EP0000537B1 - Insecticidal and acaricidal agents, their use and methods for their preparation - Google Patents

Insecticidal and acaricidal agents, their use and methods for their preparation Download PDF

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Publication number
EP0000537B1
EP0000537B1 EP78100424A EP78100424A EP0000537B1 EP 0000537 B1 EP0000537 B1 EP 0000537B1 EP 78100424 A EP78100424 A EP 78100424A EP 78100424 A EP78100424 A EP 78100424A EP 0000537 B1 EP0000537 B1 EP 0000537B1
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alkyl
oder
methyl
für
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French (fr)
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EP0000537A1 (en
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Volker Dr. Mues
Wolfgang Dr. Behrenz
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Bayer AG
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Bayer AG
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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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
    • A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
    • A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/52—Radicals substituted by halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/54—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/58—Radicals substituted by nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F5/00—Methods or arrangements for data conversion without changing the order or content of the data handled
    • G06F5/06—Methods or arrangements for data conversion without changing the order or content of the data handled for changing the speed of data flow, i.e. speed regularising or timing, e.g. delay lines, FIFO buffers; over- or underrun control therefor
    • G06F5/10—Methods or arrangements for data conversion without changing the order or content of the data handled for changing the speed of data flow, i.e. speed regularising or timing, e.g. delay lines, FIFO buffers; over- or underrun control therefor having a sequence of storage locations each being individually accessible for both enqueue and dequeue operations, e.g. using random access memory

Definitions

  • the present invention relates to new insecticidal and acaricidal synergistic active ingredient combinations of partially known benzodioxoles and other known pesticidal, in particular insecticidal, active ingredients.
  • R 7 is hydrogen, alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 4 carbon atoms and up to 3 halogen atoms, nitrile or ethynyl are preferred.
  • R 8 is phenyl, which is optionally substituted by C 1-4 -alkyl, halogen, in particular fluorine or chlorine, optionally halogen- or methyl-substituted phenoxy, optionally substituted benzyl, furthermore furanyl, tetrahydrophthalimido, Benzodioxol, which is optionally substituted by halogen, in particular chlorine, alkyl or alkenyl having up to 4 carbon atoms or benzyl, and also represents cyclopentonone, which may be substituted by C 1-4 alkyl, furfuryl, C 1-5 alkenyl is substituted.
  • the insecticidal and / or acaricidal action of the active compound combinations according to the invention is substantially higher than the action of the individual components or the sum of the actions of the individual components. It is also significantly higher than the effect of the already known combination of active ingredients from 2-iso-propoxy-phenyl-N-methyl-carbamate and piperonyl butoxide.
  • the benzodioxole derivatives which can be used according to the invention show excellent synergistic activity not only with one class of active substance, but with active substances from a wide variety of chemical groups.
  • synergistic mixtures containing benzodioxole derivatives according to the invention thus represent a valuable enrichment of technology.
  • 6-chloromethyl compounds used as intermediates can be prepared by the processes specified in US Pat. Nos. 2,485,600 and 2,485,680.
  • the carbamates (group A) of the formula (11) to be used as mixed components include: 2-methylphenyl, 2-ethyphenyl, 2-n-propylphenyl, 2-methoxyphenyl, 2-ethoxyphenyl, 2-iso-propoxyphenyl -, 4-methylphenyl, 4-ethylphenyl, 4-n-propylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-n-propoxyphenyl, 3,4,5-trimethylphenyl, 1-naphthyl, 2 3-dihydro-2,2-dimethyl-7-benzofuranyl-, 2- [1,3-dioxolane (2) yl-phenyl] - or 2,2-dimethyl-1,3-benzodioxole (4) yl- N-methyl-carbamate and the corresponding -N-methyl-N-acetyl-, -N-methyl-N-trifluoromethylthio-, -N-
  • the new active ingredient combinations of the benzodioxole derivatives of the formula (I) which can be used according to the invention with carbamates, carboxylic acid esters, phosphoric acid esters and / or haloalkanes show an outstanding increase in activity compared to the individual active ingredients or their sum.
  • Diprion spp. Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp. From the order of the Diptera z.
  • B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomox ., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipul
  • the active substance combinations can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, suspension emulsion concentrates, seed pu ders, active substance-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances and in coating compositions for seeds, also in formulations with fuel sets, such as smoking cartridges, cans, spirals, etc. as well as ULV cold and warm fog formulations.
  • customary formulations such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, suspension emulsion concentrates, seed pu ders, active substance-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances and in coating compositions for seeds, also in formulations with fuel sets, such as smoking cartridges, cans, spirals,
  • formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carrier substances, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents.
  • extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carrier substances, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • surface-active agents that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • water e.g. organic solvents can also be used as auxiliary solvents.
  • aromatics such as xylene, toluene, or alkylnaphthalenes
  • chlorinated aromatics or chlorinated aliphatic hydrogen sulfides such as chlorobenzenes, chloroethylene or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins, e.g.
  • Petroleum fractions alcohols, such as butanol or glycol, and also ether and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water; liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, e.g.
  • Aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; as solid carriers: natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock flours, such as highly disperse silica, aluminum oxide and silicates; as solid carriers for granules: broken and fractionated natural rocks such as calcite, marble, pumice, sepiblite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foaming agents: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compound combinations according to the invention are used in the form of their commercially available formulations and / or the use forms prepared from these formulations.
  • the total active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
  • the active substance concentration of the use forms can be from 0.0000001 to 100% by weight of active substance, preferably between 0.01 and 10% by weight.
  • the application takes place in a customary manner adapted to the application forms.
  • the active substance combinations When used against hygiene pests and pests of stored products, the active substance combinations are notable for an excellent residual action on wood and clay and for good stability to alkali on limed substrates.
  • Test animals Phosphoric acid ester-resistant Musca domestica (Weymann strain)
  • Solutions are prepared from the active ingredients, synergists and mixtures of active ingredients and synergists, and 2.5 ml of these are pipetted into Petri dishes on filter paper discs with a diameter of 9.5 cm. The filter paper absorbs the solutions. The petri dishes remain open until the solvent has completely evaporated. Then 25 test animals are placed in the Petri dishes and covered with a glass lid.
  • the condition of the test animals is checked continuously for up to 6 hours. The time required for a 100% knock-down effect is determined. If the LT 100 is not reached after 6 hours, the% salt of the test animals that have knocked down is determined.

Description

Die vorflegende Erfindung betrifft neue insektizide und akarizide synergistische Wirkstoffkombinationen aus teilweise bekannten Benzodioxolen und anderen bekannten pestiziden, insbesondere insektiziden, Wirkstoffen.The present invention relates to new insecticidal and acaricidal synergistic active ingredient combinations of partially known benzodioxoles and other known pesticidal, in particular insecticidal, active ingredients.

Weiterhin ist es bereits bekannt, daß die folgenden Wirkstoffe bzw. Wirkstoffgruppen pestizide, insbesondere insektizide und akarizide, Eigenschaften aufweisen:

  • A) Carbamate, wie z.B. das 2 - iso - Propoxy - phenyl - N - methyl - carbamat, 3,4,5 - Trimethyl .- phenyl - N - methyl - carbamat, 1-Naphthyl - N - methyl - carbamat, 2,3 - Dihydro - 2,2 - dimethyl - 7 - benzofuranyl - N - methylcarbamat, 2 - [1,3 - Dioxolan(2)yl - phenyl] - N - methyl - carbamat und 2,2-Dimethyl - 1,3 - benzodioxol(4)yl - N - methyl - carbamat,
  • B) Carbonsäureester, wie z.B. 2,3,4,5 - Tetrahydrophthalimidomethyl - chrysanthemat und (5 - Benzyl - furyl(3)) - methyl - 2,2 - dimethyl - 3 - (2 - methylpropenyl) - cyclopropancarboxylat,
  • C) Phosphorsäureester, wei z.B. 0,0-Dimethyl-0-(2,2-dichlorvinyl)-phosphorsäureester, und
  • D) Halogenalkane, wie z.B. 1,1,1-Trichlor-2,2-bis-(4-methoxy-phenyl)-äthan und 1,1,1-Trichlor-2,2-bis-(4-chlorphenyl)-äthan.
Furthermore, it is already known that the following active substances or groups of active substances have pesticidal, in particular insecticidal and acaricidal, properties:
  • A) carbamates, such as, for example, 2-iso-propoxy-phenyl-N-methyl-carbamate, 3,4,5-trimethyl-phenyl-N-methyl-carbamate, 1-naphthyl-N-methyl-carbamate, 2, 3 - dihydro - 2,2 - dimethyl - 7 - benzofuranyl - N - methyl carbamate, 2 - [1,3 - dioxolane (2) yl - phenyl] - N - methyl - carbamate and 2,2-dimethyl - 1,3 - benzodioxol (4) yl - N - methyl - carbamate,
  • B) carboxylic acid esters, such as, for example, 2,3,4,5-tetrahydrophthalimidomethyl chrysanthemum and (5-benzyl-furyl (3)) -methyl-2,2-dimethyl-3 - (2-methylpropenyl) cyclopropanecarboxylate,
  • C) phosphoric acid esters, for example 0.0-dimethyl-0- (2,2-dichlorovinyl) phosphoric acid ester, and
  • D) haloalkanes, such as, for example, 1,1,1-trichloro-2,2-bis (4-methoxyphenyl) ethane and 1,1,1-trichloro-2,2-bis (4-chlorophenyl) - äthan.

Weiterhin sind synergistische Mischungen von Carbamaten, z.B. 2-iso-Propoxy-phenyl-N-methyl- carbamat oder von Phosphorsäureestern, z.B. 0,0-Diäthyl-0-[2-isopropyl-4-methylpyrimidinyl (6)]-thionophosphorsäureester oder von natürlichen oder synthetischen Pyrethroiden mit Piperonyläthern, wie z.B. α-[2-(2-Butoxy-äthoxy)-äthoxy]-4,5-methylendioxy-2-propyl-toluol, bekannt (vgl. Bull.Org. Health Org. 1966, 35, Seiten 691-708; Schrader, G.: Die Entwicklung neuer insektizider Phosphorsäureester 1963, S. 158; Perkov, W.: Die Insektizide, 1966, Seiten 516-524). Doch ist die Wirksamkeit dieser synergistischen Wirkstoffkombinationen nicht befriedigend. Eine gewisse praktische Bedeutung hat bisher nur Das α-[2-(2-Butoxy-äthoxy)-äthoxy-4,5-methylendioxy-2-propyl-toluol erlangt.Synergistic mixtures of carbamates, e.g. 2-iso-propoxy-phenyl-N-methyl-carbamate or of phosphoric acid esters, e.g. 0,0-diethyl-0- [2-isopropyl-4-methylpyrimidinyl (6)] thionophosphoric acid ester or of natural or synthetic pyrethroids with piperonyl ethers, e.g. α- [2- (2-butoxy-ethoxy) ethoxy] -4,5-methylenedioxy-2-propyl-toluene, known (see Bull. Org. Health Org. 1966, 35, pages 691-708; Schrader, G .: The development of new insecticidal phosphoric acid esters 1963, p. 158; Perkov, W .: Die Insektizide, 1966, pages 516-524). However, the effectiveness of these synergistic combinations of active ingredients is unsatisfactory. So far only the α- [2- (2-butoxy-ethoxy) -ethoxy-4,5-methylenedioxy-2-propyl-toluene has attained a certain practical importance.

In der FR-PS 1.441.954 werden 3,4-Methylendioxobenzolnitrile als Synergisten für insektizide Carbamate und Phosphorsäureester genannt, die jedoch in ihrer Wirkung ebenso wie die obengenannten Mischungen unbefriedigend sind.In FR-PS 1,441,954, 3,4-methylenedioxobenzene nitriles are mentioned as synergists for insecticidal carbamates and phosphoric acid esters, but their action, like the abovementioned mixtures, is unsatisfactory.

Es wurde nur gefunden, daß neue Wirkstoffkombinationen aus Benzodioxol-Derivaten der Formel (I)

Figure imgb0001
in welcher

  • R für Alkyl, Alkenyl, Alkinyl, Aryl oder Aralkyl steht, und
    • A) Carbamaten und/oder
    • B) Carbonsäureestern, einschließlich der natürlichen sowie synthetischen Pyrethroide, und/oder
    • C) Phosphorsäureestern und/oder
    • D) Halogenalkanen

eine besonders hohe insektizide und akarizide Wirkung aufweisen.It was only found that new combinations of active ingredients from benzodioxole derivatives of the formula (I)
Figure imgb0001
 in which
  • R represents alkyl, alkenyl, alkynyl, aryl or aralkyl, and
    • A) carbamates and / or
    • B) carboxylic acid esters, including the natural and synthetic pyrethroids, and / or
    • C) phosphoric acid esters and / or
    • D) haloalkanes

have a particularly high insecticidal and acaricidal activity.

Die synergistische Wirkung der Verbindungen der allgemeinen Formel (I) zeigt sich bevorzugt bei den

  • A) Carbamaten der allgemeinen Formel (11)
    Figure imgb0002
    in welcher
    • R' für Aryl, Heterocyclus oder einen Oximrest steht,
    • R2 für Wasserstoff oder Alkyl mit 1 bis 4 Kohlenstoffatomen steht und
    • R3 für Alkyl, Alkylcarbonyl mit 1 bis 6 Kohlenstoffatomen im Alkylrest, der gegebenenfalls auch durch Hydroxy oder Methylthio substituiert sein kann, oder den Rest -S-Z steht, wobei
    • Z für einen gegebenenfalls durch Halogen substituierten aliphatischen Rest mit 1 bis 4 Kohlenstoffatomen, insbesondere CCI3 und CF3 sowie für gegebenenfalls bevorzugt durch Nitril, Halogen, insbesondere Chlor, Methyl, Trihalogenmethyl, Trifluormethylmercapto oder Nitro substituierten Arylrest, insbesondere Phenyl, oder für Methoxycarbonyl oder für den Rest
      Figure imgb0003
      steht, wobei W für Alkyl, Halogenoalkyl oder Alkylamino, Dialkylamino oder einen gegebenenfalls bevorzugt durch Halogen, Trihalogenmethyl, Nitril, Methyl oder Nitro substituierten Arylrest steht.
      Besonders bevorzugt sind Carbamate in denen
    • R1 für Phenyl oder Naphthyl steht, die gegebenenfalls substituiert sind durch Alkyl, Alkenyl, Alkoxy, Alkylmercapto oder Alkylthioalkylen mit jeweils 1 bis 5 Kohlenstoffatomen, Dialkylamino, Dialkenylamino mit bis zu 3 Kohlenstoffatomen je Alkyl-bzw. Alkenylteil, Halogen, insbesondere Chlor, Dioxolanyl oder den Rest -N=CH-N(C1-4-Alkyl)2 steht.

    Weiterhin sind besonders bevorzugt Carbamate, in denen
    • R1 für 2,3-Dihydrobenzofuranyl, Benzodioxol, Benzothienyl, Pyrimidinyl oder Pyrazolyl steht, die gegebenenfalls durch C1-4-Alkyl, insbesondere Methyl, oder Dialkylamino mit 1 bis 4 Kohlenstoffatomen je Alkylteil substituiert sind.

    Weiterhin sind besonders bevorzugt Carbamate, in denen R' für einen Oximrest der allgemeinen Formel (II a)
    Figure imgb0004
    steht, in welcher
    • R4 und R5 gleich oder verschieden sind und für Alkyl, Cycloalkyl, Alkenyl, Alkinyl, Alkoxy, Alkylmercapto, Alkoxycarbonyl, Carbonylamid, Alkylmercaptoalkyl, mit jeweils bis zu 5 Kohlenstoffatomen, Nitril, Aryl, insbesondere Phenyl, einen gegebenenfalls substituierten heterocyclischen Rest oder für Alkyl, das durch einen heterocyclischen Rest substituiert ist oder gemeinsam einen gegebenenfalls durch C1-4-Alkyl substituierten Dioxolanyl oder Dithiolanylrest stehen;
  • B) Carbonsäureestern der allgemeinen Formel (111)
    Figure imgb0005
    in welcher
    • R6 für Alkyl, Aralkyl, Aryl oder Cycloalkyl steht, die gegebenenfalls substituiert sein können und
    • R7 für Wasserstoff, Alkyl, Halogenalkyl, Alkenyl, Alkinyl, Nitril steht und
    • R8 für Aryl oder einen Heterocyclus steht, oder gemeinsam mit R7 einen gegebenenfalls substituierten Cyclopentenonring bildet.
The synergistic effect of the compounds of the general formula (I) is particularly evident in the
  • A) carbamates of the general formula (11)
    Figure imgb0002
     in which
    • R 'represents aryl, heterocycle or an oxime radical,
    • R 2 represents hydrogen or alkyl having 1 to 4 carbon atoms and
    • R 3 represents alkyl, alkylcarbonyl having 1 to 6 carbon atoms in the alkyl radical, which may optionally also be substituted by hydroxy or methylthio, or the radical -SZ, where
    • Z for an aliphatic radical with 1 to 4 carbon atoms, optionally substituted by halogen, in particular CCI 3 and CF 3, and for an aryl radical, in particular phenyl, which is optionally substituted by nitrile, halogen, in particular chlorine, methyl, trihalomethyl, or nitro, or for methoxycarbonyl or for the rest
      Figure imgb0003
       where W is alkyl, haloalkyl or alkylamino, dialkylamino or an aryl radical optionally substituted by halogen, trihalomethyl, nitrile, methyl or nitro.
      Carbamates in which are particularly preferred
    • R 1 represents phenyl or naphthyl, which are optionally substituted by alkyl, alkenyl, alkoxy, alkylmercapto or alkylthioalkylene each having 1 to 5 carbon atoms, dialkylamino, dialkenylamino having up to 3 carbon atoms per alkyl or. Alkenyl part, halogen, especially chlorine, dioxolanyl or the radical -N = CH-N (C 1-4 alkyl) 2 .

    Carbamates in which
    • R 1 represents 2,3-dihydrobenzofuranyl, benzodioxole, benzothienyl, pyrimidinyl or pyrazolyl, which are optionally substituted by C 1-4 alkyl, in particular methyl, or dialkylamino having 1 to 4 carbon atoms per alkyl part.

    Furthermore, carbamates in which R 'represents an oxime radical of the general formula (II a) are particularly preferred.
    Figure imgb0004
     is in which
    • R 4 and R 5 are identical or different and are alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkylmercapto, alkoxycarbonyl, carbonylamide, alkylmercaptoalkyl, each with up to 5 carbon atoms, nitrile, aryl, in particular phenyl, an optionally substituted heterocyclic radical or for Alkyl which is substituted by a heterocyclic radical or together is a dioxolanyl or dithiolanyl radical which is optionally substituted by C 1-4 -alkyl;
  • B) carboxylic acid esters of the general formula (III)
    Figure imgb0005
     in which
    • R 6 represents alkyl, aralkyl, aryl or cycloalkyl, which may optionally be substituted and
    • R 7 represents hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, nitrile and
    • R 8 represents aryl or a heterocycle, or together with R 7 forms an optionally substituted cyclopentenone ring.

Besonders bevorzugt sind Carbonsäureester, in denen R6 für Alkyl mit 1 bis 6 Kohlenstoffatomen, das gegebenenfalls durch gegebenenfalls halogensubstituiertes Phenyl substituiert ist, Cyclopropyl, das gegebenenfalls ducrh Alkyl, Alkenyl, Halogenalkyl oder Halogenalkenyl mit jeweils bis zu 6 Kohlenstoffatomen substituiert ist, oder für Phenyl, das gegebenenfalls durch Halogen substituiert ist, steht. Bevorzugt sind Carbonsäureester, in denen R7 für Wasserstoff, Alkyl mit 1 bis 6 Kohlenstoffatomen, Halogenalkyl mit 1 bis 4 Kohlenstoffatomen und bis zu 3 Halogenatomen, Nitril oder Äthinyl steht.Particularly preferred are carboxylic acid esters in which R 6 is alkyl with 1 to 6 carbon atoms, which is optionally substituted by optionally halogen-substituted phenyl, cyclopropyl, which is optionally substituted by alkyl, alkenyl, haloalkyl or haloalkenyl, each having up to 6 carbon atoms, or phenyl , which is optionally substituted by halogen. Carboxylic acid esters in which R 7 is hydrogen, alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 4 carbon atoms and up to 3 halogen atoms, nitrile or ethynyl are preferred.

Weiter sind besonders bevorzugt Carbonsäureester, in denen R8 für Phenyl steht, das gegebenenfalls durch C1-4-Alkyl, Halogen, insbesondere Fluor oder Chlor, gegebenenfalls halogen- oder methylsubstituiertes Phenoxy, gegebenenfalls substituiertes Benzyl substituiert ist, ferner für Furanyl, Tetrahydrophthalimido, Benzodioxol, die gegenbenenfalls durch Halogen, insbesondere Chlor, Alkyl oder Alkenyl mit bis zu 4-Kohlenstoffatomen oder Benzyl substituiert sind, steht, und ferner für Cyclopentonon steht, das gegebenenfalls durch C1-4-Alkyl, Furfuryl, C1-5-Alkenyl substituiert ist.Also particularly preferred are carboxylic acid esters in which R 8 is phenyl, which is optionally substituted by C 1-4 -alkyl, halogen, in particular fluorine or chlorine, optionally halogen- or methyl-substituted phenoxy, optionally substituted benzyl, furthermore furanyl, tetrahydrophthalimido, Benzodioxol, which is optionally substituted by halogen, in particular chlorine, alkyl or alkenyl having up to 4 carbon atoms or benzyl, and also represents cyclopentonone, which may be substituted by C 1-4 alkyl, furfuryl, C 1-5 alkenyl is substituted.

Weiter sind besonders bevorzugt die natürlich vorkommenden Pyrethroide;

  • C) Phosphorsäureester der allgemeinen Formel (IV)
    Figure imgb0006
    In welcher
    • X' unabhängig voneinander für 0 oder S steht und
    • Y' für 0, S, -NH- oder für eine direkte Bindung zwischen dem zentralen P-Atom und dem R" steht und
    • R9 und R10 gleich oder verschieden sind und für gegebenenfalls substituiertes Alkyl oder Aryl stehen,
    • R11 für gegebenenfalls substiutiertes Alkyl, Aryl, Heteroaryl, Aralkyl, Alkenyl, Dioxanyl, oder einen Oximrest oder für den gleichen Rest steht, an den es gebunden ist.

    Besonders bevorzugt sind Phosphorsäureester, in denen
    • R9 und R10 gleich oder verschieden sind und für C1-4-Alkyl oder Phenyl stehen,
    • R" für Alkyl mit 1 bis 4 Kohlenstoffatomen steht, das gegebenenfalls durch Halogen, Hydroxyl, Nitril, gegebenfalls halogensubstituiertes Phenyl, Carbonylamid, Sulfonylalkyl, Sulfoxyalkyl, Carbonylalkyl, Alkoxy, Alkylmercapto, Alkoxycarbonyl, substituiert ist, für Alkenyl mit bis zu 4 Kohlenstoffatomen, das gegebenenfalls durch Halogen, gegebenenfalls halogensubstituiertes Phenyl oder Alkoxycarbonyl substituiert ist, oder für den Oximrest der allgemeinen Formel (II a)
      Figure imgb0007
      wobei R4 und R5 die oben angegebene Bedeutung besitzen, insbesondere jedoch für Cyan oder Phenyl stehen,
    • R" steht ferner für Dioxanyl, das durch denselben Rest substituiert ist, an den R" gebunden ist, oder R" steht für den gleichen Rest, an den er gebunden ist; oder R11 steht für Phenyl, das gegebenenfalls durch Methyl, Nitro, Nitril, Halogen, Methylthio substituiert ist; R11 steht außerdem besonders bevorzugt für gegebenenfalls durch C1-4-Alkyl, Halogen substituiert Heteroaromaten, wie Pyridin, Chinolin, Chinoxalin, Pyrimidin, Diazinon, Benzo-1,2,4-triazin;
  • D) Halogenalkane der Formel (V)
    Figure imgb0008
    in welcher
    • Hal'für Chlor oder Brom
    • R12 für Wasserstoff oder Hydroxyl,
    • R13 und R14 gleich oder verschieden sind und für Halogen, Alkyl oder Alkoxy und
    • R15 für Wasserstoff oder Halogen stehen.
    • Besonders bevorzugt sind Halogenalkane, in denen
    • R12 Wasserstoff oder Hydroxyl bedeutet,
    • R13 und R14 für gleiches Halogen, Alkyl bzw. Alkoxy mit 1 bis 4 Kohlenstoffatomen je Alkyl- bzw. Alkoxyrest stehen und
    • R15 Halogen bedeutet.
Furthermore, the naturally occurring pyrethroids are particularly preferred;
  • C) phosphoric acid esters of the general formula (IV)
    Figure imgb0006
     In which
    • X 'independently of one another represents 0 or S and
    • Y 'stands for 0, S, -NH- or for a direct bond between the central P atom and the R "and
    • R 9 and R 10 are identical or different and represent optionally substituted alkyl or aryl,
    • R 11 for optionally substituted alkyl, aryl, heteroaryl, aralkyl, alkenyl, dioxanyl, or one Oxime residue or represents the same residue to which it is attached.

    Phosphoric acid esters in which
    • R 9 and R 10 are the same or different and are C 1-4 alkyl or phenyl,
    • R "represents alkyl having 1 to 4 carbon atoms, which is optionally substituted by halogen, hydroxyl, nitrile, optionally halogen-substituted phenyl, carbonylamide, sulfonylalkyl, sulfoxyalkyl, carbonylalkyl, alkoxy, alkylmercapto, alkoxycarbonyl, for alkenyl having up to 4 carbon atoms, that optionally substituted by halogen, optionally halogen-substituted phenyl or alkoxycarbonyl, or for the oxime radical of the general formula (II a)
      Figure imgb0007
       where R 4 and R 5 have the meaning given above, but in particular are cyano or phenyl,
    • R "furthermore stands for dioxanyl which is substituted by the same radical to which R" is bound, or R "stands for the same radical to which it is bound; or R 11 stands for phenyl which may optionally be substituted by methyl, nitro, Nitrile, halogen, methylthio is substituted; R 11 furthermore particularly preferably represents heteroaromatics which are optionally substituted by C 1-4 alkyl, halogen, such as pyridine, quinoline, quinoxaline, pyrimidine, diazinone, benzo-1,2,4-triazine;
  • D) haloalkanes of the formula (V)
    Figure imgb0008
     in which
    • Hal'for chlorine or bromine
    • R 12 represents hydrogen or hydroxyl,
    • R 13 and R 14 are the same or different and are halogen, alkyl or alkoxy and
    • R 15 represents hydrogen or halogen.
    • Halogenalkanes in which
    • R 12 represents hydrogen or hydroxyl,
    • R 13 and R 14 represent the same halogen, alkyl or alkoxy having 1 to 4 carbon atoms per alkyl or alkoxy radical and
    • R 15 means halogen.

Überraschenderweise ist die insektizide und/oder akarizide Wirkung der erfindungsgemäßen Wirkstoffkombinationen wesentlich höher als die Wirkung der Einzelkomponenten bzw. die Summe der Wirkungen der Einzelkomponenten. Sie ist ferner wesentlich höher als die Wirkung der bereits bekannten Wirkstoffkombination aus 2-iso-Propoxy-phenyl-N-methyl-carbamat und Piperonylbutoxyd. Außerdem zeigen die erfindungsgemäß verwendbaren Benzodioxol-Derivate ausgezeichnete synergistische Wirkamkeit nicht nur bei einer Wirkstoffklasse, sondern bei Wirkstoffen aus den verschiedensten chemischen Stoffgruppen.Surprisingly, the insecticidal and / or acaricidal action of the active compound combinations according to the invention is substantially higher than the action of the individual components or the sum of the actions of the individual components. It is also significantly higher than the effect of the already known combination of active ingredients from 2-iso-propoxy-phenyl-N-methyl-carbamate and piperonyl butoxide. In addition, the benzodioxole derivatives which can be used according to the invention show excellent synergistic activity not only with one class of active substance, but with active substances from a wide variety of chemical groups.

Somit stellen die erfindungsgemäßen Benzodioxol-Derivate enthaltenden synergistischen Mischungen eine wertvolle Bereicherung der Technik dar.The synergistic mixtures containing benzodioxole derivatives according to the invention thus represent a valuable enrichment of technology.

Die für die erfindungsgemäße Kombination zu verwendenden Synergisten sind durch die Formel (I) allgemein definiert, Vorzugsweise stehen in der Formel (I) jedoch:

  • R für geradkettiges oder verzweigtes Alkyl mit 1 bis 8 Kohlenstoffatomen, insbesondere 1 bis 5 Kohlenstoffatomen, oder für geradkettiges oder verzweigtes Alkenyl mit 2 bis 8 Kohlenstoffatomen, insbesondere mit 2 bis 5 Kohlenstoffatomen, oder für geradkettiges oder verzweigtes Alkinyl mit 2 bis 8 Kohlenstoffatomen, insbesondere mit 2 bis 5 Kohlenstoffatomen, oder für Phenyl oder Benzyl.

Als Beispiele für die erfindungsgemäß verwendbaren Benzodioxol-Derivate der Formel (I) seien im einzelnen genannt:
  • 6-Methyl-, 6-Äthyl-, 6-n-Propyl-, 6-iso-Propyl-, 6-n-Butyl-, 6-iso-Butyl-, 6-sec.-Butyl-, 6-tert.-Butyl-, 6-n-Pentyl-, 6-iso-Pentyl-, 6-tert.-Pentyl-, 6-Vinyl-, 6-Allyl-, 6-Propenyl-, 6-Methallyl-, 6-Crotonyl-, 6-Buten-1'-yl-, 6-Buten-3'-yl-, 6-Äthinyl-, 6-Propin-1'-yl-, 6-Propargyl-, 6-Phenyl-, 6-Benzyl-3.4-methylendioxy-benzonitril.
The synergists to be used for the combination according to the invention are generally defined by the formula (I), but the formula (I) preferably contains:
  • R for straight-chain or branched alkyl with 1 to 8 carbon atoms, in particular 1 to 5 carbon atoms, or for straight-chain or branched alkenyl with 2 to 8 carbon atoms, in particular with 2 to 5 carbon atoms, or for straight-chain or branched alkynyl with 2 to 8 carbon atoms, in particular with 2 to 5 carbon atoms, or for phenyl or benzyl.

Examples of the benzodioxole derivatives of the formula (I) which can be used according to the invention are:
  • 6-methyl, 6-ethyl, 6-n-propyl, 6-iso-propyl, 6-n-butyl, 6-iso-butyl, 6-sec.-butyl, 6-tert. -Butyl-, 6-n-pentyl-, 6-iso-pentyl-, 6-tert-pentyl-, 6-vinyl-, 6-allyl-, 6-propenyl-, 6-methallyl-, 6-crotonyl- , 6-buten-1'-yl, 6-buten-3'-yl, 6-ethynyl, 6-propyn-1'-yl, 6-propargyl, 6-phenyl, 6-benzyl 3,4-methylenedioxy-benzonitrile.

Diese Verbindungen sind teilweise neu, können aber nach literaturbekannten Verfahren hergestellt werden (vgl.z.B. Pailer, Schleppnik, Monatshefte für Chemie 96, 1554-1562; ebda. 98, 1603-1612).Some of these compounds are new, but can be prepared by processes known from the literature (see, e.g., Pailer, Schleppnik, Monthly Magazine for Chemistry 96, 1554-1562; ibid. 98, 1603-1612).

Das folgende Formelschema illustriert den Reaktionsverlauf:

Figure imgb0009
The following formula illustrates the course of the reaction:
Figure imgb0009

Für den Fall, daß R für n-Propyl steht, verläuft die Synthese über folgende Stufen:

  • Safrol wird zum Dihydrosafrol hydriert und der Chlormethylierung zum 6-Chlormethyl-dihydrosafrol unterworfen; Reaktion mit Urotropin nach Sommelet führt zum 6-n-Propyl-piperonal. Dessen Aldoxim wird mit Acetanhydrid zum 3.4-Methylendioxy-6-n-propyl-benzonitril dehydratisiert.
In the event that R is n-propyl, the synthesis proceeds via the following stages:
  • Safrole is hydrogenated to the dihydrosafrol and subjected to chloromethylation to 6-chloromethyl-dihydrosafrol; Reaction with urotropin according to Sommelet leads to 6-n-propyl-piperonal. Its aldoxime is dehydrated with acetic anhydride to give 3,4-methylenedioxy-6-n-propyl-benzonitrile.

Die einzelnen Stufen der angegebenen Synthesewege sind bekannt oder erfolgen nach an sich bekannten Verfahrensweisen. Beispielsweise kann die Herstellung der jeweils als Zwischenprodukte dienenden 6-Chlormethylverbindungen nach den in den US-Patentschriften 2 485 600 und 2 485 680 angegebenen Verfahren erfolgen.The individual stages of the specified synthetic routes are known or are carried out according to procedures known per se. For example, the 6-chloromethyl compounds used as intermediates can be prepared by the processes specified in US Pat. Nos. 2,485,600 and 2,485,680.

Zu den als Mischkomponenten zu verwendenden Carbamaten (Gruppe A) der Formel (11) gehoren: 2-Methylphenyl-, 2-Äthyphenyl-, 2-n-Propylphenyl-, 2-Methoxyphenyl-, 2-Äthoxyphenyl-, 2-iso-Propoxyphenyl-, 4-Methylphenyl-, 4-Athylphenyl-, 4-n-Propylphenyl-, 4-Methoxyphenyl-, 4-Äthoxyphenyl-, 4-n-Propoxyphenyl-, 3,4,5-Trimethylphenyl-, 1 -Naphthyl-, 2 3-Dihydro-2,2-dimethyl-7-benzofuranyl-, 2-[1,3-Dioxolan(2)yl-phenyl]- bzw. 2,2-Dimethyl-1,3-benzodioxol(4)yl-N-methyl-carbamat und die entsprechenden -N-methyl-N-acetyl-, -N-methyl-N-trifluormethylthio-, -N-methyl-N-dichlormonofluormethylthio-bzw. -N-methyl-N-dimethylaminothiocarbamate.The carbamates (group A) of the formula (11) to be used as mixed components include: 2-methylphenyl, 2-ethyphenyl, 2-n-propylphenyl, 2-methoxyphenyl, 2-ethoxyphenyl, 2-iso-propoxyphenyl -, 4-methylphenyl, 4-ethylphenyl, 4-n-propylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-n-propoxyphenyl, 3,4,5-trimethylphenyl, 1-naphthyl, 2 3-dihydro-2,2-dimethyl-7-benzofuranyl-, 2- [1,3-dioxolane (2) yl-phenyl] - or 2,2-dimethyl-1,3-benzodioxole (4) yl- N-methyl-carbamate and the corresponding -N-methyl-N-acetyl-, -N-methyl-N-trifluoromethylthio-, -N-methyl-N-dichloromonofluoromethylthio- or. -N-methyl-N-dimethylaminothiocarbamate.

Diese Verbindungen, ihre Herstellung und ihre Verwendung sind bekannt (vergleiche z.B. US Patentschriften 3 009 855; 2 903 478 und 3 1 1 539).These compounds, their preparation and their use are known (see e.g. U.S. Patents 3,009,855; 2,903,478 and 3,115,339).

Zu den weiterhin als Mischungskomponenten gegebenenfalls zu verwendenden Carbonsäureestern (Gruppe B) der Formel (111) geheren:

  • Essigsäure - [1 - (3,4 - dichlorphenyl) - 2,2,2-trichloräthyl] - ester, 2,3,4,5 - Tetrahydrophthalimidomethylchrysanthemat und (5 - Benzylfuryl(3)) - methyl - 2,2 - dimethyl - 3 - (2 - methylpropenyl) - cyclopropancarboxylat. Die aufgezählten Verbindungen sind bekannt und größtenteils allgemein bekannte Handelsprodukte [vergleiche R. Wegler "Chemie der Pflanzenschutz-und Schädlingsbekämpfungsmittel" Bd. 1; Seiten 87-118, Heidelberg (1970)].
The carboxylic acid esters (group B) of the formula (III) which may also be used as mixture components include:
  • Acetic acid - [1 - (3,4 - dichlorophenyl) - 2,2,2-trichloroethyl] - ester, 2,3,4,5 - tetrahydrophthalimidomethyl chrysanthemum and (5 - benzylfuryl (3)) - methyl - 2,2 - dimethyl - 3 - (2-methylpropenyl) cyclopropane carboxylate. The listed compounds are known and for the most part well-known commercial products [compare R. Wegler "Chemistry of Plant Protection and Pest Control" Vol. 1; Pages 87-118, Heidelberg (1970)].

- Zu den weiterhin als Mischungskomponenten gegebenenfalls zu verwendenden Phosphorsäureestern der Formel (IV) gehören:

  • 0,0-Dimethyl- bzw. 0,0-Diäthyl-0-(2,2-dichlor- bzw. 2,2-dibromvinyl)-phosphorsäureester,
  • 0,0 - Diäthyl - 0 - (4 - nitro - phenyl)- thionophosphorsäureester,
  • 0,0 - Dimethyl - 0 - (3-methyl - 4 - methylthio) - thionophosphorsäureester,
  • 0,0 - Dimethyl - 0 - (3 - methyl - 4 - nitro) - thionophosphorsäureester,
  • 0 - Äthyl - S - n - propyl - 0 - (2,4 - dichlorphenyl) - thionophosphorsäureester,
  • 0 - Äthyl - S - n - propyl - 0 - (4 - methylthio - phenyl) - thionophosphorsäureester,
  • 0,0 - Dimethyl - S - [4 - oxo - 1,2,3 - benzotriazin(3)yl - methyl] - thionothiolphosphorsäureester,
  • 0 - Methyl - 0 - [2 - iso - propyl - 6 - methoxy - pyrimidin(4)yl] - thionomethanphosphonsäureester,
  • 0,0 - Diäthyl - 0 - [2 - iso - propyl - 6 - methyl - pyrimidin(4)yl] - thionophosphorsäureester,
  • 0,0 - Diäthyl - 0 - [3 - chlor - 4 - methyl - cumarin(7)yl] - thionophosphorsäureester,
  • 0,0 - Dimethyl - 2,2,2 - trichlo - 1 - hydroxy - äthan - phosphonsäureester,
  • 0,0 - Dimethyl - S - (methylcarbamoylmethyl) - thionophosphorsäureester.
The phosphoric acid esters of the formula (IV) which may also be used as mixture components include:
  • 0.0-dimethyl- or 0.0-diethyl-0- (2,2-dichloro- or 2,2-dibromovinyl) phosphoric acid esters,
  • 0.0 - diethyl - 0 - (4 - nitro - phenyl) thionophosphoric acid ester,
  • 0.0 - dimethyl - 0 - (3-methyl - 4 - methylthio) thionophosphoric acid ester,
  • 0.0-dimethyl-0 - (3-methyl-4-nitro) thionophosphoric acid ester,
  • 0-ethyl-S-n-propyl-0 - (2,4-dichlorophenyl) -thionophosphoric acid ester,
  • 0-ethyl-S-n-propyl-0 - (4-methylthio-phenyl) -thionophosphoric acid ester,
  • 0.0 - dimethyl - S - [4 - oxo - 1,2,3 - benzotriazin (3) yl - methyl] thionothiolphosphoric acid ester,
  • 0 - methyl - 0 - [2 - iso - propyl - 6 - methoxy - pyrimidin (4) yl] - thionomethanephosphonic acid ester,
  • 0.0 - diethyl - 0 - [2 - iso - propyl - 6 - methyl - pyrimidin (4) yl] - thionophosphoric acid ester,
  • 0.0 - diethyl - 0 - [3 - chloro - 4 - methyl - coumarin (7) yl] - thionophosphoric acid ester,
  • 0.0 - dimethyl - 2.2.2 - trichlo - 1 - hydroxy - ethane - phosphonic acid ester,
  • 0.0 - Dimethyl - S - (methylcarbamoylmethyl) thionophosphoric acid ester.

Die Verbindungen der Formel (IV) sind bekannt und nach literaturbekannten Verfahren gut zugänglich (vergleiche zum Beispiel US-Patentschrift 2 956 073, Deutsche Auslegeschrift 1 167 324, Belgische Patentschrift 633 478).The compounds of the formula (IV) are known and are readily accessible by processes known from the literature (compare, for example, US Pat. No. 2,956,073, German Auslegeschrift 1 167 324, Belgian Patent 633 478).

Zu den weiterhin als Mischungskomponenten gegebenenfalls zu verwendenden Halogenalkanen (Gruppe D) der Formel (V) gehören:

  • 1,1,1 - Trichlor - 2,2 - bis - (4 - chlor- bzw. 4 - methoxyphenyl) - äthan, 1,1,1 - Trichlor - 2 - hydroxy - 2,2 - bis - (4 - chlorphenyl) - äthan und 1,1 - Dichlor - 2,2 - bis - (4 - äthylphenyl) - äthan.

Diese Verbindungen, ihre Herstellung und ihre Verwendung sind bekannt (vergleiche zum Beispiel US-Patentschriften 2 420 928, 2 464 600, 2 883 428 und 2 917 553).The haloalkanes (group D) of the formula (V) which may also be used as mixture components include:
  • 1,1,1 - trichloro - 2,2 - bis - (4 - chloro or 4 - methoxyphenyl) - ethane, 1,1,1 - trichloro - 2 - hydroxy - 2,2 - bis - (4 - chlorophenyl ) - ethane and 1,1 - dichloro - 2,2 - bis - (4 - ethylphenyl) - ethane.

These compounds, their preparation and their use are known (see, for example, U.S. Patents 2,420,928, 2,464,600, 2,883,428 and 2,917,553).

Wie bereits erwähnt, zeigen die neuen Wirkstoffkombinationen der erfindungsgemäß verwendbaren Benzodioxol-Derivate der Formel (I) mit Carbamaten, Carbonsäureestern, Phosphorsäureestern und/oder Halogenalkanen eine hervorragende Wirkungssteigerung gegenüber den Einzelwirkstoffen bzw. gegenüber deren Summe.As already mentioned, the new active ingredient combinations of the benzodioxole derivatives of the formula (I) which can be used according to the invention with carbamates, carboxylic acid esters, phosphoric acid esters and / or haloalkanes show an outstanding increase in activity compared to the individual active ingredients or their sum.

Die Gewichtsverhältnisse der Wirkstoffgruppen können dabei in relativ großen Bereichen schwanken. Im allgemeinen werden die Benzodioxolderivate mit den übrigen Wirkstoffen im Verhältnis 0,1:10 bis 10:0,1 eingesetzt. Besonders geeignet haben sich jedoch Mischungsverhältnisse von 0,5:1,0 bis 3,0:1,0 erwiesen. Die erfindungsgemäßen Wirkstoffkombinationen bewirken nicht nur eine schnelle knock-down-Wirkung, sondern bewirken auch die nachhaltige Abtötung aller oder einzelner Entwicklungsstadien tierischer Schädlinge, insbesondere Insekten. Zu den Schädlingen gehören diejenigen, die in die Landwirtschaft, in Forsten, im Vorrats- und Materialschutz sowie auf dem Hygienesektor vorkommen. Dazu gehören:

  • Aus der Ordnung der Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
  • Aus der Ordnung der Diplopoda z. B. Blaniulus guttulatus.
  • Aus der Ordnung der Chilopoda z. B. Geophilus carpophagus, Scutigera spec.
  • Aus der Ordnung der Symphyla z. B. Scutigerella immaculata.
  • Aus der Ordnung der Thysanura z. B. Lepisma saccharina.
  • Aus der Ordnung der Collembola z. B. Onychiurus armatus.
  • Aus der Ordnung der Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
  • Aus der Ordnung der Dermaptera z. B. Forficula auricularia.
  • Aus der Ordnung der Isoptera z. B. Reticulitermes spp.,
  • Aus der Ordnung der Anoplura z. B. Phylloxera vastatrix, Pemphiqus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.
  • Aus der Ordnung der Mallophaga z. B. Trichodectes spp., Damalinea spp.
  • Aus der Ordnung der Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci.
  • Aus der Ordnung der Heteroptera z. B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
  • Aus der Ordnung der Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomycus ribis, Doralis fabae, Doralis pomi, Ertosoma lanigerum, Hyalopterus arundinis, Macrosiphum evenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp..
The weight ratios of the active ingredient groups can fluctuate in relatively large ranges. In general, the benzodioxole derivatives with the other active ingredients are used in a ratio of 0.1: 10 to 10: 0.1. Mixing ratios of 0.5: 1.0 to 3.0: 1.0 have proven to be particularly suitable. The active compound combinations according to the invention not only bring about a quick knock-down effect, but also bring about the permanent killing of all or individual stages of development of animal pests, in particular insects. The pests include those that occur in agriculture, in forests, in the protection of stored goods and materials, and in the hygiene sector. This includes:
  • From the order of the Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
  • From the order of the Diplopoda z. B. Blaniulus guttulatus.
  • From the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spec.
  • From the order of the Symphyla z. B. Scutigerella immaculata.
  • From the order of the Thysanura z. B. Lepisma saccharina.
  • From the order of the Collembola z. B. Onychiurus armatus.
  • From the order of the Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
  • From the order of the Dermaptera z. B. Auricular Forficula.
  • From the order of the Isoptera z. B. Reticulitermes spp.
  • From the order of the Anoplura z. B. Phylloxera vastatrix, Pemphiqus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.
  • From the order of the Mallophaga z. B. Trichodectes spp., Damalinea spp.
  • From the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci.
  • From the order of the Heteroptera z. B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
  • From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomycus ribis, Doralis fabae, Doralis pomi, Ertosoma lanigerum, Hyalopterus arundinis, Macrosiphum evenae, Myzus spp., Phorodaliphumisum bilobatus, Nephotettix cincticeps Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp ..

Aus der Ordnung der Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp.,Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spondoptera spp., Trichoplusia ni, Carpocapaa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.
Aus der Ordnung der Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Paylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilia, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes seneus, Ptinus spp., Niptus hololeucua, Gibbium paylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.
Aus der Ordnung der Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
Aus der Ordnung der Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
Aus der Ordnung der Siphonaptera z. B. Xenopsylla cheopis, Ceratophyllus spp.
Aus der Ordnung der Arachnida z. B. Scorpio maurus, Latrodectus mactans.
Aus der Ordnung der Acarina z. B. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.From the order of the Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiisisppa, Fpp , Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spondoptera spp., Trichoplusia ni, Carpocapaa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Caulacoecellellaella, Galleria mellella Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.
From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Paylliodes chrysocephusisisppus, Atomilaria silpp. , Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilia, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes seneus, Ptinus spp., Giptus tribiumiumideso. Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.
From the order of the Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
From the order of the Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomox ., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
From the order of the Siphonaptera z. B. Xenopsylla cheopis, Ceratophyllus spp.
From the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans.
From the order of Acarina z. B. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,. Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

Die Wirkstoffkombinationen können in die üblichen Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Spritzpulver, Suspensionen, Pulver, Staubemittel, Schäume, Pasten, lösliche Pulver, Granulate, Aerosole, Suspensions-Emulsionskonzentrate, Saatgutpucer, Wirkstoff-imprägnierte Natur- und synthetische Stoffe, Feinstverkapselungen in polymeren Stoffen und in Hüllmassen für Saatgut, ferner in Formulierungen mit Brennsätzen, wie Raucherpatronen, -dosen, -spiralen u.a. sowie ULV-Kalt- und Warmnebel-Formulierungen.The active substance combinations can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, suspension emulsion concentrates, seed pu ders, active substance-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances and in coating compositions for seeds, also in formulations with fuel sets, such as smoking cartridges, cans, spirals, etc. as well as ULV cold and warm fog formulations.

Diese Formulierungen werden in bekannter Weise hergestellt, z.B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln, unter Druck stehenden verflüssigten Gasen und/oder festen Tragerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln. Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösungsmittel als Hilfslosungsmittel verwendet werden. Als flüssige Losungsmittel kommen im wesentlichen infrage: Aromaten, wie Xylol, Toluol, oder Alkylnaphthaline, chlorierte Aromaten oder chlorierte aliphatische Kuhlenwasserstoffe, wie Chlorbenzole, Chloräthylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, Alkohole, wie Butanol oder Glycol sowie ceren Äther und Ester, Ketone, wie Aceton, Methyläthylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser; mit verflüssigten gasförmigen Streckmitteln oder Trägerstoffen sind solche Flüssigkeiten gemeint, welche bei normaler Temparatur und unter Normaldruck gasförmig sind, z.B. Aerosol-Treibgase, wie Halogenkohlenwasserstoffe sowie Butan, Propan, Stickstoff und Kohlendioxid; als fest Trägerstoffe: natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate; als feste Trägerstoffe für Granulate: gebrochene und fraktioniert natürliche Gesteine wie Calcit, Marmor, Bims, Sepiblith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehle, Kokosnußschalen, Maiskolben und Tabakstengel; als Emulgier-und/oder schaumerzeugende Mittel: nichtionogene und anionische Emulgatoren, wie Polyoxyäthylen-Fettsäure-Ester, Polyoxyäthylen-Fettalkohol-Äther, z.B. Alkylaryl-polyglykol-äther, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergiermittel: z. B. Lignin-Sulfitablaugen und Methylcellulose.These formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carrier substances, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrogen sulfides, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butanol or glycol, and also ether and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water; liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; as solid carriers: natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock flours, such as highly disperse silica, aluminum oxide and silicates; as solid carriers for granules: broken and fractionated natural rocks such as calcite, marble, pumice, sepiblite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foaming agents: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as a dispersant: e.g. B. lignin sulfite and methyl cellulose.

Es können in den Formulierungen Haftmittel wie Carboxymethylcellulöse, natürliche und synthetische pulverige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat.Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.

Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo-Metallphthalocyaninfarbstoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugswise zwischen 0,5 und 90%.The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

Die Anwendung der erfindungsgemäßen Wirkstoffkombinationen erfolgt in Form ihrer handelsüblichen Formulierungen und/oder den aus diesen Formulierungen bereiteten Anwendungsformen.The active compound combinations according to the invention are used in the form of their commercially available formulations and / or the use forms prepared from these formulations.

Der gesamte Wirkstoffgehalt der aus den handelsüblichen Formulierungen bereiteten Anwendungsformen kann in weiten Bereichen variieren. Die Wirkstoffkonzentration der Anwendungsformen kann von 0,0000001 bis zu 100 Gew.-% Wirkstoff, vorzugsweise zwischen 0,01 und 10 Gew.- % liegen.The total active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges. The active substance concentration of the use forms can be from 0.0000001 to 100% by weight of active substance, preferably between 0.01 and 10% by weight.

Die Anwendung geschieht in einer den Anwendungsformen angepaßten üblichen Weise.The application takes place in a customary manner adapted to the application forms.

Bei der Anwendung gegen Hygiene- und Vorratsschädlinge zeichnen sich die Wirkstoffkombinationen durch eine hervorragende Residualwirkung auf Holz und Ton sowie durch eine gute Alkalistabilität auf gekälkten Unterlagen aus.When used against hygiene pests and pests of stored products, the active substance combinations are notable for an excellent residual action on wood and clay and for good stability to alkali on limed substrates.

Die folgenden Beispiele zeigen die synergistischen Eigenschaften der erfindungsgamäß verwendbaren Benzodioxol-Derivate bei folgenden bekannten Wirkstoffen:

Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
(1) Pyrethrine als 25%iger Extrakt
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028
Figure imgb0029
 The following examples show the synergistic properties of the benzodioxole derivatives which can be used according to the invention with the following known active compounds:
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
 (1) Pyrethrins as a 25% extract
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028
Figure imgb0029

Zu Vergleichszwecken wurde zusätzlich das bekannte ebenfalls als Syaergist verwendete! Piperonylbutoxid verwendet:

Figure imgb0030
For comparison purposes, the well-known Syaergist was also used! Piperonyl butoxide uses:
Figure imgb0030

In den Tabellen der folgenden Beispiele wurden die bekannten Wirkstoffe sowie der bekannte Synergist mit den vorstehend angegebenen Großbuchstaben gekennzeichnet, während für die erfindungsgemäß verwendbaren Synergisten die bei den Herstellungsbeispielen angegebenen Ziffern verwendet werden.In the tables of the following examples, the known active substances and the known synergist were identified with the capital letters given above, while the numbers given in the preparation examples are used for the synergists which can be used according to the invention.

Beispiel AExample A

LT100 -TestLT 100 test

Testtiere: Phosphorsäureesterresistente Musca domestica (Stamm Weymanns)Test animals: Phosphoric acid ester-resistant Musca domestica (Weymann strain)

Lösungsmittel: AcetonSolvent: acetone

Von den Wirkstoffen, Synergisten und Gemischen aus Wirkstoffen und Synergisten werden Lösungen hergestellt und 2,5 ml davon in Petrischalen auf Filterpapierscheiben von 9,5 cm Durchmesser pipetiert. Das Filterpapier saugt die Lösungen auf. Die Petrischalen bleiben so lange offen stehen, bis das Lösungsmittel vollstängid verdunstet ist. Anschließend gibt man 25 Testtiere in die Petrischalen und bedeckt sie mit einem Glasdeckel.Solutions are prepared from the active ingredients, synergists and mixtures of active ingredients and synergists, and 2.5 ml of these are pipetted into Petri dishes on filter paper discs with a diameter of 9.5 cm. The filter paper absorbs the solutions. The petri dishes remain open until the solvent has completely evaporated. Then 25 test animals are placed in the Petri dishes and covered with a glass lid.

Der Zustand der Testtiere wird bis zu 6 Stunden laufend kontrolliert. Es wird diejenige Zeit ermittelt, die für eine 100 %ige knock down-Wirkung erforderlich ist. Wird die LT100 nach 6 Stunden nicht erreicht, wird der % Saltz der knock down gegangenen Testtiere festgestellt.The condition of the test animals is checked continuously for up to 6 hours. The time required for a 100% knock-down effect is determined. If the LT 100 is not reached after 6 hours, the% salt of the test animals that have knocked down is determined.

Konzentrationen der Wirkstoffe, Synergisten und Gemische und ihre Wirkungen gehen aus der nachfolgenden Tabelle hervor.

Figure imgb0031
Figure imgb0032
Figure imgb0033
 Concentrations of the active substances, synergists and mixtures and their effects are shown in the table below.
Figure imgb0031
Figure imgb0032
Figure imgb0033

HerstellungsbeispielManufacturing example a) 6-Chlormethyl-dihydrosafrola) 6-chloromethyl-dihydrosafrol

164,2g (1,0 Mol) Dihydrosafrol werden mit 15 og 40%igem Formalin und 500 g konzentrierter Salzsäure 36 Stunden bei 20-30°C gerührt. Anschließend verdünnt man die Reaktionsmischung mit Wasser, extrahiert diese mit Toluol und wäscht die organische Phase mit einer Natriumbicarbonatlösung. Nach dem Trocknen der Lösung über Natriumsulfat wird eingeengt und der Rückstand destilliert. Es werden 173,5g (82% der Theorie) an 6-Chlormethyl-dihydrosafrol mit dem Siedepunkt 124°C/ 3 mm Hg erhalten.164.2 g (1.0 mol) of dihydrosafrol are stirred with 15% of 40% formalin and 500 g of concentrated hydrochloric acid at 20-30 ° C. for 36 hours. The reaction mixture is then diluted with water, extracted with toluene and the organic phase is washed with a sodium bicarbonate solution. After the solution has been dried over sodium sulfate, the mixture is concentrated and the residue is distilled. 173.5 g (82% of theory) of 6-chloromethyl-dihydrosafrol with a boiling point of 124 ° C./3 mm Hg are obtained.

b) 6-n-Propyl-3,4-methylendioxy-benzaldehydb) 6-n-propyl-3,4-methylenedioxybenzaldehyde

Zu einer Lösung aus 212,7g (1,0 Mol) 6-Chlormethyl-dihydrosafrol in 1000 ml Methylenchlorid gibt man 154 g (1,1 Mol) Urotropin und erhitzt die Reaktionsmischung unter Rückfluß und unter Rühren 4 Stunden. Danach wird abgekühlt, der ausgefallene kristalline Rückstand abgesaugt und an der Luft getrocknet. Dieser wird dann unter Rückfluß in 1000 ml 50%iger Essigsäure 4 Stunden gerührt, auf 60°C abgekühlt, mit konz. Salzsäure auf p" 2 eingestellt und weitere 10 Minuten unter Rückfluß. Danach wird die Reaktionsmischung abgekühlt, mit Wasser verdünnt und mit Methylenchlorid extrahiert. Die organische Phase wird neutral gewaschen, getrocknet, eingeengt und schließlich der Rückstand destilliert. Es werden 137 g (71% der Theorie) an 6-n-Propyl-3,4-methylendioxybenzaldehyd mit dem Siedepunkt von 115°C/ 0,01 mm Hg gewonnen.154 g (1.1 mol) of urotropin are added to a solution of 212.7 g (1.0 mol) of 6-chloromethyl-dihydrosafrol in 1000 ml of methylene chloride and the reaction mixture is heated under reflux and with stirring for 4 hours. The mixture is then cooled, the crystalline residue which has precipitated is filtered off with suction and air-dried. This is then stirred under reflux in 1000 ml of 50% acetic acid for 4 hours, cooled to 60 ° C, with conc. Hydrochloric acid is adjusted to p " 2 and reflux for a further 10 minutes. The reaction mixture is then cooled, diluted with water and extracted with methylene chloride. The organic phase is washed neutral, dried, concentrated and finally the residue is distilled. 137 g (71% of theory) on 6-n-propyl-3,4-methylenedioxybenzaldehyde with a boiling point of 115 ° C / 0.01 mm Hg.

c) 6-n-Propyl-3,4-methylendioxy-benzaldoximc) 6-n-propyl-3,4-methylenedioxybenzaldoxime

Zu einer Suspension von 37,1 g (0,533 Mol) Hydroxylaminhydrochlorid in 500 ml Äthanol gibt man 21,3 g (0,533 Mol)21.3 g (0.533 mol) are added to a suspension of 37.1 g (0.533 mol) of hydroxylamine hydrochloride in 500 ml of ethanol.

Natriumhydroxyd in 27 ml Wasser und fügt dann eine Lösung von 77,0 g (0,4 Mol) 6-n-Propyl-3,4-methylendioxy-benzaldehyd in 150 ml Äthanol zu. Nach vierstündigem Rühren unter Rückfluß kühlt man die Reaktionsmischung ab, zieht das Lösungsmittel ab und behandelt den Rückstand mit Wasser. Man saugt ab und verreibt den Rückstand mit einem Gemisch aus Petroläther/ Äther (6:1), saugt wiederum ab und trocknet an der Luft. Man erhält 72 g (87% der Theorie) an Kristallen mit dem Schmelzpunkt 83°C.Sodium hydroxide in 27 ml of water and then add a solution of 77.0 g (0.4 mol) of 6-n-propyl-3,4-methylenedioxybenzaldehyde in 150 ml of ethanol. After four hours of stirring under reflux, the reaction mixture is cooled, the solvent is stripped off and the residue is treated with water. It is suctioned off and the residue is triturated with a mixture of petroleum ether / ether (6: 1), suctioned off again and air-dried. 72 g (87% of theory) of crystals with a melting point of 83 ° C. are obtained.

d) 6-n-Propyl-3,4-methylendioxy-benzonitrild) 6-n-propyl-3,4-methylenedioxy-benzonitrile

Figure imgb0034
62,2 g (0,3 Mol) 6-n-Propyl-3,4-methylendioxy-benzaldoxim werden mit 400 ml Acetanhydrid 3 Stunden unter Rückfluß gerührt, die Reaktionslösung abgekühlt und in Wasser gegossen. Nach 2 stündigem Stehenlassen extrahiert man mit Toluol, wäscht die organische Phase erst mit Wasser, dann mit Natriumhydrogencarbonat-Lösung und nochmals mit Wasser neutral. Nach dem Trocknen über Natriumsulfat wird die organische Phase eingeengt und destilliert. Man erhält 38 g (67% der Theorie) mit dem Siedepunkt 116°C/3 mm Hg.
Figure imgb0034
 62.2 g (0.3 mol) of 6-n-propyl-3,4-methylenedioxybenzaldoxime are stirred under reflux with 400 ml of acetic anhydride for 3 hours, the reaction solution is cooled and poured into water. After standing for 2 hours, the mixture is extracted with toluene and the organic phase is washed first with water, then with sodium bicarbonate solution and again with water until neutral. After drying over sodium sulfate, the organic phase is concentrated and distilled. 38 g (67% of theory) with a boiling point of 116 ° C./3 mm Hg are obtained.

Analog können hergestellt werden:

Figure imgb0035
Figure imgb0036
Figure imgb0037
 The following can be produced analogously:
Figure imgb0035
Figure imgb0036
Figure imgb0037

Claims (4)

1. Insecticidal and acaricidal agents, characterised in that they contain an active compound combination consisting of benzodioxole derivatives of the general formula (1)
Figure imgb0039
in which
R represents alkyl, alkenyl, alkinyl, aryl or aralkyl and
A) Carbamates and/or
B) Carboxylic acid esters, including the natural and synthetic pyrethroids, and/or
C) Phosphoric acid esters and/or
D) Halogenoalkanes.
2. Insecticidal and acaricidal agents according to Claim 1, characterised in that in the active compound combination the weight ratio of benzodioxole derivatives to active compounds is between 0.1:10 and 10:0.1
3. Use of active compound combinations according to Claim 1 or 2 for combating insects and arachnidae.
4. Process for the preparation of insecticidal and acaricidal agents, characterised in that an active compound combination according to Claim 1 or 2 is mixed with extenders and/or surface-active agents.
EP78100424A 1977-07-28 1978-07-18 Insecticidal and acaricidal agents, their use and methods for their preparation Expired EP0000537B1 (en)

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DE2860292D1 (en) 1981-02-19
BR7804832A (en) 1979-04-10
US4229445A (en) 1980-10-21
IL55215A0 (en) 1978-09-29
TR19891A (en) 1980-04-09
PT68319A (en) 1978-08-01
AU3837178A (en) 1980-01-31
IT7826144A0 (en) 1978-07-26
DE2734108A1 (en) 1979-02-08
JPS5426330A (en) 1979-02-27
AT360277B (en) 1980-12-29
CS197328B2 (en) 1980-04-30
ZA784267B (en) 1979-07-25
DK334778A (en) 1979-01-29
EP0000537A1 (en) 1979-02-07
NZ187944A (en) 1980-03-05
ATA544378A (en) 1980-05-15

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