EP0740662A1

EP0740662A1 - Aryl-5-methylene-oxazole derivatives

Info

Publication number: EP0740662A1
Application number: EP95905116A
Authority: EP
Inventors: Udo Kraatz; Ulrike Wachendorff-Neumann; Christoph Erdelen; Andreas Turberg; Norbert Mencke
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1994-01-17
Filing date: 1995-01-04
Publication date: 1996-11-06
Also published as: DE4401100A1; JPH09507491A; AU1385595A; WO1995019351A1

Abstract

The invention pertains to new aryl-5-methylene-oxazole derivatives of formula (I), wherein R1 is alkyl or optionally substituted aryl; R2 is alkyl or optionally substituted phenyl, phenylalkyl, phenylalkenyl, phenoxyalkyl or phenylthioalkyl; or R?1 and R2¿ together are double-linked, optionally substituted or anellated alkandiyl, where optionally one or two non-vicinal CH¿2? groups are substituted by O and/or S; and R?3¿ is halogen, alkyl or alkoxy; R4 is halogen, alkyl, alkoxy, alkylthio, alkyl halide, alkoxy halide or alkylthio halide, and n stands for a number 0, 1, 2, 3 or 4. The invention also pertains to a method for their preparation, new intermediate products of formula (II) as well as the use of the compounds of formula (I) as pesticides.

Description

Aryl 5-methylene oxazole derivatives

The invention relates to new aryl-5-methylene-oxazole derivatives, a process for their preparation and their use for controlling animal pests.

It is already known that certain herbicides metabolize via the intermediate stage of 2-aryl-5-methylene-oxazole derivatives (see, for example, J. Agr. Food. Chem., 19 (2), 314-18, 1971; ibid. 319-24, 171). Furthermore, the preparation and use of various 2-aryl-5-methyleneoxazole derivatives are known as intermediates for herbicides (cf. US 37 45 168, J. Heterocycl. Chem., 26 (5), 1495-9, 1989); Gazz. Chim. Ital., 115 (12, Pt.B), 691-6, 1985; Z. Naturforsch., B: Chem. Sei., 44 (10), 1298-312, 1989). So far, nothing is known about the use for controlling animal pests.

The new aryl-5-methylene-oxazole derivatives of the formula (I) have now been found

in which

R ^{1 represents} alkyl or optionally substituted alyl; R ^{2 represents} alkyl or optionally substituted phenyl, phenylalkyl, phenylalkenyl, phenoxyalkyl and phenylthioalkyl; or

R ¹ and R ² together represent doubly linked, optionally substituted or fused alkanediyl, where one or two non-adjacent CH ₂ groups are optionally replaced by O and / or S; and

R ^{3 represents} halogen, alkyl or alkoxy;

R ^{4 represents} halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or haloalkylthio and

stands for a number 0, 1, 2, 3 or 4.

Furthermore, it was found that the new aryl-5-methylene-oxazole derivatives of the formula (I) are obtained if substituted benzamides of the formula (II)

in which

R, 1, R τ 2, R r> 3, R Γ 4 and n have the meaning given above,

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

Furthermore, it has been found that aryl-5-methylene-oxazole derivatives of the formula (I) are very suitable for controlling animal pests. They are particularly characterized by their high effectiveness against arthropods and nematodes.

Surprisingly, the aryl-5-methylene-oxazole derivatives of the formula (I) according to the invention show a high activity against animal pests. 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.

R ¹ is preferably C _j -C ₈ alkyl or phenyl which is optionally mono- to pentasubstituted by halogen, the same or different,

C _r C ₆ alkyl, C _r C ₆ alkoxy, C _r C ₆ - alkylthio, C _r C ₆ haloalkyl, C _r C ₆ - haloalkoxy, C ₁ -C ₆ haloalkylthio.

R ² is preferably C _j -C ₆ - alkyl, or represents in each case optionally mono- to tetrasubstituted by identical or different substituents, phenyl, benzyl, pheneth-1-yl, pheneth-2-yl, phenoxymethyl,

Phenylthiomethyl, phenoxyeth-1-yl, phenoxyeth-2-yl or styryl, where each may be mentioned as a phenyl substituent

Halogen,

C _r C ₁₈ alkyl, C ₁ -C ₈ alkoxy-C ₁ -C ₈ alkyl,

Ct -C ₈ haloalkoxy,

C _j -C ₄ haloalkyl,

C _j -C _jg - alkoxy, which is optionally interrupted by a further 1-3 oxygen atoms, C _r C ₁₈ alkylthio,

C _j -C ₈ haloalkylthio,

3, 4-difluoromethylene dioxo,

3,4-tetrafluoroethylene dioxo, optionally substituted by C _] -C ₄ alkyl, C ₃ -C ₆ cycloalkyl and / or halogen substituted benzyliminooxymethyl, in each case optionally by C _j -C ₆ alkyl, C _j -C ₈ alkoxy , Cyclohexyl or

Phenyl substituted cyclohexyl and cyclohexyloxy; optionally single or double, identical or different by halogen,

C -, - C ₄ - alkyl or C _j -C _4. haloalkyl substituted pyridyloxy; each through single to triple, the same or different C _j -C ₁₂ alkyl, halogen, C ^ haloalkyl, CC ₈ alkoxy, C _] -C ₆ haloalkoxy, CC ₈ alkoxy-C _j -C _ß alkyl, C - C ₆ alkoxy -ethyleneoxy, C _j -C ₆ alkyl thio and / or C ₁ -C ₆ haloalkylthio substituted phenyl, benzyl, phenoxy, phenylthio, benzyloxy and benzylthio, or

R ¹ and R ² together preferably represent double-linked, optionally one to four times, identically or differently substituted 2- to 6-membered, optionally benzanellated alkanediyl, optionally one or two non-adjacent CH ₂ groups by O and / or S are replaced, and suitable substituents: C _j -C ₄ -alkyl, in each case optionally mono- to tetrasubstituted by identical or different substituents, phenyl or a fused-on benzo, wherein each of the substituents mentioned in connection with the definition of R ² is phenyl as a substituent come into question.

R ³ preferably represents fluorine, chlorine, bromine, C _j -C ₄ alkyl or C _j -C ₄ alkoxy.

R ⁴ preferably represents fluorine, chlorine, bromine, C _j -C ₄ alkyl, C _j -C ₄ alkoxy, C _j - C ₄ alkylthio, C ₁ -C ₄ haloalkyl, C _] -C ₄ haloalkoxy or C _] -C ₄ haloalkylthio.

n is preferably a number 0.1, 2, 3 or 4.

R ¹ particularly preferably represents C _] -C ₄ -alkyl or phenyl, which is optionally mono- to pentasubstituted, identically or differently, by F, Cl, Br, C _r C ₄ -alkyl, C _r C ₃ -alkoxy , C _r C ₃ alkylthio which is monosubstituted to pentasubstituted by identical or different F and / or Cl-substituted C _j _-C-j alkyl, mono- to pentasubstituted by identical or different F and / or Cl substitu¬ iertes C _r C ₄ -alkoxy, SCF ₃ or SCHF ₂ .

R ² particularly preferably represents C _j -C ₄ -alkyl or represents in each case optionally mono- to tetrasubstituted by identical or different substituents, phenyl, benzyl, Pheneth- 1-yl, pheneth-2-yl, phenoxymethyl, phenylthiomethyl, phenoxy eth- 1 - yl, phenoxyeth-2-yl or stryryl, each of which may be mentioned as a phenyl substituent F, Cl, Br, C, -C ₁₈ alkyl, C _r C ₆ alkoxy-C _r C ₈ alkyl _; mono- to hexasubstituted by identical or different F and / or Cl sub- stituiertes C _j -C ₈ -alkoxy which is monosubstituted to pentasubstituted by identical or different F and / or Cl sub¬ stituiertes CC ₂ alkyl,

C _r C ₁₈ alkoxy and - (OC ₂ H ₄ ) ₁ . ₃ -O-C ₁ -C ₆ alkyl, C _r C ₁₂ - alkylthio, one to six times, by identical or different F and / or Cl sub¬ stituiertes C _j -C ₈ alkylthio, 3, 4-difluoromethylenedioxo, 3, 4 -Tetrafluorethylendioxo, optionally substituted by C _j -C ₄ - alkyl, C ₃ -C ₆ cycloalkyl, fluorine and / or chlorine-substituted Benzyliminooxymethyl, in each case optionally C ₁ -C ₄ alkyl, CC ₄ -alkoxy, cyclohexyl or phenyl substituted cyclohexyl and cyclohexyloxy; pyridyloxy optionally substituted once or twice, identically or differently by F, Cl or CF ₃ ; each through single to triple, the same or different

C _j -C _jj alkyl, F, Cl, Br, CF ₃ , CC ₄ alkoxy, simple to sixfold, identical or differently substituted by F and / or Cl, C _j -C ₄ alkoxy, CC ₄ - alkoxy-C _j -C ₄ alkyl, C _j -C ₄ -alkoxy-ethyleneoxy, C _j -C ₄ -alkylthio which is monosubstituted to hexasubstituted by identical or different F and / or Cl-substituted C -, - C ₄ - alkylthio-substituted phenyl, Benzyl, phenoxy, phenylthio, benzyloxy and

Benzylthio or

R ² together are particularly preferably double-linked, optionally mono- to tetrasubstituted, identically or differently substituted 2- to 6-membered, optionally benzanellated alkanediyl, optionally one or two non-adjacent CH ₂ groups being replaced by O and / or S. and are suitable substituents: C _j -C ₄ -alkyl and in each case optionally mono- to tetrasubstituted by identical or different substituents, phenyl or a fused benzo group, wherein in each case as substituents in question substituents mentioned for phenyl ² in connection with the definition of R come . R ³ particularly preferably represents fluorine, chlorine, methyl or methoxy.

R ⁴ particularly preferably represents fluorine, chlorine, C, -C ₃ -alkyl, C _j -C ₃ -alkoxy, CC ₃ -alkylthio, mono- to quintuple, identical or different, substituted by fluorine and or chlorine, C ₁ -C ₃ - Alkyl, single to quintuple, identical or different C _j -, - alkoxy, SCF ₃ and SCHF ₂ substituted by fluorine and / or chlorine.

n particularly preferably represents a number 0, 1, 2, 3 or 4.

It applies in each case that the radicals R ^{4 may be the} same or different for n> 1.

Compounds of the formula (1-1) are very particularly preferred

in which

R ^{1 represents} methyl, ethyl, n-propyl, i-propyl, phenyl or 4-chlorophenyl,

R represents methyl, ethyl, n-propyl, i-propyl or phenyl or benzyl, which are substituted by one of the substituents R listed in Table 1 below and

A represents one of the substituents listed in Table 2 below or

R ¹ and R ² together with the carbon atom to which they are attached represent a cyclopentyl or cyclohexyl radical. Table 1:

Table 1: - continued

Table 1. - Continued

Table 1: • - Continued

Table 2:

Very particularly preferred substituents A:

Depending on the nature of the substituents, the compounds of the formula (I) can be in the form of geometric and / or optical isomers or isomer mixtures of different compositions. The invention relates to both the pure isomers and the isomer mixtures.

The hydrocarbon radicals mentioned above in the definition of the compounds according to the invention, such as alkyl, are in each case straight-chain or branched as far as possible, even in conjunction with heteroatoms, such as alkoxy.

The general definitions given above or in preferred ranges apply both to the end products of the formula (I) and correspondingly to the starting materials or intermediate products required in each case for the preparation.

These radical definitions can be combined with one another as desired, that is to say also between the specified ranges of preferred compounds. Examples of the compounds of the formula (I) according to the invention are listed in the tables below.

Table 3:

The compounds of Table 3 correspond to the formula (II) in which A represents 2,6-difluorophenyl, R ^{1 represents} methyl and R ^{2 has} the meanings listed below:

Verb.

No. R ²

1 4-chlorophenyl,

2 4-bromophenyl,

3 4-tert-butylphenyl,

4 4-n-pentylphenyl,

5 4-neopentylphenyl,

6 4-ethoxyphenyl,

7 4-n-propoxyphenyl,

8 4-i-propoxyphenyl,

9 4-n-butoxyphenyl,

10 4-n-pentoxyphenyl,

Table 3: Continuation:

Verb.No. R ²

11 4-n-hexoxyphenyl,

12 4-trifluoromethylphenyl,

13 4-trifluoromethoxyphenyl,

14 4-chloro-2-methylphenyl,

15 2,4-dichlorophenyl,

16 4-chlorophenylphenyl

17 4-chlorophenoxyphenyl,

18 4-chlorobenzyloxyphenyl,

19 3,5-dichloro-4-trifluoromethoxyphenyl

20 4- (1, 1, 2,2-tetrafluoroethoxy) phenyl

21 4-difluoromethoxy-phenyl

If, for example, N- (3-methyl-but-1-yn-3-yl) -2,6-difluorobenzamide and sodium hydride are used, the course of the reaction of the process according to the invention can be represented by the following formula:

Formula (II) provides a general definition of the benzamides to be used as starting materials in process a) for the preparation of the compounds of the formula (I). In the formula (II), R ¹ , R ^2, R ³ , R ⁴ and n preferably or particularly preferably have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) as preferred or as were particularly preferably indicated for R ¹ , R ^2, R ³ , R ⁴ and n.

Some of the starting materials of the formula (II) are known and / or can be prepared by processes known per se (cf., for example, J. Agr. Food Chem., 19 (3), 417-21, 1971; US 34 81 979, DE 19 58 180).

The benzamides of the formula (II) required as starting materials for the preparation of the new diaryl-5-methylene-oxazole derivatives of the formula (I)

in which

R ^{1 represents} alkyl or optionally substituted aryl;

R represents alkyl or optionally substituted phenyl, phenylalkyl,

Phenylalkenyl, phenoxyalkyl and phenylthioalkyl; or R ¹ and R ² together represent doubly linked, optionally substituted or fused alkanediyl, one or two non-adjacent CH ₂ groups optionally being replaced by O and / or S; and

R ^{3 represents} halogen, alkyl or alkoxy;

R ^{4 represents} halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or

Haloalkylthio stands and

n stands for a number 0, 1, 2, 3 or 4

are new and the subject of the invention with the exception of the compounds in which R ¹ and R ² simultaneously represent methyl.

The new and known benzamides of the formula (II) are obtained, for example, by benzoyl chlorides of the formula (III)

in which

R ³ , R ⁴ and n have the meaning given above,

in a generally known and customary way according to Schotten-Baumann with propargylamines of the formula (IV)

in which R ¹ and R ~ have the meaning given above,

if appropriate in the presence of a diluent, and if appropriate in the presence of a base (cf. Organikum, VEB Deutscher Verlag der Wissenschaften, Berlin 1976, pp. 504, 513 and preparation examples).

The benzoyl chlorides of the formula (III) and the propargylamines of the formula (IV) are generally known compounds and / or can be prepared in a simple manner by known methods.

The process according to the invention for the preparation of the compounds of the formula (I) is preferably carried out in the presence of a diluent.

Suitable diluents for carrying out the process according to the invention are all customary inert organic solvents. Aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, petroleum ether, hexane, ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethyl englykoldimethyl or - di ethyl ether; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide, N-

Methyl pyrrolidone or hexamethyl phosphoric acid triamide.

The reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures between 20 ° C and 120 ° C, preferably at temperatures between 40 ° C and 100 ° C.

The process according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure - generally between 0.1 bar and 10 bar.

The process according to the invention is preferably carried out in the presence of a base. All common inorganic or organic bases come in here

Consideration. Alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, are preferably usable. Sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethyl aminopyridine, Diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene

(DBU).

To carry out the process according to the invention, the benzamides of the formula (II) required in each case are reacted with 0.1 to 80 mol%, preferably 1-50 mol% and in particular 1-20 mol% of the base. However, it may also be advantageous to use the benzamides of the formula (II), if appropriate in the presence of an inert

Conversion of diluent, without the addition of a base, by prolonged heating into the compounds of the formula (I) according to the invention. The reactions are generally carried out in a suitable diluent, and the reaction mixture is stirred for several hours at the temperature required in each case. Working up is carried out in the methods according to the invention in each case by customary methods (cf. the preparation example).

The active substances are suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. 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 e.g. 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 spec.

From the order of the Symphyla e.g. Scutigerella immaculata.

From the order of the Thysanura, for example Lepisma saccharina. From the order of the Collembola, for example Onychiurus armatus.

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

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

From the order of the anoplura e.g. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.

From the order of the Mallophaga e.g. Trichodectes spp., Damalinea spp.

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

From the order of the Heteroptera e.g. Eurygaster 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, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis,

Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella Purococcus hurocus Psylla spp.

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

Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplocapsa n.

Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia po- dana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of the Coleoptera e.g. Anobium punctatum, Rhizopertha dominica, Acanthoscelides obtectus, Bruchidius 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 psioloides , Agriotes spp.,

Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

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., Tabanus spp. Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of the Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp ..

From the order of the Arachnida e.g. Scorpio maurus, Latrodectus mactans.

From the order of the Acarina e.g. 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 similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp ..

The substances of the formula (I) according to the invention also have a fungicidal activity.

The active ingredients can be converted into the usual 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 polymeric substances and in coating compositions for seeds, furthermore in formulations with Fuel sets, such as smoking cartridges, cans, spirals, etc., as well as ULV cold and Waπnnebel formulations.

These formulations are produced known manner in b ^e, for example by mixing the active compounds with extenders, that is liquid solvents and / or solid carriers, optionally with the use of surfactants, that is emulsifiers and / or dispersants and / or foam-forming agents.

If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or 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; with liquefied gaseous extenders or carriers are such

Liquids are meant which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; Possible solid carriers are: for example 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; Solid carriers for granules are possible: for example broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco sticks; Possible emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersing agents are, for example, lignin sulfite waste 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 also 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 are used.

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

The active compounds according to the invention can be present in their commercially available formulations and in the use forms prepared from the formulations in a mixture with other active compounds, such as insecticides, attractants, sterilants, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.

The following connections are mentioned:

Acrinathrin, Alphamethrin, Betacyfluthrin, Bifenthrin, Brofenprox, Cis-Resmethrin,

Clocythrin, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cypermethrin, Deltamethrin, Esfenvalerate, Etofenprox, Fenpropathrin, Fenvalerate, Flucythrinate, Fluvalinate, Lambda-cyhalothrin, permethrin, pyresmethrin, pyrethrum, silafluofen, tralomethrin, zetamethrin,

Alanycarb, Bendiocarb, Benfuracarb, Bufencarb, Butocarboxim, Carbaryl, Cartap, Ethiofencarb, Fenobucarb, Fenoxycarb, Isoprocarb, Methiocarb, Methomyl, Metol-carb, Oxamyl, Pirimicarb, Promecarb, Propoxur, Terbam, Thiodicarb, Thiofanox,

Trimethacarb, XMC, xylylcarb,

Acephate, Azinphos A, Azinphos M, Bromophos A, Cadusafos, Carbophenothion, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cyanophos. Demeton M, Demeton-S-methyl, Demeton S, Diazinon, Dichlorvos, Dicliphos, Dichlorfenthion, Dicrotophos, Dimethoate, Dimethylvinphos, Dioxathion, Disulfoton, Edifenphos, Ethion, Etrimphos, Fenitrothion, Fenthion, Fonophos, Isothophophos, Hepthosphate, Hepten Isoxathion, Phorate, Malathion, Mecarbam, Mervinphos, Mesulfenphos, Methacrifos, Methamidophos, Naled, Omethoate, Oxydemeton M, Oxydeprofos, Parathion A, Parathion M, Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon, Moxim, Pirimhiphiphiphiros Prothiophos

Prothoate, Pyraclophos, Pyridaphenthion, Quinalphos, Salithion, Sebufos, Sulfotep, Sulprofos, Tetrachlorvinphos, Temephos, Thiomethon, Thionazin, Trichlorfon, Triazophos, Vamidothion, Buprofezin, Chlorfluazuron, Flifycloxifonuron, Flifufenoxuronuron, Tifluboxuronuron Triflumuron,

Imidacloprid, nitenpyram, N - [(6-chloro-3-pyridinyl) methyl] -N'-cyano-N-methylethanimidamide (NI-25),

Abamectin, Amitrazin, Avermectin, Azadirachtin, Bensultap, Bacillus thuringiensis, Cyromazine, Diafenthiuron, Emamectin, Ethofenprox, Fenpyrad, Fipronil, Flufenprox, Lufenuron, Metaldehyde, Milbemectin, Pymetrozine, Trebiazuronyr

Aldicarb, Bendiocarb, Benfuracarb, Carbofuran, Carbosulfan, Chlorethoxyfos, Cloethocarb, Disulfoton, Ethophrophos, Etrimphos, Fenamiphos, Fipronil, Fonofos, Fosthiazate, Furathiocarb, HCH, Isazophos, Isofenphos, Phiophimoxox, Phiophosox, Phiophos, Monophyamate, Methiocarbam, Monophyamate, Methiocarbox, Methiocarbox, Methiocorox, Phi Pyrachlofos, Sebufos, Silafluofen, Tebupirimiphos, Tefluthrin, Terbufos, Thiodicarb, Thiafenox,

Azocyclotin, Butylpyridaben, Clofentezine, Cyhexatin, Diafenthiuron, Diethion, Emamectin, Fenazaquin, Fenbutatin Oxide, Fenothiocarb, Fenpropathrin, Fenpyrad, Fenpyroximate, Fluazinam, Fluazuron, Flucycloxuron, Flufenoxuron, Methoxin, Oxoxinatex, Oxoxin, Oxoxin, Oxoxin, Oxoxin, Oxidoxin , Phosalone, Profenofos, Pyraclofos, Pyridaben, Pyrimidifen, Tebufenpyrad, Thuringiensin, triarathenes and 4-bromo-2- (4-chlorophenyl) -l- (ethoxymethyl) -5- (trifluoromethyl) -lH-pyrrole-3-carbonitrile (AC 303630).

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 connections through which the

Effect of the active ingredients is increased without the added synergist must be active itself.

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.

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 and endoparasites) such as tick ticks, leather ticks, space mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, Hair lice, featherlings, fleas and endoparasitic worms. For example, they show excellent effectiveness against ticks, such as Boophilus microplus.

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 Hamsters, guinea pigs, rats and

Infest 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 tags , Limb bands, holsters, marking devices etc.

The preparation and use of the compounds of the formula (I) according to the invention are illustrated by the following examples.

Production examples: Example 1:

To a solution of 6.7 g (30 mmol) of N- (3-methyl-but-l-in-3-yl) -2,6-difluorobenzamide in 50 ml of dimethylformamide is added in portions 0.4 g (10 mmol) of 60% sodium hydride and stirred at 60 ° C for 2 hours. The dimethylformamide is largely distilled off under reduced pressure, the residue is taken up in water and the product is extracted with methylene chloride. After drying over magnesium sulfate, the organic phase is concentrated and the residue of 4.6 g is distilled in a _bulb tube at 150 ° _{C./5 mm} .

2.8 g (41.9% of theory) of 2- (2,6-difluorophenyl) -4,5-dihydro-4,4-dimethyl-5-methylene-oxazole of the formula shown above with the refractive index n ^ ^{0 are obtained} = 1.5050.

Example 2:

Analogously to Example 1, 2- (2,6-difluorophenyl-1-aza-3-oxa-4-methylene-spiro [4,5] dec-1-ene of the formula shown above with a log _P of 4 is obtained , 05. Example 3:

Analogously to Example 1, 2- (2,6-difluorophenyl) -4,5-dihydro-4,4-diethyl-5-methylene-oxazole of the formula shown above with a log _p of 3.65 is obtained.

Preparation of the starting compounds:

A solution of 8.3 g (0.1 mol) of 3-amino-3-methyl-but-l-in in 100 ml of methylene chloride and 11.1 g (0.11 mol) of triethylamine are stirred at 20 ° C 19.4 g (0.11 mol) of 2,6-difluorobenzoyl chloride, dissolved in 20 ml of methylene chloride, was added dropwise. After the exothermic reaction has subsided, the mixture is heated under reflux for 1 hour, the solution is washed with water and, after drying over magnesium sulfate, it is concentrated on a rotary evaporator.

19.5 g (87.4% of theory) of N- (3-methyl-but-1-yn-3-yl) -2,6-di-fluorobenzamide with a melting point of 94-98 ° C. are obtained

Example: A

Plutella test

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

To produce a suitable preparation of active compound, 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 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 cabbage cockroach (Plutella maculipennis) 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.

In this test, e.g. the compounds of Preparation Examples 2 and

3 with an exemplary active ingredient concentration of 0.1% after 7 days a degree of killing of 100%.

Example B

Nephotettix test

Rice seedlings (Oryza sativa) are treated by dipping into the active ingredient preparation of the desired concentration and populated with larvae of the green rice leafhopper (Nephotettix cincticeps) 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.

In this test, for example, compound 2 of the preparation examples, with an exemplary active compound concentration of 0.1%, causes a degree of killing of 100% after 6 days.

Example C

Cockroach test

Test animals: Periplaneta americana

Solvent: 35 parts by weight of ethyl englykolmonomethylether

Emulsifier: 35 parts by weight of nonylphenol polyglycol ether

To produce a suitable formulation, three parts by weight of active compound are mixed with seven parts by weight of the solvent-emulsifier mixture mentioned above, and the emulsion concentrate thus obtained is diluted with water to the concentration desired in each case.

2 ml of this active ingredient preparation are pipetted onto filter paper discs (0 9.5 cm), which are located in Petri dishes of the appropriate size. After the filter discs have dried, 5 test animals are transferred to P. americana and covered.

After three days, the effectiveness of the drug preparation is determined. 100% means that all cockroaches have been killed; 0% means that no cockroaches have been killed.

In this test, e.g. the compound according to preparation example 1 at an exemplary active ingredient concentration of 100 ppm, a kill of 100%.

Claims

Aryl-5-methylene-oxazole derivatives of the formula (I),

in which

R represents alkyl or optionally substituted aryl;

R ^{2 represents} alkyl or optionally substituted phenyl, phenylalkyl, phenylalkenyl, phenoxyalkyl and phenylthioalkyl; or

R ¹ and R ² together represent doubly linked, optionally substituted or fused alkanediyl, where appropriate one or two non-adjacent CH ₂ groups are replaced by O and / or S; and

R represents halogen, alkyl or alkoxy;

represents halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or haloalkylthio and

stands for a number 0, 1, 2, 3 or 4.

Aryl-5-methylene-oxazole derivatives of the formula (I) according to Claim 1, in which

R ^{1 represents} C _j -C ₆ alkyl or phenyl which is optionally mono- to pentasubstituted, identically or differently, by halogen, C _r C ₆ alkyl, C, -C ₆ alkoxy, C _r C ₆ - alkylthio , C _r C ₆ haloalkyl, C _j -C ₆ haloalkoxy, C _j -C ₆ haloalkylthio, , 0

R ^ for C _r C ₆ alkyl, or for phenyl, benzyl, pheneth-1-yl, pheneth-2-yl which are optionally monosubstituted to tetrasubstituted or differently substituted,

Phenoxymethyl, phenylthiom ethyl, phenoxyeth-1-yl, phenoxyeth-2-yl or styryl, where each may be mentioned as a phenyl substituent

Halogen,

C _r C ₁₈ alkyl,

C _r C ₈ alkoxy-C _r C ₈ alkyl,

C _j -C ₈ haloalkoxy, C _r C ₄ haloalkyl,

C _j -C _jg alkoxy, which is optionally interrupted by a further 1-3 oxygen atoms,

C _r C ₁₈ alkylthio,

C _j -C ₈ haloalkylthio, 3, 4-difluoromethylene dioxo,

3,4-tetrafluoroethylene dioxo, ~ optionally substituted by C _j -C ^ alkyl, C ₃ -C ₆ cycloalkyl and / or halogen benzyliminooxymethyl, each optionally substituted by C ₁ -C ₆ alkyl, C _j -C ₈ alkoxy, cyclohexyl or phenyl substituted cyclohexyl and cyclohexyloxy; if necessary, single or double, identical or different

Halogen, C _] -C ₄ alkyl or C _j -C ₄ .Halogenalkyl substituted pyridyloxy; each through single to triple, the same or different

C _r C ₁₂ alkyl, halogen, C ₁ -C ₄ haloalkyl, C _r C ₆ alkoxy, C _r C ₆ haloalkoxy, C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl, C _j -C ₆ alkoxy ethyleneoxy, C

C ₆ alkylthio and / or C _j -C ₆ haloalkylthio substituted phenyl, benzyl, phenoxy, phenylthio, benzyloxy and benzylthio, or R ¹ and R ² together for doubly linked, optionally mono- to tetrasubstituted, identically or differently substituted 2- to 6-membered, optionally benzanellated alkanediyl, where one or two non-adjacent CH ₂ groups are optionally replaced by O and / or S and are suitable as substituents: C 1 -C 4 -alkyl, in each case optionally mono- to tetrasubstituted, identical or differently substituted phenyl or a fused benzo group, the substituents mentioned in each case being the substituents mentioned in connection with the definition of R ² for phenyl,

R ^{3 represents} fluorine, chlorine, bromine, C, -C ₄ alkyl or C _r C ₄ alkoxy,

R ⁴ for fluorine, chlorine, bromine, C _r C ₄ alkyl, C _r C ₄ alkoxy, C _r C ₄ alkylthio, C _j -C ₄ haloalkyl, C _j -C ₄ haloalkoxy or C _j -C ₄ -Halogenalkylthio stands and

n stands for a number 0.1, 2, 3 or 4.

R ^{1 represents} C ₁ -C ₄ alkyl or phenyl which is optionally mono- to pentasubstituted, identically or differently, by F, Cl, Br, C _r C ₄ alkyl, C _r C ₃ alkoxy, C _r C ₃ -Alkylthio, simple to fivefold, identically or differently substituted by F and / or Cl, C _j - C ₂ -alkyl, single to fivefold, identical or differently substituted by F and / or Cl, C _r C ₄ -alkoxy, SCF ₃ or SCHF ₂ ,

R ² for C _] -C ₄ -alkyl or for phenyl, benzyl, pheneth-1-yl, pheneth-2-yl, phenoxymethyl, phenylthiomethyl, phenoxyeth-1-yl, each mono- to tetrasubstituted in the same or different ways, Phenoxyeth-2-yl or stryryl

F, Cl, Br, C _r C ₁₈ -alkyl, C _r C ₆ -alkoxy-C _r C ₈ -alkyl, in each case as phenyl substituents, are monosubstituted to sixfold, identical or differently substituted by F and / or Cl ^ Alkoxy, single to quintuple, identical or different C ₁ -C ₂ alkyl substituted by F and / or Cl, C _r C ₁₈ alkoxy and - (OC ₂ H ₄ ) ₁ . ₃ -OC _] -C ₆ -alkyl, C _r C ₁₂ -alkylthio, single to six-fold, identical or different C _] -C ₈ -alkylthio substituted by F and / or Cl,

3,4-difluoromethylenedioxo, 3,4-Tetrafluorethylendioxo, optionally substituted by C _j -C ₄ - alkyl, C ₃ -C ₆ cycloalkyl, fluorine and / or

Chloro-substituted benzyliminooxymethyl, in each case optionally substituted by C _j -C ₄ alkyl, C _j -C ₄ alkoxy, cyclohexyl or phenyl, cyclohexyl and cyclohexyloxy; optionally single or double, identical or different by F,

Cl or CF ₃ substituted pyridyloxy; each through single to triple, the same or different

C _j -C _j - _j -Alkyl, F, Cl, Br, CF ₃ , C _j -C ₄ -alkoxy, simple to six-fold, identical or differently substituted by F and / or Cl, C _j -C ₄ -

Vlkoxy, C _r C ₄ -alkoxy-C _r C ₄ -alkyl, C _r C ₄ -alkoxy-ethyleneoxy, C _r C ₄ -

Alkylthio, simple to sixfold, identical or different C ₁ -C ₄ alkylthio substituted by F and / or Cl substituted phenyl, benzyl, phenoxy, phenylthio, benzyloxy and benzylthio or

R ¹ and R ² together represent double-linked, optionally mono- to tetrasubstituted, identically or differently substituted 2- to 6-membered, optionally benzanellated alkanediyl, optionally one or two non-adjacent CH ₂ groups by O and / or S. are replaced and are suitable as substituents: C _j -C ₄ alkyl and in each case optionally monosubstituted to tetrasubstituted, identically or differently substituted phenyl or a fused benzo group, the substituents in each case being the substituents mentioned in connection with the definition of R ² for phenyl come,

R ^{3 represents} fluorine, chlorine, methyl or methoxy,

R ⁴ for fluorine, chlorine, C _r C ₃ alkyl, C _r C ₃ alkoxy, C _r C ₃ alkylthio, simple to fivefold, the same or different substituted by fluorine and or chlorine, C _j -C ₃ alkyl, simple up to five times, the same or C _] -C ₄ alkoxy which is differently substituted by fluorine and / or chlorine,

SCF ₃ and SCHF ₂ stands and

n stands for a number 0, 1, 2, 3 or 4

Process for the preparation of aryl-5-methylene-oxazole derivatives of the formula (I) according to Claim 1, characterized in that substituted benzamides of the formula (II)

in which

R ¹ , R ² , R ³ , R ⁴ and n have the meaning given in claim 1,

Benzamides of the formula (II)

in which

R ^{1 represents} alkyl or optionally substituted aryl;

R ^{2 represents} alkyl or optionally substituted phenyl, phenylalkyl, phenylalkenyl, phenoxyalkyl and phenylthioalkyl; or R ¹ and R ² together represent doubly linked, optionally substituted or fused alkanediyl, one or two non-adjacent CH ₂ groups optionally being replaced by O and / or S; and

R ^{3 represents} halogen, alkyl or alkoxy;

n stands for a number 0, 1, 2, 3 or 4,

with the exception of the compounds in which R ¹ and R ² simultaneously represent methyl.

6. A process for the preparation of the benzamides of the formula (II), according to claim

5, characterized in that benzoyl chlorides of the formula (III)

in which

R ³ , R ⁴ and n have the meaning given above,

with propargylamines of the formula (IV)

in which R ¹ and R ^{2 have} the meaning given above,

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

7. pesticides, characterized by a content of at least one aryl-5-methylene-oxazole derivative of the formula (I) according to claim

1.

8. A method for controlling animal pests, characterized gekenn¬ characterized in that at least one aryl-5-methylene-oxazole derivative of the formula (I) according to claim 1 is allowed to act on animal pests and their habitat.

9. Use of aryl-5-methylene-oxazole derivatives of the formula (I) according to Claim 1 for combating animal pests.

10. A process for the preparation of pesticides, characterized in that aryl-5-methylene-oxazole derivatives of the formula (I) according to claim 1 are mixed with extenders and / or surface-active agents.