DE19757223A1 - New 2-phenyl-4-bi:phenyl-oxazoline derivatives - Google Patents

Abstract

Substituted 2-phenyl-4-biphenyl-oxazolines (I) are new: X<1>, X<3> = H, halo, alkyl, alkoxy or alkylthio; X<3> is especially H; X<2> = halo, alkyl, alkoxy or alkylthio; R<1> = H, halo, alkyl or CH2CR<4>=CH2; R<2> = alkyl, hydroxyalkyl or optionally substituted alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, cycloalkenylalkyl, phenylalkyl, naphthylalkyl or tetrahydronaphthylalkyl; R<3> = H, alkyl, halo or CH2CR<4>=CH2; R<4> = H or optionally substituted alkyl or aryl; compounds in which R<1> = R<3> = H are excluded.

Description

The invention relates to new biphenyloxazolines, processes for their preparation and the Use of biphenyloxazolines to control animal pests.

It is known that certain biphenyloxazolines are insecticidal and acaricidal are, for example, the compounds 2- (2,6-difluorophenyl) -4- (3'-chloro-4 '- (1,1,2,2- tetrafluoroethoxy) biphenyl-4) -2-oxazoline (EP-A-0 696 584) and 2- (2,6-difluoro phenyl) -4- (3'-chloro-4'-methylbiphenyl-4) -2-oxazoline (EP-A-0 432 661).

The level of action and / or duration of action of these known compounds is dependent however, especially against certain organisms or with low application con concentrations, not completely satisfactory in all areas of application.

New disubstituted biphenyloxazolines of the formula (I)

found,
in which
X ^{1 represents} hydrogen, halogen, alkyl, alkoxy or alkylthio,
X ^{2 represents} halogen, alkyl, alkoxy or alkylthio,
X ^{3 represents} hydrogen, halogen, alkyl, alkoxy or alkylthio, in particular hydrogen,
R ^{1 represents} hydrogen, halogen, alkyl or -CH ₂ -CR ⁴ = CH ₂ ,
R ^{2 represents} alkyl, hydroxyalkyl, each optionally substituted alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, cycloalkenylalkyl, phenylalkyl, naphthylalkyl or tetrahydronaphthylalkyl and
R ^{3 represents} halogen or alkyl and
R ^{4 represents} hydrogen or in each case optionally substituted alkyl or aryl.

The compounds of the formula fall because of one or more centers of chirality (I) generally as mixtures of stereoisomers. They can be in both their Diastereomer mixtures as well as pure diastereomers or enantiomers can be used be det.

It has also been found that the new compounds of the formula (I) are obtained if compounds of the formula (II)

in which
X ¹ , X ² , X ³ , R ³ and R ^{1 have} the meanings given above, with compounds of the formula (III)

ZR ² (III),

in which
R ^{2 has} the meaning given above and
Z represents a leaving group,
if appropriate in the presence of a diluent and if appropriate in the presence of a base.

It has also been found that the new compounds of the formula (I) are very good for loading control of animal pests, in particular insects, arachnids and Nematodes used in agriculture, in the forest, in the protection of stocks and materials as well as in the hygiene sector are suitable.

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

Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below.
X ¹ preferably represents hydrogen, fluorine, chlorine, bromine, iodine, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or C ₁ -C ₆ alkylthio.
X ² preferably represents fluorine, chlorine, bromine, iodine, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or C ₁ -C ₆ alkylthio.
X ³ preferably represents hydrogen, fluorine, chlorine, C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy, in particular hydrogen.
R ¹ preferably represents hydrogen, fluorine, chlorine, bromine, C ₁ -C ₆ alkyl or -CH ₂ -CR ⁴ = CH ₂ .
R ² preferably represents C ₁ -C ₈ alkyl, C ₁ -C ₆ hydroxyalkyl, C ₃ -C ₁₀ alkenyl, C ₃ -C ₁₂ alkynyl, optionally substituted by halogen or C ₁ -C ₄ alkyl tuiert C ₃ -C ₆ cycloalkyl or C ₃ -C ₆ cycloalkenyl,
is optionally substituted by halogen, C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ - haloalkenyl, phenyl, halophenyl, styryl or Halogenstyryl sub stituiertes C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl,
for C ₄ -C ₈ cycloalkenyl-C ₁ -C ₂ alkyl optionally substituted by halogen or C ₁ -C ₄ alkyl,
or for optionally up to four times, identical or different, by nitro, halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ haloalkyl, C ₁ -C ₁₂ alkylthio, C ₁ -C ₁₂ haloalkylthio, C ₁ - C ₁₂ alkoxy or C ₁ -C ₁₂ haloalkoxy substituted phenyl-C ₁ -C ₄ alkyl, for naphthyl-C ₁ -C ₃ alkyl or tetrahydro naphthyl-C ₁ -C ₃ alkyl.
R ³ preferably represents fluorine, bromine, chlorine or C ₁ -C ₄ alkyl.
R ⁴ preferably represents hydrogen, C ₁ -C ₁₂ alkyl or in each case optionally one to four times, identically or differently by halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ haloalkyl, C ₁ -C ₁₂ - Alkoxy or C ₁ -C ₁₂ haloalkoxy substituted phenyl.
X ¹ particularly preferably represents hydrogen, fluorine or chlorine.
X ² particularly preferably represents fluorine, chlorine, bromine, iodine, C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy.
X ³ particularly preferably represents hydrogen fluorine, chlorine, C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy, in particular hydrogen.
R ¹ particularly preferably represents hydrogen fluorine, chlorine, bromine or C ₁ -C ₄ -alkyl or -CH ₂ -CR ⁴ = CH ₂ .
R ² particularly preferably represents C ₁ -C ₆ alkyl, C ₁ -C ₄ hydroxyalkyl, C ₃ -C ₁₀ alkenyl, C ₃ -C ₅ alkynyl, optionally by halogen or C ₁ -C ₄ alkyl substituted cyclohexyl or C ₃ -C ₆ cycloalkenyl,
for C ₃ -C ₆ cycloalkyl-C ₁ -C ₄ optionally substituted by halogen, C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₃ haloalkenyl, phenyl, halophenyl, styryl or halostyryl ₄ -alkyl,
for C ₄ -C ₆ cycloalkenylmethyl which is optionally substituted by halogen or
for optionally single or double, identical or different by nitro, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -haloalkoxy substituted benzyl, for naphthylmethyl or tetrahydronaphthylmethyl.
R ³ particularly preferably represents chlorine, bromine or C ₁ -C ₃ alkyl.
R ⁴ particularly preferably represents hydrogen C ₁ -C ₄ -alkyl or, if appropriate, once or twice, identically or differently, by fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl or C ₁ -C ₄ haloalkoxy substituted phenyl.
Halogen in the radical definitions designated as preferred or particularly preferred in particular represents fluorine, chlorine and bromine.
X ¹ very particularly preferably represents hydrogen, fluorine or chlorine.
X ² very particularly preferably represents fluorine, chlorine, bromine, iodine, methyl or methoxy.
X ³ very particularly preferably represents hydrogen, fluorine, chlorine or methyl, in particular hydrogen.
R ¹ very particularly preferably represents hydrogen. Fluorine, chlorine, bromine, methyl,
Ethyl, n- or i-propyl or for allyl.
R ² very particularly preferably represents methyl, ethyl, n- or i-propyl, n-butyl, i-butyl, s-butyl, n-pentyl, n-hexyl, hydroxyethyl, hydroxypropyl, hydroxy butyl, for -CH ₂ - CH = CH ₂ , -CH ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -C∼CH or -CH (CH ₃ ) C∼H, for one of the cycloalkylalkyl groups:

for one of the following residues:

R ³ very particularly preferably represents chlorine, bromine or methyl.

Compounds of the formula (Ia) are also preferred

in which
R ¹ , R ² , R ³ , X ¹ and X ^{2 have} the abovementioned general, preferred, particularly preferred or very particularly preferred meanings.

A preferred group of compounds are also those of the formula (Ib)

in which
X ^{1 represents} hydrogen or fluorine,
X ^{2 represents} fluorine, chlorine, bromine or methyl,
R ^{1 represents} chlorine, methyl, ethyl, n- or i-propyl or allyl,
R ^{2 has} the abovementioned general, preferred, particularly preferred and very particularly preferred meanings and is particularly emphasized for optionally substituted benzyl as mentioned above, and
R ^{3 represents} chlorine, bromine and methyl, especially chlorine.

The carbons mentioned above in the definition of the compounds according to the invention hydrogen residues, such as alkyl or alkenyl, are - also in connection with heteroato as in alkoxy - as far as possible straight or branched.

The general or priority ranges listed above nitions or explanations can be among each other, that is, between the respective Areas and preferred areas can be combined as desired. They apply to the end products as well as for the preliminary and intermediate products accordingly.

According to the invention, preference is given to the compounds of the formula (I) in which one Combination of the meanings listed above as preferred (preferred) is present.

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

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

If, for example, 2- (2,6-difluorophenyl) -4- (4'-hydroxy-3 ', 5'-dichlorobiphenyl-4) -2-oxazoline and isopropyl bromide are used as starting materials, the process according to the invention can be carried out Repeat the procedure using the following reaction scheme:

The compounds required as starting materials in the process according to the invention Formula (II) are new.

The compounds of the formula (II) are obtained, for example, if compounds of the formula (VI)

in which
X ¹ , X ² , X ³ , R ¹ and R ^{3 have} the meanings given above and
R ^{5 represents} alkyl (for example methyl), aryl (for example phenyl) or alkoxy (for example methoxy or ethoxy),
cyclized in the presence of a base, optionally in the presence of a catalyst and, if appropriate, in the presence of a diluent, and then the acyl group is split off (process II).

If, for example, 2,6-difluoro-N- [2-chloro-1- (4- (4-acetoxy-3,5-n-dichlorophenyl) phenyl) phenyl) ethyl] benzamide is used as the starting material, the course of the Process II) for the preparation of the compounds of the formula (II) by the following reaction scheme:

All inert organic solutions are used as diluents in process II) medium in question. They can optionally be used mixed with water become. Hydrocarbons such as toluene, xylene, Tetralin, hexane, cyclohexane, halogenated hydrocarbons such as methylene chloride, Chloroform, chlorobenzene, o-dichlorobenzene, alcohols such as methanol, ethanol, glycol, the isomeric propanols, butanols, pentanols, ethers such as diethyl ether, diiso propyl ether, dimethoxyethane, tetrahydrofuran, dioxane, nitriles such as acetonitrile or Butyronitrile, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, further Sulfolan. Alcohols or dimethylformamide are particularly preferably used.

All customary acid acceptors can be used as the base for the cyclization.

Tertiary amines such as triethylamine, pyridine, DABCO, DBU, DBN, N, N-dimethylaniline, also alkaline earth metal oxides such as magnesium and Calcium oxide, also alkali and alkaline earth metal carbonates such as sodium carbonate, Potassium carbonate and calcium carbonate, alkali hydroxides such as sodium and potassium hy hydroxide, also alcoholates such as sodium ethanolate or potassium tert-butoxide.

If appropriate, the process is carried out in the presence of a phase transfer catalyst. As Phase transfer catalyst come for example ammonium compounds such as Tetraoctylammonium bromide or Benzyltriethylammoniumchlorid in question.

The reaction temperature can be varied within a wide range. in the generally one works at temperatures between -20 ° C and 150 ° C, preferably between -10 ° C and 100 ° C.

The reaction is generally carried out under normal pressure.

Generally, an equimolar amount of base is used. It is also possible to work with a base excess.  

Preferred diluents for the subsequent saponification are Water / alcohol mixtures used, such as water / methanol, what water / ethanol or water / propanol or water / amide mixtures such as Water / dimethylformamide (DMF) or water / dimethylacetamide.

The saponification is carried out in the presence of a base. As such come anor ganic and organic bases in question, especially alkali hydroxides such as sodium hydroxide or potassium hydroxide or ammonia.

The reaction temperature can vary within a wide range during the saponification become. Generally one works at temperatures between -10 ° C and 60 ° C, preferably between 0 ° C and 40 ° C. The implementation is generally under Normal pressure carried out.

Cyclization and cleavage of the acyl groups can be carried out both as a one-pot reaction can also be carried out in two separate steps.

The compounds of the formula (VI) required as starting materials in process D) are new.

The compounds of the formula (VI) are obtained, for example, if compounds of the formula (VII)

in which
R ¹ , R ³ and R ^{5 have} the meanings given above, with compounds of the formula (VIII)

in which
X ¹ , X ² and X ^{3 have} the meanings given above,
in the presence of an acidic catalyst, for example a Lewis acid such as iron (III) chloride, aluminum chloride or hydrogen fluoride and preferably in the presence of a diluent, for example a halogenated, in particular chlorinated hydrocarbon such as dichloromethane at temperatures between -20 ° C and 80 ° C implements (cf. WO 96/18619).

Some of the compounds of the formula (VII) are known (J. Amer. Chem. Soc. 61, 1447, 3037 (1939); J. Amer. Chem. Soc. 56, 202 (1934); J. Amer. Chem. Soc 64, 2219 (1942); J. Amer. Chem. Soc. 89, 2711 (1967); J. Org. Chem. 27, 2671 (1962); J. Indian Chem. Soc. 12, 410 (1935); DE-19 11 520) or can be prepared by known methods, for example by reacting the corresponding hydroxybiphenyls of the formula (IX) with the acid anhydrides of the formula (X) or the acid halides (in particular acid chlorides) of the formula (XI):

Some of the compounds of the formula (IX) are known (J. Org. Chem. 29, 3014 (1964), J. Amer. Chem. Soc. 56, 202 (1934)) or can be there according to the methods written.

The compounds of the formulas (X) and (XI) are generally known and common commercially or in a simple and known manner from the corresponding carboxylic acids available.

The compounds of the formula (VIII) are known (see, for example, EP-A-0 594 179, WO 96/18619) or can be prepared by the methods described there.

The compounds of the formula (VI) can also be obtained if acid chloride of the formula (XII)

in which
X ¹ , X ² and X ^{3 have} the meanings given above, with amino alcohols of the formula (XIII)

in which
R ¹ and R ^{3 have} the meanings given above,
optionally in the presence of a diluent (all solvents which are inert to these compounds can be used as diluents, preferably hydrocarbons such as gasoline, benzene, toluene, xylene and tetralin, furthermore halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o- Dichlorobenzene, also ketones, such as acetone and methyl isopropyl ketone, further ethers, such as diethyl ether, tetrahydrofuran and dioxane, moreover carboxylic esters, such as ethyl acetate, and also strongly polar solvents, such as dimethyl sulfoxide and sulfolane; if the hydrolysis stability of the acid halide permits, the reaction can can also be carried out in the presence of water) and, if appropriate, in the presence of a base (all customary acid acceptors come into consideration as the base, preferably tertiary amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene can be used (DBU), diazabicyclonones (DBN), Hünig base and N, N-dimethyl-aniline, also alkaline earth metal oxides, such as magnesium and calcium oxide, in addition to the alkali and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate and alkali - or alkaline earth metal hydroxides such as sodium hydroxide or potassium hydroxide) at temperatures between -20 ° C and + 100 ° C, preferably between 0 ° C and 30 ° C and optionally then the compounds of formula (XIV) thus obtained

in which
X ¹ , X ² , X ³ , R ¹ and R ^{3 have} the meanings given above,
with a chlorinating agent such as thionyl chloride, phosgene or phosphorus oxychloride, optionally in the presence of a diluent, for example hydrocarbons such as toluene, xylene, hexane, cyclohexane, halogenated hydrocarbons such as chlorobenzene, chloroform, methylene chloride or ethers such as diethyl ether, diisopropyl ether, dimethoxyethane, tetrahydrofuran or dioxane Reacts temperatures between 0 ° C and 120 ° C, preferably between 20 ° C and 100 ° C (cf. EP-A-0 696 584).

The compounds of the formula (XII) are generally known and are often commercially available or obtainable in a simple and known manner from the corresponding carboxylic acids.

The compounds (XII) are known (cf. EP-A-0 696 584) or can according to the methods described there are produced.

The Ver still required as starting materials in the process according to the invention Compounds of the formula (III) are generally known compounds of the organic Chemistry. Z stands for a common leaving group, for example halogen (esp special chlorine or bromine), alkylsulfonyloxy (especially methylsulfonyloxy) or optionally substituted arylsulfonyloxy (especially phenylsulfonyloxy, p-chlorophenylsulfonyloxy or tolylsulfonyloxy).

The method according to the invention is characterized in that a verb extension of formula (II) with a compound of formula (III), optionally in counter were a diluent and optionally in the presence of a base.

All customary solvents are suitable as diluents. Preferably Halogenated, aromatic or aliphatic carbons can optionally be used hydrogens, ketones, nitriles and amides. Examples include toluene and Ace clay, acetonitrile, dimethylformamide and dimethylacetamide.

All common inorganic and organic bases can be used as the base. Ge Examples include tertiary amines such as triethylamine, DBN, DBU, DABCO,  Alkali and alkaline earth metal hydroxides such. B. sodium hydroxide, potassium hydroxide and Cal cium hydroxide and alkali and alkaline earth carbonates such. B. sodium carbonate or Potassium carbonate.

The reaction temperature can be varied within a wide range. in the generally one works at temperatures between -20 ° C and 100 ° C, preferably between 0 ° C and 60 ° C.

The reaction is generally carried out under normal pressure.

The compounds of formula (II) and the compounds of formula (III) are in generally used in approximately equimolar amounts. But you can also use an excess of the compounds of formula (III).

The active ingredients are suitable for good plant tolerance and inexpensive warmth blood toxicity to control animal pests, especially insects, Arachnids and nematodes, which are used in agriculture, in forests, in stock and Material protection and in the hygiene sector. You are against normal sen sible and resistant species as well as against all or individual stages of development sam. The pests mentioned above include:

From the order of the Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.

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

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

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

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

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

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

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

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

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

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

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

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

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

From the order of the Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. Buccu latrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias  insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, tinea pellionella, Hofhiannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

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

From the order of the Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

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

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

From the order of Acarina z. B. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

Plant parasitic nematodes include Pratylenchus spp., Radopholus simills, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloido gyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.

The compounds of the formula (I) according to the invention are particularly noteworthy with excellent insecticidal and acaricidal activity.

They can be used with particularly good results in combating plant damage the insects, such as against the horseradish leaf beetle larvae (Phaedon cochleariae), the caterpillars of the owl butterfly (Spodoptera fiugiperda) and the peach aphids (Myzus persicae) or for combating plant-damaging mites, such as against the common spider mite (Tetranychus urticae).

The active compounds can be converted into the customary formulations, such as solutions genes, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble Powders, granules, suspension emulsion concentrates, active ingredient-impregnated Na tur- and synthetic substances as well as very fine encapsulation in polymeric substances.

These formulations are prepared in a known manner, e.g. B. by mixing of the active ingredients with extenders, i.e. liquid solvents and / or solid carriers gerstoffe, optionally using surfactants, so Emulsifiers and / or dispersants and / or foaming agents.

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

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

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

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferro cyan and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, Molybdenum and zinc can be used.  

The formulations generally contain between 0.1 and 95% by weight of active ingredient fabric, preferably between 0.5 and 90% and preferably in addition to extenders and / or surfactants.

The active ingredient according to the invention can be in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active ingredients, such as insecticides, attractants, sterilants, bactericides, Acaricides, nematicides, fungicides, growth regulators or herbi ziden available. Insecticides include, for example, phosphoric acid esters, Carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, by Microorganisms manufactured substances u. a.

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

Fungicides

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide; 2,6-dichloroN- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,
Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,
Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
Dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
Edifenphos, epoxyconazole, ethirimol, etridiazole,
Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanyl, Fuberilafil, Fuberri Furmecyclox,
Guazatine,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan,
Kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methruroxam, Metiram, Metsulfovax, Myclobutanil,
Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, oxadixyl, oxamocarb, oxycarboxin,
Pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,
Quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
Validamycin A, vinclozolin,
Zineb, ziram.

Bactericides

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, Octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, Teclofta lam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides

Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, Az 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,
Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrinhrhrhrinhrhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrofhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrofhrinhrinhrinhrinhrinhrinhrinhrinhrinhrofhrinhrinhrinhrhrinhrhrinhrhrinhrhrinhrinhrofhrinophhrinhrinhrinhrinhrinhrinhrinhrinhrinhrhrinhrhrinhrinhrhrinhrhrinhrhrinhrhrinhrofhrine Cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenothxinfox, Fufionophon, Fufionophon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufon
HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,
Lambda cyhalothrin, lufenuron,
Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
Naled, NC 184, NI 25, Nitenpyram
Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophhine, Pyrachlophhion, Pyrachlophion, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophion Pyridaben, pyrimidifen, pyriproxifen,
Quinalphos,
RH 5992,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozid, tebufenpyrad, tebupirimphos, teflubenzuron, tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thio methon, Thionazin, Thuringiensin, Tralomethrononium, Triaromenontronium, Triaromenhroniaz, Triaratheniazin, Triaratheniazon
Vamidothione, XMC, xylylcarb, YI 5301/5302, zetamethrin.
A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also possible.

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

The active ingredient content of the prepared from the commercially available formulations Application forms can vary widely. The drug concentration of the Use forms can be from 0.0000001 to 95% by weight of active ingredient, preferably are between 0.0001 and 1% by weight.

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

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

The active compounds according to the invention act not only against plant, hygiene and stored-product pests, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, mites, tick mites, flies (stinging and licking), parasitic fly larvae, lice, Hair, feather and fleas. These parasites include:
From the order of the Anoplurida z. B. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
From the order of the Mallophagida and the subordinates Amblycerina and Ischnocerina z. B. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.
From the order Diptera and the subordinates Nematocerina and Brachycerina z. B. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp ., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp.
From the order of the Siphonapterida z. B. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
From the order of the Heteropterida z. B. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
From the order of the Blattarida z. B. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp.
From the subclass of Acaria (Acarida) and the orders of the Meta and Mesostigmata z. B. Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp. Pneumonyssus spp., Sternostoma spp., Varroa spp.
From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata) z. B. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp. Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

For example, they show a good development-inhibiting effect against flies larvae of Lucilia cuprina.

The active compounds of the formula (I) according to the invention are also suitable for combating of althropods, the farm animals, such as. B. cattle, sheep, goats, Horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, Bees, other pets such as B. dogs, cats, house birds, aquarium fish as well as so-called experimental animals, such as. B. hamsters, guinea pigs, rats and Infest mice. By fighting these arthropods, deaths and Reductions in performance (for meat, milk, wool, skins, eggs, honey, etc.) can be reduced so that by using the active compounds according to the invention more economical and easier animal husbandry is possible.

The active compounds according to the invention are used in the veterinary sector in in a known manner by enteral administration in the form of, for example, tablets, Capsules, watering, drenching, granules, pastes, boluses, the feed-through process, suppositories, by parenteral administration, such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, through nasal Application, by dermal application in the form of, for example, diving or Bathing (dipping), spraying (spray), pouring (pour-on and spot-on), des Washing, powdering and with the help of shaped articles containing active ingredients, such as  Collars, ear tags, tail tags, limb straps, halters, Mar marking devices etc.

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

It has also been found that the compounds of the formula (I) according to the invention The technical materials show a high insecticidal effect against insects to destroy.

The following are examples and preferably - but without limitation - Called insects:

Beetle like
Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus afticanus, Lyctus planicollis, Lyctus linearesceses, Lyctus pubescuses, Lyctus pubescuses, Lyctus pubis aescus, Lyctus pubescuses, Lyctus pubescuses, Lyctus pubescuses, Lyctus linearesces, Rug Xyleborus spec. Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus.

Skin wings like
Sirexjuvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.

Termites like
Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwinien sis, Zootermopsis nevadensis, Coptotermes formosanus.

Bristle tails like
Lepisma saccarina.

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

The one to be protected against insect attack is very particularly preferably Material around wood and wood processing products.

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

The active ingredients can be used as such, in the form of concentrates or in a conventional manner Formulations such as powders, granules, solutions, suspensions, emulsions or Pastes can be applied.

The formulations mentioned can be prepared in a manner known per se, e.g. B. by mixing the active ingredients with at least one solution or Diluents, emulsifiers, dispersants and / or binders or fixatives, Water repellants, optionally desiccants and UV stabilizers and if necessary Dyes and pigments as well as other processing aids.

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

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

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

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

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

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

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

As organic-chemical binders in the context of the present invention the known water-dilutable and / or in the organic used chemical solvents soluble or dispersible or emulsifiable synthetic resins and / or binding drying oils, in particular binders consisting of or containing an acrylic resin, a vinyl resin, e.g. B. polyvinyl acetate, polyester resin, Polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modes fused 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 used.

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

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

The binder mentioned can be wholly or partly by a fixation medium (mixture) or a plasticizer (mixture) can be replaced. These additions are meant to volatilization of the active ingredients and crystallization or precipitation prevent. They preferably replace 0.01 to 30% of the binder (based on 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 alnyl stearate, oleates such as butyl oleate, glycerol ether or higher molecular weight glycol ether, glycerol ester and p-toluenesulfonic acid ester.

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

Water is also particularly suitable as a solvent or diluent, optionally mixed with one or more of the above organic chemical solvents or diluents, emulsifiers and dispersants.

A particularly effective wood protection is achieved through industrial impregnation processes, e.g. B. vacuum, double vacuum or printing process.

The ready-to-use agents can, if appropriate, still further insecticides and optionally contain one or more fungicides.

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

Insecticides such as chlorpyriphos are particularly preferred mixing partners. Phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, Permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumuron, as well as fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole, Tebuconazole, cyproconazole, metconazole, imazalil, dichlofluanid, tolylfluanid, 3-iodo-2-propynyl butyl carbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octyliso called thiazolin-3-one.

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

Manufacturing examples Example (I-1)

2- (2,6-difluorophenyl) -4- (4- (4- (propyl-2-oxy) -3,5-dichlorophenyl) phenyl) -4,5-dihydro- oxazoline

2.9 g (7 mmol) 2- (2,6-difluorophenyl) -4- (4- (4-hydroxy-3,5-dichlorophenyl) phenyl) -4.5- dihydro-oxazoline in 50 ml of acetonitrile with 1.9 g (14 mmol) of potash and 8.6 g (70 mmol) of 2-propyl bromide refluxed for 6 hours. You pour the reaction mix in water and extract the product with methylene chloride. The organic After washing with water, the phase is evaporated in vacuo and the Chromatograph the residue on silica gel in the system cydohexane / ethyl acetate (2: 1). 1.6 g of 2- (2,6-difluoropheny1) -4- (4- (4- (propyl-2-oxy) -3,5-dichlorophenyl) - are obtained. phenyl) -4,5-dihydro-oxazoline as an oil of log P (pH 7.5) = 5.65 (yield 49.5% i.e.).

Analogously or in accordance with the general regulations for the manufacture of the Compounds of formula (I) listed in the following table.  

Table 1

Preparation of starting compounds Example (II-1)

2- (2,6-difluorophenyl) -4- (4- (4-hydroxy-3,5-dichlorophenyl) phenyl) -4,5-dihydro- oxazoline

To dissolve 53 g (0.1 mol) of 2,6-difluoro-N- [2-chloro-1- (4- (4-ethoxycarbonyl-3,5- dichlorophenyl) phenyl) ethyl] -benzamide in 300 ml of dimethylformamide is added dropwise Stir at 10 ° C a solution of 6 g (0.14 mol) sodium hydroxide in 10 ml water to. After a stirring time of 5 h at 10 ° C., 100 ml of 25% ammonia solution are added and stir for 3 days at 20 ° C. The reaction mixture is then poured onto water and extracted the product with dichloromethane. The organic phase is in a vacuum evaporated and the remaining crude product stirred with diisopropyl ether. Man receives 15 g (yield = 35.8% of theory) of 2- (2,6-difluorophenyl) -4- (4- (4-hydroxy-3,5-di chlorophenyl) phenyl) -4,5-dihydro-oxazoline, mp: 176 to 179 ° C.

Analogously or in accordance with the general regulations for the manufacture of the Compounds of formula (II) given in the following table.  

Table 2

Preparation of starting compounds Example (VI-1)

2,6-difluoro-N- [2-chloro-1- (4- (4-ethoxycarbonyl-3,5-dichlorophenyl) phenylethyl] - benzamide

32.5 g (0.13 mol) of 2,6-difluoro-N- [2-chloro-1-methoxyethyl] benzamide and 40 g (0.13 mol) (2,6-dichloro-4-phenyl) phenyl ethyl carbonate in 100 ml Dissolved dichloromethane and added to 500 ml of anhydrous hydrofluoric acid at 0 ° C. After After stirring overnight at 14 ° C, the hydrofluoric acid is removed, the residue in Di chloromethane and washed with water. The organic phase will separated and evaporated in vacuo. 54 g of 2,6-difluoro-N- [2-chloro-1- (4-  (4-ethoxycarbonyl-3,5-dichlorophenyl) phenyl) ethyl] benzamide as a tough resin. log P (pH 2.3): 4.17.

The product is implemented without further cleaning.

Preparation of (2,6-dichloro-4-phenyl) phenyl, ethyl carbonate

40.6 g (0.17 mol) of 3,5-dichloro-4-hydroxybiphenyl (made according to J.C. Collert et al. JACS 56, 202 (1934)) and 17.2 g (0.17 mol) of triethylamine are dissolved in 170 ml of vinegar ester dissolved and at 10 ° C dropwise with 18.4 g (0.17 mol) of chloroformic acid ethyl ester added. After stirring overnight, the reaction solution is washed with water and concentrates the organic phase. For further cleaning, the raw product (51.2 g) chromatographed on silica gel in the chloroform system. You get 48 g (yield: 90.8% of theory) of (2,6-dichloro-4-phenyl) phenyl, ethyl carbonate as Oil. log P (pH 7.5); 4.65.  

Examples of use Example A Heliothis armigera test

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

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

Soybean shoots (Glycine max) are dipped into the active ingredient preparation desired concentration and treated with caterpillars of the cotton capsule worm (Heliothis armigera) occupied while the leaves are still moist.

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

In this test, e.g. B. the compound according to preparation example I-1 in a exemplary drug concentration of 0.1%, a kill of 100% after 6 Days.  

Example B Nephotettix test

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

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

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

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

In this test, e.g. B. the compounds according to Preparation Examples I-2 and I-3, at an exemplary drug concentration of 0.1%, a kill of 100% after 6 days.  

Example C Phaedon larval test

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

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

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

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

In this test, e.g. B. the compounds according to Preparation Examples I-1 and I-3, at an exemplary drug concentration of 0.1%, a kill of 100% after 7 days.  

Example D Plutella test

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

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

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

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

In this test, e.g. B. the compound according to preparation example I-1 in a exemplary drug concentration of 0.1%, a kill of 100% after 6 Days  

Example E Spodoptera exigua test

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

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

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars of the army worm (Spo doptera exigua) occupied while the leaves are still moist.

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

In this test, e.g. B. the compound according to preparation example I-1 in a exemplary drug concentration of 0.1%, killing 100% in 6 Days.  

Example F Spodoptera frugiperda test

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

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

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars of the army worm (Spo doptera frugiperda) occupied while the leaves are still moist.

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

In this test, e.g. B. the compounds according to Preparation Examples I-1, I-2 and I-3 are killed at an exemplary active ingredient concentration of 0.1% from 100% after 7 days.  

Example G Tetranychus test (OP-resistant / immersion treatment)

Solvent: 3 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified Amount of emulsifier and dilute the concentrate with water containing emulsifier the desired concentrations.

Bean plants (Phaseolus vulgaris) which are strong from all stages of common spinning mite (Tetranychus urticae) are infested in an active ingredient preparation of the ge wished concentration immersed.

After the desired time, the effect is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites are removed were killed.

In this test, e.g. B. the compounds according to Preparation Examples I-1, I-2 and I-3 are killed at an exemplary active ingredient concentration of 0.01% from 100% in 7 days.

Claims (8)

1. Compounds of formula (I)
in which
X ^{1 represents} hydrogen, halogen, alkyl, alkoxy or alkylthio,
X ^{2 represents} halogen, alkyl, alkoxy or alkylthio,
X ^{3 represents} hydrogen, halogen, alkyl, alkoxy or alkylthio, especially hydrogen,
R ^{1 represents} hydrogen, halogen, alkyl or -CH ₂ -CR ⁴ = CH ₂ ,
R ^{2 represents} alkyl, hydroxyalkyl, in each case optionally substituted alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, cycloalkenylalkyl, phenylalkyl, naphthylalkyl or tetrahydronaphthylalkyl,
R ^{3 represents} halogen or alkyl, and
R ^{4 represents} hydrogen or in each case optionally substituted alkyl or aryl. 2. A process for the preparation of compounds of the formula (I) according to claim 1, characterized in that compounds of the formula (II)
in which
X ¹ , X ² , X ³ , R ¹ and R ^{3 have} the meanings given in claim 1,
with compounds of the formula (III)
ZR ² (III),
in which
R ^{2 has} the meaning given in claim 1 and
Z represents a leaving group,
if appropriate in the presence of a diluent and if appropriate in the presence of a base. 3. Compounds of formula (II)
in which
X ¹ , X ² , X ³ , R ¹ and R ^{3 have} the meanings given in claim 1. 4. pesticides, characterized by a content of minde at least one compound of formula (I) according to claim 1. 5. Use of compounds of formula (I) according to claim 1 for loading pest control. 6. A method for controlling pests, characterized in that compounds of formula (I) according to claim 1 for pests and / or lets their living space take effect. 7. Process for the manufacture of pesticides, thereby ge indicates that compounds of formula (I) according to claim 1 with Extenders and / or surfactants mixed. 8. Use of compounds of formula (I) according to claim 1 for the Her provision of pesticides.