MXPA98006888A - Derivatives of tetrahidropirimidina - Google Patents

Abstract

The present invention relates to new tetrahydropyrimidine derivatives of the formula (I) wherein A means a group (Ia) - (CH2) m-COXR1 or (Ib) Het means a heterocyclic group with 5 or 6 members, containing 1, 2,3ó4 atoms of estrogen and / or 1ó2 atoms of oxygen or sulfur as ring heteroatoms, the number of the ring heteroatoms being 1,2,34 - and which is, if necessary, replaced by halogen, by cyano, by nitro, by alkyl, haloalkyl, alkenyl, haloalkenyl, alkyl, alkoxy, haloalkoxy, alkenyloxy, haloalkenyloxy, alkylthio, haloalkylthio, alkenylthio, haloalkenylthio, alkynylthio, alkynylsulfinyl, haloalkylsulphonium, alkylsulfonyl, by haloalkylsulfonyl, by ammonium, by alkylamino, by dialkylamino, by aryl, by aryloxy, by arylthio, by arylamino, by aralkyl, by formylamino, by alkylcarbonylamino , by formyl, by carbamoyl, by alkylcarbonyl and / or by alkoxycarbonyl. R 1 is hydrogen, alkyl, halogenoalkyl, alkenyl, haloalkenyl-substituted aralkyl or optionally substituted heteroarylalkyl with 5-6-membered or substituted heterocyclylalkyl with 5-6-membered, optionally substituted, R 2 means optionally substituted alkyl or aralkyl, X means oxygen or the grouping -NH and -N-alkyl, m means integers from 1 to 20 and n means integers from 0 to 2, excluding the compounds of the formula (I), in which at the same time A means the grouping (Ia), Het means (see formula) R 1 means hydrogen or ethyl, X means oxygen, m means 1 or 2 and n means 0. The invention also relates to processes for obtaining it and its use as a pesticide.

Description

DERIVATIVES OF TETRAHIDROPIRIMIDINAS.

Field of Invention The present invention relates to new tetrahydropyrimidine derivatives, to processes for their preparation and to their use for the control of animal pests.

Background of the Invention It is already known that certain bicyclic derivatives of pyrimidine, such as, especially, 6,7-dihydro-8-nitro- (5H) -1- (2-chloropyridin-5-ylmethyl or 2-chloro) - 1, 3-t-thiazol-5-ylmethyl) -imidazolamdino- [2, 3-f] -pyrimidine 6-subsitutes have insecticidal properties (see, for example, EP-A-0 247 477). However, the activity and spectrum of activity of these compounds are not always satisfactory, especially in the case of application quantities and low concentrations.

REF .: 28112 Detailed Description of the Invention New tetrahydropyrimidine derivatives of the formula (I) have been found, where A means a grouping (the) - (CH2) m-COXR1 (Ib) R2 -CH-COXR1 ,. Het means a heterocyclic group with 5 or 6 members, containing 1, 2, 3 or 4 nitrogen atoms and / or 1 or 2 oxygen atoms or sulfur atoms as ring heteroatoms - the number of ring heteroatoms being 1, 2, 3 or 4 - and which is substituted, if appropriate, by halogen, by cyano, by nitro, by alkyl, by haloalkyl, by alkenyl, by haloalkenyl, by alkyl, by alkoxy, by haloalkoxy, by alkenyloxy, by haloalkenyloxy, by alkynyloxy, by alkylthio, by haloalkylthio, by alkenylthio, by haloalkenyl thio, by alkynylthio, by alkynylsulfinyl, by haloalkylsulfonyl, by alkylsulfonyl, by haloalkylsulfonyl, by ammonium, by alkylamino, by dialkylamino, by aryl, by aryloxy , by arylthio, by arylamino, by aralkyl, by formylamino, by alkylcarbonylamino, by formyl, by carbamoyl, by alkylcarbonyl and / or by alkoxycarbonyl, R 1 is hydrogen, alkyl, halogenoalkyl, alkenyl, haloalkenyl, substituted aralkyl or optionally means heterocyclylalkyl with 5 or 6 members, optionally substituted, R 'means substituted aralkyl alkyl, if appropriate, X means oxygen or the grouping -NH- and -N- alkyl-, means integers from 1 to 20 and n means integers from 0 to 2, excluding the compounds of the formula (I), in which at the same time A means grouping (the), Het mean RJ means hydrogen or ethyl, X means oxygen, m means 1 or 2 and n means 0 It has also been found that the tetrahydropyrimidine derivatives of the formula are obtained (I), if a) nitromethylene derivatives of the formula (II) are reacted in which Het and n have the meaning indicated above, with amines of the formula (Illa) or (Illb) H2N- (CH2) -CO-X-R1 (Illa) R 'I H2N- -CH- -CO-X-R (Illb) in which R1, R2, X and m have the meaning indicated above, If appropriate, in the form of their hydrohalogenides, in the presence of at least two times a molar amount of formaldehyde, if appropriate in the presence of an acid catalyst, if appropriate, in the presence of a diluent and, if appropriate, in the presence of a base; b) N-tyrpyrimidine derivatives of the formula (IV) are reacted in which A and n have the meaning indicated above, with compounds of the formula (V) Het-CH2-L (V) in which Het has the meaning indicated above and L means an anionic dissociable group, in the presence of a base and, if necessary, in the presence of a diluent.

Finally, it has been found that the new tet rahydropyrimidine derivatives of the formula (I) have strongly marked biological properties and that, above all, they are suitable for combating animal pests, especially against insects, arachnids and nematodes, which occur in agriculture, in forestry, in the protection of stored products and materials as well as in the hygiene sector.

The terahydropyrimidine derivatives according to the invention are generally defined by the formula (I).

The substituents or the preferred ranges of the residues indicated in the above formulas and which will be cited below, are explained as follows: Het preferably means a heterocyclic group with 5 or 6 members of the group consisting of furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3- or 1,2,4-triazolyl, oxazolyl, isoxazolyl, 1,2,4 - or 1, 3, 4-oxadiazolyl, thiazolyl, isothiazolyl, 1,2,3-, 1,2,4-, 1,2,5- or 1,3,4-thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl and pyrazinyl, which is optionally substituted one or more times, in the same or different ways by fluorine, chlorine, bromine, iodine, cyano, nitro, alkyl with 1 to 4 carbon atoms, (which is optionally substituted by fluorine and / or by chlorine), by alkenyl with 2 to 4 carbon atoms (which is optionally substituted by fluorine and / or by chlorine), by alkynyl with 2 to 4 carbon atoms , by alkoxy with 1 to 4 carbon atoms (which is optionally substituted by fluorine and / or by chlorine), by alkenyloxy with 3 or 4 carbon atoms (which is optionally substituted by fluorine and / or chlorine), by alkynyloxy with 3 to 4 carbon atoms, by alkylthio with 1 to 4 carbon atoms (which is optionally substituted by fluorine and / or by chlorine), by alkenylthio with 3 to 4 carbon atoms (which it is optionally substituted by fluorine and / or by chlorine), by alkylthio having 3 to 4 carbon atoms, by alkylsulfinyl having 1 to 4 carbon atoms (which is optionally substituted by fluorine and / or by chlorine), C 1 -C 4 alkylsulfonyl (which is optionally substituted by fluorine and / or chlorine), by amino, by alkylamino, with 1 to 4 carbon atoms, by di- (C 1 -C 4) alkyl ) -amino, by phenyl, by phenoxy, by phenylthio, by phenylamino, by benzyl, by formylamino, by alkyl with 1 to 4 carbon atoms, by carbonylamino, by formyl, by carbamoyl, by alkylcarbonyl with 1 to 4 atoms of carbon and / or by alkoxycarbonyl with 1 to 4 carbon atoms.

Preferably hydrogen, alkyl with 1 to 12 carbon atoms, halogenalkyl with 1 to 6 carbon atoms, alkenyl with 2 to 6 carbon atoms, halogenalkenyl with 2 to 6 carbon atoms, means phenyl-alkyl with 1 to 4 carbon atoms substituted in -given from one to five times, in the same or in different ways, mention may be made as phenyl substituents: halogen, cyano, nitro, alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, halogen with 1 to 4 carbon atoms, haloalkoxy with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms, alkoxycarbonyl with 1 to 4 carbon atoms, amino, alkylamino with 1 to 4 carbon atoms or di (C1-C4 alkyl) amino; as it means terbicyclyl with 1 to 4 carbon atoms of 5 or 6 members, optionally substituted one to three times, in the same or in different ways, the heterocyclic group of the series consisting of furyl being chosen, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3- or 1,2,4-triazolyl, oxazolyl, isoxazolyl, 1,2,4- or 1,3,4-oxadiazolyl, thiazolyl, isotriazolyl, 1,2 , 3-, 1,2,4-, 1,2,5- or 1, 3,4-diazodiazolyl, pyridyl, pyridazinyl, pyrimidinyl and pyrazinyl, which is optionally • one to three times equal or in different forms by fluorine, by chlorine, by bromine, by iodine, by cyano, by nitro, by alkyl with 1 to 4 carbon atoms (which is optionally substituted by fluorine and / or by chlorine), by alkenyl with 2 to 4 carbon atoms (which is optionally substituted by fluorine and / or by chlorine), by alkynyl with 2 to 4 carbon atoms, by alkoxy with 1 to 4 carbon atoms, (which is substi possibly fluorinated and / or chlorinated), by alkenyloxy with 3 to 4 carbon atoms (which is optionally substituted by fluorine and / or by chlorine), by alkynyloxy with 3 to 4 carbon atoms, by alkylthio with 1 to 4 carbon atoms (which is substituted in fluorine and / or chlorine), alkenylthio with 3 to 4 carbon atoms (which is optionally substituted by fluorine and / or chlorine), alkynylthio with 3 to 4 carbon atoms, alkylsulfinyl with 1 to 3 carbon atoms, at 4 carbon atoms (which is optionally substituted by fluorine and / or by chlorine), by alkylsul fonyl having 1 to 4 carbon atoms (which is optionally substituted by fluorine and / or by chlorine), by amino , by alkylamino with 1 to 4 carbon atoms, by di- (alkyl with 1 to 4 carbon atoms-amino), by phenyl, by phenoxy, by phenylthio, by phenylamino, by benzyl, by formylamino, by alkyl with 1 to 4 carbon atoms, by carbonylamino, by formyl, by carbamoyl, by alkylcarbonyl with 1 to 4 carbon atoms and / or by alkoxy i-carbonyl with 1 to 4 carbon atoms.

Preferably, R2 means alkyl with 1 to 8 carbon atoms or benzyl optionally substituted Preferably, X means oxygen or the grouping -NH- and N (with 1 to 8 carbon atoms) alkyl-.

Preferably, m means integers from 1 to 12 Preferably, n means the numbers 0 and 1.

The compounds in which, simultaneously, are exempted A means grouping (the), Het mean R1 means hydrogen or ethyl, X means oxygen, m means 1 or 2 and n means 0 Particularly preferably, Het means a heterocyclic group of 5 or 6 members of the group consisting of pyrazolyl, 1, 2, 4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1, 2, 5-thiadiazolyl, pyridyl, pyrazinyl, and pyrimidinyl, are optionally substituted one to three times , in the same or in different forms by fluorine, chlorine, bromine, iodine, cyano, nitro, alkyl with 1 to 2 carbon atoms (which is optionally substituted by fluorine and / or chlorine) ), by alkoxy with 1 to 2 carbon atoms (which is optionally substituted by fluorine and / or by chlorine), by alkylthio having 1 to 2 carbon atoms (which is optionally substituted by fluorine and / or by chlorine) ), by alkylsul fonyl having 1 to 2 carbon atoms (which is optionally substituted by fluorine and / or by chlorine).

Particularly preferably, hydrogen, alkyl with 1 to 8 carbon atoms, halogen with 1 to 4 carbon atoms, alkenyl with 2 to 4 carbon atoms, halogenalkenyl with 2 to 4 carbon atoms, means phenyl-alkyl with 1 or 2 carbon atoms optionally substituted one to three times, in the same or in different ways, mention may be made of phenyl substituents: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, methylthio, tri-fluoromethyl, t-trifluoromethoxy, and ilt io; as it means heterocyclic alkyl with 1 to 2 carbon atoms of 5 or 6 members, optionally substituted one to three times, in the same or in different ways, the heterocyclic group of the pyrazolyl-1 series being chosen. 2,4-triazolyl, oxazolyl isoxazolyl, thiazolyl, isothiazolyl, 1, 2, 5-thiadiazolyl, pyridyl, pyrazinyl and pyrimidinyl, which are optionally substituted by fluorine, by chlorine, by bromine, by cyano, by nitro, by alkyl with 1 to 2 carbon atoms (which is optionally substituted by fluorine and / or by chlorine), by alkoxy with 1 to 2 carbon atoms (which is optionally substituted by fluorine and / or by chlorine), by alkylthio with 1 to 2 carbon atoms (which is optionally substituted by fluorine and / or by chlorine, by alkylsulfonyl having 1 to 2 carbon atoms (which is optionally substituted by fluorine and / or by chlorine).

Especially preferably R 2 means alkyl having 1 to 4 carbon atoms or benzyl which is optionally substituted by halogen (chlorine, fluorine, bromine), alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 2 carbon atoms, alkylthio with 1 to 2 carbon atoms, halogenalkyl with 1 to 2 carbon atoms, halogenalkoxy with 1 to 2 carbon atoms, halogenalkyl with 1 to 2 carbon atoms, nitro, cyano.

Particularly preferably, X means oxygen or the grouping -NH-, - (CH3) - and -N (C2H5) -.

Particularly preferably, m means integers of 1 10. Particularly preferably, n means the numbers 0 and 1.

With the exception of the compounds, in which, simultaneously A means grouping (the), Het mean Cl 7 W N R1 means hydrogen or ethyl, X means oxygen, m s igni fique 1 2 and n means 0 Very particularly preferably, Het means pyridyl and thiazolyl substituted, if appropriate, one to two times, in the same or different ways by fluorine, chlorine or bromine. .

Very particularly preferably R 1 is hydrogen, alkyl having from 1 to 8 carbon atoms, optionally substituted benzyl, one to two times, in the same or different manner, and substituents such as fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, methylthio, trifluoromethyl, t-fluoro-toxy and trifluoromethylthio; as well as pyridylmethyl and thiazolylmethyl respectively substituted, if appropriate, one to two times, in the same or different ways by fluorine, chlorine or bromine.

Very particularly preferably, R means alkyl having 1 to 4 carbon atoms or benzyl.

Very particularly preferably, X means oxygen or the grouping -NH- Very particularly preferably, m means integers of 1 Very particularly preferably, n means the numbers 0 and 1.

The compounds are excluded, in which simultaneously A means grouping (the), Het mean Cl 7 \\ N R1 means hydrogen or ethyl, X means oxygen, m means 1 or 2 and n means 0 The definitions of the remains and the explanations indicated above or indicated in the preferred ranges are valid for the final products and correspondingly for the starting products and for the intermediate products. These definitions of the remains can be combined arbitrarily with each other, that is to say even between the corresponding preferential ranges.

According to the invention, the compounds of the formula (I) are preferred, in which a combination of the meanings indicated above as preferred are present. (preferably).

According to the invention, the compounds of the formula (I) are particularly preferred, in which a combination of the meanings given above is particularly preferably present.

According to the invention, the compounds of the formula (I) are very particularly preferred, in which a combination of the meanings indicated above is very particularly preferably present.

In the definitions of the radicals indicated above and indicated below, the hydrocarbon radicals, such as alkyl or alkynyl - even in combination with heteroatoms such as alkoxy or alkylthio - are respectively straight-chain or branched chain, insofar as possible .

Preferred compounds according to the invention are products of the formulas (le) to (If): in which Het1 means substituted pyridyl, if any, and has the meaning indicated in the definition of the invention. in which Het1 means substituted pyridyl, if appropriate A has the meaning indicated in the definition of the invention. in which Het means substituted thiazolyl, and A has the meaning indicated in the definition of the invention. in which Het means substituted thiazolyl, if appropriate A has the meaning indicated in the definition of the invention.

The preferred compounds according to the invention are also groups of products of the formulas (Ia-1), (Ib-1), (Ic-1) and (Id-1): in which A has the meanings mentioned above in a general manner, preferably, particularly preferably and very particularly preferably. in which A has the meanings indicated above in a general manner, preferably, particularly preferably and very especially preferably. in which A has the abovementioned meanings generally, preferably, particularly preferably and very particularly preferably.

(Id-l) where A have the meanings given above in a general manner, preferably, particularly preferably and very particularly preferably.

If, for carrying out the process (a) according to the invention, for example, 3- (2-chloropyridin-5-yl-methyl-yl) -2-nitromethylene-imidazolidine, glycine methyl ester hydrochloride and 2 moles are used of formaldehyde, the development of the reaction can be represented by means of the following formula scheme: Cl If, for carrying out process (b) according to the invention, for example, 6,7-dihydro-6-methoxycarbonylmethyl-8-nitro- (5H) -imidazolidino- [2, 3-f] -pyrimidine and -chloro-5-chloromethyl-pyridine, the development of the reaction can be represented by means of the following formula scheme: OCH3 The n-triethyl derivatives of the formula (II) to be used as starting materials in process (a) according to the invention are known (see, for example, EP-A 0 163 855, EP-A 0 192 060 , EP-A 0 247 477, EP-A 0 316 843 and EP-A 0 316 845) and / or can be prepared according to known methods (see published European applications, not examined).

If N-t-romethylene derivatives are used in the form of their hydrohalogenides, the hydrochlorides will preferably be used.

The amines of the formula (Illa) and (Illb) to be further employed as starting materials in the process (a) according to the invention are generally known compounds of organic chemistry and / or can be obtained in the usual manner.

The n-tropirimidine derivatives of the formula (IV) to be used as starting materials in the process (b) according to the invention are not yet known. These can be obtained by reacting neither tromethene derivatives of the formula (bundle). (see for example EP-A-0 247 477) in which n has the meaning indicated above, with amines of the formula (Ill-a) and (Ill-b) according to the procedure (a).

The compounds to be used as starting materials in process (b) according to the invention are generally defined by means of formula (V). Preferably L means chlorine, bromine, iodine, acetoxy. tosyl or mesyl. The compounds of the formula (V) are substances known in general from organic chemistry.

The process (a) according to the invention is preferably carried out using diluents. Suitable diluents are water and inert organic solvents for the reaction. These preferably include aliphatic and aromatic hydrocarbons, if appropriate halogenated such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzene, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride. , chlorobenzene and o-dichlorobenzene, ethers such as diethyl- or dibutyl ether, glycol dimethyl ether and diglycoldimethyl ether, tetrahydrofuran and dioxane, alcohols, such as methanol, ethanol, n-propanol, and isopropanol. Preferably, mixtures formed by alcohols and water will be used.

The process (a) according to the invention is carried out, if appropriate, in the presence of acid, non-oxidizing catalysts. Halogenated hydrocidal acids, such as hydrochloric acid and hydrobromic acid, phosphoric acid, lower carboxylic acids such as acetic acid and propionic acid, have been especially proven.

The reaction temperatures in process (a) according to the invention can vary within wide limits. In general, temperatures are between -20 ° and + 120 ° C, preferably at temperatures between 0 ° C and + 80 ° C.

The process (a) according to the invention is generally carried out under normal pressure. However, it is also possible to work under higher pressure or at a lower pressure.

For carrying out the process (a) according to the invention, 1 to 1.5 mol, preferably 1 to 1.2 mol of amino of the formula are used per 1 mol of the n-thromethylene derivative of the formula (II). (III) and from 2 to 4 moles, preferably from 2 to 3 moles of formaldehyde.

The amines of the formula (III) can be used, if appropriate, as aqueous solutions.

When gaseous amines of the formula are used (III) these compounds can be introduced by the mixture consisting of diluents, compounds of the formula (II) and formaldehyde. For the process according to the invention, formaldehyde in aqueous solution will be used. The reactions are generally carried out in a suitable diluent and the reaction mixture will be stirred for several hours at the necessary temperature in each case. The preparation is carried out in the process according to the invention, respectively, on customary methods.

Process (b) according to the invention is preferably carried out using diluents. Suitable diluents are virtually all inert organic solvents. These preferably include aliphatic and aromatic hydrocarbons, if appropriate halogenated, such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, tetrachloride carbon, chlorobenzene and o-dichlorobenzene, ethers such as diethyl and dibutyl ether, glycidime t-ether and diglycoldime t-ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl-ethyl-, methyl-isopropyl- or methyl-isobutyl-ketone . Esters such as methyl or ethyl acetate, nitriles such as for example acetonitrile or propionitrile, amides such as for example dimethylformamide, dimethylacetamide and N-me t -pyrrolidone as well as dimethylsulfoxide, te t -methylenesulfone or hexamethylenephosphorotriamide.

Suitable bases in processes (a) and (b) according to the invention are all acid acceptors which are usually usable in this type of reaction. Preference is given to hydrides of alkali metals and alkaline earth metals, such as lithium, sodium, potassium or calcium hydride, alkali metal or alkaline earth metal hydroxides, such as lithium, sodium, potassium or hydroxide hydroxide. calcium, carbonates or bicarbonates of alkali metals or alkaline earth metals, such as sodium or potassium carbonates or bicarbonates or calcium carbonate, alkali metal acetates such as sodium or potassium acetate, alkali metal alcoholates such as t ert . -but sodium or potassium iolate, in addition basic nitrogenous compounds, such as trimethylamine, triethylamine, t-ripropylamine, tributylamine, diisobutylamine, di-cyclohexylamine, ethyldiisopropylamine, ethyldicyclohexylamin, N, N-dimethyl-il-benzylamine, N, N-dimethyl-aniline , pyridine, 2-methyl, 3-methyl, 4-methyl, 2,4-dimethyl-, 2,6-dimethyl-, 2-ethyl-, 4-ethyl- and 5-et-il-2-methyl il-pyridine, 1,5-diazabicyclo [4, 3, 0] -non-5-ene (DBN), 1,8-diazabicyclo- [5, 4, 0] -undec-7-ene (DBU) or 1 , 4-diazabicyclo- [2, 2, 2] -octane (DABCO).

The reaction temperatures in process (b) according to the invention can vary within wide limits. In general, temperatures are between 0 ° C and 100 ° C, preferably at temperatures between 10 ° C and 80 ° C.

Process (b) according to the invention is generally carried out under normal pressure. However, it is also possible to work under higher pressure or at lower pressure.

For carrying out the process (b) according to the invention, the starting materials, which are necessary in each case, are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components, used in each case, in a greater excess. The reactions are generally carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the necessary temperature in each case. Working up is carried out by customary methods.

The active compounds according to the invention are suitable, with a good compatibility for plants and a toxicity suitable for mammals, for the control of animal pests, preferably against insects, arachnids and nematodes, which occur in agriculture, in forestry, for the protection of stored products and materials as well as in the area of hygiene. They are active against normally sensitive and resistant species as well as against all or some of the stages of development. The aforementioned pests include: From the order of the isopods for example, Oniscus asellus Armadillidium vulare and Porcellio scaber.

From the order of the diplópodos, for example, Blaniulus guttulatus.

From the order of the chilopoda, for example, Geophilus carpophagus and Scutigera spec ..

Of the order of the simfilos, for example ,. Scutigerella immaculata.

From the order of the tisane, for example, Lepisma saccharina.

From the order of springtails, for example, Onychiurus armatus.

From the order of the orthoptera, for example, Blatta orientalis, Periplaneta. American, Leucophaea maderae, Germanic Blattella; Acheta domesticus, Gryllotalpa spp., Locusta migratoria migra torioides, Melanoplus dif ferentialis and Schistocerca gregaria.

From the order of dermápteros, for example, Forfícula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp ..

From the order of the anophores, for example, Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., And Linognathus spp.

From the order of the malophagous, for example, Trichodectes spp. and Damalinea spp ..

From the order of the isanoptera, for example, Hercinothrips femoralis and Thrips tabaci.

From the order of the heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex Lectularius, Rhodnius prolixus and Triatoma spp.

From the order of Homoptera, for example, Aleurodes brasicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cruptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens; Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.

From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Li thocollet is whitederlla, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoe, Lymant ria spp Bucculatrix thurberiella, Phyllocnis tis citrella, Agrotis spp., Euxoa spp Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bi s selliella, Tinea pellionella, Hofmannophila pseudospre tella, Cacoecia podana, Capua reticule, Choris tonura fumiferana, Clysia ambiguella, Homona magnánima and Tortrix viridana.

From the order of Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleriae, Diabrotica spp., Psylliodes chysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Ot iorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus , Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandica. • From the order of Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogas ter, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomia spp., Cuterebra spp., Gastrophilus spp. ., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Typula palidosa.

From the order of the siphonoptera, for example, Xenopsylla cheopis, Ceratiphyllus spp ..

From the order of arachnids, for example, Scorpio maurus, Lactrodectus mactans.

From the order of mites, for example, Acarus siró, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

The phytoparasitic nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipene trans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp ..

The compounds according to the invention of the formula (I) are characterized in particular by high insecticidal activity.

They can be used with an especially good success in the fight against insects harmful to plants, such as, for example, against the larvae of the horseradish leaf beetle (Phaedon cochlaeriae), the caterpillars of the cabbage moth (Plutella maculipennis), the green rice cicada (Nephotettix cinctriceps), the caterpillars of the nocturnal moth. (Spodoptera frugiperda) or to combat the lice of the peach leaf (Myzus persicae).

The active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, sprayable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with the active product, as well as microencapsulated in polymeric materials.

These formulations are prepared in known manner, for example by mixing the active compounds with extenders, i.e. with liquid solvents and / or solid excipients, optionally with the use of surfactants, ie emulsifiers and / or dispersants and / or foam generating means.

When water is used as an extender, organic solvents can be used, for example as auxiliary solvents. As liquid solvents are preferably: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, cloroe philenes or methylene chloride, aliphatic hydrocarbons such as ciciohexano or paraffins, for example petroleum fractions, alcohols such as butanol or glycol, as well as their ethers and esters, ketones, such as acetone, methylethylketone, methylisobutylketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethylsulfoxide as well as water.

As solid carriers there are suitable: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorilloni ta or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, of aluminum and silicates, as solid excipients for granulates are considered: for example broken and fractionated natural minerals such as calcite, marble, pumice, sepiolite, dolomite, as well as synthetic granules of inorganic and organic flours, as well as organic materials, such as sawdust, coconut husks, corn cobs and tobacco stems; as emulsifying and / or foam formers are: for example nonionic emulsifiers and anionic surfactants such as esters, polyoxyethylene fatty acid ethers, polyoxyethylene fatty alcohols, for example alkylaryl poligrl icoléteres, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as the products of albumin hydrolysis; Suitable dispersants are: for example, sulphite lignin bleach and methylcellulose.

In the formulations Tackifiers such as carboxymethylcellulose and natural and synthetic polymers powders, granules or latex form, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes, such as inorganic pigments, for example, iron oxide, titanium oxide, Prussian blue, and organic dyes, such as alizarin dyes, azo dyes and phthalocyanine dyes, and trace nutrients, such as iron salts, may be employed. , manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight of active product.

The active compounds according to the invention can be present in their commercially available formulations as well as in the application forms prepared from these formulations, in admixture with other active ingredients, such as insecticides, baits, sterilants, acaricides, nematicides, fungicides, growth regulating products or herbicides. Insecticides include, for example, esters of phosphoric acid, carbamates, esters of carbonic acid, chlorinated hydrocarbons, phenylureas, products prepared by means of microorganisms and the like.

Particularly convenient components of the mixture are, for example, the following: Fungicides: 2-Aminobutane; 2-ynyl ino-4-methyl-6-cyclopropylpyrimidine; 2 ', 6' -dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide; 2,6-dichloro-N- (4-t-fluoromethoxybenzyl) benzaide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinolysulfate; methyl- (E) -2-2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl-3-methoxy acrylate; methyl- (E) -methoxyimino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-Phenylphenol (OPP), Aldimorph, Ampropylfos, Anilazin, Azaconazole, Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blas ticidin-S, Bro uconazole, Bupirimate, Buthiobate, Calcium polysulfide, Captafol, Captan, Carbendazim, Carboxin, Chinóme thionat (Quinomethionat), Chloroneb, Chloropidrin, Chlorothalonil, Chozolinat, Cufraneb, Cymoxanil, Cyproconazole, Cyprofuram, Dichlorophen, Diclobutrazol, Diclofuanid, Diclomezin, Dicloran, Die thofencarb, Difenoconazole, Dime thirimol, Dimethomorph, Diniconazole, Dinocap, Diphenylamin, Dipyrithion, Ditalimphos, Dithianon, Dodin, Drazoxolon, Edifenphos, Epoxyconazole, Ethirimol, Etridiazole, Fenarimon, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimor, Fent inacetate, Fent inhydroxyd, Ferbam, Ferimzona, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazone, Flusulfamide, Flutolanil, Flutriafol, Folpet, Fosetyl-Aluminum, Fhalide, Fuberidazole, Furalaxil, Furmecyclox, Guazatine, Hexachlorobenzene, Hexaconazole, Hymexazole, Imazalil, Imibenconazole, Iminoctadin (PPI), Iprodion, Isoprothiolan, Kasugamycin, Copper Compositions , such as; copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxime and mixture of Bordeux, Mancopper, Mancozeb, Maneb Mepanipyrim, Mepronil, Metalaxyl, Metconazole, Me thasulfocarb, Metiram, Metsulfovax, Myclobutanil, Nickel dime tildi t iocarbamate, Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin, Perfurazoat, Penconazole, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin, Probenazole, Prochloraz, Procymidon, Propamocarb, Propiconazole, Propineb, Pyrazophos, Pyrefenox, Pyrimethalin, Pyroquilon, Quinotozen (PCNB), Sulfur and sulfur compositions, Tebuconazole, Tecloftalam, Tecnazen, Tetraconazole, Thiabendazole, Thicyofen, Thiophanat-methyl, Thiram, Tolclophos -methy1, Tolyfluanid, Triadimefon, Triadimenol, Triazoxid, Trichlamid, Tricyclazole, Tridemorph, Triflumizol, Triforin, Triticonazole, Validamycin A, Vinclozolin, Zineb, Ziram.

Bactericides: Bronopol, Dichlorophen, Nitrapyridin, nickel dimethyldithiocarbamate, Kasugamycin, Octhilinon, furanocarboxylic acid, Oxytetracyclin, Probenazol, S treptomycin, Tecloftalam, copper sulfate and other copper preparations.

Insecticides / Acaricides / Nematicides: Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldincarb, Alphame thrin, Amitraz, Avermectin, AZ 60541, Azadiracht in, Azinphos A, Azinphos M, Azocyclotin, Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Be tacyluthrin, Bifenthrin, BPMC , Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpiridaben, Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184 699, Chloethocarb, Chlorethoxyphos, Chlorfenvinphos, Chlor fluazuron, Chloromephos, Chlorpyrifos, Chlorpyrifos M, Cis -Res ethrin, Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazin, Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dymethylvinphos, Dioxathioin, Disulfoton, Edifenphos, Emamectin, It is fenvalerant, E thiofencarb, Ethion, Ethofenprox, ethoprophos, etofenprox, Etrimphos, Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, fenothiocarb, Fenoxycarb, fenpropathrin, fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, fluazinam, flucycloxuron, Flucythrinat, flufenoxuron, flufenprox, Fluvalinate , Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb, HCH, Heptenophos, Hexaflumuron, Hexythiazox, Imidacloprid, Iprobenfos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivemectin, Lamda-cyhalothrin, Lufenuron, Malathion, Mecarbam, Merviphos, Mesulfenphos, Metaldehyd, Methacrifos, Methamidophos, Methidathion, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin, Naled, NC 184, NI 25, Nitenpyram, Omethoat, Oxamyl, Oxydemethon M, Oxydeprofos, Parathiqn A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet , Phosphamdon, Phoxim, Pirimicarb, Pirimiphos M, Primiphos A, Profenofos, Profenophos, Promecarb, Propaphos, Propoxur, Prothiophos, Proth iophos, Prothoat, Pymetrozin, Pyrachlophos, Pyraclophos, Pyraclophos, Pyradaphenthion, Pyresme thrin, Pyre thrum, Pyridaden, Pyrimidifen, Pyriproxy fen, Quinalphos, RH 5992, Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos, Tebufenozid, Tebufepyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomethrin, Triarathen, Triazophos, Triazuron, Trichlorfon, Triflumuron, Trimethacarb, Vamidothion, • XMC, Xylylcarb, YI 5301 / 5302, Zetame thrin.

A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators is also possible.

The active compounds according to the invention can be present in their commercially available formulations as well as in the application forms prepared from these formulations in a mixture with synergists. The synergists are the compounds by which the effect of the active products is increased, without the added synergist having to be active in itself.

The active ingredient content of the application forms prepared from the commercially available formulations can vary within wide limits. The active compound concentration of the application forms can be between 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.

The application is carried out in a manner adapted to the forms of application.

When used against hygiene pests and stored products, the active products are characterized by an outstanding residual effect on wood and clay as well as good alkali stability on whitewashed substrates.

The active compounds according to the invention are not only effective against plant pests, hygiene and stored products, but also in the veterinary sector against animal parasites (ectoparasites) such as hard ticks, soft ticks. , scabies mites, migratory mites, flies (choppers and suckers), larvae of parasitic flies, lice, hair nits, nits of feathers and fleas. To these parasites belong: From the order of the anophores, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.

From the order of the Mallophagos and the suborders of the Amblicerines as well as the Isquichuarians, for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp ...

From the order of the dipterans and the suborders of the nematocerins as well as the gillweed, for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp Hybomitra spp., Atylotus spp., Tabanus spp Haematopota spp., Philipomyia spp., Braula spp Musca spp., Hydrotaea spp., Stomoxys spp. Haematobia spp., Morellia spp., Fannia spp. Glozzina spp., Calliphora spp., Lucilia spp Chrysomya spp., Wohlfahrtia spp., Sarcophaga spp Oestrus spp., Hypoderma spp., Gas terophilus spp. Hippobosca spp., Lipoptena spp., Melophagus spp.

From the order of the phytopterids, for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.

From the order of heteroptera, for example Cimex spp., Triatoma spp., Rhodnius spp., Pans trongylus spp.

From the order of the blataridos, for example Blatta oriental, Periplaneta americana, Blatella germanica, Supella spp ..

From the subclass of mites (Acarida) and the order of the meta- as well as mesoes t igmat os, for example Argas spp., Ornithodorus spp., Otabius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp.

From the order of the actinedides (Pros tigmata) and acarids (Astigmata), for example Acaparis spp., Cheyletiella spp., Orni thocheyle aunt spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp. , Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterilichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytoditees spp., Laminosioptes spp ..

The active compounds of the formula (I) according to the invention are also suitable for the control of arthropods, which attack animals useful in agriculture such as, for example, cows, lambs, goats, horses, pigs, donkeys , camels, hippos, rabbits, chickens, turkeys, ducks, geese, bees, other domestic animals such as, for example, dogs, cats, lounge birds, aquarium fish as well as so-called test animals, such as, for example, , hamsters, guinea pigs, rats and mice. By fighting against these arthropods deaths and decreases in productivity (in meat, milk, wool, skins, eggs, honey, etc.) are avoided, so that, by using the active products according to the invention, further maintenance is possible. economic and simple of the animals.

The application of the active compounds according to the invention is carried out, in the veterinary field, in a known manner by means of enteral administration in the form, for example, of tablets, capsules, beverages, dragees, pastes, boli, by means of the process by means of the feed " feed-through ", suppositories, by parenteral administration, such as, for example, by injection (intramuscular, subcutaneous, intravenous, intraperitoneal and similar), implants, by nasal application, by dermal application in the form of, for example, immersion or bathing (Dippen) , sprayed (Spray), irrigated (Pour-on and Spot-on), washed, powdered as well as with the aid of molded bodies containing the active product such as collars, ear tags, tail tags, limb bands, halters, marking devices, etc.

When used for livestock, poultry, pets, the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, spreadable agents), containing the active compounds in amounts of 1 to 80% by weight. weight, directly or after a dilution of 100 to 10,000 times or can be applied as a chemical bath.

It has also been found that the compounds of the formula I show a high insecticidal effect against the insects that destroy industrial materials.

In a preferred and preferential way - however without limitation - the following insects can be cited: Beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpine, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis; Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychus capucins, He terobos t rychus brunneus, Sinoxylon spec., Dinoderus minutus.

Hymenoptera, such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.

Termites, such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicala, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zooteris nevadensis, Coptotermies formosanus.

Thysanides, such as Lepisma saccarina Industrial materials will be understood in the present context as non-living materials, such as, preferably, synthetic materials, glues, glues, paper and cardboard, leather, wood and wood processing products and paints.

In a very special way, the materials to be protected against attack by insects are made of wood and wood products.

For wood and wood processing products, which can be protected by means of the agents according to the invention or of the mixtures containing them, it should be understood, for example: construction wood, wooden beams, railway sleepers, parts for bridges, boat ribs, wooden vehicles, boxes, pallets, containers, telephone poles, wooden coverings, wooden windows and doors, wooden plywood, plywood boards, carpentry works or wood products, which find application, in a very general way, at home or in the construction industry.

The active compounds can be used as such, in the form of concentrates or customary formulations in general, such as powders, granules, solutions, suspensions, emulsions or pastes.

Said formulations can be prepared in a manner known per se, for example by mixing the active ingredients with at least one solvent or diluent, emulsifier, dispersant and / or binder or binding agent, water repellent, if appropriate drying agents and stabilizers. against UV and, if necessary, dyes and pigments as well as other processing aids.

The insecticidal agents or concentrates to be used for the protection of wood and wood materials contain the active compound according to the invention in a concentration of 0.0001 to 95% by weight, especially 0.001 to 60% by weight. weight .

The amounts of the agents or concentrates used depend on the type and origin of the insects and the environment. The optimum application quantities can be determined respectively by means of series of tests prior to the application. In general, however, it is sufficient to employ from 0.0001 to 20% by weight, preferably from 0.001 to 10% by weight of the active product, referred to the material to be protected.

A solvent or a mixture of organochemical solvents and / or a solvent or mixture of organo-chemical, oleaginous or oil-like solvents, which are difficult to volate and / or a solvent or mixture of organochemical solvents, is used as solvent and / or diluent. polar and / or water and, if appropriate, an emulsifier and / or humectant.

Suitable organochemical solvents are preferably oleaginous or oleaginous solvents, with an evaporation value above 35 and a flame point above 30 ° C, preferably above 45 ° C. . As solvents which are difficult to volatile, water-insoluble, oleaginous or oil-like, corresponding mineral oils or their aromatic fractions or mixtures of solvents containing mineral oils, preferably benzine for tests, petroleum and / or alkylbenzene will be used.

Advantageously, mineral oils with a boiling range of 170 to 220 ° C, benzine for tests with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatic hydrocarbons with a boiling range of 160 to 280 ° C, terpene oil and the like.

In a preferred embodiment, liquid aliphatic hydrocarbons having a boiling range of 180 to 210 ° C or a high-boiling mixture of aromatic and aliphatic hydrocarbons having a boiling range of 180 to 220 ° C and / or spindles and / or monochloronaphtal ina, preferably a-monochloronaphtal ina.

Organic, sparingly soluble, oleaginous or oleaginous-type solvents, with an evaporation value above 35 and with a flame point above 30 ° C, preferably above 45 ° C, can be partially replaced by solvents light or medium volatile organochemicals, with the proviso that the solvent mixture has an evaporation index above 35 and a flame point above 30 ° C, preferably above 45 ° C, and that the insecticidal-fungicidal mixture is soluble or emulsifiable in this mixture of solvents.

According to a preferred embodiment, a part of the solvent or mixture of organochemical solvents or a solvent or mixture of aliphatic, polar organochemical solvents will be substituted. Preference is given to using aliphatic organochemical solvents containing hydroxyl and / or ester and / or ether groups, such as, for example, glycol ether, esters or the like.

As organic-chemical binders, synthetic resins and / or setting drying oils, known per se, dilutable with water and / or soluble or dispersing or emulsifiable in the organic-chemical solvents used, will be used within the scope of the present invention. especially binders consisting of or containing acrylic resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbonated resin such as indeno-coumaron resin, silicone resin, vegetable drying and / or drying oils and / or physical drying binders based on a natural and / or synthetic resin.

The synthetic resin, used as a binder, can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances up to 10% by weight can also be used as binders. In a complementary manner, dyes, pigments, water-repelling agents, odor correctors and inhibitors or anticorrosive agents known per se and the like can be used.

It is preferable to use at least one alkyd resin or a modified alkyd resin and / or a drying vegetable oil in the medium or concentrate according to the invention as an organochemical binder. Preferably, alkyd resins having an oil content of greater than 45% by weight, preferably from 50 to 68% by weight, are preferably used according to the invention.

The aforementioned binder can be partially or totally replaced by a fixing agent (mixture) or by a plasticizer (mixture). These additives should avoid volatilization of active products as well as crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).

The plasticizers are of the chemical class of phthalic acid esters such as dibutyl phthalate, dioctyl phthalate or benzylbutyl phthalate, phosphoric acid esters, such as tributyl phosphate, adipic acid esters, such as di-adipate. - (2-ethexyl), stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, glycerin ethers or high molecular weight glycol ethers, glycerin esters as well as esters of p-toluenesulonic acid.

The fixing agents are chemically based on polyvinylalkyl ethers such as polyvinyl methyl ether or on ketones such as benzophenone, ethylenebenzophenone.

Suitable as solvent or diluent is water, optionally mixed with one or more of the aforementioned solvents or diluents, emulsifiers and organochemical dispersants.

Especially effective protection of the wood is achieved by impregnation processes on an industrial scale, for example vacuum, double vacuum or pressure processes.

Agents ready for application may, if necessary, contain other insecticides and, if appropriate, one or more other fungicides.

The insecticides and fungicides mentioned in WO 94/29 268 are preferably used as additional components of the mixture. The compounds mentioned in this document are expressly an integral part of the present application.

Particularly preferred mixing components are insecticides, such as Chlorpyriphos, Phoxim, Silafluofin, Alphame thr in, Cyfluthrin, Cypermethrin, Del tamethrin, Permethrin, Imidacloprid, NI-25, Flufenoxuron, Hexaflumuron and Triflumuron, as well as fungicides such as Epoxiconazole, Hexaconazole, Azaconazole, Propiconazole, Tebuconazole, Cyproconazole, Metconazole, Imazalil, Dichlorfluanid, Tolyfluanid, 3-iodo-2-propynyl-butylcarbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin- 3-one.

The preparation and use of the active compounds according to the invention is apparent from the following examples.

Examples of obtaining.

Example 1.

(Procedure a) .0 g (19.6 mmol) of 3- (2-chloro-pyridin-5-yl-ethyl) -2-nitro-raethylene-imidazolidine, 3.0 g (23.9 mmol) of hydrochloride are dissolved. glycine methyl ester and 3.3 ml of triethylamine, together, with 3.6 ml of 37% formaldehyde solution in 30 ml of ethanol and heated at reflux for 5 hours.

The reaction mixture is allowed to cool and is concentrated by distilling off the solvent in vacuo. The residue is stirred with water, separated by filtration by suction and dried. 8.9 g of 6,7-dihydro-1- (2-chloropyridin-5-yl-methyl) -6-methoxycarbonyl-1-methyl-8-nitro- (5H) -imidazolidino- [2, 3 are obtained f] -pyrimidine with a melting point of 168 ° C.

Example 2 (Procedure b) 1.5 g (5.86 mmol) of 6,7-dihydro-6-ethoxycarbonyl-methyl-8- (5) -imido zolidino- [2, 3-f] -pyrimidine (example IV-1) are combined in 20 ml of acetonitrile with 1.6 g of potassium carbonate and 1.0 g (6.0 mmoles) of 2-chloro-5-chloromethyl thia zol. The reaction mixture is stirred for 6 hours at 40 ° C. It is then filtered off insoluble components and concentrated by evaporation to dryness. The residue is purified by column chromatography. 1.48 g of 6,7-dihydro-1- (2-chlorothiazol-5-yl-ethyl) -6-ethoxycarbonyl-methyl-8-nitro- (5H) -imidazolidino- [2, 3 -f are obtained. ] -pyrimidine with a melting point of 151 ° C.

Obtaining the product of partid Combine 2.0 g (20.2 mmol) of 2-ni t rqmet i len-imidazole idine in 30 ml of ethanol with 2.8 g (20.1 mmol) of glycine ethyl ester hydrochloride, 2.7 ml of triethylamine and 4 ml of 37% aqueous solution of formaldehyde and heated for 10 hours under reflux. The reaction mixture is allowed to cool and is concentrated by distilling off the solvent. The residue is partitioned between water and diethylether, the organic phase is separated, dried over sodium sulfate and concentrated by evaporation. 2.0 g of 6,7-dihydro-6-e-toxicarbonylmethyl-8-nor t- (5H) -imidazolidino- [2, 3-f] -pyrimidine with a melting point of 155-158 are obtained. ° C.

The compounds of the formula (I) indicated in the following table 1 are prepared analogously to that of examples 1 and 2 and according to the general indications for the preparation: Table 1 A means (CI ^ -COXR1 (contuation Table i).

*) Lg. P = Logarithm of the distribution coefficient P of the substance between the solvents octanol and water, determined experimentally from the reverse phase HPLC.

Compounds of the formula I R¿ A stands for -C-COXR1 In a manner analogous to that of Example 2, and in accordance with the general indications for the preparation, the starting products of the formula (IV) indicated in Table 2 below are prepared: Table 2 Ex. ns n m X R1 Physical constants IV-2 0 1 0 CH3 P.f .183-85 ° C Application examples In the . The following compounds are used as comparative substances in the following examples of application: (All compounds are known from EP-A 0 47 477).

Amplo A Trial with Phaedon larvae Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 Part by weight of alkylaryl polyglycol ether To obtain a convenient preparation of the active compound, 1 part by weight of active compound is mixed with the indicated amount of solvent and with the indicated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by immersion in the preparation of active compound of the desired concentration and covered with larvae of the green leaf beetle of the horseradish (Phaedon cochlearie), while the leaves are still moist.

After the desired time the destruction is determined in%. In this case 100% means that all beetle larvae were destroyed; 0% means that no larvae of the beetle were destroyed.

In this test, they caused, at an active sample concentration of active compound of 0.001%, for example the compounds according to the preparation examples 1, 3, 4, 7, 9, 10, 11, 12, 14, 19, 20, 22 and 23 a 100% destruction after 3 days, while the known compounds: (A) showed no effect, (B) showed only 30% destruction, (C) showed only 40% destruction and (E) It showed only 20% destruction.

Example B Essay with Plutella.

Solvent: 7 parts by weight of dimethylformamide. Emulsifier: 1 Part by weight of alkylaryl polyglycol ether.

To obtain a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amount of solvent and with the indicated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica olerácea) are treated by immersion with the preparation of the active compound of the desired concentration and are covered with caterpillars of the cabbage moth (Plutella maculipennis), while the leaves are still moist.

After the desired time, the destruction is determined in%. In this case 100% means that all caterpillars were destroyed; 0% means that no caterpillar was destroyed.

In this test, they caused, at an empirical active product concentration of 0.01%, for example the compounds according to the preparation examples 1, 6, 8, 9, 10, 11, 12, 13, 14, 15, 17 19, 21 and 22 a 100% destruction respectively after 3 days, while the known compound (E) showed no effect.

Example C Trial with Spodoptera Frugiperda.

Solvent: 7 parts by weight of dimethylformamide. Emulsifier: 1 Part by weight of alkylaryl polyglycol ether.

To obtain a suitable active product preparation, 1 part by weight of the active compound is mixed with the indicated amount of the solvent and with the indicated amount of the emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica olerácea) are treated by immersion with the preparation of the active compound of the desired concentration and are covered with caterpillars of the nocturnal moth (Spodoptera frugiperda), while the leaves are still moist.

After the desired time, the destruction is determined in%. In this case 100% means that all caterpillars were destroyed; 0% means that no caterpillar was destroyed.

In this test, they caused, at an active product concentration of 0.001%, for example, the compounds according to the preparation examples 8, 9, 10, 11, 12, 14, 15, 19 and 20, a destruction of 100% respectively after 3 days, while the known compounds (A), (D) and (F) showed no effect, either (B), (C) and (G) showed only 30% destruction.

Emplo D Test with Nephotettix.

Solvent: 7 parts by weight of dimethylformamide. Emulsifier: 1 Part by weight of alkylaryl polyglycol ether.

To obtain a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amount of solvent and with the indicated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Rice seedlings (Oryza sativa) are treated by immersion with the preparation of the active compound of the desired concentration and are covered with larvae of green rice cicadas (Nephotettix cincticeps), while the seedlings are still moist.

After the desired time, the destruction is determined in%. In this case 100% means that all the cicadas were destroyed; 0% means that no cicada was destroyed.

In this test, they caused, at an active concentration of 0.0001% active product, for example the compounds according to the preparation examples 6, 7, 8, 9, 10, 14, 15, 16, 17, and 18 100% destruction respectively after 6 days, while the known compound (E) showed only 20% destruction.

Example E Trial with Myzus persicae Solvent: 7 parts by weight of dimethylformamide. Emulsifier: 1 Part by weight of alkylaryl polyglycol ether ..

To obtain a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amount of solvent and with the indicated amount of emulsifier and the concentrate is diluted with water to the desired concentration, Bean saplings (Vicia faba) are immersed, which are attacked by the green louse of the leaves of the peach tree (Myzus persicae), in the preparation of active product at the desired concentration and are placed in plastic jars.

After the desired time, the destruction is determined as a percentage. In this case 100% means that all the lice on the leaves were destroyed; 0% means that no leaf louse was destroyed.

In this test, they caused, at a concentration emplificativa of active product of 0.001%, for example the compounds according to the following examples of obtaining: 1 = 99%, 4 = 80%, 6 and 16 = 90%, 15 = 98%, 19 = 95% and 20 = 100% respectively after 1 day, while the known compound (E) showed only 10% destruction and the compound (F) showed no effect.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following is claimed as property.

Claims (9)

Claims

1. Tetrahydropyrimidine derivatives of the formula (I) characterized because A means a grouping (the) - (CH2) m-COXR1 or (Ib) R2 I - CH-COXR1, Het means a heterocyclic group with 5 or 6 members, containing 1, 2, 3 or 4 nitrogen atoms and / or 1 or 2 oxygen atoms or sulfur atoms as ring heteroatoms - the number of ring heteroatoms being 1, 2, 3 or 4 - and which is substituted, if appropriate, by halogen, by cyano, by nitro, by alkyl, by haloalkyl, by alkenyl, by haloalkenyl, by alkyl, by alkoxy, by haloalkoxy, by alkenyloxy, by haloalkenyloxy, by alkynyloxy, by alkylthio, by haloalkylthio, by alkenylthio, by haloalkenyl, by alkynylthio, by alkynylsulfinyl, by haloalkylsulfonyl, by alkylsulfonyl, by haloalkylsulfonyl, by ammonium, by alkylamino, by dialkylamino, by aryl, by aryloxy, by arylthio, by arylamino, by aralkyl, by formylamino, by alkylcarbonylamino, by formyl, by carbamoyl, by alkylcarbonyl and / or by alkoxycarbonyl, RJ means hydrogen, alkyl, halogenoalkyl, alkenyl, haloalkenyl, substituted aralkyl or optionally means heterocyclylalkyl with 5 or 6 members, optionally substituted, R 2 means alkyl or aralkyl substituted if appropriate, X means oxygen or the grouping -NH- and -N- a 1 q.u i 1 or -, m means integers from 1 to 20 and n means integers from 0 to 2, excluding the compounds of the formula (I), in which at the same time A means grouping (the), Het mean Cl- N: R1 means hydrogen or ethyl, X means oxygen, m means 1 or 2 and n signi fique 0.

2. The process for obtaining tet rahydropyrimidine derivatives of the formula (I) according to claim 1, in which A s i gni f ica a group (l a) - (CH2) m- COXR1 or (Ib) R2 - CH-COXR1, Het means a heterocyclic group with 5 or 6 members, containing 1, 2, 3 or 4 nitrogen atoms and / or 1 or 2 oxygen atoms or sulfur atoms as ring heteroatoms - the number of the ring heteroatoms being 1, 2, 3 or 4 - and which is substituted, if appropriate, by halogen, by cyano, by nitro, by alkyl, by haloalkyl, by alkenyl, by haloalkenyl, by alkyl, by alkoxy, by haloalkoxy, by alkenyloxy, by haloalkenyloxy, by alkynyloxy, by alkylthio, by haloalkylthio, by alkenylthio, by haloalkenylthio, by alkynylthio, by alkynylsulfinyl, by haloalkylsul fonyl, by alkylsulfonyl, by haloalkylsulfonyl, by ammonium, by alkylamino, by dialkylamino, by aryl, by aryloxy, arylthio, arylamino, aralkyl, formylamino, alkylcarbonylamino, formyl, carbamoyl, alkylcarbonyl and / or alkoxycarbonyl, R 1 is hydrogen, alkyl, halogenalkyl, alkenyl, haloalkenyl, substituted aralkyl, if appropriate, or means 5-or 6-membered -cylocyclylalkyl, optionally substituted, R means substituted alkyl or aralkyl, if appropriate, X means oxygen or the grouping -NH- and -N- alkyl-, m means integers from 1 to 20 and n means integers from 0 to 2, excluding the compounds of the formula (I), in which at the same time A means grouping (the), Het mean Cl 7 \\ N RJ means hydrogen or ethyl, x means oxygen, m means 1 or 2 and n igni fique 0, characterized because a) Nitromethylene derivatives of the formula (II) in which Het and n have the meaning indicated above with amines of the formula (Illa) or (Illb) , H, N- (CH2) -CO-X-R1 (Ula) R 'H ^ -CH-C-O-X-R1 (inb) in which R1, R2, X and m have the meaning indicated above, If appropriate, in the form of their hydrohalogenides, in the presence of at least two times a molar amount of formaldehyde, if appropriate in the presence of an acid catalyst, if appropriate, in the presence of a diluent or, if appropriate, in the presence of a diluent. presence of a base; or b) N-tropirimidine derivatives of the formula (IV) are reacted in which A and n have the meaning indicated above, with compounds of the formula (V) Het-CH2-L (V) in which Het has the meaning indicated above and L means an anionic dissociable group, in the presence of a base and, if necessary, in the presence of a diluent.

Nitropyrimidine derivatives of the formula < (IV) characterized because A means one of the groupings (the) - (CH2) m- COXR1 or (Ib) R2 I -CH-COXR R 1 is hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, optionally substituted aralkyl or means substituted heterocyclylalkyl with 5 or 6 members, if appropriate, R means substituted alkyl or aralkyl, if appropriate, X means oxygen or the groupings -NH- and -N-alkyl-, m means integers from 1 to 20 and n means integers from 0 to 2

4. The process for obtaining nitropyrimidine derivatives of the formula (IV) according to claim 3, characterized in that derivatives of neither tromethenoyl of the formula (bundle) are reacted in which n means integers from 0 to 2 with amines of the formula (Illa) or (Illb) H, N- (CH '? 2'm-CO-X-R1 (Illa) I. (Illb) H ^ -CH-C-O-X-R1 in which, to claim 3, if appropriate in the form of their hydrohalogenides, in the presence of at least two times a molar amount of formaldehyde, if appropriate in the presence of an acid catalyst and, if necessary, in the presence of a diluent, and, if appropriate, in the presence of a base.

5. Pesticidal agents, characterized in that they have a content in at least one tetrahydropyrimidine of the formula (I), according to claim 1.

6. The use of the tetrahydropyrimidines of the formula (I) according to rei indication 1, for the control of pests.

7. The process for the control of pests, characterized in that the tetrahydropyrimidines of the formula (I) according to claim 1 are allowed to act on pests and / or on their environment.

8. The process for obtaining pesticidal agents, characterized in that tetrahydropyrimidines of the formula (I) according to claim 1 are mixed with extenders and / or surfactants.

9. The use of tetrahydropyrimidines of the formula (I) according to claim 1, for obtaining pesticidal agents.