COMPOUND OF FORMULA I, PESTICIDE COMPOSITION, METHOD FOR PEST CONTROL AND METHOD FOR THE PROTECTION

专利摘要:
compound of formula I, pesticide composition, method for controlling pests and method for protecting plant propagation material therefrom. the compounds of formula I wherein the substituents are as defined in claim 1, and the agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and n-oxides of such compounds can be used as insecticides and can be prepared in a known manner "per se".
公开号:BR112017014061B1
申请号:R112017014061-6
申请日:2015-12-15
公开日:2021-07-20
发明作者:Andrew Edmunds；Pierre Joseph Marcel Jung；Michel Muehlebach
申请人:Syngenta Participations Ag；
IPC主号:

专利说明:

[0001] The present invention relates to tetracyclic derivatives containing sulfur substituents active in pesticide terms, in particular active in insecticide terms, with compositions comprising these compounds, and with their use for the control of animal pests (including arthropods and in particular insects or representatives of the order Acarina).
[0002] Heterocyclic compounds with pesticidal action are known and described, for example, in WO 2012/086848, WO 2013/018928 and WO 2013/191113.
[0003] New tetracyclic derivatives with a bicyclic sulfur containing fraction active in pesticide terms have now been discovered.
[0004] Consequently, the present invention relates to compounds of the formula I,
where A is CH or N; X is S, SO or SO2; R1 is C1-C4 alkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6-cycloalkyl-C1-C4-alkyl; or is C3-C6 cycloalkyl monoor polysubstituted by substituents selected from the group consisting of halogen, cyano, C1-C4 haloalkyl and C1-C4 alkyl; or is C3-C6-cycloalkyl-C1-C4-alkyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C1-C4 haloalkyl and C1-C4 alkyl; R2 is hydrogen, halogen, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, O(C1-C4 haloalkyl), -SF5, -C(O)C1-C4 haloalkyl, cyano, C1-C6 haloalkyl or is C1-C6 haloalkyl substituted by one or two substituents selected from the group consisting of hydroxy, methoxy and cyano; or is C3-C6 cycloalkyl which may be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C1-C4 haloalkyl and C1-C4 alkyl; G1 is N or CR4; G2 is N or CR5, provided that when G1 is N, G2 is CR5; R6 is hydrogen, halogen or C1-C4 alkyl; R4 and R5, independently of one another, are hydrogen, halogen, cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl, or are C3-C6 cycloalkyl which can be mono or polysubstituted with R8; or are C3-C6 cycloalkyl-C1-C4 alkyl which can be mono or polysubstituted with R9; or R4 and R5, independently of one another, are C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 haloalkoxy, C1-C6 alkoxy, C1-C6 alkylsulfanyl, C1-C4 alkylsulfonyl , C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfanyl, C1-C4 haloalkylsulfonyl, C1-C6 haloalkylsulfinyl or hydroxyl; R8 and R9, independently of one another, are halogen, nitro, cyano, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 alkyl or C1-C4 haloalkyl; and L1, L2, L3 and L4 form together with the two carbon atoms to which L1 and L4 are attached a partially saturated, aromatic carbocyclic or heterocyclic ring system; wherein L1 is nitrogen, S(O)n, oxygen, N-R10a or C(R10a)m; L2 is nitrogen, S(O)n, oxygen, N-R10b, or C(R10b)m; L3 is nitrogen, S(O)n, oxygen, N-R10c, or C(R10c)m; L4 is nitrogen, S(O)n, oxygen, a direct bond, N-R10d or C(R10d)m; provided that no more than 2 substituents selected from L1, L2, L3 and L4 can be oxygen or sulfur; and if two L groups are oxygen, they are not adjacent to each other; and no more than three L groups can be nitrogen; n is 0 to 2; m is 1 or 2; R10a, R10b, R10c and R10d independently of one another are hydrogen, halogen, nitro, cyano, amino, hydroxyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C4 alkoxy C1-C4 alkyl, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1 haloalkylthio -C6, C1-C6 haloalkylsulfinyl, C1-C6 haloalkylsulfonyl, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 haloalkoxycarbonyl, (C1-C6alkyl)NH, (C1-C6alkyl)2N, (C1cycloalkyl) -C6)NH, (C1-C6 cycloalkyl)2N, C1-C6 alkylcarbonylamino, C1-C6 cycloalkylcarbonylamino or -SF5; additionally, one of R10a, R10b, R10c and R10d may be oxo; or R10a, R10b, R10c, and R10d, independently of one another, are C3-C6 cycloalkyl mono- or polysubstituted by substituents selected from the group consisting of C1-C4 haloalkyl, C1-C4 alkyl, and cyano; or R10a, R10b, R10c, and R10d, independently of one another, are phenyl which may be mono- or polysubstituted by substituents selected from the group consisting of halogen, C1-C4 haloalkyl, C1-C4 alkyl, C1-C4 alkoxy and cyano; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of these compounds.
[0005] Compounds of the formula I having at least one basic center can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, an acid phosphorous or a hydrohalic acid, with strong organic carboxylic acids, such as C1-C4 alkane carboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid , succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as acids C1-C4-alkane or arylsulfonics which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid O. Compounds of the formula I which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine such as morpholine, piperidine, pyrrolidine, a short chain mono, di or trialkylamine, for example ethyl, diethyl, triethyl or dimethylpropylamine, or a short chain mono, di or trihydroxyalkylamine, for example mono, di or triethanolamine.
[0006] m is 1 or 2 depending on the hybridization of the carbon atom.
[0007] If m is 2 in definition C(R10a)m, R10a can be the same or different; for example, one R10a can be hydrogen and the other methyl. This is also valid for the definitions of C(R10b)m, C(R10c)m and C(R10d)m.
[0008] The alkyl groups occurring in the definitions of the substituents may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl , hexyl, nonyl, decyl and their branched isomers. Alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, alkoxy, alkenyl and alkynyl radicals are derived from the mentioned alkyl radicals. Alkenyl and alkynyl groups can be mono or polyunsaturated.
[0009] Halogen is usually fluorine, chlorine, bromine or iodine. This also applies correspondingly to halogens in combination with other meanings, such as haloalkyls or halophenyls.
[0010] The haloalkyl groups preferably have a chain length of 1 to 6 carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl.
[0011] Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and also the isomeric radicals pentyloxy and hexyloxy.
Alkoxyalkyl groups preferably have a chain length of 1 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
[0013] Alkoxycarbonyl is for example methoxycarbonyl (which is C1 alkoxycarbonyl), ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, tert-butoxycarbonyl, n-pentoxycarbonyl or hexoxycarbonyl.
[0014] Cycloalkyl groups preferably have from 3 to 6 carbon atoms in the rings, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
As used herein, the term "C2-C6 alkynyl" refers to a straight or branched hydrocarbon chain radical group consisting only of carbon and hydrogen atoms, containing at least one triple bond, with two to six carbon atoms. carbon, and which is attached to the rest of the molecule by a single bond. The terms "alkynyl C2-C4" and "alkynyl C2-C3" are to be interpreted accordingly. Examples of C2-C6 alkynyls include, but are not limited to, ethynyl, prop-1-ynyl, but-1-ynyl, but-2-ynyl.
[0016] As used herein, the term "C2-C6 alkenyl" refers to a straight or branched hydrocarbon chain radical group consisting merely of carbon and hydrogen atoms, containing at least one double bond, having from two to six atoms. of carbon, and that is attached to the rest of the molecule by a single bond. The terms "C2C4 alkenyl" and "C2-C3 alkenyl" are to be interpreted accordingly. Examples of C2-C6 alkenyl include, but are not limited to, prop-1-enyl, but-1-enyl, but-2-enyl.
[0017] In the context of this invention, "L1, L2, L3 and L4 form together with the two carbon atoms to which L1 and L4 are attached or to which L1 and L3 are attached when L4 is bonding a partially carbocyclic ring system saturated, aromatic”, the carbocyclic ring system is preferably a group having 5 to 6 carbon atoms in the rings that are unsaturated or partially unsaturated, for example, but not limited to, phenyl and cyclohexenyl.
[0018] In the context of this invention, "L1, L2, L3 and L4 form together with the two carbon atoms to which L1 and L4 are attached or to which L1 and L3 are attached when L4 is bond, a heterocyclic ring system aromatic or partially saturated", the heterocyclic ring system is preferably a group comprising 1 to 3 heteroatoms in the ring, which are unsaturated or partially saturated, for example, but not limited to, pyrrolyl; pyrazolyl; isoxazolyl; furanyl; thienyl; imidazolyl; oxazolyl; thiazolyl; isothiazolyl; triazolyl; oxadiazolyl; thiadiazolyl; tetrazolyl; furyl; pyridyl; pyrimidyl; pyrazinyl; pyridazinyl; triazinyl, pyranyl; pyrrolidinyl, piperidinyl; pyrrolidinyl-2-one; piperidinyl-2-one.
In the context of this invention, "mono- to polysubstituted" in the definition of substituents typically means, depending on the chemical structure of the substituents, monosubstituted to seven times substituted, preferably monosubstituted to five times substituted, more preferably mono-, di- or tri- - replaced.
[0020] An example of an aromatic or partially unsaturated carbocyclic or heterocyclic ring system in which one of R10a, R10b, R10c or R10d may represent oxo is the J15 group:
wherein X, R1 and A are as defined under formula I above.
The compounds of the formula I according to the invention also include hydrates which can be formed during the formation of the salts.
Compounds of the formula I having at least one basic center can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, an acid phosphorous or a hydrohalic acid, with strong organic carboxylic acids, such as C1-C4 alkane carboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid , succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as acids C1-C4-alkane or arylsulfonics which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid O. Compounds of the formula I which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine such as morpholine, piperidine, pyrrolidine, a short chain mono, di or trialkylamine, for example ethyl, diethyl, triethyl or dimethylpropylamine, or a short chain mono, di or trihydroxyalkylamine, for example mono, di or triethanolamine.
The alkyl groups occurring in the definitions of the substituents may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl , hexyl, nonyl, decyl and their branched isomers. Alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, alkoxy, alkenyl and alkynyl radicals are derived from the mentioned alkyl radicals. Alkenyl and alkynyl groups can be mono or polyunsaturated.
[0024] Halogen is usually fluorine, chlorine, bromine or iodine. This also applies correspondingly to halogens in combination with other meanings, such as haloalkyls or halophenyls.
[0025] Haloalkyl groups preferably have a chain length of 1 to 6 carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, trichloroethyl.
[0026] Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and also the isomeric radicals pentyloxy and hexyloxy.
Alkoxyalkyl groups preferably have a chain length of 1 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
[0028] Alkoxycarbonyl is for example methoxycarbonyl (which is C1 alkoxycarbonyl), ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, tert-butoxycarbonyl, n-pentoxycarbonyl or hexoxycarbonyl.
[0029] Cycloalkyl groups preferably have from 3 to 6 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
[0030] In the context of this invention, "L1, L2, L3 and L4 form together with the two carbon atoms to which L1 and L4 are attached or to which L1 and L3 are attached when L4 is bonding an aromatic carbocyclic ring system , partially saturated or fully saturated”, the carbocyclic ring system is preferably a group having 5 to 6 carbon atoms in the rings which are saturated, unsaturated or partially unsaturated, for example phenyl, cyclopentyl and cyclohexenyl.
[0031] In the context of this invention, "L1, L2, L3 and L4 form together with the two carbon atoms to which L1 and L4 are attached or to which L1 and L3 are attached when L4 is bond an aromatic heterocyclic ring system , partially saturated or fully saturated", the heterocyclic ring system is preferably a group having 5 to 6 carbon atoms in the rings that are saturated, unsaturated or partially unsaturated, for example pyrazol, pyrrole, pyrrolidine, pyrrolidine-2-one, imidazole , triazole and pyridine-2-one.
In the context of this invention, "mono to polysubstituted" in the definition of substituents typically means, depending on the chemical structure of the substituents, monosubstituted up to seven times substituted, preferably monosubstituted up to five times substituted, more preferably mono, di or trisubstituted.
[0033] An example of an aromatic, partially unsaturated or fully saturated carbocyclic or heterocyclic ring system in which one of R10a, R10b, R10c or R10d can represent oxo is the J15 group:
wherein X, R1 and A are as defined under formula I above.
The compounds of the formula I according to the invention also include the hydrates which can be formed during the formation of salts.
Preferred compounds of formula I are those wherein R1 is C1-C4 alkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C4 alkyl; or R1 is C3-C6 cycloalkyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C1-C4 alkyl; or is C 3 -C 6 cycloalkyl-C 1 -C 4 alkyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C 1 -C 4 alkyl; R2 is hydrogen, halogen, haloC 1 -C 4 alkylsulfanyl, haloC 1 -C 4 alkylsulfinyl, haloC 1 -C 4 alkylsulfonyl, O(haloC 1 -C 4 alkyl), -SF5, -C(0)haloC 1 -C 4 alkyl, cyano or haloC 1 -C6 alkyl; or is C1-C6 haloalkyl substituted by one or two substituents selected from the group consisting of hydroxy, methoxy and cyano; or is C3-C6 cycloalkyl which may be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C1-C4 alkyl; G1 is N or CR4; G2 is N or CR5, provided that when G1 is N, G2 is CR5; R6 is hydrogen, halogen or C1-C4 alkyl; R4 and R5, independently of one another, are hydrogen, halogen, cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl, or are C3-C6 cycloalkyl which can be mono or polysubstituted with R8; or are C3-C6 cycloalkyl-C1-C4 alkyl which can be mono or polysubstituted with R9; or R4 and R5, independently of one another, are C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 haloalkoxy, C1-C6 alkoxy, C1-C6 alkylsulfanyl, C1-C4 alkylsulfonyl , C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfanyl, C1-C4 haloalkylsulfonyl, C1-C6 haloalkylsulfinyl or hydroxyl; R8 and R9, independently of one another, are halogen, nitro, cyano, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 alkyl or C1-C4 haloalkyl; and L1, L2, L3 and L4 form, together with the two carbon atoms to which L1 and L4 are attached, an aromatic or partially saturated carbocyclic or heterocyclic ring system; where L1 is nitrogen, sulfur, oxygen or C-R10a; L2 is nitrogen, sulfur, oxygen or C-R10b; L3 is nitrogen, sulfur, oxygen or C-R10c; L4 is nitrogen, sulfur, oxygen, a direct bond or C-R10d; provided that no more than 2 substituents selected from L1, L2, L3 and L4 can be oxygen or sulfur; and if two L groups are oxygen, they are not adjacent to each other; R10a, R10b, R10c, and R10d, independently of one another, are hydrogen, halogen, nitro, cyano, hydroxyl, C1C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C2 haloalkenyl -C6, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1 haloalkylsulfonyl -C4, C2-C4 alkylcarbonyl, C2-C6 alkoxycarbonyl or -SF5; additionally, one of R10a, R10b, R10c and R10d may be oxo; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of these compounds.
[0036] A preferred group of compounds of the formula I is represented by the compounds of the formula I-1
(I-1) wherein the substituents X, A, R1, R2, R6, L1, L2, L3 and L4 are as defined under formula I above. Modality (A1): Preferred are compounds of formula I-1, wherein A is CH or N; R1 is C1-C4 alkyl, C3-C6 cycloalkyl-C1-C4 alkyl or C3-C6 cycloalkyl; R2 is halogen, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 haloalkoxy, C1-C4 haloalkyl, cyano or is C3-C6 cycloalkyl which may be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C1-C4 alkyl; X and R6 are as defined under formula I above; L1, L2, L3 and L4 are as defined under formula I above; and R10a, R10b, R10c and R10d, independently of one another, are hydrogen, halogen, nitro, cyano, hydroxyl, C1C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1 -C4, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, C3-C6 cyclohaloalkyl-C1-C4-cycloalkyl, C1C6 alkoxy, C1-C6 haloalkoxy, C1-C4 alkylthio, C1 alkylsulfinyl -C4, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C2-C4 alkylcarbonyl, C2-C6 alkoxycarbonyl, -SF5; additionally, one of R10a, R10b, R10c and R10d can be oxo. Modality (A2):
[0037] An additionally preferred group of compounds of the formula I is represented by the compounds of the formula I-2
wherein the substituents X, A, R1, R2, R6, L1, L2, L3 and L4 are as defined under formula I above.
[0038] Preferred are compounds of formula I-2, wherein A is C-H or N; R1 is C1-C4 alkyl, C3-C6 cycloalkyl-C1-C4 alkyl or C3-C6 cycloalkyl; R2 is halogen, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 haloalkoxy, C1-C4 haloalkyl, cyano or is C3-C6 cycloalkyl which may be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C1-C4 alkyl; X and R6 are as defined under formula I above; L1, L2, L3 and L4 are as defined under formula I above; and R10a, R10b, R10c and R10d, independently of one another, are hydrogen, halogen, nitro, cyano, hydroxyl, C1C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1 -C4, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, C3-C6 cyclohaloalkyl-C1-C4-cycloalkyl, C1C6 alkoxy, C1-C6 haloalkoxy, C1-C4 alkylthio, C1 alkylsulfinyl -C4, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C2-C4 alkylcarbonyl, C2-C6 alkoxycarbonyl, -SF5; additionally, one of R10a, R10b, R10c and R10d can be oxo. Modality (A3):
[0039] Also preferred are compounds of formula I3;
wherein the substituents X, A, R1, R2, L1, L2, L3 and L4 are as defined under formula I above.
[0040] Preferred are compounds of formula I-3, wherein A is C-H or N; R1 is C1-C4 alkyl, C3-C6 cycloalkyl-C1-C4 alkyl or C3-C6 cycloalkyl; R2 is halogen, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 haloalkoxy, C1-C4 haloalkyl, cyano or is C3-C6 cycloalkyl which may be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C1-C4 alkyl; X and R6 are as defined under formula I above; L1, L2, L3 and L4 are as defined under formula I above; and R10a, R10b, R10c and R10d, independently of one another, are hydrogen, halogen, nitro, cyano, hydroxyl, C1C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1 -C4, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, C3-C6 cyclohaloalkyl-C1-C4-cycloalkyl, C1C6 alkoxy, C1-C6 haloalkoxy, C1-C4 alkylthio, C1 alkylsulfinyl -C4, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C2-C4 alkylcarbonyl, C2-C6 alkoxycarbonyl, -SF5; additionally, one of R10a, R10b, R10c and R10d can be oxo. Modality (A4):
[0041] Further preferred are compounds of formula I-1a
where J is selected from group J1-J27


preferably J1 to J26; and A, R1, R2, X, R10a, R10b, R10c, R10d are as defined in modality (A1), X2 is oxygen or S(O)n1, where n1 is 0, 1 or 2, and R10e is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl or and C3-C6 halocycloalkyl. Modality (A5):
[0042] Further preferred are compounds of formula I-2a
where J is selected from group J1-J27


preferably J1 to J26; and A, R1, R2, X, R10a, R10b, R10c, R10d are as defined in modality (A2), and X2 is oxygen or S(O)n1 (wherein n1 is 0, 1 or 2) and R10e is hydrogen , C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, and C3-C6 halocycloalkyl. Modality (A6):
[0043] Further preferred are compounds of formula I-3a
where J is selected from the group consisting of


preferably J1 to J26; and A, R1, R2, X, R10a, R10b, R10c, R10d are as defined in modality (A3), and X2 is oxygen or S(O)n1 (wherein n1 is 0, 1, or 2) and R10e is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, and C3-C6 halocycloalkyl. Modality (A7)
[0044] Further preferred are compounds of formula I-1a
wherein J is as defined under Modality (A4) above and A is CH or N; R1 is C1-C4 alkyl; R2 is -OCF3, -SCF3, -S(O)CF3, -S(O)2CF3 or CF3; X is as defined under formula I above; and R10a, R10b, R10c and R10d, independently of one another, are hydrogen, halogen, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy , C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl. Modality (A8):
[0045] Further preferred are compounds of formula I-2a
where J is as defined under Modality (A5) above; A is CH or N; R1 is ethyl; R2 is CF3; R10a, R10b, R10c and R10d, independently of each other, are hydrogen, Br, Cl, I, F, cyano, methyl, ethyl, isopropyl, propyl, trifluoromethyl, CF3CH2-, CH3O, -SCF3, -S(O)CF3 or - S(O)2CF3. Modality (A9):
[0046] Further preferred are compounds of formula I-3a
where J is as defined under Modality (A6) above; A is CH or N; R1 is ethyl; R2 is CF3; X is as defined under formula I above; and R10a, R10b, R10c and R10d, independently of one another, are hydrogen, Br, Cl, I, F, cyano, methyl or trifluoromethyl.
[0047] In all preferred embodiments A4-A9, J is preferably J1, J2, J3, J4, J5, J6, J12, J17, J18, J24, J19, J20 J23 or J27. In particular, J is J1, J19 or J27. Modality (A10):
[0048] Further preferred compounds of formula I are those wherein A is CH or N; X is SO2; R1 is C1-C4 alkyl; R2 is C1-C4 haloalkyl or C1-C4 haloalkylsulfanyl; G1 is N or CR4; where R4 is hydrogen; G2 is CR5; where R5 is hydrogen; R6 is hydrogen; L1, L2, L3 and L4 form together with the two carbon atoms to which L1 and L4 are attached a phenyl group or form an imidazolyl group which may be mono- or di-substituted by substituents selected from the group consisting of C1-C4 alkyl and C1-C4 haloalkyl.
The process according to the invention for preparing compounds of formula (I) is carried out by methods known to those skilled in the art, or described for example in WO 2013/191113, WO 2009/131237, WO 2011/043404 , WO 2011/040629, WO 2010/125985, WO 2012/086848, WO 2013/018928, WO 2013/180193 and WO 2013/180194, and involves the reaction of a compound of formula II,
where X01 is a halogen and R6 is as described in formula I, and where Qa is the group
wherein Z is X-R1 or a labile group, for example a halogen, and wherein X, R1, L1, L2, L3, L4 and A are as described under formula I above, and wherein the arrow on the radical Qa shows the point of attachment to the carbon atom of the carboxyl group in the compound of formula II, optionally in the presence of a suitable base in an inert solvent with a compound of formula III
wherein R2, G1 and G2 are as described in formula (I). Such reactions are well known in the literature and have been described for example in WO 2013/191113.
[0050] A further process for preparing compounds of formula I involves reacting a compound of formula III with a compound of IIa

[0051] In the presence of a Lewis acid, such as Zinc(II) Iodide or Indium(III) triflate, in an inert solvent such as chlorobenzene or 1,2-dichlorobenzene, with a catalytic amount of a copper salt (II), such as Cu(II) acetate, under an atmosphere of oxygen or air at temperatures between 100-180 °C, preferably 110-140 °C, to give compounds of formula I wherein R 6 is hydrogen. Such reactions have previously been described in the literature (see Adv. Synth. Catal. 2013, 355, 1741 - 1747 and J. Org. Chem., 2013, 78, 12494-12504). Halogenation of compounds of formula I, where R6 is hydrogen, with a halogenating agent such as N-chlorosuccinamide, N-bromosuccinamide, or N-iodosuccinamide, in a polar aprotic solvent such as acetonitrile or dimethylformamide, at room temperature, leads to compounds of formula Ia01
wherein X, G1, G2, R1, R2, L1, L2, L3, L4 and A are as described in formula (I), and X02 is halogen. Compounds of formula Ia01 can be reacted with compounds R6-M0, where M0 is a boronic acid, in the presence of a palladium catalyst to give compounds of formula I. When M0 is a boronic acid, the reaction is usually carried out in the presence of a base, for example potassium carbonate, cesium carbonate, or potassium phosphate, in an inert solvent, such as dioxane, optionally in the presence of water, with a palladium (0) catalyst, for example tetrakis(triphenylphosphine )palladium, at a temperature between 80-120 oC. Such Suzuki reactions are well presented in the literature, see for example Masuda, Naoyuki et al., WO 2012/133607.
[0052] Compounds of formula II and IIa can be prepared from compounds of formula IV,

[0053] Where Q is as described in formula I, for example, by the methods shown in scheme 1. Scheme 1

In scheme 1, an acyl halide of formula Iva is converted to a Weinreb amide V after reaction with N,O-Dimethylhydroxylamine by methods known to those skilled in the art and described for example in C. Ferri, “Reaktionen der Organischen Synthese”, Georg Thieme Verlag, Stuttgart, 1978, page 223ff. The amide of formula V is then reacted with a Grignard reagent of formula R6CH2MgHal according to the method of Weinreb (Tetrahedron Letters 1981, 22, 38153818) to give compounds of formulas VI and IIa (when R6 is H). Compounds of formulas VI and IIa can also be prepared by treating nitrile compounds of formula VII, wherein Q is as described in formula I, with a Grignard reagent of formula R6CH2MgHal, followed by acid hydrolysis (as described in C. Ferri, “Reaktionen der Organischen Synthese”, Georg Thieme Verlag, Stuttgart, 1978, page 223ff.).
The compounds of the formulas VI and IIa can be halogenated to compounds of the formula II, with for example mixtures of bromine and hydrobromic acid in acetic acid (as described in Phosphorus, Sulfur and Silicon and the Related Elements, 2013, 188 (12 ), 1835-1844) or with, for example, copper(II) bromide in an inert solvent, for example chloroform, ethyl acetate and the like, as described in J. Med. Chem., 2013, 56 (1), 84-96. Alternatively, compounds of formula II where R6 is hydrogen can be prepared directly from compounds of formula IVa by treatment with diazomethane or trimethylsilyldiazomethane and subsequent treatment with a halogen acid, e.g. hydrobromic acid or hydrochloric acid in an inert solvent such as as diethyl ether. Such procedures are well known in the literature, for example see I.J.Med.Chem., 1987, 22(5), 457-62 and WO 2009010455.
[0056] The compounds of formula Ib,
wherein Z is a labile group, for example halogen, preferably fluorine or chlorine, and wherein R6, R2, G1, G2 A, L1, L2, L3 and L4 are as described under formula I above, may be reacted with compounds of the formula VIII R1-SH (VIII), or a salt thereof, wherein R1 is as defined in formula I, optionally in the presence of a suitable base, such as alkali metal carbonates, for example sodium carbonate and potassium carbonate, or alkali metal hydrides such as sodium hydride, or alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, in an inert solvent at temperatures preferably between 25-120 °C, to generate compounds of formula Ic, wherein R1 is as described under formula I above, and in which R6, A, R2, L1, L2, L3, L4, G1 and G2 are as described under formula I above. Examples of solvents to be used include ethers such as THF, ethylene glycoldimethylether, tert-butylmethylether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile or polar aprotic solvents such as N,N-dimethylformamide, N ,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethylsulfoxide. Similar chemistry has been previously described, such as for example in WO2013/018928. Examples of salts of the compound of formula VIII include compounds of the formula VIIIa R 1 -SM (VIIIa), where R 1 is as defined above and where M is, for example, sodium or potassium. This is illustrated for the compounds of formula Ic in scheme 2: Scheme 2

[0057] Alternatively, this reaction can be carried out in the presence of a palladium catalyst, such as tris(dibenzylideneacetone)dipalladium (0), in the presence of a phosphorus ligand, such as xanthphos, in an inert solvent, for example xylene, at temperatures between 100-160°C, preferably 140°C, as described by Perrio et al. in Tetrahedron, 2005, 61, 5253-5259. The subgroup of compounds of the formula I, wherein X is SO (sulfoxide) and/or SO2 (sulfone), can be obtained by means of an oxidation reaction of the corresponding sulfide compounds of the formula I, wherein X is S (ie , a compound of formula Ic above), involving reagents such as, for example, m-chloroperoxybenzoic acid (mCPBA), hydrogen peroxide, oxone, sodium periodate, sodium hypochlorite or tert-butyl hypochlorite among other oxidants. The oxidation reaction is generally carried out in the presence of a solvent. Examples of the solvent to be used in the reaction include halogenated aliphatic hydrocarbons such as dichloromethane and chloroform; alcohols such as methanol and ethanol; Acetic Acid; Water; and its mixtures. The amount of the oxidant to be used in the reaction is generally 1 to 3 moles, preferably 1 to 1.2 moles, relative to 1 mole of the sulfide compounds Ib to produce the sulfoxide compounds I (where X = SO), and preferably 2 to 2.2 moles of oxidant, relative to 1 mole of the sulphide compounds Ic to produce the sulfone compounds I (wherein X = SO2). Such oxidation reactions are disclosed, for example, in WO 2013/018928.
[0058] The compounds of formula III
are known, are commercially available or can be prepared by methods known to a person skilled in the art. Examples of known compounds (CAS number) include 4-Amino-6-bromopyrimidine ([1159818-57-1]), 4-Pyrimidinamine ([6-(trifluoromethyl)pyrimidin-4-amine ([1232134-17-6]) , 6-aminopyrimidine-4-carbonitrile ([1353100-84-1 ]), 6-cyclopropylpyrimidin-4-amine ([7043-08-5]), 6-cyclobutylpyrimidin-4-amine ([1557338-24-5] ), 4-(Difluoromethyl)pyridin-2-amine ([1346536-47-7]), 4-Bromopyridin-2-amine ([84249-14-9]), 2-Amino-4-(trifluoromethyl)pyridine ( [106447-97-6]), 4-(1,1-difluoroethyl)pyridin-2-amine ([1522240-28-3]), 5-cyclopropylpyridazin-3-amine ([1619898-27-9]), 5-(trifluoromethyl)-3-Pyridazinamine ([1211591-88-6]), and 5-bromo-3-Pyridazinamine ([1187237-00-8]).
[0059] The compounds of formula IV,
wherein Z is X-R1 or a labile group or a group that could be transformed into a labile group such as, for example, halogen, amine or nitro, and wherein X, R1, L1, L2, L3, L4 and A are as described under formula I above, are known, are commercially available or can be prepared by methods known to a person skilled in the art. Compounds of formula IVb, wherein Q is as defined above, and wherein Z is a labile group, for example halogen, preferably fluorine, chlorine, and wherein A, L1, L2, L3 and L4 are as described under the formula I above, and wherein R01 is C1-C4 alkyl or hydrogen, can be reacted with compounds of the formula VIII R1-SH (VIII), or a salt thereof, wherein R1 is as defined in formula I, optionally in the presence of a base suitable, such as alkali metal carbonates, for example sodium carbonate and potassium carbonate, or alkali metal hydrides such as sodium hydride, or alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, in a solvent inert to temperatures preferably between 25-120 °C, to generate compounds of formula IVc, wherein R01 is C1-C4 alkyl or hydrogen, R1 is as described under formula I above, and in which A, L1, L2, L3 and L4 are as described under formula I above. Examples of solvents to be used include ethers such as THF, ethylene glycol dimethyl ether, tert-butylmethyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile or polar aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethyl sulfoxide. Examples of salts of the compound of the formula VIII include compounds of the formula VIIIa; R1-SM (VIIIa), where R1 is as defined above and where M is, for example, sodium or potassium. This is illustrated for compounds of formula IVc in scheme 3: Scheme 3

[0060] Alternatively, compounds of formula IVd, wherein Z1 is NH2 and wherein A, L1, L2, L3 and L4 are as described under formula I above, and wherein R01 is C1-C4 alkyl or hydrogen, may be transformed into compounds of the formula IVb by diazotization and reaction of the diazonium salt with a sulfide of the formula R1S-SR1. This transformation can be carried out by methods known to a person skilled in the art and as described, for example in Synthetic Communications, 31 (12), 1857-1861, 2001 or Organic & Biomolecular Chemistry, 6 (4), 745-761 , 2008. In an alternative synthesis, compounds of formula IVc, wherein Z1 is NH2 and wherein A, L1, L2, L3 and L4 are as described under formula I above, and wherein R01 is C1-C4 alkyl or hydrogen , can be transformed into compounds of the formula IVb by diazotization and reaction with sodium sulfide, followed by reduction of the disulfide with for example Zinc in acetic acid to give compounds of the formula IVe. This transformation has been described for example in US 20040116734 and Chemische Berichte, 120 (7), 1151-73, 1987. The alkylation of compound IVe with R1-XLG, wherein R1 is as described under formula I above and wherein XLG is a labile group such as halogen, preferably iodine, bromine or chlorine, in the presence of a base such as sodium carbonate, potassium carbonate or cesium carbonate, or sodium hydride, in a suitable solvent such as for example N, N-dimethylformamide, N,N-dimethylacetamide or acetonitrile, to generate a compound of formula IVb, wherein R 1 is as described under formula I above (scheme 4) Scheme 4

[0061] Compounds of formula IV can be obtained by reacting a compound of formula IVb wherein R01 is C1-C4 alkyl through hydrolysis. For example, in the case where R01 is methyl or ethyl, the hydrolysis can be carried out with water and a base, such as potassium hydroxide or lithium hydroxide, in the absence or presence of a co-solvent, such as tetrahydrofuran or methanol. In the case where R01 is, for example, tert-butyl, the hydrolysis is carried out in the presence of acid, such as trifluoroacetic acid, or hydrochloric acid. The reaction is carried out at a temperature of -120 °C to +130 °C, preferably -100 °C to 100 °C (scheme 5) Scheme 5

[0062] Alternatively, the compound of formula IV can be prepared by reacting a compound of formula VIIa wherein Z is a labile group such as nitro or halogen such as fluorine and wherein A, L1, L2, L3 and L4 are as described under formula I above by reacting a compound of formula VIII or VIIIa R 1 -SH (VIII), R 1 -SM (VIIIa), to give compounds of formula VIIb or a salt thereof, wherein R 1 is as defined in formula I, optionally in the presence of a suitable base such as alkali metal carbonates, for example sodium carbonate and potassium carbonate, or alkali metal hydrides such as sodium hydride, or alkali metal hydroxides such as sodium hydroxide and potassium hydroxide , in an inert solvent at temperatures preferably between 25-120°C, to generate compounds of the formula VIIb, in which R1 is as described under formula I above, and in which A, L1, L2, L3 and L4 are as described under formula I above. Examples of solvents to be used include ethers such as THF, ethylene glycol dimethyl ether, tert-butylmethyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile or polar aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethyl sulfoxide. Examples of salts of the compound of formula VIII include compounds of the formula VIIIa R 1 -SM (VIIIa), where R 1 is as defined above and where M is, for example, sodium or potassium. Compounds of formula IV can be prepared by hydrolysis of the cyano compound of formula VIIb under acidic or basic conditions. This transformation is well known and could be performed by methods known to a person skilled in the art (see for example: Comprehensive Organic Transformations: A Guide to Functional Group Preparations. Edited by Richard C. Larock 1989, p993, VCH publishers). This is illustrated for the compounds of formula II in scheme 6. Scheme 6

The compounds of formula VIIa are known, are commercially available or can be prepared by methods known to a person skilled in the art. Alternatively, the compound of the formula IV can be prepared by reacting a compound of the formula IX where Z is a labile group such as nitro or halogen, such as fluorine, or an X-R1 group, and where A, L1, L2 , L3 and L4 are as described under formula I above, by oxidation in the presence of an oxidant such as oxygen, hydrogen peroxide or a metal oxide such as chromium trioxide, optionally in the presence of acid such as sulfuric acid with or without metal catalyst. Such oxidations of methyl to carboxylic acids are well known in the literature (see for example: Comprehensive Organic Transformations: A Guide to Functional Group Preparations. Edited by Richard C. Larock 1989, p 823, VCH publishers). This is illustrated for the compounds of formula IV in scheme 7. Scheme 7

The compounds of formula IX are known, are commercially available or can be prepared by methods known to a person skilled in the art.
[0065] The compound of the formula IIc, wherein R is Alkyl C1C6, A, L1, L2, L3 and L4 are as described under the formula I above and Z is NH2, can be prepared by reacting a compound of the formula (XIV ) with a compound of the formula XV wherein, for example, X00 is a halogen such as, for example, bromide and R is C1-C6 alkyl such as, for example, ethyl. These reactions are known to a person skilled in the art and are, for example, described in Tetrahedron, 60 (2004) 2937-2942. This is illustrated for compounds of formula IIc in scheme 8. Scheme 8
Alternatively, the synthesis of compounds of formula I (benzimidazoles (J19 and J23) wherein: L1 = N or NR10a, L2 = C-R10b, L3 = N or N-R10c, L4 = bond; benzothiadiazoles (J20): L1 = N, L2 = S, L3 = N, L4 = bond; benzothiazoles (J12): L1 = N, L2 = C-R10b, L3 = S, L4 = bond; benzotriazoles (J18, J17 and J24): : L1 = N or N-R10a, L2 = N or N-R10b, L3 = N or N-R10c, L4 = bond; benzoxazoles (J25): L1 = N, L2 = C-R10b, L3 = O, L4 = bond) can be carried out by cyclization of intermediates of formula XII or XIII as illustrated in scheme 9. The synthesis of cyclic compounds as described in scheme 9 is well known and could be carried out by methods known to a person skilled in the art by analogy with what has been previously described in the literature . For example, for the synthesis of benzimidazoles starting from intermediate type XIII (see Monatshefte fuer Chemie 2011, 142 (1), 87-91 or Organic Preparations and Procedures International, 2013, 45 (1), 57-65 or Org. Prep. Proc. Int. 2013, 45 (2), 162-167 or Tet. Lett., 2007 48 (18), 3251-3254) or starting from intermediate type XII, as for example in J. Org. Chem ., 2011, 76 (23), 9577-9583 or Tetrahedron 2013, 69 (6), 17171719. In general see the review on the preparation of benzimidazoles in The Chemistry of Heterocyclic Compounds; Weissberger, A., Taylor, EC, Eds. Wiley-VCH: New York, NY, 1981; Vol. 40, pp 6-60. For the synthesis of benzothiazoles starting from type XIII intermediate see Tetrahedron 2005, 61 (46), 10975-10982. For a more general review of the preparation and properties of benzimidazoles see; Eur. J. Org. Chem. 2013, 228-255. For the synthesis of benzothiazoles starting from intermediate type XIII see for example Bio. Med. Chem., 2010, 18 (24), 8457-8462, using cyclocondensation chemistry as described in Scheme 9 (e.g., AcOH, NaNO2). For a more general overview of the preparation of benzotriazoles, see, for example, J. Chem. Pharm. Res., 2011, 3 (6), 375-381. For the synthesis of benzothiazoles starting from intermediate type XII see, for example, J. Comb. Chem., 2009, 11 (6), 1047-1049; Chemistry - A European Journal, 2012, 18 (16), 4840-4843, or WO13066729. Additionally, the synthesis of benzothiazoles is well known and can easily be by methods known to those skilled in the art via other type of intermediates (see, for example, J., Curr., Pharm., Res., 2010, 3 (1) , 13-23). Scheme 9: Alternative preparation of compounds of formula I:

The compounds of formulas X and XI can be prepared by in analogy to reactions described in the literature (see JP 2014208695, WO 2014125651, WO 2014119670, WO 2014119679, WO 2014119674, WO 2014119494, WO 2014119699, WO 2014119672, JP 2014111558, and WO 2013018928).
[0067] Compounds of formula Ib, and I containing an NH such as L1, L2 or L3 can be reacted with an alkylating agent such as methyl iodide in the presence of a base such as potassium carbonate or sodium hydride, to give compounds of the formula Ib, and I wherein L1, L2 or L3 is an N-CH3.
[0068] The compounds of formula IV, respectively IVe, IVf, IVg, and IVh, wherein L1 is oxygen, or S(O)n1 (wherein n1 is 0, 1 or 2), R10a, R10b and R10c are as previously defined and R10e is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, and C3-C6 halocycloalkyl, R001 is C1-C4C6 alkyl, and Z is X1-R1, can be prepared as shown in Scheme 10: Scheme 10.

[0069] As shown in scheme 10, the synthesis requires: 1. Reaction of compounds of the formula XVI, wherein Z is X1-R1, with compounds of the formula XVIII (wherein X00 is a labile group such as halogen, mesylate, or tosylate) in the presence of a base such as potassium carbonate in a solvent such as acetone, acetonitrile or dimethylformamide or a mixture of solvents such as dimethylformamide and acetone, optionally in the presence of a catalyst such as sodium iodide. The formation of allyl XVII ethers is analogous to transformations well known to those skilled in the art, and analogous reactions have been described, for example, in Organic Letters, 17 (12), 3118-3121; 2015; Tetrahedron, 2004, 60, 7973-7981. Alternatively, compounds of formula XVII can be prepared as shown in scheme 11. Scheme 11
The reaction of a compound of the formula XX, wherein R001, Z and A are as previously described and X001 is halogen, R001 is C1-C4 alkyl, Z is X-R1, and A is as defined in formula 1 with a compound of the formula XX1, where R10a, R10b, R10c, and R10e are as previously defined and L1 is sulfur or oxygen in the presence of a base, such as sodium hydride or cesium carbonate, in an inert solvent such as DMF, leads to compounds of the XVII formula. 2. A Claisen rearrangement of compounds of formula XVII under heating conditions to give compounds of formula XIX. This reaction and the conditions for carrying it out are well known to persons skilled in the art, see for example "Strategic Applications of Named Reactions in Organic Synthesis" by Kurti, Laszlo; Czako, Barbara; Publishers; 2005, page 88. 3. Cyclization of compounds of formula XIX under acidic conditions, for example organic acids such as acetic or formic acid. Such reactions (intramolecular hydroxyalkoxylation) are well known to those skilled in the art and have been described in, for example, Ang. Chem. Int. Ed., 54 (13), 4014-4017, 2015 and cited references; ChemCatChem, 5(11), 3309-3315, 2013; Chemistry - A European Journal, 16 (11), 3403-3422, 2010references cited there; J. Org. Chem., 76 (22), 9353-9361; 2011.
The compounds of formula IVe obtained can be hydrolyzed to their corresponding acid IVg by methods known to those skilled in the art. Alternatively, the subgroup of compounds of the formula IVf wherein L1 is SO (sulfoxide) and/or SO2 (sulfone) can be obtained by means of an oxidation reaction of the corresponding sulfide compounds of the formula IVe, wherein L1 is sulfur, involving reagents such as, for example, m-chloroperoxybenzoic acid (mCPBA), hydrogen peroxide, oxone, sodium periodate, sodium hypochlorite or tert-butyl hypochlorite among other oxidants. The oxidation reaction is generally carried out in the presence of a solvent. Examples of the solvent to be used in the reaction include halogenated aliphatic hydrocarbons such as dichloromethane and chloroform; alcohols such as methanol and ethanol; Acetic Acid; Water; and its mixtures. Such oxidation reactions are disclosed, for example, in rom Ger. Offen., DE 10130709, 2002 and Ped. Int. PCT, WO 9909023, 1999
[0071] The preparation of compounds of formulas XX and XVI can be prepared by persons skilled in the art, by using protocols previously described in this patent, or with procedures described in WO 2015000715, US 20140018373 (WO 2012086848) or US 20140194290 (WO 2013018928). For preparing all other compounds of formula (I) functionalized according to the definitions of formula I there are a large number of suitable known standard methods, for example alkylation, halogenation, acylation, amidation, oximation, oxidation and reduction, depending on the choice of the methods of preparation that are suitable for the properties (reactivity) of the substituents in the intermediates.
[0072] Reagents 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 carbonates or alkaline earth metals, 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 hydroxides and carbocyclic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, diisopropylamide lithium, 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).
[0073] The reagents can be reacted with each other as is, that is, without the addition of a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which can be used in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, can also act as solvents or diluents. The reaction is advantageously carried out in a temperature range from approximately -80 °C to approximately +140 °C, preferably from approximately -30 °C to approximately +100 °C, and in many cases in the range between ambient temperature and approximately +80°C.
A compound of the formula I can be converted in a manner known per se into another compound of the formula I by replacing one or more substituents of the starting compound of the formula I in the usual manner by another substituent(s) according to the invention.
[0075] Depending on the reaction conditions and the chosen starting materials, which are appropriate for each case, it is possible, for example, in a reaction step, to replace only one substituent by another substituent according to the invention, or a plurality of substituents can be replaced by other substituents according to the invention in the same reaction step.
The salts of the compounds of the 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 exchange reagent, and salts with bases are obtained by treatment with a suitable base or a suitable ion exchange reagent . Salts of compounds of the formula I can be converted in the usual way to the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or a suitable ion exchange reagent, and salts with bases, by for example, by treatment with a suitable acid or with a suitable ion exchange reagent.
The salts of the compounds of the formula I may be converted in a manner known per se to other salts of the compounds of the formula I, acid addition salts, for example, to other acid addition salts, for example by treating a salt of an inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt is formed, for example chloride of silver, is insoluble and thus precipitates from the reaction mixture.
[0078] Depending on the procedure or the reaction conditions, the compounds of the formula I, which have salt-forming properties, can be obtained in free form or in the form of salts.
[0079] The compounds of 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 isomers which are possible or as a mixture thereof, for example in form of pure isomers, such as antipodes and/or diastereoisomers, or as mixtures of isomers, such as mixtures of enantiomers, for example racemates, mixtures of diastereoisomers or mixtures of racemates, depending on the number, absolute and relative configuration of the asymmetric carbon atoms that occur in the molecule and/or depending on the configuration of the non-aromatic double bonds that occur in the molecule; the invention relates to the pure isomers and also to all mixtures of isomers that are possible and is to be understood in each case in this sense here above and below, even when stereochemical details are not specifically mentioned in each case.
[0080] Mixtures of diastereoisomers or mixtures of racemates of the compounds of the formula I, in free form or in salt form, which can be obtained depending on the starting materials and procedures that have been chosen, can be separated in a manner known in the pure diastereoisomers or racemates based on the physicochemical differences of the components, for example, by fractional crystallization, distillation and/or chromatography.
[0081] Mixtures of enantiomers, such as racemates, which can be obtained in a similar manner can be resolved into optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example by chromatography high performance liquid (HPLC) in acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific immobilized enzymes, through the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion to diastereoisomeric salts, for example by reacting a racemate of the basic end-product with an optically active acid, such as a carboxylic acid, for example camphoric, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separation of the mixture of diastereoisomers which can be obtained in this way, for example by fractional crystallization based on their differences. solubilities, to give the diastereoisomers, from which the desired enantiomer can be released by the action of suitable agents, eg basic agents.
[0082] Pure diastereoisomers or enantiomers can be obtained according to the invention not only by separation of appropriate isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example, by carrying out the process according to the invention with starting materials exhibiting appropriate stereochemistry.
[0083] N-oxides can be prepared by reacting a compound of formula I with a suitable oxidizing agent, for example the H2O2/urea adduct in the presence of an acid anhydride, eg trifluoroacetic anhydride. Such oxidations are known from the literature, for example, from J. Med. Chem. 1989, 32, 2561 or WO 2000/15615.
[0084] It is advantageous, in each case, to isolate or synthesize the isomer, for example enantiomer or diastereoisomer, biologically more effective, or the mixture of isomers, for example mixture of enantiomers or mixture of diastereomers, biologically more effective if the individual components have different biological activity.
The compounds of the formula I and, where appropriate, their tautomers, in each case in free form or in salt form, may, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those that may have been used for the crystallization of compounds that are present in solid form.
The compounds according to the following Tables 1 to 4 below can be prepared according to the methods described above. The following examples are intended to illustrate the invention and show preferred compounds of formula I. "Ph" represents the phenyl group. Table 1: This table reveals the 128 compounds of formula I-1a:








and the N-oxides or tautomers of the compounds in Table 1. Table 2: This table lists the 128 compounds of formula I-1b:









and the N-oxides and tautomers of the compounds in Table 2. Table 3: This table lists the 128 compounds of formula I-1c:









and the N-oxides and tautomers of the compounds in Table 3.
[0087] The compounds of the formula I according to the invention are valuable active ingredients from a preventive and/or curative point of view in the field of pest control, even at low application rates, which have a very favorable biocidal spectrum and are good tolerated by warm-blooded species, fish and plants. The active ingredients according to the invention act against all developmental stages or individual developmental stages of normally sensitive but 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, ie in the destruction of pests, which takes place immediately or only after some time, for example during ecdysis, or indirectly, for example at a rate of oviposition and/or reduced hatching.
Examples of the animal pests mentioned above are: of the order Acarina, for example, Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp, Eotetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp. , Phytonemus spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp., Tarsonemus spp. and Tetranychus spp.; from the order Anoplura, for example Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; from the order Coleoptera, e.g. Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp, Atomaria linearis, Chaetocnema tibialis, Cerotoma spp, Conoderus sppnitida, Cosmopolites spp. spp., Cyclocephala spp., Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemcolas, Lisppor spp. Megascelis spp., Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp., Phlyctinus spp., Popillia spp., Psylliodes spp. spp., Somaticus spp., Sphenophorus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp. and Trogoderma spp.; from the order Diptera, for example Aedes spp., Anopheles spp., Antherigona soccata, Bactrocea oleae, Bibio hoTRulanus, Bradysia spp, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Deliapp., Cuterebra spp. spp, Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyza tripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp. ., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis spp., Rivelia quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; from the order Hemiptera, for example Acanthocoris scabrator, Acrosternum spp, Adelphocoris lineolatus, Amblypelta nitida, Bathycoelia thalassina, Blissus spp, Cimex spp., Clavigralla tomentosicollis, Creontiades spp, Eussatus sppder, Distantilla spp. ., Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp., Margarodes spp, Murgantia histrionic, Neomegalotomus spp. , Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp. , Thyanta spp., Triatoma spp., Vatiga illudens; AcyTRhosium pisum, Adalges spp, Agalliana ensigera, Agonoscena targionii, Aleurodicus spp, Aleurocanthus spp, Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinseppula, Aphitus sppula, Aphidi. Bactericera cockerelli, Bemisia spp., Brachycaudus spp, Brevicoryne brassicae, Cacopsylla spp., Cavariella aegopodii Scop., Ceroplaster spp. , Diaphorina citri, Diuraphis noxia, Dysaphis spp., Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae, Hyalopterus spp. Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp., Mahanarva spp., Metcalfa pruinosa, Met opolophium dirhodum, Myndus crudus, Myzus spp., Neotoxoptera sp., Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter, Parabemisia myricae, Partriompher, Partriomph. spp., Phorodon humuli, Phylloxera spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopphum spp. ., Schizaphis spp., Sitobion spp., Sogatella furcifera, Spissistilus festinus, Tarophagus Proserpina, Toxoptera spp, Trialeurodes spp., Tridiscus sporoboli, Trionymus spp, Trioza erytreae, Zayspisgini citris; from the order Hymenoptera, for example Acromyrmex, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp. Solenopsis spp. and Vespa spp.; from the order Isoptera, for example Coptotermes spp, Corniternes cumulans, Incisitermes spp, Macrotermes spp, Mastotermes spp, Microtermes spp, Reticulitermes spp.; Solenopsis geminate of the order Lepidoptera, for example Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp., Argyrotas spp. Bucculatrix thurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis flapp. , Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis, Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea, Earias spp., Eldana saccharina, Ephestia spp., Epinotia spp. , Euproctis spp., Euxoa spp., Feltia jaculiferia, Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp., Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus, Leucop tera scitella, Lithocollethis spp., Lobesia botrana, Loxostege bifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Mythimna spp, Noctua spp. , Pandemis spp., Panolis flammea, Papaipema nebris, Pectinophora gossypiela, Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spluschia spp. Sesamia spp., Sparganothis spp., Spodoptera spp., Sylepta derogate, Synanthedon spp., Thaumetopoea spp., ToTRrix spp., Trichoplusia ni, TutaAbsolute, and Yponomeuta spp.; from the order Mallophaga, for example, Damalinea spp. and Trichodectes spp.; from the order Orthoptera, for example Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., NeocuTRilla hexadactyla, Periplaneta spp. , Scapteriscus spp, and Schistocerca spp.; from the order Psocoptera, for example Liposcelis spp.; from the order Siphonaptera, for example, Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis; from the order Thysanoptera, for example, Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., PaTRhenothrips spp., SciTRothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp; from the order Thysanura, eg Lepisma saccharina. The active ingredients according to the invention can be used to control, i.e. contain or destroy, pests of the aforementioned type which occur in particular on plants, especially on plants useful and ornamental plants in agriculture, horticulture and forests, or in organs such as fruits, flowers, foliage, stems, tubers or roots of such plants, and in some cases even plant organs which are formed at a later time remain protected against these pests.
Suitable target crops are, in particular, cereals such as wheat, barley, rye, oats, rice, maize or sorghum; sugar beet, such as sugar beet or fodder beet; fruits, for example pomoid fruits, stone fruits or soft fruits such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops such as beans, lentils, peas or soybeans; oil crops such as rapeseed, mustard, poppies, olives, sunflowers, coconut, castor beans, cocoa or groundnuts; cucurbits such as pumpkins, cucumbers or melons; fibrous plants such as cotton, flax, hemp or jute; citrus fruits such as oranges, lemons, grapefruit or mandarins; vegetables and vegetables, such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes or peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, the Plantaginaceae family and latex plants.
[0090] The compositions and/or methods of the present invention can also be used in any ornamental and/or vegetable crops, including flowers, shrubs, broadleaved trees and evergreen trees.
For example, the invention can be used on any of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g., B. elatior, B. semperflorens, B. tubereux), Bougainvillea spp., Brachycome spp., Brassica spp. (ornamental), Calceolaria spp., Capsicum annuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemum spp., Cineraria spp. (C. maritime), Coreopsis spp., Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gergnamphalium,. globosa, Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (I. Walleriana), Iresines spp., Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesia spp., Tagetes spp. (carnation), Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (P. peltatum, P. Zonale), Viola spp. (pansy), Petunia spp., Phlox spp., Plecthranthus spp., Poinsettia spp., Parthenocissus spp. (P. quinquefolia, P. tricuspidata), Primula spp., Ranunculus spp., Rhododendron spp., Rosa spp. (rose), Rudbeckia spp., Saintpaulia spp., Salvia spp., Scaevola aemola, Schizanthus wisetonensis, Sedum spp., Solanum spp., Surfinia spp., Tagetes spp., Nicotinia spp., Verbena spp., Zinnia spp. and other plants in stratification. For example, the invention can be used on any of the following vegetable species: Allium spp. (A. sativum, A. cepa, A. oschaninii, A. porrum, A. ascalonicum, A. fistulosum), Anthriscus cerefolium, Apium graveolus, Asparagus officinalis, Beta vulgarus, Brassica spp. (B. oleracea, B. pekinensis, B. rapa), Capsicum annuum, Cicer arietinum, Cichorium endivia, Cichorum spp. (C. intybus, C. endivia), Citrillus lanatus, Cucumis spp. (C. sativus, C. melo), Cucurbita spp. (C. pepo, C. maxima), Cyanara spp. (C. scolymus, C. cardunculus), Daucus carota, Foeniculum vulgare, Hypericum spp., Lactuca sativa, Lycopersicon spp. (L. esculentum, L. lycopersicum), Mentha spp., Ocimum basilicum, Petroselinum crispum, Phaseolus spp. (P. vulgaris, P. coccineus), Pisum sativum, Raphanus sativus, Rheum rhaponticum, Rosemarinus spp., Salvia spp., Scorzonera hispanica, Solanum melongena, Spinacea oleracea, Valerianella spp. (V. locusta, V. eriocarpa) and Vicia faba. Preferred ornamental species include African Violet, Begonia, Dahlia, Gerbera, Hydrangea, Verbena, Rose, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, , Fuchsia, Salvia, Hortensia, rosemary, sage, St. John's wort, mint, peppers, tomato and cucumber.
[0092] The active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, legumes, corn, rice and soybean crops. The active ingredients according to the invention are additionally especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potatoes) and Chilo supressalis (preferably in rice).
[0093] In a further aspect, the invention may also relate to a method of controlling damage to plants and their parts by plant parasitic nematodes (Endoparasitic, Semi-endoparasitic and Ectoparasitic nematodes), especially plant parasitic nematodes such as nodule nematodes root, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other species of Meloidogyne; cyst-forming nematodes, Globodera Rostochiensis and other species of Globodera; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Angina species; Stem and leaf nematodes, Aphelenchoides species; Stinger nematodes, Belonolaimus longicaudatus and other species of Belonolaimus; Pine nematodes, Bursaphelenchus xylophilus and other species of Bursaphelenchus; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Boring nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheathed nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Dagger nematodes, Hoploaimus species; False root-knot nematodes, Nacobbus species; Needle-shaped nematodes, Longidorus elongatus and other Longidorus species; Root lesion nematodes, Pratylenchus species; Lesion-forming nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Cave nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species; Scutellonema species; Root shortening and thickening nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other species of Tylenchorhynchus; Citrus nematodes, Tylenchulus species; Dagger-shaped nematodes, Xiphinema species; and other plant parasitic nematode species, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp..
[0094] The compounds of the invention may also have activity against molluscs. Examples of which include, for example, Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. Nemoralis); ochlodine; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H. obvia); Helicidae (Helicigona bushrum); Helicodiscus; Helix (H. tightens); 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.
[0095] The term "crops" is to be understood to also include crop plants that have been so transformed by the use of recombinant DNA techniques that they are capable of synthesizing one or more selectively acting toxins, such as are known, for example, to from toxin-producing bacteria, especially those of the genus Bacillus.
Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9c, or vegetative insecticidal proteins (Vip), e.g., Vip1, Vip2 , Vip3 or Vip3A; or insecticidal proteins from nematode colonizing bacteria, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomyces toxins, plant lectins, such as pea lectins, barley lectins or white bell lectins; agglutinins; proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome inactivating proteins (RIP), such as ricin, maize RIP, abrin, luphine, saporin or briodin; steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers such as sodium or calcium channel blockers , juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
[0097] In the context of the present invention are to be understood by δ-endotoxins, for example, Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A, also expressly hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are recombinantly produced by a new combination of different domains of these proteins (see, for example, WO 02/15701). Truncated toxins, for example a truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids from the naturally occurring toxin are replaced. In such amino acid substitutions, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin G recognition sequence is inserted into a Cry3A toxin (see WO 03/018810 ).
[0098] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP- A-451 878 and WO 03/052073.
[0099] Processes for the preparation of such transgenic plants are generally known to the person 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-0 367 474, EP-A-0 401 979 and WO 90/13651.
[0100] The toxin contained in transgenic plants gives plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in beetles (Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).
[0101] Transgenic plants containing one or more genes that encode an insecticide resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1Fa2 toxin and the enzyme phosphinothricin-N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresses a Cry1Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a Cry1Ab toxin); NewLeaf® (variety of potato that expresses a Cry3A toxin); NatureGard®, Agrisure® GT Advantage (glyphosate tolerant trait GA21), Agrisure® CB Advantage (corn borer (CB) trait Bt11) and Protecta®.
[0102] Additional examples of such transgenic crops are: 1. Bt11 corn from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays that was made resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Bt11 corn also transgenically expresses the PAT enzyme to achieve tolerance to the herbicide glufosinate ammonium. 2. Corn Bt176 from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays that was made resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a Cry1Ab toxin. Bt176 corn also transgenically expresses the PAT enzyme to achieve tolerance to the herbicide glufosinate ammonium. 3. MIR604 corn from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Corn that has been made insect resistant through 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. 4. MON 863 corn from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects. 5. IPC 531 cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02. 6. Corn 1507 from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified corn for the expression of Cry1F protein to achieve resistance to certain Lepidoptera insects and PAT protein to achieve tolerance to the herbicide glufosinate ammonium. 7. Corn NK603 x MON 810 from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. It consists of hybrid maize varieties conventionally improved by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 maize transgenically expresses the CP4 EPSPS protein, obtained from the Agrobacterium sp. CP4, which confers tolerance to the Roundup® herbicide (contains glyphosate), and also a Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki that provides tolerance to certain Lepidoptera, including the European corn borer.
[0103] Transgenic crops of insect resistant plants are also described in BATS (Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).
[0104] The term "crops" should be understood to also include crop plants that have been so transformed by the use of recombinant DNA techniques, capable of synthesizing antipathogenic substances that have a selective action, such as, for example, the so-called "proteins pathogenesis-related" (PRP, see, eg, EP-A-0 392 225). Examples of such anti-pathogenic substances and transgenic plants capable of synthesizing such anti-pathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191. Methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Crops can also be modified for heightened resistance to fungal (eg, Fusarium, Anthracnose, or Phytophthora), bacterial (eg, Pseudomonas) or viral (eg, potato leaf-rolling virus, virion virus) pathogens. tomato head, cucurbit mosaic virus).
[0105] Crops also include those that have heightened resistance to nematodes, such as the soybean cyst nematode.
[0106] Crops that are tolerant to abiotic stress include those that have enhanced tolerance to drought, too much salt, high temperature, glacial cold, frost, or light radiation, for example through the expression of NF-YB or other proteins known in the art .
[0107] Antipathogenic substances that can be expressed by such transgenic plants include, for example, ion channel blockers such as sodium and calcium channel blockers, for example the viral toxins KP1, KP4 or KP6; stilbene synthases; bibenzyl synthases; chitinases; glucanases; so-called "pathogenesis-related proteins" (PRPs; see eg EP-A-0 392 225); anti-pathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see eg WO 95/33818) or protein or polypeptide factors involved in plant defense against pathogens (so-called "plant disease resistance genes" ", as described in WO 03/000906).
[0108] Other areas of use of the compositions according to the invention are the protection of stored goods and warehouses, and the protection of raw materials such as wood, textiles, floor or building coverings, and also in the hygiene sector, in particular the protection of humans, domestic animals and productive livestock against pests of the mentioned type. The present invention also provides a method 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 compositions of the invention to the target pests, their locus or a surface or substrate by brushing, rolling, spraying, spreading or dipping. By way of example, an IRS (internal residual spray) application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention. In another embodiment, the application of such compositions to a substrate such as a non-woven or woven material in the form of (or which can be used in the manufacture of) knits, clothing, bedding, curtains and tents is contemplated. A further object of the invention is therefore a substrate selected from non-woven or woven material, comprising a composition containing a compound of formula I.
[0109] In one embodiment, the method for controlling such pests comprises applying a pesticide-effective amount of the compositions of the invention to the target pest, its locus, or a surface or substrate so as to provide an effective residual pesticidal activity on the surface or substrate. Such application may be by brushing, rolling, spraying, spreading or dipping the pesticidal composition of the present invention. By way of example, an IRS application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention, so as to provide effective residual pesticidal activity on the surface. In another embodiment, the application of such compositions for residual pest control to a substrate such as a woven material in the form of (or which can be used in the manufacture of) knitwear, clothing, bedding, curtains and tents is contemplated.
[0110] Substrates including nonwovens, fabrics or knits to be treated can be made of natural fibers such as cotton, raffia, jute, linen, sisal, plain warp, or wool, or synthetic fibers such as polyamide, polyester, polypropylene, polyacrylonitrile or the like. Polyesters are particularly suitable. Methods of treating textiles are known, e.g., WO 2008/151984, WO 2003/034823, US 5631072, WO 2005/64072, WO 2006/128870, EP 1724392, WO2005113886 or WO 2007/090739.
[0111] Other areas of use of the compositions according to the invention are the area of tree injection/trunk treatment for all ornamental trees, as well as all types of fruit trees and chestnut trees.
[0112] In the area of tree injection/trunk treatment, the compounds according to the present invention are especially suitable against wood-boring insects of the order Lepidoptera as mentioned above and of the order Coleoptera, especially against wood-borers listed in the following tables A and B: Table A. Examples of exotic wood punches of economic importance.

Table B. Examples of economically important native woodborers.





[0113] The present invention can also be used to control any insect pests that may be present in grass, including, for example, beetles, caterpillars, fire ants, earth pearls, diplopods, armadillos, mites, paquinhas, mealy bugs, mealy bugs, ticks, leafhoppers, southern grass bugs and white larvae. The present invention can also be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults.
[0114] In particular, the present invention can be used to control insect pests that feed on turfgrass roots including grubs (such as Cyclocephala spp. (for example, masked beetle C. lurida), Rhizotrogus spp. (for example, european beetle, R. majalis), Cotinus spp. (eg, green June beetle, C. nitida), Popillia spp. /June), Ataenius spp. (eg Black turf Ataenius, A. spretulus), Maladera spp. (eg Asian garden beetle, M. castanea) and Tomarus spp.), Earthpears (Margarodes spp.), paquinhas (orange, southern and short-winged; Scapteriscus spp., Gryllotalpa africana) and crane fly larvae (European crane fly, Tipula spp.). The present invention can also be used to control culm-dwelling lawn insect pests, including military caterpillars (such as corn fall armyworm Spodoptera frugiperda, and grazing caterpillar Pseudaletia unipuncta), threadworm, weevils (Sphenophorus spp., such as S. venatus verstitus and S. parvulus), and turf moths (such as Crambus spp. and the tropical turf moth, Herpetogramma phaeopteralis).
[0115] The present invention can also be used to control grass insect pests that live above ground and feed on grass leaves, including grass bugs (such as southern grass bugs, Blissus insularis), grass mites Bermuda shorts (Eriophyes cynodoniensis), Rhodes grass mealy bugs (Antonina graminis), leafhopper with two lines (Propsapia bicincta), leafhoppers, spinachworms (family Noctuidae), and green aphids.
[0116] The present invention can also be used to control other grass pests such as imported red fire ants (Solenopsis invicta) that raise a lot of ants in the grass.
[0117] In the hygiene sector, the compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, scabies mites, thrombotic mites, flies (biting and licking), parasitic fly larvae, lice, lice of hair, bird lice and fleas.
[0118] Examples of such parasites are: From the order Anopluride: Haematopinus spp., Linognathus spp., Pediculus spp. and Phtirus spp., Solenopotes spp.. From the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp.. From the order Diptera and from the suborders Nematocerin and Brachycerina, for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp. spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Morellia spp. , Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., WohlfahTRia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.. From the order Siphonapterida, e.g. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.. From the order Heteropterida, e.g. Cimex spp., Triatoma spp., Rhodnius spp., Panstrong.ylus spp. order Blattarida, for example Blatta orientalis, Periplaneta americana, Blattelagermanica and Supella spp.. From the subclass Acaria (Acarida) and from the orders Meta- and Meso-stigmata, for example Argas 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.. From the orders Actinedida (Prostigmata) and Acaridida (Astigmata), for example Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Trombicula spp. Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes. and Laminosioptes spp.
[0119] The compositions according to the invention are also suitable for protection against insect infestations in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and cardboard, leather, floor coverings and buildings.
The compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobctuus carpini , Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, spec. of Xyleborus, spec. from Tryptodendron, Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, spec. of Sinoxylon and Dinoderus minutus, and also Hymenoptera such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus augur, and termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicolaensis, Reticuliteres, Reticulitermes, Reticuliteres, Reticuliteres, nevadensis and Coptotermes formosanus, and silverfish such as Lepisma saccharina.
[0121] The compounds according to the invention can be used as pesticidal agents in unmodified form, but are generally formulated into compositions in various forms using formulation aids such as carriers, solvents and surface-active substances. The formulations may be in various physical forms, e.g., in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent granules, emulsifiable concentrates, microemulsifiable concentrates, oil-in-oil emulsions. water, flowable oils, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water soluble concentrates (with water or a water-miscible organic solvent as carrier), polymer films impregnated or other known forms, eg, from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can be used directly or diluted before use. Dilutions can be made, for example, with water, in liquid fertilizers, micronutrients, biological organisms, oil or solvents.
[0122] The formulations can be prepared, for example, by mixing the active ingredient with the formulation adjuvants, in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.
[0123] The active ingredients can also be contained in very thin microcapsules. Microcapsules contain the active ingredients in a porous carrier. This allows the active ingredients to be released into the environment in controlled amounts (eg slow release). Microcapsules are usually 0.1 to 500 microns in diameter. They contain active ingredients in an amount of about 25 to 95% by weight of the capsule weight. The active ingredients may be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. Encapsulation membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person expert in the technique. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
[0124] Formulation aids which are suitable for the preparation of the compositions according to the invention are known per se. As liquid carriers can 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, acetic acid alkyl esters, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether , diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol , ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, acetate d and glycerol, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxymethyl ketone and isoamyl, isobutyl methyl ketone, methyl laurate, methyl octanoate, 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, xylene sulphonic acid, paraffin, mineral oil, trichlorethylene, perchlorethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and higher molecular weight alcohols, ta is such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like.
[0125] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cotton seed husks, wheat flour , soy flour, pumice, wood flour, crushed walnut shells, lignin and similar substances.
[0126] A large number of surface active substances can be advantageously used in solid and liquid formulations, especially in those formulations that can be diluted with a carrier before use. Surface active substances can be anionic, cationic, nonionic or polymeric and can be used 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 nonylphenol ethoxylate; alcohol/alkylene oxide addition products such as tridecyl alcohol ethoxylate; soaps such as sodium stearate; salts of alkyl naphthalene sulfonates such as sodium dibutyl naphthalene sulfonate; dialkyl esters of sulfosuccinate salts such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters such as sorbitol oleate; quaternary amines such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids such as polyethylene glycol stearate, block copolymers of ethylene oxide and propylene oxide, and esters of mono- and di-alkyl phosphate salts; and also additional substances described, e.g., in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981).
[0127] Additional adjuvants that can be used in pesticide formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, substances neutralizers or pH modifiers and buffers, corrosion inhibitors, fragrances, wetting agents, adhesion enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze, microbicides and liquid and solid fertilizers.
[0128] The compositions according to the invention may include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally 0.01 to 10%, based on the mixture to be applied. For example, the oil additive can be added to a spray tank at the desired concentration after a spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of vegetable oils, for example those derived from methyl, or a animal oil, such as fish oil or beef tallow. Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th Edition, Southern Illinois University, 2010.
[0129] The inventive compositions generally comprise from 0.1 to 99% by weight, especially from 0.1 to 95% by weight, of the compounds of the present invention and from 1 to 99.9% by weight of a formulation aid which preferably includes from 0 to 25% by weight of a surface-active substance. While commercial products can preferably be formulated as concentrates, the end user will normally employ diluted formulations.
[0130] Application rates vary within wide limits and depend on the nature of the soil, the application method, the crop plant, the pest to be controlled, prevailing weather conditions, and other factors controlled by the application method, the time of application and the target culture. As a general guideline, the compounds can be applied at a rate of 1 to 2000 L/ha, especially 10 to 1000 L/ha.
[0131] Preferred formulations may have the following compositions (% by weight): Emulsifiable concentrates: active ingredient: 1 to 95%, preferably 60 to 90% surfactant: 1 to 30%, preferably 5 to 20% liquid carrier: 1 to 80%, preferably 1 to 35% Dust: active ingredient: 0.1 to 10%, preferably 0.1 to 5% solid carrier: 99.9 to 90%, preferably 99.9 to 99% Suspension concentrates: ingredient active: 5 to 75%, preferably 10 to 50% water: 94 to 24%, preferably 88 to 30% surfactant: 1 to 40%, preferably 2 to 30% Wettable powders: active ingredient: 0.5 to 90%, preferably 1 to 80% surfactant: 0.5 to 20%, preferably 1 to 15% solid carrier: 5 to 95%, preferably 15 to 90% Granules: active ingredient: 0.1 to 30%, preferably 0.1 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%
[0132] The Examples below further illustrate, but do not limit, the invention.


[0133] The combination is thoroughly mixed with the adjuvants and the mixture is carefully ground in a suitable mill, providing wettable powders that can be diluted with water to give suspensions of the desired concentration.

[0134] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, giving powders that can be used directly for seed treatment.


[0135] Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.

[0136] Ready-to-use powders are obtained by mixing the combination with the vehicle and grinding the mixture in a suitable mill. Such powders can also be used for dry coatings for seeds.

[0137] The blend is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

[0138] The finely ground blend is evenly applied, in a mixer, to kaolin moistened with polyethylene glycol. In this way, non-dusty coated granules are obtained.

[0139] The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using these dilutions, live plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or dipping. Flowable concentrate for seed treatment

[0140] The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using these dilutions, live plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or dipping. Suspension of Slow Release Capsules
[0141] 28 parts of a combination are mixed with 2 parts of an aromatic solvent and 7 parts of the mixture of diisocyanate/polymethylene-polyphenylisocyanate toluene (8:1). This mixture is emulsified in a mixture of 1.2 parts polyvinyl alcohol, 0.05 parts defoamer and 51.6 parts water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water is added. The mixture is stirred until the polymerization reaction is complete. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The suspension formulation for capsules contains 28% of the active ingredients. The average diameter of the capsules is 8 to 15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in an apparatus suitable for that purpose.
[0142] Formulation types include an emulsion concentrate (EC), a suspension concentrate (SC), a suspoemulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a microemulsion (ME), a dispersion in oil (OD), an oil miscible fluid (OF), a miscible liquid in oil (OL), a soluble concentrate (SL), an ultra low volume suspension (SU), an ultra low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP ), a soluble granule (SG) or any technically possible formulation in combination with agriculturally acceptable adjuvants. Preparatory examples:
[0143] "Mpt." means melting point in °C. Free radicals represent methyl groups. 1H NMR measurements were recorded on a Brucker 400MHz spectrometer, chemical shifts are given in ppm from a TMS standard. Spectra were measured in the indicated deuterated solvents. LCMS Methods: Method A:
[0144] The spectra were recorded on a Waters Mass Spectrometer (SQD, SQDII or ZQ Single Quadrupole Mass Spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Range of the cone: 30-60 V, Extractor: 2.00 V, Source Temperature: 150 °C, Desolvation Temperature: 350 °C, Cone Gas Flow: 0 L/Hour, Desolvation Gas Flow: 650 L/ Hour, Mass range: 100 to 900 Da) and a Waters UPLC Acquity: Binary pump, heated column compartment and diode array detector. Solvent degasser, binary pump, heated column compartment and diode array detector. Column: UPLC HSS T3 from Waters, 1.8mm, 30x2.1mm, Temp: 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 to 100% B in 1.2 min; Flow (ml/min) 0.85. Example P1:3-ethylsulfonyl-2-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]quinolone (compound P1, Table P).

[0145] To stirred solution of ethyl 3-aminoquinoline-2-carboxylate (3.6 g, 16.66 mmol, prepared as described in WO 2011093365) and diethyl sulfide (4.51 mL, 36.6 mmol), in dichloroethane (30 ml), t-butyl nitrite was added dropwise at room temperature. The reaction mixture was heated to 40°C for 2 hours. After completion of the reaction (TLC analysis), the reaction mixture was diluted with dichloromethane and washed with water (2 x 10 mL). The combined organic layer was dried over Na2SO4, filtered, and concentrated in vacuo. The crude was purified by flash silica gel chromatography to give the title compound as a yellow liquid. 1H NMR (400 MHz, CDCl 3 ): (ppm): 8.14 (d, 1H); 8.06(s, 1H); 7.75 (d, 1H); 7.68 (m, 1H); 7.58 (m, 1H); 4.54 (q, 2H); 3.03(q, 2H); 1.48(t, 3H) 1.40(t, 3H). Step B: 3-ethylsulfanylquinoline-2-carboxylic acid

[0146] To a stirred solution of ethyl 3-aminoquinoline-2-carboxylate (1 g, 3.8 mmol) in THF (8 mL) was added NaOH (2N, 8.36 mmol) at room temperature. The reaction mixture was stirred for 16 hours at room temperature. After completion of the reaction (TLC analysis), the reaction mixture was extracted with ethyl acetate (2 x 10 mL). The aqueous phase was then acidified to pH = 4 with 10% citric acid solution and extracted with ethyl acetate (3 X 20 ml). The combined organic extracts were dried over Na2SO4, filtered, and concentrated in vacuo. Trituration with ether gave the desired title compound as a yellow solid. 1H NMR (400 MHz, DMSO-d6): (ppm): 13.7 (s, 1H); 8.42 (s, 1H); 8.00(m, 2H); 7.75 (m, 1H); 7.68 (m, 1H); 3.09 (q, 2H); 1.29 (t, 3H). Step C:3-Ethylsulfanyl-N-methoxy-N-methyl-quinoline-2-Carboxamide

[0147] 3-Ethylsulfanylquinoline-2-carboxylic acid (0.8 g, 3.43 mmol) was dissolved in dichloromethane (12 mL) under an atmosphere of argon. To this were added 2 drops of dimethylformamide and then oxalyl chloride (0.3889 ml, 4.458 mmol). The reaction was stirred for 3 hours at room temperature, at which time LCMS analysis of an aliquot treated with MeOH showed that complete conversion to 3-ethylsulfanylquinoline-2-carbonyl chloride had occurred. The reaction mixture was concentrated in vacuo and used without further purification for the next step.
[0148] A solution of N-methoxymethanamine hydrochloride (0.3345 g, 3.429 mmol) in dichloromethane (13 mL) and triethylamine (1.67 mL, 12.00 mmol) was cooled to 0 °C and treated with 3- ethylsulfanylquinoline-2-carbonyl (0.863 g, 3.429 mmol) dissolved in 3 mL of dichloromethane at 0 °C.
[0149] The reaction mixture was allowed to warm to room temperature and stirred for 30 min. LCMS analysis after this time showed completion of the reaction. The reaction mixture was diluted with saturated aqueous NH4Cl, and the aqueous layer was extracted 3 times with dichloromethane. The combined organic layers were successively washed with water and brine, dried over Na 2 SO 4 , filtered and concentrated in vacuo to give the crude product. This was purified by flash chromatography with a 24 g column and a 0-100% cyclohexane + ethyl acetate gradient to give the title compound as a yellow oil. 1H NMR (400 MHz, CHLOROFORM-d) ppm: 1.34 (t, J=7.34 Hz, 3H); 3.03 (q, J=7.34 Hz, 2H); 3.46 (s, 3H); 3.57 (s, 3H); 7.55 - 7.62 (m, 1H); 7.68 - 7.74 (m, 1H); 7.79 (d, J=8.44 Hz, 1H); 8.10 (d, J=8.44 Hz, 1H); 8.17 (s, 1H). LCMS (method 1); RT = 0.87 min, [M+H] 277. Step D: 1-(4-ethylsulfanyl-3-isoquinolyl)ethanone

[0150] A solution of bromo(methyl)magnesium (1.4 M in THF:Toluene 1:3 (1.9 mL, 2.605 mmol) in dry toluene (9 mL) was cooled to 0 °C and treated with 3- ethylsulfanyl-N-methoxy-N-methyl-quinoline-2-carboxamide (0.6 g, 2.171 mmol) dissolved in 3 mL of toluene The reaction mixture was stirred for 1 hour at 0°C and then 1 hour at room temperature LCMS analysis after this time showed completion of the reaction.The reaction mixture was slowly quenched with saturated aqueous NH4Cl and 10% HCl (15 mL) and the resulting mixture vigorously stirred for 15 min at room temperature. with ethyl acetate and the combined organic phases washed successively with 10% HCl aq sol, water and brine, dried over Na 2 SO 4 , filtered and concentrated in vacuo The crude product was purified by flash chromatography with a 12 g column and a column gradient cyclohexane + 0-80% ethyl acetate to give the title compound as a yellow solid.1H NMR (400 MHz, CLO ROFORMIUM-d) ppm: 1.46 (t, J=7.34 Hz, 3H); 2.87 (s, 3H); 3.04 (q, J=7.34 Hz, 2H); 7.58 - 7.65 (m, 1H); 7.65 - 7.71 (m, 1H); 7.76 (d, J=6.60 Hz, 1H); 7.99 (s, 1H); 8.10 (d, J=8.44 Hz, 1H). LCMS (method 1); RT= 1.04 min, [M+H] 232. Step E: 1-(4-ethylsulfonyl-3-isoquinolyl)ethanone

[0151] A solution of 1-(4-ethylsulfanyl-3-isoquinolyl)ethanone (0.375 g, 1.621 mmol) in dichloromethane (8 mL) was cooled to 0 °C and treated with meta-chloroperbenzoic acid (0.8393 g, 3.405 mmol). The reaction was stirred 30 min at 0 °C and then warmed to room temperature and stirred for 1 hr. LCMS analysis after this time showed completion of the reaction. The reaction mixture was quenched with 1 M NaOH (10 mL) and aqueous sodium thiosulfate solution (5 mL). The aqueous layer was extracted 3 times with dichloromethane and the combined organic phases washed successively with 1 M NaOH, brine, dried over Na 2 SO 4 , filtered and concentrated in vacuo to give the title product as a white solid. This was used in the next step without further purification. 1H NMR (400 MHz, CHLOROFORM-d) ppm: 1.39 (t, J=7.34 Hz, 3H); 2.85 (s, 3H); 3.68 (q, J=7.46 Hz, 2H); 7.74 - 7.81 (m, 1H); 7.98 (ddd, J=8.53, 7.06, 1.28 Hz, 1H); 8.04 (d, J=8.44 Hz, 1H); 8.22 (d, J=8.07 Hz, 1H); 8.91 (s, 1H). LCMS (method 1); RT = 0.84 min, [M+H] 264. Step F: 2-bromo-1-(3-ethylsulfonyl-2-quinolyl)ethanone

[0152] 1-(4-Ethylsulfonyl-3-isoquinolyl)ethanone (0.4 g, 1.519 mmol) was dissolved in chloroform (2 mL) and ethyl acetate (2 mL) in microwave flask and treated with bromide of copper(II) (0.6786 g, 3.038 mmol). The reaction mixture was then stirred in the microwave for 1 h at 140 °C. After this time, the reaction mixture was dissolved in dichloromethane, dried over Na2SO4, filtered and concentrated in vacuo. This was purified by flash silica gel chromatography to give the title compound as a white solid. 1H NMR (400 MHz, CHLOROFORM-d) ppm: 1.41 (t, J=7.52 Hz, 3H); 3.71 (q, J=7.46 Hz, 2H); 4.96 (s, 2H); 7.79 - 7.87 (m, 1H); 8.01 (ddd, J=8.53, 7.06, 1.28 Hz, 1H); 8.07 (d, J=8.07 Hz, 1H); 8.24 (d, J=8.44 Hz, 1H); 8.97 (s, 1H). LCMS (method 1); RT = 0.93 min, [MH] 342/344. Step G: 3-ethylsulfonyl-2-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]quinolone (compound P1, Table P)

[0153] In a microwave vial, 6-(trifluoromethyl)pyrimidin-4-amine (0.09532 g, 0.5845 mmol) and 2-bromo-1-(3-ethylsulfonyl-2-quinolyl)ethanone ( 0.2 g, 0.5845 mmol) dissolved in acetonitrile (7 mL) was stirred and heated for 1 hour at 150 °C. After this time, the reaction mixture was evaporated and the resulting solid dissolved in dichloromethane and washed with sol. sat NaHCO3. The organic layer was then washed with brine, dried over Na2SO4, filtered and concentrated in vacuo. Purification by flash chromatography with a 12g column and a gradient of dichloromethane + 0-10% ethylacetate gave the title compound as a white solid. 1H NMR (400 MHz, CHLOROFORM-d) ppm 1.40 (t, J=7.34 Hz, 3H); 3.96 (q, J=7.34 Hz, 2H); 7.77 (t, J=7.52 Hz, 1H); 7.92 - 8.01 (m, 1H); 8.01 (s, 1H); 8.09 (d, J=8.44 Hz, 1H); 8.25 (d, J=8.44 Hz, 1H); 8.43 (s, 1H); 9.12 (s, 1H); 9.24 (s, 1H). LCMS (method 1); RT = 0.91 min, [M+H] 407. Example P2 :2-[6-ethylsulfonyl-1-methyl-2-(trifluoromethyl)benzimidazol-5-yl]-7-(trifluoromethyl)imidazo[1,2 -c] pyrimidine (compound P2, Table P)

[0154] To a solution of 4-chloro-2-fluoro-5-nitro-benzoic acid (20 g, 91.095 mmol, commercially available, CAS [35112-05-1]) in 1-Methyl-2-pyrrolidone (250 mL) at 90 °C was added sodium t-butoxide (9.6302 g, 100.20 mmol). After 10 min, ethylsulfanylsodium (9.366 g, 100.20 mmol) was added and the reaction mixture stirred at 90°C for two hours. After this time, the reaction mixture was poured into water (1 L) and then acidified to pH 1 with conc. A precipitate formed and was filtered and then suspended in diethyl ether and filtered. The solid formed was filtered and shown to be pure 2,4-bis(ethylsulfanyl)-5-nitro-benzoic acid. The filtrate was concentrated in vacuo to give the title compound. 1H NMR (300 MHz, CDCl 3 ) ppm 13.84 (s, 1H) 8.52 (s, 1H); 7.6 (s, 1H); 3.09 (q, 2H); 1.3 (t, 3H). LC-MS (Method A): RT 1.00 min (260, MH-) (262, MH+). Step B: Synthesis of 2-ethylsulfanyl-4-(methylamino)-5-nitro-benzoic acid

[0155] To a solution of 4-chloro-2-ethylsulfanyl-5-nitro-benzoic acid (8.9 g, 34 mmol) in tetrahydrofuran (20 mL, 244 mmol) was added dropwise methylamine (2 mol/L ) in tetrahydrofuran (100 mL, 200 mmol). The mixture was stirred overnight at room temperature. LCMS analysis showed only minimal conversion to the desired product, after which the suspension was transferred to an autoclave, 30 mL of 2N methylamine was added, and the reaction was stirred at 80°C for 5 hours. After this time, an additional 20 mL of 2N methylamine was added, then the reaction was stirred in an autoclave for two days. The reaction mixture was concentrated in vacuo and the residue taken up in water, which was made basic with 1N sodium hydroxide, then extracted with ethyl acetate. The water phase was acidified with conc. 37% and extracted with ethyl acetate. All organic layers were combined, dried over magnesium sulfate, and concentrated in vacuo. The residue was purified by flash chromatography to give the title compound as a yellow-brown solid. 1H NMR (300 MHz, CDCl 3 ) ppm 12.87 (s, 1H) 8.68 (s, 1H); 6.55 (s, 1H); 3.05 (s, 3H); 3.00 (q, 2H) 1.33 (t, 3H). LC-MS (Method A): RT 1.04 min (257, MH+). Step C: 6-Ethylsulfanyl-1-methyl-2-(trifluoromethyl)benzimidazol-5-carboxylic acid

[0156] To a solution of 2-ethylsulfanyl-4-(methylamino)-5-nitro-benzoic acid (0.300 g, 1.17 mmol) in 2,2,2-trifluoroacetic acid (10 mL, 129 mmol) at 0°C °C, zinc (0.260 g, 3.98 mmol) was added and the cooling bath was removed. After 30 min, the reduction of the nitro group was complete according to LC/MS and a small amount of the title compound was observed. The brown solution was then heated to 70 °C product for 1 hr, after which LCMS showed completion of the reaction. The mixture was concentrated to half its volume, then poured into water and extracted with ethyl acetate. The organic phase was washed with water and brine, dried over magnesium sulfate and concentrated in vacuo. The residue was purified by flash chromatography to give the title compound. 1H NMR (300 MHz, CDCl 3 ) ppm 13.03 (s, 1H) 8.30 (s, 1H); 7.64 (s, 1H); 4.00 (s, 3H); 3.06 (q, 2H) 1.32 (t, 3H). LC-MS (Method A): RT 1.06 min (303, MH-) (305, MH+). Step D: Synthesis of 6-ethylsulfanyl-N-methoxy-N,1-dimethyl-2-(trifluoromethyl)benzimidazol-5-carboxamide

[0157] A solution of 6-ethylsulfanyl-1-methyl-2-(trifluoromethyl)benzimidazol-5-carboxylic acid (0.70 g, 2.3 mmol) in dichloromethane (11 mL) was treated with dimethylformamide (2 drops) and then oxalyl chloride (0.26 mL, 3.0 mmol) was added (gas formation) and the reaction mixture was stirred at room temperature overnight. After 16 hours, 0.2 ml oxalyl chloride was added and no further gas evolution was observed. The reaction mixture was evaporated to give 6-ethylsulfanyl-1-methyl-2-(trifluoromethyl)benzimidazol-5-carbonyl chloride which was used without further purification. A suspension of N-methoxymethanamine hydrochloride (0.23 g, 2.3 mmol) in dichloromethane (11 mL) was treated with triethylamine (1.1 mL, 8.0 mmol). The reaction mixture was cooled to 0 °C and 6-ethylsulfanyl-1-methyl-2-(trifluoromethyl)benzimidazol-5-carbonyl chloride (0.74 g, 2.3 mmol) dissolved in 3 mL of dichloromethane was added slowly. at this temperature. The reaction mixture was stirred 1.5 hours at 0°C. LC-MS analysis showed the formation of desired product. The reaction mixture was allowed to warm to room temperature and was quenched with water. The organic layer was separated and the aqueous layer was extracted 2 times with dichloromethane. The combined organic layer was dried over Na2SO4, filtered and concentrated in vacuo. The crude product was purified on silica gel cartridge to give the title compound. 1H NMR (400 MHz, CHLOROFORM-d) ppm 1.30 (t, J=7.34 Hz, 3H) 3.00 (q, J=7.34Hz, 2H) 3.34 (sl, 3 H) 3.44 - 3.58 (brs, 3H) 3.96 (s, 3H) 7.53 (s, 1H) 7.82 (s, 1H). LC-MS (Method A) M+H (348); TR=0.87 min. Step E:1-[6-Ethylsulfanyl-1-methyl-2-(trifluoromethyl)benzimidazol-5-yl]ethanone

[0158] In a three-neck flask under argon, 1.4 mol/L methylmagnesium bromide in THF/Toluene (1:3) (1.4 mL, 1.9 mmol) was diluted in toluene (8.4 mL) . The solution was cooled to 0 °C and 6-ethylsulfanyl-N-methoxy-N,1-dimethyl-2-(trifluoromethyl)benzimidazol-5-carboxamide (0.56 g, 1.6 mmol), dissolved in 5 mL of toluene and 2 mL of THF were added dropwise. The reaction mixture was stirred 1 hour at 0°C and 1 hour at room temperature. LC-MS analysis showed the presence of starting material in the reaction mixture. The solution was cooled back to 0 °C and methylmagnesium bromide (1.4 mL, 1.9 mmol) was added again. After 2 hours at room temperature, LC-MS showed completion of the reaction.
[0159] The crude was slowly quenched with sat aq NH 4 Cl (10 mL) and 1 M HCl (5 mL) and the resulting mixture was vigorously stirred for 1 hour at room temperature. The aqueous layer was extracted twice with ethylacetate. The combined organic phases were washed with aq 1M HCl sol, water and brine, dried over anhydrous Na 2 SO 4 , filtered and concentrated in vacuo. The crude product was purified by flash chromatography on silica gel cartridge to give the title compound as a beige solid. 1H NMR (400 MHz, CHLOROFORM-d) ppm 1.42 (t, J=7.34 Hz, 3H) 2.69 (s, 3H) 2.99 (q, J=7.34Hz, 2 H) 3.95 (d, J=0.73 Hz, 3H) 7.30 (s, 1H) 8.31 (s, 1H) LC-MS (Method A) M+H (303); TR=0.95min. Step F: 1-[6-Ethylsulfonyl-1-methyl-2-(trifluoromethyl)benzimidazol-5-yl]ethanone

[0160] At 0°C, MCPBA (0.20 g, 0.88 mmol) was added portionwise to a solution of 1-[6-ethylsulfanyl-1-methyl-2-(trifluoromethyl)benzimidazol-5-yl ]ethanone (0.13 g, 0.43 mmol) in chloroform (3.9 mL). Upon addition of the first portion there was a small exothermic reaction. The temperature was increased to 12 °C. The beige suspension was stirred at room temperature. After 5 days, LC/MS analysis showed the desired mass formation. Saturated aqueous sodium thiosulfate solution (slightly exothermic) and aq NaHCO3 were added and the mixture was stirred at room temperature for 40 min. The organic layer was separated, washed again with aq NaHCO 3 and dried over Na 2 SO 4 , filtered and concentrated in vacuo at 40 °C to give the crude product containing mostly 1-[6-ethylsulfonyl-1-methyl-2-(trifluoromethyl)benzimidazole -5-yl]ethanone. This was used in the next step without further purification. 1H NMR (400 MHz, CHLOROFORM-d) ppm 1.35 (t, J=7.34 Hz, 3H) 2.72 (s, 3H) 3.55 (q, J=7.46 Hz, 2 H) 4.07 (s, 3H) 7.99 (s, 1H) 8.25 (s, 1H). LC-MS (Method A) M+H (335); TR=0.83min Step G: 2-Bromo-1-[6-ethylsulfonyl-1-methyl-2-(trifluoromethyl)benzimidazol-5-yl]ethanone

[0161] 1-[6-Ethylsulfonyl-1-methyl-2-(trifluoromethyl)benzimidazol-5-yl]ethanone (0.30 g, 0.90 mmol) was dissolved in chloroform (1.5 mL) and ethylacetate ( 1.5 mL) in a microwave vial and dibromocopper (0.40 g, 1.8 mmol) was added. The reaction mixture was stirred in the microwave for 55' at 140°C. LC-MS analysis showed the formation of desired product, starting material and by-product. The reaction mixture was filtered and the precipitate was washed with dichloromethane, then the filtrate was concentrated in vacuo. The crude obtained was purified by flash chromatography to give mostly 2-bromo-1-[6-ethylsulfonyl-1-methyl-2-(trifluoromethyl)benzimidazol-5-yl]ethanone but also starting material and by-product. The mixture was used for the next step without further purification. LC-MS (Method A) M+H (413-415); TR=0.90min Step H:2-[6-ethylsulfonyl-1-methyl-2-(trifluoromethyl)benzimidazol-5-yl]-7-(trifluoromethyl)imidazo[1,2-c]pyrimidine

[0162] In a microwave vial, 2-bromo-1-[6-ethylsulfonyl-1-methyl-2-(trifluoromethyl)benzimidazol-5-yl]ethanone (0.25 g, 0.61 mmol) and 6-(trifluoromethyl)pyrimidin-4-amine (0.10 g, 0.61 mmol) was dissolved in acetonitrile (3.0 mL). The flask was shaken 1 h at 150 °C in the microwave system. LC-MS analysis showed formation of the desired product. The reaction mixture was evaporated in vacuo. The residue was dissolved in dichloromethane and washed with sat. NaHCO 3 (10 mL) with 1 mL of 1 N NH 4 OH. The organic layer was washed with brine, dried over Na 2 SO 4 , filtered and concentrated in vacuo. The crude product was purified by flash chromatography on silica gel cartridge to give a mixture of starting material and desired product. A second purification had to be done and then the obtained mixture was purified by reverse phase to give the title compound as a white solid. 1H NMR (400 MHz, CHLOROFORM-d) ppm 1.26 (t, J=7.34 Hz, 3H) 3.54 (q, J=7.46 Hz, 2H) 4.11 (s, 3 H) 7.96 (s, 1H) 8.12 (d, J=6.24 Hz, 2H) 8.43 (s, 1H) 9.18 (s, 1H). LC-MS (Method A) M+H (478); TR=0.95min Example P3: Synthesis of 6-ethylsulfonyl-1-methyl-2-(trifluoromethyl)-5-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]benzimidazole (Compound P3 , Table P).
4-(Trifluoromethyl)pyridin-2-amine (0.15 g, 0.90 mmol), 1-[6-ethylsulfonyl-1-methyl-2-(trifluoromethyl)benzimidazol-5-yl]ethanone (0.15 g , 0.45 mmol, step F, Example P2), o-phenanthroline monohydrate (0.016 g, 0.090 mmol), diiodozinc (0.029 g, 0.090 mmol), diacetotoxic copper hydrate (0.018 g, 0.090 mmol) and 1,2- dichlorobenzene (1.5 mL) were placed in a vial. The beige suspension was stirred at 120°C overnight.
[0163] After 15 hours the reaction mixture was allowed to cool down to rt. LC/MS analysis showed the mass of the desired product. Dichloromethane was added, the mixture was filtered and the residue was washed with dichloromethane and methanol. The mother liquor was evaporated (still contains dichloromethane). The crude obtained was purified by flash chromatography on silica gel and then by reverse phase chromatography to give the title compound as a white solid. 1H NMR (400 MHz, CHLOROFORM-d) ppm 1.21 - 1.27 (t, 3H) 3.51 (q, J=7.34 Hz, 2H) 4.10 (s, 3H) 7 .05 (dd, J=7.15, 1.65Hz, 1H) 7.96 (s, 1H) 8.06 (s, 1H) 8.13 (s, 1H) 8.31 ( d, J=7.34 Hz, 1H) 8.43 (s, 1H). LC/MS (method A) M+H[477]; TR= 0.99 min Example P4 :2-[6-ethylsulfonyl-1-methyl-2-(trifluoromethyl)benzimidazol-5-yl]-7-(trifluoromethylsulfanyl)imidazo[1,2-c]pyrimidine (Compound P4, P4, Table P)

[0164] To a solution of 6-bromopyrimidin-4-amine (1.75 g, 10 mmol) in dry acetonitrile (45 mL) was added (bpy)CuSCF3 (4.8 g, 15 mmol). The mixture was refluxed at 100°C for 2 hours under a nitrogen atmosphere. After this time the mixture was filtered and concentrated in vacuo. The crude product was purified by silica gel column chromatography to give the product 6-((trifluoromethyl)thio)pyrimidin-4-amine. 1H-NMR (400Mz, DMSO-d6) : 6.60 (s, 1H), 7.26 (s, 2H), 8.29 (s, 1H). 19F-NMR (300Mz, DMSO-d6): -42.45 (s, 3F). Step B: Synthesis of 2-[6-ethylsulfonyl-1-methyl-2-(trifluoromethyl)benzimidazol-5-yl]-7-(trifluoromethylsulfanyl)imidazo[1,2-c]pyrimidine (Compound P4, Table P)

[0165] In a microwave vial, 2-bromo-1-[6-ethylsulfonyl-1-methyl-2-(trifluoromethyl)benzimidazol-5-yl]ethanone (0.13 g, 0.31 mmol, step G, example P2) and 6-(trifluoromethylsulfanyl)pyrimidin-4-amine (0.061 g, 0.31 mmol) were dissolved in acetonitrile (1.6 mL). The vial was shaken 1 hour at 150 °C in the microwave. LC-MS analysis showed formation of the desired product. The reaction mixture was evaporated and the crude obtained was purified by flash chromatography on silica gel and then by reverse phase chromatography to give the title compound. 1H NMR (400 MHz, CHLOROFORM-d) ppm 1.29 (t, J=1.00 Hz, 3H) 3.5 (q, J=7Hz, 2H) 4.1 (s, 3H) 8.0 (s, 1 H) 8.1 (s, 1 H) 8.2 (s, 1 H) 8.5 (s, 1 H) 9.1 (d, J=1 Hz, 1 H) LC/MS (method A) M+H [510]; TR= 1.00 min Table P: Examples of compounds of formula (I) Preparations and Physical and Spectroscopic Data

[0166] The activity of the compositions according to the invention can be considerably expanded, and adapted to prevailing circumstances, by adding other active ingredients in terms of insecticides, acaricides and/or fungicides. Mixtures of the compounds of the formula I with other active ingredients in terms of insecticides, acaricides and/or fungicides can also have additional surprising advantages which can also be described, in a broader sense, as synergistic activity. For example, better tolerance for plants, reduced phytotoxicity, insects can be controlled in their different stages of development or better behavior during their production, for example during crushing or mixing, during their storage or during their use. Suitable additions to active ingredients herein are, for example, representative of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formaidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons , acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
[0167] The following mixtures of compounds of formula I with active ingredients are preferred (the abbreviation "TX" means "a compound selected from the group consisting of the compounds described in Tables 1 to 3 and P of the present invention"):
[0168] The activity of the compositions according to the invention can be considerably expanded, and adapted to prevailing circumstances, by adding other active ingredients in terms of insecticides, acaricides and/or fungicides. Mixtures of the compounds of the formula I with other active ingredients in terms of insecticides, acaricides and/or fungicides can also have additional surprising advantages which can also be described, in a broader sense, as synergistic activity. For example, better tolerance for plants, reduced phytotoxicity, insects can be controlled in their different stages of development or better behavior during their production, for example during crushing or mixing, during their storage or during their use.
[0169] Suitable additions to active ingredients here are, for example, representative of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formaidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids , chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
[0170] The following mixtures of the compounds of formula I with active ingredients are preferred (the abbreviation "TX" means "a compound selected from the group consisting of the compounds described in Tables 1 to 23 and P of the present invention"): an adjuvant selected from group of substances consisting of petroleum oils (628) + TX, an acaricide selected from the group of substances consisting of 1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910) + TX, 2-benzenesulfonate ,4-dichlorophenyl (IUPAC/from Chemical Abstracts name) (1059) + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name) (1295) + TX, 4-chlorophenyl phenyl sulfone (name IUPAC) (981) + TX, abamectin (1) + TX, acequinocil (3) + TX, acetoprol [CCN] + TX, acrinathrin (9) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, alpha-cypermethrin (202) + TX, amidition (870) + TX, amidoflumete [CCN] + TX, amidothioate (872) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz ( 24) + TX, aramite (881) + TX, arsenous oxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azobenzene (IUPAC name) (888) + TX, azocyclotin (46) + TX, nitrogenate (889) + TX, benomyl (62) + TX, benoxaphos [CCN] + TX, benzoximate (71) + TX, benzyl benzoate (name IUPAC) [CCN] + TX, biphenazate (74) + TX, bifenthrin (76) + TX, binapacril (907) + TX, brofenvalerate + TX, bromocyclene (918) + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, bromopropylate (94) + TX, buprofezine (99) + TX, butocarboxim (103) + TX, butoxycarboxim (104) + TX, butylpyridaben + TX, calcium polysulfide (IUPAC name) (111) + TX , camfechlor (941) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbophenothione (947) + TX, CGA 50'439 (development code) (125) + TX , quinomethionate (126) + TX, chlorbenside (959) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorfenapyr (130) + TX, chlorphenetol (968 ) + TX, chlorfenson (970) + TX, chlorofensulfide (971) + TX, chlorfenvinphos (131) + TX, chlorobenzylate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, clofentezine (158) + TX, closantel [CCN] + TX, coumaphos (174) + TX, crotamiton [CCN] + TX, crotoxiphos (1010) + TX, cufraneb (1013) + TX, cyanoate (1020) + TX, cyflumethophen ( CAS Reg. No: 400882-07-7) + TX, cyhalothrin (196) + TX, cyhexatin (199) + TX, cypermethrin (201) + TX, DCPM (1032) + TX, DDT (219) + TX , demefion (1037) + TX, demefion-O (1037) + TX, demefion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-O (1038) + TX , demeton-O-methyl (224) + TX, demetonS (1038) + TX, demeton-S-methyl (224) + TX, demeton-S-methylsulfone (1039) + TX, diafenthiuron (226) + TX, dialyphos ( 1042) + TX, diazinon (227) + TX, dichlofluanide (230) + T X, dichlorvos (236) + TX, dicliphos + TX, dicofol (242) + TX, dicrotophos (243) + TX, dienochlor (1071) + TX, dimefox (1081) + TX, dimethoate (262) + TX, dynactin ( 653) + TX, dinax (1089) + TX, dinex-diclexin (1089) + TX, dinobuton (269) + TX, dinocap (270) + TX, dinocap-4 [CCN] + TX, dinocap-6 [CCN] + TX, dinocton (1090) + TX, dinopenton (1092) + TX, dinosulfone (1097) + TX, dinoterbon (1098) + TX, dioxathion (1102) + TX, diphenylsulfone (IUPAC name) (1103) + TX, disulfiram [CCN] + TX, disulfoton (278) + TX, DNOC (282) + TX, dofenapin (1113) + TX, doramectin [CCN] + TX, endosulfan (294) + TX, endothion (1121) + TX, EPN ( 297) + TX, eprinomectin [CCN] + TX, ethion (309) + TX, ethoate-methyl (1134) + TX, etoxazol (320) + TX, etrymphos (1142) + TX, fenazaflor (1147) + TX, phenazaquim (328) + TX, fenbutatin oxide (330) + TX, phenothiocarb (337) + TX, fenpropathrin (342) + TX, fenpyrad + TX, fenpyroximate (345) + TX, fenson (1157) + TX, fentriphanil (1161 ) + TX, fenvalerate (349) + TX, fi pronil (354) + TX, fluacripyrim (360) + TX, fluazuron (1166) + TX, flubenzimine (1167) + TX, flucycloxuron (366) + TX, flucitrinate (367) + TX, fluenethyl (1169) + TX, flufenoxuron (370) + TX, flumethrin (372) + TX, fluorbenside (1174) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formotion (1192) + TX, formparanate (1193) + TX, gamma-HCH (430) + TX, gliodin (1205) + TX, halfenprox (424) + TX, heptenophos (432) + TX, hexadecyl cyclopropanecarboxylate (IUPAC/Chemical Abstracts name) (1216) + TX, hexythiazox (441) + TX, iodomethane (IUPAC name) (542) + TX, isocarbophos (473) + TX, O-(methoxyaminothiophosphoryl)isopropyl salicylate (IUPAC name) (473) + TX, ivermectin [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, iodfenphos (1248) + TX, lindane (430) + TX, lufenuron (490 ) + TX, malathion (492) + TX, malonobene (1254) + TX, mecarbam (502) + TX, mephospholan (1261) + TX, mesulfen [ CCN] + TX, methacrylphos (1266) + TX, methamidophos (527) + TX, metidation (529) + TX, methiocarb (530) + TX, methomyl (531) + TX, methyl bromide (537) + TX, metolcarb (550) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime [CCN] + TX, mipafox (1293) + TX, monocrotophos (561) + TX, morphotion (1300) + TX, moxidectin [CCN] + TX, naled (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) + TX, nifluridide (1309) + TX, nikomycins [CCN] + TX, nitrilacarb (1313) + TX, nitrilacarb complex 1:1 zinc chloride (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxideprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum oils (628) + TX, fencapton (1330) + TX, phentoate (631) + TX, phorate (636) + TX, phosalone (637) + TX, phospholan (1338) + TX, phosmet (638) + TX, phosphamidon (639) + TX, foxim (642) + TX, pyrimiphos-methyl (652) + TX, polychloroterpenes (traditional name) (1347) + TX, polynactins (653) + TX, proclonol (1350) + TX, profenophos (662) + TX, promacil ( 1354) + TX, propargite (671) + TX, propetamphos (673) + TX, propoxur (678) + TX, protidation (1360) + TX, protoate (1362) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridafenthion (701) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, quinphos (711) + TX, quinthiophos ( 1381) + TX, R-1492 (development code) (1382) + TX, RA-17 (development code) (1383) + TX, rotenone (722) + TX, escradano (1389) + TX, sebufos + TX , selamectin [CCN] + TX, SI-0009 (compound code) + TX, sophamide (1402) + TX, spirodiclofen (738) + TX, spiromesifen (739) + TX, SSI-121 (development code) (1404 ) + TX, sulfiram [CCN] + TX, sulfluramide (750) + TX, sulfotep (753) + TX, sulfur (754) + TX, SZI-121 (development code) (757) + TX, tau-flu valinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, terbam + TX, tetrachlorvinphos (777) + TX, tetradifon (786) + TX, tetranactin (653) + TX, tetrasul (1425) + TX, thiafenox + TX, thiocarboxime (1431) + TX, thiophanox (800) + TX, thiometon (801) + TX, thioquinox (1436) + TX, thuringiensin [CCN] + TX, triamiphos (1441) + TX, triarathene (1443) + TX, triazophos (820) + TX, triazuron + TX, trichlorfon (824) + TX, tripenophos (1455) + TX, trinactin (653) + TX, vamidothion (847) + TX, vaniliprol [CCN] and YI-5302 (compound code) + TX, an algaecide selected from the group of substances consisting of betoxazine [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cibutrine [CCN] + TX, diclone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinocamine (714) + TX, quinonamide (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide o (IUPAC name) (347) + TX, an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomate (1011) + TX, doramectin [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin [CCN] + TX, ivermectin [CCN] + TX, milbemycin oxime [CCN] + TX, moxidectin [CCN] + TX, piperazine [CCN] + TX, selamectin [CCN] + TX, spinosad (737) and thiophanate (1435) + TX, an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1122) + TX, phenthion (346) + TX, pyridin-4-amine ( IUPAC name) (23) and strychnine (745) + TX, a bactericide selected from the group of substances 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 (name IUPAC) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithion (1 105) + TX, dodicin (1112) + TX, phenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargaphen [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX , nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, hydroxyquinoline sulfate potassium (446) + TX, probenazol (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, teclophthalam (766) + TX, and thiomersal [CCN] + TX, a biological agent selected from group of substances consisting of Adoxophyes orana GV (12) + TX, Agrobacterium radiobacter (13) + TX, Amblyseius spp. (19) + TX, Anagrapha falcifera NPV (28) + TX, Anagrus atomus (29) + TX, Aphelinus abdominalis (33) + TX, Aphidius colemani (34) + TX, Aphidoletes aphidimyza (35) + TX, Autographa californica NPV (38) + TX, Bacillus firmus (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 subsp. kurstaki (scientific name) (51) + TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51) + TX, Beauveria bassiana (53) + TX, Beauveria brongniartii (54) + TX, Chrysoperla carnea (151) + TX, Cryptolaemus montrouzieri (178) + TX, Cydia pomonella GV (191) + TX, Dacnusa sibirica (212) + TX, Diglyphus isaea (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus (300) + TX, Helicoverpa zea NPV (431) + TX, Heterorhabditis bacteriophora e H. megidis (433) + TX, Hippodamia convergens (442) + TX, Leptomastix dactylopii (488) + TX, Macrolophus caliginosus (491) + TX, Mamestra brassicae NPV (494) + TX, Metaphycus helvolus (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 (575) + TX, Orius spp. (596) + TX, Paecilomyces fumosoroseus (613) + TX, Phytoseiulus persimilis (644) + TX, Spodoptera exigua nuclear polyhedrosis virus (scientific name) (741) + TX, Steinernema bibionis (742) + TX, Steinernema carpocapsae (742) + TX, Steinernema feltiae (742) + TX, Steinernema glaseri (742) + TX, Steinernema riobrave (742) + TX, Steinernema riobravis (742) + TX, Steinernema scapterisci (742) + TX, Steinernema spp. (742) + TX, Trichogramma spp. (826) + TX, Typhlodromus occidentalis (844) and Verticillium lecanii (848) + TX, a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX, a chemosterilizer selected from the group of substances consisting of afolate [CCN] + TX, bisazir [CCN] + TX, busulfan [CCN] + TX, diflubenzuron (250) + TX, dimatif [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl afolate [CCN] + TX, morzid [CCN] + TX, penfluron [CCN] + TX, tepa [CCN] + TX , thiohempa [CCN] + TX, thiotepa [CCN] + TX, tretamine [CCN] and uredepa [CCN] + TX, an insect pheromone selected from the group of substances consisting of (E)-dec-5-en-acetate 1-yl with (E)-dec-5-en-1-ol (IUPAC name) (222) + TX, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829) + TX, (E)-6-methyl-hept-2-en-4-ol (IUPAC name) (541) + TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate (name IUPAC) (779) + TX, (Z)-dodec-7-acetate and n-1-yl (IUPAC name) (285) + TX, (Z)-hexadec-11-enal (IUPAC name) (436) + TX, (Z)-hexadec-11-en-1-yl acetate ( IUPAC name) (437) + TX, (Z)-hexadec-13-en-11-in-1-yl acetate (IUPAC name) (438) + TX, (Z)-icos-13-en-10- one (IUPAC name) (448) + TX, (Z)-tetradec-7-en-1-al (IUPAC name) (782) + TX, (Z)-tetradec-9-en-1-ol (IUPAC name) ) (783) + TX, (Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784) + TX, (7E,9Z)-dodeca-7,9-dien-1-acetate ila (IUPAC name) (283) + TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780) + TX, (9Z,12E)-tetradeca-acetate 9,12-dien-1-yl (IUPAC name) (781) + TX, 14-methyloctadec-1-ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol with 4-methylnonan-5- one (IUPAC name) (544) + TX, alpha-multistriatin [CCN] + TX, brevicomin [CCN] + TX, codlelure [CCN] + TX, codlemone (167) + TX, cuelure (179) + TX, disparlure ( 277) + TX, dodec-8-en-1-yl acetate (IUPAC name) (286) + TX, dodec-9-en-1-yl acetate (IUPAC name) (287) + TX, dodeca-8 + TX, acetate of 10-dien-1-yl (IUPAC name) (284) + TX, dominicalure [CCN] + TX, ethyl 4-methyloctanoate (IUPAC name) (317) + TX, eugenol [CCN] + TX, frontalin [CCN ] + TX, gossyplure (420) + TX, grandlure (421) + TX, grandlure I (421) + TX, grandlure II (421) + TX, grandlure III (421) + TX, grandlure IV (421) + TX, hexalure [CCN] + TX, ipsdienol [CCN] + TX, ipsenol [CCN] + TX, japonylure (481) + TX, lineatin [CCN] + TX, litlure [CCN] + TX, looplure [CCN] + TX, medlure [CCN] + TX, megatomoic acid [CCN] + TX, methyl eugenol (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 [CCN] + TX, oryctalure (317) + TX, ostramone [CCN] + TX, siglure [CCN ] + TX, sordidine (736) + TX, sulcatol [CCN] + TX, tetradec-11-en-1-yl acetate (IUPAC name) (785) + TX, trimedlure (839) + TX, trimedlure A (839 ) + TX, trimedlure B1 (839) + TX, trimedlure B2 (839) + TX, trimedlure C (839) and trunc-call [CCN] + TX, an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy (polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX , dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexamide [CCN] + TX, methochin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN ] + TX, an insecticide selected from the group of substances consisting of 1-dichloro-1-nitroethane (IUPAC/from Chemical Abstracts name) (1058) + TX, 1,1-dichloro-2,2-bis(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-d) acetate ichlorophenyl)ethyl (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 methylcarbamate) ,3-dioxolan-2-yl)phenyl (IUPAC/Chemical Abstracts name) (1084) + TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986) + TX, phosphate from 2-chlorovinyl diethyl (IUPAC name) (984) + TX, 2-imidazolidone (IUPAC name) (1225) + TX, 2-isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 2-methylcarbamate methyl(prop-2-ynyl)aminophenyl (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-xylyl methylcarbamate (IUPAC name) ) (1285) + TX, 5,5-dimethyl-3-dimethylcarbamate oxocyclohex-1-enyl (IUPAC name) (1085) + TX, abamectin (1) + TX, acephate (2) + TX, acetamiprid (4) + TX, acetion [CCN] + TX, acetoprol [CCN] + TX, acrinathrin (9) + TX, acrylonitrile (IUPAC name) (861) + TX, alanicarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, aldrin (864) + TX, allethrin (17) + TX, allosamidine [CCN] + TX, alixicarb (866) + TX, alpha-cypermethrin (202) + TX, alpha-ecdysone [CCN] + TX, aluminum phosphide (640) + TX, amidition (870) + TX , amidothioate (872) + TX, aminocarb (873) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, anabasine (877) + TX, atidation (883 ) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azadirachtin (41) + TX, azamethiphos (42) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, nitrogenate (889) + TX, Bacillus thuringiensis delta endotoxins (52) + TX, barium hexafluorosilicate [CCN] + TX, barium polysulfide (IUPAC/Chemical Abstracts name) (892) + TX, bartr ina [CCN] + TX, Bayer 22/190 (development code) (893) + TX, Bayer 22408 (development code) (894) + TX, bendiocarb (58) + TX, benfuracarb (60) + TX, bensultape (66) + TX, beta-cyfluthrin (194) + TX, beta-cypermethrin (203) + TX, bifenthrin (76) + TX, bioallethrin (78) + TX, S-cyclopentenyl isomer of bioallethrin (79) + TX , bioethanomethrin [CCN] + TX, biopermethrin (908) + TX, bioresmethrin (80) + TX, bis(2-chloroethyl) ether (IUPAC name) (909) + TX, bistrifluron (83) + TX, borax (86 ) + TX, brofenvalerate + TX, bromfenvinphos (914) + TX, bromocyclene (918) + TX, bromo-DDT [CCN] + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, bufencarb (924 ) + TX, buprofezin (99) + TX, butacarb (926) + TX, butthiophos (927) + TX, butocarboxim (103) + TX, butonate (932) + TX, butoxycarboxim (104) + TX, butylpyridaben + TX, cadusaphos (109) + TX, calcium arsenate [CCN] + TX, calcium cyanide (444) + TX, calcium polysulfide (IUPAC name) (111) + TX, camfechlor (941) + TX, c arbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbon disulfide (IUPAC/Chemical Abstracts name) (945) + TX, carbon tetrachloride (IUPAC name) (946) + TX, carbophenothione (947) + TX, carbosulfan (119) + TX, cartap (123) + TX, cartap hydrochloride (123) + TX, cevadine (725) + TX, chlorbicyclene (960) + TX, chlordane (128) + TX , chlordecone (963) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorideoxiphos (129) + TX, chlorfenapyr (130) + TX, chlorfenvinphos (131) + TX, chlorfluazuron (132) + TX, chlormephos (136) + TX, chloroform [CCN] + TX, chloropicrin (141) + TX, chlorphoxim (989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX, chlorpyriphos-methyl (146) + TX, chlorthiophos (994) + TX, chromafenozide (150) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, cis-resmethrin + TX, cismethrin (80) + TX, clocitrile + TX, cloethocarb (999) + TX, closantel [CCN] + TX, clothianidin (165) + TX, copper acetoarsenite [CCN] + TX, a copper rsenate [CCN] + TX, copper oleate [CCN] + TX, coumaphos (174) + TX, coumitoate (1006) + TX, crotamiton [CCN] + TX, crotoxyphos (1010) + TX, crufomate (1011) + TX, cryolite (177) + TX, CS 708 (development code) (1012) + TX, cyanophenphos (1019) + TX, cyanophos (184) + TX, cyanoate (1020) + TX, cyclethrin [CCN] + TX , cycloprothrin (188) + TX, cyfluthrin (193) + TX, cyhalothrin (196) + TX, cypermethrin (201) + TX, cyphenothrin (206) + TX, cyromazine (209) + TX, citioate [CCN] + TX, d-limonene [CCN] + TX, d-tetramethrin (788) + TX, DAEP (1031) + TX, dazomete (216) + TX, DDT (219) + TX, decarbofuran (1034) + TX, deltamethrin (223) + TX, demefion (1037) + TX, demefion-O (1037) + TX, demefion-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-methylsulfone (1039) + TX, diafenthiuron (226) + TX, dialyphos (1042) + TX, diamidaphos (1044) + TX, diazinon (227) + T X, dicapton (1050) + TX, diclofenthion (1051) + TX, dichlorvos (236) + TX, dicliphos + TX, dicresyl [CCN] + TX, dicrotophos (243) + TX, dicyclanil (244) + TX, dieldrin ( 1070) + TX, 5-methylpyrazol-3-yl diethyl phosphate (IUPAC name) (1076) + TX, diflubenzuron (250) + TX, dilor [CCN] + TX, dimefluthrin [CCN] + TX, dimefox (1081) + TX, dimetan (1085) + TX, dimethoate (262) + TX, dimethrin (1083) + TX, dimethylvinphos (265) + TX, dimethylan (1086) + TX, dinax (1089) + TX, dinex-diclexin (1089 ) + TX, dinoprop (1093) + TX, dinosam (1094) + TX, dinoseb (1095) + TX, dinotefuran (271) + TX, diofenolan (1099) + TX, dioxabenzophos (1100) + TX, dioxacarb (1101) + TX, dioxathion (1102) + TX, disulfoton (278) + TX, dithychrophos (1108) + TX, DNOC (282) + TX, doramectin [CCN] + TX, DSP (1115) + TX, ecdysterone [CCN] + TX, EI 1642 (development code) (1118) + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, EMPC (1120) + TX, empentrin (292) + TX, endosulfan (294) + TX, endothion (1121 ) + TX, endrin (1122) + TX, EPBP (1123) + TX, EPN (297) + TX, epofenonan (1124) + TX, eprinomectin [CCN] + TX, esfenvalerate (302) + TX, etaphos [CCN] + TX, ethiofencarb (308) + TX, ethion (309) + TX, ethiprole (310) + TX, ethoate-methyl (1134) + TX, ethoprophos (312) + TX, ethyl format (IUPAC name) [CCN] + TX, ethyl-DDD (1056) + TX, ethylene dibromide (316) + TX, ethylene dichloride (chemical name) (1136) + TX, ethylene oxide [CCN] + TX, ethofenprox (319) + TX, ethrymphos (1142) + TX, EXD (1143) + TX, famfur (323) + TX, phenamiphos (326) + TX, fenazaflor (1147) + TX, fenchlorphos (1148) + TX, fenetacarb (1149) + TX, fenfluthrin (1150) + TX, fenitrothion (335) + TX, phenobucarb (336) + TX, fenoxacrim (1153) + TX, phenoxycarb (340) + TX, fenpyrithrin (1155) + TX, fenpropathrin (342) + TX, fenpyrad + TX, fensulfothion (1158) + TX, fenthion (346) + TX, fenthion-ethyl [CCN] + TX, fenvalerate (349) + TX, fipronil (354) + TX, flonicamid (358) + TX, flubendiamide (No. CAS Reg.: 27245165-7) + TX, flucofuron (1168) + TX, flucycloxuron (366) + TX, flucitrinate (367) + TX, fluenethyl (1169) + TX, flufenorim [CCN] + TX, flufenoxuron (370 ) + TX, flufenprox (1171) + TX, flumethrin (372) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, phonophos (1191) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formotion (1192) + TX, formparanate (1193) + TX, phosmethylan (1194) + TX, fospirate (1195) + TX, phosthiazate (408) + TX, phosthiethane (1196) + TX, furathiocarb (412) + TX, furethrin (1200) + TX, gamma-cyhalothrin (197) + TX, gamma-HCH (430) + TX, guazatine (422) + TX, guazatine acetates (422) + TX , GY-81 (development code) (423) + TX, halfenprox (424) + TX, halofenozide (425) + TX, HCH (430) + TX, HEOD (1070) + TX, heptachlor (1211) + TX, heptenophos (432) + TX, heterophos [CCN] + TX, hexaflumuron (439) + TX, HHDN (864) + TX, hydramethylnone (443) + TX, hydrogen cyanide (444) + TX, hydroprene (445) + TX , hi quincarb (1223) + TX, imidacloprid (458) + TX, imiprotrin (460) + TX, indoxacarb (465) + TX, iodomethane (IUPAC name) (542) + TX, IPSP (1229) + TX, isazophos (1231) + TX, isobenzane (1232) + TX, isocarbophos (473) + TX, isodrine (1235) + TX, isofenphos (1236) + TX, isolane (1237) + TX, isoprocarb (472) + TX, O-(methoxyaminothiophosphoryl) isopropyl salicylate (IUPAC name) (473) + TX, isoprothiolane (474) + TX, isothioate (1244) + TX, isoxation (480) + TX, ivermectin [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, iodfenphos (1248) + TX, juvenile hormone I [CCN] + TX, juvenile hormone II [CCN] + TX, juvenile hormone III [CCN] + TX, celevan (1249) + TX, quinoprene ( 484) + TX, lambda-cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepimectin (CCN) + TX, leptophos (1250) + TX, lindane (430) + TX, lirimphos (1251) + TX , lufenuron (490) + TX, litidation (1253) + TX, m-cumenyl methylcarbamate (IUPAC name) (1014) + TX, magnesium phosphide (IUPAC name) (640) + TX, malathion (4 92) + TX, malonobene (1254) + TX, mazidox (1255) + TX, mecarbam (502) + TX, mecarfon (1258) + TX, menazone (1260) + TX, mephospholan (1261) + TX, mercurous chloride ( 513) + TX, mosulfenphos (1263) + TX, metaflumizone (CCN) + TX, metam (519) + TX, metam-potassium (519) + TX, metham-sodium (519) + TX, methacrylic (1266) + TX , methamidophos (527) + TX, methanesulfonyl fluoride (IUPAC/Chemical Abstracts name) (1268) + TX, metidation (529) + TX, methiocarb (530) + TX, methocrotophos (1273) + TX, methomyl (531) + TX, metoprene (532) + TX, methoquin-butyl (1276) + TX, methotrin (533) + TX, methoxychlor (534) + TX, methoxyfenozide (535) + TX, methyl bromide (537) + TX, isothiocyanate methyl (543) + TX, methylchloroform [CCN] + TX, methylene chloride [CCN] + TX, methofluthrin [CCN] + TX, metolcarb (550) + TX, methoxadiazone (1288) + TX, mevinphos (556) + TX , mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime [CCN] + TX, mipafox (1293) + TX, mirex (1294) + TX, monocrotophos (561) + TX, morphotion (1300) + TX, moxidectin [CCN] + TX, naphthalophos [CCN] + TX, naled (567) + TX, naphthalene (IUPAC/Chemical Abstracts name) (1303) + TX, NC-170 (development code ) (1306) + TX, NC-184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (578) + TX, nifluridide (1309) + TX, nitenpyram (579) + TX, nithiazine ( 1311) + TX, nitrilacarb (1313) + TX, nitrilacarb complex 1:1 zinc chloride (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, nornicotine (traditional name) (1319) + TX, novaluron (585) + TX, noviflumuron (586) + TX, O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate (IUPAC name) (1057) + TX, phosphorothioate O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl (IUPAC name) (1074) + TX, O,O-diethyl phosphorothioate O-6-methyl-2-propylpyrimidin-4 - ila (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) + T X, oxidemeton-methyl (609) + TX, oxideprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, para-dichlorobenzene [CCN] + TX, parathion (615) + TX , parathion-methyl (616) + TX, penfluron [CCN] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (IUPAC name) (623) + TX, permethrin (626) + TX, petroleum oils (628) + TX, PH 6038 (development code) (1328) + TX, fencapton (1330) + TX, phenothrin (630) + TX, phentoate (631) + TX, phorate (636) + TX, phosalone (637) + TX , phospholan (1338) + TX, phosmet (638) + TX, phosnichlor (1339) + TX, phosphamidon (639) + TX, phosphine (IUPAC name) (640) + TX, phoxim (642) + TX, phoxim-methyl (1340) + TX, pyrimetaphos (1344) + TX, pyrimicarb (651) + TX, pyrimiphos-ethyl (1345) + TX, pyrimiphos-methyl (652) + TX, polychlorodicyclopentadiene isomers (IUPAC name) (1346) + TX , polychloroterpenes (traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, praletrin (655) + TX, precocious I [CCN] + TX, pr ecocene II [CCN] + TX, precocene III [CCN] + TX, primidone (1349) + TX, profenophos (662) + TX, proflutrin [CCN] + TX, promacil (1354) + TX, promecarb (1355) + TX , propaphos (1356) + TX, propetamphos (673) + TX, propoxur (678) + TX, protidation (1360) + TX, prothiophos (686) + TX, protoate (1362) + TX, protrifenbuto [CCN] + TX, pymetrozine (688) + TX, pyraclophos (689) + TX, pyrazolophos (693) + TX, pyresmethrin (1367) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX , pyridaben (699) + TX, pyridalyl (700) + TX, pyridafenthion (701) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, pyriproxyfen (708) + TX, quassia [CCN] + TX, quinthiophos (711) + TX, quinalphos-methyl (1376) + TX, quinothion (1380) + TX, quintiophos (1381) + TX, R-1492 (development code) (1382) + TX, rafoxanide [CCN] + TX , resmethrin (719) + TX, rotenone (722) + TX, RU 15525 (development code) (723) + TX, RU 25475 (development code) (1386) + TX, ryania (1387) + TX, ryanodine (traditional name) (1387) + TX, sabadilla (725) + TX, escradano (1389) + TX, sebufos + TX, selamectin [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 ( compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, silafluofen (728) + TX, SN 72129 (development code) (1397) + TX, arsenite sodium [CCN] + TX, sodium cyanide (444) + TX, sodium fluoride (IUPAC/Chemical Abstracts name) (1399) + TX, sodium hexafluorosilicate (1400) + TX, sodium pentachlorophenoxide (623) + TX, sodium selenate (IUPAC name) (1401) + TX, sodium thiocyanate [CCN] + TX, sophamide (1402) + TX, spinosad (737) + TX, spiromesifen (739) + TX, spirotetramate [CCN] + TX, sulcofuron (746) + TX, sulcofuron-sodium (746) + TX, sulfluramide (750) + TX, sulfotep (753) + TX, sulfuryl fluoride (756) + TX, sulprophos (1408) + TX, oils of tar (758) + TX, tau-fluvalinate (398) + TX, tazimcarb (1412) + TX, TDE (1414) + TX, tebufenozide (762) + TX, tebufe npirade (763) + TX, tebupyrimphos (764) + TX, teflubenzuron (768) + TX, tefluthrin (769) + TX, temephos (770) + TX, TEPP (1417) + TX, teralethrin (1418) + TX, terbam + TX, terbuphos (773) + TX, tetrachloroethane [CCN] + TX, tetrachlorvinphos (777) + TX, tetramethrin (787) + TX, theta-cypermethrin (204) + TX, thiacloprid (791) + TX, thiafenox + TX , thiamethoxam (792) + TX, ticrophos (1428) + TX, thiocarboxime (1431) + TX, thiocyclam (798) + TX, thiocyclam hydrogenoxalate (798) + TX, thiodicarb (799) + TX, thiophanox (800) + TX, thiometon (801) + TX, thionazine (1434) + TX, thiosultap (803) + TX, thiosultap-sodium (803) + TX, thuringiensin [CCN] + TX, tolfenpyrad (809) + TX, tralomethrin (812) + TX, transfluthrin (813) + TX, transpermethrin (1440) + TX, triamiphos (1441) + TX, triazamate (818) + TX, triazophos (820) + TX, triazuron + TX, trichlorfon (824) + TX, trichlormetaphos -3 [CCN] + TX, trichloronat (1452) + TX, tripenophos (1455) + TX, triflumuron (835) + TX, trimetacarb (840) + TX, triprene (1459) + TX, vamidothion (847) + TX, vaniliprol [CCN] + TX, veratridine (725) + TX, veratrine (725) + TX, XMC (853) + TX, xylylcarb (854) + TX, YI-5302 (code of compound) + TX, zeta-cypermethrin (205) + TX, zetamethrin + TX, zinc phosphide (640) + TX, zolaprophos (1469) and ZXI 8901 (development code) (858) + TX, cyantraniliprol [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 [187166-401 + 187166-15-0] + TX, spirotetramat [203313-25-1] + TX, sulfoxaflor [946578-00-3] + TX, flufiprol [704886-18-0] + TX, meperfluthrin [ 915288-13-0] + TX, tetramethylfluthrin [84937-88-2] + TX, triflumezopyrim (disclosed in WO 2012/092115) + TX, a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (IUPAC name ) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX , copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, triphenmorph ( 1454) + TX, trimetacarb (840) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, pyriprole [39473071-3] + TX, fluxamethamide (WO 2007/ 026965) + TX, a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, 1,2-dibromo-3-chloropropane (IUPAC/Chemical Abstracts name) (1045) + TX, 1,2 -dichloropropane (IUPAC/from Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 1, 3,4-dichlorotetrahydrothiophene 1-dioxide (IUPAC/from Chemical Abstracts name) (1065) + TX, 3-(4- chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1,3,5-thiadiazinen-3-ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine ( 210) + TX, abamectin (1) + TX, acetoprol [CCN] + TX, alanicarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, AZ 60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben + TX, cadusaphos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbosulfan (119) + TX, chloropicrin ( 141) + TX, chlorpyriphos (145) + TX, cloethocarb (999) + TX, cytokinins (210) + TX, dazomete (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidaphos (1044 ) + TX, diclofenthion (1051) + TX, dicliphos + TX, dimethoate (262) + TX, doramectin [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin [CCN] + TX, ethoprophos (312) + TX, ethylene dibromide (316) + TX, phenamiphos (326) + TX, fenpyrad + TX, fensulfothion (1158) + TX, phosthiazate (408) + TX, phosthiethane (1196) + TX, f urfural [CCN] + TX, GY-81 (development code) (423) + TX, heterophos [CCN] + TX, iodomethane (IUPAC name) (542) + TX, isamidophos (1230) + TX, isazophos (1231) + TX, ivermectin [CCN] + TX, kinetin (210) + TX, mecarphon (1258) + TX, metam (519) + TX, metam-potassium (519) + TX, metam-sodium (519) + TX, bromide of methyl (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime [CCN] + TX, moxidectin [CCN] + TX, composition of Myrothecium verrucaria (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosphocarb [CCN] + TX, sebufos + TX, selamectin [CCN] + TX, spinosad (737) + TX, terbam + TX, terbuphos (773) + TX, tetrachlorothiophene (IUPAC/Chemical Abstracts name) (1422) + TX, thiafenox + TX, thionazine (1434) + TX, triazophos (820) + TX, triazuron + TX, xylenols [CCN ] + TX, YI-5302 (compound code) and zeatin (210) + TX, fluensulfone [318290-98-1] + TX, a nitrification inhibitor selected from the substance group consisting of potassium ethylxanthate [CCN] and nitrapirin (580) + TX, a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazol (658) and extract of Reynoutria sachalinensis (720) + TX, a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (name IUPAC) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminum phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891) + TX, bistiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX , cholecalciferol (850) + TX, coumachlor (1004) + TX, coumafuril (1005) + TX, coumatetralil (175) + TX, crimidine (1009) + TX, difenacoum (246) + TX, diphethione (249) + TX, diphacinone (273) + TX, ergocalciferol (301) + TX, flocoumaphen (357) + TX, fluoroacetamide (379) + TX, flupropadine (1183) + TX, flupropadine hydrochloride (1183) + TX, gamma-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444) + TX, iodomethane (IUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (IUPAC name) (640) + TX, methyl bromide (537) + TX, norbormide (1318) + TX, phosacetin (1336 ) + TX, phosphine (IUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371) + TX, sciliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851) and zinc phosphide (640) + TX, a synergistic agent selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934) + TX, 5-(1,3-benzodioxol-5- il)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (code development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393 ) + TX, sesasmoline (1394) and sulfoxide (1406) + TX, an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, oxychloride of copper (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, methiocarb (530) + TX, pyridin -4-amine (IUPAC name) (23) + TX, thyram (804) + TX, trimetacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX, a virucide selected from the group of substances consisting of in imanin [CCN] and ribavirin [CCN] + TX, a wound protector selected from the group of substances consisting of mercuric oxide (512) + TX, octylinone (590) and thiophanate-methyl (802) + TX, and biologically active compounds selected from cons group being in azaconazole [60207-31-0] + TX, bitertanol [70585-36-3] + TX, bromuconazole [116255-48-2] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [119446- 68-3] + TX, diniconazole [83657-24-3] + TX, epoxiconazol [10632508-0] + TX, fenbuconazol [114369-43-6] + TX, fluquinconazol [136426-54-5] + TX, flusilazol [85509-19-9] + TX, flutriafol [76674-21-0] + TX, hexaconazole [79983-71-4] + TX, imazalil [35554-44-0] + TX, imibenconazole [86598-92-7 ] + TX, ipconazol [125225-28-7] + TX, metconazol [125116-23-6] + TX, myclobutanil [88671-89-0] + TX, pefurazoate [101903-30-4] + TX, penconazol [ 66246-88-6] + TX, prothioconazole [178928-706] + TX, pyrifenox [88283-41-4] + TX, prochloraz [67747-095] + TX, propiconazole [60207-90-1] + TX, simeconazole [14950890-7] + TX, tebuconazol [107534-96-3] + TX, tetraconazol [112281-77-3] + TX, triadimefon [43121-43-3] + TX, triadimenol [55219-65-3] + TX, triflumizole [99387-89-0] + TX, triticonazol [131983-72-7] + TX, ancymidol [12771-68-5] + TX, fenarimol [60168-88 -9] + TX, nuarimol [63284-71-9] + TX, bupirimate [41483-43-6] + TX, dimethirimol [5221-53-4] + TX, ethirimol [23947-60-6] + TX, dodemorph [1593-77-7] + TX, fenpropidin [67306-00-7] + TX, fenpropimorph [67564-91-4] + TX, spiroxamine [118134-30-8] + TX, tridemorph [81412-433] + TX, cyprodinil [121552-61-2] + TX, mepanipyrim [11023547-7] + TX, pyrimethanil [53112-28-0] + TX, fenpiclonil [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, ofurace [58810-48-3] + TX, oxadixyl [77732-09-3] + TX, benomyl [17804-35-2] + TX, carbendazim [10605-21-7] + TX, debacarb [62732- 91-6] + TX, fuberidazole [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, boscalide [188425-85 -6] + TX, carboxy [5234-68-4] + TX, f enfuram [24691-80-3] + TX, flutolanil [66332-96-5] + TX, mepronil [55814-41-0] + TX, oxycarboxin [5259-88-1] + TX, penthiopyrad [183675-82- 3] + TX, thifluzamide [130000-40-7] + TX, guazatine [108173-90-6] + TX, dodine [2439-10-3] [112-65-2] (free base) + TX, iminoctadine [13516-27-3] + TX, azoxystrobin [131860-33-8] + TX, dimoxystrobin [149961-52-4] + TX, enestroburin {Proc. BCPC, Int. Congr., Glasgow, 2003, 1, 93} + TX, fluoxastrobin [361377-29-9] + TX, kresoxim-methyl [14339089-0] + TX, metominostrobin [133408-50-1] + TX , trifloxystrobin [141517-21-7] + TX, oryzastrobin [24859316-0] + 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, putir [9006-42-2] + TX, propineb [12071-83-9] + TX, take [ 137-26-8] + TX, zineb [12122-67-7] + TX, ziram [137-30-4] + TX, captafol [2425-06-1] + TX, captan [133-06-2] + TX, dichlofluanid [1085-98-9] + TX, fluoroimide [41205-21-4] + TX, folpet [133-07-3] + TX, tolylfluanid [731-27-1] + TX, bordeaux mixture [8011-63-0] + TX, copper hydroxide [20427-59-2] + TX, copper oxychloride [1332-40-7] + TX, copper sulfate [7758-98-7] + TX, oxide copper [1317-391] + TX, copper [53988-93-5] + TX, oxine-copper [10380-286] + TX, dinocap [131-72-6] + TX, nitrothal-isopropyl [1055274-6 ] + TX, edifenphos [17109-49-8] + TX , iprobenphos [2608747-8] + TX, isoprothiolane [50512-35-1] + TX, phosdifen [36519-00-3] + TX, pyrazolophos [13457-18-6] + TX, tolclophos-methyl [57018-04 -9] + TX, acibenzolar-S-methyl [135158-54-2] + TX, anilazine [101-05-3] + TX, bentiavalcarb [413615-357] + TX, blasticidin-S [2079-00-7 ] + TX, quinomethionate [2439-01-2] + TX, chloroneb [2675-77-6] + TX, chlorothalonil [1897-45-6] + TX, cyflufenamide [180409-60-3] + TX, cymoxanil [ 57966-95-7] + TX, diclone [117-80-6] + TX, diclocimet [139920-32-4] + TX, diclomezine [62865-36-5] + TX, dichloran [99-30-9] + TX, diethfencarb [87130-20-9] + TX, dimethomorph [110488-70-5] + TX, SYP-LI90 (Flumorf) [211867-47-9] + TX, ditianon [3347-22-6] + TX, ethaboxam [162650-77-3] + TX, etridiazol [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 a [126833-17-8] + TX, fosetyl-aluminum [39148-248] + TX, himexazol [10004-44-1] + TX, iprovalicarb [14092317-7] + TX, IKF-916 (Ciazofamid) [120116 -88-3] + TX, kasugamycin [6980-18-3] + TX, metasulfocarb [66952-49-6] + TX, metrafenone [220899-03-6] + TX, pencycuron [66063-056] + TX, phthalide [27355-22-2] + TX, polyoxins [11113-80-7] + TX, probenazol [27605-76-1] + TX, propamocarb [25606-411] + TX, proquinazid [189278-12-4] + TX, pyroquilon [5736932-1] + TX, quinoxyphen [124495-18-7] + TX, quintazene [8268-8] + TX, sulfur [7704-34-9] + TX, tiadinil [223580-516] + TX, triazoxide [72459-58-6] + TX, tricyclazole [4181478-2] + TX, triforine [26644-46-2] + TX, validamycin [3724847-8] + TX, zoxamide (RH7281) [156052-68 -5] + TX, mandipropamide [374726-62-2] + TX, isopyrazam [881685-58-1] + TX, sedaxane [874967-67-6] + TX, (9-dichloromethylene-1,2,3, 3-Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid 4-tetrahydro-1,4-methane-naphthalen-5-yl)-amide (disclosed in WO 2007/048556) + TX, (3', 3-Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid 4',5'-trifluoro-biphenyl-2-yl)-amide (disclosed in WO 2006/087343) + 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-pyridinyl)-2H,11Hnaphtho[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-methylpropyl)-4-[2,2,2-trifluoro-1 -methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide [926914-55-8] + TX, flufiprol [704886-18-0] + TX, cyclaniliprol [1031756-98-5] + TX, tetraniliprol [1229654-66-3] + TX, guadipyr (described in WO 2010/060231) + TX and cycloxapride (described in WO 2005/077934) + TX; and microbials including: Acinetobacter lwoffii + TX, Acremonium alternatum + TX + TX, Acremonium cephalosporium + TX + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, Adoxophyes orana granulovirus (AdoxGV) (Agrobacterium strain TX) + TX K84 (Galltrol-A®) + TX, Alternaria alternate + TX, Alternaria cassia + TX, Alternaria destruens (Smolder®) + TX, Ampelomyces quisqualis (AQ10®) + TX, Aspergillus flavus AF36 (AF36®) + TX, Aspergillus flavus NRRL 21882 (Aflaguard®) + TX, Aspergillus spp. + TX, Aureobasidium pullulans + TX, Azospirillum + TX, (MicroAZ® + TX, TAZO B®) + TX, Azotobacter + TX, Azotobacter chroococcum (Azotomeal®) + TX, Azotobacter cysts (Bionatural Blooming Blossoms®, TX) + TX amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus chitinosporus strain CM-1 + TX, Bacillus chitinosporus strain AQ746 + TX, Bacillus licheniformis strain HB-2 (Biostart™ Rhizoboost®) + TX, Bacillus licheniformis strain 3086 (Eco ® + TX, Green Releaf®) + TX, Bacillus circulans + TX, Bacillus firmus (BioSafe®, BioNem-WP®, VOTiVO®) + TX, Bacillus firmus strain I-1582 + TX, Bacillus macerans + TX, Bacillus marismortui + TX, Bacillus megaterium + TX, Bacillus mycoides strain AQ726 + TX, Bacillus papillae (Milky Spore Powder®) + TX, Bacillus pumilus spp. + TX, Bacillus pumilus strain GB34 (Yield Shield®) + TX, Bacillus pumilus strain AQ717 + TX, Bacillus pumilus strain QST 2808 (Sonata® + TX, Ballad Plus®) + TX, Bacillus spahericus (VectoLex®) + TX, Bacillus spp. + TX, strain of Bacillus spp. AQ175 + TX, strain of Bacillus spp. AQ177 + TX, strain of Bacillus spp. AQ178 + TX, Bacillus subtilis strain QST 713 (CEASE® + TX, Serenade® + TX, Rhapsody®) + TX, Bacillus subtilis strain QST 714 (JAZZ®) + TX, Bacillus subtilis strain AQ153 + TX, strain of Bacillus subtilis AQ743 + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain QST3004 + TX, Bacillus subtilis strain var. amyloliquefaciens FZB24 (Taegro® + TX, Rhizopro®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1Ab + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis israel® + TX (BMP123, Aqua) + TX, VectoBac®) + TX, Bacillus thuringiensis kurstaki (Javelin® + TX, Deliver® + TX, CryMax® + TX, Bonide® + TX, Scutella WP® + TX, Turilav WP® + TX, Astuto® + TX, Dipel WP® + TX, Biobit® + TX, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF/3P®) + TX, Bacillus thuringiensis strain BD#32 + TX, Bacillus thuringiensis strain AQ52 + TX, Bacillus thuringiensis var. aizawai (XenTari® + TX, DiPel®) + TX, bacteria spp. (GROWMEND® + TX, GROWSWEET® + TX, Shootup®) + TX, Clavipacter michiganensis bacteriophage (AgriPhage®) + TX, Bakflor® + TX, Beauveria bassiana (Beaugenic® + TX, Brocaril WP®) + TX, Beauveria bassiana GHA (Mycotrol ES® + TX, Mycotrol O® + TX, BotaniGuard®) + TX, Beauveria brongniartii (Engerlingspilz® + TX, Schweizer Beauveria® + TX, Melocont®) + TX, Beauveria spp. + TX, Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Bacillus thuringiensis tenebrionis (Novodor®) + TX, BtBooster + TX, Burkholderia cepacia (Deny® + TX, Intercept® + TX Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp. + TX, Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reukaufii + TX, Candida saitoana (Bio-Coat® + TX, Biocure®) + TX, Candida sake + TX, Candida spp. + TX, Candida tenius + TX, Cedecea dravisae + TX, Cellulomonas flavigena + TX, Chaetomium cochliodes (Nova-Cide®) + TX, Chaetomium globosum (Nova-Cide®) + TX, Chromobacterium subtsugae strain PRAA4-1T (Grandevo®) ) + TX, Cladosporium cladosporioides + TX, Cladosporium oxysporum + TX, Cladosporium chlorocephalum + TX, Cladosporium spp. + TX, Cladosporium tenuissimum + TX, Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp. + TX, Cryptococcus albidus (YIELDPLUS®) + TX, Cryptococcus humicola + TX, Cryptococcus infirmo-miniatus + TX, Cryptococcus laurentii + TX, Cryptophlebia leucotreta granulovirus (Cryptex®) + TX, Cupriavidus Cymondia pomonensis + TX, X®) + TX, Cydia pomonella granulovirus (Madex® + TX, Madex Plus® + TX, Madex Max/Carpovirusine®) + TX, Cylindrobasidium laeve (Stumpout®) + TX, Cylindrocladium + TX, Debaryomyces hansenii + TX, Drechensislera hawaiin + TX, Enterobacter cloacae + TX, Enterobacteriaceae + TX, Entomophtora virulenta (Vektor®) + TX, Epicoccum nigrum + TX, Epicoccum purpurascens + TX, Epicoccum spp. + TX, Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean®/Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop® + TX, Prestop®) + TX, Gliocladium roseum + TX, Gliocladium spp. (SoilGard®) + TX, Gliocladium virens (Soilgard®) + TX, Granulovirus (Granupom®) + TX, Halobacillus halophilus + TX, Halobacillus litalis + TX, Halobacillus trueperi + TX, Halomonas spp. + TX, Halomonas subglaciescola + TX, Halovibrio variabilis + TX, Hanseniaspora uvarum + TX, Helicoverpa armigera nucleopolyhedrovirus (Helicovex®) + TX, Helicoverpa zea nuclear polyhedrosis virus (Gemstar®) + TX, Isoflavone - formononetin (My TX) + Kloeckera apiculata + TX, Kloeckera spp. + TX, Lagenidium giganteum (Laginex®) + TX, Lecanicillium longisporum (Vertiblast®) + TX, Lecanicillium muscarium (Vertikil®) + TX, Lymantria Dispar nucleopolyhedrosis virus (Disparvirus®) + TX, Marinococcus halophilus + TX, Meira konigi , Metarhizium anisopliae (Met52®) + TX, Metarhizium anisopliae (Destruxin WP®) + TX, Metschnikowia fruticola (Shemer®) + TX, Metschnikowia pulcherrima + TX, Microdochium dimerum (Antibot®) + TX, Microseropsiero TX, Micromono + TX, Muscodor albus 620 (Muscudor®) + TX, Muscodor roseus strain A3-5 + TX, Mycorrhizae spp. (AMykor® + TX, Root Maximizer®) + TX, Myrothecium verrucaria strain AARC-0255 (DiTera®) + TX, BROS PLUS® + TX, Ophiostoma piliferum strain D97 (Sylvanex®) + TX, Paecilomyces farinosus + TX, Paecilomyces fumosoroseus (PFR-97® + TX, PreFeRal®) + TX, Paecilomyces linacinus (Biostat WP®) + TX, Paecilomyces lilacinus strain 251 (MeloCon WG®) + TX, Paenibacillus polymyxa + TX, Pantoea Blight-Blightmerans ( 1®) + TX, Pantoea spp. + TX, Pasteuria spp. (Econem®) + TX, Pasteuria nishizawae + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart® + TX, TagTeam®) + TX, Penicillium brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseogenpuricium + TX, TX, purfulvum , Penicillium spp. + TX, Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, phosphate solubilizing bacteria (Phosphomeal®) + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + Pichia + TX, TX, Pichia Membraneefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas corrugate + TX (Pseudomonas corrugate) (Att. + TX, Pseudomonas fluorescens strain A506 (BlightBan A506®) + TX, Pseudomonas putida + TX, Pseudomonas reactans + TX, Pseudomonas spp. + TX, Pseudomonas syringae (Bio-Save®) + TX, Pseudomonas viridiflava + TX, Pseudomons fluorescens (Zequanox®) + TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®) + TX, Puccinia Puccinia + TX thlaspeos (Wood Warrior®) + TX, Pythium paroecandrum + TX, Pythium oligandrum (Polygandron® + TX, Polyversum®) + TX, Pythium periplocum + TX, Rhanella aquatilis + TX, Rhanella spp. + TX, Rhizobia (Dormal® + TX, Vault®) + TX, Rhizoctonia + TX, strain of Rhodococcus globerulus 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 minorium, TX® (SARRITOR®.) + TX, Scytalidium uredinicola + TX, Spodoptera exigua nuclear polyhedrosis virus (Spod-X® + TX, Spexit®) + TX, Serratia marcescens + TX, Serratia plymuthica + TX, Serratia spp. + TX, Sordaria fimicola + TX, Spodoptera littoralis nucleopolyhedrovirus (Littovir®) + TX, Sporobolomyces roseus + TX, Stenotrophomonas maltophilia + TX, Streptomyces ahygroscopicus + TX, Streptomyces albaduncus + TX, Streptomyces galles TX, Streptomyces exfoliates + TX, Streptomyces exfoliates + TX, Streptomyces griseoviridis (Mycostop®) + TX, Streptomyces lydicus (Actinovate®) + TX, Streptomyces lydicus WYEC-108 (ActinoGrow®) + TX, Streptomyces violaceus + TX, Tilletiopsis + TX, Tilletiopsis + TX, Tilletiopsis + TX. + TX, Trichoderma asperellum (T34 Biocontrol®) + TX, Trichoderma gamsii (Tenet®) + TX, Trichoderma atroviride (Plantmate®) + TX, Trichoderma hamatum TH 382 + TX, Trichoderma harzianum rifai (Mycostar®) + TX, Trichonum T-22 (Trianum-P® + TX, PlantShield HC® + TX, RootShield® + TX, Trianum-G®) + TX, Trichoderma harzianum T-39 (Trichodex®) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma spp. LC 52 (Sentinel®) + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + TX, Trichoderma taxi + TX, Trichoderma virens + TX, Trichoderma virens (formerly Gliocladium virens GL-21) SoilGuard®) + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, Trichosporon spp. + TX, Trichothecium spp. + TX, Trichothecium roseum + TX, Typhula phacorrhiza strain 94670 + TX, Typhula phacorrhiza strain 94671 + TX, Ulocladium atrum + TX, Ulocladium oudemansii (Botry-Zen®) + TX, Ustilago maydis + TX, various bacteria and supplementary micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Verticillium lecanii (Mycotal® + TX, Vertalec®) + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv. Poae (Camperico®) + TX, Xenorhabdus bovienii + TX, Xenorhabdus nematophilus; and Plant extracts including: pine oil (Retenol®) + TX, azadirahtin (Plasma Neem Oil® + TX, AzaGuard® + TX, MeemAzal® + TX, Molt-X® + TX, Botanical IGR (Neemazad®, Neemix®) + TX, canola oil (Lilly Miller Vegol®) + TX, Chenopodium ambrosioides near ambrosioides (Requiem®) + TX, Chrysanthemum extract (Crisant®) + TX, neem oil extract (Trilogy®) + TX, essential oils of Labiatae (Botania®) + TX, extracts of clove oil, rosemary, peppermint and thyme (Garden insect killer®) + TX, Glycinebetaine (Greenstim®) + TX, garlic + TX, lemongrass oil (GreenMatch ®) + TX, nepeta oil + TX, Nepeta catarina (Oil of catnip) + TX, Nepeta catarina + TX, nicotine + TX, oregano oil (MossBuster®) + TX, Pedaliaceae oil (Nematon®) + TX, pyrethrum + TX, Quillaja saponaria (NemaQ®) + TX, Reynoutria sachalinensis (Regalia® + TX, Sakalia®) + TX, rotenone (Eco Roten®) + TX, plant extract of Rutaceae (Soleo®) + TX, soybean oil (Ortho ecosense®) + TX, tea tree oil (Ti morex Gold®) + TX, thyme oil + TX, AGNIQUE® MMF + TX, BugOil® + TX, extract blend of rosemary, sesame, peppermint, thyme and cinnamon (EF 300®) + TX, extract blend of cloves, rosemary and peppermint (EF 400®) + TX, blend of clove oil, peppermint and garlic and mint (Soil Shot®) + TX, kaolin (Screen®) + TX, Algae Storage Glucame browns (Laminarin®) + TX; and pheromones including: Black-headed Fireworm Pheromone (3M Sprayable Blackheaded Fireworm Pheromone®) + TX, Moth Pheromone (Paramount dispenser-(CM)/ Isomate C-Plus®) + TX, Grape Berry Moth Pheromone (3M MEC-GBM Sprayable Pheromone®) + TX, Leaf Wrapper Pheromone (3M MEC - LR Sprayable Pheromone®) + TX, Muscamona (Snip7 Fly Bait® + TX, Starbar Premium Fly Bait®) + TX, Moth Pheromone oriental fruit (3M oriental fruit moth sprayable pheromone®) + TX, peach borer pheromone (Isomate-P®) + TX, tomato worm pheromone (3M sprayable pheromone®) + TX, entostat powder (palm extract ) (Exosex CM®) + TX, Tetradecatrienyl acetate + TX 13- Hexadecatrienal + TX, (E + TX,Z)-7 + TX, 9-dodecadien-1-yl acetate + TX, 2-Methyl-1- Butanol + TX, Calcium Acetate + TX, Scenturion® + TX, Biolure® + TX, Check-Mate® + TX, Lavanduilla Senecioate; and Macrobians including: Aphelinus abdominalis + TX, Aphidius ervi (Aphelinus-System®) + TX, Acerophagus papaya + TX, Adalia bipunctata (Adalia-System®) + TX, Adalia bipunctata (Adaline®) + TX, Adalia bipunctata (Aphidalia® ) + TX, Ageniaspis citricola + TX, Ageniaspis fuscicollis + TX, Amblyseius andersoni (Anderline® + TX, Andersoni-System®) + TX, Amblyseius californicus (Amblyline® + TX, Spical®) + TX, Amblysius cucumxeris ( TX, Bugline cucumeris®) + TX, Amblyseius fallacis (Fallacis®) + TX, Amblyseius swirskii (Bugline swirskii® + TX, Swirskii-Mite®) + TX, Amblyseius womersleyi (WomerMite®) + hesperidus TX, Amblyseius atomus + TX, Anagyrus fusciventris + TX, Anagyrus kamali + TX, Anagyrus loecki + TX, Anagyrus pseudococci (Citripar®) + TX, Anicetus benefices + TX, Anisopteromalus calandrae + TX, Anthocoris nemoralis (Anthocoris-System®) + TX abdominalis (Apheline® + TX, Aphiline®) + TX, Aphelinus asychis + TX, Aphidius colemani (Aphipar®) + TX, Aphidiu s ervi (Ervipar®) + TX, Aphidius gifuensis + TX, Aphidius matricariae (Aphipar-M®) + TX, Aphidoletes aphidimyza (Aphidend®) + TX, Aphidoletes aphidimyza (Aphidoline®) + TX, Aphytis metis TX + TX, Aprostocetus hagenowii + TX, Atheta coriaria (Staphyline®) + TX, Bombus spp. + TX, Bombus terrestris (Natupol Beehive®) + TX, Bombus terrestris (Beeline® + TX, Tripol®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus + TX, Chrysoperla carnea (Chrysoline®) + TX, Chrysoperla carnea (Chrysopa carnea ®) + TX, Chrysoperla rufilabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichus phyllocnistoides + TX, Closterocerus chamaeleon + TX, Closterocerus spp. + TX, Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug® + TX, Cryptoline TX, TX) + TX , Dacnusa sibirica + TX, Dacnusa sibirica (Minusa®) + TX, Diglyphus isaea (Diminex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diaparchasmidatamorpha longica + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea + TX, Diglyphus isaea (Miglyphus® + TX, Digline®) + TX, Dacnusa sibirica (DacDigline® + TX, Minex®) + TX, Diversinervus spp. + TX, Encarsia citrine + TX, Encarsia formosa (Encarsia max® + TX, Encarline® + TX, En-Strip®) + TX, Eretmocerus eremicus (Enermix®) + TX, Encarsia guadeloupae + TX, Encarsia haitiensis + TX, Episyrphus balteatus (Syrphidend®) + TX, Eretmoceris siphonini + TX, Eretmocerus californicus + TX, Eretmocerus eremicus (Ercal® + TX, Eretline e®) + TX, Eretmocerus eremicus (Bemimix®) + TX, Eretmocerus TX, Eretmocerus TX Bemipar® + TX, Eretline m®) + TX, Eretmocerus siphonini + TX, Exochomus quadripustulatus + TX, Feltiella acarisuga (Spidend®) + TX, Feltiella acarisuga (Feltiline®) + TX, Fopius arisanus + TX, Fopius ceratitivo Formononetin (Wirless Beehome®) + TX, Franklinothrips vespiformis (Vespop®) + TX, Galendromus occidentalis + TX, Goniozus legneri + TX, Habrobracon hebetor + TX, Harmonia axyridis (HarmoBeetle®) + TX, Heterorhabd. (Lawn Patrol®) + TX, Heterorhabditis bacteriophora (NemaShield HB® + TX, Nemaseek® + TX, Terranem-Nam® + TX, Terranem® + TX, Larvanem® + TX, B-Green® + TX, NemAttack ® + TX , Nematop®) + TX, Heterorhabditis megidis (Nemasys H® + TX, BioNem H® + TX, Exhibitline hm® + TX, Larvanem-M®) + TX, Hippodamia convergens + TX, Hypoaspis aculeifer (Aculeifer-System® + TX , Entomite-A®) + TX, Hypoaspis miles (Hypoline m® + TX, Entomite-M®) + TX, Lbalia leucospoides + TX, Lecanoideus floccissimus + TX, Lemophagus errabundus + TX, Leptomastidea abnormis + Leptoparyl ®) + TX, Leptomastix epona + TX, Lindorus lophanthae + TX, Lipolexis oregmae + TX, Lucilia caesar (Natufly®) + TX, Lysiphlebus testaceipes + TX, Macrolophus caliginosus (Mirical-N® + TX, Macroline c® + TX, Mirical®) + TX, Mesoseiulus longipes + TX, Metaphycus flavus + TX, Metaphycus lounsburyi + TX, Micromus angulatus (Milacewing®) + TX, Microterys flavus + TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®) + TX, Neodryinus typhlocybae + TX, Neoseiulus californicus + TX, Neoseiulus cucumeris (THRYPEX®) + TX, Neoseiulus fallacis + TX, Nesideocoris tenuis (NesidioBug® + TX, Nesibug®) + TX, TX,® (Bisphyra a) Orius insidiosus (Thripor-I® + TX, Oriline i®) + TX, Orius laevigatus (Thripor-L® + TX, Oriline I®) + TX, Orius majusculus (Oriline m®) + TX, Orius 184/195 strigicollis ( Thripor-S®) + TX, Pauesia juniperorum + TX, Pediobius foveolatus + TX, Phasmarhabditis hermaphrodita (Nemaslug®) + TX, Phymastichus coffea + TX, Phytoseiulus macropilus + TX, Phytoseiulus persimilis + pspidex® (Spidex®) TX, Podisus maculiventris (Podisus®) + TX, Pseudacteon curvatus + TX, Pseudacteon obtusus + TX, Pseudacteon tricuspis + TX, Pseudaphycus maculipennis + TX, Mexican Pseudleptomastix + TX, Psyllae- shusticus TX + TX, Psyllae- shusticus TX + spp. + TX, Rhyzobius lophanthae + TX, Rodolia cardinalis + TX, Rumina decollate + TX, Semielacher petiolatus + TX, Sitobion avenae (Ervibank®) + TX, Steinernema carpocapsae (Nematac C® + TX, Millenium® + TX, BioNem C® TX, NemAttack® + TX, Nemastar® + TX, Capsanem®) + TX, Steinernema feltiae (NemaShield® + TX, Nemasys F® + TX, BioNem F® + TX, Steinernema-System® + TX, NemAttack® + TX, Nemaplus® + TX, Exhibitline sf® + TX, Sciarid® + TX, Entonem®) + TX, Steinernema kraussei (Nemasys L® + TX, BioNem L® + TX, Exhibitline srb®) + TX, Steinernema riobrave (BioVector ® + TX, BioVektor®) + TX, Steinernema scapterisci (Nematac S®) + TX, Steinernema spp. + TX, Steinernematid spp. (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX (Trichogramma brassicae) Tricho-Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator; and other biologicals including: abscisic acid + TX, bioSea® + TX, Chondrostereum purpureum (Chontrol Paste®) + TX, Colletotrichum gloeosporioides (Collego®) + TX, Copper Octanoate (Cueva®) + TX, Delta Traps (Trapline d® ) + TX, Erwinia amylovora (Harpina) (ProAct® + TX, Ni-HIBIT Gold CST®) + TX, Ferri-phosphate (Ferramol®) + TX, Funnel Traps (Trapline y®) + TX, Gallex® + TX , Grower's Secret® + TX, Homo-brassonolid + TX, Iron Phosphate (Lilly Miller Worry Free Ferramol Slug & Snail Bait®) + TX, MCP Hail Trap (Trapline f®) + TX, Microctonus hyperodae + TX, Mycoleptodiscus terrestris (Des-X®) + TX, BioGain® + TX, Aminomite® + TX, Zenox® + TX, Pheromone Trap (Thripline ams®) + TX, Potassium Bicarbonate (MilStop®) + TX, Acid Potassium Salts fatty acids (Sanova®) + TX, potassium silicate solution (Sil-Matrix®) + TX, potassium iodide + potassium thiocyanate (Enzicur®) + TX, SuffOil- X® + TX, Spider venom + TX, Nosema locustae (Semaspore Organic Grasshopper Control®) + TX, Sticky Traps (Trapline YF® + TX, Rebell Amarillo®) + TX and Traps (Takitrapline y + b®) + TX.
[0171] References in parentheses after active ingredients, eg [3878-19-1] refer to the Chemical Abstracts Registry Number. The mixing partners described above are known. When active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: CSD TomLin; The British Crop Protection Council], are described there with the entry number given in parentheses here above for the particular compound; for example, the compound "abamectin" is described under entry number (1). Where “[CCN]” is previously added to the particular compound, the compound in question is included in the “Compendium of Pesticide Common Names”, which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2004]; for example, the compound "acetoprol" is described under the internet address http://www.alanwood.net/pesticides/acetoprol.html.
[0172] In this document, most of the active ingredients described above are named by a so-called "common name", the relevant "ISO common name" or another "common name" which is used in particular cases. If the designation is not a "common name", the nature of the designation used instead is given in parentheses for the particular compound; in this case, the IUPAC name, the IUPAC/Chemical Abstracts name, a “chemical name”, a “traditional name”, a “compound name” or a “development code” is used. "CAS Reg. No" means the Chemical Abstracts Registration Number.
[0173] The mixture of active ingredients of the compounds of formula I selected from Tables 1 to 3 and P with active ingredients described above comprises a compound selected from Tables 1 to 3 and P and an active ingredient as described above preferably in a mixing ratio from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5: 1 and 1:5, with a ratio of 2:1 to 1:2 being especially preferred, and a ratio of 4:1 to 2:1 being likewise preferred, above all a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. These mixing ratios are by weight.
[0174] Mixtures as described above can be used in a method of controlling pests, which comprises applying a composition comprising a mixture as described above to pests or their environment, with the exception of a method of surgical or therapeutic treatment of the body human or animal and diagnostic methods practiced on the human or animal body.
[0175] Mixtures comprising a compound of formula I selected from Tables 1 to 3 and P and one or more ingredients as described above can be applied, for example, in a single "ready-to-mix" form, in a mix to combined spray consisting of separate formulations of the individual active ingredient components, such as a "mixing tank", and in a combined use of the individual active ingredients when applied in a sequential manner, ie one after the other, within a period reasonably short, such as a few hours or days. The order of application of the compounds of formula I selected from Tables 1 to 3 and P and the active ingredients as described above is not essential for carrying out the present invention.
[0176] The compositions according to the invention may also comprise other solid or liquid auxiliaries, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (eg soy oil, rapeseed oil or epoxidized coconut oil), defoamers , for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients to achieve specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
[0177] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries, for example, by grinding, sieving and/or compressing a solid active ingredient and in the presence of at least one auxiliary, by example by intimate mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of compounds I for the preparation of these compositions are also an object of the invention.
[0178] Application methods for the compositions, that is, pest control methods of the aforementioned type, such as spraying, atomizing, dusting, brushing, covering, dispersing or pouring - which must be selected to suit the objectives requirements of the prevailing circumstances - and the use of the pest control compositions of the aforementioned type, are further objects of the invention. Typical concentration rates are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The application rate per hectare is generally from 1 to 2000 g of active ingredient per hectare, in particular from 10 to 1000 g/ha, preferably from 10 to 600 g/ha.
[0179] A preferred method of application in the crop protection area is application to the foliage of plants (foliar application), being possible to select the frequency and rate of application to meet the danger of infestation with the pest in question. Alternatively, the active ingredient can reach the plants through the root system (systemic action), by soaking the plant site with a liquid composition or by incorporating the active ingredient in solid form at the plant site, for example in the soil, for example in the granule form (soil application). In the case of paddy fields, such granules can be calibrated in the flooded paddy field.
[0180] The compounds of the invention and their compositions are also suitable for the protection of plant propagation material, for example seeds, such as fruits, tubers or grains, or nursery plants, against pests of the aforementioned type. The propagation material can be treated with the compost before planting, for example a seed can be treated before sowing. Alternatively, the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted at the application site, for example in the seed furrow during the rowing process. These methods of treatment for the plant propagation material and the plant propagation material thus treated are further objects of the invention. Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 and 200 grams per 100 kg of seeds, preferably between 5 and 150 grams per 100 kg of seeds, such as between 10 and 100 grams per 100 kg of seeds.
[0181] The term seed encompasses plant seeds and propagules of all types including but not limited to true seeds, seed pieces, shoots, calluses, bulbs, fruits, tubers, grains, rhizomes, cuttings, cuttings and the like and means in a preferred modality true seeds.
[0182] The present invention also comprises seeds coated or treated with or containing a compound of formula I. The term "coated or treated with and/or containing" generally means that the active ingredient is mostly on the surface of the seed upon application, although a greater or lesser part of the ingredient may penetrate the seed material, depending on the method of application. When said seed product is (re)planted, it can absorb the active ingredient. In one embodiment, the present invention makes available a plant propagation material adhered thereto with a compound of formula I. Additionally, a composition comprising a plant propagation material treated with a compound of formula I is thereby made available.
[0183] Seed treatment comprises all suitable seed treatment techniques known in the art, such as seed treatment, seed coating, seed dusting, seed soaking and seed pelleting. The seed treatment application of the compound of formula I can be carried out by any known methods, such as spraying or dusting the seeds before sowing or during sowing/planting of the seeds. Biological Examples: Example B1: Diabrotica balteata (corn rootworm):
[0184] Corn sprouts placed on an agar overlay in 24-well microtiter plates were treated with aqueous test solutions prepared from stock solutions in DMSO at 10'000 ppm by spray. After drying, the plates were infested with L2 larvae (6 to 10 per well). Samples were evaluated for mortality and growth inhibition compared to untreated samples 4 days after infestation.
[0185] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1 and P2. Example B2:Euschistus heros (Neotropical brown stink bug):
[0186] Soybean sheets on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from stock solutions in DMSO at 10'000 ppm. After drying, the leaves were infested with N2 nymphs. Samples were evaluated for mortality and growth inhibition compared to untreated samples 5 days after infestation.
[0187] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1 and P2. Example B3:Myzus persicae (Green peach aphid): Feeding/contact activity
[0188] Sunflower leaf discs were placed on agar in a 24-well microtiter plate and sprayed with aqueous test solutions prepared from stock solutions in DMSO at 10'000 ppm. After drying, the leaf discs were infested with a population of mixed-age aphids. Samples were evaluated for mortality 6 days after infestation.
[0189] The following compound resulted in at least 80% mortality at an application of 200 ppm: P1 and P2. Example B4:Myzus persicae (Green peach aphid): Systemic activity
[0190] Roots of pea seedlings infested with a population of mixed-age aphids were placed directly into aqueous test solutions prepared from 10'000 DMSO stock solutions. Samples were evaluated for mortality 6 days after placing the seedlings in test solutions.
[0191] The following compound resulted in at least 80% mortality at a test rate of 24 ppm: P2. Example B5:Plutella xylostella (Cruciferous Moth):
[0192] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from stock solutions in DMSO at 10'000 ppm by pipetting. After drying, the plates were infested with L2 larvae (10 to 15 per well). Samples were evaluated for mortality and growth inhibition compared to untreated samples 5 days after infestation.
[0193] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1 and P2. Example B6:Spodoptera littoralis (Egyptian cotton canopy)
Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from stock solutions in DMSO at 10'000 ppm. After drying, the leaf discs were infested with five L1 larvae. Samples were evaluated for mortality, anti-feeding effect and growth inhibition compared to untreated samples 3 days after infestation. Control of Spodoptera littoralis by a test sample is given when at least one of the categories mortality, anti-feeding effect, and growth inhibition is higher than the untreated sample.
[0195] The following compound resulted in at least 80% control at an application rate of 200 ppm: P1. Example B6:Spodoptera littoralis (Egyptian cotton canopy)
[0196] Test compounds were applied by pipette from stock solutions in DMSO at 10'000 ppm in 24-well plates and mixed with agar. Lettuce seeds were placed on the agar and the multi-well plate was closed by another plate that also contained agar. After 7 days, the compost was taken up by the roots and the lettuce grew to the lid plate. The lettuce leaves were then cut into the lid plate. Spodoptera eggs were pipetted through a plastic stencil onto a wet gel staining paper and the lid plate went with it. Samples were evaluated for mortality, anti-feeding effect and growth inhibition compared to untreated samples 6 days after infestation.
[0197] The following compound gave an effect of at least 80% in at least one of the three categories (mortality, antifeeding, or growth inhibition) at a test rate of 12.5 ppm: P1. Example B7: Frankliniella occidentalis (California Thrips): Feeding/Contact Activity
[0198] Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from stock solutions in DMSO at 10'000. After drying, the leaf discs were infested with a mixed-age population of Frankliniella. Samples were evaluated for mortality 7 days after infestation.
[0199] The following compound resulted in at least 80% mortality at an application of 200 ppm: P2. Example B8: Thrips tabaci(Onion thrips) Food/contact activity
[0200] Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from stock solutions in DMSO at 10'000 ppm. After drying, the leaf discs were infested with a population of mixed-age thrips. Samples were evaluated for mortality 6 days after infestation.
[0201] The following compound resulted in at least 80% mortality at an application rate of 200 ppm: P2.

权利要求:
Claims (4)
[0001]
1. Compound of formula I,
[0002]
2. Pesticidal composition characterized in that it comprises at least one compound of formula I, as defined in claim 1, or, where appropriate, a tautomer thereof, in each case in free form or in agrochemically usable salt form, as active ingredient and at least one help.
[0003]
3. A method for controlling pests, characterized in that it comprises applying a composition, as defined in claim 2, to pests or their environment, with the exception of a method for treating the human or animal body by surgery or therapy and diagnostic methods practiced on the body human or animal.
[0004]
4. Method for the protection of plant propagation material from attack by pests, characterized in that it comprises treatment of the propagation material, or the place where the propagation material is planted, with a composition, as defined in claim 2.

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法律状态:
2019-09-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-05-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-07-20| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/12/2015, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP14200413.4|2014-12-29|

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EP14200413|2014-12-29|

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PCT/EP2015/079877|WO2016107742A1|2014-12-29|2015-12-15|Pesticidally active tetracyclic derivatives with sulfur containing substituents|

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