DE19651429A1 - Tetrahydropyrimidine derivatives - Google Patents

Abstract

The present invention relates to novel tetrahydropyrimidine derivatives of the formula (I) in which A is a group (Ia) -(CH2)m -COXR<1> or (Ib); Het is a five- or six-membered heterocyclic group containing 1, 2, 3 or 4 nitrogen atoms and/or one or two oxygen or sulphur atoms as hetero-atom ring components, where the number of hetero-atoms is 1, 2, 3 or 4, and which may be substituted by halogen, cyano, nitro, alkyl, alkyl halide, alkenyl, alkenyl halide, alkinyl, alkoxy, alkoxy halide, alkenyloxy, alkenyloxy halide, alkinyloxy, alkyl thio, alkyl thio halide, alkenyl thio, alkenyl thio halide, alkinyl thio, alkyl sulphinyl, alkyl sulphinyl halide, alkyl sulphonyl, alkyl sulphonyl halide, amino, alkyl amino, dialkyl amino, aryl, aryloxy, aryl thio, aryl amino, aralkyl, formyl amino, alkyl carbonyl amino, formyl, carbamoyl, alkyl carbamoyl, alkyl carbamoyl and/or alkoxy carbonyl; R<1> is hydrogen, alkyl, alkyl halide, alkenyl, alkyl halide, alkenyl, alkenyl halide, possible substituted aralkyl or possible substituted heterocyclyl alkyl; R<2> is possibly substituted alkyl or aralkyl; X is oxygen or the groups -NH- and -N-alkyl-; m is a whole number from 1 to 20; and n is a whole number from 0 to 2; in which compounds are excepted in which A is the group (Ia), Het is (1), R<1> is hydrogen or ethyl, X is oxygen, m is 1 or 2 and n is 0. The invention also relates to a process for their production and their use as pesticides.

Description

The present invention relates to new tetrahydropyrimidine derivatives, processes for their manufacture and their use for combating animal damage succeed.

It is already known that certain bicyclic pyrimidine derivatives, such as esp special 6-substituted 6,7-dihydro-8-nitro- (5H) -1- (2-chloropyridin-5-yl-methyl or 2-chloro-1,3-thiazol-5-yl-methyl) imidazolidino- [2,3-f] pyrimidines, insecticides Have properties (see, for example, EP-A-0 247 477). The effectiveness and us However, the width of these connections is particularly low quantities and concentrations are not always fully satisfactory.

New tetrahydropyrimidine derivatives of the formula (I) have been found

in which
A for a grouping (Ia) - (CH₂) _m -COXR¹ or

stands,
Het represents a five- or six-membered heterocyclic grouping which contains 1, 2, 3 or 4 nitrogen atoms and / or one or two oxygen or sulfur atoms as heteroatom ring members - the number of ring heteroatoms being 1, 2, 3 or 4 is - and which is optionally halogen, cyano, nitro, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkenyloxy, haloalkenyloxy, alkynyloxy, alkylthio, haloalkylthio, alkenylthio, haloalkenylthio, alkynylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl alkylsulfonyl, amino, alkylamino, dialkylamino, aryl, aryloxy, arylthio, arylamino, aralkyl, formylamino, alkylcarbonylamino, formyl, carbamoyl, alkylcarbonyl and / or alkoxycarbonyl,
R1 represents hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, optionally substituted aralkyl or optionally substituted 5- or 6-membered heterocyclylalkyl,
R² represents optionally substituted alkyl or aralkyl,
X represents oxygen or the groupings -NH- and -N-alkyl-,
m represents integers from 1 to 20 and
n stands for integers from 0 to 2,
where compounds of formula (I) in which simultaneously
A stands for the grouping (Ia),
Het for

R¹ is hydrogen or ethyl,
X for oxygen,
m for 1 or 2 and
n stands for 0,
with exception of.

Furthermore, it was found that the tetrahydropyrimidine derivatives of the formula (I) if you get

• a) Nitromethylene derivatives of the formula (II) in which
  Het and n have the meaning given above,
  with amines of the formula (IIIa) or (IIIb) in which
  R¹, R², X and m have the meaning given above,
  if appropriate in the form of their hydrohalides in the presence of at least twice the molar amount of formaldehyde, if appropriate in the presence of an acid catalyst and if appropriate in the presence of a diluent and if appropriate in the presence of a base;
  or
• b) nitropyrimidine derivatives of the formula (IV) in which
  A and n have the meaning given above,
  with compounds of the formula (V) Het-CH₂-L (V) in which
  Het has the meaning given above and
  L represents an anionic leaving group,
  in the presence of a base and optionally in the presence of a diluent.

Finally, it was found that the new tetrahydropyrimidine derivatives of Formula (I) have strong biological properties and especially for Control of animal pests, especially insects, arachnids and nematodes, which are used in agriculture, in the forest, in the reserve and Material protection as well as in the hygiene sector are suitable.

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

Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below:
Het preferably represents a five- or six-membered heterocyclic grouping from the series 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 may be mono- or polysilicon, identical or different, by fluorine, chlorine, bromine, iodine, cyano, nitro, C₁-C₁-alkyl (which is optionally substituted by fluorine and / or chlorine), C₂-C₄-alkenyl (which may be is substituted by fluorine and / or chlorine), C₂-C₄-alkynyl, C₁-C₄-alkoxy (which is optionally substituted by fluorine and / or chlorine), C₃-C₄-alkenyloxy (which is optionally substituted by fluorine and / or chlorine is), C₃-C₄-alkynyloxy, C₁-C₄-alkylthio (which is optionally substituted by fluorine and / or chlorine), C₃-C₄-alkenylthio (which may be you rch is substituted by fluorine and / or chlorine), C₃-C₄-alkynylthio, C₁-C₄-alkylsulfonyl (which is optionally substituted by fluorine and / or chlorine), C₁-C₄-alkylsulfonyl (which is optionally substituted by fluorine and / or chlorine is), amino, C₁-C₄-alkylamino, di- (C₁-C₄-alkyl) -amino, phenyl, phenoxy, phenylthio, phenylamino, benzyl, formylamino, C₁-C₄-alkyl, carbonylamino, formyl, carbamoyl, C₁- C₄-alkyl-carbonyl and / or C₁-C₄-alkoxy-carbonyl is substituted.
R¹ preferably represents hydrogen, C₁-C₁₂-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, optionally optionally up to five times, identical or differently substituted phenyl-C₁-C₄-alkyl, where as Phenyl substituents may be mentioned:
Halogen, cyano, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-haloalkylthio, C₁-C₄-alkoxycarbonyl, amino, C₁-C₄ alkylamino or di (C₁-C₄ alkyl) amino; and for optionally mono- to trisubstituted, identically or differently substituted 5- or 6-membered heterocyclyl-C₁-C₄-alkyl, the heterocyclic grouping from the series 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 may be monosubstituted to triple, identically or differently, by fluorine, chlorine, bromine, iodine, cyano, nitro, C₁-C₄-alkyl (which if appropriate by Fluorine and / or chlorine is substituted), C₂-C₄-alkenyl (which is optionally substituted by fluorine and / or chlorine), C₂-C₄-alkynyl, C₁-C₄-alkoxy (which is optionally substituted by fluorine and / or chlorine) ), C₃-C₄-alkenyloxy (which is optionally substituted by fluorine and / or chlorine), C₃-C₄-alkynyloxy, C₁-C₄-alkylthio (which is given benenfa lls is substituted by fluorine and / or chlorine), C₃-C₄-alkenylthio (which is optionally substituted by fluorine and / or chlorine), C₃-C₄-alkynylthio, C₁-C₄-alkylsulfinyl (which is optionally substituted by fluorine and / or chlorine is), C₁-C₄-alkylsulfonyl (which is optionally substituted by fluorine and / or chlorine), amino, C₁-C₄-alkylamino, di- (C₁-C₄-alkyl) -amino, phenyl, phenoxy, phenylthio, phenylamino, benzyl , Formylamino, C₁-C₄-alkyl, carbonylamino, formyl, carbamoyl, C₁-C₄-alkyl-carbonyl and / or C₁-C₄-alkoxy-carbonyl are substituted.

R² preferably represents C _1-8 alkyl or optionally substituted benzyl,
X preferably represents oxygen or the groupings -NH- and -N (C₁-C₈) alkyl-.

m preferably represents integers from 1 to 12.

n preferably represents the numbers 0 and 1.

Connections are excluded in which at the same time
A stands for the grouping (Ia),
Het for

R¹ is hydrogen or ethyl,
X for oxygen
m for 1 or 2 and
n stands for 0.

Het is particularly preferably a five- or six-membered hetero cyclic grouping from the series pyrazolyl, 1,2,4-triazolyl, oxazolyl, Isoxazolyl, thiazolyl, isothiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrazinyl  and pyrimidinyl, which are optionally one to three times the same or different from fluorine, chlorine, bromine, iodine, cyano, nitro, C₁-C₂-alkyl (which is optionally substituted by fluorine and / or chlorine), C₁-C₂ alkoxy (which is optionally substituted by fluorine and / or chlorine is), C₁-C₂-alkylthio (which may be replaced by fluorine and / or chlorine is substituted), C₁-C₂-alkylsulfonyl (which is optionally substituted by fluorine and / or chlorine is substituted).

R¹ particularly preferably represents hydrogen, C₁-C₈-alkyl, C₁-C₄-halogeno alkyl, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl, for optionally mono- to trisubstituted, identically or differently substituted, phenyl-C₁-C₂-alkyl, where the following may be mentioned as phenyl substituents:
Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy and trifluoromethylthio;
and for optionally mono- to trisubstituted, identically or differently substituted 5- or 6-membered heterocyclyl-C₁-C₂-alkyl, the heterocyclic group from the series pyrazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrazinyl and pyrimidinyl, which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C₁-C₂-alkyl (which is optionally substituted by fluorine and / or chlorine), C₁-C₂- Alkoxy (which is optionally substituted by fluorine and / or chlorine), C₁-C₂-alkylthio (which is optionally substituted by fluorine and / or chlorine), C₁-C₂-alkylsulfonyl (which is optionally substituted by fluorine and / or chlorine) are.

R² particularly preferably represents C _1-4 -alkyl or benzyl, if appropriate by halogen (chlorine, fluorine, chromium), C _1-4 -alkyl, C _1-2 -alkoxy, C _1-2 -alkylthio, C _1-2 haloalkyl, C _1-2 haloalkoxy, C _1-2 haloalkylthio, nitro, cyano;
X particularly preferably represents oxygen or the groupings -NH-, -N (CH₃) - and -N (C₂H₅) -.

m particularly preferably represents integers from 1 to 10.

n particularly preferably represents the numbers 0 and 1.  

Connections are excluded in which at the same time
A stands for the grouping (Ia),
Het for

R¹ is hydrogen or ethyl,
X for oxygen,
m for 1 or 2 and
n stands for 0.

Het very particularly preferably represents in each case simply up to two multiple, identical or different substituted by fluorine, chlorine or bromine Pyridyl and thiazolyl.

R¹ very particularly preferably represents hydrogen, C₁-C₈-alkyl, optionally optionally monosubstituted or disubstituted, identically or differently substituted benzyl, the following being mentioned as substituents:
Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy and trifluoromethylthio;
as well as for pyridylmethyl and thiazolylmethyl substituted by fluorine, chlorine or bromine and substituted by fluorine, chlorine or bromine, if appropriate in each case once to twice.

R² very particularly preferably represents C _1-4 alkyl or benzyl;

X very particularly preferably represents oxygen or the -NH grouping.

m very particularly preferably represents integers from 1 to 8.

n very particularly preferably stands for the numbers 0 and 1.

Connections are excluded in which at the same time
A stands for the grouping (Ia),
Het for

R¹ is hydrogen or ethyl,
X for oxygen,
m for 1 or 2 and
n stands for 0.

The residue definitions listed above or in preferred areas or explanations apply to the end products and to the initial and Intermediates accordingly. These residual definitions can be thus also be combined as desired between the respective preferred areas.

According to the invention, preference is given to the compounds of the formula (I) in which a combination of the Be listed as preferred (preferred) interpretations are available.

According to the invention, particular preference is given to the compounds of the formula (I), in which are a combination of those listed as particularly preferred above Meanings exist.

The compounds of the formula are very particularly preferred according to the invention (I) in which a combination of the above is particularly preferred listed meanings is present.

In the residue definitions listed above and below are hydrocarbons residues such as alkyl or alkenyl - also in compounds with heteroatoms such as Alkoxy or Alylthio - if possible straight or branched.

Preferred compounds according to the invention are substances of the formulas (Ic) to (If):

in which
Het¹ represents optionally substituted pyridyl and
A has the meaning given in the definition of the invention.

in which
Het¹ represents optionally substituted pyridyl and
A has the meaning given in the definition of the invention.

in which
Het² represents optionally substituted thiazolyl and
A has the meaning given in the definition of the invention.

in which
Het² represents optionally substituted thiazolyl and
A has the meaning given in the definition of the invention.

Preferred compounds according to the invention are also groups of substances of the formulas (Ia-1), (Ib-1), (Ic-1) and (Id-1):

in which
A stands for the above-mentioned general preferred, particularly preferred and very particularly preferred meanings.

in which
A stands for the above-mentioned general preferred, particularly preferred and very particularly preferred meanings.

in which
A stands for the above-mentioned general preferred, particularly preferred and very particularly preferred meanings.

in which
A stands for the above-mentioned general preferred, particularly preferred and very particularly preferred meanings.

Is used to carry out process (a) according to the invention in for example 3- (2-chloropyridin-5-yl-methyl) -2-nitromethylene-imidazolidine, glycine methyl ester hydrochloride and 2 moles of formaldehyde, so the reaction can can be outlined by the following formula:

Is used to carry out process (b) according to the invention for example 6,7-dihydro-6-methoxycarbonylmethyl-8-nitro- (5H) -imidazolidino- [2,3-f]  pyrimidine and 2-chloro-5-chloromethyl-pyridine, so the course of the reaction can the following formula scheme are outlined:

Those to be used as starting materials in process (a) according to the invention Nitromethylene derivatives of the formula (II) are known (cf., 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 produced according to known methods (cf. the above mentioned open European applications).

If the nitromethylene derivatives are used in the form of their hydrohalides, the hydrochlorides are preferred.

Those in process (a) according to the invention also as starting materials amines of formula (III-a) and (III-b) using are generally known Compounds of organic chemistry and / or can in the usual way be preserved.

Those to be used as starting materials in process (b) according to the invention Nitropyrimidine derivatives of the formula (IV) are not yet known. You can can be obtained by using nitromethylene derivatives of the formula (IIa) (cf. e.g. EP-A 0 247 477)

in which
n has the meaning given above,
with amines of the formula (III-a) and (III-b) according to process (a).

Those in process (b) according to the invention also as starting materials Compounds using are generally defined by formula (V). L preferably represents chlorine, bromine, iodine, acetoxy, tosyl or mesyl. The Compounds of formula (V) are generally known substances of the organic Chemistry.

Process (a) according to the invention is preferably carried out using Diluents performed. Water is used as the diluent and for the reaction of inert organic solvents. This includes preferably aliphatic and aromatic, optionally halogenated carbons Hydrogen such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligoin, Benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, tetrachlor carbon, chlorobenzene and o-dichlorobenzene, ethers such as diethyl and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and di oxane, alcohols such as methanol, ethanol, n-propanol and isopropanol. Prefers mixtures of alcohols and water are used.

Process (a) according to the invention is optionally carried out in the presence of acidic, non-oxidizing catalysts. Have proven particularly successful there are hydrohalic acids such as hydrochloric acid and hydrobromic acid, phosphorus acid, lower carboxylic acids such as acetic acid and propionic acid.

The reaction temperatures in process (a) according to the invention can be in can be varied over a wide range. Generally one works at Tempe temperatures between -20 ° C and 120 ° C, preferably at temperatures between 0 ° C and + 80 ° C.

Process (a) according to the invention is generally carried out under atmospheric pressure carried out. However, it is also possible to increase or decrease it Pressure to work.  

To carry out process (a) according to the invention, 1 mol is used Nitromethylene derivative of the formula (II), 1 to 1.5 mol, preferably 1 to 1.2 mol Amine of formula (III) and 2 to 4 moles, preferably 2 to 3 moles of formaldehyde a.

The amines of formula (III) can optionally be used as aqueous solutions be set. When using gaseous amines of the formula (III) can these compounds through the mixture of diluent, Verbin tions of formula (II) and formaldehyde are passed. For the fiction according to the procedure, formaldehyde is used in aqueous solution. The reaction NENs are generally carried out in a suitable diluent and the reaction mixture is kept at the required for several hours Temperature stirred. Working up takes place in the process according to the invention ren according to usual methods.

Process (b) according to the invention is preferably carried out using Diluents performed. Virtually all come as diluents inert organic solvents in question. These preferably include alipha tables and aromatic, optionally halogenated hydrocarbons such as pen tan, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, Xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorine benzene and o-dichlorobenzene, ethers such as diethyl and dibutyl ether, glycol di methyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as Acetone, methyl ethyl, methyl isopropyl or methyl isobutyl ketone, esters such as Methyl acetate or ethyl acetate, nitriles such. B. acetonitrile or propio nitrile, amides such as B. dimethylformamide, dimethylacetamide and N-methyl pyrrolidone and dimethyl sulfoxide, tetramethylene sulfone or hexamethylene meth phosphoric triamide.

All of the more customary bases can be used in processes (a) and (b) according to the invention wise used for such reactions acid binders who the. Alkali metal and alkaline earth metal hydrides are preferred, such as lithium, sodium, potassium or calcium hydride, alkali metal or alkaline earth metal hydroxides, such as lithium, sodium, potassium or calcium hydroxide, alkali metal or alkaline earth metal carbonates or bicarbonates, such as sodium or Potassium carbonate or bicarbonate or calcium carbonate, alkali metal acetate, such as sodium or potassium acetate, alkali metal alcoholates, such as sodium or  Potassium tert-butoxide, also basic nitrogen compounds, such as trime thylamine, triethylamine, tripropylamine, tributylamine, diisobutylamine, di cyclohexylamine, ethyldiisopropylamine, ethyldicyclohexylamine, N, N-dimethyl benzylamine, N, N-dimethyl-aniline, pyridine, 2-methyl, 3-methyl, 4-methyl, 2,4-dimethyl, 2,6-dimethyl, 2-ethyl, 4-ethyl and 5-ethyl-2-methyl-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 be in can be varied over a wide range. Generally one works at Tempe temperatures 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 carried out. However, it is also possible to increase or decrease it Pressure to work.

To carry out process (b) according to the invention, the respective required starting materials in general in approximately equimolar amounts used. However, it is also possible to use either of the two To use components in a larger excess. The reactions who generally in a suitable diluent in the presence of a Acid acceptor performed, and the reaction mixture is at several hours the required temperature is stirred. The processing takes place after usual methods.

With good plant tolerance and favorable warm-blood toxicity, the active substances are suitable for combating animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored products and materials, and in the hygiene sector. They can be used as pesticides before. They are effective against normally sensitive and resistant species and against all or individual stages of development. The pests mentioned above include:
From the order of the Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Por cellio scaber.

From the order of the Diplopoda z. B. Blaniulus guttulatus.  

From the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spec.

From the order of the Symphyla z. B. Scutigerella immaculata.

From the order of the Thysanura z. B. Lepisma saccharina.

From the order of the Collembola z. B. Onychiurus armatus.

From the order of Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of the Dermaptera z. B. Auricular Forficula.

From the order of the Isoptera z. B. Reticulitermes spp.

From the order of the Anoplura z. B. Pediculus humanus corporis, Haematopinus spp., Linognathus spp.

From the order of the Mallophaga z. B. Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci.

From the order of Heteroptera z. B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., 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 z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp.,  Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Spodoptera litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmaunophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus 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, Costelytra zealandica.

From the order of the Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysoinyia 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, Tipula paludosa.

From the order of the Siphonaptera z. B. Xenopsylla cheopis, Ceratophyllus spp.

From the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans.

From the order of Acarina z. B. Acarus siro, Argas spp., Omithodoros 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 plant parasitic nematodes include z. B. Pratylenchus spp., Radopho lus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., xiphinema spp., Trichodorus spp.

The compounds of the formula (I) according to the invention are particularly noteworthy with a high level of insecticidal activity.

They can be used with particularly good success to combat plant damage insects, such as against the horseradish leaf beetle larvae (Phae don cochlaeriae), the caterpillars of the cockroach (Plutella maculipennis), the green one Rice leafhopper (Nephotettix cinctriceps), the caterpillars of the owl butterfly (Spodoptera frugiperda) or the peach aphids (Mycus persicae).

The active ingredients can be converted into the usual formulations, such as Lö solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, sol Liche powder, granules, suspension emulsion concentrates, active ingredient impregnated nated natural and synthetic substances as well as very fine encapsulation in polymers Fabrics.

These formulations are prepared in a known manner, e.g. B. by Ver mixing the active ingredients with extenders, i.e. liquid solvents and / or solid carriers, optionally using surface-active agents Agents, that is emulsifiers and / or dispersants and / or foam generators resources.

In the case of the use of water as an extender, e.g. B. also organic Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic carbons Hydrogen, such as cyclohexane or paraffins, e.g. B. petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and their ethers and Esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclo hexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.  

The following are suitable as solid carriers:
e.g. B. ammonium salts and natural rock powders, such as kaolins, clays, talcum, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, are suitable as solid carriers for granules: z. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foaming agents come into question: z. B. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for. B. alkylaryl polyglycol ethers, alkyl sulfates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersants come into question: z. B. lignin sulfite and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural, can be used in the formulations Liche and synthetic powdery, granular or latex-shaped polymers used 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, e.g. B. iron oxide, titanium oxide, ferro cyan and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, Cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95% by weight Active ingredient, preferably between 0.5 and 90%.

The active ingredient according to the invention can be present in its commercially available formulations and in the use forms prepared from these formulations in admixture with other active ingredients, such as insecticides, attractants, sterilants, Bak tericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenyl ureas, substances produced by microorganisms and others
Particularly cheap mixing partners are e.g. B. the following:

Fungicides

2-aminobutane; 2-anilino-4-methyl-6-cydopropyl-pyrimidine; 2 ′, 6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxanide; 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophen oxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,
Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,
Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
Dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
Edifenphos, Epoxyconazole, Ethirimol, Etridiazol, Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fen propimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludi oxonil, Fluoromide, Fluulfonazolutolanilofolafilolazolutol, Fluulilazazolutol, Fluolinilazolutol, Fluulilazazolutol , Fosetyl aluminum, fthalides, fuberidazole, furalaxyl, furmecyclox,
Guazatine,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan,
Kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,
Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, oxadixyl, oxamocarb, oxycarboxin,
Pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,
Quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, Tecloftalam, Tecnazen, Tetraconazole, Thiabendazole, Thicyofen, Thiophanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, Triadi menol, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Triforazol, Tri,
Validamycin A, vinclozolin,
Zineb, ziram.

Bactericides

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, Kasugamy cin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, Tec loftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides

Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alpha methrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,
Bacillus thuringiensis, Bendiocarb, Benfuracarb, B ensultap, Betacyfluthrin, Bifen thrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorflu azuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrinhrhrhrinhrhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrofhrinhrinhrinhrinhrinhrinhrofhrinothrinothrinhrhrinhrhrinhrinhrinhrofhrinothrinothrinothrinhrhrinhrhrinhrinhrofhrinothrinothrinothrinophrinothrinophrinothrinophrinothrinophrinophrine , Cyhexatin, cyper methrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Di azinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflu benzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Etho prophos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipro nil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Fufionatexfonophon, Fufionproxophon, Fufonproxophone, Fufonproxophon, Fufonproxophon, Fufonfox, Fufionfox, Fufionfox, Fufone
HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Iver mectin, Lambda-cyhalothrin, Lufenuron,
Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
Naled, NC 184, M 25, Nitenpyram,
Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophhine, Pyrachlophhion, Pyrachlophion, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophion Pyridaben, pyrimidifen, pyriproxifen,
Quinalphos,
RH 5992,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiome thon, Thionazin, Thuringiensin, Tralomenhronon, Triaromenhriazonium, Triaromenhroniazonium
Vamidothione, XMC, xylylcarb, YI 5301/5302, zetamethrin.

A mixture with other known active ingredients, such as herbicides or with Fertilizers and growth regulators are possible.

The active compounds according to the invention can also be used in their commercially available form formulations and in the application forms prepared from these formulations in a mixture with synergists. Synergists are connections through which the effect of the active ingredients is increased without the added synergist must be actively active itself.

The active ingredient content of the prepared from the commercially available formulations Application forms can vary widely. The drug concentration The use forms can range from 0.0000001 to 95% by weight of active ingredient preferably between 0.0001 and 1 wt .-%.

The application takes place in a customary manner adapted to the application forms Wise.

When used against hygiene and storage pests, the stands out Active ingredient through an excellent residual effect on wood and clay as well due to good stability to alkali on limed substrates.

The active compounds according to the invention act not only against plant, hygiene and stored-product pests, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, Featherlings and fleas. These parasites include:
From the order of the Anoplurida z. B. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.

From the order of the Mallophagida and the subordinates Amblycerina as well Ischnocerina e.g. B. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.

From the order Diptera and the subordinates Nematocerina as well Brachycerina e.g. B. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotoinus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tahanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp.

From the order of the Siphonapterida z. B. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.

From the order of the Heteropterida z. B. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.

From the order of the Blattarida z. B. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp.

From the subclass of Acaria (Acarida) and the orders of the Meta and Mesostigmata e.g. B. Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneu monyssus spp., Sternostoma spp., Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata) z. B. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,  Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

The active compounds of the formula (I) according to the invention are also suitable for combating treatment of arthropods, the farm animals, such as. B. cattle, sheep, Goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, Geese, bees, other pets such as B. dogs, cats, house birds, aqua reindeer fish and so-called experimental animals, such as B. hamsters, guinea pigs, Infect rats and mice. By fighting these arthropods are said to Death trap and reduced performance (for meat, milk, wool, skins, eggs, Honey, etc.) can be reduced, so that by using the invention Active ingredients a more economical and easier animal husbandry is possible.

The active compounds according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, Tab Latvian, capsules, watering, drenching, granules, pastes, boluses, feed-through Method, of suppositories, by parenteral administration, such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), Implants, by nasal application, by dermal application in the form of for example diving or bathing (dipping), spraying (spray), pouring on (Pour-on and spot-on), washing, powdering and with the help of active molded articles, such as collars, ear tags, tail tags, link measuring tapes, holsters, marking devices etc.

When used for cattle, poultry, pets etc. you can use the active ingredients of the formula (I) as formulations (for example powders, emulsions, flowable Agents), which contain the active ingredients in an amount of 1 to 80 wt .-%, directly or after 100 to 10,000 times dilution or as chemical Use bath.

It has also been found that the compounds of the formula (I) show a high insecticidal activity against insects, the technical mate destroy rialien.

The following insects may be mentioned by way of example and preferably, but without limitation:
Beetle like
Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearesces rugus, Lyctus pubescescus, Lyctus pubis linearis, Lyctus linearesces rug Xyleborus spec. Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus.

Skin wings like
Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.

Termites like
Kalotermes flavicollis, Cryptoterines brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwi niensis, Zootermopsis nevadensis, Coptotermes formosanus.

Bristle tails, such as Lepisma saccarina.

In the present context, technical materials include non-living ones To understand materials, such as preferably plastics, adhesives, glues, Pa paper and cardboard, leather, wood and wood processing products and paints.

It is very particularly preferred to prevent insect attack protective material around wood and wood processing products.

Among wood and wood processing products, which by the invention Agents or mixtures containing them can be protected is exemplary to understand: timber, wooden beams, railway sleepers, bridge parts, jetties, Wooden vehicles, boxes, pallets, containers, telephone poles, wooden panels, Wooden windows and doors, plywood, chipboard, carpentry or wood products that are used in general in house construction or in joinery Find.

The active ingredients can be used as such, in the form of concentrates or in general usual formulations such as powders, granules, solutions, suspensions, emul sions or pastes.  

The formulations mentioned can be prepared in a manner known per se be, e.g. B. by mixing the active ingredients with at least one solution or Diluent, emulsifier, dispersing and / or binding or fixing agent tels, water repellants, possibly desiccants and UV stabilizers and opp if necessary dyes and pigments and other processing aids.

The insecticidal agents used to protect wood and wood-based materials or concentrates contain the active ingredient according to the invention in a concentra tration from 0.0001 to 95 wt .-%, in particular 0.001 to 60 wt .-%.

The amount of agents or concentrates used depends on the type and type come from insects and depending on the medium. The optimal amount to use can be determined by test series in the application. in the in general, however, it is sufficient from 0.0001 to 20% by weight, preferably 0.001 up to 10 wt .-% of the active ingredient, based on the material to be protected put.

An organic chemical solution serves as the solvent and / or diluent medium or solvent mixture and / or an oily or oily heavy volatile organic chemical solvent or solvent mixture and / or a polar organic chemical solvent or solvent mixture and / or water and optionally an emulsifier and / or wetting agent.

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

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

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

The organic non-volatile oily or oily solvents with a Evaporation rate above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partly due to slightly or medium volatile organic Mix solvent to be replaced, provided that the solvent mix also an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide fungicide Mixture is soluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, part of the organic chemical Solvent or solvent mixture or an aliphatic polar orga niche chemical solvent or solvent mixture replaced. Preferably come aliphati containing hydroxyl and / or ester and / or ether groups organic chemical solvents such as glycol ethers, esters or the like for use.

As an organic chemical binder in the present Er finding the known water-dilutable and / or in the used organic chemical solvents soluble or dispersible or emulsifiable Ren synthetic resins and / or binding drying oils, especially binders best hend from or containing an acrylate resin, a vinyl resin, e.g. B. polyvinyl acetate, Polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene Coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or Resin used.

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

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

The binder mentioned can be wholly or partly by means of a fixing agent tel (mixture) or a plasticizer (mixture) can be replaced. These additions are meant to volatilization of the active ingredients and crystallization or precipitation prevent. They preferably replace 0.01 to 30% of the binder (based on to 100% of the binder used).

The plasticizers come from the chemical classes of phthalic acid esters such as Dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, glycerol ether or higher molecular weight Gly kolether, glycerol ester and p-toluenesulfonic acid ester.

Fixing agents are chemically based on polyvinyl alkyl ethers such as. B. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.

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

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

The ready-to-use agents can optionally also be other insecticides and optionally contain one or more fungicides.

Additional mixing partners are preferably those in Wo 94/29 268 Insecticides and fungicides mentioned in question. The ones mentioned in this document Connections are an integral part of this application.  

Insecticides such as chlorine can be used as very particularly preferred mixing partners pyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, delta methrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and tri flumuron, and fungicides such as epoxyconazole, hexaconazole, azaconazole, Pro piconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorfluanide, Tolylfluanid, 3-iodo-2-propynyl butyl carbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one.

The manufacture and use of the active compounds according to the invention start out the following examples.

Manufacturing examples example 1 (Method a)

5.0 g (19.6 mmol) of 3- (2-chloropyridin-5-yl-methyl) -2-nitro-methylene-imidazdidine, 3.0 g (23.9 mmol) glycine methyl ester hydrochloride and 3.3 ml triethylamine together with 3.6 ml of 37% formaldehyde solution in 30 ml of ethanol dissolved and heated under reflux for 5 hours.

The reaction mixture is allowed to cool and concentrated by distilling off the solution solvent in a vacuum. The residue is stirred with water and suction filtered and dried.

8.9 g of 6,7-dihydro-1 - (- chloropyridin-5-yl-methyl) -6-methoxycarbonyl are obtained methyl-8-nitro- (5H) -imidazolidino- [2,3-f] pyrimidine, melting point 168 ° C.

Example 2 (Method b)

1.5 g (5.86 mmol) of 6,7-dihydro-6-ethoxycarbonyl-methyl-8- (5H) -imidazolidino- [2,3-f] pyrimidine (Ex. IV-1) in 20 ml of acetonitrile are mixed with 1.6 potassium carbonate and 1.0 g (6.0 mmol) of 2-chloro-5-chloromethylthiazole. The reaction ge mixed is stirred at 40 ° C for 6 hours. After that it becomes insoluble divide filtered and evaporated to dryness. The residue becomes columnar matographically cleaned.

1.48 g of 6,7-dihydro-1- (2-chlorothiazol-5-yl-methyl) -6-ethoxycarbonyl are obtained methyl-8-nitro- (5H) -imidazolidino- [2,3-f] pyrimidine, melting point 151 ° C.  

Manufacture of the starting product

2.0 g (20.2 mmol) of 2-nitromethylene-imidazolidine in 30 ml of ethanol are mixed with 2.8 g (20.1 mmol) glycine ethyl ester hydrochloride, 2.7 ml triethylamine and 4 ml 37% aqueous formaldehyde solution and heated under reflux for 10 hours. The reaction mixture is allowed to cool and concentrated by distilling off the solution agent. The residue is partitioned between water and diethyl ether, the organic phase is separated off, dried over sodium sulfate and concentrated.

2.0 g of 6,7-dihydro-6-ethoxycarbonylmethyl-8-nitro- (5H) -imidazolidino- [2,3-f] pyrimidine, melting point 155-158 ° C.

Analogous to Examples 1 and 2 and according to the general information on The compounds listed in Table 1 below are prepared of formula (I):

Table 1

Compounds of formula I.
A stands for

Analogous to Example 2 and according to the general information on the preparation the starting materials of the formula listed in Table 2 below (IV) received:

Table 2

Examples of use

The following application examples list the following Compounds used as reference substances:

Example A Phaedon larval test

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

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the wanted concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with horseradish leaf beetle larvae (Phaedon cochleariae) occupied while the leaves are still moist.

After the desired time, the kill is determined in%. Here means 100% that all beetle larvae have been killed; 0% means that no beetles Larvae were killed.

In this test, at an exemplary active ingredient concentration of 0.001% z. B. the compounds of Preparation Examples 1, 3, 4, 7, 9, 10, 11, 12, 14, 19, 20, 22 and 23 a kill of 100% after 3 days each, during the known compounds: (A) no effect, (B) only 30% kill, (C) showed only 40% kill and (E) only 20% kill.  

Example B Plutella test

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

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the wanted concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars (Plu tella maculipennis) as long as the leaves are still moist.

After the desired time, the kill is determined in%. Here means 100% that all caterpillars have been killed; 0% means that no caterpillars were killed.

In this test, at an exemplary active ingredient concentration of 0.01% z. B. the compounds of Preparation Examples 1, 6, 8, 9, 10, 11, 12, 13, 14, 15, 17, 19, 21 and 22 a 100% kill every 3 days, while the known compound (E) had no effect.  

Example C Spodoptera Frugiperda test

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

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the wanted concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars of the owl butterfly (Spodoptera frugiperda) occupied while the leaves are still moist.

After the desired time, it is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.

In this test, at an exemplary active ingredient concentration of 0.001% z. B. the compounds of Preparation Examples 8, 9, 10, 11, 12, 14, 15, 19 and 20 a kill of 100% each after 3 days, while the known Compounds (A), (D) and (F) have no effect and (B), (C) and (G) only showed a kill of 30%.  

Example D Nephotettix test

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

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the wanted concentration.

Rice seedlings (Oryza sativa) are dipped into the active ingredient preparation the desired concentration and treated with green rice leafhopper larvae (Nephotettix cincticeps) occupied while the seedlings are still moist.

After the desired time, the kill is determined in%. Here means 100% that all cicadas have been killed; 0% means no cicadas were killed.

In this test, at an exemplary active ingredient concentration of 0.0001% z. B. the compounds of Preparation Examples 6, 7, 8, 9, 10, 14, 15, 16, 17 and 18 a 100% kill each after 6 days while the known compound (E) only showed a kill of 20%.  

Example E Myzus test

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

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the wanted concentration.

Broad bean seedlings (Vicia faba) by the green peach aphid (Myzus persicae) are infested in the drug preparation of the desired Submerged concentration and placed in a plastic can.

After the desired time, the kill is determined in percent. Thereby be indicates 100% that all aphids have been killed; 0% means that none Aphids were killed off.

In this test, at an exemplary active ingredient concentration of 0.001%, z. B. the compounds of the following production examples following killings gene:
1 = 99%, 4 = 80% 6 and 16 = 90%, 15 = 98%, 19 = 95% and 20 = 100%,
in each case after 1 day, while the known compounds (E) only killed 10% and (F) had no effect.

Claims (9)

1. tetrahydropyrimidine derivatives of the formula (I) in which
A for one of the groupings (Ia) - (CH₂) _m -COXR¹ or stands,
Het represents a five- or six-membered heterocyclic grouping which contains 1, 2, 3 or 4 nitrogen atoms and / or one or two oxygen or sulfur atoms as heteroatom ring members - the number of ring heteroatoms being 1, 2, 3 or 4 - and which is optionally halogen, cyano, nitro, alkyl, halo genalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkenyloxy, haloalkenyloxy, alkynyloxy, alkylthio, halo genalkylthio, alkenylthio, haloalkenylthio, alkynylthio, alkyl sulfinyl, haloalkylsulfinyl, Alkylsulfonyl, haloalkylsulfonyl, amino, alkylamino, dialkylamino, aryl, aryloxy, arylthio, arylamino, aralkyl, formylamino, alkylcarbonylamino, formyl, carbamoyl, alkylcarbonyl and / or alkoxycarbonyl,
R1 represents hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, optionally substituted aralkyl or optionally substituted 5- or 6-membered heterocyclylalkyl,
R² represents optionally substituted alkyl or aralkyl,
X represents oxygen or the groupings -NH- and -N-alkyl-,
m represents integers from 1 to 20 and
n stands for integers from 0 to 2,
being connections in which simultaneously
A stands for the grouping (Ia),
Het for R¹ is hydrogen or ethyl,
X for oxygen,
m for 1 or 2 and
n stands for 0,
with exception of. 2. A process for the preparation of the tetrahydropyrimidine derivatives of the formula (I) according to claim 1 in which
A for one of the groupings (Ia) - (CH₂) _m -COXR¹ or (Ib) stands,
Het represents a five- or six-membered heterocyclic grouping which contains 1, 2, 3 or 4 nitrogen atoms and / or one or two oxygen or sulfur atoms as heteroatom ring members - the number of ring heteroatoms being 1, 2, 3 or 4 - and which is optionally halogen, cyano, nitro, alkyl, halo genalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkenyloxy, haloalkenyloxy, alkynyloxy, alkylthio, halo genalkylthio, alkenylthio, haloalkenylthio, alkynylthio, alkyl sulfinyl, haloalkylsulfinyl, Alkylsulfonyl, haloalkylsulfonyl, amino, alkylamino, dialkylamino, aryl, aryloxy, arylthio, arylamino, aralkyl, formylamino, alkylcarbonylamino, formyl, carbamoyl, alkylcarbonyl and / or alkoxycarbonyl,
R1 represents hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, optionally substituted aralkyl or optionally substituted 5- or 6-membered heterocyclylalkyl,
R² represents optionally substituted alkyl or aralkyl,
X represents oxygen or the groupings -NH- and -N-alkyl-,
m represents integers from 1 to 20 and
n stands for integers from 0 to 2,
being connections in which simultaneously
A stands for the grouping (Ia),
Het for R¹ is hydrogen or ethyl,
X for oxygen,
m for 1 or 2 and
n stands for 0,
with exception of,
characterized in that one

• a) Nitromethylene derivatives of the formula (II) in which
  Het and n have the meaning given above,
  with amines of the formula (IIIa) or (IIIb) in which
  R¹, R², X and have the meaning given above,
  if appropriate in the form of their hydrohalides in the presence of at least twice the molar amount of formaldehyde, if appropriate in the presence of an acid catalyst and if appropriate in the presence of an acid catalyst and if appropriate in the presence of a diluent and if appropriate in the presence of a base;
  or
• b) nitropyrimidine derivatives of the formula (IV) in which
  A has the meaning given above,
  with compounds of the formula (V) Het-CH₂-L (V) in which
  Het has the meaning given above and
  L represents an anionic leaving group,
  in the presence of a base and optionally in the presence of a diluent.

3. Nitropyrimidine derivatives of the formula (IV) in which
A for one of the groupings (Ia) - (CH₂) _m -COXR¹ or stands.
R¹ is hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, optionally substituted aralkyl or optionally substituted 5- or 6-membered heterocyclylalkyl,
R² represents optionally substituted alkyl or aralkyl,
X represents oxygen or the groupings -NH- and -N-alkyl-,
m represents integers from 1 to 20 and
n stands for integers from 0 to 2. 4. A process for the preparation of the nitropyrimidine derivatives of the formula (IV) according to claim 3, characterized in that nitromethylene derivatives of the formula (IIa) in which
n stands for integers from 0 to 2,
with amines of the formula (IIIa) or (IIIb) in which
R¹, R², X and m have the meaning given in claim 3,
if appropriate in the form of their hydrohalides in the presence of at least twice the molar amount of formaldehyde, if appropriate in the presence of an acid catalyst and if appropriate in the presence of a diluent and if appropriate in the presence of a base. 5. pesticide, characterized by a content of min at least one tetrahydropyrimidine of the formula (I), according to Claim 1. 6. Use of tetrahydropyrimidines of the formula (I) according to Claim 1 to control pests. 7. A method for controlling pests, characterized in that tetrahydropyrimidines of the formula (I) according to Claim 1 for pests linge and / or their living space. 8. Process for the preparation of pesticides, thereby ge indicates that tetrahydropyrimidines of the formula (I) according to An saying 1 mixed with extenders and / or surfactants. 9. Use of tetrahydropyrimidines of the formula (I) according to Claim 1 for the production of pesticides.