WO2018224455A1

WO2018224455A1 - Substituted cyclopropyl derivatives

Info

Publication number: WO2018224455A1
Application number: PCT/EP2018/064677
Authority: WO
Inventors: Birgit GOCKEL; Nikolas HUWYLER; Karsten Koerber; Arun Narine; Martin John MCLAUGHLIN
Original assignee: Basf Se
Priority date: 2017-06-07
Filing date: 2018-06-05
Publication date: 2018-12-13

Abstract

The invention relates to cyclopropyl compounds of formula (I), wherein the variables have the meanings as defined in the specification, to compositions comprising them, to active compound combinations comprising them, and to their use for protecting growing plants and animals from attack or infestation by invertebrate pests, furthermore, to seed comprising such compounds.

Description

Substituted cyclopropyl derivatives

Description

The invention relates to cyclopropyl compounds of formula I

wherein

R^1a is H, halogen, halomethyl, or Ci-C4-alkyl;

R^1b is halogen, halomethyl, or Ci-C4-alkyl;

R^1c, R^1d are independently H, or Ci-C₄-alkyl;

R^2a is halogen, halomethyl, or halomethoxy;

R^2b, R^2c are independently H, or as defined for R^2a;

HE is a fivemembered unsaturated heterocycle comprising 1 , 2, 3 or 4 heteroatoms selected from N(0)_n, O, and S(0)_m as ring members, wherein the carbon ring members are unsub- stituted or substituted with R^A; and any nitrogen ring members are substituted with R^N; n is 0, or 1 ;

m is 0, 1 , or 2;

R^A is independently halogen, CN, NO2, Ci-C₄-alkyl, Ci-C₄-haloalkyl, C2-C₄-alkenyl, C2- C₄-haloalkenyl, C2-C₄-alkynyl, C2-C₄-haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocyclo- alkyl, Ci-C₄-alkoxy, Ci-C₄-haloalkoxy, S(0)_m-Ci-C₄-alkyl, S(0)_m-Ci-C₄-haloalkyl, Ci-

C₄-haloalkylcarbonyl, C(=0)R³³, C(=0)OR³³, C(=0)N(R³ )R³²; or phenyl, which is unsubstituted or substituted with halogen, CN, or Ci-C₄-alkyl or Ci-C2-haloalkyl; R^N is independently H, Ci-C₄-alkyl, Ci-C₄-haloalkyl, C2-C₄-alkenyl, C2-C₄-haloalkenyl, C2-C₄-alkynyl, C2-C₄-haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C1-C4- haloalkylcarbonyl, C(=0)R³³, C(=0)OR³³, C(=0)N(R³ )R³²; or phenyl, which is unsubstituted or substituted with halogen, CN, or Ci-C₄-alkyl or Ci-C2-haloalkyl; R³ is H, halogen, CN, N0₂, OH, N(R³ )R³², Ci-C₆-alkyl, C₃-C₇-cycloalkyl, C₂-C₆-alkenyl, C₃- C7-cycloalkenyl, C2-C6-alkynyl, Ci-C6-alkoxy, Ci-C6-haloalkyl, C3-C7-halocycloalkyl, C2-C6- haloalkenyl, C3-C7-halocycloalkenyl, Ci-C6-haloalkoxy, S(0)_m-Ci-C6-alkyl, or S(0)_m-Ci-C6- haloalkyi, in which aliphatic groups are unsubstituted, partially or fully substituted with one or more R^a;

R³¹ is H, or d-Ce-alkyl,

R³² is H, d-Ce-alkyl, Ci-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl, C2-C6-haloalkynyl, or C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C3-C6-cycloalkylmethyl, or C3-C6-halocycloalkylmethyl which rings are unsubstituted or substituted with a

CN;

R^a is CN, N₃, N0₂, SCN, SF₅, Si(Ci-C₄-alkyl)₃, OR³³, OSO2R³³, S(0)_nR³³, N(R³ )R³², C(=0)N(R³ )R³², C(=S)N(R³ )R³², C(=0)OR³³, CH=NOR³³, C₃-C₈-cycloalkyl, C₃-C₈- halocycloalkyl, which cyclic moieties may be substituted with R³⁴; phenyl which is unsubstituted or substituted with one or more R^A; and 3- to 7-membered saturated, partially or fully unsaturated heterocycle comprising 1 , 2 or 3 heteroatoms O, N(0)_n or S(0)m as ring members, which heterocycle is unsubstituted or substituted with one or more R^A,

R³³ H, d-Ce-alkyl, Ci-C₆-haloalkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl, CH₂-CN, C₃-C₆- cycloalkyl, C3-C6-halocycloalkyl, C3-C6-cycloalkylmethyl, C3-C6-halocyclo- alkylmethyl, phenyl and hetaryl which aromatic rings are unsubstituted or partially or fully substituted with R^A;

R³⁴ is independently OH, CN, Ci-C₆-alkoxy, Ci-C₆-haloalkoxy, S(0)_m-Ci-C₆-alkyl, S(0)_m-Ci-C₆-haloalkyl, C(=0)N(R³ )R³², C₃-C₆-cycloalkyl, or C₃-C₆-halocyclo- alkyl which cycles are unsubstituted or substituted with one or more R³⁴⁴; or phenyl, partially or fully unsaturated heterocycle which rings are unsubstituted or substituted with one or more R^A;

R³⁴⁴ is independently OH, CN, Ci-C₂-alkyl, or Ci-C₂-haloalkyl;

T¹,T²,T³ are independently from each other N(0)_n, or C-R⁴, with the proviso that at least one thereof is C-R⁴;

R⁴ is idependently as defined for R³;

A is A1 : C(=U)NR⁵R⁶, or

A2: (CH₂)_nNR⁵C(=U)R⁶; wherein

U is O, or S; and

R⁵ is H, OH, C(=0)R³¹, C(=0)OR³¹, CN, Ci-Ce-alkyl, Ci-C₆-alkoxy, C₂-C₄-alkenyl, C₂-C₄-alky- nyl, C3-C8-cycloalkyl, C₂-Cio-alkenyl, C₂-Cio-alkynyl, N(R³¹)R³², phenyl or saturated, partially or fully unsaturated heterocycle, which groups are unsubstituted or substituted with one or more R^a; and wherein the rings are bonded directly or via Ci-C₄-alkyl spacer; R⁶ is H, Ci-Ce-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₃-C₈-cycloalkyl, C₃-C₈-cycloalkyl-Ci-C₄- alkyl, Ci-C6-alkylcarbonyl, Ci-C6-alkoxycarbonyl, phenyl or saturated, partially or fully unsaturated heterocycle, which groups are unsubstituted or substituted with one or more R^aa; and wherein the rings are bonded directly or via Ci-C₄-alkyl spacer;

R^aa is halogen, CN, Ci-Ce-alkyl, OR³¹, C(=NOR⁵¹)R⁵²; C(=0)N(R³ )R³², C(=S)N(R³ )R³², or C(=0)OR³¹; or two R^aa bound to the same C-atom form together C3-C6-cycloalkyl; R⁵¹,R⁵² are independently H, Ci-Ce-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₃-C₈-cyclo- alkyl, C3-C8-cycloalkyl-Ci-C₄-alkyl, phenyl or saturated, partially or fully unsaturated heterocycle, which groups are unsubstituted or substituted with one or more halogen, CN, N0₂; and wherein the rings are bonded directly or via Ci-C₄-alkyl spacer; and the N-oxides, stereoisomers and agriculturally or veterinarily acceptable salts thereof.

The invention also provides an agricultural composition comprising at least one compound of formula I, a stereoisomer thereof and/or an agriculturally acceptable salt thereof and at least one liquid and/or solid carrier, especially at least one inert liquid and/or solid agriculturally acceptable carrier.

The invention also provides a veterinary composition comprising at least one compound of formula I, a stereoisomer thereof and/or a veterinarily acceptable salt thereof and at least one liquid and/or solid carrier, especially at least one inert veterinarily liquid and/or solid acceptable carrier. The invention also provides a method for controlling invertebrate pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a cultivated plant, plant propagation materials (such as seed), soil, area, material or environment in which the pests are growing or may grow, or the materials, cultivated plants, plant propagation ma- terials (such as seed), soils, surfaces or spaces to be protected from pest attack or infestation with a pesticidally effective amount of a compound of formula I or a salt thereof as defined herein.

The invention also relates to plant propagation material, in particular seed, comprising at least one compound of formula I and/or an agriculturally acceptable salt thereof.

The invention further relates to a method for treating or protecting an animal from infestation or infection by parasites which comprises bringing the animal in contact with a parasiticidally effective amount of a compound of formula I or a veterinarily acceptable salt thereof. Bringing the animal in contact with the compound I , its salt or the veterinary composition of the invention means applying or administering it to the animal.

WO 2016/168059 describe structurally closely related active compounds. 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, in particular their agriculturally acceptable salts. Compounds of formula I can be prepared by the methods as described below, in the synthesis descriptions of the working examples, or by standard methods of organic chemistry which are known to a person skilled in the art. The substituents, variables and indices are as defined above for formula I , if not otherwise specified.

Compounds of formula I (la, lb, or lc) can be prepared by reacting a carboxylic acid of formula III, wherein X^E is OH, or a carboxylic acid derivative of formula III', wherein X^E is a leaving group, preferably a halogen such as CI or Br, or Ci-C6-alkoxy, such as OCH3 or OC2H5, with an amine of formula II in an amidation reaction. The amidation reaction is preferably carried out with acid chlorides of formula III' or by prior transformation of carboxylic acids of formula III with oxalyl chloride [(COCI)2] or thionylchloride (SOC ) to the corresponding acid chlorides of formula III', followed by reaction with an amine of formula II. Suitable reaction conditions are described in the literature, e.g. in WO2004/22536. The reaction is preferrably carried out in the presence of an organic base such as, NEt.3, N-ethyl-N,N-diisopropylamine (iP^NEt), pyridine, or substituted pyridines such as collidine or lutidine. Optionally a nucleophilic catalyst such as 4- (N,N-dimethylamino)pyridine ("DMAP") can be employed in the reaction. Suitable solvents are halogenated hydrocarbons such as, dichloromethane, chloroform, and chlorobenzene, or polar aprotic solvents such as tetrahydrofurane (THF), 1 ,4-dioxane, and N,N-dimethylformamide (DMF), or aromatic hydrocarbons such as benzene, toluene, 0-, m-, and p-xylene, or mixtures thereof. The transformation is usually carried out at temperatures from -40 °C to 100 °C, preferably from 0 °C to 30 °C. The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of I Is, based

Alternatively, amidation of the carboxylic acid III is carried out in the presence of a coupling re- agent. Suitable coupling reagents (activators) are known and are e.g. 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]pyri- dinium 3-oxid hexafluorophosphate ("HATU"), 0-(benzotriazol-1 -yl)-N,N,N',N'-tetramethyluroni- um hexafluorophosphate ("HBTU"), and 1 -[bis(dimethylamino)methylen]-5-chlorobenzotriazoli- urn 3-oxide hexafluorophosphate ("HCTU"), or phosphonium-derived activators, such as (Ben- zotriazol-1 -yloxy)tris(dimethylamino)phosphonium hexafluorophosphate ("BOP"), (benzotriazol- 1 -yl-oxytripyrrolidinophosphonium hexafluorophosphate) ("Py-BOP"), bromotripyrrolidinophos- phonium hexafluorophosphate ("Py-BrOP"). Generally, the activator is used in excess. The benzotriazole and phosphonium coupling reagents are generally used in a basic medium. In turn, carboxylic acids of formula III can be prepared by hydrolyzation of an ester of formula III', that is a compound of formula III wherein X^E is Ci-C6-alkoxy such as, for example, OCH3, OC2H5, or OC(CH3)3. Hydrolyzation can be carried out under standard conditions known to a person skilled in the art, e.g. under aqueous acidic conditions using e.g. hydrochloric acid, sulfuric acid (H2SO4) or trifluoroacetic acid (TFA), or under aqueous basic conditions using e.g. an alkali metal hydroxide, such as LiOH, NaOH or KOH. Amines of formula I Is and carboxylic acids of formula 1Mb or lllc, respectivel, are commercially available, or can be made as described in literature, or by standard methods of organic chemistry which are known to a person skilled in the art. Compounds of formula Γ, that is compounds of formula I wherein U is S, can be prepared by reacting the corresponding oxocompound (U is O) with Lawesson's reagent (CAS 19172-47-5), see, e.g., Jesberger et al. Synthesis, 2003, 1929-1958 and references therein. Solvents such as HMPA or THF at an elevated temperature such as 60 °C to 100 °C can be used. Preferred reaction conditions are in THF at 65 °C.

In turn, esters of formula Ilia', wherein X^E is Ci-C6-alkoxy such as OCH3 or OC2H₅, can be obtained by reacting a compound of formula IV, wherein X^Ar is halogen or OS(=0)2CF3 ("OTf"), with carbon monoxide in the presence of a palladium catalyst and an alcohol ROH, wherein R is Ci-C6-alkyl. Suitable reaction conditions are described in the literature (cf. WO2010/72781 ;

Alterantively, compounds of formula Ilia can be prepared by subjecting a compound of formula IV, that is a compound of formula IV wherein X^Ar is Br, or I, to halogen-metal exchange followed by the in situ reaction of this metallated intermediate with carbon dioxide. Suitable reaction conditions are described in the literature, e.g. in WO2009/132000, EP1582523. Suitable metalating agents are, e.g. iP^MgCI, iPr2MgCI-LiCI ("TurboGrignard"), n-butyllithium, tert-butyllithium. Optionally, the reaction can be performed in the presence of an additional amine ligand such as, e.g., Ν,Ν,Ν',Ν'-tetramethylethylenediamine ("TMEDA"). Suitable solvents are ethers such as, e.g., THF, 2-methyltetrahydrofurane, diethyl ether (Et.20), or aliphatic hydrocarbons such as pentane, hexane, cyclohexane, or mixtures thereof. If desired, the obtained carboxylic acids of formula Ilia can be further transformed into the corresponding esters of formula Ilia', wherein X^E is OR, in an esterification reaction. Esterification can be carried out under standard conditions known to a person skilled in the art, e.g. in the presence of an acid promotor such as e.g.

H2SO4, and the corresponding alcohol ROH.

Amines of formula Mb can be prepared by reacting a compound of formula IV, wherein X^Ar is halogen or OS(=0)2CF3 ("OTf"), in the presence of a palladium catalyst with an amine of formula R⁵NH2 in Buchwald-Hartwig Amination reaction. Suitable reaction conditions are reported in the literature (cf. WO2016/168059; P. Ruiz-Castillo and S. L. Buchwald Chem. Rev. 2016, 1 16, 12564-12649).

It is understood by a person skilled in the art that, in the presence of feasible Ti, 2, T3, R³, and X^Ar, nucleophilic aromatic substitution between a compound of formula IV and an amine of formula R⁵NH2 may represent a practical alternative. Suitable reaction conditions are described in the literature (cf. WO2010/100189).

Amines of formula lie can be prepared by reacting a compound of la-1 , that is a compound of formula la wherein R⁶ is hydrogen, with a reducing agent such as, e.g. lithium aluminum hydride (UAIH4), borane tetrahydrofuran complex ("BH3-THF"), borane dimethyl sulfide complex

(BH3-SMe2), in a reduction reaction. Suitable reaction conditions are described in the literature (cf. WO2016/961 15, WO2005/58301 , WO2014/202703). Suitable solvents are ethers such as THF, Et.20, tert-butylmethylether (TBME), or aromatic hydrocarbons such as benzene, toluene, 0-, m-, and p-xylene, or halogenated hydrocarbons such as, e.g. methylene chloride, chloroform, 1 ,2-dichloroethane, or mixtures thereof.

Alternatively, compounds of formula lc, that is compounds of formula I wherein A is A2, and U is O, can be prepared by reductive amidation of a nitrile of formula lid in the presence of hydrogen and a carboxylic acid derivative of formula III' wherein X^E is a leaving group, preferably halogen such as CI or Br, or Ci-C6-alkoxy, such as OCH3, or OC2H5.

The transformation is usually carried out at temperatures of from -50°C to 150°C, preferably from -10°C to 50°C, in an inert solvent, in the presence of a base and a catalyst [cf. J. Org. Chem. 1988, 53, 2847]. Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons such as toluene, 0-, m-, and p-xylene, ethers such as Et^O, diisopropylether (DIPE), TBME, di- oxane, anisole, and THF, esters such as ethyl acetate, methyl acetate, isopropyl acetate, alco- hols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert.-butanol, moreover DMF, and dimethylacetamide (DMA), acids such as acetic acid, and water, preferably ethers and alcohols. It is also possible to use mixtures of the solvents mentioned. Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as LiOH, NaOH, KOH and Ca(OH)2, alkali metal and alkaline earth metal carbonates, such as L12CO3, Na2C03, K2CO3 and CaC03, and also alkali metal bicarbonates, such as NaHC03,

KHCO3, moreover organic bases, e.g. tertiary amines, such as trimethylamine (ΝΜβ3), triethyla- mine (NEt.3), diisopropylethylamine, and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine, and DMAP, and also bicyclic amines. Particular preference is given to alkali metal bicarbonates and carbonates, such as NaHC03 or K2CO3. The bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent. The reaction step can only be performed in the presence of a hydrogenation catalyst. As used herein, the term "hydrogenation catalyst" covers heterogeneous and homogeneous hydrogenation catalysts, but preferably refers to heterogeneous catalysts. It is known in the art that platinum, palladium, rhodium, and ruthenium form highly active catalysts. Non-precious metal catalysts, such as catalysts based on nickel, such as Raney nickel and Urushibara nickel, are economical alternatives. In a preferred embodiment, the hydrogenation catalyst is platinum or palladium on a carrier, Raney nickel, and Raney cobalt. Raney nickel is particularly preferred. The reaction is carried out in the presence of hydrogen or a hydrogen source, preferably hydrogen is used. The reaction is in general carried out under at- mospheric pressure, which usually is in the range from 0.1 to 10 bar, preferably in the range of from 0.1 to 1 bar. The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of III', based on lid.

Compounds of formula 4a-1 , that is compounds of formula IV wherein HE is HE1 and Z¹ is O, can be prepared by reacting a compound of formula 5a in a Paal-Knorr Furan Synthesis type reaction. Suitable reaction conditions are described in literature (cf. WO2012/76704,

WO2014/100206, WO2016/71216, WO2015/81257). The reaction is generally carried out in the presence of an activating agent such as, e.g. trichlorophosphate (POC ), Burgess reagent (CAS 29684-56-8), para-toluenesulfonyl chloride ("TsCI"), trifluoromethylsulfonic anhydride ("Tf20"), thionyl chloride (SOC ), or a combination of reagents that produces a suitable activating agent in situ such as, e.g. Br2/PPh3, /PPhs, CCI₄/PPh3, or strong Bronstedt acids such as, e.g. hbSC , and para-toluenesulphonic acid ("TsOH"). Optionally, if an activating agent or an in situ produced activating agent is used, an amine base may be employed in the reaction such as, e.g. a tertiary amine like NEt.3, Ν,Ν-diisopropylethylamine, or aromatic amines such as e.g. pyridine, collidine, lutidine, DMAP. Suitable solvents are halogenated hydrocarbons such as, methylene chloride, chloroform, 1 ,2-dichloroethane, or polar aprotic solvents such as, acetoni- trile, THF, 1 ,4-dioxane, DMF, or aromatic hydrocarbons such as benzene, toluene, 0-, m-, and p-xylene.

Compounds of formula 4a-2, that is compounds of formula IV wherein HE is HE1 and Z¹ is S, can be prepared by reacting a compound of formula 5a with a thiating/activating agent such as Lawesson's reagent (CAS 19172-47-5), tetraphosphorus decasulfide (P₄Sio), or diphosphorus pentasulfide (P2S5). Suitable reaction conditions are described in the literature (cf.

WO2012/76704, WO2015/26574, WO201 1/159067, EP2009006). Suitable solvents are ethers such as THF, 1 ,4-dioxane, or aromatic hydrocarbons such as toluene, 0-, m-, and p-xylene. The transformation is usually carried out at temperatures from 20 °C to 200 °C, preferably from 60 °C to 140 °C.

Compounds of formula 4a-3, that is compounds of formula IV wherein HE is HE1 and Z¹ is NR^AZ, can be prepared by reacting a compound of formula 5a with the corresponding amine H₂NR^AZ, or a suitable ammonium salt HsNR^AZX thereof, wherein X represents a halogen or car- boxylate, in a Paal-Knorr Pyrrole Synthesis type of reaction. Suitable reaction conditions are described in the literature (cf. WO2013/53657, WO2008/51405, WO2012/139775). If amines H2lMR^AZ are employed, the reaction is generally carried out in the presence of an acid catalyst or promotor, whereas with ammonium salts HsNR^AZX an additional acid catalyst or promotor may be optionally employed in the reaction. Suitable acids are Bronsted acids such as, acetic acid, propionic acid, pivalic acid, TFA, TsOH, HCI, or Lewis acids such as titanium(IV) isopropiolate, titanium(IV) tetrachloride, and scandium tris(trifluoromethanesulfonate). Preferably, if R^AZ is H, ammonium salts such as ammonium acetate, ammonium bicarbonate, ammonium carbonate, and the like are employed in the reaction. Suitable solvents are aromatic hydrocarbons such as benzene, toluene, 0-, m-, and p-xylene, and the like, or halogenated hydrocarbons such as methylene chloride, chloroform, 1 ,2-dichloroethane, or polar aprotic solvents such as THF, 1 ,4- dioxane, or DMF. Compounds of formula 5a-1 , that is compounds of formula 5a wherein Z² is N, and Z³ is N or CR^A, can be prepared by reacting a carboxylic acid of formula 6a, wherein X^E is OH, or a carbo- xylic acid derivative of formula 6b, wherein X^E is a leaving group, preferably a halogen such as CI or Br, or Ci-C6-alkoxy, such as OCH3 or OC2H5, with an amine of formula 9 in an amidation reaction. The amidation reaction is preferably carried out with acid chlorides of formula 6b or by prior transformation of carboxylic acids of formula 6a with [(COCI)2] or SOC to the corresponding acid chlorides of formula 6b, followed by reaction with an amine of formula 9. Suitable reaction conditions are described in literature (cf. WO2004/22536). The reaction is generally carried out in the presence of an organic base such as NEt.3, iP^NEt, pyridine, or substituted pyridines such as collidine or lutidine. Optionally a nucleophilic catalyst such as DMAP can be employed in the reaction. Suitable solvents are halogenated hydrocarbons such as dichloromethane, chloroform, and chlorobenzene, or polar aprotic solvents such as THF, 1 ,4-dioxane, and DMF, or aromatic hydrocarbons such as benzene, toluene, 0-, m-, and p-xylene, or mixtures thereof. The transformation is usually carried out at temperatures from -40 °C to 100 °C, preferably from 0 °C to 30 °C. The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of 9, based on 6.

Alternatively, amidation of the carboxylic acid 6a is carried out in the presence of a coupling reagent. Suitable coupling reagents (activators) are known and are e.g. carbodiimides, such as DCC and Ν,Ν-diisopropyhcarbodiimide ("DCI"), benzotriazole derivatives such as HATU, HBTU, and HCTU, or phosphonium-derived activators, such as BOP, Py-BOP, 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 5a-2, that is compounds of formula 5a wherein Z² is N or CR^A, and Z³ is N, can be prepared by reacting an amine of formula 7a with a carboxylic acid of formula 10a, wherein X^E is OH, or a carboxylic acid derivative of formula 10b, wherein X^E is a leaving group, preferably a halogen such as CI or Br, or Ci-C6-alkoxy, such as OCH3 or OC2H5, in an amidation reaction. The amidation reaction is carried out analoguously as described above for compounds of formula 5a-1.

Compounds of formula 5a-3, that is compounds of formula 5a wherein Z² and Z³ are both CR^A, can be prepared by reacting an enone of formula 8 with an aldehyde of formula 11 in a Stetter reaction. Suitable reaction conditions are described in literature (cf. WO2003/101959). The reaction is generally carried out in the presence of a nucleophilic catalyst such as NaCN or KCN, or thiazolium salts such as 3-ethyl-5-(2-hydroxyethyl)-4-methyl-1 ,3-thiazolium bromide, 5-(2-hy- droxyethyl)-4-methyl-3-(phenylmethyl)thiazolium chloride, or 3,4-dimethyl-5-(2-hydroxyethyl)- thiazolium iodide. The thiazolium salts are generally employed in the presence of a base such as tertiary amines like NEt.3, iP^NEt, or amidine bases such as 1 ,8-diazabicyclo[5.4.0]undec-7- ene. Suitable solvents are e.g. alcohols such as ethanol, or isopropanol, or polar aprotic solvents such as THF, 1 ,4-dioxane, DMF, or DMSO. The transformation is usually carried out at temperatures from 0 °C to 150 °C, preferably from 20 °C to 80 °C. Altenatively, compounds of formula 5a-3 can be prepared by reacting an aldehyde of formula 12 with an enone of formula 13 in a Stetter reaction under the conditions as described above.

Compounds of formula 4b-1 , that is compounds of formula IV wherein HE is HE2 and Z² is N, can be prepared by reacting a dipolarophile of formula 14, wherein Z³ is CR^A or N, with an in sit ,3-dipolar cycloaddition reaction, as shown below.

The 1 ,3-dipolar cycloaddition can, e.g., be performed as nitrile imine cycloaddition reaction (i.e. Z¹ = NR^AZ) between an in situ produced nitrile imine of formula 5b-1 and a dipolarophile of formula 14. Nitrile imines of formula 5b-1 are well known and can be generated, e.g., from a hy- drazonyl halogenide of formula 15a, wherein Y^H1 is a halogen like CI or Br, and Y^H2 is H or S(=0)2(aryl), by means of an elimination reaction. Suitable reaction conditions are described in literature (cf. US5892048; E. Strocci et al. European Journal of Medicinal Chemistry, 2012, 48, 391 -401 ). The reaction is generally carried out in the presence of an activating agent such as an organic base like NEt.3, iP^NEt, or sodium ethanolate, or an inorganic base such as Ag2CC"3, Na2CC"3, NaOH, or a Lewis acid such as AICI3, or ytterbium(lll) triflate. Suitable solvents are aromatic hydrocarbons such as benzene, toluene, 0-, m-, and p-xylene, or halogenated hydrocar- bons such as methylene chloride, chloroform, 1 ,2-dichloroethane, chlorobenzene, 1 ,2-dichloro- benzene, or polar aprotic solvents such as THF, 1 ,4-dioxane, acetonitrile, ethyl acetate, or lower alkanols, and also mixtures thereof. In turn, hydrazonyl halogenide of formula 15a, can either be prepared in a separate step from compounds of formula 7 or, preferably, be produced in situ as described in H. Wamhoff et al. Synthesis, 1987, 876-879.

Alternatively, nitrile imines of formula 5b-1 can also be generated, for example, from a hydra- zone of formula 15b', wherein Y^H1 is H, and Y^H2 is S(=0)2(aryl), by means of an elimination reaction. Suitable reaction conditions are described in literature (cf. Y. Kong et al. Org. Lett. 2014, 16, 576-579; M. Tang et al. Synthesis 2016, 48, 3065-3076).

It is understood by a person skilled in the art that several alternative methods for the generation of nitrile imines of formula 5b-1 , or surrogate thereof, can be used which, in certain settings, may be advantageous. Suitable alternatives for the generation of nitrile imines are described in literature (cf. J. T. Sharp, "The Chemistry of Heterocyclic Compounds, Volume 59: Synthetic Applications of 1 ,3-Dipolar Cycloaddition Chemistry Toward Heterocycles and Natural Products", Eds. A. Padwa, W. H. Pearson, Chapter 7, John Wiley & Sons, Inc., 2002; H. Wamhoff et al. Synthesis, 1987, 876-879).

The 1 ,3-dipolar cycloaddition can also be performed as nitrile oxide cycloaddition reaction (i.e. Z¹ = O) between an in situ produced nitrile oxide of formula 5b-2 and a dipolarophile of formula 14. Nitrile oxides can be derived from aldoximes of formula 16', wherein X is H. The reaction typically proceeds through the intermediacy of in situ generated hydroxamic acid halogenides, wherein X is halogen, usually CI, 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 dipolarophile 14. Depending on the exact conditions, employment of an additional amine base such as NEt.3, Ν,Ν-diisopropylethylamine, or pyridine may be neces- sary. The reaction can be run in a wide variety of solvents including aromatic hydrocarbons such as benzene, toluene, 0-, m-, and p-xylene, or halogenated hydrocarbons such as methylene chloride, chloroform, 1 ,2-dichloroethane, chlorobenzene, 1 ,2-dichlorobenzene, or polar aprotic solvents such as THF, 1 ,4-dioxane, acetonitrile, ethyl acetate, DMF, or lower alkanols, and also mixtures thereof. In turn, aldoximes of formula 16', that is compounds of formula 16 wherein X is H, can be obtained by reacting aldehydes of formula 12 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 NEt.3, pyridine, or sodium acetate, or inorganic bases such as NaOH or K2CO3.

It is understood by a person skilled in the art that several alternative methods for the generation of nitrile oxides of formula 5b-2, or surrogate thereof, can be used which, in certain settings, may be advantageous. Suitable alternatives for the generation of nitrile oxides are described in literature (cf. V. Jager and P. A. Colinas, "The Chemistry of Heterocyclic Compounds, Volume 59: Synthetic Applications of 1 ,3-Dipolar Cycloaddition Chemistry Toward Heterocycles and Natural Products", Eds. A. Padwa, W. H. Pearson, Chapter 6, John Wiley & Sons, Inc., 2002). Furthermore, the 1 ,3-dipolar cycloaddition can also be performed as nitrile sulfide cycloaddition reaction (i.e. Z¹ = S) between an in situ produced nitrile sulfide of formula 5b-3 and a dipolarophile of formula 14. Nitrile sulfides can be generated in situ by the thermolysis of 5-substi- tuted 1 ,3,4-oxathiazol-2-ones of formula 17. Suitable reaction conditions are described in literature (cf. WO2016/100766, R. K. Howe et al. J. Org. Chem. 1978, 43, 3736-3742). Suitable solvents are aromatic hydrocarbons such as toluene, o-, m-, and p-xylene, or halogenated hydrocarbons such as chlorobenzene, 1 ,2-dichlorobenzene, or aliphatic hydrocarbons such as n-do- decane, decalin. The transformation is usually carried out at temperatures from 100 °C to 250 °C, preferably from 150 °C to 220 °C.

It is understood by a person skilled in the art that, in certain cases, the replacement of an al- kyne of formula 14, wherein Z³ is CR^A, with an appropriate alkyne surrogate such as a vinyl hal- ide, beta-ketoester, beta-ketonitrile, enamines, or vinyl azide may be preferred in the 1 ,3-dipolar cycloaddition reaction. Suitable examples are described in literature (cf. WO2010/127855, EP946508, WO2005/49578).

Compounds of formula 4c-1 , that is compounds of formula IV wherein HE is HE3 and Z² is N, can be prepared by reacting a dipolarophile of formula 5c, wherein Z³ is CR^A or N, with an in situ produced 1 ,3-dipol of formula 18 in a 1 ,3-dipolar cycloaddition reaction, as shown below. The nitrile immine, nitrile oxide, and nitrile sulfide cycloaddition reactions can be carried out an- aloguously as described above for the synthesis of compounds of formula 4b-1.

Compounds of formula 4b-2, that is compounds of formula IV wherein HE is HE2. Z² is CR^A, and Z³ is N, can be prepared by reacting a compound of formula 19 with a suitable ammonia equivalent in a condensation reaction. Suitable reaction conditions are described in literature (cf. US2012/129891 ; WO2014/72903; W. Huang et al. Tetrahedron 1996, 52, 10131 -10136; A. Commeureuc et al. Org. Lett. 2003, 5, 2785-2788). Suitable ammonia equivalents are e.g. ammonium acetate, ammonium formate, ammonium trifluoroacetate, acetamide/BF3-OEt2. Suitable solvents are, e.g. carboxylic acids such as acetic acid, or polar aprotic solvents such as THF, DMF, or aromatic hydrocarbons such as toluene, o-, m-, and p-xylene, or halogenated hydrocarbons such as dichloromethane, chloroform, 1 ,2-dichlorobenzene, or mixtures thereof. The transformation is usually carried out at temperatures from 40 °C to 200 °C, preferably from 60 °C to 160 °C. Compounds of formula 4b-2', that is compounds of formula IV wherein HE is HE2, Z² and Z³ are CR^A, can be prepared as described in M. Shindo et al. Org. Lett. 2007, 9, 1

In turn, compounds of formula 19a, that is compounds of formula 19 wherein Z¹ is O and Z² is CR^A, can be prepared by reacting an alpha-hydroxy ketone of formula 20a with a carboxylic acid of formula 10a, wherein X^E is OH, or a carboxylic acid derivative of formula 10b, wherein X^E is a leaving group, preferably a halogen such as CI or Br, or Ci-C6-alkoxy, such as OCH3 or OC2H5, in an esterification reaction. The esterification reaction is preferably carried out with acid chlorides of formula 10b or by prior transformation of carboxylic acids of formula 10a with [(COCI)2] or SOC to the corresponding acid chlorides of formula 10b, followed by reaction with an alpha- hydroxy ketone of formula 20a. Suitable reaction conditions are described in literature (cf.

US2009/318396). The reaction is preferrably carried out in the presence of an organic base such as NEt.3, iP^NEt, pyridine, substituted pyridines such as collidine or lutidine. Optionally a nucleophilic catalyst such as DMAP can be employed in the reaction. Suitable solvents are hal- ogenated hydrocarbons such as dichloromethane, chloroform, and chlorobenzene, or polar aprotic solvents such as THF, 1 ,4-dioxane, acetonitrile, and DMF, or aromatic hydrocarbons such as benzene, toluene, 0-, m-, and p-xylene, or mixtures thereof. The transformation is usually carried out at temperatures from -40 °C to 100 °C, preferably from 0 °C to 40 °C. The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of 10b, based on 20a.

Alternatively, esterification of the alpha-hydroxy ketone 20a is carried out with a carboxylic acid of formula 10a in the presence of a coupling reagent. Suitable coupling reagents (activators) are known and are, e.g. selected from carbodiimides, such as DCC, DCI, 1 -ethyl-(3-(3-di- methylamino)propyl)-carbodiimide ("EDCI"). The reaction is generally carried out in the presence of an amine base such as DMAP. Suitable solvents are halogenated hydrocarbons such as dichloromethane, chloroform, and chlorobenzene, or polar aprotic solvents such as THF, 1 ,4- dioxane, and DMF, or aromatic hydrocarbons such as benzene, toluene, 0-, m-, and p-xylene, or mixtures thereof. The transformation is usually carried out at temperatures from -40 °C to 100 °C, preferably from 0 °C to 40 °C. The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of 10a, based on 20a. Suitable reaction conditions are described in literature (cf. J.-W. Lin et al, Org. Lett. 2014, 16, 5328-5331 ).

Compounds of formula 19b, that is compounds of formula 19 wherein Z¹ is S and Z² is CR^A, can be prepared by reacting a compound of formula 20b with a carboxylic acid of formula 10a, wherein X^E is OH, in the presence of a coupling reagent, analogous as described above for the synthesis of compounds of formula 19a. Suitable reaction conditions are described in literature (cf. T. Hatanaka et al. Org. Biomol. Chem. 2016, 14, 10589-10592).

Alternatively, compounds of formula 19 can be prepared by reacting an alpha-haloketone of formula 20c, wherein X is a halogen such as chloride, bromide, or iodide, with a carboxylic acid of formula 10a, or a thiocarboxylic acid of formula 10c, resp., as shown above. Suitable reaction conditions are described in literature (cf. M. Soural et al. Eur. J. Org. Chem. 2009, 3867-3870; R. Seshadri et al. J. Med. Chem. 1986, 29, 1269-1273; US4299769). The reaction is generally carried out in the presence of a base such as amine bases like NEt.3, iP^NEt, pyridine, substituted pyridines such as collidine or lutidine, or alkali metal carbonates, such as U2CO3, K2CO3, CS2CO3, or alkali metal alkoxides such as sodium methylate, potassium tert-butoxide, or alkali metal hydrides such as NaH. Suitable solvents are polar aprotic solvents such as DMF, acetoni- trile, THF, or lower alkanols such as methanol, or ethanol.

Compounds of formula 4c-2, that is compounds of formula IV wherein HE is HE3 and Z² is CR^A, can be prepared from compounds of formula 21 , analoguously as described above for compounds of formula 4b-2. A person skilled in the art understands that the same holds true for the synthesis of compounds of formula 21 , which can be obtained in analogy to the compounds

Compounds of formula 4d-1 , that is compounds of formula IV wherein HE is HE4, and Z² Z³ are N, can be prepared by reacting an azide of formula 23 with a compound of formula 14' in a 1 ,3-dipolar cycloaddition. Suitable reaction conditions are described in literature (cf.

WO2013/71035). The reaction is typically performed in the presence of a copper salt such as Cul, CuSC , copper(ll) acetate. Optionally, an amine base such as NEt.3, or iP^NEt and/or an additive such as sodium ascorbate, ascorbic acid can be employed in the reaction. Suitable solvents are polar aprotic solvents such as DMF, THF, or alcohols such as methanol, ethanol, tert- butanol, or aromatic hydrocarbons such as, toluene, 0-, m-, and p-xylene, or water, and it is also possible to use mixtures of the solvents mentioned.

Preferrably, the azide of formula 23 is generated in situ from an amine of formula 24 by treatment with a diazotransfer reagent. Suitable reaction conditions are described in literature (cf. Neal M. Smith et al. Synlett, 2009, No. 9, 1391 -1394; WO2014/48065). Suitable diazotransfer reagents are e.g. imidazole-1 -sulfonyl azide hydrochloride, trifluoromethanesulfonyl azide, tri- methylsilylazide. The reaction is generally performed in the presence of a copper salt such as CuSC . Optionally, an amine base such as NEt.3, or iP^NEt, and/or an additive such as sodium ascorbate, ascorbic acid can be employed in the reaction. Suitable solvents are alcohols such as methanol, ethanol, tert-butanol, or polar aprotic solvents such as DMF, THF, or or aromatic hydrocarbons such as toluene, 0-, m-, and p-xylene, or water, and it is also possible to use mixtures of the solvents mentioned.

Alternatively, it is also possible to form an azide of formula 23 in a separate step as described in literature (cf. E. D. Goddard-Borger et al., Org. Lett. 2007, 9, 3797).

Compounds of formula 24 can be obtained from acids of formula 6a, by Curtius rearrangement of the corresponding acyl azides of formula 25. This transformation is usually carried out at temperatures of from -20°C to 120°C, preferably from 0°C to 80°C, in an inert solvent, in the pres- ence of a base or an acid. Suitable reaction conditions are described in literature (cf. N. B. M. Arts et al, Tetrahedron, 1978, 34, 1271 -1279). Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and petrol ether, aromatic hydrocarbons such as toluene, 0-, m-, and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, and chlorobenzene, ethers such as Et.20, DIPE, MTBE, dioxane, anisole, and THF, nitrils such as acetonitrile, and proponitrile, ketons such as acetone, methyl ethyl ketone, diethyl ketone, and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n- butanol, and tert-butanol, preferably alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol. It is also possible to use mixtures of the solvents mentioned. Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal carbonates, such as U2CO3, K2CO3, and CaC03, and alkali metal bicarbonates, such as NaHC03, moreover organic bases, for example tertiary amines, such as ΝΜβ3, NEt.3, iP^NEt, and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine, and DMAP, and bicyclic amines. Particular preference is given to alkali metal and alkaline earth metal carbonates, such as L12CO3, K2CO3, tertiary amines such as ΝΜβ3, pyridine. The bases are gener- ally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent. Suitable acids and acidic catalysts are in general inorganic acids such as HF, HCI, HBr, H2SO4 and HCIO4, Lewis acids, such as BF₃, AICI₃, FeCI₃, SnCI₄, TiCI₄, and ZnC , moreover organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, toluene sulphonic acid, benzene sulphonic acid, camphor sulphonic acid, citric acid, and TFA. The acids are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.

Compounds of formula 4e-1 , that is compounds of formula IV wherein HE is HE5, and Z², Z³ are N, can be prepared by reacting an azide of formula 26 with a compound of formula 5c in a 1 ,3-dipolar cycloaddition, analogously as described above for the synthesis of compounds of formula 4d-1. In turn, amines of formula 26 are commercially available, or can be made by standard methods of organic chemistry which are known to a person skilled in the art.

Alternatively, compounds of formula 28, that is compounds of formula I, II, III, or IV wherein HE is HE4, and compounds of formula 30, that is compounds of formula I, II, III, or IV wherein HE is HE5, can be prepared by reacting a compound of formula 27 or 28, respectively, in a cyclopro- panation reaction. Suitable reaction conditions for the cyclopropanation are described in literature (cf. WO2016/168059; V. A. Kobelevskaya et al. Russ. J. Org. Chem. 2017, 53, 144-146; US6887870). R^AR1 in 27 and 28 denotes either the corresponding arene as depicted in I, Mb, lie, Ilia, or IV, or it denotes a leaving group such as a halogen like I, Br, or CI, or a sulfonic ester such as OS(=0)2CF3, which can be used to introduce the corresponding arene in a later Stille, Suzuki, or Hiyama cross coupling reaction. R^AR2 in 29 and 30 denotes either the corresponding arenes as depicted in I, Mb, lie, Ilia, or IV, or it denotes a suitable amine protecting group that can later be removed and the liberated amine reacted with an appropriate arene in a Buchwald- Hartwig, Ullmann, or Chan-Lam amination reaction, or a nucleophilic aromatic substitution reactio

For compounds of formula 28 and 30, wherein R^1a and R^1b are CI, Br, or I, the cyclopropana- tion reaction is preferably carried out with chloroform, bromoform, or iodoform as the carbene precursors which are then transformed in situ into the respective carbene upon treatment with a suitable base. The carbene precursors are preferably used in excess with respect to compounds 27 and 29, resp., or as the solvent, if appropriate. Suitable bases are, e.g. alkali metal and alkaline earth metal hydroxides such as NaOH, KOH, Ca(OH)2, or alkali metal alcoholates such as, sodium methylate, or potassium tert-butylate. Suitably, the alkali metal and alkaline earth metal hydroxides can be employed as an aqueous solution in a biphasic reaction mixture together with an organic solvent. In these cases, the carbene precursors are preferably used as the solvents. Optionally, if biphasic conditions are used, a phase transfer catalyst can be employed in the reaction such as N-benzyl-N,N,N-triethylammonium chloride, tetrabutylammomium bromide, tetra(n-butyl)ammonium iodide, or N-hexadecyl-N,N,N-trimethylammonium bromide. The transformation is usually carried out at temperatures of from -50°C to 100°C, preferably from 0°C to 50°C. Otherwise, if the reaction is performed in the absence of water, suitable organic solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and petrol ether, or ethers such as Et.20, TBME, or halogenated hydrocarbons such as dichloromethane, or mixtures thereof. In these cases, the transformation is usually carried out at temperatures of from -100°C to 50°C, preferably from -50°C to 25°C.

Alternatively, in cases, where R^1a and R^1b are both CI, compounds of formula 28 and 30, can be prepared by reacting a compound of formula 27 or 29, resp., in a cyclopropanation with bromo(dichloro)methyltrimethylsilane (TMSCC Br). This transformation is usually carried out at temperatures of from -100°C to 50°C, preferably from -78°C to 30°C, in an inert solvent, in the presence of a base [cf. Lee et al, Chem. Eur. J. 2016, 22, 7609-7616]. Suitable solvents are hal- ogenated hydrocarbons, ethers such as dioxane, anisole, and THF, nitrils such as acetonitrile, and propionitrile, moreover DMSO, DMF, and DMA, preferably THF, acetonitrile, and DMF. It is also possible to use mixtures of the solvents mentioned. Suitable bases are, in general, organic bases, preferably ammonium salts such as tetrabutylammonium fluorides, preferably NBu₄F, and NBu₄Ph3SiF2. The bases are generally employed in equimolar amounts; however, they can also be used in small excess.

For compounds of formula 28 and 30, wherein R^1a and R^1b are F, the cyclopropanation reaction is preferably carried out with trimethyl(trifluoromethyl)silane, trimethylsilyl 2,2-difluoro-2- (fluorosulfonyl)acetate, sodium chlorodifluoroacetate, sodium bromodifluoroacetate as the car- bene precursor. Suitable reaction conditions are described in literature (cf. WO2014/150677; WO2006/103503; WO2016/22724).

Compounds of formula 27 can be prepared by reacting an amine of formula 31 with a styrene of formula 32, wherein Y^cc is a halogen such as I, Br, or CI, or a boronic acid B(OH)2, or a tri- fluoroborate salt such as BF3K, in an Ullmann-type (Y^cc = I, Br, CI) or a Chan-Lam-type (Y^cc = B(OH)2, BF3K) amidation reaction. Suitable reaction conditions are described in literature (cf. M. S. Kabir et al. Org. Lett., 2010, 12, 464^167; WO2009/140342; A. de Meijere et al., "Metal-Catalyzed Cross-Coupling Reactions and More", Wiley-VCH, 2014). The reaction is generally carried out in the presence of a copper salt such as, for example, copper(ll) acetate, Cul, CuBr, CuCI, and in the presence of an amine like pyridine, 2-pyridin-2-yl-1 H-benzoimidazole, 1 ,10-phenant- roline, NEt.3, ethylenediamine, or an inorganic base such as an alkali metal carbonate like K2CO3, CS2CO3, or an alkali metal phosphate such as potassium phosphate. It is also possible to employ both, an amine and an inorganic base, in the reaction. Suitable solvents in the Ullmann-type amidation are, e.g. polar aprotic solvents such as DMF, DMA, DMSO, acetonitrile, THF, 1 ,4-dioxane, or aromatic hydrocarbons such as toluene, 0-, m-, and p-xylene, or mixtures thereof. Suitable solvents in the Chan-Lam-type amidation are, e.g., halogenated hydrocarbons such as dichloromethane, chloroform, 1 ,2-dichloroethane, or alcohols such as methanol, etha- nol, or polar aprotic solvents such as DMF, DMA, DMSO, acetonitrile, THF, 1 ,4-dioxane, or water, or mixtures thereof. Optionally, the Chan-Lam-type coupling can be carried out in the pres- ence of molecular oxygen. Alternatively, amines of formula 31 and styrenes of formula 32, wherein Y^cc is a halogen such as I, Br, or CI, can also be reacted with one another in the presence of a palladium catalyst in a Buchwald-Hartwig amidation reaction. Suitable reaction conditions are described in literature (cf. P. Ruiz-Castillo and S. L. Buchwald Chem. Rev. 2016,1 16, 12564-12649; A. de Meijere et al., "Metal-Catalyzed Cross-Coupling Reactions and More", Wiley-VCH, 2014). In turn, compounds of formula 31 and 32 are commercially available or can be prepared as described in literature, or by standard methods of organic chemistry which are

27

Alternatively, compounds of formula 27 can be prepared by reacting an olefin of formula 33 with an arene of formula 34, wherein X^cc is a halogen such as I, Br, or CI, in a Heck reaction. Suitable reaction conditions are described in literature (cf. WO2007/21937; US2003/153568; A. de Meijere et al., "Metal-Catalyzed Cross-Coupling Reactions and More", Wiley-VCH, 2014). The reaction is generally carried out in the presence of a palladium catalyst such as

Pd(OAc)2/tris(o-tolyl)phosphine, bis(triphenylphosphine)palladium(l l) dichloride, tetrakis(triphe- nylphosphine)palladium(O), Pd(tBu3P)2, [1 ,1 '-Bis(di-tert-butylphosphino)ferrocene]dichloropalla- dium(l l), and in the presence of a base such as an amine base like NEt.3, iP^NEt, N-methyl-N,N- dicyclohexylamine, or an alkali metal carbonate such as Na2C03, K2CO3, CS2CO3. Suitable solvents are polar aprotic solvents such as DMF, DMA, acetonitrile, THF, or aromatic hydrocarbons such as toluene, 0-, m-, and p-xylene, or mixtures thereof. In turn, compounds of formula 33 and 34 are commercially available or can be prepared as described in the literature, or by standard methods of organic chemistry which are known to a person skilled in the art.

Compounds of formula 29 can be prepared by reacting either a compound of formula 35 with a compound of formula 36, or a compound of formula 37 with a compound of formula 38, resp., in a transition-metal catalyzed cross-coupling reaction. X^cc and Y^cc are either the kind of function- nal group that undergoes oxidative addition with a transition-metal catalyst such as I, Br, CI or OS(=0)2CF3, or the kind of functional group that undergoes transmetallation with a transition- metal catalyst such as, for example, SnR.3, S1R3, BR2, AIR2, ZnR, and the like. A person skilled in the art will understand that the groups X^cc and Y^cc are interdependently chosen in such a way that they are always of the opposite kind and not of the same. Preferably, palladium cata- lysts are used as the transition-metal catalysts. Suitable reaction conditions are described in literature (cf. A. de Meijere et al., "Metal-Catalyzed Cross-Coupling Reactions and More", Wiley- VCH, 2014).

In turn, compounds of formula 35, 36, 37, and 34 are commercially available or can be prepared as described in the literature, or by standard methods of organic chemistry which are known to a person skilled in the art.

Hydrazides of formula 7a-1 and 7b-1 , resp., can be prepared by reacting a carboxylic acid of formula 6a, wherein X^E is OH , or a carboxylic acid derivative of formula 6b, wherein X^E is a leaving group, preferably a halogen such as CI or Br, or Ci-C6-alkoxy, such as OCH3 or OC2H5, with a hydrazine of formula H2NNHR^AZ in an amidation-type reaction. The amidation-type reaction is preferably carried out with esters of formula 6b and a hydrazine of formula H2NNHR^AZ. Suitable reaction conditions are described in literature (cf. WO2013/144295, WO2013/182274). Preferably, if R^AZ is H, the hydrazine is used in the form of its corresponding hydrate of formula

Η2ΝΝΗ2Ή2Ο. Suitable solvents are alcohols such as methanol, ethanol, iso-propanol, tert-buta- nol, or polar aprotic solvents such as 1 ,4-dioxane, acetonitrile, or water, and mixtures thereof. The transformation is usually carried out at temperatures from 20 °C to 180 °C, preferably from 20 °C to 100 °C. The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of the hydrazine, bas

Alternatively, the amidation-type reaction is can carried out with acid chlorides of formula 6b or by prior transformation of carboxylic acids of formula 6a with [(COCI)2] or SOC to the corresponding acid chlorides of formula 6b, followed by reaction with an hydrazine of formula

H₂NNHR^AZ. Suitable reaction conditions are described in literature (cf. WO2016/168059, US201 1/195954). The reaction is preferrably carried out in the presence of an organic base such as NEt.3, iP^NEt, pyridine, or substituted pyridines such as collidine or lutidine. Optionally a nucleophilic catalyst such as DMAP can be employed in the reaction. Suitable solvents are hal- ogenated hydrocarbons such as dichloromethane, chloroform, and chlorobenzene, or polar aprotic solvents such as THF, 1 ,4-dioxane, and DMF, or aromatic hydrocarbons such as benzene, toluene, o-, m-, and p-xylene, or mixtures thereof. The transformation is usually carried out at temperatures from -40 °C to 120 °C, preferably from 0 °C to 40 °C. The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of the hydrazine, based on 6.

Furthermore, the amidation-type reaction of a carboxylic acid of formula 6a with a hydrazine of formula H2NNHR^AZ can also be carried out in the presence of a coupling reagent. Suitable coupling reagents (activators) are known and are, e.g. selected from carbodiimides, such as DCC and DCI, benzotriazole derivatives such as HATU, HBTU, and HCTU, or phosphonium-derived activators, such as BOP, Py-BOP, Py-BrOP. Generally, the activator is used in excess. The benzotriazole and phosphonium coupling reagents are generally used in a basic medium. In turn, carboxylic acids of formula 6a and carboxylic acid derivatives of formula 6b are known from WO2016/168059, and US6887870.

Weinreb amides of formuly 6c can be prepared by reacting a carboxylic acid of formula 6a, wherein X^E is OH, or a carboxylic acid derivative of formula 6b, wherein X^E is a leaving group, preferably a halogen such as CI or Br, or Ci-C6-alkoxy, such as OCH3 or OC2H5, with the Weinreb amine of formula CHsNH(OCH3) in an amidation-type reaction. Most preferrably, the Weinreb amine is used as its hydrochloride salt (CAS 6638-79-5) and the reaction is carried out with the corresponding esters of formula 6b, in the presence of a Lewis acid activator such as ΜββΑΙ, or Me2AICI. Suitable reaction conditions are described in literature (cf. US6887870). Suitable solvents are halogenated hydrocarbons such as dichloromethane, chloroform, and chloro- benzene, or aromatic hydrocarbons such as benzene, toluene, 0-, m-, and p-xylene, or polar aprotic solvents such as THF, Et^O, or aliphatic hydrocarbons such as pentane, hexane, cyclo- hexane, petrol ether, or mixtures thereof. Alternatively, Weinreb amides of formula 6c can also be obtained by reacting acyl chlorides of formula 6b or carboxylic acids of formula 6a, respectively, with the Weinreb amine CH₃NH(OCH₃) or its hydrochloride salt (CAS 6638-79-5) under analogous amidation reaction conditions as described above, e.g. for the synthesis of compounds I, 5a-1 , and 7a-1.

Amides of formula 6d, wherein R^A1 and R^A2 are H can be prepared by reacting a carboxylic acid of formula 6a, wherein X^E is OH, or a carboxylic acid derivative of formula 6b, wherein X^E is a leaving group, preferably a halogen such as CI or Br, or Ci-C6-alkoxy, such as OCH3 or OC2H5, with ammonia or a suitable ammonia equivalent (e.g. NH4OH) in an amidation reaction, as described above e.g. for the synthesis of compounds I, 5a-1 , and 7a-1. Suitable reaction conditions are described in literature (cf. US2006/287365, M.-X. Wang et al. Adv. Synth. Catal. 2003, 345, 695-698).

Ketones of formula 20d can be prepared by reacting a Weinreb amide of formula 6c with the corresponding organolithium or organomagnesium compound of formula M-CR^AH2, wherein M is Li, or MgX (X = CI, Br, I), in a Weinreb Ketone Synthesis reaction. Suitable reaction conditions are described in literature (cf. US6887870, EP2746260). Suitable solvents are ethers such as THF, Et.20, DIPE, TBME, or or aliphatic hydrocarbons such as pentane, hexane, cyclohexane, petrol ether, or mixtures thereof. The transformation is usually carried out at temperatures from -100 °C to 50 °C, preferably from -78 °C to 25 °C.

Ketones of formula 8 can be prepared by reacting a Weinreb amide of formula 6c with the corresponding organolithium or organomagnesium compound of formula M-C(R^A)=CR^AH, wherein M is Li, or MgX (X = CI, Br, I) in a Weinreb Ketone Synthesis reaction under the same conditions as described above for the synthesis of Ketones of formula 20d. Aldehydes of formula 12 can be prepared by reacting a Weinreb amide of formula 6c with a metal hydride reducing agent such as UAIH4, diisopropylaluminum hydride (iP^AIH). Suitable reaction conditiona are described in literature (cf. J. Cheng et al. J. Med. Chem. 2016, 59, 578- 591 ; Y. Zou et al. Angew. Chem. Int. Ed. 2008, 47, 101 10-101 13). Suitable solvents are ethers such as THF, Et.20, DIPE, TBME, or aliphatic hydrocarbons such as pentane, hexane, cyclohex- ane, petrol ether, or aromatic hydrocarbons such as benzene, toluene, o-, m-, and p-xylene, or halogenated hydrocarbons such as dichloromethane, chloroform, 1 ,2-dichloroethane, or mixtures thereof. The transformation is usually carried out at temperatures from -100 °C to 50 °C, preferably from -78 °C to 25 °C.

Alkynes of formula 5a', wherein Z³ is CH, can be prepared by reacting an aldehyde of formula 12 with dimethyl (1 -diazo-2-oxopropyl)phosphonate (CAS 90965-06-3) in an Ohira-Bestmann reaction. Suitable reaction conditions are described in literature (cf. H.-J. Bestmann and coworkers, Synlett, 1996, 521 -522; WO2017/37221 ). The reaction is generally carried out in the presence of a base such as alkali metal carbonates like K2CO3. Suitable solvents are alcohols such as methanol. The transformation is usually carried out at temperatures from -20 °C to 60 °C, preferably from 0 °C to 25 °C. Alternatively, alkynes of formula 5a', can be prepared by reacting an aldehyde of formula 12 with dimethyl diazomethylphosphonate (CAS 27491 -70-9) in a Seyferth-Gilbert reaction. Suitable reaction conditions are described in literature (cf. Y.Wu et al. Eur. J. Org. Chem. 2001 , 3779-3788; B.M.Trost et al. JACS 1996, 1 18, 5146-5147). The re- action is generally carried out in the presence of a base such as an alkali metal alcoholate like potassium tert-butylate, or an alkali metal amide such as sodium hexamethyldisilazane

(NaN[Si(CH3)3]2), potassium hexamethyldisilazane (KN[Si(CH3)3]2), lithium diidopropylamide ("LDA"), or an organolithium base such as n-butyllithium. Suitable solvents are ethers such as THF, or aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and petrol ether, or mix- tures thereof.

Compounds of formula 5a can be prepared by deprotonating a compound of formula 5a', wherein Z³ is CH, with a base under stoichiometric formation of the corresponding acetylide, which is subsequently reacted in situ with an appropriate electrophile such as alkyl halides and alkyl sulfonic esters (R^AX; X = CI, Br, I, OS(=0)₂Me, OS(=0)₂CF₃), aldehydes (R³³C(=0)H), or ketones (R³³C(=0)R³³), C0₂, acyl halides, and acid anhydrides (R³³C(=0)X; X = F, CI, Br,

OC(=0)t-Bu), chloroformate esters (R³³OC(=0)CI), or carbamoylchlorides (R³ (R³²)NC(=0)CI), isocyanates (R³²-N=C=0), or Weinreb amides (R³³C(=0)N(OMe)Me). Suitable reaction conditions are described in literature (cf. WO2016/22724, WO2013/173441 , WO2009/2427). Suitable bases are alkali metal amides such as lithium hexamethyldisilazane (LiN[Si(CH3)3]2),

NaN[Si(CH₃)₃]₂, KN[Si(CH₃)₃]₂, LDA, lithium tetramethylpiperidide ("LTMP"), or organolithium compunds such as n-butyllithium, sec-butyllithium, tert-butyllithium, or organomagnesium compounds such as isopropylmagnesium chloride, isopropylmagnesium bromide, ethylmagnesium bromide. Optionally, a copper salt such as CuCI, CuBr, Cul, and/or an amine such as NEt.3, pyridine, TMEDA, hexamethylphosphoramide, can be employed in the reaction. Suitable solvents are ethers such asTHF, Et^O, DIPE, TBME, 1 ,4-dioxane, or aliphatic hydrocarbons such as pentane, hexane, cyclohexane, petrol ether, or aromatic hydrocarbons such as benzene, toluene, 0-, m-, and p-xylene, or mixtures thereof. Alternatively, compounds of formula 5a can be prepared by reacting a compound of formula 5a', wherein Z³ is CH, with a suitable R^AX (X = I, Br, CI, OS(=0)₂CF₃, and the like) in a Sono- gashira or a Sonogashira-type reaction. Suitable reaction conditions are described in literature (cf. A. de Meijere et al., "Metal-Catalyzed Cross-Coupling Reactions and More", Wiley-VCH, 2014). The reaction is generally carried out in the presence of a palladium catalyst such as tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium(ll) dichloride, palladium^!) acetate, and in the presence of a base such as an amine base like NEt.3, iP^NEt, diiso- propylamine, diethylamine, piperidine, pyrrolidine, n-butylamine, or alkali metal carbonates, such as K2CO3, CS2CO3. The base is generally used in equimolar amounts or in excess, but it can also be used as the solvent if appropriate. Preferrably, a copper salt is employed in the reaction such as CuCI, CuBr, and Cul. Amine bases may be used as the only solvent, or in combination with an additional solvent. Suitable additional solvents are polar aprotic solvents such as THF, DMF, acetonitrile, or aromatic hydrocarbons such as benzene, toluene, 0-, m-, and p-xy- lene, or mixtures thereof.

Compounds of formula 5c, that is compounds of formula 5 wherein Z³ is N, can be prepared by dehydration of a compound of formula 6d. The reaction is generally carried out in the presence of an activating/dehydrating agent such as trichlorophosphate, trifluoroacetic anhydride, SOC , P2O5, or burgess reagent (CAS 29684-56-8). Suitable reaction conditions are described in literature (cf. M.-X. Wang et al. Tetrahedron Asymm. 2004, 15, 347-354; WO2013/17657). Optionally, a base can be employed in the reaction such as an amine base like pyridine, NEt.3, iPr2NEt, or 1 H-imidazole. Suitable solvents are polar aprotic solvents such as DMF, DMA, THF, 1 ,4-dioxane, or halogenated hydrocarbons such as dichloromethane, chloroform, and chloro- benzene, or aromatic hydrocarbons such as benzene, toluene, 0-, m-, and p-xylene, or mixtures thereof.

Compounds of formula 20c, wherein X is CI, Br or I, can be prepared by treating a ketone of formula 20d with a halogenating agent in an alpha-halogenation reaction. Suitable reaction conditions are described in literature (cf. US2010/196321 , WO2013/24081 ). Suitable halogenating agents are chlorine, bromine, iodine, NCS, N-bromosuccinimide ("NBS"), N-iodosuccinimide, sulfuryl dichloride, phenyltrimethylammonium tribromide, tetraethylammonium trichloride, CuBr2. Optionally, an acid can be employed in the reaction such as a Bronsted acid like acetic acid,

HBr, HCI, H2SO4, TsOH, or Lewis acids such as AICI3. Suitable solvents are halogenated hydrocarbons such as dichloromethane, chloroform, 1 ,2-dichloroethane, or ethers such as THF, Et.20, TBME, 1 ,4-dioxane, or alcohols such as methanol, ethanol, and the like, or ethyl acetate, or acetic acid, or water, or mixtures thereof. Alternatively, the halogenation reaction can also be performed by prior transformation of ketone 20d into the corresponding alkali metal enolate using an alkali metal amide base such as LiN[Si(CH3)3]2, LDA, LTMP, followed by its in situ reaction with a halogenating agent such as NCS, NBS, N-iodosuccinimide, TsCI, trifluoromethane- sulfonyl chloride, hexachloroethane, chlorine, bromine, iodine. Suitable reaction conditions are described in literature (cf. US6887870). Suitable solvents are ethers such as THF, Et^O, or ali- phatic hydrocarbons such as pentane, hexane, cyclohexane, and petrol ether, or mixtures thereof. If desired, it is also possible to intercept the alkali metal enolate with a chlorotrialkylsi- lane such as chlorotrimethylsilane, chlorotriethylsilane, tert-butyldimethylsilyl chloride, to give the corresponding silyl enol ether which can be isolated and treated with a suitable halogenating agent in a separate step. Suitable halogenating agents are chlorine, bromine, iodine, NCS, NBS, N-iodosuccinimide, sulfuryl dichloride, phenyltrimethylammonium tribromide, tetraethyl- ammonium trichloride. Suitable reaction conditions are described in literature (cf.

WO2017/005786).

Compounds of formula 20b, wherein Z^K is SH, can be prepared by reacting a compound of for- mula 20b, wherein X is CI, Br, or I, with NaHS, Na2S, thiacetic acid. Suitable reaction conditions are described in literature (cf. F. Asinger Monatshefte fuer Chemie 1982, 1 13, 1 191 -1212;

WO2006/12643; US4061761 ). Optionally, a base can be employed in the reaction such as alkali metal and alkaline earth metal hydroxides, such as LiOH, NaOH, KOH, Ca(OH)2, or alkali metal alcoholates such as sodium methylate, sodium ethylate, or alkali metal carbonates, such as Na2C03, K2CO3. Suitable solvents are alcohols such as methanol, ethanol, or polar aprotic solvents such as DMF, THF, acetonitrile, 1 -methyl-pyrrolidin-2-one, or water, or mixtures thereof. If thiocarboxylic acids are employed in the reaction it is alo possible to perform the hydrolysis in a separate step as described in M. C. Pirrung et al. J. Med. Chem. 2002, 45, 4359-4370.

Compounds of formula 20a, wherein Z^K is OH, can be prepared by transformation of a ketone of formula 20d into the corresponding alkali metal enolate using an alkali metal amide base such as LiN[Si(CH₃)₃]₂, NaN[Si(CH₃)₃]₂, KN[Si(CH₃)₃]₂, LDA, LTMP, followed by its in situ reaction with an oxygenating agent such as Vedejs' reagent (CAS 23319-63-3; MoOs-pyr-HMPA; "MoOPH"), or a Davis' oxaziridine such as N-(benzenesulfonyl)-3-phenyloxaziridine. Suitable reaction conditions are described in literatue (cf. Vedejs et al. J. Org. Chem. 1978, 43, 188-196; H.Kusama et al. J. Am. Chem. Soc. 2000, 122, 381 1 -3820; K.C. Nicolaou et al. JACS 2009, 131 , 10587-10597). Suitable solvents are ethers such as THF, or aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and petrol ether, or aromatic hydrocarbons such as benzene, toluene, 0-, m-, and p-xylene, or mixtures thereof. The transformation is usually carried out at temperatures from -100 °C to 50 °C, preferably from -78 °C to 25 °C. If desired, it is also possi- ble to intercept the alkali metal enolate with a chlorotrialkylsilane such as chlorotrimethylsilane, chlorotriethylsilane, tert-butyldimethylsilyl chloride to give the corresponding silyl enol ether which can be isolated and treated with a suitable peroxy acid in a separate step in a Rubottom oxidation. Suitable reaction conditions are described in literature (cf. D.R. Williams et al. Org. Lett. 2016, 18, 424-427). If desired, it is also possible to generate the silyl enol ether by treat- ment of a ketone of formula 20d with a trialkylsilyl triflate in the presence of an amine base such as NEt₃, iPr2NEt. Suitable solvents are halogenated hydrocarbons such as dichloromethane, chloroform, 1 ,2-dichloroethane, or ethers such as THF.

Compounds of formula 7a-2, wherein Z^K is NH2 can be prepared by reacting a compound of formula 20c, wherein X is CI, Br, or I, with an amination reagent such as hexamethylenetetra- mine (CAS 100-97-0), sodium diformamide (CAS 18197-26-7), followed by treatment with an acid such as a mineral acid like HCI. The acid treatment is preferrabyl carried out in a separate step. Suitable reaction conditions are described in literature (cf. WO2014/100533;

WO2015/18027; WO2015/5901 ).

Arenes of formula 9, 10, 11 , 13, and 22 are commercially available, or can be made as de- scribed in the literature, or are prepared in analogy as described above for the compounds of formula 5, 6, 7, 8, 12, and 20.

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 cannot 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 derivatiza- tion, 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 the customary manner, e.g. by mixing with water, separating the phases, and, if appropriate, purifying the crude products by chromatography, e.g. on alumina or on silica gel. Some of the intermediates and end products may be obtained in the form of colorless or pale brown viscous oils which are freed or purified from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, they may be purified by recrystallization or trituration.

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.

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-C_m 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 -methyl- butyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, n-hexyl, 1 ,1 -dimethylpro- pyl, 1 ,2-dimethylpropyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -di- methylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dime- thylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1 -ethyl-1 -methyl- propyl, and 1 -ethyl-2-methylpropyl.

The term "haloalkyl" as used herein and in the haloalkyl moieties of haloalkylcarbonyl, haloalk- oxycarbonyl, 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-C2-haloalkyl, in particular from Ci-C2-fluoroalkyl such as fluoromethyl, difluoromethyl, trifluo- romethyl, 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, frequently 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 com- prising 1 to 4, preferably 1 or 2 carbon atoms as defined above. Examples are CH2OCH3, 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-flu- oroethoxy, 2-chloro-2,2-difluoro-ethoxy, 2,2dichloro-2-fluorethoxy, 2,2,2-trichloroethoxy, penta- fluoroethoxy 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)-Ci-C6-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 (= Ci-C4-al- kylsulfonyl), 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, pro- pargyl (2-propyn-1 -yl), 1 -propyn-1 -yl, 1 -methylprop-2-yn-1 -yl), 2-butyn-1 -yl, 3-butyn-1 -yl, 1 -pen- tyn-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 cycloal- kylthio denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 10 or from 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl 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-fluo- rocyclopropyl, 1 ,2-, 2,2- and 2,3-difluorocyclopropyl, 1 ,2,2-trifluorocyclopropyl, 2,2,3,3-tetrafluo- rocyclpropyl, 1 - and 2-chlorocyclopropyl, 1 ,2-, 2,2- and 2,3-dichlorocyclopropyl, 1 ,2,2-trichloro- cyclopropyl, 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-dichlo- rocyclopentyl 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 10 carbon atoms, preferably from 3- to 8 car- bon atoms. Exemplary cycloalkenyl groups include cyclopropenyl, cycloheptenyl or cycloocte- nyl.

The term "halocycloalkenyl" as used herein and in the halocycloalkenyl moieties of halocyclo- alkenyloxy and halocycloalkenylthio 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 10 carbon atoms, preferably from 3- to 8 carbon 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 3,3-difluorocyclopropen- 1 -yl and 3,3-dichlorocyclopropen-1 -yl.

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 methy- lene 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-oxid (S-oxothietanyl), 2- and 3-thietanyl-S-dioxid (S-dioxothietanyl), 2- and 3- pyrrolidinyl, 2- and 3-tetrahydrofuranyl, 1 ,3-dioxolan-2-yl, thiolan-2-yl, S-oxothiolan-2-yl, S-diox- othiolan-2-yl, 4- and 5-oxazolidinyl, 1 ,3-dioxan-2-yl, 1 - and 3-thiopyran-2-yl, S-oxothiopyranyl, and S-dioxothiopyranyl.

The term "hetaryl" includes monocyclic 5- or 6-membered heteroaromatic radicals comprising as ring members 1 , 2, or 3 heteroatoms selected from N, O and S. Examples of 5- or 6-membered heteroaromatic radicals include pyridyl, i.e. 2-, 3-, and 4-pyridyl, pyrimidinyl, i.e. 2-, 4- and 5-pyrimidinyl, pyrazinyl, pyridazinyl, i.e. 3- and 4-pyridazinyl, thienyl, i.e. 2- and 3-thienyl, furyl, i.e. 2- and 3-furyl, pyrrolyl, i.e. 1 -, 2- and 3-pyrrolyl, oxazolyl, i.e. 2-, 4- and 5-oxazolyl, isoxazo- lyl, i.e. 3-, 4- and 5-isoxazolyl, thiazolyl, i.e. 2-, 3- and 5-thiazolyl, isothiazolyl, i.e. 3-, 4- and 5-isothiazolyl, pyrazolyl, i.e. 1 -, 3-, 4- and 5-pyrazolyl, imidazolyl, i.e. 1 -, 2-, 4- and 5-imidazolyl, oxadiazolyl, e.g. 2- and 5-[1 ,3,4]oxadiazolyl, thiadiazolyl, e.g. 1 ,3,4-thiadiazol-5-yl, 1 ,2,4-thiadia- zol-3-yl, triazolyl, e.g. 1 ,3,4-triazol-2-yl, and 1 ,2,4-triazol-3-yl.

The terms "heterocyclyolalkyl" and "hetarylalkyl" refer to heterocyclyl or hetaryl, resp., as defined above which are bound via a Ci-C4-alkyl group, in particular a methyl group (= heterocy- clylmethyl or hetarylmethyl, resp.), 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 formula I.

In a preferred embodiment, the compounds I are present in form of a mixture of compounds I.A, I.B, I.C, and I.D, where the trans-configurated compounds I.B and I.D are present in an amount of more than 50% by weight, in particular of at least 70% by weight, specifically of at least 90% by weight, based on the total weight of compounds I.A to I.D. The trans-isomers I.B and I.D are usually present as a 1 :1 mixture.

In one particularly preferred embodiment of the invention, the method comprises step of contacting the plant, parts of it, its propagation material, the pests, their food supply, habitat or breeding grounds a pesticidally effective amount of a trans compound, which may be part of a mixture of I.B and I.D.

Separation of the enantiomers can be achieved by methods known in the art, e.g. Kovalenko, Kulinkovich, Tetrahedron: Asymmetry 201 1 , 22, 26; or WO 2016/168059. R^1a and R^1b are preferably identical. R^1c and R^1d are preferably both H.

These groups represent preferably H, or halogen, such as CI or Br.

In one embodiment R^1a and R^1b are both halogen, such as CI or Br.

In another embodiment R^1a is H, and R^1b is halogen, such as CI or Br. R^2a is preferably selected from F, CI, Br, CF₃, and OCF₃.

R^2b and R^2c are independently preferably selected from H, F, CI, Br, CF3, and OCF3.

Particularly preferred is each one of the following combinations of R^2a, R^2b and R^2c wherein each line of Table A denotes a substitution pattern of the phenyl ring ("A") bearing the R^2a, R^2b and R^2c moieties.

Table A

Groups A-8, A-9, and A-1 1 are more preferred patterns in formula I compounds. A-9 is particularly preferred. HE is preferably selected from groups HE1 , HE2, HE3, HE4, and HE5,

wherein the ring members:

Z is O, S(0)m, or NR^AZ; and

Z², Z³, and Z⁴ independently are N(0)_n, and C-R^A; wherein

R^AZ is a group R^A, preferably H, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloal- koxy, and

# marks the bond to the cyclopropyl ring, and

+ marks the bond to the T¹ to T³ containing heterocycle.

Preferred meanings of R^A in a group C-R^A as substituents of a HE ring are H, Ci-C3-alkyl, and d-Cs-haloalkyl.

Preferred Z¹ are O, NR^AZ, and S. More preferred Z¹ are O, NH, and S.

Preferred Z² to Z⁴ are N or CR⁴.

Preferred HE rings consist of 1 , 2, or 3 hetero ring atoms.

Particularly preferred HE rings are selected from the following:

Formula I, wherein HE is selected from HE1.1 , HE1.2, and HE1.3 resp., is formula I.H 1.1 , I.H1 .2, a

In one embodiment the T¹, T², and T³ containing ring ("Ring T") represents a group D1 :

wherein + marks the bond to HE, and

R³, R^D1, R^D2, and R^D3 are independently preferably H, halogen, CN, OH, NH₂, Ci-C₄-alkyl, cyclopropyl, or Ci-C4-haloalkyl. More preferably R^D1 and R^D2 are independently H, or halomethyl such as CF3, or halogen such as CI or F, and R³ and R^D3 are H.

More preferably one of R^D1 and R^D2 is a halogen such as CI or F, and R³ and R⁴³ are H.

Particularly R³, R^D1 and R^D3 are H, and R⁴² is F.

In another embodiment R^D1 is CI, and R³, R⁴², and R⁴³ are H.

In another embodiment the T¹, T², and T³ containing ring ("Ring T") represents a group D2:

wherein + marks the bond to HE, and

R³, and R^D1 are independently preferably H, halogen, or Ci-C4-haloalkyl; more preferably H, CF₃, CI, or F.

In another embodiment the T¹, T², and T³ containing ring ("Ring T") represents a group D3:

wherein + marks the bond to HE, and

R³, and R^D3 are independently preferably H, halogen, or Ci-C4-haloalkyl; more preferably H, CF₃, CI, or F.

In another embodiment the T¹, T², and T³ containing ring ("Ring T") represents a group D4:

wherein + marks the bond to HE, and

R³, R^D1 and R^D3 are independently preferably H, halogen, or Ci-C4-haloalkyl; more preferably H, CF₃, CI, or F.

Variable U in groups A is preferably O.

R⁵ is preferably H, alkyl such as CH₃ or CH₂CH₃.

R⁶ is preferably Ci-C4-alkyl, Ci-C4-haloalkyl, C₃-C6-cycloalkyl, or phenyl, which rings are bonded either directly or via a CH2 spacer, and which rings are unsubstituted or substituted with 1 , 2, or 3 substituents R^a which are preferably CN, CH₃, or halogen; or

C₃-C4-alkenyl, C₃-C4-alkynyl, CH2C(=0)OR³¹, or benzyl wherein the ring is unsubstituted or corresponds to a group P. Preferred R³¹ meanings are Ci-C6-alkyl such as CH₃, C2H5, CH(CH₃)₂, and C(CH₃)₃, or phenyl, or benzyl.

In a preferred embodiment R⁶ is benzyl or phenyl which are unsubstituted or substituted with halogen, and Ci-C4-haloalkyl. Particularly preferred meaning for R⁶ is a group P, wherein # is the bond to the amide-N:

and R⁶¹, R⁶², and R⁶³ are halogen or Ci-C4-haloalkyl.

In a particularly preferred embodiment R⁶¹ is Br, R⁶², is CF₃, and R⁶³ is CF(CF₃)2.

In a particularly preferred embodiment n is 0.

Particularly preferred is each one of the following combinations of R⁶¹, R⁶², and R⁶³ wherein each line of Table P denotes a substitution pattern of the phenyl ring ("P") bearing the R⁶¹, R⁶², and R⁶³ moieties, wherein n is 0. Table P (n = 0)

Groups P-21 , P-25, P-26, P-28, P-29, P-30, and P-31 are more preferred patterns in formula I compounds. P-25 and P-28 are particularly preferred.

In one preferred embodiment A is A1 .

In another embodiment A is A2, wherein the index n is preferably 0 or 1 . Preferred embodiments relate to each of following compounds of formula I, wherein the variabl

In particular with a view to their use, preference is given to the compounds of formula I compiled in the tables below, which compounds correspond to formulae 1.1 ^*, 1.2^*, 1.3^*, 1.4^*, 1.5^*, 1.6^*, resp. 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 R⁶ is CH3, and the other variables for a corn- pound correspond in each case to one row of Table B

Table 2 : Compounds of formula 1.2^* in which R⁶ is CH3, and the other variables for a corn- pound correspond in each case to one row of Table B

Table 3 : Compounds of formula 1.3^* in which R⁶ is CH3, and the other variables for a corn- pound correspond in each case to one row of Table B

Table 4 : Compounds of formula 1.4^* in which R⁶ is CH3, and the other variables for a corn- pound correspond in each case to one row of Table B

Table 5 : Compounds of formula 1.5^* in which R⁶ is CH3, and the other variables for a corn- pound correspond in each case to one row of Table B

Table 6 : Compounds of formula 1.6^* in which R⁶ is CH3, and the other variables for a corn- pound correspond in each case to one row of Table B

Table 7 : Compounds of formula 1.1 ^* in which R⁶ is C2H5, and the other variables for a corn- pound correspond in each case to one row of Table B

Table 8 : Compounds of formula 1.2^* in which R⁶ is C2H5, and the other variables for a corn- pound correspond in each case to one row of Table B

Table 9 : Compounds of formula 1.3^* in which R⁶ is C2H5, and the other variables for a corn- pound correspond in each case to one row of Table B Table 10 : Compounds of formula 1.4^* in which R⁶ is C2H5, and the other variables for a compound correspond in each case to one row of Table B

Table 1 1 : Compounds of formula 1.5^* in which R⁶ is C2H5, and the other variables for a compound correspond in each case to one row of Table B

Table 12 : Compounds of formula 1.6^* in which R⁶ is C2H5, and the other variables for a compound correspond in each case to one row of Table B

Table 13 : Compounds of formula 1.1 ^* in which R⁶ is CH(CH3)2, and the other variables for a compound correspond in each case to one row of Table B

Table 14 : Compounds of formula 1.2^* in which R⁶ is CH(CH3)2, and the other variables for a compound correspond in each case to one row of Table B

Table 15 : Compounds of formula 1.3^* in which R⁶ is CH(CH3)2, and the other variables for a compound correspond in each case to one row of Table B

Table 16 : Compounds of formula 1.4^* in which R⁶ is CH(CH3)2, and the other variables for a compound correspond in each case to one row of Table B

Table 17 : Compounds of formula 1.5^* in which R⁶ is CH(CH3)2, and the other variables for a compound correspond in each case to one row of Table B

Table 18 : Compounds of formula 1.6^* in which R⁶ is CH(CH3)2, and the other variables for a compound correspond in each case to one row of Table B

Table 19 : Compounds of formula 1.1 ^* in which R⁶ is CH2CH(CH3)2, and the other variables for a compound correspond in each case to one row of Table B

Table 20 : Compounds of formula 1.2^* in which R⁶ is CH2CH(CH3)2, and the other variables for a compound correspond in each case to one row of Table B

Table 21 : Compounds of formula 1.3^* in which R⁶ is CH2CH(CH3)2, and the other variables for a compound correspond in each case to one row of Table B

Table 22 : Compounds of formula 1.4^* in which R⁶ is CH2CH(CH3)2, and the other variables for a compound correspond in each case to one row of Table B

Table 23 : Compounds of formula 1.5^* in which R⁶ is CH2CH(CH3)2, and the other variables for a compound correspond in each case to one row of Table B

Table 24 : Compounds of formula 1.6^* in which R⁶ is CH2CH(CH3)2, and the other variables for a compound correspond in each case to one row of Table B

Table 25 : Compounds of formula 1.1 ^* in which R⁶ is CH2CH=CH2, and the other variables for a compound correspond in each case to one row of Table B

Table 26 : Compounds of formula 1.2^* in which R⁶ is CH2CH=CH2, and the other variables for a compound correspond in each case to one row of Table B

Table 27 : Compounds of formula 1.3^* in which R⁶ is CH2CH=CH2, and the other variables for a compound correspond in each case to one row of Table B

Table 28 : Compounds of formula 1.4^* in which R⁶ is CH2CH=CH2, and the other variables for a compound correspond in each case to one row of Table B

Table 29 : Compounds of formula 1.5^* in which R⁶ is CH2CH=CH2, and the other variables for a compound correspond in each case to one row of Table B

Table 30 : Compounds of formula 1.6^* in which R⁶ is CH2CH=CH2, and the other variables for a compound correspond in each case to one row of Table B

Table 31 : Compounds of formula 1.1 ^* in which R⁶ is CH2CF3, and the other variables for a compound correspond in each case to one row of Table B Table 32 : Compounds of formula 1.2^* in which R⁶ is CH2CF3, and the other variables for a compound correspond in each case to one row of Table B

Table 33 : Compounds of formula 1.3^* in which R⁶ is CH2CF3, and the other variables for a compound correspond in each case to one row of Table B

Table 34 : Compounds of formula 1.4^* in which R⁶ is CH2CF3, and the other variables for a compound correspond in each case to one row of Table B

Table 35 : Compounds of formula 1.5^* in which R⁶ is CH2CF3, and the other variables for a compound correspond in each case to one row of Table B

Table 36 : Compounds of formula 1.6^* in which R⁶ is CH2CF3, and the other variables for a compound correspond in each case to one row of Table B

Table 37 : Compounds of formula 1.1 ^* in which R⁶ is CH2CH2CF3, and the other variables for a compound correspond in each case to one row of Table B

Table 38 : Compounds of formula 1.2^* in which R⁶ is CH2CH2CF3, and the other variables for a compound correspond in each case to one row of Table B

Table 39 : Compounds of formula 1.3^* in which R⁶ is CH2CH2CF3, and the other variables for a compound correspond in each case to one row of Table B

Table 40 : Compounds of formula 1.4^* in which R⁶ is CH2CH2CF3, and the other variables for a compound correspond in each case to one row of Table B

Table 41 : Compounds of formula 1.5^* in which R⁶ is CH2CH2CF3, and the other variables for a compound correspond in each case to one row of Table B

Table 42 : Compounds of formula 1.6^* in which R⁶ is CH2CH2CF3, and the other variables for a compound correspond in each case to one row of Table B

Table 43 : Compounds of formula 1.1 ^* in which R⁶ is CH2C6H5, and the other variables for a compound correspond in each case to one row of Table B

Table 44 : Compounds of formula 1.2^* in which R⁶ is CH2C6H5, and the other variables for a compound correspond in each case to one row of Table B

Table 45 : Compounds of formula 1.3^* in which R⁶ is CH2C6H5, and the other variables for a compound correspond in each case to one row of Table B

Table 46 : Compounds of formula 1.4^* in which R⁶ is CH2C6H5, and the other variables for a compound correspond in each case to one row of Table B

Table 47 : Compounds of formula 1.5^* in which R⁶ is CH2C6H5, and the other variables for a compound correspond in each case to one row of Table B

Table 48 : Compounds of formula 1.6^* in which R⁶ is CH2C6H5, and the other variables for a compound correspond in each case to one row of Table B

Table 49 : Compounds of formula 1.1 ^* in which R⁶ is CH2C(=0)OCH3, and the other variables for a compound correspond in each case to one row of Table B

Table 50 : Compounds of formula 1.2^* in which R⁶ is CH2C(=0)OCH3, and the other variables for a compound correspond in each case to one row of Table B

Table 51 : Compounds of formula 1.3^* in which R⁶ is CH2C(=0)OCH3, and the other variables for a compound correspond in each case to one row of Table B

Table 52 : Compounds of formula 1.4^* in which R⁶ is CH2C(=0)OCH3, and the other variables for a compound correspond in each case to one row of Table B

Table 53 : Compounds of formula 1.5^* in which R⁶ is CH2C(=0)OCH3, and the other variables for a compound correspond in each case to one row of Table B Table 54 : Compounds of formula 1.6^* in which R⁶ is CH2C(=0)OCH3, and the other variables for a compound correspond in each case to one row of Table B

Table 55 : Compounds of formula 1.1 ^* in which R⁶ is P-21 , and the other variables for a compound correspond in each case to one row of Table B

Table 56 : Compounds of formula 1.2^* in which R⁶ is P-21 , and the other variables for a compound correspond in each case to one row of Table B

Table 57 : Compounds of formula 1.3^* in which R⁶ is P-21 , and the other variables for a compound correspond in each case to one row of Table B

Table 58 : Compounds of formula 1.4^* in which R⁶ is P-21 , and the other variables for a com- pound correspond in each case to one row of Table B

Table 59 : Compounds of formula 1.5^* in which R6 is P-21 , and the other variables for a compound correspond in each case to one row of Table B

Table 60 : Compounds of formula 1.6^* in which R6 is P-21 , and the other variables for a compound correspond in each case to one row of Table B

Table 61 : Compounds of formula 1.1 ^* in which R⁶ is P-25, and the other variables for a compound correspond in each case to one row of Table B

Table 62 : Compounds of formula 1.2^* in which R⁶ is P-25, and the other variables for a compound correspond in each case to one row of Table B

Table 63 : Compounds of formula 1.3^* in which R⁶ is P-25, and the other variables for a com- pound correspond in each case to one row of Table B

Table 64 : Compounds of formula 1.4^* in which R⁶ is P-25, and the other variables for a compound correspond in each case to one row of Table B

Table 65 : Compounds of formula 1.5^* in which R⁶ is P-25, and the other variables for a compound correspond in each case to one row of Table B

Table 66 : Compounds of formula 1.6^* in which R⁶ is P-25, and the other variables for a compound correspond in each case to one row of Table B

Table 67 : Compounds of formula 1.1 ^* in which R⁶ is P-28, and the other variables for a compound correspond in each case to one row of Table B

Table 68 : Compounds of formula 1.2^* in which R⁶ is P-28, and the other variables for a com- pound correspond in each case to one row of Table B

Table 69 : Compounds of formula 1.3^* in which R⁶ is P-28, and the other variables for a compound correspond in each case to one row of Table B

Table 70 : Compounds of formula 1.4^* in which R⁶ is P-28, and the other variables for a compound correspond in each case to one row of Table B

Table 71 : Compounds of formula 1.5^* in which R⁶ is P-28, and the other variables for a compound correspond in each case to one row of Table B

Table 72 : Compounds of formula 1.6^* in which R⁶ is P-28, and the other variables for a compound correspond in each case to one row of Table B

Table 73 : Compounds of formula 1.1 ^* in which R⁶ is C-C3H5, and the other variables for a compound correspond in each case to one row of Table B

Table 74 : Compounds of formula 1.2^* in which R⁶ is C-C3H5, and the other variables for a compound correspond in each case to one row of Table B

Table 75 : Compounds of formula 1.3^* in which R⁶ is C-C3H5, and the other variables for a compound correspond in each case to one row of Table B Table 76 : Compounds of formula 1.4^* in which R⁶ is C-C3H5, and the other variables for a compound correspond in each case to one row of Table B

Table 77 : Compounds of formula 1.5^* in which R⁶ is C-C3H5, and the other variables for a compound correspond in each case to one row of Table B

Table 78 : Compounds of formula 1.6^* in which R⁶ is C-C3H5, and the other variables for a compound correspond in each case to one row of Table B

Table 79 : Compounds of formula 1.1 ^* in which R⁶ is (1 -CN)-c-CsH4, and the other variables for a compound correspond in each case to one row of Table B

Table 80 : Compounds of formula 1.2^* in which R⁶ is (1 -CN)-c-CsH4, and the other variables for a compound correspond in each case to one row of Table B

Table 81 : Compounds of formula 1.3^* in which R⁶ is (1 -CN)-c-CsH4, and the other variables for a compound correspond in each case to one row of Table B

Table 82 : Compounds of formula 1.4^* in which R⁶ is (1 -CN)-c-CsH4, and the other variables for a compound correspond in each case to one row of Table B

Table 83 : Compounds of formula 1.5^* in which R⁶ is (1 -CN)-c-CsH4, and the other variables for a compound correspond in each case to one row of Table B

Table 84 : Compounds of formula 1.6^* in which R⁶ is (1 -CN)-c-CsH4, and the other variables for a compound correspond in each case to one row of Table B Table B

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. aldi- carb, 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, azame- thiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlorme- phos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethopro- phos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofen- phos, 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, triazo- phos, 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, bio- resmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma- cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cy- permethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, heptafluthrin, imiprothrin, me- perfluthrin,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-pen- tylidenehydrazinecarboximidamide; 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, ki- noprene 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.I OB etoxazole;

M.1 1 Microbial disruptors of insect midgut membranes, e.g. bacillus thuringiensis OK bacillus sphaericus and the insecticdal proteins they produce such as bacillus thuringiensis subsp. is- raelensis, bacillus sphaericus, bacillus thuringiensis subsp. aizawai, bacillus thuringiensis subsp. kurstakiand bacillus thuringiensis subsp. tenebrionis, or the Bt crop proteins: CrylAb, Cry1 Ac, Cry1 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 as e.g. bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron or triflumuron;

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

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

M.18 Ecdyson receptor agonists such as diacylhydrazines, e.g. methoxyfenozide, tebufeno- zide, halofenozide, fufenozide or chromafenozide;

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

M.20 Mitochondrial complex III electron transport inhibitors, e.g. M.20A hydramethylnon, or 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 or tolfen- pyrad, or M.21 B rotenone;

M.22 Voltage-dependent sodium channel blockers, e.g. M.22A indoxacarb, or M.22B meta- flumizone, or M.22B.1 : 2-[2-(4-Cyanophenyl)-1 -[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(di- fluoromethoxy)phenyl]-hydrazinecarboxamide or M.22B.2: N-(3-Chloro-2-methylphenyl)-2-[(4- chlorophenyl)[4-[methyl(methylsulfonyl)amino]phenyl]methylene]-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 or 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, as e.g. flubendiamide, chlor- antraniliprole (rynaxypyr®), cyantraniliprole (cyazypyr®), tetraniliprole, 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 -(trifluorome- thyl)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)ben- zoyl]-1 ,2-dimethylhydrazinecarboxylate; M.28.5a) N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanyli- dene)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-phenyl]-2-(3-chlo- ro-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-pyridyl)-5-(trifluoromethyl)py- razole-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-(trifluo- romethyl)pyrazole-3-carboxamide; M.28.5i) N-[2-(5-Amino-1 ,3,4-thiadiazol-2-yl)-4-chloro-6-me- thylphenyl]-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-py- razole-5-carboxamide; M.28.5k) 3-Bromo-N-[2,4-dichloro-6-(methylcarbamoyl)phenyl]-1 -(3,5- dichloro-2-pyridyl)-1 H-pyrazole-5-carboxamide; M.28.5I) N-[4-Chloro-2-[[(1 ,1 -dimethylethyl)ami- no]carbonyl]-6-methylphenyl]-1 -(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-1 H-pyrazole-5-carbox- amide;

M.28.6: cyhalodiamide; or;

M.29. active compounds of unknown or uncertain mode of action, as e.g. afidopyropen, afoxo- laner, azadirachtin, amidoflumet, benzoximate, bifenazate, broflanilide, bromopropylate, chino- methionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, flupyradifurone, fluralaner, metoxadiazone, piperonyl butoxide, pyflubumide, pyrida- lyl, pyrifluquinazon, sulfoxaflor, tioxazafen, triflumezopyrim,

M.29.3: 1 1 -(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1 ,4-dioxa-9-azadispiro[4.2.4.2]-tetradec- 1 1 -en-10-one, M.29.4: 3-(4'-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1 -azaspi- ro[4.5]dec-3-en-2-one, M.29.5: 1 -[2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(tri- fluoromethyl)-1 H-1 ,2,4-triazole-5-amine, or actives on basis of bacillus firmus (Votivo, 1-1582); M.29.6, selected from 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-acetamide; M.29.6b) (E/Z)-N-[1 -[(6-chloro-5-fluoro-3-pyridyl)methyl]- 2-pyridylidene]-2,2,2-trifluoro-acetamide; M.29.6c) (E/Z)-2,2,2-trifluoro-N-[1 -[(6-fluoro-3-pyri- dyl)methyl]-2-pyridylidene]acetamide; M.29.6d) (E/Z)-N-[1 -[(6-bromo-3-pyridyl)methyl]-2-pyridyli- dene]-2,2,2-trifluoro-acetamide; M.29.6e) (E/Z)-N-[1 -[1 -(6-chloro-3-pyridyl)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-propanamide.); M.29.6j) N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-tri- fluoro-thioacetamide; 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-dichlorophenyl)-5-(tri- fluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1 -oxothietan-3-yl)benzamide; or M.29.9.b): fluxa- metamide; M.29.10: 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1 H-pyrazole; M.29.1 1 , selected from M.29.1 1 b) to M.29.1 1 p): M.29.1 1.b) 3-(benzoylmethylamino)-N-[2-bro- mo-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)propyl]-6-(trifluoromethyl)phenyl]-2-fl^

amide; M.29.1 1.c) 3-(benzoylmethylamino)-2-fluoro-N-[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoro- methyl)ethyl]-6-(trifluoromethyl)phenyl]-benzamide; M.29.1 1 .d) N-[3-[[[2-iodo-4-[1 ,2,2,2-tetraflu- oro-1 -(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-meth

amide; M.29.1 1 .e) N-[3-[[[2-bromo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]-6-(trifluorome- thyl)phenyl]amino]carbonyl]-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)pheny^ no]carbonyl]phenyl]-N-methyl-benzamide; M.29.1 1 .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-meth benzamide; M.29.1 1 .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]carbamo- yl]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]phe- nyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; M.29.1 1 .1) N-[5-[[2-bromo-6-chlo- ro-4-[2,2,2-trifluoro-1 -hydroxy-1 -(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cy- ano-2-methyl-benzamide; M.29.1 1 .m) N-[5-[[2-bromo-6-chloro-4-[1 ,2,2,3,3,3-hexafluoro-1 -(tri- fluoromethyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide;

M.29.1 1.n) 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)pro- pyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; M.29.1 1.o) 4-cyano-N-[2-cyano-5-[[2,6-di- chloro-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]phenyl]carbamoyl]phenyl]-2-methyl-ben- zamide; M.29.1 1.p) N-[5-[[2-bromo-6-chloro-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]phe- nyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; M.29.12, selected from

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)thia- zol-5-yl]pyridine-2-carboxamide; M.29.12. e) N-Methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridi- ne-2-carboxamide; M.29.12.f) N-Ethyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthio-propan- amide; M.29.12.g) N-Methyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthio-propanamide; 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-propanamide; 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-pyri- dazin-4-yl-pyrazole-4-carboxamide; or M.29.16b) 1 -(1 ,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyr- idazin-4-yl-pyrazole-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-me- thyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; M.29.16e) N-ethyl-1 -(2-fluoro-1 -methyl-propyl)-5- methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; M.29.16f) 1 -(1 ,2-dimethylpropyl)-N,5-dimethyl- N-pyridazin-4-yl-pyrazole-4-carboxamide; M.29.16g) 1 -[1 -(1 -cyanocyclopropyl)ethyl]-N,5-dime- thyl-N-pyridazin-4-yl-pyrazole-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 selected from M.29.17a) to

M.29.17j): M.29.17a) N-(1 -methylethyl)-2-(3-pyridinyl)-2H-indazole-4-carboxamide; M.29.17b) N-cyclopropyl-2-(3-pyridinyl)-2H-indazole-4-carboxamide; M.29.17c) N-cyclohexyl-2-(3-pyridi- nyl)-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-car- boxamide; 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-pyri- dinyl )-N-(2-pyrimidinylmethyl )-2H-indazole-5-carboxamide; M.29.17j) N-[(5-methyl-2-pyrazi- nyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide, M.29.18 selected from M.29.18a) to M.29.18d): M.29.18a) N-[3-chloro-1 -(3-pyridyl)pyrazol-4-yl]-N-ethyl-3-(3,3,3-trifluoropropylsulfa- nyl)propanamide; M.29.18b) N-[3-chloro-1 -(3-pyridyl)pyrazol-4-yl]-N-ethyl-3-(3,3,3-trifluoropro- pylsulfinyl)propanamide; M.29.18c) N-[3-chloro-1 -(3-pyridyl)pyrazol-4-yl]-3-[(2,2-difluorocyclo- propyl)methylsulfanyl]-N-ethyl-propanamide; M.29.18d) N-[3-chloro-1 -(3-pyridyl)pyrazol-4-yl]-3- [(2,2-difluorocyclopropyl)methylsulfinyl]-N-ethyl-propanamide; M.29.19 sarolaner, or M.29.20 lo- tilaner.

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.alan- wood.net/pesticides.

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 (paichongding in China) is known from WO

07/101369. M.22B.1 is described in CN 10171577 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

07/006670, WO2013/024009 and WO2013/024010, M.28.5i) is described in WO201 1/085575, M.28.5j) in WO2008/134969, M.28.5k) in US201 1/046186 and M.28.5I) in WO2012/034403. 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. M.29.6a) to M.29.6i) listed under M.29.6 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 WO2013/050317. 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, M.29.1 1 i) to M.29.1 1.p) in WO 2010/127926. 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 WO

2010/129497. 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 M.29.16i) and M.29.16j) are described in WO2015/055497. M.29.17a) to M.29.17.j) are described in WO2015/038503. M.29.18a) to M.29.18d) are described in US2014/0213448.

M.29.19 is described in WO2014/036056. 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 Q₀ 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-meth- oxyimino-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-chloro- phenyl)pyrazol-3-yl]oxymethyl]phenyl]-4-methyl-tetrazol-5-one (A.1 .24), 1 -[2-[[1 -(4-chlorophe- nyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one (A.1.25), 1 -[2-[[1 -(4-chloro- phenyl)pyrazol-3-yl]oxymethyl]-3-fluoro-phenyl]-4-methyl-tetrazol-5-one (A.1.26), 1 -[2-[[1 -(2,4- dichlorophenyl)pyrazol-3-yl]oxymethyl]-3-fluoro-phenyl]-4-methyl-tetrazol-5-one (A.1 .27), 1 -[2- [[4-(4-chlorophenyl)thiazol-2-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one (A.1.28), 1 - [3-chloro-2-[[4-(p-tolyl)thiazol-2-yl]oxymethyl]phenyl]-4-methyl-tetrazol-5-one (A.1.29), 1 -[3-cy- clopropyl-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)phe- noxy]methyl]phenyl]tetrazol-5-one (A.1 .32), 1 -methyl-4-[3-methyl-2-[[1 -[3-(trifluoromethyl)phe- nyl]-ethylideneamino]oxymethyl]phenyl]tetrazol-5-one (A.1 .33), (-^2.r)-5-[1 -(2,4-dichlorophe- nyl)pyrazol-3-yl]-oxy-2-methoxyimino-/V,3-dimethyl-pent-3-enamide (A.1 .34), (^2 )-5-[1 -(4- chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-/V,3-dimethyl-pent-3-enamide (A.1 .35), (Z,2E)-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-methyl-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-isobutoxycarbonyloxy-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]amino]-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-methoxypicolinamido]-6-me- thyl-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), me- pronil (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-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide (A.3.19), N-(2-(1 ,3,3-trimethyl-butyl)-phe- nyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide (A.3.20), 3-(difluoromethyl)-1 -methyl-Nil ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.21 ), 3-(trifluoromethyl)-1 -methyl-Nil ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.22), 1 ,3-dimethyl-N-(1 ,1 ,3-trimethylin- dan-4-yl)pyrazole-4-carboxamide (A.3.23), 3-(trifluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylin- dan-4-yl)pyrazole-4-carboxamide (A.3.24), 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole- 4-carboxamide (A.3.25), N-(7-fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-1 ,3-dimethyl-pyrazole-4-carbox- amide (A.3.26), N-[2-(2,4-dichlorophenyl)-2-methoxy-1 -methyl-ethyl]-3-(difluoromethyl)-1 -me- thyl-pyrazole-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); ni- trophenyl 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), tri- adimenol (B.1 .28), triticonazole (B.1 .29), uniconazole (B.1 .30), 1 -[reA(2^3 )-3-(2-chlorophe- nyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1 H-[1 ,2,4]triazolo (B.1 .31 ), 2-\re (2^3 )-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-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -cyclopropyl-2-(1 ,2,4-triazol-1 -yl)ethanol (B.1.34), 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1.35), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1.36), 2-[4-(4-chloro- phenoxy)-2-(trifluoromethyl)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-chlorophenoxy)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1 .39), 2-[4-(4-chlorophe- noxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol (B.1 .40), 2-[4-(4-fluorophen- oxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol (B.1 .41 ), 2-[2-chloro-4-(4-chloro- phenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pent-3-yn-2-ol (B.1 .51 ); imidazoles: imazalil (B.1.42), pe- furazoate (B.1.43), prochloraz (B.1 .44), triflumizol (B.1.45); pyrimidines, pyridines and pipera- zines: fenarimol (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)methanol (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), spirox- amine (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), kiral- axyl (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 hy- drochloride-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-1 -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 hy- droxide (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), guazatine (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]dithi- ino[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 (1.2.2), carpropamid (1.2.3), di- cyclomet (I.2.4), fenoxanil (I.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 .1 1 ), 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-propylchromen-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 -yl- oxy)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-dihy- dro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone (K.1 .29), N-(cyclopropylmethoxy- imino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide (K.1.30), N'-(4-(4- chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine (K.1.31 ), N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-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-trimethylsilanyl-propoxy)-phenyl)-N- ethyl-N-methyl formamidine (K.1 .34), methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-qui- nolin-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-meth- ylene]amino]oxymethyl]-2-pyridyl]carbamate (K.1 .42), 2-[2-[(7,8-difluoro-2-methyl-3-quino- lyl)oxy]-6-fluoro-phenyl]propan-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)quino- line (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; WO13/047749, 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 13/047441 , WO 13/162072, WO 13/092224, WO 1 1/135833). 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, micro- bial 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), in- secticidal 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-sul- fonates, 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 ethox-ylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Exam-pies 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. Ex- amples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpoly- glucosides. Examples of polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vi- nylalcohols, or vinylacetate.

Suitable cationic surfactants are quaternary surfactants, e.g. quaternary ammonium com- pounds 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 poly- acrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyeth- yleneamines.

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 polyvinylpyrrolidone, 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 substance. 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 solu- tion 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. alko- hol 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. methyl- methacrylate, 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 radi-cal 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 insolu-ble organic sol- vent (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 for-mation of a pol- yurea 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 agrochem- ical 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 invention or partially premixed components, e. g. components comprising compounds of the in- vention 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. Further- more, 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 appli- cation, 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; le- guminous 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), chic- ory, 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 combi- nation 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 mutagen- ized or integrated into the genetic material of the plant. The one or more mutagenized or integrated genes are preferably selected from pat, epsps, crylAb, bar, cry1 Fa2, crylAc, cry34Ab1 , cry35AB1 , cry3A, cryF, cry1 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 glufosi- nate 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. ima- zamox. 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 RoundupReady® (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 Wide- Strike®, 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 insecti- cidal 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 insecti- cidal 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, tar- get 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 m², preferably from 0.001 to 20 g per 100 m².

For use in treating crop plants, e.g. by foliar application, the rate of application of the active in- gredients 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 in- sects, 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, Bras- sica 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 treat- ment 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 af- ter 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 1000 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 invention may also be used for improving the health of a plant. Therefore, the 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 phyto- toxic 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 (for example, 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, ter- mites, 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, for example, 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 polyor- ganosaccharides, 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.phero- base.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 hu- man being (e.g. when the pests invade into houses and public facilities).

Customary application rates in the protection of materials are, for example, from 0.001 g to 2000 g or from 0.01 g to 1000 g of active compound per m² treated material, desirably from 0.1 g to 50 g per m².

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, Aisophiia pometaria, Ampelophaga rubiginosa, Amyeiois transiteiia, Anacampsis sarciteiia, Ana- gasta kuehniella, Anarsia lineatella, An/so ta senator/a, Antheraea pernyi, Anticarsia (=Therme- sia) spp. such as A. gemmatalis; 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 viridigrisea, Autog- rapha gamma, Autographa nigrisigna, Barathra brassicae, Bedellia spp., Bonagota salubricola, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp. such as C. m urinaria, C. podana; Cactoblastis cactorum, Cadra cauteiia, Ca lingo brazi lien sis, Calop- tilis 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 pariana, Choristoneura spp. such as C. conflictana, C. fumiferana, C. longi- cellana, C. murinana, C. occidentalis, C. rosaceana; Chrysodeixis (=Pseudoplusia) spp. such as C. eriosoma, C. includens; Cirphis unipuncta, Clysia ambiguella, Cnaphalocerus spp., Cna- phalocrocis medinalis, Cnephasia spp., Cochylis hospes, Coleophora spp., Co lias eurytheme, Conopomorpha spp., Conotrachelus spp., Cop/tarsia spp., Corcyra cephalonica, Crambus ca/ig- inosellus, Crambus teterrellus, Crocidosema (=Epinotia) aporema, Cydalima (=Diaphania) per- spectalis, Cydia (=Carpocapsa) spp. such as C. pomonella, C. latiferreana; Dalaca noctuides, Datana integerrima, Dasychira pinicola, Dendrolim us spp. such as D. pini, D. spectabilis, D. sibi- ricus; Desmia funeralis, Diaphania spp. such as D. nitidalis, D. hyalinata; Diatraea grandiosella, Diatraea saccharaiis, Diphthera f estiva, Ear/as spp. such as E. insuiana, E. vitteiia; Ecdytolopha aurantianu, Egira (=Xylomyges) curia/is, E/asmopa/pus lignosellus, Eldana saccharina, Endopi- za viteana, Ennomos subsignaria, Eoreuma loftini, Ephestia spp. such as E. cauteiia, E. eiuteiia, E. kuehniella; Epinotia aporema, Epiphyas postvittana, Erannis tiliaria, Erionota thrax, Etiella spp., Eulia spp., Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Faronta albilinea, Feltia spp. such as F. subterranean; Galleria mellonella, Gracillaria spp., Gra- pholita spp. such as G. funebrana, G. molesta, G. inopinata; Ha lysidota spp., Harrisina ameri- cana, Hedylepta spp., Helicoverpa spp. such as H. armigera (=Heliothis armigera), H. zea (=He- liothis zea); Heliothis spp. such as H. assulta, H. subflexa, H. virescens; Hellula spp. such as H. undalis, H. roga talis; Helocoverpa gelotopoeon, Hemileuca oliviae, Herpetogramma licarsisalis, Hibernia defoliaria, Hofmannophila pseudospretella, Homoeosoma electellum, Homona mag- nanima, Hypena sea bra, Hyphantria cunea, Hyponomeuta pad el la, Hyponomeuta malinellus, Kakivoria flavofasciata, Keiferia lycopersicella, Lambdina fiscellaria fiscellaria, Lambdina fiscel- laria lugubrosa, Lamprosema indicata, Laspeyresia molesta, Leguminivora glycinivorella, Ler- odea eufala, Leucinodes orbonalis, Leucoma salicis, Leucoptera spp. such as L. coffeella, 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. cerera/is; Lyman tria spp. such as L. dispar, L. monacha; Lyonetia clerkella, Lyonetia prunifoliella, Malacosoma spp. such as M. americanum, M. californicum, M. constrict- tum, 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 testuiaiis, Megaiopyge lanata, Meianchra picta, Meianitis leda, Mods spp. such as M. lapites, M. repanda; Mods latipes, Monochroa fragariae, Mythimna separata, Nemapogon cloacella, Ne- oleucinodes elegantalis, Nepytia spp., Nymphula spp., Oiketicus spp., Omiodes indicata, Om- phisa anastomosalis, Operophtera brumata, Orgy/a pseudotsugata, Or/a spp., Orthaga thyri- sa/is, Ostrinia spp. such as O. nubilalis; Oulema oryzae, Paleacrita vernata, Panolis flammea, Parnara spp., Papaipema nebris, Papilio cresphontes, Paramyelois transitella, Paranthrene re- galis, Paysandisia archon, Pectinophora spp. such as P. gossypiella; Peridroma saucia, Per/ieu- coptera 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; Pilocro- cis tripunctata, Plathypena scabra, Platynota spp. such as P. flavedana, P. idaeusalis, P. stul- tana; Platyptilia carduidactyla, Plebejus argus, Plodia interpunctella, Plusia spp, Plutella maculi- pennis, Plutella xylostella, Pontia protodica, Prays spp., Prodenia spp., Proxenus /epigone, Pseudaletia spp. such as P. sequax, P. unipuncta; Pyrausta nubilalis, Rachiplusia nu, Richia al- bicosta, Rhizobius ventralis, Rhyacionia frustrana, Sabulodes aegrotata, Schizura concinna, Schoenobius spp., Schreckensteinia festaliella, Scirpophaga pp. such as S. incertulas, S. inno- tata; Scotia segetum, Sesamia spp. such as S. inferens, Seudyra subfiava, Sitotroga cereaieiia, 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, Tec/a solanivora, Telehin Ileus, Thaumatopoea pityo- campa, Thaumatotibia (=Cryptophlebia) leucotreta, Thaumetopoea pityocampa, T heel a spp., Theresimima ampelophaga, Thyrinteina spp, Tildenia inconspicuella, Tinea spp. such as T. clo- acella, T. pellionella; Tineola bisselliella, Tortrix spp. such as T. viridana; Trichophaga tapetz- ella, Trichoplusia spp. such as T. ni; Tuta (=Scrobipalpula) absoluta, Udea spp. such as U. rubi- galis, U. rubigalis; Virachola spp., Yponomeuta pa del la, 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; Agri- otes 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., Apogonia spp., 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 trifur- cata, Cetonia aurata, Ceuthorhynchus spp. such as C. assimilis, C. napi; Chaetocnema tibialis, Cleonus mendicus, Conoderus spp. such as C. vespertinus; Conotrachelus nenuphar, Cosmop- olites spp., Costelytra zealandica, Crioceris asparagi, Cryptolestes ferrugineus, Cryptorhynchus lapathi, Ctenicera spp. such as C. destructor; Curculio spp., Cylindrocopturus spp., Cycloceph- ala spp., Dactylispa balyi, Dectes texanus, Dermestes spp., Diabrotica spp. such as D. undec- impunctata, D. speciosa, D. longicornis, D. semi punctata, D. virgifera; Diaprepes abbreviates, Dichocrocis spp., Dicladispa armigera, DHoboderus abderus, Diocalandra frumenti (Diocalandra stigmaticollis), Enaphalodes rufulus, Epilachna spp. such as E. varivestis, E. vigintioctomacu- lata; Epitrix spp. such as E. hirtipennis, E. similaris; Eutheoia humiiis, Eutinobothrus brasiiiensis, Faustinus cubae, Gibbium psylloides, Gnathocerus cornutus, Hellula undalis, Heteronychus arator, Hylamorpha elegans, Hylobius abietis, Hylotrupes bajulus, Hypera spp. such as H. brun- neipennis, H. postica; Hypomeces squamosus, Hypothenem us spp., Ips typographus, Lachno- sterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp. such as L. bilineata, L. melanopus; Leptinotarsa spp. such as L. decern lineata ; Leptispa pyg- maea, Limonius californicus, Lissorhoptrus 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., Me/anotus communis, Meligethes spp. such as M. aeneus; Melolontha spp. such as M. hippocastani, M. melolontha; Metamasius hemip- terus, Microtheca spp., Migdolus spp. such as M. fryanus, Monocham us spp. such as M. alternates; Naupactus xanthographus, Niptus hololeucus, Oberia b re vis, Oemona hirta, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorrhynchus sulcatus, Otiorrhyn- chus ovatus, Otiorrhynchus sulcatus, Oulema melanopus, Oulema oryzae, Oxyce ton/a jucunda, Phaedon spp. such as P. brassicae, P. cochleariae; Phoracantha recurva, Phyllobius pyri, Phyl- lopertha horticola, Phyllophaga spp. such as P. helleri; Phyllotreta spp. such as P. chrysoceph- ala, P. nemorum, P. striolata, P. vittula; Phyllopertha horticola, Pop/ilia japonica, Premnotrypes spp., Psacothea hilaris, Psylliodes chrysocephala, Prostephanus truncates, Psylliodes spp., Pti- nus spp., Pulga saltona, Rhizopertha dominica, Rhynchophorus spp. such as R. billineatus, R. ferrugineus, R. pal ma rum, 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; Strophomorphus ctenotus, Symphyletes spp., Tanymecus spp., Tenebrio moli- tor, Tenebrioides mauretanicus, Tribolium spp. such as T. castaneum; Trogoderma spp., Ty- chius spp., Xylotrechus spp. such as X. pyrrhoderus; and, Zabrus spp. such 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; Bactro- cera in va dens, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capitata, 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. intestinaiis; 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 pectoraiis, Mansonia titiiianus, Mayetioia 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. antiqua, P. brassicae, P. coarctata; Phytomyza gymnostoma, Prosimuiium mixtum, Psiia 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. calcitrans; 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 for example, Baliothrips biformis, Dichromothrips cor- betti, Dichromothrips ssp., Echinothrips americanus, Enneothrips flavens, Frankliniella spp. such as F. fusca, F. occidentalis, F. tritici; Heliothrips spp., Hercinothrips femora/is, Kakothrips spp., Microcephalothrips abdominalis, Neohydatothrips samayunkur, Pezothrips kellyanus, Rhipiphorothrips cruentatus, Scirtothrips spp. such as S. citri, S. dorsalis, S. perseae; Stenchae- tothrips spp, Taeniothrips cardamoni, Taeniothrips inconsequens, Thrips spp. such as T. imagines, T. hawaiiensis, T. oryzae, T. pa I mi, T. parvispinus, T. tabaci;

insects from the order of Hemiptera for example, Acizzia jamatonica, Acrosternum spp. such as A. are/Acyrthosipon spp. such as A. onobrychis, A. pisum; Adelges laricis, Adelges tsu- gae, Adelphocoris spp., such as A. rapidus, A. superbus; Aeneolamia spp., Agonoscena spp., Aulacorthum solani, Aleurocanthus woglumi, Aleurodes spp., Aleurodicus disperses, Aleurolo- bus barodensis, Aleurothrixus spp., Amrasca spp., Anasa tristis, Antestiopsis spp., Anuraphis cardui, 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.

schneideri, A. spiraeco/a; Arbor/d/a apica/is, Ar/ius critatus, Aspidiella spp., Aspidiotus spp., Ata- nus spp., Aulacaspis yasumatsui, Aulacorthum solani, Bactericera cockerelli (Paratrioza cockerelli), Bemisia spp. such as B. argentifolii, B. tabaci (Aleurodes tabaci); Blissus spp. such as B. leucopterus; Brachycaudus spp. such as B. cardui, B. helichrysi, B. persicae, B. prunicola;

Brachycolus spp., Brachycorynella asparagi, Brevicoryne brassicae, Cacopsylla spp. such as C. fulguralis, C. pyricola (Psylla piri); Calligypona marginata, Calocoris spp., Campylomma livida, Capitophorus horn/, Carneocephala fulgida, Cavelerius spp., Ceraplastes spp., Ceratovacuna lanigera, Ceroplastes ceriferus, Cerosipha gossypii, Chaetosiphon fragaefolii, Chionaspis tega- lensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbiia, Cimex spp. such as C. hemipterus, C. lectularius; Coccomytilus halli, Coccus spp. such as C. hesperi- dum, C. pseudomagno/iarum, Corythucha arcuata, Creont/ades d/iutus, Cryptomyzus r/b/s, Chrysomphalus aon/dum, Cryptomyzus r/b/s, Ctenaryta/na spatu/ata, Cyrtope/t/s 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., Dreyfus/a nordmann/anae, Dreyfus/a p/ceae, Drosicha spp., Dysaphis spp. such as D. plantaginea, D. pyri, D. radicola; Dysaulacorthum pseudosolani, Dysdercus spp. such as D. cingulatus, D. intermedins; Dysmicoccus spp., Edessa spp., Geocoris spp., Em- poasca spp. such as E. fabae, E. so/ana; Ep/d/asp/s leper//, Er/osoma spp. such as E. lanig- erum, E. pyricola; Erythroneura spp., Eurygaster spp. 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 I. purchase; Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lecanoideus floccissimus, Lepidosaphes spp. such as L. ulmi; Leptocorisa spp., Leptoglossus phyllopus, Lipaphis erysimi, Lygus spp. such as L. hesperus, L. lineolaris, L. pra- tensis; Maconellicoccus hirsutus, Marchalina hellenica, 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 saccharicida, Phenacoc- cus 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; Pinnaspis aspidistrae, Planococcus spp. such as P. citri, P. ficus; Prosapia bicincta, Protopulvinaria pyri- formis, Psallus seriatus, Pseudacysta persea, Pseudaulacaspis pentagona, Pseudococcus spp. such as P. comstocki; Psylla spp. such as P. ma/I; Pteroma/us spp., Pulvinaria amygdali, Pyrilla spp., Quadraspidiotus pp., such as Q. perniciosus; Quesada gigas, Rastrococcus spp., Redu- vius senilis, Rhizoecus americanus, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosi- phum spp. such as R. pseudobrassicas, R. insertum, R. maidis, R. pad/; Sagatodes spp., Sahl- bergella singularis, Saissetia spp., Sappaphis mala, Sappaph/s mail, Scaptocoris spp., Scaph- o/des titan us, Schizaphis graminum, Schizoneura lanuginosa, Scotinophora spp., Selenaspidus articulatus, Sitobion avenae, Sogata spp., Sogatella furcifera, Solubea insularis, Spissistilus festinus (=Stictocephala festina), Stephanitis nashi, Stephanitis pyrioides, Stephanitis takeyai, Tenalaphara malayensis, Tetraleurodes perseae, Therioaphis maculate, Thyanta spp. such as T. accerra, T. perditor; Tibraca spp., Tomaspis spp., Toxoptera spp. such as T. aurantii; Trialeu- rodes spp. such as T. abutilonea, T. ricini, T. vaporariorum; Triatoma spp., Trioza spp., Typhlo- cyba spp., Unaspis spp. such as U. citri, U. 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, Dorymyrmex spp., Dryocosmus kuriphilus, For- mica spp., Hoplocampa spp. such as H. minuta, H. testudinea; Iridomyrmex humilis, Lasius spp. such as L. niger, Linepithema humile, Liometopum spp., Leptocybe invasa, Monomorium spp. such as M. pharaonis, Monomorium, Nylandria fuiva, Pachycondyla chinensis, Paratrechina lon- gicornis, Paravespula spp., such as P. germanica, P. pennsylvanica, P. vulgaris; Pheidole spp. such as P. megacephala; Pogonomyrmex spp. 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. xy/oni, Sphecius speciosus, Sphex spp., 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. squamosal; 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, Kraus- saria angulifera, Locusta spp. such as L. migratoria, L. pardalina; Melanoplus spp. such as M. bivittatus, M. femurrubrum, M. mexicanus, M. sanguinipes, M. spretus; Nomadacris septemfas- data, Oedaleus senegalensis, Scapteriscus spp., Schistocerca spp. such as S. americana, 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, Rhi- picephalus spp. such as R. sanguineus, R. appendiculatus, Rhipicephalus everts/, Rhizogly- phus spp., Sarcoptes spp. such asS. Scabiei, and Family Eriophyidae including Acer/a spp. such as A. she/doni, A. anthocoptes, Acallitus spp., Aoy/o s spp. such as A. lycopersici, A. pel- ekassi, Aculus spp. such as A schlechtendali; Colomerus vitis, Epitrimerus pyri, Phyllocoptruta oleivora; Eriophytes ribis and Eriophyes spp. such as Eriophyes sheldonr, Family Tarsonemidae including Hemitarsonem us 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 T. cinnabarinus, T. evansi, T. kanzawai, T, pacificus, T. phaseulus, T. telarius and T. urticae, Bryobia praetiosar, Panonychus spp. such as P. u/mi, P. citri, Metatetranychus spp. and Oligonychus spp. such as O. pratensis, O. perseae, Vasates lycopersici, Raoiella indica, /¾/77/7yCarpoglyphidae including Carpogly- phus spp.; Penthaleidae spp. such as Halotydeus destructor, Family Demodicidae with species such as Demodexspp.; Family Trombicidea including Trombicula spp:, Family Macronyssidae including Ornothonyssus spp:, Family Pyemotidae including Pyemotes tritici, Tyrophagus pu- trescentiae; Family Acaridae including Acarus siro, Family Araneida including Latrodectus mac- tans, Tegenaria agrestis, Chiracanthium sp, Lycosa sp Achaearanea tepidariorum and Loxos- celes reclusa,

Pests from the Phylum Nematoda, for example, plant parasitic nematodes such as root-knot nematodes, Meloidogyne spp. such as M. hapla, M. incognita, M. javanica; cyst-forming nema- todes, Globodera spp. such as G. rostochiensis; Heterodera spp. such as H. avenae, H. glycines, H. schachtii, H. trifo/ii; Seed gall nematodes, Anguina spp:, Stem and foliar nematodes, Aphe/enchoides spp. such as A besseyi; Sting nematodes, Be/ono/aim us spp. such as B. longi- caudatus; Pine nematodes, Bursaphelenchus spp. such as B. lignicolus, B. xylophilus; Ring nematodes, Criconema spp., Criconemella spp. such as C. xenoplax and C. ornata; and, Cricone- moides spp. such as Criconemoides in formis; Mesocriconema spp.; Stem and bulb nematodes, Ditylenchus spp. such as D. destructor, D. dipsaci; Awl nematodes, Dolichodorus spp.; Spiral nematodes, Heliocotylenchus multicinctus; Sheath and sheathoid nematodes, Hemicycliophora spp. and Hemicriconemoides spp. ; Hirshmanniella spp.; Lance nematodes, Hoploaimus spp.; False rootknot nematodes, Nacobbus spp.; Needle nematodes, Longidorus spp. such as L. elongatus; Lesion nematodes, Pratylenchus spp. such as P. brachyurus, P. neglectus, P. penetrans, P. curvitatus, P. goodeyi; Burrowing nematodes, Radopholus spp. such as R. similis; Rhadopholus spp.; Rhodopholus spp.; Reniform nematodes, Rotylenchus spp. such as R. ro- bustus, R. reniformis; Scutellonema spp.; Stubby-root nematode, Trichodorus spp. such as T. obtusus, T. primitivus; Paratrichodorus spp. such as P. minor; Stunt nematodes, Tylenchorhyn- chus spp. such as T. claytoni, T. dub/us; Citrus nematodes, Ty/enchu/us spp. such as T. semi- 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; Giobitermes suifureus, Heterotermes spp. such as H. aureus, H. longiceps, H. tenuis; Leucotermes flavipes, Odontotermes spp., I ncisitermes 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. siyc 7 as Z. angusticoiiis, Z. nevadensis, Reticulitermes spp. such as R. hesperus, R. tibia/is, R. spera- tus, R. flavipes, R. grassei, R. lucifugus, R. santonensis, R. virginicus; Termes natalensis,

Insects from the order Blattaria e.g. Blatta spp. such as B. orientalis, B. lateralis; Blattella spp. such as B. asahinae, B. germanica; Leucophaea maderae, Panchlora nivea, Periplaneta 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., Ctenoce- phalides spp. such as C. felis, C. cam^'s, Xenopsylla cheopis, Pulex irritans, Trichodectes cam^'s, Tung a penetrans, and Nosopsyllus fascia tus,

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 for example, 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 human us; Pthirus pubis, Haematopinus spp. such as Haematopinus eurysternus, Haematopinus suis, Linognathus spp. such as Linognathus vituii; Bovicoia bovis, Menopon gaiiinae, 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, for example, Dreissena spp.; class Gastropoda, for example, 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, for example, Ancyiostoma duodenaie, Ancyiostoma ceyianicum, Acyiostoma braziiiensis, Ancyiostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia t/^'mori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp., Dictyocaulus filaria, Diphyl- lobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocu- laris, Enterobius vermicularis, Faciola spp., Haemonchus spp. such as Haemonchus contortus; Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesoph- agostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonim us spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercora lis, Stronyloides spp., Taenia saginata, Taenia solium, T rich in ell a spiralis, Trichinella nativa, Trichinella britovi, Trichi- nella 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 control- ling 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 effec- tive 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 compo- sitions comprising said mixtures.

The compounds of the invention and compositions comprising them can be applied orally, parenterally 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. Fur- thermore, 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 environment 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 cam^'s, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus; cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Peri plane ta am erica na, Peri plan eta japonica, Peri- planeta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis; flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes aibopictus, 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 pip/ens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Derma tobia hominis, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Glossina pa/pa/is, Glossina fuscipes, Glossina tachinoides, Ha em a tobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Leptoconops torrens, Lu cilia caprina, Lu cilia cuprina, Lu cilia sericata, Lycoria pectoral is, Manso- nia spp., Musca domestica, Muscina stabulans, Oestrus ovis, Phlebotomus argentipes, Psoro- phora columbiae, Psorophora discolor, Prosimulium mixtum, Sarcophaga haemorrhoidalis, Sar- cophaga sp., Sim u Hum vittatum, Stomoxys calcitrans, 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, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus; ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocy- clus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor varia- bilis, Amblyomma americanum, Ambryomma macu latum, 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., Kne- midocoptes spp., Cytodites spp., and Laminosioptes spp; Bugs (Heteropterida): Cimex lectular- ius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Panstrongyius ssp., and Ar/ius cr/tatus; Anop\ur\da, 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., CapiHaria spp.; Rhabditida, e.g. Rhabditis spp., Strongyloides spp., Helicephalobus spp.; 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 dentatus, Ollula- nus 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 Dioctophyma 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 equi; CamaWanlda, e.g. Dracunculus medinensis (guinea worm); Spirurida, e.g. Thelazia spp., Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp. a, Dipetalonema spp., Se tar/a 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 caninum, 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, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The formula I compounds may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the formula I compounds may be formulated into an implant for subcutaneous administration. In addition the formula I compound may be transdermally 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 suspend- ing 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 collars, 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

A. Preparation examples

With appropriate modification of the starting materials, the procedures given in the synthesis description were used to obtain further compounds I. The compounds obtained in this manner are listed in the table that follows, together with physical data.

The products shown below were characterized by melting point determination, by NMR spectroscopy or by the masses ([m/z]) or retention time (RT; [min.]) determined by HPLC-MS or HPLC spectrometry.

HPLC-MS = high performance liquid chromatography-coupled mass spectrometry;

HPLC method A: HPLC Phenomenex Kinetex 1 .7 m XB-C18 100A; 50 x 2.1 mm; mobile phase: A: water + 0.1 % trifluoroacetic acid (TFA); B: acetonitrile; temperature: 60°C; gradient: 5-100% B in 1.50 minutes; 100% B 0.25 min; flow: 0.8-1 .Oml/min in 1.51 minutes at 60°C. MS: ESI positive, m/z 100-1400. HPLC method B: HPLC Phenomenex Kinetex 1 .7μηι XB-C18 100A, 50 x 2.1 mm; mobile phase: A: water + 0,1 % TFA; B: acetonitrile; temperature: 60°C; gradient:5% B to 100% B in 1 ,50 minutes; 100% B 0.25min; Flow: 0.8ml/min to 1 .0ml/min in 1 .51 min; MS method: ESI positive; Mass range (m/z): 100-700.

The synthesis of (1 RS,3RS)-2,2-dichloro-3-(3,5-dichlorophenyl)cyclopropanecarboxylic acid and methyl (1 RS,3RS)-2,2-dichloro-3-(3,5-dichlorophenyl)cyclopropanecarboxylate was performed in analogy to WO 2016/168056, WO 2016/168058, and WO 2016/168059. Example 1 : Synthesis of N-benzyl-2-chloro-5-[5-[(1 RS,3RS)-2,2-dichloro-3-(3,5-dichloro- phenyl)cyclopropyl]-1 ,3,4-thiadiazol-2-yl]benzamide [1-3-1 ].

Step 1 : Synthesis of 3-Bromo-4-chloro-benzohydrazide:

To a solution of commercially available methyl 3-bromo-4-chlorobenzoate (5.00 g, 20.0 mmol) dissolved in MeOH (100 ml.) at 20-25°C was added Η₂ΝΝΗ₂Ή₂0 (3.07 g, 61.3 mmol) and the mixture was heated at reflux temperature over night. After that time, the resulting mixture was concentrated under reduced pressure, the residue was suspended in MTBE, the solid contents collected via filtration and dried in a vacuum oven to afford the title compound (4.34 g, 87%).

LC-MS: Mass calculated for C₇H₇BrCIN₂0⁺ [(M+H)⁺)] 248.9, found 248.9; RT = 0.756 min.

Step 2: Synthesis of 3-bromo-4-chloro-N'-[(1 RS,3RS)-2,2-dichloro-3-(3,5-dichlorophenyl)cyclo- propanecarbonyl]benzohydrazide:

To a solution of 3-bromo-4-chloro-benzohydrazide (3.00 g, 12.0 mmol), (1 RS,3RS)-2,2-di- chloro-3-(3,5-dichlorophenyl)cyclopropanecarboxylic acid (3.00 g, 10.0 mmol), and PyBroP (5.59 g, 12.0 mmol) dissolved in CH₂CI₂ (100 ml.) at 20-25°C was added iPr₂NEt (5.43 g,

42.0 mmol) dropwise and the resulting reaction mixture was stirred at 20-25°C over night. Concentration of the reaction mixture under reduced pressure and purification by column chromatography (EtOAc/cyclohexane 0:100 to 100:00, gradient) afforded the title compound (4.53 g, 85%)

LC-MS: Mass calculated for Ci₇HnBrCI₅N₂0₂ ⁺ [(M+H)⁺)] 530.8, found 530.7; RT= 1 .334 min

Step 3: Synthesis of 2-(3-bromo-4-chloro-phenyl)-5-[(1 RS,3RS)-2,2-dichloro-3-(3,5-dichloro- phenyl)cyclopropyl]-1 ,3,4-thiadiazole:

To a solution of 3-bromo-4-chloro-N'-[(1 RS,3RS)-2,2-dichloro-3-(3,5-dichlorophenyl)cyclopro- panecarbonyl]benzohydrazide (4.52 g, 8.51 mmol) dissolved in toluene (200 ml.) at 20-25°C was added 2,4-bis(4-methoxyphenyl)-2,4-dithioxo-1 ,3,2,4-dithiadiphosphetane (6.19 g,

15.3 mmol) and the reaction mixture was heated at 100 °C for 2 hours. Then the reaction mixture was allowed to cool to 20-25°C, concentrated under reduced pressure, and the residue was purified by column chromatography (EtOAc/cyclohexane 0:100 to 30:70, gradient), affording the tiltle compound (3.02 g, 67%)

LC-MS: Mass calculated for Ci₇H₉BrCI₅N₂S⁺ [(M+H)⁺)] 528.8, found 528.8; RT= 1 .624 min

Step 4: Synthesis of N-benzyl-2-chloro-5-[5-[(1 RS,3RS)-2,2-dichloro-3-(3,5-dichlorophenyl)- cyclopropyl]-1 ,3,4-thiadiazol-2-yl]benzamide [1-3-1]: In a 100 mL Premex autoclave, 2-(3-bromo-4-chloro-phenyl)-5-[(1 RS,3RS)-2,2-dichloro-3-(3,5- dichlorophenyl)cyclopropyl]-1 ,3,4-thiadiazole (200 mg, 0.378 mmol), benzylamine (162 mg, 1 .51 mmol), Et₃N (57.3 mg, 0.567 mmol), Pd(OAc)₂ (8.5 mg, 0.038 mmol), and 4,5-bis(diphenyl- phosphino)-9,9-dimethylxanthene (44 mg, 0.076 mmol) were mixed in toluene (35 mL) at 20- 25°C, before the vessel was sealed, pressurized with CO gas (7 bar), and the reaction mixture heated at 80 °C for 5 hours. Then the reaction mixture was allowed to cool to 20-25°C, purged with N2, diluted with EtOAc, filtered through a short pad of Celite, and concentrated under reduced pressure. Purification by column chromatography (EtOAc/cyclohexane 0:100 to 40:60, gradient) afforded the tiltle compound (95.0 mg, 43%).

LC-MS: Mass calculated for C25Hi₇CI₅N30S⁺ [(M+H)⁺)] 584.0, found 583.8; RT= 1.483 min

Example 2: Synthesis of 2-chloro-N-cyclopropyl-5-[5-[(1 RS,3RS)-2,2-dichloro-3-(3,5-dichloro- phenyl)cyclopropyl]-1 ,3,4-oxadiazol-2-yl]benzamide [1-1 -2]. Step 1 : Synthesis of 2-(3-bromo-4-chloro-phenyl)-5-[(1 RS,3RS)-2,2-dichloro-3-(3,5-dichloro- phenyl)cyclopropyl]-1 ,3,4-oxadiazole:

3-Bromo-4-chloro-N'-[(1 RS,3RS)-2,2-dichloro-3-(3,5-dichlorophenyl)cyclopropanecarbonyl]- benzohydrazide (2.70 g, 5.08 mmol), which was prepared as described above in Example 1 , was dissolved in POCI3 (20 mL) and the resulting mixture was heated at 85 °C for 4 hours. Then the reaction mixture was partially concentrated under reduced pressure, poured on ice water (100 mL), and the aqueous phase was extracted with CH2CI2 (3 ^χ 50 mL). The combined organic extracts were dried over Na2S0₄, filtered and concentrated under reduced pressure. Purification by column chromatography (EtOAc/cyclohexane 0:100 to 100:0, gradient) afforded the title compound (1 .14 g, 44%).

LC-MS: Mass calculated for Ci7H₉BrCI₅N20⁺ [(M+H)⁺)] 512.8, found 512.8; RT= 1.597 min

Step 2: Synthesis of 2-chloro-N-cyclopropyl-5-[5-[(1 RS,3RS)-2,2-dichloro-3-(3,5-dichloro- phenyl)cyclopropyl]-1 ,3,4-oxadiazol-2-yl]benzamide [1-1 -2]:

In a 100 mL Premex autoclave, 2-(3-bromo-4-chloro-phenyl)-5-[(1 RS,3RS)-2,2-dichloro-3-(3,5- dichlorophenyl)cyclopropyl]-1 ,3,4-oxadiazole (300 mg, 0.584 mmol), cyclopropylamine

(50.0 mg, 0.876 mmol), Na₂C0₃ (61 .9 mg, 0.584 mmol), Pd(OAc)₂ (13.1 mg, 0.058 mmol), and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (67.6 mg, 0.1 17 mmol) were mixed in toluene (35 mL) at 20-25°C, before the vessel was sealed, pressurized with CO gas (7 bar), and the reaction mixture heated at 80 °C for 16 hours. Then the reaction mixture was allowed to cool to 20-25°C, purged with N2, and concentrated under reduced pressure. Purification by column chromatography (EtOAc/cyclohexane 0:100 to 100:0, gradient) afforded the tiltle compound (173 mg, 57%).

LC-MS: Mass calculated for C2iHi5CI₅N₃02⁺ [(M+H)⁺)] 517.8, found 517.9; RT= 1.331 min Example 3: Synthesis of 2-chloro-N-cyclopropyl-5-[5-[(1 RS,3RS)-2,2-dichloro-3-(3,5-dichloro- phenyl)cyclopropyl]-4H-1 ,2,4-triazol-3-yl]benzamide [1-2-1 ]:

Step 1 : Synthesis of (1 RS,3RS)-2,2-dichloro-3-(3,5-dichlorophenyl)cyclopropanecarbohydra- zide: To a solution of methyl (1 RS,3RS)-2,2-dichloro-3-(3,5-dichlorophenyl)cyclopropanecarboxylate (1 .80 g, 5.73 mmol) in MeOH (20 mL) at 20-25°C was added Η₂ΝΝΗ₂Ή₂0 (5.80 g, 63.7 mmol) and the resulting mixture was stirred at reflux temperature for 1 hour. Then the reaction mixture was concentrated under reduced pressure, the residue re-dissolved in EtOAc (25 mL), and the organic phase was washed with NaCI solution (sat. aqueous, 2 x 5 mL), dried over Na₂S0₄, filtered and concentrated under reduced pressure to afford the tiltle compound (1 .53 g, 85%) in crude form and was used in the next step without further purification.

LC-MS: Mass calculated for Ci₀H₉CI₄N₂O⁺ [(M+H)⁺)] 314.9, found 314.7; RT= 1 .023 min. Step 2: Synthesis of ethyl 3-bromo-4-chloro-benzenecarboximidate:

To a solution of commercially available 3-bromo-4-chloro-benzonitrile (2.00 g, 9.24 mmol) dissolved in EtOH (20 mL) at 0 °C was added acetyl chloride (7.25 g, 92,4 mmol) dropwise, the cooling bath was left to slowly expire and the reaction mixture was stirred at 20-25 °C over night, then the reaction mixture was concentrated under reduced pressure, the residue washed with Et₂0 (2 x 10 mL) and then dissolved in NaHC03 solution (sat. aqueous, 10 mL). The aqueous phase was extracted with EtOAc (3 x 10 mL), and the combined organic extracts were dried over Na₂S0₄, filtered and concentrated under reduced pressure to afford the title compound (2.02 g, 83%) in crude form, which could be used in the next step without further purification. LC-MS: Mass calculated for C₉Hi₀BrCINO⁺ [(M+H)⁺)] 264.0, found 263.8; RT= 0.821 min.

Step 3: Synthesis of 3-(3-bromo-4-chloro-phenyl)-5-[(1 RS,3RS)-2,2-dichloro-3-(3,5-dichloro- phenyl)cyclopropyl]-4H-1 ,2,4-triazole:

(1 RS,3RS)-2,2-dichloro-3-(3,5-dichlorophenyl)cyclopropanecarbohydrazide (1.70 g,

5.41 mmol) and 3-bromo-4-chloro-benzenecarboximidate (2.24 g, 7.68 mmol) were dissolved in acetic acid (50 mL) and the reaction mixture was heated at 80 °C for 2 h. Then the reaction mixture was allowed to cool to 20-25°C and concentrated under reduced pressure. The residue was further dried via azeotropical destination with toluene (2 x), re-dissolved in EtOAc (50 mL), and the organic phase was washed with NaHC03 solution (1 x 10 mL), NaCI solution (1 x 10 mL), dried over Na₂S0₄, filtered and concentrated under reduced pressure. Purification by col- umn chromatography (EtOAc/cyclohexane 0:100 to 100:0, gradient) afforded the tiltle compound (1 .47 g, 53%).

LC-MS: Mass calculated for Ci₇HioBrCI₅N3⁺ [(M+H)⁺)] 513.9, found 513.8; RT= 1 .522 min.

Step 4: From the above 3-(3-bromo-4-chloro-phenyl)-5-[(1 RS,3RS)-2,2-dichloro-3-(3,5-dichlo- rophenyl)cyclopropyl]-4H-1 ,2,4-triazole, the desired 2-chloro-N-cyclopropyl-5-[5-[(1 RS,3RS)-2,2- dichloro-3-(3,5-dichloro-phenyl)cyclopropyl]-4H-1 ,2,4-triazol-3-yl]benzamide was obtained analogously to Example 2 (Step 2). Table C.1 - Compounds of formula 1.1

^;' The given isomer in at least 85% by weight

Table C.2 - Compounds of formula

^;' The given isomer in at least 85% by weight

Table C.3 - Compounds of formula 1.3

^;' The given isomers in at least 85% by weight

II. Evaluation of pesticidal activity:

The activity of the compounds of formula I of the invention could be demonstrated and evaluated in biological tests described in the following.

If not otherwise specified the respective active compound is dissolved at the desired concen- tration in a mixture of 1 :1 (vohvol) distilled water : acetone. The test solution is prepared at the day of use.

B.1 Diamond back moth (Plutella xylostella)

The active compound was dissolved at the desired concentration in a mixture of 1 :1 (vohvol) distilled water : aceteone. Surfactant (Kinetic HV) was added at a rate of 0.01 % (vol/vol). The test solution was 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 1-1 -2, I-3-2, I-3-3, and I-3-4, resp., at 300 ppm showed over 75% mortality in comparison with untreated controls.

B.2 Green Peach Aphid (Myzus persicae)

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 mem brane.

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, us- ing a custom built pipetter, at two replications.

After application, 5 - 8 adult aphids were placed on the artificial membrane inside the microtiter 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 I-3-2, and I-3-3, resp., at 2500 ppm showed over 50% mortality in comparison with untreated controls.

B.3 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 1-3-2, and 1-3-3, resp., at 2500 ppm showed over 50% mortality in comparison with untreated controls.

B.4 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 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.

In this test, compounds 1-1 -1 , 1-3-1 , 1-1 -2, I-3-2, I-3-3, 1-1 -4, I-3-4, and 1-1-5, resp., at 2500 ppm showed over 75% mortality in comparison with untreated controls. B.5 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 1-3-1 , 1-1-2, I-3-2, I-3-3, and I-3-4, resp., at 2500 ppm showed over 75% mortality in comparison with untreated controls.

B.6 Orchid thrips (dichromothrips corbetti)

Dichromothrips corbel/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 I-3-2, and I-3-3, resp., at 300 ppm showed over 75% mortality in comparison with untreated controls.

Claims

Cyclopropyl compounds of formula I

wherein

R^1a is H, halogen, halomethyl, or Ci-C4-alkyl;

R^{1 b} is halogen, halomethyl, or Ci-C4-alkyl;

R^1c, R^1d are independently H, or Ci-C₄-alkyl;

R^2a is halogen, halomethyl, or halomethoxy;

R^2b, R^2c are independently H , or as defined for R^2a;

HE is a fivemembered unsaturated heterocycle comprising 1 ,

2,

3 or 4 heteroatoms selected from N(0)_n, O and S(0)_m as ring members, wherein the carbon ring members are unsubstituted or substituted with R^A; and any nitrogen ring members are substituted with R^N;

n is 0, or 1 ;

m is 0, 1 , or 2;

R^A is independently halogen, CN, NO2, Ci-C₄-alkyl, Ci-C₄-haloalkyl, C2-C₄-alke- nyl, C2-C₄-haloalkenyl, C2-C₄-alkynyl, C2-C₄-haloalkynyl, C3-C6-cycloalkyl, C3- C6-halocycloalkyl, Ci-C₄-alkoxy, Ci-C₄-haloalkoxy, S(0)_m-Ci-C₄-alkyl, S(0)_m- Ci-C₄-haloalkyl, Ci-C₄-haloalkylcarbonyl, C(=0)R³³, C(=0)OR³³,

C(=0)N(R³¹)R³²; or phenyl, which is unsubstituted or substituted with halogen, CN , or Ci-C₄-alkyl or Ci-C₂-haloalkyl;

m is 0, 1 , or 2;

R^N is independently H, Ci-C₄-alkyl, Ci-C₄-haloalkyl, C2-C₄-alkenyl, C2-C₄-halo- alkenyl, C2-C₄-alkynyl, C2-C₄-haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocyclo- alkyl, Ci-C₄-haloalkylcarbonyl, C(=0)R³³, C(=0)OR³³, C(=0)N(R³ )R³²; or phenyl, which is unsubstituted or substituted with halogen, CN, or Ci-C₄-alkyl or Ci-C2-haloalkyl;

R³ is H, halogen, CN, N0₂, OH, N(R³ )R³², Ci-Ce-alkyl, C₃-C₇-cycloalkyl, C₂-C₆-alkenyl, C3-C7-cycloalkenyl, C2-C6-alkynyl, Ci-C6-alkoxy, Ci-C6-haloalkyl, C3-C7-halocycloal- kyl, C2-C6-haloalkenyl, C3-C7-halocycloalkenyl, Ci-C6-haloalkoxy, S(0)_m-Ci-C6-alkyl, or S(0)m-Ci-C6-haloalkyl, in which aliphatic groups are unsubstituted, partially or fully substituted with one or more R^a;

R³¹ is H, or Ci-Ce-alkyl,

R³² is H, Ci-Ce-alkyl, Ci-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆- alkynyl, C2-C6-haloalkynyl, or C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C3-C6- cycloalkylmethyl, or C3-C6-halocycloalkylmethyl which rings are unsubstituted or substituted with a CN; R^a is CN, N₃, N0₂, SCN, SF₅, Si(Ci-C₄-alkyl)₃, OR³³, OSO2R³³, S(0)_nR³³,

N(R³ )R³², C(=0)N(R³ )R³², C(=S)N(R³ )R³², C(=0)OR³³, CH=NOR³³, C₃-C₈- cycloalkyl, Cs-Cs-halocycloalkyl, which cyclic moieties may be substituted with R³⁴; phenyl which is unsubstituted or substituted with one or more R^A; and 3- to 7-membered saturated, partially or fully unsaturated heterocycle comprising

1 , 2 or 3 heteroatoms O, N(0)_n or S(0)_m as ring members, which heterocycle is unsubstituted or substituted with one or more R^A,

R³³ H, Ci-Ce-alkyl, Ci-C₆-haloalkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl, CH₂-CN, C₃-C₆- cycloalkyl, C3-C6-halocycloalkyl, C3-C6-cycloalkylmethyl, C3-C6-halocyclo- alkylmethyl, phenyl and hetaryl which aromatic rings are unsubstituted or partially or fully substituted with R^A;

R³⁴⁴ is independently OH, CN, Ci-C₂-alkyl, or Ci-C₂-haloalkyl;

n is O, or 1 ;

R⁴ is idependently as defined for R³;

A is A1 : -C(=U)NR⁵R⁶, or

A2: -(CH₂)_nNR⁵C(=U)R⁶; wherein

U is O, or S; and

R⁵ is H, OH, C(=0)R³¹, C(=0)OR³¹, CN, Ci-Ce-alkyl, Ci-C₆-alkoxy, C₂-C₄-alkenyl, C₂-

C₄-alkynyl, Cs-Cs-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, N(R³¹)R³², phenyl or saturated, partially or fully unsaturated heterocycle, which groups are unsubstituted or substituted with one or more R^a; and wherein the rings are bonded directly or via Ci- C₄-alkyl spacer;

R⁶ is H, Ci-Ce-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₃-C₈-cycloalkyl, C₃-C₈-cycloalkyl-Ci-

C₄-alkyl, Ci-C6-alkylcarbonyl, Ci-C6-alkoxycarbonyl, phenyl or saturated, partially or fully unsaturated heterocycle, which groups are unsubstituted or substituted with one or more R^aa; and wherein the rings are bonded directly or via Ci-C₄-alkyl spacer;

R^aa is halogen, CN, Ci-Ce-alkyl, OR³¹, C(=NOR³¹)R³²; C(=0)N(R³ )R³²,

C(=S)N(R³¹)R³², or C(=0)OR³¹; or two R^aa bound to the same C-atom form together C₃-C6-cycloalkyl;

R⁵¹,R⁵²are independently H, Ci-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Cs-Cs-cycloalkyl, C3-Cs-cycloalkyl-Ci-C₄-alkyl, phenyl or saturated, partially or fully unsatu- rated heterocycle, which groups are unsubstituted or substituted with one or more halogen, CN, NO2; and wherein the rings are bonded directly or via Ci- C₄-alkyl spacer;

and the N-oxides, stereoisomers and agriculturally or veterinarily acceptable salts thereof. Compounds of formula I according to claim 1 , which correspond to formula I.H1.1 ^*.

3. Compounds of formula I according to claim 1 , which correspond to formula I.H1.2^*.

4. Compounds of formula I according to claim 1 , which correspond to formula I.H1 .3^*.

Compounds of formula I according to any of claims 1 to 4, wherein

R^1a is H or halogen, and R^1b is halogen.

Compounds of formula I according to any of claims 1 to 5, wherein

T¹, T², and T³ are C-R⁴, and R³ and R⁴ are H, halogen, CN, OH, NH₂, Ci-C₄-alkyl, cyclo- propyl, or Ci-C₄-haloalkyl.

Compounds of formula I according to any of claims 1 to 6, wherein A is a group A1.

Compounds of formula I according to claim 7, wherein A1 is -C(=0)NHR⁶.

Compounds of formula I according to any of claims 1 to 8, wherein R⁶ is Ci-C6-alkyl, benzyl, or C3-C6-cycloalkyl or phenyl which rings are unsubstituted or substituted with CN, halogen and/or Ci-C₄-haloalkyl.

An agricultural or veterinary composition comprising at least one compound according to any one of claims 1 to 9 and/or at least one agriculturally or veterinarily acceptable salt thereof, and at least one inert liquid and/or solid agriculturally or veterinarily acceptable carrier. An agricultural composition for combating animal pests comprising at least one compound as defined in any of claims 1 to 9 and at least one inert liquid and/or solid acceptable carrier and, if desired, at least one surfactant.

A method for combating or controlling invertebrate pests, which method comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound as defined in any one of claims 1 to 9.

A method for protecting growing plants from attack or infestation by invertebrate pests, which method comprises contacting a plant, or soil or water in which the plant is growing, with a pesticidally effective amount of at least one compound as defined in any of claims 1 to 9.

Seed comprising a compound as defined in any of claims 1 to 9, or the enantiomers, dia- stereomers or salts thereof, in an amount of from 0.1 g to 10 kg per 100 kg of seed.

A method for treating or protecting an animal from infestation or infection by invertebrate pests which comprises bringing the animal in contact with a pesticidally effective amount of at least one compound of the formula I as defined in any of claims 1 to 9, a stereoisomer thereof and/or at least one veterinarily acceptable salt thereof.