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WO2018091389A1 - Dérivés hétérocycliques à activité pesticide comportant des substituants contenant du soufre - Google Patents

Dérivés hétérocycliques à activité pesticide comportant des substituants contenant du soufre Download PDF

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WO2018091389A1
WO2018091389A1 PCT/EP2017/078988 EP2017078988W WO2018091389A1 WO 2018091389 A1 WO2018091389 A1 WO 2018091389A1 EP 2017078988 W EP2017078988 W EP 2017078988W WO 2018091389 A1 WO2018091389 A1 WO 2018091389A1
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formula
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halogen
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Andrew Edmunds
Michel Muehlebach
Pierre Joseph Marcel Jung
André Jeanguenat
Sebastian RENDLER
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Syngenta Participations AG
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Syngenta Participations AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems

Definitions

  • the present invention relates to pesticidally active, in particular insecticidally active heterocyclic derivatives containing sulphur substituents, to intermediates for the preparation of those compounds, to compositions comprising those compounds, and to their use for controlling animal pests (including arthropods and in particular insects or representatives of the order Acarina).
  • Heterocyclic compounds with pesticidal action are known and described, for example, in
  • the present invention accordingly relates to compounds of formula I,
  • A represents CH or N
  • Q is phenyl which is mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkoxy, Ci-C4alkoxy and Ci-C4haloalkylsulfanyl; or
  • Q is pyrimidyl which is mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4haloalkoxy, Ci-C4alkoxy and
  • Ci-C4haloalkylsulfanyl or
  • Q is pyrazolyl which is linked via a nitrogen atom to the ring which contains the substituent A, said pyrazolyl can be substituted by halogen, cyano or Ci-C4haloalkyl; or
  • Q is triazolyl which is linked via a nitrogen atom to the ring which contains the substituent A, said triazolyl can be substituted by halogen, cyano or Ci-C4haloalkyl;
  • X is S, SO or S0 2 ;
  • Ri is Ci-C4alkyl, Ci-C4haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl or C3-C6cyclo- alkyl-Ci-C 4 alkyl;
  • R2 is halogen, Ci-C6haloalkyl, Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl or Ci-C6haloalkoxy;
  • Xi is O, S or NR3, wherein R3 is hydrogen, Ci-C4alkyl, C2-C6alkenyl, C2-C6alkynyl, Ci-C4alkoxy- Ci-C4alkyl or C3-C6cycloalkyl; and
  • Gi is N or CH; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N- oxides of the compounds of formula I.
  • Compounds of formula I which have at least one basic centre 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 phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as Ci-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as Ci-C4alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for
  • Compounds of formula I which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or
  • dimethylpropylamine or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.
  • alkyl groups occurring in the definitions of the substituents can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl, hexyl, and their branched isomers.
  • Alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, alkoxy, alkenyl and alkynyl radicals are derived from the alkyl radicals mentioned.
  • the alkenyl and alkynyl groups can be mono- or polyunsaturated.
  • Ci-di-alkylamino is dimethylamino.
  • Halogen is generally fluorine, chlorine, bromine or iodine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl or halophenyl.
  • HaloalkyI groups preferably have a chain length of from 1 to 6 carbon atoms.
  • Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2- trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 , 1-difluoro-2,2,2-trichloroethyl, 2,2,3,3- tetrafluoroethyl and 2,2,2-trichloroethyl.
  • Alkoxy groups preferably have a preferred chain length of from 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.
  • Alkoxyalkyl groups preferably have a chain length of 1 to 6 carbon atoms.
  • Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n- propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
  • Haloalkylsulfanyl groups preferably have a chain length of from 1 to 4 carbon atoms.
  • Haloalkylsulfanyl is, for example, difluoromethylsulfanyl, trifluoromethylsulfanyl or 2,2,2-trifluoroethylsulfanyl. Similar considerations apply to the radicals Ci-C4haloalkylsulfinyl and Ci-C4haloalkylsulfonyl, which may be, for example, trifluoromethylsulfinyl, trifluoromethylsulfonyl or 2,2,2-trifluoroethylsulfonyl.
  • the cycloalkyl groups preferably have from 3 to 6 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • Haloalkoxy groups preferably have a chain length of from 1 to 6 carbon atoms.
  • Haloalkoxy is, for example, difluoromethoxy, trifluoromethoxy or 2,2,2-trifluoroethoxy.
  • Q as a "triazolyl group which is linked via a nitrogen atom" may be selected from (1 H-1 ,2,3-triazol-1-yl)-; (2H-1 ,2,3-triazol-2-yl)-; (4H-1 ,2,4-triazol-4-yl)- and (1 H-1 ,2,4- triazol-1-yl)-.
  • "mono- to polysubstituted" in the definition of the substituents means typically, depending on the chemical structure of the substituents, monosubstituted to four-times substituted, preferably monosubstituted to three-times substituted, more preferably mono-, or double- substituted.
  • Free radicals represent methyl groups.
  • the compounds of formula I according to the invention also include hydrates which may be formed during the salt formation.
  • a preferred group of compounds of formula I is represented by the compounds of formula 1-1
  • X is S, SO or S0 2 ;
  • Rx is independently selected from the group consisting of hydrogen, halogen, cyano, Ci-C4alkyl, Ci- C4haloalkyl, Ci-C4haloalkoxy, Ci-C4alkoxy, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, and Ci-C4haloalkylsulfanyl with the proviso that at least one Rx is different from hydrogen.
  • Ri is preferably ethyl
  • R2 is preferably Ci-C6halo- alkyl or Ci-C4haloalkylsulfanyl
  • X is preferably SO2
  • Xi is preferably N(CH3).
  • Preferred compounds of formula 1-1 are represented by compounds of formula 1-1 a,
  • Rx is independently selected from the group consisting of hydrogen and halogen with the proviso that at least one Rx is different from hydrogen.
  • Ri is preferably ethyl
  • R2 is preferably Ci-C6halo- alkyl.
  • Even more preferred compounds of formula l-1a are those in which R2 is CF3, Ri is ethyl, A is nitrogen, Gi is nitrogen and Rx is independently hydrogen or halogen, preferably fluorine or chlorine, with the proviso that at least one Rx is different from hydrogen.
  • R2 is preferably Ci-C6haloalkyl and Ri is preferably ethyl.
  • R2 is CF3, Ri is ethyl, A is nitrogen, Gi is nitrogen and Rx is is CF3, fluorine or chlorine.
  • a further preferred group of compounds of formula I is represented by the compounds of formula I-2
  • X is S, SO or S0 2 ;
  • Rx is independently selected from the group consisting of hydrogen, halogen, cyano, Ci-C4alkyl, Ci- C4haloalkyl, Ci-C4haloalkoxy, Ci-C4alkoxy, Ci-C4alkylsulfanyl, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, and Ci-C4haloalkylsulfanyl; with the proviso that at least one Rx is different from hydrogen.
  • Ri is preferably ethyl
  • R2 is preferably Ci-C6halo-alkyl or Ci-C4haloalkylsulfanyl
  • X is preferably SO2
  • Xi is preferably N(CH3).
  • Preferred compounds of formula I-2 are represented by compounds of formula l-2a
  • R2 is preferably Ci-C6haloalkyl and Ri is preferably ethyl.
  • R2 is CF3, Ri is ethyl, A is nitrogen, Gi is nitrogen and Rx is hydrogen or halogen, preferably fluorine or chlorine, with the proviso that at least one Rx is different from hydrogen.
  • both Rx are independently fluorine or chlorine.
  • a preferred group of compounds of formula I is represented by the compounds of formula I-3 wherein Gi , Ri, R2, A and Xi are as defined under formula I above;
  • X is S, SO or S0 2 ;
  • Rxa is independently selected from the group consisting of hydrogen, halogen, cyano or Ci- C4haloalkyl.
  • Ri is preferably ethyl
  • R2 is preferably Ci alkyl or Ci-C4haloalkylsulfanyl
  • X is preferably SO2
  • Xi is preferably N(CH3).
  • Preferred compounds of formula I-3 are represented by compounds of formula l-3a
  • X is S, SO or S0 2 ;
  • Rxa is hydrogen, halogen, cyano or Ci-C4haloalkyl.
  • Ri is preferably ethyl
  • R2 is preferably Ci-CehaloalkyI or Ci-C4haloalkylsulfanyl
  • X is preferably SO2
  • Xi is preferably N(CH3).
  • Preferred compounds of formula 1-4 are represented by compounds of formula l-4a
  • Ri is Ci-C 4 alkyl
  • R2 is Ci-C4haloalkyl
  • X is S or S0 2 ; A is N; and
  • Q is phenyl, which is mono- or disubstituted by substituents selected from the group consisting of halogen and Ci-C4haloalkyl;
  • Q is pyrazolyl, mono-substituted by Ci-C4haloalkyl
  • compounds of formula I can be prepared (as depicted in scheme 1 ) by reacting compounds of formula II with compounds of formula III, wherein Xbi can be a halogen, preferentially chlorine, bromine or iodine, or a sulfonate, like for example a trifluoromethanesulfonate and Ybi can be a boron-derived functional group, as for example B(OH)2 or B(ORbi)2 wherein Rbi can be a Ci-C6alkyl group or the two groups ORbi can form together with the boron atom a five- or six-membered ring, as for example a pinacol boronic ester (Suzuki cross-coupling, see for example Tetrahedron Letters, 43(39), 6987-6990; 2002).
  • Xbi can be a halogen, preferentially chlorine, bromine or iodine, or a sulfonate, like for example a tri
  • A, Xi , Ri , R 2 , X and Q are as described in formula I.
  • the reaction can be catalyzed by a palladium based catalyst, for example tetrakis(triphenylphosphine) palladium(O), bis(triphenylphosphine)palladium(ll) dichloride, chloro(2-dicyclohexylphosphino-2',4',6'- triisopropyl-1 , 1'-biphenyl)[2-(2'-amino-1 , 1'-biphenyl)]palladium(ll) (XPhos palladacycle),
  • a palladium based catalyst for example tetrakis(triphenylphosphine) palladium(O), bis(triphenylphosphine)palladium(ll) dichloride, chloro(2-dicyclohexylphosphino-2',4',6'- triisoprop
  • reaction temperature can preferably range from ambient temperature to the boiling point of the reaction mixture, or alternatively heating may be performed under microwave
  • compounds of formula II wherein Xbi can be a halogen, preferentially chlorine, bromine or iodine, or a sulfonate, like for example a trifluoromethanesulfonate, may be reacted with compounds of formula III, wherein Ybi is a magnesium halide group, such as -MgBr (Kumada cross-coupling), optionally in the presence of additives, such as zind halides (Journal of Organic Chemistry, 75(19), 6677-6680; 2010).
  • Xbi can be a halogen, preferentially chlorine, bromine or iodine, or a sulfonate, like for example a trifluoromethanesulfonate
  • Ybi is a magnesium halide group, such as -MgBr (Kumada cross-coupling), optionally in the presence of additives, such as zind halides (Journal of
  • the reaction may be catalyzed by a palladium based catalyst, or may involve a nickel based catalyst, such as 1 ,3-is(diphenylphosphino)propanenickel dichloride (dppp)NiCl2.
  • a palladium based catalyst or may involve a nickel based catalyst, such as 1 ,3-is(diphenylphosphino)propanenickel dichloride (dppp)NiCl2.
  • Xbi can be a halogen, preferentially chlorine, bromine or iodine, or a sulfonate, like for example a trifluoromethanesulfonate
  • Ybi is a zinc halide group, such as -ZnBr (Negishi cross- coupling), as illustrated for example in Synthetic Communications, 28(2), 225-232; 1998.
  • the reaction may be catalyzed by a palladium based catalyst, such as for example, (1 ,1 'bis(diphenylphosphino)- ferrocene)dichloropalladium Pd(dppf)Cl2 or bis(triphenylphosphine)palladium(ll) dichloride, optionally in the presence of phosphine additives (such as, for example, 2-dicyclohexyl-phosphino-2',6'- dimethoxy-biphenyl S-PHOS), in a solvent, like, for example 1 ,2-dimethoxyethane, dioxane, toluene, or tetrahydrofuran, preferably under inert atmosphere.
  • the reaction temperature can preferentially range from ambient temperature to the boiling point of the reaction mixture.
  • Compounds of formula I can also be made (as depicted in scheme 2) by reacting compounds of formula IV with compounds of formula V, wherein Xb2 can be a halogen, preferentially chlorine, bromine or iodine, or a sulfonate, like for example a trifluoromethanesulfonate and Yb2 can be a boron- derived functional group, as for example B(OH)2 or B(ORb2)2 wherein Rb2 can be a Ci-C6alkyl group or the two groups ORb2 can form together with the boron atom a five- or six-membered ring, as for example a pinacol boronic ester.
  • A, Xi , Ri , R2, X and Q are as described in formula I.
  • the reaction can be catalyzed by a palladium based catalyst, for example
  • reaction temperature can preferentially range from ambient temperature to the boiling point of the reaction mixture, or alternatively heating may be performed under microwave irradiation.
  • these compounds can be advantageously accessed by reacting a compound of the formula IV with a compound of the formula Va, wherein Yb2 can be a boron-derived functional group, such as for example B(OH)2 or B(ORb2)2 wherein Rb2 can be a Ci-C6alkyl group or the two groups ORb2 can form together with the boron atom a five - or six-membered ring, as for example a pinacol boronic ester (scheme 2a).
  • Yb2 can be a boron-derived functional group, such as for example B(OH)2 or B(ORb2)2 wherein Rb2 can be a Ci-C6alkyl group or the two groups ORb2 can form together with the boron atom a five - or six-membered ring, as for example a pinacol boronic ester (scheme 2a).
  • A, Ri , R2, X and Xi are as defined under formula I above and Q is as described in formula I, with the condition that the attachment point is a nitrogen atom.
  • the reaction also known as Chan-Lam coupling (P. Y. S. Lam, C. G. Clark, S. Saubern, J. Adams, M. P.Winters, D. M. T. Chan, A. Combs, Tetrahedron Lett. 1998, 39, 2941 ), is commonly performed with one to two equivalents of a base, like pyridine or triethylamine, in presence of one to two equivalents of a copper derivative, like for example copper (II) acetate and under an oxygen-containing atmosphere.
  • the reaction can be run in an inert solvent, like dichloromethane, dioxane or dimethylformamide, usually at or around room temperature.
  • Such a reaction with a heterocycle Q-H (which contains an appropriate NH functionality) of formula Va may 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 copper(l) iodide, with or without an additive such as L-proline, ⁇ , ⁇ '- dimethylcyclohexane-1 ,2-diamine or ⁇ , ⁇ '-dimethylethylene-diamine, in an inert solvent such as N- methylpyrrolidone NMP or ⁇ , ⁇ -dimethylformamide DMF at temperatures between 30-150°C, optionally under microwave irradiation.
  • a base such as potassium carbonate K2CO3 or cesium carbonate CS2CO3
  • a copper catalyst for example copper(l) iodide
  • an additive such as L-proline, ⁇ , ⁇ '- dimethylcyclohexane-1 ,2-diamine or ⁇ , ⁇
  • Optional additive such as N,N-dimethylethylene-diamine
  • Compounds of formula l-a3, wherein A, Ri, R2, Xi and Q have the values defined in formula I, and X is -SO2-, can be prepared by oxidation of compounds of formula l-a2, wherein A, Ri, R2, Xi and Q have the values defined in formula I, and X is -SO-.
  • the reaction can be performed with reagents like, for example, a peracid such as peracetic acid or m-chloroperbenzoic acid, or a hydroperoxide, as for example, hydrogen peroxide or tert-butylhydroperoxide, or an inorganic oxidant, like a monoperoxo- disulfate salt or potassium permanganate.
  • Compounds of formula l-a1 may also be prepared (scheme 4) by reacting a compound of the formula VI with a compound of the formula VII, wherein A, Ri, R2, Xi and Q have the values defined in formula I and X is sulphur and M is a metal or non-metal cation.
  • the cation M is assumed to be monovalent, but polyvalent cations associated with more than one S-Ri group can also be considered.
  • Prefered cations are, for example lithium, sodium, potassium or cesium.
  • Xb3 is a leaving group like, for example, fluorine, chlorine, bromine or iodine, an aryl- or alkylsulfonate, but many other leaving groups could be considered.
  • the reaction can be performed in a solvent, preferably aprotic (such as ⁇ , ⁇ -dimethylformamide or acetonitrile), at temperatures below 0°C or up to boiling temperature of the reaction mixture.
  • Xb3 is a leaving group like, for example, fluorine, chlorine, bromine or iodine, or an aryl- or alkylsulfonate such as trifluoromethanesulfonate, or any other similar leaving group
  • Xb4 can be a halogen, preferentially chlorine, bromine or iodine, or a sulfonate, like for example a trifluoromethanesulfonate, most preferably bromine or iodine
  • Yb4 can be a boron- derived functional group, as for example B(OH)2 or B(ORb4)2 wherein Rb4 can be a Ci-C6alkyl group or the two groups ORb4 can form together with the boron atom a five- or six-membered ring, as for example a pinacol boronic ester
  • reaction can be catalyzed by a palladium based catalyst, for example tetrakis(triphenyl- phosphine)palladium(O), bis(triphenylphosphine) palladium(ll) dichloride or (1 ,1 'bis(diphenyl- phosphino)-ferrocene)dichloropalladium-dichloromethane (1 : 1 complex), in presence of a base, like sodium carbonate, tripotassium phosphate or cesium fluoride, in a solvent (such as toluene, 1 ,2- dimethoxy-ethane DME, ethanol, iso-propyl alcohol, tetrahydrofuran or dioxane) or a solvent mixture, like, for example a mixture of 1 ,2-dimethoxyethane and water, or of dioxane and
  • a palladium based catalyst for example tetrakis(triphenyl- phos
  • compounds of formula VII I wherein Xb4 can be a halogen, preferentially chlorine, bromine or iodine, or a sulfonate, like for example a trifluoromethanesulfonate, may be reacted with compounds of formula IX, wherein Yb4 is a magnesium halide group, such as -MgBr (Kumada cross- coupling), optionally in the presence of additives, such as zind halides (Journal of Organic Chemistry, 75(19), 6677-6680; 2010).
  • the reaction may be catalyzed by a palladium based catalyst, or may involve a nickel based catalyst, such as 1 ,3-is(diphenylphosphino)propanenickel dichloride
  • the reaction may be catalyzed by a palladium based catalyst, such as for example, (1 ,1 'bis(diphenylphosphino)- ferrocene)dichloropalladium Pd(dppf)Cl2 or bis(triphenylphosphine)palladium(l l) dichloride, optionally in the presence of phosphine additives (such as, for example, 2-dicyclohexyl-phosphino-2',6'- dimethoxy-biphenyl S-PHOS), in a solvent, like, for example 1 ,2-dimethoxyethane, dioxane, toluene, or tetrahydrofuran, preferably under inert atmosphere.
  • the reaction temperature can preferentially range from ambient temperature to the boiling point of the reaction mixture.
  • compounds of formula VI can also be prepared by reacting compounds of formula X, wherein Xb3 is a leaving group like, for example, fluorine, chlorine, bromine or iodine, or an aryl- or alkylsulfonate such as trifluoromethanesulfonate, or any other similar leaving group, with compounds of formula XI , wherein Xb5 can be a halogen, preferentially chlorine, bromine or iodine, or a sulfonate, like for example a trifluoromethanesulfonate, most preferably bromine or iodine, and Yb5 can be a boron-derived functional group, as for example B(OH)2 or B(ORb5)2 wherein Rb5 can be a Ci-C6alkyl group or the two groups ORbs can form together with the boron atom a five- or six-membered ring, as for example a pin
  • X and XI , A, Xi , 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(l l) dichloride or (1 , 1 'bis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane (1 : 1 complex), in presence of a base, like sodium carbonate, tripotassium phosphate or cesium fluoride, in a solvent (such as toluene, 1 ,2-dimethoxy-ethane DME, ethanol, iso-propyl alcohol, tetrahydrofuran or dioxane) or a solvent mixture, like, for example a mixture of 1 ,2-dimethoxyethane and water, or of dioxane
  • Compounds of formula I can also be prepared (scheme 7) by reacting compounds of formula XIII and compounds of formula XIV under various formal dehydration conditions, wherein A, Ri, R2, X, Xi 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 201 1/043404, WO 201 1/040629, WO 2010/125985, WO 2012/086848, WO 2013/018928, WO 2013/191 1 13, WO 2013/180193 and WO 2013/180194.
  • Such processes are well known and have been described for example in WO 201 1/040629 or WO 2009131237 (Xi is oxygen), WO 201 1088990 or Inorg.
  • compounds of formula XV can be converted to compounds of formula I (wherein Xi is O) using triphenylphosphine, di-isopropyl azodicarboxylate in an inert solvent such as THF at temperatures between 25-50°C.
  • THF inert solvent
  • X is S X is SO or S02 may be prepared by reacting a compound of formula XXVII, wherein A and Q are as defined above, and wherein R50 is Ci-C4alkyl and in which Xbi is a leaving group such as, for example, a halogen (preferably fluorine, chlorine or bromine) or nitro, with a compound of formula Vila, or a salt thereof VII, wherein Ri is as defined in formula I, optionally in the presence of a suitable base, such as alkali metal carbonates, for example sodium carbonate and potassium carbonate, or alkali metal hydrides such as sodium hydride, or alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, optionally in the presence of a catalytic amount of an additive, such as an ammonium salt (for example tetrabutylammonium bromide TBAB), in an inert solvent at temperatures preferably between 25- 120°C.
  • a suitable base such as alkali metal carbonates
  • solvent to be used examples include ethers such as THF, ethylene glycol dimethyl ether, tert-butylmethyl ether, and 1 ,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, polar aprotic solvents such as ⁇ , ⁇ -dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethyl sulfoxide, or water.
  • salts of the compound of formula Vila include compounds of the formula VII
  • Ri is as defined above and wherein M is, for example, sodium or potassium.
  • Oxidation of compounds of formula XIV, wherein X is S, and wherein A, Ri and Q are as defined above, with a suitable oxidizing agent, into compounds of formula XlVb, wherein X is SO or SO2 may be achieved under conditions already described above.
  • Benze Reaction may be prepared by a Suzuki reaction, which involves for example, reacting compounds of formula XXVIII, wherein A, R50 and Xbi are as defined above, and wherein Xbi is a leaving group like, for example, chlorine, bromine or iodine (preferably bromine), or an aryl- or alkylsulfonate such as trifluoromethane-sulfonate, with compounds of formula III, wherein Q is optionally substituted phenyl, pyridyl or pyrimidyl, and wherein Ybi can be a boron-derived functional group, such as for example B(OH)2 or B(ORbi)2 wherein Rbi can be a Ci-C4alkyl group or the two groups ORbi can form together with the boron atom a five membered ring, as for example a pinacol boronic ester.
  • XXVIII wherein A, R50 and Xbi are as
  • the reaction may be catalyzed by a palladium based catalyst, for example fefra/c/ ' s(triphenylphosphine)-palladium(0), or bis(triphenylphosphine)palladium(ll) dichloride or (1 , 1 'bis(diphenylphosphino)ferrocene)dichloro- palladium-dichloromethane (1 :1 complex), in presence of a base, like sodium carbonate or cesium fluoride, in a solvent or a solvent mixture, like, for example a mixture of 1 ,2-dimethoxyethane and water or of dioxane and water, preferably under inert atmosphere.
  • the reaction temperature can preferentially range from room temperature to the boiling point of the reaction mixture.
  • Suzuki reactions are well known to those skilled in the art and have been reviewed, for example, in J.Orgmet. Chem. 576, 1999, 147-168.
  • compounds of formula XXVII wherein A, Q, R50 and Xbi are as defined above, may be prepared by a Stille reaction between compounds of formula Ilia, wherein Q is as defined above, and wherein Yb2o is a trialkyl tin derivative, preferably tri-n-butyl tin, and compounds of formula XXVIII, wherein A, R50 and Xbi are as defined above, and wherein Xbi is a leaving group like, for example, chlorine, bromine or iodine (preferably bromine), or an aryl- or alkylsulfonate such as trifluoromethane- sulfonate.
  • Such Stille reactions are usually carried out in the presence of a palladium catalyst, for example fefra/c/ ' s(triphenylphosphine)palladium(0), or bis(triphenylphosphine)palladium(ll) dichloride, in an inert solvent such as ⁇ , ⁇ -dimethylformamide, acetonitrile, toluene or dioxane, optionally in the presence of an additive, such as cesium fluoride, or lithium chloride, and optionally in the presence of a further catalyst, for example copper(l)iodide.
  • a palladium catalyst for example fefra/c/ ' s(triphenylphosphine)palladium(0), or bis(triphenylphosphine)palladium(ll) dichloride
  • an inert solvent such as ⁇ , ⁇ -dimethylformamide, acetonitrile, toluene or dioxane
  • XXIX XXVIII may be prepared from the corresponding carboxylic acid compounds of formula XXIX, wherein A, Xbi and Xb ⁇ are as defined above, by reaction with an alcohol of formula XXX, wherein R50 is Ci-C4alkyl , optionally in the presence of an acid (such as sulfuric acid), or alternatively optionally in presence of an activating agent, such as for example oxalyl chloride (COCI)2.
  • an activating agent such as for example oxalyl chloride (COCI)2.
  • compounds of formula XXVII wherein A, R50 and Xbi are as defined above, may be prepared from compounds of formula XXVI II , wherein A, R50 and Xbi are as defined above, and wherein bi is a leaving group like, for example, chlorine, bromine or iodine (preferably bromine), or an aryl- or alkylsulfonate such as trifluoromethane- sulfonate, by reaction with a heterocycle Q-H (which contains an appropriate NH functionality) Va, wherein Q is optionally substituted pyrazolyl or triazolyl, 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 copper(l) iodide, with or without an additive such as L-proline, N,N'-dimethylcyclohexane-1 ,2-
  • compounds of formula VI wherein Xb3 is a leaving group like, for example, fluorine, chlorine, bromine or iodine, or an aryl- or alkylsulfonate such as trifluoromethane- sulfonate, or any other similar leaving group, can be prepared by reacting compounds of formula XVI, wherein A and Q have the values defined for formula I , with an activating agent, like, for example oxalyl chloride or thionyl chloride or a carbodiimid reagent to generate the activated species XVI-a, followed by reaction with compounds of formula XI II , wherein R2 and Xi are as described in formula I .
  • the intermediate compounds of formula XVII may be isolated, but are preferentially converted into the compounds of formula VI in a similar way as described above for the transformation of compounds XV into compounds of formula I.
  • Compounds of formula XXI can be prepared as described in scheme 10a, by reacting compounds of formula XX, wherein A is CH or nitrogen, and Xb3a is a leaving group like, for example nitro, fluorine, chlorine, bromine or iodine, or an aryl- or alkylsulfonate such as trifluoromethane-sulfonate, and Xb4 can be a halogen, preferentially chlorine, bromine or iodine, or a sulfonate, like for example a trifluoromethanesulfonate, most preferably bromine or iodine, with a compound of formula VII, wherein Ri is as defined in formula I, and M is a metal or non-metal cation.
  • Ri is as defined in formula I
  • M is a metal or non-metal cation.
  • the cation M is assumed to be monovalent, but polyvalent cations associated with more than one S-R1 group can also be considered.
  • Prefered cations are, for example lithium, sodium, potassium or cesium.
  • the reaction can be performed in a solvent, preferably polar aprotic, such as THF, N,N-dimethylformamide or MeCN, at temperatures between -78°C and the boiling temperature of the reaction mixture.
  • Compounds of formula XVIII-c can be prepared by hydrolysis of compounds of formula XXI under acidic (e.g. HCI or H2SO4) or basic conditions (e.g. NaOH or KOH) as described in scheme 10a, under conditions known to a person skilled in the art.
  • Compounds of formula M-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 Xi and R2 are as defined in formula I.
  • the intermediate compounds of formula XXII may be isolated, but are preferentially converted into the compounds of formula M-a2 in a similar way as described above (transformation of compounds XV into compounds of formula I).
  • X can be S, SO or SO2.
  • the reaction can be performed with reagents like, for example a peracid as peracetic acid or m-chloroperbenzoic acid, or a hydroperoxide as for example hydrogen peroxide or tert-butylhydroperoxide, or an inorganic oxidant, like a mono-peroxodisulfate salt or potassium permanganate, preferentially meta-chloro- perbenzoic acid.
  • reagents like, for example a peracid as peracetic acid or m-chloroperbenzoic acid, or a hydroperoxide as for example hydrogen peroxide or tert-butylhydroperoxide, or an inorganic oxidant, like a mono-peroxodisulfate salt or potassium permanganate, preferentially meta-chloro- perbenzoic acid.
  • a compound of formula XVIII-c, wherein X is S, SO or SO2 can alternatively be prepared by analogous methods to those described in the literature (scheme 10b).
  • a compound of formula XVIII- c, wherein X is S may be prepared by saponification of a compound of formula XXIV, wherein RLG is Ci-C4alkyl, under conditions known to a person skilled in the art (Ri is as defined in formula I, A is N or CH, and Xb4 can be a halogen, preferentially chlorine, bromine or iodine, or a sulfonate, like for example a trifluoromethanesulfonate, most preferably bromine or iodine).
  • X is S in X is SO or SO2
  • XXIV-a Compounds of formula XXIV, wherein RLG is Ci-C4alkyl, may be prepared by treatment of compounds of formula XXIII, wherein Xb3a is a leaving group like, for example nitro, fluorine, chlorine, bromine or iodine, or an aryl- or alkylsulfonate such as trifluoromethanesulfonate, and wherein RLG is Ci-C4alkyl, with a reagent M-S-Ri of formula VII, wherein Ri is as defined in formula I and M is a metal or non- metal cation, under conditions described above.
  • Xb3a is a leaving group like, for example nitro, fluorine, chlorine, bromine or iodine, or an aryl- or alkylsulfonate such as trifluoromethanesulfonate
  • RLG Ci-C4alkyl
  • ester compounds of formula XXIV may be prepared from the corresponding carboxylic acid compounds of formula XVIII-c, wherein X is S, by reaction with an alcohol of formula RLGOH, wherein RLG is Ci-C4alkyl , optionally in the presence of an acid (such as sulfuric acid), or alternatively optionally in presence of an activating agent, such as for example oxalyl chloride (COCI)2.
  • an activating agent such as for example oxalyl chloride (COCI)2.
  • COCI oxalyl chloride
  • the cation M is assumed to be monovalent, but polyvalent cations associated with more than one S-R1 group can also be considered.
  • Prefered cations are, for example lithium, sodium, potassium or cesium.
  • the reaction can be performed in a solvent, preferably polar aprotic, at temperatures below 0°C or up to boiling temperature of the reaction mixture.
  • the reaction can be performed with reagents like, for example a peracid as peracetic acid or m-chloroperbenzoic acid, or a hydroperoxide as for example hydrogen peroxide or tert-butylhydroperoxide, or an inorganic oxidant, like a mono-peroxodisulfate salt or potassium permanganate, preferentially meta-chloroperbenzoic acid.
  • reagents like, for example a peracid as peracetic acid or m-chloroperbenzoic acid, or a hydroperoxide as for example hydrogen peroxide or tert-butylhydroperoxide, or an inorganic oxidant, like a mono-peroxodisulfate salt or potassium permanganate, preferentially meta-chloroperbenzoic acid.
  • compounds of formula M-a2 wherein A, Ri , R2 and Xi have the values defined in formula I, and X is -SO-, and wherein Xb4 is a halogen, preferentially chlorine, bromine or iodine, or a sulfonate like for example a trifluoromethane- sulfonate, can be prepared by oxidation of compounds of formula Il-a1 , wherein A, Ri , R2 and Xi have the values defined in formula I, and X is -S-, and wherein Xb4 is a halogen, preferentially chlorine, bromine or iodine, or a sulfonate, like for example a trifluoromethanesulfonate.
  • These reactions can be performed in various organic or aqueous solvents compatible to these conditions, by temperatures from below 0°C up to the boiling point of the solvent system.
  • step A hydrogen abstraction on a compound of the formula lll-a wherein Zbi is hydrogen, with a strong base (step A), like butyllithium or lithium diisopropylamide or (i-PrMgCI, LiCI), followed by reaction of the metallated intermediate of the formula lll-b, wherein Zb ⁇ is a metal such as Li + or MgCI + for example, with, for example, a trialkylborate (step B).
  • Another way to access an organometal intermediate of the formula lll-b is from a compound of the formula lll-a wherein Zbi is chlorine, bromine or iodine, via metal-halogen exchange with an organometallic species (step C), like butyllithium or an organomagnesium compound, or direct metallation with a metal, like magnesium.
  • organometallic species like butyllithium or an organomagnesium compound
  • Compounds of formula IV, wherein A, X, Xi , Ri and R2 are as described in formula I, can be prepared from compounds of formula II (scheme 14), wherein A, X, Xi , Ri and R2 are as described in formula I.
  • compounds of formula II, wherein Xbi is chlorine, bromine or iodine can be treated with an organometallic species like, for example, butyllithium or an organomagnesium compound, to generate an intermediate compound of the formula ll-a, wherein Zb3 is as defined in the scheme, via metal- halogen exchange.
  • This reaction is preferentially performed in an anhydrous aprotic solvent, such as THF, at low temperature (between -120°C and 0°C), preferentially between -1 10°C and -60°C).
  • the intermediate organometal compound of formula ll-a is preferably directly converted into compound of formula IV by reaction with a boronate compound B(ORb2)3, wherein Rb2 is a a Ci-C6alkyl group.
  • the boronic acid IV wherein Yb ⁇ is -B(OH)2, or a dialkylboronate IV, wherein Yb ⁇ is -B(ORb2)2, can be formed.
  • reaction generating a cyclic boronate IV, wherein Yb ⁇ is
  • a reaction can be performed in an aprotic solvent, in presence of a base, preferentially a weak base, such as potassium acetate KOAc.
  • a base preferentially a weak base, such as potassium acetate KOAc.
  • [1 , 1 '-Bis(diphenylphosphino)ferrocene]dichloropalladium(ll), also known as palladium dppf dichloride or Pd(dppf)Cl2 is a common catalyst for this type of reaction.
  • the temperature of the reaction is preferably comprised between 0°C and the boiling point of the reaction mixture, or alternatively heating may be performed under microwave irradiation.
  • the reactants can be reacted in the presence of a base.
  • suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines.
  • sodium hydroxide sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert- butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine,
  • the reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethylamine, pyridine, N-methylmorpholine or ⁇ , ⁇ -diethylaniline, may also act as solvents or diluents.
  • the reaction is advantageously carried out in a temperature range from approximately -80°C to approximately +140°C, preferably from approximately -30°C to approximately +100°C, in many cases in the range between ambient temperature and approximately +80°C.
  • a compound of formula I can be converted in a manner known per se into another compound of formula I by replacing one or more substituents of the starting compound of formula I in the customary manner by (an)other substituent(s) according to the invention.
  • Salts of compounds of formula I can be prepared in a manner known per se.
  • acid addition salts of compounds of formula I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • Salts of compounds of formula I can be converted in the customary manner into the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds of formula I can be converted in a manner known per se into other salts of compounds of formula I, acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • the compounds of formula I which have salt- forming properties can be obtained in free form or in the form of salts.
  • the compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.
  • Diastereomer mixtures or racemate mixtures of compounds of formula I, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diasteromers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
  • Enantiomer mixtures such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid
  • N-oxides can be prepared by reacting a compound of the formula I with a suitable oxidizing agent, for example the hbCh/urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride.
  • a suitable oxidizing agent for example the hbCh/urea adduct
  • an acid anhydride e.g. trifluoroacetic anhydride.
  • the compounds of formula I and, where appropriate, the tautomers thereof, 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 which may have been used for the crystallization of compounds which are present in solid form.
  • the compounds according to the following Tables below can be prepared according to the methods described above. The examples which follow are intended to illustrate the invention and show preferred compounds of formula I. The tables below illustrate specific compounds of the invention.
  • Table A-1 provides 22 compounds A-1.001 to A-1.022 of formula (I) wherein X is SO2, Ri is ethyl and A is N and wherein R2, Gi , Xi and Q are defined as in table X.
  • Table A-2 provides 22 compounds A-2.001 to A-2.022 of formula (I) wherein X is SO, Ri is ethyl and A is N and wherein R2, Gi, Xi and Q are defined as in table X.
  • Table A-3 provides 22 compounds A-3.001 to A-3.022 of formula (I) wherein X is S, Ri is ethyl and A is N and wherein R2, Gi, Xi and Q are defined as in table X.
  • the compounds of formula I according to the invention are preventively and/or curatively valuable active ingredients 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 or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina.
  • the insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i. e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate. Examples of the abovementioned animal pests are:
  • Hyalomma spp. Ixodes spp., Olygonychus spp, Ornithodoros spp., Polyphagotarsone latus,
  • Panonychus spp. Phyllocoptruta oleivora, Phytonemus spp, Polyphagotarsonemus spp, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp, Tarsonemus spp. and Tetranychus spp.;
  • Haematopinus spp. Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.;
  • Agriotes spp. Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis, Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp, Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemLineata, Lissorhoptrus spp., Liogenys spp, Maecolaspis spp, Maladera castanea, Megas
  • Acyrthosium pisum Adalges spp, Agalliana ensigera, Agonoscena targionii, Aleurodicus spp, Aleurocanthus spp, Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp, Brachycaudus spp, Brevicoryne brassicae, Cacopsylla spp, Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp, Cofana spec
  • Macrosiphum spp. Mahanarva spp, Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp., Neotoxoptera sp, Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter, Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Peregrinus maidis, Perkinsiella spp, Phorodon humuli, Phylloxera spp, Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp., Pulvinaria
  • Coptotermes spp Corniternes cumulans, Incisitermes spp, Macrotermes spp, Mastotermes spp, Microtermes spp, Reticulitermes spp.; Solenopsis geminate
  • Blatta spp. Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscus spp, and Schistocerca spp.;
  • the active ingredients according to the invention can be used for controlling, i. e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
  • Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts,
  • compositions and/or methods of the present invention may be also used on any ornamental and/or vegetable crops, including flowers, shrubs, broad-leaved trees and evergreens.
  • the invention may be used on any of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g. B. elatior, B. semperflorens, B. tubereux), Bougainvillea spp., Brachycome spp., Brassica spp.
  • Ageratum spp. Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g. B. elatior, B. semperflorens, B. tubereux), Bougainvillea spp., Brachycome spp.
  • Calceolaria spp. (ornamental), Calceolaria spp., Capsicum annuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemum spp., Cineraria spp. (C. maritime), Coreopsis spp., Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp.,
  • Gomphrena globosa Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (/. 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.
  • Canna 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.
  • the invention may be used on any of the following vegetable species: Allium spp. (A. sativum, A., cepa, A. oschaninii, A. Porrum, A. ascalonicum, A. fistulosum), Anthriscus cerefolium, Apium graveolus, Asparagus officinalis, Beta vulgarus, Brassica spp. (B. Oleracea, B. Pekinensis, B. rapa), Capsicum annuum, Cicer arietinum, Cichorium endivia, Cichorum spp. (C. intybus, C. endivia), Citrillus lanatus, Cucumis spp. (C. sativus, C.
  • Preferred ornamental species include African violet, Begonia, Dahlia, Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hortensia, rosemary, sage, St. Johnswort, mint, sweet pepper, tomato and cucumber.
  • the active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and
  • the active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca(preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
  • the invention may also relate to a method of controlling damage to plant and parts thereof by plant parasitic nematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasitic nematodes), especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolai
  • Needle nematodes Longidorus elongatus and other Longidorus species; Pin nematodes,
  • Pratylenchus species Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans,
  • Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. Nemoralis); ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H. obvia); Helicidae Helicigona arbustorum); Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g. CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecd
  • ⁇ -endotoxins for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins.
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ).
  • Truncated toxins for example a truncated CrylAb, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising 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.
  • deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a
  • transgenic crops are:
  • Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. Bt1 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
  • MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
  • MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
  • NK603 * MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 * MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1 Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain
  • Lepidoptera include the European corn borer.
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225).
  • PRPs pathogenesis-related proteins
  • Examples of such antipathogenic substances and transgenic plants capable of synthesising 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 are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • Crops may also be modified for enhanced resistance to fungal (for example Fusarium, Anthracnose, or Phytophthora), bacterial (for example Pseudomonas) or viral (for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus) pathogens.
  • Crops also include those that have enhanced resistance to nematodes, such as the soybean cyst nematode.
  • Crops that are tolerance to abiotic stress include those that have enhanced tolerance to drought, high salt, high temperature, chill, frost, or light radiation, for example through expression of NF-YB or other proteins known in the art.
  • Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A-0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in WO 03/000906).
  • ion channel blockers such as blockers for sodium and calcium channels
  • the viral KP1 , KP4 or KP6 toxins stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called
  • compositions according to the invention are the protection of stored goods and store rooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.
  • the present invention also provides a method for controlling pests (such as mosquitoes and other disease vectors; see also http://www.who.int/malaria/vector_control/irs/en/).
  • the method for controlling pests comprises applying the compositions of the invention to the target pests, to their locus or to a surface or substrate by brushing, rolling, spraying, spreading or dipping.
  • an IRS (indoor residual spraying) application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention.
  • the method for controlling such pests comprises applying a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate.
  • a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate.
  • Such application may be made by brushing, rolling, spraying, spreading or dipping the pesticidal composition of the invention.
  • an IRS application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention so as to provide effective residual pesticidal activity on the surface.
  • it is contemplated to apply such compositions for residual control of pests on a substrate such as a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.
  • Substrates including non-woven, fabrics or netting to be treated may be made of natural fibres such as cotton, raffia, jute, flax, sisal, hessian, or wool, or synthetic fibres such as polyamide, polyester, polypropylene, polyacrylonitrile or the like.
  • the polyesters are particularly suitable.
  • the methods of textile treatment are known, e.g. WO 2008/151984, WO 03/034823, US 5631072, WO 2005/64072, WO2006/128870, EP 1724392, WO 2005/1 13886 or WO 2007/090739.
  • Further areas of use of the compositions according to the invention are the field of tree injection/trunk treatment for all ornamental trees as well all sort of fruit and nut trees.
  • the compounds according to the present invention are especially suitable against wood-boring insects from the order Lepidoptera as mentioned above and from the order Coleoptera, especially against woodborers listed in the following tables A and B: Table A. Examples of exotic woodborers of economic importance.
  • Agrilus sayi Bayberry, Sweetfern
  • Rhododendron Rhadodendron, Azalea, Laurel, Poplar, Willow, Mulberry
  • Phloeotribus liminaris Peach, Cherry, Plum, Black cherry,
  • the present invention may be also used to control any insect pests that may be present in turfgrass, including for example beetles, caterpillars, fire ants, ground pearls, millipedes, sow bugs, mites, mole crickets, scales, mealybugs ticks, spittlebugs, southern chinch bugs and white grubs.
  • the present invention may be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults.
  • the present invention may be used to control insect pests that feed on the roots of turfgrass including white grubs (such as Cyclocephala spp. (e.g. masked chafer, C. lurida),
  • white grubs such as Cyclocephala spp. (e.g. masked chafer, C. lurida)
  • Rhizotrogus spp. e.g. European chafer, R. majalis
  • Cotinus spp. e.g. Green June beetle, C. nitida
  • Popillia spp. e.g. Japanese beetle, P. japonica
  • Phyllophaga spp. e.g. May/June beetle
  • Ataenius spp. e.g. Black turfgrass ataenius, A. spretulus
  • Maladera spp. e.g. Asiatic garden beetle, M.
  • the present invention may also be used to control insect pests of turfgrass that are thatch dwelling, including armyworms (such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta), cutworms, billbugs (Sphenophorus spp. , such as S. venatus verstitus and S. parvulus), and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis).
  • armyworms such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta
  • cutworms such as S. venatus verstitus and S. parvulus
  • sod webworms such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis.
  • the present invention may also be used to control insect pests of turfgrass that live above the ground and feed on the turfgrass leaves, including chinch bugs (such as southern chinch bugs, Blissus insularis), Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug (Antonina graminis), two-lined spittlebug (Propsapia bicincta), leafhoppers, cutworms (Noctuidae family), and greenbugs.
  • the present invention may also be used to control other pests of turfgrass such as red imported fire ants (Solenopsis invicta) that create ant mounds in turf.
  • compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • Anoplurida Haematopinus spp., Linognathus spp., Pediculus spp. and Phtirus spp., Solenopotes spp..
  • Mallophagida Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp.,
  • 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., Fanni
  • Siphonaptrida for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp..
  • Heteropterida for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp..
  • Actinedida Prostigmata
  • Acaridida Acaridida
  • Acarapis spp. Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp.,
  • Pterolichus spp. Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp..
  • compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
  • compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec.,Tryptodendron spec, Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec, and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus
  • Reticulitermes santonensis Reticulitermes lucifugus
  • Mastotermes darwiniensis Zootermopsis nevadensis and Coptotermes formosanus
  • bristletails such as Lepisma saccharina.
  • the compounds according to the invention can be used as pesticidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances.
  • formulation adjuvants such as carriers, solvents and surface-active substances.
  • the formulations can be in various physical forms, e.g.
  • Such formulations can either be used directly or diluted prior to use.
  • the dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • the formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions.
  • the active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.
  • the active ingredients can also be contained in very fine microcapsules.
  • Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release).
  • Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 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.
  • the encapsulating 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.
  • 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.
  • the formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se.
  • liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, 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, A/,A/-dimethylformamide, dimethyl s
  • Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
  • a large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.
  • Surface- active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes.
  • Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonat.es, 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 est
  • Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.
  • 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.
  • the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared.
  • Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively).
  • Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.
  • the inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to
  • a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • the rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
  • Preferred formulations can have the following compositions (weight %): Emulsifiable concentrates:
  • active ingredient 1 to 95 %, preferably 60 to 90 %
  • surface-active agent 1 to 30 %, preferably 5 to 20 %
  • liquid carrier 1 to 80 %, preferably 1 to 35 % Dusts:
  • active ingredient 0.1 to 10 %, preferably 0.1 to 5 %
  • solid carrier 99.9 to 90 %, preferably 99.9 to 99 %
  • active ingredient 5 to 75 %, preferably 10 to 50 %
  • surface-active agent 1 to 40 %, preferably 2 to 30 %
  • active ingredient 0.5 to 90 %, preferably 1 to 80 %
  • surface-active agent 0.5 to 20 %, preferably 1 to 15 %
  • solid carrier 5 to 95 %, preferably 15 to 90 %
  • active ingredient 0.1 to 30 %, preferably 0.1 to 15 %
  • solid carrier 99.5 to 70 %, preferably 97 to 85 %
  • Powders for drv seed treatment a) b) c) active ingredients 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 %
  • the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
  • Emulsions of any required dilution which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed. Extruder qranules
  • 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 stream of air.
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • Flowable concentrate for seed treatment active ingredients 40 % propylene glycol 5 % copolymer butanol PO/EO 2 %
  • Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1 ).
  • This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved.
  • a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added.
  • the mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • Formulation types include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo- emulsion (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 micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (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 feasible formulation in combination with agricultural
  • Mp means melting point in °C. Free radicals represent methyl groups. H NMR measurements were recorded on a Brucker 400MHz spectrometer, chemical shifts are given in ppm relevant to a TMS standard. Spectra measured in deuterated solvents as indicated. Either one 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)-.
  • Solvent degasser binary pump, heated column compartment and diode-array detector.
  • Solvent degasser binary pump, heated column compartment and diode-array detector.
  • Step 1 Preparation of methyl 5-bromo-3-chloro-pyridine-2-carboxylate
  • Step 2 Preparation of methyl 3-chloro-5-[3-(trifluoromethyl)pyrazol-1-yl]pyridine-2-carboxylate
  • Step 3 Preparation of 3-ethylsulfanyl-5-[3-(trifluoromethyl)pyrazol-1-yl]pyridine-2-carboxylic acid
  • Step 5 Preparation of 2-[3-ethylsulfanyl-5-[3-(trifluoromethyl)pyrazol-1-yl]-2-pyridyl]-3-methyl-6- (trifluoromethyl)imidazo[4,5-b]pyridine (compound P1 )
  • Step 1 Preparation of 3-ethylsulfanyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]-5-[4- (trifluoromethyl)phenyl]pyridine-2-carboxamide
  • Step 2 Preparation of 2-[3-ethylsulfanyl-5-[4-(trifluoromethyl)phenyl]-2-pyridyl]-3-methyl-6- (trifluoromethyl)imidazo[4,5-b]pyridine (compound P3)
  • Step 1 Preparation of 2-[3-ethylsulfanyl-5-(1 ,2,4-triazol-1-yl)-2-pyridyl]-3-methyl-6-(trifluoromethyl) imidazo[4,5-b]pyridine (compound P7
  • Step 2 Preparation of 2-[3-ethylsulfonyl-5-(1 ,2,4-triazol-1-yl)-2-pyridyl]-3-methyl-6-(trifluoromethyl) imidazo[4,5-b]pyridine (compound P8
  • compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients.
  • mixtures of the compounds of formula I with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing , during their storage or during their use.
  • Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
  • TX means "one compound selected from the group consisting of the compounds described in Tables A-1 , A-2, A-3 and P1 of the present invention”: an adjuvant selected from the group of substances consisting of petroleum oils (628) + TX, an acaricide selected from the group of substances consisting of 1 , 1 -bis(4-chlorophenyl)-2- ethoxyethanol (lUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate (lUPAC/Chemical Abstracts name) (1059) + TX, 2-fluoro-A/-methyl-A/-1 -naphthylacetamide (lUPAC name) (1295) + TX, 4-chlorophenyl phenyl sulfone (lUPAC name) (981 ) + TX, abamectin (1 ) + TX, acequinocy
  • prothidathion (1360) + TX, prothoate (1362) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridaphenthion (701 ) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, quinalphos (71 1 ) + TX, quintiofos (1381 ) + TX, R-1492 (development code) (1382) + TX, RA-17 (development code) (1383) + TX, rotenone (722) + TX, schradan (1389) + TX, sebufos + TX, selamectin [CCN] + TX, SI-0009 (compound code) + TX, sophamide (1402) + TX, spirodiclofen (
  • an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (lUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hyd rated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (lUPAC name) (347) and triphenyltin hydroxide (lUPAC name) (347) + TX,
  • an anthelmintic selected from the group of substances consisting of abamectin (1 ) + TX, crufomate (101 1 ) + TX, doramectin [CCN] + TX, emamectin (291 ) + TX, emamectin benzoate (291 ) + TX, eprinomectin [CCN] + TX, ivermectin [CCN] + TX, milbemycin oxime [CCN] + TX, moxidectin [CCN] + TX, piperazine [CCN] + TX, selamectin [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,
  • an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1 122) + TX, fenthion (346) + TX, pyridin-4-amine (lUPAC name) (23) and strychnine (745) + TX, a bactericide selected from the group of substances consisting of 1-hydroxy-1 /- -pyridine-2-thione
  • streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX, and thiomersal [CCN] + TX, a biological agent selected from the group of substances consisting of Adoxophyes orana GV (12) + TX, Agrobacterium radiobacter (13) + TX, Amblyseius spp.
  • Bacillus thuringiensis subsp. israelensis (scientific name) (51 ) + TX
  • Bacillus thuringiensis subsp. japonensis (scientific name) (51 ) + TX
  • Bacillus thuringiensis subsp. kurstaki (scientific name) (51 ) + TX
  • Helicoverpa zea NPV (431 ) + TX, Heterorhabditis bacteriophora and H. megidis (433) + TX, Hippodamia convergens (442) + TX, Leptomastix dactylopii (488) + TX, Macrolophus caliginosus (491 ) + TX, Mamestra brassicae NPV (494) + TX, Metaphycus helvolus (522) + TX, Metarhizium anisopliae var. acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae
  • a soil sterilant selected from the group of substances consisting of iodomethane (lUPAC name) (542) and methyl bromide (537) + TX,
  • a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir [CCN] + TX, busulfan [CCN] + TX, diflubenzuron (250) + TX, dimatif [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate [CCN] + TX, morzid [CCN] + TX, penfluron [CCN] + TX, tepa [CCN] + TX, thiohempa [CCN] + TX, thiotepa [CCN] + TX, tretamine [CCN] and uredepa [CCN] + TX,
  • an insect pheromone selected from the group of substances consisting of (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol (lUPAC name) (222) + TX, (E)-tridec-4-en-1-yl acetate (lUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (lUPAC name) (541 ) + TX, (E,Z)-tetradeca-4, 10-dien-1-yl acetate (lUPAC name) (779) + TX, (Z)-dodec-7-en-1-yl acetate (lUPAC name) (285) + TX, (Z)-hexadec-l 1- enal (lUPAC name) (436) + TX, (Z)-hexadec-l 1-en-1-yl acetate (lUPAC name) (437) + TX, (Z)- hexade
  • an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (lUPAC name) (591 ) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (lUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (lUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1 137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,
  • an insecticide selected from the group of substances consisting of 1-dichloro-1-nitroethane
  • hexafluorosilicate [CCN] + TX barium polysulfide (lUPAC/Chemical Abstracts name) (892) + TX, barthrin [CCN] + TX, Bayer 22/190 (development code) (893) + TX, Bayer 22408 (development code) (894) + TX, bendiocarb (58) + TX, benfuracarb (60) + TX, bensultap (66) + TX, beta- cyfluthrin (194) + TX, beta-cypermethrin (203) + TX, bifenthrin (76) + TX, bioallethrin (78) + TX, bioallethrin S-cyclopentenyl isomer (79) + TX, bioethanomethrin [CCN] + TX, biopermethrin (908) + TX, bioresmethrin (80) + TX, bis(2-chloroethyl)
  • chlorphoxim (989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, chromafenozide (150) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, cis-resmethrin + TX, cismethrin (80) + TX, clocythrin + TX, cloethocarb (999) + TX, closantel [CCN] + TX, clothianidin (165) + TX, copper acetoarsenite
  • polychlorodicyclopentadiene isomers (lUPAC name) (1346) + TX, polychloroterpenes (traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, prallethrin (655) + TX, precocene I [CCN] + TX, precocene II [CCN] + TX, precocene III [CCN] + TX, primidophos (1349) + TX, profenofos (662) + TX, profluthrin [CCN] + TX, promacyl (1354) + TX, promecarb (1355) + TX, propaphos (1356) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothiofos (686) + TX, prothoate (1362) + TX
  • a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (lUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (lUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913)
  • a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, 1 ,2-dibromo-3-chloropropane (lUPAC/Chemical Abstracts name) (1045) + TX, 1 ,2-dichloropropane (lUPAC/ Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene (lUPAC name) (1063) + TX, 1 ,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1 ,1- dioxide (lUPAC/Chemical Abstracts name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (lUPAC name) (980) + TX, 5-methyl-6-thioxo-1 ,3,5-thiadiazinan-3-ylacetic acid (lUPAC name) (1286
  • a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,
  • a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (720) + TX
  • a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1 ,3-dione (lUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, alpha- chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891 ) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX,
  • a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (lUPAC name) (934) + TX, 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (lUPAC name) (903) + TX, farnesol with nerolidol (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, sesasmolin (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, guazatine (422) + TX, guazatine acetates (422) + TX, methiocarb (530) + TX, pyridin-4-amine (lUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX,
  • a virucide selected from the group of substances consisting of imanin [CCN] and ribavirin [CCN] + TX,
  • a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (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 [1 16255-48-2] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [1 19446-68-3] + TX, diniconazole [83657-24-3] + TX, epoxiconazole
  • Acinetobacter Iwoffii + 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, Aspergillus flavus AF36 (AF36®) + TX, Aspergillus flavus NRRL 21882 (Aflaguard®) + TX, Aspergillus spp.
  • Bacillus subtilis strain 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, Bacillus subtilis strain AQ743 + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain QST3004 + TX, Bacillus subtilis var.
  • amyloliquefaciens strain FZB24 (Taegro® + TX, Rhizopro®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis CrylAb + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis israelensis (BMP123® + TX, Aquabac® + TX, VectoBac®) + TX, Bacillus thuringiensis kurstaki (Javelin® + TX, Deliver® + TX, CryMax® + TX, Bonide® + TX, Scutella WP® + TX, Turilav WP ® + TX, Astuto® + TX, Dipel WP® + TX, Biobit® + TX, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®
  • aizawai (XenTari® + TX, DiPel®) + TX, bacteria spp. (GROWMEND® + TX, GROWSWEET® + TX, Shootup®) + TX, bacteriophage of Clavipacter michiganensis (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 reuêtii + TX, Candida saitoana (Bio-Coat® + TX, Biocure®) + TX, Candida sake + TX, Candida 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 TX
  • Cupriavidus campinensis + TX Cydia pomonella granulovirus (CYD-X®) + TX
  • Drechslera hawaiinensis + TX Enterobacter cloacae + TX
  • Enterobacteriaceae + TX Entomophtora virulenta (Vektor®) + TX
  • Epicoccum nigrum + TX Epicoccum purpurascens + TX, Epicoccum
  • 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
  • Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Pseudomonas fluorescens strain A506 (BlightBan A506®) + TX, Pseudomonas putida + TX, Pseudomonas reactans + TX, Pseudomonas spp.
  • TX Scytalidium uredinicola + TX, Spodoptera exigua nuclear polyhedrosis virus (Spod-X® + TX, Spexit®) + TX, Serratia marcescens + TX, Serratia plymuthica + TX, Serratia spp. + TX, Sordaria fimicola + TX, Spodoptera littoralis nucleopolyhedrovirus (Littovir®) + TX,
  • Trichoderma gamsii TX
  • Trichoderma atroviride Plant®
  • Trichoderma harzianum rifai Mycostar®
  • 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,
  • Plant extracts including: pine oil (Retenol®) + TX, azadirachtin (Plasma Neem Oil® + TX, AzaGuard® + TX, MeemAzal® + TX, Molt-X® + TX, Botanical IGR (Neemazad® + TX, Neemix®) + TX, canola oil (Lilly Miller Vegol®) + TX, Chenopodium ambrosioides near ambrosioides (Requiem®) + TX, Chrysanthemum extract (Crisant®) + TX, extract of neem oil (Trilogy®) + TX, essentials oils of Labiatae (Botania®) + TX, extracts of clove rosemary peppermint and thyme oil (Garden insect killer®) + TX, Glycinebetaine (Greenstim®) + TX, garlic + TX, lemongrass oil (GreenMatch®) + TX, neem oil +
  • pheromones including: blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®) + TX, Codling Moth Pheromone (Paramount dispenser-(CM)/ Isomate C-Plus®) + TX, Grape Berry Moth Pheromone (3M MEC-GBM Sprayable Pheromone®) + TX, Leafroller pheromone (3M MEC - LR Sprayable Pheromone®) + TX, Muscamone (Snip7 Fly Bait® + TX, Starbar Premium Fly Bait®) + TX, Oriental Fruit Moth Pheromone (3M oriental fruit moth sprayable pheromone®) + TX, Peachtree Borer Pheromone (Isomate-P®) + TX, Tomato Pinworm Pheromone (3M Sprayable pheromone®) + TX, Entostat powder (extract from palm tree) (Exosex CM®) + TX, (E + ⁇ , ⁇ +
  • 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
  • TX Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug® + TX, Cryptoline®) + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica + TX, Dacnusa sibirica
  • Diglyphus isaea (Diminex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea + TX, Diglyphus isaea (Miglyphus® + TX, Digline®) + TX, Dacnusa sibirica (DacDigline® + TX, Minex®) + TX, Diversinervus spp.
  • TX 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
  • the active ingredient mixture of the compounds of formula I selected from Tables -1 , A-2, A-3 and P1 with active ingredients described above comprises a compound selected from Tables -1 , A-2, A-3 and P1 and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1 :6000, especially from 50: 1 to 1 :50, more especially in a ratio of from 20:1 to 1 :20, even more especially from 10: 1 to 1 : 10, very especially from 5:1 and 1 :5, special preference being given to a ratio of from 2: 1 to 1 :2, and a ratio of from 4:1 to 2: 1 being likewise preferred, above all in a ratio of 1 :1 , or 5: 1 , or 5:2, or 5:3, or 5:4, or 4:1 , or 4:2, or 4:3, or 3: 1 , or 3:2, or 2:1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or
  • the 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 the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.
  • the mixtures comprising a compound of formula I selected from Tables -1 , A-2, A-3 and P1 and one or more active ingredients as described above can be applied, for example, in a single "ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • the order of applying the compounds of formula I selected from Tables -1 , A-2, A-3 and P1 and the active ingredients as described above is not essential for working the present invention.
  • compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
  • auxiliaries such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides
  • compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • compositions that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention.
  • Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient.
  • the rate of application 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.
  • a preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question.
  • the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.
  • the compounds of the invention and compositions thereof are also be suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type.
  • the propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing.
  • the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling.
  • These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention.
  • Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds.
  • seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.
  • the present invention also comprises seeds coated or treated with or containing a compound of formula I.
  • coated or treated with and/or containing generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the ingredient may penetrate into the seed material, depending on the method of application. When the said seed product is (re)planted, it may absorb the active ingredient.
  • the present invention makes available a plant propagation material adhered thereto with a compound of formula (I). Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound of formula (I).
  • Seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.
  • the seed treatment application of the compound formula (I) can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds.
  • Example B1 Bemisia tabaci (Cotton white fly)
  • Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10 ⁇ 00 ppm DMSO stock solutions. After drying the leaf discs were infested with adult white flies. The samples were checked for mortality 6 days after incubation. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P2, P4, and P7.
  • Example B2 Diabrotica balteata (Corn root worm)
  • Maize sprouts, placed on an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10 ⁇ 00 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 4 days after infestation. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P1 , P2, P3, P4, P6, P7, and P8.
  • Example B3 Euschistus heros (Neotropical Brown Stink Bug)
  • Soybean leaves on agar in 24-well microtiter plates were sprayed with agueous test solutions prepared from 10 ⁇ 00 ppm DMSO stock solutions. After drying the leaf were infested with N-2 nymphs. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation. 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, P4, P6, P7 and P8.
  • Example B4 Myzus persicae (Green peach aphid)
  • Sunflower leaf discs were placed on agar in a 24-well microtiter plate and sprayed with agueous test solutions prepared from 10 ⁇ 00 ppm DMSO stock solutions. After drying, the leaf discs were infested with an aphid population of mixed ages. The samples were assessed for mortality 6 days after infestation. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P2, P4, P6, P7 and P8.
  • Example B5 Myzus persicae (Green peach aphid)
  • Roots of pea seedlings infested with an aphid population of mixed ages were placed directly in the agueous test solutions prepared from 10 ⁇ 00 DMSO stock solutions. The samples were assessed for mortality 6 days after placing seedlings in test solutions. The following compounds resulted in at least 80% mortality at a test rate of 24 ppm: P4.
  • Example B6 Plutella xylostella (Diamond back moth)
  • 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10 ⁇ 00 ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (10 to 15 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation.
  • 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: P2, P3, P4, P6, P7 and P8.
  • Example B7 Spodoptera littoralis (Egyptian cotton leaf worm)
  • Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10 ⁇ 00 ppm DMSO stock solutions. After drying the leaf discs were infested with five L1 larvae. The samples were assessed for mortality, anti-feedant effect, and growth inhibition in comparison to untreated samples 3 days after infestation. Control of Spodoptera littoralis by a test sample is when at least one of mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample. The following compounds resulted in at least 80% control at an application rate of 200 ppm: P1 , P2, P4, P6, P7 and P8.
  • Example B8 Spodoptera littoralis (Egyptian cotton leaf worm)
  • Test compounds were applied by pipette from 10 ⁇ 00 ppm DMSO stock solutions into 24-well plates and mixed with agar. Lettuce seeds were placed on the agar and the multi well plate was closed by another plate which contains also agar. After 7 days the compound was absorbed by the roots and the lettuce grew into the lid plate. The lettuce leaves were now cut off into the lid plate. Spodoptera eggs were pipetted through a plastic stencil on a humid gel blotting paper and the plate closed with it. The samples were assessed for mortality, anti-feedant effect and growth inhibition in comparison to untreated samples 6 days after infestation. 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, P4, P6 and P8.
  • Example B9 Frankliniella occidentalis (Western flower thrips)
  • Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with agueous test solutions prepared from 10 ⁇ 00 DMSO stock solutions. After drying the leaf discs were infested with a Frankliniella population of mixed ages. The samples were assessed for mortality 7 days after infestation. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P6 and P7.
  • Example B10 Activity against Aedes aegypti (Yellow fever mosguito)
  • Test solutions at an application rate of 200ppm in ethanol, were applied to 12-well tissue culture plates. Once the deposits were dry, five, two to five days old adult female Aedes aegypti were added to each well, and sustained with a 10% sucrose solution in a cotton wool plug. Assessment of knockdown was made one hour after introduction, and mortality was assessed at 24 and 48 hours after introduction. The following compounds gave at least 80% control of Aedes aegypti after 48h: P1 , P2, P3, P5, P6, P7 and P8002E
  • Example B1 1 Activity against Anopheles stephensi (Indian malaria mosquito)
  • Test solutions at an application rate of 200 ppm in ethanol, were applied to 12 well tissue culture plates. Once the deposits were dry, five, two to five day old adult female Anopheles stephensi were added to each well, and sustained with a 10% sucrose solution in a cotton wool plug. Assessment of knockdown was made one hour after introduction, and mortality was assessed at 24 and 48 hours after introduction. The following compounds gave at least 80% control of Anopheles stephensi after 48h and/or 24h: P2, P6, P7, and P8.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne des composés de formule (I) dans laquelle les substituants sont tels que définis dans la revendication 1 ainsi que les sels, stéréoisomères, énantiomères, tautomères et N-oxydes agrochimiquement acceptables de ces composés, qui peuvent être utilisés en tant qu'insecticides et peuvent être préparés de manière connue.
PCT/EP2017/078988 2016-11-17 2017-11-13 Dérivés hétérocycliques à activité pesticide comportant des substituants contenant du soufre Ceased WO2018091389A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3730493A4 (fr) * 2017-12-22 2021-08-04 Sumitomo Chemical Company Limited Composé hétérocyclique et agent de lutte contre les arthropodes nuisibles contenant celui-ci
WO2024189139A1 (fr) 2023-03-14 2024-09-19 Syngenta Crop Protection Ag Lutte contre des nuisibles résistants aux insecticides

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EP1724392A2 (fr) 2005-05-04 2006-11-22 Fritz Blanke Gmbh & Co. Kg Procédé d'apprêtage anti-microbien de surfaces textiles
WO2006128870A2 (fr) 2005-06-03 2006-12-07 Basf Aktiengesellschaft Composition pour impregnation de fibres, tissus et filets a action protectrice contre les ravageurs
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WO2007048556A1 (fr) 2005-10-25 2007-05-03 Syngenta Participations Ag Dérivés d'amides hétérocycliques utiles en tant que microbiocides
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WO2009131237A1 (fr) 2008-04-21 2009-10-29 住友化学株式会社 Composition de lutte contre les arthropodes nuisibles, et composé hétérocyclique fusionné
WO2010060231A1 (fr) 2008-11-25 2010-06-03 Qin Zhaohai Aminonitroguanidines condensées, leur synthèse et leur emploi en tant qu'insecticides botaniques
WO2010125985A1 (fr) 2009-04-28 2010-11-04 Sumitomo Chemical Company, Limited Composé hétérocyclique à cycles fusionnés et son utilisation
WO2011040629A1 (fr) 2009-09-30 2011-04-07 Sumitomo Chemical Company, Limited Composition et procédé permettant de lutter contre les arthropodes nuisibles
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3730493A4 (fr) * 2017-12-22 2021-08-04 Sumitomo Chemical Company Limited Composé hétérocyclique et agent de lutte contre les arthropodes nuisibles contenant celui-ci
US11555035B2 (en) 2017-12-22 2023-01-17 Sumitomo Chemical Company, Limited Heterocyclic compound and harmful arthropod-controlling agent containing same
WO2024189139A1 (fr) 2023-03-14 2024-09-19 Syngenta Crop Protection Ag Lutte contre des nuisibles résistants aux insecticides

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