Pesticide-active benzyl-amide and azine-amide compounds

Abstract

Compounds of formula (I) wherein the substituents are as defined in claim 1, and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds can be used as insecticides. #imgabs0#

Description

[0001] The present invention relates to pesticidal, in particular insecticidal, benzene-amide and azine-amide compounds, processes for their preparation, compositions comprising those compounds, and their use for controlling animal pests, including arthropods, and in particular insects or representatives of the order Acarina.

[0002] WO 2017192385 describes certain heteroaryl-1,2,4-triazole and heteroaryl-tetrazolyl compounds for use in controlling ectoparasites in animals (such as mammals and non-mammals).

[0003] Novel pesticidally active benzene-amide and azine-amide compounds have now been discovered.

[0004] Thus, in a first aspect, the present invention relates to compounds having formula I

[0005]

[0006] in:

[0007] Q is

[0008]

[0009] A1, A2, A3 and A4 are independently CR5 or N, provided that no more than three of A1, A2, A3 and A4 are N;

[0010] R1 is hydrogen, C1-C6 alkyl, C1-C6 cyanoalkyl, aminocarbonyl C1-C6 alkyl, hydroxycarbonyl C1-C6 alkyl, C1-C6 nitroalkyl, trimethylsilyl C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C4 cycloalkyl C1-C2 alkyl wherein the C3-C4 cycloalkyl is optionally substituted with 1 or 2 halogen atoms, oxetan-3-yl-CH2-, or benzyl optionally substituted with halogen or C1-C6 haloalkyl;

[0011] R2 is phenyl, pyridine, pyrimidine, pyrazine or pyridazine, wherein the phenyl, pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to three substituents, provided that the one or more substituents are not on any carbon adjacent to the carbon to which C=O is attached, and each substituent is independently selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 haloalkylthio, C1-C3 alkoxy, C1-C3 haloalkoxy, halogen, NO2, SF5, CN, CONH2, COOH and C(S)NH2;

[0012] R3 is C1-C3 alkyl or C1-C3 haloalkyl;

[0013] R4 is pyridine, pyrimidine, pyrazine or pyridazine, wherein the pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to three substituents independently selected from C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen or hydroxy;

[0014] R5 is hydrogen, halogen, CN, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkoxycarbonyl or di(C1-C3 alkoxy)methane; provided that if A1, A2, A3 and A4 are all CH, then R4 is not pyridin-3-yl; or the stereoisomers, enantiomers, tautomers and N-oxides of the compound of formula I, or an agrochemically acceptable salt thereof.

[0015] Compounds of formula I with at least one basic center can form acid addition salts, for example, with strong inorganic acids (e.g. mineral acids, such as perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrohalic acids), strong organic carboxylic acids (e.g. unsubstituted or, for example, halogen-substituted C1-C4-alkanecarboxylic acids, such as acetic acid, for example saturated or unsaturated dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, for example hydroxycarboxylic acids, such as ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or for example benzoic acid), or organic sulfonic acids (e.g. unsubstituted or, for example, halogen-substituted C1-C4-alkanesulfonic acids or arylsulfonic acids, such as methanesulfonic acid or p-toluenesulfonic acid). Compounds of formula I having at least one acidic group can, for example, form salts with bases, such as mineral salts, for example alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts; or with ammonia or organic amines (for example morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, for example ethylamine, diethylamine, triethylamine or dimethylpropylamine, or mono-, di- or trihydroxy-lower alkylamines, for example monoethanolamine, diethanolamine or triethanolamine).

[0016] In each case, the compounds of formula I according to the invention are in free form, in oxidized form, such as N-oxides, or in salt form (eg in the form of agronomically usable salts).

[0017] N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen-containing heteroaromatic compounds. They are described, for example, by A. Albini and S. Pietra in 1991 in the book "Heterocyclic N-oxides", published by CRC Press, Boca Raton.

[0018] The compounds of formula I according to the invention also include hydrates which may be formed during salt formation.

[0019] As used herein, the term "C1-C n The term “alkyl” refers to a saturated straight or branched hydrocarbon group having 1 to n carbon atoms, attached through any carbon atom, such as any one of 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, and 1-ethyl-2-methylpropyl.

[0020] As used herein, the term "C1-C n “Haloalkyl” refers to a straight-chain or branched saturated alkyl group (as defined above) having 1 to n carbon atoms, attached via any of these 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, any of the following: chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoroethyl, 2,2-difluoropropyl, 2,3-difluoroethyl, 2,2-difluoropropyl, 2,3-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trichloroethyl, 2-fluoro-2-ethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2,2-difluoropropyl, 2,3-difluoroethyl, 2,2-difluoropropyl, 2,3-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-fluoro-2-ethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, 2-fluoro-2-ethyl, 2-fluoro-2 fluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl. Accordingly, the term "Ci-C2 fluoroalkyl" shall mean a Ci-C2 alkyl group having 1, 2, 3, 4 or 5 fluorine atoms, such as any of the following: difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl or pentafluoroethyl.

[0021] As used herein, the term "C1-C n"Alkoxy" refers to a straight or branched saturated alkyl group having 1 to n carbon atoms (as described above) attached via an oxygen atom, i.e., any of methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy. As used herein, the term "halogenated C1-C n "Alkoxy" refers to C1-C n Alkoxy groups wherein one or more hydrogen atoms on the alkyl group are replaced by the same or different halogen atoms - examples include trifluoromethoxy, 2-fluoroethoxy, 3-fluoropropoxy, 3,3,3-trifluoropropoxy, 4-chlorobutoxy.

[0022] As used herein, the term "C1-C n "Cyanoalkyl" refers to a straight or branched chain saturated C1-C n Alkyl groups (as defined above) wherein one of the hydrogen atoms in these groups is replaced by a cyano group: for example, cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, 3-cyanopropyl, 1-(cyanomethyl)-2-ethyl, 1-(methyl)-2-cyanoethyl, 4-cyanobutyl, and the like.

[0023] As used herein, the term "C3-C n "Cycloalkyl" refers to a 3-n-membered cycloalkyl group such as cyclopropane, cyclobutane, cyclopropane, cyclopentane and cyclohexane.

[0024] 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 rest of the molecule. In this case, the C3-C4 cycloalkyl-C1-C2 alkyl- group is substituted, and the substituent(s) may be on the cycloalkyl or alkyl chain.

[0025] As used herein, the term "aminocarbonyl C1-C n "Alkyl" refers to an alkyl group in which one of the hydrogen atoms in the group is replaced by a CONH2 group.

[0026] As used herein, the term "hydroxycarbonyl C1-C n "Alkyl" refers to an alkyl group in which one of the hydrogen atoms in the group is replaced by a COOH group.

[0027] As used herein, the term "C1-C n "Nitroalkyl" refers to an alkyl group in which one of the hydrogen atoms in the group is replaced by a NO2 group.

[0028] As used herein, the term "C1-C n Halogenated alkylthio (or "C1-C n"Haloalkylsulfanyl" refers to a C1-C3 haloalkyl moiety attached through a sulfur atom.

[0029] As used herein, the term "trimethylsilyl C1-C n "Alkyl" refers to an alkyl group in which one of the hydrogen atoms in the group is replaced by a -Si(CH3)3 group.

[0030] As used herein, the term "C2-C n "Alkenyl" refers to a straight or branched alkenyl chain having two to n carbon atoms and one or two double bonds, for example vinyl, prop-1-enyl, but-2-enyl.

[0031] As used herein, the term "C2-C n "Haloalkenyl" refers to a C2-C4 group substituted by one or more halogen atoms which may be the same or different. n Alkenyl moiety.

[0032] As used herein, the term "C2-C n "Alkynyl" refers to a straight or branched alkynyl chain having from two to n carbon atoms and one triple bond, for example ethynyl, prop-2-ynyl, but-3-ynyl,

[0033] As used herein, the term "C2-C n "Haloalkynyl" refers to a C2-C4 substituted by one or more halogen atoms which may be the same or different. n Alkynyl moiety.

[0034] Halogen is typically fluorine, chlorine, bromine or iodine. This also applies correspondingly to halogen in combination with other meanings, such as haloalkyl.

[0035] The pyridine, pyrimidine, pyrazine and pyridazine groups (unsubstituted or substituted) of R2 and R4 are each attached to the remainder of the compound through a carbon atom in each ring.

[0036] As used herein, the term "control" means reducing the number of pests, eliminating pests and / or preventing further pest damage, thereby reducing damage to plants or plant-derived products.

[0037] As used herein, staggered lines, such as in Q-1 and R4-1, indicate the point of connection / attachment to the rest of the compound.

[0038] As used herein, the term "pest" refers to insects and molluscs found in agriculture, horticulture, forestry, storage of products of plant origin (e.g., fruit, grain, and wood); and those pests associated with damage to man-made structures. The term pest includes all stages of the pest life cycle.

[0039] As used herein, the term "effective amount" refers to an amount of a compound or a salt thereof, which provides the desired effect after single or multiple administrations.

[0040] An effective amount is readily determined by one skilled in the art by using known techniques and observing the results obtained under similar circumstances. In determining an effective amount, many factors are considered, including, but not limited to: the type of plant or derived product to be applied; the pest to be controlled and its life cycle; the specific compound to be applied; the type of application; and other relevant circumstances.

[0041] As will be understood by one of ordinary skill in the art, compounds having Formula I contain stereocenters, which are indicated by asterisks in the structures below:

[0042]

[0043] wherein R1, R2, R3 and Q are as defined in the first aspect.

[0044] The present invention contemplates both the racemates and the individual enantiomers.Compounds having preferred stereochemistry are described below.

[0045] Particularly preferred compounds of the present invention are compounds having formula I'a:

[0046]

[0047] wherein R1, R2, R3 and Q are as defined in the first aspect, and stereoisomers, enantiomers, tautomers and N-oxides of compounds of formula (I'a), and agrochemically acceptable salts thereof.

[0048] As used herein, the term "optionally substituted" means that the referenced group is unsubstituted or substituted with the specified substituent, for example, "C3-C4 cycloalkyl optionally substituted with 1 or 2 halogen atoms" means C3-C4 cycloalkyl, C3-C4 cycloalkyl substituted with 1 halogen atom, and C3-C4 cycloalkyl substituted with 2 halogen atoms.

[0049] Examples according to the present invention are provided as listed below.

[0050] In an embodiment of each aspect of the invention, Q is

[0051]

[0052] A. wherein A1, A2, A3 and A4 are independently CR5 or N, provided that not more than three of A1, A2, A3 and A4 are N; R5 are independently hydrogen, halogen, CN, C1-C3 alkyl, C1-C3 haloalkyl or C3-C4-cycloalkyl; and R4 is pyridine, pyrimidine, pyrazine or pyridazine, wherein the pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to three substituents independently selected from C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen or hydroxy; or

[0053] B. wherein A1, A2, A3 and A4 are independently CR5 or N, provided that no more than three of A1, A2, A3 and A4 are N; R5 are independently hydrogen, fluorine, chlorine, CN, methyl, trifluoromethyl or cyclopropyl; and R4 is pyridine, pyrimidine, pyrazine or pyridazine, wherein the pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to three substituents independently selected from C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen or hydroxyl; or

[0054] C. wherein A1, A2, A3 and A4 are independently CR5 or N, provided that no more than three of A1, A2, A3 and A4 are N; R5 are independently hydrogen, fluorine, chlorine, CN, methyl, trifluoromethyl or cyclopropyl; and R4 is pyridine, pyrimidine, pyrazine or pyridazine, wherein the pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to three substituents independently selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chlorine, fluorine or hydroxyl; or

[0055] D. wherein A1, A2, A3 and A4 are independently CR5 or N, provided that no more than three of A1, A2, A3 and A4 are N; R5 are independently hydrogen, fluorine, chlorine, CN, methyl, trifluoromethyl or cyclopropyl; and R4 is pyridine, pyrimidine, pyrazine or pyridazine, wherein the pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with a substituent independently selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chlorine, fluorine or hydroxyl; or

[0056] E. wherein A1, A2, A3 and A4 are independently CR5 or N; R5 are independently hydrogen, fluorine, chlorine, CN, methyl, trifluoromethyl or cyclopropyl, provided that no more than three of A1, A2, A3 and A4 are N and no more than one of A1, A2, A3 and A4 is CR5, wherein R5 is fluorine, chlorine, CN, methyl, trifluoromethyl or cyclopropyl; and R4 is pyridine, pyrimidine, pyrazine or pyridazine, wherein the pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with a substituent independently selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chlorine, fluorine or hydroxyl; or

[0057] F. Selected from Q-1 to Q-12

[0058]

[0059] wherein R4, independent of Q, is selected from pyridine, pyrimidine, pyrazine or pyridazine, wherein the pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to three substituents, the one to three substituents being independently selected from C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen or hydroxy; or

[0060] G. is selected from Q-1 to Q-12, wherein R4 is pyridine, pyrimidine, pyrazine or pyridazine, wherein the pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to three substituents independently selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chloro, fluoro or hydroxy; or

[0061] H. is selected from Q-1 to Q-12, wherein R4 is pyridine, pyrimidine, pyrazine or pyridazine, wherein the pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with a substituent independently selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chloro, fluoro or hydroxy; or

[0062] I. is selected from Q-1, Q-5, Q-6, Q-7, Q-11 and Q-12, wherein R4, independently of Q, is selected from pyridine, pyrimidine, pyrazine or pyridazine, wherein the pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to three substituents independently selected from C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen or hydroxyl; or

[0063] J. is selected from Q-1, Q-5, Q-6, Q-7, Q-11 and Q-12, wherein R4 is pyridine, pyrimidine, pyrazine or pyridazine, wherein the pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to three substituents independently selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chloro, fluoro or hydroxy; or

[0064] K. is selected from Q-1, Q-5, Q-6, Q-7, Q-11 and Q-12, wherein R4 is pyridine, pyrimidine, pyrazine or pyridazine, wherein the pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with a substituent independently selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chloro, fluoro or hydroxy; or

[0065] L. is selected from Q-1, Q-5, Q-6, Q-7, Q-11 and Q-12, wherein R4 is selected from R4-1 to R4-7

[0066]

[0067] (wherein n is 0, 1, 2 or 3) and R6 when n is 2 or 3 are independently selected from C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl and halogen; or

[0068] M. is selected from Q-1, Q-5, Q-6, Q-7, Q-11 and Q-12, wherein R4 is selected from R4-1 to and R4-3, n is 0, 1, 2 or 3; and R6 when n is 2 or 3 are independently selected from C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl and halogen; or

[0069] N. is selected from Q-1, Q-5, Q-6, Q-7, Q-11 and Q-12, wherein R4 is selected from R4-1 to R4-3, n is 0, 1, 2 or 3; and R6 when n is 2 or 3 are independently selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chloro and fluoro; or

[0070] O. is selected from Q-1, Q-5, Q-6, Q-7, Q-11 and Q-12, wherein R4 is selected from R4-1 to and R4-3, n is 0 or 1; and R6 when 1 is selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chloro and fluoro; or

[0071] P. is selected from Q-1, Q-6 and Q-7, wherein R4 is selected from R4-1, R4-2 and R4-3, wherein n is 0, 1, 2 or 3, and R6 when n is 2 or 3 are independently selected from cyclopropyl, fluoro and chloro; or

[0072] Q. is selected from Q-1, Q-6 and Q-7, wherein R4 is selected from R4-1, R4-2 and R4-3, wherein n is 0 or 1, and R6 is selected from cyclopropyl, fluoro and chloro; or

[0073] R. is Q-7, wherein R4 is selected from R4-1, R4-2 and R4-3, wherein n is 0 or 1, and R6 is selected from cyclopropyl, fluoro and chloro.

[0074] In each of the above embodiments of Q, R5 is fluoro or hydrogen, preferably hydrogen.

[0075] In an embodiment of each aspect of the invention, R1 is

[0076] A. hydrogen; C1-C6 alkyl optionally substituted by a substituent selected from the group consisting of: CN, CONH2, COOH, NO2 and -Si(CH3)3; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C4 cycloalkyl-C1-C2 alkyl-, wherein the C3-C4 cycloalkyl- is optionally substituted by 1 or 2 halogen atoms; oxetan-3-yl-CH2-; or benzyl optionally substituted by halogen or C1-C3 haloalkyl; or

[0077] B. hydrogen; C1-C6 haloalkyl; C1-C6 alkyl optionally substituted by CN or Si(CH3)3; C3-C6 alkynyl; C3-C4 cycloalkyl-C1-C2 alkyl-, wherein the C3-C4 cycloalkyl is optionally substituted by 1 or 2 halogen atoms; oxetane-3-yl-CH2-; or benzyl optionally substituted by halogen; or

[0078] C. hydrogen, C1-C6 alkyl, C3-C4 cycloalkyl, C1-C2 alkyl- (wherein the C3-C4 cycloalkyl is optionally substituted by 1 or 2 halogen atoms), or oxetan-3-yl-CH2-; or

[0079] D. hydrogen, C1-C6 alkyl, or C3-C4 cycloalkyl C1-C2 alkyl-; or

[0080] E. hydrogen; C1-C6 haloalkyl; C1-C6 alkyl optionally substituted by CN or Si(CH3)3; C3-C6 alkynyl; or C3-C4 cycloalkyl-C1-C2 alkyl-, wherein the C3-C4 cycloalkyl is optionally substituted by 1 or 2 halogen atoms; or

[0081] F. hydrogen; C1-C6 haloalkyl; C1-C6 alkyl; C3-C6 alkynyl; or C3-C4 cycloalkyl-C1-C2 alkyl-, wherein the C3-C4 cycloalkyl is optionally substituted by 1 or 2 halogen atoms; or

[0082] G. cyclopropyl-CH2-, n-propyl, CH≡CCH2-, CF3CH2CH2-, FCH2CH2-, FCH2CH2CH2-, 2,2-difluorocyclopropyl-CH2-, 2,2-dichlorocyclopropyl-CH2-, hydrogen, CH3, (CH3)3SiCH2-, CH3CH2-, or CNCH2-; or

[0083] H. cyclopropyl-CH2-, n-propyl, CH≡CCH2-, CF3CH2CH2-, FCH2CH2-, FCH2CH2CH2-, 2,2-difluorocyclopropyl-CH2- or 2,2-dichlorocyclopropyl-CH2-; or

[0084] I. cyclopropyl-CH2-, n-propyl, CH≡CCH2-, CF3CH2CH2-, FCH2CH2-, FCH2CH2CH2-, 2,2-difluorocyclopropyl-CH2-, hydrogen, CH3, (CH3)3SiCH2-, or CH3CH2-; or

[0085] J. cyclopropyl-CH2-, n-propyl, CH≡CCH2-, CF3CH2CH2-, FCH2CH2-, FCH2CH2CH2-, or 2,2-difluorocyclopropyl-CH2-; or

[0086] K. cyclopropyl-CH2-, n-propyl, CH≡CCH2-, CF3CH2CH2-, FCH2CH2-, or FCH2CH2CH2-; or

[0087] L. cyclopropyl -CH2-, CH≡CCH2-, hydrogen or CH3; or

[0088] M.CH≡CCH2- or cyclopropyl-CH2-; or

[0089] N. hydrogen, methyl or cyclopropyl-CH2-; or

[0090] O. Hydrogen or cyclopropyl-CH2-.

[0091] In an embodiment of each aspect of the invention, R2 is

[0092] A. phenyl, pyridine, pyrimidine, pyrazine or pyridazine, wherein the phenyl, pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to three substituents, provided that the one or more substituents are not on any carbon adjacent to the carbon to which the -C(O)- group is bonded, and the one to three substituents are each independently selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 haloalkylthio, C1-C3 alkoxy, C1-C3 haloalkoxy, halogen, NO2, SF5, CN, CONH2, COOH and C(S)NH2; or

[0093] B. phenyl, pyridine, pyrimidine, pyrazine or pyridazine, wherein the phenyl, pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to two substituents, provided that the one or more substituents are not on any carbon adjacent to the carbon to which C═O is attached, and each substituent is independently selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, halogen or CN; or

[0094] C. phenyl, 3-pyridine or 4-pyridine substituted with one or two substituents independently selected from the group consisting of C1-C3 haloalkyl, C1-C3 haloalkoxy, halogen, CN or C(S)NH2, provided that the one or more substituents are not on any carbon adjacent to the carbon to which the -C(O)- group is bonded; or

[0095] D. phenyl, 3-pyridine or 4-pyridine substituted with one or two substituents independently selected from the group consisting of C1-C3 haloalkyl, C1-C3 haloalkoxy, halogen or CN, provided that the one or more substituents are not on any carbon adjacent to the carbon to which the -C(O)- group is bonded; or

[0096] E. phenyl or 3-pyridine substituted with one or two substituents independently selected from the group consisting of C1-C3 haloalkyl, C1-C3 haloalkoxy, halogen, or CN, provided that the one or more substituents are not on any carbon adjacent to the carbon to which the -C(O)- group is bonded; or

[0097] F. 3,5-bis(trifluoromethyl)phenyl, 3,5-dichlorophenyl, 3-trifluoromethoxyphenyl, 3-chloro-5-trifluoromethylphenyl, 3-cyanophenyl, 3-chloro-5-trifluoromethoxyphenyl, 5-trifluoromethylpyridin-3-yl, 3-bromo-5-trifluoromethylphenyl, 3-cyano-5-trifluoromethylphenyl, or 2,6-bis(trifluoromethyl)pyridin-4-yl; or

[0098] G. 3,5-bis(trifluoromethyl)phenyl, 3,5-dichlorophenyl, 3-trifluoromethoxyphenyl, 3-chloro-5-trifluoromethylphenyl, 3-cyanophenyl, 3-chloro-5-trifluoromethoxyphenyl, 5-trifluoromethylpyridin-3-yl, 3-bromo-5-trifluoromethylphenyl or 3-cyano-5-trifluoromethyl-phenyl; or

[0099] H. 3,5-bis(trifluoromethyl)phenyl, 3,5-dichlorophenyl, 3-trifluoromethoxyphenyl, 3-chloro-5-trifluoromethylphenyl, 3-cyanophenyl, 3-chloro-5-trifluoromethoxyphenyl or 5-trifluoromethylpyridin-3-yl; or

[0100] I. is 3,5-bis(trifluoromethyl)phenyl, 3-chloro-5-trifluoromethylphenyl, 3-cyanophenyl-3-chloro-5-trifluoromethoxyphenyl, 5-trifluoromethylpyridin-3-yl or 3-cyano-5-trifluoromethylphenyl; or

[0101] J. 3,5-bis(trifluoromethyl)phenyl, 3-chloro-5-trifluoromethylphenyl, 3-chloro-5-trifluoromethoxyphenyl or 5-trifluoromethylpyridin-3-yl; or

[0102] K. 3,5-bis(trifluoromethyl)phenyl; or

[0103] L.Z1 to Z 14 one of; or

[0104]

[0105] M.Z1、Z2、Z3、Z5、Z6、Z 10 , Z 11 , Z 12 or Z 14 one of; or

[0106] N.Z1、Z3、Z5、Z 10 , Z 11 , Z 12 or Z 14 one of; or

[0107] O.Z1, Z 10 , Z 12 or Z 14 one of; or

[0108] P.Z1.

[0109] In an embodiment of each aspect of the invention, R3 is

[0110] A. C1-C3 alkyl or C1-C3 haloalkyl; or

[0111] B. C1-C3 alkyl; or

[0112] C. Methyl.

[0113] In an embodiment, the invention provides compounds having Formula Ia to IL, wherein R1, R2, R3 and R4 are as defined for Formula I.

[0114]

[0115] Whenever reference is made or interpreted herein to a compound of Formula I, such reference or interpretation applies equally to compounds of Formulas Ia to IL. Thus, the embodiments for R1, R2, R3, and R4 of Formula I also apply equally to compounds of Formulas Ia to IL. In the embodiments, compounds of Formulas Ia, Ie, If, Ig, Ik, and IL are preferred, and preferably, compounds of Formula Ig are preferred.

[0116] Thus, the present invention provides compounds of formula I having substituents R1, R2, R3 and Q (with R4 and A1 to A4) as defined above in all combinations / permutations. Thus, for example, provided are compounds of formula I wherein Q is embodiment A (i.e., wherein Q is A1, A2, A3 and A4, which are independently CR5 or N, with the proviso that no more than three of A1, A2, A3 and A4 are N; R5 are independently hydrogen, halogen, CN, C1-C3 alkyl, or C1-C3 haloalkyl; and R4 is pyridine, pyrimidine, pyrazine or pyridazine, wherein the pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to three substituents independently selected from C1-C3 alkyl, C1-C3 haloalkyl, ... haloalkyl, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 haloalkyl, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 haloalkyl, C1-C3 haloalkyl, C1-C3 haloalkyl 3-haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen or hydroxy); R1 is Example D (i.e., R1 is hydrogen, C1-C6 alkyl, or C3-C4 cycloalkylC1-C2 alkyl-); R2 is Example H (i.e., R2 is 3,5-bis(trifluoromethyl)phenyl, 3,5-dichlorophenyl, 3-trifluoromethoxyphenyl, 3-chloro-5-trifluoromethylphenyl, 3-cyanophenyl, 3-chloro-5-trifluoromethoxyphenyl or 5-trifluoromethylpyridin-3-yl); and R3 is Example C (i.e., R3 is methyl).

[0117] In embodiments of each aspect of the invention, the compound of formula I has as R1 hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C4 cycloalkylC1-C2 alkyl- (wherein the C3-C4 cycloalkyl is optionally substituted with 1 or 2 halogen atoms), or oxetan-3-yl-CH2-; as R2 phenyl, pyridine, pyrimidine, pyrazine or pyridazine, wherein the phenyl, pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to two substituents, provided that the one or more substituents are not in the group attached to C=O. on any carbon adjacent to a carbon, and the substituents are each independently selected from: C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkoxy, C1-C3 haloalkoxy, halogen or CN; C1-C3 alkyl as R3; Q-1 to Q-12 as Q, wherein R4 on Q is pyridine, pyrimidine, pyrazine or pyridazine, wherein the pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to three substituents, the one to three substituents being independently selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chlorine, fluorine or hydroxyl.

[0118] In embodiments of each aspect of the invention, the compound of formula I has as R1 hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C4 cycloalkyl, C1-C2 alkyl- (wherein the C3-C4 cycloalkyl is optionally substituted with 1 or 2 halogen atoms), or oxetan-3-yl-CH2-; as R2 Z1 to Z 14as one of; C1-C3 alkyl as R3, Q-1 to Q-12 as Q, wherein R4 on Q is pyridine, pyrimidine, pyrazine or pyridazine, wherein the pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to three substituents independently selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chlorine, fluorine or hydroxyl.

[0119] In embodiments of each aspect of the invention, the compound of formula I has hydrogen, C1-C6 alkyl, C3-C6 alkenyl, C3-C6 alkynyl, C3-C4 cycloalkyl, C1-C2 alkyl- as R1; Z1 to Z 14 as one of; C1-C3 alkyl as R3; Q-1 to Q-12 as Q, wherein R4 on Q is selected from R4-1 to R4-3, n is 0, 1, 2 or 3; and R6 when n is 2 or 3 are independently selected from C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl and halogen.

[0120] In embodiments of each aspect of the present invention, the compound of formula I has cyclopropyl -CH2-, CH2=CHCH2-, CH≡CCH2-, hydrogen or CH3 as R1; Z1, Z2, Z3, Z5, Z6, Z 10 , Z 11 , Z 12 or Z 14 as R3 C1-C3 alkyl; as Q Q-1 to Q-12, wherein R4 on Q is selected from R4-1 and R4-3, n is 0 or 1; and R6 when 1 is selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chlorine and fluorine.

[0121] In embodiments of each aspect of the present invention, the compound of formula I has cyclopropyl -CH2-, CH2=CHCH2-, CH≡CCH2-, hydrogen or CH3 as R1; Z1, Z2, Z3, Z5, Z6, Z 10 , Z 11 , Z 12 or Z 14 as one of; C1-C3 alkyl as R3; Q-1, Q-5, Q-6, Q-7, Q-11 and Q-12 as Q, wherein R4 on Q is selected from R4-1 to R4-3, n is 0, 1, 2 or 3; and R6 when n is 2 or 3 are independently selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chlorine and fluorine.

[0122] In embodiments of each aspect of the present invention, the compound of formula I has cyclopropyl -CH2-, CH2=CHCH2-, CH≡CCH2-, hydrogen or CH3 as R1; Z1, Z2, Z3, Z5, Z6, Z 10, Z 11 , Z 12 or Z 14 as one of; methyl as R3; Q-1, Q-5, Q-6, Q-7, Q-11 and Q-12 as Q, wherein R4 on Q is selected from R4-1 to R4-3, n is 0, 1, 2 or 3; and R6 when n is 2 or 3 are independently selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chlorine and fluorine.

[0123] In embodiments of each aspect of the present invention, the compound of formula I has cyclopropyl -CH2-, CH2=CHCH2-, CH≡CCH2-, hydrogen or CH3 as R1; Z1, Z2, Z3, Z5, Z6, Z 10 , Z 11 , Z 12 or Z 14 as one of; methyl as R3; Q-1, Q-5, Q-6, Q-7, Q-11 and Q-12 as Q, wherein R4 on Q is selected from R4-1 to R4-3, n is 0 or 1; and R6 when n is 1 is selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chlorine and fluorine.

[0124] In embodiments of each aspect of the present invention, the compound of formula I has cyclopropyl-CH2-, hydrogen or CH3 as R1; Z1, Z3, Z5, Z 10 , Z 11 , Z 12 or Z 14 as R3 methyl; as Q-1, Q-6 and Q-7, wherein R4 on Q is selected from R4-1 to and R4-3, n is 0 or 1; and R6 when n is 1 is selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chlorine and fluorine.

[0125] In embodiments of each aspect of the present invention, the compound of formula I has cyclopropyl-CH2-, hydrogen or CH3 as R1; Z1, Z 10 , Z 12 or Z 14 as R3 methyl; as Q-1, Q-6 and Q-7, wherein R4 on Q is selected from R4-1 to R4-3, n is 0 or 1; and R6 when n is 1 is selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chlorine and fluorine.

[0126] In embodiments of each aspect of the present invention, the compound of formula I has cyclopropyl-CH2-, hydrogen or CH3 as R1; Z1, Z3, Z5, Z 10 , Z 11 , Z 12 or Z 14as R3 methyl; as Q-7, wherein R4 on Q is selected from R4-1 to R4-3, n is 0 or 1; and R6 when n is 1 is selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chlorine and fluorine.

[0127] In embodiments of each aspect of the present invention, the compound of formula I has cyclopropyl-CH2-, hydrogen or CH3 as R1; Z1, Z 10 , Z 12 or Z 14 as R3 methyl; as Q-7, wherein R4 on Q is selected from R4-1 to R4-3, n is 0 or 1; and R6 when n is 1 is selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chlorine and fluorine.

[0128] In embodiments of each aspect of the invention, the compound of formula I has as R1 hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C4 cycloalkyl, C1-C2 alkyl- (wherein the C3-C4 cycloalkyl is optionally substituted with 1 or 2 halogen atoms), or oxetan-3-yl-CH2-; as R2 Z1, Z 10 , Z 12 or Z 14 as R3 C1-C3 alkyl, as Q Q-7, wherein R4 on Q is selected from R4-1 to R4-3, n is 0 or 1; and R6 when n is 1 is selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chlorine and fluorine.

[0129] In an embodiment of each aspect of the invention, the compound of formula I has cyclopropyl -CH2- or hydrogen as R1; Z1 as R2; methyl as R3; Q-7 as Q, wherein R4 on Q is R4-1, n is 0 or 1; and R6 when n is 1 is selected from cyclopropyl, chloro and fluoro.

[0130] In embodiments, the compound of Formula I is selected from compounds of Formula Ia, Ie, If, Ig, Ik, and IL, wherein R1, R2, R3, and R4 are as defined herein.

[0131] In an embodiment, the compound of formula I is Ig, wherein R1 is cyclopropyl-CH2-, hydrogen, or CH3; R2 is Z1, Z3, Z5, Z 10 , Z 11 , Z 12 or Z 14 ; R3 methyl; R4 is selected from R4-1 to R4-3, n is 0 or 1; and R6 when n is 1 is selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chlorine and fluorine.

[0132] In an embodiment, the compound of formula I is Ig, wherein R1 is cyclopropyl-CH2- or hydrogen; R2 is Z1, Z 10 , Z 12 or Z 14 ; R3 methyl; R4 is selected from R4-1 to R4-3, n is 0 or 1; and R6 when n is 1 is selected from methyl, trifluoromethyl, methoxy, cyclopropyl, chlorine and fluorine.

[0133] In an embodiment, the compound of formula I is Ig, wherein R1 is cyclopropyl-CH2- or hydrogen; R2 is Z1; R3 is methyl; R4 is selected from R4-1 to R4-3, n is 0 or 1; and R6 when n is 1 is selected from cyclopropyl, chloro and fluoro.

[0134] In a second aspect, the present invention provides a composition comprising a compound of formula I as defined in the first aspect, one or more adjuvants and diluents, and optionally one or more other active ingredients.

[0135] In a third aspect, the present invention provides a method for combating and controlling insects, mites, nematodes or molluscs, which method comprises applying an insecticidal, acaricidal, nematicidal or molluscicidal effective amount of a compound as defined in the first aspect or a composition as defined in the second aspect to the pest, a location of the pest or a plant susceptible to attack by the pest.

[0136] In a fourth aspect, the present invention provides a method for protecting plant propagation material from attack by insects, mites, nematodes or molluscs, which method comprises treating the propagation material or the site in which the propagation material is planted with an effective amount of a compound of formula I as defined in the first aspect or a composition as defined in the second aspect.

[0137] In a fifth aspect, the present invention provides plant propagation material (eg seeds) comprising, treated with or adhered to a compound of formula I as defined in the first aspect or a composition as defined in the second aspect.

[0138] In another aspect, the present invention provides a method for controlling parasites in or on an animal in need thereof, the method comprising administering an effective amount of a compound of the first aspect. The present invention further provides a method for controlling ectoparasites on the body surface of an animal in need thereof, the method comprising administering an effective amount of a compound having Formula I as defined in the first aspect. The present invention further provides a method for preventing and / or treating a disease transmitted by an ectoparasite, the method comprising administering an effective amount of a compound having Formula I as defined in the first aspect to an animal in need thereof.

[0139] Those skilled in the art can prepare compounds of Formula I according to known methods. More specifically, compounds of Formula I and I'a and their intermediates can be prepared as described in the following schemes and examples. For the sake of clarity, certain stereocenters are not specified and are not intended to limit the teaching of these schemes in any way.

[0140] The method for preparing the compound of formula I can be carried out by methods known to those skilled in the art.

[0141]

[0142] wherein R1, R2, R3 and Q are as defined in the first aspect, and can be obtained by an amine having formula II

[0143]

[0144] wherein R1, R3 and Q are as defined for compounds of formula I, are prepared by reaction with a carboxylic acid derivative of formula III

[0145]

[0146] wherein R2 is as defined for compounds of formula I. The chemistry is described in more detail in Scheme 1.

[0147] Option 1:

[0148]

[0149] In Scheme 1, a compound of formula III (wherein R2 is as defined in formula I) is activated to a compound of formula IIIa by methods known to those skilled in the art and described, for example, in Tetrahedron, 61 (46), 10827-10852, 2005. For example, a compound wherein X0 is a halogen is formed by treating a compound of formula III with, for example, oxalyl chloride or thionyl chloride in the presence of a catalytic amount of DMF in an inert solvent such as dichloromethane or THF at a temperature between 20° C. and 100° C. (preferably 25° C.). Treatment of IIIa with a compound of formula II (wherein R1, R3 and Q are as defined above) optionally in the presence of a base such as triethylamine or pyridine yields a compound of formula I. Alternatively, compounds of formula III can be prepared by treating them with dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) or 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium-3-oxide hexafluorophosphate (HATU) in an inert solvent such as pyridine, DMF, acetonitrile, CH2Cl2 or THF, optionally in the presence of a base such as triethylamine, at temperatures between 50°C and 180°C to give activated species IIIa (wherein X0 is X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, X12, X13, X14, X15, X16, X17, X18, X19, X20, X21, X22, X33, X19, X23, X24, X35, X40, X51, X61, X7, X8, X9, X10, X11, X12, X13, X14, X15, X16, X17, X18, X19, X22, X18, X19, X23, X19, X24, X18, X19, X25, X26, X37, X40, X51, X61, X7, X8, X9, X10, X11, X12, X13, X14, X15, X16, X17, X18, X19, X1 01 、X 02 and X 03 ) to prepare compounds of formula I. Finally, acids of formula III can also be prepared by reacting with coupling agents such as propanephosphonic anhydride ) reaction activation to obtain a compound of formula IIIa (wherein X0 is X 04 ), as described, for example, in Synthesis 2013, 45, 1569. Further reaction with amines of formula II gives compounds of formula I.

[0150] Compounds of formula II (wherein R1, R3 and Q are as defined in formula I) (which, when structurally introduced into the definition of Q, corresponds to compounds of formula IIa) can be prepared according to Scheme 2:

[0151] Option 2.

[0152]

[0153] In Scheme 2, a compound of formula IV (wherein Xa1 is a halogen or an arylsulfonate or an alkylsulfonate such as a triflate and R3, A1, A2, A3 and A4 are as defined in formula I) is reacted with a tin compound of formula V (wherein R4 is as defined in formula I) in the presence of a palladium catalyst (e.g., tetrakistriphenylphosphine palladium(0) or (1,1'bis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane (1:1 complex)) in an inert solvent (e.g., DMF, acetonitrile or dioxane), optionally in the presence of an additive (e.g., potassium fluoride or cesium fluoride, or lithium chloride), and optionally in the presence of an additional catalyst (e.g., copper(I) iodide) to give a compound of formula VI (wherein R3, R4, A1, A2, A3 and A4 are as defined in formula I). Such Steele couplings are also well known to those skilled in the art and have been described, for example, in J. Org. Chem., 2005, 70, 8601-8604, J. Org. Chem., 2009, 74, 5599-5602, and Angew. Chem. Int. Ed., 2004, 43, 1132-1136. Compounds of formula VI can be treated with compounds of formula VII (wherein R1 is as defined in formula I), for example analogously to WO 2002 / 088073, page 35, in the presence of NaBH(OAc)3 or NaBH3CN (preferably with NaBH3CN as reducing agent), in a suitable solvent (preferably in acetic acid) at room temperature to form compounds of formula IIa (wherein R1, R3, R4, A1, A2, A3 and A4 are as defined in formula I). Another reagent system for reductive amination uses a combination of Ti(i-OPr) and NaBH4 in the presence of an amine of formula VII to provide compounds of formula II (see Synthesis 2003(14), 2206).

[0154] Compounds of formula VI, wherein R3, R4, Al, A2, A3 and A4 are as defined in formula I, can also be prepared by a Suzuki reaction (Scheme 3), which involves, for example, reacting a compound of formula IV, wherein R3, Al, A2, A3 and A4 are as defined in formula I and Xa1 is a leaving group such as, for example, chloro, bromo or iodo, or an arylsulfonate or alkylsulfonate such as trifluoromethanesulfonate, with a compound of formula VIIIa, wherein Y b1 It can be a boron-derived functional group such as B(OH)2 or B(OR b1 )2, where R b1 Can be C1-C4 alkyl or two groups OR b1The reaction can be carried out using a palladium-based catalyst such as tetrakis(triphenylphosphine)-palladium or (1,1'-bis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane (1:1 complex) in the presence of a base such as sodium carbonate or cesium fluoride, in a solvent or solvent mixture such as, for example, a mixture of 1,2-dimethoxyethane and water, or a mixture of dioxane and water, or a mixture of DMF and water, preferably under an inert atmosphere. The reaction temperature can preferably range from room temperature to the boiling point of the reaction mixture. This type of Suzuki reaction is well known to those skilled in the art and has been reviewed in, for example, J.Orgmet.Chem. [Journal of Organometallic Chemistry] 576, 1999, 147–168.

[0155] Option 3

[0156]

[0157] Reductive amination as described in Scheme 2 produces compounds of formula IIa. Compounds of formula IV are generally commercially available.

[0158] In an alternative method (Scheme 4), a compound of formula VI (wherein R3, R4, A1, A2, A3 and A4 are as defined in formula I) can be reduced in the usual manner (see for example WO2012 / 082997, page 141) (for example in MeOH to give an alcohol of formula IX) by reduction with for example NaBH4 to a compound of formula IX, which is then reacted with a compound of formula R A SO2Cl compound (where R A is CH3 or p-CH3-C6H4) in an inert solvent (preferably in dichloromethane) and activated in the presence of a base (such as triethylamine) to give a compound of formula X (wherein Xb2 is -OSO2R A ), or by methods known to those skilled in the art by treatment with a phosphorus compound of formula P(Xb2)3 (wherein Xb2 is halogen) to an alkyl halide to prepare a compound of formula X (wherein Xb2 is halogen) and described, for example, in Organische Chemie. [Organic Chemistry] Edition 4, Wiley-VCH Verlag [Wiley-VCH Publisher], Weinheim 2005, pages 393 et ​​seq. Finally, the compound of formula X is reacted with an amine of formula VII to give a compound of formula IIa, wherein R1, R3, R4 and A1 to A4 are as defined in formula I.

[0159] Option 4

[0160]

[0161] Compounds of formula VI are commercially available or can be prepared as shown in Scheme 5:

[0162] Option 5:

[0163]

[0164] As shown in Scheme 5, a compound of formula XI (wherein A1 to A4 are as defined in formula I, Ra1 is C1-C6 alkyl and X a1 is a leaving group as defined above) can be converted to a compound of formula XII (wherein R4, and A1 to A4 are as defined in formula I and Ra1 is C1-C6 alkyl) by reaction with a compound of formula V (Steele reaction) or a compound of formula VIII (Suzuki reaction) in the presence of a palladium catalyst as described in Schemes 2 and 3. The compound of formula XII is then converted to a carboxylic acid by methods known in the art (see, for example, WO2011 / 143365, page 138). Activation of the carboxylic acid (see Scheme 1) and treatment with N-methoxy-N-methylamine (according to Weinreb et al. Tet. Lett. [Tetrahedron Letters]. 1981, 39, 3815) gives a Weinreb amide of formula XIII (wherein R4 and A1 to A4 are as defined in formula I). Treatment of compound XIII with a Grignard reagent R3MgBr (eg MeMgBr) at a lower temperature (preferably at 0°C to 25°C) affords an alkyl ketone of formula VI (wherein R3, R4 and A1 to A4 are as defined in formula I).

[0165] 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, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxide and carbocyclic amines. Examples that 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).

[0166] The reactants can be reacted as such, i.e. without the addition of solvents or diluents. However, in most cases, it is advantageous to add an inert solvent or diluent or a mixture of these substances. If the reaction is carried out in the presence of a base, an excess of a base such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline can also serve as a solvent or diluent.

[0167] These reactions are advantageously carried out in a temperature range of from about -80°C to about +140°C, preferably from about -30°C to about +100°C, in many cases in a range between ambient temperature and about +80°C.

[0168] Depending on the reaction conditions and the starting materials chosen as appropriate in the respective case, it is possible, for example, to replace only one substituent with another substituent according to the invention in one reaction step or to replace several substituents with several other substituents according to the invention in one and the same reaction step.

[0169] Salts of compounds of formula I can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent, and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.

[0170] Salts of compounds of the formula I can be converted in a customary manner into the free compounds I, acid addition salts (for example by treatment with suitable basic compounds or with suitable ion exchange reagents) and salts with bases (for example by treatment with suitable acids or with suitable ion exchange reagents).

[0171] Salts of compounds of the formula I can be converted in a manner known per se into other salts, acid addition salts of compounds of the formula I, for example into other acid addition salts, for example by treating salts of inorganic acids (such as hydrochlorides) with suitable metal salts of the acid (such as sodium, barium or silver salts, for example with silver acetate) in a suitable solvent in which the inorganic salt formed (such as silver chloride) is insoluble and therefore precipitates from the reaction mixture.

[0172] Depending on the procedure or reaction conditions, those compounds of the formula I which have salt-forming properties can be obtained in free form or in the form of salts.

[0173] Depending on the number of asymmetric carbon atoms present in the molecule, the absolute and relative configuration and / or on the configuration of non-aromatic double bonds present in the molecule, the compounds of the formula I and, where appropriate, their tautomers (in each case in free form or in salt form) may be present in the form of one of the possible isomers or as a mixture of these, for example in the form of pure isomers, such as enantiomers and / or diastereomers, or as isomer mixtures, such as enantiomeric mixtures, for example racemates, diastereomeric mixtures or racemic mixtures; the present invention relates to the pure isomers and also to all possible isomer mixtures, and this is to be understood in each case above and below, even when stereochemical details are not explicitly mentioned in each case.

[0174] Diastereomeric mixtures or racemic mixtures of compounds of formula I in free form or in salt form, the acquisition of which may depend on the starting materials and procedures chosen, can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example, by fractional crystallization, distillation and / or chromatography.

[0175] Enantiomeric mixtures obtainable in an analogous manner (e.g., racemates) can be resolved into the optical antipodes by known methods, for example, by recrystallization from optically active solvents; by chromatography on chiral adsorbents, for example, high performance liquid chromatography (HPLC) on acetylcellulose; by cleavage with specific immobilized enzymes with the aid of suitable microorganisms; by forming containing compounds, for example, using chiral crown ethers, in which only one enantiomer is complexed; or by conversion into diastereomeric salts, for example, by reacting the basic end product racemate with an optically active acid (e.g., 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 obtainable in this way, for example, by fractional crystallization based on their different solubilities, thereby obtaining the diastereomers from which the desired enantiomer can be freed by the action of suitable reagents, for example, basic reagents.

[0176] Pure diastereomers or enantiomers can be obtained according to the invention not only by separation of the appropriate isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the method according to the invention with starting materials having the appropriate stereochemistry.

[0177] N-oxides can be prepared by reacting a compound of formula I with a suitable oxidizing agent (e.g. H O / urea adduct) in the presence of an anhydride (e.g. trifluoroacetic anhydride). Such oxidations are known from the literature, for example from J. Med. Chem., 32 (12), 2561-73, 1989 or WO 2000 / 15615.

[0178] If the individual components have different biological activities, it is advantageous to isolate or synthesize the biologically more effective isomers, such as enantiomers or diastereomers or isomer mixtures, such as enantiomeric mixtures or diastereomeric mixtures, in each case.

[0179] If appropriate, the compounds of formula I and, where appropriate, their tautomers (in each case in free form or in salt form) can also be obtained in the form of hydrates and / or include other solvents, such as those which can be used for crystallization of compounds present in solid form.

[0180] The compounds of formula I according to the following tables A-1 to A-15 can be prepared according to the above methods. The examples which follow are intended to illustrate the invention and to show preferred compounds of formula I (in the form of compounds of formula Ia).

[0181]

[0182] Table A-1 provides 14 compounds A-1.001 to A-1.014 of formula a, wherein R1 is H, R4 is pyrimidin-2-yl, and R2 is as defined in Table Z.

[0183] For example, compound A-1.010 is

[0184]

[0185] Table Z: Definition of substituents for R2:

[0186]

[0187]

[0188] Table A-2 Provided are 14 compounds A-2.001 to A-2.014 of formula Ia wherein R1 is H, R4 is 2-pyridyl, and R2 is as defined in Table Z.

[0189] Table A-3 Provided are 14 compounds A-3.001 to A-3.014 of formula Ia wherein R1 is H, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0190] Table A-4 Provided are 14 compounds A-4.001 to A-4.014 of formula Ia wherein R1 is CH3, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0191] Table A-5 Provided are 14 compounds A-5.001 to A-5.014 of Formula Ia wherein R1 is CH3, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0192] Table A-6 Provided are 14 compounds A-6.001 to A-6.014 of Formula Ia wherein R1 is CH3, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0193] Table A-7 Provided are 14 compounds A-7.001 to A-7.014 of formula Ia wherein R1 is allyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0194] Table A-8 Provided are 14 compounds A-8.001 to A-8.014 of formula Ia, wherein R1 is allyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0195] Table A-9 Provided are 14 compounds A-9.001 to A-9.014 of formula Ia wherein R1 is allyl, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0196] Table A-10 Provided are 14 compounds A-10.001 to A-10.014 of formula Ia, wherein R1 is prop-2-ynyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0197] Table A-11 Provided are 14 compounds A-11.001 to A-11.014 of formula Ia, wherein R1 is prop-2-ynyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0198] Table A-12 Provided are 14 compounds A-12.001 to A-12.014 of formula Ia wherein R1 is prop-2-ynyl, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0199] Table A-13Provided are 14 compounds A-13.001 to A-13.014 of Formula Ia, wherein R1 is CH2Cyp, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0200] Table A-14 Provided are 14 compounds A-14.001 to A-14.014 of Formula Ia, wherein R1 is CH2Cyp, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0201] Table A-15 Provided are 14 compounds A-15.001 to A-15.014 of Formula Ia, wherein R1 is CH2Cyp, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0202] The compounds of formula I according to the following tables G-1 to G-15 can be prepared according to the above methods. The examples which follow are intended to illustrate the invention and to show preferred compounds of formula I (in the form of compounds of formula Ib).

[0203]

[0204] Table G-1 Fourteen compounds G-1.001 to G-1.014 of Formula Ib are provided wherein R1 is H, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0205] Table G-2 Provided are 14 compounds G-2.001 to G-2.014 of Formula Ib wherein R1 is H, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0206] Table G-3 Provided are 14 compounds G-3.001 to G-3.014 of Formula Ib wherein R1 is H, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0207] Table G-4 Provided are 14 compounds G-4.001 to G-4.014 of Formula Ib wherein R1 is CH3, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0208] Table G-5 Provided are 14 compounds G-5.001 to G-5.014 of Formula Ib wherein R1 is CH3, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0209] Table G-6Provided are 14 compounds G-6.001 to G-6.014 of Formula Ib wherein R1 is CH3, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0210] Table G-7 Provided are 14 compounds G-7.001 to G-7.014 of Formula Ib wherein R1 is allyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0211] Table G-8 Provided are 14 compounds G-8.001 to G-8.014 of Formula Ib wherein R1 is allyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0212] Table G-9 Provided are 14 compounds G-9.001 to G-9.014 of Formula Ib wherein R1 is allyl, R4 is (3-chloro-2-pyridyl) and R2 is as defined in Table Z.

[0213] Table G-10 Provided are 14 compounds G-10.001 to G-10.014 of formula Ib wherein R1 is prop-2-ynyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0214] Table G-11 Provided are 14 compounds G-11.001 to G-11.014 of formula Ib wherein R1 is prop-2-ynyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0215] Table G-12 Provided are 14 compounds G-12.001 to G-12.014 of Formula Ib wherein R1 is prop-2-ynyl, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0216] Table G-13 Provided are 14 compounds G-13.001 to G-13.014 of Formula Ib wherein R1 is CH2Cyp, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0217] Table G-14 Provided are 14 compounds G-14.001 to G-14.014 of Formula Ib wherein R1 is CH2Cyp, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0218] Table G-15Provided are 14 compounds G-15.001 to G-15.014 of Formula Ib wherein R1 is CH2Cyp, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0219] The compounds of formula I according to the following tables H-1 to H-15 can be prepared according to the above methods. The examples which follow are intended to illustrate the invention and to show preferred compounds of formula I (in the form of compounds of formula Ic).

[0220]

[0221] Table H-1 Provided are 14 compounds H-1.001 to H-1.014 of Formula Ic, wherein R1 is H, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0222] Table H-2 Provided are 14 compounds H-2.001 to H-2.014 of Formula Ic wherein R1 is H, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0223] Table H-3 Provided are 14 compounds H-3.001 to H-3.014 of Formula Ic wherein R1 is H, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0224] Table H-4 Provided are 14 compounds H-4.001 to H-4.014 of Formula Ic wherein R1 is CH3, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0225] Table H-5 Provided are 14 compounds H-5.001 to H-5.014 of Formula Ic wherein R1 is CH3, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0226] Table H-6 Provided are 14 compounds H-6.001 to H-6.014 of Formula Ic wherein R1 is CH3, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0227] Table H-7 Provided are 14 compounds H-7.001 to H-7.014 of Formula Ic wherein R1 is allyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0228] Table H-8Provided are 14 compounds H-8.001 to H-8.014 of Formula Ic wherein R1 is allyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0229] Table H-9 Provided are 14 compounds H-9.001 to H-9.014 of Formula Ic wherein R1 is allyl, R4 is (3-chloro-2-pyridyl) and R2 is as defined in Table Z.

[0230] Table H-10 Provided are 14 compounds H-10.001 to H-10.014 of Formula Ic, wherein R1 is prop-2-ynyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0231] Table H-11 Provided are 14 compounds H-11.001 to H-11.014 of Formula Ic, wherein R1 is prop-2-ynyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0232] Table H-12 Provided are 14 compounds of Formula Ic H-12.001 to H-12.014 wherein R1 is prop-2-ynyl, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0233] Table H-13 Provided are 14 compounds H-13.001 to H-13.014 of Formula Ic, wherein R1 is CH2Cyp, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0234] Table H-14 Provided are 14 compounds H-14.001 to H-14.014 of Formula Ic, wherein R1 is CH2Cyp, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0235] Table H-15 Provided are 14 compounds H-15.001 to H-15.014 of Formula Ic, wherein R1 is CH2Cyp, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0236] The compounds of formula I according to the following tables I-1 to I-15 can be prepared according to the above methods. The examples which follow are intended to illustrate the invention and to show preferred compounds of formula I (in the form of compounds of formula Id).

[0237]

[0238] Table I-1Provided are 14 compounds I-1.001 to I-1.014 of formula Id, wherein R1 is H, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0239] Table I-2 Provided are 14 compounds of formula Id, I-2.001 to I-2.014, wherein R1 is H, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0240] Table I-3 Provided are 14 compounds of formula Id, I-3.001 to I-3.014, wherein R1 is H, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0241] Table I-4 Provided are 14 compounds of formula Id, I-4.001 to I-4.014, wherein R1 is CH3, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0242] Table I-5 Provided are 14 compounds of Formula Id, I-5.001 to I-5.014, wherein R1 is CH3, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0243] Table I-6 Provided are 14 compounds of formula Id, I-6.001 to I-6.014, wherein R1 is CH3, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0244] Table I-7 Provided are 14 compounds of formula Id, I-7.001 to I-7.014, wherein R1 is allyl, R4 is pyrimidin-2-yl, and R2 is as defined in Table Z.

[0245] Table I-8 Provided are 14 compounds of formula Id, I-8.001 to I-8.014, wherein R1 is allyl, R4 is 2-pyridyl, and R2 is as defined in Table Z.

[0246] Table I-9 Provided are 14 compounds of formula Id, I-9.001 to I-9.014, wherein R1 is allyl, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0247] Table I-10 Provided are 14 compounds of formula Id, I-10.001 to I-10.014, wherein R1 is prop-2-ynyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0248] Table I-11 Provided are 14 compounds of formula Id, I-11.001 to I-11.014, wherein R1 is prop-2-ynyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0249] Table I-12 Provided are 14 compounds of formula Id, I-12.001 to I-12.014, wherein R1 is prop-2-ynyl, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0250] Table I-13 Provided are 14 compounds of Formula Id, I-13.001 to I-13.014, wherein R1 is CH2Cyp, R4 is pyrimidin-2-yl, and R2 is as defined in Table Z.

[0251] Table I-14 Provided are 14 compounds of Formula Id, I-14.001 to I-14.014, wherein R1 is CH2Cyp, R4 is 2-pyridyl, and R2 is as defined in Table Z.

[0252] Table I-15 Provided are 14 compounds of Formula Id, I-15.001 to I-15.014, wherein R1 is CH2Cyp, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0253] The compounds of formula I according to the following tables B-1 to B-15 can be prepared according to the above methods. The examples which follow are intended to illustrate the invention and show preferred compounds of formula I (in the form of compounds of formula Ie).

[0254]

[0255] Table B-1 Provided are 14 compounds B-1.001 to B-1.014 of formula Ie, wherein R1 is H, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0256] Table B-2 Provided are 14 compounds B-2.001 to B-2.014 of Formula Ie wherein R1 is H, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0257] Table B-3 Provided are 14 compounds B-3.001 to B-3.014 of formula Ie wherein R1 is H, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0258] Table B-4 Provided are 14 compounds B-4.001 to B-4.014 of Formula Ie wherein R1 is CH3, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0259] Table B-5 Provided are 14 compounds B-5.001 to B-5.014 of Formula Ie, wherein R1 is CH3, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0260] Table B-6 Provided are 14 compounds B-6.001 to B-6.014 of Formula Ie, wherein R1 is CH3, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0261] Table B-7 Provided are 14 compounds B-7.001 to B-7.014 of formula Ie, wherein R1 is allyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0262] Table B-8 Provided are 14 compounds B-8.001 to B-8.014 of formula Ie, wherein R1 is allyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0263] Table B-9 Provided are 14 compounds B-9.001 to B-9.014 of formula Ie wherein R1 is allyl, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0264] Table B-10 Provided are 14 compounds B-10.001 to B-10.014 of formula Ie, wherein R1 is prop-2-ynyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0265] Table B-11 Provided are 14 compounds B-11.001 to B-11.014 of formula Ie, wherein R1 is prop-2-ynyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0266] Table B-12 Provided are 14 compounds B-12.001 to B-12.014 of Formula Ie, wherein R1 is prop-2-ynyl, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0267] Table B-13Provided are 14 compounds B-13.001 to B-13.014 of Formula Ie, wherein R1 is CH2Cyp, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0268] Table B-14 Provided are 14 compounds B-14.001 to B-14.014 of Formula Ie, wherein R1 is CH2Cyp, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0269] Table B-15 Provided are 14 compounds B-15.001 to B-15.014 of Formula Ie, wherein R1 is CH2Cyp, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0270] The compounds of formula I according to the following tables C-1 to C-15 can be prepared according to the above methods. The following examples are intended to illustrate the present invention and show preferred compounds of formula I (in the form of compounds of formula If)

[0271]

[0272] Table C-1 Provided are 14 compounds C-1.001 to C-1.014 of formula If, wherein R1 is H, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0273] Table C-2 Provided are 14 compounds C-2.001 to C-2.014 of formula If, wherein R1 is H, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0274] Table C-3 Provided are 14 compounds C-3.001 to C-3.014 of formula If wherein R1 is H, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0275] Table C-4 Provided are 14 compounds C-4.001 to C-4.014 of Formula If, wherein R1 is CH3, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0276] Table C-5 Provided are 14 compounds C-5.001 to C-5.014 of Formula If, wherein R1 is CH3, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0277] Table C-6Provided are 14 compounds C-6.001 to C-6.014 of Formula If, wherein R1 is CH3, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0278] Table C-7 Provided are 14 compounds C-7.001 to C-7.014 of Formula If, wherein R1 is allyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0279] Table C-8 Provided are 14 compounds C-8.001 to C-8.014 of Formula If, wherein R1 is allyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0280] Table C-9 Provided are 14 compounds C-9.001 to C-9.014 of Formula If, wherein R1 is allyl, R4 is (3-chloro-2-pyridyl) and R2 is as defined in Table Z.

[0281] Table C-10 Provided are 14 compounds C-10.001 to C-10.014 of formula If, wherein R1 is prop-2-ynyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0282] Table C-11 Provided are 14 compounds C-11.001 to C-11.014 of formula If, wherein R1 is prop-2-ynyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0283] Table C-12 Provided are 14 compounds C-12.001 to C-12.014 of formula If, wherein R1 is prop-2-ynyl, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0284] Table C-13 Provided are 14 compounds C-13.001 to C-13.014 of Formula If, wherein R1 is CH2Cyp, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0285] Table C-14 Provided are 14 compounds C-14.001 to C-14.014 of Formula If, wherein R1 is CH2Cyp, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0286] Table C-15Provided are 14 compounds C-15.001 to C-15.014 of Formula If, wherein R1 is CH2Cyp, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0287] The compounds of formula I according to the following tables D-1 to D-30 can be prepared according to the above methods. The following examples are intended to illustrate the present invention and show preferred compounds of formula I (in the form of compounds of formula Ig)

[0288]

[0289] Table D-1 Provided are 14 compounds D-1.001 to D-1.014 of formula Ig wherein R1 is H, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0290] Table D-2 Provided are 14 compounds D-2.001 to D-2.014 of formula Ig wherein R1 is H, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0291] Table D-3 Provided are 14 compounds D-3.001 to D-3.014 of formula Ig wherein R1 is H, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0292] Table D-4 Provided are 14 compounds D-4.001 to D-4.014 of formula Ig wherein R1 is CH3, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0293] Table D-5 Provided are 14 compounds D-5.001 to D-5.014 of formula Ig wherein R1 is CH3, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0294] Table D-6 Provided are 14 compounds D-6.001 to D-6.014 of formula Ig wherein R1 is CH3, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0295] Table D-7 Provided are 14 compounds D-7.001 to D-7.014 of formula Ig wherein R1 is allyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0296] Table D-8Provided are 14 compounds D-8.001 to D-8.014 of formula Ig wherein R1 is allyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0297] Table D-9 Provided are 14 compounds D-9.001 to D-9.014 of formula Ig wherein R1 is allyl, R4 is (3-chloro-2-pyridyl) and R2 is as defined in Table Z.

[0298] Table D-10 Provided are 14 compounds D-10.001 to D-10.014 of formula Ig wherein R1 is prop-2-ynyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0299] Table D-11 Provided are 14 compounds D-11.001 to D-11.014 of formula Ig wherein R1 is prop-2-ynyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0300] Table D-12 Provided are 14 compounds D-12.001 to D-12.014 of formula Ig wherein R1 is prop-2-ynyl, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0301] Table D-13 Provided are 14 compounds D-13.001 to D-13.014 of Formula Ig wherein R1 is CH2Cyp, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0302] Table D-14 Provided are 14 compounds D-14.001 to D-14.014 of Formula Ig wherein R1 is CH2Cyp, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0303] Table D-15 Provided are 14 compounds D-15.001 to D-15.014 of Formula Ig wherein R1 is CH2Cyp, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0304] Table D-16 Provided are 14 compounds D-16.001 to D-16.014 of formula Ig wherein R1 is H, R4 is 5-fluoro-2-pyridyl and R2 is as defined in Table Z.

[0305] Table D-17Provided are 14 compounds D-17.001 to D-17.014 of formula Ig wherein R1 is H, R4 is 5-bromo-2-pyridyl and R2 is as defined in Table Z.

[0306] Table D-18 Provided are 14 compounds D-18.001 to D-18.014 of formula Ig wherein R1 is H, R4 is 5-bromo-pyrimidin-2-yl and R2 is as defined in Table Z.

[0307] Table D-19 Provided are 14 compounds D-19.001 to D-19.014 of formula Ig wherein R1 is CH3, R4 is 5-fluoro-2-pyridyl and R2 is as defined in Table Z.

[0308] Table D-20 Provided are 14 compounds D-20.001 to D-20.014 of formula Ig, wherein R1 is CH3, R4 is 5-bromo-2-pyridyl and R2 is as defined in Table Z.

[0309] Table D-21 Provided are 14 compounds D-21.001 to D-21.014 of formula Ig wherein R1 is CH3, R4 is 5-bromo-pyrimidin-2-yl and R2 is as defined in Table Z.

[0310] Table D-22 Provided are 14 compounds D-22.001 to D-22.014 of formula Ig wherein R1 is allyl, R4 is 5-fluoro-2-pyridyl and R2 is as defined in Table Z.

[0311] Table D-23 Provided are 14 compounds D-23.001 to D-23.014 of formula Ig wherein R1 is allyl, R4 is 5-bromo-2-pyridyl and R2 is as defined in Table Z.

[0312] Table D-24 Provided are 14 compounds D-24.001 to D-24.014 of formula Ig wherein R1 is allyl, R4 is 5-bromo-pyrimidin-2-yl and R2 is as defined in Table Z.

[0313] Table D-25 Provided are 14 compounds D-25.001 to D-25.014 of formula Ig wherein R1 is prop-2-ynyl, R4 is 5-fluoro-2-pyridyl and R2 is as defined in Table Z.

[0314] Table D-26Provided are 14 compounds D-26.001 to D-26.014 of formula Ig wherein R1 is prop-2-ynyl, R4 is 5-bromo-2-pyridinyl and R2 is as defined in Table Z.

[0315] Table D-27 Provided are 14 compounds D-27.001 to D-27.014 of formula Ig wherein R1 is prop-2-ynyl, R4 is 5-bromo-pyrimidin-2-yl and R2 is as defined in Table Z.

[0316] Table D-28 Provided are 14 compounds D-28.001 to D-28.014 of formula Ig wherein R1 is CH2Cyp, R4 is 5-fluoro-2-pyridyl and R2 is as defined in Table Z.

[0317] Table D-29 Provided are 14 compounds D-29.001 to D-29.014 of formula Ig wherein R1 is CH2Cyp, R4 is 5-bromo-2-pyridinyl and R2 is as defined in Table Z.

[0318] Table D-30 Provided are 14 compounds D-30.001 to D-30.014 of formula Ig, wherein R1 is CH2Cyp, R4 is 5-bromo-pyrimidin-2-yl and R2 is as defined in Table Z.

[0319] The compounds of formula I according to the following tables E-1 to E-15 can be prepared according to the above methods. The following examples are intended to illustrate the present invention and show preferred compounds of formula I (in the form of compounds of formula Ik)

[0320]

[0321] Table E-1 Provided are 14 compounds E-1.001 to E-1.014 of formula Ik, wherein R1 is H, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0322] Table E-2 Provided are 14 compounds E-2.001 to E-2.014 of formula Ik wherein R1 is H, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0323] Table E-3 Provided are 14 compounds E-3.001 to E-3.014 of formula Ik wherein R1 is H, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0324] Table E-4Provided are 14 compounds E-4.001 to E-4.014 of formula Ik wherein R1 is CH3, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0325] Table E-5 Provided are 14 compounds E-5.001 to E-5.014 of formula Ik wherein R1 is CH3, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0326] Table E-6 Provided are 14 compounds E-6.001 to E-6.014 of formula Ik wherein R1 is CH3, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0327] Table E-7 Provided are 14 compounds E-7.001 to E-7.014 of formula Ik wherein R1 is allyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0328] Table E-8 Provided are 14 compounds E-8.001 to E-8.014 of formula Ik wherein R1 is allyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0329] Table E-9 Provided are 14 compounds E-9.001 to E-9.014 of formula Ik wherein R1 is allyl, R4 is (3-chloro-2-pyridyl) and R2 is as defined in Table Z.

[0330] Table E-10 Provided are 14 compounds E-10.001 to E-10.014 of formula Ik wherein R1 is prop-2-ynyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0331] Table E-11 Provided are 14 compounds E-11.001 to E-11.014 of formula Ik wherein R1 is prop-2-ynyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0332] Table E-12 Provided are 14 compounds E-12.001 to E-12.014 of formula Ik wherein R1 is prop-2-ynyl, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0333] Table E-13Provided are 14 compounds E-13.001 to E-13.014 of formula Ik wherein R1 is CH2Cyp, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0334] Table E-14 Provided are 14 compounds E-14.001 to E-14.014 of formula Ik wherein R1 is CH2Cyp, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0335] Table E-15 Provided are 14 compounds E-15.001 to E-15.014 of formula Ik wherein R1 is CH2Cyp, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0336] The compounds of formula I according to the following tables F-1 to F-15 can be prepared according to the above methods. The examples which follow are intended to illustrate the invention and to show preferred compounds of formula I (in the form of compounds of formula IL).

[0337]

[0338] Table F-1 Provided are 14 compounds F-1.001 to F-1.014 of formula IL, wherein R1 is H, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0339] Table F-2 Provided are 14 compounds F-2.001 to F-2.014 of formula IL wherein R1 is H, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0340] Table F-3 Provided are 14 compounds F-3.001 to F-3.014 of formula IL wherein R1 is H, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0341] Table F-4 Provided are 14 compounds F-4.001 to F-4.014 of formula IL wherein R1 is CH3, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0342] Table F-5 Provided are 14 compounds F-5.001 to F-5.014 of formula IL wherein R1 is CH3, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0343] Table F-6Provided are 14 compounds F-6.001 to F-6.014 of formula IL wherein R1 is CH3, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0344] Table F-7 Provided are 14 compounds F-7.001 to F-7.014 of formula IL wherein R1 is allyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0345] Table F-8 Provided are 14 compounds F-8.001 to F-8.014 of formula IL wherein R1 is allyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0346] Table F-9 Provided are 14 compounds F-9.001 to F-9.014 of formula IL wherein R1 is allyl, R4 is (3-chloro-2-pyridyl) and R2 is as defined in Table Z.

[0347] Table F-10 Provided are 14 compounds F-10.001 to F-10.014 of formula IL, wherein R1 is prop-2-ynyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0348] Table F-11 Provided are 14 compounds F-11.001 to F-11.014 of formula IL wherein R1 is prop-2-ynyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0349] Table F-12 Provided are 14 compounds F-12.001 to F-12.014 of formula IL wherein R1 is prop-2-ynyl, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0350] Table F-13 Provided are 14 compounds F-13.001 to F-13.014 of formula IL wherein R1 is CH2Cyp, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0351] Table F-14 Provided are 14 compounds F-14.001 to F-14.014 of formula IL wherein R1 is CH2Cyp, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0352] Table F-15Provided are 14 compounds F-15.001 to F-15.014 of formula IL wherein R1 is CH2Cyp, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0353] The compounds of formula I according to the following tables J-1 to J-15 can be prepared according to the above methods. The examples which follow are intended to illustrate the invention and show preferred compounds of formula I (in the form of compounds of formula Ij).

[0354]

[0355] Table J-1 Provided are 14 compounds J-1.001 to J-1.014 of formula Ih wherein R1 is H, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0356] Table J-2 Provided are 14 compounds J-2.001 to J-2.014 of formula Ih wherein R1 is H, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0357] Table J-3 Provided are 14 compounds J-3.001 to J-3.014 of formula Ih wherein R1 is H, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0358] Table J-4 Provided are 14 compounds J-4.001 to J-4.014 of formula Ih wherein R1 is CH3, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0359] Table J-5 Provided are 14 compounds J-5.001 to J-5.014 of formula Ih wherein R1 is CH3, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0360] Table J-6 Provided are 14 compounds J-6.001 to J-6.014 of formula Ih wherein R1 is CH3, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0361] Table J-7 Provided are 14 compounds J-7.001 to J-7.014 of formula Ih wherein R1 is allyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0362] Table J-8Provided are 14 compounds J-8.001 to J-8.014 of formula Ih wherein R1 is allyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0363] Table J-9 Provided are 14 compounds J-9.001 to J-9.014 of formula Ih wherein R1 is allyl, R4 is (3-chloro-2-pyridyl) and R2 is as defined in Table Z.

[0364] Table J-10 Provided are 14 compounds J-10.001 to J-10.014 of formula Ih wherein R1 is prop-2-ynyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0365] Table J-11 Provided are 14 compounds J-11.001 to J-11.014 of formula Ih wherein R1 is prop-2-ynyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0366] Table J-12 Provided are 14 compounds J-12.001 to J-12.014 of formula Ih wherein R1 is prop-2-ynyl, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0367] Table J-13 Provided are 14 compounds J-13.001 to J-13.014 of Formula Ih wherein R1 is CH2Cyp, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0368] Table J-14 Provided are 14 compounds J-14.001 to J-14.014 of Formula Ih wherein R1 is CH2Cyp, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0369] Table J-15 Provided are 14 compounds J-15.001 to J-15.014 of Formula Ih wherein R1 is CH2Cyp, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0370] The compounds of formula I according to the following tables K-1 to K-15 can be prepared according to the above-described methods. The examples which follow are intended to illustrate the invention and to show preferred compounds of formula I (in the form of compounds of formula Ii).

[0371]

[0372] Table K-1Provided are 14 compounds K-1.001 to K-1.014 of formula Ii, wherein R1 is H, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0373] Table K-2 Provided are 14 compounds K-2.001 to K-2.014 of formula Ii, wherein R1 is H, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0374] Table K-3 Provided are 14 compounds K-3.001 to K-3.014 of formula Ii wherein R1 is H, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0375] Table K-4 Provided are 14 compounds K-4.001 to K-4.014 of Formula Ii, wherein R1 is CH3, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0376] Table K-5 Provided are 14 compounds K-5.001 to K-5.014 of Formula Ii, wherein R1 is CH3, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0377] Table K-6 Provided are 14 compounds K-6.001 to K-6.014 of Formula Ii wherein R1 is CH3, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0378] Table K-7 Provided are 14 compounds K-7.001 to K-7.014 of formula Ii, wherein R1 is allyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0379] Table K-8 Provided are 14 compounds K-8.001 to K-8.014 of formula Ii, wherein R1 is allyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0380] Table K-9 Provided are 14 compounds K-9.001 to K-9.014 of formula Ii wherein R1 is allyl, R4 is (3-chloro-2-pyridyl) and R2 is as defined in Table Z.

[0381] Table K-10 Provided are 14 compounds K-10.001 to K-10.014 of formula Ii, wherein R1 is prop-2-ynyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0382] Table K-11 Provided are 14 compounds K-11.001 to K-11.014 of formula Ii, wherein R1 is prop-2-ynyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0383] Table K-12 Provided are 14 compounds K-12.001 to K-12.014 of formula Ii wherein R1 is prop-2-ynyl, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0384] Table K-13 Provided are 14 compounds K-13.001 to K-13.014 of Formula Ii, wherein R1 is CH2Cyp, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0385] Table K-14 Provided are 14 compounds K-14.001 to K-14.014 of Formula Ii, wherein R1 is CH2Cyp, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0386] Table K-15 Provided are 14 compounds K-15.001 to K-15.014 of Formula Ii, wherein R1 is CH2Cyp, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0387] The compounds of formula I according to the following tables L-1 to L-15 can be prepared according to the above methods. The examples which follow are intended to illustrate the invention and show preferred compounds of formula I (in the form of compounds of formula Ij).

[0388]

[0389] Table L-1 Provided are 14 compounds L-1.001 to L-1.014 of formula Ij, wherein R1 is H, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0390] Table L-2 Provided are 14 compounds L-2.001 to L-2.014 of formula Ij wherein R1 is H, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0391] Table L-3 Provided are 14 compounds L-3.001 to L-3.014 of formula Ij wherein R1 is H, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0392] Table L-4 Provided are 14 compounds L-4.001 to L-4.014 of formula Ij wherein R1 is CH3, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0393] Table L-5 Provided are 14 compounds L-5.001 to L-5.014 of formula Ij, wherein R1 is CH3, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0394] Table L-6 Provided are 14 compounds L-6.001 to L-6.014 of formula Ij, wherein R1 is CH3, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0395] Table L-7 Provided are 14 compounds L-7.001 to L-7.014 of formula Ij, wherein R1 is allyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0396] Table L-8 Provided are 14 compounds L-8.001 to L-8.014 of formula Ij, wherein R1 is allyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0397] Table L-9 Provided are 14 compounds L-9.001 to L-9.014 of formula Ij, wherein R1 is allyl, R4 is (3-chloro-2-pyridyl) and R2 is as defined in Table Z.

[0398] Table L-10 Provided are 14 compounds L-10.001 to L-10.014 of formula Ij, wherein R1 is prop-2-ynyl, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0399] Table L-11 Provided are 14 compounds L-11.001 to L-11.014 of formula Ij, wherein R1 is prop-2-ynyl, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0400] Table L-12 Provided are 14 compounds L-12.001 to L-12.014 of formula Ij, wherein R1 is prop-2-ynyl, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0401] Table L-13Provided are 14 compounds L-13.001 to L-13.014 of formula Ij, wherein R1 is CH2Cyp, R4 is pyrimidin-2-yl and R2 is as defined in Table Z.

[0402] Table L-14 Provided are 14 compounds L-14.001 to L-14.014 of formula Ij, wherein R1 is CH2Cyp, R4 is 2-pyridyl and R2 is as defined in Table Z.

[0403] Table L-15 Provided are 14 compounds L-15.001 to L-15.014 of formula Ij, wherein R1 is CH2Cyp, R4 is (3-chloro-2-pyridinyl) and R2 is as defined in Table Z.

[0404] The compounds of formula I according to the following tables M-1 to M-60 can be prepared according to the above methods. The examples which follow are intended to illustrate the invention and to show preferred compounds of formula I (in the form of compounds of formula Ik).

[0405]

[0406] Table M-1 Provided are 14 compounds M-1.001 to M-1.014 of formula Ik, wherein R1 is H, R4 is pyrimidin-2-yl, R5a is Br and R2 is as defined in Table Z.

[0407] Table M-2 Provided are 14 compounds M-2.001 to M-2.014 of formula Ik wherein R1 is H, R4 is pyrimidin-2-yl, R5a is CH3 and R2 is as defined in Table Z.

[0408] Table M-3 Provided are 14 compounds M-3.001 to M-3.014 of formula Ik wherein R1 is H, R4 is pyrimidin-2-yl, R5a is cyclopropyl and R2 is as defined in Table Z.

[0409] Table M-4 Provided are 14 compounds M-4.001 to M-4.014 of formula Ik wherein R1 is H, R4 is 2-pyridyl, R5a is Br and R2 is as defined in Table Z.

[0410] Table M-5 Provided are 14 compounds M-5.001 to M-5.014 of Formula Ik wherein R1 is H, R4 is 2-pyridyl, R5a is CH3 and R2 is as defined in Table Z.

[0411] Table M-6Provided are 14 compounds M-6.001 to M-6.014 of formula Ik wherein R1 is H, R4 is 2-pyridyl, R5a is cyclopropyl and R2 is as defined in Table Z.

[0412] Table M-7 Provided are 14 compounds M-7.001 to M-7.014 of formula Ik wherein R1 is H, R4 is 5-fluoro-2-pyridyl, R5a is Br and R2 is as defined in Table Z.

[0413] Table M-8 Provided are 14 compounds M-8.001 to M-8.014 of formula Ik wherein R1 is H, R4 is 5-fluoro-2-pyridyl, R5a is CH3 and R2 is as defined in Table Z.

[0414] Table M-9 Provided are 14 compounds M-9.001 to M-9.014 of formula Ik wherein R1 is H, R4 is 5-fluoro-2-pyridyl, R5a is cyclopropyl and R2 is as defined in Table Z.

[0415] Table M-10 Provided are 14 compounds M-10.001 to M-10.014 of formula Ik, wherein R1 is H, R4 is 5-bromo-2-pyridyl, R5a is Br and R2 is as defined in Table Z.

[0416] Table M-11 Provided are 14 compounds M-11.001 to M-11.014 of formula Ik, wherein R1 is H, R4 is 5-bromo-2-pyridyl, R5a is CH3 and R2 is as defined in Table Z.

[0417] Table M-12 Provided are 14 compounds M-12.001 to M-12.014 of formula Ik wherein R1 is H, R4 is 5-bromo-2-pyridyl, R5a is cyclopropyl and R2 is as defined in Table Z.

[0418] Table M-13 Provided are 14 compounds M-13.001 to M-13.014 of formula Ik, wherein R1 is H, R4 is 5-bromo-2-pyrimidinyl, R5a is Br and R2 is as defined in Table Z.

[0419] Table M-14 Provided are 14 compounds M-14.001 to M-14.014 of formula Ik, wherein R1 is H, R4 is 5-bromo-2-pyrimidinyl, R5a is CH3 and R2 is as defined in Table Z.

[0420] Table M-15Provided are 14 compounds M-15.001 to M-15.014 of formula Ik wherein R1 is H, R4 is 5-bromo-2-pyrimidinyl, R5a is cyclopropyl and R2 is as defined in Table Z.

[0421] Table M-16 Provided are 14 compounds M-16.001 to M-16.014 of formula Ik, wherein R1 is CH3, R4 is pyrimidin-2-yl, R5a is Br and R2 is as defined in Table Z.

[0422] Table M-17 Provided are 14 compounds M-17.001 to M-17.014 of Formula Ik, wherein R1 is CH3, R4 is pyrimidin-2-yl, R5a is CH3 and R2 is as defined in Table Z.

[0423] Table M-18 Provided are 14 compounds M-18.001 to M-18.014 of formula Ik, wherein R1 is CH3, R4 is pyrimidin-2-yl, R5a is cyclopropyl and R2 is as defined in Table Z.

[0424] Table M-19 Provided are 14 compounds M-19.001 to M-19.014 of formula Ik, wherein R1 is CH3, R4 is 2-pyridyl, R5a is Br and R2 is as defined in Table Z.

[0425] Table M-20 Provided are 14 compounds M-20.001 to M-20.014 of Formula Ik, wherein R1 is CH3, R4 is 2-pyridyl, R5a is CH3 and R2 is as defined in Table Z.

[0426] Table M-21 Provided are 14 compounds M-21.001 to M-21.014 of formula Ik, wherein R1 is CH3, R4 is 2-pyridyl, R5a is cyclopropyl and R2 is as defined in Table Z.

[0427] Table M-22 Provided are 14 compounds M-22.001 to M-22.014 of formula Ik wherein R1 is CH3, R4 is 5-fluoro-2-pyridyl, R5a is Br and R2 is as defined in Table Z.

[0428] Table M-23 Provided are 14 compounds M-23.001 to M-23.014 of formula Ik, wherein R1 is CH3, R4 is 5-fluoro-2-pyridyl, R5a is CH3 and R2 is as defined in Table Z.

[0429] Table M-24Provided are 14 compounds M-24.001 to M-24.014 of formula Ik wherein R1 is CH3, R4 is 5-fluoro-2-pyridyl, R5a is cyclopropyl and R2 is as defined in Table Z.

[0430] Table M-25 Provided are 14 compounds M-25.001 to M-25.014 of formula Ik wherein R1 is CH3, R4 is 5-bromo-2-pyridyl, R5a is Br and R2 is as defined in Table Z.

[0431] Table M-26 Provided are 14 compounds M-26.001 to M-26.014 of formula Ik wherein R1 is CH3, R4 is 5-bromo-2-pyridyl, R5a is CH3 and R2 is as defined in Table Z.

[0432] Table M-27 Provided are 14 compounds M-27.001 to M-27.014 of formula Ik, wherein R1 is CH3, R4 is 5-bromo-2-pyridyl, R5a is cyclopropyl and R2 is as defined in Table Z.

[0433] Table M-28 Provided are 14 compounds M-28.001 to M-28.014 of formula Ik, wherein R1 is CH3, R4 is 5-bromo-2-pyrimidinyl, R5a is Br and R2 is as defined in Table Z.

[0434] Table M-29 Provided are 14 compounds M-29.001 to M-29.014 of formula Ik, wherein R1 is CH3, R4 is 5-bromo-2-pyrimidinyl, R5a is CH3 and R2 is as defined in Table Z.

[0435] Table M-30 Provided are 14 compounds M-30.001 to M-30.014 of formula Ik, wherein R1 is CH3, R4 is 5-bromo-2-pyrimidinyl, R5a is cyclopropyl and R2 is as defined in Table Z.

[0436] Table M-31 Provided are 14 compounds M-31.001 to M-31.014 of formula Ik wherein R1 is prop-2-ynyl, R4 is pyrimidin-2-yl, R5a is Br and R2 is as defined in Table Z.

[0437] Table M-32 Provided are 14 compounds M-32.001 to M-32.014 of formula Ik wherein R1 is prop-2-ynyl, R4 is pyrimidin-2-yl, R5a is CH3 and R2 is as defined in Table Z.

[0438] Table M-33 Provided are 14 compounds M-33.001 to M-33.014 of formula Ik wherein R1 is prop-2-ynyl, R4 is pyrimidin-2-yl, R5a is cyclopropyl and R2 is as defined in Table Z.

[0439] Table M-34 Provided are 14 compounds M-34.001 to M-34.014 of formula Ik wherein R1 is prop-2-ynyl, R4 is 2-pyridyl, R5a is Br and R2 is as defined in Table Z.

[0440] Table M-35 Provided are 14 compounds M-35.001 to M-35.014 of formula Ik wherein R1 is prop-2-ynyl, R4 is 2-pyridyl, R5a is CH3 and R2 is as defined in Table Z.

[0441] Table M-36 Provided are 14 compounds M-36.001 to M-36.014 of formula Ik wherein R1 is prop-2-ynyl, R4 is 2-pyridyl, R5a is cyclopropyl and R2 is as defined in Table Z.

[0442] Table M-37 Provided are 14 compounds M-37.001 to M-37.014 of formula Ik wherein R1 is prop-2-ynyl, R4 is 5-fluoro-2-pyridyl, R5a is Br and R2 is as defined in Table Z.

[0443] Table M-38 Provided are 14 compounds M-38.001 to M-38.014 of formula Ik, wherein R1 is prop-2-ynyl, R4 is 5-fluoro-2-pyridyl, R5a is CH3 and R2 is as defined in Table Z.

[0444] Table M-39 Provided are 14 compounds M-39.001 to M-39.014 of formula Ik wherein R1 is prop-2-ynyl, R4 is 5-fluoro-2-pyridyl, R5a is cyclopropyl and R2 is as defined in Table Z.

[0445] Table M-40 Provided are 14 compounds M-40.001 to M-40.014 of formula Ik, wherein R1 is prop-2-ynyl, R4 is 5-bromo-2-pyridinyl, R5a is Br and R2 is as defined in Table Z.

[0446] Table M-41Provided are 14 compounds M-41.001 to M-41.014 of formula Ik, wherein R1 is prop-2-ynyl, R4 is 5-bromo-2-pyridyl, R5a is CH3 and R2 is as defined in Table Z.

[0447] Table M-42 Provided are 14 compounds M-42.001 to M-42.014 of formula Ik wherein R1 is prop-2-ynyl, R4 is 5-bromo-2-pyridyl, R5a is cyclopropyl and R2 is as defined in Table Z.

[0448] Table M-43 Provided are 14 compounds M-43.001 to M-43.014 of formula Ik, wherein R1 is prop-2-ynyl, R4 is 5-bromo-2-pyrimidinyl, R5a is Br and R2 is as defined in Table Z.

[0449] Table M-44 Provided are 14 compounds M-44.001 to M-44.014 of formula Ik, wherein R1 is prop-2-ynyl, R4 is 5-bromo-2-pyrimidinyl, R5a is CH3 and R2 is as defined in Table Z.

[0450] Table M-45 Provided are 14 compounds M-45.001 to M-45.014 of formula Ik wherein R1 is prop-2-ynyl, R4 is 5-bromo-2-pyrimidinyl, R5a is cyclopropyl and R2 is as defined in Table Z.

[0451] Table M-46 Provided are 14 compounds M-46.001 to M-46.014 of formula Ik, wherein R1 is CH2Cyp, R4 is pyrimidin-2-yl, R5a is Br and R2 is as defined in Table Z.

[0452] Table M-47 Provided are 14 compounds M-47.001 to M-47.014 of Formula Ik, wherein R1 is CH2Cyp, R4 is pyrimidin-2-yl, R5a is CH3 and R2 is as defined in Table Z.

[0453] Table M-48 Provided are 14 compounds M-48.001 to M-48.014 of formula Ik, wherein R1 is CH2Cyp, R4 is pyrimidin-2-yl, R5a is cyclopropyl and R2 is as defined in Table Z.

[0454] Table M-49 Provided are 14 compounds M-49.001 to M-49.014 of formula Ik, wherein R1 is CH2Cyp, R4 is 2-pyridyl, R5a is Br and R2 is as defined in Table Z.

[0455] Table M-50 Provided are 14 compounds M-50.001 to M-50.014 of Formula Ik, wherein R1 is CH2Cyp, R4 is 2-pyridyl, R5a is CH3 and R2 is as defined in Table Z.

[0456] Table M-51 Provided are 14 compounds M-51.001 to M-51.014 of formula Ik wherein R1 is CH2Cyp, R4 is 2-pyridyl, R5a is cyclopropyl and R2 is as defined in Table Z.

[0457] Table M-52 Provided are 14 compounds M-52.001 to M-52.014 of Formula Ik, wherein R1 is CH2Cyp, R4 is 5-fluoro-2-pyridyl, R5a is Br and R2 is as defined in Table Z.

[0458] Table M-53 Provided are 14 compounds M-53.001 to M-53.014 of Formula Ik, wherein R1 is CH2Cyp, R4 is 5-fluoro-2-pyridyl, R5a is CH3 and R2 is as defined in Table Z.

[0459] Table M-54 Provided are 14 compounds M-54.001 to M-54.014 of formula Ik wherein R1 is CH2Cyp, R4 is 5-fluoro-2-pyridyl, R5a is cyclopropyl and R2 is as defined in Table Z.

[0460] Table M-55 Provided are 14 compounds M-55.001 to M-55.014 of Formula Ik wherein R1 is CH2Cyp, R4 is 5-bromo-2-pyridyl, R5a is Br and R2 is as defined in Table Z.

[0461] Table M-56 Provided are 14 compounds M-56.001 to M-56.014 of formula Ik, wherein R1 is CH2Cyp, R4 is 5-bromo-2-pyridyl, R5a is CH3 and R2 is as defined in Table Z.

[0462] Table M-57 Provided are 14 compounds M-57.001 to M-57.014 of formula Ik, wherein R1 is CH2Cyp, R4 is 5-bromo-2-pyridyl, R5a is cyclopropyl and R2 is as defined in Table Z.

[0463] Table M-58Provided are 14 compounds M-58.001 to M-58.014 of Formula Ik, wherein R1 is CH2Cyp, R4 is 5-bromo-2-pyrimidinyl, R5a is Br and R2 is as defined in Table Z.

[0464] Table M-59 Provided are 14 compounds M-59.001 to M-59.014 of Formula Ik, wherein R1 is CH2Cyp, R4 is 5-bromo-2-pyrimidinyl, R5a is CH3 and R2 is as defined in Table Z.

[0465] Table M-60 Provided are 14 compounds M-60.001 to M-60.014 of formula Ik, wherein R1 is CH2Cyp, R4 is 5-bromo-2-pyrimidinyl, R5a is cyclopropyl and R2 is as defined in Table Z.

[0466] Certain intermediate compounds of the amine of formula II can also be obtained

[0467] Some of them are novel. Specific examples of compounds of formula II are wherein Q is Q-1 to Q-12, R3 is methyl, and R1 is CH2Cyp; wherein Q is Q-1 to Q-12, R3 is methyl, and R1 is prop-2-ynyl; wherein Q is Q-1 to Q-12, R3 is methyl, and R1 is allyl; wherein Q is Q-1 to Q-12, R3 is methyl, and R1 is hydrogen; and wherein Q is Q-1 to Q-12, R3 is methyl, and R1 is methyl.

[0468] The compounds of formula I according to the invention are active ingredients of preventive and / or therapeutic value in the field of pest control. Even at low application rates, they have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish, and plants. These active ingredients according to the invention act on all or individual developmental stages of normally sensitive and also resistant animal pests (such as insects or representatives of the order Acarina). The insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i.e., by destruction of the pests either immediately or only after a certain period of time (e.g., during molting), or indirectly, for example, by reducing egg laying and / or hatching rates.

[0469] Examples of the animal pests mentioned above are:

[0470] from the order Acarina, e.g.

[0471] 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., 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.;

[0472] From the order Phthirus, e.g.

[0473] Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp., and Phylloxera spp.;

[0474] From the order Coleoptera, e.g.

[0475] Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotoma spp., Conoderus spp., Cosmopolites spp., Cotinisnitida, Curculio spp., Cyclocephala spp., Dermestes spp., Diabrotica spp., Diloboderus abderus), Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagriavilosa, Leptinotarsa ​​decemLineata, Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Maladera castanea, Megascelis spp., Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp., Phlyctinus spp., Popillia spp. spp.), Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Somaticus spp.), Sphenophorus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp., and Trogoderma spp.

[0476] From the order Diptera, e.g.

[0477] Aedes spp., Anopheles spp., Antherigonas occata., Bactrocea oleae, Bibio hortulanus, Bradysia spp., Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyza tripunctata, Glossina spp., Hypoderma spp.), Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis spp., Riveria quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp., and Tipula spp.;

[0478] From the order Hemiptera, e.g.

[0479] Acanthocoris scabrator, green stink bug, alfalfa blind bug, white moth (Aleurodes spp.), Amblypelta nitida, shrimp shield stink bug (Bathycoelia thalassina), soil long stink bug, stink bug, Clavigralla tomentosicollis, blind bug (Creontiades spp.), cocoa blind bug, Dichelops furcatus, cotton red stink bug, Edessa spp., American stink bug (Euchistus spp.), six-spotted cabbage stink bug (Eurydemapulchrum), flat shield stink bug, brown winged stink bug, concave giant long-legged stink bug (Horciasno bilellus), rice stink bug, grass stink bug, tropical scale stink bug, cabbage spotted stink bug (Murgantia histrionic), Neomegalotomus spp., Nesidiocoris tenuis, Green stink bug, Nysius simulans, Oebalus insularis, Skin stink bug, Wall stink bug, Red assassin bug, Cocoa stink bug, Scaptocoris castanea, Black stink bug (Scotinophara spp.), Thyanta spp., Triatomine bug, Cassava web stink bug (Vatiga illudens);

[0480] Aphids, Adalges, Agalliano ensigera, Agonascena targionii, Aleurodicus spp., Aleurocanthus spp., Sugarcane hole whitefly, Aleurothrixus floccosus, Aleyrodes brassicae, Amarascabiguttula, Amritodus atkinson, Kidney shield scale, Aphididae, Aphid, Aspidiotus spp., Eggplant groove aphid, Bactericera cockerelli, Whitefly, Brachycaudus spp., Cabbage aphid, Cavariella, Cavariella aegopodii Scop.), wax scale, brown round scale, net-seed grass leaf scale, Cicadella, Cofana spectra, Cryptomelania, Cicadulina, brown soft scale, corn yellow-winged leafhopper, naked whitefly, citrus psyllid, wheat two-tailed aphid, western round tailed aphid, small green leafhopper, apple aphid, grape leafhopper, wax clam, red eucalyptus psyllid (Glycaspis brimblecombei), cabbage constrictor aphid, large tailed aphid (Hyalopterus spp.), super-tumored aphid species, lemon fruit green leafhopper (Idioscopus clypealis), Jacobiasca lybica, Laodelphax, ball-hard scale, oyster shield scale, radish aphid (Lopaphis erysimi), Lyogenys maidis, long-supplemented aphid, Mahanarva, Metcalfa pruinosa), wheat aphid, Myndus crudus, aphid spp., Taiwan leek aphid, black-tailed leafhopper spp., brown planthopper (Nilaparvata spp.), pear green aphid, Odonaspis ruthae, parasitic sugarcane woolly aphid, bayberry whitefly, Caulis psyllid, scutellaria spp., gall aphid spp., corn waxhopper, flat-horned planthopper spp., hopscotch aphid, phylloxera spp., Mosella spp., white-shielded scale spp., mealybug spp., cotton blind bug (Pseudatomoscelis seriatus), psyllid spp., cotton scale (Pulvinaria aethiopica), round-shielded scale spp., Quesada gigas, electric leafhopper (Recilia dorsalis), constrictor aphid spp., black-helmeted scale spp., leafhopper spp., dichotomous aphid spp., wheat aphid (Sitobion spp.), white-backed planthopper, Spissistilus festinus, Tarophagus proserpina, aphids, whiteflies, Tridiscus sporoboli, Trionymus spp., African psyllids, orange-winged scale, Zyginaflammigera, and Zyginidia scutellaris;

[0481] from the order Hymenoptera, e.g.

[0482] Acromyrmex, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Pogonomyrmex spp., Slenopsis invicta, Solenopsis spp., and Vespa spp.

[0483] From the order Isoptera, e.g.

[0484] Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Tropical fire ants (Solenopsis geminate)

[0485] From the order Lepidoptera, for example,

[0486] Long-winged torrefies, brown-banded torrefies, clear-winged torrefies, ground moths, cotton leafworms, Amylois spp., pea moths, yellow torrefies, silver moths (Argyresthia spp.), banded torrefies, yarrow-patterned torrefies, cotton miners, corn borers, powdery patch moths, peach fruit moths, grass borers, leaf rollers, Chrysoteuchia topiaria, grape fruit moths, leaf rollers, cloud rollers, pattern rollers, sheath moths, lepidoptera, Cosmophila flava, grass borers, cabbage borers, apple anomaly torrefies, boxwood moths, torrefies, boxwood moths, stem borers, Sudanese cotton bollworms, diamond borers, South American corn seedling borers (Elasmopalpus lignosellus), African stem borer, mealybug, Epinotia spp., fine-spotted moth, Etiella zinckinella, flower moth, ringworm, yellow tussock moth, root cutter, Feltia jaculiferia, Grapholita spp., green budworm, Spodoptera spp., cabbage borer, Herpetogramma spp., gypsy moth, tomato borer, Lasmopalpus lignosellus, spiral leafminer, leafminer, grape flower moth, Loxostege bifidalis, tussock moth, leafminer, leaf moth, cabbage armyworm, tobacco hornworm, Mythimna spp., Noctuidae, fall moth, Orniodes indica, European corn borer, Ostrinia spp., Ctenophora spp., Spodoptera spp., Spodoptera spp., Pectinophora gossypiela, Coffee leafminer, One-star armyworm, Potato moth, Pieris spp., Pieris spp., Diamondback moth, Bud moth spp., Leaf moth spp., Peppermint moth, Richia albicosta, Scirpophaga spp., Spodoptera spp., Long-palpated Spodoptera spp., Spodoptera spp., Cotton leaffolder, Cnaphalocrocis spp., Heteroptera spp., Leaf roller spp., Cabbage looper, Tomato leafminer, and Lycoris spp.;

[0487] From the order Mallophaga, for example,

[0488] Damalina spp. and Trichodectes spp.;

[0489] From the order Orthoptera, for example,

[0490] Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtillahexadactyla, Periplaneta spp., Scapteriscus spp., and Schistocerca spp.;

[0491] From the order Psocoptera, for example,

[0492] Liposcelis spp.;

[0493] From the order Siphonaptera, for example,

[0494] Ceratophyllus spp., Ctenocephalides spp., and Xenopsylla cheopis;

[0495] From the order Thysanoptera, for example,

[0496] Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp.

[0497] From the order of the Thysanura, for example, Lepisma saccharina.

[0498] In another aspect, the present invention may also relate to a method for controlling damage to plants and parts thereof by plant-parasitic nematodes (endoparasitic, semi-endoparasitic and ectoparasitic nematodes), in particular the following plant-parasitic nematodes, such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other species of root knot nematodes; cyst-forming nematodes, Globodera rostochiensis and other species of Globodera; Heterodera avenae, Heteroderaglycines, Heterodera exigua and other species of Globodera; schachtii), Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus, and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus, and other Bursaphelenchus species; Ring nematodes, nematodes), Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stemand bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci, and other Ditylenchus species; Awl nematodes, Dolichodorus species;Spiral nematodes, Heliocotylenchus multicinctus, and other species of the genus Helicotylenchus; Sheath and sheathoid nematodes, species of the genera Hemicycliophora, and species of the genera Hemicriconemoides; Hirshmanniella species; Lancenematodes, species of the genus Hoploaimus; False rootknot nematodes, species of the genus Nacobbus; Needle nematodes, Longidoruse longatus, and other species of the genus Longidorus; Pin nematodes, species of the genus Pratylenchus; Lesion nematodes. nematodes), Pratylenchus negletus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi, and other Pratylenchus species; Burrowing nematodes, Radopholus similis, and other Radopholus species; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis, and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus) and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, and other Tylenchorhynchus species;Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant-parasitic nematode species, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp.;

[0499] The compounds described herein also have activity against mollusks. Examples include, for example, the family Pomacea; the family Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); the family Bradybaenidae (Bradybaena fruticum); the genus Cepaea (C. hortensis, C. nemoralis); the genus Ochlodina; the genus Deroceras (Wild Gray slugs (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H. obvia); Helicidae (Helicigona arbustorum; Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.

[0500] The active ingredients according to the invention can be used for controlling, that is to say suppressing or destroying pests of the aforementioned type, which occur in particular on plants, especially on useful and ornamental plants in agriculture, horticulture and forestry, or on organs of these plants, such as fruits, flowers, leaves, stems, tubers or roots, and in some cases even plant organs formed at a later point in time still remain protected against these pests.

[0501] In particular, suitable target crops are cereals, such as wheat, barley, rye, oats, rice, corn or sorghum; beets, such as sugar beets or fodder beets; fruits, such as pome, stone or soft fruit, such as apples, pears, plums, peaches, apricots, cherries or berries, such as strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soybeans; oilseed crops, such as rapeseed, mustard, poppy, olives, sunflower, coconut, castor, cocoa beans, or peanuts; cucurbits such as pumpkin, cucumber, or melon; fiber plants such as cotton, flax, hemp, or jute; citrus fruits such as oranges, lemons, grapefruits, or tangerines; vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, or bell peppers; lauraceae such as avocado, cinnamon, or camphor; and also tobacco, nuts, coffee, eggplant, sugarcane, tea, pepper, grapevines, hops, plantago, and latex plants.

[0502] The compositions and / or methods of the present invention may also be used on any ornamental and / or vegetable crop, including flowers, shrubs, broadleaf trees, and evergreen plants.

[0503] For example, the present invention can be used with any of the following ornamental plant species: Ageratum, Alonso spp., Anemone, Amur sunflower, Anthemis, Antirrhinum, Aster, Begonia (e.g., Rieger begonia, Begonia spp., Begonia tubéreux), Bougainvillea, Brachycome spp., Brassica (ornamental plants), Calceolaria, Capsicum, Catharanthus roseus, Canna, Cornflower, Chrysanthemum, Cineraria (Cinnamon), Coreopsis, Crassula coccinea, Cuphea ignea, Dahlia, Delphinium, Dicentra, Dorotheantus spp.), Lisianthus, Forsythia, Fuchsia, Geranium gnaphalium, Gerbera, Globe amaranth, Heliotrope, Sunflower, Hibiscus, Hydrangea, Hydrangea, Rhododendron, Impatiens (African balsam), Iresines spp., Kalanchoe, Lantana, March flower, Lion's ear, Lilium, Japanese lily, Physalis, Monarda, Monarda, Tagetes, Dianthus (carnation), Canna, Oxalis, Daisy, Pelargonium (Pelargonium pelargonium, Pelargonium pelargonium), Viola (pansy), Petunia, Phlox, Plectranthus spp.), poinsettia, creeper (Parthenocissus quinquefolia, Parthenocissus quinquefolia), primrose, ranunculus, azalea, Rosa (rose), rudbeckia, African violet, salvia, Scaevola aemola, Schizanthus wisetonensis, sedum, nightshade, Solanum spp., marigold, tobacco, verbena, zinnia, and other bedding plants.

[0504] For example, the present invention can be used with any of the following vegetable species: Allium (garlic, onion, shallot (A.oschaninii), leek, shallot, scallion), beaked parsley, celery, asparagus, beets, Brassica (cabbage, Chinese cabbage, turnip), peppers, chickpeas, endive, chicory (chicory, endive), watermelon, Cucurbita (cucumber, cantaloupe), Cucurbita (zucchini, Indian pumpkin), Cynara (artichoke, cardoon), carrot, fennel, Hypericum, lettuce, Lycopersicon (tomato, cherry tomato), mint, basil, parsley, Phaseolus (bean, pea), pea, radish, rhubarb, rosemary, sage, black salsify, eggplant, spinach, Valerian (V. eriocarpa), and broad beans.

[0505] Preferred ornamental plant species include African violet, begonia, dahlia, gerbera, hydrangea, verbena, rose, kalanchoe, poinsettia, aster, cornflower, coreopsis, delphinium, monarda, phlox, rudbeckia, sedum, petunia, violet, impatiens, geranium, chrysanthemum, ranunculus, fuchsia, salvia, hydrangea, rosemary, sage, St. John's wort, mint, sweet pepper, tomato, and cucumber.

[0506] The active ingredients according to the invention are particularly suitable for controlling the bean aphid, cucumber leaf beetle, tobacco budworm, green peach aphid, diamondback moth and sea worm on cotton, vegetables, corn, rice and soybean crops. The active ingredients according to the invention are also particularly suitable for controlling the cabbage looper (Mamestra) (preferably on vegetables), the codling moth (Cydia pomonella) (preferably on apples), the green leafhopper (Empoasca) (preferably on vegetables, vineyards), the potato leaf beetle (Leptinotarsa) (preferably on potatoes) and the striped stem borer (Chilo suppressalis) (preferably on rice).

[0507] Compounds of formula I are particularly useful for controlling

[0508] 2. Pests of the order Hemiptera, for example one or more of the following species: Bemisia tabaci, Aphis craccivora, Myzus persicae, Rhopalosiphum padi, Nilaparvata lugens, and Euschistus heros (preferably in vegetables, soybeans and sugarcane);

[0509] Pests of the order Lepidoptera, for example one or more of the following species: Spodoptera littoralis, Spodoptera frugiperda, Plutella xylostella, Cnaphalocrocis medinalis, Cydia pomonella, Chrysodeixis includes, Chilo suppressalis, Elasmopalpus lignosellus, Pseudoplusia includes and Tuta absoluta (preferably in vegetables and corn);

[0510] a pest of the order Thysanoptera, such as the family Thripidae, for example one or more of Thrips tabaci and Frankliniella occidentalis (preferably in vegetables); and

[0511] • Soil pests (eg Coleoptera), for example the following species: Diabrotica balteata, Agriotes spp., and Leptinotarsa ​​decemlineata (preferably in vegetables and corn).

[0512] The term "crops" is to be understood as also including crop plants which have been transformed by the use of recombinant DNA techniques such that they are able to synthesize one or more selectively acting toxins, such as are known, for example, from toxigenic bacteria, in particular those of the genus Bacillus.

[0513] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, such as insecticidal proteins from Bacillus cereus or Bacillus japonicus; or insecticidal proteins from Bacillus thuringiensis, such as delta-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or vegetative insecticidal proteins (Vips), such as Vip1, Vip2, Vip3, or Vip3A; or insecticidal proteins of bacterial colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophila, or Xenorhabdus spp. nematophilus); toxins produced by animals, such as scorpion toxins, spider toxins, bee toxins and other insect-specific neurotoxins; toxins produced by fungi, such as streptomycin, plant lectins, such as pea lectin, barley lectin or snowdrop lectin; agglutinin; protease inhibitors, such as trypsin inhibitor, silk proteinase inhibitor, potato glycoprotein, cystatin, papain inhibitor; ribosome inactivating protein (RIP), such as ricin, maize-RIP, abrin, luffain, saporin or bryophyllin; steroid metabolizing enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysteroid inhibitors, HMG-COA-reductase, ion channel blockers, such as sodium channel or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

[0514] In the context of the present invention, δ-endotoxins (e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C) or vegetative insecticidal proteins (Vips) (e.g., Vip1, Vip2, Vip3, or Vip3A) are understood to include, but are not limited to, mixed toxins, truncated toxins, and modified toxins. Mixed toxins are recombinantly produced by combining the different domains of those proteins (see, e.g., WO 02 / 15701). Truncated toxins, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of a naturally occurring toxin are replaced. In such amino acid replacements, it is preferred that a non-naturally occurring protease recognition sequence be inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see WO 03 / 018810).

[0515] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed in, for example, EP-A-0 374 753, WO 93 / 07278, WO 95 / 34656, EP-A-0 427 529, EP-A-451 878 and WO 03 / 052073.

[0516] Methods for preparing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP-A-0 367474, EP-A-0 401 979 and WO 90 / 13651.

[0517] The toxins contained in the transgenic plants confer tolerance to harmful insects. Such insects can be found in any insect taxonomic group, but are particularly common among beetles (Coleoptera), two-winged insects (Diptera), and moths (Lepidoptera).

[0518] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known and some are commercially available. Examples of such plants are: (corn variety expressing Cry1Ab toxin); YieldGard (corn variety expressing Cry3Bb1 toxin); YieldGard (corn varieties expressing Cry1Ab and Cry3Bb1 toxins); (corn variety expressing Cry9C toxin); Herculex (a corn variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) that confers tolerance to the herbicide glufosinate ammonium); NuCOTN (cotton variety expressing Cry1Ac toxin); Bollgard (cotton variety expressing Cry1Ac toxin); Bollgard (cotton varieties expressing Cry1Ac and Cry2Ab toxins); (cotton variety expressing Vip3A and Cry1Ab toxins); (potato variety expressing Cry3A toxin); GT Advantage (GA21 glyphosate tolerance trait), CB Advantage (Bt11 corn borer (CB) trait) and

[0519] Further examples of such genetically modified crops are:

[0520] 1. Bt11 maize, from Syngenta Seeds SAS, Chemin de Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. This genetically modified maize confers resistance to attack by the European corn borer (Ostrinia nubilalis and Sesamia serrata) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenicly expresses the PAT enzyme to confer tolerance to the herbicide glufosinate ammonium.

[0521] 2. Bt176 maize, from Syngenta Seeds, 27 Rue de Hobbitt, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. This genetically modified maize confers resistance to attack by the European corn borer (Ostrinia nubilalis and Sesamia serrata) through transgenic expression of the Cry1Ab toxin. Bt176 maize also transgenically expresses the enzyme PAT to confer tolerance to the herbicide glufosinate ammonium.

[0522] 3. MIR604 maize, available from Syngenta Seeds, 27 Rue de Hobbit, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. This maize plant is rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin G protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03 / 018810.

[0523] 4. MON 863 maize, from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses the Cry3Bb1 toxin and confers resistance to certain coleopteran insects.

[0524] 5. IPC 531 cotton, from Monsanto Europe SA, 270-272 Avenue Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0525] 6.1507 maize, from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Genetically modified maize expressing the protein Cry1F for resistance to certain lepidopteran insects and the protein PAT for tolerance to the herbicide glufosinate ammonium.

[0526] 7. NK603×MON 810 maize, from Monsanto Europe, 270-272 Avenue Tervuren, B-1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. This is a conventionally bred hybrid maize variety, produced by crossing the genetically modified varieties NK603 and MON 810. NK603×MON 810 maize transgenically expresses the protein CP4 EPSPS obtained from the Agrobacterium strain CP4, rendering it herbicide tolerant. (contains glyphosate), and also Cry1Ab toxin from Bacillus thuringiensis subsp. kurstakia, which confers resistance to certain lepidopteran insects, including the European corn borer.

[0527] 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 )middle.

[0528] The term "crop" should be understood to also include crop plants that have been transformed using recombinant DNA technology to enable them to synthesize selectively acting antipathogenic substances, such as, for example, so-called "pathogenesis-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 publications mentioned above.

[0529] Crops can also be modified to increase resistance to fungal (eg, Fusarium, Anthracnose, or Phytophthora), bacterial (eg, Pseudomonas), or viral (eg, Potato Leaf Roll Virus, Tomato Spotted Wilt Virus, Cucumber Mosaic Virus) pathogens.

[0530] Crops also include those with increased resistance to nematodes, such as Heterodera glycines.

[0531] Crops with tolerance to abiotic stress include those with increased tolerance to drought, high salinity, high temperature, cold, frost or light radiation, for example, through expression of NF-YB or other proteins known in the art.

[0532] Antipathogenic substances that can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers of sodium channels and calcium channels, for example viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; so-called "pathogenesis-related proteins" (PRPs; see, for example, EP-A-0 392 225); antipathogenic substances produced by microorganisms, such as peptide antibiotics or heterocyclic antibiotics (see, for example, WO 95 / 33818) or proteins or polypeptide factors which are involved in plant pathogen defense (so-called "plant disease resistance genes", as described in WO 03 / 000906).

[0533] Other areas of use of the compositions according to the invention are the protection of stored goods and storage rooms and the protection of raw materials such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, in particular the protection of humans, domestic animals and productive livestock from pests of the types mentioned.

[0534] The present invention provides a compound of the first aspect for use in treatment. The present invention provides a compound of the first aspect for use in controlling parasites in or on an animal. The present invention further provides a compound of the first aspect for use in controlling ectoparasites in an animal. The present invention further provides a compound of the first aspect for use in preventing and / or treating a disease transmitted by an ectoparasite.

[0535] The present invention provides use of the compound of the first aspect in the preparation of a medicament for controlling parasites in or on an animal. The present invention further provides use of the compound of the first aspect in the preparation of a medicament for controlling parasites external to an animal. The present invention further provides use of the compound of the first aspect in the preparation of a medicament for preventing and / or treating diseases transmitted by ectoparasites.

[0536] The present invention provides the use of the compound of the first aspect in controlling parasites in or on the body of an animal. The present invention further provides the use of the compound of the first aspect in controlling parasites external to an animal.

[0537] When used in the context of parasites in or on animals, the term "control" means reducing the number of pests or parasites, eliminating pests or parasites and / or preventing further infestation by pests or parasites.

[0538] When used in the context of parasites in or on animals, the term "treat" means to inhibit, slow, halt or reverse the progression or severity of existing symptoms or disease.

[0539] When used in the context of parasites in or on animals, the term "prevent" means avoiding symptoms or disease from developing in the animal.

[0540] When used in the context of parasites in or on animals, the term "animal" can refer to mammals and non-mammals, such as birds or fish. In the case of a mammal, it can be a human or a non-human mammal. Non-human mammals include, but are not limited to, livestock and companion animals. Livestock include, but are not limited to, cattle, camels, pigs, sheep, goats, and horses. Companion animals include, but are not limited to, dogs, cats, and rabbits.

[0541] A "parasite" is a harmful organism that lives in or on a host animal and benefits by obtaining nutrients at the host animal's expense. An "endoparasite" is a parasite that lives inside the host animal. An "ectoparasite" is a parasite that lives on the host animal's surface. Ectoparasites include, but are not limited to, Acari, 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 genera Rhipicaphalus, such as Rhipicaphalus microplus (Boophilus microplus) and Rhipicephalus sanguineus; Amblyomrna; Dermacentor; Haemaphysalis; Hyalomma; Ixodes; Rhipicentor; Margaropus; Argas; Otobius; and Ornithodoros. Mites include, but are not limited to, members of the 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 orders Siphonaptera, Diptera, Phthiraptera, Lepidoptera, Coleoptera, and Homoptera. Members of the order Siphonaptera include, but are not limited to, Ctenocephalides felis and Ctenocephatides canis.Members of the order Diptera include, but are not limited to, Musca spp.; skin flies, such as Gasterophilus intestinalis and Oestrus ovis; biting flies; horse flies, such as Haematopota spp. and Tabunus spp.; haematobia, such as Haematobia irritans; Stomoxys; Lucilia; midges; and mosquitoes. Members of the order Phthiraptera include, but are not limited to, blood-sucking and chewing lice, such as Bovicola ovis and Bovicola bovis.

[0542] When used in the context of parasites in or on an animal, the term "effective amount" refers to the amount or dosage of a compound of the invention, or a salt thereof, which, upon administration to an animal in a single or multiple doses, provides the desired effect in or on the animal. An attending diagnostician, who is skilled in the art, can readily determine an effective amount by using known techniques and by observing the results obtained in similar situations. In determining an effective amount, the attending diagnostician will consider a variety of factors, including, but not limited to: the species of mammal; its size, age, and general health; the parasite to be controlled and the degree of infestation; the specific disease or disorder involved; the degree of involvement or severity of the disease or disorder; the response of the individual; the specific compound to be administered; the mode of administration; the bioavailability characteristics of the administered formulation; the dosage regimen selected; concomitant medications used; and other relevant circumstances.

[0543] The compounds of this invention can be administered to animals by any route having 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 poured, applied, sprayed, sprayed or immersed in the form of a spray race. Alternatively, the compounds of this invention can be administered via an ear tag or collar.

[0544] Salt forms of the compounds of the present invention include both pharmaceutically acceptable salts and veterinarily acceptable salts, which may be different from agrochemically acceptable salts. Pharmaceutically and veterinarily acceptable salts and common methods 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). It will be appreciated by those skilled in the art that the compounds of the present invention can be readily converted into salts using techniques and conditions known to those skilled in the art, and can be separated as salts such as hydrochlorides. Additionally, it will be appreciated by those skilled in the art that the compounds of the present invention can be readily converted into the corresponding free alkalis from the corresponding salts and can be separated as the corresponding free alkalis converted from the corresponding salts.

[0545] 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 the composition of the present invention to the target pests, their locus, or a surface or substrate by painting, rolling, spraying, coating, or dipping. By way of example, IRS (indoor residual spraying) application to surfaces (such as walls, ceilings, or floor surfaces) is contemplated by the methods of the present invention. In another embodiment, application of such compositions to substrates such as nonwoven or fabric materials in the form of (or for use in the manufacture of) netting, coverings, bedding, curtains, and tents is contemplated.

[0546] In one embodiment, the method for controlling this type of harmful organism comprises applying the composition of the present invention of pest-killing effective dose to target harmful organism, their place or surface or matrix, so that on this surface or matrix, effective pest-killing activity of retention is provided.Such application can be carried out by brushing, rolling, spraying, coating or impregnation pest-killing composition of the present invention.By way of example, the IRS application of surface (such as wall, ceiling or floor surface) is considered by method of the present invention, so that effective pest-killing activity of retention is provided on this surface.In another embodiment, it is considered to use such composition for the residual control of the harmful organism on matrix, and this matrix is ​​the fabric material such as the form (or can be used in the manufacture of these articles) in netting, covering, quilt, curtain and tent.

[0547] The substrate to be treated (including nonwovens, fabrics or nettings) can be made of natural fibers such as cotton, raffia, jute, flax, sisal, burlap or wool, or synthetic fibers such as polyamide, polyester, polypropylene, polyacrylonitrile, etc. Polyester is particularly suitable. Methods for textile treatment are known, for example WO 2008 / 151984, WO 2003 / 034823, US 5631072, WO 2005 / 64072, WO 2006 / 128870, EP 1724392, WO 2005113886 or WO 2007 / 090739.

[0548] A further area of ​​use of the compositions according to the invention is in the field of tree injection / trunk treatment of all ornamental trees as well as all kinds of fruit and nut trees.

[0549] In the field of tree injection / trunk treatment, the compounds according to the invention are particularly suitable for combating wood-boring insects from the orders Lepidoptera mentioned above and from the orders Coleoptera, in particular against the wood-boring insects listed in the following Tables A and B:

[0550] Table A. Examples of economically important exotic wood-boring insects.

[0551]

[0552] Table B. Examples of economically important native wood-boring insects.

[0553]

[0554]

[0555]

[0556] The present invention can also be used to control any insect pest that may be present in turfgrass, including, for example, beetles, caterpillars, fire ants, ground pearls, millipedes, woodlice, mites, mole crickets, scale insects, mealybugs, ticks, cicadas, southern wheat stink bugs, and white grubs. The present invention can be used to control insect pests at all stages of their life cycle, including eggs, larvae, nymphs, and adults.

[0557] In particular, the present invention can be used to control insect pests that feed on the roots of turfgrasses, including grubs (such as Cyclocephala spp. (e.g., marked beetles, C. lurida), Rhizotrogus spp. (e.g., European beetles, European root beetles (R. majalis)), Cotinus spp. (e.g., Green June beetles, C. nitida), Popillia spp. (e.g., Japanese beetles, P. japonica), Phyllophaga spp. (e.g., May / June beetles), Ataenius spp. (e.g., Black turfgrass ataenius, A. spretulus), Maladera spp. (e.g., Asiatic garden beetles, A. spp.), and other insect pests. beetle, M. castanea, and Tomarus genera), ground pearls (Margarodes spp.), mole crickets (tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana), and leatherjackets (European crane fly, Tipula spp.).

[0558] The present invention can also be used to control insect pests of turfgrass in thatched homes, including armyworms (such as the fall armyworm Spodoptera frugiperda, and the common armyworm Pseudaletia unipuncta), cutworms, weevils (Sphenophorus spp., such as S. venatus verstitus and S. parvulus), and grass borers (such as Crambus spp. and the tropical grass borer, Herpetogramma phaeopteralis).

[0559] The present invention can also be used to control insect pests in turfgrasses that live above ground and feed on turfgrass leaves, including wheat stink bugs (such as the southern wheat stink bug, Blissus insularis), Bermudagrass mite (Eriophyes cynodoniensis), Grass mealybug (Antonina graminis), Propsapia bicincta, leafhoppers, cutworms (Noctuidae), and Schizaphis graminis.

[0560] The present invention can also be used to control other pests in turfgrass, such as introduced fire ants (Solenopsis invicta) that create nests in lawns.

[0561] In the hygiene field, the compositions according to the invention are effective against ectoparasites such as hard ticks, soft ticks, scabies, autumn mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.

[0562] Examples of such parasites are:

[0563] From the order of the Pediculus: Haemaphysalis, Longipalig, Pediculus hominis, Phtirus spp., Phtirus spp.

[0564] From the order Trichophagus: Felicola spp., Brachycera spp., Duckling spp., Cattle lice spp., Werneckiella spp., Lepikentron spp., Cattle lice spp., Trichodesmium spp., and Felicola spp.

[0565] From the order Diptera and the suborders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca domestica, Hydrotaea spp., Haematobia spp. spp.), Morellia spp., Toilet fly spp., Glossina spp., Calliphora spp., Green fly spp., Chrysopa spp., Wohlfahrtia spp., Sarcophaga spp., Mylidae spp., Dermatophagoides spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., and Melophagus spp.

[0566] From the order of the Siphonapterida, for example, Pulex spp., Ctenopsida, Xenopsyllas spp., Ceratophyllum spp.

[0567] From the order of the Heteropterida, for example, Cimex spp., Triatomine spp., Echinops spp., Panstrongylus spp.

[0568] From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattelagermanica and Supella spp.

[0569] Subclass Acaria (family Acarida) and orders Meta-stigmata and Meso-stigmata, for example, Acaria spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.

[0570] From the orders Actinedida (Prostigmata) and Acaridida (Astigmata), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp. spp.), Itch spp., Dermestida spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., and Laminosioptes spp.

[0571] The compositions according to the invention are also suitable for protecting materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings from infestation by insects.

[0572] The compositions according to the invention can be used, for example, against the following pests: beetles, such as the North American house beetle, the hairy green tiger beetle, the furniture beetle, the death beetle, Ptilinuspecticornis, Dendrobium pertinex, the fine-toothed fork-tailed beetle, Priobium carpini, the brown powder beetle, the African powder beetle, the southern powder beetle, the flat-stomached beetle, the soft-haired powder beetle, the flat-legged powder beetle, the scale-haired powder beetle, the wood beetle, the wood beetle, the black beetle, the red-bellied oak beetle, the brown heteroptera beetle, the double-spined beetle and the bamboo beetle, and also members of the Hymenoptera, such as the blue-black wood beetle, the giant wood beetle, the Taiga wood beetle and Urocerus The compounds of formula I and I'a or their salts are particularly suitable for controlling one or more pests selected from the following 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" represents "a compound selected from the group consisting of the compounds defined in Tables A-1 to A-15, B-1 to B-15, C-1 to C-15, D-1 to D-30, E-1 to E-15, F-1 to F-15, G-1 to G-15, H-1 to H-15, I-1 to I-15, J-1 to J-15, K-1 to K-15, L-1 to L-15 and M-1 to M-60 and Table P") controls one or more pests selected from the following families: Noctuidae, Plutellae, Chrysomelidae, Thripidae, Pentatomidae, Cirrhidae, Delphacidae, Aphididae, Noctuidae, Sphagidae, Meloidogyne, and Heteroderae.

[0573] The compounds of formula I and I'a or their salts are particularly suitable for controlling one or more pests 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, Rhopalosiphum spp, Pseudoplusia spp and Chilos spp. In a preferred embodiment of each aspect, compound TX (wherein the abbreviation "TX" represents "a compound selected from the group consisting of the compounds defined in Tables A-1 to A-15, B-1 to B-15, C-1 to C-15, D-1 to D-30, E-1 to E-15, F-1 to F-15, G-1 to G-15, H-1 to H-15, I-1 to I-15, J-1 to J-15, K-1 to K-15, L-1 to L-15 and M-1 to M-60 and Table P") controls one or more pests selected from the genera: Spodoptera, Diamondback moth, Thrips, Thrips, American stink bug, Codling moth, Nilaparvata, Tufts aphid, Aphis, Rootworm, Aphis, Spodoptera, and Graminaria.

[0574] The compounds of formula I and I'a, or salts thereof, are particularly useful for controlling one or more of: Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis includens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum padi, and Chilo suppressalis.

[0575] In a preferred embodiment of each aspect, compound TX (wherein the abbreviation "TX" means "a compound selected from the group consisting of the compounds defined in Tables A-1 to A-15, B-1 to B-15, C-1 to C-15, D-1 to D-30, E-1 to E-15, F-1 to F-15, G-1 to G-15, H-1 to H-15, I-1 to I-15, J-1 to J-15, K-1 to K-15, L-1 to L-15 and M-1 to M-60 and Table P") controls One or more of the following: Spodoptera littoralis, Plutella xylostella, Western flower thrips, Thrips tabaci, Brown soybean toon, Codling moth, Brown rice hopper, Green peach aphid, Soybean looper, Bean aphid, Cucumber leaf beetle, Grain aphid and Chilo suppressalis, for example, Spodoptera littoralis+TX, Plutella xylostella+TX, Western flower thrips+TX, Thrips tabaci+TX, Brown soybean toon+TX, Codling moth+TX, Brown rice hopper+TX, Green peach aphid+TX, Soybean looper+TX, Bean aphid+TX, Cucumber leaf beetle+TX, Grain aphid+TX and Chilo suppressalis+TX.

[0576] In embodiments of each aspect, one compound selected from the compounds defined in Tables A-1 to A-15, B-1 to B-15, C-1 to C-15, D-1 to D-30, E-1 to E-15, F-1 to F-15, G-1 to G-15, H-1 to H-15, I-1 to I-15, J-1 to J-15, K-1 to K-15, L-1 to L-15 and M-1 to M-60, and Table P, is suitable for controlling Spodoptera littoralis, Plutella xylostella, Western flower thrips, Thrips tabaci, Brown sturgeon, Codling moth, Brown rice hopper, Myzus persicae, Soybean looper, Bean aphid, Cucumber leaf beetle, Grain stem aphid and Chilo suppressalis in cotton, vegetables, maize, corn, rice and soybean crops.

[0577] In an embodiment, a compound selected from the compounds defined in Tables A-1 to A-15, B-1 to B-15, C-1 to C-15, D-1 to D-30, E-1 to E-15, F-1 to F-15, G-1 to G-15, H-1 to H-15, I-1 to I-15, J-1 to J-15, K-1 to K-15, L-1 to L-15 and M-1 to M-60 and Table P is suitable for controlling Mamestra (preferably on vegetables), Cydia pomonella (preferably on apples), Empoasca (preferably on vegetables, vineyards), Leptinotarsa ​​(preferably on potatoes) and Chilo suppressalis (preferably on rice).

[0578] The compounds according to the present invention may have any number of benefits, including, among others, favorable levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (e.g., higher biological activity, favorable activity spectrum, increased safety profile (against non-target organisms above and below ground, such as fish, birds, and bees), improved physico-chemical properties, or increased biodegradability). In particular, it has been unexpectedly discovered that certain compounds of Formula I can exhibit favorable safety profiles relative to non-target arthropods, particularly pollinators, such as honey bees, solitary bees, and bumble bees. Most particularly, relative to the Italian honey bee (Apis mellifera).

[0579] The compounds according to the invention can be used as pesticides in unmodified form, but they are usually formulated into compositions in various ways using formulation adjuvants such as carriers, solvents and surfactants. These formulations can be in different physical forms, for example, in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, mobile oils, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or water-miscible organic solvents as carriers), impregnated polymer films or in other known forms, for example, from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, 1st edition, second revision (2010). Such formulations can be used directly or diluted before use. Dilution can be performed with, for example, water, liquid fertilizers, micronutrients, biological organisms, oils or solvents.

[0580] These formulations can be prepared, for example, by mixing the active ingredient with formulation adjuvants to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surfactants or combinations thereof.

[0581] These active ingredients can also be contained in very fine microcapsules. Microcapsules contain active ingredients in porous carriers. This allows the active ingredients to be released (e.g., slowly released) into the environment in controlled amounts. Microcapsules typically have a diameter of from 0.1 to 500 microns. The amount of active ingredient they contain is approximately from 25% to 95% of the capsule weight by weight. These active ingredients can be in the form of a holistic solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulated membrane can include, 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, very fine microcapsules can be formed, in which the active ingredient is contained in the form of finely dispersed particles in a solid matrix of a base material, but these microcapsules themselves are not wrapped.

[0582] Formulation adjuvants suitable for preparing the compositions according to the invention are known per se. As liquid carriers there may be used: 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 acetates, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol rosinate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl Formamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol, alkyl pyrrolidone, 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, acetic acid glyceryl, diacetic acid glyceryl, triacetic acid glyceryl, decaglycerol Hexadecane, Hexanediol, Isoamyl Acetate, Isobornyl Acetate, Isooctane, Isophorone, Cumene, Isopropyl Myristate, Lactic Acid, Lauramine, Mesityl Oxide, Methoxypropanol, Methyl Isoamyl Ketone, Methyl Isobutyl Ketone, Methyl Laurate, Methyl Caprylate, Methyl Oleate, Methylene Chloride, m-Xylene, n-Hexane, n-Octylamine, Octadecanoic Acid, Octylamine Acetate, 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, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol and higher molecular weight alcohols such as amyl alcohol, tetrahydrofuranol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc.

[0583] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour, soy flour, pumice, wood flour, ground walnut shells, lignin, and similar substances.

[0584] Many surface-active substances can be used advantageously in both solid and liquid formulations, especially those which can be diluted with a carrier before use. Surface-active substances can be anionic, cationic, nonionic or polymeric and they can act as emulsifiers, 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 addition products, such as ethoxylated nonylphenol; alcohol / alkylene oxide addition products, such as ethoxylated tridecanol; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; salts of dialkylsulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary ammoniums, such as dodecyltrimethylammonium 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 phosphates; as well as other substances, such as described in: McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Company (MC Publishing Company). Corp., Ridgewood New Jersey (1981).

[0585] Other adjuvants that can be used in pesticidal formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, substances and buffers that neutralize or change the pH, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze agents, microbicides, and liquid and solid fertilizers.

[0586] The composition according to the invention may comprise an additive comprising an oil of plant or animal origin, a mineral oil, an alkyl ester of such an oil or a mixture of such an oil and an oil derivative. The amount of the oil additive in the composition according to the invention is generally from 0.01% to 10% based on the mixture to be applied. For example, the oil additive may be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oil or an oil of plant origin, such as rapeseed oil, olive oil or sunflower oil; emulsified vegetable oils; alkyl esters of oils of plant origin, such as methyl derivatives; or oils of animal origin, such as fish oil or tallow. Preferred oil additives include C8-C 22 Alkyl esters of fatty acids, especially C 12 -C 18 Methyl derivatives of fatty acids, such as the methyl esters of lauric acid, palmitic acid, and oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th edition, Southern Illinois University, 2010.

[0587] These compositions according to the invention generally comprise from 0.1% to 99% by weight, in particular from 0.1% to 95% by weight, of a compound according to the invention and from 1% to 99.9% by weight of formulation adjuvants, which preferably include from 0% to 25% by weight of surface-active substances. While commercial products may preferably be formulated as concentrates, the end user will generally use dilute formulations.

[0588] The application rate varies within wide limits and depends on the nature of the soil, the application method, the crop plants, the harmful organisms to be controlled, the prevailing climatic conditions, and other factors dictated by the application method, the time of application, and the target crop. In general, the compound can be applied at a rate of from 1 l / ha to 2000 l / ha, in particular from 10 l / ha to 1000 l / ha.

[0589] A preferred formulation may have the following composition (wt %):

[0590] Emulsifiable concentrates :

[0591] Active ingredient: 1% to 95%, preferably 60% to 90%

[0592] Surfactant: 1% to 30%, preferably 5% to 20%

[0593] Liquid carrier: 1% to 80%, preferably 1% to 35%

[0594] Dust Agent :

[0595] Active ingredient: 0.1% to 10%, preferably 0.1% to 5%

[0596] Solid carrier: 99.9% to 90%, preferably 99.9% to 99%

[0597] Suspension concentrate:

[0598] Active ingredient: 5% to 75%, preferably 10% to 50%

[0599] Water: 94% to 24%, preferably 88% to 30%

[0600] Surfactant: 1% to 40%, preferably 2% to 30%

[0601] wettable powder :

[0602] Active ingredient: 0.5% to 90%, preferably 1% to 80%

[0603] Surfactants: 0.5% to 20%, preferably 1% to 15%

[0604] Solid carrier: 5% to 95%, preferably 15% to 90%

[0605] Granules:

[0606] Active ingredient: 0.1% to 30%, preferably 0.1% to 15%

[0607] Solid carrier: 99.5% to 70%, preferably 97% to 85%

[0608] The following examples further illustrate (but do not limit) the present invention.

[0609] <![CDATA[ wettable powder ]]> a) b) c) Active ingredient 25％ 50％ 75％ Sodium lignin sulfonate 5％ 5％ - Sodium lauryl sulfate 3％ - 5％ Sodium diisobutylnaphthalenesulfonate - 6％ 10％ Phenol polyglycol ether (7-8 mol of ethylene oxide) - 2％ - Highly dispersed silicic acid 5％ 10％ 10％ Kaolin 62％ 27％ -

[0610] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a wettable powder which can be diluted with water to give a suspension of the desired concentration.

[0611] <![CDATA[ Powder for dry seed treatment ]]> a) b) c) Active ingredient 25％ 50％ 75％ Light mineral oil 5％ 5％ 5％ Highly dispersed silicic acid 5％ 5％ - Kaolin 65％ 40％ - talc - 20％

[0612] The combination is thoroughly mixed with adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a dust that can be used directly for seed treatment.

[0613] <![CDATA[ Emulsifiable concentrates ]]> Active ingredient 10％ Octylphenol polyglycol ether (4-5 mol of ethylene oxide) 3％ Calcium dodecylbenzenesulfonate 3％ Castor oil polyethylene glycol ether (35 mol ethylene oxide) 4％ Cyclohexanone 30％ Xylene mixture 50％

[0614] Emulsions of any desired dilution which can be used in plant protection can be obtained from these concentrates by dilution with water.

[0615] <![CDATA[ Dust powder ]]> a) b) c) Active ingredient 5％ 6％ 4％ talc 95％ - - Kaolin - 94％ - Mineral fillers - - 96％

[0616] Ready-to-use dusts are obtained by mixing the combination with a carrier and grinding the mixture in a suitable grinder. Such dusts can also be used for dry seed dressing of seeds.

[0617] <![CDATA[ Extruder pellets ]]> Active ingredient 15％ Sodium lignin sulfonate 2％ Carboxymethyl cellulose 1％ Kaolin 82％

[0618] The combination is mixed and ground with the adjuvants, and the mixture is moistened with water.

[0619] The mixture is extruded and then dried in a stream of air.

[0620] <![CDATA[ Coated granules ]]> Active ingredient 8％ Polyethylene glycol (molecular weight 200) 3％ Kaolin 89％

[0621] This finely ground combination is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

[0622] Suspension concentrates

[0623] Active ingredient 40％ Propylene glycol 10％ Nonylphenol polyglycol ether (15 mol of ethylene oxide) 6％ Sodium lignin sulfonate 10％ Carboxymethyl cellulose 1％ Silicone oil (in the form of a 75% emulsion in water) 1％ water 32％

[0624] The finely ground combination is intimately mixed with adjuvants to give a suspension concentrate from which a suspension of any desired dilution can be obtained by dilution with water. Using such a dilution, living plants as well as plant propagation material can be treated and protected against infection by microorganisms by spraying, pouring or immersion.

[0625] Flowable concentrate for seed treatment

[0626]

[0627] The finely ground combination is intimately mixed with adjuvants to give a suspension concentrate from which a suspension of any desired dilution can be obtained by dilution with water. Using such a dilution, living plants as well as plant propagation material can be treated and protected against infection by microorganisms by spraying, pouring or immersion.

[0628] Extended-release capsule suspension

[0629] 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of a defoamer, and 51.6 parts of water until the desired particle size is reached. To this emulsion, 2.8 parts of a mixture of 1,6-hexanediamine in 5.3 parts of water are added. The mixture is stirred until polymerization is complete. The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% active ingredient. The diameter of the medium capsules is 8 to 15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for this purpose.

[0630] Formulation types include emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oil dispersions (OD), oil suspensions (OF), oil-soluble concentrates (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume concentrates (UL), finished products (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG), or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0631] Preparation example:

[0632] "Mp" means melting point in ° C. Free radicals represent methyl groups. Recorded on a Brucker 400 MHz spectrometer 1 H NMR measurements, chemical shifts are given in ppm relative to TMS standards. Spectra were measured in deuterated solvents as indicated. The compounds were characterized using any of the following LCMS methods. Characteristic LCMS values ​​obtained for each compound are the retention time ("Rt", reported in minutes) and the measured molecular ion (M+H). + .

[0633] LCMS method:

[0634] LC-MS Method 1:

[0635] Spectra were recorded on a mass spectrometer from Waters (SQD, SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative, capillary: 3.00 kV, cone range: 30 V, extractor: 2.00 V, source temperature: 150°C, desolvation temperature: 350°C, cone gas flow: 50 l / h, desolvation gas flow: 650 l / h; mass range: 100 to 900 Da) and an Acquity UPLC from Waters: binary pump, heated column compartment, diode array detector and ELSD detector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, temperature: 60° C., DAD wavelength range (nm): 210 to 500, solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; gradient: 10%-100% B in 1.2 min; flow rate (ml / min) 0.85

[0636] LC-MS Method 2:

[0637] Spectra were recorded on an ACQUITY mass spectrometer from Waters Corporation (SQD or SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative, capillary: 3.0 kV, cone: 30 V, extractor: 3.00 V, source temperature: 150°C, desolvation temperature: 400°C, cone gas flow: 60 L / hr, desolvation gas flow: 700 L / hr, mass range: 140 to 800 Da) and an ACQUITY UPLC from Waters Corporation (with solvent degasser, binary pump, heated column compartment, and diode array detector). Column: Waters UPLC HSST3, 1.8 μm, 30×2.1 mm, temperature: 60°C, DAD wavelength range (nm): 210 to 400, solvent gradient: A = water / methanol 9:1 + 0.1% formic acid, B = acetonitrile + 0.1% formic acid, gradient: 0%-100% B in 2.5 min; flow rate (ml / min) 0.75

[0638] LC-MS Method 3:

[0639] Spectra were recorded on an Agilent mass spectrometer (single quadrupole mass spectrometer) equipped with multimode electrospray and APCI (polarity: positive and negative ion, capillary: 4.00 kV, corona current 4.0 μA, charging voltage, 2.00 kV, nitrogen flow: 9.0 L / min, nebulizer pressure: 40 psig, mass range: 100 to 1000 m / z, drying gas temperature 250° C., evaporator temperature 200° C.) and on an Agilent LCMS: quaternary pump, heated column compartment, variable wavelength detector. Column: Eclipse XDB C18, 5.0 μm, 150×4.6 mm, column temperature: ambient, wavelength (nm): 220 nm, solvents: A=0.05% TFA in water, B=0.05% TFA in acetonitrile. Gradient: time / %B: 0 / 5, 0.5 / 5, 3.5 / 90, 5 / 90, 5.1 / 5, 7 / 5; flow rate: 1.0 ml / min.

[0640] Example H1 : N-(cyclopropylmethyl)-N-[1-[3-(2-pyridyl)pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl) Synthesis of (4-amino)benzamide

[0641]

[0642] Step 1: Preparation of 1-[3-(2-pyridyl)pyrazin-2-yl]ethanone

[0643]

[0644] At room temperature, tetrakis(triphenylphosphine)palladium(0) (1.5 g, 1.3 mmol) and tributyl(2-pyridyl)stannane (2.1 mL, 6.4 mmol) were added to a solution of 1-(3-chloropyrazine-2-yl)ethanone (CAS 121246-90-0, 1.0 g, 6.4 mmol) in toluene (26 mL), and the resulting black mixture was stirred overnight at 100 ° C. The mixture was cooled to room temperature and quenched with a saturated solution of NaHCO . The aqueous layer was extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and then KF was added to the solution to remove stannane. The crude product was purified by silica gel chromatography to give 1-[3-(2-pyridyl)pyrazine-2-yl]ethanone.

[0645] 1 H NMR (400 MHz, chloroform-d) δ / ppm: 2.74 (s, 3H) 7.33-7.38 (m, 1H), 7.87 (td, J = 7.70, 1.83 Hz, 1H), 8.22 (dt, J = 7.79, 1.05 Hz, 1H), 8.57 (d, J = 2.20 Hz, 1H), 8.59-8.64 (m, 1H), 8.68 (d, J = 2.20 Hz, 1H).

[0646] LC-MS (method 1): retention time 0.34 min, m / z 200 [M+H + ].

[0647] Step 2: Preparation of N-(cyclopropylmethyl)-1-[3-(2-pyridyl)pyrazin-2-yl]ethanamine

[0648]

[0649] Method 1:

[0650] By 1- [3- (2- pyridyl) pyrazine -2- base] ethyl ketone (1.2g, 4.8mmol, 80 mass %) sample dissolution in methanol (19mL).At room temperature by syringe in the mixture, add cyclopropylmethylamine (1.3mL, 14mmol) and titanium isopropoxide (IV) (1.9mL, 6.3mmol).Reaction mixture is stirred overnight, and then at room temperature slowly add sodium borohydride (190mg, 4.8mmol) (gas evolution is observed).After 1 hour, display reaction is completed by LCMS analysis.Reaction mixture is quenched with water droplets and concentrated in vacuo.Crude product is passed through silica gel chromatography, obtains N- (cyclopropylmethyl) -1- [3- (2- pyridyl) pyrazine -2- base] ethylamine.

[0651] 1 H NMR (400 MHz, chloroform-d) δ / ppm: -0.09-0.01 (m, 2H), 0.33-0.40 (m, 2H), 0.79-0.92 (m, 1H), 1.48 (d, J = 6.60 Hz, 3H), 1.99 (dd, J = 11.74, 7.70 Hz, 1H), 2.44 (dd, J = 11.74, 6.24 Hz, 1 H),4.63(q,J=6.60Hz,1H),7.37(ddd,J=7.43,4.86,1.28Hz,1H),7.82-7.90(m,1H), 7.90-7.96(m,1H),8.53(d,J=2.57Hz,1H),8.62(d,J=2.20Hz,1H),8.70-8.75(m,1H).

[0652] LC-MS (method 1): retention time 0.51 min, m / z 255 [M+H + ].

[0653] Method 2:

[0654] A mixture of 1-(3-pyrimidin-2-yl-2-pyridyl)ethanone (0.20 g, 1.0 mmol), cyclopropylmethylamine (0.15 g, 2.0 mmol) and p-toluenesulfonic acid (0.017 g, 0.10 mmol) prepared as described above in toluene (4.5 mL) was refluxed for 16 hours using a Dean-Stark apparatus. The mixture was then cooled to room temperature, the solvent removed and the residue dried under reduced pressure. The crude product was dissolved in dry methanol (4.5 mL) and sodium borohydride (0.039 g, 1.0 mmol) was added at 0°C. The resulting mixture was stirred at room temperature overnight. Water was added to the mixture at 0°C and the crude product was purified to give N-(cyclopropylmethyl)-1-(3-pyrimidin-2-yl-2-pyridyl)ethanamine.

[0655] LC-MS (method 1): retention time 0.51 min, m / z 255 [M+H + ].

[0656] Step 3: N-(cyclopropylmethyl)-N-[1-[3-(2-pyridyl)pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)- Preparation of 4-(2-amino-4-methyl)benzamide

[0657]

[0658] N-(Cyclopropylmethyl)-1-[3-(2-pyridyl)pyrazin-2-yl]ethanamine (0.370 g, 1.16 mmol) was dissolved in DMF and N,N-diisopropylethylamine (0.399 mL, 2.33 mmol) was added. After stirring at room temperature for 10 minutes, 3,5-bis(trifluoromethyl)benzoic acid (337 mg, 1.28 mmol) was added, followed by HATU [O-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium hexafluorophosphate], 0.664 mg, 1.75 mmol). The resulting mixture was stirred at room temperature overnight and poured into a saturated solution of NH4Cl. The mixture was extracted with ethyl acetate, and the combined organic phases were dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by chromatography to give N-(cyclopropylmethyl)-N-[1-[3-(2-pyridyl)pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide.

[0659] 19 F NMR (377 MHz, chloroform-d) δ / ppm -63.02.

[0660] LC-MS (method 1): retention time 1.18 minutes, m / z 495 [M+H + ].

[0661] Example H2 : N-(cyclopropylmethyl)-N-[1-[4-pyrimidin-2-yl-6-(trifluoromethyl)-3-pyridinyl]ethyl]- Preparation of 3,5-bis(trifluoromethyl)benzamide (Compound P10)

[0662]

[0663] Step 1: Preparation of N-(cyclopropylmethyl)-1-[3-(2-pyridyl)pyrazin-2-yl]ethanamine

[0664]

[0665] To a suspension of 4-chloro-6-(trifluoromethyl)pyridine-3-carboxylic acid (CAS: 1060810-66-3, 1.00 g, 4.43 mmol) in anhydrous dichloromethane (13 mL) containing two drops of anhydrous dimethylformamide was added oxalyl chloride (0.586 mL, 6.65 mmol) at room temperature. The mixture was stirred for 30 minutes and stirred at reflux for 10 minutes to complete the conversion. The mixture was then evaporated to dryness. N, O-dimethylhydroxylamine hydrochloride (0.662 g, 6.65 mmol) was added to the residue. Dichloromethane (13 mL) and triethylamine (1.87 mL, 13.3 mmol) were added, and the mixture was stirred at room temperature for 2 hours. The reactants were evaporated to dryness in the presence of silica gel. Purification on silica gel gave N-(cyclopropylmethyl)-1-[3-(2-pyridyl)pyrazin-2-yl]ethylamine.

[0666] LC-MS (method 1): retention time 0.84 min, m / z 269 [M+H + ].

[0667] Step 2: Preparation of 1-[4-chloro-6-(trifluoromethyl)-3-pyridyl]ethanone

[0668]

[0669] To a solution of N-(cyclopropylmethyl)-1-[3-(2-pyridyl)pyrazin-2-yl]ethanamine (1.0 g, 3.7 mmol) in anhydrous tetrahydrofuran (9.3 mL) was added a methylmagnesium bromide solution (3.4 mol / L, 1.8 mL, 6.0 mmol) at 0°C and then stirred at 0°C for 1 hour. The conversion was not complete, so additional methylmagnesium bromide (0.8 mL, 2.7 mmol) was added at 0°C and then stirred at 0°C for another hour to complete the conversion. Water was carefully added at 0°C and the product was extracted with ethyl acetate. Purification by silica gel chromatography gave 1-[4-chloro-6-(trifluoromethyl)-3-pyridyl]ethanone.

[0670] LC-MS (method 1): retention time 0.90 min, m / z 224 [M+H + ].

[0671] Step 3: Preparation of 1-[4-pyrimidin-2-yl-6-(trifluoromethyl)-3-pyridyl]ethanone

[0672]

[0673] Copper (I) iodide (35 mg, 0.18 mmol) and Pd (PPh 3 ) 4 (210 mg, 0.18 mmol) were weighed into a vial. Tributyl (pyrimidin-2-yl) stannane (0.67 g, 1.8 mmol) and 1-[4-chloro-6-(trifluoromethyl)-3-pyridyl] ethanone (0.45 g, 2.0 mmol) were added to the mixture. The entire mixture was suspended in anhydrous toluene (8.2 mL). The reaction mixture was heated under reflux for 18 hours, then diluted with ethyl acetate and filtered through a diatomaceous earth pad. The filtrate was concentrated under reduced pressure. Purification was performed by silica gel chromatography to obtain 1-[4-pyrimidin-2-yl-6-(trifluoromethyl)-3-pyridyl] ethanone.

[0674] LC-MS (method 1): retention time 0.86 min, m / z 268 [M+H + ].

[0675] 1 H NMR (400 MHz, chloroform-d) δ / ppm: 2.57 (s, 3H), 7.37-7.43 (m, 1H), 8.65 (s, 1H), 8.76 (s, 1H), 8.91 (d, J=5.14 Hz, 2H).

[0676] Step 4: Preparation of N-(cyclopropylmethyl)-1-[4-pyrimidin-2-yl-6-(trifluoromethyl)-3-pyridinyl]-ethylamine

[0677]

[0678] To a solution of 1-[4-pyrimidin-2-yl-6-(trifluoromethyl)-3-pyridyl]ethanone (440 mg, 1.60 mmol, 1.00 equiv) in methanol (7.0 mL) was added cyclopropylamine (0.44 mL, 360 mg, 4.90 mmol, 3.00 equiv) and titanium (IV) isopropoxide (0.65 mL, 0.630 g, 2.10 mmol, 1.30 equiv) at room temperature. The reaction mixture was warmed to 35° C. and stirred for 20 hours. The reaction mixture was concentrated in vacuo, redissolved in toluene (8.0 mL), cyclopropylmethylamine (0.44 mL, 360 mg, 4.90 mmol, 3.00 equiv) and titanium (IV) isopropoxide (0.65 mL, 0.630 g, 2.10 mmol, 1.30 equiv) were added, and the mixture was heated to 70° C. for 2 hours. Under reduced pressure, after removing volatile matter, methanol (10mL) is added and sodium borohydride (64mg, 1.60mmol, 1.00 equivalent) is slowly added into the solution of stirring. After stirring at room temperature for 20 minutes, at 0 DEG C, by saturated NH for reaction mixture Cl solution is quenched. After further stirring for 30 minutes, reaction mixture is diluted with ethyl acetate, and slurries are filtered through diatomite plug. Organic filtrate is washed with salt water, dried (MgSO ), filtered and evaporated. After removing volatile matter in a vacuum, the required product in thick material is obtained, and its purity is enough for next step.

[0679] LC-MS (method 1): retention time 0.69 minutes, m / z 323 [M+H + ].

[0680] Step 5: N-(cyclopropylmethyl)-N-[1-[4-pyrimidin-2-yl-6-(trifluoromethyl)-3-pyridinyl]ethyl]-3, Preparation of 5-bis(trifluoromethyl)benzamide

[0681]

[0682] At 0 ° C, to N- (cyclopropylmethyl) -1- [4- pyrimidin-2-yl -6- (trifluoromethyl) -3-pyridyl] -ethylamine (0.47g, 1.20mmol, 2.00 equivalents) and trimethylamine (0.18g, 1.70mmol, 3.00 equivalents) in dichloromethane (5.8mL) solution was added dropwise 3,5- bis (trifluoromethyl) benzoyl chloride (0.16g, 0.58mmol, 1.00 equivalents). The reaction mixture was stirred at room temperature for 1 hour, then Isolute was added and the volatiles were evaporated in vacuo. Purified by flash chromatography (Combiflash, silica gel, 5%-25% ethyl acetate in cyclohexane) to obtain the desired product as a colorless solid.

[0683] LC-MS (method 1): retention time 1.21 minutes, m / z 563 [M+H +].

[0684] Example H3 : N-[1-[2-(1,2-dihydropyrimidin-2-yl)-1,2-dihydropyrazin-3-yl]ethyl]-3,5-bis(tri Synthesis of (4-(2-fluoromethyl)benzamide (Compound P12)

[0685]

[0686] Step 1: Preparation of 1-(3-chloropyrazin-2-yl)ethylamine hydrochloride

[0687]

[0688] At room temperature, ammonium acetate (49.7g, 639mmol) and sodium cyanoborohydride (2.11g, 31.9mmol) are added in batches to a solution of 1-(3-chloropyrazine-2-yl) ethanone [CAS 121246-90-0] (5.00g, 31.9mmol) in methanol (80mL). The resulting suspension is stirred at room temperature overnight and then concentrated in vacuo. The residue is dissolved in ethyl acetate and 2M NaOH. The organic layer is dried (MgSO4), filtered and evaporated. The residue is dissolved in diethyl ether, and the HCl (25mL) in ethyl acetate is added dropwise. The precipitate formed is filtered and dried to obtain 1-(3-chloropyrazine-2-yl) ethylamine hydrochloride as a beige solid.

[0689] 1 H NMR (400MHz, DMSO-d) δ / ppm: 1.52 (s, 3H) 4.77 (br s, 1H) 8.61 (d, J = 2.57Hz, 1H) 8.78 (d, J = 2.2Hz, 1H).

[0690] LC-MS (method 1): retention time 0.17 minutes, m / z 158 [M+H + ].

[0691] Step 2: N-[1-(3-chloropyrazin-2-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide

[0692]

[0693] 1- (3- chloropyrazine -2- bases) ethylamine hydrochloride (2.50g, 12.9mmol) is suspended in 2-methyltetrahydrofuran (51mL). N, N- diisopropylethylamine (6.68mL, 38.6mmol) is added, followed by 3,5- bis (trifluoromethyl) benzoyl chloride [CAS 785-56-8] (2.41mL, 12.9mmol). The resulting suspension is stirred at room temperature overnight. The reaction mixture is diluted with ethyl acetate, and water is added. The organic layer is separated, dried (MgSO4), filtered and evaporated. Purified by flash chromatography (Combiflash, silica gel, 5%-50% ethyl acetate in cyclohexane) to obtain N- [1- (3- chloropyrazine -2- bases) ethyl] -3,5- bis (trifluoromethyl) benzamide as a colorless solid.

[0694] 1 H NMR (400 MHz, chloroform-d) δ / ppm: 1.65 (d, J = 6.97 Hz, 3H) 5.77–5.83 (m, 1H) 7.63 (brd, J = 6.97 Hz, 1H) 8.08 (s, 1H) 8.30 (s, 2H) 8.41 (d, J = 2.57 Hz, 1H) 8.54 (d, J = 2.57 Hz, 1H)

[0695] LC-MS (method 1): retention time 1.09 minutes, m / z 398 [M+H + ].

[0696] Step 3: N-[1-(3-pyrimidin-2-ylpyrazin-2-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (P12) Preparation

[0697]

[0698] To a solution of N-[1-(3-chloropyrazin-2-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (300 mg, 0.754 mmol) in toluene (3 mL) under argon was added tributyl(pyrimidin-2-yl)stannane (334 mg, 0.905 mmol), followed by copper(I) iodide (14.7 mg, 0.0754 mmol) and tetrakis(triphenylphosphine)palladium(0) (91.8 mg, 0.0754 mmol). The resulting reaction mixture was heated at 140° C. under microwave irradiation for 1 hour, and then the volatiles were evaporated in vacuo. Purification by flash chromatography (Combiflash, silica gel, 5%-100% ethyl acetate in cyclohexane) and reverse phase chromatography (Combiflash, preparative HPLC, 20%-100% acetonitrile in water + 0.2% formic acid) gave N-[1-(3-pyrimidin-2-ylpyrazin-2-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide as a solid.

[0699] 1 H NMR(400MHz,DMSO-d)δ / ppm:1.63(d,J=6.97Hz,3H)5.61–5.68(m,1H)7.59(br t,J=5.14x(2)hz,1H)8.28(s,1H)8.37(s,2H)8.71(s,1H)8.79(s,1H)8.97(br d,J=4.4Hz,2H)9.35(br d,J=6.6Hz,1H)

[0700] LC-MS (method 1): retention time 0.97 min, m / z 442 [M+H + ].

[0701] Example H4 : Synthesis of N-[1-[3-(2-pyridyl)pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide become

[0702]

[0703] Step 1: Preparation of N-[1-[3-(2-pyridyl)pyrazin-2-yl]ethyl]prop-2-en-1-amine

[0704]

[0705] To a solution of 1-[3-(2-pyridyl)pyrazine-2-yl]ethanone [obtained as described in H1, step 1] (700 mg, 3.51 mmol) in methanol (14 mL) was added propane-2-ene-1-amine (0.79 mL, 10.5 mmol) and titanium (V) isopropoxide (1.4 mL, 4.6 mmol) via a syringe. After stirring overnight at room temperature, sodium borohydride was slowly added at room temperature (gas evolution was observed). After 1 hour, the reaction mixture was quenched dropwise with the addition of water and concentrated in vacuo in the presence of silica gel. The crude product was purified by flash chromatography (Combiflash, silica gel, 0%-20% methanol in dichloromethane) to give N-[1-[3-(2-pyridyl)pyrazine-2-yl]ethyl]propane-2-ene-1-amine.

[0706] 1 H NMR(400MHz, chloroform-d)δ / ppm:1.49(d,J=6.6,3H)2.99-3.02(m,2H)4.58-4.63(q,J=6.6x(3),1H)4.92–5.01(m,1 H)5.74–5.84(m,1H)7.36–7.39(m,1H),7.85(m,2H)8.54(d,J=2.2,1H)8.64,(d,J=2.2,1H)8.71–8.73(m,1H)

[0707] Step 3: Preparation of 1-[3-(2-pyridyl)pyrazin-2-yl]ethanamine

[0708]

[0709] Under an argon atmosphere, 1,3-dimethylbarbituric acid (292 mg, 1.87 mmol) and tetrakis(triphenylphosphine)palladium(0) (14.5 mg, 0.125 mmol) were added to a solution of N-[1-[3-(2-pyridyl)pyrazin-2-yl]ethyl]prop-2-en-1-amine (150 mg, 0.264 mmol) in dichloromethane (5 mL) under an argon atmosphere. The resulting orange solution was stirred at 35 ° C for 1 hour. The reaction mixture was then filtered through celite, washed with dichloromethane and concentrated in vacuo. The crude product was purified by chromatography to give 1-[3-(2-pyridyl)pyrazin-2-yl]ethylamine.

[0710] LC-MS (method 1): retention time 0.24 minutes, m / z 201 [M+H + ].

[0711] Step 4: Preparation of N-[1-[3-(2-pyridyl)pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide Preparation

[0712]

[0713] To a solution of 1-[3-(2-pyridyl)pyrazin-2-yl]ethanamine (125 mg, 0.624 mmol) and N,N-diisopropylethylamine (0.214 mL, 1.25 mmol) in N,N-dimethylformamide (1.87 mL) was added 3,5-bis(trifluoromethyl)benzoic acid (181 mg, 0.687 mmol) followed by HATU[O-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium hexafluorophosphate] (356 mg, 0.936 mmol) at room temperature. The resulting mixture was stirred at room temperature overnight and poured into a saturated solution of NH4Cl. The mixture was extracted with ethyl acetate, and the combined organic phases were dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by chromatography to give N-[1-[3-(2-pyridyl)pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide.

[0714] 1H NMR (400 MHz, chloroform-d) δ / ppm: 1.62 (d, J = 6.97 Hz, 3H) 6.25–6.32 (m, 1H) 7.43–7.47 (m, 1H) 7.91–7.69 (m, 1H) 8.02 (s, 1H) 8.11–8.13 (m, 1H), 8.29 (s, 2H) 8.63 (s, J = 2.2 Hz, 1H) 8.66 (d, J = 2.2 Hz, 1H) 8.79–8.81 (m, 1H)

[0715] LC-MS (method 1): retention time 1.07 minutes, m / z 441 [M+H + ].

[0716] Example H5 : N-[1-(5-Methyl-3-pyrimidin-2-yl-pyrazin-2-yl)ethyl]-3,5-bis(trifluoromethyl)benzyl Synthesis of amides

[0717]

[0718] Step 1: Preparation of lithium 3-chloro-5-methyl-pyrazine-2-carboxylate

[0719]

[0720] To a solution of 3-chloro-5-methyl-pyrazine-2-carboxylic acid methyl ester [CAS 859063-65-3] (3.00 g, 16.1 mmol) in methanol (4.8 mL), tetrahydrofuran (32.2 mL) and water (4.82 mL) was added lithium hydroxide (424 mg, 17.7 mmol) and the resulting suspension was stirred at room temperature for 2 hours. The volatiles were evaporated in vacuo to give lithium 3-chloro-5-methyl-pyrazine-2-carboxylate as a colorless solid.

[0721] LC-MS (method 1): retention time 0.24 minutes, m / z 173 [M+H + ].

[0722] Step 2: 3-Chloro-5-methyl-pyrazine-2-carbonyl chloride

[0723]

[0724] To a solution of 3-chloro-5-methyl-pyrazine-2-carboxylic acid lithium (3.00 g, 16.8 mmol) in dichloromethane (50 mL) was added oxalyl chloride (1.65 mL, 18.5 mmol) and the resulting suspension was stirred at room temperature for 3 hours. The volatiles were evaporated under reduced pressure to give 3-chloro-5-methyl-pyrazine-2-carbonyl chloride.

[0725] LC-MS (Method 1) [after MeOH quenching]: retention time 0.69 min, m / z 187 [M+H +].

[0726] Step 3: Preparation of 3-chloro-N-methoxy-N,5-dimethyl-pyrazine-2-carboxamide

[0727]

[0728] To a suspension of 3-chloro-5-methyl-pyrazine-2-carbonyl chloride (3.10 g, 16.2 mmol) in tetrahydrofuran (50 mL) is added N, O-dimethylhydroxylamine hydrochloride (1.78 g, 17.9 mmol) and N, N-diisopropylethylamine (9.92 mL, 56.8 mmol). The reaction mixture is stirred at room temperature for 1 hour, and then diluted with ethyl acetate and water. The organic layer is dried (MgSO ), filtered and evaporated in vacuo. Purified by flash chromatography (Combiflash, silica gel, 10%-35% ethyl acetate in cyclohexane), 3-chloro-N-methoxy-N, 5-dimethyl-pyrazine-2-carboxamide as a yellow solid is obtained.

[0729] 1 H NMR (400 MHz, chloroform-d) δ / ppm: 2.63 (s, 3H) 3.44 (s, 3H) 3.60 (s, 3H) 8.39 (s, 1H)

[0730] LC-MS (method 1): retention time 0.63 minutes, m / z 216 [M+H + ].

[0731] Step 4: Preparation of 1-(3-chloro-5-methyl-pyrazin-2-yl)ethanone

[0732]

[0733] Under argon atmosphere, at 0 DEG C, methylmagnesium bromide (1M in THF, 5.1mL, 5.1mmol) solution is added in toluene (19mL). Subsequently, a solution (exothermic) of 3-chloro-N-methoxy-N,5-dimethyl-pyrazine-2-carboxamide (500mg, 2.30mmol) in toluene (5mL) is added dropwise over 5 minutes. After the addition is complete, the reaction mixture is stirred at 0 DEG C for 15 minutes, allowed to warm to room temperature and continued to stir for 5 hours. The reaction mixture is quenched with 1M HCl aqueous solution (exothermic) and ethyl acetate is added. The organic layer is dried (MgSO ), filtered and evaporated in vacuo to obtain 1- (3-chloro-5-methyl-pyrazine-2-yl) ethyl ketone as a solid.

[0734] 1 H NMR (400 MHz, chloroform-d) δ / ppm: 2.65 (s, 3H) 2.71 (s, 3H) 8.43 (s, 1H)

[0735] LC-MS (method 1): retention time 0.71 min, m / z 171 [M+H + ].

[0736] Step 5: Preparation of 1-(3-chloro-5-methyl-pyrazin-2-yl)ethanamine hydrochloride

[0737]

[0738] At room temperature, ammonium acetate (2.7g, 35mmol) and sodium cyanoborohydride (0.16g, 2.3mmol) are added in batches to a solution of 1-(3-chloro-5-methyl-pyrazine-2-yl) ethyl ketone (400mg, 2.3mmol) in methanol (5.9mL). The gained suspension is stirred at room temperature over the weekend. Vacuum concentration gives residue, which is treated with ethyl acetate and 2M NaOH solution. The organic layer is dried (MgSO ), filtered and evaporated. The residue is dissolved in diethyl ether, and the HCl in ethyl acetate is added dropwise. The gained precipitate is filtered out and dried to give 1-(3-chloro-5-methyl-pyrazine-2-yl) ethylamine hydrochloride as a pale solid.

[0739] LC-MS (method 1): retention time 0.19 minutes, m / z 172 [M+H + ].

[0740] Step 6: N-[1-(3-chloro-5-methyl-pyrazin-2-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide

[0741]

[0742] 1- (3- chloro-5-methyl-pyrazine-2-yl) ethylamine hydrochloride (193 mg, 0.927 mmol) is suspended in 2-methyltetrahydrofuran (5.56 mL) and N, N- diisopropylethylamine (0.486 mL, 2.78 mmol) is added, followed by addition of 3,5- bis (trifluoromethyl) benzoyl chloride [CAS785-56-8] (0.190 mL, 1.02 mmol). The resulting suspension is stirred at room temperature for 1 hour. The reaction mixture is diluted with ethyl acetate, and water is added. The organic layer is separated, dried (MgSO ), filtered and evaporated. Purified by flash chromatography (Combiflash, silica gel, 5%-20% ethyl acetate in cyclohexane) to obtain N- [1- (3- chloro-5-methyl-pyrazine-2-yl) ethyl] -3,5- bis (trifluoromethyl) benzamide as a colorless solid.

[0743] 1H NMR (400 MHz, chloroform-d) δ / ppm: 1.62 (d, J = 6.97, 3H) 2.61 (s, 3H) 5.71–5.78 (m, 1H) 7.62 (br d, J = 6.97 Hz, 1H) 8.05 (s, 1H) 8.30 (s, 2H), 8.40 (s, 1H)

[0744] LC-MS (method 1): retention time 1.14 minutes, m / z 412 [M+H + ].

[0745] Step 7: N-[1-(5-methyl-3-pyrimidin-2-yl-pyrazin-2-yl)ethyl]-3,5-bis(trifluoromethyl)benzoyl Preparation of amines

[0746]

[0747] To a solution of N-[1-(3-chloro-5-methyl-pyrazin-2-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (240 mg, 0.583 mmol) in toluene (2.3 mL) under argon was added tributyl(pyrimidin-2-yl)stannane (258 mg, 0.700 mmol), followed by copper(I) iodide (11.3 mg, 0.0583 mmol) and tetrakis(triphenylphosphine)palladium(0) (70.1 mg, 0.0583 mmol). The resulting reaction mixture was heated at 140° C. under microwave irradiation for 1 hour, and then the volatiles were evaporated in vacuo. Purification by flash chromatography (Combiflash, silica gel, 5%-100% ethyl acetate in cyclohexane) and reverse phase chromatography (Combiflash, preparative HPLC, 20%-100% acetonitrile in water + 0.2% formic acid) gave N-[1-(5-methyl-3-pyrimidin-2-yl-pyrazin-2-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide as a solid.

[0748] 1 H NMR (400MHz, chloroform-d) δ / ppm: 1.61 (d, J=6.6Hz, 3H) 2.75 (s, 3H) 6.10–6.17 (m, 1H) 7.46 (m, 1H), 7.83 (br d,J=6.97Hz,1H)8.02(s,1H)8.26(s,2H)8.61(br s,1H)9.04(brd,J=2.2Hz,2H)

[0749] LC-MS (method 1): retention time 1.01 min, m / z 456 [M+H + ].

[0750] Example H6: N-[1-[3-(5-chloro-2-pyridyl)pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzoyl Synthesis of amines

[0751]

[0752] To a solution of N-[1-(3-chloropyrazin-2-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide [see Example H3, Step 2 above] (450 mg, 1.13 mmol) in DMF (7.5 mL) was added (5-chloro-2-pyridyl)boronic acid (356 mg, 2.26 mmol), followed by palladium(II) acetate (13.1 mg, 0.0565 mmol), 1,1'-bis(diphenylphosphino)ferrocene (66.0 mg, 0.113 mmol), copper(I) iodide (212 mg, 1.13 mmol) and cesium carbonate (745 mg, 2.263 mmol). The resulting suspension was stirred at 100° C. for 3 hours. The reaction mixture was filtered and directly purified by reverse phase chromatography (Combiflash, preparative HPLC, 20%-100% acetonitrile in water + 0.2% formic acid) and repurified by flash chromatography (Combiflash, silica gel, 5%-50% ethyl acetate in cyclohexane) to give N-[1-[3-(5-chloro-2-pyridinyl)pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide as a solid.

[0753] LC-MS (method 1): retention time 1.20 minutes, m / z 475 [M+H + ].

[0754]

[0755]

[0756]

[0757]

[0758]

[0759]

[0760]

[0761]

[0762]

[0763]

[0764]

[0765]

[0766]

[0767]

[0768]

[0769]

[0770]

[0771] By adding other insecticides, acaricides and / or fungicidal active ingredients, the activity of the composition according to the present invention can be significantly widened and adapted to prevailing conditions. Mixtures of compounds of Formula I with other insecticides, acaricides and / or fungicidal active ingredients can also have other unexpected advantages, which can also be described as synergistic in a wider sense. For example, plants can be better tolerated, have reduced phytotoxicity, insects can be controlled at their different developmental stages, or behave better during their production (e.g., during grinding or mixing, during their storage or during their use).

[0772] Representative of suitable active ingredients for addition here are, for example, active ingredients from the following classes: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.

[0773] Preference is given to the following mixtures of a compound of formula I with an active ingredient (wherein the abbreviation "TX" means "a compound selected from the group consisting of the compounds defined in Tables A-1 to A-15, B-1 to B-15, C-1 to C-15, D-1 to D-30, E-1 to E-15, F-1 to F-15, G-1 to G-15, H-1 to H-15, I-1 to I-15, J-1 to J-15, K-1 to K-15, L-1 to L-15 and M-1 to M-60 and Table P"):

[0774] Auxiliary agent, which is selected from the group consisting of: petroleum (alias) (628) + TX,

[0775] Acaricide selected from the group consisting of: 1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910) + TX, 2,4-dichlorophenylbenzenesulfonate (IUPAC / Chemical Abstracts name) (1059) + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name) (1295) + TX, 4-chlorophenylphenylsulfone (IUPAC name) (981) + TX, abamectin (1) + TX, acequinoxaline (3) + TX X, acetothionil [CCN] + TX, flumethrin (9) + TX, aldicarb (16) + TX, aldicarb (863) + TX, α-cypermethrin (202) + TX, cypermethrin (870) + TX, sulfamethoxam [CCN] + TX, aminothioate (872) + TX, amitriptyline (875) + TX, amitriptyline hydrogen oxalate (875) + TX, amitraz (24) + TX, cypermethrin (881) + TX, arsenic trioxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azinphos-methyl (44) + TX, azinphos-methyl (45) + TX, azobenzene (IUPAC name) (888) + TX, triazotin (46) + TX, azothoate (889) + TX, benomyl (62) + TX, benoxafos (alias) [CCN] + TX, benzoximate (71) + TX, benzyl benzoate (IUPAC name) [CCN] + TX, biphenylhydrazine Ester (74) + TX, bifenthrin (76) + TX, binachlor (907) + TX, bromethrin (alias) + TX, bromocyclen (918) + TX, bromophos (920) + TX, ethyl bromophos (921) + TX, bromopropylate (94) + TX, buprofezin (99) + TX, butanone (103) + TX, butanone sulfone (104) + TX, butylpyridaben (alias) + TX, lime sulfur mixture (calcium polysulfide)(IUPAC name)(111)+TX、campheechlor)(941)+TX、carbanolate(943)+TX、carbaryl(115)+TX、carbofuran(118)+TX、carbothion(947)+TX、CGA 50'439(research code)(125)+TX、chinomethionat(126)+TX、chlorbenside(959)+TX、chlordimeform(964)+TX、chlordimeform hydrochloride(964)+TX、Chlorfenapyr (130) + TX, chlorfenapyr (968) + TX, chlorfenson (970) + TX, chlorfensulfide (971) + TX, chlorfenapyr (131) + TX, chlorobenzilate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, methyl chlorpyrifos (146) + TX, chlorfenapyr (131) + TX, chlorobenzilate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, methyl chlorpyrifos (146) + TX, phos)(994)+TX、cinerin I(696)+TX、cinerin II(696)+TX、cinerins(696)+TX、clofentezine(158)+TX、closantel(other name)[CCN]+TX、coumaphos(174)+TX、crotamiton(other name)[CCN]+TX、crotoxyphos(1010)+TX、thiophene(1013)+TX、cyanthoate(1020)+TX、cyfluthrin(CAS Reg. No.: 400882-07-7)+TX、cyhalothrin(196)+TX、cyclohexanone(199)+TX 、Cypermethrin (201) + TX、DCPM (1032) + TX、DDT ​​(219) + TX、demephion (1037) + TX、demephion-O (1037) + TX、demephion-S (1037) + TX、demeton (1038) + TX、demeton-methyl (224) + TX、demeton-O (1038) + TX、demeton-O-methyl (224) + TX、demeton-S (1038) + TX、demeton-S-methyl (224) + TX、demeton-S-methylsulfon (1039) + TX、butanecarb (226) + TX、phosphamidon (dialifos)(1042)+TX、diazinon(227)+TX、benzenefluanid(230)+TX、dichlorvos(236)+TX、dicliphos(alias)+TX、kailesan(242)+TX、dicrotophos(243)+TX、biandigram(1071)+TX、dimefox(1081)+TX、dimethoate(262)+TX、dinactin(alias)(653)+TX、dinex(1089)+TX、dinex-diclexine(1089)+TX、dinobuton(269)+TX、Dinocap (270) + TX, dinocap-4 [CCN] + TX, dinocap-6 [CCN] + TX, dinitropropane (1090) + TX, dinopenton (1092) + TX, dinosulfon (1097) + TX, dinoterbon (1098) + TX, dioxafoate (1102) + TX, diphenylsulfone (IUPAC name) (1103) + TX, disulfiram (alias) [CCN] + TX, disulfoton (278) + TX, DNOC (282) + TX, dofenapyn ( 1113)+TX, doramectin (alias) [CCN]+TX, endosulfan (294)+TX, endothion (1121)+TX, EPN (297)+TX, eprinomectin (alias) [CCN]+TX, ethion (309)+TX, ethoate-methyl (1134)+TX, etoxazole (320)+TX, etrimfos (1142)+TX, fenazaflor (1147)+TX, fenazaquin (328)+TX, fenbutatin oxide)(330)+TX, fenothiocarb)(337)+TX, cypermethrin (342)+TX, fenpyrad (alias)+TX, fenpyroximate(345)+TX, fenson(1157)+TX, fentrifanil(1161)+TX, cypermethrin(349)+TX, fipronil(354)+TX, fluacrypyrim(360)+TX, fluzolan(1166)+TX, flubenzimine(1167)+TX, flufenoxim(366)+TX, flucythrin nate)(367)+TX、fluenetil)(1169)+TX、flufenoxuron(370)+TX、flumethrin(372)+TX、fluorbenside(1174)+TX、fluvalinate(1184)+TX、FMC1137(research code)(1185)+TX、anthraquinone(405)+TX、anthraquinone hydrochloride(405)+TX、formothion(1192)+TX、formparanate(1193)+TX、γ-HCH(430)+TX、glyodin(1205)+TX、halfenprox (424) + TX, heptenophos (432) + TX, hexadecyl cyclopropanecarboxylate (IUPAC / Chemical Abstracts name) (1216) + TX, hexathiazolin (441) + TX, iodomethane (IUPAC name) (542) + TX, isocarbophos (alias) (473) + TX, isopropyl O-(methoxyaminothiophosphoryl) salicylate (IUPAC name) (473) + TX, ivermectin (alias) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, lindane (430) + TX, lufenuron (4 90)+TX, malathion (492)+TX, malonoben (1254)+TX, mecarbam (502)+TX, mephosfolan (1261)+TX, methylthiophene (CCN)+TX, methacrifos (1266)+TX, methylamidophos (527)+TX, methidathion (529)+TX, methiocarb (530)+TX, methomyl (531)+TX, methyl bromide (537)+TX, metolcarb (550)+TX, metolcarb (556)+TX, mexacarbate (1290)+TX, milbemycin (557)+TX, milbemycin oxime)(alias)[CCN]+TX、mipafox(1293)+TX、monocrotophos(561)+TX、morphothion(1300)+TX、moxidectin(alias)[CCN]+TX、naled(567)+TX、NC-184(compound code)+TX、NC-512(compound code)+TX、nifluridide(1309)+TX、nikkomycin(alias)[CCN]+TX、nitrilacarb(1 313)+TX, nitrilacarb 1:1 zinc chloride complex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250 (compound code)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp'-DDT (219)+TX, parathion (615)+TX, permethrin (626)+TX,Petroleum oil (alias) (628) + TX, fenthion (1330) + TX, fenthion (631) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosphamidon (639) + TX, phoxim (642) + TX, methylpirimiphos (652) + TX, polychloroterpenes (traditional name) (1347) + TX, polynactins (alias) (653) + TX, prochloraz (1350) + TX, profenofos (662) + TX, promac yl)(1354)+TX, propargyl(671)+TX, propetamphos(673)+TX, propoxur(678)+TX, prothidathion(1360)+TX, prothoate(1362)+TX, pyrethrin I(696)+TX, pyrethrin II(696)+TX, pyrethrins(696)+TX, pyrethrin(699)+TX, pyridaphenthion(701)+TX, pyrimidifen(706)+TX, pyrimidifen(1370)+TX TX, quinalphos (711) + TX, quintiofos (1381) + TX, R-1492 (research code) (1382) + TX, RA-17 (research code) (1383) + TX, rotenone (722) + TX, schradan (1389) + TX, sebufos (alias) + TX, selamectin (alias) [CCN] + TX, SI-0009 (compound code) + TX, sophamide (1402) + TX, tebufenoxam (738) + TX, spiromesifen (739) + TX, SSI-121 (research code) (1404) + TX, Sufilam (alias) [CCN] + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulfur (754) + TX, SZI-121 (research code) (757) + TX, fluvalinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, terbufenamide (alias) + TX, stirofos (777) + TX, tetradifon (786) + TX, tetranactin (alias) (653) + TX,Tetrasul (1425) + TX, thiafenox (other name) + TX, thiocarboxime (1431) + TX, thiofanox (800) + TX, thiometon (801) + TX, thuringiensin (CCN) + TX, triamiphos (1441 )+TX, triarathene (1443)+TX, triazophos (820)+TX, triazuron (alias)+TX, trichlorfon (824)+TX, trifenofos (1455)+TX, trinactin (alias) (653)+TX, aphidox (847)+TX, vaniliprole [CCN] and YI-5302 (compound code)+TX,

[0776] an algaecide selected from the group consisting of bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichloronaphthoquinone (1052) + TX, dichlorophen (232) + TX, endoxan (295) + TX, fentin (347) + TX, slaked lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX,

[0777] Anthelmintics selected from the group consisting of abamectin (1) + TX, fusulin (1011) + TX, doramectin (alias) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alias) [CCN] + TX, ivermectin (alias) [CCN] + TX, milbemycin oxime (alias) [CCN] + TX, moxidectin (alias) [CCN] + TX, piperazine [CCN] + TX, selamectin (alias) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,

[0778] Avicides selected from the group consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX,

[0779] Bactericide selected from the group consisting of: 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, dodesine (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, mercaptophenone ( Synonyms) [CCN] + TX, 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, chlorpheniramine (766) + TX, and thimerosal (synonyms) [CCN] + TX,

[0780] Biological agent selected from the group consisting of: Adoxophyes oranaGV (12) + TX, Agrobacterium radiobacter (alias) (13) + TX, Amblyseius spp. (alias) (19) + TX, Anagrapha falciferaNPV (alias) (28) + TX, Anagrus atomus (alias) (29) + TX, Aphelinus abdominalis (alias) (33) + TX, Aphidius colemani (alias) (34) + TX, Aphidoletes aphidimyza (alias) (35) + TX, Autographa californica NPV)(alias)(38)+TX、Bacillus firmus)(alias)(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)(scientific name)(51)+TX、Bacillus thuringiensis Kurstak subsp.kurstaki)(scientific name)(51)+TX、Bacillus thuringiensis subsp.tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alias) (53) + TX, Beauveria brongniartii (alias) (54) + TX, Chrysoperla carnea (alias) (151) + TX, Cryptolaemus montrouzieri (178) + TX, Cydia pomonella GV (alias) (191) + TX, Dacnusa sibirica (alias) (212) + TX, Diglyphus isaea (alias) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus) (alias) (300) + TX, Helicoverpa zeaNPV (431) + TX, Heterorhabditis bacteriophora and H. megidis (alias) (433) + TX, Hippodamia convergens (alias) (442) + TX, Leptomastix dactylopii (alias) (488) + TX, Macrolophus caliginosus (alias) (491) + TX, Mamestra brassicaeNPV (494) + TX, Metaphycus helvolus (alias) (522) + TX, Metarhizium anisopliae var.acridum)(scientific name)(523)+TX, Metarhizium anisopliae var.anisopliae)(scientific name)(523)+TX, Neodiprion sertifer NPV and N.lecontei NPV)(other names)(575)+TX, Orius spp.)(Other names)(596)+TX、Paecilomyces fumosoroseus)(Other names)(613)+TX、Phytoseiulus persimilis)(Other names)(644)+TX、Spodoptera exigua multinucleocapsid nuclear polyhedrosis virus(scientific name)(741)+TX、Steinernema bibionis)(Other names)(742)+TX、Steinernema carpocapsae)(Other names)(742)+TX、Steinernema feltiae)(Other names)(742)+TX、Steinernema glaseri)(Other names)(742)+TX、Steinernema riobrave)(Other names)(742)+TX、Steinernema riobravis (alias) (742) + TX, Steinernemascapterisci (alias) (742) + TX, Steinernema spp. (alias) (742) + TX, Trichogramma spp. (alias) (826) + TX, Typhlodromus occidentalis (alias) (844) and Verticillium lecanii (alias) (848) + TX,.

[0781] Soil disinfectant selected from the group consisting of methyl iodide (IUPAC name) (542) and methyl bromide (537) + TX,

[0782] A chemical sterilant selected from the group consisting of: apholanate [CCN] + TX, bis(aziridine) methylaminophosphine sulfide (bisazir) (alias) [CCN] + TX, busulfan (alias) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alias) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methylsulfonate Methotepa [CCN] + TX, methylapholate [CCN] + TX, morzid [CCN] + TX, penfluron (another name) [CCN] + TX, tepa [CCN] + TX, thiohempa (another name) [CCN] + TX, thiotepa (another name) [CCN] + TX, trotamide (another name) [CCN] and urethaneimide (another name) [CCN] + TX,

[0783] An insect pheromone selected from the group consisting of (E)-dec-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-4,10-dien-1-yl acetate (IUPAC name) (779) + TX, (Z)-dodec-7-en-1-yl acetate (IUPAC name) (285) + TX, (Z)-hexadecan-11-enal (IUPAC name) (436) + TX, (Z)-hexadecan-11-en-1-yl acetate (IUPAC name) (437) + TX X, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438) + TX, (Z)-eicos-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)-tetradec-9-en-1-yl acetate (IUPAC name) (784) + TX, (7E,9Z)-dodec-7,9-dien-1-yl acetate (IUPAC name) (283) + TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate (IUPAC name) (780) + TX, (9Z,12E)-tetradec-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 (alias) [CCN] + TX, western pine beetle gathering pheromone (brevicomin) (alias) [CCN] + TX, codlelure (alias) [CCN] + TX, codlemon mone)(alias)(167)+TX、cuelure)(alias)(179)+TX、disparlure)(277)+TX、1-dodecane-8-en-1-yl acetate(IUPAC name)(286)+TX、1-dodecane-9-en-1-yl acetate(IUPAC name)(287)+TX、10-10-dien-1-yl acetate(IUPAC name)(284)+TX、dominicalure(alias)[CCN]+TX、ethyl 4-methyloctanoate(IUPAC name) C name) (317) + TX, eugenol (alias) [CCN] + TX, southern pine beetle gathering pheromone (frontalin) (alias) [CCN] + TX, gossyplure (alias) (420) + TX, grandlure (421) + TX, grandlure I (alias) (421) + TX, grandlure II (alias) (421) + TX, grandlure III (alias) (421) + TX, grandlure IV (alias) (421) + TX, hexalure )[CCN]+TX、ipsdienol(alias)[CCN]+TX、ipsenol(alias)[CCN]+TX、japonilure(alias)(481)+TX、lineatin(alias)[CCN]+TX、litlure(alias)[CCN]+TX、looplure(alias)[CCN]+TX、medlure[CCN]+TX、megatomoic acid(alias)[CCN]+TX、methyl eugenol(alias)(540)+TX、muscalure(563)+TX、octadeca-2,13-dien-1-yl acetate(IUPAC name)(588)+TX、octadeca-3,13-Dien-1-yl acetate (IUPAC name) (589) + TX, orfralure (alias) [CCN] + TX, oryctalure (alias) (317) + TX, ostramone (alias) [CCN] + TX, siglure [CCN] + TX, sordidin (alias) (736) + TX, sulcatol (alias) [ CCN] + TX, tetradec-11-en-1-yl acetate (IUPAC name) (785) + TX, Mediterranean fruit fly attractant (trimedlure) (839) + TX, Mediterranean fruit fly attractant A (alternative name) (839) + TX, Mediterranean fruit fly attractant B1 (alternative name) (839) + TX, Mediterranean fruit fly attractant B2 (alternative name) (839) + TX, Mediterranean fruit fly attractant C (alternative name) (839) and trunc-call (alternative name) [CCN] + TX,

[0784] An insect repellent selected from the group 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, DEET [CCN] + TX, dimethyl carbate) [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,

[0785] Insecticides selected from the group consisting of: 1-dichloro-1-nitroethane (IUPAC / Chemical Abstracts name) (1058) + TX, 1,1-dichloro-2,2-di(4-ethylphenyl)ethane (IUPAC name) (1056) + TX, 1,2-dichloropropane (IUPAC / Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1-bromo-2-chloroethane (IUPAC / Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451) + TX, 2,2-dichlorovinyl 2-Ethylsulfinylethyl methyl phosphate (IUPAC name) (1066) + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate (IUPAC / Chemical Abstracts name) (1109) + TX, 2-(2-butoxyethoxy)ethyl thiocyanate (IUPAC / Chemical Abstracts name) (935) + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC / Chemical Abstracts name) (1084) + TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986) + TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984) + TX, 2-imidazolidinone (IUPAC name) (1225) + TX, 2-isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate (IUPAC name) (1284) + TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433) + TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917) + TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283) + TX, 4-methyl(prop-2-ynyl)amino-3,5-ditolyl methylcarbamate (IUPAC name) (1285 )+TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPAC name) (1085)+TX, abamectin (1)+TX, acephate (2)+TX, acetamiprid (4)+TX, domesticaphos (alias) [CCN]+TX, acetofennili [CCN]+TX, flumethrin (9)+TX, acrylonitrile (IUPAC name) (861)+TX, cypermethrin (15)+TX, aldicarb (16)+TX, aldicarb (863)+TX, chloronaphthalene (864)+TX, allethrin (17)+TX, alomycin (alias) [CCN]+TX, chlorpyrifos (866)+TX, α-cypermethrin (202)+TX,α-Ecdysone (alias) [CCN] + TX, aluminum phosphide (640) + TX, cypermethrin (870) + TX, thioamide (872) + TX, cypermethrin (873) + TX, cypermethrin (875) + TX, cypermethrin hydrogen oxalate (875) + TX, amitraz (24) + TX, neonicotinoid (877) + TX, ethidathion (883) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azadirachtin (alias) (41) + TX, methyl pyriphos (42) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azophos (889) + TX, Bacillus thuringiensis delta endotoxins (alias) (52) + TX, barium hexafluorosilicate (alias) [CCN] + TX, barium polysulfide (IUPAC / Chemical Abstracts name) (892) + TX, cypermethrin [CCN] + TX, Bayer 22 / 190 (research code) (893) + TX, Bayer 22408 (research code) (894) + TX, Benthiocarb (58) + TX, Benfuracarb (60) + TX, Dimethoprim (66) + TX, β-cyfluthrin (194) + TX, β-cypermethrin (203) + TX, Bifenthrin (76) + TX, Bio-allethrin (78) + TX, Bio-allethrin S-cyclopentenyl isomer (alias) (79) + TX, Penta Cyclomethrin (bioethanomethrin) [CCN] + TX, biopermethrin (908) + TX, pyrethrin (80) + TX, bis(2-chloroethyl) ether (IUPAC name) (909) + TX, bistrifluan (83) + TX, borax (86) + TX, bromethrin (alias) + TX, bromophenazone (914) + TX, bromomethoxine (918) + TX, bromo-DDT (alias) [CCN] + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, chlorpyrifos (924) + TX, thiamethoxam (99) + TX, chlorpyrifos (926) + TX, demethylated butylpyrimidinphos (butathiofos) (927) + TX, butanone carbendazim (103) + TX, butyl ester phosphine (932) + TX, butanone carbendazim (104) + TX, butyl pyridaben (alias) + TX, sulfamethoxam (109) + TX, calcium arsenate [CCN] + TX, calcium cyanide ( 444)+TX, calcium polysulfide (IUPAC name) (111)+TX, toxaphene (941)+TX, chlormethinol (943)+TX, carbaryl (115)+TX, chlorpyrifos (118)+TX, carbon disulfide (IUPAC / Chemical Abstracts name) (945)+TX, carbon tetrachloride (IUPAC name) (946)+TX, trithion (947)+TX, butanesulfonyl (119)+TX, cartap (123)+TX,Cartap hydrochloride (123) + TX, sivaldin (alias) (725) + TX, borneol (960) + TX, chlordane (128) + TX, chlordane (963) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorpyrifos (129) + TX, chlorfenapyr (130) + TX, chlorfenapyr (131) + TX, chlorfluanid ( 132) + TX, chloromethylphos (136) + TX, chloroform [CCN] + TX, chloropicrin (141) + TX, chlorphoxim (989) + TX, pyridamole (990) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorpyrifos (994) + TX, chlorfenapyr (150) + TX, cypermethrin I (696) +TX, cypermethrin II (696) +TX, cypermethrins (696) +TX, cis-resmethrin (alias) +TX, cis-resmethrin (80) +TX, cypermethrin (alias) +TX, cypermethrin (999) +TX, closantel (alias) [CCN] +TX, clothianidin (165) +TX, copper acetylarensite [CCN] +TX, copper arsenate [CCN] +TX, copper oleate [CCN] +TX, coumaphos (174) +TX, cypermethrin (1006) +TX, crotamiton (alias) [CCN] +TX, baclofos (1010) +TX, cypermethrin (1011) +TX, cryolite (alias) (177) +TX, CS 708 (research code) (1012) + TX, benzonitrile phosphonium (1019) + TX, cypermethrin (184) + TX, cypermethrin (1020) + TX, cypermethrin [CCN] + TX, cypermethrin (188) + TX, flucythrin (193) + TX, flucythrin (196) + TX, cypermethrin (201) + TX, cypermethrin (206) + TX, cyproconazole (209) + TX, cypermethrin (alias) [CCN] + TX, d-limonene (alias) [CCN] + TX, d-tetramethrin (alias) (788) + TX, DAEP (1031) + TX, dazomethrin (216) + TX, DDT (21 9)+TX, decarbofuran (1034)+TX, deltamethrin (223)+TX, tanafur (1037)+TX, tanafur-O (1037)+TX, tanafur-S (1037)+TX, demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O (1038)+TX, demeton-O-methyl (224)+TX, demeton-S (1038)+TX, demeton-S-methyl (224)+TX, demeton-S-methyl (224)+TX, demeton-S-methyl (1039)+TX, diafuron (226)+TX,Phosphorus chlorimide (1042) + TX, diamidophos (1044) + TX, diazinon (227) + TX, isochlorophos (1050) + TX, dichlorvos (1051) + TX, dichlorvos (236) + TX, dicliphos (alias) + TX, dicresyl (alias) [CCN] + TX, dicrotophos (243) + TX, dicynamidone (244) + TX, dieldrin (1070) + TX, diethyl 5-methylpyrazol-3-yl phosphate (IUPAC name) (1076) + TX, diflubenzuron (250) + TX, diprophylline (alias) [CCN] + TX, tetrafluthrin [CCN] + TX, methylphosphine (1081) + TX, dimethoate (1085) + TX, dimethoate (262) + TX X, pyrethrin (1083) + TX, methyl chlorpyrifos (265) + TX, dimethoate (1086) + TX, dimethoate (1089) + TX, dimethoate (dinex-diclexine) (1089) + TX, propanol (1093) + TX, pentotropol (1094) + TX, danosulfuron (1095) + TX, dinotefuran (271) + TX, fenpyroxene (1099) +TX, vegetable and fruit phosphorus (1100) +TX, dioxocarb (1101) +TX, dimethoate (1102) +TX, disulfophos (278) +TX, dithiocarb (1108) +TX, DNOC (282) +TX, doramectin (alias) [CCN] +TX, DSP (1115) +TX, ecdysone (alias) [CCN] +TX, EI 1642 (research code) (1118) + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, EMPC (1120) + TX, ethynethrin (292) + TX, endosulfan (294) + TX, fenthion (1121) + TX, endrin (1122) + TX, EPBP (1123) + TX, EPN (297) + TX, fenvalerate (1124) + TX, eprinomectin (alias) [CCN] + TX, cypermethrin (302) + TX, Oxfordshire etaphos (alias) )[CCN]+TX、Ethiofencarb(308)+TX、Ethiophos(309)+TX、Ethiopromide(310)+TX、Ethiopromide-methyl(1134)+TX、Ethiopromide(312)+TX、Ethyl formate(IUPAC name)[CCN]+TX、Ethyl-DDD(alias)(1056)+TX、Ethylene dibromide(316)+TX、Ethylene dichloride(chemical name)(1136)+TX、Ethylene oxide[CCN]+TX、Ethofenprox(319)+TX、Ethiopromide(1142)+TX、EXD(1143)+TX、Amoxifen (323) + TX, fenamiphos (326) + TX, anti-mite azole (1147) + TX, pyraclostrobin (1148) + TX, fenthiocarb (1149) + TX, fenfluramide (1150) + TX, fenthiocarb (335) + TX, fenthiocarb (336) + TX, fenoxacrim (1153) + TX, fenoxycarb (340) + TX, cypermethrin (1155) + TX, cypermethrin (342) + TX, fenpyrad (alias) + TX, fensulfuron (1158) + TX, fenthiocarb (346) + TX, fensulfuron Phospho-ethyl [CCN] + TX, cypermethrin (349) + TX, fipronil (354) + TX, flonicamid (358) + TX, flubendiamide (CAS Registry No.: 272451-65-7) + TX, flucofuron (1168) + TX, flufenacet (366) + TX, flucythrin (367) + TX, diflubenzuron (1169) + TX, flufenacet [CCN] + TX, flufenacet (370) + TX, triflumuron (1171) + TX, flumethrin (372) + TX, fluvalinate (1184) + TX, FMC 1137 (research code) (1185) + TX, diflubenzuron (1191) + TX, fenfluramine (405) + TX, fenfluramine hydrochloride (405) + TX, anthiophos (1192) + TX, formparanate (1193) + TX, fenthiophos (1194) + TX, forspiramate (1195) + TX, thiathiophene (408) + TX , butyclophos (1196) + TX, furathiocarb (412) + TX, pyrethroid (1200) + TX, γ-cyhalothrin (197) + TX, γ-HCH (430) + TX, biguanide salt (422) + TX, biguanide acetate (422) + TX, GY-81 (research code) (423) + TX, benzylfenpropimorph (424) + TX, chlorfenapyr (425) + TX 、HCH(430)+TX、HEOD(1070)+TX、Feibuda(1211)+TX、Heptenphos(432)+TX、Cetirizine[CCN]+TX、Hexaflumuron(439)+TX、HHDN(864)+TX、Hydrazamylhydrazone(443)+TX、Hydrocyanic acid(444)+TX、Methoprene(445)+TX、Hyquincar b)(1223)+TX、Imidacloprid(458)+TX、Imidacloprid(460)+TX、Indoxacarb(465)+TX、Methyl iodide(IUPAC name)(542)+TX、IPSP(1229)+TX、Chlorpheniramine(1231)+TX、Carbochlor(1232)+TX、Isocarb(alias)(473)+TX、Isocarb(1235)+TX、Isothioate (1236) + TX, transplanting agent (1237) + TX, isoprocarb (472) + TX, O-(methoxyaminothiophosphoryl) salicylic acid isopropyl ester (IUPAC name) (473) + TX, blastifungin (474) + TX, isothioate (1244) + TX, oxadiazon (480) + TX, ivermectin (alias) [CCN] + TX, jasmonate I (696) + TX, jasmonate II (696) + TX, iodonium chloride (1248) + TX, juvenile hormone I (alias) [CCN] + TX, juvenile hormone II (alias) [CCN] + TX, juvenile hormone III (alias) [CCN] + TX, chlorpentyl (1249) + TX, methoprene (484) + TX, λ-cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepidomycin (CCN) + TX, parabromophos (1250) + TX, lindane (430) + TX, lirimfos (1251) + TX, lufenuron (490) + TX, thiazophos (1253) + TX, m-isopropylphenyl methylcarbamate (IUPAC name) (1014) + TX, magnesium phosphide (IUPAC name) (640) + TX, malathion (492) + TX, tebuconazole (1254) + TX, phosphazolin (1255) + TX, cypermethrin (502) + TX, tetramethylphos (1258) + TX, cypermethrin (12 60)+TX, diammonium chloride (1261)+TX, mercurous chloride (513)+TX, mesulfenfos (1263)+TX, metaflumizone (CCN)+TX, metamizole (519)+TX, metamizole potassium (alias) (519)+TX, metamizole sodium (519)+TX, acarbamate (1266)+TX, methamidophos (527)+TX, methanesulfonyl fluoride (IUPAC / Chemical Abstracts name) (1268)+TX, methidathion (529)+TX, methiocarb (530)+TX, thiophanate-methyl (1273)+TX, methomyl (531)+TX, methoprene (532)+TX, mequindox (1276)+TX, Methothrin (alias) (533) + TX, methoxychlor (534) + TX, anthracene (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methyl chloroform (alias) [CCN] + TX, dichloromethane [CCN] + TX, metofluthrin [CCN] + TX, cypermethrin (550) + TX, oxadiazine (1288) + TX, cypermethrin (556) + TX, zikwei (1290) + TX, milbemidin (557) + TX, milbemidin oxime (alias) [CCN] + TX, propylamine fluorophosphate (1293) + TX, anthelmintic (1294) + TX, monocrotophos (561) + TX, phosphamidon (1300) + TX,Moxidectin (alias) [CCN] + TX, naphthyl phosphine (alias) [CCN] + TX, dibromophosphine (567) + TX, naphthalene (IUPAC / Chemical Abstracts name) (1303) + TX, NC-170 (research code) (1306) + TX, NC-184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (578) + TX, fluazifop (1309) + TX, nitenpyram (579) + TX, nithiazine (1 311) + TX, valfenuron (1313) + TX, valfenuron 1:1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, nornicotine (traditional name) (1319) + TX, flubendiamide (585) + TX, noviflumuron (586) + TX, O-5-dichloro-4-iodophenyl O-ethylethylphosphonothioate (IUPAC name) (1057) + TX, O,O-diethyl O-4-methyl O-2-oxo-2H-chromen-7-ylphosphonothioate (IUPAC name) (1074) + TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-ylphosphonothioate (IUPAC name) (1075) + TX, O,O,O',O'-tetrapropyl dithiopyrophosphate (IUPAC name) (1424) + TX, oleic acid (IUPAC name) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, sulfone dextromethorphan-methyl (609) + TX, isothiophos (1324) + TX, sulfone (1325) + TX, pp'-DDT (219) + TX, p-dichlorobenzene [CCN] + TX, parathion (615) + TX, parathion-methyl (616) + TX, flubendiamide (alias) [CCN] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (IUPAC name) (623) + TX, permethrin (626) + TX, petroleum oil (alias) (628) + TX, PH 60-38 (research code) (1328) + TX, fenthion (1330) + TX, phenothrin (630) + TX, fenthion (631) + TX, phorate (636) + TX, phosalone (637) + TX, thiophanate (1338) + TX, phosmet (638) + TX, parachlorothion (1339) + TX, phosphamidon (639) + TX, phosphine (IUPAC name) (640) + TX, phoxim (642) + TX, phoxim-methyl (1340) + TX, pirimetaphos (1344) + TX, pirimetaphos (651) + TX, ethylpirimitaphos (1345) + TX, methylpirimitaphos (652) + TX, polychlorodicyclopentadiene isomers (IUPAC name) (1346) + TX,Polychloroterpenes (traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, pralinethrin (655) + TX, precocious chlorpyrifos I (other name) [CCN] + TX, precocious chlorpyrifos II (other name) [CCN] + TX, precocious chlorpyrifos III (other name) [CCN] + TX, primidophos (1349) + TX, profenofos (662) + TX, fluthrin [CCN] +TX, cypermethrin (1354) +TX, cypermethrin (1355) +TX, propanil (1356) +TX, chlorpyrifos (673) +TX, propoxur (678) +TX, ethidium (1360) +TX, prothiophos (686) +TX, thiophos (1362) +TX, protrifenbute [CCN] +TX, pymetrozine (688) +TX, pyraclofos (689) +TX, cypermethrin (693) + TX, pyresmethrin (1367) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethroids (696) + TX, pyrethroids (699) + TX, pyridalyl (700) + TX, pyridazine (701) + TX, pyrimidine (706) + TX, pyrimidine (1370) + TX, pyriproxyfen (708) + TX, quassia extract (qu assia)(alias)[CCN]+TX、quinalphos(711)+TX、quinalphos-methyl(1376)+TX、quinalphos(1380)+TX、quintiofos(1381)+TX、R-1492(research code)(1382)+TX、rafoxanide(alias)[CCN]+TX、resmethrin(719)+TX、rotenone(722)+TX、RU 15525(research code)(723)+TX、RU 25475 (research code) (1386) + TX, ryania (alternative name) (1387) + TX, ryanodine (traditional name) (1387) + TX, sabafos (alternative name) (725) + TX, octamethoxazole (1389) + TX, cadusifos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) +TX, SI-0404 (compound code) +TX, SI-0405 (compound code) +TX, flusilate (728) +TX, SN72129 (research code) (1397) +TX, sodium arsenite [CCN] +TX, sodium cyanide (444) +TX, sodium fluoride (IUPAC / Chemical Abstracts name) (1399) +TX, sodium hexafluorosilicate (1400) +TX, sodium pentachlorophenate (623) +TX,Sodium selenate (IUPAC name) (1401) + TX, sodium thiocyanate [CCN] + TX, thiothion (1402) + TX, spinosad (737) + TX, spiromesifen (739) + TX, spirotetramat (CCN) + TX, sulcofuron (746) + TX, sulcofuron-sodium (746) + TX, flubendiamide (750) + TX, thiophanate (753) + TX, sulfanilamide (756) + TX, thiopromide (1408) + TX, tar (alias) (758) + TX, τ-fluvalinate (398) + TX, thiabendazole (1412) + TX, TDE (1414) + TX, tebufenozide (762) + TX, tebufenpyrad (763) + TX, butylpyrimidin (764) + TX, flubendiamide (768) + TX, tefluthrin (769) + TX, tebufenox (770) + TX, TEPP (1417) + TX, cyclopentyl thiocyanate (1418) + TX, terbufos (773) + TX, tetrachloroethane [CCN] + TX, cypermethrin (777) + TX, tetramethrin (787) + TX, θ-cypermethrin (204) + TX, thiacloprid (791) + TX, thiafenox (792) + TX, thiophenesulfonate (793) + TX, thiamethoxam (794) + TX, thiamethoxam (795) + TX, thiamethoxam (796) + TX, thiamethoxam (797) + TX, thiamethoxam (798) + TX, thiamethoxam (799) + TX, thiamethoxam (791 ... ofos)(1428)+TX, cypermethrin(1431)+TX, cyclohexane(798)+TX, cyclohexane hydrogen oxalate(798)+TX, thiodicarb(799)+TX, long-lasting carbendazim(800)+TX, methyl sulfophos(801)+TX, cypermethrin(1434)+TX, thiosultap(803)+TX, thiosultap-sodium(803)+TX, thuringin (alias) [CCN]+TX, tolfenpyrad(809)+TX, tralomethrin(812)+TX, transfluthrin(813)+TX, transpermethrin(1440)+TX X, cypermethrin (1441) + TX, triazophos (818) + TX, triazophos (820) + TX, triazophos (alias) + TX, trichlorfon (824) + TX, trichlormetaphos-3 (alias) [CCN] + TX, chlorpyrifos (1452) + TX, trichlorprop (1455) + TX, thiocarb (835) + TX, thiocarb (840) + TX, methoprene (1459) + TX, thiocarb (847) + TX, vaniliprole [CCN] + TX, veratridine (alias) (725) + TX, veratridine (alias) (725) + TX, XMC (853) + TX,Methotrexate (854) + TX, YI-5302 (compound code) + TX, ζ-cypermethrin (205) + TX, zetamethrin (alias) + TX, zinc phosphide (640) + TX, zolaprofos (1469) and ZXI8901 (research code) (858) + TX, cyantraniliprole [736994-63-19] + TX, chlorantraniliprole [500008-45-7] + TX, cyenopyrafen [560121-52-0] + TX, cyflumetofen [400882-07-7] + TX, pyrifluquinazon [337458-27-2] + TX, Spinetoram [187166-40-1 + 187166-15-0] + TX, spirotetramat [203313-25-1] + TX, sulfoxaflor [946578-00-3] + TX, flufiprole [704886-18-0] + TX, chlorfluanid [915288-13-0] + TX, tetramethylfluthrin [84937-88-2] + TX, triflumezopyrim (disclosed in WO2012 / 092115) + TX, fluxametamide (WO 2007 / 026965)+TX, ε-metofluthrin[240494-71-7]+TX, ε-momfluorothrin[1065124-65-3]+TX, fluazaindolizine[1254304-22-7]+TX, chlor-alkali propargylthrin[399572-87-3]+TX, fluxametamide[928783-29-3]+TX, cyhalothrin odiamide) [1262605-53-7] + TX, tioxazafen [330459-31-9] + TX, broflanilide [1207727-04-5] + TX, flufiprole [704886-18-0] + TX, cyclobromofenamide [1031756-98-5] + TX, flucyantamide [1229654-66-3] + TX, pyraclostrobin (described in WO 2010 / 060231) + TX, cycloxanil (described in WO 2005 / 077934) + TX, Spiropyrion + TX, Afidopyropen + TX, flupyrimin + TX, Momfluorothrin + TX, kappa-bifenthrin + TX,κ-Sefluthrin+TX, Dichloromezotiaz+TX, Tetrachloraniliprole+TX, benzpyrimoxan+TX;,

[0786] Molluscicides selected from the group consisting of di(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetyl arsenite [CCN] + TX, copper sulfate (172) + TX, triphenyltin (347) + TX, iron phosphate (IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-ethanolamine ( 576)+TX, pentachlorophenol (623)+TX, sodium pentachlorophenoxide (623)+TX, thiabendazole (1412)+TX, thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX, trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347)+TX, pyriprole [394730-71-3]+TX,

[0787] A nematicide selected from the group consisting of: 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) Abstract name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1,3,5-thiadiazin-3-yl acetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alias) (210) + TX, abamectin (1) + TX, acetofenamide [CCN] + TX, cotton bell carb (15) + TX, aldicarb (16) + TX, aldicarb (863) + TX, AZ60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridabenz (alias) + TX, chlorpyrifos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbofuran (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, chlorpyrifos (999) + TX, cytokinin (alias) (210) + TX , dazomethane (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafos (1044) + TX, dimethoate (1051) + TX, dicliphos (alias) + TX, dimethoate (262) + TX, doramectin (alias) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alias) [CCN] + TX, ethoprophos (312 )+TX, ethylene dibromide (316)+TX, fenamiphos (326)+TX, fenpyrad (alias)+TX, fensulfuron (1158)+TX, thiazophos (408)+TX, butythiophos (1196)+TX, furfural (alias) [CCN]+TX, GY-81 (research code) (423)+TX, thiophene [CCN]+TX, iodomethane (IUPAC name) (542)+TX, isamidophos (1230)+TX, chlorinated Azophos (1231) + TX, Ivermectin (alias) [CCN] + TX, Kinetin (alias) (210) + TX, Methyl azophos (1258) + TX, Metamectin (519) + TX, Metamectin potassium salt (alias) (519) + TX, Metamectin sodium salt (519) + TX, Methyl bromide (537) + TX, Methyl isothiocyanate (543) + TX, Milbemycin oxime (alias) [CCN] + TX, Moxidectin (alias) [CCN] + TX, Myrotheciumverrucaria) combination (alias) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosphamidon [CCN] + TX, clomiphene (alias) + TX, selamectin (alias) [CCN] + TX, spinosad (737) + TX, terbufos (alias) + TX, terbufos (773) + TX, tetrachlorothiophene (IUPAC / Chemical Abstract name) (1422) + TX, thiafenox (alias) + TX, cypermethrin (1434) + TX, triazophos (820) + TX, triazuron (alias) + TX, dimethylol [CCN] + TX, YI-5302 (compound code) and zeatin (alias) (210) + TX, fluensulfone [318290-98-1] + Tx, fluopyram + TX,

[0788] Nitrification inhibitors selected from the group consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,

[0789] Plant activators selected from the group consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alias) (720) + TX,

[0790] Rodenticide selected from the group consisting of: 2-isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, α-chlorohydrin [CCN] + TX, aluminum phosphide (640) + TX, antoquinol (880) + TX, arsenic trioxide (882) + TX, barium carbonate (891) + TX, bisulfamethoxazole (912) + TX, brodifacoum (89) + TX, bromadiolone (91) + TX, Bromoclazine (92) + TX, Calcium Cyanide (444) + TX, Chloralose (127) + TX, Chloralone (140) + TX, Cholecalciferol (alias) (850) + TX, Chlorodiclofenac (1004) + TX, Cholecalciferol (1005) + TX, Cytodextrin (175) + TX, Cytodextrin (1009) + TX, Cytodextrin (246) + TX, Cytodextrin (249) + TX, Cytodextrin (273) + TX, Calcifedol (301) + TX, Fludioxaline (357) + TX, fluoroacetamide (379) + TX, fluridine (1183) + TX, fluridine hydrochloride (1183) + TX, γ-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, thiamethoxam (1318) + TX, thiamethoxam (13 36)+TX, phosphine (IUPAC name) (640)+TX, phosphorus [CCN]+TX, warfarin (1341)+TX, potassium arsenite [CCN]+TX, warfarin (1371)+TX, scilla glycoside (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,

[0791] Synergists selected from the group consisting of 2-(2-butoxyethoxy)ethyl piperate (IUPAC name) (934) + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (alias) (324) + TX, MB-599 (research code) (498) + TX, MGK264 (research code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (research code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX,

[0792] An animal repellent selected from the group consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper cyclohexane [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, salamine (804) + TX, trimethacarb (840) + TX, zinc cyclohexane [CCN] and ziram (856) + TX,

[0793] Virucidal agents selected from the group consisting of: imipenem (alias) [CCN] and ribavirin (alias) [CCN] + TX,

[0794] Wound protection agent selected from the group consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX,

[0795] and a biologically active compound selected from the group consisting of: azaconazole [60207-31-0] + TX, bifenthiazolin [70585-36-3] + TX, oxadiazol [116255-48-2] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [119446-68-3] + TX, diniconazole [83657-24-3] + TX, epoxiconazole [106325-08-0] + TX, fenbuconazole [114369-43-6] + TX, fluquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol [76674-21-0] + TX, hexaconazole [7 9983-71-4]+TX, imazalil[35554-44-0]+TX, imidazole[86598-92-7]+TX, ipconazole[125225-28-7]+TX, metconazole[125116-23-6]+TX, myclobutanil[88671-89-0]+TX, pyrifenox[88283-41-4]+TX, prochloraz[67747-09-5]+TX, propiconazole[60207-90-1]+TX, simconazole econazole) [149508-90-7] + TX, tebuconazole [107534-96-3] + TX, fluconazole [112281-77-3] + TX, triadimefon [43121-43-3] + TX, triadimefon [55219-65-3] + TX, triflumuron [99387-89-0] + TX, trichlorfon [131983-72-7] + TX, tricyclamide [12771-68-5] + TX, chlorfenapyr [60168-88-9] + TX, fluchlorapyramide [63284-71-9] + TX, bupirimate [41483-43-6] + TX, mefenamic acid ( dimethirimol) [5221-53-4] + TX, ethirimol [23947-60-6] + TX, dodecacyclic morpholine [1593-77-7] + TX, fenpropidine [67306-00-7] + TX, fenpropimorph [67564-91-4] + TX, spiroxafil [118134-30-8] + TX, tridecafil [81412-43-3] + TX, cyprodinil [121552-61-2] + TX, pyraclostrobin [110235-47-7] + TX, pyrimethanil [53112-28-0] + TX,Flunix [74738-17-3] + TX, fludioxonil [131341-86-1] + TX, benalaxyl [71626-11-4] + TX, furalaxyl [57646-30-7] + TX, metalaxyl [57837-19-1] + TX, R metalaxyl [70630-17-0] + TX, furamide [58810-48-3] + TX, oxadixyl [77732-09-3] + TX, benomyl [17804-35-2] + TX, carbendazim [10605-21-7] + TX, debacarb )[62732-91-6]+TX、maisuining[3878-19-1]+TX、thiabendazole[148-79-8]+TX、chlozolinate[84332-86-5]+TX、dichlozoline[24201-58-9]+TX、iprodione[36734-19-7]+TX、myclozoline[54864-61-8]+TX、procymidone[32809-16-8]+TX、vinclozoline[50471-44-8]+TX、boscalid(b oscalid) [188425-85-6] + TX, carboxin [5234-68-4] + TX, furanilide [24691-80-3] + TX, flutolanil [66332-96-5] + TX, sulfamethoxazole [55814-41-0] + TX, oxycarboxin [5259-88-1] + TX, penthiopyrad [183675-82-3] + TX, thiopyrad [130000-40-7] + TX, biguanide [108173-90-6] + TX, dodine [2439-10-3] [112-65-2] (free bond) + TX X, iminoctadine [13516-27-3] + TX, azoxystrobin [131860-33-8] + TX, etherstrobin [149961-52-4] + TX, enestrobin {Proc. BCPC, Int. Congr., Glasgow. 2003, 1, 93} + TX, fluoxastrobin [361377-29-9] + TX, methyl etherstrobin [143390-89-0] + TX, oxazolidinone [133408-50-1] + TX, trifloxystrobin [141517-21-7] + TX, trifloxystrobin [248593-16-0] + TX, picoxystrobin [117428-22-5] + TX,Pyraclostrobin [175013-18-0] + TX, ferbam [14484-64-1] + TX, mancozeb [8018-01-7] + TX, maneb [12427-38-2] + TX, metiram [9006-42-2] + TX, propineb [12071-83-9] + TX, salamine [137-26-8] + TX, maneb [12122-67-7] + TX, ziram [137-30-4] + TX, captafol [2425-06-1] + TX, captan [133-06-2] + TX, difluanid [1085-98-9] + TX, oxazolidinone (f luoroimide) [41205-21-4] + TX, folpet [133-07-3] + TX, toluenesulfonamide [731-27-1] + TX, Bordeaux mixture [8011-63-0] + TX, copper hydroxide (copperhydroxid) [20427-59-2] + TX, copper chloride (copperoxychlorid) [1332-40-7] + TX, copper sulfate (coppersulfat) [7758-98-7] + TX, copper oxide (copperoxid) [1317-39-1] + TX, mancopper (mancopper) [539 88-93-5]+TX, oxine-copper[10380-28-6]+TX, dinocap[131-72-6]+TX, nitrothal-isopropyl[10552-74-6]+TX, kewensan[17109-49-8]+TX, iprobenphos[26087-47-8]+TX, isoprothiol[50512-35-1]+TX, phosdiphen[36519-00-3]+TX, pyrazophos[13 457-18-6]+TX, tolclofos-methyl[57018-04-9]+TX, acibenzolar-S-methyl[135158-54-2]+TX, difop-butyl[101-05-3]+TX, benzthiazolin[413615-35-7]+TX, blasticidin-S[2079-00-7]+TX, chinomethionat[2439-01-2]+TX, chloroneb[2675-77-6]+TX, chlorothalonil[1897-45-6]+TX,Cyfluanid [180409-60-3] + TX, Cymoxanil [57966-95-7] ​​+ TX, Dichloronaphthoquinone [117-80-6] + TX, Diclocymet [139920-32-4] + TX, Diclomezine [62865-36-5] + TX, Dicloran [99-30-9] + TX, Diethofencarb [87130-20-9] + TX, Dimethomorph [110488-70-5] + TX, SYP-LI90 (Flumorph) [211867-47-9] + TX , dithianon [3347-22-6] + TX, ethaboxam [162650-77-3] + TX, etridiazole [2593-15-9] + TX, famoxadone [131807-57-3] + TX, fenamidone [161326-34-7] + TX, fenoxanil [115852-48-7] + TX, fentin [668-34-8] + TX, ferimzone [89269-64-7] + TX, fluazinam [ 79622-59-6]+TX, fluopicolide[239110-15-7]+TX, flusulfamide[106917-52-6]+TX, fenhexamid[126833-17-8]+TX, fosetyl-aluminium[39148-24-8]+TX, hymexazol[10004-44-1]+TX, propineb[140923-17-7]+TX, IKF-916 (Cyazofamid)[120116-88-3]+TX, kasugamycin n) [6980-18-3] + TX, methasulfocarb [66952-49-6] + TX, mefenacet [220899-03-6] + TX, pencycuron [66063-05-6] + TX, phthalide [27355-22-2] + TX, polyoxins [11113-80-7] + TX, probenazole [27605-76-1] + TX, propamocarb [25606-41-1] + TX, proquinazid [189278-12-4] + TX,Pyroquilon [57369-32-1] + TX, quinoxyfen [124495-18-7] + TX, pentachloronitrobenzene [82-68-8] + TX, sulfur [7704-34-9] + TX, thiazolin [223580-51-6] + TX, triazoxide [72459-58-6] + TX, tricyclazole [41814-78-2] + TX, triamcinol [26644-46-2] + TX, validamycin [37248-47-8] + TX, oxadiazolamide ( zoxamide)(RH7281)[156052-68-5]+TX, mandipropamid[374726-62-2]+TX, isopyrazam[881685-58-1]+TX, sedaxane[874967-67-6]+TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methylene-naphthalen-5-yl)-amide (disclosed in WO 2007 / 048556) + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide (disclosed in WO2006 / 087343) + TX, [(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6, 6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methyl-cyclopropanecarboxylate [915972-17-7] + TX and 1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methyl- 1H-pyrazole-4-carboxamide [926914-55-8] + TX, lancotrione [1486617-21-3] + TX, cloflupyridin-84 [943832-81-3] + TX, ipfentrifluconazole [1417782-08-1] + TX, mefentrifluconazole [1417782-03-6] + TX, quinofumelin [861647-84-9] + TX, D-trans-chlorpromazine [399572-87-3] + TX, chloranilamide [1262605-53-7] + TX, triflurimidine [1254304-22-7] + TX,fluxametamide[928783-29-3]+TX, ε-metofluthrin[240494-71-7]+TX, ε-momfluorothrin[1065124-65-3]+TX, pydiflumetofen[1228284-64-7]+TX, kappa-bifenthrin[439680-76-9]+TX, broflanilide[1207727-04-5]+TX, dichloromezotiaz[1263629-39-5]+TX, dipymetitrone[16114-35-5]+TX, pyraziflumid[942515-63-1]+TX, and kappa-tefluthrin[391634-71-2]+TX; and

[0796] Microorganisms, including: Acinetobacter lwoffii + TX, Acremonium spp. + TX + TX, Acremonium cephalosporin + TX + TX, Acremonium diospyri + TX, Acremonium clavuli + TX, AdoxGV +TX, Agrobacterium radioactive strain K84 +TX, Alternaria destruens +TX, Alternaria Cassiae +TX, Alternaria properties (Alternaria destruens) +TX, Powdery mildew +TX, Aspergillus flavus AF36 +TX, Aspergillus flavus NRRL 21882 +TX, Aspergillus +TX, Aureobasidium +TX, Azospirillum +TX, ( +TX、TAZO )+TX, Azotobacter+TX, Azotobacter chroocuccum +TX, Azotobacter cysts (BionaturalBlooming )+TX, Bacillus amyloliquefaciens+TX, Bacillus cereus+TX, Bacillus chitinosporus strain CM-1+TX, Bacillus chitinosporus strain AQ746+TX, Bacillus licheniformis strain HB-2 (Biostart TM )+TX, Bacillus licheniformis strain 3086 ( +TX、Green )+TX, Bacillus circulans+TX, Bacillus firmus ( +TX, +TX, )+TX, Bacillus firmus strain I-1582+TX, Bacillus megaterium+TX, Bacillus megaterium+TX, Bacillus mycoides strain AQ726+TX, Bacillus papillomavirus (Milky Spore )+TX, Bacillus pumilus+TX, Bacillus pumilus strain GB34 (Yield )+TX, Bacillus pumilus strain AQ717+TX, Bacillus pumilus strain QST 2808( +TX, Ballad )+TX, Bacillus spahericus +TX, Bacillus +TX, Bacillus strain AQ175 +TX, Bacillus strain AQ177 +TX, Bacillus strain AQ178 +TX, Bacillus subtilis strain QST 713 ( +TX, +TX, )+TX, Bacillus subtilis strain QST 714 +TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilis strain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis variant Bacillus amyloliquefaciens strain FZB24 ( +TX, )+TX, Bacillus thuringiensis Cry 2Ae+TX, Bacillus thuringiensis Cry1Ab+TX, Bacillus thuringiensis aizawai GC 91 +TX, Bacillus thuringiensis israelensis ( +TX, +TX, )+TX, Bacillus thuringiensis Kurstaki ( +TX, +TX, +TX, +TX, Scutella +TX, Turilav +TX, +TX、Dipel +TX, +TX, )+TX, Bacillus thuringiensis subsp. Kurstaki BMP 123 +TX, Bacillus thuringiensis subsp. Kurstaki HD-1 +TX, Bacillus thuringiensis strain BD#32+TX, Bacillus thuringiensis strain AQ52+TX, Bacillus thuringiensis var.aizawai ( +TX, )+TX, bacteria spp. +TX, +TX, )+TX, Clavipacter michiganensis phage +TX, +TX, Beauveria bassiana ( +TX, Brocaril )+TX, Beauveria bassiana GHA (Mycotrol +TX, Mycotrol +TX, )+TX, Beauveria brongniartii ( +TX, Schweizer +TX, )+TX, Beauveria spp.+TX, Botrytis cineria+TX, Bradyrhizobium japonicum +TX, Brevibacillus brevis +TX, Bacillus thuringiensis subspecies brionis +TX, BtBooster+TX, Burkholderia cepacia ( +TX, +TX、Blue )+TX, Burkholderia gladii+TX, Burkholderia gladioli+TX, Burkholderia spp.+TX, Canadian thistle fungus (CBHCanadian )+TX, Candida butyri+TX, Candida famata+TX, Candida fructus+TX, Candida glabrata+TX, Candida guilliermondii+TX, Candida melibiosica+TX, Candida oleophila strain O+TX, Candida parapsilosis+TX, Candida pelliculosa+TX, Candida pulcherrima+TX, Candida reukaufii+TX, Candida saitoana( +TX, )+TX, Candida sake+TX, Candida spp.+TX, Candida tenius+TX, Cedecea dravisae+TX, Cellulomonas flavigena+TX, Chaetomium cochliodes +TX, Chaetomium globosum +TX, Chromobacterium subtsugae strain PRAA4-1T +TX, Cladosporium cladosporioides+TX, Cladosporium oxysporum+TX, Cladosporium chlorocephalum+TX, Cladosporium spp.+TX, Cladosporium tenuissimum+TX, Clonostachys rosea +TX, Colletotrichum acutatum +TX, Coniothyrium minitans (Cotans )+TX, Coniothyrium spp.+TX, Cryptococcus albidus +TX, Cryptococcus humicola +TX, Cryptococcus infirmo-miniatus +TX, Cryptococcus laurentii +TX, Cryptophlebia leucotreta granulovirus +TX, Cupriavidus campinensis +TX, Cydia pomonella granulovirus +TX, codling moth granulosis virus ( +TX, Madex +TX, Madex Max / )+TX, Cylindrobasidium laeve+TX, Cylindrocladium+TX, Debaryomyces hansenii+TX, Drechslera hawaiinensis+TX, Enterobacter cloacae+TX, Enterobacteriaceae+TX, Entomophtora virulenta +TX, Epicoccum nigrum +TX, Epicoccum purpurascens +TX, Epicoccum +TX, Filobasidium floriforme +TX, Fusarium oxysporum +TX, Fusarium thunbergii +TX, Fusarium oxysporum ( / Biofox )+TX, Fusarium spp.+TX, Fusarium spp.+TX, Galactomyces geotrichum+TX, Gliocladium catenulatum ( +TX, )+TX, Gliocladium rubrum+TX, Gliocladium spp. +TX, Gliocladium virens +TX, granulovirus +TX, Halobacillus halophilus +TX, Halobacillus litoralis +TX, Halobacillus trueperi +TX, Halomonas +TX, Halomonas subglaciescola +TX, Halovibriovariabilis +TX, Hansenula vitis var. vinifera +TX, Helicoverpa armigera nuclear polyhedrosis virus +TX, corn earworm nuclear polyhedrosis virus +TX, isoflavone-formononetin +TX, Kloeckner yeast +TX, Kloeckner yeast +TX, Lagenidium giganteum +TX, Lecanicillium longisporum +TX, Lecanicillium muscarium +TX, Lymantria dispar nuclear polyhedrosis virus +TX, Halococcus halophilus +TX, Meira geulakonigii +TX, Metarhizium anisopliae +TX, Metarhizium anisopliae (Destruxin )+TX, Metschnikowia fruticola +TX, Metschnikowia pulcherrima +TX, Microdochium dimerum +TX, Micromonospora coerulea +TX, Microsphaeropsis ochracea +TX, Muscodor albus 620 +TX, Muscodorroseus strain A3-5+TX, Mycorrhizae spp. ( +TX、Root )+TX, Myrotheca verrucosa strain AARC-0255 +TX、BROS +TX, Ophiostomapiliferum strain D97 +TX, Paecilomyces farinosus +TX, Paecilomyces fumosorum +TX, )+TX, Paecilomyces lilacinus (Biostat )+TX, Paecilomyces lilacinus strain 251 (MeloCon )+TX, Paenibacillus polymyxa+TX, Pantoea agglomerans (BlightBan )+TX, Pantoea+TX, Pasteurella +TX, Pasteuria nishizawae+TX, Penicillium chrysogenum+TX, Penicillium billai( +TX, )+TX, Penicillium breviscompactum+TX, Penicillium vulgaris+TX, Penicillium griseo-yellow+TX, Penicillium purpurogenum+TX, Penicillium spp.+TX, Penicillium viridum+TX, Phlebiopsis gigantean +TX, phosphate-solubilizing bacteria +TX, Cryptophyton+TX, Phytophthora palmatum +TX, Pichia anomala +TX, Pichia guilermondii +TX, Pichia membrane +TX, Pichia nail +TX, Pichia stipitis +TX, Pseudomonas aeruginosa +TX, Pseudomonas aureofasciens (Spot-Less )+TX, Pseudomonas cepacia+TX, Pseudomonas chlororaphis +TX, Pseudomonas corrugate +TX, Pseudomonas fluorescens strain A506 (BlightBan )+TX, Pseudomonas putida+TX, Pseudomonas reactans+TX, Pseudomonas spp.+TX, Pseudomonas syringae +TX, Pseudomonas aureus +TX, Pseudomonas fluorescens +TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex )+TX、Puccinia canaliculata+TX、Pucciniathlaspeos(Wood )+TX、Pythium oligandrum+TX、Pythium oligandrum +TX, )+TX, Pythium+TX, Rhanellaaquatilis+TX, Rhanella spp.+TX, Rhizobia( +TX, )+TX, Rhizoctonia+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 +TX, Scytalidium spp. +TX, Scytalidium uredinicola +TX, Spodoptera exiguanuclear polyhedrosis virus ( +TX, )+TX, Serratia marcescens+TX, Serratia plymuthica+TX, Serratia spp.+TX, Sordaria fimicola+TX, Spodoptera littoralis nucleopolyhedrovirus +TX, Sporobolomyces roseus +TX, Stenotrophomonas maltophilia +TX, Streptomyces ahygroscopicus +TX, Streptomyces albaduncus +TX, Streptomyces exfoliates +TX, Streptomyces galbus +TX, Streptomyces griseoplanus +TX, Streptomyces griseoviridis +TX, Streptomyces lydicus +TX, Streptomyces lydicus WYEC-108 +TX, Streptomyces violaceus +TX, Tilletiopsis minor +TX, Tilletiopsis spp. +TX, Trichoderma asperellum (T34 )+TX, Trichoderma gamsii+TX, Trichoderma atroviride +TX, Trichoderma hamatum TH 382+TX, Trichoderma harzianum rifai +TX, Trichoderma harzianum T-22 ( +TX, PlantShield +TX, +TX, )+TX, Trichoderma harzianum T-39 +TX, Trichoderma inhamatum +TX, Trichoderma koningii +TX, Trichoderma spp. LC 52 +TX, Trichoderma lignorum +TX, Trichoderma longibrachiatum +TX, Trichoderma polysporum (Binab )+TX, Trichoderma taxi+TX, Trichoderma virens+TX, Trichoderma virens (formerly known as Gliocladium virens GL-21) +TX, Trichoderma viride +TX, Trichoderma viride strain ICC 080 +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 +TX, Ustilago maydis +TX, various bacteria and supplementary nutrients (Natural )+TX, various fungi (Millennium )+TX, Verticillium chlamydosporium+TX, Verticillium lecanii ( +TX, )+TX、Vip3Aa20 +TX, Virgibaclillus marismortui+TX, Xanthomonas campestris pv.Poae +TX, Xenorhabdus burnetii +TX, Xenorhabdus nematophila; and

[0797] Plant extracts, including pine oil +TX, Azadirachtin (Plasma Neem +TX, +TX, +TX, +TX, plant IGR ( +TX, )+TX, canola oil (Lilly Miller )+TX, Chenopodium ambrosioides near ambrosioides +TX, chrysanthemum extract +TX, neem oil extract +TX, Labiatae essential oil +TX, clove-rosemary-mint and thyme oil extract (Garden insect )+TX, betaine +TX, garlic +TX, lemongrass oil +TX, neem oil +TX, catnip (Nepeta cataria) (catnip oil) +TX, catnip +TX, nicotine +TX, oregano oil +TX, Pedaliaceae oil +TX, Pyrethrum+TX, Soapbark Tree (Quillaja saponaria) +TX, Reynoutria sachalinensis ( +TX, )+TX, rotenone (Eco )+TX, Rutaceae plant extract +TX, soybean oil (Ortho )+TX, tea tree oil (Timorex )+TX, thyme oil+TX, MMF+TX, +TX, Rosemary-Sesame-Peppermint-Thyme and Cinnamon Extract Blend (EF )+TX, clove-rosemary and mint extract mixture (EF )+TX, Clove-Peppermint-Garlic Oil and Mint Blend (Soil )+TX, kaolin +TX, storage glucan of brown algae as well as

[0798] Pheromones, including: 3M Sprayable Blackheaded Fireworm )+TX, codling moth pheromone (Paramount dispenser-(CM) / Isomate )+TX, Grape Leaf Roller Pheromone (3M MEC-GBM Sprayable )+TX, leaf roller pheromone (3MMEC–LR Sprayable )+TX, housefly pheromone (Muscamone)(Snip7Fly +TX、Starbar Premium Fly )+TX, 3M oriental fruit moth sprayable )+TX, Peachtree Borer pheromone +TX, Tomato Pinworm Pheromone (3M Sprayable )+TX, Entostat powder (palm tree extract) (Exosex )+TX、(E+TX,Z+TX,Z)-3+TX,8+TX,11-tetradecatriene acetate+TX、(Z+TX,Z+TX,E)-7+TX,11+TX,13-hexadecatrienal+TX、(E+TX,Z)-7+TX,9-dodecadien-1-ol acetate+TX、2-methyl-1-butanol+TX、calcium acetate+TX、 +TX, +TX, +TX, Lavandulyl senecioate; and

[0799] Macrobial agents, including: Aphidius ervi + TX, Aphidius ervi +TX, Acerophagus papaya+TX, Coccinella bispot +TX, Coccinella bispotata +TX, Coccinella bispotata +TX, Ageniaspis citricola+TX, Amblyseius andersoni ( +TX, )+TX, Amblyseius californicus ( +TX, )+TX, Amblyseius cucumeris ( +TX, Bugline )+TX, Pseudo-Amblyseius +TX, Bugline +TX, )+TX, Amblyseius osbornei +TX, Amitus hesperidum +TX, Anagrus atomus +TX, Anagyrus fusciventris +TX, Anagyrus kamali +TX, Anagyrus loecki +TX, Anagyrus pseudococci +TX, Red wax scale flat-horned jumping wasp (Anicetus benefices) +TX, Golden wasp (Anisopteromalus calandrae) +TX, Woodland flower stink bug (Anthocoris nemoralis) +TX, Short-spur Aphid Wasp ( +TX, )+TX, Aphelinus asychis+TX, Aphidius colemani +TX, Alphididae +TX, tobacco aphid wasp+TX, peach red aphid wasp +TX, aphid-eating gall midge +TX, aphid-eating gall midge +TX, Lingnan aphid wasp +TX, Indian golden aphid wasp +TX, cockroach egg long-tailed biting wasp (Aprostocetus hagenowii) +TX, rove beetle (Atheta coriaria) +TX, Bombus spp. +TX, European Bombus (Natupol )+TX, European Bumblebee ( +TX, )+TX, Cephalonomia stephanoderis+TX, Black-backed Red Ladybug (Chilocorus nigritus)+TX, Common Lacewing (Chrysoperla carnea) +TX, Common Lacewing +TX, Chrysoperla rufilabris+TX, Cirrospilus ingenuus+TX, Cirrospilusquadristriatus+TX, Citrostichus phyllocnistoides+TX, Closterocerus chamaeleon+TX, Closterocerus+TX, Coccidoxenoides perminutus +TX, Coccophagus cowperi+TX, Coccophagus lycimnia+TX, Coccophagus lycimnia+TX, Coccophagus luteola+TX, Coccophagus moniliformis+TX, +TX, )+TX、Japanese square-headed beetle+TX、Siberian jawed braconid wasp+TX、Siberian jawed braconid wasp +TX, pea leafminer +TX, small black ladybug (Delphastuscatalinae) +TX, Delphastus pusillus+TX, Diachasmimorpha krausii+TX, Long-tailed fly miner+TX, Diaparsis jucunda+TX, Diaphorencyrtusaligarhensis+TX, Pea leafminer+TX, Pea leafminer +TX, )+TX, Siberian Braconid Wasp ( +TX, )+TX, Encarsia genus+TX, Encarsia spp.+TX, +TX, +TX, )+TX, Eretmocerus eremicus +TX, Encarsia guadeloupae +TX, Encarsia haitiensis +TX, Slender Hoverfly +TX, Eretmoceris siphonini+TX, Eretmocerus californicus+TX, Eretmocerus eremicus( +TX, Eretline )+TX, Eretmocerus eremicus +TX, Heinrich's aphid wasp+TX, Monterey's aphid wasp ( +TX, Eretline )+TX, Eretmocerus siphonini+TX, Four-spotted Ladybird (Exochomus quadripustulatus)+TX, Feltiella acarisuga +TX, Acarina +TX, Alishan fly miner +TX, Fopiusceratitivorus +TX, Wirless )+TX, thrips slender waist +TX, Galendromus occidentalis +TX, Goniozus legneri +TX, Echinops serratus +TX, Harmonia axyridis +TX, Heterorhabditis spp. (Lawn )+TX, Heterorhabditis elegans (NemaShield +TX, +TX, +TX, +TX, +TX, +TX, NemAttack +TX, )+TX, Heterorhabditis megidis (Nemasys +TX, BioNem +TX、Exhibitline +TX, )+TX, Hippodamiaconvergens+TX, Hypoaspis aculeifer ( +TX, )+TX、Hypoaspis miles(Hypoline +TX, )+TX, Black Branch Gall Wasp+TX, Lecanoideus floccissimus+TX, Lemophaguserrabundus+TX, Leptomastidea abnormis+TX, Leptomastix dactylopii +TX, Leptomastix epona+TX, Lindoruslophanthae+TX, Lipolexis oregmae+TX, Greenfly +TX, Tea-footed Aphid Wasp+TX, Dark-spine Blight Bug (Macrolophus caliginosus) ( +TX、Macroline +TX, )+TX, Mesoseiulus longipes+TX, Metaphycus flavus+TX, Metaphycus lounsburyi+TX, and Metaphycus hornbeam +TX, Microterys flavus +TX, Muscidifurax raptorellus and Spalangia cameroni +TX, Neodryinus typhlocybae+TX, California Neoseiulus californicus+TX, Amblyseius cucumeris +TX, Neoseiulus fallacis+TX, Nesideocoris tenuis( +TX, )+TX, Bronze Blackfly +TX, Orius insidiosus ( +TX, Oriline )+TX, Orius laevigatus ( +TX, Oriline )+TX、Orius majusculus(Oriline )+TX, small black flower stink bug +TX, Pauesia juniperorum+TX, Pediobius foveolatus+TX, Phasmarhabditis hermaphrodita +TX, Phymastichus coffea+TX, Phytoseiulus macropilus+TX, Phytoseiulus chilensis ( +TX、Phytoline )+TX, Cypripedium scaly-bellied +TX, Pseudacteon curvatus+TX, Pseudacteon obtusus+TX, Pseudacteon tricuspis+TX, Pseudaphycus maculipennis+TX, Pseudleptomastix mexicana+TX, Psyllaephagus pilosus+TX, Psyttalia concolor (complex)+TX, Rhyzobius lophanthae+TX, Australian ladybird+TX, Rumina decollate+TX, Semielacher petiolatus+TX, Aphid +TX, Steinernema carinii (Nematac +TX, +TX, BioNem +TX, +TX, +TX, )+TX, Steinernema carinata ( +TX, Nemasys +TX, BioNem +TX, +TX, +TX, +TX、Exhibitline +TX, +TX, )+TX, Steinernema kraussei (Nemasys +TX, BioNem +TX、Exhibitline )+TX, Steinernema riobrave ( +TX, )+TX, Steinernema scapterisci (Nematac )+TX, Steinernematid genus+TX, Steinernematid genus (Guardian )+TX, Deep-point mite-feeding ladybug +TX, bright-bellied enameled wasp+TX, Tetrastichus setifer+TX, Thropobiussemiluteus+TX, Chinese long-tailed wasp (Torymus sinensis)+TX, Tricholine )+TX, Trichogrammatid wasp +TX, Trichogramma spleniformis +TX, Trichogramma microplus +TX, Trichogramma ostriniae +TX, Trichogramma platneri +TX, Trichogramma shoriperid +TX, and Trichogramma striata; and

[0800] Other biological agents, including: abscisic acid + TX, +TX, Chondrostereum purpureum (Chontrol )+TX, Colletotrichum spondyloticum +TX, copper octanoate +TX, Delta trap (Trapline )+TX, Erwinia amylovora (Harpin) ( +TX、Ni-HIBIT Gold )+TX, ferric phosphate +TX, Trapline )+TX、 +TX, Grower's +TX, homobrassinolide +TX, iron phosphate (Lilly Miller Worry Free Ferramol Slug & Snail )+TX, MCP Hail Trap (Trapline )+TX, Microctonus hyperodae+TX, Mycoleptodiscus terrestris +TX, +TX, +TX, +TX, Pheromone Trap (Thripline )+TX, potassium bicarbonate +TX, potassium salt of fatty acids +TX, potassium silicate solution +TX, potassium iodide + potassium thiocyanate +TX, +TX, spider venom +TX, locust microsporidia (Semaspore Organic Grasshopper )+TX, Trapline +TX, Rebell )+TX and trap (Takitrapline )+TX;

[0801] or a biologically active compound or agent selected from the group consisting of flumethrin + TX, diflovidazine + TX, flometoquin + TX, fluhexafon + TX, diamondback moth granulovirus + TX, codling moth granulovirus + TX, imipenem + TX, tobacco budworm nuclear polyhedrosis virus + TX, Heliothis punctigera nuclear polyhedrosis virus + TX, zea worm nuclear polyhedrosis virus + TX, fall armyworm nuclear polyhedrosis virus + TX, diamondback moth nuclear polyhedrosis virus + TX, para-cymene + TX, pyflubumide + TX, pyrafluprole + TX, QRD 420 + TX, QRD 452 + TX, QRD 460 + TX, terpenoid mixture + TX, terpenoid + TX, tetranimid + TX, and α-terpinene + TX;

[0802] Or active substances mentioned by the following codes + TX: code AE ​​1887196 (BSC-BX60309) + TX, code NNI-0745GR + TX, code IKI-3106 + TX, code JT-L001 + TX, code ZNQ-08056 + TX, code IPPA152201 + TX, code HNPC-A9908 (CAS: [660411-21-2]) + TX, code HNPC-A2005 (CAS: [860028-12-2]) + TX, code JS118 + TX, code ZJ0967 + TX, code ZJ2242 + TX, code JS7119 (CAS: [929545-74-4]) + TX, code S N-1172+TX, code HNPC-A9835+TX, code HNPC-A9955+TX, code HNPC-A3061+TX, code Chuanhua89-1+TX, code IPP-10+TX, code ZJ3265+TX, code JS9117+TX, code ZJ3757+TX, code ZJ4042+TX, code ZJ4014+TX, code ITM-121+TX, code DPX-RAB55(DKI-2301)+TX, code NA-89+TX, code MIE-1209+TX, code MCI-8007+TX, code BCS-CL73507 +TX, code S-1871+TX, code DPX-RDS63+TX, Quinofumelin+TX, mefentrifluconazol+TX, fenpicoxamid+TX, fluindapyr+TX, inpyrfluxam+TX or indif lumetpyr+TX, isoflucypram+TX, pyrapropoyne+TX, florylpicoxamid+TX, metyltetraprole+TX, ipflufenoquin+TX, pyridachlometyl+TX or c hlopyridiflu+TX, tetrachlorantraniliprole+TX, tetrachloraniliprole+TX, Tyclopyrazoflor+TX, flupyrimin+TX or pyrifluramide+TX, benzpyrimoxan+TX, Benzosufyl+TX or oxazosulfyl+TX, etpyrafen+TX, acynonapyr+TX or pyrinonafen+TX, oxotrione+TX,Bixlozone+TX or clofendizone+TX or dicloroxizone+TX, cyclopyranil+TX or pyrazocyclonil+TX or cyclopyrazonil+TX, α-bromadiolone+TX, code AKD-1193+TX, oxathiapiprolin+TX, fluopyram+TX, fluoxopyrosad+TX, and flupyradifurone+TX.

[0803] References in brackets after the active ingredient, e.g. [3878-19-1] refer to Chemical Abstracts Registry Numbers. The mixed partners described above are known. In the case where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; 13th edition; Editor: CDSTomLin; The British Crop Protection Council]], they are described therein by the entry number given above in parentheses for the specific compound; e.g. the compound "abamectin" is described by entry number (1). In the case where "[CCN]" is added above to a specific compound, the compound in question is included in the "Compendium of Pesticide Common Names", which can be found on the Internet [A.Wood; Compendium of Pesticide Common Names ,Copyright 1995-2004]; for example, the compound "acetoprole" is described on the Internet at http: / / www.alanwood.net / pesticides / acetoprole.html.

[0804] Most of the active ingredients mentioned above are referred to above by their so-called "common names," with the relevant "ISO common name" or another "common name" being used in individual cases. If a name is not a "common name," the kind of name used is replaced by the name given in parentheses for the specific compound; in this case, the IUPAC name, IUPAC / Chemical Abstracts name, "Chemical Name," "Traditional Name," "Compound Name," or "Research Code" is used, or if neither one of those names nor the "common name" is used, the "synonym" is used. "CAS Registry Number" means the Chemical Abstracts Registry Number.

[0805] Active ingredient mixtures of a compound of formula I (selected from Tables A-1 to A-15, B-1 to B-15, C-1 to C-15, D-1 to D-30, E-1 to E-15, F-1 to F-15, G-1 to G-15, H-1 to H-15, I-1 to I-15, J-1 to J-15, K-1 to K-15, L-1 to L-15 and M-1 to M-60 and compounds defined in Table P) with the active ingredients described above include a compound selected from Tables A-1 to A-15, B-1 to B-15, C-1 to C-15, D-1 to D-30, E-1 to E-15, F-1 to F-15, G-1 to G-15, H-1 to H-15, I-1 to I-15, J-1 to J-15, K-1 to K-15, L-1 to L-15 and M-1 to M-60 and a compound as defined in Table P and an active ingredient as described above, preferably in a mixing ratio of from 100:1 to 1:6000, in particular is from 50:1 to 1:50, more particularly in a ratio of from 20:1 to 1:20, even more particularly from 10:1 to 1:10, very particularly from 5:1 and 1:5, particularly preferably in a ratio of from 2:1 to 1:2, and likewise preferably in a ratio of from 4:1 to 2:1, in particular in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2: or 1:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. Those mixing ratios are by weight.

[0806] The mixtures as described above may be used in a method for controlling pests which comprises applying a composition comprising a mixture as described above to the pests or their environment, excluding methods for treating the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body.

[0807] Mixtures of a compound of formula I (selected from Tables A-1 to A-15, B-1 to B-15, C-1 to C-15, D-1 to D-30, E-1 to E-15, F-1 to F-15, G-1 to G-15, H-1 to H-15, I-1 to I-15, J-1 to J-15, K-1 to K-15, L-1 to L-15, and M-1 to M-60, and a compound defined in Table P) and one or more active ingredients as described above can be applied, for example, as follows: in a single "water-in-use" form, in a combined spray mixture (the mixture is composed of separate formulations of these single active ingredient components, such as a "tank mix"), and in combination when applied in a sequential manner (i.e., one after another reasonably short period of time, such as a few hours or days). The order in which the compound of formula I is applied with the active ingredients as described above is not critical for practicing the present invention.

[0808] The compositions according to the invention may also contain other solid or liquid adjuvants, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soybean oil), defoamers (for example silicone oils), preservatives, viscosity regulators, adhesives and / or tackifiers, fertilizers or other active ingredients for achieving specific effects, such as bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0809] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries, for example by grinding, screening and / or compressing the solid active ingredient; and in the presence of at least one auxiliary, for example by intimately mixing the active ingredient with one or more auxiliary agents and / or grinding the active ingredient with one or more auxiliary agents. These methods for preparing the compositions and the use of compound I for preparing these compositions are also subject matter of the present invention.

[0810] Methods of applying these compositions, i.e. methods for controlling the above-mentioned types of pests, such as spraying, atomizing, dusting, brushing, seed dressing, broadcasting or pouring (which are selected to be suitable for the intended purpose of the prevailing situation) and the use of these compositions for controlling the above-mentioned types of pests are further subjects of the present invention. Typical concentration rates are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of the active ingredient. The application rate per hectare is generally 1 g to 2000 g of active ingredient per hectare, in particular 10 g / ha to 1000 g / ha, preferably 10 g / ha to 600 g / ha.

[0811] In the field of crop protection, the preferred method of application is application to the leaves of the plants (foliar application), the frequency and rate of application possibly being selected to suit the risk of infestation by the pest in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by saturating the locus of the plants with a liquid composition or by introducing the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of rice crops, such granules can be metered into flooded rice fields.

[0812] The compound with formula I of the present invention and composition thereof are also suitable for the protection (for example seed, as fruit, tuber or grain, or nursery plant) of plant propagation material, to resist the harmful organism of above-mentioned type.Can be with described compound before planting, described propagation material is processed, for example, can be processed before sowing seed.Alternately, described compound can be applied to seed grain (coating), and this is by being immersed in liquid composition by grain or by coating solid composition layer realization.Also may apply described composition when described propagation material is planted to application site, for example, described composition is applied to seed furrow during sowing.These treatment methods for plant propagation material and the plant propagation material of therefore processing are other themes of the present invention.Typical treatment ratio will depend on plant and harmful organism / fungus to be controlled, and usually between 1 gram to 200 grams of every 100kg seed, preferably between 5 grams to 150 grams of every 100kg seed, as between 10 grams to 100 grams of every 100kg seed.

[0813] The term seed includes all kinds of seeds and plant propagules including but not limited to true seeds, seed pieces, suckers, kernels, bulbs, fruits, tubers, grains, rhizomes, cuttings, cuttings and the like and in preferred embodiments means true seeds.

[0814] The present invention also includes seeds coated or treated with a compound of formula I or seeds containing a compound of formula I. Although more or less of the component may penetrate into the seed material, depending on the method of application, the term "coating or treatment and / or containing" generally means that at the time of application, in most cases, the active ingredient is on the surface of the seed. When the seed product is (re)planted, it can absorb the active ingredient. In an embodiment, the present invention makes it possible to obtain plant propagation materials having a compound of formula I adhered thereto. In addition, a composition comprising plant propagation materials treated with a compound of formula I can be obtained.

[0815] Seed treatment includes all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting. Seed treatment with the compound of Formula I can be achieved by any known method and used, such as, spraying or by dusting before sowing or during sowing / planting of these seeds.

[0816] The compounds of the present invention may be distinguished from other similar compounds by greater efficacy and / or different pest control at lower application rates, which can be determined by one skilled in the art using experimental procedures, using lower concentrations (if necessary) such as 10 ppm, 5 ppm, 2 ppm, 1 ppm or 0.2 ppm, or lower application rates such as 300 mg, 200 mg or 100 mg of AI / m 2 Greater efficacy may be observed through increased safety (to above- and below-ground non-target organisms such as fish, birds, and bees), improved physicochemical properties, or increased biodegradability.

[0817] In each aspect and embodiment of the present invention, "consisting essentially of and variations thereof are preferred embodiments of "comprising" and variations thereof, and "consisting of and variations thereof are preferred embodiments of "consisting essentially of and variations thereof.

[0818] The disclosure of this application enables each and every combination of the embodiments disclosed herein.

[0819] Biological examples:

[0820] The following examples illustrate the present invention. Certain compounds of the present invention may differ from known compounds in that they exhibit greater efficacy at lower application rates, which can be demonstrated by one of ordinary skill in the art using the experimental procedures outlined in the examples, using lower application rates (if necessary) such as 50 ppm, 24 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

[0821] Example B1: Cucumber leaf beetle (Diabrotica balteata) (corn rootworm)

[0822] Corn sprouts placed on an agar layer in a 24-well microtiter plate were treated with an aqueous test solution prepared from a 10,000ppm DMSO stock solution by spraying. After drying, the plates were infested with L2 larvae (6 to 10 / well). Four days after infestation, these samples were evaluated for mortality and growth inhibition compared to untreated samples.

[0823] The following compounds gave at least 80% control in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:

[0824] P1, P3, P5, P6, P7, P9, P11, P12, P13, P15, P16, P18, P19, P20, P21, P22, P23, P24, P25 and P33.

[0825] Example B2: Euschistus heros) (Neotropical brown stink bug)

[0826] Soybean leaves on agar in 24-well microtiter plates were sprayed with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, the leaves were infested with N2 nymphs. Five days after infestation, these samples were evaluated for mortality and growth inhibition compared to untreated samples.

[0827] The following compounds gave at least 80% control in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:

[0828] P5, P12, P14, P15, P16, P17, P20, P21, P22 and P23.

[0829] Example B3: Frankliniella occidentalis occidentalis) (Western flower thrips): feeding / contact activity

[0830] Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with an aqueous test solution prepared from a 10,000 μL DMSO stock solution. After drying, the leaf discs were infested with a mixed-age population of flower thrips. Seven days after infestation, these samples were evaluated for mortality.

[0831] The following compounds produced at least 80% mortality at an application rate of 200 ppm:

[0832] P19.

[0833] Example B4: Chilo suppressalis (Striped Rice Stem Borer rice stemborer))

[0834] 24 hole microtiter plates with artificial feed are handled by pipetting with the aqueous test solution prepared from 10 '000ppm DMSO stock solution.After drying, plate is infested (6-8 only / hole) with L2 stage larvae. 6 days after infestation, compared to untreated sample, these samples are assessed for mortality rate, antifeedant effect and growth inhibition. When at least one in these classifications (mortality rate, antifeedant effect and growth inhibition) was higher than untreated sample, the control of test sample to Chilo suppressalis was realized.

[0835] The following compounds produced at least 80% control in at least one of the three categories (mortality, antifeedant effect, or growth inhibition) at an application rate of 200 ppm:

[0836] P5, P12, P13, P14, P15, P16, P17, P18, P19, P20, P21, P22, P23, P24, P32, P33 and P36.

[0837] Example B5: Diamondback moth (Plutella xylostella) moth))

[0838] 24-well microtiter plates with artificial diet were treated by pipetting with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, Plutella xylostella eggs were pipetted through a plastic template onto gel blotting paper and the plates were sealed with the plastic template. Eight days after infestation, these samples were evaluated for mortality and growth inhibition compared to untreated samples.

[0839] The following compounds gave at least 80% control in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:

[0840] P2, P3, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16, P17, P19, P20, P21, P22, P23, P24, P25, P26, P27, P32, P33 and P35.

[0841] Example B6: Myzus persicae (Green peach aphid): Feeding / contact activity

[0842] Sunflower leaf disks were placed on agar in 24-well microtiter plates and sprayed with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, the leaf disks were infested with a population of mixed-age aphids. Six days after infestation, the samples were evaluated for mortality.

[0843] The following compounds produced at least 80% mortality at an application rate of 200 ppm:

[0844] P23 and P24.

[0845] Example B7: Myzus persicae (Green peach aphid): Systemic activity

[0846] The roots of pea seedlings infested with a population of mixed-age aphids were placed directly into an aqueous test solution prepared from a 10,000 DMSO stock solution. Six days after the seedlings were placed in the test solution, the samples were evaluated for mortality.

[0847] The following compounds produced at least 80% mortality at a test rate of 24 ppm:

[0848] P14, P22 and P23.

[0849] Example B8: Myzus persicae (Green peach aphid). Intrinsic activity

[0850] The test compound prepared from 10,000ppm DMSO stock solution was applied to a 24-well microtiter plate by a pipette and mixed with a sucrose solution. The plate was closed with stretched parafilm. A plastic template with 24 holes was placed on the plate, and the pea seedlings to be infected were directly placed on the parafilm. The plate infected was sealed with gel blotting paper and another plastic template, and then inverted. After infecting for 5 days, these samples were evaluated for mortality.

[0851] The following compounds produced at least 80% mortality at a test rate of 12 ppm:

[0852] P5, P12, P14, P15, P16, P17, P19, P20, P21, P22, P23 and P24.

[0853] Example B9: Spodopteralittoralis (Egyptian cotton leafworm)

[0854] The cotton leaf disk is placed on the agar in the 24 hole microtiter plates and sprayed with the aqueous test solution prepared from 10 '000ppm DMSO stock solution.After drying, the leaf disk is infested with five L1 stage larvae.Infested afterwards 3 days, compared to untreated sample, these samples were assessed at mortality rate, antifeedant effect and growth inhibition.When at least one in these classifications (mortality rate, antifeedant effect and growth inhibition) was higher than untreated sample, realized the control of test sample to Spodoptera littoralis.

[0855] The following compounds produced at least 80% control in at least one of the three categories (mortality, antifeedant effect, or growth inhibition) at an application rate of 200 ppm:

[0856] P3, P5, P7, P9, P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, P20, P21, P22, P23, P24, P25, P32 and P33.

[0857] Example B10: Spodoptera littoralis (Egyptian cotton leafworm)

[0858] Test compound is applied to 24 orifice plates and mixed with agar from 10,000ppm DMSO stock solution through pipette. Lettuce seeds are placed on agar and sealed this multi-well plate with another plate that also contains agar. After 7 days, root absorbed the compound and lettuce growth has entered the cover plate. Then, these lettuce leaves are cut into the cover plate. Spodoptera ova are pipetted through plastic templates on moist gel blotting paper and with its sealed cover plate. After infecting, 6 days, compared to untreated sample, these samples were assessed for mortality rate, antifeedant effect and growth inhibition.

[0859] The following compounds gave at least 80% control of at least one of the three categories (mortality, feed rejection, or growth inhibition) at a test rate of 12.5 ppm:

[0860] P14, P16, P20, P21, P22 and P23.

[0861] Example B11: Tetranychus urticae (Two-spotted spider mite): feeding / contact activity

[0862] Bean leaf discs on agar in 24-well microtiter plates were sprayed with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, the leaf discs were infested with a mixed age mite population. Eight days after infestation, these samples were evaluated for mortality of the mixed population (mobile platform).

[0863] The following compounds produced at least 80% mortality at an application rate of 200 ppm:

[0864] P18, P23 and P24.

[0865] Example B12: Thrips tabaci (Onion thrips) feeding / contact activity

[0866] Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, the leaf discs were infested with a mixed-age population of thrips. Six days after infestation, these samples were evaluated for mortality.

[0867] The following compounds produced at least 80% mortality at an application rate of 200 ppm:

[0868] P5.

[0869] Example B13: Myzus persicae (Green peach aphid):

[0870] The test compound prepared from 10,000ppm DMSO stock solution is applied to 96-well microtiter plates and mixed with sucrose solution by liquid handling robot. Parafilm is stretched on 96-well microtiter plates, and a plastic template with 96 holes is placed on this plate. Aphids are screened into the holes directly on this parafilm. The plate infected is sealed with gel blotting card and a second plastic template, and then inverted. After infecting, these samples were assessed for mortality rate 5 days.

[0871] The following compounds produced at least 80% mortality at an application rate of 50 ppm:

[0872] P5, P14, P15, P16, P17, P18, P19, P20, P21, P22, P23, P24 and P25.

[0873] Example B14: Diamondback moth (Plutella xylostella) Moth)):

[0874] The 96-well microtiter plates containing artificial feeds were processed by a liquid handling robot using an aqueous test solution prepared from a 10,000ppm DMSO stock solution. After drying, eggs (approximately 30 per well) were infested on a mesh lid suspended above the feed. These eggs were hatched and the L1 larvae moved downward to the feed. After infestation, these samples were assessed for mortality.

[0875] The following compounds gave an average mortality of at least 80% at an application rate of 500 ppm:

[0876] P1, P2, P3, P5, P6, P7, P8, P9, P10, P11, P14, P15, P16, P17, P18, P19, P20, P21, P22, P23, P25, P26, P27 and P28.

Claims

1. A compound having formula I in: Q is selected from Q-1 to Q-12 wherein R4 is pyridine, pyrimidine, pyrazine or pyridazine, wherein the pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to three substituents independently selected from C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen or hydroxyl; R1 is cyclopropyl -CH2-, CH≡CCH2-, hydrogen or Me; R2 is Z1 to Z 10 one R3 is C1-C3 alkyl or C1-C3 haloalkyl; or an agrochemically acceptable salt of the compound of formula I.

2. The compound according to claim 1, wherein R3 is methyl.

3. The compound according to claim 1 or 2, wherein R4 is 2-pyridine or 2-pyrimidine, which 2-pyridine or 2-pyrimidine is optionally substituted with a substituent selected from halogen and C1-C3 alkoxy.

4. The compound according to claim 1 or 2, wherein R1 is cyclopropyl -CH2- or hydrogen.

5. A composition comprising a compound as defined in any one of claims 1 to 4, one or more adjuvants and diluents, and optionally one or more other active ingredients.

6. A method for combating and controlling insects, acarines, nematodes or molluscs for non-therapeutic purposes, which method comprises applying an insecticidal, acaricidal, nematicidal or molluscicidal effective amount of a compound as defined in any one of claims 1 to 4 or a composition as defined in claim 5 to the pest, the locus of the pest or a plant susceptible to attack by the pest.

7. A method for protecting plant propagation material from attack by insects, mites, nematodes or molluscs, the method comprising treating the propagation material or the site in which the propagation material is planted with an effective amount of a compound as defined in any one of claims 1 to 4 or a composition as defined in claim 5.

8. Use of a compound as defined in any one of claims 1 to 4 or a composition as defined in claim 5 for the preparation of a medicament for controlling parasites in or on an animal in need thereof.

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