EP0000760A1 - Benzodioxolane derivatives, process for their preparation and their use as synergists in insecticides and acaricides - Google Patents

Benzodioxolane derivatives, process for their preparation and their use as synergists in insecticides and acaricides Download PDF

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Publication number
EP0000760A1
EP0000760A1 EP78100554A EP78100554A EP0000760A1 EP 0000760 A1 EP0000760 A1 EP 0000760A1 EP 78100554 A EP78100554 A EP 78100554A EP 78100554 A EP78100554 A EP 78100554A EP 0000760 A1 EP0000760 A1 EP 0000760A1
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spp
alkyl
methyl
oder
für
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German (de)
French (fr)
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Volker Dr Mues
Wolfgang Dr. Behrenz
Gebhard Dr. Rauleder
Helmut Dr. Waldmann
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Bayer AG
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    • 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
    • C07D317/72—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 spiro-condensed with carbocyclic rings
    • 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
    • A01N43/04—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 one hetero atom
    • A01N43/06—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 one hetero atom five-membered rings
    • A01N43/12—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 one hetero atom five-membered rings condensed with a carbocyclic 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
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member 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
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic 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
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/22—O-Aryl or S-Aryl esters thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • 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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic radicals
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic radicals
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic 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

Definitions

  • the present invention relates to new benzodioxole derivatives, a process for their preparation and their use in insecticidal and acaricidal compositions as synergists.
  • carbamates e.g. 2-iso-propoxy-phenyl-N-methyl carbamate or of phosphoric acid esters, e.g. 0,0-diethyl-0- [2-isopropyl-4-methyl-pyrimidin (6) yl] -thionophosphoric acid ester or of natural or synthetic pyrethroids with piperonyl ethers.
  • phosphoric acid esters e.g. 0,0-diethyl-0- [2-isopropyl-4-methyl-pyrimidin (6) yl] -thionophosphoric acid ester or of natural or synthetic pyrethroids.
  • piperonyl ethers such as ⁇ - [2- (2-hutoxy-ethoxy) -ethoxy] -4,5-methylenedioxy-2-propyl-toluene, known (see Bull. Org. Health Org.
  • carboxylic acid esters in which R represents alkyl having 1 to 6 carbon atoms, which is optionally substituted by optionally substituted phenyl, cyclopropyl, which is optionally substituted by alkyl, alkenyl, haloalkyl or haloalkenyl, each having up to 6 carbon atoms, or for Phenyl which is optionally substituted.
  • Carboxylic acid esters in which R 9 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 10 is phenyl which is optionally substituted by C 1-4 alkyl, halogen, in particular fluorine or chlorine, optionally substituted phenoxy; and optionally substituted benzyl is further substituted for furanyl, tetrahydrophthalimido, benzodioxole, which may be substituted by halogen, in particular chlorine, alkyl or alkenyl with up to 4-carbon atoms or benzyl is substituted, and also stands for cyclopentenone which is optionally substituted by C 1-4 alkyl, furfuryl, C 1-5 alkenyl.
  • haloalkanes should be mentioned in particular 1,1,1-trichloro-2,2-bis (4-chloro- or 4-ethoxyphenyl) -ethane, 1,1,1-trichloro-2-hydroxy-2,2-bis- (4-chlorophenyl ) -ethane and 1,1-dichloro-2,2-bis (4-ethylphenyl) -ethane.
  • insecticidal and / or acaricidal action of such active compound combinations is considerably 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 active ingredient combinations with the well-known synergist piperonyl butoxide.
  • 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.
  • benzodioxole derivatives according to the invention thus represent a valuable addition to the technology.
  • Examples are: 5- (3.4-methylenedioxybenzyl) dioxolane 2-methyl-5- (3.4-methylenedioxybenzyl) dioxolane 2-ethyl-5- (3.4-methylenedioxybenzyl) dioxolane 2-n-propyl-5- (3.4-methylenedioxybenzyl) dioxolane 2-1-propyl-5- (3.4.-methylenedioxybenzyl) dioxolane 2-n-butyl 5- (3.4.-methylenedioxybenzyl) dioxolane 2-i-butyl-5- (3.4-methylenedioxybenzyl) dioxolane 2-t-butyl-5- (3.4-methylenedloxybenzyl) dioxolane 2-allyl-5- (3.4-methylenedioxybenzyl ) -dioxolane 2-methallyl-5- (3,4-methylenedioxybenzyl) dioxolane 2-crotyl-5- (3,4-methylenedioxybenzyl) dio
  • the compounds of the formula II which serve as starting compounds for the preparation of the benzodioxole derivatives according to the invention are 3- (3,4-methylenedioxyphenyl) propanediol-1,2 and 3,4-methylenedioxybenzylethylene oxide. Both compounds are known, as are the carbonyl compounds of the formula III.
  • the process for the preparation of the compounds according to the invention is optionally carried out with the use of suitable solvents or diluents.
  • suitable solvents or diluents Practically all inert organic solvents can be considered as such. These include in particular aliphatic and aromatic, optionally chlorinated, hydrocarbons, such as benzene, toluene, xylene, methylene chloride, chloroform and carbon tetrachloride.
  • the X are OH
  • acidic catalysts e.g. Sulfuric acid or p-toluenesulfonic acid
  • a catalyst such as boron trifluoride
  • the reaction temperature can be varied within a wide range. Generally one works between 25 and 15o ° C, preferably between 7o and 12o ° C ..
  • the reaction is generally allowed to proceed at normal pressure.
  • the compounds when using 3- (3,4-methylenedioxyphenyl) propanediol-1,2 as the starting product, the compounds are preferably used in equimolar amounts.
  • An excess of one or the other reaction component has no significant advantages.
  • the two reaction components are reacted in one of the specified solvents in the presence of an acid catalyst at the specified temperatures.
  • the resulting water is removed by azeotropic distillation.
  • the carbonyl component is used in excess and thus serves as a reaction component and solvent.
  • the reaction is preferably carried out in the presence of one of the specified catalysts at the specified temperatures. Working up after the reaction is carried out as usual by shaking with an organic solvent, washing, drying the organic phase and distilling off the solvent.
  • the compounds according to the invention are characterized by their boiling point.
  • active ingredient combinations of the benzodioxole derivatives of the formula (I) according to the invention with carbamates, carboxylic acid esters, phosphoric acid esters, cycloalkanes and haloalkanes show an excellent increase in activity compared to the individual active ingredients or their sum.
  • Psylliodes chrysocephala Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermesthren spp., Dermesthren spp spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon ⁇ solstitialis, Costelytra zealandica.
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium phara onis, Vespa spp.
  • Diptera e.g. Aedes spp., Anopholes app., 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 sppanus, Bibio hort , Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
  • Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,. Chori .; Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..
  • the active substance combinations can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension - emulsion concentrates, seed powders, active substance-impregnated natural and synthetic substances , Fine encapsulation 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 heat mist formulations.
  • formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents.
  • extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally 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.
  • organic solvents can, for example, also be used as auxiliary solvents.
  • liquid solvents aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar , 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, for example aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; as solid carrier substances: natural rock meals, such as kaolin
  • Adhesives such as carboxymethyl cellulose and 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 active substance content of the use forms prepared from the commercially available formulations can vary widely.
  • 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 ingredient combinations are notable for an excellent residual action on wood and clay and for good stability to alkali on limed substrates.
  • Test animals Musca domestica, Weymann strain (resistant to carbamates and phosphoric acid esters)
  • 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. Will the 100 is not reached after 6 hours, the percentage of knock-down test animals is determined.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)

Abstract

Benzodioxolderivate der Formel <IMAGE> in welcher R¹ und R² gleich oder verschieden sein können und für H, Alkyl, Alkenyl, Alkinyl und Aryl stehen oder R¹ und R² zusammen für eine Alkylengruppe stehen, und ein Verfahren zu ihrer Herstellung. Diese neuen Benzodioxolderivate weisen zusammen mit A) Carbamaten und/oder B) Carbonsäureestern, einschliesslich der natürlichen sowie synthetischen Pyrethrolde, und/oder C) Phosphorsäureestern und/oder D) Cycloalkanen und/oder E) Halogenalkanen eine besonders hohe insektizide und akarizide Wirkund auf.Benzodioxole derivatives of the formula <IMAGE> in which R¹ and R² can be the same or different and represent H, alkyl, alkenyl, alkynyl and aryl or R¹ and R² together represent an alkylene group, and a process for their preparation. These new benzodioxole derivatives, together with A) carbamates and / or B) carboxylic acid esters, including the natural and synthetic pyrethrolds, and / or C) phosphoric acid esters and / or D) cycloalkanes and / or E) haloalkanes, have a particularly high insecticidal and acaricidal activity.

Description

Die vorliegende Erfindung betrifft neue Benzodioxolderivate, ein Verfahren zu ihrer Herstellung sowie ihre Verwendung in insektiziden und akariziden Mitteln als Synergisten.The present invention relates to new benzodioxole derivatives, a process for their preparation and their use in insecticidal and acaricidal compositions as synergists.

Es sind bereits synergistische Mischungen von Carbamaten,. z.B. 2-iso-Propoxy-phenyl-N-methylcarbamat oder von Phosphorsäureestern, z.B. 0,0-Diäthyl-0-[2-isopropyl-4-methyl- pyrimidin(6)yl]-thionophosphorsäureester oder von natürlichen oder synthetischen Pyrethroiden mit Piperonyläthern. wie z.B.α-[2-(2-Hutoxy-äthoxy)-äthoxy]-4,5-methylendioxy-2-propyl-toluol, bekannt (vergleiche 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-methylen- dioxy-2-propyl-toluol erlangt.There are already 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-methyl-pyrimidin (6) yl] -thionophosphoric acid ester or of natural or synthetic pyrethroids with piperonyl ethers. such as α- [2- (2-hutoxy-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-methylene-dioxy-2-propyl-toluene has achieved a certain practical importance.

Es wurden nun die neuen Benzodioxolderivate der Formel (I)

Figure imgb0001
in welcher

  • R1 und R2 gleich oder verschieden sein können und für H, Alkyl, Alkenyl, Alkinyl und Aryl stehen oder
  • R1 und R2 zusammen für eine Alkylengruppe,stehen gefunden.
The new benzodioxole derivatives of the formula (I)
Figure imgb0001
 in which
  • R 1 and R 2 may be the same or different and represent H, alkyl, alkenyl, alkynyl and aryl or
  • R 1 and R 2 together represent an alkylene group.

Es wurde außerdem gefunden, daß diese Verbindungen hergestellt werden können, indem man eine Verbindung der Formel II

Figure imgb0002
in welcher

  • X für OH oder beide Reste X für -O- stehen,
  • mit einer Carbonylverbindung der allgemeinen Formel III
    Figure imgb0003
    in welcher
  • R1 und R2 die oben angegebene Bedeutung haben, gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt.
It has also been found that these compounds can be prepared by using a compound of formula II
Figure imgb0002
 in which
  • X is OH or both radicals X are -O-,
  • with a carbonyl compound of the general formula III
    Figure imgb0003
     in which
  • R 1 and R 2 have the meaning given above, optionally in the presence of a diluent.

Es wurde außerdem gefunden, daß diese neuen Benzodioxolderivate zusammen mit

  • A) Carbamaten und/oder
  • B) Carbonsäureestern, einschließlich der natürlichen sowie synthetisohen.Pyrethroide, und/oder
  • C) Phosphorsäureestern und/oder
  • D) Cycloalkanen und/oder
  • E) Halogenalkanen
eine besonders hohe insektizide und akarizide Wirkung aufweisen.It has also been found that these new benzodioxole derivatives coexist with
  • A) carbamates and / or
  • B) carboxylic acid esters, including the natural and synthetic pyrethroids, and / or
  • C) phosphoric acid esters and / or
  • D) cycloalkanes and / or
  • E) 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 (IV)
    Figure imgb0004
    in welcher
    • 3 R für Aryl, heterocyclische Reste oder Oximrest steht,
    • 4 R für Wasserstoff oder Alkyl mit 1 bis 4 Kohlenstoffatomen steht und
    • Figure imgb0005
      C1-4-Alkyl, insbesondere Methyl, oder Dialkylamino mit 1 bis 4 Kohlenstoffatomen je Alkylteil substituiert sind. Weiterhin sind besonders bevorzugt Carbamate, in denen R3 für einen Oximrest der allgemeinen Formel (IVa)
      Figure imgb0006
      steht, in welcher
    • R 6 und R 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;
      Besonders erwähnt seien folgende Carbamate 2-Methylphenyl-, 2-Äthylphenyl-, 2-n-Propylphenyl-, 2-Methoxyphenyl-, 2-Äthoxyphenyl-, 2-iso-Propoxyphenyl-, 4-Methylphenyl-, 4-Äthylphenyl-, 4-n-Propylphenyl-, 4-Methoxyphenyl-, 4- Äthoxyphenyl-, 4-n-Propoxyphenyl-, 3,4,5-Trimethylphenyl-, 1-Naphthyl-, 2.3-Dihydro-2,2-dimethyl-7-benzoturanyl-, 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.
  • B) Carbonsäursestern der allgemeinen Formel (V)
    Figure imgb0007
    Ln welcher
    • R8 für Alkyl, Aralkyl, Aryl oder Cycloalkyl steht, die gegebenenfalls substituiert sein können und
    • 9 R für Wasserstoff, Alkyl, Halogenalkyl, Alkenyl, Alkinyl oder Nitril steht und
    • R10 für Aryl oder einen Heterocyclus steht, oder gemeinsam mit R9 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 (IV)
    Figure imgb0004
     in which
    • 3 R represents aryl, heterocyclic radicals or oxime radical,
    • 4 R represents hydrogen or alkyl having 1 to 4 carbon atoms and
    • Figure imgb0005
      C 1-4 alkyl, especially methyl, or dialkylamino having 1 to 4 carbon atoms per alkyl part are substituted. Carbamates in which R 3 represents an oxime radical of the general formula ( IV a) are furthermore particularly preferred.
      Figure imgb0006
       is in which
    • R 6 and R are identical or different and are alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkylmercapto, alkoxycarbonyl, carbonylamide, alkylmercaptoalkyl, each having 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;
      The following carbamates, 2-methylphenyl-, 2-ethylphenyl-, 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-benzoturanyl -, 2- [1,3-Dioxolan (2) yl-phenyl] - or 2,2-dimethyl-1,3-benzodioxol- (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.
  • B) carboxylic acid esters of the general formula (V)
    Figure imgb0007
     Ln what
    • R 8 represents alkyl, aralkyl, aryl or cycloalkyl, which may optionally be substituted and
    • 9 R represents hydrogen, alkyl, haloalkyl, alkenyl, alkynyl or nitrile and
    • R 10 represents aryl or a heterocycle, or together with R 9 forms an optionally substituted cyclopentenone ring.

Besonders bevorzugt sind Carbonsäureester,in denen R für Alkyl mit 1 bis 6 Kohlenstoffatomen, das gegebenenfalls durch gegebenenfalls substituiertes Phenyl substituiert ist, Cyclopropyl, das gegebenenfalls durch Alkyl,Alkenyl, Halogen- alkyl oder Halogenalkenyl mit jeweils bis zu 6 Kohlenstoffatomen substituiert ist, oder für Phenyl, das gegebenenfalls substituiert ist, steht. Bevorzugt sind Carbonsäureester, in denen R9 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 represents alkyl having 1 to 6 carbon atoms, which is optionally substituted by optionally substituted phenyl, cyclopropyl, which is optionally substituted by alkyl, alkenyl, haloalkyl or haloalkenyl, each having up to 6 carbon atoms, or for Phenyl which is optionally substituted. Carboxylic acid esters in which R 9 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 R10 für Phenyl steht, das gegebenenfalls durch C1-4-Alkyl, Halogen, insbesondere Fluor oder Chlor, gegebenenfalls substituiertes Phenoxy; sowie gegebenenfalls substituiertes Benzyl substituiert ist, ferner für Furanyl, Tetrahydrophthalimido, Benzodioxol, die gegebenenfalls durch Halogen, insbesondere Chlor, Alkyl oder Alkenyl mit bis zu 4-Kohlenstoffatomen oder Benzyl substituiert sind, steht, und ferner für Cyclopentenon steht, das gegebenenfalls durch C1-4-Alkyl, Furfuryl, C1-5-Alkenyl substituiert ist.Further particularly preferred are carboxylic acid esters in which R 10 is phenyl which is optionally substituted by C 1-4 alkyl, halogen, in particular fluorine or chlorine, optionally substituted phenoxy; and optionally substituted benzyl is further substituted for furanyl, tetrahydrophthalimido, benzodioxole, which may be substituted by halogen, in particular chlorine, alkyl or alkenyl with up to 4-carbon atoms or benzyl is substituted, and also stands for cyclopentenone which is optionally substituted by C 1-4 alkyl, furfuryl, C 1-5 alkenyl.

Weiter sind besonders bevorzugt die natürlich vorkommenden Pyrethroide;

  • Besonders erwähnt seien folgende Carbonsäureester
Essigsäure-[2,-(3,4-dichlorphenyl)-2,2,2-trichloräthyl]-ester, 2,3,4,5-Tetrahvdrophthalimidomethvlchrvsanthemat und (5-Benzyl-3-furyl)-methyl-2,2-dimethyl-3-(2-methyl- propenyl)-cyclopropan-carboxylat.Furthermore, the naturally occurring pyrethroids are particularly preferred;
  • The following carboxylic acid esters are particularly mentioned
Acetic acid [2, - (3,4-dichlorophenyl) -2,2,2-trichloroethyl] ester, 2,3,4,5-tetrahvdrophthalimidomethvlchrvsanthemat and (5-benzyl-3-furyl) -methyl-2,2 -dimethyl-3- (2-methyl-propenyl) cyclopropane carboxylate.

C) Phosphorsäureestern der allgemeinen Formel (VI)

Figure imgb0008
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 Rest R13 steht und
  • R11 und R12 gleich oder verschieden sind und für Alkyl oder Aryl stehen und
  • R13 für Alkyl, Aryl, Heteroaryl, Aralkyl, Alkenyl, Dioxanyl, oder einen Oximrest oder für den gleichen Rest steht, an den es gebunden ist.
C) phosphoric acid esters of the general formula (VI)
Figure imgb0008
 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 radical R 13 and
  • R 11 and R 12 are the same or different and represent alkyl or aryl and
  • R 13 represents alkyl, aryl, heteroaryl, aralkyl, alkenyl, dioxanyl, or an oxime radical or the same radical to which it is attached.

Besonders bevorzugt sind Phosphorsäureester, in denen

  • R11 und R12 gleich oder verschieden sind und für C1-4-Alkyl oder Phenyl stehen,
  • R 13 für Alkyl mit 1 bis 4 Kohlenstoffatomen steht, das gegebenenfalls durch Halogen, Hydroxyl, Nitril, gegebenfalls substituiertes 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 (IVa)
    Figure imgb0009
    wobei R6 und R7 die oben angegebene Bedeutung besitzen, insbesondere jedoch für Cyan oder Phenyl stehen,
  • R13 steht ferner für Dioxanyl, das durch denselben Rest substituiert ist, an den R gebunden ist, oder R13 steht für den gleichen Rest, an den er gebunden ist, oder R13 steht für Phenyl, das gegebenenfalls durch Methyl, Nitro, Nitril, Halogen, Methylthio substituiert ist; R13 steht außerdem besonders bevorzugt für gegebenenfalls durch C1-4-Alkyl, Halogen substituierte Heteroaromaten, wie Pyridin, Chinolin, Chinoxalin, Pyrimidin, Diazinon, Benzo-1,2,4-triazin.
Phosphoric acid esters in which
  • R 11 and R 12 are the same or different and represent C 1-4 alkyl or phenyl,
  • R 13 represents alkyl having 1 to 4 carbon atoms, which is optionally substituted by halogen, hydroxyl, nitrile, optionally 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 (IVa)
    Figure imgb0009
     where R 6 and R 7 have the meaning given above, but in particular are cyano or phenyl,
  • R 13 also represents dioxanyl which is substituted by the same radical to which R is bonded, or R 13 represents the same radical to which it is bonded, or R 13 represents phenyl which is optionally substituted by methyl, nitro, nitrile , Halogen, methylthio is substituted; R 13 also particularly preferably represents heteroaromatics which are optionally substituted by C 1-4 -alkyl, halogen, such as pyridine, quinoline, quinoxaline, pyrimidine, diazinon, benzo-1,2,4-triazine.

Besonders erwähnt seien folqende Phosphorsäureester

  • 0,0-Dimethyl- bzw. 0,0-Diäthyl-0-(2,2-dichlor- bzw. 2,2-dibromvinyl)-phosphorsäureeater,
  • 0,0-Diäthyl-0-(4-nitro-phenyl)-thionophosphorsäureester, 0,0-Dimethyl-0-(3-methyl-4-methylthio)-thionophosphor- säureester,
  • 0,0-Dimethyl-0-(3-methyl-4-nitro)-thionophosphorsäureester, 0-Äthyl-S-n-propyl-0-(2,4-dichlorphenyl)-thionophosphor- säureester,
  • 0-äthyl-S-n-propyl-0-(4-methylthio-phenyl)-thionophosphor- säureester,
  • 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]-thiono- methanphosphonsäureester,
  • 0,0-Diäthyl-0-[2-iso-propyl-6-methyl-pyrimidin(4)yl]-thiono- phosphorsäureester,
  • 0,0-Diäthyl-0-[3-chlor-4-methyl-cumarin(7)yl]-thionophosphor- säureester,
  • 0,0-Dimethyl-2,2,2-trichlor-1-hydroxy-äthem-phosphonsäureester, 0,0-Dimethyl-S-(methylcarbamoylmethyl)-thionophosphorsäureester.
Particular mention should be made of the following phosphoric acid esters
  • 0.0-dimethyl- or 0.0-diethyl-0- (2,2-dichloro- or 2,2-dibromovinyl) phosphoric acid,
  • 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-Sn-propyl-0- (2,4-dichlorophenyl) thionophosphoric acid ester,
  • 0-ethyl-Sn-propyl-0- (4-methylthio-phenyl) -thionophosphoric acid ester,
  • 0.0-dimethyl-S- [4-oxo-1,2,3-benzotriazine (3) yl-methyl] thionothiolphosphate,
  • 0-methyl-0- [2-iso-propyl-6-methoxypyrimidine (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-trichloro-1-hydroxy-ether-phosphonic acid ester, 0.0-dimethyl-S- (methylcarbamoylmethyl) thionophosphoric acid ester.

D) Cycloalkanen der Formel (VII)

Figure imgb0010
in welcher

  • Hal Halogen, vorzugsweise Chlor, bedeutet. Besonders erwähnt sei 1,2,3,4,5,6-Hexachlorohexan.
D) cycloalkanes of the formula (VII)
Figure imgb0010
 in which
  • Hal is halogen, preferably chlorine. 1,2,3,4,5,6-hexachlorohexane should be mentioned in particular.

E) Halogenalkanen der Formel (VIII)

Figure imgb0011
in welcher

  • Hal' für Chlor oder Brom
  • R14 für Wasserstoff oder Hydroxyl,
  • R 15 und R16 gleich oder verschieden sind und für Halogen, Alkyl oder Alkoxy und
  • R17 für Wasserstoff oder Halogen stehen.
E) haloalkanes of the formula (VIII)
Figure imgb0011
 in which
  • Hal 'for chlorine or bromine
  • R 14 represents hydrogen or hydroxyl,
  • R 15 and R 16 are the same or different and are halogen, alkyl or alkoxy and
  • R 17 represents hydrogen or halogen.

Besonders bevorzugt sind Halogenalkane, in denen

  • R 14 Wasserstoff oder Hydroxyl bedeutet,
  • R 15 und R 16 für gleiches Halogen, Alkyl bzw. Alkoxy mit 1 bis 4 Kohlenstoffatomen je Alkyl- bzw. Alkoxyrest stehen und
  • R17 Halogen bedeutet.
Halogenalkanes in which
  • R 14 represents hydrogen or hydroxyl,
  • R 15 and R 16 represent the same halogen, alkyl or alkoxy having 1 to 4 carbon atoms per alkyl or alkoxy radical and
  • R 17 means halogen.

Besonders zu erwähnen seien folgende Halogenalkane 1,1,1-Trichlor-2,2-bis-(4-chlor- bzw. 4-äethoxyphenyl)-äthan, 1,1,1-Trichlor-2-hydroxy-2,2-bis-(4-chlorphenyl)-äthan und 1,1-Dichlor-2,2-bis-(4-äthylphenyl)-äthan.The following haloalkanes should be mentioned in particular 1,1,1-trichloro-2,2-bis (4-chloro- or 4-ethoxyphenyl) -ethane, 1,1,1-trichloro-2-hydroxy-2,2-bis- (4-chlorophenyl ) -ethane and 1,1-dichloro-2,2-bis (4-ethylphenyl) -ethane.

Überraschenderweise ist die insektizide und/oder akarizide Wirkung solcher Wirkstoffkombinationen wesentlich höher als die Wirkung der Einzelkomponenten bzw. die Summe der Wirkungen der Einzelkomponenten. Sie ist ferner wesentlich höher als die Wirkung von Wirkstoffkombination mit dem bekannten Synergisten Piperonylbutoxyd.Surprisingly, the insecticidal and / or acaricidal action of such active compound combinations is considerably 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 active ingredient combinations with the well-known synergist piperonyl butoxide.

Außerdem zeigen die erfindungsgemäß verwendbaren Benzodioxolderivate ausgezeichnete synergistische Wirksamkeit nicht nur bei einer Wirkstoffklasse, sondern bei Wirkstoffen aus den verschiedensten chemischen Stoffgruppen.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 Benzodioxolderivate eine wertvolle Bereicherung der Technik dar.The benzodioxole derivatives according to the invention thus represent a valuable addition to the technology.

Die neuen Benzodioxolderivate sind durch die Formel (I) allgemein definiert. Vorzugsweise stehen in der Formel (I) jedoch

  • R1 und R2 für Wasserstoff, geradkettiges oder verzweigtes Alkyl bzw. Alkenyl mit bis zu 10 C-Atomen, sowie für gegebenenfalls substituiertes Phenyl oder
  • R und R 2 stehen zusammen für eine geradkettige oder verzweigte Alkylkette mit bis zu 10 C-Atomen.
Formula (I) provides a general definition of the new benzodioxole derivatives. Preferably, however, are in the formula (I)
  • R 1 and R 2 for hydrogen, straight-chain or branched alkyl or alkenyl with up to 10 C atoms, and for optionally substituted phenyl or
  • R and R 2 together represent a straight-chain or branched alkyl chain with up to 10 carbon atoms.

Als Beispiele seien im einzelnen genannt: 5-(3.4-Methylendioxybenzyl)-dioxolan 2-Methyl-5-(3.4-methylendioxybenzyl)-dioxolan 2-Äthyl-5-(3.4-methylendioxybenzyl)-dioxolan 2-n-Propyl-5-(3.4-methylendioxybenzyl)-dioxolan 2-1-Propyl-5-(3.4.-methylendioxybenzyl)-dioxolan 2-n-Butyl-5-(3.4.-methylendioxybenzyl)-dioxolan 2-i-Butyl-5-(3.4-methylendioxybenzyl)-dioxolan 2-t-Butyl-5-(3.4-methylendloxybenzyl)-dioxolan 2-Allyl-5-(3.4-methylendioxybenzyl)-dioxolan 2-Methallyl-5-(3,4-methylendioxybenzyl)-dioxolan 2-Crotyl-5-(3.4-methylendioxybenzyl)dioxolan 2-Äthinyl-5-(3.4-methylendioxybenzyl)-dioxolan 2-Phenyl-5-(3.4-methylendioxybenzyl)-dioxolan 2-(3.4-Methylendioxyphenyl)-5-(3.4-methylendioxybenzyl)-dioxolan 2,2-Dimethyl-5-(3.4-methylendioxybenzyl)-dioxolan 2-Methyl-2-äthyl-5-(3.4-methylendioxybenzyl)-dioxolan 2-Methyl-2-n-propyl-5-(3.4-methylendioxybenzyl)-dioxolan 2-Methyl-2-i-propyl-5-(3.4-methylendioxybenzyl)-dioxolan 2-Methyl-2-n-butyl-5-(3.4-methylendioxybenzyl)-dioxolan 2-Methyl-2-i-butyl-5-(3.4-methylendioxybenzyl)-dioxolan 2-Methyl-2-t-butyl-5-(3.4-methylendioxybenzyl)-dioxolan 2,2-Diäthyl-5-(3.4-methylendioxybenzyl)-dioxolan 2,2-Di-n-propyl-5-(3.4-methylendioxybenzyl)-dioxolan 2,2-Di-n-butyl-5-(3.4-methylendioxybenzyl)-dioxolan 2-Methyl-2-phenyl-5-(3.4-methylendioxybenzyl)-dioxolan 2-Spirocyclopentan-5-(3.4-methylendioxybenzyl)-dioxolan 2-Spirocyclohexan-5-(3.4-methylendioxybenzyl)-dioxolan 2-(2.4.4-Trimethyl-spirocyclohexan)-S-(3,4-methylendioxybenzyl)-dioxolan.Examples are: 5- (3.4-methylenedioxybenzyl) dioxolane 2-methyl-5- (3.4-methylenedioxybenzyl) dioxolane 2-ethyl-5- (3.4-methylenedioxybenzyl) dioxolane 2-n-propyl-5- (3.4-methylenedioxybenzyl) dioxolane 2-1-propyl-5- (3.4.-methylenedioxybenzyl) dioxolane 2-n-butyl 5- (3.4.-methylenedioxybenzyl) dioxolane 2-i-butyl-5- (3.4-methylenedioxybenzyl) dioxolane 2-t-butyl-5- (3.4-methylenedloxybenzyl) dioxolane 2-allyl-5- (3.4-methylenedioxybenzyl ) -dioxolane 2-methallyl-5- (3,4-methylenedioxybenzyl) dioxolane 2-crotyl-5- (3,4-methylenedioxybenzyl) dioxolane 2-ethynyl-5- (3,4-methylenedioxybenzyl) dioxolane 2-phenyl-5- ( 3.4-methylenedioxybenzyl) dioxolane 2- (3.4-methylenedioxyphenyl) -5- (3.4-methylenedioxybenzyl) dioxolane 2,2-dimethyl-5- (3.4-methylenedioxybenzyl) dioxolane 2-methyl-2-ethyl-5- (3.4 -methylenedioxybenzyl) -dioxolane 2-methyl-2-n-propyl-5- (3.4-methylenedioxybenzyl) -dioxolane 2-methyl-2-i-propyl-5- (3.4-methylenedioxybenzyl) -dioxolane 2-methyl-2-n -butyl-5- (3.4-methylenedioxybenzyl) dioxolane 2-methyl-2-i-butyl-5- (3.4-methylenedioxybenzyl) dioxolane 2-methyl-2-t-butyl-5- (3.4-methylenedioxybenzyl) dioxolane 2,2-diethyl-5- (3,4-methylenedioxyb enzyl) dioxolane 2,2-di-n-propyl-5- (3.4-methylenedioxybenzyl) dioxolane 2,2-di-n-butyl-5- (3.4-methylenedioxybenzyl) dioxolane 2-methyl-2-phenyl- 5- (3.4-methylenedioxybenzyl) dioxolane 2-spirocyclopentane-5- (3.4-methylenedioxybenzyl) dioxolane 2-spirocyclohexane-5- (3.4-methylenedioxybenzyl) dioxolane 2- (2.4.4-trimethyl spirocyclohexane) -S- ( 3,4-methylenedioxybenzyl) dioxolane.

Bei den als Ausgangsverbindungen zur Herstellung der erfindungsgemäBen Benzodioxolderivate dienenden Verbindungen der Formel II handelt es sich um 3-(3,4-Methylendioxyphenyl)-propandiol-1,2 und um 3,4-Methylendioxybenzyl-äthylenoxid. Beide Verbindungen sind bekannt, ebenso wie die Carbonylverbindungen der Formel III.The compounds of the formula II which serve as starting compounds for the preparation of the benzodioxole derivatives according to the invention are 3- (3,4-methylenedioxyphenyl) propanediol-1,2 and 3,4-methylenedioxybenzylethylene oxide. Both compounds are known, as are the carbonyl compounds of the formula III.

Das Verfahren zur Herstellung der erfindungsgemäßen Verbindungen wird gegebenenfalls unter Mitverwendung geeigneter Lösungs- oder Verdünnungsmittel durchgeführt. Als solche kommen praktisch alle inerten organischen Solventien infrage. Hierzu gehören insbesondere aliphatische und aromatische, gegebenenfalls chlorierte, Kohlenwasserstoffe, wie Benzol, Toluol, Xylol, Methylenchlorid, Chloroform und Tetrachlorkohlenstoff.The process for the preparation of the compounds according to the invention is optionally carried out with the use of suitable solvents or diluents. Practically all inert organic solvents can be considered as such. These include in particular aliphatic and aromatic, optionally chlorinated, hydrocarbons, such as benzene, toluene, xylene, methylene chloride, chloroform and carbon tetrachloride.

Für den Fall, daß die X für OH stehen, arbeitet man in Gegenwart von sauren Katalysatoren, wie z.B. Schwefelsäure oder p-Toluolsulfonsäure und für den Fall, daß die beiden X für ein Sauerstoffatom stehen, arbeitet man in Gegenwart eines Katalysators, wie Bortrifluorid.In the event that the X are OH, one works in the presence of acidic catalysts, e.g. Sulfuric acid or p-toluenesulfonic acid and in the event that the two X represent an oxygen atom, one works in the presence of a catalyst such as boron trifluoride.

Die Reaktionstemperatur kann innerhalb eines größeren Bereichs variiert werden. Im allgemeinen arbeitet man zwischen 25 und 15o°C, vorzugsweise zwischen 7o und 12o°C..The reaction temperature can be varied within a wide range. Generally one works between 25 and 15o ° C, preferably between 7o and 12o ° C ..

Die Umsetzung läßt man im allgemeinen bei Normaldruck ablaufen.The reaction is generally allowed to proceed at normal pressure.

Zur Durchführung des Verfahrens setzt man bei Verwendung von 3-(3,4-Methylendioxyphenyl)-propandiol-1,2 als Ausgangsprodukt die Verbindungen vorzugsweise in äquimolaren Mengen ein. Ein Überschuß der einen oder anderen Reaktionskomponente bringt keine wesentlichen Vorteile. Im allgemeinen werden die beiden Reaktionskomponenten in einem der angegebenen Lösungsmittel in Gegenwart eines sauren Katalysators bei den angegebenen Temperaturen umgesetzt. Das dabei entstehende Wasser wird durch azeotrope Destillation entfernt.To carry out the process, when using 3- (3,4-methylenedioxyphenyl) propanediol-1,2 as the starting product, the compounds are preferably used in equimolar amounts. An excess of one or the other reaction component has no significant advantages. In general, the two reaction components are reacted in one of the specified solvents in the presence of an acid catalyst at the specified temperatures. The resulting water is removed by azeotropic distillation.

Verwendet man 3,4-Methylendioxybenzyläthylenoxyd als Ausgangskomponente, so ist eine bevorzugte Austührungsform die, daß die Carbonylkomponente im Überschuß eingesetzt wird und so als Reaktionskomponente und Lösungsmittel dient. Die Umsetzung erfolgt vorzugsweise in Gegenwart eines der angegebenen Katalysators bei den angegebenen Temperaturen. Die Aufarbeitung nach beendeter Reaktion erfolgt wie üblich durch Ausschütteln mit einem organischen Lösungsmittel, Waschen, Trocknen der organischen Phase und Abdestillieren des Lösungsmittels.If 3,4-methylenedioxybenzylethylene oxide is used as the starting component, a preferred embodiment is that the carbonyl component is used in excess and thus serves as a reaction component and solvent. The reaction is preferably carried out in the presence of one of the specified catalysts at the specified temperatures. Working up after the reaction is carried out as usual by shaking with an organic solvent, washing, drying the organic phase and distilling off the solvent.

Die erfindungsgemäßen Verbindungen werden durch ihren Siedepunkt charakterisiert.The compounds according to the invention are characterized by their boiling point.

Wie bereits erwähnt, zeigen Wirkstoffkombinationen der erfindungsgemäßen Benzodioxolderivate der Formel (I) mit Carbamaten, Carbonsäureestern, Phosphorsäureestern, Cycloalkanen und Halogenalkanen eine hervorragende Wirkungssteigerung gegenüber den Einzelwirkstoffen bzw. gegenüber deren Summe.As already mentioned, active ingredient combinations of the benzodioxole derivatives of the formula (I) according to the invention with carbamates, carboxylic acid esters, phosphoric acid esters, cycloalkanes and haloalkanes show an excellent 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. Als besonders geeignet haben sich jedoch Mischverhältnisse von 0,5:1,0 bis 3,0:1,0 erwiesen. Diese Wirkstoffkpmbinationen bewirken nicht nur eine schnelle knock-down-Wirkung, sondern bewirken auch die nachhaltige Abtötung von tierischen Schädlingen, insbesondere Insekten und Spinnentieren, die in der Landwirtschaft, in Forsten, im Vorrats- und Materialschutz sowie auf dem Hygienesektor vorkommen. Sie sind gegen normale sensible und resistente Arten sowie gegen alle oder einzelne Entwicklungsstadien wirksam. Zu den oben erwähnten Schädlingen gehören:

  • Aus der Ordnung der Isopoda zum Beispiel Oniscus asellus,
  • Armadillidium vulgare, Porcellio scaber.
  • Aus der Ordnung der Diplopoda zum Beispiel Blaniulus guttulatus.
  • Aus der Ordnung der Chilopoda zum Beispiel Geophilus carpophagus, Scutigera spec.
  • Aus der Ordnung der Symphyla z.B. Scutigerella immaculata.
  • Aus der Ordnung der Thysanura z.B. Lopisma saccharina.
  • Aus der Ordnung der Collembola z.B. Onychiurus armatus.
  • Aus der Ordnung der
    Figure imgb0012
    z.B. Blatta orientalis,
  • Periplaneta americana, Leucophaea maderae, Blattellagermanica,
  • Acheta donesticus, Gryllotalpa spp., Locusta migratoria
  • migratarioides, 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, Heematopinus app., 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, Cryptomyzus ribis, Doralis fabae,
  • Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis,
  • Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum
  • padi, Empoasca app., Euscelis billobatus, Nephotettix
  • cincticeps, Lecanium corni, Saissetia oleae, Laodelphax
  • striatellus, Nilaparvata lugens, Aonidiella aurantii,
  • Aspidiotus hederas, Pseudococcus spp., Psylla spp.
  • Aus der Ordnung der Lepidoptera z.B. Pectinophora gossypiella,
  • Bupalus piniarius, Creimatobia brumata, Lithocolletis
  • blancardella, Hypenomeuta 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, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.
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. These combinations of active ingredients not only result in a quick knock-down effect, but also cause the sustainable killing of animal pests, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stocks and materials, and in the hygiene sector. They are effective against normal sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above include:
  • From the order of the Isopoda, for example, Oniscus asellus,
  • Armadillidium vulgare, Porcellio scaber.
  • From the order of the Diplopoda, for example, Blaniulus guttulatus.
  • From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spec.
  • From the order of the Symphyla, for example, Scutigerella immaculata.
  • From the order of the Thysanura, for example Lopisma saccharina.
  • From the order of the Collembola, for example Onychiurus armatus.
  • From the order of the
    Figure imgb0012
    eg Blatta orientalis,
  • Periplaneta americana, Leucophaea maderae, Blattellagermanica,
  • Acheta donesticus, Gryllotalpa spp., Locusta migratoria
  • migratarioides, Melanoplus differentialis, Schistocerca gregaria.
  • From the order of the Dermaptera, for example, Forficula auricularia.
  • From the order of the Isoptera, for example Reticulitermes spp.
  • From the order of the Anoplura, for example Phylloxera vastatrix,
  • Pemphiqus spp., Pediculus humanus corporis, Heematopinus app., Linognathus spp,
  • From the order of the Mallophaga, for example Trichodectes spp., Damalinea spp.
  • From the order of the Thysanoptera, for example Hercinothrips femoralis, Thrips tabaci.
  • From the order of the Heteroptera, for example Eurygaster spp.,
  • Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
  • From the order of the Homoptera, for example Aleurodes brassicae,
  • Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii,
  • Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae,
  • Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis,
  • Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum
  • padi, Empoasca app., Euscelis billobatus, Nephotettix
  • cincticeps, Lecanium corni, Saissetia oleae, Laodelphax
  • striatellus, Nilaparvata lugens, Aonidiella aurantii,
  • Aspidiotus hederas, Pseudococcus spp., Psylla spp.
  • From the order of the Lepidoptera, for example Pectinophora gossypiella,
  • Bupalus piniarius, Creimatobia brumata, Lithocolletis
  • blancardella, hypenomeuta 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, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonodanaanaanaanaanaanaanaanaanaa, Capa , 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.,From the order of the Coleoptera e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp.,

Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon` solstitialis, Costelytra zealandica.Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermesthren spp., Dermesthren spp spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, 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 phara onis, Vespa spp., Aus der Ordnung der Diptera z.B. Aedes spp., Anopholes app., 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.From the order of Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium phara onis, Vespa spp., From the order of Diptera e.g. Aedes spp., Anopholes app., 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 sppanus, Bibio hort , Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

Aus der Ordnung der Siphonaptera z.D. Xenopsylla cheopis, Ceratophyllus spp.. Aus der Ordnung der Arachnida z.B. Scorpio maurus, Latrodectus mactans.From the order of the Siphonaptera z.D. Xenopsylla cheopis, Ceratophyllus spp .. From the order of the Arachnida e.g. 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 Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,. Chori .; Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..

Die Wirkstoffkombinationen können in die Üblichen Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Spritzpulver, Suspensionen, Pulver, Stäubemittel, Schäume, Pasten, lösliche Pulver, Granulate, Aerosole, Suspension-Emulsions- konzentrate, Saatgutpuder, Wirkstoff-imprägnierte Natur-und synthetische Stoffe, Feinstverkapselungen in polymeren Stoffen und in Hüllmassen für Saatgut, ferner in Formulierungen mit Brennsätzen, wie Räucherpatronen, -dosen, -spiralen u.ä. sowie ULV-Kalt- und Wärmenebel-Formulierungen.The active substance combinations can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension - emulsion concentrates, seed powders, active substance-impregnated natural and synthetic substances , Fine encapsulation 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 heat mist 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 Trägerstoffen, 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 Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen infrage: Aromaten, wie Xylol, Toluol, oder Alkylnaphthaline, chlorierte Aromaten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chloräthylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine z.B. Erdölfraktionen, Alkohole, wie Butanol oder Glycol sowie deren 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 Temperatur und unter Normaldruck gasförmig sind, z.B. Aerosol-Treibgase, wie Halogenkohlenwasserstoffe sowie Butan, Propan, Stickstoff und Kohlendioxid; als feste Tägerstoffe: natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorrillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate; als feste Trägerstoffe für Granulate: gebrochene und fraktionierte natürliche Cesteine wie Calcit, Marmor, Bims, Sepiolith, 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, Arylsulfonata sowie Eiweißhydrolysate; als Dispergiermittel: z.B. Ligrin-, Sulfitablaugen und Methylcellulose.These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, 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 hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar , 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, for example aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; as solid carrier substances: natural rock meals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorrillonite or diatomaceous earth and synthetic rock meals, such as highly disperse silica, aluminum oxide and silicates; as solid carriers for granules: broken and fractionated natural cestones such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems as emulsifiers and / or foam-generating agents: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as a dispersing agent: eg ligrin, sulfite waste and methyl cellulose.

Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische pulverige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat.Adhesives such as carboxymethyl cellulose and 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, vorzugsweise 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 Wirkstoffgehalt der aus den handelsüblichen Formulierungen bereiteten Anwendungsformen kann in weiten Bereichen vairieren. Die Wirkstoffkonzentration der Anwendungsformen kann von 0,0000001 bis zu 100 Gew.-% Wirkstoff, vorzugsweise zwischen 0,01 und 10 Gew.-% liegen.The active substance content of the use forms prepared from the commercially available formulations can vary widely. 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 Wirkstoffkombinotionen 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 ingredient combinations are notable for an excellent residual action on wood and clay and for good stability to alkali on limed substrates.

Beispiel A Example A LT100 - TestLT 100 test

Testtiere: Musca domestica, Stamm Weymanns (gegen Carbamate und Phosphorsäureester resistent)Test animals: Musca domestica, Weymann strain (resistant to carbamates and phosphoric acid esters)

Lösungsmittel: AcetonSolvent: acetone

Von den Wirkstoffen, Synergistan und Gemischen aus Kirkstoffer, und Synergisten warden 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 vollständig verdunstet ist. Anschließend gibt man 25 Testtiere in die Petrischalen und bedeckt sie mit einem Glasdeckel,Solutions of the active ingredients, synergistas and mixtures of Kirkstoffer and synergists are prepared and 2.5 ml of them are pipetted into Petri dishes on filter paper disks 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 you put 25 test animals in the Petri dishes and cover them 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

Figure imgb0013
100 nach 6 Stunden nicht erreicht, wird der %-Satz 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. Will the
Figure imgb0013
100 is not reached after 6 hours, the percentage of knock-down test animals is determined.

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

Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
 Concentrations of the active substances, synergists and mixtures and their effects are shown in the table below.
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019

Allgemeine Herstellungsverfahren:General manufacturing processes:

  • a) 0,1 Mol 3-(3.4-Methylendioxyphenyl)-propandiol-1.2 wird mit 0,1 Mol der entsprechenden Carbonylverbindung mit 0,5 g p-Toluolsulfonsäure in 300 ml Benzol am Wasserabscheider gekocht bis zur Beendigung der Reaktion. Man kühlt ab, wäscht zur Entfernung des Katalysators mit verdünnter Natronlauge, dann mit Wasser neutral, trocknet Uber Na2S04, zieht das Lösungsmittel ab und destilliert.a) 0.1 mol of 3- (3.4-methylenedioxyphenyl) propanediol-1.2 is boiled with 0.1 mol of the corresponding carbonyl compound with 0.5 g of p-toluenesulfonic acid in 300 ml of benzene on a water separator until the reaction has ended. The mixture is cooled, washed with dilute sodium hydroxide solution to remove the catalyst, then neutral with water, dried over Na2SO4, the solvent is stripped off and distilled.
  • b) 0,1 Mol 3,4-Methylendioxybenzyl-äthylenoxid wird mit 0,5 Mol Carbonylverbindung vermischt. Bei der Zugabe weniger Tropfen Bortrifluorid-ätherat tritt eine starke exotherme Reaktion ein, die durch Kühlung mit einem Eisbad zwischen 50 und 100°C gehalten werden kann. Nach Abklingen rührt man noch 1 Stunde bei 60°C nach, nimmt mit Toluol auf, wäscht mit Wasser neutral, trocknet über Na2SO4, zieht das Lösungsmittel ab und destilliert.b) 0.1 mol of 3,4-methylenedioxybenzylethylene oxide is mixed with 0.5 mol of carbonyl compound. With the addition of a few drops of boron trifluoride etherate, a strong exothermic reaction occurs, which can be kept between 50 and 100 ° C by cooling with an ice bath. After it has subsided, the mixture is stirred for a further 1 hour at 60 ° C., taken up in toluene, washed neutral with water, dried over Na 2 SO 4 , the solvent is stripped off and distilled.

Nach diesen Herstellungsverfahren werden folgende Verbindungen erhalten:

Figure imgb0020
The following compounds are obtained by these production processes:
Figure imgb0020

Claims (7)

1. Benzodioxolderivate der Formel (I)
Figure imgb0021
in welcher R1 und R2 gleich oder verschieden sein können und für H, Alkyl, Alkenyl, Alkinyl und Aryl stehen oder R und R zusammen für eine Alkylengruppe stehen. 1. Benzodioxole derivatives of the formula (I)
Figure imgb0021
 in which R 1 and R 2 may be the same or different and represent H, alkyl, alkenyl, alkynyl and aryl or R and R together represent an alkylene group. 2. Verfahren zur Herstellung der Benzodioxolderivate der Formel I gemäβ Anspruch 1, dadurch gekennzeichnet, daß man eine Verbindung der Formel II
Figure imgb0022
in welcher X ' für OH oder beide Reste X für -O- stehen mit einer Carbonylverbindung der allgemeinen Formel III
Figure imgb0023
Figure imgb0024
in welcher und R2 die oben angegebene Bedeutung haben, gegebenenfalls i Gegenwart eines Verdünnungsmittels umsetzt. 2. A process for the preparation of the benzodioxole derivatives of the formula I according to claim 1, characterized in that a compound of the formula II
Figure imgb0022
 in which X 'is OH or both radicals X are -O- with a carbonyl compound of the general formula III
Figure imgb0023
Figure imgb0024
 in which and R 2 have the meaning given above, if appropriate in the presence of a diluent. 3. Insektizide und akarizide Mittel, gekennzeichnet durch einen Gehalt an einer Wirkstoffkombination, bestehend aus Benzodioxolderivaten der Formel I gemäβ Anspruch 1 und A) Carbamaten, und/oder B) Carbonsäureestorm und/oder C)
Figure imgb0025
und/oder D) Cycloalkanen und/oder E) Halogenalkaner. 3. Insecticides and acaricidal agents, characterized by a content of an active ingredient combination consisting of benzodioxole derivatives of the formula I according to claim 1 and A) carbamates, and / or B) carboxylic acid and / or C)
Figure imgb0025
and or D) cycloalkanes and / or E) haloalkanes. 4. Insektizide und akarizide Mittel gemäß Anspurch 3, dadurch gekennzeichnet, daβ in der Wirkstoffkombination das Gewichtsverhä von Benzodioxolderivaten zu Wirkstoffen zwischen 0,1:10 und 10:0,1 liegt.4. Insecticides and acaricides according to Claim 3, characterized in that the weight ratio of benzodioxole derivatives to active substances is between 0.1: 10 and 10: 0.1 in the combination of active substances. 5. Verfahren zur Bekämpfung von Insekten und Spinnentieren dadurch gekennseichnet, daß men eine Wimkstoffkombination gemäß Anspruch 3 oder 4 auf Indekten und Spinnentieren und/oder ihran Lebensraum einrwirken läßt.5. A method of combating insects and arachnids characterized in that men can act on a combination of Wimpstoff according to claim 3 or 4 on insects and arachnids and / or their habitat. 6. Verwendung von Wirkstoffkombination gemäß Anspruch 3 oder 4 zur Bekämufung von Insekten und Spinnentieren.6. Use of active ingredient combination according to claim 3 or 4 for combating insects and arachnids. 7. Verfahren zur Herstellung von insektiziden und akariziden Mitteln, dadurch gekennseichnet daß man eine Wirkstoffkombination gemäß Anspruch 3 oder 4 mit Streckmitteln und/oder oberflachenaktiven Mitteln vermischt.7. Process for the preparation of insecticidal and acaricidal agents, characterized in that an active ingredient combination according to claim 3 or 4 is mixed with extenders and / or surface-active agents.
EP78100554A 1977-08-10 1978-07-31 Benzodioxolane derivatives, process for their preparation and their use as synergists in insecticides and acaricides Withdrawn EP0000760A1 (en)

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DE19772736017 DE2736017A1 (en) 1977-08-10 1977-08-10 BENZODIOXOL DERIVATIVES, METHOD FOR THEIR PRODUCTION AND THEIR USE AS SYNERGISTS IN INSECTICIDES AND ACARICIDES
DE2736017 1977-08-10

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BR (1) BR7805091A (en)
DE (1) DE2736017A1 (en)
DK (1) DK351678A (en)
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US5371069A (en) * 1990-12-12 1994-12-06 Giuaudan-Roure Corporation Organoleptic compositions

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US3008968A (en) * 1958-02-11 1961-11-14 Int Flavors & Fragrances Inc Process for making 2-methyl-3-(3'-4'-methylenedioxyphenyl)-propanal

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CN111269220B (en) * 2020-02-18 2021-07-16 中国农业大学 Compound with piperine skeleton structure, preparation and application thereof

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BR7805091A (en) 1979-05-08
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