Description

The invention relates to compounds of formula I,

jrein

is O, or S;

B ² and B ³ are independently of each other N and CR ^B , with the proviso that at most one of B ¹ , B ² and B ³ is N;

R ^B is H, CI, F, Br, CF ₃ , or OCF ₃ ;

Y is taken together with the carbon atom of CR ² and the C ² and C ³ -atoms of the adjacent X ¹ containing ring to form a 5- to 7-membered saturated or partially unsaturated carbo- or heterocycle where the heterocycle contains 1 to 3 heteroatoms selected from N, O, or S; R ¹ is H, halogen, CN, N0 ₂ , Ci-Ce-alkyl, Ci-C ₆ -haloalkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, Ci-C ₆ - alkoxy, Ci-C6-haloalkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C4-C6-cycloalkynyl, OR ^a , NR ^a R , N0 ₂ , C(=0)OR ^a , C(=0)N(R ^a ) ₂ , or S(0) _m R ^a ; which R ¹ groups are unsubstituted or substituted with one or more R ^a ; or two geminal R ¹ may together form a group =0, =C(R ^a ) ₂ , =NOH, or =NOCH ₃ ;

R ^a and R , independently of each other, are H, Ci-C6-alkyl, Ci-C6-alkoxy, Ci-C6-halo- alkoxy, Ci-C ₆ -alkyl-S(0)m-Ci-C ₆ -alkyl, Ci-C ₆ -alkyl-S(0)m-Ci-C ₃ -haloalkyl, C ₃ -C ₆ - cycloalkyl, C ₂ -C6-alkenyl, C ₂ -C6-alkynyl, C ₂ -C6-alkenyloxy, C ₂ -C6-alkynyloxy, S(0) _m - Ci-C6-alkyl, S(0) _m -Ci-C6-haloalkyl, which groups are unsubstituted or substituted by one or more R ^c ;

R ^c is halogen, CN, CrC ₄ -alkyl, or CrC ₄ -haloalkyl;

m is 0, 1 , or 2;

R ^1a is H, halogen, Ci-C ₄ -alkyl, or Ci-C ₄ -haloalkyl;

n is 1 , 2, 3, or 4;

# is a direct bond, or together with CR ² and NR ³ forms an azetidine ring;

if # is a direct bond:

R ² is H, halogen, CN, N0 ₂ , Ci-C ₆ -alkyl, Ci-C ₆ -haloalkyl, Ci-C ₆ -alkoxy, Ci-C ₆ -haloalk- oxy, Ca-Ce-cycloalkyl, OR ^a , NR ^a R ^b , N0 ₂ ; and

R ³ is a group as defined for R ^a ;

R ⁴ is a group as defined for R ^a ; or Ci-C ₆ -alkyl-S(0)m-Ci-C ₆ -alkyl, Ci-C ₆ -alkyl-S(0)m-Ci-C ₃ -ha- loalkyl, C3-C6-cycloalkyl-Ci-C ₄ -alkyl, 3- to 7-membered heterocyclyl bonded directly or via Ci-C4-alkylene spacer, which heterocycles contain 1 to 3 heteroatoms selected from N, O, or S, wherein S-atoms as ring members are present as S, SO, or S0 ₂ ; and which R ⁴ groups are unsubstituted or substituted by one or more R ^c ; and

and R ⁵ , independently of each other, are H, halogen, or OH;

d the N-oxides, stereoisomers and agriculturally or veterinarily acceptable salts thereof. Moreover, the invention relates to processes and intermediates for preparing the compounds of formula I, and also to active compound combinations, and compositions comprising them, and to their use for protecting growing plants from attack or infestation by invertebrate pests. Furthermore, the invention relates to methods of applying such compounds. The invention also relates to seed comprising such compounds.

Invertebrate pests and in particular arthropods and nematodes destroy growing and harvested crops and attack wooden dwelling and commercial structures, thereby causing large economic loss to the food supply and to property. There is an ongoing need for new agents for combating invertebrate pests such as insects, arachnids and nematodes.

W010/070068, W01 1/157748, W012/107533, WO 12/120135, WO 12/158396, and WO 16/077158 describe dihydroisoxazoles with heterocyclic substituents. These compounds are mentioned to be useful for combating invertebrate pests.

Nevertheless, there remains a need for highly effective and versatile agents for combating invertebrate pests. It is therefore an object of the invention to provide compounds having a good pesticidal activity and showing a broad activity spectrum against a large number of different invertebrate pests, especially against difficult to control pests, such as insects.

It has been found that these objects can be achieved by compounds of formula I as depicted and defined below, and by their stereoisomers, salts, tautomers and N-oxides.

The compounds of the formula I can be prepared by the methods as described below or and in the synthesis descriptions of the working examples, or by standard methods of organic chemistry. The substituents, variables and indices are as defined above for formula I, if not otherwise specified.

Compounds la, that is compounds of formula I wherein R ^5b is hydrogen, can be prepared by reacting compounds of formula lla in an imination/Michael addition reaction with hydroxylamine, as shown below in Scheme . Suitable reaction conditions are described in WO2012/158396 and WO2015/128358. Suitably, hydroxylamine is used as the hydrochloride salt. The reaction is generally carried out in the presence of a base such as, NaOH, KOH, Na2C03. Suitable solvents are aqueous, such as water or mixtures of water with polar organic solvents, such as tetrahydrofuran (THF), dioxane and lower alkanols.

In turn, compounds of formula lla can be prepared in analogy to reports in literature such as, EP2172462 and WO2014/39489. by means of an aldol condensation reaction between compounds of formula Ilia and compounds of formula IVa. Compounds of formula IVa are commercially available, or can be made by standard methods which are described in literature, such as WO2010/125130 and WO2014/206911 , and known to a person skilled in the art.

Scheme 1

Alternatively, compounds of formula la can be prepared in a 1 ,3-dipolar cycloaddition between styrene compounds of formula IVb and nitrile oxides derived from aldoximes of formula Illb wherein Z is hydrogen, as outlined below in Scheme 2. The reaction typically proceeds through the intermediacy of in situ generated hydroxamic acid halogenides, usually chloride, by reaction with chlorine, hypochlorite, N-chlorosuccinimide ("NCS"), or chloramine-T. The halogenating agent is combined with the aldoxime before addition, or in the presence of styrene compound IVb. Depending on the exact conditions, employment of an additional amine base such as triethylamine, Ν,Ν-diisopropylethylamine, or pyridine may be necessary. The reaction can be run in a wide variety of solvents including Ν,Ν-dimethylformamide (DMF), dichloromethane, chlorobenzene, toluene, acetonitrile, THF, ethyl acetate. Compounds of formula IVb are commercially available, or can be made by standard methods which are described in literature, such as WO2012/59441 , WO2008/150393 and WO2012/4326, and known to a person skilled in the art.

Aldoximes of formula Illb', that is compounds of formula Illb wherein Z is hydrogen, can be obtained by reacting aldehydes of formula Illc with hydroxylamine, preferably as its

hydrochloride salt. The reactions are typically performed in the presence of solvents such as, lower alcohols, like methanol and ethanol, water, DMF, acetonitrile, or mixtures thereof.

Optionally, a base can be employed in the reaction such as organic bases like triethylamine, pyridine, or sodium acetate, or inorganic bases such as NaOH or K2CO3.

Compounds I wherein R ^5b is not hydrogen can be prepared from compounds of formula la or la', that is compounds of formula I wherein both, R ^5a and R ⁵ are hydrogen, in analogy to the methods described in WO2010/020521 and WO2015/128358 by reacting these with a base such as lithium diisopropylamide, lithium hexamethyldisilazide, or the like, followed by the addition of an electrophile, e.g. a halogenating agent, such as 4-iodotoluene difluoride, N- fluorobenzenesulfonimide ("NFSI"), N-chlorosuccinimide ("NCS"), N-bromosuccinimide ("NBS"), or N-iodosuccinimide ("NIS"), an alkylating agent, such as alkyl halide, e.g. methyl iodide, a sulfanylating agent, such as methanesulfenyl chloride, S-methyl methanethiosulfonate or dimethyldisulfide, or, for introducing OH, a hydroxylating agent such as, e.g. N- sulfonyloxaziridines, or oxodiperoxymolybdenum(pyridine)-(hexamethylphosphoric triamide) ("MoOPH"). Compounds of formula 111 , in turn, can be obtained by reacting a compound of formula llld with (chloromethylene)dimethyliminium chloride, which can either be obtained from commercial sources or generated in situ by treatment of DMF with an activating agent, usually

trichlorophosphate, in a Vilsmeier-Haak formylation reaction. Suitable reaction conditions are described in US2014/275035 and US2012/123127.

Typical solvents are dichloromethane, chloroform, 1 ,2-dichloroethane, DMF, and mixtures thereof. Alternatively, compounds of formula II lc can be prepared by reacting coumpounds of formula I lie, wherein Q is a halogen, preferably I or Br, with carbon monoxide and a reducing agent in a formylation reaction. Suitable reaction conditions are described in WO2006/35954, WO2012/42006, and WO2010/72781.

The reaction is generally performed in the presence of a palladium catalyst such as, e.g.

bis(triphenylphosphine)palladium(ll) dichloride [PdCl2(PPh ₃ )], palladium(ll) acetate [Pd(OAc)2], (1 ,1 '-bis(diphenylphosphino)ferrocene)palladium(ll) dichloride [PdCI ₂ (dppf)], tetrakis(triphenyl- phosphine)palladium, or the like, and under a carbon monoxide atmosphere of a pressure between 1-50 bars. Suitable reducing agents are, e.g., triethylsilane (EtaSiH), and sodium formate (HC0 ₂ Na). Suitable solvents are DMF, Ν,Ν-dimethylacetamide (DMA), acetonitrile, 1- methyl-2-pyrrolidone, dimethylsulfoxide (DMSO). Optianally, a base can be employed in the reaction, such as Na2C03, triethylamine, Ν,Ν-diisopropylethylamine. Compounds of formula llle, can be prepared from compounds of formula llld in a halogenation reaction. Suitable reaction conditions are described in WO2010/141273 and US2003/236297. The reaction is typically carried out by treating a comound of formula llld with a halogenating agent such as N-chloro- succinimide ("NCS"), sulfuryl chloride, N-bromosuccinimide ("NBS"), bromine, N-iodosuccin- imide ("NIS"), iodine, or the like. Suitable solvents are chloroform, DMF, THF, and

dichloromethane. Optionally, an acid can be employed, such as Bronstedt acids like acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, or sulfuric acid, or Lewis acids such as aluminum chloride (AlC ), iron(lll) chloride (FeC ), iron(lll) bromide (FeBr3), or the like.

Alternatively, compounds of formula llle can be prepared from compounds of formula llle', wherein Q is NO ₂ , by a sequence involving a reduction reaction to the corresponding amine followed by a Sandmeyer reaction. Suitable reaction conditions are described in the literature and are known to a person skilled in the art.

Compounds of formula Ilia, on the other hand, can be accessed by reaction of compounds of formula llld with the respective acid chloride or acid anhydride in a Friedel-Crafts acylation reaction. Suitable reaction conditions are described in S. Kasai et al. Bioorganic and Medicinal Chemistry 201 1 , 19, 6261-6273 and EP1422218.

The reaction is generally carried out in the presence of a Lewis acid activator such as AICI3, tin(IV) chloride (SnCU), FeC , borontrifluoride etherate (BF3-OEt2). Suitable solvents are dichloromethane, chloroform, 1 ,2-dichloroethane, nitromethane, or the like. Alternatively, compounds of formula Ilia can be prepared from compounds of formula llle, wherein Q is a halogen, preferably I or Br, by reacting it with the corresponding alkyl vinyl ether or enamine in a Heck reaction, followed by aqueous acid mediated hydrolysis. Suitable reaction conditions are described in WO2014/206907, WO2010/7278, and A. Laksmikanta et al. Tetrahedron

Letters 2010, 51 ,381 1-3814.

The reaction is generally carried out in the presence of a palladium catalyst, such as

Pd(OAc)2, Pd(OAc)2/1 ,3-bis(diphenylphosphino)propane, Pd(OAc)2/triphenylphosphine, palladium on acticated carbon, and a base such as K ₂ CO3, trimethylamine, N,N-dicyclohexyl- amine, thalium acetate, and pyrrolidine. Suitable solvents are DMF, DMSO, THF, 1 -methyl-2- pyrrolidone, DMA, lower alkanols, water, or mixtures thereof. The corresponding alkyl vinyl ethers are commercially available, or can be prepared by standard methods known to a person skilled in the art. The corresponding enamines are generated in situ by combining the corresponding aldehyde with a secondary amine such as pyrrolidie.

Compounds of formula V, that is compounds of formula llld wherein R ¹ , R ² , and R ³ are hydrogen and Y is a 5- or 6-membered carbocyclic ring, can be prepared by reacting compounds of formula VI with an acid chloride or the corresponding carboxylic acid in an amidation reaction, as shown below in Scheme 3. The amidation reaction is preferably carried out with the acid chloride or, if the acid chloride is not commercially available, by prior transformation of the carboxylic acids with oxalyl chloride [(COCI)2] or thionylchloride (SOCI2) to the corresponding acid chlorides, followed by reaction with the amine of formula VI. Alternatively, amidation is carried out in the presence of a coupling reagent. Suitable coupling reagents (activators) are known and are, e.g. selected from carbodiimides, such as N,N-dicyclohexylcarbodiimide ("DCC") and Ν,Ν-diisopropylcarbodiimide ("DCI"), benzotriazole derivatives such as 1- [Bis(dimethylamino)methylene]-1 H-1 ,2,3-triazolo[4,5-b]pyridinium 3-oxid hexafluorophosphate ("HATU"), 0-(Benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate ("HBTU"), and 1-[Bis(dimethylamino)methylen]-5-chlorobenzotriazolium 3-oxide hexafluorophosphate ("HCTU"), or phosphonium-derived activators, such as (Benzotriazol-1 - yloxy)tris(dimethylamino)phosphonium hexafluorophosphate ("BOP"), (benzotriazol-1-yl- oxytripyrrolidinophosphonium hexafluorophosphate) ("Py-BOP"),

bromotripyrrolidinophosphonium hexafluorophosphate ("Py-BrOP). Generally, the activator is used in excess. The benzotriazole and phosphonium coupling reagents are generally used in a basic medium.

Compounds of formula VI, in turn, can be obtained from coumpounds of formula VII by a reduction reaction. The reactions are typically carried out under an atmosphere of molecular hydrogen, usually at a pressure between 1-30 bars, and in the presence of a metal catalyst such as palladium on activated carbon ("Pd/C"), Raney-nickel ("Ra-Ni"), platinum(IV) oxide (Pt02), platinum on activated carbon ("Pt/C). Suitable solvents include lower alcohols like methanol, ethanol, and isopropanol, and THF, dioxane, water, or mixtures thereof. Optionally, an acid can be employed in the reaction such as, e.g. hydrochloric acid, or acetic acid.

Alternatively, the reduction reaction can be performed by reacting compounds of formula VII with an excess of borane tetrahydrofuran complex under the conditions as described in U . Villa: o=0, n=2 VII VI

Vlllb: o=2, n=0 V Vlllc: o=1 , n=2

Vllld: o=2, n=1

Vllle: o=1 , n=1

In turn, compounds of formula VII can be prepared by reacting compounds of formula VIII with hydroxylamine, preferably used as its hydrochloride salt. Suitable reaction conditions can be found in US2003/114666. The reactions are typically performed in the presence of solvents such as lower alcohols like methanol, and ethanol, and water, DMF, acetonitrile, or mixtures thereof. Optionally, a base can be employed in the reaction, such as e.g. organic bases like triethylamine, pyridine, sodium acetate, or inorganic bases such as NaOH, or K2CO3.

Compounds of formula Villa, that is compounds of formula VIII wherein m = 0, n = 2, and X ¹ is S, can be prepared as described in H. Yamabe et al. J. Am. Chem. Soc. 2005, 127, 3248-3249. Compounds of formula Villa', that is compounds of formula 1 wherein m = 0, n = 2, and X ¹ is O, can be prepared as described in S. Joy et al. Tetrahedron Lett. 2013, 54, 5573-5576.

Compounds of formula Vlllb, that is compounds of formula VIII wherein m = 2, n = 0, and X ¹ is S or O, can be prepared as described in H. Yamabe et al. J. Am. Chem. Soc. 2005, 127, 3248- 3249.

Compounds of formula VI lie, that is compounds of formula VIII wherein m = 1 , n = 2, and X ¹ is S can be prepared as described in A. Padwa et al. J. Org. Chem. 1989, 54, 299-308.

Compounds of formula VI lid, that is compounds of formula VIII wherein m = 2, n = 1 , and X ¹ is S can be prepared as described in A. Padwa et al. J. Org. Chem. 1989, 54, 299-308. Compounds of formula Vllle, that is compounds of formula VIII wherein m = 1 , n = 1 and X is S, can be prepared as described in C. S. Frampton et al. Tetrahedron Lett. 1997, 38, 5081-5084.

Compounds of formula Vllle', that is compounds of formula VIII wherein m = 1 , n = 1 and X is O, can be prepared by reacting compounds of formula Xa, Xb, or a mixture thereof, wherein R is an organic residue, in a decarboxylation reaction, as shown below in Scheme 4. The reaction generally proceeds through the intermediacy of the corresponding carboxylic acids Xa' or Xb', resp., wherein R is H, and is carried out under acidic conditions. The carboxylic acids can either be generated in situ as described in WO2006/32273, WO2007/1 1910, and WO20 5/103507, or can be formed in a separate step as described in US2003/232818, and US2009/221565.

S

In turn, compounds of formula Xa, or Xb, can be prepared by reacting compounds of formula IX in a Dieckmann reaction. Suitable reaction conditions are described in US2009/62318, US2005/85554, and WO2012/58065. The reaction is generally carried out in the presence of a base such as NaH, potassium tert-butylate, lithium diisopropyl amide, lithium hexamethyl- disilazide, sodium methanolate, sodium ethanolate. Suitable solvents are THF, toluene, or lower alkanols. Compounds of formula IX can be prepared as described in US2006/3990, and Y.-K. Shue et al. Journal of Organic Chemistry 1991 , 56, 2936-2938.

Compounds of formula XIV and XIV, that is compounds of formula II Id wherein R ¹ is H, CR ² -#- NR ³ forms an azetidine ring, and Y is a 5-membered heterocyclic ring, can be prepared by reacting compounds of formula XIII or XIN', resp., in a Grignard addition/nucleophilic ring-closure reaction with compounds of formula XVa, as shown below in Scheme 5. Suitable reaction conditions are described in US2012/232026, WO2014/36056, and EP1582523. The reactions are typically carried out by treatment of compounds of formula XIII or XIN', resp, preferably with W = CI, with i-PrMgCI LiCI before adding compounds of formula XVa. Suitable solvents are THF, or the like. Compounds of formula XVa are commercially available or can be made by methods known to a person skilled in the art. Compounds of formula XIII or XI I Γ can be derived from compounds of formula XII and ΧΙΓ, resp., by in situ activation of the primary alcohol, followed by nucleophilic substitution with the appropriate halogenide W. Suitable reaction conditions for W = CI are described in WO2016/4136, and S. J. Hwang et al. Org. Lett. 2009, 11 , 4588-4591.

The reaction is typically carried out by treatment of a solution of compounds of formula XII or ΧΙΓ, resp., with an activating/chlorinating agent such as thionyl chloride (SOC ), oxalyl chloride [(COCI)2], phosphosous trichloride (PCI3), phosophorous pentachloride (PC ), or

methanesulfonyl chloride (MeSC^CI). Suitable solvents are dichloromethane, chloroform, DMF, DMA, benzene, tetrahydrofurane, or mixtures thereof. Optionally, a base such as triethylamine, Ν,Ν-diisopropylethylamine, pyridine, or the like, and/or a nucleophilic catalyst such as, e.g. 4- (N,N-dimethlamino)pyridine ("DMAP") can be employed in the reaction. Suitable reaction conditions for W = Br are described in A. Kimishima et al. Tetrahedron Lett. 2012, 53, 2813- 2816. The reaction is typically carried out by treatment of a solution of compound of formula XII or ΧΙ , resp., with an activating/brominating agent such as a combination of CBr4/PP i3, or phosphorous tribromide (PBr ₃ ). Suitable solvents are dichloromethane, THF, diethyl ether, DMF, benzene, or mixtures thereof. Optionally, a base can be employed in the reaction such as triethylamine, pyridine, or the like.

Scheme 5

In turn, compounds of formula XII or XM' can be obtained from compounds of formula XI and ΧΓ, respectively, wherein R ⁶ is an alkyl group or hydrogen by treatment with a reducing agent. For compounds of formula XI or XI', respectively, wherein R ⁶ is an alkyl group, preferentially methyl, ethyl, or the like, suitable reaction conditions are described in WO2011/66183. The reaction is typically performed with diisobutylaluminum hydride (1-BU ₂ AIH), or lithium aluminum hydride (L1AIH4) as the reducing agent, and at temperatures between -78°C and 20-25°C.

Suitable solvents are, e.g. THF, diethyl ether, toluene, dichloromethane, hexanes, or mixtures thereof. For compounds of formula XI or XI', respectively, wherein R ⁶ is hydrogen, suitable reaction conditions are described in WO2012/33390. Typically, the reaction is performed with borane tetrahydrofuran complex (BH3 THF), borane dimethylsulfide complex (BH3-SMe2), or lithium aluminum hydride (LiAIH ₄ ) as the reducing agent and at temperatures between 0°C and 60°C. Suitable solvents are THF, diethyl ether, or the like. Compounds of formula Xla, that is compounds of formula XI wherein X ¹ is S, and R ⁶ is hydrogen, can be prepared as described in J.-M. Duffault et al. Synthetic Communiations 1998, 28, 2467-2481.

Compounds of formula Xlb, that is compounds of formula XI wherein X ¹ is O, and R ⁵ is alkyl, can be prepared as described in Y. Kondo et al. J. Am. Chem. Soc. 1999, 121 , 3539-3540. Compounds of formula Xla', that is compounds of formula ΧΓ wherein X ¹ is S, and R ⁶ is alkyl, can be prepared as described in Y. Kondo et al. J. Am. Chem. Soc. 1999, 121 , 3539-3540. Compounds of formula Xlb', that is compounds of formula XI' wherein X ¹ is O, and R ⁶ is hydrogen, can be prepared as described in K. Kolodziejczyk et al. Monatsheft fur Chemie 2009, 140, 1349-1359.

Compounds of formula XXI, that is compounds of formula llld wherein R ¹ is H, CR ² -#-NR ³ forms an azetidine ring, Y is a 5-membered carbocyclic ring, m is 0,1 , or 2, n is 0,1 or 2, and m+n = 2 can be prepared by reacting a compound of formula XX with an acid chloride or the corresponding carboxylic acid in an amidation reaction, as shown below in Scheme 6. The amidation reaction is preferably carried out with the acid chloride or, if the acid chloride is not commercially available, by prior transformation of the carboxylic acids with oxalyl chloride

[(COCI)2] or thionylchloride (SOC ) to the corresponding acid chlorides, followed by reaction with an amine of formula VI. Alternatively, amidation is carried out in the presence of a coupling reagent. Suitable coupling reagents (activators) are well known and are selected from carbodi- imides, such as Ν,Ν-dicyclohexylcarbodiimide ("DCC") and Ν,Ν-diisopropylcarbodiimide ("DCI"), benzotriazole derivatives such as 1 -[Bis(dimethylamino)methylene]-1 H-1 ,2,3-triazolo[4,5- b]pyridinium 3-oxid hexafluorophosphate ("HATU"), 0-(Benzotriazol-1-yl)-N,N,N',N'- tetramethyluronium hexafluorophosphate ("HBTU") and 1-[Bis(dimethylamino)methylen]-5- chlorobenzotriazolium 3-oxide hexafluorophosphate ("HCTU"), or phosphonium-derived activators, such as (Benzotriazol-1 -yloxy)tris(dimethylamino)phosphonium hexafluorophosphate ("BOP"), (benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate) ("Py-BOP"), bromotripyrrolidinophosphonium hexafluorophosphate ("Py-BrOP). Generally, the activator is used in excess. The benzotriazole and phosphonium coupling reagents are generally used in a basic medium.

Compounds of formula XX, in turn, can be obtained from a compound of formula XIX, usually with SO2R = 4-methylbenzene sulfonyl ("TS"), by a reduction/nucleophilic displacement reaction. Suitable reaction conditions are described in US2013/331375, WO2007/30061 , and J. Froehlich et al. Heterocycles 1994, 37, 1879-1892.

The reaction is generally carried out in the presence of a metal hydride reducing agent, usually lithium aluminum hydride (UAIH4). Suitable solvents are THF, diethyl ether, or the like.

Compounds of formula XIX, on the other hand, can be prepared by reacting compounds of formula XVIII with a sulfonylating agent, preferably the corresponding sulfonyl chloride. Suitable reaction conditions are described in WO2007/30061 , and in J. Froehlich et al. Heterocycles 1994, 37, 1879-1892. The reaction is generally carried out in the presence of a base such as triethylamine (EtsN), pyridine, sodium hydride (NaH), or the like. Suitable solvents are dichloromethane, chloroform, THF, pyridine or the like. Optionally, a nucleophilic catalyst can be employed in the reaction such as, e.g. 4-(N,N-dimethlamino)pyridine ("DMAP"). Scheme 6

XVIIIa : o=0, n=2

Villa XVIIa: o=0, n=2

XVIIIb: o=2, n=0 Vlllb XVIIb: o=2, n=0 XVIIIc: o=1 , n=1

XVIIIb: o=2, n=0

XVIIIc: o=1 , n=1 XIX XX XXI

Compounds of formula XVIIIa or XVIIIb can be prepared by reacting compounds of formula XVIIa or XVIIb, resp., with formaldehyde or a formaldehyde surrogate such as

paraformaldehyde, or the like. Suitable reaction conditions are described in J. Froehlich et al. Heterocycles 1994, 37, 1879-1892, and WO2015/42243. The reaction is generally carried out in the presence of a base such as N-benzyltrimetylammonium hydroxide, NaH, lithium

diisopropylamine. Suitable solvents are methanol, pyridine, toluene, DMF, THF, or mixtures thereof. In turn, compounds of formula XVIIa or XVIIb can be prepared by reacting compounds of formula Villa, Vlllla', Vlllb, or Vlllb', resp., with para-toluenesulfonylmethyl isocyanide ("TosMIC") in a Van Leusen reaction. Suitable reaction conditions are described, e.g. in

WO201 1/69063, or in J. Froehlich et al. Journal fur Praktische Chemie (Leipzig), 1990, 332, 995-1003. The reaction is generally carried out in the presence of a base such as potassium tert-butylate (KOtBu), or the like. Suitable solvents are 1 ,2-dimethoxyethane, lower alkanols, DMSO, THF, or mixtures thereof. Compounds of formula XVIIIc, on the other hand, can be obtained from compounds of formula XVI lc by a chemoselective reduction reaction. Suitable reaction conditions can be found in EP2090570, WO2013/13308, and in F. F. Fleming et al. Journal of Organic Chemistry, 2005, 70, 3845-3849.

The reaction is generally carried out in the presence of a hydride donor agent such as sodium tetrahydroborate (NaBH ₄ ), lithium tetrahydroborate (L1BH4), calcium borohydride (Ca(BH ₄ )2), or the like. Suitable solvents are THF, lower alkanols, water, or mixtures thereof. In turn, compounds of formula XVIIc can be prepared by reaction of compounds of formula XVIc with a cyanoacetate ester of formula XVb in a cyclization reaction. Suitable reaction conditions are described in US6689906, US6548498, and US2002/61874. The reaction is generally carried out in the presence of a base such as sodium alkoxide, potassium alkoxide, Na2CC>3, K2CO3, NaH, or the like. Suitable solvents are DMF, lower alkanols, acetonitrile, DMSO, or the like.

Cyanoacetate esters of formula XVb are commercially available, or can be made by standard methods which are known to a person skilled in the art. Compounds of formula XVIc, wherein X ¹ is S, and W and W ² are a halogen, usually CI or Br, can be prepared as described in T. Dey et al. Tetrahedron Lett. 2010, 51 , 2089-2091 , K. Hammer et al. Acta Chemica Scandinavica 1997, 51 , 392-402, and US2009/326187. Compounds of formula XVIc', that is compounds of formula XVIc wherein X ¹ is O, and W ¹ and W ² are a halogen, usually CI or Br, can be prepared as described in T. Dey et al. Tetrahedron Lett. 2010, 51 , 2089-2091 , and L. M. Pevzner Russian Journal of General Chemistry 2000, 70, 25-36.

Compounds of formula XXV and XXV, that is compounds of formula llld wherein R ¹ is H, CR ² -#-NR ³ forms an azetidine ring, W ³ is H, halogen or NO2, and Y is a 5-membered heterocyclic ring, can be prepared by reacting a compound of formula XXIV or XXIV, resp., wherein W ⁴ is halogen or alkoxy, in a nucleophilic substitution reaction. Suitable reaction conditions are described in WO2013/9517, US2003/229079, EP1216249, and US2008/71084. The reaction is generally performed in the presence of a base such as K ₂ C0 ₃ , NaH, Cs ₂ C0 ₃ , lower alkoxides, or the like. Suitable solvents are DMF, DMSO, N-methyl-2-pyrrolidone, THF, lower alkanols, toluene, or the like. Optionally, a copper salt can be employed in the reaction such as, e.g. copper(l) iodide, copper(l) bromide, copper(ll) oxide, or the like. In turn, compounds of formula XXIV or XXIV can be obtained by metallating compounds of formula XXIII and XXIII', respectively, wherein G is H, Br, or I, with a strong base or metallating agent and reacting it with compounds of formula XXII. Suitable reaction conditions are described in US2004/19205, and WO201 1/69063. Suitable strong bases and metallating agents, resp., are lithium diisopropylamine, butyllithium, iP^MgCI-LiCI ("TurboGrignard"), tert-butyllithium, magnesium, lithium tetramethylpiperidine. Suitable solvents are THF, diethyl ether, toluene, hexanes, or the like, as well as mixtures thereof. Optionally, a Lewis acid activator can be employed in the reaction such as, e.g. BF3-OEt2, or Sc(OTf)3. Compounds of formula XXII, XXIII and ΧΧΙΙΓ are commercially available or can be prepared as described in the literature, or by standard methods which are known to a person skilled in the art.

Scheme 7

Alternatively, compounds of formula llld', that is compounds of formula llld wherein R ¹ , R ² , and R ³ are hydrogen, Y is a 5- or 6-membered carbocyclic ring, and X ¹ is O can be prepared by reacting a compound of formula XXVIII in a ττ-acid catalyzed rearrangement reaction. Suitable reaction conditions are described in P. Alonso et al. Angew. Chem. 2015, 127, 15726-15730, A. Blanc et al. J. Org. Chem. 2009, 74, 5342-5348, M. Yoshida et al. Tetrahedron Letters 2008, 49, 5021-5023, and C.-Y. Lo et al. Journal of Organic Chemistry 2002, 67, 3930-3932.

Suitable ττ-acid catalysts are, e.g. cationic gold(l)-phosphine complexes, platinum(ll) salts, mercury(ll) salts, gold(lll) salts, and AgOTf/pTsOH. In turn, compounds of formula XXVIII can be prepared by reacting compounds of formula XXVII', which are compounds of formula XXVII wherein R ⁸ is hydrogen, with a peroxicarboxylic acid, preferably meta-chloroperbenzoic acid, in a Prilezhaev reaction. Suitable reaction conditions are described in P. Alonso et al. Angew.

Chem. 2015, 127, 15726-15730, and A. Blanc et al. J. Org. Chem. 2009, 74, 5342-5348. In turn, compounds of formula XXVII' can be prepared from a compound of formula XXVII, wherein R ⁸ is a silyl protecting group such as, e.g. trimethylsilyl, triethylsilyl, or the like, in a deprotection reaction. Suitable reaction conditions are described in P. Alonso et al. Angew. Chem. 2015, 127, 15726-15730, US2005/245530, and US2010/105700.

Compounds of formula XXVII, on the other hand, can be prepared by reacting copmpounds of formula XXVI, wherein W ⁵ is OS(0)2CF3, Br, or I, with a mono-protected acetylene such as trimethylsilylacetylene, in a Sonogashira cross-coupling reaction. Suitable reaction conditions are described in P. Alonso et al. Angew. Chem. 2015, 127, 15726-15730, and US2005/245530.

The reaction is generally carried out in the presence of a palladium catalyst such as tetra- kis(triphenylphosphine)palladium, Dichlorobis(triphenylphosphine)palladium, or the like, a co- catalytic copper(l) salt such as copper iodide, and an amine base such as trimethylamine, diethylamine, piperidine, N,N-diisopropylamine, Ν,Ν-diisopropylethylamine, or the like. Suitable s

XXVIa: o=1, n=2 XXVII XXVIII Illd"

XXVIb: o=2, n=1

Compound XXVIa, that is compounds of formula XXVI wherein m = 1 , n = 2, and W ³ is OS(0) ₂ CF ₃ can be prepared as described in US2005/245530. Compound XXVIb, that is compounds of formula XXVI wherein m = 2, n = 1 , and W ³ is OS(0)2CF3 can be prepared as described in EP 3070086. Other compounds of formula XXVI can be prepared from the corresponding ketones in analogy to the above examples by standard methods of organic chemistry, which are known ba a person skilled in the art.

As a rule, the compounds of formula I including their stereoisomers, salts, and N-oxides, and their precursors in the synthesis process, can be prepared by the methods described above. If individual compounds can not be prepared via the above-described routes, they can be prepared by derivatization of other compounds I or the respective precursor or by customary modifications of the synthesis routes described. For example, in individual cases, certain compounds of formula I can advantageously be prepared from other compounds of formula I by derivatization, e.g. by ester hydrolysis, amidation, esterification, ether cleavage, olefination, reduction, oxidation and the like, or by customary modifications of the synthesis routes described.

The reaction mixtures are worked up in a customary manner, e.g. by mixing with water, separating the phases and, if appropriate, chromatographic purification of the crude products. Some of the intermediates and end products are obtained in the form of colourless or slightly brownish viscous oils which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion.

If individual compounds I cannot be obtained by the routes described above, they can be prepared by derivatization of other compounds I. However, if the synthesis yields mixtures of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (e.g. under the action of light, acids or bases). Such conversions may also take place after use, e.g. in the treatment of plants in the treated plant, or in the harmful fungus to be controlled.

The radicals attached to the backbone of formula I may contain one or more centers of chirality. In this case the compounds of formula I are present in the form of different

enantiomers or diastereomers, depending on the substituents. The invention relates to every possible stereoisomer of the formula I, i.e. to single enantiomers or diastereomers, as well as to mixtures thereof.

As already indicated above, the compounds of formula I may be present in the form of different structural isomers depending on the position of substituents. The invention relates to every possible structural isomer as indicated in the compounds of formula I, and mixtures thereof.

The compounds of formula I may be amorphous or may exist in one or more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities. The invention relates to amorphous and crystalline compounds of formula I, mixtures of different crystalline states of the respective compound I, as well as amorphous or crystalline salts thereof.

Salts of the compounds of the formula I are preferably veterinary and/or agriculturally acceptable salts, preferably agriculturally acceptable salts. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality.

Veterinary and/or agriculturally useful salts of the compounds of formula I encompass especially the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the pesticidal action of the compounds of formula I.

Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting compounds of formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

The term "N-oxide" includes any compound of formula I which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety.

The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix C _n - Cm indicates in each case the possible number of carbon atoms in the group.

The term "halogen" denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine.

The term "alkyl" as used herein and in the alkyl moieties of alkylamino, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl and alkoxyalkyl denotes in each case a straight-chain or branched al- kyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably from 1 to 3 carbon atoms. Examples of an alkyl group are methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1- methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethyl propyl, n-hexyl, 1 ,1-di- methylpropyl, 1 ,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methyl- pentyl, ,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 and in the haloalkyl moieties of haloalkylcarbonyl, halo- alkoxycarbonyl, haloalkylthio, haloalkylsulfonyl, haloalkylsulfinyl, haloalkoxy and

haloalkoxyalkyl, denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms. Preferred haloalkyl moieties are selected from Ci-C4-haloalkyl, more preferably from Ci- C3-haloalkyl or Ci-C ₂ -haloalkyl, in particular from Ci-C ₂ -fluoroalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and the like.

The term "alkoxy" as used herein denotes in each case a straight-chain or branched alkyl group which is bonded via an oxygen atom and has usually from 1 to 10 carbon atoms, fre- quently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Examples of an alkoxy group are methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, 2-butyloxy, iso-butyloxy, tert.-butyloxy, and the like.

The term "alkoxyalkyl" as used herein refers to alkyl usually comprising 1 to 10, frequently 1 to 4, preferably 1 to 2 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually comprising 1 to 4, preferably 1 or 2 carbon atoms as defined above. Examples are CH ₂ OCH3, CH2-OC2H5, 2-(methoxy)ethyl, and 2-(ethoxy)ethyl.

The term "haloalkoxy" as used herein denotes in each case a straight-chain or branched alkoxy group having from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms, in particular fluorine atoms. Preferred haloalkoxy moieties include C1-C4- haloalkoxy, in particular Ci-C2-fluoroalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoro- methoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2- fluoroethoxy, 2-chloro-2,2-difluoro-ethoxy, 2,2dichloro-2-fluorethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and the like.

The term "alkylthio "(alkylsulfanyl: S-alkyl)" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-alkylthio), more preferably 1 to 3 carbon atoms, which is attached via a sulfur atom.

The term "haloalkylthio" as used herein refers to an alkylthio group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.

The term "alkylsulfinyl" (alkylsulfoxyl: S(=0)-CrC ₆ -alkyl), as used herein refers to a straight- chain or branched saturated alkyl group (as mentioned above) having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-alkylsulfinyl), more preferably 1 to 3 carbon atoms bonded through the sulfur atom of the sulfinyl group at any position in the alkyl group. The term "haloalkylsulfinyl" as used herein refers to an alkylsulfinyl group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.

The term "alkylsulfonyl" (S(=0)2-alkyl) as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (= C1-C4- alkylsulfonyl), preferably 1 to 3 carbon atoms, which is bonded via the sulfur atom of the sulfonyl group at any position in the alkyl group.

The term "haloalkylsulfonyl" as used herein refers to an alkylsulfonyl group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.

The term "alkylcarbonyl" refers to an alkyl group as defined above, which is bonded via the carbon atom of a carbonyl group (C=0) to the remainder of the molecule.

The term "haloalkylcarbonyl" refers to an alkylcarbonyl group as mentioned above, wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine. The term "alkoxycarbonyl" refers to an alkylcarbonyl group as defined above, which is bonded via an oxygen atom to the remainder of the molecule.

The term "haloalkoxycarbonyl" refers to an alkoxycarbonyl group as mentioned above, wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.

The term "alkenyl" as used herein denotes in each case a singly unsaturated hydrocarbon radical having usually 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms, e.g. vinyl, allyl (2-propen-1 -yl), 1 -propen-1-yl, 2-propen-2-yl, methallyl (2-methylprop-2-en-1-yl), 2-buten-1 -yl, 3- buten-1 -yl, 2-penten-1-yl, 3-penten-1-yl, 4-penten-1-yl, 1-methylbut-2-en-1-yl, 2-ethylprop-2-en- 1-yl and the like.

The term "haloalkenyl" as used herein refers to an alkenyl group as defined above, wherein the hydrogen atoms are partially or totally replaced with halogen atoms.

The term "alkynyl" as used herein denotes in each case a singly unsaturated hydrocarbon radical having usually 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms, e.g. ethynyl, propargyl (2-propyn-1 -yl), 1 -propyn-1-yl, 1-methylprop-2-yn-1-yl), 2-butyn-1-yl, 3-butyn-1-yl, 1- pentyn-1 -yl, 3-pentyn-1-yl, 4-pentyn-1-yl, 1-methylbut-2-yn-1-yl, 1-ethylprop-2-yn-1-yl and the like.

The term "haloalkynyl" as used herein refers to an alkynyl group as defined above, wherein the hydrogen atoms are partially or totally replaced with halogen atoms.

The term "cycloalkyl" as used herein and in the cycloalkyl moieties of cycloalkoxy and cyclo- alkylthio denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 10 or from 3 to 6 carbon atoms, such as cyclopropyl (C-C3H5), cyclobutyl (C-C4H7), cyclopentyl (c- C5H9), cyclohexyl (c-CeHu), cycloheptyl (C-C7H13), cyclooctyl (c-CsH-is), cyclononyl (C-C9H17) and cyclodecyl (C-C10H19), or cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

The term "halocycloalkyl" as used herein and in the halocycloalkyl moieties of halocycloalkoxy and halocycloalkylthio denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 10 C atoms or 3 to 6 C atoms, wherein at least one, e.g. 1 , 2, 3, 4 or 5 of the hydrogen atoms, are replaced by halogen, in particular by fluorine or chlorine. Examples are 1 - and 2- fluorocyclopropyl, 1 ,2-, 2,2- and 2,3-difluorocyclopropyl, 1 ,2,2-trifluorocyclopropyl, 2,2,3,3- tetrafluorocyclpropyl, 1 - and 2-chlorocyclopropyl, 1 ,2-, 2,2- and 2,3-dichlorocyclopropyl, 1 ,2,2- trichlorocyclopropyl, 2,2,3,3-tetrachlorocyclpropyl, 1-,2- and 3-fluorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluorocyclopentyl, 1 -,2- and 3-chlorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5- dichlorocyclopentyl and the like.

The term "cycloalkenyl" as used herein and in the cycloalkenyl moieties of cycloalkenyloxy and cycloalkenylthio denotes in each case a monocyclic singly unsaturated non-aromatic radical having usually from 3 to 10, e.g. 3 or 4 or from 5 to 0 carbon atoms, preferably from 3- to 8 carbon atoms. Exemplary cycloalkenyl groups include cyclopropenyl, cycloheptenyl or cyclo- octenyl.

The term "cycloalkenylalkyl" refers to a cycloalkenyl group as defined above which is bonded via an alkylene group, such as a Ci-Cs-alkyl group or a Ci-C4-alkyl group, in particular a methylene group (= cycloalkenylmethyl), to the remainder of the molecule.

The term "carbocycle" or "carbocyclyl" includes in general a 3- to 12-membered, preferably a 3- to 8-membered or a 5- to 8-membered, more preferably a 5- or 6-membered mono-cyclic, non-aromatic ring comprising 3 to 12, preferably 3 to 8 or 5 to 8, more preferably 5 or 6 carbon atoms. Preferably, the term "carbocycle" covers cycloalkyl and cycloalkenyl groups as defined above.

The term "heterocycle" or "heterocyclyl" includes in general 3- to 12-membered, preferably 5- or 6-membered, in particular 6-membered monocyclic heterocyclic non-aromatic radicals. The heterocyclic non-aromatic radicals usually comprise 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, wherein S-atoms as ring members may be present as S, SO or SO2. Examples of 5- or 6-membered heterocyclic radicals comprise saturated or unsaturated, non- aromatic heterocyclic rings, such as 2- and 3-azetidinyl, 2- and 3-oxetanyl, 2- and 3-thietanyl, 2- and 3-thietanyl-S-oxide(S-oxothietanyl), 2- and 3-thietanyl-S-dioxide(S-dioxothiethanyl), 2- and 3-pyrrolidinyl, 2- and 3-tetrahydrofuranyl, 1 ,3-dioxolan-2-yl, thiolan-2-yl, S-oxothiolan-2-yl, S-di- oxothiolan-2-yl, 4- and 5-oxazolidinyl, 1 ,3-dioxan-2-yl, 1- and 3-thiopyran-2-yl, S-oxothiopyranyl, and S-dioxothiopyranyl.

The terms "heterocyclyolalkyl" refer to heterocyclyl as defined above which are bound via a Ci-C4-alkyl group, in particular a methyl group (= heterocyclylmethyl), to the remainder of the molecule.

With respect to the variables, the particularly preferred embodiments of the intermediates correspond to those of the compounds of the formula I.

In a particular embodiment, the variables of the compounds of the formula I have the following meanings, these meanings, both on their own and in combination with one another, being particular embodiments of the compounds of the formula I.

One embodiment relates to compounds of formula I wherein X ¹ is S.

Another embodiment relates to compounds of formula I wherein X ¹ is O. In one preferred embodiment B ¹ , B ² , and B ³ denote CR ^B ; the B ¹ to B ³ containnig ring is accordingly a phenyl group A with three substituents R ² , being R ^Ba , R ^B , and R ^Bc , wherein the "+" denotes the bond to the dihydroisoxazole moiety:

Formula I compounds wherein the B ¹ to B ³ containnig ring is a group A correspond accordingly to formula .

R ^Ba is preferably selected from F, CI, Br, CF ₃ , and OCF ₃ .

R ^Bb and R ^Bc are independently preferably selected from H, F, CI, Br, CF ₃ , and OCF ₃ .

Particularly preferred is each one of the following combinations of R ^Ba , R ^B and R ^Bc wherein each line of Table A denotes a substitution pattern "A" of the phenyl ring bearing the R ^Ba , R ^B and R ^Bc groups.

Table A

Groups A-8, A-9, and A-11 are more preferred patterns in formula I compounds. A-9, and A-1 1 are particularly preferred.

In formula I compounds containing several R ¹ different from H such R ¹ groups can be identical or different from each other. R ¹ is preferably H. In the compounds of the invention ^5a and R ^5b are preferably H.

In one embodiment Y is a carbocyclic ring, preferably a five- or six-membered saturated ring. In one embodiment Y is a heterocyclic ring, preferably a saturated heterocyclic ring with one hetero atom, which particularly is oxygen.

In one preferred embodiment this saturated heterocyclic ring is a five-membered ring.

In another preferred embodiment this saturated heterocyclic ring is a six-membered ring. In one embodiment the heteroatom in ring Y is bonded to C ³ of the thiophene ring. In a preferred embodiment the heterocycle Y is a 2,5-dihydrofuran. In still another embodiment the heteroatom in ring Y is bonded to C ² of the thiophene ring.

In formula I.A and I.B at least one of Y ¹ and Y ² is CHR ¹ ; if only one of Y ¹ and Y ² is CHR ¹ , the other position is oxygen. Formula I.A compounds are particularly preferred.

In another embodiment the saturated heterocyclic ring Y is a six-membered ring.

In another embodiment Y is a six-membered saturated carbocyclic ring.

In another embodiment Y is a six-membered saturated heterocyclic ring.

In formula I.C and I.D at least one, and preferably one of Y ¹ and Y ² is CHR ¹ ; if only one of Y ¹ and Y ² is CHR ¹ , the other position is oxygen.

In one embodiment of fomula I # is a direct bond. In these compounds R ² and R ³ are preferably H.

In another embodiment of formula I # forms together with CR ² and NR ³ an azetidine ri In another embodiment of formula I Y is a carbocycle, and # is a direct bond.

Such preferred embodiments of formula I are the following:

Formula 1.6 compounds are particularly preferred.

In another embodiment of formula I Y is a carbocycle, # is together with CR ² and NR ³ an azetidine ring.

In another embodiment Y is a dihydrofuran, and # is together with CR ² and NR ³ an azetidine rin

Formula 1.10 compounds are particularly preferred.

In another embodiment Y is a 3,6-dihydro-2H-pyran, and # is together with CR ² and NR ³ an azetidine ring. Such preferred embodiments of formula I are the following:

Formula 1.14 compounds are particularly preferred .

In the formula I compounds R ⁴ is preferably selected from Ci-C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ - cycloalkyl-Ci-C ₂ -alkyl, Ci-C ₂ -haloalkyl, Ci-C ₂ -alkoxy-Ci-C ₂ -alkyl, Ci-C ₂ -haloalkoxy-Ci-C ₂ -alkyl, CH ₂ S(0) _m -Ci-C4-alkyl, and CH ₂ S(0)m-Ci-C ₂ -haloalkyl, or 3-to 6-membered saturated heterocycles with 1 or 2 heteroatoms selected from O and S, wherein S-atoms as ring members may be present as S, SO, or S0 ₂ . R ⁴ is particularly selected from CH ₃ , C2H5, CH2CH2CH3, CH2CF3, C-C3H5, I -CN-C-C3H4, CH2SCH3, CH ₂ S(0)CH ₃ , CH ₂ S(0) ₂ CH ₃ , and CH ₂ S(0)2C ₂ H5. In another embodiment of formula I compounds R ⁴ is selected from cyclopropyl-Ci-C ₂ -alkyl, and 3- to 6-membered heterocyclyl, which rings are bonded directly or via a CrC ₂ -alkylene spacer.

One embodiment relates to formula I compounds wherein

X ¹ is O, or S;

B ¹ , B ² and B ³ are independently of each other N and CR ^B , with the proviso that at most one of B ¹ , B ² and B ³ is N ;

R ^B is H , CI, F, Br, CF ₃ , or OCF ₃ ;

Y is taken together with the carbon atom of CR ² and the C ² and C ³ -atoms of the adjacent X ¹ containing ring to form a 5- to 7-membered saturated or partially unsaturated carbo- or heterocycle where the heterocycle contains 1 to 3 heteroatoms selected from N, O, or S; R ¹ is H , halogen, CN , N0 ₂ , Ci-Ce-alkyl , Ci-C ₆ -haloalkyl, Ci-C ₆ -alkoxy, Ci-C ₆ -haloalkoxy, C ₃ - Ce-cycloalkyl, OR ^a , NR ^a R ^b , N0 ₂ , C(=0)OR ^a , C(=0)N(R ^a ) ₂ , or S(0) _m R ^a ;

R ^a and R ^b , independently of each other, are H, Ci-C6-alkyl , Ci-C6-alkoxy, Ci-C6-alkyl- S(0)m-Ci-C ₆ -alkyl, Ci-C6-alkyl-S(0) _m -Ci-C ₆ -haloalkyl, C ₃ -C ₆ -cycloalkyl, C ₂ -C ₆ - alkenyl , C ₂ -C ₆ -alkynyl, C ₂ -C ₆ -alkenyloxy, C ₂ -C ₆ -alkynyloxy, C ₅ -Ci ₄ -cycloalkyl, which groups are unsubstituted or substituted by one or more R ^c ;

R ^c is halogen, cyano, Ci-C4-alkyl, or Ci-C4-haloalkyl;

m is 0, 1 , or 2;

# is a direct bond, or together with CR ² and NR ³ forms an azetidine ring;

if # is a direct bond:

R ² is H , halogen, CN , N0 ₂ , Ci-C ₆ -alkyl , Ci-C ₆ -haloalkyl, Ci-C ₆ -alkoxy, Ci-C ₆ -haloalk- oxy, C ₃ -C ₆ -cycloalkyl, OR ^a , NR ^a R ^b , N0 ₂ ; and

R ³ is group as defined for R ^a ;

R ⁴ is a group as defined for R ^a ;

R ^5a and R ⁵ , independently of each other, are H, halogen, or OH ;

and the N-oxides, stereoisomers and agriculturally or veterinarily acceptable salts thereof. In particular with a view to their use, preference is given to the compounds of the formula I compiled in the tables below. Each of the groups mentioned for a substituent in the tables is furthermore per se, independently of the combination in which it is mentioned, a particularly preferred aspect of the substituent in question.

Table 1 Compounds of formula 1.1 in which R ¹ is H, and the combination of A and R ⁴ for a compound corresponds in each case to one row of Table R

Table 2 Compounds of formula 1.2 in which R ¹ is H, and the combination of A and R ⁴ for a compound corresponds in each case to one row of Table R

Table 3 Compounds of formula 1.3 in which R ¹ is H, and the combination of A and R ⁴ for a compound corresponds in each case to one row of Table R

Table 4 Compounds of formula 1.4 in which R ¹ is H, and the combination of A and R ⁴ for a compound corresponds in each case to one row of Table R

Table 5 Compounds of formula 1.5 in which R ¹ is H, and the combination of A and R ⁴ for a compound corresponds in each case to one row of Table R

Table 6 Compounds of formula 1.6 in which R ¹ is H, and the combination of A and R ⁴ for a compound corresponds in each case to one row of Table R

Table 7 Compounds of formula 1.7 in which R ¹ is H, and the combination of A and R ⁴ for a compound corresponds in each case to one row of Table R

Table 8 Compounds of formula 1.8 in which R ¹ is H, and the combination of A and R ⁴ for a compound corresponds in each case to one row of Table R

Table 9 Compounds of formula 1.9 in which R ¹ is H, and the combination of A and R ⁴ for a compound corresponds in each case to one row of Table R

Table 10 Compounds of formula 1.10 in which R ¹ is H, and the combination of A and R ⁴ for a compound corresponds in each case to one row of Table R

Table 1 1 Compounds of formula 1.11 in which R ¹ is H, and the combination of A and R ⁴ for a compound corresponds in each case to one row of Table R

Table 12 Compounds of formula 1.12 in which R ¹ is H, and the combination of A and R ⁴ for a compound corresponds in each case to one row of Table R

Table 13 Compounds of formula 1.13 in which R ¹ is H, and the combination of A and R ⁴ for a compound corresponds in each case to one row of Table R

Table 14 Compounds of formula 1.14 in which R ¹ is H, and the combination of A and R ⁴ for a compound corresponds in each case to one row of Table R

Table 15 Compounds of formula 1.15 in which R ¹ is H, and the combination of A and R ⁴ for a compound corresponds in each case to one row of Table R

Table R

Nr. A R ⁴ Nr. A R ⁴

R-1 A-9 CH ₃ R-7 A-9 CH2CF3

R-2 A-1 1 CH ₃ R-8 A-1 1 CH2CF3

R-3 A-9 C2H5 R-9 A-9 CH2OCH3

R-4 A-1 1 C2H5 R-10 A-1 1 CH2OCH3

R-5 A-9 CH2CH2CH3 R-11 A-9 CH2OCH2CH3

R-6 A-1 1 CH2CH2CH3 R-12 A-1 1 CH2OCH2CH3

As used herein, the term "compound(s) of the invention" or "compound(s) according to the invention" refers to the compound(s) of formula (I) as defined above, which are also referred to as "compound(s) of formula I" or "compound(s) I" or "formula I compound(s)", and includes their salts, tautomers, stereoisomers, and N-oxides.

The invention also relates to a mixture of at least one compound of the invention with at least one mixing partner as defined herein after. Preferred are binary mixtures of one compound of the invention as component I with one mixing partner as defined herein after as component II. Preferred weight ratios for such binary mixtures are from 5000: 1 to 1 :5000, preferably from

1000:1 to 1 :1000, more preferably from 100:1 to 1 :100, particularly preferably from 10:1 to 1 :10 In such binary mixtures, components I and II may be used in equal amounts, or an excess of component I , or an excess of component II may be used.

Mixing partners can be selected from pesticides, in particular insecticides, nematicides, and acaricides, fungicides, herbicides, plant growth regulators, fertilizers, and the like. Preferred mixing partners are insecticides, nematicides and fungicides. The following list M of pesticides, grouped and numbered according the Mode of Action Classification of the Insecticide Resistance Action Committee (IRAC), together with which the compounds of the invention can be used and with which potential synergistic effects might be produced, is intended to illustrate the possible combinations, but not to impose any limitation: M.1 Acetylcholine esterase (AChE) inhibitors from the class of: M.1A carbamates, e.g.

aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; or from the class of M.1 B organophosphates, e.g. acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O- (methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos- methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon and vamidothion;

M.2. GABA-gated chloride channel antagonists such as: M.2A cyclodiene organochlorine compounds, as e.g. endosulfan or chlordane; or M.2B fiproles (phenylpyrazoles), as e.g.

ethiprole, fipronil, flufiprole, pyrafluprole and pyriprole;

M.3 Sodium channel modulators from the class of M.3A pyrethroids, e.g. acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma- cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta- cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, heptafluthrin, imiprothrin, meperfluthrin,metofluthrin, momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethylfluthrin, tetramethrin, tralomethrin and transfluthrin; or M.3B sodium channel modulators such as DDT or

methoxychlor;

M.4 Nicotinic acetylcholine receptor agonists (nAChR) from the class of M.4A neonicotinoids, e.g. acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or the compounds M.4A.2: (2E-)-1-[(6-Chloropyridin-3-yl)methyl]-N'-nitro-2- pentylidenehydrazinecarboximidamide; or M4.A.3: 1-[(6-Chloropyridin-3-yl)methyl]-7-methyl-8- nitro-5-propoxy-1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridine; or from the class M.4B nicotine;

M.5 Nicotinic acetylcholine receptor allosteric activators from the class of spinosyns, e.g. spinosad or spinetoram;

M.6 Chloride channel activators from the class of avermectins and milbemycins, e.g.

abamectin, emamectin benzoate, ivermectin, lepimectin or milbemectin;

M.7 Juvenile hormone mimics, such as M.7A juvenile hormone analogues as hydroprene, kinoprene and methoprene; or others as M.7B fenoxycarb or M.7C pyriproxyfen; M.8 miscellaneous non-specific (multi-site) inhibitors, e.g. M.8A alkyl halides as methyl bromide and other alkyl halides, or M.8B chloropicrin, or M.8C sulfuryl fluoride, or M.8D borax, or M.8E tartar emetic;

M.9 Selective homopteran feeding blockers, e.g. M.9B pymetrozine, or M.9C flonicamid;

M.10 Mite growth inhibitors, e.g. M.10A clofentezine, hexythiazox and diflovidazin, or M.10B etoxazole;

M.11 Microbial disruptors of insect midgut membranes, e.g. bacillus thuringiens!s or bacillus sphaericus and the insecticdal proteins they produce such as bacillus thuringiensis subsp. israelensis, bacillus sphaericus, bacillus thuringiensis subsp. aizawai, bacillus thuringiensis subsp. kurstaki and bacillus thuringiensis subsp. tenebrionis, or the Bt crop proteins: Cry1 Ab, CrylAc, Cryl Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb and Cry34/35Ab1 ;

M.12 Inhibitors of mitochondrial ATP synthase, e.g. M.12A diafenthiuron, or M.12B organotin miticides such as azocyclotin, cyhexatin or fenbutatin oxide, or M.12C propargite, or M.12D tetrad if on;

M.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient, e.g.

chlorfenapyr, DNOC or sulfluramid;

M.14 Nicotinic acetylcholine receptor (nAChR) channel blockers, e.g. nereistoxin analogues as bensultap, cartap hydrochloride, thiocyclam or thiosultap sodium;

M.15 Inhibitors of the chitin biosynthesis type 0, such as benzoylureas, e.g. bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron or triflumuron;

M.16 Inhibitors of the chitin biosynthesis type 1 , e.g. buprofezin;

M.17 Moulting disruptors, Dipteran, as e.g. cyromazine;

M.18 Ecdyson receptor agonists such as diacylhydrazines, e.g. methoxyfenozide,

tebufenozide, halofenozide, fufenozide or chromafenozide;

M.19 Octopamin receptor agonists, e.g. amitraz;

M.20 Mitochondrial complex III electron transport inhibitors, e.g. M.20A hydramethylnon, M.20B acequinocyl, or M.20C fluacrypyrim;

M.21 Mitochondrial complex I electron transport inhibitors, e.g. M.21A METI acaricides and insecticides such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, or M.21 B rotenone;

M.22 Voltage-dependent sodium channel blockers, e.g. M.22A indoxacarb, M.22B

metaflumizone, M.22B. : 2-[2-(4-Cyanophenyl)-1 -[3-(trifluoromethyl)phenyl]ethylidene]-N-[4- (difluoromethoxy)phenyl]-hydrazinecarboxamide, or M.22B.2: N-(3-Chloro-2-methylphenyl)-2- [(4-chlorophenyl)[4-[methyl(methylsulfonyl)amino]phenyl]meth ylene]-hydrazinecarboxamide;

M.23 Inhibitors of the of acetyl CoA carboxylase, such as Tetronic and Tetramic acid derivatives, e.g. spirodiclofen, spiromesifen, or spirotetramat;

M.24 Mitochondrial complex IV electron transport inhibitors, e.g. M.24A phosphine such as aluminium phosphide, calcium phosphide, phosphine, zinc phosphide, or M.24B cyanide;

M.25 Mitochondrial complex II electron transport inhibitors, such as beta-ketonitrile derivatives, e.g. cyenopyrafen, or cyflumetofen;

M.28 Ryanodine receptor-modulators from the class of diamides, e.g. flubendiamide, chloran- traniliprole (rynaxypyr®), cyantraniliprole (cyazypyr®), tetraniliprole, or M.28.1 : (R)-3-Chlor-N1 - {2-methyl-4-[1 ,2,2,2 -tetrafluor-1-(trifluormethyl)ethyl]phenyl}-N2-(1 -methyl-2-methylsulfonyl- ethyl)phthalamid and M.28.2: (S)-3-Chlor-N 1-{2-methyl-4-[1 ,2,2,2 -tetrafluor-1- (trifluormethyl)ethyl]phenyl}-N2-(1 -methyl-2-methylsulfonylethyl)phthalamid, M.28.3:

cyclaniliprole, M.28.4: methyl-2-[3,5-dibromo-2-({[3-bromo-1-(3-chlorpyridin-2-yl)-1 H-pyrazol-5- yl]carbonyl}amino)benzoyl]-1 ,2-dimethylhydrazinecarboxylate; M.28.5a) to M.28.5d) and

M.28.5h) to M.28.5I): M.28.5a) N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl ]- phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3 -carboxamide; M.28.5b) N-[4-chloro- 2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-6-methyl-pheny l]-2-(3-chloro-2-pyridyl)-5- (trifluoromethyl)pyrazole-3-carboxamide; M.28.5c) N-[4-chloro-2-[(di-2-propyl-lambda-4- sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyri dyl)-5-(trifluoromethyl)pyrazole-3- carboxamide; M.28.5d) N-[4,6-dichloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carba moyl]- phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3 -carboxamide; M.28.5h) N-[4,6- dibromo-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl ]-2-(3-chloro-2-pyridyl)-5- (trifluoromethyl)pyrazole-3-carboxamide; M.28.5i) N-[2-(5-amino-1 ,3,4-thiadiazol-2-yl)-4-chloro- 6-methylphenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1 H-pyrazole-5-carboxamide; M.28.5j) 3- Chloro-1-(3-chloro-2-pyridinyl)-N-[2,4-dichloro-6-[[(1-cyano -1- methylethyl)amino]carbonyl]phenyl]-1 H-pyrazole-5-carboxamide; M.28.5k) 3-Bromo-N-[2,4- dichloro-6-(methylcarbamoyl)phenyl]-1-(3,5-dichloro-2-pyridy l)-1 H-pyrazole-5-carboxamide; M.28.5I) N-[4-Chloro-2-[[(1 ,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chloro -2- pyridinyl)-3-(fluoromethoxy)-1 H-pyrazole-5-carboxamide; or

M.28.6: cyhalodiamide; or;

M.29. insecticidal active compounds of unknown or uncertain mode of action, e.g. afidopyro- pen, afoxolaner, azadirachtin, amidoflumet, benzoximate, bifenazate, broflanilide,

bromopropylate, chinomethionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, flupyradifurone, fluralaner, metoxadiazone, piperonyl butoxide, pyflubumide, pyridalyl, pyrifluquinazon, sulfoxaflor, tioxazafen, triflumezopyrim,

M.29.3: 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1 ,4-dioxa-9-azadispiro[4.2.4.2]-tetradec- 11-en-10-one,

M.29.4: 3-(4'-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1-az aspiro[4.5]dec-3-en-2-one, M.29.5: 1-[2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]pheny l]-3-(trifluoromethyl)-1 H-1 ,2,4- triazole-5-amine, or actives on basis of bacillus firmus (Votivo, 1-1582); or

a compound selected from M.29.6 consisting of M.29.6a) to M.29.6k): M.29.6a) (E/Z)-N-[1-[(6- chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-ace tamide; M.29.6b) (E/Z)-N-[1-[(6-chloro- 5-fluoro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-a cetamide; M.29.6c) (E/Z)-2,2,2-trifluo- ro-N-[1 -[(6-fluoro-3-pyridyl)methyl]-2-pyridylidene]acetamide; M.29.6d) (E/Z)-N-[1 -[(6-bromo-3- pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide; M.29.6e) (E/Z)-N-[1-[1 -(6-chloro-3-pyri- dyl)ethyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide; M.29.6f) (E/Z)-N-[1-[(6-chloro-3- pyridyl)methyl]-2-pyridylidene]-2,2-difluoro-acetamide; M.29.6g) (E/Z)-2-chloro-N-[1-[(6-chloro-3- pyridyl)methyl]-2-pyridylidene]-2,2-difluoro-acetamide; M.29.6h) (E/Z)-N-[1-[(2-chloropyrimidin- 5-yl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide; M.29.6i) (E/Z)-N-[1-[(6-chloro-3- pyridyl)methyl]-2-pyridylidene]-2,2,3,3,3-pentafluoro-propan amide.); M.29.6j) N-[1-[(6-chloro-3- pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-thioacetamid e; or M.29.6k) N-[1-[(6-chloro-3- pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-N'-isopropyl -acetamidine;

M.29.8: fluazaindolizine; M.29.9.a): 4-[5-(3,5-dichlorop enyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1- oxothietan-3-yl)benzamide; M.29.9.b): fluxametamide;

M.29.10: 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]- 1 H-pyrazole;

a compound selected from M.29.11 , consisting of M.29.11 b) to M.29.11 p): M.29.11.b) 3- (benzoylmethylamino)-N-[2-bromo-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)propyl]-6-

(trifluoromethyl)phenyl]-2-fluoro-benzamide; M.29.11.c) 3-(benzoylmethylamino)-2-fluoro-N-[2- iodo-4-[1 ,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6-(trifluoromet hyl)phenyl]-benzamide;

M.29.1 1.d) N-[3-[[[2-iodo-4-[1 ,2,2,24etrafluoro-1-(trifluoromethyl)ethyl]-6- (trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-methyl-benz amide; M.29.1 1.e) N-[3-[[[2- bromo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]amino]car bonyl]-2- fluorophenyl]-4-fluoro-N-methyl-benzamide; M.29.1 1.f) 4-fluoro-N-[2-fluoro-3-[[[2-iodo-4-[1 ,2,2,2- tetrafluoro-1-(trifluoromethyl)ethyl]-6-(trifluoromethyl)phe nyl]amino]carbonyl]phenyl]-N-methyl- benzamide; M.29.11 .g) 3-fluoro-N-[2-fluoro-3-[[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)- ethyl]-6-(trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-me thyl-benzamide; M.29.11 .h) 2- chloro-N-[3-[[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6-

(trifluoromethyl)phenyl]amino]carbonyl]phenyl]- 3-pyridinecarboxamide; M.29.1 1.i) 4-cyano-N- [2-cyano-5-[[2,6-dibromo-4-[1 , 2,2,3,3, 3-hexafluoro-1-(trifluoromethyl)- propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; M.29.1 1.j) 4-cyano-3-[(4-cyano-2-methyl- benzoyl)amino]-N-[2,6-dichloro-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)propyl]phenyl]-2- fluoro-benzamide; M.29.1 1.k) N-[5-[[2-chloro-6-cyano-4-[1 ,2,2,3,3, 3-hexafluoro-1 -

(trifluoromethyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl] -4-cyano-2-methyl-benzamide;

M.29.1 1.1) N-[5-[[2-bromo-6-chloro-4-[2,2,2-trifluoro-1-hydroxy-1-

(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]- 4-cyano-2-methyl-benzamide;

M.29.1 1.m) N-[5-[[2-bromo-6-chloro-4-[1 ,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)- propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-be nzamide; M.29.1 1.n) 4-cyano-N-

[2-cyano-5-[[2,6-dichloro-4-[1 , 2,2,3, 3,3-hexafluoro-1-(trifluoromethyl)- propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; M.29.1 1.o) 4-cyano-N-[2-cyano-5-[[2,6- dichloro-4-[ ,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl ]phenyl]-2-methyl- benzamide; M.29.11 .p) N-[5-[[2-bromo-6-chloro-4-[1 ,2,2,2-tetrafluoro-1- (trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-c yano-2-methyl-benzamide;

a compound selected from M.29.12, consisting of M.29.12a) to M.29.12m): M.29.12.a) 2-(1 ,3- Dioxan-2-yl)-6-[2-(3-pyridinyl)-5-thiazolyl]-pyridine; M.29.12.b) 2-[6-[2-(5-Fluoro-3-pyridinyl)-5- thiazolyl]-2-pyridinyl]-pyrimidine; M.29.12.c) 2-[6-[2-(3-Pyridinyl)-5-thiazolyl]-2-pyridinyl]- pyrimidine; M.29.12. d) N-Methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-car boxamide; M.29.12.e) N-Methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-car boxamide; M.29.12.f) N- Ethyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthio-pr opanamide; M.29.12. g) N-Methyl-N- [4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthio-propanamid e; M.29.12. h) N,2-Dimethyl-N-[4- methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthio-propanamide; M.29.12. i) N-Ethyl-2-methyl-N-[4- methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthio-propanamide; M.29.12.j) N-[4-Chloro-2-(3- pyridyl)thiazol-5-yl]-N-ethyl-2-methyl-3-methylthio-propanam ide; M.29.12.k) N-[4-Chloro-2-(3- pyridyl)thiazol-5-yl]-N,2-dimethyl-3-methylthio-propanamide; M.29.12.1) N-[4-Chloro-2-(3- pyridyl)thiazol-5-yl]-N-methyl-3-methylthio-propanamide; M.29.12.m) N-[4-Chloro-2-(3- pyridyl)thiazol-5-yl]-N-ethyl-3-methylthio-propanamide; M.29.14a) 1 -[(6-Chloro-3-pyridinyl)methyl]-1 , 2,3,5, 6,7-hexahydro-5-methoxy-7-methyl-8-nitro- imidazo[1 ,2-a]pyridine; or M.29.14b) 1-[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro- 1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridin-5-ol;

M.29.16a) 1 -isopropyl-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxam ide; or M.29.16b) 1- (1 ,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol e-4-carboxamide; M.29.16c) N,5- dimethyl-N-pyridazin-4-yl-1 -(2,2,2-trifluoro-1 -methyl-ethyl)pyrazole-4-carboxamide; M.29.16d) 1 - [1 -(1 -cyanocyclopropyl)ethyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-p yrazole-4-carboxamide;

M.29.16e) N-ethyl-1-(2-fluoro-1-methyl-propyl)-5-methyl-N-pyridazin-4- yl-pyrazole-4- carboxamide; M.29.16†) 1-(1 ,2-dimethylpropyl)-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4- carboxamide; M.29.16g) 1-[1-(1 -cyanocyclopropyl)ethyl]-N,5-dimethyl-N-pyridazin-4-yl-pyraz ole- 4-carboxamide; M.29.16h) N-methyl-1-(2-fluoro-1 -methyl-propyl]-5-methyl-N-pyridazin-4-yl- pyrazole-4-carboxamide; M.29.16i) 1-(4,4-difluorocyclohexyl)-N-ethyl-5-methyl-N-pyridazin-4-yl - pyrazole-4-carboxamide; or M.29.16j) 1-(4,4-difluorocyclohexyl)-N,5-dimethyl-N-pyridazin-4-yl- pyrazole-4-carboxamide,

M.29.17 consisting of M.29.17a) to M.29.17j): M.29.17a) N-(1-methylethyl)-2-(3-pyridinyl)-2H- indazole-4-carboxamide; M.29. 7b) N-cyclopropyl-2-(3-pyridinyl)-2H-indazole-4-carboxamide; M.29.17c) N-cyclohexyl-2-(3-pyridinyl)-2H-indazole-4-carboxamide; M.29.17d) 2-(3-pyridinyl)-N- (2,2,2-trifluoroethyl)-2H-indazole-4-carboxamide; M.29.17e) 2-(3-pyridinyl)-N-[(tetrahydro-2- furanyl)methyl]-2H-indazole-5-carboxamide; M.29.17f) methyl 2-[[2-(3-pyridinyl)-2H-indazol-5- yl]carbonyl]hydrazinecarboxylate; M.29.17g) N-[(2,2-difluorocyclopropyl)methyl]-2-(3-pyridinyl)- 2H-indazole-5-carboxamide; M.29.17h) N-(2,2-difluoropropyl)-2-(3-pyridinyl)-2H-indazole-5- carboxamide; M.29.17i) 2-(3-pyridinyl )-N-(2-pyrimidinylmethyl )-2H-indazole-5-carboxamide; M.29.17j) N-[(5-methyl-2-pyrazinyl)methyl]-2-(3-pyridinyl)-2H-indazole -5-carboxamide, or M.29.18 a compound selected from M.29.18a) to M.29.18d): M.29.18a) N-[3-chloro-1-(3-pyri- dyl)pyrazol-4-yl]-N-ethyl-3-(3,3,3-trifluoropropylsulfanyl)p ropanamide; M.29.18b) N-[3-chloro-1 - (3-pyridyl)pyrazol-4-yl]-N-ethyl-3-(3,3,3-trifluoropropylsul finyl)propanamide; M.29.18c) N-[3-chlo- ro-1 -(3-pyridyl)pyrazol-4-yl]-3-[(2,2-difluorocyclopropyl)methyl sulfanyl]-N-ethyl-propanamide; M.29.18d) N-[3-chloro-1-(3-pyridyl)pyrazol-4-yl]-3-[(2,2-difluorocyclo propyl)methylsulfinyl]-N- ethyl-propanamide;

M.29.19 sarolaner,

M.29.20 lotilaner.

The commercially available compounds of the group M listed above may be found in The Pesticide Manual, 16th Edition, C. MacBean, British Crop Protection Council (2013) among other publications. The online Pesticide Manual is updated regularly and is accessible through http://bcpcdata.com/pesticide-manual.html.

Another online data base for pesticides providing the ISO common names is

http://www.alanwood.net/pesticides.

The M.4 cycloxaprid is known from WO2010/069266 and WO201 1/069456, M.4A.2 guadipyr, is known from WO2013/003977, and M.4A.3 (approved as paichongding in China) is known from WO2007/101369. M.22B.1 is described in CN10171577 and M.22B.2 in CN102126994. M.28.1 and M.28.2 are known from WO2007/101540. M.28.3 is described in WO2005/077934. M.28.4 is described in WO2007/043677. M.28.5a) to M.28.5d) and M.28.5h) are described in WO 2007/006670, WO2013/024009 and WO2013/024010, Μ.28.5Ϊ) is described in

WO201 1/085575, M.28.5j) in WO2008/134969, M.28.5k) in US2011/046186 and M.28.5I) in WO20 2/034403. M.28.6 can be found in WO2012/034472. M.29.3 is known from WO2006/089633 and M.29.4 from WO2008/06791 1. M.29.5 is described in WO2006/043635, and biological control agents on the basis of bacillus firmus are described in WO2009/124707. Compounds M.29.6a) to Μ.29.6Ϊ) are described in WO2012/029672, and M.29.6j) and M.29.6k) in WO2013/129688. M.29.8 is known from WO2013/055584. M.29.9.a) is described in

WO20 3/050317. M.29.9.b) is described in WO2014/126208. M.29.10 is known from

WO2010/060379. Broflanilide and M.29.1 1 .b) to M.29.1 1.h) are described in WO2010/018714, and M.29.1 1 i) to M.29.1 1 .p) in WO2010/127926. M.29.12.a) to M.29.12.c) are known from WO2010/006713, M.29.12.d) and Μ.29.12.Θ) are known from WO2012/000896, and M.29.12.†) to M.29.12.m) from WO2010/129497. M.29.14a) and M.29.14b) are known from

WO2007/101369. M.29.16.a) to M.29.16h) are described in WO2010/034737, WO2012/084670, and WO2012/143317, resp., and Μ.29.16Ϊ) and M.29.16j) are described in WO2015/055497. M.29.17a) to M.29.17J) are described in WO2015/038503. M.29.18a) to M.29.18d) are described in US2014/0213448. M.29.19 is described in W02014/036056. M.29.20 is known from WO2014/090918.

The following list of fungicides, in conjunction with which the compounds of the invention can be used, is intended to illustrate the possible combinations but does not limit them:

A) Respiration inhibitors

Inhibitors of complex III at Q ₀ site (e. g. strobilurins): azoxystrobin (A.1 .1 ), coumethoxy- strobin (A.1 .2), coumoxystrobin (A.1.3), dimoxystrobin (A.1.4), enestroburin (A.1.5), fenamin- strobin (A.1 .6), fenoxystrobin/flufenoxystrobin (A.1 .7), fluoxastrobin (A.1 .8), kresoxim-methyl (A.1 .9), mandestrobin (A.1 .10), metominostrobin (A.1 .1 1 ), orysastrobin (A.1 .12), picoxy.strobin (A.1 .13), pyraclostrobin (A.1.14), pyrametostrobin (A.1.15), pyraoxystrobin (A.1.16), trifloxystro- bin (A.1 .17), 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylideneaminooxymethyl)-phenyl)-2- methoxyimino-N-methyl-acetamide (A.1.18), pyribencarb (A.1 .19), triclopyricarb/chlorodincarb (A.1 .20), famoxadone (A.1 .21 ), fenamidone (A.1 .21 ), methyl-/V-[2-[(1 ,4-dimethyl-5-phenyl-pyra- zol-3-yl)oxylmethyl]phenyl]-N-methoxy-carbamate (A.1.22), 1 -[3-chloro-2-[[1 -(4-chlorophenyl)- 1 H-pyrazol-3-yl]oxymethyl]phenyl]-4-methyl-tetrazol-5-one (A.1 .23), 1-[3-bromo-2-[[1 -(4- chlorophenyl)pyrazol-3-yl]oxymethyl]phenyl]-4-methyl-tetrazo l-5-one (A.1 .24), 1 -[2-[[1 -(4- chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-meth yl-tetrazol-5-one (A.1.25), 1 -[2-[[1 - (4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-fluoro-phenyl]-4-m ethyl-tetrazol-5-one (A.1 .26), 1-[2- [[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxymethyl]-3-fluoro-phe nyl]-4-methyl-tetrazol-5-one

(A.1 .27), 1 -[2-[[4-(4-chlorophenyl)thiazol-2-yl]oxymethyl]-3-methyl-phe nyl]-4-methyl-tetrazol-5- one (A.1 .28), 1 -[3-chloro-2-[[4-(p-tolyl)thiazol-2-yl]oxymethyl]phenyl]-4-m ethyl-tetrazol-5-one (A.1 .29), 1 -[3-cyclopropyl-2-[[2-methyl-4-(1-methylpyrazol-3-yl)phenoxy ]methyl]phenyl]- 4-methyl-tetrazol-5-one (A.1 .30), 1 -[3-(difluoromethoxy)-2-[[2-methyl-4-(1 -methylpyrazol- 3-yl)phenoxy]methyl]phenyl]-4-methyl-tetrazol-5-one (A.1 .31 ), 1 -methyl-4-[3-methyl- 2-[[2-methyl-4-(1 -methylpyrazol-3-yl)phenoxy]methyl]phenyl]tetrazol-5-one (A.1.32), 1 -methyl-4- [3-methyl-2-[[1 -[3-(trifluoromethyl)phenyl]-ethylideneamino]oxymethyl]pheny l]tetrazol-5-one (A.1 .33), (2^2£)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]-oxy-2-methoxyimino-/V,3-d imethyl-pent-3- enamide (A.1 .34), (2^2. )-5-[1 -(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-/V,3-dimeth yl- pent-3-enamide (A.1 .35), (^2.r)-5-[1-(4-chloro-2-fluoro-phenyl)pyrazol-3-yl]oxy-2- methoxyimino- V,3-dimethyl-pent-3-enamide (A.1 .36),

inhibitors of complex III at Qi site: cyazofamid (A.2.1 ), amisulbrom (A.2.2), [(3S,6S,7R,8R)- 8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]- 6-met yl-4,9-dioxo-1 ,5-dioxonan- 7-yl] 2-methylpropanoate (A.2.3), [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy- pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate (A.2.4), [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycar onyloxy-4-methoxy-pyridine-2-carbonyl)amino]-6- methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate (A.2.5), [(3S,6S,7R,8R)-8-benzyl-3-[[3- (1 ,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2-carbonyl]am ino]-6-methyl-4,9-dioxo-1 ,5- dioxonan-7-yl] 2-methylpropanoate (A.2.6); (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridi- nyl)carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1 ,5-dioxonan-7-yl 2-methylpropanoate (A.2.7), (3S,6S,7R,8R)-8-benzyl-3-[3-[(isobutyryloxy)methoxy]-4-metho xypicolinamido]-6- methyl-4,9-dioxo-1 ,5-dioxonan-7-yl isobutyrate (A.2.8);

inhibitors of complex II (e. g. carboxamides): benodanil (A.3.1 ), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.1 1 ), isopyrazam (A.3.12), mepronil (A.3.13), oxycarboxin (A.3.14), penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), tecloftalam (A.3.17), thifluzamide (A.3.18), N-(4'-trifluoromethylthiobiphenyl-2-yl)-3-di- fluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide (A.3.19), N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)- 1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide (A.3.20), 3-(difluoromethyl)-1 -methyl-N-(1 , 1 ,3- trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.21 ), 3-(trifluoromethyl)-1 -methyl-N-(1 , 1 ,3-tri- methylindan-4-yl)pyrazole-4-carboxamide (A.3.22), 1 ,3-dimethyl-N-(1 , 1 ,3-trimethylindan-4- yl)pyrazole-4-carboxamide (A.3.23), 3-(trifluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4- yl)pyrazole-4-carboxamide (A.3.24), 1 ,3,5-trimethyl-N-(1 , 1 ,3-trimethylindan-4-yl)pyrazole-4-car- boxamide (A.3.25), N-(7-fluoro-1 , 1 ,3-trimethyl-indan-4-yl)-1 ,3-dimethyl-pyrazole-4-carboxamide (A.3.26), N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methyl-ethyl]-3-(diflu oromethyl)-1 -methyl-pyra- zole-4-carboxamide (A.3.27);

- other respiration inhibitors (e. g. complex I, uncouplers): diflumetorim (A.4.1 ), (5,8-difluoro- quinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2- yloxy)-phenyl]-ethyl}-amine (A.4.2); nitrophenyl derivates: binapacryl (A.4.3), dinobuton (A.4.4), dinocap (A.4.5), fluazinam (A.4.6); ferimzone (A.4.7); organometal compounds: fentin salts, such as fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.1 1 ); and silthiofam (A.4.12); B) Sterol biosynthesis inhibitors (SBI fungicides)

C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole (B.1 .1 ), bitertanol (B.1 .2), bromuconazole (B.1 .3), cyproconazole (B.1 .4), difenoconazole (B.1.5), diniconazole (B.1 .6), diniconazole-M (B.1 .7), epoxiconazole (B.1 .8), fenbuconazole (B.1.9), fluquinconazole (B.1 .10), flusilazole (B.1.1 1 ), flutriafol (B.1.12), hexaconazole (B.1 .13), imibenconazole (B.1 .14), ipconazole (B.1 .15), metconazole (B.1 .17), myclobutanil (B.1 .18), oxpoconazole (B.1 .19), paclo- butrazole (B.1 .20), penconazole (B.1.21 ), propiconazole (B.1 .22), prothioconazole (B.1 .23), simeconazole (B.1 .24), tebuconazole (B.1.25), tetraconazole (B.1.26), triadimefon (B.1 .27), tria- dimenol (B.1 .28), triticonazole (B.1 .29), uniconazole (B.1.30), 1 -[/-e ^> A(2S;3 )-3-(2-chlorophenyl)- 2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1 H-[1 ,2,4]triazolo (B.1.31 ), 2-[re/-(2S;3R)-3- (2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-2H-[ 1 ,2,4]triazole-3-thiol (B.1.32), 2-[2- chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol (B.1.33), 1 -[4-(4-chlorophen- oxy)-2-(trifluoromethyl)phenyl]-1 -cyclopropyl-2-(1 ,2,4-triazol-1-yl)ethanol (B.1 .34), 2-[4-(4-chlo- rophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1.35), 2-[2-chloro-4-(4- c lorophenoxy) phenyl]- 1-(1 ,2,4-triazol-1-yl)butan-2-ol (B.1 .36), 2-[4-(4-chlorophenoxy)-2-(triflu- oromethyl)phenyl]-3-methyl-1-(1 ,2,4-triazol-1-yl)butan-2-ol (B.1.37), 2-[4-(4-chlorophenoxy)-2- (trifluoromethyl)phenyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol (B.1 .38), 2-[2-chloro-4-(4-chlorophen- oxy)phenyl]-3-methyl-1-(1 ,2,4-triazol-1-yl)butan-2-ol (B.1.39), 2-[4-(4-chlorophenoxy)-2-(triflu- oromethyl)phenyl]-1-(1 ,2,4-triazol-1-yl)pentan-2-ol (B.1.40), 2-[4-(4-fluorophenoxy)-2-(trifluoro- methyl)phenyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol (B.1.41), 2-[2-chloro-4-(4-chlorophenoxy)phe- nyl]-1-(1 ,2,4-triazol-1-yl)pent-3-yn-2-ol (B.1.51); imidazoles: imazalil (B.1.42), pefurazoate (B.1.43), prochloraz (B.1 .44), triflumizol (B.1 .45); pyrimidines, pyridines and piperazines: fenari- mol (B.1.46), nuarimol (B.1.47), pyrifenox (B.1.48), triforine (B.1.49), [3-(4-chloro-2-fluoro- phenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(3-pyridyl)meth anol (B.1 .50);

Delta14-reductase inhibitors: aldimorph (B.2.1 ), dodemorph (B.2.2), dodemorph-acetate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spiroxamine (B.2.8);

Inhibitors of 3-keto reductase: fenhexamid (B.3.1 );

C) Nucleic acid synthesis inhibitors

phenylamides or acyl amino acid fungicides: benalaxyl (C.1.1 ), benalaxyl-M (C.1.2), kiralaxyl (C.1.3), metalaxyl (C.1 .4), metalaxyl-M (mefenoxam, C.1.5), ofurace (C.1.6), oxadixyl (C.1.7);

others: hymexazole (C.2.1 ), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine (C.2.6), 5-fluoro-2-(4- fluorophenylmethoxy)pyrimidin-4-amine (C.2.7);

D) Inhibitors of cell division and cytoskeleton

tubulin inhibitors, such as benzimidazoles, thiophanates: benomyl (D1.1 ), carbendazim (D1.2), fuberidazole (D1.3), thiabendazole (D1.4), thiophanate-methyl (D1 .5); triazolopyrimidi- nes: 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl )-[1 ,2,4]triazolo[1 ,5-a]pyrimidine (D1.6);

other cell division inhibitors: diethofencarb (D2.1 ), ethaboxam (D2.2), pencycuron (D2.3), fluopicolide (D2.4), zoxamide (D2.5), metrafenone (D2.6), pyriofenone (D2.7);

E) Inhibitors of amino acid and protein synthesis

- methionine synthesis inhibitors (anilino-pyrimidines): cyprodinil (E.1.1 ), mepanipyrim (E.1.2), pyrimethanil (E.1.3);

protein synthesis inhibitors: blasticidin-S (E.2.1), kasugamycin (E.2.2), kasugamycin hydrochloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6), polyoxine (E.2.7), validamycin A (E.2.8);

F) Signal transduction inhibitors

MAP / histidine kinase inhibitors: fluoroimid (F.1.1 ), iprodione (F.1.2), procymidone (F.1.3), vinclozolin (F.1.4), fenpiclonil (F.1.5), fludioxonil (F.1.6);

G protein inhibitors: quinoxyfen (F.2.1 );

G) Lipid and membrane synthesis inhibitors

- Phospholipid biosynthesis inhibitors: edifenphos (G.1 .1 ), iprobenfos (G.1.2), pyrazophos (G.1.3), isoprothiolane (G.1 .4);

lipid peroxidation: dicloran (G.2.1), quintozene (G.2.2), tecnazene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7);

phospholipid biosynthesis and cell wall deposition: dimethomorph (G.3.1), flumorph (G.3.2), mandipropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7) and N-(1-(1-(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4- fluorophenyl) ester (G.3.8);

compounds affecting cell membrane permeability and fatty acides: propamocarb (G.4.1); - fatty acid amide hydrolase inhibitors: oxathiapiprolin (G.5.1 ), 2-{3-[2-(1-{[3,5-bis(difluoro- methyl-1 H-pyrazol- -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5-yl}phenyl methanesulfonate (G.5.2), 2-{3-[2-(1 -{[3, 5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]acetyl}piperidin-4- yl) 1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate (G.5.3);

H) Inhibitors with Multi Site Action

- inorganic active substances: Bordeaux mixture (H.1.1 ), copper acetate (H.1.2), copper hydroxide (H.1.3), copper oxychloride (H.1.4), basic copper sulfate (H.1.5), sulfur (H.1.6);

thio- and dithiocarbamates: ferbam (H.2.1), mancozeb (H.2.2), maneb (H.2.3), metam (H.2.4), metiram (H.2.5), propineb (H.2.6), thiram (H.2.7), zineb (H.2.8), ziram (H.2.9);

organochlorine compounds (e. g. phthalimides, sulfamides, chloronitriles): anilazine (H.3.1), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.1 1), N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl- benzenesulfonamide (H.3.12);

guanidines and others: guanidine (H.4.1 ), dodine (H.4.2), dodine free base (H.4.3), guaza- tine (H.4.4), guazatine-acetate (H.4.5), iminoctadine (H.4.6), iminoctadine-triacetate (H.4.7), iminoctadine-tris(albesilate) (H.4.8), dithianon (H.4.9), 2,6-dimethyl-1 H,5H-[1 ,4]dithiino[2,3- c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone (H.4.10);

I) Cell wall synthesis inhibitors

inhibitors of glucan synthesis: validamycin (1.1.1), polyoxin B (1.1 .2);

- melanin synthesis inhibitors: pyroquilon (1.2.1 ), tricyclazole (I.2.2), carpropamid (I.2.3), dicyclomet (I.2.4), fenoxanil (1.2.5);

J) Plant defence inducers

acibenzolar-S-methyl (J.1.1 ), probenazole (J.1 .2), isotianil (J.1.3), tiadinil (J.1 .4), prohexa- dione-calcium (J.1.5); phosphonates: fosetyl (J.1.6), fosetyl-aluminum (J.1.7), phosphorous acid and its salts (J.1.8), potassium or sodium bicarbonate (J.1 .9);

K) Unknown mode of action

bronopol (K.1 .1), chinomethionat (K.1.2), cyflufenamid (K.1.3), cymoxanil (K.1.4), dazomet (K.1.5), debacarb (K.1.6), diclomezine (K.1.7), difenzoquat (K.1.8), difenzoquat-methylsulfate (K.1.9), diphenylamin (K.1.10), fenpyrazamine (K.1.11 ), flumetover (K.1.12), flusulfamide (K.1.13), flutianil (K.1.14), methasulfocarb (K.1.15), nitrapyrin (K.1.16), nitrothal-isopropyl (K.1.18), oxathiapiprolin (K.1.19), tolprocarb (K.1.20), oxin-copper (K.1.21), proquinazid

(K.1.22), tebufloquin (K.1.23), tecloftalam (K.1.24), triazoxide (K.1.25), 2-butoxy-6-iodo-3-pro- pylchromen-4-one (K.1.26), 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-(prop-2-yn- 1-yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1-yl]ethanone (K.1.27), 2- [3, 5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yloxy)phenyl]-4, 5- dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1-yl]ethanone (K.1.28), 2-[3,5- bis(difluoromethyl)-1 H-pyrazol-1-yl]-1 -[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5- dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1-yl]ethanone (K.1.29), N-(cyclo- propylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)- methyl)-2-phenyl acetamide (K.1.30), N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phen yl)-N-ethyl-N- formamidine (K.1.31 ), N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phen yl)-N-ethyl-N- methyl formamidine (K.1.32), N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy )- phenyl)-N-ethyl-N-methyl formamidine (K.1.33), N'-(5-difluoromethyl-2-methyl-4-(3-tri- methylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.34), methoxy-acetic acid 6- tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester (K.1.35), 3-[5-(4-methylphenyl)-2,3-dimethyl- isoxazolidin-3-yl]-pyridine (K.1.36), 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]- pyridine (pyrisoxazole) (K.1.37), N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide (K.1.38), 5-chloro-1-(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole (K.1.39), 2-(4- chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2- prop-2-ynyloxy-acetamide, ethyl (Z)-3-amino-2-cyano-3-phenyl-prop-2-enoate (K.1.40), picarbutrazox (K.1.41 ), pentyl N-[6-[[(Z)- [(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2 -pyridyl]carbamate (K.1.42), 2-[2- [(7,8-difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro-phenyl]prop an-2-ol (K.1.43), 2-[2-fluoro-6-[(8- fluoro-2-methyl-3-quinolyl)oxy]phen-yl]propan-2-ol (K.1.44), 3-(5-fluoro-3,3,4,4-tetramethyl-3,4- dihydroisoquinolin-1-yl)quinoline (K.1.45), 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1- yl)quinoline (K.1.46), 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl) quinoline (K.1.47), 9-fluoro-2,2-dimethyl-5-(3-quinolyl)-3H-1 ,4-benzoxazepine (K.1.48).

The fungicides described by common names, their preparation and their activity e.g. against harmful fungi is known (cf.: http://www.alanwood.net pesticides/); these substances are commercially available.

The fungicides described by lUPAC nomenclature, their preparation and their pesticidal activity is also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031 ; EP-A 226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941 ; EP-A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1 122 244, JP 2002316902; DE 19650197;

DE 10021412; DE 102005009458; US 3,296,272; US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501 ; WO 01/56358; WO 02/22583; WO 02/40431 ; WO 03/10149; WO 03/1 1853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491 ; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721 ; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624, WO 1 1/028657, WO2012/168188, WO 2007/006670, WO 201 1/77514; W013/047749, WO

10/069882, WO 13/047441 , WO 03/16303, WO 09/90181 , WO 13/007767, WO 13/010862, WO 13/127704, WO 13/024009, WO 13/024010 and WO 3/047441 , WO 13/ 62072,

WO 13/092224, WO 11/135833).

Suitable mixing partners for the compounds of the invention also include biopesticides.

Biopesticides have been defined as a form of pesticides based on micro-organisms (bacteria, fungi, viruses, nematodes, etc.) or natural products (compounds, such as metabolites, proteins, or extracts from biological or other natural sources) (U.S. Environmental Protection Agency: http://www.epa.gov/pesticides/biopesticides/). Biopesticides fall into two major classes, microbial and biochemical pesticides:

(1 ) Microbial pesticides consist of bacteria, fungi or viruses (and often include the metabolites that bacteria and fungi produce). Entomopathogenic nematodes are also classified as microbial pesticides, even though they are multi-cellular.

(2) Biochemical pesticides are naturally occurring substances or or structurally-similar and functionally identical to a naturally-occurring substance and extracts from biological sources that control pests or provide other crop protection uses as defined below, but have non-toxic mode of actions (such as growth or developmental regulation, attractents, repellents or defence activators (e.g. induced resistance) and are relatively non-toxic to mammals.

Biopesticides for use against crop diseases have already established themselves on a variety of crops. For example, biopesticides already play an important role in controlling downy mildew diseases. Their benefits include: a 0-Day Pre-Harvest Interval, the ability to use under moderate to severe disease pressure, and the ability to use in mixture or in a rotational program with other registered pesticides.

A major growth area for biopesticides is in the area of seed treatments and soil amendments. Biopesticidal seed treatments are e.g. used to control soil borne fungal pathogens that cause seed rots, damping-off, root rot and seedling blights. They can also be used to control internal seed borne fungal pathogens as well as fungal pathogens that are on the surface of the seed. Many biopesticidal products also show capacities to stimulate plant host defenses and other physiological processes that can make treated crops more resistant to a variety of biotic and abiotic stresses or can regulate plant growth. Many biopesticidal products also show capacities to stimulate plant health, plant growth and/or yield enhancing activity.

The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound of the invention or a mixture thereof.

An agrochemical composition comprises a pesticidally effective amount of a compound of the invention or a mixture thereof. The term "pesticidally effective amount" is defined below.

The compounds of the invention or the mixtures thereof can be converted into customary types of agro-chemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.

The compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.

Examples for suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifi- ers and binders.

Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclo-'hexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.

Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch;

fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.

Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl- sulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkyhnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol eth- oxylates.

Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are homo- or copolymers of

vinylpyrrolidone, vinylalcohols, or vinylacetate.

Suitable cationic surfactants are quaternary surfactants, e.g. quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines. Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compounds of the invention on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.

Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.

Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazoli- nones and benzisothiazolinones.

Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.

Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.

Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).

Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

Examples for composition types and their preparation are:

i) Water-soluble concentrates (SL, LS)

10-60 wt% of a compound I according to the invention and 5-15 wt% wetting agent (e.g.

alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) up to 100 wt%. The active substance dissolves upon dilution with water.

ii) Dispersible concentrates (DC)

5-25 wt% of a compound I according to the invention and 1-10 wt% dispersant (e. g. polyvinylpyrrolidone) are dissolved in up to 100 wt% organic solvent (e.g. cyclohexanone). Dilution with water gives a dispersion.

iii) Emulsifiable concentrates (EC)

15-70 wt% of a compound I according to the invention and 5-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in up to 100 wt% water- insoluble organic solvent (e.g. aromatic hydrocarbon). Dilution with water gives an emulsion. iv) Emulsions (EW, EO, ES)

5-40 wt% of a compound I according to the invention and 1-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% water-insoluble organic solvent (e.g. aromatic hydrocarbon). This mixture is introduced into up to 100 wt% water by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion.

v) Suspensions (SC, OD, FS)

In an agitated ball mill, 20-60 wt% of a compound I according to the invention are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0,1-2 wt% thickener (e.g. xanthan gum) and up to 100 wt% water to give a fine active substance suspension. Dilution with water gives a stable suspension of the active sub-stance. For FS type composition up to 40 wt% binder (e.g. polyvinylalcohol) is added. vi) Water-dispersible granules and water-soluble granules (WG, SG)

50-80 wt% of a compound I according to the invention are ground finely with addition of up to 100 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.

vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)

50-80 wt% of a compound I according to the invention are ground in a rotor-stator mill with addition of 1-5 wt% dispersants (e.g. sodium lignosulfonate), 1 -3 wt% wetting agents (e.g. alcohol ethoxylate) and up to 100 wt% solid carrier, e.g. silica gel. Dilution with water gives a stable dispersion or solution of the active substance.

viii) Gel (GW, GF)

In an agitated ball mill, 5-25 wt% of a compound I according to the invention are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1-5 wt% thickener (e.g. car- boxymethylcellulose) and up to 100 wt% water to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.

ix) Microemulsion (ME)

5-20 wt% of a compound I according to the invention are added to 5-30 wt% organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alkohol ethoxylate and arylphenol ethoxylate), and water up to 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.

x) Microcapsules (CS)

An oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g.

methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylme- thene-4,4'-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine) results in the formation of a polyurea microcapsule. The monomers amount to 1-10 wt%. The wt% relate to the total CS composition.

xi) Dustable powders (DP, DS)

1-10 wt% of a compound I according to the invention are ground finely and mixed intimately with up to 100 wt% solid carrier, e.g. finely divided kaolin.

xii) Granules (GR, FG)

0.5-30 wt% of a compound I according to the invention is ground finely and associated with up to 100 wt% solid carrier (e.g. silicate). Granulation is achieved by extrusion, spray-drying or the fluidized bed.

xiii) Ultra-low volume liquids (UL)

1-50 wt% of a compound I according to the invention are dissolved in up to 100 wt% organic solvent, e.g. aromatic hydrocarbon.

The compositions types i) to xi) may optionally comprise further auxiliaries, such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1-1 wt% anti-foaming agents, and 0.1 -1 wt% colorants. The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active sub-stance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).

Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the active substances or the compositions cormprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.

The user applies the composition according to the invention usually from a predosage de-vice, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.

According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.

In a further embodiment, either individual components of the composition according to the in- vention or partially premixed components, e. g. components comprising compounds of the invention and/or mixing partners as defined above, may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.

In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising compounds of the invention and/or mixing partners as defined above, can be applied jointly (e.g. after tank mix) or consecutively.

The compounds of the invention are suitable for use in protecting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, from attack or infestation by animal pests. Therefore, the invention also relates to a plant protection method, which comprises contacting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, to be protected from attack or infestation by animal pests, with a pesticidally effective amount of a compound of the invention.

The compounds of the invention are also suitable for use in combating or controlling animal pests. Therefore, the invention also relates to a method of combating or controlling animal pests, which comprises contacting the animal pests, their habitat, breeding ground, or food supply, or the crops, plants, plant propagation materials, such as seeds, or soil, or the area, material or environment in which the animal pests are growing or may grow, with a pesticidally effective amount of a compound of the invention.

The compounds of the invention are effective through both contact and ingestion.

Furthermore, the compounds of the invention can be applied to any and all developmental stages, such as egg, larva, pupa, and adult.

The compounds of the invention can be applied as such or in form of compositions comprising them as defined above. Furthermore, the compounds of the invention can be applied together with a mixing partner as defined above or in form of compositions comprising said mixtures as defined above. The components of said mixture can be applied simultaneously, jointly or separately, or in succession, that is immediately one after another and thereby creating the mixture "in situ" on the desired location, e.g. the plant, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.

The application can be carried out both before and after the infestation of the crops, plants, plant propagation materials, such as seeds, soil, or the area, material or environment by the pests.

Suitable application methods include inter alia soil treatment, seed treatment, in furrow application, and foliar application. Soil treatment methods include drenching the soil, drip irrigation (drip application onto the soil), dipping roots, tubers or bulbs, or soil injection. Seed treatment techniques include seed dressing, seed coating, seed dusting, seed soaking, and seed pelleting. In furrow applications typically include the steps of making a furrow in cultivated land, seeding the furrow with seeds, applying the pesticidally active compound to the furrow, and closing the furrow. Foliar application refers to the application of the pesticidally active compound to plant foliage, e.g. through spray equipment. For foliar applications, it can be advantageous to modify the behavior of the pests by use of pheromones in combination with the compounds of the invention. Suitable pheromones for specific crops and pests are known to a skilled person and publicly available from databases of pheromones and semiochemicals, such as http://www.pherobase.com.

As used herein, the term "contacting" includes both direct contact (applying the

compounds/compositions directly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus, i.e. habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest is growing or may grow, of the animal pest or plant).

The term "animal pest" includes arthropods, gastropods, and nematodes. Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects. Insects, which are of particular relevance for crops, are typically referred to as crop insect pests.

The term "crop" refers to both, growing and harvested crops.

The term "plant" includes cereals, e.g. durum and other wheat, rye, barley, triticale, oats, rice, or maize (fodder maize and sugar maize / sweet and field corn); beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, nectarines, almonds, cherries, papayas, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as beans, lentils, peas, alfalfa or soybeans; oil plants, such as rapeseed (oilseed rape), turnip rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, pumpkins, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as eggplant, spinach, lettuce (e.g. iceberg lettuce), chicory, cabbage, asparagus, cabbages, carrots, onions, garlic, leeks, tomatoes, potatoes, cucurbits or sweet peppers; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rapeseed, sugar cane or oil palm; tobacco; nuts, e.g. walnuts; pistachios; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers (e.g. carnation, petunias, geranium/pelargoniums, pansies and impatiens), shrubs, broad-leaved trees (e.g. poplar) or evergreens, e.g. conifers; eucalyptus; turf; lawn; grass such as grass for animal feed or ornamental uses. Preferred plants include potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rapeseed, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.

The term "plant" is to be understood as including wild type plants and plants, which have been modified by either conventional breeding, or mutagenesis or genetic engineering, or by a combination thereof.

Plants, which have been modified by mutagenesis or genetic engineering, and are of particular commercial importance, include alfalfa, rapeseed (e.g. oilseed rape), bean, carnation, chicory, cotton, eggplant, eucalyptus, flax, lentil, maize, melon, papaya, petunia, plum, poplar, potato, rice, soybean, squash, sugar beet, sugarcane, sunflower, sweet pepper, tobacco, tomato, and cereals (e.g. wheat), in particular maize, soybean, cotton, wheat, and rice. In plants, which have been modified by mutagenesis or genetic engineering, one or more genes have been mutagenized or integrated into the genetic material of the plant. The one or more mutagenized or integrated genes are preferably selected from pat, epsps, cryl Ab, bar, cryl Fa2, cryl Ac, cry34Ab1 , cry35AB1 , cry3A, cryF, cryl F, mcry3a, cry2Ab2, cry3Bb1 , cry1A.105, dfr, barnase, vip3Aa20, barstar, als, bxn, bp40, asnl , and ppo5. The mutagenesis or integration of the one or more genes is performed in order to improve certain properties of the plant. Such properties, also known as traits, include abiotic stress tolerance, altered growth/yield, disease resistance, herbicide tolerance, insect resistance, modified product quality, and pollination control. Of these properties, herbicide tolerance, e.g. imidazolinone tolerance, glyphosate tolerance, or glufosinate tolerance, is of particular importance. Several plants have been rendered tolerant to herbicides by mutagenesis, e.g. Clearfield® oilseed rape being tolerant to imidazolinones, e.g. imazamox. Alternatively, genetic engineering methods have been used to render plants, such as soybean, cotton, corn, beets and oil seed rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which are commercially available under the trade names

Roundup eady® (glyphosate) and LibertyLink® (glufosinate). Furthermore, insect resistance is of importance, in particular lepidopteran insect resistance and coleopteran insect resistance. Insect resistance is typically achieved by modifying plants by integrating cry and/or vip genes, which were isolated from Bacillus thuringiensis (Bt), and code for the respective Bt toxins.

Genetically modified plants with insect resistance are commercially available under trade names including WideStrike®, Bollgard®, Agrisure®, Herculex®, YieldGard®, Genuity®, and Intacta®. Plants may be modified by mutagenesis or genetic engineering either in terms of one property (singular traits) or in terms of a combination of properties (stacked traits). Stacked traits, e.g. the combination of herbicide tolerance and insect resistance, are of increasing importance. In general, all relevant modified plants in connection with singular or stacked traits as well as detailed information as to the mutagenized or integrated genes and the respective events are available from websites of the organizations "International Service for the Acquisition of Agri- biotech Applications (ISAAA)" (http://www.isaaa.org/gmapprovaldatabase) and "Center for Environmental Risk Assessment (CERA)" (http://cera-gmc.org/GMCropDatabase).

It has surprisingly been found that the pesticidal activity of the compounds of the invention may be enhanced by the insecticidal trait of a modified plant. Furthermore, it has been found that the compounds of the invention are suitable for preventing insects to become resistant to the insecticidal trait or for combating pests, which already have become resistant to the insecticidal trait of a modified plant. Moreover, the compounds of the invention are suitable for combating pests, against which the insecticidal trait is not effective, so that a complementary insecticidal activity can advantageously be used.

The term "plant propagation material" refers to all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e.g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emergence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting.

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

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.

In the case of soil treatment, in furrow application or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m ² , preferably from 0.001 to 20 g per 100 m ² .

For use in treating crop plants, e.g. by foliar application, the rate of application of the active ingredients of this invention may be in the range of 0.0001 g to 4000 g per hectare, e.g. from 1 g to 2 kg per hectare or from 1 g to 750 g per hectare, desirably from 1 g to 100 g per hectare, more desirably from 10 g to 50 g per hectare, e.g., 10 to 20 g per hectare, 20 to 30 g per hectare, 30 to 40 g per hectare, or 40 to 50 g per hectare.

The compounds of the invention are particularly suitable for use in the treatment of seeds in order to protect the seeds from insect pests, in particular from soil-living insect pests, and the resulting seedling's roots and shoots against soil pests and foliar insects. The invention therefore also relates to a method for the protection of seeds from insects, in particular from soil insects, and of the seedling's roots and shoots from insects, in particular from soil and foliar insects, said method comprising treating the seeds before sowing and/or after pregermination with a compound of the invention. The protection of the seedling's roots and shoots is preferred. More preferred is the protection of seedling's shoots from piercing and sucking insects, chewing insects and nematodes.

The term "seed treatment" comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking, seed pelleting, and in-furrow application methods. Preferably, the seed treatment application of the active compound is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.

The invention also comprises seeds coated with or containing the active compound. The term "coated with and/or containing" generally signifies that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the said propagation product is (re)planted, it may absorb the active ingredient.

Suitable seed is e.g. seed of cereals, root crops, oil crops, vegetables, spices, ornamentals, e.g. seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.

In addition, the active compound may also be used for the treatment of seeds from plants, which have been modified by mutagenisis or genetic engineering, and which e.g. tolerate the action of herbicides or fungicides or insecticides. Such modified plants have been described in detail above.

Conventional seed treatment formulations include e.g. flowable concentrates FS, solutions LS, suspoemulsions (SE), powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter. Preferably, the formulations are applied such that germination is not included.

The active substance concentrations in ready-to-use formulations, which may be obtained after two-to-tenfold dilution, are preferably from 0.01 to 60% by weight, more preferably from 0.1 to 40 % by weight.

In a preferred embodiment a FS formulation is used for seed treatment. Typically, a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.

Especially preferred FS formulations of the compounds of the invention for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the active ingredient, from 0.1 to 20 % by weight (1 to 200 g/l) of at least one surfactant, e.g. 0.05 to 5 % by weight of a wetter and from 0.5 to 15 % by weight of a dispersing agent, up to 20 % by weight, e.g. from 5 to 20 % of an anti-freeze agent, from 0 to 15 % by weight, e.g. 1 to 15 % by weight of a pigment and/or a dye, from 0 to 40 % by weight, e.g. 1 to 40 % by weight of a binder (sticker /adhesion agent), optionally up to 5 % by weight, e.g. from 0.1 to 5 % by weight of a thickener, optionally from 0.1 to 2 % of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a filler/vehicle up to 100 % by weight.

In the treatment of seed, the application rates of the compounds of the invention are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, more preferably from 1 g to 000 g per 100 kg of seed and in particular from 1 g to 200 g per 100 kg of seed, e.g. from 1 g to 100 g or from 5 g to 100 g per 100 kg of seed.

The invention therefore also relates to seed comprising a compound of the invention, or an agriculturally useful salt thereof, as defined herein. The amount of the compound of the invention or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed. For specific crops such as lettuce the rate can be higher.

The compounds of the present invention may also be used for improving the health of a plant. Therefore, the present invention also relates to a method for improving plant health by treating a plant, plant propagation material and/or the locus where the plant is growing or is to grow with an effective and non-phytotoxic amount of a compound of the invention.

As used herein "an effective and non-phytotoxic amount" means that the compound is used in a quantity which allows to obtain the desired effect but which does not give rise to any phytotoxic symptom on the treated plant or on the plant grown from the treated propagule or treated soil.

The terms "plant" and "plant propagation material" are defined above.

"Plant health" is defined as a condition of the plant and/or its products which is determined by several aspects alone or in combination with each other such as yield (e.g. increased biomass and/or increased content of valuable ingredients), quality (e.g. improved content or composition of certain ingredients or shelf life), plant vigour (e.g. improved plant growth and/or greener leaves ("greening effect"), tolerance to abiotic e.g. drought) and/or biotic stress (e.g. disease) and production efficiency (e.g. harvesting efficiency, processability).

The above identified indicators for the health condition of a plant may be interdependent and may result from each other. Each indicator is defined in the art and can be determined by methods known to a skilled person.

The compounds of the invention are also suitable for use against non-crop insect pests. For use against said non-crop pests, compounds of the invention can be used as bait composition, gel, general insect spray, aerosol, as ultra-low volume application and bed net (impregnated or surface applied). Furthermore, drenching and rodding methods can be used.

As used herein, the term "non-crop insect pest" refers to pests, which are particularly relevant for non-crop targets, such as ants, termites, wasps, flies, ticks, mosquitos, crickets, or cockroaches.

The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). The bait employed in the composition is a product, which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it. The attractiveness can be manipulated by using feeding stimulants or sex pheromones. Food stimulants are chosen, e.g. but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or

polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature (e.g. http://www.pherobase.com), and are known to those skilled in the art.

For use in bait compositions, the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound.

Formulations of the compounds of the invention as aerosols (e.g in spray cans), oil sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are preferably composed of the active compound, solvents, furthermore auxiliaries such as emulsifiers, perfume oils, if appropriate stabilizers, and, if required, propellants.

The oil spray formulations differ from the aerosol recipes in that no propellants are used.

For use in spray compositions, the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.

The compounds of the invention and its respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.

Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with compounds of the invention and its respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like. Insecticidal compositions for application to fibers, fabric, knitgoods, nonwovens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder.

The compounds of the invention and its compositions can be used for protecting wooden materials such as trees, board fences, sleepers, frames, artistic artifacts, etc. and buildings, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).

Customary application rates in the protection of materials are, e.g. from 0.001 g to 2000 g or from 0.01 g to 1000 g of active compound per m ² treated material, desirably from 0.1 g to 50 g per m ² .

Insecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and/or insecticide. The compounds of the the invention are especially suitable for efficiently combating animal pests such as arthropods, gastropods and nematodes including but not limited to:

insects from the order of Lepidoptera, e.g. Achroia grisella, Acleris spp. such as A. fimbriana, A. gloverana, A. variana; Acrolepiopsis assectella, Acronicta major, Adoxophyes spp. such as A. cyrtosema, A. orana; Aedia leucomelas, Agrotis spp. such as A. exclamationis, A. fucosa, A. ipsilon, A. orthogoma, A. segetum, A. subterranea; Alabama argillacea, Aleurodicus dispersus, Alsophila pometaria, Ampelophaga rubiginosa, Amyelois transitella, Anacampsis sarcitella, Anagasta kuehniella, Anarsia lineatella, Anisota senator/a, Antheraea pernyi, Anticarsia

(=Thermesia) spp. such as A. gemma talis; Apamea spp., Aproaerema modicella, Archips spp. such as A. argyrospila, A. fuscocupreanus, A. rosana, A. xyloseanus; Argyresthia conjugella, Argyroploce spp., Argyrotaenia spp. such as A. velutinana; Athetis mindara, Austroasca viridi- grisea, Autographa gamma, Autographa nigrisigna, Barathra brassicae, Bedellia spp., Bonagota salubricola, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp. such as C. murinana, C. podana; Cactoblastis cactorum, Cadra cautella, Calingo brazilien- s/5, Caloptilis theivora, Capua reticulana, Carposina spp. such as C. niponensis, C. sasakii; Cephus spp., Chaetocnema aridula, Cheimatobia brumata, Chilo spp. such as C. Indicus, C. suppressalis, C. partellus; Choreutis par/ana, Choristoneura spp. such as C. conflictana, C. fumiferana, C. longicellana, C. murinana, C. occidentalis, C. rosaceana; Chrysodeixis

(=Pseudoplusia) spp. such as C. eriosoma, C. includens; Cirphis unipuncta, Clysia ambiguella, Cnaphalocerus spp., Cnaphalocrocis medinalis, Cnephasia spp., Cochylis hospes, Coleophora spp., Colias eurytheme, Conopomorpha spp., Conotrachelus spp., Cop/tarsia spp., Corcyra cephalonica, Crambus caliginosellus, Crambus teterrellus, Crocidosema (=Epinotia) aporema, Cydalima (=Diaphania) perspectalis, Cydia (=Carpocapsa) spp. such as C. pomonella, C. latiferreana; Dalaca noctuides, Datana integerrima, Dasychira pinicola, Dendrolimus spp. such as Z7. / /) Z7. spectabilis, D. sibiricus; Desmia funeralis, Diaphania spp. such as Z7. nitidalis, D. hyalinata; Diatraea grandiosella, Diatraea saccharalis, Diphthera festiva, Earias spp. such as F. insulana, E. vittella; Ecdytolopha aurantianu, Egira (=Xylomyges) curia/is, Elasmopalpus lignosellus, Eldana saccharina, Endopiza viteana, Ennomos subsignaria, Eoreuma loftini, Ephestia spp. such as £. cautella, E. elutella, E. kuehniella; Epinotia aporema, Epiphyas postvittana, Erannis tiliaria, Erionota thrax, Etiei/a spp., Eu/ia spp., Eupoecilia ambiguella,

Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Faronta albiiinea, Felt/a spp. such as F subterranean; Galleria mellonella, Gracillaria spp., Grapholita spp. such as <3. funebrana, G. molesta, G. inopinata; Halysidota spp., Harrisina amerlcana, Hedylepta spp., Helicoverpa spp. such as H. armigera (=Heliothis armigera), H. zea (=Heliothis zea); Heliothis spp. such as H. assulta, H. subflexa, H. virescens; Hellula spp. such as H. undalis, H. rogatalis; Helocoverpa gelotopoeon, Hemileuca oliviae, Herpetogramma Iicarsisalis, Hibernia defoliaria, Hofmannophila pseudospretella, Homoeosoma electellum, Homona magnanima, Hypena scabra, Hyphantria cunea, Hyponomeuta padella, Hyponomeuta malinellus, Kakivoria flavofasciata, Keiferia lycopersicella, Lambdina fiscellaria fiscellaria, Lambdina fiscellaria lugubrosa, Lamprosema indicata, Laspeyresia molesta, Leguminivora glycinivorella, Lerodea eufala, Leucinodes orbonalis, Leucoma salicis, Leucoptera spp. such as L. coffee/la, L. scitella; Leuminivora lycinivorella, Lithocolletis blancardella, Lithophane antennata, Llattia octo (=Amyna axis), Lobes/a botrana, Lophocampa spp., Loxagrotis albicosta, Loxostege spp. such as L. sticticalis, L. cereralis; Lymantria spp. such as L. dispar, L. monacha; Lyonetia clerkella, Lyonetia prunifoliella, Malacosoma spp. such as M. americanum, M. californicum, M. constrictum, M. neustria; Mamestra spp. such as M. brassicae, M. configurata; Mamstra brassicae, Manduca spp. such as M. quinquemaculata, M. sexta; Marasmia spp, Marmara spp., Maruca testulalis, Megaiopyge lanata, Meianchra picta, Meianitis leda, Mods spp. such as M. lapites, M. repanda; Mods latipes, Monochroa fragariae, Mythimna separata, Nemapogon cloacella, Neoleucinodes elegantalis, Nepytia spp., Nymphula spp., Oiketicus spp., Omiodes indicata, Omphisa anastomosalis, Operophtera brumata, Orgy/a pseudotsugata, Or/a spp., Orthaga thyrisalis, Ostrinia spp. such as O. nubilalis; Oulema oryzae, Paleacrita vernata, Panolis flammea, Parnara spp., Papaipema nebris, Papilio cresphontes, Paramyelois transitella, Paranthrene rega/is, Paysandisia archon, Pectinophora spp. such as P. gossypiella; Peridroma saucia, Perileucoptera spp., such as P. coffeella; Phalera bucephala, Phryganidia californica,

Phthorimaea spp. such as P. operculella; Phyllocnistis citrella, Phyllonorycter spp. such as P. blancardella, P. crataegella, P. issikii, P. ringoniella; Pieris spp. such as P. brassicae, P. rapae, P. napi; Pilocrocis tripunctata, Plathypena scabra, Platynota spp. such as P. flavedana, P. idaeusalis, P. stultana; Platyptilia carduidactyla, Plebejus argus, Plodia interpunctella, Plus/a spp, Plutella maculipennis, Plutella xylostella, Pontia protodica, Prays spp., Prodenia spp., Proxenus lepigone, Pseudaletia spp. such as P. sequax, P. unipuncta; Pyrausta nubilalis, Rachiplusia nu, Richia albicosta, Rhizobius ventralis, Rhyacionia frustrana, Sabulodes aegrotata, Schizura concinna, Schoenobius spp., Schreckensteinia festaliella, Scirpophaga spp. such as S. incertulas, S. innotata; Scotia segetum, Sesamia spp. such as S. inferens, Seudyra subflava, Sitotroga cerealella, Sparganothis pilleriana, Spilonota lechriaspis, S. ocellana, Spodoptera (=Lamphygma) spp. such as S. cosmoides, S. eridania, S. exigua, S. frugiperda, S. latisfascia, S. littoralis, S. litura, S. omithogalli; Stigmella spp., Stomopteryx subsecivella, Strymon bazochii, Sylepta derogata, Synanthedon spp. such as S. exitiosa, Tecia solanivora, Telehin licus, Thaumatopoea pityocampa, Thaumatotibia (-Cryptophlebia) leucotreta,

Thaumetopoea pityocampa, Thecla spp., Theresimima ampelophaga, Thyrinteina spp, Tildenia inconspicuella, Tinea spp. such as T. cloacella, T. pellionella; Tineola bisselliella, Tortrixspp. such as T. viridana; Trichophaga tapetzella, Trichoplusia spp. such as T. ni; Tuta

(=Scrobipalpula) absolute, Udea spp. such as U. rubigalis, U. rubigalis; Virachola spp.,

Yponomeuta padella, and Zeiraphera canadensis;

insects from the order of Coleoptera, e.g. Acalymma vittatum, Acanthoscehdes obtectus, Adoretus spp., Agelastica alni, Agrilus spp. such as A. anxius, A. planipennis, A. sinuatus;

Agriotes spp. such as A. fuscicollis, A. lineatus, A. obscurus; Alphitobius diaperinus,

Amphimallus solstitialis, Anisandrus dispar, Anisoplia austriaca, Anobium punctatum, Anomala corpulenta, Anomala rufocuprea, Anoplophora spp. such as A. glabripennis; Anthonomus spp. such as A. eugenii, A. grandis, A. pomorum; Anthrenus spp., Aphthona euphoridae, Apion spp., Apogoniaspp., Athous haemorrhoidalis, Atomaria spp. such as A. linearis; Attagenus spp., Aulacophora femora/is, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp. such as B. lentis, B. pisorum, B. rufimanus; Byctiscus betulae, Callidiellum rufipenne, Callopistria floridensis, Callosobruchus chinensis, Cameraria ohridella, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorhynchus spp. such as C. assimilis, C. napi; Chaetocnema tibialis, Cleonus mendicus, Conoderus spp. such as C. vespertinus;

Conotrachelus nenuphar, Cosmopolites spp., Costelytra zeal and ica, Crioceris asparagi, Cryptolestes ferrugineus, Cryptorhynchus lapathi, Ctenicera spp. such as C. destructor;

Curculio spp., Cylindrocopturus spp., Cyclocephala spp., Dactylispa balyi, Dectes texanus, Dermestes spp., Diabrotica spp. such as D. undecimpunctata, D. speciosa, D. longicornis, D. semipunctata, D. virgifera; Diaprepes abbreviates, Dichocrocis spp., Dicladispa armigera, Diloboderus abderus, Diocalandra frumenti (Diocalandra stigmaticollis), Enaphalodes rufulus, Epilachna spp. such as E. varivestis, E. vigintioctomaculata; Epitrix pp. such as E. hirtipennis, E. similaris; Eutheola humilis, Eutinobothrus brasiliensis, Faustinus cubae, Gibbium psylloides, Gnathocerus cornutus, Hellula undalis, Heteronychus arator, Hylamorpha elegans, Hylobius abietis, Hylotrupes bajulus, Hypera spp. such as H. brunneipennis, H. postica; Hypomeces squamosus, Hypothenemus spp., Ips typographus, Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp. such as L. bilineata, L. melanopus; Leptinotarsa spp. such as L decemlineata; Leptispa pygmaea, Limonius californicus, Lisso- rhoptrus oryzophilus, Lixus spp., Luperodes spp., Lyctus spp. such as L. bruneus; Liogenys fuscus, Macrodactylus spp. such as M. subspinosus; Maladera matrida, Megaplatypus mutates, Megascelis spp., Melanotus communis, Meligethes spp. such as M. aeneus; Melolontha spp. such as M hippocastani, M. melolontha; Metamasius hemipterus, Microtheca spp., Migdolus spp. such as M fryanus, Monochamus spp. such as alternatus; Naupactus xanthographus, Niptus hololeucus, Oberia brevis, Oemona hirta, Oryctes rhinoceros, Oryzaephilus surina men- sis, Oryzaphagus oryzae, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Otiorrhynchus sulca- tus, Oulema melanopus, Oulema oryzae, Oxycetonia jucunda, Phaedon spp. such as P. brassi- cae, P. cochleariae; Phoracantha recurva, Phyllobius pyri, Phyllopertha horticola, Phyllophaga spp. such as P. helleri; Phyllotreta spp. such as P. chrysocephala, P. nemorum, P. striolata, P. vittula; Phyllopertha horticola, Popillia japonica, Premnotrypes spp., Psacothea hilaris, Psylli- odes chrysocephala, Prostephanus truncates, Psylliodes spp., Ptinus spp., Pulga saltona, Rhi- zopertha dominica, Rhynchophorus spp. such as R. billineatus, R. ferrugineus, R. palmarum, R. phoenicis, R. vulneratus; Saperda Candida, Scolytus schevyrewi, Scyphophorus acupunctatus, Sitona lineatus, Sitophilus spp. such as S. granaria, S. oryzae, S. zeamais; Sphenophorus spp. such as S. levis; Stegobium paniceum, Sternechus spp. such as S. subsignatus; Strophomor- phus ctenotus, Symphyletes spp., Tanymecus spp., Tenebrio molitor, Tenebrioides mauretani- cus, Tribolium spp. such as T. castaneum; Trogoderma spp., Tychius spp., Xylotrechus spp. such as pyrrhoderus; and, Zabrus spp. st cA as Z. tenebrioides;

insects from the order of Diptera e.g. Aedes spp. such as A. aegypti, A. albopictus, A. vexans; Anastrepha ludens, Anopheles spp. such as A. albimanus, A. crucians, A. freeborni, A. gam- biae, A. leucosphyrus, A. maculipennis, A. minimus, A. quadrimaculatus, A. sinensis; Bac- trocera invadens, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capi- tata, Chrysomyia spp. such as C. bezziana, C. hominivorax, C. macellaria; Chrysops atlanticus, Chrysops discalis, Chrysops silacea, Cochliomyia spp. such as C. hominivorax; Contarinia spp. such as C. sorghicola; Cordylobia anthropophaga, Culex spp. such as C. nigripalpus, C. pipi- ens, C. quinquefasciatus, C. tarsalis, C. tritaeniorhynchus; Culicoides furens, Culiseta inornata, Culiseta melanura, Cuterebra spp., Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Dasi- neura oxycoccana, Delia spp. such as D. antique, D. coarctata, D. platura, D. radicum; Dermat- obia hominis, Drosophila spp. such as D. suzukii, Fannia spp. such as F. canicularis; Gastraphi- lus spp. such as G. intestinalis; Geomyza tipunctata, Glossina spp. such as G. fuscipes, G. mor- sitans, G. pa/pa/is, G. tachinoides; Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia spp. such as H. platura; Hypoderma spp. such as H. lineata; Hyppobosca spp., Hydrellia philippina, Leptoconops torrens, Liriomyza spp. such as L. sativae, L. trifolii; Lucilia spp. such as L. caprina, L. cuprina, L. sericata; Lycoria pectoralis, Mansonia titillanus, Mayetiola spp. such as M. destructor; Musca spp. such as M. autumnalis, M. domestica; Muscina stabu- lans, Oestrus spp. such as O. ovis; Opomyza florum, Oscinella spp. such as O. frit; Orseolia oryzae, Pegomya hysocyami, Phlebotomus argentipes, Phorbia spp. such as P. antique, P. brassicae, P. coarctata; Phytomyza gymnostoma, Prosimulium mixtum, Psila rosae, Psorophora columbiae, Psorophora discolor, Rhagoletis spp. such as R. cerasi, R. cingulate, R. indifferens, R. mendax, R. pomonella; Rivellia quadrifasciata, Sarcophaga spp. such as S. haemorrhoidalis; Simulium vittatum, Sitodiplosis mosellana, Stomoxys spp. such as S. cafe/trans; Tabanus spp. such as T. atratus, T. bovinus, T. lineola, T. similis; Tannia spp., Thecodiplosis japonensis, Tip- ula oleracea, Tipula paludosa, and Wohlfahrtia spp;

insects from the order of Thysanoptera, e.g. Baliothrips biformis, Dichromothrips corbetti, Di- chromothrips ssp., Echinothrips americanus, Enneothrips flavens, Frankliniella spp. such as F. fusca, F. occidentalis, F. tritici; Helioth rips spp., Hercinothrips femoralis, Kakothrips spp., Micro- cephalothrips abdominalis, Neohydatothrips samayunkur, Pezothrips kellyanus, Rhipiphoro- thrips cruentatus, Scirtothrips spp. such as S. citri, S. dorsalis, S. perseae; Stenchaetothrips spp, Taeniothrips cardamoni, Taeniothrips inconsequens, Thrips spp. such as T. imagines, T. hawaiiensis, T. oryzae, T. palmi, T. parvispinus, T. tabaci;

insects from the order of Hemiptera, e.g. Acizzia jamatonica, Acrosternum spp. such as A. hilare; Acyrthosipon spp. such as A. onobrychis, A. pisum; Adelges laricis, Adelges tsugae, Ad el phocoris spp., such as A. rapidus, A. superbus; Aeneolamia spp., Agonoscena spp., Au- lacorthum solan/, Aleurocanthus woglumi, Aleurodes spp., Aleurodicus disperses, Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anasa tristis, Antestiopsis spp., Anuraphis car- dui, Aonidiella spp., Aphanostigma piri, Aphidula nasturtii, Aphis spp. such as A. craccivora, A. fabae, A. forbesi, A. gossypii, A. grossulariae, A. maidiradicis, A. pomi, A. sambuci, A. Schneider/, A. spiraecola; Arboridia apicalis, Arilus critatus, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacaspis yasumatsui, Aulacorthum solan i, Bactericera cockerel// (Paratrioza cockerelli), Bemisia spp. such as B. argentifolii, B. tabaci (Aleurodes tabaci); Blissus spp. such as B. leu- copterus; Brachycaudus spp. such as B. cardui, B. helichrysi, B. persicae, B. prunicola; Brachy- coius spp., Brachycorynella asparagi, Brevicoryne brassicae, Cacopsylla spp. such as C. fulgu- ralis, C. pyricola (Psylla piri); Calligypona marginata, Calocoris spp., Campylomma livida, Capi- tophorus horni, Carneocephala fulgida, Caveleri us spp., Ceraplastes spp., Ceratovacuna lanig- era, Ceroplastes ceriferus, Cerosipha gossypii, Chaetosiphon fragaefolii, Chionaspis tegalensis, Ch/orita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Cimex spp. such as C. hemipterus, C. lectularius; Coccomytilus halli, Coccus spp. such as C. hesperidum, C. pseudomagnoliarurrr, Corythucha arcuata, Creontiades dilutus, Cryptomyzus ribis,

Chrysomphalus aonidum, Cryptomyzus ribis, Ctenarytaina spatulata, Cyrtopeltis notatus, Dalbu- lus spp., Dasynus piperis, Dialeurodes spp. such as D. citrifolii; Dalbulus maidis, Diaphorina spp. such as D. citri; Diaspis spp. such as D. bromeliae; Dichelops furcatus, Diconocoris he- wetti, Dora/is spp., Dreyfusia nordmannianae, Dreyfusia piceae, Drosicha spp., Dysaphis spp. such as D. plantaginea, D. pyri, D. radicola; Dysaulacorthum pseudosolani, Dysdercus spp. such as D. c/ngu/atus, D. intermedius; Dysmicoccus spp., Edessa spp., Geocoris spp., Em- poasca spp. such as E fabae, E. so/ana; Epidiaspis leperii, Eriosoma spp. such as E. lanig- erum, E. pyricola; Erythroneura spp., Eurygaster pp. such as E. integriceps; Euscelis bilobatus, Euschistus spp. such as E. heros, E. impictiventris, E. servus; Fiorinia theae, Geococcus coffeae, Glycaspis brimblecombei, Halyomorpha spp. such as H. halys; Heliopeltis spp., Ho- malodisca vitripennis (=H. coagulata), Horcias nobilellus, Hyalopterus pruni, Hyperomyzus lac- tucae, lcerya spp. such as /. purchase; Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lecanoideus floccissimus, Lepidosaphes spp. such as L ulmi; Leptocorisa pp., Leptoglossus phyllopus, Lipaphis erysimi, Lygus spp. such as L. hesperus, L. lineolaris, L. pra- tensis; Maconellicoccus hirsutus, Marchalina helienica, Macropes excavatus, Macrosiphum spp. such as M. rosae, M. avenae, M. euphorbiae; Macrosteles quadrilineatus, Mahanarva fimbrio- lata, Megacopta cribraria, Megoura viciae, Melanaphis pyrarius, Melanaphis sacchari, Melano- callis (=Tinocallis) caryaefoliae, Metcafiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzocallis coryli, Murgantia spp., Myzus spp. such as M. ascalonicus, M. cerasi, M. nicotianae, M. persicae, M. varians; Nasonovia ribis-nigri, Neotoxoptera formosana, Neomegalotomus spp, Nephotettix spp. such as N. malayanus, N. nigropictus, N. parvus, N. vi- rescens; Nezara spp. such as N. viridula; Niiaparvata lugens, Nysius huttoni, Oebalus spp. such as O. pugnax; Oncometopia spp., Orthezia praelonga, Oxycaraenus hyalinipennis, Parabemisia myricae, Parlatoria spp., Parthenolecanium spp. such as P. corn/ P. persicae; Pemphigus spp. such as P. bursar/us, P. populivenae; Peregrinus maidis, Perkinsiella saccharic/da, Phena- coccus spp. such as P. aceris, P. gossypii; Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp. such as P. devastatrix, Piesma quadrata, Piezodorus spp. such as P. guildinii; Pin- naspis aspidistrae, Planococcus spp. such as P. citri, P. ficus; Prosapia bicincta, Protopulvinaria pyriformis, Psallus seriatus, Pseudacysta persea, Pseudaulacaspis pentagona, Pseudococcus spp. such as P. comstocki; Psylla spp. such as P. mali; Pteromalus spp., Pulvinaria amygdali, Pyrilla spp., Quadraspidiotus spp., such as Q. perniciosus; Quesada gigas, Rastrococcus spp., Reduvius senilis, Rhizoecus americanus, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalo- siphum spp. such as /?. pseudobrassicas, R. insertum, R. maidis, R. padi; Saga todes spp., Sahlbergella singularis, Saissetia spp., Sappaphis mala, Sappaphis mali, Scaptocoris spp., Scaphoides titanus, Schizaphis gram in urn, Schizoneura lanuginosa, Scotinophora spp., Ste/e- naspidus articulatus, Sitobion avenae, Sogata spp., Sogatella furcifera, Solubea insularis, Spis- sistilus festinus (=Stictocephala festina), Stephanitis nashi, Stephanitis pyrioides, Stephanitis takeyai, Tenalaphara malayensis, Tetraleurodes perseae, Therioaphis maculate, Thyanta spp. such as accerra, T. perditor; Tibraca spp., Tomaspis spp., Toxoptera spp. such as aurantii; Trialeurodes spp. such as 7^ abutilonea, T. ricini, T. vaporariorum; Triatoma spp., Trioza spp., Typhlocyba spp., Unaspis spp. such as £/ c/iVjr) 6/. yanonensis; and Viteus vitifolii,

Insects from the order Hymenoptera e.g. Acanthomyops interjectus, Athalia rosae, Atta spp. such as A. capiguara, A. cephaiotes, A. cephaiotes, A. laevigata, A. robusta, A. sexdens, A. tex- ana, Bombus spp., Brachymyrmex spp., Camponotus spp. such as C. floridanus, C. pennsyl- vanicus, C. modoc; Cardiocondyla nuda, Chalibion sp, Crematogaster spp., Dasymutilla occi- dentalis, Diprion spp., Dolichovespula maculata, Dory my rmex spp., Dryocosmus kuriphilus, Formica spp., Hoplocampa spp. such as ^■ . minuta, H. testudinea; Iridomyrmex humilis, Lasius spp. such as Z.. n/ er, Linepithema humile, Liometopum spp., Leptocybe invasa, Monomorium spp. such as M pharaonis, Monomorium, Nylandria fulva, Pachycondyla chinensis, Paratrechina lon- gicornis, Paravespula spp., such as P. germanica, P. pennsylvanica, P. vulgaris; Pheidole spp. such as P. megacephala; Pogonomyrmex pp. such as P. barbatus, P. californicus, Polistes ru- biginosa, Prenolepis impairs, Pseudomyrmex gracilis, Schelipron spp., Sirex cyaneus, Solenop- sis spp. such as S. geminata, S.invicta, S. molesta, S. richteri, S. xyloni, Sphecius speciosus, Sphexspp., Tapinoma spp. such as T. melanocephalum, T. sessile; Tetramorium spp. such as T. caespitum, T. bicarinatum, Vespa spp. such as V. crabro; Vespula spp. such as V. squamo- sal; Wasmannia auropunctata, Xylocopa sp;

Insects from the order Orthoptera e.g. Acheta domesticus, Calliptamus italicus, Chortoicetes terminifera, Ceuthophilus spp., Diastrammena asynamora, Dociostaurus maroccanus, Gryllo- talpa spp. such as G. africana, G. gryllotalpa; Gryllus spp., Hieroglyphus daganensis,

Kraussaria angulifera, Locusta spp. such as L. migratoria, L. pardalina; Melanoplus spp. such as M. bivittatus, M. femurrubrum, M. mexicanus, M. sanguinipes, M. spretus; Nomadacris sep- temfasciata, Oedaleus senegalensis, Scapteriscus spp., Schistocerca spp. such as S. ameri- cana, S. gregaria, Stemopelmatus spp., Tachycines asynamorus, and Zonozerus variegatus; Pests from the Class Arachnida e.g. Acari,e.g. of the families Argasidae, Ixodidae and Sar- coptidae, such as Amblyomma spp. (e.g. A. americanum, A. variegatum, A. maculatum), Argas spp. such as A. persicu), Boophilus spp. such as B. annulatus, B. decoloratus, B. microplus, Dermacentor spp. such as D.silvarum, D. andersoni, D. variabilis, Hyalomma spp. such as H. truncatum, Ixodes spp. such as /. ricinus, I. rubicundus, I. scapularis, I. holocyclus, I. pacificus, Rhipicephalus sanguineus, Ornithodorus spp. such as O. moubata, O. hermsi, O. turicata, Orni- thonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes spp. such as P. ovis,

Rhipicephalus spp. such as R. sanguineus, R. appendiculatus, Rhipicephalus everts/, Rhizogly- phus spp., Sarcoptes spp. such asS. Scabier, and Family Eriophyidae including Aceria spp. such as A. sheldoni, A. anthocoptes, Acallitus spp., Aculops spp. such as A. lycopersici, A. pel- ekassi, Aculus spp. such as A. schlechtendali; Colomerus vitis, Epitrimerus pyri, Phyllocoptruta oieivora; Eriophytes nbis and Eriophyes spp. such as Eriophyes sheldoni, Family Tarsonemidae including Hemitarsonemus spp., Phytonemus pallidus and Polyphagotarsonemus latus, Steno- tarsonemus spp. Steneotarsonemus spinki, Family Tenuipalpidae including Brevipalpus spp. such as B. phoenicis, Family Tetranychidae including Eotetranychus spp., Eutetranychus spp., Oligonychus spp., Petrobia latens, Tetranychus spp. such as 7^ cinnabarinus, T. evansi, T. kan- zawai, T, pacificus, T. phaseulus, T. telarius and urticae; Bryobia praetiosa; Panonychus spp. such as P. £///77/; P. ofrv; Metatetranychus spp. and Oligonychus s p. such as C. pratensis, O. perseae, Vasates lycopersici, Raoiella indica, Fa/w/y Carpoglyphidae including Carpoglyphus spp.; Penthaleidae spp. such as Halotydeus destructor, Family Demodicidae with species such as Demodexspp:, Family Trombicidea including Trombicula spp:, Family Macronyssidae includ- ing Orn othonyss us spp. Family Pyemotidae including Pyemotes tritici, Tyrophagus putrescen- tiae; Family Acaridae including Acarus siro, Family Araneida including Latrodectus mactans, Tegenaria ag rest is, Chiracanthium sp, Lycosa sp Achaearanea tepidariorum and Loxosceles reclusa;

Pests from the Phylum Nematoda, e.g. plant parasitic nematodes such as root-knot nema- todes, Meloidogyne spp. such as M. hapla, M. incognita, M. javanica; cyst-forming nematodes, Globodera spp. such as G. rostochiensis; Heterodera spp. such as H. avenae, H. glycines, H. schachtii, H. trifolii; Seed gall nematodes, Anguina spp.; Stem and foliar nematodes, Aphelen- choides spp. such as A. besseyi; Sting nematodes, Belonolaimus spp. such as B. longicauda- ή/s/ Pine nematodes, Bursaphelenchus spp. such as z?. lignicolus, B. xylophilus; Ring nema- todes, Criconema spp., Criconemella pp. such as C. xenop/axand C. ornata; and, Cricone- moides spp. such as Criconemoides informis; Mesocriconema spp.; Stem and bulb nematodes, Ditylenchus spp. such as £>. destructor, D. dipsaci; Awl nematodes, Dolichodorus spp.; Spiral nematodes, Heliocotylenchus multicinctus; ^{^} Sheath and sheathoid nematodes, Hemicyciiophora spp. and Hemicriconemoides spp. ; Hirshmanniella spp.; ^{^} Lance nematodes, Hoploaimus spp.; False rootknot nematodes, Nacobbus spp.; Needle nematodes, Longidorus spp. such as Z.. elongatus; Lesion nematodes, Pratylenchus spp. such as . brachyurus, P. neglectus, P. penetrans, P. curvitatus, P. goodeyi; Burrowing nematodes, Radopholus spp. such as ?. similis; Rhadopholus spp.; Rhodopholus spp.; Reniform nematodes, Rotylenchus spp. such as /?. /r>- bustus, R. reniformis; Scutellonema spp.; Stubby-root nematode, Trichodorus spp. such as 7^ obtusus, T. primitivus; Paratrichodorus spp. such as P. minor; Stunt nematodes, Tylenchorhyn- chus spp. such as T. claytoni, T. dub/us; Citrus nematodes, Tylenchulus spp. such as 7^ se/ro- penetrans; Dagger nematodes, Xiphinema spp.; and other plant parasitic nematode species;

Insects from the order Isoptera e.g. Calotermes flavicollis, Coptotermes spp. such as C. for- mosanus, C. gestroi, C. acinaciformis; Cornitermes cumulans, Cryptotermes spp. such as C. brevis, C. cavifrons; Globitermes sulfureus, Heterotermes spp. such as H. aureus, H. longiceps, H. tenuis; Leucotermes flavipes, Odontotermes spp., Incisitermes spp. such as /. minor, I.

Snyder, Marginitermes hubbardi, Mastotermes spp. such as M. darwiniensis Neocapritermes spp. such as N. opacus, N. parvus; Neotermes spp., Procornitermes spp., Zootermopsis spp. such as Z. angusticollis, Z. nevadensis, Reticulitermes spp. such as ?. hesperus, R. tibialis, R. speratus, R. flavipes, R. grassei, R. lucifugus, R. santonensis, R. virgin icus; Termes natalensis,

Insects from the order Blattaria e.g. B/atta spp. such as B. orientalis, B. lateralis; Blattella spp. such as B. asahinae, B. germanica; Leucophaea maderae, Panchlora nivea, Pen planeta spp. such as P. americana, P. australasiae, P. brunnea, P. fuligginosa, P. japonica; Supella longi- palpa, Parcoblatta pennsylvanica, Eurycotis floridana, Pycnoscelus surinamensis,

Insects from the order Siphonoptera e.g. Cediopsylla simples, Ceratophyllus spp., Cten- ocephalides spp. such as C. fells, C. canis, Xenopsylla cheopis, Pulex irritans, Trichodectes cam ^' s, Tunga penetrans, and Nosopsyllus fasciatus,

Insects from the order Thysanura e.g. Lepisma saccharina , Ctenolepisma urbana, and Ther- mobia domestica,

Pests from the class Chilopoda e.g. Geophilus spp., Scutigera spp. such as Scutigera coleop- trata,

Pests from the class Diplopoda e.g. Blaniulus guttulatus, Ju/us spp., Narceus spp.,

Pests from the class Symphyla e.g. Scutigerella immaculata,

Insects from the order Dermaptera, e.g. Forficula auricularia,

Insects from the order Collembola, e.g. Onychiurus spp., such as Onychiurus armatus, Pests from the order Isopoda e.g., Armadillidium vulgare, Oniscus asellus, Porcellio scaber, Insects from the order Phthiraptera, e.g. Damalinia spp., Pediculus spp. such as Pediculus hu- manus capitis, Pediculus humanus corporis, Pediculus humanus humanus; Pthirus pubis, Haematopinus spp. such as Haematopinus eurysternus, Haematopinus suis, Linognathus spp. such as Linognathus vituli; Bovicola bovis, Menopon gallinae, Menacanthus stramineus and So- lenopotes capillatus, Trichodectes spp.,

Examples of further pest species which may be controlled by compounds of fomula (I) include: from the Phylum Mollusca, class Bivalvia, e.g. Dreissena spp.; class Gastropoda, e.g. Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Ga/ba spp., Lymnaea spp., Oncomelania spp., Pomacea canaliclata, Succinea spp. /from the class of the helminths, e.g. Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubri- coides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonor- chis spp., Cooper/a spp., Dicrocoelium spp., Dictyocaulus filaria, Diphyllobothrium latum, Dra- cunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius ver- micularis, Faciola spp., Haemonchus spp. such as Haemonchus con tortus; Heterakis spp., Hy- menolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonim us spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercora lis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti.

The compounds of the invention are suitable for use in treating or protecting animals against infestation or infection by parasites. Therefore, the invention also relates to the use of a compound of the invention for the manufacture of a medicament for the treatment or protection of animals against infestation or infection by parasites. Furthermore, the invention relates to a method of treating or protecting animals against infestation and infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiti- cidally effective amount of a compound of the invention.

The invention also relates to the non-therapeutic use of compounds of the invention for treating or protecting animals against infestation and infection by parasites. Moreover, the invention relates to a non-therapeutic method of treating or protecting animals against infestation and infection by parasites, which comprises applying to a locus a parasiticidally effective amount of a compound of the invention.

The compounds of the invention are further suitable for use in combating or controlling parasites in and on animals. Furthermore, the invention relates to a method of combating or controlling parasites in and on animals, which comprises contacting the parasites with a parasitically effective amount of a compound of the invention.

The invention also relates to the non-therapeutic use of compounds of the invention for controlling or combating parasites. Moreover, the invention relates to a non-therapeutic method of combating or controlling parasites, which comprises applying to a locus a parasiticidally effective amount of a compound of the invention.

The compounds of the invention can be effective through both contact (via soil, glass, wall, bed net, carpet, blankets or animal parts) and ingestion (e.g. baits). Furthermore, the compounds of the invention can be applied to any and all developmental stages.

The compounds of the invention can be applied as such or in form of compositions comprising the compounds of the invention.

The compounds of the invention can also be applied together with a mixing partner, which acts against pathogenic parasites, e.g. with synthetic coccidiosis compounds, polyetherantibiotics such as Amprolium, Robenidin, Toltrazuril, Monensin, Salinomycin, Maduramicin, Lasalocid, Narasin or Semduramicin, or with other mixing partners as defined above, or in form of compositions comprising said mixtures.

The compounds of the invention and compositions comprising them can be applied orally, par- enterally or topically, e.g. dermally. The compounds of the invention can be systemically or non- systemically effective.

The application can be carried out prophylactically, therapeutically or non-therapeutically. Furthermore, the application can be carried out preventively to places at which occurrence of the parasites is expected.

As used herein, the term "contacting" includes both direct contact (applying the compounds/compositions directly on the parasite, including the application directly on the animal or excluding the application directly on the animal, e.g. at it's locus for the latter) and indirect con- tact (applying the compounds/compositions to the locus of the parasite). The contact of the parasite through application to its locus is an example of a non-therapeutic use of the compounds of the invention.

The term "locus" means the habitat, food supply, breeding ground, area, material or environ- ment in which a parasite is growing or may grow outside of the animal.

As used herein, the term "parasites" includes endo- and ectoparasites. In some embodiments of the invention, endoparasites can be preferred. In other embodiments, ectoparasites can be preferred. 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, chiggers, gnats, mosquitoes and fleas.

The compounds of the invention are especially useful for combating parasites of the following orders and species, respectively:

fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus; cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Peri- planeta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis;1\\es, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimacula- tus, Calliphora vicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pi pi ens, Culex nig ri palpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dermatobia hominis, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Leptoconops torrens, Lu cilia caprina, Lu cilia cuprina, Lu cilia sericata, Lycoria pectoralis, Manso- nia spp., Musca domes tica, Muscina stabulans, Oestrus ovis, Phlebotomus argentipes, Psoro- phora columbiae, Psorophora discolor, Prosimulium mixtum, Sarcophaga haemorrhoidalis, Sar- cophaga sp., Simulium vittatum, Stomoxys calci trans, Tabanus bovinus, Tabanus atratus, Taba- nus lineola, and Tabanus similis; lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bo vf cola bo vis, Menopon gallinae, Menacanthus stramineus and Solenopotes ca pi I la tus; ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocy- clus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor varia- bill ^' s, Amblyomma americanum, Ambryomma maculatum, Ornithodorus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Ornithonyssus bacoti and Dermanyssus gallinae, Actinedida (Prostigmata) und Acaridida (Astigmata), e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listro- phorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemi- docoptes spp., Cytodites spp., and Laminosioptes spp; Bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp., and Ar- ilus critatus; Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp.; Mallophagida (suborders Arnblycerina and Ischnocerina), e.g. 7/7- menopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Trichodectes spp., and Felicola spp.; Roundworms Nematoda: Wipeworms and Trichinosis (Trichosyringida), e.g. Trichinellidae (Trichinella spp.), Trichuridae ' Trichuris spp., Capillaria spp.; Rhabditida, e.g. Rhabditis spp., Strongyloides spp., Helicephalobus s/j ./ Strongylida, e.g. Strongylus spp., Ancylostoma spp., Necator americanus, Bunostomum spp. (Hookworm), Tri- chostrongylus spp., Haemonchus contortus, Ostertagia spp., Cooper/a spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oesophagostomum spp., Stephanurus den tat us, Ollu- lanus spp., Chabertia spp., Stephanurus dentatus, Syngamus trachea, Ancylostoma spp., Unci- naria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Proto- strongylus spp., Angiostrongylus spp., Parelaphostrongylus spp., Aleurostrongylus abstrusus, and D/octophy a renale; Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris e^' Camallanida, e.g. Dracunculus medinensis (guinea worm); Spirurida, e.g. Thelazia spp., Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp.a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Habronema spp.; Thorny headed worms (Acanthocephala), e.g. Acanthocephalus spp., Macracanthorhynchus hirudinaceus and Oncicola spp.; Planarians (Plathelminthes): Flukes (Trematoda), e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Dicrocoelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilharzia spp., Alaria alata, Paragonimus spp., and Nanocyetes spp:, Cercomeromorpha, in particular Cestoda (Tapeworms), e.g. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium can/hum, Multi- ceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis spp., Moniezia spp., Anoplo- cephala spp., Sirometra spp., Anoplocephala spp., and Hymenolepis spp..

As used herein, the term "animal" includes warm-blooded animals (including humans) and fish. Preferred are 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. Particularly pre- ferred are domestic animals, such as dogs or cats.

In general, "parasiticidally 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 parasiticidally effective amount can vary for the various compounds/com- positions 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.

Generally, it is favorable to apply the compounds of the invention in total amounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day.

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 water. 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, e.g. 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 formulations 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, particu- larly 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 preparations;

- 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.

Compositions suitable for injection are prepared by dissolving the active ingredient in a suita- ble solvent and optionally adding further auxiliaries such as acids, bases, buffer salts, preservatives, and solubilizers. Suitable auxiliaries for injection solutions are known in the art. The solutions are filtered and filled sterile.

Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being necessary.

Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on. Solutions for use on the skin are prepared according to the state of the art and according to what is described above for injection solutions, sterile procedures not being necessary.

Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared as described in the case of the injection solutions with sufficient thickener that a clear material having an ointment-like consistency results. Suitable thickeners are known in the art.

Pour-on formulations are poured or sprayed onto limited areas of the skin, the active com- pound penetrating the skin and acting systemically. Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures. If appropriate, other auxiliaries such as colorants, bioabsorption-promoting substances, antioxidants, light stabilizers, adhesives are added. Suitable such auxiliaries are known in the art. Emulsions can be administered orally, dermally or as injections. Emulsions are either of the water-in-oil type or of the oil-in-water type. They are prepared by dissolving the active compound either in the hydrophobic or in the hydrophilic phase and homogenizing this with the solvent of the other phase with the aid of suitable emulsifiers and, if appropriate, other auxiliaries such as colorants, absorption-promoting substances, preservatives, antioxidants, light stabilizers, viscosity-enhancing substances. Suitable hydrophobic phases (oils), suitable hydrophilic phases, suitable emulsifiers, and suitable further auxiliaries for emulsions are known in the art.

Suspensions can be administered orally or topically/dermally. They are prepared by suspending the active compound in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers. Suitable suspending agents, and suitable other auxiliaries for suspensions including wetting agents are known in the art.

Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above only by their higher viscosity.

For the production of solid preparations, the active compound is mixed with suitable excipi- ents, if appropriate with addition of auxiliaries, and brought into the desired form. Suitable auxiliaries for this purpose are known in the art.

The compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the compound of the invention.

Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 per cent by weight, preferably from 0.1 to 65 per cent by weight, more preferably from 1 to 50 per cent by weight, most preferably from 5 to 40 per cent by weight.

Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 per cent by weight, preferably of 1 to 50 per cent by weight.

Furthermore, the preparations comprise the compounds of formula I against endoparasites in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 per cent by weight, very particularly preferably of 0.005 to 0.25 per cent by weight.

Topical application may be conducted with compound-containing shaped articles such as col- lars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.

Generally it is favorable to apply solid formulations which release compounds of the invention in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks. Examples

The invention is now illustrated in further details by the following examples, without imposing any limitation thereto.

Compounds can be characterized e.g. by coupled High Performance Liquid Chromatography / mass spectrometry (HPLC/MS), by ¹ H-NMR and/or by their melting points.

Analytical HPLC - Phenomenex Kinetex 1 ,7μιη XB-C18 100A; 50 x 2,1 mm. Elution: acetoni- trile + 0.1 % trifluoroacetic acid (TFA) / water + 0.1 % trifluoroacetic acid (TFA) in a ratio of from 5:95 to 95:5 in 1.5 minutes at 50°C. ¹ H-NMR: The signals are characterized by chemical shift (ppm, δ [delta]) vs. tetramethylsilane, respectively CDC for ¹³ C-NMR, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following abbreviations are used to characterize the multiplicity of the signals: m = multiplett, q = quartett, t = triplett, d = doublet and s = singulett.

Abbreviations used are: d for day(s), h for hour(s), min for minute(s), r.t./room temperature for 20-25°C, Rt for retention time; Ph for phenyl, OAc for acetate, CH for cyclohexane, EtOAc for ethyl acetate, and t-BuOH for tert-butanol.

Example V. 1-[2-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4 H-isoxazol-3-yl]spiro[4H- thieno[2,3-c]furan-6,3'-azetidine]-1 '-yl]-2-methylsulfonyl-ethanone [C-10]

Step 1 : tert-butyl 3-hydroxy-3-[3-(hydroxymethyl)-2-thienyl]azetidine-1-carboxy late

To a solution of 3-thiophenemethanol (10.0 g, 87.6 mmol, 1.00 equiv.) in THF (100 mL) at -70°C was added a solution of butyllithium (55.3 mL of a 1 .6 M solution in hexanes, 88.5 mmol, 1.01 equiv.) and stirred for 1 h. Additional butyllithium (52 mL of a 1.6 M solution in hexanes, 83 mmol, 0.95 equiv.) was added at this temperature. After 30 min, the mixture was allowed to warm to -10°C and recooled to -70°C. A solution of N-Boc-azetidinone ( 4.70 g, 85.8 mmol, 0.98 equiv.) in THF (15 mL) was added and the cooling bath was replaced with ice-cooling. The mixture was stirred at 0°C until completely dissolved. Saturated aqueous NH4CI solution was added and the pH of the mixture was adjusted to 6 by addition of 2 N HCI. Dilution with MTBE and extraction with EtOAc afforded an organic layer that was separated and washed with water and brine. Drying of the organic layer over Na2S0 ₄ and filtration gave a crude product which was chromatographed on silica gel to afford the title compound (16.6 g, 68%). ¹ H NMR (400 MHz, CDCb): δ = 1.41 (s, 9H), 4.20 (d, 2H), 4.30 (d, 2H), 4.65 (s, 2H), 6.91 (d, 1 H), 7.12 (d, 1 H).

Step 2: tert-butyl spiro[4H-thieno[2,3-c]furan-6,3'-azetidine]-1 '-carboxylate

To a solution of tert-butyl 3-hydroxy-3-[3-(hydroxymethyl)-2-thienyl]azetidine-1-carboxy late (Example 1 , Step 1 , 16.6 g, 58.2 mmol, 1.00 equiv.) in THF (250 mL) was added triethyl amine (40.3 mL, 291 mmol, 5 equiv.) and a solution of mesyl chloride (5.4 mL, 70 mmol, 1.2 equiv.) in THF (20 mL) at 0°C. Upon completed addition, the mixture was allowed to reach r.t. and heated to 45°C for 4 h. After cooling, saturated aqueous NaHCOs solution was added and the mixture was extracted with EtOAc. Combined organic layers were washed with brine and dried over Na2S0 ₄ . Concentration in vacuum gave a residue which was dissolved in THF (100 mL) and methanol (100 mL). Solid K ₂ CO3 (34.8 g, 252 mmol, 5 equiv.) was added at r.t. and the mixture was stirred for 2 h. After concentration in vacuum, water was added and the resulting mixture was extracted with EtOAc. Combined organic layers were washed with brine and dried over Na2S0 ₄ . Concentration in vacuum gave a crude product which was purified via silica gel chromatography to yield the title compound (7.90 g, 51 %). ¹ H NMR (500 MHz, CDCb): δ = 1.46 (s, 9H), 4.19 (d, 2H), 4.33 (d, 2H), 4.98 (s, 2H), 6.75 (d, 1 H), 7.36 (d, 1 H).

Step 3: tert-butyl 2-bromospiro[4H-thieno[2,3-c]furan-6,3'-azetidine]-1 '-carboxylate

To a solution of tert-butyl spiro[4H-thieno[2,3-c]furan-6,3'-azetidine]-1 '-carboxylate (Step 2,

7.90 g, 29.6 mmol, 1.00 equiv.) and DMAP (180 mg, 1.48 mmol, 0.05 equiv.) in acetonitrile (100 mL) was added a solution of NBS (6.31 1 g, 35.46 mmol, 1.200 equiv.) in acetonitrile (70 mL) at 0°C. After 6 min at this temperature, the mixture was allowed to reach r.t. and stirred for another 2 h. Aqueous 10% NaHS03 was added and diluted with water. The mixture was extracted with EtOAc and the organic layer was separated, dried over Na ₂ SC>4 and concentrated in vacuum. Chromatography on silica gel yielded the title compound (8.70 g, 85%). ¹ H NM (400 MHz, CDCIa): δ = 1.47 (s, 9H), 4.15 (d, 2H), 4.29 (d, 2H), 4.98 (s, 2H), 6.80 (s, 1 H).

Step 4: tert-butyl 2-acetylspiro[4H-thieno[2,3-c]furan-6,3'-azetidine]-1'-carbo xylate

A mixture of tert-butyl 2-bromospiro[4H-thieno[2,3-c]furan-6,3'-azetidine]-1'-carbox ylate (Step 3, 8.70 g, 25.1 mmol, 1.00 equiv.), N-butyl vinyl ether (8.17 mL, 62.8 mmol, 2.5 equiv.), Pd(OAc) ₂ (338 mg, 1.51 mmol, 0.06 equiv.), 1 ,3-bis(diphenylphosphino)propane (1.24 g, 3.01 mmol, 12.0 mol-%), triethylamine (7.0 mL, 50 mmol, 2.0 equiv.) and 1-butanol (100 mL) were degassed in an ultrasonic bath. The resulting mixture was heated at reflux for 3 h and cooled to 0°C, before it was slowly added to an ice cold aqueous 2 N HCI. The resulting slurry was vigorously stirred at r.t. for 30 min, before EtOAc (80 mL) was added. The layers were separated and the organic layer was washed with water and brine. After drying over Na2SC>4, all volatiles were removed in vacuum and the residue was purified via column chromatography on silica gel to afford the title compound (5.20 g, 67%). H NMR (400 MHz, CDCI3): δ = 1.48 (s, 9H), 2.55 (s, 3H), 4.19 (d, 2H), 4.32 (d, 2H), 5.00 (s, 2H), 7.38 (s, 1 H).

Step 5: tert-butyl 2-[3-(3,5-dichloro-4-fluoro-phenyl)-4,4,4-trifluoro-3-hydrox y-butanoyl]spi- ro[4H-thieno[2,3-c]furan-6,3'-azetidine]-1'-carboxylate

A mixture of 1-(3,5-dichloro-4-fluoro-phenyl)-2,2,2-trifluoro-ethanone (8.77 g, 33.6 mmol, 2.00 equiv.), tert-butyl 2-acetylspiro[4H-thieno[2,3-c]furan-6,3'-azetidine]-1 '-carboxylate (Step 4, 5.20 g, 16.8 mmol, 1.00 equiv.) and triethyl amine (0.47 mL, 3.4 mmol, 0.20 equiv.) in n-heptane (20 mL) was stirred at 60°C for 1 day. After cooling to r.t., the resulting precipitate was collected by filtration and dried to obtain the title compound (8.28 g, 86%). ¹ H NMR (500 MHz, CDC ): δ = 1.47 (s, 9H), 3.63 (m, 2H), 4.19 (m, 2H), 4.37 (m, 2H), 5.02 (s, 2H), 5.86 (s, 1 H), 7.51-7.62 (m, 3H).

Step 6: tert-butyl 2-[(E/Z)-3-(3,5-dichloro-4-fluoro-phenyl)-4,4,4-trifluoro-bu t-2-enoyl]spiro[4H- th ieno[2,3-c]fu ran-6 ,3'-azetidi ne]- 1 '-carboxylate

To a solution of tert-butyl 2-[3-(3,5-dichloro-4-fluoro-phenyl)-4,4,4-trifluoro-3-hydrox y-buta- noyl]spiro[4H-thieno[2,3-c]furan-6,3'-azetidine]-1 '-carboxylate (Step 5, 8.28 g, 14.5 mmol, LOOequiv.) in toluene (100 mL) was added pyridine (5.8 mL, 73 mmol, 5 equiv.) and thionyl chloride (3.7 mL, 51 mmol, 3 equiv.) successively. The resulting reaction mixture was stirred at 80°C for 2 h, before it was cooled to r.t.. MTBE and aqueous 5% K2CO3 solution was added it was stirred vigorously. The aqueous layer was removed and discarded. The organic layer was washed with aqueous 2 N HCI, saturated aqueous NaHCC>3 solution and brine, before it was dried over Na2SC>4. After concentration in vacuum, the crude title compound (8.20 g, quantita- tive) was obtained and used in the next transformation without further purification.

Step 7: tert-butyl 2-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-i soxazol-3- yl]spiro[4H-thieno[2,3-c]furan-6,3'-azetidine]-1 '-carboxylate

To a solution of tert-butyl 2-[(E/Z)-3-(3,5-dichloro-4-fluoro-phenyl)-4,4,4-trifluoro-bu t-2- enoyl]spiro[4H-thieno[2,3-c]furan-6,3'-azetidine]-1'-carboxy late (Step 6, -97% purity, 8.20 g, 14.5 mmol, 1.00 equiv.) in THF (60 mL) was added NaOH (2.4 g, 59 mmol, 4 equiv.) and a solution of hydroxylamine hydrochloride (2.063 g, 29.69 mmol, 2.000 equiv.) in water (7.5 mL) at r.t.. After completed reaction, the mixture was concentrated in vacuum and water and EtOAc were added. The organic layer was separated and washed with water and brine. The resulting solu- tion was dried over Na2SC>4 and concentrated in vacuum. The residue was purified by chromatography on silica gel to afford the title compound (8.00 g, 90% with 95% purity). ¹ H NM (500 MHz, CDCIa): δ = 1.47 (s, 9H), 3.66 (d, 1 H), 4.05 (d, 1 H), 4.19 (m, 2H), 4.32 (m, 2H), 4.98 (m, 2H), 6.92 (s, 1 H), 7.57 (m, 2H).

Step 8: 2-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-i soxazol-3-yl]spiro[4H- thieno[2,3-c]furan-6,3'-azetidin-1 -ium];2,2,2-trifluoroacetate

To a solution of tert-butyl 2-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-i soxazol-3- yl]spiro[4H-thieno[2,3-c]furan-6,3'-azetidine]-1 '-carboxylate (Step 7, 4.50 g, 7.83 mmol, 1.00 equiv.) in dichloromethane (75 mL) was added trifluoroacetic acid (31 mL, 0.40 mol, 51 equiv.) at 0°C. After completed reaction, the mixture was concentrated at 20°C bath temperature and evaporated to dryness to afford the title compound (6 g, quantitative) which was used in the following transformations without purification measures.

Step 9: preparation of 1-[2-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4 H-isoxazol-3- yl]spiro[4H-thieno[2,3-c]furan-6,3'-azetidine]-1'-yl]-2-meth ylsulfonyl-ethanone

To a solution of 2-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-i soxazol-3-yl]spi- ro[4H-thieno[2,3-c]furan-6,3'-azetidin-1-ium];2,2,2-trifluor oacetate (Step 8, 500 mg, 0.860 mmol, 1.00 equiv.) in THF (10 mL) was added DMAP (10 mg) and triethyl amine (0.48 mL, 0.003 mol, 4 equiv.) at 0°C. After 1 h at this temperature, a solution of 2-methylsulfonylacetyl chloride (161 mg, 1.03 mmol, 1 .20 equiv.) in THF (3 mL) was added and the cooling bath was removed. After 16 h at this temperature, water was added and the mixture was extracted with ethyl acetate. Combined organic layers were washed with aqueous 2 N HCI, brine and dried over Na2S04. The resulting solution was concentrated in vacuum and purified via flash chromatography on silica gel to afford the title compound (170 mg, 34%). ¹ H NMR (400 MHz, CDCI ₃ ): δ = 3.17 (s, 3H), 3.65 (d, 1 H), 3.86 (s, 2H), 4.04 (d, 1 H), 4.40 (d, 1 H) ,4.47 (d, 1 H), 4.65 (d, 1 H), 4.70 (d, 1 H), 5.02 (m, 2H), 6.96 (s, 1 H), 7.56 (m, 2H).

Example 2: 1-[2-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4 H-isoxazol-3-yl]spiro[4,5- dihydrothieno[2,3-c]pyran-7,3'-azetidine]-1 '-yl]propan-1-one [C-1]

Step 1 : tert-butyl 3-hydroxy-3-[3-(2-hydroxyethyl)-2-thienyl]azetidine-1-carbox ylate

To a solution of 3-thiopheneethanol (10.0 g, 87.6 mmol, 1 .00 equiv.) in THF (80 mL) at -70°C was added a solution of butyllithium (49 mL of a 1.6 M solution in hexanes, 0.079 mol, 1 .01 equiv.) and stirred for 1 h. Additional butyllithium (46 mL of a 1.6 M solution in hexanes, 0.074 mol, 0.95 equiv.) was added at this temperature. After 30 min, the mixture was allowed to warm to -10°C and recooled to -70°C. A solution of N-Boc-azetidinone (13.09 g, 0.076 mol, 0.98 equiv.) in THF (20 mL) was added and the cooling bath was replaced with ice-cooling. The mixture was stirred at 0°C until completely dissolved. Saturated aqueous NH4CI solution was added and the pH of the mixture was adjusted to 6 by addition of 2 N HCI. Dilution with MTBE and extraction with EtOAc afforded an organic layer that was separated and washed with water and brine. Drying of the organic layer over Na2SC>4 and filtration gave a crude product which was chromatographed on silica gel to afford the title compound (12.6 g, 55%). ¹ H NMR (400 MHz, CDCI3): δ = 1.43 (s, 9H), 2.81 (m, 2H), 3.84 (m, 2H), 4.26 (d, 2H), 4.37 (d, 2H), 6.88 (d, 1 H), 7.21 (d, 1 H).

Step 2: tert-butyl spiro[4,5-dihydrothieno[2,3-c]pyran-7,3'-azetidine]-1'-carbo xylate To a solution of tert-butyl 3-hydroxy-3-[3-(2-hydroxyethyl)-2-thienyl]azetidine-1-carbox ylate (Example 2, Step 1 , 7.50 g, 25.1 mmol, 1.00 equiv.) in THF (150 mL) was added triethyl amine (17.4 mL, 125 mmol, 5 equiv.) and a solution of mesyl chloride (2.3 mL, 30 mmol, 1.2 equiv.) in THF (2 mL) at 0°C. Upon completed addition, the mixture was allowed to reach r.t. and heated to 45°C for 4 h. After cooling, saturated aqueous NaHC03 solution was added and the mixture was extracted with EtOAc. Combined organic layers were washed with brine and dried over Na2SC>4. Concentration in vacuum gave a residue which was dissolved in THF (100 mL) and methanol (100 mL). Solid K2CO3 (21 .7 g, 157 mmol, 5 equiv.) was added at r.t. and the mixture was stirred for 2 h. After concentration in vacuum, water was added and the resulting mixture was extracted with EtOAc. Combined organic layers were washed with brine and dried over Na2S04. Concentration in vacuum gave a crude product which was purified via silica gel chromatography to yield the title compound (5.66 g, 80%). ¹ H NMR (400 MHz, CDCI ₃ ): δ = 1.48 (s, 9H), 2.74 (m, 2H), 3.92 (m, 2H), 4.07-4.25 (m, 4H), 6.79 (d, 1 H), 7.22 (d, 1 H).

Step 3: tert-butyl 2-bromospiro[4,5-dihydrothieno[2,3-c]pyran-7,3'-azetidine]-1 '-carboxylate To a solution of tert-butyl spiro[4,5-dihydrothieno[2,3-c]pyran-7,3'-azetidine]-1 '-carboxylate (Step 2, 5.66 g, 20.1 mmol, 1.00 equiv.) and DMAP (122 mg, 1.01 mmol, 0.05 equiv.) in ace- tonitrile (100 mL) was added a solution of NBS (4.30 g, 24.1 mmol, 1.20 equiv.) in acetonitrile (70 mL) at 0°C. After 6 min at this temperature, the mixture was allowed to reach r.t. and stirred for another 2 h. Aqueous 10% NaHSC>3 was added and diluted with water. The mixture was ex- tracted with EtOAc and the organic layer was separated, dried over Na2S04 and concentrated in vacuum. Chromatography on silica gel yielded the title compound (6.90 g, 95%).

Step 4: tert-butyl 2-acetylspiro[4,5-dihydrothieno[2,3-c]pyran-7,3'-azetidine]- 1 '-carboxylate A mixture of tert-butyl 2-bromospiro[4,5-dihydrothieno[2,3-c]pyran-7,3'-azetidine]-1 '-carboxylate (Step 3, 6.90 g, 19.2 mmol, 1.00 equiv.), N-butyl vinyl ether (6.20 mL, 47.9 mmol, 2.5 equiv.), Pd(OAc)2 (258 mg, 1.15 mmol, 0.06 equiv.), 1 ,3-bis(diphenylphosphino)propane (947 mg, 2.30 mmol, 12.0 mol-%), triethylamine (5.4 mL, 38 mmol, 2.0 equiv.), and 1-butanol (100 mL) were degassed in an ultrasonic bath. The resulting mixture was heated at reflux for 3 h and cooled to 0°C, before it was slowly added to an ice cold aqueous 2 N HCI. The resulting slurry was vigorously stirred at r.t. for 30 min, before ethyl acetate (80 mL) was added. The layers were separated and the organic layer was washed with water and brine. After drying over

Na2S04, all volatiles were removed in vacuum and the residue was purified via column chromatography on silica gel to afford the title compound (3.90 g, 63%). ¹ H NMR (400 MHz, CDCI ₃ ): δ = 1.48 (s, 9H), 2.53 (s, 3H), 2.76 (m, 2H), 3.94 (m, 2H), 4.14 (d, 2H), 4.18 (d, 1 H), 7.39 (s, 1 H). Step 5: tert-butyl 2-[3-(3,5-dichloro-4-fluoro-phenyl)-4,4,4-trifluoro-3-hydrox y-buta- noyl]spiro[4,5-dihydrothieno[2,3-c]pyran-7,3'-azetidine]-1 '-carboxylate

A mixture of 1-(3,5-dichloro-4-fluoro-phenyl)-2,2,2-trifluoro-ethanone (6.30 g, 24.1 mmol, 2.00 equiv.), tert-butyl 2-acetylspiro[4,5-dihydrothieno[2,3-c]pyran-7,3'-azetidine]- 1 '-carboxylate (Step 4, 3.90 g, 12.1 mmol, 1.00 equiv.) and triethyl amine (0.34 mL, 2.4 mmol, 0.20 equiv.) in n-hep- tane (15 mL) was stirred at 60°C for 1 day. After cooling to r.t., the resulting precipitate was col- lected by filtration and dried to obtain the title compound (5.95 g, 84%). ¹ H NMR (400 MHz,

CDCI3): δ = 1.48 (s, 9H), 2.78 (m, 2H), 3.60 (dd, 2H), 3.94 (m, 2H), 4.10 (dd, 2H), 4.21 (m, 1 H), 5.90 (s, 1 H), 7.55 (s, 1 H), 7.58 (m, 2H).

Step 6: tert-butyl 2-[(E/Z)-3-(3,5-dichloro-4-fluoro-phenyl)-4,4,4-trifluoro-bu t-2-enoyl]spiro[4,5- dihydrothieno[2,3-c]pyran-7,3'-azetidine]-1 '-carboxylate To a solution of tert-butyl 2-[3-(3,5-dichloro-4-fluoro-phenyl)-4,4,4-trifluoro-3-hydrox y-buta- noyl]spiro[4,5-dihydrothieno[2,3-c]pyran-7,3'-azetidine]-1'- carboxylate (Step 5, 5.95 g, 10.2 mmol, LOOequiv.) in toluene (100 ml_) was added pyridine (4.1 ml_, 51 mmol, 5 equiv.) and thio- nyl chloride (2.59 ml_, 36 mmol, 3 equiv.) successively. The resulting reaction mixture was stirred at 80°C for 2 h, before it was cooled to r.t.. MTBE and aqueous 5% K2CO3 solution was added it was stirred vigorously. The aqueous layer was removed and discarded. The organic layer was washed with aqueous 2 N HCI, saturated aqueous NaHCC>3 solution and brine, before it was dried over Na2S0 ₄ . After concentration in vacuum, the crude title compound (5.3 g, 92%) was obtained and used in the next transformation without further purification.

Step 7: tert-butyl 2-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-i soxazol-3- yl]spiro[4,5-dihydrothieno[2,3-c]pyran-7,3'-azetidine]-1 '-carboxylate

To a solution of tert-butyl 2-[(E/Z)-3-(3,5-dichloro-4-fluoro-phenyl)-4,4,4-trifluoro-bu t-2- enoyl]spiro[4,5-dihydrothieno[2,3-c]pyran-7,3'-azetidine]-1 '-carboxylate (Step 6, 5.30 g, 9.36 mmol, 1.00 equiv.) in THF (60 mL) was added NaOH (1.5 g, 37 mmol, 4 equiv.) and a solution of hydroxylamine hydrochloride (1.30 g, 18.7 mmol, 2.00 equiv.) in water (7.5 mL) at r.t.. After completed reaction, the mixture was concentrated in vacuum and water and EtOAc were added. The organic layer was separated and washed with water and brine. The resulting solution was dried over Na2S0 ₄ and concentrated in vacuum. The residue was purified by chromatography on silica gel to afford the title compound (5.5 g, 98% purity, quantitative yield). ¹ H NMR (500 MHz, CDCI3): δ = 1.47 (s, 9H), 2.71 (m, 2H), 3.66 (d, 1 H), 3.92 (m, 2H), 4.05 (d, 1 H), 4.10 (dd, 2H), 4.17 (m, 1 H), 6.96 (s, 1 H), 7.57 (m, 2H).

Step 8: 2-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-i soxazol-3-yl]spiro[4,5-dihy- drothieno[2,3-c]pyran-7,3'-azetidin-1-ium];2,2,2-trifluoroac etate

To a solution of tert-butyl 2-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-i soxazol-3- yl]spiro[4,5-dihydrothieno[2,3-c]pyran-7,3'-azetidine]-1 '-carboxylate (Step 7 (5.50 g, 9.46 mmol, 1.00 equiv.) in dichloromethane (75 mL) was added trifluoroacetic acid (37 mL, 0.48 mol, 51 equiv.) at 0°C. After completed reaction, the mixture was concentrated at 20°C bath temperature and evaporated to dryness to afford the title compound (5.60 g, quantitative) which was used in the following transformations without purification.

Step 9: 1 -[2-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H -isoxazol-3-yl]spiro[4,5-dihy- drothieno[2,3-c]pyran-7,3'-azetidine]-1 '-yl]propan-1-one

To a solution of 2-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-i soxazol-3- yl]spiro[4,5-dihydrothieno[2,3-c]pyran-7,3'-azetidin-1 -ium];2,2,2-trifluoroacetate (Step 8, 500 mg, 0.840 mmol, 1.00 equiv.) in THF (10 mL) was added DMAP (10 mg) and diisopropyl ethylamine (0.86 mL, 5.1 mmol, 6 equiv.) at 0°C. After 30 min at this temperature, a solution of propionyl chloride (93 mg, 1.01 mmol, 1.20 equiv.) in THF (2 mL) was added and the cooling bath was removed. After 16 h at this temperature, water was added and the mixture was extracted with ethyl acetate. Combined organic layers were washed with aqueous 2 N HCI, brine and dried over Na2S0 ₄ . The resulting solution was concentrated in vacuum and purified via flash chroma- tography on silica gel to afford the title compound (276 mg, 58%). ¹ H NMR (400 MHz, CDCI3): δ = 1.16 (m, 3H), 2.19 (m, 2H), 2.72 (m, 2H), 3.66 (d, 1 H), 3.94 (m, 2H), 4.06 (d, 1 H), 4.14-4.38 (m, 4H), 6.97 (s, 1 H), 7.57 (m, 2H). Example 3: N-[2-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4 H-isoxazol-3-yl]-4, 5,6,7- tetrahydrobenzothiophen-4-yl]-2-methylsulfonyl-acetamide [C-7]

Step 1 : tert-butyl N-[(2Z)-2-(dimethylaminomethylene)-3-oxo-cyclohexyl]carbamat e

A solution of tert-butyl N-(3-oxocyclohexyl)carbamate (3.5 g, 16 mmol) and 1-tert-butoxy- Ν,Ν,Ν',Ν'-tetramethyl-methanediamine (8.6 g, 49 mmol) in DMF (100 ml.) was stirred at 60°C for 15 h. The reaction mixture was then concentrated to dryness and used without purification in the next step.

Step 2: [3-(tert-butoxycarbonylamino)-2-formyl-cyclohexen-1-yl] trifluoromethanesulfonate To a stirred solution of crude tert-butyl N-[(2Z)-2-(dimethylaminomethylene)-3-oxo-cyclo- hexyl]carbamate (4.4 g) and 2,6-di-tert-butylpyridine (9.4 g, 49 mmol) in CH ₂ CI ₂ (120 mL) at - 78°C was added triflic anhydride (9.2 g, 33 mmol). After 30 min at -78°C the reaction was quenched with a saturated aq. solution of NaHCC>3. The organic layer was separated and washed with saturated aq. solution of NaHC03 (2 *), dried over MgS04 and concentrated. Purification by silica gel chromatography using a gradient of CH / EtOAc afforded the title compound (1.68 g, 27% yield). ¹ H NMR (400 MHz, Chloroform-d) 5 10.01 (s, 1 H), 4.85 - 4.77 (m, 1 H), 4.51 (d, J = 7.6 Hz, 1 H), 2.64 - 2.55 (m, 2H), 2.03 - 1 .76 (m, 3H), 1.59 (tt, J = 12.7, 3.9 Hz, 2H), 1 .45 (s, 9H).

Step 3: tert-butyl N-(2-acetyl-4,5,6,7-tetrahydrobenzothiophen-4-yl)carbamate

To To a stirred solution of [3-(tert-butoxycarbonylamino)-2-formyl-cyclohexen-1-yl] trifluoro- methanesulfonate (1.48 g, 4.0 mmol) in DMF (30 mL) at 0°C was added a solution of NaSH (0.33 g, 5.9 mmol) in water (3 mL). The reaction mixture was stirred at 0°C for 15 min then 1- chloroacetone (0.40 g, 4.4 mmol) was added and the reaction mixture was allowed to warm to r.t.. After 1 h, a solution of NaOH (0.24 g, 5.9 mmol) in water (3 mL) was added to the reaction mixture, cooling the reaction mixture with an ice-bath to maintain an internal temperature of - 25°C. After 3 h the reaction mixture was diluted with water (300 mL) and extracted with MTBE (3 ^x ), dried over MgS0 ₄ and concentrated. Purification by silica gel chromatography using a gradient of CH / EtOAc afforded the title compound as a light brown solid (450 mg, 38% yield). H NMR (400 MHz, Chloroform-o!) δ 7.55 (s, 1 H), 4.77 (q, J= 10.6, 8.5 Hz, 2H), 2.89 - 2.70 (m, 2H), 2.50 (s, 3H), 2.07 (ddt, J= 11.7, 9.2, 4.2 Hz, 1 H), 1.95 - 1.84 (m, 2H), 1.79 - 1.67 (m, 1 H), 1.49 (s, 9H).

Step 4: tert-butyl N-[2-[3-(3,5-dichloro-4-fluoro-phenyl)-4,4,4-trifluoro-3-hyd roxy-butanoyl]- 4,5,6,7-tetrahydrobenzothiophen-4-yl]carbamate

A suspension of tert-butyl N-(2-acetyl-4,5,6,7-tetrahydrobenzothiophen-4-yl)carbamate (0.89 g, 3.0 mmol), 1-(3,5-dichloro-4-fluoro-phenyl)-2,2,2-trifluoro-ethanone (0.78 g, 3.0 mmol) and triethylamine (0.084 mL, 0.60 mmol) in n-heptane (5 mL) was stirred at 60°C for 6 d. The reaction mixture was cooled to 0°C and the title compound was isolated at a precipitate by vacuum filtration washing with cold n-heptane, which was used without further purification (1.25 g, 75% yield).

Step 5: tert-butyl N-[2-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4 H-isoxazol-3-yl]- 4,5,6,7-tetrahydrobenzothiophen-4-yl]carbamate

A suspension of tert-butyl N-[2-[3-(3,5-dichloro-4-fluoro-phenyl)-4,4,4-trifluoro-3-hyd roxy-buta- noyl]-4,5,6,7-tetrahydrobenzothiophen-4-yl]carbamate (1.10 g, 2.0 mmol), CsOH H ₂ 0 (0.96 g, 5.7 mmol), NH ₂ OH HCI (0.26 g, 3.7 mmol) in CH ₂ CI ₂ (20 mL) was stirred from 0°C to r.t. for 16 h. The reaction mixture was then concentrated by dryness and suspended in MTBE then wash with aq. 1 M HCI (3 *) and water (3 *), dried over MgS0 ₄ and concentrated to afford the title compound. ¹ H NMR (500 MHz, Chloroform-d) δ 7.56 (dd, J = 6.1 , 2.4 Hz, 4H), 7.09 (d, J = 1.8 Hz, 2H), 4.74 (d, J = 9.7 Hz, 2H), 4.04 (dd, J = 16.9, 4.9 Hz, 2H), 3.64 (dd, J = 17.0, 6.8 Hz, 2H), 3.22 (s, 1 H), 2.76 (qd, J = 15.0, 12.9, 8.7 Hz, 4H), 2.04 (dt, J = 1 1.5, 6.1 Hz, 2H), 1 .89 (s, 3H), 1.77 - 1.70 (m, 2H), 1.60 (s, 5H), 1.48 (d, J = 9.7 Hz, 19H), 1.19 (s, 3H).

Step 6: [2-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H- isoxazol-3-yl]-4,5,6,7-tetrahy- drobenzothiophen-4-yl]ammonium trifluoroacetate

A solution of tert-butyl N-[2-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4 H-isoxazol-3- yl]-4,5,6,7-tetrahydrobenzothiophen-4-yl]carbamate (1.05 g, 1.9 mmol) in CH ₂ CI ₂ (10 mL) and trifluoroacetic acid (5 mL) was stirred at r.t. for 16 h. The reaction mixture was then concentrated to dryness azeotropically drying with CH2Cl2 (3 *) to afford the title compound (1.07 g), which was used without further purification.

Step 7: N-[2-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4 H-isoxazol-3-yl]-4,5,6,7- tetrahydrobenzothiophen-4-yl]-2-methylsulfonyl-acetamide

A suspension of [2-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H- isoxazol-3-yl]-

4,5,6,7-tetrahydrobenzothiophen-4-yl]ammonium trifluoroacetate (0.25 g, 0.44 mmol), 2-methyl- sulfonylacetic acid (0.07 g, 0.5 mmol), DIPEA (0.18 g, 1 ,4 mmol), PyBroP (0.25 g, 0.53 mmol) in CH2CI2 (40 mL) was stirred at r.t. for 16 h. The reaction mixture was then diluted with water and the organic phase dried over MgSC and concentrated. Purification by silica gel chromatog- raphy using a gradient of CH / EtOAc afforded the title compound as a 1 :1 mixture of diastere- omers (0.13 g, 51 % yield). LC/MS: Rt : 1.3 min; MS: m / z = 573 (M+). ¹ H NMR (500 MHz, Chloroform-d) δ 7.56 (dd, J = 6.0, 1.5 Hz, 4H), 7.10 (d, J = 4.0 Hz, 2H), 6.57 (d, J = 8.6 Hz, 1 H), 6.50 (d, J = 8.6 Hz, 1 H), 5.08 (dq, J = 13.8, 6.8 Hz, 2H), 4.14 - 3.99 (m, 3H), 3.95 - 3.80 (m, 4H), 3.70 - 3.56 (m, 2H), 3.13 (d, J = 5.2 Hz, 6H), 2.87 - 2.72 (m, 4H), 2.14 - 2.02 (m, 3H), 1.76 (ddt, J = 16.6, 12.0, 6.2 Hz, 2H), 1.61 (s, 4H), 1.34 - 1.22 (m, 1 H).

Table C

Biological examples:

Example B-1 : Action on Yellow fever mosquito (Aedes aegypti)

For evaluating control of yellow fever mosquito {Aedes aegypti) the test unit consisted of 96- well-microtiter plates containing 200μΙ of tap water per well and 5-15 freshly hatched A. aegypti larvae.

The active compounds were formulated using a solution containing 75% (v/v) water and 25% (v/v) DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 2.5μΙ, using a custom built micro atomizer, at two replications.

After application, microtiter plates were incubated at 28 + 1 °C, 80 + 5 % RH for 2 days. Larval mortality was then visually assessed.

In this test, compounds C-1 , C-3, C-6, C-7, C-8, C-9, C-10, C-1 1 , C-12, C-13, C-14, C-15, and C-16, resp., at 800 ppm showed at least 75 % mortality in comparison with untreated controls.

Example B-2: Action on Orchid thrips (dichromothrips corbetti)

Dichromothrips corbetti ^' adults used for bioassay were obtained from a colony maintained continuously under laboratory conditions. For testing purposes, the test compound is diluted in a 1 : 1 mixture of acetone:water (vohvol), plus Kinetic® HV at a rate of 0.01 % v/v.

Thrips potency of each compound was evaluated by using a floral-immersion technique. All petals of individual, intact orchid flowers were dipped into treatment solution and allowed to dry in Petri dishes. Treated petals were placed into individual re-sealable plastic along with about 20 adult thrips. All test arenas were held under continuous light and a temperature of about 28°C for duration of the assay. After 3 days, the numbers of live thrips were counted on each petal. The percent mortality was recorded 72 hours after treatment.

In this test, compounds C-7, C-10, C-11 , C-12, C-13, C-14, C-15, and C-16, resp., at 300 ppm showed at least 75 % mortality in comparison with untreated controls.

Example B-3: Action on Boll weevil (Anthonomus grandis)

For evaluating control of boll weevil [Anthonomus grandis) the test unit consisted of 96-well- microtiter plates containing an insect diet and 5-10 A. grandis eggs.

The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 5 μΙ, using a custom built micro atomizer, at two replications.

After application, microtiter plates were incubated at about 25 + 1 °C and about 75 + 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.

In this test, compounds C-1 , C-2, C-3, C-4, C-5, C-7, C-8, C-10, C-1 1 , C-12, C-13, C-14, C-15, and C-16, resp., at 800 ppm showed at least 75 % mortality in comparison with untreated controls.

Example B-4: Action on Tobacco budworm (Heliothis virescens)

For evaluating control of tobacco budworm (Heliothis virescens) the test unit consisted of 96- well-microtiter plates containing an insect diet and 15-25 H. virescens eggs.

The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 10 μΙ, using a custom built micro atomizer, at two replications.

After application, microtiter plates were incubated at about 28 + 1 °C and about 80 + 5

In this test, compounds C-1 , C-2, C-3, C-4, C-5, C-6, C-7, C-8, C-9, C-10, C-11 , C-12, C-13, C-14, C-15, and C-16, resp., at 800 ppm showed at least 75 % mortality in comparison with untreated controls.

Example B-5: Action on Vetch aphid (Megoura viciae)

For evaluating control of vetch aphid {Megoura viciae) through contact or systemic means the test unit consisted of 24-well-microtiter plates containing broad bean leaf disks.

The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the leaf disks at 2.5 μΙ, using a custom built micro atomizer, at two replications.

After application, the leaf disks were air-dried and 5 - 8 adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids were then allowed to suck on the treated leaf disks and incubated at about 23 + 1 °C and about 50 + 5 % relative humidity for 5 days. Aphid mortality and fecundity was then visually assessed.

In this test, compounds C-1 , C-2, C-3, C-10, C-11 , C-12, C-13, C-14, C-15, and C-16, resp., at 800 ppm showed at least 75 % mortality in comparison with untreated controls. Example B-6: Action on Green Peach Aphid (Myzus persicae) (mixed life stages)

For evaluating control of green peach aphid {Myzus persicae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial membrane.

The compounds were formulated using a solution containing 75% v/v water and 25% v/v

DMSO. Different concentrations of formulated compounds were pipetted into the aphid diet, using a custom built pipetter, at two replications.

After application, 5 - 8 adult aphids were placed on the artificial membrane inside the microliter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at about 23 + 1 °C and about 50 + 5 % relative humidity for 3 days. Aphid mortality and fecundity was then visually assessed.

In this test, compounds C-1 , C-2, C-3, C-5, C-6, C-7, C-9, C-10, C-1 1 , C-12, C-13, C-14, C-15, and C-16, resp., at 800 ppm showed at least 75 % mortality in comparison with untreated controls.

Example B-7: Action on Diamond back moth {Plutella xylostella)

The active compound is dissolved at the desired concentration in a mixture of 1 :1 (vohvol) distilled water : acetone. Surfactant (Kinetic® HV) is added at a rate of 0.01 % (vol/vol). The test solution is prepared at the day of use.

Leaves of cabbage were dipped in test solution and air-dried. Treated leaves were placed in petri dishes lined with moist filter paper and inoculated with ten 3 ^rd instar larvae. Mortality was recorded 72 hours after treatment. Feeding damages were also recorded using a scale of 0- 100%.

In this test, compounds C-1 , C-2, C-3, C-4, C-5, C-6, C-7, C-8, C-9, C-10, C-11 , C-12, C-13, C-14, C-15, and C-16, resp., at 100 ppm showed at least 75 % mortality in comparison with untreated controls.