DE4304197A1 - Substituted oxazoles - Google Patents

Description

The invention relates to new substituted oxazoles, several processes for their manufacture position and its use as a pesticide.

It is known that certain substituted oxadiazoles such as the verbin 3- (3-Chlorophenyl) -5- (2-chlorophenyl) -1,2,4-oxadiazole acaricidal and insecticidal Have properties (see e.g. EP 36711).

The amount of action or duration of action of these known compounds is dependent yes, especially with certain pests and / or with low application concentrations are not completely satisfactory in all areas of application.

There have been new substituted oxazoles of the general formula (I)

in which
R ^{1 represents} hydrogen, alkyl or halogen,
R ^{2 represents} alkyl or halogen,
Ar represents a phenyl radical which is optionally substituted by halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkoxyalkyl, alkoxyalkoxy, optionally substituted cycloalkyl, optionally substituted cycloalkyloxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylalkyl and / or optionally substituted arylalkyloxy is substituted;
X for a grouping of the formula -CH ₂ -CH ₂ -; -CH ₂ -CH ₂ -CH ₂ -; -CH = CH-; -CH ₂ -CH = CH-; -CH ₂ -O-; -CH ₂ -S-; -CH ₂ -N (R ³ ) -; -CH ₂ -O-CH ₂ -; -CH ₂ -O-CH ₂ -CH ₂ - or -CH ₂ -O-CO-, where
R ^{3 represents} hydrogen, alkyl or alkanoyl; and
n stands for a number 0 or 1,
found.

The compounds of formula (I) may optionally, depending on the type of the substituents, as geometric and / or optical isomers or isomer mixtures different composition. The present invention extends to both the pure isomers and mixtures of isomers.

It was also found that the new substituted oxazoles of the general formula (I) are obtained
if

• a) for the preparation of compounds of general formula (I) in which n 0 means

Benzonitriles of the general formula (II),

in which
R ¹ and R ^{2 have} the meaning given above,
with α-chlorostyrenes of the general formula (III),

in which
Ar has the meaning given above,
first in a first stage with chlorine (preferably as a gas), if appropriate in the presence of a catalyst and if appropriate in the presence of a diluent and then in a second stage with water in the presence of a reaction auxiliary, if appropriate in the presence of a phase transfer catalyst and if appropriate in the presence of a diluent; or

• b) for the preparation of the compounds of the general formula (1), in which
  X is a grouping of the formula -CH ₂ -O-; -CH ₂ -S-; -CH ₂ -N (R ³ ) -; -CH ₂ -O-CH ₂ -; -CH ₂ -O-CH ₂ -CH ₂ - or -CH ₂ -O-CO- and
  n is 1, where R ^{3 has} the meaning given above,

Chloromethyloxazoles of the general formula (IV),

in which
R ¹ and R ^{2 have} the meaning given above,
with alcohol, phenol, carboxylic acid, amine or thiol derivatives of the general formula (V),

H-X₁-Ar (V)

in which
X ¹ for -O-; -S-; -N (R ³ ) -; -O-CH ₂ -; -O-CH ₂ -CH ₂ - or -O-CO-, where
R ^{3 has} the meaning given above,
if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary; or

• c) for the preparation of the compounds of general formula (I) in which
  X is a grouping of the formula -CH ₂ -CH ₂ -; -CH ₂ -CH ₂ -CH ₂ -; -CH = CH- or -CH ₂ -CH = CH- and n 1 mean

Chloromethyl-oxazoles of the general formula (IV),

in which
R ¹ and R ^{2 have} the meaning given above,
with phenylacetylene compounds of the general formula (VI),

H-C≡C-Ar (VI)

in which
Ar has the meaning given above,
or with benzyl sulfones of the general formula (VII),

Ar-SO ₂ -CH ₂ -Ar (VII)

in which
Ar has the meaning given above,
if appropriate in the presence of a diluent, if appropriate in the presence of a phase transfer catalyst and if appropriate in the presence of a reaction auxiliary and if appropriate subsequently subsequently the substituted oxazoles of the general formula (I), in which X is -CH = CH- or -CH ₂ -CH = CH - and n is 1, for the preparation of compounds of the general formula (I) in which X is -CH ₂ -CH ₂ or -CH ₂ -CH ₂ -CH ₂ - and n is 1,
hydrogenated in a subsequent second stage with hydrogen gas in the presence of a catalyst and optionally in the presence of a diluent.

Finally it was found that the new substituted oxazoles of the general Formula (1) good activity against pests, in particular against arthropods, preferably against acarids (mites) and insects.  

Preferred substituents or ranges of those listed in the above and below General formulas are explained below:

In the general formulas, alkyl and the alkyl part of alkoxy mean straight chain or branched alkyl having preferably 1 to 18, particularly preferably 1 to 16 and very particularly preferably 1 to 12 carbon atoms. Especially alkyl with 1 to 8 and in particular with 1 to 6 and whole is emphasized especially with 1 to 4 carbon atoms.

Examples include: methyl, ethyl, n- and i-propyl, n-, sec.-, i- and t-butyl, 1,1-dimethyl-propyl, n-hexyl, 1,1,3,3-tetramethyl-butyl, methoxy, ethoxy, n- and i-propyloxy and n-, sec.-, i- and t-butyloxy.

Alkenyl and the alkenyl portion of alkenyloxy are straight or branched and preferably contain 2 to 12, particularly preferably 2 to 8 and very particularly preferably 3 or 4 carbon atoms, examples being allyl and allyloxy be.

Alkynyl and the alkynyl part of alkynyloxy are straight-chain or branched and ent preferably hold 2 to 12, particularly preferably 2 to 8 and very particularly preferably 3 or 4 carbon atoms, with propargyl and propargyloxy as examples be mentioned.

Alkoxyalkyl and alkoxyalkoxy each contain in the alkyl and alkoxy parts preferably 1 to 8, particularly preferably 1 to 6 and very particularly preferably 1 up to 4 carbon atoms, the alkyl and alkoxy parts being straight-chain or branched could be. Examples include methoxymethyl, methoxyethyl, ethoxymethoxy and Called ethoxyethoxy.

Cycloalkyl and the cycloalkyl part of cycloalkoxy preferably contain 3 to 8, in particular 3 to 7 and very particularly preferably 3 to 6 carbon atoms, where Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentyloxy and cyclohexyl oxy may be mentioned by way of example.  

Aryl and the aryl parts in aryloxy, aralkyl and aralkyloxy preferably contain 6 or 10 carbon atoms, phenyl or naphthyl particularly and phenyl entirely are particularly preferred.

The alkyl parts in aralkyl and aralkyloxy are straight-chain or branched and preferably contain 1 to 8, particularly preferably 1 to 6 and very particularly preferably 1 to 4 carbon atoms.

Alkanoyl can be straight-chain or branched in the alkyl part and preferably contains 2 to 7, particularly preferably 2 to 5 and very particularly preferably 2 to 4 Carbon atoms.

Unless otherwise stated, Hal and halogen mean fluorine, chlorine, Bromine or iodine, preferably fluorine, chlorine or bromine and particularly preferably fluorine or chlorine.

Ar can be one or more times, preferably 1 to 5 times, particularly preferably 1 to 3 times and very particularly preferably 1 or 2 times by the same or different Be substituted. In the case that Ar is phenyl, there are Substituents preferably in the 4- and / or 2-positions of the phenyl ring. Ar preferably carries at least one substituent.

Cycloalkyl, cycloalkoxy, aryl, aryloxy, aralkyl and aralkyloxy can be used in the Cycloalkyl, aryl and / or alkyl parts one or more, preferably 1 to 5, in particular 1 to 3 and very particularly preferably 1 or 2 identical or carry different substituents. Preferred substituents are alkyl and / or Alkoxy with preferably 1 to 8, in particular 1 to 6 and very particularly preferred 1 to 4 carbon atoms mentioned, examples being methyl, ethyl, n- and i-propyl, Methoxy and ethoxy are listed.

In the general formulas, R ¹ preferably represents hydrogen, fluorine, chlorine, bromine or C ₁ -C ₆ alkyl.

In the general formulas, R ² preferably represents fluorine, chlorine, bromine or C ₁ -C ₆ alkyl.

In the general formulas, Ar preferably represents a phenyl radical which may be replaced by halogen; C ₁ -C ₁₈ alkyl; C ₂ -C ₁₂ alkenyl; C ₂ -C ₁₂ alkynyl; C ₁ -C ₁₈ alkoxy; C ₂ -C ₁₂ alkenyloxy; C ₂ -C ₁₂ alkynyloxy; C ₁ -C ₈ alkoxy-C ₁ -C ₈ alkyl; C ₁ -C ₈ alkoxy-C ₁ -C ₈ alkoxy; optionally substituted by C ₁ -C ₈ alkyl and / or C ₁ -C ₈ -alkoxy-substituted C ₃ -C ₈ -cycloalkyl; optionally substituted by C ₁ -C ₈ alkyl and / or C ₁ -C ₈ -alkoxy-substituted C ₃ -C ₈ cycloalkoxy; C ₆ or C ₁₀ aryl optionally substituted by C ₁ -C ₈ alkyl and / or C ₁ -C ₈ alkoxy; C ₆ or C ₁₀ aryloxy optionally substituted by C ₁ -C ₈ alkyl and / or C ₁ -C ₈ alkoxy; optionally substituted by C ₁ -C ₈ alkyl and / or C ₁ -C ₈ -alkoxy-substituted C ₆ - or C ₁₀ aryl-C ₁ -C ₈ alkyl and / or optionally substituted by C ₁ -C ₈ - alkyl and / or C ₁ -C ₈ alkoxy substituted C ₆ - or C ₁₀ aryl-C ₁ -C ₈ alkoxy is substituted.

In the general formulas, X preferably represents -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH = CH-, -CH ₂ -CH = CH-, -CH ₂ -O-, - CH ₂ -S-, -CH ₂ -N (R ³ ) -, -CH ₂ -O-CH ₂ -, -CH ₂ -O-CH ₂ -CH ₂ - or -CH ₂ -O-CO, where
R ^{3 represents} hydrogen, C ₁ -C ₆ alkyl or C ₂ -C ₇ alkanoyl.

In the general formulas, n is preferably 0 or 1.

In the general formulas, R ¹ particularly preferably represents hydrogen, fluorine, chlorine or C ₁ -C ₄ -alkyl.

In the general formulas, R ² particularly preferably represents fluorine, chlorine or C ₁ -C ₄ alkyl.

In the general formulas, Ar particularly preferably represents a phenyl radical which may be replaced by halogen; C ₁ -C ₁₆ alkyl; C ₂ -C ₈ alkenyl; C ₂ -C ₈ alkynyl; C ₁ -C ₁₆ alkoxy; C ₂ -C ₈ alkenyloxy; C ₂ -C ₈ alkynyloxy; C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl; C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkoxy; C ₃ -C ₇ cycloalkyl optionally substituted by C ₁ -C ₆ alkyl and / or C ₁ -C ₆ alkoxy; C ₃ -C ₇ cycloalkoxy optionally substituted by C ₁ -C ₆ alkyl and / or C ₁ -C ₆ alkoxy; C ₆ or C ₁₀ aryl optionally substituted by C ₁ -C ₆ alkyl and / or C ₁ -C ₆ alkoxy; C ₆ or C ₁₀ aryloxy optionally substituted by C ₁ -C ₆ alkyl and / or C ₁ -C ₆ alkoxy; optionally substituted by C ₁ -C ₆ alkyl and / or C ₁ -C ₆ -alkoxy-substituted C ₆ - or C ₁₀ aryl-C ₁ -C ₆ alkyl and / or optionally substituted by C ₁ -C ₆ alkyl and / or C ₁ -C ₆ alkoxy substituted C ₆ - or C ₁₀ aryl-C ₁ -C ₆ alkoxy is substituted.

In the general formulas, X particularly preferably represents -CH ₂ -CH ₂ -, -CH ₂ - CH ₂ -CH ₂ -, -CH = CH-, -CH ₂ -CH = CH-, -CH ₂ -O-, -CH ₂ -S-, -CH ₂ -N (R ³ ) -, -CH ₂ -O- CH ₂ -, -CH ₂ -O-CH ₂ -CH ₂ - or -CH ₂ -O-CO, where
R ^{3 represents} hydrogen, C ₁ -C ₄ alkyl or C ₂ -C ₅ alkanoyl.

In the general formulas, n is particularly preferably 0 or 1.

In the general formulas, R ¹ very particularly preferably represents hydrogen, fluorine or chlorine.

In the general formulas, R ² very particularly preferably represents fluorine, chlorine, methyl or ethyl.

In the general formulas, Ar very particularly preferably represents a phenyl radical which may be replaced by fluorine; Chlorine; C ₁ -C ₁₂ alkyl; C ₂ -C ₈ alkenyl; C ₂ -C ₈ alkynyl; C ₁ -C ₁₂ alkoxy; C ₂ -C ₈ alkenyloxy; C ₂ -C ₈ alkynyloxy; C ₁ -C ₄ -alkoxy-C ₁ - C ₄ alkyl; C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkoxy; C ₃ -C ₇ cycloalkyl optionally substituted by C ₁ -C ₄ alkyl and / or C ₁ -C ₄ alkoxy; C ₃ -C ₇ cycloalkoxy optionally substituted by C ₁ -C ₄ alkyl and / or C ₁ -C ₄ alkoxy; optionally substituted by C ₁ - C ₄ alkyl and / or C ₁ -C ₄ alkoxy substituted phenyl; phenoxy optionally substituted by C ₁ -C ₄ alkyl and / or C ₁ -C ₄ alkoxy; phenyl-C ₁ -C ₄ -alkyl optionally substituted by C ₁ -C ₄ alkyl and / or C ₁ -C ₄ alkoxy and / or optionally substituted by C ₁ -C ₄ alkyl and / or C ₁ -C ₄ - Alkoxy substituted phenyl-C ₁ -C ₄ alkoxy is substituted.

In the general formulas, X very particularly preferably represents -CH ₂ -CH ₂ -, -CH ₂ - CH ₂ -CH ₂ -, -CH = CH-, -CH ₂ -CH = CH-, -CH ₂ -O- , -CH ₂ -S-, -CH ₂ -N (R ³ ) -, -CH ₂ -O- CH ₂ -, -CH ₂ -O-CH ₂ -CH ₂ - or -CH ₂ -O-CO, in which
R ^{3 represents} hydrogen, C ₁ -C ₆ alkyl or C ₂ -C ₄ alkanoyl.

In the general formulas, n very particularly preferably represents 0 or 1.

In the general formulas, R ^{1 is} particularly emphasized for fluorine or chlorine.

In the general formulas, R ^{2 is} particularly emphasized for fluorine or chlorine.

In the general formulas, Ar is particularly emphasized for a phenyl radical which may be replaced by fluorine; Chlorine; C ₁ -C ₄ alkyl; C ₃ -C ₄ alkenyl; C ₃ -C ₄ alkynyl; C ₃ -C ₄ alkoxy; C ₃ -C ₄ alkenyloxy; C ₃ -C ₄ alkynyloxy; C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl; C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkoxy; C ₃ -C ₆ cycloalkyl optionally substituted by C ₁ -C ₄ alkyl and / or C ₁ -C ₄ alkoxy; C ₃ -C ₆ cycloalkoxy optionally substituted by C ₁ -C ₄ alkyl and / or C ₁ -C ₄ alkoxy; phenyl optionally substituted by C ₁ -C ₄ alkyl and / or C ₁ -C ₄ alkoxy; phenyloxy optionally substituted by C ₁ -C ₄ alkyl and / or C ₁ -C ₄ alkoxy; phenyl-C ₁ -C ₄ -alkyl optionally substituted by C ₁ -C ₄ -alkyl and / or C ₁ -C ₄ -alkoxy and / or optionally by C ₁ -C ₄ -alkyl and / or C ₁ -C ₄ - Alkoxy substituted phenyl-C ₁ -C ₄ alkoxy is substituted.

In the general formulas, X is particularly emphasized for -CH ₂ -CH ₂ -, -CH ₂ - CH ₂ -CH ₂ -, -CH = CH-, -CH ₂ -CH = CH-, -CH ₂ -O-, -CH ₂ -S-, -CH ₂ -N (R ³ ) -, -CH ₂ -O- CH ₂ -, -CH ₂ -O-CH ₂ -CH ₂ - or -CH ₂ -O-CO, where
R ^{3 represents} hydrogen, C ₁ -C ₄ alkyl or C ₂ -C ₄ alkanoyl.

In the general formulas, n stands for 1.

In the general formulas, R ¹ is particularly emphasized for chlorine.

In the general formulas, R ² is particularly emphasized for fluorine.

In the general formulas, Ar is particularly emphasized for a phenyl radical which is substituted by C ₁ -C ₈ -alkyl (preferably C ₁ -C ₆ -alkyl, very particularly preferably tC ₄ H ₉ ).

In the general formulas, X is particularly emphasized for -CH ₂ -CH ₂ -, -CH = CH-, -CH ₂ -O- or -CH ₂ -O-CO.

In the general formulas, n is particularly emphasized for 1.

In the general formulas, Ar stands for phenyl, which by a substituent, preferably in the 2- or 4-position, particularly preferably in the 4-position of the phenyl ring.

For the groups specified for X, the link on the left is attached to the Oxazol ring bound and the respective binding shown on the right to the phenyl ring Ar bound.

The general or preferred areas listed above Residual definitions or explanations can be among themselves, that is, between the respective areas and preferred areas can be combined as desired. They apply to the end products as well as for the preliminary and intermediate products accordingly.

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

According to the invention, particular preference is given to the compounds of the general Formula (I) in which a combination of the above is particularly preferred listed meanings is present.

According to the invention, the compounds of general formula (I) used, in which a combination of these as above very particularly preferred meanings are present.  

According to the invention, the compounds of general formula (I) in which a combination of the above as special highlighted meanings is present.

According to the invention, the compounds of general formula (I) in which a combination of these above as a whole especially highlighted meanings is present.

For example, 2-fluoro-6-chlorobenzonitrile and 4- (t-butyl) -α-chlorine are used styrene as starting compounds, so the reaction sequence of the Invention according to process variant (a) using the following formula:

If, for example, 2- (2,6-difluorophenyl) -4-chloromethyl-1,3-oxazole and 4- (i-Propyl) -benzyl alcohol as starting materials, so the course of the reaction Process variant (b) according to the invention using the following formula represent:

For example, 2- (2-fluoro-6-chlorophenyl) -4-chloromethyl-1,3-oxazole is used and 4- (t-butyl) -phenylacetylene as starting materials, the course of the reaction can be process variant (c) according to the invention using the following formula represent:

The to carry out process variant (a) according to the invention as Benzonitriles of the formula (II) required as starting materials are known or obtainable in Analogy to known processes (cf., for example, Tetrahedron Lett. 28, 111-114 [1987]; US 4,680,406; Tetrahedron Lett. 27, 2203-2206 [1986]; EP 49 186; DE 29 02 877).

Those used to carry out process variant (a) according to the invention as Starting materials required a-chlorostyrenes of the formula (III) are known or available in analogy to known processes (cf. e.g. DE 21 04 313; PCT Int. Appl. WO 91/19695; Liq. Cryst. 5, 233-249 [1989] and CA 116: 163143b).

The to carry out the process variants (b) and (c) as Starting products required chloromethyloxazoles of the formula (IV) are new and Part of the present invention.  

They are obtained if benzonitriles of the general formula (II)

in which
R ¹ and R ^{2 have} the meaning given above,
with 2,3-dichloro-1-propene of the general formula (VIII),

initially in a first stage with chlorine (preferably as a gas), optionally in Presence of a catalyst and optionally in the presence of a diluent agent and then in a second stage with water in the presence of a Reaction auxiliary, optionally in the presence of a phase transfer catalyst and optionally in the presence of a diluent.

Implementation of the process for the preparation of compounds of general Formula (IV) is carried out in accordance with the implementation of process variants (a) Preparation of the compounds of general formula (I) by instead of Compounds of the general formula (III) the compounds of the general formula (VIII) can be used.

2,3-dichloro-1-propene of the formula (VIII) is a generally known compound of organic chemistry (CA-Reg.No. 78-88-6).

Those used to carry out process variant (b) according to the invention as Starting products required alcohol, phenol, carboxylic acid, amine or  Thiol derivatives of the general formula (V) are generally known compounds of organic chemistry.

The one used to carry out process variant (c) according to the invention required phenylacetylene compounds of the formula (VI) generally known compounds of organic chemistry.

The alternative for carrying out process variant (c) according to the invention as Starting products required benzyl sulfones of the general formula (VII) also well known compounds of organic chemistry.

As a diluent for carrying out the first stage of the invention Process (a) are inert organic solvents. This includes ins special halogenated hydrocarbons, such as chlorobenzene, dichlor benzene, dichloromethane or chloroform.

As a diluent for carrying out the second stage of the invention Process (a) are inert organic solvents. This includes ins special aliphatic, alicyclic or aromatic, optionally halogenated Hydrocarbons, such as gasoline, benzene, toluene, xylene, chlorobenzene, Dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetra chlorinated carbon; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones such as acetone, butanone or Methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-Me thylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate esters or ethyl acetate, sulfoxides such as dimethyl sulfoxide, alcohols such as Methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol colmonoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

The second stage of process (a) according to the invention can optionally also be carried out in a two-phase system, such as water / toluene or water / dichloromethane, optionally in the presence of a suitable phase transfer catalyst. Examples of such catalysts are: tetrabutylammonium iodide, tetrabutylammonium bromide, tetrabutylammonium chloride, tributyl-methylphosphonium bromide, trimethyl-C ₁₃ / C ₁₅ -alkylammonium chloride, trimethyl-C ₁₃ / C ₁₅ -alkylammonium bromide, dibenzyl-dimethyl-ammonium-ammonium ₁₂ / C ₁₄ -alkyl-benzylammonium chloride, dimethyl-C ₁₂ / C ₁₄ alkyl-benzylammonium bromide, tetrabutylammonium hydroxide, triethylbenzylammonium chloride, methyltrioctylammonium chloride, trimethylbenzylammonium chloride, 15-crown-5, 18-crown-6 or tris- [2- (2-methoxyethoxy ) ethyl] amine.

As catalysts for carrying out the first stage of the process according to the invention rens (a) are conventional Friedel-Crafts catalysts. Preferably ver Lewis acids are used, such as zinc (II) chloride, tin (IV) chloride, iron (III) chloride or aluminum III chloride.

The second stage of process (a) according to the invention is preferably in Ge in the presence of a suitable reaction auxiliary. As such, everyone comes usual inorganic or organic bases in question. These include at for example, alkaline earth or alkali metal hydroxides, carbonates or hydrogen carbonates te such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, potassium hydrogen carbonate or sodium hydrogen carbonate and tertiary Amines such as triethylamine, tributylamine, N, N-dimethylaniline or pyridine.

The reaction temperatures can be carried out when carrying out the first stage of the invention Process (a) according to the invention can be varied over a wide range. Generally mine work at temperatures between -20 ° C and + 60 ° C, preferably at Temperatures between 0 ° C and + 40 ° C.

The reaction temperatures can be carried out when carrying out the second stage of the Process (a) according to the invention can also be varied within a relatively wide range. In general, one works at temperatures between 20 ° C and 120 ° C preferably at temperatures between 40 ° C and 100 ° C.  

The first stage and the second stage of process (a) according to the invention usually carried out under normal pressure. However, it is also possible under him to work under high pressure.

To carry out process (a) according to the invention, Ben is employed per mole zonitrile of formula (II) generally 1.0 to 4.0 mol, preferably 1.0 to 2.0 mol of α-chlorostyrene of the formula (III). The implementation of the reaction, workup and The reaction products are isolated by known processes (cf. also the manufacturing examples). As the chlorination component is preferred Chlorine gas used, which in amounts of at least 1 mol, preferably 1.5 to 2 mol (with respect to the compound of formula (II)) is used. Water is in Amounts of at least 1 mole, but preferably in a larger excess (1.5 to 10 mol) used (in relation to the compound of formula (II)).

As a diluent for carrying out process (b) according to the invention inert organic solvents are suitable. These include in particular ali phatic, alicyclic or aromatic, optionally halogenated hydrocarbons substances such as gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, Petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol koldimethyl or diethyl ether; Ketones, such as acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides such as N, N-dime thylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or Hexamethylphosphoric triamide; Esters such as methyl acetate or acetic acid ethyl esters or sulfoxides, such as dimethyl sulfoxide.

Process (b) according to the invention is preferably carried out in the presence of a th reaction aid performed. As such come all the usual inorganic or organic bases in question. These include, for example, alkaline earth or Alkali metal hydroxides, carbonates or bicarbonates, such as Na trium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, Potassium bicarbonate or sodium bicarbonate and tertiary amines, such as Triethylamine, tributylamine, N, N-dimethylaniline, dimethylbenzylamine or pyridine.  

Process (b) according to the invention is usually carried out under normal pressure leads. However, it is also possible to work under increased or reduced pressure ten.

The reaction temperatures can be carried out when carrying out the process according to the invention Process (b) can be varied over a wide range. Generally works one at temperatures between 20 ° C and 150 ° C, preferably at temperatures between 40 ° C and 120 ° C.

To carry out the process according to the invention, chlorine is employed per mole of chlorine methyloxazole of formula (IV) generally 1.0 to 2.0 mol, preferably 1.0 to 1.5 moles of alcohol, phenol, carboxylic acid, amine or thiol derivative of the formula (V) and optionally 1.0 to 2.0 mol, preferably 1.0 to 1.5 mol of basic Reaction aids. You can also use alcohol, phe nol, carboxylic acid, amine or thiol component of the formula (V) in the form of an ent use speaking alkali metal salt. This procedure eliminates the need for Use of additional basic reaction aids. The implementation of the reaction, The reaction products are worked up and isolated according to generally customary known methods.

As a diluent for carrying out process (c) according to the invention inert organic solvents are suitable. These include in particular ali phatic, alicyclic or aromatic, optionally halogenated hydrocarbons substances such as gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, Petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol koldimethyl or diethyl ether or amides, such as N, N-dimethylformamide, N, N- Dimethylacetantide, N-methylformanilide, N-methylpyrrolidone or hexamethyl phosphoric triamide.

Process (c) according to the invention is preferably carried out in the presence of a th reaction aid performed. As such come all the usual inorganic or organic bases in question. These include, for example, alkyl lithium  compounds such as butyllithium; Alkaline earth or alkali metal hydrides, hydroxides, amides, alcoholates, carbonates or bicarbonates, such as natri anhydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, Sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, potassium hydrogen carbonate or ammonium carbonate.

Process (c) according to the invention can, in particular in the case of the reaction of sulfones of the formula (VII), optionally also be carried out in a two-phase system, such as, for example, water / toluene or water / dichloromethane, if appropriate in the presence of a suitable phase transfer catalyst. Trime thyl-C ₁₃ / C ₁₅ trimethyl-C ₁₃ / C tetrabutylammonium bromide Tetrabutylammoni, tetrabutylammonium chloride, tributyl-methylphosphonium, -alkylammoniumchlorid, ₁₅ -alkylammoniumbromid, dibenzyl dimethyl ammonium methyl sulfate, _{dimethyl-C12:} As examples of such catalysts may be mentioned / C ₁₄ -alkyl-benzylammonium chloride, dimethyl-C ₁₂ / C ₁₄ -alkyl-benzylammonium bromide, tetrabutylammonium hydroxide, triethylbenzylammonium chloride, methyltrioctylammonium chloride, trimethylbenzylammonium chloride, 15-crown-5, 18-crown-6 or tris- [2- (2 -meth oxyethoxy) ethyl] amine.

The reaction temperatures can be carried out when carrying out the process according to the invention Process (c) can be varied over a wide range. Generally works one at temperatures between -80 ° C and 180 ° C, preferably at temperatures between -20 ° C and 100 ° C.

The process (c) according to the invention is carried out per mole Chloromethyloxazole of formula (IV) generally 1.0 to 2.0 mol, preferably 1.0 up to 1.2 mol of phenylacetylene compound of the formula (VI) or of benzyl sulfone Formula (VII) and optionally 1.0 to 5.0 mol, preferably 1.0 to 2.5 mol basic reaction auxiliary. The implementation of the reaction, workup and The reaction products are isolated in analogy to known processes.

The possibly following the implementation of the Ver drive (c) required catalytic hydrogenation of the double bond is carried out in analogy  carried out according to generally accepted procedures. These are used as diluents all usual inert organic solvents in question. With special preference alcohols such as methanol, ethanol, n- or i-propanol, ethylene glycol are used monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether. All come as hydrogenation catalysts customary hydrogenation catalysts, such as, for example, nickel, platinum or palladium, optionally also on a suitable carrier material, such as coal or silicon dioxide in question. The hydrogenation is generally at one Pressure between 1 and 100 bar and a temperature in the range of 20 ° C to 200 ° C performed with molecular hydrogen. The implementation of the reaction, workup and isolation of the reaction products is carried out in analogy to generally customary known methods.

The purification of the end products of formula (I) and the intermediates of Formula (IV) is carried out using customary methods, for example by Column chromatography or by recrystallization.

The characterization takes place in the usual way in organic chemistry, e.g. B. with the help of the melting point or in the case of non-crystallizing compounds with the help of proton nuclear magnetic resonance spectroscopy ( ¹ H-NMR).

The active compounds are suitable for controlling animal pests, preferably Arthropods and nematodes, especially insects and arachnids, which in the Agriculture, in forests, in the protection of stored goods and materials, and on hygiene sector occur. They are preferably used as crop protection agents control of plant-damaging insects, mites and nematodes (preferably Insects and mites). They are against normally sensitive and resistant species effective against all or individual stages of development.

The pests mentioned above include:
From the order of the Isopoda z. B. Oniscus aseilus, Armadillidium vulgare, Porcellio scaber;
from the order of the Diplopoda z. B. Blaniulus guttulatus;
from the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spec .;
from the order of the Symphyla z. B. Scutigerella immaculata;
from the order of the Thysanura z. B. Lepisma saccharina;
from the order of the Collembola z. B. Onychiurus armatus;
from the order of Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leuco phaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta mi gratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria;
from the order of the Dermaptera z. B. Auricular Forficula;
from the order of the Isoptera z. B. Reticulitermes spp .;
from the order of the Anoplura z. B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp .;
from the order of the Mallophaga z. B. Trichodectes spp., Damalinea spp .;
from the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci;
from the order of Heteroptera z. B. Eurigaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectuiarius, Rhodnius prolixus, Triatoma spp .;
from the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeuro des vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lahigerum, Hyalopterus arundinis, Macrosiphum ave nae, Myzus sppii, Phorodonosp. , Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax stria tellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp .;
from the order of the Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella ma culipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiisisppppas, Fpp., Phyllocn in sulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Pro denia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuellonissellaella, Galleria , Tmea pellionella, Hofinannophila pseudospretella, Cacoecia podana, Capua re ticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana;
from the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa deeemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysoce phalivestus, suril ., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhyn chus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus sppus, Nidesusium sololuc spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica;
from the order of the Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp .;
from the order of the Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chry somyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosox spp., Stom spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa;
from the order of the Siphonaptera z. B. Xenopsylla cheopis. Ceratophyllus spp .; from the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans;
from the order of Acarina z. B. Acarus siro, Argas spp., Ornithodoros spp., Derma nyssus gallinae, Eriophyes ribis, Phyilocoptruta oleivora, Boophilus spp., Rhipice phalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Psoroptes spp spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

The active compounds according to the invention are notable in particular for a high level insecticidal and acaricidal activity.

They can be used with particularly good results in combating plant damage the insects, such as against the larvae of horseradish leaf beetles (Phaedon cochleariae) or against the common spider mite (Tetranychus urticae).

The active ingredients can depend on their respective physical and / or chemical properties can be converted into the usual formulations, such as  Solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, Active ingredient-impregnated natural and synthetic substances, very fine encapsulation in polymeric substances and in coating compositions for seeds, also in formulations with Fuel sets, such as smoking cartridges, cans, spirals, etc., as well as ULV cold and Warm fog formulations.

These formulations are prepared in a known manner, e.g. B. by mixing of the active ingredients are under pressure with extenders, i.e. liquid solvents the liquefied gases and / or solid carriers, optionally under Ver Use of surface-active agents, i.e. emulsifiers and / or dispersants agents and / or foaming agents. In case of using water as Extenders can e.g. B. also organic solvents as auxiliary solvents be used. The following are essentially suitable as liquid solvents: Aro mat, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methyl lene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. Earth oil fractions, alcohols, such as butanol or glycol, and their ethers and esters, Ke clays, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water; with liquefied gaseous extenders or carriers are such liquids that means gaseous at normal temperature and pressure are, e.g. B. aerosol propellants, such as halogenated hydrocarbons and butane, propane, Nitrogen and carbon dioxide; as solid carriers come into question: B. natural Rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, Montmorillonite or diatomaceous earth and synthetic rock powder, such as hochdis perse silica, aluminum oxide and silicates; as solid carriers for granules come into question: z. B. broken and fractionated natural rocks such as calcite, Marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, Coconut shells, corn cobs and tobacco stalks; as an emulsifying and / or foaming agent Witnesses are possible: B. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkyl  aryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hy drolysate; as dispersants come into question: z. B. Lignin sulfite and Me ethyl cellulose.

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

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

The pesticides according to the invention contain in a preferred Embodiment at least one surfactant.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with other active compounds, such as insecticides, attractants, sterilants, acaricides, ne maticides, 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
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 compounds is increased without the added synergist itself having to be active.

The active substance content of the users prepared from the commercially available formulations Forms of application can vary widely. The drug concentration of the An Application forms can be from 0.0000001 to 95 percent by weight of active ingredient, preferably be between 0.0001 and 1 percent by weight.

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

The preparation and use of the active compounds according to the invention is carried out by the following examples are explained.

Manufacturing examples: Example 1: (Method b)

5 g (0.02 mol) of 2- (2-chloro-6-fluorophenyl) -4-chloromethyloxazole and 3.5 g (0.02 mol) 4-t-Butylphenol sodium salt in 60 ml acetonitrile are on for 12 hours Reflux temperature heated. The solvent is worked up in vacuo removed and the residue over silica gel (mobile phase: hexane / dichloromethane 10: 1) chromatographed.

4.8 g (67% of theory) of 2- (2-chloro-6-fluorophenyl) -4- (4-tert.- butylphenoxymethyl) oxazole as an oil.

MS: m / e (rel. Int.) = 359 (M⁺, 23), 344 (M⁺-CH ₃ , 2), 210 (100), 182 (87), 155 (22).

Preparation of the starting compound: Example 1A:

To 30.3 g (0.1 mole) of N- (1,3-dichloropropen-2-yl) -2-chloro-6-fluoro-benzimide chloride (E / Z mixture) in 75 ml of toluene are added with stirring at room temperature 17.5 g (0.435 mol) sodium hydroxide and 2 g benzyldimethyldodecylammonium chloride in 50 ml of water and then heated to reflux temperature for 5 hours. For Working up, the cooled reaction mixture is mixed with water and Dichloromethane, the organic phase is separated off, dried over sodium sulfate, removed the solvent in vacuo, takes up the residue in 250 ml of acetonitrile, gives 0.4 g of palladium acetate and heated to reflux temperature for 24 hours. The solvent is then distilled off and the residue in a high vacuum distilled.

18.3 g (75% of theory) of 2- (2-chloro-6-fluorophenyl) -4- are obtained. chloromethyloxazole with a boiling point of 118-120 ° C at 0.1 mbar.

MS: m / e (rel. Int.) = 245 (M⁺, 52), 210 (M⁺-Cl, 100), 182 (70), 155 (45), 120 (34).

In a mixture of 17.5 g (0.255 mol) of 2-chloro-6-fluoro-benzonitrile (cf. e.g. DE 25 47 037), 25 g (0.22 mol) of 2,3-dichloropropene and 0.2 g of ferric chloride are added 10 ° C to 15 ° C chlorine initiated. After the implementation of 2,3-dichloropropene (control by gas chromatography) a further 25 g of 2,3-dichloropropene are added and continues to introduce chlorine. The reaction mixture is worked up fractionally distilled.

24.7 g (75% of theory) of N- (1,3-dichloropropen-2-yl) -2-chloro-6-fluorine are obtained benzimide chloride (E / Z mixture) from the boiling range 150 ° C to 165 ° C at 0.1 mbar.  

In a corresponding manner and in accordance with the general information on the manufacture the following compounds of the general formula (I):

Biological examples Example A: Tetranychtis test (OP-resistant)

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

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

Bean plants (Phaseolus vulgaris), strongly affected by all stages of development of the ge my spider mite (Tetranychus urticae) are infested in an active ingredient preparation of the desired concentration submerged.

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

In this test, e.g. B. the compounds of Preparation Examples 1 and 2 an exemplary concentration of 0.01% (weight percent) after 7 days 95 to 98% kill.  

Example B Phaedon larval test

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

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

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

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

In this test, e.g. B. the connection of preparation example 1 in a exemplary concentration of 0.1% (percentages by weight) 100%.

Claims (14)

1. Substituted oxazoles of the general formula (I), in which
R ^{1 represents} hydrogen, alkyl or halogen,
R ^{2 represents} alkyl or halogen,
Ar represents a phenyl radical which is optionally substituted by halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkoxyalkyl, alkoxyalkoxy, optionally substituted cycloalkyl, optionally substituted cycloalkyloxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylalkyl and / or optionally substituted arylalkyloxy is substituted;
X for a grouping of the formula -CH ₂ -CH ₂ -; -CH ₂ -CH ₂ -CH ₂ -; -CH = CH-; -CH ₂ -CH = CH-; -CH ₂ -O-; -CH ₂ -S-; -CH ₂ -N (R ³ ) -; -CH ₂ -O-CH ₂ -; -CH ₂ -O-CH ₂ -CH ₂ - or -CH ₂ -O-CO-, where
R ^{3 represents} hydrogen, alkyl or alkanoyl; and
n stands for a number 0 or 1. 2. Substituted oxazoles according to claim 1, in which
R ^{1 represents} hydrogen, fluorine, chlorine, bromine or C ₁ -C ₆ alkyl;
R ^{2 represents} fluorine, chlorine, bromine or C ₁ -C ₆ alkyl;
Ar represents a phenyl radical which may be halogen; C ₁ -C ₁₈ alkyl; C ₂ -C ₁₂ alkenyl; C ₂ -C ₁₂ alkynyl; C ₁ -C ₁₈ alkoxy; C ₂ -C ₁₂ alkenyloxy; C ₂ -C ₁₂ alkynyloxy; C ₁ -C ₈ alkoxy-C ₁ -C ₈ alkyl; C ₁ -C ₈ alkoxy-C ₁ -C ₈ alkoxy; optionally substituted by C ₁ -C ₈ alkyl and / or C ₁ -C ₈ -alkoxy-substituted C ₃ - C ₈ cycloalkyl; optionally substituted by C ₁ -C ₈ alkyl and / or C ₁ -C ₈ -alkoxy sub stituiertes C ₃ -C ₈ cycloalkoxy; optionally substituted by C ₁ -C ₈ alkyl and / or C ₁ - C ₈ -alkoxy-substituted C ₆ - or C ₁₀ aryl; C ₆ or C ₁₀ aryloxy optionally substituted by C ₁ -C ₈ alkyl and / or C ₁ -C ₈ alkoxy; where appropriate by C ₁ -C ₈ alkyl and / or C ₁ -C ₈ -alkoxy-substituted C ₆ - or C ₁₀ aryl-C ₁ -C ₈ alkyl and / or optionally substituted by C ₁ -C ₈ alkyl and / or C ₁ -C ₈ alkoxy substituted C ₆ - or C ₁₀ aryl-C ₁ -C ₈ alkoxy is substituted;
X for -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH = CH-, -CH ₂ -CH = CH-, -CH ₂ -O-, -CH ₂ -S-, -CH ₂ -N (R ³ ) -, -CH ₂ -O-CH ₂ -, -CH ₂ -O-CH ₂ -CH ₂ - or -CH ₂ -O-CO, where
R ^{3 represents} hydrogen, C ₁ -C ₆ alkyl or C ₂ -C ₇ alkanoyl; and
n stands for 0 or 1. 3. Substituted oxazoles according to claim 1, in which
R ^{1 represents} hydrogen, fluorine, chlorine or C ₁ -C ₄ alkyl;
R ^{2 represents} fluorine, chlorine or C ₁ -C ₄ alkyl;
Ar represents a phenyl radical which may be halogen; C ₁ -C ₁₆ alkyl; C ₂ -C ₈ alkenyl; C ₂ -C ₈ alkynyl; C ₁ -C ₁₆ alkoxy; C ₂ -C ₈ alkenyloxy; C ₂ -C ₈ alkynyloxy; C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl; C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkoxy; optionally C ₃ -C ₇ cycloalkyl substituted by C ₁ -C ₆ alkyl and / or C ₁ -C ₆ alkoxy; C ₃ -C ₇ cycloalkoxy optionally substituted by C ₁ -C ₆ alkyl and / or C ₁ -C ₆ alkoxy; optionally substituted by C ₁ -C ₆ alkyl and / or C ₁ - C ₆ -alkoxy-substituted C ₆ - or C ₁₀ aryl; C ₆ or C ₁₀ aryloxy optionally substituted by C ₁ -C ₆ alkyl and / or C ₁ -C ₆ alkoxy; where appropriate by C ₁ -C ₆ alkyl and / or C ₁ -C ₆ -alkoxy-substituted C ₆ - or C ₁₀ aryl-C ₁ -C ₆ alkyl and / or optionally substituted by C ₁ -C ₆ alkyl and / or C ₁ -C ₆ alkoxy substituted C ₆ - or C ₁₀ aryl-C ₁ -C ₆ alkoxy is substituted;
X for -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH = CH-, -CH ₂ -CH = CH-, -CH ₂ -O-, -CH ₂ -S-, -CH ₂ -N (R ³ ) -, -CH ₂ -O-CH ₂ -, -CH ₂ -O-CH ₂ -CH ₂ - or -CH ₂ -O-CO, where
R ^{3 represents} hydrogen, C ₁ -C ₄ alkyl or C ₂ -C ₅ alkanoyl; and
n stands for 0 or 1. 4. Substituted oxazoles according to claim 1, in which
R ^{1 represents} chlorine;
R ^{2 represents} fluorine;
Ar represents a phenyl radical which is substituted by C ₁ -C ₈ alkyl;
X represents CH ₂ -CH ₂ -, -CH = CH-, -CH ₂ -O- or -CH ₂ -O-CO and
n stands for 1. 5. A process for the preparation of the substituted oxazoles of the general formula (I) according to claim 1, characterized in that

• a) for the preparation of compounds of the general formula (I) in which n is 0,

Benzonitriles of the general formula (II), in which
R ¹ and R ^{2 have} the meaning given above,
with α-chlorostyrenes of the general formula (III), in which
Ar has the meaning given above,
first in a first stage with chlorine, if appropriate in the presence of a catalyst and if appropriate in the presence of a diluent and then in a second stage with water in the presence of a reaction auxiliary, if appropriate in the presence of a phase transfer catalyst and if appropriate in the presence of a diluent; or

• b) for the preparation of the compounds of general formula (I) in which
  X is a grouping of the formula -CH ₂ -O-; -CH ₂ -S-; -CH ₂ -N (R ³ ) -; -CH ₂ -O-CH ₂ -; -CH ₂ -O-CH ₂ -CH ₂ - or -CH ₂ -O-CO- and
  n is 1, where R ^{3 has} the meaning given above,

Chloromethyloxazoles of the general formula (IV), in which
R ¹ and R ^{2 have} the meaning given above,
with alcohol, phenol, carboxylic acid, amine or thiol derivatives of the general formula (V), HX ¹ -Ar (V) in which
X ¹ for -O-; -S-; -N (R ³ ) -; -O-CH ₂ -; -O-CH ₂ -CH ₂ - or -O-CO-, where
R ^{3 has} the meaning given above,
if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary; or

• c) for the preparation of the compounds of general formula (I) in which
  X is a grouping of the formula -CH ₂ -CH ₂ -; -CH ₂ -CH ₂ -CH ₂ -; -CH = CH- or -CH ₂ -CH = CH- and n 1 mean

Chloromethyl-oxazoles of the general formula (IV), in which
R ¹ and R ^{2 have} the meaning given above,
with phenylacetylene compounds of the general formula (VI), HC≡C-Ar (VI) in which
Ar has the meaning given above,
or with benzyl sulfones of the general formula (VII), Ar-SO ₂ -CH ₂ -Ar (VII) in which
Ar has the meaning given above,
if appropriate in the presence of a diluent, if appropriate in the presence of a phase transfer catalyst and if appropriate in the presence of a reaction auxiliary and if appropriate subsequently the substituted oxazoles of the general formula (I) thus obtainable, in which X is -CH = CH- or -CH ₂ -CH = CH - and n is 1, for the preparation of compounds of the general formula (I) in which X is -CH ₂ -CH ₂ or -CH ₂ -CH ₂ -CH ₂ and n 1,
hydrogenated in a subsequent second stage with hydrogen gas in the presence of a catalyst and optionally in the presence of a diluent. 6. pesticide, characterized by a content of at least one compound of formula (I), according to claims 1 or 5. 7. Use of compounds of formula (I) according to claims 1 or 5 to control pests. 8. A method for controlling pests, characterized in that Compounds of formula (I) according to claims 1 or 5 on the pests linge and / or their living space. 9. Process for the preparation of pesticides, characterized characterized in that compounds of formula (I) according to claims 1 or 5 mixed with extenders and / or surface-active agents.   10. chloromethyloxazoles of the general formula (IV), in which
R ^{1 represents} hydrogen, alkyl or halogen; and
R ^{2 represents} alkyl or halogen. 11. A process for the preparation of the chloromethyloxazoles according to claim 10, characterized in that benzonitriles of the general formula (II) in which
R ¹ and R ^{2 have} the meaning given in claim 10,
with 2,3-dichloro-1-propene of the general formula (VIII), first in a first stage with chlorine, if appropriate in the presence of a catalyst and if appropriate in the presence of a diluent and then in a second stage with water in the presence of a reaction auxiliary, if appropriate in the presence of a phase transfer catalyst and if appropriate in the presence of a diluent.