pesticide-active heterocyclic derivatives with sulfur-containing substituents, pesticide composition

专利摘要:
HETEROCYCLIC DERIVATIVES ACTIVE FROM THE PESTICIDE POINT OF VIEW WITH SUBSTITUTES CONTAINING SULFUR, PESTICIDE COMPOSITION, METHOD FOR PEST CONTROL AND METHOD FOR PROTECTING PLANT MATERIAL OF THE ATTACK PLANTS IN ITS PLANTS (I) are as defined in claim 1, and the salts, stereoisomers, enantiomers, tautomers and agrochemically acceptable Noxides of these compounds can be used as insecticides and can be prepared in a manner known per se.
公开号:BR112017003366B1
申请号:R112017003366-6
申请日:2015-08-18
公开日:2020-12-08
发明作者:André Stoller；André Jeanguenat；Andrew Edmunds；Pierre Joseph Marcel Jung；Daniel EMERY；Michel Muehlebach；Peter Renold
申请人:Syngenta Participations Ag；
IPC主号:

专利说明:

[0001] The present invention relates to heterocyclic derivatives active in pesticidal terms, in particular active in insecticidal suits, containing sulfur substituents, with intermediates for the preparation of these compounds, with compositions comprising these compounds, and with their use for pest control animals (including arthropods and in particular insects or representatives of the order Acarina).
[0002] Heterocyclic compounds with pesticidal action are known and described, for example, in WO 2012/086848 and WO 2013/018928.
[0003] New derivatives of pesticide-active 6/5-bicyclic ring derivatives with sulfur substituents containing phenyl and pyridine have now been discovered.
[0004] Consequently, the present invention relates to compounds of formula I,
characterized by A represents CH or N; Q is a fused 5- to 10-membered monocyclic or bicyclic heterocyclic ring system that can be aromatic, partially saturated or fully saturated and contains 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, and it is not possible that each system ring containing more than 2 oxygen atoms and not more than 2 sulfur atoms, said five to ten membered ring system may be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, cyan, oxo, OH, NH2, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6thioalkyl, C1-C6sulfonyl, C1-C6-alkoxy-C6-alkylamino, C1-alkoxy-C6-alkyl, alkyl-alkyl-C1-alkyl haloC1- C4sulfanyl, haloC1-C4sulfinyl, haloC1-C4sulfonyl, C1-C6carbonylalkyl, haloC1-C6carbonylalkyl, phenyl, pyrimidinyl, thiazolyl, pyridinyl, pyrazinyl, pyridazinyl, pyridazinyl pyrazinyloxy, imidazolyl, dihydro-oxazolyl, oxazolyl, dioxolanyl, 1,3-dioxanil and 5,6-dihydro- [1,4,2] dioxazinyl; wherein said phenyl, pyrimidinyl, thiazolyl, pyridinyl, pyrazinyl, pyridazinyl, pyrazinyloxy, imidazolyl, dihydro-oxazolyl, oxazolyl, dioxolanyl, 1,3-dioxanil and 5,6-di-idro- [1,4,2 ] dioxazinyl may themselves be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, C1-C6 alkyl, C1-C4-alkylphosphinoylmethyl-aminocarbonyl, C1-2 alkoxycarbonylamino, C1-C6alkoxy, C1-C6alkyl, C1-6alkyl and C1-6alkyl diC1-C6amino alkyl; X is S, SO or SO2; R1 is C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6-cycloalkylC1-C4 or C3-C6 cycloalkyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C1-C4 alkyl; or R1 is C3-C6-cycloalkylC1-C4 alkyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C1-C4 alkyl; or R1 is C2-C6 alkenyl, C2-C6 haloalkenyl or C2-C6 alkynyl; R2 is halogen, cyano, C1-C6 haloalkyl or C1-C6 haloalkyl substituted by one or two substituents selected from the group consisting of hydroxyl, methoxy and cyano; or R2 is C1-C4sulfanyl haloalkyl, C1-C4sulfinyl haloalkyl, C1-C4sulfonyl haloalkyl, O (C1-C4 haloalkyl), or -C (O) C1-C4 haloalkyl; or R2 is C3-C6 cycloalkyl which may be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano and C1-C4 alkyl; X1 is O, S or NR3, where R3 is hydrogen, C1-C4 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C4 alkoxy-C1-C4 alkyl or C3-C6 cycloalkyl; and salts, stereoisomers, enantiomers, tautomers and agrochemically acceptable N-oxides of these compounds.
[0005] 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, a phosphorous acid or a halide acid, with strong organic carboxylic acids, such as C1-C4 alkanocarboxylic acids which are unsubstituted or substituted, for example, with halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example o 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 acids organic sulfonics, such as aryl or (C1-C4) alkane sulfonic acids that are unsubstituted or substituted, for example with halogen, for example methane or p-toluenesuic acid lphonic. 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 salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a short chain mono, di or trialkylamine, for example ethyl, diethyl, triethyl or dimethylpropylamine, or a short chain mono, di or trihydroxyalkylamine, for example mono, di or triethanolamine.
[0006] The alkyl groups occurring 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, pentila, hexila, nonila, decila and its branched isomers. The alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, alkoxy, alkenyl and alkynyl radicals are derived from the mentioned alkyl radicals. Alkenyl and alkynyl groups can be mono- or polyunsaturated. diC1-alkyl-amino is dimethylamino.
[0007] Halogen is usually fluorine, chlorine, bromine or iodine. This also applies, correspondingly, to halogens in combination with other meanings, such as haloalkyls or halophenyls.
[0008] The haloalkyl groups preferably have a chain length of 1 to 6 carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichlorethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl.
[0009] Alkoxy groups preferably have a preferred chain length of 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and also the isomeric pentyloxy and hexyloxy radicals.
[0010] The alkoxyalkyl groups preferably have a chain length of 1 to 6 carbon atoms.
[0011] Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
[0012] An alkylsulfanyl is, for example, methylsulfanyl, ethylsulfanyl, propylsulfanyl, isopropylsulfanyl, butylsulfanyl, pentylsulfanyl, and hexylsulfanyl.
[0013] An alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, a butylsulfinyl, pentylsulfinyl, and hexylsulfinyl.
[0014] An alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, pentylsulfonyl, and hexylsulfonyl.
[0015] Alkoxycarbonyl is, for example, methoxycarbonyl (which is C1 -carbonyl), ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, tert-butoxycarbonyl, n-pentoxycarbonyl or hexoxycarbonyl.
[0016] Cycloalkyl groups preferably have 3 to 6 carbon atoms in the ring, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
[0017] The haloalkoxy groups preferably have a chain length of 1 to 4 carbon atoms. Haloalkoxy is, for example, difluoromethoxy, trifluoromethoxy or 2,2,2-trifluoroethoxy.
[0018] In the context of this invention, "mono- to polysubstituted" in the definition of substituents typically means, depending on the chemical structure of the substituents, monosubstituted up to seven times substituted, preferably monosubstituted up to five times substituted, more preferably mono-, double - or triple substituted.
[0019] Free radicals represent methyl groups. In heterocycles J, which represent embodiments of the substituent Q, the free radical represents a bond.
The compounds of formula I according to the invention also include hydrates that can be formed during the formation of salts.
[0021] In accordance with the present invention, the fused monocyclic or bicyclic ring system with five to ten members which can be aromatic, partially saturated or fully saturated and contains 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it is not possible for each ring system to contain more than 2 oxygen atoms and no more than 2 sulfur atoms or a fused three to ten membered monocyclic or bicyclic ring system that can be aromatic, partially saturated or fully saturated ; depending on the number of ring members, for example, selected from the group consisting of the following heterocyclic groups: pyrrolyl; pyrazolyl; isoxazolyl; furanil; thienyl; imidazolyl; oxazolyl; thiazolyl; isothiazolyl; triazolyl; oxadiazolyl; thiadiazolyl; tetrazolyl; furyl; pyridyl; pyrimidyl; pyrazinyl; pyridazinyl; triazinyl, pyranyl; quinazolinyl; isoquinolinyl; indolizinyl; isobenzofuranylnaphyridinyl; quinoxalinyl; cinolinyl; phthalazinyl; benzothiazolyl; benzoxazolyl; benzotriazolyl; indazolyl; indolyl; pyrrolidinyl; piperidinyl; morpholinyl; indolinyl; tetrahydroquinolinyl; (1H-pyrrol-1-yl) -; (1H-pyrrol-2-yl) -; (1H-pyrrol-3-yl) -; (1H-pyrazol-1-yl) -; (1H-pyrazol-3-yl) -; (3H-pyrazol-3-yl) -; (1H-pyrazol-4-yl) -; (3-isoxazolyl) -; (5-isoxazolyl) -; (2-furanyl) -; (3-furanyl) -; (2-thienyl) -; (3-thienyl) -; (1H-imidazol-2-yl) -; (1H-imidazol-4-yl) -; (1H-imidazol-5-yl) -; (2-oxazol-2-yl) -; (oxazol-4-yl) -; (oxazol-5-yl) -; (thiazol-2-yl) -; (thiazol-4-yl) -; (thiazol-5-yl) -; (isothiazol-3-yl) -; (isothiazol-5-yl) -; (1H-1,2,3-triazol-1-yl) -; (1H-1,2,4-triazol-3-yl) -; (4H1,2,4-triazol-4-yl) -; (1H-1,2,4-triazol-1-yl) - (1,2,3-oxadiazol-2-yl) -; (1,2,4-oxadiazol-3-yl) -; (1,2,4-oxadiazol-4-yl) -; (1,2,4-oxadiazol-5-yl) -; (1,2,3-thiadiazol-2-yl) -; (1,2,4-thiadiazol-3-yl) -; (1,2,4-thiadiazol-4-yl) -; (1,3,4-thiadiazol-5-yl) -; (1H-tetrazol-1-yl) -; (1H-tetrazol-5-yl) -; (2H-tetrazol-5-yl) -; (2-pyridyl) -; (3-pyridyl) -; (4-pyridyl) -; (2-pyrimidinyl) -; (4-pyrimidinyl) -; (5-pyrimidinyl) -; (2-pyrazinyl) -; (3-pyridazinyl) -; (4-pyridazinyl) -; (1,3,5-triazin-2-yl) -; (1,2,4-triazin-5-yl) -; (1,2,4-triazin-6-yl) -; (1,2,4-triazin-3-yl) -; (furazan-3-yl) -; (2-quinolinyl) -; (3-quinolinyl) -; (4-quinolinyl) -; (5-quinolinyl) -; (6-quinolinyl) -; (3-isoquinolnil) -; (4-isoquinolnil) -; (2-quinozolinyl) -; (2-quinoxalinyl) -; (5- quinoxalinyl) -; (pyrido [2,3-b] pyrazin-7-yl) -; (benzoxazol5-yl) -; (benzothiazol-5-yl) -; (benzo [b] thien-2-yl) - and (benzo [1,2,5] oxadiazol-5-yl) -.
[0022] In a preferred embodiment of the invention, Q is a fused monocyclic or bicyclic ring system with five to ten members that can be aromatic, partially saturated or fully saturated and contains 1 to 4 hetero atoms selected from the group consisting of nitrogen , oxygen and sulfur, since it is not possible for each ring system to contain more than 2 oxygen atoms and no more than 2 sulfur atoms, said ring system with five to ten members may be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6thioalkyl, C1-C6sulfonyl, C1-C6carbonylalkyl, C1-alkylamino, C1-6 alkylamino, C1-6 alkylamino, C1- amino , haloC1-C4sulfanyl, haloC1-C4sulfinyl, haloC1-C4sulfonyl, haloC1-C6carbonyl, haloC1-C6carbonyl, phenyl, pyrimidinyl, thiazolyl, pyridinyl, pyrazinyl, pyrida zinyl, pyrazinyloxy, imidazolyl, dihydro-oxazolyl, oxazolyl, dioxolanyl, 1,3-dioxanyl and 5,6-dihydro- [1,4,2] dioxazinyl; wherein said phenyl, pyrimidinyl, thiazolyl, pyridinyl, pyrazinyl, pyridazinyl, pyrazinyloxy, imidazolyl, dihydro-oxazolyl, oxazolyl, dioxolanyl, 1,3-dioxanil and 5,6-di-idro- [1,4,2 ] dioxazinyl which may themselves be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, C1-C6 alkyl, C1-C4-phosphinoylmethyl-aminocarbonyl, C1-carbonylamino, C1-C6 alkoxy, C1-C6 alkyl, C1-6 alkylaminoC1- alkyl and C1-C6amino dialkyl.
[0023] In preferred compounds of formula I, Q is selected from the group consisting of J-1 to J-56
in particular selected from J-1 to J-40; where each group J-1 to J-56 is mono-, di- or tri-substituted by Rx, where each Rx is independently selected from the group consisting of hydrogen, halogen, cyano, C1-C6 alkyl, C1- C6 haloalkyl, C1-C6 alkoxy , C1-C6 haloalkoxy, C1-C6 alkyl, C1- C6 sulfonyl, C1-C6 alkoxycarbonyl, C1-C6 amino, alkyl C1-C6 amino, alkoxyC1-C6carbonylamino, haloalkylC1- C4 sulfonyl, haloalkyl, haloalkyl, haloalkyl, haloalkyl, haloalkyl , phenyl, pyrimidinyl, thiazolyl, pyridinyl, pyrazinyl, pyridazinyl, pyrazinyloxy, imidazolyl, dihydro-oxazolyl, oxazolyl, dioxolanyl, 1,3-dioxanil and 5,6-dihydro- [1,4,2] dioxazinil; wherein said phenyl, pyrimidinyl, thiazolyl, pyridinyl, pyrazinyl, pyridazinyl, pyrazinyloxy, imidazolyl, dihydro-oxazolyl, oxazolyl, dioxolanyl, 1,3-dioxanil and 5,6-di-idro- [1,4,2 ] dioxazinyl may themselves be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, C1-C6 alkyl, C1-C4-alkylphosphinoylmethyl-aminocarbonyl, C1-2 alkoxycarbonylamino, C1-C6alkoxy, C1-C6alkyl, C1-6alkyl, C1-6 alkylamino diC1-C6amino alkyl.
[0024] A preferred group of compounds of formula I is represented by compounds of formula I-1
wherein R2 and Q are as defined under formula I above; and where Xa1 is S, SO or SO2; Ra1 is methyl, ethyl, n-propyl, ipropyl or cyclopropylmethyl; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and Noxides of these compounds. In this preferred group of compounds of the formula I-1, R2 is preferably C1-C4 haloalkyl, Xa1 is preferably SO2 and Ra1 is preferably ethyl. In the compounds of formula I-1, Q preferably selected from the group consisting of heterocycles

wherein Rx is independently selected from the group consisting of hydrogen, halogen, cyano, amino, C3-C6 cycloalkyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 alkyl, C1-C6tio alkyl, C1-C6sulfonyl, C6sulfonyl, C6-alkoxy, alkoxyC1 C1-C6aminoalkyl, C1-C6aminoalkyl, C1-C6alkoxycarbonylamino, haloC1-C4sulfanyl, haloC1-C4sulfinyl, haloalkylC1-C4sulfonyl, alkylcidinyl, pyridyl, pyridyl, pyridyl, pyridyl, pyridyl, pyridyl, pyridyl dihydro-oxazolyl, oxazolyl, dioxolanyl, 1,3-dioxanyl and 5,6-dihydro- [1,4,2] dioxazinyl; wherein said phenyl, pyrimidinyl, thiazolyl, pyridinyl, pyrazinyl, pyridazinyl, pyrazinyloxy, imidazolyl, dihydro-oxazolyl, oxazolyl, dioxolanyl, 1,3-dioxanil and 5,6-di-idro- [1,4,2 ] dioxazinyl may themselves be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, C1-C6 alkyl, C1-C4-alkylphosphinoylmethyl-aminocarbonyl, C1-2 alkoxycarbonylamino, C1-C6alkoxy, C1-C6alkyl, C1-6alkyl and C1-6alkyl diC1-C6amino alkyl. In the compounds of formula I1, Rx is preferably independently selected from hydrogen, halogen, cyano, amino, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 haloalkoxy, C3-C6 cycloalkyl and phenyl, said phenyl may be mono- or polysubstituted by halogen
[0025] An additionally preferred group of compounds of formula I is represented by compounds of formula I-2
wherein R2 and Q are as defined under formula I above; and where Xa2 is S, SO or SO2; Ra2 is methyl, ethyl, n-propyl, ipropyl or cyclopropylmethyl; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and Noxides of these compounds. In this preferred group of compounds of the formula I-2, R2 is preferably haloC1-C4alkyl, Xa2 is preferably SO2 and Ra2 is preferably ethyl. In the compounds of formula I-2, Q preferably selected from the group consisting of heterocycles
in particular selected from J-5a and J-30a; where Rx is independently selected from the group consisting of hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkyl, C1-C6sulfonyl alkyl, C1-C6carbonyl, alkylC1-C6-alkyl, di-alkyl-C1-C6-alkyl C1-C6amino, C1-6 alkoxycarbonylamino, haloC1-C4sulfanyl, haloC1- C4sulfinyl, haloC1-C4sulfonyl, haloalkyl-C6carbonyl, haloalkylC1-C6carbonyl, pyridinyl, pyridine, pyridine, pyriminazole, pyrimazole, pyrimazazole oxazolyl, dioxolanil, 1,3-dioxanil and 5,6-dihydro- [1,4,2] dioxazinil; wherein said phenyl, pyrimidinyl, thiazolyl, pyridinyl, pyrazinyl, pyridazinyl, pyrazinyloxy, imidazolyl, dihydro-oxazolyl, oxazolyl, dioxolanyl, 1,3-dioxanil and 5,6-di-idro- [1,4,2 ] dioxazinyl may themselves be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, C1-C6 alkyl, C1-C4-alkylphosphinoylmethyl-aminocarbonyl, C1-2 alkoxycarbonylamino, C1-C6alkoxy, C1-C6alkyl, C1-6alkyl and C1-6alkyl diC1-C6amino alkyl, in particular hydrogen and C1-C4 haloalkyl.
[0026] Especially preferred compounds of formula I are represented by compounds of formula Ia-1
characterized by X2 is S or SO2; X3 is N- (C1-C4 alkyl); R4 is C1-C4 alkyl; R6 is C1-C4 haloalkyl; and Qa is selected from the group consisting of heterocycles
in particular selected from heterocycles
where each preferred group Qa is mono-, di- or tri-substituted by Rx, where each Rx is independently selected from the group consisting of hydrogen, halogen, cyano, C1-C6 alkyl, C1- C6 haloalkyl, C1-C6 alkoxy, C1-C6 alkoxy, C1-C6thioalkyl, C1-C6sulfonylalkyl, C1-C6carbonylalkyl, C1-C6alkylamino, di-C1-C6amino, C1-C6carbonylaminoalkyl, haloalkylC1-C4sulfanyl, haloalkylCyl-alkylcarbonyl, haloalkylalkyl, haloalkylalkyl, 1-6 thiazolyl, pyridinyl, pyrazinyl, pyridazinyl, pyrazinyloxy, imidazolyl, dihydro-oxazolyl, oxazolyl, dioxolanyl, 1,3-dioxanyl and 5,6-dihydro- [1,4,2] dioxazinil; wherein said phenyl, pyrimidinyl, thiazolyl, pyridinyl, pyrazinyl, pyridazinyl, pyrazinyloxy, imidazolyl, dihydro-oxazolyl, oxazolyl, dioxolanyl, 1,3-dioxanil and 5,6-di-idro- [1,4,2 ] dioxazinyl may themselves be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, C1-C6 alkyl, C1-C4-alkylphosphinoylmethyl-aminocarbonyl, C1-2 alkoxycarbonylamino, C1-C6alkoxy, C1-C6alkyl, C1-6alkyl and C1-6alkyl diC1-C6amino alkyl.
[0027] In said preferred compounds of formula Ia-1, Qa is preferably mono- or disubstituted by Rx, whereby each Rx is independently preferably selected from the group consisting of hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl , C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6thioalkyl, phenyl and halo-phenyl (preferably 4-halo-phenyl). In particular in said preferred compounds of formula Ia-1, Qa is preferably mono- or disubstituted by Rx, whereby each Rx is independently preferably preferably selected from hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkoxy, phenyl and halo-phenyl (preferably 4-halo-phenyl).
[0028] Even more preferred compounds of formula I are represented by compounds of formula Ia-2
characterized by X4 is SO2; X5 is N- (C1-C4 alkyl); R7 is C1-C4 alkyl; R8 is C1-C4 haloalkyl; and Qb is preferably selected from the group consisting of those in particular selected from the group consisting of heterocycles
in particular selected from the group consisting of heterocycles
where each Rx is independently selected from the group consisting of hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-6 alkyl, C1-C6 sulfonyl alkyl, C1-C6 carbonyl, C1-6 alkyl, C1-6 alkyl, C1-6 alkyl -C1-C6 alkylamino, C1- C6 alkoxycarbonylamino, haloalkylC1-C4sulfanyl, haloalkylC1- C4sulfinyl, haloalkylC1-C4sulfonyl, C1-C6carbonyl, haloalkylyl, oxidyl, pyrazinyl, pyrazine, pyrazine, pyrazine, pyrazine, pyrazole, , oxazolyl, dioxolanil, 1,3-dioxanil and 5,6-dihydro- [1,4,2] dioxazinil; wherein said phenyl, pyrimidinyl, thiazolyl, pyridinyl, pyrazinyl, pyridazinyl, pyrazinyloxy, imidazolyl, dihydro-oxazolyl, oxazolyl, dioxolanyl, 1,3-dioxanil and 5,6-di-idro- [1,4,2 ] dioxazinyl may themselves be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, C1-C6 alkyl, C1-C4-alkylphosphinoylmethyl-aminocarbonyl, C1-2 alkoxycarbonylamino, C1-C6alkoxy, C1-C6alkyl, C1-6alkyl and C1-6alkyl diC1-C6amino alkyl.
[0029] In said preferred compounds of formula Ia-2, Rx is independently especially preferably selected from the group consisting of hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6io alkyl, phenyl and halo-phenyl (preferably 4-halo-phenyl). In particular in said preferred compounds of formula Ia-2, Rx is independently especially preferably preferably selected from hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy, haloC1-C6 alkoxy, phenyl and halo-phenyl (preferably 4-halo-phenyl).
[0030] Additional preferred compounds of formula I are represented by compounds of formula Ia-3
characterized by R9 is C1-C4 haloalkyl; R10 is C1-C4 alkyl; and Qc is selected from

in particular selected from

characterized by each Rx is independently selected from the group consisting of is hydrogen, hydroxy, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, haloC1- C4carbonylamino, halogen, amino, cyano, C1-C6sulfanyl alkyl, and phen, said phenyl may be replaced by halogen.
[0031] An especially preferred group of compounds of formula I is represented by the compounds of formula Ia-3 above, wherein R9 is C1-C4 haloalkyl; R10 is C1-C4 alkyl; and Qc is selected from
in particular selected from
characterized by Rx is hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy or C1-C6 haloalkoxy, in particular C1-C4 alkyl, C1-C4 alkoxy, haloC1-C4 or halogen.
[0032] The process according to the invention for preparing the compounds of formula I is carried out, in principle, by methods known to those skilled in the art. More specifically, compounds of formula I can be prepared (as illustrated in scheme 1) by reacting compounds of formula II with compounds of formula III, where Xb1 can be a halogen, preferably chlorine, bromine or iodine, or a sulfonate, such as a trifluoromethanesulfonate and Yb1 can be a functional group derived from boron, such as B (OH) 2 or B (ORb1) 2 where Rb1 can be a C1-C6 alkyl group or the two ORb1 groups can form together with the boron atom is a five- or six-membered ring, such as a pinacol boronic ester. In formulas II and III, A, X1, R1, R2, X and Q are as described in formula I. The reaction can be catalyzed by a palladium-based catalyst, for example tetrakis (triphenylphosphine) palladium (0), dichloride bis (triphenylphosphine) palladium (II), chlorine (2-dicyclohexylphosphino-2 ', 4', 6'-triisopropyl-1,1'-biphenyl) [2- (2'-amino-1,1 ' -biphenyl)] palladium (II) (XPhos paladacycle), or (1,1'-bis (diphenylphosphino) -ferrocene) dichloropalladium-dichloromethane (1: 1 complex), in the presence of a base, such as sodium carbonate, phosphate tripotassium or cesium fluoride, in a solvent (such as 1,2-dimethoxyethane tetrahydrofuran or dioxane) or a mixture of solvents, such as a mixture of 1,2-dimethoxyethane and water, or dioxane and water, preferably under an inert atmosphere. The reaction temperature can preferably vary from room temperature to the boiling point of the reaction mixture, or alternatively the heating can be carried out under microwave irradiation. Scheme 1:

[0033] The compounds of formula II, in which A, X1, R1, R2 and X are as described in formula I, and in which Xb1 is a halogen, preferably chlorine, bromine or iodine, can be prepared in analogy to descriptions found in WO15 / 000715.
[0034] The compounds of formula I can also be prepared (as illustrated in scheme 2) by reacting compounds of formula IV with compounds of formula V, where Xb2 can be a halogen, preferably chlorine, bromine or iodine, or a sulfonate , such as a trifluoromethanesulfonate and Yb2 can be a functional group derived from boron, such as B (OH) 2 or B (ORb2) 2 where Rb2 can be a C1-C6 alkyl group or the two ORb2 groups can form together with the boron atom a ring with five or six members, such as a pinacol boronic ester. In formulas IV and V, A, X1, R1, R2, X and Q are as described in formula I. The reaction can be catalyzed by a palladium-based catalyst, for example tetrakis (triphenylphosphine) - palladium (0), dichloride bis (triphenylphosphine) palladium (II) or (1,1'bis (diphenylphosphino) -ferrocene) dichloropalladium-dichloromethane (complex 1: 1), in the presence of a base, such as sodium carbonate or cesium fluoride, in a solvent (such as 1,2-dimethoxyethane, tetrahydrofuran or dioxane) or a mixture of solvents, such as, for example, a mixture of 1,2-dimethoxyethane and water, or dioxane and water, preferably under an inert atmosphere. The reaction temperature can preferably vary from room temperature to the boiling point of the reaction mixture, or alternatively the heating can be carried out under microwave irradiation. Layout 2

[0035] The compounds of formula IV
characterized by R1, R2, X, X1 and A are as defined under formula I above, and Yb2 is -B (OH) 2, -B (ORb2) 2, in which Rb2 is a C1-C6 alkyl or Yb2 is
(a 4,4,5,5-tetramethyl-1,3,2-dioxaborolane group), are new, specially developed for the preparation of the compounds of formula I according to the invention and therefore represent a further subject of the invention. The definitions of preferred substituents for formulas I, I-1, I-2, Ia-1, Ia-2 and Ia-3 are also valid for the preferred compounds of formula IV.
[0036] In the particular case where the compounds of the formula I have the group Q attached via a nitrogen atom (ie, those situations where Q is a nitrogen-containing hetero-ring system), these compounds can be advantageously accessed by reaction of a compound of the formula IV with a compound of the formula Va, where Yb2 can be a boron-derived functional group, such as for example B (OH) 2 or B (ORb2) 2 where Rb2 can be a C1-C6 alkyl group or both ORb2 groups can form together with the boron atom a five- or six-membered ring, such as a pinacol boronic ester (scheme 2a). In formulas IV and Va, A, R1, R2, X and X1 are as defined under formula I above and Q is as described in formula I, with the proviso that the attachment point is a nitrogen atom. The reaction, also known as Chan-Lam coupling (PYS Lam, CG Clark, S. Saubern, J. Adams, MPWinters, DMT Chan, A. Combs, Tetrahedron Lett. 1998, 39, 2941), is commonly performed with a to two equivalents of a base, such as pyridine or triethylamine, in the presence of one to two equivalents of a copper derivative, such as copper (II) acetate and under an atmosphere containing oxygen. The reaction can be operated in an inert solvent, such as dichloromethane, dioxane or dimethylformamide, usually at or around room temperature. Scheme 2a

[0037] In the particular case where the compounds of formula I have the group Q attached via a nitrogen atom (ie, those situations where Q is a nitrogen-containing hetero-ring system), these compounds can be advantageously accessed by reaction of a compound of formula II with a compound of formula Va, where Xb1 can be a halogen, preferably chlorine, bromine or iodine, or a sulfonate, such as a trifluoromethanesulfonate (scheme 2b). In formulas II and Va, A, R1, R2, X and X1 are as defined under formula I above and Q is as described in formula I, with the proviso that the attachment point is a nitrogen atom. Such a reaction with a heterocycle QH (which contains an appropriate NH functionality) of the formula Va can be operated in the presence of a base, such as potassium carbonate K2CO3 or cesium carbonate Cs2CO3, optionally in the presence of a copper catalyst, for example example copper (I) iodide, with or without an additive such as L-proline, N, N'-dimethylcyclohexane-1,2-diamine or N, N'-dimethylethylene diamine, in an inert solvent such as N-methylpyrrolidone NMP or N, N-dimethylformamide DMF at temperatures between 30-150 ° C, optionally under microwave irradiation. Scheme 2b

[0038] Such a reaction (CN Bond Formation) is illustrated below (scheme 2c) for the QH heterocycle J-30a, where J30a and Rx are as defined above, to give a compound of the formula I- (J-30a ), a subgroup of compounds of formula I, in which Rx, A, X, R1, X1 and R2 are as previously defined. Scheme 2c

[0039] The compounds of formula I-a3, where A, R1, R2, X1 and Q have the values defined in formula I, and X is -SO2-, can be prepared by oxidizing compounds of formula I-a2, where A, R1, R2, X1 and Q have the values defined in formula I, and X is –SO–. The reaction can be carried out with reagents such as, for example, a peracid such as peracetic acid or chloroperoperbenzoic acid, or a hydroperoxide, such as, for example, hydrogen peroxide or tert-butylhydroperoxide, or an inorganic oxidant, such as a monoperoxo disulfate salt or potassium permanganate. Similarly, compounds of formula I-a2, where A, R1, R2, X1 and Q have the values defined in formula I, and X is –SO–, can be prepared by oxidizing compounds of formula I- a1, where A, R1, R2, X1 and Q have the values defined in formula I, and X is –S–, under analogous conditions described above. These reactions can be carried out in various organic or aqueous solvents compatible with these conditions, at temperatures below 0 ºC up to the boiling point of the solvent system. The transformation of compounds of formula 1-a1 into compounds of formulas 1-a2 and 1-a3 is shown in scheme 3. Scheme 3

[0040] The compounds of formula I-a1 can also be prepared (scheme 4) by reacting a compound of formula VI with a compound of formula VII, in which A, R1, R2, X1 and Q have the values defined in the formula I and X is sulfur and M is a metal or non-metal cation. In scheme 4, the M cation is assumed to be monovalent, but polyvalent cations associated with more than one S-R1 group can also be considered. Preferred cations are, for example, lithium, sodium, potassium or cesium. For this transformation to work, Xb3 is a labile group such as, for example, fluorine, chlorine, bromine or iodine, or an aryl- or alkylsulfonate, but many other labile groups could be considered. The reaction can be carried out in a solvent, preferably aprotic, at temperatures below 0 ºC or up to the boiling temperature of the reaction mixture. Layout 4

[0041] The compounds of formula VI, where Xb3 is a labile group such as, for example, fluorine, chlorine, bromine or iodine, or an aryl- or alkylsulfonate such as trifluoromethanesulfonate, or any other similar labile group, can be prepared ( scheme 5) by reacting compounds of formula VIII with compounds of formula IX, where Xb4 can be a halogen, preferably chlorine, bromine or iodine, or a sulfonate, such as a trifluoromethanesulfonate, most preferably bromine or iodine and Yb4 can be a functional group derived from boron, such as B (OH) 2 or B (ORb4) 2 where Rb4 can be a C1-C6 alkyl group or the two ORb4 groups can form together with the boron atom a ring with five or six limbs, such as a pinacol boronic ester. In formulas VI, VIII and IX, A, X1, R2 and Q are as described in formula I. The reaction can be catalyzed by a palladium-based catalyst, for example tetrakis (triphenylphosphine) palladium (0), bis ( triphenylphosphine) palladium (II) or (1,1'bis (diphenylphosphino) -ferrocene) dichloropalladium-dichloromethane (1: 1 complex), in the presence of a base, such as sodium carbonate or cesium fluoride, in a solvent (such as 1,2-dimethoxyethane, tetrahydrofuran or dioxane) or a mixture of solvents, such as, for example, a mixture of 1,2-dimethoxyethane and water, or dioxane and water, preferably under an inert atmosphere. The reaction temperature can preferably vary from room temperature to the boiling point of the reaction mixture, or alternatively the heating can be carried out under microwave irradiation. Layout 5

[0042] In an alternative way illustrated in scheme 6, compounds of formula VI can also be prepared by reacting compounds of formula X, where Xb3 is a labile group such as, for example, fluorine, chlorine, bromine or iodine, or an aryl- or alkylsulfonate such as trifluoromethanesulfonate, or any other similar labile group, with compounds of the formula XI, wherein Xb5 may be a halogen, preferably chlorine, bromine or iodine, or a sulfonate, such as a trifluoromethanesulfonate, most preferably bromine or iodine and Yb5 can be a functional group derived from boron, such as B (OH) 2 or B (ORb5) 2 where Rb5 can be a C1-C6 alkyl group or the two ORb5 groups can form together with the atom boron a ring with five or six members, such as a pinacol boronic ester. In formulas VI, X and XI, A, X1, R2 and Q are as described in formula I. The reaction can be catalyzed by a palladium-based catalyst, for example tetrakis (triphenylphosphine) palladium (0), bis ( triphenylphosphine) palladium (II) or (1,1'bis (diphenylphosphino) -ferrocene) dichloropalladium-dichloromethane (1: 1 complex), in the presence of a base, such as sodium carbonate or cesium fluoride, in a solvent (such as 1,2-dimethoxyethane, tetrahydrofuran or dioxane) or a mixture of solvents, such as, for example, a mixture of 1,2-dimethoxyethane and water, or dioxane and water, preferably under an inert atmosphere. The reaction temperature can preferably vary from room temperature to the boiling point of the reaction mixture, or alternatively the heating can be carried out under microwave irradiation. Layout 6

[0043] The compounds of formula I can also be prepared (scheme 7) by reacting compounds of formula XIII and compounds of formula XIV under various conditions of formal dehydration, where A, R1, R2, X, X1 and Q have the values defined in formula I. These methods are known to those skilled in the art or described for example in WO 2009/131237, WO 2011/043404, WO 2011/040629, WO 2010/125985, WO 2012/086848, WO 2013/018928, WO 2013/191113, WO 2013/180193 and WO 2013/180194. Such processes are well known and have been described for example in WO 2011/040629 or WO 2009131237 (X1 is oxygen), WO 2011088990 or Inorg. Chimica Acta, 358 (9), 2701-2710; 2005 (X1 is sulfur) and J. Am. Chem. Soc., 132 (5), 1545-1557, 2010 or WO 2008128968 (X1 is NR3). The preparation of compounds of formula XIII, where X1 and R2 are as defined above, is described in detail, for example, in WO 2015/000715. Layout 7

[0044] The process describing the reaction between compounds of formula XIII and compounds of formula XIV towards compounds of formula I is summarized in more detail in scheme 8: Scheme 8

[0045] The compounds of formula XIV, in which A, R1, X and Q are as previously described, are activated (scheme 8) in compounds of formula XIV-a by methods known to those skilled in the art and described in for example Tetrahedron, 61 (46), 10827-10852, 2005. For example, compounds where X0 is chlorine are formed by treatment with, for example, oxalyl chloride or thionyl chloride in the presence of catalytic amounts of DMF in inert solvents such as chloride methylene or THF at temperatures between 20 ° C and 100 ° C, preferably 25 ° C. Treatment of XIV-a with compounds of the formula XIII, wherein R2 and X1 are as described in formula I, optionally in the presence of a base, e.g., triethylamine or pyridine, leads to compounds of the formula XV. Alternatively, compounds of formula I can be prepared by treating compounds of formula XIV with dicyclohexyl carbodiimide (DCC) or 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) to give the activated species XIV-a , where X0 is X01 and X02 respectively, in an inert solvent, e.g., pyridine, or tetrahydrofuran (THF) optionally in the presence of a base, e.g., triethylamine, at temperatures between 50-180 ° C. The compounds of formula XV thus obtained can then be converted into compounds of formula I by dehydration, eg by heating the compounds under microwave irradiation, in the presence of an acid catalyst, for example methanesulfonic acid, or acid for -toluenesulfonic, in an inert solvent such as N-methyl pyrrolidone at temperatures between 25-180 ° C, preferably 130-170 ° C. Such processes were previously described in WO 2010/125985. Alternatively, compounds of formula XV can be converted to compounds of formula I (where X1 is O) using triphenylphosphine, diisopropyl azodicarboxylate in an inert solvent such as THF at temperatures between 25-50 ° C. Such Mitsunobu conditions have been previously described for such transformations (see WO 2009/131237).
[0046] In an analogous manner (scheme 9), the compounds of formula VI, wherein Xb3 is a labile group such as, for example, fluorine, chlorine, bromine or iodine, or an aryl- or alkylsulfonate such as trifluoromethanesulfonate, or any another similar labile group, can be prepared by reacting compounds of formula XVI, in which A and Q have the values defined for formula I, with an activating agent, such as, for example, oxalyl chloride or carbodiimide chloride to generate the activated species XVI-a, followed by reaction with compounds of formula XIII, in which R2 and X1 are as described in formula I. The intermediate compounds of formula XVII can be isolated, but are preferably converted to the compounds of formula VI in a similar way as described above for the transformation of compounds XV into compounds of formula I. Scheme 9

[0047] In a similar manner as described above, compounds of formula VIII can be prepared as described in scheme 10, by reacting compounds of formula XVIII, respectively an activated form XVIII-a of compounds of formula XVIII, where A is carbon or nitrogen, and Xb3 is a labile group such as, for example, fluorine, chlorine, bromine or iodine, or an aryl- or alkylsulfonate such as trifluoromethane-sulfonate, and Xb4 can be a halogen, preferably chlorine, bromine or iodine, or a sulfonate, such as a trifluoromethanesulfonate, most preferably bromine or iodine, with compounds of the formula XIII, where X1 and R2 are as described in formula I. The intermediate compounds of the formula XIX can be isolated, but are preferably converted to the compounds of formula VIII in a similar manner as described above (transformation of compounds XV into compounds of formula I). Layout 10

[0048] The compounds of formula XXI can be prepared as described in scheme 10a, by reacting compounds of formula XX, where A is CH or nitrogen, and Xb3a is a labile group such as, for example, nitro, fluorine, chlorine, bromine or iodine, or an aryl- or alkylsulfonate such as trifluoromethane-sulfonate, and Xb4 can be a halogen, preferably chlorine, bromine or iodine, or a sulfonate, such as a trifluoromethanesulfonate, most preferably bromine or iodine, with a compound of formula VII, where R1 is as defined in formula I, and M is a metal or non-metal cation. In scheme 10a, the cation M is assumed to be monovalent, but polyvalent cations associated with more than one S-R1 group can also be considered. Preferred cations are, for example, lithium, sodium, potassium or cesium. The reaction can be carried out in a solvent, preferably polar aprotic, such as THF or MeCN, at temperatures between -78 ° C and the boiling temperature of the reaction mixture. Layout 10a

[0049] The compounds of formula XVIII-c can be prepared by hydrolysis of compounds of formula XXI under acidic conditions (eg, HCl or H2SO4) or basic conditions (eg, NaOH or KOH) as described in scheme 10a , under conditions known to a person skilled in the art. The compounds of formula II-a2 can be prepared, as described in scheme 10a, by reacting compounds of formula XVIII-c, respectively an activated form XVIII-d of compounds of formula XVIII-c, with compounds of formula XIII, wherein X1 and R2 are as described in formula I. The intermediate compounds of formula XXII can be isolated, but are preferably converted to the compounds of formula IIa2 in a similar manner as described above (transformation of compounds XV into compounds of formula I). In compounds of formulas XXI, XVIII-c, XVIII-d, XXII and II-a2, X can be S, SO or SO2. The appropriate forms of oxidation of the sulfur atom in compounds of formulas XXI, XVIII-c, XVIII-d, XXII and II-a2, where X is SO or SO2, can be prepared by oxidizing compounds of formulas XXI, XVIII- c, XVIII-d, XXII and II-a2 where X is S. The reaction can be carried out with reagents such as a perishable one such as peracetic acid or m-chloroperbenzoic acid, or a hydroperoxide such as hydrogen peroxide or tertbutylhydroperoxide, or an inorganic oxidant, such as a mono-peroxodisulfate salt or potassium permanganate, preferably meta-chloroperbenzoic acid.
[0050] The compounds of formula XVIII-c, where X is S, SO or SO2, can alternatively be prepared by methods analogous to those described in the literature (scheme 10b). For example, a compound of formula XVIII-c, where X is S, can be prepared by saponification of a compound of formula XXIV, in which RLG is C1-C4 alkyl, under conditions known to a person skilled in the art (R1 is as defined in formula I, A is N or CH, and Xb4 can be a halogen, preferably chlorine, bromine or iodine, or a sulfonate, such as a trifluoromethanesulfonate, most preferably bromine or iodine). Layout 10b

[0051] The compounds of the formula XXIV, in which RLG is C1-C4 alkyl, can be prepared by treating compounds of the formula XXIII, in which Xb3a is a labile group such as, for example, nitro, fluorine, chlorine, bromine or iodine, or an aryl- or alkylsulfonate such as trifluoromethanesulfonate, and where RLG is C1-C4 alkyl, with an MS-R1 reagent, where R1 is as defined in formula I and M is a metal or non-metal cation, under conditions described above . Such processes involving for example sodium methane- or ethanethiolate as M-S-R1 reagents are well known and have been described previously in, for example, WO2014 / 152738. The compounds of formula XXIV can be oxidized to compounds of formula XXIV-a using methods known to those skilled in the art and described for example in Scheme 12, and then saponified to compounds of formula XVIII-c, where X is SO or SO2. Alternatively, compounds of formula XXIV can first be saponified to compounds of formula XVIII-c, where X is S, and then oxidized to compounds of formula XVIII-c, where X is SO or SO2. The compounds of the formula XXIII are commercial or have been described in WO 2012/086848.
[0052] The compounds of formula II-a1, where X is sulfur, can be prepared (scheme 11) by reacting a compound of formula VIII, where A, R2 and X1 are as defined in formula I, and where Xb3 is a labile group such as, for example, fluorine, chlorine, bromine or iodine, or an aryl- or alkylsulfonate such as trifluoromethanesulfonate, preferably fluorine or chlorine, where Xb4 is a halogen, preferably chlorine, bromine or iodine, or a sulfonate , such as a trifluoromethanesulfonate, most preferably bromine or iodine, with a compound of formula VII, where R1 is as defined in formula I, and M is a metal or non-metal cation. In scheme 11, the M cation is assumed to be monovalent, but polyvalent cations associated with more than one S-R1 group can also be considered. Preferred cations are, for example, lithium, sodium, potassium or cesium. The reaction can be carried out in a solvent, preferably polar aprotic, at temperatures below 0 ° C or up to the boiling temperature of the reaction mixture. Layout 11

[0053] The compounds of formula II-a3, in which A, R1, R2 and X1 have the values defined in formula I, and X is –SO2–, and where Xb4 is a halogen, preferably chlorine, bromine or iodine, or a sulfonate, such as a trifluoromethanesulfonate, can be prepared (scheme 12) by oxidizing compounds of formula II-a2, where A, R1, R2 and X1 have the values defined in formula I, and X is –SO– , and where Xb4 is a halogen, preferably chlorine, bromine or iodine, or a sulfonate, such as a trifluoromethanesulfonate. The reaction can be carried out with reagents such as a peracid such as peracetic acid or m-chloroperbenzoic acid, or a hydroperoxide such as hydrogen peroxide or tertbutylhydroperoxide, or an inorganic oxidant, such as a mono-peroxodisulfate or permanganate salt potassium, preferably meta-chloroperbenzoic acid. Similarly, compounds of formula II-a2, where A, R1, R2 and X1 have the values defined in formula I, and X is –SO–, and where Xb4 is a halogen, preferably chlorine, bromine or iodine, or a sulfonate, such as a trifluoromethanesulfonate, can be prepared by oxidizing compounds of formula II-a1, where A, R1, R2 and X1 have the values defined in formula I, and X is –S–, and wherein Xb4 is a halogen, preferably chlorine, bromine or iodine, or a sulfonate, such as a trifluoromethanesulfonate. These reactions can be carried out in various organic or aqueous solvents compatible with these conditions, at temperatures below 0 ºC up to the boiling point of the solvent system. Layout 12

[0054] Many compounds of formulas V and XI, where Q has the values defined in formula I, and where Xb2 and Xb5 are as defined above, are commercially available or may be accessible to the person skilled in the art, by analogy with procedures described in the literature.
[0055] A large number of compounds of the formula III are commercially available or can be prepared by those skilled in the art. Many chemical transformations, well known to those skilled in the art, can be used to access boronic acid derivatives of formula III, starting from various starting materials and easily available, for example, to name just a few (scheme 13 ), abstraction of hydrogen in a heteroaromatic compound of formula III-a in which Zb1 is hydrogen, with a strong base (step A), such as butyllithium or lithium diisopropylamide or (i-PrMgCl, LiCl), followed by reaction of metallized intermediate of formula III-b, wherein Zb2 is a metal such as Li + or MgCl + for example, with, for example, a trialkylborate (step B). Another way to access an organometal intermediate of formula III-b is from a compound of formula III-a in which Zb1 is chlorine, bromine or iodine, by exchanging metal-halogen with an organometallic species (step C), like butyllithium or an organomagnesium compound, or direct metallization with a metal, like magnesium.
[0056] The introduction of a pinacolborate functional group through a palladium-catalyzed reaction with bispinacol diborane in a compound of formula III-a, in which Zb1 is chlorine, bromine, iodine or triflate, is another common strategy (scheme 13, step D). In the compounds of formulas III-a, III-b and III within scheme 13, Q has the values defined for formula I. An expert person will be able to select a suitable preparation method to access compounds of formula III from III-a depending on the values of Q. Scheme 13

[0057] The same preparation methods described in scheme 13 can be applied for the synthesis of intermediates of formula IX.
[0058] The compounds of formula IV, in which A, X, X1, R1 and R2 are as described in formula I, can be prepared from compounds of formula II (scheme 14), in which A, X, X1, R1 and R2 are as described in formula I. In fact, compounds of formula II, in which Xb1 is chlorine, bromine or iodine, can be treated with an organometallic species such as, for example, butyllithium or an organomagnesium compound, to generate an intermediate compound of formula II-a, in which Zb3 is as defined in the scheme, through metalhalogen exchange. This reaction is preferably carried out in an anhydrous aprotic solvent, such as THF, at low temperature (between -120 ° C and 0 ° C), preferably between -110 ° C and - 60 ° C). The intermediate organometal compound of formula II-a is preferably directly converted to the compound of formula IV by reaction with a boronate compound B (ORb2) 3, where Rb2 is a C1-C6 alkyl group. Depending on the nature of the boronate, the reaction treatment conditions and the processing conditions, boronic acid IV, where Yb2 is –B (OH) 2, or a dialkylboronate IV, where Yb2 is –B (ORb2) 2, can be formed.
[0059] The introduction of a pinacolborate functional group through a palladium-catalyzed reaction with bispinacol diborane B2Pin2 in a compound of formula II, where A, X, X1, R1 and R2 are as described in formula I, and where Xb1 is chlorine, bromine, iodine or triflate, it is another common strategy. This reaction, generating a cyclic boronate IV, in which Yb2 is
, can be carried out in an aprotic solvent, in the presence of a base, preferably a weak base, such as potassium acetate KOAc. [1,1'- Bis (diphenylphosphino) ferrocene] dichloropalladium (II), also known as palladium dppf chloride or Pd (dppf) Cl2, is a common catalyst for this type of reaction. The reaction temperature is preferably between 0 ° C and the boiling point of the reaction mixture, or alternatively the heating can be carried out under microwave irradiation. Layout 14

[0060] Reagents can be reacted in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal carbonates or alkaline earth metals, alkali metal dialkylamides or alkaline earth metals or alkaline earth alkali metals or alkaline earth metals, alkylamines, alkylene diamines, free or 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).
[0061] The reagents can be reacted with each other as is, that is, without the addition of a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases that can be used in excess, such as triethylamine, pyridine, N-methylmorpholine or N, Ndiethylaniline, can also act as solvents or diluents.
[0062] 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.
[0063] A compound of the formula I can be converted, in a manner known per se, to another compound of the formula I by substituting one or more substituents of the starting compound of the formula I, in the usual manner, for another (s) (s) according to the invention.
[0064] Depending on the reaction conditions and the starting materials chosen, which are appropriate for each case, it is possible, for example, in a reaction step, to replace only one substituent with another substituent according to the invention, or a plurality of substituents can be replaced by other substituents according to the invention in the same reaction step.
[0065] 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 .
[0066] The salts of the compounds of the formula I can be converted in the usual way to the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or 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.
[0067] The salts of the compounds of the formula I can be converted in a manner known per se to other salts of the compounds of the formula I, acid addition salts, for example, in other acid addition salts, for example, by treatment an inorganic acid salt such as hydrochloride with an appropriate metal salt such as a sodium, barium or silver salt, 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.
[0068] Depending on the reaction procedure or conditions, the compounds of formula I, which have salt-forming properties can be obtained in free form or in the form of salts.
[0069] The compounds of formula I and, where appropriate, their tautomers, in each case in free form or in the form of salt, can be present in the form of one of the isomers that are possible or as a mixture of these, for example in as 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 should be understood accordingly in each case above in this document and below in this document, even when the stereochemical details are not specifically mentioned in each case.
[0070] Mixtures of diastereoisomers or mixtures of racemates of the compounds of formula I, in free form or in salt form, which can be obtained depending on the starting materials and the procedures that have been chosen, can be separated in a manner known in the art. pure diastereoisomers or racemates based on the physicochemical differences of the components, for example, by fractional crystallization, distillation and / or chromatography.
[0071] 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 diastereoisomeric salts, for example by reaction of a basic final product racemate 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 diastereoisomers that can be obtained in this way, for example by fractional crystallization based on their different solubilities, to give the diastereoisomers, from which the desired enantiomer can be released by the action of suitable agents, for example basic agents.
[0072] 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.
[0073] 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., 32 (12), 2561-73, 1989 or WO 00/15615.
[0074] It is advantageous, in each case, to isolate or synthesize the isomer, for example enantiomer or diastereoisomer, biologically more effective, or the mixture of isomers, for example mixture of enantiomers or mixture of diastereomers, biologically more effective if the individual components have different biological activity.
[0075] 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.
[0076] The compounds according to the following Tables 1 to 6 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 X: This table discloses 46 definitions of substituents X.001 to X.046 of formula I-1a:
where Ra1, R2 and QRx are as defined below: Table X:


and the N-oxides of the compounds in Table X. Table 1: This table discloses the 46 compounds 1,001 to 1,046 of the formula I-1a, where Xa1 is S, and Ra1, R2 and QRx are as defined in Table X. For example , compound No. 1.001 has the following structure:
Table 2: This table discloses the 46 compounds 2,001 to 2,046 of formula I-1a, where Xa1 is SO, and Ra1, R2 and QRx are as defined in Table X. Table 3: This table discloses the 46 compounds 3,001 to 3,046 of formula I-1a, where Xa1 is SO2, and Ra1, R2 and QRx are as defined in Table X. Table Y: This table discloses 46 definitions of substituents Y.001 to Y.046 of formula I-2a:
where Ra2, R2 and QRx are as defined below: Table Y:



and the N-oxides of the compounds in Table Y. Table 4: This table discloses the 46 compounds 4,001 to 4,046 of the formula I-2a, where Xa2 is S, and Ra2, R2 and QRx are as defined in Table Y. Table 5 : This table discloses the 46 compounds 5.001 to 5.046 of formula I-2a, where Xa2 is SO, and Ra2, R2 and QRx are as defined in Table Y. Table 6: This table discloses the 46 compounds 6.001 to 6.046 of formula I -2a, where Xa2 is SO2, and Ra2, R2 and QRx are as defined in Table Y.
[0077] 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 manifest itself directly, ie, in the destruction of pests, which takes place immediately or only after some time, for example during screening, or indirectly, for example at a rate of reduced oviposition and / or hatching.
[0078] Examples of the animal pests mentioned above are: of the order Acarina, for example, Acalitus spp, Aculus spp, Acaricalus spp, Aceria spp, Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp, Eotetranychus spp, Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp, Ornithodoruspp, Olephyphos spp. , Phytonemus spp, Polyphagotarsonemus spp, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus 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, Lerahoptruspanpea, Lerahoptrusppea, Lerahoptruspea, 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, Aonidi. Bactericera cockerelli, Bemisia spp, Brachycaudus spp, Brevicoryne brassicae, Cacopsylla spp, Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp, Cesperana sptra, Cesperana spectra, Cry , 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, Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Rilia dorsalis ., 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 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, Acleris 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, Litho collethis 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. Pandem ., Panolis flammea, Papaipema nebris, Pectinophora gossypiela, Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Pseudoplusia spp, Rachiplusia 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; of the order Thysanura, for example, Lepisma saccharina.
[0079] 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.
[0080] Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, corn or sorghum; beet, such as sugar beet or fodder; fruits, for example pome fruits, stone fruits or soft fruits, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soy; oil crops, such as rapeseed, mustard, poppies, olives, sunflowers, coconut, castor, 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 and greens, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, the Plantaginaceae family and latex plants.
[0081] The compositions and / or methods of the present invention can also be used in any ornamental and / or vegetable crops, including flowers, shrubs, broadleaved trees and evergreen trees.
[0082] For example, the invention can be used in any of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g., B. elatior, B. semperflorens, B. tubéreux), Bougainvillea spp., Brachycome spp., Brassica spp. (ornamental), Calceolaria spp., Capsicum annuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemum spp., Cineraria spp. (C. maritime), Coreopsis spp., Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp. globosa, Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (I. Walleriana), Iresines spp., Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesia spp., Tagetes spp., Dianthus spp. (carnation), Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (P. peltatum, P. Zonale), Viola spp. (pansy), Petunia spp., Phlox spp., Plecthranthus spp., Poinsettia spp., Parthenocissus spp. (P. quinquefolia, P. tricuspidata), Primula spp., Ranunculus spp., Rhododendron spp., Rosa spp. (pink), Rudbeckia spp., Saintpaulia spp., Salvia spp., Scaevola aemola, Schizanthus wisetonensis, Sedum spp., Solanum spp., Surfinia spp., Tagetes spp., Nicotinia spp., Verbena spp., Zinnia spp. and other stratifying plants.
[0083] For example, the invention can be used in any of the following species of vegetables: Allium spp. (A. sativum, A .. cepa, A. oschaninii, A. Porrum, A. ascalonicum, A. fistulosum), Anthriscus cerefolium, Apium graveolus, Asparagus officinalis, Beta vulgarus, Brassica spp. (B. Oleracea, B. Pekinensis, B. rapa), Capsicum annuum, Cicer arietinum, Cichorium endivia, Cichorum spp. (C. intybus, C. endivia), Citrillus lanatus, Cucumis spp. (C. sativus, C. melo), Cucurbita spp. (C. pepo, C. maxima), Cyanara spp. (C. scolymus, C. cardunculus), Daucus carota, Foeniculum vulgare, Hypericum spp., Lactuca sativa, Lycopersicon spp. (L. esculentum, L. lycopersicum), Mentha spp., Ocimum basilicum, Petroselinum crispum, Phaseolus spp. (P. vulgaris, P. coccineus), Pisum sativum, Raphanus sativus, Rheum rhaponticum, Rosemarinus spp., Salvia spp., Scorzonera hispanica, Solanum melongena, Spinacea oleracea, Valerianella spp. (V. locusta, V. eriocarpa) and Vicia faba.
[0084] Preferred ornamental species include African violet, Begonia, Dahlia, Gerbera, Hydrangea, Verbena, Pink, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hortensia, rosemary, sage, St. John's wort, mint, pepper, tomato and cucumber.
[0085] The active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, legumes and vegetables, corn, rice and soybeans. The active ingredients according to the invention are also especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potatoes) and Chilo supressalis (preferably in rice).
[0086] In a further aspect, the invention may 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, Aphelenchoides species; Stinger nematodes, Belonolaimus longicaudatus and other species of Belonolaimus; Nematodes of pine trees, Bursaphelenchus xylophilus and other species of Bursaphelenchus; Ringed nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Punching nematodes, Dolichodorus species; Spiraled nematodes, Heliocotylenchus multicinctus and other species of Helicotylenchus; Sheathed nematodes, species of Hemicycliophora and species of Hemicriconemoides; Hirshmanniella species; Dagger nematodes, Hoploaimus species; False nematodes of root galls, Nacobbus species; Needle-shaped nematodes, Longidorus elongatus and other Longidorus species; Root lesion nematodes, species of Pratylenchus; Lesion-forming nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other species of Pratylenchus; Cave nematodes, Radopholus similis and other species of Radopholus; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis and other species of Rotylenchus; Scutellonema species; Root shortening and thickening nematodes, Trichodorus primitivus and other species of Trichodorus, species of Paratrichodorus; Stem nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other species of Tylenchorhynchus; Citrus nematodes, species of Tylenchulus; Dagger-shaped nematodes, Xiphinema species; and other species of plant parasitic nematodes, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp. and Quinisulcius spp ..
[0087] The compounds of the invention may also have activity against molluscs. Examples of these include, for example, Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. Nemoralis); 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.
[0088] The term "cultures" should be understood to also include cultivation plants 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, from bacteria producing toxins, especially those of the Bacillus genus.
[0089] The toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example, insecticidal proteins of Bacillus cereus or Bacillus popilliae; or Bacillus thuringiensis insecticidal proteins, such as δ-endotoxins, for example, CrylAb, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9c, or vegetative insecticidal proteins (Vip), for example, Vip1, Vip2, Vip3 or Vip3A ; or insecticidal proteins from nematode-colonizing bacteria, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect specific neurotoxins; toxins produced by fungi, such as Streptomyces toxins, plant lectins, such as pea lectins, barley lectins, or white bell lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome inactivating proteins (RIP), such as ricin, more RIP, abrina, lufina, saporina or briodina; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA reductase, ion channel blockers, such as sodium or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
[0090] In the context of the present invention it is to be understood as δ-endotoxins, for example, CrylAb, CrylAc, CrylF, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A, also expressly hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are recombinantly produced by a new combination of different domains of these proteins (see, for example, WO 02/15701). Truncated toxins, for example a truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids from the naturally occurring toxin are replaced. In such amino acid substitutions, preferably non-naturally occurring protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin G recognition sequence is inserted into a Cry3A toxin (see WO 03/018810 ).
[0091] 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.
[0092] 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. Deoxyribonucleic acids of the CryI type and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
[0093] The toxin contained in transgenic plants gives plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in beetles (Coleoptera), double-winged insects (Diptera) and moths (Lepidoptera).
[0094] Transgenic plants are known to contain one or more genes that encode an insecticidal resistance and express one or more toxins, and some of them are commercially available. Examples of such plants are: YieldGard® (corn variety that expresses a Cry1Ab toxin); YieldGard Rootworm® (corn variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (corn variety that expresses a Cry1Ab and a Cry3Bb1 toxin); Starlink® (corn variety that expresses a Cry9C toxin); Herculex I® (corn variety that expresses a Cry1Fa2 toxin and the enzyme phosphinothricin-N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresses a Cry1Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac toxin and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a Cry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); NatureGard®, Agrisure®GT Advantage (glyphosate tolerant trait GA21), Agrisure®CB Advantage (trait of corn borer (CB) Bt11) and Protecta®. Additional examples of such transgenic crops are: 1. Bt11 maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96/05/10. Genetically modified Zea mays that has been made resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenically expresses the PAT enzyme to achieve tolerance to the herbicide glufosinate ammonium. 2. Bt176 maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96/05/10. Genetically modified Zea mays that has been made resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a Cry1Ab toxin. Bt176 maize also expresses transgenically the PAT enzyme to achieve tolerance to the herbicide glufosinate ammonium. 3. MIR604 maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96/05/10. Maize that has been made resistant to insects by the transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by inserting a cathepsin G protease recognition sequence. The preparation of such transgenic corn plants is described in WO 03/018810. 4. MON 863 maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02/9. MON 863 expresses a Cry3Bb1 toxin and 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. Corn genetically modified for the expression of the Cry1F 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. Maize NK603 x MON 810 from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. It consists of hybrid maize varieties conventionally improved by crossing the genetically modified varieties NK603 and MON 810. Maize NK603 x MON 810 transgenically expresses the protein CP4 EPSPS, obtained from the Agrobacterium sp. CP4, which gives tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki that provides tolerance to certain Lepidoptera, including the European corn borer.
[0095] 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, (http://bats.ch).
[0096] 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.
[0097] Cultures can also be modified for enhanced resistance to fungal pathogens (for example, Fusarium, Anthracnose, or Phytophthora), bacterial (for example, Pseudomonas) or viral (for example, potato leaf rollers, viruses of the tomato head, virus of the mosaic of the cucurbits).
[0098] Crops also include those that have enhanced resistance to nematodes, such as the soy cyst nematode.
[0099] 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 .
[0100] Antipathogenic substances that can be expressed by such transgenic plants include, for example, ion channel blockers, such as sodium and calcium channel blockers, for example the viral toxins KP1, KP4 or KP6; stilbene synthases; bibenzyl synthases; chitinases; glucanases; so-called "pathogenesis-related proteins" (PRPs; see eg EP-A-0 392 225); 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).
[0101] Other areas of use of the compositions according to the invention are the protection of stored goods and warehouses, and the protection of raw materials such as wood, textiles, floor 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.
[0102] The present invention also provides a method for controlling pests (such as mosquitoes and other disease vectors; see also http://www.who.int/malaria/vector_control/irs/en/). In one embodiment, the method for controlling pests comprises applying the compositions of the invention to the target pests, at their location or on a surface or substrate by brushing, rolling, spraying, spreading or dipping. As an example, an application by IRS (internal residual spraying) of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention. In another embodiment, the application of such compositions is contemplated on a substrate such as a non-woven or woven material in the form of (or that can be used in the manufacture of) knitwear, clothing, bedding, curtains and tents.
[0103] In one embodiment, the method for controlling such pests comprises applying a pesticide-effective amount of the compositions of the invention to the target pests, at their location, or on a surface or substrate, in order to provide residual pesticidal activity effective on the surface or substrate. Such application can be made by brushing, rolling, spraying, spreading or immersing the pesticidal composition of the present invention. As an 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, the application of such compositions for residual pest control to a substrate such as a woven material in the form of (or that can be used in the manufacture of) knits, clothing, bedding, curtains and tents is contemplated.
[0104] 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. Methods for treating textiles are known, e.g., WO 2008/151984, WO 03/034823, US 5631072, WO 2005/64072, WO2006 / 128870, EP 1724392, WO 2005/113886 or WO 2007/090739.
[0105] 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.
[0106] In the area of tree injection / log 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 that follow: TABLE A. EXAMPLES OF DRILLS FROM EXOTIC WOOD OF ECONOMIC IMPORTANCE.
TABLE B. EXAMPLES OF NATIVE WOOD DRILLS OF ECONOMIC IMPORTANCE.





[0107] The present invention can also be used to control any insect pests that may be present in grass, including, for example, beetles, caterpillars, fire ants, land pearls, millipedes, ball armadillos, mites, little birds, mealybugs, floury bugs, ticks, leafhoppers, stinkbugs from southern grasses and white larvae. The present invention can also be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults.
[0108] In particular, the present invention can be used to control insect pests that feed on lawn roots including cormorants (such as Cyclocephala spp. (E.g. masked beetle C. lurida), Rhizotrogus spp. (P. European beetle, R. majalis), Cotinus spp. (e.g. S. João beetle, C. nitida), Popillia spp. (e.g., Japanese beetle, P. japonica), Phyllophaga spp. (eg May / June beetle), Ataenius spp. (eg Black lawn Ataenius, A. spretulus), Maladera spp. (eg Asian garden beetle, M. castanea) and Tomarus spp .), pearls-of-land (Margarodes spp.), paquinhas (orange, southern and with short wings; Scapteriscus spp., Gryllotalpa africana) and typical (common European melga, Tipula spp.).
[0109] The present invention can also be used to control lawn insect pests that inhabit the stalk, including military caterpillars (such as Corn Cartridge Caterpillar Spodoptera frugiperda, and Pseudaletia unipuncta grazing caterpillar), screw caterpillars, weevils (Sphenophorus spp., such as S. venatus verstitus and S. parvulus), and lawn moths (such as Crambus spp. and the tropical lawn moth, Herpetogramma phaeopteralis).
[0110] The present invention can also be used to control grass insect pests that live above the ground and feed on grass leaves, including grass stink bugs (such as southern grass stink bugs, Blissus insularis), tree mites Bermuda grass (Eriophyes cynodoniensis), floury bedbugs from Rhodes grass (Antonina graminis), leafhopper with two lines (Propsapia bicincta), leafhoppers, caterpillars (family Noctuidae) and green aphids.
[0111] The present invention can also be used to control other grass pests such as imported red fire ants (Solenopsis invicta) that create a lot of ants in the grass.
[0112] In the hygiene sector, the compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, scabies mites, thrombiculid mites, flies (biting and licking), parasitic fly larvae, lice, lice hair, bird lice and fleas. Examples of such parasites are:
[0113] Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculus spp. and Phtirus spp., Solenopotes spp.
[0114] Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp.
[0115] 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.
[0116] Of the order Siphonapterida, for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
[0117] Of the order Heteropterida, for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp ..
[0118] Of the order Blattarida, for example Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp ..
[0119] From the subclass Acaria (Acarida) and the orders Metastigmata and Mesostigmata, for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.
[0120] 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., Cytoditespp. and Laminosioptes spp.
[0121] The compositions according to the invention are also suitable for protection against insect infestations in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and cardboard, leather, floor coverings and buildings.
[0122] 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.
[0123] The compounds according to the invention can be used as pesticidal agents in unmodified form, but are generally formulated in compositions in various forms using formulation aids, such as carriers, solvents and surfactants. The formulations can be in various physical forms, eg in the form of dust powders, gels, wettable powders, water dispersible granules, water dispersible tablets, effervescent granules, emulsifiable concentrates, microemulsifiable concentrates, oil-in-emulsions. water, flowable oils, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as a carrier), impregnated polymer films or other known forms, eg from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Review (2010). Such formulations can be used directly or diluted before use. Dilutions can be made, for example, with water, in liquid fertilizers, micronutrients, biological organisms, oil or solvents.
[0124] Formulations can be prepared, for example, by mixing the active ingredient with formulation aids, in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surfactants or combinations thereof.
[0125] The active ingredients can also be contained in very thin microcapsules. The microcapsules contain the active ingredients in a porous carrier. This allows the active ingredients to be released into the environment in controlled quantities (for example, slow release). The microcapsules usually have a diameter of 0.1 to 500 microns. They contain active ingredients in an amount of about 25 to 95% by weight of the capsule weight. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. Encapsulation membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene / butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
[0126] Formulation aids which are suitable for the preparation of the compositions according to the invention are known per se. Liquid carriers can be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl and ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, acetic acid alkyl esters, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether , diethylene glycol methyl ether, N, N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol , ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, acetate d and glycerol, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, iso-octane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methanol propylene oxide, methanol propylene oxide and isoamyl, methyl and isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octilamine acetate, oleic acid, oleislamine, o -xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichlorethylene, perchlorethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and higher molecular weight alcohols ions such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like.
[0127] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, atapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cotton seed husks, wheat flour , soy flour, pumice, wood flour, crushed nut shells, lignin and similar substances.
[0128] A large number of surface active substances can be advantageously used in solid and liquid formulations, especially those formulations that can be diluted with a carrier before use. Surface active substances can be anionic, cationic, nonionic or polymeric and can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol / alkylene oxide addition products, such as tridecyl alcohol ethoxylate; soaps, such as sodium stearate, salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di (2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate, block copolymers of ethylene oxide and propylene oxide, and esters of mono- and di-alkylphosphate salts; and also additional substances described, eg, in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981).
[0129] Additional adjuvants that can be used in pesticidal formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, antifoams, complexing agents, substances neutralizing or pH modifiers and buffers, corrosion inhibitors, fragrances, wetting agents, enhancement of adhesion, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze, microbicides, and liquid and solid fertilizers.
[0130] The compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10%, based on the mixture to be applied. For example, the oil additive can be added to a spray tank at the desired concentration after a spray mixture has been prepared. Preferred oil additives comprise mineral oils or a vegetable oil, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of vegetable oils, for example methyl derivatives, or a animal oil, such as fish oil or beef tallow. Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially methyl derivatives of C12-C18 fatty acids, for example methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th Edition, Southern Illinois University, 2010.
[0131] The inventive compositions generally comprise from 0.1 to 99% by weight, especially from 0.1 to 95% by weight, of the compounds of the present invention and from 1 to 99.9% by weight of a formulation adjuvant which preferably includes from 0 to 25% by weight of a surfactant. While commercial products can preferably be formulated as concentrates, the end user will normally employ diluted formulations.
[0132] Application rates vary within wide limits and depend on the nature of the soil, the application method, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors controlled by the application method, the application time and the target culture. As a general guideline, the compounds can be applied at a rate of 1 to 2000 L / ha, especially from 10 to 1000 L / ha. Preferred formulations can have the following compositions (% by weight): Emulsifiable concentrates: active ingredient: 1 to 95%, preferably 60 to 90% surfactant: 1 to 30%, preferably 5 to 20% liquid carrier: 1 to 80% , preferably 1 to 35% Dust: active ingredient: 0.1 to 10%, preferably 0.1 to 5% solid carrier: 99.9 to 90%, preferably 99.9 to 99% Suspension concentrates: active ingredient: 5 75%, preferably 10 to 50% water: 94 to 24%, preferably 88 to 30% surfactant: 1 to 40%, preferably 2 to 30% Wettable powders: active ingredient: 0.5 to 90%, preferably 1 to 80% surfactant: 0.5 to 20%, preferably 1 to 15% solid carrier: 5 to 95%, preferably 15 to 90% Granules: active ingredient: 0.1 to 30%, preferably 0.1 to 15% carrier solid: 99.5 to 70%, preferably 97 to 85%
[0133] The following Examples further illustrate, but do not limit, the invention.


[0134] The combination is thoroughly mixed with the adjuvants and the mixture is carefully ground in a suitable mill, providing wettable powders that can be diluted with water to give suspensions of the desired concentration.

[0135] 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.


[0136] Emulsions of any required dilution, which can be used to protect plants, can be obtained from this concentrate by dilution with water.

[0137] Ready-to-use powders are obtained by mixing the combination with the vehicle and grinding the mixture in a suitable mill. Such powders can also be used for dry seed coatings.

[0138] The combination is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a draft.


[0139] The finely ground combination is uniformly applied, in a mixer, to kaolin moistened with polyethylene glycol. In this way, coated, non-dusty granules are obtained. Concentrated suspension

[0140] The finely ground combination is intimately mixed with the adjuvants, giving a concentrated suspension 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. Flowable concentrate for seed treatment


[0141] The finely ground combination is intimately mixed with the adjuvants, giving a concentrated suspension 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. Suspension of Slow Release Capsules
[0142] 28 parts of a combination are mixed with 2 parts of an aromatic solvent and 7 parts of the toluene diisocyanate / polymethylene polyphenylisocyanate mixture (8: 1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is reached. To this emulsion is added a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water. The mixture is stirred until the polymerization reaction is complete. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The suspension formulation for capsules contains 28% of the active ingredients. The average diameter of the capsules is 8 to 15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in an apparatus suitable for that purpose.
[0143] Formulation types include an emulsion concentrate (EC), a suspension concentrate (SC), a suspoemulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a microemulsion (ME), an oil dispersion (OD), an oil miscible fluid (OF), a miscible liquid in oil (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP ), a soluble granule (SG) or any technically possible formulation in combination with agriculturally acceptable adjuvants. Preparatory examples:
[0144] "Pf" means melting point in ° C. Free radicals represent methyl groups. The 1H NMR measurements 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. Any of the LCMS methods below was used to characterize the compounds. The characteristic LCMS values obtained for each compound were the retention time ("Rt", recorded in minutes) and the measured molecular ion (M + H) + or (M-H) -. LCMS methods: Method 1:
[0145] 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: UPLC HSS T3 from Waters, 1.8 μm, 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 minutes B 0% , 100%; 1.2-1.5 minutes B 100%; Flow (mL / minute) 0.85. Method 2:
[0146] The spectra were recorded on a Waters ACQUITY SQD Mass Spectrometer (Mass Spectrometer with single quadrupole), Ionization Method: Electrospray; Polarity: positive ions; capillary (kV) 3.00, Cone (V) 20.00, Extractor (V) 3.00, Source Temperature (° C) 150, Desolvation Temperature (° C) 400, Gas Flow in the Cone (L / Hour) 60, Desolvation Gas Flow (L / Hour) 700; Mass range: 100 to 800 Da, DAD wavelength range (nm): 210 to 400. Waters UPLC ACQUITY method with the following HPLC gradient conditions (Solvent A: Water / Methanol 9: 1, formic acid 0.1% and Solvent B: Acetonitrile, 0.1% formic acid)

[0147] Column type: UPLC ACQUITY HSS T3 by Waters; Column length: 30 mm; Column internal diameter: 2.1 mm; Particle Size: 1.8 microns; Temperature: 60 C. Method 3: Waters ACQUITY SQD Mass Spectrometer (single quadrupole mass spectrometer) Ionization method: Electrospray Polarity: positive ions
[0148] Capillary (kV) 3.00, Cone (V) 15.00, Extractor (V) 3.00, Source Temperature (° C) 150, Desolvation Temperature (° C) 400, Gas Flow in the Cone (L / Hour) 60, Desolvation Gas Flow (L / Hour) 700 Mass range: 100 to 800 From the DAD wavelength range (nm): 210 to 400 Waters UPLC ACQUITY method with the following conditions of HPLC gradient (Solvent A: Water / Methanol 9: 1, 0.1% formic acid and Solvent B: Acetonitrile, 0.1% formic acid)

[0149] Column type: Waters UPLC ACQUITY HSS T3; Column length: 30 mm; Column internal diameter: 2.1 mm; Particle Size: 1.8 microns; Temperature: 60 C. Method 4:
[0150] The spectra were recorded on a Waters Mass Spectrometer (SQD, SQDII single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 3.00 kV, Cone range : 30 V, Extractor: 2.00 V, Source Temperature: 150 ° C, Desolvation Temperature: 350 ° C, Cone Gas Flow: 50 L / h, Desolvation Gas Flow: 650 L / h, Range mass: 100 to 900 Da) and UPLC IClass Acquity from Waters: Binary pump, heated column compartment, diode array detector and ELSD detector. Column: UPLC HSS T3 from Waters, 1.8 μm, 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: 10 to 100% B in 1.2 min; Flow (ml / min) 0.85. EXAMPLE P1: Preparation of 2- [3-ethylsulfonyl-5- (6-methoxy-3-pyridyl) -2-pyridyl] -3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine (compound P1 ):
Step A-1: Preparation of tert-butyl N- [4-amino-6- (trifluoromethyl) -3-pyridyl] carbamate

[0151] To a solution of 6- (trifluoromethyl) pyridine-3,4-diamine (3,140 g, 17.73 mmol) (commercially available) in tetrahydrofuran (50 mL), was added tert-butoxycarbonyl and tert-butyl carbonate (4.643 g, 1.2 equiv.). The reaction mixture was stirred at 50 ° C for 20 hours, after which more tert-butoxycarbonyl and tert-butyl carbonate (1.1 g, 0.3 equiv.) Was added. After a further 20 hours of stirring, the reaction mixture was evaporated under reduced pressure to leave a solid residue which was adsorbed on dichloromethane, cooled to 0 ° C and the resulting suspension filtered. The crystalline residue was tert-butyl N- [4-amino-6- (trifluoromethyl) -3-pyridyl] carbamate. LCMS (method 1): 278 (M + H) +; retention time: 0.79 min. 1H NMR (400 MHz, CD3CN) δ ppm: 8.28 (s, 1 H); 7.09 (s, 1 H); 6.94 (bs, 1 H); 5.24 (bs, 2 H); 1.50 (s, 9H). Step A-2: Preparation of tert-butyl N- [4-amino-6- (trifluoromethyl) -3-pyridyl] -N-methyl-carbamate

[0152] A solution of tert-butyl N- [4-amino-6- (trifluoromethyl) -3-pyridyl] carbamate (synthesis described here above) (3.920 g, 14.14 mmol) in N, N-dimethylformamide ( 20 ml) was added to a stirred suspension of sodium hydride (0.648 g, 1.05 equiv.) In N, N-dimethylformamide (30 ml) over 20 minutes at 20-25 ° C. Fifteen minutes after the gas evolution ceased, iodomethane (2.21 g, 1.1 equiv.) Was added. The temperature rose to 30 ° C and was maintained at this level for 30 minutes. The reaction mixture was then carefully poured into water (200 ml) and the product was extracted twice with ethyl acetate. The organic phase was washed with brine, dried over sodium sulfate and evaporated under reduced pressure. The obtained pale brown solid was purified by column chromatography on silica gel, eluting with a mixture of ethyl acetate and heptanes. After recrystallization from ethyl acetate-heptanes, tert-butyl N- [4-amino-6- (trifluoromethyl) -3-pyridyl] -N-methyl-carbamate was isolated as colorless crystals. LCMS (method 1): 292 (M + H) +; retention time: 0.85 min. 1H NMR (400 MHz, CDCl3) δ ppm: 8.21 (s, 1 H); 7.00 (s, 1 H); 5.58 (bs, 2 H); 3.18 (s, 3H); 1.43 (s, 9H). Step A-3: Preparation of N3-methyl-6- (trifluoromethyl) pyridine-3,4-diamine

[0153] A solution of tert-butyl N- [4-amino-6- (trifluoromethyl) -3-pyridyl] -N-methyl-carbamate (3.530 g, 12.12 mmol) (preparation described above) in 1 , 4-dioxane (50 ml) was treated with 2N aqueous HCl solution (18.18 ml, 3 equiv.) And the resulting mixture was heated. The gas evolution started at around 70 ° C until the reaction mixture boiled for 20 minutes. Most of the dioxane was then removed under reduced pressure and the residual solution was treated with sodium bicarbonate (3.1 g, 36.9 mmol) after cooling to 20 ° C. There was formation of a thick paste that was extracted with ethyl acetate. The organic phase was washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The title compound was obtained as colorless crystals. LCMS (method 1): 192 (M + H) +; retention time: 0.25 min. 1H NMR (400 MHz, CDCl3) δ ppm: 7.90 (s, 1 H); 6.93 (s, 1 H); 4.09 (bs, 2 H); 3.40 (bs, 1H); 2.95 (s, 3 H). Step B-1: Preparation of methyl 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylate

[0154] To a solution of methyl 5-bromo-3-chloro-pyridine-2-carboxylate (0.100 g, 0.399 mmol) (commercial product) in tetrahydrofuran, stirred at 0 ° C, was added ethylsulfanyl sodium (0.034 g, 1 equiv.). After 1 hour at that temperature, the ice bath was removed and stirring was continued for 20 hours. The reaction mixture was then poured into water (15 ml) and extracted twice with ethyl acetate. The organic phases were dried over sodium sulfate and the solvent was removed. The residue was subjected to flash chromatography on silica gel and the selected fractions evaporated to give methyl 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylate as a colorless solid. LCMS (method 1): 276, 278 (M + H) +; retention time: 0.92 min. 1H NMR (400 MHz, CDCl3) δ ppm: 8.46 (s, 1 H); 7.79 (s, 1 H); 4.00 (s, 3 H); 2.94 (q, J = 7.4 Hz, 2H); 1.42 (t, J = 7.4 Hz, 3H). Step B-2: Preparation of 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylic acid

[0155] A solution of methyl 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylate (3,900 g, 14.12 mmol) (preparation described above) in a mixture of methyl alcohol (75 mL) and water ( 20 ml) stirred at 20 ° C was treated with 2N aqueous sodium hydroxide solution (7.04 ml, 1.05 equiv.). The mixture was stirred for two hours, then most of the alcohol was removed under reduced pressure. The residue was then treated with 2N aqueous HCl solution and the resulting precipitate was filtered off, washed with water and dried in vacuo. The title compound was obtained as a colorless solid. LCMS (method 1): 260, 262 (MH) -; retention time: 0.77 min. 1H NMR (400 MHz, d6-DMSO) δ ppm: 13.4 (bs, 1 H); 8.50 (s, 1 H); 8.07 (s, 1 H); 3.04 (q, J = 7.53 Hz, 2 H); 1.27 (t, J = 7.53 Hz, 3 H). Step C-1: Preparation of 2- (5-bromo-3-ethylsulfanyl-2-pyridyl] -3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine

[0156] To a suspension of 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylic acid (2,800 g, 10.68 mmol) in dichloromethane (10 mL) was added a drop of N, N-dimethylformamide, followed by chloride oxalyl oxide (2.034 g, 1.400 ml, 1.5 equiv.). After the end of the gas evolution, the reaction mixture was a pale red solution. The latter was evaporated under reduced pressure at a bath temperature of 60 ° C. The residue formed dark red crystals of 5-bromo-3-ethylsulfanyl-pyridine-2-carbonyl chloride.
[0157] To a clear solution of N3-methyl-6- (trifluoromethyl) pyridine-3,4-diamine (2.042 g, 10.68 mmol) in tetrahydrofuran (30 mL) was added a solution of 5-bromo-chloride 3-ethylsulfanyl-pyridine-2-carbonyl (described here above) dissolved in tetrahydrofuran (20 ml). The resulting mixture was heated to reflux temperature. A bulky white precipitate formed. After cooling to 20 ° C, the mixture was filtered and the filtrate evaporated under reduced pressure. The residue and the filter cake were combined and dissolved in water. The solution was neutralized by adding a saturated aqueous solution of sodium bicarbonate and the product was extracted twice with ethyl acetate. The organic solution was dried over sodium sulfate and evaporated under reduced pressure to give the crude product as a dark brown gum. This gum was adsorbed on meta-xylene (10 ml), para-toluenesulfonic acid (monohydrate) (2.032 g, 1 equiv.) Was added and the mixture was heated to 150 ° C for 8 hours. The reaction mixture was then poured into water (300 ml) and extracted twice with ethyl acetate. The crude dark brown product, after evaporation of the solvent under reduced pressure, was purified by column chromatography on silica gel, eluting with ethyl acetate and heptanes. The selected fractions were evaporated to give the title compound as a colorless solid. LCMS (method 1): 417, 419 (M + H) +; retention time: 1.04 min. 1H NMR (400 MHz, CDCl3) δ ppm: 8.96 (s, 1 H); 8.56 (s, 1 H); 8.20 (s, 1 H); 7.88 (s, 1 H); 4.07 (s, 3 H); 2.98 (q, J = 7.44 Hz, 2 H); 1.38 (t, J = 7.44 Hz, 3H).
[0158] Similarly, 2- (4-bromo-2-ethylsulfanyl-phenyl) -3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine (solid, mp 113-114 ° C) from 4-bromo-2-ethylsulfanyl-benzoic acid and N3-methyl-6- (trifluoromethyl) pyridine-3,4-diamine. LCMS (method 1): 416/418 (M + H) +; retention time: 1.07 min. 1H NMR (400 MHz, CDCl3) δ ppm: 1.26 (t, 3H), 2.89 (q, 2H), 3.80 (s, 3H), 7.31 (d, 1H), 7.50 (dd, 1H), 7.61 (d, 1H), 8.13 (d, 1H), 8.93 (s, 1H). Step C-2: Preparation of 2- (5-bromo-3-ethylsulfonyl-2-pyridyl] -3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine

[0159] A solution of 2- (5-bromo-3-ethylsulfanyl-2-pyridyl) -3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine (2,000 g, 4.79 mmol) in dichloromethane (50 mL) was stirred in an ice bath and meta-chloroperbenzoic acid (2.54 g, 70% pure, 2.5 equiv.) was added in portions, such that the temperature of the reaction mixture was maintained below 10 ° C. The bath was then removed and the mixture was stirred an additional 4 hours at 20 ° C. After completion of the reaction, the mixture was stirred with saturated aqueous sodium bicarbonate solution. The phases were separated and the aqueous phase was extracted with dichloromethane. The organic layers were combined, dried over sodium sulfate and evaporated. The residue was subjected to column chromatography on silica gel, eluting with ethyl acetate in heptanes. The selected fractions were evaporated and the residue was triturated with heptanes to give the title compound as a colorless solid. LCMS (method 1): 449, 451 (M + H) +; retention time: 0.95 min. 1H NMR (400 MHz, CDCl3) δ ppm: 9.06 (s, 1 H); 9.00 (s, 1 H); 8.68 (s, 1 H); 8.11 (s, 1 H); 3.90 (s, 3 H); 3.82 (q, 2 H); 1.38 (t, 3H).
[0160] Similarly, 2- (4-bromo-2-ethylsulfonyl-phenyl) -3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine (solid, mp 180-181 ° C) from 2- (4-bromo-2-ethylsulfanyl-phenyl) -3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine. LCMS (method 1): 448/450 (M + H) +; retention time: 0.95 min. 1H NMR (400 MHz, CDCl3) δ ppm: 1.27 (t, 3H), 3.38 (q, 2H), 3.74 (s, 3H), 7.43 (d, 1H), 7.98 (dd, 1H), 8.09 (d, 1H), 8.37 (d, 1H), 8.95 (s, 1H). Step C-3: Preparation of 2- [3-ethylsulfonyl-5- (6-methoxy-3-pyridyl) -2-pyridyl] -3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine ( compound P1)

[0161] A solution of 2- (5-bromo-3-ethylsulfonyl-2-pyridyl) -3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine (preparation described above) (0.015 g, 0.035 mmol), potassium carbonate (2.0 equiv.) and aminobiphenyl palladium chloride pre-catalyst X-Phos (0.1 eq) in tetrahydrofuran (0.7 ml) and water (0.3 ml) were purged with argon before being added to (6-methoxy-3-pyridyl) boronic acid (2.0 equiv.) in a flask under an argon atmosphere. The reaction mixture was then heated in a microwave oven at 120 ° C for 15 minutes. The extent of the reaction was measured by UPLC-MS (method 2). After removing the solvent, water (2 ml) was added and the mixture was extracted three times with ethyl acetate (2 ml). The combined organic phases were concentrated and the residue was dissolved in N, N-dimethylformamide and subjected to HPLC chromatography coupled with MS, the fractionation being triggered by ionization, to give the title compound P1. LCMS (method 2): 478 (M + H) +; retention time: 1.52 min. EXAMPLE 2: Preparation of 2 - [3-ethylsulfonyl-5- (3- (trifluoromethyl) pyrazol-1-yl] -2-pyridyl] -3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine (compound P2 )

[0162] A solution of 2- [3-ethylsulfonyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -2-pyridyl] -3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine (preparation described hereinafter, compound I1) (0.050 g, 0.101 mmol) in pyridine (1.0 ml) 3-trifluoromethyl-1H-pyrazole (0.018 g, 1, 3 equiv.) And copper (II) acetate (0.009 g, 0.5 equiv.). The reaction mixture was stirred under an oxygen atmosphere (flask) for 60 hours, then it was diluted with water and the mixture was extracted twice with ethyl acetate. The combined organic extract was dried over sodium sulfate and evaporated. The residue was subjected to flash chromatography on silica gel eluting with ethyl acetate-heptane mixtures. Evaporation of the selected fractions gave the title compound P2. LCMS (method 1): 505 (M + H) +; retention time: 1.04 min. EXAMPLE P3: Preparation of 2- [5- (4-cyclopropyl-6-methyl-pyrimidin-2-yl) -3-ethylsulfonyl-2-pyridyl] -3-methyl-6- (trifluoromethyl) imidazo [4,5- c] pyridine (compound P23) (P23)
Step 1: Preparation of 5-bromo-3-ethylsulfanyl-pyridine-2-carbonitrile

[0163] To a solution of 5-bromo-2-cyano-3-nitropyridine (58.0 g, 242 mmol, 1.0 eq.) In 1000 mL of N, N-dimethylformamide under argon, sodium ethanethiolate (23.7 g, 254 mmol, 1.05 eq.) Was slowly added at a temperature between -40 and -50 ° C. The dark mixture was allowed to stir at rt overnight. After dilution with tert-butylmethylether, the mixture was quenched with water. The organic layer was washed with water and brine, dried over sodium sulfate, filtered and evaporated. The crude brown oil was purified by column chromatography, eluting with ethyl acetate / cyclohexane to give a light orange solid. 1H NMR (400 MHz, CDCl3) δ ppm: 8.50 (s, 1 H); 7.81 (s, 1 H); 3.06 (q, 2 H); 1.40 (t, 3H). Step 2: Preparation of 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylic acid

[0164] A solution of 5-bromo-3-ethylsulfanyl-pyridine-2-carbonitrile (43 g, 170 mmol, 1.0 eq.) In 800 ml of 32% aqueous hydrogen chloride was heated to 60 ° C during the night. Dioxane (100 ml) was added and the mixture was further stirred at 60 ° C for 48 h. The reaction mixture was cooled to 0-5 ° C, treated with an aqueous solution of sodium hydroxide (30% NaOH) to pH 11 and washed with 2 x 200 ml of tert-butylmethylether. The water phase was acidified with 10% HCl back to pH 4, the resulting solid was filtered, washed with water and dried in vacuo. LCMS (method 1): 262, 264 (M + H) +; retention time: 0.77 min. 1H NMR (400 MHz, CDCl3) δ ppm: 8.50 (s, 1 H); 8.06 (s, 1 H); 3.03 (q, 2 H); 1.24 (t, 3H). Step 3: Preparation of 2- (5-bromo-3-ethylsulfanyl-2-pyridyl) - 3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine
Preparation according to EXAMPLE P1, step C-1 above. Step 4: Preparation of 2- (5-bromo-3-ethylsulfonyl-2-pyridyl) - 3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine
Preparation according to EXAMPLE P1, step C-2 above. Step 5: Preparation of 2- [3-ethylsulfonyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -2-pyridyl] -3-methyl-6- ( trifluoromethyl) imidazo [4,5-c] pyridine (compound I1)

[0165] A mixture of 2- (5-bromo-3-ethylsulfonyl-2-pyridyl) -3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine (preparation described above) (0.050 g, 0.111 mmol), potassium acetate (0.027 g, 2.5 equiv.) and 4,4,5,5-tetramethyl-2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- il) -1,3,2-dioxaborolane (0.042 g, 1.5 equiv.) in 1,2-dimethoxyethane (3 mL) was gently purged with argon, then 1,1'-bis (diphenylphosphino) -ferrocene complex ) dichloropalladium-dichloromethane (1: 1) (0.005 g, 0.05 equiv.) was added and the pale yellow mixture was stirred under an inert atmosphere, while heating to 90 ° C. After consumption of the starting bromide, the dark reaction mixture was diluted with water (20 ml) and extracted twice with ethyl acetate. The combined organic phases were dried over sodium sulfate and concentrated under reduced pressure. The dark brown gum was adsorbed on diethyl ether and filtered through a pad of celite®. The filtrate was extracted with a mixture of water (5 ml) and 1 N aqueous sodium hydroxide (0.2 ml), and then the aqueous phase was treated with 1 N aqueous hydrochloric acid (0.3 ml). The precipitated solid was extracted twice with diethyl ether. The organic phase was washed with brine, dried over sodium sulfate and evaporated under reduced pressure to give the title compound as a colorless solid. LCMS (method 1): 413 (MH) -; 827 (2M-H) -; 415 (M + H) + for the corresponding boronic acid; retention time: 0.77 min (in this case, M corresponds to the corresponding boronic acid and not the pinacol ester, but the NMR shows the pinacol part). 1H NMR (400 MHz, CDCl3) δ ppm: 9.28 (s, 1 H); 8.99 (s, 1 H); 8.87 (s, 1 H); 8.11 (s, 1 H); 3.88 (s, 3 H); 3.76 (q, J = 7.4 Hz, 2 H); 1.41 (s, 12 H); 1.38 (t, J = 7.4 Hz, 3 H). Step 6: Preparation of 2- [5- (4-cyclopropyl-6-methyl-pyrimidin-2-yl) -3-ethylsulfonyl-2-pyridyl] -3-methyl-6- (trifluoromethyl) imidazo [4,5- c] pyridine (compound P23)

[0166] 2- [3-Ethylsulfonyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -2-pyridyl] -3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine (300 mg, 0.544 mmol, 1.0 eq.) was dissolved in 4 ml of dioxane in a microwave flask followed by 2-chloro-4-cyclopropyl-6-methyl- pyrimidine (127 mg, 0.725 mmol, 2.0 eq.) and sodium carbonate (0.54 ml, 1.09 mmol, 3.0 eq.). The mixture was purged with argon for 10 min. and tetrakis (triphenylphosphine) palladium (0) (Pd (PPh3) 4, 21 mg, 0.0181 mmol, 5% per mol) was added. The cloudy, orange-brown solution was irradiated in the microwave at 110 ° C for 15 minutes. The mixture was quenched with 10 ml of water, extracted with 3 x 10 ml of ethyl acetate, the organic phase was washed with brine, dried over sodium sulfate, filtered and evaporated. The crude brown resin was purified by column chromatography on silica gel, eluting with ethyl acetate / cyclohexane. LCMS (method 1): 503 (M + H) +; retention time: 1.12 min. Mp: 224-226oC. 1H NMR (400 MHz, CDCl3) δ ppm: 9.94 (s, 1 H); 9.43 (s, 1 H); 9.00 (s, 1 H); 8.12 (s, 1 H); 7.08 (s, 1 H); 3.91 (s, 3 H), 3.81 (q, 2 H); 2.59 (s, 3 H); 2.06 (m. 1 H); 1.41 (3, 3 H); 1.28 (m, 2 H); 1.14 (m, 2 H). EXAMPLE P4: Preparation of 2- [5- (4-chloropyrazol-1-yl) -3-ethylsulfonyl-2-pyridyl] -3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine (compound P16 )
Step 1: Preparation of 2- [5- (4-chloropyrazol-1-yl) -3-ethylsulfanyl-2-pyridyl] -3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine (compound P14 )

[0167] To a solution of 2- (5-bromo-3-ethylsulfanyl-2-pyridyl) -3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine (300 mg, 0.690 mmol) and 4 -chloro-1H-pyrazole (84 mg, 0.794 mmol) in N, N-dimethylformamide (2 mL) under argon, copper (I) iodide (13.2 mg, 0.069 mmol), N, N'-dimethylethylenediamine ( 12.3 mg, 14.8 μL, 0.138 mmol) and potassium carbonate (38.5 mg, 0.276 mmol). The mixture was heated to 125 ° C overnight. After cooling, the reaction mixture was diluted with tert-butyl ether and water, the layers separated, the aqueous phase extracted twice with tert-butyl ether and methyl, the combined organic layers washed with water and brine, dried over sodium sulfate and evaporated to dryness. The residue was purified by C18 reverse phase column chromatography (acetonitrile gradient in water) to give 2- [5- (4-chloropyrazol-1-yl) -3-ethylsulfanyl-2-pyridyl] -3-methyl-6 - (trifluoro-methyl) imidazo [4,5-c] pyridine (compound P14) as a solid (160 mg), mp 200-202 ° C. LCMS (method 1): 439/441 (M + H) +, retention time 1.07 min. Step 2: Preparation of 2- [5- (4-chloropyrazol-1-yl) -3-ethylsulfonyl-2-pyridyl] -3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine (compound P16 )

[0168] Obtained from 2- [5- (4-chloropyrazol-1-yl) -3-ethylsulfanyl-2-pyridyl] -3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine ( 146 mg, 0.323 mmol) and meta-chloroperbenzoic acid (199 mg, 0.807 mmol, 70%) in dichloromethane (6 mL) according to the procedure EXAMPLE P1, step C-2. The mixture was stirred at room temperature for 3 hours. Purification by flash chromatography (cyclohexane / ethyl acetate 3: 1) gave 2- [5- (4-chloropyrazol-1-yl) -3-ethylsulfonyl-2-pyridyl] -3-methyl-6- (trifluoromethyl) imidazo [4,5-c] pyridine (compound P16) as a solid (142 mg), mp 207-210 ° C. LCMS (method 1): 471/473 (M + H) +, retention time 1.01 min. 1H NMR (400 MHz, CDCl3) δ ppm: 1.41 (t, 3H), 3.88 (q, 2H), 3.93 (s, 3H), 7.82 (s, 1H), 8.12 (s, 1H), 8.16 (s, 1H), 8.73 (d, 1H), 9.00 (s, 1H), 9.39 (d, 1H). Table P1: Examples of compounds of formula (I)














Table I1: Example of an intermediate compound of the formula (IV)

[0169] The activity of the compositions according to the invention can be increased considerably, and adapted to prevailing circumstances, by adding other active ingredients in terms of insecticides, acaricides and / or fungicides. Mixtures of the compounds of formula I with other 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 for plants, reduced phytotoxicity, insects can be controlled in their different stages of development or better behavior during their production, for example, during crushing or mixing, during storage or during use.
[0170] Suitable additions to active ingredients here are, for example, representative of the following classes of active ingredients: organophosphate compounds, nitrophenol derivative, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethylamine derivatives, macrolides, neonicotinoids and preparations of Bacillus thuringiensis.
[0171] 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 and 6 and P1 of the present invention"): an adjuvant selected from group of substances consisting of petroleum oils (alternative name) (628) + TX, an acaricide selected from the group of substances consisting of 1,1-bis (4-chlorophenyl) -2-ethoxyethanol (IUPAC name) (910) + TX , 2,4-dichlorophenyl benzenesulfonate (IUPAC / Chemical Abstracts name) (1059) + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name) (1295) + TX, 4-chlorophenyl sulfone 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 pipermethrin (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, arsenious 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, butocarboxim (103) + TX, butoxycarboxim (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, clordimeform (964) + TX, clori chlordimeform (964) + TX, chlorfenapyr (130) + TX, chlorfenetol (968) + TX, chlorfenson (970) + TX, chlorophensulfide (971) + TX, chlorfenvinphos (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, cyphlumetofen (CAS No: 400882-07-7) + TX, cyhalothrin (196) + TX, cyhexatin (199) + TX, cypermethrin (201) + TX, DCPM (1032) + TX, DDT (219) + TX, demefion (1037) + TX, demefion-O (1037) + TX, demefion-S (1037) + TX, demeton (1038) + TX, demetonmethyl (224) + TX, demeton-O (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S- methyl (224) + TX, demeton-S-methylsu lfona (1039) + TX, diafentiuron (226) + TX, dialiphos (1042) + TX, diazinon (227) + TX, diclofluanide (230) + TX, dichlorvós (236) + TX, diclifós (alternative name) + TX, dicofol (242) + TX, dicrotophos (243) + TX, dienochlor (1071) + TX, dimefox (1081) + TX, dimetoate (262) + TX, dinactin (alternative name) (653) + TX, dinex (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] + TX, ethion (309) + TX, etoate-methyl (1134) + TX, ethoxazole (320) + TX, etrimphós (1142) + TX, phenazaflor (1147) + TX, Phenazakin (328 ) + TX, fenbutatin 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, fluazuron (1166) + TX, flubenzimine (1167) + TX, flucicloxuron (366) + TX, flucitrinate ( 367) + TX, fluenethyl (1169) + TX, flufenoxuron (370) + TX, flumethrin (372) + TX, fluorbenside (1174) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, formethanate (405) + TX, formethanate hydrochloride (405) + TX, formotion (1192) + TX, formparanate (1193) + TX, HCH range (430) + TX, gliodine (1205) + TX, halfenprox ( 424) + TX, heptenophos (432) + TX, hexadecyl cyclopropanecarboxylate (IUPAC / Chemical Abstracts name) (1216) + TX, hexitiazox (441) + TX, iodomethane (IUPAC name) (542) + TX, isocarbofos (name alternative) (473) + TX, O- (methoxyminothiophosphoryl) isopropyl salicylate (IUPAC name) (473) + TX, ivermectin (alternative name) [CCN] + TX, Jasmine I (696) + TX, Jasmine II (696) + TX, Iodphenphen (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, metacrifos (1266) + TX, metamidophos (527) + TX, metidation (529) + TX, metiocarb (530) + TX, methyl (531) + TX, methyl bromide (537) + TX, metolcarb (550) + TX, mevinfos (556) + TX, mexacarbato (1290 ) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, monocrotophos (561) + TX, morfotion (1300) + TX, moxidectin (alternative name) [ CCN] + TX, naled (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) + T X, 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, fencapton (1330) + TX, phentoate (631) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, fosmet (638) + TX, phosphamidon (639) + TX, foxim (642) + TX, pyrimiphos-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, propetamfos (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, quinalfos (711) + TX, quintiofós (1381) + TX, R-1492 (development code) (1382) + TX, RA-17 (development code) (1383) + TX, rotenone ( 722) + TX, escradano (1389) + TX, sebufós (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, sofamide (1402) + TX, spirodiclofen (738) + TX, spiromesifene (739) + TX, SSI121 (development code) (1404) + TX, sulfiram (alternative name) [CCN] + TX, sulfluramid (750) + TX, sulfotep (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, tiofanox (800) + TX, thiometon (801) + TX, thioquinox (1436) + TX, thuringian (alternative name) [CCN] + TX, triamiphos (1441) + TX, triaratene (1443) + TX, triazophos (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, endothal (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, endocrine (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, casugamycin (483) + TX, nickel casugamycin hydrochloride (483) + TX, bis (dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapirin (580) + TX, octylinone (590) + TX, oxolinic acid (606) + TX, oxy tetracycline (611) + TX, potassium hydroxyquinoline sulphate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, keyboard software (766) + TX, and thiomersal (alternative name) [CCN] + TX, a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis (alternative name) (33) + TX, Aphidius colemani ( alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide ( scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51) + TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51) + TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alternative name) (53) + TX, Beauveria brongniartii (alternative name) (54) + TX, Chrysoperla carnea (alternative name) (151) + TX, Cryptolaemus montrouzieri ( alternative name) (178) + TX, Cydia pomonella GV (alternative name) (191) + TX, Dacnusa sibirica (alternative name) (212) + TX, Diglyphus isaea (alternative name) (254) + TX, Encarsia formosa (name (293) + TX, Eretmocerus eremicus (alternative name) (300) + TX, Helicoverpa zea NPV (alternative name) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alternative name) (433) + TX, Hippodamia convergens (alternative name) (442) + TX, Leptomastix dactylopii (alternative name) (488) + TX, Macrolophus caliginosus (alternative name) (491) + TX, Mamestra brassicae NPV (alternative name) (494) + TX, Metaphycus helvolus (alternative name) (522) + TX, Metarhizium anisopliae var. acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. lecontei NPV (alternative name) (575) + TX, Orius spp. (alternative name) (596) + TX, Paecilomyces fumosoroseus (alternative name) (613) + TX, Phytoseiulus persimilis (alternative name) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741) + TX, Steinernema bibionis (alternative name) (742) + TX, Steinernema carpocapsae (alternative name) (742) + TX, Steinernema feltiae (alternative name) (742) + TX, Steinernema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinernema riobravis (alternative name) (742) + TX, Steinernema scapterisci (alternative name) (742) + TX, Steinernema spp. (alternative name) (742) + TX, Trichogramma spp. (alternative name) (826) + TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848) + TX, 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, diflubenzurom (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methotepa [CCN] + TX, methyl afolate [CCN ] + TX, morzid [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-1-yl acetate with (E ) -dec-5- en-1-ol (IUPAC name) (222) + TX, (E) -tridec-4-en1-yl acetate (IUPAC name) (829) + TX, (E) -6-methyl-hept-2-en-4-ol (IUPAC name) (541) + TX, (E, Z) -tetradeca-4,10-dien-1-yl acetate (IUPAC name) (779) + TX, (Z) -dodec-7- en-1-yl acetate (IUPAC name) (285) + TX, (Z) -hexadec-11-enal (IUPAC name) (436) + TX, (Z) -hexadec-11-en-1-yl acetate (IUPAC name) (437) + TX, (Z) -hexadec-13-en-11-in-1-yl acetate (IUPAC name) (438) + TX, (Z) -icos-13-en-10-one (IUPAC name) (448) + TX, (Z) -tetradec-7-en-1-al (IUPAC name) (782) + TX, (Z) -tetradec-9-en-1-ol (IUPAC name) (783) + TX, acetate (Z) -tetradec-9-en-1-yl (IUPAC name) (784) + TX, (7E, 9Z) -dodeca-7,9-dien-1-yl acetate (IUPAC name) (283) + TX, (9Z, 11E) -tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780) + TX, (9Z, 12E) -tetradeca-9,12-dien-1-yl acetate (IUPAC name) (781) + TX, 14-methyloctadec-1-ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one (IUPAC name) (544) + TX, alpha-multistriatin (alternative name) [CCN] + TX, brevicomine (n alternative name) [CCN] + TX, codlelure (alternative name) [CCN] + TX, codlemona (alternative name) (167) + TX, cuelure (alternative name) (179) + TX, disparlure (277) + TX, acetate dodec-8-en-1-yl (IUPAC name) (286) + TX, dodec-9-en-1-yl (IUPAC name) acetate (287) + TX, dodeca-8 + TX, 10 acetate -dien-1-ila (IUPAC name) (284) + TX, dominicalure (alternative name) [CCN] + TX, ethyl 4-methyloctanoate (IUPAC name) (317) + TX, eugenol (alternative name) [CCN] + TX, frontine (alternative name) [CCN] + TX, gossiplure (alternative name) (420) + TX, grandlure (421) + TX, grandlure I (alternative name) (421) + TX, grandlure II (alternative name) (421) + TX, grandlure III (alternative name) (421) + TX, grandlure IV (alternative name) (421) + TX, hexalure [CCN] + TX, ipsdienol (alternative name) [CCN] + TX, ipsenol ( alternative name) [CCN] + TX, japonilure (alternative name) (481) + TX, lineatin (alternative name) [CCN] + TX, litlure (alternative name) [CCN] + TX, looplure (alternative name) ternative) [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-1-yl (IUPAC name) (588) + TX, octadeca acetate3,13-dien-1-yl (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-11-en-1-yl acetate (IUPAC name) (785) + TX, trimedlure (839) + TX, trimedlure A (alternative name) (839) + TX, trimedlure B1 (alternative name) ( 839) + TX, trimedlure B2 (alternative name) (839) + TX, trimedlure C (alternative name) (839) and trunccall (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, dib adipate utila (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, phthalate dimethyl [CCN] + TX, ethylhexanediol (1137) + TX, hexamide [CCN] + TX, methoxy-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] + picaridin [CCN] + TX, an insecticide selected from the group of substances consisting of 1-dichloro-1-nitroethane (IUPAC / Chemical Abstracts name) (1058) + TX, 1,1-dichloro-2,2-bis (4-ethylphenyl) ethane ( IUPAC name) (1056), + TX, 1,2-dichloropropane (IUPAC / Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1 -bromo-2-chloroethane (IUPAC name / Chemical Abstracts) (916) + TX, 2,2,2-trichloro-1- (3,4-dichlorophenyl) ethyl acetate (IUPAC name) (1451) + TX, phosphate 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl (IUPAC name) (1066) + TX, 2- (1,3-dithiolan-2-yl) phenyl (IUPAC / Chemical Abstracts name) dimethylcarbamate (11 09) + TX, 2- (2-butoxyethoxy) ethyl thiocyanate (IUPAC / Chemical Abstracts name) (935) + TX, 2- (4,5-dimethyl-1,3-dioxolan2-yl) phenyl methylcarbamate ( IUPAC / Chemical Abstracts name) (1084) + TX, 2- (4-chloro-3,5-xylyloxy) ethanol (IUPAC name) (986) + TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984) + TX, 2-imidazolidone (IUPAC name) (1225) + TX, 2-isovalerylindan1,3-dione (IUPAC name) (1246) + TX, 2-methyl (prop-2-inyl) aminophenyl methylcarbamate (IUPAC name) (1284) + TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433) + TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917) + TX, 3-methyl-1- dimethylcarbamate phenylpyrazol-5-yl (IUPAC name) (1283) + TX, 4-methyl (prop-2-inyl) amino-3,5-xylyl methylcarbamate (IUPAC name) (1285) + TX, 5.5- dimethylcarbamate dimethyl-3-oxocyclohex-1-enyl (IUPAC name) (1085) + TX, abamectin (1) + TX, acephate (2) + TX, acetamipride (4) + TX, acetion (alternative name) [CCN] + TX , acetoprol [CCN] + TX, acrinatrin (9) + TX, acrylonitrile (IUPA name C) (861) + TX, alanicarb (15) + TX, aldicarb (16) + TX, aldoxycarb (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 (IUPAC / Chemical name Abstracts) (892) + TX, bartrina [CCN] + TX, Bayer 22/190 (development code) (893) + TX, Bayer 22408 (development code then) (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-cyclopentenyl isomer of bioalethin (alternative name) (79) + TX, bioethanometrine [CCN] + TX, biopermetrin (908) + TX, bioresmethrin (80) + TX, ether bis (2-chloroethyl) (IUPAC name) (909) + TX, bistrifluron (83) + TX, borax (86) + TX, brofenvalerate (alternative name) + TX, bromphenvenins (914) + TX, bromocyclene (918) + TX, bromo-DDT (alternative name) [CCN] + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, bufencarb (924) + TX, buprofezina (99) + TX, butacarb (926) + TX, butatiophos (927) + TX, butocarboxy (103) + TX, butonate (932) + TX, butoxycarboxy (104) + TX, butylpyridabene (alternative name) + TX, cadusafós (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 (IUPAC / Chemical Abstracts name) (945) + TX, carbon tetrachloride (IUPAC name) (946) + TX, carbophenothione (947) + TX, carbosulfan (119) + TX, cartap (123) + TX, cartap hydrochloride (123) + TX, cevadine (alternative name) (725) + TX, chlorobenzene (960) + TX, chlordane (128) + TX, chlordecone (963 ) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorethoxyphos (129) + TX, chlorfenapyr (130) + TX, chlorfenvinphos (131) + TX, chlorfluazuron (132) + TX, chlormefos ( 136) + TX, chloroform [CCN] + TX, chloropicrin (141) + TX, chlorfoxin (989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX, chlorpyrifosmethyl (146) + TX, chlorhephos (994 ) + TX, chromafenozide (150) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerines (696) + TX, cis-resmethrin (alternative 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, cytate (alternative name) [CCN] + TX, dlimonene (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-O (1037) + TX, demefion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-O (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038 ) + TX, demeton-S-methyl (224) + TX, demeton-S-methylsulfone (1039) + TX, diafentiuron (226) + TX, dialiphos (1042) + TX, diamidafós (1044) + TX, diazinon (227) + TX, dicapton (1050) + TX, diclofention (1051) + TX, dichlorvós (236) + TX, diclifós (alternative name) + TX, dicresil (alternative name) [CCN] + TX, dicrotofós (243) + TX, dicyclanil (244) + TX, dieldrina (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, dinoprop (1093) + TX, dinosam (1094) + TX, dinoseb (1095) + TX, dinotefuran (271) + TX, diophenolan (1099) + TX, dioxabenzofos (1100) + TX , dioxacarb (1101) + TX, dioxationa (1102) + TX, disulfoton (278) + TX, dichrophos (1108) + TX, DNOC (282) + TX, doramectin (alternative name) [CCN] + TX, DSP (1115 ) + T X, ecdysterone (alternative name) [CCN] + TX, EI 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, esfenvalerate (302) + TX, etafós (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, dichloride ethylene (chemical name) (1136) + TX, ethylene oxide [CCN] + TX, etofenprox (319) + TX, etrimphós (1142) + TX, EXD (1143) + TX, famfur (323) + TX, fenamiphos (326) + TX, fenazaflor (1147) + TX, phenlorphos (1148) + TX, fenetacarb (1149) + TX, fenflutrina (1150) + TX, fenitrotion (335) + TX, fenobucarb (336) + TX, fenoxacrim ( 1153) + TX, phenoxycarb (340) + TX, phenpiritrin (1155) + TX, fenpropatrin (342) + TX, fenpirad (alternative name) + TX, fensulfotion (1158) + TX, fention (346) + TX, fention-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, fluenethyl (1169) + TX, flufenorin [CCN] + TX, flufenoxuron (370) + TX, flufenprox (1171) + TX, flumethrin (372) + TX, fluvalinate (1184) + TX, FMC 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, gamacialotrina (197) + TX, gama-HCH (430) + TX, guazatina (422) + TX, guazatina acetates (422) + TX , GY-81 (development code) (423) + TX, halfenprox (424) + TX, halofenozide (425) + TX, HCH (430) + TX, HEOD (1070) + TX, heptachlor (1211) + TX, heptenophos (432) + TX, heterophos [CCN] + TX, hexaflumuron (439) + TX, HHDN (864) + TX, hydramethylnone (443) + TX, hydrogen cyanide (444) + TX, hydroprene (445) + TX hi quincarb (1223) + TX, imidacloprid (458) + TX, imiprotrine (460) + TX, indoxacarb (465) + TX, iodomethane (IUPAC name) (542) + TX, IPSP (1229) + TX, isazophos (1231) + TX, isobenzane (1232) + TX, isocarbophos (alternative name) (473) + TX, isodrine (1235) + TX, isofenfos (1236) + TX, isolane (1237) + TX, isoprocarb (472) + TX, O - isopropyl (methoxyminothiophosphoryl) salicylate (IUPAC name) (473) + TX, isoprothiolan (474) + TX, isothioate (1244) + TX, isoxation (480) + TX, ivermectin (alternative name) [CCN] + TX, jasmine I (696) + TX, Jasmine II (696) + TX, iodphenates (1248) + TX, youth hormone I (alternative name) [CCN] + TX, youth hormone II (alternative name) [CCN] + TX, youth hormone III (alternative name) [CCN] + TX, celevan (1249) + TX, quinoprene (484) + TX, lambda-cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepimectin (CCN) + TX, leptophos (1250) + TX, lindane (430) + TX, lirimphos (1251) + TX, lufenuron (490) + TX, litidation (1253) + TX, methylcarbamate d and m-cumenyl (IUPAC name) (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, metaflumizone (CCN) + TX, metam ( 519) + TX, metam-potassium (alternative name) (519) + TX, metam-sodium (519) + TX, metacryphs (1266) + TX, metamidophos (527) + TX, methanesulfonyl fluoride (IUPAC name / Chemical Abstracts ) (1268) + TX, metidation (529) + TX, metiocarb (530) + TX, metocrotophos (1273) + TX, methomyl (531) + TX, methoprene (532) + TX, methoxy-butyl (1276) + TX , methotrine (alternative name) (533) + TX, methoxychloride (534) + TX, methoxyfenozide (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methyl chloroform (alternative name ) [CCN] + TX, methylene chloride [CCN] + TX, metoflutrin [CCN] + TX, metolcarb (550) + TX, methoxyzone (1288) + TX, mevinfos (556 ) + TX, mexacarbato (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, mirex (1294) + TX, monocrotophos (561) + TX , morfotion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naphthalophos (alternative name) [CCN] + TX, naled (567) + TX, naphthalene (IUPAC / Chemical Abstracts name) (1303) + TX, NC-170 (development code) (1306) + TX, NC-184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (578) + TX, nifluridide (1309) + TX, 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, O5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate (IUPAC name) ( 1057) + TX, O phosphorothioate, O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl (IUPAC name) (1074) + TX, O phosphorothioate, O-dieti l O-6-methyl-2-propylpyrimidin-4-yl (IUPAC name) (1075) + TX, O, O, O 'dithiopyrophosphate, O'-tetrapropyl (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, laurate pentachlorophenyl (IUPAC name) (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 (IUPAC name) (640) + TX, foxim (642) + TX, foxim-methyl (1340) + TX, pyrimetafos (1344) + TX, pyrimicarb (651) + TX , pirimiphos-ethyl (1345) + TX, pirimiphos-methyl (652) + TX, polychlorinated cyclopentadiene isomers (IUPAC name) (1346) + TX, polychlorinated terpenes (traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, praline ( 655) + TX, precocene I (alternative name) [CCN] + TX, precocene II (alternative name) [CCN] + TX, precocene III (alternative name) [CCN] + TX, primidofos (1349) + TX, profenofos ( 662) + TX, proflutrin [CCN] + TX, promacil (1354) + TX, promecarbe (1355) + TX, propafos (1356) + TX, propetamfos (673) + TX, propoxur (678) + TX, protidation (1360 ) + TX, protiofos (686) + TX, protoate (1362) + TX, protrifenbut [CCN] + TX, pyrometrozine (688) + TX, pyraclofes (689) + TX, pyrazophos (693) + TX, pyrethmethrin (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, quinalfosmetil (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 (name traditional) (1387) + TX, sabadila (alternative name) (725) + TX, escradano (1389) + TX, sebufós (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (code compound) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, silafluofen (728) + TX, SN 72129 (code (development)) (1397) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoride (IUPAC / Chemical Abstracts name) (1399) + TX, sodium hexafluorosilicate (1400) + TX, sodium pentachlorophenoxide (623) + TX, sodium selenate (IUPAC name) (1401) + TX, thioci sodium anate [CCN] + TX, sofamide (1402) + TX, spinosad (737) + TX, spiromesifene (739) + TX, spirotetramate [CCN] + TX, sulcofuron (746) + TX, sulcofuron-sodium (746) + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulfuryl fluoride (756) + TX, sulprofós (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, teflubenzurom (768) + TX, teflutrin (769 ) + TX, temephos (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) + TX, thionazine (1434) + TX, thiosultap (803) + TX, thiosultap-sodium (803) + TX, turingiensin (alternative name) [CCN] + TX, tolfenpirade (809) + TX, tralometrine (812) + TX, transflutrin (813) + TX, transpermethrin (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, triphenophones (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 (alternative name) + TX, zinc phosphide (640) + TX, zolaprofos (1469) and ZXI 8901 (development code) (858) + TX, cyantraniliprol [736994-63-19] + TX, chloranthraniliprole [500008-45-7] + TX, cyanopyraphene [560121-52-0] + TX, ciflumetofeno [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, tetramethylflutrine [84937-88-2] + TX, triflumezopirim (disclosed in WO 2012/092115) + TX, fluxametamide (WO 2007/026965) + TX, epsilon-metoflutrina [240494-71-7] + TX, epsilon-momfluorotrina [1065124-65-3] + TX, fluazaindolizine [1254304-22 -7] + TX, chloropralethrine [399572-87-3] + TX, fluxametamide [928783-29-3] + TX, cyhalodiamide [1262605-53-7] + TX, thioxazafene [330459-31- 9] + TX, broflanilide [1207727-04-5] + TX, flufiprol [704886-18-0] + TX, cyclaniliprol [1031756-98-5] + TX, tetraniliprol [1229654-66-3] + TX, guadipir (described in WO2010 / 060231) + TX, cicloxapride (described in WO2005 / 077934) + TX, a molluscicide selected from the group of substances consisting of bis (tributyltin) oxide (IUPAC name) (913) + TX, bromoacet amide [CCN] + TX, calcium arsenate [CCN] + TX, cloetocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, phentin (347) + TX, ferric phosphate (IUPAC name) (352) + TX, metaldehyde (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 (IUPAC / Chemical Abstracts name) (1045) + TX, 1,2-dichloropropane (IUPAC / Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4-diclo 1,1-dioxide rotetrahydrothiophene (IUPAC / Chemical Abstracts name) (1065) + TX, 3- (4-chlorophenyl) - 5-methylrodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1,3,5 acid -tiadiazinan-3-ilacetic (IUPAC name) (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, butylpyridaben (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 (name alternative) (210) + TX, dazomete (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafós (1044) + TX, diclofention (1051) + TX, diclifós (alternative name) + TX , dimetoate (262) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternate name) [CCN] + TX, etoprofós (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, oxamil (602) + TX, phorate ( 636) + TX, phosphamidon (639) + TX, fosfocarb [CCN] + TX, sebufós (alternative name) + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) + TX, terbam (alternative name) + TX, terbufós (773) + TX, tetrachlorothiophene (IUPAC / 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, a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and extract of Reynoutria sachalinensis (alternative name) (720) + TX, a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1,3-dione (name IUPAC) (1246) + TX, 4- (quinoxalin-2-ylamino) benzenesulfonamide (IUPAC name) (748) + TX, alpha-hydrochlorine [CCN] + TX, aluminum phosphide (640) + TX, antu (880) + TX, oxy of arsenic (882) + TX, barium carbonate (891) + TX, bistiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91) + TX, bromethalin (92) + TX, calcium cyanide (444 ) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol (alternative name) (850) + TX, coumaclor (1004) + TX, coumafuril (1005) + TX, coumatetralil (175) + TX, crimidine (1009) + TX, difenacoum (246) + TX, difetialone (249) + TX, difacinone (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, matt (1336) + TX, phosphine (IUPAC name) ( 640) + TX, phosphorus [CCN] + TX, pindone (1341) + TX, potassium arsenite [CCN] + TX, pirinuron (1371) + TX, scilirosida (1390) + TX, arsenite sodium [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 -hexylcyclohex2-enona (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, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatin (422) + TX, guazatin acetates (422) + TX, metiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, strip (804) + TX, trimetacarb (840) + TX, naphthenate zinc [CCN] and ziram (856) + TX, a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX, a wound protector selected from the group of substances consisting of mercuric oxide (512) + TX, octylinone (590) and thiophanate-methyl (802) + TX, and biologically active compounds selected from 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, ipco nazol [125225-28-7] + TX, metconazole [125116-23-6] + TX, myclobutanil [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, benalaxil [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, dimoxystrobin [149961-52-4] + TX, enestroburin {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, mancozebe [8018-01-7] + TX, manebe [12427-38-2] + TX, entered [9006-42-2] + TX, propineb [12071-83-9] + TX, take out [137-26-8] + TX, zinebe [12122-67-7] + TX, take out [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, oxine-copper [10380-28- 6] + TX, dinocape [131-72-6] + TX , nitrotal-isopropyl [10552- 74-6] + TX, edifenfós [17109- 49-8] + TX, iprobenfós [26087- 47-8] + TX, isoprothiolan [50512-35-1] + TX, phosdiphen [36519-00-3] + TX, pyrazophos [13457-18-6] + TX , tolclofósmetil [57018-04-9] + TX, acibenzolar-S-methyl [135158-54-2] + TX, anilazine [101-05-3] + TX, bentiavalicarb [413615-35- 7] + TX, blasticidine -S [2079-00-7] + TX, quinomethionate [2439-01-2] + TX, chloronebe [2675-77-6] + TX, chlorothalonil [1897-45-6] + TX, ciflufenamide [180409-60 -3] + TX, cymoxanil [57966-95-7] + TX, diclone [117-80-6] + TX, diclocimet [139920-32-4] + TX, diclomezine [62865-36-5] + TX, dichloran [99-30-9] + TX, dietofencarb [87130-20-9] + TX, dimetomorph [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, fentin [668-34-8] + TX, ferimzone [89269-64-7] + TX, fluazinam [79622-59-6] + TX, fluopicolide [ 239110-15-7] + TX, flusulfamide [106917-52-6] + TX , phenhexamide [126833-17-8] + TX, fosetyl aluminum [39148-24- 8] + TX, himexazole [10004-44-1] + TX, iprovalicarb [140923-17-7] + TX, IKF-916 (Cyzofamide) [120116-88-3] + TX, casugamycin [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, piroquilon [57369-32-1] + TX, quinoxyphene [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, triforine [26644-46-2] + TX, validamycin [37248- 47-8] + TX, zoxamide (RH7281) [156052-68-5] + TX, mandipropamide [374726-62-2] + TX, isopyrazam [881685-58-1] + TX, silkxane [874967 -67-6] + TX, (9-dichloromethylene1,2,3,4-tetrahydro-1,4-methane-naphthalen-5-yl) -amide of 3-difluoromethyl-1-methyl-1H-pyrazole-4 acid -carboxylic (disclosed and m WO 2007/048556) + TX, (3 ', 4', 5'-trifluoro-biphenyl-2-yl) - 3-difluoromethyl-1-methyl-1H-pyrazol-4-carboxylic acid amide (disclosed in WO 2006/087343) + TX, [(3S, 4R, 4aR, 6S, 6aS, 12R, 12aS, 12bS) -3 [(cyclopropylcarbonyl) oxy] - 1,3,4,4a, 5,6,6a, 12, 12a, 12bdecahidro-6,12-dihydroxy-4,6a, 12b-trimethyl-11-oxo-9- (3-pyridinyl) -2H, 11Hnafto [2,1-b] pyran [3,4-e] piran- 4-yl] methylcyclopropanecarboxylate [915972-17-7] + TX and 1,3,5-trimethylN- (2-methyl-1-oxopropyl) -N- [3- (2-methylpropyl) -4- [2,2 , 2-trifluoro-1-methoxy-1- (trifluoromethyl) ethyl] phenyl] -1Hpyrazolo-4-carboxamide [926914-55-8] + TX, and microbial including: Acinetobacter lwoffii + TX, Acremonium alternatum + TX + TX, Acremonium cephalosporium + TX + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, Adoxophyes orana granulovirus (AdoxGV) (Capex®) + TX, Agrobacterium radiobacter strain K84 (Galltrol-A®) + TX, Alternaria alternate + TX, Alternaria cassia + TX, Alternaria destruens (Smolder®) + TX, Ampelomyces quisqualis (AQ10®) + TX, Aspergillu s flavus AF36 (AF36®) + TX, Aspergillus flavus NRRL 21882 (Aflaguard®) + TX, Aspergillus spp. + TX, Aureobasidium pullulans + TX, Azospirillum + TX, (MicroAZ® + TX, TAZO B®) + TX, Azotobacter + TX, Azotobacter chroocuccum (Azotomeal®) + TX, Azotobacter cysts (Bionatural Blooming Blossoms®) + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus chitinosporus strain CM1 + TX, Bacillus chitinosporus strain AQ746 + TX, Bacillus licheniformis strain HB-2 (Biostart ™ Rhizoboost®) + TX, strain of Bacillus licheniform® TX, Green Releaf®) + TX, Bacillus circulans + TX, Bacillus firmus (BioSafe® + TX, BioNem-WP® + TX, VOTiVO®) + TX, Bacillus firmus strain I-1582 + TX, Bacillus macerans + TX, Bacillus marismortui + TX, Bacillus megaterium + TX, Bacillus mycoides strain AQ726 + TX, Bacillus papillae (Milky Spore Powder®) + TX, Bacillus pumilus spp. + TX, Bacillus pumilus strain GB34 (Yield Shield®) + TX, Bacillus pumilus strain AQ717 + TX, Bacillus pumilus strain QST 2808 (Sonata® + TX, Ballad Plus®) + TX, Bacillus spahericus (VectoLex®) + TX, Bacillus spp. + TX, Bacillus spp. AQ175 + TX, strain of Bacillus spp. AQ177 + TX, strain of Bacillus spp. AQ178 + TX, Bacillus subtilis strain QST 713 (CEASE® + TX, Serenade® + TX, Rhapsody®) + TX, Bacillus subtilis strain QST 714 (JAZZ®) + TX, Bacillus subtilis strain AQ153 + TX, strain Bacillus subtilis AQ743 + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis QST3004 + TX strain, Bacillus subtilis var. amyloliquefaciens FZB24 (Taegro® + TX, Rhizopro®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1Ab + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis israelensis (BMP123® + TX, Aquab123® + TX, Aquab123 + TX, VectoBac®) + TX, Bacillus thuringiensis kurstaki (Javelin® + TX, Deliver® + TX, CryMax® + TX, Bonide® + TX, Scutella WP® + TX, Turilav WP® + TX, Astuto® + TX, Dipel WP® + TX, Biobit® + TX, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF / 3P®) + TX, Bacillus thuringiensis strain BD # 32 + TX, Bacillus thuringiensis strain AQ52 + TX, Bacillus thuringiensis var. aizawai (XenTari® + TX, DiPel®) + TX, bacteria spp. (GROWMEND® + TX, GROWSWEET® + TX, Shootup®) + TX, Clavipacter michiganensis bacteriophage (AgriPhage®) + TX, Bakflor® + TX, Beauveria bassiana (Beaugenic® + TX, Brocaril WP®) + TX, Beauveria bassiana GHA (Mycotrol ES® + TX, Mycotrol O® + TX, BotaniGuard®) + TX, Beauveria brongniartii (Engerlingspilz® + TX, Schweizer Beauveria® + TX, Melocont®) + TX, Beauveria spp. + TX, Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Bacillus thuringiensis tenebrionis (Novodor®) + TX, BtBooster + TX, Burkholderia cepacia (Deny® + TX, Intercept® + TX, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp. + TX, Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reukaufii + TX, Candida saitoana (Bio-Coat® + TX, Biocure®) + TX, Candida sake + TX, Candida spp. + TX, Candida tenius + TX, Cedecea dravisae + TX, Cellulomonas flavigena + TX, Chaetomium cochliodes (Nova-Cide®) + TX, Chaetomium globosum (Nova-Cide®) + TX, Chromobacterium subtsugae strain PRAA4-1T (Grandevo® ) + TX, Cladosporium cladosporioides + TX, Cladosporium oxysporum + TX, Cladosporium chlorocephalum + TX, Cladosporium spp. + TX, Cladosporium tenuissimum + TX, Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp. + TX, Cryptococcus albidus (YIELDPLUS®) + TX, Cryptococcus humicola + TX, Cryptococcus infirmo-miniatus + TX, Cryptococcus laurentii + TX, Cryptophlebia leucotreta granulovirus (Cryptex®) + TX, Cupriavidus campinensis + TX, X®) + TX, Cydia pomonella granulovirus (Madex® + TX, Madex Plus® + TX, Madex Max / Carpovirusine®) + TX, Cylindrobasidium laeve (Stumpout®) + TX, Cylindrocladium + TX, Debaryomyces hansenii + TX, Drechslera hawaiinensis + TX, Enterobacter cloacae + TX, Enterobacteriaceae + TX, Virulent Entomophtora (Vektor®) + TX, Epicoccum nigrum + TX, Epicoccum purpurascens + TX, Epicoccum spp. + TX, Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean® / Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop® + TX, Prestop®) + TX, Gliocladium roseum + TX, Gliocladium spp. (SoilGard®) + TX, Gliocladium virens (Soilgard®) + TX, Granulovirus (Granupom®) + TX, Halobacillus halophilus + TX, Halobacillus coastalis + TX, Halobacillus trueperi + TX, Halomonas spp. + TX, Halomonas subglaciescola + TX, Halovibrio variabilis + TX, Hanseniaspora uvarum + TX, Helicoverpa armigera nucleopolyhedrovirus (Helicovex®) + TX, Helicoverpa zea nuclear polyhedrosis virus (Gemstar®) + TX, Isoflavone - formononetine (Myconate®) + TX, Kloeckera apiculata + TX, Kloeckera spp. + TX, Lagenidium giganteum (Laginex®) + TX, Lecanicillium longisporum (Vertiblast®) + TX, Lecanicillium muscarium (Vertikil®) + TX, Lymantria Dispar nucleopolyhedrosis virus (Disparvirus®) + TX, Marinococcus halophilus + TX, Mula geula , Metarhizium anisopliae (Met52®) + TX, Metarhizium anisopliae (Destruxin WP®) + TX, Metschnikowia fruticola (Shemer®) + TX, Metschnikowia pulcherrima + TX, Microdochium dimerum (Antibot®) + TX, Micromonospora Microscope + TX, Muscodor albus 620 (Muscudor®) + TX, Muscodor roseus A3-5 strain + TX, Mycorrhizae spp. (AMykor® + TX, Root Maximizer®) + TX, Myrothecium verrucaria strain AARC-0255 (DiTera®) + TX, BROS PLUS® + TX, Ophiostoma piliferum strain D97 (Sylvanex®) + TX, Paecilomyces farinosus + TX, Paecilomyces fumosoroseus (PFR-97® + TX, PreFeRal®) + TX, Paecilomyces linacinus (Biostat WP®) + TX, strain of Paecilomyces lilacinus 251 (MeloCon WG®) + TX, Paenibacillus polymyxa + TX, Pantoea agglomerans (Blight agglomerans) 1®) + TX, Pantoea spp. + TX, Pasteuria spp. (Econem®) + TX, Pasteuria nishizawae + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart® + TX, TagTeam®) + TX, Penicillium brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum , Penicillium spp. + TX, Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, phosphate solubilizing bacteria (Phosphomeal®) + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guiler TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas chlororaphis (AtEze®) + TX + TX, Pseudomonas fluorescens A506 strain (BlightBan A506®) + TX, Pseudomonas putida + TX, Pseudomonas reactans + TX, Pseudomonas spp. + TX, Pseudomonas syringae (Bio-Save®) + TX, Pseudomonas viridiflava + TX, Pseudomons fluorescens (Zequanox®) + TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®) + TX, Puccinia canaliculata + TX, Puccinia thlaspeos (Wood Warrior®) + TX, Pythium paroecandrum + TX, Pythium oligandrum (Polygandron® + TX, Polyversum®) + TX, Pythium periplocum + TX, Rhanella aquatilis + TX, Rhanella spp. + TX, Rhizobia (Dormal® + TX, Vault®) + TX, Rhizoctonia + TX, strain of Rhodococcus globerulus AQ719 + TX, Rhodosporidium diobovatum + TX, Rhodosporidium toruloides + TX, Rhodotorula spp. + TX, Rhodotorula glutinis + TX, Rhodotorula graminis + TX, Rhodotorula mucilagnosa + TX, Rhodotorula rubra + TX, Saccharomyces cerevisiae + TX, Salinococcus roseus + TX, Sclerotinia minor + TX, Sclerotinia minor (SARRITOR®) + TX, Scytalidium spp. + TX, Scytalidium uredinicola + TX, Spodoptera require nuclear polyhedrosis virus (Spod-X® + TX, Spexit®) + TX, Serratia marcescens + TX, Serratia plymuthica + TX, Serratia spp. + TX, Sordaria fimicola + TX, Spodoptera littoralis nucleopolyhedrovirus (Littovir®) + TX, Sporobolomyces roseus + TX, Stenotrophomonas maltophilia + TX, Streptomyces ahygroscopicus + TX, Streptomyces albaduncus + TX, Streptomyces exfoliates TX, Streptomyces exfoliates TX + TX, Streptomyces griseoviridis (Mycostop®) + TX, Streptomyces lydicus (Actinovate®) + TX, Streptomyces lydicus WYEC-108 (ActinoGrow®) + TX, Streptomyces violaceus + TX, Tilletiopsis minor + TX, Tilletiopsis spp. + TX, Trichoderma asperellum (T34 Biocontrol®) + TX, Trichoderma gamsii (Tenet®) + TX, Trichoderma atroviride (Plantmate®) + TX, Trichoderma hamatum TH 382 + TX, Trichoderma harzianum rifai (Mycostar®) + TX, Trichoderma harzianum T-22 (Trianum-P® + TX, PlantShield HC® + TX, RootShield® + TX, Trianum-G®) + TX, Trichoderma harzianum T-39 (Trichodex®) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma spp. LC 52 (Sentinel®) + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + TX, Trichoderma taxi + TX, Trichoderma virens + TX, Trichoderma virens (formerly Gliocladium virens GL-21) ( SoilGuard®) + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, Trichosporon spp. + TX, Trichothecium spp. + TX, Trichothecium roseum + TX, Typhula phacorrhiza strain 94670 + TX, Typhula phacorrhiza strain 94671 + TX, Ulocladium atrum + TX, Ulocladium oudemansii (BotryZen®) + TX, Ustilago maydis + TX, various bacteria and additional micronutrients (Natural supplementary micronutrients ( II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Verticillium lecanii (Mycotal® + TX, Vertalec®) + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv. Poae (Camperico®) + TX, Xenorhabdus bovienii + TX, Xenorhabdus nematophilus; and Plant extracts including: pine oil (Retenol®) + TX, azadirahtina (Plasma Neem Oil® + TX, AzaGuard® + TX, MeemAzal® + TX, Molt-X® + TX, Botanical IGR (Neemazad® + TX, Neemix ®) + TX, canola oil (Lilly Miller Vegol®) + TX, Chenopodium ambrosioides near ambrosioides (Requiem®) + TX, Chrysanthemum extract (Crisant®) + TX, neem oil extract (Trilogy®) + TX, Labiatae essential oils (Botania®) + TX, extracts of clove oil, rosemary, peppermint and thyme (Garden insect killer®) + TX, Glycinabetaine (Greenstim®) + TX, garlic + TX, lemongrass oil (GreenMatch®) + TX, neem oil + TX, Nepeta cataria (Catnip oil) + TX, Nepeta catarina + TX, nicotine + TX, oregano oil (MossBuster®) + TX, Pedaliaceae oil (Nematon®) + TX, pyrethrum + TX, Quillaja saponaria (NemaQ®) + TX, Reynoutria sachalinensis (Regalia® + TX, Sakalia®) + TX, rotenone (Eco Roten®) + TX, Rutaceae plant extract (Soleo®) + TX, oil soybean (Ortho ecosense®) + TX, tree oil from tea (Timorex Gold®) + TX, thyme oil + TX, AGNIQUE® MMF + TX, BugOil® + TX, mix of rosemary, sesame, peppermint, thyme and cinnamon extracts (EF 300®) + TX, mix of clove, rosemary and peppermint extract (EF 400®) + TX, mixture of clove oil, peppermint and garlic and mint (Soil Shot®) + TX, kaolin (Screen®) + TX, storage glucamate brown algae (Laminarin®); and pheromones including: black-headed fire worm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®) + TX, moth pheromone (Paramount dispenser- (CM) / Isomate CPlus®) + TX, grape berry moth pheromone (3M MEC-GBM Sprayable Pheromone®) + TX, Foil pheromone (3M MEC - LR Sprayable Pheromone®) + TX, Muscamona (Snip7 Fly Bait® + TX, Starbar Premium Fly Bait®) + TX, Pheromone of the oriental moth fruit (3M oriental fruit moth sprayable pheromone®) + TX, Peach borer pheromone (IsomateP®) + TX, Tomato worm pheromone (3M Sprayable pheromone®) + TX, entostat powder (palm extract) (Exosex CM ®) + TX, (E + TX, Z + TX, Z) -3 + TX, 8 + TX, 11-tetradecatrienyl acetate + TX, (Z + TX, Z + TX, E) -7 + TX, 11 + TX, 13-Hexadecatrienal + TX, (E + TX, Z) -7 + TX, 9-dodecadien-1-yl acetate + TX, 2-Methyl-1-butanol + TX, Calcium acetate + TX, Scenturion ® + TX, Biolure® + TX, Check-Mate® + TX, Lavulil Senecioate; and Macrobials including: Aphelinus abdominalis + TX, Aphidius ervi (Aphelinus-System®) + TX, Acerophagus papaya + TX, Adalia bipunctata (Adalia-System®) + TX, Adalia bipunctata (Adaline®) + TX, Adalia bipunctata (Aphidalia® ) + TX, Ageniaspis citricola + TX, Ageniaspis fuscicollis + TX, Amblyseius andersoni (Anderline® + TX, Andersoni-System®) + TX, Amblyseius californicus (Amblyline® + TX, Spical®) + TX, Amblyseius cucumeris (Thripex® + TX, Bugline cucumeris®) + TX, Amblyseius fallacis (Fallacis®) + TX, Amblyseius swirskii (Bugline swirskii® + TX, Swirskii-Mite®) + TX, Amblyseius womersleyi (WomerMite®) + TX, Amitus hesperidum + TX, Anagrus atomus + TX, Anagyrus fusciventris + TX, Anagyrus kamali + TX, Anagyrus loecki + TX, Anagyrus pseudococci (Citripar®) + TX, Anicetus beneficices + TX, Anisopteromalus calandrae + TX, Anthocoris nemoralis (Anthocoris-TX), Anthocoris-Systemelin) abdominalis (Apheline® + TX, Aphiline®) + TX, Aphelinus asychis + TX, Aphidius colemani (Aphipar®) + TX, Aphidiu s herb (Ervipar®) + TX, Aphidius gifuensis + TX, Aphidius matricariae (Aphipar-M®) + TX, Aphidoletes aphidimyza (Aphidend®) + TX, Aphidoletes aphidimyza (Aphidoline®) + TX, Aphytis lingnanensis + TX, Aphytis lingnanensis + TX + TX, Aprostocetus hagenowii + TX, Atheta coriaria (Staphyline®) + TX, Bombus spp. + TX, Bombus terrestris (Natupol Beehive®) + TX, Bombus terrestris (Beeline® + TX, Tripol®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus + TX, Chrysoperla carnea (Chrysoline®) + TX, Chrysoperla carnea (Chrysopala ®) + TX, Chrysoperla rufilabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichus phyllocnistoides + TX, Closterocerus chamaeleon + TX, Closterocerus spp. + TX, Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug® + TX, Cryptoline®us + TX, Cyptoline® , Dacnusa sibirica + TX, Dacnusa sibirica (Minusa®) + TX, Diglyphus isaea (Diminex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha diaicaisundaica longicaataata + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea + TX, Diglyphus isaea (Miglyphus® + TX, Digline®) + TX, Dacnusa sibirica (DacDigline® + TX, Minex®) + TX, Diversinervus spp. + TX, Encarsia citrina + TX, Encarsia formosa (Encarsia max® + TX, Encarline® + TX, En-Strip®) + TX, Eretmocerus eremicus (Enermix®) + TX, Encarsia guadeloupae + TX, Encarsia haitiensis + TX, Episyrphus balteatus (Syrphidend®) + TX, Eretmoceris siphonini + TX, Eretmocerus californicus + TX, Eretmocerus eremicus (Ercal® + TX, Eretline e®) + TX, Eretmocerus eremicus (Bemimix®) + TX, Eretmocerus hayati + TX, Eretmocerus hayati + TX Bemipar® + TX, Eretline m®) + TX, Eretmocerus siphonini + TX, Exochomus quadripustulatus + TX, Feltiella acarisuga (Spidend®) + TX, Feltiella acarisuga (Feltiline®) + TX, Fopius arisanus + TX, Fopius ceratitivorus + TX, Formononetina (Wirless Beehome®) + TX, Franklinothrips vespiformis (Vespop®) + TX, Galendromus occidentalis + TX, Goniozus legneri + TX, Habrobracon hebetor + TX, Harmonia axyridis (HarmoBeetle®) + TX, Heterorhabditis spp. (Lawn Patrol®) + TX, Heterorhabditis bacteriophora (NemaShield HB® + TX, Nemaseek® + TX, Terranem-Nam® + TX, Terranem® + TX, Larvanem® + TX, B-Green® + TX, NemAttack® + TX , Nematop®) + TX, Heterorhabditis megidis (Nemasys H® + TX, BioNem H® + TX, Exhibitline hm® + TX, Larvanem-M®) + TX, Hippodamia convergens + TX, Hypoaspis aculeifer (Aculeifer-System® + TX , Entomite-A®) + TX, Hypoaspis miles (Hypoline m® + TX, Entomite-M®) + TX, Lbalia leucospoides + TX, Lecanoideus floccissimus + TX, Lemophagus errabundus + TX, Leptomastidea abnormis + TX, Leptomastix dactylopii ®) + TX, Leptomastix epona + TX, Lindorus lophanthae + TX, Lipolexis oregmae + TX, Lucilia caesar (Natufly®) + TX, Lysiphlebus testaceipes + TX, Macrolophus caliginosus (Mirical-N® + TX, Macroline c® + TX, Mirical®) + TX, Mesoseiulus longipes + TX, Metaphycus flavus + TX, Metaphycus lounsburyi + TX, Micromus angulatus (Milacewing®) + TX, Microterys flavus + TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®) + TX, Neodryinus typhlocybae + TX, Neoseiulus californicus + TX, Neoseiulus cucumeris (THRYPEX®) + TX, Neoseiulus fallacis + TX, Nesideocoris tenuis (NesidioBug® + TX, Nesibug®) + TX, Ophyra aenescens (Biofly )® Orius insidiosus (Thripor-I® + TX, Oriline i®) + TX, Orius laevigatus (Thripor-L® + TX, Oriline l®) + TX, Orius majusculus (Oriline m®) + TX, Orius strigicollis (ThriporS®) + TX, Pauesia juniperorum + TX, Pediobius foveolatus + TX, Phasmarhabditis hermaphrodita (Nemaslug®) + TX, Phymastichus coffea + TX, Phytoseiulus macropilus + TX, Phytoseiulus persimilis (Spidex® + TX, Phytususis®) Podisus®) + TX, Pseudacteon curvatus + TX, Pseudacteon obtusus + TX, Pseudacteon tricuspis + TX, Pseudaphycus maculipennis + TX, Mexican Pseudleptomastix + TX, Psyllaephagus pilosus + TX, Psyllaephagus pilosus + TX, Psyttalia concolor (complex) + TX, Quadrastichus + TX, Rhyzobius lophanthae + TX, Rodolia cardinalis + TX, Rumina decollate + TX, Semielacher petiolatus + TX, Sitobion avenae (Ervibank®) + TX, Steinernema carpocapsae (Nematac C® + TX, Millenium® + TX, BioNem C® + TX, NemAttack® + TX, Nemastar® + TX, Capsanem®) + TX, Steinernema feltiae (NemaShield® + TX, Nemasys F® + TX, BioNem F® + TX, Steinernema-System® + TX, NemAttack® + TX, Nemaplus® + TX, Exhibitline sf® + TX, Scia-rid® + TX, Entonem®) + TX, Steinernema kraussei (Nemasys L® + TX, BioNem L® + TX, Exhibitline srb®) + TX, Steinernema riobrave (BioVector ® + TX, BioVektor®) + TX, Steinernema scapterisci (Nematac S®) + TX, Steinernema spp. + TX, Steinernematid spp. (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX, Trichogramma brassicae ( Tricho-Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator; and other biologicals including: abscisic acid + TX, bioSea® + TX, Chondrostereum purpureum (Chontrol Paste®) + TX, Colletotrichum gloeosporioides (Collego®) + TX, Copper Octanoate (Cueva®) + TX, Delta Traps (Trapline d® ) + TX, Erwinia amylovora (Harpina) (ProAct® + TX, Ni-HIBIT Gold CST®) + TX, Ferri-phosphate (Toolol®) + TX, Funnel traps (Trapline y®) + TX, Gallex® + TX , Grower's Secret® + TX, Homo-brassonolid + TX, Iron Phosphate (Lilly Miller Worry Free Tool Slug & Snail Bait®) + TX, MCP hail trap (Trapline f®) + TX, Microctonus hyperodae + TX, Mycoleptodiscus terrestris (Des-X®) + TX, BioGain® + TX, Aminomite® + TX, Zenox® + TX, Pheromone trap (Thripline ams®) + TX, potassium bicarbonate (MilStop®) + TX, acid potassium salts fatty (Sanova®) + TX, potassium silicate solution (Sil-Matrix®) + TX, potassium iodide + potassium thiocinate (Enzicur®) + TX, SuffOilX® + TX, Spider poison + TX, Nosema locustae ( Semaspore Organic Gr asshopper Control®) + TX, Sticky Traps (Trapline YF® + TX, Rebell Amarillo®) + TX and Traps (Takitrapline y + b®) + TX.
[0172] References in parentheses after the active ingredients, for example, [3878-19-1] refer to the Chemical Abstracts Registration Number. The mixing partners described above are known. When the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], are described there with the entry number given in curly brackets here above for the particular compound; for example, the compound "abamectin" is described under 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 © 1995-2004]; for example, the compound "acetoprol" is described at http://www.alanwood.net/pesticides/acetoprole.html.
[0173] 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. "CAS Reg. No." means the Chemical Abstracts Registration Number.
[0174] The mixture of active ingredients of the compounds of formula I selected from Tables 1 to 6 and P1 with active ingredients described above comprises a compound selected from Tables 1 to 6 and P1 and an active ingredient as described above preferably in a mixing ratio from 100: 1 to 1: 6000, especially from 50: 1 to 1:50, more especially in a ratio of 20: 1 to 1:20, even more especially from 10: 1 to 1:10, most especially from 5: 1 and 1: 5, with a particular 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. These mixing ratios are by weight.
[0175] Mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to pests or their environment, with the exception of a method of surgical or therapeutic treatment of the body human or animal and diagnostic methods practiced on the human or animal body.
[0176] Mixtures comprising a compound of formula I selected from Tables 1 to 6 and P1 and one or more ingredients as described above can be applied, for example, in a single "ready-to-mix" form, in a mixture for combined spray composed of separate formulations of the components of the individual active ingredients, such as a "mixing tank", and in a combined use of the individual active ingredients when applied sequentially, that is, one after the other, within a period reasonably short, such as a few hours or days. The order of application of the compounds of formula I selected from tables 1 to 6 and P1 and of the active ingredients as described above is not essential for the realization of the present invention.
[0177] The compositions according to the invention can also comprise other solid or liquid auxiliaries, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example, soybean oil, rapeseed oil or epoxidized coconut oil), antifoams , for example silicone oil, preservatives, viscosity regulators, binders and / or adhesion agents, fertilizers or other active ingredients to achieve specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
[0178] 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). These processes for the preparation of the compositions and the use of compounds I for the preparation of these compositions are also an object of the invention.
[0179] 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 must be selected to suit the objectives of the prevailing circumstances - and the use of pest control compositions of the type mentioned above, are other objects of the invention. Typical concentration rates are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The application rate per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g / ha, preferably 10 to 600 g / ha.
[0180] A preferred method of application in the area of crop protection is the application to the foliage of plants (foliar application), being possible to select the frequency and application rate to meet the danger of infestation with the pest in question. Alternatively, the active ingredient can reach plants through the root system (systemic action), by soaking the plant site with a liquid composition or by incorporating the active ingredient in solid form at the plant site, for example in the soil, for example in granules (application to soil). In the case of rice fields, these granules can be calibrated in the flooded rice field.
[0181] The compounds of the invention and their compositions are also suitable for the protection of plant propagating material, for example seeds, such as fruits, tubers or grains, or nursery plants, against pests of the aforementioned type. The propagation material can be treated with the compost before planting, for example, a seed can be treated before sowing. Alternatively, the compound can be applied to the seed grains (coating), either by soaking the grains 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 so treated are further objects of the invention. Typical treatment rates depend on the plant and pest / fungi to be controlled and are generally between 1 and 200 grams per 100 kg of seeds, preferably between 5 and 150 grams per 100 kg of seeds, such as between 10 and 100 grams per 100 kg of seeds.
[0182] The term seed covers seeds and plant propagules of all types including but not limited to real seeds, pieces of seeds, sprouts, corns, bulbs, fruits, tubers, grains, rhizomes, cuttings, cuttings and similar and means in a preferential way true seeds.
[0183] The present invention also comprises seeds coated or treated with or containing a compound of formula I. The term "coated or treated with and / or containing" generally means that the active ingredient is mostly on the seed surface at the time of application, although a larger or smaller part of the ingredient can penetrate the seed material, depending on the method of application. When said seed product is (re) planted, it can absorb the active ingredient. In one embodiment, the present invention makes available a plant propagating material to which a compound of formula (I) is adhered. In addition, a composition comprising a plant propagating material treated with a compound of formula (I) is hereby made available.
[0184] Seed treatment comprises all suitable seed treatment techniques known in the art, such as seed treatment, seed coating, seed dusting, seed soaking and seed pelleting. The application of the seed treatment with the compound of the formula (I) can be carried out by any known methods, such as spraying or sprinkling the seeds before sowing or during sowing / planting of seeds. Biological Examples: Example B1: Bemisia tabaci (White cotton fly)
[0185] Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying, the leaf discs were infested with adult whiteflies. The samples were evaluated for mortality 6 days after incubation.
[0186] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P2, P5, P6, P8, P10, P11, P16, P17, P19, P20, P21, P22, P25, P27 , P33, P35, P39, P40, P45, P46, P59, P64, P66, P67, P70, P77, P80, P81, P85, P86, P88, P90, P91, P94, P96, P100, P103, P106, P108 and P111. Example B2: Diabrotica balteata (Corn rootworm)
[0187] Corn sprouts, placed on an agar layer in 24-well microtiter plates, were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). Samples were assessed for mortality and growth inhibition, compared to untreated samples 4 days after infestation.
[0188] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P1, P2, P3, P5, P6, P7, P11, P12, P13, P14, P15, P16, P17, 1P8 , P19, P20, P21, P22, P23, P25, P26, P27, P28, P29, P30, P32, P33, P34, P35, P36, P37, P38, P39, P40, P41, P43, P44, P45, P46 , P48, P50, P52, P54, P55, P56, P58, P59, P60, P61, P64, P65, P66, P67, P70, P71, P72, P73, P75, P76, P77, P78, P82, P84, P85 , P86, P87, P88, P89, P90, P91, P92, P93, P94, P95, P96, P98, P99, P100, P101, P102, P103, P104, P105, P106, P107, P108, P109, P110 and P111 . Example B3: Euschistus heros (Neotropical stink bug)
[0189] Soy leaves were sprayed on agar in 24-well microtiter places with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying, the leaves were infested with N-2 nymphs. The samples were evaluated for mortality compared to untreated samples 5 days after infestation.
[0190] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P4, P2, P3, P5, P6, P8, P11, P12, P15, P16, P18, P19, P20, P21 , P22, P23, P25, P26, P27, P30, P32, P33, P34, 3P5, P36, P37, P38, P39, P40, P41, P42, P43, P44, P45, P46, P49, P50, P51, P52 , P53, P54, P55, P56, P57, P58, P59, P60, P61, P62, P63, P64, P65, P66, P67, P68, P69, P70, P71, P72, P73, P75, P77, P81, P84 , P85, P86, P88, P89, P90, P91, P92, P93, P94, P95, P96, P97, P98, P99, P100, P101, P102, P103, P104, P106, P108, P109, P110 and P111. Example B4: Myzus persicae (Green peach aphid)
[0191] Sunflower leaf discs were placed on agar in a 24-well microtiter plate and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying, the leaf discs were infested with a population of aphids of mixed ages. Samples were assessed for mortality 6 days after infestation.
[0192] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P8, P9, P11, P12, P15, P16, P18, P19 , P20, P21, P22, P23, P25, P26, P27, P30, P32, P33, P34, P35, P36, P37, P39, P40, P41, P42, P43, P44, P45, P46, P49, P50, P51 , P52, P53, P54, P55, P56, P57, P58, P59, P60, P61, P62, P63, P64, P65, P66, P67, P69, P70, P71, P72, P73, P75, P77, P78, P80 , P81, P82, P84, P85, P86, P87, P88, P89, P90, P91, P92, P93, P94, P95, P96, P97, P98, P100, P101, P102, P103, P104, P105, P106, P108 , P109, P110 and P111. Example B5: Myzus persicae (Green peach aphid)
[0193] Roots of pea seedlings, infested with a population of aphids of mixed ages, were placed directly in the aqueous test solutions prepared from stock solutions in DMSO at 10'000. The samples were evaluated for mortality 6 days after placing the seedlings in the test solutions.
[0194] The following compounds resulted in at least 80% mortality at a test rate of 24 ppm: P3, P5, P6, P8, P9, P18, P22, P26, P27, P33, P34, P35, P37, P49 , P53, P56, P58, P60, P61, P67, P70, P84, P87, P94, P102, P106, P109, P110 and P111. Example B6: Plutella xylostella (Cruciferous moth)
[0195] 24-well microtiter plates with an artificial diet were treated with aqueous test solutions prepared from stock solutions in DMSO at 10'000 ppm by pipetting. After drying, the plates were infested with L2 larvae (10 to 15 per well). Samples were assessed for mortality and growth inhibition, compared to untreated samples 5 days after infestation.
[0196] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1, P2, P3, P4, P6, P7, P8 , P9, P11, P12, P18, P26, P27, P32, P37, P43, P45, P51, P52, P53, P55, P56, P57, P58, P60, P61, P62, P63, P65, P69, P71, P72 , P73, P75, P77, P80, P82, P84, P2, P5, P14, P15, P16, P17, P19, P20, P21, P22, P23, P24, P25, P28, P29, P34, P35, P36, P38 , P39, P40, P41, P44, P46, P48, P50, P54, P59, P64, P66, P67, P70, P79, P81, P85, P86, P88, P89, P90, P91, P92, P93, P94, P95 , P96, P97, P98, P99, P100, P101, P102, P103, P104, P105, P106, P107, P108, P109, P110 and P111. Example B7: Spodopteralittoralis (Egyptian cotton curuquerêdo)
[0197] Cotton sheet discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying, the leaf discs were infested with five L1 larvae. Samples were evaluated for mortality, anti-food effect and growth inhibition, compared to untreated samples 3 days after infestation. The control of Spodoptera littoralis by a test sample occurs when at least one of the mortality, anti-food effect and growth inhibition is superior to the untreated sample.
[0198] The following compounds resulted in a control of at least 80% at an application rate of 200 ppm: P1, P2, P4, P5, P6, P7, P8, P11, P12, P14, P15, P16, P17, P18, P19, P20, P21, P22, P23, P24, P25, P27, P28, P29, P32, P34, P35, P36, P38, P39, P40, P41, P43, P44, P45, P46, P48, P50, P51, P52, P53, P54, P55, P56, P57, P59, P60, P61, P63, P64, P65, P66, P68, P69, P70, 71, P72, P77, P80, P82, P84, P85, P9, P86, P88, P89, P90, P91, P92, P93, P94, P95, P96, P97, P98, P100, P101, P102, P103, P104, P105, P106, P107, P108, P109, P110 and P111. Example B8: Spodoptera littoralis (Egyptian cotton curuquerê)
[0199] The test compounds were applied with a pipette from stock solutions in DMSO at 10'000 ppm in 24-well plates and mixed with agar. Lettuce seeds were placed on the agar and the 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 wet gel blotting paper and the plate was closed with it. The samples were evaluated for mortality, anti-food effect and growth inhibition, compared to untreated samples 6 days after infestation.
[0200] The following compounds gave an effect of at least 80% in at least one of the three categories (mortality, anti-feeding or growth inhibition) at a test rate of 12.5 ppm: P2, P5, P6, P11, P16 , P18, P19, P20, P21, P22, P25, P27, P32, P35, P39, P40, P41, P44, P46, P50, P52, P53, P54, P56, P57, P59, P61, 66, P70, P71 , P72, P77, P82, P84, P85, P64, P86, P88, P89, P90, P91, P92, P93, P96, P100, P103, P104, P105 and P108. Example B9: Tetranychus urticae (two-spotted spider mite)
[0201] Agar bean leaf discs were sprayed onto 24-well microtiter plates with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying, the leaf discs were infested with a population of mites of mixed ages. Samples were assessed for mortality in a mixed population (mobile stages) 8 days after infestation.
[0202] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P21, P25, P27, P35, P64, P71 and P110. Example B10: Thrips tabaci (Onion thrips)
[0203] Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying, the leaf discs were infested with a population of thrips of mixed ages. Samples were assessed for mortality 6 days after infestation.
[0204] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P8, P11, P16, P17, P20, P21, P25, P85, P91, P94, P100, P106, P110 and P111 . Example B11: Frankliniella occidentalis (Western flower thrips)
[0205] Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying, the leaf discs were infested with a mixed-age Frankliniella population. The samples were evaluated for mortality 7 days after infestation.
[0206] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P5, P8, P11, P16, P17, P18, P19, P20, P21, P25, P27, P32, P35, P56 , P70, P85, P89, P91, P92, P93, P94, P96, P100, P104, P106, P110 and P111. Example B12: Activity against Aedes aegypti (Yellow fever mosquito)
[0207] Test solutions, at an application rate of 200 ppm 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.
[0208] The following compounds provided at least 80% control of Aedes aegypti after 48h: P2, P11, P16, P17, P18, P19, P20, P21, P25, P85, P86, P88, P89, P90, P92, P93 , P94, P100, P101, P108, P110 and P111.

权利要求:
Claims (10)
[0001]
:
[0002]
1. Compound of formula I-1
[0003]
2. Compound of formula I-2
[0004]
3. Compound of formula Ia-1
[0005]
4. Compound of formula Ia-2
[0006]
5. Compound of formula Ia-3
[0007]
6. A compound of the formula Ia-3, according to claim 5, characterized by the fact that: R9 is C1-C4 haloalkyl; R10 is C1-C4 alkyl; and Qc is
[0008]
7. Pesticidal composition characterized by the fact that it comprises at least one compound of formula I-1 as defined in claim 1, of formula I-2 as defined in claim 2, of formula Ia-1 as defined in claim 3, of formula Ia- 2 as defined in claim 4 of formula Ia-3 as defined in claim 5, or, where appropriate, in each case in free form or in the form of an agrochemically usable salt, as an active ingredient and at least one auxiliary.
[0009]
8. Pest control method, characterized by understanding the application of a composition as defined in claim 7 to pests or their environment, with the exception of a method for treating the human or animal body by surgery or therapy, and diagnostic methods used in the human or animal body.
[0010]
9. Method for the protection of plant propagation material from attack by pests, characterized in that it comprises the treatment of propagation material or the site where the propagation material is planted, with a composition as defined in claim 7.

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BR112017003366A2|2018-07-03|

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JP2017526678A|2017-09-14|

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WO2016030229A1|2016-03-03|

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US20170267672A1|2017-09-21|

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法律状态:
2019-08-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-04-22| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|

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2020-09-08| B09A| Decision: intention to grant|

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2020-12-08| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/08/2015, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP14182118|2014-08-25|

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EP14182118.1|2014-08-25|

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EP15159505.5|2015-03-17|

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EP15159505|2015-03-17|

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PCT/EP2015/068953|WO2016030229A1|2014-08-25|2015-08-18|Pesticidally active heterocyclic derivatives with sulphur containing substituents|

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