EP1412334A1 - Pyrazoline derivatives and their use as pesticides - Google Patents

Abstract

The invention relates to novel pyrazoline derivatives of formula (I), in which R?1, R2, R3 and R4¿ have the meanings as cited in the description, to a number of methods for producing these substances, to their use for controlling pests, and to novel intermediate products and methods for the production thereof.

Description

PYRAZOLINE DERIVATIVES AND THEIR USE AS A PEST CONTROL

The present invention relates to new pyrazoline derivatives, ner processes for their preparation and their use as pesticides.

It is known that certain substituted pyrazolines have insecticidal and acaricidal properties (cf. e.g. DE-A 44 16 112, EP-A 0 679 644 or EP-A 0 438 690). However, the action of these compounds is not always entirely satisfactory, especially at low active compound concentrations and application rates.

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

in which

R ^{1 represents} cyano, alkoxycarbonyl, carbamoyl, thiocarbamoyl, alkylaminocarbonyl or dialkylaminocarbonyl,

R ^{2 represents} halogen, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfonyl, haloalkylsulfmyl, haloalkylsulfonyl or cyano,

R ^{3 represents} halogen, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, haloalkylsulfmyl, haloalkylsulfonyl or cyano and

R ^{4 represents} hydrogen, cyanomethyl or alkoxycarbonyl. Depending on the type and number of the substituents, the Nerbindungen of the formula (I) can optionally be present as geometric and / or optical isomers, regioisomers or confectioning isomers or their isomer mixtures in different compositions. Both the pure isomers and the isomer mixtures are claimed according to the invention.

Furthermore, it was found that the pyrazoline derivatives of the formula (I) can be obtained by

a) pyrazolines of the formula (II)

R ¹ and R ^{2 have} the meanings given above,

with isocyanates of the formula (III)

in which

R ^{3 has} the meanings given above if appropriate in the presence of a ner diluent and if appropriate in the presence of a catalyst; and

b) optionally the pyrazoline derivatives of the formula (Ia) obtained in this way

R ¹ , R ² and R ^{3 have} the meanings given above,

with halides of the formula (IN)

Shark ¹ - R ⁴ (IV) in which

R ^{4 has} the meanings given above and

Shark ^{1 represents} halogen,

if appropriate in the presence of a ner diluent and if appropriate in the presence of a base.

It was also found that pyrazoline derivatives of the formula (Ib) in which

R ¹ , R ² and R ^{3 have} the meanings given above,

also get by

c) pyrazolines of the formula (II)

R ¹ and R ^{2 have} the meanings given above,

with carbamic acid chlorides of the formula (N)

in which

R ^{3 has} the meanings given above,

in the presence of a diluent and optionally in the presence of a base.

Finally, it was found that the new pyrazoline derivatives of the formula (I) have highly pronounced biological properties and above all to control animal pests, in particular insects, arachnids and nematodes, which are used in agriculture, in forests, in the protection of stocks and materials as well as in the hygiene sector are suitable.

Formula (I) generally defines the pyrazoline derivatives according to the invention.

Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below:

R ¹ preferably represents cyano, -CC ₄ alkoxy-carbonyl, carbamoyl, thiocarbamoyl, -C-C ₄ -alkylamino-carbonyl or di-Cι-C ₄ -alkylamino-carbonyl.

R ² preferably represents fluorine, chlorine, bromine, iodine; -C-C ₄ haloalkyl, C1-C4 haloalkoxy, C _r C - alkylthio, C ^ haloalkylthio, C ₁ -C alkylsulfonyl, CC ^ haloalkylsulfonyl or cyano.

R ³ preferably represents fluorine, chlorine, bromine, iodine; -C-C ₄ haloalkyl, Cj-C ₄ haloalkoxy, C _j -C haloalkylthio, C i -C haloalkylsulfmyl, C ₁ -C ₄ haloalkylsulfonyl or cyano.

R ⁴ preferably represents hydrogen, cyanomethyl or C jC -alkoxy-carbonyl. R ¹ particularly preferably represents cyano, -CC ₄ -alkoxy-carbonyl, carbamoyl, thiocarbamoyl, -C-C2-alkylamino-carbonyl or di- -C-C2-alkylamino-carbonyl.

R ² particularly preferably represents fluorine, chlorine, bromine, iodine, cyano; -C-C2-alkyl thio, C _j ^ -alkylsulfonyl and for Cj -C2-haloalkyl, C _j ^ -haloalkoxy, Cι-C2-haloalkylthio or Cι-C ₂ -haloalkylsulfonyl, each with 1 to 5 identical or different halogen atoms from the series fluorine, chlorine and bromine.

R ³ particularly preferably represents chlorine, bromine, iodine, cyano; as well as for C1-C2-haloalkyl, Ci ^ -haloalkoxy, C _] -C2-haloalkylthio, Ci ^ -haloalkylsulfmyl or C _! -C2-Haloalkylsulfonyl, each with 1 to 5 identical or different halogen atoms from the fluorine, chlorine and bromine series.

R ⁴ particularly preferably represents hydrogen, cyanomethyl or C1-C4-alkoxycarbonyl.

Preference is furthermore given to compounds of the formula (I) in which R ^{1 represents} cyano.

Also preferred are compounds of formula (I) in which R ^{4 represents} hydrogen or CH ₂ CN.

Also preferred are compounds of formula (I) in which R ^{2 represents} halogen, preferably fluorine, chlorine, bromine or iodine, particularly preferably fluorine, chlorine or bromine, very particularly preferably chlorine.

The general definitions or explanations given above or in preferred areas apply to the end products and to the initial and Intermediates accordingly. These residual definitions can be combined with one another, i.e. also between the respective preferred areas.

According to the invention, preference is given to the compounds of the formula (I) in which there is a combination of the meanings listed above as preferred.

According to the invention, particular preference is given to the compounds of the formula (I) in which there is a combination of the meanings listed above as being particularly preferred.

In the radical definitions given above and below, carbon radicals, such as alkyl - are also straight-chain or branched as far as possible, also in conjunction with heteroatoms such as alkoxy.

If, for example, 3- (4-chlorophenyl) -4- (4-cyanopyrazol-l-yl) -4,5-dihydro-1H-pyrazole and 4-chlorophenyl isocyanate are used as starting materials, the reaction sequence of process (a) according to the invention can be carried out by the following formula scheme can be reproduced:

If, for example, 3- (4-chloro-henyl) -4- (4-cyano-pyrazol-l-yl) -4,5-di-hydro-l-pyrazolecarboxylic acid-4-chloroanilide and bromoacetonitrile are used as starting materials, the reaction can proceed of process (b) according to the invention can be represented by the following formula:

If, for example, 3- (4-chlorophenyl) -4- (4-cyanopyrazol-l-yl) -4,5-dihydro-1 H-pyrazole and N-cyanomethyl-N- (4-trifluoromethoxyphenyl) carbamoyl chloride are used as Starting materials, the course of the reaction of process (c) according to the invention can be represented by the following formula:

Formula (II) provides a general definition of the pyrazolines to be used as starting materials for carrying out processes (a) and (c) according to the invention. In this formula, R ¹ and R ² preferably or particularly preferably have those meanings which have already been mentioned as preferred or particularly preferred for these radicals in connection with the description of the compounds of the formula (I) according to the invention.

The pyrazolines of formula (II) are new and also the subject of this application. You will get by one substituted acetophenones of the formula (VI)

in which

R ¹ and R ^{2 have} the meanings given above,

in a first stage with bis-dialkylaminomethanes of the formula (VII)

(Alk) ₂ N-CH ₂ - N (Alk) ₂ (VII)

in which

Alk represents C _r C ₄ alkyl,

in the presence of an inert organic solvent (preferably

Halogenated hydrocarbons, e.g. Methylene chloride or ethylene chloride) at temperatures between 0 ° C and 120 ° C, preferably between 20 ° C and 80 ° C (see e.g. EP-A 0 546 420) and the resulting dialkylaminoalkyl ketones of the formula (VIII)

in which

R ¹ , R ² and Alk have the meanings given above, optionally isolated and reacted in a second stage with hydrazine (hydrate) in the presence of an inert organic solvent (preferably alcohols, such as methanol or ethanol) at temperatures between 0 ° C. and 80 ° C., preferably between 20 ° C. and 50 ° C. (see also the manufacturing examples).

Formula (III) provides a general definition of the isocyanates to be used as starting materials in process (a) according to the invention. In this formula, R ³ preferably or particularly preferably has those meanings which have already been associated with the description of the compounds of the invention

Formula (I) for this radical have been mentioned as preferred or particularly preferred.

The isocyanates of the formula (III) are generally known compounds of organic chemistry and / or can be obtained in a generally known manner.

Formula (VI) provides a general definition of the substituted acetophenones to be used as starting materials for carrying out process (d) according to the invention. In this formula, R ¹ and R ² preferably or particularly preferably have those meanings which have already been mentioned as preferred or particularly preferred for these radicals in connection with the description of the compounds of the formula (I) according to the invention.

The substituted acetophenones of formula (VI) are new and also the subject of this application. You will get by one

e) haloacetophenones of the formula (IX)

in which R ^{2 has} the meanings given above and

Shark ^{2 represents} halogen,

with pyrazoles of the formula (X)

in which

R ^{1 has} the meanings given above,

in the presence of an organic or inorganic base (eg potassium carbonate) and optionally in the presence of an inert organic solvent (eg acetonitrile) at temperatures between 0 ° C and 100 ° C, preferably between 20 ° C and 80 ° C (see, for example, EP-A 0438 690 and also the production examples).

Formula (VII) provides a general definition of the bis-dialkylaminomethanes to be used as starting materials in process (d) according to the invention. In this formula, Alk preferably represents methyl.

Bis-dialkylaminomethanes of the formula (VII) are generally known compounds of organic chemistry and / or can be obtained in a generally known manner. Formula (IX) provides a general definition of the haloacetophenones to be used as starting materials for carrying out process (e) according to the invention. In this formula, R ² preferably or particularly preferably has those meanings which are already in connection with the description of the invention Ner compounds of the formula (I) were mentioned as preferred or particularly preferred for this radical. Shark ² is preferably chlorine or bromine.

Formula (X) provides a general definition of the pyrazoles to be used as starting materials in the ner process (e) according to the invention. In this formula, R ¹ preferably or particularly preferably has those meanings which have already been mentioned as preferred or particularly preferred for this radical in connection with the description of the novel compounds of the formula (I) according to the invention.

The haloacetophenones of the formula (IX) and the pyrazoles of the formula (X) are generally known compounds of organic chemistry and / or can be obtained in a generally known manner.

The substituted acetophenones of the formula (Via)

in which

R ⁵ and R ⁶ independently of one another represent hydrogen or alkyl,

can also be obtained by using

f) substituted acetophenones of the formula (VIb)

in which

R ^{2 has} the meanings given above,

in a first stage with mineral acids (such as preferably hydrochloric acid or

Sulfuric acid) in the presence of an inert solvent (preferably a polar solvent, such as water or acetic acid) at temperatures between 50 ° C and 140 ° C, preferably between 80 ° C and 120 ° C, the mineral acid being used in excess; and the resulting substituted acetophenones of the formula (VIc)

in which

R ^{2 has} the meanings given above,

isolated and in a second stage first with thionyl chloride and then with ammonia or an amine of the formula (XI)

HNR ⁵ R ⁶ (XI) in which

R ⁵ and R ^{6 have} the meanings given above,

in the presence of an inert, organic solvent (for example methylene chloride or tetrahydrofuran) at temperatures between 0 ° C. and 100 ° C., preferably between 20 ° C. and 80 ° C., the ammonia or the amine is used in excess, which also have the function of a base here (cf. also the preparation examples).

Formula (VIb) provides a general definition of the substituted acetophenones to be used as starting materials for carrying out process (f) according to the invention. In this formula, R ² preferably or particularly preferably has those meanings which have already been mentioned as preferred or particularly preferred for this radical in connection with the description of the compounds of the formula (I) according to the invention.

The substituted acetophenones of the formula (VIb) are likewise compounds of the invention and can be obtained by process (e).

Formula (XI) generally defines the amines to be used as starting materials in process (f) according to the invention. In this formula, R ⁵ and R ⁶ independently of one another preferably represent hydrogen or Cj-C ₄ - alkyl, particularly preferably represents hydrogen or C -C ₂ alkyl!.

The amines of the formula (XI) are generally known compounds of organic chemistry.

Formula (IV) provides a general definition of the halides to be used as starting materials for carrying out process (b) according to the invention. In this formula, R ⁴ preferably or particularly preferably has those meanings which have already been mentioned as preferred or particularly preferred for this radical in connection with the description of the compounds of the formula (I) according to the invention. Shark ¹ preferably represents chlorine or bromine.

The halides of the formula (IV) are generally known compounds of organic chemistry. Formula (V) provides a general definition of the carbamic acid chlorides to be used as starting materials in process (c) according to the invention. In this formula, R ³ preferably or particularly preferably has those meanings which have already been mentioned as preferred or particularly preferred for this radical in connection with the description of the compounds of the formula (I) according to the invention.

Some of the carbamic acid chlorides of the formula (V) are known (cf. e.g. DE 27 30 325). Not yet known and also the subject of this application are carbamic acid chlorides of the formula (Va)

in which

R ^{7 represents} haloalkyl, haloalkoxy or haloalkylthio, preferably the corresponding preferred meanings of R ³ .

The carbamic acid chlorides of the formula (Va) are obtained, for example, by

g) cyanomethylanilines of the formula (XII)

in which R ^{7 has} the meanings given above,

with phosgene in the presence of an inert organic diluent (e.g. toluene) and in the presence of a base (preferably tertiary organic amines such as triethylamine) at temperatures between -10 ° C and

+ 120 ° C, preferably between 0 ° C and 100 ° C, wherein the phosgene can be used in a slight excess (see also the preparation examples).

The cyanomethylanilines of the formula (XII) are new and also the subject of these

Registration. You can get one by, for example

h) known anilines of the formula (XIII)

in which

R ^{7 has} the meanings given above,

in the presence of acetic acid with paraformaldehyde and alkali metal cyanide at temperatures between 20 ° C and 60 ° C (see e.g. Helv. Chim. Acta 1954, 37, 166 and the preparation examples).

In a particular embodiment of process (c), it is also possible to carry out the process in a so-called one-pot process, starting from the cyanomethylanilines of the formula (XII).

Process (a) according to the invention is preferably carried out using diluents. Practically all inert organic solvents can be used as diluents. These preferably include aliphatic ones and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl and dibutyl ether, methyl ether tert-butyl ether, methyl tert-amyl ether, glycol dimethyl 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 ester , Nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide, dimethyl acetamide and N-methylpyrrolidone and dimethyl sulfoxide, tetramethylene sulfone or hexamethylphosphoric acid triamide.

Process (a) according to the invention is preferably also carried out using a catalyst. In particular, tertiary organic amines such as triethylamine are suitable as catalysts.

The reaction temperatures in process (a) according to the invention can be varied within a substantial range. In general, temperatures between 0 ° C and 120 ° C, preferably at temperatures between 20 ° C and 80 ° C.

Process (a) according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.

To carry out process (a) according to the invention, the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components used in a smaller excess. Working up is carried out using customary methods (cf. the production examples).

Processes (b) and (c) according to the invention are preferably carried out using diluents. Suitable diluents are all inert organic solvents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl - And dibutyl ether, glycol dimethyl 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 as acetonitrile or propionitrile, amides such as eg dimethylformamide, dimethylacetamide and N-methylpyrrolidone and dimethyl sulfoxide, tetramethylene sulfone or hexamethylphosphoric triamide.

Bases which can be used in carrying out processes (b) and (c) according to the invention are all acid binders which can customarily be used for such reactions. Alkali metal and alkaline earth metal hydrides, such as lithium, sodium, potassium or calcium hydride; Alkali metal and alkaline earth metal hydroxides, such as lithium, sodium, potassium or calcium hydroxide; Alkali metal and alkaline earth metal carbonates or bicarbonates, such as sodium or potassium carbonate or bicarbonate or calcium carbonate; Alkali metal acetates, such as sodium or potassium acetate, alkali metal alcoholates, such as sodium or potassium tert-butoxide; basic nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine, ethyldiisopropylamine, ethyldicyclohexylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline, pyridine, 2-methyl-, 3-methyl- , 4-methyl, 2,4-dimethyl, 2,6-dimethyl, 2-ethyl, 4-ethyl and 5-ethyl-2-methylpyridine, 1,5-diazabicyclo- [4.3.0] - non-5-ene (DBN), 1,8-diaza-bicyclo [5.4.0] -undec-7-ene (DBU), 1,4-diaza-bicyclo [2.2.2] octane (DABCO).

The reaction temperatures in process (b) according to the invention can be varied within a substantial range. In general, temperatures between 0 ° C and 120 ° C, preferably at temperatures between 20 ° C and 80 ° C. Process (b) according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.

To carry out process (b) according to the invention, the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use the halide and the base in excess. Working up is carried out using customary methods (cf. the production examples).

The reaction temperatures in process (c) according to the invention can be varied within a substantial range. In general, temperatures between - 10 ° C and + 130 ° C, preferably at temperatures between 0 ° C and 110 ° C.

Process (c) according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.

To carry out process (c) according to the invention, the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use the chloride and the base in excess. Working up is carried out using customary methods (cf. the production examples).

With good plant tolerance and favorable warm-blooded toxicity, the active substances are suitable for controlling animal pests, especially insects,

Arachnids and nematodes found in agriculture, in forests, in the protection of stocks and materials, and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above include: From the order of the Isopoda, for example Oniscus asellus, Armadillidium vulgare, Porcellio scaber.

From the order of the Diplopoda e.g. Blaniulus guttulatus.

From the order of the Chilopoda e.g. Geophilus carpophagus, Scutigera spp. From the order of the Symphyla e.g. Scutigerella immaculata.

From the order of the Thysanura e.g. Lepisma saccharina.

From the order of the Collembola e.g. Onychiurus armatus.

From the order of the Orthoptera e.g. Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria. From the order of the Blattaria e.g. Blatta orientalis, Periplaneta americana,

Leucophaea maderae, Blattella germanica.

From the order of the Dermaptera e.g. Forficula auricularia.

From the order of the Isoptera e.g. Reticulitermes spp.

From the order of the Phthiraptera e.g. Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp.

From the order of the Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci,

Thrips palmi, Frankliniella accidentalis.

From the order of the Heteroptera e.g. Eury gaster spp., Dysdercus intermedius,

Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp. From the order of the Homoptera e.g. 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 striatatausidumonidia, aphantella lantophosphate aphidata, pseudophilia stratata, pseudophilia stratata, pseudophilia stratata, pseudophyllum aphid, sap ., Psylla spp.

From the order of the Lepidoptera e.g. Pectinophora gossypiella, Bupalus piniarius,

Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Fuxia spp.

Earias insulana, Heliothis spp., Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Chorua magnone fella, Chorus Tortrix viridana, Cnaphalocerus spp., Oulema oryzae.

From the order of the Coleoptera e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephuspp 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., Agribiole spp., Tenebrio molitor. Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica, Lissorhoptrus oryzophilus.

From the order of the Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera e.g. 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, Hylemyia spp., Liriomy From the order of the Siphonaptera, for example Xenopsylla cheopis, Ceratophyllus spp. From the class of the Arachnida, for example, Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., ., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp., Brevipalpus spp. The plant-parasitic nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Tripusichpp. Spp., Xiphinema spp.

The substances according to the invention can be used with particularly good success for combating plant-damaging insects, such as e.g. against the larvae of the cucumber beetle (Diabrotica balteata), the caterpillars of the cotton capsule worm (Heliothis virescens), the larvae of the horseradish beetle (Phaedon cochleariae), the caterpillars of the cockroach (Plutella xylostella) and caterpillars of the army worm

(Spodoptera exigua and Spodoptera frugioerda).

The substances according to the invention also show a very good duration of action, e.g. against the caterpillars of the cotton capsule worm (Heliothis virescens) or the caterpillars of the army worm (Spodoptera frugiperda).

If appropriate, the compounds according to the invention can also be used in certain concentrations or application rates as herbicides and microbicides, for example as fungicides, antifungals and bactericides. If appropriate, they can also be used as intermediates or precursors for the synthesis of further active compounds.

According to the invention, all plants and parts of plants can be treated. Plants are understood here to mean all plants and plant populations, such as desired and unwanted wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including those which can or cannot be protected by plant breeders' rights

Plant varieties. Under plant parts, all above-ground and underground Parts and organs of the plants, such as sprout, leaf, flower and root, are to be understood, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, and roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and

Seeds.

The treatment of the plants and parts of plants with the active compounds according to the invention is carried out directly or by acting on their surroundings, living space or storage space according to the customary treatment methods, e.g. by dipping, spraying,

Evaporation, nebulization, scattering, spreading and, in the case of propagation material, in particular seeds, furthermore by means of single- or multi-layer coating.

The active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances and very fine encapsulations in polymers substances.

These formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is liquid solvents and / or solid

Carriers, where appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.

If water is used as an extender, e.g. also organic

Solvents are used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. 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.

Possible solid carriers are: e.g. Ammonium salts and natural rock flours, such as kaolins, clays,

Talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates, are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are possible: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue 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 of active compound, preferably between 0.5 and 90%. The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the activity spectrum or to prevent the development of resistance. In many cases, synergistic effects are obtained, ie the effectiveness of the mixture is greater than that

Effectiveness of the individual components.

The following connections can be considered as mixed partners:

fungicides:

Aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole,

azoxystrobin,

Benalaxyl, benodanil, benomyl, benzamacril, benzamacrylic isobutyl, bialaphos,

Binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,

Calcium polysulphide, carpropamid, capsimycin, captafol, captan, carbendazim, carbonyl xin, carvone, chinomethionat (Quinomethionat) Chlobenthiazon, chlorfenazole, chlorides roneb, chloropicrin, chlorothalonil, chlozolinate, Clozylacon, Cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram, debacarb , Dichlorophene, diclobutrazole, diclofluanide, diclomezin, dicloran,

Diethofencarb, Difenoconazol, Dimethirimol, Dimethomorph, Diniconazol, Diniconazol-M, Dinocap, Diphenylamine, Dipyrithione, Ditalimfos, Dithianon, Dodemoφh, Dodine, Drazoxolon, Ediphenphos, Epoxiconazol, Etaconamol, Fenidamololololimololololololololololololazolololidolololololazololololazolololololololololazolololololazololololololololololololololololololol, formerly Fenhexamid, fenipropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzon, fluazinam, flumetover, fluoromid, fluquinconazole, flurprimidol, flusilazole, flusulfamide, flutolanil, flutriafos, fodyl, falidium-fulyltol, fylamino-fetyl, f-allyl-fulyltol, f-allylfosol, fylam-allyl, f-alphosol, f-alphol-fetyl, f-alphosol Fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox, guazatin,

Hexachlorobenzene, hexaconazole, hymexazole, Imazalil, imibenconazole, iminoctadine, iminoctadineal besilate, iminoctadine triacetate,

Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Iprovalicarb, Irumamycin,

Isoprothiolan, isovaledione,

Kasugamycin, Kresoxim-methyl, copper preparations such as: copper hydroxide, copper phthalate, copper oxychloride, copper sulfate, copper oxide, oxy-copper and

Bordeaux mixture,

Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl,

Metconazole, methasulfocarb, methfuroxam, metiram, metomeclam, metsulfovax,

Mildiomycin, Myclobutanil, Myclozolin, Nickel-dimethyldithiocarbamate, Nitrothal-Isopropyl, Nuarimol,

Ofurace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,

Paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen, picoxystrobin,

Pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidone,

Propamocarb, propanosine sodium, propiconazole, propineb, pyraclostrobin, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,

Quinconazole, quintozen (PCNB), quinoxyfen,

Sulfur and sulfur preparations, spiroxamines,

Tebuconazole, tecloftalam, tecnazen, tetcyclacis, tetraconazole, thiabendazole,

Thicyofen, Thifluzamide, Thiophanate-methyl, Thiram, Tioxymid, Tolclofos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazbutil, Triazoxid, Trichlamid, Tricyclazol,

Tridemorph, trifloxystrobin, triflumizole, triforin, triticonazole,

uniconazole

Validamycin A, vinclozolin, viniconazole,

Zarilamid, Zineb, Ziram and Dagger G,

OK 8705,

OK-8801, α- (l, 1-dimethylethyl) -ß- (2-phenoxyethyl) - 1 H-1, 2,4-triazole-1-ethanol, α- (2,4-dichlorophenyl) -ß-fluorine -ß-propyl-lH-l, 2,4-triazole-l-ethanol, α- (2,4-dichlorophenyl) -ß-methoxy-α-methyl- 1 H- 1, 2,4-triazole-1 - ethanol, - (5-methyl-l, 3-dioxan-5-yl) -ß - [[4- (trifluoromethyl) phenyl] methylene] -lH-l, 2,4-triazol-1-ethanol,

(5RS, 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (1 H-1, 2,4-triazol-1-yl) -3-octanone,

(E) -α- (methoxyimino) -N-methyl-2-phenoxy-phenylacetamide, 1 - (2,4-dichlorophenyl) -2- (1 H-1, 2,4-triazol-1-yl) -ethanone -O- (phenylmethyl) oxime,

1 - (2-methyl-1-naphthalenyl) - 1 H-pyrrole-2,5-dione, l- (3,5-dichlorophenyl) -3- (2-propenyl) -2,5-pyrrolidinedione,

1 - [(diiodomethyl) sulfony 1] -4-methyl 1-benzene,

1 - [[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl] -1 H-imidazole, 1 - [[2- (4-chloro-phenyl) -3-phenyloxiranyl] - methyl] - 1 Hl, 2,4-triazole,

1 - [1 - [2- [(2,4-dichlorophenyl) methoxy] phenyl] ethenyl] -1 H-imidazole, 1-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol,

2 ', 6 ^, -dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-l, 3-thiazole-5-carboxanilide, 2,6-dichloro-5- (methylthio) -4-pyrimidinyl- thiocyanate,

2,6-dichloro-N- (4-trifluoromethylbenzyl) -benzamide,

2,6-dichloro-N - [[4- (trifluoromethyl) phenyl] methyl] benzamide,

2- (2,3,3-triiodo-2-propenyl) -2H-tetrazole,

2 - [(1-methylethyl) sulfonyl] -5- (trichloromethyl) -1, 3,4-thiadiazole, 2 - [[6-deoxy-4-O- (4-O-methyl-β-D-glycopyranosyl ) -α-D-glucopyranosyl] amino] -4-methoxy-1H-pyrrolo [2,3-d] pyrimidine-5-carbonitrile,

2-aminobutane,

2-bromo-2- (bromomethyl) -pentandinitril,

2-chloro-N- (2,3-dihydro-l, l, 3-trimethyl-lH-inden-4-yl) -3-pyridinecarboxamide, 2-chloro-N- (2,6-dimethylphenyl) -N- (isothiocyanatomethyl) -acetamide,

2-phenylphenol (OPP),

3,4-dichloro-l- [4- (difluoromethoxy) phenyl] -lH-pyrrole-2,5-dione,

3,5-dichloro-N- [cyano [(l-methyl-2-propynyl) -oxy] -methyl] -benzamide,

3 - (1,1-dimethylpropyl-1-oxo-1 H-indene-2-carbonitrile, 3- [2- (4-chlorophenyl) -5-ethoxy-3-isoxazolidinyl] pyridine,

4-chloro-2-cyano-N, N-dimethyl-5- (4-methylphenyl) -lH-imidazol-l-sulfonamide, 4-methyl-tetrazolo [1, 5-a] quinazolin-5 (4H) -one, 8-hydroxyquinoline sulfate,

9H-xanthene-9-carboxylic acid-2- [(phenylamino) -carbony 1] -hydrazide, bis- (l-methylethyl) -3-methyl-4 - [(3-methylbenzoyl) -oxy] -2,5- thiophene dicarboxylate, ice 1 - (4-chlorophenyl) -2- (1 H-1, 2,4-triazol-1-yl) -cy cloheptanol, cis-4- [3- [4- (l, l-dimethylpropyl ) -phenyl-2-methylpropyl] -2,6-dimethyl-morpholine hydrochloride,

Ethyl - [(4-chlorophenyl) azo] cyanoacetate,

Potassium hydrogen carbonate, methane tetrathiol sodium salt,

Methyl 1 - (2,3-dihydro-2,2-dimethyl-1 H-inden-1-yl) - 1 H-imidazole-5-carboxylate, methyl-N- (2,6-dimethylphenyl) -N- (5-isoxazolylcarbonyl) -DL-alaninate, methyl-N- (chloroacetyl) -N- (2,6-dimethylphenyl) -DL-alaninate, N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro -2-oxo-3-furanyl) acetamide, N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-thienyl) acetamide,

N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide, N- (4-cyclohexylphenyl) -1, 4,5,6-tetrahydro-2-pyrimidinamine, N- (4-hexylphenyl ) -l, 4,5,6-tetrahydro-2-pyrimidinamine, N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) acetamide, N- (6 methoxy) -3-pyridyl) cyclopropanecarboxamide,

N- [2,2,2-trichloro-1 - [(chloroacetyl) amino] ethyl] benzamide, N- [3-chloro-4,5-bis (2-propynyloxy) phenyl] -N ' -methoxy-methanimidamide, N-formyl-N-hydroxy-DL-alanine sodium salt, O, O-diethyl- [2- (dipropylamino) -2-oxoethyl] ethylphosphoramidothioate, O-methyl-S-phenyl-phenylpropylphosphoramidothioate,

S-methyl-1, 2,3-benzothiadiazole-7-carbothioate, spiro [2H] -l-benzopyran-2, r (3Η) -isobenzofuran] -3'-one, 4- (3,4-dimethoxyphenyl) - 3- (4-fluorophenyl) acryloyl] morpholine bactericides:

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, teclofalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:

Abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb, aldoxycarb, alpha-cypermethrin, alphamethrin, amitraz, avermectin, AZ 60541, popilliae azadirachtin, azamethiphos, azinphos A, azinphos M, azocyclotin, Bacillus, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis .

Baculoviruses, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfüracarb, Bensultap, Benzoximate, Betacyfluthrin, Bifenazate, Bifenthrin, Bioethanomethrin, Biopermethrin, Bistrifluron, BPMC, Bromophos A, Butenoc, Carboboxofylbenzofofosin, Carbofimosyl, Carbofimosyl, Carbofimosin , Carbosulfan, cartap,

Chloethocarb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chloφyrifos, Chloφyrifos M, Chlovaporthrin, Chromafenozide, Cis-Resmethrin, Cispermethrin, Clocythrin, Cloethocarb, Clofentezyan, Cyclophrine, Cyclophrine, Cyclophrinine, Clothianhrinin, Cytophrine, Clothianhrinin, Cyclophrinine .

Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlorvos, Dicofol, Diflubenzuron, Dimethoat, Dimethylvinphos, Diofenolan, Disulfoton, Docusat-sodium, Dofenapyn, Eflusilanate, Emamectomine, Emanectin, Endamulfin, Endamphine Esfenvalerate, Ethiofencarb, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfos,

Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate, Fipronil, Fluazuron, Flubrocythrinate, Flucycloxuron, Flcythrinate, Fluftoxinhrininate, Fufonoxhrhrininate, Fumetoxinhrininate, Fumetoxin , Furathiocarb,

granulosis Halofenozide, HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene, Imidacloprid, Indoxacarb, Isazofos, Isofenphos, Isoxathion, Ivermectin, Kernpolyederviruses Lambda-cyhalothrin, Lufenuron Malathion, Mecarbam, Metaldehyde, Methamidophyllis, Methamidophosphate, Methamidophosphate

Metharhizin flavoviride, methidathione, methiocarb, methoprene, methomyl, methoxyfenozide, metolcarb, metoxadiazone, Mevinphos, Milbemectin, milbemycin, Monocrotophos, Naled, Nitenpyram, Nithiazine, Novaluron Omethoat, Oxamyl Myd

Paecilomyces fumosoroseus, Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A, Pirimiphos M, Profenofos, Promecarb, Propargite, Propoxur, Prothiofos, Prothrohrinos, Pothrohrinos, Pothrohrine, Pothrohrinate , Pyridaben, pyridathione, pyrimidifen, pyriproxyfen,

Quinalphos, Ribavirin

Salithion, Sebufos, Silafluofen, Spinosad, Spirodiclofen, Sulfotep, Sulprofos, Tau-fluvalinate, Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos, Temivinphos, Terbufos, Tetrachlorifinphonidone hydrogen oxalate, thiodicarb, thiofanox, thuringiensin, tralocythrin, tralomethrin, triarathenes, triazamates, triazophos, triazuron, trichlophenidines, trichlorfon. Triflumuron, Trimethacarb, Vamidothion, Vaniliprole, Verticillium lecanii

Yl 5302

Zeta-cypermethrin, zolaprofos

(IR-cis) - [5- (phenylmethyl) -3-furanyl] methyl-3 - [(dihydro-2-oxo-3 (2H) - furanylidene) methyl] -2,2-dimethylcyclopropane carboxylate (3-phenoxyphenyl ) -methyl-2,2,3,3-tetramethylcyclopropanecarboxylat l - [(2-chloro-5-thiazolyl) methyl] tetrahydro-3,5-dimethyl-N-nitro-l, 3,5-triazin-2 (1H) - imine

2- (2-chloro-6-fluoφhenyl) -4- [4- (l, l-dimethylethyl) phenyl] -4,5-dihydro-oxazol

2- (acetyloxy) -3-dodecyl-1,4-naphthalenedione 2-chloro-N - [[[4- (l-phenylethoxy) phenyl] amino] carbonyl] benzamide

2-Chloro-N - [[[4- (2,2-dichloro-1,1-difluoroethoxy) phenyl] amino] carbonyl] benzamide

3-methylphenyl propyl carbamate

4- [4- (4-ethoxyphenyl) -4-methylpentyl] -l-fluoro-2-phenoxy-benzene

4-Chloro-2- (l, 1-dimethylethyl) -5 - [[2- (2,6-dimethyl-4-phenoxyphenoxy) ethyl] thio] - 3 (2H) pyridazinone

4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) - pyridazinone

4-Chloro-5 - [(6-chloro-3-pyridinyl) methoxy] -2- (3, 4-dichloφhenyl) -3 (2H) -pyridazinone

Bacillus thuringiensis strain EG-2348 benzoic acid [2-benzoyl-l- (l, l-dimethylethyl) hydrazide

Butanoic acid 2,2-dimethyl-3- (2,4-dichloφhenyl) -2-oxo-1-oxaspiro [4.5] dec-3-en-4-yl ester

[3 - [(6-chloro-3-pyridinyl) methyl] -2-thiazolidinylidene] -cyanamide

Dihydro-2- (nitromethylene) -2H-1,3-thiazine-3 (4H) -carboxaldehyde ethyl- [2- [[1,6-dihy dro-6-oxo-1 - (phenylmethyl) -4-pyridazinyl ] oxy] ethyl] carbamate

N- (3,4,4-trifluoro-1-oxo-3-butenyl) gly

N- (4-chloro-phenyl) -3 - [4- (difluoromethoxy) pheny 1] -4.5 -dihy dro-4-phenyl- 1 H-pyrazole-

1-carboxamide

N - [(2-chloro-5-thiazolyl) methyl] -N'-methyl-N "-nitro-guanidine N-methyl-N '- (1-methyl-2-propenyl) -1, 2-hydrazinedicarbothioamide

N-methyl-N'-2-propenyl-1, 2-hydrazinedicarbothioamide

O, O-diethyl [2- (dipropylamino) -2-oxoethyl] -ethylphosphoramidothioat

N-cyanomethyl-4-trifluoromethyl-nicotinamide

3,5-dichloro-l- (3,3-dichloro-2-propenyloxy) -4- [3- (5-trifluoromethylpyridin-2-yloxy) propoxy] benzene A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also possible.

When used as insecticides, the active compounds according to the invention can also be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists. Synergists are compounds that increase the effectiveness of the active ingredients without the added synergist itself having to be active.

The active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges. The active substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, 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 pests and pests of stored products, the active ingredient is distinguished by an excellent residual action on wood and clay as well as a good stability to alkali on limed substrates.

As already mentioned above, all plants and their parts can be treated according to the invention. In a preferred embodiment, plant species and plant cultivars and their parts occurring wildly or obtained by conventional biological breeding methods, such as crossing or protoplast fusion, are treated. In a further preferred embodiment, transgenic plants and plant cultivars which have been obtained by genetic engineering methods, if appropriate in combination with conventional methods (genetic modified organisms) and their parts are treated. The term “parts” or “parts of plants” or “parts of plants” was explained above. Plants of the plant varieties which are in each case commercially available or in use are particularly preferably treated according to the invention. Plant cultivars are understood to mean plants with new properties (“traits”) which have been cultivated both by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, bio- and genotypes.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, growing season, nutrition), the treatment according to the invention can also result in superadditive (“synergistic”) effects. For example, reduced application rates and or widening the spectrum of action and / or strengthening the effect of the substances and agents which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher

Nutritional value of the harvested products, higher shelf life and / or workability of the harvested products possible, which go beyond the effects that are actually to be expected.

The preferred transgenic plants or plant cultivars to be treated according to the invention include all plants which have received genetic material through the genetic engineering modification, which gives these plants particularly advantageous, valuable properties (“traits”). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripening, higher harvest yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or Machinability of the harvested products Further and particularly highlighted examples of such properties are an increased defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, Bacteria and / or viruses and an increased tolerance of the plants to certain herbicidal active ingredients. The important cultivated plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and grapes) are mentioned as examples of transgenic plants, with corn, soybeans , Potato, cotton and rapeseed are highlighted. The properties (“traits”) which are particularly emphasized are the plants' increased defense against insects by toxins arising in the plants, in particular those which are caused by the genetic material from Bacillus thuringiensis (for example by the genes CryΙA (a), CryΙA (b), CryΙA (c), CryllA, CrylllA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CrylF as well as their combinations) are produced in the plants (hereinafter "Bt plants"). The increased defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins are also particularly emphasized as properties (“traits”). Traits ") are also particularly emphasized the increased tolerance of the plants to certain herbicidal active ingredients, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example" PAT "gene). The genes which impart the desired properties (" traits ") can also occur in combinations with one another in the transgenic plants. Examples of "Bt plants" are maize varieties,

Cotton varieties, soy varieties and potato varieties named under the trade names YIELD GARD® (e.g. corn, cotton, soy), KnockOut® (e.g. corn), StarLink® (e.g. corn), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf ® (potato) are sold. Examples of herbicide-tolerant plants include maize, cotton and soybeans, which are among the

Trade names Roundup Ready® (tolerance against glyphosate e.g. corn, cotton, soy), Liberty Link® (tolerance against phosphinotricin, e.g. rapeseed), IMI® (tolerance against imidazolinones) and STS® (tolerance against sulfonylureas e.g. corn). As herbicide-resistant plants (conventionally grown on herbicide tolerance), the varieties marketed under the name Clearfield® (eg maize) should also be mentioned. Of course, these statements also apply to plant varieties developed in the future or coming onto the market in the future with these or future-developed genetic properties (“traits”).

The plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula (I) or the active compound mixtures according to the invention. The preferred ranges given above for the active substances or mixtures also apply to the treatment of these plants. Plant treatment with the compounds or mixtures specifically listed in the present text should be particularly emphasized.

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 Hangings, featherlings and fleas. These parasites include:

From the order of the Anoplurida e.g. Haematopinus spp., Linognathus spp.,

Pediculus spp., Phtirus spp., Solenopotes spp.

From the order of the Mallophagida and the subordinates Amblycerina and Ischnocerina e.g. 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 and Brachycerina e.g. 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 ., 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 e.g. Pulex spp., Ctenocephalides spp.,

Xenopsylla spp., Ceratophyllus spp. From the order of the Heteropterida, for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.

From the order of the Blattarida e.g. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp. From the subclass of Acaria (Acarida) and the orders of the Meta and

Mesostigmata e.g. Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietssus spp., ., Sternostoma spp., Varroa spp. From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata) e.g.

Acarapis spp., Cheyletiella spp., Omithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectolich spp., Pod ., 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 controlling arthropods which are used in agricultural animals, e.g. Cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as e.g. Dogs, cats, house birds, aquarium fish and so-called experimental animals, such as Infest hamsters, guinea pigs, rats and mice. By combating these arthropods, deaths and reduced performance (in the case of meat, milk, wool, skins, eggs, honey, etc.) are to be reduced, so that the use of the active compounds according to the invention enables more economical and simple animal husbandry.

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, tablets, capsules, drinkers, drenches, granules, pastes, boluses, the feed-through method, suppositories, by parenteral administration, for example by injections

(intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, through nasal Application, through 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 shaped articles containing active ingredients, such as collars, ear tags, tail marks , Limb straps, holsters, marking devices etc.

When used for cattle, poultry, pets, etc., the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, flowable agents) which contain the active compounds in an amount of 1 to 80% by weight, directly or apply after 100 to 10,000-fold dilution or use it as a chemical bath.

It has also been found that the compounds according to the invention have a high insecticidal action against insects which destroy industrial materials.

The following insects may be mentioned by way of example and preferably, but without limitation:

Beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Emobius mollis, Priobium caφini, Lyctus brunneus, Lyctus africanus, Lyctus planicollisis, Lyctus pubcollis, Lyctus pubicollis, Lyctus pubicollis, Lyctus pubisole 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 saccharina.

In the present context, technical materials are to be understood as non-living materials, such as preferably plastics, adhesives, glues, papers and cartons, leather, wood, wood processing products and paints.

The one to be protected against insect attack is very particularly preferably

Material around wood and wood processing products.

Wood and wood processing products which can be protected by the agent according to the invention or mixtures containing it are to be understood as examples:

Lumber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wooden cladding, wooden windows and doors, plywood, chipboard, carpentry or wooden products that are generally used in house construction or joinery.

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

The formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredients with at least one solvent or diluent, emulsifier, dispersant and / or binder or fixative, water repellants, optionally siccatives and UV stabilizers and added - if necessary dyes and pigments and other processing aids. The insecticidal compositions or concentrates used to protect wood and wood-based materials contain the active compound according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.

The amount of the agents or concentrates used depends on the type and occurrence of the insects and on the medium. The optimal amount can be determined in each case by test series. In general, however, it is sufficient to use 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected.

An organic-chemical solvent or solvent mixture and / or an oily or oily or low-volatility 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 agents.

The organic chemical solvents used are preferably oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C. Corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene, are used as such low-volatility, water-insoluble, oily and oily solvents.

Mineral oils with a boiling range of 170 to 220 ° C, test gasoline with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° C are advantageous. Teφentinöl and the like. For use.

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

The organic semi-volatile oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partially replaced by slightly or medium-volatile organic chemical solvents, with the proviso that the solvent mixture also has an evaporation number above 35 and has 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 is replaced by an aliphatic polar organic chemical solvent or solvent mixture. Aliphatic organic chemical solvents containing hydroxyl and / or ester and / or ether groups, such as, for example, glycol ethers, esters or the like, are preferably used.

In the context of the present invention, the known organic-chemical binders are the water-dilutable synthetic resins and / or synthetic resins which are soluble or dispersible or emulsifiable in the organic-chemical solvents used and / or binding drying oils, in particular binders consisting of or containing Acrylate resin, a vinyl resin, e.g. 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 synthetic resin are used.

The synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous nous substances up to 10 wt .-%, are used. In addition, known dyes, pigments, water-repellants, odor correctors and inhibitors or anticorrosive agents and the like can be used.

According to the invention, at least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is preferably contained in the agent or in the concentrate as the organic chemical binder. Alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight, are preferably used according to the invention.

All or part of the binder mentioned can be replaced by a fixing agent (mixture) or a plasticizer (mixture). These additives are intended to prevent volatilization of the active ingredients and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 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, higher glycerol glycerol or glycerol ether - Kolether, glycerol ester and p-toluenesulfonic acid ester.

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

Water is also particularly suitable as a solvent or diluent, if appropriate in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants.

A particularly effective wood protection is achieved by industrial impregnation processes, e.g. vacuum, double vacuum or pressure processes. The ready-to-use compositions can optionally contain further insecticides and, if appropriate, one or more fungicides.

The insecticides and fungicides mentioned in WO 94/29 268 are preferably suitable as additional admixing partners. The ones mentioned in this document

Connections are an integral part of this application.

Insecticides such as chloropyriphos, phoxime, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthron, trifluoropuron, methifluoropuron, methifluoropuron, methifluoropuron

as well as fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorofluoride, tolylfluanid, 3-iodo-2-propynylbutylcarbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro -octyl-isothiazolin-3-one.

At the same time, the compounds according to the invention can be used to protect objects, in particular ship hulls, sieves, nets, structures, quay systems and signaling systems which come into contact with sea or brackish water.

Overgrowth by sessile oligochaetes, such as lime tube worms, and by mussels and species from the group Ledamoφha (barnacles), such as various types of Lepas and Scalpellum, or by species from the group Balanomoφha (barnacles), such as

Baianus or pollicipes species, increases the frictional resistance of ships and, as a result, leads to a significant increase in operating costs due to increased energy consumption and, moreover, frequent dry dock stays.

In addition to fouling by algae, for example Ectocaφus sp. and Ceramium sp., the vegetation comes in particular through sessile Entomostraken groups, which are summarized under the name Cirripedia (barnacles).

It has now surprisingly been found that the compounds according to the invention, alone or in combination with other active ingredients, are excellent

Have antifouling effect.

By using compounds according to the invention alone or in combination with other active ingredients, the use of heavy metals such as e.g. in bis (trialkyltin) sulfides, tri-butyltin laurate, tri-rc-butyltin chloride, copper (I) oxide,

Triethyltin chloride, tri - «- butyl (2-phenyl-4-chloro-phenoxy) -tin, tributyltin oxide, molybdenum disulfide, antimony oxide, polymeric butyl titanate, phenyl- (bispyridine) - bismuth chloride, tri-w-butylzirine fluoride, manganese ethylenebisto- dimethylcarbamate, zinc thiocarbamate, Zinc and copper salts of 2-pyridinthiol-1-oxide, bisdimethyldithiocarbamoylzinkethylenististhiocarbamate,

Zinc oxide, copper (I) ethylene bisdithiocarbamate, copper thiocyanate, copper phthalate and tributyltin halides can be omitted or the concentration of these compounds can be significantly reduced.

The ready-to-use antifouling paints can also be used if necessary

Contain active ingredients, preferably algicides, fungicides, herbicides, molluscicides or other antifouling active ingredients.

Suitable combination partners for the antifouling agents according to the invention are preferably:

Algicides like

2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine, dichlorophene, diuron, endothal, fentin acetate, isoproturon, methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn; Fungicides like

Benzo [t>] thiophenecarboxylic acid cyclohexylamide-S, S-dioxide, dichlofluanid, fluorofolpet, 3-iodo-2-propynyl-butylcarbamate, tolylfluanid and azoles such as azaconazole, cyproconazole, epoxyconazole, hexaconazole, metconazole, propiconazole, propiconazole

Molluscicides like

Fentin acetate, metaldehyde, methiocarb, niclosamide, thiodicarb and trimethacarb;

or conventional antifouling agents such as

4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatrylsulfone, 2- (N, N-dimethylthiocarbamoylthio) -5-nitrothiazyl, potassium, copper, sodium and zinc salts of 2-pyridinethiol -l-oxide, pyridine-triphenylborane, tetrabutyldistannoxane, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulfide and 2,4,6-trichloφhenylmaleimide ,

The antifouling agents used contain the active compound according to the invention of the compounds according to the invention in a concentration of 0.001 to 50% by weight, in particular of 0.01 to 20% by weight.

The antifouling agents according to the invention further contain the usual ingredients such as e.g. in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.

In addition to the algicidal, fungicidal, molluscicidal and insecticidal active compounds according to the invention, antifouling paints contain in particular binders.

Examples of recognized binders are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, acrylic resins in a solvent system, in particular in an aqueous system, vinyl chloride / vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organic solvent systems, butadiene / styrene / acrylonitrile rubbers, drying oils, such as linseed oil, resin esters or modified hard resins in combination with tar or bitumen, asphalt and epoxy compounds, small amounts of chlorinated rubber, chlorinated polypropylene and ninyl resins.

Paints may also contain inorganic pigments, organic pigments or dyes, which are preferably insoluble in sea water. Paints may also contain materials such as rosin to enable controlled release of the active ingredients. The paints may also contain plasticizers, modifiers that affect the rheological properties, and other conventional ingredients. The self-compounds according to the invention or the abovementioned mixtures can also be incorporated into self-polishing antifouling systems.

The active ingredients are also suitable for controlling animal pests, in particular insects, arachnids and mites, which live in closed spaces such as apartments, factory halls, offices, vehicle cabins, etc. occurrence. To control these pests, they can be used alone or in combination with other active ingredients and auxiliaries in household insecticide products. They are effective against sensitive and resistant species and against all stages of development. These pests include:

From the order of the Scoφionidea e.g. Buthus occitanus.

From the order of the Acarina e.g. Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat,

Rhipicephalus sanguineus, Trombicula alfreddugesi, Νeutrombicula autumnalis,

Dermatophagoides pteronissimus, Dermatophagoides forinae.

From the order of the Araneae e.g. Aviculariidae, Araneidae.

From the order of the Opiliones e.g. Pseudoscoφiones chelifer, Pseudoscoφiones cheiridium, Opiliones phalangium.

From the order of the Isopoda, for example Oniscus asellus, Porcellio scaber. From the order of the Diplopoda, for example, Blaniulus guttulatus, Polydesmus spp.

From the order of the Chilopoda e.g. Geophilus spp.

From the order of the Zygentoma e.g. Ctenolepisma spp., Lepisma saccharina,

Lepismodes inquilinus. From the order of the Blattaria e.g. Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa,

Supella longipalpa.

From the order of the Saltatoria e.g. Acheta domesticus. From the order of the Dermaptera e.g. Forficula auricularia.

From the order of the Isoptera e.g. Kalotermes spp., Reticulitermes spp.

From the order of the Psocoptera e.g. Lepinatus spp., Liposcelis spp.

From the order of the Coleptera e.g. Anthrenus spp., Attagenus spp., Dermestes spp.,

Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.

From the order of the Diptera e.g. Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis,

Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca domestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa.

From the order of the Lepidoptera e.g. Achroia grisella, Galleria mellonella, Plodia inteφunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.

From the order of the Siphonaptera e.g. Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis. From the order of the Hymenoptera e.g. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.

From the order of the anoplura e.g. Pediculus humanus capitis, Pediculus humanus coφoris, Phthirus pubis. From the order of the Heteroptera e.g. Cimex hemipterus, Cimex lectularius,

Rhodinus prolixus, Triatoma infestans. The application in the field of household insecticides is carried out alone or in combination with other suitable active ingredients such as phosphoric acid esters, carbamates, pyrethroids, growth regulators or active ingredients from other known classes of insecticides.

They are used in aerosols, non-pressurized sprays, e.g. Pump and atomizer sprays, automatic foggers, foggers, foams, gels, vaporizer products with Nerdampfeφlätchen from cellulose or plastic, liquid evaporators, gel and membrane evaporators, propeller-driven evaporators, energy-free or passive evaporation systems, moth paper, moth bags and moth gel, as granules or pellets in lures or bait stations.

The preparation and use of the substances according to the invention can be seen from the following examples.

Preparation Examples:

Example 1:

To a mixture of 1.1 g (4.1 mmol) of 3- (4-chlorophenyl) -4- (4-cyanopyrazol-l-yl) - 4,5-dihydro-lH-pyrazole (Ex. II-l) , 0.1 ml of triethylamine and 80 ml of methyl tert-butyl ether are added at 70 ° C to 0.63 g (4.1 mmol) of 4-chloro-phenyl isocyanate. The mixture is stirred for 15 minutes at 70 ° C and then allowed to cool slowly to room temperature. The precipitated product is filtered off and washed with a little methyl tert-butyl ether.

1.4 g (80% of theory) of 3- (4-chlorophenyl) -4- (4-cyanopyrazol-l-yl) -4,5-dihydro-l-pyrazolecarboxylic acid-4-chloroanilide are obtained with the logP (pH2 ) = 3.64.

Example 2: (Method b)

2.4 g of 3- (4-chlorophenyl) -4- (4-cyanopyrazole) l are added to a suspension of 0.2 g (5 mmol) of sodium hydride (60% in mineral oil) in 20 ml of tetrahydrofuran at 0 ° C -yl) -4,5-dihydro-l-pyrazolecarboxylic acid-4-trifluoromethoxyanilide (5 mmol) and then 1.2 g (10 mmol) bromoacetonitrile. The mixture is heated under reflux for 18 hours and then evaporated in vacuo. 50 ml of water are added to the residue and the reaction product is extracted with ethyl acetate. The organic phase is dried over sodium sulfate and evaporated in vacuo. The residue is purified by preparative HPLC.

0.15 g (6% of theory) of 3- (4-chloro-phenyl) -4- (cyanopyrazol-l-yl) -4,5-dihydro-1-pyrazolecarboxylic acid (N-cyanomethyl) -4 '-trifluoromethoxy are obtained anilide with the logP (pH2) = 3.68.

(Method c)

To a mixture of 2.7 g (10 mmol) of 3- (4-chlorophenyl) -4- (4-cyanopyrazol-l-yl) - 4,5-dihydro-lH-pyrazole (Ex. II-l), 1 , 5 ml of triethylamine and 50 ml of methylene chloride are added at 0 ° C to 2.78 g (10 mmol) of N-cyanomethyl-N- (4-trifluoromethoxyphenyl) carbamic acid chloride (Ex. Va-1). The mixture is stirred for 18 hours at room temperature and then washed twice with 30 ml of water. The organic Phase is dried over sodium sulfate and evaporated in vacuo. The residue is stirred with ethanol, suction filtered and washed with ethanol.

4.05 g (79% of theory) of 3- (4-chlorophenyl) -4- (4-cyanopyrazol-l-yl) -4.5- dihydro-l-pyrazolecarboxylic acid- (N-cyanomethyl-4- trifluoromethoxyanilide with the logP

(pH2) = 3.68.

(Method c, one-pot method)

To a solution of 16 g (0.054 mol) of triphosgene (carbonic acid bis-trichloromethyl ester) in 100 ml of methylene chloride, a solution of 34.56 g (0.16 mol) of N-cyanomethyl- (4- trifluoromethoxy) aniline (Ex. XII-1) and 16.5 g (0.163 mol) of triethylamine in 75 ml of methylene chloride and the mixture is stirred for half an hour at room temperature. A solution of 43.4 g (0.16 mol) of 3- (4-chloro-phenyl) -4- (4-cyanopyrazol-l-yl) -4,5-dihydro-1H-pyrazole (Ex. II- l) and 16.5 g (0.163 mol) of triethylamine in 75 ml of methylene chloride. The mixture is stirred for 18 hours at room temperature and then washed twice with 100 ml of water. The organic phase is dried over sodium sulfate and evaporated in vacuo. The residue is stirred with ethanol, suction filtered and washed with ethanol.

This gives 65.3 g (79% of theory) of 3- (4-chloro-phenyl) -4- (4-cyanopyrazol-l-yl) -4,5-dihydro-l-pyrazolecarboxylic acid (N-cyanomethyl) -4-trifluoromethoxyanilide with the logP (pH2) = 3.68.

Analogously to Examples 1 and 2 or according to the general information on the preparation, the compounds of the formula (I) given in Table 1 below are obtained: Table 1:

Preparation of the starting products of the formula (II)

Example (II-l):

To a solution of 5 g (0.02 mol) of 2- (4-cyanopyrazol-l-yl) -4'-chloroacetophenone (Ex. VI-1) in 50 ml of methylene chloride, 2.16 g (0.021 mol ) Bis-dimethylaminomethane and reflux the mixture for 18 hours. Then the solvent is distilled off in vacuo and the residue is dissolved in 50 ml of ethanol. After adding 1.13 g (0.0226 mol) of hydrazine hydrate, the reaction mixture is stirred at 30 ° C. for 3 hours. The precipitated product is filtered off, washed with a little cold ethanol and with water.

3.3 g (61% of theory) of 3- (4-chlorophenyl) -4- (4-cyanopyrazol-l-yl) -4,5-dihydro-1H-pyrazole with logP (pH2) = 2 are obtained, 11th

The compounds of the formula (II) given in Table 2 below are obtained analogously to Example (II-1) or according to the general information on the preparation:

Table 2:

Preparation of the starting products of the formula (V)

Example (Va-1)

A solution of 20.7 g (0.0958 mol) of N-cyanomethyl-4-trifluoromethoxyaniline (Example XII-1) is added dropwise to a solution of 10.4 g (0.105 mol) of phosgene in 100 ml of toluene at 0.degree. and 11.6 g (0.115 mol) of triethylamine in 150 ml of toluene and the mixture is stirred for 18 hours at room temperature. Then the excess phosgene is blown out. It is washed with water, the organic phase is dried over sodium sulfate and then the solvent is distilled off in vacuo.

This gives 26.3 g (94% of theory) of N-cyanomethyl-N- (4-trifluoromethoxy) phenylcarbamoyl chloride with the refractive index njj 1, 4816.

The compounds of the formula (Va) given in Table 4 below are obtained analogously to Example (Va-1) or according to the general information on the preparation:

Table 3

Preparation of the precursors of formula (VI)

Example (VI-1):

A mixture of 9.3 g (0.04 mol) of 2-bromo-4'-chloroacetophenone, 3.9 g (0.042 mol) of 4-cyanopyrazole (preparation see JP H59-196868), 6.1 g (0.044 mol ) Potassium carbonate and 50 ml of acetonitrile is stirred for 16 hours at room temperature. Then about 200 ml of water are added to the reaction mixture, the precipitated product is suctioned off and washed with water. 9.5 g (97% of theory) of 2- (4-cyano-pyrazol-l-yl) -4'-chloroacetophenone with the logP (pH2) = 2.20 are obtained.

Example (VI-2):

1st stage:

A mixture of 15 g (0.061 mol) of 2- (4-cyanopyrazol-l-yl) -4'-chloroacetophenone, 50 ml of concentrated hydrochloric acid and 50 ml of acetic acid is boiled under reflux for 5 hours. The reaction mixture is then diluted with water, the precipitated product is filtered off with suction and washed with water. 14.4 g (89% of theory) of 1- (4-chlorophenacyl) pyrazole-4-carboxylic acid are obtained with the logP (pH2) = 1.67. 2nd stage:

2 to 3 drops of dimethylformamide and then 6 g (0.05 mol) of thionyl chloride are added to a solution of 7.9 g (0.03 mol) of 1- (4-chlorophenacyl) pyrazole-4-carboxylic acid in 50 ml of methylene chloride. The mixture is boiled under reflux for 3 hours and then evaporated in vacuo. The residue is dissolved in 30 ml of tetrahydrofuran and this solution is dropped in 30 ml of dimethylamine solution (40% in water). The mixture is stirred for 2 hours at room temperature and then the solvent is evaporated off in vacuo. The residue is mixed with 100 ml of water and extracted with ethyl acetate. The organic phase is dried over sodium sulfate and evaporated in vacuo. 2.8 g (32% of theory) of 1- (4-chlorophenacyl) pyrazole-4-carboxylic acid dimethylamide with the logP (pH2) = 1.62 are obtained.

Analogous to Examples (VI-1) and (VI-2) or according to the general information on

The compounds of the formula (VI) given in Table 3 below are obtained:

Table 4:

Preparation of the precursors of formula (XII)

Example (XII-1)

7.9 g (0.26 mol) of paraformaldehyde are added to a solution of 44 g (0.25 mol) of 4-trifluoromethoxyaniline in 200 ml of acetic acid at 15 ° C. and a solution of 20 is then added dropwise at 15-20 ° C. 6 g (0.318 mol) of potassium cyanide in 50 ml of water. The mixture is stirred at 30 ° C for 18 hours. Then the solvent is distilled off in vacuo, about 200 ml of water are added to the residue, the precipitated product is filtered off with suction and washed with good water.

This gives 52.4 g (97% of theory) of N-cyanomethyl-4-trifluoromethoxyaniline in the form of colorless crystals with the logP (ρH2) = 2.49.

The compounds of the formula (XII) given in Table 5 below are obtained analogously to Example (XII-1) or according to the general information on the preparation:

Table 5:

The logP values specified in the tables and manufacturing examples above are determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a phase reversal column (C 18). Temperature: 43 ° C.

The determination is carried out in the acidic range at pH 2.3 with 0.1% aqueous phosphoric acid and acetonitrile as eluents; linear gradient from 10% acetonitrile to 90% acetonitrile.

The calibration is carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms) whose logP values are known (determination of the logP values on the basis of the retention times by linear interpolation between two successive alkanones). Application examples:

Example A

Diabrotica test (larvae in the soil)

Solvent: 7 parts by weight of dimethylformamide emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted to the desired concentration with water containing emulsifier.

Pots filled with earth are poured with the active ingredient preparation. Immediately after the preparation, 5 corn kernels are laid out per pot and after 3 days the Diabrotica balteata larvae are placed on the treated soil. The concentration given relates to the amount of active ingredient per unit volume in the soil (mg / 1).

After the desired time, the accumulated maize plants are counted and the

Efficiency right. 100% means that all maize plants have emerged; 0% means that no maize plants have emerged.

Active substances, active substance concentration and test results are shown in the following table. Table A plant-damaging insects

Diabrotica test

Active substances Active ingredient Degree of killing in% after 10 ^d m ppm

Example B

Heliothis virescens test

Solvent: 30 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted to the desired concentration with water containing emulsifier.

Soybean shoots (Glycine max) are treated by dipping into the active ingredient preparation of the desired concentration and populated with Heliothis virescens caterpillars 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 have been killed.

Active substances, active substance concentration and test results are shown in the following table.

Table B insect pests

Heliothis virescens test

Active ingredients Active degree of killing concentration in% after 7 ^d in ppm

Table B insect pests

Heliothis virescens test

Active ingredients Active degree of killing concentration in% after 7 ^d in ppm

Example C

Phaedon larvae test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted to the desired amount with water containing emulsifier

Concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with larvae of the horseradish leaf beetle (Phaedon cochleariae) while the leaves are still moist.

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

Active substances, active substance concentration and test results are shown in the following table.

Table C insect pests

Phaedon larval test

Active ingredients Active degree of killing concentration in% after 7 ^d in ppm

Table C insect pests

Phaedon larval test

Active ingredients Active degree of killing concentration in% after 7 ^d in ppm

Table C insect pests

Phaedon larval test

Active ingredients Active degree of killing concentration in% after 7 ^d in ppm

Example D

Plutella Test

Solvent: 30 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted to the desired amount with water containing emulsifier

Concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the cockroach (Plutella xylostella) 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 have been killed.

Active substances, active substance concentration and test results are shown in the following table.

Table D insect pests

Plutella Test

Active ingredients Active ingredient Degree of killing in% after 7 ^days in ppm

Table D insect pests

Plutella Test

Active ingredients Active degree of killing concentration in% after 7 ^d in ppm

Example E

Spodoptera exigua test

Solvent: 30 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted to the desired amount with water containing emulsifier

Concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the army worm (Spodoptera exigua) 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 have been killed.

Active substances, active substance concentration and test results are shown in the following table.

Table E insect pests

Spodoptera exigua test

Active ingredients Active ingredient Degree of killing in% after 7 ^days in ppm

Example F

Spodoptera frugiperda test

Solvent: 30 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted to the desired concentration with water containing emulsifier.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the army worm (Spodoptera frugiperda) 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 have been killed.

Active substances, active substance concentration and test results are shown in the following table.

Table F plant-damaging insect Spodoptera frugiperda test

Active ingredients Active degree of killing concentration in% after 7 ^d in ppm

Table F plant-damaging insect Spodoptera frugiperda test

Active ingredients Active degree of killing concentration in% after 7 ^d in ppm

Table F plant-damaging insect Spodoptera frugiperda test

Active ingredients Active degree of killing concentration in% after 7 ^d in ppm

Example G

Effectiveness test: Heliothis virescens

Solvent: 4 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted to the desired concentration with water containing emulsifier.

Cotton plants (Gossypium hirsutum) are sprayed with an active ingredient preparation of the desired concentration. After the specified days, Heliothis virescens larvae are placed on the treated leaves in infection chambers.

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

Active substances, active substance concentration and test results are shown in the following table.

Table G insect pests

Effectiveness test: Heliothis virescens

Active substances Active ingredient Degree of killing concentration in% in ppm 7 ^d after infection

Example H

Effectiveness test: Spodoptera frugiperda

Solvent: 4 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted to the desired concentration with water containing emulsifier.

Cotton plants (Gossypium hirsutum) are sprayed with an active ingredient preparation of the desired concentration. After the specified days, larvae of the army worm (Spodoptera frugiperda) are transferred to the treated in infection chambers

Leaves set.

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

Active substances, active substance concentration and test results are shown in the following table.

Table H insect pests

Effectiveness test: Spodoptera frugiperda

Active substances Active ingredient Degree of killing concentration in% in ppm 7 ^d after infection

Example I

Diabrotica balteata test (larvae in the soil)

Limit concentration test / soil insects - treatment of transgenic plants

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

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the specified amount is given

Amount of emulsifier and dilute the concentrate with water to the desired concentration.

The active ingredient preparation is poured onto the floor. The concentration of the active ingredient in the preparation is practically irrelevant, the only decisive factor is the amount of active ingredient per unit volume of soil, which is given in ppm (mg / 1). You fill the bottom in 0.25 1 pots and let them stand at 20 ° C.

Immediately after the preparation, 5 pre-germinated maize kernels of the YIELD variety are added to each pot

GUARD (trademark of Monsanto Comp., USA). After 2 days, the appropriate test insects are placed in the treated soil. After a further 7 days, the effectiveness of the active ingredient is determined by counting the maize plants that have emerged (1 plant = 20% activity). Example J

Heliothis virescens - test (treatment of transgenic plants)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier and the concentrate is diluted with water to the desired level

Concentration.

Soybean shoots (Glycine max) of the Roundup Ready variety (trademark of Monsanto Comp. USA) are treated by dipping into the preparation of active compound of the desired concentration and are populated with the tobacco bud caterpillar Heliothis virescens 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 have been killed.

Example K

Blowfly larva test / development-inhibiting effect

Test animals: Lucilia cuprina larvae

Solvent: dimethyl sulfoxide

20 mg of active ingredient are dissolved in 1 ml of dimethyl sulfoxide, lower concentrations are made by dilution with distilled water.

About 20 Lucilia cuprina larvae are placed in a test tube containing approx. 1 cm ³ horse meat and 0.5 ml of the active ingredient preparation to be tested. The effectiveness of the active substance preparation is determined after 24 h and 48 h. The test tubes are then transferred to beakers with a bottom covered with sand. After a further 2 days, the test tubes are removed and the dolls are counted.

The effect of the active substance preparation is assessed according to the number of flies hatched after 1.5 times the development time of an untreated control. 100% means that no flies have hatched; 0% means that all flies hatched normally.

Active substances, active substance concentration and test results are shown in the following table.

Table K-1 Blowfly larva test / development inhibitory effect

Active ingredients Concentration in effect / ppm killing in% after 48 h

Table Kl Blowfly larva test / development-inhibiting effect

Active ingredients Concentration in effect / ppm killing in% after 48 h

Table K-2 Blowfly larval test / development inhibitory effect

Active ingredients concentration in effect / ppm kill in% after 14 d

Table K-2 Blowfly larval test / development inhibitory effect

Active ingredients concentration in effect / ppm kill in% after 14 d

Example L

Test with Boophilus microplus resistant / SP-resistant Parkhurst strain

Test animals: adult sucked females

Solvent: dimethyl sulfoxide

20 mg of active ingredient are dissolved in 1 ml of dimethyl sulfoxide. Lower concentrations are made by dilution in the same solvent.

The test is carried out in 5-fold determination. 1 μl of the solutions is injected into the abdomen, the animals are transferred into dishes and kept in an air-conditioned room. The effects are checked after 7 days on the laying of fertile eggs. Eggs whose fertility is not externally visible are kept in glass tubes until larvae hatch in the climatic chamber. An effect of 100% means that no tick has laid fertile eggs.

Active substances, active substance concentration and test results are shown in the following table.

Table L Test with Boophilus microplus resistant / SP-resistant Parkhurst strain

Active substances concentration μg effect / animal killing in%

Example M

Test with flies (Musca domestica)

Test animals: adult Musca domestica, trunk Reichswald (OP, SP,

Carbamate resistant) Solvent: dimethyl sulfoxide

20 mg of active ingredient are dissolved in 1 ml of dimethyl sulfoxide. Lower concentrations are made by dilution with distilled water.

2 ml of this active ingredient preparation are pipetted onto filter paper dishes (0 9.5 cm), which are located in Petri dishes of the appropriate size. After the filter discs have dried, 25 test animals are transferred to the Petri dishes and covered.

After 1, 3, 5, 24 and 48 hours (or after the times given in the tables below), the effectiveness of the active ingredient preparation is determined. 100% means that all flies have been killed, 0% means that none of the flies have been killed.

Active substances, active substance concentration and test results are shown in the following table.

Table M test with flies (Musca domestica)

Active ingredients concentration in effect / ppm kill in%

Example N

cockroach test

Test animals: Periplaneta americana solvent: dimethyl sulfoxide

20 mg of active ingredient are dissolved in 1 ml of dimethyl sulfoxide. Lower concentrations are made by diluting with distilled water.

4 test animals are immersed in the drug preparation to be tested for 1 minute. After being transferred to a plastic cup and stored for 7 days in an air-conditioned room, the degree of killing is determined. 100% means that all cockroaches have been killed, 0% means that none of the cockroaches have been killed.

Active substances, active substance concentration and test results are shown in the following table.

Table N cockroach test

Active ingredients concentration in effect / ppm kill in%

Table N cockroach test

Active ingredients concentration in effect / ppm kill in%

Claims

claims

Pyrazoline derivatives of the formula (I),

R ^{1 represents} cyano, alkoxycarbonyl, carbamoyl, thiocarbamoyl, alkylaminocarbonyl or dialkylaminocarbonyl,

R ^{2 represents} halogen, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl or cyano,

R ^{3 represents} halogen, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl or cyano and

R ^{4 represents} hydrogen, cyanomethyl or alkoxycarbonyl.

Pyrazoline derivatives of formula (I) according to claim 1, in which

R ^{1 represents} cyano, Cj-C ₄ -alkoxy-carbonyl, carbamoyl, thiocarbamoyl, C _r C -alkylamino-carbonyl or di-C ₁ -C ₄ -alkylamino-carbonyl, R ² for fluorine, chlorine, bromine, iodine; C _j -C4-haloalkyl, -C-C ₄ -haloalkoxy, C1-C4- alkylthio, Cι-C -haloalkylthio, C ₁ -C ₄ -alkylsulfonyl, Cι-C4 ~ haloalkylsulfonyl or cyano,

R ³ for fluorine, chlorine, bromine, iodine; C _j ^ -haloalkyl, C1-C4-haloalkoxy, -C-C4-haloalkylthio, Cι-C ₄ -haloalkylsulfinyl, Oj ^ -haloalkylsulfonyl or cyano and

R ^{4 represents} hydrogen, cyanomethyl or -CC4 alkoxycarbonyl.

Pyrazoline derivatives of formula (I) according to claim 1, in which

R ^{1 represents} cyano, C ¹ -C 4 -alkoxycarbonyl, carbamoyl, thiocarbamoyl, CC -alkylamino-carbonyl or di-C ₁ -C ₂ -alkylamino-carbonyl,

R ² for fluorine, chlorine, bromine, iodine, cyano; C _r C ₂ - alkylthio, C _r C ₂ -

Alkylsulfonyl and for C ₁ -C ₂ -haloalkyl, C ₁ -C ₂ -haloalkoxy,

CC - haloalkylthio or -CC ₂ haloalkylsulfonyl, each having 1 to 5 identical or different halogen atoms from the series fluorine, chlorine and bromine,

R ^{3 represents} chlorine, bromine, iodine, cyano; as well as for C _] -C ₂ haloalkyl, Cι-C ₂ -

Halogenalkoxy, C j -C ₂ haloalkylthio, C 1 -C ₂ haloalkylsulfinyl or C ₁ -C ₂ haloalkylsulfonyl each having 1 to 5 identical or different halogen atoms from the series fluorine, chlorine and bromine and

R ^{4 represents} hydrogen, cyanomethyl or C ₁ -C alkoxycarbonyl.

Pyrazoline derivatives of formula (I) according to claim 1, in which

R ¹ stands for cyano. Process for the preparation of pyrazoline derivatives of the formula (I) according to Claim 1, characterized in that

a) pyrazolines of the formula (II)

in which

R ¹ and R ^{2 have} the meanings given in Claim 1,

with isocyanates of the formula (III)

in which

R ^{3 has} the meanings given in claim 1,

if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst; and

b) optionally the pyrazoline derivatives of the formula (Ia) according to the invention thus obtained

R ¹ , R ² and R ^{3 have} the meanings given in claim 1,

with halides of the formula (IV) Hai ¹ - R ⁴ (IV) in which

R ^{4 has} the meanings given in claim 1 and

Shark ^{1 represents} halogen,

if appropriate in the presence of a diluent and if appropriate in the presence of a base, or

c) pyrazoline derivatives of the formula (Ib)

in which

R ¹ , R ² and R ^{3 have} the meanings given in claim 1,

obtained by

Pyrazolines of formula (II)

in which

R ¹ and R ^{2 have} the meanings given in Claim 1,

with carbamic acid chlorides of the formula (V)

in which

R ^{3 has} the meanings given in claim 1,

in the presence of a diluent and optionally in the presence of a base.

6. pesticide, characterized by a content of at least one compound of the formula (I) according to claim 1 in addition to extenders and / or surface-active substances.

7. Use of compounds of formula (I) according to claim 1 for controlling pests.

Process for combating pests, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on pests and / or their habitat.

Process for the preparation of pesticides, characterized in that compounds of the formula (I) according to Claim 1 are mixed with extenders and / or surface-active substances.

10. pyrazolines of the formula (II)

in which

R ¹ and R ^{2 have} the meanings given in claim 1.

11. A method for producing pyrazolines of the formula (II) according to claim 10, characterized in that

d) substituted acetophenones of the formula (VI) in which

R ¹ and R ^{2 have} the meanings given in Claim 1,

in a first stage with bis-dialkylaminomethanes of the formula (VII)

(Alk) ₂ N-CH— N (Alk) ₂ ( _V H)

in which

Alk represents C j -C ₄ alkyl,

in the presence of an inert, organic solvent (preferably halogenated hydrocarbons) at temperatures between 0 ° C. and 120 ° C., preferably between 20 ° C. and 80 ° C., and the resulting dialkylaminoalkyl ketones of the formula (VIII)

in which

R ¹ and R ^{2 have} the meanings given in claim 1 and

Alk has the meanings given above, optionally isolated and reacted in a second stage with hydrazine (hydrate) in the presence of an inert, organic solvent (preferably alcohols) at temperatures between 0 ° C. and 80 ° C., preferably between 20 ° C. and 50 ° C.

12. Carbamic acid chlorides of the formula (Va)

in which

R ^{7 represents} haloalkyl, haloalkoxy or haloalkylthio.

13. A process for the preparation of substituted carbamic acid chlorides of the formula (Va) according to claim 12, characterized in that

g) cyanomethylanilines of the formula (XII)

in which

R ^{7 has} the meanings given in claim 12,

with phosgene in the presence of an inert organic diluent and in the presence of a base at temperatures between -10 ° C and + 120 ° C, the phosgene can be used in a slight excess.

14. Substituted acetophenones of the formula (VI)

in which

R ¹ and R ^{2 have} the meanings given in claim 1.

15. A process for the preparation of substituted acetophenones of the formula (VI) according to claim 14, characterized in that

d) haloacetophenones of the formula (IX)

in which

R ^{2 has} the meanings given in claim 1 and

Shark ^{2 represents} halogen,

with pyrazoles of the formula (X)

R ¹

N (X) IH in which R ^{1 has} the meanings given in claim 1,

in the presence of an organic or inorganic base and optionally in the presence of an inert organic solvent, at temperatures between 0 ° C and 100 ° C, preferably between 20 ° C and 80 ° C.

16. cyanomethylanilines of the formula (XII)

in which

R ^{7 represents} haloalkyl, haloalkoxy or haloalkylthio.

17. A process for the preparation of substituted cyanomethylanilines of the formula

(XII) according to claim 16, characterized in that one

h) anilines of the formula (XIII)

in which

R ^{7 has} the meanings given in claim 16,

in the presence of acetic acid with paraformaldehyde and alkali metal cyanide at temperatures between 20 ° C and 60 ° C. Pyrazoline derivatives

Summary

New pyrazoline derivatives of the formula (I)

in which

R ¹ , R ² , R ³ and R ^{4 have} the meanings given in the description,

several processes for the production of these substances and their use for controlling pests, and new intermediates and processes for their production.