Pesticide-active polycyclic derivatives with sulfur-containing substituents

Abstract

Polycyclic derivatives of formula (I), #imgabs0# in which the substituents are as defined in claim 1, as well as agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds, can be used as pesticides and can be prepared in a manner known per se.

Description

[0001] The present application is a divisional application of Chinese invention patent application No. 201680006282.3, entitled “Polycyclic derivatives with pesticidal activity having sulfur-containing substituents”, filed on January 14, 2016, and has a priority date of January 19, 2015.

[0002] The present invention relates to pesticidally active, in particular insecticidal, polycyclic derivatives containing sulphur substituents, to compositions containing those compounds and to their use for controlling animal pests, including arthropods and in particular insects or representatives of the order Acarina.

[0003] Heterocyclic compounds with pesticidal action are known and described, for example, in WO 2012 / 086848, WO 2013 / 018928, WO 2014 / 142292, WO 2015 / 133603, WO 2015 / 000715 and WO 2015 / 121136. Novel pesticidally active polycyclic ring derivatives having sulphur-containing phenyl and pyridyl substituents have now been found.

[0004] The present invention therefore relates to compounds of formula I,

[0005]

[0006] in

[0007] A represents CH, N or N-oxide;

[0008] A1 is CH, N or N-oxide;

[0009] Q is phenyl which may be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl and -C(O)C1-C4 haloalkyl; or

[0010] Q is a five- to ten-membered monocyclic or fused bicyclic ring system which is linked to the ring containing the group A via a carbon atom, said ring system being aromatic, partially saturated or fully saturated and containing 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, with the proviso that each ring system cannot contain more than 2 oxygen atoms and more than 2 sulfur atoms, said five- to ten-membered ring system being mono-substituted up to substituted with substituents independently selected from the group consisting of or

[0011] Q is a partially saturated or fully saturated five- to six-membered aromatic ring system which is linked to the ring comprising the group A via a nitrogen atom, said ring system being mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-haloalkoxy, C1-C4-alkoxy, C1-C4-alkylsulfanyl, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, -C(O)C1-C4-alkyl, C1-C4-haloalkylsulfanyl, C1-C4-haloalkylsulfinyl, C1-C4-haloalkylsulfonyl and -C(O)C1-C4-haloalkyl; and said ring system contains 1, 2 or 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, with the proviso that said ring system cannot contain more than one oxygen atom and more than one sulfur atom; or

[0012] Q is C3-C6 cycloalkyl, or C3-C6 cycloalkyl which is mono- or poly-substituted by substituents selected from the group consisting of halogen, cyano, CONH2, carboxyl, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl and phenyl, wherein the phenyl group may be mono- or poly-substituted by substituents selected from the group consisting of halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl and -C(O)C1-C4 haloalkyl; or

[0013] Q is C2-C6 alkenyl, or C2-C6 alkenyl which is mono- or poly-substituted by substituents selected from the group consisting of halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl and phenyl, wherein the phenyl group may be mono- or poly-substituted by substituents selected from the group consisting of halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl and -C(O)C1-C4 haloalkyl; or

[0014] Q is C2-C6 alkynyl, or C2-C6 alkynyl which is mono- or poly-substituted by substituents selected from the group consisting of halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, tri(C1-C4 alkyl)silyl and phenyl, wherein the phenyl group may be mono- or poly-substituted by substituents selected from the group consisting of halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 halo-alkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl and -C(O)C1-C4 haloalkyl; or

[0015] Q is C1-C6 alkyl, or C1-C6 alkyl which is mono- or poly-substituted by substituents selected from the group consisting of halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, tri(C1-C4 alkyl)silyl and phenyl, wherein the phenyl group may be mono- or poly-substituted by substituents selected from the group consisting of halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 halo-alkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl and -C(O)C1-C4 haloalkyl;

[0016] X is S, SO or SO2;

[0017] R1 is C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C4 alkyl; or

[0018] R1 is C3-C6 cycloalkyl-C1-C4 alkyl which is mono- or poly-substituted by substituents selected from the group consisting of halogen, cyano and C1-C4 alkyl; or

[0019] R1 is C2-C6 alkenyl, C2-C6 haloalkenyl or C2-C6 alkynyl;

[0020] R2 is halogen, cyano, C1-C6 haloalkyl, or C1-C6 haloalkyl substituted by one or two substituents selected from the group consisting of hydroxy, methoxy, and cyano; or

[0021] R2 is C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, O(C1-C4 haloalkyl), or -C(O)C1-C4 haloalkyl; or

[0022] R2 is a C3-C6 cycloalkyl group which may be mono- or poly-substituted by substituents selected from the group consisting of halogen, cyano and C1-C4 alkyl;

[0023] X1 is NR5; wherein R5 is hydrogen, C1-C4 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C4 alkoxy-C1-C4 alkyl or C3-C6 cycloalkyl; or

[0024] X1 is oxygen or sulfur;

[0025] R3 is hydrogen or C1-C2-alkyl;

[0026] R4 is hydrogen, halogen or C1-C3 haloalkyl;

[0027] and agrochemically acceptable salts, stereoisomers, enantiomers, and tautomers of the compound of formula I.

[0028] Compounds of formula I with at least one basic center can form, for example, acid addition salts with strong inorganic acids (for example mineral acids, such as perchloric acid, sulfuric acid, nitric acid, phosphoric acid or hydrohalic acids), strong organic carboxylic acids (for example unsubstituted or, for example, halogen-substituted C1-C4-alkanecarboxylic acids, such as acetic acid (for example, saturated or unsaturated dicarboxylic acids), such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid (for example, hydroxycarboxylic acids), such as ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid), or organic sulfonic acids (for example unsubstituted or, for example, halogen-substituted C1-C4-alkane- or arylsulfonic acids, such as methane- or p-toluenesulfonic acid). The compounds of formula I having at least one acidic group can, for example, form salts with bases, such as mineral salts, for example alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts; or with ammonia or organic amines, for example morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, for example ethylamine, diethylamine, triethylamine or dimethylpropylamine, or mono-, di- or tri-hydroxy lower alkylamines, for example monoethanolamine, diethanolamine or triethanolamine.

[0029] The alkyl groups appearing in the definitions of substituents may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, and their branched isomers. Alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, alkoxy, alkenyl and alkynyl residues are derived from the alkyl residues mentioned. Alkenyl and alkynyl groups may be monounsaturated or polyunsaturated. C1-di-alkylamino is dimethylamino.

[0030] Halogen is typically fluorine, chlorine, bromine or iodine. This also applies accordingly to halogen in combination with other meanings, such as haloalkyl or halophenyl.

[0031] The haloalkyl group preferably has 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.

[0032] Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and also the isomeric pentoxy and hexoxy groups.

[0033] Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.

[0034] Alkoxycarbonyl is, for example, methoxycarbonyl (which is a C1 alkoxycarbonyl), ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, tert-butoxycarbonyl, n-pentoxycarbonyl or hexyloxycarbonyl.

[0035] The alkylsulfanyl group is, for example, a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, an isopropylsulfanyl group, a butylsulfanyl group, a pentylsulfanyl group, and a hexylsulfanyl group.

[0036] The alkylsulfinyl group is, for example, a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, a pentylsulfinyl group, and a hexylsulfinyl group.

[0037] The alkylsulfonyl group is, for example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a pentylsulfonyl group, and a hexylsulfonyl group.

[0038] The haloalkylsulfanyl group is, for example, trifluoromethylsulfanyl, 2,2,2-trifluoroethylsulfanyl, and pentafluoroethylsulfanyl.

[0039] The haloalkylsulfinyl group is, for example, trifluoromethylsulfinyl, 2,2,2-trifluoroethylsulfinyl, or pentafluoroethylsulfinyl.

[0040] The haloalkylsulfonyl group is exemplified by a trifluoromethylsulfonyl group, a 2,2,2-trifluoroethylsulfonyl group, and a pentafluoroethylsulfonyl group.

[0041] Cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0042] Examples of partially saturated or fully saturated five- to six-membered aromatic ring systems in the context of the present invention which are linked via a nitrogen atom to the ring comprising the radical A are, for example, pyrazole, pyrrole, pyrrolidine, pyrrolidin-2-one, piperidine, morpholine, imidazole, triazole and pyridin-2-one.

[0043] In the context of the present invention, "monosubstituted to polysubstituted" in the definition of a substituent typically means, depending on the chemical structure of the substituent, monosubstituted to septately substituted, preferably monosubstituted to pentasubstituted, more preferably mono-, di- or trisubstituted.

[0044] The compounds of formula I according to the present invention also include hydrates which may be formed during salt formation.

[0045] According to the present invention, depending on the number of ring members, a five- to ten-membered monocyclic or fused bicyclic heterocyclic ring system (the five- to ten-membered monocyclic or fused bicyclic heterocyclic ring system may be aromatic, partially saturated or fully saturated and the five- to ten-membered monocyclic or fused bicyclic heterocyclic ring system contains 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, with the proviso that each ring system may not contain more than 2 oxygen atoms and more than 2 sulfur atoms), or a three- to ten-membered monocyclic or fused bicyclic ring system (the three- to ten-membered monocyclic or fused bicyclic ring system may be aromatic, partially saturated or fully saturated), is preferably selected from the group consisting of the following heterocyclic groups:

[0046] pyrrolyl; pyrazolyl; isoxazolyl; furanyl; thienyl; imidazolyl; oxazolyl; thiazolyl; isothiazolyl; triazolyl; oxadiazolyl; thiadiazolyl; tetrazolyl; furyl; pyridinyl; pyrimidinyl; pyrazinyl; pyridazinyl; triazinyl, pyranyl; quinazolinyl; isoquinolinyl; indolizinyl; isobenzofuranyl naphthyridinyl; quinoxalinyl; cinnolinyl; phthalazinyl; benzothiazolyl; benzoxazolyl; benzotriazolyl; indazolyl; indolyl; (1H-pyrrol-1-yl)-; (1H-pyrrol-2-yl)-; (1H-pyrrol-3-yl)-; (1H-pyrazol-1-yl)-; (1H-pyrazol-3-yl)-; (3H-pyrazol-3-yl)-; (1H -pyrazol-4-yl)-; (3-isoxazolyl)-; (5-isoxazolyl)-; (2-furyl)-; (3-furyl)-; (2-thienyl)-; (3-thienyl)-; (1H-imidazol-2-yl)-; (1H-imidazol-4-yl)-; (1H-imidazol-5-yl)-; (2-oxazol-2-yl)-; (oxazol-4-yl)-; (oxazol-5-yl)-; (thiazol-2-yl)-; (thiazol-4-yl)-; (thiazol-5-yl)-; (isothiazol-3-yl)-; (isothiazol-5-yl)-; (1H-1,2,3-triazol-1-yl)-; (1H-1,2,4-triazol-3-yl)-; (4H-1,2,4-triazol-4-yl)- ; (1H-1,2,4-triazol-1-yl)-; (1,2,3-oxadiazol-2-yl)-; (1,2,4-oxadiazol-3-yl)-; (1,2,4-oxadiazol-4-yl)-; (1,2,4-oxadiazol-5-yl)-; (1,2,3-thiadiazol-2-yl)-; (1,2,4-thiadiazol-3-yl)-; (1,2,4-thiadiazol-4-yl)-; (1,3,4-thiadiazol-5-yl)-; (1H-tetrazol-1-yl)-; (1H-tetrazol-5-yl)-; (2H-tetrazol-5-yl)-; (2-pyridyl)-; (3-pyridyl)-; (4-pyridyl)-; (2-pyrimidinyl)-; (4-pyrimidinyl)-; (5-pyrimidinyl)- (pyridinyl)-; (2-pyrazinyl)-; (3-pyridazinyl)-; (4-pyridazinyl)-; (1,3,5-triazin-2-yl)-; (1,2,4-triazin-5-yl)-; (1,2,4-triazin-6-yl)-; (1,2,4-triazin-3-yl)-; (furazan-3-yl)-; (2-quinolinyl)-; (3-quinolinyl) -; (4-quinolinyl)-; (5-quinolinyl)-; (6-quinolinyl)-; (3-isoquinolinyl)-; (4-isoquinolinyl)-; (2-quinazolinyl)-; (2-quinoxalinyl)-; (5-quinoxalinyl)-; (pyrido[2,3-b]pyrazin-7-yl)-; (benzoxazol-5-yl)-; (benzothiazol-5-yl)-;(Benzo[b]thiophen-2-yl)- and (benzo[1,2,5]oxadiazol-5-yl)-; indolinyl and tetrahydroquinolinyl. ;

[0047] In preferred compounds of formula I, Q is selected from the group consisting of J-0 to J-50:

[0048]

[0049] wherein each of the groups J-0 to J-50 is monosubstituted, disubstituted or trisubstituted by Rx, wherein

[0050] Each Rx is independently selected from the group consisting of hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, -C(O)C1-C4 alkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl and -C(O)C1-C4 haloalkyl.

[0051] A preferred group of compounds of formula I is represented by compounds of formula I-1

[0052]

[0053] wherein R2, R4, A, X and Q are as defined above under Formula I; and wherein R1 is methyl, ethyl, n-propyl, isopropyl or cyclopropylmethyl; R4 is hydrogen, halogen or C1-C3 haloalkyl; X1 is N-methyl, oxygen or sulfur; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of compounds of Formula I-1.

[0054] In the preferred group of compounds of formula I-1, R2 is preferably C1-C4 haloalkyl, halogen, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl; X is SO2; R1 is preferably ethyl; X1 is preferably N-methyl; and R4 is preferably hydrogen or C1-C2 haloalkyl.

[0055] In said preferred group of compounds of formula I-1, Q is selected from the group consisting of: J-0 to J-50 (wherein the arrow indicates the point of attachment of the heterocycle to the group Q):

[0056]

[0057] wherein each group J-0 to J-50 is monosubstituted, disubstituted or trisubstituted by Rx, wherein each Rx is independently selected from the group consisting of hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, -C(O)C1-C4 alkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl and -C(O)C1-C4 haloalkyl.

[0058] Another preferred compound of formula I is represented by a compound of formula I-2

[0059]

[0060] wherein R2, R4, A, X and Q are as defined above under formula I; and wherein R1 is methyl, ethyl, n-propyl, isopropyl or cyclopropylmethyl; R4 is hydrogen, halogen or C1-C3 haloalkyl; X1 is N-methyl, oxygen or sulfur; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of these compounds of formula I-2.

[0061] In the preferred group of compounds of formula I-2, R2 is preferably C1-C4 haloalkyl, halogen, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl; X is SO2; R1 is preferably ethyl; X1 is preferably N-methyl; and R4 is preferably hydrogen or C1-C2 haloalkyl.

[0062] In said preferred group of compounds of formula I-2, Q is selected from the group consisting of: J-0 to J-50 (wherein the arrow indicates the point of attachment of the heterocycle to the group Q):

[0063]

[0064] wherein each radical J-0 to J-50 is monosubstituted, disubstituted or trisubstituted by Rx, wherein each Rx is independently selected from the group consisting of hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, -C(O)C1-C4 alkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl and -C(O)C1-C4 haloalkyl.

[0065] In particular, preferred compounds of formula I-1 are those of formula I-1a

[0066]

[0067] in

[0068] A is N or CH;

[0069] X is S or SO2;

[0070] R1 is a C1-C4 alkyl group;

[0071] R2 is C1-C4 haloalkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl;

[0072] R4 is hydrogen or C1-C2 haloalkyl;

[0073] Q a1 is selected from the group consisting of the following substituents:

[0074]

[0075] wherein each Rx is independently selected from the group consisting of hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, -C(O)C1-C4 alkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl and -C(O)C1-C4 haloalkyl.

[0076] More preferred compounds of formula I-1a are those wherein each Rx is independently selected from hydrogen, halogen, C1-C4 alkyl and C1-C4 haloalkyl.

[0077] A particularly preferred group of compounds of formula I-1a is represented by compounds of formula I-1a2

[0078]

[0079] in

[0080] A is N or CH;

[0081] R2 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl;

[0082] R4 is hydrogen or C1-C2 haloalkyl;

[0083] And Q a1 Selected from the group consisting of the following substituents

[0084]

[0085] wherein each Rx is independently hydrogen, halogen, C1-C4 alkyl or C1-C4 haloalkyl.

[0086] In the preferred compounds of formula I-1a2, Rx are each independently preferably halogen, hydrogen or C1-C4 haloalkyl; R1 is preferably ethyl; and R4 is preferably hydrogen.

[0087] In particular, preferred compounds of formula I-1a2 are those wherein Q a1 Selected from J-0z1, J-0z2, J0z3, J-1 Z 、J-5 Z 、J-30 Z and J-43 Z those of;

[0088]

[0089] wherein each Rx is independently hydrogen, halogen or C1-C4 haloalkyl.

[0090] More highly preferred compounds of formula I-2 are those of formula I-2a

[0091]

[0092] in

[0093] A is N or CH;

[0094] X is S or SO2;

[0095] R1 is a C1-C4 alkyl group;

[0096] R2 is C1-C4 haloalkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl;

[0097] R4 is hydrogen or C1-C1-C2 haloalkyl;

[0098] Q a1 Preferably selected from the group consisting of the following substituents

[0099]

[0100] wherein each Rx is independently selected from the group consisting of hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, -C(O)C1-C4 alkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl and -C(O)C1-C4 haloalkyl.

[0101] More preferred compounds of formula I-2a are those wherein each Rx is independently selected from hydrogen, halogen, C1-C4 alkyl and C1-C4 haloalkyl;

[0102] A particularly preferred group of compounds of formula I-2a is represented by compounds of formula I-2a2

[0103]

[0104] in

[0105] A is N or CH;

[0106] R2 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl;

[0107] R4 is hydrogen or C1-C2 haloalkyl;

[0108] And Q a1 is selected from the group of substituents:

[0109]

[0110] wherein each Rx is independently hydrogen, halogen, C1-C4 alkyl or C1-C4 haloalkyl.

[0111] In the preferred compounds of formula I-2a2, each Rx is independently of one another preferably halogen, hydrogen or C1-C4 haloalkyl; R1 is preferably ethyl; and R4 is preferably hydrogen.

[0112] The most highly preferred compounds of formula I-2a2 are those wherein Q a1 Selected from J-0z1, J-0z2, J0z3, J-1 Z 、J-5 Z 、J-30 Z and J-43 Z those of;

[0113]

[0114] wherein each Rx is independently hydrogen, halogen or C1-C4 haloalkyl.

[0115] In all preferred embodiments of the compounds of formula I mentioned above, the substituents Q and Qa1 are preferably selected from

[0116] a) phenyl, which may be substituted with halogen or C1-C4 haloalkyl;

[0117] b) pyrazole, which may be substituted with C1-C4 haloalkyl;

[0118] d) cyclopropyl, which may be substituted by cyano;

[0119] e) triazole, which may be substituted by halogen;

[0120] f) C2-C6 alkynyl, which may be substituted by phenyl, wherein the phenyl may be substituted by halogen; and

[0121] g) C2-C6 alkenyl, which may be substituted by phenyl, wherein the phenyl may be substituted by halogen.

[0122] Particularly preferred embodiments of compounds of formula I are represented by compounds of formula I-2a3

[0123]

[0124] in

[0125] R2 is C1-C4 haloalkyl;

[0126] R4 is hydrogen or C1-C4 alkyl; and

[0127] Q is selected from

[0128] a) phenyl, which may be substituted with halogen or C1-C4 haloalkyl;

[0129] b) pyrazole, which may be substituted with C1-C4 haloalkyl;

[0130] d) cyclopropyl, which may be substituted by cyano;

[0131] e) triazole, which may be substituted by halogen;

[0132] f) C2-C6 alkynyl, which may be substituted by phenyl, wherein the phenyl may be substituted by halogen; and

[0133] g) C2-C6 alkenyl, which may be substituted by phenyl, wherein the phenyl may be substituted by halogen.

[0134] In further embodiments of the present invention, compounds of formula I are preferred, wherein

[0135] R1 is a C1-C4 alkyl group;

[0136] R2 is C1-C4 haloalkyl or C1-C4 haloalkylsulfanyl;

[0137] R3 is hydrogen;

[0138] R4 is hydrogen or C1-C4 haloalkyl;

[0139] Q is phenyl, which may be mono-, di- or tri-substituted by substituents selected from the group consisting of halogen and C1-C4 haloalkyl; or

[0140] Q is C2-C6 alkenyl, which may be monosubstituted with phenyl, which may itself be monosubstituted with C1-C4 haloalkyl; or

[0141] Q is pyrazolyl, which may be monosubstituted by C1-C4 haloalkyl or halogen; or

[0142] Q is a pyrimidinyl group or a C3-C6 cycloalkyl group, which may be substituted with a cyano group; or

[0143] Q is a triazolyl group, which may be substituted with halogen; or

[0144] Q is a C1-C4 alkyl group, which may be substituted with a cyano group; or

[0145] Q is a C2-C6 alkynyl group, which may be monosubstituted with a phenyl group, which itself may be monosubstituted or disubstituted with a halogen group;

[0146] X is S or SO2;

[0147] X1 is N-C1-C4 alkyl; in particular N-CH3;

[0148] A is CH or N; and

[0149] A1 is CH or N.

[0150] The process according to the invention for preparing the compound of formula I is carried out in principle by methods known to a person skilled in the art and is as follows:

[0151] Compounds of formula I, wherein A, A1, R2, R1, R3, R4, X, X1 and Q are as defined in formula I, can be prepared by a Suzuki reaction (as shown in Scheme 1) involving, for example, reacting a compound of formula II, wherein Xb1 is a leaving group such as chloro, bromo or iodo, or an aryl- or alkylsulfonate such as trifluoromethanesulfonate, with a compound of formula IIIa, wherein Yb1 It may be a boron-derived functional group such as, for example, B(OH)2 or B(OR b1 )2, where R b1 It can be a C1-C4 alkyl group or two groups OR b1 The reaction can be carried out by using a palladium-based catalyst such as tetrakis(triphenylphosphine)-palladium or (1,1'-bis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane (1:1 complex) in the presence of a base (such as sodium carbonate or cesium fluoride) in a solvent or solvent mixture (such as a mixture of 1,2-dimethoxyethane and water or dioxane and water), preferably under an inert atmosphere. The reaction temperature may preferably range from room temperature to the boiling point of the reaction mixture. Such Suzuki reactions are well known to those skilled in the art and have been reviewed in, for example, J.Orgmet.Chem. 576, 1999, 147-168.

[0152] Solution 1 :

[0153]

[0154] Alternatively, the compound of formula I may be prepared by reacting the compound of formula IIIb (wherein Y b2 The compound of formula II is prepared by the Stirler reaction of a trialkyltin derivative, preferably tri-n-butyltin) with a compound of formula II. Such a Stirler reaction is typically carried out in the presence of a palladium catalyst such as tetrakis(triphenylphosphine)palladium(0) or (1,1'bis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane (1:1 complex), in an inert solvent such as DMF, acetonitrile, or dioxane, optionally in the presence of an additive such as cesium fluoride or lithium chloride, and optionally in the presence of another catalyst such as copper(I) iodide. Such Stiller couplings are also familiar to those skilled in the art and have been described, for example, in J. Org. Chem., 2005, 70, 8601-8604, J. Org. Chem., 2009, 74, 5599-5602, and Angew. Chem. Int. Ed., 2004, 43, 1132-1136.

[0155] Compounds of formula I, wherein Q is a nitrogen-carrying heterocyclic system, and wherein A, Al, R2, R1, R3, R4, X, X1, and Q are as defined in formula I, can be prepared from compounds of formula II, wherein A, Al, R2, R1, R3, R4, X, and X1 are as defined in formula I, and Xb1 is a leaving group such as chloro, bromo, or iodo, or an aryl- or alkylsulfonate such as trifluoromethanesulfonate, by reacting the heterocycle Q, which contains an appropriate NH functionality, in the presence of a base such as an alkali metal hydride such as sodium hydride, or an alkali metal carbonate such as cesium carbonate or potassium carbonate, optionally in the presence of a copper catalyst such as copper(I) iodide, in an inert solvent such as N-methylpyrroledione or DMF at a temperature between 30° C. and 150° C. This reaction is particularly advantageous for compounds of formula I wherein A is methane. Alternatively, such compounds can be prepared from compounds of formula II by reacting heterocycle Q (which contains an appropriate NH functionality) in the presence of a base (e.g., an alkali metal hydride such as sodium hydride, or an alkali metal carbonate such as cesium carbonate or potassium carbonate) in a suitable solvent such as N-methylpyrroledione or DMF at a temperature between 30° C. and 150° C. For heterocycle J-30 Z , which is illustrated in Scheme 2, gives compounds of Formula Iaa (wherein A, A1, R2, R1, R3, R4, X and R x is as defined previously).

[0156] Option 2

[0157]

[0158] Compounds of formula I can also be prepared by the Suzuki reaction as described above (as depicted in Scheme 3), which involves reacting a compound of formula IV with a compound of formula V, wherein X b2 can be halogen (preferably chlorine, bromine, or iodine) or a sulfonate (such as, for example, triflate), and Y b3 It may be a boron-derived functional group (such as, for example, B(OH)2 or B(OR b2 )2, where R b2 It can be a C1-C4 alkyl group or two groups OR b2 Together with the boron atom, they may form a five-membered ring (such as, for example, pinacol borate). In Formula IV, A, A1, X, X1, R1, R2, R3 and R4 are as described in Formula I.

[0159] The reaction can be catalyzed by a palladium-based catalyst (e.g., tetrakis(triphenylphosphine)palladium) in the presence of a base (e.g., sodium carbonate) in a solvent or solvent mixture (e.g., a mixture of 1,2-dimethoxyethane and water), preferably under an inert atmosphere. The reaction temperature can preferentially be in the range of room temperature to the boiling point of the reaction mixture.

[0160] Option 3

[0161]

[0162] In a similar manner, a compound of formula I can be prepared by reacting a compound of formula V with a compound of formula VI (wherein A, A1, A2, X, X1, R1, R2, R3 and R4 are as described above, and Y b4 It can be prepared by Stiller coupling of a trialkyltin derivative, preferably tri-n-butyltin (Scheme 3).

[0163] Compounds of formula IIa (wherein A is nitrogen and A1, X1, R1, R2, R3 and R4 are as described in formula I, and Xb1 is chlorine or bromine) can be prepared according to the method shown in Scheme 4:

[0164] Solution 4.

[0165]

[0166] Thus, compounds of formula IVa are oxidized by methods known to those skilled in the art and described, for example, in WO 2010 / 125985 to give compounds of formula VIIa, wherein A1, X1, R1, R2, R3 and R4 are as described in formula I and Xb1 is chlorine or bromine. Compounds of formula VIIa are treated with phosphorus oxychloride or phosphorus oxychloride, optionally in the presence of a base such as triethylamine and optionally in a solvent such as dichloromethane, DMF or dioxane (see, for example, Syn. Comm., 31(16), 2507-2511, 2001). Compounds of formula II, wherein A is CH, i.e. compounds of formula IIb, can be prepared as shown in Scheme 5:

[0167] Option 5.

[0168]

[0169] Thus, compounds of formula IVb, wherein A1, X1, R1, R2, R3 and R4 are as described in formula I and Xb1 is chlorine or bromine, can be halogenated, for example, with bromine or chlorine in a suitable solvent (e.g. glacial acetic acid) at temperatures between 0° C. and 150° C., optionally in a microwave reactor, to compounds of formula VIIb, wherein A1, X1, R1, R2, R3 and R4 are as described in formula I and Xb1 is chlorine or bromine. Alternatively, the reaction can be carried out in the presence of a Lewis acid catalyst such as ferric chloride or aluminum chloride (Friedel-Crafts halogenation). Similar reactions have been described in the literature (see, for example, Ger. Offen., 19840337, 2000; Med. Chem. Lett., 3(6), 450-453, 2012 and Macromolecules, 47(14), 4607-4614, 2014). Oxidation of VIIb according to methods known to those skilled in the art and described, for example, in WO 2010 / 125985 yields compounds of formula IIb, wherein A1, X1, R1, R2, R3 and R4 are as described in formula I and Xb1 is chlorine or bromine.

[0170] The compound of formula I can also be prepared by making a compound of formula VIII,

[0171]

[0172] (wherein X, R1, R3, R4, Q and A are as described above under Formula I), with a compound of Formula IX,

[0173]

[0174] (wherein A1 and R2 are as described above under Formula I, and wherein R5 is hydrogen or as described above under Formula I), in the presence of a dehydrating agent such as, for example, polyphosphoric acid, at a temperature between 150°C and 250°C to yield a compound of Formula I, wherein the substituents are as described above and under Formula I. These methods are well known and have been described, for example, in WO 2008 / 128968, WO 2012 / 086848, WO 2013 / 018928, WO 2014 / 142292 and WO 2006 / 003440. For compounds of Formula Ia, this method is outlined in Scheme 6:

[0175] Option 6

[0176]

[0177] As can be seen in Scheme 6, the formation of compounds of formula Ia occurs via the intermediate state of compounds of formula X (and / or its positional isomers Xa). Intermediate X or intermediate Xa can be formed as a pure entity, or intermediates X and Xa can be produced as a mixture of regioisomeric acylation products. In many cases, it is advantageous to prepare compounds of formula (Ia) via such intermediates X / Xa, which can be isolated and optionally purified. This is illustrated in Scheme 7 for compounds of formula Ia:

[0178] Option 7

[0179]

[0180] Compounds of formula X and / or Xa (or mixtures thereof) or salts thereof (wherein Q is as defined above, and wherein X, R1, R2, R3, R4, A and A1 are as described above under formula I, and wherein R5 is hydrogen or as described above under formula I) can be prepared by the following:

[0181] i) activating a compound of formula VIII (wherein Q is as defined above) by methods known to those skilled in the art and described, for example, in Tetrahedron, 2005, 61(46), 10827-10852 to form an activated species VIIIa (wherein Q is as defined above and wherein X 01 is halogen, preferably chlorine). For example, compound VIIIa (wherein X is halogen) is formed by treating VIII with, for example, oxalyl chloride (COCl) 2 or thionyl chloride SOCl 2 in the presence of a catalytic amount of N,N-dimethylformamide (DMF) in an inert solvent such as dichloromethane or tetrahydrofuran at a temperature between 20° C. and 100° C. (preferably 25° C.). 01 is halogen, preferably chlorine). Alternatively, treatment of compounds of formula VIII with, for example, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) or dicyclohexylcarbodiimide (DCC) in an inert solvent such as pyridine or tetrahydrofuran, optionally in the presence of a base such as triethylamine, at temperatures between 25°C and 180°C, will yield activated species VIIIa (wherein X 01 They are Afterwards

[0182] ii) treating the activated species VIIIa with a compound of formula IX (or a salt thereof) (wherein A1 and R2 are as described above under formula I, and R5 is hydrogen, C1-C4 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C4 alkoxy-C1-C4 alkyl or C3-C6 cycloalkyl) in an inert solvent such as dichloromethane, tetrahydrofuran, dioxane or toluene, optionally in the presence of a base such as triethylamine or pyridine, at a temperature of 0°C to 80°C to form a compound of formula X and / or Xa (or a mixture thereof).

[0183] Compounds of formula X and / or Xa (or mixtures thereof) can be further converted to compounds of formula Ia (wherein Q is as defined above, and wherein A, Al, R1, R2, R3 and R4 are as described above under formula I, and wherein R5 is hydrogen or as described above under formula I) by dehydration, for example by heating compounds X and / or Xa (or mixtures thereof) in an inert solvent such as N-methylpyrrolidine at a temperature between 25° C. and 180° C. (preferably 100° C. and 170° C.), optionally under microwave conditions, in the presence of an acid catalyst such as, for example, methanesulfonic acid or p-toluenesulfonic acid (TsOH), or by heating in acetic acid at a temperature between 100° C. and 180° C. Such methods have been previously described, for example, in WO 2010 / 125985 and WO 2015 / 000715. Compounds of formula VIII are obtained by hydrolysis of compounds of formula VIIIb, VIIIc and VIIId (see below) using conditions known to those skilled in the art. An alternative synthesis of compounds of formula I is illustrated in Scheme 8.

[0184] Plan 8.

[0185]

[0186] As shown in Scheme 8, compounds of formula XII (wherein R1, R4 are as described in formula I and Xb3 is halogen) can be reacted with compounds of formula IIIa (Suzuki reaction) or IIIb as previously described in Scheme 1 to give compounds of formula VIIIb. Alternatively, compounds of formula XII can be reacted with compounds of formula XIII (wherein Q is a heterocycle and hydrogen is attached to the nitrogen atom of the heterocycle) in the presence of a base, optionally in the presence of a copper catalyst. The chemistry is similar to that illustrated in Scheme 2. Compounds of formula VIIIb are then treated with ammonia in a suitable solvent (e.g., methanol or ethanol) to give amides of formula XI, where R1, R4 and Q are as described in formula I. Amides of formula XI are reacted with compounds of formula IXa (wherein A1, R2 and X1 are as described in formula I) to produce compounds of formula Xc. This amide nitrogen heteroarylation reaction is typically carried out under transition metal-catalyzed C-N bond-forming conditions involving a catalytic system (e.g., such as [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II)) typically consisting of a metal such as a palladium source (e.g., a palladium(0) precursor such as Pd2(dibenzylideneacetone)3, or a palladium(II) precursor such as Pd(OAc)2) and a ligand (e.g., phosphine-based or N-heterocyclic carbene-based); a base such as an alkoxide (e.g., sodium tert-butoxide or potassium tert-butoxide), a carbonate, phosphate, or silylamide (e.g., potassium carbonate or cesium carbonate, potassium phosphate, or lithium hexamethyldisilazane), or a hydroxide (e.g., sodium hydroxide or potassium hydroxide); and a solvent such as toluene, tetrahydrofuran, dioxane, dimethoxyethane, N,N-dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide, and aqueous solutions thereof. These methods are well known to those skilled in the art and are described in, for example, WO 2014 / 142292. Under the above-mentioned amide cross-coupling reaction conditions, compounds of formula Xc can be separated and converted into compounds of formula Ib as described in scheme 7), but can also spontaneously close to compounds of formula Ib, particularly in the case where X1 is NR5. The oxidation of compounds of formula Ib to compounds of formula I can be achieved by methods known to those skilled in the art, such as using meta-chloroperbenzoic acid in an inert solvent (such as chloroform or dichloromethane). Alternatively, the reaction order can be changed so that the compound of formula XI is first oxidized to a compound of formula XIa, and then converted to a compound of formula I using the same reaction as described above. Compounds of formula XIIa and XIIb can be obtained by the reactions shown in schemes 9 and 10.

[0187] Plan 9.

[0188]

[0189] Plan 10

[0190]

[0191] In Scheme 9, the compound of Formula XIV (wherein R 001 is C1-C4 alkyl) can be oxidized and the N-oxide of formula XV converted to the compound of formula XII using the method described in Scheme 4. Similarly, the compound of formula XIVa (wherein R 001 Is C1-C4 alkyl) can be halogenated to a compound of formula XVa and then converted to a compound of formula XIIb using the chemical method described in Scheme 5. Compounds with formula IV are known in the literature (e.g., in WO 2015 / 000715). Compounds with formula XIV and XIVa have been described in, for example, WO 2014132971, WO 2014123205, WO 2014119670, WO 2014119679, WO 2014119674, WO 2014119699, WO 2014119672, and WO 2014104407. Compounds with formula IXa are either described in the literature (see, for example, WO 2014 / 142292) or are commercially available.

[0192] Compounds of formula (I) wherein Q is C3-C6 cycloalkyl or C3-C6 cycloalkyl mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C1-C4 haloalkyl, and phenyl can be prepared by the methods described above (specifically, compounds of formula (I) wherein Q is cyclopropyl can be prepared by the Suzuki reaction involving cyclopropyl-boronic acid as illustrated in Scheme 1). For the specific case of compounds of formula (I) wherein Q is C3-C6 cycloalkyl substituted by cyano (e.g., compound Iaaa) and C3-C6 cycloalkyl substituted by C1-C4 haloalkyl (e.g., compound Iaab), these compounds can be prepared by the methods shown in Scheme 11.

[0193] Plan 11

[0194]

[0195] As shown in Scheme 11, a compound of formula II, wherein X is S, SO or SO (particularly SO), and wherein A1, A, X1, R1, R2, R3 and R4 are as defined above, and Xb1 is a leaving group such as, for example, chloro, bromo or iodo (preferably bromo) or an aryl sulfonate or an alkyl sulfonate such as trifluoromethanesulfonate, is treated with trimethylsilyl-acetonitrile (TMSCN) in the presence of zinc (II) fluoride, ZnF2, and a palladium (0) catalyst such as tris(diphenyleneacetone) dipalladium (0)-chloroform adduct (Pd2(dba)3) and a ligand such as Xantphos, in an inert solvent such as N,N-dimethylformamide, DMF, at a temperature between 100°C and 180°C, optionally under microwave heating, to give a compound of formula Iaaa, wherein X is S, SO or SO2 (particularly SO2). Such chemical methods have been described in the literature, for example in Organic Letters (Org. Lett.), 16 (24), 6314-6317; 2014. Compounds of formula XVII (wherein Qx is a direct bond or (CH2)) can be reacted with a compound of formula XVII in the presence of a base (such as sodium hydride, potassium carbonate K2CO3 or cesium carbonate Cs2CO3) in an inert solvent (such as N,N-dimethylformamide DMF, acetone or acetonitrile) at a temperature between 0°C and 120°C. n , and n is 1, 2 or 3, and wherein Xb 10 is a leaving group such as a halogen (preferably chlorine, bromine or iodine)) to give a compound of formula Iaab (wherein X is S, SO or SO2 (particularly SO2), and wherein A1, A, X1, R1, R2, R3 and R4 are as defined above, and wherein Qx is a direct bond or is (CH2) n , and n is 1, 2 or 3). Alternatively, compounds of formula Iaa can be prepared directly from compounds of formula II by treating with compounds of formula XVI (wherein Qx is as described in XVII) in the presence of a catalyst (such as Pd2(dba)3) and a ligand (such as BINAP), a strong base (such as lithium hexamethyldisilazane LiHMDS) in an inert solvent (such as tetrahydrofuran (THF) at a temperature between 30°C and 80°C. Such chemistry has been described, for example, in J. Am. Chem. Soc., 127(45), 15824-15832, 2005.

[0196] Compounds of formula Iaab can be further used to prepare compounds of formula Iaac and Iaad (Scheme 15). In practice, compounds of formula Iaab (wherein X is S, SO or SO2, and wherein A1, A, X1, R1, R2, R3 and R4 are as defined above, and wherein Qx is a direct bond or (CH2)) can be reacted under conditions known to those skilled in the art (aqueous alkaline or acidic conditions; for example, lithium hydroxide or sodium hydroxide in an alcoholic solvent such as methanol at a temperature between 20°C and reflux conditions). n , and n is 1, 2 or 3) is hydrolyzed to a compound of formula Iaac (wherein X is S, SO or SO2, and wherein A1, A, X1, R1, R2, R3 and R4 are as defined above, and wherein Qx is a direct bond or (CH2) n , and n is 1, 2 or 3). Compounds of formula Iaac are treated with a reagent such as sulfur tetrafluoride SF4 or Fluolead (4-tert-butyl-2,6-dimethylphenylsulfur trifluoride) optionally in the presence of hydrogen fluoride HF at a temperature between 20°C and 100°C to produce compounds of formula Iaad (wherein X is S, SO or SO2, and wherein A1, A, X1, R1, R2, R3 and R4 are as defined above, and wherein Qx is a direct bond or is (CH2) n , and n is 1, 2 or 3).

[0197] Compounds of formula Iaab can also be used to prepare compounds of formula Iaae (Scheme 12).

[0198] Plan 12

[0199]

[0200] As shown in Scheme 12, compounds of formula Iaab (wherein X is S, SO or SO2, and wherein A1, A, X1, R1, R2, R3 and R4 are as defined above, and wherein Qx is a direct bond or (CH2)) can be reacted under conditions known to those skilled in the art (aqueous basic or acidic conditions; for example, lithium hydroxide or sodium hydroxide in an alcoholic solvent such as methanol at a temperature between 20°C and reflux conditions; or aqueous sulfuric acid, optionally in the presence of a co-solvent, at a temperature between 20°C and reflux conditions). n , and n is 1, 2 or 3) is hydrolyzed to a compound of formula Iaae (wherein X is S, SO or SO2, and wherein A1, A, X1, R1, R2, R3 and R4 are as defined above, and wherein Qx is a direct bond or (CH2) n , and n is 1, 2 or 3).

[0201] Alternatively, compounds of formula Iaab may be prepared as shown in Schemes 13 and 14. As shown in Scheme 13, the chemistry used is the same as that described in Scheme 11, except that the substrates of the reaction are different. Thus, compounds XIIa and / or XIIb described previously (wherein X is S or SO2 (particularly SO2), and wherein A, R1, R3 and R4 are as defined above, and wherein Xb3 is a halogen (such as, for example, chlorine, bromine or iodine (preferably chlorine) or an aryl- or alkylsulfonate (such as a triflate) and wherein R 0001 is C1-C4 alkyl) is reacted with trimethylsilyl-acetonitrile TMSCN as described in Scheme 11 to produce a compound of formula XVIII (wherein X is S or SO2 (specifically SO2), and wherein A, R1, R3 and R4 are as defined above, and wherein R 001 is C1-C4 alkyl). These are converted to compounds of formula VIIId (wherein X is S or SO2 (particularly SO2), and wherein Qx, A, R1, R3 and R4 are as defined above, and wherein R 001 is C1-C4 alkyl). Compounds of formula VIIId are readily hydrolyzed by methods known to those skilled in the art to give compounds of formula VIIIe (wherein X is S or SO2 (particularly SO2), and wherein Qx, A, R1, R3 and R4 are as defined above).

[0202] Plan 13

[0203]

[0204] The chemistry shown in Scheme 14 has been described in detail previously (see, for example, Scheme 7). This chemistry involves the formation of an activated species VIIIf (wherein X is S or SO2 (particularly SO2), and wherein Qx, A, R1, R3 and R4 are as defined above, and wherein LG1 is typically chlorine), followed by amide coupling with a compound of formula IXb (wherein X1, A1 and R2 are as previously defined) to give a compound of formula Xd. Compounds of formula Xd can be converted to compounds of formula Iaab by the formal dehydration step previously described in Scheme 7. All substituent definitions in Scheme 14 are as previously described.

[0205] Plan 14

[0206]

[0207] The reactants may be reacted in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal 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 hydroxide, and carbocyclic amines. Examples that may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, 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).

[0208] The reactants can be reacted as is, i.e. without the addition of solvents or diluents. However, in most cases, 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, the base used in excess (e.g., triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline) can also serve as a solvent or diluent.

[0209] The reaction is advantageously carried out at a temperature of from about -80°C to about +140°C, preferably from about -30°C to about +100°C, in many cases at a temperature between ambient temperature and about +80°C.

[0210] A compound of formula I can be converted into another compound of formula I in a manner known per se by replacing one or more substituents of the starting compound of formula I with another or further substituent(s) according to the invention in a conventional manner.

[0211] Depending on the reaction conditions and the starting materials chosen as appropriate in the respective case, it is possible, for example, to replace only one substituent with another substituent according to the invention in one reaction step or to replace several substituents with several other substituents according to the invention in one and the same reaction step.

[0212] Salts of compounds of formula I can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula I are obtained by treatment with a suitable acid or a suitable ion exchange reagent, and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchange reagent.

[0213] Salts of compounds of formula I can be converted in a customary manner into the free compounds I, acid addition salts (for example by treatment with suitable basic compounds or with suitable ion exchange reagents) and base salts (for example by treatment with suitable acids or with suitable ion exchange reagents).

[0214] The salts of the compounds of formula I can be converted in a manner known per se into other salts, acid addition salts of the compounds of formula I, for example into other acid addition salts, for example by treating a salt of an inorganic acid (such as the hydrochloride) with a suitable metal salt of the acid (such as the sodium salt, barium salt or silver salt, for example with silver acetate) in a suitable solvent in which the inorganic salt formed (such as silver chloride) is insoluble and therefore precipitates from the reaction mixture.

[0215] Depending on the procedure or reaction conditions, the compounds of formula I which have salt-forming properties can be obtained in free form or in the form of salts.

[0216] Depending on the number of asymmetric carbon atoms present in the molecule, the absolute and relative configuration and / or according to the configuration of non-aromatic double bonds present in the molecule, the compounds of the formula I and, where appropriate, their tautomers, in each case in free form or in salt form, may be present in the form of one of the possible isomers or as a mixture thereof, for example in the form of pure isomers, such as enantiomers and / or diastereomers, or as isomer mixtures, such as enantiomeric mixtures, for example racemates, diastereomeric mixtures or racemic mixtures; the present invention relates to the pure isomers as well as to all possible isomer mixtures and is to be understood above and below as such, even if stereochemical details are not explicitly mentioned in all cases.

[0217] Diastereomeric mixtures or racemic mixtures of compounds of formula I in free form or in salt form, the acquisition of which may depend on the starting materials and procedures chosen, can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and / or chromatography.

[0218] Enantiomeric mixtures obtainable in an analogous manner (e.g. racemates) can be resolved into the optical antipodes by known methods, for example by recrystallization from optically active solvents; by chromatography on chiral adsorbents, for example high performance liquid chromatography (HPLC) on acetylcellulose; by cleavage with specific immobilized enzymes with the aid of suitable microorganisms; by forming inclusion compounds, for example using chiral crown ethers, in which only one enantiomer is complexed; or by conversion into diastereomeric salts, for example by reacting the basic end product racemate with an optically active acid (e.g. a carboxylic acid, such as camphoric acid, tartaric acid or malic acid or a sulfonic acid, such as camphorsulfonic acid) and separating the diastereomeric mixtures obtainable in this way, for example by fractional crystallization on the basis of their different solubilities, thereby obtaining the diastereomers from which the desired enantiomer can be freed by the action of suitable reagents (e.g. a basic reagent).

[0219] Pure diastereomers or enantiomers can be obtained according to the invention not only by separation of the appropriate isomer mixtures, but also by generally known diastereoselective or enantioselective synthesis methods, for example by using starting materials of the appropriate stereochemistry according to the invention.

[0220] N-oxides can be prepared by reacting a compound of formula I with a suitable oxidizing agent (e.g. H O / urea adduct) in the presence of an anhydride (e.g. trifluoroacetic anhydride). Such oxidations are known from the literature, for example from J. Med. Chem., 32 (12), 2561-73, 1989 or WO 00 / 15615.

[0221] It is advantageous in each case to isolate or synthesize the biologically more effective isomers, such as enantiomers or diastereomers or isomer mixtures, such as enantiomeric mixtures or diastereomeric mixtures, if the individual components have different biological activities.

[0222] The compounds of formula I and, where appropriate, their tautomers (in each case in free form or in salt form) can, if appropriate, also be obtained in the form of hydrates and / or include other solvents, such as those which can be used for crystallization of compounds present in solid form.

[0223] The compounds according to the following Tables 1 to 6 can be prepared according to the above methods. The examples which follow are intended to illustrate the invention and to show preferred compounds of formula I.

[0224] Table X: This table discloses 33 substituents designated as X.001 to X.033 for the chemical formulas (Iaa), (Iab), (Iac), (Iad), (Iae) and (Iaf), which are disclosed after Table X.

[0225]

[0226]

[0227] Table 1: The table discloses 33 compounds 1.001 to 1.033 of formula (Iaa):

[0228]

[0229] wherein n is 0, and R2 is CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X. For example, compound 1.004 has the following structure:

[0230]

[0231] Table 2:

[0232] The table discloses 33 compounds 2.001 to 2.033 of formula (Iaa) wherein n is 2, and R2 is CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0233] Table 3:

[0234] The table discloses 33 compounds 3.001 to 3.033 of formula (Iaa) wherein n is 0, and R2 is CF2CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0235] Table 4:

[0236] The table discloses 33 compounds 4.001 to 4.033 of formula (Iaa) wherein n is 2, and R2 is CF2CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0237] Table 5:

[0238] The table discloses 33 compounds 5.001 to 5.033 of formula (Iaa) wherein n is 0, and R2 is CF(CF3)2, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0239] Table 6:

[0240] The table discloses 33 compounds 6.001 to 6.033 of formula (Iaa) wherein n is 2, and R2 is CF(CF3)2, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0241] Table 7:

[0242] The table discloses 33 compounds 7.001 to 7.033 of formula (Iaa) wherein n is 0, and R2 is OCF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001 to X.033.

[0243] Table 8:

[0244] The table discloses 33 compounds 8.001 to 8.033 of formula (Iaa) wherein n is 2, and R2 is OCF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0245] Table 9:

[0246] The table discloses 33 compounds 9.001 to 9.033 of formula (Iaa) wherein n is 0, and R2 is SCF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001 to X.033.

[0247] Table 10:

[0248] The table discloses 33 compounds 10.001 to 10.033 of formula (Iaa) wherein n is 2, and R2 is SCF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001 to X.033.

[0249] Table 11:

[0250] The table discloses 33 compounds 11.001 to 11.033 of formula (Iaa) wherein n is 0, and R2 is SOCF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0251] Table 12:

[0252] The table discloses 33 compounds 12.001 to 12.033 of formula (Iaa) wherein n is 2, and R2 is SOCF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0253] Table 13:

[0254] The table discloses 33 compounds 13.001 to 13.033 of formula (Iaa) wherein n is 0, and R2 is SO2CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0255] Table 14:

[0256] The table discloses 33 compounds 14.001 to 14.033 of formula (Iaa) wherein n is 2, and R2 is SO2CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0257] Table 15:

[0258] The table discloses 33 compounds 15.001 to 15.027 of formula (Iaa) wherein n is 0, and R2 is Br, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001 to X.033.

[0259] Table 16:

[0260] The table discloses 33 compounds 16.001 to 16.033 of formula (Iaa) wherein n is 2, and R2 is Br, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0261] Table 17:

[0262] The table discloses 33 compounds 17.001 to 17.033 of formula (Iaa) wherein n is 0, and R2 is CF2CH3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0263] Table 18:

[0264] The table discloses 33 compounds 18.001 to 18.033 of formula (Iaa) wherein n is 2, and R2 is CF2CH3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0265] Table 19:

[0266] The table discloses 33 compounds 19.001 to 19.033 of formula (Iaa) wherein n is 0, and R2 is OCF2CHFCF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0267] Table 20:

[0268] The table discloses 33 compounds 20.001 to 20.033 of formula (Iaa) wherein n is 2, and R2 is OCH2CHFCF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0269] Table 21:

[0270] The table discloses 33 compounds 21.001 to 21.033 of formula (Iaa) wherein n is 0, and R2 is OCH2CHF2, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0271] Table 22:

[0272] The table discloses 33 compounds 22.001 to 22.033 of formula (Iaa) wherein n is 2, and R2 is OCH2CHF2, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0273] Table 23:

[0274] The table discloses 33 compounds 23.001 to 23.033 of formula (Iaa) wherein n is 0, and R2 is C(CF3)2OCH3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0275] Table 24:

[0276] The table discloses 33 compounds 24.001 to 24.033 of formula (Iaa) wherein n is 2, and R2 is C(CF3)2OCH3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0277] Table 25:

[0278] The table discloses 33 compounds 25.001 to 25.033 of formula (Iaa) wherein n is 0, and R2 is CF3, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0279] Table 26:

[0280] The table discloses 33 compounds 26.001 to 26.024 of formula (Iaa) wherein n is 2, and R2 is CF3, R1 is ethyl, R4 is CF3, and Q is as defined in rows X.001-X.033 of Table X.

[0281] Table 27:

[0282] The table discloses 33 compounds 27.001 to 27.033 of formula (Iaa) wherein n is 0, and R2 is CF2CH3, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0283] Table 28:

[0284] The table discloses 28 compounds 28.001 to 28.033 of formula (Iaa) wherein n is 2, and R2 is CF2CH3, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0285] Table 29:

[0286] The table discloses 27 compounds 29.001 to 29.033 of formula (Iaa) wherein n is 0, and R2 is CF(CF3)2, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0287] Table 30:

[0288] The table discloses 33 compounds 30.001 to 30.033 of formula (Iaa) wherein n is 2, and R2 is CF(CF3)2, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0289] Table 31:

[0290] The table discloses 33 compounds 31.001 to 31.033 of formula (Iaa) wherein n is 0, and R2 is OCF3, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0291] Table 32:

[0292] The table discloses 33 compounds 32.001 to 32.033 of formula (Iaa) wherein n is 2, and R2 is OCF3, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0293] Table 33:

[0294] The table discloses 33 compounds 33.001 to 33.033 of formula (Iaa) wherein n is 0, and R2 is SCF3, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0295] Table 34:

[0296] The table discloses 33 compounds 34.001 to 34.033 of formula (Iaa) wherein n is 2, and R2 is SCF3, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0297] Table 35:

[0298] The table discloses 33 compounds 35.001 to 35.033 of formula (Iaa) wherein n is 0, and R2 is SOCF3, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0299] Table 36:

[0300] The table discloses 33 compounds 36.001 to 36.033 of formula (Iaa) wherein n is 2, and R2 is SOCF3, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0301] Table 37:

[0302] The table discloses 33 compounds 37.001 to 37.033 of formula (Iaa) wherein n is 0, and R2 is SO2CF3, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0303] Table 38:

[0304] The table discloses 33 compounds 38.001 to 38.033 of formula (Iaa) wherein n is 2, and R2 is SO2CF3, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0305] Table 39:

[0306] The table discloses 33 compounds 39.001 to 39.033 of formula (Iaa) wherein n is 0, and R2 is Br, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0307] Table 40:

[0308] The table discloses 33 compounds 40.001 to 40.033 of formula (Iaa) wherein n is 2, and R2 is Br, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0309] Table 41:

[0310] The table discloses 33 compounds 41.001 to 41.033 of formula (Iaa) wherein n is 0, and R2 is CF2CH3, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0311] Table 42:

[0312] The table discloses 33 compounds 42.001 to 42.033 of formula (Iaa) wherein n is 2, and R2 is CF2CH3, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0313] Table 43:

[0314] The table discloses 33 compounds 43.001 to 43.033 of formula (Iaa) wherein n is 0, and R2 is OCF2CHFCF3, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0315] Table 44:

[0316] The table discloses 33 compounds 44.001 to 44.033 of formula (Iaa) wherein n is 2, and R2 is OCF2CHFCF3, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0317] Table 45:

[0318] The table discloses 33 compounds 45.001 to 45.033 of formula (Iaa) wherein n is 0, and R2 is OCF2CHFCF3, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0319] Table 46:

[0320] The table discloses 33 compounds 46.001 to 46.033 of formula (Iaa) wherein n is 2, and R2 is OCF2CHFCF3, R1 is ethyl, R4 is CF3, and Q is as defined in Table X, rows X.001-X.033.

[0321] Table 47:

[0322] The table discloses 33 compounds 47.001 to 47.033 of formula (Iaa) wherein n is 0, and R2 is C(CF3)2OCH3, R1 is ethyl, R4 is CF3, and Q is as defined in rows X.001-X.033 of Table X.

[0323] Table 48:

[0324] The table discloses 33 compounds 48.001 to 48.033 of formula (Iaa) wherein n is 2, and R2 is C(CF3)2OCH3, R1 is ethyl, R4 is CF3, and Q is as defined in rows X.001-X.033 of Table X.

[0325] Table 49: The table discloses 33 compounds 49.001 to 49.033 of formula (Iab):

[0326]

[0327] wherein n is 0, and R2 is CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X. For example, compound 49.017 has the following structure:

[0328]

[0329] Table 50:

[0330] The table discloses 33 compounds 50.001 to 50.024 of formula (Iab) wherein n is 2, and R2 is CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0331] Table 51:

[0332] The table discloses 33 compounds 51.001 to 51.033 of formula (Iab) wherein n is 0, and R2 is CF2CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0333] Table 52:

[0334] The table discloses 33 compounds 52.001 to 52.033 of formula (Iab) wherein n is 2, and R2 is CF2CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0335] Table 53:

[0336] The table discloses 33 compounds 53.001 to 53.033 of formula (Iab) wherein n is 0, and R2 is CF(CF3)2, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0337] Table 54:

[0338] The table discloses 33 compounds 53.001 to 53.033 of formula (Iab) wherein n is 2, and R2 is CF(CF3)2, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0339] Table 55:

[0340] The table discloses 33 compounds 55.001 to 55.033 of formula (Iab) wherein n is 0, and R2 is SCF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0341] Table 56:

[0342] The table discloses 33 compounds 56.001 to 56.033 of formula (Iab) wherein n is 2, and R2 is SCF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in Table X, rows X.001-X.033.

[0343] Table 57: The table discloses 33 compounds 57.001 to 57.033 of formula (lac):

[0344]

[0345] wherein n is 0, and R2 is CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X. For example, compound 57.021 has the following structure:

[0346]

[0347] Table 58:

[0348] The table discloses 33 compounds 58.001 to 58.024 of formula (lac) wherein n is 2, and R2 is CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001 to X.033 of Table X.

[0349] Table 59:

[0350] The table discloses 33 compounds 59.001 to 59.033 of formula (lac) wherein n is 0, and R2 is CF2CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0351] Table 60:

[0352] The table discloses 33 compounds 60.001 to 60.033 of formula (lac) wherein n is 2, and R2 is CF2CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0353] Table 61:

[0354] The table discloses 33 compounds 61.001 to 61.033 of formula (lac) wherein n is 0, and R2 is CF(CF3)2, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0355] Table 62:

[0356] The table discloses 33 compounds 62.001 to 62.033 of formula (lac) wherein n is 2, and R2 is CF(CF3)2, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0357] Table 63:

[0358] The table discloses 33 compounds 63.001 to 63.033 of formula (lac) wherein n is 0, and R2 is SCF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001 to X.033 of Table X.

[0359] Table 64:

[0360] The table discloses 33 compounds 64.001 to 64.033 of formula (lac) wherein n is 2, and R2 is SCF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001 to X.033 of Table X.

[0361] Table 65: The table discloses 33 compounds 65.001 to 65.033 of formula (Iad):

[0362]

[0363] wherein n is 0, and R2 is CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X. For example, compound 65.016 has the following structure:

[0364]

[0365] Table 66:

[0366] The table discloses 33 compounds 66.001 to 66.024 of formula (Iad) wherein n is 2, and R2 is CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0367] Table 67:

[0368] The table discloses 33 compounds 67.001 to 67.033 of formula (Iad) wherein n is 0, and R2 is CF2CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0369] Table 68:

[0370] The table discloses 33 compounds 68.001 to 68.033 of formula (Iad) wherein n is 2, and R2 is CF2CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0371] Table 69:

[0372] The table discloses 33 compounds 69.001 to 69.033 of formula (Iad) wherein n is 0, and R2 is CF(CF3)2, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0373] Table 70:

[0374] The table discloses 33 compounds 70.001 to 70.033 of formula (Iad) wherein n is 2, and R2 is CF(CF3)2, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0375] Table 71:

[0376] The table discloses 33 compounds 71.001 to 71.033 of formula (Iad) wherein n is 0, and R2 is SCF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0377] Table 72:

[0378] The table discloses 33 compounds 72.001 to 72.033 of formula (Iad) wherein n is 2, and R2 is SCF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0379] Table 73: The table discloses 33 compounds 73.001 to 73.033 of formula (lae):

[0380]

[0381] wherein n is 0, and R2 is CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X. For example, compound 73.024 has the following structure:

[0382]

[0383] Table 74:

[0384] The table discloses 33 compounds 74.001 to 74.024 of formula (lae) wherein n is 2, and R2 is CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001 to X.033 of Table X.

[0385] Table 75:

[0386] The table discloses 33 compounds 75.001 to 75.033 of formula (lae) wherein n is 0, and R2 is CF2CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0387] Table 76:

[0388] The table discloses 33 compounds 76.001 to 76.033 of formula (lae) wherein n is 2, and R2 is CF2CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0389] Table 77:

[0390] The table discloses 33 compounds 77.001 to 77.033 of formula (lae) wherein n is 0, and R2 is CF(CF3)2, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0391] Table 78:

[0392] The table discloses 33 compounds 78.001 to 78.033 of formula (lae) wherein n is 2, and R2 is CF(CF3)2, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0393] Table 79:

[0394] The table discloses 33 compounds 79.001 to 79.033 of formula (lae) wherein n is 0, and R2 is SCF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0395] Table 80:

[0396] The table discloses 33 compounds 80.001 to 80.033 of formula (lae) wherein n is 2, and R2 is SCF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0397] Table 81: The table discloses 33 compounds 81.001 to 81.033 of formula (laf):

[0398]

[0399] wherein n is 0, and R2 is CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X. For example, compound 81.007 has the following structure:

[0400]

[0401] Table 82:

[0402] The table discloses 33 compounds 82.001 to 82.033 of formula (laf) wherein n is 2, and R2 is CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0403] Table 83:

[0404] The table discloses 33 compounds 83.001 to 83.033 of formula (Iaf) wherein n is 0, and R2 is CF2CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0405] Table 84:

[0406] The table discloses 33 compounds 84.001 to 84.033 of formula (laf) wherein n is 2, and R2 is CF2CF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0407] Table 85:

[0408] The table discloses 33 compounds 85.001 to 85.033 of formula (Iaf) wherein n is 0, and R2 is CF(CF3)2, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0409] Table 86:

[0410] The table discloses 33 compounds 86.001 to 86.033 of formula (Iaf) wherein n is 2, and R2 is CF(CF3)2, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0411] Table 87:

[0412] The table discloses 33 compounds 87.001 to 87.033 of formula (laf) wherein n is 0, and R2 is SCF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001 to X.033 of Table X.

[0413] Table 88:

[0414] The table discloses 33 compounds 88.001 to 88.033 of formula (laf) wherein n is 2, and R2 is SCF3, R1 is ethyl, R4 is hydrogen, and Q is as defined in rows X.001-X.033 of Table X.

[0415] The compounds of formula I according to the invention are active ingredients of preventive and / or therapeutic value in the field of pest control. Even at low application rates, they 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 on all or individual developmental stages of normally sensitive and 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., by destroying the pests either immediately or only after a certain period of time (e.g., during molting), or indirectly, for example, by reducing egg laying and / or hatching rates.

[0416] Examples of the above-mentioned animal pests are:

[0417] From the order Acarina, e.g.

[0418] Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp., Eotetranychus spp., Eriophyes spp., Hemitarsonemus spp.), Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp., Tarsonemus spp.) and Tetranychus spp.;

[0419] From the order Phthirus, e.g.

[0420] Haematoptes, Longignathus, Pediculus, Pemphigus, and Psyllids;

[0421] From the order Coleoptera, e.g.

[0422] Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotoma spp., Conoderus spp., Cosmopolites spp., Cotinisnitida, Curculio spp., Cyclocephala spp., Dermestes spp., Diabrotica spp., Diloboderus abderus), Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagriavilosa, Leptinotarsa ​​decemLineata, Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Maladera castanea, Megascelis spp., Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp., Phlyctinus spp., Popillia spp.), Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp.), Somaticus spp., Sphenophorus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp., and Trogoderma spp.;

[0423] From the order Diptera, e.g.

[0424] Aedes spp., Anopheles spp., Antherigonas occata., Bactrocea oleae, Bibio hortulanus, Bradysia spp., Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyza tripunctata, Glossina spp., Hypoderma spp.), Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis spp., Riveria quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp., and Tipula spp.;

[0425] From the order Hemiptera, e.g.

[0426] Acanthocoris scabrator, Green stink bug, Alfalfa blind bug, Amblypelta nitida, Bathycoelia thalassina, Soil stink bug, Cockspur, Clavigralla tomentosicollis, Creontiades spp., Cocoa stink bug, Dichelops furcatus, Cotton stink bug, Edessa spp., Euchistus spp., Eurydema pulchrum, Flat shield bug, Brown-winged stink bug, Horcias nobilellus, Rice stink bug, Lygus, Tropical scale, Murgantiahistrionic, Neomegalotomus spp., Nesidiocoris tenuis, Green stink bug, Nysius simulans, Oebalus insularis, Skin stink bug, Wall stink bug, Red assassin bug, Cocoa stink bug, Scaptocoris castanea, Black stink bug (Scotinophara spp.), Thyanta spp., Triatomine bug, Cassava web bug (Vatiga illudens);

[0427] Aphids, Adalges spp., Agallina ensigera, Agonascena targionii, Aleurodicus spp., Aleurocanthus spp., Sugarcane hole whitefly, Aleurothrixus floccosus, Cabbage whitefly (Aleyrodes brassicae), Cotton leafhopper (Amarasca biguttula), Amritodus atkinson, Kidney shield scale spp., Aphididae, Aphid, Scale spp., Eggplant groove aphids, Bactericera cockerelli, Whitefly spp., Brachycaudus spp., Cabbage aphid, Kamasu, Cavariella aegopodii Scop., Wax scale spp., Brown round scale, Net seed grass leaf round scale, Cicadell spp., large white leafhopper (Cofanaspectra), Cryptomelania spp., Cicadulina spp., brown soft scale, corn yellow-winged leafhopper, naked whitefly spp., citrus psyllid, wheat two-tailed aphid, western round-tailed aphid, small green leafhopper spp., apple aphid, grape spotted leafhopper spp., wax clam spp., red eucalyptus psyllid (Glycaspis brimblecombei), cabbage constriction aphid, Hyalopterus spp., super-tumor aphid species, lemon fruit green leafhopper (Idioscopus clypealis), Jacobiasca lybica, Laodelphax striatum spp., ball-hard scale, oyster shield scale spp., radish aphid (Lopaphis erysimi), Lyogenys maidis, long-tube aphid spp., Mahanarva spp., moth wax hopper family (Metcalfa pruinosa), wheat netless aphid, Myndus crudus, aphids, Taiwan leek aphids, black-tailed leafhoppers, brown planthoppers (Nilaparvata spp.), pear green aphids, Odonaspis ruthae, parasitic sugarcane aphids, bayberry whitefly, Caulis psyllids, scutellaria spp., gall aphids, corn waxhoppers, flat-horned planthoppers, hopscotch aphids, root-knotted aphids, Mosella spp., white-shielded scales, mealybugs, cotton blind bugs (Pseudatomoscelis seriatus), psyllids, cotton scales (Pulvinaria aethiopica), round-shielded scales (Quesada gigas), electric leafhoppers (Recilia dorsalis), constricted tube aphids, black-helmeted scales, leafhoppers, Schizophrenia spp., wheat aphids (Sitobion spp.), white-backed planthopper, Spissistilus festinus, Tarophagus Proserpina, aphids, whiteflies, Tridiscus sporoboli, sunflower mealybugs (Trionymus spp.), African psyllids, orange-headed scale, Zygina flammigera, Zyginidia scutellaris;

[0428] From the order Hymenoptera, e.g.

[0429] Acromyrmex, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Pogonomyrmex spp., Slenopsis invicta, Solenopsis spp., and Vespa spp.

[0430] From the order Isoptera, e.g.

[0431] Coptotermes, Corniternes cumulans, Coptotermes, Macrotermes, Macrotermes, Microtermes, Reticulitermes; tropical fire ants

[0432] From the order Lepidoptera, e.g.

[0433] Long-winged torrefies, brown-banded torrefies, clear-winged torrefies, ground moths, cotton leafworms, Amylois spp., pea moths, yellow torrefies, silver moths (Argyresthia spp.), banded torrefies, yarrow-patterned torrefies, cotton miners, corn borers, powdery moths, peach fruit moths, grass borers, leaf rollers, Chrysoteuchia topiaria, grape fruit moths, leaf rollers, cloud torrefies, pattern torrefies, sheath moths, lepidoptera, Cosmophila flava, grass borers, cabbage borers, apple torrefies, boxwood moths, torrefies, boxwood moths, stem borers, Sudan bollworms, diamond borers, African stem borers, powdery moths, leaf torrefies (Epinotia) spp.), fine-spotted moth, Etiella zinckinella, flower tortoise, ring-needle moth, yellow tussock moth, root cutter, Feltia jaculiferia, Grapholita spp., green budworm, Spodoptera spp., cabbage borer, Herpetogramma spp., American white moth, tomato borer, Lasmopalpus lignosellus, spiral leafminer, leafminer, grape flower tortoise, Loxostege bifidalis, tussock moth, miner, leaf moth, cabbage armyworm, tobacco hornworm, Mythimna spp., Noctuidae, fall moth, Orniodes indica, European corn borer, super-small tortoise, brown tortoise, small-eyed tortoise, stem borer, Pectinophora gossypi-ela, coffee leafminer, armyworm, potato moth, cabbage butterfly, Pieris spp., diamondback moth, budworm spp., leaf moth spp., mint leafminer, Richia albicosta, Scirpophaga spp., stem borer, stalkworm, Spodoptera spp., cotton leaf roller, stalkworm, Heteroptera spp., leaf roller, cabbage looper, tomato leafminer, and brood moth spp.;

[0434] From the order Maloca, e.g.

[0435] Liceus and Trichodesmosis;

[0436] From the order Orthoptera, e.g.

[0437] Blatta, Blattella, Mole Cricket, Madeira Cockroach, Locust, Northern Mole Cricket (Neocurtillahexadactyla), Periplaneta, Mole Cricket (Scapteriscus spp.), and Desert Locust;

[0438] From the order Rodentia, e.g.

[0439] Liposcelis spp.;

[0440] From the order Siphonaptera, e.g.

[0441] Ceratophyllum, Ctenophora, and Xenops;

[0442] From the order Thysanoptera, e.g.

[0443] Calliothrips phaseoli, Flower Thrips spp., Sun Thrips spp., Brown-banded Thrips spp., Parthenothrips spp., African Orange Hard Thrips (Scirtothrips aurantii), Bean Thrips (Sericothrips variabilis), Banded Thrips spp., Thrips spp.;

[0444] From the order Thysanura, for example, the silverfish (Lepisma saccharina).

[0445] The active ingredients according to the invention can be used for controlling, that is to say suppressing or destroying pests of the aforementioned type, which occur in particular on plants, especially on useful and ornamental plants in agriculture, horticulture and forestry, or on organs of these plants, such as fruits, flowers, leaves, stems, tubers or roots, and in some cases even plant organs formed at a later point in time still remain protected against these pests.

[0446] Suitable target crops are, in particular, cereals such as wheat, barley, rye, oats, rice, corn or sorghum; beets such as sugar beets or fodder beets; fruits such as pome, stone or soft fruit such as apples, pears, plums, peaches, apricots, cherries or berries such as strawberries, raspberries or blackberries; leguminous crops such as beans, lentils, peas or soybeans; oilseed crops such as rapeseed, mustard, poppy, olives, sunflowers, coconuts, castor beans, cocoa beans or peanuts; melon crops such as pumpkin, cucumber or melon; fiber plants such as cotton, flax or jute; citrus fruits such as oranges, lemons, grapefruit or tangerines; vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes or bell peppers; lauraceae such as avocado, cinnamon or camphor; and also tobacco, nuts, coffee, eggplant, sugarcane, tea, pepper, grapevines, hops, plantaginaceae and latex plants.

[0447] The compositions and / or methods of the present invention may also be used on any ornamental and / or vegetable crop, including flowers, shrubs, broadleaf trees, and evergreen plants.

[0448] For example, the present invention can be used on any of the following ornamental plant species: Ageratum, Alonso spp., Anemone, Amur sunflower, Anthemis, Antirrhinum, Aster, Begonia (e.g., Rieger Begonia, Begonia spp., Begonia tubéreux), Bougainvillea, Brachycome spp., Brassica (ornamental plants), Calceolaria, Capsicum, Catharanthus roseus, Canna, Knapweed, Chrysanthemum, Cineraria (Cineraria), Coreopsis, Crassula coccinea, Cuphea ignea, Dahlia, Delphinium, Dicentra, Dorotheantus spp.), Lisianthus, Forsythia, Fuchsia, Geranium gnaphalium, Gerbera, Globe amaranth, Heliotrope, Sunflower, Hibiscus, Hydrangea, Hydrangea, Rhododendron, Impatiens (African balsam), Iresines spp., Kalanchoe, Lantana, March flower, Lion's ear, Lilium, Japanese lily, Physalis, Monarda, Monarda, Tagetes, Dianthus (carnation), Canna, Oxalis, Daisy, Pelargonium (Pelargonium pelargonium, Pelargonium pelargonium), Viola (pansy), Petunia, Phlox, Plectranthus spp.), poinsettia, creeper (Parthenocissus quinquefolia, Parthenocissus quinquefolia), primrose, ranunculus, azalea, Rosa (rose), rudbeckia, African violet, salvia, Scaevola aemola, Schizanthus wisetonensis, sedum, nightshade, Solanum spp., marigold, tobacco, verbena, zinnia, and other bedding plants.

[0449] For example, the present invention can be used on any of the following vegetable species: Allium (garlic, onion, shallot (A.oschaninii), leek, shallot, scallion), beet parsley, celery, asparagus, beet, Brassica (Brassica oleracea, Chinese cabbage, turnip), peppers, chickpeas, endive, chicory (chicory, endive), watermelon, Cucurbita (cucumber, cantaloupe), Cucurbita (zucchini, Indian pumpkin), Cynara (artichoke, cardoon), carrot, fennel, Hypericum, lettuce, Lycopersicon (tomato, cherry tomato), mint, basil, parsley, Phaseolus (bean, pea), pea, radish, edible rhubarb, rosemary, sage, black salsify, eggplant, spinach, Valerian (V.eriocarpa), and broad bean.

[0450] Preferred ornamental plant species include African violets, begonias, dahlias, gerberas, hydrangeas, verbenas, roses, kalanchoe, poinsettias, aster, cornflowers, coreopsis, delphiniums, monarda, phlox, rudbeckias, sedums, petunias, violets, impatiens, geraniums, chrysanthemums, ranunculus, fuchsias, salvias, hydrangeas, rosemary, sage, St. John's wort, mint, bell peppers, tomatoes, and cucumbers.

[0451] The active ingredients according to the invention are particularly suitable for controlling the bean aphid, cucumber leaf beetle, tobacco budworm, peach aphid, diamondback moth and sea moth on cotton, vegetables, corn, rice and soybean crops. The active ingredients according to the invention are also particularly suitable for controlling the cabbage looper (preferably on vegetables), the codling moth (preferably on apples), the green leafhopper (preferably on vegetables, in vineyards), the potato leaf beetle (preferably on potatoes) and the striped stem borer (preferably on rice).

[0452] In another aspect, the present invention may also relate to a method for controlling damage to plants or parts thereof caused by plant-parasitic nematodes (endoparasitic, semi-endoparasitic and ectoparasitic nematodes), in particular the following 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; cereal cyst nematodes, Heterodera avenae, Heterodera glycines, Heterodera schachtii and Heterodera schachtii. schachtii), Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus, and other Sting nematode species; Pine nematodes, Bursaphelenchus xylophilus, and other Bursaphelenchus species; Ring nematodes, Criconemoides species, Criconemella species, Criconemoides species, and Mesocriconema species;Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci, and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus, and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species, and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; False root knot nematodes Needle nematodes, Longidoruse longatus, and other Longidorus species; Pinnematodes, Pratylenchus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi, and other Pratylenchus species; Burrowing nematodes, Radopholus similis, and other Radopholus species;Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis, and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus, and other Trichodorus species; Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes), Xiphinema species; and other plant-parasitic nematode species, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp.;

[0453] The compounds of the present invention also have activity against mollusks. Examples of such mollusks include, for example, the family Apple Snail; the genus Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); the family Bradybaena fruticum; the genus Helicoverpa (C. hortensis, C. nemoralis); the family Ochlodina; the genus Deroce ras) (Wild Gray Slug (D. agrestis), D. empiricorum, Field Gray Slug (D. laeve), Garden Gray Slug (D. reticulatum)); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H. obvia); 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.

[0454] The term "crops" is to be understood as also including crop plants which have been transformed by the use of recombinant DNA techniques in such a way that they are able to synthesize one or more selectively acting toxins, such as are known, for example, from toxigenic bacteria, in particular those of the genus Bacillus.

[0455] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, such as those from Bacillus cereus or Bacillus japonicus; or insecticidal proteins from Bacillus thuringiensis, such as delta-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or vegetative insecticidal proteins (Vips), such as Vip1, Vip2, Vip3, or Vip3A; or insecticidal proteins from nematode-parasitic bacteria, such as Photorhabdus or Xenorhabdus, such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, spider toxins, wasp toxins, and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomyces toxins; lectins; plant lectins, such as pea lectin, barley lectin or snowdrop lectin; lectins; protease inhibitors, such as trypsin inhibitors, serine protease inhibitors, potato storage protein (patatin), cysteine ​​protease inhibitors, papain inhibitors; ribosome inactivating proteins (RIP), such as ricin, corn-RIP, abrin, luffa seed toxin, saporin or bryophyllin; steroid metabolizing enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as sodium channel or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

[0456] In the context of the present invention, δ-endotoxins such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vips), such as Vip1, Vip2, Vip3 or Vip3A, should be understood to include, but are not limited to, mixed toxins, truncated toxins and modified toxins. Mixed toxins are recombinantly produced by combining different regions of those proteins (see, for example, WO 02 / 15701). Truncated toxins such as truncated Cry1Ab are known. In the case of modified toxins, one or more amino acids of a naturally occurring toxin are replaced. In such amino acid replacements, it is preferred that a non-naturally occurring protease recognition sequence be inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see WO 03 / 018810).

[0457] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed in, for example, EP-A-0 374 753, WO 93 / 07278, WO 95 / 34656, EP-A-0 427 529, EP-A-451 878 and WO 03 / 052073.

[0458] Methods for preparing such transgenic plants are known to those skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP-A-0 367474, EP-A-0 401 979 and WO 90 / 13651.

[0459] The toxins included in the transgenic plants render the plants tolerant to harmful insects. Such insects can be found in any insect taxonomic group, but are particularly common among beetles (Coleoptera), two-winged insects (Diptera), and moths (Lepidoptera).

[0460] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known and some of them are commercially available. Examples of such plants are: (corn variety expressing Cry1Ab toxin); YieldGard (corn variety expressing Cry3Bb1 toxin); YieldGard (corn varieties expressing Cry1Ab and Cry3Bb1 toxins); (corn variety expressing Cry9C toxin); Herculex (a corn variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) that confers tolerance to the herbicide glufosinate-ammonium); NuCOTN (cotton variety expressing Cry1Ac toxin); Bollgard (cotton variety expressing Cry1Ac toxin); Bollgard (cotton varieties expressing Cry1Ac and Cry2Ab toxins); (cotton variety expressing Vip3A and Cry1Ab toxins); (potato variety expressing Cry3A toxin); GT Advantage (GA21 glyphosate tolerance trait), CB Advantage (Bt11 corn borer (CB) trait) and

[0461] Other examples of such genetically modified crops are:

[0462] 1. Bt11 corn, from Syngenta Seeds SAS, Chemin de Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. This genetically modified maize plant is resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia inermis) by transgenic expression of a truncated Cry1Ab toxin. Bt11 corn also transgenically expresses the PAT enzyme to confer tolerance to the herbicide glufosinate-ammonium.

[0463] 2. Bt176 maize, from Syngenta Seeds, 27 Rue de Hobbitt, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. This genetically modified maize strain is resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia inermis) by transgenic expression of the Cry1Ab toxin. Bt176 maize also transgenically expresses the PAT enzyme to confer tolerance to the herbicide glufosinate-ammonium.

[0464] 3. MIR604 maize, available from Syngenta Seeds, 27 Rue de Hobbit, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. This maize is 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.

[0465] 4. MON 863 maize, from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses the Cry3Bb1 toxin and confers resistance to certain coleopteran insects.

[0466] 5. IPC 531 cotton, from Monsanto Europe SA, 270-272 Avenue Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0467] 6.1507 maize, from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Genetically modified maize expressing the protein Cry1F for resistance to certain lepidopteran insects and the protein PAT for tolerance to the herbicide glufosinate-ammonium.

[0468] 7. NK603 x MON 810 corn, from Monsanto Europe SA, 270-272 Boulevard Tervuren, B-1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. This corn is a conventionally bred hybrid corn variety, produced by crossing the genetically modified varieties NK 603 and MON 810. NK603 x MON 810 corn transgenically expresses the protein CP4 EPSPS obtained from the Agrobacterium strain CP4, rendering it herbicide tolerant. (contains glyphosate), and Cry1Ab toxin from Bacillus thuringiensis subsp. kurstakia, which confers resistance to certain lepidopteran insects, including the European corn borer.

[0469] Transgenic crops of insect-resistant plants are also described in the BATS (Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) report 2003 ( http: / / bats.ch )middle.

[0470] The term "crops" should be understood to also include crops that have been transformed using recombinant DNA technology so that they can synthesize antipathogenic substances with selective action, such as, for example, so-called "pathogenesis-related proteins" (PRPs, see, for example, EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants that can synthesize such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95 / 33818, and EP-A-0 353 191. Methods for producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above.

[0471] Crops can also be modified to increase resistance to fungal (eg, Fusarium, Anthracnose, or Phytophthora), bacterial (eg, Pseudomonas), or viral (eg, Potato Leaf Roll Virus, Tomato Spotted Wilt Virus, Cucumber Mosaic Virus) pathogens.

[0472] Crops also include those with increased resistance to nematodes, such as Heterodera glycines.

[0473] Crops with tolerance to abiotic stress include those with increased tolerance to drought, high salinity, high temperature, cold, frost or light radiation, for example, through expression of NF-YB or other proteins known in the art.

[0474] Antipathogenic substances that can be expressed by such transgenic plants include, for example, ion channel blockers (e.g. sodium and calcium channel blockers, such as viral KP1, KP4 or KP6 toxins); stilbene synthases; bibenzyl synthases; chitinases; glucanases; so-called "pathogenesis-related proteins" (PRPs, see, for example, EP-A-0 392 225); antipathogenic substances produced by microorganisms, such as peptide antibiotics or heterocyclic antibiotics involved in plant pathogen defense (see, for example, WO 95 / 33818) or protein or polypeptide factors (so-called "plant disease resistance genes", as described in WO 03 / 000906).

[0475] Further areas of use of the compositions according to the invention are the protection of stored goods and storage spaces and of raw materials such as wood, textiles, floor coverings or buildings, and in the hygiene sector, in particular the protection of humans, domestic animals and productive livestock from pests of the types mentioned.

[0476] The present invention also provides methods for controlling pests (such as mosquitoes and other disease vectors; see also http: / / www.who.int / malaria / vector_control / irs / en / ). In one embodiment, the method for controlling pests comprises applying the composition of the present invention to the target pests, their locus, or a surface or substrate by painting, rolling, spraying, coating, or dipping. By way of example, IRS (indoor residual spraying) application to surfaces (such as walls, ceilings, or floor surfaces) is contemplated by the methods of the present invention. In another embodiment, application of such a composition to a substrate, such as a nonwoven or fabric material in the form of (or that can be used in the manufacture of) netting, coverings, bedding, curtains, and tents is contemplated.

[0477] In one embodiment, the method for controlling such harmful organism comprises applying the composition of the present invention of pest-killing effective dose to target harmful organism, their place or surface or matrix, so that on this surface or matrix, effective pest-killing activity of retention is provided.Such application can be carried out by brushing, rolling, spraying, coating or impregnation of pest-killing composition of the present invention.By way of example, the IRS application of surface (as wall, ceiling or floor surface) has been expected by method of the present invention, so that effective pest-killing activity of retention is provided on this surface.In another embodiment, it has been expected to use such composition for the control of the retention of harmful organism on matrix, and this matrix is ​​the fabric material of the form (or can be used for the manufacture of these articles) such as being in netting, covering, quilt, curtain and tent.

[0478] The substrate to be treated (including nonwovens, fabrics or nettings) can be made of natural fibers such as cotton, raffia, jute, flax, sisal, burlap or wool, or synthetic fibers such as polyamide, polyester, polypropylene, polyacrylonitrile or the like. Polyester is particularly suitable. Methods for treating textiles are known, for example WO 2008 / 151984, WO 2003 / 034823, US 5631072, WO 2005 / 64072, WO 2006 / 128870, EP 1724392, WO 2005113886 or WO 2007 / 090739.

[0479] A further area of ​​use of the compositions according to the invention is in the field of tree injection / trunk treatment of all ornamental trees as well as all kinds of fruit and nut trees.

[0480] In the field of tree injection / trunk treatment, the compounds according to the invention are particularly suitable for combating wood-boring insects from the aforementioned orders Lepidoptera and from the orders Coleoptera, in particular against the wood-boring insects listed in the following Tables A and B:

[0481] Table A. Examples of economically important exotic wood-boring insects.

[0482]

[0483] Table B. Examples of economically important native wood-boring insects.

[0484]

[0485]

[0486]

[0487] The present invention can also be used to control any insect pest that may be present in turfgrass, including, for example, beetles, caterpillars, fire ants, ground pearls, millipedes, woodlice, mites, mole crickets, scale insects, mealybugs, cicadas, southern wheat stink bugs, and white grubs. The present invention can be used to control insect pests at all stages of their life cycle, including eggs, larvae, nymphs, and adults.

[0488] Specifically, the present invention can be used to control insect pests that feed on the roots of turfgrasses, such as grubs (e.g., Cyclocephala spp. (e.g., masked beetle, C. lurida), Rhizotrogus spp. (e.g., European beetle, European root-cutting gill beetle (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, P. beetle (M. castanea), and Tomarus spp.), ground pearls (Margarodes spp.), mole crickets (tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana), and leatherjackets (European crane fly, Tipula spp.).

[0489] The present invention can also be used to control insect pests of turfgrass in thatched homes, including armyworms (such as the fall armyworm Spodoptera frugiperda, and the common armyworm Pseudaletia unipuncta), cutworms, weevils (Sphenophorus spp., such as S. venatus verstitus and S. parvulus), and grass borers (such as Crambus spp. and the tropical grass borer, Herpetogramma phaeopteralis).

[0490] The present invention can also be used to control insect pests in turfgrasses that live above ground and feed on turfgrass leaves, including wheat stink bugs (such as the southern wheat stink bug, Blissus insularis), Bermudagrass mite (Eriophyes cynodoniensis), Grass mealybug (Antonina graminis), Propsapia bicincta, leafhoppers, cutworms (Noctuidae), and Schizaphis graminis.

[0491] The present invention can also be used to control other pests in turfgrass, such as introduced fire ants (Solenopsis invicta) that create nests in lawns.

[0492] In the hygiene field, the compositions according to the invention are effective against ectoparasites such as hard ticks, soft ticks, scabies, autumn mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.

[0493] Examples of such parasites are:

[0494] Order: Pediculus: Haematopodiformes, Longignathiformes, Human Pediculus, Pubic Pediculus, and Blind Pediculus.

[0495] Trichophagus: Trichodesmida, Trichodesmida, Trichodesmida, Trichodesmida, Trichodesmida, and Trichodesmida.

[0496] From the order Diptera and the suborders Longicornis and Brachyceras, for example, Aedes, Anopheles, Culex, Simuli, True Simuli, Phlebotomus, Lucilia, Culicoides, Spotted Horsefly, Humpback Horsefly, Yellow Horsefly, Tabanus, Mastodon, Philipomyia, Bee Fly, Housefly, Odontostomys, Biting Fly, Black Horn Fly, Morefly, Toilet Fly, Glossina, Calliphora, Greenfly, Chrysomelidae, Slough Fly, Sarcophagnum, Mylomys, Dermestria, Gastromys, Lice Fly, Sheep Fly and Ixodid Fly.

[0497] From the order of the Siphonaptera, for example, the genera Siphonaptera, Ctenocephalides, Xenopsyda, and Ceratophyllum.

[0498] From the order Heteroptera, e.g., Cimex, Triatoma, and Triatoma.

[0499] Blattodea, such as the Oriental cockroach, American cockroach, German cockroach, and Chaparral.

[0500] Subclass Acari (family Acaridae) and orders Metastigmata and Mestigmata, for example, Acutus, Ornithodoros, Ototrichum, Ixodes, Amblyomma, Boophilus, Dermacentor, Haemaphysalis, Hyalomma, Rhipicephalus, Dermatosaurus, Trichodesmium, Pneumonia, Thoraxygophora and Varroa.

[0501] The orders Acarina (suborder Prospira) and Acarina (suborder Aspira), for example, the genera Bee Shield Mite, Chelicerata, Aviche, Mestocephalus, Acari, Demodex, Chigger Mite, Yak Mite, Mestocephalus, Tyrophagus, Wood Mite, Neck Mite, Wing Mite, Itch Mite, Dermacentor, Otoscabies, Scabies, Otoscabies, Bird Mite, Cell Mite and Chicken Mite.

[0502] The compositions according to the invention are also suitable for protecting materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings, etc. from infestation by insects.

[0503] The composition according to the invention can be used, for example, to combat the following pests: beetles, such as the North American house beetle, the long-haired beetle, the furniture beetle, the red-haired beetle, the comb-horn vein beetle, the dendrobium, the pine bud branch beetle, the pine product beetle, the brown powder beetle, the African powder beetle, the southern powder beetle, the oak powder beetle, the soft-haired powder beetle, the breast powder beetle, the scale-haired powder beetle, the wood beetle, the strip wood beetle, the coffee black long beetle, Tree borers, such as the brown borer, the dimorphothecus, and the bamboo borer; and hymenoptera, such as the blue-black bumblebee, the spruce bumblebee, the Taiga bumblebee, and the giant bumblebee; and termites, such as the European wood termite, the hexatermes, the Indian structural wood termite, the yellow-breasted Reticulitermes, the Sant's Reticulitermes, the Darwin's termite, the Nevada termite, and the formosan termite; and borers, such as silverfish.

[0504] The compounds according to the present invention can be used as pesticides in an unmodified form, but they are usually formulated into compositions using formulation adjuvants such as carriers, solvents, and surfactants in a variety of ways. These formulations can be in different physical forms, for example, in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, flowable oils, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or water-miscible organic solvents as carriers), impregnated polymer films, or in other known forms, for example, from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, 1st edition, second revision (2010). Such formulations can be used directly or can be diluted before use. Dilution can be achieved with, for example, water, liquid fertilizers, micronutrients, biological organisms, oils or solvents.

[0505] These formulations can be prepared, for example, by mixing the active ingredient with 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, vegetable or animal oils, modified vegetable or animal oils, organic solvents, water, surface-active substances or combinations thereof.

[0506] These active ingredients can also be contained in very fine microcapsules. Microcapsules contain active ingredients in porous carriers. This allows the active ingredients to be released into the environment in controlled amounts (e.g., slow release). Microcapsules typically have a diameter of from 0.1 micron to 500 microns. The amount of active ingredient they contain is approximately from 25% to 95% of the capsule weight by weight. These active ingredients can be in the form of a holistic solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulated membrane can include, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymer, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane, or chemically modified polymers and starch xanthate, or other polymers known to those of ordinary skill in the art. Alternatively, very fine microcapsules can be formed, in which the active ingredient is contained in the form of finely dispersed particles in a solid matrix of a base material, but these microcapsules themselves are not wrapped.

[0507] Formulation adjuvants suitable for preparing the compositions according to the invention are known per se. As 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, acetic acid of alkyl acetates, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol rosinate, diethylene glycol ethyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl methylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol, alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, α-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glyceryl acetate, glyceryl diacetate, glyceryl triacetate, Hexadecane, Hexylene Glycol, Isoamyl Acetate, Isobornyl Acetate, Isooctane, Isophorone, Cumene, Isopropyl Myristate, Lactic Acid, Laurylamine, Mesityl Oxide, Methoxypropanol, Methyl Isoamyl Ketone, Methyl Isobutyl Ketone, Methyl Laurate, Methyl Caprylate, Methyl Oleate, Methylene Chloride, m-Xylene, n-Hexane, n-Octylamine, Octadecanoic Acid, Octylamine Acetate, Oleic Acid, Oleylamine, o-Xylene, Phenol, Polyethylene Glycol, Propionic Acid, Propyl Lactate , propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol and higher molecular weight alcohols such as amyl alcohol, tetrahydrofuranol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc.

[0508] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour, soy flour, pumice, wood flour, walnut shell flour, lignin and similar substances.

[0509] Many surface-active substances can be used advantageously in both solid and liquid formulations, especially those which can be diluted with a carrier before use. Surface-active substances can be anionic, cationic, nonionic or polymeric and they can act 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 ethoxylated nonylphenol; alcohol / alkylene oxide addition products, such as ethoxylated tridecanol; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary ammoniums, such as dodecyltrimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkyl phosphates; and also the detergents and emulsifiers described, for example, in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Company (MC Publishing Company). and others as described in Pharmacopoeia Publishing Corp., Ridgewood, NJ (1981).

[0510] Other adjuvants that can be used in pesticidal formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, substances and buffers that neutralize or change the pH, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze agents, microbicides, and liquid and solid fertilizers.

[0511] The composition according to the invention may comprise an additive comprising an oil of plant or animal origin, a mineral oil, an alkyl ester of such an oil or a mixture of such an oil with an oil derivative. The amount of the oil additive in the composition according to the invention is generally from 0.01% to 10% of the mixture to be applied. For example, the oil additive may be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oil or an oil of plant origin, such as rapeseed oil, olive oil or sunflower oil; emulsified vegetable oils; alkyl esters of oils of plant origin, such as methyl derivatives; or oils of animal origin, such as fish oil or tallow. Preferred oil additives include C8-C 22 Alkyl esters of fatty acids, especially C 12 -C 18Methyl derivatives of fatty acids, such as the methyl esters of lauric acid, palmitic acid, and oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th edition, Southern Illinois University, 2010.

[0512] These compositions of the invention generally comprise from 0.1% to 99% by weight, in particular from 0.1% to 95% by weight, of a compound of the invention and from 1% to 99.9% by weight of a formulation adjuvant, which preferably includes from 0 to 25% by weight of a surfactant. While commercial products may preferably be formulated as concentrates, the end user will generally use dilute formulations.

[0513] The rate of application varies within wide limits and depends on the nature of the soil, the method of application, the crop plants, the harmful organisms to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application, and the target crop. In general, the compound can be applied at a rate of from 1 l / ha to 2000 l / ha, in particular from 10 l / ha to 1000 l / ha.

[0514] A preferred formulation may have the following composition (wt %):

[0515] Emulsifiable concentrates :

[0516] Active ingredient: 1% to 95%, preferably 60% to 90%

[0517] Surfactant: 1% to 30%, preferably 5% to 20%

[0518] Liquid carrier: 1% to 80%, preferably 1% to 35%

[0519] Dust agent :

[0520] Active ingredient: 0.1% to 10%, preferably 0.1% to 5%

[0521] Solid carrier: 99.9% to 90%, preferably 99.9% to 99%

[0522] Suspension concentrates :

[0523] Active ingredient: 5% to 75%, preferably 10% to 50%

[0524] Water: 94% to 24%, preferably 88% to 30%

[0525] Surfactant: 1% to 40%, preferably 2% to 30%

[0526] wettable powder :

[0527] Active ingredient: 0.5% to 90%, preferably 1% to 80%

[0528] Surfactants: 0.5% to 20%, preferably 1% to 15%

[0529] Solid carrier: 5% to 95%, preferably 15% to 90%

[0530] Granules:

[0531] Active ingredient: 0.1% to 30%, preferably 0.1% to 15%

[0532] Solid carrier: 99.5% to 70%, preferably 97% to 85%

[0533] The following examples further illustrate (but do not limit) the present invention.

[0534] <![CDATA[ wettable powder ]]> a) b) c) Active ingredient 25％ 50％ 75％ Sodium lignin sulfonate 5％ 5％ - Sodium lauryl sulfate 3％ - 5％ Sodium diisobutylnaphthalenesulfonate - 6％ 10％ Phenol polyglycol ether (7-8 mol ethylene oxide) - 2％ - Highly dispersed silicic acid 5％ 10％ 10％ Kaolin 62％ 27％ -

[0535] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain wettable powders which can be diluted with water to give a suspension of the desired concentration.

[0536]

[0537]

[0538] The combination is thoroughly mixed with adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a dust that can be used directly for seed treatment.

[0539] <![CDATA[ Emulsifiable concentrates ]]> Active ingredient 10％ Octylphenol polyglycol ether (4-5 mol ethylene oxide) 3％ Calcium dodecylbenzenesulfonate 3％ Castor oil polyethylene glycol ether (35 mol ethylene oxide) 4％ Cyclohexanone 30％ Xylene mixture 50％

[0540] Emulsions of any desired dilution which can be used in plant protection can be obtained from these concentrates by dilution with water.

[0541] <![CDATA[ Dust Agent ]]> a) b) c) Active ingredient 5％ 6％ 4％ talc 95％ - - Kaolin - 94％ - Mineral fillers - - 96％

[0542] Ready-to-use dusts are obtained by mixing the combination with a carrier and grinding the mixture in a suitable grinder. Such dusts can also be used for dry dressing of seeds.

[0543] <![CDATA[ Extruder granules ]]> Active ingredient 15％ Sodium lignin sulfonate 2％ Carboxymethyl cellulose 1％ Kaolin 82％

[0544] The combination is mixed with the adjuvants and ground, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

[0545] <![CDATA[ Coated granules ]]> Active ingredient 8％ Polyethylene glycol (molecular weight 200) 3％ Kaolin 89％

[0546] This finely ground combination is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

[0547] Suspension concentrates

[0548] Active ingredient 40％ Propylene glycol 10％ Nonylphenol polyglycol ether (15 mol ethylene oxide) 6％ Sodium lignin sulfonate 10％ Carboxymethyl cellulose 1％ Silicone oil (in the form of a 75% emulsion in water) 1％ water 32％

[0549] The finely ground combination is intimately mixed with an adjuvant to give a suspension concentrate from which a suspension of any desired dilution can be obtained by dilution with water. Using such a dilution, living plants as well as plant propagation material can be treated and protected against microbial infestation by spraying, pouring or immersion.

[0550] Flowable concentrate for seed treatment

[0551] Active ingredient 40％ Propylene glycol 5％ Copolymer butanol PO / EO 2％ Tristyrylphenol with 10-20 moles of EO 2％ 1,2-Benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5％ Monoazo pigment calcium salt 5％ Silicone oil (in the form of a 75% emulsion in water) 0.2％ water 45.3％

[0552] The finely ground combination is intimately mixed with an adjuvant to give a suspension concentrate from which a suspension of any desired dilution can be obtained by dilution with water. Using such a dilution, living plants as well as plant propagation material can be treated and protected against microbial infestation by spraying, pouring or immersion.

[0553] Extended-release capsule suspension

[0554] 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of a defoamer, and 51.6 parts of water until the desired particle size is reached. To this emulsion, 2.8 parts of a mixture of 1,6-hexanediamine in 5.3 parts of water are added. The mixture is stirred until the polymerization reaction is complete. The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% active ingredient. The diameter of the medium capsules is 8 to 15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for this purpose.

[0555] Formulation types include emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oil dispersions (OD), oil suspensions (OF), oil-soluble liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), finished drugs (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG), or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0556] Preparation example:

[0557] "Mpt." refers to the melting point in ° C. Free radical refers to a methyl group. 1 H NMR measurements were recorded on a Brucker 400 MHz spectrometer and chemical shifts are given in ppm relative to a TMS standard. Spectra were measured in deuterated solvents as specified.

[0558] LCMS method:

[0559] Method 1 :

[0560] Spectra were recorded on a Waters mass spectrometer (SQD, SQDII or ZQ single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative, capillary: 3.00 kV, cone range: 30 V-60 V, extractor: 2.00 V, source temperature: 150° C., desolvation temperature: 350° C., cone gas flow: 0 L / Hr, desolvation gas flow: 650 L / Hr; mass range: 100 Da to 900 Da) and an Acquity UPLC from Waters: binary pump, heated column compartment and diode array detector). Solvent degasser, binary pump, heated column compartment and diode array detector. Column: Waters UPLC HSS T3, 1.8 mm, 30 x 2.1 mm, temperature: 60°C, DAD wavelength range (nm): 210 to 500, solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; gradient: 10%-100% B in 1.2 min; flow rate (mL / min) 0.85

[0561] Example H1: 2-[3-Ethylsulfonyl-6-[3-(trifluoromethyl)pyrazol-1-yl]-2-pyridinyl]-3-methyl-6- (Trifluoromethyl)imidazo[4,5-c]pyridine (Compound P3, Table P):

[0562] (Compound P3, Table P)

[0563] Step A: tert-Butyl N-[4-amino-6-(trifluoromethyl)-3-pyridinyl]carbamate

[0564]

[0565] To a solution of 6-(trifluoromethyl)pyridine-3,4-diamine (3.14 g, 17.73 mmol, prepared as described in US 7,767,687) in tetrahydrofuran (50 ml) was added tert-butoxycarbonyl tert-butyl carbonate (4.64 g, 21.27 mmol) and the mixture was stirred at 50 ° C. After 8 hours, an additional 1.1 g (5.0 mmol) of tert-butoxycarbonyl tert-butyl carbonate was added and stirring was continued at 50 ° C. for another 4 hours. The reaction mixture was then concentrated in vacuo, and the brown residue was suspended in dichloromethane, filtered and dried in vacuo to give the title compound as white crystals. LCMS (Method A): Retention time: 0.79 min; 278 (M+H).

[0566] Step B: tert-N-[4-amino-6-(trifluoromethyl)-3-pyridinyl]-N-methyl-carbamic acid butyl ester

[0567]

[0568] To a stirred suspension of sodium hydride (0.648 g, 14.85 mmol) in 30 ml of N,N-dimethylformamide was added dropwise tert-butyl N-[4-amino-6-(trifluoromethyl)-3-pyridyl]carbamate (3.92 g, 14.14 mmol) dissolved in 20 ml of N,N-dimethylformamide at 20-25 ° C over a period of 20 min. After stirring at ambient temperature for 15 min, iodomethane (2.21 g, 15.55 mmol) was added. After 30 min at ambient temperature, the mixture was poured onto 200 ml of water, extracted twice with ethyl acetate, and the combined organic fractions were washed sequentially with water and brine, dried over Na2SO4, and concentrated in vacuo. The crude product was recrystallized from ethyl acetate / heptane to give the title compound (3.18 g) as white crystals. LCMS (method A): retention time: 0.85 min; 292 (M+H).

[0569] Step C: N3-methyl-6-(trifluoromethyl)pyridine-3,4-diamine

[0570]

[0571] To a clear, colorless solution of N-[4-amino-6-(trifluoromethyl)-3-pyridyl]-N-methyl-carbamic acid tert-butyl ester (3.53 g, 12.119 mmol) in dioxane was added hydrogen chloride (18 mL of a 2M solution in water, 36.36 mmol), and the mixture was heated to reflux. After gas evolution ceased, the reaction mixture was cooled to room temperature and treated with solid sodium bicarbonate (3.1 g, 36.9 mmol). The slurry was diluted with water and extracted twice with ethyl acetate. The combined organic layers were washed sequentially with water and brine, dried over Na2SO4 and concentrated in vacuo to give 2.25 g of the title compound as colorless crystals, MPt 138°C-140°C. LCMS (method A): retention time 0.24 min, 192 (M+H).

[0572] Alternatively, N3-methyl-6-(trifluoromethyl)pyridine-3,4-diamine can be obtained by the following procedure:

[0573] To a solution of 6-(trifluoromethyl)pyridine-3,4-diamine (2.0 g, 12.2 mmol) and potassium carbonate (3.2 g, 23.1 mmol) in acetonitrile (10 mL) was added iodomethane (0.8 mL). The reaction mixture was stirred at 30 ° C for 18 hours. The potassium carbonate was filtered off, and the filtrate was dried in vacuo and purified using a silica gel chromatography column (petroleum: ethyl acetate = 4: 3) to provide the title compound (0.32 g) as a light yellow solid. 1 H NMR (400MHz, DMSO-d6): δ (ppm) 7.57 (s, 1H), 6.83 (s, 1H), 5.82 (s, 2H), 5.23 (d, J = 4.8Hz, 1H), 2.80 (d, J = 4.8Hz, 3H). 19 F NMR (300MHz, DMSO-d6): δ (ppm)-60.12 (s, 3F).

[0574] Step D: N-[4-amino-6-(trifluoromethyl)-3-pyridinyl]-3-ethylsulfonyl-N-methyl-pyridine-2-carboxylate Amide and 3-ethylsulfonyl-N-[5-(methylamino)-2-(trifluoromethyl)-4-pyridinyl]pyridine-2-carboxamide:

[0575]

[0576] To a solution of N3-methyl-6-(trifluoromethyl)pyridine-3,4-diamine (16.70 g, 87.37 mmol) in THF (167.0 mL) was added Et3N (22.32 g, 218.4 mmol). The reaction mixture was cooled to 0 ° C., and at 0-10 ° C., 3-ethylsulfonylpyridine-2-carbonyl chloride (18.37 g, 78.63 mmol, prepared as described in WO2013 018928) dissolved in dichloromethane (170 mL) was added dropwise to the mixture over 1 hour. After 1.5 hours, LC / MS detected the desired product at Rt=0.74. The ice bath was removed, and the reaction mixture was allowed to warm to ambient temperature and stirred for 12 hours. The reaction mixture was then diluted with saturated NH4Cl, the organic phase was separated, and the aqueous phase was stripped with dichloromethane. The combined organic phases were washed with water, brine, dried over Na SO dried, filtered and concentrated in vacuo to give a crude product. The crude product was dissolved in dichloromethane and adsorbed on a Teflon bulk adsorbent and purified on a silica gel column (Rf 00) eluting with cyclohexane / ethyl acetate. This gave a crude title product as a mixture of amide regioisomers which was used in the next step without further purification.

[0577] LCMS (Method 1); Rt=0.73 min, [M+H]389 and 0.8 min [M+H]389.

[0578] Step E: 2-(3-ethylsulfonyl-2-pyridinyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine:

[0579]

[0580] A yellow solution of the crude product mixture from Step D (26.72 g, 68.80 mmol) in acetic acid 270 mL was stirred overnight at 120° C. After cooling, the mixture was diluted with toluene and concentrated in vacuo.

[0581] The crude product was dissolved in dichloromethane and adsorbed onto Teflon bulk adsorbent and purified on a silica gel column (TORENT) eluting with heptane:EtOAc to give the title product as a beige solid.

[0582] LCMS (method 1): retention time 0.78 minutes, (M+H)=371. 1H NMR (400 MHz, chloroform-d) δ ppm: 1.36 (t, J = 7.3 Hz, 3H); 3.77 (q, J = 7.3 Hz, 2H); 3.90 (s, 3H); 7.77 (dd, J = 8.1, 4.8 Hz, 1H); 8.12 (s, 1H); 8.55 (dd, J = 8.1, 1.8 Hz, 1H); 9.00 (s, 1H); 9.02 (dd, J = 4.8, 1.8 Hz, 1H).

[0583] Step F: 2-(3-Ethylsulfonyl-1-oxido-pyridin-1-ium-2-yl)-3-methyl-6-(trifluoromethyl)imidazole 4,5-c]pyridine (A):

[0584]

[0585] Method A:

[0586] To a solution of 2-(3-ethylsulfonyl-2-pyridinyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (18.70 g, 50.49 mmol) in dichloromethane (187.0 mL) was added m-chloroperbenzoic acid (13.69 g, 55.53 mmol). The yellow solution was stirred at ambient temperature for 18 hours. After this time, the reaction mixture was cooled to ambient temperature and diluted with aqueous sodium thiosulfate solution. The reaction mixture was extracted with dichloromethane, and the combined organic fractions were washed with Na2CO3, dried over MgSO4, and concentrated in vacuo. The crude product was dissolved in dichloromethane and adsorbed on Teflon bulk adsorbent and purified on a silica gel column (TORENT) eluting with heptane / ethyl acetate and then dichloromethane:methanol. This gave the title product as the first eluting product.

[0587] LCMS (method 1): retention time 0.72 min, (M+H)=387. 1 H NMR (400Mhz, chloroform-d) δppm; 1.35 (t, J = 7.5Hz, 3H); 3.39-3.52 (m, 1H); 3.66-3.82 (m, 1H); 3.87 (s, 3H); 7.71 (dd, J =8.1, 6.6Hz, 1H); 8.00 (dd, J = 8.1, 0.7Hz, 1H); 8.13 (d, J = 0.7Hz, 1H); 8.55 (dd, J = 6.6, 0.7Hz, 1H) 9.03 (s, 1H).

[0588] The second eluting product is

[0589] 2-(3-ethylsulfonyl-2-pyridyl)-3-methyl-5-oxido-6-(trifluoromethyl)imidazo[4, 5-c]pyridin-5-ium (B):

[0590]

[0591] LCMS (method 1): retention time 0.64 min, (M+H)=387. 1 H NMR (400Mhz, chloroform-d) δppm: 1.37 (t, J = 7.5Hz, 3H); 3.76 (q, J = 7.5Hz, 2H); 3.77 (s, 3H); 7.77 (dd, J = 8. 1,4.8Hz,1H);8.09(s,1H);8.55(dd,J=8.1,1.5Hz,1H);8.71(s,1H);9.01(dd,J=4.8,1.5Hz,1H).

[0592] Isolated as the third eluting product

[0593] 2-(3-Ethylsulfonyl-1-oxido-pyridin-1-ium-2-yl)-3-methyl-5-oxido-6-(trifluoromethyl)imidazole 4,5-c]pyridin-5-ium (C):

[0594]

[0595] LCMS (method 1): retention time 0.55 min, (M+H)=403. 1 H NMR (400Mhz, chloroform-d) δppm: 1.36 (t, J = 7.3Hz, 3H); 3.33-3.54 (m, 1H); 3.60-3.80 (m, 1H); 7.72 (dd, J = 8 .1, 6.6Hz, 1H); 7.99 (dd, J = 8.1, 0.7Hz, 1H); 8.10 (s, 1H); 8.54 (dd, J = 6.6, 0.7Hz, 1H); 8.68 (s, 1H).

[0596] The ratio of the products is (A):(B):(C) 9:15:1.

[0597] Method B:

[0598] At 0 ° C, to a solution of 2-(3-ethylsulfonyl-2-pyridinyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (1.00 g, 2.70 mmol) and urea hydroperoxide (0.288 g, 1.10 equivalents, 2.97 mmol) in dichloromethane (10.0 mL) was slowly added trifluoroacetic anhydride (1.15 g, 0.759 mL, 5.40 mmol). After 30 minutes, the ice bath was removed and the reaction mixture was allowed to warm to ambient temperature. LC / MS after 3 hours detected the desired product at Rt=0.72, product B at Rt=0.64, and product D at Rt=0.55. It was stirred at ambient temperature over the weekend. Processing and purification according to method A gave the same three products (A):(B):(C) in a ratio of 9:3:1.

[0599] Step G: 2-(6-chloro-3-ethylsulfonyl-2-pyridinyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c] Pyridine

[0600]

[0601] 2- (3- ethylsulfonyl -1- oxidation - pyridin -1- ium -2- bases) -3- methyl -6- (trifluoromethyl) imidazo [4,5-c] pyridine (1.38g, 1.00 equivalents, 3.57mmol) and phosphorus oxychloride (29.61g, 18mL, 53.5 equivalents, 191.2mmol) are mixed in a microwave vial and heated in a microwave at 130 DEG C for 6 hours. After this time, LC / MS shows that the reaction is complete. The reaction mixture is concentrated in vacuo and purified on a silica gel column (Rf200) using cyclohexane: ethyl acetate elution to give the title compound as a white solid:

[0602] LCMS (Method 1): Retention time 0.95 min, (M+H)=405 / 407. 1 H NMR (400 MHz, chloroform-d) δ ppm: 1.41 (t, J = 7.5 Hz, 3H); 3.64 (q, J = 7.5 Hz, 2H); 4.11 (s, 3H); 7.89 (d, J = 8.4 Hz, 1H); 8.49 (d, J = 8.4 Hz, 1H); 9.65 (s, 1H).

[0603] Step H: 2-[3-ethylsulfonyl-6-[3-(trifluoromethyl)pyrazol-1-yl]-2-pyridinyl]-3-methyl-6- (Trifluoromethyl)imidazo[4,5-c]pyridine (Compound P3, Table P):

[0604] (Compound P3, Table P)

[0605] The solution of 3-(trifluoromethyl)-1H-pyrazole (0.034g, 0.25mmol) in DMF (2.0mL, 26mmol) is cooled to 0 DEG C and processed with sodium hydride (60% in oil, 0.013g, 0.32mmol).The reaction was stirred at 0 DEG C for 20 minutes, and then processed with 2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (0.10g, 0.25mmol) and allowed to heat the reaction and stir at ambient temperature. After 30 minutes, LCMS showed that the reaction was complete.The reaction was diluted with tert-butyl dimethyl ether, and then saturated NaHCO solution was quenched.The organic layer was separated, washed with water and salt water 2x, through Na SO Drying, filtered and concentrated in a vacuum. The crude product was dissolved in dichloromethane, adsorbed on Teflon bulk adsorbent and then purified on a silica gel column (Rf 200) (eluting with cyclohexane / ethyl acetate) to give the title compound as a white solid. Mpt. 261° C.-263° C.

[0606] LCMS (method 1): retention time 1.07 min, (M+H)=505. 1 H NMR (400Mhz, chloroform-d) δppm: 1.38 (t, J = 7.5Hz, 3H); 3.73 (q, J = 7.5Hz, 2H); 3.93 (s, 3H); 6.80 (d, J = 2.6Hz, 1H); 8 .15 (d, J = 0.7Hz, 1H); 8.45 (d, J = 8.8Hz, 1H); 8.59 (dd, J = 2.6, 0.92Hz, 1H) 8.68 (d, J = 8.8Hz, 1H) 9.04 (s, 1H).

[0607] Example H2: 2-[6-(4-chlorophenyl)-3-ethylsulfonyl-2-pyridinyl]-3-methyl-6-(trifluoromethyl)imidazole 4,5-c]pyridine (Compound P1, Table P):

[0608] (Compound P1, Table P)

[0609] In a SUPELCO vial, 2-(6-chloro-3-ethylsulfonyl-2-pyridinyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (Step G, Example P1, 0.04 g, 0.1 mmol) dissolved in 1,4-dioxane (1 mL) was treated with (4-chlorophenyl)boronic acid (0.02 g, 0.1 mmol) and anhydrous K2CO3 (0.04 g, 0.3 mmol) and the mixture was purged with argon for 10 minutes. Palladium-tris-triphenylphosphine (0.01 g, 0.01 mmol) was then added and the solution was heated at 100 ° C. LCMS analysis after 4 hours showed that the reaction was complete. The reaction mixture was diluted with water and ethyl acetate, the organic layer was separated, washed with brine, dried over Na2SO4, filtered, evaporated and concentrated in vacuo. The crude product was dissolved in dichloromethane, adsorbed on Teflon bulk adsorbent and then purified on a silica gel column (Rf200) (eluting with cyclohexane / ethyl acetate) to give the title compound as a yellow solid. Mpt 255-256°C.

[0610] LCMS (method 1): retention time 1.11 min, (M+H)=481 / 483. 1 H NMR (400Mhz, chloroform-d) δppm: 1.39 (t, J = 7.5Hz, 3H); 3.79 (q, J = 7.5Hz, 2H); 3.95 (s, 3H); 7.51 (d, J = 8.8Hz , 2H); 8.06 (d, J = 8.8Hz, 2H); 8.11 (d, J = 8.4Hz, 1H;) 8.15 (s, 1H); 8.57 (d, J = 8.4Hz, 1H); 9.02 (s, 1H).

[0611] Example H3: 2-[3-ethylsulfonyl-6-[(E)-2-[2-(trifluoromethyl)phenyl]vinyl]-2-pyridinyl]- 3-Methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (Compound P2, Table P):

[0612] (Compound P2, Table P)

[0613] In a microwave vial, 2-(6-chloro-3-ethylsulfonyl-2-pyridinyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (Step G, Example P1, 0.10 g, 0.25 mmol), anhydrous KCO (0.068 g, 0.49 mmol), 2-(trifluoromethyl)styrene (0.043 g, 0.037 mL, 0.25 mmol) dissolved in acetonitrile were degassed with argon. To this mixture was added palladium(II) acetate (0.0051 g, 0.022 mmol), and the mixture was then heated at 140° C. for 45 minutes. After this time, additional portions of 2-(trifluoromethyl)styrene (0.074 mL) and palladium(II) acetate (0.0028 g, 0.050 equiv, 0.012 mmol) were added and the mixture was heated in a microwave at 140° C. for 1 hour. At this time, reaction mixture is filtered through hyflo, and filtrate is diluted with ethyl acetate and successively uses 1N HCl, water and salt water washing, through Na SO Drying is filtered and concentrated in a vacuum.Crude product is dissolved in dichloromethane, is adsorbed on Teflon bulk adsorbent, and is purified with cyclohexane / ethyl acetate wash-out on silica gel column (Rf 00).Be further purified by reversed-phase HPLC, provide the title compound that is white foam.

[0614] LCMS (method 1): retention time 1.14 min, (M+H)=541. 1 H NMR (400Mhz, chloroform-d) δppm: 1.40 (t, J = 7.3Hz, 3H); 3.86 (q, J = 7.34Hz, 2H); 4.00 (s, 3H); 7.24 (d, J = 15.7Hz, 1H); 7.46-7.52 (m, 1H); 7.62 ( t,J=7.5Hz,1H);7.71-7.77(m,2H)7.85(d,J=7.75Hz,1H)8.14(s,1H)8.25(dd,J=15.7,2.20Hz,1H)8.51(d,J=8.4Hz,1H)9.03(s,1H).

[0615] Example H4: 2-[3-Ethylsulfonyl-5-(trifluoromethyl)-6-[4-(trifluoromethyl)phenyl]-2-pyridinyl]-3- Methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (Compound P4, Table P)

[0616] (Compound P4, Table P)

[0617] Step A: 3-ethylsulfanyl-5-(trifluoromethyl)pyridine-2-carboxylic acid methyl ester:

[0618]

[0619] A solution of 3-chloro-5-(trifluoromethyl)pyridine-2-formic acid methyl ester (30g, 125mmol, CAS registration number [655235-65-7]) was dissolved in DMF (630mL), sodium ethanethiolate (12.87g, 138mmol) was added portionwise, keeping the temperature below 20°C. The reaction mixture was allowed to stir overnight, after which LCMS analysis showed that the reaction was complete. The mixture was diluted with water, extracted with AcOEt (3 times), and the combined organic phases were washed with saturated aqueous NH4Cl and salt water, dried over MgSO4 and concentrated in vacuo. The crude title compound was used for the next step without further purification.

[0620] LCMS (Method 1); Rt=0.96 min, [M+H]266. 1 H NMR (400 MHz, chloroform-d) δ

[0621] ppm: 1.43 (t, J = 7.5Hz, 3H); 3.00 (q, J = 7.5Hz, 2H); 4.04 (s, 3H); 7.87 (d, J = 1.1Hz, 1H); 8.66 (d, J = 1.1Hz, 1H).

[0622] Step B: Methyl 3-ethylsulfonyl-5-(trifluoromethyl)pyridine-2-carboxylate

[0623]

[0624] A solution of 3-ethylsulfanyl-5-(trifluoromethyl)pyridine-2-formic acid methyl ester (5.94g, 22.4mmol) in dichloromethane (200mL) was cooled to 0°C. At 0°C, m-CPBA (11.0g, 44.8mmol) was added to this solution in small portions. After 2 hours, the solution was allowed to warm to ambient temperature and stirred at ambient temperature for 3 hours, after which LCMS showed that the reaction was complete. The reaction mixture was poured into an aqueous solution of NaHCO and a saturated aqueous solution of sodium thiosulfate. The mixture was then extracted with dichloromethane (3x), washed with brine, dried over MgSO and concentrated in vacuo. The crude product was purified by Combi flash chromatography using a gradient elution of cyclohexane+0-30% ethyl acetate. This gave the title compound as a white solid.

[0625] LCMS (Method 1); Rt=0.76 min, [M+H]298. 1 H NMR (400 MHz, chloroform-d) δ ppm: 1.39 (t, J = 7.5 Hz, 3H); 3.57 (q, J = 7.5 Hz, 2H); 4.08 (s, 3H); 8.61 (d, J = 1.8 Hz, 1H); 9.11 (d, J = 1.8 Hz, 1H).

[0626] Step C: Methyl 3-ethylsulfonyl-1-oxido-5-(trifluoromethyl)pyridin-1-ium-2-carboxylate

[0627]

[0628] A solution of 3-ethylsulfonyl-5-(trifluoromethyl)pyridine-2-formic acid methyl ester (7.5g, 25mmol, prepared as described above) in dichloromethane (80mL) is cooled to 0 DEG C and urea hydrogen peroxide complex (5.1g, 53mmol) is added in small portions. Trifluoroacetic anhydride (11g, 7.2mL, 50.0mmol) is added to the mixture, keeping the reaction temperature at 0 DEG C. The reaction mixture is allowed to be warmed to room temperature and stirred overnight. After this, the reaction is quenched with aqueous sodium bisulfite solution and stirred for 15 minutes. The gained mixture is poured into 0.5M HCl and extracted 3 times with dichloromethane. The organic extracts merged are washed with NaHCO aqueous solution, through Na SO dried, filtered and concentrated in a vacuum. The crude product is purified by Combi flash chromatography with the gradient elution of cyclohexane+0-100% ethyl acetate to give the title compound as a white solid.

[0629] LCMS (Method 1); Rt=0.70 min, [M+H]314. 1 H NMR (400 MHz, chloroform-d) δ ppm: 1.39 (t, J = 7.5 Hz, 3H); 3.38 (q, J = 7.5 Hz, 2H); 4.08 (s, 3H); 7.93 (d, J = 0.7 Hz, 1H); 8.62 (d, J = 0.7 Hz, 1H).

[0630] Step D: Methyl 6-chloro-3-ethylsulfonyl-5-(trifluoromethyl)pyridine-2-carboxylate

[0631]

[0632] The sample of 3-ethylsulfonyl-1-oxidation-5-(trifluoromethyl)pyridin-1-ium-2-methyl-formiate (1.43g, 4.57mmol) and phosphorus oxychloride (24.3mL) is placed in two microwave vials, and the vial is stirred at 130 DEG C in microwave for 6 hours.After this time, the contents of the vial are merged and concentrated in vacuo. The crude product is purified by eluting with cyclohexane / ethyl acetate on silica gel column (Rf200), to give the title product as white crystals.

[0633] 1 H NMR (400 MHz, chloroform-d) δ ppm: 1.39 (t, J = 7.5 Hz, 3H); 3.55 (q, J = 7.5 Hz, 2H); 4.07 (s, 3H); 8.61 (s, 1H).

[0634] Step E: Methyl 3-ethylsulfonyl-5-(trifluoromethyl)-6-[4-(trifluoromethyl)phenyl]pyridine-2-carboxylate ester:

[0635]

[0636] A solution of methyl 6-chloro-3-ethylsulfonyl-5-(trifluoromethyl)pyridine-2-carboxylate (0.285 g, 0.86 mmol) in 1,4-dioxane (7 mL) was treated with [4-(trifluoromethyl)phenyl]boronic acid (0.212 g, 1.12 mmol) and anhydrous KCO (0.356 g, 3.00 eq, 2.58 mmol) and the mixture was purged with argon for 10 minutes. To this mixture was added tetrakis(triphenylphosphine)palladium(0) (0.0993 g, 0.100 eq, 0.0859 mmol) and the solution was heated at 100 ° C for 3 hours, after which time LCMS showed good reaction conversion. The reaction mixture was diluted with a saturated solution of NH4Cl, water, and ethyl acetate. The organic phase was separated, washed with brine, dried over Na2SO4, filtered, and concentrated in vacuo. The crude product was dissolved in dichloromethane and adsorbed onto Teflon bulk adsorbent. Purification on a silica gel column (Rf 200) eluting with cyclohexane / ethyl acetate gave the title compound as a white solid.

[0637] LCMS (Method 1); Rt=1.09 min, [M+H]442. 1 H NMR (400 MHz, chloroform-d) δ ppm: 1.44 (t, J = 7.5 Hz, 3H); 3.59 (q, J = 7.5 Hz, 2H); 4.06 (s, 3H); 7.70 (d, J = 8.0 Hz, 2H); 7.78 (d, J = 8.0 Hz, 2H); 8.73 (s, 1H).

[0638] Step F: 3-Ethylsulfonyl-5-(trifluoromethyl)-6-[4-(trifluoromethyl)phenyl]pyridine-2-carboxylic acid:

[0639]

[0640] At ambient temperature, 3-ethylsulfonyl-5-(trifluoromethyl)-6-[4-(trifluoromethyl)phenyl]pyridine-2-carboxylic acid methyl ester (0.28 g, 0.63 mmol) was dissolved in tetrahydrofuran / H2O 3: 1 (10 mL) and treated with lithium hydroxide hydrate (0.028 g, 0.67 mmol). LCMS analysis after stirring for 3 hours showed a reaction. The reaction mixture was concentrated in vacuo and absorbed in ethyl acetate and 10% aqueous HCl. The organic layer was separated and washed with brine, dried over Na2SO4, filtered and concentrated in vacuo to give the title compound as a beige solid, which was used in the next step without further purification.

[0641] LCMS (Method 1); Rt=0.88 min, [M+H]428. 1 H NMR (400 MHz, chloroform-d) δ ppm 1.42 (t, J = 7.3 Hz, 3H): 3.75 (q, J = 7.3 Hz, 2H): 4.98 (br. s., 1H); 7.70 (d, J = 7.8 Hz, 2H); 7.79 (d, J = 7.8 Hz, 2H): 8.86 (s, 1H).

[0642] Step G: 3-Ethylsulfonyl-N-[5-(methylamino)-2-(trifluoromethyl)-4-pyridinyl]-5-(trifluoromethyl)- N-[4-amino-6-(trifluoromethyl)phenyl]pyridine-2-carboxamide and N-[4-amino-6-(trifluoromethyl)-3-pyridyl]-3-ethyl Sulfonyl-N-methyl-5-(trifluoromethyl)-6-[4-(trifluoromethyl)phenyl]pyridine-2-carboxamide:

[0643]

[0644] A solution of 3-ethylsulfonyl-5-(trifluoromethyl)-6-[4-(trifluoromethyl)phenyl]pyridine-2-carboxylic acid (0.10 g, 0.23 mmol), EDCI (0.049 g, 0.26 mmol) and N3-methyl-6-(trifluoromethyl)pyridine-3,4-diamine (0.049 g, 0.26 mmol, step C, example P1) in pyridine (3.0 mL) was stirred at 120 ° C. After 2 hours, LC / MS showed sufficient reaction progress for treatment. The reaction mixture was poured into water and extracted with ethyl acetate (X3). The combined organic layer was washed with brine, dried over Na2SO4 and concentrated in vacuo. The crude product was dissolved in dichloromethane and adsorbed on Teflon bulk adsorbent. Purified on a silica gel column (Rf200), eluted with a cyclohexane / ethyl acetate gradient, to give a mixture of the title compound as a yellow solid.

[0645] LCMS (Method 1); Rt = 1.10 min, [M+H] 601; Rt = 1.14 min, [M+H] 601;

[0646] Step H: 2-[3-ethylsulfonyl-5-(trifluoromethyl)-6-[4-(trifluoromethyl)phenyl]-2-pyridinyl]-3- Methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (Compound P4, Table P):

[0647] (Compound P4, Table P)

[0648] A yellow solution of 3-ethylsulfonyl-N-[5-(methylamino)-2-(trifluoromethyl)-4-pyridinyl]-5-(trifluoromethyl)-4-pyridinyl]-5-(trifluoromethyl)-6-[4-(trifluoromethyl)phenyl]pyridine-2-carboxamide and N-[4-amino-6-(trifluoromethyl)-3-pyridinyl]-3-ethylsulfonyl-N-methyl-5-(trifluoromethyl)-6-[4-(trifluoromethyl)phenyl]pyridine-2-carboxamide (0.055 g, 0.092 mmol) in acetic acid (1 mL) was stirred at 120 ° C for 18 hours. After this time, LCMS analysis showed that the reaction was complete. The reaction mixture was cooled to ambient temperature, diluted with toluene and concentrated in vacuo. The crude product was dissolved in dichloromethane and adsorbed on Teflon bulk adsorbent. Purification on a silica gel column (Rf 200) eluting with a cyclohexane / ethyl acetate gradient gave a mixture of the title compounds as a white solid. Mpt. 140-142°C.

[0649] LCMS (Method 1); Rt=1.17 min, [M+H]583. 1 H NMR (400 MHz, chloroform-d) δ ppm 1.47 (t, J = 7.5 Hz, 3H); 3.94 (q, J = 7.5 Hz, 2H); 7.72-7.76 (m, 2H); 7.78-7.82 (m, 2H); 3.94 (q, J = 7.34 Hz, 2H); 3.96 (s, 3H); 8.92 (s, 1H); 9.01 (s, 1H).

[0650] Example H5: 2-(6-cyclopropyl-3-ethylsulfonyl-2-pyridinyl)-3-methyl-6-(trifluoromethyl)imidazolin [4,5-c]pyridine (Compound P15, Table P)

[0651] (Compound P15, Table P)

[0652] Step A: 3,6-Dichloropyridine-2-carbonyl chloride

[0653]

[0654] A sample of 3,6-dichloropyridine-2-carboxylic acid (5.00 g, 24.7 mmol) was diluted in dichloromethane (200 mL) and dimethylformamide (0.124 mL, 1.6 mmol) was added. Oxalyl chloride (3.15 mL, 34.6 mmol) was added dropwise to the solution at room temperature over 10 minutes (gas evolution). The reaction mixture was stirred at room temperature, and after 2.5 hours, an additional 1 ml of oxalyl chloride was added and stirring continued for 1 hour. After this time, the reaction mixture was concentrated in vacuo and used in the next step without further purification.

[0655] Step B: 3,6-dichloro-N-[5-(methylamino)-2-(trifluoromethyl)-4-pyridinyl]pyridine-2-carboxamide

[0656]

[0657] To a solution of N3-methyl-6-(trifluoromethyl)pyridine-3,4-diamine (52.0 g, 272 mmol) in tetrahydrofuran (260 mL) was added triethylamine (95.8 mL, 680 mmol). The red solution was cooled to 0 ° C, and at 0-10 ° C, 3,6-dichloropyridine-2-carbonyl chloride (51.5 g, 245 mmol) in dichloromethane (156 mL) was added dropwise over 90 minutes. The ice bath was removed after 1 hour, and the mixture was stirred at room temperature. After 2 hours, LC-MS analysis showed the main desired substance. The reaction mixture was stirred overnight, and then washed with a saturated solution of NH4Cl, and the mixture was concentrated in vacuo to remove tetrahydrofuran. The residue was then extracted with 1.2 L dichloromethane (800 mL) ethyl acetate and 1 L dichloromethane. The combined organic layer was dried over Na2SO4, filtered and concentrated in vacuo to give the title compound as a brown solid.

[0658] LCMS (method 1): 366 (M+H + ); retention time: 0.83 min.

[0659] Step C: 2-(3,6-dichloro-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine

[0660]

[0661] A yellow solution of 3,6-dichloro-N-[5-(methylamino)-2-(trifluoromethyl)-4-pyridyl]pyridine-2-carboxamide (99.3g, 272mmol) in acetic acid (298mL) was stirred at 110°C bath temperatures for 16 hours. The reaction mixture was allowed to reach room temperature, after which time LC-MS analysis showed the desired substance. Toluene was added and the mixture was concentrated in a vacuum. Cyclohexane and dichloromethane were added to the residue, and the obtained mixture was stirred at 800mbar at 50°C under vacuum. The slurry was further diluted with cyclohexane, and the solid was filtered on a pump. The filter cake was washed with cyclohexane (mixed with a small amount of DCM) and dried under vacuum. Toluene was added, and the mixture was evaporated and dried at 60°C and 20mbar vacuum to remove traces of acetic acid, giving the title compound as a brown solid.

[0662] LCMS (method 1): 348 (M+H + ); retention time: 0.95min.

[0663] 1 H NMR (400 MHz, chloroform-d) δ ppm 4.04 (s, 3H) 7.51 (d, J = 8.44 Hz, 1H) 7.93 (d, J = 8.44 Hz, 1H) 8.19 (s, 1H) 8.99 (s, 1H)

[0664] Step D: 2-(6-chloro-3-ethylsulfanyl-2-pyridinyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c] Pyridine

[0665]

[0666] Under argon, a sample of 2-(3,6-dichloro-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (1.14 g, 3.28 mmol) was dissolved in tetrahydrofuran. Sodium ethanethiolate (0.311 g, 3.28 mmol) was added in batches at room temperature. The brown reaction mixture was stirred at room temperature for 2 hours, when LC-MS analysis showed that the reaction was complete and the desired product was formed. The reaction mixture was treated with NH4Cl and then with water and ethyl acetate. The organic layer was separated, washed with water and brine, dried over Na2SO4, filtered and concentrated in vacuo. The crude product was purified by flash chromatography on silica gel to give the title compound as a beige solid.

[0667] LCMS (method 1): 373 (M+H+); retention time: 1.02 min.

[0668] 1H NMR (400 MHz, chloroform-d) δ ppm 1.35 (t, J = 7.34 Hz, 3H) 2.97 (q, J = 7.34 Hz, 2H) 4.11 (s, 3H) 7.44 (d, J = 8.44 Hz, 1H) 7.76 (d, J = 8.44 Hz, 1H) 8.20 (d, J = 0.73 Hz, 1H) 8.97 (s, 1H)

[0669] Step E: 2-(6-chloro-3-ethylsulfonyl-2-pyridinyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c] Pyridine

[0670]

[0671] At 0 ° C, m-CPBA (2.35g, 10.5mmol) is added to a solution of 2-(6-chloro-3-ethylsulfanyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (1.86g, 4.99mmol) in chloroform (46.5mL). After addition, the ice bath is kept for 10 minutes, and the milky solution is then allowed to warm to room temperature. The reaction mixture is stirred at room temperature overnight. After this time, a portion of M-CPBA (1.12g, 4.99mmol) is added and the mixture is stirred at room temperature for 2 hours. LC-MS analysis shows that the reaction is complete. Saturated aqueous sodium thiosulfate solution and saturated aqueous NaHCO are added and the mixture is stirred for 1 hour. The organic layer is separated, extracted with NaHCO, dried over NaSO and evaporated. The crude product is purified by flash chromatography on silica gel to give the title compound as a white solid.

[0672] LCMS (method 1): 406 (M+H+); retention time: 0.95 min.

[0673] 1 H NMR (400 MHz, chloroform-d) δ ppm 1.37 (t, J = 7.34 Hz, 3H) 3.79 (q, J = 7.46 Hz, 2H) 3.94 (s, 3H) 7.75 (d, J = 8.44 Hz, 1H) 8.11 (s, 1H) 8.47 (d, J = 8.44 Hz, 1H) 9.00 (s, 1H)

[0674] Step F: 2-(6-cyclopropyl-3-ethylsulfonyl-2-pyridinyl)-3-methyl-6-(trifluoromethyl)imidazo[4, 5-c]pyridine (Compound P15, Table P)

[0675] (Compound P15, Table P)

[0676] In a Supelco vial, 2-(6-chloro-3-ethylsulfonyl-2-pyridinyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (0.40 g, 0.99 mmol) was dissolved in 1,4-dioxane (10 mL, 120 mmol). Cyclopropylboronic acid (0.18 g, 2.0 mmol) and potassium carbonate (0.41 g, 3.0 mmol) were added, and the mixture was purged with argon. Tetrakis(triphenylphosphine)palladium (0.11 g, 0.099 mmol) was then added, the vial was capped and the brown solution was heated at 100 ° C for 19 hours. LC-MS analysis showed the formation of the desired product. Water and ethyl acetate were added, the organic layer was separated, washed with brine, dried over Na2SO4, filtered and concentrated in vacuo. The crude product obtained was purified by flash chromatography on silica gel. The obtained mixture was dissolved in ethyl acetate and washed again with NaHCO3. The organic layer was washed with brine, dried over Na2SO4, filtered and evaporated.The obtained solid was purified again by reverse phase to give the title compound as a white solid.

[0677] LCMS (method 1): 411 (M+H + ); retention time: 1.01 min.

[0678] 1H NMR (400Mhz, chloroform-d) δppm 1.11-1.13(m,1H)1.11-1.23(m,4H)1.33(t,J=7.34Hz,3H)2.22(ddd,J=7.70,4.77,2.93Hz,1H)3.7 0(q,J=7.34Hz,2H)3.84(s,3H)7.54(d,J=8.44Hz,1H)8.09(s,1H)8.30(d,J=8.44Hz,1H)8.97(s,1H)

[0679] Example H6: 2-[6-(3,5-difluorophenyl)-3-ethylsulfonyl-2-pyridinyl]-3-methyl-6-(trifluoromethyl) Imidazo[4,5-c]pyridine (Compound P8, Table P)

[0680] (Compound P8, Table P)

[0681] In a Supelco vial, 2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (100 mg, 0.2470 mmol), (3,5-difluorophenyl)boric acid (46 mg, 0.2964 mmol) and potassium carbonate (102 mg, 0.7411 mmol) were dissolved in 1,4-dioxane (2.5 mL). The resulting mixture was flushed with argon for 5 minutes. After this time, tetrakis(triphenylphosphine)palladium (28 mg, 0.02470 mmol) was added, and the vial was sealed and heated at 95 ° C for 16 hours. LC-MS analysis showed that the reaction was complete. The reaction mixture was cooled to room temperature and quenched with water. The aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with a saturated solution of NaHCO 3 and a saturated NaCl solution, dried over Na 2 SO 4 , filtered and concentrated in vacuo. The crude product was purified by silica gel flash chromatography to give the title compound as a yellow solid.

[0682] LCMS (method 1): 483 (M+H + ); retention time: 1.09 min.

[0683] 1 H NMR (400 MHz, chloroform-d) δ ppm 1.42 (t, J = 7.34 Hz, 3H) 3.84 (q, J = 7.34 Hz, 2H) 3.99 (s, 3H) 7.00-7.05 (m, 1H) 7.68 (d, J = 5.87 Hz, 2H) 8.12 (d, J = 8.44 Hz, 1H) 8.17 (s, 1H) 8.64 (d, J = 8.44 Hz, 1H) 9.06 (s, 1H)

[0684] Example H7: 2-[3-Ethylsulfonyl-6-[3-(trifluoromethyl)pyrazol-1-yl]-2-pyridinyl]-3-methyl-6- (Trifluoromethylsulfanyl)imidazo[4,5-c]pyridine (Compound P9, Table P)

[0685] (Compound P9, Table P)

[0686] Step A: Methyl 3-ethylsulfonyl-6-[3-(trifluoromethyl)pyrazol-1-yl]pyridine-2-carboxylate

[0687]

[0688] To a stirred solution of 6-chloro-3-ethylsulfonyl-pyridine-2-formic acid methyl ester (526mg, 2mmol), 3-(trifluoromethyl)-1H-pyrazole (1.361g, 10mmol) in dioxane (25mL) was added CuI (38mg, 0.2mmol), N, N'-dimethylethylenediamine (880mg, 1mmol) and potassium carbonate (1.38g, 10mmol). The reaction system was refluxed at 120 ° C for 4 hours under a nitrogen atmosphere. After cooling to room temperature, the reaction mixture was filtered and concentrated in vacuo. The crude product was purified by silica gel column chromatography to give the title compound.

[0689] 1HNMR (400MHz, CDCl3): δppm 1.36(t,3H),3.49(q,2H),4.06(s,3H),6.69(s,1H),8.26(d,J=8.4Hz,1H),8.44(d,J=8.4Hz,1H),8.68(s,1H); ESI-MS(+):386(M+Na)+

[0690] Step B: 3-Ethylsulfonyl-6-[3-(trifluoromethyl)pyrazol-1-yl]pyridine-2-carboxylic acid

[0691]

[0692] To a stirred solution of methyl 3-ethylsulfonyl-6-[3-(trifluoromethyl)pyrazol-1-yl]pyridine-2-carboxylate (218 mg, 0.6 mmol) in THF (10 mL) was added NaOH (120 mg, 3 mmol) and H O (30 mL). The reaction was stirred at room temperature for 2 hours. After this time, the pH was adjusted to 2 with HCl, and the reaction mixture was extracted 3 times with ethyl acetate. The combined organic layers were dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo to give the title compound.

[0693] 1HNMR (400MHz, DMSO-d6): δppm 1.18 (t, 3H), 3.54 (q, 2H), 7.12 (s, 1H), 8.21 (d, J = 8.8Hz, 1H), 8.53 (d, J = 8.4Hz, 1H), 8.86 (s, 1H); ESI-MS (+): 348 (MH)-

[0694] Step C: 2-[3-ethylsulfonyl-6-[3-(trifluoromethyl)pyrazol-1-yl]-2-pyridinyl]-3-methyl-6- (Trifluoromethylsulfanyl)imidazo[4,5-c]pyridine (Compound P9, Table P)

[0695] (Compound P9, Table P)

[0696] To a stirred solution of 3-ethylsulfonyl-6-[3-(trifluoromethyl)pyrazol-1-yl]pyridine-2-carboxylic acid (180 mg, 0.52 mmol), N3-methyl-6-(trifluoromethylsulfanyl)pyridine-3,4-diamine (250 mg, 1.11 mmol) and HATU (0.78 g, 2 mmol) in DMF (30 mL) was added DIPEA (2 mL, 10 mmol). The reaction mixture was stirred at room temperature overnight. The reaction mixture was then diluted with ethyl acetate and H2O, the organic layer was washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The crude product was used in the next step without further purification. A solution of the crude product in acetic acid (20 mL) was refluxed at 120 ° C for 24 hours. The reaction mixture was then evaporated to dryness. The residue was purified by silica gel chromatography (petroleum: EtOAc=4: 1) to give the title compound as a white solid.

[0697] LCMS (method 1): 537 (M+H + ); retention time: 1.17 min.

[0698] 1HNMR (400MHz, CDCl3): δ (ppm) 1.37 (t, 3H), 3.73 (q, 2H), 3.90 (s, 3H), 6.79 (s, 1H), 8.14 (s, 1H), 8.45 (d, J = 4.8Hz, 1H), 8.65 (s, 1H), 8.67 (d, J = 4.8Hz, 1H), 8.98 (s, 1H); 19FNMR (376MHz, CDCl3): δ (ppm) -46.40 (s, 3F), -68.19 (s, 3F)

[0699] Example 2-(3-ethylsulfonyl-6-pyrimidin-2-yl-2-pyridinyl)-3-methyl-6-(trifluoromethylsulfanyl)imidazole Oxazo[4,5-c]pyridine (Compound P10, Table P)

[0700] (Compound P10, Table P)

[0701] Step A: N-methyl-4-nitro-6-(trifluoromethylsulfanyl)pyridin-3-amine

[0702]

[0703] By (bpy)CuSCF (14.4g, 45mmol) and 6-bromo-N-methyl-4-nitro-pyridine-3-amine (6.96g, 30mmol) in 120mL CH the sample in CN refluxed 48 hours under nitrogen.Reaction mixture is removed and allowed to be cooled to room temperature from oil bath, and then passed through SiO filter.Silica gel is eluted with diethyl ether and concentrated in a vacuum.Resistates is carried out to purifying by silica gel column chromatography, to provide title compound.

[0704] 1HNMR (400MHz, DMSO-d6): δ (ppm) 3.10 (d, J = 5.2Hz, 3H), 8.21 (s, 1H) 8.49 (q, 1H), 8.67 (s, 1H); 19FNMR (376MHz, DMSO-d6): δ (ppm)-36.79 (s, 3F); ESI-MS: 252 (MH)-.

[0705] Step B: N3-methyl-6-(trifluoromethylsulfanyl)pyridine-3,4-diamine

[0706]

[0707] To a solution of N-methyl-4-nitro-6-(trifluoromethylsulfanyl)pyridin-3-amine (3.42 g, 13.5 mmol) in methanol (50 mL) was added Raney nickel (20% wt). To this mixture was added hydrazine hydrate (10 mL) dropwise at room temperature. The reaction mixture was stirred at room temperature for 30 minutes. The Raney nickel was filtered off through celite; the filtrate was dried in vacuo and purified by silica gel chromatography to give the title compound as a white solid.

[0708] 1HNMR (400MHz, DMSO-d6): δppm 2.78 (d, J=5.2Hz, 3H), 5.20 (q, 1H), 5.77 (s, 2H), 6.82 (s, 1H), 7.53 (s, 1H); 19FNMR (376MHz, DMSO-d6): δppm-45.49 (s, 3F); ESI-MS (+): 224 (M+H)+.

[0709] Step C: Methyl 3,6-dichloropyridine-2-carboxylate

[0710]

[0711] At room temperature, SOCl (150 mL) was added dropwise to a solution of 3,6-dichloropyridine-2-formic acid (76.8 g, 0.4 mol) in methanol (500 mL). The reaction mixture was stirred at room temperature for 3 hours. After this, the reaction mixture was poured into water and extracted three times with ethyl acetate. The organic layer merged was dried over sodium sulfate, filtered and concentrated in a vacuum to provide the title compound.

[0712] 1HNMR (400MHz, DMSO-d6): δppm 3.90 (s, 3H), 7.80 (d, J = 8.8Hz, 1H), 8.20 (d, J = 8.8Hz, 1H); ESI-MS (+): 228 (M + Na) +.

[0713] Step D: 6-Chloro-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester

[0714]

[0715] At 0 DEG C, sodium thioethanethioate (7.2g, 85.8mmol) was added to a solution of 3,6-dichloropyridine-2-methyl formate (16g, 77.6mmol) in DMF (150mL). After addition, the reaction mixture was stirred at room temperature for 30 minutes. After this time, LCMS analysis showed that the reaction was complete. The reaction mixture was poured into water, and the precipitate formed was filtered and dried under an infrared oven to obtain the title compound as a white solid.

[0716] 1HNMR (400MHz, CDCl3): δppm 1.38 (t, 3H), 2.92 (q, 2H), 3.98 (s, 3H), 7.40 (d, J = 8.8Hz, 1H), 7.66 (d, J = 8.8Hz, 1H); ESI-MS (+): 254 (M + Na) +.

[0717] Step E: 6-Chloro-3-ethylsulfonyl-pyridine-2-carboxylic acid methyl ester

[0718]

[0719] A solution of 6-chloro-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester (11.55 g, 50 mmol) and m-CPBA (25.8 g, 150 mmol) in 200 mL of dichloromethane was stirred at room temperature for 2 hours. After this time, the mixture was poured into a saturated solution of NaHCO and NaSO and extracted three times with DCM. The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by silica gel column chromatography to give the title compound.

[0720] 1HNMR (400MHz, CDCl3): δppm 1.33 (t, 3H), 3.51 (q, 2H), 4.02 (s, 3H), 7.63 (d, J = 8Hz, 1H), 8.29 (d, J = 8Hz, 1H); ESI-MS (+): 286 (M + Na) +.

[0721] Step F: 3-Ethylsulfonyl-6-pyrimidin-2-yl-pyridine-2-carboxylic acid methyl ester

[0722]

[0723] To a stirred solution of 6-chloro-3-ethylsulfonyl-pyridine-2-formic acid methyl ester (526mg, 2mmol) and tributyl (pyrimidin-2-yl) stannane (1.107g, 3mmol) in dioxane (25mL), add CuI (76mg, 0.4mmol) and PdCl (PPh ) (140mg, 0.2mmol). The reaction mixture was refluxed at 120° C. for 4 hours under a nitrogen atmosphere. After being cooled to room temperature, the reaction mixture was filtered and concentrated in a vacuum. The crude product was purified by silica gel column chromatography to provide the title compound.

[0724] 1HNMR (400MHz, CDCl3): δppm 1.36(t,3H),3.58(q,2H),4.05(s,3H),7.42(t,1H),8.53(d,J=8.4Hz,1H),8.81(d,J=8.4Hz,1H),9.00(d,J=4.8Hz,2H); ESI-MS(+):330(M+Na)+

[0725] Step G: 3-Ethylsulfonyl-6-pyrimidin-2-yl-pyridine-2-carboxylic acid

[0726]

[0727] To the stirred solution of 3-ethylsulfonyl-6-pyrimidine-2-yl-pyridine-2-formic acid methyl ester (522mg, 1.7mmol) in tetrahydrofuran (10mL), add NaOH (340mg, 8.5mmol) and water (30ml).The reaction system was at room temperature stirred 2 hours, and now LCMS analysis display reaction is complete.With HCl, pH value is adjusted to 2, and reaction mixture is extracted three times with ethyl acetate.Organic layer is filtered and concentrated in vacuo through anhydrous sodium sulfate drying, to provide title compound.

[0728] 1HNMR (400MHz, DMSO-d6): δppm 1.22(t,3H),3.57(q,2H),7.66(m,1H),7.68(d J=4.8Hz, 1H), 8.55 (d, J=8.4Hz, 1H), 8.70 (d, J=8.4Hz, 1H), 9.07 (d, J= 4.8Hz, 2H).

[0729] Step H: 2-(3-ethylsulfonyl-6-pyrimidin-2-yl-2-pyridinyl)-3-methyl-6-(trifluoromethylsulfanyl) Imidazo[4,5-c]pyridine (Compound P10, Table P)

[0730] (Compound P10, Table P)

[0731] To a stirred solution of 3-ethylsulfonyl-6-pyrimidin-2-yl-pyridine-2-carboxylic acid (470 mg, 1.6 mmol), N3-methyl-6-(trifluoromethylsulfanyl)pyridine-3,4-diamine (430 mg, 1.92 mmol) and HATU (1.216 g, 3.2 mmol) in DMF (30 mL) was added DIPEA (2.8 ml, 16 mmol). The reaction was stirred at room temperature overnight. After this time, the reaction mixture was diluted with ethyl acetate and H2O, and the organic layer was washed with brine, dried over anhydrous sodium sulfate and concentrated in vacuo. The crude product was used in the next step without further purification.

[0732] A solution of the crude product in acetic acid (20 mL) was refluxed at 120° C. for 24 h. The reaction mixture was evaporated to dryness and the residue was purified by silica gel chromatography to give the title compound as a white solid.

[0733] LCMS (method 1): 481 (M+H+); retention time: 0.93 min

[0734] 1HNMR (400MHz, CDCl3): δ (ppm) 1.38 (t, 3H), 3.80 (q, 2H), 3.93 (s, 3H), 7.44 (t, 1H), 8.10 (s, 1H), 8.7 0(d,J=8.4Hz,1H),8.96(m,2H),9.0(d,J=4.8Hz,2H); 19FNMR(376MHz, CDCl3): δ(ppm)-45.77(s,3F);

[0735] Example H8: 2-(6-cyclopropyl-3-ethylsulfonyl-2-pyridinyl)-3-methyl-6-(trifluoromethylsulfanyl)imidazole Oxazo[4,5-c]pyridine (Compound P13, Table P)

[0736] (Compound P13, Table P)

[0737] Step A: 6-Cyclopropyl-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester

[0738]

[0739] To a stirred solution of 6-chloro-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester (462 mg, 2 mmol) and cyclopropylboronic acid (344 mg, 4 mmol) in dioxane (25 mL) was added potassium carbonate (552 mg, 4 mmol) and Pd(PPh 3 ) 4 (230 mg, 0.2 mmol). The reaction system was refluxed at 120° C. under a nitrogen atmosphere for 24 hours. After cooling to room temperature, the reaction mixture was filtered and concentrated in vacuo. The crude product was purified by silica gel column chromatography to give the title compound.

[0740] 1HNMR (400MHz, CDCl3): δ (ppm) 0.98 (m, 4H), 1.32 (t, 3H), 2.08 (m, 1H), 2.88 (q, 2H) ,3.95(s,3H),7.08(d,J=8.4Hz,1H),7.57(d,J=8Hz,1H); ESI-MS(+):260(M+Na)+.

[0741] Step B: 6-Cyclopropyl-3-ethylsulfanyl-pyridine-2-carboxylic acid

[0742]

[0743] To a stirred solution of 6-cyclopropyl-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester (320 mg, 1.35 mmol) in THF (10 mL) was added NaOH (280 mg, 7 mmol) and H O (30 mL). The reaction was stirred at room temperature for 4 hours. The pH was adjusted to 2 with HCl, and the reaction mixture was extracted three times with ethyl acetate. The combined organic layers were dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo to give the title compound.

[0744] 1HNMR (400MHz, DMSO-d6): δppm 0.93(m,4H),1.18(t,3H),2.07(m,1H),2.91(q,2H),7.36(d,J=8.0Hz,1H),7.73(d,J=8.4Hz,1H),12.93(bs,1H); ESI-MS(-):222(MH)-.

[0745] Step C: 6-Bromo-2-(6-cyclopropyl-3-ethylsulfanyl-2-pyridinyl)-3-methyl-imidazo[4,5-c]pyridinyl pyridine

[0746]

[0747] To a stirred solution of 6-cyclopropyl-3-ethylsulfanyl-pyridine-2-carboxylic acid (280 mg, 1.25 mmol), 6-bromo-N3-methyl-pyridine-3,4-diamine (303 mg, 1.5 mmol) and HATU (0.78 g, 2 mmol) in DMF (30 mL) was added DIPEA (2 mL, 10 mmol). The reaction mixture was stirred at room temperature overnight. The reaction mixture was then diluted with ethyl acetate and H o, and the organic layer was washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The crude product was used in the next step without further purification. A solution of the crude product in acetic acid (20 mL) was refluxed at 120 ° C for 24 hours. The reaction mixture was concentrated and purified by silica gel column chromatography to obtain the title compound as a white solid.

[0748] 1HNMR (400MHz, CDCl3): δ (ppm) 1.04 (m, 4H), 1.31 (t, 3H), 2.1 (m, 1H), 2.91 (q, 2H), 3.92 (s, 3H) ,7.25(d,J=8.4Hz,1H),7.66(d,J=8Hz,1H),7.94(s,1H),8.62(s,1H); ESI-MS(+):413(M+Na)+.

[0749] Step D: 6-Bromo-2-(6-cyclopropyl-3-ethylsulfonyl-2-pyridinyl)-3-methyl-imidazo[4,5-c]pyridinyl Pyridine (Compound P12, Table P)

[0750] (Compound P12, Table P)

[0751] A sample of 6-bromo-2-(6-cyclopropyl-3-ethylsulfanyl-2-pyridinyl)-3-methyl-imidazo[4,5-c]pyridine (285 mg, 0.73 mmol) and m-CPBA (630 mg, 3.66 mmol) in 40 mL of DCM was stirred at room temperature for 2 hours. The mixture was then poured into a saturated solution of NaHCO and NaSO in water and extracted three times with dichloromethane. The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by silica gel column chromatography to give the title compound.

[0752] LCMS (method 1): 421 / 423 (M+H + ); retention time: 0.97 min

[0753] 1HNMR (400MHz, CDCl3): δ (ppm) 1.16 (m, 4H), 1.34 (t, 3H), 2.05 (m, 1H), 3.69 (q, 2H), 3.76(s,3H),7.53(d,J=8.0Hz,1H),7.86(s,1H),8.30(d,J=8.4Hz,1H),8.66(s,1H);

[0754] Step E: 2-(6-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethylsulfanyl)imidazole Oxazo[4,5-c]pyridine (Compound P13, Table P)

[0755] (Compound P13, Table P)

[0756] By (bpy) CuSCF (410mg, 1.28mmol) and 6-bromo-2-(6-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-3-methyl-imidazo [4,5-c] pyridine (270mg, 0.64mmol) in 20mL CH CN sample was refluxed under nitrogen for 48 hours. The reaction mixture was removed from the oil bath and allowed to cool, and passed through SiO filtered, eluted with diethyl ether. The filtrate was washed with salt water and concentrated in a vacuum. The residue was purified by silica gel column chromatography to give the title compound.

[0757] LCMS (method 1): 444 (M+H+); retention time: 1.07 min

[0758] 1HNMR (400MHz, CDCl3): δ (ppm) 1.19 (m, 4H), 1.34 (t, 3H), 2.12 (m, 1H), 3.71 (q, 2H), 3.81(s,3H),7.54(d,J=8.4Hz,1H),8.10(s,1H),8.31(d,J=8.8Hz,1H),8.92(s,1H)

[0759] Example H9: 6-(6-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-7-methyl-3-(trifluoromethyl)imidazolin [4,5-c]pyridazine (Compound P22, Table P)

[0760] (Compound P22, Table P)

[0761] Step A: 3-Chloro-6-iodopyridazine

[0762]

[0763] Hydroiodic acid (250 mL) is added to a mixture of 3,6-dichloropyridazine (149 g, 1 mol) and NaI (180 g, 1.2 mol) in 500 mL of CHCl . After addition, the mixture is stirred at ambient temperature for 24 hours, poured into water, and extracted 3 times with dichloromethane. The combined organic layers are dried over sodium sulfate, filtered, and concentrated in vacuo to give the title compound.

[0764] 1 H-NMR(400Mz,DMSO-d6)δ:7.63(d,1H),8.16(d,1H).

[0765] Step B: 3-Chloro-6-(trifluoromethyl)pyridazine

[0766]

[0767] Under nitrogen, by TMSCF (198.8g, 1.4mol) is added into the mixture of 3-chloro-6-iodopyridazine (240g, 1mol), KF (81g, 1.4mol) and CuI (228g, 1.2mol) in 1L DMF.After the interpolation, this mixture was stirred 2 hours at 50 ℃.Then this mixture was poured into water and extracted with ether (three times).The organic layer merged is dried over sodium sulfate, filtered and concentrated in a vacuum.Resistates is carried out to purification by silica gel flash column chromatography, to provide title compound.

[0768] 1 H-NMR(400Mz,DMSO-d6)δ:8.30(d,1H),8.38(d,1H); 19 F-NMR(400Mz,DMSO-d6)δ:-64.93(s,3F).

[0769] Step C: N-methyl-6-(trifluoromethyl)pyridazin-3-amine:

[0770]

[0771] A solution of MeNH2 (100 g, 30% in EtOH) was added to a mixture of 3-chloro-6-(trifluoromethyl)pyridazine (91 g, 0.5 mol) in 100 ml of EtOH. After addition, the mixture was stirred at 50° C. for 2 hours and then poured into water. The precipitated solid was filtered and dried in vacuo to give the title compound.

[0772] 1 H-NMR(400Mz,DMSO-d6)δ:2.93(d,3H),6.95(d,1H),7.58(q,1H),7.63(d,1H); 19 F-NMR(400Mz,DMSO-d6)δ:-59.88(s,3F); ESI-MS(+):178(M+H) + .

[0773] Step D: 4-Bromo-N-methyl-6-(trifluoromethyl)pyridazin-3-amine:

[0774]

[0775] Bromine (32g, 0.2mol) is added to a mixture of N-methyl-6-(trifluoromethyl)pyridazine-3-amine (17.7g, 0.1mol) in 100mL of MeCN. After the addition, the mixture was stirred at ambient temperature for 48 hours. After this time, the mixture was poured into ammonium hydroxide (10% solution) and extracted with ethyl acetate (three times). The combined organic layer was dried over sodium sulfate, filtered and concentrated in vacuo. Residue was purified by silica gel flash column chromatography to give the title compound.

[0776] 1 H-NMR(400Mz,DMSO-d6)δ:3.03(d,3H),7.45(q,1H),8.23(s,1H); 19 F-NMR(400Mz,DMSO-d6)δ:-59.47(s,3F); ESI-MS(+):256 / 258(M+H) + .

[0777] Step E:N 3 -Methyl-6-(trifluoromethyl)pyridazine-3,4-diamine:

[0778]

[0779] 4-Bromo-N-methyl-6-(trifluoromethyl)pyridazine-3-amine (3g, 11.8mmol) and 120mL of ammonium hydroxide are placed in a 250mL autoclave. Then, nitrogen is introduced into the autoclave, and the pressure is increased to 2MPa. The mixture is stirred at 130 ℃ for 48 hours, poured into water, and extracted with ethyl acetate (three times). The organic layer merged is dried over sodium sulfate, filtered and concentrated in a vacuum. Residue is purified by silica gel column chromatography to provide the title compound.

[0780] 1 H-NMR(400Mz,DMSO-d6)δ:2.97(d,3H),6.27(s,2H),6.50(q,1H),6.67(s,1H); 19 F-NMR(400Mz,DMSO-d6)δ:-61.96(s,3F); ESI-MS(+):193(M+H) + .

[0781] Step F: 6-Cyclopropyl-3-ethylsulfanyl-pyridine-2-carbonyl chloride

[0782]

[0783] To a mixture of 6-cyclopropyl-3-ethylsulfanyl-pyridine-2-carboxylic acid (223 mg, 1 mmol) in 10 mL of dichloromethane was added oxalyl chloride (380 mg, 3 mmol) and stirred at room temperature for 30 minutes. Excess oxalyl chloride and dichloromethane were removed under reduced pressure to give the title compound in almost quantitative yield (241 mg). The crude title compound was used directly in the next step without further purification.

[0784] Step G: 6-(6-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-7-methyl-3-(trifluoromethyl)imidazo[4, 5-c]pyridazine (Compound P22, Table P)

[0785] (Compound P22, Table P)

[0786] A sample of 6-cyclopropyl-3-ethylsulfanyl-pyridine-2-carbonyl chloride (241 mg, 1 mmol) was added to a mixture of N3-methyl-6-(trifluoromethyl)pyridazine-3,4-diamine (211 mg, 1.1 mmol) in 20 mL of THF, and the mixture was refluxed for 48 hours. After this time, the mixture was poured into water and extracted three times with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by silica gel column chromatography to give the title compound.

[0787] 1H NMR (400MHz, DMSO) δ0.97-1.00(m,2H),1.02-1.07(m,2H),1.19(t,3H),2.22-2. 28(m,1H),2.98(q,2H),4.08(s,3H),7.58(d,1H),7.98(d,1H),8.71(s,1H); 19F NMR (400MHz, DMSO) δ-62.23 (s, 3F); ESI-MS (+): 380 (M+H)+, 434 (M+Na+MeOH)+.

[0788] Example H10: 6-(6-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-7-methyl-3-(trifluoromethyl)imidazolin [4,5-c]pyridazine (Compound P14, Table P)

[0789] (Compound P14, Table P)

[0790] A solution of 6-(6-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazine (70 mg, 0.18 mmol) and m-CPBA (93 mg, 0.54 mmol) in 10 mL of dichloromethane was stirred at room temperature for 2 hours. The mixture was then poured into a saturated solution of NaHCO and NaSO in water and extracted three times with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by silica gel column chromatography to give the title compound.

[0791] LCMS (method 1): 413 (M+H + ); retention time: 1.01 min.

[0792] 1H NMR (400MHz, DMSO-d6) δ1.05-1.07(m,2H),1.13-1.18(m,2H),1.15(t,3H),2.38-2.42(m,1H),3.63(q ,2H),3.88(s,3H),7.88(d,1H),8.34(d,1H),8.72(s,1H);19F-NMR(400Mz,DMSO-d6)δ:-64.55(s,3F);

[0793] Example H11: 2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine-2- 1-[4-[[4-pyridyl]-2-pyridyl]acetonitrile] (Compound P23, Table P)

[0794] (Compound P23, Table P)

[0795] In a microwave vial, 2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (0.20 g, 0.49 mmol) was dissolved in DMF (1.0 mL). The vial was flushed with argon and TMSCN (0.10 mL, 0.74 mmol), difluorozinc (0.031 g, 0.30 mmol), Pd2(dba)3 (0.0091 g, 0.0099 mmol) and XANTPHOS (0.012 g, 0.020 mmol) were added. The vial was capped and heated in a microwave at 140 ° C for 30 minutes. The reaction mixture was diluted with ethyl acetate and filtered through hyflo. The filtrate was extracted with water and brine, dried over Na2SO4, filtered and concentrated in vacuo. The crude product was purified by flash chromatography on silica gel to give the title compound.

[0796] LCMS (method 1): 410 (M+H+); retention time: 0.84 min.

[0797] 1H NMR (400Mhz, chloroform CHLOROFORM-d) δppm 1.40(t,J=7.52Hz,3H)3.83(q,J=7.34Hz,2H)3.97(s,3H)4.17(s,2H)7.89(d,J=8.44Hz,1H)8.15(s,1H)8.63(d,J=8.07Hz,1H)9.04(s,1H)

[0798] Example H12: 1-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine-2- [4-[4-[4-pyridyl]-2-pyridyl]cyclopropanecarbonitrile (Compound P17, Table P)

[0799] (Compound P17, Table P)

[0800] A sample of 2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-2-pyridinyl]acetonitrile (0.11 g, 0.27 mmol) was dissolved in acetonitrile (2.8 mL). Cesium carbonate (0.27 g, 0.81 mmol) was added, followed by 1,2-dibromoethane (0.047 mL, 0.54 mmol). The mixture was stirred at 80 ° C for 1 hour. LC-MS analysis showed the consumption of the starting material and the substance of the desired product. The reaction was quenched with water and acetonitrile and evaporated. The residue was diluted with ethyl acetate, washed with water and brine, dried over Na2SO4, filtered and concentrated in vacuo. The crude product was purified by flash chromatography on silica gel to give the title compound.

[0801] LCMS (method 1): 436 (M+H+); retention time: 0.94 min.

[0802] 1H NMR (400 MHz, chloroform-d) δ ppm 1.38 (t, J = 7.52 Hz, 3H) 1.88-2.02 (m, 4H) 3.73 (d, J = 7.70 Hz, 2H) 3.86 (s, 3H) 8.12-8.19 (m, 2H) 8.54 (d, J = 8.44 Hz, 1H) 9.02 (s, 1H)

[0803] Example H13: 2-[3-Ethylsulfonyl-6-[2-(3-fluorophenyl)ethynyl]-2-pyridinyl]-3-methyl-6-(trifluorophenyl)ethynyl (4,5-c]pyridine (compound P20, Table P)

[0804] (Compound P20, Table P)

[0805] By 2- (6- chloro -3- ethylsulfonyl -2- pyridyl) -3- methyl -6- (trifluoromethyl) imidazo [4,5-c] pyridine (0.10g, 0.25mmol), 1- ethynyl -3- fluoro- benzene (0.044mL, 0.37mmol), DIPEA (0.086mL, 0.49mmol), copper (I) iodide (0.0024g, 0.012mmol) in tetrahydrofuran (4.0mL) sample is mixed in a bottle, and the clear light yellow solution is flushed with argon. PdCl is added (PPH) (0.0088g, 0.012mmol), and the mixture is stirred at room temperature overnight. After this time, the reaction display is complete. The crude mixture is purified by flash chromatography to give the title compound as a beige solid.

[0806] LCMS (method 1): 489 (M+H + ); retention time: 1.11 min.

[0807] 1 H NMR (400 MHz, chloroform-d) δ ppm 1.39 (t, J = 7.34 Hz, 3H) 3.78 (q, J = 7.46 Hz, 2H) 3.96 (s, 3H) 7.14-7.24 (m, 1H) 7.32-7.38 (m, 1H) 7.37-7.48 (m, 2H) 7.92 (d, J = 8.44 Hz, 1H) 8.14 (s, 1H) 8.54 (d, J = 8.44 Hz, 1H) 9.02 (s, 1H)

[0808] The compounds in Tables 1-88 can be prepared similarly to the above methods.

[0809] Table P: Examples of compounds of formula (I)

[0810]

[0811]

[0812]

[0813]

[0814]

[0815] By adding other active ingredients with insecticidal, acaricidal and / or fungicidal activity, the activity of the compositions according to the invention can be significantly broadened and adapted to the prevailing circumstances. Mixtures of compounds of formula I with other active ingredients with insecticidal, acaricidal and / or fungicidal activity can also have further, unexpected advantages, which can also be described in a broader sense as synergistic activities. For example, plants can tolerate them better, their phytotoxicity can be reduced, insects can be controlled at different stages of their development, or their behavior can be improved during production (e.g., during grinding or mixing, during storage or during use).

[0816] Suitable additives to the active ingredients 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.

[0817] The following mixtures of compounds of formula I and active ingredients are preferred (the abbreviation "TX" means "a compound selected from the group consisting of the compounds described in Tables 1 to 88 and P of the present invention"):

[0818] Adjuvant, the adjuvant is selected from the group consisting of: petroleum (628) + TX,

[0819] Acaricide, the acaricide being selected from the group consisting of: 1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910) + TX, 2,4-dichlorophenylbenzenesulfonate (IUPAC / Chemical Abstracts name) (1059) + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name) (1295) + TX, 4-chlorophenylphenylsulfone (IUPAC name) (981) + TX, avermectin (1) + TX, acequinoxaline (3) + TX, acetofennig [CCN] + TX, flumethrin (9) + TX, aldicarb (16) + TX, aldicarb (863) + TX, α-cypermethrin (202) + TX, cypermethrin (870) + TX, sulfamethoxam [CCN] + TX, aminothioate (872) + TX, amitriptyline (875) + TX, amitriptyline hydrogen oxalate (875) + TX, amitraz (24) + TX, cypermethrin (881) + TX, arsenic trioxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azinphos-methyl (44) + TX, azinphos-methyl (45) + TX, azobenzene (IUPAC name) (888) + TX, azacyclotin (46) + TX, azothoate (889) + TX, benclofenac (62) + TX, benoxafos [CCN] + TX, benzoximate (71) + TX, benzyl benzoate (IUPAC name) [CCN] + TX, bifenazate (74) + TX, flumethrin (76) + TX, fenthion (907) + TX, bromomethrin + TX, bromocyclene (918) + TX, bromophos (920) + TX, ethyl bromophos (921) + TX, bromopropylate (94) + TX, thiamethoxam (99) + TX, butanone (103) + TX, butanone sulfone (104) + TX, butanone sulfone (butylpyridaben) + TX, calcium polysulfide (IUPAC name) (111) + TX, campheechlor (941) + TX, carbanolate (943) + TX, ferric pyrrolidone (115) + TX, carbofuran (118) + TX, carbothion (947) + TX, CGA 50'439 (research code) (125) + TX, chinomethionat (126) + TX, chlorbenside (959) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX,Chlorfenapyr (130) + TX, chlorfenapyr (968) + TX, chlorfenson (970) + TX, chlorfensulfide (971) + TX, chlorfenapyr (131) + TX, chlorobenzilate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, methyl chlorpyrifos (146) + TX, chlorfenapyr (131) + TX, chlorobenzilate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, methyl chlorpyrifos (146) + TX, chlorfenapyr (131) + TX ophos)(994)+TX, cinerin I(696)+TX, cinerin 11(696)+TX, cinerins(696)+TX, clofentazine(158)+TX, closantel[CCN]+TX, coumaphos(174)+TX, crotamiton[CCN]+TX, crotoxyphos(1010)+TX, thiophene(1013)+TX, cyanthoate(1020)+TX, cyfluthrin(CAS Reg. No.: 400882-07-7)+TX, cyhalothrin(196)+TX, cypermethrin(199)+TX, chlorfenapyr Pyrethroids (201) + TX, DCPM (1032) + TX, DDT (219) + TX, demephion (1037) + TX, demephion-O (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, methyl demeton (224) + TX, demeton-O (1038) + TX, methyl demeton-O (224) + TX, demeton-S (1038) + TX, methyl demeton-S (224) + TX, demeton-S-methylsulfon (1039) + TX, chlorfenapyr (226) + TX, Phosmet (dialifos) (1042) + TX, diazinon (227) + TX, dichlorosulfonamide (230) + TX, dichlorvos (236) + TX, dicliphos + TX, chlorpyrifos (242) + TX, dicrotophos (243) + TX, pendimethalin (1071) + TX, dimefox (1081) + TX, dimethoate (262) + TX, dinacti (653) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX, dinobuton (269) + TX,Dinocap (270) + TX, dinocap-4 [CCN] + TX, dinocap-6 [CCN] + TX, dinitropropane (1090) + TX, dinopenton (1092) + TX, dinosulfon (1097) + TX, dinoterbon (1098) + TX, dioxafoate (1102) + TX, diphenylsulfone (IUPAC name) (1103) + TX, disulfiram [CCN] + TX, disulfoton (278) + TX, DNOC (282) + TX, dofenapyn ) (1113) + TX, doramectin [CCN] + TX, endosulfan (294) + TX, endothion (1121) + TX, EPN (297) + TX, eprinomectin [CCN] + TX, ethion (309) + TX, ethoate-methyl (1134) + TX, etoxazole (320) + TX, etrimfos (1142) + TX, fenazaflor (1147) + TX, quinazaquin (328) + TX, fenbutatin oxide)(330)+TX, fenothiocarb)(337)+TX, cypermethrin(342)+TX, fenpyrad+TX, fenpyroximate(345)+TX, fenson(1157)+TX, fentrifanil(1161)+TX, cypermethrin(349)+TX, fipronil(354)+TX, fluacrypyrim(360)+TX, fluorine Zolon (1166) + TX, flubenzimine (1167) + TX, flufenoxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1169) + TX, flufenoxuron (370) + TX, flumethrin (372) + TX, fluorbenside (1174) + TX, fluvalinate (1184) + TX, FMC 1137 (research code) (1185) + TX, cypermethrin (405) + TX, cypermethrin hydrochloride (405) + TX, formothion (1192) + TX, formparanate (1193) + TX, γ-HCH (430) + TX, glyodin (1205) + TX,Halfenprox (424) + TX, heptenophos (432) + TX, hexadecylcyclopropanecarboxylate (IUPAC / Chemical Abstracts name) (1216) + TX, hexathiazolin (441) + TX, iodomethane (IUPAC name) (542) + TX, isocarbophos (473) + TX, isopropyl O-(methoxyaminothiophosphoryl) salicylate (IUPAC name) (473) + TX, ivermectin [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, lindane (430) + TX, lufenuron (490) +TX, malathion (492) +TX, malonoben (1254) +TX, mecarbam (502) +TX, mephosfolan (1261) +TX, CCN +TX, methacrifos (1266) +TX, methamidophos (527) +TX, methidathion (529) +TX, methiocarb (530) +TX, methomyl (531) +TX, methyl bromide (537) +TX, metolcarb (550) +TX, metolcarb (556) +TX, mexacarbate (1290) +TX, milbemycin (557) +TX, milbemycin oxime oxime) [CCN] + TX, mipafox (1293) + TX, monocrotophos (561) + TX, morphothion (1300) + TX, moxidectin [CCN] + TX, naled (567) + TX, NC-184 (compound code) + TX, NC-152 (compound code) + TX, nifluridide (1309) + TX, nikkomycin [CCN] + TX, nitrilacarb (1313) + TX, nitrilacarb (1314) + TX, rb)1:1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, oxydemeton (594) + TX, oxamyl (602) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum (628) + TX, fenthion (1330) + TX, fenthion (631) + TX,Phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosphamidon (639) + TX, phoxim (642) + TX, pirimiphos-methyl (652) + TX, polychloroterpenes (traditional name) (1347) + TX, polynactins (653) + TX, prochlorperazine (1350) + TX, profenofos (662) + TX, promacyl (1354) + TX, propargite (671) + TX, propetamphos (673) +TX, propoxur (678) +TX, prothidathion (1360) +TX, prothoate (1362) +TX, pyrethrin I (696) +TX, pyrethrin II (696) +TX, pyrethrins (696) +TX, pyrethrin (699) +TX, pyridaphenthion (701) +TX, pyrimidifen (706) +TX, pyrimidifen (1370) +TX, quinalphos (711) +TX, quintiofos (1381) +TX, R-1492 (research code) (1382) +TX, RA-17 (research code) (1383) +TX, rotenone (722) +TX, schradan (1389) +TX, sebufos +TX, selamectin [CCN] +TX, SI-0009 (compound code) +TX, sophamide (1402) +TX, tebufenoxam (738) +TX, spiromesifen (739) +TX, SSI-121 (research code) (1404) +TX, sulfilam [CCN] +TX, sulfluramid (750) +TX TX, sulfotep (753) + TX, sulfur (754) + TX, S21-121 (research code) (757) + TX, fluvalinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, terbufenamide (terbam) + TX, stirofos (777) + TX, tetradifon (tetradifon) (786) + TX, tetranactin (653) + TX, tetrasul (1425) + TX, thiafenox + TX, thiocarboxime (1431) + TX,Thiofanox (800) + TX, thiometon (801) + TX, thiomethon (1436) + TX, thuringiensin [CCN] + TX, triamiphos (1441) + TX, triarathene (1443) + TX, triazophos (820) + TX, triazuron + TX, trichlorfon (824) + TX, trifenofos (1455) + TX, trinactin (653) + TX, thiamethoxam (847) + TX, vaniliprole [CCN] and YI-5302 (compound code) + TX,

[0820] An algaecide selected from the group consisting of: 3-benzo[b]thiophen-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dihydronaphthoquinone (dichlone) (1052) + TX, dichlorophen (232) + TX, endoxan (295) + TX TX, fentin (347) + TX, slaked lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, fentin acetate (IUPAC name) (347) and fentin hydroxide (IUPAC name) (347) + TX,

[0821] An anthelmintic selected from the group consisting of abamectin (1) + TX, clefonate (1011) + TX, doramectin [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin [CCN] + TX, ivermectin [CCN] + TX, milbemycin [CCN] + TX, moxidectin [CCN] + TX, piperazine [CCN] + TX, selamectin [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,

[0822] Avicide selected from the group consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX,

[0823] A bactericide selected from the group consisting of 1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodesine (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, Mercurophene [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, chlorpheniramine (766) + TX, and thimerosal [CCN] + TX,

[0824] A biological agent selected from the group consisting of: Adoxophyes orana GV (12) + TX, Agrobacterium radiobacterium (13) + TX, Amblyseius spp. (19) + TX, Anagrapha falcifera NPV (28) + TX, Anagrus atomus (29) + TX, Aphelinus abdominalis (33) + TX, Aphidius colemani (34) + TX, Aphidoletes aphidimyza (35) + TX, Autographa californica NPV (38) + TX, Bacillus firmus (48) + TX, Bacillus sphaericus Neide)(scientific name)(49)+TX、Bacillus thuringiensis Berliner)(scientific name)(51)+TX、Bacillus thuringiensis subsp.aizawai)(scientific name)(51)+TX、Bacillus thuringiensis subsp.israelensis)(scientific name)(51)+TX、Bacillus thuringiensis subsp.japonensis)(scientific name)(51)+TX、Bacillus thuringiensis subsp.kurstaki)(scientific name)(51)+TX、Bacillus thuringiensis subsp.tenebrionis (scientific name) (51) + TX, Beauveria bassiana (53) + TX, Beauveria brongniartii (54) + TX, Chrysoperla carnea (151) + TX, Cryptolaemus montrouzieri (178) + TX, Cydia pomonella GV (191) + TX, Dacnus asibirica (212) + TX, Diglyphus isaea (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus (300) + TX, Helicoverpa zea worm nuclear polyhedrosis virus 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 (scientific name) (523) + TX, Pine sawfly (. Neodiprion sertifer) nuclear polyhedrosis virus and red-headed pine sawfly (N.lecontei) nuclear polyhedrosis virus (575) + TX, small flower stink bug (596) + TX, Paecilomyces fumosoroseus (613) + TX, Chilean plant mite (Phytoseiulus persimilis) (644) + TX, beet armyworm (Spodopteraexigua multicapsid) multinucleocapsid nuclear polyhedrosis virus (scientific name) (741) + TX, hairy mosquito nematode (Steinernema bibionis) (742) + TX, small coiled moth nematode (Steinernema carpocapsae) (742) + TX, noctuid nematode (742) + TX, Steinernema glaseri (742) + TX, Steinernema riobrave (another name) (742) + TX, Steinernema riobravis (742) + TX, Steinernema scapterisci (742) + TX, Steinernema spp. (742) + TX, Trichogramma (826) + TX, Typhlodromus occidentalis (844) and Verticillium lecanii (848) + TX,

[0825] Soil disinfectant selected from the group consisting of methyl iodide (IUPAC name) (542) and methyl bromide (537) + TX,

[0826] A chemical sterilant selected from the group consisting of apholanate [CCN] + TX, bis(aziridine) methylaminophosphine sulfide (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, thiohexamethylenetepa [CCN] + TX, trotamide [CCN] and urethaneimide [CCN] + TX,

[0827] Insect pheromone, the insect pheromone is selected from the group consisting of: (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol (IUPAC name) (222) + TX, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, (E,Z)-tetradec-4,10-dien-1-yl acetate (IUPAC name) (779) + TX, (Z)-dodec-7-en-1-yl acetate (IUPAC name) (285) + TX, (Z)-hexadecan-11-enal (IUPAC name) (436) + TX, (Z)-hexadecan-11-en-1-yl acetate (IUPAC name) (437) +TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438) +TX, (Z)-eicos-13-en-10-one (IUPAC name) (448) +TX, (Z)-tetradec-7-en-1-al (IUPAC name) (782) +TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783) +TX, (Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784) +TX, (7E,9Z)-dodec-7,9-dien-1-yl acetate (IUPAC name) (283) +TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate (IUPAC name) (780) +TX, (9Z,12E)-tetradec-9,12-Dien-1-yl acetate (IUPAC name) (781) + TX, 14-methyloctadecene-1-ene (IUPAC name) (545) + TX, 4-methylnonanal-5-ol and 4-methylnonanal-5-one (IUPAC name) (544) + TX, α-multistriatin [CCN] + TX, brevicomin [CCN] + TX, codlelure [CCN] + TX, Codlemone (167) + TX, cuelure (179) + TX, disparlure (277) + TX, dodec-8-en-1-yl acetate (IUPAC name) (286) + TX, dodec-9-en-1-yl acetate (IUPAC name) (287) + TX, dodec-8 + TX, 10-dien-1-yl acetate (IUPAC name) (284) + TX, dominicalure [CCN] +TX, ethyl 4-methyloctanoate (IUPAC name) (317) +TX, eugenol [CCN] +TX, southern pine beetle aggregation pheromone (frontalin) [CCN] +TX, gossyplure (420) +TX, grandlure (421) +TX, grandlure mixture I (421) +TX, grandlure mixture II (421) +TX, grandlure mixture III (421) +TX, grandlure mixture IV (421) +TX, vinegar Hexalure[CCN]+TX, ipsdienol[CCN]+TX, ipsenol[CCN]+TX, japonilure(481)+TX, lineatin[CCN]+TX, litlure[CCN]+TX, looplure[CCN]+TX, medlure[CCN]+TX, megatomoic acid[CCN]+TX, methyl eugenol(540)+TX, muscalure(563)+TX, 18-2,13-dien-1-yl acetate(IUPAC name)(588)+TX, 18-3,13-Dien-1-yl acetate (IUPAC name) (589) + TX, orfralure [CCN] + TX, oryctalure (317) + TX, ostramone [CCN] + TX, siglure [CCN] + TX, sordidin (736) + TX, sulcatol [CCN] + TX, tetradecene-11-yl acetate (IUPAC name) (785) + TX, terdecene (839) + TX, terdecene A (839) + TX, terdecene B1 (839) + TX, terdecene B2 (839) + TX, terdecene C (839) and trunc-call [CCN] + TX,

[0828] An insect repellent selected from the group consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, DEET [CCN] + TX, DEET [CCN] + TX, dimethyl carbate [CCN] + TX, ethyl hexanediol (1137) + TX, hexylurea [CCN] + TX, methoquin-butyl (1276) + TX, methyl neodecylamide [CCN] + TX, oxamate [CCN] and hydroxybenzoate [CCN] + TX,

[0829] An insecticide selected from the group consisting of 1-dichloro-1-nitroethane (IUPAC / Chemical Abstracts name) (1058) + TX, 1,1-dichloro-2,2-di(4-ethylphenyl)ethane (IUPAC name) (1056) + TX, 1,2-dichloropropane (IUPAC / Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1-bromo-2-chloroethane (IUPAC / Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451) + TX, 2,2- Dichlorovinyl 2-ethylsulfinylethyl methyl phosphate (IUPAC name) (1066) + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate (IUPAC / Chemical Abstracts name) (1109) + TX, 2-(2-butoxyethoxy)ethyl thiocyanate (IUPAC / Chemical Abstracts name) (935) + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC / Chemical Abstracts name) (1084) + TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986) + TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984) + TX, 2-imidazolidinone (IUPAC name) (1225) + TX, 2-isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate (IUPAC name) (1284) + TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433) + TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917) + TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283) + TX, 4-methyl(prop-2-ynyl)amino-3,5-ditolyl methylcarbamate (IUPAC name) (IUPAC name) (1285) + TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPAC name) (1085) + TX, avermectin (1) + TX, acephate (2) + TX, acetamiprid (4) + TX, domesticaphos [CCN] + TX, acetophenone [CCN] + TX, flumethrin (9) + TX, acrylonitrile (IUPAC name) (861) + TX, cypermethrin (15) + TX, aldicarb (16) + TX, aldicarb (863) + TX, chloronaphthalene (864) + TX, allethrin (17) + TX, aloamicin [CCN] + TX, chlorpyrifos (866) + TX, α-cypermethrin (202) + TX,α-Ecdysone [CCN] + TX, aluminum phosphide (640) + TX, cypermethrin (870) + TX, thioamide (872) + TX, cypermethrin (873) + TX, cypermethrin (875) + TX, cypermethrin hydrogen oxalate (875) + TX, amitraz (24) + TX, neonicotinoid (877) + TX, ethidathion (883) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azadirachtin (41) + TX, methyl pyriphos (42) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azophos (889) + TX, Bacillus thuringiensis delta endotoxins (52) + TX, barium hexafluorosilicate [CCN] + TX, barium polysulfide (IUPAC / Chemical Abstracts name) (892) + TX, cypermethrin [CCN] + TX, Bayer 22 / 190 (research code) (893) + TX, Bayer 22408 (research code) (894) + TX, benzylcarb (58) + TX, benfuracarb (60) + TX, sulfamethoxazole (66) + TX, β-cyfluthrin (194) + TX, β-cypermethrin (203) + TX, bifenthrin (76) + TX, bioethanomethrin (78) + TX, bioethanomethrin S-cyclopentenyl isomer (79) + TX, bioethanomethrin [CCN] + T X, biopermethrin (908) + TX, pyrethrin (80) + TX, bis(2-chloroethyl) ether (IUPAC name) (909) + TX, bistrifluan (83) + TX, borax (86) + TX, bromethrin + TX, bromophenazone (914) + TX, bromophenazone (918) + TX, bromo-DDT [CCN] + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, thiocarb (924) + TX, thiophene Azinone (99) + TX, cypermethrin (926) + TX, butathiofos (927) + TX, butanone (103) + TX, butyl phosphonate (932) + TX, butanone sulfonate (104) + TX, butyl pyridabenz + TX, cadasone (109) + TX, calcium arsenate [CCN] + TX, calcium cyanide (444) + TX, calcium polysulfide (IUPAC name) (111) + TX, toxaphene (941) + TX X, chlorpyrifos (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbon disulfide (IUPAC / Chemical Abstracts name) (945) + TX, carbon tetrachloride (IUPAC name) (946) + TX, trithion (947) + TX, butanesulfonyl (119) + TX, cartap (123) + TX, cartap hydrochloride (123) + TX, simvastatin (725) + TX, borneol (960) + TX,Chlordane (128) + TX, Chlorpheniramine (963) + TX, Chlordimeform (964) + TX, Chlordimeform hydrochloride (964) + TX, Chlorpheniramine (129) + TX, Chlorfenapyr (130) + TX, Chlorfenapyr (131) + TX, Chlorfluanid (132) + TX, Chloromethyl (136) + TX, Chloroform [CCN] + TX, Chloropicrin (141) + TX, Chlorphoxim (989) + TX, Methicillin (990) + TX, Chlorpyrifos (145) + TX, Chlorpyrifos-methyl (146) + TX, Chlorfenapyr (994) + TX, Cyclofenazol (150) + TX, Hedychrysin I (696) + TX, Hedychrysin II (69 6)+TX, cypermethrins (696)+TX, cis-resmethrin+TX, cis-resmethrin (cismethrin) (80)+TX, cypermethrin+TX, cypermethrin (999)+TX, closantel[CCN]+TX, clothianidin (165)+TX, copper acetyl arsenite[CCN]+TX, copper arsenate[CCN]+TX, copper oleate[CCN]+TX, coumaphos (174)+TX, cypermethrin (1006)+TX, crotamiton[CCN]+TX, baclofos (1010)+TX, clofosinate (1011)+TX, cryolite (177)+TX, CS 708 (research code) (1012) + TX, benzonitrile (1019) + TX, cypermethrin (184) + TX, cypermethrin (1020) + TX, cyclopyrimidine [CCN] + TX, cypermethrin (188) + TX, cyfluthrin (193) + TX, cyhalothrin (196) + TX, cypermethrin (201) + TX, cypermethrin (206) + TX, cyproconazole (209) + TX, cypermethrin [CCN] + TX, d-limonene [CCN] + TX, d-tetramethrin (788) + TX, DAEP (1031) + TX, dazomet (216) + TX, DDT (219) + TX, decarbofuran (1034) + TX 、Deltamethrin (223) + TX、Tianafon (1037) + TX、Tianafon-O (1037) + TX、Tianafon-S (1037) + TX、Demeton (1038) + TX、Demeton-methyl (224) + TX、Demeton-O (1038) + TX、Demeton-O-methyl (224) + TX、Demeton-S (1038) + TX、Demeton-S-methyl (224) + TX、Demeton-S-methyl sulfone (1039) + TX、Diafenthiuron (226) + TX、Chlorophos (1042) + TX、Methylaminophos (1044) + TX、Diazinon (227) + TX、Isochlorophos (1050) + TX、Diamethoxam (1051) + TX、Dichlorvos (236) + TX、Dicliphos + TX, dicresyl [CCN] + TX, dicrotophos (243) + TX, dicynilide (244) + TX, dieldrin (1070) + TX, diethyl 5-methylpyrazol-3-yl phosphate (IUPAC name) (1076) + TX, diflubenzuron (250) + TX, dilor [CCN] + TX, tetrafluthrin [CCN] + TX, methylfluanid (1081) + TX, dimethoate (1085) + TX, dimethoate (262) + TX, pyrethrin (1083) + TX, methylchlorfenapyr (265) + TX, dimethoate (1086) + TX, chlorpyrifos ( 1089)+TX, dinex-diclexine (1089)+TX, propanol (1093)+TX, pentotropol (1094)+TX, danosid (1095)+TX, dinotefuran (271)+TX, fenpropathrin (1099)+TX, vesiculophos (1100)+TX, dioxocarb (1101)+TX, dimethoate (1102)+TX, ethoxyphos (278)+TX, dithiophos (1108)+TX, DNOC (282)+TX, doramectin [CCN]+TX, DSP (1115)+TX, ecdysone [CCN]+TX, EI1642 (research code) (1118) + TX, avermectin (291) + TX, avermectin benzoate (291) + TX, EMPC (1120) + TX, fenthrin (292) + TX, endosulfan (294) + TX, fenthion (1121) + TX, endrin (1122) + TX, EPBP (1123) + TX, EPN (297) + TX, fenthion (1124) + TX, eprinomectin [CCN] + TX, cypermethrin (302) + TX, etaphos [CCN] + TX, ethiofencarb (308) + TX, ethiofencarb (309) + TX, ethiprole (310) + TX, methyl (1 134) + TX, ethoprophos (312) + TX, ethyl formate (IUPAC name) [CCN] + TX, ethyl-DDD (1056) + TX, ethylene dibromide (316) + TX, ethylene dichloride (chemical name) (1136) + TX, ethylene oxide [CCN] + TX, ethoxyfen (319) + TX, ethiprox (1142) + TX, EXD (1143) + TX, sulfamethoxam (323) + TX, fenamiphos (326) + TX, cypermethrin (1147) + TX, pyrifos (1148) + TX, fenthiocarb (1149) + TX, fenfluramine (1150) + TX, fenitrothion (335) + TX, fenthiocarb (336) + TX,Fenoxacrim (1153) + TX, fenoxycarb (340) + TX, cypermethrin (1155) + TX, cypermethrin (342) + TX, fenpyrad + TX, fenthion (1158) + TX, fenthion (346) + TX, fenthion-ethyl [CCN] + TX, cypermethrin (349) + TX, fipronil (354) + TX, flonicamid (358) + TX, flubendiamide (CAS Reg. No.: 272451-65-7) + TX, flucofuron (1168) + TX, flucyclopenthix (366) + TX, flucythrin (367) + TX, diflubenzuron (116 9)+TX, flufenacet[CCN]+TX, flufenoxuron(370)+TX, triflumethrin(1171)+TX, flumethrin(372)+TX, fluvalinate(1184)+TX, FMC1137(research code)(1185)+TX, diflubenzuron(1191)+TX, flufenoxam(405)+TX, flufenoxam hydrochloride(405)+TX, anthracene(1192)+TX, formparanate(1193)+TX, fenthion(1194)+TX, forspiramate(1195)+TX, thiathrin(408)+TX, fenthion(1196)+TX, furathiocarb(412)+TX, pyrethroid(1 200)+TX, γ-cyhalothrin (197)+TX, γ-HCH (430)+TX, biguanide salt (422)+TX, biguanide acetate (422)+TX, GY-81 (research code) (423)+TX, benzylfenthion (424)+TX, chlorfenapyr (425)+TX, HCH (430)+TX, HEOD (1070)+TX, febuda (1211)+TX, heptylphos (432)+TX, cypermethrin [CCN]+TX, hexaflumuron (439)+TX, HHDN (864)+TX, hydrazone (443)+TX, hydrocyanic acid (444)+TX, methoprene (445)+TX, hyquincarb )(1223)+TX、Imidacloprid(458)+TX、Imidacloprid(460)+TX、Indoxacarb(465)+TX、Methyl iodide(IUPAC name)(542)+TX、IPSP(1229)+TX、Chlorpheniramine(1231)+TX、Carbochlorin(1232)+TX、Carbofuran(473)+TX、Isocarb(1235)+TX、Isothioate(1236)+TX、Transplanting agent(1237)+TX、Isoprocarb(472)+TX、Isopropyl O-(methoxyaminothiophosphoryl)salicylate(IUPAC name)(473)+TX、Isopropyl thioate(474)+TX、Isosulfate(1244)+TX、Oxamethasone(480)+TX、Ivermectin [CCN] + TX, jasperdin I (696) + TX, jasperdin II (696) + TX, iodine (1248) + TX, juvenile hormone I [CCN] + TX, juvenile hormone II [CCN] + TX, juvenile hormone III [CCN] + TX, chlorfenapyr (1249) + TX, methoprene (484) + TX, λ-cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepidomectin (CCN) + TX, parabromophos (1250) + TX, lindane (430) + TX, lirimfos (1251) + TX, lufenuron (490) + TX, thiazothion (1253) + TX, m-isopropylphenyl methyl Aminocarbamate (IUPAC name) (1014) + TX, magnesium phosphide (IUPAC name) (640) + TX, malathion (492) + TX, tebuconazole (1254) + TX, phosphazolin (1255) + TX, cypermethrin (502) + TX, tetramethylphos (1258) + TX, cypermethrin (1260) + TX, diazinon (1261) + TX, mercurous chloride (513) + TX, mesulfenfos (1263) + TX, metaflumizone (CCN) + TX, metamizole (519) + TX, metamizole potassium (519) + TX, metamizole sodium (519) + TX, cypermethrin (1266) + TX, methamidophos (527) +TX, methanesulfonyl fluoride (IUPAC / Chemical Abstracts name) (1268) +TX, methidathion (529) +TX, methiocarb (530) +TX, ethiophanate (1273) +TX, methomyl (531) +TX, methoprene (532) +TX, mequindox (1276) +TX, methethrin (533) +TX, methoxychlor (534) +TX, anisyl (535) +TX, methyl bromide (537) +TX, methyl isothiocyanate (543) +TX, methyl chloroform [CCN] +TX, dichloromethane [CCN] +TX, metofluthrin [CCN] +TX, metoclopramide (550) +TX, dimethoate (1288) +TX, mefenphos (55 6)+TX, Zikwei (1290)+TX, Mimbetin (557)+TX, Milbemycin [CCN]+TX, Propylene fluoride (1293)+TX, Mirex (1294)+TX, Monocrotophos (561)+TX, Moxifen (1300)+TX, Moxidectin [CCN]+TX, Naphthyl fluoride [CCN]+TX, Dibromophos (567)+TX, Naphthalene (IUPAC / Chemical Abstracts Name) (1303)+TX, NC-170 (research code) (1306)+TX, NC-184 (compound code)+TX, Nicotine (578)+TX, Nicotine sulfate (578)+TX, Flufenamide (1309)+TX, Nitenpyram (579)+TX,Nithiazine (1311) + TX, valfenuron (1313) + TX, valfenuron 1:1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, nornicotine (traditional name) (1319) + TX, flubendiamide (585) + TX, noviflumuron (586) + TX, O-5-dichloro-4-iodophenyl O-ethylethyl phosphonothioate (IUPAC name) (1057) + TX, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphonothioate (IUPAC name) (1074) + TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphonothioate (IUPAC name) (Name) (1075) + TX, O,O,O',O'-tetrapropyl dithiodipyrophosphate (IUPAC name) (1424) + TX, oleic acid (IUPAC name) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, sulfone-methyl (609) + TX, isosulfoxon (1324) + TX, sulfone-methyl (1325) + TX, pp'-DDT (219) + TX, p-dichlorobenzene [CCN] + TX, parathion (615) + TX, parathion-methyl (616) + TX, chlorfenuron [CCN] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (IUPAC name) (623) + TX, permethrin (626) + TX, petroleum oils (628) + TX, PH 60-38 (study code) (1328) + TX, fenthion (1330) + TX, phenothrin (630) + TX, fenthion (631) + TX, phorate (636) + TX, phosalone (637) + TX, thiophanate (1338) + TX, phosmet (638) + TX, parachlorothion (1339) + TX, phosphamidon (639) + TX, phosphine (IUPAC name) (640) + TX, phoxim (642) + TX, phoxim-methyl (1340) + TX, pirimetaphos (1344) + TX, pirimetaphos (65 1)+TX, chlorfenapyr-ethyl (1345)+TX, chlorfenapyr-methyl (652)+TX, polychlorodicyclopentadiene isomers (IUPAC name) (1346)+TX, polychloroterpenes (traditional name) (1347)+TX, potassium arsenite [CCN]+TX, potassium thiocyanate [CCN]+TX, propylthiophene (655)+TX, precocious phosphine I [CCN]+TX, precocious phosphine II [CCN]+TX, precocious phosphine III [CCN]+TX, acetyl pyrimidophos (1349)+TX, profenofos (662)+TX, profluthrin [CCN]+TX,Fencarb (1354) + TX, Fencarb (1355) + TX, Fencarb (1356) + TX, Fencarb (673) + TX, Fencarb (678) + TX, Fencarb (1360) + TX, Fencarb (686) + TX, Fencarb (1362) + TX, Fencarb (CCN) + TX, Fencarb (688) + TX, Fencarb (689) + TX, Fencarb (693) + TX, Fencarb (1367) + TX, Fencarb I (696) + TX, Fencarb II (696) + TX, Fencarb (696) + TX 、pyridaben (699) + TX, pyridalyl (700) + TX, pyridafenphos (701) + TX, pyridafenphos (706) + TX, pyrimethanil (1370) + TX, pyriproxyfen (708) + TX, quassia extract [CCN] + TX, quinalphos (711) + TX, quinalphos-methyl (1376) + TX, quinalphos (1380) + TX, quintiofos (1381) + TX, R-1492 (research code) (1382) + TX, rafoxanide [CCN] + TX, resmethrin (719) + TX, rotenone (722) + TX, RU 15525 (research code) (723) + TX, RU 25475 (research code) (1386) + TX, ryania (1387) + TX, ryanodine (traditional name) (1387) + TX, sabafos (725) + TX, octamidine (1389) + TX, cadastrefos + TX, selamectin [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, flusilate (728) + TX, SN72129 (research code) (1397) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoride (I UPAC / Chemical Abstracts name) (1399) + TX, sodium hexafluorosilicate (1400) + TX, sodium pentachlorophenol (623) + TX, sodium selenate (IUPAC name) (1401) + TX, sodium thiocyanate [CCN] + TX, threonylthion (1402) + TX, spinosad (737) + TX, spiromesifen (739) + TX, spirotetramat (CCN) + TX, sulcofuron (746) + TX, sulcofuron-sodium (746) + TX, sulfluramid (750) + TX, thiophanate (753) + TX, sulfonyl fluoride (756) + TX, thiopromide (1408) + TX,Tars (758) + TX, τ-fluvalinate (398) + TX, thiabendazim (1412) + TX, TDE (1414) + TX, tebufenozide (762) + TX, tebufenpyrad (763) + TX, butylpyrimidin (764) + TX, flubendiamide (768) + TX, tefluthrin (769) + TX, tebuconazole (770) + TX, TEPP (1417) + TX, cypermethrin (1418) + TX, terbufoline (terbam) + TX, terbufophos (773) + TX, tetrachloroethane [CCN] + TX, chlorpyrifos (777) + TX, tetramethrin (787) + TX )+TX, θ-cypermethrin (204)+TX, thiacloprid (791)+TX, thiafenox+TX, thiamethoxam (792)+TX, thicrofos (1428)+TX, cypermethrin (1431)+TX, cyclohexane (798)+TX, cyclohexane hydrogen oxalate (798)+TX, thiodicarb (799)+TX, long-lasting carbendazim (800)+TX, methyl sulfamethoxam (801)+TX, thiosulfuron (1434)+TX, thiosultap (803)+TX, thiosultap-s odium)(803)+TX, thuringin [CCN]+TX, tolfenpyrad (809)+TX, tralomethrin (812)+TX, transfluthrin (813)+TX, transpermethrin (1440)+TX, cypermethrin (1441)+TX, triazophos (818)+TX, triazophos (820)+TX, triazophos+TX, trichlorfon (824)+TX, trichlormetaphos-3[CCN]+TX, chlorpyrifos (1452)+TX, trichlorprop (1455)+TX 、thiocarb (835) + TX, cypermethrin (840) + TX, methoprene (1459) + TX, aphidoxonil (847) + TX, vaniliprole [CCN] + TX, veratridine (725) + TX, veratridine (725) + TX, XMC (853) + TX, methoprene (854) + TX, YI-5302 (compound code) + TX, ζ-cypermethrin (205) + TX, zetamethrin + TX, zinc phosphide (640) + TX, zolaprofos (1469) and ZXI 8901 (research code) (858) + TX, cyantraniliprole [736994-63-19] + TX, chlorantraniliprole [500008-45-7] + TX, cyenopyrafen [560121-52-0] + TX, cyflumetofen [400882-07-7] + TX,Pyrifluquinazon [337458-27-2] + TX, spinetoram [187166-40-1 + 187166-15-0] + TX, spirotetramat [203313-25-1] + TX, sulfoxaflor [946578-00-3] + TX, flufiprole [704886-18-0] + TX, chlorfluanid [915288-13-0] + TX, tetramethylfluthrin [84937-88-2] + TX, triflumezopyrim (disclosed in WO 2012 / 092115) + TX, fluxametamide (WO 2007 / 026965) + TX, epsilon-metofluthrin [240494-71-7] + TX, epsilon-momfluorothrin [1065124-65-3] + TX, fluazaindolizine [1254304-22-7] + TX, chloroprallethrin [399572-87-3] + TX, fluxametamide [928783-29-3] +TX, cyhalodiamide [1262605-53-7] +TX, tioxazafen [330459-31-9] +TX, broflanilide [1207727-04-5] +TX, butene fipronil [704886-18-0] +TX, cyclic bromofenapyr [1031756-98-5] +TX, tetraniliprole [1229654-66-3] +TX, pyrimidine (described in WO 2010 / 060231) +TX, cycloheximide (described in WO 2005 / 077934) +TX,

[0830] Molluscicide selected from the group consisting of di(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetyl arsenite [CCN] + TX, copper sulfate (172) + TX, triphenyltin (347) + TX, iron phosphate (IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide ethanolamine salt (57 6)+TX, pentachlorophenol (623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX, thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX, trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347)+TX, pyriprole [394730-71-3]+TX,

[0831] A nematicide selected from the group consisting of: AKD-3088 (compound code) + TX, 1,2-dibromo-3-chloropropane (IUPAC / Chemical Abstracts name) (1045) + TX, 1,2-dichloropropane (IUPAC / Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane and 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC / Chemical Abstracts name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1,3,5-thiadiazin-3-yl acetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (210) + TX, abamectin (1) + TX, acetofenamide [CCN] + TX, cotton boll carb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, AZ60541 (compound code) + TX, benclothiaz [CCN] + TX, benclothiaz (62) + TX, butylpyridaben + TX, cadusafos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbofuran (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, cloethocarb (999) + TX, cell division Cytokinins (210) + TX, dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafos (1044) + TX, dichlofenthion (1051) + TX, dicliphos + TX, dimethoate (262) + TX, emamectin [CCN] + TX, emamectin benzoate (291) + TX, eprinomectin (291) + TX, [CCN] + TX, ethoprophos (3 12)+TX, dibromoethane (316)+TX, fenamiphos (326)+TX, tebufenpyrad+TX, fenpyrad (1158)+TX, fosthiazate (408)+TX, fosthietan (1196)+TX, furfural [CCN]+TX, GY-81 (research code) (423)+TX, heterophos [CCN]+TX, iodomethane (IUPAC name) (542)+TX X, isamidofos (1230) + TX, isazofos (1231) + TX, kinetin [CCN] + TX, mecarphon (210) + TX, mecarphon (1258) + TX, metamizole (519) + TX, metamizole potassium salt (519) + TX, metamizole sodium salt (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime [CCN] + TX, moxidectin [CCN] + TX, Myrotheciumverrucaria) component (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosphocarb [CCN] + TX, sebufos + TX, selamectin [CCN] + TX, spinosad (737) + TX, terbufos + TX, terbufos (773) + TX, tetrachlorothiophene (IUPAC / Chemical Abstracts Name) (1422) + TX, thiaf enox+TX, thionazin (1434)+TX, triazophos (820)+TX, triazuron+TX, dimethylphenol [CCN]+TX, YI-5302 (compound code) and zeatin (210)+TX, fluensulfone [318290-98-1]+TX,

[0832] A nitrification inhibitor selected from the group consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,

[0833] A plant activator selected from the group consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (720) + TX,

[0834] A rodenticide selected from the group consisting of: 2-isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, α-chlorohydrin [CCN] + TX, aluminum phosphide (640) + TX, antoquinone (880) + TX, arsenic trioxide (882) + TX, barium carbonate (891) + TX, bisulfamethoxazole (912) + TX, brodifacoum (89) + TX, Bromadiolone (91) + TX, Bromadiolone (92) + TX, Calcium Cyanide (444) + TX, Azotobacterium (127) + TX, Chlorodiolone (140) + TX, Vitamin D3 (850) + TX, Chlorodiol (1004) + TX, Cytodextrin (1005) + TX, Cytodextrin (175) + TX, Cytodextrin (1009) + TX, Cytodextrin (246) + TX, Cytodextrin (249) + TX, Sodium Diphacin (273) + TX, Vitamin D2 (301) + TX, Fludioxaline (357) + TX, fluoroacetamide (379) + TX, fludioxaline (1183) + TX, fludioxaline hydrochloride (1183) + TX, γ-HCH (430) + TX, HCH (430) + TX, hydrocyanic acid (444) + TX, iodomethane (IUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (IUPAC name) (640) + TX, methyl bromide (537) + TX, fludioxaline (1318) + TX, chlorfenapyr (13 36)+TX, phosphine (IUPAC name) (640)+TX, phosphorus [CCN]+TX, warfarin (1341)+TX, potassium arsenite [CCN]+TX, warfarin (1371)+TX, scilla glycoside (1390)+TX, sodium arsenite [CCN]+TX, sodium cyanide (444)+TX, sodium fluoroacetate (735)+TX, strychnine (745)+TX, thallium sulfate [CCN]+TX, warfarin (851) and zinc phosphide (640)+TX,

[0835] A synergist selected from the group consisting of 2-(2-butoxyethoxy)ethyl piperonyl ester (IUPAC name) (934) + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (324) + TX, MB-599 (research code) (498) + TX, MGK 264 (research code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (research code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX,

[0836] An animal repellent selected from the group consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper cyclohexane [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetate (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, salamine (804) + TX, trimethacarb (840) + TX, zinc cyclohexane [CCN] and ziram (856) + TX,

[0837] a virucide selected from the group consisting of imipenem [CCN] and ribavirin [CCN] + TX,

[0838] A wound protective agent selected from the group consisting of mercuric oxide (512) + TX, octhiazone (590) and thiophanate-methyl (802) + TX,

[0839] and biologically active compounds selected from the group consisting of azaconazole [60207-31-0] + TX, bifenthionol [70585-36-3] + TX, oxadiazol [116255-48-2] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [119446-68-3] + TX, diniconazole [83657-24-3] + TX, fluoxepiconazole [106325-08-0] + TX, fenbuconazole [114369-43-6] + TX, fluquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol [76674-21-0] + TX, hexamethylenetetracycline [106325-08-0] + TX, fenbuconazole [114369-43-6] + TX, fluquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, fluconazole [76674-21-0] + TX, hexamethylenetetracycline [106325-08-0] + TX, hexamethylenetetracycline [106325-08-0] + TX, hexamethylenetetracycline [114369-43-6] + TX, fluquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, fluquinconazole [76674-21-0] + TX, hexamethylenetetracycline [106325-08-0] + TX, hexamethylene Azoconazole [79983-71-4] + TX, imazalil [35554-44-0] + TX, imipenem [86598-92-7] + TX, ipconazole [125225-28-7] + TX, metconazole [125116-23-6] + TX, myclobutanil [88671-89-0] + TX, pyrifenox [101903-30-4] + TX, penconazole [66246-88-6] + TX, prothioconazole [178928-70-6] + TX, pyrifenox [88283-41-4] + TX, prochloraz [67747-09-5] + TX, propiconazole [60207-90-1] + TX, silfenazole ( simeconazole) [149508-90-7] + TX, tebuconazole [107534-96-3] + TX, fluconazole [112281-77-3] + TX, triadimefon [43121-43-3] + TX, triadimefon [55219-65-3] + TX, triflumuron [99387-89-0] + TX, trichlorfon [131983-72-7] + TX, tricyclamic acid [12771-68-5] + TX, chlorfenapyr [60168-88-9] + TX, fluchlorapyr [63284-71-9] + TX, bupirimate [41483-43-6] + TX, dimethirimol [5221-53-4] + TX, ethirimol [23947-60-6] + TX, dodecacyclic morpholine [1593-77-7] + TX, fenpropidine [67306-00-7] + TX, fenpropimorph [67564-91-4] + TX, spiroxafil [118134-30-8] + TX, tridecafil [81412-43-3] + TX, cyprodinil [121552-61-2] + TX, pyraclostrobin [110235-47-7] + TX, pyrimethanil [53112-28-0] + TX,Flunix [74738-17-3] + TX, fludioxonil [131341-86-1] + TX, benalaxyl [71626-11-4] + TX, furalaxyl [57646-30-7] + TX, metalaxyl [57837-19-1] + TX, R metalaxyl [70630-17-0] + TX, furamide [58810-48-3] + TX, oxadixyl [77732-09-3] + TX, benomyl [17804-35-2] + TX, carbendazim [10605-21-7] + TX, debaclofen carb)[62732-91-6]+TX、maisuining[3878-19-1]+TX、thiabendazole[148-79-8]+TX、chlozolinate[84332-86-5]+TX、dichlozoline[24201-58-9]+TX、Iprodione[36734-19-7]+TX、myclozoline[54864-61-8]+TX、procymidone[32809-16-8]+TX、vinclozoline[50471-44 -8]+TX, boscalid[188425-85-6]+TX, carboxin[5234-68-4]+TX, furanilide[24691-80-3]+TX, flutolanil[66332-96-5]+TX, mefenamic acid[55814-41-0]+TX, oxycarboxin[5259-88-1]+TX, penthiopyrad[183675-82-3]+TX, thiopyrad[130000-40-7]+TX, biguanide[108173-90-6]+TX, dodine[2439-10-3] [112-65-2] (free base) + TX, iminoctadine [13516-27-3] + TX, azoxystrobin [131860-33-8] + TX, etherstrobin [149961-52-4] + TX, enestrobin {Proc. BCPC, Int. Congr., Glasgow. 2003, 1, 93} + TX, fluoxastrobin [361377-29-9] + TX, methyl etherstrobin [143390-89-0] + TX, oxazolidinone [133408-50-1] + TX, trifloxystrobin [141517-21-7] + TX, trifloxystrobin [248593-16-0] + TX,Picoxystrobin [117428-22-5] + TX, pyraclostrobin [175013-18-0] + TX, ferbam [14484-64-1] + TX, mancozeb [8018-01-7] + TX, maneb [12427-38-2] + TX, metiram [9006-42-2] + TX, propineb [12071-83-9] + TX, salamine [137-26-8] + TX, maneb [12122-67-7] + TX, ferbam [137-30-4] + TX, captafol [2425-06-1] + TX, captan [133-06-2] + TX, benzyl alcohol Amine [1085-98-9] + TX, fluoroimide [41205-21-4] + TX, folpet [133-07-3] + TX, toluenesulfonamide [731-27-1] + TX, Bordeaux mixture [8011-63-0] + TX, copper hydroxide (copperhydroxid) [20427-59-2] + TX, copper chloride (copperoxychlorid) [1332-40-7] + TX, copper sulfate (coppersulfat) [7758-98-7] + TX, copper oxide (copperoxid) [1317-39-1] + T X, mancopper [53988-93-5] + TX, oxine-copper [10380-28-6] + TX, dinocap [131-72-6] + TX, phthalocyanine (nitrothal-isopropyl) [10552-74-6] + TX, kewensan [17109-49-8] + TX, iprobenphos [26087-47-8] + TX, isoprothiol [50512-35-1] + TX, phosdiphen [36519-00-3] + TX, Pyrazophos[13457-18-6]+TX、tolclofos-methyl[57018-04-9]+TX、acibenzolar-S-methyl[135158-54-2]+TX、dichlorvos[101-05-3]+TX、benthiopyrad[413615-35-7]+TX、blasticidin-S[2079-00-7]+TX、chinomethionat[2439-01-2]+TX、chloroneb[2675-77-6]+TX、Chlorothalonil [1897-45-6] + TX, cyfluanid [180409-60-3] + TX, cymoxanil [57966-95-7] ​​+ TX, dichlone [117-80-6] + TX, diclocymet [139920-32-4] + TX, diclomezine [62865-36-5] + TX, dicloran [99-30-9] + TX, diethofencarb [87130-20-9] + TX, dimethomorph [110488-70-5] + TX, SYP LI90 (Flumorph) [211867-47-9] + TX, dithianon [3347-22-6] + TX, ethaboxam [162650-77-3] + TX, etridiazole [2593-15-9] + TX, famoxadone [131807-57-3] + TX, fenamidone [161326-34-7] + TX, fenoxanil [115852-48-7] + TX, fentin [668-34-8] + TX, pyrimidine (ferimzone) [89269-64-7] + TX, fluazinam [79622-59-6] + TX, fluopicolide [239110-15-7] + TX, flusulfamide [106917-52-6] + TX, fenhexamid [126833-17-8] + TX, fosetyl-aluminium [39148-24-8] + TX, hymexazol [10004-44-1] + TX, propineb [140923-17-7] + TX, IKF 916 (Cyazofamid) [120116-88-3] + TX, kasugamycin [6980-18-3] + TX, methasulfocarb [66952-49-6] + TX, mefenacet [220899-03-6] + TX, pencycuron [66063-05-6] + TX, phthalide [27355-22-2] + TX, polyoxins [11113-80-7] + TX, probenazole [27605-76-1] + TX, propamocarb [25606-41-1] + TX,Proquinazid [189278-12-4] + TX, pyroquilon [57369-32-1] + TX, quinoxyfen [124495-18-7] + TX, pentachloronitrobenzene [82-68-8] + TX, sulfur [7704-34-9] + TX, thiazolin [223580-51-6] + TX, triazoxide [72459-58-6] + TX, tricyclazole [41814-78-2] + TX, triamcinol [26644-46-2] + TX, validamycin [37248-47-8] + TX, zoxamide (RH7281) [156052-68-5] + TX, mandipropamid [374726-62-2] + TX, isopyrazam [881685-58-1] + TX, sedaxane [874967-67-6] + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide (disclosed in WO2007 / 048556) + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide (disclosed in WO 2006 / 087343) + TX, [(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridyl)-2H,11H-naphtho[2,1-b ] pyrano[3,4-e]pyran-4-yl]methyl-cyclopropanecarboxylate [915972-17-7] + TX and 1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide [926914-55-8] + TX; and

[0840] Microbial agents, including: Acinetobacter lwoffii + TX, Acremonium alternatum + TX + TX, Acremonium cephalosporium + TX + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, and AdoxGV +TX, Agrobacterium radioactive strain K84 +TX, Alternaria interspersed +TX, Alternaria cassia +TX, Alternaria destructans +TX, Powdery mildew +TX, Aspergillus flavus AF36 +TX, Aspergillus flavus NRRL 21882 +TX, Aspergillus +TX, Aureobasidium +TX, Azospirillum +TX, ( +TX、TAZO )+TX, Azotobacter+TX, Round brown nitrogen-fixing bacteria +TX, cystic nitrogen-fixing bacteria (Bionatural Blooming )+TX, Bacillus amyloliquefaciens+TX, Bacillus cereus+TX, Bacillus chitinosporus strain CM-1+TX, Bacillus chitinosporus strain AQ746+TX, Bacillus licheniformis strain HB-2 (Biostart TM )+TX, Bacillus licheniformis strain 3086 ( +TX、Green )+TX, Bacillus circulans+TX, Bacillus firmus ( +TX, +TX, )+TX, Bacillus firmus strain I-1582+TX, Bacillus macerans+TX, Bacillus marismortui+TX, Bacillus megaterium+TX, Bacillus mycoides strain AQ726+TX, Bacillus japonicus (Milky Spore )+TX, Bacillus pumilus+TX, Bacillus pumilus strain GB34 (Yield )+TX, Bacillus pumilus strain AQ717+TX, Bacillus pumilus strain QST 2808( +TX, Ballad )+TX, Bacillus sphaericus +TX, Bacillus +TX, Bacillus strain AQ175 +TX, Bacillus strain AQ177 +TX, Bacillus strain AQ178 +TX, Bacillus subtilis strain QST 713 ( +TX, +TX, )+TX, Bacillus subtilis strain QST 714 +TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilis strain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis strain FZB24 ( +TX, )+TX, Bacillus thuringiensis Cry2Ae+TX, Bacillus thuringiensis Cry1Ab+TX, Bacillus thuringiensis aizawai GC 91 +TX, Bacillus thuringiensis israelensis ( +TX, +TX, )+TX, Bacillus thuringiensis kurstaki ( +TX, +TX, +TX, +TX, Scutella +TX, Turilav +TX, +TX、Dipel +TX, +TX, )+TX, Bacillus thuringiensis subsp. Kurstaki BMP 123 +TX, Bacillus thuringiensis subsp. Kurstaki HD-1 +TX, Bacillus thuringiensis strain BD#32+TX, Bacillus thuringiensis strain AQ52+TX, Bacillus thuringiensis var. ayuzawa ( +TX, )+TX, bacteria ( +TX, +TX, )+TX, Clavipacter michiganensis phage +TX, +TX, Beauveria bassiana ( +TX, Brocaril )+TX, Beauveria bassiana GHA (Mycotrol +TX, Mycotrol +TX, )+TX, Beauveria bassiana ( +TX, Schweizer +TX, )+TX, Beauveria bassiana+TX, Botrytis cinerea+TX, Bradyrhizobium sojae +TX, Bacillus brevis +TX, Bacillus thuringiensis tenebrionis +TX, BtBooster+TX, Burkholderia cepacia ( +TX, +TX、Blue )+TX, Burkholderia gladii+TX, Burkholderia gladioli+TX, Burkholderia spp.+TX, CBH Canadian )+TX, Candida cheese+TX, Candida anonymum+TX, Candida fructus+TX, Candida glabrata+TX, Candida guilliermondii+TX, Candida orijin+TX, Candida olive strain O+TX, Candida parapsilosis+TX, Candida mycofilm+TX, Candida ferrugifera+TX, Candida reukaufii+TX, Candida saitoana( +TX, )+TX, Candida sakei+TX, Candida spp.+TX, Candida gracilis+TX, Cedecea dravisae+TX, Xanthomonas spp.+TX, Spirochaete +TX, Chaetomium globosum +TX, Chromobacterium subtsugae strain PRAA4-1T +TX, Cladosporium cladosporium+TX, Cladosporium oxysporum+TX, Cladosporium chlorocephalum+TX, Cladosporium genus+TX, Cladosporium tenuis+TX, Gliocladium roseum +TX, Colletotrichum acutatum +TX, Cotans )+TX, Conchoderma+TX, Cryptococcus albus +TX, Cryptococcus terrestris +TX, Cryptococcus infirmo-miniatus +TX, Cryptococcus laurentii +TX, Apple tridentata granulosis virus +TX, Cupriavidus campinensis +TX, Codling moth granulosis virus +TX, codling moth granulosis virus ( +TX, Madex +TX, MadexMax / )+TX、Cylindrobasidium laeve +TX, Cladosporium spp.+TX, Debaryomyces hansenii+TX, Drechslera hawaiinensis+TX, Enterobacter cloacae+TX, Enterobacteriaceae+TX, Entomophilus virulens +TX, Epicoccum nigrum +TX, Epicoccum purpurascens +TX, Epicoccum +TX, Filobasidium floriforme +TX, Fusarium acuminate +TX, Fusarium thunbergii +TX, Fusarium oxysporum ( / Biofox )+TX, Fusarium spp.+TX, Fusarium spp.+TX, Galactomyces geotrichum+TX, Glechoma spp. ( +TX, )+TX, Gliocladium roseum+TX, Gliocladium spp. +TX, Gliocladium viride +TX, Granulovirus +TX, Halobacillus halophilus +TX, Halobacillus litoralis +TX, Halobacillus trueperi +TX, Halomonas +TX, Halomonas subglaciescola +TX, Halovibriovariabilis +TX, Hansenula vitis var. vinifera +TX, Helicoverpa armigera nuclear polyhedrosis virus +TX, corn earworm nuclear polyhedrosis virus +TX, isoflavone-formononetin +TX, Kloeckner yeast +TX, Kloeckner yeast +TX, Lagenidium giganteum +TX, Lecanicillium longisporum +TX, Lecanicillium muscarium +TX, Lymantria dispar nuclear polyhedrosis virus +TX, Halococcus halophilus +TX, Meira geulakonigii +TX, Metarhizium anisopliae +TX, Metarhizium anisopliae (Destruxin )+TX, Metschnikowia fruticola +TX, Metschnikowiapulcherrima +TX, Microdochium dimerum +TX, Micromonospora coerulea +TX, Microsphaeropsis ochracea +TX, Muscodor albus 620 +TX, Muscodor roseus strain A3-5+TX, Mycorrhizae spp. ( +TX、Root )+TX, Myrotheca verrucosa strain AARC-0255 +TX、BROS +TX, Ophiostoma piliferum strain D97 +TX, Paecilomyces farinosus +TX, Paecilomyces fumosorum +TX, )+TX, Paecilomyces linacinus (Biostat )+TX, Paecilomyces lilacinus strain 251 (MeloCon )+TX, Paenibacillus polymyxa+TX, Pantoea agglomerans (BlightBan )+TX, Pantoea+TX, Pasteurella +TX, Pasteuria nishizawae+TX, Penicillium chrysogenum+TX, Penicillium billai( +TX, )+TX, Penicillium breviscompactum+TX, Penicillium vulgaris+TX, Penicillium griseo-yellow+TX, Penicillium purpurogenum+TX, Penicillium spp.+TX, Penicillium viridum+TX, Phlebiopsis gigantean +TX, phosphate-solubilizing bacteria +TX, Cryptophyton+TX, Phytophthora palmatum +TX, Pichia anomala +TX, Pichia guilermondii +TX, Pichia membrane +TX, Pichia nail +TX, Pichia stipitis +TX, Pseudomonas aeruginosa +TX, Pseudomonas aureofasciens (Spot-Less )+TX, Pseudomonas cepacia+TX, Pseudomonas chlororaphis +TX, Pseudomonas corrugate +TX, Pseudomonas fluorescens strain A506 (BlightBan )+TX, Pseudomonas putida+TX, Pseudomonas reactans+TX, Pseudomonas spp.+TX, Pseudomonas syringae +TX, Pseudomonas aureus +TX, Pseudomonas fluorescens +TX, Pseudozyma flocculosa strain PF-A22UL (Sporodex )+TX、Puccinia canaliculata+TX、Puccinia thlaspeos(Wood )+TX、Pythium paroecandrum+TX、Pythium oligandrum +TX, )+TX, Pythium+TX, Rhanella aquatilis+TX, Rhanella+TX, Rhizobium ( +TX, )+TX, Rhizoctonia spp.+TX, Rhodococcus sphaeroides strain AQ719+TX, Rhodosporidium diobovatum+TX, Rhodosporidium toro +TX, Rhodotorula spp.+TX, Rhodotorula glutinosus+TX, Rhodotorula graminis+TX, Rhodotorula mucilagnosa+TX, Rhodotorula crenosa+TX, Saccharomyces cerevisiae+TX, Salinococcus roseus+TX, Sclerotinia microtypingii+TX, Sclerotinia microtypingii +TX, Cylindrotheca spp.+TX, Scytalidium uredinicola+TX, Spodoptera exigua nuclear polyhedrosis virus ( +TX, )+TX, Serratia marcescens+TX, Serratia puertoris+TX, Serratia spp.+TX, Spodoptera littoralis nuclear polyhedrosis virus +TX, Rhodosporidium +TX, Stenotrophomonas maltophilia +TX, Streptomyces albaduncus +TX, Streptomyces albaduncus +TX, Streptomyces defoliatus +TX, Streptomyces flavus +TX, Streptomyces griseus +TX, Streptomyces griseus +TX, Streptomyces lydicus +TX, Streptomyces lydicus WYEC-108 +TX, Streptomyces violaceus +TX, Tilletiopsis minor +TX, Tilletiopsis genus +TX, Trichoderma aculeatus (T34 )+TX, Trichoderma gamsii +TX, Trichoderma aureum +TX, Trichoderma th 382+TX, Trichoderma harzianum rifai +TX, Trichoderma harzianum T-22 ( +TX, PlantShield +TX, +TX, )+TX, Trichoderma harzianum T-39 +TX, Trichoderma inhamatum +TX, Trichoderma koningii +TX, Trichoderma LC 52 +TX, Trichoderma lignin +TX, Trichoderma longifolia +TX, Trichoderma polysporum (Trichoderma polysporum) (Binab )+TX, Trichoderma taxol +TX, Trichoderma viride +TX, Trichoderma viride (formerly known as Gliocladium viride GL-21) +TX, Trichoderma viride +TX, Trichoderma viride strain ICC 080 +TX, Trichosporon spp. +TX, Trichothecene spp. +TX, Trichothecene spp. +TX, Trichothecene spp. +TX, Typhula phacorrhiza strain 94670 +TX, Typhula phacorrhiza strain 94671 +TX, Ulocladium oudemansii +TX, Ulocladium oudemansii +TX, Ustilago maydis +TX, various bacteria and supplementary nutrients (Natural )+TX, various fungi (Millennium )+TX, Verticillium chlamydosporium+TX, Verticillium lecanii ( +TX, )+TX、Vip3Aa20 +TX, Virgibaclillus marismortui+TX, Xanthomonas campestris pv.Poae +TX, Xenorhabdus burnetii +TX, Xenorhabdus nematophila; and

[0841] Plant extracts, including pine oil +TX, Azadirachtin (Plasma Neem +TX, +TX, +TX, +TX, plant IGR ( +TX, )+TX, rapeseed oil (Lilly Miller )+TX, Chenopodium ambrosioidesnear ambrosioides +TX, Chrysanthemum extract +TX, extract of neem oil +TX, essential oils of Lamiaceae +TX, clove rosemary mint extract and thyme essential oil (Garden insect )+TX, betaine +TX, garlic +TX, lemongrass essential oil +TX, neem essential oil +TX, catnip (mint essential oil) +TX, nepeta catarina +TX, nicotine +TX, oregano essential oil +TX, Sesame essential oil +TX, pyrethrum+TX, soapberry +TX, Reynoutria sachalinensis ( +TX, )+TX, rotenone (Eco )+TX, Rutaceae plant extract +TX, soybean oil (Ortho )+TX, tea tree essential oil (Timorex )+TX, thyme essential oil+TX, MMF+TX, +TX, a blend of rosemary, sesame, mint, thyme and cinnamon extracts (EF )+TX, clove rosemary and mint extract mixture (EF )+TX, clove mint garlic oil and mint mixture (Soil )+TX, kaolin +TX, brown algae that store glucose as well as

[0842] Pheromones, including: Blackhead Firefly Pheromone (3M Spray Blackhead Firefly )+TX, Codling moth pheromone (Paramount dispenser - (CM) / Isomate )+TX, grape leaf roller pheromone (3M MEC-GBM spray type )+TX, leaf roller pheromone (3M MEC-LR spray type )+TX, housefly pheromone (Snip7Fly +TX、Starbar Premium Fly )+TX, Pear Borer Pheromone (3M Pear Borer Spray Type )+TX, peach borer pheromone +TX, Tomato Pinworm Pheromone (3M Spray Type )+TX, Entostat powder (extract from palm tree) (Exosex )+TX, (E+TX, Z+TX, Z)-3+TX, 8+TX, 11-tetradecatrienyl acetate+TX, (Z+TX, Z+TX, E)-7+TX, 11+TX, 13-hexadecatrienal+TX, (E+TX, Z)-7+TX, 9-dodecadien-1-yl acetate+TX, 2-methyl-1-butanol+TX, calcium acetate+TX, +TX, +TX, +TX, lavandinol ester; and

[0843] Macrobiotics, including: Aphidius ervi + TX, Aphidius ervi +TX, Acerophagus papaya+TX, Coccinella bispot +TX, Coccinella bispotata +TX, Coccinella bispotata +TX, Ageniaspiscitricola+TX, Amblyseius andersoni ( +TX, )+TX, Amblyseius californicus ( +TX, )+TX, Amblyseius cucumeris ( +TX, Bugline )+TX, Pseudo-Amblyseius +TX, Bugline +TX, )+TX, Amblyseius osbornei +TX, Amitus hesperidum +TX, Anagrusatomus +TX, Anagyrus fusciventris +TX, Anagyrus kamali +TX, Anagyrus loecki +TX, Anagyrus pseudococci +TX, Red wax scale flat-horned jumping wasp (Anicetus benefices) +TX, Golden wasp (Anisopteromalus calandrae) +TX, Woodland flower stink bug (Anthocoris nemoralis) +TX, Short-spur Aphid Wasp ( +TX, )+TX, Aphelinus asychis+TX, Aphidius colemani +TX, Alphididae +TX, tobacco aphid wasp+TX, peach red aphid wasp +TX, aphid-eating gall midge +TX, aphid-eating gall midge +TX, Lingnan aphid wasp +TX, Indian golden aphid wasp +TX, cockroach egg long-tailed biting wasp (Aprostocetus hagenowii) +TX, rove beetle (Atheta coriaria) +TX, Bombus spp. +TX, European Bombus (Natupol )+TX, European Bumblebee ( +TX, )+TX, Cephalonomia stephanoderis+TX, Black-backed Red Ladybug (Chilocorus nigritus)+TX, Common Lacewing (Chrysoperla carnea) +TX, Common Lacewing +TX, Chrysoperla rufilabris+TX, Cirrospilus ingenuus+TX, Cirrospilus quadristriatus+TX, Citrostichus phyllocnistoides+TX, Closterocerus chamaeleon+TX, Closterocerus genus+TX, Coccidoxenoides perminutus +TX, Coccophagus cowperi+TX, Coccophagus lycimnia+TX, Coccophagus lycimnia+TX, Coccophagus luteola+TX, Coccophagus moniliformis+TX, +TX, )+TX, Japanese square-headed beetle+TX, Siberian jawed braconid wasp+TX, Siberian jawed braconid wasp +TX, pea leafminer +TX, small black ladybug (Delphastus catalinae) +TX, Delphastus pusillus+TX, Diachasmimorpha krausii+TX, Long-tailed fly miner+TX, Diaparsisjucunda+TX, Diaphorencyrtus aligarhensis+TX, Pea leafminer+TX, Pea leafminer +TX, )+TX, Siberian Braconid Wasp ( +TX, )+TX, Encarsia genus+TX, Encarsia spp.+TX, +TX, +TX, )+TX, Eretmoceruseremicus +TX, Encarsia guadeloupae +TX, Encarsia haitiensis +TX, Slender Hoverfly +TX, Eretmoceris siphonini+TX, Eretmocerus californicus+TX, Eretmocerus eremicus( +TX, Eretline )+TX, Eretmocerus eremicus +TX, Heinrich's aphid wasp+TX, Montessori's aphid wasp ( +TX, Eretline )+TX, Eretmocerussiphonini+TX, Four-spotted Ladybird (Exochomus quadripustulatus)+TX, Feltiella acarisuga +TX, Acarina +TX, Alishan fly miner +TX, Fopiusceratitivorus +TX, Wirless )+TX, thrips slender waist +TX, Galendromus occidentalis +TX, Goniozus legneri +TX, Echinops serratus +TX, Harmonia axyridis +TX, Heterorhabditis spp. (Lawn )+TX, Heterorhabditis elegans (NemaShield +TX, +TX, +TX, +TX, +TX, +TX, +TX, )+TX, Heterorhabditis megidis (Nemasys +TX, BioNem +TX、Exhibitline +TX, )+TX, Hippodamia convergens+TX, Hypoaspisaculeifer ( +TX, )+TX, Hypoaspismiles (Hypoline +TX, )+TX, Black Branch Gall Wasp+TX, Lecanoideus floccissimus+TX, Lemophagus errabundus+TX, Leptomastidea abnormis+TX, Leptomastix dactylopii +TX, Leptomastix epona+TX, Lindorus lophanthae+TX, Lipolexis oregmae+TX, Greenfly +TX, Tea-footed Aphid Wasp+TX, Dark-spine Blight Bug (Macrolophus caliginosus) ( +TX, +TX, )+TX, Mesoseiulus longipes+TX, Metaphycus flavus+TX, Metaphycus lounsburyi+TX, and Metaphycus hornbeam +TX, Microterys flavus +TX, Muscidifurax raptorellus and Spalangia cameroni +TX, Neodryinustyphlocybae+TX, California New Small Seiureus+TX, Cucumber Amblyseius +TX, Neoseiulus fallacis+TX, Nesideocoris tenuis( +TX, )+TX, Bronze Blackfly +TX, Orius insidiosus ( +TX, Oriline )+TX, Orius laevigatus ( +TX, Oriline )+TX、Oriline )+TX, small black flower stink bug +TX, Pauesiajuniperorum+TX, Pediobius foveolatus+TX, Phasmarhabditis hermaphrodita +TX, Phymastichus coffea+TX, Phytoseiulus macropilus+TX, Phytoseiulus chilensis ( +TX, )+TX, Cypripedium scaly-bellied +TX, Pseudacteon curvatus+TX, Pseudacteon obtusus+TX, Pseudacteon tricuspis+TX, Pseudaphycus maculipennis+TX, Pseudleptomastix mexicana+TX, Psyllaephagus pilosus+TX, Psyttalia concolor (complex)+TX, Rhyzobius lophanthae+TX, Australian ladybird+TX, Ruminadecollate+TX, Semielacher petiolatus+TX, Aphid +TX, Steinernema carinata (Nematac +TX, +TX, BioNem +TX, +TX, +TX, )+TX, Steinernema carinata ( +TX, Nemasys +TX, BioNem +TX, +TX, +TX, +TX、Exhibitline +TX, +TX, )+TX, Steinernema kraussei (Nemasys +TX, BioNem +TX、Exhibitline )+TX, Steinernema riobrave ( +TX, )+TX, Steinernema scapterisci (Nematac )+TX, Steinernematid genus+TX, Steinernematid genus (Guardian )+TX, Deep-point mite-feeding ladybug +TX, bright-bellied enameled wasp+TX, Tetrastichus setifer+TX, Thropobius semiluteus+TX, Chinese long-tailed wasp (Torymus sinensis)+TX, Tricholine )+TX, Trichogrammatid wasp +TX, Trichogramma spleniformis +TX, Trichogramma microplus +TX, Trichogramma ostriniae +TX, Trichogramma platneri +TX, Trichogramma shoriperid +TX, and Trichogramma striata; and

[0844] Other biological agents, including: abscisic acid + TX, +TX, Chondrostereum purpureum (Chontrol )+TX, Colletotrichum spondyloticum +TX, copper octanoate +TX, Delta trap (Trapline )+TX, Erwinia amylovora (Harpin) ( +TX、Ni-HIBIT Gold )+TX, ferric phosphate +TX, Trapline )+TX、 +TX, Grower's +TX, homobrassinolide +TX, iron phosphate (LillyMiller Worry Free Ferramol Slug & Snail )+TX, MCP Hail Trap (Trapline )+TX, Microctonus hyperodae+TX, Mycoleptodiscus terrestris +TX, +TX, +TX, +TX, Pheromone Trap (Thripline )+TX, potassium bicarbonate +TX, potassium salt of fatty acids +TX, potassium silicate solution +TX, potassium iodide + potassium thiocyanate +TX, +TX, spider venom +TX, locust microsporidia (Semaspore Organic Grasshopper )+TX, Trapline +TX, Rebell )+TX and trap (Takitrapline y+ )+TX.

[0845] References in brackets after the active ingredient, e.g. [3878-19-1], refer to Chemical Abstracts Registration Numbers. The mixed partners described above are known. When the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: CDS Tomlin; The British Crop Protection Council], they are described in that manual under the entry number given above in brackets for the specific compound; e.g. the compound "abamectin" is described under entry number (1). When "[CCN]" is added above for a specific compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is available on the internet: [A. Wood; Compendium of Pesticide Common Names (CCN)] Compendium of Pesticide Common Names ),copyright 1995-2004]; for example, the compound "acetoprole" is described on the Internet at the address http: / / www.alanwood.net / pesticides / acetoprole.html.

[0846] Most of the active ingredients mentioned above are referred to above by a so-called "common name," a related "ISO common name," or, in individual cases, another "common name." If the name is not a "common name," the nature of the name used is actually specified in parentheses for the specific compound; in that case, the IUPAC name, IUPAC / Chemical Abstracts name, "chemical name," "traditional name," "compound name," or "development code" is used. "CAS Registry Number" means the Chemical Abstracts Registry Number.

[0847] Active ingredient mixtures of a compound of formula I selected from Tables 1 to 88 and P and the above-mentioned active ingredients comprise a compound selected from Tables 1 to 88 and P and the above-mentioned active ingredients, 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, particularly preferably in a ratio of from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 is likewise preferred, especially in a ratio of 1:1, or 5:1, or 5:2, or 5: or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. Those mixing ratios are by weight.

[0848] The mixtures as described above may be used in a method for controlling pests which comprises applying a composition comprising the mixtures as described above to the pests or their environment, in addition to methods for treating the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body.

[0849] Mixtures comprising a compound of formula I selected from Tables 1 to 88 and P and one or more active ingredients as described above can be applied, for example, in a single "ready-to-use" form, as a combined spray mixture consisting of separate formulations of the single active ingredients (e.g., a "tank mix"), and when applied in a sequential manner (i.e., one after another reasonably short period of time, e.g., a few hours or days) using a combination of the separate active ingredients. The order in which the compounds of formula I selected from Tables 1 to 88 and P and the active ingredients as described above are applied is not critical for practicing the present invention.

[0850] The compositions according to the invention may also contain other solid or liquid adjuvants, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soybean oil), defoamers (for example silicone oils), preservatives, viscosity regulators, adhesives and / or tackifiers, fertilizers or other active ingredients for achieving specific effects, such as bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0851] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries, for example by grinding, screening and / or compressing the solid active ingredient; and in the presence of at least one auxiliary, for example by intimately mixing the active ingredient with one or more auxiliary agents and / or grinding the active ingredient with one or more auxiliary agents. These methods for preparing the compositions and the use of compound I for preparing these compositions are also subject matter of the present invention.

[0852] The methods of applying these compositions, i.e., methods for controlling the aforementioned types of pests, such as spraying, atomizing, dusting, brushing, coating, broadcasting, or pouring - which are selected to suit the intended purpose of the prevailing situation - and the use of these compositions for controlling the aforementioned types of pests are further subjects of the present invention. Typical concentration ratios are between 0.1 ppm and 1000 ppm, preferably between 0.1 ppm and 500 ppm, of the active ingredient. The application rate per hectare is generally between 1 g and 2000 g of active ingredient per hectare, in particular between 10 g / ha and 1000 g / ha, preferably between 10 g / ha and 600 g / ha.

[0853] In the field of crop protection, the preferred method of application is application to the leaves of the plants (foliar application), the frequency and rate of application possibly being selected to suit the risk of infestation by the pest in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by saturating the locus of the plants with a liquid composition or by introducing 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 rice crops, such granules can be metered into flooded rice fields.

[0854] These compounds of the present invention and composition thereof are also suitable for the protection (for example seed, as fruit, tuber or grain, or nursery plants) of plant propagation material against the harmful organism of above-mentioned type.Can be processed with this compound before planting, for example, can process seed before sowing.Alternately, this compound can be applied to seed grain (coating), and this is by being immersed in the liquid composition by grain or by applying solid composition layer and realizing.When this propagation material is planted in the time of application place, it is also possible for example to apply these compositions into seed furrow during drilling.These treatment methods for plant propagation material and the plant propagation material therefore processed are other themes of the present invention.Typical treatment ratio will depend on plant to be controlled and harmful organism / fungus, and usually between 1 gram to 200 grams of every 100kg seed, preferably between 5 grams to 150 grams of every 100kg seed, as between 10 grams to 100 grams of every 100kg seed.

[0855] The term seed includes all kinds of seeds and plant propagules including but not limited to true seeds, seed pieces, suckers, kernels, bulbs, fruits, tubers, grains, rhizomes, cuttings, cuttings and the like and in preferred embodiments refers to true seeds.

[0856] The present invention also includes seeds coated or treated with a compound of formula I or seeds containing a compound of formula I. The term "coating or treatment and / or containing" generally refers to when applied, in most cases, the active ingredient is on the surface of the seed, although more or less of the ingredient may penetrate into the seed material, depending on the method of application. When the seed product is (re)planted, it can absorb the active ingredient. In one embodiment, the present invention makes it possible to adhere to plant propagation materials having a compound of formula (I). In addition, compositions comprising plant propagation materials treated with a compound of formula (I) are thus available.

[0857] Seed treatment includes all applicable seed treatment techniques as known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting. Seed treatment with a compound of formula (I) can be achieved by any known method and used, such as spraying or by dusting before sowing or during sowing / planting.

[0858] Biological examples:

[0859] Example B1: Bemisia tabaci (cotton whitefly): feeding / contact activity

[0860] Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, the leaf discs were infested with adult whiteflies. After incubation for 6 days, the samples were checked for mortality. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P9, P13, and P14.

[0861] Example B2: Cucumber Leaf Beetle (Corn Rootworm)

[0862] The corn buds that are placed on the agar layer in 24 hole microtiter plates are handled with the aqueous test solution prepared from 10 '000ppm DMSO stock solution by spraying.After drying, each plate is infested (6 to 10 / well) with L2 stage larvae. After infesting 4 days, compared to untreated sample, these samples are assessed for mortality rate and growth inhibition. The following compound has provided at least 80% effect in these two classifications (mortality rate or growth inhibition) at least one at the 200ppm rate of application: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14 and P15.

[0863] Example B3: Heroic American stink bug (Neotropical brown stink bug)

[0864] Soybean leaves on agar in 24-well microtiter plates were sprayed with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, the leaves were infested with N2 nymphs. Five days after infestation, the samples were evaluated for mortality and growth inhibition compared to untreated samples. 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:

[0865] P1, P3, P8, P9, P10, P13, P14, and P15

[0866] Example B4: Myzus persicae (Green peach aphid): Feeding / contact activity

[0867] Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, the leaf discs were infested with a mixed-age aphid population. Six days after infestation, the samples were evaluated for mortality. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P10, P13, P14, and P15.

[0868] Example B5: Myzus persicae (green peach aphid). Systemic activity

[0869] The roots of pea seedlings infested with aphids of mixed ages were placed directly into an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After the seedlings were placed in the test solution for 6 days, these samples were evaluated for mortality. The following compounds gave at least 80% mortality at a test rate of 24 ppm: P10.

[0870] Example B6: Plutella xylostella (Diamond back moth)

[0871] 24 hole microtiter plates with artificial diet are handled by pipetting with the aqueous test solution of preparing from 10 ' 000ppm DMSO stock solution.After drying, each plate is infested (10 to 15 / well) with L2 stage larvae.After infesting 5 days, compared to untreated sample, these samples are assessed for mortality and growth inhibition. The following compound has provided at least 80% effect in at least one of these two classifications (mortality or growth inhibition) at the 200ppm rate of application: P1, P2, P3, P4, P6, P8, P9, P10, P11, P12, P13, P14 and P15.

[0872] Example B7: Spodoptera littoralis (Egyptian cotton leafworm)

[0873] The cotton leaf disk is placed on the agar in the 24-well microtiter plate and sprayed with the aqueous test solution of preparation from 10,000ppm DMSO stock solution. After drying, the leaf disk is infested with five L1 stage larvae. After infesting 3 days, compared to untreated sample, these samples were assessed for mortality rate, antifeedant effect and growth inhibition. When at least one was higher than untreated sample in the classification (mortality rate, antifeedant effect and growth inhibition), the test sample provided control to the sea lily wing armyworm. The following compound obtains at least 80% control under the 200ppm rate of application: P1, P2, P3, P4, P5, P6, P8, P9, P10, P11, P12, P13, P14 and P15.

[0874] Example B8: Systemic activity against Spodoptera littoralis (Egyptian cotton leafworm)

[0875] Test compound is applied to 24-well plates and mixed with agar with a pipette from 10,000ppm DMSO stock solution. Lettuce seeds are placed on agar and sealed with another plate that also comprises agar. After 7 days, root absorbed compound and lettuce growth has entered the cover plate. Then, these lettuce leaves are cut into the cover plate. Noctua ovum is pipetted through the plastic template on the moist gel imprint paper and the cover plate that it is sealed. After infecting 6 days, compared to untreated samples, these samples are assessed for mortality rate, antifeedant effect and growth inhibition. The following compound has provided at least 80% effect of at least one in three categories (mortality rate, antifeedant effect or growth inhibition) under the 12.5ppm test ratio:

[0876] P10, P13, P14 and P15.

[0877] Example B9: Tetranychus urticae (Two-spotted spider mite): feeding / contact activity

[0878] Bean leaf discs on agar in 24-well microtiter plates were sprayed with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, the leaf discs were infested with a mixed-age mite population. Eight days after infestation, the samples were evaluated for mortality in the mixed population (mobile platform). The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P10 and P13.

[0879] Example B10: Thrips tabaci (Onion Thrips) feeding / contact activity

[0880] Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, the leaf discs were infested with a mixed-age population of thrips. Six days after infestation, the samples were evaluated for mortality. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P3 and P10.

[0881] Example B11: Aedes aegypti (yellow fever mosquito):

[0882] Test solutions were applied to 12-well tissue culture dishes at an application rate of 200 ppm in ethanol. Once the sediment dried, five-day-old, two- to five-day-old adult female Aedes aegypti mosquitoes were added to each well, along with a 10% sucrose solution held in a cotton plug. Knockdown assessments were performed one hour after introduction, and mortality was assessed 24 and 48 hours after introduction. The following compounds provided at least 80% control of Aedes aegypti mosquitoes after 48 and / or 24 hours: P9, P10, P11, P13, P14, and P15.

[0883] Example B12: Anopheles stephensi (Indian malaria mosquito):

[0884] Test solutions were applied to 12-well tissue culture dishes at an application rate of 200 ppm in ethanol. Once the sediment had dried, five-day-old, two- to five-day-old adult female Anopheles stephensi mosquitoes were added to each well, and a 10% sucrose solution was placed in a cotton plug. Knockdown was assessed one hour after introduction, and mortality was assessed 24 and 48 hours after introduction. The following compounds gave at least 80% control of Anopheles stephensi mosquitoes after 48 and / or 24 hours: P10 and P13.

[0885] Comparative Examples:

[0886] Prior art compound: Compound V12.03 described on page 196 of WO 2015 / 000715:

[0887]

[0888] The compounds of the present invention:

[0889]

[0890] Compounds V12.03, P1, and P3 are structurally identical except for the substitution pattern of the pyridine moiety. The pyridine moiety of prior art compound V12.03 is unsubstituted, while compounds P1 and P3 of the present invention are substituted at the 6-position of the pyridine ring with a pyrazole and a phenyl group, respectively. The pyrazole group is substituted with a trifluoromethyl group, and the phenyl group is substituted with a chlorine group.

[0891] Example B13:

[0892] Insecticidal activity against Diabrotica cucumeris (corn rootworm), Plutella xylostella (diamond black moth), and Spodoptera littoralis (Egyptian cotton leafworm). Tests were conducted as described in Biological Examples B2, B6, and B7, respectively, with larval feeding / contact activity reported as Breakpoint (BP) 80 ) value (parts per million) (i.e. the lowest concentration giving 80% larval mortality).

[0893] Table B13: Effects on cucumber leaf beetle (corn rootworm), diamondback moth (Plutella xylostella) (Plutella xylostella) (Diamond black moth)) and Spodoptera littoralis (Egyptian cotton leafworm).

[0894]

[0895] As can be seen from Table B13, compared with the prior art compound V12.03, the compounds P1 and P3 according to the present invention showed excellent insecticidal effects on Diabrotica cucumeris (corn rootworm), Plutella xylostella (Diamond blackmoth) and Spodoptera littoralis (Egyptian cotton leafworm).

[0896] This unexpected enhancement of insecticidal activity was not expected given the structural similarity of these compounds.

[0897] Example B14: Comparison of insecticidal activity of compounds of the present invention and prior art compounds:

[0898] To demonstrate the unexpected increase in insecticidal activity compared to the prior art, the following compounds have been tested for insecticidal activity:

[0899] Prior art compound: Compound V12.01 described on page 196 of WO 2015 / 000715:

[0900]

[0901] The compounds of the present invention:

[0902]

[0903] Compounds V12.01, P4, and P5 are structurally identical except for the substitution pattern of the pyridine moiety. The pyridine moiety of prior art compound V12.03 is unsubstituted at the 6-position, while compounds P1 and P3 of the present invention are substituted at the 6-position of the pyridine moiety with a phenyl moiety. The phenyl moiety is substituted at the 3- and 4-positions, respectively, with a trifluoromethyl group. In all three compounds, the 5-position of the pyridine moiety is substituted with a trifluoromethyl group.

[0904] Example B14:

[0905] Insecticidal activity against Diabrotica cucumeris (corn rootworm). The test was conducted as described in Biological Example B6, with larval feeding / contact activity reported as the turning point (BP 80 ) value (parts per million) (i.e. the lowest concentration giving 80% larval mortality).

[0906] Table B14: Insecticidal activity against Diabrotica cucumeris (corn rootworm).

[0907]

[0908]

[0909] Table B14: Insecticidal Effect

[0910] As can be seen from Table B14, compared with the prior art compound V12.01, the compounds P4 and P5 according to the present invention showed excellent insecticidal effects on Diabrotica striata (corn rootworm).

[0911] This unexpected enhancement of insecticidal activity was not expected given the structural similarity of these compounds.

Claims

1. A compound of formula I, R1 is a C1-C4 alkyl group; R2 is C1-C4 haloalkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or halogen; R3 is hydrogen; R4 is hydrogen or C1-C3 haloalkyl; Q is phenyl, which may be mono-, di- or tri-substituted by substituents selected from the group consisting of: Halogen and C1-C4 haloalkyl; or Q is C2-C6 alkenyl, which may be monosubstituted with phenyl, which itself may be monosubstituted with C1-C4 haloalkyl; or Q is pyrazolyl, which may be monosubstituted with C1-C4 haloalkyl or halogen; or Q is a pyrimidinyl group or a C3-C6 cycloalkyl group, which may be substituted with a cyano group; or Q is a triazolyl group, which may be substituted with halogen; or Q is a C1-C4 alkyl group, which may be substituted with a cyano group; X is S or SO2; X1 is N-C1-C4 alkyl; A is N; and A1 is CH or N; and agrochemically acceptable salts, stereoisomers, enantiomers, and tautomers of those compounds.

2. The compound of formula (I) according to claim 1, wherein X1 is N-CH3.

3. The compound of formula (I) according to claim 1 or 2, wherein R1 is ethyl; X is SO2; X1 is N-CH3; A is N; and A1 is CH or N Q is phenyl, which may be mono-, di- or tri-substituted by substituents selected from the group consisting of halogen and C1-C4 haloalkyl; or Q is a C2 alkenyl group, which may be monosubstituted with a phenyl group, which itself may be monosubstituted with a C1-C4 haloalkyl group; or Q is pyrazolyl J30 The pyrazolyl group may be monosubstituted with C1-C4 haloalkyl or halogen; or Q is pyrimidinyl J-5 or cyclopropyl J43 The cyclopropyl group may be substituted by a cyano group; or Q is triazole J34 or J35 The triazole group may be substituted with halogen; or Q is a C1-C4 alkyl group, which may be substituted by a cyano group.

4. The compound of formula (I) according to claim 1, selected from the group consisting of:

5. A pesticidal composition comprising as active ingredient at least one compound of formula I according to claim 1 or, where appropriate, its tautomers, in each case in free form or in the form of an agrochemically usable salt, and at least one adjuvant.

6. A method for controlling harmful organisms, which method comprises applying a composition according to claim 5 to these harmful organisms or their environment, except for methods for treating the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body.

7. A method for protecting seeds from attack by pests, which method comprises treating the seeds or the locus where the seeds are planted with a composition according to claim 5.

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