CN1245397A - Insecticidal compositions and methods - Google Patents

Insecticidal compositions and methods Download PDF

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CN1245397A
CN1245397A CN97181510A CN97181510A CN1245397A CN 1245397 A CN1245397 A CN 1245397A CN 97181510 A CN97181510 A CN 97181510A CN 97181510 A CN97181510 A CN 97181510A CN 1245397 A CN1245397 A CN 1245397A
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alkenyl
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M·S·克拉夫
F·G·P·厄尔利
S·J·敦巴
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Syngenta Ltd
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Zeneca Ltd
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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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

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Abstract

An insecticidal composition comprising a first insecticidally active ingredient, to which insect pests have developed a degree of resistance, an insecticidally inert carrier or diluent and, optionally, one or more surface active agents, characterised in boosting the activity of the composition to overcome the resistance of the insect pests, the composition further contains a sufficient amount of a compound of formula (I), wherein A represents a bidentate group of formula -CH2CH2- or CH=CH; Ar is phenyl, pyridinyl, pyridazinyl or pyrazinyl, all being optionally substituted with halogen, C1-4 alkyl, C1-4 alkoxy, C2-4 alkenyl, C2-4 alkynyl or cyano; R is hydrogen, C1-4 alkyl (optionally substituted with cyano, CO2(C1-4 alkyl) or phenyl (itself optionally substituted with halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl or C1-4 haloalkoxy)), C2-4 haloalkyl (the alpha -carbon being unsubstituted), C3-4 alkenyl or C3-4 alkynyl; provided that when R is alkenyl or alkynyl said group does not have an unsaturated carbon atom bonding directly to the ring nitrogen of formula (I); or an acid addition salt, quaternary ammonium salt or N-oxide derived therefrom; and a method of using such a composition to combat insect pests.

Description

Pesticidal combination and method
The present invention relates to be used to prevent and treat the Pesticidal combination of resistant insect and with the method for this composition for preventing and controlling resistant insect.
The invention provides a kind of Pesticidal combination, it contains insect has produced resistance to a certain degree to it first insecticidal active ingredient, the carrier of no insecticidal activity or thinner, with optional a kind or kinds of surface activating agent, it is characterized in that in order to improve composition, in composition, also contain a kind of general formula (I) compound of q.s in the activity that overcomes on the pest resistance: Wherein A represents general formula-CH 2CH 2-or the group of CH=CH; Ar is phenyl, pyridine radicals, pyridazinyl or pyrazinyl, all available halogen of all these groups (particularly fluorine, chlorine or bromine), C 1-4Alkyl (particularly methyl), C 1-4Alkoxyl (particularly methoxyl group), C 2-4Alkenyl, C 2-4Alkynyl group or cyano group are selected arbitrarily to replace; R is a hydrogen, C 1-4Alkyl (is used cyano group, CO 2(C 1-4Alkyl) or phenyl (itself can be used halogen, C 1-4Alkyl, C 1-4Alkoxyl, C 1-4Alkylhalide group or C 1-4The halogen alkoxyl is selected arbitrarily to replace) select arbitrarily to replace), C 2-4Alkylhalide group (α-carbon is not substituted), C 3-4Alkenyl or C 3-4Alkynyl group; Condition is when R is alkenyl or alkynyl group, said group not with the ring of general formula (I) in the unsaturated carbon atom that directly links to each other of nitrogen; Or the addition salts of the acid of deriving thus, quaternary ammonium salt or N-oxide.Preferred first insecticidal active ingredient: the ratio of general formula (1) compound is in the scope of 1: 100～100: 1 (for example 1: 10～10: 1) w/w.
Because each group can be on the outer or interior relative position, so general formula (I) can exist with the form more than a kind of isomer, present invention includes outer and inner form, and the mixture of all proportions and by along and any other isomer of producing of anti-replacement form or chiral centre.
Halogen comprises fluorine, chlorine, bromine and iodine.
Moieties can be the form of straight or branched, methyl for example, and ethyl, just or isopropyl, or just, different, the second month in a season or the tert-butyl group.
Alkylhalide group is fluoroalkyl (trifluoromethyl for example, 2,2,2-trifluoroethyl or 2,2-two fluoro ethyls) or chlorine alkyl particularly.For R, alkylhalide group is for example 2,2,2-trifluoroethyl or 2,2-two fluoro ethyls.
Alkenyl or alkynyl group can be the forms of straight or branched, and in suitable place, alkenyl part may be (E)-or (Z) configuration.For example vinyl, pi-allyl or propargyl.
Suitable acid-addition salts comprises and inorganic acid hydrochloric acid for example, hydrobromic acid, sulfuric acid, nitric acid and phosphoric acid, or organic acid oxalic acid for example, citric acid, lactic acid, butyric acid, toluic acid, caproic acid and phthalic acid, or sulfonic acid pyrovinic acid for example, the addition salts of benzene sulfonic acid and toluenesulfonic acid.The example of other organic carboxyl acid comprises halogenated acid, for example trifluoroacetic acid.
One special aspect, the invention provides a kind of new Pesticidal combination, it contains a kind of insect and it is produced the insecticidal active ingredient of resistance to a certain degree and the inert diluent of no insecticidal activity, and optional one or more surfactants, it is characterized in that said composition contains general formula (Ia) compound of q.s in order to improve the activity that composition overcomes pest resistance:
Figure A9718151000061
Wherein X represents hydrogen or halogen, chlorine or bromine more especially, and R represents the low alkyl group or the rudimentary alkylhalide group of 4 carbon atoms of as many as, or benzyl or halogen benzyl.
On the other hand, the invention provides the compound of general formula (I), wherein Ar selects the pyridin-3-yl that replaces arbitrarily at 5 with chlorine or bromine.
On the other hand, the invention provides a kind of method of improving the activity of a kind of insecticide when control produces the insect of certain resistance to it, this method comprises that the Pesticidal combination that will contain the insecticide relevant with general formula (I) is applied to the place of pest or pest.
Insect may produce resistance to it, and the compositions and methods of the invention comprise the insecticide example that uses as follows:
Pyrethroid: cyhalothrin, time, decis, sumicidin, esfenvalerate, cyfluthrin, β-cyfloxylate, ether chrysanthemum ester, another example is a tefluthrin.
Organophosphorus compounds: chlopyrifos, Profenofos, orthene, Rogor, parathion-methyl, Terbufos, nuvacron, second Toyodan, Toyodan.
Carbamates: tears go out, carbofuran, carbaryl, Methomyl, Osbac, Aphox.
Benzoyl area kind: TH-6040, UC 62644, Teflubenzuron, fluorine bell urea, flufenoxuron, the fluorine third oxygen urea, flucycloxuron.
Other: amitraz, four mite piperazines, azoles mite ester, Hexythiazox, propargite, tebufenpyrad, fenazaquin, pyridaben, SPINOSYN 105, triaguron, Buprofezin, Olivomitecidin, sharp strength spy, the luxuriant ether of Difenamide ， Evil, Imidacloprid, another example are that fluorine azoles worm is clear.
Owing to the insect of more difficult control that one or more above-mentioned insecticides generation resistances are become is as follows:
Homoptera: aphid (as black peach aphid, Myzus nicotiana ' e; Beans winged euonymus aphid, cotten aphid, rhopalosiphum padi, sandlwood potato aphid, potato aphid).
Aleyrodid (for example cassava aleyrodid, sweet potato whitefly, greenhouse whitefly).
Leafhopper (for example rice leafhopper, brown planthopper).
Semiptera (for example U.S. herbage educates stinkbug, and the beanpod grass is educated stinkbug)
Lepidoptera (diamond-back moth for example, tobacco budworm, greedy noctuid, apple skin steinernema)
Diptera (for example clover liriomyza bryoniae)
Coleoptera (for example the horseradish ape is chrysomelid, and cotton boll resembles)
The present invention also provides a kind of SPINOSYN 105 and general formula (I) compound compositions of containing:
Figure A9718151000071
Wherein A represents general formula-CH 2CH 2-group; Ar is phenyl, pyridine radicals, pyridazinyl or pyrazinyl, all available halogen of all groups (particularly fluorine, chlorine or bromine), C 1-4Alkyl (particularly methyl), C 1-4Alkoxyl (particularly methoxyl group), C 2-4Alkenyl, C 2-4Alkynyl group or cyano group are selected arbitrarily to replace; R is a hydrogen, C 1-4Alkyl (is used cyano group, CO 2(C 1-4Alkyl) or phenyl (itself can be used halogen, C 1-4Alkyl, C 1-4Alkoxyl, C 1-4Alkylhalide group or C 1-4The halogen alkoxyl is selected arbitrarily to replace) select arbitrarily to replace), C 2-4Alkylhalide group (its α-carbon is not substituted), C 3-4Alkenyl or C 3-4Alkynyl group; Condition is when R is alkenyl or alkynyl group, and said group does not have the unsaturated carbon atom that nitrogen directly links to each other in the ring with general formula (I); Or the acid-addition salts of deriving thus, quaternary ammonium salt or N-oxide.Preferred SPINOSYN 105: the ratio of general formula (I) compound is within the scope of 1: 100～100: 1 (for example 1: 10～10: 1) w/w.(SPINOSYN 105 is seen, for example the summary of research of EP 0375316 or 1997 Beltwide cotton pests and control meeting collection p.1082-1086).
On the other hand, the invention provides a kind of insect of eliminating and preventing and treating at the three unities, the method of evil mite and nematode, it comprises that A represents general formula-CH in the general formula (I) with the compositions-treated pest of the effective dose that contains SPINOSYN 105 and general formula (I) compound or the place of pest 2-CH 2-group; Ar is phenyl, pyridine radicals, pyridazinyl or pyrazinyl, all available halogen of all these groups (particularly fluorine, chlorine or bromine), C 1-4Alkyl (particularly methyl), C 1-4Alkoxyl (particularly methoxyl group), C 2-4Alkenyl, C 2-4Alkynyl group or cyano group are selected arbitrarily to replace; R is a hydrogen, C 1-4Alkyl (is used cyano group, CO 2(C 1-4Alkyl) or phenyl (itself can be used halogen, C 1-4Alkyl, C 1-4Alkoxyl, C 1-4Alkylhalide group or C 1-4The halogen alkoxyl is selected arbitrarily to replace) select arbitrarily to replace), C 2-4Alkylhalide group (its α-carbon is not substituted), C 3-4Alkenyl or C 3-4Alkynyl group; Condition is when R is alkenyl or alkynyl group, said group not with the ring of general formula (I) in the unsaturated carbon atom that directly links to each other of nitrogen; Or the acid-addition salts of deriving thus, quaternary ammonium salt or N-oxide.Insect, mite or nematode comprise for example Lepidoptera of insect, diptera, and Homoptera and coleoptera (comprising the chrysomelid genus of bar, i.e. northern corn root-worm), and agricultural (this speech comprises as food and fiber product growing crop); Gardening and livestock breeding, forestry, the product of plant resource, as fruit, the relevant insect of storage of cereal and timber, and the insect relevant with the transmission of animal with the mankind.The example of insect and evil mite comprises: black peach aphid, cotten aphid, beans winged euonymus aphid, Aedes aegypti, Anopheles, Culex, band line red cotton bug, housefly, Pieris brassicae, diamond-back moth, the horseradish ape is chrysomelid, kidney circle matter a red-spotted lizard belongs to Aleyrodes, sweet potato whitefly, Groton bug, American cockroach, oriental cockroach, Spodoptera littoralis, tobacco budworm, bromine continent epidemic disease locust, the chrysomelid genus of bar, Agrotis, spot dogstail snout moth's larva, brown planthopper, rice leafhopper, panonychus ulmi, citrus red mite (crm), Tetranychus urticae, Wei Shi tetranychid (Tetranychus ni) Tetranychus cinnabarinus, the tangerine rust mite, Polyphagotarsonemus latus Banks, short whisker Acarapis.
Preferred general formula (I) compound is general formula (Ia) compound in composition of the present invention, wherein X is a chlorine or bromine, R is 2,2-two fluoro ethyls or 2,2, the 2-trifluoroethyl, comprise, for example 3-(5-chloropyridine-3-yl)-3-cyano group-8-(2,2, the 2-trifluoroethyl)-8-azabicyclo [3.2.1] octane (compd A) and 3-(5-chloropyridine-3-yl)-3-cyano group-8-(2,2-two fluoro ethyls)-8-azabicyclo [3.2.1] octane (compd B).
Preferred general formula (I) compound is 3-(5-chloropyridine-3-yl)-3-cyano group-8-azabicyclo [3.2.1] octane (Compound C) in composition of the present invention.
General formula (I) compound can be by adopting the method (for example J.Med.Chem. (1975) 18 (5) 496-501) described in the document, by adopting one or more synthetic technologys described below, or by preparing in conjunction with literature method and these methods that describe below.In all describe below, R 5All be alkyl or phenyl alkyl (particularly benzyl).
General formula (I) compound can be chosen in suitable alkali arbitrarily, and for example potash exists down, and by handling the compound of general formula (II) compound and general formula R L, wherein to be suitable leaving group prepare because of for example halide or triflate L.
General formula (II) compound (being that R is general formula (I) compound of hydrogen) can prepare by general formula (III) compound deprotection, for example they are handled with chloro-formate (for example chloro-carbonic acid vinyl acetate), make formed carbamate carry out acidic hydrolysis (for example using hydrochloric acid) again by (i); Or (ii) under the situation of suitable rising temperature, they are handled with azodicarboxylate (for example diethylazodicarboxylate).
General formula (I) compound is (for example in the presence of alkali and alkaline metal iodide) under suitable condition, in appropriate solvent (for example N, dinethylformamide), is made by general formula (III) compound and compound R Hal (wherein Hal is a halogen) reaction.
In addition, general formula (I) compound can be from general formula (II), at suitable reductant for example in the presence of the formic acid, by with aldehyde (R 6CHO; R herein 6CH 2=R) reduction amination prepares.
General formula (III) compound can be by at first using suitable alkali, for example diisopropyl lithamide (LDA) or two (trimethyl silyl) lithamide are handled general formula (IV) compound, then formed product and compd A rHal (Hal is a halogen herein) reaction are made.
In addition, general formula (I) compound can be by handling general formula (VI) compound and suitable alkali, for example diisopropyl lithamide (LDA) or two (trimethyl silyl) lithamide make formed product and compd A rHal (Hal is a halogen) reaction herein then.
General formula (VI) compound can be in the presence of the compound of general formula R Hal (Hal is a halogen herein), and by handling general formula (VII) compound and suitable alkali, for example potash prepares.
In addition, general formula (VI) compound can be at suitable alkali, and for example potassium ethoxide exists down, makes by handling general formula (VIII) compound and tosyl methylisothiocyanate ester.
General formula (VIII) compound can be by being similar to the synthetic technology of Robinson, Robert tropinone, for example from 2-ethyoxyl-3, the 4-dihydropyran prepare (see, for example, organic synthesis (Collective Volume 4), p.816).
General formula (I) compound, wherein A is CH=CH, can be by in appropriate solvent (for example dimethylbenzene), under the suitable temperature (for example refluxing), heating general formula (I) compound, wherein A is CH 2CH Z(wherein Z is suitable group, for example thionic-4-toloxyl) makes.
General formula (I) compound, wherein A is CH 2CHZ (wherein Z is suitable group, for example thionic-4-toloxyl) can exist down at suitable alkali (for example N, N-dimethyl amine yl pyridines), and by handling general formula (I) compound, wherein A is CH 2CH (OH) prepares with suitable chloro-formate (for example 4-tolyl chloride thionic formic acid esters).
General formula (I) compound, wherein A is CH 2CH (OH) can pass through general formula (I) compound, and wherein A is CH 2CH (OZ '), Z ' are that the acidic hydrolysis of hydrolyzable groups (for example t-butyldimethylsilyl) prepares.
General formula (I) compound, wherein A is CH 2CH (OZ '), Z ' is that hydrogen or hydrolyzable groups (for example t-butyldimethylsilyl) can pass through corresponding general formula (VI) compound and suitable alkali, for example diisopropyl lithamide (LDA) or two (trimethyl silyl) lithamide reaction makes formed product and compd A rHal (Hal is a halogen) reaction herein then.
General formula (VI) compound, wherein A is CH 2CH (OZ '); Z ' is that hydrogen or hydrolyzable groups (for example t-butyldimethylsilyl) can prepare by handling corresponding general formula (V) compound and tosyl isothiocyanates (being known as (4-tosyl) methylisothiocyanate ester) in the presence of suitable alkali (for example potassium tert-butoxide).
General formula (V) compound, wherein A is CH 2CH (OZ '), Z ' are that hydrolyzable groups (for example t-butyldimethylsilyl) can be by handling general formula (V) compound, and wherein A is CH 2CH (OH) and compound Z ' L, wherein L is a leaving group, prepares
In addition, general formula (I) compound, wherein A is CH=CH, can adopt suitable dehydrating agent, and for example the dimethylamino sulfur trifluoride makes general formula (I) compound, and wherein A is CH 2-CH (OH), dehydration makes.
General formula (I) compound, wherein A is CH=CH, can pass through general formula (I) compound, wherein A is CH 2CH (OZ '), Z ' are suitable group (SO for example 2CH 3), (for example 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene reaction makes with suitable amine.
General formula (I) compound, wherein A is CH 2CH (OZ '), Z ' are suitable group (SO for example 2CH 3) can pass through general formula (I) compound, wherein A is CH 2CH (OH) makes with the reaction of suitable acid chloride (for example mesyl chloride).
The amount of the present composition of using for pest control is an active ingredient, generally from 0.01-10kg/ha, and preferred 0.1～6kg/ha.
Composition of the present invention is with pulvis, wetting powder, granule (slowly or rapid release), emulsification or suspension concentrating agents, solution, emulsion, coating agent for seed, the composition of cigarette/mist agent or sustained release, for example microcapsule granule or suspending agent form are applied to soil, plant or seed, the place of pest, or the habitat of pest.
Pulvis is by mixing active ingredient and thin solid carrier and/or the thinner of one or more powder, natural clay for example, kaolin, pyrophyllite, bentonite, aluminium oxide, montmorillonite, diatomite, chalk, calcium phosphate, calcium carbonate and magnesium carbonate, sulphur, lime, flour, talcum and other organic and inorganic solid carrier process.
Granule can be by active component being adsorbed on porous granule materials float stone for example, atlapulgite, Emathlite, diatomite, on the levigate corncob, or the material that is adsorbed on hard core sand for example, silicate, carbonate, sulphate prepares on the phosphate.Generally be used for auxiliary infiltration, the reagent of bonding or coated solid carrier comprises the petroleum solvent of fat and fragrance, alcohol, polyvinyl acetate, polyvinyl alcohol, aldehyde, ketone, ester, dextrin, sugar and rape oil, and active ingredient.Other additive also can comprise emulsifier, wetting agent or dispersant.
The formulation of microcapsule formulations (micro-capsule suspension CS) or other sustained release also can be used, and is used in particular for slowly discharging over a period to come and seed treatment.
In addition, composition of the present invention can be to be used for soaking, and irrigates the liquid preparation that adds or spray, and they generally are at one or more known wetting agents, the aqueous dispersions or the aqueous emulsion of the active ingredient under dispersant or emulsifier (surfactant) exist.The composition that is used with aqueous dispersions or aqueous emulsion form generally is to provide with the active ingredient that contains high-load or the concentrated milk oil (EC) of plurality of active ingredients or the form of suspension concentrates (SC).EC is a kind of fluid composition of homogeneous phase, contains the active ingredient that is dissolved in nonvolatile substantially organic solvent usually.SC is the dispersion liquid of the fine particle of solid active ingredient in water.In use, these dense preparations of first dilute with water, again by spray application in processed area.
The suitable liquid flux of concentrated milk oil comprises methyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, dimethylbenzene, toluene, chlorobenzene, paraffin, kerosene, white oil, alcohol (for example butanols), methyl naphthalene, trimethylbenzene, trichloro-ethylene, N-N-methyl-2-2-pyrrolidone N-and oxolane alcohol (THFA).
Wetting agent, dispersant and emulsifier can be cations, anion or nonionic, suitable cationic agent comprises for example quaternary ammonium compound such as softex kw.Suitable anionic agent comprises for example soap, sulfuric acid list fatty ester salt, as lauryl sodium sulfate, the salt of the aryl compound of sulfonation, neopelex for example, sodium lignin sulfonate, calcium lignosulfonate or ammonium lignosulphonate, or sulfonic acid dibutyl naphthalene and diisopropyl and triisopropyl sodium naphthalene sulfonate mixture.Suitable non-ionic agent for example comprises oxirane and fatty alcohol for example oleyl alcohol or hexadecanol, with alkyl phenol octyl phenol for example, the condensation product of nonyl phenol and octyl cresol.Other nonionics is the partial ester of deriving from long-chain fatty acid and hexitan, the condensed products of said partial ester and oxirane, and lecithin.
Usually require these dense preparation ability long term storage, and after this storage, still can form and in the enough time, to keep homogeneous phase by dilute with water, so that the water formulation of using with conventional sprayer.These dense preparations can contain the total amount of each active ingredient of 10-85% (weight meter).When being diluted to water formulation, these preparations can contain the active ingredient of different amounts according to their application target.
Composition of the present invention can be pulvis (dry seeds inorganic agent DS or water-dispersible powder WS) or the liquor (dense flowable FS, liquid seeds inorganic agent LS, or micro-capsule suspension CS) that is used for seed treatment.
In use, composition of the present invention can pass through any known applying pesticides method for compositions, for example dusts, spraying, or the mixing of granule are applied to insect, the place of pest, the habitat of pest, or by pest invade and harass just on growing plants.
Composition of the present invention in appropriate circumstances can for example insecticide or synergist mix mutually with one or more other active ingredients.Other the suitable active ingredient that is included in the composition of the present invention can be the activity profile that can enlarge the present composition, or can increase the compound of their lasting effect in the area of pest.They can increase the activity of general formula (I) compound, maybe can replenish active by increasing speed of action or overcoming antagonism.Included other special active ingredient depends on the purposes of mixture and the type of required supplementary function.The example of suitable insecticide comprises as follows:
A) pyrethroid, permethrin for example, esfenvalerate, decis, time, particularly cyfloxylate, bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, to the pyrethroid of fish safety, ether chrysanthemum ester for example, natural pyrethrin, tetramethrin, S-Dtrans allethrin ester, five Flumethrins, prallethrin and 5-benzyl-3-furfuryl-(E)-(1R, 3S)-2,2-dimethyl-3-(2-Evil thiophene alkane-3-methyl) cyclopropanecarboxylcompound;
B) organophosphorus compounds, Profenofos for example, second Toyodan, parathion-methyl, gusathion m, methyl one O five or nine, heptan worm phosphorus, thiometon, Nemacur, nuvacron, Hostathion, acephatemet, Rogor, phosphamidon, malathion, chlopyrifos, zolone, Terbufos, half rope phosphorus, Dyfonate, thimet, phoxim, methyl insect wax phosphorus, pirimiphos ethyl, Folithion or basudin;
C) carbamate (comprising aryl-carbamate), for example Aphox removes line and becomes carbofuran, furathiocarb, benzene worm prestige, Aldicarb, thiofurox, carbosulfan ， Evil worm prestige, Osbac, unden or methomyl;
D) benzoyl area kind, for example desinsection is grand or UC 62644;
E) organo-tin compound plictran for example, fenbutatin oxide, azoles ring tin;
F) macrolide, for example Olivomitecidin or milbemycin, Avermectin for example, Olivomitecidin, milbemycin,
G) hormone and pheromone;
H) organochlorine compound hexachloro-benzene for example, dichlorodiphenyl trichloroethane, Niran or dieldrin;
I) for example galecron or amitraz of amidine class;
J) fumigant;
K) Imidacloprid;
L) SPINOSYN 105.
Except top listed all kinds of chemical insecticides, has other insecticide of special target, if be suitable for also can be used in the mixture of the desirable purposes of mixture.For example, be used for the selective insecticide of special crop, for example use in paddy rice, the extraordinary insecticide of snout moth's larva is cartap or Buprofezin for example, also may be utilized.In addition, for the extraordinary insecticide in special insect strain/stage for example kills ovum-larvicide four mite piperazines, thiazole mite, Hexythiazox, tetradiphon, kill moth agent for example dicofol or propargite, miticide is fenisobromolate for example, chlorobenzilate, or growth regulator amdro for example, the fly eradication prestige, Entocon ZR 512, UC 62644 and TH-6040 also can be included in the composition.
The suitable synergist example that adopts in composition comprises Butacide, sesoxane, Safroxan and dodecyl imidazoles.
Following examples explanation the present invention.
Embodiment 1
Test by following employing black peach aphid resistance product plain (R2) illustrate that the present composition overcomes the effect of resistance, black peach aphid is owing to esterase E4 level increases, and to organic phosphorus compound (OPs), pyrethroid and carbamate are categorized as " resistance by force ".The composition of test is listed below.
Program is as follows:
Handle the previous day:
Little plastic basin is to be filled to approximately 1/3rd with 1% agar solution, cuts the about 1 inch Chinese cabbage of diameter (kind Tip Top) disk, is placed on the agar, under the top margin.Place the radish cotyledon of having contaminated from the teeth outwards, spend the night, the roundleaf sheet is contaminated; Cotyledon is withered, and aphid climbs on the disk.
Handle the same day:
Remove dried cotyledon, by the requirement that 1 consumption repeats for 10 times, each basin is labelled.With Burkhard Potter tower, by the amount of 300 l/ha each solution of spraying.Air one drying is just put the lid that has the ventilation osculum on basin, at 20 ℃, test was deposited 3 days.By this program, aphid passes through directly contact and when they were mobile on the blade face, residual ingested by dispenser.
Handled back 3 days:
Calculate death and the aphid number of surviving in each basin.Analyze data, the results are shown in the following table.
Subject composition death rate %1. Aphox (20ppm) 57.682. Aphox (20ppm)+compd A (1ppm) 98.973. Aphox (20ppm)+compd B (1ppm) 95.244. chlopyrifos (20ppm) 2.285. chlopyrifos (20ppm)+compd A (1ppm) 95.336. chlopyrifos (20ppm)+compd B (1ppm) 96.377. time (0.5ppm) 5.68. time (0.5ppm)+compd A (1ppm) 1009. time (0.5ppm)+compd B (1ppm) 94.19
Similar result of the test to the Nissl tetranychid is as follows:
Subject composition lethality %10. time (0.02ppm) 1511. compd As (250ppm) 4412. time (0.02ppm)+compd A (250ppm) 85
Embodiment 2
According to Beadle and Lees{Beadle D.J., Lees G (1986) Neuropharmacology and action of agricultural chemicals (being edited by people such as M.G.Ford) are p.423-444, Chichester:EllisHorwood} and Pinnock and Sattelle{Pinnock R.D., Sattelle D.B. (1987) Neuscience method magazine 20 is the simplification translation of described method p.195-202}, the cell of the thoracic ganglia of preparation locust.To each test, use single animal.Kill insects is containing 214mM Na +3.1mM K +9mM Ca 2+221mM Cl -10mM TES is adjusted under the saline of pH7.0, takes out its thoracic ganglia.All aixs cylinder processing each neuromere that pruned away is removed the sheath layer with meticulous pliers, then neuromere be cut into half or 1/4th, transfer to again in 1mg/ml (approximately) clostridiopetidase A (the Sigma type III) solution in cockroach physiological saline.After 30-50 minute, wash tissue in (room temperature), smash to pieces by the Pasteur pipette of electric mill light with no enzyme physiological saline.The suspension of gained is tiled in the Shi Panshang of the 50mm Fu Erken tightening seal that contains the medium that just is enough to cover disk.
These cells { Beadle D.J. that spends the night of in Beadle and the described medium of Hicks, surviving, Hicks D. (1985), insect is neural to be cultivated, in comprehensive Entomological Physiology, (Insect Nerve Culture in biochemistry and the pharmacology, In Comprehensive Insect Physiology, Biochemistry ﹠amp; Pharmacology, vol.5).Nervous system: structure and kinesitherapy nerve function (Nervous System:Structure ﹠amp; Motor Function, edited by G.A.Kerkutand E.I.Gilbert) p.181-211, Oxford:Pergamon Press}, in order to differentiate mixture, cultivate embryo's cell in the medium of additional 50 IU/ml penicillin/streptomycins and 50 μ g/ml gentamicins at Liebowitz ' s L-15 medium and Graces Insect T.C. medium (Gibco BRL) equal portions.In 1-2 hour of test, use and the identical physiologic saline for substitute medium of dissecting usefulness.Pour into cell with physiological saline, until obtain the result.
Adopt film potential under interior (electric current-clamp circuit) technical notes of conventional cell.The little pipette of borosilicate that the isolated cells body and function contains the silver/silver chloride electrode in 3M KCl (aqueous solution) electrolyte is pegged.Little pipette is to dial the tool preparation with the level of Sutler P97, can anti-20M Ω.By intracellular electrode,, or draw the positive current of activity-potential (inhibition), pulse repeatedly, electro photoluminescence cell with the negative current of evaluated for film resistance.
Compound C (10 μ M) and compd A (100 μ M) impose on cell membrane from being positioned near second little pipette (compartment of terrain) of inlet.This little pipette links to each other with voltage generator (MSC PLi100 Picoiniector), by the compound of nitrogen control impuls ejection arrival.SPINOSYN 105 is used by the physiological saline of perfusion.
Compound C (in the drawings referring to " comp.C ") is drawn the depolarising of cell, with in the film resistance one combine, shorten by voltage response and represent (Fig. 1) the negative current section.Reaction to compd A (in the drawings referring to " comp.A ") in same cell is presented among Fig. 2.There are not depolarising and or even slight hyperpolarization.
SPINOSYN 105 is being illustrated in Fig. 3 and 4 to the influence in the reaction of Compound C, and these figure have shown the reaction (Fig. 3) to the 50ms pulse of 4 Compound C, in the presence of 1 μ M SPINOSYN 105 to the contrast (Fig. 4) of the reaction of single 50ms pulse.These influence to small part is reversible, at flow velocity 1.3ml/min, wash about 30 minutes after, recovered the normal profilograph (Fig. 5) of compound reaction.SPINOSYN 105 has activity under minimum experimental concentration 100pM in this test.
SPINOSYN 105 is being illustrated in Fig. 6～11 to the influence in the reaction of compd A.Fig. 6～8 have been showed for just being enough to draw once the level that suppresses (0.4nA), the speed of step activity in per 1.8 seconds, the reaction of the auxiliary voltage of the 90ms pulse of 60 positive currents (I П) of using by electrode.In each case, the 90ms pulse of using a compd A in the middle of 10 steps.Square wave at the bottom of each figure is represented the duration of I П, and this also is the duration of the pulse of compd A in 10 activities.First example (Fig. 6) is the control under the situation that does not have SPINOSYN 105, and it shows not reaction of compd A.Fig. 7 is the record in the presence of 50nM SPINOSYN 105, has shown the variation of the preceding static profilograph of diving (energy) and suppressing of I П.In Fig. 7, the separation of each activity shows, during administered compound A (comprising movable 1～10), the profilograph that suppresses is that stable (Fig. 7 a), but follow (Fig. 7 b: movable 10-13) that uses of compd A, have depolarising, the result shortens the time of stimulation-inhibition and the last cancellation that suppresses on the peak of reaction.When it static of cellular-restoring dived (energy), the profilograph of inhibition also recovered (Fig. 7 c: activity 20,30,40,50 and 60).This inhibition stops type cell depolarization to be simulated by the continuous positive current of electrode, thinks that the elimination that suppresses is the Δ V that reduces owing to a step-moving point, and it is more much smaller than unpolarized sign.Fig. 8 is the record that enters after and then SPINOSYN 105 is used within 10-12 minute of washing.Have cancelling that some clearly influence; Inhibition does not disappear but still has some depolarisings.Shown in Fig. 8 a (movable 10-13), shortened the time of stimulation-inhibition.
Fig. 9～11st do not having (Fig. 9) and having in the presence of the SPINOSYN 105 (Figure 10) and after washing 10～12 minutes (Figure 11), the curve map that the stationary voltages that is caused by compd A changes.These figure are with each in 60 activities shown in Fig. 6～8 respectively, constitute at the voltage of following of 19ms point (just in time before I П).It is identical that the range scale of each figure keeps, and helps the reaction of comparative compound A.Be not elevated on the level of ambient interferences in " reaction " that do not have (Fig. 9) in the presence of the SPINOSYN 105 to compd A, and (Figure 10) has one clearly greater than the depolarising of 14mV in the presence of SPINOSYN 105.Along with SPINOSYN 105 is washed off, voltage steadily descend (Figure 11).
Therefore, Compound C is the neurogenous potential depolarizing agent of a kind of insect, and SPINOSYN 105 is reversibly strengthened this effect.In the presence of SPINOSYN 105, can reach effective depolarising reaction with compd A.
Referring to general formula is listed in down hereinbefore:

Claims (8)

1. Pesticidal combination, it contains a kind of insect has produced resistance to a certain degree to it first insecticidal active ingredient, a kind of carrier of desinsection inertia or thinner, with optional one or more surfactants, it is characterized in that said composition also contains a kind of general formula (I) compound of q.s in order to improve composition in the activity that overcomes on the pest resistance:
Figure A9718151000021
Wherein A represents general formula-CH 2CH 2-or the group of CH=CH; Ar is phenyl, pyridine radicals, pyridazinyl or pyrazinyl, all available halogen of all these groups, C 1-4Alkyl, C 1-4Alkoxyl, C 2-4Alkenyl, C 2-4Alkynyl group or cyano group are selected arbitrarily to replace; R is a hydrogen, C 1-4Alkyl (is used cyano group, CO 2(C 1-4Alkyl) or phenyl (itself can be used halogen, C 1-4Alkyl, C 1-4Alkoxyl, C 1-4Alkylhalide group or C 1-4The halogen alkoxyl is selected arbitrarily to replace) select arbitrarily to replace), C 2-4Alkylhalide group (α-carbon is not substituted), C 3-4Alkenyl or C 3-4Alkynyl group; When R is alkenyl or alkynyl group, said group not with general formula (I) ring in the unsaturated carbon atom that directly links to each other of nitrogen; Or the acid-addition salts of deriving thus, quaternary ammonium salt or N-oxide.
2. composition as claimed in claim 1, wherein first insecticidal active ingredient is selected from compound composed as follows: time, cyfloxylate, decis, sumicidin, esfenvalerate, cyfluthrin, β-cyhalothrin, ether chrysanthemum ester, tefluthrin, chlopyrifos, Profenofos, orthene, Rogor, parathion-methyl, Terbufos, nuvacron, the second Toyodan, Toyodan, Aldicarb, carbofuran, carbaryl, Methomyl, Osbac, Aphox, TH-6040, UC 62644, Teflubenzuron, fluorine bell urea, flufenoxuron, the fluorine third oxygen urea, flucycloxuron, amitraz, four mite a kind of cicada mentioned in ancient books, azoles mite ester, Hexythiazox, propargite, tebufenpyrad, fenazaquin, pyridaben, SPINOSYN 105, triaguron, Buprofezin, Avermectin, sharp strength spy, the luxuriant ether of Difenamide ， Evil, Imidacloprid and fluorine azoles worm are clear.
3. improve a kind of insect and these insecticides are produced the to a certain degree method of the biocidal activity of resistance, it comprises the place that a kind of Pesticidal combination that contains this insecticide and relevant general formula (I) compound is applied to pest or pest, and A represents general formula-CH in the general formula (I) 2CH 2-or the group of CH=CH; Ar is phenyl, pyridine radicals, pyridazinyl or pyrazinyl, all available halogen of all these groups, C 1-4Alkyl, C 1-4Alkoxyl, C 2-4Alkenyl, C 2-4Alkynyl group or cyano group are selected arbitrarily to replace; R is a hydrogen, C 1-4Alkyl (is used cyano group, CO 2(C 1-4Alkyl) or phenyl (itself can be used halogen, C 1-4Alkyl, C 1-4Alkoxyl, C 1-4Alkylhalide group or C 1-4The halogen alkoxyl is selected arbitrarily to replace) select arbitrarily to replace), C 2-4Alkylhalide group (α-carbon is not substituted), C 3-4Alkenyl or C 3-4Alkynyl group; Condition is R when being alkenyl or alkynyl group, said group not with the ring of general formula (I) in the unsaturated carbon atom that directly links to each other of nitrogen; Or the addition salts of the acid of deriving thus, quaternary ammonium salt or N-oxide.
One kind eliminate or control the insect of the three unities, the method for evil mite or nematode, it comprise with effective dose according to the compositions-treated pest of claim 1 or the place of pest.
5. contain SPINOSYN 105 and general formula (I) compound compositions: Wherein A represents general formula-CH 2CH 2-group; Ar is phenyl, pyridine radicals, pyridazinyl or pyrazinyl, all available halogen of all these groups (particularly fluorine, chlorine or bromine), C 1-4Alkyl (particularly methyl), C 1-4Alkoxyl (particularly methoxyl group), C 2-4Alkenyl, C 2-4Alkynyl group or cyano group are selected arbitrarily to replace; R is a hydrogen, C 1-4Alkyl (is used cyano group, CO 2(C 1-4Alkyl) or phenyl (itself can be used halogen, C 1-4Alkyl, C 1-4Alkoxyl, C 1-4Alkylhalide group or C 1-4The halogen alkoxyl is selected arbitrarily to replace) select arbitrarily to replace), C 2-4Alkylhalide group (α-carbon is not substituted), C 3-4Alkenyl or C 3-4Alkynyl group; Condition is when R is alkenyl or alkynyl group, said group not with the ring of general formula (I) in the unsaturated carbon atom that directly links to each other of nitrogen; Or the addition salts of the acid of deriving thus, quaternary ammonium salt or N-oxide.
6. the insect of eliminating and preventing and treating at the three unities, the method for evil mite or nematode, it comprises the place that contains SPINOSYN 105 and general formula (I) compound compositions processing pest or pest with effective dose, A represents general formula-CH in the general formula (I) 2CH 2-group; Ar is phenyl, pyridine radicals, pyridazinyl or pyrazinyl, all available halogen of all these groups (particularly fluorine, chlorine or bromine), C 1-4Alkyl (particularly methyl), C 1-4Alkoxyl (particularly methoxyl group), C 2-4Alkenyl, C 2-4Alkynyl group or cyano group are selected arbitrarily to replace; R is a hydrogen, C 1-4Alkyl (is used cyano group, CO 2(C 1-4Alkyl) or phenyl (itself can be used halogen, C 1-4Alkyl, C 1-4Alkoxyl, C 1-4Alkylhalide group or C 1-4The halogen alkoxyl is selected arbitrarily to replace) select arbitrarily to replace), C 2-4Alkylhalide group (α-carbon is not substituted), C 3-4Alkenyl or C 3-4Alkynyl group; Condition is when R is alkenyl or alkynyl group, said group not with the ring of general formula (I) in the unsaturated carbon atom that directly links to each other of nitrogen; Or the addition salts of the acid of deriving thus, quaternary ammonium salt or N-oxide.
7. according to the method for claim 4 or 6, wherein pest is the insect that is grown on the plant.
8. as desired composition or method in above-mentioned arbitrary the claim, its formula of (I) compound is:
3-(5-chloropyridine-3-yl)-3-cyano group-8-(2,2, the 2-trifluoroethyl)-8-azabicyclo [3.2.1] octane;
3-(5-chloropyridine-3-yl)-3-cyano group-8-(2,2-two fluoro ethyls)-8-azabicyclo [3.2.1] octane; Or
3-(5-chloropyridine-3-yl)-3-cyano group-8-chlorine dicyclo [3.2.1] octane of mixing.
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CN105072910A (en) * 2013-03-28 2015-11-18 先正达参股股份有限公司 Methods of controlling neonicotinoid resistant pests
CN105120667A (en) * 2013-03-28 2015-12-02 先正达参股股份有限公司 Methods of controlling neonicotinoid resistant pests
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CN105072910A (en) * 2013-03-28 2015-11-18 先正达参股股份有限公司 Methods of controlling neonicotinoid resistant pests
CN105120667A (en) * 2013-03-28 2015-12-02 先正达参股股份有限公司 Methods of controlling neonicotinoid resistant pests
CN105494383A (en) * 2016-02-05 2016-04-20 烟台顺隆化工科技有限公司 Pesticide for prevention and treatment of opogona sacchari

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