Pesticidal Active Pyridazinone Compounds.
Patent Information
- Application Number
- JP2024534296
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2021-12-10
- Filing Date
- 2022-12-05
- Publication Date
- 2025-12-15
AI Technical Summary
Existing technologies lack effective pesticidal compounds for controlling arthropods such as insects and mites in agriculture and horticulture.
Development of pesticidally active pyridazinone compounds, particularly pyridazin-3-one compounds, with specific structural variations that exhibit pesticidal activity.
The pyridazinone compounds effectively control arthropods, providing a viable solution for reducing pest damage in agricultural and horticultural settings.
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Abstract
Description
[Technical Field]
[0001] The present invention relates to pesticidal pyridazinone compounds having pesticidal activity, for example as active ingredients. The present invention also relates to the preparation of these pyridazinone compounds, intermediates useful for the preparation of these pyridazinone compounds, the preparation of these intermediates, pesticide compositions containing at least one of these pyridazinone compounds, the preparation of these compositions, and the use of these pyridazinone compounds or compositions for controlling arthropods, particularly insects, or animal pests, including representatives of the order Acarina, in agriculture or horticulture. In particular, pesticidal pyridazin-3-one compounds are disclosed. [Background technology]
[0002] WO 2021 / 083936, WO 2021 / 148639 and WO 2021 / 177160 describe certain quinazoline, quinazolinone and quinoline compounds.
[0003] It has now been unexpectedly found that certain novel pyridazinone compounds, particularly pyridazin-3-one compounds, possess pesticidal activity. Summary of the Invention [Means for solving the problem]
[0004] The present invention therefore provides in a first aspect a compound of formula (I): [ka] (In the formula: A 1 , A 2 and A 3 are, independently of each other, N or CR Y is; or A 1 =A 2 -A 3 are summarized as follows: NR-C(=X 0 )-N;X0 is O or S; A 4 and A 5 are, independently of each other, N or CR Y and; Q is [ka] wherein the wavy line represents the bond of Q to the remainder of the compound of formula (I). and; R is hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; R 1 is hydrogen, C1-C6 alkyl, C1-C6 cyanoalkyl, aminocarbonylC1-C6 alkyl, hydroxycarbonylC1-C6 alkyl, C1-C6 nitroalkyl, trimethylsilaneC1-C6 alkyl, C1-C3 alkoxy-C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C4 cycloalkylC1-C2 alkyl, or C3 -C4 cycloalkylC1-C2 alkyl- (wherein the C3-C4 cycloalkyl group is substituted by 1 or 2 halogen atoms), oxetan-3-yl-CH2-, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, benzyl, or benzyl substituted by 1 to 3 substituents independently selected from halogen, C1-C6 alkoxy, and C1-C6 haloalkyl; R 2a and R 2b is hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 haloalkylsulfanyl, C1-C3 alkoxy, C1-C3 haloalkoxy, halogen, NO2, SF5, CN, C(O)NH2, C(O)OH, C(S)NH2, C3-C6 cycloalkyl, R X C3-C6 cycloalkyl substituted by 1 to 3 substituents independently selected from: C3-C6 cycloalkylcarbonyl, phenyl, R Xphenyl substituted with 1 to 3 substituents independently selected from: heteroaryl, R X heteroaryl substituted with 1 to 3 substituents independently selected from: OR 6 , piperidin-2-one-1-yl, R X Piperidin-2-one-1-yl substituted by 1 to 2 substituents independently selected from: pyridin-2-one-1-yl, R X pyridin-2-one-1-yl substituted by 1 to 2 substituents independently selected from: azetidin-1-yl, R X azetidin-1-yl substituted by 1 to 2 substituents independently selected from X pyrrolidin-1-yl substituted by 1 to 2 substituents independently selected from: C-C cycloalkyl-C-C alkyl; Z C3-C6 cycloalkylC1-C4 alkyl substituted by 1 to 2 substituents independently selected from; C3-C6 cycloalkylC1-C3 alkoxy, R X C3-C6 cycloalkyl, C1-C3 alkoxy substituted by 1 to 2 substituents independently selected from; C1-C5 cyanoalkyl, C1-C5 cyanoalkoxy, C1-C4 alkylsulfanyl, R X C1-C4 alkylsulfanyl substituted by 1 to 3 substituents independently selected from: C1-C4 alkylsulfonyl, R X C1-C4 alkylsulfonyl substituted by 1 to 3 substituents independently selected from: X each independently selected from C1-C4 alkylsulfinyl substituted by 1 to 3 substituents independently selected from: R 3 is C1-C3 alkyl or C1-C3 haloalkyl; R 4 teeth [ka] (In the formula, the wavy line represents R 4 and Q a or Q b (represents a bond with and; A 14 , A 24 and A 34 are, independently of each other, N or CH; R 4c is C1-C3 alkyl, C1-C3 haloalkyl, allyl, propargyl or C3-C6 cycloalkylC1-C4 alkyl; R 5 is hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, C3-C4 alkoxyC(O)-, (C1-C3 alkoxy)2CH-, halogen, -CN, NHC(O)-, amino (i.e., -NH), (C1-C3 alkyl)amino, di(C1-C3 alkyl)amino, hydroxy, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl , C1-C3 alkoxy-C1-C3 alkyl, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl, (C1-C3 alkyl)sulfonylamino, (C1-C3 alkyl)sulfonyl(C1-C3 alkyl)amino, (C1-C3 alkyl)NHC(O)-, (C1-C3 alkyl)NC(O)-, (C1-C3 cycloalkyl)NHC(O)-, (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O)-, (C1-C3 alkyl)C(O)(C1-C3 alkyl)N-, (C1-C3 alkyl)C(O)NH-, (C1-C3 alkyl)C(O)-, (C1-C3 alkoxy)C(O)-, HC(O)-, diphenylmethanimine, C1-C3 haloalkoxy, phenyl or a 5-membered aromatic heterocycle; or R 5 is phenyl substituted with 1 to 3 substituents selected from C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, —CN, and hydroxyl; or R 5 is a 5-membered aromatic heterocycle substituted with 1 to 3 substituents selected from C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, —CN, and hydroxyl; R 5a and R 5b are independently selected from hydrogen, halogen, —CN, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy and C1-C3 haloalkoxy; R 6 is phenyl, benzyl, heteroaryl or C3-C6 cycloalkyl; or R 6 are phenyl, benzyl, heteroaryl, or C-C cycloalkyl, each of which, independently of each other, is R X and is substituted with 1 to 3 substituents independently selected from: R X are independently selected from halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, NO2, SF5, CN, —C(O)NH2, —C(S)NH2, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl and C1-C4 alkylsulfonyl; R Y is selected from hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, hydroxy, C1-C3 alkoxy, C1-C3 haloalkoxy, halogen, —CN, and cyclopropyl; and R Z is selected from oxo, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, and CN. and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides thereof.
[0005] The present invention also provides processes for preparing compounds of formula (I), as well as intermediate compounds useful in the preparation of compounds of formula (I).
[0006] In a second aspect, the present invention provides compositions comprising a compound of formula (I), one or more adjuvants and diluents, and optionally one or more other active ingredients.
[0007] In a third aspect, the present invention provides a method for the control and extermination of insects, mites, nematodes or molluscs, the method comprising the step of applying to the pest, the pest's habitat or plants susceptible to attack by the pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) or a composition comprising such a compound.
[0008] In a fourth aspect, the present invention provides a method for protecting plant propagation material from attack by insects, mites, nematodes or mollusks, the method comprising the step of treating the propagation material or the locus where the propagation material is to be planted with an effective amount of a compound of formula (I) or a composition comprising such a compound.
[0009] In a fifth aspect, the present invention provides plant propagation material such as seeds comprising, treated with or having attached thereto a compound of formula (I) or a composition comprising such a compound.
[0010] In a further aspect, the present invention provides a method for controlling parasites in or on an animal in need thereof, which method comprises administering an effective amount of a compound of the first aspect. The present invention further provides a method for controlling ectoparasites on an animal in need thereof, which method comprises administering an effective amount of a compound of formula (I) as defined in the first aspect. The present invention further provides a method for preventing and / or treating diseases caused by ectoparasites, which method comprises administering an effective amount of a compound of formula (I) as defined in the first aspect to an animal in need thereof. DETAILED DESCRIPTION OF THE INVENTION
[0011] Compounds of formula (I) having at least one basic centre can, for example, form acid addition salts with strong inorganic acids, such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrohalic acids; strong organic carboxylic acids, for example C1-C4 alkanecarboxylic acids which are unsubstituted or substituted, for example, by halogens, such as acetic acid; saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid; hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or for example benzoic acid; or organic sulfonic acids, for example C1-C4 alkane- or arylsulfonic acids which are unsubstituted or substituted, for example, by halogens, such as methane- or p-toluenesulfonic acid. The compounds of formula (I) having at least one acidic group can, for example, form salts with bases, for example inorganic salts, for example alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or organic amines, for example morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or mono-, di- or trihydroxy-lower alkylamines, for example mono-, di- or triethanolamine.
[0012] In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form as N-oxides, or in salt form, for example in agriculturally usable salt form.
[0013] N-oxides are oxidized forms of tertiary amines or nitrogen-containing aromatic heterocyclic compounds, as described, for example, in the book "Heterocyclic N-oxides", A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
[0014] The compounds of formula (I) according to the present invention also include hydrates which may be formed during salt formation.
[0015] As used herein, "C1-C n The term "alkyl" refers to a saturated straight or branched hydrocarbon group having 1 to n carbon atoms attached via any of the carbon atoms, such as any one of the following groups: 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] As used herein, "C1-C nThe term "haloalkyl" refers to a straight or branched saturated alkyl group (as defined above) having 1 to n carbon atoms attached via any of the carbon atoms, wherein some or all of the hydrogen atoms in these groups may be replaced by fluorine, chlorine, bromine and / or iodine, i.e., for example, 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, and any one of 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, and nonafluorobutyl. Thus, the term "C1-C2 fluoroalkyl" refers to a C1-C2 alkyl group having 1, 2, 3, 4 or 5 fluorine atoms, such as any one of difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl or pentafluoroethyl.
[0017] As used herein, "C1-C nThe term "alkoxy" refers to a straight or branched saturated alkyl group having 1 to n carbon atoms (as defined above) attached through an oxygen atom, i.e., for example, any one of methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy, or 1,1-dimethylethoxy groups. As used herein, "C1-C n The term "haloalkoxy" refers to a C1-C alkyl group in which one or more hydrogen atoms of the alkyl group are replaced with the same or different halo atoms. n It refers to an alkoxy group and examples include trifluoromethoxy, 2-fluoroethoxy, 3-fluoropropoxy, 3,3,3-trifluoropropoxy, and 4-chlorobutoxy.
[0018] As used herein, "C1-C n Alkoxy C1-C m The term "alkyl" refers to an alkoxy group having 1 to n carbon atoms (as defined above) attached through an oxygen atom to an alkyl group having 1 to m carbon atoms (as defined above), which alkyl group is attached to the remainder of the molecule.
[0019] As used herein, "C1-C n The term "cyanoalkyl" refers to a linear or branched saturated C1-C alkyl group having 1 to n carbon atoms (as defined above). n It refers to alkyl groups in which one of the hydrogen atoms in these groups is replaced by a cyano group -CN, such as cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, 3-cyanopropyl, 1-(cyanomethyl)-2-ethyl, 1-(methyl)-2-cyanoethyl, 4-cyanobutyl, and the like.
[0020] As used herein, "C1-C n The term "nitroalkyl" refers to a linear or branched saturated C1-C2 alkyl group having 1 to n carbon atoms (as defined above) in which one of the hydrogen atoms in these groups is replaced by a nitro group -NO2. nIt refers to an alkyl group, such as nitromethyl, 2-nitroethyl, 2-nitropropyl, 3-nitropropyl, 1-(nitromethyl)-2-ethyl, 1-(methyl)-2-nitroethyl, 4-nitrobutyl, and the like.
[0021] As used in this specification, "C3 to C n The term "cycloalkyl" refers to a 3 to n-membered cycloalkyl group, such as cyclopropane, cyclobutane, cyclopentane, and cyclohexane.
[0022] As used in this specification, "C3 to C n The term "cycloalkylcarbonyl" refers to a 3 to n-membered cycloalkyl group attached to a carbonyl (C=O) group, which is attached to the remainder of the molecule. Similarly, as used herein, "C1-C n Alkylcarbonyl, C1-C n The terms "alkoxycarbonyl," "phenyloxycarbonyl," and "benzyloxycarbonyl" refer to alkyl, alkoxy, phenyloxy, and benzyloxy groups bound to a carbonyl (C=O) group, which in turn is attached to the remainder of the molecule.
[0023] As used herein, the term "C3-C4 cycloalkyl C1-C2 alkyl" refers to a 3- or 4-membered cycloalkyl group having a methylene or ethylene group attached to the remainder of the molecule. When a C3-C4 cycloalkyl-C1-C2 alkyl group is substituted, the substituents may be on the cycloalkyl group and / or the alkyl group.
[0024] As used herein, the term "C3-C6 cycloalkyl C1-C4 haloalkoxy" refers to a 3- to 6-membered cycloalkyl group bound to a 1- to 4-membered haloalkoxy group, which is bound to the remainder of the molecule.
[0025] As used herein, "aminocarbonyl C1-Cn The term "alkyl" refers to an alkyl group in which one of the hydrogen atoms in the group has been replaced by a CONH2 group.
[0026] As used herein, "hydroxycarbonyl C1-C n The term "alkyl" refers to an alkyl group in which one of the hydrogen atoms in the group has been replaced by a C(O)OH group.
[0027] As used herein, "C1-C n The term "alkylsulfanyl" refers to a C1-C alkyl group bonded through a sulfur atom. n Similarly, as used herein, "C1-C" refers to an alkyl moiety. n Haloalkylthio" or "C1-C n The term "haloalkylsulfanyl" refers to a C1-C alkyl group bonded through a sulfur atom. n It refers to the haloalkyl moiety. Similarly, "C3-C n The term "cycloalkylsulfanyl" refers to a 3 to n-membered cycloalkyl moiety attached through a sulfur atom.
[0028] As used herein, "C1-C n The term "alkylsulfinyl" refers to a C1-C alkyl group bonded through the sulfur atom of the S(=O) group. n Similarly, as used herein, "C1-C" refers to an alkyl moiety. n The term "haloalkylsulfinyl" refers to a C1-C alkyl group bonded through the sulfur atom of the S(=O) group. n It refers to the haloalkyl moiety. Similarly, "C3-C n The term "cycloalkylsulfinyl" refers to a 3 to n-membered cycloalkyl moiety attached through the sulfur atom of an S(=O) group.
[0029] As used herein, "C1-C n The term "alkylsulfonyl" refers to a C1-C alkyl group bonded through the sulfur atom of the S(=O)2 group.n Similarly, as used herein, "C1-C" refers to an alkyl moiety. n The term "haloalkylsulfonyl" refers to a C1-C2 alkyl group bonded through the sulfur atom of the S(=O)2 group. n It refers to the haloalkyl moiety. Similarly, "C3-C n The term "cycloalkylsulfonyl" refers to a 3- to n-membered cycloalkyl moiety attached through the sulfur atom of an S(=O)2 group.
[0030] As used herein, "trimethylsilane C1-C n The term "alkyl" refers to an alkyl group in which one of the hydrogen atoms in the group has been replaced by a -Si(CH3)3 group.
[0031] As used in this specification, "C2 to C n The term "alkenyl" refers to a straight or branched alkenyl chain having 2 to n carbon atoms and one or two double bonds, for example, ethenyl, prop-1-enyl, but-2-enyl.
[0032] As used in this specification, "C2 to C n The term "haloalkenyl" refers to a C-C alkyl group substituted with one or more halo atoms, which may be the same or different. n Refers to the alkenyl moiety.
[0033] As used in this specification, "C2 to C n The term "alkynyl" refers to a straight or branched alkynyl chain having 2 to n carbon atoms and one triple bond, for example, ethynyl, prop-2-ynyl, but-3-ynyl.
[0034] As used in this specification, "C2 to C n The term "haloalkynyl" refers to a C-C alkyl group substituted with one or more halo atoms, which may be the same or different. n Refers to the alkynyl moiety.
[0035] Halogen or "halo" is generally fluorine, chlorine, bromine or iodine. This also applies correspondingly to halogen in compounds with other meanings, such as haloalkyl.
[0036] As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic ring having 1 to 3 heteroatoms independently selected from N, O, and S. Examples are heteroaryls J-1 to J-39 shown in Scheme J below. Preferred heteroaryls are pyridyl, pyrimidyl, and pyrazolyl.
[0037] Table J: Heteroaryls J-1 to J-39: The arrows in heteroaryls J-1 to J-39 represent the points of attachment to the remainder of the compound. [ka]
[0038] As used herein, the term "optionally substituted" means that the group to which it is being referred is unsubstituted or substituted with a specified substituent; for example, "C3-C4 cycloalkyl optionally substituted with 1 or 2 halo atoms" means C3-C4 cycloalkyl, C3-C4 cycloalkyl substituted with 1 halo atom, and C3-C4 cycloalkyl substituted with 2 halo atoms.
[0039] As used herein, for example, Q a , Q b , R 4a , R 4b The wavy line at the and T represents the point of connection / attachment to the remainder of the compound.
[0040] As used herein, the term "control" refers to reducing the number of pests, eliminating pests, and / or preventing further pest damage so that damage to plants or plant-derived products is reduced.
[0041] As used herein, the term "pest" refers to insects and mollusks found in agriculture, horticulture, forestry, and storage of plant-based products (such as fruit, grain, and lumber); and pests associated with damage to man-made structures. The term pest encompasses all stages in the life cycle of a pest.
[0042] As used herein, the term "effective amount" refers to the amount of a compound or salt thereof that produces a desired effect in single or multiple applications.
[0043] An effective amount is readily determined by one skilled in the art by the use of known techniques and by observing results obtained under analogous circumstances. Determining an effective amount takes into account many factors, including, but not limited to, the type of plant or plant-derived product to which it is applied; the pest to be controlled and its life cycle; the particular compound applied; the type of application; and other relevant circumstances.
[0044] As one skilled in the art would appreciate, compounds of formula (I) may be represented by the following formula (I * ): [ka] (In the formula, A 1 , A 2 , A 3 , A 4 , A 5 , Q, R 1 , R 2a , R 2b and R 3 is as defined in the first aspect) The compound contains a stereogenic center indicated by an asterisk.
[0045] The present invention contemplates both the racemate and the individual enantiomers. Compounds with preferred stereochemistry are shown below. Particularly preferred compounds of the present invention are compounds of formula (I'): [ka] (In the formula, A 1 , A 2 , A 3 , A 4 , A 5 , Q, R 1 , R 2a , R 2b and R 3 is as defined in the first aspect) and the stereoisomers, enantiomers and tautomers of the compounds of formula (I'), as well as the N-oxides and agrochemically acceptable salts thereof.
[0046] Embodiments of the present invention are provided as follows.
[0047] In an embodiment of each aspect of the present invention, A 1 , A 2 and A 3 is defined as follows: AA 1 , A 2 and A 3 are, independently of each other, N or CR Y or A 1 =A 2 -A 3 are summarized as follows: NR-C(=X 0 )-N; where X 0 is O or S; BA 1 , A 2 and A 3 are, independently of each other, N or CR Y with the proviso that no more than two of the three are N; or A 1 =A 2 -A 3 are summarized as follows: NR-C(=X 0 )-N; or CA1 and A 3 is N, and A 2 is CR Y or A 1 =A 2 -A 3 are collectively NR-C(=O)-N; or DA 1 , A 2 and A 3 are, independently of each other, N or CH; or A 1 =A 2 -A 3 are collectively NR-C(=O)-N; or EA 1 , A 2 and A 3 are, independently of one another, N or CH, provided that not more than two of the three are N; or A 1 =A 2 -A 3 are collectively NH-C(=O)-N; or FA 1 is N, and A 2 and A 3 is CH; or A 1 =A 2 -A 3 are collectively NH-C(=O)-N; or GA 1 and A 2 is CH, and A 3 is N; or A 1 =A 2 -A 3 are collectively NR-C(=O)-N; or HA 1 and A 3 is N, and A 2 is CH; or A 1 =A 2 -A 3 are collectively NH-C(=O)-N; or IA 1 , A 2 and A 3 are, independently of each other, N or CR Ywith the proviso that no more than two of the three are N; or JA 1 and A 3 is N, and A 2 is CR Y is; or KA 1 , A 2 and A 3 are, independently of one another, N or CH; or LA 1 , A 2 and A 3 are, independently of one another, N or CH, provided that not more than two of the three are N; or MA 1 is N, and A 2 and A 3 is CH; or NA 1 and A 2 is CH, and A 3 is N; or Office Automation 1 and A 3 is N, and A 2 is CH; or PA 1 =A 2 -A 3 are summarized as follows: NR-C(=X 0 )-N; or QA 1 =A 2 -A 3 are collectively referred to as N(CH3)-C(=X 0 )-N; or RA 1 =A 2 -A 3 are collectively referred to as NH-C(=X 0 )-N; or SA 1 =A 2 -A 3 are collectively NR-C(=O)-N; or TA 1 =A 2 -A 3 are collectively N(CH3)-C(=O)-N; or UA 1 =A 2 -A 3 are collectively NH-C(=O)-N; or VA 1 =A 2 -A 3 are collectively NR-C(=S)-N; or WA 1 =A 2 -A 3 are collectively NH-C(=S)-N; or XA 1 =A 2 -A 3 are collectively N(CH3)-C(=S)-N.
[0048] In an embodiment of each aspect of the present invention, AX 0 is O or S; or BX 0 is O; or CX 0 is S.
[0049] In an embodiment of each aspect of the present invention, AA 4 is CR Y and A 5 is N; or BA 4 is CR Y and A 5 is CH; or CA 4 is CH, and A 5 is N; or DA 4 is N, and A 5 is CH; or EA 4 and A 5 are both CH.
[0050] In an embodiment of each aspect of the present invention, AA 1 is N and A 2 and A 3 is CH, and A4 and A 5 are both CH; or BA 1 and A 2 is CH and A 3 is N, and A 4 and A 5 are both CH; or CA 1 and A 3 is N and A 2 is CH, and A 4 is CR Y and A 5 is CH; or DA 1 and A 3 is N and A 2 is CH, and A 4 is CH, and A 5 is N; or EA 1 and A 3 is N and A 2 is CH, and A 4 is N, and A 5 is CH; or FA 1 and A 3 is N and A 2 is CH, and A 4 is N or CH, and A 5 is CH; or GA 1 and A 3 is N and A 2 is CH, and A 4 is CH, and A 5 is N or CH; or HA 1 and A 3 is N and A 2 is CH, and A 4 and A 5 are both N; or IA 1 and A 3 is N and A 2 is CH, and A 4 and A5 are both CH; or JA 1 =A 2 -A 3 are collectively NR-C(=O)-N, and A 4 and A 5 are both CH; or KA 1 =A 2 -A 3 are collectively N(CH3)-C(=O)-N, and A 4 and A 5 are both CH; or LA 1 =A 2 -A 3 are collectively NH-C(=O)-N, and A 4 and A 5 are both CH.
[0051] In an embodiment of each aspect of the invention, R is A. hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy or C1-C3 haloalkoxy; or B. hydrogen, methyl, ethyl, difluoroethyl or trifluoroethyl; or C. hydrogen; methyl, ethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, or D. hydrogen; or E. methyl, or 2,2,2-trifluoroethyl; or F. methyl; or G. Methyl or Hydrogen is.
[0052] In an embodiment of each aspect of the present invention, R 1 teeth A. Hydrogen, C1-C6 alkyl, C1-C6 cyanoalkyl, aminocarbonyl C1-C6 alkyl, hydroxycarbonyl C1-C6 alkyl, C1-C6 nitroalkyl, trimethylsilane C1-C6 alkyl, C1-C3 alkoxy-C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C4 cycloalkyl C1-C2 alkyl-, or C3-C4 cycloalkyl, C1-C2 alkyl- (wherein the C3-C4 cycloalkyl group is substituted with 1 or 2 halogen atoms), oxetan-3-yl-CH2-, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, or benzyl substituted with 1 to 3 substituents selected from benzyl, halogen, C1-C6 alkoxy, and C1-C6 haloalkyl; or B. hydrogen, C1-C6 alkyl, C1-C6 cyanoalkyl, aminocarbonylC1-C6 alkyl, hydroxycarbonylC1-C6 alkyl, C1-C6 nitroalkyl, trimethylsilaneC1-C6 alkyl, C1-C3 alkoxy-C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C4 cycloalkylC1-C2 alkyl-, C3-C4 cycloalkylC1-C2 alkyl- (wherein the C3-C4 cycloalkyl group is substituted with 1 or 2 halogen atoms), oxetan-3-yl-CH2-, phenyloxycarbonyl, benzyloxycarbonyl or benzyl; or C. hydrogen, C1-C6 alkyl, C1-C6 cyanoalkyl, aminocarbonylC1-C6 alkyl, hydroxycarbonylC1-C6 alkyl, C1-C6 nitroalkyl, trimethylsilaneC1-C6 alkyl, C1-C3 alkoxy-C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C4 cycloalkylC1-C2 alkyl-, benzyloxycarbonyl or benzyl; or D. hydrogen, C1-C6 alkyl, C1-C6 cyanoalkyl, aminocarbonylC1-C6 alkyl, hydroxycarbonylC1-C6 alkyl, C1-C3 alkoxy-C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C4 cycloalkylC1-C2 alkyl-, benzyloxycarbonyl or benzyl; or E. hydrogen, C1-C6 alkyl, C1-C6 cyanoalkyl, C1-C3 alkoxy-C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C4 cycloalkylC1-C2 alkyl-, benzyloxycarbonyl or benzyl; or F. hydrogen, C1-C3 alkyl, C1-C3 cyanoalkyl, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C3-C4 cycloalkylC1-C2 alkyl-, benzyloxycarbonyl or benzyl; or G. hydrogen, C1-C3 alkyl, C1-C3 cyanoalkyl, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C3-C4 cycloalkylC1-C2 alkyl-, benzyloxycarbonyl or benzyl; or H. hydrogen, methyl, ethyl, cyanomethyl, methoxymethyl, cyclopropyl-methyl, allyl, propargyl, benzyloxycarbonyl or benzyl; or I. hydrogen, methyl or cyclopropyl-methyl; or J. hydrogen or methyl; or K. Hydrogen is.
[0053] In an embodiment of each aspect of the present invention, R 2a teeth A. Hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 haloalkylsulfanyl, C1-C3 alkoxy, C1-C3 haloalkoxy, halogen, NO2, SF5, CN, C(O)NH2, C(O)OH, C(S)NH2, C3-C6 cycloalkyl, R x C3-C6 cycloalkyl, C3-C6 cycloalkylcarbonyl, phenyl, R x phenyl, heteroaryl, R substituted with 1 to 3 substituents independently selected from x heteroaryl substituted with 1 to 3 substituents independently selected from: OR 6 , piperidin-2-one-1-yl, R x piperidin-2-one-1-yl, pyridin-2-one-1-yl, R substituted by 1 to 2 substituents independently selected from x pyridin-2-one-1-yl, azetidin-1-yl, R substituted by 1 to 2 substituents independently selected from x Azetidin-1-yl, pyrrolidin-1-yl, R substituted with 1 to 2 substituents independently selected from x pyrrolidin-1-yl, C3-C6 cycloalkyl, C1-C4 alkyl, substituted by 1 to 2 substituents independently selected from z C3-C6 cycloalkylC1-C4 alkyl, C3-C6 cycloalkylC1-C3 alkoxy, substituted by 1 to 2 substituents independently selected from R x C3-C6 cycloalkyl, C1-C3 alkoxy, C1-C5 cyanoalkyl, C1-C5 cyanoalkoxy, C1-C4 alkylsulfanyl, R x C1-C4 alkylsulfanyl, C1-C4 alkylsulfonyl substituted by 1 to 3 substituents independently selected from R x C1-C4 alkylsulfonyl, C1-C4 alkylsulfinyl, and R xC1-C4 alkylsulfinyl substituted by 1 to 3 substituents independently selected from: B. Heteroaryl selected from halogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, phenyl, J-1 to J-39 (C3-C4 cycloalkyl, phenyl or heteroaryl each independently represent 1 to 3 substituents R X Replaced with );OR 6 , piperidin-2-one-1-yl, pyridin-2-one-1-yl, R X azetidin-1-yl, pyrrolidin-1-yl, optionally substituted with R X C3-C6 cycloalkyl, C1-C4 alkyl optionally substituted with R X C3-C6 cycloalkyl, C1-C3 alkoxy, C1-C5 cyanoalkyl, C1-C5 cyanoalkoxy, optionally substituted with R X C1-C4 alkylsulfonyl optionally substituted with R X C1-C4 alkylsulfinyl optionally substituted with C. Heteroaryl selected from halogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, phenyl, J-1 and J-25 (C3-C4 cycloalkyl, phenyl or heteroaryl each independently have 1 to 3 substituents R X Replaced with );OR 6 , piperidin-2-one-1-yl, pyridin-2-one-1-yl, R X azetidin-1-yl, pyrrolidin-1-yl, optionally substituted with R X C3-C6 cycloalkyl, C1-C4 alkyl optionally substituted with R X C3-C6 cycloalkyl, C1-C3 alkoxy, C1-C5 cyanoalkyl, C1-C5 cyanoalkoxy, optionally substituted with R X C1-C4 alkylsulfonyl optionally substituted with R X C1-C4 alkylsulfinyl optionally substituted with D. Halogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, phenyl, pyrazolyl (C3-C4 cycloalkyl, phenyl, pyrazolyl each independently have 1 to 3 substituents R X Replaced with );OR 6 , piperidin-2-one-1-yl, pyridin-2-one-1-yl, R X azetidin-1-yl, pyrrolidin-1-yl, optionally substituted with R X C3-C6 cycloalkyl, C1-C4 alkyl optionally substituted with R X C3-C6 cycloalkyl, C1-C3 alkoxy, C1-C5 cyanoalkyl, C1-C5 cyanoalkoxy, optionally substituted with R X C1-C4 alkylsulfonyl optionally substituted with R X C1-C4 alkylsulfinyl optionally substituted with E. Halogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, phenyl or pyrazolyl (C3-C4 cycloalkyl, phenyl, pyrazolyl each independently have 1-2 substituents R X ), OR 6 , R X azetidin-1-yl optionally substituted with R X C3-C6 cycloalkyl, C1-C4 alkyl optionally substituted with R X C3-C6 cycloalkyl, C1-C3 alkoxy optionally substituted with R X C1-C4 alkylsulfonyl optionally substituted with R X C1-C4 alkylsulfinyl optionally substituted with F. Halogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, 1-2 substituents R X C3-C4 cycloalkyl substituted with OR 6 , C3-C6 cycloalkyl C1-C4 alkyl, R XC3-C6 cycloalkyl, C1-C4 alkyl, C1-C4 alkylsulfonyl, substituted with R X C1-C4 alkylsulfonyl, C1-C4 alkylsulfinyl substituted with R X C1-C4 alkylsulfinyl substituted with; or G. Halogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C3-C4 cycloalkyl substituted with 1-2 halogens, C1-C3 alkyl, or C1-C3 haloalkyl; C3-C4 cycloalkylmethyl, C3-C4 cycloalkylmethyl substituted with 1-2 halogens, C1-C3 alkyl, or C1-C3 haloalkyl; or C1-C2 alkylsulfonyl substituted with 1-3 halogens; or H: halogen, C1-C3 alkyl, C1-C3 haloalkyl, cyclopropyl, cyclopropyl substituted with 1-2 halogens, methyl or trifluoromethyl, cyclopropylmethyl substituted with 1-2 halogens or trifluoromethyl; or C1-C2 alkylsulfonyl substituted with 1-3 halogens; or I. halogen, C1-C3 haloalkyl, cyclopropyl substituted with 1-2 fluorines, methyl or trifluoromethyl, cyano, cyclopropylmethyl substituted with 1-2 fluorines, or trifluoromethylsulfonyl; or J. C3-C6 cycloalkyl substituted with 1 to 3 substituents independently selected from halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 haloalkylthio, C1-C3 alkoxy, C1-C3 haloalkoxy, CN, C3-C6 cycloalkyl, C1-C3 alkyl, C1-C3 haloalkyl, cyano, and halogen; C3-C6 cycloalkyl C1-C4 alkyl, C3-C6 cycloalkyl C1-C4 alkyl substituted with 1 to 5 substituents independently selected from C3-C6 cycloalkyl C1-C3 alkyl, C1-C3 alkyl, C1-C3 haloalkyl, cyano, and halogen; C1-C5 cyanoalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfinyl, C1-C4 haloalkylsulfinyl, C3-C6 cycloalkylsulfanyl, C3-C6 cycloalkylsulfinyl, or C3-C6 cycloalkylsulfonyl; or K. C3-C6 cycloalkyl substituted with 1 or 2 substituents independently selected from halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 haloalkylthio, C1-C3 alkoxy, C1-C3 haloalkoxy, CN, C3-C6 cycloalkyl, C1-C3 haloalkyl, cyano, and halogen; C3-C6 cycloalkylC1-C4 alkyl, C3-C6 cycloalkylC1-C4 alkyl substituted with 1 to 3 substituents independently selected from C1-C3 haloalkyl, cyano, and halogen; C1-C5 cyanoalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfinyl, C1-C4 haloalkylsulfinyl, C3-C6 cycloalkylsulfanyl, C3-C6 cycloalkylsulfinyl, or C3-C6 cycloalkylsulfonyl; or L. halogen, C1-C3 haloalkyl, C1-C3 haloalkylthio, C1-C3 haloalkoxy, C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted with 1 or 2 substituents independently selected from C1-C3 haloalkyl, cyano, and halogen; C3-C6 cycloalkylC1-C4 alkyl, C3-C6 cycloalkylC1-C4 alkyl substituted with 1 to 3 substituents independently selected from C1-C3 haloalkyl, cyano, and halogen; C1-C5 cyanoalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfinyl, C1-C4 haloalkylsulfinyl, C3-C6 cycloalkylsulfanyl, C3-C6 cycloalkylsulfinyl, or C3-C6 cycloalkylsulfonyl; or M. halogen or C1-C3 haloalkyl; or N. chlorine, fluorine, bromine, difluoromethyl or trifluoromethyl; or O. Fluorine, chlorine, bromine or trifluoromethyl; or P. trifluoromethyl; or Q. Chlorine or trifluoromethyl; R. Chlorine, bromine, iodine or trifluoromethyl.
[0054] In an embodiment of each aspect of the present invention, R 2b teeth A. Hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 haloalkylsulfanyl, C1-C3 alkoxy, C1-C3 haloalkoxy, halogen, NO2, SF5, CN, C(O)NH2, C(O)OH, C(S)NH2, C3-C6 cycloalkyl, R x C3-C6 cycloalkyl, C3-C6 cycloalkylcarbonyl, phenyl, R x phenyl, heteroaryl, R substituted with 1 to 3 substituents independently selected from x heteroaryl substituted with 1 to 3 substituents independently selected from: OR 6 , piperidin-2-one-1-yl, R xpiperidin-2-one-1-yl, pyridin-2-one-1-yl, R substituted by 1 to 2 substituents independently selected from x pyridin-2-one-1-yl, azetidin-1-yl, R substituted by 1 to 2 substituents independently selected from x Azetidin-1-yl, pyrrolidin-1-yl, R substituted with 1 to 2 substituents independently selected from x pyrrolidin-1-yl, C3-C6 cycloalkyl, C1-C4 alkyl, substituted by 1 to 2 substituents independently selected from z C3-C6 cycloalkylC1-C4 alkyl, C3-C6 cycloalkylC1-C3 alkoxy, substituted by 1 to 2 substituents independently selected from R x C3-C6 cycloalkyl, C1-C3 alkoxy, C1-C5 cyanoalkyl, C1-C5 cyanoalkoxy, C1-C4 alkylsulfanyl, R x C1-C4 alkylsulfanyl, C1-C4 alkylsulfonyl substituted by 1 to 3 substituents independently selected from R x C1-C4 alkylsulfonyl, C1-C4 alkylsulfinyl, and R x C1-C4 alkylsulfinyl substituted by 1 to 3 substituents independently selected from: B. halogen, C1-C3 haloalkyl, C1-C3 haloalkylthio, C1-C3 alkoxy, C1-C3 haloalkoxy or CN; or C. halogen, C1-C3 haloalkyl or C1-C3 haloalkoxy; or D. halogen or C1-C3 haloalkyl; or E. chlorine, fluorine, bromine, difluoromethyl or trifluoromethyl; or F. fluorine, chlorine, bromine or trifluoromethyl; or G. trifluoromethyl; or H. chlorine or trifluoromethyl; or I. Chlorine, bromine, iodine or trifluoromethyl is.
[0055] In an embodiment of each aspect of the present invention, R 3 teeth A. C1-C3 alkyl or C1-C3 haloalkyl; or B. methyl or trifluoromethyl; or C. Methyl is.
[0056] In an embodiment of each aspect of the present invention, Q is A. [ka] or BQ a and R 4 is R 4a or R 4b is; or CQ a and R 4 is R 4a is; or DQ a and R 4 is R 4b is; or EQ b and R 4 is R 4a or R 4b is; or FQ b and R 4 is R 4a is; or GQ b and R 4 is R 4b is.
[0057] In an embodiment of each aspect of the present invention, Q a teeth AQ a -1~Q a -16; or BQ a -1, Q a -6, Q a -7, Q a-10 and Q a -15; or CQ a -1 or Q a -15; or DQ a -1~Q a -16, and R 4 is R 4a is; or EQ a -1~Q a -16, and R 4 is R 4b is; or FQ a -1, Q a -6, Q a -7, Q a -10 and Q a -15 and R 4 is R 4a is; or GQ a -1, Q a -6, Q a -7, Q a -10 and Q a -15 and R 4 is R 4b is; or HQ a -1 or Q a -15 and R 4 is R 4a is; or IQ a -1 or Q a -15 and R 4 is R 4b is; or JQ a -1 and R 4 is R 4a or R 4b is. [ka]
[0058] In an embodiment of each aspect of the present invention, Q b teeth AQ b -1~Q b-13; or BQ b -1; or CQ b -1~Q b -13 and R 4 is R 4a is; or DQ b -1~Q b -13 and R 4 is R 4b is; or EQ b -1 and R 4 is R 4a is; or FQ b -1 and R 4 is R 4a is. [ka]
[0059] In an embodiment of each aspect of the present invention, R 4 teeth, A. [ka] (In the formula, the wavy line represents Q a or Q b R 4 represents a bond; and A 14 , A 24 and A 34 are, independently of one another, N or CH; or B. [ka] (In the formula, the wavy line represents Q a or Q b R 4 represents a bond; and A 14 , A 24 and A 34 are, independently of one another, N or CH) or C. [ka] (In the formula, the wavy line represents Q a or Q b R 4 represents a bond; and A 14 is N or CH).
[0060] In an embodiment of each aspect of the present invention, R 4 R 4a If AA 14 , A 24 and A 34 are, independently of one another, N or CH, provided that at least one is N; or BA 14 , A 24 and A 34 are, independently of each other, N or CH, provided that one is N and the other two are CH; or CA 14 , A 24 and A 34 are, independently of one another, N or CH, provided that at least one is CH; or DA 14 , A 24 and A 34 are, independently of each other, N or CH, provided that one is CH and the other two are N; EA 14 is N and A 24 is N or CH, and A 34 is N or CH; or FA 14 is N or CH, and A 24 is N, and A 34 is N or CH; or GA 14 is N or CH, and A 24 is N or CH, and A 34 is N; or HA 14 is CH and A 24 is N or CH, and A 34 is N or CH; or IA 14is N or CH, and A 24 is CH, and A 34 is N or CH; or JA 14 is N or CH, and A 24 is N or CH, and A 34 is CH; or KA 14 is N and A 24 is N, and A 34 is N or CH; or LA 14 is N and A 24 is CH, and A 34 is N or CH; or MA 14 is CH and A 24 is N, and A 34 is N or CH; or NA 14 is CH and A 24 is CH, and A 34 is N or CH; or Office Automation 14 is N and A 24 is N or CH, and A 34 is N; or PA 14 is N and A 24 is N or CH, and A 34 is CH; or QA 14 is CH and A 24 is N or CH, and A 34 is N; or RA 14 is CH and A 24 is N or CH, and A 34 is CH; or SA 14 is N or CH, and A 24 is N, and A 34 is N; or TA 14 is N or CH, and A 24 is N, and A 34 is CH; or UA 14 is N or CH, and A 24 is CH, and A 34 is N; or VA 14 is N or CH, and A 24 is CH, and A 34 is CH; or WA 14 is N and A 24 is N, and A 34 is N; or XA 14 is N and A 24 is N, and A 34 is CH; or YA 14 is N and A 24 is CH, and A 34 is N; or ZA 14 is CH and A 24 is N, and A 34 is N; or A.A. 14 is N and A 24 is CH, and A 34 is CH; or B.B.A. 14 is CH and A 24 is N, and A 34 is CH; or CC.A 14 is CH and A 24 is CH, and A 34 is N; or DD.A 14 is CH and A 24 is CH, and A 34 is CH.
[0061] In an embodiment of each aspect of the present invention, R 4 R 4b If AA 14 is CH; or BA 14 is N.
[0062] In an embodiment of each aspect of the present invention, R 4a is an oxo-triazinyl moiety or an oxo-diazinyl moiety or an oxo-pyridyl moiety. 4a is an oxo-diazinyl moiety. In an embodiment of each aspect of the invention, R 4a is an oxopyridyl, oxopyrimidyl, oxopyrazinyl or oxopyridazinyl moiety. In an embodiment of each aspect of the invention, R 4b is an oxo-dihydro-pyridyl or oxo-dihydro-pyridazinyl moiety. 4a and R 4b are each bonded to the remainder of the compound through a carbon atom in the ring (the "bonding carbon atom"). The bonding carbon atom and the carbonyl group C=O are para to each other in the oxopyridyl, oxopyrimidyl, oxopyrazinyl, or oxopyridazinyl moiety. R 4a and R 4b has a nitrogen atom substituted at the ortho position relative to the carbonyl group C=O. The substituted nitrogen atom is 4c In an embodiment of each aspect of the present invention, R 4a is an oxopyridyl moiety (A 14 , A 24 and A 34 is CH, i.e., R 4a is that of embodiment DD). In an embodiment of each aspect of the present invention, R 4a has an unsubstituted nitrogen atom in the second ortho position relative to the carbonyl group C=O. In this case, R 4a is an oxopyrimidinyl moiety (A 14 and A 24 is CH, and A 34 is N, i.e., R 4a is of embodiment CC), where the carbonyl group C=O is between the two nitrogen atoms of the ring. In an embodiment of each aspect of the invention, R 4a has one unsubstituted nitrogen atom meta to the carbonyl group C=O. In this case, R 4a is an oxopyrazinyl moiety (A14 and A 34 is CH and A 24 is N, i.e., R 4a is of embodiment BB), or an oxopyridazinyl moiety (A 14 is N and A 24 and A 34 is CH, i.e., R 4a is that of embodiment AA). In an embodiment of each aspect of the invention, R 4a is an oxopyridazinyl moiety (A 14 is N and A 24 and A 34 is CH, i.e., R 4a is that of embodiment AA). In an embodiment of each aspect of the invention, R 4b is an oxo-dihydro-pyridazinyl moiety (A 14 is N, i.e., R 4b is that of embodiment B). In an embodiment of each aspect of the present invention, R 4b is an oxo-dihydro-pyridyl moiety (A 14 is CH, i.e., R 4b is that of embodiment A).
[0063] In an embodiment of each aspect of the present invention, R 4c teeth A. C1-C3 alkyl, C1-C3 haloalkyl, allyl, propargyl, or C3-C6 cycloalkyl C1-C4 alkyl; or B. C1-C2 alkyl, C1-C2 haloalkyl, allyl, propargyl or C3-C4 cycloalkyl C1-C2 alkyl; or C. methyl, ethyl, difluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoromethyl, allyl, propargyl or cyclopropylmethyl; or D. methyl, ethyl, difluoromethyl, 2,2-difluoroethyl, allyl, propargyl or cyclopropylmethyl; or E. methyl, ethyl, allyl, propargyl or cyclopropylmethyl; or F. methyl or ethyl; or G. methyl or allyl; or H. methyl or propargyl; or I. methyl or cyclopropylmethyl; or J. Methyl is.
[0064] Q is Q a In an embodiment of each aspect of the present invention, R 5 teeth A. Hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, C3-C4 alkoxyC(O)-, (C1-C3 alkoxy)2CH-, halogen, CN, NHC(O), amino (i.e., NH), (C1-C3 alkyl)amino, di(C1-C3 alkyl)amino, hydroxy, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulf nyl, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl, (C1-C3 alkyl)sulfonylamino, (C1-C3 alkyl)sulfonyl(C1-C3 alkyl)amino, (C1-C3 alkyl)NHC(O), (C1-C3 alkyl)NC(O), (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, (C1-C3 alkyl)C(O), (C1-C3 alkoxy)C(O), HC(O), diphenylmethanimine, C1-C3 haloalkoxy, phenyl or a 5-membered aromatic heterocycle; or R 5is phenyl substituted with 1 to 3 substituents selected from C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, CN, and hydroxyl; or R 5 is a 5-membered aromatic heterocycle substituted with 1 to 3 substituents selected from C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, CN, and hydroxyl; or B. hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, halogen, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl, (C1-C3 alkyl)C(O), (C1-C3 alkoxy)C(O), HC(O), C1-C3 haloalkoxy, or a 5-membered aromatic heterocycle, wherein the 5-membered aromatic heterocycle can be optionally substituted with 1 to 3 substituents selected from C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, CN, or hydroxy; or C. hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, halogen, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl, (C1-C3 alkyl)C(O), (C1-C3 alkoxy)C(O), HC(O), or C1-C3 haloalkoxy; or D. hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, halogen, Cl, Br, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl, (C1-C3 alkyl)C(O), (C1-C3 alkoxy)C(O) or C1-C2 haloalkoxy; or E. hydrogen, C1-C3 alkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, C1-C3 haloalkoxy, halogen, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl, (C1-C3 alkyl)C(O), HC(O) or (C1-C3 alkoxy)C(O); or F. hydrogen, C1-C2 alkyl, C1-C2 alkoxy, C3-C4 cycloalkyl, C1-C2 haloalkoxy, halogen, C1-C2 alkoxy-C1-C2 alkyl, C1-C2 alkoxy-C1-C2 alkoxy-C1-C2 alkyl, (C1-C2 alkyl)C(O), HC(O) or (C1-C2 alkoxy)C(O); or G. hydrogen, methyl, trifluoromethoxy, methoxy, cyclopropyl, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, difluoromethoxy, 2,2,2-trifluoroethyl, chloro, bromo, methoxyethoxy, methylcarbonyl or methoxycarbonyl; or H. hydrogen, methyl, trifluoromethoxy, methoxy, cyclopropyl, difluoromethoxy, chloro, bromo, methoxyethoxy, methylcarbonyl or methoxycarbonyl; or I. hydrogen, methyl, methoxy, cyclopropyl, chloro or methoxyethoxy; or J. hydrogen or methyl; or K. Hydrogen.
[0065] Q is Q b In an embodiment of each aspect of the present invention, R 5a teeth A. hydrogen, halogen, CN, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy or C1-C3 haloalkoxy; or B. hydrogen, halogen, CN, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl or C1-C3 alkoxy; or C. hydrogen, halogen, CN, C1-C3 alkyl, C1-C3 haloalkyl or C1-C3 alkoxy; or D. hydrogen, halogen, CN, C1-C3 alkyl or C1-C3 alkoxy; or E. Hydrogen or halogen; or F. Hydrogen is.
[0066] Q is Q b In an embodiment of each aspect of the present invention, R 5b teeth A. hydrogen, halogen, CN, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy or C1-C3 haloalkoxy; or B. hydrogen, halogen, or C1-C3 alkoxy; or C. Hydrogen is.
[0067] In an embodiment of each aspect of the present invention, R 6 teeth A. phenyl, benzyl, heteroaryl, or C3-C6 cycloalkyl, each of which is independently R X or BR X phenyl, benzyl, cyclopropyl or cyclopropyl substituted with one substituent selected from is.
[0068] In an embodiment of each aspect of the present invention, R X teeth: A. halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, NO2, SF5, CN, —C(O)NH2, —C(S)NH2, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl and C1-C4 alkylsulfonyl; or B. halogen, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy or CN; or C: F, Cl, Br, OCF2H, OCH3 or CN are independently selected from
[0069] In an embodiment of each aspect of the present invention, R Y teeth: A. hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, hydroxy, C1-C3 alkoxy, C1-C3 haloalkoxy, halogen, CN, and cyclopropyl; or B. hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, halogen, CN, and cyclopropyl; or C. hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, cyclopropyl; or D. hydrogen, C1-C3 alkyl, chlorine, C1-C3 haloalkyl, and C1-C3 alkoxy; or E. hydrogen, methyl, trifluoromethyl and methoxy; or F. Hydrogen, chlorine, methyl; or G. Chlorine, Hydrogen are independently selected from
[0070] In an embodiment of each aspect of the present invention, R Z teeth: A. oxo, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, and CN; or B. oxo, halogen, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy or CN; or C. Oxo, F, Cl, Br, OCF2H, OCH3 or CN are independently selected from
[0071] The present invention therefore provides a compound having the substituent A as defined above. 1 , A 2 , A 3 , A 4 , A 5 , X 0 , Q a , Q b , R, R 1 , R 2a , R2b , R 3 , R 4c , R 5 , R 5a , R 5b , R 6 , R X , R Y and R Z in all combinations / orders of the formula (I).
[0072] Thus, compounds of formula (I) may be, for example, A containing embodiment S 1 , A 2 and A 3 (i.e., A 1 =A 2 -A 3 are collectively NR-C(=O)-N), A of embodiment E 4 and A 5 (i.e., A 4 and A 5 are both CH), R of embodiment B (i.e., R is hydrogen, methyl, ethyl, difluoroethyl, or trifluoroethyl), R of embodiment I 1 (i.e., R 1 is hydrogen, methyl or cyclopropyl-methyl), R of embodiment M 2a (i.e., R 2a is halogen or C1-C3 haloalkyl), R in embodiment O 2a (i.e., R 2a R of embodiment E is fluorine, chlorine, bromine or trifluoromethyl. 2b (i.e., R 2b is chlorine, fluorine, bromine, difluoromethyl or trifluoromethyl), R of embodiment B 3 (i.e., R 3 is methyl or trifluoromethyl), Q of embodiment C (i.e., Q is R 4 R 4a Q a where Q a is of embodiment H (i.e., Q a Q A -1 or Q A -15), R 4ais of embodiment I (i.e., A 14 is N or CH, and A 24 is CH, and A 34 is N or CH), R of embodiment G 4c (i.e., R 4c is methyl or allyl)).
[0073] Compounds of formula (I) can also be used, for example, as A in embodiment J 1 , A 2 and A 3 (i.e., A 1 and A 3 is N, and A 2 is CR Y ), R of embodiment F Y (i.e., R Y is hydrogen, chlorine, methyl), A of embodiment E 4 and A 5 (i.e., A 4 and A 5 and R of embodiment F are both CH. 1 (i.e., R 1 is hydrogen, C1-C3 alkyl, C1-C3 cyanoalkyl, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C3-C4 cycloalkylC1-C2 alkyl-, benzyloxycarbonyl, or benzyl), R in embodiment M 2a (i.e., R 2a is halogen or C1-C3 haloalkyl. 2b (i.e., R 2b is halogen, C1-C3 haloalkyl, or C1-C3 haloalkoxy), R in embodiment C 3 (i.e., R 3 is methyl), Q of embodiment C (i.e., Q is R 4 R 4a Q a where Q a Q A -1 and R 4ais of embodiment AA (i.e., A 14 is N and A 24 is CH, and A 34 is CH), R of embodiment I 4c (i.e., R 4c is methyl or cyclopropylmethyl)).
[0074] The compounds of formula (I) can also be used, for example, as A in embodiment C. 1 , A 2 and A 3 (i.e., A 1 and A 3 is N, and A 2 is CR Y or A 1 =A 2 -A 3 are collectively NR-C(=O)-N), R of embodiment G Y (i.e., R Y is hydrogen or chlorine) and R of embodiment G (i.e., R is methyl or hydrogen), A of embodiment E 4 and A 5 (i.e., A 4 and A 5 and R of embodiment J are both CH. 1 (i.e., R 1 is hydrogen or methyl); R in embodiment R 2a (i.e., R 2a is chlorine, bromine, iodine or trifluoromethyl), R of embodiment I 2b (i.e., R 2b is chlorine, bromine, iodine or trifluoromethyl), R in embodiment C 3 (i.e., R 3 is methyl), Q in embodiment B (i.e., Q is R 4 R 4a or R 4b Q a where Q a Q A -1 and R 4a is of embodiment AA (i.e., A 14 is N and A 24is CH, and A 34 is CH), R 4b is of embodiment B (i.e., A 14 is N), and R of embodiment F 4c (i.e., R 4c is methyl or ethyl).
[0075] In one embodiment, the compound of formula (I) has the formula (I * ), (I * ), (I *c ), (I *d ), (I *e ) or (I *f ) (the asterisk indicates a stereogenic center), where A 1 , A 2 , A 3 , A 4 , A 5 , R, R 1 , R 2a , R 2b , R 3 , R 4c , R 5 , R 5a , R 5b , and R Y are as defined in the first aspect, each having the corresponding embodiments described above. [ka]
[0076] In one embodiment, the compound having the preferred stereochemistry shown in formula (I') is *a ), (I *b ), (I *c ), (I *d ), (I *e ) or (I *f In a preferred embodiment, a compound of formula (I') having the following stereochemistry is also preferred: a ), (I' b ), (I' c ), (I' d ), (I' e ) or (I' f) compounds: [ka] (In the formula, A 1 , A 2 , A 3 , A 4 , A 5 , R, R 1 , R 2a , R 2b , R 3 , R 4c , R 5 , R 5a , R 5b , and R Y is as defined in the first aspect), and a compound of formula (I' a ), (I' b ), (I' c ), (I' d ), (I' e ) or (I' f Preferred are the stereoisomers, enantiomers, tautomers and N-oxides of the compounds of formula (I) and agrochemically acceptable salts thereof.
[0077] The compounds of formula (I) can be prepared by those skilled in the art according to known methods. More specifically, the compounds of formula (I), formula (I'), and intermediates thereof can be prepared as described below in the schemes and examples. Certain stereogenic centers have been left unidentified for the sake of brevity and are not intended to limit the teachings of the schemes in any way.
[0078] The process according to the invention for preparing compounds of formula (I) is carried out by methods known to those skilled in the art.
[0079] Compounds of formula (I) [ka] (In the formula, A 1 , A 2 , A 3 , A 4 , A 5 , R 1 , R 3 , Q, R2a and R 2b has the same meaning as above for compounds of formula (I)) is an amine of formula (III) [ka] or a salt thereof (such as a hydrohalide, preferably a hydrochloride or hydrobromide, or a trifluoroacetate, or any other equivalent salt), where R 1 , R 3 and Q have the same meaning as above for compounds of formula (I)) and compounds of formula (II) [ka] (In the formula, A 1 , A 2 , A 3 , A 4 , A 5 , R 2a and R 2b has the same meaning as above for compounds of formula (I), and X 1 is a leaving group such as halogen, hydroxy or sulfonate).
[0080] Throughout this specification, for example, in the following Schemes 1 to 11, or Tables A-1 to A-78, B-1 to B-78, C-1 to C-21, and D-1 to D-21, T is [ka] where A 1 , A 2 , A 3 , A 4 , A 5 , R 2a and R 2b has the same meaning as above for compounds of formula (I), and the wavy line represents a bond to the remainder of a compound, such as a compound of formula (I), (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (II), (IV), (IVa), (X), (XI), (XVII) in Schemes 1-11.
[0081] Scheme 1: [ka] The compound of formula (I) can be prepared, for example, by the reaction of a compound of formula (II) 1 is a leaving group such as halogen, hydroxy or sulfonate, e.g. chloride, and T has the above meaning) with a compound of formula (III) or a salt thereof, wherein R 1 , R 3 and Q have the same meaning as above for compounds of formula (I). 1 When is hydroxy, it may be advantageous to carry out the reaction in the presence of a dehydrating reagent, for example, a peptide coupling reagent, such as, for example, a carbodiimide or propanephosphonic acid cyclic anhydride (T3P®). Such reactions can be carried out solvent-free or in a solvent, preferably an organic solvent such as, for example, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N-dimethylacetamide, or N,N-dimethylformamide, at a temperature in the range of −100 to +300° C., preferably ambient temperature to 200° C., with or without the addition of a catalyst, for example, a metal catalyst such as a palladium complex, and with or without the addition of a base, for example, an inorganic base such as, for example, sodium carbonate, potassium carbonate, or cesium carbonate, or an organic base such as, for example, triethylamine, diisopropylethylamine, or pyridine. Compounds of formula (II) are known or can be prepared analogously to the descriptions found, for example, in WO 2021 / 083936 and WO 2021 / 177160, or they can be prepared by methods known to those skilled in the art.
[0082] Scheme 2: [ka] Compounds of formula (III) or salts thereof can be prepared, for example, as shown in Scheme 2. Compounds of formula (V) (wherein R 3and Q have the same meaning as above for compounds of formula (I), and X 2 is a leaving group such as a halogen or sulfonate, e.g. bromide), an amine of formula (XIX) or a salt thereof, wherein R 1 have the same meaning as above for compounds of formula I), to give compounds of formula (III) 1 and R 3 has the same meaning as above for compounds of formula I. This reaction can be carried out solvent-free or in a solvent, preferably an organic solvent such as acetonitrile, at a temperature range of −100 to +300° C., preferably ambient temperature to 200° C., with or without the addition of a base, such as an inorganic base, such as potassium carbonate, or an organic base, such as triethylamine.
[0083] Alternatively, a compound of formula (VII) 3 and Q have the same meaning as above for the compounds of formula (I), or a salt thereof of formula (XIX) (wherein R 1 have the same meaning as above for compounds of formula I), to give compounds of formula (III) 1 and R 3has the same meaning as above for compounds of formula I). This reaction is carried out 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, in the presence or absence of an acid, such as acetic acid or a Lewis acid, such as zinc bromide or titanium(IV) isopropoxide, in a solvent, such as methanol, or without a solvent. This reaction can be carried out in a temperature range of −100 to +300° C., preferably ambient to 200° C. Such methods, including amine alkylation and reductive alkylation of amines (e.g., in the presence of NaBH(OAc) or NaBHCN, preferably in a suitable solvent, such as acetic acid, at room temperature, as in WO 2002 / 088073; or alternatively, by using a combination of Ti(i-OiPr) and NaBH as described in Synthesis 2003(14), 2206), and the range of conditions for carrying them out, are well known to those skilled in the art. An amine of formula (XIX) or a salt thereof (wherein R 1 has the same meaning as above for compounds of formula (I)) are known or they can be prepared by methods known to those skilled in the art.
[0084] Scheme 3: [ka] Alternatively, a compound of formula (I) can be prepared, for example, by reacting a compound of formula (IV) where T has the same meaning as above in Scheme 1 and R 1 has the same meaning as above for compounds of formula (I)) and compounds of formula (V) 3 and Q have the same meaning as above for compounds of formula (I), and X 2is a leaving group such as a halogen or sulfonate, e.g., chloride or bromide). The reaction can be carried out solvent-free or in a solvent, preferably an organic solvent such as acetonitrile, at a temperature range of −100 to +300° C., preferably ambient temperature to 200° C., with or without the addition of a base, e.g., an inorganic base, e.g., potassium carbonate, or an organic base, e.g., triethylamine. Such methods for the alkylation of amines, and the range of conditions for carrying them out, are well known to those skilled in the art.
[0085] Alternatively, the compound of formula (I) can be prepared by reacting a compound of formula (IVa) (wherein T has the same meaning as above in Scheme 1) with a compound of formula (VII) (wherein R 3 and Q have the same meaning as above for compounds of formula (I). This reaction is carried out 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, e.g., palladium on carbon, in the presence or absence of an acid such as acetic acid or a Lewis acid such as zinc bromide, in a solvent such as methanol or without a solvent. The reaction can be carried out in a temperature range of -100 to +300°C, preferably ambient to 200°C. Such methods for the reductive alkylation of amines and the range of conditions for carrying them out are well known to those skilled in the art.
[0086] Scheme 4: [ka] Compounds of formula (V) can be prepared, for example, as shown in Scheme 4. Treatment of compounds of formula (VIII) with a halogenating agent such as chlorine or bromine, or N-bromosuccinimide, for example, gives compounds of formula (V) (wherein the leaving group X 2is a halogen, such as chloride or bromide, to give a hydroxy group. The reaction may be carried out with or without a solvent, preferably in a solvent, with or without an additive, such as a radical initiator, for example, benzoyl peroxide or isoisobutyronitrile. The reaction may be carried out with or without exposure to visible or UV light, and may be carried out at temperatures ranging from -100 to +300°C, preferably ambient to 200°C.
[0087] Alternatively, compounds of formula (VII) can be treated with a reducing agent followed by reaction with a sulfonyl chloride, for example methanesulfonyl chloride, to give compounds of formula (V) (wherein the leaving group X 2 is a sulfonate, e.g., mesylate). This reaction can be carried out in a solvent or without a solvent, in the presence of a base, such as an inorganic base, e.g., potassium carbonate, or an organic base, e.g., an amine base, e.g., trimethylamine, or in the absence of a base, and can be carried out at a temperature ranging from -100 to +300°C, preferably ambient temperature to 200°C. Suitable reducing agents can be, for example, hydrogen or hydrides, e.g., sodium borohydride, in a solvent, e.g., methanol, or without a solvent, in the presence or absence of an acid, e.g., acetic acid or a Lewis acid, e.g., zinc bromide, with or without a catalyst, e.g., a hydrogenation catalyst, e.g., palladium on carbon. This reaction can be carried out at a temperature ranging from -100 to +300°C, preferably ambient temperature to 200°C. Such methods for halogenation, reduction of carbonyl compounds, and sulfonylation of alcohols, as well as the range of conditions for carrying them out, are well known to those skilled in the art. Compounds of formula (VII) and compounds of formula (VIII) are known or they can be prepared by methods known to those skilled in the art.
[0088] Scheme 5: [ka] Alternatively, a compound of formula (Ib) wherein T has the same meaning as above in Scheme 1 and R 1 , R3 and Q have the same meanings as above for compounds of formula (I), except that R 1 is different from hydrogen) can be prepared, for example, as shown in Scheme 5. Compounds of formula (Ia) (wherein T has the same meaning as above in Scheme 1 and R 3 and Q have the same meaning as above for compounds of formula (I) can be prepared by reacting a compound of formula (VI) 1 has the same meaning as above for compounds of formula (I), except that R 1 is different from hydrogen, and X 3 is a leaving group such as a halogen or sulfonate, e.g., chloride, bromide, iodide, or mesylate, to provide a compound of formula (Ib). This reaction can be carried out neat or in a solvent, preferably an organic solvent such as acetonitrile, N,N-dimethylformamide (DMF), or N,N-dimethylacetamide (DMF), or mixtures thereof, at a temperature ranging from −100 to +300° C., preferably ambient temperature to 200° C., with or without the addition of a base, e.g., an inorganic base such as sodium carbonate, potassium carbonate, or cesium carbonate, or an organic base such as triethylamine, diisopropylethylamine, or pyridine. Such methods for alkylating amines and the range of conditions for carrying them out are well known to those skilled in the art.
[0089] A compound of formula (VI) 1 has the same meaning as above for compounds of formula (I), except that R 1 is different from hydrogen, and X 3 is a leaving group such as a halogen or sulfonate, e.g., chloride, bromide, iodide or mesylate) are known or can be prepared by methods known to those skilled in the art.
[0090] Scheme 6: [ka] Compounds of formula (Ic), wherein T has the same meaning as above in Scheme 1, and R 3 and R 4 Compounds of formula (II), where T has the same meaning as above for compounds of formula (I), can be prepared, for example, as shown in Scheme 6. Compounds of formula (II), where X has the same meaning as above for compounds of formula (I), can be prepared, for example, as shown in Scheme 6. 1 is a leaving group such as a halogen or sulfonate, e.g., chloride) with a compound of formula (IX) or a salt thereof, wherein R 3 has the same meaning as above for compounds of formula (I) to give compounds of formula (X) (wherein T has the same meaning as above for Scheme 1 and R 3 has the same meaning as above for compounds of formula (I). This reaction can be carried out solventlessly or in a solvent, preferably an organic solvent such as acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, N,N-dimethylacetamide or N,N-dimethylformamide, at a temperature in the range of −100 to +300° C., preferably ambient temperature to 200° C., in the presence or absence of a catalyst, for example a metal catalyst such as a palladium complex, and with or without the addition of a base, for example an inorganic base such as sodium carbonate, potassium carbonate or cesium carbonate, or an organic base such as triethylamine, diisopropylethylamine or pyridine.
[0091] Compounds of formula (X) (where T has the same meaning as above in Scheme 1 and R 3 has the same meaning as above for compounds of formula (I)) to give compounds of formula (XI) 3has the same meaning as above for compounds of formula (I). This reaction can be carried out solventlessly or in a solvent, preferably an organic solvent such as dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran or dioxane, at a temperature in the range of −100 to +300° C., preferably ambient temperature to 100° C. or ambient temperature to 50° C., either without a base or in the presence of a base, such as an inorganic base, for example sodium carbonate, potassium carbonate or cesium carbonate, or an organic base, for example triethylamine, diisopropylethylamine or pyridine.
[0092] Compounds of formula (XI) where T has the same meaning as above in Scheme 1 and R 3 has the same meaning as above for the compound of formula (I)) and a hydrazine compound of formula (XII) or a tautomer thereof or a salt thereof (wherein R 4 has the same meaning as above for compounds of formula (I), preferably R 4 is defined above for compounds of formula (I), 4a and R 3 and R 4 has the same meaning as above for compounds of formula (I), preferably R 4 is defined above for compounds of formula (I), 4a The reaction can be carried out solventlessly or in a solvent, preferably an organic solvent such as 1,4-dioxane or acetic acid, or a mixture of 1,4-dioxane and acetic acid, at a temperature ranging from −100 to +300° C., preferably from ambient temperature to 200° C., or from ambient temperature to 80° C. In this conversion sequence, the intermediate compounds of formula (X) and formula (XI) can be used as crude products for the subsequent step, or they can be purified, for example by chromatography, and used in purified form in the next conversion.
[0093] A compound of formula (IX) or a salt thereof (wherein R 3 has the same meaning as above for compounds of formula (I)) are known or they can be prepared by methods known to those skilled in the art.
[0094] Compound of formula (Ii) [ka] (In the formula, A 1 , A 2 , A 3 , A 4 , A 5 , R 1 , R 3 , R 4 , R 5 , R 2a and R 2b has the same meaning as above for compounds of formula (I)) can be reacted with an amine of formula (IIIa) or a salt thereof (such as a hydrohalide, preferably a hydrochloride or a hydrobromide, or a trifluoroacetate, or any other equivalent salt) under the conditions already described in Scheme 1. [ka] (In the formula, R 1 , R 3 , R 4 and R 5 is as described in formula (I)) and a compound of formula (II) [ka] (In the formula, A 1 , A 2 , A 3 , A 4 , A 5 , R 2a and R 2b is as described in formula (I), and X 1 can be prepared by reaction with a leaving group such as a halogen or sulfonate, e.g., chloride.
[0095] Scheme 7: [ka] Compounds of formula (Ie) wherein T has the same meaning as above in Scheme 1 and R 1 , R 3 , R 4c and R 5 has the same meaning as above for compounds of formula (I) to prepare compounds of formula (Id) 1 , R 3 , R 4c and R 5 (has the same meaning as above for compounds of formula (I)) can be prepared by hydrogenation (Scheme 7). This reaction can be carried out in the presence of hydrogen or by transfer hydrogenation, for example in the presence of formic acid or a formate. This reaction can be carried out in the presence of a catalyst, for example a homogeneous or heterogeneous catalyst. For example, this reaction is carried out in the presence of a palladium catalyst, such as palladium on carbon. This reaction can be advantageously carried out in a solvent or without a solvent, preferably in a solvent such as methanol or ethanol. This reaction can be carried out in a temperature range of -100 to +300°C, preferably ambient temperature to 200°C, or ambient temperature to 80°C, optionally in a pressure vessel.
[0096] Scheme 7a: [ka] Similarly, compounds of formula (Ih) wherein T has the same meaning as above in Scheme 1 and R 1 , R 3 , R 4c , R 5a and R 5b has the same meaning as above for compounds of formula (I) to prepare compounds of formula (Ig) 1 , R 3 , R 4c , R 5a and R5b has the same meaning as above for compounds of formula (I) by hydrogenation under conditions similar to those described in Scheme 7 (Scheme 7a).
[0097] Scheme 8: [ka] Compounds of formula (XII-1), which are a subset of compounds of formula (XII), 4 is specifically R 4a or a salt thereof (such as a hydrohalide, preferably a hydrochloride or hydrobromide, or a trifluoroacetate, or any other equivalent salt) (wherein A 14 , A 24 , A 34 and R 4c has the same meaning as defined above for compounds of formula (I), can be used to prepare compounds of formula (XV) 14 , A 24 , A 34 and R 4c has the same meaning as defined above for compounds of formula (I), and X 4 can be prepared by treatment of a compound of formula (XV) with hydrazine or hydrazine hydrate or a salt thereof (wherein A is a leaving group such as a halogen, sulfonate, C1-C4-sulfanyl, C1-C4-sulfinyl or C1-C4-sulfonyl) (Scheme 8). The reaction can be carried out neat or in a solvent such as water, an alcohol such as methanol or ethanol, or methoxycyclopentane, at temperatures between -100°C and 200°C, more usually between 0°C and 150°C, for example 100°C. Such reactions are known from the literature, for example Bioorganic & Medicinal Chemistry Letters (2012), 22(2), 1226-1229. Many compounds of formula (XV) are known, or even commercially available, or can be prepared by known methods. In particular, compounds of formula (XV) (wherein A 14 , A 24 , A 34and R 4c has the same meaning as defined above for compounds of formula (I), and X 4 is a leaving group such as, for example, halogen, sulfonate, C1-C4-sulfanyl, C1-C4-sulfinyl or C1-C4-sulfonyl) to form a compound of formula (XVa) or a tautomer thereof, 14 , A 24 and A 34 has the same meaning as defined above for compounds of formula (I), and X 4 is a leaving group such as, for example, halogen, sulfonate, C1-C4-sulfanyl, C1-C4-sulfinyl or C1-C4-sulfonyl), 4c -X 6 Reagent (wherein R 4c has the same meaning as defined above for compounds of formula (I), and X 6 can be prepared by treatment with a leaving group such as a halogen or sulfonate, e.g., chloride, bromide, iodide, or mesylate. This reaction can be carried out solvent-free or in a solvent, preferably an organic solvent such as acetonitrile, N,N-dimethylformamide (DMF), or N,N-dimethylacetamide (DMA), or mixtures thereof, at a temperature range of −100 to +300° C., preferably ambient temperature to 200° C., with or without the addition of a base, e.g., an inorganic base such as sodium carbonate, potassium carbonate, or cesium carbonate, or an organic base such as triethylamine, diisopropylethylamine, or pyridine. Such alkylation methods and the range of conditions for carrying them out are well known to those skilled in the art and are described, for example, in Bioorganic & Medicinal Chemistry Letters (2012), 22(2), 1226-1229. Formula R 4c -X 6 and compounds of formula (XVa) or their tautomers are known or even commercially available, or they can be prepared by known methods.
[0098] Compounds of formula (XIIa), which are a subset of compounds of formula (XII-1), 14 is N) or a salt thereof (wherein A 24 , A 34 and R 4c has the same meaning as defined above for compounds of formula (I)) is (XIIb) and / or (XIIc) [ka] or salts thereof (wherein A 24 , A 34 and R 4c has the same meaning as defined above for compounds of formula (I).
[0099] The present invention covers all such tautomers and mixtures thereof in all proportions.
[0100] Scheme 9: [ka] A compound of formula (XVI) 14 , A 24 , A 34 and R 4c has the same meaning as defined above for compounds of formula (I), and M 1 is a metal-containing substituent, such as a boron substituent or a tin substituent, such as tributylstannyl (M 1 -SnBu3), Borono (M 1 is -B(OH)2), or a boronate such as 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl, to give a compound of formula (XV) 14 , A 24 , A 34 and R 4c has the same meaning as defined above for compounds of formula (I), and X 4can be prepared by treatment of 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2-dioxaborolane (a leaving group such as halogen, sulfonate, C1-C4-sulfanyl, C1-C4-sulfinyl, or C1-C4-sulfonyl) with tributyl(tributylstannyl)stannane, hypoboric acid, or 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)diboron) (Scheme 9). This reaction can be carried out in the presence of a catalyst, such as a metal catalyst, for example, a palladium catalyst, e.g., palladium acetate, and a phosphine ligand, such as 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos). This reaction can be carried out in the presence of a base, such as an alkoxide or carboxylate base, for example, potassium acetate. The reaction can be carried out neat or in a solvent such as, for example, dioxane or toluene as solvent, at temperatures between −100° C. and 200° C., more usually between 0° C. and 150° C., such as 100° C. Some compounds of formula (XVI) are known, or even commercially available, or they can be prepared by known methods.
[0101] Scheme 10: [ka] Compounds of formula (If) wherein T has the same meaning as above in Scheme 1 and A 14 , A 24 , A 34 , R 1 , R 3 , R 4c , R 5a and R 5b has the same meaning as above for compounds of formula (I)) to a compound of formula (XVII) 1 , R 3 , R 5a and R 5b has the same meaning as above for compounds of formula (I), and wherein X5 is a leaving group such as, for example, chlorine, bromine or iodine) to a compound of formula (XVI) 14 , A 24 , A 34 and R 4c has the same meaning as defined above for compounds of formula (I), and M 1 is a metal-containing substituent having the same meaning as above in Scheme 9 (Scheme 10). This reaction can be carried out in the presence of a catalyst, such as a palladium catalyst, for example, 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride (PdCl2dppf), in the presence of a base, such as a carbonate base, for example, CS2CO3, or a carboxylate base, for example, potassium acetate. This reaction can be carried out solvent-free or in a solvent, for example, dioxane, at temperatures between -100°C and 200°C, more typically 0°C and 150°C, for example, 85°C. Such reactions, known as Suzuki-Miyaura or Stille cross-coupling reactions, are well known to those skilled in the art.
[0102] Compounds of formula (XVII) where T has the same meaning as above in Scheme 1 and R 1 , R 3 , R 5a and R 5b has the same meaning as above for compounds of formula (I), and X 5 is a leaving group such as, for example, chlorine, bromine or iodine) can be reacted with a compound of formula (XVIIa) or a salt thereof, wherein R 1 , R 3 , R 5a and R 5b has the same meaning as above for compounds of formula (I), and X 5 is a leaving group such as, for example, chlorine, bromine or iodine) to a compound of formula (II) 1is a leaving group such as a halogen or sulfonate, e.g., chloride) under conditions similar to those already described above in Scheme 1.
[0103] A compound of formula (XVIIa) or a salt thereof, wherein T has the same meaning as above in Scheme 1, and R 1 , R 3 , R 5a and R 5b has the same meaning as above for compounds of formula (I), and X 5 is a leaving group such as, for example, chlorine, bromine or iodine) are known from documents such as, for example, WO 2021 / 170881, WO 2021 / 037614, WO 2020 / 208036, WO 2020 / 201398 or WO 2020 / 070049 or can be prepared analogously to the descriptions found in these documents.
[0104] Scheme 11: [ka] A compound of formula (XXII) 3 and R 4a is as defined for compounds of formula (I)) can be prepared by reacting a compound of formula (XX) 3 and R 4a is as defined for compounds of formula (I), and X - is an anion), for example, by treatment with a hydroxide or carbonate base, such as sodium hydroxide or potassium carbonate, or with an ion exchange resin (Scheme 11). Such techniques are well known to those skilled in the art and are available from the literature and textbooks.
[0105] Anion X -is the conjugate base of an acid such as an inorganic acid, e.g., hydrochloric acid, hydrobromic acid, hydrogen fluoride, hydrogen iodide, sulfuric acid, etc., or an organic acid, e.g., a carboxylic acid or a sulfonic acid, e.g., trifluoroacetic acid, or methanesulfonic acid, or p-toluenesulfonic acid. Many such acids are known to those skilled in the art.
[0106] A compound of formula (XX) 3 and R 4a is as defined for compounds of formula (I) and X is an anion) can be prepared by reacting a compound of formula (XXI) 3 and R 4a (wherein R is as defined for compounds of formula (I)) can be prepared by treatment with an acid such as those listed above. The reaction can be carried out neat or in a solvent such as an organic solvent such as methanol, CPME, tetrahydrofuran, 2-methyltetrahydrofuran, dichloromethane, or dioxane, or an inorganic solvent such as water, or a mixture of such solvents. The reaction can be carried out at a temperature range of -100°C to 200°C, more usually 0°C to 150°C, such as ambient temperature.
[0107] A compound of formula (XXI) 3 and R 4a is as defined in the compound of formula (I)) can be obtained, for example, by the compound of formula (XII-1) or a tautomer thereof or a salt thereof (wherein R 4a is as defined for compounds of formula (I)) to a compound of formula (XVIII) 3 can be prepared by treatment with a compound of formula (XVIII) (wherein R is as defined for the compound of formula (I)). The reaction can be carried out solvent-free or in a solvent, such as an organic solvent, or in a mixture of solvents such as dioxane and acetic acid as solvent. The reaction can be carried out in the presence or absence of a drying agent, such as in the presence of molecular sieves, at temperatures between -100°C and 200°C, more typically between 0°C and 150°C, such as 80°C. Compounds of formula (XVIII) (wherein R 3are as defined for compounds of formula (I)) are known, for example from WO 2021 / 083936 or WO 2021 / 165195, or can be prepared analogously to the descriptions found in these documents.
[0108] Scheme 12: [ka] Compounds of formula (XX-1), which are a subset of compounds of formula (XX), 3 and R 4c has the same meaning as defined above for compounds of formula (I), and X - is an anion having the same meaning as above in Scheme 11) can be obtained by the compound of formula (XXI-1), which is a subset of the compound of formula (XXI), 3 and R 4c has the same meaning as defined above for compounds of formula (I)) by treatment with acid under the conditions already described above in Scheme 11 (conversion of XXI to XX) (Scheme 12).
[0109] Compounds of formula (XXI-1), which are a subset of compounds of formula (XXI), 3 and R 4c has the same meaning as defined above for compounds of formula (I)) can be converted to a compound of formula (XXIII) or a tautomer thereof (wherein R 3 has the same meaning as defined above for compounds of formula (I), 4c -X 6 Reagent (wherein R 4c has the same meaning as defined above for compounds of formula (I), and X 6 can be prepared by treatment with a leaving group such as a halogen or sulfonate, for example chloride, bromide, iodide or mesylate.
[0110] A compound of formula (XXIII) or a tautomer thereof (wherein R 3 has the same meaning as defined above for compounds of formula (I), can be obtained by reacting a compound of formula (XXIV) (wherein R 3 has the same meaning as defined above for compounds of formula (I), and X 7 can be prepared by treatment of a leaving group such as a halogen, for example chloride, bromide or iodide) with, for example, a benzaldoxime PhC=NOH, preferably (E)-benzaldehyde oxime.
[0111] A compound of formula (XXIV) 3 has the same meaning as defined above for compounds of formula (I), and X 7 is a leaving group such as halogen, e.g., chloride, bromide, or iodide) can be converted to a compound of formula (XXV) or a tautomer thereof or a salt thereof (wherein X is a leaving group such as halogen, e.g., chloride, bromide, or iodide) under conditions similar to those already described above in Scheme 11 (conversion of XII-1+XVIII to XXI). 7 is a leaving group such as halogen, for example chloride, bromide or iodide), 3 can be prepared by treatment with a compound of formula (XXV) or a tautomer or a salt thereof (wherein X is as defined for the compound of formula (I)). 7is a leaving group such as a halogen, for example chloride, bromide or iodide) are known or even commercially available, or they can be prepared by known methods.
[0112] Compounds of formula (XXIII) (all substituents are as defined above in Scheme 12) may exist in different tautomeric forms: [ka] where the wavy line represents the bond to the remainder of the compound of formula (XXIII) The present invention covers all such tautomers and mixtures thereof in all proportions.
[0113] Scheme 13: [ka] Compounds of formula (XXVII) 3 and R 4c has the same meaning as defined above for compounds of formula (I), and X - is an anion having the same meaning as above in Scheme 11) can be reacted with a compound of formula (XXVI), 3 and R 4c has the same meaning as defined above for compounds of formula (I)) by treatment with acid under the conditions already described above in Scheme 11 (conversion of XXI to XX) (Scheme 13).
[0114] A compound of formula (XXVI) 3 and R 4c has the same meaning as defined above for the compound of formula (I)) can be obtained by reacting the compound of formula (XXI-I) above (wherein R 3 and R 4c has the same meaning as defined above for compounds of formula (I)) by hydrogenation under conditions similar to those already described in Scheme 7 above.
[0115] Scheme 14: [ka] Compounds of formula (XXVIII) or salts thereof (such as hydrohalides, preferably hydrochlorides or hydrobromides, or trifluoroacetates, or any other equivalent salts) (wherein R 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I), compounds of formula (VII-1) (wherein R 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I)) by a reductive amination reaction under conditions similar to those already described above in Scheme 2 (conversion of VII to III) (Scheme 14).
[0116] Compounds of formula (VII-1), which are a subset of compounds of formula (VII), 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I) to give compounds of formula (XXIX) (wherein R 3 , R 5a and R 5b has the same meaning as defined above for compounds of formula (I), and wherein X 8 is a leaving group such as halogen, for example chloride, bromide or iodide), compounds of formula (XVI-1) (wherein R 4c has the same meaning as defined above for compounds of formula (I), and M 1is a metal-containing substituent having the same meaning as above in Scheme 9. Compounds of formula (XXIX), where R 3 , R 5a and R 5b has the same meaning as defined above for compounds of formula (I), and wherein X 8 is a leaving group such as a halogen, for example chloride, bromide or iodide) are known or even commercially available, or they can be prepared by known methods.
[0117] Alternatively, compounds of formula (VII-1), which are a subset of compounds of formula (VII), (wherein R 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I), can be converted to compounds of formula (XXXI) (Scheme 15), typically carried out using Dess-Martin periodinane (or a similar hypervalent iodine reagent) in a chlorinated solvent such as dichloromethane or chloroform at a temperature between 0 and 50°C, preferably at about room temperature: 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I).
[0118] Scheme 15: [ka] Alternatively, a compound of formula (XXVIII) or a salt thereof (such as a hydrohalide, preferably a hydrochloride or a hydrobromide, or a trifluoroacetate, or any other equivalent salt), wherein R 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I)) can be prepared by reacting a compound of formula (XXX) 3 , R 4c , R5a and R 5b has the same meaning as defined above for compounds of formula (I), and Z3 is -NPhth (N-phthalimido group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), which are typically known to those skilled in the art and can be found, 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 These can be prepared by treatment with hydrazine (preferably hydrazine hydrate or hydrazine monohydrate) in an alcoholic solvent such as ethanol or isopropanol (Z3 is -NPhth) under deprotection conditions described in the literature, such as (US Pat. No. 6,277,069; see also US Pat. No. 6,277,069), or with an acid such as trifluoroacetic acid or hydrochloric acid in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, or dioxane (Z3 is -NBoc2) (Scheme 15).
[0119] A compound of formula (XXX) 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I), and Z3 is -NPhth (N-phthalimido group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group)) is a group that can be used to prepare compounds of formula (XXXI), 3 , R 4c , R 5a and R 5bhas the same meaning as defined above for compounds of formula (I)) by the Mitsunobu reaction. Such a reaction involves treating a compound of formula (XXXI) with an azodicarboxylate, such as diethyl azodicarboxylate or diisopropyl azodicarboxylate, in the presence of a phosphine, such as triphenylphosphine or tributylphosphine, and in the presence of an amine, such as phthalimide (HNPhth) or bis(tert-butoxycarbonyl)amine (HNBoc2). Mitsunobu reactions (and conditions for carrying them out) are known to those skilled in the art and are described, for example, in Chem. Rev. 2009, 109, 2551-2651.
[0120] A compound of formula (XXXI) 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I)) can be reacted with silyl ether compounds of formula (XXXII) 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I), and wherein each group Ra is independently C1-C4 alkyl, can be prepared by deprotection, for example, by treatment with a fluoride, for example, tetrabutylammonium fluoride, in an inert solvent, for example, tetrahydrofuran or 2-methyltetrahydrofuran. The reaction can be carried out at a temperature ranging from -10°C to 80°C, for example, 0°C to 30°C. Such deprotection reactions are known to those skilled in the art and are described in literature, 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.
[0121] Alternatively, a compound of formula (XXXI) 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I), can be converted to a subset of compounds of formula (VII), compounds of formula (VII-1) above (Scheme 14), where R 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I).
[0122] A compound of formula (XXXII) 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I), and wherein each group Ra is independently C1-C4 alkyl, in the preparation of silyl ether compounds of formula (XXXIII), 3 , R 5a and R 5b has the same meaning as defined above for compounds of formula (I), and X 9is a leaving group, such as a halogen, e.g., bromide or iodide, and wherein each of the groups Ra is independently C1-C4 alkyl, can be prepared by metallation, such as treatment with a turbo-Grignard reagent (iPrMgCl·LiCl) or butyllithium. Such metallation is known to those skilled in the art and is described in literature, for example, Carey, Francis A. (2007). "Organometallic compounds of Group I and II metals". Advanced Organic Chemistry: Reaction and Synthesis Pt. B (Kindle ed.). Springer. ISBN 978-0-387-44899-2. The lithium or magnesium species thus generated can be transmetallated, for example, with a zinc halide, e.g., zinc chloride, to give compounds of formula (XV-1), which are a subset of compounds of formula (XV). 4c has the same meaning as defined above for compounds of formula (I), and X 4 is a leaving group such as a halogen, e.g., bromide or iodide), in the presence of a palladium catalyst, e.g., tris(dibenzylideneacetone)dipalladium(0), and a ligand, e.g., a phosphine ligand, e.g., tri(2-furyl)phosphine, in an inert solvent such as tetrahydrofuran or 2-methyltetrahydrofuran. This reaction can be carried out at a temperature ranging from −100° C. to 100° C., e.g., −78° C. to 80° C. This transformation is known to those skilled in the art as the Negishi coupling reaction, and is described in literature such as Jie Jack Li, Name Reactions, A Collection of Detailed Mechanisms and Synthetic Applications, Springer, ISBN: 978-3-030-50865-4.
[0123] A compound of formula (XXXIII) 3 , R 5a and R5b has the same meaning as defined above for compounds of formula (I), and X 9 is a leaving group, such as a halogen, for example bromide or iodide, and wherein each of the groups Ra is independently C1-C4 alkyl, to prepare a compound of formula (XXXIV), where R 3 , R 5a and R 5b has the same meaning as defined above for compounds of formula (I), and X 9 is a leaving group, such as a halogen, for example bromide or iodide, by treatment with a silylating agent of formula RaSi-Xa, where Xa is a leaving group, for example chloride, bromide, iodide, or triflate, and where each group Ra is independently C1-C4 alkyl (RaSi is trialkylsilyl, for example dimethyl-tert-butylsilyl; in compound RaSi-Xa, Ra is a linear or branched C1-C4 alkyl, such as methyl or tert-butyl), in the presence of an amine base, for example imidazole, in an inert solvent, for example tetrahydrofuran or 2-methyltetrahydrofuran. The reaction can be carried out at a temperature ranging from 0°C to 100°C, for example 10°C to 80°C. Such silylation reactions are known to those skilled in the art and are described in, for example, 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.
[0124] A compound of formula (XXXIV) 3 , R 5a and R 5b has the same meaning as defined above for compounds of formula (I), and X 9is a leaving group, such as a halogen, for example bromide or iodide, to give a compound of formula (XXXV), 5a and R 5b has the same meaning as defined above for compounds of formula (I), and X 9 is a leaving group, such as a halogen, for example bromide or iodide), by treatment with a base such as a lithium amide base, for example lithium 2,2,6,6-tetramethylpiperidide, followed by reaction of the lithiated species with an aldehyde compound of formula (XXXVI), where R 3 has the same meaning as above in formula (I). This reaction can be carried out without a solvent or in a solvent, for example, an organic solvent such as tetrahydrofuran or 2-methyltetrahydrofuran. This reaction can be carried out at a temperature range of -100°C to 100°C, for example, -80°C to 0°C, for example, 0°C or -78°C. A compound of formula (XXXV) (wherein R 5a and R 5b has the same meaning as defined above for compounds of formula (I), and X 9 is a leaving group, such as a halogen, for example bromide or iodide, and a compound of formula (XXXVI) 3 has the same meaning as above in formula (I)) are known or even commercially available, or they can be prepared by known methods.
[0125] Scheme 16: [ka] Compounds of formula (XXVIIIb) or salts thereof (such as hydrohalides, preferably hydrochlorides or hydrobromides, or trifluoroacetates, or any other equivalent salts) (wherein R 1 , R 3 , R 4c , R 5a and R 5bhas the same meaning as defined above for compounds of formula (I)) can be converted to compounds of formula (XXVIIIa) or salts thereof (wherein R 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I), 1 is as defined in Formula I) can be prepared by the process according to (Scheme 16).
[0126] A compound of formula (XXVIIIa) or a salt thereof (wherein R 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I)) is a compound of formula (XXVIII) or a salt thereof, wherein R 3 , R 4c , R 5a and R 5b(having the same meaning as defined above for the compound of formula (I)) can be obtained by biocatalytic deracemization of lipases such as Candida antarctica lipase B or Pseudomonas fluorescens lipase, eventually in immobilized form (e.g. Novozym® 435), in the presence of an acyl donor, e.g. ethyl methoxyacetate or vinyl acetate, in a suitable solvent such as acetonitrile or methyl tert-butyl ether, at temperatures between 20°C and 100°C. Such processes are described, for example, in J. Org. Chem. 2007, 72, 6918-6923 or Adv. Synth. Catal. 2007, 349, 1481-1488. The possible stereochemical consequences of such enzymatic deracemization are known to those skilled in the art and are described, for example, in J. Org. Chem. 1991, 56, 2656-2665 or J. Am. Chem. Soc. 2015, 137, 3996-4009.
[0127] Scheme 17: [ka] In an alternative process (Scheme 17), a compound of formula (XXVIIIa) or a salt thereof (wherein R 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I)) can be prepared by reacting a compound of formula (XXX-1) 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I), and Z is -NPhth (N-phthalimido group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group) under the deprotection conditions already described above in Scheme 15 (conversion of XXX to XXVIII).
[0128] A compound of formula (XXX-1) (wherein R 3 , R 4c , R 5a and R 5b has the same meaning as defined above for the compounds of formula (I), and Z3 is -NPhth (N-phthalimido group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group)) is a group that can be used to prepare compounds of formula (XXXI-1) (wherein R 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I), can be obtained by Mitsunobu reaction with phthalimide (HNPhth) or bis(tert-butoxycarbonyl)amine (HNBoc2) under the conditions already described above in Scheme 15 (conversion of XXXI to XXX). Such processes, which proceed with inversion of the stereocenter, are known to those skilled in the art.
[0129] A compound of formula (XXXI-1) (wherein R 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I)) can be reacted with a ketone of formula (VII-1) 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I). Such reduction can be carried out in the presence of a catalyst, e.g., a ruthenium or rhodium catalyst, with a chiral ligand, e.g., RuCl[(R,R)-TsDPEN] (mesitylene) or RuBF4[(R,R)-TsDPEN] (p-cymene), in the presence of a hydrogen donor system, e.g., HC(O)OH / Et3N or HCO2NH4. Such processes are described in the literature, e.g., J. Org. Chem. 2017, 82, 5607.
[0130] Alternatively, a compound of formula (XXVIIIa) or a salt thereof (wherein R 3, R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I), can be converted to azide compounds of formula (XXXVIII), for example by treatment with triphenylphosphine (or tributylphosphine) and water (two-step Staudinger reduction) or by hydrogenation, for example using a palladium catalyst in the presence of hydrogen, 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I). Techniques and conditions for such azide reduction are well known to those skilled in the art and are available from the literature and textbooks.
[0131] A compound of formula (XXXVIII) 3 , R 4c , R 5a and R 5b has the same meaning as defined above for compounds of formula (I)) can be reacted with an alcohol compound of formula (XXXI-1) (wherein R 3 , R 4c , R 5a and R 5b have the same meaning as defined above for compounds of formula (I). Such processes, which proceed with inversion of the stereocenter, are known to those skilled in the art and are described in the literature, for example in Adv. Synth. Catal. 2018, 360, 2157-2165.
[0132]
[0082] Any of the compounds of formula (XX), (XXII) (substituents as defined in Scheme 11), formula (XX-1) (substituents as defined in Scheme 12), formula (XXVII) (substituents as defined in Scheme 13), formula (XXVIII) (substituents as defined in Schemes 14 / 15), formula (XXVIIIa) (substituents as defined in Schemes 16 / 17) and formula (XXVIIIb) (substituents as defined in Scheme 16), or a salt (where appropriate) or a free base (where appropriate) thereof, represent a particular subset of the compounds of formula (III) as defined above in Scheme 1 and may therefore be used according to the description outlined in said Scheme 1 for the preparation of compounds of formula (I).
[0133] A compound of formula (XXVIII), (XXVIIIa) or (XXVIIIb) (substituents are defined as in Schemes 14, 15, 16 and 17), part of which [ka] (In the formula, R 4c is as defined above in formula (I), and the wavy line represents the bond to the remainder of the compound of formula (XXVIII), (XXVIIIa) or (XXVIIIb) [ka] The chemical descriptions are similar to those found in Schemes 14, 15, 16 and 17, except that starting materials of formula XVI-1 and XV-1 are replaced by compounds of formula XVI-2 and XV-2, respectively: [ka] (In the formula, R 4c , X 4 and M 1 The definition of remains the same) It can be obtained by replacing
[0134] Such compounds of formula XVI-2 and XV-2 are known or even commercially available, or they can be prepared by known methods.
[0135] Depending on the procedure or reaction conditions, the reactants can be reacted in the presence 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 metal alkylsilylamides, alkylamides, alkylenediamides, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxide 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).
[0136] The reactants can be reacted with each other as they are, i.e., without the addition of a solvent or diluent. However, in most cases, it is advantageous to add an inert solvent or diluent or a mixture thereof. When the reaction is carried out in the presence of a base, the base used in excess, such as triethylamine, pyridine, N-methylmorpholine, or N,N-diethylaniline, can also serve as the solvent or diluent.
[0137] The reaction is advantageously carried out in the temperature range of about -80°C to about +140°C, preferably about -30°C to about +100°C, and in many cases in the range of room temperature to about +80°C.
[0138] Depending on the respective suitable reaction conditions and the choice of starting materials, it is possible, for example, to simply replace one substituent with another substituent according to the invention in one reaction step, or multiple substituents can be replaced with other substituents according to the invention in the same reaction step.
[0139] 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) can be obtained by treatment with a suitable acid or with a suitable ion exchange reagent, and base salts can be obtained by treatment with a suitable base or with a suitable ion exchange reagent.
[0140] Salts of compounds of formula (I) may be converted in customary manner into the free compounds of formula (I), acid addition salts, for example by treatment with a suitable basic compound or a suitable ion exchange reagent, and into salts with a base, for example by treatment with a suitable acid or a suitable ion exchange reagent.
[0141] Salts of compounds of formula (I) may be converted into other salts, such as acid addition salts, of compounds of formula (I) in a manner known per se, for example by treating the inorganic acid salt, such as the hydrochloride, with a suitable metal salt, such as the sodium, barium or silver salt of the acid, for example silver acetate, in a suitable solvent in which the inorganic salt that forms silver chloride is insoluble and therefore precipitates from the reaction mixture.
[0142] Depending on the procedure or reaction conditions, compounds of formula (I) having salt-forming properties may be obtained in free form or in salt form.
[0143] The compounds of formula (I) and, where appropriate, their tautomers, can exist in the form of one of the possible isomers or as mixtures thereof, in the form of pure isomers, such as enantiomers and / or diastereomers, or as enantiomeric mixtures, such as racemates, diastereomeric mixtures or racemic mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms occurring in the molecule and / or depending on the configuration of non-aromatic double bonds occurring in the molecule, respectively in free form or in salt form; the invention relates to the pure isomers and also to all possible isomeric mixtures, and is to be understood in this sense above and below, respectively, even if details of the stereochemistry are not specifically stated in each case.
[0144] Diastereomeric or racemic mixtures of compounds of formula (I), in free or salt form, obtained depending on which starting materials and procedures are selected, can be separated in known manner into pure diastereomers or racemates on the basis of the physical chemical differences of the components, for example, by fractional crystallization, distillation, and / or chromatography.
[0145] Enantiomeric mixtures, such as racemates, obtained in a similar manner can be resolved into their optical antipodes by known methods, for example by recrystallization from optically active solvents, by chromatography on chiral adsorbents, for example by high-performance liquid chromatography (HPLC) on acetylcellulose using suitable microorganisms, by cleavage with specific immobilized enzymes via the formation of inclusion compounds, for example with chiral crown ethers, in which only one enantiomer is complexed, or by conversion to diastereomeric salts, for example by reacting the basic final product racemate with an optically active acid, such as a carboxylic acid, for example camphoric acid, tartaric acid or malic acid, or a sulfonic acid, for example camphorsulfonic acid, and separating the diastereomeric mixtures thus obtained, for example by fractional crystallization based on their different solubilities, to give diastereomers from which the desired enantiomer can be released by the action of a suitable substance, for example a basic substance.
[0146] Pure diastereomers or enantiomers can be obtained according to the present invention not only by separating the appropriate isomeric mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, e.g. by carrying out the process according to the present invention using stereochemically characterized starting materials.
[0147] The N-oxides can be prepared by reacting the compounds of formula (I) with a suitable oxidizing agent, such as the H2O2 / urea adduct, in the presence of an acid anhydride, such as trifluoroacetic anhydride. Such oxidations are known from the literature, for example, J. Med. Chem., 32(12), 2561-73, 1989 or WO 2000 / 15615.
[0148] When the individual components have different biological activities, it may be advantageous to isolate or synthesize the respective more biologically active isomer, e.g., enantiomer or diastereomer, or mixture of isomers, e.g., mixture of enantiomers or diastereomers.
[0149] The compounds of formula (I) and, where appropriate, their tautomers may also be obtained in free or salt form, optionally in the form of a hydrate, and / or contain other solvents, such as solvents that may have been used for the crystallization of the compounds present in solid form.
[0150] The compounds of formula (I) according to the following Tables A-1 to A-78, B-1 to B-78, C-1 to C-21, and D-1 to D-21 can be prepared according to the above method. The following examples are intended to illustrate the invention and to show preferred compounds of formula (I) in the form of compounds of formula (IA), (IB), (IC), and (ID). [ka]
[0151] Tables A-1 to A-78 (Formula IA) Table A-1 provides 32 compounds A-1.001 to A-1.032 of formula IA, where A14 is N and A 24 is N and A 344 is N and R 1 is H and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z. For example, A-1.002 is [ka] is.
[0152] Table A-2 provides 32 compounds A-2.001 to A-2.032 of formula IA, where A 14 is N and A 24 is N and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0153] Table A-3 provides 32 compounds A-3.001 to A-3.032 of formula IA, where A 14 is N and A 24 is N and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0154] Table A-4 provides 32 compounds A-4.001 to A-4.032 of formula IA, where A 14 is N and A 24 is N and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0155] Table A-5 provides 32 compounds A-5.001 to A-5.032 of formula IA, where A 14 is N and A 24 is N and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0156] Table A-6 provides 32 compounds A-6.001 to A-6.032 of formula IA, where A 14 is N and A 24 is N and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0157] Table A-7 provides 32 compounds A-7.001 to A-7.032 of formula IA, where A 14 is N and A 24 is N and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0158] Table A-8 provides 32 compounds A-8.001 to A-8.032 of formula IA, where A 14 is N and A 24 is N and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0159] Table A-9 provides 32 compounds A-9.001 to A-9.032 of formula IA, where A 14 is N and A 24 is N and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0160] Table A-10 provides 32 compounds A-10.001 to A-10.032 of formula IA, where A 14 is N and A 24 is N and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0161] Table A-11 provides 32 compounds A-11.001 to A-11.032 of formula IA, where A 14 is N and A 24 is N and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0162] Table A-12 provides 32 compounds A-12.001 to A-12.032 of formula IA, where A 14 is N and A 24 is N and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0163] Table A-13 provides 32 compounds A-13.001 to A-13.032 of formula IA, where A 14 is N and A 24 is N and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0164] Table A-14 provides 32 compounds A-14.001 to A-14.032 of formula IA, where A 14 is N and A 24 is N and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0165] Table A-15 provides 32 compounds A-15.001 to A-15.032 of formula IA, where A 14 is N and A 24 is N and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0166] Table A-16 provides 32 compounds A-16.001 to A-16.032 of formula IA, where A 14 is N and A 24 is N and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0167] Table A-17 provides 32 compounds A-17.001 to A-17.032 of formula IA, where A 14 is N and A 24 is N and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0168] Table A-18 provides 32 compounds A-18.001 to A-18.032 of formula IA, where A 14 is N and A 24 is N and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0169] Table A-19 provides 32 compounds A-19.001 to A-19.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0170] Table A-20 provides 32 compounds A-20.001 to A-20.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0171] Table A-21 provides 32 compounds A-21.001 to A-21.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0172] Table A-22 provides 32 compounds A-22.001 to A-22.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0173] Table A-23 provides 32 compounds A-23.001 to A-23.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0174] Table A-24 provides 32 compounds A-24.001 to A-24.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0175] Table A-25 provides 32 compounds A-25.001 to A-25.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0176] Table A-26 provides 32 compounds A-26.001 to A-26.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0177] Table A-27 provides 32 compounds A-27.001 to A-27.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0178] Table A-28 provides 32 compounds A-28.001 to A-28.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0179] Table A-29 provides 32 compounds A-29.001 to A-29.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0180] Table A-30 provides 32 compounds A-30.001 to A-30.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0181] Table A-31 provides 32 compounds A-31.001 to A-31.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0182] Table A-32 provides 32 compounds A-32.001 to A-32.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0183] Table A-33 provides 32 compounds A-33.001 to A-33.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0184] Table A-34 provides 32 compounds A-34.001 to A-34.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0185] Table A-35 provides 32 compounds A-35.001 to A-35.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0186] Table A-12 provides 32 compounds A-12.001 to A-12.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0187] Table A-37 provides 32 compounds A-37.001 to A-37.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0188] Table A-38 provides 32 compounds A-38.001 to A-38.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0189] Table A-39 provides 32 compounds A-39.001 to A-39.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0190] Table A-40 provides 32 compounds A-40.001 to A-40.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0191] Table A-41 provides 32 compounds A-41.001 to A-41.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0192] Table A-42 provides 32 compounds A-42.001 to A-42.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0193] Table A-43 provides 32 compounds A-43.001 to A-43.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0194] Table A-44 provides 32 compounds A-44.001 to A-44.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0195] Table A-45 provides 32 compounds A-45.001 to A-45.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0196] Table A-46 provides 32 compounds A-46.001 to A-46.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0197] Table A-47 provides 32 compounds A-47.001 to A-47.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0198] Table A-48 provides 32 compounds A-48.001 to A-48.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0199] Table A-49 provides 32 compounds A-49.001 to A-49.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0200] Table A-50 provides 32 compounds A-50.001 to A-50.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0201] Table A-51 provides 32 compounds A-51.001 to A-51.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0202] Table A-52 provides 32 compounds A-52.001 to A-52.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0203] Table A-53 provides 32 compounds A-53.001 to A-53.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0204] Table A-54 provides 32 compounds A-54.001 to A-54.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0205] Table A-55 provides 32 compounds A-55.001 to A-55.032 of formula IA, where A 14 is CH and A 24 is CH and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0206] Table A-56 provides 32 compounds A-56.001 to A-56.032 of formula IA, where A 14 is CH and A 24 is CH and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0207] Table A-57 provides 32 compounds A-57.001 to A-57.032 of formula IA, where A 14 is CH and A 24 is CH and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0208] Table A-58 provides 32 compounds A-58.001 to A-58.032 of formula IA, where A 14 is CH and A 24 is CH and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0209] Table A-59 provides 32 compounds A-59.001 to A-59.032 of formula IA, where A 14 is CH and A 24 is CH and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0210] Table A-60 provides 32 compounds A-60.001 to A-60.032 of formula IA, where A 14 is CH and A 24 is CH and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0211] Table A-61 provides 32 compounds A-61.001 to A-61.032 of formula IA, where A 14 is CH and A 24 is CH and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0212] Table A-62 provides 32 compounds A-62.001 to A-62.032 of formula IA, where A 14 is CH and A 24 is CH and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0213] Table A-63 provides 32 compounds A-63.001 to A-63.032 of formula IA, where A 14 is CH and A 24 is CH and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0214] Table A-64 provides 32 compounds A-64.001 to A-64.032 of formula IA, where A 14 is CH and A 24 is CH and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0215] Table A-65 provides 32 compounds A-65.001 to A-65.032 of formula IA, where A 14 is CH and A 24 is CH and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0216] Table A-66 provides 32 compounds A-66.001 to A-66.032 of formula IA, where A 14 is CH and A 24 is CH and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0217] Table A-67 provides 32 compounds A-67.001 to A-67.032 of formula IA, where A 14 is CH and A 24 is CH and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0218] Table A-68 provides 32 compounds A-68.001 to A-68.032 of formula IA, where A 14 is CH and A 24 is CH and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0219] Table A-69 provides 32 compounds A-69.001 to A-69.032 of formula IA, where A 14 is CH and A 24 is CH and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0220] Table A-70 provides 32 compounds A-70.001 to A-70.032 of formula IA, where A 14 is CH and A 24 is CH and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0221] Table A-71 provides 32 compounds A-71.001 to A-71.032 of formula IA, where A 14 is CH and A 24 is CH and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0222] Table A-72 provides 32 compounds A-72.001 to A-72.032 of formula IA, where A 14 is CH and A 24 is CH and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0223] Table A-73 provides 32 compounds A-73.001 to A-73.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2CH3 and T is as defined in Table Z.
[0224] Table A-74 provides 32 compounds A-74.001 to A-74.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2CH3 and T is as defined in Table Z.
[0225] Table A-75 provides 32 compounds A-75.001 to A-75.032 of formula IA, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2CH3 and T is as defined in Table Z.
[0226] Table A-76 provides 32 compounds A-76.001 to A-76.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2CH3 and T is as defined in Table Z.
[0227] Table A-77 provides 32 compounds A-77.001 to A-77.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2CH3 and T is as defined in Table Z.
[0228] Table A-78 provides 32 compounds A-78.001 to A-78.032 of formula IA, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2CH3 and T is as defined in Table Z.
[0229] Tables B-1 to B-78 (Formula IB) Table B-1 provides 32 compounds B-1.001 to B-1.032 of formula IB, where A 14 is N and A 24 is N and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0230] Table B-2 provides 32 compounds B-2.001 to B-2.032 of formula IB, where A 14 is N and A 24 is N and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0231] Table B-3 provides 32 compounds B-3.001 to B-3.032 of formula IB, where A 14 is N and A 24 is N and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0232] Table B-4 provides 32 compounds B-4.001 to B-4.032 of formula IB, where A 14 is N and A 24 is N and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0233] Table B-5 provides 32 compounds B-5.001 to B-5.032 of formula IB, where A 14 is N and A 24 is N and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0234] Table B-6 provides 32 compounds B-6.001 to B-6.032 of formula IB, where A 14 is N and A 24 is N and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0235] Table B-7 provides 32 compounds B-7.001 to B-7.032 of formula IB, where A 14 is N and A 24 is N and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0236] Table B-8 provides 32 compounds B-8.001 to B-8.032 of formula IB, where A 14 is N and A 24 is N and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0237] Table B-9 provides 32 compounds B-9.001 to B-9.032 of formula IB, where A 14 is N and A 24 is N and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0238] Table B-10 provides 32 compounds B-10.001 to B-10.032 of formula IB, where A 14 is N and A 24 is N and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0239] Table B-11 provides 32 compounds B-11.001 to B-11.032 of formula IB, where A 14 is N and A 24 is N and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0240] Table B-12 provides 32 compounds B-12.001 to B-12.032 of formula IB, where A 14 is N and A 24 is N and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0241] Table B-13 provides 32 compounds B-13.001 to B-13.032 of formula IB, where A 14 is N and A 24 is N and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0242] Table B-14 provides 32 compounds B-14.001 to B-14.032 of formula IB, where A 14 is N and A 24 is N and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0243] Table B-15 provides 32 compounds B-15.001 to B-15.032 of formula IB, where A 14 is N and A 24 is N and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0244] Table B-16 provides 32 compounds B-16.001 to B-16.032 of formula IB, where A 14 is N and A 24 is N and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0245] Table B-17 provides 32 compounds B-17.001 to B-17.032 of formula IB, where A 14 is N and A 24 is N and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0246] Table B-18 provides 32 compounds B-18.001 to B-18.032 of formula IB, where A 14 is N and A 24 is N and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0247] Table B-19 provides 32 compounds B-19.001 to B-19.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0248] Table B-20 provides 32 compounds B-20.001 to B-20.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0249] Table B-21 provides 32 compounds B-21.001 to B-21.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0250] Table B-22 provides 32 compounds B-22.001 to B-22.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0251] Table B-23 provides 32 compounds B-23.001 to B-23.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0252] Table B-24 provides 32 compounds B-24.001 to B-24.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0253] Table B-25 provides 32 compounds B-25.001 to B-25.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0254] Table B-26 provides 32 compounds B-26.001 to B-26.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0255] Table B-27 provides 32 compounds B-27.001 to B-27.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0256] Table B-28 provides 32 compounds B-28.001 to B-28.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0257] Table B-29 provides 32 compounds B-29.001 to B-29.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0258] Table B-30 provides 32 compounds B-30.001 to B-30.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0259] Table B-31 provides 32 compounds B-31.001 to B-31.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0260] Table B-32 provides 32 compounds B-32.001 to B-32.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0261] Table B-33 provides 32 compounds B-33.001 to B-33.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0262] Table B-34 provides 32 compounds B-34.001 to B-34.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0263] Table B-35 provides 32 compounds B-35.001 to B-35.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0264] Table B-36 provides 32 compounds B-36.001 to B-36.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0265] Table B-37 provides 32 compounds B-37.001 to B-37.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0266] Table B-38 provides 32 compounds B-38.001 to B-38.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0267] Table B-39 provides 32 compounds B-39.001 to B-39.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0268] Table B-40 provides 32 compounds B-40.001 to B-40.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0269] Table B-41 provides 32 compounds B-41.001 to B-41.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0270] Table B-42 provides 32 compounds B-42.001 to B-42.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0271] Table B-43 provides 32 compounds B-43.001 to B-43.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0272] Table B-44 provides 32 compounds B-44.001 to B-44.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0273] Table B-45 provides 32 compounds B-45.001 to B-45.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0274] Table B-46 provides 32 compounds B-46.001 to B-46.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0275] Table B-47 provides 32 compounds B-47.001 to B-47.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0276] Table B-48 provides 32 compounds B-48.001 to B-48.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0277] Table B-49 provides 32 compounds B-49.001 to B-49.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0278] Table B-50 provides 32 compounds B-50.001 to B-50.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0279] Table B-51 provides 32 compounds B-51.001 to B-51.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0280] Table B-52 provides 32 compounds B-52.001 to B-52.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0281] Table B-53 provides 32 compounds B-53.001 to B-53.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0282] Table B-54 provides 32 compounds B-54.001 to B-54.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0283] Table B-55 provides 32 compounds B-55.001 to B-55.032 of formula IB, where A 14 is CH and A 24 is CH and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0284] Table B-56 provides 32 compounds B-56.001 to B-56.032 of formula IB, where A 14 is CH and A 24 is CH and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0285] Table B-57 provides 32 compounds B-57.001 to B-57.032 of formula IB, where A 14 is CH and A 24 is CH and A 34 is N and R 1 is H and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0286] Table B-58 provides 32 compounds B-58.001 to B-58.032 of formula IB, where A 14 is CH and A 24 is CH and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0287] Table B-59 provides 32 compounds B-59.001 to B-59.032 of formula IB, where A 14 is CH and A 24 is CH and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0288] Table B-60 provides 32 compounds B-60.001 to B-60.032 of formula IB, where A 14 is CH and A 24 is CH and A 34 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0289] Table B-61 provides 32 compounds B-61.001 to B-61.032 of formula IB, where A 14 is CH and A 24 is CH and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0290] Table B-62 provides 32 compounds B-62.001 to B-62.032 of formula IB, where A 14 is CH and A 24 is CH and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0291] Table B-63 provides 32 compounds B-63.001 to B-63.032 of formula IB, where A 14 is CH and A 24 is CH and A 34 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0292] Table B-64 provides 32 compounds B-64.001 to B-64.032 of formula IB, where A 14 is CH and A 24 is CH and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0293] Table B-65 provides 32 compounds B-65.001 to B-65.032 of formula IB, where A 14 is CH and A 24 is CH and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0294] Table B-66 provides 32 compounds B-66.001 to B-66.032 of formula IB, where A 14 is CH and A 24 is CH and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0295] Table B-67 provides 32 compounds B-67.001 to B-67.032 of formula IB, where A 14 is CH and A 24 is CH and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0296] Table B-68 provides 32 compounds B-68.001 to B-68.032 of formula IB, where A 14 is CH and A 24 is CH and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0297] Table B-69 provides 32 compounds B-69.001 to B-69.032 of formula IB, where A 14 is CH and A 24 is CH and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0298] Table B-70 provides 32 compounds B-70.001 to B-70.032 of formula IB, where A 14 is CH and A 24 is CH and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0299] Table B-71 provides 32 compounds B-71.001 to B-71.032 of formula IB, where A 14 is CH and A 24 is CH and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0300] Table B-72 provides 32 compounds B-72.001 to B-72.032 of formula IB, where A 14 is CH and A 24 is CH and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0301] Table B-73 provides 32 compounds B-73.001 to B-73.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2CH3 and T is as defined in Table Z.
[0302] Table B-74 provides 32 compounds B-74.001 to B-74.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2CH3 and T is as defined in Table Z.
[0303] Table B-75 provides 32 compounds B-75.001 to B-75.032 of formula IB, where A 14 is N and A 24 is CH and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2CH3 and T is as defined in Table Z.
[0304] Table B-76 provides 32 compounds B-76.001 to B-76.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2CH3 and T is as defined in Table Z.
[0305] Table B-77 provides 32 compounds B-77.001 to B-77.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2CH3 and T is as defined in Table Z.
[0306] Table B-78 provides 32 compounds B-78.001 to B-78.032 of formula IB, where A 14 is CH and A 24 is N and A 34 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2CH3 and T is as defined in Table Z.
[0307] Tables C-1~C-21 (Formula IC) Table C-1 provides 32 compounds C-1.001 to C-1.032 of formula IC, where A 14 is N and R 1 is H and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0308] Table C-2 provides 32 compounds C-2.001 to C-2.032 of formula IC, where A 14 is N and R 1 is H and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0309] Table C-3 provides 32 compounds C-3.001 to C-3.032 of formula IC, where A 14 is N and R 1 is H and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0310] Table C-4 provides 32 compounds C-4.001 to C-4.032 of formula IC, where A 14 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0311] Table C-5 provides 32 compounds C-5.001 to C-5.032 of formula IC, where A 14 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0312] Table C-6 provides 32 compounds C-6.001 to C-6.032 of formula IC, where A 14 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0313] Table C-7 provides 32 compounds C-7.001 to C-7.032 of formula IC, where A 14 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0314] Table C-8 provides 32 compounds C-8.001 to C-8.032 of formula IC, where A 14 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0315] Table C-9 provides 32 compounds C-9.001 to C-9.032 of formula IC, where A 14 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0316] Table C-10 provides 32 compounds C-10.001 to C-10.032 of formula IC, where A 14 is CH and R 1 is H and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0317] Table C-11 provides 32 compounds C-11.001 to C-11.032 of formula IC, where A 14 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0318] Table C-12 provides 32 compounds C-12.001 to C-12.032 of formula IC, where A 14 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0319] Table C-13 provides 32 compounds C-13.001 to C-13.032 of formula IC, where A 14 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0320] Table C-14 provides 32 compounds C-14.001 to C-14.032 of formula IC, where A 14 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0321] Table C-15 provides 32 compounds C-15.001 to C-15.032 of formula IC, where A 14 is CH and R 1 is CH3 and R 3 is CH3 and R 4cis CH2-cyclopropyl and T is as defined in Table Z.
[0322] Table C-16 provides 32 compounds C-16.001 to C-16.032 of formula IC, where A 14 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0323] Table C-17 provides 32 compounds C-17.001 to C-17.032 of formula IC, where A 14 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0324] Table C-18 provides 32 compounds C-18.001 to C-18.032 of formula IC, where A 14 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0325] Table C-19 provides 32 compounds C-19.001 to C-19.032 of formula IC, where A 14 is N and R 1 is H and R 3 is CH3 and R 4c is CH2CH3 and T is as defined in Table Z.
[0326] Table C-20 provides 32 compounds C-20.001 to C-20.032 of formula IC, where A 14 is N and R 1is CH3 and R 3 is CH3 and R 4c is CH2CH3 and T is as defined in Table Z.
[0327] Table C-21 provides 32 compounds C-21.001 to C-21.032 of formula IC, where A 14 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2CH3 and T is as defined in Table Z.
[0328] Tables D-1~D-21 (Formula ID) Table D-1 provides 32 compounds D-1.001 to D-1.032 of formula ID, where A 14 is N and R 1 is H and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0329] Table D-2 provides 32 compounds D-2.001 to D-2.032 of formula ID, where A 14 is N and R 1 is H and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0330] Table D-3 provides 32 compounds D-3.001 to D-3.032 of formula ID, where A 14 is N and R 1 is H and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0331] Table D-4 provides 32 compounds D-4.001 to D-4.032 of formula ID, where A14 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0332] Table D-5 provides 32 compounds D-5.001 to D-5.032 of formula ID, where A 14 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0333] Table D-6 provides 32 compounds D-6.001 to D-6.032 of formula ID, where A 14 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0334] Table D-7 provides 32 compounds D-7.001 to D-7.032 of formula ID, where A 14 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0335] Table D-8 provides 32 compounds D-8.001 to D-8.032 of formula ID, where A 14 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0336] Table D-9 provides 32 compounds D-9.001 to D-9.032 of formula ID, where A 14 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0337] Table D-10 provides 32 compounds D-10.001 to D-10.032 of formula ID, where A 14 is CH and R 1 is H and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0338] Table D-11 provides 32 compounds D-11.001 to D-11.032 of formula ID, where A 14 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0339] Table D-12 provides 32 compounds D-12.001 to D-12.032 of formula ID, where A 14 is CH and R 1 is H and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0340] Table D-13 provides 32 compounds D-13.001 to D-13.032 of formula ID, where A 14 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0341] Table D-14 provides 32 compounds D-14.001 to D-14.032 of formula ID, where A 14 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0342] Table D-15 provides 32 compounds D-15.001 to D-15.032 of formula ID, where A 14 is CH and R 1 is CH3 and R 3 is CH3 and R 4c is CH2-cyclopropyl and T is as defined in Table Z.
[0343] Table D-16 provides 32 compounds D-16.001 to D-16.032 of formula ID, where A 14 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH3 and T is as defined in Table Z.
[0344] Table D-17 provides 32 compounds D-17.001 to D-17.032 of formula ID, where A 14 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2-CF2H and T is as defined in Table Z.
[0345] Table D-18 provides 32 compounds D-18.001 to D-18.032 of formula ID, where A 14 is CH and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4cis CH2-cyclopropyl and T is as defined in Table Z.
[0346] Table D-19 provides 32 compounds D-19.001 to D-19.032 of formula ID, where A 14 is N and R 1 is H and R 3 is CH3 and R 4c is CH2CH3 and T is as defined in Table Z.
[0347] Table D-20 provides 32 compounds D-20.001 to D-20.032 of formula ID, where A 14 is N and R 1 is CH3 and R 3 is CH3 and R 4c is CH2CH3 and T is as defined in Table Z.
[0348] Table D-21 provides 32 compounds D-21.001 to D-21.032 of formula ID, where A 14 is N and R 1 is CH2-cyclopropyl and R 3 is CH3 and R 4c is CH2CH3 and T is as defined in Table Z.
[0349] [Table 1-1] [Table 1-2] [Table 1-3]
[0350] Certain intermediate compounds of formula II(i), III(i), IV(i), IVa(i), V(i), VI(i), VII(i), VIII(i), IX(i), X(i), XI(i), XII(i), XIV(i), XV(i), XVI(i), XX(i), XXI(i) and XXII(i) are also provided, some of which are novel, for example: a compound of formula XII(i) or a tautomer thereof or a salt thereof: [ka] (In the formula, A 14 , A 24 , A 34 and R 4c is as defined in any one of Tables A-1 to A-78 and Tables B-1 to B-78), with the proviso that said compound is [ka] 6-hydrazinyl-2-methyl-3(2H)-pyridazinone or its tautomer; or [ka] 6-hydrazinyl-2-ethyl-3(2H)-pyridazinone or its tautomer isn't it. - a compound of formula XVI(i): [ka] (In the formula, A 14 and A 24 One of the groups is N and the other is CH, and R 4c is as defined in any one of Tables A-1 to A-78 and Tables B-1 to B-78, and M 1 is a metal-containing substituent, for example a boron or tin substituent, such as tributylstannyl, boron or 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl, provided that the compound of formula XVI(i) is: -2-methyl-6-trimethylstannyl-pyridazin-3-one (CAS 2254337-53-4), -[5-oxo-4-(2,2,2-trifluoroethyl)pyrazin-2-yl]boronic acid (CAS 2509138-33-2), -5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-(2,2,2-trifluoroethyl)pyrazin-2-one (CAS 2509138-04-7), -(2-methyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridazin-3-one (CAS 1610374-18-9), -2-Isopropyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridazin-3-one (CAS 2768712-84-9), -(1-methyl-6-oxo-pyridazin-3-yl)boronic acid (CAS 1872185-45-9), or -(1-Isopropyl-6-oxo-pyridazin-3-yl)boronic acid (CAS 2334476-21-8) isn't it. Compounds of formula XX(i), XXI(i) and XXII(i) [ka] (In the formula, A 14 , A 24 , A 34 and R 4c R containing 4a is as defined in any one of Tables A-1 through A-78 and Tables B-1 through B-78, and X - is an anion, i.e., the conjugate base of an acid, such as an inorganic acid, e.g., hydrochloric acid, hydrobromic acid, hydrogen fluoride, hydrogen iodide, sulfuric acid, etc., or an organic acid, e.g., a carboxylic acid or a sulfonic acid, e.g., trifluoroacetic acid, methanesulfonic acid, or p-toluenesulfonic acid). 14 is N and A 24 is CH and A 34 is CH, and R 4cis selected from methyl or ethyl. compounds of formula XXVI(i), XXVII(i) and XXVII-a(i) [ka] (In the formula, A 14 and R 4c R containing 4b is as defined in any one of Tables C-1 to C-21 and Tables D-1 to D-21, and X - is an anion, i.e., the anion of the conjugate base of an acid, such as an inorganic acid, e.g., hydrochloric acid, hydrobromic acid, hydrogen fluoride, hydrogen iodide, sulfuric acid, etc., or an organic acid, e.g., a carboxylic acid or a sulfonic acid, e.g., trifluoroacetic acid, or methanesulfonic acid, or paratoluenesulfonic acid. Preferably, A 14 is N, and R 4c is selected from methyl or ethyl).
[0351] In a further aspect, the present invention therefore provides compounds of formula II(i), III(i), IV(i), IVa(i), V(i), VI(i), VII(i), VIII(i), IX(i), X(i), XI(i), XII(i), XIV(i), XV(i), XVI(i), XX(i), XXI(i) and XXII(i), wherein, in each case, where appropriate, A 1 , A 2 , A 3 , A 4 , A 5 , X 0 , R 1 , R 2a , R 2b , R 3 , Q a (R 5 , R 4c , and R 4a or R 4b as R 4 ), Q b (R 5a , R 5b , R 4c , and R 4a or R 4b as R4 ), R 4 , R 4a (A 14 , A 24 , A 34 and R 4c ), R 4b (A 14 and R 4c ), R X , R Y , and R Z is as defined for formula (I) in the first aspect, and -T is [ka] (wherein the wavy line represents the bond to the remainder of the compound of formula (II), (IV), (IVa), (X), (XI), (XVII); for compounds of formula II(i), X 1 is a leaving group such as halogen, hydroxy or sulfonate, e.g., chloride; for compounds of formula V(i), X 2 is a leaving group such as a halogen, e.g., chloride or bromide, or a sulfonate, e.g., mesylate; for compounds of formula VI(i), X 3 is a leaving group such as a halogen, e.g., chloride, bromide, iodide, or a sulfonate, e.g., mesylate; for compounds of formula XV(i), X 4 is a leaving group such as, for example, halogen, for example chloro, sulfonate, C1-C4-sulfanyl, C1-C4-sulfinyl or C1-C4-sulfonyl; for compounds of formula XVI(i), M 1 is, for example, a boron or tin substituent, such as tributylstannyl, borono, or 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl; - for compounds of formula XX(i), X -is an anion, i.e., the conjugate base of an acid, such as an inorganic acid, e.g., hydrochloric acid, hydrobromic acid, hydrogen fluoride, hydrogen iodide, sulfuric acid, etc., or an organic acid, e.g., a carboxylic acid or a sulfonic acid, e.g., trifluoroacetic acid or methanesulfonic acid or p-toluenesulfonic acid.
[0352] Furthermore, where appropriate, the corresponding embodiments exemplified in formula (I) also apply to compounds of formula II(i), III(i), IV(i), IVa(i), V(i), VI(i), VII(i), VIII(i), IX(i), X(i), XI(i), XII(i), XIV(i), XV(i), XVI(i), XX(i), XXI(i) and XXII(i).
[0353] The compounds of formula (I) according to the invention are preventively and / or therapeutically useful active ingredients in the field of pest control, even at low application rates, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded animal species, fish, and plants. The active ingredients according to the invention act not only against normally susceptible animal pests, such as insects or representatives of the order Acarina, but also against all or individual developmental stages of resistant animal pests. The insecticidal or acaricidal activity of the active ingredients according to the invention can be manifested directly (i.e., killing pests immediately or only after a certain period of time, for example, during molting) or indirectly (e.g., reducing egg production and / or hatchability).
[0354] Examples of the above animal pests are: From the order Acarina, for example: Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp., Eotetranychus spp. spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus spp.), Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp., Tarsonemus spp. and Tetranychus spp.; From the order Anoplura, for example: Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; From the order Coleoptera, for example: Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotoma spp., Conoderus spp., Cosmopolites spp., Cotinis nitida, 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., Maladera castanea, Megascelis spp. spp., Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp., Phlyctinus spp., Popillia spp.), Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabaeidae, 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. 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. spp.), Rhagoletis spp., Rivelia quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; From the order Hemiptera, for example: Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Aleurodes spp., Amblypelta nitida, Bathycoelia thalassina, Blissus spp., Cimex spp., Clavigrella tomentosicollis, Creontiades spp., Distantiella theobroma, Dichelops furcatus, 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 insularis, Piesma spp., Piezodorus spp., Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp.), Thyanta spp., Triatoma spp., Vatiga illudens;. From the order Homoptera, for example: Acyrthosium pisum, Adalges spp., Agalliana ensigera, Agonoscena targionii, Aleurodicus spp., Aleurocanthus spp., Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp. spp.), Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp., Brachycaudus spp., Brevicoryne brassicae, Cacopsylla spp., Cavariella aegopodii Scop., Ceroplaster spp.), Chrysomphalus aonidium, 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., Lecanium corni, Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp., Mahanarva spp., Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp.), Neotoxoptera spp., Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter, Bayberry whitefly (Parabemisia myricae), Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Corn planthopper (Peregrinus maidis), Perkinsiella spp., Hop wart aphid (Phorodon humuli, Phylloxera spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp., Scaphoideus spp. spp.), Schizaphis spp., Sitobion spp.), Sogatella furcifera, Spisstilus festinus, Tarophagus Proserpina, Toxoptera spp., Trialeurodes spp., Tridiscus sporoboli, Trionymus spp., Trioza erytreae, Unaspis citri, Zygina flammigera, Zyginidia scutellaris; From the order Hymenoptera, for example: Acromyrmex ants, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis ants, Neodiprion spp., Pogonomyrmex spp., Slenopsis invicta, Solenopsis spp. and Vespa spp.; From the order Isoptera, for example: Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Solenopsis geminate 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, Cryptophlebia leucotreta, Cydalima perspectalis perspectalis, Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea, Earias spp.), Elasmopalpus lignosellus, Eldana saccharina, Ephestia spp., Epinotia spp., Estigmene acrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltia jaculiferia, Grapholita spp., Hedya nubiferana, Heliothis spp. spp.), Hellula undalis, Herpetogramma spp., Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostege bifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Mythimna spp., Noctua spp., Operophtera spp., Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp.), pine sawyer moth (Panolis flammea), Papaipema nebris, pink bollworm (Pectinophora gossypiela), coffee leafminer (Perileucoptera coffeella), Pseudaletia unipuncta, potato tuber moth (Phthorimaea operculella), cabbage white butterfly (Pieris rapae), Pieris spp., diamondback moth (Plutella xylostella), Prays spp., Pseudoplusia spp., Rachiplusia nu, Richia albicosta, Scirpophaga spp., Sesamia spp.), Sparganothis spp., Spodoptera spp., Sylepta derogate, Synanthedon spp., Thaumetopoea spp., 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., Scapteriscus spp. and Schistocerca spp.; From the order Psocoptera, for example: Liposcelis spp.; From the order Siphonaptera, for example: Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis; From the order Thysanoptera, for example: Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp.; From the order Thysanura, for example, Lepisma saccharina.
[0355] In a further aspect, the present invention also relates to plant parasitic nematodes (endoparasitic, semi-endoparasitic and ectoparasitic nematodes), in particular the root-knot nematode Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes Globodera rostochiensis and other Globodera species; wheat cyst nematode Heterodera avenae, soybean cyst nematode Heterodera glycines, sugar beet cyst nematode Heterodera schachtii, clover cyst nematode Heterodera trifolii and other cyst nematodes (Heterodera species); seed gall nematodes, Anguina species; stem and peel nematodes, Aphelenchoides species; sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; pine wood nematode, Bursaphelenchus xylophilus and other Bursaphelenchus species; ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; fire nematodes, Dolichodorus species;Screw nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Spear nematodes, Hoploaimus species; False root-knot nematodes, Nacobbus species; Tylenchidae, Longidorus elongatus elongatus and other Longidorus species; pin nematodes, Pratylenchus species; root-lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; root-lesion nematodes, Radopholus similis and other Radopholus species; false nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species; Scutellonema species; Trichodorus primitivus and other Trichodorus species, Paratrichodorus species;plant-parasitic nematodes such as the claytonid nematode, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; the burrowing nematode, Tylenchulus species; plant-parasitic nematodes such as the giant sting nematode, Xiphinema species; and plant-parasitic nematodes such as Subanguina species, Hypsoperine species, Macroposthonia species, Melinius species, Punctodera species and Quinisulcius species. The present invention may also relate to a method for preventing damage to plants and parts thereof by other plant-parasitic nematode species, such as Pseudomonas spp.;
[0356] The compounds of the present invention may also have activity against mollusks, such as, for example, the family Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena furticum); fruticum); Cepaea (C. hortensis, C. nemoralis); Ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum) tum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H. obvia); Helicidae (Helicigona albustrum) arbustorum); Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Monoa These include the genera Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.
[0357] The active ingredients according to the invention can be used to control, i.e. suppress or destroy, pests of the above-mentioned types occurring in particular on plants, in particular on useful plants and ornamental plants in agriculture, horticulture and forestry, or on organs of such plants, such as the fruits, flowers, foliage, stems, tubers or roots, and in some cases even plant organs formed at a later time remain protected from these pests.
[0358] Suitable target crops are, in particular, cereals such as wheat, barley, rye, oats, rice, maize or sorghum; beets such as sugar beet or fodder beet; fruits, such as pome fruits, stone fruits or soft fruits, for example apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; legumes, such as beans, lentils, peas or soybeans; rapeseed, mustard, poppy, olive, sunflower, palm, castor, cocoa or groundnut. citrus fruits such as oranges, lemons, grapefruits or tangerines; vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes or peppers; plants of the Lauraceae family such as avocado, cinnamon or camphor; and also tobacco, tree nuts, coffee, eggplant, sugarcane, tea, pepper, grapes, hops, plantains and latex plants.
[0359] The compositions and / or methods of the present invention may be used on any ornamental and / or vegetable crop, including flowers, shrubs, broadleaf trees and evergreen trees.
[0360] For example, the present invention relates to the use of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g., B. elatior, B. semperflorens, B. tubereux), Bougainvillea spp., Brachycome spp. 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., Bleeding hearts spectabilis, Dorotheantus spp., Lisianthus (Eustoma grandiflorum), Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Globetrotter (Gomphrena globosa), Heliotropium spp., Helianthus spp., Hibiscus spp.), Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (I. Walleriana), Iresines spp., Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp. spp.), Nemesia spp., Tagetes spp., Dianthus spp. (carnations), Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (ivy geranium (P. peltatum), P. Zonale), Viola spp. (pansies), Petunia spp., Phlox spp., Plecthranthus spp., Poinsettia spp. spp.), Parthenocissus spp. (American Creeper (P. quinquefolia), Ivy (P. tricuspidata)), Primula spp., Ranunculus spp., Rhododendron spp., Rosa spp. (roses), Rudbeckia spp., Saintpaulia spp., Salvia spp.), Scaevola aemola, Schizanthus wisetonensis, Sedum spp., Solanum spp., Surfinia spp., Tagetes spp., Nicotinia spp., Verbena spp., Zinnia spp., and other bedding plants.
[0361] For example, the present invention relates to the use of the following vegetable species: Allium spp. (garlic (A. sativum), onion (A. cepa), shallot (A. oschaninii), leek (A. porrum), scallion (A. ascalonicum), green onion (A. fistulosum)), chervil (Anthriscus cerefolium), celery (Apium graveolus), asparagus (Asparagus officinalis), beet (Beta vulgarus), Brassica spp. (B. oleracea, Chinese cabbage (B. pekinensis), turnip (B. rapa)), chili pepper (Capsicum annuum), chickpea (Cicer arietinum), endive (Cichorium endivia), Cichorum spp. spp.) (chicory (C. intybus), endive (C. endivia)), watermelon (Citrillus lanatus), Cucumis spp. (saffron (C. sativus), melon (C. melo)), Cucurbita spp. (Cucurbita pepo, Cucurbita maxima), Cyanara spp. (artichoke (C. scolymus), cardoon (C. cardunculus)), carrot (Daucus carota), fennel (Foeniculum vulgare), Hypericum spp., lettuce (Lactuca sativa), tomato spp. spp.) (tomato (L. esculentum), tomato (L. lycopersicum)), mint species (Mentha spp.), basil (Ocimum basilicum), parsley (Petroselinum crispum), Phaseolus species (Phaseolus spp.) (P. vulgaris, runner bean (P.The present invention may be used in any of the following plants: pea (Pisum sativum), radish (Raphanus sativus), rhubarb (Rheum rhaponticum), rosemary (Rosemarinus spp.), salvia (Salvia spp.), yellow rosemary (Scorzonera hispanica), eggplant (Solanum melongena), spinach (Spinacea oleracea), Valerianella spp. (V. locusta, V. eriocarpa), and broad bean (Vicia faba).
[0362] Preferred ornamental species include Saintpaulia, Begonia, Dahlia, Gerbera, Hydrangea, Vervain, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hydrangea, Rosemary, Sage, St. John's Wort, Mint, Bell Pepper, Tomato, and Cucumber.
[0363] The active ingredients according to the invention are particularly suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetables, corn, rice and soybean crops. The active ingredients according to the invention are particularly suitable for controlling Mamestra (preferably on vegetables), codling moth (Cydia pomonella) (preferably on apple), Empoasca (preferably on vegetables and vineyards), Leptinotarsa (preferably on potato) and Chilo supressalis (preferably on rice).
[0364] The compounds of formula (I) are particularly suitable for controlling: Hemiptera pests, such as one or more of the following: Bemisia tabaci, Aphis craccivora, Myzus persicae, Rhopalosiphum padi, Nilaparvata lugens and Euschistus heros (preferably on vegetables, soybeans and sugarcane) Lepidoptera pests, for example one or more of the species Spodoptera littoralis, Spodoptera frugiperda, Plutella xylostella, Cnaphalocrocis medinalis, Cydia pomonella, Chrysodeixis includes, Chilo suppressalis, Elasmopalpus lignosellus, Pseudoplusia includesns and Tuta absoluta (preferably on vegetables and corn). pests of the order Thysanoptera, such as Thripidae, for example Thrips tabaci and Frankliniella occidentalis (preferably on vegetables); Soil pests (such as those of the order Coleoptera), for example the species Diabrotica balteata, Agriotes spp. and Leptinotarsa decemLineata (preferably on vegetables and corn)
[0365] The term "crop plant" should also be understood to include crop plants that have been transformed by the use of recombinant DNA techniques so as to be capable of synthesizing one or more selectively acting toxins, such as those known to be derived from toxin-producing bacteria, particularly bacteria of the genus Bacillus.
[0366] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or δ-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, insecticidal proteins from Bacillus thuringiensis or plant insecticidal proteins (Vip), such as Vip1, Vip2, Vip3 or Vip3A; or bacterial-colonizing nematodes, such as Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus, etc. insecticidal proteins of Azotoxins; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and neurotoxins specific to other insects; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectin, barley lectin or snowdrop lectin; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin and papain inhibitors; ricin, corn-RIP, abrin, rufin, saporin ribosome-inactivating proteins (RIPs) such as erythrin or bryodin; steroid metabolic enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers such as blockers of sodium channels or calcium channels, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.
[0367] In the context of the present invention, delta-endotoxins are understood to mean, for example, Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or plant insecticidal proteins (Vip), such as Vip1, Vip2, Vip3, or Vip3A, and also specifically hybrid toxins, truncated toxins, and modified toxins. Hybrid toxins are produced recombinantly by combining different domains of these proteins (see, for example, WO 02 / 15701). Truncated toxins, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the native toxin are replaced. In such amino acid substitutions, preferably a non-naturally occurring protease recognition sequence is inserted into the toxin, for example, in the case of Cry3A055, a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see WO 03 / 018810).
[0368] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP 0 374 753, WO 93 / 07278, WO 95 / 34656, EP 0 427 529, EP 451 878 and WO 03 / 052073.
[0369] Methods for the preparation of such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above. Deoxyribonucleic acids of the CryI type and their preparation are known, for example, from WO 95 / 34656, EP 0 367 474, EP 0 401 979 and WO 90 / 13651.
[0370] The toxins contained in the transgenic plants confer resistance to pests found in a range of insect taxa, but are particularly common in beetles (Coleoptera), two-winged insects (Diptera), and moths (Lepidoptera).
[0371] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known, and some of them are commercially available. Examples of such plants include YieldGard® (a corn variety expressing the Cry1Ab toxin); YieldGard Rootworm® (a corn variety expressing the Cry3Bb1 toxin); YieldGard Plus® (a corn variety expressing the Cry1Ab and Cry3Bb1 toxins); Starlink® (a corn variety expressing the Cry9C toxin); Herculex I® (a corn variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) for tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety expressing the Cry1Ac toxin); Bollgard I® (a cotton variety expressing the Cry1Ac toxin); Bollgard II® (a cotton variety expressing Cry1Ac and Cry2Ab toxins); VipCot® (a cotton variety expressing Vip3A and Cry1Ab toxins); NewLeaf® (a potato variety expressing Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), and Protecta®.
[0372] Further examples of such transgenic crops are: 1. Bt11 maize, registration number C / FR / 96 / 05 / 10, manufactured by Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St. Sauveur, France). This genetically modified maize is resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) through the transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also genetically expresses the enzyme PAT to confer tolerance to the herbicide glufosinate ammonium.
[0373] 2. Bt176 maize, registration number C / FR / 96 / 05 / 10, manufactured by Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St. Sauveur, France). This genetically modified maize is resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) through transgenic expression of the Cry1Ab toxin. Bt176 maize also genetically expresses the enzyme PAT to confer tolerance to the herbicide glufosinate ammonium.
[0374] 3. MIR604 maize, registration number C / FR / 96 / 05 / 10, manufactured by Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St. Sauveur, France). This maize has been made insect-resistant by transgenic expression of a modified Cry3A toxin. The toxin is Cry3A055, modified by the insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03 / 018810.
[0375] 4. MON 863 maize, registration number C / DE / 02 / 9, manufactured by Monsanto Europe SA (270-272 Avenue de Tervuren, B-1150 Brussels, Belgium). MON 863 expresses the Cry3Bb1 toxin and confers resistance to certain Coleoptera insects.
[0376] 5. IPC 531 cotton, registration number C / ES / 96 / 02, manufactured by Monsanto Europe SA (270-272 Avenue de Tervuren, B-1150 Brussels, Belgium).
[0377] 6. 1507 Maize, registration number C / NL / 00 / 10, manufactured by Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium. Genetically modified maize for expression of the protein Cry1F for resistance to certain Lepidoptera insects and the protein PAT for resistance to the herbicide glufosinate ammonium.
[0378] 7. NK603 x MON 810 maize, registration number C / GB / 02 / M3 / 03, manufactured by Monsanto Europe SA (270-272 Avenue de Tervuren, B-1150 Brussels, Belgium). This maize consists of a conventionally bred hybrid maize variety by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 maize also genetically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which confers resistance to the herbicide Roundup® (containing glyphosate), and the Cry1Ab toxin, obtained from Bacillus thuringiensis subsp. kurstaki, which confers resistance to certain Lepidoptera, including the European corn borer.
[0379] Transgenic crops of insect-resistant plants are also described in the BATS (Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http: / / bats.ch).
[0380] The term "crop plant" should also be understood to include crop plants that have been transformed by the use of recombinant DNA technology so as to be able to synthesize antipathogenic substances with selective action, such as, for example, so-called "pathogenicity-related proteins" (PRPs, see, for example, EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesizing such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95 / 33818 and EP-A-0 353 191. Methods for producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the above-mentioned publications.
[0381] Crops can also be improved to increase resistance to fungal (e.g., Fusarium, anthracnose, or Phytophthora), bacterial (e.g., Pseudomonas), or viral (e.g., potato leaf curl virus, tomato spotted wilt virus, cucumber mosaic virus) pathogens.
[0382] Crops also include those that have a high resistance to nematodes, such as the soybean cyst nematode.
[0383] Crops that are tolerant to abiotic stress include those that have increased tolerance to drought, high salinity, high temperature, low temperature, frost, or light due to, for example, expression of NF-YB or other proteins known in the art.
[0384] Antipathogenic substances that can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers of sodium or calcium channels, e.g., viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; so-called "pathogenesis-related proteins" (PRPs; see, for example, EP 0 392 225); antipathogenic substances produced by microorganisms, such as peptide or heterocyclic antibiotics (see, for example, WO 95 / 33818) or proteins or polypeptide factors involved in plant pathogen defense (the so-called "plant disease resistance genes" described in WO 03 / 000906).
[0385] Further fields of use of the compositions according to the invention are the protection of stored goods and storage rooms and of raw materials (such as wood and textiles), floor coverings and buildings, and in the hygiene sector, in particular the protection of humans, domestic animals and productive livestock from pests of the above-mentioned types.
[0386] The present invention provides compounds of the first aspect for use in therapy. The present invention provides compounds of the first aspect for use in controlling parasites in or on animals. The present invention further provides compounds of the first aspect for use in controlling ectoparasites on animals. The present invention further provides compounds of the first aspect for use in the prevention and / or treatment of diseases transmitted by ectoparasites.
[0387] The present invention provides the use of a compound of the first aspect for the manufacture of a 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.
[0388] The present invention provides the use of a compound of the first aspect in the control of parasites in or on an animal. The present invention further provides the use of a compound of the first aspect in the control of ectoparasites on an animal.
[0389] When used in reference to parasites in or on animals, the term "control" refers to the reduction of pest or parasite numbers, the eradication of pests or parasites, and / or the prevention of further pest or parasite infestation.
[0390] The term "treating" when used in reference to parasites in or on an animal refers to suppressing, slowing, arresting or reversing the progression or severity of an existing condition or disease.
[0391] When used in reference to parasites in or on an animal, the term "prevent" refers to the avoidance of symptoms or disease developing in the animal.
[0392] When used in reference to parasites in or on animals, the term "animal" can refer to mammals and non-mammals such as birds or fish. In the case of mammals, this can 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.
[0393] A "parasite" is a pest that lives in or on a host animal and benefits from nutrients provided at the expense of the host animal. An "endoparasite" is a parasite that lives inside the body of a host animal. An "ectoparasite" is a parasite that lives on a host animal. Ectoparasites include, but are not limited to, mites, insects, and crustaceans (e.g., sea lice). The subclass Acari (or Acarina) includes ticks and mites. Ticks include, but are not limited to, members of the following genera: Rhipicaphalus, such as Rhipicaphalus (Boophilus) microplus and Rhipicephalus sanguineus; Amblyomma; Dermacentor; Haemaphysalis; Hyalomma; Ixodes; Rhipicentor; Margaropus; Argas; Otobius; and Ornithodoros. Mites include, but are not limited to, members of the following genera: Chorioptes, such as Chorioptes bovis; Psoroptes, such as Psoroptes ovis; Cheyletiella; Dermanyssus, such as Dermanyssus gallinae; Ortnithonyssus; Demodex, such as Demodex canis; Sarcoptes, such as Sarcoptes scabiei; and Psorergates.Insects include, but are not limited to, members of the following orders: Siphonaptera, Diptera, Chelonia, Lepidoptera, Coleoptera, and Homoptera. Members of the Siphonaptera order include, but are not limited to, the cat flea (Ctenocephalides felis) and the dog flea (Ctenocephatides canis). Members of the order Diptera include, but are not limited to, Musca species; bot flies, such as Gasterophilus intestinalis and Oestrus ovis; stable flies; horse flies, such as Haematopota species and Tabunus species; haematobia, such as Haematobia irritans; Stomoxys; Lucilia; midges; and mosquitoes. Members of the order Chestnuti include, but are not limited to, sucking and biting lice, such as Bovicola ovis and Bovicola bovis.
[0394] When used in connection with parasites in or on animals, the term "effective amount" refers to the amount or dosage of a compound of the present invention or a salt thereof that, upon administration to the animal in one or more doses, produces the desired effect in or on the animal. An effective amount can be readily determined by the attending diagnostician, as one skilled in the art, by using known techniques and observing results obtained under analogous circumstances. In determining an effective amount, the attending diagnostician will take into account numerous factors, including, but not limited to, the species of mammal; its size, age, and general health; the parasite and level of infestation to be controlled; the particular disease or disorder involved; the degree of complication or severity of the disease or disorder; the individual's response; the particular compound administered; the mode of administration; the bioavailability characteristics of the administered preparation; the selected dosage regimen; the use of concomitant medications; and other relevant circumstances.
[0395] The compounds of the present invention can be administered to animals by any route that has the desired effect, including, but not limited to, topical, oral, parenteral, and subcutaneous administration. Topical administration is preferred. Formulations suitable for topical administration include, for example, solutions, emulsions, and suspensions, and can be in the form of pour-ons, spots, spray-ons, spray-laces, or dips. Alternatively, the compounds of the present invention can be administered by ear tag or collar.
[0396] Salt forms of the compounds of the present invention include both pharmaceutically and veterinarily acceptable salts, which may differ from agrochemically acceptable salts. Pharmaceutically and veterinarily acceptable salts and general methodologies for preparing them are well known in the art. See, for example, Gould, PL, "Salt selection for basic drugs," International Journal of Pharmaceutics, 33:201-217 (1986); Bastin, RJ, et al., "Salt Selection and Optimization Procedures for Pharmaceutical New Chemical Entities," Organic Process Research and Development, 4:427-435 (2000); and Berge, SM, et al., "Pharmaceutical Salts," Journal of Pharmaceutical Sciences, 66:1-19 (1977). Those skilled in the art of synthesis will understand that the compounds of the present invention can be easily converted to salts such as hydrochlorides and isolated as such salts using techniques and conditions well known to those skilled in the art. Additionally, those skilled in the art of synthesis will recognize that compounds of the present invention can be readily converted from a corresponding salt to the corresponding free base, and isolated as such a salt.
[0397] The present invention also provides methods for controlling pests (such as mosquitoes and other disease vectors; see also http: / / www.who.int / malaria / vector_control / irs / en / ). In one embodiment, the method for controlling pests comprises applying a composition of the present invention to the target pest, its habitat, or a surface or substrate by brushing, rolling, spraying, painting, or dipping. By way of example, IRS (indoor residual spray) application of surfaces such as walls, ceilings, or floors is contemplated by the method of the present invention. In another embodiment, it is contemplated to apply such compositions to substrates such as nonwoven or woven materials in the form of (or in a form that can be used to manufacture) netting, clothing, bedding, curtains, and tents.
[0398] In one embodiment, a method for controlling such pests comprises applying a pesticidally effective amount of a composition of the present invention to a target pest, its habitat, or a surface or substrate to provide effective, residual pest control activity to the surface or substrate. Such application may be by brushing, rolling, spraying, painting, or dipping the pesticidal composition of the present invention. For example, IRS application to surfaces such as walls, ceilings, or floors is contemplated by the method of the present invention to provide effective, residual pest control activity to the surface. In another embodiment, the application of such compositions for residual pest control on substrates such as fabric materials in the form of (or in the form that can be used to manufacture) netting, clothing, bedding, curtains, and tents is contemplated.
[0399] The substrates to be treated, including nonwovens, fabrics, or nets, can be made of natural fibers such as cotton, raffia, jute, flax, sisal, hemp, or wool, or synthetic fibers such as polyamide, polyester, polypropylene, or polyacrylonitrile. Polyesters are particularly suitable. Methods for treating textiles are known, for example, from WO 2008 / 151984, WO 2003 / 034823, U.S. Pat. No. 5,631,072, WO 2005 / 64072, WO 2006 / 128870, EP 1 724 392, WO 2005 113 886, or WO 2007 / 090739.
[0400] A further field of use for the compositions according to the invention is that of trunk injection / trunk treatment of all ornamental trees and all kinds of fruit and nut-bearing trees.
[0401] In the field of trunk injection / trunk treatment, the compounds according to the invention are particularly suitable against wood-boring insects of the above-mentioned orders Lepidoptera and Coleoptera, in particular the woodborers listed in Tables A and B below.
[0402] [Table 2]
[0403] [Table 3-1] [Table 3-2] [Table 3-3]
[0404] The present invention may be used to control any insect pest that may be present in turfgrass, including, for example, beetles, caterpillars, fire ants, ground pearls, millipedes, pill bugs, mites, mole crickets, scale insects, mealybugs, mites, boxworms, southern chinch bugs, and grubs. The present invention may also be used to control insect pests in various stages of their life cycle, including eggs, larvae, nymphs, and adults.
[0405] In particular, the present invention relates to the treatment of grubs (Cyclocephala spp. (e.g., masked chafer, C. lurida), Rhizotrogus spp. (e.g., European chafer, R. majalis), Cotinus spp. (e.g., blue swallowtail, C. nitida), Popillia spp. (e.g., Japanese beetle, P. japonica), Phyllophaga spp. (e.g., May / June beetle), Ataenius spp., and the like). spp. (e.g., Black turfgrass ataenius, A. spretulus), Maladera spp. (e.g., red-veined scarab beetle, M. castanea) and Tomarus spp.), cotton bollworms (Margarodes spp.), mole crickets (tawny, southern and brachypterous; Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula The compounds of the present invention can be used to control insect pests that feed on the roots of turfgrass, including Pseudomonas spp.
[0406] The present invention may also be used to control straw-dwelling insect pests of turfgrass, including cutworms (such as Spodoptera frugiperda and the common armyworm (Pseudaletia unipuncta)), cutworms, weevils (such as Sphenophorus spp., S. venatus vestitus, and S. parvulus) and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis).
[0407] The present invention may also be used to control insect pests that live on the ground and feed on turfgrass leaves, including the lesser stink bug (such as the southern kinkbag, Blissus insularis), bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug (Antonina graminis), two-lined spittlebug (Prosapia bicincta), leafhoppers, cutworms (Noctuidae), and greengrass aphids.
[0408] The present invention may also be used to control other pests of turfgrass, such as the red fire ant (Solenopsis invicta), which creates ant mounds in turfgrass.
[0409] In the hygiene field, the compositions according to the invention are effective against ectoparasites such as hard ticks, soft ticks, scabies mites, chiggers, flies (stable flies and licking flies), parasitic fly larvae, lice, pubic lice, biting lice and fleas.
[0410] Examples of such parasites are: Among the Anoplurida, the genera Haematopinus, Linognathus, Pediculus, Phtirus, and Solenopotes are included.
[0411] From the order Mallophagida, the genera Trimenopon, Menopon, Trinoton, Bovicola, Werneckiella, Lepikentron, Damalina, Trichodectes and Felicola.
[0412] Among the order Diptera and its suborders Nematocerina and Brachycerina, for example, the genera Aedes, Anopheles, Culex, Simulium, Eusimulium, Phlebotomus, Lutzomyia, Culicoides, Chrysops, Hybomitra, Atylotus, Tabanus, 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.), sheep flies (Oestrus spp.), cow flies (Hypoderma spp.), bot flies (Gasterophilus spp.), hood flies (Hippobosca spp.), deer flies (Lipoptena spp.) and sheep hood flies (Melophagus spp.).
[0413] Among the Siphonapterida, for example, the human flea genus (Pulex spp.), the dog flea genus (Ctenocephalides spp.), the mouse flea genus (Xenopsylla spp.), and the long flea genus (Ceratophyllus spp.).
[0414] From the order Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp., and Panstrongylus spp.
[0415] From the order Blattaria, for example, the Asian cockroach (Blatta orientalis), the American cockroach (Periplaneta americana), the German cockroach (Blattela germanica) and the genus Supella.
[0416] Among the subclass Acaria (Acarida) and the suborder Metastigmata and Mesostigmata, for example, the genera Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp. spp.), Pneumonyssus spp., Sternostoma spp. and Varroa spp.
[0417] From the orders Actinedida (Prostigmata) and Acaridida (Astigmata), for example, the genera Acarapis, Cheyletiella, Ornithocheyletia, Myobia, Psorergates, Demodex, Trombicula, Listrophorus, Acarus, Tyrophagus, Caloglyphus, Hypodectes spp.), Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.
[0418] The compositions according to the invention are also suitable for protecting against insect infestation in materials such as wood, textiles, plastics, adhesives, glues, paints, paper and cardboard, leather, floor coverings and building materials.
[0419] The compositions according to the invention can be used, for example, against the following pests: European house borer (Hylotrupes bajulus), Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, pine wood beetle (Ernobius mollis), longhorn beetle (Priobium carpini), flat-headed beetle (Lyctus brunneus), African flat-headed beetle (Lyctus africanus), American flat-headed beetle (Lyctus planicollis), oak flat-headed beetle (Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec.and Dinoderus minutus, as well as hymenopteran insects such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, and Urocerus augur, as well as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, and other insects of the genus Kalotermes. Termites such as Mastotermes darwiniensis, Zootermopsis nevadensis, and Coptotermes formosanus, as well as wood mites such as Lepisma saccharina.
[0420] The compounds of formula (I) and (I') or salts thereof are particularly suitable for controlling one or more pests selected from the families: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae and Heteroderidae. In a preferred embodiment of each aspect, compound TX (wherein the abbreviation "TX" means "one compound selected from the compounds defined in Tables A-1 to A-78, B-1 to B-78, C-1 to C-21 and D-1 to D-21") controls one or more pests selected from the families: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae and Heteroderidae.
[0421] The compounds of formula (I) and (I') or salts thereof are effective against pests of the genera 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. spp. In a preferred embodiment of each aspect, the compound TX (here, the abbreviation "TX" means "one compound selected from the compounds defined in Tables A-1 to A-78, B-1 to B-78, C-1 to C-21, and D-1 to D-21") is selected from the group consisting of Spodoptera spp., Plutella spp., Frankliniella spp., Thrips spp., Euschistus spp., Cydia spp., Nilaparvata spp., Myzus spp., Aphis spp., Diabrotica spp. The present invention relates to the control of one or more pests selected from the group consisting of Rhopalosiphum spp, Pseudoplusia spp and Chilo spp.
[0422] The compounds of formula (I) and (I') or salts thereof are particularly suitable for controlling one or more of Spodoptera littoralis, diamondback moth (Plutella xylostella), western flower thrips (Frankliniella occidentalis), onion thrips (Thrips tabaci), Euschistus heros, codling moth (Cydia pomonella), brown planthopper (Nilaparvata lugens), green peach aphid (Myzus persicae), Chrysodeixis includens, bean aphid (Aphis craccivora), Diabrotica balteata, Rhopalosiphum padi and rice stem borer (Chilo suppressalis).
[0423] In a preferred embodiment of each aspect, compound TX (wherein the abbreviation "TX" means "one compound selected from the compounds defined in Tables A-1 to A-78, B-1 to B-78, C-1 to C-21, and D-1 to D-21") is effective against Egyptian armyworm (Spodoptera littoralis), diamondback moth (Plutella xylostella), western flower thrips (Frankliniella occidentalis), onion thrips (Thrips tabaci), Euschistus heros, codling moth (Cydia pomonella), brown planthopper (Nilaparvata lugens), green peach aphid (Myzus persicae), Chrysodeixis includens, bean aphid (Aphis craccivora, Diabrotica balteata, Rhopalosiphum Padia, and Chilo suppressalis such as Egyptian armyworm (Spodoptera littoralis) + TX, diamondback moth (Plutella xylostella) + TX; western flower thrips (Frankliniella occidentalis) + TX, onion thrips (Thrips tabaci) + TX, Euschistus heros + TX, codling moth (Cydia pomonella) + TX, brown planthopper (Nilaparvata lugens) + TX, green peach aphid (Myzus persicae) + TX, Chrysodeixis includens + TX, bean aphid (Aphis craccivora + TX, Diabrotica balteata + TX, Rhopalosiphum Padi + TX and Chilo suppressalis + TX are controlled.
[0424] In one embodiment of each aspect, one compound from Tables A-1 to A-78, B-1 to B-78, C-1 to C-21, and D-1 to D-21 is used to control Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Codling moth, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis includens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum Padi and Chilo suppressalis.
[0425] In one embodiment, one compound from Tables A-1 to A-78, B-1 to B-78, C-1 to C-21 and D-1 to D-21 is suitable for controlling Mamestra (preferably in vegetables), codling moth (Cydia pomonella) (preferably in apple), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potato) and Chilo supressalis (preferably in rice).
[0426] The compounds of the present invention may have 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 (e.g., high biological activity, advantageous spectrum of activity, high safety profile (e.g., improved physicochemical properties or high biodegradability against above- and below-ground non-target organisms such as fish, birds and bees)). In particular, it has surprisingly been found that certain compounds of formula (I) may exhibit advantageous safety profiles, especially against non-target arthropods, such as pollinators such as honeybees, solitary bees and bumblebees, most particularly the European honeybee (Apis mellifera).
[0427] Although the compounds of the present invention can be used as pesticides in their native form, they are generally formulated into compositions using formulation aids such as carriers, solvents, and surfactants in various ways. The formulations can be in various physical forms, such as dustable powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-based flowables, aqueous dispersions, oil-based dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (containing water or a water-miscible organic solvent as a carrier), impregnated polymer films, or other forms known from, for example, the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can be used directly or diluted before use. Dilution can be carried out, for example, with water, liquid fertilizers, trace elements, biological materials, oils, or solvents.
[0428] The formulations can be prepared by mixing the active ingredient with formulation aids to obtain a composition in the form of, for example, finely divided solids, granules, solutions, dispersions, or emulsions. The active ingredient can also be formulated with other adjuvants, such as finely divided solids, mineral oil, vegetable or animal oil, modified vegetable or animal oil, organic solvent, water, surfactant, or combinations thereof.
[0429] The active ingredient can also be contained in extremely fine microcapsules. Microcapsules contain the active ingredient in a porous carrier, allowing the active ingredient to be released into the environment in controlled amounts (e.g., sustained release). Microcapsules typically have diameters of 0.1 to 500 microns. They contain the active ingredient in an amount of about 25 to 95% by weight of the capsule. The active ingredient can be in the form of a bulk solid, fine particles in a solid or liquid dispersion, or a suitable solution. The encapsulating membrane can comprise, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymer, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane, or chemically modified polymers, and starch xanthate, or other polymers known to those skilled in the art. Alternatively, extremely fine microcapsules can be formed containing the active ingredient in the form of fine particles in a base solid matrix, but the microcapsules themselves are not encapsulated.
[0430] The formulation auxiliaries suitable for preparing the compositions according to the invention are known per se. Examples of liquid carriers include water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietic acid, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-Trichloroethane, 2-heptanone, α-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate Examples of suitable solvents include ethanol, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol and high molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, and N-methyl-2-pyrrolidone.
[0431] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, Kiesslager, limestone, calcium carbonate, bentonite, calcium montmorillonite, cotton hulls, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin, and similar materials.
[0432] Many surface-active substances can be used advantageously in both solid and liquid formulations, especially in formulations that can be diluted with a carrier before use. The surface-active substances can be anionic, cationic, nonionic, or polymeric, and they can be used as emulsifying agents, wetting agents, or suspending agents, or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates such as calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide adducts such as nonylphenol ethoxylate; alcohol / alkylene oxide adducts such as tridecyl alcohol ethoxylate; soaps such as sodium stearate; salts of alkylnaphthalenesulfonates such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinates such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters such as sorbitol oleate; quaternary amines such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkyl phosphate esters; and further substances described, for example, in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood, New Jersey (1981).
[0433] Additional adjuvants that may be used in the pest control formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, antifoaming agents, complexing agents, neutralizing or pH adjusting and buffering agents, corrosion inhibitors, fragrances, wetting agents, uptake enhancers, trace elements, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze agents, fungicides and liquid and solid fertilizers.
[0434] The compositions of the present invention may contain additives including vegetable or animal oils, mineral oils, alkyl esters of such oils, or mixtures of such oils and oil derivatives. The amount of oil additive in the compositions of the present invention is generally 0.01 to 10% based on the mixture to be applied. For example, the oil additive can be added to the spray tank at the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oils or vegetable oils such as rapeseed oil, olive oil, or sunflower oil, emulsified vegetable oils, alkyl esters of vegetable oils such as methyl derivatives, or animal oils such as fish oil or beef tallow. Preferred oil additives are C8 to C 22 Alkyl esters of fatty acids, especially C 12 ~C 18 Methyl derivatives of fatty acids, including, for example, the methyl esters of lauric acid, palmitic acid, and oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Many oil derivatives are listed in the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.
[0435] The compositions of the present invention generally comprise 0.1 to 99% by weight, especially 0.1 to 95% by weight, of the compounds of the present invention and 1 to 99.9% by weight of formulation aids, which preferably include 0 to 25% by weight of surfactants. Although commercial products may preferably be formulated as concentrates, end users will typically utilize diluted formulations.
[0436] The application rates vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pests to be controlled, the prevailing weather conditions and other factors which depend on the method, time of application and the target crop. As a general guideline, the compounds may be applied in amounts of 1 to 2000 l / ha, especially 10 to 1000 l / ha.
[0437] Formulation types include emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water dispersible granules (WG), emulsifiable granules (EG), emulsions, water-in-oil (EO), emulsions, oil-in-water (EW), microemulsions (ME), oil dispersions (OD), oil-miscible flowables (OF), oil-miscible liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), technical concentrates (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG) or any technically preferred formulation in combination with agriculturally acceptable adjuvants.
[0438] A preferred formulation may have the following composition (by weight): Emulsifiable concentrate: Active ingredient: 1-95%, preferably 60-90% Surfactant: 1 to 30%, preferably 5 to 20% Liquid carrier: 1 to 80%, preferably 1 to 35%
[0439] Powder: Active ingredient: 0.1 to 10%, preferably 0.1 to 5% Solid carrier: 99.9 to 90%, preferably 99.9 to 99%
[0440] Suspension concentrate: Active ingredient: 5-75%, preferably 10-50% Water: 94-24%, preferably 88-30% Surfactant: 1 to 40%, preferably 2 to 30%
[0441] Wettable powder: Active ingredient: 0.5 to 90%, preferably 1 to 80% Surfactant: 0.5 to 20%, preferably 1 to 15% Solid carrier: 5 to 95%, preferably 15 to 90%
[0442] Granules: Active ingredient: 0.1 to 30%, preferably 0.1 to 15% Solid carrier: 99.5 to 70%, preferably 97 to 85%
[0443] The following mixtures of compounds of formula (I) with active ingredients are preferred (the abbreviation "TX" means "one compound selected from the compounds defined in Tables A-1 to A-78, B-1 to B-78, C-1 to C-21, and D-1 to D-21, and Table P"): An adjuvant selected from the group of substances consisting of petroleum (alternative name) (628) + TX; Abamectin +TX, Acequinocyl +TX, Acetamiprid +TX, Acetoprole +TX, Acrinathrin +TX, Acinonapyr +TX, Afidopiropen +TX, Afoxolaner +TX, Alanycarb +TX, Allethrin +TX, α-Cypermethrin +TX, Alphamethrin +TX, Amidoflumet +TX, Aminocarb +TX, Azocyclotine +TX, Bensultap +TX, Benzoximate +TX, Benzpyrimoxane + TX, beta-cyfluthrin + TX, beta-cypermethrin + TX, bifenazate + TX, bifenthrin + TX, binapacryl + TX, bioallethrin + TX, S bioallethrin + TX, bioresmethrin + TX, bistrifluron + TX, brofuranilide + TX, brofluthrinate + TX, bromophos-ethyl + TX, buprofezin + TX, butocarboxim + TX, cadusafos + TX, carbaryl + TX, carbosulfan + TX, Kartap+TX, CAS number: 1632218-00-8+TX, CAS number: 1808115-49-2+TX, CAS number: 2032403-97-5+ TX, CAS number:2044701-44-0+TX, CAS number:2128706-05-6+TX, CAS number:2095470-94-1+TX, CAS number:2 377084-09-6+TX, CAS number: 1445683-71-5+TX, CAS number: 2408220-94-8+TX, CAS number: 2408220-91- 5+TX, CAS number: 1365070-72-9+TX, CAS number: 2171099-09-3+TX, CAS number: 2396747-83-2+TX, CAS number :2133042-31-4+TX, CAS number:2133042-44-9+TX, CAS number:1445684-82-1+TX, CAS number:1445684- 82-1+TX, CAS number:1922957-45-6+TX, CAS number:1922957-46-7+TX, CAS number:1922957-47-8+TX, CA S number: 1922957-48-9+TX, CAS number: 2415706-16-8+TX, CAS number: 1594624-87-9+TX, CAS number: 159463 7-65-6+TX, CAS number: 1594626-19-3+TX, CAS number: 1990457-52-7+TX, CAS number: 1990457-55-0+TX,CAS No.: 1990457-57-2+TX, CAS No.: 1990457-77-6+TX, CAS No.: 1990457-66-3+TX, CAS No.: 1990457-85-6+TX, CAS No.: 2220132-55-6+TX, CAS No.: 1255091-74-7+TX, CAS No.: RNA (Colorado potato beetle (Leptinotarsa decemLineata)-specific recombinant double-stranded interference (GS2) + TX, CAS No.: 2719848-60-7 + TX, CAS No.: 1956329-03-5 + TX, chlorantraniliprole + TX, chlordane + TX, chlorfenapyr + TX, chlorprallethrin + TX, chromafenozide + TX, clenpirin + TX, cloetocarb + TX, clothianidin + TX, 2-chlorophenyl N-methylcarbamate (CPMC) + TX, cyanofenphos +TX, cyantraniliprole +TX, cyclaniliprole +TX, cyclobutrifluram +TX, cycloprothrin +TX, cycloxapride +TX, cyenopyrafen +TX, cetopyrafen (or ethopyrafen) +TX, cyflumetofen +TX, cyfluthrin +TX, cyhalodiamide +TX, cyhalothrin +TX, cypermethrin +TX, cyphenothrin +TX, cyprofanilide +TX, cyromazine +TX, deltamethrin +TX, diafenthin Uron + TX, Dialifos + TX, Dibrom + TX, Dichloromezothiaz + TX, Diflobidazin + TX, Diflubenzuron + TX, Dinpropylidaz + TX, Dinactin + TX, Dinocap + TX, Dinotefuran + TX, Dioxabenzophos + TX, Emamectin (or Emamectin benzoate) + TX, Empenthrin + TX, Epsilon-Monfluorothrin + TX, Epsilon-Metofluthrin + TX, Esfenvalerate + TX, Ethion + TX, Ethion Tiprole +TX, Etofenprox +TX, Etoxazole +TX, Famflur +TX, Fenazaquin +TX, Fenfluthrin +TX, Fenmezodithiaz +TX, Fenitrothion +TX, Fenobucarb +TX, Fenothiocarb +TX, Fenoxycarb +TX, Fenpropathrin +TX, Fenpyroximate +TX, Fensulfothion +TX, Fenthion +TX, Fentin acetate +TX, Fenvalerate +TX, Fipronil +TX,Flometquine +TX, Flonicamid +TX, Fluacrypyrim +TX, Fluazaindolizine +TX, Fluazuron +TX, Flubendiamide +TX, Flubenzoimine +TX, Fluchlordiniliprole +TX, Flucythrinate +TX, Flucycloxuron +TX, Flucythrinate +TX, Fluensulfone +TX, Flufenerim +TX, Flufenprox +TX, Flufiprole +TX, Fluhexafon +TX, Flumethrin +TX, Fluopyram +TX, Flupentiofenox +TX, Flupyradifurone +TX, Flupirimine +TX X, fluralaner + TX, fluvalinate + TX, fluxamethamide + TX, fosthiazate + TX, gamma-cyhalothrin + TX, guadipyr + TX, halofenozide + TX, halfenprox + TX, heptafluthrin + TX, hexythiazox + TX, hydramethylnon + TX, imicyafos + TX, imidacloprid + TX, imiprothrin + TX, indazapiroxameth + TX, indoxacarb + TX, iodomethane + TX, iprodione + TX, isocycloceram + TX, isothioate + TX, ivermectin + TX, kappa-bifu Fentrin + TX, kappa-tefluthrin + TX, lambda-cyhalothrin + TX, lepimectin + TX, lotilaner + TX, lufenuron + TX, metaflumizone + TX, metaldehyde + TX, metam + TX, methomyl + TX, methoxyfenozide + TX, metofluthrin + TX, metolcarb + TX, mexacarbate + TX, milbemectin + TX, momfluorotrin + TX, niclosamide + TX, nicofluprole + TX, nitenpyram + TX, nithiazine + TX, omethoate + TX, oxamyl + TX, oxazosulfil + TX, parathion Onethyl + TX, Permethrin + TX, Fenothrin + TX, Phosphocarb + TX, Piperonyl butoxide + TX, Pirimicarb + TX, Pirimiphos-ethyl + TX, Pirimiphos-methyl + TX, Polyhedrosis virus + TX, Prallethrin + TX, Profenofos + TX, Profluthrin + TX, Propargite + TX, Propetamphos + TX, Propoxur + TX, Prothiofos + TX, Protrifenbut + TX, Piflubumid + TX, Pymetrozine + TX, Pyraclofos + TX, Pyrafluprole + TX, Pyridaben + TX, Pyridalyl + TX,Pyrifluquinazone +TX, Pyrimidifen +TX, Pyriminostrobin +TX, Pyriprole +TX, Pyriproxyfen +TX, Resmethrin +TX, Sarolaner +TX, Selamectin +TX, Silafluofen +TX, Spinetoram +TX, Spinosad +TX, Spirobudifen +TX, Spirodiclofen +TX, Spiromesifen +TX, Spiropydione +TX, Spirotetramat +TX, Spidoxamat +TX, Sulfoxaflor +TX, Te Bufenozide + TX, Tebufenpyrad + TX, Tebupirimiphos + TX, Tefluthrin + TX, Temephos + TX, Tetrachlorantraniliprole + TX, Tetradifon + TX, Tetramethrin + TX, Tetramethylfluthrin + TX, Tetranactin + TX, Tetraniliprole + TX, Theta-Cypermethrin + TX, Thiacloprid + TX, Thiamethoxam + TX, Thiocyclam + TX, Thiodicarb + TX, Thiofanox + TX, Thiometon +TX, Thiosultap +TX, Tigoraner +TX, Thiolantraniliprole +TX, Thioxazafen +TX, Tolfenpyrad +TX, Toxaphene +TX, Tralomethrin +TX, Transfluthrin +TX, Triazamate +TX, Triazophos +TX, Trichlorfon +TX, Trichloronate +TX, Trichlorfon +TX, Trifluenfuronate +TX, Triflumezopyrim +TX, Cyclopyrazoflurane +TX, Zeta-cypermethrin Phosphorus +TX, seaweed extract and fermentation product derived from Melasse +TX, seaweed extract and fermentation product derived from Melasse containing urea +TX, amino acids +TX, potassium and molybdenum and EDTA-chelated manganese +TX, seaweed extract and fermented plant product +TX, seaweed extract and fermented plant product containing plant hormones +TX, vitamins +TX, EDTA-chelated copper +TX, zinc +TX, and iron +TX, azadirachtin +TX, Bacillus aizawai +TX, Bacillus chitinosporus AQ746 (NRRL accession number B-21618) +TX, Bacillus firmus +TX, Bacillus kurstaki +TX,Bacillus mycoides AQ726 (NRRL accession number B-21664) + TX, Bacillus pumilus (NRRL accession number B-30087) + TX, Bacillus pumilus AQ717 (NRRL accession number B-21662) + TX, Bacillus sp. AQ178 (ATCC accession number 53522) + TX, Bacillus sp. AQ175 (ATCC accession number 55608) + TX, Bacillus sp. AQ177 (ATCC accession number 55609) + TX, Bacillus subtilis unspecified + TX, Bacillus subtilis AQ153 (ATCC accession number 55614) + TX, Bacillus subtilis AQ30002 (NRRL accession number B-50421) + TX, Bacillus subtilis AQ30004 (NRRL accession number B-50455) + TX, Bacillus subtilis AQ713 (NRRL accession number B-21661) + TX, Bacillus subtilis AQ743 (NRRL accession number B-21665) + TX, Bacillus thuringiensis AQ52 (NRRL accession number B-21619) + TX, Bacillus thuringiensis thuringiensis BD#32 (NRRL accession number B-21530) + TX, Bacillus thuringiensis subspec. kurstaki BMP123 + TX, Beauveria bassiana + TX, D-limonene + TX, granulovirus + TX, harpin + TX, Helicoverpa armigera nucleopolyhedrovirus + TX, Helicoverpa zea nucleopolyhedrovirus + TX, Heliothis virescens nucleopolyhedrovirus + TX, Heliothis punctigera nucleopolyhedrovirus + TX, Metarhizium spp.) + TX, Muscodor albus 620 (NRRL accession number 30547) + TX, Muscodor roseus A3-5 (NRRL accession number 30548) + TX, Neem tree-based products + TX, Paecilomyces fumosoroseus + TX, Paecilomyces lilacinus + TX, Pasteuria nishizawae + TX, Pasteuria penetrans + TX, Pasteuria ramosa + TX, Pasteuria thornei + TX, Pasteuria usugae usgae + TX, P-cymene + TX, Plutella xylostella granulosis virus + TX, Plutella xylostella nucleopolyhedrovirus + TX, polyhedrovirus + TX, pyrethrum + TX, QRD420 (terpenoid blend) + TX, QRD452 (terpenoid blend) + TX, QRD460 (terpenoid blend) + TX, Quillaja saponaria + TX, Rhodococcus globerulus AQ719 (NRRL accession number B-21663) + TX, Spodoptera frugiperda nucleopolyhedrovirus + TX, Streptomyces gallus galbus (NRRL accession number 30232) + TX, Streptomyces sp. (NRRL accession number B-30145) + TX, terpenoid blend + TX, and Verticillium spp. + TX; an algicide selected from the group of substances consisting of bethoxadin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, sibutrin [CCN] + TX, dichloron (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamide (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX; an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomate (1011) + TX, cyclobutrifluram + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX; an avian repellent selected from the group of substances consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX; 1-Hydroxy-1H-pyridine-2-thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodisin (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargafen (alternative name) [CCN] + T a fungicide selected from the group of substances consisting of X, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX, and thiomersal (alternative name) [CCN] + TX; Adoxophyes orana GV (alternate name) (12) + TX, Agrobacterium radiobacter (alternate name) (13) + TX, Amblyseius spp. (alternate name) (19) + TX, Anagrapha falcifera NPV (alternate name) (28) + TX, Anagrus atomus (alternate name) (29) + TX, Aphelinus abdominalis (alternate name) (33) + TX, Aphidius colemani (alternate name) (34) + TX, Aphidoletes aphidimyza (alternate name) (35) + TX, Autographa californica californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide (scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51) + TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. japonensis subsp. japonensis) (scientific name) (51) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51) + TX, Bacillus thuringiensis subsp. tenebrionis (Bacillus thuringiensis subsp.tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alternate name) (53) + TX, Beauveria brongniartii (alternate name) (54) + TX, Chrysoperla carnea (alternate name) (151) + TX, Cryptolaemus montrouzieri (red ladybird beetle) (alternate name) (178) + TX, Cydia pomonella GV (alternate name) (191) + TX, Dacnusa sibirica (alternate name) (212) + TX, Diglyphus isaea (alternate name) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus (alternate name) (300) + TX, Helicoverpa zea NPV (alternate name) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alternate name) (433) + TX, Hippodamia convergens (alternate name) (442) + TX, Leptomastix dactylopii (alternate name) (488) + TX, Macrolophus caliginosus (alternate name) (491) + TX, Mamestra brassicae brassicae NPV (alternate name) (494) + TX, Metaphycus helvolus (alternate name) (522) + TX, Metarhizium anisopliae var. acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. leconti (N.lecontei NPV (alternate name) (575) + TX, Orius spp. (alternate name) (596) + TX, Paecilomyces fumosoroseus (alternate name) (613) + TX, Phytoseiulus persimilis (alternate name) (644) + TX, Spodoptera exigua multicapsid nucleopolyhedrovirus (scientific name) (741) + TX, Steinernema bibionis (alternate name) (742) + TX, Steinernema carpocapsae (alternate name) (742) + TX, Steinernema felziae feltiae (alternate name) (742) + TX, Steinernema glaseri (alternate name) (742) + TX, Steinernema riobrave (alternate name) (742) + TX, Steinernema riobravis (alternate name) (742) + TX, Steinernema scapterisci (alternate name) (742) + TX, Steinernema spp. (alternate name) (742) + TX, Trichogramma spp. (alternate name) (826) + TX, Typhlodromus occidentalis a biological agent selected from the group of substances consisting of Verticillium lecanii (alternative name) (848) + TX; a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX; chemical disinfectants selected from the group of substances consisting of Apholate [CCN] + TX, Visadyl (alternative name) [CCN] + TX, Busulfan (alternative name) [CCN] + TX, Diflubenzuron (250) + TX, Dimatif (alternative name) [CCN] + TX, Hemel [CCN] + TX, Hempa [CCN] + TX, Metepa [CCN] + TX, Methiotepa [CCN] + TX, Methyl Apholate [CCN] + TX, Morzide [CCN] + TX, Penfluron (alternative name) [CCN] + TX, Tepa [CCN] + TX, Thiohempa (alternative name) [CCN] + TX, Thiotepa (alternative name) [CCN] + TX, Tretamine (alternative name) [CCN] and Uredepa (alternative name) [CCN] + TX; (E)-Deca-5-en-1-yl acetate and (E)-dec-5-en-1-ol (IUPAC name) (222) + TX, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, (E,Z)-tetradec-4,1 0-Dien-1-yl acetate (IUPAC name) (779) + TX, (Z)-Dodec-7-en-1-yl acetate (IUPAC name) (285) + TX, (Z)-Hexadec-11-enal (IUPAC name) (436) + TX, (Z)-Hexadec-11-en-1-yl acetate (IUPAC name) (437) + TX, (Z)-Hex Sadec-13-en-11-yn-1-yl acetate (IUPAC name) (438) + TX, (Z)-Icos-13-en-10-one (IUPAC name) (448) + TX, (Z)-tetradec-7-en-1-al (IUPAC name) (782) + TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783) + TX, ( Z)-Tetradeca-9-en-1-yl acetate (IUPAC name) (784) + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283) + TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780) + TX, (9Z,12E)-tetradeca-9,12-Dien-1-yl acetate (IUPAC name) (781) + TX, 14-methyloctadec-1-ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol and 4-methylnonan-5-one (IUPAC name) (544) + TX, alpha-multistriatin (alternative name) [CCN] + TX, Brevicomin (alternative name) [CCN] + TX, Codrelure (alternative name) [CCN] + TX, Codlemone (alternative name) (167) + TX, Cure (alternative name) (179) + TX , Disparlure (277) + TX, Dodec-8-en-1-yl acetate (IUPAC name) (286) + TX, Dodec-9-en-1-yl acetate (IUPAC name) (287) + TX, Dodec-8 + TX, 10-dien-1-yl acetate (IUPAC name) (284) + TX, Dominicalure (alternative name) [CCN] + TX, Ethyl 4-methyloctanoate (IUPAC name) (317) + TX, Eugenol (alternative name) [CCN] + TX, Frontalin (alternative name) [CCN] + T X, a 1:1 mixture of the (Z,E) and (Z,Z) isomers of Gossyplure® (alternative name: hexadeca-7,11-dien-1-yl-acetate) (420) + TX, Grandolure (421) + TX, Grandolure I (alternative name) (421) + TX, Grandolure II (alternative name) (421) + TX, Grandolure III (alternative name) (421) + TX, Grandolure IV (alternative name) (421) + TX, Hexalure [CCN] + TX, Ipsdienol (alternative name) [CCN] + TX, Ipsenol (alternative name) [CCN] + TX, Japonirua (alternative name) (481) + TX, Lineatin (alternative name) [CCN] + TX, Litirua (alternative name) [CCN] + TX, Lupulua (alternative name) [CCN] + TX, Medurua [CCN] + TX, Megatomoic acid (alternative name) [CCN] + TX, Methyleugenol (alternative name) (540) + TX, Muscalua (563) + TX, Octadeca-2,13-dien-1-yl acetate (IUPAC name) (588) + TX, Octadeca-3,13-Dien-1-yl acetate (IUPAC name) (589) + TX, Olfrulure (alternative name) [CCN] + TX, Orictalure (alternative name) (317) + TX, Ostramon (alternative name) [CCN] + TX, Siglua [CCN] + TX, Soldigin (alternative name) (736) + TX, Sulcatol (alternative name) [CCN] + TX, Tetradec-11-en-1-yl acetate (IU an insect pheromone selected from the group of substances consisting of Trimedulla (PAC name) (785) + TX, Trimedulla (839) + TX, Trimedulla A (alternate name) (839) + TX, Trimedulla B1 (alternate name) (839) + TX, Trimedulla B2 (alternate name) (839) + TX, Trimedulla C (alternate name) (839) and Trunk-call (alternate name) [CCN] + TX; an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethylcarbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX; Bis(tributyltin)oxide (IUPAC name) (913) + TX, Bromoacetamide [CCN] + TX, Calcium arsenate [CCN] + TX, Cloethocarb (999) + TX, Copper acetarsenite [CCN] + TX, Copper sulfate (172) + TX, Fentin (347) + TX, Ferric phosphate (IUPAC name) (352) + TX, Metaldehyde (518) + TX, Methiocarb (530) + TX, Niclosamide (576) + TX, Niclosamide-olamine (576) + TX, Pentachloroethylene (Phenylalanine) a molluscicide selected from the group of substances consisting of: chlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, thazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, triphenmorph (1454) + TX, trimethacarb (840) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, pyriprole [394730-71-3] + TX; AKD-3088 (compound code) + TX, 1,2-dibromo-3-chloropropane (IUPAC / Chemical Abstracts Name) (1045) + TX, 1,2-dichloropropane (IUPAC / Chemical Abstracts Name) (1062) + TX, 1,2-dichloropropane and 1,3-dichloropropene (IUPAC Name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC / Chemical Abstracts Name) (1065) + TX, 3-(4-chlorophenyl) -5-Methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alternative name) (210) + TX, abamectin (1) + TX, acetoprole [CCN] + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxicarb (863) + TX, AZ60541 (compound code) + TX, benclotiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alternative name) + TX, Cadusafos (109) + TX, Carbofuran (118) + TX, Carbon Disulfide (945) + TX, Carbosulfan (119) + TX, Chloropicrin (141) + TX, Chlorpyrifos (145) + TX, Cloetocarb (999) + TX, Cyclobutrifluram + TX, Cytokinin (alternative name) (210) + TX, Dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, Diamidafos (1044) + TX, Diclofenthion (1051) + TX, Dicrifos (alternative name) + TX, Dimethoate (262) + T X, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ethoprophos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fenpyrad (alternative name) + TX, fensulfothion (1158) + TX, fosthiazate (408) + TX, fostietan (1196) + TX, furfural (alternative name) [CCN] + TX, GY-81 (development code) (423) + TX, heterophos [CCN] + TX,Iodomethane (IUPAC name) (542) + TX, Isamidophos (1230) + TX, Isazophos (1231) + TX, Ivermectin (alternative name) [CCN] + TX, Kinetin (alternative name) (210) + TX, Mecarfone (1258) + TX, Metam (519) + TX, Metam-potassium (alternative name) (519) + TX, Metam-sodium (519) + TX, Methyl bromide (537) + TX, Methyl isothiocyanate (543) + TX, Milbemycin oxime (alternative name) [CCN] + TX, Moxidectin (alternative name [CCN] + TX, Myrothecium verrucaria) Composition (alternative name) (565) + TX, NC-184 (compound code) + TX, Oxamyl (602) + TX, Phorate (636) + TX, Phosphamidon (639) + TX, Phosphocarb [CCN] + TX, Cebufos (alternative name) + TX, Selamectin (alternative name) [CCN] + TX, Spinosad (737) + TX, Terbam (alternative name) + TX, Terbufos (773) + TX, Tetrachlorothiophene (IUP a nematicide selected from the group of substances consisting of AC / Chemical Abstracts Name) (1422) + TX, Thiafenox (alternative name) + TX, Thionazine (1434) + TX, Triazophos (820) + TX, Triazuron (alternative name) + TX, Xylenol [CCN] + TX, YI-5302 (compound code) and Zeatin (alternative name) (210) + TX, Fluensulfone [318290-98-1] + TX, Fluopyram + TX; a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX; a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX; 2-Isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminum phosphide (640) + TX, anthracene (880) + TX, arsenic trioxide (882) + TX, barium carbonate (891) + TX, bisthiosemi (912) + TX, brodifacoium (89) + TX, bromadiolone (including alpha-bromadiolone) +TX, Bromethalin (92) +TX, Calcium cyanide (444) +TX, Chloralose (127) +TX, Chlorophacinone (140) +TX, Cholecalciferol (alternative name) (850) +TX, Coumacrol (1004) +TX, Coumafuryl (1005) +TX, Coumatetralyl (175) +TX, Crimidine (1009) +TX, Difenacoum (246) +TX, Difethialone (249) +TX, Diphacinone (273) +TX, Ergocalciferol (301) +TX, Flo Coumaphene (357) + TX, Fluoroacetamide (379) + TX, Flupropaline (1183) + TX, Flupropaline Hydrochloride (1183) + TX, gamma-HCH (430) + TX, HCH (430) + TX, Hydrogen Cyanide (444) + TX, Iodomethane (IUPAC name) (542) + TX, Lindane (430) + TX, Magnesium Phosphide (IUPAC name) (640) + TX, Methyl Bromide (537) + TX, Norbormide (1318) + TX, Fosacetim (1336) + TX, Fosacetim a rodenticide selected from the group of substances consisting of sphingosine (IUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371) + TX, sciliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851) and zinc phosphide (640) + TX; a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934) + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol and nerolidol (alternative names) (324) + TX, MB-599 (development code) (498) + TX, MGK264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piperotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesamolin (1394) and sulfoxide (1406) + TX; an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetate (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN], and ziram (856) + TX; a virucidal agent selected from the group of substances consisting of Imanin (alternative name) [CCN] and Ribavirin (alternative name) [CCN] + TX; a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octilinone (590) and thiophanate-methyl (802) + TX; 1,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX, 2,4-dichlorophenylbenzenesulfonate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 4-chlorophenylphenylsulfone + TX, acetoprole + TX, aldoxicarb + TX, amidithione + TX, amidothioate + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, alamite + TX, arsenic oxide + TX, azobenzene + TX, azotoate + TX, benomyl + TX, benoxaphos + TX, ben Dibenzoate + TX, Bixafen + TX, Brofenvalerate + TX, Bromocyclen + TX, Bromophos + TX, Bromopropylate + TX, Buprofezin + TX, Butocarboxim + TX, Butoxycarboxim + TX, Butylpyridaben + TX, Calcium polysulfide + TX, Camphechlor + TX, Carbanolate + TX, Carbophenothion + TX, Cimiazol + TX, Thiomethionate + TX, Chlorbeside + TX, Chlordimeform + TX, Chlordimeform hydrochloride + TX, Chlorphenetole + TX, Chlor Fenson +TX, Chlorphenesulfide +TX, Chlorobenzilate +TX, Chlormebform +TX, Chlormethiuron +TX, Chloropropylate +TX, Chlorthiophos +TX, Cinerin I +TX, Cinerin II +TX, Cinerins +TX, Closantel +TX, Coumaphos +TX, Crotamiton +TX, Crotoxyphos +TX, Kufraeb +TX, Cyanthoate +TX, DCPM +TX, DDT +TX, Demefion +TX, Demefion-O +TX, Demefion-S +TX, Demeton-methyl +TX, Demeton-O +TX, Demeton- O-Methyl + TX, Demeton-S + TX, Demeton-S-methyl + TX, Demeton-S-methyl sulfone + TX, Dichlofluanid + TX, Dichlorvos + TX, Dicrifos + TX, Dienochlor + TX, Dimefox + TX, Zinex + TX, Zinex-Diclexin + TX, Dinocap-4 + TX, Dinocap-6 + TX, Dinocton + TX, Dinopenton + TX, Dinosulfone + TX, Dinotervon + TX, Dioxathion + TX, Diphenylsulfone + TX, Disulfiram + TX, DNOC + TX, Dofenapine + TX, Doramectin + TX,Endothion + TX, Epirinomectin + TX, Ethoate-methyl + TX, Etrimphos + TX, Fenazaflor + TX, Fenbutatin oxide + TX, Fenothiocarb + TX, Fenpyrad + TX, Fen-pyroximate + TX, Fenpyrazamine + TX, Fenson + TX, Fentrifanil + TX, Flubenzimine + TX, Flucycloxuron + TX, Fluenethyl + TX, Fluorobenside + TX, FMC 1137+TX, formetanate+TX, formetanate hydrochloride+TX, formparanate+TX, gamma-HCH+TX, gliodin+TX, halfenprox+TX, hexadecylcyclopropanecarboxylate+TX, isocarbophos+TX, jasmolin I+TX, jasmolin II+TX, jodofenphos+TX, lindane+TX, malonoven+TX, mecarbam+TX, mefosfolan+TX, mesulfen+TX, Methacrifos + TX, methyl bromide + TX, metolcarb + TX, mexacarbate + TX, milbemycin oxime + TX, mipafox + TX, monocrotophos + TX, morphothion + TX, moxidectin + TX, naled + TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, nifururizide + TX, nikkomycin + TX, nitrilacarb + TX, nitrilocarb Liracarb 1:1 zinc chloride complex +TX, omethoate +TX, oxydeprophos +TX, oxydisulfoton +TX, pp'-DDT +TX, parathion +TX, permethrin +TX, fenkapton +TX, phosalone +TX, phospholan +TX, phosphamidon +TX, polychloroterpenes +TX, polynactin +TX, proclonol +TX, promacyl +TX, propoxur +TX, protidathion +TX, prothoate +TX, pyrethrins I+TX, Pyrethrin II+TX, Pyrethrin+TX, Pyridaphenthion+TX, Pirimitate+TX, Quinalphos+TX, Quinthiofos+TX, R-1492+TX, Phosglycine+TX, Rotenone+TX, Schladan+TX, Cebufos+TX, Selamectin+TX, Sofamid+TX, SSI-121+TX, Sulfiram+TX, Sulfuramide+TX, Sulfotep+TX, Sulfur+TX, Diflobidazine+TX, Tau-Fluvalinate+TX,TEPP+TX, Terbam+TX, Tetradifon+TX, Tetrasul+TX, Thiafenox+TX, Thiocarboxim+TX, Thiofanox+TX, Thiometon+TX, Thioquinox+TX, Thuringiensin+TX, Triamiphos+TX, Triaten+TX, Triazophos+TX, Triazuron+TX, Trifenofos+TX, Trinactin+TX, Vamidothion+TX, Vaniliprole+TX, Bethoxazin+T X, copper dioctanoate +TX, copper sulfate +TX, sibutrin +TX, dichloren +TX, dichlorophen +TX, endothall +TX, fentin +TX, hydrated lime +TX, nabam +TX, quinoclamine +TX, quinoneamide +TX, simazine +TX, triphenyltin acetate +TX, triphenyltin hydroxide +TX, crufomate +TX, piperazine +TX, thiophanate +TX, chloralose +TX, fenthion +TX, pyridine -4-Amine + TX, Strychnine + TX, 1-Hydroxy-1H-pyridine-2-thione + TX, 4-(Quinoxalin-2-ylamino)benzenesulfonamide + TX, 8-Hydroxyquinoline Sulfate + TX, Bronopol + TX, Copper Hydroxide + TX, Cresol + TX, Dipyrithione + TX, Doditin + TX, Fenaminosulf + TX, Formaldehyde + TX, Hydralgafen + TX, Kasugamycin + TX, Kasugamycin Hydrochloride Hydrate + TX, Nickel Bis(dimethyldithiocarbamate) + TX, Nitrapyrin + TX, Octilinone + TX, Oxolinic Acid + TX, Oxytetracycline + TX, Hydroxyquinoline Potassium Sulfate + TX, Probenazole + TX, Streptomycin + TX, Streptomycin Sesquisulfate + TX, Tecloftalam + TX, Thiomersal + TX, Adoxophyes orana GV+TX, Agrobacterium radiobacter+TX, Amblyseius spp.+TX, Anagrapha falcifera NPV+TX, Anagrus atomus+TX, Aphelinus abdominalis+TX,Aphidius colemani + TX, Aphidoletes aphidimyza + TX, Autographa californica NPV + TX, Bacillus sphaericus Neide + TX, Beauveria brongniartii + TX, Chrysoperla carnea + TX, Cryptolaemus montrouzieri + TX, Codling moth (Cydia pomonella) GV + TX, Leaf-grating wasp (Dacnusa sibirica) + TX, Diglyphus isaea + TX, Encarsia formosa + TX, Desert wasp (Eretmocerus eremicus) + TX, Heterorhabditis bacteriophora and H. megidis + TX, Hippodamia convergens + TX, Leptomastix dactylopii + TX, Macrolophus caliginosus + TX, Mamestra brassicae NPV + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, pine sawfly (Neodiprion sertifer) NPV and N. lecontei NPV + TX, Orius spp. + TX, Paecilomyces fumosoroseus + TX, Phytoseiulus persimmon (Phytoseiulus persimilis + 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, Trichogramma spp. + TX, Typhlodromus occidentalis + TX, Verticillium lecanii) + TX, apholate + TX, Visadil + TX, busulfan + TX, dimatif + TX, hemel + TX, hempa + TX, metepa + TX, methiotepa + TX, methyl apholate + TX, molzide + TX, penfluron + TX, tepa + TX, thiohempa + TX, thiotepa + TX, trethamine + TX, uredepa + TX, (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol + TX, ( E)-Trideca-4-en-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E,Z)-tetradec-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate tate + 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, (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradec- 9,12-dien-1-yl acetate + TX, 14-methyloctadec-1-ene + TX, 4-methylnonan-5-ol and 4-methylnonan-5-one + TX, alpha-multistriatin + TX, Brevicomin + TX, Codrelle + TX, Codlemone + TX, Querle + TX, Disparle + TX, Dodec-8-en-1-yl acetate + TX, Dodec-9-en-1-yl acetate + TX, Dodec-8 + TX,10-Dien-1-yl acetate + TX, Dominicalure + TX, Ethyl 4-methyloctanoate + TX, Eugenol + TX, Frontalin + TX, Grandolure + TX, Grandolure I + TX, Grandolure II + TX, Grandolure III + TX, Grandolure IV + TX, Hexalure + TX, Ipsdienol + TX, Ipsenol + TX, Japonilure + TX, Lineatin + TX, Littlea + TX, Looplure + TX, Medulure + TX, Megatomoic acid + TX, Methyleugenol + TX, Muscalure + TX, Octadeca-2,13-dien-1 -yl acetate + TX, Octadeca-3,13-dien-1-yl acetate + TX, Olfural + TX, Orictalure + TX, Ostramon + TX, Siglua + TX, Soldigin + TX, Sulcatol + TX, Tetradec-11-en-1-yl acetate + TX, Trimedulure + TX, Trimedulure A + TX, Trimedulure B1 + TX, Trimedulure B2 + TX, Trimedulure C + TX, Trunc-call + TX, 2-(octylthio)-ethanol + TX, Butapyronoxyl + TX, Butoxy(polypropylene glycol) (Iron) + TX, Dibutyl adipate + TX, Dibutyl phthalate + TX, Dibutyl succinate + TX, Diethyl toluamide + TX, Dimethylcarbate + TX, Dimethyl phthalate + TX, Ethyl hexanediol + TX, Hexamide + TX, Methoxybutyl + TX, Methyl neodecanoamide + TX, Oxamate + TX, Picaridin + TX, 1-Dichloro-1-nitroethane + TX, 1,1-Dichloro-2,2-bis(4-ethylphenyl)-ethane + TX, 1,2-Dichloropropane and 1,3-Dichloropropene + TX, 1-Bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)acetic acid ethyl + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethyl carbamate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methyl carbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidone + TX,2-Isovalerylindan-1,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate + TX, 2-thiocyanatoethyl laurate + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-methyl-1-phenylpyrazol-5-yldimethylcarbamate + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate + TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate + TX, acetione + TX, acrylonitrile + TX, aldrin + TX, allosamidin + TX, alixycarb + TX, α-ecdysone + TX, aluminum phosphide + TX, aminocarb + TX, anabasine + TX, atidathion + TX, azamethiphos + TX, Bacillus thuringiensis (Bacillus thuringiensis) delta-endotoxin +TX, barium hexafluorosilicate +TX, barium polysulfide +TX, bartholin +TX, Bayer 22 / 190 +TX, Bayer 22408 +TX, beta-cyfluthrin +TX, beta-cypermethrin +TX, bioethanomethrin +TX, biopermethrin +TX, bis(2-chloroethyl) ether +TX, borax +TX, bromfenvinphos +TX, bromo-DDT +TX, bufencarb +TX, butacarb +TX, butathiophos +TX, butonate +TX, calcium arsenate +TX, calcium cyanide +TX, carbon disulfide +TX, carbon tetrachloride +TX, cartap hydrochloride +TX, sevadin +T X, chlorbicyclen + TX, chlordane + TX, chlordecone + TX, chloroform + TX, chloropicrin + TX, chlorphoxim + TX, chlorprazophos + TX, cis-resmethrin + TX, cismethrin + TX, clocitrin + TX, copper acetoarsenite + TX, copper arsenate + TX, copper oleate + TX, chumithoate + TX, cryolite + TX, CS708 + TX, cyanofenphos + TX, cyanophos + TX, cyclethrin + TX, cythioate + TX, d-tetramethrin + TX, DAEP + TX, dazomet + TX, decarbofuran + TX, diamidaphos + TX, dikapton + TX, dichlorophenthion + TX, dicresyl + TX, dicyclanil + TX, dieldrin + TX,Diethyl 5-methylpyrazol-3-yl phosphate + TX, Dilol + TX, Dimefluthrin + TX, Dimethane + TX, Dimethryn + TX, Dimethylvinphos + TX, Dimethylan + TX, Dinoprop + TX, Dinosam + TX, Dinoseb + TX, Diofenolan + TX, Dioxabenzophos + TX, Dicyclophos + TX, DSP + TX, Ecdysterone + TX, EI 1642+TX, EMPC+TX, EPBP+TX, Ethaphos+TX, Ethiofencarb+TX, Ethyl formate+TX, Ethylene dibromide+TX, Dichloroethane+TX, Ethylene oxide+TX, EXD+TX, Fenchlorphos+TX, Fenetacarb+TX, Fenitrothion+TX, Fenoxacrim+TX, Fenpyrithrin+TX, Fensulfothion+TX, Fenthion-ethyl+TX, Flucofuron+TX, Fosmetiran+TX, Fospirate+TX, Fostietan+TX, F Lathiocarb +TX, Frethrin +TX, Guazatine +TX, Guazatine acetate +TX, Sodium tetrathiocarbonate +TX, Halfenprox +TX, HCH +TX, HEOD +TX, Heptachlor +TX, Heterofos +TX, HHDN +TX, Hydrogen cyanide +TX, Hikincarb +TX, IPSP +TX, Isazophos +TX, Isobenzane +TX, Isodrin +TX, Isofenphos +TX, Isolane +TX, Isoprothiolane +TX, Isoxathion +TX, Juvenile hormone I +TX, Juvenile hormone II + TX, Juvenile hormone III + TX, Kelevan + TX, Kinoprene + TX, Lead arsenate + TX, Leptophos + TX, Lilimphos + TX, Ritidathion + TX, m-Cumenylmethylcarbamate + TX, Magnesium phosphide + TX, Magidox + TX, Mecarfone + TX, Menasone + TX, Mercurous chloride + TX, Mesulfenphos + TX, Metam + TX, Metam-potassium + TX, Metam-sodium + TX, Methanesulfonyl fluoride + TX, Metocrotophos + TX, Methoprene + TX, Methotrin + TX, Methoxychlor + TX, Methylisothiazolinone Thiocyanate + TX, methyl chloroform + TX, methylene chloride + TX, methoxadiazone + TX, Mirex + TX, naphthalophos + TX, naphthalene + TX, NC-170 + TX, nicotine + TX, nicotine sulfate + TX, nithiazine + TX, nornicotine + TX, O-5-dichloro-4-iodophenyl O-ethyl ethyl phosphonothioate + TX, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate + TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate phosphate + TX, O,O,O',O'-tetrapropyldithiopyrophosphate + TX, oleic acid + TX, para-dichlorobenzene + TX, parathion-methyl + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH60-38 + TX, fenkapton + TX, phosnichlor + TX, phosphine + TX, phoxim-methyl + TX, pyrimetaphos + TX, polychlorodicyclopentadiene isomers + TX, potassium arsenite + TX, potassium thiocyanate + TX, precocene I + TX, precocene II + TX, precocene III + TX TX, pyrimidophos + TX, profluthrin + TX, promecarb + TX, prothiofos + TX, pyrazophos + TX, pyresmethrin + TX, cassia + TX, quinalphos-methyl + TX, quinothione + TX, rafoxanide + TX, resmethrin + TX, rotenone + TX, kadethrin + TX, ryania + TX, ryanodine + TX, sabadila + TX, shradan + TX, cebufos + TX, SI-0009 + TX, tiapronil + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium hexafluorosilicate + TX,Pentachlorophenoxide sodium salt +TX, sodium selenate +TX, sodium thiocyanate +TX, sulcofuron +TX, sulcofuron sodium +TX, sulfuryl fluoride +TX, sulprofos +TX, tar oil +TX, thazimcarb +TX, TDE +TX, tebupirimfos +TX, temephos +TX, telallethrin +TX, tetrachloroethane +TX, cyclofos +TX, thiocyclam +TX, thiocyclam hydrogen oxalate +TX, Thionazine +TX, Thiosultap +TX, Thiosultap-sodium +TX, Tralomethrin +TX, Transpermethrin +TX, Triazamate +TX, Trichlormethaphos-3 +TX, Trichloronat +TX, Trimethacarb +TX, Tolprocarb +TX, Triclopyricarb +TX, Triplene +TX, Veratridine +TX, Veratrine +TX, XMC +TX, Zetamethrin +TX, Zinc Phosphide +TX, Zolapro Phos + TX, meperfluthrin + TX, tetramethylfluthrin + TX, bis(tributyltin) oxide + TX, bromoacetamide + TX, ferric phosphate + TX, niclosamide-olamine + TX, tributyltin oxide + TX, pyrimorph + TX, triphenmorph + TX, 1,2-dibromo-3-chloropropane + TX, 1,3-dichloropropene + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-(4- chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, 2-fluoro-N-(3-methoxyphenyl)-9H-purin-6-amine + TX, benclothiaz + TX, cytokinin + TX, DCIP + TX, rufural + TX, isamidophos + TX, kinetin + TX, Myrothecium verrucaria (Myrothecium verrucaria) composition +TX, tetrachlorothiophene +TX, xylenol +TX, zeatin +TX, potassium ethylxanthogenate +TX, acibenzolar +TX, acibenzolar-S-methyl +TX, giant knotweed (Reynoutria sachalinensis) extract +TX, alpha-chlorohydrin +TX, anth +TX, barium carbonate +TX, bisthiosemi +TX, brodifacoum +TX, bromadiolone +TX,Bromethalin + TX, chlorophacinone + TX, cholecalciferol + TX, coumachlor + TX, coumafuryl + TX, coumatetralyl + TX, crimidine + TX, difenacoum + TX, difethialone + TX, diphacinone + TX, ergocalciferol + TX, flocoumafen + TX, fluoroacetamide + TX, flupropazine + TX, flupropazine hydrochloride + TX, norbormide + TX, fosacetim + TX, phosphorus + TX, pindone + TX, pyrinuron + TX, sciliroside + TX, sodium fluoroacetate + TX, thallium sulfate + TX, warfarin + TX, 2-(2-butoxyethoxy)ethyl piperonylate + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, farnesol and nerolidol + TX, berubutin + TX, MGK264 + TX, piperonyl butoxide + TX, piprotal + TX, propyl isomer + TX, S421 + TX, sesamex + TX, sesasmolin + TX, sulfoxide + TX, anthraquinone + TX, copper naphthenate + TX, copper oxychloride + TX, dicyclopentadiene + TX, thiram + TX, Zinc naphthenate + TX, ziram + TX, imanin + TX, ribavirin + TX, chlorinconazid + TX, mercury(II) oxide + TX, thiophanate-methyl + TX, azaconazole + TX, bitertanol + TX, bromuconazole + TX, cyproconazole + TX, difenoconazole + TX, diniconazole + TX, epoxiconazole + TX, fenbuconazole + TX, fluquinconazole + TX, flusilazole + TX, flutriafol + TX, furametpyr + TX, hexaconazole + TX, imazalil + TX, imibenconazole + TX X, ipconazole + TX, metconazole + TX, myclobutanil + TX, paclobutrazol + TX, pefurazoate + TX, penconazole + TX, prothioconazole + TX, pyrifenox + TX, prochloraz + TX, propiconazole + TX, pyrisoxazole + TX, simeconazole + TX, tebuconazole + TX, tetraconazole + TX, triadimefon + TX, triadimenol + TX, triflumizole + TX, triticonazole + TX, ancymidol + TX, fenarimol + TX, nuarimol + TX, bupirimate + TX,Dimethirimol + TX, Ethirimol + TX, Dodemorph + TX, Fenpropidin + TX, Fenpropimorph + TX, Spiroxamine + TX, Tridemorph + TX, Cyprodinil + TX, Mepanipyrim + TX, Pyrimethanil + TX, Fenpiclonil + TX, Fludioxonil + TX, Benalaxyl + TX, Furalaxyl + TX, -Metalaxyl- + TX, R-Metalaxyl + TX, Ofrace + TX, Oxadixyl + TX, Carbendazim + TX, Debacarb + TX, Fuberidazole- + TX, Thiabendazole + TX, Chlozolinate + TX, Diclozolin + TX, Mycrozolin + TX, Procymidone + TX, Vinclozolin + TX, Boscalid + TX, Carboxin + TX, Fenfuram + TX, Flutolanil + TX, Mepronil + TX, Oxycarboxin + TX, Penthiopyrad + TX, Thifluzamide + TX, Dodine + TX, Iminoctadine + TX, Azoxystrobin + TX, Dimoxystrobin + TX, Enestrobulin + TX, Phenaminestrobin + TX, Flufenoxystrobin + TX, Fluoxastrobin + TX, Kresoxim-methyl + TX, Metominostrobin + TX, trifloxystrobin + TX, oryzastrobin + TX, picoxystrobin + TX, pyraclostrobin + TX, pyrametostrobin + TX, pyraoxystrobin + TX, ferbam + TX, mancozeb + TX, maneb + TX, metiram + TX, propineb + TX, zineb + TX, captafol + TX, captan + TX, fluoroimide + TX, folpet + TX, tolylfluanid + TX, Bordeaux mixture + TX, copper oxide + TX, mancopper + TX, oxine-copper + TX, nitrothal-isopropyl + TX, edifenphos + TX, Iprobenfos + TX, Fosdifen + TX, Turcofos-methyl + TX, Anilazine + TX, Benthiavalicarb + TX, Blasticidin-S + TX, Chloroneb + TX, Chlorothalonil + TX, Cyflufenamid + TX, Cymoxanil + TX, Diclocymet + TX, Diclomedine + TX, Dicloran + TX, Diethofencarb + TX, Dimethomorph + TX, Flumorph + TX, Dithianon + TX, Ethaboxam + TX, Etridiazole + TX, Famoxadone + TX, Fenamidon + TX, Fenoxanil + TX, Ferimzone + TX,Fluazinam + TX, Fluopicolide + TX, Flusulfamide + TX, Fluxapyroxad + TX, Fenhexamid + TX, Fosetyl-aluminum + TX, Hymexazole + TX, Iprovalicarb + TX, Cyazofamid + TX, Metasulfocarb + TX, Metrafenone + TX, Pencycuron + TX, Phthalide + TX, Polyoxin + TX, Propamocarb + TX, Pyribencarb + TX, Proquinazid + TX, Pyroquilon + TX, Pyriophenone + TX, Quinoxyfen + TX, Quintozene + TX, Tiadinil + TX, Triazoxide + TX, Tricyclazole + TX, Triforine + TX, Validamycin + TX, Valifenalate + TX, Zoxamide + TX, Mandipropamide + TX, Fluveneteram + TX, Isopyrazam + TX, Sedaxane + TX, Benzovindiflupyr + TX, Pydiflumetofen + TX, 3-Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, Isoflucipram + TX, Isotianil + TX, Dipimethitrone + TX, 6-Ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile + TX, 2-(Difluoromethyl)- (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine ...[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, (phenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine + TX, fluindapyr + TX, methoxystrobin (jiaxiangjunzhi) + TX, rubenmixianan + TX, dichlorbenziazox + TX, mandestrobin + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]- ]phenyl]propan-2-ol + TX, oxathiapiproline + TX, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, pyraziflumide + TX, inpirfluxam + TX, turolprocarb + TX, mefentrifluconazole + TX, ipfentrifluconazole + TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, N'-(2,5-Dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + 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]methanesulfonic acid + TX, but-3-ynyl N-[6-[ [(Z)-[(1-Methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, ethyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, pyridaclomethyl + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carbo oxamide + TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX, aminopyrifen + TX, ametoctrazine + TX, amisulbrom + TX, penflufen + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl] Oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX, florylpicoxamide + TX, fenpicoxamide + TX, tebufloquine + TX, ipulfenoquine + TX, quinofumelin + TX, isofetamide + TX, ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate + TX (which may be prepared from the method described in WO 2020 / 056090), ...(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enoxy]phenyl]methyl]pyrazole-3-carboxylate + TX (which can be prepared by the method described in WO 2020 / 056090), Methyl N-[[4-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate + TX (which may be prepared from the method described in WO 2020 / 097012), methyl N-[[4-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate + TX (which may be prepared from the method described in WO 2020 / 097012), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[ 2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide + TX (which may be prepared from the method described in WO 2020 / 109391), 6-chloro-N-[2-(2-chloro-4-methyl-phenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide + TX (which may be prepared from the method described in WO 2020 / 109391), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide + TX )-N-[2-(3,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide + TX (which may be prepared from the method described in WO 2020 / 109391), 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, benzothiostrobin + TX, Fenamacril + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, fluopyram + TX, flufenoxadiazam + TX, flutianil + TX, fluopimomide + TX, pyrapropoin + TX, picarbutrazox + TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + 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, Methyltetraprole + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidinemethanol + TX, Fluoxapiproline + TX, Enoxastrobin +TX, methyl (Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazol-2-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)-2-[5-(3-isopropylpyrazol-1-yl)-2-methyl-phenoxy]-3-methoxy-prop-2-enoate +TX, methyl (Z)-3-methoxy-2-[2-methyl-5-(3-propylpyrazole- methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]prop-2-enoate + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]prop-2-enoate + TX (these compounds can be prepared from the method described in WO 2020 / 079111), 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 + TX (These compounds may be prepared from the method described in WO 2020 / 193387), 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, trinexapac + TX, cumoxystrobin + TX, zhongshengmycin + TX, copper thiodiazole + TX, zinc thiazole + TX, amethotractin + TX, iprodione + TX, seboxylamine + TX; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + 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-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N- N'-methyl-formamidine + TX, N'-[5-chloro-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 + TX (these compounds can be prepared by the method described in WO 2015 / 155075); N'- [5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared by the method described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine + TX, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds can be prepared by the method described in WO 2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoro 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-[(1R)-1- benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline Phosphorus-3-carboxamide + 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, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + 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 (these compounds can be prepared by the method described in WO 2017 / 153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline Phosphorus + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-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, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX (these compounds are, can be prepared by the method described in WO 2017 / 025510; 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, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazoline) 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)isoquinoline + TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole + TX (these compounds can be prepared by the methods described in WO 2016 / 156085);N-Methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N,2-Dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N-Ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX phenyl]phenyl]methyl]propanamide + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2 ,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate + TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine + TX. The compounds in this paragraph can be prepared by the methods described in WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 093348 and WO 2017 / 118689;2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound can be prepared by the method described in WO 2017 / 029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound can be prepared by the method described in WO 2017 / 029179); 3 -[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); (4-phenoxyphen N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzene (N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzene) with TX (this compound can be prepared by the method described in WO 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone with TX (this compound can be prepared by the method described in WO 2011 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzene Carbothioamide + TX; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX (this compound can be prepared by the method described in WO 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX;N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared by the method described in WO 2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX (this compound can be prepared by the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX (these compounds can be prepared by the method described in WO 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX (this compound can be prepared by the method described in WO 2018 / 06 5414); ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate + TX (this compound can be prepared by the method described in WO 2018 / 158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX a biologically active agent selected from N-[(Z)-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-[N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX (these compounds can be prepared by the methods described in WO 2018 / 202428); Microorganisms including: 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 alternata + TX, Alternaria cassia + TX, cassia) + TX, Alternaria destruens (Smolder®) + TX, Ampelomyces quisqualis (AQ10®) + TX, Aspergillus flavus AF36 (AF36®) + TX, Aspergillus flavus NRRL21882 (Aflaguard®) + TX, Aspergillus spp.) + TX, Aureobasidium pullulans + TX, Azospirillum + TX, (MicroAZ® + TX, TAZO B®) + TX, Azotobacter + TX, Azotobacter chroocuccum (Azotomeal®) + TX, Azotobacter cysts (Bionatural Blooming Blossoms®) + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus chitinosporus strain CM-1 + TX, Bacillus chitinosporus strain AQ746+TX, Bacillus licheniformis strain HB-2 (Biostart™ Rhizoboost®)+TX, Bacillus licheniformis strain 3086 (EcoGuard®+TX, Green Releaf®)+TX, Bacillus circulans+TX, Bacillus firmus (BioSafe®+TX, BioNem-WP®+TX, VOTiVO®)+TX, Bacillus firmus strain I-1582+TX, Bacillus macerans+TX, Bacillus marismortii (Bacillus marismortui + TX, Bacillus megaterium + TX, Bacillus mycoides strain AQ726 + TX, Bacillus papillae (Milky Spore Powder®) + TX, Bacillus pumilus spp.) +TX, Bacillus pumilus strain GB34 (Yield Shield®) +TX, Bacillus pumilus strain AQ717 +TX, Bacillus pumilus strain QST 2808 (Sonata® +TX, Ballad Plus®) +TX, Bacillus spahericus (VectoLex®) +TX, Bacillus spp. +TX, Bacillus spp. strain AQ175 +TX, Bacillus spp. strain AQ177 +TX, Bacillus spp. spp. strain AQ178+TX, Bacillus subtilis strain QST 713 (CEASE®+TX, Serenade®+TX, Rhapsody®)+TX, Bacillus subtilis strain QST 714 (JAZZ®)+TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilis strain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis var. amyloliquefaciensamyloliquefaciens strain FZB24 (Taegro® +TX, Rhizopro®) +TX, Bacillus thuringiensis Cry2Ae +TX, Bacillus thuringiensis Cry1Ab +TX, Bacillus thuringiensis aizawai GC91 (Agree®) +TX, Bacillus thuringiensis israelensis (BMP123® +TX, Aquabac® +TX, VectoBac®) +TX, Bacillus thuringiensis kurstaki Bacillus thuringiensis kurstaki (Javelin® + TX, Deliver® + TX, CryMax® + TX, Bondide® + TX, Scutella WP® + TX, Turilav WP® + TX, Astuto® + TX, Dipel WP® + TX, Biobit® + TX, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF / 3P®) + TX, Bacillus thuringiensis strain BD#32 ... thuringiensis strain AQ52+TX, Bacillus thuringiensis var. aizawai (XenTari®+TX, DiPel®)+TX, Bacteria spp.) (GROWMEND® +TX, GROWSWEET® +TX, Shootup®) +TX, Clavipacter michiganensis bacteriophage (AgriPhage®) +TX, Bakflor® +TX,. Beauveria bassiana (Beaugenic® +TX, Brocaril WP®) +TX, Beauveria bassiana GHA (Mycotrol ES® +TX, Mycotrol O® +TX, BotaniGuard®) +TX, Beauveria brongniartii (Engerlingspilz® +TX, Schweizer Beauveria® +TX, Melocont®) +TX, Beauveria spp. +TX, Botrytis cineria +TX, Bradyrhizobium japonicum (TerraMax®) +TX, Brevibacillus brevis brevis + TX, Bacillus thuringiensis tenebrionis (Novodor®) + TX, BtBooster + TX, Burkholderia cepacia (Deny® + TX, Intercept® + TX, 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 pulcherrima + TX, Candida reukaufii + TX, Candida saitoana (Bio-Coat® + TX, Biocure®) + TX, Candida sake + TX, Candida spp.) + TX, Candida tenius + TX, Cedecea dravisae + TX, Cellulomonas flavigena + TX, Chaetomium cochliodes (Nova-Cide®) + TX, Chaetomium globosum (Nova-Cide®) + TX, Chromobacterium subtsugae strain PRAA4-1T (Grandevo®) + TX, Cladosporium cladosporioides + TX, Cladosporium oxysporum + TX, Cladosporium chlorocephalum chlorocephalum + 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®) + TX, Cydia pomonella granulovirus (Madex® + TX, Madex Plus® + TX, 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 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® + TX, Prestop®) + TX, Gliocladium roseum roseum + TX, Gliocladium spp. (SoilGard®) + 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 nucleopolyhedrovirus (Gemstar®) + TX, isoflavone-formononetin (Myconate®) + TX, Kloeckera apiculata + TX, Kloeckera spp.) + TX, Lagenidium giganteum (Laginex®) + TX, Greenhouse whitefly (Lecanicillium longisporum) (Vertiblast®) + TX, Lecanicillium muscarium (Vertikil®) + TX, Gypsy moth (Lymantria dispar) nucleopolyhedrovirus (Disparvirus®) + TX, Marinococcus halophilus + TX, Meira geulakonigii + TX, Metarhizium anisopliae (Met52®) + TX, Metarhizium anisopliae (Destruxin®) + TX, WP®) + TX, Metschnikowia fruticola (Shemer®) + TX, Metschnikowia pulcherrima + TX, Microdochium dimerum (Antibot®) + TX, Micromonospora coerulea + TX, Micromonospora coerulea + TX, Microsphaeropsis ochracea + TX, Muscodor albus 620 (Muscudor®) + TX, Muscodor roseus strain A3-5 + TX, Mycorrhizae spp.) (AMykor® +TX, Root Maximizer®) +TX, Myrothecium verrucaria strain AARC-0255 (DiTera®) +TX, BROS PLUS® +TX, Ophiostoma piliferum strain D97 (Sylvanex®) +TX, Paecilomyces farinosus +TX, Paecilomyces fumosoroseus (PFR-97® +TX, PreFeRal®) +TX, Paecilomyces linacinus (Biostat WP®) +TX, Paecilomyces lilacinus strain 251 (MeloCon WG®) + TX, Paenibacillus polymyxa + TX, Pantoea agglomerans (BlightBan C9-1®) + TX, Pantoea spp. + TX, Pasteuria spp. (Econem®) + TX, Pasteuria nishizawae + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart® + TX, TagTeam®) + TX, Penicillium brevicompactum brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp.) + TX, Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, Phosphhomeal® + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guilermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX. Pseudomonas aeruginosa + TX, Pseudomonas aureofaciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Pseudomonas fluorescens strain A506 (BlightBan A506®) + TX, Pseudomonas putida + TX, Pseudomonas reactans + TX, Pseudomonas species spp.) + TX, Pseudomonas syringae (Bio-Save®) + TX, Pseudomonas viridiflava + TX, Pseudomonas fluorescens (Zequanox®) + TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®) + TX, Puccinia canaliculata + TX, Puccinia thlaspeos (Wood Warrior®) + TX, Pythium paroecandrum + TX, Pythium oligandrum) (Polygandron® + TX, Polyversum®) + TX, Pythium periplocum + TX, Rhanella aquatilis + TX, Rhanella spp.) + TX, rhizobia (Dormal® + TX, Vault®) + TX, Rhizoctonia spp. + TX, Rhodococcus globerulus strain AQ719 + TX, Rhodosporidium diobovatum + TX, Rhodosporidium toruloides + TX, Rhodotorula spp. + TX, Rhodotorula glutinis + TX, Rhodotorula graminis + TX, Rhodotorula mucilagnosa + TX, Rhodotorula rubra + TX, Saccharomyces cerevisiae + TX, Salinococcus roseus + TX, Sclerotinia minor + TX, Sclerotinia minor (SARRITOR®) + TX, Scytalidium spp. + TX, Scytalidium uredinicola + TX, Spodoptera exigua nucleopolyhedrovirus (Spod-X® + TX, Spexit®) + TX, Serratia marcescens + TX, Serratia plymuthica + TX, Serratia spp.) + TX, Sordaria fimicola + TX, Spodoptera littoralis nuclear polyhedrosis virus (Littovir®) + TX, Sporobolomyces roseus + TX, Stenotrophomonas maltophilia + TX, Streptomyces ahygroscopicus + TX, Streptomyces albaduncus + TX, Streptomyces exfoliates + TX, Streptomyces galbus + TX, Streptomyces griseoplanus griseoplanus + TX, Streptomyces griseoviridis (Mycostop®) + 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 gamsii (Tenet®) + TX, Trichoderma atroviride (Plantmate®) + TX, Trichoderma hamatum TH 382 + TX, Trichoderma harzianum rifai (Mycostar®) + TX, Trichoderma harzianum T-22 (Trianum-P® + TX, PlantShield HC® + TX, RootShield® + TX, Trianum-G®) + TX, Trichoderma harzianum harzianum) T-39 (Trichodex®) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma spp.) LC 52 (Sentinel®) + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + TX, Trichoderma taxi + TX, Trichoderma virens + TX, Trichoderma virens (formerly Gliocladium virens GL-21) (SoilGuard®) + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, Trichosporon spp. + TX, Trichothecium spp.) + TX, Trichothecium roseum + 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 supplemental micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Verticillium lecanii lecanii (Mycotal® + TX, Vertalec®) + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv. Poae (Camperico®) + TX, Xenorhabdus bovienii + TX, Xenorhabdus nematophilus; Plant extracts including: pine oil (Retenol®) +TX, azadirachtin (Plasma), Neem Oil® +TX, AzaGuard® +TX, MeemAzal® +TX, Molt-X® +TX, botanical insect growth regulators (Neemazad® +TX, Neemix®) +TX, rapeseed oil (Lilly Miller Vegol®) +TX, American ant's weed (Chenopodium ambrosioides near ambrosioides) (Requiem®) +TX, Chrysanthemum extract (Crisant®) +TX, neem oil extract (Trilogy®) +TX, Labiatae essential oil (Botania®) +TX, clove, rosemary, peppermint, and thyme oil extracts (Garden insect killer®) + TX, glycine betaine (Greenstim®) + TX, garlic + TX, lemongrass oil (GreenMatch®) + TX, neem oil + TX, catnip (Nepeta cataria) (catnip oil) + TX, catnip (Nepeta catarina) + TX, nicotine + TX, oregano oil (MossBuster®) + TX, sesame (Pedaliaceae) oil (Nematon®) + TX, pyrethrum + TX, soapberry (Quillaja saponaria) (NemaQ®) + TX, giant knotweed (Reynoutria sachalinensis) (Regalia® + TX, Sakalia®) + TX, rotenone (Eco Roten®) + TX, Rutaceae extract (Soleo®) + TX, soybean oil (Ortho ecosense®) +TX, tea tree oil (Timorex Gold®) +TX, thyme oil +TX, AGNIQUE® MMF +TX, BugOil® +TX, a mixture of rosemary, sesame, peppermint, thyme and cinnamon extracts (EF300®) + TX, a mixture of clove rosemary and peppermint extracts (EF 400®) + TX, a mixture of clove peppermint garlic oil and mint (Soil Shot®) + TX, kaolin (Screen®) + TX, brown algae storage glucan (Laminarin®); Pheromones, including: blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®) + TX, codling moth pheromone (Paramount dispenser-(CM) / Isomate C-Plus®) + TX, grape berry moth pheromone (3M MEC-GBM Sprayable Pheromone®) + TX, leafroller pheromone (3M MEC-LR Sprayable Pheromone®) + TX, muscamone (Snip7 Fly Bait® + TX, Starbar Premium Fly Bait®) + TX, oriental fruit moth pheromone (3M oriental fruit moth sprayable pheromone®) + TX, peachtree Borer pheromone (Isomate-P®) + TX, Tomato Pinworm pheromone (3M Sprayable pheromone®) + TX, Entostat powder (palm tree extract) (Exosex CM®) + TX, (3E,8Z,11Z)-3,8,11-tetradecatrienyl acetate + TX, (7Z,11Z,13E)-7,11,13-hexadecatrienal + TX, (E,Z)-7,9-dodecadien-1-yl acetate + TX, 2-methyl-1-butanol + TX, calcium acetate + TX, Scenturion® + TX, Biolure® + TX, Check-Mate® + TX, Lavandulyl senecioate + TX; Macroorganisms including: Aphelinus abdominalis + TX, Aphidius ervi (Aphelinus-System®) + 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® + TX, Andersoni-System®) + TX, Amblyseius californicus californicus (Amblyline® + TX, Spical®) + TX, Amblyseius cucumeris (Thripex® + TX, Bugline cucumeris®) + TX, Amblyseius fallacis (Fallacis®) + TX, Amblyseius swirskii (Bugline swirskii® + TX, Swirskii-Mite®) + TX, Amblyseius womersleyi (WomerMite®) + TX, Amitus hesperidum + TX, Anagrus atomus + TX, Anagyrus fusciventris fusciventris) + TX, Anagyrus kamali + TX, Anagyrus loecki + TX, Anagyrus pseudococcus (Anagyruspseudococci (Citripar®) + TX, Anicetus benefices + TX, Anisopteromalus calandrae + TX, Anthocoris nemoralis (Anthocoris-System®) + TX, Aphelinus abdominalis (Apheline® + TX, Aphiline®) + TX, Aphelinus asychis + TX, Aphidius colemani (Aphipar®) + TX, Aphidius ervi (Ervipar®) + TX, Aphidius gifuensis + TX, Aphidius matricariae matricariae (Aphipar-M®) + TX, Aphidoletes aphidimyza (Aphidend®) + TX, Aphidoletes aphidimyza (Aphidoline®) + TX, Aphytis lingnanensis + TX, Aphytis melinus + TX, Aprostocetus hagenowii + TX, Atheta coriaria (Staphyline®) + TX, Bombus spp. + TX, Bombus terrestris (Natupol Beehive® + TX, Bombus terrestris (Beeline® + TX, Tripol®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus + TX, Chrysoperlacarnea (Chrysoline®) + TX, Chrysoperla carnea (Chrysopa®) + TX, Chrysoperla rufilabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichus phyllocnistoides + 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® + TX, Cryptoline®) + TX, Cybocephalus nipponicus (Dacnusa sibirica) + TX, Dacnusa sibirica (Minusa®) + TX, Diglyphus isaea (Diminex®) + TX, Delphastus catarinae (Delphastus catalinae) (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsisjucunda + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea + TX, Diglyphus isaea (Miglyphus® + TX, Digline®) + TX, Dacnusa sibirica (DacDigline® + TX, Minex®) + TX, Diversinervus spp. + TX, Encarsia citrina + TX, Encarsia formosa (Encarsia max® + TX, Encarline® + TX, En-Strip®) + TX, Eretmocerus eremicus (Enermix®) + TX, Encarsia guadeloupae + TX, Encarsia haitiensis + TX, Episyrphus balteatus (Syrphidend®) + TX, Eretmoceris siphonini + TX, Eretmocerus californicus + TX, Eretmocerus eremicus (Ercal® + TX, Eretline e®) + TX, Eretmocerus eremicus (Bemimix®) + TX, Eretmocerus hayati + TX, Eretmocerus mundus mundus) (Bemipar® + TX, Eretline m®) + TX, Eretmocerus siphonini + TX, Exochomus quadripustulatus + TX, Feltiellaacarisuga (Spidend®) + TX, Feltiella acarisuga (Feltiline®) + 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 axyridis (HarmoBeetle®) + TX, Heterorhabditis spp. (Lawn Patrol®) + TX, Heterorhabditis bacteriophora (NemaShield HB® + TX, Nemaseek® + TX, Terranem-Nam® + TX, Terranem® + TX, Larvanem® + TX, B-Green® + TX, NemAttack® + TX, Nematop®) + TX, Heterorhabditis megidis (Nemasys H® + TX, BioNem H® + TX, Exhibitline hm® + TX, Larvanem-M®) + TX, Hippodamia convergens) + TX, Hypoaspis aculeifer (Aculeifer-System® + TX, Entomite-A®) + TX, Hypoaspis miles (Hypoline m® + TX, Entomite-M®) + TX, Lbalia leucospoides + TX, Lecanoideus floccissimus + TX, Lemophagus errabundus + TX, Leptomastidea abnormis + TX, Leptomastix dactylopii (Leptopar®) + TX, Leptomastix epona + TX, Lindorus lophanthae + TX, Lipolexis oregmae + TX, Lucilia caesar (Natufly®) + TX, Lysiphlebus testacapes testaceipes + TX, Macrolophus caliginosus (Mirical-N® + TX, Macroline c® + TX, 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, Miyako Phytoseiulus (Neoseiulus californicus) + TX, Neoseiulus cucumeris (THRYPEX®) + TX, Neoseiulus fallasis (Neoseiulusfallacis + TX, Nesideocoris tenuis (NesidioBug® + TX, Nesibug®) + TX, Ophyra aenescens (Biofly®) + TX, Orius insidiosus (Thripor-I® + TX, Oriline i®) + TX, Orius laevigatus (Thripor-L® + TX, Oriline l®) + TX, Orius majusculus (Oriline m®) + TX, Orius strigicollis (Thripor-S®) + TX, Pauesia juniperum (Pauesia juniperorum + TX, Pediobius foveolatus + TX, Phasmarhabditis hermaphrodita (Nemaslug®) + TX, Phymastichus coffea + TX, Phytoseiulus macropilus + TX, Phytoseiulus persimilis (Spidex® + TX, Phytoline p®) + TX, Podisus maculiventris (Podisus®) + TX, Pseudacteon curvatus + TX, Pseudacteon obtusus + TX, Pseudacteon tricuspis tricuspis + TX, Pseudaphycus maculipennis + TX, Pseudleptomastix mexicana + TX, Psyllaephagus pilosuspilosus + 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® + TX, Millennium® + TX, BioNem C®+TX, NemAttack®+TX, Nemastar®+TX, Capsanem®+TX, Steinernema feltiae (NemaShield®+TX, Nemasys F®+TX, BioNem F®+TX, Steinernema-System®+TX, NemAttack®+TX, Nemaplus®+TX, Exhibitline sf®+TX, Scia-rid®+TX, Entonem®)+TX, Steinernema kraussei (Nemasys L®+TX, BioNem L®+TX, Exhibitline srb®)+TX, Steinernema riobrave riobrave (BioVector® + TX, BioVektor®) + TX, Steinernema scapterisci (Nematac S®) + TX, Steinernema spp. + TX, Steinernema spp. (Guardian Nematodes®) + TX, Stethorus punctilumpunctillum (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 pratoneri platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator + TX; Other biological agents include: abscisic acid +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® +TX, Ni-HIBIT Gold CST®) +TX, fatty acids derived from natural by-products of extra virgin olive oil (FLIPPER®) +TX, ferric phosphate (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, BioGain® +TX, Aminomite® +TX, Zenox® +TX, pheromone trap (Thripline ams®) + TX, potassium bicarbonate (MilStop®) + TX, potassium salts of fatty acids (Sanova®) + TX, potassium silicate solution (Sil-Matrix®) + TX, potassium iodide + potassium thiocyanate (Enzicur®) + TX, SuffOil-X® + TX, spider venom + TX, Nosema locustae (Semaspore Organic Grasshopper)Control®) + TX, sticky traps (Trapline YF® + TX, Rebell Amarillo®) + TX and traps (Takitrapline y+b®) + TX; (1) an antibacterial agent selected from the group consisting of: (1.1) Examples of such bacteria are: Bacillus mojavensis strain R3B (accession number NCAIM(P)B001389) from Certis USA LLC (a subsidiary of Mitsui & Co., Ltd.) (WO 2013 / 034938) + TX; Bacillus pumilus, in particular the strain BU F-33 with NRRL accession number 50185 (available as part of the CARTISSA® range from BASF, EPA registration number 71840-19) + TX; Bacillus subtilis, in particular the strain QST713 / AQ713 (SERENADE OPTI or SERENADE OPTI® from Bayer CropScience LP, US). No. 6,060,051 (available as ASO, NRRL accession number B21661) +TX; Bacillus subtilis strain BU1814 (available as VELONDIS® PLUS, VELONDIS® FLEX, and VELONDIS® EXTRA from BASF SE) +TX; Bacillus subtilis var. amyloliquefaciens strain FZB24 (available as TAEGRO® or TAEGRO® ECO (EPA registration number 70127-5) from Novozymes) +TX, with accession number DSM10271 +TX; Bacillus subtilis CX-9060 from Certis USA LLC (a subsidiary of Mitsui & Co., Ltd.) +TX; Bacillus sp. sp.), in particular strain D747 (available as DOUBLE NICKEL® from Kumiai Chemical Industry Co., Ltd.), having accession number FERM BP-8234, U.S. Pat. No. 7,094,592+TX; Paenibacillus sp., having accession number NRRL B-50972 or accession number NRRL B-67129) strain, WO 2016 / 154297 +TX; Paenibacillus polymyxa, in particular strain AC-1 (e.g., TOPSEED® from Green Biotech Company Ltd.) +TX; Pantoea agglomerans, in particular strain E325 (accession number NRRL B-21856) (available as BLOOMTIME BIOLOGICAL™ FD BIOPESTICIDE from Northwest Agri Products) +TX; Pseudomonas proradix from Sourcon Padena (e.g., PRORADIX®) +TX; and (1.2) Examples are fungi: Aureobasidium pullulans, in particular blastospores of the strain DSM 14940, blastospores of the strain DSM 14941 or a mixture of blastospores of the strains DSM 14940 and DSM 14941 (for example BOTECTOR® and BLOSSOM PROTECT® from bio-ferm, CH) + TX; Pseudozyma aphidis (disclosed in WO 2011 / 151819 by Yissum Research Development Company of the Hebrew University of Jerusalem) + TX; Saccharomyces cerevisiae cerevisiae), in particular the strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938 or CNCM No. 1-3939 (disclosed in WO 2010 / 086790 from Lesaffre et Compagnie, FR) + TX; (2) A biological bactericide or fungicide selected from the following group: (2.1) Examples are bacteria such as: Agrobacterium radiobacter strain K84 (e.g., GALLTROL-A® from AgBioChem, CA) + TX; Agrobacterium radiobacter strain K1026 (e.g., NOGALL® from BASF SE) + TX; Bacillus subtilis var. amyloliquefaciens strain FZB24 with accession number DSM10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA registration number 70127-5)) + TX; Bacillus amyloliquefaciens, in particular strain D747 (available as Double Nickel™ from Kumiai Chemical Industry Co., Ltd., with accession number FERM BP-8234, U.S. Pat. No. 7,094,592) +TX; Bacillus amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL accession number B-50768, WO 2014 / 028521) (STARGUS® from Marrone Bio Innovations) +TX; Bacillus amyloliquefaciens strain FZB42, accession number DSM 23117 (available as RHIZOVITAL® from ABiTEP, DE) +TX; Bacillus amyloliquefaciens isolate B246 (e.g. AVOGREEN™ from the University of Pretoria) +TX; Bacillus licheniformis, in particular strain SB3086 with accession number ATCC 55406, WO 2003 / 000051 (available as ECOGUARD™ Biofungicide and GREEN RELEAF™ from Novozymes) +TX +TX;Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (QUARTZO® (WG) and PRESENCE® (WP) from FMC Corporation) + TX; Bacillus methylotrophicus strain BAC-9912 (from the Chinese Academy of Sciences' Institute of Applied Ecology) + TX; Bacillus mojavensis strain R3B (accession number NCAIM(P)B001389) from Certis USA LLC (a subsidiary of Mitsui & Co., Ltd.) (WO 2013 / 034938) + TX; Bacillus mycoides mycoides, isolate, having accession number B-30890 (available from Certis USA LLC, a subsidiary of Mitsui & Co., Ltd., as BMJ TGAI® or WG and LifeGard®) +TX; Bacillus pumilus, particularly strain QST2808 (available from Bayer CropScience LP, US as SONATA®, having accession number NRRL B-30087, and described in U.S. Pat. No. 6,245,551) +TX; Bacillus pumilus, particularly strain GB34 (available from Bayer AG, DE as Yield Shield®) +TX; Bacillus pumilus, particularly strain BU, having NRRL accession number 50185 F-33 (available as part of the CARTISSA product line from BASF, EPA registration number 71840-19) + TX; Bacillus subtilis, specifically strain QST713 / AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, with NRRL accession number B21661, as described in U.S. Pat. No. 6,060,051) + TX;Bacillus subtilis Y1336 (available from BioNTech, Taiwan as BIOBAC® WP, registered in Taiwan as a biological fungicide under registration numbers 4764, 5454, 5096, and 5277) +TX; Bacillus subtilis strain MBI 600 (available from BASF SE as SUBTILEX), having accession number NRRL B-50595, U.S. Pat. No. 5,061,495 +TX; Bacillus subtilis strain GB03 (available from Bayer AG, DE as Kodiak®) +TX; Bacillus subtilis strain BU1814 (available from BASF SE as SUBTILEX), having accession number NRRL B-50595, U.S. Pat. No. 5,061,495 +TX; available as VELONDIS® PLUS, VELONDIS® FLEX, and VELONDIS® EXTRA from SE (+TX); Bacillus subtilis CX-9060 from Certis USA LLC (a subsidiary of Mitsui & Co., Ltd.); Bacillus subtilis KTSB strain (FOLIACTIVE® from Donaghys) (+TX); Bacillus subtilis IAB / BS03 (AVIV® from STK Bio-Ag Technologies, PORTENTO® from Idai Nature) (+TX); Bacillus subtilis strain Y1336 (available as BIOBAC® WP from BioNTech, Taiwan, registered as a biological fungicide in Taiwan under registration numbers 4764, 5454, 5096, and 5277) + TX; Paenibacillus epiphyticus from BASF SE (WO 2016 / 020371) + TX; Paenibacillus polymyxa ssp. plantarum from BASF SE (WO 2016 / 020371) + TX;Paenibacillus sp. strains having accession number NRRL B-50972 or accession number NRRL B-67129, WO 2016 / 154297 +TX; Pseudomonas chlororaphis strain AFS009, having accession number 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™ from Bioagri and Koppert) +TX; Pseudomonas fluorescens 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 number DSM7206) (MYCOSTOP® from Verdera, PREFENCE® from BioWorks, see Crop Protection 2006, 25, 468-475) +TX; Streptomyces lydicus strain WYEC108 (Streptomyces lydicus strain WYCD108US) (ACTINO-IRON® and ACTINOVATE® manufactured by Novozymes) +TX; and (2.2) Examples of fungi are: Ampelomyces quisqualis, in particular the strain AQ 10 (for example AQ 10® from IntrachemBio Italia) + TX; Ampelomyces quisqualis strain AQ10 with accession number CNCM1-807 (for example AQ 10® from IntrachemBio Italia) + TX; Aspergillus flavus strain NRRL 21882 (product known as AFLA-GUARD® from Syngenta / ChemChina) + TX; Aureobasidium pullulans, in particular blastospores of the strain DSM 14940 + TX; Aureobasidium pullulans, in particular the strain DSM Aureobasidium pullulans, in particular a mixture of blastospores of strains DSM 14940 and DSM 14941 (e.g., Botector® by bio-ferm, CH) + TX; Chaetomium cupreum (accession number CABI 353812) (e.g., BIOKUPRUM® by AgriLife) + TX; Chaetomium globosum (available as RIVADIOM® by Rivale) + TX; Cladosporium cladosporioides, st...
Claims
1. Compounds of formula (I) 【Chemistry 1】 (In the formula: A 1 , A 2 and A 3 are each independently N or CR Y or A 1 =A 2 -A 3 are collectively NR-C(=X)-N; X is O or S; A 4 and A 5 are each independently N or CR Y and Q is 【Chemistry 2】 wherein the wavy line represents the bond of Q to the remainder of the compound of formula (I). and R is hydrogen, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy or C 1 ~C 3 haloalkoxy; R 1 is hydrogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Cyanoalkyl, aminocarbonyl C 1 ~C 6 Alkyl, hydroxycarbonyl C 1 ~C 6 Alkyl, C 1 ~C 6 Nitroalkyl, trimethylsilane C 1 ~C 6 Alkyl, C 1 ~C 3 Alkoxy-C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 3 ~C 4 Cycloalkyl C 1 ~C 2 Alkyl, C 3 ~C 4 Cycloalkyl C 1 ~C 2 Alkyl (wherein the C 3 ~C 4 cycloalkyl groups are substituted with 1 or 2 halogen atoms), oxetan-3-yl-CH 2 -, C 1 ~C 6 Alkylcarbonyl, C 1 ~C 6 Alkoxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, benzyl, or halogen, C 1 ~C 6 Alkoxy and C 1 ~C 6 benzyl substituted with 1 to 3 substituents independently selected from haloalkyl; R 2a and R 2b is hydrogen, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Haloalkylsulfanyl, C 1 ~C 3 Alkoxy, C 1 ~C 3 Haloalkoxy, halogen, NO 2 , S.F. 5 ,CN,C(O)NH 2 , C(O)OH, C(S)NH 2 , C 3 ~C 6 Cycloalkyl, R X C substituted with 1 to 3 substituents independently selected from 3 ~C 6 Cycloalkyl; C 3 ~C 6 Cycloalkylcarbonyl, phenyl, R X phenyl substituted with 1 to 3 substituents independently selected from X heteroaryl substituted with 1 to 3 substituents independently selected from: OR 6 , piperidin-2-one-1-yl, R X piperidin-2-one-1-yl substituted by 1 to 2 substituents independently selected from: pyridin-2-one-1-yl, R X pyridin-2-one-1-yl substituted by 1 to 2 substituents independently selected from: azetidin-1-yl, R X azetidin-1-yl substituted with 1 to 2 substituents independently selected from: pyrrolidin-1-yl, R X Pyrrolidin-1-yl substituted by 1 to 2 substituents independently selected from 3 ~C 6 Cycloalkyl-C 1 ~C 4 Alkyl, R Z C substituted with 1 to 2 substituents independently selected from 3 ~C 6 Cycloalkyl-C 1 ~C 4 Alkyl; C 3 ~C 6 Cycloalkyl-C 1 ~C 3 Alkoxy, R X C substituted with 1 to 2 substituents independently selected from 3 ~C 6 Cycloalkyl-C 1 ~C 3 Alkoxy; C 1 ~C 5 Cyanoalkyl, C 1 ~C 5 Cyanoalkoxy, C 1 ~C 4 Alkylsulfanyl, R X C substituted with 1 to 3 substituents independently selected from 1 ~C 4 Alkylsulfanyl; C 1 ~C 4 Alkylsulfonyl, R X C substituted with 1 to 3 substituents independently selected from 1 ~C 4 Alkylsulfonyl; C 1 ~C 4 alkylsulfinyl, and R X C substituted with 1 to 3 substituents independently selected from 1 ~C 4 alkylsulfinyl; R 3 is C 1 ~C 3 Alkyl or C 1 ~C 3 haloalkyl; R 4 teeth 【Transformation 3】 (Wherein, the wavy line represents R 4 and Q a or Q b (represents a bond with and A 14 , A 24 and A 34 are, independently of each other, N or CH; R 4c is C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, allyl, propargyl or C 3 ~C 6 Cycloalkyl C 1 ~C 4 is alkyl; R 5 is hydrogen, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 3 ~C 4 Cycloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 AlkoxyC(O)-, (C 1 ~C 3 alkoxy) 2 CH-, halogen, -CN, NH 2 C(O)—, amino (i.e., NH 2 ), (C 1 ~C 3 alkyl)amino, di(C 1 ~C 3 alkyl) amino, hydroxy, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, (C 1 ~C 3 alkyl)sulfonylamino, (C 1 ~C 3 alkyl)sulfonyl(C 1 ~C 3 alkyl)amino, (C 1 ~C 3 alkyl)NHC(O)-, (C 1 ~C 3 alkyl) 2 NC(O)-, (C 1 ~C 3 cycloalkyl)NHC(O)-, (C 1 ~C 3 cycloalkyl)(C 1 ~C 3 alkyl)NC(O)-, (C 1 ~C 3 alkyl)C(O)(C 1 ~C 3 alkyl)N-, (C 1 ~C 3 alkyl)C(O)NH—, (C 1 ~C 3 alkyl)C(O)-, (C 1 ~C 3 Alkoxy)C(O)-, HC(O)-, diphenylmethanimine, C 1 ~C 3 haloalkoxy, phenyl, or a 5-membered aromatic heterocycle; or R 5 is C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 phenyl substituted with 1 to 3 substituents selected from cycloalkyl, halogen, —CN, and hydroxyl; or R 5 is C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 a 5-membered aromatic heterocycle substituted with 1 to 3 substituents selected from cycloalkyl, halogen, —CN, and hydroxyl; R 5a and R 5b are each independently hydrogen, halogen, —CN, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 3 ~C 4 Cycloalkyl, C 1 ~C 3 Alkoxy and C 1 ~C 3 haloalkoxy; R 6 is phenyl, benzyl, heteroaryl or C 3 ~C 6 is cycloalkyl; or R 6 is phenyl, benzyl, heteroaryl or C 3 ~C 6 cycloalkyl, each of which is independently R X substituted with 1 to 3 substituents independently selected from R X is a halogen, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 1 ~C 3 Haloalkoxy, NO 2 , S.F. 5 , CN, -C(O)NH 2 , -C(S)NH 2 , C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl and C 1 ~C 4 independently selected from alkylsulfonyl; R Y is hydrogen, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, hydroxy, C 1 ~C 3 Alkoxy, C 1 ~C 3 selected from haloalkoxy, halogen, —CN, and cyclopropyl; R Z is oxo, halogen, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 1 ~C 3 haloalkoxy and CN and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of the compounds of formula I above.
2. A 1 and A 3 is N, and A 2 is CR Y and R Y is hydrogen, chlorine, methyl, trifluoromethyl or methoxy.
3. A 1 =A 2 -A 3 2. The compound of claim 1, wherein: are taken together NR-C(=O)-N; and R is hydrogen, methyl, ethyl, 2,2-difluoroethyl, or 2,2,2-trifluoroethyl.
4. A 4 and A 5 are, independently of each other, N or CH.
5. A 4 and A 5 and are both CH.
6. -R 4 is R 4a In the case: A 14 is N and A 24 is N or CH, and A 34 is N or CH; or A 14 is N and A 24 is N or CH, and A 34 is CH; or A 14 is N and A 24 is CH, and A 34 is N or CH; or A 14 is N and A 24 is CH, and A 34 is CH; and -R 4 is R 4b In the case: A 14 is N; or A 14 The compound of claim 1 , wherein is CH.
7. R 4c is methyl, ethyl, propyl, difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, allyl, propargyl, cyclopropylmethyl, cyclobutylmethyl, 2-cyclopropylethyl, or 3-cyclopropylpropyl.
8. -A 14 is N, and R 4 is R 4a If A 24 and A 34 is CH; and -R 4c The compound of claim 1 , wherein is methyl or ethyl.
9. X 0 The compound of claim 1 , wherein
10. R 1 is hydrogen, methyl, ethyl, cyanomethyl, methoxymethyl, cyclopropyl-methyl, allyl, propargyl, benzyloxycarbonyl or benzyl.
11. R 2a is a halogen, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Haloalkylsulfanyl, C 1 ~C 3 Haloalkoxy, C 1 ~C 3 C optionally substituted with 1 or 2 substituents independently selected from haloalkyl, cyano, and halogen; 3 ~C 6 Cycloalkyl, C 1 ~C 3 C optionally substituted with 1 to 3 substituents independently selected from haloalkyl, cyano, and halogen; 3 ~C 6 Cycloalkyl C 1 ~C 4 Alkyl, C 1 ~C 5 Cyanoalkyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 4 Haloalkylsulfonyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Haloalkylsulfinyl, C 3 ~C 6 Cycloalkylsulfanyl, C 3 ~C 6 cycloalkylsulfinyl, or C 3 ~C 6 The compound of claim 1 which is a cycloalkylsulfonyl.
12. R 2b is a halogen, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Haloalkylsulfanyl, C 1 ~C 3 Haloalkylsulfonyl, C 1 ~C 3 Alkoxy, C 1 ~C 3 The compound of claim 1 which is haloalkoxy or CN.
13. R 2a and R 2b is independently selected from chloro, bromo, iodo, and trifluoromethyl.
14. R 3 is C 1 ~C 3 The compound of claim 1 , wherein the aryl group is alkyl.
15. R 3 The compound of claim 1 , wherein is methyl.
16. -Q is Q a If: R 5 is hydrogen, methyl, trifluoromethoxy, methoxy, cyclopropyl, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, difluoromethoxy, 2,2,2-trifluoroethyl, chloro, bromo, methoxyethoxy, methylcarbonyl or methoxycarbonyl; and -Q is Q b If: R 5a is hydrogen, halogen, CN, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 3 ~C 4 Cycloalkyl, C 1 ~C 3 Alkoxy or C 1 ~C 3 haloalkoxy; and R 5b is hydrogen, halogen, CN, C 1 ~C 3 Haloalkyl, C 3 ~C 4 Cycloalkyl, C 1 ~C 3 Alkoxy or C 1 ~C 3 The compound of claim 1 which is a haloalkoxy.
17. A composition comprising a compound according to any one of claims 1 to 16, one or more auxiliaries and diluents, and optionally one or more other active ingredients.
18. (i) a method for combating and controlling insects, mites, nematodes or molluscs, which method comprises the step of applying to the pest, the habitat of the pest or to plants susceptible to attack by the pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound according to any one of claims 1 to 16; or (ii) a method for protecting plant propagation material from attack by insects, mites, nematodes or mollusks, the method comprising treating the propagation material or the locus where the propagation material is to be planted with an effective amount of a compound according to any one of claims 1 to 16; or (iii) A method for controlling parasites in or on an animal in need thereof, comprising administering an effective amount of a compound according to any one of claims 1 to 16. (i) a method for the extermination and control of insects, mites, nematodes or molluscs, the method comprising the step of applying to the pest, the pest's habitat or to plants susceptible to attack by the pest an insecticidally, acaricidally, nematicidally or molluscicidal effective amount of the composition of claim 17; or (ii) a method for protecting plant propagation material from attack by insects, mites, nematodes or mollusks, the method comprising treating the propagation material or the locus where the propagation material is to be planted with an effective amount of the composition of claim 17; or (iii) A method for controlling parasites in or on an animal in need thereof, comprising the step of administering an effective amount of the composition of claim 17.
20. Plant propagation material, such as seeds, comprising, treated with or having attached thereto a compound according to any one of claims 1 to 16.
21. Plant propagation material such as seeds comprising, treated with or having attached thereto the composition of claim 17.
22. Compound of Formula XII(i) 【Chemistry 4】 (In the formula, A 14 , A 24 , A 34 and R 4c is as defined in claim 1, 6, 7 or 8) or a tautomer thereof, However, the compound 【Transformation 5】 is not 6-hydrazinyl-2-methyl-3(2H)-pyridazinone or a tautomer thereof, or 【Transformation 6】 6-hydrazinyl-2-ethyl-3(2H)-pyridazinone, or a tautomer thereof is neither a compound nor a tautomer thereof.
23. Compounds of Formula XX(i), XXI(i) or XXII(i) 【Transformation 7】 (In the formula, R 4a is as defined in any one of claims 1, 6 or 7; X - teeth, a conjugate base of an inorganic acid selected from hydrochloric acid, hydrobromic acid, hydrogen fluoride, hydrogen iodide, and sulfuric acid; and Conjugate base of an organic acid selected from carboxylic acids and sulfonic acids wherein the anion is selected from: