BR112019022730B1 - HETEROCYCLIC DERIVATIVES WITH PESTICIDE-ACTIVE SULFUR-CONTAINING SUBSTITUTES - Google Patents

Abstract

Compounds of formula (I), (I), wherein the substituents are as defined in claim 1, and the agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of these compounds, can be used as insecticides and can be prepared from a way known per se.

Description

[0001] The present invention relates to heterocyclic derivatives containing sulfur substituents active in pesticide terms, in particular active in insecticide terms, with processes for their preparation, with compositions comprising these compounds and with their use for controlling 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

[0003] WO 2014/123206, WO 2014/132972 and WO 2015/121136. New heterocyclic acyl sulfilimine and sulfoximine derivatives with pesticide-active phenyl- and pyridyl-containing sulfur substituents have now been discovered.

[0004] The present invention accordingly relates to compounds of formula I, where A is CH or N; X is S, SO or SO2; R1 is C1-C4 alkyl, C1-C4 haloalkyl or C3-C6 cycloalkyl-C1-C4 alkyl; R7 and R8 are, independently of each other, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C6 cyanoalkyl, C1-C4 alkoxy, C1-C4 alkyl, pyridyl or phenyl, wherein said pyridyl or phenyl may be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl and — C(O)haloalkyl C1-C4; or R7 and R8, together with the sulfur atom to which they are attached, form a saturated ring system with four to six members, said ring system may be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, alkyl C1-C4, C1-C4 alkoxy and C1-C4 haloalkyl; and said ring system may contain a heteroatom selected from the group consisting of nitrogen, oxygen and sulfur; n is 0 or 1; Q is a radical selected from the group consisting of the formulas Q1 to Q4 wherein the arrow denotes the point of attachment to the ring incorporating the radical A; and wherein X1 is O, S or NR3, wherein R3 is C1-C4 alkyl; R2 is halogen, C1-C6 haloalkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C1-C6 haloalkoxy; G1 is N or CH; G2 and G3 are, independently of each other, N or CH; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of the compounds of formula I.

[0005] Compounds of formula I which have 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, acid nitrous, a phosphorous acid or a hydrohalic acid, with strong organic carboxylic acids, such as C1-C4 alkanecarboxylic acids that are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, e.g. 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 acids organic sulfonic acids, such as C1-C4 alkane- or arylsulfonic acids that are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid. Compounds of formula I which have at least one acid 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 mono-, di- or tri-lower alkyl amine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or tri - hydroxy-short-chain alkyl-amine, for example mono-, di- or triethanolamine.

[0006] The alkyl groups occurring in the definitions of substituents can have a straight or branched chain 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. The alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, alkoxy, alkenyl and alkynyl radicals are derivatives of the mentioned alkyl radicals. The alkenyl and alkynyl groups can be mono- or polyunsaturated.

[0007] Halogen is generally fluorine, chlorine, bromine or iodine. This also applies, correspondingly, to halogens in combination with other meanings, such as haloalkyl or halophenyl.

[0008] 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; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

[0009] Alkoxy groups preferably have a preferred chain length of 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, iso-butoxy, sec-butoxy and tert-butoxy and also the isomeric radicals of pentyloxy and hexyloxy; preferably methoxy and ethoxy.

[0010] The alkoxyalkyl groups preferably have a chain length of 1 to 6 carbon atoms, more preferably a chain length of 1 to 4 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.

[0011] Alkylsulfanyl is, for example, methylsulfanyl, ethylsulfanyl, propylsulfanyl, isopropylsulfanyl, butylsulfanyl, pentylsulfanyl and hexylsulfanyl.

[0012] Alkylsulfinyl is for example methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, a butylsulfinyl, pentylsulfinyl and hexylsulfinyl.

[0013] Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, pentylsulfonyl and hexylsulfonyl.

[0014] Cycloalkyl groups preferably have 3 to 6 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0015] Haloalkoxy groups preferably have a chain length of 1 to 4 carbon atoms. Haloalkoxy is, for example, difluoromethoxy, trifluoromethoxy or 2,2,2-trifluoroethoxy.

[0016] Haloalkylsulfanyl groups preferably have a chain length of 1 to 4 carbon atoms. Haloalkylsulfanyl is, for example, difluoromethylsulfanyl, trifluoromethylsulfanyl or 2,2,2-trifluoroethylsulfanyl. Similar considerations apply to C1-C4 haloalkylsulfinyl and C1-C4 haloalkylsulfonyl radicals, which may be, for example, trifluoromethylsulfinyl, trifluoromethylsulfonyl or 2,2,2-trifluoroethylsulfonyl.

[0017] 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 four times substituted, preferably monosubstituted up to three times substituted, more preferably mono- or doubly substituted.

[0018] Free radicals represent methyl groups.

[0019] The compounds of formula I according to the invention also include hydrates that can be formed during the formation of salts.

[0020] Preferred values of X1, Q, R1, R2, R7, R8,

[0021] Most preferably, X1 is NCH3.

[0022] Preferably, Q is a radical selected from the group consisting of the formulas Q1a, Q1b, Q2a, Q3a and Q4a , where the arrow denotes the point of attachment to the ring incorporating the radical A.

[0023] Most preferably, Q is the radical Q1a, Q1b or Q2a.

[0024] Preferably, R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl.

[0025] More preferably, R1 is C1-C4 alkyl or cyclopropylmethyl.

[0026] Even more preferably, R1 is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl.

[0027] Most preferably, R1 is ethyl.

[0028] Preferably, R2 is halogen, C1 C4 haloalkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl.

[0029] More preferably, R2 is halogen or C1-C3 haloalkyl.

[0030] Even more preferably, R2 is C1-C2 haloalkyl.

[0031] Most preferably, R2 is trifluoromethyl.

[0032] Preferably, R7 and R8 are each independently C1-C6 alkyl; or R7 and R8 together with the sulfur atom to which they are attached form a saturated ring system with four to six members, which may contain an oxygen atom.

[0033] More preferably, R7 and R8 are each independently C1-C4 alkyl; or R7 and R8 together with the sulfur atom to which they are attached form a saturated four- or five-membered ring system, without an oxygen atom, or a saturated six-membered ring system, which may contain an oxygen atom.

[0034] Even more preferably, R7 and R8 are each independently methyl, ethyl, n-propyl or isopropyl; or R7 and R8 together with the sulfur atom to which they are attached form a saturated four-membered ring system lacking an oxygen atom, or a saturated six-membered ring system containing an oxygen atom (most preferably, the saturated six-membered ring system is -CH2CH2OCH2CH2-).

[0035] Most preferably, R7 is methyl and R8 is ethyl; or R7 and R8 are both methyl; or R7 and R8 are both ethyl.

[0036] Preferably, X is S or SO2.

[0037] Most preferably, X is SO2.

[0038] Preferably, A is N.

[0039] Preferably n is 1.

[0040] Embodiments according to the invention are provided as shown below.

[0041] Modality 1 provides compounds of formula I, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined above.

[0042] Modality 2 provides compounds, or a salt, stereoisomer, enantiomer, tautomer or agrochemically acceptable N-oxide thereof, according to modality 1 in which Q is a radical selected from the group consisting of the formulas Q1a, Q1b, Q2a, Q3a and Q4a , where the arrow denotes the point of attachment to the ring incorporating the radical A.

[0043] Modality 3 provides compounds, or a salt, stereoisomer, enantiomer, tautomer or agrochemically acceptable N-oxide thereof, according to modality 1 or 2 in which R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1C4 alkyl .

[0044] Modality 4 provides compounds, or a salt, stereoisomer, enantiomer, tautomer or agrochemically acceptable N-oxide thereof, according to any of modalities 1, 2 or 3 in which R2 is halogen, C1C4 haloalkyl, C1-haloalkylsulfanyl C4, C1-C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl.

[0045] Embodiment 5 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to any of embodiments 1, 2, 3 or 4 in which R7 and R8 are each independently alkyl C1-C6; or R7 and R8 together with the sulfur atom to which they are attached form a saturated ring system with four to six members, which may contain an oxygen atom.

[0046] Modality 6 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to any of modalities 1, 2, 3, 4 or 5 where X is S or SO2.

[0047] Modality 7 provides compounds, or a salt, stereoisomer, enantiomer, tautomer or agrochemically acceptable N-oxide thereof, according to any of modalities 1, 2, 3, 4, 5 or 6 in which R1 is C1 alkyl -C4 or cyclopropylmethyl.

[0048] Modality 8 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to any of modalities 1, 2, 3, 4, 5, 6 or 7 in which R2 is halogen or C1-C3 haloalkyl.

[0049] Modality 9 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to any of modalities 1, 2, 3, 4, 5, 6, 7 or 8 in which R7 and R8 are each independently C1-C4 alkyl; or R7 and R8 together with the sulfur atom to which they are attached form a saturated four- or five-membered ring system, without an oxygen atom, or a saturated six-membered ring system, which may contain an oxygen atom.

[0050] Modality 10 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to any of modalities 1, 2, 3, 4, 5, 6, 7, 8 or 9 where X is SO2.

[0051] Modality 11 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to any of modalities 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 wherein R1 is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl.

[0052] Modality 12 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to any of modalities 1, 2, 3, 4, 5, 6, 7, 8, 9 , 10 or 11 wherein R2 is C1-C2 haloalkyl.

[0053] Modality 13 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to any of modalities 1, 2, 3, 4, 5, 6, 7, 8, 9 , 10, 11 or 12 wherein R7 and R8 are each independently methyl, ethyl, n-propyl or isopropyl; or R7 and R8 together with the sulfur atom to which they are attached form a saturated four-membered ring system lacking an oxygen atom, or a saturated six-membered ring system containing an oxygen atom (most preferably, the saturated six-membered ring system is -CH2CH2OCH2CH2-).

[0054] Modality 14 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to any of modalities 1, 2, 3, 4, 5, 6, 7, 8, 9 , 10, 11, 12 or 13 where R1 is ethyl.

[0055] Modality 15 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to any of modalities 1, 2, 3, 4, 5, 6, 7, 8, 9 , 10, 11, 12, 13 or 14 wherein R2 is trifluoromethyl.

[0056] Modality 16 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to any of modalities 1, 2, 3, 4, 5, 6, 7, 8, 9 , 10, 11, 12, 13, 14 or 15 wherein R7 is methyl and R8 is ethyl; or R7 and R8 are both methyl; or R7 and R8 are both ethyl.

[0057] Modality 17 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to any of modalities 2, 3, 4, 5, 6, 7, 8, 9, 10 , 11, 12, 13, 14, 15 or 16 where Q is the radical Q1a.

[0058] Modality 18 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to any of modalities 2, 3, 4, 5, 6, 7, 8, 9, 10 , 11, 12, 13, 14, 15 or 16 where Q is the radical Q1b.

[0059] Modality 19 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to any of modalities 2, 3, 4, 5, 6, 7, 8, 9, 10 , 11, 12, 13, 14, 15 or 16 where Q is the radical Q2a.

[0060] Modality 20 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to any of modalities 2, 3, 4, 5, 6, 7, 8, 9, 10 , 11, 12, 13, 14, 15 or 16 where Q is the radical Q3a.

[0061] Modality 21 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to any of modalities 2, 3, 4, 5, 6, 7, 8, 9, 10 , 11, 12, 13, 14, 15 or 16 where Q is the radical Q4a.

[0062] Modality 22 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to any of modalities 1, 2, 3, 4, 5, 6, 7, 8, 9 , 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or 21 where A is N.

[0063] Modality 23 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to any of modalities 1, 2, 3, 4, 5, 6, 7, 8, 9 , 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or 21 where A is CH.

[0064] Modality 24 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to any of modalities 1, 2, 3, 4, 5, 6, 7, 8, 9 , 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 or 23 where n is 0.

[0065] Modality 25 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to any of modalities 1, 2, 3, 4, 5, 6, 7, 8, 9 , 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 or 23 where n is 1.

[0066] A preferred group of compounds of formula I is represented by compounds of formula I-1 wherein Q, A, n, R7 and R8 are as defined under formula I above; and wherein Xa1 is S, SO or SO2; Ra1 is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl.

[0067] In said preferred group of compounds of formula I-1, A is preferably N, Xa1 is preferably S or SO2, more preferably SO2, and Ra1 is preferably ethyl. In a further preferred group of compounds of formula I-1, A is preferably CH, Xa1 is preferably S or SO2, more preferably SO2, and Ra1 is preferably ethyl.

[0068] In another preferred group of compounds of formula I-1, n is 0 or 1, preferably n is 1, and R7 and R8 are, independently of each other, C1-C6 alkyl, even more preferably methyl or ethyl.

[0069] In yet another preferred group of compounds of formula I-1, n is 0 or 1, preferably n and 1, and R7 and R8, together with the sulfur atom to which they are attached, form a saturated ring system with four to six members, which may contain an oxygen atom, preferably, said ring system is not substituted, and said ring system does not contain an oxygen atom or contains an oxygen atom.

[0070] An additional preferred embodiment of said especially preferred groups of compound of formula I-1 comprises compounds in which A is N or CH; Xa1 is preferably SO2; Ra1 is preferably ethyl; n is 0 or 1; and R7 and R8 are, independently of each other, C1C6 alkyl, even more preferably methyl or ethyl; or R7 and R8, together with the sulfur atom to which they are attached, form a saturated six-membered ring system, which may contain an oxygen atom, preferably said ring system is unsubstituted, and said ring system contains an oxygen atom; or R7 and R8, together with the sulfur atom to which they are attached, form a four-membered saturated ring system, which may contain an oxygen atom, preferably said ring system is unsubstituted, and said ring system is not contains oxygen atom.

[0071] In compounds of formula I-1 and all preferred embodiments of compounds of formula I-1 mentioned above, Q is preferably selected from Q1 and Q2, wherein X1, R2, G1 and G3 are defined under formula I above . In said especially preferred group of compounds of formula I1, X1 is preferably NR3, in which R3 is C1-C4 alkyl, more preferably methyl; R2 is preferably C1-C6 haloalkyl, more preferably trifluoromethyl; G1 is CH or N; and G3 is preferably N.

[0072] In another preferred embodiment of compounds of formula I-1 and all preferred embodiments of compounds of formula I-1 mentioned above, Q is preferably selected from Q1 to Q4, wherein X1, R2, G1, G2 and G3 are defined under formula I above. In said especially preferred group of compounds of formula I-1, X1 is preferably NR3, in which R3 is C1-C4 alkyl, more preferably methyl; R2 is preferably C1-C6 haloalkyl, more preferably trifluoromethyl; G1 is CH or N, more preferably G1 is CH or N when Q is Q1 and G1 is N when Q is Q4; G2 is preferably CH; and G3 is preferably N.

[0073] An additional preferred group of compounds of formula I is represented by compounds of formula I-2 wherein X1, R2, G1, A, n, R7 and R8 are as defined under formula I above; and wherein Xa2 is S, SO or SO2; Ra2 is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl.

[0074] In said preferred group of compounds of formula I-2, A is preferably N; Xa2 is preferably S or SO2, more preferably SO2; and Ra2 is preferably ethyl. In a further preferred group of compounds of formula I-2, A is preferably CH; Xa2 is preferably S or SO2, more preferably SO2; and Ra2 is preferably ethyl.

[0075] In another especially preferred group of compounds of formula I-2, X1 is preferably NR3, in which R3 is C1-C4 alkyl, more preferably methyl; R2 is preferably C1-C6 haloalkyl, more preferably trifluoromethyl; and G1 is CH or N.

[0076] In compounds of formula I-2 and all preferred embodiments of compounds of formula I-2 mentioned above, n is 0 or 1, more preferably n is 1; and R7 and R8 are defined under formula I above. A further preferred embodiment of said especially preferred group of compounds of formula I-2 comprises compounds in which R7 and R8 are, independently of each other, C1-C6 alkyl, even more preferably methyl or ethyl; or R7 and R8, together with the sulfur atom to which they are attached, form a four- to six-membered saturated ring system, which may contain one oxygen atom; preferably, said ring system is not substituted, and said ring system does not contain an oxygen atom or contains an oxygen atom; or, more preferably, R7 and R8, together with the sulfur atom to which they are attached, form a saturated, unsubstituted, four-membered ring system containing no oxygen atom or a saturated, unsubstituted ring system, with six-membered, which contains one oxygen atom.

[0077] Another preferred group of compounds of formula I is represented by compounds of formula I-3 in which where A is N; R2 is C1-C6 haloalkyl, preferably trifluoromethyl; G1 is N or CH; n is 0 or 1, preferably n is 1; R7 and R8 are, independently of each other, C1-C6 alkyl, preferably methyl or ethyl; or R7 and R8, together with the sulfur atom to which they are attached, form a saturated six-membered ring system, which may contain an oxygen atom, preferably said ring system is unsubstituted, and said ring system contains an oxygen atom; or R7 and R8, together with the sulfur atom to which they are attached, form a four-membered saturated ring system, which does not contain an oxygen atom, preferably, said ring system is not substituted.

[0078] An additional preferred group of compounds of formula I is represented by compounds of formula I-4 wherein R2, G3, A, n, R7 and R8 are as defined under formula I above; and wherein Xa3 is S, SO or SO2; Ra3 is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl.

[0079] In said preferred group of compounds of formula I-4, A is CH or N; Xa3 is preferably S or SO2, more preferably SO2; and Ra3 is preferably ethyl. In another preferred group of compounds of formula I-4, R2 is preferably C1-C6 haloalkyl, even more preferably trifluoromethyl; and G3 is CH or N, preferably N.

[0080] In compounds of formula I-4 and all preferred embodiments of compounds of formula I-4 mentioned above, n is 0 or 1, more preferably n is 1; and R7 and R8 are defined under formula I above. A further preferred embodiment of said especially preferred group of compounds of formula I-4 comprises compounds in which R7 and R8 are, independently of each other, C1-C6 alkyl, even more preferably methyl or ethyl; or R7 and R8, together with the sulfur atom to which they are attached, form a four- to six-membered saturated ring system, which may contain one oxygen atom; preferably, said ring system is not substituted, and said ring system does not contain an oxygen atom or contains an oxygen atom; or, more preferably, R7 and R8, together with the sulfur atom to which they are attached, form a saturated, unsubstituted, four-membered ring system that does not contain an oxygen atom.

[0081] Another preferred group of compounds of formula I is represented by compounds of formula I-5 where A is CH or N; R2 is C1-C6 haloalkyl, preferably trifluoromethyl; G3 is N or CH, preferably N; n is 0 or 1, preferably n is 1; R7 and R8 are, independently of each other, C1-C6 alkyl, preferably methyl or ethyl; or R7 and R8, together with the sulfur atom to which they are attached, form a saturated six-membered ring system, which may contain an oxygen atom, preferably said ring system is unsubstituted, and said ring system contains an oxygen atom; or R7 and R8, together with the sulfur atom to which they are attached, form a four-membered saturated ring system, which does not contain an oxygen atom, preferably, said ring system is not substituted.

[0082] Another preferred group of compounds of formula I is represented by compounds of formula I-5-A where A is CH or N; R2 is C1-C6 haloalkyl, preferably trifluoromethyl; G3 is N; n is 0 or 1, preferably n is 1; R7 and R8 are, independently of each other, C1-C6 alkyl, preferably methyl or ethyl; or R7 and R8, together with the sulfur atom to which they are attached, form a saturated four-membered ring system, which does not contain an oxygen atom, preferably, said ring system is not substituted.

[0083] An additional preferred group of compounds of formula I is represented by compounds of formula I-6 wherein X1, R2, G1, A, n, R7 and formula I above; and wherein Xa4 is ethyl, n-propyl, i-propyl or cyclopropylmethyl.

[0084] In said preferred group of compounds of formula I-6, A is preferably N; Xa4 is preferably S or SO2, more preferably SO2; and Ra4 is preferably ethyl. In a further preferred group of compounds of formula I-6, A is preferably CH; Xa4 is preferably S or SO2, more preferably SO2; and Ra4 is preferably ethyl.

[0085] In another especially preferred group of compounds of formula I-6, X1 is preferably NR3, in which R3 is C1-C4 alkyl, more preferably methyl; R2 is preferably C1-C6 haloalkyl, more preferably trifluoromethyl; and G1 is CH or N, more preferably N.

[0086] In compounds of formula I-6 and all preferred embodiments of compounds of formula I-6 mentioned above, n is 0 or 1, more preferably n is 1; and R7 and R8 are defined under formula I above. A further preferred embodiment of said especially preferred group of compounds of formula I-6 comprises compounds in which R7 and R8 are, independently of each other, C1-C6 alkyl, even more preferably methyl or ethyl; or R7 and R8, together with the sulfur atom to which they are attached, form a four- to six-membered saturated ring system; preferably, said ring system is not substituted, and said ring system does not contain an oxygen atom or contains an oxygen atom; or, more preferably, R7 and R8, together with the sulfur atom to which they are attached, form a saturated, unsubstituted, four-membered ring system containing no oxygen atom or a saturated, unsubstituted ring system, with six-membered, which contains one oxygen atom.

[0087] Another preferred group of compounds of formula I is represented by compounds of formula I-7 where A is N or CH; in particular A is N; R2 is C1-C6 haloalkyl, preferably trifluoromethyl; G1 is N or CH, preferably G1 is N; n is 0 or 1, preferably n is 1; R7 and R8 are, independently of each other, C1-C6 alkyl, preferably methyl or ethyl; or R7 and R8, together with the sulfur atom to which they are attached, form a saturated six-membered ring system, preferably said ring system is unsubstituted, and said ring system contains an oxygen atom; or R7 and R8, together with the sulfur atom to which they are attached, form a four-membered saturated ring system, which does not contain an oxygen atom, preferably, said ring system is not substituted.

[0088] Another preferred group of compounds of formula I is represented by compounds of formula I-7-A where A is N or CH; R2 is C1-C6 haloalkyl, preferably trifluoromethyl; G1 is N; n is 1; R7 and R8 are, independently of each other, C1-C6 alkyl, preferably methyl or ethyl; or

[0089] R7 and R8, together with the sulfur atom to which they are attached, form a saturated ring system with six members, preferably, said ring system is not substituted, and said ring system contains an oxygen atom; or R7 and R8, together with the sulfur atom to which they are attached, form a four-membered saturated ring system, which does not contain an oxygen atom, preferably, said ring system is not substituted.

[0090] An additional preferred group of compounds of formula I is represented by compounds of formula I-8 wherein R2, G2, G3, A, n, R7 and R8 are as defined under formula I above; and wherein Xa5 is S, SO or SO2; Ra5 is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl.

[0091] In said preferred group of compounds of formula I-8, A is N; Xa5 is preferably S or SO2, more preferably SO2; and Ra5 is preferably ethyl. In a further preferred group of compounds of formula I8, A is preferably CH; Xa5 is preferably S or SO2, more preferably SO2; and Ra5 is preferably ethyl. In another preferred group of compounds of formula I8, R2 is preferably C1-C6 haloalkyl, even more preferably trifluoromethyl; G2 is preferably CH; and G3 is preferably N.

[0092] In compounds of formula I-8 and all preferred embodiments of compounds of formula I-8 mentioned above, n is 0 or 1, more preferably n is 1; and R7 and R8 are defined under formula I above. A further preferred embodiment of said especially preferred group of compound of formula I-8 comprises compounds in which R7 and R8 are, independently of each other, C1-C6 alkyl, even more preferably methyl or ethyl; or R7 and R8, together with the sulfur atom to which they are attached, form a four- to six-membered saturated ring system, which may contain an oxygen atom, preferably said ring system is unsubstituted, and said system ring does not contain an oxygen atom or contains an oxygen atom. Another preferred group of compounds of formula I is represented by compounds of formula I-9 where A is N or CH; R2 is C1-C6 haloalkyl, preferably trifluoromethyl; G2 is preferably CH; G3 is preferably N; n is 0 or 1, preferably n is 1; R7 and R8 are, independently of each other, C1-C6 alkyl, preferably methyl or ethyl; or R7 and R8, together with the sulfur atom to which they are attached, form a saturated six-membered ring system, which may contain an oxygen atom, preferably said ring system is unsubstituted, and said ring system contains an oxygen atom; or R7 and R8, together with the sulfur atom to which they are attached, form a saturated six-membered ring system, which may contain an oxygen atom, preferably said ring system is unsubstituted, and said ring system contains an oxygen atom; or R7 and R8, together with the sulfur atom to which they are attached, form a four-membered saturated ring system, which does not contain an oxygen atom, preferably, said ring system is not substituted.

[0093] Another preferred group of compounds of formula I is represented by compounds of formula I-9-A where A is N; R2 is C1-C6 haloalkyl, preferably trifluoromethyl; G2 is CH; G3 is N; n is 1; and R7 and R8 are, independently of each other, C1-C6 alkyl, preferably methyl or ethyl.

[0094] A particularly preferred group of compounds of formula I is represented by those in which A is CH or N; n is 0 or 1; R7 and R8 are, independently of each other, C1-C6 alkyl, preferably methyl or ethyl; or R7 and R8, together with the sulfur atom to which they are attached, form a saturated six-membered ring system, which may contain an oxygen atom, preferably said ring system is unsubstituted, and said ring system contains an oxygen atom; or R7 and R8, together with the sulfur atom to which they are attached, form a four-membered saturated ring system, which does not contain an oxygen atom, preferably, said ring system is unsubstituted; and Q is a radical selected from the group consisting of the formulas Q1a, Q1b, Q2a, Q3a and Q4a in particular selected from the group consisting of the formulas Q1a, Q1b and Q2a, wherein the arrow denotes the point of attachment to the ring incorporating the radical A; and in which R2 is a C1-C6 haloalkyl, preferably trifluoromethyl;

[0095] The compounds according to the invention may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (e.g., greater biological activity, a advantageous spectrum of activity, an increased safety profile, improved physicochemical properties or increased biodegradability). In particular it has surprisingly been discovered that certain compounds of formula (I) can show an advantageous safety profile with respect to non-target arthropods, in particular pollinators such as honey bees, solitary bees and bumblebees. Most particularly, Apis mellifera.

[0096] The process according to the invention for preparing the compounds of formula I is carried out in principle by methods known to those skilled in the art. More specifically, the subgroup of compounds of formula I, where X is SO (sulfoxide) and/or SO2 (sulfone), can be obtained through an oxidation reaction of the corresponding sulfide compounds of formula I, where X is S, 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 conducted in the presence of a solvent. Examples of the solvent to be used in the reaction include aliphatic halogenated hydrocarbons, such as dichloromethane and chloroform; alcohols, such as methanol and ethanol; Acetic Acid; water, and its mixtures. The amount of 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 I to produce the sulfoxide compounds I, and preferably 2 to 2 .2 moles of oxidant, relative to 1 mole of the sulfide compounds I to produce the sulfone compounds I. Such oxidation reactions are disclosed, for example, in WO 2013/018928.

[0097] The subgroup of compounds of formula I in which n is 1, defining compounds of formula Ia, in which X, R1, R7, R8, A and Q are as defined in formula I, Scheme 1:

[0098] can be prepared by reacting compounds of formula II, in which X, R1, A and Q are as defined in formula I, and in which X00 is a leaving group such as a halogen, preferably chlorine, or in which X00 is a radical X01 or R7 and R8 are as defined in formula I (Scheme 1), optionally in the presence of an acylation catalyst, such as 4-dimethylaminopyridine (DMAP), preferably in the presence of a base, such as triethylamine, diisopropylethylamine or pyridine, in an inert solvent at temperatures between 0 and 50 °C. Examples of solvent to be used include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, tert-butylmethyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane and chloroform, nitriles such as such as acetonitrile or polar aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethyl sulfoxide. Certain bases, such as pyridine and triethylamine, can be successfully employed as both base and solvent.

[0099] Compounds of formula III, where R7 and R8 are as defined in formula I, are known compounds, are commercially available or can be prepared by known methods described in the literature, such as in the Journal of the Chemical Society, 3004 -5; 1965 or e-EROS Encyclopedia of Reagents for Organic Synthesis, 1-8; 2013. Of advantage are methods of preparation for compounds of formula III starting from readily available sulfide compounds of formula V (see Chem. Commun. 53, 348-351; 2017 and additional references cited therein) or from compounds of corresponding sulfoxides of formula VI (see Angewandte Chemie, International Edition, 55, 72037207; 2016 and additional references cited therein), wherein R7 and R8 are as defined in formula I,

[0100] involving, for example, ammonia, ammonium carbamate or ammonium acetate as a suitable nitrogen source and mediated by hypervalent iodine reagents, such as diacetoxy-iodobenzene, in solvents such as toluene, acetonitrile or methanol, at temperatures between 0 and 100 °C, preferably around room temperature.

[0101] Compounds of formula V and compounds of formula VI, wherein R7 and R8 are as defined in formula I, are known compounds, are commercially available or can be prepared by known methods described in the literature. In particular, compounds of formula V can be oxidized to compounds of formula VI under standard oxidation conditions already described above.

[0102] Alternatively, the compounds of formula Ia, wherein X, R1, R7, R8, A and Q are as defined in formula I, Scheme 2

[0103] can be prepared by an oxidation step from the subgroup of compounds of formula I in which n is 0, defining compounds of formula Ib, in which X, R1, R7, R8, A and Q are as defined in formula I (scheme 2). In such transformations, classical oxidation reagents can be used such as, for example, KMnO4 (European Journal of Organic Chemistry, 2013 (34), 7800-7808; 2013), NaMnO4, mCPBA, NaIO4/RuO2 (Tetrahedron Letters, (6 ), 503-6; 1978), NaIO4/RuCl3, H2O2 (optionally in the presence of a catalyst, such as for example sodium tungstate Na2WO4; WO07/006670) or oxone. Such oxidations can be additionally carried out in analogy to descriptions found in, for example, WO2008/097235 and WO2008/106006, relating to the use of ruthenium salts in combination with alkali metal periodates and alternatively to the use of alkali metal permanganates. Suitable solvents for oxidation are, for example, dichloromethane, chloroform, methanol, ethanol, water or acetic acid, or mixtures thereof, at temperatures ranging from -10° to 50°C, preferably between 10 and 30°C.

[0104] Compounds of formula Ib, wherein X, R1, R7, R8, A and Q are as defined in formula I, can be prepared by reacting compounds of formula IV, wherein X, R1, A and Q are as defined in formula I, with a sulfoxide reagent S(O)R7R8 of formula VI, wherein R7 and R8 are as defined in formula I, for example by involving phosphorus pentoxide (Monatsh. Chem. 101, 396-404 ; 1970) or trifluoroacetic anhydride (J. Org. Chem. 40, 2758-2764; 1975), in the presence of triethylamine, and in solvents such as chloroform or dichloromethane, at temperatures between -80 and 100 °C, preferably between -70 and 60°C.

[0105] Compounds of formula IV, wherein X, R1, A and Q are as defined in formula I, can be prepared by reacting compounds of formula II, wherein X, R1, A and Q are as defined in formula I, and in which X00 is a leaving group such as a halogen, preferably chlorine, or in which X00 is a radical X01 or with ammonia NH3 (or a salt thereof) or an ammonia equivalent such as for example ammonium hydroxide NH4OH, ammonium chloride NH4Cl, ammonium acetate NH4OAc, ammonium carbonate (NH4)2CO3 and other NH3 substitutes, optionally in the presence of an acylation catalyst, such as 4-dimethylamino-pyridine (DMAP), preferably in the presence of a base, such as triethylamine, diisopropylethylamine or pyridine, in an inert solvent at temperatures between 0 and 50 ° C. Examples of solvent to be used include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, tert-butylmethyl ether and 1,4-dioxane, esters such as ethyl acetate, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such such as dichloromethane and chloroform, nitriles such as acetonitrile or polar aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethyl sulfoxide or water or mixtures thereof. Certain bases, such as pyridine and triethylamine, can be successfully employed as both base and solvent.

[0106] Alternatively, compounds of formula Ib, wherein X, R1, R7, R8, A and Q are as defined in formula I, can be prepared by reacting compounds of formula II, wherein X, R1, A and Q are as defined in formula I, and in which X00 is a leaving group such as a halogen, preferably chlorine, or in which X00 is a radical X01 or carbonyl of compound II), with a sulfilimine reagent S(NH)R7R8 of formula VII (or a salt thereof), wherein R7 and R8 are as defined in formula I, optionally in the presence of an acylation catalyst, such as 4 -dimethylaminopyridine (DMAP), preferably in the presence of a base, such as triethylamine, diisopropylethylamine or pyridine, in an inert solvent at temperatures between 0 and 50 °C. Examples of solvent to be used include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, tert-butylmethyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane and chloroform, nitriles such as such as acetonitrile or polar aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethyl sulfoxide. Certain bases, such as pyridine and triethylamine, can be successfully employed as both base and solvent.

[0107] The compounds of formula VII (or a salt thereof), wherein R7 and R8 are as defined in formula I, are known compounds, are commercially available or can be prepared by known methods, in particular they can be conveniently prepared from of sulfide compounds of formula V, wherein R7 and R8 are as defined in formula I,

[0108] as described in the literature, as for example in Justus Liebigs Annalen der Chemie, 618, 53-8, 1958; Chemische Berichte, 99 (10), 3108-17, 1966; Tetrahedron Letters, (40), 4137-40, 1972; or WO2014/053401.

[0109] The compounds of formula II, in which X, R1, A and Q are as defined in formula I, and in which X00 is a leaving group such as a halogen, preferably chlorine, or in which X00 is a radical X01 or X02 (where the arrow denotes the point of attachment to the C=O carbonyl fraction of compound II), Scheme 3:

[0110] can be prepared by activating a compound of formula VIII, wherein X, R1, A and Q are as defined in formula I, by methods known to those skilled in the art and described in, for example, Tetrahedron, 2005, 61 (46), 1082710852 (scheme 3). For example, compounds II where DMF in inert solvents such as methylene chloride CH2Cl2 or tetrahydrofuran THF at temperatures between 20 and 100 °C, preferably 25 °C. Alternatively, treatment of compounds of formula VIII with, for example, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide EDC (also known as EDAC or EDCI) or dicyclohexyl carbodiimide DCC will generate an activated species II, wherein X00 is X01 or

[0111] Compounds of formula VIII, wherein X, R1, A and Q are as defined in formula I, can be prepared by saponification of the corresponding ester compounds of formula IX, wherein X, R1, A and Q are as defined defined in formula I, and in which Rx is C1-C6 alkyl, under conditions known to one skilled in the art (using for example conditions such as: aqueous sodium, potassium or lithium hydroxide in methanol, ethanol, tetrahydrofuran or dioxane at room temperature, or even reflux conditions). Alternatively, treating ester compounds of formula IX with halide anions, preferably chloride anions, originating from, for example, lithium chloride (or alternatively sodium or potassium chloride), in solvents such as N,N- dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone, can also generate the carboxylic acid compounds of formula VIII. Reaction temperatures for such a range of O-demethylation preferably range from 20 ° C to the boiling point of the reaction mixture, or the reaction can be carried out under microwave irradiation.

[0112] Compounds of formula IX, in which X, R1, A and Q are as defined in formula I, and in which Rx is C1C6 alkyl, can be prepared by a carbonylation reaction from compounds of formula (X) , wherein X, R1, A and Q are as defined in formula I, and wherein Xa is a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an aryl-, alkyl- or haloalkylsulfonate such as trifluoromethanesulfonate. In such alkoxycarbonylations, the compounds of formula (X) are reacted with carbon monoxide CO, usually under pressure, in the presence of metal catalyst such as a palladium catalyst (e.g. palladium(II) acetate; palladium(II) dichloride ,1'-bis(diphenylphosphine)ferrocene]palladium (II) Pd(dppf)Cl2; bis(triphenylphosphine)palladium (II) dichloride PdCl2(PPh3)2; ), optionally in the presence of a phosphine ligand such as triphenylphosphine or 1,1'-bis(diphenylphosphine)ferrocene, in an alcohol solvent RxOH (typically methanol or ethanol), wherein Rx is C1-C6 alkyl, optionally in the presence of a co-solvent (e.g. toluene, dioxane or N,N-dimethylformamide) and, preferably, in the presence of a base, such as for example trimethylamine, at temperatures between 20° and 200°C, preferably between 50° and 180°C.

[0113] Alternatively, the compound of formula VIII, wherein X, R1, A and Q are as defined in formula I, Scheme 4:

[0114] can be prepared (Scheme 4) by hydrolysis of compounds of formula XI, wherein X, R1, A and Q are as defined in formula I, under aqueous acidic or basic conditions (see, for example, Synthetic Organic Methodology, Comprehensive Organic Transformations: A Guide to Functional Group Preparations, Larock, R. C. 1989, p. Typically, compounds of formula tetrahydrofuran, ethylene glycol dimethyl ether or 1,4-dioxane) at temperatures ranging between room temperature and 180 °C, preferably between 50 °C and the boiling point of the reaction mixture. Such hydrolysis conditions, and variants thereof, are well known to one skilled in the art.

[0115] Compounds of formula XI, wherein X, R1, A and Q are as defined in formula I, can be prepared by a cyanation of compounds of formula (X), wherein defined in formula I, and in which Xa is a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an aryl-, alkyl- or haloalkylsulfonate such as trifluoromethanesulfonate. In such reactions, compounds of formula (X) are reacted with a cyanide source such as copper(I) cyanide, optionally in the presence of an additional copper catalyst, for example copper(I) iodide, in solvents such as dimethylsulfoxide, N-methyl pyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide, at temperatures between 0 and 200 °C, preferably between 50 and 180 °C, optionally under microwave irradiation. Alternatively, this transformation can be achieved under palladium or nickel catalysis with for example zinc cyanide (see, for example, Med. Chem. Commun., 2010, 1, 309-318).

[0116] Alternatively, the compound of formula VIII, wherein X, R1, A and Q are as defined in formula I, Scheme 5:

[0117] can be prepared (Scheme 5) by oxidative cleavage of alkene compounds of formula XII, in which X, R1, A and Q are as defined in formula I, and in which the olefin moiety can be mono-, di - or tri-substituted by Ry, and in which Ry is hydrogen, C1-C6 alkyl, C1-C6 alkoxy or phenyl (preferably Ry is hydrogen). Oxidative cleavage conditions comprise for example the use of osmium tetroxide OsO4 (alternatively manganese oxide, ruthenium or wolframate reagents) or a substitute thereof such as dipotassium osmate dihydrate (K2OsO4.2H2O), in the presence of a co -oxidant such as ozone (see in particular J. Am. Chem. Soc. 2002, 124, 3824-3825) or sodium periodate NaIO4, in solvents such as acetone, tert-butanol, N,N-dimethylformamide or 1,4 -dioxane, usually in mixtures with water, at temperatures between 0 and 80 °C, preferably between 0 °C and room temperature. Such reactions can proceed with the intermediation of the corresponding 1,2-diol and/or aldehyde originating in compounds of formula XII, which can be isolated, but advantageously the olefins of formula XII are directly oxidatively cleaved to the carboxylic acids of formula VIII. This type of transformations involving OsO4 and NaIO4 is known in the literature, as described for example in Eur. J. Org. Chem. 2014, 5664-5669.

[0118] The compounds of formula XII, in which X, R1, A and Q are as defined in formula I, and in which the olefin fraction can be mono-, di- or tri-substituted by Ry, in which Ry is hydrogen, C1-C6 alkyl, C1-C6 alkoxy or phenyl (preferably Ry is hydrogen) can be prepared by olefination of compounds of formula (X), wherein X, R1, A and Q are as defined in formula I, and in wherein Methods, by Lutz Ackermann, Wiley, 2009). In particular, compounds of formula XII may be prepared by a Stille reaction between compounds of formula (X) and a suitable tin reagent (a trialkyl tin derivative, preferably tri-n-butyl tin), such as by example tributyl(vinyl)tin when Ry is preferably hydrogen. Such Stille reactions are usually carried out in the presence of a palladium catalyst, for example tetrakis(triphenylphosphine)palladium(0) or bis(triphenylphosphine)palladium(II) dichloride, in an inert solvent such as N,N-dimethylformamide , acetonitrile, toluene or dioxane, optionally in the presence of an additive such as cesium fluoride or lithium chloride and optionally in the presence of an additional catalyst, for example copper (I) iodide. Such Stille couplings are also well known to those skilled in the art and have been described in, for example, J. Org. Chem., 2005, 70, 8601-8604, J. Org. Chem., 2009, 74, 5599-5602, and Angew. Chem. Int. Ed., 2004, 43, 1132-1136.

[0119] The compounds of formula (X), in which X, R1, A and Q are as defined in formula I, and in which Xa is a leaving group, in particular those compounds in which Xa is a halogen, are known compounds or they may be prepared by known methods or may be synthesized in analogy to described methods found in the literature. See in particular WO 2016/071214 (Q is Q2, G3 is N) and WO 2015/000715 (Q is Q2, G3 is CH), WO 2016/026848 and WO 2016/005263 (Q is Q1, G1 is CH), WO 2016/059145 (Q is Q1, G1 is N), WO 2016/020286 and WO 2017/134066 (Q is Q3) and WO 2012/086848, WO 2013/018928 (Q is Q4).

[0120] Certain compounds of formula VIII and/or IX, in which X, R1, A and Q are as defined in formula I, and in which Rx is C1-C6 alkyl, are known in the literature, see in particular WO17/146221 , WO16/104746, WO14/142292, WO14/132972 and WO14/123206.

[0121] Reactants can be reacted in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal carbonates or alkaline earth metals, dialkylamides of alkali metals or alkaline earth metals or alkylsilylamides of alkali metals or alkaline earth metals, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples that may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, di- lithium isopropylamide, 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).

[0122] The reactants can be reacted with each other as such, i.e., without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture thereof. If the reaction is carried out in the presence of a base, bases that are employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, can also act as solvents or diluents.

[0123] The reaction is advantageously carried out in a temperature range of approximately -80 °C to approximately +140 °C, preferably from approximately -30 °C to approximately +100 °C, in many cases in the range between the temperature ambient and approximately +80 °C.

[0124] A compound of formula I can be converted in a manner known per se into another compound of formula I by replacing one or more substituents of the starting compound of formula I in the usual way, with another substituent(s) according to the invention.

[0125] Depending on the choice of reaction conditions and starting materials that are suitable in each case it is possible, for example, in a reaction step to replace only one substituent with 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.

[0126] Salts of compounds of formula I can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula I are obtained by treatment with a suitable acid or a suitable ion exchange reagent and salts with bases are obtained by treatment with a suitable base or a suitable ion exchange reagent. .

[0127] The salts of the compounds of formula I can be converted in the usual way into free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchange reagent and salts with bases, for example, by treatment with a suitable acid or a suitable ion exchange reagent.

[0128] Salts of compounds of formula I can be converted in a manner known per se into other salts of compounds of formula I, acid addition salts, for example, into other acid addition salts, for example by treatment of an inorganic acid salt 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 silver chloride, is insoluble and thus precipitates from the reaction mixture.

[0129] Depending on the procedure or reaction conditions, compounds of formula I, which have salt-forming properties, can be obtained in free form or in the form of salts.

[0130] 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 that are possible or as a mixture of these, 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 pure isomers and also to all mixtures of isomers that are possible and is to be understood in each case in this sense previously and hereafter, even when stereochemical details are not specifically mentioned in each case.

[0131] Mixtures of diastereoisomers or mixtures of racemates of the compounds of formula I, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen, can be separated in a known way in pure diastereoisomers or racemates based on the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.

[0132] Mixtures of enantiomers, such as racemates, that can be obtained in a similar way can be resolved at the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high performance liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, 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 basic end product racemate 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 separating of the mixture of diastereoisomers that can be obtained in this way, for example by fractional crystallization based on their different solubilities, to give the diastereoisomers, from which the desired enantiomer can be released by the action of suitable agents, for example basic agents.

[0133] Pure diastereoisomers or enantiomers can be obtained according to the invention not only by separating suitable mixtures of isomers, but also by generally known methods of diastereoselective or enantioselective synthesis, for example carrying out the process according to the invention with starting materials for suitable stereochemistry.

[0134] 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, e.g. e.g., trifluoroacetic anhydride. Such oxidations are known from the literature, for example from J. Med. Chem., 32 (12), 2561-73, 1989 or WO 00/15615.

[0135] It is advantageous to isolate or synthesize in each case the isomer, for example enantiomer or diastereoisomer, or mixture of isomers, for example mixture of enantiomers or mixture of diastereoisomers, biologically more effective if the individual components have a different biological activity.

[0136] The compounds of 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, e.g. those that may have been used for the crystallization of compounds that are present in solid form.

[0137] The compounds according to the following Tables 1 to 12 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.

[0138] Table 1: This table discloses the 28 compounds 1,001 to 1,028 of formula I-1a: where X11 is S, and A, R11, G1, R2, n, R7 and R8 are as defined below: Table 1:

[0139] and the N-oxides of the compounds in Table 1.

[0140] Table 2: This table discloses the 28 compounds 2001 to 2028 of formula I-1a, where X11 is SO, and A, R11, G1, R2, n, R7 and R8 are as defined in Table 1.

[0141] Table 3: This table discloses the 28 compounds 3,001 to 3,028 of formula I-1a, where X11 is SO2, and A, R11, G1, R2, n, R7 and R8 are as defined in Table 1.

[0142] Table 4: This table discloses the 26 compounds 4,001 to 4,026 of formula I-2a:

[0143] where X11 is S, and A, R11, G3, R2, n, R7 and R8 are as defined below: Table 4:

[0144] and the N-oxides of the compounds in Table 4.

[0145] Table 5: This table discloses the 26 compounds 5,001 to 5,026 of formula I-2a, where X11 is SO, and A, R11, G3, R2, n, R7 and R8 are as defined in Table 4.

[0146] Table 6: This table discloses the 26 compounds 6,001 to 6,026 of formula I-2a, where X11 is SO2, and A, R11, G3, R2, n, R7 and R8 are as defined in Table 4.

[0147] Table 7: This table discloses the 26 compounds 7,001 to 7,026 of formula I-3a:

[0148] where X11 is S, and A, R11, G1, R2, n, R7 and R8 are as defined below: Table 7:

[0149] and the N-oxides of the compounds in Table 7.

[0150] Table 8: This table discloses the 26 compounds 8,001 to 8,026 of formula I-3a, where X11 is SO, and A, R11, G1, R2, n, R7 and R8 are as defined in Table 7.

[0151] Table 9: This table discloses the 26 compounds 9,001 to 9,026 of formula I-3a, where X11 is SO2, and A, R11, G1, R2, n, R7 and R8 are as defined in Table 7.

[0152] Table 10: This table discloses the 14 compounds 10,001 to 10,014 of formula I-4a:

[0153] where X11 is S, and A, R11, G2, G3, R2, n, R7 and R8 are as defined below: Table 10:

[0154] and the N-oxides of the compounds in Table 10.

[0155] Table 11: This table discloses the 14 compounds 11,001 to 11,014 of formula I-4a, where X11 is SO, and A, R11, G2, G3, R2, n, R7 and R8 are as defined in Table 10.

[0156] Table 12: This table discloses the 14 compounds 12,001 to 12,014 of formula I-4a, where X11 is SO2, and A, R11, G2, G3, R2, n, R7 and R8 are as defined in Table 10.

[0157] The compounds of formula I according to the invention are preventatively and/or curatively valuable active ingredients in the field of pest control, even at low application rates, which have a very favorable biocidal spectrum and are well tolerated by species of warm blood, 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 representative elements of the order Acarina. The insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i.e. in the destruction of pests, which takes place immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate, corresponding to good activity with a destruction (mortality) rate of at least 50 to 60%.

[0158] Examples of the above-mentioned animal pests are: of the order Acarina, e.g.

[0159] Acalitus spp, Aculus spp, Acaricalus spp, Aceria spp, Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp , Eotetranychus spp, Eriophyes spp., Hemitarsonemus spp, Hyalomma spp., Ixodes spp., Olygonychus spp, Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp, Polyphagotarsonemus spp, Psoroptes s pp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp, Tarsonemus spp. and Tetranychus spp.;

[0160] of the order Anoplura, for example,

[0161] Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.;

[0162] of the order Coleoptera, for example,

[0163] Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis, Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp, Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decem Lineata, Lissorhoptrus spp., Liogenys spp, Maecolaspis spp, Maladera castanea, spp, Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp, Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., maticus spp, Sphenophorus spp, Sternechus subsignatus, Tenebrio spp., Tribolium spp. and Trogoderma spp.;

[0164] of the order Diptera, for example,

[0165] Aedes spp., Anopheles spp, Antherigona soccata, Bactrocea oleae, Bibio hortulanus, Bradysia spp, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp, Drosophila melanogaster , Fannia spp., Gastrophilus spp., Geomyza tripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit , Pegomyia hyoscyami, Phorbia spp., Rhagoletis spp, Rivelia quadrifasciata, Scatella spp, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;

[0166] of the order Hemiptera, for example,

[0167] Acanthocoris scabrator, Acrosternum spp, Adelphocoris lineolatus, Amblypelta nitida, Bathycoelia thalassina, Blissus spp, Cimex spp., Clavigralla tomentosicollis, Creontiades spp, Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp, Euchistus s pp., Eurydema pulchrum , Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp, Margarodes spp, Murgantia histrionic, Neomegalotomus spp, Nesidiocoris tenuis, Nezara spp., Nysius simulans, Oebalus insularis, Piesma spp., Piezodorus spp, Rhodnius spp. , Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp. , Thyanta spp , Triatoma spp., Vatiga illudens;

[0168] Acyrthosium pisum, Adalges spp, Agalliana ensigera, Agonoscena targionii, Aleurodicus spp, Aleurocanthus spp, Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., pidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp, Brachycaudus spp, Brevicoryne brassicae, Cacopsylla spp, Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp, Cofana spectra, Cryptomyzus spp, Cicadulina spp, Coccus hesperid one, Dalbulus maidis , Dialeurodes spp, Diaphorina citri, Diuraphis noxia, Dysaphis spp, Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae, Hyalopterus spp, Hyperomyzus pallidus, Idioscopus clypealis, Jacobiasca lybica, Laodelphax spp., Lecanium corni, Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp., Mahanarva spp, Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp., Neotoxoptera sp, Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats, naspis ruthae , Oregma lanigera Zehnter, Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Peregrinus maidis, Perkinsiella spp, Phorodon humuli, Phylloxera spp, Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, lla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Sogatella furcifera, Spissistilus festinus, Tarophagus Proserpina, Toxoptera spp, Trialeurodes spp, Tridiscus spor oboli , Trionymus spp, Trioza erytreae , Unaspis citri, Zygina flammigera, Zyginidia scutellaris, ;

[0169] of the order Hymenoptera, for example,

[0170] Acromyrmex, Arge spp, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Pogonomyrmex spp, Slenopsis invicta, Solenopsis spp. and Vespa spp.;

[0171] of the order Isoptera, for example,

[0172] Coptotermes spp, Corniternes cumulans, Incisitermes spp, Macrotermes spp, Mastotermes spp, Microtermes spp, Reticulitermes spp.; Solenopsis geminate

[0173] of the order Lepidoptera, for example,

[0174] Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp, Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp, Crocidolomia binotalis, Cryptophlebia leucotreta , Cydalima perspectalis, Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea, Earias spp., Eldana saccharina, Ephestia spp., Epinotia spp, Estigmene acrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa SPP ., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Mythimna spp, Noctua spp, Operophtera spp., Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Papaipema nebris, Pectinophora gossypiela, Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Pseudoplusia spp, Rachiplusia nu, Richia albicosta, Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Sylepta derogate, Synanthedon spp. , Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tuta absolute, and Yponomeuta spp.;

[0175] of the order Mallophaga, for example,

[0176] Damalinea spp. and Trichodectes spp.;

[0177] of the order Orthoptera, for example,

[0178] Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp. , Scapteriscus spp, and Schistocerca spp.;

[0179] of the order Psocoptera, for example,

[0180] Liposcelis spp.;

[0181] of the order Siphonaptera, for example,

[0182] Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis;

[0183] of the order Thysanoptera, for example,

[0184] Calliothrips phaseoli, Frankliniella spp., Heliothrips spp, Hercinothrips spp., Parthenothrips spp, Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp;

[0185] of the order Thysanura, for example, Lepisma saccharina.

[0186] The active ingredients according to the invention can be used for control, i.e., containment or destruction, of pests of the above-mentioned type occurring in particular on plants, especially on useful plants and ornamental plants in agriculture, horticulture and in forests, or in organs such as fruits, flowers, foliage, stems, tubers or roots of such plants, and in some cases even plant organs that are formed at a later time remain protected against these pests.

[0187] Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beetroot, such as sugar or fodder beet; fruits, for example pome fruits, stone fruits or soft fruits, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; legume crops such as beans, lentils, peas or soybeans; oil crops such as rapeseed, mustard, poppies, olives, sunflowers, coconut, castor beans, cocoa or peanuts; cucurbits, such as pumpkins, cucumbers or melons; fibrous plants such as cotton, flax, hemp or jute; citrus fruits, such as oranges, lemons, grapefruits or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes or 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.

[0188] The compositions and/or methods of the present invention can also be used on any ornamental and/or vegetable crops, including flowers, shrubs, broadleaf trees and evergreen trees.

[0189] 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 gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (I. Walleriana), Iresines spp., Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesia spp., Tagetes spp., Dianthus spp. (clove), 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. (pink), 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 layering.

[0190] For example, the invention can be used on any of the following species of vegetables: 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.

[0191] Preferred ornamental species include African violet, Begonia, Dahlia, Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hortensia, rosemary, sage, St. John's wort, mint, peppers, tomatoes and cucumbers.

[0192] 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, maize, 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 suppressalis (preferably in rice).

[0193] 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, maize, 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 suppressalis (preferably in rice).

[0194] 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 knot nematodes from the root, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other species of Meloidogyne; cyst-forming nematodes, Globodera grossochiensis and other species of Globodera; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii and other species of Heterodera; Seed-knot nematodes, Anguina species; Stem and foliar nematodes, species of Aphelenchoides; Sting 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 species of Ditylenchus; Piercing nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus and other species of Helicotylenchus; Sheath 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 species of Longidorus; Root lesion nematodes, Pratylenchus species; Lesion-forming nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other species of Pratylenchus; Cave nematodes, Radopholus similis and other species of Radopholus; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis and other species of Rotylenchus; Scutellonema species; Root shortening and thickening nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunting nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other species of Tylenchorhynchus; Citrus nematodes, Tylenchulus species; Dagger-shaped nematodes, Xiphinema species; and other species of plant parasitic nematodes, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp. and Quinisulcius spp.

[0195] The compounds of the invention may also have activity against molluscs. Examples of these include, for example, Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. nemoralis); Ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H. obvia); Helicidae Helicigona shrubrum); Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.

[0196] The term “crops” is to be understood as also including 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 Bacillus genus.

[0197] 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. e.g., CrylAl, Cry1Ac, Cry1F, Cry1Fa2, Cry2Al, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. e.g., Vipl, 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 whitebell lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome inactivating proteins (RIP), such as ricin, maize RIP, abren, lufin, saporin or bryodin; steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyltransferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA reductase, ion channel blockers such as sodium or calcium channel blockers, hormone juvenile esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.

[0198] In the context of the present invention, they are to be understood as δ-endotoxins, for example CrylAl, CrylAc, Cry1F, Cry1Fa2, Cry2Al, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vipl, Vip2, Vip3 or Vip3A, also expressly hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of these proteins (see, for example, WO 02/1570l). Truncated toxins, for example a truncated CrylAb, are known. In the case of engineered toxins, one or more amino acids of 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 ).

[0199] 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.

[0200] The processes for preparing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Deoxyribonucleic acids of the CryI type and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

[0201] The toxin contained in transgenic plants gives the 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).

[0202] Transgenic plants containing one or more genes that encode insecticide resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (a variety of apple that expresses a Cry1Ab toxin); YieldGard Rootworm® (a variety of apple that expresses a Cry3Bb1 toxin); YieldGard Plus® (a variety of apple that expresses a Cry1Ab and a Cry3Bb1 toxin); Starlink® (a variety of apple 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® 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® (potato variety that expresses a Cry3A toxin); NatureGard®, Agrisure® GT Advantage (glyphosate tolerant trait GA21), Agrisure® CB Advantage (corn borer (CB) trait Bt11) and Protecta®.

[0203] Additional examples of such transgenic crops are: 1. Bt11 maize 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 has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenically expresses the PAT enzyme to achieve tolerance to the herbicide glufosinate ammonium. 2. Maís 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 has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a Cry1Ab toxin. Bt176 maize also transgenically expresses the PAT enzyme to obtain tolerance to the herbicide glufosinate ammonium. 3. Maís MIR604 from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize that has been made resistant to insects by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055, modified by insertion of a cathepsin G protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810. 4. Maís MON 863 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-type 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. Pioneer Overseas Corporation Maís 1507, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Maize genetically modified for the expression of the Cry1F protein to obtain resistance to certain Lepidoptera insects and the PAT protein to achieve tolerance to the herbicide glufosinate ammonium. 7. Maís 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. The NK603 x MON 810 maize transgenically expresses the CP4 EPSPS protein, obtained from the CP4 strain of Agrobacterium sp., which confers tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1Ab toxin obtained from Bacillus thuringiensis subsp. Kurstaki that confers tolerance to certain Lepidoptera, including the European corn borer. 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).

[0204] The term “crops” is to be understood as also including crop plants that have been so transformed by the use of recombinant DNA techniques that they are capable of synthesizing anti-pathogenic substances having a selective action, such as, for example, the so-called “pathogenesis-related proteins” (PRP, see, e.g., 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.

[0205] 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 KP1, KP4 or KP6 viral toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; so-called “pathogenesis-related proteins” (PRP; see, e.g., EP-A-0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see, e.g., WO 95/33818) or protein factors or polypeptides involved in the defense of plants against pathogens (so-called “disease resistance genes of plants”, as described in WO 03/000906).

[0206] Additional 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 coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the aforementioned type.

[0207] 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 application by IRS (internal residual spraying) of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention. In another embodiment it is contemplated applying 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) knitwear, clothing, bedding, curtains and tents.

[0208] In one embodiment, the method for controlling such pests comprises applying a pesticide-effective amount of the compositions of the invention to the target pests, their locus, or a surface or substrate so as to provide effective residual pesticidal activity in the surface or substrate. Such application can be done by brushing, rolling, spraying, spreading or dipping the pesticide composition of the invention. By way of example, an IRS application to a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention to provide effective residual pesticidal activity on the surface. In another embodiment it is contemplated applying such compositions for residual pest control to a substrate such as a woven material in the form of (or that can be used in the manufacture of) mesh, clothing, bedding, curtains and tents.

[0209] The substrates including non-wovens, fabrics or knits to be treated may be made of natural fibers such as cotton, raffia, jute, linen, sisal, single warp, or wool, or synthetic fibers such as polyamide, polyester, polypropylene, polyacrylonitrile or similar. Polyesters are particularly suitable. Textile treatment methods are known, e.g. e.g., WO 2008/151984, WO 2003/034823, US 5631072, WO 2005/64072, WO2006/128870, EP 1724392, WO2005113886 or WO 2007/090739.

[0210] Additional areas of use of the compositions according to the invention are the tree injection/trunk treatment area for all ornamental trees as well as all types of fruit and chestnut trees.

[0211] 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-boring insects listed in the following tables A and B: Table A. Examples of exotic wood drills with economic importance. Table B. Examples of economically important native wood drillers.

[0212] 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, ground pearls, millipedes, armadillos, mites, paquinhas, mealybugs, mealy bugs, leafhoppers, southern grass bugs and white grubs. The present invention can be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults.

[0213] In particular, the present invention can be used to control insect pests that feed on lawn roots including corots (such as Cyclocephala spp. (e.g., masked beetle, C. lurida), Rhizotrogus spp. ( e.g., European beetle, R. majalis), Cotinus spp. (e.g., St. John's beetle, C. nitida), Popillia spp. , Phyllophaga spp. (e.g., May/June beetle), Ataenius spp. (e.g., black lawn beetle, A. spretulus), Maladera spp. M. castanea) and Tomarus spp.), ground pearls (Margarodes spp.), paquinhas (orange, southern and with short wings; Scapteriscus spp., Gryllotalpa africana) and tipulas (common European melga, Tipula spp.) .

[0214] The present invention can also be used to control thatch-inhabiting lawn insect pests, including armyworms (such as fall armyworm Spodoptera frugiperda, and pasture armyworm Pseudaletia unipuncta), cutworms, weevils (Sphenophorus spp., such as S. venatus verstitus and S. parvulus) and lawn moths (such as Crambus spp. and the tropical lawn moth, Herpetogramma phaeopteralis). The present invention can also be used to control grass insect pests that live above ground and feed on grass blades, including grass bugs (such as southern grass bugs, Blissus insularis), Bermuda grass mites (Eriophyes cynodoniensis), Rhodes grass mealy bugs (Antonina graminis), two-lined planthopper (Propsapia bicincta), leafhoppers, screwworms (family Noctuidae), and green aphids.

[0215] The present invention can also be used to control other grass pests such as red imported fire ants (Solenopsis invicta) that create ant mounds in grass.

[0216] In the hygiene sector, the compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, scabies-causing mites, trombiculid mites, flies (biting and licking), larvae of parasitic flies, lice, lice hair, bird lice and fleas.

[0217] Examples of such parasites are:

[0218] From the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculus spp. and Phtirus spp., Solenopotes spp.

[0219] From the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp.

[0220] From the order Diptera and the suborders Nematocerina and Brachycerina, for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp. , Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.

[0221] From the order Siphonapterida, for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp. From the order Heteropterida, for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp..

[0222] From the order Blattarida, for example Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp.. From the subclass Acaria (Acarida) and the orders Metastigmata and Mesostigmata, 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.

[0223] From the orders Actinedida (Prostigmata) and Acaridida (Astigmata), for example Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

[0224] 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.

[0225] 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, Priobium carpini, Lyctus brunneus , Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, species of Urocerus gigas, Urocerus gigas taignus and Urocerus augur and termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and Coptotermes formosanus, and silver minnows such as Lepi sma saccharina .

[0226] 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 adjuvants, such as carriers, solvents and surface-active substances. The formulations can be in various physical forms, e.g. e.g., in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, fluidizable 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), impregnated polymer films or in other known forms, e.g. e.g., from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can be used directly or diluted before use. Dilutions can be made, for example, with water, liquid fertilizers, micronutrients, biological organisms, oil or solvents.

[0227] Formulations can be prepared, e.g. e.g., by mixing the active ingredient with formulation adjuvants to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.

[0228] The active ingredients can also be contained in very fine microcapsules. The microcapsules contain the active ingredients in a porous carrier. This allows the active ingredients to be released into the environment in controlled amounts (e.g., slow release). Microcapsules usually have a diameter of 0.1 to 500 microns. They contain active ingredients in an amount of approximately 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 may 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 which are known to the skilled artisan. in technique. Alternatively, very fine microcapsules may 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.

[0229] Formulation adjuvants that are suitable for preparing 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 abiethate, diethylene glycol butyl ether, diethylene glycol ethyl ether, 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, glycerol acetate, glycerol diacetate , glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, iso-octane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methylisoamylketone, methylisobutylketone, methyl laurate, octanoate methyl, 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, carbonate propylene, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methyl ether of propylene glycol, diethylene glycol methyl ether, methanol, ethanol, isopropanol and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2- pyrrolidone and the like.

[0230] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomite, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour , soy flour, pumice stone, wood flour, crushed nut shells, lignin and similar substances.

[0231] A large number of surface-active substances can be advantageously used in both 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; alkylarylsulfonate salts, 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, alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; 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 salts of mono- and dialkylphosphate esters; and also additional substances described e.g. ex. in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981).

[0232] Additional adjuvants that can be used in pesticide formulations include crystallization inhibitors, viscosity modifiers, suspending agents, colorants, antioxidants, foaming agents, light absorbers, mixing aids, antifoams, complexing agents, neutralizing or modifying substances pH levels and buffers, corrosion inhibitors, fragrances, wetting agents, uptake enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides and liquid and solid fertilizers.

[0233] 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 may 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 oils of vegetable origin, for example methyl derivatives, or an oil of animal origin, 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.

[0234] The inventive compositions generally comprise from 0.1 to 99% by weight, especially from 0.1 to 95% by weight, of compounds of the present invention and from 1 to 99.9% by weight of a formulation adjuvant that preferably includes from 0 to 25% by weight of a surfactant substance. Although commercial products may preferably be formulated as concentrates, the end user will typically employ diluted formulations.

[0235] Application rates vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions and other factors governed by the method of application, the timing application and target culture. As a general guideline, compounds can be applied at a rate of 1 to 2000 L/ha, especially 10 to 1000 L/ha.

[0236] Preferred formulations may have the following compositions (% by weight):

[0237] 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%

[0238] Dust: active ingredient: 0.1 to 10%, preferably 0.1 to 5% solid carrier: 99.9 to 90%, preferably 99.9 to 99%

[0239] Suspension concentrates: active ingredient: 5 to 75%, preferably 10 to 50% water: 94 to 24%, preferably 88 to 30% surfactant: 1 to 40%, preferably 2 to 30%

[0240] 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%

[0241] Granules: active ingredient: 0.1 to 30%, preferably 0.1 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%

[0242] The following Examples further illustrate, but do not limit, the invention.

[0243] The combination is completely mixed with the adjuvants and the mixture is completely crushed in a suitable mill, resulting in wettable powders that can be diluted with water to give suspensions of the desired concentration.

[0244] The combination is completely mixed with the adjuvants and the mixture is completely crushed in a suitable mill, resulting in powders that can be used directly for seed treatment.

[0245] Emulsions of any required dilution, which can be used to protect plants, can be obtained from this concentrate by dilution with water.

[0246] Ready-to-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry seed coatings.

[0247] The combination is mixed and crushed with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

[0248] The finely crushed combination is uniformly applied, in a mixer, to kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this way. Suspension concentrate

[0249] The finely crushed 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 such dilutions, live plants as well as plant propagation material can be treated and protected against infestation by microorganisms by spraying, pouring or immersing.

[0250] Fluidizable concentrate for seed treatment

[0251] The finely crushed 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 such dilutions, live plants as well as plant propagation material can be treated and protected against infestation by microorganisms by spraying, pouring or immersing.

Suspension of Slow Release Capsules

[0252] 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate mixture (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 is added a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts water. The mixture is stirred until the polymerization reaction is complete. The capsule suspension obtained is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% active ingredients. The average diameter of the capsules is 8-15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for that purpose.

[0253] 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), an oil dispersion (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.

Preparative Examples:

[0254] “Pf” means melting point in °C. Free radicals represent methyl groups. 1H NMR measurements were recorded on a Brucker 400 MHz spectrometer, chemical shifts are given in ppm relative to a TMS standard. Spectra measured in deuterated solvents as indicated. Any of the LCMS methods below were used to characterize the compounds. The characteristic LCMS values obtained for each compound were the retention time (“Tr”, recorded in minutes) and the measured molecular ion (M+H)+.

LCMS and GCMS methods: Method 1:

[0255] Spectra were recorded on a Waters Mass Spectrometer (ZQ Single Quadrupole Mass Spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone Range: 30- 60 V, Extractor: 2.00 V, Source Temperature: 150 °C, Desolvation Temperature: 350 °C, Cone Gas Flow: 0 L/h, Desolvation Gas Flow: 650 L/h, Range masses: 100 to 900 Da) and a Waters Acquity UPLC: Binary pump, heated column compartment and diode array detector. Solvent degasser, binary pump, heated column compartment and diode array detector. Column: Waters UPLC HSS T3, 1.8 Qm, 30 x 2.1 mm, Temp: 60 °C, DAD wavelength range (nm): 210 to 500, Solvent Gradient: A = water + MeOH 5% + 0.05% HCOOH, B= Acetonitrile + 0.05% HCOOH: gradient: 0 min B 0%, A 100%; 1.2-1.5 min 100% B; Flow (mL/min) 0.85.

Method 2:

[0256] Spectra were recorded on a Waters Mass Spectrometer (SQD or ZQ Single Quadrupole Mass Spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone Range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150 °C, Desolvation Temperature: 350 °C, Cone Gas Flow: 0 L/h, Desolvation Gas Flow: 650 L/h, Mass range: 100 to 900 Da) and a Waters Acquity UPLC: Binary pump, heated column compartment and diode array detector. Solvent degasser, binary pump, heated column compartment and diode array detector. Column: Waters UPLC HSS T3, 1.8 Qm, 30 x 2.1 mm, Temp: 60 °C, DAD wavelength range (nm): 210 to 500, Solvent Gradient: A = water + MeOH 5% + 0.05% HCOOH, B = Acetonitrile + 0.05% HCOOH; gradient: 0 min B at 0%, A at 100%; 2.7-3.0 min 100% B; Flow (mL/min) 0.85.

Method 3:

[0257] Spectra were recorded on an Agilent Technologies Mass Spectrometer (6410 Triple Quadrupole Mass Spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Exchange, Capillary: 4.00 kV, Shred: 100 .00 V, Gas Temperature: 350 oC, Gas Flow: 11 L/min, Nebulizer Gas: 45 psi, Mass Range: 110-1000 Da, DAD Wavelength Range: 210-400 nm). Column: KINETEX EVO C18, length 50 mm, diameter 4.6 mm, particle size 2.6 μm. Column oven temperature 40 °C. Solvent gradient: A = Water with 0.1% formic acid: Acetonitrile (95:5 v/v). B = Acetonitrile with 0.1% formic acid. Gradient = 0 min A at 90%, B at 10%; 0.9-1.8 min A at 0%, B at 100%, 2.2-2.5 min A at 90%, B at 10%. Flow rate 1.8 mL/min.

Method 4:

[0258] Spectra were recorded on a Waters Mass Spectrometer (Acquity SDS Mass Spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Exchange, Capillary: 3.00 kV, Cone Voltage: 41, 00 V, Source temperature: 150 oC, Desolvation Gas Flow: 1000 L/h, Desolvation temperature: 500 oC, Gas Flow @ Cone: 50 L/h, Mass range: 110-800 Da, Range of PDA wavelengths: 210-400 nm. Column: Acquity UPLC HSS T3 C18, length 30 mm, diameter 2.1 mm, particle size 1.8 μm. A = Water with 0.1% formic acid: Acetonitrile (95:5 v/v). 2 min A at 50%, B at 50%; 0.7-1.3 min A at 0%, B at 100%; .8 mL/min. a) Synthesis of Examples of Compounds of Formula (I):

[0259] EXAMPLE P-P1: Preparation of N-(ethyl-methyl-oxo-À6-sulfanilidene)-5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin- 2-yl]pyridine-3-carboxamide (compound P8): (dimethylamino)pyridine (1 mg) were added to a solution of ethyl-imino-methyl-oxo-À6-sulfane (78.2 mg, 0.693 mmol) in tetrahydrofuran (5 mL) at 0-5 °C, followed by by dropwise addition of a solution of 5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridine-3-carbonyl chloride (intermediate I3) ( 300 mg, 0.693 mmol) in tetrahydrofuran (5 mL). The reaction mixture was stirred at 0-5°C for 30 minutes. The solvent was removed under reduced pressure and the residue purified by Combiflash on silica gel (0-80% ethyl acetate in cyclohexane) to give N-(ethyl-methyl-oxo-À6-sulfanilidene)-5-ethylsulfonyl- 6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridine-3-carboxamide (compound P8) as a solid, mp 113-114°C. LCMS (method 1): 504 (M+H)+, retention time 0.87 min.

[0260] EXAMPLE P—P2: Preparation of N- (dimethyl-À4-sulfanilidene)-5-ethylsulfonyl-6-[3-methyl-6- (trifluoromethyl)imidazo[4,5-c]pyridin-2-yl] pyridine-3-carboxamide (compound P5):

[0261] To a suspension of 5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridine-3-carboxamide (intermediate I4) (430 mg, 1.04 mmol) and phosphorus pentoxide (295 mg, 2.08 mmol) in dry chloroform (10 mL) under argon was added a mixture of dimethyl sulfoxide (284 mg, 0.26 mL, 3.64 mmol) and triethylamine ( 111 mg, 152 DL, 1.09 mmol) dropwise while maintaining the internal temperature below 35-40 °C. The mixture was stirred at room temperature overnight. More of the mixture of dimethylsulfoxide (3.64 mmol) and trimethylamine (1.09 mmol) was added and stirring continued at room temperature for 60 hours. The reaction mixture was carefully poured into an ice-cold aqueous NaOH solution while maintaining the internal temperature below 10 °C. The aqueous phase was extracted several times with chloroform, the combined organic layers washed with water and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by Combiflash on silica gel (methanol in 0-10% ethyl acetate) to give N-(dimethyl-À4-sulfanilidene)-5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo [4,5-c]pyridin-2-yl]pyridine-3-carboxamide (compound P5) as a solid. LCMS (method 1): 474 (M+H)+, retention time 0.79 min.

[0262] EXAMPLE P-P3: Preparation of N-[dimethyl(oxo)-À6-sulfanilidene]-5-ethylsulfonyl-6-[6-(trifluoromethyl)pyrazolo[4,3-c]pyridin-2-yl]pyridine -3- carboxamide (compound P24)

[0263] A solution of 5-ethylsulfonyl-6-[6-(trifluoro-methyl)pyrazolo[4,3-c]pyridin-2-yl]pyridine-3-carboxylic acid (intermediate I15) (110 mg, 0. 27 mmol), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI, 59 mg, 0.30 mmol) and imino-dimethyl-oxo-À6-sulfane (30 mg, 0.30 mmol) in pyridine (2 ml) was stirred at 80°C for 3 hours. The reaction mixture was poured into water and extracted with ethyl acetate, the combined extracts were washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by Combiflash on silica gel (ethyl acetate/hexane 9:1) to give N-[dimethyl(oxo)-À6-sulfanilidene]-5-ethylsulfonyl-6-[6-(trifluoromethyl)pyrazolo[4, 3-c]pyridin-2-yl]pyridine-3-carboxamide (compound P24) as a solid, mp 268-270°C. LCMS (method 3): 476 (M+H)+, retention time 1.41 min. 1H NMR (400 MHz, DMSO-d6) δ ppm 1.29 (t, J=7.30 Hz, 3H), 3.58 (s, 6H), 4.00 (q, J=7.30 Hz, 2H), 8.40 (s, 1H), 8.97 (d, J=1.96 Hz, 1H), 9.39 (d, J=1.96 Hz, 1H), 9.52 (m, 2H). Table P: Examples of compounds of formula (I) b) Synthesis of Intermediates:

[0264] EXAMPLE P-I1: Preparation of 5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridine-3-carbonyl chloride (intermediate I3 ) and 5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridine-3-carboxamide (intermediate I4)

[0265] Step P-I1.1: Synthesis of methyl 5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridine-3-carboxylate ( intermediate I1)

[0266] A high pressure reactor under argon was charged with a degassed solution of 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoro-methyl)imidazo[4,5- c]pyridine (WO16/005263) (10.0 g, 22.26 mmol) in methanol (111 mL). Triethylamine (2.7 g, 3.44 mL, 26.71 mmol) and dichloro[1,3-bis(diphenylphosphine)propane]palladium (II) (PdCl2(dippp), 0.66 g, 1.11 mmol) were added. The reaction vessel was pressurized with carbon monoxide at 5 bar and heated to 100 °C for 24 hours. After cooling, the mixture was filtered over Celite and the filtrate was concentrated. The residue was suspended in ethyl acetate, the solid isolated by filtration and washed with water. This solid material was dissolved in dichloromethane, the solution dried over sodium sulfate, filtered and concentrated to give 5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl ]Crude pyridine-3-carboxylate (intermediate I1) as a solid, mp 200-202°C. This material was used without further purification. LCMS (method 1): 429 (M+H)+, retention time 0.94 min.

[0267] Step P-I1.2: Synthesis of 5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridine-3-carboxylic acid (intermediate I2)

[0268] To a solution of methyl 5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridine-3-carboxylate (5 g, 11, 67 mmol) into a 3:1 mixture of tetrahydrofuran and water (134 mL) at 0-5 °C was added lithium hydroxide monohydrate (514 mg, 12.25 mmol). The reaction mixture was stirred at room temperature overnight, then diluted with tert-butylmethyl ether. The phases were separated, the water layer acidified to pH 2 with aqueous hydrochloric acid and the resulting suspension isolated by filtration. This solid residue was dissolved in dichloromethane, the solution dried over sodium sulfate, filtered and concentrated to give 5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2- acid crude yl]pyridine-3-carboxylic acid (intermediate I2) as a solid, mp 313-314°C. This material was used without further purification. LCMS (method 1): 415 (M+H)+ and 413 (MH)-, retention time 0.78 min.

[0269] Step P-I1.3: Synthesis of 5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridine-3-carbonyl chloride ( intermediate I3)

[0270] To a solution of 5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridine-3-carboxylic acid (3.0 g, 7 .2 mmol) in dichloromethane (80 mL) at 05°C was added oxalyl chloride (0.76 mL, 8.7 mmol) and the mixture was stirred at room temperature overnight. The reaction mixture was concentrated to dryness to give crude 5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridine-3-carbonyl chloride ( intermediate I3) as a solid. This material was used without further purification. 1H NMR (400 MHz, d6-acetone) δ ppm 1.34 (t, 3H), 3.96 (q, 2H), 4.08 (s, 3H), 8.23 (s, 1H), 9, 08 (d, J=2.0 Hz, 1H), 9.28 (s, 1H), 9.69 (d, J=2.0 Hz, 1H).

[0271] Step P-I1.4: Synthesis of 5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridine-3-carboxamide (intermediate I4 )

[0272] Triethylamine (0.725 mL, 5.2 mmol) and 4-(dimethylamino)pyridine (4 mg) were added to a solution of 0.5 M ammonia in dioxane (69 mL, 34.5 mmol) at 0- 5 °C, followed by dropwise addition of a solution of 5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridine-3-carbonyl ( intermediate I3) (1.5 g, 3.47 mmol) in tetrahydrofuran (6 mL). The reaction mixture was stirred at 0-5°C for 30 minutes, then concentrated to dryness under reduced pressure to give 5-ethyl-sulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c crude ]pyridin-2-yl]pyridine-3-carboxamide (intermediate I4) as a solid, mp 251-252°C. LCMS (method 1): 414 (M+H)+, retention time 0.76 min.

[0273] EXAMPLE P-I2: Preparation of 3-ethylsulfonyl-4-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]benzoic acid

[0274] To a solution of methyl 3-ethylsulfonyl-4-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]benzoate (intermediate I12) (800 mg, 1.94 mmol) in Dry N,N-dimethylformamide (15 mL) was added dry lithium chloride LiCl (410 mg, 9.68 mmol) and the mixture was heated in the microwave at 150 °C for one hour. Repeatedly more LiCl (14 x 82 mg) was added, whereby heating at 150°C for one hour was continued after each addition. The reaction mixture was diluted with water and ethyl acetate, the phases were separated, the water layer acidified to pH 4-5 with 0.1 N aqueous hydrochloric acid and the product completely extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated to give crude 3-ethylsulfonyl-4-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]benzoic acid (intermediate I13). like a solid. This material was added dry in vacuo over phosphorus pentoxide at 40°C overnight and used without further purification.

[0275] LCMS (method 1): 400 (M+H)+ and 398 (MH)-, retention time 0.82 min. EXAMPLE P-I3: Preparation of 5-ethylsulfonyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]pyridine-3-carboxylic acid (intermediate I10)

[0276] Step P-I3.1: Synthesis of 5-ethylsulfonyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]pyridine-3-carbonitrile (intermediate I9 )

[0277] To a solution of 6-(5-bromo-3-ethylsulfonyl-2-pyridyl)-7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazine (WO16/059145) (900 mg, 2.0 mmol) in 1-methyl-2-pyrrolidone (11 mL) copper (I) cyanide (716 mg, 8.0 mmol) was added and the reaction mixture was purged with argon. Copper (I) iodide (38 mg, 0.20 mmol) was added and the mixture heated in the microwave at 150 °C for one hour. The reaction mixture was poured into ice water, the resulting suspension filtered, and the solid washed with cold water. The solid residue was treated with tetrahydrofuran, the solution filtered and the filtrate concentrated to dryness under reduced pressure and this work-up repeated with toluene three times. The crude solid was further stirred in cold ethyl acetate, the suspension filtered and the solid dried under vacuum at 50°C overnight to give 5-ethylsulfonyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4 ,5-c]pyridazin-6-yl]pyridine-3-carbonitrile (intermediate I9). This material was used without further purification. 1H NMR (400 MHz, CDCl3) δ ppm 1.45 (t, J=7.3 Hz, 3H), 3.91 (q, J=7.3 Hz, 2H), 4.15 (s, 3H) , 8.25 (s, 1H), 8.85 (d, J=1.8 Hz, 1H), 9.29 (d, J=1.8 Hz, 1H). LCMS (method 1): 397 (M+H)+, retention time 0.87 min.

[0278] Step P-I3.2: Synthesis of 5-ethylsulfonyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]pyridine-3-carboxylic acid (intermediate I10)

[0279] A solution of 5-ethylsulfonyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]pyridine-3-carbonitrile (2.7 g, 6.8 mmol) in 50% aqueous sulfuric acid (40 mL) was heated at 100 °C for 2 hours. The reaction mixture was diluted with ice water, the resulting solid filtered, washed with ice water and dried in vacuo over phosphorus pentoxide at 50°C overnight to give 5-ethylsulfonyl-6-[7-methyl-3-( trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]pyridine-3-carboxylic acid (intermediate I10). LCMS (method 1): 416 (M+H)+ and 414 (M-H)-, retention time 0.76 min.

[0280] EXAMPLE P-I4: Preparation of 5-ethylsulfonyl-6-[6-(trifluoro-methyl)pyrazolo[4,3-c]pyridin-2-yl]pyridine-3-carboxylic acid (intermediate I15)

[0281] Step P-I4.1: Synthesis of 2-(3-ethylsulfonyl-5-vinyl-2-pyridyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine

[0282] To a solution of 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine (WO16/020286) (970 mg, 2.23 mmol ) in dry toluene (10 mL) was added tributyl(vinyl)tin (1.09 g, 97%, 3.34 mmol) and the reaction mixture was purged with argon for 15 minutes. Tetrakis(triphenylphosphine)palladium (0) (129 mg, 0.111 mmol) was added and the mixture heated at 110°C for two hours. The reaction mixture was poured into water (50 mL) and extracted with ethyl acetate (3 x 30 mL). The combined extracts were washed with brine, dried over sodium sulfate and evaporated under reduced pressure. The residue was purified by Combiflash on silica gel (ethyl acetate/hexane 1:1) to give 2-(3-ethylsulfonyl-5-vinyl-2-pyridyl)-6-(trifluoromethyl)pyrazolo[4,3-c] pyridine. LCMS (method 4): 383 (M+H)+, retention time 1.02 min. Step P-I4.2: Synthesis of 5-ethylsulfonyl-6-[6-(trifluoro-methyl)pyrazolo[4,3-c]pyridin-2-yl]pyridine-3-carboxylic acid (intermediate I15)

[0283] To a solution of 2-(3-ethylsulfonyl-5-vinyl-2-pyridyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine (100 mg, 0.26 mmol) in 1.4 -dioxane at 0 °C potassium(VI) osmate dihydrate (48 mg, 0.13 mmol; CAUTION!) was added, followed by a solution of sodium periodate (117 mg, 0.55 mmol) in water ( 2 mL). The reaction mixture was stirred at room temperature for 3 hours. Additional sodium periodate (0.26 mmol) was added and the mixture further stirred at room temperature for 2 hours. The reaction mixture was poured into water (20 mL) and acidified using 2 N aqueous hydrochloric acid. The product was extracted with ethyl acetate (3 x 20 mL), the combined extracts washed with brine, dried over sodium sulfate and evaporated. under reduced pressure to give crude 5-ethylsulfonyl-6-[6-(trifluoro-methyl)pyrazolo[4,3-c]pyridin-2-yl]pyridine-3-carboxylic acid (intermediate I15) as a solid. This material was used without further purification. 1H NMR (400 MHz, DMSO-d6) δ ppm 1.31 (t, 3H), 4.03 (q, 2H), 8.41 (s, 1H), 8.93 (d, 1H), 9, 39 (d, 1H), 9.53 (m, 2H), 10.32 (s, 1H). LCMS (method 3): 401 (M+H)+ and 399 (MH)-, retention time 1.32 min. Table Q: Examples of intermediate compounds of formulas (II), (IV), (VIII), (IX) and (XI)

[0284] 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 formula I with other insecticidal, acaricidal and/or fungicidal active ingredients can also have additional surprising advantages that can also be described, in a broader sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled at their different stages of development or better behavior during their production, for example during crushing or mixing, during their storage or during their use.

[0285] Suitable additions to active ingredients here are, for example, representative of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids , chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations. 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 12 and Table P of the present invention”):

[0286] an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX,

[0287] an acaricide selected from the group of substances consisting of 1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate (IUPAC name/Chemical Abstracts) (1059) + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name) (1295) + TX, 4-chlorophenylphenylsulfone (IUPAC name) (981) + TX, abamectin (1) + TX, acequinocil (3) + TX, acetoprol [CCN] + TX, acrinathrin (9) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, alpha-cypermethrin (202) + TX, amidithion (870) + TX, amidoflumeth [CCN] + TX, amidothioate (872) + TX, amitone (875) + TX, amitone hydrogen oxalate (875) + TX, amitraz (24) + TX, aramite (881) + TX, arsenic 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 (alternative name) [CCN] + TX, benzoximate (71) + TX, benzyl benzoate (IUPAC name) [ CCN] + TX, bifenazate (74) + TX, bifenthrin (76) + TX, binapacryl (907) + TX, brofenvalerate (alternative name) + TX, bromocyclene (918) + TX, bromophos (920) + TX, bromophos- ethyl (921) + TX, bromopropylate (94) + TX, buprofezin (99) + TX, butocarboxym (103) + TX, butoxycarboxym (104) + TX, butylpyridabene (alternative name) + TX, calcium polysulfide (IUPAC name) (111) + TX, camphechlor (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, chlorfensone (970) + TX, chlorfensulfide (971) + TX, chlorfenvinphos (131) + TX, chlorobenzylate (975) + TX, chloromebuform (977) + TX, chlormethiurone (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 (alternative name) [CCN] + TX, coumafos (174) + TX, crotamitone (alternative name) [CCN] + TX, crotoxiphos (1010) + TX, kofraneb (1013) + TX, cyanhoate (1020) + TX, cyflumetofen (CAS Reg. No.: 400882-07-7) + TX, cyhalothrin (196) + TX, ciexatin (199) + TX, cypermethrin (201) + TX, DCPM (1032) + TX, DDT ( 219) + TX, demephione (1037) + TX, demephione-O (1037) + TX, demephione-S (1037) + TX, demetone (1038) + TX, demetone-methyl (224) + TX, demetone-O ( 1038) + TX, demetone-O- methyl (224) + TX, demetone-S (1038) + TX, demetone-S- methyl (224) + TX, demetone-S-methylsulfone (1039) + TX, diafentiurone (226 ) + TX, dialiphos (1042) + TX, diazinone (227) + TX, diclofluanid (230) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicofol (242) + TX, dicrotophos (243 ) + TX, dienochlor (1071) + TX, dimefox (1081) + TX, dimethoate (262) + TX, dynactin (alternative name) (653) + TX, dinex (1089) + TX, dinex-diclexin (1089) + TX, dinobutone (269) + TX, dinocape (270) + TX, dinocape-4 [CCN] + TX, dinocape-6 [CCN] + TX, dinoctone (1090) + TX, dinopentone (1092) + TX, dinosulfone ( 1097) + TX, dinoterbone (1098) + TX, dioxathione (1102) + TX, diphenyl sulfone (IUPAC name) (1103) + TX, disulfiram (alternative name) [CCN] + TX, disulfotone (278) + TX, DNOC (282) + TX, dofenapine (1113) + TX, doramectin (alternative name) [CCN] + TX, endosulfan (294) + TX, endothione (1121) + TX, EPN (297) + TX, eprinomectin (alternative name ) [CCN] + TX, ethione (309) + TX, ethoate-methyl (1134) + TX, ethoxazole (320) + TX, etrinfos (1142) + TX, fenazaflor (1147) + TX, fenazaquine (328) + TX , fenbutatin oxide (330) + TX, phenothiocarb (337) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fenpyroximate (345) + TX, phensone (1157) + TX, fentriphanil (1161) + TX, fenvalerate (349) + TX, fipronil (354) + TX, fluacripyrim (360) + TX, fluazurone (1166) + TX, flubenzimine (1167) + TX, flucicloxurone (366) + TX, flucitrinate (367) + TX, flueethyl (1169) + TX, flufenoxurone (370) + TX, flumethrin (372) + TX, fluorbenside (1174) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formotiona (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, hexithiazox (441) + TX, iodomethane (IUPAC name) (542) + TX, isocarbophos (alternative name) ( 473) + TX, isopropyl O-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenfos (1248) + TX, lindane (430) + TX, lufenurone (490) + TX, malathion (492) + TX, malonobene (1254) + TX, mecarbam (502) + TX, mephospholane (1261) + TX, messulfen (alternative name) [CCN] + TX, metacriphos (1266) + TX, methamidophos (527) + TX, methidathione (529) + TX, methiocarb (530) + TX, methomyl (531) + TX, methyl bromide (537 ) + TX, metolcarb (550) + TX, mevinfos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX , monocrotophos (561) + TX, morphothione (1300) + TX, moxidectin (alternative name) [CCN] + TX, nalede (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) compound) + TX, nifluridide (1309) + TX, nicomycins (alternative name) [CCN] + TX, nitrilacarb (1313) + TX, nitrilacarb complex 1:1 zinc chloride (1313) + TX, NNI-0101 (code of compound) + TX, NNI- 0250 (compound code) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxideprofos (1324) + TX, oxydisulfotone (1325) + TX, pp'-DDT ( 219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, phencaptone (1330) + TX, phentoate (631) + TX, phorate (636) + TX, fosalone (637) + TX, phospholan (1338) + TX, phosmet (638) + TX, phosfamidone (639) + TX, phoxim (642) + TX, pirimiphos- methyl (652) + TX, polychloroterpenes (name traditional) (1347) + TX, polynactins (alternative name) (653) + TX, proclonol (1350) + TX, profenofos (662) + TX, promacil (1354) + TX, propargite (671) + TX, propetanphos (673 ) + TX, propoxur (678) + TX, protidathion (1360) + TX, protoate (1362) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridabene ( 699) + TX, pyridafenthion (701) + TX, pyrimidifene (706) + TX, pyrimitate (1370) + TX, quinalphos (711) + TX, quinthiophos (1381) + TX, R-1492 (development code) (1382 ) + TX, RA-17 (development code) (1383) + TX, rotenone (722) + TX, escradane (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX , SI-0009 (compound code) + TX, sofamide (1402) + TX, spirodiclofen (738) + TX, spiromesifene (739) + TX, SSI-121 (development code) (1404) + TX, sulfiram (name alternative) [CCN] + TX, sulfluramide (750) + TX, sulfotepe (753) + TX, sulfur (754) + TX, SZI-121 (development code) (757) + TX, tau-fluvalinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, terbam (alternative name) + TX, tetrachlorvinphos (777) + TX, tetradifone (786) + TX, tetranactin (alternative name) (653) + TX, tetrasul [CCN] + TX, triamifos (1441) + TX, triaratene (1443) + TX, triazophos (820) + TX, triazurone (alternative name) + TX, trichlorphone (824) + TX, tripenophos (1455) + TX, trinactin (alternative name ) (653) + TX, vamidothione (847) + TX, vaniliprole [CCN] and YI-5302 (compound code) + TX,

[0288] an algaecide selected from the group of substances consisting of betoxazine [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutrin [CCN] + TX, diclone ( 1052) + TX, dichlorophene (232) + TX, endotal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamide ( 1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX,

[0289] an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomate (1011) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate ( 291) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,

[0290] an avicid 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,

[0291] 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 (IUPAC name) (169) + TX, cresol [CCN ] + TX, dichlorophene (232) + TX, dipyrithione (1105) + TX, dodicine (1112) + TX, phenaminosulfe (1144) + TX, formaldehyde (404) + TX, hydrargafen (alternative name) [CCN] + TX, kasugamycin (483) + TX, hydrated kasugamycin hydrochloride (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octylinone (590) + TX, oxolinic acid ( 606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX, and thiomersal (alternative name) [CCN] + TX,

[0292] a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis (alternative name) (33) + TX, Aphidius colemani ( alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide ( scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51) + TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51) + TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alternative name) (53) + TX, Beauveria brongniartii (alternative name) (54) + TX, Chrysoperla carnea (alternative name) (151) + TX, Cryptolaemus montrouzieri ( alternative name) (178) + TX, Cydia pomonella GV (alternative name) (191) + TX, Dacnusa sibirica (alternative name) (212) + TX, Diglyphus isaea (alternative name) (254) + TX, Encarsia formosa (name scientific) (293) + TX, Eretmocerus eremicus (alternative name) (300) + TX, Helicoverpa zea NPV (alternative name) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alternative name) (433) + TX, Hippodamia convergens (alternative name) (442) + TX, Leptomastix dactylopii (alternative name) (488) + TX, Macrolophus caliginosus (alternative name) (491) + TX, Mamestra brassicae NPV (alternative name) (494) + TX, Metaphycus helvolus (alternative name) (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 (alternative name) (575) + TX, Orius spp. (alternative name) (596) + TX, Paecilomyces fumosoroseus (alternative name) (613) + TX, Phytoseiulus persimilis (alternative name) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741) + TX, Steinernema bibionis (alternative name) (742) + TX, Steinernema carpocapsae (alternative name) (742) + TX, Steinernema feltiae (alternative name) (742) + TX, Steinernema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinernema riobravis (alternative name) (742) + TX, Steinernema scapterisci (alternative name) (742) + TX, Steinernema spp. (alternative name) (742) + TX, Trichogramma spp. (alternative name) (826) + TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848) + TX,

[0293] a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX,

[0294] a chemosterilant selected from the group of substances consisting of afolate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzurone (250) + TX, dimatife ( alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl afolate [CCN] + TX, morzide [CCN] + TX, penflurone (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine (alternative name) [CCN] and uredepa (alternative name) [CCN] + TX,

[0295] an insect pheromone selected from the group of substances consisting of (E)-dec-5-en-1-yl acetate 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 (IUPAC name) (779) + TX, (Z)-dodec-7-en-1-yl acetate ( IUPAC name) (285) + TX, (Z)- hexadec-11-enal (IUPAC name) (436) + TX, (Z)- hexadec-11-en-1-yl acetate (IUPAC name) (437) + TX, (Z)-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-yl acetate (IUPAC name) ( 283) + TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780) + TX, (9Z,12E)-tetradeca-9,12-dien-acetate 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 (alternative name) [CCN] + TX, brevicomin (alternative name) [CCN] + TX, codlelure (alternative name) [CCN] + TX, codlemona (alternative name) (167) + TX , cuelure (alternative name) (179) + TX, disparlure (277) + TX, dodec-8-en-1-yl acetate (IUPAC name) (286) + TX, dodec-9-en-1-acetate yl (IUPAC name) (287) + TX, dodeca-8 + TX, 10-dien-1-yl acetate (IUPAC name) (284) + TX, dominicalure (alternative name) [CCN] + TX, 4-methyloctanoate ethyl (IUPAC name) (317) + TX, eugenol (alternative name) [CCN] + TX, frontalin (alternative name) [CCN] + TX, gossyplure (alternative name) (420) + TX, grandlure (421) + TX, grandlure I (alternative name) (421) + TX, grandlure II (alternative name) (421) + TX, grandlure III (alternative name) (421) + TX, grandlure IV (alternative name) (421) + TX, hexalure [CCN] + TX, ipsdienol (alternative name) [CCN] + TX, ipsenol (alternative name) [CCN] + TX, japonilure (alternative name) (481) + TX, lineatin (alternative name) [CCN] + TX , litlure (alternative name) [CCN] + TX, looplure (alternative name) [CCN] + TX, medlure [CCN] + TX, megatomoic acid (alternative name) [CCN] + TX, methyl eugenol (alternative name) ( 540) + TX, muscalure (563) + TX, octadeca-2,13-dien-1-yl acetate (IUPAC name) (588) + TX, octadeca-3,13-dien-1-yl acetate (name IUPAC) (589) + TX, orfralure (alternative name) [CCN] + TX, orictalure (alternative name) (317) + TX, ostramona (alternative name) [CCN] + TX, siglure [CCN] + TX, sordidine ( alternative name) (736) + TX, sulcatol (alternative name) [CCN] + TX, tetradec-11-en-1-yl acetate (IUPAC name) (785) + TX, trimedlure (839) + TX, trimedlure A (alternative name) (839) + TX, trimedlure B1 (alternative name) (839) + TX, trimedlure B2 (alternative name) (839) + TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) ) [CCN] + TX,

[0296] 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, dibutyl phthalate dimethyl [CCN] + TX, ethyl hexanediol (1137) + TX, hexamide [CCN] + TX, methochin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX ,

[0297] an insecticide selected from the group of substances consisting of 1-dichloro-1-nitroethane (IUPAC/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-dichlorophenyl)ethyl acetate (IUPAC name) (1451) + TX, phosphate 2,2-dichlorovinyl and 2-ethylsulfinylethylmethyl (IUPAC name) (1066) + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate (IUPAC/Chemical Abstracts name) (1109) + TX, thiocyanate 2-(2-butoxyethoxy)ethyl (IUPAC/Chemical Abstracts name) (935) + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/Chemical Abstracts name ) (1084) + TX, 2- (4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986) + TX, 2-chlorovinyldiethyl phosphate (IUPAC name) (984) + TX, 2- imidazolidone ( IUPAC name) (1225) + TX, 2-isovalerylindane-1,3-dione (IUPAC name) (1246) + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate (IUPAC name) (1284) + TX , 2-thiocyanatoethyl laurate (IUPAC name) (1433) + TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917) + TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283) + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name) (1285) + TX, 5,5-dimethyl-3-oxocycle dimethylcarbamate -hex-1-enyl (IUPAC name) (1085) + TX, abamectin (1) + TX, acephate (2) + TX, acetamiprid (4) + TX, acethione (alternative name) [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, alosamidine (alternative name) [CCN] + TX, alixicarb (866) + TX, alpha-cypermethrin (202) + TX, alpha-ecdysone (alternative name) [CCN] + TX, phosphide aluminum (640) + TX, amidithion (870) + TX, amidothioate (872) + TX, aminocarb (873) + TX, amitone (875) + TX, amitone hydrogen oxalate (875) + TX, amitraz (24) + TX, anabasine (877) + TX, atidathion (883) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azadirachtin (alternative name) (41) + TX, azamethiphos ( 42) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, nitrogenate (889) + TX, delta endotoxins from Bacillus thuringiensis (alternative name) (52) + TX, barium hexafluorosilicate (name alternative) [CCN] + TX, barium polysulfide (IUPAC/Chemical Abstracts name) (892) + TX, barthrin [CCN] + TX, Bayer 22/190 (development code) (893) + TX, Bayer 22408 (code development) (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 (alternative name) (79) + TX, bioethanometrin [CCN] + TX, biopermethrin (908) + TX, bioresmethrin (80) + TX, bis(2-chloroethyl) ether (IUPAC name) (909) + TX, bistriflurone (83) + TX, borax (86) + TX, brofenvalerate (alternative name) + TX, bromfenvinphos (914) + TX, bromocyclene (918 ) + TX, bromoDDT (alternative name) [CCN] + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, bufencarb (924) + TX, buprofezin (99) + TX, butacarb (926) + TX, butathiofos (927) + TX, butocarboxym (103) + TX, butonate (932) + TX, butoxycarboxym (104) + TX, butylpyridabene (alternative name) + TX, cadusafos (109) + TX, calcium arsenate [CCN ] + TX, calcium cyanide (444) + TX, calcium polysulfide (IUPAC name) (111) + TX, camphechlor (941) + TX, carbanolate (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, cartape (123 ) + TX, cartape hydrochloride (123) + TX, cevadine (alternative name) (725) + TX, chlorbicyclene (960) + TX, chlordane (128) + TX, chlordecone (963) + TX, chlordimeform (964) + TX, Chlordimeform hydrochloride (964) + TX, Chlorethoxyphos (129) + TX, Chlorfenapyr (130) + TX, Chlorfenvinphos (131) + TX, Chlorfluazurone (132) + TX, Chlormephos (136) + TX, Chloroform [CCN] + TX, chloropicrin (141) + TX, chlorfoxim (989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, chromafenozide (150 ) + TX, kinerin I (696) + TX, cinerin II (696) + TX, kinerins (696) + TX, cis-resmethrin (alternative name) + TX, cysmethrin (80) + TX, clocitrin (alternative name) + TX, cloetocarb (999) + TX, closantel (alternative name) [CCN] + TX, clothianidin (165) + TX, copper acetoarsenite [CCN] + TX, copper arsenate [CCN] + TX, copper oleate [CCN ] + TX, coumaphos (174) + TX, coumitoate (1006) + TX, crotamiton (alternative name) [CCN] + TX, crotoxiphos (1010) + TX, crufomate (1011) + TX, cryolite (alternative name) (177 ) + TX, CS 708 (development code) (1012) + TX, cyanofenphos (1019) + TX, cyanophos (184) + TX, cyantoate (1020) + TX, cyclothrin [CCN] + TX, cycloprothrin (188) + TX, cyfluthrin (193) + TX, cyhalothrin (196) + TX, cypermethrin (201) + TX, cyfenothrin (206) + TX, cyromazine (209) + TX, cythioate (alternative name) [CCN] + TX, d- limonene (alternative name) [CCN] + TX, d-tetramethrin (alternative name) (788) + TX, DAEP (1031) + TX, dazomet (216) + TX, DDT (219) + TX, decarbofuran (1034) + TX, deltamethrin (223) + TX, demefion (1037) + TX, demefion-O (1037) + TX, demefion-S (1037) + TX, demethone (1038) + TX, demethone-methyl (224) + TX, demetone-O (1038) + TX, demetone-O- methyl (224) + TX, demetone-S (1038) + TX, demetone-S- methyl (224) + TX, demetone-S-methylsulfone (1039) + TX , diafentiurone (226) + TX, dialyphos (1042) + TX, diamidaphos (1044) + TX, diazinone (227) + TX, dicaptone (1050) + TX, diclofenthion (1051) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicresyl (alternative name) [CCN] + TX, dicrotophos (243) + TX, dicyclanyl (244) + TX, dieldrin (1070) + TX, diethyl phosphate and 5-methylpyrazole-3- ila (IUPAC name) (1076) + TX, diflubenzurone (250) + TX, dilor (alternative name) [CCN] + TX, dimefluthrin [CCN] + TX, dimefox (1081) + TX, dimethane (1085) + TX, dimethoate (262) + TX, dimethrin (1083) + TX, dimethylvinphos (265) + TX, dimethylane (1086) + TX, dinex (1089) + TX, dinex-diclexin (1089) + TX, dinoprop (1093) + TX , dinosam (1094) + TX, dinoseb (1095) + TX, dinotefuran (271) + TX, diophenolan (1099) + TX, dioxabenzofos (1100) + TX, dioxacarb (1101) + TX, dioxathione (1102) + TX, disulfotone (278) + TX, diticrophos (1108) + TX, DNOC (282) + TX, doramectin (alternative name) [CCN] + TX, DSP (1115) + TX, ecdysterone (alternative name) [CCN] + TX, EI 1642 (development code) (1118) + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, EMPC (1120) + TX, empentrin (292) + TX, endosulfan (294) + TX, endothione (1121) + TX, endrin (1122) + TX, EPBP (1123) + TX, EPN (297) + TX, epofenonan (1124) + TX, eprinomectin (alternative name) [CCN] + TX, esfenvalerate (302) + TX, etaphos (alternative name) [CCN] + TX, ethiofencarb (308) + TX, ethion (309) + TX, etiprol (310) + TX, ethoate-methyl (1134) + TX, etoprophos (312) + TX , ethyl formate (IUPAC name) [CCN] + TX, ethyl-DDD (alternative name) (1056) + TX, ethylene dibromide (316) + TX, ethylene dichloride (chemical name) (1136) + TX, oxide ethylene [CCN] + TX, etofenprox (319) + TX, etrinphos (1142) + TX, EXD (1143) + TX, fanfur (323) + TX, fenamifos (326) + TX, fenazaflor (1147) + TX, fenchlorphos (1148) + TX, fenetacarb (1149) + TX, fenfluthrin (1150) + TX, fenitrothion (335) + TX, fenobucarb (336) + TX, fenoxacrim (1153) + TX, fenoxycarb (340) + TX, fenpyrythrin (1155) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fensulfothione (1158) + TX, phenthion (346) + TX, phenthion-ethyl [CCN] + TX, fenvalerate (349) + TX , fipronil (354) + TX, flonicamide (358) + TX, flubendiamide (N. ° Reg. CAS.: 272451-65-7) + TX, flucofurone (1168) + TX, flucicloxurone (366) + TX, flucitrinate (367) + TX, fluenethyl (1169) + TX, flufenerim [CCN] + TX, flufenoxurone (370 ) + TX, flufenprox (1171) + TX, flumethrin (372) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, fonofos (1191) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formotiona (1192) + TX, formparanate (1193) + TX, fosmethylane (1194) + TX, fospirate (1195) + TX, fosthiazate (408) + TX, fosthiethane (1196) + TX, furatiocarb (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, hexaflumurone (439) + TX, HHDN (864) + TX, hydramethylnone (443) + TX, hydrogen cyanide (444) + TX, hydroprene (445) + TX , hiquincarb (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 (alternative name) (473) + TX, isodrine (1235) + TX, isofenphos (1236) + TX, isolane (1237) + TX, isoprocarb (472) + TX, Isopropyl O-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473) + TX, isoprothiolane (474) + TX, isothioate (1244) + TX, isoxathione (480) + TX, ivermectin (alternative name) [CCN] + TX, jasmolina I (696) + TX, jasmolina II (696) + TX, jodfenfos (1248) + TX, juvenile hormone I (alternative name) [CCN] + TX, juvenile hormone II (alternative name) [CCN] + TX, hormone juvenile III (alternative name) [CCN] + TX, quelevane (1249) + TX, quinoprene (484) + TX, lambda-cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepimectin (CCN) + TX , leptophos (1250) + TX, lindane (430) + TX, lyrinfos (1251) + TX, lufenurone (490) + TX, lithidathione (1253) + TX, m-cumenyl methylcarbamate (IUPAC name) (1014) + TX , magnesium phosphide (IUPAC name) (640) + TX, malathion (492) + TX, malonobene (1254) + TX, mazidox (1255) + TX, mecarbam (502) + TX, mecarfone (1258) + TX, menazone (1260) + TX, mephospholane (1261) + TX, mercurous chloride (513) + TX, mesulfenphos (1263) + TX, metaflumizone (CCN) + TX, metam (519) + TX, metam-potassium (alternative name) ( 519) + TX, methamsodium (519) + TX, metacrifos (1266) + TX, methamidophos (527) + TX, methanesulfonyl fluoride (IUPAC/Chemical Abstracts name) (1268) + TX, methidathione (529) + TX , methiocarb (530) + TX, methocrotophos (1273) + TX, methomyl (531) + TX, methoprene (532) + TX, methochin-butyl (1276) + TX, methotrin (alternative name) (533) + TX, methoxychlor (534) + TX, methoxyfenozide (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methylchloroform (alternative name) [CCN] + TX, methylene chloride [CCN] + TX , metofluthrin [CCN] + TX, metolcarb (550) + TX, methoxadiazone (1288) + TX, mevinfos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [ CCN] + TX, mipafox (1293) + TX, mirex (1294) + TX, monocrotophos (561) + TX, morphothione (1300) + TX, moxidectin (alternative name) [CCN] + TX, naphthalophos (alternative name) [ CCN] + TX, nalede (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, novalurone (585) + TX, noviflumurone (586) + TX, O-5-dichloro-4-iodophenyl and O-ethyl ethylphosphonothioate (IUPAC name) (1057) + TX, O,O-diethyl and O-4-methyl-2-oxo- phosphorothioate 2H-chromen-7-yl (IUPAC name) (1074) + TX, O,O-diethyl and O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate (IUPAC name) (1075) + TX, dithiopyrophosphate O,O,O',O'-tetrapropyl (IUPAC name) (1424) + TX, oleic acid (IUPAC name) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydemetone- methyl (609) + TX, oxideprophos (1324) + TX, oxydisulfotone (1325) + TX, pp'-DDT (219) + TX, para-dichlorobenzene [CCN] + TX, parathion (615) + TX, parathion-methyl ( 616) + TX, penflurone (alternative name) [CCN] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (IUPAC name) (623) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, PH 60-38 (development code) (1328) + TX, phencaptone (1330) + TX, phenothrin (630) + TX, phentoate (631) + TX, phorate (636) + TX, fosalone (637) + TX, phospholane (1338) + TX, phosmet (638) + TX, fosnichlor (1339) + TX, phosfamidone (639) + TX, phosphine (IUPAC name) (640) + TX, phoxim (642) + TX, phoxim-methyl (1340) + TX, pirimiphos (1344) + TX, pirimicarb (651) + TX, pirimiphos-ethyl (1345) + TX, pirimiphos-methyl (652) + TX, polychlorodicyclopentadiene isomers (IUPAC name) (1346) + TX, polychloroterpenes (traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, pralethrin (655) + TX, precone I (alternative name) [CCN ] + TX, precono II (alternative name) [CCN] + TX, precono III (alternative name) [CCN] + TX, primidone (1349) + TX, profenofos (662) + TX, profluthrin [CCN] + TX, promacil (1354) + TX, promecarb (1355) + TX, propaphos (1356) + TX, propetanphos (673) + TX, propoxur (678) + TX, protidathion (1360) + TX, prothiophos (686) + TX, protoate ( 1362) + TX, protrifenbut [CCN] + TX, pymetrozine (688) + TX, pyraclophos (689) + TX, pyrazophos (693) + TX, pyresmethrin (1367) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridabene (699) + TX, pyridalyl (700) + TX, pyridafenthion (701) + TX, pyrimidifene (706) + TX, pyrimitate (1370) + TX, pyriproxyfen ( 708) + TX, quassia (alternative name) [CCN] + TX, quinalphos (711) + TX, quinalphos-methyl (1376) + TX, quinothione (1380) + TX, quinthiophos (1381) + TX, R-1492 ( development code) (1382) + TX, rafoxanide (alternative name) [CCN] + TX, resmethrin (719) + TX, rotenone (722) + TX, RU 15525 (development code) (723) + TX, RU 25475 (development code) (1386) + TX, riania (alternative name) (1387) + TX, ryanodina (traditional name) (1387) + TX, sabadila (alternative name) (725) + TX, escradano (1389) + TX , sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, silafluofen (728) + TX, SN 72129 (development code) (1397) + TX, sodium arsenite [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, thiocyanate sodium [CCN] + TX, sofamide (1402) + TX, spinosad (737) + TX, spiromesifene (739) + TX, spirotetramate (CCN) + TX, sulcofurone (746) + TX, sulcofurone-sodium (746) + TX, sulfluramide (750) + TX, sulfothepe (753) + TX, sulfuryl fluoride (756) + TX, sulprophos (1408) + TX, tar oils (alternative name) (758) + TX, tau-fluvalinate (398 ) + TX, tazimcarb (1412) + TX, TDE (1414) + TX, tebufenozide (762) + TX, tebufenpyrad (763) + TX, tebupirinphos (764) + TX, teflubenzurone (768) + TX, tefluthrin (769) + TX, temephos (770) + TX, TEPP (1417) + TX, teralethrin (1418) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachloroethane [CCN] + TX, tetrachlorvinphos (777) + TX, tetramethrin (787) + TX, theta-cypermethrin (204) + TX, thiacloprid (791) + TX, thiafenox (alternative name) + TX, thiamethoxam (792) + TX, ticrofos (1428) + TX, thiocarboxime ( 1431) + TX, thiocyclam (798) + TX, thiocyclam hydrogen oxalate (798) + TX, thiodicarb (799) + TX, thiofanox (800) + TX, thiometone (801) + TX, thionazine (1434) + TX , thiosultape (803) + TX, thiosultape-sodium (803) + TX, thuringiensin (alternative name) [CCN] + TX, tolfenpyrad (809) + TX, tralomethrin (812) + TX, transfluthrin (813) + TX, transpermethrin (1440) + TX, triamifos (1441) + TX, triazamate (818) + TX, triazophos (820) + TX, triazurone (alternative name) + TX, trichlorphone (824) + TX, trichlormetaphos-3 (alternative name) [ CCN] + TX, trichloronate (1452) + TX, tripenofos (1455) + TX, triflumurone (835) + TX, trimetacarb (840) + TX, triprene (1459) + TX, vamidothione (847) + TX, vaniliprole [CCN ] + TX, veratridine (alternative name) (725) + TX, veratrin (alternative name) (725) + TX, XMC (853) + TX, xylylcarb (854) + TX, YI-5302 (compound code) + TX , zeta-cypermethrin (205) + TX, zetamethrin (alternative name) + TX, zinc phosphide (640) + TX, zolaprophos (1469) and ZXI 8901 (development code) (858) + TX, cyantraniliprol [736994-63 -19] + TX, chlorantraniliprol [500008-45-7] + TX, cyenopirafen [560121-52-0] + TX, cyflumetofen [400882-077] + TX, pyrifluquinazone [337458-27-2] + TX, spinetoram [ 187166-40-1 + 187166-15-0] + TX, spirotetramate [20331325-1] + 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, fluxametamide (WO 2007/026965) + TX, epsilon-metofluthrin [240494-71-7] + TX, epsilon-momfluorothrin [1065124-65-3] + TX, fluazaindolizine [1254304-22-7] + TX, chloropralethrin [399572-87-3] + TX, fluxametamide [928783-29-3] + TX, cyhalodiamide [1262605-537] + TX, thioxazaphene [330459-31-9] + TX, broflanilide [1207727-04-5] + TX, flufiprol [704886-18-0] + TX, cyclaniliprol [1031756-98-5] + TX, tetraniliprol [122965466-3] + TX, guadipyr (described in WO2010/060231) + TX, cycloxapride (described in WO 2005/077934) + TX, spiropidion + TX, Afidopyropene + TX, flupyrimin + TX, Momfluorothrin + TX, capa-bifenthrin + TX, capa-tefluthrin + TX, Dichloromezothiaz + TX, Tetrachloraniliprol + TX, benzpyrimoxane + 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, cloetocarb (999) + TX, acetoarsenite of copper [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 , 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 (name IUPAC/Chemical Abstracts) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 1,1-3-dioxide ,4-dichlorotetrahydrothiophene (IUPAC/Chemical Abstracts name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1 acid ,3,5-thiadiazinan-3-ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alternative name) (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, butylpyridabene (alternative name) + TX, cadusafos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbosulfan (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, chloretocarb (999) + TX , cytokinins (alternative name) (210) + TX, dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidaphos (1044) + TX, diclofenthion (1051) + TX, dicliphos (name alternative) + TX, dimethoate (262) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, etoprophos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fenpyrad (alternative name) + TX, fensulfothione (1158) + TX, fosthiazate (408) + TX, fosthiethane (1196) + TX, furfural (alternative name) [CCN] + TX, GY-81 (development code) (423) + TX, heterophos [CCN] + TX, iodomethane (IUPAC name) (542) + TX, isamidophos (1230) + TX, isazophos (1231) + TX, ivermectin (alternative name) [CCN] + TX, kinetin (alternative name) (210) + TX, mecarfon (1258) + TX, metam (519) + TX, metam-potassium (name alternative) (519) + TX, methamsodium (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) alternative) [CCN] + TX, composition of Myrothecium verrucaria (alternative name) (565) + TX, NC- 184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidone (639 ) + TX, phosphocarb [CCN] + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) + TX, terbame (alternative name) + TX, terbufos (773) + TX, tetrachlorothiophene (IUPAC/Chemical Abstracts name) (1422) + TX, thiafenox (alternative name) + TX, thionazine (1434) + TX, triazophos (820) + TX, triazurone (alternative name) + TX, xylenols [CCN] + TX, YI-5302 (compound code) and zeatin (alternative name) (210) + TX, fluensulfone [318290-98-1] + TX, fluopyram + TX, a nitrification inhibitor selected from the group of substances consisting of ethylxanthate potassium [CCN] and nitrapyrin (580) + TX, a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria extract sachalinensis (alternative name) (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 ( IUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminum phosphide (640) + TX, antu (880) + TX, arsenic 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 (alternative name) (850) + TX, coumaclor (1004) + TX, coumafuril (1005) + TX, coumatetralyl (175) + TX, crimidine (1009) + TX, difenacoum (246) + TX, diffethialone (249) + TX, diphacinone (273) + TX, ergocalciferol (301) + TX, flocoumafen (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, fosacetim (1336) + TX, phosphine (IUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone ( 1341) + TX, potassium arsenite [CCN] + TX, pyrinurone (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-(piperonylate) 2-butoxyethoxy)ethyl (IUPAC name) (934) + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343 ) + TX, propyl isomer (1358) + TX, S421 (developmental code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX,

[0298] an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171) + TX, diazinone (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX , thiram (804) + TX, trimetacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX, a virucide selected from the group of substances consisting of imannin (alternative name) [CCN] and ribavirin (name alternative) [CCN] + TX,

[0299] a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octilinone (590) and thiophanate-methyl (802) + TX,

[0300] and biologically active compounds selected from the group consisting of 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, epoxiconazole [106325-08-0] + TX, fenbuconazole [114369-436] + TX, fluquinconazole [ 136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol [76674-21-0] + TX, hexaconazole [79983-71-4] + TX, imazalil [35554-44-0] + TX, imibenconazole [86598-92-7] + TX, ipconazole [12522528-7] + TX, metconazole [125116-23-6] + TX, myclobutanil [88671-89-0] + TX, pefurazoate [101903-30 -4] + TX, penconazole [66246-88-6] + TX, prothioconazole [178928-70-6] + TX, pirifenox [88283-41-4] + TX, prochloraz [67747-095] + TX, propiconazole [ 60207-90-1] + TX, simeconazole [149508-90-7] + TX, tebuconazole [107534-96-3] + TX, tetraconazole [112281-77-3] + TX, triadimephone [43121-433] + TX , triadimenol [55219-65-3] + TX, triflumizole [99387-89-0] + TX, triticonazole [131983-72-7] + TX, ancimidol [12771-68-5] + TX, fenarimol [60168-88 -9] + TX, nuarimol [63284-71-9] + TX, bupyrimate [41483-43-6] + TX, dimethyrimole [5221-53-4] + TX, ethyrimole [23947-60-6] + TX, dodemorph [1593-77-7] + TX, fenpropidine [67306-00-7] + TX, fenpropimorph [67564-91-4] + TX, spiroxamine [118134-30-8] + TX, tridemorph [81412-43- 3] + TX, cyprodinil [121552-61-2] + TX, mepanipyrim [110235-47-7] + 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 [7063017-0 ] + TX, ofurace [58810-48-3] + TX, oxadixyl [7773209-3] + 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, clozolinate [84332-86-5] + TX, diclozoline [24201-58-9] + TX , iprodione [36734-19-7] + TX, myclozolin [54864-618] + TX, procymidone [32809-16-8] + TX, vinclozolin [50471-44-8] + TX, boscalid [188425-85-6 ] + TX, carboxin [5234-68-4] + TX, fenfuram [24691-80-3] + TX, flutolanil [66332-96-5] + TX, mepronil [55814-41-0] + TX, oxycarboxin [ 5259-88-1] + TX, penthiopyrad [18367582-3] + TX, thifluzamide [130000-40-7] + TX, guazatine [108173-90-6] + TX, dodina [2439-10-3] [112 -65-2] (free base) + TX, iminoctadine [13516-27-3] + TX, azoxystrobin [131860-33-8] + TX, dimoxystrobin [14996152-4] + TX, enestroburin {Proc. BCPC, Congr. Int., Glasgow, 2003, 1, 93} + TX, fluoxastrobin [361377-29-9] + TX, kresoxim-methyl [143390-89-0] + TX, metominostrobin [133408-50-1] + TX, trifloxystrobin [141517-21-7] + TX, orisastrobin [248593-16-0] + TX, picoxystrobin [117428-22-5] + TX, pyraclostrobin [175013-18-0] + TX, ferbam [14484-64-1 ] + TX, mancozeb [8018-01-7] + TX, maneb [12427-38-2] + TX, metiram [9006-42-2] + TX, propineb [12071-83-9] + TX, tiram [ 137-26-8] + TX, zineb [12122-67-7] + TX, ziram [13730-4] + TX, Captafol [2425-06-1] + TX, Captan [133-062] + TX, Diclofluanid [1085-98-9] + TX, fluoroimide [41205-21-4] + TX, folpet [133-07-3] + TX, tolylfluanide [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, copper oxide [1317 -39-1] + TX, mancobre [53988-93-5] + TX, oxina-copper [10380-28-6] + TX, dinocape [131-72-6] + TX, nitrotal-isopropyl [10552-74 -6] + TX, edifenfos [1710949-8] + TX, iprobenfos [26087-47-8] + TX, isoprothiolane [50512-35-1] + TX, phosdifen [36519-00-3] + TX, pyrazophos [ 13457-18-6] + TX, tolclofos-methyl [57018-04-9] + TX, acibenzolar-S-methyl [135158-54-2] + TX, anylazine [10105-3] + TX, bentiavalicarb [413615- 35-7] + TX, blasticidin-S [2079-00-7] + TX, quinomethionate [2439-012] + TX, chloroneb [2675-77-6] + TX, chlorothalonil [189745-6] + 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, dichlorane [99-30-9] + TX, diethofencarb [87130-20-9] + TX, dimethomorph [110488-70-5] + TX, SYP-LI90 (Flumorph) [211867-47-9] + TX, dithianone [3347-22-6] + TX, etaboxam [162650-77-3] + TX, etridiazole [2593-15-9] + TX, famoxadone [131807-57-3] + TX, fenamidone [161326 -34-7] + TX, fenoxanil [115852-48-7] + TX, fentin [668-34-8] + TX, ferimzone [89269-64-7] + TX, fluazinam [79622-59-6] + TX, fluopicolide [239110-15-7] + TX, flusulfamide [106917-52-6] + TX, fenexamide [126833-17-8] + TX, fosetyl aluminum [39148-24-8] + TX, himexazole [ 10004-441] + TX, iprovalicarb [140923-17-7] + TX, IKF-916 (Ciazofamide) [120116-88-3] + TX, kasugamycin [6980-183] + TX, metasulfocarb [66952-49-6 ] + TX, metrafenone [220899-03-6] + TX, pencicurone [66063-05-6] + TX, phthalide [27355-22-2] + TX, polyoxins [11113-80-7] + TX, probenazole [ 27605-76-1] + TX, propamocarb [25606-41-1] + TX, proquinazide [189278-12-4] + TX, pyroquilone [5736932-1] + TX, quinoxifen [124495-18-7] + TX , quintazene [82-68-8] + TX, sulfur [7704-34-9] + TX, thiadinyl [223580-51-6] + TX, triazoxide [72459-58-6] + TX, tricyclazole [41814-78 -2] + TX, triporin [26644-46-2] + TX, validamycin [37248-47-8] + TX, zoxamide (RH7281) [156052-68-5] + TX, mandipropamide [374726-62-2] + TX, isopyrazam [881685-58-1] + TX, sedaxane [874967-67-6] + TX, (9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methane-naphthalen- 3-Difluoromethyl-1-methyl-1H-pyrazol-4-carboxylic acid 5-yl)-amide (disclosed in WO 2007/048556) + TX, (3',4',5'-trifluoro-biphenyl-2- yl)-3-difluoromethyl-1-methyl-1H-pyrazol-4-carboxylic acid 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, 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- pyrazolo-4-carboxamide [926914-55-8] + TX, lancotrione [1486617-21-3] + TX, florpyrauxifene [943832-81-3] + TX, ipfentrifluconazole [1417782-08- 1] + TX, mefentrifluconazole [1417782-03-6] + TX, quinofumelin [861647-84-9] + TX, chloropralethrin [399572-87-3] + TX, cyalodiamide [1262605-53-7] + TX, fluazaindolizine [1254304-22-7] + TX, fluxametamide [928783-29-3] + TX, epsilon-metofluthrin [240494-71-7] + TX, epsilon-momfluorothrin [1065124-65-3] + TX, pidiflumetofen [1228284 -64-7] + TX, capa-bifenthrin [439680-76-9] + TX, broflanilide [1207727-04-5] + TX, dichloromezothiaz [1263629-39-5] + TX, dipimetitron [16114-35-5 ] + TX, pyraziflumid [942515-63-1] + TX and capatefluthrin [391634-71-2] + TX, and

[0301] microbial including: Acinetobacter lwoffii + TX, Acremonium alternatum + TX + TX, Acremonium cephalosporium + TX + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, Adoxophyes orana granulovirus (AdoxGV) (Capex®) + TX, strain of Agrobacterium radiobacter 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 chroocuccum (Azotomeal®) + TX, Azotobacter cysts (Bionatural Blooming Blossoms®) + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus chitinosporus strain CM-1 + TX, Bacillus chitinosporus strain AQ746 + TX, Bacillus licheniformis strain HB-2 (Biostart™ Rhizoboost®) + TX, Bacillus licheniformis strain 3086 ( EcoGuard® + TX, Green Releaf®) + TX, Bacillus circulans + TX, Bacillus firmus (BioSafe® + TX, BioNem-WP® + TX, VOTiVO®) + TX, Bacillus firmus strain I-1582 + TX, Bacillus macerans + TX, Bacillus 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 Bacillus subtilis AQ743 + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain QST3004 + TX, Bacillus subtilis var. amyloliquefaciens FZB24 (Taegro® + TX, Rhizopro®) + TX, Bacillus thuringiensis Cry2Ae + TX, Bacillus thuringiensis Cry1Ab + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis israelensis (BMP123® + TX, Aquabac ® + 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 strain thuringiensis 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, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp. + TX, Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reukaufii + TX, Candida saitoana (Bio-Coat® + 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 campinensis + TX, Cydia pomonella granulovirus (CYD -X®) + TX, Cydia pomonella granulovirus (Madex® + TX, Madex Plus® + TX, Madex Max/Carpovirusine®) + TX, Cylindrobasidium laeve (Stumpout®) + TX, Cylindrocladium + TX, Debaryomyces hansenii + TX, Drechslera hawaiinensis + TX, Enterobacter cloacae + TX, Enterobacteriaceae + TX, Entomophtora viruenta (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 littoralis + 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 (Myconate®) + 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 geulakonigii + TX, Metarhizium anisopliae (Met52®) + TX, Metarhizium anisopliae (Destruxin WP®) + TX, Metschnikowia fruticola (Shemer®) + TX, Metschnikowia pulcherrima + TX, Microdochium dimerum (Antibot®) + TX, Micromonospora coerulea + TX, Microsphaeropsis ochracea + TX, Muscodor albus 620 (Muscudor®) + TX, Muscodor roseus strain A3-5 + TX, Mycorrhizae spp. (AMykor® + TX, Root Maximizer®) + TX, Myrothecium verrucaria strain AARC-0255 (DiTera®) + TX, BROS PLUS® + TX, Ophiostoma piliferum strain D97 (Sylvanex®) + TX, Paecilomyces farinosus + TX, Paecilomyces fumosoroseus (PFR-97® + TX, PreFeRal®) + TX, Paecilomyces linacinus (Biostat WP®) + TX, Paecilomyces lilacinus strain 251 (MeloCon WG®) + TX, Paenibacillus polymyxa + TX, Pantoea agglomerans (BlightBan C9- 1®) + TX, Pantoea spp. + TX, Pasteuria spp. (Econem®) + TX, Pasteuria nishizawae + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart® + TX, TagTeam®) + TX, Penicillium brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX , Penicillium spp. + TX, Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, phosphate solubilizing bacteria (Phosphomeal®) + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guilermondii + TX, Pichiamembraneefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Pseudomonas fluorescens 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 canaliculata + TX, Puccinia thlaspeos (Wood Warrior®) + TX, Pythium paroecandrum + TX, Pythium oligandrum (Polygandron® + TX, Polyversum®) + TX, Pythium periplocum + TX, Rhanella aquatilis + TX, Rhanella spp. + TX, Rhizobia (Dormal® + TX, Vault®) + TX, Rhizoctonia + TX, Rhodococcus globerulus strain AQ719 + TX, Rhodosporidium diobovatum + TX, Rhodosporidium toruloides + TX, Rhodotorula spp. + TX, Rhodotorula glutinis + TX, Rhodotorula graminis + TX, Rhodotorula mucilagnosa + TX, Rhodotorula rubra + TX, Saccharomyces cerevisiae + TX, Salinococcus roseus + TX, Sclerotinia minor + TX, Sclerotinia minor (SARRITOR®) + TX, Scytalidium spp. + TX, Scytalidium uredinicola + TX, Spodoptera exigua 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 exfoliates + TX, Streptomyces galbus + TX, ces griseoplanus + TX, Streptomyces griseoviridis (Mycostop®) + TX, Streptomyces lydicus (Actinovate®) + TX, Streptomyces lydicus WYEC-108 (ActinoGrow®) + TX, Streptomyces violaceus + TX, Tilletiopsis minor + TX, Tilletiopsis spp. + TX, Trichoderma asperellum (T34 Biocontrol®) + TX, Trichoderma gamsii (Tenet®) + TX, Trichoderma atroviride (Plantmate®) + TX, Trichoderma hamatum TH 382 + TX, Trichoderma harzianum rifai (Mycostar®) + TX, Trichoderma harzianum T-22 (Trianum-P® + TX, PlantShield HC® + TX, RootShield® + TX, Trianum-G®) + TX, Trichoderma harzianum T-39 (Trichodex®) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma spp. LC 52 (Sentinel®) + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + TX, Trichoderma taxi + TX, Trichoderma virens + TX, Trichoderma virens (formerly Gliocladium virens GL- 21) ( SoilGuard®) + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, Trichosporon spp. + TX, Trichothecium spp. + TX, Trichothecium roseum + TX, Typhula phacorrhiza strain 94670 + TX, Typhula phacorrhiza strain 94671 + TX, Ulocladium atrum + TX, Ulocladium oudemansii (Botry-Zen®) + TX, Ustilago maydis + TX, various bacteria and supplemental micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Verticillium lecanii (Mycotal® + TX, Vertalec®) + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv. Poae (Camperico®) + TX, Xenorhabdus bovienii + TX, Xenorhabdus nematophilus; It is

[0302] Plant extracts including: pine oil (Retenol®) + TX, azadirachtin (Plasma Neem Oil® + TX, AzaGuard® + TX, MeemAzal® + TX, Molt-X® + TX, botanical IGR (Neemazad® + TX , 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, oil extracts of clove, rosemary, peppermint and thyme (Garden insect killer®) + TX, Glycinabetaine (Greenstim®) + TX, garlic + TX, grass oil - lemon (GreenMatch®) + TX, neem oil + TX, Nepeta cataria (Nepenta oil) + 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, Rutaceae plant extract (Soleo®) + TX , soybean oil (Ortho ecosense®) + TX, tea tree oil (Timorex Gold®) + TX, thyme oil + TX, AGNIQUE® MMF + TX, BugOil® + TX, blend of rosemary extracts, sesame, peppermint, thyme and cinnamon (EF 300®) + TX, mixture of clove, rosemary and peppermint extracts (EF 400®) + TX, mixture of clove, peppermint and garlic and spearmint oil (Soil Shot ®) + TX, kaolin (Screen®) + TX, brown algae storage glucam (Laminarin®); It is

[0303] pheromones including: blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®) + TX, Fruit Caterpillar Pheromone (Paramount-(CM)/Isomate C-Plus® dispenser) + TX, Moth Pheromone of Grape Berries (3M MEC-GBM Sprayable Pheromone®) + TX, Leaf Roller Pheromone (3M MEC - LR Sprayable Pheromone®) + TX, Muscamona (Snip7 Fly Bait® + TX, Starbar Premium Fly Bait®) + TX , Oriental Fruit Moth Pheromone (3M oriental fruit moth sprayable pheromone®) + TX, Peach Borer Pheromone (Isomate-P®) + TX, Tomato Worm Pheromone (3M Sprayable pheromone®) + TX, Entostat Powder (palm tree extract) (Exosex CM®) + TX, (E + TX,Z + TX,Z)- 3 + TX, 8 + TX, 11-tetradecatrienyl acetate + TX, (Z + TX,Z + TX, E)-7 + TX, 11 + 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, Lavandulyl senecioate; It is

[0304] 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, Amblyseius cucumeris (Thripex ® + TX, Bugline cucumeris®) + TX, Amblyseius fallacis (Fallacis®) + TX, Amblyseius swirskii (Bugline swirskii® + TX, Swirskii-Mite®) + TX, Amblyseius womersleyi (WomerMite®) + TX, Amitus hesperidum + TX , Anagrus atomus + TX, Anagyrus fusciventris + TX, Anagyrus kamali + TX, Anagyrus loecki + TX, Anagyrus pseudococci (Citripar®) + TX, Anicetus benefices + TX, Anisopteromalus calandrae + TX, Anthocoris nemoralis (Anthocoris-System®) + TX , Aphelinus abdominalis (Apheline® + TX, Aphiline®) + TX, Aphelinus asychis + TX, Aphidius colemani (Aphipar®) + TX, Aphidius ervi (Ervipar®) + TX, Aphidius gifuensis + TX, Aphidius matricariae (Aphipar-M® ) + TX, Aphidoletes aphidimyza (Aphidend®) + TX, Aphidoletes aphidimyza (Aphidoline®) + TX, Aphytis lingnanensis + TX, Aphytis melinus + TX, Aprostocetus hagenowii + TX, Atheta coriaria (Staphyline®) + TX, Bombus spp. + TX, Bombus terrestris (Natupol Beehive®) + TX, Bombus terrestris (Beeline® + TX, Tripol®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus + TX, Chrysoperla carnea (Chrysoline®) + TX, Chrysoperla carnea (Chrysopa ®) + TX, Chrysoperla rufilabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichus phyllocnistoides + TX, Closterocerus chamaeleon + TX, Closterocerus spp. + TX, Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug® + TX, Cryptoline®) + TX, Cybocephalus nipponicus + TX , Dacnusa sibirica + TX, Dacnusa sibirica (Minusa®) + TX, Diglyphus isaea (Diminex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea + TX, Diglyphus isaea (Miglyphus® + TX, Digline®) + TX, Dacnusa sibirica (DacDigline® + TX, Minex®) + TX, Diversinervus spp. + TX, Encarsia citrina + TX, Encarsia formosa (Encarsia max® + TX, Encarline® + TX, En-Strip®) + TX, Eretmocerus eremicus (Enermix®) + TX, Encarsia guadeloupae + TX, Encarsia haitiensis + TX, Episyrphus balteatus (Syrphidend®) + TX, Eretmoceris siphonini + TX, Eretmocerus californicus + TX, Eretmocerus eremicus (Ercal® + TX, Eretline e®) + TX, Eretmocerus eremicus (Bemimix®) + TX, Eretmocerus hayati + TX, Eretmocerus mundus ( Bemipar® + TX, Eretline m®) + TX, Eretmocerus siphonini + TX, Exochomus quadripustulatus + TX, Feltiella acarisuga (Spidend®) + TX, Feltiella acarisuga (Feltiline®) + TX, Fopius arisanus + TX, Fopius ceratitivorus + TX, Formononetina (Wirless Beehome®) + TX, Franklinothrips vespiformis (Vespop®) + TX, Galendromus occidentalis + TX, Goniozus legneri + TX, Habrobracon hebetor + TX, Harmonia axyridis (HarmoBeetle®) + TX, Heterorhabditis spp. (Lawn Patrol®) + TX, Heterorhabditis bacteriophora (NemaShield HB® + TX, Nemaseek® + TX, Terranem-Nam® + TX, Terranem® + TX, Larvanem® + TX, B-Green® + TX, NemAttack® + TX , Nematop®) + TX, Heterorhabditis megidis (Nemasys H® + TX, BioNem H® + TX, Exhibitline hm® + TX, Larvanem-M®) + TX, Hippodamia convergens + TX, Hypoaspis aculeifer (Aculeifer- System® + TX , Entomite-A®) + TX, Hypoaspis miles (Hypoline m® + TX, Entomite-M®) + TX, Lbalia leucospoides + TX, Lecanoideus floccissimus + TX, Lemophagus errabundus + TX, Leptomastidea abnormis + TX, Leptomastix dactylopii (Leptopar ®) + TX, Leptomastix epona + TX, Lindorus lophanthae + TX, Lipolexis oregmae + TX, Lucilia caesar (Natufly®) + TX, Lysiphlebus testceipes + 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, Ophyra aenescens (Biofly®) + TX, Orius insidiosus (Thripor-I ® + TX, Oriline i®) + TX, Orius laevigatus (Thripor-L® + TX, Oriline l®) + TX, Orius majusculus (Oriline m®) + TX, Orius strigicollis (Thripor-S®) + TX, Pauesia juniperorum + TX, Pediobius foveolatus + TX, Phasmarhabditis hermaphrodita (Nemaslug®) + TX, Phymastichus coffea + TX, Phytoseiulus macropilus + TX, Phytoseiulus persimilis (Spidex® + TX, Phytoline p®) + TX, Podisus maculiventris (Podisus®) + TX, Pseudacteon curvatus + TX, Pseudacteon obtusus + TX, Pseudacteon tricuspis + TX, Pseudaphycus maculipennis + TX, Pseudleptomastix americana + TX, Psyllaephagus pilosus + TX, Psyttalia concolor (complex) + TX, Quadrastichus spp. + TX, Rhyzobius lophanthae + TX, Rodolia cardinalis + TX, Rumina decollate + TX, Semielacher petiolatus + TX, Sitobion avenae (Ervibank®) + TX, Steinernema carpocapsae (Nematac C® + 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; It is

[0305] other biologics 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-brassonolide + TX, Iron Phosphate (Lilly Miller Worry Free Ferramol Slug & Snail Bait®) + TX, MCP Hail Trap (Trapline f®) + TX, Microctonus hyperodae + TX, Mycoleptodiscus terrestris (Des-X®) + TX, BioGain® + TX, Aminomite® + TX, Zenox® + TX, Pheromone Trap (Thripline ams®) + TX, Potassium Bicarbonate (MilStop®) + TX, Potassium Salts of fatty acids (Sanova®) + TX, potassium silicate solution (Sil-Matrix®) + TX, potassium iodide + potassium thiocyanate (Enzicur®) + TX, SuffOil-X® + TX, Spider venom + TX , Nosema locustae (Semaspore Organic Grasshopper Control®) + TX, Sticky traps (Trapline YF® + TX, Rebell Amarillo®) + TX and Traps (Takitrapline y + b®) + TX;

[0306] or a biologically active compound or agent selected from: Broflutrinate + TX, Diflovidazine + TX, Flometoquine + TX, Flu-hexaphone + TX, Plutella xylostella granulosis virus + TX, Cydia pomonella granulosis virus + TX, Imiciafos + TX, Heliothis virescens nucleopolyhedrovirus + TX, Heliothis punctigera nucleopolyhedrovirus + TX, Helicoverpa zea nucleopolyhedrovirus + TX, Spodoptera frugiperda nucleopolyhedrovirus + TX, Plutella xylostella nucleopolyhedrovirus + TX, p- cymene + TX, Piflubumide + TX, Pirafluprol + TX, QRD 420 + TX, QRD 452 + TX, QRD 460 + TX, Terpenoid combinations + TX, Terpenoids + TX, Tetraniliprol + TX, and α-terpinene + TX; or an active substance referenced by a code + TX, such as AE code 1887196 (BSC-BX60309) + TX, code NNI-0745 GR + TX, code IKI-3106 + TX, code JT-L001 + TX, code ZNQ-08056 + TX, code IPPA152201 + TX, code HNPC-A9908 (CAS: [660411-21-2]) + TX, code HNPC-A2005 (CAS: [86002812-2]) + TX, code JS118 + TX, code ZJ0967 + TX, code ZJ2242 + TX, code JS7119 (CAS: [929545-74-4]) + TX, code SN-1172 + TX, code HNPC-A9835 + TX, code HNPC-A9955 + TX, code HNPC-A3061 + TX , Chuanhua code 89-1 + TX, IPP-10 code + TX, ZJ3265 code + TX, JS9117 code + TX, ZJ3757 code + TX, ZJ4042 code + TX, ZJ4014 code + TX, ITM-121 code + TX, DPX code -RAB55 (DKI-2301) + TX, code NA- 89 + TX, code MIE-1209 + TX, code MCI-8007 + TX, code BCS-CL73507 + TX, code S-1871 + TX, code DPX-RDS63 + TX, Quinofumelina + TX, mefentrifluconazole + TX, fenpicoxamide + TX, fluindapir + TX, inpirfluxam + TX or indiflumetpir + TX, isoflucipram + TX, pirapropoin + TX, florylpicoxamide + TX, methyltetraprol + TX, ipflufenoquine + TX, pyridaclomethyl + TX or clopiridiflu + TX, tetrachlorantraniliprole + TX, tetrachloraniliprole + TX, Ticlopirazoflor + TX, flupirimin + TX or pirifluramide + TX, benzpyrimoxane + TX, benzosufil + TX or oxazosulfyl + TX, etpirafen + TX, acinonapyr + TX or pyrinonaphen + TX, oxotrione + TX, bixlozone + TX or clofendizone + TX or dichloroxyzone + TX, cyclopyranil + TX or pyrazocyclonil + TX or cyclopyrazonil + TX, alpha-bromadiolone + TX and code AKD-1193 + TX.

[0307] References in parentheses after the active ingredients, e.g. e.g., [3878-19-1] refer to the Chemical Abstracts Registry Number. The mixing partners described above are known. Where the active ingredients are included in “The Pesticide Manual” [The Pesticide Manual - A World Compendium; Thirteenth edition; Editor: C. D. S. TomLin; The British Crop Protection Council], are described there with the entry number given in curly brackets here above for the particular compound; for example, the compound “abamectin” is described under accession number (1). When “[CCN]” is added above the particular compound, the compound in question is included in the “Compendium of Pesticide Common Names”, which is accessible via 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/acetoprole.html.

[0308] Most of the active ingredients described above are previously referred to by a so-called “common name”, the relevant “ISO common name” or another “common name” being used in individual cases. If the designation is not a “common name,” the nature of the designation used instead is given in 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, or, if none of these designations are used nor a “common name”, an “alternative name” is used. "At the. CAS Reg” means Chemical Abstracts Registration Number.

[0309] The mixture of active ingredients of compounds of formula I selected from Tables 1 to 12 and Table P with active ingredients described above comprises a compound selected from Tables 1 to 12 and Table P and an active ingredient as described above preferably in a ratio of 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, most especially in a ratio of 5:1 and 1:5, with special preference being given to a ratio of 2:1 to 1:2, and a ratio of 4:1 to 2:1 is also preferred, above all in a ratio of 1:1 , or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1 , or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2 , or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000 , or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750 These mixing ratios are by weight.

[0310] Mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to pests or their environment, with the exception of a method for methods of treating the human body or animal through surgery or therapy and diagnosis performed on the human or animal body.

[0311] Mixtures comprising a compound of formula I selected from Tables 1 to 12 and Table P and one or more ingredients as described above can be applied, for example, in a single “ready-to-mix” form, in a mixture for combined spraying 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, i.e., 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 12 and Table P and the active ingredients as described above is not essential for carrying out the present invention.

[0312] The compositions according to the invention may also comprise additional solid or liquid auxiliaries, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example coconut oil, rapeseed oil or epoxidized soybean oil), defoamers , for example silicone oil, preservatives, viscosity regulators, binders and/or adhesion agents, fertilizers or other active ingredients to achieve specific effects, for example bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0313] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries, for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary, e.g. by intimate mixing and/or grinding of the active ingredient with the auxiliary (auxiliary). These processes for preparing the compositions and the use of compounds I for preparing these compositions are also a subject of the invention.

[0314] 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 are to be selected to suit the desired objectives of the prevailing circumstances - and the use of the compositions for controlling pests of the aforementioned type are other subjects 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 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.

[0315] A preferred method of application in the area of crop protection is application to the foliage of plants (foliar application), making it possible to select the frequency and rate of application to meet the danger of infestation with the pest in question. Alternatively, the active ingredient may reach the plants through the root system (systemic action), by drenching the plant locus with a liquid composition or by incorporating the active ingredient in solid form into the plant locus, e.g. in the soil, e.g. form of granules (application to the soil). In case of paddy crops, such granules can be calibrated in the flooded paddy field.

[0316] 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. Propagation material can be treated with compost before planting, for example seed can be treated before sowing. Alternatively, the compound can be applied to the seed kernels (coating), 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 row formation process. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention. Typical treatment rates depend on the plant and the pests/fungi to be controlled, and generally range 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.

[0317] The term seed encompasses seeds and propagules of plants of all types including but not limited to true seeds, pieces of seeds, corms, calluses, bulbs, fruits, tubers, grains, rhizomes, cuttings, shoots from cuttings and the like and means in a preferred embodiment true seeds.

[0318] 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 at the time of application, although a greater or lesser part of the ingredient may penetrate the seed material, depending on the application method. 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 to which a compound of formula (I) is adhered. Additionally, a composition comprising a plant propagation material treated with a compound of formula (I) is thus made available.

[0319] 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. Application of seed treatment with 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 the seeds.

[0320] Biological Examples: The following Examples serve to illustrate the invention. Certain compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, e.g. 50 ppm, 25 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm, 0.2 ppm or 0.05 ppm.

[0321] Example B1: Activity against Plutella xylostella (Cowder Moth)

[0322] 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.

[0323] 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, P3, P4, P6, P7, P8, P9 , P10, P12, P13, P14, P15, P16, P17, P18, P19, P21, P22, P23, P24.

[0324] Example B2: Activity against Myzus persicae (Green peach aphid)

[0325] 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 mixed-age aphid population. Samples were evaluated for mortality 6 days after infestation.

[0326] The following compounds resulted in mortality of at least 80% at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P12, P13, P14, P15 , P16, P17, P18, P19, P22, P23.

[0327] Example B3: Activity against Myzus persicae (Green peach aphid)

[0328] Pea seedling roots, infested with a population of mixed-age aphids, were placed directly into aqueous test solutions prepared from stock solutions in 10'000 DMSO. Samples were evaluated for mortality 6 days after placing the seedlings in the test solutions.

[0329] The following compounds resulted in mortality of at least 80% at a test rate of 24 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P12, P13, P14, P15 , P16, P17, P18, P19, P22, P23.

[0330] Example B4: Activity against Frankliniella occidentalis (Western flower thrips): 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.

[0331] The following compounds resulted in mortality of at least 80% at an application rate of 200 ppm: P1, P4, P7, P8, P9, P10, P14, P15, P19, P22.

[0332] Example B5: Activity against Bemisia tabaci (Cotton whitefly)

[0333] 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 adult whiteflies. Samples were checked for mortality 6 days after incubation.

[0334] The following compounds resulted in mortality of at least 80% at an application rate of 200 ppm: P1, P3, P4, P5, P6, P8, P9, P10, P12, P14, P15, P16, P18, P19 , P22, P23.

[0335] Example B6: Activity against Euschistus heros (Neotropical Brown Stink Bug)

[0336] Soybean leaves 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 N-2 nymphs. Samples were evaluated for mortality and growth inhibition compared to untreated samples 5 days after infestation.

[0337] 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, P2, P3, P4, P5, P6, P8 , P9, P10, P13, P14, P15, P16, P17, P18, P19, P21, P22, P23.

[0338] Example B7: Activity against Diabrotica balteata (Corn rootworm)

[0339] Apple shoots placed on an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from stock solutions in DMSO at 10,000 ppm by spraying. 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.

[0340] 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, P4, P5, P6, P7, P8, P9 , P13, P14, P15, P16, P18, P22, P23, P24.

[0341] Example B8: Activity against Spodoptera littoralis (Egyptian cotton leafworm)

[0342] 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, antifeeding 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, antifeeding effect and growth inhibition is higher than the untreated sample.

[0343] The following compound resulted in at least 80% control at an application rate of 200 ppm: P4, P8, P13, P14, P15, P16, P21, P24.

[0344] Example B9: Activity against Thrips tabaci (Onion Thrips)

[0345] 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 mixed-age population of thrips. Samples were evaluated for mortality 6 days after infestation.

[0346] The following compounds resulted in mortality of at least 80% at an application rate of 200 ppm: P1.

Claims (17)

1. Compound of formula I characterized by the fact that A is CH or N; X is S, SO or SO2; R1 is C1-C4 alkyl, C1-C4 haloalkyl or C3-C6 cycloalkyl-C1-C4 alkyl; R7 and R8 are, independently of each other, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C6 cyanoalkyl, C1-C4 alkoxy, C1-C4 alkyl, pyridyl or phenyl, wherein said pyridyl or phenyl may be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl and — C (O)C1-C4haloalkyl; or R7 and R8, together with the sulfur atom to which they are attached, form a saturated ring system with four to six members, said ring system may be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C1-alkyl C4, C1-C4 alkoxy and C1-C4 haloalkyl; and said ring system may contain a heteroatom selected from the group consisting of nitrogen, oxygen and sulfur; n is 0 or 1; Q is a radical selected from the group consisting of the formulas Q1 to Q4 wherein the arrow denotes the point of attachment to the ring incorporating the radical A; and wherein XI is NR3, wherein R3 is C1-C4 alkyl; R2 is halogen, C1-C6 haloalkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C1-C6 haloalkoxy; G1 is N; G2 and G3 are, independently of each other, N or CH; and agrochemically acceptable salts and N-oxides of the compounds of formula I. 2. Compound of formula I, according to claim 1, characterized by the fact that R1 is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl. 3. Compound of formula I, according to claim 1, characterized by the fact that Q is Q1; and R1 is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl. 4. Compound of formula I, according to claim 1, characterized by the fact that X is SO2; R1 is ethyl; Q is Q1; XI is NR3, and R3 is methyl; A is N; R2 is C1-C6 haloalkyl; G1 is N; n is 0 or 1; R7 and R8 are, independently of each other, C1-C6 alkyl; or R7 and R8, together with the sulfur atom to which they are attached, form a six-membered saturated ring system, which may contain an oxygen atom. 5. Compound of formula I, according to claim 1, characterized by the fact that Q is Q2; and R1 is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl. 6. Compound of formula I, according to claim 1, characterized by the fact that Q is Q2; X is SO2; R1 is ethyl; R2 is C1-C6 haloalkyl; n is 0 or 1; and R7 and R8 are, independently of each other, C1-C6 alkyl; Or R7 and R8, together with the sulfur atom to which they are attached, form a six-membered saturated ring system, which may contain an oxygen atom. 7. Compound of formula I, according to claim 1, characterized by the fact that Q is Q4; and R1 is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl. 8. Compound of formula I, according to claim 1, characterized by the fact that Q is Q4; X is SO2; R1 is ethyl; XI is NR3, and R3 is methyl; A is N; R2 is C1-C6 haloalkyl; n is 0 or 1; and R7 and R8 are, independently of each other, C1-C6 alkyl; or R7 and R8, together with the sulfur atom to which they are attached, form a six-membered saturated ring system, which may contain an oxygen atom. 9. Pesticide composition, characterized by the fact 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 an active ingredient and at least one auxiliary. 10. Method for controlling pests, characterized in that it comprises: applying a composition, as defined in claim 10, 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 human or animal body. 11. Method for protecting plant propagation material from attack by pests, characterized in that it comprises: treating the propagation material or the place where the propagation material is planted, with a composition, as defined in claim 10 . 12. Compound of formula I, according to claim 1, characterized by the fact that X is SO2; R1 is ethyl; R2 is trifluoromethyl; and XI is NR3, and R3 is methyl. 13. Compound of formula I, according to claim 12, characterized by the fact that R7 and R8 are, independently of each other, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C6 cyanoalkyl or C1 alkoxy -C4alkyl C1-C4. 14. Compound of formula I, according to claim 12, characterized by the fact that R7 and R8, together with the sulfur atom to which they are attached, form a saturated ring system with four to six members, said ring system may be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy and C1-C4 haloalkyl; and said ring system may contain a heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. 15. Compound of formula I, according to claim 12, characterized by the fact that R7 and R8, together with the sulfur atom to which they are attached, form a saturated ring system with four to six members, and said system ring may contain a heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. 16. Compound of formula I, according to claim 12, characterized by the fact that R7 and R8 are, independently of each other, methyl or ethyl; or R7 and R8, together with the sulfur atom to which they are attached, form a six-membered saturated ring system, which may contain an oxygen atom; or form a four-membered saturated ring system. 17. Compound characterized by the fact that it is selected from: