 |
| A:H=1:2 | 12.16 | 203.21 | 79.62 | 255.22 |
| A:H=1:6 | 16.52 | 149.58 | 73.80 | 202.69 |
| A:H=1:10 | 19.47 | 126.91 | 72.21 | 175.76 |
| A:H=1:20 | 22.85 | 108.14 | 70.89 | 152.56 |
| A:H=1:30 | 24.83 | 99.52 | 70.42 | 141.33 |
| A:H=1:40 | 26.53 | 93.14 | 70.18 | 132.72 |
| A:H=1:50 | 28.49 | 86.73 | 70.03 | 123.85 |
| A:H=20:1 | 22.84 | 108.19 | 97.91 | 110.49 |
| A:I=10:1 | 21.06 | 117.33 | 96.02 | 122.20 |
| A:I=8:1 | 19.82 | 124.67 | 95.13 | 131.05 |
| A:I=5:1 | 16.88 | 146.39 | 92.70 | 157.91 |
| A:I=2:1 | 15.73 | 157.09 | 85.40 | 183.94 |
| A:I=1:1 | 14.72 | 167.87 | 78.11 | 214.92 |
| A:I=1:2 | 13.76 | 179.58 | 70.81 | 253.62 |
| A:I=1:6 | 18.69 | 132.21 | 62.47 | 211.65 |
| A:I=1:10 | 22.75 | 108.62 | 60.19 | 180.45 |
| A:I=1:20 | 26.71 | 92.51 | 58.30 | 158.70 |
| A:I=1:30 | 29.84 | 82.81 | 57.62 | 143.71 |
| A:I=1:40 | 32.71 | 75.54 | 57.28 | 131.89 |
| A:I=1:50 | 35.09 | 70.42 | 57.07 | 123.39 |
From test result table 8-11, sulphonyl bacterium azoles respectively with network ammonia copper, copper 8-hydroxyquinolinate, nitro humus acid copper, mix ammonia
The organic copper series bactericidal agents such as base acid copper are (10：1)～(1：50) compound in the range of, the CTC values for preventing and treating Muskmelon Fusarium wilt are all higher than
120, with obvious synergistic function.(5：1)～(1：20) compound in the range of, the CTC for preventing and treating citrus bacterial canker disease is big
In 150, synergy highly significant.
Land for growing field crops test examples
In order to clear and definite methylsulfonyl bacterium azoles it is alone with organic copper series bactericidal agent with it is mixed when control of plant bacterial wilt, c itrus canker
Disease, the prevention effect of Muskmelon Fusarium wilt, and can the result (i.e. synergistic effect) of clear and definite Toxicity Determination be demonstrate,proved in field
Real, at home different regions have carried out substantial amounts of field test to present invention applicant.
Comparison medicament：
Comparison medicament 7：30% nitro humus acid copper WP (self-control)
Nitro humus acid copper 30g, APES phosphate 6g, lauryl sodium sulfate 3g, kaolin are added to
100g, mixture carries out air-flow crushing, and 30% nitro humus acid copper wettable powder is obtained
Comparison medicament 8：30% copper citrate WP (self-control)
Copper citrate 30g, dibutyl naphthalenesulfonic acid formaldehyde condensation products 6g, APES formaldehyde condensation products sulfat
3g, soil powder add to 100g, and mixture carries out air-flow crushing, and 30% copper citrate wettable powder is obtained
Comparison medicament 9：30% butanedioic acid copper WP (self-control)
Butanedioic acid copper 30g, dibutyl naphthalenesulfonic acid formaldehyde condensation products 6g, lauryl sodium sulfate 3g, diatomite add to 100g,
Mixture carries out air-flow crushing, and 30% butanedioic acid copper wettable powder is obtained.
Comparison medicament 10：30% methylsulfonyl bacterium azoles WP (self-control)
Methylsulfonyl bacterium azoles 30g, sodium lignin sulfonate 6g, lauryl sodium sulfate 3g, attapulgite add to 100g, mixture
Air-flow crushing is carried out, 30% methylsulfonyl bacterium azoles wettable powder is obtained.
Field efficacy embodiment one：The field control effectiveness test of preventing and treating citrus bacterial canker disease
Test method and computational methods reference《GB/T17980.103-2004 pesticide field efficacy medicine tests criterion (two)
103 parts：Bactericidal agent for preventing and treating citrus bacterial canker disease》, it is into 3 plants of age fruit tree per cell, 4 repetitions are often processed, if clear water is processed as
Blank, in early stage spray pesticide is carried out, and is spaced second dispenser in 7 days.Before first time medicine, after second medicine
7 days, 14 days investigation results after second medicine, classification investigation incidence, calculates disease index, preventive effect in units of blade.Knot
Fruit is shown in Table 12：
The methylsulfonyl bacterium azoles of table 12 prevents and treats respectively the field control effectiveness test result of citrus bacterial canker disease with network ammonia copper, oxine-copper composite
From test of pesticide effectiveness result table 12, during preventing and treating citrus bacterial canker disease, methylsulfonyl bacterium azoles respectively with network ammonia copper, copper 8-hydroxyquinolinate
, in the case where active ingredient dosage is more less than single dose, prevention effect is apparently higher than single dose for the bactericide of compounding.Wherein, second
The prevention effect of 7d is high by more than 16.02% compared with single dose after secondary medicine.14d can also keep preventing and treating effect well after second medicine
Really (more than 78%), the lasting period is long.
Field efficacy embodiment two：The field control effectiveness test of control of plant bacterial wilt
Test method：Reference《Pesticide field efficacy medicine test criterion (NY/T1464.32-2010)》Regulation application method,
Spray dispenser for the first time when beginning sees diseased plant, second spray dispenser after 10d.Altogether twice, each process plot area is for dispenser
45m2, number of repetition 4 times.The 10d after second dispenser, 20d investigate whole plant of each cell, record total strain number and diseased plant
Number, calculates diseased plant rate and preventive effect.The results are shown in Table 13：
The methylsulfonyl bacterium azoles of table 13 respectively with the field control effectiveness test of the compounding control of plant bacterial wilt such as copper rosinate, copper acetate
As a result
From test of pesticide effectiveness result table 13, during preventing and treating citrus bacterial canker disease, methylsulfonyl bacterium azoles respectively with nitro humus acid copper,
The bactericide that kilnitamin copper, copper rosinate, copper acetate are compounded is prevented in the case where active ingredient dosage is more less than single dose
Effect is controlled apparently higher than single dose.Wherein, the prevention effect of 10d is high by more than 20.58% compared with single dose after second medicine.Second
20d can also keep good prevention effect (more than 78%) after secondary medicine, and the lasting period is long.
Field efficacy embodiment three：The field control effectiveness test of preventing and treating Muskmelon Fusarium wilt
Test method and computational methods reference《GB/T17980.113-2004 pesticide field efficacy medicine tests criterion (two)
113 parts：Bactericidal agent for preventing and treating cucurbits fusarium wilt》, per plot area 30m2,4 repetitions often being processed, non-dispenser is processed as blank right
According to, carrying out spraying dispenser around root system in early stage, second medicine is applied in 10 days in interval.Before medicine, 15 after second medicine
My god, 30 days investigation results after medicine, investigate all plant of each cell, record total strain number, diseased plant number calculate diseased plant rate, preventive effect.
The results are shown in Table 14, table 15：
The methylsulfonyl bacterium azoles of table 14 prevents and treats respectively the field control effectiveness test result of Muskmelon Fusarium wilt with network ammonia copper, oxine-copper composite
From test of pesticide effectiveness result table 14, during preventing and treating Muskmelon Fusarium wilt, methylsulfonyl bacterium azoles respectively with network ammonia copper, copper 8-hydroxyquinolinate
, in the case where active ingredient dosage is more less than single dose, prevention effect is apparently higher than single dose for the bactericide of compounding.Wherein, second
The prevention effect of 15d is high by more than 20.43% compared with single dose after secondary medicine.30d can also keep preventing and treating well after second medicine
Effect (more than 78%), the lasting period is long.
The methylsulfonyl bacterium azoles of table 15 respectively with the field control effectiveness test of the compounding preventing and treating Muskmelon Fusarium wilt such as copper rosinate, copper acetate
As a result
From test of pesticide effectiveness result table 15, during preventing and treating Muskmelon Fusarium wilt, methylsulfonyl bacterium azoles respectively with nitro humus acid copper,
The bactericide that kilnitamin copper, copper rosinate, copper acetate are compounded is prevented in the case where active ingredient dosage is more less than single dose
Effect is controlled apparently higher than single dose.Wherein, the prevention effect of 15d is high by more than 20.26% compared with single dose after second medicine.Second
30d can also keep good prevention effect (more than 78%) after secondary medicine, and the lasting period is long.
Claims (8)
1. a kind of complex composition of azoles of bacterium containing methylsulfonyl and organic copper series bactericidal agent, it is characterised in that the complex composition
It is made up of methylsulfonyl bacterium azoles and organic copper series bactericidal agent, wherein the chemical name of methylsulfonyl bacterium azoles is 2- (p-fluorophenyl) -5- first
Sulfonyl -1,3,4- oxadiazoles；
The weight ratio of the methylsulfonyl bacterium azoles and organic copper series bactericidal agent is 10:1~1: 50.
2. the complex composition of the azoles of bacterium containing methylsulfonyl according to claim 1 and organic copper series bactericidal agent, it is characterised in that
The organic copper series bactericidal agent is selected from network ammonia copper, copper 8-hydroxyquinolinate, nitro humus acid copper, kilnitamin copper, copper rosinate, citric acid
Any one in copper, butanedioic acid copper, nonylphenolsulfonate copper, copper acetate.
3., according to the arbitrary described azoles of bacterium containing methylsulfonyl of claim 1-2 and the complex composition of organic copper series bactericidal agent, it is special
Levy and be：The weight ratio of the methylsulfonyl bacterium azoles and organic copper series bactericidal agent is 5:1~1: 20.
4. the preparation of a kind of azoles of bacterium containing methylsulfonyl and organic copper series bactericidal agent, it is characterised in that by weight, containing 0.1% ~ 90%
The arbitrary described complex composition of claim 1-3, remaining is acceptable auxiliary material on agricultural chemicals, is then prepared into agricultural bactericidal
Agent.
5. the preparation of the azoles of bacterium containing methylsulfonyl according to claim 4 and organic copper series bactericidal agent, it is characterised in that with weight
Meter, described agriculture chemicals fungicide contains the arbitrary described complex composition of 1% ~ 80% claim 1-4.
6. the azoles of bacterium containing methylsulfonyl according to claim 4 or 5 and the preparation of organic copper series bactericidal agent, it is characterised in that institute
The formulation for stating disinfectant use in agriculture preparation is wettable powder, water dispersible granules, suspending agent or granule.
7. the preparation of the azoles of bacterium containing methylsulfonyl according to claim 6 and organic copper series bactericidal agent, it is characterised in that：On agricultural chemicals
Acceptable auxiliary material is a kind of mixture of the and auxiliary agent in solvent and filler.
8. the complex composition as described in claim 1-3 is arbitrary is in crop bacterium venereal disease evil and/or fungal disease is prevented and treated
Purposes.
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| CN107821397A (en) * | 2017-11-13 | 2018-03-23 | 柳州市惠农化工有限公司 | A kind of composition pesticide containing copper rosinate and nonylphenolsulfonate copper |
Citations (4)
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|---|---|---|---|---|
| US5166165A (en) * | 1990-10-20 | 1992-11-24 | Bayer Aktiengesellschaft | Fungicidal agents based on heterocyclically substituted sulphones |
| CN102499247A (en) * | 2011-10-17 | 2012-06-20 | 贵州大学 | Oxadiazole sulfone compound for controlling bacterial crop diseases |
| CN103416411A (en) * | 2013-07-08 | 2013-12-04 | 中国中化股份有限公司 | Agricultural sterilization composition adopting flumorph and organic copper |
| CN103788015A (en) * | 2014-01-22 | 2014-05-14 | 贵州大学 | Derivatives containing thiadiazole or oxadiazole and application of derivatives in prevention and control of agricultural plant diseases |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5166165A (en) * | 1990-10-20 | 1992-11-24 | Bayer Aktiengesellschaft | Fungicidal agents based on heterocyclically substituted sulphones |
| CN102499247A (en) * | 2011-10-17 | 2012-06-20 | 贵州大学 | Oxadiazole sulfone compound for controlling bacterial crop diseases |
| CN103416411A (en) * | 2013-07-08 | 2013-12-04 | 中国中化股份有限公司 | Agricultural sterilization composition adopting flumorph and organic copper |
| CN103788015A (en) * | 2014-01-22 | 2014-05-14 | 贵州大学 | Derivatives containing thiadiazole or oxadiazole and application of derivatives in prevention and control of agricultural plant diseases |
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