Pesticidally active dihydro-benzoxazinone compounds

Abstract

Compounds of formula (I), wherein the substituents are as defined in claim 1, and the agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds, can be used as insecticides.

Description

109934 | 83191 FF 1 PESTICIDALLY ACTIVE DIHYDRO-BENZOXAZINONE COMPOUNDSTECHNICAL FIELD

[0001] The present invention relates to pesticidally active dihydro-benzoxazinone compounds, e.g. asactive ingredients, which have pesticidal activity, in particular insecticidally active dihydro-benzoxazinonecompounds. The invention also relates to the preparation of these dihydro-benzoxazinone compounds, tointermediates useful in the preparation of these dihydro-benzoxazinone compounds, to the preparation ofthese intermediates, to agrochemical compositions which comprise at least one of these dihydro-benzoxazinone compounds, to preparation of these compositions and to the use of these dihydro-benzoxazinone compounds or compositions in agriculture or horticulture, for controlling animal pests,including arthropods, and in particular insects or representatives of the order Acarina. BACKGROUND

[0002] WO 2023 / 037249, WO 2023 / 285175, WO 2022 / 157188 and WO 2019 / 197468 describe certainfused heterobicyclic carboxamide derivatives with pesticidal activity. WO 2017 / 123860 describes dihydro-benzoxazinone carboxamide derivatives as ROCK (rho-associated protein kinase) inhibitors.WO 2021 / 069567, WO 2021 / 069575, WO 2019 / 201835, and WO 2019 / 197468 describe some heteroaryI-triazole and heteroaryI- pyrazine compounds as pesticides. WO 2025 / 045835, WO 2025 / 045837 andWO 2025 / 045838 also disclose heteroaryI-triazole and heteroaryI- pyrazine compounds as pesticides.BRIEF SUMMARY

[0003] It has now surprisingly been found that certain novel 1,4-dihydro-3,1-benzoxazin-2-onecompounds have pesticidal activity. More specifically, certain novel 2-oxo-1,4-dihydro-3,1-benzoxazine-8-carboxamides (or 1,4-dihydro-2-oxo-2H-3,1-benzoxazine-8-carboxamide derivatives) and aza analoguesthereof, have pesticidal activity.

[0004] Hence, the present invention accordingly relates, in a first aspect, to a compound of the formula(I):wherein A1is CH or N;109934 | 83191 FF 2, where the staggered line represents theconnection of Q to the rest of compound of the formula (I); R1is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2- C6alkynyl, C3-C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; R2a and R2a' are, independently from each other, hydrogen, halogen, cyano, C1-C3alkyl, orC3-C4cycloalkyl; or R2aand R2a'form a C3-C6cycloalkyl group together with the carbon atom they are attached to; R2bis hydrogen, halogen, C1-C3haloalkyl, C1-C3haloalkoxy, cyano, SF5, C1-C3alkylsulfanyl, C1-C3alkylsulfinyl, C1-C3alkylsulfonyl, C1-C3haloalkylsulfanyl, C1-C3haloalkylsulfinyl, C1- C3haloalkylsulfonyl, C1-C5cyanoalkyl, C1-C5cyanoalkoxy, C3-C4cycloalkylC1-C2alkyl, C3- C4cycloalkylC1-C2haloalkyl, C3-C4cycloalkylcarbonyl, or C3-C4cycloalkyl optionally substituted with one or two substituents independently selected from the group consisting of halogen, -CN, C1-C3alkyl, and C1-C3haloalkyl; R3is C1-C3alkyl or C1-C3haloalkyl; R4is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4b; or R4is oxo-pyridazinyl optionallyN-substituted with a single substituent R4c;R4a is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, thiazolyl, pyrazol-1-yl, or N-linked triazolyl,each of which, independently of each other, is optionally substituted with a single substituent R4b; orR4a is oxo-pyridazinyl optionally N-substituted with a single substituent R4c;R4b is hydrogen, halogen, cyano, hydroxy, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, -C(O)NR10R11, -N(R11)C(O)OR10, or -N(R11)C(O)R10; R4cis C1-C3alkyl, C1-C3haloalkyl, allyl, propargyl, or C3-C6cycloalkylC1-C4alkyl; R5, R5aand R5bare independently hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3- C4cycloalkyl; R10is hydrogen, C1-C3alkyl, C3-C6cycloalkyl, C3-C4cycloalkylC1-C2alkyl, C1-C3cyanoalkyl,cyanoC3-C6cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C4haloalkyl;R11 is hydrogen, hydroxy, C1-C3alkyl, C3-C4cycloalkyl, cyanoC3-C6cycloalkyl, C1-C3cyanoalkyl, C1-C3alkoxyC1-C3alkyl, C1-C3haloalkyl, or C1-C3alkoxy; X is an oxygen atom or a sulfur atom; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of thecompound of formula (I).

[0005] The present invention also provides a method of preparation of compounds of formula (I) as wellas intermediate compounds useful in the preparation of compounds of formula (I).109934 | 83191 FF 3

[0006] In a second aspect, the present invention makes available a composition comprising a compoundof formula (I) as defined in the first aspect, one or more auxiliaries and diluent, and optionally one or more other active ingredient.

[0007] In a third aspect, the present invention makes available a method of combating and controllingpests, such as insects, acarines, nematodes, or molluscs, which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest a pesticidally, such as insecticidally, acaricidally, nematicidally, or molluscicidally, effective amount of a compound as defined in the first aspect or of a composition as defined in the second aspect.

[0008] In a fourth aspect, the present invention makes available a method for the protection of plantpropagation material from the attack by a pest, such as insects, acarines, nematodes, or molluscs, which comprises treating the propagation material or the site where the propagation material is planted, with aneffective amount of a compound of formula (I) as defined in the first aspect or of a composition as definedin the second aspect.

[0009] In a fifth aspect, the present invention makes available a plant propagation material, such as aseed, comprising, or treated with, or coated with, or adhered thereto, a compound of formula (I) as definedin the first aspect or of a composition as defined in the second aspect.

[0010] The present invention in a further aspect provides a method of controlling parasites in or on ananimal in need thereof comprising administering an effective amount of a compound of formula (I) as defined in the first aspect. The present invention further provides a method of controlling ectoparasites onan animal in need thereof comprising administering an effective amount of a compound of formula (I) asdefined in the first aspect. The present invention further provides a method for preventing and / or treatingdiseases transmitted by ectoparasites comprising administering an effective amount of a compound offormula (I) as defined in the first aspect, to an animal in need thereof.DETAILED DESCRIPTION

[0011] Compounds of formula (I) which have at least one basic centre can form, for example, acidaddition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as C1-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid,malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, forexample ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or withorganic sulfonic acids, such as C1-C4alkane- or arylsulfonic acids which are unsubstituted or substituted,for example by halogen, for example methane- or p-toluenesulfonic acid. Compounds of formula (I) whichhave at least one acidic group can form, for example, salts with bases, for example mineral salts such asalkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts withammonia or an organic amine, such as mor-pholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.

[0012] In each case, the compounds of formula (I) according to the invention are in free form, in oxidizedform as a N-oxide or in salt form, e.g. an agronomically usable salt form.109934 | 83191 FF 4

[0013] N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containingheteroaromatic compounds. They are described for instance in the book "Heterocyclic N-oxides" by A.Albini and S. Pietra, CRC Press, Boca Raton 1991.

[0014] The compounds of formula (I) according to the invention also include hydrates which may beformed during the salt formation.

[0015] The term "C1-Cnalkyl" as used herein refers to a saturated straight-chain or branched hydrocarbonradical attached via any of the carbon atoms having 1 to n carbon atoms, for example, any one of the radicals methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1- ethylpropyl, n-hexyl, n-pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3- methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, or 1-ethyl-2-methylpropyl.

[0016] The term "C1-Cnhaloalkyl" as used herein refers to a straight-chain or branched saturated alkylradical attached via any of the carbon atoms having 1 to n carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these radicals may be replaced by fluorine, chlorine, bromine and / or iodine, i.e., for example, any one of chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2- chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3- fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3- pentafluoropropyl,heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2- bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl. Accordingly "C1-C2fluoroalkyl" refers to a C1-C2alkyl radical which carries 1, 2, 3, 4, or 5 fluorine atoms, for example, any one of difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2- tetrafluoroethyl or pentafluoroethyl.

[0017] The term "C1-Cnalkoxy" as used herein refers to a straight-chain or branched saturated alkylradical having 1 to n carbon atoms (as mentioned above) which is attached via an oxygen atom, i.e., for example, any one of the radicals methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy,2-methylpropoxy or 1,1-dimethylethoxy. The term "haloC1-Cnalkoxy" as used herein refers to a C1-Cnalkoxyradical where one or more hydrogen atoms on the alkyl radical is replaced by the same or different haloatom(s) - examples include trifluoromethoxy, 2-fluoroethoxy, 3-fluoropropoxy, 3,3,3-trifluoropropoxy, 4-chlorobutoxy.

[0018] The term "C1-Cncyanoalkyl" as used herein refers to a straight chain or branched saturated alkylradical having 1 to n carbon atoms (as mentioned above), where one of the hydrogen atoms in these radicals is replaced by a cyano group: for example, cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, 3- cyanopropyl, 1-(cyanomethyl)-2-ethyl, 1-(methyl)-2-cyanoethyl, 4-cyanobutyl, and the like.

[0019] The term "C3-Cncycloalkyl" as used herein refers to a saturated monocyclic hydrocarbon radicalattached via any of the ring carbon atoms and having 3 to n carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.109934 | 83191 FF 5

[0020] The term "cyanoC3-Cncycloalkyl" as used herein refers to a C3-Cncycloalkyl where one of thehydrogen atoms in these radicals is replaced by a cyano group. For example, a cyanoC3-C4cycloalkyl refers to a cyclopropyl or a cyclobutyl radical where one of the hydrogen atoms in these radicals is replaced by a cyano group.

[0021] The term "C3-Cncycloalkylcarbonyl" as used herein refers to a C3-Cncycloalkyl radical bonded toa carbonyl (C=O) group, which carbonyl group is connected to the rest of the molecule. Similarly the terms "C1-Cnalkylcarbonyl", "C1-Cnalkoxycarbonyl", "phenyloxycarbonyl" and "benzyloxycarbonyl" as used herein refers to an C1-Cnalkyl, C1-Cnalkoxy, phenyloxy and benzyloxy group bonded to a carbonyl (C=O) group, which carbonyl group is connected to the rest of the molecule.

[0022] The term "C3-C4cycloalkylC1-C2alkyl" as used herein refers to a cyclopropyl or cyclobutyl radicalbonded via a methylene or ethylene bridge to the rest of the molecule. When the C3-C4cycloalkylC1-C2alkylradical is substituted, the substituent(s) can be bonded to the C3-C4cycloalkyl radical and / or to the C1- C2alkyl bridge.

[0023] The term "C1-Cnalkylsulfanyl" as used herein refers to a C1-Cnalkyl moiety linked through a sulfuratom. Similarly, the term "C1-Cnhaloalkylthio" or "C1-Cnhaloalkylsulfanyl" as used herein refers to a C1-Cnhaloalkyl moiety linked through a sulfur atom. Similarly, the term "C3-Cncycloalkylsulfanyl" refers to 3-nmembered cycloalkyl moiety linked through a sulfur atom.

[0024] The term "C1-Cnalkylsulfinyl" as used herein refers to a C1-Cnalkyl moiety linked through the sulfuratom of the S(=O) group. Similarly, the term "C1-Cnhaloalkylsulfinyl " or "C1-Cnhaloalkylsulfinyl" as usedherein refers to a C1-Cnhaloalkyl moiety linked through the sulfur atom of the S(=O) group. Similarly, theterm "C3-Cncycloalkylsulfinyl" refers to 3-n membered cycloalkyl moiety linked through the sulfur atom ofthe S(=O) group.

[0025] The term "C1-Cnalkylsulfonyl" as used herein refers to a C1-Cnalkyl moiety linked through thesulfur atom of the S(=O)2 group. Similarly, the term "C1-Cnhaloalkylsulfonyl " or "C1-Cnhaloalkylsulfonyl" asused herein refers to a C1-Cnhaloalkyl moiety linked through the sulfur atom of the S(=O)2 group. Similarly,the term "C3-Cncycloalkylsulfonyl" refers to 3-n membered cycloalkyl moiety linked through the sulfur atomof the S(=O)2 group.

[0026] The term "C2-Cnalkenyl" as used herein refers to a straight or branched alkenyl chain having fromtwo to n carbon atoms and one or two double bonds, for example, ethenyl, prop-1-enyl, but-2-enyl.

[0027] The term "C2-Cnalkynyl" as used herein refers to a straight or branched alkynyl chain having fromtwo to n carbon atoms and one triple bond, for example, ethynyl, prop-2-ynyl, but-3-ynyl.

[0028] Halogen or "halo" is generally fluorine, chlorine, bromine or iodine. This also applies,correspondingly, to halogen in combination with other meanings, such as haloalkyl.

[0029] The term "optionally substituted" as used herein means that the group referenced is eitherunsubstituted or is substituted by a designated substituent, for example, "C3-C4cycloalkyl is optionally substituted with 1 or 2 halo atoms" means C3-C4cycloalkyl, C3-C4cycloalkyl substituted with 1 halo atom and C3-C4cycloalkyl substituted with 2 halo atoms.

[0030] As used herein, the term "controlling" refers to reducing the number of pests, eliminating pestsand / or preventing further pest damage such that damage to a plant or to a plant derived product is reduced.

[0031] As used herein, the term "pest" refers to insects, and molluscs that are found in agriculture,horticulture, forestry, the storage of products of vegetable origin (such as fruit, grain and timber); and those109934 | 83191 FF 6pests associated with the damage of man-made structures. The term pest encompasses all stages in thelife cycle of the pest.

[0032] As used herein, the term "effective amount" refers to the amount of the compound, or a saltthereof, which, upon single or multiple applications provides the desired effect.

[0033] An effective amount is readily determined by the skilled person in the art, by the use of knowntechniques and by observing results obtained under analogous circumstances. In determining the effective amount a number of factors are considered including, but not limited to: the type of plant or derived product to be applied; the pest to be controlled & its lifecycle; the particular compound applied; the type of application; and other relevant circumstances.

[0034] As one of ordinary skill in the art will appreciate, compounds of formula (I) contain a stereogeniccentre which is indicated with an asterisk in formula (I*) below:where A1, R1, R2a, R2a', R2b, R3, Q and X are as defined in the first aspect.

[0035] The present invention contemplates both racemates and individual enantiomers. Compounds offormula (I') having a preferred stereochemistry are set out below:

[0036] Particularly preferred compounds of the present invention are compounds of formula (I’), whereA1, R1, R2a, R2a', R2b, R3, Q and X are as defined in the first aspect, and stereoisomers, enantiomers,tautomers and N-oxides of the compounds of formula (I’), and agrochemically acceptable salts thereof.

[0037] Particularly preferred compounds of formula (I’) include compounds of formula (I’a) as shownbelow, where X is O, and A1, R1, R2a, R2a', R2b, R3 and Q are as defined in the first aspect, andstereoisomers, enantiomers, tautomers and N-oxides of the compounds of formula (I’a), andagrochemically acceptable salts thereof:109934 | 83191 FF 7

[0038] Compounds of the formula (I), (I*), (I*a), and preferred compounds thereof of the formula (I’) and(I’a), where A1, R1, R2a, R2a', R2b, R3, Q and X are as defined in the first aspect, may exist in differenttautomeric forms, represented as the fragment (I”-1), the fragment (I”-2), and, when at least one of R2aor R2a’is hydrogen, the fragment (I”-3):where the staggered line represents the connection to the remainder of said compounds ofthe formula (I), (I*), (I*a), (I’) and (I’a). This invention covers all such tautomers and mixtures thereofin all proportions.

[0039] Particularly preferred compounds of the present invention are compounds of formula (I), (I*), (I*a),and preferred compounds thereof of the formula (I’) and (I’a), where A1 is CH, and where R1, R2a, R2a', R2b,R3, Q and X are as defined in the first aspect. These compounds may exist in different tautomeric forms asrepresented below, with the fragments (I’’’-1), the fragment (I’’’-2), and, when at least one of R2a or R2a’ ishydrogen, the fragment (I’’’-3):

[0040] More preferably, compounds of the present invention are compounds of formula (I), (I*), (I*a), andpreferred compounds thereof of the formula (I’) and (I’a), where A1 is CH, X is oxygen. and where R1, R2a,R2a', R2b, R3, and Q are as defined in the first aspect. These compounds may exist in different tautomeric forms as represented below, with the fragments (Iiv-1), the fragment (Iiv-2), and, when at least one of R2aor R2a’is hydrogen, the fragment (Iiv-3):109934 | 83191 FF 8

[0041] Embodiments according to the invention are provided as set out below.

[0042] In an embodiment of each aspect of the invention, A1 is N. In another embodiment of each aspectof the invention, A1is CH. In a preferred embodiment of each aspect of the invention, A1is CH.

[0043] In an embodiment of each aspect of the invention, X is O (i.e. an oxygen atom). In an embodimentof each aspect of the invention, X is S (i.e. a sulfur atom). Preferably, in embodiments of each aspect of theinvention, X is O.

[0044] In an embodiment of each aspect of the invention, R1 is as follows:A. R1 is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; or B. R1 is hydrogen, methyl, ethyl, or cyclopropyl-methyl; orC. R1 is hydrogen, methyl, or cyclopropylmethyl; orD. R1 is hydrogen or methyl; orE. R1 is methyl; orF. R1 is hydrogen.

[0045] In preferred embodiments of each aspects of the invention, R1 is hydrogen, methyl, orcyclopropylmethyl; or R1is hydrogen or methyl. Most preferably, R1is hydrogen.

[0046] In an embodiment of each aspect of the invention, R2a is as follows:A. R2a is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; orB. R2a is hydrogen, halogen, or C1-C3alkyl; orC. R2a is halogen, -CN, or C1-C3alkyl; orD. R2a is hydrogen, methyl, ethyl, or fluoro; orE. R2a is methyl, ethyl, or fluoro; orF. R2a is fluoro or methyl.

[0047] In an embodiment of each aspect of the invention, R2a' is as follows:A. R2a' is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; orB. R2a' is hydrogen, halogen, or C1-C3alkyl; orC. R2a' is halogen, cyano, or C1-C3alkyl; orD. R2a' is hydrogen, methyl, ethyl, or fluoro; orE. R2a' is methyl, ethyl, or fluoro; orF. R2a' is fluoro or methyl.

[0048] In preferred embodiments of each aspect of the invention:A. R2a and R2a' are, independently from each other, hydrogen, halogen, cyano, C1-C3alkyl, orC3-C4cycloalkyl; or R2aand R2a'form a C3-C6cycloalkyl group together with the carbon atom they are attached to; or109934 | 83191 FF 9 B. R2a and R2a' are both hydrogen, halogen, cyano, C1-C3alkyl, or C3-C4cycloalkyl; R2a and R2a'form a C3-C6cycloalkyl group together with the carbon atom they are attached to; or C. R2a and R2a' are, independently from each other, hydrogen, halogen, or C1-C3alkyl; orD. R2a and R2a' are both hydrogen, halogen or C1-C3alkyl; or R2a and R2a' form a cyclopropyl ora cyclobutyl together with the carbon atom they are attached to; or E. R2a and R2a' are both fluoro or methyl, or they form a cyclopropyl together with the carbonatom they are attached to; or F. R2a and R2a' form a cyclopropyl together with the carbon atom they are attached to; orG. R2a and R2a' are both fluoro or methyl.

[0049] In preferred embodiments of each aspect of the invention, R2a and R2a' are identically selected,or they form a C3-C6cycloalkyl group together with the carbon atom they are attached to. For instance, R2aand R2a'are both hydrogen, fluoro, methyl, or ethyl, or R2aand R2a'form a cyclopropyl together with the carbon atom they are attached to. More preferably, R2aand R2a'are methyl.

[0050] In an embodiment of each aspect of the invention, R2b is as follows:A. R2b is hydrogen, halogen, C1-C3haloalkyl, C1-C3haloalkoxy, cyano, SF5, C1-C3alkylsulfanyl,C1-C3alkylsulfinyl, C1-C3alkylsulfonyl, C1-C3haloalkylsulfanyl, C1-C3haloalkylsulfinyl, C1- C3haloalkylsulfonyl, C1-C5cyanoalkyl, C1-C5cyanoalkoxy, C3-C4cycloalkylC1-C2alkyl, C3-C4cycloalkylC1-C2haloalkyl, C3-C4cycloalkylcarbonyl, or C3-C4cycloalkyl optionally substitutedwith one or two substituents independently selected from the group consisting of halogen, -CN,C1-C3alkyl, and C1-C3haloalkyl; or B. R2b is hydrogen, halogen, C1-C3haloalkyl, C1-C3haloalkoxy, cyano, SF5, C1-C3alkylsulfanyl,C1-C3alkylsulfinyl, C1-C3alkylsulfonyl, C1-C3haloalkylsulfanyl, C1-C3haloalkylsulfinyl, C1- C3haloalkylsulfonyl, C1-C5cyanoalkyl, C1-C5cyanoalkoxy, C3-C4cycloalkylC1-C2alkyl, C3-C4cycloalkylC1-C2haloalkyl, C3-C4cycloalkylcarbonyl, cyclopropyl, or cyclopropyl substituted withone or two substituents independently selected from the group consisting of halogen, -CN,methyl, and trifluoromethyl; or C. R2b is halogen, C1-C3haloalkyl, C1-C3haloalkoxy, C1-C3alkylsulfonyl, C1-C3haloalkylsulfonyl,C1-C5cyanoalkyl, C3-C4cycloalkylC1-C2alkyl, or cyclopropyl; or D. R2b is halogen, C1-C3haloalkyl, C1-C3haloalkylsulfonyl, or cyclopropyl; orE. R2b is chloro, bromo, iodo, difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, trifluoromethylsulfonyl, or cyclopropyl; or F. R2b is chloro, bromo, iodo, cyclopropyl, difluoromethyl, or trifluoromethyl; orG. R2b is chloro, bromo, cyclopropyl, difluoromethyl, or trifluoromethyl; orH. R2b is chloro, bromo, cyclopropyl, or trifluoromethyl; orI. R2b is chloro or trifluoromethyl; orJ. R2b is chloro, bromo, cyclopropyl, difluoromethyl, or trifluoromethyl; orK. R2b is chloro, cyclopropyl, difluoromethyl, or trifluoromethyl; orL. R2b is chloro, difluoromethyl, or trifluoromethyl; orM. R2b is difluoromethyl or trifluoromethyl; orN. R2b is chloro, bromo, cyclopropyl, difluoromethyl, trifluoromethyl, or difluoromethoxy.109934 | 83191 FF 10

[0051] In preferred embodiments of each aspect of the invention, R2b is chloro, bromo, iodo, cyclopropyl,difluoromethyl, or trifluoromethyl, such as R2b is chloro, difluoromethyl, or trifluoromethyl, or R2b is chloro,or trifluoromethyl. For instance, R2b is difluoromethyl or trifluoromethyl. In other preferred embodiments ofeach aspect of the invention, R2bis chloro, bromo, cyclopropyl, difluoromethyl, trifluoromethyl, ordifluoromethoxy. In other preferred embodiments of each aspect of the invention, R2b is trifluoromethyl.

[0052] In an embodiment of each aspect of the invention, R3 is as follows:A. R3 is C1-C3alkyl or C1-C3haloalkyl; orB. R3 is methyl or trifluoromethyl; orC. R3 is methyl.

[0053] In preferred embodiments of each aspect of the invention, R3 is methyl.

[0054] In an embodiment of each aspect of the invention, Q is Qa. In embodiments where Q is Qa, R5 isas follows: A. R5 is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; orB. R5 is hydrogen, halogen, or C1-C3alkyloxy; orC. R5 is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; orD. R5 is hydrogen, halogen, or C1-C3alkyloxy; orE. R5 is hydrogen, halogen, or C1-C3alkyl; orF. R5 is hydrogen, chloro, bromo, methyl, cyclopropyl, methoxy, 2-methoxyethoxy,difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methylcarbonyl, methoxycarbonyl, or 1,3,4-oxadiazol-2-yl; or G. R5 is hydrogen, bromo, iodo, methoxy, 2-methoxyethoxy; orH. R5 is hydrogen, bromo, iodo, methyl, ethyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, or 2-methoxyethoxy; or I. R5 is hydrogen; orJ. R5 is hydrogen, bromo, iodo, methyl, ethyl, cyclopropyl, methoxy, 2-methoxyethoxy; orK. R5 is hydrogen, bromo, methyl, ethyl, cyclopropyl, methoxy, or ethoxy; orL. R5 is hydrogen, bromo, methyl, ethyl, cyclopropyl, or methoxy.

[0055] In preferred embodiments, R5 is as follows:A. R5 is hydrogen, bromo, iodo, methyl, ethyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, or 2-methoxyethoxy; or B. R5 is hydrogen, bromo, methyl, cyclopropyl, methoxy, or ethoxy; orC. R5 is hydrogen, cyclopropyl, or methoxy; orD. R5 is hydrogen; orE. R5 is hydrogen, bromo, methyl, ethyl, cyclopropyl, or methoxy.

[0056] For instance, Qa is selected from Qa-1 to Qa-17109934 | 83191 FF 11109934 | 83191 FF 12

[0057] As an example, Qa is Qa-1, Qa-4, Qa-5 Qa-6, Qa-7, Qa-10, Qa-15, or Qa-17; Qa is Qa-1, Qa-4, Qa-5Qa-6, Qa-7, Qa-10, or Qa-15; or Qais selected from Qa-1, Qa-6, Qa-7, Qa-10, and Qa-15. Preferably, Q is Qa- 1, Qa-4, Qa-5, Qa-10, Qa-15, or Qa-17; or Q is Qa-1, or Qa-15. Most preferably, Q is Qa-1.

[0058] In another embodiment of each aspect of the invention, Q is Qb. In embodiments where Q is Qb,R5aand R5bare as follows: A. R5a is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; orB. R5a is hydrogen, halogen, or C1-C3alkyloxy; orC. R5a is hydrogen, halogen, or C1-C3alkyl; orD. R5a is hydrogen, chloro, fluoro, methyl, cyclopropyl, trifluoromethyl, methoxy,difluoromethoxy, or cyano; or E. R5a is hydrogen, chloro, fluoro, cyclopropyl, trifluoromethyl, methoxy, or difluoromethoxy; orF. R5a is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy; orG. R5a is hydrogen;and A. R5b is hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; orB. R5b is hydrogen, halogen, or C1-C3alkyloxy; orC. R5b is hydrogen, halogen, or C1-C3alkyl; orD. R5b is hydrogen, chloro, fluoro, or methoxy; orE. R5b is hydrogen, fluoro, or methoxy; orF. R5b is hydrogen.

[0059] In preferred embodiments where Q is Qb:A. R5a is hydrogen, chloro, fluoro, cyclopropyl, trifluoromethyl, methoxy, or difluoromethoxy andR5bis hydrogen, fluoro, or methoxy; or B. R5a is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy, and R5b is hydrogen,chloro, fluoro, or methoxy; or C. R5a is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy, and R5b is hydrogen,fluoro, or methoxy; or D. R5a is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy and R5b is hydrogen;or E. R5a is hydrogen, and R5b is hydrogen, fluoro, or methoxy; orF. R5a and R5b are hydrogen.

[0060] For instance, Qb is selected from Qb-1 to Qb-13:109934 | 83191 FF 13Qb-13

[0061] As an example, Qb is Qb-1, Qb-2, Qb-3, Qb-5, Qb-6, Qb-8, Qb-9, Qb-10, or Qb-11; or Qb is selectedfrom Qb-1, Qb-2, Qb-3, Qb-5, Qb-8, Qb-9, Qb-10, and Qb-11. For instance, Qbis Qb-1, Qb-2, Qb-3, Qb-5, Qb- 8, Qb-10, or Qb-11. Preferably, Qbis Qb-1, Qb-3, Qb-5, Qb-10, or Qb-11. Most preferably, Qbis Qb-1.

[0062] In embodiments where Q is Qa, R4 is as follows:A. R4 is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently ofeach other, is optionally substituted with a single substituent R4b; or R4is oxo-pyridazinyl optionally N-substituted with a single substituent R4c; or109934 | 83191 FF 14B. R4 is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, Qc-7, Qc-8, or Qc-9; orC. R4 is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, or Qc-9; orD. R4 is Qc-1, Qc-2, Qc-3, Qc-4, or Qc-9; orE. R4 is Qc-1, Qc-2, or Qc-3; orF. R4 is 5-cyano-2-pyridyl, 5-carbamoyl-2-pyridyl, pyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6- (methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 5-bromopyrazin-2-yl, 6-methoxypyridazin-3- yl, 1-methyl-6-oxo-pyridazin-3-yl, 5-cyanothiazol-2-yl, 5-carbamoyl-thiazol-2-yl; orG. R4 is 5-cyano-2-pyridyl, pyrimidin-2-yl, 5-bromopyrimidin-2-yl, 5-bromopyrazin-2-yl, 6-cyanopyrimidin-4-yl, 5-cyanothiazol-2-yl, 6-carbamoyl-pyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 1-methyl-6-oxo-pyridazin-3-yl, pyrazin-2-yl, 5-carbamoyl-2- pyridyl; orH. R4 is pyrimidin-2-yl, 5-cyano-2-pyridyl, 5-bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, or 6-carbamoylpyrimidin-4-yl; orI. R4 is 5-cyano-2-pyridyl, 5-carbamoyl-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 5- bromopyrazin-2-yl, 5-carbamoylpyrazin-2-yl, 6-methoxypyridazin-3-yl, 1-methyl-6-oxo-pyridazin- 3-yl, 5-cyanothiazol-2-yl, 5-carbamoyl-thiazol-2-yl; orJ. R4 is pyrimidin-2-yl, 5-cyano-2-pyridyl, 5-carbamoyl-2-pyridyl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-carbamoylpyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, 6-cyanopyrimidin-4- yl, pyrazin-2-yl, 5-bromopyrazin-2-yl, 5-carbamoylpyrazin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, or 5-cyanothiazol-2-yl; orK. R4 is 5-cyano-2-pyridyl, 5-carbamoyl-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl,109934 | 83191 FF 15 6-(methylcarbamoyl)pyrimidin-4-yl, pyrazin-2-yl, 5-bromopyrazin-2-yl, 5-carbamoylpyrazin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, or 5-cyanothiazol-2-yl; or L. R4 is 5-cyano-2-pyridyl, 5-carbamoyl-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 5- chloropyrazin-2-yl, 5-bromopyrazin-2-yl, 5-carbamoylpyrazin-2-yl, 6-methoxypyridazin-3-yl, 1- methyl-6-oxo-pyridazin-3-yl, 5-cyanothiazol-2-yl, 5-carbamoyl-thiazol-2-yl, and R4ais 5-cyano-2- pyridyl or 5-carbamoyl-2-pyridyl; or M. R4 is 5-cyano-2-pyridyl, 5-carbamoyl-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, pyrazin-2-yl, 5-chloropyrazin-2-yl, 5-bromopyrazin-2-yl, 5- carbamoylpyrazin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, 5-cyanothiazol-2-yl, or 5- carbamoylthiazol-2-yl.

[0063] In preferred embodiments of each aspect of the invention, R4 is Qc-1, Qc-2, Qc-3, Qc-4, Qc-6, orQc-9, or R4is Qc-1, Qc-2, Qc-3, Qc-4, or Qc-9. More preferably, R4is Qc-1, Qc-2, or Qc-3. For instance, R4is 5-cyano-2-pyridyl, 5-carbamoyl-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5- bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4- yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 5-bromopyrazin-2-yl, 5-carbamoylpyrazin-2-yl, 6- methoxypyridazin-3-yl, 1-methyl-6-oxo-pyridazin-3-yl, 5-cyanothiazol-2-yl, 5-carbamoyl-thiazol-2-yl; or R4is pyrazin-2-yl, pyrimidin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, 6-methoxypyridazin-3-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, 6-cyanopyrimidin-4-yl, 5-carbamoyl-thiazol-2-yl, or 5-cyanothiazol-2-yl, such as preferably R4 is 5-cyano-2-pyridyl, 5-carbamoyl-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5- bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4- yl, pyrazin-2-yl, 5-bromopyrazin-2-yl, 5-carbamoylpyrazin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, or 5-cyanothiazol-2-yl; or R4 is pyrimidin-2-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, or 6-cyanopyrimidin-4-yl. More preferably, R4is pyrimidin-2-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, or 6-cyanopyrimidin-4-yl.

[0064] In other preferred embodiments of each aspect of the invention, R4 is Qc-1, Qc-2, Qc-3, Qc-4, Qc-6, or Qc-9. Preferably, R4is 5-cyano-2-pyridyl, 5-carbamoyl-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, pyrazin-2-yl, 5-chloropyrazin-2-yl, 5-bromopyrazin-2-yl, 5- carbamoylpyrazin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, 5-cyanothiazol-2-yl, or 5-carbamoylthiazol-2-yl.

[0065] In embodiments where Q is Qb, R4a is as follows:A. R4a is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, thiazolyl, pyrazol-1-yl, or N-linked triazolyl,each of which, independently of each other, is optionally substituted with a single substituent R4b; or R4a is oxo-pyridazinyl optionally N-substituted with a single substituent R4c; orB. R4a is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, Qc-7, Qc-8, Qc-9, Qc-10, or Qc-11:109934 | 83191 FF 16; or A. R4a is Qc-1, Qc-2, Qc-3, Qc-4, or Qc-9; orB. R4a is Qc-1, Qc-2, or Qc-3; orC. R4a is Qc-1; orD. R4a is 5-cyano-2-pyridyl; i.e. R4a is Qc-1, with cyano as R4b; orE. R4a is 5-cyano-2-pyridyl or 5-carbamoyl-2-pyridyl; i.e. R4a is Qc-1, with cyano or -C(O)NH2 asR4b.

[0066] In preferred embodiments of each aspect of the invention, R4a is Qc-1, Qc-2, Qc-3, Qc-4, or Qc-9,such as R4ais Qc-1, Qc-2, or Qc-3. More preferably, R4ais Qc-1.

[0067] In preferred embodiments of each aspect of the invention, the pyridyl, pyrimidinyl, pyrazinyl,thiazolyl, and oxo-pyridazinyl rings of R4and R4aare each connected to the remainder of the compound viaa carbon atom. In other words, a carbon atom of the pyridyl, pyrimidinyl, pyrazinyl, thiazolyl, or oxo-pyridazinyl rings of R4and R4ais linked to Qaor Qb, respectively.

[0068] In an embodiment of each aspect of the invention, R4b is as follows:A. R4b is hydrogen, halogen, cyano, hydroxy, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, -C(O)NR10R11, -N(R11)C(O)OR10, or -N(R11)C(O)R10; or B. R4b is hydrogen, halogen, cyano, hydroxy, C1-C3alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, -C(O)NR10R11, or -NHC(O)R10; or C. R4b is hydrogen, fluoro, chloro, iodo, cyano, C1-C3alkyl, C1-C3alkoxy, -C(O)NR10R11, -NHC(O)R10or -N(CH3)C(O)R10; or D. R4b is hydrogen, chloro, iodo, cyano, C1-C3alkyl, methoxy, -C(O)NR10R11, -NHC(O)R10 or -N(CH3)C(O)R10; or E. R4b is hydrogen, cyano, C1-C3alkyl, C1-C3alkoxy, -C(O)NR10R11, -NHC(O)R10 or -N(CH3)C(O)R10; or F. R4b is hydrogen, cyano, C1-C3alkyl, methoxy, -C(O)NHR11, -NHC(O)R10 or -N(CH3)C(O)R10;109934 | 83191 FF 17 G. R4b is hydrogen, cyano, methyl, ethyl, methoxy, ethoxy, -C(O)NHR11, -C(O)N(CH3)R11, -NHC(O)R10or -N(CH3)C(O)R10; or H. R4b is hydrogen, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, -C(O)N(CH3)2, -C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or -NHC(O)OCH3; or I. R4b is hydrogen, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, or -NHC(O)OCH3; orJ. R4b is hydrogen, fluoro, chloro, bromo, cyano, methyl, ethyl, methoxy, ethoxy, -C(O)NHR11, -C(O)N(CH3)R11, -NHC(O)R10, -N(CH3)C(O)R10, or -N(CH3)C(O)OR10; or K. R4b is hydrogen, fluoro, chloro, bromo, cyano, methyl, ethyl, methoxy, ethoxy, -C(O)NHR11, -C(O)N(CH3)R11, -NHC(O)R10, or -N(CH3)C(O)R10; or L. R4b is hydrogen, fluoro, chloro, bromo, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, -C(O)N(CH3)2, -C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or -NHC(O)OCH3; or M. R4b is hydrogen, fluoro, chloro, bromo, cyano, methyl, ethyl, methoxy, ethoxy, -C(O)NH2, -C(O)NHCH3, or -NHC(O)OCH3; or N. R4b is hydrogen, fluoro, chloro, bromo, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, or -NHC(O)OCH3; or O. R4b is hydrogen, fluoro, chloro, bromo, cyano, -C(O)NH2, or -C(O)NHCH3.

[0069] In an embodiment of each aspect of the invention, for instance where Q is Qa-1, Qa-4, Qa-5, Qa-10, Qa-15, Qa-17, or Qb-1; or Q is Qa-1 or Qb-1, R10 is as follows:A. R10 is hydrogen, C1-C3alkyl, C3-C6cycloalkyl, C3-C4cycloalkylC1-C2alkyl, C1-C3cyanoalkyl,cyanoC3-C6cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C4haloalkyl; orB. R10 is hydrogen, C1-C3alkyl, C3-C4cycloalkyl, cyclopropylC1-C2alkyl, C1-C3cyanoalkyl,cyanoC3-C4cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C4haloalkyl; orC. R10 is hydrogen, C1-C3alkyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2-cyanoethyl,cyanoC3-C4cycloalkyl, or C1-C3alkoxyC1-C3alkyl; or D. R10 is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2-cyanoethyl, 2-cyanocyclopropyl, methoxymethyl, 2-methoxyethyl, or ethoxymethyl; or E. R10 is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, or cyanomethyl; orF. R10 is hydrogen, methyl, ethyl, isopropyl, or cyclopropyl; orG. R10 is hydrogen, methyl, or cyanomethyl; orH. R10 is hydrogen or methyl;and R11is as follows: A. R11 is hydrogen, hydroxy, C1-C3alkyl, C3-C4cycloalkyl, cyanoC3-C6cycloalkyl, C1-C3cyanoalkyl, C1-C3alkoxyC1-C3alkyl, C1-C3haloalkyl, or C1-C3alkoxy; or B. R11 is hydrogen, hydroxy, C1-C3alkyl, C1-C3cyanoalkyl, cyanoC3-C4cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C3alkoxy; or C. R11 is hydrogen, C1-C3alkyl, C3-C4cycloalkyl, C1-C3cyanoalkyl, or C1-C3alkoxy; orD. R11 is hydrogen, C1-C3alkyl, cyanocyclopropyl, C1-C3alkoxyC1-C3alkyl, or methoxy; orE. R11 is hydrogen, C1-C3alkyl, cyanomethyl, 2-cyanoethyl, methoxymethyl, or C1-C3alkoxy; orF. R11 is hydrogen, C1-C3alkyl, cyclopropyl, or C1-C3alkoxy; orG. R11 is hydrogen, C1-C3alkyl, cyclopropyl, or methoxy; or109934 | 83191 FF 18 H. R11 is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, cyclopropyl, 1-cyanocyclopropyl,or methoxy; or I. R11 is hydrogen or methyl; orJ. R11 is hydrogen.

[0070] In preferred embodiments of each aspect of the invention, R10 is hydrogen, methyl, orcyanomethyl, such as R10is hydrogen or methyl. Also in embodiments of each aspect of the invention, R11is hydrogen or methyl, such as R11is hydrogen.

[0071] In preferred embodiments of each aspect of the invention, R4b is hydrogen, fluoro, chloro, bromo,cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, -C(O)N(CH3)2, -C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or -NHC(O)OCH3; or R4bis hydrogen, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, -C(O)N(CH3)2, -C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or -NHC(O)OCH3. More preferably, R4b is hydrogen, fluoro, chloro,bromo, cyano, -C(O)NH2, or -C(O)NHCH3; or R4b is hydrogen, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, or -NHC(O)OCH3.

[0072] In preferred embodiments of each aspect of the invention, the group R4b is in the meta or paraposition with respect to the link of R4or R4ato the remainder of the compound, i.e. to the Qaor Qbring, respectively.

[0073] In an embodiment of each aspect of the invention, R4c is as follows:A. R4c is C1-C3alkyl, C1-C3haloalkyl, allyl, propargyl, or C3-C6cycloalkylC1-C4alkyl; orB. R4c is C1-C3alkyl, C1-C3haloalkyl, or C3-C6cycloalkylC1-C4alkyl; orC. R4c is methyl, ethyl, difluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoromethyl, allyl, propargyl, orcyclopropylmethyl; or D. R4c is methyl, ethyl, allyl, propargyl, or cyclopropylmethyl; orE. R4c is methyl, ethyl, or cyclopropylmethyl; orF. R4c is methyl or cyclopropylmethyl; orG. R4c is methyl.

[0074] In preferred embodiments of each aspect of the invention, R4c is methyl.

[0075] Accordingly, the present invention makes available a compound of formula (I) having thesubstituents A1, Q (i.e. Qa with R4 and R5, or Qb with R4a, R5a and R5b), R1, R2a and R2a', R2b, R3, R10, R11,and X as defined above, in all combinations and each permutation.

[0076] For instance, compounds of formula (I) are made available, where A1 is CH or N; X is an oxygenatom or a sulfur atom; Q is Qaor Qb; R1is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; R2aand R2a'are, independently from each other, hydrogen, halogen, cyano, C1-C3alkyl, or C3-C4cycloalkyl; or R2aand R2a'form a C3-C6cycloalkyl group together with the carbon atom they are attached to; R2b is hydrogen, halogen,C1-C3haloalkyl, C1-C3haloalkoxy, cyano, SF5, C1-C3alkylsulfanyl, C1-C3alkylsulfinyl, C1-C3alkylsulfonyl, C1- C3haloalkylsulfanyl, C1-C3haloalkylsulfinyl, C1-C3haloalkylsulfonyl, C1-C5cyanoalkyl, C1-C5cyanoalkoxy, C3- C4cycloalkylC1-C2alkyl, C3-C4cycloalkylC1-C2haloalkyl, C3-C4cycloalkylcarbonyl, or C3-C4cycloalkyl optionally substituted with one or two substituents independently selected from the group consisting ofhalogen, -CN, C1-C3alkyl, and C1-C3haloalkyl; R3 is C1-C3alkyl or C1-C3haloalkyl; R4 is pyridinyl, pyrimidyl,pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently of each other, is optionally substituted witha single substituent R4b; or R4 is oxo-pyridazinyl optionally N-substituted with a single substituent R4c; R4a109934 | 83191 FF 19 is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, thiazolyl, pyrazol-1-yl, or N-linked triazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4b; or R4ais oxo-pyridazinyloptionally N-substituted with a single substituent R4c; R4b is hydrogen, halogen, cyano, hydroxy, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, -C(O)NR10R11, -N(R11)C(O)OR10, or -N(R11)C(O)R10; R4c is C1-C3alkyl, C1-C3haloalkyl, allyl, propargyl, or C3-C6cycloalkylC1-C4alkyl; R5, R5a and R5b are independentlyhydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3-C4cycloalkyl; R10is hydrogen, C1-C3alkyl, C3- C6cycloalkyl, C3-C4cycloalkylC1-C2alkyl, C1-C3cyanoalkyl, cyanoC3-C6cycloalkyl, C1-C3alkoxyC1-C3alkyl, orC1-C4haloalkyl; R11 is hydrogen, hydroxy, C1-C3alkyl, C3-C4cycloalkyl, cyanoC3-C6cycloalkyl, C1-C3cyanoalkyl, C1-C3alkoxyC1-C3alkyl, C1-C3haloalkyl, or C1-C3alkoxy.

[0077] Compounds of formula (I) are made available, where A1 is CH or N, preferably A1 is CH; X is O;R1is hydrogen, methyl, ethyl, or cyclopropyl-methyl, such as R1is hydrogen or methyl; R2aand R2a'are both hydrogen, fluoro, methyl, or ethyl; or R2aand R2a'form a cyclopropyl, a cyclobutyl, or a cyclopentyl, together with the carbon atom they are attached to; R2bis chloro, bromo, iodo, difluoromethyl, or trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, trifluoromethylsulfonyl, or cyclopropyl; R3is methyl ortrifluoromethyl; Q is Qa, wherein R5 is hydrogen, bromo, iodo, methyl, ethyl, methoxy, 2-methoxyethoxy,such as Qais Qa-1, Qa-4, Qa-5, Qa-6, Qa-7, Qa-10, Qa-15, or Qa-17; R4is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc- 6, Qc-7, Qc-8, or Qc-9, such as R4is pyrimidin-2-yl, 5-cyano-2-pyridyl, 5-carbamoyl-2-pyridyl, 5- fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-carbamoylpyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, or 6-cyanopyrimidin-4-yl, pyrazin-2-yl, 5-bromopyrazin-2-yl, 5-carbamoylpyrazin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, or 5- cyanothiazol-2-yl; wherein R4bis hydrogen, fluoro, chloro, bromo, cyano, methyl, ethyl, methoxy, ethoxy, - C(O)NHR11, -C(O)N(CH3)R11, -NHC(O)R10or -N(CH3)C(O)R10; R10is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2-cyanoethyl, 2-cyanocyclopropyl, methoxymethyl, 2- methoxyethyl, or ethoxymethyl; and R11is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, cyclopropyl, 1-cyanocyclopropyl, or methoxy; or R4cis methyl, ethyl, difluoromethyl, 2,2-difluoroethyl, 2,2,2- trifluoromethyl, allyl, propargyl, or cyclopropylmethyl.

[0078] For instance, compounds of formula (I) are made available, where A1 is CH or N, preferably A1 isCH; X is O; R1 is hydrogen, methyl, ethyl, or cyclopropyl-methyl, such as R1 is hydrogen or methyl; R2a andR2a'are both hydrogen, fluoro, methyl, or ethyl; or R2aand R2a'form a cyclopropyl, a cyclobutyl, or a cyclopentyl, together with the carbon atom they are attached to; R2bis chloro, bromo, iodo, difluoromethyl, or trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, trifluoromethylsulfonyl, or cyclopropyl; R3is methylor trifluoromethyl; Q is Qa, wherein R5 is hydrogen, bromo, iodo, methoxy, 2-methoxyethoxy, such as Qa isQa-1, Qa-6, Qa-7, Qa-10, or Qa-15; R4is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, Qc-7, Qc-8, or Qc-9, such as R4is pyrimidin-2-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6- (methoxycarbonylamino)pyrimidin-4-yl, or 6-cyanopyrimidin-4-yl; wherein R4bis hydrogen, cyano, methyl, ethyl, methoxy, ethoxy, -C(O)NHR11, -C(O)N(CH3)R11, -NHC(O)R10or -N(CH3)C(O)R10; R10is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2-cyanoethyl, 2-cyanocyclopropyl, methoxymethyl, 2-methoxyethyl, or ethoxymethyl; and R11is hydrogen, methyl, ethyl, cyanomethyl, 2- cyanoethyl, cyclopropyl, 1-cyanocyclopropyl, or methoxy; or R4cis methyl, ethyl, difluoromethyl, 2,2- difluoroethyl, 2,2,2-trifluoromethyl, allyl, propargyl, or cyclopropylmethyl.109934 | 83191 FF 20

[0079] Compounds of formula (I) are made available, where A1 is CH or N, preferably A1 is CH; X is O;R1is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl, such as R1is hydrogen, methyl, or cyclopropylmethyl; R2ais hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; R2a'is hydrogen, halogen, or C1-C3alkyl; R2bis halogen, C1-C3haloalkyl, C1-C3haloalkoxy, C1-C3alkylsulfonyl, C1-C3haloalkylsulfonyl, C1-C5cyanoalkyl, C3- C4cycloalkylC1-C2alkyl, or cyclopropyl, such as R2bis chloro, bromo, iodo, cyclopropyl, difluoromethyl, ortrifluoromethyl; R3 is methyl or trifluoromethyl; Q is Qa and Qa is Qa-1, Qa-4, Qa-5, Qa-10, Qa-15, or Qa-17; R4is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, or Qc-9, such as R4is pyrimidin-2-yl, 5-cyano-2-pyridyl, 5-carbamoyl- 2-pyridyl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, 6-cyanopyrimidin-4-yl, pyrazin-2-yl, 5-bromopyrazin-2-yl, 5-carbamoylpyrazin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, or 5- cyanothiazol-2-yl; wherein R4bis hydrogen, fluoro, chloro, bromo, cyano, methyl, ethyl, methoxy, ethoxy, - C(O)NHR11, -C(O)N(CH3)R11, -NHC(O)R10or -N(CH3)C(O)R10; R10is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2-cyanoethyl, 2-cyanocyclopropyl, methoxymethyl, 2- methoxyethyl, or ethoxymethyl; and R11is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, cyclopropyl, 1-cyanocyclopropyl, or methoxy.

[0080] Compounds of formula (I) are made available, where A1 is CH or N, preferably A1 is CH; X is O;R1is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl, such as R1 is hydrogen, methyl, or cyclopropylmethyl; R2ais hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; R2a' is hydrogen, halogen, or C1-C3alkyl; R2b ishalogen, C1-C3haloalkyl, C1-C3haloalkoxy, C1-C3alkylsulfonyl, C1-C3haloalkylsulfonyl, C1-C5cyanoalkyl, C3-C4cycloalkylC1-C2alkyl, or cyclopropyl, such as R2bis chloro, bromo, iodo, cyclopropyl, difluoromethyl, ortrifluoromethyl; R3 is methyl or trifluoromethyl; Q is Qa and Qa is Qa-1 or Qa-15; R4 is Qc-1, Qc-2, or Qc-3,such as R4is pyrimidin-2-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin- 4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, or 6-cyanopyrimidin-4-yl; wherein R4bis hydrogen, cyano, methyl, ethyl, methoxy, ethoxy, -C(O)NHR11, -C(O)N(CH3)R11, -NHC(O)R10or -N(CH3)C(O)R10; R10is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2-cyanoethyl, 2- cyanocyclopropyl, methoxymethyl, 2-methoxyethyl, or ethoxymethyl; and R11is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, cyclopropyl, 1-cyanocyclopropyl, or methoxy.

[0081] For instance, compounds of formula (I) are made available, where A1 is CH or N, preferably A1 isCH; X is O; R1 is hydrogen, methyl, ethyl, or cyclopropyl-methyl, such as R1 is hydrogen or methyl; R2a andR2a'are both hydrogen, fluoro, methyl, or ethyl; or R2aand R2a'form a cyclopropyl, a cyclobutyl, or a cyclopentyl, together with the carbon atom they are attached to; R2bis chloro, bromo, iodo, difluoromethyl, or trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, trifluoromethylsulfonyl, or cyclopropyl; R3is methylor trifluoromethyl; Q is Qb, wherein R5a and R5b are independently hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3-C4cycloalkyl, such as R5aand R5bare hydrogen; such as Qbis Qb-1, Qb-3, Qb-5, Qb-10, or Qb-11; and R4ais Qc-1, Qc-2, Qc-3, Qc-4, or Qc-9; wherein R4bis hydrogen, cyano, methyl, ethyl, methoxy, ethoxy, -C(O)NHR11, -C(O)N(CH3)R11, -NHC(O)R10or -N(CH3)C(O)R10; R10is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2-cyanoethyl, 2-cyanocyclopropyl, methoxymethyl, 2-methoxyethyl, or ethoxymethyl; and R11is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, cyclopropyl, 1-cyanocyclopropyl, or methoxy.109934 | 83191 FF 21

[0082] Compounds of formula (I) are made available, where A1 is CH or N, preferably A1 is CH; X is O;R1is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3- C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl, such as R1is hydrogen, methyl, or cyclopropylmethyl; R2ais hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; R2a'is hydrogen, halogen, or C1-C3alkyl; R2bis halogen, C1-C3haloalkyl, C1-C3haloalkoxy, C1-C3alkylsulfonyl, C1-C3haloalkylsulfonyl, C1-C5cyanoalkyl, C3- C4cycloalkylC1-C2alkyl, or cyclopropyl, such as R2bis chloro, bromo, iodo, cyclopropyl, difluoromethyl, ortrifluoromethyl; R3 is methyl or trifluoromethyl; Q is Qb and Qb is Qb-1; R4a is Qc-1, Qc-2, or Qc-3, such asR4a is 5-cyano-2-pyridyl or 5-carbamoyl-2-pyridyl; wherein R4b is hydrogen, cyano, methyl, ethyl, methoxy,ethoxy, -C(O)NHR11, -C(O)N(CH3)R11, -NHC(O)R10or -N(CH3)C(O)R10; R10is hydrogen, methyl, ethyl,isopropyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2-cyanoethyl, 2-cyanocyclopropyl, methoxymethyl,2-methoxyethyl, or ethoxymethyl; and R11is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, cyclopropyl, 1-cyanocyclopropyl, or methoxy.

[0083] Compounds of formula (I) are made available, where A1 is CH or N, preferably A1 is CH; X is O;R1is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl, such as R1 is hydrogen, methyl, or cyclopropylmethyl; R2ais hydrogen, halogen, C1-C3alkyl, or C3-C4cycloalkyl; R2a' is hydrogen, halogen, or C1-C3alkyl; R2b ishalogen, C1-C3haloalkyl, C1-C3haloalkoxy, C1-C3alkylsulfonyl, C1-C3haloalkylsulfonyl, C1-C5cyanoalkyl, C3-C4cycloalkylC1-C2alkyl, or cyclopropyl, such as R2bis chloro, bromo, iodo, cyclopropyl, difluoromethyl, ortrifluoromethyl; R3 is methyl or trifluoromethyl; Q is Qb and Qb is Qb-1; R4a is Qc-1, Qc-2, or Qc-3, such asR4ais 5-cyano-2-pyridyl; wherein R4bis hydrogen, cyano, methyl, ethyl, methoxy, ethoxy, -C(O)NHR11, - C(O)N(CH3)R11, -NHC(O)R10or -N(CH3)C(O)R10; R10is hydrogen, methyl, ethyl, isopropyl, cyclopropyl, cyclopropylmethyl, cyanomethyl, 2-cyanoethyl, 2-cyanocyclopropyl, methoxymethyl, 2-methoxyethyl, or ethoxymethyl; and R11is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, cyclopropyl, 1-cyanocyclopropyl, or methoxy. Compounds of formula (I) are made available, where A1 is CH; X is O; R1 ishydrogen, methyl, ethyl, or cyclopropyl-methyl, such as R1is hydrogen; R2aand R2a'are both fluoro or methyl, or they form a cyclopropyl together with the carbon atom they are attached to; R2bis chloro,difluoromethyl, or trifluoromethyl; R3 is methyl; Q is Qa-1, Qa-4, Qa-5, Qa-10, Qa-15, Qa-17, or Qb-1; R4 ispyrimidin-2-yl, 5-cyano-2-pyridyl, 5-carbamoyl-2-pyridyl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5- bromopyrimidin-2-yl, 6-carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6- (methoxycarbonylamino)pyrimidin-4-yl, 6-cyanopyrimidin-4-yl, pyrazin-2-yl, 5-bromopyrazin-2-yl, 5-carbamoylpyrazin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, or 5-cyanothiazol-2-yl, or R4a is 5-cyano-2-pyridyl or5-carbamoyl-2-pyridyl.

[0084] Compounds of formula (I) are made available, where A1 is CH; X is O; R1 is hydrogen, methyl,ethyl, or cyclopropyl-methyl, such as R1 is hydrogen; R2a and R2a' are both fluoro or methyl, or they form acyclopropyl together with the carbon atom they are attached to; R2bis chloro or trifluoromethyl; R3is methyl; Q is Qa-1 or Qb-1; R4is pyrazin-2-yl, pyrimidin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, 6-methoxypyridazin-3-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6- (methoxycarbonylamino)pyrimidin-4-yl, 6-cyanopyrimidin-4-yl, 5-carbamoyl-thiazol-2-yl, or 5-cyanothiazol- 2-yl, or R4ais 5-cyano-2-pyridyl.

[0085] Compounds of formula (I) are made available, where A1 is CH; X is O; R1 is hydrogen; R2a andR2a'form a cyclopropyl together with the carbon atom they are attached to; R2bis chloro, cyclopropyl,109934 | 83191 FF 22 difluoromethyl, or trifluoromethyl; R3is methyl; Q is Qa-1 Qa-4, Qa-5, Qa-10, Qa-15, Qa-17, such as Q is Qa- 1; R4is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, Qc-9; and R4bis hydrogen, fluoro, chloro, bromo, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, or -NHC(O)OCH3.

[0086] Compounds of formula (I) are made available, where A1 is CH; X is O; R1 is hydrogen; R2a andR2a'form a cyclopropyl together with the carbon atom they are attached to; R2bis chloro, cyclopropyl, or trifluoromethyl; R3is methyl; Qais Qa-1 or Qa-15, such as Qais Qa-1; R4is Qc-1, Qc-2, or Qc-3; and R4bis hydrogen, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, or -NHC(O)OCH3.

[0087] Compounds of formula (I) are also made available, where A1 is CH; X is O; R1 is hydrogen;R2aand R2a' are both fluoro or methyl; R2b is difluoromethyl or trifluoromethyl; R3 is methyl; Qb is Qb-1, Qb-3, Qb-5, Qb-10, or Qb-11, such as Qbis Qb-1; R4ais Qc-1, Qc-2, or Qc-3; and R4bis hydrogen, fluoro, chloro, bromo, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, -C(O)N(CH3)2, -C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or -NHC(O)OCH3.Compounds of formula (I) are also made available, where A1is CH; X is O; R1ishydrogen;R2a and R2a' are both fluoro or methyl; R2b is chloro or trifluoromethyl; R3 is methyl; Qb is Qb-1,Qb-3, Qb-5, Qb-10, or Qb-11, such as Qbis Qb-1; R4ais Qc-1, Qc-2, or Qc-3; and R4bis hydrogen, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, -C(O)N(CH3)2, -C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or - NHC(O)OCH3.

[0088] Compounds of formula (I) are also made available, where A1 is CH; X is O; R1 is hydrogen;R2aand R2a' are both fluoro or methyl; R2b is difluoromethyl or trifluoromethyl; R3 is methyl; Qb is Qb-1, Qb-3, Qb-5, Qb-10, or Qb-11, such as Qbis Qb-1; R4ais Qc-1, Qc-2, or Qc-3; and R4bis hydrogen, fluoro, chloro, bromo, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, -C(O)N(CH3)2, -C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or -NHC(O)OCH3.

[0089] Compounds of formula (I) are also made available, where A1 is CH; X is O; R1 is hydrogen; R2aand R2a'form a cyclopropyl together with the carbon atom they are attached to; R2bis chloro ortrifluoromethyl; R3 is methyl; Qb is Qb-1, Qb-3, Qb-5, Qb-10, or Qb-11, such as Qb is Qb-1; R4a is Qc-1, Qc-2,or Qc-3; and R4bis hydrogen, cyano, methyl, methoxy, -C(O)NH2, -C(O)NHCH3, -C(O)N(CH3)2, - C(O)NHCH2CN, -C(O)N(CH3)CH2CN, or -NHC(O)OCH3.

[0090] Compounds of formula (I) are also made available, where A1 is CH or N; X is an oxygen atom ora sulfur atom, such as X is O; R1is hydrogen; R2aand R2a'are both fluoro or methyl, or they form a cyclopropyl together with the carbon atom they are attached to; R2bis difluoromethyl or trifluoromethyl; R3is methyl; Q is Qa-1, Qa-15, or Qb-1; R4is 5-cyano-2-pyridyl, 5-carbamoyl-2-pyridyl, pyrimidin-2-yl, 5- fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, -(methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 5-bromopyrazin-2-yl, 5-carbamoylpyrazin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, 5-carbamoyl-thiazol-2-yl, or 5- cyanothiazol-2-yl, such as R4is 5-cyano-2-pyridyl, 5-carbamoyl-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin- 2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, pyrazin-2-yl, 5-bromopyrazin-2-yl, 5-carbamoylpyrazin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, or 5-cyanothiazol-2-yl; and R4a is 5-cyano-2-pyridyl or 5-carbamoyl-2-pyridyl.

[0091] Compounds of formula (I) are also made available, where A1 is CH or N; X is an oxygen atom ora sulfur atom, such as X is O; R1is hydrogen; R2aand R2a'are both fluoro or methyl, or they form a cyclopropyl together with the carbon atom they are attached to; R2bis chloro or trifluoromethyl; R3is methyl; Q is Qa-1, Qa-15, or Qb-1; R4is pyrazin-2-yl, pyrimidin-2-yl, 5-cyano-2-pyridyl, 6-carbamoylpyrimidin-4-yl,109934 | 83191 FF 23 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, 6-cyanopyrimidin-4-yl, 5- carbamoyl-thiazol-2-yl, or 5-cyanothiazol-2-yl, such as R4is pyrimidin-2-yl, 5-cyano-2-pyridyl, 6- carbamoylpyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6-(methoxycarbonylamino)pyrimidin-4-yl, or 6-cyanopyrimidin-4-yl; and R4ais 5-cyano-2-pyridyl.

[0092] Compounds of formula (I) are made available, where A1 is CH; X is O; R1 is hydrogen; R2a andR2a'are methyl; R2bis chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, or cyclopropyl; R3is methyl; Q is Qa-1 Qa-4, Qa-5, Qa-10, Qa-15, Qa-17, such as Q is Qa-1; R4is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc- 6, Qc-9; R4bis hydrogen, fluoro, chloro, bromo, cyano, methoxy, -C(O)NH2, -C(O)NHCH3, or -NHC(O)OCH3; and R4cis methyl.

[0093] Compounds of formula (I) are also made available, where A1 is CH or N; X is an oxygen atom ora sulfur atom, such as X is O; R1is hydrogen; R2aand R2a'are both fluoro or methyl, or they form a cyclopropyl together with the carbon atom they are attached to; R2bis chloro, bromo, difluoromethyl, trifluoromethyl, difluoromethoxy, or cyclopropyl; R3is methyl; Q is Qa-1, Qa-4, Qa-5, Qa-10, Qa-15, or Qa-17or Qb-1; R4 is 5-cyano-2-pyridyl, 5-carbamoyl-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6- (methylcarbamoyl)pyrimidin-4-yl, pyrazin-2-yl, 5-chloropyrazin-2-yl, 5-bromopyrazin-2-yl, 5- carbamoylpyrazin-2-yl, 1-methyl-6-oxo-pyridazin-3-yl, 5-cyanothiazol-2-yl, or 5-carbamoylthiazol-2-yl; and R4ais 5-cyano-2-pyridyl or 5-carbamoyl-2-pyridyl.

[0094] Compounds of formula (I) are made available, where A1 is CH; X is O; R1 is hydrogen; R2a andR2a'are methyl; R2bis chloro, bromo, or trifluoromethyl; R3is methyl; Q is Qa-1; R4is Qc-2 or Qc-3; R4bis hydrogen, -C(O)NH2, or -C(O)NHCH3. Synthesis

[0095] Compounds of formula (I) can be prepared by those skilled in the art following known methods.More specifically compounds of formulae (I), and (I’a), and intermediates therefor can be prepared as described below in the schemes and examples. Certain stereogenic centers have been left unspecified for clarity. This is not intended to limit the teaching of the schemes in any way.

[0096] Compounds of formula (I), wherein Q, R1 and R3 are as defined for compounds of formula (I), canbe made, for example, as shown in Scheme 1.Scheme 1 where T representshave the same meaning as given for compounds of formula (I), and the staggered line represents the connection to the109934 | 83191 FF 24 remainder of the compound T is attached to, such as the compounds of the formula (I), (Ia), (Ia-1), (Ib), (II), (IV), (IVa), (X), (XI) in Schemes 1 to 6.

[0097] Compounds of the formula (I) can be made, for example, by reaction of a compound of the formula(II), wherein X1is hydroxy or a leaving group, such as a halogen or sulfonate, for instance chloride, and wherein T has the meaning given above, with a compound of formula (III), or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or anyother equivalent salt), wherein R1, R3 and Q have the same meaning as given above for compounds of theformula (I). In the case that X1is hydroxy, it may be advantageous to carry out the reaction in the presence of a dehydration reagent, for instance a peptide coupling reagent, such as, for example, a carbodiimide,HATU (1-[bis(dimethylamino)-methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate,also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium) or propanephosphonic acid cyclic anhydride (T3P®). Such reactions can be conducted neat or in a solvent, preferably in a solvent,such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethylacetate, N,N-dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +300 °C,preferably between ambient temperature and 200 °C, with or without the presence of a catalyst, for instancean acylation catalyst, such as 4-dimethylaminopyridine (DMAP), and with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine or pyridine.

[0098] Compounds of the formula (II) are either known, or they can be prepared by methods known to aperson skilled in the art. In particular, compounds of the formula (II) wherein X1is a leaving group, such as a halogen, for instance chloride, can be formed by treatment of compounds of formula (II) wherein X1is hydroxy with, for example, oxalyl chloride or thionyl chloride, in the presence of catalytic quantities of N,N- dimethylformamide (DMF), in an inert solvent, such as, for instance, dichloromethane (DCM) or tetrahydrofuran (THF), in a temperature range of 0°C to 100°C, preferably about 25°C. Such methods areknown to those skilled in the art and described for example in Tetrahedron 2005, 61 (46), 10827-10852.VIII VIIScheme 2

[0099] Compounds of formula (III), or a salt thereof, wherein Q, R1 and R3 have the same meaning asgiven above for compounds of the formula (I), can be made, for example, as shown in Scheme 2. Treatmentof a compound of the formula (V), wherein R3 and Q have the same meaning as given above for compoundsof the formula (I) and X2 is a leaving group, such as a halogen or sulfonate, for instance bromide, with anamine of the formula (XIX), or a salt thereof, wherein R1has the same meaning as given above forcompounds of the formula (I), gives compounds of the formula (III), wherein Q, R1 and R3 have the samemeaning as given above for compounds of the formula (I). The reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature rangeof -100 to +300 °C, preferably at a temperature ranging from ambient temperature to 200 °C, with or without109934 | 83191 FF 25 the addition of a base, such as an inorganic base, for instance, potassium carbonate, or an organic base, such as, for example, triethylamine.

[0100] Alternatively, treatment of a compound of the formula (VII), wherein R3 and Q have the samemeaning as given above for compounds of the formula (I), with an amine of the formula (XIX), or a salt thereof, wherein R1has the same meaning as given above for compounds of the formula (I), givescompounds of the formula (III), wherein Q, R1 and R3 have the same meaning as given above forcompounds of the formula (I). This reaction is done in the presence of a reducing agent, such as hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide or titanium(IV) isopropoxide, in a solvent or without a solvent, such as, for instance,methanol. The reaction can be conducted in a temperature ranging from -100 to +300 °C, preferablybetween ambient temperature and 200 °C. Such methods, and the range of conditions to perform them, forthe alkylation of amines and for the reductive alkylation of amines (e.g. in the presence of NaBH(OAc)3 or NaBH3CN, in a suitable solvent, preferably in acetic acid, at room temperature, analogous to WO2002 / 088073; or alternatively, by the use of a combination of Ti(i-OiPr)4 and NaBH4 as described in Synthesis 2003 (14), 2206) are well known to a person skilled in the art. The amines of formula (XIX), or a salt thereof, wherein R1has the same meaning as given above for compounds of the formula (I), are either known, or they can be prepared by methods known to a person skilled in the art.Scheme 3

[0101] Alternatively, compounds of formula (I) can be made, for example, by reaction of compound ofthe formula (IV), wherein T has the same meaning as given above in Scheme 1, and R1has the samemeaning as given above for compounds of the formula (I), with a compound of the formula (V), wherein R3and Q have the same meaning as given above for compounds of the formula (I), and X2is a leaving group, such as a halogen or sulfonate, for instance chloride or bromide. The reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperaturerange of -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the additionof a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine. Such methods for the alkylation of amines, and the range of conditions to perform them, are well known to a person skilled in the art.

[0102] Alternatively, a compound of the formula (I) can be made by reaction of a compound of the formula(IVa), wherein T has the same meaning as given above in Scheme 1, with a compound of the formula (VII),wherein R3 and Q have the same meaning as given above for compounds of the formula (I). This reactionis done in the presence of a reducing agent, such as hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or109934 | 83191 FF 26 without a solvent, such as, for instance, methanol. The reaction can be conducted in a temperature rangeof -100 to +300 °C, preferably between ambient temperature and 200 °C. Such methods for the reductivealkylation of amines, and the range of conditions to perform them, are well known to a person skilled in the art.VIII V VIIScheme 4

[0103] Compounds of formula (V), wherein R3 and Q have the same meaning as given above forcompounds of the formula (I), and X2is a leaving group, such as a halogen or sulfonate, for instance chloride or bromide, can be made, for example, as shown in scheme 4. Treatment of a compound of theformula (VIII), wherein R3 and Q have the same meaning as given above for compounds of the formula (I),with a halogenating agent, such as chlorine, bromine, N-chlorosuccinimide or N-bromosuccinimide, forexample, gives compound of the formula (V), wherein the leaving group X2is a halogen, for instance chloride or bromide. This reaction is done with or without a solvent, preferably in a solvent, with or without an additive, such as a radical starter, such as, for example, benzoyl peroxide or azoisobutyronitrile. The reaction can be done with or without exposure to visible light, or to UV light, and it can be conducted in atemperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C.

[0104] Alternatively, a compound of the formula (VII), wherein R3 and Q have the same meaning asgiven above for compounds of the formula (I), can be treated with a reducing agent, followed by reactionwith a sulfonyl chloride, for instance methanesulfonyl chloride, to give a compound of the formula (V), wherein the leaving group X2is a sulfonate, for instance a mesylate. This reaction can be done in a solvent, or without a solvent, in the presence of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as an amine base, for instance trimethylamine, or without a base, andit can be conducted in a temperature range of -100 to +300 °C, preferably between ambient temperatureand 200 °C. A suitable reducing agent could be, for example, hydrogen, or a hydride, such as sodiumborohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, for instance, methanol. The reaction can be conducted in atemperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C. Such methodsfor the halogenation, the reduction of carbonyl compounds and the sulfonylation of alcohols, and the range of conditions to perform them, are well known to a person skilled in the art. The compounds of the formula(VII) and the compounds of formula (VIII), wherein R3 and Q have the same meaning as given above forcompounds of the formula (I), are either known, or they can be prepared by methods known to a person skilled in the art.Ia VI Ia-1109934 | 83191 FF 27 Scheme 5

[0105] Alternatively, compounds of formula (Ia-1), wherein T has the same meaning as given above inScheme 1, and R1, R3and Q have the same meaning as given above for compounds of the formula (I), except that R1is different from hydrogen, can be made, for example, as shown in scheme 5. A compoundof the formula (Ia), wherein T has the same meaning as given above in Scheme 1, and R3 and Q have thesame meaning as given above for compounds of the formula (I), can be reacted with a compound of the formula (VI), wherein R1has the same meaning as given above for compounds of the formula (I), except that R1is different from hydrogen, and wherein X30is a leaving group, such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate, to give a compound of formula (Ia-1). This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF) or N,N-dimethylacetamide (DMA),or mixtures thereof, in a temperature range of -100 to +300 °C, preferably between ambient temperatureand 200 °C, with or without the addition of a base, such as an inorganic base, for instance sodium,potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine, or pyridine. Such methods for the alkylation of amines, and the range of conditionsto perform them, are well known to a person skilled in the art and are described for example inWO2021 / 083936. Compounds of the formula (VI), wherein R1has the same meaning as given above for compounds of the formula (I), except that R1is different from hydrogen, and wherein X30is a leaving group, such as a halogen or sulfonate, for instance a chloride, bromide, iodide or mesylate, are either known, or they can be prepared by methods known to a person skilled in the art.

[0106] Compounds of formula (Ib), wherein T has the same meaning as given above in Scheme 1, andR3, R4and R5have the same meaning as given above for compounds of the formula (I), can be made, for example, as shown in scheme 6. Reaction of a compound of the formula (II), wherein T has the same meaning as given above in Scheme 1 and wherein X1is hydroxy or a leaving group, such as a halogen or sulfonate, for instance chloride, with a compound of the formula (IX), or a salt thereof, wherein R3has the same meaning as given above for compounds of the formula (I), gives a compound of the formula (X), wherein T has the same meaning as given above in Scheme 1, and wherein R3has the same meaning as109934 | 83191 FF 28 given above for compounds of the formula (I). In the case that X1is hydroxy, it may be advantageous to carry out the reaction in the presence of a dehydration reagent, for instance a peptide coupling reagent,such as, for example, a carbodiimide, HATU (1-[bis(dimethylamino)-methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, also known as Hexafluorophosphate AzabenzotriazoleTetramethyl Uronium) or propanephosphonic acid cyclic anhydride (T3P®). The reaction can be conductedneat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile,tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N-dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +300 °C, preferably between ambient temperatureand 200 °C, with or without the presence of a catalyst, for instance an acylation catalyst, such as 4-dimethylaminopyridine (DMAP), and with or without the addition of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine, or pyridine.

[0107] Subsequent treatment of compound of the formula (X), wherein T has the same meaning as givenabove in Scheme 1, and wherein R3has the same meaning as given above for compounds of the formula(I), with the known compound (XIII), wherein R5 is hydrogen, C1-C3alkyl or C3-C4cycloalkyl (e.g. XIII is N,N-dimethylformamide dimethyl acetal, also named DMF-DMA) gives a compound of the formula (XI), wherein T has the same meaning as given above in Scheme 1, R3has the same meaning as given above for compounds of the formula (I), and in which R5is hydrogen, C1-C3alkyl or C3-C4cycloalkyl. This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instancedichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran or dioxane, in a temperature range of -100 to+300 °C, preferably between ambient temperature and 100 °C, or between ambient temperature and 50°C, without a base or in the presence of a base, such as an inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for example, triethylamine, diisopropylethylamine, or pyridine.

[0108] Further reaction of compound of the formula (XI), wherein T has the same meaning as givenabove in Scheme 1, R3has the same meaning as given above for compounds of the formula (I), and in which R5is hydrogen, C1-C3alkyl or C3-C4cycloalkyl, with a hydrazine compound of the formula (XII) or a tautomer thereof, or a salt thereof, wherein R4has the same meaning as given above for compounds of the formula (I), gives the compound of the formula (Ib), wherein T has the same meaning as given above in Scheme 1, R3and R4have the same meaning as given above for compounds of the formula (I), and in which R5is hydrogen, C1-C3alkyl or C3-C4cycloalkyl. This reaction can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance 1,4-dioxane, or acetic acid, or a mixture of1,4-dioxane and acetic acid, in a temperature range of -100 to +300 °C, preferably between ambienttemperature and 200 °C, or between ambient temperature and 80 °C. Within this sequence oftransformations, the intermediate compounds of formula (X) and of formula (XI) can be used as crude products for the subsequent step, or they can be purified, for instance by chromatography, and used in purified form for the next transformation.

[0109] Compounds of the formula (IX), or a salt thereof, wherein R3 has the same meaning as givenabove for compounds of the formula (I), are either known, or they can be prepared by methods known to aperson skilled in the art. Hydrazine compounds of formula (XII) or a tautomer thereof, or a salt thereof,109934 | 83191 FF 29wherein R4 has the same meaning as given above for compounds of the formula (I), are either known, orthey can be prepared by methods known to a person skilled in the art.

[0110] Compounds of the formula (Ik)can be prepared by the reaction of an amine of the formula (IIIf), or a salt thereofwherein R1, R3, R4 and R5 are as described in formula (I), with a compound of the formula (IIa)wherein A1, R2a, R2a’ and R2b are as described in formula (I) and X1 is hydroxy or a leaving group,such as a halogen or a sulfonate, for instance chloride, under conditions already described in Scheme 1.109934 | 83191 FF 30

[0111] Compounds of formula (Ic) can be made, for example, as shown in scheme 7. Reaction of acompound of the formula (XVII) (wherein X05 is a leaving group such as chlorine, bromine, iodine, arysulfonate, alkylsulfonate or trifluoromethanesulfonate) with an amine of the formula (XIX), or a salt thereof, gives compounds of the formula (XVI) , or a salt thereof. This reaction is done in the presence of a reducing agent, such as hydrogen, or a hydride, such as sodium borohydride, with or without a catalyst, such as a hydrogenation catalyst, for example palladium on carbon, with or without the presence of an acid, such as acetic acid, or a Lewis acid, such as zinc bromide, in a solvent or without a solvent, such as, forinstance, methanol. The reaction can be conducted in a temperature range of -100 to +300 °C, preferablybetween ambient temperature and 200 °C. Such methods, and the range of conditions to perform them, forthe reductive alkylation of amines are well known to a person skilled in the art.

[0112] Subsequent reaction of the intermediate of the formula (XVI) , or a salt thereof, with a compoundof the formula (IIa) gives a compound of the formula (XIV). This reaction can be conducted neat or in asolvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, in a temperature rangeof -100 to +300 °C, preferably between ambient temperature and 200 °C, with or without the presence of acatalyst, for instance a metal catalyst, such as a palladium complex, and with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine.

[0113] Subsequently, the intermediate of the formula (XIV) is reacted with a compound of the formula(XV) to give the compound of formula (Ic), wherein A1, R2a, R2a’, R2b, R1, R3 and R4a have the same meaningas given above for compounds of the formula (I), and M1 in R4a-M1 is a metal, such as, for example, lithium,or –MgCl, –ZnBr, or –B(OH)2; or R4a-M1 represents a boronate, such as a pinacol ester of a boronic acid,or a stannane such as R4a-Sn(n-Bu)3. Such transformations are known to a person skilled in the art asSuzuki-, Kumada-, Negishi- or Stille-coupling reactions, respectively. Such reactions are carried out in a109934 | 83191 FF 31temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, in thepresence of a catalyst, such as a metal catalyst, for instance a palladium catalyst, and a ligand, such as,for example, a phosphine ligand, an N-heterocyclic carbene (NHC) ligand, or a phosphite ligand. Thereaction can be done in the presence or absence of an additional metal catalyst, such as, for example, a copper salt, for instance CuI. The reaction is done with or without a base, which can be an inorganic base, such as potassium carbonate, or sodium hydroxide, or cesium carbonate, or an organic base, such as an amine base, for instance triethyl amine. This reaction is done with or without a solvent, preferentially in a solvent. Where the reaction mixture is heated, the reaction can be conducted under microwave irradiationor with conventional heating, such as heating the reaction vessel in an oil bath.

[0114] By an alternative route, compound (XVII) can be reacted with a compound of the formula (XV) togive intermediate (XVIII). This reaction is done essentially under in the same range of conditions as described for the transformation of intermediate (XIV) to the compound of formula (Ic).

[0115] Subsequently, the intermediate (XVIII) is reacted with a compound of the formula (IVb) to give acompound of the formula (Ic), wherein R1 is hydrogen and A1, R2a, R2a’, R2b, R3 and R4a have the samemeaning as given above for compounds of the formula (I). This reaction is done in the presence of a reducing agent, essentially under the same conditions as described above for the transformation of compound (XVII) to intermediate (XVI).

[0116] By yet another alternative route, the intermediate compound of the formula (XVIII) can be reactedwith an amine of the formula (XIX), or a salt thereof, to give the intermediate of the formula (IIIa), or a salt thereof. This reaction is done in the presence of a reducing agent, essentially under the same conditions as described above for the transformation of compound (XVII) to intermediate (XVI).

[0117] Subsequently, the intermediate of the formula (IIIa), or a salt thereof, is reacted with a compoundof the formula (IIa) to give the compound of the formula (Ic), wherein A1, R2a, R2a’, R2b, R1, R3 and R4a havethe same meaning as given above for compounds of the formula (I). This reaction is done essentially under the same conditions as described above for the transformation of intermediate (XVI) to intermediate (XIV).

[0118] Within these different multistep sequences, the intermediate compounds of formulas (XIV), (XVI),(XVIII) and (IIIa) can be used as crude products for the respective subsequent step, or they can be purified, for instance by chromatography, and used in purified form for the next transformation. Compounds of the formula (XVII) are known, or they can be prepared by methods known to a person skilled in the art.

[0119] Compounds of the formula (Id)can be prepared by the reaction of an amine of the formula (IIIb), or a salt thereof109934 | 83191 FF 32wherein R1, R3, R4a, R5a, and R5b are as described in formula (I), with a compound of the formula (IIa)wherein A1, R2a, R2a’ and R2b are as described in formula (I) and X1 is hydroxy or a leaving group,such as a halogen or a sulfonate, for instance chloride, under conditions already described in Scheme 1.

[0120] The chemistry is described in more detail in Scheme 8.Scheme 8

[0121] Reaction of a compound of the formula (IIa), wherein X1 is a leaving group, such as a halogen orsulfonate, for instance chloride, with a compound of formula (IIIb), or a salt thereof, gives a compound ofthe formula (Id), wherein A1, R2a, R2a’, R2b, R1, R3, R4a, R5a, and R5b have the same meaning as given abovefor compounds of the formula (I). The reaction can be conducted neat or in a solvent, preferably in a solvent,such as an organic solvent, for instance acetonitrile, in a temperature range of -100 to +300 °C, preferablybetween ambient temperature and 200 °C, with or without the presence of a catalyst, for instance a metalcatalyst, such as a palladium complex, and with or without the addition of a base, such as an inorganic base, for instance potassium carbonate, or an organic base, such as, for example, triethylamine.

[0122] The formation of compounds of formula (IIIb) is outlined in Scheme 9.Scheme 9109934 | 83191 FF 33

[0123] Compounds of formula (IIIb), or a salt thereof, can be prepared by treatment of compounds offormula (IIIc), or a salt thereof, wherein R3, R4a, R5a, and R5b are as described in formula (I), with compoundsof formula (XX) wherein R1a is for example H, methyl or cyclopropyl, e.g. in the presence of NaBH(OAc)3or NaBH3CN, in a suitable solvent, preferably in acetic acid at room temperature analogous to WO2002 / 088073, page 35. Alternatively, another reagent system for the reductive amination uses a combination of Ti(i-OiPr)4 and NaBH4 (see Synthesis 2003 (14), 2206).

[0124] Amines of formula (IIIc), or a salt thereof, may be obtained by biocatalyzed deracemization ofamines of formula (IIId), or a salt thereof. This may be done for instance using a lipase, e.g. CandidaAntarctica lipase B or Pseudomonas fluorescens lipase, eventually in immobilized form (e.g. Novozym®435) in presence of an acyl donor, e.g. ethyl methoxyacetate or vinyl acetate, in a suitable solvent such asacetonitrile or methyl tert-butyl ether at temperatures between 20 °C to 100 °C. Such processes aredescribed for instance in J. Org. Chem.2007, 72, 6918-6923 or Adv. Synth. Catal.2007, 349, 1481-1488.The expected stereochemical outcome of such enzymatic deracemization are known of those skilled in the art and are documented in the literature, for instance in J. Org. Chem.1991, 56, 2656-2665 or J. Am. Chem.Soc.2015, 137, 3996−4009.

[0125] In an alternative process, compounds of formula (IIIc), or a salt thereof (such as a hydrohalidesalt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalentsalt), can be obtained from compounds of the formula (XXII), wherein R3, R4a, R5a, and R5b are as describedin formula (I), following the synthesis described in Scheme 10.Scheme 10

[0126] Amines of formula (IIIc), or a salt thereof, may be obtained from intermediates of formula (XXII),wherein R3, R4a, R5a, and R5b are as described in formula (I) and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), typically by treatment with either hydrazine (preferablyhydrazine hydrate or hydrazine monohydrate) in an alcohol solvent such as ethanol or isopropanol (Z3 is -NPhth), or with an acid such as trifluoroacetic acid or hydrochloric acid in the presence of a suitable solventsuch as dichloromethane, tetrahydrofuran or dioxane (Z3 is -NBoc2), under deprotection conditions known to a person skilled in the art, and described in the literature, such as, for example, in: Protective Groups in Organic Synthesis, 3rd Edition Theodora W. Green (The Rowland Institute for Science) and Peter G. M.Wuts (Pharmacia and Upjohn Company), John Wiley & Sons, Inc., New York, NY. 1999, ISBN 0-471-16019-9.109934 | 83191 FF 34

[0127] Such intermediates of formula (XXII), wherein R3, R4a, R5a, and R5b are as described in formula(I) and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), can be obtainedfrom alcohols of formula (XXI), wherein R3, R4a, R5a, and R5b are as described in formula (I), by a Mitsunobureaction, which involves treating alcohols of formula (XXI) with an azodicarboxylate, such as diethylazodicarboxylate or diisopropyl azodicarboxylate in the presence of a phosphine, such astriphenylphosphine or tributylphosphine, and of an amine such as phthalimide (HNPhth) or bis(tert-butoxycarbonyl)amine(HNBoc2). Mitsunobu reactions are known by those skilled in the art to proceed withinversion of the stereocenter, as described for instance in Chem. Rev.2009, 109, 2551-2651.

[0128] Alternatively, amines of formula (IIIc) may be obtained by reduction of azides of formula (XXIII),wherein R3, R4a, R5a, and R5b are as described in formula (I), by treatment with triphenylphosphine andwater (Staudinger reaction) or by hydrogenation for example using a palladium catalyst in the presence of hydrogen. Azides of formula (XXIII) may be obtained by treatment of alcohols of formula (XXI), wherein R3,R4a, R5a, and R5b are as described in formula (I), with an azidation reagent such as diphenyl phosphorylazide in a solvent such as toluene or THF in presence of a base such as DBU. Such processes are known by those skilled in the art to proceed with inversion of the stereocenter and are described in the literaturefor instance in Adv. Synth. Catal.2018, 360, 2157–2165.

[0129] Alcohols of formula (XXI) may be obtained by enantioselective reduction of ketones of formula(XXIV), wherein R3, R4a, R5a, and R5b are as described in formula (I). Such reductions can be done using acatalyst, for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCl[(R,R)- TsDPEN](mesitylene) or RuBF4[(R,R)-TsDPEN](p-cymene) in the presence of a hydrogen donor system such as, for example, HCOOH / Et3N or HCO2NH4. Such processes are described in the literature forinstance in J. Org. Chem.2017, 82, 5607.

[0130] Alternatively, compounds of formula (IIIc) may also be prepared as outlined in Scheme 11.Scheme 11

[0131] Amines of formula (IIIc), or a salt thereof (such as a hydrohalide salt, preferably a hydrochlorideor a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), can be prepared bydeprotection of amines of formula (XXV), wherein R3, R4a, R5a, and R5b are as described in formula (I), for109934 | 83191 FF 35 instance using an acid such as trifluoroacetic acid or hydrochloric acid, optionally in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran or dioxane.

[0132] Amines of formula (XXV) can be obtained by condensation of diamines of formula (XLVII),wherein R5a and R5b are as described in formula (I), on diketones of formula (XXVI), wherein R3 and R4aare as described in formula (I). This condensation can take place in the presence of a suitable solvent such as ethanol or isopropanol in presence of an oxidant such as air or DDQ.

[0133] Diketones of formula (XXVI) may be formed by oxidation of hydroxyketones of formula (XXVII),wherein R3 and R4a are as described in formula (I). This oxidation can involve for instance SO3-pyridine inpresence of solvents such as dichloromethane or dimethyl sulfoxide DMSO, or mixtures thereof, and a base for instance triethylamine or alternatively sodium hypochlorite in presence of a catalyst such as TEMPO / Bu4NHSO4. Examples of such oxidations can be found in the literature, for instance in Synlett,2014, 25, 596 or J. Am. Chem. Soc.1990, 112, 5290-5313.

[0134] Hydroxyketones of formula (XXVII) may be synthesized by cross-benzoin condensation betweenaldehydes of formula (XXIX), wherein R4a is as described in formula (I), and aldehydes of formula (XXVIII),wherein R3is as described in formula (I).

[0135] Aldehydes of formula (XXVIII) are commercially available in chiral form, like for instance Boc-L-alaninal (CAS 79069-50-4) or tert-butyl N-[(1S)-1-(cyclopropylmethyl)-2-oxo-ethyl]carbamate (CAS881902-36-9). Cross-benzoin condensations are done in the usual way by employing an organocatalyst such as a triazolium salt or a thiazolium salt, in the presence of a base such as potassium tert-butoxide orN,N-isopropylethylamine, in a suitable solvent such as DCM or THF, at a temperature between -20 °C andthe boiling point of the solvent. Examples of catalysts for such transformations have been described in theliterature for instance in J. Am. Chem. Soc.2014, 136, 7539-7542 or in Org. Lett.2016, 18, 4518-4521.109934 | 83191 FF 36 Scheme 12

[0136] As shown in Scheme 12, compounds of formula (Id) can be alternatively prepared by reaction ofcompounds of formula (XXX) (wherein A1, R2a, R2a’, R2b, R1, R3, R5a, and R5b are as defined in formula (I)and X07 is a leaving group like, for example, chlorine, bromine, iodine) with compounds of formula (XXXI)(Stille reaction; R4a in XXXI is as defined in formula I) or compounds of formula (XXXII) (Suzuki-Miyaurareaction; R4a in XXXII is as defined in formula (I) and W is a boronic acid B(OH)2 group, or a correspondingboronate, such as a pinacol ester of said boronic acid) in the presence of a palladium catalyst as described in detail in Scheme 7.

[0137] Compounds of formula (XXX) can be prepared by coupling of amines of formula (XXXIII) andcompounds of formula (IIa), wherein A1, R2a, R2a’, R2b and X1 are described in Scheme 1, under theconditions described in detail in Scheme 1. Under the same conditions, if R1 = H, compounds of formula(XXX) may be obtained directly from compounds of formula (XXXIV).

[0138] Compounds of formula (XXXIII) can be prepared by treatment of compounds of formula (XXXIV),with compounds of formula (XX) (wherein R1a is for example H, methyl or cyclopropyl), e.g. in the presenceof NaBH(OAc)3 or NaBH3CN, in a suitable solvent, preferably in acetic acid at room temperature analogous to WO2002 / 088073, page 35. Alternatively, another reagent system for the reductive amination uses a combination of Ti(i-OiPr)4 and NaBH4 (see Synthesis 2003 (14), 2206).

[0139] Amines of formula (XXXIV) can be prepared by deracemization procedure method, which involvesfor example, a selective acylation of one enantiomer. Such an example is described in Scheme 13 more in details.Scheme 13

[0140] Amines of formula (XXXIV) may be obtained by biocatalyzed deracemization of amines of formula(XXXIVa), wherein R3, R5a, and R5b are as in formula (I) and X07 is a leaving group such as bromine, chlorineor iodine. This may be done for instance using a lipase, e.g. Candida Antarctica lipase B or Pseudomonasfluorescens lipase, eventually in immobilized form (e.g. Novozym® 435) in presence of an acyl donor, e.g.ethyl methoxyacetate or vinyl acetate, in a suitable solvent such as acetonitrile or methyl tert-butyl ether attemperatures between 20 °C to 100 °C. Such processes are described for instance in J. Org. Chem.2007,72, 6918-6923 or Adv. Synth. Catal.2007, 349, 1481-1488. The expected stereochemical outcome of suchenzymatic deracemization are known of those skilled in the art and are documented in the literature, forinstance in J. Org. Chem.1991, 56, 2656-2665 or J. Am. Chem. Soc.2015, 137, 3996−4009.

[0141] Alternatively, resolution of amines of formula (XXXIVa) to give amines of formula (XXXIV) maybe achieved using a chiral auxiliary, as described in Scheme 14.109934 | 83191 FF 37Scheme 14

[0142] Amines of formula (XXXIV) can be prepared from intermediates of formula (XXXVII), wherein R3,R5a, and R5b are as in compounds of the formula (I), X07 is a leaving group such as bromine, chlorine oriodine, and X12* is a chiral auxiliary, by treatment with acids such as HCl or bases such as NaOH. Chiralauxiliaries of formula (XXXVI) are for instance mandelic acid or (1R)-menthylchloroformate. Intermediates of formula (XXXVII) can be formed by coupling of a chiral auxiliary of formula (XXXVI), wherein X0 is a leaving group, such as chlorine, with amines of the formula (XXXIVa) following the conditions detailed in Scheme 1. Examples of such deracemization processes are reported in the literature, for instance in J. Org. Chem.2007, 72, 485-493.

[0143] Alternatively, amines of formula (XXXIV), or a salt thereof (such as a hydrohalide salt, preferablya hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), can be formed as described in Scheme 15.Scheme 15

[0144] Amines of formula (XXXIV), or a salt thereof, may be obtained from intermediates of formula(XXIIa), wherein R3, R5a, and R5b are as described in formula (I), X07 is a leaving group such as a halogenor sulfonate, for instance bromide, and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), typically by treatment with either hydrazine (preferably hydrazine hydrate orhydrazine monohydrate) in an alcohol solvent such as ethanol or isopropanol (Z3 is -NPhth), or with an acidsuch as trifluoroacetic acid or hydrochloric acid in the presence of a suitable solvent such asdichloromethane, tetrahydrofuran or dioxane (Z3 is -NBoc2), under deprotection conditions known to a person skilled in the art, and described in the literature, such as, for example, in: Protective Groups in109934 | 83191 FF 38 Organic Synthesis, 3rd Edition Theodora W. Green (The Rowland Institute for Science) and Peter G. M. Wuts (Pharmacia and Upjohn Company), John Wiley & Sons, Inc., New York, NY. 1999, ISBN 0-471- 16019-9.

[0145] Such intermediates of formula (XXIIa), wherein R3, R5a, and R5b are as described in formula (I),X07 is a leaving group such as a halogen or sulfonate, for instance bromide, and Z3 is -NPhth (N-phthalimide group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), can be obtained from alcohols of formula (XXIa),wherein R3, R5a, and R5b are as described in formula (I) and X07 is a leaving group, by a Mitsunobu reaction,which involves treating alcohols of formula (XXIa) with an azodicarboxylate, such as diethylazodicarboxylate or diisopropyl azodicarboxylate, in the presence of a phosphine, such astriphenylphosphine or tributylphosphine, and of an amine such as phthalimide(HNPhth) or bis(tert-butoxycarbonyl)amine (HNBoc2). Mitsunobu reactions are known by those skilled in the art to proceed withinversion of the stereocenter, as described for instance in Chem. Rev.2009, 109, 2551-2651.

[0146] Alternatively, amines of formula (XXXIV) may be obtained by reduction of azides of formula(XXIIIa), wherein R3, R5a, and R5b are as described in formula (I) and X07 is a leaving group such as ahalogen or sulfonate, for instance bromide, by treatment with triphenylphosphine and water (Staudinger reaction) or by hydrogenation for example using a palladium catalyst in the presence of hydrogen. Azides of formula (XXIIIa) may be obtained by treatment of alcohols of formula (XXIa) with an azidation reagentsuch as diphenyl phosphoryl azide in a solvent such as toluene or THF in presence of a base such as DBU.Such processes are known by those skilled in the art to proceed with inversion of the stereocenter and aredescribed in the literature for instance in Adv. Synth. Catal.2018, 360, 2157–2165.Alcohols of formula (XXIa) may be obtained by enantioselective reduction of ketones of formula (XXIVa),wherein R3, R5a, and R5b are as described in formula (I) and X07 is a leaving group such as a halogen orsulfonate, for instance bromide. Such reductions can be done using catalysts, for instance a ruthenium or a rhodium catalyst with a chiral ligand such as RuCl[(R,R)-TsDPEN](mesitylene) or RuBF4[(R,R)- TsDPEN](p-cymene) in the presence of a hydrogen donor system such as, for example, HCOOH / Et3N or HCO2NH4. Such processes are described in the literature for instance in J. Org. Chem.2017, 82, 5607.Scheme 16

[0147] As shown in Scheme 16, compounds of the formula (IIa-1), a subset of compounds of the formula(II) wherein A1, R2a, R2a’ and R2b are as described in formula (I) and X1 is hydroxy, can be prepared bysaponification of compounds of the formula (IIb), wherein A1, R2a, R2a’ and R2b are as described in formula(I), and in which Ra is C1-C6alkyl or benzyl, under conditions known to a person skilled in the art by using,for example, conditions such as: aqueous sodium, potassium or lithium hydroxide in methanol, ethanol, tetrahydrofuran, 2-methyltetrahydrofuran or dioxane at room temperature, or up to refluxing conditions; oralternatively treating compounds of the formula (IIb) with an acid, such as, for example, a hydrohalide acid,109934 | 83191 FF 39preferably hydrochloric or hydrobromic acid, or trifluoroacetic acid, optionally in presence of a solvent, suchas tetrahydrofuran, 2-methyltetrahydrofuran dioxane or dichloromethane, at temperatures ranging from 0°Cto 150°C.

[0148] Compounds of the formula (IIb), wherein A1, R2a, R2a’ and R2b are as described in formula (I), andin which Ra is C1-C6alkyl or benzyl, can be prepared by means of a carbonylation reaction on compoundsof the formula (XL), wherein A1, R2a, R2a’ and R2b are as described in formula (I), and in which X3 is ahalogen, preferably Br, Cl or I (even more preferably Cl or Br), in the presence of an alcohol RaOH, whereinRa is C1-C6alkyl or benzyl. Typically in such a carbonylation reaction, the compounds of formula (XL) arereacted with carbon monoxide CO (usually under pressure, for example in the range of 5 to 200 bar), in thepresence of a metal catalyst such as a palladium catalyst (for example: palladium(II) acetate, or [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) PdCl2(dppf)), optionally in the presence of aphosphine ligand, preferably in the presence of a base such as triethylamine, diisopropylethylamine orpyridine, in an alcohol RaOH solvent (optionally in presence of an inert organic co-solvent), and attemperatures ranging between 0 and 250°C, preferably between room temperature and 200°C.

[0149] Alternatively, compounds of the formula (IIa-1), wherein A1, R2a, R2a’ and R2b are as described informula (I), can be prepared by i. performing a lithium-halogen (Li-X3) exchange on compounds of theformula (XL), wherein A1, R2a, R2a’and R2bare as described in formula (I), and in which X3is a halogen, preferably Br, Cl or I (even more preferably Cl or Br), followed by ii. quenching the formed organolithiumspecies with carbon dioxide. Such lithium-halogen exchange reactions can be performed using, forexample, organolithium compounds such as butyllithium (BuLi), preferably two to three equivalents withrespect to substrate (XL), in an anhydrous aprotic solvent, such as tetrahydrofuran, 2-methyl-tetrahydrofuran or N,N′-dimethylpropylene-urea (DMPU), and at temperatures ranging from -120 to 0°C,preferably between -78 and 0°C. The formed lithiated intermediate is preferably quenched in situ withcarbon dioxide (gasous, or alternatively solid carbon dioxide known as dry ice) to generate the compoundsof the formula (IIa-1). As an alternative to perform the lithium-halogen exchange under above conditions,compounds of the formula (XL) can be treated first with, for instance, isopropylmagnesium chloride (orisopropylmagnesium bromide), preferably 1-1.5 equivalents, followed by treatment with an organolithiumreagent such as butyllithium (BuLi), preferably 1-1.5 equivalents.Scheme 17

[0150] As shown in Scheme 17, compounds of the formula (XL), wherein A1, R2a, R2a’ and R2b are asdescribed in formula (I), and in which X3is a halogen, preferably Br, Cl or I (even more preferably Cl or Br), can be prepared by a halogenation reaction, which involves for example, reacting the compounds of the formula (XL-1), wherein A1, R2a, R2a’and R2bare as described in formula (I), with halogenating reagentssuch as N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS) or N-iodosuccinimide (NIS), 1,3-dichoro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) or 1,3-diodo-5,5-dimethylhydantoin, sulfuryl chloride or alternatively chlorine, bromine or iodine, optionally in presence of a base such as109934 | 83191 FF 40 sodium, potassium or cesium carbonate, and optionally in the presence of a catalyst or an additive. Such halogenation reactions are carried out in an inert solvent, such as chloroform, carbon tetrachloride, 1,2- dichloroethane, acetic acid, trifluoroacetic acid, sulfuric acid, ethers, N,N-dimethyl-formamide, N,N- dimethylacetamide, acetonitrile or acetonitrile-water mixtures, at temperatures between 20-200°C, preferably between room temperature to 120°C.

[0151] Compounds of the formula (XL-1), wherein A1, R2a, R2a’ and R2b are as described in formula (I),can be prepared (ring closure reaction) by treating compounds of the formula (XL-2), wherein A1, R2a, R2a’and R2bare as described in formula (I), with carbonyldiimidazole (CDI), phosgene or phosgene surrogatessuch as di- or triphosgene, optionally in the presence of a base, such as triethylamine,diisopropylethylamine or pyridine, in an inert solvent such as acetonitrile, tetrahydrofuran, 2-methyl- tetrahydrofuran, ethyl acetate, toluene, chlorobenzene, N,N-dimethylacetamide or N,N-dimethyl- formamide, in a temperature range of -20 to +80 °C, preferably between 0°C and ambient temperature, inanalogy to descriptions found for example in Bioorg. Med. Chem. Lett. 2007, 17, 189-192, or in WO18 / 017490.

[0152] Compounds of the formula (XL-2), wherein A1 and R2b are as described in formula (I), R2a ishydrogen, C1-C3alkyl, or C3-C4cycloalkyl and R2a’ is C1-C3alkyl or C3-C4cycloalkyl, can be prepared byreacting compounds of the formula (XL-3), wherein A1and R2bare as described in formula (I), and R2ais hydrogen, C1-C3alkyl, or C3-C4cycloalkyl, with a reagent R2a’-MgX10(Grignard reagent), wherein R2a’is C1-C3alkyl or C3-C4cycloalkyl, and X10is chloro or bromo, in an anhydrous aprotic solvent, such astetrahydrofuran, 2-methyltetrahydrofuran or dioxane, and at temperatures ranging from -120°C to roomtemperature, preferably between -40°C and room temperature, for example at about 0°C, in analogy todescriptions found for example in Bioorg. Med. Chem. Lett.2007, 17, 189-192, or in WO 18 / 017490.

[0153] Compounds of the formula (XL-3), wherein A1 and R2b are as described in formula (I), and R2a ishydrogen, C1-C3alkyl, or C3-C4cycloalkyl, are either known, or they can be prepared by methods known to a person skilled in the art.Scheme 18

[0154] Alternatively, compounds of the formula (XL-1), wherein A1, R2a, R2a’ and R2b are as described informula (I), can be prepared (Scheme 18) by treating compounds of the formula (XL-4), wherein A1, R2a,R2a’ and R2b are as described in formula (I), with a base such as sodium or potassium carbonate, in forinstance alcohol solvents (such as methanol, ethanol or isopropanol), and at temperatures preferablybetween room temperature and the boiling point of the reaction mixture.109934 | 83191 FF 41

[0155] Compounds of the formula (XL-4), wherein A1, R2a, R2a’ and R2b are as described in formula (I),can be prepared by reacting compounds of the formula (XL-5), wherein A1 and R2b are as described informula (I), and R2ais hydrogen, C1-C3alkyl, or C3-C4cycloalkyl, with a reagent R2a’-MgX10(Grignard reagent,preferably about 1-1.5 equivalent), wherein R2a’ is C1-C3alkyl or C3-C4cycloalkyl, and X10 is chloro or bromo,under analogous conditions already described above in Scheme 17 (transformation of XL-3 into XL-2). Upon workup conditions, one of the Boc group (tert-butyloxycarbonyl) gets cleaved in the generation of (XL-4), in analogy to descriptions found for example in WO 2019 / 149164.

[0156] Compounds of the formula (XL-5), wherein A1 and R2b are as described in formula (I), and R2a ishydrogen, C1-C3alkyl, or C3-C4cycloalkyl, can be prepared by reacting compounds of the formula (XL-6),wherein A1and R2bare as described in formula (I), and Rb is C1-C6alkyl or benzyl, with a reagent R2a-MgX10(Grignard reagent, preferably about 1-1.5 equivalent), wherein R2a is C1-C3alkyl or C3-C4cycloalkyl, and X10is chloro or bromo, under analogous conditions already described above in Scheme 17 (transformation ofXL-3 into XL-2).

[0157] In the sequence from (XL-6) to (XL-4) via (XL-5), the intermediate compounds of the formula (XL-5) can be isolated and purified, or the overall reaction may be performed in a 2-steps one-pot fashion.

[0158] In the particular situation where R2a is equal to R2a’, the above process from (XL-6) to (XL-4) isadapted by adding preferably about 2 to 4 equivalents of the reagent R2a-MgX10 (while R2a’-MgX10 is omitted)to substrate (XL-6), followed by workup, as detailed for example in WO 2019 / 149164.Scheme 19

[0159] Compounds of the formula (XL-6), wherein A1 and R2b are as described in formula (I), and Rb isC1-C6alkyl or benzyl, can be prepared (Scheme 19) by bis-Boc protection of compounds of the formula (XL-7), wherein A1and R2bare as described in formula (I), and Rb is C1-C6alkyl or benzyl, under conditions illustrated for example in WO 2019 / 149164, and otherwise known to a person skilled in the art, and described in the literature, such as, for example, in: Protective Groups in Organic Synthesis, 3rd Edition Theodora W. Green (The Rowland Institute for Science) and Peter G. M. Wuts (Pharmacia and Upjohn Company), John Wiley & Sons, Inc., New York, NY.1999, ISBN 0-471-16019-9.

[0160] Compounds of the formula (XL-7), wherein A1 and R2b are as described in formula (I), and Rb isC1-C6alkyl or benzyl, are either known, or they can be prepared by methods known to a person skilled in the art.109934 | 83191 FF 42= Scheme 19a

[0161] Alternatively, compounds of the formula (XL-2), wherein A1 and R2b are as described in formula(I), R2ais hydrogen, C1-C3alkyl, or C3-C4cycloalkyl and R2a’is C1-C3alkyl or C3-C4cycloalkyl, may be prepared from compounds of the formula (XL-7), wherein A1and R2bare as described in formula (I), and Rb is C1-C6alkyl or benzyl, in analogy to descriptions and conditions already mentioned in Schemes 17 and 18, and with or without isolation of the intermediate compounds of the formula (XL-3).Scheme 20

[0162] Alternatively (Scheme 20), compounds of the formula (IIb), wherein A1, R2a, R2a’ and R2b are asdescribed in formula (I), and in which Ra is C1-C6alkyl or benzyl, can be prepared by ring closing compounds of the formula (XL-8), wherein A1, R2a, R2a’and R2bare as described in formula (I), and in which Ra is C1-C6alkyl or benzyl, with carbonyldiimidazole (CDI), phosgene or phosgene surrogates such as di- ortriphosgene, under analogous conditions already described above in Scheme 17 (transformation of XL-2into XL-1).

[0163] Compounds of the formula (XL-8), wherein A1 and R2b are as described in formula (I), R2a ishydrogen, C1-C3alkyl, or C3-C4cycloalkyl and R2a’ is C1-C3alkyl or C3-C4cycloalkyl, and in which Ra is C1-C6alkyl or benzyl, can be prepared by reacting compounds of the formula (XL-9), wherein A1 and R2b areas described in formula (I), R2ais hydrogen, C1-C3alkyl, or C3-C4cycloalkyl, and in which Ra is C1-C6alkyl or benzyl, with a reagent R2a’-MgX10(Grignard reagent), wherein R2a’is C1-C3alkyl or C3-C4cycloalkyl, and X10is chloro or bromo, under analogous conditions already described above in Scheme 17 (transformation ofXL-3 into XL-2).metal-X4exchange, quench withScheme 21109934 | 83191 FF 43

[0164] Compounds of the formula (XL-9), wherein A1 and R2b are as described in formula (I), R2a ishydrogen, C1-C3alkyl, or C3-C4cycloalkyl, and in which Ra is C1-C6alkyl or benzyl, may be prepared(Scheme 21) by i. performing a metal-halogen (metal-X4) exchange, for example a magnesium-X4exchange, on compounds of the formula (XL-10), wherein A1 and R2b are as described in formula (I), X4 isa halogen, preferably bromine, chlorine or iodine (even more preferably bromine or chlorine), and in whichRa is C1-C6alkyl or benzyl, followed by ii. quenching the formed organomagnesium species with for instanceethyl formate or N,N-dimethylformamide (R2ais hydrogen), or with an acylating agent of the formula R2a(CO)O(CO)R2a(alternatively the corresponding acid chloride R2aC(O)Cl or the Weinreb amideR2aC(O)N(Me)OMe), wherein R2a is C1-C3alkyl, or C3-C4cycloalkyl. Such magnesium-halogen exchangereactions can be performed using, for example, Grignard reagents such as isopropylmagnesium chlorideor bromide, optionally in the presence of lithium chloride (for instance by involving isopropylmagnesium chloride lithium chloride complex, known as Turbo Grignard). The magnesium-halogen exchange reaction can be performed in an anhydrous aprotic solvent, such as tetrahydrofuran, 2-methyltetrahydrofuran ordioxane, and at temperatures ranging from -120 to 0°C, preferably between -78 and 0°C.

[0165] Alternatively, compounds of the formula (XL-9), wherein A1 and R2b are as described in formula(I), R2ais specifically methyl, and in which Ra is C1-C6alkyl or benzyl, can be prepared by reactingcompounds of the formula (XL-10), wherein A1 and R2b are as described in formula (I), X4 is a halogen,preferably bromine, chlorine or iodine, and in which Ra is C1-C6alkyl or benzyl, with butyl vinyl ether (Heck reaction) or tributyl(1-ethoxyvinyl)stannane (Stille reaction), typically under palladium catalysis cross-coupling conditions known to a person skilled in the art, followed by hydrolysis of the formed enol ether. Anexample of such a Stille coupling / hydrolysis sequence is reported in WO 23 / 066371.

[0166] Compounds of the formula (XL-10), wherein A1 and R2b are as described in formula (I), X4 is ahalogen, preferably bromine, chlorine or iodine, and in which Ra is C1-C6alkyl or benzyl, can be preparedby performing a halogenation reaction on compounds of the formula (XL-11), wherein A1and R2bare asdescribed in formula (I), and in which Ra is C1-C6alkyl or benzyl, under analogous conditions alreadydescribed above in Scheme 17 (transformation of XL-1 into XL).

[0167] Compounds of the formula (XL-11), wherein A1 and R2b are as described in formula (I), and inwhich Ra is C1-C6alkyl or benzyl, are either known, or they can be prepared by methods known to a person skilled in the art.

[0168] Certain compounds of formula (III), or a salt thereof (such as a hydrohalide salt, preferably ahydrochloride or a hydrobromide salt, or any other equivalent salt), wherein R1, R3 and Q have the samemeaning as given above for compounds of the formula (I), are known in the literature.

[0169] For example, compounds of the formula (IIIa) and (IIIb), or a salt thereof as defined above,wherein R1, R3, R4a, R5a and R5b are as described in formula (I), particularly those compounds of the formula(IIIa) and (IIIb), or a salt thereof as defined above, wherein R3 and R4a are as described in formula (I) andin which R1, R5a and R5b are hydrogen, can be prepared in analogy to descriptions found for example in WO2021 / 083936, WO 2021 / 069575 and WO 2022 / 258481.109934 | 83191 FF 44

[0170] Similarly, compounds of the formula (IIIe) and (IIIf), or a salt thereof as defined above, whereinR1, R3, R4 and R5 are as described in formula (I), particularly those compounds of the formula (IIIe) and(IIIf), or a salt thereof as defined above, wherein R3 and R4 are as described in formula (I) and in which R1is hydrogen or methyl and R5 is hydrogen, methyl or cyclopropyl, can be prepared in analogy to descriptionsfound for example in WO 2021 / 083936, WO 2021 / 099303, WO 2021 / 105091, WO 2021 / 165195 andWO 2021 / 224323, WO 2022 / 268648, WO 2023 / 104714 and WO 2023 / 247360.

[0171] In particular, compounds of the formula (IIIg), wherein R1, R3 and R5 are as described in formula(I) and X5 is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), can be prepared according toreactions outlined in Scheme 22.

[0172] Compounds of the formula (IIIg), wherein R1, R3 and R5 are as described in formula (I) and X5is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), can be prepared from compounds offormula (IIIg-1), wherein R1, R3 and R5 are as described in formula (I) and X5 is a halogen, preferably Br, Clor I (even more preferably Br or Cl), and X- is an anion, by treatment with a base, such as for example a hydroxide base or a carbonate base, for example sodium hydroxide or potassium carbonate, or an ion109934 | 83191 FF 45 exchange resin. Such procedures are well known to a person skilled in the art and known from the literature and textbooks. The anion X- is the conjugate base of an acid, such as an inorganic acid, for instance hydrochloric acid, hydrobromic acid, hydrogen fluoride, hydrogen iodide, sulfuric acid, or the like, or of an organic acid, such as a carboxylic acid or a sulfonic acid, for instance trifluoroacetic acid, or methane sulfonic acid, or para-toluene sulfonic acid. A great number of such acids are known to a person skilled in the art.

[0173] Compounds of formula (IIIg-1), wherein R1, R3 and R5 are as described in formula (I) and X5 is ahalogen, preferably Br, Cl or I (even more preferably Br or Cl), and X- is an anion, can be made fromcompounds of the formula (IIIg-2), wherein R1, R3 and R5 are as described in formula (I) and X5 is a halogen,preferably Br, Cl or I (even more preferably Br or Cl), by treatment with an acid, such as the acids listed above. The reaction can be done neat or in a solvent, for instance an organic solvent, such as in methanol, tetrahydrofuran, dichloromethane, trifluoromethylbenzene or in dioxane, or in an inorganic solvent, such as in water, or in a mixture of such solvents. The reaction can be done in a temperature range between -100 °C and 200 °C, more commonly between 0 °C and 150 °C, such as, for example, at ambienttemperature.

[0174] Compounds of the formula (IIIg-2), wherein R1, R3 and R5 are as described in formula (I) and X5is a halogen, preferably Br, Cl or I (even more preferably Br or Cl), can be prepared by reaction ofcompounds of the formula (XII-1), or a tautomer thereof, or a salt thereof, wherein X5 is a halogen,preferably Br, Cl or I (even more preferably Br or Cl), with a compound of the formula (IIIg-3), wherein R1,R3 and R5 are as defined for compounds of the formula (I). The reaction can be done neat, or in a solvent,for instance an organic solvent, such as dioxane or acetic acid, or a mixture thereof. The reaction can be performed in the presence or in the absence of a drying agent, such as for example in the presence ofmolecular sieves, at a temperature between -100 °C and 200 °C, more commonly between 0 °C and150 °C, such as, for example, at 80 °C.

[0175] Compounds of the formula (XII-1), or a tautomer thereof, or a salt thereof, wherein X5 is ahalogen, preferably Br, Cl or I (even more preferably Br or Cl), are known or even commercially available,or they can be made by known methods. Compounds of the formula (IIIg-3), wherein R1, R3 and R5 are asdefined for compounds of the formula (I), are known, for instance from WO2021 / 083936 or WO2021 / 165195, or they can be made in analogy to descriptions found therein.

[0176] Alternatively, compounds of the formula (IIIf-1), wherein R1, R4 and R5 are as defined forcompounds of the formula (I), or a salt thereof (IIIf-2), in which X- is an anion as defined above in Scheme22 (compounds of the formula (IIIf-1) are representatives of compounds of the formula (IIIf) in which R3 isCH3), can be made (Scheme 23) from compounds of the formula (IIIf-3), wherein R1, R4 and R5 are asdefined for compounds of the formula (I), following the chemistry and conditions described above in Scheme22 (transformation IIIg-2 into IIIg via IIIg-1).109934 | 83191 FF 46Scheme 23

[0177] Compounds of the formula (IIIf-3), wherein R1 and R4 are as defined for compounds of the formula(I), and in which R5 is hydrogen or C1-C3alkyl, can be prepared by reacting compounds of the formula (IIIg-3), in which R3 is CH3 and wherein R1 is as defined for compounds of the formula (I) and R5 is hydrogen orC1-C3alkyl, with hydrazine compounds of the formula (XII) or a tautomer thereof, or a saltthereof, wherein R4 is as defined for compounds of the formula (I), under analogous conditionsalready described above in Scheme 6 (transformation XI + XII into Ib).

[0178] Alternatively, compounds of the formula (IIIf-3), wherein R1 and R4 are as defined for compoundsof the formula (I), and in which R5is C1-C3alkyl or C3-C4cycloalkyl, can be prepared by reacting compoundsof the formula (IIIf-4), wherein R1 is as defined for compounds of the formula (I) and R5 is C1-C3alkyl or C3-C4cycloalkyl, and RL is -NH2 or -OC1-C4alkyl, with hydrazine compounds of the formula (XII) or a tautomerthereof, or a salt thereof, wherein R4 is as defined for compounds of the formula (I),under analogous conditions already described above in Scheme 6 (transformation XI + XII into Ib) ordetailed in J Org Chem, 2011, 76, 1177-1179.

[0179] Compounds of the formula (IIIf-4), wherein R1 is as defined for compounds of the formula (I) andR5is C1-C3alkyl or C3-C4cycloalkyl, and RLis -NH2 or -OC1-C4alkyl, can be prepared by reacting compoundsof the formula (IIIf-5), wherein R1 is as defined for compounds of the formula (I), with compounds of theformula (IIIf-6) or a tautomer thereof, or a salt thereof (such as a hydrohalide salt, preferably a hydrochlorideor a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), wherein R5is C1-C3alkyl or C3-C4cycloalkyl, and RLis -NH2 or -OC1-C4alkyl, in the presence of a coupling reagent, such as, for example, HATU (1-[bis(dimethylamino)-methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, also known as Hexafluorophosphate Azabenzotriazole Tetramethyl Uronium), PyBOP (benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate) or propanephosphonic acid cyclic anhydride (T3P®). Such reactions can be conducted neat or in a solvent, preferably in a solvent, such as an organic solvent, for instance acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N-dimethylacetamide or N,N-dimethylformamide, in a temperature range of -100 to +300 °C, preferably between ambient temperature and 200 °C, and with or without the addition of a base, such asan inorganic base, for instance sodium, potassium or cesium carbonate, or an organic base, such as, for109934 | 83191 FF 47 example, triethylamine, diisopropylethylamine or pyridine. Such conditions are described for example in J Org Chem, 2011, 76, 1177-1179.

[0180] Compounds of the formula (IIIf-5), wherein R1 is as defined for compounds of the formula (I), areknown or even commercially available, or they can be made by known methods.

[0181] Compounds of the formula (IIIf-6) or a tautomer thereof, or a salt thereof, wherein R5 is C1-C3alkylor C3-C4cycloalkyl, and RL is -NH2 (compound IIIf-6 is an alkyl or cycloalkyl amidine, for examplecyclopropanecarboxamidine) or -OC1-C4alkyl (compound IIIf-6 is an alkyl or cycloalkyl imidate, for exampleethyl propanimidate), are known or even commercially available, or they can be made by known methods.

[0182] Compounds of the formula (XL-12), wherein A1, R2a and R2a’ are as described in formula (I), andin which X3is a halogen, preferably Br, Cl or I (even more preferably Cl or Br), form a particular subset ofcompounds of the formula (XL), wherein R2b is difluoromethyl.Scheme 24

[0183] Such compounds of the formula (XL-12) can be prepared (Scheme 24) by reacting compoundsof the formula (XL-13), wherein A1, R2a and R2a’ are as described in formula (I), and in which X3 is a halogen,preferably Br, Cl or I (even more preferably Cl or Br), with fluorinating reagents such as diethylaminosulfur trifluoride (DAST), bis-(2-methoxy-ethyl)aminosulfur trifluoride (trade name: Deoxo-Fluor),difluoro(morpholino)sulfonium tetrafluoroborate (trade name: XtalFluor-M) or the combination of sulfurylfluoride and tetramethylammonium fluoride (see Org. Lett. 2019, 21, 5, 1350-1353), in solvents such as acetonitrile, toluene, dichloromethane or 1,2-dichloroethane, or mixtures thereof, and at temperatures ranging from 0°C to the boiling point of the reaction mixture, preferably between 0°C to room temperature.

[0184] Compounds of the formula (XL-13), wherein A1, R2a and R2a’ are as described in formula (I), andin which X3is a halogen, preferably Br, Cl or I (even more preferably Cl or Br), can be prepared by ahalogenation reaction of compounds of the formula (XL-14), wherein A1, R2a and R2a’ are as described informula (I), under analogous conditions already above in Scheme 17 (transformation XL-1 into XL).

[0185] Compounds of the formula (XL-14), wherein A1, R2a and R2a’ are as described in formula (I), canbe prepared by i. performing a metal-halogen (in this instance metal-R2b) exchange, for example amagnesium-R2b exchange, on compounds of the formula (XL-1), wherein A1, R2a and R2a’ are as describedin formula (I), and R2bis a halogen, preferably Cl, Br or I (even more preferably Br or I), followed by ii. quenching the formed organomagnesium species with for instance N,N-dimethylformamide, 4-formylmorpholine or any other equivalent formyl donor. Such magnesium-halogen exchange reactions canbe performed using, for example, Grignard reagents such as isopropylmagnesium chloride or bromide, optionally in the presence of lithium chloride (for instance by involving isopropylmagnesium chloride lithiumchloride complex, known as Turbo Grignard). The magnesium-halogen exchange reaction can beperformed in an anhydrous aprotic solvent, such as tetrahydrofuran, 2-methyltetrahydrofuran or dioxane,and at temperatures ranging from -120 to 0°C, preferably between -78 and 0°C.109934 | 83191 FF 48

[0186] Compounds of the formula (XL-15), wherein A1, R2a and R2a’ are as described in formula (I), forma particular subset of compounds of the formula (XL-1), wherein R2b is difluoromethoxy.Scheme 25

[0187] Such compounds of the formula (XL-15) can be prepared (Scheme 25) by difluoromethylation ofcompounds of the formula (XL-16), wherein A1, R2a and R2a’ are as described in formula (I), underconditions known to a person skilled in the art. Typically, compounds of the formula (XL-16) are reactedwith a :CF2 carbene species, generated from difluoromethylating agents such a difluoroacetateXcCF2COONa or a difluoromethyl(phosphonate) XcCF2P(O)(OEt)2 reagent, wherein Xccan be chloro orbromo, in the presence of a base such as for example sodium or potassium carbonate, or sodium orpotassium hydroxide, in an appropriate solvent like for example acetonitrile, Ν,Ν-dimethylformamide or N-methyl-2-pyrrolidone (NMP), optionally in a mixture with water, optionally in the presence of an additive(such as 2'-hydroxyacetophenone), and at temperature between -40°C to 80°C. Such methods have beendescribed in the literature, for example in Org. Lett.2013, 15(19), 5036-5039; Tetrahedron 2009, 65(27), 5278-5283; or Chem. Commun.2017, 53, 5706.

[0188] Compounds of the formula (XL-16), wherein A1, R2a and R2a’ are as described in formula (I), canbe prepared by reacting compounds of the formula (XL-1), wherein A1, R2a and R2a’ are as described informula (I), and R2b is a halogen, preferably Cl, Br or I (even more preferably Br or I), with for examplebenzaldoxime PhC=NOH, preferably (E)-benzaldehyde oxime, in the presence of a base, such as potassium or cesium carbonate, optionally in the presence of a palladium catalyst such as RockPhos-G3- palladacycle ([(2-Di-tert-butylphosphino-3-methoxy-6-methyl-2′,4′,6′-triisopropyl-1,1′-biphenyl)-2-(2- aminobiphenyl)]palladium(II) methanesulfonate), in an aprotic solvent such as acetonitrile or N,N- dimethylformamide DMF, at temperatures between 0 and 100°C, preferably between room temperature and 80°C, as described, for example, in Angew. Chem. Int. Ed.56 (16), 4478–4482, 2017.

[0189] Alternatively, compounds of the formula (XL-16), wherein A1, R2a and R2a’ are as described informula (I), can be prepared from compounds of the formula (XL-1), wherein A1, R2a and R2a’ are asdescribed in formula (I), and R2bis a halogen, preferably Cl, Br or I (even more preferably Br or I), by a borylation (typically involving 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2- dioxaborolane; also known as bis(pinacolato)diborane) / oxidation (typically involving H2O2) sequence, underconditions known to a person skilled in the art, and detailed for example in Organic Letters 2016, 18, 5248-5251 or Journal of Organic Chemistry 2024, 89, 12452-12461.

[0190] The chemistry shown above (Scheme 25) for the transformation XL-1 to XL-15 can be performedwith some additional protection / deprotection steps as shown in Scheme 25a.109934 | 83191 FF 49Scheme 25a

[0191] The chemistry and conditions for the transformation of compounds of the formula (XL-1-a) to (XL-15-a) (Scheme 25a) is analogous to the descriptions above for the transformation of compounds of the formula (XL-1) to (XL-15) (Scheme 25), wherein the definition of the substituents A1, R2a, R2a’and R2bremains as detailed in said Scheme 25, and in which PG is a protective group, such as, for example, an acetyl, a tert-butyloxycarbonyl (Boc), or a para-methoxy benzyl group. Protection conditions (transformation XL-1 to XL-1-a), respectively deprotection conditions (transformation XL-15-a to XL-15) are well known to a person skilled in the art, and described in the literature, such as, for example, in: Protective Groups in Organic Synthesis, 3rd Edition Theodora W. Green (The Rowland Institute for Science) and Peter G. M. Wuts (Pharmacia and Upjohn Company), John Wiley & Sons, Inc., New York, NY. 1999, ISBN 0-471- 16019-9. For instance, Boc protection of XL-1 to generate XL-1-a, wherein PG is tert-butyloxycarbonyl (Boc), can be achieved by treatment of XL-1 with Boc-anhydride, optionally in the presence of an inert solvent (for example acetonitrile), and at temperatures between room temperature and the boiling point of the reaction mixture. Deprotection of XL-15-a, wherein PG is tert-butyloxycarbonyl (Boc), can be achieved by treatment with for instance hydrochloric acid (for example as a solution in dioxane), optionally in the presence of an inert solvent (for example ethyl acetate), and at temperatures between room temperature and the boiling point of the reaction mixture.Scheme 26

[0192] Alternatively, compounds of the formula (IIa-1), wherein A1, R2a, R2a’ and R2b are as described informula (I), can be prepared (Scheme 26) by means of a permanganate oxidation of compounds of theformula (XL-18), wherein A1, R2a, R2a’ and R2b are as described in formula (I). Typically, an aqueous solutionof (XL-18), optionally in the presence of a co-solvent such as tert-butanol, is treated with potassium permanganate (preferably in excess) and the mixture heated to the boiling point of the reaction mixture, under conditions described for example in Bioorg. Med. Chem.2023, 86, 117288 or Organic Syntheses, Coll. Vol.3, p.740 (1955); Vol.20, p.79 (1940). Instead, chromium trioxide in concentrated sulfuric acid maybe used as oxidant as detailed for example in ACS Medicinal Chemistry Letters (2014), 5(8), 921-926.

[0193] Compounds of the formula (XL-18), wherein A1, R2a, R2a’ and R2b are as described in formula (I),can be prepared via ring closure reaction of compounds of the formula (XL-19), wherein A1, R2a, R2a’ and109934 | 83191 FF 50 R2bare as described in formula (I), under conditions already described in Scheme 17 (transformation XL-2 into XL-1).

[0194] Compounds of the formula (XL-19), wherein A1 and R2b are as described in formula (I), R2a ishydrogen, C1-C3alkyl, or C3-C4cycloalkyl and R2a’is C1-C3alkyl or C3-C4cycloalkyl, can be prepared byreacting compounds of the formula (XL-20), wherein A1 and R2b are as described in formula (I), and R2a ishydrogen, C1-C3alkyl, or C3-C4cycloalkyl, with a reagent R2a’-MgX10(Grignard reagent), wherein R2a’is C1-C3alkyl or C3-C4cycloalkyl, and X10is chloro or bromo, under conditions already described in Scheme 17 (transformation XL-3 into XL-2).Scheme 27

[0195] Alternatively, compounds of the formula (XL-19), wherein A1 and R2b are as described in formula(I), R2ais hydrogen, C1-C3alkyl, or C3-C4cycloalkyl and R2a’is C1-C3alkyl or C3-C4cycloalkyl, can be prepared(Scheme 27) from compounds of the formula (XL-21), wherein A1 and R2b are as described in formula (I),and Rb is C1-C6alkyl or benzyl, and with or without isolation of the intermediate compounds of the formula (XL-20), under conditions already described in Scheme 19a (transformation XL-7 into XL-2, optionally via intermediate XL-3).

[0196] Compounds of the formula (XL-18-1), wherein A1, R2a and R2a’ are as described in formula (I),form a particular subset of compounds of the formula (XL-18), wherein R2b is cyclopropyl.Scheme 28

[0197] Such compounds of the formula (XL-18-1) can be prepared (Scheme 28) by reacting compoundsof the formula (XL-18), wherein A1, R2a and R2a’ are as described in formula (I), and R2b is a halogen,preferably Cl, Br or I (even more preferably Br or I), with compounds of the formula (XL-18-A), wherein M is a boron-derived functional group, such as for example BF3K (compound XL-18-A is potassium cyclopropyltrifluoroborate), B(OH)2 (compound XL-18-A is cyclopropylboronic acid) or B(ORc)2, wherein Rc can be a C1-C4alkyl group or the two groups ORc can form together with the boron atom a five membered ring, such as for example a pinacol boronic ester (Suzuki cross-coupling), or alternatively, with compounds109934 | 83191 FF 51 of the formula (XL-18-A), wherein M is a zinc-derived functional group, such as for example ZnBr (compound XL-18-A is cyclopropylzinc bromide) or ZnCl (Negishi cross-coupling).

[0198] Suzuki cross-coupling reactions may be conducted in the presence of a palladium- or nickel-based catalyst, for example tetrakis(triphenylphosphine)palladium, or (1,1'bis(diphenylphosphino)ferrocene)-dichloropalladium-dichloromethane (1:1 complex), or chloro[(tri-tert- butylphosphine)-2-(2-aminobiphenyl)] palladium(II) (P(t-Bu)3 Pd G2), in the presence of a base, such as sodium carbonate, potassium carbonate, cesium carbonate or cesium fluoride, in a solvent or a solvent mixture, like, for example a mixture of toluene and water or of 1,2-dimethoxyethane and water or of dioxane and water or of acetonitrile and water, preferably under inert atmosphere. The reaction temperature can preferentially range from ambient temperature to the boiling point of the reaction mixture. Such Suzukireactions are well known to those skilled in the art and have been reviewed in, for example, in J.Orgmet.Chem.576, 1999, 147–168.

[0199] Negishi cross-coupling reactions may be conducted in the presence of a palladium- or nickel-based catalyst, such as for example, (1,1'bis(diphenylphosphino)-ferrocene)dichloropalladium Pd(dppf)Cl2, bis(triphenylphosphine)palladium(II) dichloride or palladium-PEPPSI-type complexes (such as PEPPSI™- IPr catalyst, CAS 905459-27-0), optionally in the presence of phosphine additives (such as, for example, 2-dicyclohexyl-phosphino-2',6'-dimethoxy-biphenyl S-PHOS), in a solvent, like, for example 1,2- dimethoxyethane, dioxane, toluene, 2-methyltetrahydrofuran or tetrahydrofuran, preferably under inert atmosphere. The reaction temperature can preferentially range from ambient temperature to the boiling point of the reaction mixture. Such Negishi reactions are well known to those skilled in the art and havebeen illustrated for example in Synthetic Communications, 28(2), 225-232; 1998.

[0200] Compounds of the formula (XL-18), wherein A1, R2a and R2a’ are as described in formula (I), andR2bis chloro, bromo or iodo, can be prepared by a halogenation reaction of compounds of the formula (XL-18), wherein A1, R2a and R2a’ are as described in formula (I), and R2b is hydrogen, under analogousconditions already above in Scheme 17 (transformation XL-1 into XL) or in analogy to descriptions found in WO 2018 / 007217.

[0201] Compounds of the formula (XL-18-A), wherein M is BF3K, B(OH)2, ZnBr or ZnCl, are either known,commercial, or they can be prepared by methods known to a person skilled in the art.

[0202] Depending on the procedure or the reaction conditions, the reactants can be reacted in thepresence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metalalkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturatedcycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine,diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine,benzyltrimethylammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).109934 | 83191 FF 52

[0203] The reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. Inmost cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such astriethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also act as solvents or diluents.

[0204] The reactions are advantageously carried out in a temperature range from approximately -80°Cto approximately +140°C, preferably from approximately -30°C to approximately +100°C, in many cases in the range between ambient temperature and approximately +80°C.

[0205] Depending on the choice of the reaction conditions and starting materials which are suitable ineach case, it is possible, for example, in one reaction step only to replace one substituent by another substituent according to the invention, or a plurality of substituents can be replaced by other substituents according to the invention in the same reaction step.

[0206] Salts of compounds of formula (I) can be prepared in a manner known per se. Thus, for example,acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.

[0207] Salts of compounds of formula (I) can be converted in the customary manner into the freecompounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.

[0208] Salts of compounds of formula (I) can be converted in a manner known per se into other salts ofcompounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.

[0209] Depending on the procedure or the reaction conditions, the compounds of formula (I), which havesalt-forming properties can be obtained in free form or in the form of salts.

[0210] The compounds of formula (I) and, where appropriate, the tautomers thereof, in each case in freeform or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and / or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and / or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.

[0211] Diastereomer mixtures or racemate mixtures of compounds of formula (I), in free form or in saltform, which can be obtained depending on which starting materials and procedures have been chosen canbe separated in a known manner into the pure diastereomers or racemates on the basis of thephysicochemical differences of the components, for example by fractional crystallization, distillation and / or chromatography.109934 | 83191 FF 53

[0212] Enantiomer mixtures, such as racemates, which can be obtained in a similar manner can beresolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the diastereomers, from which the desired enantiomer can be set free by the action of suitable agents, for example basic agents.

[0213] Pure diastereomers or enantiomers can be obtained according to the invention not only byseparating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.

[0214] N-oxides can be prepared by reacting a compound of the formula (I) with a suitable oxidizingagent, for example the H2O2 / urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride.Such oxidations are known from the literature, for example from J. Med. Chem., 32 (12), 2561-73, 1989 orWO 2000 / 15615.

[0215] It is advantageous to isolate or synthesize in each case the biologically more effective isomer, forexample enantiomer or diastereomer, or isomer mixture, for example enantiomer mixture or diastereomer mixture, if the individual components have a different biological activity.

[0216] The compounds of formula (I) and, where appropriate, the tautomers thereof, in each case in freeform or in salt form, can, if appropriate, also be obtained in the form of hydrates and / or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.

[0217] The compounds of formula (I) according to the following Tables A-1 to A-24 and Tables B-1 to B-5 can be prepared according to the methods described above. The examples which follow are intended toillustrate the invention and show preferred compounds of formula (I), in the form of a compound of formula(I-A) and (I-B).Tables A-1 to A-24 (formula I-A)

[0218] Table A-1 provides 20 compounds A-1.001 to A-1.020 of formula I-A wherein R2a and R2a’ areboth H, A1 is CH, R2b is Cl, R1 is H and Q are as defined in table Z.

[0219] For example, compound A-22.011 is109934 | 83191 FF 54

[0220] Table A-2 provides 20 compounds A-2.001 to A-2.020 of formula I-A wherein R2a and R2a’ areboth H, A1 is CH, R2b is Cl, R1 is CH3 and Q are as defined in table Z.

[0221] Table A-3 provides 20 compounds A-3.001 to A-3.020 of formula I-A wherein R2a and R2a’ areboth H, A1 is CH, R2b is Br, R1 is H and Q are as defined in table Z.

[0222] Table A-4 provides 20 compounds A-4.001 to A-4.020 of formula I-A wherein R2a and R2a’ areboth H, A1 is CH, R2b is Br, R1 is CH3 and Q are as defined in table Z.

[0223] Table A-5 provides 20 compounds A-5.001 to A-5.020 of formula I-A wherein R2a and R2a’ areboth H, A1 is CH, R2b is I, R1 is H and Q are as defined in table Z.

[0224] Table A-6 provides 20 compounds A-6.001 to A-6.020 of formula I-A wherein R2a and R2a’ areboth H, A1 is CH, R2b is I, R1 is CH3 and Q are as defined in table Z.

[0225] Table A-7 provides 20 compounds A-7.001 to A-7.020 of formula I-A wherein R2a and R2a’ areboth H, A1 is CH, R2b is CF3, R1 is H and Q are as defined in table Z.

[0226] Table A-8 provides 20 compounds A-8.001 to A-8.020 of formula I-A wherein R2a and R2a’ areboth H, A1 is CH, R2b is CF3, R1 is CH3 and Q are as defined in table Z.

[0227] Table A-9 provides 20 compounds A-9.001 to A-9.020 of formula I-A wherein R2a and R2a’ areboth CH3, A1 is CH, R2b is Cl, R1 is H and Q are as defined in table Z.

[0228] Table A-10 provides 20 compounds A-10.001 to A-10.020 of formula I-A wherein R2a and R2a’ areboth CH3, A1 is CH, R2b is Cl, R1 is CH3 and Q are as defined in table Z.

[0229] Table A-11 provides 20 compounds A-11.001 to A-11.020 of formula I-A wherein R2a and R2a’ areboth CH3, A1 is CH, R2b is Br, R1 is H and Q are as defined in table Z.

[0230] Table A-12 provides 20 compounds A-12.001 to A-12.020 of formula I-A wherein R2a and R2a’ areboth CH3, A1 is CH, R2b is Br, R1 is CH3 and Q are as defined in table Z.

[0231] Table A-13 provides 20 compounds A-13.001 to A-13.020 of formula I-A wherein R2a and R2a’ areboth CH3, A1 is CH, R2b is I, R1 is H and Q are as defined in table Z.

[0232] Table A-14 provides 20 compounds A-14.001 to A-14.020 of formula I-A wherein R2a and R2a’ areboth CH3, A1 is CH, R2b is I, R1 is CH3 and Q are as defined in table Z.

[0233] Table A-15 provides 20 compounds A-15.001 to A-15.020 of formula I-A wherein R2a and R2a’ areboth CH3, A1 is CH, R2b is CF3, R1 is H and Q are as defined in table Z.

[0234] Table A-16 provides 20 compounds A-16.001 to A-16.020 of formula I-A wherein R2a and R2a’ areboth CH3, A1 is CH, R2b is CF3, R1 is CH3 and Q are as defined in table Z.

[0235] Table A-17 provides 20 compounds A-17.001 to A-17.020 of formula I-A wherein R2a and R2a’ areboth CH2CH3, A1 is CH, R2b is Cl, R1 is H and Q are as defined in table Z.

[0236] Table A-18 provides 20 compounds A-18.001 to A-18.020 of formula I-A wherein R2a and R2a’ areboth CH2CH3, A1 is CH, R2b is Cl, R1 is CH3 and Q are as defined in table Z.109934 | 83191 FF 55

[0237] Table A-19 provides 20 compounds A-19.001 to A-19.020 of formula I-A wherein R2a and R2a’ areboth CH2CH3, A1 is CH, R2b is Br, R1 is H and Q are as defined in table Z.

[0238] Table A-20 provides 20 compounds A-20.001 to A-20.020 of formula I-A wherein R2a and R2a’ areboth CH2CH3, A1 is CH, R2b is Br, R1 is CH3 and Q are as defined in table Z.

[0239] Table A-21 provides 20 compounds A-21.001 to A-21.020 of formula I-A wherein R2a and R2a’ areboth CH2CH3, A1 is CH, R2b is I, R1 is H and Q are as defined in table Z.

[0240] Table A-22 provides 20 compounds A-22.001 to A-22.020 of formula I-A wherein R2a and R2a’ areboth CH2CH3, A1 is CH, R2b is I, R1 is CH3 and Q are as defined in table Z.

[0241] Table A-23 provides 20 compounds A-23.001 to A-23.020 of formula I-A wherein R2a and R2a’ areboth CH2CH3, A1 is CH, R2b is CF3, R1 is H and Q are as defined in table Z.

[0242] Table A-24 provides 20 compounds A-24.001 to A-24.020 of formula I-A wherein R2a and R2a’ areboth CH2CH3, A1 is CH, R2b is CF3, R1 is CH3 and Q are as defined in table Z.Table Z: Substituent definitions of Q109934 | 83191 FF 56Tables B-1 to B-5 (formula I-B)

[0243] Table B-1 provides 19 compounds B-1.001 to B-1.019 of formula I-B wherein R2a and R2a’ areboth CH3, A1is CH, R2bis CF3, R1is H, R5is CH3 and R4xare as defined in table Z1.

[0244] Table B-2 provides 19 compounds B-2.001 to B-2.019 of formula I-B wherein R2a and R2a’ areboth CH3, A1is CH, R2bis CF3, R1is H, R5is CH2CH3and R4xare as defined in table Z1.

[0245] Table B-3 provides 19 compounds B-3.001 to B-3.019 of formula I-B wherein R2a and R2a’ areboth CH3, A1 is CH, R2b is CF3, R1 is H, R5 is cyclopropyl and R4x are as defined in table Z1.

[0246] Table B-4 provides 19 compounds B-4.001 to B-4.019 of formula I-B wherein R2a and R2a’ areboth CH3, A1is CH, R2bis CF3, R1is H, R5is OCH3 and R4xare as defined in table Z1.

[0247] Table B-5 provides 19 compounds B-5.001 to B-5.019 of formula I-B wherein R2a and R2a’ areboth CH3, A1is CH, R2bis CF3, R1is H, R5is Br and R4xare as defined in table Z1.

[0248] Table B-6 provides 19 compounds B-6.001 to B-6.019 of formula I-B wherein R2a and R2a’ areboth CH3, A1is CH, R2bis I, R1is H, R5is CH3and R4xare as defined in table Z1.

[0249] Table B-7 provides 19 compounds B-7.001 to B-7.019 of formula I-B wherein R2a and R2a’ areboth CH3, A1is CH, R2bis I, R1is H, R5is CH2CH3 and R4xare as defined in table Z1.

[0250] Table B-8 provides 19 compounds B-8.001 to B-8.019 of formula I-B wherein R2a and R2a’ areboth CH3, A1is CH, R2bis I, R1is H, R5is cyclopropyl and R4xare as defined in table Z1.109934 | 83191 FF 57

[0251] Table B-9 provides 19 compounds B-9.001 to B-9.019 of formula I-B wherein R2a and R2a’ areboth CH3, A1is CH, R2bis I, R1is H, R5is OCH3 and R4xare as defined in table Z1.109934 | 83191 FF 58 Index R4x Index R4x Index R4x

[0252] Also made available are certain intermediate compounds as shown in Schemes 1 to 22, some ofwhich are novel. For example: ^A compound of formula IIa-1, as shown below, where A1, R2a, R2a' and R2b are as defined forcompounds of formula (I); for instance where A1, R2a, R2a’ and R2b are as described in Tables A-1 to A-24 and Tables B-1 to B-5; in particular where A1 is CH, R2a and R2a' are both methyl orethyl, preferably methyl, and R2b is chloro, bromo, cyclopropyl, difluoromethyl, trifluoromethyl, ordifluoromethoxy, preferably difluoromethyl or trifluoromethyl. ^A compound of formula IIb, as shown below, where A1, R2a, R2a' and R2b are as defined forcompounds of formula (I), Rais C1-C6alkyl or benzyl, preferably Rais methyl or ethyl; for instance where A1, R2a, R2a’ and R2b are as described in Tables A-1 to A-24 and Tables B-1 toB-5, in particular where A1is CH, R2aand R2a'are both methyl or ethyl, preferably methyl, and R2b is chloro, bromo, cyclopropyl, difluoromethyl or trifluoromethyl, preferably difluoromethyl,trifluoromethyl, or difluoromethoxy.IIa-1 IIb

[0253] Certain compounds of formula IIa-1 and IIb where both R2a and R2a’ are hydrogen are known.Therefore, these compounds are excluded from the present invention, namely:CAS number Name Structure2226281-82-7 1,4-dihydro-2-oxo-6-(trifluoromethyl)-2H-3,1- benzoxazine-8-carboxylic acid109934 | 83191 FF 59 CAS number Name Structure2114259-41-3 methyl 1,4-dihydro-2-oxo-2H-3,1-benzoxazine-8-carboxylate 2113426-11-0 ethyl 1,4-dihydro-2-oxo-2H-3,1-benzoxazine-8-carboxylate 1785224-83-0 1,4-dihydro-2-oxo-2H-3,1-benzoxazine-8-carboxylic acid ^A compound of formula XL-18, as shown below, where A1, R2a, R2a' and R2b are as definedfor compounds of formula (I); for instance where A1, R2a, R2a’and R2bare as described in Tables A-1 to A-24 and Tables B-1 to B-5, in particular where A1is CH, R2aand R2a'are both methyl or ethyl, preferably methyl, and R2bis chloro, bromo, cyclopropyl, difluoromethoxy, difluoromethyl or trifluoromethyl, preferably chloro, cyclopropyl, difluoromethoxy, difluoromethyl or trifluoromethyl, more preferably cyclopropyl, difluoromethoxy, difluoromethyl or trifluoromethyl O ONH2a' R 2a R 1 A 2b R XL-18

[0254] Certain compounds of formula XL-18 are known. Therefore, these compounds are excluded fromthe present invention, namely: CAS number Name Structure157405-32-8 8-methyl-1,4-dihydro-3,1-benzoxazin-2-one109934 | 83191 FF 60 CAS number Name Structure765266-61-3 8-methylspiro[1H-3,1-benzoxazine-4,1'-cyclopentane]- 2-one 857282-07-6 4,4,8-trimethyl-1H-3,1-benzoxazin-2-one 874472-99-8 6-bromo-4,4,8-trimethyl-1H-3,1-benzoxazin-2-one 2138345-00-1 6,8-dimethyl-1,4-dihydro-3,1-benzoxazin-2-one 2138408-13-4 6-chloro-8-methyl-1,4-dihydro-3,1-benzoxazin-2-one

[0255] As can be readily identified, when R2a and R2a’ are different, the compound contains a chiralcentre. Preferably, in compounds IIa-1 and IIb, R2aand R2a’are identical. This avoids the presence of a chiral centre in said compounds. Pest control

[0256] The compounds of formula (I) according to the invention are preventively and / or curativelyvaluable ac-tive ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. The active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina. The109934 | 83191 FF 61 insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i.e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and / or hatching rate.

[0257] Examples of the above mentioned animal pests are:^ from the order Acarina, for example, Acalitus spp., Aculus spp., Acaricalus spp., Aceriaspp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp.,Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp.,Eotetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp.,Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptrutaoleivora, Phytonemus spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus spp.,Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp., Tarsonemus spp. and Tetranychusspp.; ^from the order Anoplura, for example, Haematopinus spp., Linognathus spp., Pediculusspp., Pemphigus spp. and Phylloxera spp.; ^from the order Coleoptera, for example, Agriotes spp., Amphimallon majale, Anomalaorientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomarialinearis, Chaetocnema tibialis, Cerotoma spp., Conoderus spp., Cosmopolites spp., Cotinisnitida, Curculio spp., Cyclocephala spp., Dermestes spp., Diabrotica spp., Diloboderus abderus,Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa,Leptinotarsa decemlineata, Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Maladeracastanea, Megascelis spp., Melighetes aeneus, Melolontha spp., Myochrous armatus,Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp., Phlyctinus spp., Popillia spp.,Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabeidae spp., Sitophilus spp.,Sitotroga spp., Somaticus spp., Sphenophorus spp., Sternechus subsignatus, Tenebrio spp.,Tribolium spp. and Trogoderma spp.; ^from the order Diptera, for example, Aedes spp., Anopheles spp., Antherigona soccata,Bactrocea oleae, Bibio hortulanus, Bradysia spp., Calliphora erythrocephala, Ceratitis spp.,Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp., Drosophila melanogaster,Fannia spp., Gastrophilus spp., Geomyza tripunctata, Glossina spp., Hypoderma spp.,Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp.,Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis spp., Riveliaquadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipulaspp.; ^from the order Hemiptera, for example, Acanthocoris scabrator, Acrosternum spp.,Adelphocoris lineolatus, Aleurodes spp., Amblypelta nitida, Bathycoelia thalassina, Blissus spp.,Cimex spp., Clavigralla tomentosicollis, Creontiades spp., Distantiella theobroma, Dichelopsfurcatus, Dysdercus spp., Edessa spp., Euchistus spp., Eurydema pulchrum, Eurygaster spp.,Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp., Margarodes spp.,Murgantia histrionic, Neomegalotomus spp., Nesidiocoris tenuis, Nezara spp., Nysius simulans,Oebalus insularis, Piesma spp., Piezodorus spp., Rhodnius spp., Sahlbergella singularis,109934 | 83191 FF 62Scaptocoris castanea, Scotinophara spp. , Thyanta spp , Triatoma spp., Vatiga illudens,Acyrthosium pisum, Adalges spp., Agalliana ensigera, Agonoscena targionii, Aleurodicus spp.,Aleurocanthus spp., Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae,Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotusspp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp., Brachycaudus spp., Brevicorynebrassicae, Cacopsylla spp., Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalusaonidium, Chrysomphalus dictyospermi, Cicadella spp., Cofana spectra, Cryptomyzus spp.,Cicadulina spp., Coccus hesperidum, Dalbulus maidis, Dialeurodes spp., Diaphorina citri,Diuraphis noxia, Dysaphis spp., Empoasca spp., Eriosoma larigerum, Erythroneura spp.,Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae, Hyalopterus spp.,Hyperomyzus pallidus, Idioscopus clypealis, Jacobiasca lybica, Laodelphax spp., Lecaniumcorni, Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp., Mahanarvaspp., Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp., Neotoxopterasp, Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats, Odonaspis ruthae, Oregmalanigera Zehnter, Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigus spp.,Peregrinus maidis, Perkinsiella spp., Phorodon humuli, Phylloxera spp., Planococcus spp.,Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp., Pulvinariaaethiopica, Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphum spp.,Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Sogatella furcifera,Spissistilus festinus, Tarophagus Proserpina, Toxoptera spp., Trialeurodes spp., Tridiscussporoboli, Trionymus spp., Trioza erytreae , Unaspis citri, Zygina flammigera, Zyginidiascutellaris ;^ from the order Hymenoptera, for example, Acromyrmex, Arge spp., Atta spp., Cephus spp.,Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomoriumpharaonis, Neodiprion spp., Pogonomyrmex spp., Slenopsis invicta, Solenopsis spp. and Vespaspp.;^ from the order Isoptera, for example, Coptotermes spp., Corniternes cumulans, Incisitermesspp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Solenopsisgeminata;^ from the order Lepidoptera, for example, Acleris spp., Adoxophyes spp., Aegeria spp.,Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp.,Argyresthia spp., Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca,Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Chrysoteuchia topiaria,Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp.,Colias lesbia, Cosmophila flava, Crambus spp., Crocidolomia binotalis, Cryptophlebialeucotreta, Cydalima perspectalis, Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsiscastanea, Earias spp., Elasmopalpus lignosellus, Eldana saccharina, Ephestia spp., Epinotiaspp., Estigmene acrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella, Euproctis spp.,Euxoa spp., Feltia jaculiferia, Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis,Herpetogramma spp., Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus,Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostege bifidalis, Lymantria spp.,109934 | 83191 FF 63 Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Mythimna spp., Noctuaspp., Operophtera spp., Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp.,Panolis flammea, Papaipema nebris, Pectinophora gossypiela, Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella,Prays spp., Pseudoplusia spp., Rachiplusia nu, Richia albicosta, Scirpophaga spp., Sesamiaspp., Sparganothis spp., Spodoptera spp., Sylepta derogate, Synanthedon spp., Thaumetopoeaspp., Tortrix spp., Trichoplusia ni, Tuta absoluta, and Yponomeuta spp.;^ from the order Mallophaga, for example, Damalinea spp. and Trichodectes spp.;^ from the order Orthoptera, for example, Blatta spp., Blattella spp., Gryllotalpa spp.,Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp. , Scapteriscusspp., and Schistocerca spp.; ^from the order Psocoptera, for example, Liposcelis spp.;^ from the order Siphonaptera, for example, Ceratophyllus spp., Ctenocephalides spp. andXenopsylla cheopis; ^from the order Thysanoptera, for example, Calliothrips phaseoli, Frankliniella spp.,Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothripsvariabilis, Taeniothrips spp., Thrips spp;^ from the order Thysanura, for example, Lepisma saccharina.

[0258] In a further aspect, the invention may also relate to a method of controlling damage to plant andparts thereof by plant parasitic nematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasiticnematodes), especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla,Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae,Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gallnematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes,Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchusxylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemellaspecies, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchusdestructor, Ditylenchus dipsaci and other Ditylenchus species; Awl nematodes, Dolichodorus species;Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoidnematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lancenematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes,Longidorus elongatus and other Longidorus species; Pin nematodes, Pratylenchus species; Lesionnematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchusgoodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholusspecies; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchusspecies; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorusspecies, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubiusand other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes,Xiphinema species; and other plant parasitic nematode species, such as Subanguina spp., Hypsoperinespp., Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp..109934 | 83191 FF 64

[0259] The compounds of the invention may also have activity against the molluscs. Examples of whichinclude, for example, Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae(Bradybaena fruticum); Cepaea (C. hortensis, C. nemoralis); Ochlodina; Deroceras (D. agrestis, D.empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia(H. itala, H. obvia); Helicidae (Helicigona arbustorum); Helicodiscus; Helix (H. aperta); Limax (L.cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Lymnaea; Milax (M. gagates, M.marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.

[0260] The active ingredients according to the invention can be used for controlling, i.e. containing ordestroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.

[0261] Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize orsorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coco-nut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions,tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and alsotobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines, hops, the plantain family and latex plants.

[0262] The compositions and / or methods of the present invention may be also used on any ornamentaland / or vegetable crops, including flowers, shrubs, broad-leaved trees and evergreens.

[0263] For example the invention may be used on any of the following ornamental species: Ageratumspp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp.,Begonia spp. (e.g. B. elatior, B. semperflorens, B. tubéreux), Bougainvillea spp., Brachycome spp.,Brassica spp. (ornamental), Calceolaria spp., Capsicum annuum, Catharanthus roseus, Canna spp.,Centaurea spp., Chrysanthemum spp., Cineraria spp. (C. maritime), Coreopsis spp., Crassula coccinea,Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustomagrandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Gomphrena globosa,Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestesphyllostachya, Impatiens spp. (I. Walleriana), Iresines spp., Kalanchoe spp., Lantana camara, Lavateratrimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp.,Nemesia spp., Tagetes spp., Dianthus spp. (carnation), Canna spp., Oxalis spp., Bellis spp., Pelargoniumspp. (P. peltatum, P. Zonale), Viola spp. (pansy), Petunia spp., Phlox spp., Plecthranthus spp., Poinsettiaspp., Parthenocissus spp. (P. quinquefolia, P. tricuspidata), Primula spp., Ranunculus spp., Rhododendronspp., Rosa spp. (rose), Rudbeckia spp., Saintpaulia spp., Salvia spp., Scaevola aemola, Schizanthuswisetonensis, Sedum spp., Solanum spp., Surfinia spp., Tagetes spp., Nicotinia spp., Verbena spp., Zinniaspp. and other bedding plants.109934 | 83191 FF 65

[0264] For example the invention may be used on any of the following vegetable species: Allium spp.(A. sativum, A.. cepa, A. oschaninii, A. Porrum, A. ascalonicum, A. fistulosum), Anthriscus cerefolium,Apium graveolus, Asparagus officinalis, Beta vulgarus, Brassica spp. (B. Oleracea, B. Pekinensis, B. rapa),Capsicum annuum, Cicer arietinum, Cichorium endivia, Cichorum spp. (C. intybus, C. endivia), Citrilluslanatus, Cucumis spp. (C. sativus, C. melo), Cucurbita spp. (C. pepo, C. maxima), Cyanara spp. (C.scolymus, C. cardunculus), Daucus carota, Foeniculum vulgare, Hypericum spp., Lactuca sativa,Lycopersicon spp. (L. esculentum, L. lycopersicum), Mentha spp., Ocimum basilicum, Petroselinumcrispum, Phaseolus spp. (P. vulgaris, P. coccineus), Pisum sativum, Raphanus sativus, Rheumrhaponticum, Rosemarinus spp., Salvia spp., Scorzonera hispanica, Solanum melongena, Spinaceaoleracea, Valerianella spp. (V. locusta, V. eriocarpa) and Vicia faba.

[0265] Preferred ornamental species include African violet, Begonia, Dahlia, Gerbera, Hydrangea,Verbena, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hortensia, rosemary, sage, St. Johnswort, mint, sweet pepper, tomato and cucumber.

[0266] The active ingredients according to the invention are especially suitable for controlling Aphiscraccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops. The active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).

[0267] The compounds of formula (I) are particularly suitable for control of^ a pest of the order Hemiptera, for example, one or more of the species Bemisia tabaci,Aphis craccivora, Myzus persicae, Rhopalosiphum padi, Nilaparvata lugens, and Euschistus heros (preferably in vegetables, soybeans, and sugarcane); ^a pest of the order Lepidoptera, for example, one or more of the species Spodopteralittoralis, Spodoptera frugiperda, Plutella xylostella, Cnaphalocrocis medinalis, Cydia pomonella, Chrysodeixis includes, Chilo suppressalis, Elasmopalpus lignosellus, Pseudoplusia includens, and Tuta absoluta (preferably in vegetables and corn); ^a pest of the order Thysanoptera, such as the family Thripidae, for example, one or more ofThrips tabaci and Frankliniella occidentalis (preferably in vegetables); and^ soil pests (such as of the order Coleoptera), for example, the species Diabrotica balteata,Agriotes spp. and Leptinotarsa decemlineata (preferably in vegetables and corn).

[0268] The term "crops" is to be understood as including also crop plants which have been sotransformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.

[0269] Toxins that can be expressed by such transgenic plants include, for example, insecticidalproteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteinsfrom Bacillus thuringiensis, such as δ-endotoxins, e.g. Cry1Ab, Cry1Ac, Cry1F, Cry1FA2, Cry2Ab, Cry3A,Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1, Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as109934 | 83191 FF 66 Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers ofsodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase,bibenzyl synthase, chitinases and glucanases.

[0270] In the context of the present invention there are to be understood by δ-endotoxins, for exampleCry1Ab, Cry1Ac, Cry1F, Cry1FA2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02 / 15701). Truncated toxins, for example a truncated Cry1Ab, are known.In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. Insuch amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03 / 018810).

[0271] Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed,for example, in EP-A-0374753, WO 93 / 07278, WO 95 / 34656, EP-A-0427529, EP-A-451878 and WO03 / 052073.

[0272] The processes for the preparation of such transgenic plants are generally known to the personskilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP-A-0367474, EP-A-0401979 and WO 90 / 13651.

[0273] The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles(Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).

[0274] Transgenic plants containing one or more genes that code for an insecticidal resistance andexpress one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1Ab and a Cry3Bb1toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses aCry1FA2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry1Ac toxin); BollgardI® (cotton variety that expresses a Cry1Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a Cry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); Nature-Gard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

[0275] Further examples of such transgenic crops are:109934 | 83191 FF 67 1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31790 St. Sauveur,France, registration number C / FR / 96 / 05 / 10. Genetically modified Zea mays which has beenrendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamianonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31790 St. Sauveur,France, registration number C / FR / 96 / 05 / 10. Genetically modified Zea mays which has beenrendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamianonagrioides) by transgenic expression of a Cry1Ab toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31790 St. Sauveur,France, registration number C / FR / 96 / 05 / 10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion ofa cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03 / 018810. 4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses a Cry3Bb1 toxin andhas resistance to certain Coleoptera insects. 5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150Brussels, Belgium, registration number C / ES / 96 / 02. 6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels,Belgium, registration number C / NL / 00 / 10. Genetically modified maize for the expression of the protein Cry1F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium. 7. NK603 × MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 × MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (containsglyphosate), and also a Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki whichbrings about tolerance to certain Lepidoptera, include the European corn borer.

[0276] Transgenic crops of insect-resistant plants are also described in BATS (Zentrum für Biosicherheitund Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http: / / bats.ch).

[0277] The term "crops" is to be understood as including also crop plants which have been sotransformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis- related proteins" (PRPs, see e.g. EP-A-0392225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, fromEP-A-0392225, WO 95 / 33818 and EP-A-0353191. The methods of producing such transgenic plants are109934 | 83191 FF 68 generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

[0278] Crops may also be modified for enhanced resistance to fungal (for example Fusarium,Anthracnose, or Phytophthora), bacterial (for example Pseudomonas) or viral (for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus) pathogens.

[0279] Crops also include those that have enhanced resistance to nematodes, such as the soybean cystnematode.

[0280] Crops that are tolerant to abiotic stress include those that have enhanced tolerance to drought,high salt, high temperature, chill, frost, or light radiation, for example through expression of NF-YB or other proteins known in the art.

[0281] Antipathogenic substances which can be expressed by such transgenic plants include, forexample, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A-0392225); antipathogenic substances produced bymicroorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95 / 33818) orprotein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in WO 03 / 000906).

[0282] Further areas of use of the compositions according to the invention are the protection of storedgoods and store rooms and the protection of raw materials, such as wood, textiles, floor coverings orbuildings, and also in the hygiene sector, especially the protection of humans, domestic animals andproductive livestock against pests of the mentioned type.

[0283] The present invention provides a compound of the first aspect for use in therapy. The presentinvention provides a compound of the first aspect, for use in controlling parasites in or on an animal. The present invention further provides a compound of the first aspect, for use in controlling ectoparasites on an animal. The present invention further provides a compound of the first aspect, for use in preventing and / or treating diseases transmitted by ectoparasites.

[0284] The present invention provides the use of a compound of the first aspect, for the manufacture ofa medicament for controlling parasites in or on an animal. The present invention further provides the use of a compound of the first aspect, for the manufacture of a medicament for controlling ectoparasites on an animal. The present invention further provides the use of a compound of the first aspect, for the manufacture of a medicament for preventing and / or treating diseases transmitted by ectoparasites.

[0285] The present invention provides the use of a compound of the first aspect, in controlling parasitesin or on an animal. The present invention further provides the use of a compound of the first aspect , in controlling ectoparasites on an animal.

[0286] The term "controlling" when used in context of parasites in or on an animal refers to reducing thenumber of pests or parasites, eliminating pests or parasites and / or preventing further pest or parasite infestation.

[0287] The term "treating" when used in context of parasites in or on an animal refers to restraining,slowing, stopping or reversing the progression or severity of an existing symptom or disease.

[0288] The term "preventing" when used in context of parasites in or on an animal refers to the avoidanceof a symptom or disease developing in the animal.109934 | 83191 FF 69

[0289] The term "animal" when used in context of parasites in or on an animal may refer to a mammaland a non-mammal, such as a bird or fish. In the case of a mammal, it may be a human or non-human mammal. Non-human mammals include, but are not limited to, livestock animals and companion animals. Livestock animals include, but are not limited to, cattle, camelids, pigs, sheep, goats and horses. Companion animals include, but are not limited to, dogs, cats and rabbits.

[0290] A "parasite" is a pest which lives in or on the host animal and benefits by deriving nutrients at thehost animal's expense. An "endoparasite" is a parasite which lives in the host animal. An "ectoparasite" is a parasite which lives on the host animal. Ectoparasites include, but are not limited to, acari, insects and crustaceans (e.g. sea lice). The Acari (or Acarina) sub-class comprises ticks and mites. Ticks include, butare not limited to, members of the following genera: Rhipicaphalus, for example, Rhipicaphalus (Boophilus)microplus and Rhipicephalus sanguineus; Amblyomrna; Dermacentor; Haemaphysalis; Hyalomma; Ixodes;Rhipicentor; Margaropus; Argas; Otobius; and Ornithodoros. Mites include, but are not limited to, membersof the following genera: Chorioptes, for example Chorioptes bovis; Psoroptes, for example Psoroptes ovis;Cheyletiella; Dermanyssus; for example Dermanyssus gallinae; Ortnithonyssus; Demodex, for exampleDemodex canis; Sarcoptes, for example Sarcoptes scabiei; and Psorergates. Insects include, but are notlimited to, members of the orders: Siphonaptera, Diptera, Phthiraptera, Lepidoptera, Coleoptera andHomoptera. Members of the Siphonaptera order include, but are not limited to, Ctenocephalides felis andCtenocephatides canis. Members of the Diptera order include, but are not limited to, Musca spp.; bot fly,for example Gasterophilus intestinalis and Oestrus ovis; biting flies; horse flies, for example Haematopotaspp. and Tabunus spp.; haematobia, for example haematobia irritans; Stomoxys; Lucilia; midges; andmosquitoes. Members of the Phthiraptera class include, but are not limited to, blood sucking lice andchewing lice, for example Bovicola ovis and Bovicola bovis.

[0291] The term "effective amount" when used in context of parasites in or on an animal refers to theamount or dose of the compound of the invention, or a salt thereof, which, upon single or multiple doseadministration to the animal, provides the desired effect in or on the animal. The effective amount can bereadily determined by the attending diagnostician, as one skilled in the art, by the use of known techniques and by observing results obtained under analogous circumstances. In determining the effective amount a number of factors are considered by the attending diagnostician, including, but not limited to: the species of mammal; its size, age, and general health; the parasite to be controlled and the degree of infestation; the specific disease or disorder involved; the degree of involvement or the severity of the disease or disorder; the response of the individual; the particular compound administered; the mode of administration; the bioavailability characteristics of the preparation administered; the dose regimen selected; the use of concomitant medication; and other relevant circumstances.

[0292] The compounds of the invention may be administered to the animal by any route which has thedesired effect including, but not limited to topically, orally, parenterally'and subcutaneously. Topical administration is preferred. Formulations suitable for topical administration include, for example, solutions, emulsions and suspensions and may take the form of a pour-on, spot-on, spray-on, spray race or dip. In the alternative, the compounds of the invention may be administered by means of an ear tag or collar.

[0293] Salt forms of the compounds of the invention include both pharmaceutically acceptable salts andveterinary acceptable salts, which can be different to agrochemically acceptable salts. Pharmaceuticallyand veterinary acceptable salts and common methodology for preparing them are well known in the art.109934 | 83191 FF 70 See, for example, Gould, P.L., "Salt selection for basic drugs", International Journal of Pharmaceutics, 33: 201 -217 (1986); Bastin, R.J., et al. "Salt Selection and Optimization Procedures for Pharmaceutical New Chemical Entities", Organic Process Research and Development, 4: 427-435 (2000); and Berge, S.M., et al., "Pharmaceutical Salts", Journal of Pharmaceutical Sciences, 66: 1-19, (1977). One skilled in the art of synthesis will appreciate that the compounds of the invention are readily converted to and may be isolated as a salt, such as a hydrochloride salt, using techniques and conditions well known to one of ordinary skill in the art. In addition, one skilled in the art of synthesis will appreciate that the compounds of the invention are readily converted to and may be isolated as the corresponding free base from the corresponding salt.

[0294] The present invention also provides a method for controlling pests (such as mosquitoes and otherdisease vectors; see also http: / / www.who.int / malaria / vector_control / irs / en / ). In one embodiment, the method for controlling pests comprises applying the compositions of the invention to the target pests, to their locus or to a surface or substrate by brushing, rolling, spraying, spreading or dipping. By way of example, an IRS (indoor residual spraying) application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention. In another embodiment, it is contemplated to apply such compositions to a substrate such as non-woven or a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.

[0295] In one embodiment, the method for controlling such pests comprises applying a pesticidallyeffective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate. Such application may be made by brushing, rolling, spraying, spreading or dipping the pesticidal composition of the invention. By way of example, an IRS application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention so as to provide effective residual pesticidal activity on the surface. In another embodiment, it is contemplated to apply such compositions for residual control of pests on a substrate such as a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.

[0296] Substrates including non-woven, fabrics or netting to be treated may be made of natural fibressuch as cotton, raffia, jute, flax, sisal, hessian, or wool, or synthetic fibres such as polyamide, polyester, polypropylene, polyacrylonitrile or the like. The polyesters are particularly suitable. The methods of textile treatment are known, e.g. WO 2008 / 151984, WO 2003 / 034823, US 5631072, WO 2005 / 64072, WO 2006 / 128870, EP 1724392, WO 2005 / 113886 or WO 2007 / 090739.

[0297] Further areas of use of the compositions according to the invention are the field of treeinjection / trunk treatment for all ornamental trees as well all sort of fruit and nut trees.

[0298] In the field of tree injection / trunk treatment, the compounds according to the present inventionare especially suitable against wood-boring insects from the order Lepidoptera as mentioned above andfrom the order Coleoptera, especially against woodborers listed in the following tables A and B: Table A. Examples of exotic woodborers of economic importance. Family Species Host or Crop InfestedBuprestidae Agrilus planipennis Ash Cerambycidae Anoplura glabripennis Hardwoods109934 | 83191 FF 71 Family Species Host or Crop InfestedScolytidae Xylosandrus crassiusculus Hardwoods X. mutilatus Hardwoods Tomicus piniperda Conifers Table B. Examples of native woodborers of economic importance. Family Species Host or Crop InfestedBuprestidae Agrilus anxius Birch Agrilus politus Willow, Maple Agrilus sayi Bayberry, Sweetfern Agrilus vittaticolllis Apple, Pear, Cranberry, Serviceberry, HawthornChrysobothris femorata Apple, Apricot, Beech, Boxelder, Cherry, Chestnut, Currant, Elm, Hawthorn, Hackberry, Hickory, Horsechestnut, Linden, Maple, Mountain-ash, Oak, Pecan, Pear, Peach, Persimmon, Plum, Poplar, Quince, Redbud, Serviceberry, Sycamore, Walnut, Willow Texania campestris Basswood, Beech, Maple, Oak, Sycamore, Willow, Yellow-poplar Cerambycidae Goes pulverulentus Beech, Elm, Nuttall, Willow, Black oak, Cherrybark oak, Water oak, Sycamore Goes tigrinus Oak Neoclytus acuminatus Ash, Hickory, Oak, Walnut, Birch, Beech, Maple, Eastern hophornbeam, Dogwood, Persimmon, Redbud, Holly, Hackberry, Black locust, Honeylocust, Yellow-poplar, Chestnut, Osage- orange, Sassafras, Lilac, Mountain-mahogany, Pear, Cherry, Plum, Peach, Apple, Elm, Basswood, Sweetgum Neoptychodes trilineatus Fig, Alder, Mulberry, Willow, Netleaf hackberry Oberea ocellata Sumac, Apple, Peach, Plum, Pear, Currant, Blackberry109934 | 83191 FF 72 Family Species Host or Crop InfestedOberea tripunctata Dogwood, Viburnum, Elm, Sourwood, Blueberry, Rhododendron, Azalea, Laurel, Poplar, Willow, Mulberry Oncideres cingulata Hickory, Pecan, Persimmon, Elm, Sourwood, Basswood, Honeylocust, Dogwood, Eucalyptus, Oak, Hackberry, Maple, Fruit trees Saperda calcarata Poplar Strophiona nitens Chestnut, Oak, Hickory, Walnut, Beech, Maple Scolytidae Corthylus columbianus Maple, Oak, Yellow-poplar, Beech, Boxelder, Sycamore, Birch, Basswood, Chestnut, Elm Dendroctonus frontalis Pine Dryocoetes betulae Birch, Sweetgum, Wild cherry, Beech, Pear Monarthrum fasciatum Oak, Maple, Birch, Chestnut, Sweetgum, Blackgum, Poplar, Hickory, Mimosa, Apple, Peach, Pine Phloeotribus liminaris Peach, Cherry, Plum, Black cherry, Elm, Mulberry, Mountain-ash Pseudopityophthorus Oak, American beech, Black cherry, Chickasaw pruinosus plum, Chestnut, Maple, Hickory, Hornbeam, Hophornbeam Sesiidae Paranthrene simulans Oak, American chestnut Sannina uroceriformis Persimmon Synanthedon exitiosa Peach, Plum, Nectarine, Cherry, Apricot, Almond, Black cherry Synanthedon pictipes Peach, Plum, Cherry, Beach, Black Cherry Synanthedon rubrofascia Tupelo Synanthedon scitula Dogwood, Pecan, Hickory, Oak, Chestnut, Beech, Birch, Black cherry, Elm, Mountain-ash, Viburnum, Willow, Apple, Loquat, Ninebark, Bayberry Vitacea polistiformis Grape

[0299] The present invention may be also used to control any insect pests that may be present inturfgrass, including for example beetles, caterpillars, fire ants, ground pearls, millipedes, sow bugs, mites, mole crickets, scales, mealybugs, ticks, spittlebugs, southern chinch bugs and white grubs. The present109934 | 83191 FF 73 invention may be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults.

[0300] In particular, the present invention may be used to control insect pests that feed on the roots ofturfgrass including white grubs (such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogusspp. (e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green June beetle, C. nitida), Popillia spp. (e.g.Japanese beetle, P. japonica), Phyllophaga spp. (e.g. May / June beetle), Ataenius spp. (e.g. Black turfgrassataenius, A. spretulus), Maladera spp. (e.g. Asiatic garden beetle, M. castanea) and Tomarus spp., groundpearls (Margarodes spp.), mole crickets (tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpaafricana) and leatherjackets (European crane fly, Tipula spp.).

[0301] The present invention may also be used to control insect pests of turfgrass that are thatchdwelling, including armyworms (such as fall armyworm Spodoptera frugiperda, and common armywormPseudaletia unipuncta), cutworms, billbugs (Sphenophorus spp., such as S. venatus verstitus and S.parvulus), and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogrammaphaeopteralis).

[0302] The present invention may also be used to control insect pests of turfgrass that live above theground and feed on the turfgrass leaves, including chinch bugs (such as southern chinch bugs, Blissusinsularis), Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug (Antonina graminis), two-lined spittlebug (Propsapia bicincta), leafhoppers, cutworms (Noctuidae family), and greenbugs.

[0303] The present invention may also be used to control other pests of turfgrass such as red importedfire ants (Solenopsis invicta) that create ant mounds in turf.

[0304] In the hygiene sector, the compositions according to the invention are active against ectoparasitessuch as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.

[0305] Examples of such parasites are:^ Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp.,Solenopotes spp.. ^Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp.,Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp.. ^Of the order Diptera and the suborders Nematocerina and Brachycerina, for example Aedesspp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.. ^Of the order Siphonapterida, for example Pulex spp., Ctenocephalides spp., Xenopsyllaspp., Ceratophyllus spp.. ^Of the order Heteropterida, for example Cimex spp., Triatoma spp., Rhodnius spp.,Panstrongylus spp.. ^Of the order Blattarida, for example Blatta orientalis, Periplaneta americana, Blattelagermanica and Supella spp..109934 | 83191 FF 74 ^Of the subclass Acaria (Acarida) and the orders Meta- and Meso-stigmata, for exampleArgas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp.,Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.. ^Of the orders Actinedida (Prostigmata) and Acaridida (Astigmata), for example Acarapisspp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp..

[0306] The compositions according to the invention are also suitable for protecting against insectinfestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.

[0307] The compositions according to the invention can be used, for example, against the followingpests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spp., Tryptodendron spp., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spp., and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus augur, and termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and Coptotermes formosanus, and bristletails such as Lepisma saccharina.

[0308] The compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling oneor more pests selected from the family: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae. In apreferred embodiment of each aspect, a compound TX (where the abbreviation "TX" means “one compoundselected from the compounds defined in Tables A-1 to A-24, Tables B-1 to B-5, and Table P”) controls oneor more of pests selected from the family: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae.

[0309] The compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling oneor more of pests selected from the genus: Spodoptera spp., Plutella spp., Frankliniella spp., Thrips spp., Euschistus spp., Cydia spp., Nilaparvata spp., Myzus spp., Aphis spp., Diabrotica spp., Rhopalosiphumspp., Pseudoplusia spp and Chilo spp.

[0310] In a preferred embodiment of each aspect, a compound TX (where the abbreviation "TX" means“one compound selected from the compounds defined in Tables A-1 to A-24, Tables B-1 to B-5, and TableP”) controls one or more of pests selected from the genus: Spodoptera spp., Plutella spp., Frankliniella spp., Thrips spp., Euschistus spp., Cydia spp., Nilaparvata spp., Myzus spp., Aphis spp., Diabrotica spp.,Rhopalosiphum spp., Pseudoplusia spp and Chilo spp.

[0311] The compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling oneor more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus109934 | 83191 FF 75 heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum padi, and Chilo suppressalis.

[0312] In a preferred embodiment of each aspect, a compound TX (where the abbreviation "TX" means“one compound selected from the compounds defined in Tables A-1 to A-24, Tables B-1 to B-5, and TableP”) controls one or more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum Padia, and Chilo Suppressalis, such as Spodopteralittoralis + TX, Plutella xylostella + TX; Frankliniella occidentalis + TX, Thrips tabaci + TX, Euschistus heros+ TX, Cydia pomonella + TX, Nilaparvata lugens + TX, Myzus persicae + TX, Chrysodeixis incIudens + TX,Aphis craccivora + TX, Diabrotica balteata + TX, Rhopalosiphum Padi + TX, and Chilo suppressalis + TX.

[0313] In an embodiment of each aspect, a compound selected from the compounds defined in TablesA-1 to A-24, Tables B-1 to B-5, and Table P, and Table P is suitable for controlling Spodoptera littoralis,Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis incIudens, Aphis craccivora, Diabrotica balteata, RhopalosiphumPadia, and Chilo Suppressalis in cotton, vegetable, maize, cereal, rice and soya crops.

[0314] In an embodiment of each aspect, a compound selected from the compounds defined in TablesA-1 to A-24, Tables B-1 to B-5, and Table P is suitable for controlling Mamestra (preferably in vegetables),Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).

[0315] Compounds according to the invention may possess any number of benefits including, inter alia,advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (against non-target organisms above and below ground (such as fish, birds and bees), improved physico-chemical properties, or increased biodegradability). In particular, it has been surprisingly found that certain compounds of formula (I) may show an advantageous safety profile with respect to non-target arthropods, in particular pollinators such as honey bees, solitary bees, and bumble bees, most particularly, Apis mellifera.

[0316] The following combinations of a compound of formula I with another active substance in a weightratio of 1:1 are preferred (where the abbreviation “TX” means "one compound selected from the compoundsdefined in Tables A-1 to A-24, Tables B-1 to B-5, and Table P”):(7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol + TX, (E)-tridec-4-en-1-yl acetate + TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec- 11-enal + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-icos-13-en-10-one + TX, (Z)-tetradec- 7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, 1-(4-chlorophenyl)- 2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)benzene + TX, 1,2-dibromo-3-chloropropane + TX, 1,2-dichloropropane + TX, 1,2-dichloropropane with 1,3-dichloropropene + TX, 1,3-dichloropropene + TX, 14-methyloctadec-1-ene + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 2-(octylthio)ethanol + TX, 2-[5-(2-chloro-3,3,3-trifluoro-prop-1-enyl)-1-methyl-imidazol-2-yl]-5-cyclopropyl-3-ethylsulfonyl- pyridine + TX, 2-chlorophenyl N-methylcarbamate (CPMC) + TX, 3-(4-chlorophenyl)-5-109934 | 83191 FF 76 methylrhodanine + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 4-(quinoxalin-2- ylamino)benzenesulfonamide + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one + TX, 5-methyl-6- thioxo-1,3,5-thiadiazinan-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, 8-hydroxyquinoline sulfate + TX, abamectin + TX, acequinocyl + TX, acetamiprid + TX, acetoprole + TX, acrinathrin + TX, acynonapyr + TX, Adoxophyes orana GV + TX, afidopyropen + TX, afoxolaner + TX, Agrobacterium radiobacter + TX, AKD-3088 + TX, alanycarb + TX, aldicarb + TX, aldoxycarb + TX, allethrin + TX, alpha-cypermethrin + TX, alphamethrin + TX, alpha-multistriatin + TX, Amblyseius spp. + TX, amidoflumet + TX, amino acids + TX, aminocarb + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, apholate + TX, Autographa californica NPV + TX, AZ 60541 + TX, azadirachtin + TX, azocyclotin + TX, Bacillus aizawai + TX, Bacillus chitinosporus AQ746 (NRRL Accession No B-21 618) + TX, Bacillus firmus + TX, Bacillus kurstaki + TX, Bacillus mycoides AQ726 (NRRL Accession No. B-21664) + TX, Bacillus pumilus (NRRL Accession No B-30087) + TX, Bacillus pumilus AQ717 (NRRL Accession No. B-21662) + TX, Bacillus sp. AQ175 (ATCC Accession No. 55608) + TX, Bacillus sp. AQ177 (ATCC Accession No.55609) + TX, Bacillus sp. AQ178 (ATCC Accession No.53522) + TX, Bacillus sphaericus Neide + TX, Bacillus subtilis AQ153 (ATCC Accession No.55614) + TX, Bacillus subtilis AQ30002 (NRRL Accession No. B-50421) + TX, Bacillus subtilis AQ30004 (NRRL AccessionNo. B- 50455) + TX, Bacillus subtilis AQ713 (NRRL Accession No. B-21661) + TX, Bacillus subtilisAQ743 (NRRL Accession No. B-21665) + TX, Bacillus subtilis unspecified + TX, Bacillus thuringiensis AQ52 (NRRL Accession No. B-21619) + TX, Bacillus thuringiensis BD#32 (NRRL Accession No B- 21530) + TX, Bacillus thuringiensis Berliner + TX, Bacillus thuringiensis subsp. Aizawai + TX, Bacillus thuringiensis subsp. Israelensis + TX, Bacillus thuringiensis subsp. Japonensis + TX, Bacillus thuringiensis subsp. Kurstaki + TX, Bacillus thurin-giensis subsp. Tenebrionis + TX, Bacillus thuringiensis subspec. kurstaki BMP 123 + TX, Beauveria bassiana + TX, Beauveria brongniartii + TX, benclothiaz + TX, benomyl + TX, bensultap + TX, bentioflumin (CAS Number: 2566451-67-8) + TX, benzoximate + TX, benzpyrimoxan + TX, betacyfluthrin + TX, beta-cypermethrin + TX, bethoxazin + TX, bifenazate + TX, bifenthrin + TX, binapacryl + TX, bioallethrin + TX, bioresmethrin + TX, bis(tributyltin) oxide + TX, bisazir + TX, bistrifluron + TX, bisulflufen + TX, brevicomin + TX, broflanilide + TX, brofluthrinate + TX, bromoacetamide + TX, bromophos-ethyl + TX, bronopol + TX, busulfan + TX, butocarboxim + TX, butopyronoxyl + TX, butoxy(polypropylene glycol) + TX, butylpyridaben + TX, cadusafos + TX, calcium arsenate + TX, carbaryl + TX, carbofuran + TX, carbon disulfide + TX, carbosulfan + TX, cartap + TX, CAS number: 1594624-87-9 + TX, CAS number: 1922957-47-8 + TX, CAS number: 1255091-74-7 + TX, CAS number: 1365070-72-9 + TX, CAS Number: 158062-71-6 + TX, CAS number: 1594626-19-3 + TX, CAS number: 1594637-65-6 + TX, CAS number: 1632218-00-8 + TX, CAS number: 1808115-49-2 + TX, CAS number: 1922957-46-7 + TX, CAS number: 1922957-48-9 + TX, CAS number: 1956329-03-5 + TX, CAS number: 1990457-52- 7 + TX, CAS number: 1990457-55-0 + TX, CAS number: 1990457-57-2 + TX, CAS number: 1990457- 66-3 + TX, CAS number: 1990457-77-6 + TX, CAS number: 1990457-85-6 + TX, CAS number: 2032403-97-5 + TX, CAS number: 2044701-44-0 + TX, CAS number: 2095470-94-1 + TX, CAS number: 2128706-05-6 + TX, CAS number: 2133042-31-4 + TX, CAS number: 2133042-44-9 + TX, CAS number: 2171099-09-3 + TX, CAS number: 2220132-55-6 + TX, CAS number: 2396747-83-2 +109934 | 83191 FF 77 TX, CAS number: 2408220-91-5 + TX, CAS number: 2408220-94-8 + TX, CAS number: 2415706-16- 8 + TX, CAS Number: 2583740-14-9 + TX, CAS Number: 2583751-98-6 + TX, CAS number: 2719848- 60-7 + TX, CAS Number: 2898489-71-7 + TX, CAS Number: 2922115-20-4 + TX, CAS Number: 3060345-80-1 + TX, CAS Number: 3061364-30-2 + TX, CAS Number: 34763-86-5 + TX, CAS number: RNA (Leptinotarsa decemlineata-specific recombinant double-stranded interfering GS2) + TX, chlorantraniliprole + TX, chlordane + TX, chlorfenapyr + TX, chloropicrin + TX, chloroprallethrin + TX, chlorpyrifos + TX, chromafenozide + TX, Chrysoperla carnea + TX, clenpirin + TX, cloethocarb + TX, clothianidin + TX, codlelure + TX, codlemone + TX, copper acetoarsenite + TX, copper dioctanoate + TX, copper hydroxide + TX, copper sulfate + TX, cresol + TX, crufomate + TX, Cryptolaemus montrouzieri + TX, cuelure + TX, cyanofenphos + TX, cyantraniliprole + TX, cybenzoxasulfyl (CAS Number: 2128706-04-5) + TX, cybutryne + TX, cyclaniliprole + TX, cyclobutrifluram + TX, cycloprothrin + TX, cycloxaprid + TX, Cydia pomonella GV + TX, cyenopyrafen + TX, cyetpyrafen + TX, cyflumetofen + TX, cyfluthrin + TX, cyhalodiamide + TX, cylohalothrin + TX, cypermethrin + TX, cyphenothrin + TX, cyproflanilide + TX, cyromazine + TX, cytokinins + TX, Dacnusa sibirica + TX, dazomet + TX, DBCP + TX, DCIP + TX, deltamethrin + TX, diafenthiuron + TX, dialifos + TX, diamidafos + TX, dibrom + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, dichlofenthion + TX, dichlone + TX, dichlorophen + TX, dicliphos + TX, dicloromezotiaz + TX, diethyltoluamide + TX, diflubenzuron + TX, Diglyphus isaea + TX, dimatif + TX, dimethoate + TX, dimethyl carbate + TX, dimethyl phthalate + TX, dimpropyridaz + TX, dinactin + TX, dinocap + TX, dinotefuran + TX, dioxabenzofos + TX, dipyrithione + TX, disparlure + TX, D-limonene + TX, dodec- 8-en-1-yl acetate + TX, dodec-9-en-1-yl acetate + TX, dodeca-8,10-dien-1-yl acetate + TX, dodicin + TX, dominicalure + TX, doramectin + TX, emamectin + TX, emamectin benzoate + TX, empenthrin +TX, Encarsia formosa + TX, endothal + TX, endrin + TX, eprinomectin + TX, epsilon - momfluorothrin+ TX, epsilon-metofluthrin + TX, Eretmocerus eremicus + TX, esfenvalerate + TX, ethion + TX, ethiprole + TX, ethoprophos + TX, ethyl 4-methyloctanoate + TX, ethyl hexanediol + TX, ethylene dibromide + TX, etofenprox + TX, etoxazole + TX, etpyrafen + TX, eugenol + TX, Extract of seaweed and fermentation product derived from melasse + TX, Extract of seaweed and fermentation product derived from melasse comprising urea + TX, Extract of seaweed and fermented plant products + TX, Extract of seaweed and fermented plant products comprising phytohormones, vitamins, EDTA- chelated copper, zinc, and iron + TX, famphur + TX, fenaminosulf + TX, fenamiphos + TX, fenazaquin + TX, fenfluthrin + TX, fenitrothion + TX, fenmezoditiaz + TX, fenobucarb + TX, fenothiocarb + TX, fenoxycarb + TX, fenpropathrin + TX, fenpyrad + TX, fenpyroximate + TX, fensulfothion + TX, fenthion+ TX, fentin + TX, fentinacetate + TX, fenvalerate + TX, ferric phosphate + TX, fipronil + TX,flometoquin + TX, flonicamid + TX, fluacrypyrim + TX, fluazaindolizine + TX, fluazuron + TX, flubendiamide + TX, flubenzimine + TX, fluchlordiniliprole + TX, flucitrinate + TX, flucycloxuron + TX, flucythrinate + TX, fluensulfone [318290-98-1] + TX, fluensulfone + TX, flufenerim + TX, flufenprox + TX, flufiprole + TX, fluhexafon + TX, flumethrin + TX, fluopyram + TX, flupentiofenox + TX, flupyradifurone + TX, flupyrimin + TX, flupyroxystrobin + TX, fluralaner + TX, fluvalinate + TX, fluxametamide + TX, formaldehyde + TX, fosthiazate + TX, fosthietan + TX, frontalin + TX, furfural + TX, galquin (CAS Number: 2644770-30-7) + TX, gamma-cyhalothrin + TX, Gossyplure® (1:1 mixture of the (Z,E) and (Z,Z) isomers of hexadeca-7,11-dien-1-yl-acetate) + TX, grandlure + TX, grandlure I109934 | 83191 FF 78 + TX, grandlure II + TX, grandlure III + TX, grandlure IV + TX, Granulovirus + TX, guadipyr + TX, GY- 81 + TX, halfenprox + TX, halofenozide + TX, Harpin + TX, Helicoverpa armigera Nucleopolyhedrovirus + TX, Helicoverpa zea NPV + TX, Helicoverpa zea Nucleopolyhedrovirus + TX, Heliothis punctigera Nucleopolyhedrovirus + TX, Heliothis virescens Nucleopolyhedrovirus + TX, hemel + TX, hempa + TX, heptafluthrin + TX, heterophos + TX, Heterorhabditis bacteriophora and H. megidis + TX, hexalure + TX, hexamide + TX, hexythiazox + TX, Hippodamia convergens + TX, hydramethylnon + TX, hydrargaphen + TX, hydrated lime + TX, imicyafos + TX, imidacloprid + TX, imiprothrin + TX, Indazapyroxamet + TX, indoxacarb + TX, iodomethane + TX, iprodione + TX, ipsdienol + TX, ipsenol + TX, isamidofos + TX, isazofos + TX, isocycloseram + TX, Isoflualanam (CAS number: 2892524-05-7) + TX, isothioate + TX, ivermectin + TX, japonilure + TX, kappa- bifenthrin + TX, kappa-tefluthrin + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, kinetin + TX, lambda-cyhalothrin + TX, ledprona + TX, lepimectin + TX, Leptomastix dactylopii + TX, lineatin + TX, litlure + TX, looplure + TX, lotilaner + TX, lufenuron + TX, Macrolophus caliginosus + TX, Mamestra brassicae NPV + TX, mecarphon + TX, medlure + TX, megatomoic acid + TX, metaflumizone + TX, metaldehyde + TX, metam + TX, metam-potassium + TX, metam-sodium + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, Metarhizium spp. + TX, metepa + TX, methiocarb + TX, methiotepa + TX, methomyl + TX, methoquin-butyl + TX, methoxyfenozide + TX, methyl apholate + TX, methyl bromide + TX, methyl eugenol + TX, methyl isothiocyanate + TX, methylneodecanamide + TX, metofluthrin + TX, metolcarb + TX, mexacarbate + TX, milbemectin + TX, milbemycin oxime + TX, momfluorothrin + TX, morzid + TX, moxidectin + TX, muscalure + TX, Muscodor albus 620 (NRRL Accession No.30547) + TX, Muscodor roseus A3-5 (NRRL Accession No.30548) + TX, Myrothecium verrucaria composition + TX, nabam + TX, NC-184 + TX, Neem tree based products + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, nickel bis(dimethyldithiocarbamate) + TX, niclosamide + TX, niclosamide-olamine + TX, nicofluprole + TX, nitenpyram + TX, nithiazine + TX, nitrapyrin + TX, octadeca-2,13-dien-1-yl acetate + TX, octadeca-3,13-dien-1-yl acetate + TX, octhilinone + TX, omethoate + TX, orfralure + TX, Orius spp. + TX, oryctalure + TX, ostramone + TX, oxamate + TX, oxamyl + TX, oxazosulfyl + TX, oxolinic acid + TX, oxytetracycline + TX, Paecilomyces fumosoroseus + TX, Paecilomyces lilacinus + TX, parathion-ethyl + TX, Pasteuria nishizawae + TX, Pasteuria penetrans + TX, Pasteuria ramosa + TX, Pasteuria thornei + TX, Pasteuria usgae + TX, P-cymene + TX, penfluron + TX, pentachlorophenol + TX, permethrin + TX, phenothrin + TX, phorate + TX, phosphamidon + TX, phosphocarb + TX, Phytoseiulus persimilis + TX, picaridin + TX, pioxaniliprole + TX, piperazine + TX, piperflanilide (CAS number: 2615135-05-0) + TX, piperonylbutoxide + TX, pirimicarb + TX, pirimiphos-ethyl + TX, pirimiphos-methyl + TX, Plutella xylostella Granulosis virus + TX, Plutella xylostella Nucleopolyhedrovirus + TX, Polyhedrosis virus + TX, potassium and molybdenum and EDTA-chelated manganese + TX, potassium ethylxanthate + TX, potassium hydroxyquinoline sulfate + TX, prallethrin + TX, probenazole + TX, profenofos + TX, profluthrin + TX, propargite + TX,propetamphos + TX, propoxur + TX, prothiophos + TX, protrifenbute + TX, pyflubumide + TX,pymetrozine + TX, pyraclofos + TX, pyrafluprole + TX, pyrethrum + TX, pyridaben + TX, pyridalyl + TX, pyridin-4-amine + TX, pyrifluquinazon + TX, pyrimidifen + TX, pyriminostrobin + TX, pyriprole [394730-71-3] + TX, pyriprole + TX, pyriproxyfen + TX, QRD 420 (a terpenoid blend) + TX, QRD 452109934 | 83191 FF 79 (a terpenoid blend) + TX, QRD 460 (a terpenoid blend) + TX, Quillaja saponaria + TX, quinoclamine + TX, quinonamid + TX, resmethrin + TX, Rhodococcus globerulus AQ719 (NRRL Accession No B- 21663) + TX, sarolaner + TX, S-bioallethrin + TX, sebufos + TX, selamectin + TX, siglure + TX, silafluofen + TX, simazine + TX, sodium pentachlorophenoxide + TX, sordidin + TX, spidoxamat + TX, spinetoram + TX, spinosad + TX, spirobudifen + TX, spirodiclofen + TX, spiromesifen + TX, spiropidion + TX, spirotetramat + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus + TX, Spodoptera frugiperda Nucleopolyhedrovirus + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Streptomyces galbus (NRRL Accession No.30232) + TX, Streptomyces sp. (NRRL Accession No. B-30145) + TX, streptomycin + TX, streptomycin sesquisulfate + TX, strychnine + TX, sulcatol + TX, sulfiflumin + TX, sulfoxaflor + TX, tazimcarb + TX, tebufenozide + TX, tebufenpyrad + TX, tebupirimiphos + TX, tecloftalam + TX, tefluthrin + TX, temephos + TX, tepa + TX, terbam + TX, terbufos + TX, terpenoid blend + TX, tetrachlorantraniliprole + TX, tetrachlorothiophene + TX, tetradec-11-en-1-yl acetate + TX, tetradiphon + TX, tetramethrin + TX, tetramethylfluthrin + TX, tetranactin + TX, tetraniliprole + TX, theta- cypermethrin + TX, thiacloprid + TX, thiafenox + TX, thiamethoxam + TX, thiocyclam + TX, thiodicarb + TX, thiofanox + TX, thiohempa + TX, thiomersal + TX, thiometon + TX, thionazin + TX, thiophanate + TX, thiosultap + TX, thiotepa + TX, tiapyrachlor (CAS Number: 1255091-74-7) + TX, tigolaner + TX, tiorantraniliprole + TX, tioxazafen + TX, tolfenpyrad + TX, toxaphene + TX, tralomethrin + TX, transfluthrin + TX, tretamine + TX, triazamate + TX, triazophos + TX, triazuron + TX, tributyltin oxide + TX, trichlorfon + TX, trichloronate + TX, trichlorphon + TX, Trichogramma spp. + TX, trifenmorph + TX, trifluenfuronate + TX, triflumezopyrim + TX, trimedlure + TX, trimedlure A + TX, trimedlure B1 + TX, trimedlure B2 + TX, trimedlure C + TX, trimethacarb + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, trunc-call + TX, tyclopyrazoflor + TX, Typhlodromus occidentalis + TX, uredepa + TX, Verticillium lecanii + TX, Verticillium spp. + TX, xylenols + TX, YI-5302 + TX, zeatin + TX, zeta- Cypermethrin + TX; N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N- [(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-ethyl-N’-[5- methoxy-2-methyl-4-[(2-trifuoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine (these compounds may be prepared from the methods described in WO2019 / 110427) + TX, (3- methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone (these compounds may be prepared from the methods described in WO 2017 / 220485) + TX, (4- phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate (this compound may be prepared from the methods described in WO 2014 / 006945) + TX, (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)- 1,2,4-oxadiazol-3-yl]phenyl]methanone + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX, (9Z,11E)- tetradeca-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate + TX, (E)-6- methylhept-2-en-4-ol + TX, (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol + TX, (E)-tridec-4-en-1-yl acetate + TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate, + TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)- hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-icos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-109934 | 83191 FF 80 tetradec-9-en-1-yl acetate + TX, (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino- N,3-dimethyl-pent-3-enamide (this compound may be prepared from the methods described in WO 2018 / 153707) + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent- 3-enamide + TX, , [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]- 4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl] methanesulfonate + TX, 1-(4,5-dimethylbenzimidazol-1- yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3- dimethyl-isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl- isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline (these compounds may be prepared from the methods described in WO2017 / 025510) + TX, 1,1-bis(4- chlorophenyl)-2-ethoxyethanol + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane + TX, 1,2-dibromo-3- chloropropane + TX, 1,2-dichloropropane with 1,3-dichloropropene + TX, 1,3-dichloropropene + TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1-[2-[[1-(4- chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one + TX, 10-dien-1-yl acetate + TX, 14-methyloctadec-1-ene + TX, 1-bromo-2-chloroethane + TX, 1-dichloro-1-nitroethane + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl]phenyl]methyl]urea + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX, 2- (difluoromethyl) - N- ((3R) - 1, 1, 3- trimethylindan-4- yl) pyridine- 3- carboxamide + TX, 2- (difluoromethyl) - N- ((3R) - 1, 1, 3- trimethylindan- 4-yl)pyridine- 3- carboxamide + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-(2-butoxyethoxy)ethyl piperonylate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3- dioxolan-2-yl)phenyl methylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2- (difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)- N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-[(3S)-3- ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (this compound may be prepared from the methods described in WO 2014 / 095675) + TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4- yl]pyridine-3-carboxamide + TX, 2-(octylthio)ethanol + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethylacetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX, 2,4-dichlorophenyl benzenesulfonate + TX, 2,6-Dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)- tetrone (this compound may be prepared from the methods described in WO 2011 / 138281) + TX, 2- [2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol + TX, 2-[6-(4-bromophenoxy)-2- (trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound may be prepared from the methods described in WO 2017 / 029179) + TX, 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]- 1-(1,2,4-triazol-1-yl)propan-2-ol (this compound may be prepared from the methods described in WO 2017 / 029179) + TX, 2-chlorovinyl diethyl phosphate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 2-imidazolidone + TX, 2-isovalerylindan-1,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate + TX, 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]acetamide (this compound may be prepared from the methods described in WO 2018 / 065414) + TX, 2-thiocyanatoethyl laurate + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8- dihydro-6H-cyclopenta[e]benzimidazole (these compounds may be prepared from the methods109934 | 83191 FF 81 described in WO2016 / 156085) + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1- yl)quinolone + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3- trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO 2016 / 156290) + TX, 3-[2-(1- chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO 2016 / 156290) + TX, 3-bromo-1- chloroprop-1-ene + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, 3- difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, 3- ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate + TX, 4- (2- bromo- 4- fluorophenyl) - N- (2- chloro- 6-fluorophenyl) - 1, 3- dimethyl- 1H- pyrazol- 5- amine + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5- dimethyl-pyrazol-3-amine + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide + TX, 4,4-difluoro-1-(5- fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(6- methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7- methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2- hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1- difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile + TX, 4-[[6-[2- (2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile + TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, 4-chlorophenyl phenyl sulfone + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2- enone + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3- one + TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate + TX, 5-amino-1,3,4-thiadiazole-2- thiol zinc salt (2:1) + TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid + TX, 6-chloro-3-(3- cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4- carboxamide (may be prepared from the methods described in WO 2020 / 109391) + TX, 6-chloro-3- (3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine- 4-carboxamide (may be prepared from the methods described in WO 2020 / 109391) + TX, 6-chloro- 4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline + TX, 6-chloro-N-[2-(2-chloro-4- methyl-phenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4- carboxamide (may be prepared from the methods described in WO 2020 / 109391) + TX, 6-ethyl-5,7- dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile + TX, 6-isopentenylaminopurine + TX, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8- fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8- hydroxyquinoline sulfate + TX, acethion + TX, acetoprole + TX, acibenzolar + TX, acibenzolar-S- methyl + TX, acrylonitrile + TX, Adoxophyes orana GV + TX, Agrobacterium radiobacter + TX, aldoxycarb + TX, aldrin + TX, allosamidin + TX, allyxycarb + TX, alpha-chlorohydrin + TX, alpha- ecdysone + TX, alpha-multistriatin + TX, aluminium phosphide + TX, Amblyseius spp. + TX,109934 | 83191 FF 82 amectotractin + TX, ametoctradin + TX, amidithion + TX, amidothioate + TX, aminocarb + TX, aminopyrifen + TX, amisulbrom + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, anabasine + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, ancymidol + TX, anilazine + TX, anisiflupurin + TX, anthraquinone + TX, antu + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, apholate + TX, aramite + TX, arsenous oxide + TX, athidathion + TX, Autographa californica NPV + TX, azaconazole + TX, azamethiphos + TX, azobenzene + TX, azothoate + TX, azoxystrobin + TX, Bacillus sphaericus Neide + TX, Bacillus thuringiensis delta endotoxins + TX, barium carbonate + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, barthrin + TX, Bayer 22 / 190 + TX, Bayer 22408 + TX, Beauveria brongniartii + TX, benalaxyl + TX, benclothiaz + TX, benomyl + TX, benoxafos + TX, benthiavalicarb + TX, benzothiostrobin + TX, benzovindiflupyr + TX, benzyl benzoate + TX, beta-cyfluthrin + TX, beta- cypermethrin + TX, bethoxazin + TX, bioethanomethrin + TX, biopermethrin + TX, bis(2-chloroethyl) ether + TX, bis(tributyltin) oxide + TX, bisazir + TX, bisthiosemi + TX, bitertanol + TX, bixafen + TX, blasticidin-S + TX, borax + TX, bordeaux mixture + TX, boscalid + TX, brevicomin + TX, brodifacoum + TX, brofenvalerate + TX, bromadiolone + TX, bromethalin + TX, bromfenvinfos + TX, bromoacetamide + TX, bromocyclen + TX, bromo-DDT + TX, bromophos + TX, bromopropylate + TX, bromuconazole + TX, bronopol + TX, bufencarb + TX, bupirimate + TX, buprofezin + TX, busulfan + TX, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2- pyridyl]carbamate + TX, butacarb + TX, butathiofos + TX, butocarboxim + TX, butonate + TX, butopyronoxyl + TX, butoxy(polypropylene glycol) + TX, butoxycarboxim + TX, butylpyridaben + TX, calcium arsenate + TX, calcium cyanide + TX, calcium polysulfide + TX, camphechlor + TX, captafol + TX, captan + TX, carbanolate + TX, carbendazim + TX, carbon disulfide + TX, carbon tetrachloride + TX, carbophenothion + TX, carboxin + TX, cartap hydrochloride + TX, CAS Number: 2049581-78-2 + TX, CAS Number: 2454319-63-0 + TX, CAS Number: 3052252-62-4 + TX, CAS Number: 3052252- 63-5 + TX, CAS Number: 83-46-5 + TX, cevadine + TX, chinomethionat + TX, chloralose + TX, chlorbenside + TX, chlorbicyclen + TX, chlordane + TX, chlordecone + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorfenethol + TX, chlorfenson + TX, chlorfensulfide + TX, chlorobenzilate + TX, chloroform + TX, chloroinconazide + TX, chloromebuform + TX, chloromethiuron + TX, chloroneb + TX, chlorophacinone + TX, chloropicrin + TX, chloropropylate + TX, chlorothalonil + TX, chlorphoxim + TX, chlorprazophos + TX, chlorthiophos + TX, chlozolinate + TX, cholecalciferol + TX, Chrysoperla carnea + TX, cinerin I + TX, cinerin II + TX, cinerins + TX, cismethrin + TX, cis- resmethrin + TX, clocythrin + TX, closantel + TX, codlelure + TX, codlemone + TX, copper acetoarsenite + TX, copper arsenate + TX, copper dioctanoate + TX, copper hydroxide + TX, copper naphthenate + TX, copper oleate + TX, copper oxide + TX, copper oxychloride + TX, copper sulfate + TX, coumachlor + TX, coumafuryl + TX, coumaphos + TX, coumatetralyl + TX, coumethoxystrobin (jiaxiangjunzhi) + TX, coumithoate + TX, coumoxystrobin + TX, cresol + TX, crimidine + TX, crotamiton + TX, crotoxyphos + TX, crufomate + TX, cryolite + TX, Cryptolaemus montrouzieri + TX, CS 708 + TX, cuelure + TX, cufraneb + TX, cyanofenphos + TX, cyanophos + TX, cyanthoate + TX, cyazofamid + TX, cybutryne + TX, cyclethrin + TX, cyclobutrifluram + TX, Cydia pomonella GV + TX, cyflufenamid + TX, cymiazole + TX, cymoxanil + TX, cyproconazole + TX, cyprodinil + TX, cythioate + TX, cytokinins + TX, Dacnusa sibirica + TX, DAEP + TX, dazomet + TX, DCIP + TX, DCPM + TX, DDT + TX, debacarb109934 | 83191 FF 83 + TX, decarbofuran + TX, demephion + TX, demephion-O + TX, demephion-S + TX, demeton-methyl + TX, demeton-O + TX, demeton-O-methyl + TX, demeton-S + TX, demeton-S-methyl + TX, demeton- S-methylsulfon + TX, diamidafos + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, dicapthon + TX, dichlobentiazox + TX, dichlofenthion + TX, dichlofluanid + TX, dichlone + TX, dichlorophen + TX, dichlorvos + TX, dichlozoline + TX, dicliphos + TX, diclocymet + TX, diclomezine + TX, dicloran + TX, dicresyl + TX, dicyclanil + TX, dicyclopentadiene + TX, dieldrin + TX, dienochlor + TX, diethofencarb + TX, diethyl 5-methylpyrazol-3-yl phosphate + TX, diethyltoluamide + TX, difenacoum + TX, difenoconazole + TX, difethialone + TX, diflovidazin + TX, Diglyphus isaea + TX, dilor + TX, dimatif + TX, dimefluthrin + TX, dimefox + TX, dimetan + TX, dimethirimol + TX, dimethomorph + TX, dimethrin + TX, dimethyl carbate + TX, dimethyl phthalate + TX, dimethylvinphos + TX, dimetilan + TX, dimoxystrobin + TX, dinex + TX, dinex-diclexine + TX, diniconazole + TX, dinocap-4 + TX, dinocap-6 + TX, dinocton + TX, dinopenton + TX, dinoprop + TX, dinosam + TX, dinoseb + TX, dinosulfon + TX, dinoterbon + TX, diofenolan + TX, dioxabenzofos + TX, dioxathion + TX, diphacinone + TX, diphenyl sulfone + TX, dipymetitrone + TX, dipyrithione + TX, disparlure + TX, disulfiram + TX, dithianon + TX, dithicrofos + TX, DNOC + TX, dodec-8-en-1-yl acetate + TX, dodec- 9-en-1-yl acetate + TX, dodeca-8 + TX, dodemorph + TX, dodicin + TX, dodine + TX, dofenapyn + TX, dominicalure + TX, doramectin + TX, DSP + TX, d-tetramethrin + TX, ecdysterone + TX,edifenphos + TX, EI 1642 + TX, EMPC + TX, Encarsia formosa + TX, endothal + TX, endothion + TX,enestroburin + TX, enoxastrobin + TX, EPBP + TX, epoxiconazole + TX, eprinomectin + TX, Eretmocerus eremicus + TX, ergocalciferol + TX, etaphos + TX, ethaboxam + TX, ethiofencarb + TX, ethirimol + TX, ethoate-methyl + TX, ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1- enoxy]phenyl]methyl]pyrazole-3-carboxylate (may be prepared from the methods described in WO 2020 / 056090) + TX, ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2- yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate (may be prepared from the methods described in WO 2020 / 056090) + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole- 4-carboxylate + TX, ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4- carboxylate (this compound may be prepared from the methods described in WO 2018 / 158365) + TX, ethyl 4-methyloctanoate + TX, ethyl formate + TX, ethyl hexanediol + TX, ethylene dibromide + TX, ethylene dichloride + TX, ethylene oxide + TX, etridiazole + TX, etrimfos + TX, eugenol + TX, EXD + TX, famoxadone + TX, farnesol + TX, farnesol with nerolidol + TX, fenamidone + TX, fenaminosulf + TX, fenaminstrobin + TX, fenarimol + TX, fenazaflor + TX, fenbuconazole + TX, fenbutatin oxide + TX, fenchlorphos + TX, feneptamidoquin (CAS Number: 2132414-04-9) + TX, fenethacarb + TX, fenfuram + TX, fenhexamid + TX, fenitrothion + TX, fenopyramid (CAS Number: 2344721-61-3) + TX, fenothiocarb + TX, fenoxacrim + TX, fenoxanil + TX, fenpiclonil + TX, fenpicoxamid + TX, fenpirithrin + TX, fenpropidin + TX, fenpropimorph + TX, fenpyrad + TX, fenpyrazamine + TX, fenpyroximate + TX, fenson + TX, fensulfothion + TX, fenthion + TX, fenthion-ethyl + TX, fentin + TX, fentrifanil + TX, ferbam + TX, ferimzone + TX, ferric phosphate + TX, flocoumafen + TX, florylpicoxamid + TX, fluazinam + TX, flubeneteram + TX, flubenzimine + TX, flucofuron + TX, flucycloxuron + TX, fludioxonil + TX, fluenetil + TX, flufenoxadiazam + TX, flufenoxystrobin + TX, fluindapyr + TX, flumetylsulforim + TX, flumorph + TX, fluopicolide + TX, fluopimomide + TX, fluopyram + TX, fluorbenside + TX, fluoroacetamide + TX, fluoroimide + TX, fluoxapiprolin + TX, fluoxastrobin + TX, fluoxytioconazole +109934 | 83191 FF 84 TX, flupropadine + TX, flupropadine hydrochloride + TX, fluquinconazole + TX, flusilazole + TX, flusulfamide + TX, flutianil + TX, flutolanil + TX, flutriafol + TX, fluxapyroxad + TX, FMC 1137 + TX, folpet + TX, formaldehyde + TX, formetanate + TX, formetanate hydrochloride + TX, formparanate + TX, fosetyl-aluminium + TX, fosmethilan + TX, fospirate + TX, fosthietan + TX, frontalin + TX, fuberidazole + TX, furalaxyl + TX, furametpyr + TX, furathiocarb + TX, furethrin + TX, furfural + TX, gamma-HCH + TX, glyodin + TX, grandlure + TX, grandlure I + TX, grandlure II + TX, grandlure III + TX, grandlure IV + TX, guazatine + TX, guazatine acetates + TX, halfenprox + TX, HCH + TX, hemel + TX, hempa + TX, HEOD + TX, heptachlor + TX, heterophos + TX, Heterorhabditis bacteriophora and H. megidis + TX, hexaconazole + TX, hexadecyl cyclopropanecarboxylate + TX, hexalure + TX, hexamide + TX, HHDN + TX, Hippodamia convergens + TX, hydrargaphen + TX, hydrated lime + TX, hydrogen cyanide + TX, hymexazol + TX, hyquincarb + TX, imanin + TX, imazalil + TX, imibenconazole + TX, iminoctadine + TX, inpyrfluxam + TX, ipconazole + TX, ipfentrifluconazole + TX, ipflufenoquin + TX, iprobenphos + TX, iprodione + TX, iprovalicarb + TX, ipsdienol + TX, ipsenol + TX, IPSP + TX, isamidofos + TX, isazofos + TX, isobenzan + TX, isocarbophos + TX, isodrin + TX, isofenphos + TX, isofetamid + TX, isoflucypram + TX, isolane + TX, isoprothiolane + TX, isopyrazam + TX, isotianil + TX, isoxathion + TX, japonilure + TX, jasmolin I + TX, jasmolin II + TX, jodfenphos + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, kadethrin + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, kelevan + TX, kinetin + TX, kinoprene + TX, kresoxim-methyl + TX, lead arsenate + TX, Leptomastix dactylopii + TX, leptophos + TX, lindane + TX, lineatin + TX, lirimfos + TX, litlure + TX, looplure + TX, lvbenmixianan + TX, lythidathion + TX, Macrolophus caliginosus + TX, magnesium phosphide + TX, malonoben + TX, Mamestra brassicae NPV + TX, mancopper + TX, mancozeb + TX, mandestrobin + TX, mandipropamid + TX, maneb + TX, mazidox + TX, m-cumenyl methylcarbamate + TX, mecarbam + TX, mecarphon + TX, medlure + TX, mefentrifluconazole + TX, megatomoic acid + TX, menazon + TX, mepanipyrim + TX, meperfluthrin + TX, mephosfolan + TX, mepronil + TX, mercuric oxide + TX, mercurous chloride + TX, mesulfen + TX, mesulfenfos + TX, metalaxyl + TX, metam + TX, metam-potassium + TX, metam- sodium + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, metarylpicoxamid + TX, metconazole + TX, metepa + TX, methacrifos + TX, methanesulfonyl fluoride + TX, methasulfocarb + TX, methiotepa + TX, methocrotophos + TX, methoprene + TX, methoquin-butyl + TX, methothrin + TX, methoxychlor + TX, methyl (Z)-2-(5- cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate + TX, methyl (Z)-2-(5-cyclopentyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate (these compounds may be prepared from the methods described in WO2020 / 193387) + TX, methyl (Z)-2-[5-(3-isopropylpyrazol-1-yl)-2-methyl-phenoxy]-3-methoxy- prop-2-enoate + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-(3-propylpyrazol-1-yl)phenoxy]prop-2- enoate + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-(4-propyltriazol-2-yl)phenoxy]prop-2-enoate + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]prop-2-enoate (these compounds may be prepared from the methods described in WO2020 / 079111) + TX, methyl (Z)-3- methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop-2-enoate + TX, methyl apholate + TX, methyl bromide + TX, methyl eugenol + TX, methyl isothiocyanate + TX, methyl N-[[4-[1-(2,6- difluoro-4-isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (may be prepared from the methods described in WO 2020 / 097012) + TX, methyl N-[[4-[1-(4-cyclopropyl-2,6-difluoro-109934 | 83191 FF 85 phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (may be prepared from the methods described in WO 2020 / 097012) + TX, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl- phenyl]methyl]carbamate + TX, methylchloroform + TX, methylene chloride + TX, methylneodecanamide + TX, metiram + TX, metolcarb + TX, metomi-nostrobin + TX, metoxadiazone + TX, metrafenone + TX, metyltetraprole + TX, MGK 264 + TX, milbemycin oxime + TX, mipafox + TX, mirex + TX, monocrotophos + TX, morphothion + TX, morzid + TX, moxidectin + TX, muscalure + TX, myclobutanil + TX, myclozoline + TX, Myrothecium verrucaria composition + TX, N-((1R)-1- benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide (these compounds may be prepared from the methods described in WO2017 / 153380) + TX, N-((1S)-1-benzyl-3-chloro-1-methyl- but-3-enyl)-8-fluoro-quinoline-3-carboxamide (these compounds may be prepared from the methods described in WO2017 / 153380) + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl- formamidine + TX, N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N,N- dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine (THESE COMPOUNDS may be prepared from the methods described in WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 093348 and WO 2017 / 118689) + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro- quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3- carboxamide + TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3- carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3,3,3- trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(E)-methoxyiminomethyl]-4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[(Z)-methoxyiminomethyl]-4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl]propanamide + TX, N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl- pyrazole-4-carboxamide + TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)- 1-methyl-pyrazole-4-carboxamide + TX, N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl- N-methyl-formamidine (this compound may be prepared from the methods described in WO 2016 / 202742) + TX, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl- formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl- formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N- methyl-formamidine (these compounds may be prepared from the methods described in WO2015 / 155075) + TX, N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl- formamidine (this compound may be prepared from the methods described in IPCOM000249876D) + TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl- formamidine + TX, N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N- methyl-formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N- methyl-formamidine + TX, N-[N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl]benzamide (these compounds may be prepared from the methods described in WO 2018 / 202428) + TX, N’-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl- phenyl]-N-isopropyl-N-methyl-formamidine (these compounds may be prepared from the methods described in WO2018 / 228896) + TX, nabam + TX, naftalofos + TX, naled + TX, naphthalene + TX,109934 | 83191 FF 86 NC-170 + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, nerolidol + TX, N-ethyl-2-methyl-N- [[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N-ethyl-N’-[5-methoxy- 2-methyl-4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX, nickel bis(dimethyldithiocarbamate) + TX, niclosamide-olamine + TX, nicotine + TX, nicotine sulfate + TX, nifluridide + TX, nikkomycins + TX, N-isopropyl-N’-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy- 1-phenyl-ethyl)phenyl]-N-methyl-formamidine + TX, nithiazine + TX, nitrapyrin + TX, nitrilacarb + TX, nitrilacarb 1:1 zinc chloride complex + TX, nitrothal-isopropyl + TX, N-methoxy-N-[[4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N-methyl-4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-methyl-4-[5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl]benzenecarbothioamide + TX, norbormide + TX, nuarimol + TX, O,O,O',O'-tetrapropyl dithiopyrophosphate + TX, octadeca-2,13-dien-1-yl acetate + TX, octadeca-3,13-dien-1-yl acetate + TX, octhilinone + TX, ofurace + TX, oleic acid + TX, omethoate + TX, orfralure + TX, Orius spp. + TX, oryctalure + TX, orysastrobin + TX, ostramone + TX, oxadixyl + TX, oxamate + TX, oxathiapiprolin + TX, oxine-copper + TX, oxolinic acid + TX, oxycarboxin + TX, oxydeprofos + TX, oxydisulfoton + TX, oxytetracycline + TX, paclobutrazole + TX, Paecilomyces fumosoroseus + TX, para-dichlorobenzene + TX, parathion + TX, parathion-methyl + TX, pefurazoate + TX, penconazole + TX, pencycuron + TX, penflufen + TX, penfluron + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, penthiopyrad + TX, permethrin + TX, PH 60-38 + TX, phenamacril + TX, phenkapton + TX, phosacetim + TX, phosalone + TX, phosdiphen + TX, phosfolan + TX, phosglycin + TX, phosnichlor + TX, phosphamidon + TX, phosphine + TX, phosphorus + TX, phoxim-methyl + TX, phthalide + TX, Phytoseiulus persimilis + TX, picarbutrazox + TX, picaridin + TX, picoxystrobin + TX, pindone + TX, piperazine + TX, piperonyl butoxide + TX, piprotal + TX, pirimetaphos + TX,polychlorodicyclopentadiene isomers + TX, polychloroterpenes + TX, polynactins + TX, polyoxins +TX, potassium arsenite + TX, potassium ethylxanthate + TX, potassium hydroxyquinoline sulfate + TX, potassium thiocyanate + TX, pp'-DDT + TX, precocene I + TX, precocene II + TX, precocene III + TX, primidophos + TX, probenazole + TX, prochloraz + TX, proclonol + TX, procymidone + TX, profluthrin + TX, promacyl + TX, promecarb + TX, propamocarb + TX, propiconazole + TX, propineb + TX, propoxur + TX, propyl isomer + TX, proquinazid + TX, prothidathion + TX, prothioconazole + TX, prothiofos + TX, prothoate + TX, pydiflumetofen + TX, pyraclostrobin + TX, pyrametostrobin + TX, pyraoxystrobin + TX, pyrapropoyne + TX, pyraziflumid + TX, pyrazophos + TX, pyresmethrin + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrins + TX, pyribencarb + TX, pyridachlometyl + TX, pyridaphenthion + TX, pyridin-4-amine + TX, pyrifenox + TX, pyrimethanil + TX, pyrimitate + TX, pyrimorph + TX, pyrinuron + TX, pyriofenone + TX, pyrisoxazole + TX, pyroquilon + TX, quassia + TX, quinalphos + TX, quinalphos-methyl + TX, quinoclamine + TX, quinofumelin + TX, quinonamid + TX, quinothion + TX, quinoxyfen + TX, quintiofos + TX, quintozene + TX, R-1492 + TX, rafoxanide + TX, resmethrin + TX, Reynoutria sachalinensis extract + TX, ribavirin + TX, R metalaxyl + TX, rotenone + TX, ryania + TX, ryanodine + TX, S421 + TX, sabadilla + TX, schradan + TX, scilliroside + TX, seboctylamine + TX, sebufos + TX, sedaxane + TX, selamectin + TX, sesamex + TX, sesasmolin + TX, SI-0009 + TX, siglure + TX, simazine + TX, simeconazole + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium fluoroacetate + TX, sodium hexafluorosilicate + TX, sodium pentachlorophenoxide + TX, sodium selenate + TX, sodium tetrathiocarbonate + TX, sodium109934 | 83191 FF 87 thiocyanate + TX, sophamide + TX, sordidin + TX, spiroxamine + TX, SSI-121 + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX,Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernemaspp. + TX, streptomycin + TX, streptomycin sesquisulfate + TX, strychnine + TX, sulcatol + TX, sulcofuron + TX, sulcofuron-sodium + TX, sulfiram + TX, sulfluramid + TX, sulfotep + TX, sulfoxide + TX, sulfur + TX, sulfuryl fluoride + TX, sulprofos + TX, tar oils + TX, tau-fluvalinate + TX, tazimcarb + TX, TDE + TX, tebuconazole + TX, tebufloquin + TX, tebupirimfos + TX, tecloftalam + TX, temephos+ TX, tepa + TX, TEPP + TX, terallethrin + TX, terbam + TX, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, tetrachloroethane + TX, tetrachlorothiophene + TX, tetraconazole + TX, tetradec-11-en-1-yl acetate + TX, tetradifon + TX, tetramethylfluthrin + TX, tetrasul + TX, thallium sulfate + TX, thiabendazole + TX, thiafenox + TX, thiapronil + TX, thicrofos + TX, thifluzamide + TX, thiocarboxime + TX, thiocyclam + TX, thiocyclam hydrogen oxalate + TX, thiodiazole copper + TX, thiofanox + TX, thiohempa + TX, thiomersal + TX, thiometon + TX, thionazin + TX, thiophanate + TX, thiophanate-methyl + TX, thioquinox + TX, thiosultap + TX, thiosultap-sodium + TX, thiotepa + TX, thiram + TX, thuringiensin + TX, tiadinil + TX, tolclofos-methyl + TX, tolprocarb + TX, tolylfluanid + TX, tralomethrin + TX, transpermethrin + TX, tretamine + TX, triadimefon + TX, triadimenol + TX, triamiphos + TX, triarathene + TX, triazamate + TX, triazophos + TX, triazoxide + TX, triazuron + TX, tributyltin oxide + TX, trichlormetaphos-3 + TX, trichloronat + TX, Trichogramma spp. + TX, triclopyricarb + TX, tricyclazole + TX, tridemorph + TX, trifenmorph + TX, trifenofos + TX, trifloxystrobin + TX, triflumizole + TX, triforine + TX, trimedlure + TX, trimedlure A + TX, trimedlure B1 + TX, trimedlure B2 + TX, trimedlure C + TX, trimethacarb + TX, trinactin + TX, trinexapac + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, triprene + TX, triticonazole + TX, trunc-call + TX, Typhlodromus occidentalis + TX, uredepa + TX, validamycin + TX, valifenalate + TX, vamidothion + TX, vaniliprole + TX, veratridine + TX, veratrine + TX, verbutin + TX, Verticillium lecanii + TX, vinclozoline + TX, warfarin + TX, XMC + TX, xylenols + TX, zeatin + TX, zetamethrin + TX, zhongshengmycin + TX, zinc naphthenate + TX, zinc phosphide + TX, zinc thiazole+ TX, zineb + TX, ziram + TX, zolaprofos + TX, zoxamide + TX, α- (1, 1- dimethylethyl) - α- [4'-(trifluoromethoxy) [1, 1'- biphenyl] - 4- yl] -5- pyrimidinemethanol + TX;Acinetobacter lwoffii + TX, Acremonium alternatum + TX, Acremonium cephalosporium + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, Adoxophyes orana granulovirus (AdoxGV) (Capex®) + TX, Agrobacterium radiobacter strain K84 (Galltrol-A®) + TX, Alternaria alternate + TX, Alternaria cassia + TX, Alternaria destruens (Smolder®) + TX, Ampelomyces quisqualis (AQ10®) + TX, Aspergillus flavus AF36 (AF36®) + TX, Aspergillus flavus NRRL 21882 (Aflaguard®) + TX, Aspergillus spp. + TX, Aureobasidium pullulans + TX, Azospirillum (MicroAZ®, TAZO B®) + TX, Azotobacter + TX, Azotobacter chroocuccum (Azotomeal®) + TX, Azotobacter cysts (Bionatural Blooming Blossoms®) + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus chitinosporus strain AQ746 + TX, Bacillus chitinosporus strain CM-1 + TX, Bacillus circulans + TX, Bacillus firmus (BioSafe®, BioNem-WP®) in particular strain CNMC 1-1582 (e.g. VOTIVO® from BASF SE) + TX, Bacillus licheniformis strain 3086 (EcoGuard®, Green Releaf®) + TX, Bacilluslicheniformis strain HB-2 (Biostart™ formerly Rhizoboost®) + TX, Bacillus macerans + TX, Bacillusmarismortui + TX, Bacillus megaterium + TX, Bacillus mycoides strain AQ726 + TX, Bacillus papillae109934 | 83191 FF 88 (Milky Spore Powder®) + TX, Bacillus pumilus spp. + TX, Bacillus pumilus strain AQ717 + TX, Bacillus pumilus strain GB34 (Yield Shield®) + TX, Bacillus pumilus strain QST 2808 (Sonata®, Ballad Plus®) + TX, Bacillus sphaericus (VectoLex®) + TX, Bacillus spp. + TX, Bacillus spp. strain AQ175 + TX, Bacillus spp. strain AQ177 + TX, Bacillus spp. strain AQ178 + TX, Bacillus subtilis strain AQ153 + TX, Bacillus subtilis strain AQ743 + TX, Bacillus subtilis strain QST 713 (CEASE®, Serenade®, Rhapsody®) + TX, Bacillus subtilis strain QST 714 (JAZZ®) + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain QST3004 + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24(Taegro®, Rhizopro®) + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillusthuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1Ab + TX, Bacillus thuringiensis israelensis (BMP123®, Aquabac®, VectoBac®) + TX, Bacillus thuringiensis kurstaki (Javelin®, Deliver®, CryMax®, Bonide®, Scutella WP®, Turilav WP ®, Astuto®, Dipel WP®, Biobit®, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF / 3P®) + TX, Bacillus thuringiensis strain AQ52 + TX, Bacillus thuringiensis strain BD#32 + TX, Bacillus thuringiensis tenebrionis (Novodor®, BtBooster) + TX, Bacillus thuringiensis var. aizawai (XenTari®, DiPel®) + TX, bacteria spp. (GROWMEND®, GROWSWEET®, Shootup®) + TX, bacteriophage of Clavipacter michiganensis (AgriPhage®, Bakflor®) + TX, Beauveria bassiana (Beaugenic®, Brocaril WP®) + TX, Beauveria bassiana GHA (Mycotrol ES®, Mycotrol O®, BotaniGuard®) + TX, Beauveria brongniartii (Engerlingspilz®, Schweizer Beauveria®, Melocont®) + TX, Beauveria spp. + TX, Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Burkholderia cepacia (Deny®, Intercept®, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp. + TX, Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reukaufii + TX, Candida saitoana (Bio-Coat®, Biocure®) + TX, Candida sake + TX, Candida spp. + TX, Candida tenius + TX, Cedecea davisae + TX, Cellulomonas flavigena + TX, Chaetomium cochliodes (Nova-Cide®) + TX, Chaetomium globosum (Nova-Cide®) + TX, Chromobacteriumsubtsugae strain PRAA4-1T (Grandevo®) + TX, Cladosporium chlorocephalum + TX, Cladosporiumcladosporioides + TX, Cladosporium oxysporum + TX, Cladosporium spp. + TX, Cladosporium tenuissimum + TX, Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp. + TX, Cryptococcus albidus (YIELDPLUS®) + TX, Cryptococcus humicola + TX, Cryptococcus infirmo-miniatus + TX, Cryptococcus laurentii + TX, Cryptophlebia leucotreta granulovirus (Cryptex®) + TX, Cupriavidus campinensis + TX, Cydia pomonella granulovirus (CYD-X®, Madex®, Madex® Plus, Madex Max, Carpovirusine® + TX, Cylindrobasidium laeve (Stumpout®) + TX, Cylindrocladium + TX, Debaryomyces hansenii + TX, Drechslera hawaiinensis + TX, Enterobacter cloacae + TX, Enterobacteriaceae + TX, Entomophtora virulenta (Vektor®) + TX, Epicoccum nigrum + TX, Epicoccum purpurascens + TX, Epicoccum spp. + TX, Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean®, Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop®, Prestop®) + TX, Gliocladium roseum + TX, Gliocladium spp. (SoilGard®)109934 | 83191 FF 89 + TX, Gliocladium virens (Soilgard®) + TX, Granulovirus (Granupom®) + TX, Halobacillus halophilus + TX, Halobacillus litoralis + TX, Halobacillus trueperi + TX, Halomonas spp. + TX, Halomonas subglaciescola + TX, Halovibrio variabilis + TX, Hanseniaspora uvarum + TX, Helicoverpa armigera nucleopolyhedrovirus (Helicovex®) + TX, Helicoverpa zea nuclear polyhedrosis virus (Gemstar®) + TX, Isaria fumosorosea (previously known as Paecilomyces fumosoroseus strain, PFR-97®, PreFeRal®) + TX, Isoflavone formononetin (Myconate®) + TX, Kloeckera apiculata + TX, Kloeckera spp. + TX, Lagenidium giganteum (Laginex®) + TX, Lecanicillium lecanii (formerly known as Verticillium lecanii (Mycotal®) conidia of strain KV01 (e.g. Vertalec® by Koppert / Arysta) + TX, Lecanicillium longisporum (Vertiblast®) + TX, Lecanicillium muscarium (Vertikil®) + TX, Lymantria Dispar nucleopolyhedrosis virus (Disparvirus®) + TX, Marinococcus halophilus + TX, Meira geulakonigii + TX, Metarhizium anisopliae (Destruxin WP®) + TX, Metarhizium anisopliae (Met52®) + TX, Metschnikowia fruticola (Shemer®) + TX, Metschnikowia pulcherrima + TX, Microdochium dimerum (Antibot®) + TX, Micromonospora coerulea + TX, Microsphaeropsis ochracea + TX, Muscodor albus 620 (Muscudor®) + TX, Muscodor roseus in particular strain A3-5 (Accession No. NRRL 30548) + TX, Mycorrhizae spp. (AMykor®, Root Maximizer®) + TX, Myrothecium verrucaria strain AARC-0255 (DiTera®, BROS PLUS®) + TX, Ophiostoma piliferum strain D97 (Sylvanex®) + TX, Paecilomyces farinosus + TX, Paecilomyces lilacinus strain 251 (MeloCon WG®) + TX, Paecilomyces linacinus (Biostat WP®) + TX, Paenibacillus polymyxa + TX, Pantoea agglomerans (BlightBan C9-1®) + TX, Pantoea spp. + TX, Pasteuria nishizawae in particular strain Pn1 (CLARIVA from Syngenta / ChemChina); + TX, Pasteuria spp. (Econem®) + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart®, TagTeam®) + TX, Penicillium brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp. + TX, Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, phosphate solubilizing bacteria (Phosphomeal®) + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guilliermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Pseudomonas fluorescens (Zequanox®) + TX, Pseudomonas fluorescens strain A506 (BlightBan A506®) + TX, Pseudomonas putida + TX, Pseudomonas reactans + TX, Pseudomonas spp. + TX, Pseudomonas syringae (Bio-Save®) + TX, Pseudomonas viridiflava + TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®) + TX, Puccinia canaliculata + TX, Puccinia thlaspeos (Wood Warrior®) + TX, Pythium paroecandrum + TX, Pythium oligandrum (Polygandron®, Polyversum®) + TX, Pythium periplocum + TX, Rhanella aquatilis + TX, Rhanella spp. + TX, Rhizobia (Dormal®, Vault®) + TX, Rhizoctonia + TX, Rhodococcus globerulus strain AQ719 + TX, Rhodosporidium diobovatum + TX, Rhodosporidium toruloides + TX, Rhodotorula glutinis + TX, Rhodotorula graminis + TX, Rhodotorula mucilagnosa + TX, Rhodotorula rubra + TX, Rhodotorula spp. + TX, Saccharomyces cerevisiae + TX, Salinococcus roseus + TX, Sclerotinia minor (SARRITOR®) + TX, Sclerotinia minor + TX, Scytalidium spp. + TX, Scytalidium uredinicola + TX, Serratia marcescens + TX, Serratia plymuthica + TX, Serratia spp. + TX, Sordaria fimicola + TX, Spodoptera exigua nuclear polyhedrosis virus (Spod-X®, Spexit®) + TX, Spodoptera littoralis nucleopolyhedrovirus (Littovir®) + TX, Sporobolomyces roseus + TX, Stenotrophomonas maltophilia109934 | 83191 FF 90 + TX, Streptomyces albaduncus + TX, Streptomyces exfoliates + TX, Streptomyces galbus + TX, Streptomyces griseoplanus + TX, Streptomyces griseoviridis (Mycostop®) + TX, Streptomyces hygroscopicus + TX, Streptomyces lydicus (Actinovate®) + TX, Streptomyces lydicus WYEC-108 (ActinoGrow®) + TX, Streptomyces violaceus + TX, Tilletiopsis minor + TX, Tilletiopsis spp. + TX, Trichoderma asperellum (T34 Biocontrol®) + TX, Trichoderma atroviride (Plantmate®) + TX, Trichoderma gamsii (Tenet®) + TX, Trichoderma hamatum TH 382 + TX, Trichoderma harzianum rifai (Mycostar®) + TX, Trichoderma harzianum T-22 (Trianum-P®, PlantShield HC®, RootShield®, Trianum-G® + TX, Trichoderma harzianum T-39 (Trichodex®) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + TX, Trichoderma spp. LC 52 (Sentinel®) + TX, Trichoderma taxi + TX, Trichoderma virens (formerly Gliocladium virens GL-21) (SoilGuard®) + TX, Trichoderma virens + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, Trichosporon spp. + TX, Trichothecium roseum + TX, Trichothecium spp. + TX, Typhula phacorrhiza strain 94670 + TX, Typhula phacorrhiza strain 94671 + TX, Ulocladium atrum + TX, Ulocladium oudemansii (Botry-Zen®) + TX, Ustilago maydis + TX, various bacteria and supplementary micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv. Poae (Camperico®) + TX, Xenorhabdus bovienii + TX, Xenorhabdus nematophilus + TX; AGNIQUE® MMF + TX, azadirachtin (Plasma Neem Oil®, AzaGuard®, MeemAzal®, Molt-X® e.g. AZATIN XL from Certis, US) + TX, Botanical IGR (Neemazad®, Neemix®) + TX, BugOil® + TX, canola oil (Lilly Miller Vegol®) + TX, Chenopodium ambrosioides near ambrosioides (Requiem®) + TX, Chrysanthemum extract (Crisant®) + TX, essentials oils of Labiatae (Botania®) + TX, extract of neem oil (Trilogy®) + TX, extracts of clove rosemary peppermint and thyme oil (Garden insect killer®) + TX, garlic + TX, Glycinebetaine (Greenstim®) + TX, kaolin (Screen®) + TX, lemongrass oil (GreenMatch®) + TX, Melaleuca alternifolia extract (also called tea tree oil) (Timorex Gold®) + TX, mixture of clove pepermint garlic oil and mint (Soil Shot®) + TX, mixture of clove rosemary and peppermint extract (EF 400®) + TX, mixture of rosemary sesame pepermint thyme and cinnamon extracts (EF 300®) + TX, neem oil + TX, Nepeta cataria (Catnip oil) + TX, Nepeta catarina + TX, nicotine + TX, oregano oil (MossBuster®) + TX, Pedaliaceae oil (Nematon®) + TX, pine oil (Retenol®) + TX, pyrethrum + TX, Quillaja saponaria (NemaQ®) + TX, Reynoutria sachalinensis (Regalia®, Sakalia®) + TX, rotenone (Eco Roten®) + TX, Rutaceae plant extract (Soleo®) + TX, soybean oil (Ortho ecosense®) + TX, storage glucam of brown algae (Laminarin®) + TX, thyme oil + TX; (E,Z)-7,9-Dodecadien-1-yl acetate + TX, (E,Z,Z)-3,8,11 Tetradecatrienyl acetate + TX, (Z,Z,E)-7,11,13-Hexadecatrienal + TX, 2-Methyl-1-butanol + TX, Biolure® + TX, blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®) + TX, Calcium acetate + TX, Check-Mate® + TX, Codling Moth Pheromone (Paramount dispenser-(CM) / Isomate C-Plus®) +TX, Entostat powder (extract from palm tree) (Exosex CM®) + TX, Grape Berry Moth Pheromone (3MMEC-GBM Sprayable Pheromone®) + TX, Lavandulyl senecioate + TX, Leafroller pheromone (3MMEC – LR Sprayable Pheromone®) + TX, Muscamone (Snip7 Fly Bait® + TX, Oriental Fruit MothPheromone (3M oriental fruit moth sprayable pheromone®) + TX, Peachtree Borer Pheromone109934 | 83191 FF 91 (Isomate-P®) + TX, Scenturion® + TX, Starbar Premium Fly Bait®) + TX, Tomato Pinworm Pheromone (3M Sprayable pheromone®) + TX; Acerophagus papaya + TX, Adalia bipunctata (Adalia-System®) + TX, Adalia bipunctata (Adaline®) + TX, Adalia bipunctata (Aphidalia®) + TX, Ageniaspis citricola + TX, Ageniaspis fuscicollis + TX, Amblyseius andersoni (Anderline®, Andersoni-System®) + TX, Amblyseius californicus (Amblyline®, Spical®) + TX, Amblyseius cucumeris (Thripex®, Bugline cucumeris®) + TX, Amblyseius fallacis (Fallacis®) + TX, Amblyseius swirskii (Bugline swirskii®, Swirskii-Mite®) + TX, Amblyseius womersleyi (WomerMite®) + TX, Amitus hesperidum + TX, Anagrus atomus + TX, Anagyrus fusciventris + TX, Anagyrus kamali + TX, Anagyrus loecki + TX, Anagyrus pseudococci (Citripar®) + TX, Anicetus benefices + TX, Anisopteromalus calandrae + TX, Anthocoris nemoralis (Anthocoris-System®) + TX, Aphelinus abdominalis (Apheline®, Aphiline®), + TX, Aphelinus asychis + TX, Aphidius colemani (Aphipar®) + TX, Aphidius ervi (Aphelinus-System®) + TX, Aphidius ervi (Ervipar®) + TX, Aphidius gifuensis + TX, Aphidius matricariae (Aphipar-M®) + TX, Aphidoletes aphidimyza (Aphidend®, Aphidoline®) + TX, Aphytis lingnanensis + TX, Aphytis melinus + TX, Aprostocetus hagenowii + TX, Atheta coriaria (Staphyline®) + TX, Bombus spp. + TX, Bombus terrestris (Beeline®, Tripol®) + TX, Bombus terrestris (Natupol Beehive®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus + TX, Chrysoperla carnea (Chrysoline®, Chrysopa®) + TX,Chrysoperla rufilabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichusphyllocnistoides + TX, Closterocerus chamaeleon + TX, Closterocerus spp. + TX, Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug®, Cryptoline®) + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica (Minusa®, DacDigline®, Minex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea (Diminex®, Miglyphus®, Digline®) + TX, Diversinervus spp. + TX, Encarsia citrina + TX, Encarsia formosa (Encarsia max®, Encarline®, En-Strip®) + TX, Encarsia guadeloupae + TX, Encarsia haitiensis + TX, Episyrphus balteatus (Syrphidend®) + TX, Eretmoceris siphonini + TX, Eretmocerus californicus + TX, Eretmocerus eremicus (Enermix®, Ercal®, Eretline e®, Bemimix®) + TX, Eretmocerus hayati + TX, Eretmocerus mundus (Bemipar®, Eretline m®) + TX, Eretmocerus siphonini + TX, Exochomus quadripustulatus + TX, Feltiella acarisuga (Feltiline®) + TX, Feltiella acarisuga (Spidend®) + TX, Fopius arisanus + TX, Fopius ceratitivorus + TX, Formononetin (Wirless Beehome®) + TX, Franklinothrips vespiformis (Vespop®) + TX, Galendromus occidentalis + TX, Goniozus legneri + TX, Habrobracon hebetor + TX, Harmonia axyridis (HarmoBeetle®) + TX, Heterorhabditis bacteriophora (NemaShield HB®, Nemaseek®, Terranem-Nam®, Terranem®, Larvanem®, B-Green®, NemAttack ®, Nematop®) + TX, Heterorhabditis megidis (Nemasys H®, BioNem H®, Exhibitline hm®, Larvanem-M®) + TX, Heterorhabditis spp. (Lawn Patrol®) + TX, Hippodamia convergens + TX, Hypoaspis aculeifer (Aculeifer-System®, Entomite-A®) + TX, Hypoaspis miles (Hypoline m®, Entomite-M®) + TX, Lbalia leucospoides + TX, Lecanoideus floccissimus + TX, Lemophagus errabundus + TX, Leptomastidea abnormis + TX, Leptomastix dactylopii + TX, Leptomastix epona + TX, Lindorus lophanthae + TX, Lipolexis oregmae + TX, Lucilia caesar (Natufly®) + TX, Lysiphlebus testaceipes + TX, Macrolophus caliginosus (Mirical-N®,109934 | 83191 FF 92 Macroline c®, Mirical®) + TX, Mesoseiulus longipes + TX, Metaphycus flavus + TX, Metaphycus lounsburyi + TX, Micromus angulatus (Milacewing®) + TX, Microterys flavus + TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®) + TX, Neodryinus typhlocybae + TX, Neoseiulus californicus + TX, Neoseiulus cucumeris (THRYPEX®) + TX, Neoseiulus fallacis + TX, Nesideocoris tenuis (NesidioBug®, Nesibug®) + TX, Ophyra aenescens (Biofly®) + TX, Orius insidiosus (Thripor- I®, Oriline i®) + TX, Orius laevigatus (Thripor-L®, Oriline l®) + TX, Orius majusculus (Oriline m®) + TX, Orius strigicollis (Thripor-S®) + TX, Pauesia juniperorum + TX, Pediobius foveolatus + TX, Phasmarhabditis hermaphrodita (Nemaslug®) + TX, Phymastichus coffea + TX, Phytoseiulus macropilus + TX, Phytoseiulus persimilis (Spidex®, Phytoline p®) + TX, Podisus maculiventris (Podisus®) + TX, Pseudacteon curvatus + TX, Pseudacteon obtusus + TX, Pseudacteon tricuspis + TX, Pseudaphycus maculipennis + TX, Pseudleptomastix mexicana + TX, Psyllaephagus pilosus + TX, Psyttalia concolor (complex) + TX, Quadrastichus spp. + TX, Rhyzobius lophanthae + TX, Rodolia cardinalis + TX, Rumina decollate + TX, Semielacher petiolatus + TX, Sitobion avenae (Ervibank®) + TX, Steinernema carpocapsae (Nematac C®, Millenium®, BioNem C®, NemAttack®, Nemastar®, Capsanem®) + TX, Steinernema feltiae (NemaShield®, Nemasys F®, BioNem F®, Steinernema- System®, NemAttack®, Nemaplus®, Exhibitline sf®, Scia-rid®, Entonem®) + TX, Steinernema kraussei (Nemasys L®, BioNem L®, Exhibitline srb®) + TX, Steinernema riobrave (BioVector®,BioVektor®) + TX, Steinernema scapterisci (Nematac S®) + TX, Steinernema spp. + TX,Steinernematid spp. (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX, Trichogramma brassicae (Tricho-Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator + TX; abscisic acid + TX, Aminomite® + TX, BioGain® + TX, bioSea® + TX, Chondrostereum purpureum (Chontrol Paste®) + TX, Colletotrichum gloeosporioides (Collego®) + TX, Copper Octanoate (Cueva®) + TX, Delta traps (Trapline d®) + TX, Erwinia amylovora (Harpin) (ProAct®, Ni- HIBIT Gold CST®) + TX, fatty acids derived from a natural by-product of extra virgin olive oil (FLIPPER®) + TX, Ferri-phosphate (Ferramol®) + TX, Funnel traps (Trapline y®) + TX, Gallex® + TX, Grower's Secret® + TX, Homo-brassonolide + TX, Iron Phosphate (Lilly Miller Worry Free Ferramol Slug & Snail Bait®) + TX, MCP hail trap (Trapline f®) + TX, Microctonus hyperodae + TX, Mycoleptodiscus terrestris (Des-X®) + TX, Nosema locustae (Semaspore Organic Grasshopper Control®) + TX, Pheromone trap (Thripline ams®) + TX, potassium bicarbonate (MilStop®) + TX, potassium iodide + potassiumthiocyanate (Enzicur®) + TX, potassium salts of fatty acids (Sanova®) + TX, potassium silicate solution (Sil-Matrix®) + TX, Spider venom + TX, Sticky traps (Trapline YF®, Rebell Amarillo®) + TX, SuffOil-X® + TX, Traps (Takitrapline y + b®) + TX, vadescana (CAS Number: 2643947-26-4) + TX, Zenox® + TX; Bacillus mojavensis strain R3B (Accession No. NCAIM (P) B001389) (WO 2013 / 034938) from Certis USA LLC + TX, Bacillus pumilus, in particular strain BU F-33, having NRRL Accession No.50185 (CARTISSA® from BASF, EPA Reg. No. 71840-19) + TX, Bacillus subtilis CX-9060 from CertisUSA LLC, Bacillus sp., in particular strain D747 (available as DOUBLE NICKEL® from Kumiai Chemical Industry Co., Ltd.), having Accession No. FERM BP-8234, U.S. Patent No.7,094,592 + TX,109934 | 83191 FF 93 Bacillus subtilis strain BU1814, (VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA from BASF SE) + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No. 70127- 5)) + TX, Bacillus subtilis, in particular strain QST713 / AQ713 (having NRRL Accession No. B-21661 and described in U.S. Patent No.6,060,051, available as SERENADE® OPTI or SERENADE® ASO from Bayer CropScience LP, US) + TX, Paenibacillus polymyxa, in particular strain AC-1 (e.g. TOPSEED® from Green Biotech Company Ltd.) + TX, Paenibacillus sp. strain having Accession No. NRRL B-50972 or Accession No. NRRL B-67129, WO 2016 / 154297 + TX, Pantoea agglomerans, inparticular strain E325 (Accession No. NRRL B-21856) (available as BLOOMTIME BIOLOGICAL™ FDBIOPESTICIDE from Northwest Agri Products) + TX, Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena) + TX; Aureobasidium pullulans, in particular blastospores of strain DSM14940, blastospores of strain DSM 14941 or mixtures of blastospores of strains DSM14940 and DSM14941 (e.g., BOTECTOR® and BLOSSOM PROTECT® from bio-ferm, CH) + TX, Pseudozyma aphidis (as disclosed in WO2011 / 151819 by Yissum Research Development Company of the Hebrew University of Jerusalem) + TX, Saccharomyces cerevisiae, in particular strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No.1-3938 or CNCM No.1-3939 (WO 2010 / 086790) from Lesaffre et Compagnie, FR + TX; Agrobacterium radiobacter strain K84 (e.g. GALLTROL-A® from AgBioChem, CA) + TX,Bacillus amyloliquefaciens isolate B246 (e.g. AVOGREEN™ from University of Pretoria) + TX,Bacillus amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL Accession No. B-50768, WO 2014 / 028521) (STARGUS® from Marrone Bio Innovations) + TX, Bacillus amyloliquefaciens strain FZB42, Accession No. DSM 23117 (available as RHIZOVITAL® from ABiTEP, DE) + TX,Bacillus amyloliquefaciens, in particular strain D747 (available as Double Nickel™ from KumiaiChemical Industry Co., Ltd., having accession number FERM BP-8234, US Patent No.7,094,592) + TX, Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (QUARTZO® (WG) and PRESENCE® (WP) from FMC Corporation) + TX, Bacillus licheniformis, in particular strain SB3086, having Accession No. ATCC 55406, WO 2003 / 000051 (available as ECOGUARD® Biofungicide andGREEN RELEAF™ from Novozymes) + TX, Bacillus methylotrophicus strain BAC-9912 (from ChineseAcademy of Sciences’ Institute of Applied Ecology) + TX, Bacillus mycoides, isolate, having AccessionNo. B-30890 (available as BMJ TGAI® or WG and LifeGard™ from Certis USA LLC) + TX, Bacilluspumilus, in particular strain GB34 (available as Yield Shield® from Bayer AG, DE) + TX, Bacillus pumilus, in particular strain QST2808 (available as SONATA® from Bayer CropScience LP, US, having Accession No. NRRL B-30087 and described in U.S. Patent No. 6,245,551) + TX, Bacillussubtilis CX-9060 from Certis USA LLC + TX, Bacillus subtilis IAB / BS03 (AVIV™ from STK Bio-AgTechnologies, PORTENTO® from Idai Nature) + TX, Bacillus subtilis KTSB strain (FOLIACTIVE® from Donaghys) + TX, Bacillus subtilis strain BU1814, (available as VELONDIS® PLUS, VELONDIS® FLEX and VELONDIS® EXTRA from BASF SE) + TX, Bacillus subtilis strain GB03 (available as Kodiak® from Bayer AG, DE) + TX, Bacillus subtilis strain MBI 600 (available as SUBTILEX from BASF SE), having Accession Number NRRL B-50595, U.S. Patent No. 5,061,495 + TX, Bacillus subtilis strain Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological109934 | 83191 FF 94 fungicide in Taiwan under Registration Nos.4764, 5454, 5096 and 5277) + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 having Accession No. DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No. 70127-5)) + TX, Bacillus subtilis Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under Registration Nos. 4764, 5454, 5096 and 5277) + TX, Paenibacillus epiphyticus (WO 2016 / 020371) from BASF SE + TX, Paenibacillus polymyxa ssp. plantarum (WO 2016 / 020371) from BASF SE + TX, Paenibacillus sp. strain having Accession No. NRRL B-50972 or Accession No. NRRLB-67129, WO 2016 / 154297 + TX, Pseudomonas chlororaphis strain AFS009, having Accession No.NRRL B-50897, WO 2017 / 019448 (e.g., HOWLER™ and ZIO® from AgBiome Innovations, US) + TX,Pseudomonas chlororaphis, in particular strain MA342 (e.g. CEDOMON®, CERALL®, and CEDRESS® by Bioagri and Koppert) + TX, Pseudomonas fluorescens strain A506 (e.g. BLIGHTBAN® A506 by NuFarm) + TX, Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena) + TX, Streptomyces griseoviridis strain K61 (also known as Streptomyces galbus strain K61) (Accession No. DSM 7206) (MYCOSTOP® from Verdera, PREFENCE® from BioWorks, cf. Crop Protection 2006, 25, 468-475) + TX, Streptomyces lydicus strain WYEC108 (also known as Streptomyces lydicus strain WYCD108US) (ACTINO-IRON® and ACTINOVATE® from Novozymes) + TX; Trichoderma atroviride strain T11 (IMI352941 / CECT20498) + TX, Ampelomyces quisqualis strain AQ10, having Accession No. CNCM 1-807 (e.g., AQ 10® by IntrachemBio Italia) + TX, Ampelomyces quisqualis, in particular strain AQ 10 (e.g. AQ 10® by IntrachemBio Italia) + TX, Aspergillus flavus strain NRRL 21882 (products known as AFLA-GUARD® from Syngenta / ChemChina) + TX, Aureobasidium pullulans, in particular blastospores of strain DSM 14941 + TX, Aureobasidium pullulans, in particular blastospores of strain DSM14940 + TX, Aureobasidium pullulans, in particular mixtures of blastospores of strains DSM14940 and DSM 14941 (e.g. Botector®by bio-ferm, CH) + TX, Chaetomium cupreum (Accession No. CABI 353812) (e.g. BIOKUPRUM™ byAgriLife) + TX, Chaetomium globosum (available as RIVADIOM® by Rivale) + TX, Cladosporium cladosporioides, strain H39, having Accession No. CBS122244, US 2010 / 0291039 (by Stichting Dienst Landbouwkundig Onderzoek) + TX, Coniothyrium minitans, in particular strain CON / M / 91-8(Accession No. DSM9660, e.g. Contans ® from Bayer CropScience Biologics GmbH) + TX,Cryptococcus flavescens, strain 3C (NRRL Y-50378), + TX, Dactylaria candida, Dilophosphora alopecuri (available as TWIST FUNGUS®), Fusarium oxysporum, strain Fo47 (available as FUSACLEAN® by Natural Plant Protection) + TX, Gliocladium catenulatum (Synonym: Clonostachys rosea f. catenulate) strain J1446 (e.g. Prestop ® by Lallemand) + TX, Gliocladium roseum (also knownas Clonostachys rosea f rosea) strain IK726 (Jensen DF, et al. Development of a biocontrol agent forplant disease control with special emphasis on the near commercial fungal antagonist Clonostachys rosea strain ’IK726’, Australasian Plant Pathol. 2007,36(2):95-101) + TX, Gliocladium roseum (also known as Clonostachys rosea f rosea), in particular strain 321U from Adjuvants Plus, strain ACM941 as disclosed in Xue A.G. (Efficacy of Clonostachys rosea strain ACM941 and fungicide seed treatments for controlling the root tot complex of field pea, Can Jour Plant Sci 2003, 83(3): 519-524) + TX, Metschnikowia fructicola, in particular strain NRRL Y-30752 + TX, Microsphaeropsis ochracea, Penicillium steckii (DSM 27859, WO 2015 / 067800) from BASF SE + TX, mixtures of Trichoderma asperellum strain ICC 012 (also known as Trichoderma harzianum ICC012), having Accession No.109934 | 83191 FF 95 CABI CC IMI 392716 and Trichoderma gamsii (formerly T. viride) strain ICC 080, having AccessionNo. IMI 392151 (e.g., BIO-TAM™ from Isagro USA, Inc. or BIODERMA® by Agrobiosol de Mexico,S.A. de C.V.) + TX, Penicillium vermiculatum + TX, Phlebiopsis gigantea strain VRA 1992 (ROTSTOP® C from Danstar Ferment) + TX, Pseudozyma flocculosa, strain PF-A22 UL (available as SPORODEX® L by Plant Products Co., CA) + TX, Saccharomyces cerevisiae strain LAS117 cell walls (CEREVISANE® from Lesaffre, ROMEO® from BASF SE) + TX, Saccharomyces cerevisiae strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938, CNCM No. 1-3939 (WO 2010 / 086790) from Lesaffre et Compagnie, FR + TX, Saccharomyces cerevisiae, in particular strain LASO2 (from Agro-Levures et Dérivés) + TX, Simplicillium lanosoniveum + TX, strain T34 (e.g. T34 Biocontrol by Biocontrol Technologies S.L., ES) or strain ICC 012 from Isagro + TX, strain WRL-076 (NRRL Y- 30842), U.S. Patent No. 7,579,183 + TX, Talaromyces flavus, strain V117b + TX, Trichoderma asperelloides JM41R (Accession No. NRRL B-50759) (TRICHO PLUS® from BASF SE) + TX, Trichoderma asperellum, in particular strain SKT-1, having Accession No. FERM P-16510 (e.g. ECO- HOPE® from Kumiai Chemical Industry) + TX, Trichoderma asperellum, in particular, strain kd (e.g. T-Gro from Andermatt Biocontrol) + TX, Trichoderma atroviride strain 77B (T77 from Andermatt Biocontrol) + TX, Trichoderma atroviride strain ATCC 20476 (IMI 206040) + TX, Trichoderma atroviride strain LC52 (e.g. Tenet by Agrimm Technologies Limited) + TX, Trichoderma atroviride strain LU132 (e.g. Sentinel from Agrimm Technologies Limited) + TX, Trichoderma atroviride strain NMI no. V08 / 002388 + TX, Trichoderma atroviride strain NMI no. V08 / 002389 + TX, Trichoderma atroviride strain NMI no. V08 / 002390 + TX, Trichoderma atroviride strain no. V08 / 002387 + TX, Trichoderma atroviride strain SKT-1 (FERM P-16510), JP Patent Publication (Kokai) 11-253151 A + TX, Trichoderma atroviride strain SKT-2 (FERM P-16511), JP Patent Publication (Kokai) 11-253151 A + TX, Trichoderma atroviride strain SKT-3 (FERM P-17021), JP Patent Publication (Kokai) 11- 253151 A + TX, Trichoderma atroviride, in particular strain SC1 (Accession No. CBS 122089, WO 2009 / 116106 and U.S. Patent No.8,431,120 (from Bi-PA)) + TX, Trichoderma atroviride,strain CNCM 1-1237 (e.g. Esquive® WP from Agrauxine, FR) + TX, Trichoderma fertile (e.g. product TrichoPlus from BASF) + TX, Trichoderma gamsii (formerly T. viride) + TX, Trichoderma gamsii (formerly T. viride) strain ICC 080 (IMI CC 392151 CABI) (available as BIODERMA® by AGROBIOSOL DE MEXICO, S.A. DE C.V.), + TX, Trichoderma gamsii strain ICC080 (IMI CC 392151 CABI, e.g. BioDerma by AGROBIOSOL DE MEXICO, S.A. DE C.V.), + TX, Trichoderma harmatum + TX, Trichoderma harmatum, having Accession No. ATCC 28012 + TX, Trichoderma harzianum + TX, Trichoderma harzianum rifai T39 (e.g. Trichodex® from Makhteshim, US) + TX, Trichoderma harzianum strain Cepa SimbT5 (from Simbiose Agro), + TX, Trichoderma harzianum strain DB 103 (available as T-GRO® 7456 by Dagutat Biolab) + TX, Trichoderma harzianum strain ITEM 908 (e.g. Trianum-P from Koppert) + TX, Trichoderma harzianum strain T-22 (e.g. Trianum-P from Andermatt Biocontrol or Koppert) + TX, Trichoderma harzianum strain TH35 (e.g. Root-Pro by Mycontrol) + TX, Trichoderma polysporum strain IMI 206039 (e.g. Binab TF WP by BINAB Bio-Innovation AB, Sweden)+ TX, Trichoderma stromaticum having Accession No. Ts3550 (e.g. Tricovab by CEPLAC, Brazil) +TX, Trichoderma virens (also known as Gliocladium virens) in particular strain GL-21 (e.g. SoilGard by Certis, US) + TX, Trichoderma virens strain G-41, formerly known as Gliocladium virens (Accession No. ATCC 20906) (e.g., ROOTSHIELD® PLUS WP and TURFSHIELD® PLUS WP from BioWorks,109934 | 83191 FF 96 US) + TX, Trichoderma viride in particular strain B35 (Pietr et al., 1993, Zesz. Nauk. A R w Szczecinie 161: 125-137) + TX, Trichoderma viride strain TV1(e.g. Trianum-P by Koppert) + TX, Ulocladium oudemansii strain U3, having Accession No. NM 99 / 06216 (e.g., BOTRY-ZEN® by Botry-Zen Ltd, New Zealand and BOTRYSTOP® from BioWorks, Inc.) + TX, Verticillium albo-atrum (formerly V. dahliae) strain WCS850 having Accession No. WCS850, deposited at the Central Bureau for Fungi Cultures (e.g., DUTCH TRIG® by Tree Care Innovations) + TX, Verticillium chlamydosporium + TX; a mixture of Azotobacter vinelandii and Clostridium pasteurianum (available as INVIGORATE® from Agrinos) + TX, a mixture of Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (available as QUARTZO® (WG), PRESENCE® (WP) from FMC Corporation) + TX, Azorhizobium caulinodans, in particular strain ZB-SK-5 + TX, Azospirillum brasilense (e.g., VIGOR®from KALO, Inc.) + TX, Azospirillum lipoferum (e.g., VERTEX-IF™ from TerraMax, Inc.) + TX,Azotobacter chroococcum, in particular strain H23 + TX, Azotobacter vinelandii, in particular strain ATCC 12837 + TX, Bacillus amyloliquefaciens BS27 (Accession No. NRRL B-5015) + TX, Bacillus amyloliquefaciens in particular strain FZB42 (e.g. RHIZOVITAL® from ABiTEP, DE) + TX, Bacillus amyloliquefaciens in particular strain IN937a + TX, Bacillus amyloliquefaciens pm414 (LOLI-PEPTA® from Biofilm Crop Protection) + TX, Bacillus amyloliquefaciens SB3281 (ATCC # PTA-7542, WO 2017 / 205258) + TX, Bacillus amyloliquefaciens TJ1000 (available as QUIKROOTS® from Novozymes) + TX, Bacillus cereus family member EE128 (NRRL No. B-50917) + TX, Bacillus cereus family member EE349 (NRRL No. B-50928) + TX, Bacillus cereus in particular strain BP01 (ATCC 55675, e.g. MEPICHLOR® from Arysta Lifescience, US) + TX, Bacillus mycoides BT155 (NRRL No. B-50921) + TX, Bacillus mycoides BT46-3 (NRRL No. B-50922) + TX, Bacillus mycoides EE118 (NRRL No. B-50918) + TX, Bacillus mycoides EE141 (NRRL No. B-50916) + TX, Bacillus pumilus in particular strain GB34 (e.g. YIELD SHIELD® from Bayer Crop Science, DE), + TX, Bacillus pumilus in particular strain QST2808 (Accession No. NRRL No. B-30087) + TX, Bacillus siamensis in particular strain KCTC 13613T + TX, Bacillus subtilis in particular strain AQ30002 (Accession No. NRRL No. B- 50421 and described in U.S. Patent Application No. 13 / 330,576) + TX, Bacillus subtilis in particular strain AQ30004 (NRRL No. B-50455 and described in U.S. Patent Application No.13 / 330,576) + TX, Bacillus subtilis in particular strain MBI 600 (e.g. SUBTILEX® from BASF SE) + TX, Bacillus subtilis rm303 (RHIZOMAX® from Biofilm Crop Protection) + TX, Bacillus subtilis strain BU1814 (available as TEQUALIS® from BASF SE) + TX, Bacillus tequilensis in particular strain NII-0943 + TX, Bacillus thuringiensis BT013A (NRRL No. B-50924) also known as Bacillus thuringiensis 4Q7 + TX, Bradyrhizobium japonicum (e.g. OPTIMIZE® from Novozymes) + TX, Delftia acidovorans in particular strain RAY209 (e.g. BIOBOOST® from Brett Young Seeds) + TX, Lactobacillus sp. (e.g. LACTOPLANT® from LactoPAFI) + TX, Mesorhizobium cicer (e.g., NODULATOR from BASF SE) + TX, Paenibacillus polymyxa in particular strain AC-1 (e.g. TOPSEED® from Green Biotech Company Ltd.) + TX, Pseudomonas aeruginosa in particular strain PN1 + TX, Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena) + TX, Rhizobium leguminosarium biovar viciae (e.g., NODULATOR from BASF SE) + TX, Rhizobium leguminosarum in particular bv. viceae strain Z25 (Accession No. CECT 4585) + TX, Serratia marcescens in particular strain SRM (Accession No. MTCC 8708), + TX, Sinorhizobium meliloti strain NRG-185-1 (NITRAGIN® GOLD from Bayer CropScience) + TX, Thiobacillus sp. (e.g. CROPAID® from Cropaid Ltd UK) + TX;109934 | 83191 FF 97 Myrothecium verrucaria strain AARC-0255 (e.g. DiTera™ from Valent Biosciences) + TX,Penicillium bilaii strain ATCC 22348 (e.g. JumpStart® from Acceleron BioAg) + TX, Penicillium bilaii strain ATCC ATCC20851 + TX, Purpureocillium lilacinum (previously known as Paecilomyces lilacinus) strain 251 (AGAL 89 / 030550, e.g. BioAct from Bayer CropScience Biologics GmbH) + TX, Pythium oligandrum strain DV74 + TX, Pythium oligandrum strain M1 (ATCC 38472 e.g. Polyversum from Bioprepraty, CZ) + TX, Rhizopogon amylopogon (Myco-Sol from Agri-Enterprise, LLC, formerly Helena Chemical Company) + TX, Rhizopogon fulvigleba (e.g. Myco-Sol from Agri-Enterprise, LLC,formerly Helena Chemical Company) + TX, Talaromyces flavus strain V117b + TX, Trichodermaasperellum strain (Eco-T from Plant Health Products, ZA) + TX, Trichoderma asperellum strain kd (e.g. T-Gro from Andermatt Biocontrol) + TX, Trichoderma atroviride in particular strain no. V08 / 002387 + TX, Trichoderma atroviride strain CNCM 1-1237 (e.g. Esquive® WP from Agrauxine, FR) + TX, Trichoderma atroviride strain LC52 (also known as Trichoderma atroviride strain LU132, e.g. Sentinel from Agrimm Technologies Limited) + TX, Trichoderma atroviride strain no. NMI No. V08 / 002388 + TX, Trichoderma atroviride strain no. NMI No. V08 / 002389 + TX, Trichoderma atroviride strain no. NMI No. V08 / 002390 + TX, Trichoderma atroviride strain SC1 (described in WO2009 / 116106) + TX, Trichoderma harzianum strain 1295-22 + TX, Trichoderma harzianum strain ITEM 908 + TX, Trichoderma harzianum strain T-22 (e.g. Trianum-P from Andermatt Biocontrol or Koppert) + TX, Trichoderma harzianum strain TSTh20, + TX, Trichoderma virens strain GI-3 + TX, Trichoderma virens strain GL-21 (e.g. SoilGard® from Certis, USA) + TX, Trichoderma viride strain B35 (Pietr et al., 1993, Zesz. Nauk. A R w Szczecinie 161: 125-137) + TX, Verticillium albo-atrum (formerly V. dahliae) strain WCS850 (CBS 276.92, e.g. Dutch Trig from Tree Care Innovations) + TX; Agrobacterium radiobacter strain K84 (Galltrol from AgBiochem Inc.), + TX, Bacillus amyloliquefaciens in particular strain PTS-4838 (e.g. AVEO from Valent Biosciences, US), + TX, Bacillus mycoides, isolate J. (e.g. BmJ from Certis USA LLC), + TX, Bacillus sphaericus in particular Serotype H5a5b strain 2362 (strain ABTS-1743) (e.g. VECTOLEX® from Valent BioSciences, US), + TX, Bacillus thuringiensis israelensis strain BMP 144 (e.g. AQUABAC® by Becker Microbial Products IL) + TX, Bacillus thuringiensis subsp. aizawai strain GC-91 + TX, Bacillus thuringiensis subsp. aizawai, in particular serotype H-7 (e.g. FLORBAC® WG from Valent BioSciences, US) + TX, Bacillus thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372, e.g. XENTARI® from Valent BioSciences) + TX, Bacillus thuringiensis subsp. israelensis (serotype H-14) strain AM65-52 (Accession No. ATCC 1276) (e.g. VECTOBAC® by Valent BioSciences, US) + TX, Bacillus thuringiensis subsp. kurstaki strain ABTS 351 + TX, Bacillus thuringiensis subsp. kurstaki strain BMP 123 (from Becker Microbial Products, IL, BARITONE from Bayer CropScience) + TX, Bacillus thuringiensis subsp. kurstaki strain EG 2348 (LEPINOX from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain EG 7841 (CRYMAX from Certis, US) + TX, Bacillus thuringiensis subsp. kurstaki strain HD-1 (e.g. DIPEL® ES from Valent BioSciences, US) + TX, Bacillus thuringiensis subsp. kurstaki strain PB 54 + TX, Bacillus thuringiensis subsp. kurstaki strain SA 11 (JAVELIN from Certis,US) + TX, Bacillus thuringiensis subsp. kurstaki strain SA 12 (THURICIDE from Certis, US) + TX,Bacillus thuringiensis subsp. tenebrionis strain NB 176 (SD-5428, e.g. NOVODOR® FC from BioFa DE) + TX, Bacillus thuringiensis var. Colmeri (e.g. TIANBAOBTC by Changzhou Jianghai Chemical Factory) + TX, Bacillus thuringiensis var. japonensis strain Buibui + TX, Bacillus thuringiensis var.109934 | 83191 FF 98 kurstaki strain EVB-113-19 (e.g., BIOPROTEC® from AEF Global) + TX, Brevibacillus laterosporus + TX, Burkholderia spp. in particular Burkholderia rinojensis strain A396 (also known as Burkholderia rinojensis strain MBI 305) (Accession No. NRRL B-50319, WO 2011 / 106491 and WO 2013 / 032693, e.g. MBI206 TGAI and ZELTO® from Marrone Bio Innovations), + TX, Chromobacterium subtsugae in particular strain PRAA4-1T (e.g. MBI-203, e.g. GRANDEVO® from Marrone Bio Innovations) + TX, Lecanicillium muscarium Ve6 (MYCOTAL from Koppert) + TX, Paenibacillus popilliae (formerlyBacillus popilliae, e.g. MILKY SPORE POWDER™ or MILKY SPORE GRANULAR™ from St. GabrielLaboratories) + TX, Serratia entomophila (e.g. INVADE® by Wrightson Seeds) + TX, Serratia marcescens in particular strain SRM (Accession No. MTCC 8708) + TX, Trichoderma asperellum (TRICHODERMAX from Novozymes) + TX, Wolbachia pipientis ZAP strain (e.g., ZAP MALES® from MosquitoMate) + TX; Beauveria bassiana strain ATCC 74040 (e.g. NATURALIS® from Intrachem Bio Italia) + TX, Beauveria bassiana strain ATP02 (Accession No. DSM 24665), Apopka 97 (PREFERAL from SePRO) + TX, Beauveria bassiana strain GHA (Accession No. ATCC74250, e.g. BOTANIGUARD® ES and MYCONTROL-O® from Laverlam International Corporation) + TX, Metarhizium anisopliae 3213-1 (deposited under NRRL accession number 67074 disclosed in WO 2017 / 066094, Pioneer Hi-Bred International) + TX, Metarhizium robertsii 15013-1 (deposited under NRRL accession number 67073) + TX, Metarhizium robertsii 23013-3 (deposited under NRRL accession number 67075) + TX, Paecilomyces lilacinus strain 251 (MELOCON from Certis, US) + TX, Zoophtora radicans + TX; Adoxophyes orana (summer fruit tortrix) granulosis virus (GV) + TX, Cydia pomonella (codling moth) granulosis virus (GV) + TX, Helicoverpa armigera (cotton bollworm) nuclear polyhedrosis virus (NPV) + TX, Spodoptera exigua (beet armyworm) mNPV + TX, Spodoptera frugiperda (fall armyworm) mNPV + TX, Spodoptera littoralis (African cotton leafworm) NPV + TX; Burkholderia spp. in particular Burkholderia cepacia (formerly known as Pseudomonas cepacia) + TX, Gigaspora spp. + TX, Glomus spp. + TX, Laccaria spp. + TX, LactoBacillus buchneri + TX, Paraglomus spp. + TX, Pisolithus tinctorus + TX, Pseudomonas spp. + TX, Rhizobium spp. in particular Rhizobium trifolii + TX, Rhizopogon spp. + TX, Scleroderma spp. + TX, Streptomyces spp. + TX, Suillus spp. + TX, Agrobacterium spp. + TX, Azorhizobium caulinodans + TX, Azospirillum spp. + TX, Azotobacter spp. + TX, Bradyrhizobium spp. + TX, Gigaspora monosporum + TX; Allium sativum (NEMGUARD from Eco-Spray, BRALIC from ADAMA) + TX, Armour-Zen + TX, Artemisia absinthium + TX, Biokeeper WP + TX, Brassicaceae extract in particular oilseed rape powder or mustard powder + TX, Cassia nigricans + TX, Celastrus angulatus + TX, Chenopodium anthelminticum + TX, Chenopodium quinoa saponin extract from quinoa seeds (e.g. Heads Up® (Saponins of Quinoa) from Heads Up plant Protectants, CA) + TX, Chitin + TX, Dryopteris filix-mas + TX, Equisetum arvense + TX, Fortune Aza + TX, Fungastop + TX, Melaleuca alternifolia extract (TIMOREX GOLD from STK) + TX, naturally occurring Blad polypeptide extracted from Lupin seeds (FRACTURE® from FMC) + TX, naturally occurring Blad polypeptide extracted from Lupin seeds (PROBLAD® from Certis EU) + TX, Pyrethrins + TX, Quassia amara + TX, Quercus + TX, Quillaja extract (QL AGRI 35 from BASF) + TX, REGALIA MAXX from Marrone Bio) + TX, Requiem™ Insecticide + TX, Reynoutria sachalinensis extract (REGALLIA + TX, ryania / ryanodine + TX, Symphytum officinale + TX, Tanacetum vulgare + TX, Thymol + TX, Thymol mixed with Geraniol109934 | 83191 FF 99 (CEDROZ from Eden Research) + TX, Thymol mixed with Geraniol and Eugenol (MEVALONE from Eden Research) + TX, Triact 70 + TX, TriCon + TX, Tropaeulum majus + TX, Urtica dioica + TX, Veratrin + TX, Viscum album + TX; mercuric oxide + TX, octhilinone + TX, thiophanate-methyl + TX; MGK 264 + TX, 2-(2-butoxyethoxy)ethyl piperonylate + TX, 2-isovalerylindan-1,3-dione + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2- enone + TX, acibenzolar + TX, acibenzolar-S-methyl + TX, alpha-bromadiolone + TX, alpha- chlorohydrin + TX, aluminium phosphide + TX, anthraquinone + TX, antu + TX, arsenous oxide + TX, barium carbonate + TX, benoxacor + TX, bisthiosemi + TX, brodifacoum + TX, bromadiolone + TX, bromethalin + TX, calcium cyanide + TX, chloralose + TX, chlorophacinone + TX, cholecalciferol + TX, cloquintocet (including cloquintocet-mexyl) + TX, copper naphthenate + TX, copper oxychloride + TX, coumachlor + TX, coumafuryl + TX, coumatetralyl + TX, crimidine + TX, cyprosulfamide + TX, diazinon + TX, dichlormid + TX, dicyclopentadiene + TX, difenacoum + TX, difethialone + TX, diphacinone + TX, ergocalciferol + TX, farnesol + TX, farnesol with nerolidol + TX, fenchlorazole (including fenchlorazole-ethyl) + TX, fenclorim + TX, flocoumafen + TX, fluoroacetamide + TX, flupropadine + TX, flupropadine hydrochloride + TX, fluxofenim + TX, furilazole + TX, gamma-HCH + TX, guazatine + TX, guazatine acetates + TX, HCH + TX, hydrogen cyanide + TX, imanin + TX, iodomethane + TX, isoxadifen (including isoxadifen-ethyl) + TX, lindane + TX, magnesium phosphide + TX, MB-599 + TX, mefenpyr (including mefenpyr-diethyl) + TX, metcamifen + TX, methiocarb + TX, methyl bromide + TX, nerolidol + TX, norbormide + TX, petroleum oils + TX, phosacetim + TX, phosphine + TX, phosphorus + TX, pindone + TX, piperonyl butoxide + TX, piprotal + TX, potassium arsenite + TX, probenazole + TX, propyl isomer + TX, pyridin-4-amine + TX, pyrinuron + TX, Reynoutria sachalinensis extract + TX, ribavirin + TX, S421 + TX, scilliroside + TX, sesamex + TX, sesasmolin + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoroacetate + TX, strychnine + TX, sulfoxide + TX, thallium sulfate + TX, thiram + TX, trimethacarb + TX, warfarin + TX, zinc naphthenate + TX, zinc phosphide + TX, ziram + TX.

[0317] The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the ChemicalAbstracts Registry number. The above described mixing partners are known. Where the active ingredientsare included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition;Editor: C. D. S. TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound "abamectin" is described under entry number (1). Where "[CCN]" is added hereinabove to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995- 2004]; for example, the compound "acetoprole" is described under the internet address http: / / www.alanwood.net / pesticides / acetoprole.html.

[0318] Most of the active ingredients described above are referred to hereinabove by a so-called"common name", the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a "common name", the nature of the designation used instead is given in round brackets for the particular compound; in that case, the IUPAC name, the IUPAC / Chemical Abstracts name, a "chemical name", a "traditional name", a "compound name" or a "development code" is used or, if109934 | 83191 FF 100 neither one of those designations nor a "common name" is used, an "alternative name" is employed. "CAS Reg. No" means the Chemical Abstracts Registry Number.

[0319] The active ingredient mixture of the compounds of formula (I) selected from the compoundsdefined in the Tables A-1 to A-24, Tables B-1 to B-5, and Table P, with active ingredients described abovecomprises a compound selected from one compound defined in the Tables A-1 to A-24, Tables B-1 to B-5,and Table P, and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5:1 to 1:5, special preference being given to a ratio of from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. Those mixing ratios are by weight.

[0320] The compounds and mixtures as described above can be used in a method for controlling pests,which comprises applying a composition comprising a compound or mixture respectively as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practiced on the human or animal body.

[0321] The mixtures comprising a compound of formula (I) selected from the compounds defined in theTables A-1 to A-24, Tables B-1 to B-5, and Table P, and one or more active ingredients as described above can be applied, for example, in a single "ready-mix" form, in a combined spray mixture com-posed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequen-tial manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula (I) and the active ingredients as described above is not essential for working the present invention.

[0322] The compounds according to the invention can be used as pesticidal agents in unmodified form,but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances. The formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, micro-emulsifiable concentrates, oil-in-water emulsions, oil- flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can either be used directly or diluted prior to use. The dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.

[0323] The formulations can be prepared e.g. by mixing the active ingredient with the formulationadjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.109934 | 83191 FF 101

[0324] The active ingredients can also be contained in very fine microcapsules. Microcapsules containthe active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release). Microcapsules usually have a diameter of from 0.1to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of thecapsule weight. The active ingredients can be in the form of a monolithic solid, in the form of...

Claims

109934 | 83191 FF 165 CLAIMS1. A compound of the formula (I)line represents the connection of Q to the rest of compound of the formula (I); R1is hydrogen, C1-C6alkyl, C1-C6cyanoalkyl, C1-C3alkoxyC1-C6alkyl, C2-C6alkenyl, C2- C6alkynyl, C3-C4cycloalkylC1-C2alkyl, or C1-C6alkoxycarbonyl; R2aand R2a'are, independently from each other, hydrogen, halogen, cyano, C1-C3alkyl, or C3-C4cycloalkyl; or R2aand R2a'form a C3-C6cycloalkyl group together with the carbon atom they are attached to; R2bis hydrogen, halogen, C1-C3haloalkyl, C1-C3haloalkoxy, cyano, SF5, C1-C3alkylsulfanyl, C1-C3alkylsulfinyl, C1-C3alkylsulfonyl, C1-C3haloalkylsulfanyl, C1-C3haloalkylsulfinyl, C1- C3haloalkylsulfonyl, C1-C5cyanoalkyl, C1-C5cyanoalkoxy, C3-C4cycloalkylC1-C2alkyl, C3- C4cycloalkylC1-C2haloalkyl, C3-C4cycloalkylcarbonyl, or C3-C4cycloalkyl optionally substituted with one or two substituents independently selected from the group consisting of halogen, -CN, C1-C3alkyl, and C1-C3haloalkyl; R3is C1-C3alkyl or C1-C3haloalkyl; R4is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, or thiazolyl, each of which, independently of each other, is optionally substituted with a single substituent R4b; or R4is oxo-pyridazinyl optionallyN-substituted with a single substituent R4c;R4a is pyridinyl, pyrimidyl, pyrazinyl, pyridazinyl, thiazolyl, pyrazol-1-yl, or N-linked triazolyl,each of which, independently of each other, is optionally substituted with a single substituent R4b; orR4a is oxo-pyridazinyl optionally N-substituted with a single substituent R4c;R4b is hydrogen, halogen, cyano, hydroxy, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, -C(O)NR10R11, -N(R11)C(O)OR10, or -N(R11)C(O)R10; R4cis C1-C3alkyl, C1-C3haloalkyl, allyl, propargyl, or C3-C6cycloalkylC1-C4alkyl; R5, R5aand R5bare independently hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy, or C3- C4cycloalkyl;109934 | 83191 FF 166 R10is hydrogen, C1-C3alkyl, C3-C6cycloalkyl, C3-C4cycloalkylC1-C2alkyl, C1-C3cyanoalkyl, cyanoC3-C6cycloalkyl, C1-C3alkoxyC1-C3alkyl, or C1-C4haloalkyl; R11is hydrogen, hydroxy, C1-C3alkyl, C3-C4cycloalkyl, cyanoC3-C6cycloalkyl, C1- C3cyanoalkyl, C1-C3alkoxyC1-C3alkyl, C1-C3haloalkyl, or C1-C3alkoxy; X is an oxygen atom or a sulfur atom; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of thecompound of formula (I).

2. The compound according to claim 1, wherein A1is CH.

3. The compound according to claim 1 or 2, wherein X is oxygen.

4. The compound according to any one of claims 1 to 3, wherein R1is hydrogen, methyl, or cyclopropylmethyl.

5. The compound according to any one of claims 1 to 4, wherein R2a and R2a’ are bothhydrogen, fluoro, methyl, or ethyl; or wherein R2aand R2a'form a cyclopropyl, a cyclobutyl, or a cyclopentyl, together with the carbon atom they are attached to.

6. The compound according to any one of claims 1 to 5, wherein R2b is chloro, bromo, iodo,difluoromethyl, or trifluoromethyl.

7. The compound according to any one of claims 1 to 6, wherein R3is methyl.

8. The compound according to any one of claims 1 to 7, wherein- Q is Qa and R4 is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, Qc-7, Qc-8, or Qc-9; or- Q is Qb and R4a is Qc-1, Qc-2, Qc-3, Qc-4, Qc-5, Qc-6, Qc-7, Qc-8, Qc-9, Qc-10, or Qc-11:; R4bis hydrogen, fluoro, chloro, bromo, cyano, methyl, ethyl, methoxy, ethoxy, -C(O)NHR11, - C(O)N(CH3)R11, -NHC(O)R10, -N(CH3)C(O)R10, or -N(CH3)C(O)OR10; and R4cis methyl, ethyl, allyl, propargyl, or cyclopropylmethyl.109934 | 83191 FF 1679. The compound according to any one of claims 1 to 8, wherein R10 is hydrogen, methyl, ethyl,isopropyl, cyclopropyl, or cyanomethyl, preferably, R10 is hydrogen, methyl, or cyanomethyl; and R11is hydrogen, methyl, ethyl, cyanomethyl, 2-cyanoethyl, cyclopropyl, 1-cyanocyclopropyl, or methoxy, preferably, R11is hydrogen or methyl.

10. The compound according to any one of claims 1 to 9, wherein R4 is 5-cyano-2-pyridyl, 5-carbamoyl-2-pyridyl, pyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 5-chloropyrimidin-2-yl, 5-bromopyrimidin-2-yl, 6-cyanopyrimidin-4-yl, 6-carbamoyl-pyrimidin-4-yl, 6-(methylcarbamoyl)pyrimidin-4-yl, 6- (methoxycarbonylamino)pyrimidin-4-yl, pyrazin-2-yl, 5-chloropyrazin-2-yl, 5-bromopyrazin-2-yl, 5- carbamoylpyrazin-2-yl, 6-methoxypyridazin-3-yl, 1-methyl-6-oxo-pyridazin-3-yl, 5-cyanothiazol-2-yl,5-carbamoyl-thiazol-2-yl, and R4a is 5-cyano-2-pyridyl or 5-carbamoyl-2-pyridyl.

11. The compound according to any one of claims 1 to 10, wherein- Q is Qa and R5 is hydrogen, bromo, methyl, ethyl, cyclopropyl, or methoxy; or- Q is Qb, R5a is hydrogen, fluoro, cyclopropyl, trifluoromethyl, or difluoromethoxy; and R5b ishydrogen, fluoro, or methoxy.

12. The compound according to any one of claims 1 to 11, wherein R5 is hydrogen, bromo,methyl, ethyl, cyclopropyl, or methoxy; and R5a and R5b are hydrogen.

13. A composition comprising a compound as defined in any one of claims 1 to 12, one or more auxiliaries and diluent, and optionally one or more other active ingredient.

14. A method (i) of combating and controlling insects, acarines, nematodes or molluscs which comprisesapplying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound as defined in any one of claims 1 to 12, or of a composition as defined in claim 13; or (ii) for the protection of plant propagation material from the attack by insects, acarines,nematodes or molluscs, which comprises treating the plant propagation material or the site where the propagation material is planted, with an effective amount of a compound as defined inany one of claims 1 to 12, or of a composition as defined in claim 13; or (iii) of controlling parasites in or on an animal in need thereof, comprising administering aneffective amount of a compound as defined in any one of claims 1 to 12, or of a composition asdefined in claim 13.

15. A plant propagation material, such as a seed, comprising, or coated with, or treated with, oradhered thereto, a compound as defined in any one of claims 1 to 12, or a composition as defined inclaim 13.109934 | 83191 FF 168 16. A compound of the formula IIa-1, or II-bwhere A1, R2a, R2a' and R2b are as defined in claims 1, 2, 5 and 6; Ra is C1-C6alkyl or benzyl;the following compounds being excluded:

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