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WO1999018796A2 - Pesticidal combination - Google Patents

Pesticidal combination Download PDF

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Publication number
WO1999018796A2
WO1999018796A2 PCT/EP1998/006657 EP9806657W WO9918796A2 WO 1999018796 A2 WO1999018796 A2 WO 1999018796A2 EP 9806657 W EP9806657 W EP 9806657W WO 9918796 A2 WO9918796 A2 WO 9918796A2
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WO
WIPO (PCT)
Prior art keywords
spp
compound
pesticide
hydrogen
formula
Prior art date
Application number
PCT/EP1998/006657
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French (fr)
Other versions
WO1999018796A3 (en
Inventor
Bernard Leroux
Scot Kevin Huber
Original Assignee
Rhone-Poulenc Agro
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhone-Poulenc Agro filed Critical Rhone-Poulenc Agro
Priority to AU11554/99A priority Critical patent/AU1155499A/en
Publication of WO1999018796A2 publication Critical patent/WO1999018796A2/en
Publication of WO1999018796A3 publication Critical patent/WO1999018796A3/en

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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
    • 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
    • A01N47/08—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 one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products

Definitions

  • the present invention relates to a new pesticidal combination, a composition comprising the combination and to a method of controlling pests.
  • the invention further relates to a process for the preparation of the novel composition, to the use thereof and to plant propagation material treated therewith, and to the use of a compound of formula (I) below for the preparation of said novel composition.
  • the invention relates to a pesticidal combination comprising a compound of formula (I):
  • R ⁇ a and R2 a are independent of one another, hydrogen or halogen;
  • R3 a is hydrogen or chlorine;
  • R4 a , R5 a and Rg a are independent of one another, hydrogen, halogen or alkyl, preferably methyl;
  • A is -CF 2 CHFCF 3 , Gl.
  • R ⁇ a to Ri6a are independent of one another, hydrogen, halogen, alkyl or nitro; and provided that Rj a and R 2a are not simultaneously hydrogen; and that R4 a , R5 a and Rg a are not simultaneously hydrogen; and that when A is -CF2CHFCF3, R ⁇ a and R 2a are both fluorine, R 3a is hydrogen or chlorine, R4 a and R a are both hydrogen. and R5 a is chlorine; in the free form or in the form of a pesticidally acceptable salt thereof, and a pesticide.
  • the alkyl groups of formula (I) are generally of from C
  • the pesticidally acceptable salts of the compound of formula (I) are typically addition salts of inorganic and organic acids, preferably of hydrochloric acid, hvdrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, malonic acid, toluenesulfonic acid or benzoic acid.
  • Preferred combinations within the scope of this invention are those that contain the compound of formula (I) in the free form as an active ingredient.
  • a combination of the compound of formula (I) and only one pesticide is preferred.
  • the pesticide is an insecticide. More preferably the pesticide is:
  • Another group of preferred pesticides is:
  • the milbemycins or avermectins that may be used in the present invention include the following compounds: Ivermectin (which is 22,23-Dihydroavermectin B
  • milbemectin which is a mixture comprsing Milbemycin A 3 and Milbemycin A 4 ), doramectin (which is Spiro[l 1.15-methano-2H,13H, 17H-furo[4,3,2- pq][2,6]benzodioxacyclooctadecin- 13,2'-[2H]pyran]), moxidectin, milbemycin. and mibemycin oxime, emamectin, and emamectin benzoate.
  • the avermectins and milbemycins are generally known to the skilled addressee who has access to the Chemical Abstracts. The Pesticide Manual, 10th edition, ( 1994), The British Crop Protection Council, London.
  • benzimidazoles that may be used in the present invention include the following compounds: methyl 5-propylthio-2-benzimidazolecarbamate (albendazole): isopropyl 2-(4-thiazolyl)-5-benzimidazolecarbamate (cambendazole); 2- (methoxycarbonylamino)-5-(phenylthio)benzimidazole (fenbendazole); 5-benzoyl-2- benzimidazolecarbamic acid methyl ester (mebendazole); 2,3,5,6-tetrahydro-6- phenyl-imidazo[2,l-b]thiazole (levamisole); and oxibendazole.
  • the chloronicotinyl insecticides of the present invention include imidacloprid. acetamiprid, nitempyram. thiacloprid, CGA-293343, AKD- 1022, MTI-446, Tl-435 and nithiazine.
  • Imidacloprid, acetamiprid and nitempyram are preferred compounds.
  • the said compounds are generally known to the skilled addressee who has full access to the Chemical Abstracts. Some of these compounds are found in The Pesticide Manual. 10th edition, ( 1994), The British Crop Protection Council, London.
  • Nodulisporic acid and derivatives thereof are generally described in PCT publication number WO 96/29073.
  • Three members of this class of antiparasitic agents that are particularly preferred in the present invention include nodulisporic acid; 29,30- dihydro-20,30-oxa-nodulisporic acid; and 31-hydroxy-20.30-oxa-29,30,31,32- tetrahydro-nodulisporic acid.
  • Esters, amides, and other parasiticidally acceptable derivatives of these that known to or may be prepared by the skilled addressee, including diastereomeric forms thereof, may also be used.
  • the pesticidal combination of this invention will preferably contain a compound of formula (I) and a pesticide in a weight ratio of 500: 1 to 1:50, especially in a ratio from 200: 1 to 1 :20, more particularly from 100: 1 to 1 : 10.
  • the combination of the pesticide of formula (I) and the pesticide provides a most advantageously long acting effect.
  • An additive enhancement of the activity spectrum on the pests to be controlled can also be obtained.
  • the combination can also provide a synergistic effect that improves the activity ranges of both compounds from two points of view.
  • the concentrations of the compound of formula (I) and the pesticide may be reduced with no reduction in the activity obtained.
  • the combination also achieves a high degree of pest control where the individual compounds are substantially or completely inactive at low concentrations. This feature permits on the one hand a broadening of the activity spectrum against the controllable pests and. on the other, an enhancement of safety of application.
  • the combinations of this invention have useful preventive and/or curative properties in the field of pest control even at low concentration. They are well tolerated by warm-blooded animals, fish and plants, and they have a very favorable biocidal spectrum.
  • the compositions are effective against all, or individual, development stages of normally sensitive as well as resistant pests of animals such as insects and representatives of the order Acarina.
  • the onset of the insecticidal and/or acaricidal action of the novel compositions may follow directly, i.e.- a kill of the pests will occur immediately or only after some time, for example where moulting is effected, or indirectly, for example in diminished oviposition and/or hatching rate.
  • the mixtures of the invention are most valuable by their long term effect as well as by their good margin of safety for veterinary and nuisance insect applications. They are also most useful because of their combined activity on both ticks and fleas, especially those of pets, such as dogs or cats. The combination therefore affords excellent control of fleas over a prolonged period. Another advantage of such mixtures is that are well adapted to oral administration. A further advantage is that these combinations provide prolonged period of control and broad spectrum activity.
  • the appropriate doses are generally from 0.01 to 500 mg/kg, preferably 0.1 to 100 mg/kg for the pesticide, "mg/kg" in this instance indicating the milligrams of the pesticide per kilogram of body weight of animal.
  • the amount of IGR partner present in the mixture will vary according to the efficacy of the IGR and the precise conditions of use. One administration per week and preferably one administration per month or higher provide generally good efficacy.
  • the aforementioned animal pests typically include: of the order Lepidoptera
  • Eupioctis spp Euxoa spp Graphohta spp , Hedya nubiferana. Hehothis spp , Hellula anda s, Hyphant ⁇ a cunea, Keife ⁇ a lycopersicella, Leucoptera scitella Lithocllethis spp Lobesia botrana, Lymant ⁇ a spp Lyonetia spp , Malacosoma spp , Mamestra biassicae, Manduca sexta, Operophtera spp , Ost ⁇ nia nubilahs, Pammene spp Pandemis spp , Panohs flammea, Pectinophora gossypieua, Phtho ⁇ maea operculeua, Pie ⁇ s rapae, Pie ⁇ s spp Plutella xylostella Prays spp Scirpoph
  • Thaumetopoea spp Tort ⁇ x spp , T ⁇ choplusia m and Yponomeuta spp , ot the order Coleoptera, tor example Ag ⁇ otes spp , Anthonomus spp , Atoma ⁇ a linea ⁇ s Chaetocnema tibia s, spp , Curcuho spp , Dermestes spp , Diabrotica spp , Epilachna spp , Eremnus spp , Leptinotarsa decemhneata, Lissoihoptius spp .
  • Haematopinus spp Linognathus spp , Pediculus spp .
  • Pemphigus spp and Phylloxera spp of the order Mallophaga, tor example Damalinea spp. and Trichodectes spp.; of the order Thysanoptera. for example
  • Scotinophara spp. and Triatoma spp. of the order Homoptera, for example Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium.
  • Homoptera for example Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium.
  • Chrysomphalus dictyospermi Coccus hesperidum. Empoasca spp., Eriosoma lanigerum, Erythroneura spp.. Gascardia spp., Laodelphax spp., Lecanium corni.
  • Pseudococcus spp. Psylia spp., Pulvinaria aethiopica, Quadraspidiotus spp.,
  • Rhopalosiphum spp. Saissetia spp., Scaphoideus spp.. Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri; of the order Hymenoptera, for example Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma.
  • Hoplocampa spp. Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.; of the order Diptera. for example
  • Hyppobosca spp. Liriomyza spp., Lucilia spp.. Melanagromyza spp., Musca spp..
  • Oestrus spp. Oestrus spp., Orseolia spp.. Oscinella frit, Pegomyia hyoscyami , Phorbia spp.,
  • pests ( 1 ) of the order Lepidoptera especially Adoxophyes spp.. Alabama argillaceae, Clysia ambigulla, Clysia pomonelia, Crocidolomia binotalis, Cydia spp., Earias spp., Heliothis spp.. Lobesia botrana, Ostrinia nubilalis, Phthohmea operculeua, Sparganothis spp. and Spodoptera spp.;
  • the family Aphididae more particularly the genus Aphis, most particularly A. gossypii; in particular the family Aleurodidae, preferably Aleurothrixus floccus and Bemisia tabaci; in particular Fainilie Psyllidae, more preferably Psylia spp., (4) of the order Thysanoptera.
  • Thripidae preferably Frankliniella spp., Thrips palmi and Thrips tabaci;
  • the pesticidal combination of this invention can be used with advantage for pest control in cereals such as maize or sorghum; fruit such as pome fruit, stone fruit and soft fruit, typically apples, pears, plums, peaches, almonds, cherries, or berries, for example strawberries, raspberries and blackberries; leguminous plants, typically including beans, lentils, peas and soybeans, oil plants such as rape, mustard, poppy, 0 olives, sunflowers, coconut, castor oil plants, cocoa beans and groundnuts; cucurbits such as marrows, cucumber and melons; fibre plants such as cotton, flax, hemp and jute; citrus fruit such as oranges, lemons, grapefruit and mandarins; vegetables such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae such as avocados, cinnamon and camphor, and tobacco, nuts, coffee, egg plants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants or ornamentals
  • pesticidal combinations of this invention are the protection of stored goods and materials as well as in the hygiene sector, for example, domestic animals and productive livestock against pests of the indicated type.
  • a particularly advantageous utility of the instant invention is in the protection of structures from nuisance insects including termites and cockroaches and ants.
  • the invention also relates to compositions comprising a combination of a compound of formula (I) and the pesticide in association with a pesticidally acceptable adjuvant.
  • the pesticidal compositions are generally emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, coatable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granulates or encapsulations in polymer substances, comprising a compound of formula (I) and the pesticide.
  • the active ingredients are generally used in those compositions in pure form, the solid compounds being typically used in a specific particle size, or preferably together with at least one of the adjuvants custoinarv in formulation technology, for example extenders such as solvents, or solid carriers, or surface-active compounds ( surfactants).
  • extenders such as solvents, or solid carriers, or surface-active compounds ( surfactants).
  • Suitable solvents are typically aromatic hydrocarbons or partially hydrogenated aromatic hydrocarbons, preferably the fraction of alkylbenzenes containing 8 to 12 carbon atoms, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons such as paraffins or cyclohexane; alcohols such as ethanol, propanol or butanol; glycols and their ethers and esters such as propylene glycol dipropylene glycol ether, diethylene glycol or 2- methoxyethanol or 2-ethoxyethanol: ketones such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents such as N-methylpyrrolid-2-one.
  • dimethyl sulfoxide or N,N-dimethylformamide water, vegetable oils or epoxidised vegetable oils such as rape oil, castor oil. coconut oil or soybean oil or epoxidised rape oil. castor oil, coconut oil or soybean oil. and silicone oils.
  • the solid carriers typically used for dusts and dispersible powders are usually natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. To improve the physical properties it is also possible to add highly dispersed silicic acids or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, including pumice, broken brick, sepiolite or bentonite. and suitable nonsorbent carriers are calcite or sand. In addition, innumerable granulated materials of inorganic or organic nature may be used, especially dolomite or pulverized plant residues.
  • suitable surface-active compounds are nonionic. cationic and/or anionic surfactants or mixtures of surfactants preferably having good emulsifying, dispersing and wetting properties.
  • the surfactants listed below shall be regarded merely as exemplary; many more surfactants customarily employed in formulation technology and suitable for use in the practice of the invention are described in the relevant literature.
  • Nonionic suitactants aie pieterably polyglycol ethei de ativcs ot aliphatic oi cycloaliphatic alcohols, saturated or unsaturated tattv acids and alkylphenols said derivatives containing 3 to 30 glycol ether gioups and 8 to 20 caibon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety ot the alkylphenols
  • Further suitable nonionic surfactants are water-soluble polyadducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypiopylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit
  • Cationic suifactants are prelei bly quaternary ammonium salts ca ⁇ ying, as N- substituent, at least one Cg-C 2 alkyl radical and, as fuithei substituents, unsubstituted or halogenated lower alkyl, benzyl oi hydroxy-lowei alkyl radicals
  • the salts are preferably in the form of ha des, methyl sulfates or ethyl sulfates Examples are stearyldimethylammonium chloride and benzyl b ⁇ s(2- chloroethyl)ethylammon ⁇ um b ⁇ om ⁇ de
  • Suitable anionic surfactants may be water-soluble soaps as well as watei -soluble synthetic surface-active compounds
  • Suitable soaps aie the alkali metal salts alkaline earth metal salts and unsubstituted or substituted ammonium salts of highei fatty acids (C JO-C 2 ), e g the sodium or potassium salts ot oleic ot stea ⁇ c acid oi of natural fatty acid mixtures which can be obtained e g fiom coconut oil or tall oil
  • suitable soaps are also the fatty acid methyltau ⁇ ne salts More frequently, however, synthetic surfactants are used, preferably fatty sulfonates.
  • fatty sulfates sulfonated benzimidazole derivatives or alkylarylsulfonates.
  • the fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and usually contain a Cg-
  • C alkyl radical which also includes the alkyl moiety of acyl radicals.
  • Typical examples are the sodium or calcium salt of ligninsulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives preferably contain two sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms.
  • alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or of a condensate of naphthalenesulfonic acid and formaldehyde.
  • Corresponding phosphates e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids are also suitable.
  • compositions will usually comprise 0.1 to 99 %. preferably 0.1 to 95% of a combination of the compound of formula (I) and one or more of the pesticides and 1 to 99.9%, preferably 5 to 99.9%, of at least one solid or liquid adjuvant; usually they will contain 0 to 25%, preferably 0.1 to 20%, of surfactants (in each case percentages are by weight).
  • surfactants in each case percentages are by weight.
  • Emulsi liable concentrates combination of (I) and (II): 1 to 95 %, preferably 5 to 20 surfactant: 1 to 30 preferably 10 to 20 % solvent: 5 to 98 preferably 70 to 85 %
  • Dusts combination of (I) and (II) 0.1 to 10, preferably 0.1 to 1% solid carrier: 99.9 to 90%, preferably 99.9 to 99%
  • Suspension concentrates combination of (I) and (II): 5 to 75%, preferably 10 to 50% water: 94 to 24%, preferably 88 to 30% surfactant: 1 to 40%, preferably 2 to 30%
  • Wettable powders combination of (I) and (II): 0.5 to 90, preferably 1 to 80% surfactant : 0.5 to 20, preferably 1 to 15% solid carrier: 5 to 99, preferably 15 to 98%
  • Granules combination of (I) and (II): 0.5 to 30, preferably 3 to 15% solid carrier. 99.5 to 70%, preferably 97 to 85%
  • novel compositions may also contain further solid or liquid adjuvants such as stabilizers, e.g. vegetable oils or epoxidised vegetable oils (e.g. epoxidised coconut oil. rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders and/or tackers, as well as fertilizers or other chemical agents for obtaining special effects, typically including bactericides, fungicides, nematicides, molluscicides or herbicides.
  • stabilizers e.g. vegetable oils or epoxidised vegetable oils (e.g. epoxidised coconut oil. rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders and/or tackers, as well as fertilizers or other chemical agents for obtaining special effects, typically including bactericides, fungicides, nematicides, molluscicides
  • compositions of this invention are prepared in known manner: in the absence of adjuvants, typically by grinding, sieving and/or compressing a solid active ingredient or mixture of active ingredients, for example to a specific particle size; and in the presence of at least one adjuvant, for example by intimately mixing and/or grinding the active ingredient or mixture of active ingredients with the adjuvant or adjuvants.
  • the invention also relates to the preparation of the compositions.
  • the methods of applying the combinations typically include spraying, atomizing, dusting, coating, dressing, scattering or pouring, selected in accordance with the intended objectives and prevailing circumstances, and the use of the combinations for controlling pests of the indicated type, are further objects of the invention.
  • Typical rates of concentration are in the range from 0.01 to 1000 ppm, preferably from 0.1 to 500 ppm, of active ingredient.
  • the rate of application may vary over a wide range and will depend on the nature of soil, the type of application (eg.
  • the rates of application per hectare will usually be from 0.5g/ha to 2000 g/ha, more particularly from 10 to 1000 g/ha, preferably from 20 to 600 g/ha.
  • a preferred method of application in the field of plant protection is application to the foliage of the plants (foliar application), the number of applications and the rate of application depending on the risk of infestation by the particular pest.
  • the active ingredients can also penetrate the plants through the roots (systemic action) by drenching the locus of the plants with a liquid formulation or by applying the active ingredient in solid form to the locus of the plants, for example to the soil, e.g. in granular form (soil application). In paddy rice crops, such granules may be applied to the flooded rice field.
  • the invention compi ⁇ ses a compound ot toi mula 1 11 in Us tree lorm oi a pesticidally acceptable salt theieot and a pesticide toi simultaneous separate or sequential use in the control oi pests at a locus
  • compositions of the invention are also suitable tor protecting plant propagation material, e g seeds such as fruit, tubers or grains, or plant cuttings, against animal pests
  • the propagation material can be treated with the tormulation before planting Seeds, for example, can be dressed before sowing
  • the compounds of the in ention can also be applied to grains (eg by coating), for example by impregnating the grains with a liquid formulation or by coating them with a solid formulation
  • the composition can also be applied to the locus of planting when planting the propagation material, tor example to the seed furrow dining sowing
  • the invention ielates also to these methods of treating plant propagation material and to the plant propagation material so treated
  • Example FI Emulsifiable concentrate a) b) combination (ratio of compound of formula (I) to (II) 1 1) 25 40 %
  • Emulsions of any desired concentration can be prepared from such concentrates b dilution with water.
  • MW means Molecular Weight.
  • Example F2 Solutions a) b) c) d) combination (2: 1) 80% 10% 5% 95%
  • the solutions are suitable for use in the form of microdrops.
  • Example F3- Granulates a) b) c) d) combination ( 1 : 10) 5% 10% 8% 21% kaolin 94% - 79% 547c highly dispersed silica 1% - 13% 7% attapulgite - 90% - 18%
  • the active ingredients are dissolved in dichloro methane, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated in vacuo.
  • Example F4- Dusts a) b) combination ( 1 :5) 2% 5% highly dispersed silica 1% 5% talcum 97 % _ kaolin 90%
  • Example F5 Wettable powders a) b) c) combination ( 1 : 1 ) 25% 50% 75% sodium ligninsulfonate 5% 5% - sodium lauryl sulfate 3% - 5% sodium diisobutylnaphthalene- sulfonate - 6% 10% octylphenol polyethoxylate
  • the active ingredients are mixed with the additives, and the mixture is ground thoroughly in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentrations.
  • Example F6 Emulsifiable concentrate combination ( 1: 1) 10% octylphenol polyethoxylate
  • Emulsions of any desired concentration can be prepared from this concentrate by dilution with water.
  • Example F7 Dusts a) b) combination ( 1 :2) 5% 8% talcum 95% kaolin - 92%
  • Ready-to-use dusts are obtained by mixing the active ingredients with the carrier and grinding the mixture on a suitable mill.
  • Example F8 Extruder granules combination ( 1 :3) 10% sodium ligninsulfonate 2% carboxymethyl cellulose 1% kaolin 87%
  • the active ingredients are mixed with the additives, and the mixture is ground and moistened with water. This mixture is extruded, granulated and subsequently dried in a stream of air.
  • Example F9 Coated granulates combination ( 1: 1) 3% polyethylene glycol (MW 200) 3% kaolin 94%
  • Example F10 Suspension concentrate combination (2: 1 ) 40% ethylene glycol 10% nonylphenol polyethoxylate
  • the finely ground active ingredients are mixed intimately with the additives to give a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.
  • a synergistic effect is always obtained whenever the activity of the combination of the compound of formula (I) with a pesticide is greater than the sum of the activities of the individually applied compounds.
  • Y Percentage mortality, compared with untreated controls, after treatment with the pesticide at a rate of application of q kg/hectare.
  • a 15 kg dog is treated with Compound (C) and doramectin.
  • the treatment is made by ingestion of a 5g pill made by the compression of 0. Ig of total active ingredients with 4.0g flour and 0.9g of sugar (some appetizing flavors were also added)
  • the dog is then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
  • Example 2 Action against Fleas A 50 kg dog is treated with Compound (C) and milbemycin. The treatment is made by ingestion of a 10 g pill made by the compression of 0.3g of total active lngiedients with a 9 7g dog tood The dog is then infested with fleas After one week, no fleas are observed, and eggs are substantially reduced
  • Example 3 A 5 kg cat is treated with Compound (C) and ivermecun. The treatment is made by ingestion of a 0.5g pill made by the compression of 0.05g of total active ingredients with 0 4g flour and 0. Ig of sugar (some appetizing flavors were also added) The cat was then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
  • Compound (C) and ivermecun The treatment is made by ingestion of a 0.5g pill made by the compression of 0.05g of total active ingredients with 0 4g flour and 0. Ig of sugar (some appetizing flavors were also added) The cat was then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
  • a 15 kg dog is treated with Compound (C) and oxibendazole
  • the treatment is made by ingestion of a 5g pill made by the compression of 0.1 g of total active ingredients with 4.0g flour and 0.9g of sugar (some appetizing flavors were also added)
  • the dog is then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
  • a 50 kg dog is treated with Compound (C) and fenbendazole.
  • the treatment is made by ingestion of a 10 g pill made by the compression of 0.3g of total active ingredients with a 9.7g dog food.
  • the dog is then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
  • Example 6 A 5 kg cat is treated with Compound (C) and levamizole. The treatment is made by ingestion of a 0.5g pill made by the compression of 0.05g of total active ingredients with 0.4g flour and O. lg of sugar (some appetizing flavors were also added) The cat was then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
  • Example 7 A 5 kg cat is treated with Compound (C) and levamizole. The treatment is made by ingestion of a 0.5g pill made by the compression of 0.05g of total active ingredients with 0.4g flour and O. lg of sugar (some appetizing flavors were also added) The cat was then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
  • Example 7 A 5 kg cat is treated with Compound (C) and levamizole. The treatment is made by ingestion of a 0.5g pill made by the compression of 0.05g of total active ingredients with
  • a 50 kg dog is treated with Compound (C) and nitempyran.
  • the treatment is made by ingestion of a 10 g pill made by the compression of 0.3g of total active ingredients with a 9.7g dog food.
  • the dog is then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
  • a 5 kg cat is treated with Compound (C) and imidacloprid.
  • the treatment is made by ingestion of a 0.5g pill made by the compression of 0.05g of total active ingredients with 0.4g flour and O. lg of sugar (some appetizing flavors were also added)
  • the cat was then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
  • Example 9 A 15 kg dog is treated with Compound (C) and pyrantel. The treatment is made by ingestion of a 5g pill made by the compression of 0. Ig of total active ingredients with 4.0g flour and 0.9g of sugar (some appetizing flavors were also added) The dog is then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
  • a 50 kg dog is treated with Compound (C) and pyrantel palmoate.
  • the treatment is made by ingestion of a 10 g pill made by the compression of 0.3g of total active ingredients with a 9.7g dog food.
  • the dog is then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
  • a 5 kg cat is treated with Compound (C) and praziquantel.
  • the treatment is made by ingestion of a 0.5g pill made by the compression of 0.05g of total active ingredients with 0.4g flour and 0. Ig of sugar (some appetizing flavors were also added)
  • the cat was then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
  • Example 12 Artificial growth medium was treated with Compound C at rates of 4, 1, 0.25, 0.06 and 0.015 ppm. Artificial growth medium was treated with Imidacloprid at 6.25 ppm. Artificial growth medium was treated with 5 combinations of Compound C and imidacloprid as indicated below. Artificial growth medium was treated with avermectin at 1.6 ppm. Larvae of Spodoptera Eridania were placed in the media and allowed to stay. Mortality was measured at 3 and 5 days after the larvae were introduced (DAT). The following results in Table 2 show synergism for combinations of avermectin and compound C and imidacloprid and compound C:
  • Example 13 Example 1 is repeated with nodulisporic acid and Compound C. After one week, there are no fleas on the dog and the number of eggs is reduced.

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Abstract

A pesticidal combination comprising a compound of formula (I) and a pesticide.

Description

Pesticidal Combination
The present invention relates to a new pesticidal combination, a composition comprising the combination and to a method of controlling pests. The invention further relates to a process for the preparation of the novel composition, to the use thereof and to plant propagation material treated therewith, and to the use of a compound of formula (I) below for the preparation of said novel composition.
Certain mixtures of pesticides have been proposed in the literature for pest control. However, the biological properties of these known mixtures are unable to satisfy the requirements made,, of them in the field of pest control in all respects, so that there is still a need to provide further mixtures having synergistic properties for pest control, in particular for controlling insects and representatives of the orders. This need is met in whole or in part by the provisions of this invention.
Accordingly, the invention relates to a pesticidal combination comprising a compound of formula (I):
Figure imgf000003_0001
(I) wherein:
Rιa and R2a are independent of one another, hydrogen or halogen; R3a is hydrogen or chlorine; R4a, R5a and Rga are independent of one another, hydrogen, halogen or alkyl, preferably methyl; A is -CF2CHFCF3, Gl. G2, G3 or G4:
Figure imgf000004_0001
(Gl) (G2) (G3) (G4) wherein Rηa to Ri6a are independent of one another, hydrogen, halogen, alkyl or nitro; and provided that Rja and R2a are not simultaneously hydrogen; and that R4a, R5a and Rga are not simultaneously hydrogen; and that when A is -CF2CHFCF3, Rιa and R2a are both fluorine, R3a is hydrogen or chlorine, R4a and R a are both hydrogen. and R5a is chlorine; in the free form or in the form of a pesticidally acceptable salt thereof, and a pesticide.
The alkyl groups of formula (I) are generally of from C| to C4 and optionally substituted by one or more halogens. It will be understood that the compounds of formula (I) and the pesticide include enantiomers and/or diastereomers thereof. The invention embraces these and mixtures thereof.
The compounds of formula (I) wherein A is (Gl), (G2), (G3) or (G4) are preferred, (Gl) being very preferred. The compound of formula (I) wherein Rιa=R2a=F; R3a=R5a=Me; R4a=Cl; R6a=H; A=G1; R7a=R9a=Cl; R8a=R10a=H, hereinafter known as Compound (C) is very highly preferred.
The compound l-(5-chloro-4-[l,l,2,3,3,3-hexafluoroprop-l-oxy]phenyl)-3-(2.6- difluorobenzoyl)urea (novaluron) of formula (I) is described in European Patent Publication 0271923. The compound l-(2,5-dichloro-4-[l, l,2.3,3,3-hexafluoroρrop- l-oxy]phenyl)-3-(2,6-difluorobenzoyl)urea (lufenuron) of formula (I) is described in, inter alia The Pesticide Manual, 10th edition, ( 1994), The British Crop Protection Council, London, page 628. The general preparation of compounds of formula (I) may be found in U.S. Patent 5,135,953 and references recited therein.
The pesticidally acceptable salts of the compound of formula (I) are typically addition salts of inorganic and organic acids, preferably of hydrochloric acid, hvdrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, malonic acid, toluenesulfonic acid or benzoic acid.
Preferred combinations within the scope of this invention are those that contain the compound of formula (I) in the free form as an active ingredient.
A combination of the compound of formula (I) and only one pesticide is preferred.
Other compounds of formula (I) which may be used in the present invention are those listed in Table (I).
lable 1
Figure imgf000006_0001
Preferably the pesticide is an insecticide. More preferably the pesticide is:
(A) a milbemycin or avermectin;
(B) a chloronicotinyl insecticide; (C) a benzimidazole; or
(D) nodulisporic acid or a derivative thereof.
Another group of preferred pesticides is:
Spinosad or a derivative thereof, AKD-1022, chlorfenapyr, diofenolan. flufenprox, MTI-446, pymetrozine, JKU-0422, nitroscanate, piperazine, praziquantel, pyrantel. and pyrantel palmoate
The milbemycins or avermectins that may be used in the present invention include the following compounds: Ivermectin (which is 22,23-Dihydroavermectin B| ), abamectin (which is a mixture comprising Avermectin B|a, and Avermectin B|h). and milbemectin (which is a mixture comprsing Milbemycin A3 and Milbemycin A4), doramectin (which is Spiro[l 1.15-methano-2H,13H, 17H-furo[4,3,2- pq][2,6]benzodioxacyclooctadecin- 13,2'-[2H]pyran]), moxidectin, milbemycin. and mibemycin oxime, emamectin, and emamectin benzoate. The avermectins and milbemycins are generally known to the skilled addressee who has access to the Chemical Abstracts. The Pesticide Manual, 10th edition, ( 1994), The British Crop Protection Council, London.
The benzimidazoles that may be used in the present invention include the following compounds: methyl 5-propylthio-2-benzimidazolecarbamate (albendazole): isopropyl 2-(4-thiazolyl)-5-benzimidazolecarbamate (cambendazole); 2- (methoxycarbonylamino)-5-(phenylthio)benzimidazole (fenbendazole); 5-benzoyl-2- benzimidazolecarbamic acid methyl ester (mebendazole); 2,3,5,6-tetrahydro-6- phenyl-imidazo[2,l-b]thiazole (levamisole); and oxibendazole. These and other benzimidazoles may be found in the Chemical Abstracts to which the skilled addressee has access. The chloronicotinyl insecticides of the present invention include imidacloprid. acetamiprid, nitempyram. thiacloprid, CGA-293343, AKD- 1022, MTI-446, Tl-435 and nithiazine. Imidacloprid, acetamiprid and nitempyram are preferred compounds. The said compounds are generally known to the skilled addressee who has full access to the Chemical Abstracts. Some of these compounds are found in The Pesticide Manual. 10th edition, ( 1994), The British Crop Protection Council, London.
Nodulisporic acid and derivatives thereof are generally described in PCT publication number WO 96/29073. Three members of this class of antiparasitic agents that are particularly preferred in the present invention include nodulisporic acid; 29,30- dihydro-20,30-oxa-nodulisporic acid; and 31-hydroxy-20.30-oxa-29,30,31,32- tetrahydro-nodulisporic acid. Esters, amides, and other parasiticidally acceptable derivatives of these that known to or may be prepared by the skilled addressee, including diastereomeric forms thereof, may also be used.
The pesticidal combination of this invention will preferably contain a compound of formula (I) and a pesticide in a weight ratio of 500: 1 to 1:50, especially in a ratio from 200: 1 to 1 :20, more particularly from 100: 1 to 1 : 10.
The combination of the pesticide of formula (I) and the pesticide provides a most advantageously long acting effect. An additive enhancement of the activity spectrum on the pests to be controlled can also be obtained. The combination can also provide a synergistic effect that improves the activity ranges of both compounds from two points of view.
On the one hand, the concentrations of the compound of formula (I) and the pesticide may be reduced with no reduction in the activity obtained. On the other hand, the combination also achieves a high degree of pest control where the individual compounds are substantially or completely inactive at low concentrations. This feature permits on the one hand a broadening of the activity spectrum against the controllable pests and. on the other, an enhancement of safety of application.
The combinations of this invention have useful preventive and/or curative properties in the field of pest control even at low concentration. They are well tolerated by warm-blooded animals, fish and plants, and they have a very favorable biocidal spectrum. The compositions are effective against all, or individual, development stages of normally sensitive as well as resistant pests of animals such as insects and representatives of the order Acarina. The onset of the insecticidal and/or acaricidal action of the novel compositions may follow directly, i.e.- a kill of the pests will occur immediately or only after some time, for example where moulting is effected, or indirectly, for example in diminished oviposition and/or hatching rate. The mixtures of the invention are most valuable by their long term effect as well as by their good margin of safety for veterinary and nuisance insect applications. They are also most useful because of their combined activity on both ticks and fleas, especially those of pets, such as dogs or cats. The combination therefore affords excellent control of fleas over a prolonged period. Another advantage of such mixtures is that are well adapted to oral administration. A further advantage is that these combinations provide prolonged period of control and broad spectrum activity. The appropriate doses are generally from 0.01 to 500 mg/kg, preferably 0.1 to 100 mg/kg for the pesticide, "mg/kg" in this instance indicating the milligrams of the pesticide per kilogram of body weight of animal. The amount of IGR partner present in the mixture will vary according to the efficacy of the IGR and the precise conditions of use. One administration per week and preferably one administration per month or higher provide generally good efficacy.
The aforementioned animal pests typically include: of the order Lepidoptera
Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argulaceae, Amylois spp., Anticarsia gemmatalis, Archips spp.. Argyrotaenia spp., Autographa spp., Busseola fusca. Cadra cautella. Carposina nipponensis, Chilo spp., Choi istoneui a spp Clvsia ambigueua Cnaphalouous spp Cnephasia spp Cochv hs spp , Coleophoi a spp , Ciocidolomia binotaus Ciyptophlebia leucotieta C dia spp , Diatraea spp , Diparopsis castanea Eaπas spp , Ephestia spp . Eucosma spp Eupoeciha ambiguena. Eupioctis spp , Euxoa spp Graphohta spp , Hedya nubiferana. Hehothis spp , Hellula anda s, Hyphantπa cunea, Keifeπa lycopersicella, Leucoptera scitella Lithocllethis spp Lobesia botrana, Lymantπa spp Lyonetia spp , Malacosoma spp , Mamestra biassicae, Manduca sexta, Operophtera spp , Ostπnia nubilahs, Pammene spp Pandemis spp , Panohs flammea, Pectinophora gossypieua, Phthoπmaea operculeua, Pieπs rapae, Pieπs spp Plutella xylostella Prays spp Scirpophaga spp Sesamia spp , Sparganothis spp Spodoptera spp Synanthedon spp . Thaumetopoea spp , Tortπx spp , Tπchoplusia m and Yponomeuta spp , ot the order Coleoptera, tor example Agπotes spp , Anthonomus spp , Atomaπa lineaπs Chaetocnema tibia s,
Figure imgf000010_0001
spp , Curcuho spp , Dermestes spp , Diabrotica spp , Epilachna spp , Eremnus spp , Leptinotarsa decemhneata, Lissoihoptius spp . Melolontha spp , Orvzaephilus spp , Otioihynchus spp , PhK ctinus spp Popilha spp , Psylliodes spp Rhizopertha spp , Scar beidae, Sitophilus spp , Sitoti oga spp , Tenebπo spp , Tπbohum spp and Trogoderma spp , of the order Orthoptera , for example
Blatta spp , Blattella spp , Gryllotalpa spp , Leucophaea maderae, Locusta spp , Peπplaneta spp and Schistocerca spp , of the order Isoptera, for example Reticulitermes spp , of the order Psocoptera. for example Liposce s spp , ot the order Anoplura, foi example
Haematopinus spp , Linognathus spp , Pediculus spp . Pemphigus spp and Phylloxera spp , of the order Mallophaga, tor example Damalinea spp. and Trichodectes spp.; of the order Thysanoptera. for example
Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci and Scirtothrips aurantii; of the order Heteroptera, for example
Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp. Eurygaster spp..
Leptocorisa spp.. Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis,
Scotinophara spp. and Triatoma spp.; of the order Homoptera, for example Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium.
Chrysomphalus dictyospermi, Coccus hesperidum. Empoasca spp., Eriosoma lanigerum, Erythroneura spp.. Gascardia spp., Laodelphax spp., Lecanium corni.
Lepidosaphes spp.. Macrosiphus spp., Myzus spp.. Nephotettix spp., Nilaparvata spp., Paratoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp..
Pseudococcus spp., Psylia spp., Pulvinaria aethiopica, Quadraspidiotus spp.,
Rhopalosiphum spp., Saissetia spp., Scaphoideus spp.. Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri; of the order Hymenoptera, for example Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma.
Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.; of the order Diptera. for example
Aedes spp.. Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp.,
Hyppobosca spp., Liriomyza spp., Lucilia spp.. Melanagromyza spp., Musca spp..
Oestrus spp., Orseolia spp.. Oscinella frit, Pegomyia hyoscyami , Phorbia spp.,
Rhagoletis pomonella. Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; υf the order Siphonaptera for example Ceratophyllus spp. and Xenopsylla cheopis; of the order Thysanura, for example Lepisma saccharina and of the order Acarina. for example
Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptrum oleivora, Polyphagotarsonemus latus, Psoroptes spp.. Rhipicephalus spp., Rhizoglyphus spp.. Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.
Within the scope of this invention it is possible to control in particular pests ( 1 ) of the order Lepidoptera, especially Adoxophyes spp.. Alabama argillaceae, Clysia ambigulla, Clysia pomonelia, Crocidolomia binotalis, Cydia spp., Earias spp., Heliothis spp.. Lobesia botrana, Ostrinia nubilalis, Phthohmea operculeua, Sparganothis spp. and Spodoptera spp.;
(2) of the order Coleoptera in particular the family Curculionidae, more particularly Anthonomus spp., more particularly still A. grandis, very particularly the family Chrysomelidae, most preferably Leptinotarsa decemlineata;
(3) of the order Homoptera
in particular the family Aphididae, more particularly the genus Aphis, most particularly A. gossypii; in particular the family Aleurodidae, preferably Aleurothrixus floccus and Bemisia tabaci; in particular Fainilie Psyllidae, more preferably Psylia spp., (4) of the order Thysanoptera.
in particular the family Thripidae, preferably Frankliniella spp., Thrips palmi and Thrips tabaci;
3)
(5) of the order Acarina, in particular the family Eriophyidae, more particularly Aculus schlechtendali and Phyllocoptruta oleivora;
0 (6) of the order Diptera, in particular the family Agromyzidae, more particularly Liriomyza trifolii;
(7) of the order Isoptera, Reticulitermes spp. 5
(8) of the order Orthoptera, Blattella spp. and Periplaneta spp.
With the novel pesticidal combinations it is possible to control, i.e. inhibit or 0 destroy, in particular pests of the above mentioned type that occur in plants, especially, in cultivated plants and ornamentals, in horticulture and in forestry, or in parts of such plants as fruit, blossoms, leaves, stems, tubers or roots, while in some cases parts of plants that grow later can also be protected against these pests.
5 The pesticidal combination of this invention can be used with advantage for pest control in cereals such as maize or sorghum; fruit such as pome fruit, stone fruit and soft fruit, typically apples, pears, plums, peaches, almonds, cherries, or berries, for example strawberries, raspberries and blackberries; leguminous plants, typically including beans, lentils, peas and soybeans, oil plants such as rape, mustard, poppy, 0 olives, sunflowers, coconut, castor oil plants, cocoa beans and groundnuts; cucurbits such as marrows, cucumber and melons; fibre plants such as cotton, flax, hemp and jute; citrus fruit such as oranges, lemons, grapefruit and mandarins; vegetables such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae such as avocados, cinnamon and camphor, and tobacco, nuts, coffee, egg plants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants or ornamentals, in particular in maize, sorghum, pome fruit, stone fruit, leguminous plants, cucurbits, cotton, citrus fruit, vegetables, egg plants, vines, hops or ornamentals; preferably in maize, sorghum, apples, pears, plums, peaches, peas, soybeans, olives, sunflowers, coconuts, cocoa beans, cabbages, tomatoes, potatoes, vines or cotton; and, most preferably, in vines, citrus fruit, apples, pears, tomatoes and cotton.
Further utilities of the pesticidal combinations of this invention are the protection of stored goods and materials as well as in the hygiene sector, for example, domestic animals and productive livestock against pests of the indicated type.
A particularly advantageous utility of the instant invention is in the protection of structures from nuisance insects including termites and cockroaches and ants.
The invention also relates to compositions comprising a combination of a compound of formula (I) and the pesticide in association with a pesticidally acceptable adjuvant.
Depending on the intended objectives and the prevailing circumstances, the pesticidal compositions are generally emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, coatable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granulates or encapsulations in polymer substances, comprising a compound of formula (I) and the pesticide.
The active ingredients are generally used in those compositions in pure form, the solid compounds being typically used in a specific particle size, or preferably together with at least one of the adjuvants custoinarv in formulation technology, for example extenders such as solvents, or solid carriers, or surface-active compounds ( surfactants).
Suitable solvents are typically aromatic hydrocarbons or partially hydrogenated aromatic hydrocarbons, preferably the fraction of alkylbenzenes containing 8 to 12 carbon atoms, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons such as paraffins or cyclohexane; alcohols such as ethanol, propanol or butanol; glycols and their ethers and esters such as propylene glycol dipropylene glycol ether, diethylene glycol or 2- methoxyethanol or 2-ethoxyethanol: ketones such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents such as N-methylpyrrolid-2-one. dimethyl sulfoxide or N,N-dimethylformamide; water, vegetable oils or epoxidised vegetable oils such as rape oil, castor oil. coconut oil or soybean oil or epoxidised rape oil. castor oil, coconut oil or soybean oil. and silicone oils.
The solid carriers typically used for dusts and dispersible powders are usually natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. To improve the physical properties it is also possible to add highly dispersed silicic acids or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, including pumice, broken brick, sepiolite or bentonite. and suitable nonsorbent carriers are calcite or sand. In addition, innumerable granulated materials of inorganic or organic nature may be used, especially dolomite or pulverized plant residues.
Depending on the type of compound to be formulated, suitable surface-active compounds are nonionic. cationic and/or anionic surfactants or mixtures of surfactants preferably having good emulsifying, dispersing and wetting properties. The surfactants listed below shall be regarded merely as exemplary; many more surfactants customarily employed in formulation technology and suitable for use in the practice of the invention are described in the relevant literature. Nonionic suitactants aie pieterably polyglycol ethei de ativcs ot aliphatic oi cycloaliphatic alcohols, saturated or unsaturated tattv acids and alkylphenols said derivatives containing 3 to 30 glycol ether gioups and 8 to 20 caibon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety ot the alkylphenols Further suitable nonionic surfactants are water-soluble polyadducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypiopylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit Representative examples of nonionic surfactants are nonylphenol polyethoxyethanols, polvefhoxylated castoi oil polyadducts of polypropylene and polyethylene oxide, tπbutylphenol polyethoxylate polyethylene glycol and octylphenol polyethoxylate
Figure imgf000016_0001
acid esters of polyoxyethylene sorbitan, e g polyoxyethylene soibitan tnoleate, are also suitable nonionic surfactants
Cationic suifactants are prelei bly quaternary ammonium salts caπying, as N- substituent, at least one Cg-C2 alkyl radical and, as fuithei substituents, unsubstituted or halogenated lower alkyl, benzyl oi hydroxy-lowei alkyl radicals The salts are preferably in the form of ha des, methyl sulfates or ethyl sulfates Examples are stearyldimethylammonium chloride and benzyl bιs(2- chloroethyl)ethylammonιum bιomιde
Suitable anionic surfactants may be water-soluble soaps as well as watei -soluble synthetic surface-active compounds Suitable soaps aie the alkali metal salts alkaline earth metal salts and unsubstituted or substituted ammonium salts of highei fatty acids (C JO-C2 ), e g the sodium or potassium salts ot oleic ot steaπc acid oi of natural fatty acid mixtures which can be obtained e g fiom coconut oil or tall oil Further suitable soaps are also the fatty acid methyltauπne salts More frequently, however, synthetic surfactants are used, preferably fatty sulfonates. fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates. The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and usually contain a Cg-
C alkyl radical, which also includes the alkyl moiety of acyl radicals. Typical examples are the sodium or calcium salt of ligninsulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain two sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms.
Typical examples of alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or of a condensate of naphthalenesulfonic acid and formaldehyde. Corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids are also suitable.
The compositions will usually comprise 0.1 to 99 %. preferably 0.1 to 95% of a combination of the compound of formula (I) and one or more of the pesticides and 1 to 99.9%, preferably 5 to 99.9%, of at least one solid or liquid adjuvant; usually they will contain 0 to 25%, preferably 0.1 to 20%, of surfactants (in each case percentages are by weight). Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations having a substantial lower concentration of active ingredient. Particularly preferred formulations will be made up as follows: (throughout the specification and accompanying claims, percentages are by weight and the symbol (II) means the pesticide): Emulsi liable concentrates: combination of (I) and (II): 1 to 95 %, preferably 5 to 20 surfactant: 1 to 30 preferably 10 to 20 % solvent: 5 to 98 preferably 70 to 85 %
Dusts: combination of (I) and (II) 0.1 to 10, preferably 0.1 to 1% solid carrier: 99.9 to 90%, preferably 99.9 to 99%
Suspension concentrates: combination of (I) and (II): 5 to 75%, preferably 10 to 50% water: 94 to 24%, preferably 88 to 30% surfactant: 1 to 40%, preferably 2 to 30%
Wettable powders: combination of (I) and (II): 0.5 to 90, preferably 1 to 80% surfactant : 0.5 to 20, preferably 1 to 15% solid carrier: 5 to 99, preferably 15 to 98%
Granules: combination of (I) and (II): 0.5 to 30, preferably 3 to 15% solid carrier. 99.5 to 70%, preferably 97 to 85%
The novel compositions may also contain further solid or liquid adjuvants such as stabilizers, e.g. vegetable oils or epoxidised vegetable oils (e.g. epoxidised coconut oil. rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders and/or tackers, as well as fertilizers or other chemical agents for obtaining special effects, typically including bactericides, fungicides, nematicides, molluscicides or herbicides. The compositions of this invention are prepared in known manner: in the absence of adjuvants, typically by grinding, sieving and/or compressing a solid active ingredient or mixture of active ingredients, for example to a specific particle size; and in the presence of at least one adjuvant, for example by intimately mixing and/or grinding the active ingredient or mixture of active ingredients with the adjuvant or adjuvants. The invention also relates to the preparation of the compositions.
The methods of applying the combinations, i.e. the methods of controlling pests at a locus of the indicated type, typically include spraying, atomizing, dusting, coating, dressing, scattering or pouring, selected in accordance with the intended objectives and prevailing circumstances, and the use of the combinations for controlling pests of the indicated type, are further objects of the invention. Typical rates of concentration are in the range from 0.01 to 1000 ppm, preferably from 0.1 to 500 ppm, of active ingredient. The rate of application may vary over a wide range and will depend on the nature of soil, the type of application (eg. foliar application, seed dressing application to the seed furrow), the cultivated plant, the pest to be controlled, the prevailing climatic conditions and other factors governed by the type of application, time of application and target crop. The rates of application per hectare will usually be from 0.5g/ha to 2000 g/ha, more particularly from 10 to 1000 g/ha, preferably from 20 to 600 g/ha.
A preferred method of application in the field of plant protection is application to the foliage of the plants (foliar application), the number of applications and the rate of application depending on the risk of infestation by the particular pest. However, the active ingredients can also penetrate the plants through the roots (systemic action) by drenching the locus of the plants with a liquid formulation or by applying the active ingredient in solid form to the locus of the plants, for example to the soil, e.g. in granular form (soil application). In paddy rice crops, such granules may be applied to the flooded rice field. It is also contemplated that the invention compi ιses a compound ot toi mula 1 11 in Us tree lorm oi a pesticidally acceptable salt theieot and a pesticide toi simultaneous separate or sequential use in the control oi pests at a locus
The compositions of the invention are also suitable tor protecting plant propagation material, e g seeds such as fruit, tubers or grains, or plant cuttings, against animal pests The propagation material can be treated with the tormulation before planting Seeds, for example, can be dressed before sowing The compounds of the in ention can also be applied to grains (eg by coating), for example by impregnating the grains with a liquid formulation or by coating them with a solid formulation The composition can also be applied to the locus of planting when planting the propagation material, tor example to the seed furrow dining sowing The invention ielates also to these methods of treating plant propagation material and to the plant propagation material so treated
The invention is illustrated by the following non-limiting Examples
Formulation Examples (% = per cent by weight, ratios = weight ratios)
Example FI Emulsifiable concentrate a) b) combination (ratio of compound of formula (I) to (II) 1 1) 25 40 %
Ca dodecylbenzenesulfonate 5 8 % 6 % polyethoxylated castor oil (36 mol EO (that is ethylene oxide)) 5 % tπbutylphenol polyethoxylate
(30 mol EO) 12% 4% cyclohexanone 15% 20% xylene mixture 65 % 25% 20% Emulsions of any desired concentration can be prepared from such concentrates b dilution with water. MW means Molecular Weight.
Example F2: Solutions a) b) c) d) combination (2: 1) 80% 10% 5% 95%
2-methoxyethanol 20% - - - polyethylene glycol MW 400 - 70% - -
N-methyl-2-pyrrolidone _ 20% _ - epoxidised coconut oil 1% 5% petroleum spirit (boiling range 160-190°C) 94 %
The solutions are suitable for use in the form of microdrops.
Example F3- Granulates a) b) c) d) combination ( 1 : 10) 5% 10% 8% 21% kaolin 94% - 79% 547c highly dispersed silica 1% - 13% 7% attapulgite - 90% - 18%
The active ingredients are dissolved in dichloro methane, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated in vacuo.
Example F4- Dusts a) b) combination ( 1 :5) 2% 5% highly dispersed silica 1% 5% talcum 97 % _ kaolin 90%
Ready-to-use dusts are obtained by intimately mixing the carriers with the active ingredients. Example F5: Wettable powders a) b) c) combination ( 1 : 1 ) 25% 50% 75% sodium ligninsulfonate 5% 5% - sodium lauryl sulfate 3% - 5% sodium diisobutylnaphthalene- sulfonate - 6% 10% octylphenol polyethoxylate
(7-8 mol EO) - 2% - highly dispersed silica 5% 10% 10% kaolin 62% 27% -
The active ingredients are mixed with the additives, and the mixture is ground thoroughly in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentrations.
Example F6: Emulsifiable concentrate combination ( 1: 1) 10% octylphenol polyethoxylate
(4-5 mol EO) 3% calcium dodecylbenzenesulfonate 3% polyethoxylated castor oil
(36 mol EO) 4% cyclohexanone 30% xvlene mixture 50%
Emulsions of any desired concentration can be prepared from this concentrate by dilution with water. Example F7: Dusts a) b) combination ( 1 :2) 5% 8% talcum 95% kaolin - 92%
Ready-to-use dusts are obtained by mixing the active ingredients with the carrier and grinding the mixture on a suitable mill.
Example F8: Extruder granules combination ( 1 :3) 10% sodium ligninsulfonate 2% carboxymethyl cellulose 1% kaolin 87%
The active ingredients are mixed with the additives, and the mixture is ground and moistened with water. This mixture is extruded, granulated and subsequently dried in a stream of air.
Example F9: Coated granulates combination ( 1: 1) 3% polyethylene glycol (MW 200) 3% kaolin 94%
In a mixer, the finely ground active ingredients are applied uniformly to kaolin, which has been moistened with polyethylene glycol, to give dust-free coated granules. Example F10: Suspension concentrate combination (2: 1 ) 40% ethylene glycol 10% nonylphenol polyethoxylate
( 15 mol EO) 6% sodium ligninsulfonate 10% carboxymethyl cellulose 1%
37% aqueous formaldehyde solution 0.2% silicone oil in the form of a 75% aqueous emulsion 0.8% water 32%
The finely ground active ingredients are mixed intimately with the additives to give a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.
It is often more expedient to formulate the compound of formula (I) and one of the pesticides singly and then to mix them in the desired ratio in the applicator as a tank mixture in water shortly before application.
Biological Examples (% = per cent by weight, unless otherwise indicated)
A synergistic effect is always obtained whenever the activity of the combination of the compound of formula (I) with a pesticide is greater than the sum of the activities of the individually applied compounds.
For example, the expected pesticidal activity We of a given combination of two pesticides can be calculated as follows (q.v. COLBY, S.R., "Calculating synergistic and antagonstic response of herbicide combinations". Weeds 15, pages 20-22. 1967): We = X + Y ' ( 100 - X) 100
wherein
X = Percentage mortality, compared with untreated controls, after treatment with the compound of formula (I) at a rate of application of p g/hectare (= 0%).
Y = Percentage mortality, compared with untreated controls, after treatment with the pesticide at a rate of application of q kg/hectare.
We = The expected pesticidal activity (percentage mortality compared with untreated controls) after treatment with the compound of formula (I) and the pesticide at a rate of application of p + q kg a.i./ha.
If the actually observed value is greater than the expected value We, then there is synergism.
The synergistic effect of the combination of a compound of formula (I) with an pesticide is demonstrated in the following non-limiting Example.
Example 1 : Action against Fleas
A 15 kg dog is treated with Compound (C) and doramectin. The treatment is made by ingestion of a 5g pill made by the compression of 0. Ig of total active ingredients with 4.0g flour and 0.9g of sugar (some appetizing flavors were also added) The dog is then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
Example 2: Action against Fleas A 50 kg dog is treated with Compound (C) and milbemycin. The treatment is made by ingestion of a 10 g pill made by the compression of 0.3g of total active lngiedients with a 9 7g dog tood The dog is then infested with fleas After one week, no fleas are observed, and eggs are substantially reduced
Example 3: A 5 kg cat is treated with Compound (C) and ivermecun. The treatment is made by ingestion of a 0.5g pill made by the compression of 0.05g of total active ingredients with 0 4g flour and 0. Ig of sugar (some appetizing flavors were also added) The cat was then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
Example 4"
A 15 kg dog is treated with Compound (C) and oxibendazole The treatment is made by ingestion of a 5g pill made by the compression of 0.1 g of total active ingredients with 4.0g flour and 0.9g of sugar (some appetizing flavors were also added) The dog is then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
Example 5:
A 50 kg dog is treated with Compound (C) and fenbendazole. The treatment is made by ingestion of a 10 g pill made by the compression of 0.3g of total active ingredients with a 9.7g dog food. The dog is then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
Example 6: A 5 kg cat is treated with Compound (C) and levamizole. The treatment is made by ingestion of a 0.5g pill made by the compression of 0.05g of total active ingredients with 0.4g flour and O. lg of sugar (some appetizing flavors were also added) The cat was then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced. Example 7:
A 50 kg dog is treated with Compound (C) and nitempyran. The treatment is made by ingestion of a 10 g pill made by the compression of 0.3g of total active ingredients with a 9.7g dog food. The dog is then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
Example 8:
A 5 kg cat is treated with Compound (C) and imidacloprid. The treatment is made by ingestion of a 0.5g pill made by the compression of 0.05g of total active ingredients with 0.4g flour and O. lg of sugar (some appetizing flavors were also added) The cat was then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
Example 9: A 15 kg dog is treated with Compound (C) and pyrantel. The treatment is made by ingestion of a 5g pill made by the compression of 0. Ig of total active ingredients with 4.0g flour and 0.9g of sugar (some appetizing flavors were also added) The dog is then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
Example 10:
A 50 kg dog is treated with Compound (C) and pyrantel palmoate. The treatment is made by ingestion of a 10 g pill made by the compression of 0.3g of total active ingredients with a 9.7g dog food. The dog is then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
Example 1 1 :
A 5 kg cat is treated with Compound (C) and praziquantel. The treatment is made by ingestion of a 0.5g pill made by the compression of 0.05g of total active ingredients with 0.4g flour and 0. Ig of sugar (some appetizing flavors were also added) The cat was then infested with fleas. After one week, no fleas are observed, and eggs are substantially reduced.
Example 12: Artificial growth medium was treated with Compound C at rates of 4, 1, 0.25, 0.06 and 0.015 ppm. Artificial growth medium was treated with Imidacloprid at 6.25 ppm. Artificial growth medium was treated with 5 combinations of Compound C and imidacloprid as indicated below. Artificial growth medium was treated with avermectin at 1.6 ppm. Larvae of Spodoptera Eridania were placed in the media and allowed to stay. Mortality was measured at 3 and 5 days after the larvae were introduced (DAT). The following results in Table 2 show synergism for combinations of avermectin and compound C and imidacloprid and compound C:
Example 13: Example 1 is repeated with nodulisporic acid and Compound C. After one week, there are no fleas on the dog and the number of eggs is reduced.
Spodoptera eridania Mortiilily Test; Compound C and Imidacloprid and Avermectin
Figure imgf000029_0001
L = number living, D = number dead, %F = % foliage consumption, %M = % mortality

Claims

A pesticidal combination comprising a compound of formula ( I):
Figure imgf000030_0001
(I) wherein:
Rja and R2a are independent of one another, hydrogen or halogen; R a is hydrogen or chlorine; R_j.a, R5a and Rga are independent of one another, hydrogen, halogen or alkyl, preferably methyl; A is -CF7CHFCF3, G l, G2, G3 or G4:
Figure imgf000030_0002
(Gl)
(G2) (G3) (G4) wherein R a to R\ a are independent of one another, hydrogen, halogen, alkyl or nitro; and provided that R[a and R2a are not simultaneously hydrogen; and that R4a, R5a and
Rga are not simultaneously hydrogen; and that when A is -CF CHFCF3, Rja and R2a are both fluorine, R3a is hydrogen or chlorine, R4a and Rβa are both hydrogen, and R5a is chlorine; in the free form or in the form of a pesticidally acceptable salt thereof; and a pesticide, preferably an insecticide.
A combination according to Claim 1 wherein A is G l , G2. G3. or
G4.
3. A combination according to Claim 1 or Claim 2 wherein A is Gl .
4. A combination according to any one of the foregoing claims wherein the compound of formula (I) is one wherein Ria=R2a=F' ^3a=^5a=^e ' R4a=Cl; Rόa=H; A=G1 ; R7a=R9a=Cl; R8a=Rl0a=H.
5. A combination according to any one of the foregoing claims wherein the pesticide is
(A) a milbemycin or avermectin; (B) a chloronicotinyl insecticide;
(C) a benzimidazole; or
(D) nodulisporic acid or a derivative thereof.
6. A combination according to any one of claims 1-4 wherein the pesticide is Spinosad or a derivative thereof, AKD-1022, chlorfenapyr, diofenolan, flufenprox, MTI-446, pymetrozine, JKU-0422. nitroscanate, piperazine, praziquantel, pyrantel, or pyrantel palmoate.
7. A combination according to any one of the foregoing claims which is long acting.
8. A composition according to any one of the foregoing claims which is synergistic.
9. A combination according to any one of the foregoing claims wherein the ratio of the compound of formula (I) and the pesticide is synergistic.
10. A composition comprising a combination according to any one of claims 1-9 in association with a pesticidally acceptable adjuvant.
1 1. A method of controlling pests at a locus which comprises applying thereto a combination or composition as described in claims 1- 10.
12. A product comprising a compound of formula (I) in its free form or a pesticidally acceptable salt thereof and a pesticide for simultaneous, separate or sequential use in the control of pests at a locus.
PCT/EP1998/006657 1997-10-09 1998-10-07 Pesticidal combination WO1999018796A2 (en)

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US9730453B2 (en) 2008-12-31 2017-08-15 Makhteshim Chemical Works Ltd. Method for controlling insects in plants
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AU2009334332B2 (en) * 2008-12-31 2015-04-30 Adama Makhteshim Ltd. Method for controlling insects in plants
WO2011092141A3 (en) * 2010-01-28 2012-03-29 Syngenta Participations Ag Insecticidal combination
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CN103734143A (en) * 2013-12-28 2014-04-23 上海艳紫化工科技有限公司 Spinosad compound insecticidal suspending agent

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