Compounds of formula (I)    as defined herein, to processes for preparing them, to pesticidal, in particular insecticidal, acaricidal, molluscicidal and nematicidal compositions comprising them and to methods of using them to combat and control pests such as insect, acarine, mollusc and nematode pests.

The present invention relates to pyrazole derivatives, to processes for preparing them, to intermediates for preparing them, to pesticidal, in particular insecticidal, acaricidal, molluscicidal and nematicidal compositions comprising those derivatives and to methods of using them to combat and control pests such as insect, acarine, mollusc and nematode pests.

It has now surprisingly been found that certain pyrazole derivatives have highly potent insecticidal properties. Other compounds in this area are known from WO2014/122083, WO2012/107434, WO2015/067646, WO2015/067647, WO2015/067648, WO2015/150442, WO2015/193218 and WO2010/051926.

Thus, as embodiment 1, the present invention provides a compound of formula (I),

As embodiment 2, there is provided the compound according to embodiment 1 wherein R2is selected from halogen and cyano.

As embodiment 3, there is provided the compound according to embodiment 1 or 2 wherein R2is selected from chloro and cyano.

As embodiment 4, there is provided the compound according to any one of embodiment 1 to 3 wherein R2is cyano.

As embodiment 5, there is provided the compound according to any one of embodiment 1 to 4 wherein Q is cyano.

As embodiment 5.1, there is provided the compound according to any one of embodiment 1 to 4 wherein Q is H.

As embodiment 7, there is provided the compound according to any one of embodiments 1 to 6 wherein R1is selected from H, isobutyl, 2,2,2-trifluoroethyl, —C(═O)CH3, —C(═O)OCH3, —C(═O)OCH2CH3, —C(═O)CH(CH3)(CH3), —CH2—C—CH, —CH2CN, —CH2—O—CH3and —CH2—cyclopropyl.

As embodiment 9, there is provided the compound according to any one of embodiments 1 to 8 wherein Y1and Y3are independently selected from chloro, bromo, —CF3, —OCHF2and methyl.

As embodiment 10, there is provided the compound according to embodiment 1 of formula (I)

As embodiment 11, there is provided the compound according to embodiment 1 of formula (I)

As embodiment 11.1, there is provided the compound according to embodiment 10 or 11 wherein Y5is -i-CF(CF3)(CF3).

As embodiment 12: A compound or salt according to embodiment 1 selected from

Definitions

The term “cycloalkyl” — in isolation or as part of a chemical group — represents saturated or partially unsaturated mono-, bi- or tricyclic hydrocarbons, preferably 3 to 10 carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl or adamantyl.

The term “heterocycloalkyl” — in isolation or as part of a chemical group — represents saturated or partially unsaturated mono-, bi- or tricyclic hydrocarbons, preferably 3 to 10 carbon atoms , for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl or adamantyl, wherein one or more of the ring atoms, preferably 1 to 4, more preferably 1, 2 or 3 of the ring atoms are independently selected from N, O, S, P, B, Si and Se, more preferably N, O and S, wherein no O atoms can be located next to each other.

The term “halogen” or “halo” represents fluoro, chloro, bromo or iodo, particularly fluoro, chloro or bromo. The chemical groups which are substituted with halogen, for example haloalkyl, halocycloalkyl, haloalkyloxy, haloalkylsulfanyl, haloalkylsulfinyl or haloalkylsulfonyl are substituted one or up to the maximum number of substituents with halogen. If “alkyl”, “alkenyl” or “alkynyl” are substituted with halogen, the halogen atoms can be the same or different and can be bound at the same carbon atom or different carbon atoms.

Haloalkyls having 1 to 4 carbon atoms and 1 to 9, preferably 1 to 5 of the same or different halogen atoms selected from fluoro, chloro or bromo, are preferred.

Haloalkyls having 1 or 2 carbon atoms and 1 to 5 gleichen of the same or different halogen atoms selected from fluoro or chloro, for example difluoromethyl, trifluoromethyl or 2,2-difluoroethyl, are particularly preferred.

Haloalkoxy having 1 to 4 carbon atoms are preferred.

Alkylsulfinyls having 1 to 4 carbon atoms are preferred.

Alkylsulfonyls having 1 to 4 carbon atoms are preferred.

The term “alkylcarbonyl” represents straight or branched chain alkyl—C(═O), preferably having 2 to 7 carbon atoms, for example methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, s-butylcarbonyl and t-butylcarbonyl.

Alkylcarbonyls having 1 to 4 carbon atoms are preferred.

The term “alkoxycarbonyl” — in isolation or as part of a chemical group — represents straight or branched chain alkoxycarbonyl, preferably having 1 to 6 carbon atoms or 1 to 4 carbon atoms in the alkoxy part, for example methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, s-butoxycarbonyl and t- butoxycarbonyl.

The term “alkylaminocarbonyl” represents straight or branched chain alkylaminocarbonyl having preferably 1 to 6 carbon atoms orr 1 to 4 carbon atoms in the alkyl part, for example methylaminocarbonyl, ethylaminocarbonyl, n-proylaminocarbonyl, isopropyl- aminocarbonyl, s-butylaminocarbonyl and t-butylaminocarbonyl.

The term “N,N-Dialkylamino-carbonyl” “represents straight or branched chain N,N-dialkylaminocarbonyl with preferably 1 to 6 carbon atoms or 1 to 4 carbon atoms in the alkyl part, for example N,N-Dimethylamino-carbonyl, N,N-diethylamino-carbonyl, N,N-di(n- propylamino)-carbonyl, N,N-di-(isopropylamino)-carbonyl and N,N-di-(s-butylamino)-carbonyl.

The term “aryl” represents a mono-, bi- or polycyclical aromatic system with preferably 6 to 14, more preferably 6 to 10 ring-carbon atoms, for example phenyl, naphthyl, anthryl, phenanthrenyl, preferably phenyl. “Aryl” also represents polycyclic systems, for example tetrahydronaphtyl, indenyl, indanyl, fluorenyl, biphenyl. Arylalkyls are examples of substituted aryls, which may be further substituted with the same or different substituents both at the aryl or alkyl part. Benzyl and 1 -phenylethyl are examples of such arylalkyls.

A compound according to any one of embodiments 1 to 12 which has at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrose acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as C1-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as C1-C4alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane-or p-toluenesulfonic acid. A compounds according to any one of embodiments 1 to 12 which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.

Compounds according to any one of embodiments 1 to 12 also include hydrates which may be formed during the salt formation.

As used herein, when one embodiment refers to several other embodiments by using the term “according to any one of”, for example “according to any one of embodiments 1 to 5”, then said embodiment refers not only to embodiments indicated by the integers such as 1 and 2 but also to embodiments indicated by numbers with a decimal component such as 1.1, 1.2 or 2.1, 2.2, 2.3. For example, “according to any one of embodiments 1 to 3” means for example according to any one of embodiments 1, 1.1, 2, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7.

The compounds according to any one of embodiments 1 to 12 may be made by a variety of methods well known to a person skilled in the art or as shown in Schemes 1 to 5. Further instructions regarding the preparation can be found in WO2015/067646, WO2015/150442, WO2015/193218, WO2014/122083, WO2012/107434 and WO2011/113756.

The compounds according to any one of embodiments may be made by a variety of methods known to a person skilled in the art or as shown in Schemes 1 to 5.

For example, compounds of formula (I) can be prepared according to Scheme 1.

wherein Y1, Y3, Y5, A, R1, Q and R2are as defined in any one of embodiments 1 to 12.

1) Compounds of formula (I) may be prepared by reacting a compound of formula (II) wherein P is OH, C1-C6alkoxy or Cl, F or Br, with an amine of formula (IV), as shown in Scheme 1. When P is OH such reactions are usually carried out in the presence of a suitable coupling reagent, such as N,N′-dicyclohexylcarbodiimide (“DCC”), 1-ethyl-3-(3-dimethylamino-propyl)carbodiimide hydrochloride (“EDC”) or bis(2-oxo-3-oxazolidinyl)phosphonic chloride (“BOP-CI”), in the presence of a base, and optionally in the presence of a nucleophilic catalyst, such as hydroxybenzotriazole (“HOBT”). When P is Cl, such reactions are usually carried out in the presence of a base, and optionally in the presence of a nucleophilic catalyst. Alternatively, it is possible to conduct the reaction in a biphasic system comprising an organic solvent, preferably ethyl acetate, and an aqueous solvent, preferably a solution of sodium hydrogen carbonate. When P is C1-C6alkoxy it is sometimes possible to convert the ester directly to the amide by heating the ester and amine together in a thermal process. Suitable bases include pyridine, triethylamine, 4-(dimethylamino)-pyridine (“DMAP”) or diisopropylethylamine (Hunig’s base). Preferred solvents are N,N-dimethylacetamide, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, ethyl acetate and toluene. The reaction is carried out at a temperature of from 0° C. to 100° C., preferably from 15° C. to 30° C., in particular at ambient temperature.

2) Acid halides of formula (II), wherein P is Cl, F or Br, may be made from carboxylic acids of formula (II), wherein P is OH, under standard conditions, known from a person skilled in the art.

3) Carboxylic acids of formula (II), wherein P is OH, may be formed from esters of formula (II), wherein P is C1-C6alkoxy under standard conditions, known from a person skilled in the art.

4) Compounds of formula (I) may be prepared by reacting a compound of formula (III) wherein X is a leaving group, for example a halogen, such as bromo, with carbon monoxide and an amine of formula (IV), in the presence of a catalyst, such as palladium(II) acetate or bis(triphenylphosphine)palladium(II) dichloride, optionally in the presence of a ligand, such as triphenylphosphine, and a base, such as sodium carbonate, pyridine, triethylamine, 4-(dimethylamino)-pyridine (“DMAP”) or diisopropylethylamine (Hunig’s base), in a solvent, such as water, N,N-dimethylformamide or tetrahydrofuran. The reaction is carried out at a temperature of from 50° C. to 200° C., preferably from 100° C. to 150° C. The reaction is carried out at a pressure of from 50 to 200 bar, preferably from 100 to 150 bar.

6) Compounds of formula (II), wherein P is OH, may be prepared by reacting a compound of formula (III) wherein X is a leaving group, for example a triflate or a halogen, such as bromo, with carbon monoxide or potassium formate, in the presence of a catalyst, such as palladium(II) acetate or bis-(triphenylphosphine)palladium(II) dichloride, optionally in the presence of a ligand, such as triphenylphosphine, diphenylphosphinoferrocene (“dppf”) and a base, such as sodium carbonate, pyridine, triethylamine, 4-(dimethylamino)-pyridine (“DMAP”) or diisopropylethylamine (Hunig’s base), in a solvent, such as water, N,N-dimethylformamide, methyltetrahydrofuran or tetrahydrofuran. The reaction is carried out at a temperature of from 50° C. to 200° C., preferably from 100° C. to 150° C. The reaction is carried out at a pressure of CO from 50 to 200 bar, preferably from 100 to 150 bar.

7) Compounds of formula (II), wherein P is C1-C6alkoxy, may be prepared by reacting a compound of formula (III) wherein X is a leaving group, for example a triflate or a halogen, such as bromo, with carbon monoxide and an alcohol, in the presence of a catalyst, such as palladium(II) acetate or bis-(triphenylphosphine)palladium(II) dichloride, optionally in the presence of a ligand, such as triphenylphosphine, and a base, such as sodium carbonate, pyridine, triethylamine, 4-(dimethylamino)-pyridine (“DMAP”) or diisopropylethylamine (Hunig’s base), in a solvent, such as water, N,N-dimethylformamide, methyltetrahydrofuran or tetrahydrofuran. The reaction is carried out at a temperature of from 50° C. to 200° C., preferably from 100° C. to 150° C. The reaction is carried out at a pressure of carbon monoxide from 50 to 200 bar, preferably from 100 to 150 bar.

8) Alternatively, compounds of formula (II), wherein P is OH, may be prepared by reacting a compound of formula (III) wherein X is a halogen, such as bromo, with magnesium or butyllithium, in order to prepare the intermediate Grignard reagent or respectively the organolithium reagent, followed by its reaction with carbon dioxide, in a solvent, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, methyltetrahydrofuran or tetrahydrofuran. The reaction is carried out at a temperature of from -80° C. to 60° C., preferably from -20° C. to 40° C. The preparation of the intermediate Grignard reagent (halogen-metal reactions) can also be performed using isopropylmagnesium chloride, in the presence or absence of alkali salts, such as lithium chloride.

wherein Y1, Y3, Y5, A and R2are as defined in any one of embodiments 1 to 12.

9) Compounds of formula (II), wherein P is OH or C1-C6alkoxy, may be prepared by reacting a compound of formula (V) wherein U represents a boronic acid, boronic ester or trifluoroboronate or—SnBu3or —ZnCI with a compound of formula (VII), wherein XBrepresents bromine, chlorine, iodine or triflate, using known processes from the literature using palladium-catalyzed reactions. For instance, the reactions can be carried out in the presence of a catalyst, such as palladium(II) acetate, palladium(0) tetrakis-triphenylphosphine or bis(triphenylphosphine)palladium(II) dichloride, optionally in the presence of a ligand, such as triphenylphosphine, diphenylphosphinoferrocene (“dppf”) and a base, such as sodium carbonate, pyridine, triethylamine, 4-(dimethylamino)-pyridine (“DMAP”) or diisopropylethylamine (Hunig’s base), in a solvent, such as water, N,N-dimethylformamide, methyltetrahydrofuran or tetrahydrofuran. The reaction is carried out at a temperature of from 50° C. to 200° C., preferably from 100° C. to 150° C. The compounds of the general structure (VII) are either commercially available or may be prepared by processes known from to the person skilled in the art.

10) Compounds of formula (III) wherein X is a leaving group, for example a triflate or a halogen, such as bromo, may be prepared by reacting a compound of formula (V) wherein U representes a boronic acid, boronic ester or trifluoroboronate or —SnBu3or —ZnCI with a compound of formula (VI), wherein XBrepresents bromo, chloro, iodo or triflate, using known processes from the literature using palladium-catalyzed reactions. For instance, the reactions can be carried out in the presence of a catalyst, such as palladium(II) acetate, palladium(0) tetrakis-triphenylphosphine or bis(triphenylphosphine)palladium(II) dichloride, optionally in the presence of a ligand, such as triphenylphosphine, diphenylphosphinoferrocene (“dppf”) and a base, such as sodium carbonate, pyridine, triethylamine, 4-(dimethylamino)-pyridine (“DMAP”) or diisopropylethylamine (Hunig’s base), in a solvent, such as water, N,N-dimethylformamide, methyltetrahydrofuran or tetrahydrofuran. The reaction is carried out at a temperature of from 50° C. to 200° C., preferably from 100° C. to 150° C. The compounds of the general structure (VI) are either commercially available or may be prepared by processes known from to the person skilled in the art. The compounds of the general structure (V) may be prepared as described in the literature (WO2015067647).

wherein Y1, Y3, Y5, A, R1, Q and R2are as defined in any one of embodiments 1 to 12.

11) Compounds of formula (I), may be prepared by reacting a compound of formula (V) wherein U represents a boronic acid, boronic ester or trifluoroboronate or —SnBu3or —ZnCI with a compound of formula (VIII), wherein XBrepresents bromo, chloro, iodo or triflate, using known processes from the literature using palladium-catalyzed reactions. The compounds of the general structure (VIII) may be prepared by processes known from to the person skilled in the art.

wherein Y1, Y3, Y5, A, R1, Q and R2are as defined in any one of embodiments 1 to 12.

12) Compounds of formula (I), may be prepared by reacting a compound of formula (IX) wherein X is a halogen, with a compound of formula (X), using known processes from the literature, either by nucleophilic substitution at the aromatic ring (X= Cl or F), or by a transition metal-catalyzed reaction (X= Br or I), for instance, using a palladium or copper-catalyzed reactions. The compounds of the general structure (IX) and (Xa) may be prepared by processes known from to the person skilled in the art.

wherein Y1, Y3, Y5, R1, Q and R2are as defined in any one of embodiments 1 to 12.

13) Compounds of formula (la), may be prepared by reacting a compound of formula (XII) with a compound of formula (XI), using known processes from the literature, optionally in the presence of copper or a copper catalyst, such as copper sulfate or copper (I) iodide, and optionally in the presence of a base, such as N-ethyldiisopropylamine, in the presence of a solvent or a mixture of solvents, such as t-butanol, water. In the case of a Cu(ll) catalyst, a reducing agent, such as sodium ascorbate may be used. In the case of a Cu(0) catalyst, such as an amine salt, an oxidising agent may be used. (See, for example: Angewandte Chemie, International Edition (2009), 48(27), 4900-4908 and cited references, Angew. Chem. Int. Ed. 2008, 47, 2182 - 2184 and cited references, and Eur. J. Org. Chem. 2006, 51-68 and cited references. The compounds of the general structure (XI) and (XII) may be prepared by processes known from to the person skilled in the art, or as is described in WO2011/113756.

A compound according to any one of embodiments 1 to 12 can be converted in a manner known per se into another compound according to any one of embodiments 1 to 12 by replacing one or more substituents of the starting compound according to any one of embodiments 1 to 12 in the customary manner by (an)other substituent(s) according to the invention.

Depending on the choice of the reaction conditions and starting materials which are suitable in each case, it is possible, for example, in one reaction step only to replace one substituent by another substituent according to the invention, or a plurality of substituents can be replaced by other substituents according to the invention in the same reaction step.

Salts of compounds of formula (I) can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds according to any one of embodiments 1 to 12 are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.

Salts of compounds according to any one of embodiments 1 to 12 can be converted in the customary manner into the free compounds, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.

Salts of compounds according to any one of embodiments 1 to 12 can be converted in a manner known per se into other salts of compounds according to any one of embodiments 1 to 12, acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.

Depending on the procedure or the reaction conditions, the compounds according to any one of embodiments 1 to 12, which have salt-forming properties can be obtained in free form or in the form of salts.

The compounds according to any one of embodiments 1 to 12 and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the stereoisomers which are possible or as a mixture of these, for example in the form of pure stereoisomers, such as antipodes and/or diastereomers, or as stereoisomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure stereoisomers and also to all stereoisomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.

Diastereomer mixtures or racemate mixtures of compounds according to any one of embodiments 1 to 12, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diasteromers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.

Enantiomer mixtures, such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl celulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the diastereomers, from which the desired enantiomer can be set free by the action of suitable agents, for example basic agents.

Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable stereoisomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.

N-oxides can be prepared by reacting a compound according to any one of embodiments 1 to 12 with a suitable oxidizing agent, for example the H2O2/urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride. Such oxidations are known from the literature, for example from J. Med. Chem., 32 (12), 2561-73, 1989 or WO00/15615.

It is advantageous to isolate or synthesize in each case the biologically more effective stereoisomer, for example enantiomer or diastereomer, or stereoisomer mixture, for example enantiomer mixture or diastereomer mixture, if the individual components have a different biological activity.

The compounds according to any one of embodiments 1 to 12 and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.

The following Examples illustrate, but do not limit, the invention.

The compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm or 0.8 ppm.

The present invention also provides intermediates useful for the preparation of compounds according to any one of embodiments 1 to 12. Certain intermediates are novel and as such form a further aspect of the invention.

One group of novel intermediates are compounds of formula (II)

wherein Y1, Y3, Y5, A and R2are as defined in any one of embodiments 1 to 12, and P is hydroxy, C1-C15-alkoxy or halogen, such as bromo, chloro or fluoro. The preferences for Y1, Y3, Y5, A and R2are the same as the preferences set out for the corresponding substituents of a compound according to any one of embodiments 1 to 12.

Another group of novel intermediates are compounds of formula (III)

wherein Y1, Y3, Y5, A and R2are as defined in any one of embodiments 1 to 12, and X is a halogen, amino, hydroxyl, C1-Csalkoxy, cyano, C1-C8alkylsulfonyloxy, C1-C8haloalkylsulfonyloxy, C1-Csarylsulfonyloxy, optionally substituted C1-C8arylsulfonyloxy (aryl is preferably phenyl), diazonium salts (e.g. X is —N2+CI—, —N2+BF4—, —N2+Br, —N2+PF6-), phosphonate esters (e.g. —OP(O)(OR′)2, wherein R′ is methyl or ethyl), preferably bromo, iodo, chloro, cyano, trifluoromethylsulfoxy, p-toluenesulfoxy, diazonium chloride. The preferences for Y1, Y3, Y5, A and R2are the same as the preferences set out for the corresponding substituents of a compound according to any one of embodiments 1 to 12.

One group of novel intermediates are compounds of formula (XI)

wherein R1, R2and Q are as defined in any one of embodiments 1 to 12. The preferences for R1, R2and Q are the same as the preferences set out for the corresponding substituents of a compound according to any one of embodiments 1 to 12.

One group of novel intermediates are compounds of formula (X)

wherein R1, R2, A and Q are as defined in any one of embodiments 1 to 12. The preferences for R1, R2, A and Q are the same as the preferences set out for the corresponding substituents of a compound according to any one of embodiments 1 to 12.

One group of novel intermediates are compounds of formula (VIII)

wherein R1, R2and Q are as defined in any one of embodiments 1 to 12 and X is a halogen, amino, cyano, C1-C8alkylsulfonyloxy, C1-C8haloalkylsulfonyloxy, C1-C8arylsulfonyloxy, optionally substituted C1-C8arylsulfonyloxy (aryl is preferably phenyl), diazonium salts (e.g. X is —N2+Cl—, —N2+BF4—, —N2+Br—, —N2+PF6-), phosphonate esters (e.g. —OP(O)(OR′)2, wherein R′ is methyl or ethyl), preferably bromo, iodo, chloro, cyano, trifluoromethylsulfoxy, p-toluenesulfoxy and diazonium chloride. The preferences for R1, R2and Q are the same as the preferences set out for the corresponding substituents of a compound according to any one of embodiments 1 to 12.

The compounds according to any one of embodiments 1 to 12 are preventively and/or curatively valuable active ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. The active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina. The insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i. e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate.

The active ingredients according to the invention can be used for controlling, i. e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.

The active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops. The active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca(preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).

The term “crops” is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.

In the context of the present invention there are to be understood by δ-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO02/15701). Truncated toxins, for example a truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO03/018810).

Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO93/07278, WO95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).

Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry1 Ac toxin); Bollgard I® (cotton variety that expresses a Cry1Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a Cry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I’Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modifiedZea mayswhich has been rendered resistant to attack by the European corn borer (Ostrinia nubilalisandSesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I’Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modifiedZea mayswhich has been rendered resistant to attack by the European corn borer (Ostrinia nubilalisandSesamia nonagrioides) by transgenic expression of a Cry1Ab toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I’Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02.6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry1 F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.7. NK603 × MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 × MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained fromAgrobacteriumsp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1Ab toxin obtained fromBacillus thuringiensissubsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS (Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch). The term “crops” is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called “pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO95/33818 and EP-A-0 353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

Crops may also be modified for enhanced resistance to fungal (for example Fusarium, Anthracnose, or Phytophthora), bacterial (for example Pseudomonas) or viral (for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus) pathogens.

Crops also include those that have enhanced resistance to nematodes, such as the soybean cyst nematode.

Crops that are tolerant to abiotic stress include those that have enhanced tolerance to drought, high salt, high temperature, chill, frost, or light radiation, for example through expression of NF-YB or other proteins known in the art.

Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called “pathogenesis-related proteins” (PRPs; see e.g. EP-A-0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO95/33818) or protein or polypeptide factors involved in plant pathogen defence (so-called “plant disease resistance genes”, as described in WO 03/000906).

Further areas of use of the compositions according to the invention are the protection of stored goods and store rooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.

The present invention also provides a method for controlling pests (such as mosquitoes and other disease vectors; see also http://www.who.int/malaria/vector_control/irs/en/). In one embodiment, the method for controlling pests comprises applying the compositions of the invention to the target pests, to their locus or to a surface or substrate by brushing, rolling, spraying, spreading or dipping. By way of example, an IRS (indoor residual spraying) application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention. In another embodiment, it is contemplated to apply such compositions to a substrate such as non-woven or a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.

In another embodiment, the method for controlling such pests comprises applying a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate. Such application may be made by brushing, rolling, spraying, spreading or dipping the pesticidal composition of the invention. By way of example, an IRS application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention so as to provide effective residual pesticidal activity on the surface. In another embodiment, it is contemplated to apply such compositions for residual control of pests on a substrate such as a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.

Substrates including non-woven, fabrics or netting to be treated may be made of natural fibres such as cotton, raffia, jute, flax, sisal, hessian, or wool, or synthetic fibres such as polyamide, polyester, polypropylene, polyacrylonitrile or the like. The polyesters are particularly suitable. The methods of textile treatment are known, e.g. WO 2008/151984, WO 2003/034823, US 5631072, WO 2005/64072, WO2006/128870, EP 1724392, WO2005113886 or WO 2007/090739.

Further areas of use of the compositions according to the invention are the field of tree injection/trunk treatment for all ornamental trees as well all sort of fruit and nut trees.

In the field of tree injection/trunk treatment, the compounds according to the present invention are especially suitable against wood-boring insects from the orderLepidopteraas mentioned above and from the orderColeoptera, especially against woodborers listed in the following tables A and B:

In the hygiene sector, the compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.

The compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.

In one aspect, the invention therefore also relates to pesticidal compositions such as emulsifiable concentrates, suspension concentrates, microemulsions, oil dispersibles, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances, which comprise - at least - one of the active ingredients according to any one of embodiments 1 to 12 and which are to be selected to suit the intended aims and the prevailing circumstances. In these compositions, the active ingredient is employed in pure form, a solid active ingredient for example in a specific particle size, or, preferably, together with — at least — one of the auxiliaries conventionally used in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants).

Examples of suitable solvents are: unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably the fractions C8to C12of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols such as ethanol, propanol or butanol, glycols and their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-methylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, unepoxidized or epoxidized vegetable oils, such as unexpodized or epoxidized rapeseed, castor, coconut or soya oil, and silicone oils.

Solid carriers which are used for example for dusts and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly disperse silicas or highly disperse absorbtive polymers. Suitable adsorptive carriers for granules are porous types, such as pumice, brick grit, sepiolite or bentonite, and suitable non-sorptive carrier materials are calcite or sand. In addition, a large number of granulated materials of inorganic or organic nature can be used, in particular dolomite or comminuted plant residues.

Suitable surface-active compounds are, depending on the type of the active ingredient to be formulated, non-ionic, cationic and/or anionic surfactants or surfactant mixtures which have good emulsifying, dispersing and wetting properties. The surfactants mentioned below are only to be considered as examples; a large number of further surfactants which are conventionally used in the art of formulation and suitable according to the invention are described in the relevant literature.

Suitable non-ionic surfactants are, especially, polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, of saturated or unsaturated fatty acids or of alkyl phenols which may contain approximately 3 to approximately 30 glycol ether groups and approximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatic hydrocarbon radical or approximately 6 to approximately 18 carbon atoms in the alkyl moiety of the alkyl phenols. Also suitable are water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopolypropylene glycol or alkyl polypropylene glycol having 1 to approximately 10 carbon atoms in the alkyl chain and approximately 20 to approximately 250 ethylene glycol ether groups and approximately 10 to approximately 100 propylene glycol ether groups. Normally, the abovementioned compounds contain 1 to approximately 5 ethylene glycol units per propylene glycol unit. Examples which may be mentioned are nonylphenoxypolyethoxyethanol, castor oil polyglycol ether, polypropylene glycol/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol or octylphenoxypolyethoxyethanol. Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are, especially, quarternary ammonium salts which generally have at least one alkyl radical of approximately 8 to approximately 22 C atoms as substituents and as further substituents (unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates. Examples are stearyltrimethylammonium chloride and benzylbis(2-chloroethyl)ethylammonium bromide.

Examples of suitable anionic surfactants are water-soluble soaps or water-soluble synthetic surface-active compounds. Examples of suitable soaps are the alkali, alkaline earth or (unsubstituted or substituted) ammonium salts of fatty acids having approximately 10 to approximately 22 C atoms , such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which are obtainable for example from coconut or tall oil; mention must also be made of the fatty acid methyl taurates. However, synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates. As a rule, the fatty sulfonates and fatty sulfates are present as alkali, alkaline earth or (substituted or unsubstituted) ammonium salts and they generally have an alkyl radical of approximately 8 to approximately 22 C atoms, alkyl also to be understood as including the alkyl moiety of acyl radicals; examples which may be mentioned are the sodium or calcium salts of lignosulfonic acid, of the dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonyl groups and a fatty acid radical of approximately 8 to approximately 22 C atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of decylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensate. Also possible are, furthermore, suitable phosphates, such as salts of the phosphoric ester of a p-nonylphenol/(4-14)ethylene oxide adduct, or phospholipids.

As a rule, the compositions comprise 0.1 to 99%, especially 0.1 to 95%, of active ingredient and 1 to 99.9%, especially 5 to 99.9%, of at least one solid or liquid adjuvant, it being possible as a rule for 0 to 25%, especially 0.1 to 20%, of the composition to be surfactants(% in each case meaning percent by weight). Whereas concentrated compositions tend to be preferred for commercial goods, the end consumer as a rule uses dilute compositions which have substantially lower concentrations of active ingredient.

Typically, a pre-mix formulation for foliar application comprises 0.1 to 99.9%, especially 1 to 95%, of the desired ingredients, and 99.9 to 0.1%, especially 99 to 5%, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50%, especially 0.5 to 40%, based on the pre-mix formulation.

Normally, a tank-mix formulation for seed treatment application comprises 0.25 to 80%, especially 1 to 75%, of the desired ingredients, and 99.75 to 20%, especially 99 to 25%, of a solid or liquid auxiliaries (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 40%, especially 0.5 to 30%, based on the tank-mix formulation.

Typically, a pre-mix formulation for seed treatment application comprises 0.5 to 99.9%, especially 1 to 95%, of the desired ingredients, and 99.5 to 0.1%, especially 99 to 5%, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50%, especially 0.5 to 40%, based on the pre-mix formulation.

Whereas commercial products will preferably be formulated as concentrates (e.g., pre-mix composition (formulation)), the end user will normally employ dilute formulations (e.g., tank mix composition).

Preferred seed treatment pre-mix formulations are aqueous suspension concentrates. The formulation can be applied to the seeds using conventional treating techniques and machines, such as fluidized bed techniques, the roller mill method, rotostatic seed treaters, and drum coaters. Other methods, such as spouted beds may also be useful. The seeds may be presized before coating. After coating, the seeds are typically dried and then transferred to a sizing machine for sizing. Such procedures are known in the art.

In general, the pre-mix compositions of the invention contain 0.5 to 99.9 especially 1 to 95, advantageously 1 to 50%, by mass of the desired ingredients, and 99.5 to 0.1, especially 99 to 5%, by mass of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries (or adjuvant) can be a surfactant in an amount of 0 to 50, especially 0.5 to 40%, by mass based on the mass of the pre-mix formulation.

Examples of formulation types suitable for tank-mix compositions are solutions, dilute emulsions, suspensions, or a mixture thereof, and dusts.

Preferred compositions are composed in particular as follows (% = percent by weight):

EXAMPLES

The following compounds according to embodiment 1 may be prepared according to the methods described herein or according to known methods.

Experimental

The following examples are intended to illustrate the invention and are not to be construed as being limitations thereon.

“Mp” means melting point in °C.1H NMR measurements were recorded on a Brucker 400 MHz spectrometer, chemical shifts are given in ppm relevant to a TMS standard. Spectra measured in deuterated solvents as indicated.

LC MS Method A Standard

LC MS Method B Standard Long

LC MS Method C Unpolar

Example 1: Preparation of 2-cyano-N-cyclopropyl-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxamide

To a solution of ethyl 2,5-dibromothiophene-3-carboxylate (4 g) in 12 mL DMF were added copper cyanide (1.23 g) and Pd(PPh3)4(291 mg) and the reaction mixture was heated to 80° C. for 21 h. The reaction mixture was poured onto 200 mL of a stirred mixture of ethyl acetate/cyclohexane (3:1), the solids were filtered off through a pad of celite and the filtrate was washed three times with a saturated aqueous solution of sodium carbonate then once with brine. The organic phase was dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (silica, cyclohexne / ethyl acetate) to afford the title product as a white solid.1H NMR (400 MHz, CDCI3) δ ppm 1.45 (t, 3 H), 4.55 (q, 3 H), 7.58 (s, 1H). LC-MS (Method A): tR= 0.99 min, m/z = 260 [M+1], 262 [M+3].

b) Preparation of 5-bromo-2-cvano-thiophene-3-carboxvlic acid

A solution of ethyl 5-bromo-2-cyano-thiophene-3-carboxylate (0.250 g) in tetrahydrofurane (3.44 ml) and water (0.96 ml) was treated with lithium hydroxide (0.101 g) and was stirred at 20° C. for 2 hours. The reaction mixture was acidified with conc. Aqueous hydrochloric acid and the mixture was extracted with ethyl acetate. The organic layer was washed with water, then with brine and dried over sodium sulfate. Evaporation of the solvent yielded the title compound as a yellow powder that was used without purification for the following step.

c) Preparation of 5-bromo-2-cyano-N-cyclopropyl-thiophene-3-carboxamide

A solution of 5-bromo-2-cyano-thiophene-3-carboxylic acid (0.228 g) in dichloromethane (4.55 ml) was treated with oxalyl chloride (0.231 g) and a catalytic amount of N,N-dimethylformamide. After 0.5 hour, the reaction mixture was concentrated under reduced pressure and the residue was dissolved in tetrahydrofurane (4.5 ml). This solution was slowly added to a solution of cyclopropylamine (0.106 g) in tetrahydrofurane (4.5 ml) under stirring. After 15 hours, the reaction mixture was treated with an aqueous solution of sodium hydrogen carbonate and extracted twice with dichloromethane. The organic phase was dried over sodium sulfate. The crude product was purified by chromatography over silica gel, eluting with a mixture of ethyl acetate-cyclohexane (3:7). Evaporation of the selected fractions left the title compound as a pale yellow solid.

d) Preparation of [2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]hydrazine

To a suspension of 2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]aniline ) (3.3 g) in 15 mL solution of HCl (6N) at 0-5° C. was added dropwise a solution of NaNO2(897 mg) in 10 mL water then the solution was stirred for 20 min at 0-5° C. then it was added dropwise at room temperature to the solution of SnCl2(5.68 g) in 25 mL aqueous HCl (6N). The precipiate was filtered and washed with water. The resulting wet cake was suspended in water and the pH was adjusted to 10 and the organic material was extracted into ethyl acetate, the organic phase was dried over sodium sulfate, filtered and evaporated. The crude product was purified by flash chromatography (silica, DCM) to afford the title product as a white solid.

e) Preparation of 1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazole

To the a solution of [2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]hydrazine (424 mg) in EtOH (1.43 mL) were added tetramethoxypropane (202 mg) and H2SO4(62 mg) and the reaction mixture was heated to 80° C. for 3 h. The reaction mixture was partitioned between ethyl acetate and a saturated solution of NaHCO3, the layers were separated, the aqueous phase was extracted with ethyl acetate and the combined organic phase was dried over magniesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography (silica, cyclohexane / gradient of ethyl acetate) to afford the title compound.

f) Preparation of 1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-4-iodo-pyrazole

To a solution of 1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazole (1.81 g) in 25 mL acetonitrile was added dropwise a solution of N-iodosuccinimide (5.36 g) in 35 mL acetonitrile over 10 min and the reaction mixture was heated to reflux for 5 h. The reaction mixture was concentrated under reduced pressure then poured onto of a mixture of ethyl acetate/water, the aqueous phase was separated and extracted twice with ethyl acetate. The combined organic phases were washed with a saturated solution of sodium carbonate then brine and dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (silica, cyclohexne / ethyl acetate) to afford the title product as a beige solid.

g) Preparation of 1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazole

In a microwave tube, 1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-4-iodo-pyrazole (2.23 g), 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-,3,2-dioxaborolane (1.11 g) and potassium acetate (1.09 g) were dissolved in 11 ml dimethylsulfoxide. The mixture was purged with argon for 5 min. [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium (66 mg) was added and the mixture was heated to 80° C. for 4 h. The reaction mixture was diluted with ethyl acetate, filtered through a pad of celite, the filtrate was washed with a saturated solution of ammonium chloride and brine. The organic phase was dried over sodium sulfate, filtered and evaporated. The resulting brown oil was progressed to the next step without purification.

h) Preparation of ethyl 2-cyano-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxylate

In a flask, 1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazole (467 mg), 1 ethyl 5-bromo-2-cyano-thiophene-3-carboxylate (200 mg) were dissolved in 5.4 mL of DMF. The mixture was purged with argon for 5 min then Pd(PPh3)4(89 mg) and a solution of potassium carbonate (322 g) in 0.76 mL of water were added and the mixture was heated at 85° C. for 3 h. The reation mixture was diluted with ethyl acetate, filtered through a pad of celite, the filtrate was washed with water and brine. The organic phase was dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude brown oil was purified by flash chromatography (silica, ethyl acetate/cyclohexane) to afford the tilte compound as an oil.

i) Preparation of 2-cyano-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxylic acid

A mixture of ethyl 2-cyano-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-pyrazol-4-yl]thiophene-3-carboxylate (220 mg), lithium hydroxide (28 mg), tetrahydrofuran (3.1 mL) and water (0.4 mL) was stirred at room temperature for 3 h. The mixture was acidified with 1 N HCl and the product was extracted with ethyl acetate. The extract was dried over sodium sulfate, filtered and evaporated to afford a white solid.

j) Preparation of 2-cyano-N-cyclopropyl-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxamide

To a stirred solution of 2-cyano-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-pyrazol-4-yl]thiophene-3-carboxylic acid (265 mg) in DMF (2 mL) were added HATU (228 mg), cyclopropylamine (33 mg), N,N.diisopropylethylamine (177 mg) and the reaction mixture was stirred at room temperature overnight. The reaction mixture was partitioned between ethyl acetate and a saturated solution of ammonium chloride, the layers were separated and the organic phase was washed with brine, dried over magniesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography (silica, cyclohexane / gradient of ethyl acetate) to afford a white solid.

Example 2: Preparation of 2-chloro-N-cyclopropyl-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxamide

a) Preparation of 2-chloro-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxylic acid

In a flask, 1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazole (892 mg), 5-bromo-2-chloro-thiophene-3-carboxylic acid (200 mg) were dissolved in 4.9 mL of DMF. The mixture was purged with argon for 5 min. Pd(PPh3)4(96 mg) and a solution of potassium carbonate (347 mg) in 1.0 mL of water were added and the mixture was heated at 80° C. for 3 h. The mixture was diluted with ethyl acetate and poured onto a solution of HCl 0.5 M, the mixture was extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and evaporated. The crude was redisolved in DCM and extracted with an aqueous solution of NaOH (0.5 M), the combined basic water phase was acidified to pH=2 with an aqueous solution of HCl (6N) and extracted with ethyl acetate three times. The combined organic phases were dried over sodium sulfate, filtrated and evaporated to give the title product as a beige solid.

b) Preparation of 2-chloro-N-cyclopropyl-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxamide

To a stirred solution of 2-chloro-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)-ethyl]phenyl]pyrazol-4-yl]thiophene-3-carboxylic acid (175 mg) in DMF (1.2 mL) were added HATU (164 mg), cyclopropylamine (24 mg), N,N.diisopropylethylamine (127 mg) and the reaction mixture was stirred at room temperature for 2 h. The reaction mixture was partitioned between ethyl acetate and a saturated solution of ammonium chloride, the layers were separated and the organic phase was washed with brine, dried over magniesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography (silica, cyclohexane / gradient of ethyl acetate) to afford the title compound as a white solid.

a) Preparation of 2-azido-1,3-dichloro-5-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]benzene

To a stirred solution of con.HCI (80 mL) and H2O (40 mL), 2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]aniline (5.00 g) was added followed by NaNO2(1.00 g) at 0° C. The reaction mixture was stirred for 10 min,tBuOH (40 mL) and NaN3(1.5 g) were added and the whole was stirred for 18 h. The aqueous layer was extracted twice with ethyl acetate (200 ml).The combined organic phases were dried over sodium sulfate and concentrated. The residue was purified by column chromatography (PE: EA=10:1) to afford the title compound (4 g)1H NMR (400 MHz, cdcl3) δ 7.53 (s, 2H).

b) Preparation of ethyl 2-chloro-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]thiophene-3-carboxylate

c) Preparation of 2-chloro-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]thiophene-3-carboxylic acid

To a solution of ethyl 2-chloro-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]thiophene-3-carboxylate (1.54 g) in EtOH (10 ml) was added NaOH (220 mg) and water (1 ml). The mixture was stirred for 2 h at room temperature and then acidified with 1 N HCl. The mixture was extracted with dichloromethane. The extract was dried over magnesium sulfate and evaporated to afford title compound as a yellow solid.

To a solution of 2-chloro-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]thiophene-3-carboxylic acid (100 mg) in 3 ml of DMF was added 1-aminocyclopropanecarbonitrile hydrochloride (50 mg), HATU (110 mg) and DIPEA (100 mg) and the reaction mixture was stirred at room temperature overnight and then poured into water (50 mL). The aqueous solution was then extracted 3 times with ethyl acetate (150 mL), the combined organic phases were washed twice with brine (200 mL) before being dried on magnesium sulfate, filtered and concentrated. The residue was purified by flash chromatography on silica gel using PE/EA(4:1) as eluent to afford title compound (65 mg).

To a solution of 2-chloro-N-(1-cyanocyclopropyl)-5-[1-[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]triazol-4-yl]thiophene-3-carboxamide (60.0 mg) and Cs2CO3(80 mg) in DMF (0.5 mL) was added iodoethane (60 mg) at room temperature. The mixture was stirred at 50° C. for 1 h, and then diluted with ethyl acetate. The organic layer was washed with water and brine, dried over Na2SO4and concentrated. The residue was further purified by column chromatography eluting with PE:EA=2:1 to give title product (30 mg).

Preparation of Intermediates

Preparation of 2-cyano-N-cyclopropyl-5-(2-trimethylsilylethynyl)thiophene-3-carboxaide

To a solution of 5-bromo-2-cyano-N-cyclopropyl-thiophene-3-carboxamide (1.49 g) in tetrahydrufurane (38.5 ml), under inert atmosphere, was addedN,N-diisopropylethylamine (0.952 g), then cuprous iodide (0.053 g), bis-triphenylphosphine palladium dichloride (0.197 g) and trimethylsilylacetylene (0.826 g).The reaction mixture was stirred for 18 hours at 20° C., at which time, LC-MS analysis showed that the starting material was consumed. The reaction mixture was diluted with ethyl acetate and washed three times with water, then with brine and dried over sodium sulfate. The crude product was purified by chromatography over silica gel, eluting with a mixture of ethyl acetate-cyclohexane. Evaporation of the selected fractions delivered the title compound.

Preparation of 2-cyano-N-cyclopropyl-5-ethynyl-thiophene-3-carboxamide

A solution of 2-cyano-N-cyclopropyl-5-(2-trimethylsilylethynyl)thiophene-3-carboxamide (described above) (1.36 g) in tetrahydrufurane (47 ml), cooled at 0° C., under inert atmosphere, was treated dropwise with a solution of tetrabutylammonium fluoride (1 M in tetrahydrofurane) (9.48 ml). After 20 minutes, LC-MS analysis showed the consumption of the starting material. The reaction was poured into water and the resulting mixture was extracted three times with ethyl acetate. The combined organic layers were washed with brine and dried over sodium sulfate. After removal of the solvent under reduced pressure, the crude product was submitted to chromatography over silica gel, eluting with a mixture of ethyl acetate and cyclohexane. Evaporation of the selected fractions delivered the title compound.

Preparation of methyl 2-chloro-5-iodo-thiophene-3-carboxylate

To a solution of 1.7 g of methyl 2-chlorothiophene-3-carboxylate and 0.1 g of HClO4in 20 mL of CH3CN was added 2.3 g of NIS. The reaction was stirred at room temperature for 6 h then stirred at 50° C. for 24 h. Then the reaction mixture was poured into water and extracted with ethyl acetate three times. The combined organic layers were dried over sodium sulfate, filtered and concentrated under vacuum to give 2.2 g of the title compound.

Preparation of methyl 2-chloro-5-(2-trimethylsilylethynyl)thiophene-3-carboxylate

To a 5 mL dry solution of Et3N solution was successively added 1.2 g of methyl 2-chloro-5-iodo-thiophene-3-carboxylate, 400 mg of ethynyl(trimethyl)silane, 28 mg of PdCl2(PPh3)238 mg of Cul under a N2atmosphere. The mixture was heated at 70° C. for 2 h. After cooling the mixture to room temperature, EtOAc was added and the suspension was filtered through a Celite pad. The filtrate was collected and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel (petroleum ether / ethyl acetate=2:1) to give 1.2 g of title compound.

To a solution of 1.3 g of methyl 2-chloro-5-(2-trimethylsilylethynyl)thiophene-3-carboxylate in 50 mL of THF (50 mL), 10 mL of tetrabutylammonium fluoride (1 M solution in THF) was added dropwise at room temperature. The reaction mixture was stirred at room temperature for 0.5 h. Then the reaction mixture was poured into water and extracted with ethyl acetate three times. The combined organic layers were dried over sodium sulfate, filtered and concentrated under vacuum to give 0.8 g of title product which was used without further purification.

Preparation of 2,5-dibromo-N-cyclopropyl-thiophene-3-carboxamide

A solution of 5-bromo-2-cyano-thiophene-3-carboxylic acid (2.0 g) in dichloromethane (34.97 ml) was treated with oxalyl chloride (1.77 g) and a catalytic amount of N,N-dimethylformamide at room temperature. After 1.5 hour, the reaction mixture was concentrated under reduced pressure and the residue was dissolved in tetrahydrofuran (35 mL). This solution was slowly added to a solution of cyclopropylamine (815 mg) in tetrahydrofuran (35 mL) under stirring. After 1 hour, the reaction mixture was treated with an aqueous solution of sodium bicarbonate and extracted twice with dichloromethan. The organic phase was dried over sodium sulfate. The crude product was purified by chromatography over silica gel, eluting with a mixture of ethyl acetate-cyclohexane (2:8). Evaporation of the selected fractions left the title compound as a white powder.

Preparation of 5-bromo-2-cyano-N-cyclopropyl-thiophene-3-carboxamide

A solution of 5-bromo-2-cyano-thiophene-3-carboxylic acid (221 mg g) in dichloromethan (7.62 ml) was added 1-amino-1-cyclopropanecarbonitrile hydrochloride (124 mg), triethylamne (292 mg), HOAT (146 mg) and EDC hydrochloride (205 mg) and the reaction mixture was stirred at room temperature for 17 h. The reaction mixture was concentrated under vaccum and the residue was purified by chromatography over silica gel, eluting with a mixture of ethyl acetate-cyclohexane. Evaporation of the selected fractions left the title compound as a yellow solid.

The following compounds which have been characterized were prepared in analogy to Example 1, 2, 14 and 16.

Formulation examples (% = percent by weight)Example F1: Emulsion concentratesa)b)c)Active ingredient25%40%50%Calcium dodecylbenzenesulfonate5%8%6%Castor oil polyethylene glycol ether (36 mol of EO)5%--Tributylphenoxypolyethylene glycol ether (30 mol of EO)-12%4%Cyclohexanone-15%20 %Xylene mixture65%25 %20 %Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.

Example F4: Dustsa)b)Active ingredient2%5%Highly disperse silica1%5%Talc97%-Kaolin-90%Ready-to-use dusts are obtained by intimately mixing the carriers and the active ingredient.

Example F7: Coated qranulesActive ingredient3%Polyethylene glycol (MW 200)3%Kaolin94%In a mixer, the finely ground active ingredient is applied uniformLy to the kaolin, which has been moistened with the polyethylene glycol. This gives dust-free coated granules.

Example F8: Suspension concentrateActive ingredient40%Ethylene glycol10%Nonylphenoxypolyethylene glycol ether (15 mol of EO)6%Sodium lignosulfonate10%Carboxymethylcellulose1%37% aqueous formaldehyde solution0.2%Silicone oil (75% aqueous emulsion)0.8%Water32%The finely ground active ingredient is mixed intimately with the additives. Suspensions of any desired concentration can be prepared from the thus resulting suspension concentrate by dilution with water.

Example F9: Powders for dry seed treatmenta)b)c)active ingredient25%50%75%light mineral oil5%5%5%highly dispersed silicic acid5%5%-Kaolin65%40%-Talcum--20%The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.

Example F10: Emulsifiable concentrateactive ingredient10%octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide)3%calcium dodecylbenzenesulfonate3%castor oil polyglycol ether (35 mol of ethylene oxide)4%Cyclohexanone30%xylene mixture50%Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.

Example F11: Flowable concentrate for seed treatmentactive ingredients40%propylene glycol5%copolymer butanol PO/EO2%Tristyrenephenole with 10-20 moles EO2%1 ,2-benzisothiazolin-3-one (in the form of a 20% solution in water)0.5%monoazo-pigment calcium salt5%Silicone oil (in the form of a 75% emulsion in water)0.2%Water45.3%

The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

The activity of the compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients. The mixtures of the compounds according to any one of embodiments 1 to 12 with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use.

The following mixtures of the compounds according to any one of embodiments 1 to 12 with active ingredients are preferred (the abbreviation “TX” means “one compound selected from the compounds according to any one of embodiments 1 to 12, preferably one compound from embodiment 12):

The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The above described mixing partners are known. Where the active ingredients are included in “The Pesticide Manual” [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound “abamectin” is described under entry number (1). Where “[CCN]” is added hereinabove to the particular compound, the compound in question is included in the “Compendium of Pesticide Common Names”, which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2004]; for example, the compound “acetoprole” is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html.

Most of the active ingredients described above are referred to hereinabove by a so-called “common name”, the relevant “ISO common name” or another “common name” being used in individual cases. If the designation is not a “common name”, the nature of the designation used instead is given in round brackets for the particular compound; in that case, the IUPAC name, the IUPAC/Chemical Abstracts name, a “chemical name”, a “traditional name”, a “compound name” or a “develoment code” is used or, if neither one of those designations nor a “common name” is used, an “alternative name” is employed. “CAS Reg. No” means the Chemical Abstracts Registry Number.

The active ingredient mixture of the compounds according to any one of embodiments 1 to 12 with active ingredients described above comprises a compound according to any one of embodiments 1 to 12 and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5:1 and 1:5, special preference being given to a ratio of from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1 :6000, or 1:3000, or 1 :1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750. Those mixing ratios are by weight.

The mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.

The mixtures comprising a compound of according to any one of embodiments 1 to 12 and one or more active ingredients as described above can be applied, for example, in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds according to any one of embodiments 1 to 12 and the active ingredients as described above is not essential for working the present invention.

The compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.

The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds I for the preparation of these compositions are also a subject of the invention.

The application methods for the compositions, that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring — which are to be selected to suit the intended aims of the prevailing circumstances — and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention. Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.

A preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.

The compounds of the invention and compositions thereof are also be suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type. The propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing. Alternatively, the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention. Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds.

The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.

The present invention also comprises seeds coated or treated with or containing a compound according to any one of embodiments 1 to 12. The term “coated or treated with and/or containing” generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the ingredient may penetrate into the seed material, depending on the method of application. When the said seed product is (re)planted, it may absorb the active ingredient. In an embodiment, the present invention makes available a plant propagation material adhered thereto with according to any one of embodiments 1 to 12. Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound according to any one of embodiments 1 to 12.

Seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting. The seed treatment application of the compound according to any one of embodiments 1 to 12 can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds.

The pesticidal/insecticidal properties of the compounds according to any one of embodiments 1 to 12 can be illustrated via the following tests:

Maize sprouts placed onto an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10 ′000 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality 4 days after infestation. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: 1, 2, 3, 4, 10, 11, 12, 13, 14 and 15.

Soybean leaves on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10 ′000 ppm DMSO stock solutions. After drying the leaves were infested with N2 nymphs. The samples were assessed for mortality 5 days after infestation. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 and 12.

Sunflower leaf discs were placed onto agar in a 24-well microtiter plate and sprayed with aqueous test solutions prepared from 10 ′000 ppm DMSO stock solutions. After drying, the leaf discs were infested with an aphid population of mixed ages. The samples were assessed for mortality 6 days after infestation. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: 1, 2, 4, 5 and 8.

24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10 ′000 ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (10 to 15 per well). The samples were assessed for mortality 5 days after infestation. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15.

Cotton leaf discs were placed onto agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10 ′000 ppm DMSO stock solutions. After drying the leaf discs were infested with five L1 larvae. The samples were assessed for mortality 3 days after infestation. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 and 16.

Bean leaf discs on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10 ′000 ppm DMSO stock solutions. After drying the leaf discs were infested with a mite population of mixed ages. The samples were assessed for mortality on mixed population (mobile stages) 8 days after infestation. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12.

Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10 ′000 ppm DMSO stock solutions. After drying the leaf discs were infested with a thrips population of mixed ages. The samples were assessed for mortality 6 days after infestation. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: 1, 2, 3, 4, 10, 11, 12, 13, 14, 15 and 16.

The compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

Furthermore, besides of the insecticidal properties, the compounds according to any one of embodiments 1 to 12 have surprisingly shown to have improved degradation properties compared with prior art compounds. Additionally, the compounds according to any one of embodiments 1 to 12 have surprisingly shown to be less toxic to the environment, e.g. to bees or aquatic organisms, compared with prior art compounds.