Nitromethylene-tetrahydropyrimidine derivatives, process for their preparation and insecticidal, miticidal, tickicidal, and nematicidal means

The present invention relates to new nitromethylene tetrahydropyrimidine derivatives, processes for their preparation and insecticidal, miticidal, tickicidal and nematicidal compositions which contain such derivatives as active compounds.

In particular, the present invention relates to novel nitromethylene tetrahydropyrimidine derivatives of the general formula (I) below<chemistry id="chem0001" num="0001"><img file="EP0136636A2_D0001.tif" /></chemistry>in the<ul id="ul0001" list-style="none"><li>X represents halogen.</li></ul>

The nitromethylene tetrahydropyrimidine derivatives of formula (I) according to the present invention can be prepared by the following general method i), to which the present invention also extends.

A process for the preparation of the nitromethylene tetrahydropyrimidine derivatives of the general formula (I) comprises the reaction of a compound of the general formula (II)<chemistry id="chem0002" num="0002"><img file="EP0136636A2_D0002.tif" /></chemistry>in which X has the meaning given above, with 1-nitro-2,2-bis (methylthio) ethylene of the formula<chemistry id="chem0003" num="0003"><img file="EP0136636A2_D0003.tif" /></chemistry>

The present invention further relates to insecticidal, miticidal, tickicidal and nematicidal compositions which contain nitromethylene-tetrahydropyrimidine derivatives of the formula (I) as active ingredients.

DE-OS 25 14 402 known before the filing date of the present application states that 2-nitromethylene-imidazoline derivatives and 2-nitromethylene-hexahydropyrimidine derivatives of the general formula below<chemistry id="chem0004" num="0004"><img file="EP0136636A2_D0004.tif" /></chemistry>show insecticidal activity. The general formula above includes cases where n = 2, R₁= Phenyl (CI-C2) alkyl group and R₂ = R₃ = Hydrogen, and the description of DE-OS 25 14 402 describes a compound of the following formula:<chemistry id="chem0005" num="0005"><img file="EP0136636A2_D0005.tif" /></chemistry>

However, in the above formula, R₁ not a benzyl group with a substituent. It has now been found that the new nitromethylene tetrahydropyrimidine compounds of the general formula (I) have an excellent control action against harmful insects, mites, ticks and nematodes.

Those designated by the general formula (I) above. Nitromethylene tetrahydropyrimidine derivatives of the present invention are neither covered by the general formula described in the above-cited DE-OS, nor are they described anywhere else in the previously published technical literature.

The compounds of the present invention are characterized by the fact that their chemical structure is 2-nitromethylene tetrahydropyrimidine as the basic skeleton and a halogen-substituted benzyl group on the nitrogen atom is substituted in the 1-position of the tetrahydropyrimidine ring. The phenyl nucleus is preferably substituted in the 3- or 4-position by halogen.

It has also been found that the compounds of the present invention have a particularly outstanding pest control activity, that of the compounds of the formula (A-1) described in the above-mentioned DE-OS 25 14 402 and the compounds of the present invention most similar, far surpassing, and that the compounds of the present invention show a pronounced control action against insect pests, which have developed the same resistance to insecticides of the organic phosphate type and of the carbamate type due to long-term use, in particular to sucking insects such as cockroaches, lantern carriers and cicadas.

Furthermore, it has been found that the compounds of the present invention exhibit particularly superior control effects when applied to a water surface, and in relation to residual effects in water, those compounds which are very similar to the compounds of the present invention, for example the compounds of the formula given above (A-1), are far superior.

An object of the present invention is to make the new nitromethylene tetrahydropyrimidine derivatives of the general formula (I), a process for their preparation and their use as insecticidal, miticidal, tickicidal and nematicidal agents available.

This, as well as other objects and advantages of the present invention, will become more apparent from the following description.

The active compounds according to the present invention show a precise control action against harmful insects, mites or ticks and nematodes without exhibiting any phytotoxicity to crop plants. Furthermore, the compounds of the present invention can be used to control and eradicate a wide range of pests, including sucking insects, biting insects and other plant parasites, pests of stored grain and pests which are hazardous to health. Specific examples of these pests are listed below:<ul id="ul0002" list-style="none"><li>Examples of insects include</li></ul>

Insects of the order Coleoptera

Callosobruchus chinensis, Sitophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomala rufocuprea, Leptinotarsa ​​decemlineata, Diabrotica spp., Monochamus alternatus, Lissorhoptus oryusophneus and Lyctus brunus.

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 and Phyll.

Insects of the order Hemiptera

Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicae, Aphis pomi, Aphis gossypii, Rhopalosiphum pseudobrassicas, Stephanitis nashi, Nazara spp., Cimex lectularius, Trialeuryls vaporariorum .. and Ps

Insects of the order Orthoptera

Blatella germanica, Periplaneta americana, Gryllotalpa africana and Locusta migratoria migratoriodes.

Insects of the order Isoptera

Deucotermes speratus and Coptotermes formosanus.

Insects of the order Diptera

Musca domestica, Aedes aegypti, Hylemia platura, Culex pipiens, Anopheles sinensis and Culex tritaeniorhynchus.

Mites

Tetranychus telarius, Panonychus citri, Aculus pelekassi and Torronomus spp ..

Nematodes

Meloidogyne incognita, Bursaphelenchus lignicolus Mamiya et Kiyohara, Aphelenchoides besseyi, Heterodera glycines and Pratylenchus spp ..

In the field of veterinary medicine, the new compounds according to the present invention are effective against various harmful animal parasites (endo and ectoparasites) such as ticks, insects and worms. Examples of such animal parasites are given below.

Ticks

Oranithodoros spp., Ixodes spp. and Boophilus spp ..

insects

Gastrophilus spp., Stomoxys spp., Trichodectes spp. Rhodnius spp. and Ctenocephalidex canis

Substances that have pesticidal activity against all of these pests are sometimes referred to simply as "insecticides" in the present application.

The nitromethylene tetrahydropyrimidine derivatives of the general formula (I) according to the present invention can be prepared in a simple manner, for example using the following process i).

Procedure i)

<chemistry id="chem0006" num="0006"><img file="EP0136636A2_D0006.tif" /></chemistry>

(In the formulas, X has the meaning given above).

In the above reaction scheme, X denotes a halogen atom, especially a fluorine, chlorine, bromine or iodine atom.

In the process for producing the compound of the general formula (I) represented by the above reaction scheme, specific examples of the starting compound of the general formula (II) include N- (3-chlorobenzyl) trimethylene diamine, N- (4-chlorobenzyl) tri - methylenediamine, N- (4-bromobenzyl) trimethylene diamine and N- (4-fluorobenzyl) trimethylene diamine.

The above method is described in detail by the following typical example.<chemistry id="chem0007" num="0007"><img file="EP0136636A2_D0007.tif" /></chemistry>

The above process for the preparation of the compounds according to the present invention can expediently be carried out in a solvent or diluent. Any inert solvent or diluent can be used for this purpose.

Examples of such solvents or diluents include water; aliphatic, alicyclic and aromatic hydrocarbons (which may or may not be chlorinated) such as hexane, cyclohexane, petrolet , ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, trichloroethylene and chlorobenzene, ethers such as diethyl ether, methyl ethyl ether, di- isopropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, Nitriles such as acetonitrile, propionitrile and acrylonitrile, alcohols such as methanol, ethanol, isopropanol, butanol and ethylene glycol, esters such as ethyl acetate and amyl acetate, acid amides such as dimethylformamide and dimethylacetamide, sulfones and sulfoxides such as dimethyl sulfoxide and sulfolane and bases such as pyridine.

The above process can be carried out over a wide temperature range. In general, it can be carried out at a temperature between -20 ° C and the boiling point of the mixture, advantageously at a temperature between about 0 ° C and about 100 ° C. The reaction is expediently carried out under normal atmospheric pressure, but it is also possible to work at elevated or reduced pressure.

The compounds of the general formula (I) according to the present invention can also be prepared with the aid of another process ii) which is shown schematically below.

Procedure ii)

<chemistry id="chem0008" num="0008"><img file="EP0136636A2_D0008.tif" /></chemistry>

(In the formulas, X has the meaning given above and Hal denotes a halogen atom).

In the above reaction scheme, X denotes a halogen atom, especially a fluorine, chlorine, bromine or iodine atom.

In the process for producing the compound of the general formula (I) represented by the above reaction scheme, specific examples of the starting compound of the general formula (III) include 3-chlorobenzyl chloride, 4-chlorobenzyl chloride, 4-bromobenzyl chloride and 4-fluorobenzyl chloride. The corresponding bromides should also be mentioned.

The above method ii) is described in detail by the following reference example.<chemistry id="chem0009" num="0009"><img file="EP0136636A2_D0009.tif" /></chemistry>

The above process can be carried out using the same solvents or diluents as those exemplified above for process i).

The above reaction can be carried out in the presence of an acid-binding agent. Examples of the acid-binding agent may include the hydroxides, carbonates, hydrogen carbonates and alcoholates of alkali metals, as well as tertiary amines such as triethylamine, diethylaniline and pyridine, all of which are generally used.

As in the case of process i), process ii) can be carried out within a wide range of temperature and expediently under normal atmospheric pressure. It is also possible to work at elevated or reduced pressure.

As insecticidal, miticidal, tickicidal and nematicidal compositions, the compounds of the present invention can be used immediately after dilution with water or in the form of various formulations, such as those obtained using agriculturally acceptable auxiliaries, by processes which are used in the practical production of Agrochemicals are widely used. In practice, these various formulations are used either immediately or after dilution with water to the desired concentration.

Examples of the agriculturally acceptable auxiliaries mentioned here are diluents (solvents, extenders, carriers), surface-active agents (solubilizers, emulsifiers, dispersants, wetting agents), stabilizers, adhesives, aerosol propellants and synergistic agents.

Examples of the solvents are water and organic solvents, for example hydrocarbons [for example n-hexane, petroleum ether, petroleum fractions (for example paraffin waxes, kerosene, light oils, middle oils and heavy oils), benzene, toluene and xylenes 7, halogenated hydrocarbons (for example methylene chloride, carbon tetrachloride, Ethylene chloride, ethylene dibromide, chlorobenzene and chloroform), alcohols (e.g. methanol, ethanol, propanol and ethylene glycol), ethers (e.g. Diethyl ether, ethylene oxide and dioxane), alcohol ethers (e.g. ethylene glycol monomethyl ether), ketones (e.g. acetone and isophorone), esters (e.g. ethyl acetate and amyl acetate), amides (e.g. dimethylformamide and dimethylacetamide) and sulfoxides (e.g. dimethyl sulfoxide).

Examples of the extenders or carriers include inorganic powders, for example hydrated lime, magnesium lime, gypsum, calcium carbonate, silicon dioxide, pearlite, pumice stone, calcite, diatomaceous earth, amorphous silicon dioxide, aluminum oxide, zeolites and clay minerals (for example pyrophyllite, talc, montmorillonite, beidellite, kaemite, vermiculite and mica), vegetable powders such as cereal powder, types of starch, process_- Starch types, sugar, glucose and crushed stems of plants, as well as powder from synthetic resins such as phenol resins, urea resins and vinyl chloride resins.

Examples of the surfactants include anionic surfactants such as alkyl sulfonic acid esters (e.g. sodium lauryl sulfate), aryl sulfonic acids (e.g. alkyl aryl sulfonic acid salts and sodium alkyl naphthalene sulfonates), succinic acid salts and salts of sulfuric acid esters of polyethylene glycol alkyl aryl ethers, cationic surfactants such as alkyl amines Laurylamine, stearyltrimethylammonium chloride and alkyldimethylbenzylammoniumchloride) and polyoxyethylene alkylamines, non-ionic surface-active agents such as polyoxyethylene glycol ethers (e.g. polyoxyethylene alkylaryl ethers and their condensation products), polyoxyethylene glycol esters (e.g. polyoxyethylene fatty acid esters) and esters of polyhydric alcohols (e.g. polyoxyethylene urethane surfaces) and amine polyoxyethylene surfactants.

Examples of other auxiliaries include stabilizers, adhesives (e.g. agricultural soaps, casein lime, sodium alginate, polyvinyl alcohol, vinyl acetate-type adhesives and acrylic adhesives), aerosol propellants (e.g. trichlorofluoromethane, dichlorofluoromethane, 1,2,2-trichloro-1 , 1,2-trifluoroethane, chlorobenzene, liquefied natural gas (LNG) and lower ethers), combustion control agents for fumigants (e.g. Nitrites, zinc powder and dicyandiamide), oxygen-releasing agents (e.g. chlorates), action-extending agents, dispersion stabilizers (e.g. casein, tragacanth, carboxymethyl cellulose (CMC) and polyvinyl alcohol (PVA)) and synergistic agents.

The compounds of the present invention can be formulated into various preparations using the methods commonly used in the agrochemical field. Examples of such use forms are emulsifiable concentrates, oil preparations, wettable powders, soluble powders, suspensions, dusts, granules, powdery preparations, fumigants, tablets, aerosols, pastes and capsules.

The insecticidal, miticidal or nematicidal agents according to the present invention can contain about 0.1 to about 95% by weight, preferably about 0.5 to 90% by weight, of the above-mentioned active ingredient.

For practical use, the suitable amount of the active compound in the aforementioned various formulations and ready-to-use preparations is generally about 0.0001 to about 20% by weight, preferably about 0.005 to about 10 Ge_w.-_%.

The content of the active ingredient can be suitably varied depending on the type of formulation, the method, the purpose, the time and the place of its use and the state of the occurrence of the harmful insects, mites or ticks and nematodes to be controlled.

If necessary, the compounds according to the present invention can also be used in combination with other agrochemicals, for example with other insecticides, fungicides, other miticides, other nematicides, anti-virus agents, herbicides, plant growth regulators and attractants / for example Organophosphate compounds, carbamate compounds, dithio (or thiol) carbamate compounds, organochlorine compounds, dinitro compounds, organic sulfur or organometallic compounds, antibiotics, substituted diphenyl ether compounds, urea compounds and triazine compounds_7 and / or fertilizers .

Various agents and ready-to-use preparations containing the active substance referred to above can be used by means of various methods which are generally used for applying agrochemicals, for example by spraying (spraying liquids, atomizing, atomizing, dusting, scattering granules, water) -Surface treatment, casting etc.), smoking, soil treatment (mixing with the floor, spraying, steaming, Casting etc.), surface application (e.g. coating, application in the form of tapes, powder coating, covering etc.), immersion and bait. They can also be applied using the so-called ultra-low-volume spraying process. According to this method, the active ingredient can even be incorporated in a concentration of 100%.

The application rate per unit area is, for example, about 0.03 to about 10 kg / ha, preferably about 0.3 to about 6 kg / ha. In special cases, the application rates can or should even be outside the specified range.

According to the present invention, an insecticidal, miticidal, tickicidal or nematicidal agent can be made available which contains the compound of the general formula (I) as well as a diluent (a solvent and / or an extender and / or a carrier) and / or contains a surfactant and, if necessary, a stabilizer, an adhesive, a synergistic agent, etc.

The present invention further provides a method for controlling insects, mites or ticks and nematodes, which consists in that a compound of the general formula (I) alone or in the form of a mixture with a diluent (a solvent and / or an extender and / or a carrier) and / or a surfactant and, if necessary, a stabilizer, an adhesive, a synergistic agent, etc. is applied to harmful insects, mites or ticks and nematodes and / or their habitat or the place where they occur.

The present invention is illustrated in detail by the following examples, but is not limited to these specific examples alone.

example 1

N- (4-Chlorobenzyl) trimethylene diamine (8.45 g) and 1-nitro-2,2-bis (methylthio) ethylene (6.60 g) were refluxed in 100 ml of ethanol for 16 hours. The reaction mixture was cooled to room temperature, and the precipitated crystals were collected by filtration and washed with a small amount of ethanol, whereby 1- (4-chlorobenzyl) -2- (nitromethylene) tetrahydropyrimidine (9.8 g) of the formula below was obtained . Melting point: 172-174 ° C.<chemistry id="chem0010" num="0010"><img file="EP0136636A2_D0010.tif" /></chemistry>

Table 1 below lists the compounds of the present invention which were synthesized from the corresponding starting materials in the same manner as in Example 1.<tables id="tabl0001" num="0001"><img file="EP0136636A2_D0011.tif" /></tables>

Example 2 (wettable powder)

15 Parts of Compound No. 1 of the invention, 80 parts of a mixture (1: 5) of powdered diatomaceous earth and clay powder, 2 parts of sodium alkylbenzenesulfonate and 3 parts of sodium alkylnaphthalenesulfonate / formaldehyde condensate are pulverized and mixed to form a wettable powder. This is diluted with water and sprayed onto harmful insects, mites or nematodes and / or their habitat or the place where they occur.

Example 3 (Emulsifiable concentrate)

30th Parts of Compound No. 3 of the invention, 55 parts of xylene, 8 parts of polyoxyethylene alkylphenyl ether and 7 parts of calcium alkylbenzenesulfonate are mixed together with stirring, thereby producing an emulsifiable concentrate. This is diluted with water and sprayed onto harmful insects, mites or nematodes and / or their habitat or the place where they occur.

Example 4 (dusts)

2nd Parts of Compound No. 4 of the invention and 98 parts of clay powder are pulverized and mixed, thereby producing a dusting agent. This is spread over harmful insects, mites or nematodes and / or their habitat or the place where they occur.

Example 5 (granules)

Water (25 parts) is added to a mixture of 10 parts of Compound No. 2 of the invention, 30 parts of bentonite (montmorillonite), 58 parts of talc and 2 parts of lignin sulfonate, and the mixture is kneaded well. The mixture is processed by an extruder granulator into granules with a grain size of 0.43 to 2.0 mm (10 to 40 mesh), which is then dried at 40 ° C to 50 ° C, whereby a granulate is formed. The granules are spread over harmful insects, mites or nematodes and / or their habitat or the place where they occur.

Example 6 (granules)

A rotary mixer is charged with 95 parts of clay mineral particles having a particle size distribution between 0.2 and 2 mm, and while rotating the mixer, 5 parts by weight of compound No. 3 of the invention are applied to the clay mineral particles for uniform wetting thereof sprayed on. The moist mixture is dried at 40 ° C to 50 ° C, whereby a granulate is formed. The granules are spread over harmful insects, mites or nematodes and / or their habitat or the place where they occur.

Example 7 (oil preparation)

Compound No. 1 of the invention (0.5 part) and 99.5 parts of kerosene are mixed together with stirring, thereby forming an oil preparation. This is sprayed onto harmful insects, mites or nematodes and / or their habitat or the place where they occur.

Example 8 (biological test)

Test with organophosphorus-resistant Nephotettix cincticeps:

Preparation of a test preparation:

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

To prepare a suitable test preparation, 1 part by weight of the active compound 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:

Rice plants of about 10 cm in height, each planted in 12 cm diameter pots, were sprayed with 10 ml of the water-diluted solutions having a predetermined active ingredient concentration and prepared as indicated above. The sprayed chemical was allowed to dry and a 7 cm diameter and 14 cm high wire basket was placed over the rice plants and exposed to 30 adult female specimens of Nephotettix cincticeps which were resistant to organophosphorus insecticides. The pots were each kept in a constant temperature room, and 24 hours later, the number of dead insects was determined and the extermination ratio was calculated.

The results are shown in Table 2.<tables id="tabl0002" num="0002"><img file="EP0136636A2_D0012.tif" /></tables>

Example 9 (biological test)

Test with organophosphorus-resistant Myzodes persicae (green peach aphids):

Test procedure:

Grown green peach aphids were placed on eggplant seedlings (black elongated eggplants) about 20 cm high, grown in unglazed 15 cm diameter pots (about 200 aphids per seedling). One day after exposure, an aqueous dilution of each of the active compounds prepared in Example 8 at a predetermined concentration was sprayed onto the plants in a sufficient amount using a spray gun. After spraying, the pots were left in a greenhouse at 28 ° C. The destruction ratio was calculated 24 hours after spraying. The test was carried out as a duplicate determination for each compound.

The results are shown in Table 3.<tables id="tabl0003" num="0003"><img file="EP0136636A2_D0013.tif" /></tables>