5,5-BICYCLICAL HETEROCYCLES REPLACED WITH SUBSTITUTES CONTAINING SULFUR, PESTICIDE POINT OF VIEW ASS

专利摘要:
5.5-bicyclic heterocycles substituted with sulfur-containing substituents, active from a pesticidal point of view. compounds of the formula i, and the agrochemically acceptable salts, stereoisomers, enentiomers, tautomers and n-oxides of these compounds, including all stereoisomers and tautomeric forms, and in which the substituents are as defined in claim 1, are useful for controlling animal pests and can be prepared in a known way "per se".
公开号:BR112016014499B1
申请号:R112016014499-6
申请日:2014-12-19
公开日:2020-09-29
发明作者:Michel Muehlebach；Andrew Edmunds；André Stoller；Natalie Anne Miller；Ottmar Franz Hueterf
申请人:Syngenta Participations Ag；
IPC主号:

专利说明:

[0001] The present invention relates to sulfur-containing heterocyclic derivatives, active from a pesticidal point of view, to processes for their preparation, to compositions comprising these compounds, and to their use to control animal pests (including arthropods, and in particular , insects or representatives of the order Acarina).
[0002] Heterocyclic compounds with pesticidal action are known and described, for example, in WO 2009/131237, WO 2011/043404, WO 2011/040629, WO 2010/125985, WO 2012/086848, and WO 2013/018928.
[0003] New 5.5-heterocyclic derivatives with pesticidal properties have now been found.
[0004] Consequently, the present invention relates to compounds of formula I,
Characterized by the fact that Xi and X2, independently of each other, are N or C-R5, where R5 is hydrogen, C1-C4 alkyl groups, halogen, cyan or C1-C4 alkoxy; X3 is O, S or N-RÊÍ where Re θ hydrogen or a C1-C4 alkyl group; R2 is a halogen, a C1-C4 haloalkyl group or C1-C4 haloalkyl substituted with one or two substituents selected from the group consisting of hydroxyl, methoxy and cyano groups; or R2 is a C1-C4 haloalkylthio C1-C4 haloalkylsulfonyl group (C1-C4 haloalkyl), Sfs phenylcarbonylthio, cyano, mercapto, or C4 alkoxycarbonyl; R3 is hydrogen, a C1-C4 alkyl group, C1-C4 haloalkyl, halogen, cyan or C1-C4 alkoxy; Q is a radical selected from the group consisting of formulas Q1 to Q6:
wherein the arrow indicates the point of attachment to the 5,5-bicyclic heteroaromatic system; and where X is S, SO or SO2; each R is, independently of one another, hydrogen, a C1-C4 halogen or haloalkyl group; R is C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6_cycloalkyl, C1-C6 haloalkyl, C3-C6 halocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl or C2 "alkynyl; and R is hydrogen or a halogen; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers, and N-oxides of these compounds.
[0005] The alkyl groups that occur in the definitions of the substituents can be straight or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl and hexyl. The alkoxy, alkenyl and alkynyl radicals are derived from the mentioned alkyl radicals. The alkenyl and alkynyl groups can be mono- or polyunsaturated.
[0006] Halogen is usually fluorine, chlorine, bromine or iodine. This also applies, correspondingly, to halogens in combination with other meanings, such as haloalkyls or halophenyls.
[0007] The haloalkyl groups preferably have a chain length of 1 to 6 carbon atoms. A 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- trichlorethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichlorethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl, in particular trifluoromethyl.
[0008] Alkoxy groups preferably have a preferred chain length of 1 to 6 carbon atoms. An 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.
[0009] The alkoxyalkyl groups preferably have a chain length of 1 to 6 carbon atoms.
[0010] Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
[0011] Cycloalkyl groups preferably have 3 to 6 carbon atoms in the ring, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Phenyl, also as part of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl, phenoxyalkyl, can be substituted. In this case, the substituents can be in the ortho, meta and / or para position. Preferred positions for the substituents are ortho and para positions relative to the point of attachment to the ring.
[0012] The compounds of formula I that 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 alkanocarboxylic acids which are unsubstituted or substituted, for example with halogens, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example 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 benzoic acid organic sulfonic acids, such as alkane- or aryl-C1 -C4 sulfonic acids that are unsubstituted or substituted, for example with halogen, for example methane- or p-toluenesulfonic. The compounds of formula I that have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali or alkaline earth metal salts, for example sodium, potassium or magnesium, or salts with ammonia or an amine organic, such as morpholine, piperidine, pyrrolidine, a short chain mono, di or trialkylamine, for example ethyl, diethyl, triethyl or dimethylpropylamine, or a short chain mono, di or trihydroxyalkylamine, for example mono, di or triethanolamine.
[0013] The salts of the compounds of formula I can be prepared in a manner known per se. Thus, for example, acid addition salts of the 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 .
[0014] The salts of the compounds of formula I can be converted in the usual way to the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchange reagent, and the salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchange reagent.
[0015] The salts of the compounds of formula I can be converted in a manner known per se to other salts of the compounds of formula I, the acid addition salts, for example, to other acid addition salts, for example, by treatment of a inorganic acid salt such as hydrochloride with an appropriate 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.
[0016] Depending on the procedure or the conditions of the reactions, the compounds of formula I, which have salt-forming properties can be obtained in free form or in the form of salts.
[0017] The compounds of formula I and, where appropriate, their tautomers, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and / or include other solvents, for example those that may have been used for the crystallization of compounds that are present in solid form.
[0018] Preferably, R is hydrogen, a halogen or haloalkyl group C1-C4; R2 is a halogen group, C1-C4 haloalkyl, C1-C4 haloalkyl substituted with one or two hydroxy groups, or R2 is a C1-C4 haloalkylthio group, C1-C4 haloalkylsulfonyl, O (Cj-C4 haloalkyl), SF5, phenylcarbonylthio , cyano, mercapto, or C1-C4 alkoxycarbonyl; and agrochemically acceptable salts and N-oxides of these compounds.
[0019] Preferred compounds of formula I are represented by compounds of formulas I-1 to I-8

wherein X4i is S, SO or S02; R71 is hydrogen, a C1-C4 halo or haloalkyl group; Rsi is a methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl group; and where X51 is 0 or S; R91 is a C1-C4 halogen or haloalkyl group; and R101 is hydrogen, a C1-C4 alkyl group, halogen, cyano, methoxy or ethoxy; X42 is S, SO or S02; R82 θ a methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl group; and where X52 θ 0 or S; R92 is a C1-C4 halogen or haloalkyl group; and R102 is hydrogen, a C1-C4 alkyl group, halogen, cyano, methoxy or ethoxy; X43 is S, SO or S02; R73 is hydrogen, a halogen or C1-C4 haloalkyl group; Rg3 is a methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl group; and where X5 is 0 or S; R93 is a C1-4 halo or haloalkyl group; and R103 θ hydrogen, a C1-C4 alkyl group, halogen, cyano, methoxy or ethoxy; X44 is S, SO or SO2; R74 is hydrogen, a C1-4 halo or haloalkyl group; R84 is a methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl group; and where X84 is 0 or S; Rg4 is a C1-4 halo or haloalkyl group; and RIO4 is hydrogen, a C1-C4 alkyl group, halogen, cyano, methoxy or ethoxy; X45 is S, SO or SO2; R75 θ hydrogen, a C1-4 halo or haloalkyl group; R85 is a methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl group; and where X55 is 0 or S; R95 is a C1-4 halo or haloalkyl group; and Rios is hydrogen, a C1-C4 alkyl group, halogen, cyano, methoxy or ethoxy; X46 is S, SO or S02; R76 is hydrogen, a C1-4 halo or haloalkyl group; R88 is a methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl group; and where X56 is 0 or S; R96 is a C1-4 halo or haloalkyl group; and Rios is hydrogen, a C1-4 alkyl group, halogen, cyano, methoxy or ethoxy; X47 is S, SO or S02; R77 is hydrogen, a C1-4 halo or haloalkyl group; R87 is a methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl group; and where X57 is 0 or S; R97 is a C1-4 halo or haloalkyl group; and R107 is hydrogen, a C1-C4 alkyl group, halogen, cyano, methoxy or ethoxy; X48 is S, SO or S02; R78 is hydrogen, a C1-4 halo or haloalkyl group; R8S is a methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl group; and where X58 is O or S; R98 is a C1-4 halo or haloalkyl group; and RIOB is hydrogen, a C1-4 alkyl group, halogen, cyano, methoxy or ethoxy; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers, and N-oxides of these compounds.
[0020] A preferred group of compounds of formula I is represented by compounds of formula I-1
where X4x is S, SO or S02; R71 is hydrogen, a C1-4 halo or haloalkyl group; Rei is a methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl group; and where X51 is 0 or S; R91 is a C1-4 halo or haloalkyl group; and R101 is hydrogen, a C1-4 alkyl group, halogen, cyano, methoxy or ethoxy; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of these compounds, in particular and agrochemically acceptable salts and N-oxides of those compounds.
Preferred compounds of formula 1-1 have X51 defined as S. In said preferred compounds of formula 1-1, R91 is in particular trifluoromethyl or 1,1,2,2,2-pentafluoroethyl, in particular trifluoromethyl.
[0022] Other preferred compounds of formula 1-1 have R9i defined as trifluoromethyl or 1,1,2,2,2-pentafluoroethyl, in particular trifluoromethyl.
[0023] Preferably in the compounds of formula 1-1, X4i is S, SO or SO2 and R71 is hydrogen, a halogen or trifluoromethyl group.
[0024] In preferred compounds of formula 1-1, X41 is as defined above and R7i is hydrogen.
[0025] In preferred compounds of formula 1-1, X4i is as defined above and R'i is a halogen group.
[0026] Other preferred compounds of formula 1-1 are those where X41 is as defined above and R7i is a trifluoromethyl group.
[0027] In especially preferred compounds of formula I-1 where X51 is S and Ri01 is hydrogen or a methyl group, X41 is S02, R71 is hydrogen, Rei is an ethyl or cyclopropylmethyl group and R91 is a trifluoromethyl or 1 group, 1,2,2,2-pentafluoroethyl; in particular trifluoromethyl, or X41 is SO2, R71 is a trifluoromethyl group, Rsi is an ethyl or cyclopropylmethyl group and R9I is a trifluoromethyl or 1,1,2,2,2-pentafluoroethyl group; in particular trifluoromethyl, or X4i is SO, R71 is hydrogen, Rgi is an ethyl or cyclopropylmethyl group and R9X is a trifluoromethyl or 1,1,2,2,2-pentafluoroethyl group; in particular trifluoromethyl, or X41 is SO, R7I is a trifluoromethyl group, Rgi is an ethyl or cyclopropylmethyl group and R91 is a particular trifluoromethyl group, or X4i is S, R71is hydrogen, R81is an ethyl or cyclopropylmethyl group and R91 is a trifluoromethyl group or 1,1,2,2,2-pentafluoroethyl; in particular trifluoromethyl, or X41 is S, R71 is a trifluoromethyl group, R8I is an ethyl or cyclopropylmethyl group and R91 is a trifluoromethyl or 1,1,2,2,2-pentafluoroethyl group; in particular trifluoromethyl.
[0028] Another preferred group of compounds of formula I is represented by compounds of formula I-2
where X42 is S, SO or SO2; R82 is a methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl group; and where X82 is 0 or S; R92 is a C1-C4 halogen or haloalkyl group; and RI02 is hydrogen, a C1 -C4 alkyl group, halogen, cyano, methoxy or ethoxy; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of these compounds, in particular agrochemically acceptable salts and N-oxides of those compounds.
[0029] Preferred compounds of formula 1-2 have X52 defined as S. In said preferred compounds of formula 1-2, R92 is in particular trifluoromethyl.
[0030] Other preferred compounds of formula 1-2 have R92 defined as trifluoromethyl.
[0031] In especially preferred compounds of formula I-2 where X52 is S and R102 is hydrogen or a methyl group, X42 is SO2, Rs2 is an ethyl or cyclopropylmethyl group and R92 is a trifluoromethyl group; or X42 is SO, RB2 is an ethyl or cyclopropylmethyl group and R92 is a trifluoromethyl group; or X42 is S, R82 θ an ethyl or cyclopropylmethyl group and R92 is a trifluoromethyl group.
[0032] Another preferred group of compounds of formula I is represented by compounds of formula I-3
where X43 is S, SO or SO2; R73 is hydrogen, a halogen or C1-C4 haloalkyl group; R83 is a methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl group; and where X5 is O or S; R93 is a C1-C4 halogen or haloalkyl group; and R103 is hydrogen, a C1-C4 alkyl group, halogen, cyano, methoxy or ethoxy; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of these compounds, in particular agrochemically acceptable salts and N-oxides of those compounds.
[0033] Preferred compounds of formula 1-3 have X53 defined as S. In said preferred compounds of formula 1-3, R93 is in particular trifluoromethyl or 1,1,2,2,2-pentafluoroethyl, in particular trifluoromethyl.
[0034] Other preferred compounds of formula 1-3 have R93 defined as trifluoromethyl or 1,1,2,2,2-pentafluoroethyl, in particular trifluoromethyl.
[0035] Preferably in the compounds of formula 1-3, X43 is S, SO or SO2 and R73 is hydrogen, a halogen or trifluoromethyl group.
[0036] In preferred compounds of formula 1-3, X43 is as defined above and R33 is hydrogen.
[0037] In preferred compounds of formula 1-3, X43 is as defined above and R73 is a halogen group.
[0038] Additionally preferred compounds of formula 1-3 are those where X43 is as defined above and R73 is trifluoromethyl.
[0039] In especially preferred compounds of formula I-3 where X53 is S and R103 is hydrogen or a methyl group, X43 is SO2, R73 θ hydrogen, R83 is an ethyl or cyclopropylmethyl group and R93 is a trifluoromethyl or 1 group, 1,2,2,2-pentafluoroethyl; in particular trifluoromethyl; or X43 is SO2, R73 θ a trifluoromethyl group, R83 is an ethyl or cyclopropylmethyl group and R93 is a trifluoromethyl or 1,1,2,2,2-pentafluoroethyl group; in particular trifluoromethyl; or X43 is SO, R73 is hydrogen, R83 is an ethyl or cyclopropylmethyl group and R93 is a trifluoromethyl or 1,1,2,2,2-pentafluoroethyl group; in particular trifluoromethyl; or X43 is SO, R73 is trifluoromethyl, R83 is an ethyl or cyclopropylmethyl group and R93 is a trifluoromethyl or 1, 1,2,2,2-pentafluoroethyl group; in particular trifluoromethyl; or X43 is S, R73 is hydrogen, R83 is an ethyl or cyclopropylmethyl group and R93 is a trifluoromethyl or 1,1,2,2,2-pentafluoroethyl group; in particular trifluoromethyl; or X43 is S, R73 is a trifluoromethyl group, R83 is an ethyl or cyclopropylmethyl group and R93 is a trifluoromethyl or 1, 1,2,2,2-pentafluoroethyl group, in particular trifluoromethyl.
[0040] Another preferred group of compounds of formula I is represented by compounds of formula I-4
wherein X44 is S, SO or S02; R74 is hydrogen, a C1-C4 halo or haloalkyl group; R84 is a methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl group; and where X54 is 0 or S; R94 is a C1-C4 halogen or haloalkyl group; and RIO4 is hydrogen, a C1-C4 alkyl group, halogen, cyano, methoxy or ethoxy; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of these compounds, in particular agrochemically acceptable salts and N-oxides of those compounds.
Preferred compounds of formula 1-4 have X54 defined as S. In said preferred compounds of formula 1-4, R94 is in particular trifluoromethyl.
[0042] Other preferred compounds of formula 1-4 have R94 defined as trifluoromethyl.
[0043] Preferably in the compounds of formula 1-4, X44 is S, SO or SO2 and R74 is hydrogen, a halogen or trifluoromethyl group.
[0044] In preferred compounds of formula 1-4, X44 is as defined above and R74 is hydrogen.
[0045] In preferred compounds of formula 1-4, X44 is as defined above and R74 is a halogen group.
[0046] Additionally preferred compounds of formula 1-4 are those where X44 is as defined above and R74 is trifluoromethyl.
[0047] In especially preferred compounds of formula I-4 where X54 is S and R104 is hydrogen or a methyl group, X44 is S02, R74 is hydrogen, R84 is an ethyl or cyclopropylmethyl group and R94 is a trifluoromethyl group; or X44 is SO2, R74 is a trifluoromethyl group, R84 is an ethyl or cyclopropylmethyl group and R94 is a trifluoromethyl group; or X44 is SO, R74 is hydrogen, R84 is an ethyl or cyclopropylmethyl group and R94 is a trifluoromethyl group; or X44 is SO, R74 is a trifluoromethyl group, R84 is an ethyl or cyclopropylmethyl group and R94 is a trifluoromethyl group; or X44 is S, R74 is hydrogen, R84 is an ethyl or cyclopropylmethyl group and R94 is a trifluoromethyl group; or X44 is S, R74 is a trifluoromethyl group, R84 is an ethyl or cyclopropylmethyl group and R94 is a trifluoromethyl group.
[0048] Another preferred group of compounds of formula I is represented by compounds of formula I-5
where X45 is S, SO or SO2; R75 is hydrogen, a C1-C4 halo or haloalkyl group; R85 is a methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl group; and where X55 is O or S; R95 is a C1-4 halo or haloalkyl group; and R105 is hydrogen, a C1-4 alkyl group, halogen, cyano, methoxy or ethoxy; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of these compounds, in particular agrochemically acceptable salts and N-oxides of those compounds.
Preferred compounds of formula 1-5 have X55 defined as S. In said preferred compounds of formula 1-5, R95 is in particular trifluoromethyl.
[0050] Other preferred compounds of formula 1-5 have R95 defined as trifluoromethyl.
[0051] Preferably in compounds of formula 1-5, X4s is S, SO or S02 and R75 is hydrogen, a halogen group or
[0052] In preferred compounds of formula 1-5, X45 is as defined above and R75 is hydrogen.
[0053] In preferred compounds of formula 1-5, X45 is as defined above and R75 is a halogen group.
[0054] Other preferred compounds of formula 1-5 are those where X45 is as defined above and R75 is a trifluoromethyl group.
[0055] In especially preferred compounds of formula I-5 where X55 is S and R105 is hydrogen or a methyl group, X45 is SO2, R75 is hydrogen, Rgs is an ethyl or cyclopropylmethyl group and R95 is a trifluoromethyl group; or X45 is S02, R75 is a trifluoromethyl group, R85 is an ethyl or cyclopropylmethyl group and R95 is a trifluoromethyl group; or X45 is SO, R75 is hydrogen, R8s is an ethyl or cyclopropylmethyl group and R95 is a trifluoromethyl group; or X45 is SO, R75 is a trifluoromethyl group, R85 is an ethyl or cyclopropylmethyl group and R95 is a trifluoromethyl group; or X45 is S, R75 is hydrogen, Rgs is an ethyl or cyclopropylmethyl group and R95 is a trifluoromethyl group; or X45 is S, R75 is a trifluoromethyl group, R85 is an ethyl or cyclopropylmethyl group and R95 is a trifluoromethyl group.
[0056] Another preferred group of compounds of formula I is represented by compounds of formula I-6
where X46 is S, SO or S02; R76 is hydrogen, a C1-4 halo or haloalkyl group; R86 θ is a methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl group; and where X56 is 0 or S; R-96 θ a Cx-C4 halogen or haloalkyl group; and R106 θ hydrogen, a C1-4 alkyl group, halogen, cyano, methoxy or ethoxy; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of these compounds, in particular agrochemically acceptable salts and N-oxides of those compounds.
Preferred compounds of formula 1-6 have X56 defined as S. In said preferred compounds of formula 1-6, R96 is in particular trifluoromethyl.
[0058] Other preferred compounds of formula 1-6 have Rg is defined as trifluoromethyl.
[0059] Preferably in the compounds of formula 1-6, X46 is S, SO or SO2 and R76 is hydrogen, a halogen or trifluoromethyl group.
[0060] In preferred compounds of formula 1-6, X46 is as defined above and R76 is hydrogen.
[0061] In preferred compounds of formula 1-6, X46 is as defined above and R76 is a halogen group.
[0062] Additionally preferred compounds of formula 1-6 are those where X46 ® as defined above and R76 is trifluoromethyl.
[0063] In especially preferred compounds of formula I-6 where X56 is S and R106 is hydrogen or a methyl group, X46 θ SO2, R76 θ hydrogen, R86 is an ethyl or cyclopropylmethyl group and R96 is a trifluoromethyl group; or X46 is SO2, R76 is a trifluoromethyl group, R86 is an ethyl or cyclopropylmethyl group and R96 is a trifluoromethyl group; or X46 is SO, R76 is hydrogen, R86 is an ethyl or cyclopropylmethyl group and R96 is a trifluoromethyl group; or X46 is SO, R76 θ a trifluoromethyl group, R86 is an ethyl or cyclopropylmethyl group and R98 is a trifluoromethyl group; or X46 is S, R76 is hydrogen, R86 is an ethyl or cyclopropylmethyl group and R96 is a trifluoromethyl group; or X46 is S, R76 is a trifluoromethyl group, R86 is an ethyl or cyclopropylmethyl group and R96 is a trifluoromethyl group.
[0064] Another preferred group of compounds of formula I is represented by compounds of formula I-7
where X47 is S, SO or SO2; R77 is hydrogen, a C1-C4 halo or haloalkyl group; R87 is a methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl group; and where X57 is 0 or S; R97 is a C1-C4 halogen or haloalkyl group; and R107 is hydrogen, a C1-C4 alkyl group, halogen, cyano, methoxy or ethoxy; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers, and N-oxides of these compounds.
Preferred compounds of formula 1-7 have X57 defined as S. In said preferred compounds of formula 1-7, R97 is in particular trifluoromethyl.
[0066] Other preferred compounds of formula 1-7 have R97 defined as trifluoromethyl.
[0067] Preferably in the compounds of formula 1-7, X47 is S, SO or SO2 and R77 is hydrogen, a halogen or trifluoromethyl group.
[0068] In preferred compounds of formula 1-7, X47 is as defined above and R77 is hydrogen.
[0069] In preferred compounds of formula 1-7, X47 is as defined above and R77 is a halogen group.
[0070] Additionally preferred compounds of formula 1-7 are those where X47 is as defined above and R77 is trifluoromethyl.
[0071] In especially preferred compounds of formula I-7 where X57 is S and R107 is hydrogen or a methyl group, X47 is SO2, R77 ® hydrogen, Rβ7 is an ethyl or cyclopropylmethyl group and R97 is a trifluoromethyl group; or X47 is SO2, R77 is a trifluoromethyl group, Rg7 θ an ethyl or cyclopropylmethyl group and R97 is an X47 θ SO group, R77 is hydrogen, Rs7 θ an ethyl or cyclopropylmethyl group and R97 is a trifluoromethyl group; or X47 is SO, R77 is a trifluoromethyl group, R87 is an ethyl or cyclopropylmethyl group and R97 is a trifluoromethyl group; or X47 is S, R77 θ hydrogen, R87 is an ethyl or cyclopropylmethyl group and R97 is a trifluoromethyl group; or X47 is S, R77 is a trifluoromethyl group, R87 is an ethyl or cyclopropylmethyl group and R97 is a trifluoromethyl group.
[0072] Another preferred group of compounds of formula I is represented by compounds of formula I-8
where X48 is S, SO or S02; R78 θ hydrogen, a halogen or C1-C4 haloalkyl group; Rss is a methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl group; and where X58 is O or S; Rg8 is a C1-C4 halogen or haloalkyl group; and Rios θ hydrogen, a C1-C4 alkyl group, halogen, cyano, methoxy or ethoxy; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers, and N-oxides of these compounds.
Preferred compounds of formula 1-8 have X58 defined as S. In said preferred compounds of formula 1-8, R88 is in particular trifluoromethyl.
[0074] Other preferred compounds of formula 1-8 have R98 defined as trifluoromethyl.
[0075] Preferably in the compounds of formula 1-8, X48 is S, SO or SO2 and R78 is hydrogen, a halogen or trifluoromethyl group.
[0076] In preferred compounds of formula 1-8, X48 is as defined above and R78 is hydrogen.
[0077] In preferred compounds of formula 1-8, X48 is as defined above and R78 is a halogen group.
[0078] Additionally preferred compounds of formula 1-8 are those where X48 is as defined above and R78 is trifluoromethyl.
[0079] In especially preferred compounds of formula I-8 where X58 is S and Rios is hydrogen or a methyl group, X48 is SO2, R78 θ hydrogen, R88 is an ethyl or cyclopropylmethyl group and R9s θ a trifluoromethyl group; or X48 is SO2, R78 is a trifluoromethyl group, R88 is an ethyl or cyclopropylmethyl group and R98 is a trifluoromethyl group; or X48 is SO, R78 is hydrogen, R88 is an ethyl or cyclopropylmethyl group and R98 is a trifluoromethyl group; or X48 is SO, R78 is a trifluoromethyl group, R88 is an ethyl or cyclopropylmethyl group and R98 is a trifluoromethyl group; or X48 is S, R78 is hydrogen, R88 is an ethyl or cyclopropylmethyl group and R98 is a trifluoromethyl group; or X48 is S, R78 θ is a trifluoromethyl group, R88 is an ethyl or cyclopropylmethyl group and R98 is a trifluoromethyl group.
[0080] In the particularly preferred compounds of formula I,
Characterized by the fact that each R is, independently of each other, hydrogen or a C 1 -C 4 haloalkyl group; R1 is C1 -C4 alkyl; R2 is C1 -C4 haloalkyl; R3 is hydrogen or a C1-4 alkyl group; R4 is hydrogen; X is S, SO or SO2; Xi is N; X2 is N or C-R5; Rs is hydrogen; and X3 is S.
[0081] 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. The subgroup of compounds of formula I, where Xi is N and R3 is R3a, can be represented by the compounds of formula Ia
wherein Q, X2 / X3, R2 are as described in formula (I) and R3a θ hydrogen, a C1-C4 alkyl group or C1-C4 haloalkyl. The compounds of formula Ia can be prepared by reacting a compound of formula II-a
where X2, and R are as described in formula (I), with a compound of formula III
where Q and R3 are as defined above and LG is a halogen or an OSO2RLG leaving group, where RLG is a C1-Cg alkyl, C1-C haloalkyl group, or phenyl optionally substituted with nitro or C1-C3 alkyl groups, optionally on presence of a suitable base, in an inert solvent. Examples of suitable solvents include, for example, alcohols (such as methanol, ethanol, propanol or isopropanol), polar aprotic solvents (such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethylsulfoxide) , ethers (such as tetrahydrofuran, dioxane or 1,2-dimethoxyethane), acetonitrile, ethyl acetate, acetone, dichloromethane, benzene, toluene or xylene. The reaction is advantageously carried out in a temperature range from approximately 20 ° C to approximately +200 ° C, preferably from approximately 70 ° C to approximately +180 ° C, optionally with microwave irradiation. Examples of suitable inorganic bases include lithium, sodium, potassium or cesium hydrogen carbonate; lithium, sodium, potassium or cesium carbonate; lithium, sodium or potassium hydroxide; and suitable organic bases include trialkylamines such as trimethylamine, triethylamine and ethyldiisopropylamine; pyridines or other amine bases such as 1,4-diazobicyclo [2.2.2] octane and 1,8-diazabicyclo [5.4.0] undec-7-ene.
[0082] The compounds of formula III, where Q and R3a are as defined above and LG is a halogen, can be prepared by reacting a compound of formula IV
wherein Q and Raa are as defined above, with a halogenating agent such as N-bromo-succinimide, N-chlorosuccinimide or N-iodosuccinimide, optionally in the presence of a Br0nsted or Lewis acid, in an appropriate solvent such as, for example, acetonitrile, dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, methanol or ethanol. Alternatively, bromine, chlorine or iodine can be used as halogenating agents, optionally in the presence of a Br0nsted acid (such as, for example, acetic acid, hydrogen bromide or hydrogen chloride) or a Lewis acid (such as, aluminum chloride AICI3), in appropriate solvents such as, for example, acetonitrile, dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, ethers (such as diethyl ether, tetrahydrofuran, dioxane or 1,2-dimethoxyethane ), methanol or ethanol. Yet another option for halogenating agents consists, for example, of sulfuryl chloride SO2C12 or copper (II) halides such as for example copper bromide CuBr2 or copper chloride CuCl2, which are used in solvents such as, for example, dichloromethane , chloroform, 1,2-dichloroethane, chloroform, carbon tetrachloride, ethyl acetate, tetrahydrofuran, dioxane, methanol or ethanol, or mixtures thereof, at temperatures between 25-150 ° C, optionally in the microwave.
[0083] The subgroup of compounds of formula IV, where Q and R3a are as defined above and where X is SO (sulfoxide) and / or SO2 (sulfone), can be obtained through an oxidation reaction of the compounds corresponding sulphide compounds of formula IV, 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 others oxidizing agents. The oxidation reaction is usually 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 their mixtures. The amount of oxidant to be used in the reaction is usually 1 to 3 moles, preferably 1 to 1.2 moles, in relation to 1 mole of IV sulfide compounds to produce IV sulfoxide compounds, and preferably 2 to 2.2 moles moles of oxidant, relative to 1 mole of IV sulfide compounds to produce IV sulfone compounds.
[0084] Compounds of formula IV, where Q and Raa are as defined above and where X is S (sulfide), can be prepared by reacting a compound of formula V
where R3ae as described above and where Qa is a radical selected from the group consisting of formulas Q1a to Q6a.
where R and R4 are as defined above, and where X10 is a halogen, with a compound of formula VI R1-SH (VI), or a salt thereof, where Ri is as defined in formula I, optionally in the presence of a suitable base, such as alkali metal carbonates, for example sodium carbonate and potassium carbonate, or alkali metal hydrides such as sodium hydride, or alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, optionally in presence of a catalytic amount of an additive, such as an ammonium salt (for example tetrabutylammonium bromide TBAB), in an inert solvent at temperatures preferably between 25-120 ° C. Examples of solvents to be used include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, aprotic polar solvents such as N, N - dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethylsulfoxide, or water. Examples of salts of the compound of formula VI include compounds of the formula Via R1-SM (VIa), where R1 is as defined above and where M is, for example, sodium or potassium. Layout 1

Alternatively, compounds of formula I-a can be prepared from compounds of formula V involving the same chemistry described above, but changing the order of the steps. This alternative route is summarized in scheme 1.
[0086] The subgroup of compounds of formula I, where X is SO (sulfoxide) and / or SO2 (sulfone), can be obtained by means of 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 usually 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 their mixtures. The amount of oxidant to be used in the reaction is generally 1 to 3 moles, preferably 1 to 1.2 moles, in relation to 1 mole of the sulfide compounds I to produce the sulfoxide compounds I, and preferably from 2 to 2, 2 moles of oxidant, relative to 1 mole of the sulfide compounds I to produce the sulfone compounds I. These oxidation reactions are disclosed, for example, in WO 2013/018928.
[0087] The compounds of formula V, where Raa and Qas are as described above and the compounds of formula 11a, where X2, X3 and R2 are as described above, are known compounds or that can be prepared by known methods, described in the literature.
[0088] Reagents can react in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal carbonates or alkaline earth metals, alkali metal dialkylamides or alkaline earth metals or alkaline earth 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 can be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, diisopropylamide lithium, potassium bis (trimethylsilyl) amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N, N-dimethylamine, N, N-diethylaniline, pyridine, 4- (N, N-dimethylamino) pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU).
[0089] The reagents can react with each other as such, that is, without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases that can be used in excess, such as triethylamine, pyridine, N-methylmorpholine or N, N-diethylaniline, can also act as solvents or diluents.
[0090] The reaction is advantageously carried out in a temperature range from approximately -80 ° C to approximately + 140 ° C, preferably from approximately -30 ° C to approximately +100 ° C, and in many cases in the range between temperature environment and approximately +80 ° C.
[0091] A compound of formula I can be converted, in a manner known per se, to another compound of formula I by substituting one or more substituents of the starting compound of formula I, in the usual manner, for another (s) substituent (s) according to the invention.
[0092] Depending on the conditions of the reactions and starting materials chosen, which are appropriate for each case, it is possible, for example, in one 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.
[0093] The salts of the compounds of formula I can be prepared in a manner known per se. Thus, for example, acid addition salts of the 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 .
[0094] The salts of the compounds of formula I can be converted in the usual way to the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchange reagent, and the salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchange reagent.
[0095] The salts of the compounds of formula 1 can be converted in a manner known per se to other salts of the compounds of formula I, the acid addition salts, for example, to other acid addition salts, for example, by treatment of an inorganic acid salt such as hydrochloride with an appropriate 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 example silver chloride, is insoluble and thus precipitates from the reaction mixture.
[0096] Depending on the procedure or the conditions of the reactions, the compounds of formula I, which have salt-forming properties can be obtained in free form or in the form of salts.
[0097] The compounds of formula I and, where appropriate, their tautomers, in each case in free form or in salt form, can 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 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 it is to be understood in each case in this sense here above and here below, even when the stereochemical details are not specifically mentioned in each case.
[0098] Mixtures of diastereomers or mixtures of racemates of the compounds of formula I, in free form or in salt form, which can be obtained depending on the starting materials and procedures that have been chosen, can be separated in a known way in the diastereomers pure or racemates based on the physicochemical differences of the components, for example by fractional crystallization, distillation and / or chromatography.
[0099] Mixtures of enantiomers, such as racemates, which can be obtained in a similar way, can be resolved in optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, by example high performance liquid chromatography (HPLC) in acetylcellulose, 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 forms a complex, or by conversion to diastereomeric salts, for example by reacting a racemate of the basic final product with an optically active acid such as a carboxylic acid, for example camphoric, tartaric or malic acid, or sulfonic acid, for example camphor sulfonic acid, and separation of the mixture of diastereomers that can be obtained in this way, for example by fractional crystallization based on their solutions different abilities, to give the diastereomers, from which the desired enantiomer can be released by the action of suitable agents, for example basic agents.
[0100] Diastereoisomers or pure enantiomers can be obtained according to the invention not only by separating appropriate mixtures of isomers, but also by generally known methods of diastereoselective or enantioselective synthesis, for example, when carrying out the process according to the invention with starting materials showing appropriate stereochemistry.
[0101] N-oxides can be prepared by reacting a compound of formula I with a suitable oxidizing agent, for example the adduct of H2O2 / urea in the presence of an acid anhydride, eg trifluoroacetic anhydride. Such oxidations are known from the literature, for example, from J. Med. Chem. 1989, 32, 2561 or WO 2000/15615.
[0102] It is advantageous in each case to isolate or synthesize the isomer, for example enantiomer or diastereoisomer, or more biologically effective mixture of isomers, for example mixture of enantiomers or mixture of diastereomers, if the individual components have different biological activity.
[0103] The compounds of formula I and, where appropriate, their tautomers, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and / or include other solvents, for example those that may have been used for the crystallization of compounds that are present in solid form.
[0104] The compounds according to the following Tables 1 to 4r8- 24 below can be prepared according to the methods described above. The following examples are intended to illustrate the invention and show the preferred compounds of formula I. Table 1: This table discloses the 16 compounds 1,001 to 1,016 of formula I:
where Q is Qt, X is S, X3 is S and R, R1, R2, R3, R4, X1 and X2 are as defined below: Table 1:
and the N-oxides of the compounds in Table 1. Table 2: This table discloses the 16 compounds 2.001 to 2.016 of formula I, where Q is Qtr X is SO, X3 is S and R, Ri, R2, R3, R4, X1 and X2 are as defined in Table 1. Table 3: This table discloses the 16 compounds 3.001 to 3.016 of formula I, where Q is Q., X is SO2, X3 is S and R, RI, R2, R3, R4, X1 and X2 are as defined in Table 1. Table 4: This table discloses the 16 compounds 4,001 to 4,016 of formula I, where Q is Q2, X is S, X3 is S and R, R1, R2, R3 , R4, X1 and X2 are as defined in Table Table 5: This table discloses the 16 compounds 5.001 to 5.016 of formula I, where Q is Q2i X is SO, X3 is S and R, R1, R2, R3, R4 , X1 and X2 are as defined in Table 1. Table 6: This table discloses the 16 compounds 6,001 to 6,016 of formula I, where Q is Qz, X is SO2, X3 is S and R, R, R2, R3, R4, X1 and X2 are as defined in Table 1. Table 7: This table discloses the 16 compounds 7,001 to 7,016 of formula I, where Q is Q3a, X is S, X3 is S and R, R1, R2, R3, R4, X1 and X2 are as defined in Table 1. Q3a is defined as:
Table 8: This table discloses the 16 compounds 8,001 to 8,016 of formula I, where Q is Q3a, X is SO, X3 is S and R, R ,, R2, R3, R4, X1 and X2 are as defined in Table 1. Table 9: This table discloses the 16 compounds 9,001 to 9,016 of formula I, where Q is Q3a, X is SO2, X3 is S and R, R1, R2, R3, R4, X1 and X2 are as defined in Table 1. Table 8: This table discloses the 16 compounds 8,001 to 8,016 of formula I, where Q is Q3a, X is SO, X3 is S and R, R ,, R2, R3, R4, X1 and X2 are such as defined in Table 1. Table 9: This table discloses the 16 compounds 9,001 to 9,016 of formula I, where Q is Q3a, X is SO2, X3 is S and R, R1, R2, R3, R4, X1 and X2 are such as defined in Table 1. Table 10: This table discloses the 16 compounds 10,001 to 10,016 of formula I, where Q is Q4i X is S, X3 is S and R, R ,, R2, R3, R4, X1 and X2 are as defined in Table 1. Table 11: This table discloses the 16 compounds 11,001 to 11,016 of formula I, in 3ueQ θ Q <z X is SO, X3 is S and R, Ri, R2, R3, R4, Xi and X2 are tai s as defined in Table 1. Table 12: This table discloses the 16 compounds 12,001 to 12,016 of formula I, where Q is Q „X is SO2, X3 is S and R, Ri, R2, R3, R4, XÍ and X2 are as defined in Table 1. Table 13: This table discloses the 16 compounds 13,001 to 13,016 of formula I, where Q is Q5, X is S, X3 is S and R, Ri, R2, R3, R4, Xi and X2 are as defined in Table 1. Table 14: This table discloses the 16 compounds 14,001 to 14,016 of formula I, where Q is Q5, X is SO, X3 is S and R, Ri, R2, R3, R4, Xi and X2 are as defined in Table 1. Table 15: This table discloses the 16 compounds 15,001 to 15,016 of formula I, where Q is Q5, X is SO2, X3 is S and R, Ri, R2, R3, R4, XI and X2 are as defined in Table 1. Table 16: This table discloses the 16 compounds 16,001 to 16,016 of formula I, where Q is Q6, X is S, X3 is S and R, Ri, R2, R3, R4 , Xi and X2 are as defined in Table 1. Table 17: This table discloses the 16 compounds 17,001 to 17,016 of formula I, where Q is Q6, X is SO, X3 is S and R, Ri, R2, R3, R4Z Xi and X2 are as defined in Table 1. Table 18: This table discloses the 16 compounds 18,001 to 18,016 of formula I, where Q is Q6, X is SO2, X3 is S and R, Ri, R2, R3, R4, Xi and X2 are as defined in Table 1. Table19: This table discloses the 8 compounds 19.001 to 19.008 of formula I:
where Q is Qtr X is Sr X3 is S and R, RI, R2, R3, R4, X. and X2 are as defined below: Table 19:
and the N-oxides of the compounds in Table 19. Table 20: This table discloses the 8 compounds 20,001 to 20,008 of formula I, where Q is Q1, X is SO, X3 and S and R, R1, R2, R3, R4 , X1, and X2 are as defined in Table 19. Table 21: This table discloses the 8 compounds 21,001 to 21,008 of formula I, where Q is Q1, X is SO2, X3 is S and R, RI, R2, R3 , R4, X1 and X2 are as defined in Table 19. Table 22: This table discloses the 8 compounds 22.001 to 22.008 of formula I, where Q is Q3 ,,, X is S, X3 is S and R, R1, R2, R3, R4, X1 and X2 are as defined in Table 19. Table 23: This table discloses the 8 compounds 23,001 to 23,008 of formula I, where Q is Q3a, X is SO, X3 is S and R, RI , R2, R3, R4, X1 and X2 are as defined in Table 19. Table 24: This table discloses the 8 compounds 24.001 to 24.008 of formula I, where Q is Q3 ~, X is SO2, X3 is S and R , R1, R2, R3, R4, Xl and X2 are as defined in Table 19.
[0105] The compounds of formula I according to the invention are valuable active ingredients from a preventive and / or curative point of view in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. The active ingredients according to the invention act against all stages of development or individual stages of development of normally sensitive but also resistant animal pests, such as insects or representatives of the order Acarina. The insecticidal or acaricidal activity of the active ingredients according to the invention can be manifested directly, that is, in the destruction of pests, which occurs immediately or after some time, for example during screening, or indirectly, for example as a reduced rate of oviposition and / or hatching, with a good activity corresponding to a destruction rate (mortality) of at least 50%.
[0106] The compounds of formula I can be used to combat and control insect pest infestations such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and Isoptera and also other invertebrate pests, for example, pest mites, nematodes and mollusks. Insects, mites, nematodes and mollusks are hereinafter collectively referred to as pests. Pests that can be combated and controlled by using the compounds of the invention include pests associated with agriculture (whose term includes growing crops for food and fiber products), horticulture and livestock, companion animals, forestry and product storage of vegetable origin (such as fruit, grain and wood); such pests associated with the damage of artificial physical structures and the transmission of diseases from humans and animals; and also harmful pests (like flies).
[0107] Examples of pest species that can be controlled by the compounds of formula I include: Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Lygus spp. (capsid), Dysdercus spp. (capsid), Nilaparvata lugens (grasshopper), Nephotettixc incticeps (cicada), Nezara spp. (bedbugs), Euschistus spp. (bedbugs), Leptocorisa spp. (bedbugs), Frankliniella occidentalis (thrips), Thrips spp. (thrips), Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis (weevil), Aonidiella spp. (mealybug), Trialeurodes spp. (whitefly), Bemisia tabaci (whitefly), Ostrinia nubilalis (European corn borer), Spodoptera littoralis (cottonworm), Heliothis virescens (tobacco worm), Helicoverpa armigera (cottonworm), Helicoverpa zea (worm) cotton), Sylepta derogata (cotton leaf bug), Pieris brassicae (white butterfly), Plutella xylostella (diamante negro moth), Agrotis spp. (worm), Chilo suppressalis (rice stem borer), Migratory locust (grasshopper), Chortiocetes terminifera (grasshopper), Diabrotica spp. (root worms), Panonychus ulmi (European red mite), Panonychus citri (red mite of the citrus), Tetranychus urticae (two-spotted spider), Tetranychus cinnabarinus (carmine spider), Phyllocoptruta oleivora (citrus rust mite), Polyphagot latus (large mite), Brevipalpus spp. (flat mites), Boophilus microplus (bovine tick), Dermacentor variabilis (dog tick, American), Ctenocephalides felis (cat flea), Liriomyza spp. (miner bug), Musca domestica (house fly), Aedes aegypti (mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Lucillia spp. (blowflies), Blattella germanica (cockroach), American Periplaneta (cockroach), Blatta orientalis (cockroach), termites of Mastotermitidae (for example Mastotermes spp.), Rhinotermitidae (for example Coptotermes formosanus, Reticulitermes flavipes, R. speratu, R. virginicus, R. hesperus, and R. santonensis) and Termitidae (for example Globitermes sulphureus), Solenopsis geminata (fire ant), Monomorium pharaonis (pharaoh ant), Damalinia spp. and Linognathus spp. (lice that bite and suck), Meloidogyne spp. (root knot nematodes), Globodera spp. and Heterodera spp. (cyst nematodes), Pratylenchus spp. (lesion nematodes), Rhodopholus spp. (banana nematodes), Tylenchulus spp. (citrus nematodes), Haemonchus contortus (worm), Caenorhabditis elegans (golden nematode), Trichostrongylus spp. (gastrointestinal nematodes) and Deroceras reticulatum (slugs).
[0108] Additional examples of the pests mentioned above are: of the order Acarina, for example, Acalitus spp, Aculus spp, Acaricalus spp, Aceria spp, Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp, Eotetranychus spp, Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp, Ornithodorus spp., Ornithodoros spp. , Phytonemus spp, Polyphagotarsonemus spp, Psoroptes spp., Rhipicephalus spp., Rhizogliphus spp., Sarcoptes spp., Steneotarsonemus spp, Tarsonemus spp. and Tetranychus spp .; of the order Anoplura, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp .; of the order Coleoptera, for example, Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis, Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp., Cotinis spp., Cyclocephala spp, Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemLineata, Lissorhoppuspea, Lissorhoppuspea Megascelis spp, Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp, Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatus aubtilis, Rhizophais, Spiz. spp., Somaticus spp, Sphenophorus spp, Sternechus subsignatus, Tenebrio spp., Tribolium spp. and Trogoderma spp .; of the order Diptera, for example, Aedes spp., Anopheles spp, Antherigona soccata, Bactrocea oleae, Bibio hortulanus, Bradysia spp, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delacus spp. 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 ., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis spp, Rivelia quadrifasciata, Scatella spp, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp .; of the order Hemiptera, for example, Acanthocoris scabrator, Acrosternum spp, Adelphocoris lineolatus, Amblypelta nitida, Bathycoelia thalassina, Blissus spp, Cimex spp., Clavigralla tomentosicollis, Creontiades spp, Distantiella theobroma, Spichpist, Dichelops, Dichelops fur, ., Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp, Margarodes spp, Murgantia histrionic, Neomegalotomus spp, Nesidiocoris tenuis, Nezara spp., Nysius spansisisis, Oysal , Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp., Thyanta spp, Triatoma spp., Vatiga illudens; Acyrthosium pisum, Adalges spp, Agalliana ensigera, Agonoscena targionii, Aleurodicus spp, Aleurocanthus spp, Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aididp. Bactericera cockerelli, Bemisia spp, Brachycaudus spp, Brevicoryne brassicae, Cacopsylla spp, Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp, Cesperana sptra, Cesperana species , Diaphorina citri, Diuraphis noxia, Dysaphis spp., Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae, Hyalopterus spp, Hyperomyzus spp. Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp ,, Mahanarva spp, Metcalfa pruinosa, Met opolophium dirhodum, Myndus crudus, Myzus spp., Neotoxoptera sp, Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter, Parabemisia myricae, Paratrioza cockerelli, Peratremia spig. spp, Phorodon humuli, Phylloxera spp., Pianococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Siliapis ., Schizaphis spp., Sitobion spp., Sogatella furcifera, Spissistilus festinus, Tarophagus Proserpina, Toxoptera spp, Trialeurodes spp, Tridiscus sporoboli, Trionymus spp, Trioza erytreae, Unaspis citri, Zygina flamy, Zygina flamy of the order Heteroptera, for example, Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp .; of the order Homoptera, for example, Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyosperi, Cocusumisumum, Coccus Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Parlatoria spp., Pemphigus spp., Pianocis spp. , Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytrea; of the order Hymenoptera, for example, Acromyrmex, Arge spp, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Pogonomyrmops spp, Invogyrisops spp. Solenopsis spp. and Vespa spp .; of the order Isoptera, for example, Coptotermes spp, Corniternes cumulans, Incisitermes spp, Macrotermes spp, Mastotermes spp, Microtermes spp, Reticulitermes spp .; Solenopsis geminate; of the order Lepidoptera, for example, Aderis spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp., Argyrotaenia spp., Autographa spp., Bucculatrix thur. , Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colias lesbia, Crophusava sp. binotalis, Cryptophlebia leucotreta, Cydalima perspectalis, Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea, Earias spp., Eldana saccharina, Ephestia spp., Epinotia spp, Stigmene acrea, Etiella zinckinella, Eucosma, Eiguos spp., Euxoa spp., Feltia jaculiferia, Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp, Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus, Leucoptera scitella, Lithoc ollethis spp., Lobesia botrana, Loxostege bifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Mythimna spp, Noctua spp, Operophtera spp., Orniodes indica, Ostrinia nubilalis, Pammene spp. ., Panolis flammea, Papaipema nebris, Pectinophora gossypiela, Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Pseudoplusia spp, Rachiplusia spp. , Sparganothis spp., Spodoptera spp., Sylepta derogate, Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tuta absoluta, and Yponomeuta spp .; of the order Mallophaga, for example, Damalinea spp. and Trichodectes spp .; of the order Orthoptera, for example, Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscus spp, and Schistocerca spp .; of the order Psocoptera, for example, Liposcelis spp .; of the order Siphonaptera, for example, Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis; of the order Thysanoptera, for example, Calliothrips phaseoli, Frankliniella spp., Heliothrips spp, Hercinothrips spp., Parthenothrips spp, Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp; and of the order Thysanura, for example, Lepisma saccharina.
[0109] The active ingredients according to the invention can be used to control, that is, contain or destroy, pests of the aforementioned type that occur in particular on plants, especially useful plants and ornamental plants in agriculture, horticulture and in forests, or on 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 from these pests.
[0110] Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, corn or sorghum; beet, such as sugar beet or fodder; fruit, for example pomoideas, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soy; oil crops such as rapeseed, mustard, poppies, olives, sunflowers, coconuts, 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 plantain family, latex plants and ornamental plants.
[0111] In an additional aspect, the invention can also refer to a method of controlling damage to plants and their parts by parasitic plant nematodes (Endoparasitic, Semiendoparasitic and Ectoparasitic nematodes), especially parasitic plant nematodes such as nodule nematodes from the root, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other species of Globodera; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other species of Heterodera; Nematodes from seed galls, species of Anguina; Stem and leaf nematodes, species of Aphelenchoides, Nematodes of root stems, Belonolaimus longicaudatus and other species of Belonolaimus; Nematodes of pine trees, Bursaphelenchus xylophilus and other species of Bursaphelenchus; Ringed nematodes, species of Criconema, species of Criconemella, species of Criconemoides, species of Mesocriconema; stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other species of Ditylenchus; awl-shaped nematodes, species of Dolichodorus, Helichodeos; multicinctus and other species of Helicotylenchus; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lanceolate nematodes, Hoploaimus species; False root gall nematodes, Nacobbus species; Needle-shaped nematodes, Longidorus elongatus species and Longidorus elongatus ; Stylus nematodes, Pratylenchus species; Lesion-forming nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other species of Pratylenchus; Cavernicola nematodes, Radopholus similis and other species of Radopholus; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis and other species of Rotylenchus; Scutellonema species; Nematodes of root shortening and thickening, Trichodorus primitómatos and other species of Trichodorus, Trichodorus primitus and other species of Trichodorus and other species of Trichodorus, Trichodorus primitus and other species of Trichodorus and other species of Trichodorus. of staging, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger-shaped nematodes, Xiphinema species; and other species of plant parasitic nematodes, such as Subangups spp. , Macroposthonia spp., Melinius spp., Punctodera spp., And Quinisulcius spp ..
[0112] The compounds of the invention may also have activity against mollusks. Examples of these include, for example, Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. Nemoralis); ochlodine; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H. obvia); Helicidae Helicigona arbustorum); Helicodiscus; Helix (H. squeezes); 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.
[0113] The term "cultures" should be understood to also include cultures that have been made tolerant to herbicides such as bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, eg primisulfurone, prosulfurone and trifloxysulfurone , EPSPS inhibitors (5-enol-pyrovil-chiquimate-3-phosphate synthase), GS inhibitors (glutamine synthetase}) as a result of conventional breeding methods or genetic engineering An example of a culture that has been made tolerant to imidazolinones , eg imazamox, by conventional breeding methods (mutagenesis) is the Clearfield® summer rape (Canola). Examples of crops that have been made tolerant to herbicides or classes of herbicides by genetic engineering methods include varieties that are more resistant to glyphosate and glufosinate commercially available under the trademarks RoundupReady® and LibertyLink®.
[0114] The term "cultures" should also be understood to also include plants from cultures that have been transformed using recombinant DNA techniques, so that they are able to synthesize one or more toxins with selective action, such as those known, for example , of toxin-producing bacteria, especially those of the genus Bacillus.
[0115] The 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 of Bacillus thuringiensis, such as δ-endotoxins, e.g., CrylA (b), CrylA (c), CrylF, CryIF (a2), CrylIA (b), CrylIIA, CrylIIB (bl) or Cry9c, or vegetative insecticidal proteins (VIP), eg, VIP1, VIP2, VIP3 or VIP3A; or insecticidal proteins from bacteria that colonize nematodes, 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 toxins from Streptomycetes, plant lectins, such as pea lectins, barley lectins or white bell lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome inactivating proteins (RIP), such as ricin, RIP plus, abrina, lufina, saporina or briodina; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as sodium or calcium channel blockers, juvenile hormone, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
[0116] In the context of the present invention are to be understood as δ-endotoxins, for example, CrylA (b), CrylA (c), CrylF, CryIF (a2), CrylIA (b), CrylIIA, CrylIIB (bl) or Cry9c, or vegetative insecticidal proteins (VIP), for example VIP1, VIP2, VIP3 or VIP3A, also expressly hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are recombinantly produced by a new combination of different domains of these proteins (see, for example, WO 02/15701). Truncated toxins are known, for example, a truncated CrylA (b). In the case of modified toxins, one or more amino acids from the naturally occurring toxin are replaced. In such amino acid substitutions, protease recognition sequences not naturally present are preferably inserted into the toxin, as, for example, in the case of CryIIIA055, in which a cathepsin D recognition sequence is inserted into a CrylIIA toxin (see WO 03 / 018810). 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.
[0117] The processes for preparing these transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryox-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
[0118] The toxin contained in transgenic plants gives plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but they are especially commonly found in beetles (Coleoptera), double-winged insects (Diptera) and butterflies (Lepidoptera).
[0119] Transgenic plants are known to contain one or more genes that encode an insecticidal resistance and express one or more toxins, some of which are commercially available. Examples of such plants are: YieldGard® (a corn variety that expresses a CrylA (b) toxin); YieldGard Rootworm® (a corn variety that expresses a CrylIIB (bl) toxin); YieldGard Plus® (a corn variety that expresses a CrylA toxin (b) and a CrylIIB toxin (bl)); Starlink® (a corn variety that expresses a Cry9 toxin (c)); Herculex I® (a corn variety that expresses a CryIF toxin (a2) and the enzyme phosphinothricin N-acetyltransferase (PAT) to provide tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety that expresses a CrylA (c) toxin); Bollgard I® (a cotton variety that expresses a CrylA (c) toxin); Bollgard II® (a cotton variety that expresses a CrylA toxin (c) and a CrylIA toxin (b)); VIPCOT® (a cotton variety that expresses a VIP toxin); NewLeaf® (a potato variety that expresses a CrylIIA toxin); NatureGard® Agrisure® GT Advantage (glyphosate tolerance characteristic GA21), Agrisure® CB Advantage (corn borer (CB) Btll characteristic) and Protecta®.
[0120] Additional examples of such transgenic crops are: 1. More Btll from Syngenta Seeds SAS, Chemin de 1'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96/05/10. Genetically modified Zea mays that has been made resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylA (b) toxin. The more Btll also transgenically expresses the PAT enzyme to achieve tolerance to the herbicide glufosinate ammonium. 2. More Btl76 from Syngenta Seeds SAS, Chemin de 1'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96/05/10. Genetically modified Zea mays that has been made resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylA toxin (b). The more Btl76 also expresses the PAT enzyme transgenically to achieve tolerance to the herbicide glufosinate ammonium. 3. More MIR604 from Syngenta Seeds SAS, Chemin de 1’Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96/05/10. More that it was made resistant to insects by transgenic expression of a modified CrylIIA toxin. This toxin is modified Cry3A055 by insertion of a cathepsin D protease recognition sequence. The preparation of such more transgenic plants is described in WO 03/018810. 4. More 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 CrylHB (bl) toxin and is resistant to certain Coleoptera insects. 5. Cotton IPC 531 from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96/02. 6. Corn 1507 from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C / NL / 00/10. More genetically modified for the expression of the CrylF protein in order to achieve resistance to certain insects Lepidoptera, and the PAT protein in order to achieve tolerance to the herbicide glufosinate ammonium. 7. More 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 more hybrid varieties conventionally improved by crossing the genetically modified varieties NK603 and MON 810. The corn NK603 * MON 810 transgenically expresses the protein CP4 EPSPS, obtained from the Agrobacterium sp. CP4, which provides tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylA (b) toxin obtained from Bacillus thuringiensis subsp. kurstaki that provides tolerance to certain Lepidoptera, including the European corn borer.
[0121] Transgenic crops of insect resistant plants are also described in BATS (Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) 2003 Report.
[0122] The term "cultures" should be understood to also include culture plants that have been thus transformed by the use of recombinant DNA techniques, capable of synthesizing antipathogenic substances that have a selective action, such as, for example, the so-called "proteins" related to pathogenesis "(PRP, see, eg, EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesizing such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191. The methods of producing such transgenic plants they are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
[0123] Antipathogenic substances that can be expressed by such transgenic plants include, for example, ion channel blockers, such as sodium and calcium channel blockers, for example the viral toxins KPI, KP4 or KP6; stilbene synthases; bibenzyl synthases; chitinases; glucanases; so-called "pathogenesis-related proteins" (PRPs; see eg EP-A-0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see eg WO 95/33818) or protein or polypeptide factors involved in the defense of plants against pathogens (so-called "plant disease resistance genes" ", as described in WO 03/000906).
[0124] Cultures can also be modified to increase resistance to fungal pathogens (for example, Fusarium, Anthracnose, or Phytophthora), bacterial (for example, Pseudomonas) or viral (for example, potato leaf roll virus, virus of the tomato head, virus of the mosaic of the cucurbits).
[0125] Cultures also include those that have enhanced resistance to nematodes, such as the soy cyst nematode.
[0126] Cultures that are tolerant to abiotic stress include those that have enhanced tolerance to drought, too much salt, high temperature, glacial cold, frost, or light radiation, for example through the expression of NF-YB or other proteins known in the art .
[0127] Cultures that exhibit increased yield or quality include those that have improved fruit flowering or ripening properties (such as delayed ripening); modified content of oils, starch, amino acids, fatty acids, vitamins, phenolic or others (such as the Vistive ™ soybean variety); intensified use of nutrients (such as improved nitrogen assimilation); and plant product of improved quality (such as higher quality cotton fiber).
[0128] Other areas of use for compounds and 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, in particular the protection of humans, domestic animals and productive cattle against pests of the type mentioned.
[0129] The present invention also provides a process 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 of pest control 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 (indoor 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 the application of such compositions to a substrate such as a non-woven or woven material in the form of (or which can be used in the manufacture of) knitwear, clothing, bedding, curtains and tents.
[0130] In one embodiment, the method for controlling such pests comprises applying a pesticide-effective amount of the compositions according to the invention to the target pests, their locus, or a surface or substrate, of in order to provide effective residual pesticidal activity on the surface or substrate. Such application can be made by brushing, rolling, spraying, spreading or immersing the pesticidal composition of the present invention. By way of example, an IRS application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention, in order to provide effective residual pesticidal activity on the surface. In another embodiment, it is contemplated the application of such compositions for residual pest control to a substrate such as a woven material in the form of (or which can be used in the manufacture of) knitwear, clothing, bedding, curtains and tents.
[0131] The substrates including non-woven, woven or knitted fabrics to be treated can be made from natural fibers such as cotton, raffia, jute, linen, sisal, simple warp, or wool, or synthetic fibers such as polyamide, polyester, polypropylene, polyacrylonitrile or the like. Polyesters are particularly suitable. Textile treatment methods are known, e.g. from WO 2008/151984, WO 2003/034823, US 5631072, WO 2005/64072, W02006 / 128870, EP 1724392, WO2005113886 or WO 2007/090739.
[0132] Other 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.
[0133] In the area of tree injection / trunk treatment, the compounds according to the present invention are especially suitable against wood-piercing insects of the order Lepidoptera as mentioned above, and of the Coleoptera order, especially against wood-perforators listed in tables A and B below: Table A. Examples of exotic wood drills of economic importance.

Table B. Examples of native wood drills of economic importance.





[0134] In the hygiene sector, the compounds and compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, crop mites, flies (that bite and lick), parasitic fly larvae, lice , hair lice, flies and bird lice.
[0135] Examples of such parasites are: Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculus spp. and Phtirus spp., Solenopotes spp .. Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp .. Of the order Diptera and the sub-orders 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 .. Of the order Siphonapterida, for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp .. Of the order Heteropterida, for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp .. Da order Blattarida, for example Blatta orientalis, American periplaneta, Blattela germanica and Supella spp .. From the subclass Acaria (Acarida) and from 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 .. Of 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., Cyt. and Laminosioptes spp ..
[0136] The compounds and compositions according to the invention are also suitable to protect against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and cardboard, leather, floor coverings and constructions.
[0137] 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 mollis, Priobium , Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus species, Tryptodendron species, Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon species and Dinoderus minuten, gyroscopic and also, 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 Copteris, schotermysis and schnitzels and Cops.
[0138] The present invention therefore provides an insecticidal, acaricidal, nematicidal or molluscicidal composition, preferably an insecticidal or acaricidal composition comprising an effective amount as an insecticide, acaricidal, nematicidal or molluscicidal compound of a compound of formula I and a vehicle or suitable diluent for it.
[0139] In a further aspect, the invention provides a method to combat and control pests which comprises the application of an insecticide, acaricide, nematicide or molluscicide effective amount, preferably an insecticide and acaricide effective amount of a compound of formula I or a composition comprising a compound of formula I, to a pest, to the location of a pest, or to a plant susceptible to attack by a pest, with the exception of a method for treating the human body or animal by surgery or therapy, and diagnostic methods practiced on the human or animal body.
[0140] The compounds of formula I are preferably used against insects or mites.
[0141] The term "plant", as used herein, includes seedlings, shrubs and trees.
[0142] The invention also relates to a pesticidal composition which, in addition to comprising the compound of formula I, further comprises formulation adjuvants.
[0143] Consequently, the invention also relates to pesticidal compositions such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, paste suitable for spreading, diluted emulsions, soluble powders, dispersible powders, wettable powders, dust , granules or encapsulations in polymeric substances, which comprise - at least - one of the active ingredients according to the invention, and which must be selected so as to be suitable for the intended purposes and the prevailing circumstances.
[0144] In these compositions, the active ingredient is employed in pure form, a solid active ingredient for example in a specific particle size, or, preferably, together with - at least - one of the auxiliaries conventionally used in the formulation technique, such as diluents, for example solvents or solid carriers, or such as surfactant compounds.
[0145] Examples of suitable solvents are: non-hydrogenated or partially hydrogenated aromatic hydrocarbons, preferably the C8 to C12 fractions of alkylbenzenes, such as mixtures of xylene, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, such alcohols such as ethanol, propanol or butanol, glycols and their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, isophorone or strongly diacetyl solvents, such as diacetone, ethanol solvents -one, dimethyl or N, N-dimethylformamide sulfoxide, water, non-epoxidized or epoxidized vegetable oils, such as rapeseed, castor, coconut or non-epoxidized or epoxidized soy, and silicone oils.
[0146] Solid carriers that are used, for example, for dust and dispersible powders are, as a general rule, crushed natural minerals such as calcite, talc, kaolin, montmorillonite or atapulgite. To improve the physical properties, it is also possible to add highly dispersible silicas or highly dispersible absorbable polymers. Particulate absorbable carriers suitable for granules are of the porous type, such as pumice, brick crushed stone, sepiolite or bentonite, and suitable non-absorbable carrier materials are calcite or sand. In addition, a large number of granulated materials of an organic or inorganic nature can be used, in particular dolomite or comminuted plant residues.
[0147] Suitable surfactant compounds are, depending on the type of active ingredient to be formulated, non-ionic, cationic and / or anionic surfactants or mixtures of surfactants that have good emulsifying, dispersing and wetting properties. The surfactants mentioned below are only to be considered as examples; a large number of additional surfactants conventionally used in the formulation technique and suitable according to the invention are described in the relevant literature.
[0148] Suitable non-ionic surfactants are, in particular, derivatives of polyglycolether of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids, or alkylphenols which may contain approximately 3 to approximately 30 glycol groups and approximately 8 to approximately 20 carbon atoms in the aliphatic hydrocarbon (cyclo) radical or approximately 6 to approximately 18 carbon atoms in the alkyl fraction of the alkyl phenols. Water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylene diamine polypropylene glycol or alkyl polypropylene glycol having 1 to approximately 10 carbon atoms in the alkyl chain and approximately 20 to approximately 250 ethylene glycol groups and approximately 10 to approximately 100 propylene glycol groups are also suitable. Typically, the aforementioned compounds contain 1 to approximately 5 ethylene glycol units per propylene glycol unit. Examples that may be mentioned are nonylphenoxypolyethoxyethanol, castor oil polyglycolic ether, polyethylene oxide / polypropylene glycol adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol or octylphenoxypolyethoxyethanol. Polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan trioleate, are also suitable.
[0149] Cationic surfactants are especially quaternary ammonium salts that generally have at least one alkyl radical of approximately 8 to approximately 22 C atoms as substituents, and as additional substituents, lower alkyl radicals (halogenated or non-halogenated) or hydroxyalkyls or benzyls. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates. Examples are stearyltrimethylammonium chloride and benzylbis (2-chloroethyl) ethylammonium bromide.
[0150] Examples of suitable anionic surfactants are water-soluble soaps or water-soluble synthetic surfactant compounds. Examples of suitable soaps are ammonium salts (substituted or unsubstituted), alkaline earth or alkaline fatty acids having approximately 10 to approximately 22 C atoms, such as sodium or potassium salts of oleic or stearic acid, or mixtures of natural fatty acids that are obtainable, for example, from coconut or pine oil; mention must also be made of fatty acid methyl taurates. However, synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates. As a rule, fatty sulfonates and fatty sulfates are present as ammonium salts (substituted or unsubstituted), alkaline earth or alkaline and generally have an alkyl radical of approximately 8 to approximately 22 C atoms, with an alkyl being also understood to include the fraction alkyl of acyl radicals; examples that can be mentioned are the sodium or calcium salts of lignosulfonic acid, dodecyl sulfuric ester or a mixture of fatty alcohol sulfates prepared from natural fatty acids. This group also includes the salts of sulfuric esters and sulfonic acids in ethylene oxide / fatty alcohol adducts. Sulphonated benzimidazole derivatives preferably contain 2 sulfonyl groups and a fatty acid radical of approximately 8 to approximately 22 C atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of decylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or a condensate of naphthalenesulfonic acid / formaldehyde. Furthermore, suitable phosphates such as phosphoric ester salts of a p-nonylphenol / (4-14) ethylene oxide adduct or phospholipids are also possible. Other suitable phosphates are the triesters of phosphoric acid with aliphatic or aromatic alcohols and / or diesters of alkylphosphonic acids with aliphatic or aromatic alcohols, which are adjuvants of the high performance oily type. These triesters have been described, for example, in WO 01/47356, WO 00/56146, EP-A-0579052 or EP-A-1018299, or are commercially available under their chemical names. Preferred phosphoric acid triesters for use in the new compositions are tris- (2-ethylhexyl) phosphate, tris-n-octyl phosphate and tris-butoxyethyl phosphate, with tris- (2-ethylhexyl) phosphate being the most preferred . Suitable alkylphosphonic acid diesters are bis- (2-ethylhexyl) - (2-ethylhexyl) -phosphonate, bis- (2-ethylhexyl) - (n-octyl) - phosphonate, dibutyl-butylphosphonate and the bis (2-ethylhexyl) - tripropylenophosphonate, wherein bis- (2-ethylhexyl) - (n-octyl) -phosphonate is particularly preferred.
[0151] The compositions according to the invention can preferably additionally 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 used in the composition according to the invention is generally 0.01 to 10%, based on the spray mixture. For example, the oil additive can be added to the spray tank at the desired concentration after the spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil such as ADIGOR® and MERO®, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® (Rhône-Poulenc Canada Inc.), alkyl esters of oils of vegetable origin, for example those derived from methyl, or an oil of animal origin, such as fish oil or cow tallow. A preferred additive contains, for example, as active components, essentially 80% by weight of fish oil alkyl esters and 15% by weight of methylated rapeseed oil, and also 5% by weight of usual emulsifiers and pH modifiers. Especially preferred oil additives comprise alkyl esters of C8-C22 fatty acids, with methyl derivatives of C1-2 fatty acids being especially important, for example methyl esters of lauric acid, palmitic acid and oleic acid. These esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9). A preferred methyl ester derivative of a fatty acid is Emery® 2230 and 2231 (Cognis GmbH). These and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000. Likewise, alkoxylated fatty acids can be used as additives in the compositions of the invention, as well as additives based on polymethylsiloxane, which were described in WO 2008/037373.
[0152] The application and action of oil additives can be further improved by their combination with surfactants, such as nonionic, anionic or cationic surfactants. Examples of suitable anionic, nonionic and cationic surfactants are listed on pages 7 and 8 of WO 97/34485. Preferred surfactant substances are anionic surfactants of the dodecylbenzylsulfonate type, especially their calcium salts, and also nonionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C12-C22 fatty alcohols having an ethoxylation degree of 5 to 40. Examples of commercially available surfactants are Genapol types (Clariant AG). Also preferred are silicone surfactants, especially heptamethyltrisiloxanes modified with poly (alkyl oxide), which are commercially available, eg, as Silwet L-77®, and also perfluorinated surfactants. The concentration of surfactants in relation to the total additive is generally 1 to 30% by weight. Examples of oil additives consisting of mixtures of oils or mineral oils or their derivatives with surfactants are Edenor ME SU®, Turbocharge® (Syngenta AG, Switzerland) and Actipron® (BP Oil UK Limited, UK).
[0153] Said surfactants can also be used in formulations alone, that is, without oil additives.
[0154] Furthermore, the addition of an organic solvent to the oil additive / surfactant mixture can contribute to further intensification of the action. Suitable solvents are, for example, Solvesso® (ESSO) and Aromatic Solvent® (Exxon Corporation). The concentration of such solvents can be from 10 to 80% by weight of the total weight. Such oil additives, which may be mixed with solvents, are described, for example, in US-A-4 834 908. A commercially available oil additive disclosed therein is known by the name MERGE® (BASF Corporation). An additional oil additive that is preferred according to the invention is SCORE® (Syngenta Crop Protection Canada).
[0155] In addition to the oil additives listed above, in order to enhance the activity of the compositions according to the invention, it is also possible that alkylpyrrolidone formulations (eg Agrimax®) are added to the spray mixture. Synthetic latex formulations, such as, for example, polyacrylamide, polyvinyl or poly-1-p-mentene compounds (eg, Bond®, Courier® or Emerald®) can also be used. Solutions containing propionic acid, for example Eurogkem Pen-e-trate®, can also be mixed in the spray mixture as activity-enhancing agents.
[0156] The term "active ingredient" refers to one of the compounds of formula I, especially compounds of formula I specifically disclosed in the tables. It also refers to mixtures of the compound of formula I, in particular a compound selected from said Table 1, with other insecticides, fungicides, herbicides, phytoprotectors, adjuvants and the like, whose mixtures are specifically disclosed below.
[0157] The compositions can 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 soy oil), defoamers, for example silicone, preservatives, viscosity regulators, binders and / or adhesion agents; fertilizers, in particular nitrogen-containing fertilizers such as ammonium and urea nitrates, as described in WO 2008/017388, which can enhance the effectiveness of the inventive compounds; or other active ingredients to achieve specific effects, for example ammonium or phosphonium salts, in particular halides, (hydrogen) sulfates, nitrates, (hydrogen) carbonates, citrates, tartrates, forms and acetates, as described in WO 2007/068427 and WO 2007/068428, which can also enhance the effectiveness of the inventive compounds and which can be used in combination with penetration enhancers such as alkoxylated fatty acids; bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.
[0158] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries, for example, by grinding, sieving and / or compression of a solid active ingredient and in the presence of at least one auxiliary, for example, by intimate mixing and / or grinding the active ingredient with the auxiliary (auxiliaries).
[0159] The application methods for the compositions, that is, the pest control methods of the aforementioned type, such as spraying, atomizing, dusty, brushing, covering, dispersing or spilling - which are to be selected to suit desired objectives of the prevailing circumstances - and the use of pest control compositions of the type mentioned above, 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.
[0160] A preferred method of application in the area of crop protection is application to the foliage of plants (leaf application), being possible to select the frequency and rate of application to meet the danger of infestation with the pest in question. Alternatively, the active ingredient can reach the plants through the root system (systemic action), by soaking the plant locus with a liquid composition or by incorporating the active ingredient in solid form into the plant locus, for example in the soil, for example in granules (application to soil). In the case of rice fields, these granules can be calibrated in the flooded rice field.
[0161] The compositions according to the invention are also suitable for the protection of plant propagating material, for example seeds, such as fruit, tubers or nuclei, or nursery plants, against pests of the type mentioned above. The propagation material can be treated with the compositions before planting, for example the seed can be treated before sowing. Alternatively, the compositions can be applied to the seed nuclei (coating), either by soaking the nuclei 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 groove during the process of forming rows. These treatment methods for plant propagation material and plant propagation material comprising a compound of formula (I) as defined above, are further subjects of the invention.
[0162] Other methods of applying the compositions according to the invention include drip application in the soil, immersion of plant parts such as root bulbs or tubers, soaking the soil, as well as soil injection. These methods are known in the art.
[0163] To apply a compound of formula I as an insecticide, acaricide, nematicide or molluscicide to a pest, a pest site, or a plant susceptible to attack by a pest, a compound of formula I is usually formulated into a composition that includes, in addition to the compound of formula I, an appropriate inert diluent or carrier and, optionally, a formulation adjuvant in the form of a surfactant (SFA) as described herein or, for example, in EP-B-1062217. SFAs are chemical products capable of modifying the properties of an interface (for example liquid / solid, liquid / air or liquid / liquid interfaces) by decreasing the interfacial tension and thus leading to changes in other properties (for example dispersion, emulsification and wetting).
[0164] As a rule, the compositions comprise 0.1 to 99%, in particular 0.1 to 95%, of the active ingredient of formula I, and 1 to 99.9%, in particular 5 to 99.9%, of at least one solid or liquid adjuvant, it being possible, as a rule, that 0 to 25%, in particular 0.1 to 20%, of the composition consists of surfactants (% in each case meaning weight percentage). While concentrated compositions tend to be preferred for commercial goods, the end consumer usually uses diluted compositions that have significantly lower concentrations of the active ingredient.
[0165] 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.
[0166] When used to cure a seed, a compound of formula I is used at a rate of 0.0001g to 10g (for example 0.001 g or 0.05 g), preferably 0.005 g to 10 g, more preferably 0.005 g to 4 g, per kilogram of seed.
[0167] Preferred premix formulations for seed treatment are concentrated in aqueous suspension. The formulation can be applied to seeds using conventional treatment techniques and machines, such as fluidized bed techniques, the roller mill method, roto-static seed scrubbers, and drum coaters. Other methods such as spouting beds can also be useful. The seeds can be pre-sized before coating. After coating, the seeds are typically dried and then transferred to a sizing machine for sizing. Such procedures are known in the art.
[0168] The compositions can be chosen from a number of types of formulations, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP) , granules (GR) (slow or fast release), soluble concentrates (SL), oil-miscible liquids (OL), ultra-low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil -in- water (EW) such as water-in-oil (EO)), microemulsions (ME), suspension concentrates (SC), oil-based suspension concentrate (OD), aerosols, nebulization / fumigation formulations, suspensions capsules (CS) and seed treatment formulations. The type of formulation chosen in any case will depend on the particular intended purpose and the physical, chemical and biological properties of the compound of formula I.
[0169] Sprayable powders (DP) can be prepared by mixing a compound of formula I with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earth, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, talc and other solid organic and inorganic vehicles) and mechanical grinding of the mixture to a fine powder.
[0170] Soluble powders (SP) can be prepared by mixing a compound of formula I with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulfate) or one or more organic solids water soluble (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents, or a mixture of said agents to improve dispersibility / solubility in water. The mixture is then ground into a fine powder. Similar compositions can also be granulated to form water-soluble granules (SG).
[0171] Wettable powders (WP) can be prepared by mixing a compound of formula I with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more more suspending agents to facilitate dispersion in liquids. The mixture is then ground into a fine powder. Similar compositions can also be granulated to form water-dispersible granules (WG).
[0172] Granules (GR) can be formed by granulating a mixture of a compound of formula I and one or more powdered solid diluents or carriers, or from preformed blank granules by absorbing a compound of formula I (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, atapulgite clays, Fuller's soil, kieselguhr, diatomaceous earth or crushed corn cobs) or by adsorption of a compound of formula I (or a solution thereof, in a suitable agent) in a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary. Agents that are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and adhesive agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils ). One or more of other additives can also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
[0173] Dispersible concentrates (DC) can be prepared by dissolving a compound of formula I in water or an organic solvent, such as a ketone, alcohol or glycolether. These solutions can contain a surfactant (for example to improve dilution in water or prevent crystallization in a spray tank).
[0174] Emulsifiable concentrates (EC) or oil-in-water (EW) emulsions can be prepared by dissolving a compound of formula I in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Organic solvents suitable for use in EC include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Trademark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol) , furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), fatty acid dimethylamides (such as C8-C10 fatty acid dimethylamides) and dormant hydrocarbons. An EC product can emulsify spontaneously after addition to water, to produce an emulsion with sufficient stability to allow spray application by means of appropriate equipment. The preparation of an EW involves obtaining a compound of formula I, in the form of a liquid (if it is not a liquid at room temperature, it can be melted at a reasonable temperature, typically below 70 ° C) or in solution (for example dissolving it in an appropriate solvent) and then emulsifying the resulting liquid or solution in water containing one or more SEA, under high shear, to produce an emulsion. Solvents suitable for use in EW include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other suitable organic solvents that have low water solubility.
[0175] Microemulsions (ME) can be prepared by mixing water with a mixture of one or more solvents with one or more SEA, to spontaneously produce a thermodynamically stable liquid isotropic formulation. A compound of formula I is initially present in water or in the solvent / SFA combination. Solvents suitable for use in ME include those described hereinbefore for use in EC or EW. An ME can be an oil-in-water or water-in-oil system (the system that is present can be determined by conductivity measurements), and can be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. An ME is suitable for dilution in water, remaining as a microemulsion or forming a conventional oil-in-water emulsion.
[0176] Suspension concentrates (SC) can comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula I. SC can be prepared by grinding, in a ball or bead mill, of the solid compound of formula I in a suitable medium, optionally with one or more dispersing agents, to produce a suspension of fine particles of the compound. One or more wetting agents and a suspending agent may be included in the composition to reduce the rate at which the particles settle. Alternatively, a compound of formula I can be dry-molded and added to water, containing the agents described herein above, to prepare the desired final product.
[0177] The oil-based suspension concentrate (OD) can be prepared similarly by suspending finely divided insoluble solid particles of a compound of formula I in an organic fluid (for example, at least one mineral oil or vegetable oil). ODs may additionally comprise at least one penetration enhancer (for example, ethoxylated alcohol or a related compound), at least one nonionic surfactant and / or at least one anionic surfactant, and optionally at least one additive from the group of emulsifiers, defoaming agents, preservatives, antioxidants, dyes and / or inert fillers. An OD is intended, and is suitable for, dilution with water before use to produce a spray solution with sufficient stability to allow spray application through appropriate equipment.
[0178] Aerosol formulations comprise a compound of formula I and a suitable propellant (for example n-butane). A compound of formula I can also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurized manual spray pumps.
[0179] A compound of formula I can be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the said compound.
[0180] Capsule suspensions (CS) can be prepared in a similar way to the preparation of EW formulations, but with an additional polymerization step, such that an aqueous dispersion of oil droplets is obtained, in which each droplet of oil is encapsulated by a polymeric envelope and contains a compound of formula I and, optionally, a vehicle or diluent for it. The polymeric shell can be produced by an interfacial polycondensation reaction or by a coacervation procedure. The compositions can provide controlled release of the compound of formula I and can be used for seed treatment. A compound of formula I can also be formulated in a biodegradable polymeric matrix to provide a slow and controlled release of the compound.
[0181] A compound of formula I can also be formulated for use as a seed treatment, for example as a powder composition, including a dry seed treatment powder (DS), a water soluble powder (SS) or a water-dispersible powder for paste treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a suspension of capsules (CS). The preparations of DS, SS, WS, FS and LS compositions are very similar, respectively, to those of the DP, SP, WP, SC, OD and DC compositions described above. Seed treatment compositions may include an agent to aid in adhering the composition to the seed (for example, a mineral oil or a film-forming barrier).
[0182] A composition of the present invention may include one or more additives to improve the biological performance of the composition (for example, by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or absorption or mobility of a compound of formula I). Such additives include surfactants (SFA), oil-based spray additives, for example certain mineral oils, vegetable oils or natural vegetable oils (such as soybean oil and rapeseed), and combinations of these with other bio-enhancing adjuvants (ingredients that can assist or modify the action of a compound of formula I). An increase in the effect of the compound of formula I can be achieved, for example, by adding ammonium and / or phosphonium salts and / or, optionally, at least a penetration enhancer, such as alkoxylated fatty alcohols (eg rapeseed oil methylester) ) or vegetable oil esters.
[0183] Wetting agents, dispersing agents and emulsifying agents can be surfactants (SFA) of the cationic, anionic, amphoteric or non-ionic type.
[0184] Suitable cationic type SFAs include quaternary ammonium compounds (eg, cetyltrimethylammonium bromide), imidazolines and amine salts.
[0185] Suitable anionic SFAs include alkali metal salts of fatty acids, aliphatic monoester salts of sulfuric acid (eg, sodium lauryl sulfate), salts of sulfonated aromatic compounds (eg, sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, butylnaphthalene and mixtures of sodium diisopropyl and sodium tri-isopropylnaphthalenesulfonates), ether sulphates, ether sulphates (eg sodium lauret-3-sulphate), carboxyl ether (eg lauret-3- sodium carboxylate), phosphate esters (products of the reaction between one or more fatty alcohols and phosphoric acid (predominantly monoesters) or phosphorus pentoxide (predominantly diesters), for example, the reaction between lauryl alcohol and tetraphoric acid; additionally, these products can be ethoxylated), sulfosuccinates, paraffin or olefin sulfonates, taurates and lignosulfonates.
[0186] Suitable amphoteric-type SFAs include betaines, propionates and glycinates.
[0187] Suitable non-ionic SFAs include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkyl phenols (such as octylphenol, nonylphenol or octycresol); partial esters derived from long-chain fatty acids or hexitol anhydrides; condensation products of these partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example, esters of polyethylene glycol and fatty acid); amine oxides (for example, lauryl dimethylamine oxide); and lecithins.
[0188] Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and expandable clays (such as bentonite or atapulgite).
[0189] A compound of formula I can be applied by any of the known means of applying pesticidal compounds. For example, it can be applied, either formulated or unformulated, to pests or at a pest site (such as a pest habitat, or a growing plant susceptible to pest infestation) or anywhere on the plant, including foliage , stems, branches or roots, in the seed before it is planted or in other media where the plants are growing or will be planted (such as the soil surrounding the roots, the soil in general, water slide or hydroponic culture systems), directly or sprayed, dusty, applied by dipping, applied as a cream or paste formulation, applied as a vapor or applied by distributing or incorporating a composition (such as a granular composition or a composition packaged in a water-soluble bag) on the ground or in an aqueous environment.
[0190] A compound of formula I can also be injected into plants or sprayed on vegetation using electrodynamic spraying techniques or other low-volume methods, or applied by means of terrestrial or aerial irrigation systems.
[0191] Compositions for use as aqueous preparations (aqueous solutions or dispersions) are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, with the concentrate being added to water before use. It is often required that these concentrates, which may include DC, SC, OD, EC, EW, ME, SG, SP, WP, WG and CS, support storage for extended periods and, after such storage, be able to be added to water to form aqueous preparations that remain homogeneous for a sufficient time to allow them to be applied by conventional spray equipment. Such aqueous preparations can contain varying amounts of a compound of formula I (for example, 0.0001 to 10%, by weight) depending on the purpose for which they will be used.
[0192] A compound of formula I can be used in mixtures with fertilizers (for example, fertilizers containing nitrogen, potassium or phosphorus, and more particularly ammonium nitrate and / or urea fertilizers). Suitable types of formulation include fertilizer granules. The mixtures suitably contain up to 25% by weight of the compound of formula I.
[0193] Preferred compositions are composed particularly as follows (% = weight percentage): Emulsifiable concentrates:
Dust:
Suspension concentrates:
Wettable powders:
Sprinkles:
Examples of Preparations:
[0194] "Pf" means melting point in ° C. Free radicals represent methyl groups. The measurements by 1 H NMR were recorded on a 400MHz Brucker spectrometer, the chemical deviations are given in ppm in relation to a TMS standard. The spectra were measured in the indicated deuterated solvents. LCMS methods: Method 1 (ZCQ 13):
[0195] The 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, Gas Flow in the Cone: 0 L / Hour, Desolvation Gas Flow: 650 L / Hour, Range of masses: 100 to 900 Da) and an UPLC Acquity from Waters: 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 pm, 30 x 2.1 mm, Temp: 60 ° C; DAD wavelength range (nm): 210 to 500, Solvent Gradient: A = water + 5% MeOH + 0.05% HCOOH, B = Acetonitrile + 0.05% HCOOH; gradient: 0 min to 0% B, 100% A; 2.7-3.0 min at 100% B; Flow (mL / min) 0.85. Method 2 (API 2000):
[0196] API 2000 mass spectrometer from Applied Biosystems (Single quadrupole mass spectrometer); Ionization method: Electrospray; Polarity: positive ions. Capillary (kV) 5.5, DP (V) 50.00, Input Potential (V) 10, Focusing Potential (V) 400, Source Temperature (° C) 200, Ion Source Gas (Psi) 40, Ion Source Gas 2 (Psi) 50, Curtain Gas (Psi) 40; Pasta range: 100 to 800 amu; UV wavelength range (nm): 220 to 260; Column type: C18 Zorbax Extend; Column length: 50 mm; Column internal diameter: 4.6 mm; Particle Size: 5 microns
[0197] Instrument Shimadzu Prominance with the following gradient conditions in HPLC (Solvent A: NH4OAc lOMm in Water and Solvent B: Acetonitrile) Flow rate: 1.2 ml / min
EXAMPLE 1: Preparation of 6- (2-ethylsulfonylphenyl) -5-methyl-2-trifluoromethyl) imidazo [2,1-b] [1,3,4] thiadiazole (compound Pl, No. 9.005): Step 1: Preparation of l- (2-ethylsulfanylphenyl) propan-l-one

[0198] To a solution of 1- (2-chlorophenyl) propan-l-one (20.0 g, 118.6 mmol) in N, N-dimethylformamide (100 mL) at 0-5 ° C was added ethanethiolate sodium (24.9 g, 296.5 mmol). The suspension was warmed to room temperature, then stirred at 40 ° C for 2 hours. The reaction mixture was poured into saturated aqueous ammonium chloride, extracted with ethyl acetate, the combined organic phases washed with water and saturated sodium chloride solution, dried with sodium sulfate and evaporated to dryness. The residue was dissolved in diethyl ether, the solution treated with activated carbon, stirred, filtered through hyflo and the solvent evaporated in vacuo. The product was precipitated from n-heptane at 10 ° C, filtered and dried to give a first harvest (16.8 g). The mother liquor was concentrated, and the residue purified by chromatography on silica gel (n-heptane / dichloromethane 2: 1) to further yield 1.95 g of product as a pale yellow solid, mp 30-31 ° C. LCMS (method ZCQ13): 195 (M + H) +, retention time 1.53 min Step 2: Preparation of 1- (2 - ethylsulfonylphenyl) propan-l-one

[0199] To a solution of 1- (2-ethylsulfanylphenyl) propan-1-one (2.0 g, 10.3 mmol) in dichloromethane (50 mL) at 10 ° C was added meta-chloroperoxybenzoic acid (5.0 g, mCPBA, -75%, 21.7 mmol) and the reaction mixture was stirred overnight at room temperature. The resulting suspension was filtered and the solid washed with cold dichloromethane. The combined filtrates were washed with a 10% aqueous solution of NaHSO3, saturated aqueous sodium bicarbonate and saturated sodium chloride solution, dried with sodium sulfate and evaporated to dryness to give the product as a colorless oil (2 , 01 g). This material was used without further purification in the next step. LCMS (method ZCQ13): 227 (M + H) +, retention time 1.04 min Step 3: Preparation of 2-bromo-1- (2-ethylsulfonylphenyl) propan-l-one

[0200] To a solution of 1- (2-ethylsulfonylphenyl) propan-l-one (1.5 g, 6.63 mmol) in ethyl acetate / chloroform 1: 1 (10 mL, v / v) was added bromide copper (II) (3.0 g, 13.43 mmol) and the reaction mixture was stirred at reflux for 2 hours. The suspension was diluted with dichloromethane and filtered through hyflo. The filtrate was dried over sodium sulfate, filtered and evaporated to dryness to give the product as a pale yellow gum (2.0 g). This material was used without further purification in the next step. LCMS (method ZCQ13): 305/307 (M + H) +, retention time 1.31 min Step 4: Preparation of 6- (2-ethylsulfonylphenyl) -5-methyl-2-trifluoromethyl) imidazo [2,1- b] [1,3,4] thiadiazole (title compound Pl, 9,005)

[0201] A microwave vial was loaded with a solution of 2-bromo-1- (2-ethylsulfonylphenyl) propan-1-one (500 mg, 1.64 mmol) and 5- (trifluoromethyl) -1.3 , 4-thiadiazole-2-amine (277 mg, 1.64 mmol) in ethanol (1.5 mL) and the mixture was heated in a microwave oven at 170 ° C for 50 minutes. The reaction mixture was concentrated in vacuo, the residue diluted with ethyl acetate and saturated aqueous sodium carbonate, the phases were separated, the aqueous phase extracted with ethyl acetate, the combined organic phases washed with saturated sodium chloride solution, dried with sodium sulfate and evaporated to dryness. The residue was purified by chromatography on silica gel (ethyl acetate / cyclohexane 1: 4), to give the title compound Pl, 9,005 (105 mg) as a gum. LCMS (method ZCQ13): 376 (M + H) +, retention time 1.57 min EXAMPLE 2: Preparation of 6- (3-ethylsulfonylphenyl-2-pyridyl) -2- (trifluoromethyl) imidazo [2,1-b ] [1,3,4] thiadiazole (compound P2, No. 3,001): Step 1: Preparation of 1- (3-ethylsulfanyl-2-pyridyl) ethanone

[0202] Obtained from 1- (3-fluoro-2-pyridyl) ethanone (2.1 g, 15.1 mmol) and sodium ethanethiolate (1.59 g, 18.9 mmol) in N, N -dimethylformamide (40 ml) according to the procedure of Example 1, step 1. The mixture was stirred at room temperature for 2 hours. The impure product obtained after extraction processing was used in the next step without further purification. Pale brown crystals (2.7 g), mp 68-70 ° C. LCMS (method ZCQ13): 182 (M + H) +, retention time 1.09 min Step 2: Preparation of 1- (3-ethylsulfonyl-2-pyridyl) ethanone

[0203] Obtained from 1- (3-ethylsulfanyl-2-pyridyl) ethanone (2.7 g, 14.9 mmol) and meta-chloro-peroxybenzoic acid (7.2 g, mCPBA, ~ 75%, 31 , 3 mmol) in dichloromethane (50 mL) according to the procedure of Example 1, step 2 to give the product as a colorless oil (3.1 g). This material was used without further purification in the next step. LCMS (method ZCQ13): 214 (M + H) +, retention time 0.66 min Step 3: Preparation of 2-bromo-1- (3-ethylsulfonyl-2-pyridyl) ethanone

[0204] Obtained from 1- (3-ethylsulfonyl-2-pyridyl) ethanone (1.55 g, 7.27 mmol) and copper (II) bromide (1.78 g, 7.99 mmol) in acetate ethyl / chloroform 1: 1 (5 mL, v / v) according to the procedure of Example 1, step 3. The crude product obtained after processing was purified by chromatography on silica gel (ethyl acetate / cyclohexane 1: 9 ) to give the product as a colorless gum (0.98 g). LCMS (method ZCQ13): 292/294 (M + H) +, retention time 0.96 min Step 4: Preparation of 6- (3-ethylsulfonyl-2-pyridyl) -2- (trifluoromethyl) imidazo [2, 1 —B] [1,3,4] thiadiazole (title compound P2, 3,001)

[0205] Obtained from 2-bromo-1- (3-ethylsulfonyl-2-pyridyl) ethanone (150 mg, 0.51 mmol) and 5- (trifluoromethyl) -1,3,4-thiadiazole-2- amine (86.8 mg, 0.51 mmol) in ethanol (2 mL) according to the procedure of Example 1, step 4. The mixture was heated in a microwave oven at 170 ° C for 30 minutes. The crude product obtained after extractive processing was triturated in n-heptane, the mixture stirred for 15 minutes and left to decant. The residue was carefully discarded and the solid residue purified by chromatography on silica gel (ethyl acetate / cyclohexane 1: 3), to give the title compound P2, 3,001 (34 mg) as a solid. LCMS (method ZCQ13): 363 (M + H) +, retention time 1.31 min EXAMPLE 3: Preparation of 6- [3-ethylsulfonyl-5- (trifluoromethyl) -2-pyridyl] -5-methyl-2- (trifluoromethyl) imidazo [2,1-b] [1,3,4] thiadiazole (compound P3, No. 3,006): Step 1: Preparation of 1- [3-ethylsulfonyl-5- (trifluoromethyl) -2-pyridyl] propan-l-ona

[0206] To a solution of 1- [3-ethylsulfanyl-5- (trifluoromethyl) -2-pyridyl] propan-l-one (6.9 g, 26.2 mmol) in dichloromethane (100 mL) at 10 ° C meta-chloroperoxybenzoic acid (13.0 g, mCPBA, ~ 75%, 56.4 mmol) was added in 4 portions and the reaction mixture was stirred overnight at room temperature. The resulting suspension was filtered and the solid washed with cold dichloromethane. The combined filtrates were washed with a 10% aqueous NaHSOa solution, saturated aqueous sodium bicarbonate and saturated sodium chloride solution, dried over sodium sulfate and evaporated to dryness to give the product as a white solid (7 , 4 g), mp 122-123 ° C. This material was used in the next step without further purification. LCMS (method ZCQ13): 296 (M + H) +, retention time 1.46 min Step 2: Preparation of 2-bromo-l- [3-ethylsulfonyl-5- (trifluoromethyl) -2-pyridyl] propan-l -one

[0207] To a solution of 1- [3-ethylsulfonyl-5- (trifluoromethyl) -2-pyridyl] propan-l-one (7.4 g, 25.0 mmol) in ethyl acetate / chloroform 1: 1 ( 150 mL, v / v) copper (II) bromide (14.0 g, 62.7 mmol) was added. The mixture was heated in 5 parallel batches in a microwave oven at 140 ° C for 100 minutes. The suspension was diluted with dichloromethane and filtered through hyflo. The filtrate was dried over sodium sulfate and evaporated to dryness. The residue was purified by chromatography on silica gel (ethyl acetate / cyclohexane 1: 9) to give the product as a pale red solid (7.1 g), mp 82-83 ° C. LCMS (method ZCQ13): 374/376 (M + H) +, retention time 1.60 min Step 3: Preparation of 6- [3-ethylsulfonyl-5- (trifluoromethyl) -2-pyridyl] -5-methyl- 2- (trifluoromethyl) imidazo [2,1-b] [1,3,4] thiadiazole (title compound P3, 3,006)

[0208] A microwave vial was loaded with a solution of 2-bromo-1- [3-ethylsulfonyl-5- (trifluoromethyl) -2-pyridyl] propan-1-one (1.5 g, 4.0 mmol) and 5- (trifluoromethyl) -1,3,4-thiadiazole-2-amine (0.71 g, 4.2 mmol) in ethanol (10 mL) and the mixture was heated in a microwave oven to 150 ° C for 30 minutes. The reaction mixture was concentrated in vacuo, the residue diluted with ethyl acetate and saturated aqueous sodium carbonate, the phases were separated, the aqueous phase extracted with ethyl acetate, the combined organic phases washed with water and saturated sodium chloride solution , dried with sodium sulfate and evaporated to dryness. The residue obtained after extractive processing was triturated in n-heptane, the mixture stirred for 10 minutes and left to decant. The supernatant was carefully discarded and the gummy residue purified by chromatography on silica gel (ethyl acetate / cyclohexane 1: 8). The crude product was suspended in diethyl ether, stirred for 2 minutes, filtered and the solid dried in vacuo to give the title compound P3, 3.006 (410 mg) as a solid, mp 146-147 ° C. LCMS (method ZCQ13): 445 (M + H) +, retention time 1.86 min EXAMPLE 4: Preparation of 6- [3-ethylsulfonyl-5- (trifluoromethyl) -2-pyridyl] -2- (trifluoromethyl) imidazo [2,1— b] thiazole (compound P9): Step 1: Preparation of 1- [3-ethylsulfanyl-5- (trifluoromethyl) -2-pyridyl] ethanone

[0209] To a solution of ethanethiol (3.04 ml, 42.26 mmol) in water (180.0 ml) was added sodium hydroxide (1.61 g, 40.25 mmol) and the mixture stirred at room temperature for 1.5 hours. Subsequently, l- [3-chloro-5- (trifluoromethyl) -2-pyridyl] ethanone (9.0 g, 40.25 mmol) and tetrabutylammonium bromide (TBAB, 0.26 g, 0.8 mmol) were added at room temperature. After addition, the reaction temperature was slowly raised to 60 ° C and stirring was continued for 4 hours. The reaction was monitored by TLC and after the reaction was complete, the mixture was diluted with ethyl acetate, washed with water, saturated sodium chloride solution and dried with sodium sulfate. The solvent was removed under reduced pressure to give the desired compound as a solid (8.1 g). LCMS (API 2000 method): 250 (M + H) +, retention time 3.59 min Step 2: Preparation of 2-bromo-1- [3-ethylsulfanyl- 5- (trifluoromethyl) -2-pyridyl] ethanone

[0210] To a solution of 1- [3-ethylsulfanyl-5- (trifluoromethyl) -2-pyridyl] ethanone (8.0 g, 32.09 mmol) in ethyl acetate (80 mL) and chloroform (80 mL) copper (II) bromide CuBr2 (22.83 g, 70.60 mmol) was added and the mixture stirred at 60 ° C for 6 hours. The reaction was monitored by TLC and after the reaction was complete, the mixture was inactivated with ice water and extracted with ethyl acetate. The ethyl acetate phase was washed with saturated sodium chloride solution, dried with sodium sulfate and concentrated to give the impure product. The crude material was purified by column chromatography using hexane to give the desired compound as a solid (4.7 g). LCMS (API 2000 method): 328/330 (M + H) +, retention time 3.78 min Step 3: Preparation of 6- [3-ethylsulfanyl-5- (trifluoromethyl) -2-pyridyl] -2- { trifluoromethyl) imidazo [2,1 - b] thiazole (compound Pll):

[0211] To a stirred solution of 2-bromo-1- [3-ethylsulfanyl-5- (trifluoromethyl) -2-pyridyl] ethanone (1.0 g, 3.05 mmol) in dry 1,4-dioxane ( 10 mL), 5- (trifluoromethyl) thiazol-2-amine (515.5 mg, 3.05 mmol) was added and the reaction mixture was heated at 120 ° C for 12 hours in a sealed tube. The reaction was monitored by TLC and after the reaction was completed, the solvent was evaporated in vacuo to give rise to the impure material. Aqueous sodium hydrogen carbonate NaHCO3 was added and the mixture was extracted with ethyl acetate. The ethyl acetate phase was washed with water, saturated sodium chloride solution, dried with anhydrous sodium sulfate and concentrated to give the impure compound. The impure compound was then purified by preparative HPLC to give the desired compound P1 as a solid (140 mg). LCMS (API 2000 method): 398 (M + H) +, retention time 3.82 min Step 4: Preparation of 6- [3-ethylsulfonyl-5- (trifluoromethyl) -2-pyridyl] -2- (trifluoromethyl) imidazo [2,1- b] thiazole (title compound P9):

[0212] To a stirred solution of 6- [3-ethylsulfanyl-5- (trifluoromethyl) -2-pyridyl] -2- (trifluoromethyl) imidazo [2,1- b] thiazole (210 mg, 0.53 mmol) in dichloromethane (10 ml), meta-chloroperoxybenzoic acid (200 mg, m-CPBA, 1.16 mmol) was added at 10 ° C. After the addition, the reaction temperature was slowly raised to room temperature and stirring was continued for 1 hour. The reaction was monitored by TLC and after completion of the reaction, a saturated aqueous solution of sodium bisulfite NaHSO3 was added. The mixture was stirred for 10 minutes and extracted with dichloromethane. The combined organic layers were washed with saturated aqueous sodium hydrogen carbonate NaHCO3, water and saturated sodium chloride solution, dried with anhydrous sodium sulfate and concentrated to give the impure compound. The crude compound was then washed with pentane and dried to give the desired compound P9 as a solid, mp 178-180 ° C (72 mg). LCMS (API 2000 method): 430 (M + H) +, retention time 3.52 min
[0213] The compounds in the table below were prepared as described in the examples above. Table P1: Examples of compounds of formula (I)




[0214] Other specific examples of compounds of formula (I) are illustrated in Tables 1 to 24 below. Formulation Examples (% = weight percentage)

[0215] Emulsions of any desired concentration can be prepared from such concentrates by diluting with water.


[0216] The solutions are suitable for use in the form of microdroplets.

[0217] The active ingredient is dissolved in dichloromethane, the solution is sprayed on the carrier (s), and the solvent is subsequently evaporated under vacuum.

[0218] Ready-to-use dust is obtained by intimately mixing the carriers and the active ingredient

[0219] The active ingredient is mixed with the additives and the mixture is thoroughly ground in a suitable mill. This gives rise to wettable powders, which can be diluted with water to give suspensions of any desired concentration.

[0220] The active ingredient is mixed with the additives, and the mixture is crushed, moistened with water, extruded, granulated and dried in an air stream. Example F7: Coated granules

[0221] In a mixer, the finely crushed active ingredient is applied evenly to kaolin, which has been moistened with polyethylene glycol. This gives dust-free coated granules. Example F8: Suspension concentrate

[0222] The finely ground active ingredient is mixed intimately with the additives. Suspensions of any desired concentration can be prepared from the resulting suspension concentrate by dilution with water.

[0223] The combination is completely mixed with the adjuvants and the mixture is completely ground in a suitable mill, giving rise to powders that can be used directly for seed treatment. Example F10: Emulsifiable concentrate

[0224] Emulsions of any required dilution, which can be used to protect plants, can be obtained from this concentrate by dilution with water. Example F11: Flowable concentrate for seed treatment

[0225] The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by diluting with water. Using these dilutions, live plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, spilling or immersion.
[0226] The activity of the compositions according to the invention can be increased considerably, and adapted to prevailing circumstances, by adding other insecticidal, acaricidal and / or fungicidal active ingredients. Mixtures of the compounds of formula I with other insecticide, acaricide and / or fungicide active ingredients can also have additional surprising advantages, which can also be described, in a broader sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different stages of development or better behavior during their production, for example during crushing or mixing, during storage or during use.
[0227] Suitable additions to active ingredients here are, for example, representative of the following classes of active ingredients: organophosphate compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids , chlorinated hydrocarbons, acylureas, pyridylmethylene amino derivatives, macrolides, neonicotinoids and preparations of Bacillus thuringiensis.
[0228] 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 24 of the present invention"): an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX, an acaricide selected from the group of substances consisting of acequinocil ([57960-19-7] [CCN]) + TX, fenpyroximate [134098-61-6] [ CCN] + TX, flucitrinate [70124— 77-5] [CCN] + TX, 1,1-bis (4-chlorophenyl) -2-ethoxyethanol (IUPAC name) (910) + TX, hexithiazox [78587-05-0 ] [CCN] + TX, 2,4-dichlorophenyl benzenesulfonate (IUPAC / Chemical Abstracts name) (1059) + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name) (1295) + TX , chlorophenyl and phenyl (IUPAC name) (981) + TX, abamectin (1) + TX, acequinocil (3) + TX, acetoprol [CCN] + TX, acrinatrin (9) + TX, aldicarb (16) + TX, aldoxicarb (863) + TX, alpha-cypermethrin (202) + TX, amidition (870) + TX, amidoflumete [CCN] + TX, amidothioate (872) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, aramite (881) + TX, 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, azocyclotine (46) + TX, nitrogen (889) + TX, benomyl (62) + TX, benoxaphos (alternative name) [CCN] + TX, benzoxide (71) + TX, benzyl benzoate (IUPAC name) [CCN] + TX, biphenazate (74) + TX, bifenthrin (76) + TX, binapacril (907) + TX, brofenvalerate (alternative name) + TX, bromocyclene (918) + TX, bromophos (920) + TX, bromophos -ethyl (921) + TX, bromopropylate (94) + TX, buprofezin (99) + TX, butocarboxy (103) + TX, butoxycarboxy (104) + TX, butylpyridabene (alternative name) + TX, calcium polysulfide (IUPAC name ) (111) + TX, camfeclor (941) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbophenothione (947) + TX, CGA 50'439 (development code) (125) + TX, quinomethionate (126) + TX, clorbenside (959) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorfenapyr (130) + TX, chlorphenethol (968) + TX, chlorfenson (970) + TX, chlorophensulfite (971) + TX, chlorfenvinfos (131) + TX, chlorobenzylate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX , chloropropylate (983) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlortiofos (994) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerines (696 ) + TX, clofentezine (158) + TX, closantel (alternative name) [CCN] + TX, coumafos (174) + TX, crotamitone (alternative name) [CCN] + TX, crotoxifos (1010) + TX, cufranebe (1013 ) + TX, cyantoate (1020) + TX, kyflumetophen [400882-07-7] + TX, cyhalothrin (196) + TX, cyhexatin (199) + TX, cypermethrin (201) + TX, DCPM (1032) + TX, DDT (219) + TX, demefion (1037) + TX, demefion-0 (1037) + TX, demefion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-0 (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S-methyl (224) + TX, demeton-S-methylsulfone (1039) + TX, diafentiuron (226) + TX, dialects (1042) + TX, diazinon (227) + TX, dichlofluanide (230) + TX, dichlorvos (236) + TX, diclifos (alternative name) + TX, dicofol (242) + TX, dicrotophos (243) + TX, dienochlor (1071) + TX, dimefox (1081) + TX, dimetoate (262) + TX, dinactin (alternative name) (653) + TX, dinax (1089) + TX, dinex -diclexin (1089) + TX, dinobuton (269) + TX, dinocape (270) + TX, dinocape-4 [CCN] + TX, dinocape-6 [CCN] + TX, dinocton (1090) + TX, dinopenton (1092 ) + TX, dinosulfone (1097) + TX, dinoterbon (1098) + TX, dioxationa (1102) + TX, diphenylsulfone (IUPAC name) (1103) + TX, disulfiram (alternative name) [CCN] + TX, disulfoton (278 ) + TX, DNOC (282) + TX, dofenapin (1113) + TX, doramectin (alternative name) [CCN] + TX, endosulfan (294) + TX, endotion (1121) + TX, EPN (297) + TX, eprinomectin (alternative name) [CCN] + T X, ethion (309) + TX, ethoate-methyl (1134) + TX, ethoxazole (320) + TX, etrimphos (1142) + TX, phenazaflor (1147) + TX, phenazaquin (328) + TX, phenbutatin oxide ( 330) + TX, phenothiocarb (337) + TX, fenpropatrin (342) + TX, fenpirad (alternative name) + TX, fenpyroximate (345) + TX, fenson (1157) + TX, fentrifanil (1161) + TX, fenvalerate ( 349) + TX, fipronil (354) + TX, fluacripyrim (360) + TX, fluazurone (1166) + TX, flubenzimine (1167) + TX, flucicloxuron (366) + TX, flucitrinate (367) + TX, fluenotyl (1169) ) + TX, flufenoxuron (370) + TX, flumethrin (372) + TX, fluorbenside (1174) + TX, fluvalinate (1184) + TX, EMC 1137 (development code) (1185) + TX, formethanate (405) + TX, formethanate hydrochloride (405) + TX, formotion (1192) + TX, formparanate (1193) + TX, gamma- HCH (430) + TX, gliodine (1205) + TX, halfenprox (424) + TX, heptenophos ( 432) + TX, hexadecyl cyclopropanecarboxylate (lUPAC / Chemical Abstracts name) (1216) + TX, hexitiazox (441) + TX, iodomethane (IUP name AC) (542) + TX, isocarbophos (alternative name) (473) + TX, 0- (methoxyminothiophosphoryl) isopropyl salicylate (IUPAC name) (473) + TX, ivermectin (alternative name) [CCN] + TX, jasmine I (696) + TX, Jasmine II (696) + TX, jodfenfos (1248) + TX, lindane (430) + TX, lufenuron (490) + TX, malation (492) + TX, malonobene (1254) + TX, mecarbam (502) + TX, mefosfolan (1261) + TX, messulfene (alternative name) [CCN] + TX, metacryphs (1266) + TX, metamidophos (527) + TX, metidation (529) + TX, metiocarb (530) + TX, methyl (531) + TX, methyl bromide (537) + TX, metolcarb (550) + TX, mevinfos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (name alternative) [CCN] + TX, mipafox (1293) + TX, monocrotophos (561) + TX, morphotion (1300) + TX, moxidectin (alternative name) [CCN] + TX, nalede (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) + TX, nifluridide (1309) + TX, nicomycins (alternative name) [CCN] + TX, nitrilacarb (1313) + TX, nitrilacarb complex 1: 1 zinc chloride (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, ometoate (594) + TX, oxamyl (602) + TX, oxideprofos (1324) + TX, oxisulfoton (1325) + TX, pp'-DDT (219) + TX, paration (615) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628 ) + TX, phencapton (1330) + TX, fentoate (631) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, fosmet (638) + TX, phosphamidon (639) + TX, foxim (642) + TX, pirimiphos-methyl (652) + TX, polychloroterpenes (traditional name) (1347) + TX, polynactins (alternative name) (653) + TX, proclonol (1350) + TX, profenofos ( 662) + TX, promacil (1354) + TX, propargite (671) + TX, propetamphos (673) + TX, propoxur (678) + TX, protidation (1360) + TX, protoate (1362) + TX, pyrethrin I ( 696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridafention (701) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, quinalphos ( 711) + TX, quintiofós (1381) + TX, R-1492 (development code) (1382) + TX, RA-17 (development code) (1383) + TX, rotenona (722) + TX, scradano (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 (alternative name) [CCN] + TX, sulfluramid (750) + TX, sulfotepe (753) + TX, sulfur (754) + TX, SZI- 121 (development code) (757) + TX, tau-fluvalinate (398) + TX, tebufenpirade (763) + TX, TEPP (1417) + TX, terbam (alternative name) + TX, tetrachlorvinfos (777) + TX, tetradifon (786) + TX, tetranactin (alternative name) (653) + TX, tetrasul (1425) + TX, tiafenox (alternative name) + TX, thiocarboxime (1431) + TX, thiophanox (800) + TX, tiometon (801 ) + TX, thioquinox (1436) + TX, thuringian (alternative name) [CCN] + TX, triamiphos (1441) + TX, triaratene (1443) + TX, tri azofos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, triphenophones (1455) + TX, trinactin (alternative name) (653) + TX, vamidotion (847) + TX, vaniliprol [CCN ] and YI-5302 (compound code) + TX, an algaecide selected from the group of substances consisting of betoxazine [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX , cybutrin [CCN] + TX, diclone (1052) + TX, dichlorophene (232) + TX, endotal (295) + TX, phentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX , quinoclamine (714) + TX, quinonamide (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomato (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, an avicide selected from the group of substances consisting of chloralose (127) + TX, endrine (1122) + TX, fention (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX, a bactericide selected from the group of substances consisting of 1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222) + TX, 4- (quinoxalin-2-ylamino) benzenesulfonamide (IUPAC name ) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX , cresol [CCN] + TX, dichlorophene (232) + TX, dipyrithione (1105) + TX, dodicin (1112) + TX, phenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargafene (alternative name) [CCN ] + TX, kasugamycin (483) + TX, hydrated kasugamycin hydrochloride (483) + TX, bis (d nickel imethyldithiocarbamate (IUPAC name) (1308) + TX, nitrapirin (580) + TX, octylinin (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, hydroxyquinoline-potassium sulfate (446 ) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, keyboard software (766) + TX, and thiomersal (alternative name) [CCN] + TX, a selected biological agent of 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 turingiensis subsp. aizawai (scientific name) (51) + TX, Bacillus turingiensis 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 (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 multi-nuclear 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, a soil sterilizer selected from the group of substances consisting of iodomethane (IUPAC name) (542 ) and methyl bromide (537) + TX, a chemosterilizer selected from the group of substances consisting of afolate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methotepa [CCN] + TX, methyl afolate [CCN ] + TX, morzide [CCN] + TX, penfluron (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [CCN] + TX, tiotepa (alternative name) [CCN] + TX , tretamine (alternative name) [CCN] and uredepa (alternative name) [CCN] + TX, an insect pheromone selected from the group of substances consisting of (E) -dec-5-en-l-yl acetate with (E ) -dec-5-en-l-ol (IUPAC name) (222) + TX, (E) -tridec-4-en-l-yl acetate (IUPAC name) (829) + TX, (E) -6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, (E, Z) -tetradeca-4,10-dien-l-yl acetate (IUPAC name) (779) + TX, (Z) -dodec-7-en-l-yl acetate (IUPAC name) (285) + TX, (Z) -hexadec-ll-enal (IUPAC name) (436) + TX, (Z) -hexadec-ll-en-l-yl acetate (IUPAC name) (437) + TX, (Z) -hexadec-13-en-l1-in-l-ila (IUPAC name) (438) + TX, (Z) -icos-13-en-10-one (IUPAC name) (448) + TX , (Z) - tetradec-7-en-l-al (IUPAC name) (782) + TX, (Z) -tetradec- 9-en-l-ol (IUPAC name) (783) + TX, ( Z) - tetradec-9-en-l-yl (IUPAC name) (784) + TX, (7E, 9Z) -dodeca-7,9-dien-l-yl acetate (IUPAC name) (283) + TX , (9Z, HE) -tetradeca-9,11-dien-l-yl acetate (IUPAC name) (780) + TX, (9Z, 12E) -tetradeca-9,12-dien-l-yl acetate ( IUPAC name) (781) + TX, 14-methyloctadec-l-ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one (IUPAC name) (544) + TX , alf a-mult istriat ina (alternative name) [CCN] + TX, brevicomina (name alternative) [CCN] + TX, codlelure (alternative name) [CCN] + TX, codlemona (alternative name) (167) + TX, cuelure (alternative name) (179) + TX, disparlure (277) + TX, acetate dodec-8-en-l-yl (IUPAC name) (286) + TX, dodec-9-en-l-ila (IUPAC name) (287) + TX, dodeca-8 + TX, 10- dien-l-ila (IUPAC name) (284) + TX, dominicalure (alternative name) [CCN] + TX, ethyl 4-methyloctanoate (IUPAC name) (317) + TX, eugenol (alternative name) [CCN] + TX, frontalina (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 (name alternative) [CCN] + TX, japonilure (alternative name) (481) + TX, lineatin (alternative name) [CCN] + TX, litlure (alternative name) [CCN] + TX, looplure (alternative name) alternative) [CCN] + TX, medlure [CCN] + TX, megatomoic acid (alternative name) [CCN] + TX, methyl eugenol (alternative name) (540) + TX, muscalure (563) + TX, octadeca acetate -2,13-dien-l-ila (IUPAC name) (588) + TX, octadeca-acetate-3,13-dien-l-ila (IUPAC name) (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-ll-en-1-yl acetate (IUPAC name) (785) + TX, trimedlure (839) + TX, trimedlure A (alternative name) (839) + TX, trimedlure Bi (alternative name) ) (839) + TX, trimedlure B2 (alternative name) (839) + TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN] + TX, an insect repellent selected from the group of substances consisting of 2- (octyllium) ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy (polypropylene glycol) (936) + TX, adipate d and dibutyl (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexamide [CCN] + TX, methoxybutyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX, an insecticide selected from the group of substances consisting of momfluorotrin [609346-29-4] + TX, pirafluprol [315208-17-4] + TX, flometoquin [875775-74-9] + TX, flupiradifuron [951659-40 -8] + TX, 1-dichloro-l-nitroethane (lUPAC / Chemical Abstracts name) (1058) + TX, 1,1-dichloro-2,2-bis (4-ethylphenyl) ethane (IUPAC name) (1056) , + TX, 1,2-dichloropropane (lUPAC / Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, l-bromo-2- chloroethane (name lUPAC / Chemical Abstracts) (916) + TX, 2,2,2-trichloro-1- (3,4-dichlorophenyl) ethyl acetate (IUPAC name) (1451) + TX, 2,2- dichlorov inyl, 2-ethylsulfinylethyl methyl (IUPAC name) (1066) + TX, 2- (1,3-dithiolan-2-yl) phenyl (lUPAC / Chemical Abstracts name) (1109) + TX, 2- (thiocyanate) dimethylcarbamate 2-butoxyethoxy) ethyl (name lUPAC / Chemical Abstracts) (935) + TX, 2- (4,5-dimethyl-1,3-dioxolan-2-yl) phenyl (name lUPAC / Chemical Abstracts) (1084) + TX, 2- (4-chloro-3,5-xylyloxy) ethanol (IUPAC name) (986) + TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984) + TX, 2-imidazolidone (IUPAC name) (1225) + TX, 2-isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 2-methyl (prop-2-inyl) aminophenyl methyl (IUPAC name) (1284) + TX, laurate 2-thiocyanatoethyl (IUPAC name) (1433) + TX, 3-bromo-l-chloroprop-l-ene (IUPAC name) (917) + TX, 3-methyl-l-phenylpyrazole-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-oxocyclohex-l- dimethylcarbamate enila (IUPAC name) (1085) + TX, abamectin (1) + TX, Acephate (2) + TX, acetamipride (4) + TX, acetion (alternative name) [CCN] + TX, acetoprol [CCN] + TX, acrinatrine (9) + TX, acrylonitrile (IUPAC name) (861) + TX, alanicarb (15) + TX, aldicarb (16) + TX, aldoxicarb (863) + TX, aldrin (864) + TX, aletrine (17) + TX, alosamidine (alternative name) [CCN] + TX, alixicarb (866) + TX, alpha-cypermethrin (202) + TX, alpha-ecdysone (alternative name) [CCN] + TX, aluminum phosphide (640) + TX, amidition (870) + TX, amidothioate (872) + TX, aminocarb (873 ) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, anabasin (877) + TX, atidation (883) + TX, AVI 382 (compound code) + TX , AZ 60541 (compound code) + TX, azadiractin (alternative name) (41) + TX, azametiphos (42) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, nitrogen (889 ) + TX, Bacillus thuringiensis delta endotoxins (alternative name) (52) + TX, barium hexafluorosilicate (alternative name) [CCN] + TX, barium polysulfide (name lUPAC / Chemical Abstracts) (892) + TX, bartrine [CCN] + TX, Bayer 22/190 (development code) (893) + TX, Bayer 22408 (development code) (894) + TX, bendiocarb (58) + TX , benfuracarb (60) + TX, bensultape (66) + TX, beta-cyfluthrin (194) + TX, beta-cypermethrin (203) + TX, bifenthrin (76) + TX, bioalectrin (78) + TX, S-isomer bioalectrin cyclopentenyl (alternative name) (79) + TX, bioethanometrine [CCN] + TX, biopermetrin (908) + TX, bioresmethrin (80) + TX, bis (2-chloroethyl) ether (IUPAC name) (909) + TX, bistrifluron (83) + TX, borax (86) + TX, brofenvalerate (alternative name) + TX, bromphenven (914) + TX, bromocyclene (918) + TX, bromo-DDT (alternative name) [CCN] + TX , bromophos (920) 4- TX, bromophos-ethyl (921) + TX, bufencarb (924) + TX, buprofezin (99) + TX, butacarb (926) + TX, butatiofos (927) + TX, butocarboxim (103) + TX, butonate (932) + TX, butoxycarboxy (104) + TX, butylpyridabene (alternative name) + TX, cadusafos (109) + TX, calcium arsenate [CCN] + TX, calcium cyanide (444) + TX, calcium polysulfide (IUPAC name) (111) + TX, camfeclor (941) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbon disulfide (lUPAC / Chemical Abstracts name) (945) + TX, carbon tetrachloride (IUPAC name) (946) + TX, carbophenothione (947) + TX, carbosulfan (119) + TX, card (123) + TX, cartap hydrochloride (123) + TX, cevadine (alternative name) (725) + TX, chlorobenzene (960) + TX, chlordane (128) + TX, chlordecone (963) + TX, clordimeform (964 ) + TX, chlordimeform hydrochloride (964) + TX, chlorethoxyphos (129) + TX, chlorfenapyr (130) + TX, chlorfenvinphos (131) + TX, chlorfluazuron (132) + TX, chlorhefos (136) + TX, chloroform [ CCN] + TX, chloropicrin (141) + TX, chlorfoxin (989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorhephos (994) + TX, chromafenozida (150) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerines (696) + TX, cis-resmethrin (alternate name) + TX, cyismetrin (80) + TX, clocitrine (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, coumafos <174) + TX, coumitoate (1006) + TX, crotamitone (alternative name) [CCN] + TX, crotoxifos (1010 ) + TX, crufomato (1011) + TX, cryolite (alternative name) (177) + TX, CS 708 (development code) (1012) + TX, cyanophenphos (1019) + TX, cyanophos (184) + TX, cyantoate (1020) + TX, cyclethrin [CCN] + TX, cycloprotrin (188) + TX, cyfluthrin (193) + TX, cyhalothrin (196) + TX, cypermethrin (201) + TX, cyphenothrin (206) + TX, cyromazine ( 209) + TX, cytoate (alternative name) [CCN] + TX, d-limonene (alternative name) [CCN] + TX, d-tetramethrin (alternative name) (788) + TX, DAEP (1031) + TX, dazomete (216) + TX, DDT (219) + TX, decarbofuran (1034) + TX, deltamethrin (223) + TX, demefion (1037) + TX, demefion-0 (1037) + TX, demefi on-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-0 (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038 ) + TX, demeton-S-methyl (224) + TX, demeton-S-methylsulfone (1039) + TX, diafentiuron (226) + TX, dialiphos (1042) + TX, diamidafos (1044) + TX, diazinon (227 ) + TX, dicapton (1050) + TX, diclofention (1051) + TX, dichlorvos (236) + TX, diclifos (alternative name) + TX, dicresil (alternative name) [CCN] + TX, dicrotofós (243) + TX , dicyclanil (244) + TX, dieldrin (1070) + TX, 5-methylpyrazol-3-yl diethyl phosphate (IUPAC name) (1076) + TX, diflubenzuron (250) + TX, dilor (alternative name) [CCN] + TX, dimeflutrin [CCN] + TX, dimefox (1081) + TX, dimethane (1085) + TX, dimethoate (262) + TX, dimethrin (1083) + TX, dimethylvinfos (265) + TX, dimethylan (1086) + TX, dinax (1089) + TX, dinex-diclexin (1089) + TX, dinoprope (1093) + TX, dinosam (1094) + TX, dinosebe (1095) + TX, dinotefuran (271) + TX, diophenolan (1099) + TX, dioxabenzof os (1100) + TX, dioxacar be (1101) + TX, dioxationa (1102) + TX, disulfoton (278) + TX, dichrophos (1108) + TX, DNOC (282) + TX, doramectin (alternative name) [CCN] + TX, DSP (1115) + TX, ecdysterone (alternative name) [CCN] + TX, El 1642 (development code) (1118) + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, EMPC (1120) + TX, empentrine (292) + TX, endosulfan (294) + TX, endotion (1121) + TX, endrine (1122) + TX, EPBP (1123) + TX, EPN (297) + TX, epophenonane (1124) + TX, eprinomectin (alternative name) [CCN] + TX, es bottled (302) + TX, etafos (alternative name) [CCN] + TX, ethiofencarb (308) + TX, etion (309) + TX, etiprol (310) + TX, etoato-methyl (1134) + TX, etoprofos (312) + TX, ethyl format (IUPAC name) [CCN] + TX, ethyl-DDD (alternative name) (1056) + TX, ethylene dibromide (316) + TX , ethylene dichloride (chemical name) (1136) + TX, ethylene oxide [CCN] + TX, etofenprox (319) + TX, etrimphos (1142) + TX, EXD (1143) + TX, famfur (323) + TX , fenamiphos (326) + TX, fenazaflor (1147) + TX, phenlorphos (1148) + TX, fenetacarb (1149) + TX, fenflutrin (1150) + TX, fenitrotion (335) + TX, fenobucarb (336) + TX, fenoxacrim (1153) + TX, fenoxicarb (340) + TX, phenpiritrin (1155) + TX, fenpropatrin (342) + TX, fenpirad (alternative name) + TX, fensulfotion (1158) + TX, fention (346) + TX, phention-ethyl [CCN] + TX, fenvalerate (349) + TX, fipronil (354) + TX, flonicamide (358) + TX, flubendiamide (No. CAS Reg .: 272451-65-7) + TX, flucofuron (1168) + TX, flucicloxuron (366) + TX, flucitrinate (367) + TX, fluenotyl (1169) + TX, flufenorin [CCN] + TX, flufenoxuron (370) + TX, flufenprox (1171) + TX, flumethrin (372) + TX, fluvalinate (1184) + TX, EMC 1137 (development code) (1185) + TX, fonofos (1191) + TX, formethanate (405 ) + TX, formethanate hydrochloride (405) + TX, formotion (1192) + TX, formparanate (1193) + TX, fosmetilan (1194) + TX, phospirate (1195) + TX, fostiazate (408) + TX, fostietan ( 1196) + TX, furatiocarb (412) + TX, furetrin (1200) + TX, gamma-cyhalothrin (197) + TX, gamma-HCH (430) + TX, guazatin (422) + TX, guazatin acetates (422) + TX, GY-81 (development code) (423) + TX, halfenprox (424) + TX, halofenozide (425) + TX, HCH (430) + TX, HEOD (1070) + TX, heptachlor (1211) + TX, heptenophos (432) + TX, heterophos [CCN] + TX, hexaflumuron (439) + TX, HHDN (864) + TX, hydramethylnon (443) + TX, hydrogen cyanide (444) + TX, hydroprene (445) + TX, hiquincarb (1223) + TX, imidacloprid (458) + TX, imiprotrine (460) + TX, indoxacarb (465) + TX, iodomethane (IUPAC name) (542) + TX, IPSP (1229) + TX, isazophos (1231) + TX, isocarbophos (alternative name) (473) + TX, isodrine (1235) + TX, isophenphos (1236) + TX, isolane (1237) + TX, isoprocarb (472) + TX, 0- (methoxyminothiophosphoryl) isopropyl salicylate (IUPAC name) (473) + TX, isoprothiolane (474) + TX, isothioate (1244) + TX, isoxation (480) + TX, ivermectin (alternative name) [CCN] + TX, Jasmine I (696) + TX, Jasmine II (696) + TX, iodphenphen (1248) + TX, juvenile hormone I (alternative name) [CCN] + TX, juvenile hormone II (alternative name) [CCN] + TX, juvenile hormone III (alternative name) [CCN ] + TX, kelevan (1249) + TX, quinoprene (484) + TX, lambda-cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepimectin [CCN] + TX, leptophos (1250) + TX, lindane (430) + TX, lyrimphos (1251) + TX, lufenuron (490) + TX, litidation (1253) + TX, m-cumenyl methylcarbamate (name I UPAC) (1014) + TX, magnesium phosphide (IUPAC name) (640) + TX, malation (492) + TX, malonobene (1254) + TX, mazidox (1255) + TX, mecarbam (502) + TX, mecarfon (1258) + TX, menazone (1260) + TX, mefosfolan (1261) + TX, mercury chloride (513) + TX, mosulfenfos (1263) + TX, metafumizona [CCN] + TX, metam (519) + TX, metam-potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methacrifos (1266) + TX, metamidophos (527) + TX, methanesulfonyl fluoride (name lUPAC / Chemical Abstracts) (1268) + TX, metidation (529) + TX, metiocarb (530) + TX, metocrotophos (1273) + TX, methomyl (531) + TX, methoprene (532) + TX, methoquin-butyl (1276) + TX, methotrine (alternative name) ) (533) + TX, methoxychloride (534) + TX, methoxyfenozide (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methylchloroform (alternative name) [CCN] + TX, methylene chloride [CCN] + TX, metoflutrin [CCN] + TX, metolcarb (550) + TX, methoxyzone (1288) + TX, mevinfos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, mirex (1294) + TX, monocrotofos (561) + TX, morfotion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naphthalophos (alternative name) [CCN] + TX, nalede (567) + TX, naphthalene (lUPAC / 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, nitenpiram (579) + TX , nitiazine (1311) + TX, nitrilacarb (1313) + TX, nitrilacarb complex 1: 1 zinc chloride (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, nornicotine (traditional name) (1319) + TX, novaluron (585) + TX, noviflumuron (586) + TX, 0-5-dichloro-4-iodophenyl and O-ethyl (IUPAC name) (1057) + TX, O, O-diethyl and 0-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate (IUPAC name) (1074) + TX, O, O-diethyl and 0-6-methyl phosphorothioate -2-propylpyrimidin-4-yl (IUPAC name) (1075) + TX, 0.0, O ', 0'-tetrapropyl dithiopyrophosphate (IUPAC name) (1424) + TX, oleic acid (IUPAC name) (593 ) + TX, ometoate (594) + TX, oxamyl (602) + TX, oxidemeton-methyl (609) + TX, oxideprofos (1324) + TX, oxisulfoton (1325) + TX, pp'-DDT (219) + TX , para-dichlorobenzene [CCN] + TX, paration (615) + TX, paration-methyl (616) + TX, penfluron (alternative name) [CCN] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (name TUPAC ) (623) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, PH 60-38 (development code) (1328) + TX, phencapton (1330) + TX, phenothrin (630) + TX, phentoate (631) + TX, phorate (636) + TX, phosalone (637) + TX, phospholan (1338) + TX, fosmet (638) + TX, phosnichlor (1339) + TX, phosphamidon ( 639) + TX, phosphine (TUPAC name) (640) + TX, foxim (642) + TX, foxim-methyl (1340) + TX, pyrimetafos (1344) + TX, pirimicarb (651) + TX, pyrimiphos-ethyl ( 1345) + TX, pirimiphos-methyl (652) + TX, polychlorinated cyclopentadiene isomers (TUPAC name) (1346) + TX, polychlorinated terpenes (traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, pralethrin (655) + TX, precocene I (alternative name) [CCN] + TX, precocene II (alternative name) [CCN] + TX, precocene ITT (alternative name) [CCN] + TX, primidofos (1349) + TX, profenofos (662) + TX, proflutrin [CCN] + TX, promacil (1354) + TX, promecarb (1355) + TX, propafos (1356) + TX, propetamfos (673) + TX, propoxur (678) + TX, protidation (1360) + TX , protiophos (686) + TX, protoate (1362) + TX, protrifenbut [CCN] + TX, pyrometrozine (688) + TX, pyraclofes (689) + TX, pyrazophos (693) + TX, pyrethymine (1367) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridalil (700) + TX, pyridafention (701) + TX, pyrimidifen (706) + TX , pyrimitate (1370) + TX, pyriproxifen (708) + TX, quássia (alternative name) [CCN] + TX, quinalfos (711) + TX, quina lfos-methyl (1376) + TX, quinotion (1380) + TX, quintiofós (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, ryanodine (traditional name) (1387) + TX, sabadila (alternative name) (725) + TX, scradano (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 (name lUPAC / Chemical Abstracts) (1399) + TX, sodium hexafluorosilicate ( 1400) + TX, sodium pentachlorophenoxide (623) + TX, sodium selenate (IUPAC name) (1401) + TX, sodium thiocyanate sodium [CCN] + TX, sofamide (1402) + TX, spinosad (737) + TX, spiromesifene (739) + TX, spirotetramat [CCN] + TX, sulcofuron (746) + TX, sulcofuron-sodium (746) + TX , sulfluramid (750) + TX, sulfotepe (753) + TX, sulfuryl fluoride (756) + TX, sulprofos (1408) + TX, tar oils (alternative name) (758) + TX, tau-fluvalinate (398) + TX, tazimcarb (1412) + TX, TDE (1414) + TX, tebufenozide (762) + TX, tebufenpirade (763) + TX, tebupirimfos (764) + TX, tef lubenzuron (768) + TX, teflutrin (769) + TX, temefos (770) + TX, TEPP (1417) + TX, teralethrin (1418) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachloroethane [CCN] + TX, tetrachlorvinfos (777) + TX, tetramethrin (787) + TX, theta-cypermethrin (204) + TX, thiaclopride (791) + TX, thiafenox (alternative name) + TX, thiamethoxam (792) + TX, ticrofos (1428) + TX, thiocarboxime ( 1431) + TX, thiocyclam (798) + TX, thiocyclohydrogenoxalate (798) + TX, thiodicarb (799) + TX, thiophanox (800) + TX, tiometon (801) + T X, thionazine (1434) + TX, thiosultap (803) + TX, thiosultap-sodium (803) + TX, thuringensin (alternative name) [CCN] + TX, tolfenpirade (809) + TX, tralometrine (812) + TX, transflutrin (813) + TX, transpermetrin (1440) + TX, triamiphos (1441) + TX, triazamate (818) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorphon (824) + TX, triclormetafos-3 (alternative name) [CCN] + TX, trichloronat (1452) + TX, triphenophos (1455) + TX, triflumuron (835) + TX, trimetacarb (840) + TX, triprene (1459) + TX, vamidotion ( 847) + TX, vaniliprol [CCN] + TX, veratridine (alternative name) (725) + TX, veratrine (alternative name) (725) + TX, XMC (853) + TX, xylylcarb (854) + TX, YI- 5302 (compound code) + TX, zeta-cypermethrin (205) + TX, zetamethrin (name zolaprofos (1469) and ZXI 8901 (development code) (858) + TX, cyantraniliprole [736994-63-19] + TX, chlorantraniliprole [500008-45-7] + TX, cyclaniliprol [1031756-98-5] + TX, tetraniliprol [1229654-66-3] + TX, guadipir (d written in W02010 / 060231) + TX, cicloxapride (described in W02005 / 077934) + TX, cyienopyraphene [560121-52- 0] + TX, cyphlumetofen [400882-07-7] + TX, pyrifluquinazon [337458-27-2] + TX, espinetoram [187166-40-1 + 187166-15-0] + TX, spirotetramat [203313-25-1] + TX, sulfoxaflor [946578-00-3] + TX, flufiprol [704886-18-0] + TX, meperflutrin [915288-13-0] + TX, tetramethylflutrin [84937- 88-2] + TX and a compound of formula Bl
with the common name triflumezopirim (disclosed in WO 2012/092115) + TX; a molluscicide selected from the group of substances consisting of bis (tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloetocarb (999) + TX, acetoarsenite copper [CCN] + TX, copper sulphate (172) + TX, fentin (347) + TX, ferric phosphate (IUPAC name) (352) + TX, metalldehyde (518) + TX, metiocarb (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 [394730-71-3] + TX, a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, 1,2-dibromo-3-chloropropane (name lUPAC / Chemical Abstracts) (1045) + TX, 1,2-dichloropropane (lUPAC / Chemical Abstracts name) (1062) + TX , 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide (name lUPAC / Chemical Abstracts ) (1065) + TX, 3- (4-chlorophenyl) -5-methylrodanin (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1, 3,5-thiadiazinan-3-ylacetic acid (name IUPAC) (1286) + TX, 6-isopentenylaminopurine (alternative name) (210) + TX, abamectin (1) + TX, acetoprol [CCN] + TX, alanicarb (15) + TX, aldicarb (16) + TX, aldoxicarb (863) + TX, AZ 60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridabene (alternative name) + TX, cadusafós (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbosulfan (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, cloetocarb (999) + TX, cytokinins (alternative name) (210) + TX, dazomete (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafós (1044) + TX, diclofention (1051) + TX, diclifós (alternative name) + TX, dimetoate (262) + TX, sleep emamectin benzoate ectin (291) + TX, eprinomectin (alternative name) [CCN] + TX, etoprofos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fenpirad (alternative name) + TX, fensulfotion (1158) + TX, fostiazato (408) + TX, fostietano (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 (alternative name) (519) + TX, metam-sodium (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, composition of Myrothecium verrucaria (alternative name) (565) + TX, NC-184 (compound code ) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosfocarb [CCN] + TX, seb ufós (alternative name) + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) + TX, terbam (alternative name) + TX, terbufós (773) + TX, tetrachlorothiophene (lUPAC / Chemical Abstracts name) ( 1422) + TX, thiafenox (alternative name) + TX, thionazine (1434) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, xylenols [CCN] + TX, YI-5302 (compound code) and zeatin (alternative name) (210) + TX, fluensulfone [318290-98-1] + TX, a nitrification inhibitor selected from the group of substances consisting of potassium ethyl xanthate [CCN] and nitrapirin (580) + TX, an activator plants selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinansis extract (alternative name) (720) + TX, a rodenticide selected from group of substances consisting of 2-isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 4- (quinoxalin-2-ylamino) benzenesulfonamide (IUPAC name) (748) + TX, alpha a-hydrochloride ina [CCN] + TX, aluminum phosphide (640) + TX, antu (880) + TX, arsenious 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 I: ioo4) + TX, coumafuril (1005) + TX, coumatetralil (175) + TX, crimidine (1009) + TX, difenacoum (246) + TX, diphthialone (249) + TX, diphacinone (273) + TX, ergocalciferol (301) + TX, flocoumafene (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, pindona (1341) + TX, potassium arsenite o [CCN] + TX, pyrinuron (1371) + TX, sciliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851) and zinc phosphide (640) + TX, a synergist selected from the group of substances consisting of 2- (2-butoxyethoxy) ethyl piperonylate ( IUPAC name) (934) + TX, 5- (1,3-benzodioxol-5-yl) -3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol 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 (development code) (724) + TX, sesamex (1393) + TX, sesasmolina (1394) and sulfoxide (1406) + TX, an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171) + TX, diazin on (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatin (422) + TX, guazatin acetates (422) + TX, metiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, take out (804) + TX, trimetacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX, a virucide selected from the group of substances consisting of imanine (alternative name) [CCN ] and ribavirin (alternative name) [CCN] + TX, a wound protector selected from the group of substances consisting of mercuric oxide (512) + TX, octyline (590) and thiophanate-methyl (802) + TX, 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, diphenoconazole [119446-68-3] + TX, diniconazole [83657-24-3] + TX, epoxiconazole [106325-08-0] + TX, fenbuconazole [114369-43- 6] + TX, fluquinconazole [136426-54-5 ] + TX, flusilazole [85509-19-9] + TX, flutriafol [76674-21-0] + TX, hexaconazole [79983- 71-4] + TX, imazalil [35554-44-0] + TX, imibenconazole [86598-92-7] + TX, ipconazole [125225- 28-7] + TX, metconazole [125116-23-6] + TX , miclobutanil [88671-89-0] + TX, pefurazoate [101903-30-4] + TX, penconazole [66246-88-6] + TX, protioconazole [178928-70-6] + TX, pyrifenox [88283-41 -4] + TX, prochloraz [67747-09-5] + TX, propiconazole [60207-90-1] + TX, simeconazole [149508-90-7] + TX, tebuconazole [107534-96-3] + TX, tetraconazole [112281-77-3] + TX, triadimefon [43121-43-3] + 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, bupirimate [41483-43-6] + TX, dimethyrimol [5221-53-4] + TX, ethirimol [23947-60-6] + TX, dodemorph [1593-77-7] + TX, phenpropidine [67306-00-7] + TX, fenpropimorph [67564-91-4 ] + TX, spiroxamine [118134-30-8] + TX, tridemorph [81412-43-3] + TX, cyprodinil [121552-61-2] + TX, mepanipirim [110235-47-7] + TX, pyrimethanil [ 53112-28-0] + TX, fenpiclonil [74738-17-3] + TX, fludioxonil [131341-86-1] + TX, benalaxyl [71626-11-4] + TX, furalaxil [57646-30-7] + TX, metalaxyl [57837-19- 1] + TX, R-metalaxyl [70630-17-0] + TX, ofurace [58810-48-3] + TX, oxadixyl [77732-09-3] + TX, benomyl [17804-35-2] + TX , carbendazim [10605-21-7] + TX, debacarb [62732-91-6] + TX, fuberidazole [3878-19-1] + TX, thiabendazole [148-79-8] + TX, clozolinate [84332-86 -5] + TX, diclozoline [24201-58-9] + TX, iprodione [36734-19-7] + TX, myclozoline [54864-61-8] + TX, procymidone [32809-16-8] + TX, vinclozoline [50471- 44-8] + TX, boscalide [188425-85-6] + TX, carboxine [5234-68-4] + TX, fenfuram [24691-80-3] + TX, flutolanil [66332-96- 5] + TX, mepronil [55814-41-0] + TX, oxycarboxine [5259-88-1] + TX, pentiopyrade [183675-82-3] + TX, tifluzamide [130000-40-7] + TX, guazatin [108173-90-6] + TX, dodine [2439-10-3] [112-65-2] (free base) + TX, iminoctadine [13516-27-3] + TX, azoxystrobin [131860-33-8 ] + TX, mandestrobin [173662-97- 0] + TX, dimoxistro bina [149961-52-4] + TX, enostroburin {Proc. BCPC, Int. Congr., Glasgow, 2003, 1, 93} + TX, fluoxastrobin [361377-29-9] + TX, cresoxim-methyl [143390-89-0] + TX, metominostrobin [133408-50-1] + TX, trifloxystrobin [141517-21-7] + TX, orizastrobin [248593-16-0] + TX, picoxystrobin [117428- 22-5] + TX, pyraclostrobin [175013-18-0] + TX, ferbam [14484 -64-1] + TX, 3- [5- (4-chlorophenyl) -2,3-dimethyl-3-isoxazolidinyl] pyridine (SYP-Z048), mancozeb [8018-01-7] + TX, manebe [12427 -38-2] + TX, entered [9006-42-2] + TX, propineb [12071-83-9] + TX, remove [137-26-8] + TX, zineb [12122-67-7] + TX, ziram [137-30-4] + TX, captafol [2425-06-1] + TX, captana [133-06-2] + TX, diclofluanide [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, maneuver [53988-93- 5] + TX, copper oxine [10380-28-6] + TX, dinocape [13 1-72-6] + TX, nitrotal-isopropyl [10552-74-6] + TX, edifenfós [17109- 49-8] + TX, iprobenfós [26087-47-8] + TX, isoprotiolan [50512-35- 1] + TX, fosdifeno [36519-00-3] + TX, pyrazophos [13457-18-6] + TX, tolclofós-methyl [57018-04- 9] + TX, acibenzolar-S-methyl [135158-54- 2] + TX, anilazine [101-05-3] + TX, bentiavalicarb [413615-35-7] + TX, blasticidin-S [2079-00-7] + TX, quinomethionate [2439-01-2] + TX , chloronebe [2675-77-6] + TX, chlorothalonil [1897-45-6] + TX, cyflufenamide [180409-60-3] + TX, cymoxanil [57966-95-7] + TX, diclone [117-80 -6] + TX, diclocimet [139920-32-4] + TX, diclomezin [62865-36-5] + TX, dicloran [99-30-9] + TX, dietofencarb [87130-20-9] + TX, dimetomorfe [110488-70-5] + TX, SYP-LI90 (Flumorf) [211867-47-9] + TX, dithianon [3347-22-6] + TX, etaboxam [162650-77-3] + TX, etridiazole [2593-15-9] + TX, famoxadone [131807-57-3] + TX, phenamidone [161326-34-7] + TX, phenoxanil [115852-48- 7] + TX, fentine [668-34-8 ] + TX, ferimzone [89269-64- 7] + TX, fluazinam [79622 -59-6] + TX, fluopicolide [239110-15-7] + TX, flusulfamide [106917-52-6] + TX, phenhexamide [126833-17-8] + TX, phosethyl aluminum [39148- 24-8 ] + TX, himexazole [10004-44-1] + TX, iprovalicarb [140923-17-7] + TX, IKF-916 (Cyzofamide) [120116-88-3] + TX, kasugamycin [6980-18-3] + TX, metasulfocarb [66952-49-6] + TX, metrafenone [220899-03-6] + TX, pencicuron [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, pyroquinone [57369-32-1] + TX, quinoxifene [124495-18-7] + TX, quintozene [82-68-8] + TX, sulfur [7704-34-9] + TX, thiadinyl [223580-51-6] + TX, triazoxide [72459- 58-6] + TX, tricyclazole [41814- 78-2] + TX, triforin [26644-46-2] + TX, validamycin [37248-47-8] + TX, zoxamide (RH7281) [156052-68-5 ] + TX, mandipropamide [374726-62-2] + TX, and SDHI inhibitors selected from the group consisting of: penflufen ([494793-67-8], US 7538073 (N- [2- (l, 3 - dimethylbu tyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazolo-4-carboxamide) + TX, furamethyr ([123572-88-3] (5-chloro-N- (1,3-dihydro-1 , 1,3-trimethyl-4-isobenzofuranyl) -1,3-dimethyl-1H-pyrazolo-4-carboxamide) + TX, pentiopirad (US 5747518, [183675-82-3], (N- [2- (1 , 3-dimethylbutyl) -3-thienyl] -1-methyl- 3- (trifluoromethyl) -1H-pyrazolo-4-carboxamide) + TX, bixafen (US 7329633, [581809-46-3], (N- (3 ', 4'-dichloro-5-fluoro [1,1' -bi phenyl] -2-yl) -3- (difluoromethyl) -1-methyl-1H-pyrazolo-4-carboxamide) + TX, isopyrazam (US 7598395, [881685-58-1] (mixture of 2 isomersyn 3- (difluoromethyl) - 1-methyl-N- [(IRS, 4SR, 9RS) -1,2,3,4-tetrahydro-9-isopropyl-l , 4-methanonaphthalen-5-yl] pyrazolo-4-carboxamide and 2 anti 3- (difluoromethyl) -1-methyl-N - [(IRS, 4SR, 9SR) -1,2,3,4-tetrahydro-9 isomers -isopropyl-1,4-methanonaphthalen-5-yl] pyrazolo-4-carboxamide) + TX, silkxane (EP 1480955B1, [874967-67-6] (mixture of 2 cis 2 'isomers - [(IRS, 2RS) - 1,1'-bicycloprop-2-yl] -3- (difluoromethyl) -1-methylpyrazolo-4-carboxanilide and 2 t isomers rans 2 [(IRS, 2SR) -1,1'-bicycloprop-2-yl] -3- (difluoromethyl) -1-methylpyrazole-4-carboxanilide) + TX, fluxpyroxad (US 8008232, [907204-31-3] (3- (difluoromethyl) - 1-methyl-N- (3 ', 4', 5'-trifluoro [1,1'-biphenyl] -2-yl) -1H-pyrazolo-4-carboxamide) + TX, solatenol (WO 2007/048556 (3-difluoromethyl-1-methyl-1H-pyrazolo-4-carboxylic acid (9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methane-naphthalen-5-yl) - amide,) + TX, the compound 3- (difluoromethyl) -N-methoxy-1-methyl-N- [1-methyl-2- (2,4,6-trichlorophenyl) ethyl] pyrazole-4-carboxamide (described in WO 2010/063700) + TX, tifluzamide (US 5045554, [130000-4 0-7] (N- [2,6-dibromo-4- (trifluoromethoxy) phenyl] -2-methyl-4- (trifluoromethyl) -5 - thiazolocarboxamide) + TX, boscalid (US 5589493, [188425-85- 6 (2-chloro-N- (4'-chloro [1,1'-biphenyl] -2-yl) -3-pyridinecarboxamide) + TX, oxycarboxin ([5259-88-1] (4,4-5,6-dihydro-2-methyl-N-phenyl-1,4-oxatiin-3-carboxamide) + TX, carboxin ([5234-68- 4] (5,6-dihydro-2-methyl-N-phenyl-1,4-oxatiin-3-carboxamide) + TX, fluopyram (US 7 572818, [658066-35-4], (N- [2- [3-chloro-5- (trifluoromethyl) -2-pyridinyl] ethyl] -2- (trifluoromethyl) benzamide) + TX, flutolanil ([24691-80 -3], (2-methyl-N-phenyl-3-furancarboxamide, fenfuram), US 4093743, CA Reg. No. 66332-96-5 (N- [3- (1-methylethoxy) phenyl] -2- ( trifluoromethyl) benzamide) + TX, mepronil ([55814-41-0], (2-methyl-N- [3- (1-methylethoxy) phenyl] benzamide) + TX and benodanyl ([15310-01-7], ( 2-iodo-N-phenylbenzamide) + TX; and the compounds [(3S, 47 , 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-ll-oxo-9- (3-pyridinyl) -2H, HHnafto [2,1-b] pyran [3,4-e] piran- 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 and 4-oxo-4- [(2 -phenylethyl) amino] -butyric (disclosed in WO 2010137677) + TX.
[0229] References in parentheses before the active ingredients, eg, [3878-19-1] refer to the Chemical Abstracts Registration Number. The mixing partners described above are known. When active ingredients are included in "The Pesticide Manual" - The World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described there under the entry number given in curly brackets above in this document for the particular compound; for example, the compound "abamectin" is described under the entry number (1). When "[CCN]" is added above in this document to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessed over the internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2013]; for example, the compound "acetoprol" is described at http://www.alanwood.net/pesticides/acetoprole.html.
[0230] In this document, most of the active ingredients described above are referred to by a so-called "common name", the relevant "common name ISO" or another "common name" that is used in particular cases. If the designation is not a "common name", the nature of the alternative designation used is given in parentheses for the particular compound; in this case, the IUPAC name, the Chemical Abstracts / IUPAC name, a "chemical name", a "traditional name", a "compound name" or a "development code" are used or, if neither of these designations nor a "common name" is used, an "alternative name" is used.
[0231] The active ingredient mixture of the compounds of formula I selected from Tables 1 to 24 with active ingredients described above comprises a compound selected from Tables 1 to 24 and an active ingredient as described above, preferably at a mixing 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 from 5: 1 and 1: 5, with a preference being given to a ratio of 2: 1 to 1: 2, and a ratio of 4: 1 to 2: 1 being equally preferred, above all a ratio of 1: 1, or 5: 1, or 5: 2, or 5: 3, or 5: 4, or 4: 1, or 4: 2, or 4: 3, or 3: 1, or 3: 2, or 2: 1, or 1: 5, or 2: 5, or 3: 5, or 4: 5, or 1: 4, or 2: 4, or 3: 4, or 1: 3, or 2: 3, or 1: 2, or 1: 600, or 1: 300, or 1: 150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1: 6000, or 1: 3000, or 1: 1500, or 1: 350, or 2: 350, or 4: 350, or 1: 750, or 2: 750, or 4: 750. It is understood that such mixing ratios include, on the one hand, weight ratios and also, on the other hand, molar ratios.
[0232] Mixtures as described above can be used in a method for pest control, which comprises applying a composition comprising a mixture as described above to pests or their environment, with the exception of a method for treating the human body or by surgery or therapy, and diagnostic methods practiced on the human or animal body.
[0233] Mixtures comprising a compound of formula I selected from Tables 1 to 24 and one or more active ingredients as described above, can be applied, for example, in a simple "ready-mix" form, in a spray mixture combination prepared from separate formulations of the components of the single active ingredients, such as a "tank mix", and in a combined use of the individual active ingredients when applied sequentially, that is one after the other in a relatively short period of time , such as a few hours or days. The order of application of the compounds of formula I selected from Tables 1 to 1- & 24 and the active ingredients described above is not essential to the practice of the present invention. Biological Examples: Example Bl: Activity against Spodoptera littoralis (Egyptian cotton curuquerê) (larvicide, residual contact / feeding activity, preventive)
[0234] Agar cotton sheet discs were placed on a 24-well microtiter plate and sprayed with test solutions. After drying, the leaf discs were infested with 5 LI larvae. The samples were checked for mortality, repellent effect, feeding behavior, and growth regulation 3 days after treatment (DAT).
[0235] In this test, compounds P2, P3, P4, P5, P7, P8, P9 and PIO exhibited an activity greater than 80% at a concentration of 400ppm. Example B2: Activity against Spodoptera littoralis (Egyptian cotton curuquerê) (systemic activity):
[0236] The test compounds were applied by pipette to 24-well plates and mixed with agar. Lettuce seeds were placed on the agar and the multiple well plate was closed with another plate that also contains agar. After 7 days, the roots absorbed the compost and the lettuce grew on the cover plate. The lettuce leaves were then cut to the cover plate. Spodoptera eggs were pipetted with a plastic stencil onto a moist gel staining paper, and the plate was closed with it. The samples are checked for mortality, repellent effect, nutrition behavior, and growth regulation 5 days after infestation.
[0237] In this test, compounds P2 and P8 exhibited at least 80% activity at a concentration of 12.5 ppm. Example B3: Activity against Plutella xylostella (Crucifer moth) (larvicide, residual contact / feeding activity, preventive)
[0238] A 24-well microtiter plate (MTP) was treated with artificial diet, with test solutions by pipetting. After drying, the MTPs were infested with L2 larvae (10-15 per well). After an incubation period of 5 days, the samples are checked for larval mortality, anti-food regulation and growth.
[0239] In this test, compounds P2, P3, P4, P5, P7, P8 and P9 exhibited an activity greater than 80% at a concentration of 400ppm. Example B4: Activity against Diabrotica balteata (Corn rootworm) (L2 larvae in more shoots, feed / contact, preventive)
[0240] Too many sprouts, placed on an agar layer in 24-well microtiter plates, were treated with spray test solutions. After drying, MTPs were infested with L2 larvae (6-10 per well). After an incubation period of 5 days, the samples were checked for larval mortality and growth regulation.
[0241] In this test, compounds P2, P3, P4, P7, P8 and P9 exhibited an activity greater than 80% at a concentration of 400ppm. Example B5: Activity against Myzus persicae (green aphid) (residual / preventive feeding / contact activity), mixed population
[0242] Sunflower leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test solutions. After drying, the leaf discs were infested with a population of aphids of mixed ages. After an incubation period of 6 DAT, the samples were checked for mortality and special effects (eg, phytotoxicity).
[0243] In this test, compounds P2, P3, P5, P7, P8 and P9 exhibited an activity greater than 80% at a concentration of 400ppm. Example B6: Activity against Myzus persicae (green aphid) (Sachet test of feeding activity), mixed population
[0244] The test compounds were applied by pipette to 24-well plates and mixed with Sucrose solution. The plates were closed with a stretched Parafilm. A plastic stencil with 24 holes is placed over the plate, and infested pea seedlings were placed directly on Parafilm. The infested plate is closed with gel blotting paper and another plastic stencil and then turned upside down. Five days after infestation, the samples were checked for mortality. Application rate: 12.5 ppm.
[0245] In this test, compounds P2 and P3 exhibited an activity of at least 80% at a concentration of 12.5 ppm. Example B7: Activity against Myzus persicae (green aphid) (systemic / feeding activity, curative), mixed population
[0246] Pea seedling roots infested with a population of aphids of different ages were placed directly in the test solutions. 6 days after introduction, the samples were checked for mortality and special effects on the plant.
[0247] In this test, compounds P2 and P5 exhibited an activity of at least 80% at a concentration of 24ppm. Example B8: Activity against Euschistus heros (Neotropical Stink Bug)
[0248] Soy leaves were sprayed on agar, in 24-well microtiter plates, with aqueous test solutions prepared from stock solutions in DMSO at 10'000 ppm. After drying, the leaves were infested with N-2 nymphs. The samples were evaluated for mortality 5 days after infestation.
[0249] In this test, compounds P7 and P8 exhibited an activity greater than 80% at a concentration of 400ppm. Example B9: Activity against Aedes aegypti (Yellow fever mosquito):
[0250] Test solutions, at an application rate of 200ppm in ethanol, were applied to 12 well tissue culture plates. As soon as the deposits were dry, five adult Aedes aegypti females aged two to five days old were added to each well, and sustained with a 10% sucrose solution on a raw cotton plug. Inactivation was assessed one hour after introduction, and mortality was assessed at 24 and 48 hours after introduction.
[0251] The following compounds provided at least 80% control of Aedes aegypti after 48h: P2, P3, P4 and P8. Example B10: Activity against Anopheles stephensi (Indian malaria mosquito):
[0252] Test solutions, at an application rate of 200ppm in ethanol, were applied to 12 well tissue culture plates. As soon as the deposits were dry, five adult female Anopheles stephensi aged two to five days were added to each well, and sustained with a 10% sucrose solution on a raw cotton plug. Inactivation was assessed one hour after introduction, and mortality was assessed at 24 and 48 hours after introduction.
[0253] For example, the following compound provided at least 80% control of nopheles stephensi after 48h: P2.

权利要求:
Claims (13)
[0001]
1. Compound of formula I
[0002]
A compound of formula I according to claim 1, characterized in that it is represented by the compounds of formulas 1-1 to 1-8
[0003]
Compound of formula I according to claim 1, characterized in that it is represented by compounds of formula I-1
[0004]
Compound of formula I according to claim 1, characterized in that it is represented by compounds of formula I-2
[0005]
A compound of formula I according to claim 1, characterized in that it is represented by the compounds of formula I-3
[0006]
6. Compound of formula I according to claim 1, characterized in that it is represented by compounds of formula I-4
[0007]
Compound of formula I according to claim 1, characterized in that it is represented by compounds of formula I-5
[0008]
A compound of formula I according to claim 1, characterized in that it is represented by compounds of formula I-6
[0009]
Compound of formula I according to claim 1, characterized in that it is represented by compounds of formula I-7
[0010]
Compound of formula I according to claim 1, characterized in that it is represented by compounds of formula I-8
[0011]
An insecticidal, acaricidal, nematicidal or molluscicidal composition characterized by an insecticidal, acaricidal, nematicidal or molluscicidal effective amount of a compound of formula (I) according to claim 1, and a vehicle or diluent suitable for the same.
[0012]
12. A method for combating and controlling pests, characterized in that it comprises applying a pesticidally effective amount of a compound of formula I according to claim 1, or a composition comprising such a compound, to a pest, to the location of a pest, or to a plant susceptible to attack by a pest.
[0013]
13. A method to combat and control pests, characterized by the fact that it comprises applying a pesticidal composition according to claim 11 to a pest, a pest site, or a plant susceptible to attack by a pest.

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法律状态:
2019-05-28| B06T| Formal requirements before examination|

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2020-06-23| B09A| Decision: intention to grant|

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2020-09-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/12/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

EP13198772|2013-12-20|

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EP13198772.9|2013-12-20|

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PCT/EP2014/078734|WO2015091945A1|2013-12-20|2014-12-19|Pesticidally active substituted 5,5-bicyclic heterocycles with sulphur containing substituents|

---