WO1996018619A1

WO1996018619A1 - Substituted m-biphenyloxazoline derivatives

Info

Publication number: WO1996018619A1
Application number: PCT/EP1995/004719
Authority: WO
Inventors: Wolfgang Krämer; Udo Kraatz; Reinhard Lantzsch; Albrecht Marhold; Christoph Erdelen
Original assignee: Bayer Aktiengesellschaft
Priority date: 1994-12-12
Filing date: 1995-11-30
Publication date: 1996-06-20
Also published as: DE4444111A1; AU4300696A

Abstract

The invention concerns novel m-biphenyloxazoline derivatives of formula (I) in which R?1 and R2¿ have the meanings given in the description. The invention also concerns methods and novel intermediate products for their preparation and their use as pesticides.

Description

Substituted m-biphenyloxazoline derivatives

The invention relates to new substituted m-biphenyloxazoline derivatives, several

Processes for their preparation, new intermediates and the use of the m-biphenyloxazoline derivatives for controlling animal pests

It is known that certain substituted biphenyloxazolines are insecticidal and acaricidal (cf. e.g. EP-A 0 432 661). However, the amount and / or duration of action of these known compounds is not entirely satisfactory in all areas of application, in particular against certain organisms or at low application concentrations.

New m-biphenyloxazoline derivatives of the formula (I)

found in which

R ^{1 represents} hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkenyl, haloalkenyl, alkenyloxy, haloalkenyloxy, alkynyl, haloalkynyl, alkynyloxy, haloalkynyloxy or any optionally substituted cycloalkyl or cycloalkylalkyl and R ^{2 represents} hydrogen, alkyl, alkenyl, Alkynyl, haloalkyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl, optionally substituted aralkyl or for the radical -COR ³ , where

R ^{3 represents} alkyl, alkoxy, alkenyl, alkenyloxy, in each case optionally substituted cycloalkyl, cycloalkyloxy or cycloalkylalkyloxy, optionally substituted aryl or for the radical -NR ⁴ R ⁵ , where

R ^{4 represents} hydrogen or alkyl and

R ^{5 represents} alkyl, haloalkyl, in each case optionally substituted cycloalkyl or cycloalkylalkyl or for in each case optionally substituted phenyl or phenylalkyl.

Because of one or more centers of chirality, the compounds of the formula (I) are generally obtained as mixtures of stereoisomers. They can be used both in the form of their diastereomer mixtures and as pure diastereomers or enantiomers.

Furthermore, it was found that the new m-biphenyloxazoline derivatives of the formula (I) are obtained if a) m-biphenyl-chloroethyl-benzamides of the formula (II)

in which

R ^{1 has} the meaning given above and

R represents allyl or the radical -COR ³ , where

R ^{3 has} the meaning given above, in a first stage in the presence of a base, optionally in the presence of a catalyst and optionally in the presence of a diluent, and optionally subsequently in a second stage the 4- (m-biphenyl) oxazolines of the formula (Ia) thus obtained

in which

R ^{1 has} the meaning given above and

R represents allyl or the radical -COR ³ , where

R ^{3 has} the meaning given above, in the presence of a catalyst, optionally in the presence of an acid and a diluent, to give the 4- (4-hydroxy-3-biphenyl) oxazolines of the formula (Ib)

in which

R ^{1 has} the meaning given above; and optionally the 4- (4-hydroxy-3-biphenyl) oxyzolines of the formula (Ib) thus obtained

in which

R ^{1 has} the meaning given above, with compounds of the formula (III) MR ² (III) in which

M stands for a leaving group and

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

It was also found that the new substituted m-biphenyloxazoline derivatives of the formula (I) are very good for combating animal pests, in particular insects, arachnids and nematodes, which protect in agriculture, in forests, in the supply and material and on the hygiene sector, are suitable

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

Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below. R ¹ preferably represents hydrogen, fluorine, chlorine or bromine, C ₁ -C ₉ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkyl or C ₁ -C ₆ haloalkoxy with in each case one or more fluorine and / or chlorine atoms, for C ₁ -C ₁₂ alkenyl, C ₃ -C ₁₂ alkenyloxy or C ₃ -C ₆ haloalkenyl with one or more fluorine and / or chlorine atoms, for C ₃ - C ₁₂ -alkynyl, C ₃ -C ₁₂ -alkynyloxy or C ₃ -C ₆ -haloalkynyl with one or more fluorine and / or chlorine atoms, or for each optionally one or more times, identically or differently, by halogen or C ₁ -C ₄ -Alkyl substituted C ₃ -C ₆ cycloalkyl or C ₃ -C ₆ cycloalkyl-C ₁ -C ₄ alkyl

R ² preferably represents hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ alkenyl, C ₃ -C ₁₂ alkynyl, C ₁ -C ₆ haloalkyl with one or more fluorine and / or chlorine atoms , for C ₃ -C ₆ cycloalkyl or C ₃ -C ₆ cycloalkyl-C ₁ -C ₄ -alkyl, which are optionally mono- or polysubstituted in the cycloalkyl moiety, in each case mono- or polysubstituted, in each case halogen, C ₁ -C ₄ - as substituents Alkyl, optionally singly or multiply, identically or differently by C ₂ -C ₄ -alkenyl substituted by halogen and in each case optionally singly or multiply, identically or differently by

Halogen-substituted phenyl or styryl are suitable,

in each case optionally monosubstituted or polysubstituted by identical or different substituents, by halogen or C ₁ -C ₄ alkyl C ₄ -C ₆ cycloalkenyl or C ₄ -C ₆ cycloalkenyl-C ₁ -C ₄ alkyl,

for phenyl-C ₁ -C ₄ -alkyl or naphthylmethyl which is optionally mono- or polysubstituted in the aryl moiety, in each case mono- or polysubstituted, in each case as substituents halogen, C ₁ -C ₁₂ -alkyl, C ₁ -C ₁₂ -haloalkyl with one or more Fluorine and / or chlorine atoms, C ₁ -C ₁₂ alkoxy or C ₁ - C ₁₂ haloalkoxy with one or more fluorine and / or chlorine atoms are suitable,

or for the rest -COR ³

R ³ preferably represents C ₁ -C ₁₂ -alkyl, C ₁ -C ₁ -alkoxy, C ₃ -C ₁₂ -alkenyl, C ₃ -C ₁₂ -alkenyloxy, for each in the cycloalkyl part optionally one or more times, identical or differently substituted C ₃ -C ₆ cycloalkyl, C ₃ -C ₁₀ cycloalkyloxy or C ₃ -C ₁₀ cycloalkyl-C ₁ -C ₆ alkoxy, where in each case as substituents C ₁ -C ₄ alkyl, halogen, C ₁ -C ₄ haloalkyl with one or more fluorine and / or chlorine atoms and C ₂ -C ₄ haloalkenyl with one or more fluorine and / or chlorine atoms come into question, for each optionally mono- or polysubstituted, identically or differently substituted Phenyl or naphthyl, where in each case as phenyl or naphthyl thyl substituents halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ haloalkyl with one or more fluorine and / or chlorine atoms, C ₁ -C ₁₂ alkoxy and C ₁ -C ₁₂ haloalkoxy with one or more Fluorine and / or chlorine atoms come into question,

or for the rest -NR ⁴ -R ⁵

R ⁴ preferably represents hydrogen or C ₁ -C ₁₂ alkyl

R ⁵ preferably represents C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ haloalkyl with one or more fluorine and / or chlorine atoms, each in the cycloalkyl part optionally mono- or polysubstituted, identically or differently substituted, C ₃ -C ₆ - Cycloalkyl or C ₃ -C ₆ cycloalkyl-C ₁ -C ₄ alkyl, where in each case as substituents C ₁ -C ₄ alkyl, halogen, C ₁ -C ₄ haloalkyl with one or more fluorine and / or chlorine atoms and C ₂ -C ₄ haloalkenyl with one or more fluorine and / or chlorine atoms are suitable,

or for phenyl or phenyl-C ₁ -C ₆ -alkyl which is optionally mono- or polysubstituted by identical or different substituents, in each case as

Phenyl substituents halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ haloalkyl with one or more fluorine and / or chlorine atoms, C ₁ -C ₁₂ alkoxy and C ₁ -C ₁₂ haloalkoxy with one or more fluorine and / or chlorine atoms come into question R ¹ particularly preferably represents hydrogen, fluorine, chlorine or bromine, C ₁ -C ₆ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkyl or C ₁ - C ₄ haloalkoxy, each with two or more fluorine and / or chlorine atoms, C ₃ - C ₆ alkenyl, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyl or C ₃ -C ₆ alkynyloxy, or each optionally mono- to triple, identical or different, C ₃ -C ₆ -cycloalkyl or C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl substituted by fluorine or chlorine

R ² particularly preferably represents hydrogen, represents C ₁ -C ₆ - alkyl, C ₁ -C ₁₂ - alkenyl, C ₃ -C ₆ -alkynyl, C ₁ -C ₄ haloalkyl having two or more fluorine and / or chlorine atoms, in each case in the cycloalkyl moiety is optionally mono- to trisubstituted by identical or different substituents, C ₃ -C ₆ - cycloalkyl or C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, in each case as substituents of fluorine, chlorine, bromine, C ₁ -C ₂ alkyl, optionally single or multiple, identical or different C ₂ -C ₄ substituted by fluorine or chlorine Alkenyl and, in each case, optionally single or double, identical or different, phenyl and styryl substituted by fluorine or chlorine,

for each C ₄ -C ₆ cycloalkenyl or C ₄ -C ₆ cycloalkenylmethyl which is optionally mono- or disubstituted, identically or differently, by fluorine or chlorine,

for phenyl-C ₁ -C ₄ -alkyl which is optionally monosubstituted to trisubstituted, identically or differently, in the phenyl part, where fluorine, chlorine, C ₁ -C ₄ -alkyl, halomethyl having one or more fluorine and / or chlorine atoms, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy with one or more fluorine and / or chlorine atoms are suitable,

or for the rest -COR ³

R particularly preferably represents C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₃ -C ₆ - alkenyl, C ₃ -C ₆ alkenyloxy, in each case in the cycloalkyl moiety is optionally mono- to trisubstituted by identical or differently substituted C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyloxy or C ₃ -C ₆ cycloalkyl-C ₁ -C ₄ alkoxy, where in each case as substituents C ₁ -C ₂ alkyl, fluorine, chlorine C ₁ -C ₂ haloalkyl with 1 to 5 fluorine and / or chlorine atoms and C ₂ -alkylene with 1 to 3 fluorine and / or chlorine atoms are suitable,

for phenyl which is optionally monosubstituted to trisubstituted by identical or different substituents, the substituents being halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ -haloalkyl having 1 to 5 fluorine and / or chlorine atoms as well as C ₁ -C ₄ haloalkoxy with one or more fluorine and / or chlorine atoms,

or for the rest -NR ⁴ -R ⁵

R ⁴ particularly preferably represents hydrogen or C ₁ -C ₂ alkyl

R ³ particularly preferably represents C ₁ -C ₄ -alkyl or optionally substituted once or twice, identically or differently in the phenyl moiety

Phenyl or benzyl, in each case as substituents halogen, C ₁ -C ₂ alkyl, C ₁ -C ₂ haloalkyl with 1 to 5 fluorine and / or chlorine atoms and C ₁ -C ₂ - haloalkoxy with 1 to 5 fluorine and / or chlorine atoms come into question

R ¹ very particularly preferably represents hydrogen, chlorine, bromine or trifluoromethoxy very particularly preferably represents hydrogen,

for methyl, ethyl, propyl, butyl, pentyl, hexyl,

for propenyl, butenyl, pentenyl, hexenyl,

for propynyl, butynyl, pentynyl,

for one of the groups -CHF ₂ , -CF ₂ CHFCl, -CF ₂ CH ₂ F, -CF ₂ CHF -CF ₂ CCl ₃ , -CF ₂ CHFCF ₃ , -CH ₂ CF ₃ , -CH ₂ CF ₂ CHF ₂ , -CH ₂ CF ₂ CF ₃ , -CF ₂ -CHF-CF ₃ ,

for one of the cycloalkyl groups

for one of the cycloalkenyl groups

for one of the cycloalkylalkyl groupings

for the cycloalkenylalkyl grouping:

^•

for one of the cycloalkenylalkyl groups:

or for the rest -COR ³ . very particularly preferably represents methyl, ethyl, propyl, methoxy, ethoxy, propoxy, butoxy,

for cyclopropyl, cyclohexyl, for cyclohexyloxy,

for phenyl, 2-chlorophenyl, 3-chlorophenyl, 2,6-difluorophenyl, 2-trifluoromethoxyphenyl, 4-trifluoromethoxyphenyl; 2,4-dichlorophenyl, 3,4-dichlorophenyl,

or for the rest -NR ⁴ R ⁵ .

R ⁴ very particularly preferably represents hydrogen.

R ⁵ very particularly preferably represents methyl, ethyl or phenyl which is optionally monosubstituted by chlorine.

The hydrocarbon radicals mentioned above in the definition of the compounds according to the invention, such as alkyl or alkenyl, can - also in conjunction with

Heteroatoms such as alkoxy - be straight-chain or branched as far as possible

The general definitions or explanations of residues or explanations listed above or in preferred areas can be combined with one another, i.e. 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 a combination of the meanings listed as preferred (preferred) is present. According to the invention, particular preference is given to the compounds of the formula (I) in which a combination of the meanings listed as particularly preferred is present

According to the invention, very 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

If, according to the first stage of process (a) z B, N- [1- (4-allyloxybiphenyl-3-yl) -2-chloroethyl] -2,6-difluorobenzamide is used as the starting material, the course of the process according to the invention can be reproduced by the following reaction scheme

In the second stage of process (a), use is made, for example, of 2- (2,6-di-fluorophenyl) -4- (4-allyloxybiphenyl-3-yl) -2-oxazoline as the starting material and palladium / carbon as the catalyst, if appropriate in the presence of p-toluenesulfonic acid, the course of the process according to the invention can be represented by the following reaction scheme:

According to method (b), e.g. 2- (2,6-difluorophenyl) -4- (4-hydroxybiphenyl-3-yl) -2-oxazoline and ethyl chloroformate as starting materials, the course of the process according to the invention can be represented by the following reaction scheme.

Formula (II) provides a general definition of the m-biphenylchloroethylbenzamides required as starting materials for carrying out process (a) according to the invention. In formula (II), R preferably or particularly preferably represents allyl or the radical -COR ³ , where R ³ has the meanings given above

The m-biphenyl-chloroethyl-benzamides of the formula (II) are not yet known and are also an object of this invention Way can be obtained, for example, by using N- (1-methoxy-2-chloroethyl) -2,6-difluorobenzamide of the formula (IV)

with biphenyl derivatives of the formula (Va)

in which

R ¹ and R have the meaning given above, in the presence of a catalyst, such as, for example, ferric chloride and in the presence of a diluent, for example halogenated hydrocarbons such as methylene chloride, at temperatures between 0 ° C and 80 ° C (see also

EP-A 0 594 179 and the production examples)

The m-biphenyl-chloroethyl-benzamides of the formula (II) can also be obtained if N- (1-methoxy-2-chloroethyl) -2,6-difluorobenzamide of the formula (IV)

initially with biphenyl derivatives of the formula (Vb)

in which R ^{1 has} the meaning given above, in the presence of a catalyst, such as iron (III) chloride and in the presence of a diluent, for example halogenated hydrocarbons such as methylene chloride, at temperatures between 0 ° C and 80 ° C and the m-biphenyl thus obtained chloroethyl benzamides of the formula (Ha)

in which

R ^{1 has} the meaning given above, alkylated or acylated in a generally known manner (see, for example, J. of Chem Soc 1937, pp. 771-773).

The m-biphenyl-chloroethyl-benzamides of the formula (Ha) are not yet known and are also the subject of this invention.

The N- (1-methoxy-2-chloroethyl) -2,6-difluorobenzamide of the formula (IV) is known (cf. EP-A 0 594 179). Some of the biphenyl derivatives of the formula (Va) are known or are obtainable in a generally known manner, such as by alkylation or acylation of the corresponding OH derivatives of the formula (Vb) (see e.g. J. of Chem Soc

1937, S 771-773)

The 4- (4-hydroxy-3-biphenyl) oxazolines of the formula (Ib) required as starting materials for carrying out process (b) according to the invention are compounds according to the invention

They also represent generally interesting intermediates Formula (III) provides a general definition of the compounds required as starting materials for carrying out process (b) according to the invention

M stands for a customary leaving group. R ^{2 stands} for -COR ³ , preferably meanings for M are halogen, such as especially chlorine or bromine, anhydride and imidazolide. If R ^{2 stands} for its other meanings, preferably meanings for M are halogen, such as in particular Chlorine or bromine, alkylsulfonyloxy, such as, in particular, methyl sulfonyloxy, and optionally substituted arylsulfonyloxy, such as, in particular, phenylsulfonyloxy, p-chlorophenylsulfonyloxy or tolylsulfonyloxy

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

Suitable diluents for carrying out the first stage of process (a) according to the invention are all inert organic solvents. They can optionally be used in a mixture with water. Hydrocarbons such as toluene, xylene, tetralin, hexane, cyclohexane, halogenated hydrocarbons such as methylene chloride, chloroform are preferably used , Chlorobenzene, o-dichlorobenzene, alcohols such as methanol, ethanol, glycol, the isomeric propanols, butanols, pentanols, ethers such as diethyl ether, diisopropyl ether, dimethoxyethane, tetrahydrofuran, dioxane, nitriles such as acetonitrile or butyronitrile, amides such as dimethylformamide, sulfoxides such as dimethyl sulfide, such as dimethyl Sulfolan

Suitable bases for carrying out the first stage of process (a) according to the invention are all customary acid acceptors. Tertiary amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclonones (DBN), N, N-dimethylanin are preferably usable , furthermore alkaline earth metal oxides such as magnesium and calcium oxide, furthermore alkali and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, alkali metal hydroxides such as sodium and potassium hydroxide, furthermore alcoholates such as sodium ethanolate or potassium tert-butoxide when carrying out the first stage of the process (a) according to the invention is optionally carried out in the presence of a phase transfer catalyst As Phase transfer catalysts are, for example, tertiary ammonium compounds such as tetraoctylammonium bromide or benzyltriethylammonium chloride

The reaction temperatures can be varied within a substantial range when carrying out the first stage of process (a) according to the invention. In general, temperatures between -10 ° C and 150 ° C, preferably between -10 ° C and 80 ° C.

The first stage of process (a) according to the invention is generally carried out under normal pressure.

When carrying out the first stage of process (a) according to the invention, preference is given to working with equimolar amounts of base and compounds of the formula (II). However, it may also be possible to work with an excess of base. The processing takes place according to usual methods

Suitable diluents for carrying out the second stage of process (a) according to the invention are preferably water / alcohol mixtures, such as water / methanol, water / ethanol or water / propanol, and

Water / amide mixtures, such as water / dimethylformamide, water / dimethylacetamide and the water / toluene mixture are suitable.

The second stage of process (a) according to the invention is carried out in the presence of a catalyst. A metallic palladium / carbon mixture or palladium complex compounds (palladium in the oxidation stage +0), such as, for example, tetrakis (triphenylphosphine) palladium (O), are preferably used. .

The second step of process (a) according to the invention is optionally carried out in the presence of an acid. In principle, inorganic or organic acids or Lewis acids are suitable. For example, sulfuric acid, methanesulfonic acid, benzene sulfonic acid, p-toluenesulfonic acid, aluminum chloride, phosphorus oxychloride or boron trifluoroetherate are preferred

When carrying out the second stage of process (a) according to the invention, the reaction temperatures can be varied within a substantial range generally one works at temperatures between 0 ° C and 150 ° C, preferably between 0 ° C and 80 ° C

The second stage of process (a) according to the invention is generally carried out under atmospheric pressure. When carrying out the second stage of process (a) according to the invention, preferably 0.01 (mole) of 4- (m-biphenyl) oxazoline of the formula (Ia) is used up to 0.1 mol of catalyst and optionally 0.01 to 1 mol of acid. Working up is carried out by customary methods

All inert solvents can be used as diluents in carrying out process (b) according to the invention. Hydrocarbons, such as gasoline, benzene, toluene, xylene and tetrahedron, and furthermore halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, can also be used Ketones, such as acetone and methylsopropyl ketone, furthermore ethers, such as diethyl ether, tetrahydrofuran and dioxane, in addition carboxylic acid esters, such as ethyl acetate, and also strongly polar solvents, such as dimethyl sulfoxide and sulfolane

Suitable bases for carrying out process (b) according to the invention are all customary acid acceptors. Tertiary amines such as triethylamine, pyndine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclonones (DBN), Hunig base and N, N are preferably usable -Dimethyl-anihn, also alkaline earth metal oxides, such as magnesium and calcium oxide, also alkah and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate and alkali or alkaline earth metal hydroxides such as sodium hydroxide or potassium hydroxide

Process (b) can be varied within a substantial range. In general, temperatures between -20 ° C and + 120 ° C, preferably between 0 ° C and 80 ° C.

Process (b) according to the invention is generally carried out under normal pressure When carrying out process (b) according to the invention, the reaction is generally carried out in approximately equivalent amounts. However, it is also possible to use the compound of the formula (III) in a relatively large excess (up to 5 mol). Working up is carried out by customary methods. The active compounds are suitable to combat animal pests, in particular insects, arachnids and nematodes, which protect in agriculture, in forests, in the supply and material and in the hygiene sector.You can preferably use them as plant protection products.You are against normally sensitive and resistant species and against all or individual stages of development effective The pests mentioned above include

From the order of the Isopoda, for example Oniscus asellus, Armadillidium vulgare, Porcellio scaber

From the order of the Diplopoda, for example, Blaniulus guttulatus

From the order of the Chilopoda, for example Geophilus carpophagus, Scutigera spec From the order of the Symphyla, for example 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, for example 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, for example Reticulitermes spp

From the order of the Anoplura eg Pediculus humanus corporis, Haematopinus spp, Linognathus spp From the order of the Mallophaga eg Trichodectes spp Damalinea spp From the order of the Thysanoptera, for example Hercinothrips femoralis, Thrips tabaci

From the order of Heteroptera, for example 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, Pempheusumpp. , Phorodon humuh, Rhopalosiphum padi, Empoasca spp., Euscehs bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantn, Aspidiotus hederae s, Pseudococcuspp

From the order of the Lepidoptera, for example Pectinophora gossypiella, Bupalus pimarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella macuhpennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Agristella spp., Bucculisella spp, Earias insulana, Hehothis spp, Spodoptera exigua, Mamestra brassicae,

Panolis flammea, Spodoptera htura, Spodoptera spp, Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilahs, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pelhonellauauaanaanaellaella, Hofmannophanaacoana, Hofmannophana pella Clysia ambiguella, Homona magnanima, Tortrix viridana

From the order of the Coleoptera, for example Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodivusisisam ., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopohtes sordidus,

Ceuthorrhynchus assimihs, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Agrebri moht, Tenebrio moht Conoderus spp., Melolontha melolontha, Amphimallon solstitiahs Costelvtra zealandica

From the order of Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp From the order of Diptera, for example Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp, Gastrophilus spp., Hyppobosca , Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp, Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata,

Dacus oleae, Tipula paludosa

From the order of the Siphonaptera, for example Xenopsylla cheopis, Ceratophyllus spp

From the order of the Arachnida, for example Scorpio maurus, Latrodectus mactans

From the order of the Acarina, for example Acarus siro, Argas spp., Ormthodoros spp., Dermanyssus galhnae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp,

Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp

The active compounds according to the invention are notable for high insecticides and acaricidal activity

They can be used with particularly good success to control plant-damaging insects, for example against the larvae of the green rice leafhopper (Nephotettix cincticeps) or against the caterpillars of the cockroach (Plutella maculipennis) .The active compounds can be converted into the customary formulations, such as solutions or emulsions , Wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances and 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, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. Liquid solvents are essentially suitable. Aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, 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.

The following are suitable as solid carriers:

e.g. 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 silicic acid, aluminum oxide and silicates, are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; Possible emulsifiers and / or foam-generating agents are: eg nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, eg alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose

Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, 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, 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 0J and 95% by weight of active compound, preferably between 0.5 and 90%

The active substance according to the invention can be used 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 are present. The insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc. The following are particularly advantageous mixed partners, for example

Fungicides:

2-aminobutane, 2-anihno-4-methyl-6-cyclopropyl-pyrimidine, 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-1,3-thiazole-5- carboxanilide, 2,6-dichloroN- (4-trifluoromethylbenzyl) benzamide, (E) -2-methoxyimino-N-methyl-2- (2phenoxyphenyl) acetamide, 8-hydroxyquinoline sulfate, methyl- (E) -2- {2 - [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate, methyl (E) methoximino¬

[alpha- (o-tolyloxy) -o-tolyi] acetate, 2-phenylphenol (OPP), aldimorph, ampropylfos,

Anilazine, azaconazole,

Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,

Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate

(Quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozohnate, cufraneb,

Cymoxanil, cyproconazole, cyprofuram,

Dichlorophene, diclobutrazole, diclofluanid, diclomezm, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditahmfos, dithianon, dodine, drazoxolone,

Edifenphos, epoxyconazole, ethirimol, etridiazole,

Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanyl, Futuberfoxylol

Guazatine,

Hexachlorobenzene, hexaconazole, hymexazole,

Ima number Imibenconazol, Iminoctadin Iprobefos (IBP) Iprodion Isoprothiolan Kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,

Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,

Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,

Ofurace, oxadixyl, oxamocarb, oxycarboxin,

Pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,

Quintozen (PCNB),

Sulfur and sulfur preparations,

Tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,

Validamycin A, vinclozolin,

Zineb, ziram.

Bactericides:

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

Insecticides / acaricides / nematicides:

Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M,

Azocyclotin,

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

Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157

419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,

Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etrimphos,

Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenothxinfox, Fufionophon, Fufionophon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufon

HCH, heptenophos, hexaflumuron, hexythiazox,

Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Lambda-cyhalothrin, Lufenuron,

Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,

Naled, NC 184, NI 25, Nitenpyram,

Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,

Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet,

Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophos,

Pyradaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen,

Quinalphos,

RH 5992,

Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,

Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos,

Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomethrin, Triarathen, Triazophos, Triazuron, Trichlorfon, Triflumuron, Trimethacarb,

Vamidothion, XMC, Xylylcarb, YI 5301/5302, Zetamethrin Also a mixture with other known active ingredients, such as herbicides or with

Fertilizers and growth regulators are possible

The active compounds according to the invention can also be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists. Synergists are compounds by which the effect 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

When used against hygiene and storage pests, the active ingredient is characterized by an excellent residual effect on wood and clay as well as a good stability to alkali on limed substrates

It has also been found that the compounds of the formula 1 according to the invention have a high insecticidal action against insects which destroy industrial materials. The following are examples and preferably, but are not limited, are preferred

Called insects

Beetle like

Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptihnus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis,

Lyctus pubescens, Trogoxylon aequale, Minthes rugicolhs, Xyleborus spec Tryptodendron spec Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec Dinoderus minutus

Hautflieger like

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

Termites like

Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticuhtermes flavipes, Reticuhtermes santonensis, Reticulitermes lucifugus Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus Bristle tail, such as Lepisma saccharina.

In the present context, technical materials are understood to mean 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 substances can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredients with at least one solution or. Diluent, emulsifier, dispersant and / or binder or fixative, water repellent, optionally siccatives and UV stabilizers and optionally dyes and pigments and other processing aids

The insecticidal compositions or concentrates used to protect wood and wood-based materials contain the active ingredient according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight. The amount of the compositions or concentrates used is of the type and Occurrence of the insects and depending on the medium. The optimal amount can be determined by using 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 difficultly 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 agents

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

Mineral oils with a boiling range of 170 to 220 ° C, white spirit with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° C, turpentine oil and the like are advantageous for use

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 spindeol and / or monochloronaphthalene, preferably α-monochloronaphthalene, are used

The organic slightly volatile oily or oil-like solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partially replaced by slightly or medium-volatile organic chemical solvents, with the proviso that the solvent mixture also has an evaporation number 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

Solvents or solvent mixtures or an aliphatic polar organic-chemical solvent or solvent mixture replaced. Aliphatic compounds containing hydroxyl and / or ester and / or ether groups are preferably used. organic chemical solvents such as glycol ether, ester or the like for use

In the context of the present invention, the known organic-chemical binders are water-thinnable 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 Vinyl resin, e.g. polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as inden 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, dyes, pigments, water repellents, odor correctors and inhibitors or inhibitors known per se can be used Corrosion protection agents and the like are used

According to the invention, the organic-chemical binder is preferably at least one alkyd resin or modified alkyd resin and / or a drying vegetable O1 in the medium or in the concentrate. According to the invention, alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68%, are preferred % By weight used

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 failure.Preferably they replace 0.01 to 30% of the binder (based on to 100% of the binder used)

The plasticizers are from the chemical classes of the phthalic esters such as dibutyl, dioctyl or benzyl butyl phthalate, Phosphorsaureester such as tributyl phosphate, Adipinsaureester such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, glycerol ethers or higher molecular weight glycol ethers, Glycerinester 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, optionally in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants

A particularly effective wood preservation is achieved by industrial impregnation processes, e.g. vacuum, double vacuum or pressure processes

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

The additional admixing partners are preferably the insecticides and fungicides mentioned in WO 94/29 268. The compounds mentioned in this document are an express component of the present application

Insecticides such as chlorpyriphos, phoxime, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumuron can be used as very particularly preferred mixing partners.

as well as fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole,

Tebuconazole, cyproconazole, metconazole, imazahl, dichlorfluanid, tolylfluanid, 3-iodo-2-propynyl-butylcarbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one,

his

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

example 1

(Procedure a, first stage)

1.05 g (0.0025 mol) of N- [1- (4-allyloxybiphenyl-3-yl) -2-chloroethyl] -2,6-difluorobenzamide (Ex. II-1) are dissolved in 5 ml of dimethylformamide and 0.44 ml (0.005 mol) of 50% aqueous sodium hydroxide solution were added dropwise at 5 ° C. The reaction mixture is stirred at room temperature for 18 hours. It is then poured into 100 ml of ice water, extracted with ethyl acetate, dried over sodium sulfate and concentrated in vacuo.

0.8 g of 2- (2,6-difluorophenyl) -4- (4-allyloxybiphenyl-3-yl) -2-oxazoline of

Refractive index n _D ²⁰ = 1.5945.

Example 2

(Method a, second stage)

0.5 g of 2- (2,6-difluorophenyl) -4- (4-allyloxybiphenyl-3-yl) -2-oxazoline (Ex. 1) are dissolved in 5 ml of methanol and 1 ml of water, with 0.23 g p-Toluenesulfonic acid and 0.05 g palladium / carbon (10%) were added and the mixture was stirred at 60 ° C. for 20 hours. After filtering off the catalyst, the filtrate is concentrated, in 50 ml of methylene chloride taken up, washed with 25 ml of water, dried over sodium sulfate and concentrated in vacuo

0.4 g of 2- (2,6-difluorophenyl) -4- (4-hydroxybiphenyl-3-yl) -2-oxazoline with a log p * = 2.08 is obtained

The following compounds of the formula (I) are obtained analogously to Examples 1 and 2 or according to the general information on the preparation

Preparation of the starting materials of the formulas (II) and (IIa) Example (II-1)

14.3 g (0.055 mol) of 2- (2,6-difluorobenzoylamido) -2-methoxy-1-chloroethane and 10.5 g (0.05 mol) of 4-allyloxybiphenyl are dissolved in 50 ml of methylene chloride and at 15 ° C. 8.6 g (0.075 mol) of anhydrous ferric chloride were added in portions within 30 minutes. The reaction mixture is allowed to stir at 15 ° C.-20 ° C. for 18 hours and then poured onto 500 ml of ice water. The organic phase is separated off, washed with 100 ml of water, dried over sodium sulfate and concentrated in vacuo. After stirring with diethyl ether, 1 1, 4 g and a further 3.9 g of the desired product are obtained from the filtrate.

A total of 15.3 g (71% of theory) of N- [1- (4-allyloxybiphenyI-3-yl) -2-chloroethyl] -2,6-difluorobenzamide with a melting point of 159 ° C. are obtained.

Example (IIa-1)

1.3 g (0.005 mol) of 2- (2,6-difluorobenzoylamido) -2-methoxy-1-chloroethane and 0.85 g (0.005 mol) of 4-hydroxybiphenyl are dissolved in 20 ml of carbon tetrachloride and added dropwise at 70 ° C 0.77 g (0.005 mol) of phosphorus oxychloride were added. The reaction mixture is left to stir at 70 ° C. for 3 hours and then worked up in a generally customary manner.

1.3 g (67.2% of theory) of N- [1- (4-hydroxybiphenyl-3-yl) -2-chloroethyl] -2,6-difluorobenzamide with a melting point of 185 ° C.-188 ° C. are obtained Example (II-2)

To 19.3 g (0.05 mol) of N- [1- (4-hydroxyphenyl-3-yl) -2-chloroethyl] -2,6-difluorobenzamide (Ex. IIa-1) in 100 ml of tetrahydrofuran and 7 ml (0.05 mol) of triethylamine are added at 5 ° C to 10 ° C 6 ml (0.055 mol) of ethyl chloroformate. The reaction mixture is left to stir at room temperature for 15 hours and then concentrated. The residue is taken up in 200 ml of methylene chloride, washed with 100 ml of water, dried over sodium sulfate and concentrated in vacuo. The residue is stirred with ether and suction filtered. 16.2 g (70.4% of theory) of N- [1- (4-ethyloxycarbonyloxybiphenyl-3-yl) -2-chloroethyl] -2,6-difluorobenzamide are obtained, melting point 145 ° C.-148 ° C. .

Application examples Example A Plutella test

Solvent. 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkyl aryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted 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 Plutella maculipennis cockroach while the leaves are still moist

After the desired time, the kill is determined in%. 100% means that all the caterpillars have been killed; 0% means that no caterpillars have been killed. In this test, for example, the compound according to Preparation Example 1, with an exemplary active compound concentration of 0J%, caused 100% destruction after 7 days

Example B

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 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 none of the cicadas have been killed. In this test, for example, the compound according to Preparation Example 3 caused a kill with an active compound concentration of 0J% from 100% after 6 days

Claims

1. Compounds of formula (I)

in which

R ^{1 represents} hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkenyl, haloalkenyl, alkenyloxy, haloalkenyloxy, alkynyl, haloalkynyl, alkynyloxy, haloalkynyloxy or any optionally substituted cycloalkyl or cycloalkylalkyl and R ^{2 represents} hydrogen, alkyl, alkenyl, alkynyl , Haloalkyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl, optionally substituted aralkyl or for the radical -COR ³ , where

R ³ for alkyl, alkoxy, alkenyl, al kenyloxy, j ewei ls optionally substituted cycloalkyl, cycloalkyloxy or

Cycloalkylalkyloxy, optionally substituted aryl or for the radical -NR ⁴ R ⁵ , where

R ^{4 represents} hydrogen or alkyl and

R ^{3 represents} alkyl, haloalkyl, in each case optionally substituted cycloalkyl or cycloalkylalkyl or for in each case optionally substituted phenyl or phenylalkyl Compounds of formula (I) according to claim 1, in which

R ¹ for hydrogen, for fluorine, chlorine or bromine, for C ₁ -C ₉ alkyl, C ₁ - C ₆ alkoxy, C ₁ -C ₆ haloalkyl or C ₁ -C ₆ haloalkoxy, each with one or more fluorine - and / or chlorine atoms, for C ₃ -C ₁₂ alkenyl, C ₃ -C ₁₂ alkenyloxy or C ₃ -C ₆ haloalkenyl with one or more fluorine and / or chlorine atoms, for C ₃ -C ₁₂ alkynyl, C ₃ -C ₁₂ - alkynyloxy, or C _λ -C ₆ haloalkynyl with one or more fluorine and / or chlorine atoms, or represents in each case optionally mono- or polysubstituted by identical or different manner by halogen or C ₁ -C ₄ alkyl C ₃ -C ₆ -cycloalkyl or C ₃ -C ₆ -cycloalkyl- C ₁ -C ₄ -alkyl,

R ² for hydrogen, for C ₁ -C _p alkyl, for C ₃ -C ₁₂ alkenyl, for C ₁ -C ₁₂ alkynyl, for C ₁ -C ₆ haloalkyl with one or more fluorine and / or chlorine atoms, for each in the cycloalkyl part optionally mono- or polysubstituted, identically or differently substituted C ₃ -C ₆ -cycloalkyl or C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, in each case halogen, C ₁ -C ₄ -alkyl as substituents, optionally singly or multiply, identically or differently substituted by halogen C ₂ - C ₄ alkenyl and in each case optionally singly or multiply, identically or differently by halogen substituted phenyl or

Styryl come into question

in each case optionally monosubstituted or polysubstituted by identical or different substituents, by halogen or C ₁ -C ₄ alkyl C ₄ -C ₆ - cycloalkenyl or C ₄ -C ₆ cycloalkenyl-C ₁ -C ₄ alkyl,

substituted in the aryl moiety in each case optionally monosubstituted or polysubstituted by identical or different phenyl-C ₁ -C ₄ alkyl, or naphthylmethyl, wherein in each case as substituents halogen, C ₁ -C ₁₂ alkyl, C ₁ - C ₁₂ haloalkyl with one or more Fluorine and / or chlorine atoms, C ₁ -C ₁₂ alkoxy or C ₁ -C ₁₂ haloalkoxy with one or more fluorine and / or chlorine atoms are possible, or the radical is -COR ³ ,

R ³ for C ₁ -C ₁₂ alkyl, for C ₁ -C ₁₂ alkoxy, for C ₃ -C ₁₂ alkenyl, for C ₃ - C ₁₂ alkenyloxy, for each in the cycloalkyl part optionally one or more times, the same or different substituted C ₃ -C ₆ - Cycloalkyl, C ₃ -C ₁₀ cycloalkyloxy or C ₃ -C ₁₀ cycloalkyl-C ₁ -C ₆ - alkoxy, where in each case as substituents C ₁ -C ₄ alkyl, halogen, C ₁ - C ₄ haloalkyl with one or several fluorine and / or chlorine atoms and C ₂ -C ₄ haloalkenyl with one or more fluorine and / or chlorine atoms are suitable,

in each case optionally singly or multiply, identically or differently substituted phenyl or naphthyl, in each case being phenyl or naphthyl substituents are halogen, C ₁ -C ₁₂ alkyl, C ₁ - C ₁₂ haloalkyl with one or more fluorine and / or chlorine atoms, C ₁ -C ₁₂ alkoxy and C ₁ -C ₁₂ haloalkoxy with one or more fluorine and / or chlorine atoms, or for the radical -NR ⁴ -R ⁵ ,

R ^{4 represents} hydrogen or C ₁ -C ₁₂ alkyl and

R ³ for C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ haloalkyl with one or more fluorine and / or chlorine atoms, for each in the cycloalkyl part optionally mono- or polysubstituted, identically or differently substituted, C ₃ -C ₆ cycloalkyl or C ₃ -C ₆ cycloalkyl-C ₁ -C ₄ alkyl, where in each case substituents are C ₁ -C ₄ alkyl, halogen, C ₁ -C ₄ haloalkyl with one or more fluorine and / or chlorine atoms and C ₂ -C ₄ haloalkenyl with one or more fluorine and / or

Chlorine atoms come into question

or substituted in each case optionally monosubstituted or polysubstituted by identical or different phenyl or phenyl-C ₁ -C ₆ -alkyl, wherein the phenyl in each case halogen, C ₁ -C ₁₂ alkyl, C ₁ - C ₁₂ haloalkyl with one or more Fluorine and / or chlorine atoms, C ₁ -C ₁₂ alkoxy and C ₁ -C ₁₂ haloalkoxy with one or more fluorine and / or chlorine atoms are suitable.

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

R ¹ for hydrogen, for fluorine, chlorine or bromine, for C ₁ -C ₆ -alkyl, C ₁ - C ₄ -alkoxy, C ₁ -C ₄ -haloalkyl or C ₁ -C ₄ -haloalkoxy, each with two or more fluorine and / or chlorine atoms, for C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyl or C ₁ -C ₆ alkynyloxy, or for each in each case optionally up to three times, identical or C ₃ -C ₆ cycloalkyl or C ₃ -C ₆ cycloalkyl-C ₁ -C ₄ alkyl which is differently substituted by fluorine or chlorine,

R ² for hydrogen, for C ₁ -C ₆ alkyl, for C ₃ -C ₁₂ alkenyl, for C ₃ -C ₆ alkynyl, C ₁ -C ₄ haloalkyl with two or more fluorine and / or chlorine atoms, each for in the cycloalkyl moiety is optionally mono- to trisubstituted by identical or different substituents, C ₃ -C ₆ - cycloalkyl or C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, in each case as substituents of fluorine, chlorine, bromine, C ₁ -C ₂ Alkyl, optionally mono- or polysubstituted, identically or differently, by C ₂ -C ₄ -alkenyl substituted by fluorine or chlorine, and in each case optionally mono- or disubstituted, identically or differently, by fluorine or chlorine, phenyl and styryl,

for C ₄ -C ₆ -cycloalkenyl or C ₄ -C ₆ -cycloalkenylmethyl which is optionally substituted once or twice, identically or differently by fluorine or chlorine,

for phenyl-C ₁ -C ₄ -alkyl which is optionally monosubstituted to trisubstituted, identically or differently, in the phenyl part, where fluorine, chlorine, C ₁ -C ₄ -alkyl, halomethyl having one or more fluorine and / or chlorine atoms, C ₁ -C ₄ alkoxy or C ₁ -C ₄ - haloalkoxy come with one or more fluorine and / or chlorine atoms in question,

or represents the rest -COR ³ ,

R ³ for C ₁ -C ₄ alkyl, for C ₁ -C ₄ alkoxy, for C ₃ -C ₆ alkenyl, for C ₃ -C ₆ alkenyloxy, for each in the cycloalkyl part, if appropriate, once to three times, identically or differently substituted C ₃ -C ₆ cycloalkyl,

C ₃ -C ₆ cycloalkyloxy or C ₃ -C ₆ cycloalkyl-C ₁ -C ₄ alkoxy, where in each case as substituents C ₁ -C ₂ alkyl, fluorine, chlorine, C ₁ -C ₂ haloalkyl with 1 to 5 fluorine and / or chlorine atoms and C ₂ alkenyl with 1 to 3 fluorine and / or chlorine atoms come into question, for optionally monosubstituted to trisubstituted, identical or different, phenyl, with substituents being halogen, C ₁ -C ₄ alkyl C ₁ -C ₄ alkoxy, C ₁ -C ₂ haloalkyl with 1 to 5 fluorine and / or chlorine atoms and C ₁ -C ₄ haloalkoxy with one or more fluorine and / or chlorine atoms are suitable,

or stands for the rest -NR ⁴ -R ⁵ , R ^{4 represents} hydrogen or C ₁ -C ₂ alkyl and

R ^{3 is} C ₁ -C ₄ alkyl or phenyl or benzyl which is optionally mono- or disubstituted, identically or differently, in the phenyl moiety, in each case halogen, C ₁ -C ₂ alkyl, C ₁ -C ₂ haloalkyl as substituents with 1 to 5 fluorine and / or chlorine atoms and C ₁ -C ₂ haloalkoxy with 1 to 5 fluorine and / or chlorine atoms.

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

R ^{1 represents} hydrogen, chlorine, bromine or trifluoromethoxy,

R "for hydrogen,

for methyl, ethyl, propyl, butyl, pentyl, hexyl,

for propenyl, butenyl, pentenyl, hexenyl,

for propynyl, butynyl, pentynyl,

for one of the groups: -CHF ₂ , -CF ₂ CHFCl, -CF ₂ CH ₂ F, -CF ₂ CHF ₂ ,

-CF ₂ CCl ₃ , -CF ₂ CHFCF ₃ , -CH ₂ CF ₃ , -CH ₂ CF ₂ CHF ₂ , -CH ₂ CF ₂ CF ₃ ,

-CF ₂ -CHF-CF ₃ ,

for one of the cycloalkyl groups:

for one of the cycloalkenyl groups:

for one of the cycloalkylalkyl groupings:

for the cycloalkenylalkyl grouping:

^,

for one of the cycloalkenylalkyl groups:

,,,

or represents the rest -COR ³ ,

R ³ for methyl, ethyl, propyl,

for methoxy, ethoxy, propoxy, butoxy,

for cyclopropyl, cyclohexyl,

for cyclohexyloxy,

for phenyl, 2-chlorophenyl, 3-chlorophenyl, 2,6-difluorophenyl, 2-trifluoromethoxyphenyl, 4-trifluoromethoxyphenyl, 2,4-dichlorophenyl,

3,4-dichlorophenyl,

or represents the radical -NR ⁴ R ⁵ ,

R ^{4 represents} hydrogen and

R ^{5 represents} methyl, ethyl or phenyl which is optionally monosubstituted by chlorine. Process for the preparation of compounds of the formula (I) according to Claim 1, characterized in that a) m-biphenyl-chloroethyl-benzamide of the formula (II)

in which

R ^{1 has} the meaning given above and R represents allyl or the radical -COR ³ , where

R ^{3 has} the meaning given above, cyclized in a first stage in the presence of a base, if appropriate in the presence of a catalyst and if appropriate in the presence of a diluent and, if appropriate, then subsequently in a second stage the 4- (m-biphenyl) oxazolines of the formula obtained (Ia)

in which R ^{1 has} the meaning given above and

R represents allyl or the radical -COR ³ , where

in which R has the meaning given above; and optionally the 4- (4-hydroxy-3-biphenyl) -oxyzoiines of the formula (Ib) thus obtained

in which

M stands for a leaving group and

R ^{2 has} the meaning given above, if appropriate in the presence of a diluent and if appropriate in the presence of a base. Compounds of formula (II)

in which

R ^{1 has} the meaning given in claim 1 and

R represents allyl or the radical -COR ³ , where

R ^{3 has} the meaning given in claim 1, compounds of the formula (IIa)

in which R ^{1 has} the meaning given in claim 1, pesticides, characterized in that it contains at least one compound of the formula (I) according to claim 1. Use of the compounds of the formula (I) according to claim 1 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

1 1. 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.

12. Use of compound of formula (I) according to claim 1 for the preparation of pesticides.