CN105994281B - A kind of bactericidal composition and its application of fluorine-containing ether bacterium amide and bupirimate - Google Patents

A kind of bactericidal composition and its application of fluorine-containing ether bacterium amide and bupirimate Download PDF

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Publication number
CN105994281B
CN105994281B CN201610361933.2A CN201610361933A CN105994281B CN 105994281 B CN105994281 B CN 105994281B CN 201610361933 A CN201610361933 A CN 201610361933A CN 105994281 B CN105994281 B CN 105994281B
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bupirimate
bacterium amide
ether bacterium
bactericidal composition
fluorine ether
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CN105994281A (en
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石振龙
万维肖
郭崇友
赵东亚
程清云
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Nanjing Huazhou Pharmaceutical Co Ltd
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Nanjing Huazhou Pharmaceutical Co Ltd
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/541,3-Diazines; Hydrogenated 1,3-diazines
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

Abstract

The invention discloses bactericidal composition and its applications of a kind of fluorine-containing ether bacterium amide and bupirimate.The bactericidal composition is using fluorine ether bacterium amide and bupirimate as principle active component, and wherein the mass ratio of fluorine ether bacterium amide and bupirimate is 1~70:1~50.The bactericidal composition can be applied to prevention Cereal, fruit tree, vegetable disease, has higher synergistic function, overcomes and delayed the drug resistance of germ, and sterilization speed is fast, the lasting period is long, reduces application cost, and control effect is substantially better than the use of its single dose.The present invention can be used for preventing the fungoid on crops, it is particularly possible to which, for preventing the fungal diseases such as downy mildew, late blight, powdery mildew, significant effect is used better than single dose.

Description

A kind of bactericidal composition and its application of fluorine-containing ether bacterium amide and bupirimate
Technical field
The present invention relates to a kind of bactericidal compositions and application thereof, and especially one kind is with fluorine ether bacterium amide and bupirimate Bactericidal composition for main active and its application.
Background technology
Fluorine ether bacterium amide molecule formula:C15H8ClF7N2O2, chemical name:N- (3- chloro- 5- (trichloromethyl) pyridine -2- first Base) four chloro- 4- methoxy benzamides of -2,3,5,6-.Structural formula is as follows:
Fluorine ether bacterium amide acts on the respiratory chain of fungal mitochondria, inhibits the activity of succinate dehydrogenase, to block electricity Son transmits, and fungus spore germination, germ tube is inhibited to extend, and mycelia growth and spore mother cell form fungi growth and breed main Stage, bactericidal effect are directly caused by parent active agent, without corresponding metabolic activity, for downy mildew of garpe, Phytophthora capsici, A variety of fungal diseases such as the late blight of potato, rice sheath blight disease, cotton seedling blight all have compared with high preventive effect, are a kind of novel wide Compose fungicide.
Bupirimate (Bupirmate), molecular formula:C13H24N4O3S, chemical name:5- butyl -2- ethylaminos - 6- methylpyrimidine -4- base dimethylsulfamates.Bupirimate belongs to miazines systemic fungicide, have protection and Therapeutic effect can rapidly be absorbed by plant roots cauline leaf, and run to each position in plant, therefore resistance of rainwater washing against.With use The advantages that amount is few, high-efficiency low-toxicity.It is effective for white powder disease.
The difficulty of prevention and cure of phytopathogen is increasing at present, on the one hand, with the change of pattern of farming, melon fruits and vegetables etc. Industrial crops cultivated area gradually expands, and disease occurrence degree, generation quantity increase, and is increased in the upper difficulty of prevention;Separately On the one hand, the resistance of pathogen rises year by year under lasting medicament selection pressure, and the control effect of single dose is had a greatly reduced quality, plant Disease control is faced with significant challenge.
Invention content
The purpose of the present invention is provide a kind of applied widely, at low cost, effect good fluorine-containing in view of the above technical problems The plant bactericidal composition of ether bacterium amide and bupirimate.
It is a still further object of the present invention to provide the bactericidal compositions to cause answering on fungal disease in prevention plant epiphyte With the especially purposes on prevention downy mildew, late blight, the fungal diseases such as powdery mildew.
The purpose of the present invention is be achieved through the following technical solutions:
A kind of bactericidal composition of fluorine-containing ether bacterium amide and bupirimate, the bactericidal composition with fluorine ether bacterium amide with Bupirimate is principle active component, and wherein the mass ratio of fluorine ether bacterium amide and bupirimate is 1~70:1~50, Wherein effective ingredient is present in enhancing effective amount in composition in bactericidal composition.
The bactericidal composition, the wherein mass ratio of fluorine ether bacterium amide and bupirimate are preferably 1~50:1~ 30, further preferably 1~20:1~20, it is still more preferably 1~10:1~6.Fluorine ether bacterium amide and bupirimate Preferred mass proportioning or:70:1、50:1、30:1、20:1、10:1、5:1、2.5:1、1:1、1:2、1:4、1:6、1: 10、1:20、1:30、1:50.
In the compositions of the present invention, the mass percentage that both fluorine ether bacterium amide and bupirimate account for composition is 2~80%.It is preferred that 5~70%.
The bactericidal composition, wherein using fluorine ether bacterium amide and bupirimate as principle active component with it is known Auxiliary agent and excipient are re-dubbed any one dosage form allowed on pesticide.These known auxiliary agents, excipients have dispersant, diffusion It is poly- that calcium dodecyl benzene sulfonate, alkyl phenol polyoxyethylene ether, benzylphenol may be used in agent, antifoaming agent, wetting agent, disintegrant etc. Ethylene oxide ether, phenethyl phenol polyethenoxy ether, fatty alcohol polyoxyethylene ether and its similar products, aliphatic amine polyoxyethylene ether, fat Fat acid ethylene oxide adduct, polyoxyethylene polyoxy propylene block compound, castor oil polyoxyethylene ether, Nonyl pheno Ether, TWEEN Series, fatty alcohol polyoxyethylene ether, polyethylene glycol series, Sulfonates, carboxylate, sulfate, phosphate, phosphorous One or more of hydrochlorate, lignosulfonates, xanthans, phenol formaldehyde condensate, ammonium salt, quaternary etc. combine, figuration Agent includes cyclohexanone, dimethylbenzene, various solvent naphthas, water, antifreezing agent (such as propylene glycol), deionized water.The above auxiliary agent, excipient And other auxiliary materials can be applied alone or be used in combination.
The bactericidal composition, dosage form are missible oil, wettable powder, suspending agent, aqueous emulsion or water dispersion granule.
Application of the above-mentioned bactericidal composition on preparing prevention fungal diseases of plants drug.Especially in prevention cereal Application in terms of class, fruit tree, vegetable crop disease.
Above-mentioned application, the fungal diseases of plants are at least one of downy mildew, late blight, powdery mildew.
Beneficial effects of the present invention:
1, the fluorine ether bacterium amide and bupirimate used in the present invention, the mechanism of action is different, and mutual mixture not will produce It is low to touch, can be synergistic, dosage is reduced, cost is reduced.
2, the present composition scope of application increases, suitable for preventing the refractory fungal disease of Cereal, fruit tree, vegetables, Especially preventing downy mildew, late blight, powdery mildew etc. has significant effect.Bactericidal composition of the present invention is to sac fungus, load Bacterium, Fungi Imperfecti and Oomycete fungal disease have good control effect;And inhibit pest or fungi or bacterium to single formulation The generation of the drug resistance of (fluorine ether bacterium amide and bupirimate are any).Bactericidal composition of the present invention can generate higher collaboration Synergistic effect, and the dosage of the amount ratio independent reactive compound of the mixture substantially reduces, i.e. and the activity of mixture is more than The activity of independent component.
Beneficial effects of the present invention compared with prior art:(1) compared with single dose, the composition antagonism fungal disease is such as The fungal diseases such as downy mildew, late blight, powdery mildew have apparent synergistic function, overcome and delayed drug resistance, expand prevention Spectrum, hence it is evident that improve control effect;(2) prevention recruitment, drug cost are reduced;(3) alternative routine and the agriculture for being also easy to produce resistance Medicine;(4) compared with single dose, production and application cost reduces;(5) inhibit the generation of fungi drug resistance, it is with obvious effects to be higher than it Single dose uses.
Specific implementation mode
The invention will be further described with reference to embodiments, and the preparation method of dosage form is conventional side in embodiment Method, " % " of the present invention is mass percent.
Indoor biometrics experiment:
Mycelial growth rate method is used indoors, measures EC of the different agents to bacterial strain50Value, using co-toxicity coefficient calculating side Method calculates the co-toxicity coefficient (CTC) of mixture, determines the building performance of mixture, circular is as follows:
Using a certain single dose in mixture (EC is generally selected as standard agent50Junior), it is calculated:
Single dose toxicity index=standard agent EC50/ certain single dose EC50×100
The toxicity index of the toxicity index of theoretical toxicity index=A single doses × A single doses proportion+B single doses in mixture × B single doses proportion in mixture
The EC of survey toxicity index=standard single dose50The EC of value/mixture50Value × 100
Co-toxicity coefficient=survey toxicity index/theoretical toxicity index × 100
Co-toxicity coefficient is classified:It is antagonism when being less than 80 that mixture, which has synergetic, CTC, when CTC is more than 120, and CTC exists It is summation action between 80-120.
According to active ingredient fluorine ether bacterium amide (A):Bupirimate (B) quality proportioning is:80:1、70:1、50:1、 30:1、20:1、10:1、5:1、2.5:1、1:1、1:2、1:4、1:6、1:10、1:20、1:30、1:50、1:60、1:70 are tried It tests, measures its co-toxicity coefficient to uncinula necator (Uncinula necator.).
Table 1:Indoor biometrics result of the fluorine ether bacterium amide+bupirimate different ratio to uncinula necator
Medicament Virulence regression equation EC50(mg/L) Co-toxicity coefficient
50% fluorine ether bacterium amide WP Y=2.302X+3.047 7.053 -
25% bupirimate EC Y=1.540X+3.610 7.991 -
A:B=80:1 Y=3.632X+1.555 8.882 79.52
A:B=70:1 Y=3.254X+2.592 5.496 128.54
A:B=50:1 Y=2.047X+3.645 4.591 153.98
A:B=30:1 Y=2.653X+2.988 5.733 123.49
A:B=20:1 Y=1.854X+3.649 5.354 132.47
A:B=10:1 Y=1.220X+4.210 4.442 160.49
A:B=5:1 Y=3.388X+2.545 5.304 135.63
A:B=2.5:1 Y=2.623X+2.884 6.408 113.89
A:B=1:1 Y=1.114X+4.250 4.712 159.01
A:B=1:2 Y=1.579X+3.995 4.330 176.72
A:B=1:4 Y=3.557X+2.443 5.234 148.72
A:B=1:6 Y=2.058X+3.526 5.203 150.72
A:B=1:10 Y=1.654X+3.591 7.110 111.05
A:B=1:20 Y=1.278X+4.072 5.323 149.18
A:B=1:30 Y=3.590X+2.150 6.221 127.90
A:B=1:50 Y=1.247X+3.953 6.912 115.31
A:B=1:60 Y=2.330X+2.662 10.079 79.11
A:B=1:70 Y=4.215X+1.184 8.042 99.18
Field control effectiveness test:
The pesticidal preparations prevention uncinula necator experiment made from above-described embodiment.
1, test process:This test medicine dosage sets three concentration for the treatment of, comparison medicine respectively according to the difference of each ingredient Agent is pesticide single dose 50% fluorine ether bacterium amide WP and 25% bupirimate EC and blank clean water experiment respectively.
2, each plot area of test method is 66.7m2, it is repeated 3 times;Investigation drug effect side after investigating and prevent before dispenser Method is:5 points of grab sample in test process area carry out severity Scaling according to national field trial relevant criterion, calculate preventive effect. Test result is shown in Table 2:
Table 2:Field test effect
By indoor biometrics and field efficacy, the result shows that, fluorine ether bacterium amide has apparent with bupirimate composition Synergistic function, the control effect of composition is excellent, and control effect is better than single dose kind, agricultural apply in have answer With value.
Two kinds of reactive compounds can be processed into any one dosage form of permission, illustrate two kinds below with specific embodiment The preparation that active ingredient is processed into, but the preparation that can process of the two kinds of active components be not limited only to it is set forth below.
Embodiment 1:15% fluorine ether bacterium amide bupirimate wettable powder (1:2)
By fluorine ether bacterium amide 5g, bupirimate 10g, detergent LS (to methoxyl group aliphatic acid amido benzene sulfonic acid sodium salt) 2g, dispersing agent NNO (sodium methylene bis-naphthalene sulfonate) 4g, white carbon 5g, kaolin add to 100g mixtures and carry out air-flow crushing, system It is 15% fluorine ether bacterium amide bupirimate wettable powder to obtain active ingredient mass percent.
Embodiment 2:15% fluorine ether bacterium amide bupirimate wettable powder (1:4)
By fluorine ether bacterium amide 3g, bupirimate 12g, lauryl sodium sulfate 3g, dispersing agent NNO 4g, white carbon 5g, kaolin add to 100g mixtures and carry out air-flow crushing, and it is 15% fluorine ether bacterium amide that active ingredient mass percent, which is made, Bupirimate wettable powder.
Embodiment 3:14% fluorine ether bacterium amide bupirimate wettable powder (1:6)
By fluorine ether bacterium amide 2g, bupirimate 12g, lauryl sodium sulfate 3g, dispersing agent NNO 4g, white carbon 5g, kaolin add to 100g mixtures and carry out air-flow crushing, and it is 14% fluorine ether bacterium amide that active ingredient mass percent, which is made, Bupirimate wettable powder.
Embodiment 4:20% fluorine ether bacterium amide bupirimate suspending agent (1:1)
Weigh 10g fluorine ether bacterium amide, 10g bupirimates, lignin 2g, polyoxyethylene poly-oxygen propylene aether and its sulfuric acid Salt 4g, xanthans 0.15g, ethylene glycol 5g, siloxanes 0.10g, aluminium-magnesium silicate 0.5g complement to 100g, in sand mill with water It is 20% fluorine ether bacterium amide bupirimate suspending agent that effective ingredient percent is made under effect.
Embodiment 5:55% fluorine ether bacterium amide bupirimate aqueous emulsion (1:10)
Weigh 5g fluorine ether bacterium amide, 50g bupirimates, phenethyl phenol polyethenoxy ether phosphate 3g, agriculture breast 33# 2g, alkyl phenol polyoxyethylene ether 1g, 150# solvent naphtha 13g, add water to 100g.The above raw material is routinely prepared to the side of aqueous emulsion Method puts into the mixing of mixing kettle high speed, and it is 55% fluorine ether bacterium amide bupirimate water that effective ingredient percent, which is made, Emulsion.
Embodiment 6:42% fluorine ether bacterium amide bupirimate missible oil (1:20)
Weigh 2g fluorine ether bacterium amide, 40g bupirimates, calcium dodecyl benzene sulfonate 8g, phenethyl phenol polyoxyethylene Ether 5g, 150# solvent naphtha are to 100g.The above raw material is routinely prepared and is mixed in the method input mixing kettle of missible oil, is made effectively Ingredient percent is 42% fluorine ether bacterium amide bupirimate missible oil.
Embodiment 7:70% fluorine ether bacterium amide bupirimate missible oil (2.5:1)
Weigh 50g fluorine ether bacterium amide, 20g bupirimates, calcium dodecyl benzene sulfonate 5g, phenethyl phenol polyoxyethylene Ether 2g, castor oil polyoxyethylene ether 2g, 150# solvent naphtha to 100g.The method input that the above raw material is routinely prepared to missible oil is mixed It closes and is mixed in kettle, it is 70% fluorine ether bacterium amide bupirimate missible oil that effective ingredient percent, which is made,.
Embodiment 8:18% fluorine ether bacterium amide bupirimate water dispersion granule (5:1)
Weigh 15g fluorine ether bacterium amide, 3g bupirimates, wooden sodium sulfonate 8g, lauryl sodium sulfate 2g, ammonium sulfate 5g, polyvinyl alcohol 5g, borax 2g, diatomite complement to 100g, by the above raw material by water dispersible granular agent method be formed with effect at It is 17% fluorine ether bacterium amide bupirimate water dispersion granule to divide mass percent.
Embodiment 9:11% fluorine ether bacterium amide bupirimate missible oil (10:1)
Weigh 10g fluorine ether bacterium amide, 1g bupirimates, calcium dodecyl benzene sulfonate 6g, phenethyl phenol polyoxyethylene Ether 7g, 150# solvent naphtha are to 100g.The above raw material is routinely prepared and is mixed in the method input mixing kettle of missible oil, is made effectively Ingredient percent is 11% fluorine ether bacterium amide bupirimate missible oil.
Embodiment 10:31.5% fluorine ether bacterium amide bupirimate microemulsion (20:1)
Weigh 30g fluorine ether bacterium amide, 1.5g bupirimates, calcium dodecyl benzene sulfonate 6g, phenethyl phenol polyoxy second Alkene ether phosphate 3g, agriculture breast 33#2g, alkyl phenol polyoxyethylene ether 1g, isopropanol 10g add water to 100g.By the above raw material by normal The method that rule prepare microemulsion, which is put into mixing kettle, to be mixed, and it is 31.5% fluorine ether bacterium amide that effective ingredient percent, which is made, Bupirimate microemulsion.
Embodiment 11:31% fluorine ether bacterium amide bupirimate missible oil (30:1)
Weigh 30g fluorine ether bacterium amide, 1g bupirimates, calcium dodecyl benzene sulfonate 4g, phenethyl phenol polyoxyethylene Ether 4g, 150# solvent naphtha are to 100g.The above raw material is routinely prepared and is mixed in the method input mixing kettle of missible oil, is made effectively Ingredient percent is 31% fluorine ether bacterium amide bupirimate missible oil.
Embodiment 12:51% fluorine ether bacterium amide bupirimate suspending agent (50:1)
Weigh 50g fluorine ether bacterium amide, 1g bupirimates, lignin 2g, polyoxyethylene poly-oxygen propylene aether and its sulfuric acid Salt 4g, xanthans 0.15g, ethylene glycol 5g, siloxanes 0.10g, aluminium-magnesium silicate 0.5g complement to 100g, in sand mill with water It is 51% fluorine ether bacterium amide bupirimate suspending agent that effective ingredient percent is made under effect.
Embodiment 13:32% fluorine ether bacterium amide bupirimate microemulsion (1:15)
Weigh 2g fluorine ether bacterium amide, 30g bupirimates, calcium dodecyl benzene sulfonate 6g, phenethyl phenol polyoxyethylene Ether phosphate 3g, agriculture breast 33#2g, alkyl phenol polyoxyethylene ether 1g, isopropanol 10g add water to 100g.Routinely by the above raw material It prepares and is mixed in the method input mixing kettle of microemulsion, it is that 32% fluorine ether bacterium amide second is phonetic that effective ingredient percent, which is made, Sulfocarbolate microemulsion.
Embodiment 14:6% fluorine ether bacterium amide bupirimate aqueous emulsion (1:5)
Weigh 1g fluorine ether bacterium amide, 5g bupirimates, phenethyl phenol polyethenoxy ether phosphate 3g, agriculture breast 33#2g, Alkyl phenol polyoxyethylene ether 1g, 150# solvent naphtha 13g, adds water to 100g.The method that the above raw material is routinely prepared into aqueous emulsion The mixing of mixing kettle high speed is put into, it is 6% fluorine ether bacterium amide bupirimate water and milk that effective ingredient percent, which is made, Agent.
Embodiment 15:62% fluorine ether bacterium amide bupirimate microemulsion (1:30)
Weigh 2g fluorine ether bacterium amide, 60g bupirimates, calcium dodecyl benzene sulfonate 6g, phenethyl phenol polyoxyethylene Ether phosphate 3g, agriculture breast 33#2g, alkyl phenol polyoxyethylene ether 1g, isopropanol 10g add water to 100g.Routinely by the above raw material It prepares and is mixed in the method input mixing kettle of microemulsion, it is that 62% fluorine ether bacterium amide second is phonetic that effective ingredient percent, which is made, Sulfocarbolate microemulsion.
Embodiment 16:51% fluorine ether bacterium amide bupirimate suspending agent (1:50)
Weigh 1g fluorine ether bacterium amide, 50g bupirimates, lignin 2g, polyoxyethylene poly-oxygen propylene aether and its sulfuric acid Salt 4g, xanthans 0.15g, ethylene glycol 5g, siloxanes 0.10g, aluminium-magnesium silicate 0.5g complement to 100g, in sand mill with water It is 51% fluorine ether bacterium amide bupirimate suspending agent that effective ingredient percent is made under effect.
Embodiment 17:7% fluorine ether bacterium amide bupirimate water dispersion granule (1:2.5)
Weigh 2g fluorine ether bacterium amide, 5g bupirimates, wooden sodium sulfonate 8g, lauryl sodium sulfate 2g, ammonium sulfate 5g, polyvinyl alcohol 5g, borax 2g, white carbon 3g, diatomite complement to 100g, and the above raw material is pressed water dispersible granular agent method system It is 7% fluorine ether bacterium amide bupirimate water dispersion granule at active ingredient mass percent.

Claims (7)

1. a kind of bactericidal composition of fluorine-containing ether bacterium amide and bupirimate, it is characterised in that the bactericidal composition is with fluorine ether Bacterium amide and bupirimate are principle active component, and wherein the mass ratio of fluorine ether bacterium amide and bupirimate is 70:1 ~5:1、1:1~1:6、1:20~1:30.
2. bactericidal composition according to claim 1, it is characterised in that the fluorine ether bacterium amide and bupirimate The mass percentage that the two accounts for composition is 2-80%.
3. bactericidal composition according to claim 2, it is characterised in that the fluorine ether bacterium amide and bupirimate The mass percentage that the two accounts for composition is 10-40%.
4. bactericidal composition according to claim 1, it is characterised in that based on fluorine ether bacterium amide and bupirimate Any one dosage form for wanting active ingredient and insecticides adjuvant, excipients to be configured to allow on pesticide.
5. bactericidal composition according to claim 4, it is characterised in that the dosage form be missible oil, suspending agent, aqueous emulsion, Wettable powder or water dispersion granule.
6. application of the bactericidal composition described in claim 1 on preparing prevention fungal diseases of plants drug.
7. application according to claim 6, it is characterised in that the fungal diseases of plants is downy mildew, late blight, white At least one of powder disease.
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