DE4436268A1 - Microbicidal agents - Google Patents

Abstract

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

Description

The invention relates to synergistic insecticidal mixtures of substituted Benzoylureas and agonists or antagonists of nicotinergic acetyl choline receptors for the protection of technical materials.

It has already become known that substituted benzoylureas are used Control wood pests (see Holz-Zentralblatt, 110, 524 (1984)). One advantage is the very low vapor pressure of this connection and at the same time their very low toxicity, which is due to this is that they inhibit chitin biosynthesis.

A disadvantage of these compounds, however, is that they do not work only take effect at the next moult. During this time the Pests have already caused considerable damage.

It has also become known that agonists and antagonists of Nicotinergic acetylcholine receptors to fight insects and wood damage lingen can use. To make one even in deeper layers of wood To achieve acute effects, the active ingredient must be in relatively large concentrations be used. Subletal doses lead to one in many cases Behavioral changes in the species, 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 formula (II) are synergistically effective and to protect technical Materials, especially wood, are suitable against insect attack. Because of this  Synergism significantly lower amounts of active ingredient can be used, i. H. 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
R¹ represents halogen or hydrogen,
R² 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 haloalkoxy,
n represents the numbers 1, 2, 3 or 4, where the substituent Y can be the same or different,
R³ is halogen, haloalkyl or OR, where R is 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,
R⁴ represents halogen or haloalkyl, and
Q represents CH or N.

The benzoylureas are particularly preferably compounds of the general formula (I), where
R¹ represents fluorine, chlorine or hydrogen,
R² represents fluorine and chlorine,
X for hydrogen and
m represents the number 3,
Y for hydrogen is fluorine and / or chlorine and
n stands for the numbers 1, 2, 3 or 4, where Y can be the same or different and
R³ 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
R⁴ for haloalkyl with 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, Chlorfluazuron, Diflubenzuron, Flufenoxuron, Flucycloxuron, Hexa flumuron, 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 Patent Application Nos. 464 830, 428 941, 425 978, 386 565, 383 091, 375 907, 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. 2 611 114;
Brazilian application No. 88 03 621.

The generic formulas and definitions described in these publications NEN, as well as the individual compounds described therein, are hereby made expressly referred.

These compounds are partly called nitromethylenes and there summarized with related connections.

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

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

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

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

Formyl, alkylcarbonyl, arylcarbonyl and alkyl may be mentioned as acyl radicals sulfonyl, arylsulfonyl, (alkyl -) - (aryl -) - phosphoryl, which in turn can be substituted.

As alkyl may be mentioned C₁-C₁₀-alkyl, especially C₁-C im-alkyl, in single NEN methyl, ethyl, i-propyl, sec.- or t.-butyl, which in turn is substituted could be.

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, especially N as heteroatoms. In particular, Thio phenyl, furyl, thiazolyl, imidazolyl, pyridyl, benzthiazolyl.

Heteroarylmethyl, heteroarylethyl may be mentioned as heteroarylalkyl up to 6 ring atoms and N, O, S, especially N as heteroatoms.

Examples of preferred substituents are:
Alkyl having 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 methylamino, 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 (-SO₃H); Alkyl sulfonyl preferably having 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 heteroarylamino and heteroarylalkylamino such as chloropyridylamino and chloropyridylmethylamino.

A stands for hydrogen and for optionally substituted radicals from the Series acyl, alkyl, aryl, which preferably has the meanings given above A also represents a bifunctional group. May be mentioned  optionally substituted alkylene with 1 to 4, in particular 1 to 2, carbon atoms, where the substituents listed above are mentioned as substituents be.

A and Z together with the atoms to which they are attached can form one form saturated or unsaturated heterocyclic ring. The straight Cyclic ring can be 1 or 2 identical or different hetero contain atoms and / or hetero groups. As heteroatoms are preferred wise oxygen, sulfur or nitrogen and as hetero groups N-alkyl, where alkyl of the N-alkyl group is preferably 1 to 4, in particular 1 or contains 2 carbon atoms. Alkyl, methyl, ethyl, n- and i- Propyl and n-, i- and t-butyl called. The heterocyclic ring contains 5 up to 7, preferably 5 or 6 ring members. As examples of the heterocyc ring are pyrrolidine, piperidine, piperazine, hexamethyleneimine, Morpholine and N-methylpiperazine called.

E stands for an electron-withdrawing radical, in particular NO₂, CN, Haloalkylcarbonyl such as 1,5-halogen-C₁-C₄-carbonyl, in particular COCF₂ 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

X is a saturated or unsaturated heterocyclic Form a ring. The heterocyclic ring can be another 1 or 2 identical or contain different heteroatoms and / or hetero groups. As a straight atoms are preferably oxygen, sulfur or nitrogen and as Hetero groups N-alkyl, the alkyl or N-alkyl group being preferred  contains 1 to 4, preferably 1 or 2 carbon atoms. As alkyl may be mentioned methyl, ethyl, n- and i-propyl and n-, i- and t-butyl. Of 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.

The agonists and antagonists are particularly preferred nicotinergic acetylcholine receptors around compounds of formula (II)

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 nicotinic acetyl Choline 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 suitable excellent for protecting technical materials, especially wood before infestation by wood-destroying insects, such as

• 1. Beetle
  Hylotrupes bajulus, Chlorophorus pilosis, Anabium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearesces, Lyctus pubis linearis, Lyctus pubis linearis, Lyctus pubis linearis, speculum Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brnnneus, 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 The total amount of the mixture is full of the type and occurrence of the insects dependent. The optimal ratios and total amounts can be used by everyone Application can be determined by test series. In general it is Ratio of the compounds of the general formulas (I) and (II) 1: 100 to 100: 1, preferably 1:10 to 10: 1.

The active ingredient combination according to the invention can generally be used in all wood Protective agents or formulations are incorporated e.g. B. by mixing the Active ingredients with solvents or diluents, emulsifiers, dispersants and / or Binding or fixing agent, water repellent, if necessary siccatives and UV Stabilizers and optionally dyes and pigments and others Processing aids or as an addition to any other wood protection formulations.

An organic chemical is used as the solvent and / or diluent Solvent or solvent mixture and / or an oily or oily difficultly volatile organic chemical solvent or solvent mixture and / or a polar organic chemical solvent or solvent mixture and / or water and at least one emulsifier and / or wetting agent or consists of it.

The organic chemical solvents used are preferably oily or oily ones Solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, used. As such difficult volatile, water-insoluble, oily and oily solvents become corresponding Mineral oils or their aromatic fractions or solvents containing mineral oil mixtures, preferably white spirit, petroleum and / or alkylbenzene used.  

Mineral oils with a boiling range of 170 to 220 ° C are advantageous, test petrol with a boiling range of 170 to 220 ° C, spindle oil with a boil range from 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 up to 280 ° C, turpentine oil and the like.

In a preferred embodiment, liquid aliphatic hydrocarbons substances with a boiling range of 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, preferred as α-monochloronaphthalene used.

The organic non-volatile oily or oily solvents with a Evaporation rate above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partially organic or slightly volatile chemical solvents are replaced, provided that the solvent mix also an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide fungicide Ge 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 orga niche chemical solvent or solvent mixture replaced. Preferably come alipha containing hydroxyl and / or ester and / or ether groups organic chemical solvents such as glycol ether, esters or the like for use.

Water is also particularly suitable as a solvent or diluent, optionally in a mixture with one or more of the above-mentioned orga nisch-chemical solvents or diluents, emulsifiers and dispersers gators.

As organic-chemical binders in the context of the present invention dung known per se and / or in the used organic chemical solvents soluble or dispersing or emulsifying Resins and / or binding drying oils, especially binders  consisting of or containing an acrylic resin, a vinyl resin, e.g. B. 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 based on a natural and / or Resin used.

The synthetic resin used as a binder can be in the form of an emulsion, disper sion or solution. Bitumen or bituminous substances up to 10 wt .-%, are used. In addition, you can dyes, pigments, water-repellants, odor correction known per se Gentien and inhibitors or corrosion protection agents and the like. Be used.

According to the invention, preference is given to organic chemical binders least an alkyd resin or modified alkyd resin and / or a drying one vegetable oil contained in the medium or in the concentrate. According to the invention alkyd resins with an oil content of more than 45 wt .-% before preferably 50 to 68 wt .-% used.

The binder mentioned can be wholly or partly by a fixing agent. (mixture) or a plasticizer (mixture) can be replaced. These additions are meant to volatilization of the active ingredients and crystallization or precipitation prevent. They preferably replace 0.01 to 30% of the binder (based on to 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 Gly kolether, glycerol ester and p-toluenesulfonic acid ester.

Fixing agents are chemically based on polyvinyl alkyl ethers such as. B. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone, amines such as e.g. B. alkanolamines such as monoethanolamine or ammonia.  

Under wood, which by the active ingredient mixture according to the invention or this can be protected, is to be understood as an example: construction timber, Wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, Pallets, containers, telephone poles, wooden cladding, wooden windows and doors, Plywood, particle board, carpentry or wood products, all in general used in house building or in carpentry.

A particularly effective wood protection is provided by industrial impregnation drive, e.g. B. vacuum, double vacuum or printing process.

The insecticidal agents used to protect wood and wood-based materials or concentrates 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 enable the previously ver to replace available insecticidal agents with more effective ones. You show a good one Stability and advantageously have a broad insecticidal activity spectrum.

The mixtures according to the invention can be used in ready-to-use applications if necessary also with further insecticides and to achieve additional an effect against wood-destroying and wood-staining fungi if necessary also be mixed with one or more fungicides. In many cases then observe additional synergisms.

Examples of insecticides that can be added are:
Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, α-1 (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, Sulfprofos, Triazophos and Trichlorphon;
Carbamates such as aldicarb, bendiocarb, α-2- (1-methylpropyl) phenylmethyl carbamate, butocarboxime, butoxycarboxime, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarb;
Organosilicon compounds, preferably dimethyl (phenyl) silyl-methyl-3-phen oxybenzyl ether such as dimethyl- (4-ethoxyphenyl) -silylmethyl-3-phenoxybenzyl ether or
(Dimethylphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether such as e.g. B. Dimethyl- (9-ethoxy-phenyl) -silylmethyl-2-phenoxy-6-pyridylmethyl ether or [(phenyl) -3- (3-phenoxyphenyl) propyl] (dimethyl) -silanes such as, for. B. (4-ethoxyphenyl) - [3- (4-fluoro-3-phenoxyphenylpropyl] 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-trif methyl vinyl) cydopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin, resmethrin and tralomethrin;
Nitroimines and nitromethylenes such as 1 - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro N-nitro-1H-imidazol-2-amine (imidacloprid), N - [(6-chloro-3- pyridyl) methyl-] N² cyano-N¹-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 thnns, pyridaben, pyridafenthion, pyriproxyfen, quinalphos, RH -7988, Rotenone, Sodium fluoride, Sodium hexafluorosilicate, Sulfotep, Sulfuryl fluonde, Tar Oils, Teflubenzuron, Tefluthrin, Temephos, Terbufos, Tetrachlorvinphos, Tetramethnn, O-2-tert.-Butyl-pyrimidin-5-yl-o-isopropyl phosphorothiate, thiocyclam, thio fanox, thiometone, traiomethrin, triflumuron, tnmethacarb, vamidothion, veru cillium lacanii, XMC, xylylcarb, benfuracarb, bensultap, bifenthrin, bioallethrin, MERbioailethromophosophone, bromine-isophenophenyl, s-bromine-bosomophenyl, s-bromophenophenyl, s-bromophenyl, z-bromophenopheno, b-bromophenol , Cadusafos, Calcium Polysulfide, Carbophenothion, Cartap, Chinomethionate, Chlordane, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chloropicnn, Chlor pyrifos, Cyanophos, Beta-Cyfluthrin, Alpha-cypermethrin, Cyophenothr in, Cyrom azine, Dazomet, DDT, Demeton-S-methylsulphone, Diafenthiuron, Dialifos, Di crotophos, Diflubenzuron, Dinoseb, Deoxabenzofos, Diaxacarb, Disulfoton, DNOC, Empenthrin, Endosulfan, EPN, Etfenarbcarberion, Feni Fenoxycarb, Fensulfothion, Fipronil, Flucycloxuron, Flufenprox, Flufenoxuron, Fonofos, Formetanate, Formothion, Fosmethilan, Fura thiocarb, Heptachlor, Hexaflumuron, Hydramethylnon, Hydrogen Cyanide, Hydro prene, IPSP, Isazofosothothodinophone, Isodophane, Isodophane, Isodophane, Isodophane, Iodine, Isodophane, Isodophane, Iodine, Isodophane, Isodophane, Iodine, Iodine, Isodophane, Iodine, Iodine , Malathion, Mecarbam, Mephosfolan, Mercurous, chloride, Metam, Metarthician, anisopliae, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methoprene, Methoxychlor, Methyl isothiocyanate, Metholcarb, Mevinphos, Monocrotophos, Naled, Neodiprionotiferate, Oxodiprionotine methyl, pentachlorophenol, petroleum oils, phenothrin, phenthoates, phorates;
The additional insecticides which may optionally be added can also be astonished 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, (±) -cphenyl- (4) -1,2,4-triazol-1-yl) -cycloheptanol, tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole, triticonazole, uniconazole and their metal salts and acid adducts.

Imidazoles such as:
Imazalil, pefurazoate, prochloraz, triflumizole, 2- (1-tert-butyl) -1- (2-chlorophenyl) -3- (1,2,4-triazol-1-yl) propan-2-ol, thiazolecarboxanilides such as 2 ′, 6′-dibromo-2-methyl-4-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxanil-ide, 1-imidazole yl-1- (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-methoxyacrylate-, methyl ( E ) -2- [2- [6- (2-thioamidophenoxy) pyrimidine -4-yloxy] phenyl] -3-methoxyacr-y late, methyl ( E ) -2-t2- [6- (2-fluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxy acrylates, methyl ( E ) -2-t2- [6- (2,6-difluorophenoxy) pyrimidin-4-yloxy] phenyl] -3- methoxyacrylates, methyl ( E ) -2- [2- [3- (pyrimidin-2-yloxy) phenoxy] phenyl] -3-meth oxyacrylate, methyl ( E ) -2- [2- [3- (5-methylpyrimidin-2-yloxy) phenoxy] phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- [3- (phenylsulfonyloxy) phenoxy] phenyl] -3-meth oxyacrylate, methyl ( E ) -2- [2- [3- (4-nitrophenoxy) phenoxy] phenyl] -3-methoxyacrylic late, methyl ( E ) -2- [2-phenoxyphenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- (3,5-di methylbenzoyl) pyrrol-1-yl] -3-methoxyacrylate, methyl ( E ) -2- [ 2- (3-methoxyphen oxy) phenyl] -. 3-methoxyacrylate, methyl ( E ) -2- [2- (2-phenylethen-1-yl) phenyl] -3- methoxyacrylate, methyl ( E ) -2- [2- (3,5-dichlorophenoxy) pyridin-3-yl] -3-methoxy acrylates, methyl ( E ) -2- (2- (3- (1,1,2,2-t etrafluoroethoxy) phenoxy) phenyl) -3-methoxy acrylate, methyl ( E ) -2- (2- [3- (alpha-hydroxybenzyl) phenoxy] phenyl) -3-methoxy acrylate, methyl ( E ) -2- (2- (4-phenoxypyridin-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-methylphenoxy) pyrimidin-4-yloxy] phenyl] -3-meth oxyacrylates, methyl ( E ) -2- [2- (5-bromopyridin-2-yloxymethyl) phenyl] -3 -methoxy acrylates, methyl ( E ) -2- [2- (3- (3-iodopyridin-2-yloxy) phenoxy) phenyl] -3-methoxy acrylates, 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-methoxyacrylates, (E) -methyl-2 - {- 2- [6 - (6-methylpyridin-2-yloxy) pyrimidine-4-yloxy] phenyl} -3-methoxyacrylate, ( E ), ( E ) methyl-2- {2- (3-methoxyphenyl) methyloximinomethyl] phenyl} -3- methoxyacrylates, (E) methyl-2- {2- (6- (2-azidophen oxy) pyrimidin-4-yloxy] phenyl} 3-methoxyacrylates, ( E ), ( E ) methyl-2- {2- [6 -phenyl pyrimidin-4-yl) -methyloximinomethyl] phenyl} -3-methoxyacrylate, ( E ), ( E ) methyl-2- {2 - [(4-chlorophenyl) -methyloximinomethyl] phenyl} -3-methoxyacrylate, ( E ) methyl- 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-methoxyacrylic late;
Succinate dehydrogenase inhibitors such as:
Fenfuram, furcarbanil, cyclafluramide, furmecyclox, seedvax, metsulfovax, pyrocarbolide, oxycarboxin, shirlan, mebenil (mepronil), benodanil, flutolanil (mon cut);
Naphthalene derivatives such as terbinafine, naftifine, butenafine, 3-chloro-7- (2-aza-2,7,7-trimethyl-oct-3-en-5-yne);
Sulfenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet; Captan, Captofol;
Benzimidazoles such as Carbendazim, Benomyl, Furathiocarb, Fuberidazole, Thiophonatmethyl, Thiabendazole or their salts;
Morpholine derivatives such as fenpropimorph, falimorph, dimethomorph, dodemorph, aldimorph, fenpropidine and their arylsulfonic salts, such as. B. 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, oxazolidines, hexa-hydro-S-triazines, N-methylolchloroacetamide,
Paraformadehyde, nitropyrin, oxolinic acid, tecloftalam;
Tris-N- (cyclohexyldiazeniumdioxy) aluminum, N- (cyclohexyldiazeniumdioxy) tri butyltin or K salts, bis-N- (cyclohexyldiazeniumdioxy) copper; N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazo1in-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-propynylphenyl carbamate,
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, broni dox, tectamer such as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-acetophe non, 2,2-dibromo-3-nitrile propionamide, 1,2-dibromo-2,4-dicyanobutane, β-bromo-β-nitrostyrene;
Pyridines such as 1-hydroxy-2-pyridinthione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrithione, 1-hydroxy-4-methyl-6- (2nd , 4,4-trimethylpentyl) -2 (1H) 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 a mixture with fixing agents;
Oxides such as tributyltin oxide, Cu₂O, CuO, ZnO; Dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, tetramethylthiuram disulfide, potassium N-methyldithiocarbamate;
Nitriles such as 2,4,5,6-tetrachloroisophthalonitrile, disodium cyano-dithioimidocarbamate;
Quinolines such as 8-hydroxyquininoin 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) -1,2-dithiol-3-one, 3,5-dimethyl-tetrahydro-1,3, 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 polymeric active ingredients, or else mixtures of several of the above-mentioned fungicides.

Claims (8)

1. Microbicidal compositions containing a synergistically effective mixture of at least one benzoyl urea and at least one agonist or Antagonists of nicotinic acetylcholine receptors. 2. Composition according to claim 1, comprising at least one benzoylurea of the formula (I) in which
R¹ represents halogen or hydrogen,
R² 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 haloalkoxy,
n represents the numbers 1, 2, 3 or 4, where the substituent Y can be the same or different,
R³ is halogen, haloalkyl or OR, where R is 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,
R⁴ represents halogen or haloalkyl, and
Q represents CH or N,
and at least one compound of the 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 stands for the radicals -CH = or = N-, where the radical -CH = can be linked to the radical Z instead of an H atom;
Z for a monofunctional group from the series alkyl, -OR, -SR, represents or represents a bifunctional group which is linked to the radical A or the radical X. 3. Composition according to claim 1, comprising at least one benzoyl urea from the series triflumuron, chlorofluoruron, diflubenzuron, flufenoxuron, flucycloxuron, hexaflumuron, penfluron or teflubenzuron and at least one compound of the formulas (IIa) - (IIh) 4. Composition 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 nicotine induce acetylcholine receptors. 6. Process for protecting technical materials from insecticidal Infestation, characterized in that one has a synergistic effect Mixture of at least one benzoyl urea and at least one Agonists or antagonists of nicotinergic acetylcholine receptors applies the materials to be protected or the materials with it Mixture treated. 7. Use of a synergistically effective mixture of at least one Benzoyl urea and at least one agonist or antagonist of Nicotinergic acetylcholine receptors for the protection of technical Materials from insecticidal infestation. 8. A process for the production of wood preservatives, characterized in that that a synergistically effective mixture of at least one Benzoyl urea and at least one agonist or antagonist of  nicotinergic acetylcholine receptors, with common wood preservatives constituents and optionally other active ingredients mixed.