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WO1998039972A1 - Combinaison pesticide - Google Patents

Combinaison pesticide Download PDF

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Publication number
WO1998039972A1
WO1998039972A1 PCT/EP1998/001224 EP9801224W WO9839972A1 WO 1998039972 A1 WO1998039972 A1 WO 1998039972A1 EP 9801224 W EP9801224 W EP 9801224W WO 9839972 A1 WO9839972 A1 WO 9839972A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
spp
formula
hydrogen
haloalkyl
Prior art date
Application number
PCT/EP1998/001224
Other languages
English (en)
Inventor
Charles Lee Haas
Michael Pilato
Philip Reid Timmons
Tai-Teh Wu
Scot Kevin Huber
Bernard Leroux
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 AU68268/98A priority Critical patent/AU6826898A/en
Priority to US09/058,359 priority patent/US6057355A/en
Publication of WO1998039972A1 publication Critical patent/WO1998039972A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom

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):
  • Rl a and R.2 a are independent of one another, hydrogen or halogen
  • R3 a is hydrogen, chlorine or alkyl
  • R4 a , R5a and R6 a are independent of one another, alkyl, preferably methyl hydrogen, or halogen
  • A is Gl, G2, G3 or G4:
  • R ⁇ a to i6 a are independent of one another, hydrogen, halogen, alkyl or nitro; and provided that R ⁇ a and R2 a are not simultaneously hydrogen; and that R4 a , R5 a and Rg a are not simultaneously hydrogen; in the free form or in the form of a pesticidally acceptable salt thereof, and a 1- arylpyrazole of formula (II):
  • Rj is CN or methyl;
  • R 2 is S(O) n R 3 ;
  • R3 is alkyl or haloalkyl;
  • R4 is selected from the group consisting of hydrogen, halogen,
  • R5 and Rg are independently selected from a hydrogen atom, alkyl, haloalkyl, -C(O)alkyl, -C(O)OR 75 -S(O) r CF 3 ; or R5 and R6 form together a divalent alkylene radical which may be interrupted by one or more heteroatoms, preferably selected from oxygen, nitrogen and sulfur;
  • R7 is selected from alkyl and haloalkyl
  • Rg is selected from alkyl, haloalkyl and hydrogen
  • R9 is selected from hydrogen and alkyl
  • Rj ⁇ is selected from phenyl or heteroaryl each of which is optionally substituted by one or more hydroxy, halogen,
  • X is selected from nitrogen and C-R12;
  • Rl j and R ⁇ are independently selected from halogen or hydrogen
  • Rl3 is selected from halogen, haloalkyl, haloalkoxy, -S(O)qCF3, -SF5; m, n, q, r are independently selected from 0, 1, and 2; provided that when R ⁇ is methyl, R3 is haloalkyl, R4 is NH2, Ri 1 is Cl,
  • R 13 is CF3, and X is N.
  • alkyl groups of formula (I) are optionally substituted by one or more halogens.
  • the alkyl and alkoxy groups and moieties of the formula (II) are preferably lower alkyl and alkoxy groups, that is, groups having one to four carbon atoms.
  • the haloalkyl and haloalkoxy groups likewise preferably have one to four carbon atoms.
  • the haloalkyl and haloalkoxy groups can bear one or more halogen atoms; preferred groups of this type include -CF3 and -OCF3. It shall be understood that the ring formed by the divalent alkylene radical represented by R5 and R ⁇ and including the nitrogen atom to which R5 and Rg are attached is generally a 5, 6, or 7-membered ring.
  • Rla and R2 a are independently selected from halogen, preferably chlorine or fluorine;
  • A is Gl;
  • R3 a is methyl
  • R4 a , R5a nd Rg a are independently hydrogen, halogen, preferably chlorine, or methyl; or
  • R7 a , R8a» R9a and RiOa are independently selected from hydrogen or halogen.
  • a preferred group of 1-arylpyrazoles for use in the present invention are those of formula
  • Rl is CN
  • R4 is -NR 5 R 6 ;
  • R5 and R are independently selected from the hydrogen atom, alkyl, haloalkyl, C(O)alkyl, C(O)OR 7 ;
  • X is C-R12;
  • Rl3 is selected from a halogen atom, haloalkyl, haloalkoxy, and -SF 5 .
  • a particularly preferred group of 1 -arylpyrazoles for use in the present invention are those of formula (II) wherein:
  • Rl is CN
  • R4 is -NR5R6;
  • R5 and Rg are independently selected from the hydrogen atom, alkyl, haloalkyl, C(O)alkyl, C(O)OR 7 ;
  • X is C-R 2;
  • Rl3 is selected from a halogen atom, haloalkyl, haloalkoxy, and -SF5.
  • a very particularly preferred compound of formula (II) is 5-amino-(2,6-dichloro- ⁇ , , ⁇ -trifluoro-p-tolyl)-4-trifluoromethyl-sulf ⁇ nylpyrazole-3- carbonitrile, known as fipronil.
  • a preferred combination is that of a compound of formula (I) and a 1-arylpyrazole of formula (II) wherein Ri is CN, R2 is -S(O)Et, R 11 is Cl, X is C-Cl, R13 is CF3 and R4 is selected from -NH2, -NHMe or -NHEt, particularly 5-amino-(2,6-dichloro- ⁇ , ⁇ , ⁇ - trifluoro-p-tolyl)-4-ethylsulf ⁇ nylpyrazole-3-carbonitrile also known as Compound B.
  • a particularly preferred combination is that of a compound of formula (I) wherein
  • the pesticidally acceptable salts of the compound of formula (I) are typically addition salts of inorganic and organic acids, preferably of hydrochloric acid, hydrobromic 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 1-arylpyrazole of formula (II) is also preferred.
  • the pesticidal combination of this invention will preferably contain compound of formula (I) and 1-arylpyrazole in a weight ratio of 1:50 to 50:1, especially in a ratio from 1 :20 to 20: 1, more particularly from 10: 1 to 1: 10, still more particularly from 5: 1 to 1:5, very particularly from 2: 1 to 1:2, for example in the ratio 1: 1.
  • the combination of the pesticide of formula (I) and the 1-arylpyrazoles of formula (II) provides a generally long acting effect, generally from 30 to 180 days, preferably from 180 to 240 days, more preferably from 240 to 300, and most preferably from 300 to 360 days after treatment.
  • 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 potentiates the activity ranges of both compounds from two points of view.
  • the concentrations of the compound of formula (I) and the 1- arylpyrazoles of formula (II) are 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 the invention also have a useful antifeeding effect.
  • Such an antifeeding effect is generally not seen with the individual compounds of formula (I) or salts thereof.
  • An antifeeding effect is advantageous in that regardless of the killing action of the active ingredients, the plant is protected from damage and therefore may provide effective protection to the locus so treated with the active ingredient.
  • 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 warmblooded 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 parasites, preferably both ticks and fleas, especially those of pets, such as dogs or cats, particularly cats.
  • one administration per week preferably one administration per month, more preferably one administration every two to three months, even more preferably one administration every four to six months, even more preferably one administration every seven to eight months, and most preferably every nine to twelve months or higher provide generally good efficacy.
  • the appropriate doses are generally from 5 to 50 mg/kg, preferably 10 to 30 mg/kg for the compound of formula (II), "mg/kg” in this instance indicating the milligrams of compound of formula (II) per kilogram of body weight of animal.
  • the amount the compound of formula (I) compound present in the mixture will vary according to the efficacy the active ingredient and the precise conditions of use and is generally from 1 to 100 mg/kg, preferably from 5 to 80 mg/kg, more preferably from 10 to 50 mg/kg, and most preferably from 10 to 20 mg/ kg..
  • parasites as used in the specification and claims is meant to encompass all endoparasites and ectoparasites of warm-blooded animals as well as pests that breed in the manure of the animals.
  • the aforementioned animal pests typically include: of the order Lepidoptera
  • Grapholita spp. Hedya nubiferana, Heliothis spp., Hellula andalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella.
  • Lithocllethis spp. Lithocllethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypieua, Phthorimaea operculeua, Pieris rapae, Pieris spp., Plutella xylostella.
  • Blatta spp. Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.; of the order Isoptera, for example Reticulitermes spp.; of the order Psocoptera, for example Liposcelis spp.; of the order Anoplura, for example
  • Haematopinus spp. Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp-; of the order Mallophaga, for example
  • Scirtothrips aurantii of the order Heteroptera, 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,
  • Chrysomphalus dictyospermi Coccus hesperidum. Empoasca spp., Eriosoma lanigerum,
  • Macrosiphus spp. Myzus spp.. Nephotettix spp., Nilaparvata spp., Paratoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp.. Pseudococcus spp., Psylia spp.,
  • Hoplocampa spp. Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.; of the order Diptera. for example
  • 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.
  • Siphonaptera for example Ceratophyllus spp. and Xenopsylla cheopis
  • Thysanura for example Lepisma saccharina
  • Acarina for example
  • 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;
  • representative parasites which may be controlled by the method of this invention include members of the Arthropoda (Arthropods), including mites in suborder Mesostigmata, Sarcoptiformes, Trombidiformes and Onchychopalpida; sucking and biting lice in orders Anoplura and Mallophaga; ticks in the families Ixodidac and Argasidae; fleas in the families Pulicidae, Ceratophyllidae, and others; Cimex and other Hemiptera; Triatominae and other Heteroptera; and myiasis-related fly larvae and blood sucking adults (including mosquitoes) in the suborders Brachycera, Cyclorrhapha and Nematocera.
  • Arthropods Arthropods
  • Nematoda helminths included in the Nematoda (Strongylidia, including but not limited to Strongyloidea, Ancylostomatoidea, Trichostrongyloidea and Metastrongyloidea; Ascarida [Ascaris]; Filariina, such as but not limited to Onchocerca and Dirofilaria; Rhabditida; and trichinellida); Cestoidea, especially Cyclophyllidea, and Trematoda, including Strigeatoidea such as Schistosoma; Echinostomida such as Fasciola; and Plagiorchiida such as Paragonimus.
  • Other parasites which may be controlled by compounds represented by generic formula (I) include Acanthocephala such as Macracanthorhvnchus or Moniliformis, and Pentastomida, especially Liguatula; and protozoa, especially Coccidia such as Eimeria and Plasmodium, Piroplasmea such as Babesia; Toxoplasmea such as Tripanosoma; Trichomonadidae such as Trichomonas and Entamoebidae such as Entamoeba.
  • arthropods such as mites (mesostigmatids, itch, mange, scabies, chiggers), ticks (soft-bodied and hard-bodied), lice (sucking, biting), fleas (dog flea, cat flea, oriental rat flea, human flea), true bugs (bed bugs, Triatomid bugs), bloodsucking adult flies (horn fly, horse fly, stable fly, black fly, deer fly, louse fly, tsetse fly, mosquitoes), and parasitic fly maggots 9bot fly, blow fly, screwworm, cattle grub, fleeceworm); helminths such as nematodes (threadworm, lungworm, hookworm, whipworm, nodular worm, stomach worm, round worm, pinworm, heartworm), cestodes (tapeworms) and trematodes (liver fluke, blood fluke); protozoa such as mites (mesostigmatids, itch, mange, scabies,
  • 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, 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
  • 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.
  • the method of the present invention comprises known methods of application of the compound of the invention to the domestic animal including spraying, rubbing, application by spotting, dip, collar, ear tag, or orally.
  • the compounds of the invention are administered orally (that is into the digestive tract) or via injection. Most preferably the compounds are administered orally via a bolus.
  • the frequency of treatment of the domestic animal to be treated by the compound of formula (I) is generally from about once per week to about once per year, preferably from about once every two weeks to about once every six months, and most preferably from about once per month to about once every three months.
  • the present invention also relates to a use of a combination comprising a compound of formula (I)
  • R3 a is hydrogen, chlorine or alkyl
  • R4 a , R5a and Rg a are independent of one another, alkyl, preferably methyl hydrogen, or halogen;
  • A is Gl, G2, G3 or G4:
  • Rl is CN or methyl
  • R 2 is S(O) n R 3 ;
  • R3 is alkyl or haloalkyl
  • R4 is selected from the group consisting of hydrogen, halogen,
  • R5 and R(5 are independently selected from a hydrogen atom, alkyl, haloalkyl, -C(O)alkyl, -C(O)OR 7> -S(O) r CF3; or R5 and R 6 form together a divalent alkylene radical which may be interrupted by one or more heteroatoms, preferably selected from oxygen, nitrogen and sulfur;
  • R 7 is selected from alkyl and haloalkyl;
  • Rg is selected from alkyl, haloalkyl and hydrogen;
  • R 9 is selected from hydrogen and alkyl;
  • RlO is selected from phenyl or heteroaryl each of which is optionally substituted by one or more hydroxy, halogen,
  • X is selected from nitrogen and C-R12;
  • Rl and R 12 are independently selected from halogen or hydrogen;
  • Rl3 is selected from halogen, haloalkyl, haloalkoxy, -S(O)qCF3,
  • m, n, q, r are independently selected from 0, 1, and 2; provided that when Ri is methyl, R3 is haloalkyl, R4 is NH2, Rl l is Cl, Rl3 is CF3, and X is N; to manufacture a composition for the control of parasites in or on an animal.
  • the present invention also relates to a method of cleaning animals in good health comprising the application to the animal of a combination of a compound or formula (I):
  • R3 a is hydrogen, chlorine or alkyl
  • R4a > R5a an d R ⁇ a are independent of one another, alkyl, preferably methyl hydrogen, or halogen;
  • A is Gl, G2, G3 or G4:
  • R 7a to Ri6a are independent of one another, hydrogen, halogen, alkyl or nitro; and provided that R ⁇ a and R2 a are not simultaneously hydrogen; and that R4 a , R5 a and Rg a are not simultaneously hydrogen; in the free form or in the form of a pesticidally acceptable salt thereof, and a 1- arylpyrazole of formula (II):
  • R is CN or methyl
  • R 2 is S(O) n R 3 ;
  • R3 is alkyl or haloalkyl
  • R4 is selected from the group consisting of hydrogen, halogen,
  • R5 and R ⁇ are independently selected from a hydrogen atom, alkyl, haloalkyl, -C(O)alkyl, -C(O)OR 7> -S(O) r CF 3 ; or R5 and Rg form together a divalent alkylene radical which may be interrupted by one or more heteroatoms, preferably selected from oxygen, nitrogen and sulfur;
  • R 7 is selected from alkyl and haloalkyl;
  • Rg is selected from alkyl, haloalkyl and hydrogen;
  • R is selected from hydrogen and alkyl;
  • RlO is selected from phenyl or heteroaryl each of which is optionally substituted by one or more hydroxy, halogen,
  • X is selected from nitrogen and C-R12;
  • Rl 1 and R12 are independently selected from halogen or hydrogen;
  • Rl3 is selected from halogen, haloalkyl, haloalkoxy, -S(O)qCF3,
  • m, n, q, r are independently selected from 0, 1, and 2; provided that when Ri is methyl, R3 is haloalkyl, R4 is NH2, l l is Cl, Rl3 is CF3, and X is N; or a composition comprising the combination to the animal.
  • the method of cleaning an animal is not a method of treatment of the animal body per se, because
  • the cleaning of the animal is not intended to be done by veterinary personnel, but by persons interested in the cleaning of the animal; and (c) the purpose of such cleaning is to avoid unpleasant conditions for humans and the environment in which humans inhabit so as to not infest the said humans with arthropods carried by the animal.
  • the present invention also relates to a composition
  • a composition comprising an arthropocidally effective, substantially non-emetic amount of a compound of formula (I) and an acceptable carrier.
  • Acceptable carriers acceptable for the use of the compounds are generally known to the skilled addressee concerned with arthropod control in animals, particularly domestic animals.
  • 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 1-arylpyrazole of formula (II) 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 a 1- arylpyrazole of formula (II).
  • 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 customary 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
  • 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.
  • Another type of solid carrier that may be used in the present invention is a biodegradable polymer, particularly one which degrades inside the animal's body over an extended period of time, preferably one administration per month, more preferably two to three months, even more preferably four to six months, much more preferably seven to eight months, and most preferably nine to twelve months.
  • 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 surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
  • nonionic surfactants are water-soluble polyadducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene 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.
  • nonionic surfactants are nonylphenol polyethoxyethanols, polyethoxylated castor oil, polyadducts of polypropylene and polyethylene oxide, tributylphenol polyethoxylate, polyethylene glycol and octylphenol polyethoxylate.
  • Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable nonionic surfactants.
  • Cationic surfactants are preferably quaternary ammonium salts carrying, as N-substituent, at least one C -C22 alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals.
  • the salts are preferably in the form of halides, methyl sulfates or ethyl sulfates. Examples are stearyldimethylammonium chloride and benzyl bis(2-chloroethyl)ethylammonium bromide.
  • Suitable anionic surfactants may be water-soluble soaps as well as water-soluble synthetic surface-active compounds.
  • Suitable soaps are the alkali metal salts, alkaline earth metal salts and unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22X e-g- the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tall oil.
  • Further suitable soaps are also the fatty acid methyltaurine salts.
  • fatty sulfonates 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 C -C22 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.
  • 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 1-arylpyrazoles of formula (II) 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.
  • Particularly preferred formulations will be made up as follows: (throughout, percentages are by weight):
  • Emulsifiable 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 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.
  • 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 comprises a compound of formula (I) in its free form or a pesticidally acceptable salt thereof and a 1-arylpyrazole of formula (II) for simultaneous, separate or sequential use in the control of pests at a locus.
  • compositions of the invention are also suitable for 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 formulation before planting. Seeds, for example, can be dressed before sowing.
  • the compounds of the invention 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, for example to the seed furrow during sowing.
  • the invention relates also to these methods of treating plant propagation material and to the plant propagation material so treated.
  • Example FI Emulsifiable concentrate a) b) c) combination (ratio of compound of formula (I) to a compound (II) 1: 1) 25 40 % 50 %
  • Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
  • Example F2 Solutions a) b) c) d) combination (2: 1) 80% 10% 5% 95%
  • 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% 54% highly dispersed silica 1% - 13% 7% attapulgite - 90% - 18%
  • the active ingredients are dissolved in dichloromethane, 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 one of the pesticides (II) is greater than the sum of the activities of the individually applied compounds.
  • Y Percentage mortality, compared with untreated controls, after treatment with a arylpyrazole of formula (II) at a rate of application of q kg/hectare.
  • Example 1 Action against Spodoptera Eridania
  • Artificial growth medium is treated with Compound C at rates of 0.5, 0.25, 0.125, 0.06, and 0.03 ppm. Artificial growth medium is treated with Compound A at rates of 8, 4, 2, 1 and 0.5 ppm. Artificial growth medium is treated with the following rate combinations of Compound C and Compound A: (0.5 + 8); (0.25 + 4); (0.125 + 2); (0.06 + 1); and (0.03 +0.5).
  • Larvae of Spodoptera Eridania are placed in the medium and allowed to stay for days. Mortality is measured at 4 and 7 days after the larvae are allowed to begin to feed. The following results which show synergism in three of five rates are obtained at 4 days after treatment:
  • Example 1 The procedure of Example 1 was followed using cotton leaves sprayed to runoff with combination using the rates shown in the following tables.
  • the tables indicate individual data at the date after treatment indicated.
  • Cats, housed in cages with wire mesh bottoms, are infested with about 50 fleas at 1 week intervals for the course of the study.
  • the cats are treated by a subcutaneous injection of a mixture of Compound C at a rate of 10 mg/kg and Compound B at a rate of 20 mg/kg in polyethylene glycol.
  • sweepings of debris which are collected on plywood boards placed beneath the cages are combined with flea rearing media and evaluated for development of flea progeny.
  • Adult fleas on the cats are counted weekly, two days after each infestation, for the duration of the study by combing the cats. Greater than 95% control of development of flea progeny and >90% control of flea adults is maintained for 26 and 52 weeks post treatment.
  • Cats, housed in cages with wire mesh bottoms are infested with about 50 fleas at 1 week intervals for the course of the study.
  • the cats are treated by oral gavage via stomach tube of a mixture of Compound C at a rate of 20 mg/kg and Compound A at a rate of 20 mg/kg in a 1: 1 v/v DMSO/corn oil mixture.
  • sweepings of debris which are collected on plywood boards placed beneath the cages, ' are combined with flea rearing media and evaluated for development of flea progeny.
  • Adult fleas on the cats are counted weekly, two days after each infestation, for the duration of the study by combing the cats. Greater than 95% control of development of flea progeny and >90% control of flea adults is maintained for 26 and 52 weeks post treatment.

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

Abstract

L'invention concerne une combinaison pesticide comprenant un composé de la formule (I) et un 1-arylpyrazole de la formule (II).
PCT/EP1998/001224 1997-03-11 1998-03-05 Combinaison pesticide WO1998039972A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU68268/98A AU6826898A (en) 1997-03-11 1998-03-05 Pesticidal combination
US09/058,359 US6057355A (en) 1997-08-05 1998-04-10 Pesticidal combination

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US81542997A 1997-03-11 1997-03-11
US08/815,429 1997-03-11
US5479597P 1997-08-05 1997-08-05
US60/054,795 1997-08-05

Publications (1)

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WO1998039972A1 true WO1998039972A1 (fr) 1998-09-17

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AR (1) AR011962A1 (fr)
AU (1) AU6826898A (fr)
WO (1) WO1998039972A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0963695A1 (fr) * 1998-06-08 1999-12-15 Rhone Poulenc Agro Méthode insecticide
WO2001019189A1 (fr) * 1999-09-14 2001-03-22 Aventis Cropscience S.A. Compositions et procede pour lutter contre les insectes nuisibles au riz et a d'autres recoltes
US6413542B1 (en) 1996-03-29 2002-07-02 Merial Direct pour-on antiparasitic skin solution and methods for treating, preventing and controlling myasis
WO2005009129A1 (fr) 2003-02-26 2005-02-03 Merial Limited Derives de 1-n-arylpyrazole utilises dans la prevention de maladies vehiculees par les anthropodes ou par les moustiques
US8242161B2 (en) 2003-12-17 2012-08-14 Merial Limited Topical formulations comprising 1-N-arylpyrazole derivatives and amitraz
US8450357B2 (en) 2008-11-19 2013-05-28 Merial Limited Compositions comprising an aryl pyrazole and/or a formamidine, methods and uses thereof
WO2013126694A1 (fr) 2012-02-23 2013-08-29 Merial Limited Composition topique comprenant du fipronil et de la perméthrine et ses méthodes d'utilisation
US9173728B2 (en) 2008-11-19 2015-11-03 Merial Inc. Multi-cavity container having offset indentures for dispensing fluids

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EG22187A (en) * 1999-04-15 2002-10-31 Aventis Cropscience Sa New composition

Citations (8)

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WO1986003941A1 (fr) * 1984-12-28 1986-07-17 Union Carbide Corporation Utilisation de composes d'acyl-uree pour l'elimination d'endoparasites et d'ectoparasites chez les animaux a sang chaud
WO1986005780A1 (fr) * 1985-03-29 1986-10-09 Union Carbide Corporation Composes pesticides a base d'uree de 1-(4-phenoxyphenyl)-3-benzoyle, et procede de preparation
EP0255803A1 (fr) * 1986-08-06 1988-02-10 Ciba-Geigy Ag Procédé pour empêcher que les chiens et les chats soient à nouveau infestés par les puces
EP0295117A1 (fr) * 1987-06-12 1988-12-14 Rhone-Poulenc Agriculture Limited Dérivés de N-phénylpyrazoles
FR2713889A1 (fr) * 1993-12-21 1995-06-23 Sumitomo Chemical Co Composition pesticide contenant un régulateur de la croissance des insectes et un dérivé de N-aryldiazole.
WO1995033380A1 (fr) * 1994-06-08 1995-12-14 Ciba-Geigy Ag Composition synergique
DE19548874A1 (de) * 1995-12-27 1997-07-03 Bayer Ag Synergistische insektizide Mischungen
WO1997036485A1 (fr) * 1996-03-29 1997-10-09 Merial Association insecticide contre les puces des mammiferes, notamment des chiens et chats

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986003941A1 (fr) * 1984-12-28 1986-07-17 Union Carbide Corporation Utilisation de composes d'acyl-uree pour l'elimination d'endoparasites et d'ectoparasites chez les animaux a sang chaud
WO1986005780A1 (fr) * 1985-03-29 1986-10-09 Union Carbide Corporation Composes pesticides a base d'uree de 1-(4-phenoxyphenyl)-3-benzoyle, et procede de preparation
EP0255803A1 (fr) * 1986-08-06 1988-02-10 Ciba-Geigy Ag Procédé pour empêcher que les chiens et les chats soient à nouveau infestés par les puces
EP0295117A1 (fr) * 1987-06-12 1988-12-14 Rhone-Poulenc Agriculture Limited Dérivés de N-phénylpyrazoles
FR2713889A1 (fr) * 1993-12-21 1995-06-23 Sumitomo Chemical Co Composition pesticide contenant un régulateur de la croissance des insectes et un dérivé de N-aryldiazole.
WO1995033380A1 (fr) * 1994-06-08 1995-12-14 Ciba-Geigy Ag Composition synergique
DE19548874A1 (de) * 1995-12-27 1997-07-03 Bayer Ag Synergistische insektizide Mischungen
WO1997036485A1 (fr) * 1996-03-29 1997-10-09 Merial Association insecticide contre les puces des mammiferes, notamment des chiens et chats

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6413542B1 (en) 1996-03-29 2002-07-02 Merial Direct pour-on antiparasitic skin solution and methods for treating, preventing and controlling myasis
EP0963695A1 (fr) * 1998-06-08 1999-12-15 Rhone Poulenc Agro Méthode insecticide
WO2001019189A1 (fr) * 1999-09-14 2001-03-22 Aventis Cropscience S.A. Compositions et procede pour lutter contre les insectes nuisibles au riz et a d'autres recoltes
US6492357B1 (en) 1999-09-14 2002-12-10 Aventis Cropscience, S.A. Compositions and methods for controlling insects which damage rice and other crops
WO2005009129A1 (fr) 2003-02-26 2005-02-03 Merial Limited Derives de 1-n-arylpyrazole utilises dans la prevention de maladies vehiculees par les anthropodes ou par les moustiques
US8242161B2 (en) 2003-12-17 2012-08-14 Merial Limited Topical formulations comprising 1-N-arylpyrazole derivatives and amitraz
US9066515B2 (en) 2003-12-17 2015-06-30 Merial, Inc. Topical formulations comprising 1-N-arylpyrazole derivatives and amitraz
US8450357B2 (en) 2008-11-19 2013-05-28 Merial Limited Compositions comprising an aryl pyrazole and/or a formamidine, methods and uses thereof
US8921408B2 (en) 2008-11-19 2014-12-30 Merial Limited Compositions comprising an aryl pyrazole and/or a formamidine, methods and uses thereof
US9173728B2 (en) 2008-11-19 2015-11-03 Merial Inc. Multi-cavity container having offset indentures for dispensing fluids
WO2013126694A1 (fr) 2012-02-23 2013-08-29 Merial Limited Composition topique comprenant du fipronil et de la perméthrine et ses méthodes d'utilisation
EP3659439A1 (fr) 2012-02-23 2020-06-03 Boehringer Ingelheim Animal Health USA Inc. Composition topique comprenant du fipronil et de la perméthrine et ses procédés d'utilisation

Also Published As

Publication number Publication date
AU6826898A (en) 1998-09-29
AR011962A1 (es) 2000-09-13

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