Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • 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
  • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
  • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products

Definitions

• the invention relates to synergistic insecticidal mixtures of substituted benzoylureas and agonists or antagonists of nicotinergic acetylcholine receptors for protecting industrial materials.
• agonists and antagonists of nicotinergic acetylcholine receptors can be used to control insects and wood pests.
• the active ingredient In order to achieve an acute effect even in deeper layers of wood, the active ingredient must be used in relatively large concentrations. Subletal doses lead to a change in the behavior of the species in many cases, but are also reversible in many cases.
• mixtures of benzoylureas of the formula (I) and at least one agonist or antagonist of acetylcholine receptors of the formula (II) are synergistically active and are suitable for protecting industrial materials, in particular wood, from insect attack. Because of this synergism, significantly smaller amounts of active ingredient can be used, i.e. the effect of the mixture is greater than the effect of the individual components.
• the benzoylureas are compounds of the general formula (I) in which
• R 1 represents halogen or hydrogen
• R 2 represents halogen
• X represents hydrogen, halogen, alkyl, haloalkyl, alkoxy or haloalkoxy
• Y represents hydrogen, halogen, alkyl, haloalkyl, alkoxy or haloalkoxy
• n represents the numbers 1, 2, 3 or 4, where the substituent Y can be the same or different,
• R 3 represents halogen, haloalkyl or OR, where R represents haloalkyl or a substituted phenyl radical of the formula
• Z represents hydrogen, halogen, alkyl, haloalkyl, alkoxy or haloalkoxy and
• p represents the numbers 1, 2, 3 or 4, where Z can be the same or different, R 4 represents halogen or haloalkyl, and
• Q represents CH or N.
• benzoylureas are particularly preferably compounds of the general formula (I), where
• R 1 represents fluorine, chlorine or hydrogen
• R 2 represents fluorine and chlorine
• n the number 3
• Y is hydrogen, fluorine and / or chlorine
• n stands for the numbers 1, 2, 3 or 4, where Y can be the same or different and
• R 3 for fluorine, chlorine or OR, where
• R stands for haloalkyl with 1 to 3 carbon atoms and 1 to 7 chlorine and / or fluorine atoms, or
• R represents a substituted phenyl radical of the formula
• Z represents hydrogen, fluorine and / or chlorine
• p represents the numbers 1, 2, 3 or 4, where the substituents Z can be the same or different and R 4 is haloalkyl having 1 to 6 carbon atoms and 1 to 13 fluorine and / or chlorine atoms and
• Q represents CH or N.
• the benzoylureas are very particularly preferably:
• Triflumuron chlorofluazuron, diflubenzuron, flufenoxuron, flucycloxuron, hexaflumuron, penfluron or teflubenzuron, especially around triflumuron.
• the agonists and antagonists of the nicotinergic acetylcholine receptors are known compounds which are known from the following publications:
• 383 091 ' 907, 364 844, 315 826, 259 738, 254 859, 235 725, 212 600,
• R represents hydrogen, optionally substituted radicals acyl, alkyl, aryl,
• A represents a monofunctional group from the series hydrogen, acyl, alkyl, aryl or represents a bifunctional group which is linked to the radical Z;
• E represents an electron withdrawing group
• Atom can be linked to the radical Z;
• Formyl, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, (alkyl -) - (aryl -) - phos ⁇ horyl, which in turn may be substituted, may be mentioned as acyl radicals.
• alkyl there may be mentioned C, -C, 0 alkyl, in particular C 1 -C 4 alkyl, NEN in einzel ⁇ methyl, ethyl, i-propyl, sec- or t-butyl, which may in turn be substituted.
• Phenyl, naphthyl, especially phenyl, may be mentioned as aryl.
• Phenylmethyl and phenethyl may be mentioned as aralkyl.
• Heteroaryl with up to 10 ring atoms and N, O, S, in particular N as heteroatoms, may be mentioned as heteroaryl.
• Thiophenyl, furyl, thiazolyl, imidazolyl, pyridyl, benzthiazolyl may be mentioned individually.
• Heteroarylalkyl which may be mentioned are heteroarylmethyl, heteroarylethyl having up to 6 ring atoms and N, O, S, in particular N, as heteroatoms.
• A stands for hydrogen and optionally substituted radicals from the series acyl, alkyl, aryl, which preferably have the meanings given above, A furthermore stands for a bifunctional group.
• Substituted alkylene with 1 to 4, in particular 1 to 2, carbon atoms may be mentioned, where the substituents listed above are mentioned as substituents.
• a and Z together with the atoms to which they are attached, can form a saturated or unsaturated heterocyclic ring.
• the heterocyclic ring can contain a further 1 or 2 identical or different hetero atoms and / or hetero groups.
• the heteroatoms are preferably oxygen, sulfur or nitrogen and the hetero groups are N-alkyl, alkyl of the N-alkyl group preferably containing 1 to 4, in particular 1 or 2, carbon atoms.
• alkyl methyl, ethyl, n- and i-propyl and n-, i- and t-butyl may be mentioned.
• the heterocyclic ring contains 5 to 7, preferably 5 or 6 ring members. Examples of the heterocyclic ring are pyrrolidine, piperidine, piperazine, hexamethyleneimine,
• E stands for an electron-withdrawing radical, in particular NO 2 , CN,
• Haloalkylcarbonyl such as 1,5-halogeno-C, -C 4 -carbonyl, in particular COCF 2 may be mentioned.
• Z stands for optionally substituted radicals alkyl, -OR, -SR, -NRR, where
• R and the substituents preferably have the meaning given above.
• Z can together with the atom to which it is attached and the rest
• the heterocyclic ring can contain a further 1 or 2 identical or different heteroatoms and / or hetero groups.
• the hetero atoms are preferably oxygen, sulfur or nitrogen and the hetero groups are N-alkyl, the alkyl or N-alkyl group preferably containing 1 to 4, preferably 1 or 2, carbon atoms. Alkyl, methyl, ethyl, n- and i-propyl and n-, i- and t-butyl may be mentioned.
• the heterocyclic ring contains 5 to 7, preferably 5 or 6 ring members.
• heteroeyclic ring examples include pyrrolidine, piperidine, piperazine, hexamethyleneimine, morpholine and N-methylpiperazine.
• the agonists and antagonists of the nicotinergic acetylcholine receptors are particularly preferably compounds of the formula (II)
• n 1 or 2
• Very particularly preferred agonists and antagonists of the nicotinergic acetylcholine receptors are compounds of the following formulas: in particular the compound of the formula
• the active ingredient combination of benzoylureas of the formula (I) and agonists and antagonists of nicotinergic acetylcholine receptors of the formula (II) are outstandingly suitable for protecting industrial materials, in particular wood, from attack by wood-destroying insects, such as, for example
• Kalotermes flavicollis Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucilugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
• the ratio of the compounds of the formulas (I) and (II) used, and the total amount of the mixture depends on the type and the occurrence of the insects.
• the optimal ratios and total amounts can be used by everyone
• the ratio of the compounds of the general formulas (I) and (II) is 1: 100 to 100: 1, preferably 1:10 to 10: 1.
• the active ingredient combinations according to the invention can generally be incorporated into all wood preservatives or formulations, e.g. by mixing the
• Active ingredients with solvents or diluents, emulsifiers, dispersants and / or binders or fixatives, water repellants, optionally siccatives and UV stabilizers and optionally dyes and pigments as well as other processing aids or as an additive to any other wood preservation formulation.
• An organic-chemical solvent or solvent mixture and / or an oily or oily, low-volatile organic-chemical solvent or solvent mixture and / or a polar organic-chemical solvent or solvent serves as the solvent and / or diluent.
• the organic chemical solvents used are preferably oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C.
• Corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene, are used as such low-volatility, water-insoluble, oily and oily solvents.
• Mineral oils with a boiling range of 170 to 220 ° C., test gasoline with a boiling range of 170 to 220 ° C., spindle oil with a boiling range of 250 to 350 ° C., petroleum or aromatics with a boiling range of 160 to 280 ° C., turpentine oil are advantageous and the like.
• the organic low-volatility oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partially replaced by slightly or medium-volatile organic chemical solvents, with the proviso that the solvent mixture is also a Evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture.
• Solvent or solvent mixture or an aliphatic polar organic chemical solvent or solvent mixture replaced.
• Water is also particularly suitable as a solvent or diluent, if appropriate in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants.
• the organic-chemical binders used are the water-dilutable synthetic resins known in the art and / or soluble or dispersible or emulsifiable synthetic resins and / or binding drying oils, in particular binders consisting of or containing, which are soluble or dispersible or emulsifiable in the organic chemical solvents used an acrylate resin, a vinyl resin, eg polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders the basis of a natural and / or synthetic resin used
• the synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances of up to 10% by weight can also be used as binders. In addition, dyes, pigments, water-repellants, odor-correcting agents and inhibitors or anticorrosive agents and the like known per se can be used
• At least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is preferably contained in the agent or in the concentrate as the organic chemical binder.
• Alkyd resins having an oil content of more than 45% by weight, preferably 50 to 68% by weight, are preferably used according to the invention.
• the binder mentioned can be wholly or partly by a fixing agent.
• mixture or a plasticizer (mixture) can be replaced.
• additives are intended to prevent volatilization of the active ingredients and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used)
• the plasticizers come from the chemical classes of phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, glycerol ether or higher molecular weight glycol ether, glycerol ester and p-toluenesulfonic acid ester.
• phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate
• phosphoric acid esters such as tributyl phosphate
• adipic acid esters such as di- (2-ethylhexyl) adipate
• stearates such as butyl
• Fixing agents are chemically based on polyvinyl alkyl ethers such as e.g. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone, amines such as e.g. Alkanolamines such as monoethanolamine or ammonia.
• polyvinyl alkyl ethers such as e.g. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone, amines such as e.g. Alkanolamines such as monoethanolamine or ammonia.
• wood which can be protected by the active substance mixture according to the invention or agents containing it, is to be understood as examples: lumber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wooden cladding, wooden windows and doors, plywood , Chipboard, carpentry or wood products that are used in general in house construction or joinery.
• a particularly effective wood protection is achieved through industrial impregnation processes, e.g. Vacuum, double vacuum or pressure process.
• insecticidal agents or concentrates used to protect wood and wood-based materials contain the active ingredient combination in a concentration of
• the agents according to the invention advantageously make it possible to replace the previously available insecticidal agents with more effective ones. They show good stability and advantageously have a broad spectrum of insecticidal activity.
• the mixtures according to the invention can, if appropriate, also be mixed with further insecticides and, in order to additionally achieve an action against wood-destroying and wood-staining fungi, if appropriate also with one or more fungicides. In many cases, additional synergisms can then be observed.
• insecticides examples include:
• Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, ⁇ -l (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxy-pyrazole, chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, Diazinon, Dichlorvos, Dimethoate, Ethoate, Ethoprophos, Etrimfos, Fenitrothion, Fenthion, Heptenophas, Parathion, Parathion-methyl, Phosalone, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulfofos, Sulfofos Trichlorphone; Carbamates such as aldicarb, bendiocarb, ⁇ -2- (l-methylpropyl) phenylmethyl carbamate,
• (Dimethylphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether such as e.g. Dimethyl- (9-ethoxyphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether or [(phenyl) -3- (3-phenoxyphenyl) propyl] (dimethyl) silanes such as e.g. (4-ethoxyphenyl) - [3- (4-fluoro-3-phenoxyphenyl-propyl] dimethyl-silane, silafluofen; pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin, cycloprothrin,
• the additional insecticides which can optionally be added can also originate from the classes of the compounds of the general formulas (I) and (II).
• Possible fungicides which can still be admixed are preferably:
• Triazoles such as:
• Imidazoles such as:
• Succinate dehydrogenase inhibitors such as:
• Sulfenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet; Captan,
• Benzimidazoles such as carbendazim, benomyl, furathiocarb, fuberidazole, thiophonate methyl, thiabendazole or their salts; Morpholine derivatives such as fenpropimorph, falimorph, dimethomorph, dodemorph,
• Benzamides such as 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide
• Boron compounds such as boric acid, boric acid ester, borax;
• Formaldehyde and formaldehyde releasing compounds such as benzyl alcohol mono-
• Aldehydes such as cinnamaldehyde, formaldehyde, glutardialdehyde, ⁇ -bromocinnamaldehyde;
• Thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate, etc; quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride,
• Benzyldimethyldodecylammonium chloride didecyldimethaylammonium chloride; Iodine derivatives such as diiodomethyl p-tolyl sulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenylethyl carbamate, 2,3,3-triiodo allyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-butyl carbamate, 3-iodo-2-propynyl-n-hexyl carbamate, 3-iodo-2-propynyl cyclohexyl carbamate, 3-
• Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol,
• Microbicides with activated halogen group such as chloroacetamide, bronopol, bronidox, tectamer such as 2-bromo-2-nitro-l, 3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3- nitrile propionamide, 1,2-dibromo-2,4-dicyanobutane, ⁇ -bromo- ⁇ -nitrostyrene; Pyridines such as l-hydroxy-2-pyridinthione (and their Na, Fe, Mn, Zn salts),
• Metal soaps such as tin, copper, zinc naphtenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate;
• Metal salts such as copper hydroxycarbonate, sodium dichromate, potassium dichromate,
• Copper fluorosilicate in particular mixture with fixatives
• Oxides such as tributyltin oxide, Cu 2 O, CuO, ZnO; Dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates,
• Nitriles such as 2,4,5, 6-tetrachloroisophthalonitrile, disodium cyano-dithioimidocarbamate;
• Quinolines such as 8-hydroxyquinoline and their Cu salts; Mucochloric acid, 5-hydroxy-2 (5H) furanone;

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• Life Sciences & Earth Sciences (AREA)
• Agronomy & Crop Science (AREA)
• Pest Control & Pesticides (AREA)
• Plant Pathology (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Citations (4)

• 1994
  • 1994-10-11 DE DE19944436268 patent/DE4436268A1/de not_active Withdrawn
• 1995
  • 1995-09-28 AU AU36529/95A patent/AU3652995A/en not_active Abandoned
  • 1995-09-28 BR BR9509287A patent/BR9509287A/pt not_active Application Discontinuation
  • 1995-09-28 EP EP95934115A patent/EP0785718A1/de not_active Withdrawn
  • 1995-09-28 JP JP8512301A patent/JPH10508007A/ja active Pending
  • 1995-09-28 WO PCT/EP1995/003845 patent/WO1996010915A1/de not_active Application Discontinuation
• 1997
  • 1997-03-12 NO NO971140A patent/NO971140L/no unknown
  • 1997-04-09 FI FI971480A patent/FI971480A/fi unknown

Patent Citations (4)

Non-Patent Citations (3)

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