CN105503829A - Fipronil-pyridine compound and preparation method and application thereof - Google Patents
Fipronil-pyridine compound and preparation method and application thereof Download PDFInfo
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- CN105503829A CN105503829A CN201610004348.7A CN201610004348A CN105503829A CN 105503829 A CN105503829 A CN 105503829A CN 201610004348 A CN201610004348 A CN 201610004348A CN 105503829 A CN105503829 A CN 105503829A
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- SKCNYHLTRZIINA-UHFFFAOYSA-N ClCc(cn1)ccc1Cl Chemical compound ClCc(cn1)ccc1Cl SKCNYHLTRZIINA-UHFFFAOYSA-N 0.000 description 1
- ZOCSXAVNDGMNBV-UHFFFAOYSA-N Nc([n](-c(c(Cl)cc(C(F)(F)F)c1)c1Cl)nc1C#N)c1S(C(F)(F)F)=O Chemical compound Nc([n](-c(c(Cl)cc(C(F)(F)F)c1)c1Cl)nc1C#N)c1S(C(F)(F)F)=O ZOCSXAVNDGMNBV-UHFFFAOYSA-N 0.000 description 1
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
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- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
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Abstract
The invention relates to a novel fipronil-pyridine compound and a preparation method and application thereof. The compound has a structure shown in a general formula (I), X=F or Cl or Br, and more preferably, a compound adopting Cl as X in the formula (I) is adopted as compound. The compound is obtained through a reaction by adopting fipronil and 2-chloro-5-chloromethylpyridine as raw material under the action of an acid-binding agent in solvent. The invention further discloses the preparation method of the compound and the application of the compound in an insecticide aspect.
Description
Technical field
The invention belongs to agricultural pest management field, specifically, ethiprole-pyridine compounds relating to a kind of novelty and preparation method thereof, and the application of described compound in agricultural pest management.
Background technology
China is large agricultural country, and crop diseases and pest crop smothering occurs throughout the year, and its area is approximately 400,000,000 hectares, and need produce and use about 800,000 tons, agricultural chemicals every year, therefore agricultural chemicals has become indispensable key element in agriculture production.But the long-term unreasonable use of chemical pesticide, also brings many drawbacks, as environmental pollution, direct murder by poisoning, the Genes For Plant Tolerance property of medicine etc. to non-target organism.Therefore, research environment compatibility good, safety, low residue, economic novel agrochemical become following development trend.
The exploitation of current fluoro-containing pesticide has become the initiative main body of current novel pesticide, and fluoro-containing pesticide has become present and even the Variety comprehensive of pesticide industry development & application in the future.Ethiprole is that Rhone-Poulenc company registered and the sterilant developed in 1988, and in China, registration commodity are called Frontline, and chemical structure is as shown in following formula (III).Ethiprole, as broad spectrum pesticide, not only can prevent and treat various agricultural and fruit tree pest insect, can also prevent and treat domestic animal and sanitary insect pest.And CCMP, being namely very important heterocyclic pesticide intermediate with following formula (IV) compound, is the key intermediate producing the Pesticidal products such as efficient pesticides UC 62644, Provado and pyrrole worm be clear.
Summary of the invention
Present inventor finds, ethiprole and 2-halo-5-chloromethylpyridine, particularly 2-chloro-5-chlorine Shen yl pyridines is utilized the method for active splicing to be combined by chemosynthesis the compounds that can obtain and have good insecticidal effect.
Therefore one object of the present invention is the ethiprole-pyridine compounds providing a kind of novelty.The chemical structure of described compound is as shown in following general formula (I):
Wherein X is selected from F, Cl or Br.
Particularly preferably be the compound had as shown in the formula (II) structure:
The experiment that present inventor carries out shows, compared with other existing derivatives of ethiprole and ethiprole, and the injurious insect control effect that formula (I) compound tool is significantly improved.
Another object of the present invention is to provide the preparation method of described compound.Such as, the preparation method of formula (II) compound is as follows:
Described method by under the existence of solvent and acid binding agent, with ethiprole and CCMP for raw material reaction carries out.
In above-mentioned preparation method, described solvent is selected from following one or more: DMF, acetonitrile, tetrahydrofuran (THF), toluene, acetone, methylene dichloride, ethylene dichloride or ethyl acetate.Preferred DMF, acetonitrile, tetrahydrofuran (THF), more preferably acetonitrile.
In above-mentioned preparation method, described acid binding agent is selected from following one or more: sodium carbonate, salt of wormwood, potassium hydroxide, sodium hydroxide, sodium bicarbonate, triethylamine and sodium hydride.Preferred potassium hydroxide, sodium hydroxide, sodium hydride, more preferably potassium hydroxide.
In above-mentioned preparation method, the mol ratio of described reactant is CCMP: ethiprole=(1-100): 1, preferably (1-3): 1, more preferably 2: 1.
In above-mentioned preparation method, the temperature of described reaction is-10 DEG C-150 DEG C, preferably 25 DEG C-100 DEG C, more preferably 45 DEG C-70 DEG C.
For the preparation method that X in general formula (I) is the compound of F or Br, can pass easily through and the CCMP in aforesaid method replaced with 2-fluoro-5-chloromethylpyridine or the bromo-5-chloromethylpyridine of 2-and easily prepare.
Another object of the present invention be to provide a kind of injurious insect control composition with and preparation method thereof.Above-mentioned general formula (I) compound (particularly preferably formula (II) compound is done) that described composition comprises injurious insect control significant quantity is activeconstituents, and the content of described general formula (I) compound (particularly formula (II) compound) is preferably in the scope of 0.01%-99.99 % by weight.
In addition, described injurious insect control composition optionally can also be included in carrier conventional in injurious insect control field and auxiliary agent.
Described composition can be made into conventional formulation, such as wettable powder, suspension agent, missible oil, microemulsion, pulvis, aqua, poison bait, female medicine, granule, microcapsule, aqueous emulsion, paste, outstanding newborn enriching agent, the natural materials soaked with compound of the present invention and the synthetic materials etc. soaked with compound of the present invention.
The type of service of described composition depends on specific purposes and the application process of use, and preferably described type of service can guarantee can have meticulous according to compound of the present invention in the environment and distribute uniformly in each case.
The above-mentioned preparation of described composition can be prepared with currently known methods, such as, general formula (I) compound (particularly preferably formula (II) compound) can be mixed with subsidiary material such as solid-filling agent or liquid filling agent.If need emulsifying agent, tensio-active agent, dispersion agent, sanitas, defoamer, wetting agent, the frostproofer that pesticide field can be used conventional, seed treatment agent, one or more in the formulation auxiliary agents such as tinting material, tackiness agent and jelling agent.
Described liquid filling agent can be: one or more in aromatic hydrocarbon and non-aromatic hydrocarbon, alcohol and polyvalent alcohol, ketone, ester, ether, amine, acid amides, lactone, sulfone and sulfoxide etc.
Preferred liquid filling agent is: one or more in toluene, dimethylbenzene, chlorobenzene, acetone and dimethyl sulfoxide (DMSO).
Preferred liquid filling agent is: one or more in dimethylbenzene and dimethyl sulfoxide (DMSO).
Described solid-filling agent can be: one or more in synthetic materials of the silicon-dioxide of kaolin, clay, talcum, diatomite, pulverizing, silicate, Wingdale, pulverizing etc.
Preferred solid-filling agent is: one or more in diatomite, kaolin, talcum powder.
Emulsifying agent can be: one or more in nonionic and anionic emulsifier, polyoxyethylene aliphatic alcohol ether, alkylsulfonate, alkyl-sulphate, arylsulphonate and protein hydrolystate etc.
Preferred emulsifying agent is: dimethyl fumarate, sorbitol anhydride oleate, tween-80, tween 85, agriculture breast 602# in one or more.
Described tensio-active agent can be: one or more in polyoxyethylene nonylphenol, sulfonated lignin, polyoxyethylene polyoxypropylene block copolymer, alkylphenol polyoxyethylene phosphoric acid ester, organosilicon, sucrose glyceride etc.
Preferred tensio-active agent is: one or more in polyoxyethylene nonylphenol, sulfonated lignin.
Described dispersion agent can be: nonionic and/or ionic species, and preferred dispersion agent is: one or more in naphthalene sulfonate formaldehyde, styrene acrylic copolymer (as ATLOX-550s, by standing grain major company of Britain produce) etc.
Described sanitas can be: one or more in dichlorophen and benzyl alcohol hemiformal etc.
Described defoamer can be: one or more in soya-bean oil, Semen Maydis oil, polyoxyethylene oxypropylene glycerine, higher alcohols, phenylethyl alcohol oleic acid ester, Laurate alcohol ester phenylacetate etc.
Preferred defoamer is: one or more in Semen Maydis oil, polyoxyethylene oxypropylene glycerine.
Described wetting agent can be: one or more in Sodium dodecylbenzene sulfonate or sodium butylnaphthalenesulfonate salt etc.
Described frostproofer can be: one or more in glycerine, ethylene glycol or propylene glycol etc.
Described general formula (I) active compound (particularly preferably formula (II) compound) weight percent is in the composition 0.01%-99.99%, is preferably 0.1%-90%.
General formula of the present invention (I) compound (particularly preferably formula (II) compound), and the composition containing it can be mixed with nematocides with various sterilization agent, other sterilants, fertilizer, the part by weight scope of mixing can be 1: 1000-1000: 1, and preferably 1: 200-200: 1.Above-mentioned substance mixing may be produced potential synergy, and object is to obtain insecticidal spectrum, more labour-saving use-pattern widely.Below exemplify possible array configuration, but pesticide species is various, can not enumerates, therefore the present invention is not construed as limiting.
Sterilant: organic (sulfo-) phosphoric acid salt such as phorate, Volaton, monocrotophos, paraoxon, parathion-methyl, SD-1750, Rogor, the carbamate pesticides such as carbofuran, methomyl, Propoxur, the pyrethrins such as Deltamethrin, effective cypermethrin, cyfloxylate, the growth regulating insecticides such as chlorfluazuron, diflubenzuron, flucycloxuron, chlorine worm hydrazides, methoprene, spiral shell mite ester, spiral shell worm ethyl ester, the nicotinic insecticides such as MTI-446, clothianidin, Provado, the macrolide insecticide etc. such as Avrmectin.
Sterilant: M 9834, metaxanin, dodine, tridemorph, triazolone, triadimenol, fluorine bacterium azoles, Wocosin 50TK, thiram, zineb, maneb, anilazine, mebenil, thiabendazole, Bordeaux mixture, venus crystals, Niagara 9044, fludioxonil, sterilizing list, Difolatan, dimethomorph, flumorph, m-tetrachlorophthalodinitrile, ferimzone etc.
Fertilizer: ammonium nitrate, urea, salt of wormwood and superphosphate etc.
Nematocides: halogenated hydrocarbon, isosulfocyanate, organic phosphates, amino formate and compound mushroom etc.
The invention provides a kind of method of Control pests, it is by general formula (I) compound (preferred formula (II) compound), or the composition containing it is applied in insect and/or its living environment.
Another object of the present invention is to provide the application of a kind of described general formula (I) compound (preferred formula (II) compound) in injurious insect control field.
The infringement of compound of the present invention or may be used for protective plant/crop from insect pest containing its composition, especially insect, mite class or spider.Described compound is administered in the seed of described plant/crop, leaf, stem, the soil of root or insect and plant-growth, material or environment, to reach the effect of desinsection by above-mentioned formulation.
The controllable insect of the compounds of this invention is preferably Agricultural pests, comprises the insect of Insecta, Arachnida and nematoda.
Such as, it can be used for control black cutworm, yellow cutworm, prodenia litura, two select the lepidoptera pests such as committee noctuid, greater wax moth, applied perfume, greater wax moth, the new worm of the little food of pears, Atrijuglans hetaohei, fall webworms, tent caterpillar, apple leaf miner, lopper worm, small cabbage moth, mythimna separata, gypsymoth, bollworm, cotton snout moth's larva, swallowtail butterfly.
The coleopteran pests such as buprestid beetle, wireworm, khapra beetle, potato bug, longicorn, beans blister beetle, striped flea-beetle, bean weevil, scarab beetle, weevil.
The Diptera pests such as Mediterranean fruitfly, fruit bat, Aedes aegypti, oranges and tangerines trypetid, lucilia cuprina, housefly, vegetable leafminer, European daddy-longlegs.
The Hymenoptera insects such as termite, Xinjiang cabbage sawfly, red fire ant.
The Thysanoptera such as haplothrips aculeatus, Chinese thrips, cotton thrips.
Nezara viridula smaragdula Fabricius., blackspot cigarette fleahopper, intend the Hemipteran pest such as green stinkbug, cotton toon, tarnished plant bug.
The homoptera pests such as grape phylloxera, sugarcane plant hopper, grain aphid, brevicoryne brassicae, broad bean Empoasca spp.
The orthoptera pests such as Groton bug, mole cricket, Asiatic migrotory locust, periplaneta americana.
Cotton spider mites, panonychus ulmi, Tetranychus urticae, carmine spider mite, etc. arachnoide pest.
The plant nematodes such as root knot nematode, globodera rostochiensis, cereal cyst nematode, soybean cyst nematode, grain nematode.
Compound of the present invention and composition thereof are preferably suitable for controlling insect, more preferably be suitable for controlling Homoptera (Homoptera), acarina (Acarina), lepidopteran (Lepidoptera), Diptera (Diptera), the insect of Thysanoptera (Thysanoptera), Coleoptera (Coleoptera), is extremely preferably suitable for controlling Coleoptera (Coleoptera) insect.Compound of the present invention and composition thereof can be used for the harm of growth from harmful organism of protective plant, can be used for the farm crop in protecting agriculture, gardening and forestry, ornamental plant, medicinal crop or fruit tree.
Suitable target crop comprises: cereal, such as wheat, barley, rye, oat, rice, corn and Chinese sorghum.Oil crops, such as rape, mustard, castor-oil plant, Sunflower Receptacle and coconut.Vegetables, such as Chinese cabbage, naked oats, spinach, romaine lettuce, Caulis et Folium Brassicae capitatae, Radix Dauci Sativae, onion, tomato.Fruit tree, such as apple, pears, peach, walnut, banana.Ornamental plant, such as petunia, Flos Pelargonii, pansy and Flower of Garden Balsam.
In addition, compound of the present invention also may be used for the seed or other the organ/parts for the effect of breeding that process plant.
Compound of the present invention and composition thereof may be used for protecting timber (as trees, sleeper), buildings, furniture, leather, fibre product, electric wire, cable etc. from the harm of termite.
Compound of the present invention and composition thereof can be used for controlling stored grain crop pest as the harm of grain peat, grain weevil, sitophilus zea-mais, mouse etc.
By by target pest, its food supply, habitat, breeding place or its location contact with general formula (I) compound (particularly preferably formula (II) compound) of injurious insect control effective dose can effective Control pests.Its time of application can before or after the on-site plant growth of pestinfestation or results.
Compound of the present invention is preferably applied to the lepidoptera pests such as black cutworm, yellow cutworm, prodenia litura, small cabbage moth, mythimna separata, gypsymoth, bollworm, cotton snout moth's larva; The coleopteran pests such as wireworm, longicorn, beans blister beetle, striped flea-beetle, weevil; The control of the Diptera pests such as fruit bat, oranges and tangerines trypetid, housefly, European daddy-longlegs.
Compound of the present invention is most preferably applied to the control of Phyllotreta striolata.
" injurious insect control effective dose " used herein refers to produce appreciable results to insect the amount of required activeconstituents, described positive effect comprise gangrene, death, deformity, sterile, food refusal, cannot mating etc.The injurious insect control significant quantity of composition is according to changes such as the insecticidal effect of weather, expectation and efficiency time, target species, location, dispenser position, methods of application.Its preferred application dosage is 1.5 grams/acre to 2.5 grams/acre (effective constituent).
Another object of the present invention is to provide a kind of method of protective plant, seed, plant, fruit; described method is by general formula (I) compound (particularly preferably formula (II) compound), or the composition containing it is used in plant, seed, plant, fruit and/or its respective environment.
By the following examples the present invention is further explained.Following examples are only the description of this invention, do not have any restriction to scope of the present invention.
Accompanying drawing explanation
Fig. 1 is the MS detected result of the application's formula (II) compound.
Specific embodiment
Embodiment is prepared by first part
By following chemical reaction preparation formula (II) compound:
In 500ml round-bottomed flask, add 200mL solvent acetonitrile, add ethiprole (30.86mmol successively, 13.5g), acid binding agent potassium hydroxide (46.3mmol, 2.6g) and stir, after ethiprole all dissolves, CCMP is added, be heated to 45 DEG C of insulations, react completely through 5h ethiprole.After the cooling of question response system, add saturated sodium-chloride and divide and extract for 2 times, be separated removing water layer, surplus solution anhydrous magnesium sulfate drying, cross and filter siccative, stirring that filtrate rotary evaporation reclaims 4/5 solvent, residuum adds water, be cooled to room temperature and obtain product.Productive rate is 63%.
Carry out Structural Identification to formula (II) compound, as shown in Figure 1, the display of this result obtains formula (II) compound of object construction to its MS detected result.
LC-MS (GC-MS) data: m/z=561.9499.
Its Structural Identification analytical data is as follows:
The Structural Identification analytical data of table 1 formula (II) compound
Second section example of formulations
A) dispersible agent (DC)
Formula (II) compound: cyclohexanone: dispersion agent (ATLOX-550s)=20: 70: 10 (being parts by weight ratio).Dilute with water can obtain the preparation of formula (II) compound of 20% (w/w).
B) missible oil (EC)
According to formula (II) compound: dimethyl sulfoxide (DMSO): 910B (buying producer: Nanjing Teva-Chem. Co., Ltd.; Emulsifying agent): dimethylbenzene=5: the ratio mixing of 31: 13: 51 (being parts by weight ratio), can obtain 5% (w/w) cream preparation.
C) emulsion (EW, EO, ES)
Formula (II) compound: dimethylbenzene: calcium dodecylbenzene sulphonate: ethoxylated castor oil=25%: 35%: 5%: 5% (being weight percent content).By emulsification machinery this mixture joined in 30 % by weight water and make uniform emulsion, the preparation of formula (II) compound of 25% (w/w) can be obtained.
D) suspension (SC, OD, FS)
In ball milling, formula (II) compound is pulverized, and in following ratio it is mixed with other materials and disperse:
Formula (II) compound: dispersion agent (for ATLOX-550s): wetting agent (for Sodium dodecylbenzene sulfonate): water and/or organic solvent=20: 5: 5: 70.The preparation of formula (II) compound of 20% (w/w) can be obtained.
E) water dispersible granule and water-soluble granular formulation (WG, SG)
Prepared by the ordinary method preparing WG, SG by technology machinery (forcing machine, spray tower or fluidized-bed) with the dispersion agent (for ATLOX-550s) of identical weight, wetting agent (for Sodium dodecylbenzene sulfonate) after fine grinding formula (II) compound, the preparation of 50% (w/w) formula (II) compound can be obtained.
F) water-dispersible powder and water-soluble powder (WP, SP, SS, WS)
Abrading type (II) compound in rotor-stator mill, add the dispersion agent (for ATLOX-550s) of formula (II) compound by weight 1/3 weight, wetting agent (for Sodium dodecylbenzene sulfonate) and silica gel, namely obtain the preparation of formula (II) compound of 75% (w/w).
G) gel preparation (GF)
Formula (II) compound is pulverized in ball milling, then adds other materials in following ratio.
Formula (II) compound: dispersion agent (for ATLOX-550s): jelling agent (for Vltra tears): water/organic solvent=20: 10: 1: 70.The preparation of formula (II) compound of 20% (w/w) can be obtained.
H) pulvis (DP, DS)
Formula (II) compound: pulverizing kaolin=5: 95, after mixing the preparation of formula (II) compound of 5% (w/w).
Part III biological activity test example part
1. field activity experiment
(1) reagent is adopted:
Formula (II) compound 5% missible oil: self-control, its preparation method is shown in preparation formula EXAMPLEPART, example B).
48% chlorpyrifos ec, 2.5% deltamethrin milk oil, 5% ethiprole suspension agent and 80% DDT EC are commercially available prod.
(2) experimentation:
To the biological activity test of Phyllotreta striolata (adult, system/activity of ingesting, preventative)
5% missible oil of formula (II) compound, 48% chlorpyrifos ec, 2.5% deltamethrin milk oil, 5% ethiprole suspension agent and 80% DDT EC has been selected to carry out blade spraying in the field examination worm high-incidence season respectively.
Table 2 field test prevents and treats result (1)
Learnt when usage quantity is 30-50 gram/acre by upper table, check preventive effect after the medicine of the compounds of this invention all higher than other medicaments.Particularly after the tenth day preventive effect still up to 83.56-86.26%, apparently higher than other medicaments, particularly higher than its derived from ethiprole reach 7%, this is very significant in desinsection field.The compounds of this invention has excellent high efficiency and long-lasting as can be seen here.
2. compound structure-activity relationships comparative experiments
The chlorine substituent raising to insecticidal activity of present inventor in the structure-activity correlation Journal of Sex Research of the compounds of this invention in discoverable type (II) compound on pyridine ring is even more important, formula (II) is compared with substituent comparative compound (V) not chloride on pyridine ring, and its insecticidal activity has the raising of highly significant.
(1) reagent is adopted:
Formula (II) compound 5% missible oil: self-control, its preparation method is shown in preparation formula EXAMPLEPART, example B).
5% missible oil of comparative compound (V): comparative compound (V), its structural formula is as follows, synthesize voluntarily, and according to comparative compound (V): dimethyl sulfoxide (DMSO): 910B: dimethylbenzene=5: the weight fraction ratio mixing of 31: 13: 51,5% (w/w) cream preparation of obtained comparative compound (V).
(2) experimentation:
To the biological activity test of Phyllotreta striolata (adult, system/activity of ingesting, preventative).
5% missible oil of 5% missible oil of formula (II) compound, comparative compound (V) has been selected to carry out blade spraying in the field examination worm high-incidence season respectively.
Table 3 field test prevents and treats result (2)
By comparing discovery, insecticidal activity comparatively formula (V) the comparative compound raising nearly 7% of formula (II) compound, this is very significant in desinsection field, can greatly reduce Utilization of pesticides amount, save cost.
Part IV honeybee acute oral toxicity test example part
(1) Italy is selected to grow up worker bee (ApismelliferaL.) for biological for examination according to GB/T31270.10-2014.Raise in this laboratory purchased from Ju Feng garden, Baoding apiculture company limited for examination honeybee on May 20th, 2015.That collects same king bee colony in the morning supplies the adult worker bee of examination Italy, selects health, honeybee of the same size, tests, hungry 2h on pretreatment after adapting to 24h in laboratory conditions.Temperature is 24 DEG C ~ 26 DEG C, and relative humidity 50% ~ 70%, carries out under low light condition.
According to preliminary result, 2,1.11,0.617,0.343,0.191,0.106,0.059 μ ga.i./honeybee, 7 dosage groups (common ratio is 1.8) are set, and establish blank group (CK1) and 0.025% acetone control group (CK2).Treatment group and control group all establish 3 repetitions, each repetition 10 honeybees.Honeybee in storage honeybee cage is introduced in test cage, then in centrifuge tube feeder, add 200 μ L contain 50% aqueous sucrose solution (W/V) of different concns for examination thing, once liquid runs out of (usually needing 3h ~ 4h), foodstuff container is taken out, uses instead and do not carry out feed (quantity-unlimiting) containing the sucrose water for examination thing.For some for examination thing, under higher test dose, the feed of honeybee refusal, thus cause food consumption seldom or almost not consume, extend to 6h at most, and the consumption of food is measured (namely measuring the volume or weight that the food of this process is remaining).Control group and each treatment group all establish 3 repetitions.Toxicity symptom after observed and recorded process 24h and death toll.When control group mortality ratio lower than 10%, if the mortality difference after process 24h is when reaching more than 10%, also need extend observing time.
Under experiment condition, respectively at 24h and 48h observations after experiment, record toxicity symptom and death toll.The death standard of honeybee adopts the honeybee in this laboratory acute (per os) toxicity test (SOP numbering: AUH-SOP-A-002-01) bee death standard is investigated.The death standard of honeybee is: (1) is complete motionless without any reaction; (2) although can be movable, lose the ability of circling in the air, can not creep, touch to external world and react insensitive.
Experiment finds, mensuration liquid generally can take food at about 3h by each treatment group honeybee; Mortality difference after each process 24h is below 10%.
Table 4 compound (II) is to the acute oral toxicity experimental data of honeybee
Table 5 compound (II) is to honeybee acute oral toxicity experimental result
(2) according to above-mentioned experimental procedure, control compounds (V) acute oral is tested, the experimental result of experimental result and compound (II) and the Query Result (data query of ethiprole; Literature reference: grey great waves, Wu Changxing, Wang Xinquan, Wu Sheng dares, and Yu Ruixian, Chen Liping (2008) ethiprole and Trichlorphon are to the joint toxicity evaluation of apis mellifera. Zhejiang Agriculture science, 4,473-475.) compare, it the results are shown in following table 6.
The comparison of table 6 pair honeybee acute oral toxicity
Above experimental result shows, the application's formula (II) compound is lower by 8.82% than formula (V) compound to the Oral toxicity of honeybee lower than ethiprole 45.8%, and the security of visible the application's formula (II) compound to environmental organisms such as honeybees improve greatly.
(3) Italy is selected to grow up worker bee (ApismelliferaL.) for biological for examination according to GB/T31270.10-2014.Raise in this laboratory purchased from Ju Feng garden, Baoding apiculture company limited for examination honeybee on May 20th, 2015.That collects same king bee colony in the morning supplies the adult worker bee of examination Italy, selects health, honeybee of the same size, tests, hungry 2h on pretreatment after adapting to 24h in laboratory conditions.Temperature is 24 DEG C ~ 26 DEG C, and relative humidity 50% ~ 70%, carries out under low light condition.
According to preliminary result, 0.1,0.0555,0.03085,0.01715,0.00955,0.0053,0.00295 μ ga.i./honeybee, 7 dosage groups (common ratio is 1.8) are set, and establish blank group (CK
1) and 0.025% acetone control group (CK
2).Treatment group and control group all establish 3 repetitions, each repetition 10 honeybees.
Pipette experiment drop experiment mesonotum place of honeybee after anesthesia, every honeybee drop 2 μ L, obtains the process of each test dose noted earlier.After each process honeybee is slightly dried, loaded in honeybee cage in time before honeybee recovers completely, soak appropriate syrup with absorbent cotton and feed.
Under experiment condition, respectively at 24h and 48h observations after experiment, record toxicity symptom and death toll.The death standard of honeybee adopts honeybee Acute exposure toxicity test (the SOP numbering: AUH-SOP-A-002-01) bee death standard is investigated in this laboratory.The death standard of honeybee is: (1) is complete motionless without any reaction; (2) although can be movable, lose the ability of circling in the air, can not creep, touch to external world and react insensitive.
According to above experimental procedure, compound (II), control compounds (V) acute toxicity are tested, experimental result and ethiprole (data query; Literature reference: grey great waves, Wu Changxing, Wang Xin congruence ethiprole and Trichlorphon are to the joint toxicity evaluation (J) of apis mellifera. Zhejiang Agriculture science, 2008, (4): 473-475.2008.04.035) be listed as follows.
Table 7 pair honeybee Acute exposure toxicity test result
Above experimental result shows, the application's formula (II) compound is lower by 6% than formula (V) compound to the contact toxicity of honeybee lower than ethiprole 66.4%, and the security of visible the application's formula (II) compound to environmental organisms such as honeybees improve greatly.
In addition, found by field activity experiment, under equal prevention effect, the dosage fewer than ethiprole nearly 2/5 of compound (II), this is that therefore when field medication, compound (II) harm to environmental organisms such as honeybees will greatly reduce than ethiprole because the insecticidal activity of compound (II) is higher than ethiprole.In addition, also find in the activity experiment of field, compound (II) is compared with comparative compound (V), and it improves nearly 7% to choosing test organism insecticidal activity.
Therefore present invention finds a kind of to pest controlling activities the high and non-target organism toxicity such as (such as honeybee environmental organism) is reduced greatly agricultural chemical compound.
Above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (10)
1. ethiprole-pyridine compounds, is characterized in that, has the chemical structure shown in following general formula (I):
Wherein, X is fluorine, chlorine or bromine.
2. a compound according to claim 1, is characterized in that, has with the chemical structure shown in following formula (II):
3. a preparation method for compound as claimed in claim 2, is characterized in that, under the existence of solvent and acid binding agent, is obtained by reacting target product by ethiprole and CCMP.
4. the preparation method of compound according to claim 3, is characterized in that, described solvent is selected from following one or more: DMF, acetonitrile, tetrahydrofuran (THF), toluene, acetone, methylene dichloride, ethylene dichloride or ethyl acetate; Described acid binding agent is selected from following one or more: sodium carbonate, salt of wormwood, potassium hydroxide, sodium hydroxide, sodium bicarbonate, triethylamine or sodium hydride.
5. the preparation method of the compound according to any one of claim 3 or 4, it is characterized in that the mol ratio of reaction raw materials is CCMP: ethiprole=(1-100): 1, temperature of reaction is-10 DEG C-150 DEG C.
6. a pesticide composition, is characterized in that, containing the compound described in claim 1 or 2 and its content in the scope of 0.01%-99.99 % by weight.
7. a method for protective plant, seed, plant, fruit, is characterized in that, is used in plant, seed, plant, fruit and/or its respective environment by the compound described in claim 1 or 2 or containing its composition.
8. a method for Control pests, is characterized in that, the compound described in claim 1 or 2 or the composition containing it is applied in insect and/or its living environment.
9. the method for Control pests according to claim 8, is characterized in that, described insect is Agricultural pests.
10. the method for Control pests according to claim 9, is characterized in that, described Agricultural pests are Phyllotreta striolata.
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| US6335357B1 (en) * | 1997-04-07 | 2002-01-01 | Mitsubishi Chemical Corporation | Pyrazole derivatives, process for preparing the same, intermediates, and pest control agent containing the same as active ingredient |
| CN1329600A (en) * | 1998-12-11 | 2002-01-02 | 阿方蒂农科股份有限公司 | Method for control of arthropods in animals |
| CN1160349C (en) * | 1999-06-29 | 2004-08-04 | 日本农药株式会社 | Pyrazole derivatives and processes for producing the same, and pesticides containing the same as the active ingredient |
| WO2006000313A1 (en) * | 2004-06-26 | 2006-01-05 | Merial Ltd. | N-phenylpyrazole derivatives as pesticides |
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2016
- 2016-01-07 CN CN201610004348.7A patent/CN105503829A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6335357B1 (en) * | 1997-04-07 | 2002-01-01 | Mitsubishi Chemical Corporation | Pyrazole derivatives, process for preparing the same, intermediates, and pest control agent containing the same as active ingredient |
| CN1329600A (en) * | 1998-12-11 | 2002-01-02 | 阿方蒂农科股份有限公司 | Method for control of arthropods in animals |
| CN1160349C (en) * | 1999-06-29 | 2004-08-04 | 日本农药株式会社 | Pyrazole derivatives and processes for producing the same, and pesticides containing the same as the active ingredient |
| WO2006000313A1 (en) * | 2004-06-26 | 2006-01-05 | Merial Ltd. | N-phenylpyrazole derivatives as pesticides |
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