CN106857558B - A kind of Synergistic mite killing composition containing fluacrypyrim - Google Patents

A kind of Synergistic mite killing composition containing fluacrypyrim Download PDF

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CN106857558B
CN106857558B CN201710091857.2A CN201710091857A CN106857558B CN 106857558 B CN106857558 B CN 106857558B CN 201710091857 A CN201710091857 A CN 201710091857A CN 106857558 B CN106857558 B CN 106857558B
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tdca
grams
fluacrypyrim
thiadiazoles
mite
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CN106857558A (en
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杨维清
李洪洋
任川宏
刘伟
王树德
张燕
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Shandong Haoyuan Biotechnology Co ltd
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Xihua University
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses a kind of Synergistic mite killing compositions, with N- (5- tert-butyl -1,3,4- thiadiazoles -2- base)-N'- (2,6- disubstituted pyridines -4- base)-N, 4- dimethyl -1,2,3- thiadiazoles -5- formamidine compound (TDCA) and fluacrypyrim are that acceptable auxiliary element collectively constitutes in effective component, with pesticide, and wherein TDCA and fluacrypyrim weight ratio are 40:1 to 1:60.It is tested, is shown after two kinds of combination of active principles without antagonism, and there is significant synergistic effect, to crop safety by laboratory experiment and field efficacy.

Description

A kind of Synergistic mite killing composition containing fluacrypyrim
Technical field
The present invention relates to a kind of insecticide acaricide compositions, concretely relate to one kind containing fluacrypyrim and N- tri- and replace -1, The insecticide acaricide composition of 2,3- thiadiazoles -5- formamidine compounds, belongs to field of pesticide preparation.
Background technique
(denomination of invention: application number CN2015100098343, January 9 2015 date of application contain three nitrogen to Chinese patent 1,2,3- thiadiazoles -5- formamidine the compound of heterocycle and synthesis) in report the artificial Xihua Univ (inventor of patent application The town Wang Hui, Liu Ping, Yang Wei are clear etc.) general formula be TDCA the polysubstituted -1,2,3- thiadiazoles -5- formamidine compound of N- and its conjunction At method (formula 1).Chinese patent reports patent in (application number CN2015100237806, January 19 2015 date of application) Apply for the polysubstituted -1,2,3- thiadiazoles -5- of N- that artificial Xihua Univ (inventor Liu Ping, Yang Wei clear etc.) mutual-through type is TDCA The novel synthesis of formamidine compound is reported that the new method uses the synthesis of target product and is first cyclized, finally upper first The method of base obtains fine experiment effect.Chinese patent (application number CN2015103042053, June 9 2015 date of application Day, denomination of invention: cyclization method synthesize polynitrogen heterocycle thiadiazoles -5- formamidine compound) in report the artificial Xihua of patent application University's (inventor Yang Weiqing, Liu Ping etc.) mutual-through type is the polysubstituted -1,2,3- thiadiazoles -5- formamidine compound of N- of TDCA Novel synthesis reported that the new method is to the synthesis of target product using first upper methyl, and the method being finally cyclized, this is new The easy preparation of synthetic method high income, catalyst, catalyst is cheap, phosphorus-containing wastewater is few, to more environment-friendly.Chinese patent (patent No. ZL201510277765.4, May 28 2015 date of application, 2016 Granted publication dates August 31st, invention Title: 1,2,3- thiadiazoles -5- formamidine poly-heterocyclic compounds are as acaricidal purposes) in report patent application artificially western The general formula of Hua Da (inventor Yang Weiqing, Liu Ping, Zhang Yuanyuan etc.) is the polysubstituted -1,2,3- thiadiazoles -5- first of N- of TDCA Evil of the amidine compound as acaricidal purposes, especially for fruit tree, vegetables, cotton, peanut and other crops and ornamental plant Acarid control.But murder by poisoning power of the polysubstituted -1,2,3- thiadiazoles -5- formamidine compound of N- to part adult that general formula is TDCA It is not powerful enough, it needs and kills the high acaricide (such as avermectin, fluacrypyrim) of adult activity to carry out interworking use.Many institute's weeks Know, Insecticidal and acaricidal agent is all easy pest in the long-term use and develops drug resistance, all to extend using for a new varieties Phase, carrying out interworking use with other excellent insecticidal acaricide kinds is a kind of common strategy.
Fluacrypyrim is by first methoxy acrylic acaricide of BASF AG's exploitation of Germany.Fluacrypyrim is pure Product raw medicine is white solid, chemical formula C20H21F3N2O5, CAS accession number 229977-93-9, structural formula is as shown in Equation 3.Fluacrypyrim 106-107 °C of sterling fusing point, is insoluble in water, is relatively soluble in chloroform, toluene, acetone and other organic solvent.With well tag and Stomach poison function, it is effective to each stage of harmful mite, including ovum, deutonymph, adult mite, and quick-acting is good, the lasting period is long, complete to citrus The harmful mites such as pawl mite, Xiu Pi lice, yellow tea mite, Tetranychus cinnabarinus and Tetranychus urticae have fine preventive effect, can be used for citrus, apple, grape The mite evil of equal fruit trees is administered.
Mite class belongs to Arthropoda, Arachnoidea, Acarina, and individual is smaller.There may be all ranks in a group The mite of section, including ovum, deutonymph, young mite and adult mite.Fruit tree, vegetables, cotton, peanut and other crops and ornamental plant are intensively infested mostly The vacuum side of blade of object, and its breeding is rapidly, high these of selfing degree all determine the more difficult prevention and treatment of mite class.On the other hand, Nong Minyou The good single acaricide of habit continuous use miticidal effect, as a result causes acarid to generate resistance within many time and lose benefit With value.Therefore, using different role mechanism, different types of acaricide be solve harmful mite be also easy to produce resistance effective way it One.
Summary of the invention
The main object of the present invention is against the above deficiency, by the acaricidal rational mixture of different role mechanism, to provide One kind having synergistic effect, and miticidal effect is good, safety, while can reduce the miticide composition of use cost again.
Chinese patent (patent No. ZL201510277765.4, May 28 2015 date of application, Granted publication date On August 31st, 2016, denomination of invention: 1,2,3- thiadiazoles -5- formamidine poly-heterocyclic compounds are as acaricidal purposes) in report N- polysubstituted -1,2, the 3- thiadiazoles -5- formamidine compound (formula 1) that road general formula is TDCA is used as acaricidal purposes, special It is not the control of pest mite for fruit tree, vegetables, cotton, peanut and other crops and ornamental plant.In the compound that general formula is TDCA The detailed title of TDCA-6~TDCA-13(TDCA-6~TDCA-13 and structural formula are with reference to association patent, Chinese Patent Application No. CN2015100098343) there is preferable acaricidal activity.
What the object of the invention was realized in that:
Miticide composition of the present invention is N- (5- tert-butyl -1,3,4- thiadiazoles -2- base)-N'- (2,6- bis- with Chinese Substituted pyridines -4- base)-N, 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidine (hereinafter referred to as TDCA in the present invention), structural formula One kind compound and fluacrypyrim as shown in formula 1 are that acceptable auxiliary element is common in effective component, with pesticide Composition.
The compound that TDCA is referred to as in miticide composition of the present invention can be compound N-(5- tert-butyl -1,3,4- thiophene Diazole -2- base)-N'- (2,6- dichloropyridine -4- base)-N, 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidine (this invention simply if referred to as TDCA-6), compound N-(5- tert-butyl -1,3,4- thiadiazoles -2- base)-N'- (the chloro- 6- fluorine pyridin-4-yl of 2-)-N, 4- diformazan Base -1,2,3- thiadiazoles -5- carbonamidine (this invention simply if referred to as TDCA-7), compound N-(5- tert-butyl -1,3,4- thiadiazoles -2- Base) (this invention simply if referred to as TDCA- for-N'- (the chloro- 6- bromopyridine -4- base of 2-)-N, 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidine 8), compound N-(5- tert-butyl -1,3,4- thiadiazoles -2- base)-N'- (the chloro- 6- iodine pyridine -4- base of 2-)-N, dimethyl -1 4-, 2,3- thiadiazoles -5- carbonamidine (this invention simply if referred to as TDCA-9), compound N-(5- tert-butyl -1,3,4- thiadiazoles -2- base) - N'- (2,6- difluoro pyridine -4- base)-N, 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidine (this invention simply if referred to as TDCA-10) are changed Close object N- (5- tert-butyl -1,3,4- thiadiazoles -2- base)-N'- (the bromo- 6- fluorine pyridin-4-yl of 2-)-N, 4- dimethyl -1,2,3- Thiadiazoles -5- carbonamidine (this invention simply if referred to as TDCA-11), compound N-(5- tert-butyl -1,3,4- thiadiazoles -2- base)-N'- (the fluoro- 6- iodine pyridine -4- base of 2-)-N, 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidine (this invention simply if referred to as TDCA-12), chemical combination Object N- (5- tert-butyl -1,3,4- thiadiazoles -2- base)-N'- (2,6- dibromo pyridine -4- base)-N, 4- dimethyl -1,2,3- thiophene two Any one in azoles -5- carbonamidine (this invention simply if referred to as TDCA-13).
Miticide composition of the present invention can be TDCA-6, TDCA-7, TDCA-8, TDCA-9, TDCA-10, TDCA-11, Any one in TDCA-12, TDCA-13 is common for acceptable auxiliary element in effective component, with pesticide with fluacrypyrim Composition.
Miticide composition of the present invention be also possible to TDCA-6, TDCA-7, TDCA-8, TDCA-9, TDCA-10, TDCA-11, Any two kinds in TDCA-12, TDCA-13 and the TDCA mixture after two or more combinations be combined into again with fluacrypyrim group effectively at Point, it is collectively constituted with acceptable auxiliary element in pesticide.
The permission weight ratio of TDCA and fluacrypyrim is 60:1 to 1:80 in miticide composition of the present invention, is preferably in a proportion of 40:1 to 1:60.
Miticide composition compound of the present invention has acaricidal purposes, is especially used for fruit tree, vegetables, cotton, peanut The control of pest mite of equal crops and ornamental plant.It is raw that the present composition is applied on crop and/or ornamental plant harmful acarid Long region can effectively prevent harmful mite.Present composition administration time can be in each growth phase in acarid, including Ovum, deutonymph, young mite and adult mite.Be mentioned below be the harmful mite that the present composition can be prevented and treated some representatives, enumerate unlimited Harmful mite on following certain crops and/or ornamental plant.
As the mite class for becoming present composition control object, it can enumerate: belong to the mite of Ying Pi section: Japanese blood mite, Haemaphysalis longicornis, boophilus microplus, dermacentor reticulatus, dermacentor taiwanensis, haemaphysalis flava, ixodes persulcatus etc..Belong to the mite of Eriophyidae: tea point leaf Save tick, tealeaves goitre mite, apple rust mite, grape leaf rust mite, tulip aceria, fructus lycii burrknot tick, pseudo- pears rust tick, Pi Shi skin goitre mite Deng.Belong to the mite of Tyroglyphidae: hesperidium mite, ellipse dispersion, Acarus siro, river open country rouge mite, Rhizoylyphus echinopus etc..Belong to Tarsonemidae Mite: Webster tarsonemid, Polyphagotarsonemus latus Banks, primrose herbivore mite, double leaf tarsonemid.Belong to the mite of Eupodidae: wheat leaf pawl mite, Chinese cabbage mite.Belong to the mite of Tetranychidae: panonychus citri, panonychus ulmi, mulberry Panonychus citri, Tetranychus urticae, Tetranychus cinnabarinus, purplish red short It must mite, priet mite, Liu Shi short hairs mite, Asia beginning tetranychid, knee beginning tetranychid, northern beginning tetranychid, Lee's beginning tetranychid, Eotetranychus smithi Deng.
Although the present composition shows outstanding prevention and treatment activity to the acarid of various mite sections, to useful crop, such as Fruit tree, vegetables, cotton, peanut and other crops and/or ornamental plant only have the damage of small degree or absolutely not damage, and take The specific structure of each compound, amount of application, the useful crop object of application certainly in present composition general structure.Here it is this Invention compound can be suitable for the basic reason of control of pest mite on crop and/or ornamental plant.
Acceptable auxiliary element in described pesticide, including used in pesticide at present, unfavorable shadow will not be generated Loud all kinds of common solvents and/or inert filler and/or surfactant and/or preservative and/or antifreezing agent and/or agglomeration resistance Agent and/or defoaming agent and/or cosolvent and/or the corresponding adding ingredient such as stabilizer and/or thickener, and can be according to being produced Dosage form do corresponding selection or adjustment.
Agrochemical formulations generally comprise the miticide composition of the present invention of 0.1-99 weight %, especially 2-90 weight %.? Miticide composition concentration is in wettable powder (WP), such as the rest part in 10-90 weight %, 100 weight % is by routinely making Agent auxiliary element composition.Miticide composition concentration is in suspending agent (SC), such as 1-90 weight %, preferably 5-75 weight %, 100 Rest part in weight % is made of conventional formulation auxiliary element.Miticide composition concentration is in suspoemulsion (SE), such as 1- 90 weight %, preferably 5-75 weight %, the rest part in 100 weight % are made of conventional formulation auxiliary element.In water dispersant (WDG) miticide composition concentration is in, such as 1-95 weight %, preferably 10-70 weight %, and the rest part in 100 weight % is by normal Regulation agent auxiliary element composition.The preparation of other powder types includes 1-40 weight % reactive compound, and preferably 5-20 weight % is living Property compound, the rest part in 100 weight % are made of conventional formulation auxiliary element.
Miticide composition of the present invention is needed according to different uses or application Huan Jing ∕ condition, raw by current conventional pesticide TDCA-6 in the miticide composition and fluacrypyrim effective component and corresponding auxiliary element are sufficiently mixed by production mode for raw material, It is prepared into various forms of available corresponding dosage forms.Possible dosage form includes: wettable powder, water dispersant, suspension Agent, aqueous emulsion, suspoemulsion, microcapsule formulations etc..Such as several typical common dosage forms and preparation can be with:
Microcapsule formulations (CJ), which refer to, forms " core-shell structure copolymer " structure small container using natural or synthesis high molecular material, will Pesticide coats wherein, and the formulations of pesticide in water that suspend.Micro-capsule suspension appearance is a thick working fluid, with water Emulsion and aqueous suspension agent are similar.With micro- sem observation, its shape of microcapsules is spherical in shape, rugby shape, grain or other shapes.It is micro- Capsule diameter is generally at 3-30 microns.Small rice grain and mung bean grain size are about as much as with the observation of 400 power microscopes.Due to micro- glue Capsule pesticide has the characteristics that the lasting period is long, toxicity is low, safe ready, just becomes a developing direction of pesticides new formulation.Micro- glue The customary preparation methods of capsule have complex coacervation, Simple coacervation, interfacial polymerization, situ aggregation method, orifice-coagulating bath method etc..Most Occur some novel processing steps, such as molecular inclusion, microchannel emulsification method, supercritical fluid quick expansion again in recent years Method, yeast microcapsule method, self-assembled multilayer film method.Microcapsules often have sodium alginate, chitosan, gelatin, porous-starch with wall material Deng.Complex coacervation is most popular method in above-mentioned microcapsule preparation method.Complex coacervation preparation principle is with two kinds with phase The substance of counter charges makees embedded object, and core material disperses wherein, to change change pH values, temperature or solution concentration, due to the effect between charge, Make two kinds of wall material solubility declines and is condensed into microcapsules precipitation.A kind of positively charged colloidal solution and another kind are negatively charged Colloidal solution mutually mix, since the interaction between xenogenesis charge forms compound polyelectrolyte and separate, be deposited on Microcapsules are obtained around capsule-core.Complex coacervation is often capsule material with gelatin, Arabic gum.Gelatin is protein, in aqueous solution, Contain-NH on strand2With-COOH and its accordingly dissociate group-NH3 +With-COO-, but contain-NH3 +With-COO-Ion is how much, It is influenced by PH values.For gelatin solution in pH 4.0 or so, positive charge is most.Arabic gum is polysaccharide, water-soluble In liquid ,-COOH and-COO is contained on strand-, there is negative electrical charge.Therefore in gelatin and Arabic gum mixed aqueous solutions, PH is adjusted when being about 4.0, gelatin and Arabic gum form compound because charged phase neutralizes instead, solubility reduction, from system Middle cohesion encystation is precipitated.Curing agent formaldehyde is added, formaldehyde and gelatin generate the condensation reaction of amine aldehyde, and gelatin molecule crosslinking reticulates Structure keeps the shape of micro-capsule, becomes irreversible micro-capsule；Add 2% NaOH to adjust medium pH 8 ~ 9, it is anti-to be conducive to the condensation of amine aldehyde It should carry out completely.
Water dispersant (WDG) can fater disintegration in water, and can be uniformly dispersed in formation higher suspension dispersion in water A kind of granular preparation.The present composition and auxiliary element one can be reinstated to air-flow smashing or ultra-fine grinding, system when preparation At wettable powder, this is dry method；The present composition, auxiliary agent, adjuvant etc. are ground in sand mill using water as medium, Suspending agent is made, then re-dry is granulated, this is wet process.
Wettable powder (WP), i.e., solid powder preparation that in water can be evenly dispersed.It, can be according to conventional side when preparation Formula is firstly added the composition of TDCA-6 and fluacrypyrim of the present invention, and diatomite, clay, precipitated calcium carbonate, white carbon black is then added Etc. common diluent or inert substance, other common auxiliary elements are added, such as alkylnaphthalene sulfonate, alkylbenzene sulfonate, rouge Fat alcohol sulfate, alkyl bromination ammonium, alkyl ammomium chloride, quaternary alkylphosphonium salt, alkyl polyoxyethylene base ether sulfate, lignosulfonates, One of lignin, carboxymethyl cellulose, sodium carboxymethylcellulose, azone, thiophene ketone or several and common stabilizer, The complementary auxiliary component such as foam inhibitor, anticaking agent.
Suspoemulsion (SE) the i.e. hybrid dispersions of the insoluble pesticide of water in water, one such effective component is in suspension State, other effective components are in emulsion state.It can be by the present composition and corresponding emulsion, wet point when being prepared when preparation The auxiliary elements such as powder, thickener, stabilizer, antifreezing agent, pH adjusting agent, defoaming agent, conventionally, through wet process Ultramicro-powder It is broken to be mixed to prepare.Wherein emulsifier is alkyl phenol polyoxyethylene ether class (agriculture breast 100#), alkylbenzene sulfonate (agriculture breast 500#), benzene Ethyl phenol polyethenoxy ether class (agriculture breast 600#), alkyl phenol or aralkyl phenol polyethenoxy ether formaldehyde condensation species (Nongru-700 #) Deng one of or it is several.Wherein Ricinate is lignosulfonates, lignin, phosphate polyethers, carboxymethyl fibre Tie up element, sodium carboxymethylcellulose, crown ether, alkylnaphthalene sulfonate, alkylbenzene sulfonate, aliphatic alcohol sulfate, alkyl ammonium halide, season One of phosphonium salt, alkyl polyoxyethylene base ether sulfate, azone, thiophene ketone are several；Thickener and stabilizer are polyethylene One of alcohol, condensed phosphate, xanthan gum, aluminum magnesium silicate etc. are several；Antifreezing agent be sodium chloride, urea, ammonium sulfate, One of ethylene glycol, glycerol etc. are several；PH adjusting agent be potassium dihydrogen phosphate, dipotassium hydrogen phosphate, citric acid, sodium carbonate, One of potassium carbonate etc. is several.Organosilicon is commonly used as defoaming agent and foam inhibitor.
Suspending agent (SC) i.e. agricultural chemicals suspension agent (SC) is water insoluble solids pesticide or not mixed liquid pesticidal in water or oil Dispersion.When preparation, with water or oil for decentralized medium, by TDCA-6 of the present invention and fluacrypyrim composition and auxiliary element (such as thickener, stabilizer, Ricinate, antifreezing agent, pH adjusting agent, defoaming agent) is made through soybean dietary fiber (grinding) ?.Wherein Ricinate is phosphate polyethers, alkylnaphthalene sulfonate, alkylbenzene sulfonate, aliphatic alcohol sulfate, alkyl bromide Change ammonium, alkyl ammomium chloride, crown ether, quaternary alkylphosphonium salt, alkyl polyoxyethylene base ether sulfate, lignosulfonates, lignin, carboxymethyl One of cellulose, sodium carboxymethylcellulose, azone, thiophene ketone are several；Thickener and stabilizer are polyvinyl alcohol, condensation One of phosphate, xanthan gum, aluminum magnesium silicate etc. are several；Antifreezing agent be sodium chloride, urea, ammonium sulfate, ethylene glycol, One of glycerol etc. is several；PH adjusting agent is potassium dihydrogen phosphate, dipotassium hydrogen phosphate, citric acid, sodium carbonate, potassium carbonate etc. One of or it is several.Organosilicon is commonly used as defoaming agent and foam inhibitor.
It should be noted that specific dosage form mentioned above is the representative dosage form that present composition object can be prepared, enumerate It is not limited to these above-mentioned dosage forms.
To be administered, if appropriate formulation is diluted in a usual manner, such as wettable powder, water dispersant, Suspending agent, aqueous emulsion, suspoemulsion are diluted with water.Usually no longer with other inert materials before the application such as pulvis, granule, microcapsule formulations Matter dilution.
The amount of application of the compounds of this invention changes according to external condition, and the external condition especially prevents and treats acarid pair As, temperature, humidity, preparation formulation.It can change in a wider range, such as 0.1-500g/667m2Or more chemical combination of the present invention Object, preferably 1-50g/667m2。
Comprehensively consider the factors such as mite killing broad spectrum activity, toxicity, production cost, TDCA-6(formula 2) it is to be compared in numerous compounds The better acaricide compared with for.Therefore, in the following narrations of the present invention, general formula is mainly represented with TDCA-6 and is taken as the N- of TDCA more Generation -1,2,3- thiadiazoles -5- formamidine compound.
Concrete mode by the following examples is again described in further detail above content of the invention.But it does not answer This range for being interpreted as the above-mentioned theme of the present invention is only limitted to example below by this.The above-mentioned technical idea feelings of the present invention are not being departed from Under condition, the various replacements or change made according to ordinary skill knowledge and customary means, should all include of the invention In range.Each material composition ratio is weight % in embodiment.
Specific embodiment:
(1), example of formulations
The miticide composition TDCA-6 fluacrypyrim microcapsule formulations (CJ) of embodiment 1:6% (6% refers to original ingredient ratio, similarly hereinafter)
30 grams of TDCA-6,30 grams of fluacrypyrims, 30 grams of gelatin, 20 grams of poly-aspartates, 10 grams of Tween-60s, 50 are weighed respectively Gram Arabic gum, 10 grams of polyethylene glycol, 50 gram of 20% formalin, 10% acetum are appropriate, and (titer is i.e. by preparation process Titration operation determine usage amount, similarly hereinafter), 20% NaOH solution (titer), distilled water complementary to 1000 grams, it is spare；
It is prepared by preparation step (1) poly-aspartate and gelatin mixed solution: after gelatin is impregnated swelling with distillation appropriate amount of water, It dissolves by heating, is heated to 50 DEG C, poly-aspartate is added, appropriate distilled water is added, and 50 DEG C of heat preservations are spare in stirring.(2) Arabic The preparation of sol solution: being added appropriate distilled water in reaction unit, Arabic gum powder is added, is heated to 80 DEG C or so, gently stirs Mixing makes to dissolve, and 80 DEG C of heat preservations are spare.(3) it the preparation of TDCA-6 and fluacrypyrim effective component emulsion: by TDCA-6, fluacrypyrim, spits Temperature -60, polyethylene glycol, above-mentioned preparation gumwater, be placed in tissue mashing machine, emulsify 30 seconds to get emulsion. (4) it mixes: under the conditions of 50~55 DEG C, above-mentioned poly-aspartate and gelatin mixed solution is added, being gently mixed makes to be uniformly mixed. (5) preparation of micro-capsule: under constant stirring, 10% acetum is added dropwise in Xiang Qianshu mixed liquor, adjusts pH to 3.8~4.0；(6) The solidification of micro-capsule: under constant stirring, about 30 DEG C of distilled water being added in micro-capsule liquid, will contain micro-capsule liquid from 50~55 DEG C of water-baths In remove, be stirred continuously, natural cooling, when temperature drops to 32~35 DEG C, be added ice cube, continue stirring to temperature be 10 DEG C with Under, 20% formalin is added, continues 15~25min of stirring, then with its pH 8~9 of 20%NaOH solution tune, continue stirring 20~ 30min, observation stand and settle to micro-capsule until being precipitated.(7) it the filtering and drying of micro-capsule: completely to micro-capsule sedimentation, crosses and filters out Fall supernatant, micro-capsule distillation is washed to formaldehydeless taste, centrifugation, drying.
The miticide composition TDCA-6 fluacrypyrim water dispersible granules (WDG) of embodiment 2:20%
166.7 grams of TDCA-6,33.3 grams of fluacrypyrims, 57 grams of lignin, 43 grams of acrylic acid minor matters polymer, 40 are weighed respectively Gram dodecyl sodium sulfate, 30 grams of polyethylene glycol, bentonite complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated, It is drying to obtain water dispersible granules.
The miticide composition TDCA-6TDCA-10TDCA-13 fluacrypyrim water dispersible granules of embodiment 3:40% (WDG)
120 grams of TDCA-6,80 grams of TDCA-13,50 grams of TDCA-10,150 grams of fluacrypyrims, 50 grams of lignin, 50 are weighed respectively Gram acrylic acid minor matters polymer, 40 grams of dodecyl sodium sulfates, 60 grams of polyethylene glycol, bentonite complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated, It is drying to obtain water dispersible granules.
The miticide composition TDCA-6 fluacrypyrim wettable powder (WP) of embodiment 4:20%
181.8 grams of TDCA-6,18.2 grams of fluacrypyrims, 40 grams of lignosulfonates calcium, 40 grams of carboxymethyl celluloses are weighed respectively Plain sodium, 50 grams of aluminum magnesium silicates, 25 grams of neopelexes, 20 grams of tetrabutylammonium bromide, kaolin complementary are standby to 1000 grams With；
Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The miticide composition TDCA-6 fluacrypyrim wettable powder (WP) of embodiment 5:30%
200 grams of TDCA-6,100 grams of fluacrypyrims, 30 grams of lignosulfonates calcium, 30 grams of carboxymethyl celluloses are weighed respectively Sodium, 30 grams of aluminum magnesium silicates, 20 grams of neopelexes, 20 grams of tetrabutylammonium bromide, kaolin complementary are standby to 1000 grams With；
Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The fluacrypyrim suspending agent (SC) of embodiment 6:35%
350 grams of fluacrypyrims, 40 grams of lignosulfonates calcium, 50 grams of sodium carboxymethylcelluloses, 30 grams of alumina silicate are weighed respectively Magnesium, 40 grams of neopelexes, 60 grams of polyethylene glycol, water complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, just dispersion is carried out using high-speed shearing machine, is then ground in sand mill To effective component partial size at 2~5 μm.
The fluacrypyrim wettable powder (WP) of embodiment 7:30%
300 grams of fluacrypyrims, 60 grams of lignosulfonates calcium, 60 grams of sodium carboxymethylcelluloses, 50 grams of alumina silicate are weighed respectively Magnesium, 30 grams of neopelexes, 25 grams of tetrabutylammonium bromide, kaolin complementary are spare to 1000 grams；
Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The TDCA-6 wettable powder (WP) of embodiment 8:30%
300 grams of TDCA-6,35 grams of lignosulfonates calcium, 40 grams of sodium carboxymethylcelluloses, 32 grams of alumina silicate are weighed respectively Magnesium, 25 grams of neopelexes, 25 grams of tetrabutylammonium bromide, kaolin complementary are spare to 1000 grams；
Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The fluacrypyrim suspending agent (SC) of embodiment 9:10%
100 grams of fluacrypyrims, 40 grams of lignosulfonates calcium, 50 grams of sodium carboxymethylcelluloses, 80 grams of alumina silicate are weighed respectively Magnesium, 60 grams of neopelexes, 50 grams of polyethylene glycol, water complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, just dispersion is carried out using high-speed shearing machine, is then ground in sand mill To effective component partial size at 2~5 μm.
The TDCA-6 suspending agent (SC) of embodiment 10:10%
100 grams of TDCA-6,50 grams of lignosulfonates calcium, 60 grams of sodium carboxymethylcelluloses, 85 grams of alumina silicate are weighed respectively Magnesium, 70 grams of neopelexes, 60 grams of polyethylene glycol, water complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, just dispersion is carried out using high-speed shearing machine, is then ground in sand mill To effective component partial size at 2~5 μm.
The fluacrypyrim suspoemulsion (SE) of embodiment 11:10%
100 grams of fluacrypyrims, 15 grams of ethanol amines, 20 grams of agriculture breast 500# (calcium dodecyl benzene sulfonates, by Jinan are weighed respectively Agrochemicals Co., Ltd production, similarly hereinafter), 40 grams of agriculture breast 601#(phenethyl phenol polyethenoxy ethers, by Shandong Zibo Yongfa chemical plant Production, similarly hereinafter), 80 grams of dimethylbenzene, 60 grams of polyethylene glycol, 20 grams of ammonium sulfate, water complementary to 1000 grams, it is spare；
Preparation: fluacrypyrim, solvent xylene, emulsifier, co-emulsifier are mixed into uniform oily phase；Water, antifreeze are mixed Uniform water phase is synthesized, under the stirring of high-speed shearing machine, oil is mutually poured into water phase, is sufficiently mixed.
The TDCA-6 suspoemulsion (SE) of embodiment 12:5%
50 grams of TDCA-6,25 grams of ethanol amines, 30 grams of agriculture breast 500#, 30 grams of agriculture breast 601#, 70 grams of dimethylbenzene, 80 are weighed respectively Gram polyethylene glycol, 30 grams of ammonium sulfate, water complementary are spare to 1000 grams；
Preparation: TDCA-6, solvent xylene, emulsifier, co-emulsifier are mixed into uniform oily phase；Water, antifreeze are mixed Uniform water phase is synthesized, under the stirring of high-speed shearing machine, oil is mutually poured into water phase, is sufficiently mixed.Pass through following experiment It can be shown that the compounding of two effective component TDCA-6 and fluacrypyrim can have significantly in above-mentioned miticide composition of the invention Synergistic effect.
(2), biological Examples
Embodiment 13:TDCA-6 and fluacrypyrim composite formula screening experiment
One, (A represents fluacrypyrim to reagent agent in following reagents；B represents TDCA-6)
A agent: 10% fluacrypyrim suspoemulsion (SE) (being prepared by the method for embodiment 11)
B agent: 5% TDCA-6 suspoemulsion (SE) (being prepared by the method for embodiment 12)
AB1: fluacrypyrim TDCA-6(A:B=40:1)
AB2: fluacrypyrim TDCA-6(A:B=20:1)
AB3: fluacrypyrim TDCA-6(A:B=10:1)
AB4: fluacrypyrim TDCA-6(A:B=1:1)
AB5: fluacrypyrim TDCA-6(A:B=1:10)
AB6: fluacrypyrim TDCA-6(A:B=1:20)
AB7: fluacrypyrim TDCA-6(A:B=1:40)
AB8: fluacrypyrim TDCA-6(A:B=1:60)
Two, for trying insect
For examination insect using the red spider adopted in the citrus trees of field, raised for 3 generations indoors as test worm.
Three, experimental method
Experiment uses dip slide method.Every kind of reagent tests 5 kinds of concentration (see Table 1 for details for the specific concentration of every kind of reagent), each repetition Processing three times, repeats 120 every time, and 72 hours microscopic examination results after medicine obtain the death rate for test worm, calculates LC50With total poison Coefficient (CTC).
Four, calculation method
It is ordinate that the death rate of every kind of reagent, which is converted to corresponding probability value (y), and with the various concentration of various reagents Logarithm lgx be that abscissa using least square method obtains coefficient a, b in virulence equation (y=a+blgx).According to virulence side Journey calculates the LC of the reagent as y=5.000 (the probability value when death rate is 50%)50.It is calculated using Sun Yunpei equation Out confection co-toxicity coefficient (CTC) (bibliography: Tan Genjia, wishing Jianping etc., " fungicide bioassay calculation method and Using ", Anhui agronomy notification, 1998,4(1), 27-28).Using the calculated CTC value of Sun Yunpei equation, China is generally recognized It is greater than 150 with synergistic effect (wherein: CTC, which is greater than 200, has significant synergistic effect) for CTC, CTC is addition 50~150 Effect, CTC are antagonism less than 50.
Five, result and analysis
TDCA-6 and fluacrypyrim composition series proportion mixture are to citrus red mite The Toxicity Determination result, LC50With altogether Malicious coefficient (CTC) is shown in Table 1, table 2.
Laboratory experiment the result shows that, TDCA-6 and fluacrypyrim composition series proportion mixture citrus red mite is not shown Antagonism out, it is most of to have certain synergistic effect (the CTC value of AB5~AB7 is both greater than 150, shows there is synergistic effect), Its CTC value of AB5, AB6 is all larger than 200, shows there is significant synergistic effect.Wherein the co-toxicity coefficient of AB5 mixture it is maximum (CTC= 212), illustrate its synergistic effect maximum.
Table 1, TDCA-6 and fluacrypyrim proportion mixture are to citrus red mite The Toxicity Determination result
2 LC of table50With co-toxicity coefficient (CTC)
The death rate corresponding probit value when y represents composition series proportion mixture various concentration in table 2, x represent concentration (C) Logarithm lgC(, that is, x=lgC).
Embodiment 14: fluacrypyrim TDCA-6 composition for preventing and controlling citrus red mite field efficacy experiment
One, reagent agent
1,20% miticide composition TDCA-6 fluacrypyrim wettable powder (WP) (weight ratio TDCA-6: fluacrypyrim= 10:1) (prepared according to the method for embodiment 4)；
2,20% miticide composition TDCA-6 fluacrypyrim water dispersible granules (WDG) (weight ratio TDCA-6: fluacrypyrim= 5:1) (prepared according to the method for embodiment 2)；
3,10% fluacrypyrim suspoemulsion (being prepared by the method for embodiment 11)；
4,5% TDCA-6 suspoemulsion (SE) (being prepared by the method for embodiment 12).
Two, experimental subjects
1, place: the area Mianyang City Nong Ke, Sichuan Province kwan-yin village Citrus Orchard living is tested；
2, crop: sweet orange is tested；
3, controlling object: citrus red mite.
Three, experimental method
1, processing item: 20% miticide composition TDCA-6 fluacrypyrim wettable powder (WP) dilutes 4000 times；20% Miticide composition TDCA-6 fluacrypyrim water dispersible granules (WDG) dilute 4000 times；10% fluacrypyrim suspoemulsion (SC) dilution 2000 times；5% TDCA-6 suspoemulsion (SE) dilutes 1000 times.Blank control: clear water is used.
2, cell is arranged: each cell tree species, the age of tree, growing way and fertilizer and water management condition are almost the same.Each cell is 3 fixed It sets, four repetitions, totally 24 cell；And cell is arranged according to random area.
3, spraying time and method: primary in citrus red mite peak of occurrence period (May 26) application.Using manual pressure Contracting sprayer even spraying, to squirt blade as degree.
4, control time and method: before the application with 3 days after application, 10 days, 20 days, each investigation in 30 days it is primary.Method is Each tree wins 30 leaves in four orientation at random, and every cell wins 360, records mite quantity living on blade, calculates mite mouthful and subtract Move back rate and preventive effect.
Four, experimental result
20% miticide composition TDCA-6 fluacrypyrim wettable powder (WP) dilutes 4000 times；20% miticide composition TDCA-6 fluacrypyrim water dispersible granules (WDG) dilute 4000 times, and 3 days are respectively 92.69% to citrus red mite preventive effect after application With 91.82%；10 days are respectively 89.97% and 88.01% to citrus red mite preventive effect after application；After application 20 days to the red spider of citrus Spider preventive effect is respectively 81.32% and 80.64%；30 days are respectively 76.63% and 76.17% to citrus red mite preventive effect after application.It is right Dilute 2000 times according to the fluacrypyrim suspoemulsion (SC) of medicament 10%, 3 days after application, 10 days, 20 days, 30 days four times investigation preventive effects divide It Wei 89.09%, 86.20%, 78.25%, 67.73%.5% TDCA-6 suspoemulsion (SE) dilutes 1000 times, 3 days, 10 after application It, 20 days, 30 days four times investigation preventive effects be respectively 84.64%, 79.48%, 73.78%, see Table 3 for details by 64.93%().According to field reality Observation is tested, does not find that TDCA-6 fluacrypyrim miticide composition generates phytotoxicity phenomenon to experiment crop.
3 TDCA-6 of table and fluacrypyrim series proportion mixture are to citrus red mite field experiment result statistical form

Claims (3)

1. miticide composition, with N- (5- tert-butyl -1,3,4- thiadiazoles -2- base)-N'- (2,6- dichloropyridine -4- base)-N, 4- Dimethyl -1,2,3- thiadiazoles -5- carbonamidine and fluacrypyrim are common group of acceptable auxiliary element in effective component, with pesticide At, wherein N- (5- tert-butyl -1,3,4- thiadiazoles -2- base)-N'- (2,6- dichloropyridine -4- base)-N, 4- dimethyl -1,2, 3- thiadiazoles -5- carbonamidine and fluacrypyrim weight ratio are 40:1 to 10:1.
2. miticide composition according to claim 1 is prepared into various forms of by current conventional pesticide production method Available microcapsule formulations, suspoemulsion, water dispersible granules, wettable powder, aqueous emulsion, any dosage form in suspending agent.
3. miticide composition according to claim 1, the harmful mite for fruit tree, vegetables, cotton, peanut and ornamental plant is anti- It controls.
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CN104610250A (en) * 2015-01-09 2015-05-13 西华大学 1,2,3-thiadiazole-5-formamidine compound containing three N-heterocycles and synthesis
CN104860938A (en) * 2015-06-08 2015-08-26 西华大学 Multi-nitrogen heterocycle thiadiazoles-5-formamidine compound by cyclization method
CN104886079A (en) * 2015-05-28 2015-09-09 西华大学 Application of 1,2,3-thiadiazole-5-formamidine heterocyclic compound as acaricide

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104610250A (en) * 2015-01-09 2015-05-13 西华大学 1,2,3-thiadiazole-5-formamidine compound containing three N-heterocycles and synthesis
CN104530040A (en) * 2015-01-19 2015-04-22 西华大学 Novel method for synthesizing 1,2,3-thiadiazole-5-formamidine compound
CN104886079A (en) * 2015-05-28 2015-09-09 西华大学 Application of 1,2,3-thiadiazole-5-formamidine heterocyclic compound as acaricide
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