WO1997015192A1 - 1,3,5-oxadiazines en tant que molluscicides - Google Patents

1,3,5-oxadiazines en tant que molluscicides Download PDF

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Publication number
WO1997015192A1
WO1997015192A1 PCT/EP1996/004534 EP9604534W WO9715192A1 WO 1997015192 A1 WO1997015192 A1 WO 1997015192A1 EP 9604534 W EP9604534 W EP 9604534W WO 9715192 A1 WO9715192 A1 WO 9715192A1
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Prior art keywords
alkyl
compound
group
formula
oxido
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PCT/EP1996/004534
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English (en)
Inventor
Robert Senn
Peter Maienfisch
Andrew Leadbeater
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Novartis Ag
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Priority to AU72957/96A priority Critical patent/AU7295796A/en
Publication of WO1997015192A1 publication Critical patent/WO1997015192A1/fr

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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
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
    • 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
    • A01N47/40—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 a double or triple bond to nitrogen, e.g. cyanates, cyanamides

Definitions

  • the present invention relates to the use of oxadiazine derived compounds of the formula
  • A is an optionally substituted heterocyclyl group
  • R is hydrogen, alkyl, phenylalkyl, cycloalkyl, alkenyl or alkynyl
  • X is N-NO 2 or N-CN; or, if appropriate, tautomers thereof, in each case in free form or in moUuscicidally utilisable salt form, for controlling representatives of the phylum Mollusca, to molluscicidal compositi ⁇ ons, whose active ingredient is selected from these compounds and tautomers, in each case in free form or in moUuscicidally utilisable salt form, to a process for the preparation and to the use of these compositions, to plant propagation material treated with these com ⁇ positions and to a method of controlling representatives of the phylum Mollusca.
  • molluscs phylum Mollusca
  • Metaldehyde molluscicides show a lower toxicity level, however, they are not truly lethal to molluscs, but induce only a narcotic or desiccating effect leading to immobilisation of the molluscs.
  • oxadiazine derivatives have been proposed in the literature as arthropodacidally active ingredients in pesticides, there is no mention of any molluscicidal utility of such oxadiazines.
  • Some of the compounds I can exist in the form of tautomers. If, for example, R is hydrogen, then corresponding compounds I, i. e. those having a 3-H-4-imino-perhydro-1 ,3,5-oxadia- zine part-structure, can exist in an equilibrium with the relevant tautomers, which have a 4- amino-5,6-dihydro-2H-1 ,3,5-oxadiazine part-structure. Accordingly, the compounds I herein ⁇ above and hereinafter are, where appropriate, also to be understood as meaning corres ⁇ ponding tautomers, even when no specific mention is made of the latter in each individual case.
  • Compounds I which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids, such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as unsubstituted or substituted, for example halogen- substituted, C ⁇ -C 4 alkanecarboxylic acids, for example acetic acid, or unsaturated or satura ⁇ ted dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fu ⁇ maric acid or phthalic acid, or hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or benzoic acid, or with organic sulfonic acids, such as unsubstituted or substituted, for example halogen-substituted, C ⁇ -C alkane
  • Compounds I which have at least one acidic group can form, for example, salts with bases, for example metal salts, such as alkali metal salts or alkaline earth metal salts, for example sodium salts, potassium salts or magnesium salts, or salts with ammonia or with an organic amine, such as morpho ⁇ line, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.
  • corresponding internal salts may also be formed, where possible.
  • the free compounds I, or the salts thereof are to be un ⁇ derstood analogously hereinabove and hereinafter as meaning, if appropriate, also the cor ⁇ responding salts and the free compounds I, respectively.
  • the free form is, in each case, the free form.
  • Suitable as ring hetero atom(s) in the basic ring structure of the heterocyclyl group A which is, for example, bicyclic or, preferably, monocyclic, are all elements of the Periodic Table, which can form at least two covalent bonds (it being possible for a ring nitrogen atom to be present in its N-oxide form); if the basic ring structure of A consists of more than one ring, one or more than one ring hetero atom(s) can be present either in only one ring or in more than one ring of the basic ring structure of A.
  • Halogen as a group per se and as structural element of other groups and compounds, such as haloalkyl, haloalkylthio, haloalkoxy, halocyclopropyl, haloalkenyl, haloalkynyl, haloallyl- oxy and haloallylthio, is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine, especially fluorine or chlorine, in particular chlorine.
  • Carbon-containing groups and compounds contain, unless otherwise defined, in each case 1 up to and including 6, preferably 1 up to and including 4, in particular 1 or 2, carbon atoms.
  • Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, preferably cyclopropyl.
  • Alkyl as a group per se and as structural element of other groups and compounds, such as phenylalkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and haloalkylthio, is, in each case with due consideration of the number of carbon atoms contained in each case in the particular group or compound, either straight-chain, i.e. methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, for example isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
  • Alkenyl, haloalkenyl, alkynyl and haloalkynyl are straight-chain or branched and contain in each case two or, preferably, one unsaturated carbon-carbon bond(s).
  • the double or triple bonds of these substituents are preferably separated from the remaining part of the com ⁇ pound I by at least one saturated carbon atom. Examples which may be mentioned are allyl, methallyl, but-2-enyl, but-3-enyl, propargyl, but-2-ynyl and but-3-ynyl.
  • Halogen-substituted carbon-containing groups and compounds such as haloalkyl, halo ⁇ alkylthio, haloalkoxy, halocyclopropyl, haloalkenyl, haloalkynyl, haloallyloxy and haloallyl ⁇ thio, can be partially halogenated or perhaiogenated, where, in the case of a polyhaloge- nation, the halogen sustituents can be identical or different.
  • haloalkyl as a group per se and as a structural element of other groups and compounds, such as haloal- kylthio and haloalkoxy, are methyl which is mono- to trisubstituted by fluorine, chlorine and/or bromine, such as CHF 2 or CF 3 ; ethyl which is mono- to pentasubstituted by fluorine, chlorine and/or bromine, such as CH 2 CF 3 , CF 2 CF 3 , CF 2 CCI 3 , CF 2 CHCI 2 , CF 2 CHF 2 , CFzCFCIj, CF 2 CHBr 2 , CF 2 CHCIF, CF 2 CHBrF or CCIFCHCIF; propyl or isopropyl, each of which is mono- to heptasubstituted by fluorine, chlorine and/or bromine, such as CH 2 CHBrCH 2 Br, CF 2 CHFCF 3 , CH 2 CF 2
  • haloalkenyl examples include 2,2-difluoroethen-1-yl, 2,2-dichloroethen-l-yl, 2-chloroprop-1-en-3-yl, 2,3-dichloroprop- 1-en-3-yl and 2,3-dibromoprop-1-en-3-yl.
  • haloalkynyl examples include 2-chloroprop-1 -yn-3- yl, 2,3-dichloroprop-1-yn-3-yl and 2,3-dibromoprop-1-yn-3-yl.
  • halocyclopropyl examples include 2-chlorocyclopropyl, 2,2-difluorocyclopropyl and 2-chloro-2-fluorocyclopropyl.
  • haloallyloxy examples include 2-chloroprop-1-en-3-yloxy, 2,3-dichloroprop-1-en-3-yloxy and 2,3- dibromoprop-1-en-3-yloxy.
  • haloallylthio are 2-chloroprop1 -en-3-ylthio, 2,3- dichloroprop-1-en-3-ylthio and 2,3-dibromoprop-1-en-3-ylthio.
  • phenylalkyi an alkyl group bonded to the remainder of the compound I is substituted by a phenyl group, in this case the alkyl group preferably being straight-chained and the phenyl group preferably being bonded in a position higher than the ⁇ -position, most preferably in ⁇ -position, of the alkyl group; examples are benzyl, 2-phenylethyl und 4-phenylbutyl.
  • A is an unsubstituted or mono- to tetrasubstituted, aromatic or non-aromatic, monocyclic or bicyclic heterocyclic radical, where one to two of the substituents of A can be selected from the group consisting of halo-CrCsalkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 - C 3 alkynyl, halo-C 2 -C 3 alkenyl, halo-C 2 -C 3 alkynyl, halo-C,-C 3 alkoxy, C ⁇ -C 3 alkylthio, halo-C C 3 alkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro, and one to four of the substituents of A can be selected from the group consisting of C ⁇ -C 3 al
  • X is N-NO 2 or N-CN
  • the basic ring structure of A has 1 , 2 or 3 hetero atoms selected from the group consisting of oxygen, sulfur and nitrogen, where not more than one of the hetero atoms in the basic ring structure is an oxygen atom and not more than one of the hetero atoms in the basic ring structure is a sulfur atom, in particular in which the basic ring structure has 1 , 2 or 3 hetero atoms selected from the group consisting of oxygen, sulfur and nitrogen, where not more than one of the hetero atoms in the basic ring structure is an oxygen or a sulfur atom, preferably at least one nitrogen atom;
  • A is a pyrid-3-yl, 2-halopyrid-5-yl-, 2,3-dihalopyrid-5-yl, 2-d-C 3 alkyl- pyrid-5-yl, 1-oxido-3-pyridinio, 2-halo-1-oxido-5-pyridinio, 2,3-dihalo1-oxido-5-pyridinio or 2- halothiazol-5-yl group, in particular in which A is a pyrid-3-yl, 2-halopyrid-5-yl, 2-halo-1-oxido-5-pyridinio or 2-halo- thiazol-5-yl group, preferably in which A is a 2-chloropyrid-5-yl, 2-methylpyrid-5-yl, 1 -oxido-3-pyridinio, 2- chloro-1-oxido-5-pyridinio, 2,3-dichloro-1-oxido-5-pyridinio
  • R is d-C 6 alkyl, phenyl-d-C alkyl, C 3 -C 6 cycloalkyl, C 3 -C 4 alkenyl or C 3 -C alkynyl, preferably d-C 6 alkyl, Cs-C ⁇ cycloalkyl, C 3 -C alkenyl or C 3 -C 4 alkynyl, especially d-C 6 alkyl, phenyl-C ⁇ -C 4 alkyl, C 3 -C 4 alkenyl or C 3 -C 4 alkynyl, in particular d-C 4 alkyl, preferably methyl;
  • A is a pyridyl, 1-oxidopyridinio or thiazolyl group which is bonded via a C atom of its basic ring structure to the remaining part of the compound I and which is unsubstituted or mono- or disubstituted by substituents selected from the group consisting of halogen and C ⁇ -C 3 alkyl, R is d-C 6 alkyl, phenyl-d-C alkyl, C 3 - C 6 cycloalkyl, C 3 -C 4 alkenyl or C 3 -C alkynyl and X is N-N0 2 or N-CN;
  • the compounds I used according to the invention are active ingredients in the field of molluscicidal compositions which have a very favourable biocidal spectrum and are valuable when used preventively and/or curatively even at low rates of application, while being well tolerated by warm-blooded species, fish and plants.
  • the active ingredients used according to the invention are effective against all or individual development stages of molluscs, showing a good activity, corresponding to a mortality rate of at least 50 to 60%.
  • molluscs to be controlled according to the invention are:
  • Bradybaena (-> Bradybaena fruticum)
  • Milacidae Milax (-> M. budapestensis, M. gagates, M. marginatus, M. sowerbyi)
  • molluscs to be controlled according to the invention are the Golden Apple Snail and the Rice Water Snail.
  • the active ingredients used according to the invention allow molluscs of the abovemen ⁇ tioned type to be controlled, i. e. contained or destroyed, which attack in particular plants, especially useful plants and ornamentals in agriculture, horticulture and forests, or parts of such plants, such as fruits, flowers, foliage, stalks, tubers or roots, and, in some cases, even newly-forming parts of the plants are still protected against these pests.
  • Suitable as target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beets, such as sugar beet or fodder beet; fruit, for example pome fruit, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries, or berries, for example strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soya beans; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa, or groundnuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruits, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, cinnamon or camphor; and
  • the invention therefore also relates to molluscicidal compositions, such as food baits, emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, dusts, pellets, granules or encapsulations in polymeric substances, all of which comprise at least one of the active ingredients used according to the invention and are to be selected depending on the intended aims and the prevailing circumstances.
  • the active ingredient is used as a pure active ingredient, for example a solid active ingredient in a specific particle size or, preferably, together with at least one of the auxiliaries conventionally used in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants), stabilizers, foodstuffs, dyes or slow release modifiers.
  • auxiliaries conventionally used in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants), stabilizers, foodstuffs, dyes or slow release modifiers.
  • Solid carriers which are used, for example for dusts and dispersible powders are, as a rule, ground natural minerals, such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • highly- disperse silicas or highly-disperse absorptive polymers Possible particulate, adsorptive carriers for granules are either porous types, such as pumice, brick grit, sepiolite or bentonite, or non-sorptive carrier materials, such as calcite or sand.
  • a large number of granulated materials of inorganic or organic nature can be used, in particular dolomite or comminuted plant residues.
  • Foodstuffs are, for example, comminuted plant residues.
  • one or more of the following substances may be used as a supplement to mollusc food baits, making such food baits more palatable to the molluscs: a) a B vitamin, particularly B1 , B2, B6, nicotinic acid or nicotinamide; b) vitamin E; c) an animal or vegetable proteinaceous material, for example albumins or their hydroiytic degradation products, particularly those obtained by enzymatic hydrolysis, for example with pepsin, such as metaproteins, proteoses, peptones, polypeptides, peptides, diketopipera- zines or amino carboxylic acids; d) one or more amino carboxylic acids or their salts or amides, which may also be synthetic products; e) a nucleic acid or a hydroiytic degradation product thereof, such as a nucleotide, a nucleoside, adenine, guanine, cytosine, uracil or thymine;
  • Suitable solvents are: unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably the fractions C 8 to C 12 of alkylbenzenes, 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 or the ethers or esters thereof, such as propylene glycol, dipropylene glycol ether, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N- methylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, epoxidised or unepoxidised vegetable oils, such as ep
  • Suitable slow release modifiers which may be used in order to obtain a controlled release of the moUuscicidally active ingredient, include, for example, those substances mentioned hereinbefore as solid carriers; preferred slow release modifiers are, for example, clays, such as bentonite or kaolinite, silicon oxides, polymeric materials, such as cellulose, cellulose ethers, particularly cellulose acetate, or resins, such as urea formaldehyde resins, soya flour, waxes, stearates or oils, for example castor oil.
  • preferred slow release modifiers are, for example, clays, such as bentonite or kaolinite, silicon oxides, polymeric materials, such as cellulose, cellulose ethers, particularly cellulose acetate, or resins, such as urea formaldehyde resins, soya flour, waxes, stearates or oils, for example castor oil.
  • suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants or surfactant mixtures which have good emulsifying, dispersing and wetting properties.
  • the surfactants given hereinbe ⁇ low are only to be regarded as examples; the specialist literature describes a large number of further surfactants conventionally used in the art of formulation and suitable according to the invention.
  • Suitable non-ionic surfactants are mainly polyglycol ether derivatives of aliphatic or cycloali ⁇ phatic alcohols, saturated or unsaturated fatty acids or alkylphenols which can have appro ⁇ ximately 3 to approximately 30 glycol ether groups and approximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatic hydrocarbon radical or approximately 6 to approxima ⁇ tely 18 carbon atoms in the alkyl moiety of the alkylphenols.
  • Suitable substances are water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopoly- propylene glycol or alkylpolypropylene glycol having 1 to approximately 10 carbon atoms in the alkyl chain and approximately 20 to approximately 250 ethylene glycol ether groups and approximately 10 to approximately 100 propylene glycol ether groups.
  • the abovementioned compounds contain 1 to approximately 5 ethylene glycol units per propy ⁇ lene glycol unit.
  • nonylphenoxypolyethoxyethanols examples which may be mentioned are nonylphenoxypolyethoxyethanols, castor oil polyglycol ethers, polypropylene glycol/polyethylene oxide adducts, tributyl- phenoxypolyethoxyethanol, polyethylene glycol or octylphenoxypolyethoxyethanol.
  • Fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate, are furthermore suitable.
  • the cationic surfactants are mainly quaternary ammonium salts which have, as a rule, at least one alkyl radical having approximately 8 to approximately 22 C atoms as substituent and, as further substituents, (free or halogenated) lower alkyl or hydroxyalkyi radicals or benzyl radicals.
  • the salts are preferably in the form of halides, methylsulfates or ethylsul- fates. Examples are stearyl-trimethyl-ammonium chloride and benzyl-bis(2-chloroethyl)- ethyl-ammonium bromide.
  • Suitable anionic surfactants are, for example, water-soluble soaps or water-soluble synthe ⁇ tic surface-active compounds.
  • Soaps which are suitable are, for example, the alkali metal salts, alkaline earth metal salts or (optionally substituted) ammonium salts of fatty acids having approximately 10 to approximately 22 C atoms, such as the sodium salts or potassi ⁇ um salts of oleic or stearic acid, or of natural mixtures of fatty acids which can be obtained, for example, from coconut oil or tall oil; mention must also be made of the fatty acid methyl- taurinates.
  • fatty sulfo ⁇ nates fatty sulfates, sulfonated benzimidazole derivatives or alkyl-aryl-sulfonates.
  • the fatty sulfonates and fatty sulfates are, as a rule, in the form of alkali metal salts, alkaline earth metal salts or (optionally substituted) ammonium salts and have, as a rule, an alkyl radical having approximately 8 to approximately 22 C atoms, alkyl also including the alkyl moiety of acyl radicals; examples which may be mentioned are the sodium salts or calcium salts of lig- ninsulfonic acid, of the dodecyisulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids.
  • This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives pre ⁇ ferably have two sulfonic acid groups and one fatty acid radical having approximately 8 to approximately 22 C atoms.
  • alkyl-aryl-sulfonates are the sodium salts, calcium salts or triethanolammonium salts of dodecylbenzenesulfonic acid, of dibutylnaphthalene- sulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensation product.
  • Other substances which are possible are suitable phosphates, such as salts of the phosphoric ester of a p-nonylphenol/(4-14) ethylene oxide adduct or phospholipids.
  • the compositions comprise 0.1 to 99%, in particular 0.1 to 95%, of active ingredient and 1 to 99.9%, in particular 5 to 99.9%, of at least one solid or liquid auxiliary, where, as a rule, 0 to 25%, in particular 0.1 to 20%, of the compositions can be surfactants (% in each case meaning per cent by weight).
  • concentrated compositions are more preferred as commercially available goods, the end consumer uses, as a rule, dilute compositions, whose concentrations of active ingredient are considerably lower.
  • Food baits generally also contain binders and foodstuffs.
  • compositions can be broadened and adapted to prevailing circumstances by addition of other moUuscicidally active ingredients, such as mercaptodimethur or metaldehyde.
  • compositions can also comprise other solid or liquid auxiliaries.
  • auxiliaries such as antifoams, for example silicone oil, viscosity regulators, agents which help avoiding the drying of the compositions, attractants for molluscs, repellents for warmblooded animals, binders and/or tackifiers, and also fertilisers or other active ingredients for achieving specific effects, for example insecticides, acaricides, bactericides, fungicides, nematocides or selective herbicides.
  • compositions are prepared in a known manner, for example, in the absence of auxiliaries, by grinding, screening and/or compressing a solid active ingredient, or active ingredient mixture, for example to give a certain particle size, and, in the presence of at least one auxiliary, for example by intimately mixing and/or grinding the active ingredient, or active ingredient mixture, with the auxiliary(-ies).
  • the invention also relates to these processes for the preparation of the compositions and to the use of the compounds I for the preparation of these compositions.
  • the invention furthermore relates to the methods of application of the compositions, i.e. to the methods of controlling molluscs, such as spraying, atomising, dusting, brushing-on, seed-dressing, scattering or pouring, which are to be selected depending on the intended aims and prevailing circumstances, and to the use of the compositions for controlling molluscs.
  • Characteristic rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient.
  • the application rates per hectare are, as a rule, 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 20 to 600 g/ha.
  • a preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application) where frequency and rate of application will depend on the danger of infestation with the particular pest.
  • the active ingredient can also reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by inco ⁇ orating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In paddy rice, such granules can be metered to the flooded paddy field.
  • compositions are also suitable for protecting plant propagation material, for example seed, such as fruits, tubers or kernels, or plant cuttings, against molluscs.
  • the propagation material can be treated with the composition before planting, for example seed can be dressed before sowing.
  • the active ingredients used according to the invention can be applied to the seed kernels (coating), either by soaking the kernels in a liquid composition or by coating them with a solid composition.
  • the composition can be applied to the site of planting when the propagation material is planted, for example it can be applied to the seed furrow during sowing.
  • the invention furthermore relates to these methods for treating plant propagation material and the plant propagation material thus treated.
  • the active ingredient is mixed with the silica, and the mixture is thoroughly ground in a sui ⁇ table mill to give a finely ground pre-mix.
  • a suitable mixer the roughly ground rape, the pre-mix, the corn starch and the other additives are intimately mixed, and the mixture is sub ⁇ sequently compressed using the matrix molding technique. After cooling down and drying, finely divided particles are sieved off using a sieve having a mesh size of 0.5 mm, yielding ready-to-use mollusc food baits (particle diameter: between 2 and 2.5 mm).
  • Example F1 The procedure described in Example F1 is repeated, with the exception, that the matrix mol ⁇ ding technique is replaced by one of the other customary compacting methods.
  • Example F3 Emulsion concentrates a) b) c)
  • Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
  • Example F4 Solutions a) b) c) d)
  • Petroleum spirit (boiling range: 160-190°) - - 94 %
  • the solutions are suitable for use in the form of microdrops.
  • Example F5 Granules a) b) c) d)
  • the active ingredient is dissolved in dichloromethane, the solution is sprayed onto the car ⁇ rier, and the solvent is subsequently evaporated in vacuo.
  • Example F6 Dusts a) b)
  • Example F7 Wettable powders a) b) c)
  • the active ingredient is 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 suspen ⁇ sions of any desired concentration.
  • Example F8 Extruder granules
  • the active ingredient is mixed with the additives, and the mixture is ground, moistened with water, extruded, granulated and dried in a stream of air.
  • Example F9 Coated granules
  • the finely ground active ingredient is applied uniformly to the kaolin, which has been moistened with the polyethylene glycol. Dust-free coated granules are obtained in this manner.
  • Example F10 Suspension concentrate Active ingredient 40 % o
  • Nonylphenoxypolyethylene glycol ether (15 mol of EO) 6 %
  • Silicone oil (75 % aqueous emulsion) 0.8 %
  • the finely ground active ingredient is mixed intimately with the additives. This gives a sus ⁇ pension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.
  • Example B1 Systemic activitv against Deroceras reticulatum
  • the roots of approximately 6 cm high lettuce plants are washed clean with water and then immersed for at least two days into an aqueous test solution comprising 400 ppm of active ingredient.
  • Individual leaves are cut from the plants and transferred onto a filter paper placed in a 9 cm diameter Petri-dish. 1 ml of water is pipetted onto each filter paper in order to keep the leaves moist during the test.
  • Two medium-sized D. reticulatum slugs are intro ⁇ quizged into each dish, and the quantity of leaves eaten as well as the activity against the slugs are recorded over a period of two days.
  • the percentage reduction in population and the percentage reduction in feeding damage are determined by comparing the number of dead slugs and the feeding damage between the treated and untreated leaves. In this test, compounds of the formula I exhibit good activity.
  • Example B2 Food bait activitv against Arion rufus
  • a food bait containing 4 % of active ingredient is prepared in a manner analogous to that described in Example F1.
  • Test pellets are placed onto the floor space (0.25 m 2 ) of a trial box covered approximately 3 cm high with moistened soil, and 10 adult A. rufus slugs are intro ⁇ quizged into the box, which is then stored in a large glass tank maintained at a temperature of 12 to 16° and a relative humidity of > 95 %. Evaluations of the number of slugs affected by the bait are made at intervals up to 3 days after the introduction of the slugs. The percen ⁇ tage reduction in population (% activity) is determined by comparing the number of dead slugs between the treated and untreated boxes.
  • Example B3 Contact activitv against Deroceras reticulatum
  • the residual activity on glass is investigated by pipetting aliquots of an acetone / Triton X- 100 - test solution over the base of a 7 cm diameter glass Petri-dish to achieve a concen ⁇ tration of 600 ppm of active ingredient.
  • Four adult D. reticulatum slugs are introduced into each dish.
  • Moistened sugar bran mix is provided as food 24 hours after the introduction of the slugs.
  • Evaluations of the number of slugs affected by the active ingredient are made at intervals up to 5 days after the introduction of the slugs.
  • the percentage reduction in popu ⁇ lation (% activity) is determined by comparing the number of dead slugs between the trea ⁇ ted and untreated dishes.
  • Example B4 Seed treatment activitv against Deroceras reticulatum

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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 l'utilisation de composés dérivés d'oxadiazine et possédant la formule (I) dans laquelle A représente un groupe hétérocyclyle éventuellement substitué; R représente hydrogène, alkyle, phénylalkyle, cycloalkyle, alcényle ou alcynyle; et X représente N-NO2 ou N-CN. L'invention concerne, le cas échéant, des tautomères de ces composés, ces composés ou leurs tautomères étant dans chaque cas sous forme libre ou sous forme d'un sel utilisable dans un but molluscicide, afin de lutter contre les représentants des mollusques de type phylum. L'invention se rapporte encore à des compositions molluscicides, dont le principe actif est choisi parmi ces composés et tautomères, lesquels se présentent à chaque fois sous forme libre ou sous forme d'un sel utilisable dans un but molluscicide, à un procédé de préparation et d'utilisation de ces compositions, à la matière de propagation des plantes traitée à l'aide de ces compositions ainsi qu'à un procédé de lutte contre les représentants des mollusques de type phylum.
PCT/EP1996/004534 1995-10-26 1996-10-18 1,3,5-oxadiazines en tant que molluscicides WO1997015192A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU72957/96A AU7295796A (en) 1995-10-26 1996-10-18 1,3,5-oxadiazines as molluscicides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH3022/95 1995-10-26
CH302295 1995-10-26

Publications (1)

Publication Number Publication Date
WO1997015192A1 true WO1997015192A1 (fr) 1997-05-01

Family

ID=4246881

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/004534 WO1997015192A1 (fr) 1995-10-26 1996-10-18 1,3,5-oxadiazines en tant que molluscicides

Country Status (4)

Country Link
AR (1) AR004094A1 (fr)
AU (1) AU7295796A (fr)
WO (1) WO1997015192A1 (fr)
ZA (1) ZA968979B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1042955A1 (fr) * 1999-04-07 2000-10-11 Bayer Ag Agents anti-salissures marin contenant de thiacloprid
WO2003079782A1 (fr) * 2002-03-25 2003-10-02 Nu-Trel Products Ltd. Systeme de distribution molluscicide
WO2006128655A2 (fr) * 2005-05-31 2006-12-07 Syngenta Participations Ag Procede d'elimination des mollusques

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0580553A2 (fr) * 1992-07-22 1994-01-26 Ciba-Geigy Ag Dérivés d'oxadiazine
JPH07224062A (ja) * 1994-02-09 1995-08-22 Nippon Bayeragrochem Kk 殺虫性ニトロ化合物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0580553A2 (fr) * 1992-07-22 1994-01-26 Ciba-Geigy Ag Dérivés d'oxadiazine
JPH07224062A (ja) * 1994-02-09 1995-08-22 Nippon Bayeragrochem Kk 殺虫性ニトロ化合物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 9542, Derwent World Patents Index; AN 95-325540, XP002020557 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1042955A1 (fr) * 1999-04-07 2000-10-11 Bayer Ag Agents anti-salissures marin contenant de thiacloprid
US6245784B1 (en) 1999-04-07 2001-06-12 Bayer Aktiengesellschaft Antifouling compositions containing thiacloprid
WO2003079782A1 (fr) * 2002-03-25 2003-10-02 Nu-Trel Products Ltd. Systeme de distribution molluscicide
WO2003079781A1 (fr) * 2002-03-25 2003-10-02 Nu-Trel Products Ltd. Systeme de distribution molluscicide
WO2006128655A2 (fr) * 2005-05-31 2006-12-07 Syngenta Participations Ag Procede d'elimination des mollusques
WO2006128655A3 (fr) * 2005-05-31 2007-05-10 Syngenta Participations Ag Procede d'elimination des mollusques

Also Published As

Publication number Publication date
AR004094A1 (es) 1998-09-30
ZA968979B (en) 1997-01-29
AU7295796A (en) 1997-05-15

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