Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
  • A01N43/647—Triazoles; Hydrogenated triazoles
  • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
  • A01P7/00—Arthropodicides
  • A01P7/04—Insecticides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
  • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
  • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
  • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings

Definitions

• the present invention relates to pesticidally active, in particular insecticidally active azole amide compounds, to processes for their preparation, 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.
• the present invention accordingly relates, in a first aspect, to a compound of the formula I
• Ai is N or C-R2 C ;
• R ⁇ a is C3-C6cycloalkyl, C3-C6cycloalkyl substituted with one to three substituents independently selected from Ci-C3alkyl, Ci-C3haloalkyl, cyano, and halogen, C3-C6cycloalkylCi-C 4 alkyl, C3- C6cycloalkylCi-C 4 alkyl substituted with one to five substituents independently selected from Ci- C3alkyl, Ci-C3haloalkyl, cyano, and halogen, Ci-Cscyanoalkyl, C3-C6cycloalkoxy, Ci-C 4 alkylsulfonyl, Ci-C 4 haloalkylsulfonyl, Ci-C 4 alkylsulfinyl, or Ci-C 4 haloalkylsulfinyl;
• R ⁇ b is H, halogen, Ci-C3alkyl, Ci-C3haloalkyl, Ci-C3haloalkylthio, Ci-C3alkoxy, Ci-C3haloalkoxy, SFs, or CN;
• Ri is H, Ci-C6alkyl, Ci-C6cyanoalkyl, aminocarbonylCi-Cealkyl, hydroxycarbonylCi-Cealkyl, Ci- Cenitroalkyl, trimethylsilaneCi-C6alkyl, Ci-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C 4 cycloalkylCi-C 2 alkyl-, C3-C 4 cycloalkylCi-C 2 alkyl- wherein the C3-C 4 cycloalkyl group is substituted with 1 or 2 halo atoms, oxetan-3-yl-CH 2 -, benzyl or benzyl substituted with halo or Ci-C6haloalkyl;
• R3 is Ci-C3alkyl or Ci-C3haloalkyl
• Ci-C n cyanoalkyl refers to a straight chain or branched saturated Ci-C n alkyl radical having 1 to n carbon atoms (as mentioned above), where one of the hydrogen atoms in these radicals is be replaced by a cyano group: for example, cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, 3- cyanopropyl, 1 -(cyanomethyl)-2-ethyl, 1 -(methyl)-2-cyanoethyl, 4-cyanobutyl, and the like.
• C3-C n cycloalkyl refers to 3-n membered cycloalkyl groups such as cyclopropane, cyclobutane, cyclopentane and cyclohexane.
• C3-C n cycloalkylCi-C n alkyl“ as used herein refers to 3 or n membered cycloalkyl group with an alkyl radical, which alkyl radical is connected to the rest of the molecule.
• the C3- CncycloalkylCi-C2alkyl- group is substituted, the substituent(s) can be on the cycloalkyl group or alkyl radical.
• aminocarbonylCi-C n alkyl“ as used herein refers to an alkyl radical where one of the hydrogen atoms in the radical is replaced by a NH2C(0) group.
• Ci-C n alkylsulfanyl“ or“Ci-C n haloalkylthio“ as used herein refers to a Ci-C n alkyl moiety linked through a sulfur atom.
• the term“Ci-C n haloalkylsulfanyl“ as used herein refers to a Ci- Cnhaloalkyl moiety linked through a sulfur atom.
• the staggered line as used herein, for example, in J-1 , K-1 and L-1 , represent the point of connection/ attachment to the rest of the compound.
• the term "effective amount” refers to the amount of the compound, or a salt thereof, which, upon single or multiple applications provides the desired effect.
• an effective amount is readily determined by the skilled person in the art, by the use of known techniques and by observing results obtained under analogous circumstances. In determining the effective amount a number of factors are considered including, but not limited to: the type of plant or derived product to be applied; the pest to be controlled & its lifecycle; the particular compound applied; the type of application; and other relevant circumstances.
• Ri , R2a, R ⁇ b, R3, R4a, Rs, and Ai and A2 are as defined in the first aspect.
• the present invention contemplates both racemates and individual enantiomers. Compounds having preferred stereochemistry are set out below.
• Particularly preferred compounds of the present invention are compounds of formula I’a:
• “optionally substituted” as used herein means that the group referenced is either unsubstituted or is substituted by a designated substituent, for example,“C3-C4cycloalkyl is optionally substituted with 1 or 2 halo atoms” means C3-C4cycloalkyl, C3-C4cycloalkyl substituted with 1 halo atom and C3-C4cycloalkyl substituted with 2 halo atoms.
• Embodiments according to the invention are provided as set out below.
• R ⁇ a is
• C3-C 4 cycloalkyl C3-C 4 cycloalkyl substituted with one to three substituents independently selected from Ci-C2alkyl, Ci-C2haloalkyl, cyano, and halogen, C3-C 4 cycloalkylCi-C 2 alkyl substituted with one to five substituents independently selected from halogen, Ci- C3cyanoalkyl, C3-C 4 cycloalkoxy, Ci-C3haloalkylsulfonyl or Ci-C3haloalkylsulfinyl; or
• Ci-C3haloalkyl C.
• R3 being embodiment B (i.e. methyl);
• R 4 a being embodiment B (i.e. cyano, trifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, or 2,2- difluoroethoxy);
• Rs being embodiment A (i.e selected from J-1 to J-1 1).
• the compound of formula I has as Ri hydrogen, methyl, or cyclopropylmethyl; as R 2 one of K-1 , K-2, K-3, K-5, K-6, K-10, K-11 , K-12, and K-14: as R3 methyl; as R 4 one of L-1 to L-9; and as Rs one of J-1 to J-1 1 .
• the compound of formula I has as Ri hydrogen, methyl, or cyclopropylmethyl; as R 2 one K-1 , K-2, K-5, K-10, K-11 , and K-14: as R3 methyl; as R 4 one of L-1 to L-9; and as Rs one of J-1 to J-1 1 .
• the compound of formula I has as Ri hydrogen, methyl, or cyclopropylmethyl; as R 2 one K-5, K-10, and K-14: as R3 methyl; as R 4 one of L-1 or L-9; and as Rs one J-2 or J-8.
• the present invention in a further aspect provides a method of controlling parasites in or on an animal in need thereof comprising administering an effective amount of a compound of the first aspect.
• the present invention further provides a method of controlling ectoparasites on an animal in need thereof comprising administering an effective amount of a compound of formula I as defined om the first aspect.
• the present invention further provides a method for preventing and/or treating diseases transmitted by ectoparasites comprising administering an effective amount of a compound of formula I as defined in the first aspect, to an animal in need thereof.
• Compounds of formula I can be prepared by those skilled in the art following known methods. More specifically compounds of formulae I, and I’a, and intermediates therefor can be prepared as described below in the schemes and examples. Certain stereogenic centers have been left unspecified for the clarity and are not intended to limit the teaching of the schemes in any way.
• compounds of formula lb wherein Ri , R 2a , R ⁇ b , R3, R4a, Ai , and A 2 is defined as above and R5a is diphenylmethanimine, C3-C 4 halocycloalkyl, C2-C6alkenyl, C2-C6haloalkenyl may be prepared by reaction of compounds of formula la wherein Ri , R 2a , R 2b , R3, R4a, Ai .and A 2 is defined as above and X06 is an halogen such as chlorine, bromine or iodine with compounds of formula XIX wherein Rsa is described above and W is a boronic acid or a boronate ester or hydrogen as depicted in Scheme 6.
• Hydrazines of formula Xa or Xb wherein A2 is defined as above and Y is Ci-C3haloalkyl are either commercially available or can be prepared according to well-known methods, see e.g. J. Fluorine Chem. 2017, 203, 155, US2013/0225552, page 128, Org. Process Res. Dev. 2011, 15, 721, ACS Med. Chem. Lett. 2017, 8, 666 and Tet. Lett. 2016, 57, 1056 ; Scheme 9 outlines general synthetic methods leading to compounds of formula Xa and Xb. Such hydrazines are useful intermediates for the preparation of final compounds.
• Hydrazines of formula Xc wherein A2 is defined as above can be prepared in a quite similar way as already described in Scheme 9.
• compounds of formula XXVI wherein A2 is defined as above and Xo5 stands for a halogen or methyl sulfone are reacted with hydrazine in a suitable solvent, preferable in ethanol or isopropanol, at temperature between 20 °C to refluxing conditions to give compounds of formula Xc (see e.g. Tet. Lett. 2016, 57, 1056).
• Carboxylic acids of formula XXXI wherein F3 ⁇ 4 J and Ai is defined as above are useful intermediates for the preparation of final compounds (see Scheme 1) and may be prepared by the process shown in Scheme 1 1 .
• compounds of formula XXIX wherein R ⁇ b and Ai is defined as above, may be prepared by reaction of compounds of formula XXVII with a suitable trifluoromethylthiolation copper reagent of formula XXVIII, ligands being e.g. 1 ,10-phenanthroline or 4,4’-di-fe/?-butylbipyridine, in suitable solvents, for example, acetonitrile or DMF, usually upon heating at temperatures between 20 to 150°C, preferably between 40°C to the boiling point of the reaction mixture.
• suitable solvents for example, acetonitrile or DMF
• R 2a is not C 1 -C 4 alkylsulfonyl, C 4 -C 4 -haloalkylsulfonyl, C 1 -C 4 -alkylsulfinyl, C 1 -C 4 -haloalkylsulfinyl
• Carboxylic acids of formula XXXVIII may be prepared from compound of formula XXXVII analog as outlined in Scheme 1 1 ., by treatment with, for example aqueous LiOH, NaOH or KOH, in suitable solvents that may include, for example, THF/MeOH mixture, usually upon heating at temperatures between room temperature and 100°C, preferably between 20°C to the boiling point of the reaction mixture (see Scheme 13).
• suitable solvents may include, for example, THF/MeOH mixture
• R 2 aa H, C 1 -C 3 alkyl l C 1 -C 3 haloalkyl, cyano, halogen
• R 2 aa H, C 1 -C 3 alkyl l C 1 -C 3 haloalkyl l cyano, halogen
• Carboxylic acids of formula XLIV wherein R ⁇ b and Ai is defined as above and R2aa is H, Ci-C3alkyl, Ci- C3haloalkyl, cyano and halogen can be prepared according to reaction Scheme 15.
• compounds of formula XXVII wherein R ⁇ b and Ai is defined as above and Xo6 is chlorine, bromine or iodine are treated with iPrMgCI/LiCI-complex; subsequent reaction with CuCN and quenching with cyclopropane carbonyl chlorides of formula XLI wherein R2a is defined above provides compounds of formula XLII (analog to W02006/067445, page 148).
• compounds of formula le wherein Ri , R3 , R ⁇ a , R ⁇ b , Rs, Ai and A2 are as previously defined and Y is Ci-C3haloalkyl, can be prepared from compounds of formula XLIX, by treating with alkylating reagents of general formula L wherein Xos is preferably a leaving group such as Cl, Br, F, I, OSO2CF3, or OSO2CH3 and Y is Ci-C3haloalkyl, in the presence of a base, such as sodium hydride, K2CO3, or CS2CO3, in an inert solvent such as THF, DMF, or acetonitrile, to give compounds of formula le.
• a base such as sodium hydride, K2CO3, or CS2CO3
• an inert solvent such as THF, DMF, or acetonitrile
• Compounds of formula XLVII can also be converted to compounds of formula XLIX by reaction with (E)-benzaldehyde oxime in an aprotic solvent such as acetonitrile or DMF, in the presence of a base, such as potassium or cesium carbonate, optionally in the presence of a palladium catalyst such as RockPhos-G3-palladacycle ([(2-Di-fe/?-butylphosphino-3-methoxy-6-methyl-2',4',6'-triisopropyl-1 ,T- biphenyl)-2-(2-aminobiphenyl)]palladium(ll) methanesulfonate) at temperatures between 25-100°C.
• a palladium catalyst such as RockPhos-G3-palladacycle ([(2-Di-fe/?-butylphosphino-3-methoxy-6-methyl-2',4',6'-triisopropyl-1
• X07 is a leaving group, for example a halogen or a sulfonate, preferably chlorine, bromine, iodine ortrifluoromethanesulfonate, with reagents of the formula LVI, wherein Z2 is Ci-C 4 alkyl, in the presence of a base, such as sodium carbonate, potassium carbonate or cesium carbonate, or sodium hydride, sodium methoxide or ethoxide, potassium tert-butoxide, optionally under palladium (for example involving Pd(PP i3) 2 Cl 2 ) or copper (for example involving Cul) catalysis, in a appropriate solvent such as for example toluene, dioxane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyr
• solvent definition R 5c see text e.g. dioxane, toluene
• Ri , R2a, R ⁇ b, R3, R4a, Ai, and A2 are defined as above and Rsc is diphenylmethanimine, Ci-C 4 haloalkylsulfanyl, C3-C 4 halocycloalkyl, C2-C6haloalkenyl, may be prepared by reaction of compounds of formula la wherein Ri , R2a, R2b, R3, R4a, Ai, A2 and X06 are previously described and compounds of formula LIX wherein Rsc is described above (see also Scheme 6).
• This reaction is carried out in the presence of a palladium catalyst, for example, Pd(PPh3) 4 , in a suitable solvent, such as dioxane or toluene, in the presence of a suitable base, such as potassium or caesium carbonate usually upon heating at temperatures between room temperature and 200°C, preferably between 20°C to the boiling point of the reaction mixture, optionally under microwave heating conditions.
• a palladium catalyst for example, Pd(PPh3) 4
• a suitable solvent such as dioxane or toluene
• a suitable base such as potassium or caesium carbonate
• Rsc is Ci-C 4 haloalkylsulfanyl
• compounds of formula If can be oxidized by oxidizing agents such as m-CPBA usually upon heating at temperatures between room temperature to the boiling point of the reaction mixture, to give compounds Ig wherein Ri , R2a, R2b, R3, R 4a , Ai , and A2 are defined as above and R5d is Ci-C 4 haloalkylsulfinyl, Ci-C 4 haloalkylsulfonyl.
• oxidizing agents such as m-CPBA usually upon heating at temperatures between room temperature to the boiling point of the reaction mixture, to give compounds Ig wherein Ri , R2a, R2b, R3, R 4a , Ai , and A2 are defined as above and R5d is Ci-C 4 haloalkylsulfinyl, Ci-C 4 haloalkylsulfonyl.
• compounds of formula LX wherein Ri , R3, R4a, and A2 are defined as above may be prepared by reaction between compounds of formula LXIV, wherein R3, R 4 a, and A2 are defined as above and Xo is halogen with compounds of formula V, wherein Ri is defined in formula I, in suitable solvents that may include, for example, acetonitrile or dioxane, in the presence of a suitable base, such as sodium, potassium or cesium carbonate (or sodium or potassium hydrogene carbonate), usually upon heating at temperatures between room temperature and 200°C, preferably between 40°C to the boiling point of the reaction mixture, optionally under microwave heating conditions.
• suitable solvents may include, for example, acetonitrile or dioxane, in the presence of a suitable base, such as sodium, potassium or cesium carbonate (or sodium or potassium hydrogene carbonate), usually upon heating at temperatures between room temperature and 200°C, preferably between 40°C to the boiling point of the reaction mixture, optionally under microwave heating conditions.
• Compounds of formula LX III, wherein R3, R 4a , and A2 are defined as above, may be prepared in two steps by reaction between compounds of formula LXII wherein, R3 is defined as above and Xo is a halogen such as for example bromine, chlorine or iodine, and potassium thiocyanate and methanol in a suitable solvent such as acetone usually upon heating at temperatures between room temperature and 200°C, preferably between 20°C to the boiling point of the reaction mixture.
• Xo is a halogen such as for example bromine, chlorine or iodine
• a suitable solvent such as acetone
• substitution base e.g. KOH
• Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N- dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N- methylmorpholine, benzyltrimethylammonium hydroxide and 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
• 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 N,N-diethylaniline, may also act as solvents or diluents.
• the reactions are 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.
• 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 saltforming 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
• 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.
• Table A-1 provides 14 compounds A-1 .001 to A-1 .014 of formula lo wherein Ri is H, Rs is Cl, R4 is (5- cyano-2-pyridyl) and R2 is as defined in table Z.
• Ri is H
• Rs is Cl
• R4 is (5- cyano-2-pyridyl)
• R2 is as defined in table Z.
• A-1 .002 is
• Table A-2 provides 14 compounds A-2.001 to A-2.014 of formula lo wherein Ri is H, R 5 is Cl, R4 is [5- (trifluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-3 provides 14 compounds A-3.001 to A-3.014 of formula lo wherein Ri is H, R 5 is Cl, R4 is [5- (trifluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A- 5 provides 14 compounds A-5.001 to A-5.014 of formula lo wherein Ri is H, R 5 is Cl, R4 is [5-(2,2- difluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-6 provides 14 compounds A-6.001 to A-6.014 of formula lo wherein Ri is H, R 5 is Cl, R 4 is [5-(2,2,2- trifluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-7 provides 14 compounds A-7.001 to A-7.014 of formula lo wherein Ri is H, R 5 is Cl, R 4 is [5-(2,2,2- trifluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-8 provides 14 compounds A-8.001 to A-8.014 of formula lo wherein Ri is H, R 5 is Cl, R 4 is [5- (difluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-11 provides 14 compounds A-1 1.001 to A-1 1 .014 of formula lo wherein Ri is H, R 5 is Br, R is [5- (trifluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-12 provides 14 compounds A-12.001 to A-12.014 of formula lo wherein Ri is H, R 5 is Br, R is [5- (trifluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-13 provides 14 compounds A-13.001 to A-13.014 of formula lo wherein Ri is H, R 5 is Br, R is [5-(2,2- difluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-16 provides 14 compounds A-16.001 to A-16.014 of formula lo wherein Ri is H, R 5 is Br, R is [5-(2,2,2- trifluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-17 provides 14 compounds A-17.001 to A-17.014 of formula lo wherein Ri is H, R 5 is Br, R is [5- (difluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-19 provides 14 compounds A-19.001 to A-19.014 of formula lo wherein Ri is H, R 5 is I, R is (5-cyano-2- pyridyl) and R 2 is as defined in table Z.
• Table A-22 provides 14 compounds A-22.001 to A-22.014 of formula lo wherein Ri is H, R 5 is I, R is [5-(2,2- difluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-24 provides 14 compounds A-24.001 to A-24.014 of formula lo wherein Ri is H, R 5 is I, R is [5-(2,2,2- trifluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-25 provides 14 compounds A-25.001 to A-25.014 of formula lo wherein Ri is H, R 5 is I, R is [5-(2,2,2- trifluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-26 provides 14 compounds A-26.001 to A-26.014 of formula lo wherein Ri is H, R 5 is I, R is [5- (difluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-27 provides 14 compounds A-27.001 to A-27.014 of formula lo wherein Ri is H, R 5 is I, R is [5-
• Table A-28 provides 14 compounds A-28.001 to A-28.014 of formula lo wherein Ri is H, R 5 is NH 2 , R is (5- cyano-2-pyridyl) and R 2 is as defined in table Z.
• Table A-30 provides 14 compounds A-30.001 to A-30.014 of formula lo wherein Ri is H, R 5 is NH 2 , R 4 is [5- (trifluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-31 provides 14 compounds A-31 .001 to A-31 .014 of formula lo wherein Ri is H, R 5 is NH 2 , R is [5-(2,2- difluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-32 provides 14 compounds A-32.001 to A-32.014 of formula lo wherein Ri is H, R 5 is NH 2 , R is [5-(2,2- difluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-33 provides 14 compounds A-33.001 to A-33.014 of formula lo wherein Ri is H, R 5 is NH 2 , R is [5-(2,2,2- trifluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-34 provides 14 compounds A-34.001 to A-34.014 of formula lo wherein Ri is H, R 5 is NH 2 , R is [5-(2,2,2- trifluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-35 provides 14 compounds A-35.001 to A-35.014 of formula lo wherein Ri is H, R 5 is NH 2 , R is [5- (difluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-36 provides 14 compounds A-36.001 to A-36.014 of formula lo wherein Ri is H, R 5 is NH 2 , R is [5- (difluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-37 provides 14 compounds A-37.001 to A-37.014 of formula lo wherein Ri is H, R 5 is NHCH 3 , R 4 is (5- cyano-2-pyridyl) and R 2 is as defined in table Z.
• Table A-38 provides 14 compounds A-38.001 to A-38.014 of formula lo wherein Ri is H, R 5 is NHCH 3 , R 4 is [5- (trifluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-39 provides 14 compounds A-39.001 to A-39.014 of formula lo wherein Ri is H, R 5 is NHCH 3 , R is [5- (trifluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-40 provides 14 compounds A-40.001 to A-40.014 of formula lo wherein Ri is H, R 5 is NHCH 3 , R is [5- (2,2-difluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-41 provides 14 compounds A-41 .001 to A-41 .014 of formula lo wherein Ri is H, R 5 is NHCH 3 , R is [5- (2,2-difluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-42 provides 14 compounds A-42.001 to A-42.014 of formula lo wherein Ri is H, R 5 is NHCH 3 , R is [5- (2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-43 provides 14 compounds A-43.001 to A-43.014 of formula lo wherein Ri is H, R 5 is NHCH 3 , R is [5- (2,2,2-trifluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-44 provides 14 compounds A-44.001 to A-44.014 of formula lo wherein Ri is H, R 5 is NHCH 3 , R is [5- (difluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-45 provides 14 compounds A-45.001 to A-45.014 of formula lo wherein Ri is H, R 5 is NHCH 3 , R is [5- (difluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-47 provides 14 compounds A-47.001 to A-47.014 of formula lo wherein Ri is H, R 5 is N(CH 3 )2, R is [5- (trifluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-48 provides 14 compounds A-48.001 to A-48.014 of formula lo wherein Ri is H, R 5 is N(CH 3 )2, R is [5- (trifluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-49 provides 14 compounds A-49.001 to A-49.014 of formula lo wherein Ri is H, R 5 is N(CH 3 )2, R is [5-
• Table A-50 provides 14 compounds A-50.001 to A-50.014 of formula lo wherein Ri is H Rs is N(CH 3 )2, R 4 is [5- (2,2-difluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-51 provides 14 compounds A-51 .001 to A-51 .014 of formula lo wherein Ri is H Rs is N(CH 3 )2, R 4 is [5- (2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A- 52 provides 14 compounds A-52.001 to A-52.014 of formula lo wherein Ri is H Rs is N(CH 3 )2, R 4 is [5- (2,2,2-trifluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A- 54 provides 14 compounds A-54.001 to A-54.014 of formula lo wherein Ri is H Rs is N(CH 3 )2, R 4 is [5- (difluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-55 provides 14 compounds A-55.001 to A-55.014 of formula lo wherein Ri is H Rs is NHCOCHs, R 4 is (5- cyano-2-pyridyl) and R 2 is as defined in table Z.
• Table A- 56 provides 14 compounds A-56.001 to A-56.014 of formula lo wherein Ri is H Rs is NHCOCHs, R 4 is [5- (trifluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-58 provides 14 compounds A-58.001 to A-58.014 of formula lo wherein Ri is H Rs is NHCOCHs, R 4 is [5- (2,2-difluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-60 provides 14 compounds A-60.001 to A-60.014 of formula lo wherein Ri is H Rs is NHCOCHs, R 4 is [5- (2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-61 provides 14 compounds A-61 .001 to A-61 .014 of formula lo wherein Ri is H Rs is NHCOCHs, R 4 is [5- (2,2,2-trifluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-64 provides 14 compounds A-64.001 to A-64.014 of formula lo wherein Ri is H Rs is OCF 3 , R 4 is (5- cyano-2-pyridyl) and R 2 is as defined in table Z.
• Table A-65 provides 14 compounds A-65.001 to A-65.014 of formula lo wherein Ri is H Rs is OCF 3 , R 4 is [5- (trifluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-66 provides 14 compounds A-66.001 to A-66.014 of formula lo wherein Ri is H Rs is OCF 3 , R 4 is [5- (trifluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-67 provides 14 compounds A-67.001 to A-67.014 of formula lo wherein Ri is H Rs is OCF 3 , R 4 is [5-(2,2- difluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-68 provides 14 compounds A-68.001 to A-68.014 of formula lo wherein Ri is H Rs is OCF 3 , R 4 is [5-(2,2- difluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-69 provides 14 compounds A-69.001 to A-69.014 of formula lo wherein Ri is H Rs is OCF 3 , R 4 is [5- (2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-70 provides 14 compounds A-70.001 to A-70.014 of formula lo wherein Ri is H Rs is OCF 3 , R 4 is [5- (2,2,2-trifluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-71 provides 14 compounds A-71 .001 to A-71 .014 of formula lo wherein Ri is H Rs is OCF 3 , R 4 is [5-
• R 2 is as defined in table Z.
• Table A-72 provides 14 compounds A-72.001 to A-72.014 of formula lo wherein Ri is H Rs is OCF 3 , R 4 is [5- (difluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-73 provides 14 compounds A-73.001 to A-73.014 of formula lo wherein Ri is H Rs is OCHF 2 , R 4 is (5- cyano-2-pyridyl) and R 2 is as defined in table Z.
• Table A-74 provides 14 compounds A-74.001 to A-74.014 of formula lo wherein Ri is H Rs is OCHF 2 , R 4 is [5- (trifluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-75 provides 14 compounds A-75.001 to A-75.014 of formula lo wherein Ri is H Rs is OCHF 2 , R 4 is [5- (trifluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-76 provides 14 compounds A-76.001 to A-76.014 of formula lo wherein Ri is H Rs is OCHF 2 , R 4 is [5- (2,2-difluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-77 provides 14 compounds A-77.001 to A-77.014 of formula lo wherein Ri is H Rs is OCHF 2 , R 4 is [5- (2,2-difluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-78 provides 14 compounds A-78.001 to A-78.014 of formula lo wherein Ri is H Rs is OCHF 2 , R 4 is [5- (2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-83 provides 14 compounds A-83.001 to A-83.014 of formula lo wherein Ri is H Rs is OCH 2 CF 3 , R 4 is [5- (trifluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-95 provides 14 compounds A-95.001 to A-95.014 of formula lo wherein Ri is H, R 5 is OCH CHF , R is [5-(2,2-difluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-108 provides 14 compounds A-108.001 to A-108.014 of formula lo wherein Ri is CH 3 , R is Cl, R is [5- (difluoromethoxy)-2-pyridyl] and R is as defined in table Z.
• Table A-117 provides 14 compounds A-1 17.001 to A-1 17.014 of formula lo wherein Ri is CH 3 , Rs is Br, R 4 is [5- (difluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-124 provides 14 compounds A-124.001 to A-124.014 of formula lo wherein Ri is CH 3 , R 5 is I, R is [5- (2,2,2-trifluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-125 provides 14 compounds A-125.001 to A-125.014 of formula lo wherein Ri is CH 3 , R 5 is I, R is [5- (difluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-127 provides 14 compounds A-127.001 to A-127.014 of formula lo wherein Ri is CH 3 , R 5 is NH 2 , R is (5- cyano-2-pyridyl) and R 2 is as defined in table Z.
• Table A-130 provides 14 compounds A-130.001 to A-130.014 of formula lo wherein Ri is CH 3 , R 5 is NH 2 , R is [5- (2,2-difluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-133 provides 14 compounds A-133.001 to A-133.014 of formula lo wherein Ri is CH 3 , R 5 is NH 2 , R is [5- (2,2,2-trifluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-136 provides 14 compounds A-136.001 to A-136.014 of formula lo wherein Ri is CH 3 , R 5 is NHCH 3 , R is (5-cyano-2-pyridyl) and R 2 is as defined in table Z.
• Table A-139 provides 14 compounds A-139.001 to A-139.014 of formula lo wherein Ri is CH 3 , R 5 is NHCH 3 , R is [5-(2,2-difluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-140 provides 14 compounds A-140.001 to A-140.014 of formula lo wherein Ri is CH 3 , R 5 is NHCH 3 , R 4 is [5-(2,2-difluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-141 provides 14 compounds A-141 .001 to A-141.014 of formula lo wherein Ri is CH 3 , R 5 is NHCH 3 , R is [5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-143 provides 14 compounds A-143.001 to A-143.014 of formula lo wherein Ri is CH 3 , R 5 is NHCH 3 , R is [5-(difluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-145 provides 14 compounds A-145.001 to A-145.014 of formula lo wherein Ri is CH 3 , R 5 is N(CH 3 )2, R is (5-cyano-2-pyridyl) and R 2 is as defined in table Z.
• Table A-146 provides 14 compounds A-146.001 to A-146.014 of formula lo wherein Ri is CH 3 , R 5 is N(CH 3 )2, R is [5-(trifluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-147 provides 14 compounds A-147.001 to A-147.014 of formula lo wherein Ri is CH 3 , R 5 is N(CH 3 )2, R is [5-(trifluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-149 provides 14 compounds A-149.001 to A-149.014 of formula lo wherein Ri is CH 3 , R 5 is N(CH 3 )2, R is [5-(2,2-difluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-150 provides 14 compounds A-150.001 to A-150.014 of formula lo wherein Ri is CH 3 , R 5 is N(CH 3 )2, R is [5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-151 provides 14 compounds A-151 .001 to A-151.014 of formula lo wherein Ri is CH 3 , R 5 is N(CH 3 )2, R is [5-(2,2,2-trifluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-152 provides 14 compounds A-152.001 to A-152.014 of formula lo wherein Ri is CH 3 , R 5 is N(CH 3 )2, R is [5-(difluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-153 provides 14 compounds A-153.001 to A-153.014 of formula lo wherein Ri is CH 3 , R 5 is N(CH 3 )2, R is [5-(difluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-154 provides 14 compounds A-154.001 to A-154.014 of formula lo wherein Ri is CH 3 , R 5 is NHCOCH 3 , R is (5-cyano-2-pyridyl) and R 2 is as defined in table Z.
• Table A-155 provides 14 compounds A-155.001 to A-155.014 of formula lo wherein Ri is CH 3 , R 5 is NHCOCH 3 , R is [5-(trifluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-157 provides 14 compounds A-157.001 to A-157.014 of formula lo wherein Ri is CH 3 , R 5 is NHCOCH 3 , R is [5-(2,2-difluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-161 provides 14 compounds A-161 .001 to A-161.014 of formula lo wherein Ri is CH 3 , R is NHCOCH 3 ,
• R 4 is [5-(difluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-162 provides 14 compounds A-162.001 to A-162.014 of formula lo wherein Ri is CH 3 , R 5 is NHCOCH 3 ,
• R is [5-(difluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-163 provides 14 compounds A-163.001 to A-163.014 of formula lo wherein Ri is CH 3 , R 5 is OCF 3 , R is (5-cyano-2-pyridyl) and R 2 is as defined in table Z.
• Table A-164 provides 14 compounds A-164.001 to A-164.014 of formula lo wherein Ri is CH 3 , R 5 is OCF 3 , R is [5-(trifluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-165 provides 14 compounds A-165.001 to A-165.014 of formula lo wherein Ri is CH 3 , R 5 is OCF 3 , R is [5-(trifluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-166 provides 14 compounds A-166.001 to A-166.014 of formula lo wherein Ri is CH 3 , R 5 is OCF 3 , R is [5-(2,2-difluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-167 provides 14 compounds A-167.001 to A-167.014 of formula lo wherein Ri is CH 3 , R 5 is OCF 3 , R is [5-(2,2-difluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-168 provides 14 compounds A-168.001 to A-168.014 of formula lo wherein Ri is CH 3 , R 5 is OCF 3 , R is [5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-169 provides 14 compounds A-169.001 to A-169.014 of formula lo wherein Ri is CH 3 , R 5 is OCF 3 , R is [5-(2,2,2-trifluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-170 provides 14 compounds A-170.001 to A-170.014 of formula lo wherein Ri is CH 3 , R 5 is OCF 3 , R is [5-(difluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-171 provides 14 compounds A-171 .001 to A-171.014 of formula lo wherein Ri is CH 3 , R 5 is OCF 3 , R is [5-(difluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-172 provides 14 compounds A-172.001 to A-172.014 of formula lo wherein Ri is CH 3 , R 5 is OCFIF 2 , R is (5-cyano-2-pyridyl) and R 2 is as defined in table Z.
• Table A-173 provides 14 compounds A-173.001 to A-173.014 of formula lo wherein Ri is CH 3 , R 5 is OCFIF 2 , R is [5-(trifluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-174 provides 14 compounds A-174.001 to A-174.014 of formula lo wherein Ri is CH 3 , R 5 is OCFIF 2 , R is [5-(trifluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-175 provides 14 compounds A-175.001 to A-175.014 of formula lo wherein Ri is CH 3 , R 5 is OCFIF 2 , R is [5-(2,2-difluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-177 provides 14 compounds A-177.001 to A-177.014 of formula lo wherein Ri is CH 3 , R 5 is OCFIF 2 , R is [5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-178 provides 14 compounds A-178.001 to A-178.014 of formula lo wherein Ri is CH 3 , R 5 is OCFIF 2 , R is [5-(2,2,2-trifluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-179 provides 14 compounds A-179.001 to A-179.014 of formula lo wherein Ri is CH 3 , R 5 is OCFIF 2 , R is [5-(difluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-180 provides 14 compounds A-180.001 to A-180.014 of formula lo wherein Ri is CH 3 , R 5 is OCFIF 2 , R is [5-(difluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-181 provides 14 compounds A-181 .001 to A-181.014 of formula lo wherein Ri is CH 3 , R 5 is OCFI 2 CF 3 , R is (5-cyano-2-pyridyl) and R 2 is as defined in table Z.
• Table A-182 provides 14 compounds A-182.001 to A-182.014 of formula lo wherein Ri is CH 3 , Rs is OCH CF , R is [5-(trifluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-183 provides 14 compounds A-183.001 to A-183.014 of formula lo wherein Ri is CH 3 , R is OCH 2 CF 3 , R is [5-(trifluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-185 provides 14 compounds A-185.001 to A-185.014 of formula lo wherein Ri is CH 3 , R 5 is OCFI 2 CF 3 , R is [5-(2,2-difluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-186 provides 14 compounds A-186.001 to A-186.014 of formula lo wherein Ri is CH 3 , R 5 is OCFI 2 CF 3 , R is [5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-187 provides 14 compounds A-187.001 to A-187.014 of formula lo wherein Ri is CH 3 , R 5 is OCFI 2 CF 3 , R is [5-(2,2,2-trifluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-188 provides 14 compounds A-188.001 to A-188.014 of formula lo wherein Ri is CH 3 , R 5 is OCFI 2 CF 3 , R is [5-(difluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-189 provides 14 compounds A-189.001 to A-189.014 of formula lo wherein Ri is CH 3 , R 5 is OCFI 2 CF 3 , R is [5-(difluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-190 provides 14 compounds A-190.001 to A-190.014 of formula lo wherein Ri is CH 3 , R 5 is OCFI 2 CFIF 2 , R is (5-cyano-2-pyridyl) and R 2 is as defined in table Z.
• Table A-192 provides 14 compounds A-192.001 to A-192.014 of formula lo wherein Ri is CH 3 , R 5 is OCFI 2 CFIF 2 , R is [5-(trifluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-193 provides 14 compounds A-193.001 to A-193.014 of formula lo wherein Ri is CH 3 , R 5 is OCFI 2 CFIF 2 , R is [5-(2,2-difluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-195 provides 14 compounds A-195.001 to A-195.014 of formula lo wherein Ri is CH 3 , R 5 is OCFI 2 CFIF 2 , R is [5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-197 provides 14 compounds A-197.001 to A-197.014 of formula lo wherein Ri is CH 3 , R 5 is OCFI 2 CFIF 2 , R is [5-(difluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-198 provides 14 compounds A-198.001 to A-198.014 of formula lo wherein Ri is CH 3 , R 5 is OCFI 2 CFIF 2 , R is [5-(difluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-199 provides 14 compounds A-199.001 to A-199.014 of formula lo wherein Ri is CFI 2 Cyp, R 5 is Cl, R 4 is (5-cyano-2-pyridyl) and R 2 is as defined in table Z.
• Table A-200 provides 14 compounds A-200.001 to A-200.014 of formula lo wherein Ri is CFI 2 Cyp, R 5 is Cl, R 4 is [5-(trifluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-201 provides 14 compounds A-201 .001 to A-201.014 of formula lo wherein Ri is CFI 2 Cyp, R 5 is Cl, R 4 is [5-(trifluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-202 provides 14 compounds A-202.001 to A-202.014 of formula lo wherein Ri is CFI 2 Cyp, R 5 is Cl, R 4 is [5-(2,2-difluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-203 provides 14 compounds A-203.001 to A-203.014 of formula lo wherein Ri is CFI 2 Cyp, R 5 is Cl, R 4 is [5-(2,2-difluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-204 provides 14 compounds A-204.001 to A-204.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is Cl, R4 is [5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-206 provides 14 compounds A-206.001 to A-206.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is Cl, R4 is [5-(difluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-207 provides 14 compounds A-207.001 to A-207.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is Cl, R4 is [5-(difluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-208 provides 14 compounds A-208.001 to A-208.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is Br, R is (5-cyano-2-pyridyl) and R 2 is as defined in table Z.
• Table A-209 provides 14 compounds A-209.001 to A-209.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is Br, R is [5-(trifluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-210 provides 14 compounds A-210.001 to A-210.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is Br, R is [5-(trifluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-212 provides 14 compounds A-212.001 to A-212.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is Br, R is [5-(2,2-difluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-213 provides 14 compounds A-213.001 to A-213.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is Br, R is [5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-215 provides 14 compounds A-215.001 to A-215.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is Br, R is [5-(difluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-217 provides 14 compounds A-217.001 to A-217.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is I, R is (5-cyano-2-pyridyl) and R 2 is as defined in table Z.
• Table A-218 provides 14 compounds A-218.001 to A-218.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is I, R is [5- (trifluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-219 provides 14 compounds A-219.001 to A-219.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is I, R is [5- (trifluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-221 provides 14 compounds A-221 .001 to A-221.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is I, R is [5- (2,2-difluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-223 provides 14 compounds A-223.001 to A-223.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is I, R is [5- (2,2,2-trifluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-224 provides 14 compounds A-224.001 to A-224.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is I, R is [5- (difluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-225 provides 14 compounds A-225.001 to A-225.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is I, R is [5- (difluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-226 provides 14 compounds A-226.001 to A-226.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is NH 2 , R is (5-cyano-2-pyridyl) and R 2 is as defined in table Z.
• Table A-227 provides 14 compounds A-227.001 to A-227.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is NH 2 , R is [5-(trifluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-228 provides 14 compounds A-228.001 to A-228.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is NH 2 , R 4 is [5-(trifluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-229 provides 14 compounds A-229.001 to A-229.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is NH 2 , R is [5-(2,2-difluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-230 provides 14 compounds A-230.001 to A-230.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is NH 2 , R is [5-(2,2-difluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-231 provides 14 compounds A-231 .001 to A-231.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is NH 2 , R is [5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-232 provides 14 compounds A-232.001 to A-232.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is NH 2 , R is [5-(2,2,2-trifluoroethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-233 provides 14 compounds A-233.001 to A-233.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is NH 2 , R is [5-(difluoromethoxy)pyrimidin-2-yl] and R 2 is as defined in table Z.
• Table A-234 provides 14 compounds A-234.001 to A-234.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is NH 2 , R is [5-(difluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• Table A-235 provides 14 compounds A-235.001 to A-235.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is NHCH 3 , R is (5-cyano-2-pyridyl) and R 2 is as defined in table Z.
• Table A-237 provides 14 compounds A-237.001 to A-237.014 of formula lo wherein Ri is CH 2 Cyp, R 5 is NHCH 3 , R is [5-(trifluoromethoxy)-2-pyridyl] and R 2 is as defined in table Z.
• 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
• 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.
• Gomphrena globosa Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, I mpatiens 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.
• 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 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
• 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 d-endotoxins, e.g. CrylAb, CrylAc, Cry1 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
• 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.
• 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 Cry1 Ac toxin); Bollgard I® (cotton variety that expresses a
• transgenic crops are:
• 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-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
• NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 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 c 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 CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain
• 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.
• fungal for example Fusarium, Anthracnose, or Phytophthora
• bacterial for example Pseudomonas
• viral for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus
• 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.
• 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 provides a compound of the first aspect for use in therapy.
• the present invention provides a compound of the first aspect, for use in controlling parasites in or on an animal.
• the present invention further provides a compound of the first aspect, for use in controlling ectoparasites on an animal.
• the present invention further provides a compound of the first aspect, for use in preventing and/or treating diseases transmitted by ectoparasites.
• the present invention provides the use of a compound of the first aspect, for the manufacture of a medicament for controlling parasites in or on an animal.
• the present invention further provides the use of a compound of the first aspect, for the manufacture of a medicament for controlling ectoparasites on an animal.
• the present invention further provides the use of a compound of the first aspect, for the manufacture of a medicament for preventing and/or treating diseases transmitted by ectoparasites.
• the present invention provides the use of a compound of the first aspect, in controlling parasites in or on an animal.
• the present invention further provides the use of a compound of the first aspect , in controlling ectoparasites on an animal.
• controlling when used in context of parasites in or on an animal refers to reducing the number of pests or parasites, eliminating pests or parasites and/or preventing further pest or parasite infestation.
• preventing when used used in context of parasites in or on an animal refers to the avoidance of a symptom or disease developing in the animal.
• Ticks include, but are not limited to, members of the following genera: Rhipicaphalus, for example, Rhipicaphalus (, Boophilus ) microplus and Rhipicephalus sanguineus ; Amblyomma Dermacentor, Haemaphysalis ; Hyalomma ; Ixodes ; Rhipicentor, Margaropus ; Argas Otobius ; and Ornithodoros.
• Mites include, but are not limited to, members of the following genera: Chorioptes, for example Chorioptes bovis ; Psoroptes, for example Psoroptes ovis ; Cheyletiella ; Dermanyssus ; for example Dermanyssus gallinae ;
• Insects include, but are not limited to, members of the orders: Siphonaptera, Diptera, Phthiraptera, Lepidoptera, Coleoptera and Homoptera.
• Siphonaptera order include, but are not limited to, Ctenocephalides felis and Ctenocephatides canis.
• Members of the Diptera order include, but are not limited to, Musca spp .; bot fly, for example Gasterophilus intestinalis and Oestrus ovis ; biting flies; horse flies, for example Haematopota spp. and Tabunus spp.] haematobia, for example haematobia irritans] Stomoxys] Lucilia] midges; and mosquitoes.
• Musca spp . bot fly, for example Gasterophilus intestinalis and Oestrus ovis ; biting flies; horse flies, for example Haematopota spp. and Tabunus spp.] haematobia, for example haematobia irritans] Stomoxys] Lucilia] midges; and mosquitoes.
• Phthiraptera class include, but are not limited to, blood sucking lice and chewing lice, for example Bovicola Ovis and Bovicola Bovis.
• effective amount when used in context of parasites in or on an animal refers to the amount or dose of the compound of the invention, or a salt thereof, which, upon single or multiple dose administration to the animal, provides the desired effect in or on the animal.
• the effective amount can be readily determined by the attending diagnostician, as one skilled in the art, by the use of known techniques and by observing results obtained under analogous circumstances.
• a number of factors are considered by the attending diagnostician, including, but not limited to: the species of mammal; its size, age, and general health; the parasite to be controlled and the degree of infestation; the specific disease or disorder involved; the degree of or involvement or the severity of the disease or disorder; the response of the individual; the particular compound administered; the mode of administration; the bioavailability characteristics of the preparation administered; the dose regimen selected; the use of concomitant medication; and other relevant circumstances.
• the compounds of the invention may be administered to the animal by any route which has the desired effect including, but not limited to topically, orally, parenterally ' and subcutaneously.
• Topical administration is preferred.
• Formulations suitable for topical administration include, for example, solutions, emulsions and suspensions and may take the form of a pour-on, spot-on, spray-on, spray race or dip.
• the compounds of the invention may be administered by means of an ear tag or collar.
• Salt forms of the compounds of the invention include both pharmaceutically acceptable salts and veterinary acceptable salts, which can be different to agrochemically acceptable salts.
• 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 2003/034823, US 5631072, WO 2005/64072, W02006/128870, EP 1724392, WO 20051 13886 or WO 2007/090739.
• 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:
• 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 Sphenophorus spp. , 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.
• chinch bugs such as southern chinch bugs, Blissus insularis
• Bermudagrass mite Eriophyes cynodoniensis
• rhodesgrass mealybug Antonina graminis
• two-lined spittlebug Propsapia bicincta
• leafhoppers Tricotuidae family
• cutworms Noctuidae family
• 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.
• Examples of such parasites are: Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculus spp. and Phtirus spp., Solenopotes spp..
• Heteropterida for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus 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.
• the compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium
• rufovillosum Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, 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 and Urocerus augur, and termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes,
• Reticulitermes santonensis Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and Coptotermes formosanus, and bristletails such as Lepisma saccharina.
• the compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling one or more pests selected from the family: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae.
• a compound TX controls one or more of pests selected from the family: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae.
• the compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling one or more of pests selected from the genus: Spodoptera spp, Plutella spp, Frankliniella spp, Thrips spp, Euschistus spp, Cydia spp, Nilaparvata spp, Myzus spp, Aphis spp, Diabrotica spp, Rhopalosiphum spp, Pseudoplusia spp and Chilo spp. .
• a compound TX controls one or more of pests selected from the genus: Spodoptera spp, Plutella spp, Frankliniella spp, Thrips spp, Euschistus spp, Cydia spp, Nilaparvata spp, Myzus spp, Aphis spp, Diabrotica spp, Rhopalosiphum spp, Pseudoplusia spp and Chilo spp.
• pests selected from the genus: Spodoptera spp, Plutella spp, Frankliniella spp, Thrips spp, Euschistus spp, Cydia spp, Nilaparvata spp, Myzus spp, Aphis spp, Diabrotica spp, Rhopalosiphum spp, Pseudoplusia spp and Chilo spp.
• the compounds of formulae I, and I’a, or salts thereof, are especially suitable for controlling one or more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus herns, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis includens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum padi, and Chilo suppressalis.
• a compound TX controls one or more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus herns, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis includens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum Padia, and Chilo Suppressalis, such as Spodoptera littoralis + TX, Plutella xylostella + TX; Frankliniella occidentalis + TX, Thrips tabaci + TX, Euschistus herns + TX, Cydia pomonella + TX, Nilapan/ata lugens + TX, Myzus pers
• one compound selected from the compounds defined in the Tables A-1 to A-297 and Table P is suitable for controlling Spodoptera littoralis, Plutella xylostella,
• Myzus persicae, Chrysodeixis includens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum Padia, and Chilo Suppressalis in cotton, vegetable, maize, cereal, rice and soya crops.
• one compound from selected from the compounds defined in the Tables A-1 to A- 297 and Table P is 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).
• Compounds according to the invention may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (against non-target organisms above and below ground (such as fish, birds and bees), improved physico-chemical properties, or increased biodegradability).
• advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (against non-target organisms above and below ground (such as fish, birds and bees), improved physico-chemical properties, or increased biodegradability).
• certain compounds of formula I may show an advantageous safety profile with respect to non-target arthropods, in particular pollinators such as honey bees, solitary bees, and bumble bees.
• Apis mellifera is particularly, for example, Apis mellifera.
• 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.
• 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.
• 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 sulfoxide, 1 ,4- dioxane, di
• 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 alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of
• 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 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations.
• 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 are:
• 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 %
• 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 %
• Solvent B Acetonitrile with 0.05% formic acid
• Step A2 Preparation of methyl 2-cvclopropyl-6-(trifluoromethvDpyridine-4-carboxylate (intermediate 12) and 2-cvclopropyl-6-(trifluoromethvDpyridine-4-carboxylic acid (intermediate 13)
• the reaction mixture was diluted with ethyl acetate and the organic layer was washed with water (5 x 20 mL), once with brine, dried over magnesium sulfate, filtered and evaporated under reduced pressure.
• the crude was purified by chromatography over silica gel to afford 6-(3-bromo-5-ethyl-1 ,2,4-triazol-1 -yl)pyridine-3- carbonitrile.
• Step B2 Preparation of 6-[3-bromo-5-(1 -bromoethvD-1 .2.4-triazol-1 -yllpyridine-3-carbonitrile
• N-bromosuccinimide (0.323 g, 1 .76 mmol, 0.50 equiv.) and benzoyl peroxide (0.029 g, 0.112 mmol, 0.032 equiv.) were added again, the vial was purged with argon, closed and heated to 80 °C for 2 hours more. The reaction mixture was concentrated under reduced pressure and then purified by chromatography over silica gel to afford 6-[3-bromo-5-(1 -bromoethyl)-1 ,2,4-triazol-1 -yl]pyridine-3-carbonitrile.
• Step C Preparation of N-[1 -[5-bromo-2-(5-cvano-2-pyridyl)-1 .2.4-triazol-3-yl1ethyl1-2-cvclopropyl-6- (trifluoromethyl)pyridine-4-carboxamide (compound P20)
• N-Ethyl-N-isopropyl-propan-2-amine (0.130 mL, 0.746 mmol) was added to a solution of 6-[5-(1 - aminoethyl)-3-bromo-1 ,2,4-triazol-1 -yl]pyridine-3-carbonitrile hydrobromide (intermediate I6, 0.093 g, 0.249 mmol, 1 .00 equiv.) in acetonitrile (2.49 mL).
• Step 1 Preparation of methyl 3-cvclopropyl-5-(trifluoromethyr)benzoate (intermediate 171
• Step 3 Preparation of N-[1 -[5-bromo-2-(5-cvano-2-pyridyl)-1 .2.4-triazol-3-yl1ethyl1-3-cvclopropyl-5- (trifluoromethyl)benzamide (compound P19)
• Step 1 Preparation of methyl 3-(trifluoromethyr)-5-vinyl-benzoate (intermediate 191
• methyl 3-bromo-5-(trifluoromethyl)benzoate (CAS: 187331 -46-0, 20 g, 69.24 mmol) was dissolved in toluene (312 ml_). Then Tributyl(vinyl)Tin (25.56 ml_, 83.09 mmol) was added and the resulting solution was degassed with argon for 10min. Tetrakis(triphenylphosphine) palladium(O) (0.816543 g, 0.69 mmol) was added, and the resulting mixture was stirred at 1 10 °C for 2 hours.
• diphenyl sulfide 36.43 ml_, 21 1 .1 mmol
• 2,2,2-trifluoroethyl trifluoromethanesulfonate (6.207 ml_, 42.22 mmol) were mixed.
• the mixture was stirred for 2 min at room temperature then the autoclave was closed and heated at 150 °C for 20 hours.
• the reaction was cooled at room temperature and a white precipitate was formed.
• 75 ml of diethyl ether was added, then the white solid was filtered. It was washed four times with 30 ml_ of diethyl ether and then dried under reduced pressure.
• Step 3 Preparation of methyl 3-(trifluoromethyl)-5-[2-(trifluoromethyl)cyclopropyllbenzoate
• the desired product was prepared using the condition described in step C of Example 1 to afford N-[1 - [5-bromo-2-(5-cyano-2-pyridyl)-1 ,2,4-triazol-3-yl]ethyl]-3-(trifluoromethyl)-5-[2- (trifluoromethyl)cyclopropyl]benzamide.
• 3-Chloroperbenzoic acid (2.3 g, 1 1 mmol, 2.1 equiv.) was added portionwise to a 0°C cooled solution of methyl 3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)benzoate (intermediate 113 prepared as described above) (1 .8 g, 5.3 mmol) in dichloromethane (16 mL). After stirring for 1 hour at room temperature, more 3-chloroperbenzoic acid (2.3 g, 1 1 mmol, 2.1 equiv.) was added and the reaction mixture was stirred overnight. The precipitate formed was filtered.
• Step 4 Preparation of N-[1 -[5-bromo-2-(5-cvano-2-pyridyl)-1 .2.4-triazol-3-yl1ethyl1-3-(trifluoromethyl)-5-
• the desired product was prepared using the condition described in step C for Example 1 to afford N-[1 - [5-bromo-2-(5-cyano-2-pyridyl)-1 ,2,4-triazol-3-yl]ethyl]-3-(trifluoromethyl)-5- (trifluoromethylsulfonyl)benzamide.
• Step 4 Preparation of N-[1 -[5-bromo-2-(5-cyano-2-pyridyl)-1 ,2,4-triazol-3-yllethyll-3-
• the desired product was prepared using the condition described in step C for Example 1 to afford N-[1 - [5-bromo-2-(5-cyano-2-pyridyl)-1 ,2,4-triazol-3-yl]ethyl]-3-[cyclopropyl(difluoro)methyl]-5- (trifluoromethyl)benzamide.
• Step 1 Preparation of methyl 2-(1 -cvano-2-ethoxy-2-oxo-ethyl ' )-6-(trifluoromethyl ' )pyridine-4- carboxylate (intermediate 1181
• the reaction mass was diluted with 50 ml_ of water and 100 ml_ of ethyl acetate, cooled to 0-10 °C and slowly quenched with 1 N hydrochloric acid via dropping funnel until pH 3.
• the aqueous phase was extracted with ethyl acetate.
• the combined organic layers were dried over sodium sulfate and concentrated under reduced pressure at 50 °C.
• the crude material was purified by chromatography over silica gel with ethyl acetate in cyclohexane to afford methyl 2-(1 -cyano- 2-ethoxy-2-oxo-ethyl)-6-(trifluoromethyl)pyridine-4-carboxylate.

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