WO2006122949A1

WO2006122949A1 - Malononitriles and their use as pesticides

Info

Publication number: WO2006122949A1
Application number: PCT/EP2006/062382
Authority: WO
Inventors: Michael Hofmann; Henricus Maria Martinus Bastiaans; Jürgen LANGEWALD; Hassan Oloumi-Sadeghi; Deborah L. Culbertson
Original assignee: Basf Aktiengesellschaft
Priority date: 2005-05-20
Filing date: 2006-05-17
Publication date: 2006-11-23

Abstract

Malononitrile compounds of formula (I) wherein R1 is H, (halo)alkyl, (halo)alkenyl, or (halo)alkynyl; R2 is H1 CN, (halo)alkyl, (halo)alkenyl, (halo)alkynyl, (halo)cycloalkyl, or (halo)alkoxy; R3 and R4 are H, (halo)alkyl, (halo)alkenyl, (halo)alkynyl, (halo)cycloalkyl, or (halo)cycloalkenyl or taken together (halo)alkylene or (halo)alkenylene; A is an optionally substituted saturated or unsaturated 5-membered heterocyclic radical which may contain 2 to 4 heteroatoms selected from oxygen, nitrogen and sulfur, and which may be fused with another 5-or 6-membered saturated or unsaturated heterocyclic ring or with a phenyl ring, both rings being optionally substituted; or the enantiomers or diastereomers or salts thereof, processes and intermediates for preparing the compounds I, pesticidal compositions comprising compounds I, methods for the control of insects, acarids or nematodes by contacting the pests or their food supply, habitat or breeding grounds with a pesticidally effective amount of compounds formula (I), and a method for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of compounds of formula (I).

Description

Malononitriles and their use as pesticides

The present invention relates to malononitrile compounds of formula I

wherein

R¹ is hydrogen, Ci-Cio-alkyl, CrCio-haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C∑-Cio-alkynyl, or C₃-Ci₀-haloalkynyl;

R² is hydrogen, cyano, Ci-Cio-alkyl, CrCio-haloalkyl, C2-Cio-alkenyl, C2-C10- haloalkenyl, C₂-Cio-alkynyl, C3-Cio-haloalkynyl, C3-C₆-cycIoalkyl, C₃-C₆- halocycloalkyl, Ci-Cio-alkoxy, or Ci-Cio-haloalkoxy;

R³ and R⁴ each independently are hydrogen, Ci-Cio-alkyl_> CrCio-haloalkyl, C2-C10- alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C3-Cio-haloalkynyl, C3-Cio-cycloaIkyI,

C3-Cio-halocycIoalkyl, C₄-C6-cycloalkenyl, C₄-C6-halocycloalkenyl, or R³ and R⁴ together can be C₂-Cio-alkylene, C_∑-Cio-haloalkylene, C₄-Cio-alkenylene or

C₄-CiQ-haloalkenylene,

A is a saturated or unsaturated 5-membered heterocyclic radical which may contain 2 to 4 heteroatoms selected from oxygen, nitrogen and sulfur, and which may be fused with another 5-or 6-membered saturated or unsaturated heterocyclic ring or with a phenyl ring, wherein the saturated or unsaturated 5-membered heterocyclic radical and the 5- or 6-membered heterocyclic ring or phenyl with which it is fused each is substituted with any combination of 1 to 6 groups R^a;

R^a is hydrogen, halogen, hydroxyl, cyano, nitro, CrCio-alkyl, Ci-Ci₀-haloalkyI, C3-Cio-cylcoalkyI, Cs-Cio-halocycloalkyl, C∑-Cio-alkenyl, C2-Cio-ha!oalkenyl, C2-Cio-aIkynyl, C3-Cio-haloaIkynyl, Ci-Cio-alkoxy, CrCio-haIoalkoxy, C2-C10- alkenyloxy, C2-Cio-haloalkenyloxy, C2-Cio-alkynyloxy, C3-Cio-haIoalkynyloxy,

CrCio-alkylthio, Ci-Cio-haloalkylthio, d-Cio-alkylsulfinyl, C1-C10- haloalkylsulfinyl, Ci-Cio-alkylsulfonyl, Ci-Cio-haloalkylsulfonyl, NR⁵R⁶, d- Cio-alkoxycarbonyl, d-Cio-haloalkoxycarbonyl, C2-Cio-alkenyloxycarbonyl, C2-Cio-haloalkenyloxycarbonyI, d-Cio-alkylcarbonyl, C1-C10- haloalkylcarbonyl, Ci-Cio-alkylcarbonyloxy, Ci-Cio-haIoaIkylcarbonyloxy,

R⁵R⁶N-C(=O), phenyl, benzyl, furyl, thienyl, pyridyl, phenoxy or phenylthio, wherein the carbon atoms in the latter 7 rings are unsubstituted or substituted with any combination of 1 to 5 groups R^b; R^b is halogen, hydroxy, cyano, nitro, CrCio-alkyl, CrCio-haloalkyl, C3-C10- cylcoalkyl, C3-Cio-halocycloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-C10- alkynyl, C3-Cio-haloalkynyI, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, C₁-C₁0- alkylthio, d-do-haloalkylthio, CrCio-alkylsulfinyl, Ci-Cio-haloalkylsuIfinyl, Ci-Cio-alkylsulfonyl, d-CiQ-haloalkylsulfonyl, NR⁵R⁶, Ci-Cio-alkoxycarbonyl, Ci-Cio-haloalkoxycarbonyl, Crdo-alkylcarbonyl, Crdo-haloalkylcarbonyl or R⁵R⁶N-CO-;

R⁵, R⁶ are each independently hydrogen, d-do-alkyl, d-do-haloalkyl, d- Cio-alkylcarbonyl, Ci-Cio-haloalkylcarbonyl, benzyl, phenyl, phenylcarbonyl, Ci-Cio-alkylsulfonyl, or Ci-Cio-haloalkylsulfonyl;

or the enantiomers or diastereomers or salts thereof.

In a preferred embodiment, the present invention relates to malononitrile compounds of formula I having the formula 1.1

NC CN

wherein

R¹ is hydrogen, d-do-alkyl, d-do-haloalkyl, C₂-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, or C3-Cio-haloalkynyI;

R² is hydrogen, cyano, d-do-alkyl, d-Cio-haloalkyl, C₂-Cio-alkenyl, C₂-Ci₀- haloalkenyl, C₂-Cio-alkynyl, C3-d_o-haloalkynyl, C₃-C₆-cycIoalkyl, C₃-C₆- halocycloalkyl, Ci-Cio-alkoxy, or Ci-Cio-haloalkoxy;

R³ and R⁴ each independently are hydrogen, Ci-Ci_θ-alkyl, Ci-Ci_θ-haloalkyl, C2-C10- alkenyl, C₂-Ci_θ-haloalkenyl, C2-Cio-alkynyl, C3-Cio-haloalkynyl, C3-Cio-cycloalkyl,

Cs-Cio-halocycloalkyl, C₄-C6-cycloalkenyl, C₄-C6-halocycloalkenyl, or R³ and R⁴ together can be C2-Cio-alkylene, C2-Cio-haloalkylene, C₄-Ci₀-alkenylene or

C₄-Cio-haloalkenylene,

A is (1) a saturated 5-membered heterocyclic radical which may contain 2 to 4 het- eroatoms selected from oxygen, nitrogen and sulfur, and which may be fused with a 5-or 6-membered saturated or unsaturated heterocyclic ring or with a phenyl ring, or

(2) an unsaturated 5-membered heterocyclic radical which may contain 2 to 4 heteroatoms selected from oxygen, nitrogen and sulfur, and which may be fused with a 5-or 6-membered saturated or unsaturated heterocyclic ring or with a phenyl ring, wherein the saturated or unsaturated 5-membered heterocyclic radical and the 5- or 6-membered heterocyclic ring or phenyl with which it is fused each is substituted with any combination of 1 to 6 groups R^a; R^a is hydrogen, halogen, hydroxyl, cyano, nitro, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C3-Cio-cylcoalkyl, C₃-Cio-halocycloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C₃-Cio-haloalkynyl, CrCio-alkoxy, Ci-Cio-haloalkoxy, C₂-C₁0- alkenyloxy, C2-Cio-haloalkenyloxy, C₂-Cio-alkynyloxy, C3-Cio-haloalkynyloxy, CrCio-alkylthio, Ci-Cio-haloalkylthio, d-do-alkylsulfinyl, d-do- haloalkylsulfinyl, Ci-Cio-alkylsulfonyl, CrCio-haloalkylsulfonyl, NR⁵R⁶, d- Cio-alkoxycarbonyl, d-do-haloalkoxycarbonyl, C2-Cio-alkenyloxycarbonyl, Ca-Cio-haloalkenyloxycarbonyl, Ci-Cio-alkylcarbonyl, d-do- haloalkylcarbonyl, d-do-alkylcarbonyloxy, d-do-haloalkylcarbonyloxy, R⁵R⁶N-C(=O), phenyl, benzyl, furyl, thienyl, pyridyl, phenoxy or phenylthio, wherein the carbon atoms in the latter 7 rings are unsubstituted or substituted with any combination of 1 to 5 groups R^b;

R^b is halogen, hydroxy, cyano, nitro, d-do-alkyl, d-do-haloalkyl, C₃-do- cylcoalkyl, Cs-do-halocycloalkyl, C2-Cio-alkenyl, C∑-do-haloalkenyl, C₂-C₁0- alkynyl, C3-Cio-haloalkynyl, d-do-alkoxy, Ci-Cio-haloalkoxy, d-do- alkylthio, Ci-Cio-haloalkylthio, Ci-Cio-alkylsulfinyl, Ci-Cio-haloalkylsulfinyl, Ci-Cio-alkylsuIfonyl, d-do-haloalkylsulfonyl, NR⁵R⁶, Ci-Cio-alkoxycarbonyl, Ci-Cio-haloalkoxycarbonyl, Ci-Cio-alkylcarbonyl, d-do-haloalkylcarbonyl or R⁵R⁶N-CO-; R⁵, R⁶ are each independently hydrogen, d-do-alkyl, d-do-haloalkyl, Ci-

Cio-alkylcarbonyl, d-Cio-haloalkylcarbonyl, benzyl, phenyl, phenylcarbonyl, Ci-Cio-alkylsulfonyl, or d-do-haloalkylsulfonyl;

wherein the unsaturated 5-membered heterocyclic radical which may contain 2 to 4 heteroatoms selected from oxygen, nitrogen and sulfur, and which may be fused with a 5-or 6-membered saturated or unsaturated heterocyclic ring or with a phenyl ring is selected from the following Table Q:

Table Q

Table Q - continued

A.28 A.29 A.30

A.31 A.32 A.34 wherein R^a1, R^a2, R^a3, R^a4 and R^a5 each independently have the meaning as defined above for R^a, with the provisos that (a) for A.5, R^a1 is not methyl, ethyl, tert.-butyl, chlorine, -OCH₂CCH, or -O(CH₂)₂CCH when R^a2 is hydrogen; and

(b) for A.9, R^a1 is not methoxy or tert-butyl when R^a2 is hydrogen; and

(c) for A.20, R^a1 is not tert.-butyl; and

(d) for A.22, R^a1 is not ethyl, tert.-butyl, (i-methyl)-cyclopropyl, or neopentyl; and (e) for A.34, R^a2 is not trifluoromethyl when R^a1 and R^a1 are hydrogen, or the enantiomers or diastereomers or salts thereof.

In addition, the present invention relates to processes and intermediates for preparing the compounds I, pesticidal compositions comprising compounds I, methods for the control of insects, acarids or nematodes by contacting the insect, acarid or nematode or their food supply, habitat or breeding grounds with a pesticidally effective amount of compounds or compositions of formula I.

Moreover, the present invention also relates to a method of protecting growing plants from attack or infestation by insects or acarids by applying to the foliage of the plants, or to the soil or water in which they are growing, with a pesticidally effective amount of compositions or compounds of formula I.

This invention also provides a method for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of compositions or compounds of formula I.

In spite of the commercial insecticides, acaricides and nematicides available today, damage to crops, both growing and harvested, caused by insects and nematodes still occurs. Therefore, there is continuing need to develop new and more effective insecti- cidal, acaricidal and nematicidal agents.

It was therefore an object of the present invention to provide new pesticidal compositions, new compounds and new methods for the control of insects, acarids or nematodes and of protecting growing plants from attack or infestation by insects, arachnids or nematodes.

We have found that these objects are achieved by the compositions and the compounds of formula I. Furthermore, we have found processes and intermediates for preparing the compounds of formula I.

Malononitriles have been described in a number of patent applications: JP 2002 284608, WO 02/089579, WO 02/090320 and WO 02/ 090321 pertain to compounds that carry an optionally substituted phenyl in the position of the substituent A of the compounds I of the present invention. WO 04/006677 describes compounds that carry an optionally substituted pyridyl in the position of the substituent A of the compounds I of the present invention. JP 2004 99597 pertains to compounds that are sub- stituted with a 5-membered heterocycle with one heteroatom as substituent A.

WO 05/068432 and WO 05/068423, both published after the prioirity date of the present application, also describe certain malonodinitrile compounds that are substituted with a 5-membered heterocycle with two or three heteroatoms some of which are fused to a phenyl ring.

Compounds of formula I are obtainable, for example, by a process wherein compound (II) is reacted with compound (III) to give compounds (I):

(H) (I) wherein R¹, R², R³ and R⁴ are as defined above for compounds of formula I and Z¹ represents a halogen atom, methanesulfonyl, trifluoromethanesulfonyl or toluenesul- fonyl.

The reaction is generally carried out in the presence of a base in a solvent.

The solvent to be used in the reaction includes, for example, acid amides such as N₁N- dimethylformamide, NMP and the like, ethers such as diethyl ether, tetrahydrofuran and the like, sulfoxides and sulfones such as dimethylsulfoxide, sulfolane and the like, halogenated hydrocarbons such as 1 ,2 -dichloroethane, chlorobenzene and the like, aromatic hydrocarbons such as toluene, xylene and the like, and mixtures thereof.

The base to be used in the reaction includes, for example, inorganic bases such as sodium hydride, sodium carbonate, potassium carbonate and the like, alkali metal alkoxides such as potassium t-butoxide and the like, alkali metal amides such as lithium diisopropylamide and the like, and organic bases such as dimethylaminopyridine, 1 ,4-diazabicyclo[2.2.2]octane, 1 ,8-diazabicyclo [5.4.0]-7-undecene and the like.

The amount of the base that can be used in the reaction is usually 1 to 10 moles relative to 1 mole of compound (II). In addition, additives such as crown ethers may be added to accelerate the reaction.

The amount of compound (III) to be used in the reaction is usually 1 to 10 moles, pref- erably 1 to 2 moles relative to 1 mole of compound (II).

The reaction temperature is usually in the range of - 78° C to 150° C, preferably in the range of -2O⁰C to 80⁰C and the reaction time is usually in the range of 1 to 24 hours.

Intermediates of formula Il are novel and also subject of this invention.

After completion of the reaction, the compound of formula (I) can be isolated by em- ploying conventional methods such as adding the reaction mixture to water, extracting with an organic solvent, concentrating the extract an the like. The isolated compound (I) can be purified by a technique such as chromatography, recrystallization and the like, if necessary.

The compound (II) can be produced, for example, according to the route represented by the fol

wherein R¹ and R² are as defined above for formula I.

Step 1 : The compound (V) can be produced by reacting compound (IV) with malononi- trile (CN(CH₂)CN; see e.g. Organic Process Research & Development 2005, 9, 133- 136). The reaction is generally carried out in the presence of base in a solvent. The solvent to be used in the reaction includes, for example, acid amides such as N₁N- dimethylformamide and the like, ethers such as diethyl ether, tetrahydrofuran and the like, halogenated hydrocarbons such as chloroform, 1 ,2-dichloroethane, chlorobenzene and the like, aromatic hydrocarbons such as toluene, xylene and the like, alcohols such as methanol, ethanol, isopropyl alcohol and the like, and mixtures thereof.

The base to be used in the reaction includes, for example, tetrabutylammonium hydroxide. The amount of the base that can be used in the reaction is usually 0.01 to 0.5 moles relative to 1 mole of compound (IV).

The amount of malononitrile to be used in the reaction is usually 1 to 10 moles relative to 1 mole of compound (IV). The reaction temperature is usually in the range of - 20^cC to 200⁰C, and the reaction time is usually in the range of 1 to 24 hours.

The reaction may be carried out with removing the water formed by the reaction from the reaction system, if necessary.

After completion of the reaction, the compound of formula (V) can be isolated by employing conventional methods such as adding the reaction mixture to water, extracting with an organic solvent, concentrating the extract and the like. The isolated compound (V) can be purified by a technique such as chromatography, recrystallization and the like, if necessary.

Step 2: a) In the case where R² represents CrCio-alkyl, C₂-Ci₀-alkenyl or C2-C10- alkynyl, the compound (II) can be produced by reacting compound (V) with an or- ganometallic compound R²-Q.

The reaction is generally carried out in a solvent, and if necessary, in the presence of a copper salt.

The solvent to be used in the reaction includes, for example, ethers such as diethyl ether, tetrahydrofuran and the like, aromatic hydrocarbons such as toluene, xylene and the like, and mixtures thereof.

The organometallic compound R²-Q to be used in the reaction includes, for example, organomagnesium compounds such as methylmagnesium iodide, ethylmagnesium bromide, isopropylmagnesium bromide, vinylmagnesium bromide, ethynylmagnesium bromide, dimethylmagnesium and the like, organolithium compounds such as methyl- lithium and the like, organozinc compounds such as diethylzinc and the like, and organocopper compounds such as trifluoromethylcopper and the like. The amount of the organometallic compound that can be used in the reaction is usually 1 to 10 moles relative to 1 mole of compound (V).

The copper salt to be used in the reaction includes, for example, cuprous (I) iodide, cuprous (I) bromide and the like. The amount of the copper salt to be used in the reaction is usually not more than 1 mole relative to 1 mole of compound (V). The reaction temperature is usually in the range of - 20⁰C to 100⁰C, and the reaction time is usually in the range of 1 to 24 hours.

After completion of the reaction, the compound of formula (II) can be isolated by employing conventional methods such as adding the reaction mixture to water, extracting with an organic solvent, concentrating the extract and the like. The isolated compound (II) can be purified by a technique such as chromatography, recrystallization and the like, if necessary.

Step 2: (b) In the case where R² represents a hydrogen atom, the compound (II) can be produced by reacting compound (V) with a reducing agent.

The reaction is usually carried out in a solvent.

The solvent to be used in the reaction includes, for example, ethers such as diethyl ether, tetrahydrofuran and the like, aromatic hydrocarbons such as toluene, xylene and the like, alcohols such as methanol, ethanol, propanol and the like, water, acetic acid, ethyl acetate and mixtures thereof.

The reducing agent to be used in the reaction includes, for example, sodium boro- hydride or hydrogen in the presence of a catalyst such a Pd/C. The amount of the re- ductant to be used in the reaction is usually 0.25 to 2 moles relative to 1 mole of compound (V).

The reaction temperature is usually in the range of 0⁰C to 50° C, and the reaction time is usually in the range of sec to 24 hours.

Step 2: (c) In the case where R² represents cyano, the compound (II) can be produced by reacting compound (V) with a cyanide.

The reaction is usually carried out in a solvent. The solvent to be used in the reaction includes, for example, ethers such as diethyl ether, tetrahydrofuran and the like, aromatic hydrocarbons such as toluene, xylene and the like, and mixtures thereof.

The cyanide to be used in the reaction includes, for example, tetrabutylammonium cyanide. The amount of the cyanide to be used in the reaction is usually 1 to 10 moles relative to 1 mole of compound (IV).

The reaction temperature is usually in the range of - 20⁰C to 100⁰C, and the reaction time is usually in the range of 1 to 24 hours.

According to a further embodiment of the present invention, compounds I can be obtained by a process wherein compound (Vl) is reacted with compound (VII) to give compounds (I):

N

(Vl) (I) wherein, R¹, R², R³ and R⁴ are as defined above and Z² represents a halogen atom, methanesulfonyl, trifluoromethanesulfonyl or toluenesulfonyl.

The reaction is generally carried out in the presence of base in a solvent.

The solvent to be used in the reaction includes, for example, acid amides such as N, N- dimethylformamide NMP and the like, ethers such as diethyl ether, tetrahydrofuran and the like, sulfoxides and sulfones such as dimethylsulfoxide, sulfolane and the like, halo- genated hydrocarbons such as 1 ,2-dichloroethane, chlorobenzene and the like, aromatic hydrocarbons such as toluene, xylene and the like, and mixtures thereof.

The base to be used in the reaction includes, for example, inorganic bases such as sodium hydride, sodium carbonate, potassium carbonate and the like, alkali metal alkoxides such as potassium t-butoxide and the like, alkali metal amides such as lithium diisopropylamide and the like, and organic bases such as 4-dimethylaminopyridine, 1 ,4-diazabicyclo [2.2.2]octane, 1 ,8-diazabicyclo [5.4.0] -7-undecene and the like. The amount of the base that can be used in the reaction is usually 1 to 10 moles relative to 1 mole of compound (Vl).

The amount of compound (VII) to be used in the reaction is usually 1 to 10 moles, pref- erably 1 to 2 moles relative to 1 mole of compound (Vl).

The reaction temperature is usually in the range of - 78° C to 150° C₁ and the reaction time is usually in the range of 1 to 24 hours.

After completion of the reaction, the compound of formula (I) can be isolated by employing conventional methods such as adding the reaction mixture to water, extracting with an organic solvent, concentrating the extract and the like. The isolated compound (I) can be purified by a technique such as chromatography, recrystallization and the like, if necessary.

Compounds of formula Vl can be obtained according to procedures known in the art, e.g. as described in J. March, Advanced Organic Chemistry, 4^th Edition, Wiley, 1992, p. 468.

Compounds of formula VII can be obtained according to procedures known in the art, e.g. from the corresponding alcohols by nucleophilic replacement (J. March, Advanced Organic Chemistry, 4^th Edition, Wiley, 1992, pp. 432-433); or by sulfonylation (J. March, Advanced Organic Chemistry, 4^th Edition, Wiley, 1992, pp. 498-499); or by direct formation of halomethyl substituted heterocycles as described e.g. in WO 04/14902; or according to modifications of the above described methods.

According to a further embodiment of the present invention, compounds I.2 wherein R² is Ci-Cio-alkyl or CrCio-haloaIkyl, R¹ and R³ are hydrogen and R⁴ is vinyl, can be obtained by a process wherein compound (VIII) is reacted with compound (IX) to give com

(VIII) (IX) (I.2) wherein R² is CrCio-alkyl or Ci-Cio-haloalkyl, Bu is butyl and AIBN is azobisisobuty- ronitrile.

The reaction can be carried out according to the method described in J. Am. Chem. Soc, 110 (4), 1288-1290 (1988).

According to a further embodiment of the present invention, compounds 1.3 wherein R² is cyano, R¹ and R³ are hydrogen and R⁴ is vinyl, can be obtained by a process wherein compound (VIII) is reacted with vinylchloride and (CH3)3SiCN to give com¬

(VIII) (I.3) wherein dba is dibenzylidene acetone and dppf is 1 ,1'-bis(diphenylphosphino) ferrocene. The reaction can be carried out according to conditions described in Tetrahedron Lett., 41 , 2911-2914 (2000).

According to a further embodiment of the present invention, compounds 1.4 wherein R² is Ci-Cio-alkoxy or CrCio-haloalkoxy, R¹ and R³ are hydrogen and R⁴ is vinyl, can be obtained by a process wherein compounds (VIII) are reacted with compounds (X) to give compounds (1.4),

(VIII) (X) (I.4) wherein R² is Ci-Cio-alkoxy or CrCio-haloalkoxy, Ph is phenyl and THF is tetrahydrofu- ran. The reaction can be carried out according to the conditions described in J. Am. Chem. Soc, 120 (27), 6838-6839 (1998).

The preparation of the compounds of formula I may lead to them being obtained as isomer mixtures. If desired, these can be resolved by the methods customary for this purpose, such as crystallization or chromatography, also on optically active adsorbate, to give the pure isomers. Agronomically acceptable salts of the compounds I can be formed in a customary manner, e.g. by reaction with an acid of the anion in question.

In this specification and in the claims, reference will be made to a number of terms that shall be defined to have the following meanings:

"Salt" as used herein includes adducts of compounds I with maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid. Moreover, included as "salts" are those that can form with, for example, amines, metals, alkaline earth metal bases or quaternary ammonium bases, including zwitteri- ons. Suitable metal and alkaline earth metal hydroxides as salt formers include the salts of barium, aluminum, nickel, copper, manganese, cobalt zinc, iron, silver, lithium, sodium, potassium, magnesium or calcium. Additional salt formers include chloride, sulfate, acetate, carbonate, hydride, and hydroxide. Desirable salts include adducts of compounds I with maleic acid, dimaleic acid, fumaric acid, difumaric acid, and methane sulfonic acid.

"Halogen" will be taken to mean fluoro, chloro, bromo and iodo.

The term "alkyl" as used herein refers to a branched or unbranched saturated hydrocarbon group having 1 to 10 carbon atoms, such as d-Cβ-alkyl, for example methyl, ethyl, propyl, 1-methyIethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1 ,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyI, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1 ,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3- methylpentyl, 4-methylpentyl, 1 ,1-dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1 ,2- trimethylpropyl, 1 ,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2- methylpropyl.

The term "haloalkyl" as used herein refers to a straight-chain or branched alkyl group having 1 to 10 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example CrC₂-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, tri- chloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichloro- fluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2- fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2- difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;

Similarly, "alkoxy" and "alkylthio" refer to straight-chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages, respectively, at any bond in the alkyl group. Examples include methoxy, ethoxy, pro- poxy, isopropoxy, methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio. Similarly, "alkylsulfinyl" and "alkylsulfonyl" refer to straight-chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above) bonded through -S(=O)- or -S(=O)2-linkages, respectively, at any bond in the alkyl group. Examples include me- thylsulfinyl and methylsulfonyl.

The term "alkylcarbonyl" refers to straight-chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above) bonded through a -C(=O)- linkage, respectively, at any bond in the alkyl group. Examples include acetyl and propionyl.

The term "alkenyl" as used herein intends a branched or unbranched unsaturated hydrocarbon group having 2 to 6 carbon atoms and a double bond in any position, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyI, 1- methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl; 1- pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-i-butenyl, 2-methyl-1-butenyl, 3- methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyI-2-butenyl, 1-methyl- 3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2- dimethyI-1-propenyl, 1 ,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1- hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyI, 1 -methyl- 1 -pentenyl, 2-methyl-1- pentenyl, 3-methyl-1 -pentenyl, 4-methyl-1 -pentenyl, 1-methyI-2-pentenyl, 2-methyl-2- pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3- pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4- pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyI, 1,1-dimethyl-2-butenyI, 1,1- dimethyI-3-butenyl, 1,2-dimethyl-i-butenyl, 1 ,2-dimethyl-2-butenyl, 1 ,2-dimethyl-3- butenyl, 1 ,3-dimethyl-1-butenyl, 1 ,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2- dimethyl-3-butenyl, 2,3-dimethyl-1 -butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3- butenyl, 3,3-dimethyl-1 -butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1 -butenyl, 1-ethyl-2- butenyl, 1-ethyl-3-butenyl, 2-ethyl-1 -butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1 ,1,2- trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1- ethyl-2-methyl-2-propenyl;

The term "alkynyl" as used herein refers to a branched or unbranched unsaturated hydrocarbon group containing at least one triple bond, such as ethynyl, propynyl, 1- butynyl, 2-butynyl, and the like.

A saturated or unsaturated 5-membered heterocyclic radical which may contain 2 to 4 heteroatoms selected from oxygen, nitrogen and sulfur refers to e.g. a saturated or unsaturated 5-membered heterocyclic radical containing 2 to 4 nitrogen atoms, such as pyrazolyl, imidazolyl, triazolyi, and tetrazolyl; or saturated or unsaturated 5-membered heterocyclic radical containing 1 to 3 nitrogen atoms and 1 sulfur or 1 oxygen atom, e.g. isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyi, and tetrazolyl; or saturated or unsaturated 5-membered heterocyclic radical containing 1 or 2 nitrogen atoms and 1 oxygen atom, e.g. isoxazolyl, oxazolyl, and oxadiazolyl.

This saturated or unsaturated 5-membered heterocyclic radical which may contain 2 to 4 heteroatoms selected from oxygen, nitrogen and sulfur may be fused with another 5- or 6-membered heterocyclic ring or with a phenyl ring. The other 5-or 6-membered heterocyclic ring refers to e.g. a saturated or unsaturated 5-membered heterocyclic ring, containing 2 to 3 nitrogen atoms, such as pyrazol, imidazol, and triazol; or a saturated or unsaturated 5-membered heterocyclic ring, containing 1 to 3 nitrogen atoms and 1 sulfur or 1 oxygen atom, e.g. isoxazol, isothiazol, pyrazol, oxazol, thiazol, and imidazol; or a 5-membered heterocyclic ring containing 2 oxygen atoms, e.g. dioxolane; or a 6-membered heterocyclic ring containing 1 to 3 nitrogen atoms e.g. pyridine, pyridaz- ine, pyrimidine, pyrazine, and triazine; or a 6-membered heterocyclic ring containing 0 to 1 nitrogen atomes and 1 to 2 oxygen atoms or 1 to 2 sulfur atoms, e.g. dioxane, morpholine, dithiane, and thiomerpholine.

The fused ring system thereby is, for example, benzoxazolyl, benzthiazolyl, benzimida- zolyl, or pyrimidotriazolyl.

Cycloalkyl: monocyclic 3- to 6-, 8-, or 10-membered saturated carbon atom rings, e.g. C3-Cio-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl.

With respect to the intended use of the compounds of formula I and formula 1.1, par- ticular preference is given to the following meanings of the substituents, in each case on their own or in combination:

A compound of formula I or formula 1.1 wherein R¹ is hydrogen and R² is methyl.

A compound of formula I or formula 1.1 wherein R² is hydrogen, methyl or cyano.

A compound of formula I or formula 1.1 wherein R¹ and R² are hydrogen.

A compound of formula I or formula 1.1 wherein R¹ and R² are methyl.

A compound of formula I or formula 1.1 wherein R⁴ is hydrogen, C2-C6-alkenyl, such as vinyl, 2-propenyl, or 2-methyl-1-propenyl, C₂-C6-haloalkenyl, such as 2,2-difluorovinyl, 1-(trifluoromethyl)vinyl, 3,3-difluoro-2-propenyl, 2,3,3-trifluoro-2-propenyl, or 3,3,3- trifluoro-1-propenyl, C2-C6-haloalkynyl, Ci-Cδ-fluoroalkyl, such as fluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 3,3,3- trifluoropropyl, or 2,2,3, 3,3-pentafluoropropyl, Cs-Cβ-cycloalkyl, 2,2-dichlorocyclopropyl, cyclopropyl, or cyclobutyl. A compound of formula I or formula 1.1 wherein R³ is hydrogen.

A compound of formula I or formula 1.1 wherein R³ is hydrogen and R⁴ is a C2-C6- alkenyl.

A compound of formula I or formula 1.1 wherein R³ is hydrogen and R⁴ is vinyl, 2- propenyl or 2-methyl-1-propenyl.

A compound of formula I or formula 1.1 wherein R³ is hydrogen and R⁴ is a C₂-C₆- haloalkenyl.

A compound of formula I or formula 1.1 wherein R³ is hydrogen and R⁴ is 2,2- difluorovinyl, 1- (trifluoromethyl)vinyl, 3,3-difluoro-2-propenyl, 2,3,3-trifluoro-2-propenyl or 3,3,3-trifluoro-1-propenyl.

A compound of formula I or formula 1.1 wherein R³ is hydrogen and R⁴ is a CrCβ- haloalkyl.

A compound of formula I or formula 1.1 wherein R³ is hydrogen and R⁴ is fluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1 ,2,2,2-pentafluoroethyl, 3,3,3-trifluoropropyl or 2,2,3,3,3-pentafluoropropyl.

A compound of formula I or formula 1.1 wherein R³ is hydrogen and R⁴ is a C3-C6- cycloalkyl or C3-C6-halocycloalkyl

A compound of formula I or formula 1.1 wherein R³ is hydrogen and R⁴ is cyclopropyl, cyclobutyl or 2,2-dichlorocyclopropyl.

A compound of formula I or formula 1.1 wherein R¹, R² and R³ are hydrogen and R⁴ is vinyl, 2-propenyl or 2-methyl-2-propenyl.

A compound of formula I or formula 1.1 wherein R¹, R² and R³ are hydrogen and R⁴ is 2,2-difluorovinyl, 1-(trifluoromethyl)vinyl, 3,3-difluoro-2-propenyl, 2,3,3-trifluoro-2- propenyl or 3,3,3-trifluoro-1-propenyl.

A compound of formula I or formula 1.1 wherein R¹ and R² are methyl, R³ is hydrogen and R⁴ is 2,2-difluorovinyl, 1-(trifluoromethyl)vinyl, 3,3-difluoro-2-propenyl, 2,3,3- trifluoro-2-propenyl or 3,3,3-trifluoro-1-propenyl.

A compound of formula I or formula 1.1 wherein R¹ and R³ are hydrogen, R² is methyl and R⁴ is 2,2-difluorovinyl, 1-(trifluoromethyl)vinyl, 3,3-difluoro-2-propenyl, 2,3,3- trifIuoro-2-propenyl or 3,3,3-trifIuoro-i-propenyl.

A compound of formula I or formula 1.1 wherein R¹, R² and R³ are hydrogen, R⁴ is fluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 3,3,3-trifluoropropyl or 2,2,3,3,3-pentafluoropropyl.

A compound of formula I or formula 1.1 wherein R¹ and R³ are hydrogen, R² is methyl and R⁴ is fluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 3,3,3- trifluoropropyl or 2,2,3,3,3-pentafluoropropyl.

A compound of formula I or formula 1.1 wherein R¹ and R² are methyl, R³ is hydrogen, and R⁴ is fluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 3,3,3- trifluoropropyl or 2,2,3,3,3-pentafluoropropyl.

A compound of formula I or formula 1.1 wherein R¹, R² and R³ are hydrogen and R⁴ is cyclopropyl, cyclobutyl or 2,2-dichIorocyclopropyl.

A compound of formula I or formula 1.1 wherein A is substituted with any combination of 1 to 3 groups R^a other than hydrogen.

A compound of formula I or formula 1.1 wherein A is substituted with hydrogen.

A compound of formula I or formula 1.1 wherein R^a is hydrogen, halogen, cyano, nitro, d-Ce-alkyl, CrC₆-haloalkyl, C₃-C₆-cylcoalkyl, C₃-C₆-halocycloalkyl, Ci-C₆-aIkoxy, d- Ce-haloalkoxy, CrC₆-alkylthio, Ci-C₆-haloalkylthio, or Ci-C₆-alkylsulfonyl.

A compound of formula I or formula 1.1 wherein R^a is hydrogen, fluorine, chlorine, bromine, cyano, nitro, CrCβ-alkyl, CrC₄-haloalkyl, Ci-C4-aIkoxy, Ci-C4-haloalkoxy, CrC₄- alkylthio, or Ci-C4-haloalkyIthio.

A compound of formula I or formula 1.1 wherein the heterocyclic radical A is an unsaturated 5-membered heterocyclic ring containing 3 heteroatoms selected from nitrogen, oxygen and sulfur, preferably 2 nitrogen heteroatoms and 1 heteroatom selected from oxygen and sulfur.

A compound of formula I or formula 1.1 wherein the heterocyclic radical A is a saturated 5-membered heterocyclic ring containing 3 heteroatoms selected from nitrogen, oxygen and sulfur, preferably tetrahydrofuran, pyrrolidine, imidazolidine, tetrahydrothiophene or oxazolidine.

A compound of formula I or formula 1.1 wherein the heterocyclic radical A is tetrahydrofuran. A compound of formula I or formula 1.1 wherein the heterocyclic radical A is pyrrolidine.

A compound of formula I or formula 1.1 wherein the heterocyclic radical A is imida- zolidine.

A compound of formula I or formula 1.1 wherein the heterocyclic radical A tetrahy- drothiophene.

A compound of formula I or formula 1.1 wherein the heterocyclic radical A oxazolidine.

A compound of formula I or formula 1.1 wherein the heterocyclic radical A is a saturated 5-membered heterocyclic ring containing 3 heteroatoms selected from nitrogen, oxygen and sulfur, preferably tetrahydrofuran, pyrrolidine, imidazolidine, tetrahydrothiophene or oxazolidine, which is substituted by 1 to 2 substituents R^a selected from hydrogen, halogen and CrC4-haloalkyl, preferably from chlorine, fluorine or trifluoromethyl, most preferably from chlorine and fluorine.

A compound of formula I or formula 1.1 wherein A is substituted with any combination of 1 or 2 groups selected from fluorine, chlorine, bromine, cyano, nitro, d-Cβ-alkyl, CrC₄- haloalkyl, Ci-C₄-alkoxy, Ci-C₄-haloalkoxy, Ci-C₄-alkyithio, or Ci-C₄-haIoalkylthio.

A compound of formula I wherein A is selected from table A.

Table A

A.9 A.10 A.11 A.12

A.17 A.18 A.19

In the heterocycles A.1 to A.19 of table A, R^a1 and R^a2 preferably are each indepen- dently hydrogen, methyl, ethyl, propyl, isopropyl, cyclopropyl, 1-methyI-cyclopropyl, tert.-butyl, -CH₂-tert.-butyl, -C(CH₃)₂CH₂CH_3| 1-methylcyclohexyl, cyclohexyl, 1- methylcyclopentyl, cyclopentyl, phenyl, F₁ Cl, Br, CN, NO₂, OCHF₂, OCH₃, OCH₂CH₃, CF₃, SCH₃, or SCF₃, most preferably hydrogen, methyl, isopropyl, tert.-butyl, phenyl, F, Cl, CN, CF₃ or SCF₃.

In the groups A.1 to A.19 of table A, K^ad preferably is metnyl, etnyl, propyl, isopropyl, cyclopropyl, or phenyl. A compound of formula I wherein A is selected from table B.

Table B

A.20 A.21 A.22 A.23

A.24 A.25 A.26

A.27 A.28 In the groups A.20 to A.28 of table B, R^a1 preferably is hydrogen, methyl, ethyl, propyl, isopropyl, cyclopropyl, tert.-butyl, -CH₂-tert.-butyl, -C(CH3)2CH₂CH₃, 1- methylcyclohexyl, cyclohexyl, 1-methylcyclopentyl, cyclopentyl, CF3, phenyl, benzyl, amino, dimethylamino or NHC(=O)CH3, most preferably methyl, ethyl, propyl, isopropyl, cyclopropyl, tert-butyl, -CH₂-tert.-butyl, -C(CH₃)2CH₂CH3, CF₃, phenyl, benzyl, or NHC(=O)CH₃.

In the groups A.20 to A.28 of table B, R^a3 preferably is methyl, ethyl, propyl, isopropyl, cyclopropyl, or phenyl.

A compound of formula I wherein A is selected from table C.

Table C

A.29 A.30 A.31

A.32 A.33 A.34 In the groups A.29 to A.34 of table C the groups R^a1, R^a2, R^a4, and R^a5 preferably are each independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, cyclopro- pyl, 1-methylcycIopropyl, tert.-butyl, -CH₂-tert.-butyl, -C(CH₃)2CH₂CH3, 1- methylcyclohexyl, cyclohexyl, 1-methyIcyclopentyl, cyclopentyl, phenyl, F, Cl, Br, CN, NO₂, OCHF₂, OCH₃, OCH₂CH₃, CF₃, SCH₃, or SCF₃, most preferably hydrogen, CN₁. methyl, F, Cl, or CF₃.

In the groups A.29 to A.34 of table C R^a3 preferably is methyl, ethyl, propyl, isopropyl, cyclopropyl, or phenyl, most preferably methyl.

Preferred are compounds of formula I wherein A is selected from A.1 , A.2, A.3, A.4,

A.11 , A.12, A.15, A.17, A.18, A.21, A.23, A.24, A.25, A.26, A.27, A.28, A29, A.30, A.31 , and A.32.

Preferred are compounds of formula I wherein A is selected from A.1 , A.2, A.3, A.4, A.11, A.12, A.15, A.17 and A.18, all of table A.

Preferred are compounds of formula I wherein A is selected from A.21 , A.23, A.24, A.25, A.26, A.27, and A.28, all of table B.

Preferred are compounds of formula I wherein A is selected from A29, A.30, A.31 , and A.32, all of table C. Especially preferred are compounds of formula I wherein A is as defined at the outset for compounds of formula 1.1.

Also, especially preferred are compounds of formula 1.1. wherein A is A.1 , A.2, A.5 or A.9.

Moreover, especially preferred are compounds of formula 1.1 wherein A is A.5. Also especially preferred are compounds of formula I wherein A is A.9.

Preferred are compounds of formula I or formula 1.1 wherein A is A.1.

Also preferred are compounds of formula I or formula 1.1 wherein A is A.2.

Also preferred are compounds of formula I or formula 1.1 wherein A is A.3.

Also preferred are compounds of formula I or formula 1.1 wherein A is A.4. Also preferred are compounds of formula 1.1 wherein A is A.5.

Also preferred are compounds of formula I wherein A is A.6.

Also preferred are compounds of formula I wherein A is A.7.

Also preferred are compounds of formula I wherein A is A.8.

Also preferred are compounds of formula 1.1 wherein A is A.9. Also preferred are compounds of formula I wherein A is A.10.

Also preferred are compounds of formula I or formula 1.1 wherein A is A.11.

Also preferred are compounds formula I or formula 1.1 wherein A is A.12.

Also preferred are compounds of formula I wherein A is A.13.

Also preferred are compounds of formula I wherein A is A.14. Also preferred are compounds of formula I wherein A is A.15.

Also preferred are compounds of formula I wherein A is A.16.

Also preferred are compounds of formula I or formula 1.1 wherein A is A.17.

Also preferred are compounds of formula I or formula 1.1 wherein A is A.18.

Also preferred are compounds of formula I wherein A is A.19. Also preferred are compounds or formula 1.1 wherein A is A.20.

Also preferred are compounds of formula I or formula 1.1 wherein A is A.21.

Also preferred are compounds of formula 1.1 wherein A is A.22.

Also preferred are compounds of formula I wherein A is A.23.

Also preferred are compounds of formula I or formula 1.1 wherein A is A.24. Also preferred are compounds of formula I or formula 1.1 wherein A is A.25.

Also preferred are compounds of formula I or formula 1.1 wherein A is A.26.

Also preferred are compounds of formula I or formula 1.1 wherein A is A.27.

Also preferred are compounds of formula I or formula 1.1 wherein A is A.28.

Also preferred are compounds of formula I or formula 1.1 wherein A is A.29. Also preferred are compounds of formula I or formula Uwherein A is A.30.

Also preferred are compounds of formula I or formula Mwherein A is A.31.

Also preferred are compounds of formula I or formula l.iwherein A is A.32. Also preferred are compounds of formula I wherein A is A.33. Also preferred are compounds or formula Uwherein A is A.34.

With respect to their use, particular preference is given to the compounds IA compiled in the tables below. Moreover, the groups mentioned for a substituent in the tables are on their own, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituent in question.

Table 1 Compounds of the formula IA wherein R⁴ denotes CH=CHb and A corresponds in each case to a row of Table D.

^A /\ ^R4 (IA)

NC CN

Table 2

Compounds of the formula IA wherein R⁴ denotes CH2-CH=CH2 and A corresponds in each case to a row of Table D.

Table 3

Compounds of the formula IA wherein R⁴ denotes CH2CF3 and A corresponds in each case to a row of Table D.

Table 4

Compounds of the formula IA wherein R⁴ denotes cyclopropyl and A corresponds in each case to a row of Table D.

Table 5

Compounds of the formula IA wherein R⁴ denotes cyclobutyl and A corresponds in each case to a row of Table D.

Table 6 Compounds of the formula IA wherein R⁴ denotes 1-methyI-cyclopropyl and A corresponds in each case to a row of Table D.

Table 7

Compounds of the formula IA wherein R⁴ denotes CF3 and A corresponds in each case to a row of Table D.

Table D

In the intermediates of formula II, the substituents A, R¹ and R² have the same preferred meanings as for compound I.

The compounds of the formula I are especially suitable for efficiently combating the following pests:

insects from the order of the lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Aπticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheima- tobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandi- osella, Ear/as insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bou- liana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha mo- lesta, Heliothis armigera, Heliothis virescens, Heliothis zea, HeIIuIa undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lamb- d/^'πa fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocol- letis blancardella, Lobes/a botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgy/a pseu- dotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frus- trana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia πi and Zeiraphera canadensis,

beetles {Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscu- rus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blasto- phagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napl, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp, Diabrotica longicornis, Diabrotica semipunctata, Diabrotica 12-punctata Diabrotica speciosa, Diabrotica virgifera, EpHa- chna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, lps typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Umonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, O u lema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cocn/eariae, Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, PopiHia japonica, Sitona /meatus and Sito- philus granaria,

flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, An- astrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbi- tae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gaster- ophilus intestinalis, Gloss/ha morsitans, Gloss/ha palpalis, Gloss/ha fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Luc/I/a cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia tit/i/anus, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phor- bia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psoro- phora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sar- cophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula ol- eracea, and Tipula paludosa

thrips ( Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips ssp , Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palm/^' and Thrips tabaci,

termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Termes natalensis, and Coptotermes formosanus,

cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Peri- planeta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis,

true bugs {Hemiptera), e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis nota- tus, Dysdercus cingulatus, Dysdercus intermedins, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridu- Ia, Piesma quadrata, Solubea insularis , Thyanta perditor, Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gos- sypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrtho- siphon pisum, Aulacorthum solaπi, Bemisia argentifolii, Brachycaudus cardui, Brachy- caudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne bras- sicae, Capitophorus horn/,^' Cerosipha gossypii, Chaetosiphoπ fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Macrosiphum euphorbiae, Ma- crosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, My- zus persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Perkiπsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosi- phum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis gram/hum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, Viteus vitifolii, Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatσma spp., and Arilus critatus.

ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinea, Monomorium pha- raonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole megacephala, Dasy- mutilla occidentalis, Bombus spp. Vespula squamosa, Paravespula vulgaris, Paraves- pula pennsylvanica, Paravespula germanica, Dolichovespula macula ta, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema humile,

crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllo- talpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminifera, and Locustana pardalina,

Arachnoidea, such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Ambryomma maculatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis,

Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Ixodes paciffcus, Ornithodorus moubata, Ornithodorus hermsi, Ornithodo- rus turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus sanguineus, Rhipicephalus appendiculatus, Rhipicephalus everts/,^'

Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni, Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus, Tenuipalpidae spp. such as Brevipalpus phoeπicis, Tetra- nychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panony- chus citri, and Oligonychus pratensis, Araneida, e.g. Latrodectus mactans, and Loxos- celes reclusa,

fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides cam^'s, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,

silverfish, firebrat (Thysanura), e.g. Lepisma saccharina and Thermobia domestica,

centipedes (Chilopoda), e.g. Scutigera coleoptrata,

millipedes (Diplopoda), e.g. Narceus spp.,

Earwigs (Dermaptera^ e.g. fonϊcula auricularia,

lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthi- rus pubis, Haematopiπus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon galiinae, Menacanthus stramineus and Solenopotes capillatus,

Plant parasitic nematodes such as root-knot nematodes, Meloidogyne arenaria, Meloi- dogyne chitwoodi, Meloidogyne exigua, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica and other Meloidogyne species; cyst nematodes, Globodera rostochiensis, Globodera pallida, Globodera tabacum and other Globodera species, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; seed gall nematodes, Anguina funesta, Anguina tritici and other Anguina species; stem and foliar nematodes, Aphelenchoides besseyi, Aphelen- choides fragariae, Aphelenchoides ritzemabosi and other Aphelenchoides species; sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species, ring nematodes, Criconema species, Criconemella species, Criconemoides species, and Me- socriconema species; stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci, Ditylenchus myceliophagus and other Ditylenchus species; awl nematodes, Dolichodorus species; spiral nematodes, Helicotylenchus dihystera, Helicotylenchus multicinctus and other Helicotylenchus species, Rotylenchus robustus and other Roty- /enchus species, sheath nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; lance nematodes, Hoplolaimus columbus, Hoplolai- mus galeatus and other Hoplolaimus species, false root-knot nematodes, Nacobbus aberrans and other Nacobbus species; needle nematodes, Longidorus elongates and other Longidorus species; pin nematodes, Paratylenchus species; lesion nematodes, Pratylenchus brachyurus, Pratylenchus coffeae, Pratylenchus curvitatus, Pratylenchus goodeyi, Pratylencus neglectus, Pratylenchus penetrans, Pratylenchus scribneri, Pratylenchus vulnus, Pratylenchus zeae and other Pratylenchus species; Radinaphelen- chus cocophilus and other Radinaphelenchus species; burrowing nematodes, Rado- pholus sim/iis and other Radopholus species; reniform nematodes, Rotylenchulus reni- formis and other Rotylenchulus species; Scutellonema species; stubby root nematodes, Trichodorus primitivus and other Trichodorus species; Paratrichodorus minor and other Paratrichodorus species, stunt nematodes, Tylenchorhynchus claytoni, Tylen- chorhynchus dubius and other Tylenchorhynchus species and Merlinius species; citrus nematodes, Tylenchulus semipenetrans and other Tylenchulus species; dagger nematodes, Xiphinema americanum, Xiphinema index, Xiphinema diversicaudatum and other Xiphinema species, and other plant parasitic nematode species.

Moreover, the compounds of formula I and compositions containing them are espe- cially useful for the control of insects and acarids of the orders Lepidoptera, Coleop- tera, Diptera, Hemiptera, and Hymenoptera.

For use according to the present invention, the compounds I can be converted into the customary formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular purpose; it is intended to ensure in each case a fine and uniform distribution of the compound according to the invention.

The formulations are prepared in a known manner, e.g. by extending the active ingredient with solvents and/or carriers, if desired using emulsifiers and dispersants. Solvents/auxiliaries, which are suitable, are essentially:

- water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used.

- carriers such as ground natural minerals (e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g. highly disperse silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin-sulfite waste liquors and methylcellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol ©octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methylcellulose and ethylene oxide / propylene oxide block copolymers.

Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water.

Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active ingredient. The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

The following are examples of formulations: 1. Products for dilution with water

A Soluble concentrates (SL)

10 parts by weight of a compound according to the invention are dissolved in water or in a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active ingredient dissolves upon dilution with water. B Dispersible concentrates (DC)

20 parts by weight of a compound according to the invention are dissolved in cyclohexanone with addition of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion.

C Emulsifiable concentrates (EC)

15 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5% strength). Dilution with water gives an emulsion.

D Emulsions (EW, EO)

40 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5% strength). This mixture is introduced into water by means of an emulsifier (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion.

E Suspensions (SC, OD)

In an agitated ball mill, 20 parts by weight of a compound according to the invention are milled with addition of dispersant, wetters and water or an organic solvent to give a fine active ingredient suspension. Dilution with water gives a stable suspension of the active ingredient.

F Water-dispersible granules and water-soluble granules (WG, SG) 50 parts by weight of a compound according to the invention are ground finely with addition of dispersants and wetters and made into water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active ingredient.

G Water-dispersible powders and water-soluble powders (WP, SP) 75 parts by weight of a compound according to the invention are ground in a rotor- stator mill with addition of dispersant, wetters and silica gel. Dilution with water gives a stable dispersion or solution with the active ingredient.

2. Products to be applied undiluted

H Dustable powders (DP)

5 parts by weight of a compound according to the invention are ground finely and mixed intimately with 95% of finely divided kaolin. This gives a dustable product. I Granules (GR, FG₁ GG, MG)

0.5 parts by weight of a compound according to the invention is ground finely and associated with 95.5% carriers. Current methods are extrusion, spray drying or the fluidized bed. This gives granules to be applied undiluted.

J ULV solutions (UL)

10 parts by weight of a compound according to the invention are dissolved in an organic solvent, for example xylene. This gives a product to be applied undiluted.

The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, eg. in the form of directly sprayable solutions, powders, gels, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, microcapsules (CS), pellets or tablets, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the active ingredients according to the invention.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.

The active ingredient concentrations in the ready-to-use products can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1%.

The active ingredients may also be used successfully in the ultra-low-volume process (ULV)₁ it being possible to apply formulations comprising over 95% by weight of active ingredient, or even to apply the active ingredient without additives.

Various types of oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active ingredients, if appropriate just immediately prior to use (tank mix). These agents usually are admixed with the agents according to the invention in a weight ratio of 1 :10 to 10:1.

The compounds of formula I are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part) and through trophallaxis and transfer. According to a preferred embodiment of the invention, the compounds of formula I are employed via soil application. Soil application is especially favorable for use against ants, termites, crickets, or cockroaches.

According to another preferred embodiment of the invention, for use against non crop pests such as ants, termites, wasps, flies, mosquitoes, crickets, locusts, or cockroaches the compounds of formula I are prepared into a bait preparation.

The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks. Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources. Gels can be based on aqueous or oily matrices and can be formulated to par- ticular necessities in terms of stickiness, moisture retention or aging characteristics.

The bait employed in the composition is a product which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitoes, crickets etc. or cockroaches to eat it. This attractant may be chosen from feeding stimulants or para and / or sex pheromones. Suitable feeding stimulants are chosen, for example, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, crickets powder, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorgano- saccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey, or from salts such as ammonium sulfate, ammonium carbonate or ammonium acetate. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.

Compositions of this invention may also contain other active ingredients, for example other pesticides, insecticides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides. These additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.

The following list of pesticides together with which the compounds according to the invention can be used, is intended to illustrate the possible combinations, but not to impose any limitation: Organo(thio)phosphates: Acephate, Azamethiphos, Azinphos-methyl, Chlorpyrifos, Chlorpyrifos-methyi, Chlorfenvinphos, Diazinon, Dichlorvos, Dicrotophos, Dimethoate, Disulfoton, Ethion, Fenitrothion, Feπthion, Isoxathion, Malathion, Methamidophos, Me- thidathion, Methyl-Parathion, Mevinphos, Monocrotophos, Oxydemeton-methyl, Paraoxon, Parathion, Phenthoate, Phosalone, Phosmet, Phosphamidon, Phorate, Phoxim, Pirimiphos-methyl, Profenofos, Prothiofos, Sulprophos, Tetrachlorvinphos, Terbufos, Triazophos, Trichlorfon;

Carbamates: Alanycarb, Bendiocarb, Benfuracarb, Carbaryl, Carbofuran, Carbosulfan, Fenoxycarb, Furathiocarb, Indoxacarb, Methiocarb, Methomyl, Oxamyl, Pirimicarb, Propoxur, Thiodicarb, Triazamate;

Pyrethroids: Allethrin, Bifenthrin, Cyfluthrin, Cyhalothrin, Cyphenothrin, Cypermethrin, alpha-Cypermethrin, beta-Cypermethrin, zeta-Cypermethrin Deltamethrin, Esfenvaler- ate, Ethofenprox, Fenpropathrin, Fenvalerate, Imiprothrin, Lambda-Cyhalothrin, Perme- thrin, Prallethrin, Pyrethrin I and II, Silafluofen, Tau-FIuvalinate, Tefluthrin, Tetrame- thrin, Traiomethrin, Transfluthrin;

Growth regulators: a) chitin synthesis inhibitors: benzoyiureas: Chlorfluazuron, Cyramazin, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novaluron, Teflubenzuron, Triflumuron; Buprofezin, Diofenolan, Hexythiazox, Etoxa- zole, Clofentazine; b) ecdysone antagonists: Halofenozide, Methoxyfenozide, Te- bufenozide; c) juvenoids: Pyriproxyfen, Methoprene, Fenoxycarb; d) lipid biosynthesis inhibitors: Spirodiclofen, Spiromesifen, a tetronic acid derivative of formula r¹,

Neonicotinoids: Clothianidine, Dinotefuran, Imidacloprid, Thiamethoxam, Nitenpyram, Nithiazine, Acetamiprid, Thiacloprid;

Pyrazole pesticides: Acetoprole, Ethiprole, Fipronil, Tebufenpyrad, Tolfenpyrad, Va- niliprole;

Various: Abamectin, Acequinocyl, Amidoflumet, Amitraz, Azadirachtin, Benclothiaz, Bifenazate, Bistrifluron, Cartap, Chlorfenapyr, Chlordimeform, Cyflumetofen, Cyromaz- ine, Diafenthiuron, Dimefluthrin, Diofenolan, Emamectin, Endosulfan, Fenazaquin, FIo- nicamid, Fluacyprim, Flubendiamide, Flufenerim, Flupyrazofos, Formetanate, For- metanate hydrochloride, Hydramethylnon, Indoxacarb, Lepimectin, Metaflumizone, Milbemectin, Piperonylbutoxide, Profluthrin, Pyridaben, Pyridalyl, Pymetrozine, Pyra- fluprole, Pyriprole, Spinosad, Sulfur, Tebufenpyrad, Thiocyclam, Tolfenpyrad; N-R'-2,2- dihalo-1 -R"cyclo-propanecarboxamide-2-(2,6-dichloro- α,α,α -tri-fluoro-p- tolyl)hydrazone or N-R'-2,2-di(R'")propionamide-2-(2,6-dichloro- α,α,α -trifluoro-p-tolyl)- hydrazone, wherein R' is methyl or ethyl, halo is chloro or bromo, R" is hydrogen or methyl and R"' is methyl or ethyl; and the aminoisothiazole compound of formula T²,

wherein R' is -CH₂O CH3 or H and R" is -CF2CF2 CF3, anthranilamide compounds of formula F³

wherein B¹ is hydrogen or a chlorine atom, B² is a bromine atom or CF3, and R^B is Ci- Ce-alkyl.

The insects may be controlled by contacting the target parasite/pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of compounds of or compositions of formula I.

"Locus" means a habitat, breeding ground, plant, seed, soil, area, material or environ- ment in which a pest or parasite is growing or may grow.

In general, "pesticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various compounds/compositions used in the invention. A pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.

The compounds or compositions of the invention can also be applied preventively to places at which occurrence of the pests is expected. The compounds of formula I may also be used to protect growing plants from attack or infestation by pests by contacting the plant with a pesticidally effective amount of compounds of formula 1. As such, "contacting" includes both direct contact (applying the compounds/compositions directly on the pest and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the pest and/or plant).

In the case of soil treatment or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m², preferably from 0.001 to 20 g per 100 m².

For use in bait compositions, the typical content of active ingredient is from 0.0001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound. The composition used may also comprise other additives such as a solvent of the active material, a flavoring agent, a preserving agent, a dye or a bitter agent. Its attractiveness may also be enhanced by a special color, shape or texture.

For use in treating crop plants, the rate of application of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.

Compounds of formula I and compositions comprising them can also be used for controlling and preventing infestations and infections in animals including warm-blooded animals (including humans) and fish. They are for example suitable for controlling and preventing infestations and infections in mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur-bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels.

Infestations in warm-blooded animals and fish include, but are not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chig- gers, gnats, mosquitoes and fleas.

The compounds of formula I and compositions comprising them are suitable for systemic and/or non-systemic control of ecto- and/or endoparasites. They are active against all or some stages of development.

Administration can be carried out both prophylactically and therapeutically. Administration of the active compounds is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally. For oral administration to warm-blooded animals, the formula I compounds may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addition, the formula I compounds may be administered to the animals in their drinking wa- ter. For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula I compound, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.

Alternatively, the formula I compounds may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The formula I compounds may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the formula I compounds may be formulated into an implant for subcutaneous administration. In addition the formula I compound may be transdermal^ administered to animals. For parenteral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula I compound.

The formula I compounds may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on for- mulations and in ointments or oil-in-water or water-in-oil emulsions. For topical application, dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the formula I compound. In addition, the formula I compounds may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.

Suitable preparations are:

- Solutions such as oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, pouring-on formulations, gels;

- Emulsions and suspensions for oral or dermal administration; semi-solid prepara- tions;

- Formulations in which the active compound is processed in an ointment base or in an oil-in-water or water-in-oil emulsion base;

- Solid preparations such as powders, premixes or concentrates, granules, pellets, tablets, boluses, capsules; aerosols and inhalants, and active compound-containing shaped articles.

Generally it is favorable to apply solid formulations which release compounds of formula I in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg. The active compounds can also be used as a mixture with synergists or with other ac- tive compounds which act against pathogenic endo- and ectoparasites. In general, the compounds of formula I are applied in parasiticidally effective amount- meaning the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The parasiticidally effective amount can vary for the various compounds/compositions used in the invention. A parasiticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, target species, mode of application, and the like.

Synthesis Examples

With due modification of the starting compounds, the protocols shown in the synthesis examples below were used for obtaining further compounds I. The resulting compounds, together with physical data, are listed in the Table I which follows.

Starting materials such as (3,3,3-trifIuoropropyl)malononitrile, (3,4,4-trifluoro-3- butenyl)malononitrile or (3-butenyl)malononitrile can be obtained following procedures described in WO 04/006677, WO 02/090320 or WO 02/089579, respectively.

The products were characterized by coupled High Performance Liquid

Chromatography / mass spectrometry (HPLC/MS), by NMR or by their melting points. Analytical HPLC column: RP-18 column Chromolith Speed ROD from Merck KgaA, Germany). Elution: acetonitrile + 0.1 % trifluoroacetic acid (TFA) / water + 0.1 % trifluoroacetic acid (TFA) in a ratio of from 5:95 to 95:5 in 5 minutes at 40 ⁰C. MS: Quadrupol electrospray ionisation, 80 V (positiv modus)

The conditions for preparative HPLC were as follows: Purospher Star RP18e Hibar RT 75-25 column (3 μm), elution: acetonitrile + 0.1 % trifluoroacetic acid (TFA) / water + 0.1% trifluoroacetic acid (TFA) in a ratio of from 20:80 to 100:0 in 13 minutes, detection by UV at 205 nm, 214 nm, 254 nm, 280 nm and 400 nm or by MS.

Example 1 , compound 1-1 : Preparation of 2-[2-(4-trifluoromethyI-phenyl)-thiazol-4- ylmethyl]-2-(3,3,3-trifluoropropyl)-malononitriIe

A mixture of 278 mg (1 mmol) 4-chloromethyl-2-(4-trifluoromethyl-phenyl)-thiazole and 276 mg (2 mmol) potassium carbonate in 6 ml DMF was stirred at room temperature for 1h under an argon atmosphere. Subsequently, 162 mg (3,3,3-trifluoropropyl) malononitrile were added and the mixture was stirred overnight at room temperature. After evaporation of volatile materials in vacuo the remaining crude prouct was dissolved in dichloromethane, washed with 15 ml water (2x) and dried over magnesium sulfate. After evaporation of the solvent 81 mg (0.2 mmol, 20 %) of the desired product were obtained. (HPLC/MS: RT = 4.105 min, m/z = 404 [M+H]⁺). Table I

(I)

NC CN

->1

Examples for the action against harmful pests:

1. Activity against Boll weevil {Anthonomus grandis)

The active compounds were formulated in 1 :3 DMSO : water. 10 to 15 eggs were placed into microtiterplates filled with 2% agar-agar in water and 300 ppm formaline. The eggs were sprayed with 20 μl of the test solution, the plates were sealed with pierced foils and kept at 24-26°C and 75-85% humidity with a day/night cycle for 3 to 5 days. Mortality was assessed on the basis of the remaining unhatched eggs or larvae on the agar surface and/or quantity and depth of the digging channels caused by the hatched larvae. Tests were replicated 2 times.

In this test, compounds I-3, 1-7, 1-9 and 1-10 at 2500 ppm showed over 75 % mortality compared to 0% mortality of untreated controls.

2. Activity against Mediterranean fruitfly {Ceratitis capitata)

The active compounds were formulated in 1 :3 DMSO : water. 50 to 80 eggs were placed into microtiterplates filled with 0.5% agar-agar and 14 % diet in water. The eggs were sprayed with 5 μl of the test solution, the plates were sealed with pierced foils and kept at 27-29°C and 75-85% humidity under fluorescent light for 6 days. Mortality was assessed on the basis of the agility of the hatched larvae. Tests were replicated 2 times.

In this test, compounds I-4 and I-6 at 2500 ppm showed over 75 % mortality compared to 0% mortality of untreated controls.

3. Activity against Tobacco budworm (Heliothis virescens)

The active compounds were formulated in 1 :3 DMSO : water. 15 to 25 eggs were placed into microtiterplates filled with diet. The eggs were sprayed with 10 μl of the test solution, the plates were sealed with pierced foils and kept at 27-29°C and 75-85% humidity under fluorescent light for 6 days. Mortality was assessed on the basis of the agility and of comparative feeding of the hatched larvae. Tests were replicated 2 times.

4. Activity against Vetch aphid (Megoura viciae)

The active compounds were formulated in 1 :3 DMSO : water. Bean leaf disks were placed into microtiterplates filled with 0.8% agar-agar and 2.5 ppm OPUS™. The leaf disks were sprayed with 2.5 μl of the test solution and 5 to 8 adult aphids were placed into the microtiterplates which were then closed and kept at 22-24°C and 35-45% un- der fluorescent light for 6 days. Mortality was assessed on the basis of vital, reproduced aphids. Tests were replicated 2 times.

In this test, compound 1-6 at 2500 ppm showed over 75 % mortality compared to 0% mortality of untreated controls.

5. Activity against Wheat aphid (Rhopalosiphum pad/)

The active compounds were formulated in 1 :3 DMSO : water. Barlay leaf disk were placed into microtiterplates filled with 0.8% agar-agar and 2.5 ppm OPUS™ The leaf disks were sprayed with 2.5 μl of the test solution and 3 to 8 adult aphids were placed into the microtiterplates which were then closed and kept at 22-24°C and 35-45% humidity under fluorescent light for 5 days. Mortality was assessed on the basis of vital aphids. Tests were replicated 2 times.

In this test, compound I-6 at 2500 ppm showed over 75 % mortality compared to 0% mortality of untreated controls.

6. Activity against Cotton aphid {Aphis gossypii)

The active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic™ surfactant.

Cotton plants at the cotyledon stage (one plant per pot) were infested by placing a heavily infested leaf from the main colony on top of each cotyledon. The aphids were allowed to transfer to the host plant overnight, and the leaf used to transfer the aphids was removed. The cotyledons were dipped in the test solution and allowed to dry. After 5 days, mortality counts were made.

In this test, compounds 1-1 , 1-9 and 1-10 at 300 ppm showed over 50% mortality compared to 0% mortality of untreated controls.

7. Activity against Southern armyworm (Spodoptera eridania), 2nd instar larvae

The active compounds were formulated for testing the activity against insects and a- rachnids as a 10.000 ppm solution in a mixture of 35% acetone and water, which was diluted with water, if needed.

A Sieva lima bean leaf was dipped in the test solution and allowed to dry. The leaf was then placed in a petri dish containing a filter paper on the bottom and ten 2nd instar caterpillars. At 5 days, observations are made of mortality and reduced feeding. In this test, compound 1-3 at 300 ppm showed over 75% mortality compared to 0% mortality of untreated controls.

6. Activity against Argentine ant {Linepithema humile), harvester ant {Pogonomyrmex californicus), acrobat ant {Crematogaster spp.), carpenter ant {Camponotus floridanus), fire ant {Solenopsis invicta), house fly (Mυsca domestica), stable fly {Stomoxys calci- trans), flesh fly {Sarcophaga sp.), yellowfever mosquito (Aedes aegyptil), house mosquito {Culex quinquefasciatus), malaria mosquito {Anopheles albimanus), German cockroach {Blattella Germanica), cat flea {Ctenocephalides felis), and brown dog tick {Rhipicephalus sanguineus) via glass contact

Glass vials were treated with 0.5 ml of a solution of active ingredient in acetone and allowed to dry. Insects or ticks were placed into each vial together with some food and moisture supply. The vials were kept at 22⁰C and were observed for treatment effects at various time intervals. .

9. Activity against yellowfever mosquito {Aedes aegyptil), house mosquito {Culex quinquefasciatus) and malaria mosquito {Anopheles albimanus) larvae via water treatment

Well plates were used as test arenas. The active ingredient was dissolved in acetone and diluted with water to obtain the concentrations needed. The final solutions containing appr. 1 % acetone were placed into each well. Approximately 10 mosquito larvae (^-instars) in 1 ml water were added to each well. Larvae were fed one drop of liver powder each day. The dishes were covered and maintained at 22°C. Mortality was recorded daily and dead larvae and live or dead pupae were removed daily. At the end of the test remaining live larvae were recorded and percent mortality was calculated.

Claims

Claims:

1. Malononitrile compounds of formula I

wherein

R¹ is hydrogen, CrCio-aIkyl, Ci-Cio-haloalkyl, C₂-Cio-alkenyl, C₂-CiO- haloalkenyl, C2-Cio-alkynyl, or C₃-Cio-haloalkynyl;

R² is hydrogen, cyano, CrCio-aIkyl, CrCio-haloalkyl, C2-Cio-alkenyl, C2-C10- haloalkenyl, C₂-Cio-alkynyl, C₃-Cio-haloa!kynyl, C₃-C6-cycloalkyl, C3-C6- halocycloalkyl, Ci-Cio-alkoxy, or CrCio-haloalkoxy;

R³ and R⁴ each independently are hydrogen, Ci-Cio-alkyl, CrC₁₀-haIoalkyl, C₂- Cio-alkenyl, C₂-Cio-haloalkenyl, C₂-Cio-alkynyI, C₃-Cio-haloalkynyl, C3-C10- cycloalkyl, C3-Cio-halocycloalkyl, C₄-C6-cycloalkenyl, C₄-C₆- halocycloalkenyl, or R³ and R⁴ together can be C₂-Cio-alkylene, C₂-Cio-haloalkylene, C₄-CiO- alkenylene or C₄-Cio-haloalkenylene,

A is a saturated or unsaturated 5-membered heterocyclic radical which may contain 2 to 4 heteroatoms selected from oxygen, nitrogen and sulfur, and which may be fused with another 5-or 6-membered saturated or unsaturated heterocyclic ring or with a phenyl ring, wherein the saturated or unsaturated 5-membered heterocyclic radical and the 5-or 6-membered heterocyclic ring or phenyl with which it is fused each is substituted with any combination of 1 to 6 groups R^a;

R^a is hydrogen, halogen, hydroxyl, cyano, nitro, CrCio-aIkyl, C1-C10- haloalkyl, C₃-Cio-cylcoaIkyl, C₃-Cio-halocycIoalkyl, C₂-Cio-alkenyl, C₂- Cio-haloalkenyl, C2-Cio-alkynyl, C₃-Cio-haloalkynyl, Ci-Cio-alkoxy, Ci- Cio-haloalkoxy, C∑-Cio-alkenyloxy, C∑-Cio-haloalkenyloxy, C2-C10- alkynyloxy, C3-Cio-halo-alkynyloxy, Ci-Cio-alkylthio, C1-C10- haloalkylthio, Ci-Cio-alkylsulfinyl, Ci-Cio-haloalkylsuIfinyl, C1-C10- alkylsulfonyl, Ci-Cio-haloalkylsulfonyl, NR⁵R⁶, Ci-Cio-alkoxycarbonyl, Ci-C₁₀-haloalkoxycarbonyl, C2-Cio-alkenyloxycarbonyl, C₂-C10- haloalkenyloxycarbonyl, CrCio-alkyI-carbonyl, C₁-C10- haloalkylcarbonyl, Ci-Cio-alkylcarbonyloxy, C1-C10- haloalkylcarbonyloxy, R⁵R⁶N-C(=O), phenyl, benzyl, furyl, thienyl, pyridyl, phenoxy or phenylthio, wherein the carbon atoms in the latter 7 rings are unsubstituted or substituted with any combination of 1 to 5 groups R^b;

R^b is halogen, hydroxy, cyano, nitro, Ci-Cio-alkyl, CrCio-haloalkyl, C3- Cio-cylcoalkyl, C3-C-io-halocycloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C3-Cio-haloalkynyl, Ci-Cio-alkoxy, CrCio-haloalkoxy, Ci-Cio-alkylthio, d-Cio-haloalkylthio, Ci-Cio-alkylsulfinyl, C1-C₁0- haloalkylsulfinyl, C_rCio-alkylsulfonyl, Ci-Cio-haloalkylsulfonyl, NR⁵R⁶,

Ci-C-io-alkoxycarbonyl, Ci-Cio-haloalkoxycarbonyl, d-Cio-alkylcarbonyl, CrCio-haloalkylcarbonyl or R⁵R⁶N-CO-;

R⁵, R⁶ are each independently hydrogen, Ci-Cio-alkyl, CrCio-haloalkyl, d-Cio-alkylcarbonyl, CrCio-haloalkylcarbonyl, benzyl, phenyl, phenyl- carbonyl, Ci-Cio-alkylsulfonyl, or Ci-Cio-haloalkylsulfonyl;

or the enantiomers or diastereomers or salts thereof.

Malononitrile 1 having the formula 1.1

wherein

R¹, R², R³ and R⁴ are as defined for compounds of formula I in claim 1;

A is (1) a saturated 5-membered heterocyclic radical which may contain 2 to 4 heteroatoms selected from oxygen, nitrogen and sulfur, and which may be fused with a 5-or 6-membered saturated or unsaturated heterocyclic ring or with a phenyl ring, or

A is (2) an unsaturated 5-membered heterocyclic radical which may contain 2 to 4 heteroatoms selected from oxygen, nitrogen and sulfur, and which may be fused with a 5-or 6-membered saturated or unsaturated heterocyclic ring or with a phenyl ring,

wherein the saturated or unsaturated 5-membered heterocyclic radical and the 5-or 6-membered heterocyclic ring or phenyl with which it is fused each is substituted with any combination of 1 to 6 groups R^a, wherein R^a is as defined in claim 1 for compounds of formula I; and wherein the unsaturated 5-membered heterocyclic radical which may contain 2 to 4 heteroatoms selected from oxygen, nitrogen and sulfur, and which may be fused with a 5-or 6-membered saturated or unsaturated heterocyclic ring or with a phenyl ring is selected from the following:

A.28 A.29 A.30

A.31 A.32 A.34 wherein R^a1, R^a2, R^a3, R^a4 and R^a5 each independently have the meaning as defined in claim 1 for R^a, with the provisos that

(a) for A.5, R^a1 is not methyl, ethyl, tert.-butyl, chlorine, -OCH₂CCH, or - O(CH₂)2CCH when R^a2 is hydrogen; and

(b) for A.9, R^a1 is not methoxy or tert. -butyl when R⁸² is hydrogen; and

(c) for A.20, R^a1 is not tert-butyl; and

(d) for A.22, R^a1 is not ethyl, tert.-butyl, (i-methyl)-cyclopropyl, or neopentyl; and

(e) for A.34, R^a2 is not trifluoromethyl when R^a1 and R^a1 are hydrogen,

or the enantiomers or diastereomers or salts thereof.

3. Malononitrile compounds of formula I according to claims 1 or 2 wherein the 5- membered heterocyclic radical is substituted with any combination of 1 to 3 groups R^a, and R^a is hydrogen, halogen, cyano, nitro, Ci-C₆-alkyl, CrC₆- haloalkyl, C3-C₆-cylcoalkyl, C₃-C6-halocycIoalkyl, CrC₆-aIkoxy, CrC₆-haloalkoxy, d-Cβ-alkylthio, d-Cβ-haloalkylthio, or CrCβ-alkylsulfonyl.

4. Malononitrile compounds of formula I according to claims 1 to 3 wherein A is selected from A.1, A.2, A.3, A.4, A.11 , A.12, A.15, A.17, A.18, A.21, A.23, A.24, A.25, A.26, A.27, A.28, A29, A.30, A.31, and A.32.

A process for the preparation of compounds of formula I as defined in claims 1 to 4 which comprises reacting compounds (II) with compound (III) in the presence of a base to give compounds (I),

(") (I) wherein R¹, R², R³ and R⁴ are as defined in claims 1 to 4 for compounds of formula I and Z¹ represents a halogen atom, methanesulfonyl, trifluoromethanesul- fonyl or toluenesulfonyl.

6. A compound of the formula Il as set out in claim 5.

7. Use of compounds of formula I as defined in claims 1 to 4 for combating insects, acarids, or nematodes.

8. A method for the control of insects, acarids or nematodes by contacting the insect, acarid or nematode or their food supply, habitat, breeding ground or their locus with a pesticidally effective amount of compositions or compounds of formula I as defined in claims 1 to 4.

9. A method of protecting growing plants from attack or infestation by insects, acarids or nematodes by applying to the foliage of the plants, or to the soil or water in which they are growing, a pesticidally effective amount of compositions or compounds of formula I as defined in claims 1 to 4.

10. A method for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of compositions or compounds of formula I as defined in claims 1 to 4 or their enan- tiomers or veterinarily acceptable salts.

11. A process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises a parasiticidally effective amount of compositions or compounds of for- mula I as defined in claims 1 to 4 or their enantiomers or veterinarily acceptable salts.

12. Compositions comprising a pesticidally or parasiticidally active amount of compounds of formula I as defined in claims 1 to 4 and an agronomically or veterinar- ily acceptable carrier.