WO1998023158A1 - Compositions insecticides et procedes - Google Patents

Compositions insecticides et procedes Download PDF

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Publication number
WO1998023158A1
WO1998023158A1 PCT/GB1997/003056 GB9703056W WO9823158A1 WO 1998023158 A1 WO1998023158 A1 WO 1998023158A1 GB 9703056 W GB9703056 W GB 9703056W WO 9823158 A1 WO9823158 A1 WO 9823158A1
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WIPO (PCT)
Prior art keywords
formula
alkyl
alkenyl
alkynyl
optionally substituted
Prior art date
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PCT/GB1997/003056
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English (en)
Inventor
Martin Stephen Clough
Fergus Gerard Paul Earley
Stuart John Dunbar
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Zeneca Limited
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.)
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Publication date
Priority to APAP/P/1999/001537A priority Critical patent/AP1068A/en
Application filed by Zeneca Limited filed Critical Zeneca Limited
Priority to AU48763/97A priority patent/AU4876397A/en
Priority to IL13006097A priority patent/IL130060A0/xx
Priority to JP52438598A priority patent/JP2001504511A/ja
Priority to SK693-99A priority patent/SK69399A3/sk
Priority to CZ991842A priority patent/CZ184299A3/cs
Priority to SI9720085A priority patent/SI20002A/sl
Priority to EA199900504A priority patent/EA002032B1/ru
Priority to EP97911351A priority patent/EP0944319A1/fr
Priority to BR9713146-6A priority patent/BR9713146A/pt
Priority to CA002271747A priority patent/CA2271747A1/fr
Publication of WO1998023158A1 publication Critical patent/WO1998023158A1/fr
Priority to BG103516A priority patent/BG103516A/xx

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

Definitions

  • This invention relates to insecticidal compositions useful for the control of resistant insect pests and to a method of combating resistant insect pests therewith.
  • the present invention provides an insecticidal composition
  • a first insecticidally active ingredient to which insect pests have developed a degree of resistance
  • an insecticidally inert carrier or diluent and, optionally, one or more surface active agents, characterised in that the composition further contains a sufficient amount of a compound of formula (I):
  • Ar is phenyl, pyridinyl, pyridazinyl or pyrazinyl, all being optionally substituted with halogen (especially fluorine, chlorine or bromine), C alkyl (especially methyl), C M alkoxy (especially methoxy), C, ⁇ alkenyl, C 2 ⁇ , alkynyl or cyano;
  • R is hydrogen, C M alkyl (optionally substituted with cyano, CO 2 (C alkyl) or phenyl (itself optionally substituted with halogen, C M alkyl, C M alkoxy, C M haloalkyl or C haloalkoxy)), C 2 ⁇ haloalkyl (the ⁇ -carbon being unsubstituted), C 3 .
  • the ratio of the first insecicidally active ingredient: compound of formula (I) is in the range 1 :100 to 100:1 (for example 1 :10 to 10:1) weight/weight.
  • Halogen includes fluorine, chlorine, bromine and iodine.
  • Alkyl moieties can be in the form of straight or branched chains, for example methyl, ethyl, n- or iso-propyl, or n-, sec-, iso- or tert-butyl.
  • Haloalkyl is especially fluoroalkyl (for example trifluoromethyl, 2,2,2-trifluoroethyl or 2,2-difluoroethyl) or chloroalkyl.
  • fluoroalkyl for example trifluoromethyl, 2,2,2-trifluoroethyl or 2,2-difluoroethyl
  • chloroalkyl for example, 2,2,2-trifluoroethyl or 2,2-difluoroethyl.
  • Alkenyl and alkynyl moieties can be in the form of straight or branched chains, and, where appropriate, the alkenyl moieties can be of either (E)- or (Z)-conf ⁇ guration. Examples are vinyl, allyl and propargyl.
  • Suitable acid addition salts include those with an inorganic acid such as hydrochloric, hydro bromic, sulfuric, nitric and phosphoric acids, or an organic carboxylic acid such as oxalic, tartaric, lactic, butyric, toluic, hexanoic and phthalic acids, or sulphonic acids such as methane, benzene and toluene sulphonic acids.
  • organic carboxylic acids include haloacids such as trifluoroacetic acid.
  • the present invention provides novel insecticidal compositions comprising an insecticidally active ingredient to which insect pests have developed a degree of resistance in association with an insecticidally inert diluent and, optionally, one or more surface active agents, characterised in that the composition contains an sufficient amount of a compound of formula (la):
  • X represents hydrogen or halogen, more particularly chloro or bromo
  • R repesents lower alkyl or lower haloalkyl of up to 4 carbon atoms, or benzyl or halobenzyl, to boost the activity of the composition to overcome the resistance.
  • the present invention provides a compound of formula (I) wherein Ar is pyridin-3-yl optionally substituted in the 5-position with chlorine or bromine.
  • the invention provides a method of improving the activity of an insecticide against insect pests which have developed a level of resistance to such insecticides which comprises applying to the pests or the locus of the pests an insecticidal composition comprising the insecticide in association with a compound of formula (I).
  • Organophosphates Chlorpyrifos, profenofos, acephate, dimethoate, parathion-methyl, terbufos, monocrotophos, sulprofos, prothiofos.
  • Carbamates Aldicarb, carbofuran, carbaryl, methomyl, fenobucarb, pirimicarb.
  • Benzoyl ureas Diflubenzuron, chlorfluazuron, teflubenzuron, hexaflumuron, flufenoxuron, lufenuron, flucycloxuron. Others: Amitraz, clofentezine, fenpyroximate, hexythiazox, propargite, tebufenpyrad, fenazaquin, pyridaben, spinosad, triazamate, buprofezin, abamectin, fipronil, tebufenozide, diofenolan, imidacloprid. A further example is chlorfenapyr. Amongst the insect pest which are becoming more difficult to control because of the development of resistance to one or more of the above insecticides are the following:
  • Homoptera Homoptera: Aphids (for example Myzus persicae, Myzus nicotianae, Aphis fabae, Aphis gossypii, Rhopalosiphum padi, Aphis nasturtii, Macrosiphum euphorbiae).
  • Whitefly for example Bemisia tabaci, Bemisia argentifolii, Trialeurodes vapor ariorum).
  • Planthoppers for example Nephotettix cincticeps, Nilaparvata lugens.
  • Heteroptera for example Lygus lineolaris, Lygus hesperus
  • Lepidoptera for example Plutella xylostella, Heliothis virescens, Spodoptera exigua, Laspeyresia pomonell .
  • Diptera for example Liriomyza t ⁇ folii).
  • Coleoptera for example Phaedon cochlearae, Anthonomus grandis
  • the invention also provides a composition comprising spinosad and a compound of formula (I):
  • Ar CN wherein A represents a bidentate group of formula -CH 2 CH 2 -; Ar is phenyl, pyridinyl, pyridazinyl or pyrazinyl, all being optionally substituted with halogen (especially fluorine, chlorine or bromine), C,_ 4 alkyl (especially methyl), C,. 4 alkoxy (especially methoxy), C 2 .
  • halogen especially fluorine, chlorine or bromine
  • C,_ 4 alkyl especially methyl
  • C,. 4 alkoxy especially methoxy
  • alkenyl, C 2 _ 4 alkynyl or cyano R is hydrogen, C alkyl (optionally substituted with cyano, CO 2 (C M alkyl) or phenyl (itself optionally substituted with halogen, C alkyl, C M alkoxy, C haloalkyl or C M haloalkoxy)), C 2 haloalkyl (the ⁇ -carbon being unsubstituted), C 3J( alkenyl or C 3 ⁇ alkynyl; provided that when R is alkenyl or alkynyl said group does not have an unsaturated carbon atom bonding directly to the ring nitrogen of formula (I); or an acid addition salt, quaternary ammonium salt or N-oxide derived therefrom.
  • R is hydrogen, C alkyl (optionally substituted with cyano, CO 2 (C M alkyl) or phenyl (itself optionally substituted with halogen, C alkyl, C M alkoxy,
  • the ratio of spinosad: compound of formula (I) is in the range 1 : 100 to 100:1 (for example 1 : 10 to 10:1) weight/weight.
  • spinosad see, for example, EP-0375316 or abstracts from the 1997 Beltwide Cotton Insect Research and Control Conference pages 1082-1086.
  • the present invention provides a method of combating and controlling insect, acarine or nematode pests at a locus which comprises treating the pests or the locus of the pests with an effective amount of a composition comprising spinosad and a compound of formula (I), wherein A represents a bidentate group of formula -CH 2 CH 2 -; Ar is phenyl, pyridinyl, pyridazinyl or pyrazinyl, all being optionally substituted with halogen (especially fluorine, chlorine or bromine), C,.
  • halogen especially fluorine, chlorine or bromine
  • R is hydrogen, C M alkyl (optionally substituted with cyano, CO 2 (C alkyl) or phenyl (itself optionally substituted with halogen, C alkyl, C M alkoxy, C M haloalkyl or C M haloalkoxy)), C M haloalkyl (the ⁇ -carbon being unsubstituted), C 3 alkenyl or C ⁇ alkynyl; provided that when R is alkenyl or alkynyl said group does not have an unsaturated carbon atom bonding directly to the ring nitrogen of formula (I); or an acid addition salt, quaternary ammonium salt or N-oxide derived therefrom.
  • acarine or nematode include insect pests such as Lepidoptera, Diptera, Homoptera and Coleoptera (including Diabrotica, that is, corn rootworm), pests associated with agriculture (which term includes the growing of crops for food and fibre products), horticulture and animal husbandry, forestry, the storage of products of vegetable origin, such as fruit, grain and timber, and also those pests associated with the transmission of diseases of man and animals.
  • insect and acarine pest species include: Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Aedes aegypti (mosquito), Anopheles spp.
  • mosquitos mosquitos
  • Culex spp. mosquitos
  • Dysdercus fasciatus capsid
  • Musca domestica housefly
  • Pieris brassicae white butterfly
  • Plutella xylostella diamond back moth
  • Phaedon cochleariae mustard beetle
  • Aonidiella spp. scale insects
  • Preferred compounds of formula (I) in the compositions of the present invention are compounds of formula (la) wherein X is chloro or bromo and R is 2,2-difluoroethyl or 2,2,2- trifluoroethyl, including, for example 3-(5-chloropyrid-3-yl)-3-cyano-8-(2,2,2- trifluoroethyl)-8-azabicyclo[3.2.1]octane (Compound A) and 3-(5-chloropyrid-3-yl)-3-cyano- 8-(2,2-difluoroethyl)-8-azabicyclo[3.2.1]octane (Compound B).
  • a further preferred compound of formula (I) in the compositions of the present invention is 3-(5-chloropyrid-3-yl)-3-cyano-8-azabicyclo[3.2.1]octane (Compound C).
  • Compounds of formula (I) may be prepared by adaptation of methods described in the literature (such as J. Med. Chem. (1975) 18(5) 496-501), by use of one or more of the following synthetic techniques described below, or by combining literature methods with those methods described below.
  • R 5 is alkyl or phenylalkyl (especially benzyl).
  • Compounds of formula (I) can be prepared by treating compounds of formula (II) with a compound of formula RL where L is a suitable leaving group such as a halide or triflate, optionally in the presence of a suitable base, such as potassium carbonate.
  • L is a suitable leaving group such as a halide or triflate
  • Compounds of formula (II) (which are compounds of formula (I) wherein R is hydrogen) can be prepared by deprotecting compounds of formula (III) by, for instance, either: (i) treating them with a chloroformate ester (such as vinyl chloroformate) and subjecting the carbamate so formed to acid hydrolysis (with for example, hydrochloric acid); or (ii) treating them with an azodicarboxylate (such as diethyl azodicarboxylate) at a suitably elevated temperature.
  • a chloroformate ester such as vinyl chloroformate
  • an azodicarboxylate such as diethyl azodicarboxylate
  • a compound of formula (I) can be prepared by reacting a compound of formula (III) with a compound RHal (wherein Hal is a halogen) under suitable conditions (such as in the presence of a base and an alkali metal iodide) in a suitable solvent (such as N,N- dimethylformamide).
  • a compound RHal wherein Hal is a halogen
  • suitable conditions such as in the presence of a base and an alkali metal iodide
  • a suitable solvent such as N,N- dimethylformamide
  • Compounds of formula (III) can be prepared by treating compounds of formula (IV) first with a suitable base, such as lithium diisopropylamide (LDA) or lithium bis(trimethylsilyl)amide, and then reacting the product so formed with a compound ArHal, wherein Hal is a halogen.
  • a suitable base such as lithium diisopropylamide (LDA) or lithium bis(trimethylsilyl)amide
  • compounds of formula (I) can be prepared by treating compounds of formula (VI) with a suitable base, such as lithium diisopropylamide (LDA) or lithium bis(trimethylsilyl)amide, and reacting the product so formed with a compound ArHal, wherein Hal is a halogen.
  • a suitable base such as lithium diisopropylamide (LDA) or lithium bis(trimethylsilyl)amide
  • LDA lithium diisopropylamide
  • Hal trimethylsilyl
  • compounds of formula (VI) can be prepared by treating compounds of formula (VII) with a suitable base, such as potassium carbonate, in the presence of a compound of formula RHal, wherein Hal is a halogen.
  • compounds of formula (VI) can be prepared by treating compounds of formula (VIII) with tosylmethyl isocyanide in the presence of a suitable base, such as potassium ethoxide.
  • a suitable base such as potassium ethoxide.
  • Compounds of formula (VIII) can be prepared by a process analogous to the
  • a suitable solvent such as xylene
  • Compounds of formula (I) wherein A is CH 2 CHZ (wherein Z is a suitable group, such as a thiono-4-tolyloxy group) can be prepared by treating compounds of formula (I) wherein A is CH 2 CH(OH) with a suitable chloroformate (such as 4-tolyl chlorothiono formate) in the presence of a suitable base (such as N,N-dimethylaminopyridine).
  • a suitable chloroformate such as 4-tolyl chlorothiono formate
  • Compounds of formula (I) wherein A is CH 2 CH(OH) can be prepared by acid hydrolysis of compounds of formula (I) wherein A is CH 2 CH(OZ') wherein Z' is a hydrolysable group (such as tert-butyldimethylsilyl).
  • a compound of formula (I) wherein A is CH 2 CH(OZ') wherein Z' is hydrogen or a hydrolysable group (such as tert-butyldimethylsilyl) can be prepared by reacting a corresponding compound of formula (VI) with a suitable base, such as lithium diisopropylamide (LDA) or lithium bis(trimethylsilyl)amide, and reacting the product so formed with a compound ArHal, wherein Hal is a halogen.
  • a suitable base such as lithium diisopropylamide (LDA) or lithium bis(trimethylsilyl)amide
  • a compound of formula (VI) wherein A is CH 2 CH(OZ') wherein Z' is hydrogen or a hydrolysable group (such as tert-butyldimethylsilyl) can be prepared by treating a corresponding compound of formula (V) with tosylmethyl isocyanide (also known as (4- tolylsulfonyl)methylisocyanide in the presence of a suitable base, such as potassium tert- butoxide.
  • a compound of formula (V) wherein A is CH 2 CH(OZ') wherein Z' is a hydrolysable group (such as tert-butyldimethylsilyl) can be prepared by reacting a compound of formula
  • a compound of formula (I) wherein A is CH 2 CH(OZ'), wherein Z' is a suitable group (such as SO 2 CH 3 ) can be prepared by reacting a compound of formula (I) wherein A is CH 2 CH(OH) with a suitable acid chloride (such as mesyl chloride).
  • composition of the present invention generally applied for the control of insect pests gives a rate of active ingredient from 0.01 to 10 kg per hectare, preferably from 0.1 to 6 kg per hectare.
  • the compositions of the present invention can be applied to the soil, plant or seed, to the locus of the pests, or to the habitat of the pests, in the form of dusting powders, wettable powders, granules (slow or fast release), emulsion or suspension concentrates, liquid solutions, emulsions, seed dressings, fogging/smoke formulations or controlled release compositions, such as microencapsulated granules or suspensions.
  • Dusting powders are formulated by mixing the active ingredient with one or more finely divided solid carriers and/or diluents, for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers.
  • solid carriers and/or diluents for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers.
  • Granules are formed either by absorbing the active ingredient in a porous granular material for example pumice, attapulgite clays, Fuller's earth, kieselguhr, diatomaceous earths, ground corn cobs, and the like, or on to hard core materials such as sands, silicates, mineral carbonates, sulphates, phosphates, or the like.
  • Agents which are commonly used to aid in impregnation, binding or coating the solid carriers include aliphatic and aromatic petroleum solvents, alcohols, polyvinyl acetates, polyvinyl alcohols, ethers, ketones, esters, dextrins, sugars and vegetable oils, with the active ingredient.
  • Other additives may also be included, such as emulsifying agents, wetting agents or dispersing agents.
  • Microencapsulated formulations may also be used, particularly for slow release over a period of time, and for seed treatment.
  • the compositions of the present invention may be in the form of liquid preparations to be used as dips, irrigation additives or sprays, which are generally aqueous dispersions or emulsions of the active ingredient in the presence of one or more known wetting agents, dispersing agents or emulsifying agents (surface active agents).
  • the compositions which are to be used in the form of aqueous dispersions or emulsions are generally supplied in the form of an emulsifiable concentrate (EC) or a suspension concentrate (SC) containing a high proportion of the active ingredient or ingredients.
  • EC emulsifiable concentrate
  • SC suspension concentrate
  • An EC is a homogeneous liquid composition, usually containing the active ingredient dissolved in a substantially non- volatile organic solvent.
  • An SC is a fine particle size dispersion of solid active ingredient in water. In use, the concentrates are diluted in water and applied by means of a spray to the area to be treated.
  • Suitable liquid solvents for ECs include methyl ketones, methyl isobutyl ketone, cyclohexanone, xylenes, toluene, chlorobenzene, paraffins, kerosene, white oil, alcohols, (for example, butanol), methylnaphthalene, trimethylbenzene, trichloroethylene, N-methyl-2-pyrrolidone and tetrahydrofurfuryl alcohol (THFA).
  • methyl ketones methyl isobutyl ketone, cyclohexanone, xylenes, toluene, chlorobenzene, paraffins, kerosene, white oil, alcohols, (for example, butanol), methylnaphthalene, trimethylbenzene, trichloroethylene, N-methyl-2-pyrrolidone and tetrahydrofurfuryl alcohol (THFA).
  • Wetting agents, dispersing agents and emulsifying agents may be of the cationic, anionic or non-ionic type.
  • Suitable agents of the cationic type include, for example, quaternary ammonium compounds, for example cetyltrimethyl ammonium bromide.
  • Suitable agents of the anionic type include, for example, soaps, salts of aliphatic monoesters of sulphuric acid, for example sodium lauryl sulphate, salts of sulphonated aromatic compounds, for example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, or butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropyl- and triisopropylnaphthalene sulphonates.
  • Suitable agents of the non-ionic type include, for example, the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkyl phenols such as octyl phenol, nonyl phenol and octyl cresol.
  • Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene oxide, and the lecithins.
  • compositions of the present invention may be in the form of powders (dry seed treatment DS or water dispersible powder WS) or liquids (flowable concentrate FS, liquid seed treatment LS, or microcapsule suspension CS) for use in seed treatments.
  • compositions of the present invention are applied to the insect pests, to the locus of the pests, to the habitat of the pests, or to growing plants liable to infestation by the pests, by any of the known means of applying pesticidal compositions, for example, by dusting, spraying, or incorporation of granules.
  • compositions of the present invention may be admixed with one or more additional active ingredients such as insecticides or synergists where appropriate.
  • additional active ingredients for inclusion in a composition of the present invention may be compounds which will broaden the spectrum of activity of the compositions of the invention or increase their persistence in the location of the pest. They may synergise the activity of the compound of formula (I) or complement the activity for example by increasing the speed of effect or overcoming repellency.
  • the particular additional active ingredient included will depend upon the intended utility of the mixture and the type of complementary action required.
  • suitable insecticides include the following: a) Pyrethroids such as permethrin, esfenvalerate, deltamethrin, cyhalothrin in particular lambda-cyhalothrin, biphenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids for example ethofenprox, natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin and 5-benzyl-3-furylmethyl-(E)-(lR,3S)-2,2-dimethyl- 3-(2-oxothiolan-3-ylidenemethyl) cyclopropane carboxylate; b) Organophosphates such as profenofos, sulprofos, methyl parathion, azinphos-methyl, demeton-s-methyl, hepten
  • insecticides having particular targets may be employed in the mixture if appropriate for the intended utility of the mixture.
  • selective insecticides for particular crops for example stemborer specific insecticides for use in rice such as cartap or buprofezin can be employed.
  • insecticides specific for particular insect species/stages for example ovo-larvicides such as chlofentezine, flubenzimine, hexythiazox and tetradifon, motilicides such as dicofol or propargite, acaricides such as bromopropylate, chlorobenzilate, or growth regulators such as hydramethylron, cyromazine, methoprene, chlorofiuazuron and diflubenzuron may also be included in the compositions.
  • ovo-larvicides such as chlofentezine, flubenzimine, hexythiazox and tetradifon
  • motilicides such as dicofol or propargite
  • acaricides such as bromopropylate, chlorobenzilate
  • growth regulators such as hydramethylron, cyromazine, methoprene, chlorofiuazuron and di
  • synergists for use in the compositions include piperonyl butoxide, sesamax, safroxan and dodecyl imidazole.
  • the following Examples illustrate the invention.
  • EXAMPLE 1 The resistance breaking effect of the invention compositions is demonstrated by the following test using resistant (R2) strain of the peach aphid Myzus persicae which is classified as 'strongly resistant' to organophosphorus compounds (OPs), pyrethroids and carbamates due to an increased level of esterase E4.
  • R2 resistant
  • OPs organophosphorus compounds
  • carbamates due to an increased level of esterase E4.
  • the test compositions were as set out below. The procedure was as follows: One day before treatment:
  • the dried cotyledons were removed and the pots labelled as required - in this case for 1 rate x 10 replicates.
  • the solutions were sprayed using a Burkhard Potter tower at around 3001/ha. Once air dried, lids with ventilation slits were clipped on top and the test stored for 3 days at 20°C. By this procedure the aphids were dosed by direct contact and residual pickup as they moved across the leaf surface. 3 days after treatment: Each pot was assessed for dead and live aphids. The data was analysed and the results set out below in the following Table.
  • EXAMPLE 2 Cells from the thoracic ganglia of a locust were prepared according to a simplified version of the methods described by Beadle and Lees ⁇ Beadle D.J., Lees G. (1986), In Neuropharmacology & Pesticide Action (edited by M.G. Ford et al), pages 423-444, Chichester: Ellis Horwood ⁇ and Pinnock and Sattelle ⁇ Pinnock R.D., Sattelle D.B. (1987), J. Neuroscience Methods 20 pages 195-202 ⁇ . A single animal was used for each experiment.
  • the insect was killed and its thoracic ganglia removed under a saline consisting of 214mM Na + ; 3.1mM K + ; 9mM Ca 2+ ; 221mM Cl “ ; lOmM TES, adjusted to pH 7.0. All axonal processes were trimmed off each of the ganglia and the sheath layer removed using fine forceps. The ganglia were then cut into halves or quarters and transferred to a lmg/ml (approx.) collagenase (Sigma Type III) solution in cockroach saline. After 30-50minutes (room temperature) the tissue was washed in enzyme free saline and triturated through fire- polished pasteur-pipettes. The resulting suspension was plated out onto 50mm Falcon Tight- Seal petri-dishes containing just enough medium to cover the floor of the dish.
  • Membrane voltage was recorded using a conventional intracellular (current-clamp) technique. Isolated cell bodies were impaled with a borosilicate micro-pipette containing a silver/silver-chloride electrode in a 3M KCl(aq) electrolyte. Micro-pipettes were prepared using a Sutter P97 horizontal puller to give resistances of around 20M ⁇ . Cells were stimulated electrically through the intracellular electrode by repetitive pulses of either negative current, to assess membrane resistance, or positive current, to elicit action-potentials (spikes).
  • Compound C (lO ⁇ M) and Compound A (lOO ⁇ M) were applied (separately) to the membrane of the cell from a second micro-pipette placed in close vicinity.
  • This micro- pipette was connected to a pressure-generator (MSC PLilOO Picoinjector) and ejection of the compounds achieved by controlled pulses of nitrogen gas. Spinosad was applied through the perfusing saline.
  • Compound C (referred to as 'comp. C in the figures) elicits a depolarisation of the cell coupled to a drop in the membrane resistance as indicated by the shortening of the voltage responses to the negative current steps ( Figure 1).
  • the response to Compound A (referred to as 'comp. A' in the figures) in the same cell is shown in Figure 2. There is no depolarisation and even a slight hyperpolarisation.
  • Figures 6 to 11 show the effect of spinosad on the response to Compound A.
  • Figures 6 to 8 show the superimposed voltage responses to sixty 90ms pulses of positive current (In) applied through the electrode at a level just sufficient to elicit a spike (0.4nA), and at a rate of one step event every l. ⁇ secs.
  • a 90ms pulse of Compound A is applied during the tenth step in each case.
  • the square wave at the bottom of each graph indicates the duration of I fl which is also the duration of the Compound A pulse during the tenth step- event.
  • the first example ( Figure 6) is the control in the absence of spinosad which shows no response to Compound A.
  • Figure 7 was recorded in the presence of 50nM spinosad and shows changes in both the pre I ⁇ resting potential and the profile of the spike. Separation of the events in Figure 7 show that prior to application of Compound A (events 1 to 10 inclusive) the spike profile is stable (Figure 7a), but following Compound A application (Figure 7b: events 10-13) there is a depolarisation, resulting in a shortening of the stimulus- to-spike time and eventual abolition of the spike at the peak of the response. As the cell recovers its resting potential, the spike profile is restored (Figure 7c: events 20, 30, 40, 50 and 60).
  • FIG. 8 is of a recording made 10-12 minutes into washing following the application of spinosad. There is clearly some reversal of the effect; there is no abolition of the spike but still some depolarisation and shortening of the stimulus-to-spike time as shown by Figure 8a (events 10 to 13).
  • Figures 9 to 11 are plots of the resting potential changes evoked by Compound A in the absence ( Figure 9) and presence ( Figure 10) of spinosad and after 10 to 12 minutes washing ( Figure 11). These graphs were constructed using the incidental voltage at the 19ms point (just before I fl ) in each of the sixty events shown in Figures 6 to 8 respectively. The scale range of each graph has been kept the same to assist comparison of the Compound A responses.
  • the "response" to Compound A in the absence of spinosad ( Figure 9) does not rise above levels of background noise whereas in the presence of spinosad ( Figure 10) there is a clear depolarisation of more than 14mV. This steadily reduces as the spinosad is washed away ( Figure 11).
  • Compound C is a potent depolariser of insect neurones and spinosad reversibly potentiates this action. In the presence of spinosad, significant depolarisation responses can be achieved with Compound A.

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  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne une composition insecticide contenant un premier ingrédient insecticide actif auquel des insectes nuisibles ont développé un certain degré de résistance, un excipient ou diluant insecticide inerte et, éventuellement, un ou plusieurs agents tensioactifs, pour renforcer l'activité de la composition pour vaincre la résistance des insectes nuisibles. Ladite composition se caractérise par le fait qu'elle contient une dose suffisante d'un composé de la formule (I) dans laquelle A représente un groupe bidenté de la formule -CH2-CH2- ou CH=CH; Ar est phényle, pyridinyle, pyridazinyle ou pyrazinyle, lesdits éléments étant tous éventuellement substitués par halogène, alkyle C1-4, alcoxy C1-4, alcényle C2-4, alkynyle C2-4 ou cyano; R est hydrogène, alkyle C1-4 (éventuellement substitué par cyano, CO2(alkyle C1-4) ou phényle (lui-même éventuellement substitué par halogène, alkyle C1-4, alcoxy C1-4, haloalkyle C1-4 ou haloalcoxy C1-4)), haloalkyle C2-4 (le carbone-alpha étant insubstitué), alcényle C3-4 ou alkynyle C3-4; à condition que, si R est alcényle ou alkynyle, ledit groupe ne contienne pas un atome de carbone insaturé lié directement à l'azote cyclique de la formule (I); ou un sel d'addition d'acide, un sel d'ammonium quaternaire ou un N-oxyde dérivé dudit sel. L'invention concerne également un procédé d'utilisation de ladite composition pour lutter contre les insectes nuisibles.
PCT/GB1997/003056 1996-11-26 1997-11-06 Compositions insecticides et procedes WO1998023158A1 (fr)

Priority Applications (12)

Application Number Priority Date Filing Date Title
CZ991842A CZ184299A3 (cs) 1996-11-26 1997-11-06 Insekticidní prostředek
AU48763/97A AU4876397A (en) 1996-11-26 1997-11-06 Insecticidal compositions and methods
IL13006097A IL130060A0 (en) 1996-11-26 1997-11-06 Insecticidal compositions and methods
JP52438598A JP2001504511A (ja) 1996-11-26 1997-11-06 殺虫性組成物および方法
SK693-99A SK69399A3 (en) 1996-11-26 1997-11-06 Insecticidal composition
APAP/P/1999/001537A AP1068A (en) 1996-11-26 1997-11-06 Insecticidal compositions and methods.
SI9720085A SI20002A (sl) 1996-11-26 1997-11-06 Insekticidni sestavki in postopki
BR9713146-6A BR9713146A (pt) 1996-11-26 1997-11-06 Composição inseticida, e, processo de melhoria da atividade de um inseticida contra pestes de inseto e de combate ou de controle de pestes de inseto, de ácaro ou de mematódeo em um local.
EP97911351A EP0944319A1 (fr) 1996-11-26 1997-11-06 Compositions insecticides et procedes
EA199900504A EA002032B1 (ru) 1996-11-26 1997-11-06 Инсектицидные композиции и способы борьбы с вредителями
CA002271747A CA2271747A1 (fr) 1996-11-26 1997-11-06 Compositions insecticides et procedes
BG103516A BG103516A (en) 1996-11-26 1999-06-22 Insecticidal compositions and methods

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9624501.4 1996-11-26
GBGB9624501.4A GB9624501D0 (en) 1996-11-26 1996-11-26 Insecticial compositions and method

Publications (1)

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WO1998023158A1 true WO1998023158A1 (fr) 1998-06-04

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Application Number Title Priority Date Filing Date
PCT/GB1997/003056 WO1998023158A1 (fr) 1996-11-26 1997-11-06 Compositions insecticides et procedes

Country Status (21)

Country Link
EP (1) EP0944319A1 (fr)
JP (1) JP2001504511A (fr)
KR (1) KR20000069121A (fr)
CN (1) CN1245397A (fr)
AP (1) AP1068A (fr)
AU (1) AU4876397A (fr)
BG (1) BG103516A (fr)
BR (1) BR9713146A (fr)
CA (1) CA2271747A1 (fr)
CZ (1) CZ184299A3 (fr)
EA (1) EA002032B1 (fr)
GB (1) GB9624501D0 (fr)
HU (1) HUP0001101A3 (fr)
ID (1) ID21847A (fr)
IL (1) IL130060A0 (fr)
NZ (1) NZ335421A (fr)
OA (1) OA11053A (fr)
SI (1) SI20002A (fr)
SK (1) SK69399A3 (fr)
TR (1) TR199901157T2 (fr)
WO (1) WO1998023158A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001011961A1 (fr) * 1999-08-12 2001-02-22 Eli Lilly And Company Lutte contre les ectoparasites au moyen de spinosynes
JP2002532394A (ja) * 1998-12-16 2002-10-02 バイエル アクチェンゲゼルシャフト 活性剤の組み合わせ
JP2003506463A (ja) * 1999-08-12 2003-02-18 イーライ・リリー・アンド・カンパニー コンパニオン動物における害虫の経口処置
WO2006082213A1 (fr) * 2005-02-03 2006-08-10 Intervet International B.V. Compositions antiparasitaires contenant une combinaison synergique d'amitraz et de chlorpyrifos
US7772194B2 (en) 2001-09-17 2010-08-10 Eli Lilly And Company Pesticidal formulations
WO2013000572A1 (fr) 2011-06-30 2013-01-03 2LUTION GmbH Agents de lutte contre les parasites d'animaux
WO2014154486A1 (fr) * 2013-03-28 2014-10-02 Syngenta Participations Ag Procédés de lutte contre des organismes nuisibles résistant aux néonicotinoïdes
WO2014154488A1 (fr) * 2013-03-28 2014-10-02 Syngenta Participations Ag Procédés de lutte contre des organismes nuisibles résistant aux néonicotinoïdes
WO2014154487A1 (fr) * 2013-03-28 2014-10-02 Syngenta Participations Ag Procédés de lutte contre des organismes nuisibles résistant aux néonicotinoïdes

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030037989A (ko) * 2001-11-08 2003-05-16 알앤엘생명과학주식회사 사이로마진과 델타메트린을 유효성분으로 하는 살충제조성물
GB0211924D0 (en) * 2002-05-23 2002-07-03 Syngenta Ltd Composition
WO2013191312A1 (fr) * 2012-06-19 2013-12-27 주식회사 동부한농 Composition insecticide pour désinfecter un abri pour bétail et une ferme avicole, et son procédé de préparation
CN105494383A (zh) * 2016-02-05 2016-04-20 烟台顺隆化工科技有限公司 一种防治蔗扁蛾用杀虫剂

Citations (2)

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Publication number Priority date Publication date Assignee Title
EP0375316A1 (fr) * 1988-12-19 1990-06-27 DowElanco Composés macrolides
WO1996037494A1 (fr) * 1995-05-24 1996-11-28 Zeneca Limited Amines biclycliques utilisees comme insecticide

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
EP0375316A1 (fr) * 1988-12-19 1990-06-27 DowElanco Composés macrolides
WO1996037494A1 (fr) * 1995-05-24 1996-11-28 Zeneca Limited Amines biclycliques utilisees comme insecticide

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* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 125, no. 11, 9 September 1996, Columbus, Ohio, US; abstract no. 135391y, SPARKS, THOMAS C. ET AL: "Chemistry and biology of the spinosyns: components of spinosad (Tracer), the first entry into DowElanco's naturalyte class of insect control products" XP002054553 *
PROC. - BELTWIDE COTTON CONF. (1996), (VOL. 2), 692-696 CODEN: PCOCEN;ISSN: 1059-2644 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002532394A (ja) * 1998-12-16 2002-10-02 バイエル アクチェンゲゼルシャフト 活性剤の組み合わせ
WO2001011961A1 (fr) * 1999-08-12 2001-02-22 Eli Lilly And Company Lutte contre les ectoparasites au moyen de spinosynes
JP2003506463A (ja) * 1999-08-12 2003-02-18 イーライ・リリー・アンド・カンパニー コンパニオン動物における害虫の経口処置
JP2012001563A (ja) * 1999-08-12 2012-01-05 Eli Lilly & Co コンパニオン動物における害虫の経口処置
US7772194B2 (en) 2001-09-17 2010-08-10 Eli Lilly And Company Pesticidal formulations
US8048861B2 (en) 2001-09-17 2011-11-01 Eli Lilly And Company Pesticidal formulations
WO2006082213A1 (fr) * 2005-02-03 2006-08-10 Intervet International B.V. Compositions antiparasitaires contenant une combinaison synergique d'amitraz et de chlorpyrifos
WO2013000572A1 (fr) 2011-06-30 2013-01-03 2LUTION GmbH Agents de lutte contre les parasites d'animaux
WO2014154486A1 (fr) * 2013-03-28 2014-10-02 Syngenta Participations Ag Procédés de lutte contre des organismes nuisibles résistant aux néonicotinoïdes
WO2014154488A1 (fr) * 2013-03-28 2014-10-02 Syngenta Participations Ag Procédés de lutte contre des organismes nuisibles résistant aux néonicotinoïdes
WO2014154487A1 (fr) * 2013-03-28 2014-10-02 Syngenta Participations Ag Procédés de lutte contre des organismes nuisibles résistant aux néonicotinoïdes

Also Published As

Publication number Publication date
HUP0001101A2 (hu) 2000-08-28
TR199901157T2 (xx) 1999-07-21
ID21847A (id) 1999-08-05
EP0944319A1 (fr) 1999-09-29
JP2001504511A (ja) 2001-04-03
CA2271747A1 (fr) 1998-06-04
NZ335421A (en) 2000-11-24
CZ184299A3 (cs) 1999-08-11
AP1068A (en) 2002-05-13
EA002032B1 (ru) 2001-12-24
AU4876397A (en) 1998-06-22
IL130060A0 (en) 2000-02-29
CN1245397A (zh) 2000-02-23
OA11053A (en) 2003-03-10
KR20000069121A (ko) 2000-11-25
SI20002A (sl) 2000-02-29
BG103516A (en) 2000-06-30
GB9624501D0 (en) 1997-01-15
BR9713146A (pt) 2000-02-08
SK69399A3 (en) 1999-11-08
EA199900504A1 (ru) 1999-12-29
AP9901537A0 (en) 1999-06-30
HUP0001101A3 (en) 2000-12-28

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