WO1995030657A1 - Substituted tetrahydropyrazoles as pest control agents - Google Patents

Abstract

The present invention concerns novel substituted tetrahydropyrazoles of formula (I) in which R1 is possibly substituted aryl or hetaryl, R2 is a five or six-member, possibly substituted and possibly benzo-condensed heterocycle containing one to four nitrogen atoms, and R?3, R4, R5¿ and X have the meanings given in the description, processes for producing them and their use in pest control.

Description

SUBSTITUTED TETRAHYDROPYRAZOLES AS PESTICIDES

The present invention relates to novel substituted tetrahydropyrazoles, processes for their preparation and their use as pesticides, in particular as insecticides.

Structurally similar tetrahydropyrazoles and their use as pesticides are known from EP-A-0 490 569. However, the efficacy and range of action of these compounds is not always satisfactory at low application rates and concentrations.

New substituted tetrahydropyrazoles of formula (I) have now been found,

in which

R ¹ represents optionally substituted aryl or hetaryl, R ² represents a five- or six-membered, optionally substituted and optionally benzo-fused heterocycle containing one to four nitrogen atoms,

R ³ and R ⁴ independently of one another represent hydrogen or represent alkyl, alkylcarbonyl, alkoxycarbonyl, alkylsulfonyl, mono- or dialkylaminocarbonyl, each optionally substituted by halogen, or

R ³ and R ⁴ together represent the residue A, where

oder

A for one of the groups

or

stands,

R ⁶ represents hydrogen or alkyl,

R ⁵ represents optionally substituted alkyl or cycloalkyl or the radical

stands in which

R and R ⁸ independently of one another represent hydrogen, halogen, nitro, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, in each case optionally substituted aryloxy or arylthio, optionally substituted mono- or dialkylamino, optionally substituted cycloalkyl, alkoxycarbonyl, alkenyl, alkynyl, alkylthionyl, alkylsulfonyl, haloalkylthionyl, haloalkylsulfonyl or haloalkoxycarbonyl or wherein

R ⁷ and R ⁸ together represent alkanediyl which may contain one or two oxygen atoms and may be substituted, and

X represents oxygen or sulfur. The compounds of formula (I) can exist, depending on the nature of the substituents, as geometric and/or optical isomers or isomer mixtures of different compositions. The invention relates to both the pure isomers and the isomer mixtures.

Furthermore, it has been found that A) the substituted tetrahydropyrazoles of the formula (I) in which R ³ is hydrogen, ie the new compounds of the formula (Ia)

in welcher

in which

R ¹ , R ² , R ⁴ , R ⁵ and X have the meaning given above for formula (I), is obtained when dihydropyrazoles of the formula (II)

in which

R ¹ , R ² , R ⁴ , R ⁵ and X have the meaning given above, in the presence of a reducing agent, optionally in the presence of a catalyst and in the presence of a

diluent is reduced, and that

B) the substituted tetrahydropyrazoles of formula (I)

in which R ¹ , R ² , R ⁴ , R ⁵ and X have the meaning given above and

R ³ has the meaning given above with the exception of hydrogen, is obtained when the compounds of the above formula (Ia) in which R ¹ , R ² , R ⁴ , R ⁵ and X have the meaning given above, with compounds of formula (III)

R ³ -Hal (III) in which R ³ has the meaning given above with the exception of hydrogen and

Hal represents halogen, in particular chlorine, bromine or iodine, in the presence of a diluent and optionally in the presence of a base and that

C) the substituted tetrahydropyrazoles of formula (I) in which

R ³ and R ⁴ together represent the radical A, ie the new compounds of formula (Ib)

in welcher A, R¹, R², R⁵ und X die oben bei Formel (I) angegebene Bedeutung haben, erhält, wenn man α) zum Erhalt von Verbindungen der Formel (Ib), in welcher A für

steht, Verbindungen der Formel (Ic)

in which A, R ¹ , R ² , R ⁵ and X have the meaning given above for formula (I), is obtained when α) to obtain compounds of formula (Ib) in which A is

compounds of formula (Ic)

in welcher R¹, R², R⁵ und X die oben angegebene Bedeutung haben, mit Aldehyden der Formel (IV)

in which R ¹ , R ² , R ⁵ and X have the meaning given above, with aldehydes of the formula (IV)

R ⁶ -CHO (IV) in which

R ⁶ has the meaning given above in the presence of an acid and optionally in the presence of a diluent and ß) to obtain compounds of the formula (Ib) in which A is -CO- or -COCO-, compounds of the formula (Ic)

in which

steht, Verbindungen der Formel (Id) (erhältlich nach R ¹ , R ² , R ⁵ and X have the meaning given above, with phosgene or with oxalyl chloride, optionally in the presence of a diluent and optionally in the presence of a base and γ) to obtain compounds of formula (Ib), in which A is

compounds of formula (Id) (obtainable according to

Procedure B)

in which

R ¹ , R ² , R ⁵ , R ⁶ and X have the meanings given above, optionally in the presence of a diluent with a base. Finally, it was found that the new tetrahydropyrazoles of formula (I) have very good activity against pests and, in particular, very good insecticidal and acaricidal activity.

The tetrahydropyrazoles 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 _pyridyl , pyrazinyl, pyridazinyl, thienyl, each optionally substituted by halogen, nitro, cyano, C ₁ - C ₆ alkyl, C _{1 -C 6} alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ haloalkylthio, C 1 -C 6 alkoxycarbonyl or di-C ₁ - C ₆ alkylamino.

Thiazolyl or for the rest

wherein Y and Z independently of one another represent hydrogen, halogen, nitro, cyano, C ₁ -C ₆ alkyl, C 1 -C ₆ alkoxy, C _{1 -C 6} alkylthio, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₈ haloalkoxycarbonyl, represent phenoxy or phenylthio, each optionally substituted by halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkyl, represent C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₄ alkylthionyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ haloalkylthionyl, C ₁ -C ₄ -Halogenalkylsulfonyl, represents mono- or di-(C ₁ -C ₈ -alkyl)amino, each optionally substituted by halogen or C ₁ -C ₄ -alkoxy, or

Y and Z together represent 3,4-methylenedioxy or 3,4-ethylenedioxy, each optionally substituted by fluorine and/or chlorine. R ² preferably represents a heterocyclic radical from the series

worin

wherein

R ⁹ and R ¹⁰ independently of one another represent hydrogen, halogen, cyano, nitro, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ haloalkylthio, C ₁ -C ₆ alkoxycarbonyl or di-(C ₁ -C ₄ alkyl)amino.

R ³ and R ⁴ independently of one another preferably represent hydrogen or C ₁ -C ₅ alkyl, C _{1 -C 5 alkylcarbonyl, C 1 -C 5} alkoxycarbonyl, C ₁ -C ₅ alkylsulfonyl, mono- or di-(C _{1 -C 5} alkyl)aminocarbonyl, each _optionally substituted by fluorine, chlorine and/or bromine, or R ³ and R ⁴ together preferably represent the radical A, where

,

,

oder

A for one of the groups

,

,

or

stands.

R ⁶ preferably represents hydrogen or C ₁ -C ₄ alkyl. R ⁵ preferably represents C ₁ -C ₈ alkyl optionally substituted by halogen or C ₁ -C ₄ haloalkoxy, C 3 -C ₇ cycloalkyl optionally substituted by halogen, C ₁ -C ₄ haloalkyl or C _{1 -C 4} haloalkoxy or the radical

wonn

won

R ⁷ and R ⁸ independently of one another represent hydrogen, halogen, nitro, cyano, C ₁ -C ₈ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₈ haloalkylthio, represent phenoxy or phenylthio, each optionally substituted by halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or C ₁ -C ₈ haloalkyl, represent mono- or di-(C ₁ -C ₆ alkyl)amino, each optionally substituted by halogen, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy, represent C ₃ optionally substituted by halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkylthio -C ₇ -cycloalkyl, C ₁ -C ₈ -alkoxycarbonyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, C ₁ -C ₄ -alkylthionyl, C ₁ -C ₄ -alkylsulfonyl, C ₁ -C ₄ -haloalkylthionyl, C ₁ -C ₄ -haloalkylsulfonyl or C ₁ -C ₄ -haloalkoxycarbonyl or wherein

R ⁷ or R ⁸ together represent one of the radicals

stand. X preferably represents oxygen or sulfur. R ¹ particularly preferably represents the radical

worin Y und Z unabhängig voneinander für Wasserstoff, Fluor, Chlor, Brom, Nitro, Cyano, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₁-C₃-Alkylthio, C₁-C₃-Halogenalkyl, C₁-C₃- Halogenalkoxy, C₁-C₃-Halogenalkylthio, C₁-C₃-Alkoxycarbonyl, C₁-C₃- Halogenalkoxycarbonyl, für jeweils gegebenenfalls durch Fluor, Chlor, Brom, C₁-C₃-Alkyl, C₁-C₃-Alkoxy oder C₁-C₃-Halogenalkyl substituiertes Phenoxy oder Phenylthio, für C₂-C₄-Alkenyl, C₂-C₄-Alkinyl, C₁-C₃-Alkylthionyl, C₁-C₃-Alkylsulfonyl, C₁-C₃-Halogenalkylthionyl, C₁-C₃-Halogenalkylsulfonyl oder für jeweils gegebenenfalls durch Fluor, Chlor, Brom oder C₁-C₈-Alkoxy substituiertes Mono- oder Di-(C₁-C₃-alkyl)amino stehen oder Y und Z gemeinsam für jeweils gegebenenfalls durch Fluor und/oder Chlor substituiertes 3,4-Methylendioxy oder 3,4-Ethylendioxy stehen.

wherein Y and Z independently of one another represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₃ alkylthio, C ₁ -C ₃ haloalkyl, C ₁ -C ₃ haloalkoxy, C ₁ -C ₃ haloalkylthio, C ₁ -C ₃ alkoxycarbonyl, C ₁ -C ₃ haloalkoxycarbonyl, represents phenoxy or phenylthio, each optionally substituted by fluorine, chlorine, bromine, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy or C ₁ -C ₃ haloalkyl, represents C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₁ -C ₃ alkylthionyl, C 1 -C ₃ alkylsulfonyl, C _{1 -C 3} haloalkylthionyl, C ₁ -C ₃ -haloalkylsulfonyl or mono- or di-(C ₁ -C ₃ -alkyl)amino, each optionally substituted by fluorine, chlorine, bromine or C ₁ -C ₈ -alkoxy, or Y and Z together represent 3,4-methylenedioxy or 3,4-ethylenedioxy, each optionally substituted by fluorine and/or chlorine.

R ² particularly preferably represents a heterocyclic radical from the series

worin

wherein

R ⁹ and R ¹⁰ independently represent hydrogen, chlorine, bromine, methyl, ethyl or trifluoromethyl.

R ³ and R ⁴ independently of one another particularly preferably represent hydrogen or represent in each case optionally fluorine and/or chlorine-substituted C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylcarbonyl, C ₁ -C ₄ alkoxycarbonyl, C ₁ -C ₄ alkylsulfonyl, mono- or di-(C ₁ -C ₄ alkyl)aminocarbonyl or

R ³ and R ⁴ together particularly preferably represent the radical A, where

,

oder

steht. R⁶ steht besonders bevorzugt für Wasserstoff oder C₁-C₃-Alkyl. A for one of the groups

,

or

stands. R ⁶ particularly preferably represents hydrogen or C ₁ -C ₃ alkyl.

R ⁵ particularly preferably represents C ₁ -C ₄ alkyl optionally substituted by fluorine, chlorine, bromine or C ₁ -C ₃ haloalkoxy, C ₃ -C ₆ cycloalkyl optionally substituted by fluorine, chlorine, bromine, C ₁ -C ₈ haloalkyl or C ₁ - C ₃ haloalkoxy or the radical

wherein

R ⁷ and R ⁸ independently of one another represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₃ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₃ haloalkoxy, C ₁ -C ₄ alkylthio, C _{1 -C 3} haloalkylthio, phenoxy optionally substituted by fluorine, chlorine, _bromine , C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy or C _{1 -C 3} haloalkyl _, mono- or di-(C ₁ -C ₄ alkyl)amino each optionally substituted by fluorine, chlorine, bromine, C ₁ -C ₃ alkoxy or C _{1 -C 3} haloalkoxy,

C ₃ -alkylthio substituted C ₃ -C ₆ -cycloalkyl, for C ₁ -C ₄ -haloalkylsulfonyl or

R ⁷ and R ⁸ together for one of the residues

stehen. X steht besonders bevorzugt für Sauerstoff oder Schwefel.

stand. X particularly preferably represents oxygen or sulfur.

R ¹ particularly preferably represents the residue

worin

wherein

Y and Z independently of one another represent hydrogen, fluorine, chlorine, bromine, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₃ haloalkyl or C ₁ -C ₃ haloalkoxy or

Y and Z together for one of the remainders

stehen. R² steht ganz besonders bevorzugt für einen heterocyclischen Rest aus der Reihe

R ² most preferably represents a heterocyclic radical from the series

R³ und R⁴ stehen unabhängig voneinander ganz besonders bevorzugt für Wasserstoff oder für jeweils gegebenenfalls durch Fluor und/oder Chlor substituiertes Methyl, Ethyl, Propyl, Methylcarbonyl, Ethyl carbonyl, Methoxycarbonyl oder Ethoxycarbonyl oder

R ³ and R ⁴ independently of one another very particularly preferably represent hydrogen or represent methyl, ethyl, propyl, methylcarbonyl, ethylcarbonyl, methoxycarbonyl or ethoxycarbonyl, each optionally substituted by fluorine and/or chlorine, or

R ³ and R ⁴ together most preferably represent a radical A, where

A for one of the groups

steht. — CH ₂ — , -

stands.

R ⁵ most preferably represents C ₃ -C ₆ -cycloalkyl optionally substituted by C ₁ -C ₃ -haloalkyl or the radical

worin

wherein

R ⁷ and R ⁸ independently of one another represent hydrogen, cyano, nitro, fluorine, chlorine, bromine, C ₁ -C ₄ alkyl, C ₁ -C ₃ haloalkyl, C ₁ -C ₃ alkoxy, C ₁ -C ₃ haloalkoxy, C ₁ -C ₃ haloalkylthio or C ₁ -C ₃ haloalkylsulfonyl or

stehen. R ⁷ and R ⁸ together for one of the residues

stand.

X particularly preferably stands for oxygen.

The enantiomerically pure forms of compounds of formula (I) are included in each case.

The substituent meaning haloalkyl in the radicals haloalkyl, haloalkoxy, haloalkylthio, haloalkylthionyl and haloalkylsulfonyl preferably contains 1 to 9, particularly preferably 1 to 7 and very particularly preferably 1 to 5 identical or different halogen atoms, with particular preference being given to fluorine, chlorine and bromine and very particularly fluorine and chlorine as halogen atoms.

The above-mentioned general or preferred radical definitions and explanations can be combined with one another, i.e., even between the respective ranges and preferred ranges. They apply accordingly to the end products as well as to the precursors and intermediates. According to the invention, preference is given to the compounds of formula (I) in which a combination of the meanings listed above as preferred is present.

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

In addition to the compounds mentioned in the preparation examples, the following substituted tetrahydropyrazoles of formula (I) are mentioned:

Fortsetzung

Continuation

For example, if 3-phenyl-4-(1"H-4"-chloro-pyrazol-1"-yl)-4,5-dihydro-1-pyrazolecarboxylic acid (4-trifluoromethyl)anilide is used as the starting material and diisobutylaluminium hydride (DIBAL-H) as the reducing agent, the course of process A according to the invention can be represented by the following formula scheme:

For example, if 3-(4-chlorophenyl)-4-(1"H-4"-chloro-pyrazol-l "-yl)-tetrahydro-1-pyrazol-carboxylic acid (4-trifluoromethyl)anilide and acetyl chloride are used as starting materials, the course of process B according to the invention can be represented by the following formula scheme:

For example, if 3-(4-chlorophenyl)-4-(1"H-4"-chloro-pyrazol-1-yl)-tetrahydro-1-pyrazolecarboxylic acid (4-chloro)anilide and formaldehyde are used as starting materials, the course of the process Cα according to the invention can be represented by the following formula scheme:

For example, if 3-(4-chlorophenyl)-4-(1"H-4"-chloro-pyrazol-1 "-yl)-tetrahydro-1-pyrazol-carboxylic acid (4-trifluoromethyl)anilide and phosgene are used as starting materials, the course of the process Cß according to the invention can be described by the following formula scheme:

For example, if 2-chloroacetyl-3-(4-chlorophenyl)-4-(1H-4"chloropyrazol-1"-yl)-tetrahydro-1-pyrazolecarboxylic acid (4-chloro)anilide is used as the starting material and sodium hydride as the base, the course of the process Cγ according to the invention can be represented by the following formula scheme:

The dihydropyrazoles required as starting materials for carrying out process A according to the invention are generally defined by formula (II). In this formula (II), R ¹ , R ² , R ⁴ , R ⁵ , and X preferably or particularly preferably represent those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as preferred or particularly preferred for these substituents. The compounds of formula (II) are known or obtainable by known processes (cf. e.g. EP-A-438 690 and EP-A-490 569).

The reduction according to method A can lead to mixtures of isomers with respect to the mutual position of the substituents in the 3- and 4-position of the tetrahydropyrazole ring (cis/trans). These mixtures can optionally be

Separation methods such as column chromatography.

The tetrahydropyrazoles required as starting materials for carrying out process B according to the invention are generally defined by formula (Ia). In this formula (Ia), R ¹ , R ² , R ⁴ , R ⁵ , and X preferably or particularly preferably represent those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as preferred or particularly preferred for these substituents.

The compounds of formula (Ia) are novel and obtainable by process A according to the invention. The compounds of formula (III) which are also required as starting materials for carrying out process B according to the invention are generally known compounds of organic chemistry.

The tetrahydropyrazoles required as starting materials for carrying out the Cα and Cß processes according to the invention are generally defined by formula (Ic). In this formula (Ic), R ¹ , R ² , R ⁵ and X preferably or particularly preferably represent those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as preferred or particularly preferred for these substituents.

The compounds of formula (Ic) are novel and obtainable by the known process A.

The aldehydes of the formula (IV) which are also required as starting materials for carrying out the process Cα according to the invention are generally known compounds of organic chemistry. The tetrahydropyrazoles required as starting materials for carrying out the Cγ process according to the invention are generally defined by formula (Id). In this formula (Id), R ¹ , R ² , R ⁵ , R ⁶ , and X preferably or particularly preferably represent those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as preferred or particularly preferred for these substituents.

The compounds of formula (Id) are novel and obtainable by process B according to the invention.

Process A described above is carried out in the presence of a diluent and in the presence of a reducing agent.

Non-protic solvents, e.g. hydrocarbons such as hexane, cyclohexane, benzene, toluene or ethers such as diethyl ether, dioxane, tetrahydrofuran or diethylene glycol dimethyl ether, are preferably used as diluents.

All reducing agents commonly used for the reduction of C=N double bonds can be used as reducing agents.

Examples include complex metal hydrides such as diisobutylaluminium hydride (DIBAL-H), aluminium hydride, lithium aluminium hydride and sodium borohydride.

Hydrogen can also be used as a reducing agent. In this case, the reaction is preferably carried out in the presence of catalysts, for example, noble metal catalysts such as palladium. Protic diluents, such as alcohols (methanol, ethanol), can also be used in this process variant.

Raney nickel can also be used as a further reducing agent.

The reaction temperatures can be varied within a wider range in process A. In general, temperatures between -75°C and

100°C, preferably between -50°C and 50°C. Process A is generally carried out under normal pressure, but it can also be carried out under elevated pressure.

The reducing agent and the compound of formula (II) to be reduced are used in at least equimolar amounts, but up to a tenfold excess of the reducing agent can also be used.

Process B described above is carried out in the presence of a diluent and, if appropriate, in the presence of a base.

All inert organic solvents can be used as diluents. These preferably include hydrocarbons such as benzene, toluene, xylene, ethers such as dibutyl ether, tert-butyl methyl ether, tetrahydrofuran, dioxane, and polar solvents such as dimethyl sulfoxide, acetonitrile, sulfolane, dimethylformamide and N-methylpyrrolidone.

All common proton acceptors can be used as bases in process B. Alkali metal and alkaline earth metal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide, magnesium oxide,

Calcium oxide, sodium carbonate, potassium carbonate, and calcium carbonate, which can also be used in the presence of phase-transfer catalysts such as triethylbenzylammonium chloride, tetrabutylammonium bromide, or 18-crown-6. Furthermore, alkali metal and alkaline earth metal amides and hydrides, such as sodium amide, sodium hydride, and calcium hydride, as well as alkali metal alkoxides, such as sodium methylate, sodium ethylate, and potassium tert-butoxide, can be used.

The reaction temperatures in process B can be varied within a wide range. Generally, the reaction is carried out at temperatures between -20°C and 200°C, preferably between 0°C and 150°C. Process B is generally carried out under atmospheric pressure, but it can also be carried out under elevated pressure.

In process B, the starting materials are generally used in at least equimolar amounts, but it is also possible to use the compound of formula (III) in a larger excess. The process Cα described above is carried out in the presence of an acid and optionally in the presence of a diluent.

Organic acids are preferred as acids, for example formic acid and acetic acid. Diluents used in the Cα, Cß, and Cγ processes include all inert

Solvents that are already mentioned above in process B are suitable.

The processes Cα, Cß, and Cγ are generally carried out under normal pressure, but can also be carried out under increased pressure.

In process Cα, the starting materials of formulas (Ic) and (IV) are generally used in approximately equimolar amounts, but a larger excess of the aldehyde of formula (IV) can also be used.

The reaction temperatures in process Cα can be varied within a wide range. Generally, the reaction is carried out between -10°C and 200°C, preferably between 10°C and 150°C. The process Cβ described above is preferably carried out in the presence of a base.

All common proton acceptors can be used as bases. Amines, such as triethylamine, diisopropylethylamine, pyridine, N-methylpyrrolidone, diazabicyclooctane (DACO), diazabicyclononene (DBN), or diazabicycloundecene (DBU), are preferred.

The reaction temperatures in the Cß process can be varied within a wide range. Generally, temperatures between 20°C and 100°C are used, preferably between 0°C and 80°C.

Generally, an excess of phosgene or oxalyl chloride is used, but equimolar amounts of starting materials can also be used. The Cγ process described above is carried out in the presence of a base. Alkali metal and alkaline earth metal amides or hydrides, such as sodium amide, sodium hydride, and calcium hydride, are preferably used, as are alkali metal alkoxides such as sodium methylate, sodium ethylate, and potassium tert-butoxide. The reaction temperatures in the Cγ process can be varied within a wide range. Generally, the reaction is carried out at temperatures between -20°C and 150°C, preferably between 0°C and 120°C.

In general, the base and the compound of formula (Ic) are used in at least equimolar amounts, but an excess of base can also be used.

The processing is carried out in the usual way for all procedures.

The compounds of formula (I) according to the invention can be used for pest control. Pests are undesirable animal pests, especially insects, which damage plants or higher animals. The active compounds according to the invention, with good plant tolerance and favorable thermophilic toxicity, are suitable for controlling animal pests, preferably arthropods, especially insects found in agriculture, forestry, stored product and material protection, and the hygiene sector. They are effective against normally sensitive and resistant species, as well as against all or individual developmental stages. The above-mentioned pests include:

From the order Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Procellio scaber.

From the order of Diplopoda e.g. Blaniulus guttulatus

From the order Chilopoda e.g. Geophilus carpophagus, Scutigera spec.

From the order Symphyla, for example, Scutigerella immaculata.

From the order Thysanura, for example, Lepisma saccharina.

From the order of Collembola e.g. Onychiurus armatus.

From the order of Orthoptera e.g. Blatta orientalis, Periplaneta americana,

Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order Dermaptera, for example, Forficula auricularia.

From the order Isoptera, for example, Reticulitermes spp.

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

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

From the order Thysanoptera, for example, Hercinothrips femoralis and Thrips tabaci. From the order Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, and Triatoma spp.

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

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

Homona magnanima, Tortrix viridana.

From the order of Coleoptera e.g. A vbium punctatum, Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varive stis, Atomaria spp., Oryzaephilus surinamensis, Antho nomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Cono derus spp., Melolontha melolontha, Amphimallon solsti tialis,

Costelytra zealandica.

From the order of Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order Diptera, e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala,

Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hippobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa. From the order of Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp.. From the order of Arachnida e.g. Scorpio maurus, Latrodectus mactans.

The active ingredients according to the invention can be used as insecticides in their commercially available formulations as well as in the application forms prepared from these formulations in admixture with other active ingredients, such as insecticides, attractants, sterilants, acaricides, nematicides, fungicides, wax growth-regulating substances or herbicides. Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.

The following compounds are mentioned: Acrinathrin, Alphamethrin, Betacyfluthrin, Bifenthrin, Brofenprox, Cis-Resmethrin,

Clocythrin, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cypermethrin, Deltamethrin, Esfenvalerate, Etofenprox, Fenpropathrin, Fenvalerate, Flucythrinate, Fluvalinate, Lambda-Cyhalothrin, Permethrin, Pyresmethrin, Pyrethrum, Silafluofen, Tralomethrin, Zetamethrin, Alanycarb, Bendiocarb, Benfuracarb, Bufencarb, Butocarboxim, Carbaryl, Cartap,

Ethiofencarb, Fenobucarb, Fenoxycarb, Isoprocarb, Methiocarb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Promecarb, Propoxur, Terbam, Thiodicarb, Thiofanox, Trimethacarb, XMC, Xylylcarb,

Acephate, Azinphos A, Azinphos M, Bromophos A, Cadusafos, Carbophenothion, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cyanophos.

Demeton M, Demeton-S-methyl, Demeton S, Diazinon, Dichlorvos, Dicliphos,

Dichlorfenthion, Dicrotophos, Dimethoate, Dimethylvinphos, Dioxathione,

Disulfoton, Edifenphos, Ethion, Etrimphos, Fenitrothion, Fenthion, Fonophos,

Formothion, Heptenophos, Iprobefos, Isazophos, Isoxathion, Phorate, Malathion, Mecarbam, Mervinphos, Mesulfenphos, Methacrifos, Methamidophos, Naled,

Omethoate, Oxydemeton M, Oxydeprofos, Parathion A, Parathion M, Phenthoate,

Phorate, Phosalone, Phosmet, Phosphamdone, Phoxim, Pirimiphos A, Pirimiphos M,

Propaphos, Prothiophos, Prothoate, Pyraclophos, Pyridaphenthion, Quinalphos,

Salithion, Sebufos, Sulfotep, Sulprofos, Tetrachlorvinphos, Temephos, Thiomethone, Thionazine, Trichlorfon, Triazophos, Vamidothion,

Buprofezin, Chlorfluazuron, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Pyriproxifen, Tebufenozide, Teflubenzuron, Triflumuron,

Imidacloprid, Nitenpyram, N-[(6-Chloro-3-pyridinyl)methyl]-N'-cyano-N-methylethanimidamide (NI-25), Abamectin, Amitrazine, Avermectin, Azadirachtin, Bensultap, Bacillus thuringiensis, Cyromazine, Diafenthiuron, Emamectin, Ethofenprox, Fenpyrad, Fipronil, Flufenprox, Lufenuron, Metaldehyde, Milbemectin, Pymetrozinc, Tebufenpyrad, Triazuron, Aldicarb, Bendiocarb, Benfuracarb, carbofuran, carbosulfan, chlorethoxyfos,

Cloethocarb, Disulfoton, Ethophrophos, Etrimphos, Fenamiphos, Fipronil, Fonofos, Fosthiazate, Furathiocarb, HCH, Isazophos, Isofenphos, Methiocarb, Monocrotophos, Nitenpyram, Oxamyl, Phorate, Phoxim, Prothiofos, Pyrachlofos, Sebufos, Silafluofen, Tebupirimphos, Tefluthrin, Terbufos, Thiodicarb, Thiafenox, Azocyclotine, Butylpyridaben, Clofentezine, Cyhexatin, Diafenthiuron, Diethion,

Emamectin, Fenazaquin, Fenbutatin Oxide, Fenothiocarb, Fenpropathrin, Fenpyrad, Fenpyroximate, Fluazinam, Fluazuron, Flucycloxuron, Flufenoxuron, Fluvalinate, Fubfenprox, Hexythiazox, Ivemectin, Methidathion, Monocrotophos, Moxidectin, Naled, Phosalone, Profenofos, pyraclofos, pyridaben, pyrimidifen, tebufenpyrad, thuringiensin, triarathene and 4-bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (AC 303630).

A mixture with other known active ingredients, such as bird repellents, plant nutrients and soil structure improvers, is also possible.

The active ingredients can be used as such, in the form of their formulations or in the application forms prepared from them by further dilution, such as ready-to-use

Solutions, suspensions, emulsions, powders, pastes, and granules can be used. Application occurs in the usual way, e.g., by pouring, spraying, or scattering.

The active ingredients according to the invention can be applied both before and after the emergence of the plants.

They can also be incorporated into the soil before sowing.

The amount of active ingredient used can vary considerably. It depends essentially on the type of effect desired. In general, The application rates are between 0.01 and 10 kg of active ingredient per hectare of soil, preferably between 0.05 and 5 kg per ha.

For the production of pesticides, the active ingredients according to the invention can be converted into the usual formulations, depending on their respective physical and/or chemical properties, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active ingredient-impregnated natural and synthetic substances, microencapsulations in polymeric substances and in coating compositions for seeds, furthermore in formulations with combustion units, such as fumigation cartridges, cans, spirals, etc., as well as ULV cold and warm fog formulations.

These formulations are prepared in a known manner, e.g., by mixing the active ingredients with extenders, i.e., liquid solvents, pressurized liquefied gases, and/or solid carriers, optionally using surface-active agents, i.e., emulsifiers, dispersants, and/or foam-forming agents. If water is used as an extender, organic solvents, for example, can also be used as co-solvents. The following are essentially suitable liquid solvents: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorothylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. petroleum fractions, 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; liquefied gaseous extenders or carriers are liquids which are gaseous at normal temperature and under normal pressure, e.g. aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; Suitable solid carriers are: e.g. natural mineral flours such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic mineral flours such as highly dispersed silica,

Aluminium oxide and silicates; suitable solid carriers for granules are: e.g. crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules made of inorganic and organic flours and granules made from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and/or foam-forming agents are: e.g. non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; suitable dispersants are: e.g. lignin sulfite waste liquors and methyl cellulose.

Adhesives such as carboxymethylcellulose, natural and synthetic powdered, granular, or latex-like polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives may include mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper,

Cobalt, molybdenum and zinc are used.

The formulations generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90%. The active ingredients according to the invention are effective not only against plant, hygiene, and stored product pests, but also in the veterinary sector against ectoparasites such as hard ticks, soft ticks, mange mites, ground mites, flies (biting and licking), parasitic fly larvae, lice, biting lice, feather lice, and fleas. For example, they demonstrate excellent efficacy against ticks such as Boophilus microplus.

The active compounds of formula (I) according to the invention are also suitable for controlling arthropods which attack farm animals such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other domestic animals such as dogs, cats, house birds, aquarium fish and so-called laboratory animals such as hamsters, Guinea pigs, rats, and mice are infested. Controlling these arthropods is intended to reduce deaths and reduced productivity (in meat, milk, wool, hides, eggs, honey, etc.), thus enabling more economical and simpler animal husbandry through the use of the active ingredients according to the invention.

The active ingredients according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets, capsules, potions, drenches, granules, pastes, boluses, the feed-through method, suppositories, by parenteral administration such as injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.),

Implants, by nasal application, by dermal application in the form of, for example, dipping or bathing (dipping), spraying, pouring on (pour-on and spot-on), washing, powdering, as well as with the help of active substance-containing form bodies such as collars, ear tags, tail tags, limb bands, halters, marking devices, etc.

The present invention thus also relates to the compounds of general formula (I) for use as ectoparasiticides and to the use of the compounds of general formula (I) for producing an agent for controlling ectoparasites. Ready-to-use preparations contain the active ingredient in concentrations of

10 ppm - 20 wt%, preferably 0.1 - 10 wt%.

Preparations that are diluted before use contain the active ingredient in concentrations of 0.5 - 90% by weight, preferably 5 to 50% by weight. In general, it has proven advantageous to use amounts of about 1 to about

Administer 100 mg of active ingredient per kg of body weight per day to achieve effective results.

Unless otherwise stated, all percentages are by weight. The preparation of the compounds of formula (I) according to the invention will be illustrated by the following preparation examples.

As already mentioned above in the description of process A according to the invention, mixtures of isomers (cis/trans position of the substituents in the 3- and 4-position of the tetrahydropyrazole ring) can be formed during the reduction, which in some cases have been separated. The isomers are then referred to as isomer A and isomer B, without a precise assignment to the cis or trans form.

The biological effectiveness will be explained by the following application examples.

Manufacturing examples Example 1

35 g of 3(4'-chlorophenyl)-4-(1"H-4"-chloropyrazol-1"-yl)-4,5-dihydro-1-pyrazolecarboxylic acid (4-trifluoromethoxy)anilide are dissolved in 400 ml of anhydrous THF under protective gas (argon). At -70°C, 170 ml (equivalent to 170 mmol) of diisobutylaluminum hydride (DIBAL-H) in n-hexane are added dropwise over 60 minutes. The mixture is then stirred for 1 hour at 0°C, and then another 85 ml (Δ 85 mmol) of DIBAL-H solution is added dropwise at 0°C. The mixture is then stirred for 1 hour at 20°C, and then another 85 ml of DIBAL-H solution is added dropwise. The mixture is then stirred for a further 6 hours at room temperature. Then, 70 ml of methanol is added dropwise and poured then in 1 liter of ice water. The mixture is then acidified, extracted with ethyl acetate, the organic phase is separated, and the residue is dried over magnesium sulfate. The drying agent is then filtered off, and the filtrate is concentrated in vacuo. 20.3 g are obtained.

(cis/trans-3(4'-chlorophenyl)-4-(1 "H-4"-chloropyrazol-1 "-yl)-2,3,4,5-tetrahydro-1-pyrazolecarboxylic acid (4-trifluoromethoxy)anilide as a light yellow, viscous oil.

¹ H NMR in DMSO: δ = 9.25 (s) and 9.24 (s), 1H; δ = 8.13 (s) 1H; δ = 7.75-7.15 (m), 9H; δ = 6.05 (d) and 5.8 (d), 1H; δ = 5.5 (m) and 5.25 (m), 1H; δ = 4.6-3.7 (m), 3H. Example 2

2.8 g of 3(4 ^, -chlorophenyl)-4-(1"H-4"-chloropyrazol-1"-yl)-2,3,4,5-tetrahydro-1-pyrazolecarboxylic acid (4-trifluoromethyl)anilide are dissolved in 20 ml of ethyl acetate and then treated with 1.8 g of acetyl chloride. The reaction mixture is left to stand at room temperature for 48 hours. The crystals which then precipitate are filtered off with suction. 2-Acetyl-3(4 ^, -chlorophenyl)-4-(1"H-4"-chloropyrazol-1"-yl)-2,3,4,5-tetrahydro-1-pyrazolecarboxylic acid (4-trifluoromethyl)anilide is obtained as colorless crystals with a melting point of 164°C.

Example 3

2.8 g of cis/trans 3-(4'-chlorophenyl)-4-(1"-4"-chloropyrazol-1"-yl)-2,3,4,5-tetrahydro-1-pyrazolecarboxylic acid (4-trifluoromethyl)-anilide are dissolved in 20 ml of methylene chloride, and 0.9 g of oxalyl chloride are added. After 5 minutes, 1.2 g of pyridine are added. The mixture is stirred at room temperature for 1 hour, then 30 ml of water is added, the mixture is extracted with 100 ml of methylene chloride, the organic phase is separated, dried over MgSO ₄ and concentrated. The residue is chromatographed on a silica gel column using hexane/acetone 7:3 as the eluent. This gives 700 mg of isomer A of the compound shown above as colorless crystals with a melting point of 217°C as fraction 1, and isomer B as a yellow foam as fraction 2.

Example 4

3.0 g of cis/trans 3-(4'-chlorophenyl)-4-(1"-4"-chloropyrazol-1"-yl)-2,3,4,5-tetrahydro-1-pyrazolecarboxylic acid (4-trifluoromethoxy)anilide are dissolved in 20 ml of formic acid, 1.0 g of paraformaldehyde is added and then heated to 120°C for 30 min.

Then, at room temperature, 100 ml of diethyl ether is added, followed by 150 ml of water. The organic phase is separated, dried over _MgSO4 , and concentrated. The residue is chromatographed on a silica gel column.

As fraction 1, 700 mg of isomer A of the compound shown above is obtained as a colorless foam.

As fraction 2, 1.6 g of isomer B is obtained as a colorless substance with a melting point of 161°C.

Analogously to Preparation Examples 1 to 4 and according to the general instructions for preparation, the following tetrahydropyrazoles of the formula (I) are obtained

Application examples

Example A

Phaedon larvae test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight alkylaryl polyglycol ether

To prepare a suitable active ingredient preparation, mix 1 part by weight of active ingredient with the specified amount of solvent and the specified amount of emulsifier, and dilute the concentrate with water to the desired concentration. Cabbage leaves (Brassica oleracea) are treated by immersing them in the active ingredient preparation of the desired concentration and infested with horseradish leaf beetle larvae (Phaedon cochleariae) while the leaves are still moist.

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

In this test, for example, the compounds according to Preparation Examples 1, 5 and 6 at an exemplary active ingredient concentration of 0.001% caused a killing of 100% after 3 days.

Example B

Plutella test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active ingredient, mix 1 part by weight of active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by dipping them into the active ingredient preparation of the desired concentration and inoculated with caterpillars of the diamondback moth

(Plutella maculipennis) while the leaves are still moist.

After the desired time, the kill rate is determined in %. 100% means that all caterpillars were killed; 0% means that no caterpillars were killed. In this test, for example, the compounds according to the preparation examples

1 and 6 at an exemplary active ingredient concentration of 0.0001% a kill rate of 80% after 3 days.

Example C

Heliothis virescens test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active ingredient, mix 1 part by weight of active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

Soybean shoots (Glycine max) are treated by dipping them into the active ingredient preparation of the desired concentration and infested with the tobacco budworm (Heliothis virescens) while the leaves are still moist.

After the desired time, the kill rate is determined in %. 100% means that all caterpillars were killed; 0% means that no caterpillars were killed. In this test, for example, the compounds according to the preparation examples

1, 5, 6, 7, 8 and 10 (isomer B) at an exemplary active ingredient concentration of 0.001% a kill of at least 85% after 3 days.

Example D

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 ingredient, mix 1 part by weight of active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

Rice seedlings (Oryza sativa) are treated by dipping them into the active ingredient preparation of the desired concentration and infested with the green rice leafhopper (Nephotettix cincticeps) while the leaves are still moist.

After the desired time, the kill rate is determined in %. 100% means that all cicadas were killed; 0% means that no cicadas were killed. In this test, for example, the compounds according to the preparation examples

1, 3 (Isomer B), 5, 6, 7, 9 (Isomer A) and 11 (Isomer A) at an exemplary active ingredient concentration of 0.1% achieved 100% kill after 6 days.

Example E

Fly test

Test animals: Musca domestica, strain WHO (N)

Solvent: 35 parts by weight of ethylene glycol monomethyl ether

35 parts by weight of nonylphenol polyglycol ether

To prepare a suitable formulation, mix three parts by weight of active ingredient with seven parts of the solvent-emulsifier mixture specified above, and dilute the resulting emulsion concentrate with water to the desired concentration. 2 ml of this active ingredient preparation is pipetted onto filter paper discs (9.5 cm diameter) placed in appropriately sized Petri dishes. After the filter discs are dried, 25 test animals are transferred to the Petri dishes and covered.

After 6 hours, the efficacy of the active ingredient preparation is determined. Efficacy is expressed as a percentage. 100% means that all flies were killed; 0% means that no flies were killed.

In this test, for example, the compounds according to Preparation Examples 6 and 11 (Isomer A) caused a killing of 100% at an exemplary active ingredient concentration of 1 000 ppm.

Example F

Cockroach test

Test animals: Periplaneta americana

Solvent: 35 parts by weight of ethyl glycol monomethyl ether

35 parts by weight of nonylphenol polyglycol ether

To prepare a suitable formulation, three parts by weight of active ingredient are mixed with seven parts of the solvent-emulsifier mixture specified above, and the resulting emulsion concentrate is diluted with water to the desired concentration. 2 ml of this active ingredient preparation is pipetted onto filter paper discs (9.5 cm diameter) placed in appropriately sized Petri dishes. After the filter discs are dried, five P. americana test animals are transferred and covered.

After 3 days, the effectiveness of the active ingredient preparation is determined. 100% means that all cockroaches were killed; 0% means that no cockroaches were killed.

In this test, for example, the compounds according to Preparation Examples 1, 3 (Isomer A), 6 and 10 (Isomer B) caused a killing of 100% at an exemplary active ingredient concentration of 1 000 ppm.

Example G

Blowfly larvae test

Test animals: Lucilia cuprina larvae

Solvent: 35 parts by weight of ethylene glycol monomethyl ether

35 parts by weight of nonylphenol polyglycol ether

To prepare a suitable formulation, 3 parts by weight of active ingredient are mixed with 7 parts of the above-mentioned mixture, and the resulting emulsion concentrate is diluted with water to the desired concentration. Approximately 20 Lucilia cuprina larvae are placed in a test tube containing approximately 1 ^cm³ of horse meat and 0.5 ml of the active ingredient preparation. After 24 hours, the efficacy of the active ingredient preparation is determined. 100% means that all blowfly larvae were killed; 0% means that no blowfly larvae were killed. In this test, for example, the compounds according to Preparation Examples 6, 7, 14, 13, 18, and 10 (B-isomer) achieved 100% killing at an exemplary active ingredient concentration of 1000 ppm.

Claims

Patent claims 1. Substituted tetrahydropyrazoles of formula (I)

in which R ¹ represents optionally substituted aryl or hetaryl, R ² represents a five- or six-membered, optionally substituted and optionally benzo-fused heterocycle containing one to four nitrogen atoms, R ³ and R ⁴ independently of one another represent hydrogen or alkyl, alkylcarbonyl, each optionally substituted by halogen, Alkoxycarbonyl, alkylsulfonyl, mono- or dialkylaminocarbonyl are or R ³ and R ⁴ together represent the residue A, where A for one of the groups

,

,

or

stands, R ⁶ represents hydrogen or alkyl, R ⁵ represents optionally substituted alkyl or cycloalkyl or the radical

wherein R ⁷ and R ⁸ independently represent hydrogen, halogen, nitro, Cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, in each case optionally substituted aryloxy or arylthio, optionally substituted mono- or dialkylamino, optionally substituted cycloalkyl, for alkoxycarbonyl, alkenyl, alkynyl, alkylthionyl, alkylsulfonyl, haloalkylthionyl, haloalkylsulfonyl or haloalkoxycarbonyl or wherein R ⁷ and R ⁸ together represent alkanediyl which may contain one or two oxygen atoms and may be substituted, and X represents oxygen or sulfur, and their enantiomerically pure forms. 2. Substituted tetrahydropyrazoles of the formula (I) according to claim 1, in which R ¹ represents pyridyl, pyrazinyl, pyridazinyl, _thienyl , _thiazolyl , each optionally substituted by halogen, nitro, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ haloalkylthio, C 1 -C 6 alkoxycarbonyl or di-C ₁ -C ₆ alkylamino or the radical stands,

wherein Y and Z independently of one another represent hydrogen, halogen, nitro, cyano, C ₁ -C ₈ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkoxycarbonyl, C ₁ - C ₆ haloalkoxycarbonyl, represent phenoxy or phenylthio, each optionally substituted by halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkyl, represent C ₂ -C ₆ alkenyl, C 2 -C 6 alkynyl, C ₁ -C ₄ alkylthionyl, C _{1 -C 4} alkylsulfonyl, C ₁ -C ₄ haloalkylthionyl, C _{1 -C 4} -Halogenalkylsulfonyl, represents mono- or di-(C ₁ -C ₆ -alkylamino) which is optionally substituted by halogen or C ₁ -C ₄ -alkoxy or Y and Z together represent 3,4-methylenedioxy or 3,4-ethylenedioxy, each optionally substituted by fluorine and/or chlorine., R ² represents a heterocyclic radical from the series

stands in which R ⁹ and R ¹⁰ independently of one another represent hydrogen, halogen, cyano, nitro, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ haloalkylthio, C ₁ -C ₆ alkoxycarbonyl or di-(C ₁ -C ₄ alkyl)amino, R ³ and R ⁴ independently of one another represent hydrogen or C ₁ -C 5 alkyl, C 1 -C ₅ alkylcarbonyl, C ₁ -C ₅ alkoxycarbonyl, C ₁ -C ₅ alkylsulfonyl, mono- or di-(C _{1 -C 5} alkyl)aminocarbonyl, each optionally substituted by fluorine, chlorine and/or bromine _, or R ³ and R ⁴ together represent the residue A, where A represents one of the groups

,

,

or

stands, R ⁶ represents hydrogen or C ₁ -C ₄ alkyl, R ⁵ represents C ₁ -C ₆ alkyl optionally substituted by halogen or C ₁ -C ₄ haloalkoxy, represents C ₃ -C ₇ cycloalkyl optionally substituted by halogen, C ₁ -C ₄ haloalkyl or C ₁ -C ₄ haloalkoxy or represents the radical stands,

wherein R ⁷ and R ⁸ independently represent hydrogen, halogen, nitro, Cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, represents phenoxy or phenylthio, each optionally substituted by halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or C ₁ -C ₆ haloalkyl, represents mono- or di-(C ₁ -C ₆ alkyl)amino, each optionally substituted by halogen, C ₁ -C ₁ alkoxy or C ₁ -C ₄ haloalkoxy, represents C ₃ -C ₇ cycloalkyl, optionally substituted by halogen, C 1 -C ₄ alkyl, C ₁ -C 4 alkoxy or C ₁ -C ₄ alkylthio, represents C ₁ -C ₆ alkoxycarbonyl, C _{2 -C 6} alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₄ alkylthionyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ haloalkylthionyl, C _{1 -C 4} -haloalkylsulfonyl or C ₁ -C ₄ -haloalkoxycarbonyl or wherein R ⁷ or R ⁸ together represent one of the radicals

stand and X stands for oxygen or sulfur. 3. Substituted tetrahydropyrazoles of formula (I) according to claim 1, in which R ¹ for the rest stands,

wherein Y and Z independently represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₃ alkylthio, C ₁ - C ₃ -haloalkyl, C ₁ -C ₃ -haloalkoxy, C ₁ -C ₃ -haloalkylthio, C ₁ -C ₃ -alkoxycarbonyl, C ₁ -C ₃ -haloalkoxycarbonyl, represents phenoxy or phenylthio, each optionally substituted by fluorine, chlorine, bromine, C ₁ -C ₃ -alkyl, C ₁ -C ₈ -alkoxy or C ₁ -C ₃ -haloalkyl, represents C ₂ -C ₄ -alkenyl, C ₂ -C ₄ -alkynyl, C ₁ -C ₃ -alkylthionyl, C ₁ -C ₃ -alkylsulfonyl, C ₁ -C ₃ -haloalkylthionyl, C ₁ -C ₃ -haloalkylsulfonyl or represents mono- or di-(C ₁ -C ₃ -alkyl)amino, each optionally substituted by fluorine, chlorine, bromine or C ₁ -C ₃ -alkoxy or Y and Z together represent 3,4-methylenedioxy or 3,4-ethylenedioxy, each optionally substituted by fluorine and/or chlorine, R ² represents a heterocyclic radical from the series stands,

wherein R ⁹ and R ¹⁰ independently represent hydrogen, chlorine, bromine, methyl, ethyl or trifluoromethyl, R ³ and R ⁴ independently of one another represent hydrogen or C ₁ -C ₄ alkyl, C 1 -C 4 alkylcarbonyl, C ₁ -C ₄ alkoxycarbonyl, C ₁ -C ₄ alkylsulfonyl, mono- or di-(C _{1 -C 4} alkyl)aminocarbonyl, each optionally substituted by fluorine and/or chlorine _, or R ³ and R ⁴ together represent the residue A, where A for one of the groups

,

,

or

R ⁶ represents hydrogen or C ₁ -C ₃ alkyl, R ⁵ represents C ₁ -C ₄ alkyl optionally substituted by fluorine, chlorine, bromine or C ₁ -C ₈ haloalkoxy, represents C ₃ -C ₆ cycloalkyl optionally substituted by fluorine, chlorine, bromine, C ₁ -C ₃ haloalkyl or C ₁ -C ₃ haloalkoxy or represents the radical

wherein R ⁷ and R ⁸ independently of one another represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₃ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₃ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₃ haloalkylthio, phenoxy optionally substituted by fluorine, chlorine, bromine, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy or C ₁ -C ₃ haloalkyl, represents mono- or di-(C ₁ -C ₄ alkyl)amino which is in each case optionally substituted by fluorine, chlorine, bromine, C ₁ -C ₃ alkoxy or C ₁ -C ₃ haloalkoxy, represents C ₃ -C ₆ cycloalkyl which is optionally substituted by fluorine, chlorine, bromine, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy or C ₁ - C ₃ alkylthio, represents C ₁ - C ₄ haloalkylsulfonyl or R ⁷ and R ⁸ together for one of the residues

stand and X stands for oxygen or sulfur. 4. Substituted tetrahydropyrazoles of formula (I) according to claim 1, in which R ¹ for the rest stands,

wherein Y and Z independently of one another represent hydrogen, fluorine, chlorine, bromine, C ₁ - C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₃ haloalkyl or C ₁ -C ₃ haloalkoxy or Y and Z together for one of the remainders

stand, R ² represents a heterocyclic radical from the series

stands, R ³ and R ⁴ independently of one another represent hydrogen or methyl, ethyl, propyl, methylcarbonyl, ethylcarbonyl, methoxycarbonyl or ethoxycarbonyl, each optionally substituted by fluorine and/or chlorine, or R ³ and R ⁴ together represent a radical A, where A for one of the groups — _CH2 —

.

or

stands, R ⁵ represents C ₃ -C ₆ cycloalkyl optionally substituted by C ₁ -C ₃ haloalkyl or the radical

wherein R ⁷ and R ⁸ independently of one another represent hydrogen, cyano, nitro, fluorine, chlorine, bromine, C ₁ -C ₄ alkyl, C ₁ -C ₃ haloalkyl, C ₁ -C ₃ alkoxy, C ₁ -C ₃ haloalkoxy, C ₁ -C ₃ haloalkylthio or _C 1 -C ₃ haloalkylsulfonyl or R ⁷ and R ⁸ together for one of the residues or

stand and X stands for oxygen. 5. A process for the preparation of the substituted tetrahydropyrazoles of the formula (I) according to claim 1, characterized in that A) to obtain compounds of the formula (Ia)

in which R ¹ , R ² , R ⁴ , R ⁵ and X have the meaning given in claim 1, Dihydropyrazoles of formula (II)

in which R ¹ , R ² , R ⁴ , R ⁵ and X have the meaning given above, in the presence of a reducing agent, optionally in the presence of a catalyst and in the presence of a diluent, and that B) to obtain substituted tetrahydropyrazoles of formula (I)

in which R ¹ , R ² , R ⁴ , R ⁵ and X have the meaning given above and R ³ has the meaning given in claim 1 with the exception of hydrogen, Compounds of the above formula (Ia), in which R ¹ , R ² , R ⁴ , R ⁵ and X have the meaning given above, with compounds of the formula (III) R ³ -Hal (III) in which R ³ has the meaning given above with the exception of hydrogen and Hal stands for halogen, in the presence of a diluent and optionally in the presence of a base and that C) to obtain compounds of formula (Ib)

in which A, R ¹ , R ² , R ⁵ and X have the meaning given above for formula (I), either α) to obtain compounds of formula (Ib), in which A represents, compounds of formula (Ic)

in which R ¹ , R ² , R ⁵ and X have the meaning given above, with aldehydes of the formula (IV) R ⁶ -CHO (IV) in which R ⁶ has the meaning given in claim 1 in the presence of an acid and optionally in the presence of a diluent or ß) to obtain compounds of the formula (Ib) in which A is - CO- or -COCO-, compounds of the formula (Ic)

in which R ¹ , R ² , R ⁵ and X have the meaning given above, with phosgene or with oxalyl chloride, optionally in the presence of a diluent and optionally in the presence of a base or γ) to obtain compounds of formula (Ib), in which A is

compounds of the formula (Id)

in which R ¹ , R ² , R ⁵ , R ⁶ and X have the meanings given above, optionally in the presence of a diluent, with a base. 6. Pesticide, characterized by a content of at least one compound of formula (I) according to claim 1. 7. Use of compounds of formula (I) according to claim 1 for controlling pests. 8. A method for controlling pests, characterized in that at least one compound of formula (I) according to claim 1 is allowed to act on pests and/or their habitat. 9. A process for the preparation of pesticides, characterized in that compounds of formula (I) according to claim 1 are mixed with extenders and/or surface-active agents. 10. Use of compounds of formula (I) according to claim 1 for the preparation of pesticides.