Insecticidal composition for use in agriculture and horticulture.

The present invention relates to new insecticidal, synergistic, active substance combinations of known nitromethylene derivatives and known insecticides.

Nitromethylene derivatives and their use as insecticides have already been disclosed by the applicant of the present application (JP patent applications 20620/1984, 72966/1984 and 132943/1984).

It has already been disclosed that the following insecticides have insecticidal activity: S, S'-2-dimethylaminotrimethylene bis (thiocarbamate), N, N-dimethyl-1,2,3-trithian-4-ylamine, 2-t-butylimino-3-isopropyl-5-phenyl-1,3, 5-thiadiazinan-4-one and 1- (4-chlorophenyl) -3- (2,6-difluorobenzoyl) urea (The Pesticide Manual, 7. Edition, 1983, published by the British Crop Protection Council), N- (2,6-difluorobenzoyl) -N '- [3,5-dichloro-4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] urea (JP patent publication 53786/1982) and 3-phenoxybenzyl -2- (4-ethoxyphenyl) -2-methylpropyl ether (JP-OS 72928/1982.

However, the activities of these known insecticidal compounds are not entirely satisfactory, especially when the concentrations of these active compounds are low and when they are used only in small amounts.

It has also been disclosed that, for example, the following carboxylic acid esters have insecticidal activity: α-cyano-5-phenoxy-4-fluorobenzyl-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate (JP patent publication 57025/1982), (RS) -α-cyano-3-phenoxybenzyl (Z) - (1RS, 3RS) - (2-chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropane carboxylate, (RS) -α-cyano-3 -phenoxybenzyl-2,2,3,3-tetramethylcyclopropane carboxylate, (RS) -α-cyano-3-phenoxybenzyl- (RS) -2- (4-chlorophenyl) -3-methylbutyrate and α-cyano-3-phenoxybenzyl-1 -p-ethoxyphenyl-2,2-dichlorocyclopropane-1-carboxylate (see The Pesticide Manual, 7. Edition, 1983, published by the British Crop Protection Council).

However, the activities of these known insecticidal compounds are not entirely satisfactory, especially when their concentrations as active compounds are low or when they are used only in small amounts.

It has also been disclosed that, for example, the following carbamates have insecticidal activity: 2-isopropoxyphenyl methyl carbamate, 2-sec-butylphenyl methyl carbamate, m-tolyl methyl carbamate, 3,4, -xylyl methyl carbamate, 2,3-dihydro-2,2-dimethylbenzofuran-7-yl methyl carbamate, α-ethylthio-o-tolyl methyl carbamate and 2-dimethylamino-5,6-dimethyl carbamate (see The Pesticide Manual, 7th edition, 1983, published by the British Crop Protection Council).

However, the activities of these known carbarmates are not satisfactory when their concentrations are low or when they are used in small amounts. In addition, as a result of using these insecticides for several years, some insects have become resistant to some of these insecticides, and it has become very difficult to control and control these insects.

It has also been previously disclosed that, for example, the following organophosphate esters have insecticidal activity: O-ethyl-O-4-methylthiophenyl-S-propyl-phosphorodithioate, O-2,4-dichlorophenyl-O-ethyl-S-propyl-phosphorodithioate, O, O-diethyl-O-5-phenylisoxazol-3-yl- phosphorothioate, 2,3-dihydro-3-oxo-2-phenyl-6-pyridazinyl-diethylphosphorothioate, O, S-dimethyl-acetyl-phosphoramidothioate, O, O-diethyl-S-2-ethylthioethyl-phosphorodithioate and O, O-dimethyl S-2- (1-methylcarbamoylethylthio) ethyl phosphorothioate (see The Pesticide Manual, 7. Edition, 1983, published by the British Crop Protection Council).

However, the activities of these known organophosphates are not satisfactory when their concentrations are low or when they are used in small amounts. Furthermore, as a result of the use of these insecticides for several years, some insects have become resistant to some of these chemicals, and it has become very difficult to control and control these insects.

It has been found that new active substance combinations can be found (1) a nitromethylene derivative of the formula (I)<chemistry id="chem0001" num="0001"><img file="EP0214546A2_D0001.tif" /></chemistry> in the X denotes a lower alkyl group, a lower alkoxy group or a halogen atom, l denotes 0, 1 or 2 and m denotes 2 or 3, and at least one insecticidal compound selected from the following groups (2) to (5) have outstanding insecticidal activity due to synergistic effects: (2) Group of insecticides consisting of S, S'-2-dimethylaminotrimethylene bis (thiocarbamate), N, N-dimethyl-1,2,3, trithian-5-ylamine, 2-t-butylimino-3-isopropyl- 5-phenyl-1,3,5-thiadiazinan-4-one, 1- (4-chlorophenyl) -3- (2,6-difluorobenzoyl) urea, N- (2,6-difluorobenzoyl-N '- [3, 5-dichloro-4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] urea, 3-phenoxybenzyl-2- (4-ethoxyphenyl) -2-methylpropyl ether, 1- (4-trifluoromethoxyphenyl) -3- ( 2-chlorobenzoyl) urea, 1- [4- (2-dichloro-1-difluoroethoxy) phenyl] -3- (2-chlorobenzoyl) urea, 1- (4-trifluorophenyl) -3- (2,6-difluorobenzoyl) urea, 1- (2, 4-difluoro-3,5-dichlorophenyl) -3- (2,6-difluorobenzoyl) urea and N- [6- (2,2,3, trifluoro-3-chlorobenzodioxin (1,4))] - N '- (2,6-difluorobenzoyl) urea; (3) Group of carboxylic acid esters represented by the following formula<chemistry id="chem0002" num="0002"><img file="EP0214546A2_D0002.tif" /></chemistry> in the R¹ denotes a substituted lower alkyl group or a substituted cyclopropyl group, R² denotes a hydrogen atom or CN and X¹ and X² each represent a hydrogen or halogen atom; (4) Group of carbamates represented by the following formula<chemistry id="chem0003" num="0003"><img file="EP0214546A2_D0003.tif" /></chemistry> in the R³ denotes a substituted or unsubstituted aryl group, heterocyclic group or oxime group, R⁴ denotes a hydrogen atom or a lower alkyl group and R⁵ is a lower alkyl group or the group<chemistry id="chem0004" num="0004"><img file="EP0214546A2_D0004.tif" /></chemistry> referred to in the R⁶ represents a lower alkyl group and R⁷ represents a lower alkyl group, a lower alkoxycarbonyl group or a lower alkoxycarbonylalkyl group; (5) Group of the organophosphate esters represented by the following formula<chemistry id="chem0005" num="0005"><img file="EP0214546A2_D0005.tif" /></chemistry> in the X³ denotes an oxygen or sulfur atom, X⁴ denotes an oxygen or sulfur atom or a direct bond between the phosphorus atom and R¹⁰ in the formula, R⁸ denotes a lower alkyl group, R⁹ denotes a lower alkoxy group, a lower alkylthio group, a lower alkylcarbonylamide group or a phenyl group and R¹⁰ is a substituted or unsubstituted lower alkyl, lower alkenyl, Phenyl or heteroaryl group denotes or R⁹ and R¹⁰ together with the phosphorus atom and X⁴ in the formula denote a phosphorin ring.

Surprisingly, the insecticidal activity of the active substance combinations according to the invention is significantly greater than the sum of the effects of the individual active substances. Accordingly, there is a real synergistic effect.

By using the active substance combinations according to the invention, a cooperative and synergistic effect against rice field pests such as bugs of the order Hemiptera (for example White-backed lantern carriers) and rice leaf curlers of the order Lepidoptera, and pests on garden crops, including fruits and vegetables, such as cockroaches, cabbage moths and veil moths, can be obtained at concentrations lower than those in which the active compounds are used individually, and furthermore one can be obtained Prove residue effect.

For this reason, the insecticidal composition of the present invention offers a technical advantage which is very effective in the cultivation of agricultural and horticultural crops and which is of outstanding economic utility and applicability.

The nitromethylene derivatives of the general formula (I) used in the active substance combinations according to the invention are defined by the following formula<chemistry id="chem0006" num="0006"><img file="EP0214546A2_D0006.tif" /></chemistry> in the X denotes a lower alkyl group, a lower alkoxy group or a halogen atom, l denotes 0, 1 or 2 and m denotes 2 or 3.

In formula (I), X preferably denotes a methyl group, a methoxy group, a chlorine atom, a bromine atom or a fluorine atom, l 1 or 2 and m 2 or 3, and the bond position the pyridine ring is the 3- (or 5-) position.

The nitromethylene derivative of the general formula (I) can also occur in the form of salts. Examples of these salts include salts of inorganic acids, sulfonic acid salts, salts of organic acids and metal salts, preferably hydrochlorides, p-toluenesulfonates, copper (II) acetates and succinates. Accordingly, the term nitromethylene derivatives of the formula (I) as used here also refers to their salts.

Examples of the nitromethylene derivatives of the formula (I) which are used in the active substance combination according to the invention include 1- (3-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine, 1- (2-methyl-5-pyridylmethyl) -2- (nitromethylene) imidazolidine, 1- (2-methyl-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine, 1- (2-methoxy-5-pyridylmethyl) -2- (nitromethylene) imidazolidine, 1- (2-methoxy-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine, 1- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine, 1- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine, 1- (2-fluoro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine, 1- (2-fluoro-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine, 1- (2-bromo-5-pyridylmethyl) -2- (nitromethylene) imidazolidine, 1- (2-bromo-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine, 1- (5-chloro-2-pyridylmethyl) -2- (nitromethylene) imidazolidine, 1- (5-chloro-2-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine, 1- (2,4-dichloro-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine, 1- (2,4-dibromo-5-pyridylmethyl) -2- (nitromethylene) imidazolidine, 1- (2,3-dichloro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine, 1- (3-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine hydrochloride, 1- (2-methyl-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine p-toluenesulfonate, 1- (2-methoxy-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine succinate, 1- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine hydrochloride, 1- (2-fluoro-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine copper (II) acetate, 1- (2-bromo-5-pyridylmethyl) -2- (nitromethylene) imidazolidine succinate and 1- (2,4-dichloro-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine p-toluenesulfonate.

The insecticidal activity of the nitromethylene derivatives of the general formula (I) is described in JP patent applications 20620/1984, 72966/1984 and 132943/1984.

Examples of the known insecticides from the other insecticides selected from the above group (2) are the following: S, S'-2-dimethylaminotrimethylene bis (thiocarbamate) (Cartap), N, N-dimethyl-1,2,3-trithian-5-ylamine (thiocyclam), 2-t-butylimino-3-isopropyl-5-phenyl-1,3,5-thiadiazinan-4-one (buprofezin), 1- (4-chlorophenyl) -3- (2,6-difluorobenzoyl) urea (diflubenzuron) (The Pesticide Manual, 7th edition, 1983, published by the British Crop Protection Council). N- (2,6-difluorobenzoyl-N '- [3,5-dichloro-4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] urea (JP Patent Publication 53786 (1982) and 3-phenoxybenzyl-2- (4-ethoxyphenyl) -2-methylpropyl ether (JP-OS 72928/1982).

Preferred carboxylic acid esters (group (3)) of the formula (II) which are used in the active substance combinations according to the invention are those compounds of the formula (II) in which R¹ denotes an alkyl group which is substituted by a phenyl group which in turn is substituted by a substituent selected from halogen atom, lower alkoxy groups and lower halogenoalkoxy groups, and the alkyl group may be further substituted by a dichlorocyclopropane group, or R1 denotes an alkyl group which is substituted by a phenylamino group, which in turn can be substituted by a halogen atom and a halogenoalkyl group, the halogenoalkyl group preferably being a trifluoromethyl group, or R¹ denotes a cyclopropyl group which is represented by an alkyl group having 1 to 3 carbon atoms, preferably a methyl group is substituted, or denotes a cyclopropyl group which is substituted by an alkyl group having 1 to 3 carbon atoms, preferably a methyl group, and a halogenoalkyl group having 2 to 3 carbon atoms, R² denotes a hydrogen atom or CN and X¹ and X² each denote a hydrogen atom, a chlorine atom or a fluorine atom, preferably X¹ denotes a hydrogen or fluorine atom and X² denotes a hydrogen atom.

Examples of the carboxylic acid esters of the general formula (II) include α-cyano-5-phenoxy-4-fluorobenzyl-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropane carboxylate (cyfluthrin), 3-phenoxybenxyl- (1RS, 3RS; 1RS; 3SR) -3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropane carboxylate (permethrin), (RS) -α-cyano-3-phenoxybenzyl- (1RS; 3RS; 1RS; 3SR) -3- (2,2-dichloro-vinyl) -2,2-dimethylcyclopropane carboxylate (cypermethrin), (S) -α-cyano-3-phenoxybenzyl- (1R, 3R) -3- (2,2-dibromovinyl) -2,2-dimethylcyclopropane carboxylate (deltamethrin), (RS) -α-cyano-3-phenoxybenzyl (Z) - (1RS, 3RS) - (2-chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropane carboxylate (cyhalothrin), (RS) -α-cyano-3-phenoxybenzyl-2,2,3,3-tetramethylcyclopropane carboxylate (fenpropathrin), (RS) -α-cyano-3-phenoxybenzyl- (RS) -2- (4-chlorophenyl) -3-methylbutyrate (Fenvalerate), (RS) -α-cyano-3-phenoxybenzyl- (S) -2- (4-difluoromethoxyphenyl) -3-methylbutyrate (flucythrinate), α-cyano-3-phenoxybenzyl-1-p-ethoxyphenyl-2,2-dichlorocyclopropane-1-carboxylate and (RS) -α-cyano-3-phenoxybenzyl-N- (2-chloro-α, α, α-trifluoro-p-tolyl) -D-valinate (fluvalinate).

The carboxylic acid esters as a component of the active substance combinations according to the invention are already known. For example, they are described as insecticides in The Pesticide Manual, 7th edition, 1983, published by the British Crop Protection Council.

Preferred carbamates (group (4)) are those compounds of the formula (III) in which R³ denotes a phenyl group which is substituted by one or two identical or different alkyl groups, alkoxy groups having 1 to 4 carbon atoms or ethylthiomethyl groups, or R³ is a naphthyl group, a pyrimidinyl group which is formed by a dialkylamino group having 1 to 3 carbon atoms, preferably a dimethylamino group, and two alkyl groups with 1 to 4 carbon atoms, preferably methyl groups, or a 2,3-dihydrobenzofuranyl or benzoxazolyl group, which is preferably substituted by an alkyl group with 1 to 4 carbon atoms denotes a methyl group, is substituted or R³ is a group of the general formula<chemistry id="chem0007" num="0007"><img file="EP0214546A2_D0007.tif" /></chemistry> referred to in the R¹¹ denotes an alkyl group having 1 to 4 carbon atoms, preferably a methyl group, and R 12 denotes an alkylthio group having 1 to 4 carbon atoms, preferably a methylthio group, R⁴ denotes a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, preferably the alkyl group with 1 to 4 carbon atoms R⁴ denotes methyl, and R⁵ is an alkyl group with 1 to 4 carbon atoms, preferably a methyl group, or a group of the formula<chemistry id="chem0008" num="0008"><img file="EP0214546A2_D0008.tif" /></chemistry> referred to in the R⁶ represents an alkyl group with 1 to 5 carbon atoms and R⁷ represents an alkyl group, an alkoxycarbonyl group or an alkoxycarbonylalkyl group, each comprising 1 to 5 carbon atoms.

Examples of the carbamates of the general formula (III) include 2-isopropoxyphenylmethyl carbamate (propoxur), o-cumenyl methyl carbamate (isoprocarb), 2-sec-butylphenyl methyl carbamate (BPMC), 3,4-xylyl methyl carbamate (xylyl carb), m-tolyl methyl carbamate (Metolcarb), 3,5-xylyl methyl carbamate (XMC), α-ethylthio-o-tolylmethyl carbamate (ethiofencarb), 1-naphthylmethyl carbamate (carbaryl), 2-dimethylamino-5,6-dimethylpyrimidin-4-yl-dimethylcarbamate (Pirimicarb), 2,2-dimethyl-1,3-benzodioxol-4-ylmethyl carbamate (bendiocarb), 2,3-dihydro-2,2-dimethylbenzofuran-7-ylmethyl carbamate (carbofuran), Butyl-2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N, N-dimethyl-N, N-thiodicarbamate (furanthiocarb), 2,3-dihydro-2,2-dimethylbenzofuran-7-yl- (dibutylaminosulfenyl) (methyl) carbamate (carbosulfan) (see JP patent publication 39487/1983), 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-isopropyl-N-ethoxycarbonylethylaminosulfenyl) -N-methylcarbamate (aminosulfulan) (see JP-OS 200377/1982) and S-methyl-N- (methylcarbamoyloxy) thioacetimidate (methomyl).

The carbamates used as a component of the active substance combinations according to the invention are already known. For example, they are described in The Pesticide Manual, 7th edition, 1983, published by the British Crop Protection Council.

Preferred organophosphate esters (group (5)) are those compounds of the formula (IV) in which R⁸ denotes an alkyl group with 1 to 4 carbon atoms, R⁹ denotes an alkoxy group, an alkylthio group or an alkylcarbonylamide group, each of which comprises 1 to 4 carbon atoms or denotes a phenyl group, R¹⁰ one through one or two of halogen atoms and methyl, methylthio, Nitro and cyano groups called selected substituents substituted phenyl group or R¹⁰ denotes an alkyl group with 1 to 3 carbon atoms, optionally by a halogen atom, an alkylthio (or sulfinyl) group with 2 to 3 carbon atoms, a phenyl group, an alkoxycarbonyl group with 1 to 4 carbon atoms, an alkylcarbamoyl group with 1 to 4 carbon atoms, an alkylcarbamoylalkyl- (C_1-2) thioalkyl (C_1-2) Group or an alkoxycarbonyl-N-methylcarbamoyl group with 1 to 4 carbon atoms, a halogen-substituted benzoxazole group or an alkyl group with 1 to 3 carbon atoms, which is represented by a halogen atom and a phthalimide Group is substituted, or R¹⁰ denotes an alkenyl group with 2 to 3 carbon atoms, which is formed by one or two halogen atoms, a halogen-substituted phenyl group and an alkylcarbamoyl group, selected substituents, or R¹⁰ denotes a pyridinyl, pyrimidinyl, pyridazinyl, quinoxalinyl, isoxazolyl or oxo-1,3,4-thiadiazolyl group, which by one to three identical or different alkyl groups, alkoxy groups, dialkylamino groups all comprise 1 to 4 carbon atoms, halogen atoms or phenyl groups are substituted, or R⁹ and R¹⁰ together denote a benzodioxaphosphorin ring or in the case where X⁴ denotes a direct bond between the phosphorus atom and R¹⁰,<chemistry id="chem0009" num="0009"><img file="EP0214546A2_D0009.tif" /></chemistry> designated.

Examples of the organophosphates of the general formula (IV) are O, O-dimethyl-O-4-methylthio-m-tolyl-phosphorothioate (fenthion), O, O-dimethyl-O-4-nitro-m-tolyl phosphorothioate (fenitrothione), 4- (methylthio) phenyl-dipropyl-phosphate (Propaphos), O-4-cyanophenyl-O, O-dimethyl-phosphorothioate (Cyanophos), O-2,4-dichlorophenyl-O-ethyl-S-propyl-phosphorodithioate (Prothiofos), O-ethyl-O-4-methylthiophenyl-S-propyl-phosphorodithioate (Sulprofos), O-4-bromo-2-chlorophenyl-O-ethyl-S-propyl-phosphorothioate (Profenofos), O-ethyl-O-4-nitrophenyl-phenylphosphonothioate (EPN), O-4-cyanophenyl-O-ethyl-phenylphosphonothioate (Cyanofenphos), O, S-dimethyl-acetylphosphoramidothioat (acephate), S-2-ethylsulfinyl-1-methylethyl-O, O-dimethylphosphorothioat (Oxydeprofos), O, O-Diethyl-S-2-ethylthioethyl-phosphorodithioate (Disulfoton), S-2-ethylthioethyl-O, O-dimethylphosphorodithioate (thiometone), S-α-ethoxycarbonylbenzyl-O, O-dimethylphosphorodithioat (Phenthoate), S-1,2-bis (ethoxycarbonyl) ethyl-O, O-dimethylphosphorodithioate (malathion), O, O-dimethyl-S-methylcarbamoylmethyl-phosphorodithioate (dimethoate), O, O-dimethyl-SS- (1-methylcarbamoylethylthio) ethyl phosphorothioate (Vamidothion), S- (N-ethoxycarbonyl-N-methylcarbamoylmethyl) -O, O-diethylphosphorodithioate (Mecarbam), Dimethyl-2,2,2-trichloro-1-hydroxyethylphosphonate (trichlorophone), 1,2-dibromo-2,2-dichloroethyl dimethyl phosphate (Naled), 2,2-dichlorovinyl dimethyl phosphate (dichlorvos), 2-chloro-1- (2,4-dichlorophenyl) vinyl diethyl phosphate (chlorofenvinphos), (Z) -2-chloro-1- (2,4,5-trichlorophenyl) vinyldimethylphosphate (tetrachlorvinphos), Dimethyl- (E) -1-methyl-2- (methylcarbamoyl) vinyl phosphate (Monocrotophos), S-6-chloro-2,3-dihydro-2-oxobenzoxazol-3-ylmethyl-O, O-diethylphosphorodithioate (phosalones), S-2-chloro-1-phthalimidoethyl-O, O-diethylphosphorodithioate (Dialifos), O, O-dimethyl-O-3,5,6-trichloro-2-pyridyl phosphorothioate (chlorpyrifos-methyl), O, O-Diethyl-O-3,5,6-trichloro-2-pyridylphosphorthioat (Chlorpyrifos), O-2-diethylamino-6-methylpyrimidin-4-yl-O, O-dimethylphosphorothioate (Pirimophos-methyl), O, O-diethyl-O-2-isopropyl-6-methylpyrimidin-4-ylphosphorothioate (diazinon), O-6-ethoxy-2-ethylpyrimidin-4-yl-O, O-dimethyl-phosphorothioate (Etrimfos-), 2,3-dihydro-3-oxo-2-phenyl-6-pyridazinyl-diethylphosphorothioate (pyridaphenthione), O, O-diethyl-O-quinoxalin-2-yl phosphorothioate (Quinalphos), O, O-diethyl-O-5-phenylisoxazol-3-yl-phosphorothioate (isoxathione), S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-yl-methyl-O, O-dimethylphosphorodithioate (methidathione) and 2-methoxy-4H-1,3,2_-⁵-Benzodioxaphosphorin-2-sulfide (salithione).

The organophosphate esters, a component of the active substance combinations according to the invention, are already known and are described, for example, in The Pesticide Manual, 7th edition, 1983 (published by the British Crop Protection Council) as insecticides.

The organophosphates described above include, for example, Quinalphos, Fenthion, Sulprofos, Phenthoate, Fenitrothion, Diazinon, Isoxathion, Pyridaphenthion, Trichlorphon, Chlorpyriphos-methyl, Malathion, Monocrotophos, Propaphos, EPN, Etrimfos and preferably Tetrachloridophine in order to control pests from Letrachlorvinvin Rice fields, such as rice leaf wrapper (Cnaphalocrocis medinalis) and rice stalk borer (Chilo suppressalis).

Prothiofos, Sulprofos, Dichlorovos, Trichlorphon, Cyanophos, Pyrimophos-methyl, Chloropyrifos, Dimethoat, Phosalone, Methidathion, Chlorofenvinphos, Acephat, Salithion, Dialifos, Mecarbam, Profenofos, Naled, Phenthoath, EP, Nitronion, Fenitrothionox, Fenitrothionox, Nitronion, Fenitrothionox, Nitronion, Fenitronion, Fenitrothionium for example preferably z controlling pests of the order Lepidoptera in horticulture, such as the cockroach, cabbage moth or veil moth (Plutella maculipennis), the coal owl or heartworm (Mamestra brassicae) and leaf wrappers.

Furthermore, for example, Disulfoton, Vamidothion, Thiometon and Oxydeprofos are preferably used in horticulture, in particular for controlling pests of the order Hemiptera such as aphids, including aphids on peach trees, cotton and apple trees.

The weight ratios of the groups of active substances in the active substance combinations can be varied within relatively wide ranges. In general, 0.05 to 10 parts by weight of the active substance of group (2) of the active substances, preferably 0.1 to 5 parts by weight, per 1 part by weight of the active substance of group (1) active substances applied.

Furthermore, 0.05 to 10 parts by weight of the active substance of group (3) of active substances (carboxylic acid esters of the formula (II)), preferably 0.1 to 5 parts by weight, are generally used per 1 part by weight the active substance of group (1) of active substances applied.

Furthermore, generally 0.1 to 20 parts by weight of the active substance of group (4) of active substances (carbamates of the formula (III)), preferably 0.2 to 15 parts by weight, per 1 part by weight the active substance of group (1) of active substances applied.

Furthermore, 0.05 to 10 parts by weight of the active substance of group (5) of active substances (organophosphate ester of the formula (IV)), preferably 0.1 to 5 parts by weight, per 1 part by weight the active substance of group (1) of active substances applied.

The active substance combinations according to the invention show excellent insecticidal activity. Accordingly, they can be applied as insecticides by applying to foliage, underwater or water surface application, application to the soil, soil mixing treatment, application to a plant case etc.

The active substance combinations according to the invention show strong insecticidal activity and can therefore be used as insecticides. The active substance combinations according to the invention have no phytotoxicity against crop plants, show only a low toxicity to warm-blooded animals and can be used for the precise control of pests, in particular insects, in agriculture and forestry and in stored crop yields and products. They are active against sensitive and resistant species and against all or some stages of development.

For example, the active substance combinations according to the invention can be used effectively to control rice field pests, for example against bugs and lantern carriers of the order Hemiptera (for example the brown lantern carrier, the white-back lantern carrier and the smaller brown lantern carrier) and leafhopper Larvae of insects of the order Lepidoptera (rice stalk borer, rice leaf curler etc.) and the rice beetle (rice weevil) of the order Coleoptera, and also against pests on horticultural crops such as fruit trees and vegetables, for example larvae of insects of the order Lepidoptera (cockroach, cabbage moth or veil moth, army worm, leaf winder etc.) and scale insects of the order Hemiptera.

The active substance combinations according to the invention show potent insecticidal effects. For this reason, they can be used against the following pests.

Insects of the order Coleoptera

Callosobruchus chinensis, Sitophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomala rufocuprea, Leptinotarsa ​​decemkineata, Diabrotica spp., Monochamus alternatus, Lissorhoptrus oryzophilus and Lyctus brunneus;

Insects of the order Lepidoptera

Lymantria dispar, Malacosoma neustria, Pieris rapae, Spodoptera litura, Mamestra brassicae, Chilo suppressalis, Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella, Agrotis fucosa, Galleria mellonella, Plutella maculipennis, Heliothis virscens and Phyllocnistis citrella;

Insects of the order Hemiptera

Nephotettix cincticeps, Nilaparvata lugens, Laodelphax striatellus, Sogatella furcifera, Pseudococcus comstocki Unaspis yanonensis, Myzus persicae, Aphis pomi, Aphis gossypii Ropalosiphum pseudobrassicae, Stephanitis nashi, Nezara spp., Trialeurodes vaporariorum and Psylla spp .;

Insects of the order Orthoptera

Gryllotalpa africana and Locusta migratoria migratoriodes;

The active substance combinations can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosol, natural or synthetic substances impregnated with the active compound, very fine capsules in polymeric substances, coating compositions for use Seeds (dressings) and formulations for use with incinerators such as smoking cartridges, Smoking cans and smoking snakes as well as for cold and warm atomization using the ultra-low-volume process.

These formulations can be prepared in a known manner, for example by mixing the active substance combinations with extenders, that is to say with liquid or liquefied gaseous or solid diluents or carriers, if appropriate using surfactants, that is to say emulsifiers and / or dispersants and / or foaming agents. When using water as an extender, organic solvents can be used, for example, as auxiliary solvents.

Aromatic hydrocarbons such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzenes, choroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example mineral oil fractions, alcohols such as butanol or glycol, and the like are mainly suitable as liquid solvents, diluents or carriers their ethers and esters, ketones such as acetone, methyl ethyl ketone, Methyl isobutyl ketone or cyclohexanone or strongly polar solvents such as dimethylformamide and dimethyl sulfoxide as well as water.

Liquefied gaseous diluents or carriers are to be understood as liquids which would be gaseous at normal temperature and normal pressure, for example aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide.

Ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and ground synthetic minerals such as highly disperse silica, aluminum oxide and silicates can be used as solid carriers. Comminuted and fractionated natural stone materials, such as calcite, marble, pumice, sepiolite and dolomite, and synthetic granules made from inorganic and organic flours and granules made from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks, can be used as solid carriers for granules.

Non-ionic 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 albumin hydrolysis products can be used as emulsifying and / or foam-forming agents. Dispersants include, for example, lignin sulfite leaching and methyl cellulose.

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 formulation.

It is possible to use colorants, such as inorganic pigments such as iron oxide, titanium oxide and Prussian blue and organic dyes such as alizarin dyes, azo dyes or metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt To use molybdenum and zinc.

The formulations generally contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight of the active compound.

The active substance combinations according to the invention can be present in their commercially available formulations or in the use forms prepared from these formulations in a mixture with other active compounds, for example with insecticides, baits, sterilizing agents, acaricides, nematicides, fungicides, growth regulators or herbicides. Insecticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylureas and substances produced by microorganisms.

The active substance combinations according to the present invention can furthermore be present in their commercially available formulations or in the use forms produced from these formulations in a mixture with synergistic agents. Synergistic agents are compounds which increase the activity of the active compounds without the need for the added synergistic agent to be active itself.

The content of the active compound in the use forms prepared from the commercially available formulations can vary within wide limits. The concentration of the active compound in the use forms can be 0.00001 to 100% by weight and is preferably between 0.00004 and 1% by weight.

The compounds are used in a customary manner in a form which is appropriate for the use forms.

When used against pests in product inventories, the active substance combinations are characterized by an excellent residue effect on wood and clay as well as a good resistance to alkali on limed substrates.

The following examples illustrate the present invention in detail. However, it should be noted that the present invention is not limited to these specific examples alone.

A) Biological examples of new active substance combinations of (1) a nitromethylene derivative of the formula (I) and an insecticidal compound from group (2):

example 1

Test against cnaphalocrosis

Preparation of a test chemical:

Solvent: 3 parts by weight of xylene Emulsifier: 1 part by weight of polyoxyethylene alkylphenyl ether

To prepare a formulation of the active compounds, 1 part by weight of the active compounds was mixed with the above-mentioned amount of solvent containing the above-mentioned amount of emulsifier, and the mixture was diluted with water to a predetermined concentration.

Test procedure

Three rice seedlings 15 cm high were each planted in 9 cm diameter vinyl resin pots. Ten days after the transplantation, an aqueous dilution of the active compounds with a predetermined concentration, which was prepared as stated above, in an amount of 20 ml per pot was sprayed onto the plants using a spray gun. After the sprayed-on substance was dried in air, a cylinder of plastic mesh 9 cm in diameter and 25 cm in height was placed over each pot, and 10 larvae of rice leaf curlers (Cnaphalocrosis medinalis Gueneer) in the fourth stage of development were exposed in each pot. The pots were each placed in a constant temperature room and 2 days later the number of dead insects was counted. The destruction ratio was then calculated. The above test was carried out with two parallel tests.

The results are shown in Table 1.<ul id="ul0001" list-style="none"><li>Compound No. 2: 1- (2-methoxy-5-pyridylmethyl) -2- (nitromethylene) tetrahydrodropyrimidine,</li><li>Compound No. 3: 1- (2-bromo-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine,</li><li>Compound No. 4: 1- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine,</li><li>Compound No. 5: 1- (2-fluoro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine.</li></ul>

Compounds from the above-mentioned group (2) of insecticides which are used in the present invention:<ul id="ul0002" list-style="none"><li>[A]: Cartap,</li><li>[B]: Thiocyclam.</li></ul><tables id="tabl0001" num="0001"><img file="EP0214546A2_D0010.tif" /></tables><ul id="ul0003" list-style="none"><li>Note 1. None of the chemical mixtures or individual chemicals used in the tests of this example showed phytotoxicity.</li><li>2nd Compound of general formula (I) used in the present invention: Compound No. 1: 1- (2-methyl-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine.</li></ul>

Example 2

Test against Sogatella

Three rice seedlings about 15 cm high were each planted in pots about 13 cm in diameter, and ten days after transplanting, an aqueous dilution of the active compounds at a predetermined concentration prepared as in Example 1 was made in an amount of 20 ml per pot sprayed onto the plants using a spray gun. Ten days and twenty days after spraying, a cage was placed over each pot and ten larvae of white-backed lantern carriers (Sogatella furcifera) in the third stage of development were placed in each pot. The pots were each placed in a constant temperature room, and 2 days and 7 days later, the number of dead insects was counted. The kill rate was then calculated. The above test was carried out with two parallel tests.

The results are shown in Table 2.<tables id="tabl0002" num="0002"><img file="EP0214546A2_D0011.tif" /></tables>

Notes on Table 2:

<ul id="ul0004" list-style="none"><li>1. None of the chemical mixtures or individual chemicals used in Example 2 showed phytotoxicity.</li><li>2nd Compounds Nos. 1, 2, 3, 4 and 5 of the general formula (I) used in the present invention are the same as those given in Example 1.</li><li>3rd Compound from the above group (2) of insecticides used in the present invention: [A]: Buprofezin.</li></ul>

Example 3

Test against Plutella

Test procedure

An aqueous dilution of the active compounds at a predetermined concentration, prepared as in Example 1, was applied to cabbage seedlings about 15 cm high before heading, which had been planted in 9 cm diameter pots, in an amount of 20 ml sprayed per pot using a spray gun. The sprayed substance was allowed to air dry and ten larvae of cabbage moths (Plutella maculipennis) in the second stage of development were exposed in each pot. The pots were each placed in a constant temperature room, and the number of dead insects was counted 2 days and 7 days later. The degree of kill nis was calculated. The above test was carried out with two parallel tests.

The results are shown in Table 3.<tables id="tabl0003" num="0003"><img file="EP0214546A2_D0012.tif" /></tables><tables id="tabl0004" num="0004"><img file="EP0214546A2_D0013.tif" /></tables>

Remarks:

<ul id="ul0005" list-style="none"><li>1. None of the chemical mixtures used or individual chemicals used in Example 3 showed phytotoxicity.</li><li>2nd Compounds Nos. 1, 2, 3, 4 and 5 of the general formula (I) used in the present invention are the same compounds as in Example 1.</li><li>3rd Compounds from the above-mentioned group (2) of insecticides which are used in the present invention:<ul id="ul0006" list-style="none"><li>[A]: diflubenzuron,</li><li>[B]: N- (2,6-difluorobenzoyl) -N '- [3,5-dichloro-4- (3-chloro-5-trifluoromethyl-2-pyridyloxyl) phenyl] urea.</li></ul></li></ul>

Example 4

Test against Plutella

Test procedure

An aqueous dilution of the active compounds at a predetermined concentration, prepared as in Example 1, was applied to cabbage seedlings about 15 cm high before heading, which had been planted in 9 cm diameter pots, in an amount of 20 ml sprayed per pot using a spray gun. After air-drying the sprayed substance, ten larvae of cabbage moths (Plutella maculipennis), which were resistant to organophosphorus compounds, were exposed to the fourth stage of development in each pot. The pots were placed in a constant temperature room. Two days later, the number of dead insects was counted and the degree of kill was calculated. The above test was carried out with two parallel tests.

The results are shown in Table 4.<tables id="tabl0005" num="0005"><img file="EP0214546A2_D0014.tif" /></tables>

Remarks:

<ul id="ul0007" list-style="none"><li>1. None of the chemical mixtures or individual chemicals used in Example 4 showed phytotoxicity.</li><li>2nd Compounds Nos. 1, 2, 3, 4 and 5 of general formula (I) used in the present invention are the same as those used in Example 1.</li><li>3rd Compound from group (2) above or insecticides used in the present invention: [A]: 3-phenoxybenzyl-2- (4-ethoxyphenyl) -2-methylpropyl ether.</li></ul>

Example 5

Wettable powder

20 Parts of the active substance of formula (I), 20 parts of Cartap, 55 parts of a 1: 5 mixture of powdery diatomaceous earth and powdered clay, 2 parts of alkylbenzenesulfonate and 3 parts of sodium alkylnaphthalenesulfonate-formaldehyde condensate are pulverized and mixed together, whereby a wettable powder is obtained.

B) Biological examples of new active substance combinations of (1) a nitromethylene derivative of the formula (I) and a carboxylic ester compound of group (3) (formula (II)):

Example 6

Test against Plutella

Preparation of a test chemical:

Solvent: 3 parts by weight of xylene Emulsifier: 1 part by weight of polyoxyethylene alkylphenyl ether

To prepare a formulation of the active compounds, 1 part by weight of the active compounds was mixed with the above-mentioned amount of solvent containing the above-mentioned amount of emulsifier, and the mixture was diluted with water to a predetermined concentration.

Test procedure

An aqueous dilution of the active compounds at a predetermined concentration, prepared as set forth above, was applied to cabbage seedlings about 15 cm high before heading, which had been planted in 9 cm diameter pots, in an amount of 20 ml sprayed per pot using a spray gun. The sprayed substance was allowed to air dry and ten larvae of cabbage moths (Plutella maculipennis), which were resistant to organophosphorus compounds, were exposed to the fourth stage of development in each pot. The pots were each placed in a constant temperature room and the number of dead insects was counted 2 days later. The degree of killing was calculated. The above test was carried out with two parallel tests.

The results are shown in Table 5.<tables id="tabl0006" num="0006"><img file="EP0214546A2_D0015.tif" /></tables><tables id="tabl0007" num="0007"><img file="EP0214546A2_D0016.tif" /></tables>

Remarks:

<ul id="ul0008" list-style="none"><li>1. None of the chemical mixtures or individual chemicals used in the test of Example 6 showed phytotoxicity.</li><li>2nd Compounds of general formula (I) used in the present invention:<ul id="ul0009" list-style="none"><li>Compound No. 1: 1- (2-methyl-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine,</li><li>Compound No. 2: 1- (2-methoxy-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine,</li><li>Compound No. 3: 1- (2-bromo-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine,</li><li>Compound No. 4: 1- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine,</li><li>Compound No. 5: 1- (2-fluoro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine.</li></ul></li><li>3rd Compounds (carboxylic acid esters of the formula (II)) from the above-mentioned group (3) of the insecticides which are used in the present invention:<ul id="ul0010" list-style="none"><li>[A]: Cyfluthrin,</li><li>[B]: cyhalothrin,</li><li>[C]: fenpropathrin,</li><li>[D]: Fenvalerate,</li><li>[E]: flucythrinate,</li><li>[F]: fluvalinates,</li><li>[G]: α-cyano-5-phenoxybenzyl-1-p-ethoxyphenyl-2,2-dichlorocyclopropane-1-carboxylate.</li></ul></li></ul>

Example 7

Emulsifiable concentrate

2nd Parts of the active substance of formula (I), 2 parts of cyfluthrin, 81 parts of xylene, 8 parts of polyoxyethylene alkyl phenyl ether and 7 parts of calcium alkylbenzenesulfonate are mixed with one another with stirring, whereby an emulsifiable concentrate is obtained.

C) Biological examples of new active substance combinations of (1) a nitromethylene derivative of the formula (I) and a carbamate of group (4) (formula (III)):

Example 8

Test against Nilaparvata

Manufacture of a test chemical

Solvent: 3 parts by weight of xylene Emulsifier: 1 part by weight of polyoxyethylene alkylphenyl ether

To prepare a formulation of the active compounds, 1 part by weight of the active compounds was mixed with the above-mentioned amount of solvent containing the above-mentioned amount of emulsifier, and the mixture was diluted with water to a predetermined concentration.

Test procedure

Three rice seedlings 15 cm high were each planted in 13 cm diameter pots. Ten days after the transplantation, an aqueous dilution of the active compounds with a predetermined concentration, which was prepared as stated above, in an amount of 20 ml per pot was sprayed onto the plants using a spray gun. After air-drying the sprayed substance, a cage was placed over each pot and 10 larvae of brown rice leaf bugs (Nilaparvata lugens) in the fourth stage of development were exposed in each pot. The pots were placed in a constant temperature room. Three days later, the number of dead insects was counted and the kill rate was calculated. The above test was carried out with two parallel tests.

The results are shown in Table 6.<tables id="tabl0008" num="0008"><img file="EP0214546A2_D0017.tif" /></tables><tables id="tabl0009" num="0009"><img file="EP0214546A2_D0018.tif" /></tables>

Remarks:

<ul id="ul0011" list-style="none"><li>1. None of the chemical mixtures or individual chemicals used in the test of Example 6 showed phytotoxicity.</li><li>2nd Compounds of general formula (I) used in the present invention:<ul id="ul0012" list-style="none"><li>Compound No. 1: 1- (2-methyl-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine,</li><li>Compound No. 2: 1- (2-methoxy-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine,</li><li>Compound No. 3: 1- (2-bromo-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine,</li><li>Compound No. 4: 1- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine,</li><li>Compound No. 5: 1- (2-fluoro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine.</li></ul></li><li>3rd Compounds (carbamates of the formula (III)) from the above-mentioned group (4) of the insecticides which are used in the present invention:<ul id="ul0013" list-style="none"><li>[A]: propoxur,</li><li>[B]: BPMC,</li><li>[C]: isoprocarb,</li><li>[D]: Metolcarb,</li><li>[E]: xylylcarb,</li><li>[F]: carbofuran,</li><li>[G]: carbosulfan,</li><li>[H]: aminosulfan,</li><li>[I]: Bendiocarb.</li></ul></li></ul>

Example 9

Test against Aphis

Test procedure:

Cotton aphids (cucumber aphids; Aphis gossypii) that had been grown were exposed to eggplant seedlings about 15 cm high, grown in 9 cm diameter pots, about 100 aphids per seedling. One day after the exposure, an aqueous dilution of the active compounds prepared as in Example 8 was sprayed onto the plants at a predetermined concentration in an amount of 20 ml per pot by a spray gun. After spraying, the pots were kept in a greenhouse at 28 ° C. Two days after spraying, the number of dead insects was counted and the kill rate was calculated.

The results are shown in Table 7.<tables id="tabl0010" num="0010"><img file="EP0214546A2_D0019.tif" /></tables>

Remarks:

<ul id="ul0014" list-style="none"><li>1. None of the chemical mixtures or individual chemicals used in the tests of this example showed phytotoxicity.</li><li>2nd Compounds Nos. 1, 2, 3, 4 and 5 of general formula (I) used in the present invention are the same as those used in Example 8.</li><li>3rd Compounds (carbamates of the formula (III)) from the above-mentioned group (4) of the insecticides which are used in the present invention:<ul id="ul0015" list-style="none"><li>[A]: ethiofencarb,</li><li>[B]: Pirimicarb.</li></ul></li></ul>

Example 10

Wettable powder

20 Parts of the active substance of the formula (I), 20 parts of propoxy, 55 parts of a 1: 5 mixture of powdery diatomaceous earth and powdered clay, 2 parts of sodium alkylbenzosulfonate and 3 parts of sodium alkylnaphthalenesulfonate-formaldehyde condensate are pulverized and mixed together, whereby a wettable powder is obtained.

Example 11

Dusts

A part of the active substance of the formula (I), a part of BPMC and 98 parts of powdery clay are pulverized and mixed together to obtain a dusting agent.

Example 12

granules

A rotary mixer is charged with 96 parts of clay mineral particles with a particle size distribution between 0.2 and 2 mm, and while rotating 2 parts of the active substance of the formula (I) and 2 parts of carbofuran are sprayed onto the particles in order to uniformly wet. The particles were dried to form granules.

D) Biological examples of new active substance combinations of (1) a nitromethylene derivative of the formula (I) and an organophosphate ester of the formula (IV) from group (5):

Example 13

Test against Naphalocrocis

Preparation of a test chemical:

Solvent: 3 parts by weight of xylene Emulsifier: 1 part by weight of polyoxyethylene alkylphenyl ether

To prepare a formulation of the active compounds, 1 part by weight of the active compounds was mixed with the above-mentioned amount of solvent containing the above-mentioned amount of emulsifier, and the mixture was diluted with water to a predetermined concentration.

Test procedure

Three rice seedlings 15 cm high were each planted in 9 cm diameter vinyl resin pots. Ten days after the transplantation, an aqueous dilution of the active compounds with a predetermined concentration, which was prepared as stated above, in an amount of 20 ml per pot was sprayed onto the plants using a spray gun. After the sprayed-on substance was dried in air, a plastic net cylinder 9 cm in diameter and 25 cm in height was placed over each pot, and 10 larvae of rice leaf curlers (Onaphalocrocis medinalis) in the fourth stage of development were exposed in each pot. The pots were placed in a constant temperature room. Two days later, the number of dead insects was counted and the kill rate was then calculated. The above test was carried out with two parallel tests.

The results are shown in Table 8.<tables id="tabl0011" num="0011"><img file="EP0214546A2_D0020.tif" /></tables><tables id="tabl0012" num="0012"><img file="EP0214546A2_D0021.tif" /></tables>

Annotation:

<ul id="ul0016" list-style="none"><li>1. None of the chemical mixtures or individual chemicals used in the tests of this example showed phytotoxicity.</li><li>2nd Compounds of general formula (I) used in the present invention:<ul id="ul0017" list-style="none"><li>Compound No. 1: 1- (2-methyl-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine,</li><li>Compound No. 2: 1- (2-methoxy-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine,</li><li>Compound No. 3: 1- (2-bromo-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine,</li><li>Compound No. 4: 1- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine,</li><li>Compound No. 5: 1- (2-fluoro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine.</li></ul></li><li>3rd Compounds (organophosphate esters of the formula (IV)) from the above-mentioned group (5) of the insecticides which are used in the present invention:<ul id="ul0018" list-style="none"><li>[A]: isoxathine,</li><li>[B]: pyridaphenthion,</li><li>[C]: tetrachlorvinphos,</li><li>[D]: Sulprofos.</li></ul></li></ul>

Example 14

Test against Plutella

Test procedure

An aqueous dilution of the active compounds at a predetermined concentration, prepared as in Example 13, was applied to cabbage seedlings about 15 cm high before heading, which had been planted in 9 cm diameter pots, in an amount of 20 ml per Pot sprayed on with a spray gun. After the sprayed-on substance was dried in air, ten larvae of organophosphate-resistant cabbage moths (Plutella maculipennis) in the fourth stage of development were exposed in each pot. The pots were placed in a constant temperature room. Two days later, the number of dead insects was counted and the degree of kill was calculated. The above test was carried out with two parallel tests.

The results are shown in Table 9.<tables id="tabl0013" num="0013"><img file="EP0214546A2_D0022.tif" /></tables>

Notes on Table 9:

<ul id="ul0019" list-style="none"><li>1. None of the chemical mixtures or individual chemicals used in the tests of Example 14 showed phytotoxicity.</li><li>2nd Compounds Nos. 1, 2, 3, 4 and 5 of the general formula (I) used in the present invention are the same as those used in Example 13.</li><li>3rd Compounds (organophosphate esters of the formula (IV)) from the above-mentioned group (5) of insecticides which are used in the present invention:<ul id="ul0020" list-style="none"><li>[A]: Prothiofos,</li><li>[B]: Pirimiphos-methyl,</li><li>[C]: chlorpyrifos,</li><li>[D]: Acephate.</li></ul></li></ul>

Example 15

Test against Myzus

Test procedure

Green peach aphids (Myzus persicae) resistant to organophosphates and carbamates were exposed to eggplant seedlings about 20 cm high, grown in 9 cm diameter pots, about 100 aphids per seedling. One day after the exposure, an aqueous dilution of the active compounds having a predetermined concentration, prepared as in Example 13, in an amount of 20 ml per pot was sprayed on the plants by means of a spray gun. After spraying, the pots were left in a greenhouse at 28 ° C. Three days after spraying, the number of dead insects was counted and the degree of kill was calculated.

The results are shown in Table 10.<tables id="tabl0014" num="0014"><img file="EP0214546A2_D0023.tif" /></tables>

Notes to Table 10:

<ul id="ul0021" list-style="none"><li>1. None of the chemical mixtures or individual chemicals used in the tests of Example 15 showed phytoxicity.</li><li>2nd Compounds Nos. 1, 2, 3, 4 and 5 of the general formula (I) used in the present invention are the same as those used in Example 13.</li><li>3rd Compounds (carbamates of the formula (IV)) from the above-mentioned group (5) of the insecticides which are used in the present invention:<ul id="ul0022" list-style="none"><li>[A]: Disulfoton,</li><li>[B]: Vamidothion.</li></ul></li></ul>

Example 16

Wettable powder

20 Parts of the active substance of the formula (I), 20 parts of Prothiofos, 55 parts of a 1: 5 mixture of powdery diatomaceous earth and powdered clay, 2 parts of alkylbenzenesulfonate and 3 parts of sodium alkylnaphthalenesulfonate-formaldehyde condensate are pulverized and mixed together, giving a wettable powder is obtained.

Example 17

Dusts

A part of the active substance of formula (I), two parts of pyridaphenthione and 97 parts of powdered clay are pulverized and mixed together to obtain a dusting agent.

Example 18

granules

A rotary mixer is charged with 95 parts of clay mineral particles with a particle size distribution between 0.2 and 2 mm, and while rotating 2 parts of the active substance of the formula (I) and 3 parts of disulphon are sprayed onto the particles in order to uniformly wet. The particles were dried to form granules.