EP0785718A1

EP0785718A1 - Insecticides

Info

Publication number: EP0785718A1
Application number: EP95934115A
Authority: EP
Inventors: Hermann Uhr; Martin Kugler; Heinrich Schrage; Franz Kunisch
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1994-10-11
Filing date: 1995-09-28
Publication date: 1997-07-30
Also published as: FI971480A0; JPH10508007A; NO971140D0; AU3652995A; WO1996010915A1; BR9509287A; FI971480A; NO971140L; DE4436268A1

Abstract

Insecticide mixtures made of substituted benzoyl urea and agonists or antagonists of nicotinic acetylcholine receptors are useful for protecting technical materials.

Description

INSECTICIDE AGENT

The invention relates to synergistic insecticidal mixtures of substituted benzoylureas and agonists or antagonists of nicotinergic acetylcholine receptors for protecting industrial materials.

It has already become known that substituted benzoylureas can be used to control wood pests (see Holz-Zentralblatt, 110, 524 (1984)). An advantage is the very low vapor pressure of these compounds and at the same time their very low toxicity, which is due to the fact that they inhibit chitin biosynthesis.

A disadvantage of these compounds, however, is that they do not become effective until the next moult. During this time, the pests may already have caused considerable damage.

Furthermore, it has also become known that agonists and antagonists of nicotinergic acetylcholine receptors can be used to control insects and wood pests. 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.

It has now been found that 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,

represents the numbers 1, 2, 3, where the substituent X can be identical or different,

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

stands, where

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.

The benzoylureas are particularly preferably compounds of the general formula (I), where

R ^{1 represents} fluorine, chlorine or hydrogen,

R ^{2 represents} fluorine and chlorine,

X for hydrogen and

m represents the number 3,

Y is hydrogen, fluorine and / or chlorine and

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

stands, where

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:

European Strategy ^h Laid-Open Nos. 464 830, 428 941, 425 978, 386 565,

383 091 .: ^' 907, 364 844, 315 826, 259 738, 254 859, 235 725, 212 600,

192 060, 163 855, 154 178, 136 686, 303 570, 302 833, 306 696, 189 972, 455 000, 135 956, 471 372, 302 389;

German Offenlegungsschriften No. 3 639 877, 3 712 307;

Japanese Patent Laid-Open No. 03 220 176, 02 207 083, 63 307 857,

63 287 764, 03 246 283, 04 9371, 03 279 359, 03 255 072;

U.S. Patent Nos. 5,034,524, 4,948,798, 4,918,086, 5,039,686, 5,034,404;

PCT applications No. WO 91/17 659, 91/4965;

French application No. 2 6 1 114;

Brazilian application No. 88 03 621.

Reference is hereby expressly made to the generic formulas and definitions described in these publications and to the individual compounds described therein. Some of these compounds are summarized under the term nitromethylenes and related compounds.

These compounds can preferably be summarized under the general formula (II)

in which

R represents hydrogen, optionally substituted radicals acyl, alkyl, aryl,

Aralkyl, heteroaryl or heteroarylalkyl;

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;

X represents the radicals -CH = or = N-, the radical -CH = instead of an H-

Atom can be linked to the radical Z;

Z for a monofunctional group from the series alkyl, -O-R, -S-R,

represents or represents a bifunctional group which is linked to the radical A or the radical X.

Compounds of the formula (II) in which the radicals have the following meaning are particularly preferred: stands for hydrogen and for optionally substituted radicals from the series acyl, alkyl, aryl, aralkyl, heteroaryl, heteroarylalkyl.

Formyl, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, (alkyl -) - (aryl -) - phosρhoryl, which in turn may be substituted, may be mentioned as acyl radicals.

As 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.

Examples of preferred substituents are:

Alkyl with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methyl, ethyl, n- and i-propyl and n-, i- and t-butyl; Alkoxy preferably having 1 to 4, in particular 1 or 2, carbon atoms, such as methoxy, ethoxy, n- and i-propyloxy and n-, i- and t-butyloxy; Alkylthio with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methylthio, ethylthio, n- and i-propylthio and n-, i- and t-butylthio; Haloalkyl with preferably 1 to 4, in particular 1 or 2, carbon atoms and preferably 1 to 5, in particular 1 to 3, halogen atoms, the halogen atoms being identical or different and being halogen atoms, preferably fluorine, chlorine or bromine, in particular fluorine, such as trifluoromethyl, hydroxy; Halogen, preferably fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine, cyano; Nitro; Amino; Monoalkyl- and dialkylamino with preferably 1 to 4, in particular 1 or 2 carbon atoms per alkyl group, such as methyl amino, methyl ethylamino, n- and i-propylamino and methyl n-butylamino; Carboxyl; Carbalkoxy with preferably 2 to 4, in particular 2 or 3 carbon atoms, such as carbomethoxy and carboethoxy; Sulfo (-SO ₃ H); Alkylsulfonyl with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methylsulfonyl and ethylsulfonyl; Arylsulfonyl with preferably 6 or 10 aryl carbon atoms, such as phenylsulfonyl and heteroaryl amino and heteroarylalkylamino such as chloropyridylamino and chloropyridylmethylamino.

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. As 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,

Morpholine and N-methylpiperazine called.

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.

X stands for -CH = or -N =

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

= C - at the position of X form a saturated or unsaturated heterocyclic ring. 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.

Examples of the heteroeyclic ring are 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)

R for or Subst

stands, where

n represents 1 or 2,

Subst. For one of the substituents listed above, especially for halogen, in particular for chlorine, and A, Z, X and E have the meaning given above.

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

1. Beetle Hylotrupes bajulus, Chlorophorus pilosis, Anabium punctatum, Xestobium rufovillosum, Ptilinus pecticomis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearesces, Lyctus pubis linearis, Lyctus pubis linearis, specie Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus

2. Skin wing

Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur

3. Termites

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

Application can be determined by test series. In general, 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. mixture and / or water and at least one emulsifier and / or wetting agent or consists thereof.

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.

In a preferred embodiment, liquid aliphatic hydrocarbons with a boiling range from 180 to 210 ° C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range from 180 to 220 ° C. and / or locker oil and / or monochloronaphthalene, preferably α- Monochloronaphthalene used.

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.

According to a preferred embodiment, part of the organic chemical

Solvent or solvent mixture or an aliphatic polar organic chemical solvent or solvent mixture replaced. Aliphatic organic chemical solvents containing hydroxyl and / or ester and / or ether groups, such as, for example, glycol ethers, esters or the like, are preferably used. 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.

In the context of the present invention, 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

According to the invention, 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. These 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.

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.

The term 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.

The insecticidal agents or concentrates used to protect wood and wood-based materials contain the active ingredient combination in a concentration of

0.001 to 95% by weight, in particular 0.001 to 60% by weight.

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.

In ready-to-use applications, 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.

Examples of insecticides that can be added are:

Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, α-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, α-2- (l-methylpropyl) phenylmethyl carbamate,

Butocarboxim, Butoxycarboxim, Carbaryl, Carbofuran, Carbosulfan, Cloethocarb, Isoprocarb, Methomyl, Oxamyl, Pirimicarb, Promecarb, Propoxur and Thiodicarb; Organosilicon compounds, preferably dimethyl (phenyl) silyl-methyl-3-phenoxybenzyl ether such as dimethyl- (4-ethoxyphenyl) -silylmethyl-3-phenoxybenzylether or

(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,

Cyfluthrin, decamethrin, cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- (2-chloro-2-trifluoromethylvinyl) cyclopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerate , Flucythrinate, flumethrin, fluvalinate, permethrin, resmethrin and tralomethrin; Nitroimines and nitromethylenes such as l - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-lH-imidazol-2-amine (imidacloprid), N - [(6-chloro-3 -pyridyl) methyl-] N ² - cyano-N ^ methylacetamide (NI-25);

Abamectin, AC 303.630, Acephate, Acrinathrin, Alanycarb, Aldoxycarb, Aldrin, Amitraz, Azamethiphos, Bacillus thuringiensis, Phosmet, Phosphamidon, Phosphine, Prallethrin, Propaphos, Propetamphos, Prothoate, Pyraclofos, Pyre, Pyriproxy, Pyridafin, Pyridafin, Pyridafin, Pyridafin, Pyridafin, Pyridafin, Pyridafin, Pyridafin, Pyridafin, Pyridafin, Pyridafin, Pyridafin, Pyridafin, Pyridafin, Pyridafin, Pyrin, Pyrinsafin RH-7988, Rotenone, Sodium fluoride, Sodium hexafluorosilicate, Sulfotep, Sulfuryl fluoride, Tar Oils, Teflubenzuron, Tefluthrin, Temephos, Terbufos, Tetrachlorvinphos, Tetramethrin, O-2-tert.-Butyl-pyrimidin-5-yl-o-isopropyl -phosphorothiate, thiocyclam, thio-fanox, thiometone, tralomethrin, triflumuron, trimethacarb, vamidothion, verticillium lacanii, XMC, xylylcarb, benfuracarb, bensultap, bifenthrin, bioallethrin, MERbioomercyclophyl, bromine-cyclophosphate (S) Buprofezin, Cadusafos, Calcium Polysulfide, Carbophenothion, Cartap, Chinomethionate, Chlordane, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chloropicrin, Chlorpyrifos, Cyanophos, Beta-Cyfluthrin, Alpha-cypermethrin, Cyophenothrin, Cyromazine, Dazomet, DDT, Demeton-S-methylsulphone, Diafenthiuron, Dialifos, Dicrotophos, Diflubenzuron, Dinoseb, Deoxabenzofos, Diaxacarb, Disulfoton, DNOC, Empenthrin, Endosulfan, EPN, Esfenvalerate, Ethiofencarb, Ethion, Etofenprox, Fenobucarb, Fenoxycarb, Fensulfothion, Fipronil, Flucycloxuron, Flufenprox, Flufenoxuron, Fonofos, Foπnetanate, Formothion, Fosmethilan, Hexaframethononuronon , Hydroprene, IPSP, Isazofos, Isofenphos, Isoprothiolane, Isoxathion, Iodfenphos,

Kadethrin, Lindane, Malathion, Mecarbam, Mephosfolan, Mercurous, chloride, Metam, Metarthician, anisopliae, Methacrifos, Methami dophos, Methidathione, Methiocarb, Methoprene, Methoxychlor, Methyl isothiocyanate, Metholcarb, Mevinphos, Nicocertophiferod, Naledotophiferip, Naledotophiferip, Naledotophifer, Naledotophifer, Naledotophifer, Nalionotophifer, NPalionotine, Naledotophiferus, Omethoates, oxydemetone-methyl, pentachlorophenol, petroleum oils, phenothrin, phenthoates, phorates;

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:

Amitrole, Azocyclotin, BAS 480F, Bitertanol, Difenoconazole, Fenbuconazole, Fenchlorazole, Fenethanil, Fluquinconazole, Flusilazole, Flutriafol, Imibenconazole, Isozofos, Myclobutanil, Paclobutrazol, (±) -chlor-l- (4) lH-l, 2,4-triazole-l -yl) -cycloheptanol, tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole, triticonazole, uniconazole and their metal salts and acid adducts.

Imidazoles such as:

Imazalil, pefurazoate, prochloraz, triflumizole, 2- (l-tert-butyl) -l- (2-chlorophenyl) -3- (l, 2,4-triazol-l-yl) -propan-2-ol, thiazolecarboxanilides such as 2 ', 6'-dibromo-2-methyl-4-tiifluoromethoxy-4'-trifluoromethyl-l, 3-thiazoIe-5-carboxanilide, 1-imidazole-yl-l- (4'-chlorophenoxy) -3, 3-dimethylbutan-2-one and their metal salts and acid adducts.

Methyl (E) -2- [2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl] 3-methoxyacrylates, methyl (E) -2- [2- [6- (2-thioamidophenoxy) pyrimidine- 4-yloxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [6- (2-fluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxy-acrylate, methyl (E) -2- [2- [6- (2,6-difluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-meth-oxyacrylates, methyl (E) -2- [2- [3- (pyrimidin-2-yloxy ) phenoxy] phenyl] -3-meth- oxy acrylates, methyl (E) -2- [2- [3- (5-methylpyrimidin-2-yloxy) phenoxy] phenyl] -3-methoxyacrylates, methyl (E) -2- [2- [3- (phenyl -sulfonyloxy) phenoxy] phenyl] -3-methoxyacrylates, methyl (E) -2- [2- [3- (4-nitrophenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2-phenoxyphenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3,5-dimethylbenzoyl) pyrrol-l-yl] -3-methoxyacrylate, methyl (E) -2- [2- (3-methoxyphenoxy) phenyl] -. 3-methoxyacrylate, methyl (E) -2- [2- (2-phenylethen-l-yl) phenyl] -3- methoxyacrylate, methyl (E) -2- [ 2- (3,5-dichlorophenoxy) pyridin-3-yl] -3-methoxy-acrylates, methyl (E) -2- (2- (3- (l, l, 2,2-tetrafluoroethoxy) phenoxy) phenyl) -3-methoxy-acrylates, methyl (E) -2- (2- [3- (alpha-hydroxybenzyl) phenoxy] phenyl) -3-methoxy-acrylates, methyl (E) -2- (2- (4-phenoxypyridine -2-yloxy) phenyl) -3-methoxyacrylate, methyl (E) -2- [2- (3-n-propyloxyphenoxy) phenyl] 3-methoxyacrylate, methyl (E) -2- [2- (3-isopropyloxyphenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (2-fluorophenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3-ethoxyphenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (4-tert-butylpyridin-2-yloxy) phenyl] -3-methoxyacrylate, methyl (E) - 2- [2- [3- (3-cyanophenoxy) phenoxy] phenyl] -3-methoxy-acrylates, methyl (E) -2- [2- (3-methylpyridin-2-yloxymethyl) phenyl] -3-methoxy- acrylates, methyl (E -2- [2- [6- (2- (2-ylphenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxy acrylates, methyl (E) -2- [2- (5- bromopyridin-2-yloxymethyl) phenyl] -3-methoxy-acrylate, methyl (E) -2- [2- (3- (3-iodopyridin-2-yloxy) phenoxy) phenyl] -3-methoxy-acrylate, methyl ( E) -2- [2- [6- (2-chloropyridin-3-yloxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylates, (E, (E) methyl-2- [2- (5.6 -dimethylpyrazin-2-ylmethyloximinomethyl- phenyl] -3-methoxyacrylate, (E) -methyl-2- {2- [6- (6-methylpyridin-2-yloxy) pyrimidin-4-yloxy jphenyl} -3 methoxy acrylates, (E, (E) methyl-2- {2- (3-methoxypheny 1) methyloximinomethyl] phenyl} -3-methoxyacrylates, (E) methyl-2- {2- (6- (2-azidophen - oxy) pyrimidin-4-yloxy] phenyl) 3-methoxyacrylate, (E), (E) methyl-2- {2- [6-phenyl-pyrimidin-4-yl) -met hyloximinomethyl] phenyl} -3-methoxyacrylate, (E), (E) methyl-2- {2 - [(4-chlorophenyl) methyloximinomethyl] phenyl} -3-methoxyacrylate, (E) methy 1- 2- {2 - [6- (2-n-propylphenoxy) -1, 3,5-triazin-4-yloxy] phenyl} -3-methoxyacrylate, (E), (E) methyl-2- {2 - [(3 -nitrophenyl ) methyloximinomethyl] phenyl} -3-methoxy acrylate;

Succinate dehydrogenase inhibitors such as:

Fenfuram, furcarbanil, cyclafluramide, furmecyclox, seedvax, metsulfovax, pyrocarbolide, oxycarboxin, shirlan, mebenil (mepronil), benodanil, flutolanil (moncut); Naphthalene derivatives such as terbinafine, naftifine, butenafine, 3-chloro-7- (2-aza-

2,7,7-trimethyl-oct-3-en-5-in); Sulfenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet; Captan,

Captofol;

Benzimidazoles such as carbendazim, benomyl, furathiocarb, fuberidazole, thiophonate methyl, thiabendazole or their salts; Morpholine derivatives such as fenpropimorph, falimorph, dimethomorph, dodemorph,

Aldimorph, fenpropidine and their arylsulfonic acid salts, e.g. p-

Toluenesulfonic acid and p-dodecylphenyl sulfonic acid;

Dithiocarbamate, Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam,

Metiram, Thiram Zeneb, Ziram; Benzothiazoles such as 2-mercaptobenzothiazole;

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-

(poly) hemiformal, oxazolidine, hexa-hydro-S-triazine, N-methylolchloroacetamide, paraformadehyde, nitropyrin, oxolinic acid, tecloftalam;

Tris-N- (cyclohexyldiazeniumdioxy) aluminum, N- (cyclohexyldiazeniumdioxy) - tributyltin or K salts, bis-N- (cyclohexyldiazeniumdioxy) copper;

N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octyl-isothiazolin-3-one, 4,5- Trimethylene-isothiazolinone, 4,5-benzisothiazolinone, N-methylolchloroacetamide;

Aldehydes such as cinnamaldehyde, formaldehyde, glutardialdehyde, β-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-

Iodine-2-propiny 1-phenyl carb amate; Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol,

3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol and their alkali and

Alkaline earth metal salts;

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, β-bromo-β-nitrostyrene; Pyridines such as l-hydroxy-2-pyridinthione (and their Na, Fe, Mn, Zn salts),

Tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrithione, 1-

Hydroxy-4-methyl-6- (2,4,4-trimethylpentyl) -2 (1 H) pyridine;

Metal soaps such as tin, copper, zinc naphtenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate;

Metal salts such as copper hydroxycarbonate, sodium dichromate, potassium dichromate,

Potassium chromate, copper sulfate, copper chloride, copper borate, zinc fluorosilicate,

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,

Tetram ethythiuramdi sulfide, potassium N-methy1-dithiocarbamate;

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;

4,5-dichlorodithiazolinone, 4,5-benzdithiazolinone, 4,5-trimethylene dithiazolinone,

4,5-dichloro- (3H) -l, 2-dithiol-3-one, 3,5-dimethyl-tetrahydro-l, 3,5-thiadiazin-2-thione,

N- (2-p-chlorobenzoylethyl) hexaminium chloride, potassium N-hydroxymethyl-N'-methyl-dithiocarbamate, 2-oxo-2- (4-hydroxy-phenyl) acethydroximic acid chloride,

Phenyl- (2-chloro-cyano-vinyl) sulfone,

Phenyl- (1,2-dichloro-2-cyano-vinyl) sulfone;

Zeolites containing Ag, Zn or Cu alone or included in polymers

Active ingredients, or mixtures of several of the above-mentioned fungicides.

Claims

claims

1. Microbicidal compositions containing a synergistically effective mixture of at least one benzoylurea and at least one agonist or antagonist of nicotinergic acetylcholine receptors.

2. Agent according to claim 1, enüialtend at least one benzoyl urea of formula (I)

in which

R ^{1 represents} halogen or hydrogen,

R ^{2 represents} halogen,

X represents hydrogen, halogen, alkyl, haloalkyl, alkoxy or haloalkoxy,

m represents the numbers 1, 2, 3, where the substituent X can be the same or different,

Y represents hydrogen, halogen, alkyl, haloalkyl, alkoxy or

Halogenalkoxy stands,

R ^{3 represents} halogen, haloalkyl or OR, where R represents haloalkyl or a substituted phenyl radical of the formula stands, where

Z represents hydrogen, halogen, alkyl, haloalkyl, alkoxy or

Halogenalkoxy stands and

p for e numbers 1, 2,

3 or 4, where Z is the same or different

: a name,

P .u: rialogen or haloalkyl, and

! "Stands for CH or N,

and at least one compound of the formula (II)

^N C ^{/ (} ^ W

II

X - E

in which

R represents hydrogen, optionally substituted radicals acyl, alkyl, aryl, aralkyl, heteroaryl or heteroarylalkyl;

E represents an electron withdrawing group;

X stands for the radicals -CH = or = N-, where the radical -CH = can be linked to the radical Z instead of an H atom; for a monofunctional group from the series alkyl, -OR, -SR,

-N

N

Agent according to claim 1, containing at least one benzoyl urea from the series triflumuron, chlorofluazuron, diflubenzuron, flufenoxuron, flucycloxuron, hexaflumuron, penfluron or teflubenzuron and at least one compound of the formulas (IΙa) - (IIh)

4. Agent according to one of claims 1-3, containing the benzoylurea and the agonists or antagonists of nicotinergic acetylcholine receptors in a ratio of 1: 100 to 100: 1.

5. Wood preservative containing, in addition to conventional wood preservative components, a synergistically effective mixture of at least one benzoyl urea and at least one agonist or antagonist of nicotinergic acetylcholine receptors.

Process for protecting technical materials from insecticidal attack, characterized in that a synergistically effective mixture of at least one benzoyl urea and at least one agonist or antagonist of nicotinergic acetylcholine receptors is applied to the materials to be protected or the materials are treated with this mixture.

Use of a synergistically effective mixture of at least one benzoyl urea and at least one agonist or antagonist of nicotinergic acetylcholine receptors for protecting industrial materials from insecticidal attack.

Process for the preparation of wood preservatives, characterized in that a synergistically effective mixture of at least one benzoyl urea and at least one agonist or antagonist of nicotinergic acetylcholine receptors is mixed with conventional wood preservative constituents and, if appropriate, further active ingredients.