DE19603576A1 - Acylated 4-amino and 4-hydrazinopyrimidines - Google Patents

Abstract

The invention relates to novel compounds of formula (I) in which R<1>, R<2>, Ar, A and X have the meanings indicated in the description, and to methods of producing said compounds and their use in combating pests and as fungicides.

Description

The invention relates to new 4-amino and 4-hydrazinopyrimidines, processes for their manufacture and their use for controlling animal pests as well as fungicides.

It is already known that certain acylated 4-aminopyrimidine derivatives are insect have ticidal properties (cf. WO-A 95/18 795).

The level and / or duration of action of these previously known compounds is however, especially against certain organisms or for low users not entirely satisfactory in all areas of application.

New 4-amino and 4-hydrazinopyrimidines of the formula (I) have been found

in which
R¹ and R² independently of one another for hydrogen, halogen, nitro, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyl, haloalkoxyalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsul finyl, haloalkylsulfonyl, amino, alkylamino, dialkylamino, amino carbonyl, alkylaminocarbonyl, Dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, represent optionally substituted cycloalkyl or optionally substituted phenyl,
wherein at least one of R¹ and R² is not hydrogen;
or
R¹ and R² together with the carbon atoms to which they are attached represent an optionally substituted, saturated or unsaturated ring which optionally contains heteroatoms,
A stands for one of the groups -NR³- or -NR³-NR⁴-, where
R³ and R⁴ independently of one another represent hydrogen, alkyl, alkoxyalkyl, alkylcarbonyl, or in each case optionally substituted aryl and arylcarbonyl,
X represents oxygen or sulfur,
Y stands for a direct bond, in each case optionally substituted alkylidene, alkylideneoxy and alkylidethio or for alkenylidene and
Ar represents optionally substituted aryl or optionally substituted hetaryl.

Furthermore, it was found that the new acylated 4-amino and 4-hydra zinopyrimidines of the formula (I) are obtained when

• a) pyrimidine derivatives of the formula (II) in which
  A, R¹ and R² have the meaning given above,
  with acid halides of the formula (III) Hal-CO-Y-Ar (III) in which
  Y and Ar have the meaning given above and
  Hal stands for halogen,
  in the presence of a base and in the presence of a diluent;
  and if necessary
• b) the 4-amino- and 4-hydrazinopyrimidines of the formula (Ia) thus obtained in which
  A, R¹, R², Y and Ar have the meaning given above,
  with a sulfurizing agent, optionally in the presence of a diluent.

Furthermore, it was found that the new acylated 4-amino and 4-hydrazino pyrimidines of the formula (I) very good for controlling animal pests, especially of insects, arachnids and nematodes that are in the farmer shaft, in forests, in the protection of stored goods and materials as well as in the hygiene sector occur, are suitable.

Surprisingly, the acylated 4-amino and 4- Hydrazinopyrimidines of the formula (I) have a significantly better activity compared to animal pests known as the constitutionally similar compounds.

The acylated 4-amino and 4-hydrazinopyrimidines according to the invention are generally defined by formula (I).  

Preferred substituents or ranges of those in the above and below radicals mentioned formulas are explained below.

R¹ and R² independently of one another preferably represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C₁-C₆-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁- C₄-haloalkoxy, C₁-C₄-alkoxy- C₁-C₄-alkyl, C₁-C₄-haloalkoxy-C₁-C₄-alkyl, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl, C₁- C₂-haloalkylthio, C₁-C₂-haloalkylsulfinyl, C₁- C₂-haloalkylsulfonyl, amino, C₁-C₄-alkylamino, di (C₁-C₄) -alkylamino, aminocarbonyl, C₁-C₄-alkylaminocarbonyl, di (C₁-C₄) -alkylaminocarbonyl, aminothiocarbonyl, C₁-C₄-alkylaminothiocarbonyl, di ( C₁-C₄) -alkylaminothiocarbonyl, for optionally monosubstituted to trisubstituted, identically or differently, by halogen or C₁-C₄-alkyl substituted C₃-C₆-cycloalkyl or for optionally monosubstituted to trisubstituted, identically or differently, phenyl, the substituents being halogen, nitro, Cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C Haloalkyl, C₁-haloalkoxy and haloalkylthio C₁-C₄- eligible,
wherein at least one of the substituents R¹ and R² is not hydrogen or
R¹ and R² together with the carbon atoms to which they are attached are preferably an optionally single to triple, identical or different, halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio , C₁-C₄ haloalkyl, C₁-C₄ haloalkoxy or C₁-C₄ halo genalkylthio substituted, saturated or unsaturated 5- or 6-membered ring, which may contain 1 to 2 heteroatoms such as N, O or S atoms can.

A preferably represents one of the groupings -NR³- or -NR³-NR⁴-, wherein
R³ and R⁴ independently of one another for hydrogen, C₁-C₄-alkyl, C₁-C₄- alkoxy-C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl or for each optionally single to triple, identical or different by halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkyl thio, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or C₁-C₄-halo genalkylthio substituted phenyl or phenylcarbonyl.

X preferably represents oxygen or sulfur.

Y preferably stands for a direct bond, in each case optionally through Halogen or C₃-C₆-cycloalkyl substituted C₁-C₆-alkylidene, C₁-C₆- Alkylidenoxy and C₁-C₆-alkylidenthio or for C₂-C₆-alkenylidene.

Ar preferably represents phenyl which is monosubstituted to trisubstituted by identical or different substituents, the following being suitable as substituents:
Halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-haloalkylthio or each, if appropriate, once to three times, the same or differently substituted phenyl, phenoxy, phenylthio, benzyl, pyridinyloxy, pyrimidinyloxy, thiazolyloxy or thiadiazolyloxy, the following being suitable as substituents:
Halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-haloalkylthio; for condensed bi- or tricyclic radicals which are optionally monosubstituted to fivefold, identical or different, substituted by halogen, nitro, cyano or C₁-C₄alkyl and which can also contain heteroatoms, such as O, S or N atoms;
for optionally single to triple, identical or differently substituted 5- or 6-membered hetaryl with 1 to 3 heteroatoms, such as N, S and O atoms, the following being suitable as substituents:
Halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or C₁-C₄-haloalkylthio.

R¹ and R² independently of one another particularly preferably represent hydrogen, chlorine, bromine, nitro, cyano, methyl, ethyl, chloromethyl, trifluoromethyl, methoxy, ethoxy, trifluoromethoxy, methoxymethyl, ethoxymethyl, trifluoromethoxymethyl, methylthio, methylsulfinyl, methylsulfonyl, amino, methylamino, Dimethylamino, aminocarbonyl, aminothiocarbonyl;
for cyclopropyl, cyclopentyl or cyclohexyl optionally substituted once or twice, identically or differently, by fluorine, chlorine, bromine, methyl or ethyl;
or for phenyl which is monosubstituted to trisubstituted identically or differently, where fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy and trifluoromethylthio are possible substituents,
wherein at least one of the substituents R¹ and R² is not hydrogen or
R¹ and R² together with the carbon atoms to which they are attached are each optionally substituted once or twice, identically or differently, by fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio Phenyl, pyrazolyl, imidazolyl or thiazolyl.

A particularly preferably represents one of the groupings -NR³- or -NR³-NR⁴-, wherein
R³ and R⁴ independently of one another represent hydrogen, methyl, ethyl, meth oxymethyl, ethoxymethyl, ethoxyethyl, acetyl or, if appropriate, single or double, identical or different, substituted by fluorine, chlorine, nitro, cyano, methyl or trifluoromethyl-substituted benzoyl.

X particularly preferably represents oxygen or sulfur.

Y particularly preferably stands for a direct bond or for one of the groups strings -CH₂-, -CH (CH₃) -, -CH (C₂H₅) -, -CH (C₃H₇-i) -, -CH₂CH₂-, -CH₂O-, -CH₂S- or -CH = CH-.

Ar particularly preferably represents phenyl which is monosubstituted to trisubstituted identically or differently, the following being suitable as substituents:
Fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, n- and i-propyl, n-, i-, s- and t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, Difluoromethylthio or phenyl, phenoxy, pyridinyloxy, pyrimidinyloxy, thiazolyloxy or thiadiazolyloxy, each of which is monosubstituted to trisubstituted by identical or different substituents, the following being suitable as substituents:
Fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, n- and i-propyl, n-, i-, s- and t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio and Difluoromethylthio;
for one of the bi- or tricyclic radicals

which are optionally mono- to pentasubstituted, identical or different, by fluorine, chlorine, bromine, nitro, cyano, methyl or ethyl;
for one of the heteroaromatics of the formulas

which are optionally substituted once to three times, identically or differently are by fluorine, chlorine, nitro, cyano, methyl, ethyl, methoxy, methyl thio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio.

The Koh mentioned above in the definition of the compounds according to the invention Hydrogen residues such as alkyl can also be used in conjunction with heteroatoms such as Alkoxy - if possible, be straight-chain or branched.

The radicals listed above or listed in preferred areas Definitions or explanations can be made with each other, i.e. also between the respective areas and preferred areas can be combined as desired. they seem for the end products as well as for the preliminary and intermediate products accordingly.

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.  

Compounds of the general formulas (IA) to (ID) are particularly preferred

in which
Y and Ar stand for the abovementioned general, preferred and particularly preferred meanings.

In addition to the production examples, the following are examples Connections listed in the table:

For example, 4-amino-5-chloro-6-ethyl-pyri is used in process (a) midin and 4-bromophenylacetyl chloride as starting materials, so the course of the process according to the invention by the following reaction scheme again are given:

If, for example, N- (5-chloro-6-ethyl-4-pyri) is used according to process (b) midyl) -4- (4-nitrophenoxy) -phenylacetamide as starting material and Lawessons-Rea genz (2,4-bis- (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide) - as Sulfurizing agents, the course of the process according to the invention the following reaction scheme can be reproduced:

Those used to carry out process (a) according to the invention as starting materials required pyrimidine derivatives are generally defined by the formula (II). In of formula (II) A, R¹ and R² have preferred or particularly preferred those some meanings already in connection with the description of the Compounds of formula (I) preferred or particularly preferred for these Substituents were called.

Some of the pyrimidine derivatives of the formula (II) are known (cf., for example, Ras must, van der Plas, Recl. Trav. Chim. Pays-Bas 97: 288 (1978); J. Heterocycl. Chem. 28 (5), 1357 (1991)) or they can be obtained in a known manner (see also the following information on the preparation of new pyrimidine derivatives vate of formula (IIa)).

Not yet known and are also the subject of this application Pyrimidine derivatives of the formula (IIa)

in which
A has the meaning given above.

The new pyrimidine derivatives of the formula (IIa) are obtained by using the 4,5-dichloro-6-ethylpyrimidine of the formula (IV)

with amines or hydrazines of the formula (V)

H-A-H (V)

in which
A has the meaning given above,
in the presence of a base and optionally in the presence of a diluent.

All customary solvents can be used as diluents. Halogenated aliphatic or aromatic hydrocarbons, ethers or nitriles, such as. B. cyclohexane, toluene, Chlorobenzene, chloroform, dichloromethane, dichloroethane, dioxane, tetrahydrofuran, Diethyl ether or acetonitrile.

However, it is also possible to work in the melt without a diluent.

The method described above for the preparation of the compounds of formula (IIa) is carried out in the presence of a base.

All common proton acceptors can be used as bases. Alkali or alkaline earth metal hydroxides, alkali or earth are preferably usable alkali carbonates or bicarbonates or nitrogen bases. May be mentioned at for example sodium hydroxide, calcium hydroxide, potassium carbonate, sodium hydro gene carbonate, triethylamine, dibenzylamine, diisopropylamine, pyridine, quinoline, di azabicyclooctane (DABCO), diazabicyclonones (DBN) and diazabicycloundecene (DBU).

A corresponding excess of amine or hydrazine can preferably also be used of the formula (V) can be used.

The reaction temperatures can vary within a wide range will. In general, temperatures between -40 ° C and + 200 ° C, preferably between 0 ° C and 150 ° C.

In some cases, it turns out to be advantageous under increased pressure work.

When carrying out the method for producing the Ver Compounds of formula (IIa) are generally used per mole of 4,5-dichloro-6-ethyl  pyrimidine of the formula (IV) 1 to 3 mol, preferably 1 to 2 mol of amine or Hydrazine of formula (V).

The compounds of formula (IIa) are worked up and isolated in general my familiar way.

The 4,5-dichloro-6-ethylpyrimidine of the formula (IV) is known (cf. EP- A 0 370 391).

The amines or hydrazines of the formula (V) are generally known compounds of organic chemistry.

The also to carry out the method (a) as off Acid halides required starting materials are generally de by the formula (III) finishes. In formula (III), Y and Ar are preferred or particularly preferred those meanings that are already related to the description above of the compounds of formula (I) preferred or particularly preferred for this Substituents were called.

Hal preferably represents chlorine or bromine.

The acid halides of the formula (III) are generally known compounds of organic chemistry.

The starting materials of the formula (Ia) used in the production process (b) are compounds according to the invention and according to the information in the preparation method (a) available.

Suitable diluents for carrying out the inventive Process (a) all common solvents in question. Are preferably usable optionally halogenated aliphatic or aromatic hydrocarbons, Ethers or nitriles such as B. cyclohexane, toluene, chlorobenzene, chloroform, di chloromethane, dichloroethane, dioxane, tetrahydrofuran, diethyl ether or acetonitrile.

However, it is also possible to work in the melt without a solvent.  

The process (a) described above for the preparation of the compounds of For mel (I) is carried out in the presence of a base.

All conventional proton acceptors can be used as bases in process (a) will. Alkali or alkaline earth metal hydroxides, alkali metal or alkaline earth carbonates or bicarbonates or nitrogen bases. Called Examples include sodium hydroxide, calcium hydroxide, potassium carbonate and sodium hydrogen carbonate, triethylamine, dibenzylamine, diisopropylamine, pyridine, Quinoline, diazabicyclooctane (DABCO), diazabicyclonones (DBN) and diaza bicycloundecen (DBL).

A corresponding excess of pyrimidine derivative may also be used Formula (II) can be used.

The reaction temperatures in process (a) described above in can be varied over a wide range. Generally one works at Temperatures between -40 ° C and + 200 ° C, preferably between 0 ° C and 100 ° C.

When carrying out process (a) described above for producing the Compounds of formula (I) are generally used per mole of pyrimidine derivative of the formula (II) 0.1 to 2 mol, preferably 0.4 to 1.5 mol of the acid halide Formula (III).

The end products are worked up and isolated in a generally known manner and way.

The sulfurizing agents used in carrying out the invention Process (b) preferably in question: phosphorus pentasulfide or Lawesson-Rea genz [2,4-bis (4-methoxyphenyl) -1,3,2,4-dithiadiphosphetane-2,4-dithione] (see also Tetrahedron Vol. 41, No. 22, 5061ff (1985)).

Suitable diluents for carrying out the inventive Process (b) preferably hydrocarbons, such as toluene, xylene, tetralin, Hexane or cyclohexane in question.

The reaction temperatures can be carried out when carrying out the process according to the invention Process (b) can be varied over a wide range. Generally works  one at temperatures between 0 ° C and 200 ° C, preferably between 20 ° C and 150 ° C.

When carrying out process (b) according to the invention, the reaction is carried out per mole Compound of formula (Ia) generally between 1 and 3 moles, preferably between 1 and 2 moles of sulfurizing agent. The processing takes place according to methods.

In some cases, the pyrimidine derivatives may prove advantageous of the formula (II) directly with halides of the formula (IIIa)

Hal-CS-Y-Ar (IIIa)

in which
Hal, Y and Ar have the meaning given above,
to implement under the conditions of process a) described above.

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, Hofmannophila 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., Chrysomyia 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 characterized by excellent insecticidal activity. You can be special with good success in combating plant-damaging insects.

They show strong effects, for example, against horseradish leaf beetle larvae (Phaedon cochleariae), caterpillars caterpillars (Plutella maculipennis), caterpillars of the owl butterfly (Spodoptera frugiperda), the peach aphid (Mycus persicae) as well as against the green rice leafhopper (Nephotettix cincticeps).

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, chlorethylene or methylene chloride, aliphatic coal water serstoffe, 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 cyclohexanone, 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, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, as solid carriers for granules are possible: 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 stems; as emulsifying and / or foam-generating agents come into question: z. B. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersing agents 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 in its commercially available formulations as well as in the application forms prepared from these formulations in Mi with other active ingredients, such as insecticides, attractants, sterilants, Bactericides, acaricides, nematicides, fungicides, growth-regulating substances fen or herbicides. The insecticides include, for example, Phos phosphoric esters, carbamates, carboxylic esters, chlorinated hydrocarbons, Phenylureas, substances produced by microorganisms u. a.

Particularly cheap mixing partners are e.g. B. the following:  

Fungicides

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ′, 6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxanide; 2,6-di chloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxylmino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) 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, etridiazole,
Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanyl, Fuberilafil, Fuberri 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, tecnazene, tetraconazole, thiabendazole, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
Validamycin A, vinclozolin,
Zineb, ziram.

Bactericides

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, Kasugamy cin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, Tecloftalam, 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, Bensultap, Betacyfluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Buto carboxin, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorflua zuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrinhrhrhrinhrhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrofhrinhrinhrinhrofhrinothrinophrinothrinothrinhrhrinhrhrinhrofhrinothrinhrinhrhrinhrinhrinhrofhrinothrinophrinothrinophrinothrinophrinothrinophrinothrinophrinothrinophrinophrine , Cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenothxinfox, Fufionophon, Fufionophon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufon
HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, 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, Thio methon, Thionazin, Thuringiensin, Tralomichonon, Triaromenontron, Triaromenontron, Triarathenlarbon, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triaromenontrin, Triarathenltronium, Triaromenontrin, Triarathenltron, Triaromenontron
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 be from 0.0000001 to 95% by weight of active ingredient, preferably between 0.0001 and 1% by weight.  

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 and hygiene and storage pests, but also against in the veterinary sector animal parasites (ectoparasites) such as tortoise ticks, leather ticks, mite 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., 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., 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., Panstrongyius 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., Pneumonyssus 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 Examination 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 Deaths 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.), Implan tate, by nasal application, by dermal application in the form, for example of diving or bathing (dipping), spraying (spray), pouring on (pour-on and Spot-on), washing, powdering and with the help of active ingredients Shaped bodies, such as collars, ear tags, tail tags, limb straps, Halters, 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-fold dilution or use it as a chemical Use bath.

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

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, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, 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 protect against insect attack 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 substances as such, in the form of concentrates or in general Lichen formulations such as powders, granules, solutions, suspensions, emulsions 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. Generally in my opinion, however, it is sufficient 0.0001 to 20% by weight, preferably 0.001 to 10 wt .-%, of the active ingredient, based on the material to be protected.

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 minerals oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene used.

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

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

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

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

As an organic chemical binder in the present Er finding the known water-dilutable and / or in the used organic chemical solvents soluble or dispersing or emulsifying Resins and / or binding drying oils, especially binders consisting of or containing an acrylic resin, a vinyl resin, e.g. B. polyvinyl acetate, Polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene  Coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or Resin used.

The synthetic resin used as a binder can be in the form of an emulsion, disper sion or solution. Bitumen or bituminous substances up to 10 wt .-%, are used. In addition, you can dyes, pigments, water-repellants, odor 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 .-% before preferably 50 to 68 wt .-% used.

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

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

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

Water is also particularly suitable as a solvent or diluent, optionally in a mixture with one or more of the above organic 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 are particularly preferred as admixing partners pyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, delta methrin, permethrin, imidacloprid, M-25, flufenoxuron, hexaflumuron and tri flumuron, and fungicides such as epoxyconazole, hexaconazole, azaconazole, Pro piconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorfluanide, Tolyl fluanide, 3-iodo-2-propynyl butyl carbamate, N-octyl-isothiazolin-3-one and 4,5- Dichloro-N-octylisothiazolin-3-one.

The active compounds according to the invention also have a strong microbicidal action on and can be practical to combat unwanted microorganisms be used. The active ingredients are for use as pesticides, particularly suitable as fungicides.

Fungicides in crop protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomy cetes, Basidiomycetes, Deuteromycetes.

Bactericidal agents are used in plant protection to combat Pseudomonada ceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae used.

Some pathogens of fungal and bacterial diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:
Xanthomonas species, such as, for example, Xanthomonas campestris pv. Oryzae;
Pseudomonas species, such as, for example, Pseudomonas syringae pv. Lachrymans;
Erwinia species, such as, for example, Erwinia amylovora;
Pythium species, such as, for example, Pythium ultimum;
Phytophthora species, such as, for example, Phytophthora infestans;
Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis;
Plasmopara species, such as, for example, Plasmopara viticola;
Bremia species, such as, for example, Bremia lactucae;
Peronospora species, such as, for example, Peronospora pisi or P. brassicae;
Erysiphe species, such as, for example, Erysiphe graminis;
Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;
Podosphaera species, such as, for example, Podosphaera leucotricha;
Venturia species, such as, for example, Venturia inaequalis;
Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (conidial form: Drechslera, Syn: Helminthosporium);
Cochliobolus species, such as, for example, Cochliobolus sativus (conidial form: Drechslera, Syn: Helminthosporium);
Uromyces species, such as, for example, Uromyces appendiculatus;
Puccinia species, such as, for example, Puccinia recondita;
Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;
Tilletia species, such as, for example, Tilletia caries;
Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
Pellicularia species, such as, for example, Pellicularia sasakii;
Pyricularia species, such as, for example, Pyricularia oryzae;
Fusarium species, such as, for example, Fusarium culmorum;
Botrytis species, such as, for example, Botrytis cinerea;
Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria species, such as, for example, Leptosphaeria nodorum;
Cercospora species, such as, for example, Cercospora canescens;
Alternaria species, such as, for example, Alternaria brassicae;
Pseudocercosporella species, such as, for example, Pseudocercosporella herpotri choides.

The good plant tolerance of the active ingredients in the control of the plant Concentrations necessary for diseases allow treatment from above parts of plants, planting and seeds, and the soil.  

You can, for example, with particularly good success against the pathogen Apple Mildew (Podosphaera leucotricha) and Apple Scab (Venturia inaequalis) can be used.

In addition, they also have a good effect against diseases in fruit and vegetable growing, such as B. against the pathogen of the wrong vine mildew (Plas mopara viticola) or tomato brown rot (Phytophthora infestans); and also against rice spot disease (Pyricularia oryzae).

When used as fungicides, the active compounds according to the invention can be used as such, in the form of their commercial formulations or the applications prepared from them Forms of use, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules can be used. The application happens in the usual way, e.g. B. by pouring, spraying, spraying, Ver sprinkle, foam, brush, etc. It is also possible to replenish the active ingredients apply the ultra-low-volume process or the preparation of the active ingredient or inject the active ingredient into the soil yourself. It can also be Seeds of the plants are treated.

When treating parts of plants, the active substance concentrations can be in the application forms can be varied in a larger area: generally between 1 and 0.0001% by weight, preferably between 0.5 and 00.001% by weight.

In the seed treatment, amounts of active ingredient are generally from 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g.

When treating the soil, active ingredient concentrations are from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02% by weight at the site of action required.

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

Manufacturing examples example 1

To a solution of 3.05 g (19.4 mmol) of 4-amino-5-chloro-6-ethyl-pyrimidine (IIa 1) in 30 ml of tetrahydrofuran, 2.26 g (9.7 mmol) of 4- Bromophenylacetyl chloride and stirred for 16 hours at room temperature.

For working up, the solid is filtered off with suction, the filtrate is concentrated and the residue stood between dichloromethane and water, the org. Phase dried and constricted. If the raw product is triturated with a little ether, the pro is obtained product in the form of a solid.

1.80 g (52% of theory) of N- (5-chloro-6-ethyl-4-pyrimidyl) -4-bromophee are obtained nylacetamide, melting point 150-152 ° C.

Manufacture of the starting product

10 g (56 mmol) of 4,5-dichloro-6-ethyl-pyrimidine are concentrated in 200 ml Ammonia water stirred for 8 hours at 150 ° C in an autoclave. The fancy Solid is suctioned off and dried.

7.0 g (78% of theory) of 4-amino-5-chloro-6-ethyl-pyrimidine are obtained Melting point 136-137 ° C.  

Example 2

To a solution of 1.58 g (10 mmol) of 4-amino-5-chloro-6-ethyl-pyrimidine (IIa-1) and 0.95 g (12 mmol) of pyridine in 50 ml of dichloromethane are added dropwise at 0-10 ° C. 3.26 g (12 mmol) of 4- (4-cyano-phenoxy) phenylacetyl chloride and stirred for 16 hours at room temperature.

For working up, the reaction mixture is washed with dilute hydrochloric acid, Water, dries and evaporates.

3.66 g (93% of theory) of N- (5-chloro-6-ethyl-4-pyrimidyl) -4- (4-cyano are obtained phenoxy) phenylacetamide, melting point 77-80 ° C.

Example 3

To a solution of 3.73 (20 mmol) N- (5-chloro-6-ethyl-4-pyrimidyl) -N-methyl- hydrazine (IIa-2), 2.02 g (20 mmol) triethylamine and a spatula tip Diaza bicyclooctane (DABCO) in 50 ml of tetrahydrofuran is added dropwise at 0-10 ° C 4.21 g (20 mmol) 4-tert-butyl-phenylacetyl chloride and stirred for 16 hours in the room temperature.

For working up, the mixture is concentrated, the residue between methylene chloride and Distributed water and the org. Phase dried and concentrated.

6.55 g (91% of theory) of N '- (5-chloro-6-ethyl-4-pyrimidyl) -N'-methyl- N-4-tert-butyl-phenylacetic acid hydrazide with a melting point of 137 ° C.  

Manufacture of the starting product

To a solution of 17.7 g (100 mmol) of 4,5-dichloro-6-ethyl-pyrimidine in 150 ml 9.20 g (200 mmol) of methylhydrazine are added dropwise at 0 ° C. and 16 Stirred for hours at room temperature.

For working up, the solid is suctioned off and the filtrate is evaporated.

19.2 g (100% of theory) of N- (5-chloro-6-ethyl-4-pyrimidyl) -N-methyl hydrazine are obtained as an orange oil.
1 H-NMR (CDCl₃): 1.28 (t, 3H), 2.87 (q, 2H), 3.37 (s, 3H), 4.5 (br, 2H), 8.49 (s, 1H) ) ppm.

Example 4

3.59 g (20 mmol) of 4-amino-5-chloro-quinazoline are placed in 50 ml of tetrahydrofuran, 1.89 g (10 mmol) of 4-chlorophenyl acetyl chloride are added and 16 hours heated under reflux.

For working up, the solid is filtered off with suction, the filtrate is concentrated and the The residue is partitioned between dichloromethane and water, the organic phase dried and evaporated. When the raw product is triturated with a little ether the product is obtained in the form of a solid.

1.30 g (40% of theory) of 4- (4-chlorophenylacetylamino) -5-chlorine are obtained quinazoline, melting point 150-152 ° C.  

Example 5

4.0 g (30 mmol) adenine are placed in 20 ml pyridine, 24.1 g (90 mmol) (4- Cyano-phenoxy-4-phenyl-acetyl chloride was added and the mixture was refluxed for 3 hours heated.

For working up, the mixture is concentrated, the residue between warm sodium hydro Distributed gene carbonate solution and chloroform, the product filtered off and out Recrystallized ethanol.

8.9 g (80% of theory) of N- (4-cyano-phenoxy-4-phenyl-acetyl) adenine are obtained melting point 251-255 ° C.

Example 6

0.40 g (0.97 mmol) N- (5-chloro-6-ethyl-4-pyrimidyl) -4- (4-nitro-phenoxy) - phenylacetamide and 0.39 g (0.97 mmol) Lawessons reagent are mixed in 10 ml Toluene heated under reflux for 16 hours. The mixture is concentrated and worked up the product isolated by column chromatography.

0.08 g (19% of theory) of N- (5-chloro-6-ethyl-4-pyrimidyl) -4- (4-nitro phenoxy) phenylthioacetamide with a melting point of 102-104 ° C.  

Analog to the preparation examples 1 to 6 and according to the general An The following compounds of the formula (I) receive:

Table 1

Examples of use Example A Phaedon larval test

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

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amount of solvent and the given amount of emulsifier and dilute the concentrate with water to the ge 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, e.g. B. the compounds according to the preparation examples 8, 10, 13, 23, 24, 30, 35, 43, 52, 62, 71 and 74 in an exemplary Active ingredient concentration of 0.1% and 100% killed after 7 days.  

Example B Plutella test

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

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amount of solvent and specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars (Plutella maculipennis) occupied while the leaves are still moist.

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

In this test, e.g. B. the compounds according to the preparation examples 10, 13, 30, 43, 49, 52, 62, 63, 71 and 74 in an exemplary Active ingredient concentration of 0.1% and 100% killed after 7 days.  

Example C Spodoptera Frugiperda test

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

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amount of solvent and the given amount of emulsifier and dilute the concentrate with water to the ge 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, e.g. B. the compounds according to the preparation examples 15 13, 24, 42, 43, 47, 62, 67, 69, 71 and 74 in an exemplary Active ingredient concentration of 0.1%, killing 100 after 7 days.  

Example D Myzus test

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

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amount of solvent and specified amount of emulsifier and dilute the concentrate with water to the desired 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. Here means 100% that all aphids have been killed; 0% means that none Aphids were killed.

In this test, e.g. B. the compound according to Production Example 13 at an exemplary active ingredient concentration of 0.1%, a kill of 90% after 6 days.  

Example E Nephotettix test

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

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amount of solvent and specified amount of emulsifier and dilute the concentrate with water to the desired 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%. 100% means that all cicadas have been killed; 0% means that no cicadas are killed were.

In this test, at an exemplary active ingredient concentration of 0.1%, e.g. B. the compounds according to the preparation examples

47 and 56 80% kill;
43 and 44 90% kill;
37 a kill rate of 95% and
35 and 72 a 100% kill,

every 6 days.  

Example F Podosphaera test (apple) / protective

Solvent: 4.7 parts by weight of acetone
Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emul gator and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are used with the active ingredient preparation sprayed. After the spray coating has dried on, the plants by dusting with conidia of the powdery mildew Podosphaera leucotricha inoculated.

The plants are then grown in a greenhouse at 23 ° C and relative air humidity of approx. 70%.

Evaluation is carried out 10 days after the inoculation.

In this test, e.g. B. the compound according to Preparation Example 52 with an exemplary active ingredient concentration of 100 ppm an efficiency of 98%.  

Example G Venturia test (apple) / protective

Solvent: 4.7 parts by weight of acetone
Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emul gator and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are treated with the active ingredient sprayed fabric preparation. After the spray coating has dried on, the plants Zen with an aqueous conidia suspension of the Venturia inae apple scab pathogen Qualis inoculated and then remain at 20 ° C and 100% relative air for 1 day humidity in an incubation cabin.

The plants are then grown in a greenhouse at 20 ° C and relative air humidity of approx. 70%.

Evaluation is carried out 12 days after the inoculation.

In this test, e.g. B. the compound according to Preparation Example 52 with an active ingredient concentration of 100 ppm, an efficiency of 99%.

Claims (8)

1. Compounds of formula (I) in which
R¹ and R² independently of one another for hydrogen, halogen, nitro, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyl, haloalkoxyalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, halo genalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, amino, alkylamino, dialkylamino, aminocarbonyl, alkylkaminocarbonyl Aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, represent optionally substituted cycloalkyl or optionally substituted phenyl,
wherein at least one of R¹ and R² is not hydrogen;
or
R¹ and R² together with the carbon atoms to which they are attached represent an optionally substituted, saturated or unsaturated ring which optionally contains heteroatoms,
A stands for one of the groups -NR³- or -NR³-NR⁴-, where
R³ and R⁴ independently of one another represent hydrogen alkyl, alkoxy alkyl, alkylcarbonyl, or in each case optionally substituted aryl and arylcarbonyl,
X represents oxygen or sulfur,
Y stands for a direct bond, in each case optionally substituted alkylidene, alkylideneoxy and alkylidethio or for alkenylidene and
Ar represents optionally substituted aryl or optionally substituted hetaryl. 2. A process for the preparation of compounds of formula (I) according to claim 1, characterized in that

• a) compounds of the formula (II) in which
  A, R¹ and R² have the meaning given in claim 1,
  with compounds of the formula (III) Hal-CO-Y-Ar (III) in which
  Y and Ar have the meaning given in claim 1 and
  Hal stands for halogen,
  in the presence of a base and in the presence of a diluent;
  and if necessary
• b) the compounds of the formula (Ia) thus obtained in which
  A, R¹, R², Y and Ar have the meaning given above,
  with a sulfurizing agent, optionally in the presence of a diluent.

3. Compounds of the formula (IIa) in which
A has the meaning given in claim 1. 4. Pesticides and fungicidal agents, characterized by a content of at least one compound of the formula (I) according to An saying 1. 5. Use of compounds of formula (I) according to claim 1 for loading fighting pests and fungi. 6. Process for combating pests and fungi, characterized thereby records that compounds of formula (I) according to claim 1 Pests or fungi and / or their habitat. 7. Process for the manufacture of pesticides and fungizi the agents, characterized in that compounds of the formula  (I) according to claim 1 with extenders and / or surfactants mixed. 8. Use of compounds of formula (I) according to claim 1 for Manufacture of pesticides and fungicides.