WO1997006153A1

WO1997006153A1 - 4-alkyl-1,3-oxa(thia)zoline derivatives, their preparation and use for controlling animal pests

Info

Publication number: WO1997006153A1
Application number: PCT/EP1996/003242
Authority: WO
Inventors: Graham Holmwood; Johannes Kanellakopulos; Gerd Kleefeld; Christoph Erdelen; Ulrike Wachendorff-Neumann
Original assignee: Bayer Aktiengesellschaft
Priority date: 1995-08-04
Filing date: 1996-07-23
Publication date: 1997-02-20
Also published as: DE19528778A1; AU6658996A

Abstract

New 4-alkyl-1,3-oxa(thia)zoline derivatives have the formula (I), in which alk stands for C1-C2 alkyl; A stands for optionally substituted phenyl, pyridyl, thienyl or pyrazolyl; B stands for optionally substituted phenyl, pyridyl or thienyl; and Z stands for oxygen or sulphur. Also disclosed are a process for preparing these derivatives and their use for controlling animal pests.

Description

4-ALKYL-l, 3-0XA (THIA) Z0LIN DERIVATIVES, THEIR PRODUCTION AND THEIR USE FOR CONTROLLING ANIMAL Pests

The invention relates to new 4-alkyl-1,3-oxa (thia) zoline derivatives, several processes 5 for their preparation and their use for controlling animal

Pests

It is already known that certain 1,3-oxazoline derivatives have insecticidal and / or acaricidal properties (cf. e.g. EP-A 0 345 775 or WO-A 95/04726)

However, the level of action and / or duration of action of these previously known compounds is not completely satisfactory in all areas of application, in particular against certain organisms or at low application concentrations

New 4-alkyl-1,3-oxa (thia) zoline derivatives of the formula (I) have been found

5 in which

Alk represents C ₁ -C ₂ alkyl,

A represents in each case optionally substituted phenyl, pyridyl, thienyl or pyrazolyl,

B represents in each case optionally substituted phenyl, pyridyl or thienyl 0 and

Z represents oxygen or sulfur

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 both to the 5 pure isomers and to the isomer mixtures Furthermore, it was found that the new 4-alkyl-1,3-oxa (thia) zoline derivatives of the formula (I) are obtained if

a) amino alcohols of the formula (II)

in which

Alk and B have the meaning given above,

with a carboxylic acid of formula (III)

in which

A has the meaning given above,

with a dehydrating agent, optionally in the presence of a diluent;

or

b) amide alcohols of the formula (IV)

^{^^} _(Iy)(Iy)

in which

Alk, A and B have the meaning given above, with a dehydrating agent, optionally in the presence of a diluent;

or

c) amide derivatives of the formula (V)

in which

Alk, A and B have the meaning given above and

X represents halogen, alkylsulfonyloxy or optionally substituted

Aryl sulfonyl oxy,

with a base, optionally in the presence of a diluent;

or

d) amide alcohols of the formula (IV)

in which

Alk, A and B have the meaning given above,

with thienylating agents, optionally in the presence of a diluent. Furthermore, it was found that the new 4-alkyl-1,3-oxa (thia) zoline derivatives of the formula (I) are very suitable for controlling 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.

Alk is preferably methyl or ethyl.

A is preferably optionally up to five times, identical or different, by halogen, C _] -C ₆ alkyl, C _r C ₆ alkoxy, C _j -C ₈ alkylthio, C _r C ₆ haloalkyl, C _j -C ₈ Haloalkoxy, C _j -C ₈ haloalkylthio, nitro or cyano substituted phenyl,

optionally monosubstituted to trisubstituted by identical or different halogen, C _r C ₄ alkyl, C _r C ₄ alkoxy, C _r C ₄ haloalkyl, C, - ^ - halogenoalkyl alkoxy or cyano substituted pyridyl,

for single to triple, if necessary, the same or different

Halogen or C ₁ -C ₄ alkyl-substituted thienyl,

or represents optionally mono- to trisubstituted by identical or different manner by halogen or C _j -C ₈ -alkyl-substituted pyrazolyl,

B is preferably optionally up to five times, identical or different, by halogen, C _j -C ^ alkyl, C _j -C ^ alkoxy, C _j -C alkyl thio, C _] -C ₄ haloalkyl, C _j -C ₈ haloalkoxy, C _j -C ₈ haloalkyl thio, - (OC ₂ H ₄ ) ₁ . ₃ -OC _] -C ₆ -alkyl, 3,4-difluoromethylene dioxo, 3,4-tetrafluoroethylene dioxo, each optionally one to three times, identically or differently, by halogen, C ₁ -C ₈ -alkyl, C ₁ -C ₃ -alkoxy , C _] -C ₃ alkylthio, C _j -C ₈ haloalkyl, C _j -C ₈ haloalkoxy, C ₁ -C ₃ haloalkylthio, nitro,

Cyano, 3,4-difluoromethylene dioxo or 3,4-tetrafluoroethylene dioxo substituted phenyl, phenoxy, phenylthio, benzyl, phenethyl, phenpropyl, benzyloxy, benzylthio, phenoxymethyl, phenylthiomethyl, benzyloxymethyl, benzylthiomethyl, phenoxyethyl, phenylthioethyl, benzyloxy Benzylthioethyl, pyridyl, pyridyloxy, pyridylthio, pyridylmethyl, pyridylethyl, pyridylpropyl, pyridylmethoxy, pyridylmethylthio, pyridylmethoxymethyl, pyridylmethylthiomethyl, pyridyl oxyethyl, pyridylthioethyl, pyridylmethoxyethyl, pyridylmethoxyethyl or pyridylmethoxyethyl or pyridylmethoxyethyl or pyridylmethoxyethyl or pyridylmethoxyethyl or pyridylmethoxyethyl or pyridylmethoxyethyl or pyridylmethoxyethyl or pyridylmethoxyethyl,

for single to triple, if necessary, the same or different

Halogen, C _r C ₄ alkyl, C _r C ₄ alkoxy, C _r C ₄ haloalkyl, C _r C ₄ haloalkoxy or cyano substituted pyridyl,

or for thienyl which is optionally monosubstituted to trisubstituted, identically or differently, by halogen or C ₁ -C ₄ -alkyl.

Z preferably represents oxygen or sulfur.

Alk particularly preferably represents methyl.

A particularly preferably represents optionally mono- to triple, identical or different from F, Cl, Br, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy,

Alkylthio, mono- to heptasubstituted by identical or different F and / or Cl-substituted _C] _-C3 alkyl, mono- to heptasubstituted by identical or different F and / or Cl-substituted C, -C ₃ alkoxy, SCF ₃ , SCHF ₂ , nitro or cyano substituted phenyl.

B particularly preferably represents optionally one to three times, identical or different from F, Cl, Br, C _j -C ^ alkyl, C _j -C _{] 2} alkoxy, C _j -C, -, - alkylthio, simple to seven times , same or different by F and / or

Cl substituted C ^ C ₈ alkyl, mono- to heptasubstituted by identical or different F and / or Cl-substituted C _j -CG-alkoxy, mono- to heptasubstituted by identical or different F and / or Cl-substituted C ^ C ₈ -Alkylthio, - (OC ₂ H ₄ ) _1.3 -0-C ₁ -C ₆ -alkyl, 3,4-difluoromethylene-dioxo, 3,4-tetrafluoroethylene-dioxo, each optionally single to triple, identical or different by F, Cl, Br, C _r C ₃ alkyl, C ^ C _j alkoxy, monosubstituted to sevenfold, identically or differently substituted by F and / or Cl, C _j - C ₃ alkyl, monosubstituted to sevenfold, identical or differently substituted by F and / or Cl C _r C ₃ alkoxy, SCF ₃ , SCHF ₂ , nitro, cyano, 3,4-difluoromethylene dioxo or 3,4-tetrafluoroethylene dioxo substituted phenyl, phenoxy, phenylthio, benzyl, phenethyl, phenpropyl, benzyloxy, benzylthio, Phenoxymethyl, phenylthiomethyl, benzyloxymethyl, benzylthiomethyl, phenoxyethyl, phenylthioethyl, benzyloxyethyl, benzylthioethyl, pyridyl, pyridyloxy, pyridylthio, pyridylmethyl, pyridylethyl, pyridylpropyl, pyridylmethoxy, pyridylmethylthio, pyridylmethyl, pyridylmethyl, pyridylmethyl, pyridylmethyl, pyridylmethyl, pyridylmethyl, pyridylmethyl, pyridylmethyl

Pyridylmethylthioethyl substituted phenyl.

Z particularly preferably represents oxygen or sulfur.

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 or explanations of residues or explanations listed above or listed in preferred areas can be combined with one another, that is to say also between the respective areas and preferred areas. They apply accordingly to the end products and to the preliminary and intermediate products.

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

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

Preferred compounds according to the invention are also substances of the formula (IA)

in which R ^{1 represents} H, F, Cl or Br,

R represents the general, preferred and particularly preferred phenyl substituents mentioned above under A,

m represents the numbers 0, 1 or 2,

R represents the general, preferred and particularly preferred phenyl substituents mentioned above under B,

R ^{4 represents} the general, preferred and particularly preferred phenyl substituents mentioned above under A,

n stands for the numbers 0, 1 or 2 and

stands for oxygen or sulfur

Another preferred group of compounds of the formula (I) are those of the formula (LB)

in which

Shark represents fluorine or chlorine, preferably 6-fluorine or 6-chlorine,

R ^{5 represents} halogen, C _r C ₄ alkyl, C _r C ₄ haloalkyl, C _r C ₄ alkoxy or C _r C ₄ haloalkoxy

If, for example, 2-armno-2- (4-bromophenyl) -1-propanol and 2-chloro-4-fluorobenzoic acid are used as starting materials and polyphosphoric acid (PPS) as dehydrating agent according to process (a), the course of the process according to the invention can be changed ¬ driving can be reproduced by the following reaction scheme

According to method (b), e.g. N- [l-Hydroxy-2- (4-biphenylyl) propane-2-yl] -2-chloro-6-fluorobenzamide as a starting material and polyphosphoric acid (PPS) as a dehydrating agent, the course of the process according to the invention can be carried out by the following Reaction scheme are reproduced:

According to method (c), e.g. N- [l-chloro-2- (4-n-hexylphenyl) propan-2-yl] -2,6-difluorobenzamide as the starting material and triethylamine as the base, the course of the process according to the invention can be represented by the following reaction scheme become:

According to method (d), e.g. N- {l-Hydroxy-2- [4- (4-chlorophenoxy) phenyl] propan-2-yl} -2,4-difluorobenzamide as the starting material and phosphoric acid (V) sulfid as the thienylating agent The course of the process according to the invention can be reproduced by the following reaction scheme:

OO

The amino alcohols required as starting materials for carrying out process (a) according to the invention are generally defined by the formula (II). In formula (II), alk and B preferably or particularly preferably have those meanings which have already been mentioned above in connection with the description of the Bonds of the formula (I) have been indicated as preferred or particularly preferred for these substituents

The amino alcohols of the formula (II) are known and / or can be prepared by processes known per se, for example by using suitable amino acids with reducing agents, such as sodium borohydride in the presence of a diluent, such as tetrahydrofuran, at temperatures between -

20 ° C and + 100 ° C (see e.g. J Org Chem 1993, 58, 3568-3571 and the manufacturing examples)

The amino acids required as precursors are known and / or can be prepared by processes known per se, for example by using corresponding hydantoins in the presence of bases, if appropriate with

Pressure splits (see also the manufacturing examples)

The hydantoins required as precursors are known and / or can be prepared from the corresponding ketones using processes known per se (cf. eg Chemical Abstract 86, 29495 and the preparation examples).

The carboxylic acids also required as starting materials for carrying out process (a) according to the invention are generally defined by the formula (III). In formula (III) A preferably or particularly preferably has those meanings which have already been mentioned above in connection with the description of the compounds of formula (I) have been indicated as preferred or particularly preferred for this substituent

The carboxylic acids of formula (III) are known organic synthetic chemicals

Formula (IV) provides a general definition of the amide alcohols required as starting materials for carrying out processes (b) and (d) according to the invention. In formula (IV), alk, A and B preferably or particularly preferably have those meanings which: already in connection with the description of the compounds of formula (I) have been given as preferred or particularly preferred for these substituents.

The amide alcohols of the formula (IV) are known and / or can be prepared by processes known per se. The amide alcohols of the formula (IV) are obtained, for example, if one derives from the carboxylic acids of the formula (III)

Acid chlorides with amino alcohols of the formula (II) in the presence of an acid binder, such as e.g. Triethylamine, pyridine, potassium carbonate, sodium hydroxide or potassium t-butoxide, and in the presence of a diluent such as e.g. Toluene, chlorobenzene, acetone or acetonitrile, at temperatures between 0 ° C and 100 ° C.

Formula (V) provides a general definition of the amide derivatives required as starting materials for carrying out process (c) according to the invention. In formula (V), alk, A and B preferably or particularly preferably have those meanings which are preferred or particularly preferred for these in connection with the description of the compounds of formula (I)

Substituents were specified.

X preferably represents fluorine, chlorine, bromine, iodine, C 1 -C ₄ -alkylsulfonyloxy, phenylsulfonyloxy or tolylsulfonyloxy, in particular chlorine, bromine, methylsulfonyloxy or tolylsulfonyloxy.

The amide derivatives of the formula (V) are known and / or can be prepared by processes known per se.

The amide derivatives of the formula (V) are obtained, for example, by reacting corresponding amide alcohols of the formula (IV) with halogenating agents, such as e.g. Thionyl chloride, phosphorus tribromide, phosphorus trichloride or phosphorus (V) chloride, optionally in the presence of a diluent or with sulfonylating agents, such as e.g. Methanesulfonic acid chloride or p-toluenesulfonic acid chloride, optionally in the presence of a diluent and a base.

Aromatic, for example, come as a diluent in the halogenation

Hydrocarbons such as benzene, toluene, xylene, and halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and Dichloroethane in question The halogenating agent can be used in up to a five-fold excess

The reaction temperature in the halogenation can be varied within a substantial range. The reaction is generally carried out between 0 ° C. and the boiling point of the diluent

Suitable diluents for sulfonation are, in addition to those described above as being suitable for the halogenation reaction, for example ethers such as diethyl ether or tetrahydrofuran

Organic bases such as triethylamine, N, N-dimethylamine, pyridine and 4-N, N-dimethylaminopyne are preferably used as the base in the sulfonation

0.8 to 1.5 mol are generally used as the base per mole of the compound to be sulfonated

The sulfonation agent is generally used in at least equimolar amounts

Processes (a) and (b) according to the invention are carried out using a dehydrating agent. The dehydrating agents customary in organic chemistry can be used. Preferably, sulfuric acid, polyphosphoric acid (PPS), phosphorus (V) oxide, di- Cyclohexylcarbodnmid (DCC), phosphorus (V) -sulfιd and the system Tπphenylphosphin / Tπethylamin / Tetrachlormethan

Suitable diluents for carrying out processes (a) to (d) according to the invention are the customary organic solvents. Aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, are preferably usable.

Chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachloromethane, ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, ketones, such as acetone, butanone or methyl isobitrile, ketone , Propiomtπl or Benzomtπl, amides, such as N, N-Dιmethylformamιd and N, N-Dιmethylacetamιd, N-methyl-pyrrolidone or Hexamethylphosphorsauretriamid, esters such as methyl acetate or ethyl acetate, and sulfoxides such as dimethyl sulfoxide, optionally also alcohols such as methanol or ethanol

The reaction temperatures can be varied within a substantial range when carrying out process (a) according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably at temperatures between 10 ° C and 100 ° C.

Process (a) according to the invention is generally carried out under normal pressure. However, it is also possible to work under elevated or reduced pressure - generally between 0.1 bar and 10 bar

To carry out process (a) according to the invention, the respectively required starting materials are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components used in each case in a larger excess. The reactions are generally carried out in a suitable diluent is carried out in the presence of a dehydrating agent, and the reaction mixture is stirred for several hours at the required temperature. Working up is carried out in the processes according to the invention in each case by customary methods

In a particular embodiment of process (a) according to the invention, appropriate nitriles can also be used instead of the carboxylic acids of the formula (III), in which case a catalyst, such as zinc (II) chloride, is preferably used instead of a water-removing agent is used

When carrying out process (b) according to the invention, the reaction temperatures can be varied within a substantial range. In general, temperatures between -20 ° C. and + 150 ° C., preferably at temperatures between 0 ° C. and 100 ° C.

Process (b) according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure - generally between 0.1 bar and 10 bar To carry out process (b) according to the invention, 1 to 20 mol, preferably 1 to 5 mol, of dehydrating agent are generally employed per mole of amide alcohol of the formula (IV).

In a preferred embodiment of process (b) according to the invention, the amide alcohol of the formula (IV) is placed in a diluent and the dehydrating agent is then metered in. The reaction mixture is stirred at the required temperature until the reaction has ended and then worked up in the customary manner

Process (c) according to the invention is carried out in the presence of a base. All customary inorganic or organic bases come into consideration. Alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or are preferably used bicarbonates, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate and tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU)

When carrying out process (c) according to the invention, the reaction temperatures can be varied within a substantial range. In general, temperatures between -20 ° C. and + 150 ° C., preferably at temperatures between 0 ° C. and 100 ° C.

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

To carry out process (c) according to the invention, 1 to 3 mol, preferably 1.0 to 1.5 mol, of a base are generally employed per mol of amide devat of the formula (V) In a preferred embodiment of process (c) according to the invention, the amide derivative of the formula (V) and a base are mixed in a suitable diluent; the mixture is stirred at the required temperature until the reaction has ended and then worked up in the customary manner.

Process (d) according to the invention is carried out using a thienylating agent. The usual reagents suitable for converting organic oxygen compounds into corresponding sulfur compounds are suitable as such. Phosphorus (V) sulfide, hydrogen sulfide and its alkali metal salts and the so-called Lawesson

Reagent [2,4-bis (4-methoxyphenyl) -l, 3,2,4-dithiadiphosphetane-2,4-dithione].

The reaction temperatures can be varied within a substantial range when carrying out process (d) according to the invention. In general, temperatures between -20 ° C and + 150 ° C, preferably at temperatures between 0 ° C and 100 ° C.

Process (d) 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.

To carry out process (d) according to the invention, 1 to 5 mol, preferably 1.0 to 1 mol, are generally employed per mol of amide alcohol of the formula (IV)

2.5 moles of a thienylating agent.

In a preferred embodiment of process (d) according to the invention, the amide alcohol of the formula (IV) is initially introduced into a diluent and the thienylating agent is then metered in. The reaction mixture is then stirred at the appropriate reaction temperature until the end of the reaction and then worked up in the customary manner.

With good plant tolerance and favorable warm-blood toxicity, the active substances are suitable for combating animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored goods and materials, and in the hygiene sector. They can preferably be used as crop protection agents. They are against normal sible and resistant species and effective against all or individual stages of development. The pests mentioned above include:

From the order of the Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Por¬ celli o 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 e.g. Lepisma saccharina.

From the order of the Collembola e.g. 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. 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, for example 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 striatataidella, piotifidella, aiotaparella, aiotaparella, pod , 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, Earioaulppa, Spariasodia spp, Heliodia spp. Panolis flammea, Spodoptera litura, Spodoptera spp, Trichoplusia ni, Carpocapsa pomonella, Pieris spp, Chilo spp, Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila Pseudiauellanaulanaellaana panaellaana pellaellaana pellaellaana pellaella pella, pseudoella cellophane pentomorphic cellulitis, pseudosella cellulosicella pena cella, peculiar pseudoella cellophane , Homona magnanima, Tortrix viridana

From the order of the Coleoptera, e.g. Anobium punctatum, Rhizopertha dominica,

Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, spp Diabrotica spp, Psylliodes chrysocephala, Epilachna varivestis, Atomaria, Oryzaephilus surinamensis, Anthonomus spp, spp Sitophilus, Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica , Dermestes spp, Trogoderma spp,

Anthrenus spp, Attagenus spp, Lyctus spp, Mehgethes aeneus, Ptinus spp, Niptus hololeucus, Gibbium psylloides, Tribolium spp, Tenebrio molitor, Agriotes spp, Conoderus spp, Melolontha melolontha, Amphimallon solstitica, Costelytra zealand

From the order of the Hymenoptera, for example 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, Stomoxyspppp, Hypodermapppp, Oestranuspp, , Tannia spp, Bibio hortulanus, Oscinella fπt, Phorbia spp, Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa From the order of the Siphonaptera, for example 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., Chorioptes spp. , Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

Plant parasitic nematodes include e.g. Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp.,

Xiphinema spp., Trichodorus spp

The compounds of the formula (I) according to the invention are notable in particular for outstanding insecticidal and acaricidal activity

They can be used with particularly good success for combating plant-damaging insects and mites, such as, for example, against larvae of the green rice leafhopper (Nephotettix cincticeps) or against the common spider mite (Tetranychus urticae)

The active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, loose powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances as well as very fine encapsulation in polymeric substances

These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents

Agents, ie emulsifiers and / or dispersants and / or foam-generating agents.

If water is used as an extender, organic solvents can also be used as auxiliary solvents, for example, as liquid solvents 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, for example 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.

Solid carrier materials that come into question 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, as solid carrier materials for granules in question: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems, as emulsifying and / or foam-generating agents are possible: 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 dispersants are, for example, lignin sulfite waste liquor and methyl cellulose

Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins and synthetic phospholipids, can be used in the formulations, and further additives can be mineral and vegetable oils his

Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used

The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90% The active substance according to the invention can be present in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active substances, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms and others

Particularly cheap mixing partners are e.g. 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-cyano-phenoxy) 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, chlorozhalonolinolonolinolonolinolinolinothalonolinol, chlorothalonolinophenol

Cymoxanil, cyproconazole e, cyprofuram,

Dichlorophen, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolidone, edolololidiridolol, ethidololidiridolol, ethazolidone, ethzololidone, edolazolidone, edolazole epidone, epidonylolidone, epidonylolidone

Fenarimol, Fenbu conazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fen¬ propimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fluodioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanol, Fol-tri , Fthalides, fuberidazole, furalaxyl, furmecyclox, guazatine,

Hexachlorobenzene, hexaconazole, hymexazole,

Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan, Kasugamycin, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture, Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil, Nickel-dimethyldithiocarbamate, Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadixefuryloxoxuryl phthalide, pimaricin, piperalin, polycarbamates, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozene (PCNB), sulfur and sulfur preparations, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole Thicyofen

Thiophanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Triflumizol, Triforin, Triticonazol, Validamycin A, Vinclozolin, Zineb, Ziram.

Bactericides:

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

Insecticides / acaricides / nematicides:

Abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb, alpha-methrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M,

Azocyclotin,

Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin,

Butyl pyridaben,

Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorofiuazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clophentoshrin, Clophenthrin, Cyclin Cyfluthrin, cyhalothrin, cyhexatin,

Cypermethrin, cyromazine,

Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazion non, 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, Fluufenprox

Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb, HCH, Heptenophos, Hexaflumuron, Hexythiazox,

Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Iver¬ mectin, Lambda-cyhalothrin, Lufenuron, Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos,

Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin, Naled, NC 184, NI 25, Nitenpyram, Omethoat, Oxamyl, Oxydemethon M, Oxydeprofos, Parathion A, Parathion M, Permethron, Phathoatophin, Phenthoat ,

Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophos, Pyradaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen, Pyriproxifen, Pyriproxifen

Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,

Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thio¬ methon, Thionazin, Thuringiensin, Tralomenhroniazonium, Tronomenophoniazonium Triaromoshroniazonium Triaromenhroniazonium Triaromoshronizonium Triaromoshroniazonium Triaromoshronizonium Tronomoshronizonium Tronomoshronizonium Tri

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 furthermore be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists. Synergists are compounds through which the action of the active ingredients is increased without the added synergist itself having to be active. The active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges. The active substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight.

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

Wise.

When used against hygiene pests and pests of stored products, the active ingredient is distinguished by an excellent residual action on wood and clay and by a good alkali stability on limed substrates.

The active compounds according to the invention act not only against plant, hygiene and stored-product pests, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, Featherlings and fleas.

The active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which are used in agricultural animals, such as e.g. Cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as e.g. Dogs, cats, house birds, aquarium fish and so-called experimental animals, such as Infest hamsters, guinea pigs, rats and mice. By fighting these arthropods, deaths and reduced performance (in 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, such as Example by injections (intramuscular, subcutaneous, intravenous, intraperitonal, etc.), implants, by nasal application, by dermal application in the form of, for example, diving or bathing (dipping), spraying (spray), pouring on (pour-on and spot-on), washing, powdering and with the help of molded articles containing active ingredients, such as collars, ear tags, tail tags, limb tapes, holsters, marking devices, etc.

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

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

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

Beetle like

Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticomis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearesces, Lyctus pubis linearis, specie Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus.

Skin wings like

Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.

Termites like

Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwinisis, Zootermopsis nevadensis, Coptotermes formosanus.

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

The material to be protected against insect infestation is very particularly preferably wood and wood processing products

Wood and wood processing products, which can be protected by the agent according to the invention or mixtures containing it, are to be understood as examples - timber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, pallets, containers, telephone masts, wooden cladding, wooden windows and doors , Plywood, chipboard, carpentry or wood products that are used in general in house construction or in carpentry

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

The formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredients with at least one solvent or diluent, emulsifier, dispersant and / or binder or fixative, water repellants, optionally desiccants and UV stabilizers and if necessary dyes and pigments and other processing aids

The insecticidal compositions or concentrates used to protect wood and wood-based materials contain the active compound according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.

The amount of the agents or concentrates used depends on the type and occurrence of the insects and on the medium. The optimum amount can be determined in each case by use of test series. 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 solvent or solvent mixture and / or an oily or oil-like heavy substance serves as the solvent and / or diluent 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

As organic-chemical solvents, preference is given to using oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C. Appropriate mineral oils or theirs are used as such volatile, water-insoluble, oily and oily solvents Aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene, are used

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

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

The organic, slightly volatile oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C., can be partially replaced by slightly or medium-volatile organic-chemical solvents, with the proviso that the solvent mixture likewise has an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C., and that the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture

According to a preferred embodiment, part of the organic-chemical solvent or solvent mixture is replaced by an aliphatic polar organic-chemical solvent or solvent mixture. Aliphatic organic-chemical solvents containing hydroxyl and / or ester and / or ether groups, such as for example, are preferably used Glycol ether, ester or the like for use In the context of the present invention, the known organic-chemical binders are the water-dilutable synthetic resins and / or synthetic resins which are soluble or dispersible or emulsifiable in the organic-chemical solvents used and / or binding drying oils, in particular binders consisting of or containing an acrylate resin, a vinyl resin, for example polyvinyl acetate,

Polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or synthetic resin used.

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

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

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

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

Fixing agents are chemically based on polyvinyl alkyl ethers such as polyvinyl methyl ether or ketones such as benzophenone and ethylene benzophenone. Water is also particularly suitable as a solvent or diluent, if appropriate in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants.

A particularly effective wood protection is achieved through industrial impregnation processes, e.g. Vacuum, double vacuum or pressure processes.

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

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

Connections are an integral part of this application.

Very particularly preferred admixing partners are insecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumurazole, as well as fungazazole, eponazole, epoxazolone, epoxazole, and epungazolone, as well as fungonazole, eponazole, eponazole, and epungazolone, as well as fungazazole, epazazole, as well as fungonazole, such as epazazole, as well as Fungazazole, such as Fungazizole, like,

Tebuconazole, Cyproconazole e, Metconazole, Imazalil, Dichlorfluanid, Tolylfluanid, 3-Iodo-2-propynyl-butylcarbamate, N-Octyl-isothiazolin-3-one and 4,5-Dichlor-N-Octyl-isothiazolin-3-one.

The preparation and use of the active compounds according to the invention can be seen from the examples below.

Manufacturing examples

example 1

(Method c)

14.37 g (0.0288 mol) of N- [l-methylsulfonyloxy-2- (4-tert-butylphenyl) propan-2-yl] - 2,6-difluorobenzamide in 130 ml of absolute tetrahydrofuran are mixed with 4.16 g (0.0372 mol) of potassium tert-butoxide are added and the mixture is stirred at room temperature overnight. It is then concentrated by distilling off the solvent and the residue is partitioned between water and methylene chloride. The organic phase is separated off, dried over sodium sulfate, concentrated and chromatographed on silica gel using methylene chloride.

2.3 g (24.3% of theory) of 4- (4-tert-butylphenyl) -2- (2,6-difluorophenyl) -4-methyl-1,3-oxazoline with a refractive index wet are obtained ⁰ = 1.5392.

Manufacture of the starting product

^h CH ₃ S0 ₂ - ^ ²

9.99 g (0.0288 mol) of N- [l-hydroxy-2- (4-tert-butylphenyl) propan-2-yl] -2,6-difluoro-benzamide, 3.63 g (0. 0317 mol) of methanesulfonyl chloride and 3.5 g (0.0346 mol) of triethylamine are stirred in 100 ml of absolute tetrahydrofuran overnight at room temperature. It is then concentrated by distilling off the solvent and the residue is partitioned between ether and water. The organic phase is separated off, dried over sodium sulfate and concentrated.

14.8 g of crude N- [l-methylsulfonyloxy-2- (4-tert-butylphenyl) propan-2-yl] -2,6-difluorobenzamide are obtained as a yellow-orange oil, which can be reacted directly.

A solution of 6.83 g (0.033 mol) of 2-amino-2- (4-tert-butylphenyl) -1-propanol and 6.68 g (0.066 mol) of triethylamine in 40 ml of absolute acetonitrile is cooled in an ice bath, 5.82 g (0.033 mol) of 2,6-difluorobenzoyl chloride were added and the mixture was stirred at room temperature overnight. The reaction mixture is then poured into water and extracted with ethyl acetate.

10.1 g (88.2% of theory) of N- [l-hydroxy-2- (4-tert-butylphenyl) propan-2-yl] -2,6-difiuorbenzamide are obtained as a slowly crystallizing solid with a Content of 96% (GC / MS).

A solution of 30.9 g (0.14 mol) of 2-amino-2- (4-tert-butylphenyl) -l-propane-carboxylic acid in 400 ml of absolute tetrahydrofuran is treated with 12.7 g (0.336 Mol) sodium borohydride added, cooled to 0 ° C and within 30 minutes with a solution of 35.5 g (0.14 mol) of iodine in 100 ml of absolute tetrahydrofuran. The reaction mixture is allowed to stir under reflux overnight, then cooled and 100 ml of methanol are added dropwise. The mixture is then stirred for 30 minutes and concentrated by distilling off the solvent. The residue is taken up in 280 ml of 20% potassium hydroxide solution, stirred for 4 hours at room temperature and extracted three times with methylene chloride. The combined organic phases are washed with water, dried over sodium sulfate and concentrated. The residue is dissolved in toluene, acidified with concentrated hydrochloric acid and stirred vigorously. The solid is filtered off with suction, suspended in water / methylene chloride and made basic with dilute sodium hydroxide solution. The organic phase is separated off, dried over sodium sulfate and concentrated.

18 g (62.3% of theory) of 2-amino-2- (4-tert-butylphenyl) -1-propanol of melting point 107-08 ° C. are obtained.

34.4 g (0.14 mol) of 5- (4-tert-butylphenyl) -5-methyl-hydantoin are mixed with a solution of 20.8 g (0.52 mol) of sodium hydroxide in 115 ml of water and in

Autoclave heated at 170 ° C for 6 hours. The product mass is then suspended in 300 ml of water and neutralized to pH 7 with concentrated hydrochloric acid. The resulting solid is filtered off, washed with water and dried.

30.9 g (100% of theory) of 2-amino-2- (4-tert-butylphenyl) propane carboxylic acid are obtained as a crystalline solid.

A mixture of 4-tert-butylacetophenone, 70 g (0.73 mol) ammonium carbonate and 20 g (0.31 mol) potassium cyanide in 200 ml n-propanol and 150 ml water is heated in an autoclave at 80 ° C. for 16 hours, then cooled and stirred with 1.5 l of water. The resulting solid is filtered off, washed with 1.5 l of warm water and dried.

34.9 g (94.6% of theory) of 5- (4-tert-butylphenyl) -5-methylhydantoin are obtained.

The following compounds of the formula (I) are obtained analogously to Example 1 and in accordance with the general information on the preparation:

Table 1

Examples of use

Example A

Nephotettix test

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

To produce a suitable preparation of active compound, 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.

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, the compound according to Preparation Example 1, with an exemplary active ingredient concentration of 0.1%, shows a kill of 100% after 6 days.

Example B

Tetranychus test (OP-resistant / immersion treatment)

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 to the desired concentrations with emulsifier-containing water.

Bean plants (Phaseolus vulgaris), which are heavily affected by all stages of development of the common spider mite Tetranychus urticae, are in one

Drug preparation of the desired concentration dipped.

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

In this test, e.g. the compound according to preparation example 1 with an exemplary active ingredient concentration of 0.01% after 13 days a killing of 98%.

Claims

claims

1 compounds of formula (I)

in which

Alk represents C _r C ₂ alkyl,

B for each optionally substituted phenyl, pyridyl or

Thienyl stands and

Z represents oxygen or sulfur

2 compounds of formula (I) according to claim 1, in which

Alk represents methyl or ethyl,

A for optionally single to five times, identical or different, by halogen, C _r C ₆ alkyl, C _r C ₆ alkoxy, C _r C ₆ alkylthio, C _r C ₆ haloalkyl, C _j -C ₆ haloalkoxy, C _j -C ₈ haloalkylthio,

Nitro or cyano substituted phenyl,

for pyridyl which is optionally mono- to trisubstituted, identically or differently, by halogen, C _] -C ₄ -alkyl, C _r C ₄ -alkoxy, C _r C ₄ -haloalkyl, C _j -C ₄ -haloalkoxy or cyano,

for thienyl which is optionally monosubstituted to trisubstituted identically or differently by halogen or C _] -C ₄ -alkyl, or represents pyrazolyl which is optionally monosubstituted to trisubstituted, identically or differently, by halogen or C _r C ₃ alkyl,

B for optionally single to five times, identical or different, by halogen, C _r C ₁₂ alkyl, C _r C ₁₂ alkoxy, C ₁ -C ₁₂ alkylthio, C _r

C ₄ haloalkyl, C _r C ₈ haloalkoxy, C _r C ₈ haloalkylthio, - (OC ₂ H ₄ ) ₁ . ₃ -OC _] -C ₆ -alkyl, 3,4-difluoromethylene dioxo, 3,4-tetra-fluoroethyl endi oxo, in each case optionally one to three times, identically or differently by halogen, C.-C ₃ -alkyl, C _r C ₃ -Alkoxy, C, -C ₃ -alkylthio, C _r C ₃ -haloalkyl, C _r C ₃ -haloalkoxy, C _r C ₃ -

Haloalkylthio, nitro, cyano, 3,4-difluoromethylene dioxo or 3,4-tetrafluoroethylene dioxo substituted phenyl, phenoxy, phenylthio, benzyl, phenethyl, phenpropyl, benzyloxy, benzylthio, phenoxymethyl, phenylthiomethyl, benzyloxymethyl, benzylthiomethyl, phenoxyethyl, phenylethyl, phenylethyl, phenylethyl Benzylthioethyl,

Pyridyl, pyridyloxy, pyridylthio, pyridylmethyl, pyridylethyl, pyridylpropyl, pyridylmethoxy, pyridylmethylthio, pyridylmethoxymethyl, pyridylmethylthiom ethyl, pyridyl oxyethyl, pyridylthioethyl, pyridylmethoxyethyl or pyridylmethylthioethyl substituted phenyl

optionally monosubstituted to trisubstituted by identical or different halogen, C _r C ₄ alkyl, _C] -C ₄ alkoxy, C _j -C ₄ haloalkyl, C _j -C ₄ -haloalkoxy or cyano substituted pyridyl,

or represents optionally mono- to trisubstituted by identical or comparable secreted by halogen or C _j -C ₄ alkyl-substituted thienyl and

Z represents oxygen or sulfur

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

Alk represents methyl, A for optionally single to triple, identical or different by F, Cl, Br, C _r C ₃ alkyl, C _r C ₃ alkoxy, C ₁ -C ₃ alkylthio, simple to seven times, identical or different by F and / or Cl substituted C _j -C ₈ alkyl, mono- to sevenfold, identical or different from F and / or Cl substituted C _j -C ^ alkoxy, SCF ₃ ,

SCHF ₂ , nitro or cyano substituted phenyl,

B for optionally single to triple, identical or different by F, Cl, Br, C _r C ₁₂ alkyl, C _r C ₁₂ alkoxy, C _r C ₁₂ alkylthio, simple to seven times, identical or different by F and / or Cl substituted C _j - ^ alkyl, mono- to heptasubstituted by identical or different F and / or Cl-substituted C _j -C ₈ alkoxy, mono- to heptasubstituted by identical or different F and / or Cl sub¬ stituiertes C _r C ₈ -Alkylthio, - (OC ₂ H ₄ ) _1.3 -OC ₁ -C ₆ -alkyl, 3,4-difluoromethylene dioxo, 3,4-tetrafluoroethylene dioxo, each optionally one to three times, identically or differently by F, Cl , Br, C _j -

C ₃ alkyl, C _j -C ₃ alkoxy, simple to seven-fold, identically or differently substituted by F and / or Cl, C _j -C ₃ alkyl, simple to seven-fold, identical or different by F and / or Cl sub¬ substituted C _r C ₃ alkoxy, SCF ₃ , SCHF ₂ , nitro, cyano, 3,4-difluoromethyl endi oxo or 3,4-tetrafluoroethylene dioxo substituted phenyl, phenoxy, phenylthio, benzyl, phenethyl, phenpropyl, benzyl¬ oxy, benzylthio, phenoxymethyl, phenylthiomethyl, benzyloxymethyl, benzylthiomethyl, phenoxyethyl, phenylthioethyl, benzyloxyethyl, benzylthioethyl, pyridyl, pyridyloxy, pyridylthio, pyridylmethyl, pyridylethyl, pyridylpropyl, pyridylmethylthymethyl, pyridylmethylthymethyl, ridyl oxyethyl, pyridylthioethyl, pyridylmethoxyethyl or pyridyl¬ methylthioethyl substituted phenyl and

Z represents oxygen or sulfur.

A process for the preparation of compounds of formula (I) according to claim 1, characterized in that

a) amino alcohols of the formula (II)

in which

Alk and B have the meaning given in claim 1,

with a carboxylic acid of formula (III)

A-COOH (III) in which

A has the meaning given in claim 1,

with a dehydrating agent, optionally in the presence of a diluent;

or

b) amide alcohols of the formula (IV)

in which

Alk, A and B have the meaning given above,

with a dehydrating agent, optionally in the presence of a diluent;

or

c) amide derivatives of the formula (V)

in which

Alk, A and B have the meaning given above and

X represents halogen, alkylsulfonyloxy or optionally substituted arylsulfonyloxy,

with a base, optionally in the presence of a diluent;

or

d) amide alcohols of the formula (IV)

in which

Alk, A and B have the meaning given above,

with thienylating agents, optionally in the presence of a diluent.

Pesticides, characterized in that they contain at least one compound of the formula (I) according to Claim 1.

Use of compounds of formula (I) according to claim 1 for combating pests. 7. A method for controlling pests, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on pests and / or their habitat.

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

9. Use of compounds of formula (I) according to claim 1 for the preparation of pesticides.