Pesticide-killing heterocyclic derivatives with sulfur-containing substituents

Abstract

Disclosed are compounds of formula (I), wherein the substituents are as defined in claim 1. Furthermore, the present invention relates to agrochemical compositions comprising compounds of formula (I), the preparation of these compositions, and the use of these compounds or compositions in agriculture or horticulture for combating, preventing or controlling animal pests, including arthropods and in particular insects or representatives of the order Acarina. #imgabs0#

Description

[0001] The present invention relates to pesticidally active, in particular insecticidal, heterocyclic derivatives containing a sulphur substituent, processes for their preparation, compositions comprising those compounds and their use for controlling animal pests, including arthropods and in particular insects or representatives of the order Acarina.

[0002] Pesticidal heterocyclic derivatives containing sulphur substituents have been described previously in the literature (e.g. WO 12 / 086848, WO 13 / 018928, WO 15 / 000715, WO 15 / 121136, WO 18 / 197315, WO 18 / 206348, JP 2019 / 081800 and WO 19 / 065568).

[0003] It has now been found, surprisingly, that certain novel sulphur-containing phenyl and pyridyl derivatives having a cyanoisopropoxy group have advantageous properties as pesticides.

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

[0005]

[0006] in

[0007] A is CH or N;

[0008] R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl;

[0009] R9 is hydrogen or C1-C4 alkyl;

[0010] Q is a group selected from the group consisting of: Formulas Q1 to Q7

[0011]

[0012] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0013] And among them

[0014] X1 is O, S or NR3;

[0015] R3 is a C1-C4 alkyl group;

[0016] R2 is halogen, C1-C6 haloalkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C1-C6 haloalkoxy;

[0017] G1 and G2 are independently N or CH;

[0018] R4 is C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl or C1-C4 alkoxy; or

[0019] An agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I.

[0020] Compounds of formula I with at least one basic center can form acid addition salts, for example, with strong inorganic acids (such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrose acid, phosphoric acid or hydrohalic acids), strong organic carboxylic acids (such as unsubstituted or, for example, halogen-substituted C1-C4-alkanecarboxylic acids, for example acetic acid; such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid; such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid; or such as benzoic acid), or organic sulfonic acids (such as unsubstituted or, for example, halogen-substituted C1-C4-alkanesulfonic acids or arylsulfonic acids, for example methanesulfonic acid or p-toluenesulfonic acid). Compounds of formula I having at least one acidic group can, for example, form salts with bases, for example mineral salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts; or with ammonia or organic amines such as morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, for example ethylamine, diethylamine, triethylamine or dimethylpropylamine, or mono-, di- or trihydroxy-lower alkylamines, for example monoethanolamine, diethanolamine or triethanolamine.

[0021] The alkyl radicals 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 and alkoxy radicals are derived from the alkyl radicals mentioned.

[0022] Halogen is typically fluorine, chlorine, bromine or iodine. This also applies correspondingly to halogen in combination with other meanings, such as haloalkyl.

[0023] Haloalkyl 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; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

[0024] Alkoxy preferably has a preferred chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and also the isomeric pentoxy and hexoxy; preferably methoxy and ethoxy.

[0025] Alkoxyalkyl preferably has a chain length of 1 to 6 carbon atoms, more preferably a chain length of 1 to 4 carbon atoms.Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.

[0026] 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.

[0027] 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.

[0028] Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, pentylsulfonyl and hexylsulfonyl.

[0029] Cycloalkyl groups preferably have from 3 to 6 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0030] Haloalkylsulfanyl preferably has a chain length of 1 to 4 carbon atoms. Haloalkylsulfanyl is, for example, difluoromethylsulfanyl, trifluoromethylsulfanyl or 2,2,2-trifluoroethylsulfanyl. Similar considerations apply to the groups C1-C4 haloalkylsulfinyl and C1-C4 haloalkylsulfonyl, which can be, for example, trifluoromethylsulfinyl, trifluoromethylsulfonyl or 2,2,2-trifluoroethylsulfonyl.

[0031] The compounds of formula I according to the invention also include hydrates which may be formed during salt formation.

[0032] Examples according to the present invention are provided as listed below.

[0033] Example 1 provides a compound of formula I as defined above, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.

[0034] Embodiment 2 provides the compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0035] A is CH or N;

[0036] R1 is ethyl, propyl, isopropyl or -CH2cyclopropyl;

[0037] R9 is hydrogen, methyl or ethyl.

[0038] Embodiment 3a provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0039] A is CH or N;

[0040] R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; and

[0041] R9 is hydrogen or methyl.

[0042] Embodiment 3b provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0043] A is N;

[0044] R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; and

[0045] R9 is hydrogen or methyl.

[0046] Embodiment 4a provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0047] A is CH or N;

[0048] R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; and

[0049] R9 is hydrogen.

[0050] Embodiment 4b provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0051] A is N;

[0052] R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; and

[0053] R9 is hydrogen.

[0054] Embodiment 5a provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0055] A is CH or N;

[0056] R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; and

[0057] R9 is methyl.

[0058] Embodiment 5b provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0059] A is N;

[0060] R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; and

[0061] R9 is methyl.

[0062] Embodiment 6 provides the compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0063] Q is a group selected from Q1, Q2, Q4 and Q5

[0064]

[0065] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0066] And among them

[0067] R2 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl;

[0068] X1 is oxygen or NCH3;

[0069] R3 is a C1-C2 alkyl group;

[0070] R4 is C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy or cyclopropyl; and

[0071] G1 and G2 are independently N or CH.

[0072] Embodiment 7 provides the compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0073] Q is a group selected from Q1, Q2 and Q5

[0074]

[0075] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0076] And among them

[0077] R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl;

[0078] X1 is NCH3;

[0079] R3 is methyl;

[0080] R4 is methyl, ethyl, 2,2,2-trifluoroethyl, methoxy or cyclopropyl; and

[0081] G1 is N or CH.

[0082] Embodiment 8a provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0083] Q is a group selected from Q1, Q2 and Q5

[0084]

[0085] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0086] And among them

[0087] R2 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl or trifluoromethylsulfonyl;

[0088] X1 is NCH3;

[0089] R3 is methyl;

[0090] R4 is ethyl, methoxy or cyclopropyl; and

[0091] G1 is CH or N.

[0092] Embodiment 8b provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0093] Q is a group selected from Q1, Q2 and Q5

[0094]

[0095] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0096] And among them

[0097] R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl;

[0098] X1 is NCH3;

[0099] R3 is methyl;

[0100] R4 is ethyl or cyclopropyl; and

[0101] G1 is CH or N.

[0102] Embodiment 8c provides the compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0103] Q is a group selected from Q1, Q2, Q5 and Q7

[0104]

[0105] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0106] And among them

[0107] R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl;

[0108] X1 is O or NCH3;

[0109] R3 is methyl;

[0110] R4 is ethyl or cyclopropyl; and

[0111] G1 is CH or N.

[0112] Embodiment 8d provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0113] Q is a group selected from Q1, Q2, Q5 and Q7

[0114]

[0115] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0116] And among them

[0117] R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl;

[0118] X1 is NCH3;

[0119] R3 is methyl;

[0120] R4 is ethyl or cyclopropyl; and

[0121] G1 is CH or N.

[0122] Embodiment 9 provides the compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0123] Q is a group Q1

[0124] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0125] And among them

[0126] R2 is trifluoromethyl;

[0127] X1 is NCH3; and

[0128] G1 is CH or N.

[0129] Embodiment 10a provides the compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0130] Q is a group Q2

[0131]

[0132] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0133] And among them

[0134] R2 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl or trifluoromethylsulfonyl.

[0135] Embodiment 10b provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0136] Q is a group Q2

[0137]

[0138] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0139] And among them

[0140] R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl.

[0141] Embodiment 11 provides the compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0142] Q is a group Q5

[0143]

[0144] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0145] And among them

[0146] R2 is trifluoromethyl;

[0147] R3 is methyl; and

[0148] R4 is ethyl or cyclopropyl.

[0149] Embodiment 11a provides the compound of embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0150] Q is a group Q7

[0151]

[0152] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0153] And among them

[0154] X1 is O or NCH3.

[0155] Embodiment 12 provides the compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0156] A is CH or N;

[0157] R1 is ethyl, propyl, isopropyl or -CH2cyclopropyl;

[0158] R9 is hydrogen, methyl or ethyl;

[0159] Q is a group selected from Q1, Q2, Q4 and Q5

[0160]

[0161] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0162] And among them

[0163] R2 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl;

[0164] X1 is oxygen or NCH3;

[0165] R3 is a C1-C2 alkyl group;

[0166] R4 is C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy or cyclopropyl; and

[0167] G1 and G2 are independently N or CH.

[0168] Embodiment 13 provides the compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0169] A is CH or N;

[0170] R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl;

[0171] R9 is hydrogen or methyl;

[0172] Q is a group selected from Q1, Q2 and Q5

[0173]

[0174] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0175] And among them

[0176] R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl;

[0177] X1 is NCH3;

[0178] R3 is methyl;

[0179] R4 is methyl, ethyl, 2,2,2-trifluoroethyl, methoxy or cyclopropyl; and

[0180] G1 is N or CH.

[0181] Embodiment 14 provides the compound of embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0182] A is CH or N;

[0183] R1 is or -CH2cyclopropyl; preferably, R1 is ethyl;

[0184] R9 is hydrogen or methyl;

[0185] Q is a group selected from Q1, Q2 and Q5

[0186]

[0187] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0188] And among them

[0189] R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl;

[0190] X1 is NCH3;

[0191] R3 is methyl;

[0192] R4 is methyl, ethyl, 2,2,2-trifluoroethyl, methoxy or cyclopropyl; and

[0193] G1 is N or CH.

[0194] Embodiment 15 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0195] A is N;

[0196] R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl;

[0197] R9 is hydrogen or methyl;

[0198] Q is a group selected from Q1, Q2 and Q5

[0199]

[0200] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0201] And among them

[0202] R2 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl or trifluoromethylsulfonyl;

[0203] X1 is NCH3;

[0204] R3 is methyl;

[0205] R4 is ethyl, methoxy or cyclopropyl; and

[0206] G1 is CH or N.

[0207] Embodiment 16 provides the compound of embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein:

[0208] A is N;

[0209] R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl;

[0210] R9 is hydrogen or methyl;

[0211] Q is a group selected from Q1, Q2 and Q5

[0212]

[0213] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0214] And among them

[0215] R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl;

[0216] X1 is NCH3;

[0217] R3 is methyl;

[0218] R4 is ethyl or cyclopropyl; and

[0219] G1 is CH or N.

[0220] Embodiment 16a provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0221] A is N;

[0222] R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl;

[0223] R9 is hydrogen or methyl;

[0224] Q is a group selected from Q1, Q2, Q5 and Q7

[0225]

[0226] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0227] And among them

[0228] R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl;

[0229] X1 is O or NCH3;

[0230] R3 is methyl;

[0231] R4 is ethyl or cyclopropyl; and

[0232] G1 is CH or N.

[0233] Embodiment 17 provides the compound of embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein:

[0234] A is N;

[0235] R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl;

[0236] R9 is hydrogen or methyl;

[0237] Q is a group Q1

[0238]

[0239] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0240] And among them

[0241] R2 is trifluoromethyl;

[0242] X1 is NCH3; and

[0243] G1 is N or CH.

[0244] Embodiment 18 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0245] A is N;

[0246] R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl;

[0247] R9 is hydrogen;

[0248] Q is a group Q1

[0249]

[0250] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0251] And among them

[0252] R2 is trifluoromethyl;

[0253] X1 is NCH3; and

[0254] G1 is N or CH.

[0255] Embodiment 19 provides the compound of embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein:

[0256] A is N;

[0257] R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl;

[0258] R9 is a methyl group;

[0259] Q is a group Q1

[0260]

[0261] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0262] And among them

[0263] R2 is trifluoromethyl;

[0264] X1 is NCH3; and

[0265] G1 is N or CH.

[0266] Embodiment 20 provides the compound of embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein:

[0267] A is N;

[0268] R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl;

[0269] R9 is hydrogen;

[0270] Q is a group Q2

[0271]

[0272] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0273] And among them

[0274] R2 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl or trifluoromethylsulfonyl.

[0275] Embodiment 21 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein:

[0276] A is N;

[0277] R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl;

[0278] R9 is hydrogen;

[0279] Q is a group Q2

[0280]

[0281] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0282] And among them

[0283] R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl.

[0284] Embodiment 22 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0285] A is CH;

[0286] R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl;

[0287] R9 is hydrogen;

[0288] Q is a group Q2

[0289]

[0290] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0291] And among them

[0292] R2 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl or trifluoromethylsulfonyl.

[0293] Embodiment 23 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0294] A is CH;

[0295] R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl;

[0296] R9 is hydrogen;

[0297] Q is a group Q2

[0298]

[0299] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0300] And among them

[0301] R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl.

[0302] Embodiment 24 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein:

[0303] A is N;

[0304] R1 is ethyl;

[0305] R9 is hydrogen;

[0306] Q is a group Q5

[0307]

[0308] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0309] And among them

[0310] R2 is trifluoromethyl;

[0311] R3 is methyl; and

[0312] R4 is ethyl or cyclopropyl.

[0313] Embodiment 25 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0314] A is N;

[0315] R1 is ethyl;

[0316] R9 is hydrogen;

[0317] Q is a group Q7

[0318]

[0319] wherein the arrow indicates the point of attachment to the ring incorporating group A;

[0320] And among them

[0321] X1 is O or NCH3.

[0322] A preferred group of compounds having formula I is represented by compounds having formula I-1

[0323]

[0324] wherein R1, R2, R3, R9 and A are as defined above under Formula I; or

[0325] An agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula I-1.

[0326] In a preferred group of compounds having formula I-1, A is CH or N; R1 is ethyl, propyl or isopropyl or CH2cyclopropyl; R2 is C1-C2haloalkyl, C1-C2haloalkylsulfanyl, C1-C2haloalkylsulfinyl or C1-C2haloalkylsulfonyl; R3 is C1-C2alkyl; R9 is hydrogen, methyl or ethyl.

[0327] In another preferred group of compounds having formula I-1, A is CH or N; R1 is ethyl; R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; R3 is methyl; R9 is hydrogen or methyl, preferably, R9 is hydrogen.

[0328] In the above-mentioned compounds of formula I-1 and all preferred embodiments of compounds of formula I-1, unless otherwise stated, R1, R2, R3, R9 and A are as defined above under formula I; A is CH or N, preferably, A is N; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl or trifluoromethylsulfonyl; preferably, R2 is trifluoromethyl; R3 is methyl; and R9 is hydrogen.

[0329] Another preferred group of compounds having formula I is represented by compounds having formula I-2

[0330]

[0331] wherein R1, R2, R3, R9 and A are as defined above under Formula I; or

[0332] An agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula 1-2.

[0333] In a preferred group of compounds having formula I-2, A is CH or N; R1 is ethyl, propyl or isopropyl or CH2cyclopropyl; R2 is C1-C2haloalkyl, C1-C2haloalkylsulfanyl, C1-C2haloalkylsulfinyl or C1-C2haloalkylsulfonyl; R3 is C1-C2alkyl; R9 is hydrogen, methyl or ethyl.

[0334] In another preferred group of compounds having formula I-2, A is CH or N; R1 is ethyl; R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; R3 is methyl; R9 is hydrogen or methyl, preferably, R9 is hydrogen.

[0335] In the above-mentioned compounds of formula I-2 and all preferred embodiments of compounds of formula I-2, unless otherwise stated, R1, R2, R3, R9 and A are as defined above under formula I; preferably, A is CH or N, more preferably, A is N; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl or trifluoromethylsulfonyl; preferably, R2 is trifluoromethyl; R3 is methyl; and R9 is hydrogen.

[0336] Another preferred group of compounds having formula I is represented by compounds having formula I-3

[0337]

[0338] wherein R1, R2, R3, R9 and A are as defined above under Formula I; or

[0339] An agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula I-3.

[0340] In a preferred group of compounds having formula I-3, A is CH or N; R1 is ethyl, propyl or isopropyl or CH2cyclopropyl; R2 is C1-C2haloalkyl, C1-C2haloalkylsulfanyl, C1-C2haloalkylsulfinyl or C1-C2haloalkylsulfonyl; R3 is C1-C2alkyl; R9 is hydrogen, methyl or ethyl.

[0341] In another preferred group of compounds having formula I-3, A is CH or N; R1 is ethyl; R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; R3 is methyl; R9 is hydrogen or methyl, preferably, R9 is hydrogen.

[0342] In the above-mentioned compounds of formula I-3 and all preferred embodiments of compounds of formula I-3, unless otherwise stated, R1, R2, R3, R9 and A are as defined above under formula I; preferably, A is CH or N, more preferably, A is N; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl or trifluoromethylsulfonyl; preferably, R2 is trifluoromethyl; R3 is methyl; and R9 is hydrogen.

[0343] Another preferred group of compounds having formula I is represented by compounds having formula I-4

[0344]

[0345] wherein R1, R2, R3, R4, R9 and A are as defined above under Formula I; or

[0346] An agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula I-4.

[0347] In a preferred group of compounds having formula I-4, A is CH or N; R1 is ethyl, propyl or isopropyl or CH2cyclopropyl; R2 is C1-C2haloalkyl, C1-C2haloalkylsulfanyl, C1-C2haloalkylsulfinyl or C1-C2haloalkylsulfonyl; R3 is C1-C2alkyl; R4 is C1-C2alkyl, C1-C2haloalkyl, C1-C2alkoxy or cyclopropyl; R9 is hydrogen, methyl or ethyl.

[0348] In another preferred group of compounds having formula I-4, A is CH or N; R1 is ethyl; R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; R3 is methyl; R4 is methyl, ethyl, methoxy or cyclopropyl; R9 is hydrogen or methyl, preferably, R9 is hydrogen.

[0349] In another preferred group of compounds of formula 1-4, R4 is ethyl or cyclopropyl.

[0350] In the above-mentioned compounds of formula I-4 and all preferred embodiments of compounds of formula I-4, unless otherwise stated, R1, R2, R3, R4, R9 and A are as defined above under formula I; preferably, A is CH or N, more preferably, A is N; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl or trifluoromethylsulfonyl; preferably, R2 is trifluoromethyl; R3 is methyl; R4 is ethyl, methoxy or cyclopropyl; and R9 is hydrogen.

[0351] Another preferred group of compounds having formula I is represented by compounds having formula I-5

[0352]

[0353] wherein R1, R2, R9 and A are as defined above under Formula I; or

[0354] An agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula I-5.

[0355] In a preferred group of compounds having formula I-5, A is CH or N; R1 is ethyl, propyl or isopropyl or CH2cyclopropyl; R2 is C1-C2haloalkyl, C1-C2haloalkylsulfanyl, C1-C2haloalkylsulfinyl or C1-C2haloalkylsulfonyl; and R9 is hydrogen, methyl or ethyl.

[0356] In another preferred group of compounds having formula I-5, A is CH or N; R1 is ethyl; R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; R9 is hydrogen or methyl, preferably, R9 is hydrogen.

[0357] In the above-mentioned compounds of formula I-5 and all preferred embodiments of compounds of formula I-5, unless otherwise stated, R1, R2, R9 and A are as defined above under formula I; preferably, A is CH or N, more preferably, A is N; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl or trifluoromethylsulfonyl; preferably, R2 is trifluoromethyl; and R9 is hydrogen.

[0358] Another preferred group of compounds having formula I is represented by compounds having formula I-6

[0359]

[0360] wherein R1, R2, R9 and A are as defined above under Formula I; or

[0361] An agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula 1-6.

[0362] In a preferred group of compounds having formula I-6, A is CH or N; R1 is ethyl, propyl or isopropyl or CH2 cyclopropyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; R9 is hydrogen, methyl or ethyl.

[0363] In another preferred group of compounds having formula I-6, A is CH or N; R1 is ethyl; R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; R9 is hydrogen or methyl, preferably, R9 is hydrogen.

[0364] In the above-mentioned compounds of formula I-6 and all preferred embodiments of compounds of formula I-6, unless otherwise stated, R1, R2, R9 and A are as defined above under formula I; preferably, A is CH or N, more preferably, A is N; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl or trifluoromethylsulfonyl; preferably, R2 is trifluoromethyl; and R9 is hydrogen.

[0365] Another preferred group of compounds having formula I is represented by compounds having formula I-7

[0366]

[0367] wherein R1, R2, R9 and A are as defined above under Formula I; or

[0368] An agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula 1-7.

[0369] In a preferred group of compounds having formula I-7, A is CH or N; R1 is ethyl, propyl or isopropyl or CH2cyclopropyl; R2 is C1-C2haloalkyl, C1-C2haloalkylsulfanyl, C1-C2haloalkylsulfinyl or C1-C2haloalkylsulfonyl; R9 is hydrogen, methyl or ethyl.

[0370] In another preferred group of compounds having formula I-7, A is CH or N; R1 is ethyl; R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; R9 is hydrogen or methyl, preferably, R9 is hydrogen.

[0371] In the above-mentioned compounds of formula I-7 and all preferred embodiments of compounds of formula I-7, unless otherwise stated, R1, R2, R9 and A are as defined above under formula I; preferably, A is CH or N, more preferably, A is N; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl or trifluoromethylsulfonyl; preferably, R2 is trifluoromethyl; and R9 is hydrogen.

[0372] Another preferred group of compounds having formula I is represented by compounds having formula I-8

[0373]

[0374] wherein R1, R2, R9 and A are as defined above under Formula I; or

[0375] An agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula I-8.

[0376] In a preferred group of compounds having formula I-8, A is CH or N; R1 is ethyl, propyl or isopropyl or CH2 cyclopropyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; R9 is hydrogen, methyl or ethyl.

[0377] In another preferred group of compounds having formula I-8, A is CH or N; R1 is ethyl; R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; R9 is hydrogen or methyl, preferably, R9 is hydrogen.

[0378] In the above-mentioned compounds of formula I-8 and all preferred embodiments of compounds of formula I-8, unless otherwise stated, R1, R2, R9 and A are as defined above under formula I; preferably, A is CH or N, more preferably, A is N; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl or trifluoromethylsulfonyl; preferably, R2 is trifluoromethyl; and R9 is hydrogen.

[0379] Another preferred group of compounds having formula I is represented by compounds having formula I-9

[0380]

[0381] wherein R1, R2, R9 and A are as defined above under Formula I; or

[0382] An agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula 1-9.

[0383] In a preferred group of compounds having formula I-9, A is CH or N; R1 is ethyl, propyl or isopropyl or CH2cyclopropyl; R2 is C1-C2haloalkyl, C1-C2haloalkylsulfanyl, C1-C2haloalkylsulfinyl or C1-C2haloalkylsulfonyl; and R9 is hydrogen, methyl or ethyl.

[0384] In another preferred group of compounds having formula I-9, A is CH or N; R1 is ethyl; R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; R9 is hydrogen or methyl, preferably, R9 is hydrogen.

[0385] In the above-mentioned compounds of formula I-9 and all preferred embodiments of compounds of formula I-9, unless otherwise stated, R1, R2, R9 and A are as defined above under formula I; preferably, A is CH or N, more preferably, A is N; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl or trifluoromethylsulfonyl; preferably, R2 is trifluoromethyl; and R9 is hydrogen.

[0386] Another preferred group of compounds having formula I is represented by compounds having formula I-10

[0387]

[0388] wherein R1, R3, R9 and A are as defined above under Formula I; or

[0389] An agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula 1-10.

[0390] In a preferred group of compounds having formula I-10, A is CH or N; R1 is ethyl, propyl or isopropyl or CH2 cyclopropyl; R3 is C1-C2 alkyl; R9 is hydrogen, methyl or ethyl.

[0391] In another preferred group of compounds having formula I-10, A is CH or N; R1 is ethyl; R3 is methyl; R9 is hydrogen or methyl, preferably, R9 is hydrogen.

[0392] In the above-mentioned compounds of formula I-10 and all preferred embodiments of compounds of formula I-10, unless otherwise stated, R1, R3, R9 and A are as defined above under formula I; preferably, A is CH or N, more preferably, A is N; R3 is methyl; and R9 is hydrogen.

[0393] Another preferred group of compounds having formula I is represented by compounds having formula I-11

[0394]

[0395] wherein R1, R9 and A are as defined above under Formula I; or

[0396] An agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula 1-11.

[0397] In a preferred group of compounds having formula 1-11, A is CH or N; R1 is ethyl, propyl or isopropyl or CH2 cyclopropyl; and R9 is hydrogen, methyl or ethyl.

[0398] In another preferred group of compounds having formula 1-11, A is CH or N; R1 is ethyl; and R9 is hydrogen or methyl, preferably, R9 is hydrogen.

[0399] In the above-mentioned compounds of formula I-11 and all preferred embodiments of compounds of formula I-11, unless otherwise stated, R1, R9 and A are as defined above under formula I; preferably, A is CH or N, more preferably, A is N; and R9 is hydrogen.

[0400] Another particularly preferred group of compounds of formula I are those represented by compounds of formula I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10 or I-11, wherein,

[0401] A is CH or N, preferably, A is N;

[0402] R1 is ethyl, propyl, isopropyl or CH2cyclopropyl; preferably, R1 is ethyl;

[0403] R9 is hydrogen; and

[0404] In the case of compounds having formula I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8 and I-9

[0405] R2 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl or trifluoromethylsulfonyl; preferably, R2 is trifluoromethyl; and

[0406] In the case of compounds having formula I-1, I-2, I-3, I-4 and I-10, R3 is methyl;

[0407] And in the case of compounds having formula 1-4, R4 is ethyl, methoxy or cyclopropyl.

[0408] The compounds according to the present invention may have any number of benefits, including, among others, favorable levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (e.g., higher biological activity, favorable activity spectrum, increased safety, improved physico-chemical properties, or increased biodegradability or environmental profile). In particular, it has been unexpectedly discovered that certain compounds of formula (I) may exhibit favorable safety profiles relative to non-target arthropods, particularly pollinators such as honey bees, solitary bees, and bumblebees. Most particularly, relative to the Italian honey bee (Apis mellifera).

[0409] In another aspect, the present invention provides a composition comprising an insecticidal, acaricidal, nematicidal or molluscicidal effective amount of a compound of formula (I) as defined in any one of Examples 1-25 (above) or in any one of the Examples under Compounds of Formula I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10 or I-11, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and optionally, an adjuvant or diluent.

[0410] In another aspect, the present invention provides a method for combating and controlling insects, mites, nematodes or molluscs, which comprises applying to the pest, the location of the pest or a plant susceptible to attack by the pest an insecticidal, acaricidal, nematicidal or molluscicidal effective amount of a compound of formula (I) as defined in any one of Examples 1-25 (above) or in any one of the Examples under the compound of formula I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10 or I-11 (above) or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, or a composition as defined above.

[0411] In yet another aspect, the present invention provides a method for protecting plant propagation material from attack by insects, acarids, nematodes or molluscs, which method comprises treating the propagation material or the locus where the propagation material is planted with a composition as defined above.

[0412] The method for preparing a compound of formula I according to the present invention is carried out by methods known to those skilled in the art. Compounds of formula I (wherein A, R1, R9 and Q are as defined above under formula I) can be prepared by oxidation of compounds of formula II-a (Scheme 1), wherein A, R1, R9 and Q are as defined above under formula I. The reaction can be carried out with reagents such as peracids (e.g., peracetic acid or metachloroperbenzoic acid (mCPBA)), or hydroperoxides (e.g., hydrogen peroxide or tert-butyl hydroperoxide), or inorganic oxidants (e.g., monoperoxodisulfate (oxone), sodium periodate, sodium hypochlorite or potassium permanganate). In a similar manner, compounds of formula II-a (wherein A, R1, R9 and Q are as defined above under formula I) can be prepared by oxidation of compounds of formula II under similar conditions as described above, wherein A, R1, R9 and Q are as defined above under formula I.

[0413] Option 1:

[0414]

[0415] Similarly, compounds of formula II can be directly oxidized to compounds of formula I under the above conditions. The amount of the oxidant to be used in the reaction is generally 1 to 3 moles, preferably 1 to 1.2 moles (relative to 1 mole of sulfoxide compound II-a used to produce sulfone compound I), and preferably 2 to 2.2 moles of the oxidant (relative to 1 mole of sulfide II used to produce sulfone compound I). These reactions can be carried out in various organic or aqueous solvents compatible with these conditions at temperatures from below 0°C to the boiling point of the solvent system. Examples of solvents used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform; alcohols such as methanol and ethanol; acetic acid; water; and mixtures thereof.

[0416] Compounds of Formula II (wherein R9, R1, A and Q are as defined in Formula I)

[0417] Option 5 :

[0418]

[0419] It can be prepared by reacting a compound of formula III (wherein R9, R1, A and Q are as defined in formula I) with a compound of formula IV (preferably at least 2 equivalents, where Xb is a leaving group, such as, for example, chloro, bromo or iodo (preferably iodo or bromo), or an arylsulfonate, alkylsulfonate or haloalkylsulfonate (such as trifluoromethanesulfonate)) in the presence of a base (preferably at least 2 equivalents, such as, for example, potassium carbonate, cesium carbonate, lithium hexamethyldisilazane or lithium diisopropylamide) in a suitable solvent such as acetonitrile, tetrahydrofuran or N,N-dimethylformamide at a temperature between -78°C and 100°C, preferably between -10°C and 80°C (Scheme 5). Methyl iodide, methyl bromide or dimethyl sulfate are typical representatives of the methylating agent CH3-XbIV. Optionally, the compound of formula III is treated twice with about one equivalent (or more) of each of the methylating agent CH3-XbIV and a base.

[0420] Compounds of formula II

[0421]

[0422] in

[0423] A, R1, R9 and Q are as defined above under formula I, are novel, have been developed in particular for the preparation of compounds of formula I according to the invention, and therefore represent another object of the present invention. The preferences and preferred embodiments of the substituents of the compounds of formula I are also valid for the compounds of formula II.

[0424] Compounds of formula III (wherein R9, R1, A and Q are as defined in formula I)

[0425] Option 6:

[0426]

[0427] They can be prepared (Scheme 6) by reacting a compound of formula V, wherein R9, R1, A and Q are as defined in formula I, with a compound of formula VI, wherein Xa is a leaving group, such as, for example, chlorine, bromine or iodine, preferably chlorine or bromine, or an arylsulfonate, alkylsulfonate or haloalkylsulfonate, such as trifluoromethanesulfonate, in the presence of a base, such as, for example, potassium carbonate, cesium carbonate or sodium hydride, optionally in the presence of a catalytic amount of an additive, such as sodium iodide or potassium iodide, in a suitable solvent, such as acetone, tetrahydrofuran, acetonitrile, dimethylsulfoxide or N,N-dimethylformamide, at a temperature between -10°C and 100°C, preferably between 0°C and 80°C.

[0428] Alternatively, a compound of formula II (wherein R9, R1, A and Q are as defined in formula I)

[0429] Option 7 :

[0430]

[0431] It can be prepared under dehydrating conditions (Scheme 7) by reacting a compound of formula VII (wherein R9, R1, A and Q are as defined in formula I) with a dehydrating agent (such as trifluoroacetic acid, trifluoroacetic anhydride, phosphorus pentoxide, thionyl chloride or phosphorus oxychloride) in a suitable solvent (such as, for example, dichloromethane, dioxane or N,N-dimethylformamide) at a temperature between 0°C and 180°C, preferably between 5°C and 80°C, optionally in the presence of a base (such as triethylamine or pyridine) as described in, for example, US20100267738.

[0432] Compounds of formula VII (wherein R9, R1, A and Q are as defined in formula I)

[0433] Option 8:

[0434]

[0435] It can be prepared by reacting a compound of formula V, wherein R9, R1, A and Q are as defined in formula I, with a compound of formula VIII, wherein Xa is a leaving group, such as, for example, chloro, bromo or iodo (preferably bromo), or an arylsulfonate, alkylsulfonate or haloalkylsulfonate, such as trifluoromethanesulfonate, in the presence of a base, such as, for example, lithium hydroxide, sodium hydroxide or potassium hydroxide, sodium hydride, potassium carbonate or cesium carbonate, in a suitable solvent such as acetone, dioxane, acetonitrile, N,N-dimethylformamide or N,N-dimethylacetamide, at a temperature between -10°C and 100°C, preferably between 0°C and 80°C (Scheme 8).

[0436] Compounds of Formula V (wherein R9, R1, A and Q are as defined in Formula I)

[0437] Option 9:

[0438]

[0439] It can be prepared as follows (Scheme 9): as described in, for example, Angew. Chem. Int. Ed. [Applied Chemistry International Edition] 56 (16), 4478-4482, 2017, in the presence of a base (such as potassium carbonate or cesium carbonate), optionally in the presence of a palladium catalyst (such as RockPhos-G3-cyclopalladium complex ([(2-di-tert-butylphosphino-3-methoxy-6-methyl-2′,4′,6′-triisopropyl-1,1′-biphenyl)-2-(2-aminobiphenyl)] methanesulfonic acid) A compound of formula IX, wherein R9, R1, A and Q are as defined in formula I, and wherein X is a leaving group, such as, for example, chlorine, bromine or iodine (preferably bromine), or an arylsulfonate, alkylsulfonate or haloalkylsulfonate (such as triflate), is reacted with, for example, benzaldehyde oxime PhC═NOH, preferably (E)-benzaldehyde oxime, in the presence of palladium(II)) in an aprotic solvent such as acetonitrile or N,N-dimethylformamide DMF at a temperature between 0° C. and 100° C., preferably between room temperature and 80° C.

[0440] Alternatively, compounds of formula V, wherein R9, R1, A and Q are as defined in formula I, can be prepared from compounds of formula IX, wherein R9, R1, A and Q are as defined in formula I, and wherein X is a leaving group, such as, for example, chloro, bromo or iodo (preferably bromo), or an arylsulfonate, alkylsulfonate or haloalkylsulfonate (such as trifluoromethanesulfonate) by running the following steps in sequence:

[0441] 1) Borylation reaction, wherein a compound of formula IX is reacted with bis(pinacolato)diborane (Bpin)2, typically in the presence of a palladium catalyst. The introduction of such pinacol boronate functional groups can be carried out in an aprotic solvent such as dioxane in the presence of a base, preferably a weak base such as potassium acetate KOAc. [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (also known as dichloropalladium dppf or Pd(dppf)Cl2) is a common catalyst for this type of reaction. Other palladium source / ligand combinations involve, for example, tris(dibenzylideneacetone)diphosphine and tricyclohexylphosphine. The reaction temperature is preferably between 0°C and the boiling point of the reaction mixture, or the reaction can be carried out under microwave irradiation. The intermediate product of this borylation reaction is then further subjected to

[0442] 2) an oxidation step in which the intermediate product is treated with hydrogen peroxide, H2O2, such as a 30% H2O2 solution in water, typically in an inert solvent such as tetrahydrofuran or dioxane at a temperature between 0° C. and 100° C., preferably around room temperature. The described process for preparing compounds of formula V from compounds of formula IX may include the isolation and purification of the borylated intermediate, however this process is also advantageously carried out by incorporating the crude intermediate into oxidation step 2.

[0443] Compounds of formula IX (wherein R9, R1, A and Q are as defined in formula I and wherein X is a leaving group), in particular those wherein X is halogen, are known compounds or can be prepared by known methods or can be synthesized analogously to described methods found in the literature. See in particular WO 2016 / 071214 (Q is Q2, G2 is N) and WO 2015 / 000715 (Q is Q2, G2 is CH), WO 2016 / 026848 and WO 2016 / 005263 (Q is Q1, G1 is CH, G2 is N), WO 2016 / 059145 (Q is Q1, G1 is N, G2 is N), WO 2016 / 020286 and WO 2017 / 134066 (Q is Q4), WO 2017 / 089190, WO 2017 / 084879 and WO 2016 / 023954 (Q is Q5), WO 2015 / 000715 (Q is Q3), and WO 2012 / 086848, WO 2013 / 018928 (Q is Q1, G1 is N or CH, G2 is CH).

[0444] a compound of formula IV wherein Xb is a leaving group such as, for example, chloro, bromo or iodo (preferably iodo or bromo), or an arylsulfonate, alkylsulfonate or haloalkylsulfonate (such as trifluoromethanesulfonate); and

[0445] Compounds of formula VI wherein Xa is a leaving group such as, for example, chloro, bromo or iodo (preferably bromo), or an arylsulfonate, alkylsulfonate or haloalkylsulfonate (such as trifluoromethanesulfonate); and

[0446] Compounds of formula VIII (wherein Xa is a leaving group such as, for example, chloro, bromo or iodo (preferably bromo), or an arylsulfonate, alkylsulfonate or haloalkylsulfonate (such as trifluoromethanesulfonate);

[0447] All are known compounds, commercially available or can be prepared by known methods described in the literature.

[0448] A subgroup of compounds of formula V (wherein R9 is C1-C4 alkyl, defining compounds of formula Vc, where R1, A and Q are as defined in formula I)

[0449] Option 10:

[0450]

[0451] Can be prepared from compounds of formula Vb (wherein R1, A and Q are as defined in formula I, and wherein Xb is halogen (preferably chlorine, bromine or iodine)) typically under palladium catalysis (alternatively nickel catalysis) cross-coupling conditions by C-C bond formation reaction (Scheme 10). Such Suzuki-Miyaura cross-coupling reactions between compounds of formula Vb and C1-C4 alkylboronic acid of formula R9B(OH)2 (wherein R9 is as defined in formula I) or the corresponding C1-C4 alkylboronic ester derivative or the corresponding 6-membered tri(C1-C4 alkyl)boroxane derivative of formula (R9BO)3 (wherein R9 is as defined in formula I) are well known to those skilled in the art. In the specific case where R9 is methyl, compounds of formula Vb can be reacted, for example, with trimethylboroxane (also known as 2,4,6-trimethyl-1,3,5,2,4,6-trioxatriborinane) in the presence of a palladium catalyst such as tetrakis(triphenylphosphine)palladium(0) or [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II)dichloromethane complex and a base such as sodium carbonate or potassium carbonate in a solvent such as N,N-dimethylformamide, dioxane or a dioxane-water mixture at temperatures between room temperature and 160° C., optionally under microwave heating conditions, and preferably under an inert atmosphere. Such conditions are described, for example, in Tetrahedron Letters (2000), 41(32), 6237-6240.

[0452] Compounds of formula Vb (wherein R1, A and Q are as defined in formula I, and wherein Xb is a halogen (preferably chlorine, bromine or iodine)) can be prepared by a halogenation reaction comprising, for example, reacting a subgroup of compounds of formula V (wherein R9 is hydrogen, defining compounds of formula Va, wherein R1, A and Q are as defined in formula I) with a halogenating agent (such as N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS) or N-iodosuccinimide (NIS), or alternatively chlorine, bromine or iodine) optionally in the presence of a base (such as sodium carbonate, potassium carbonate or cesium carbonate). Such halogenation reactions are carried out in an inert solvent (such as chloroform, carbon tetrachloride, 1,2-dichloroethane, acetic acid, ether, N,N-dimethylformamide, acetonitrile or acetonitrile-water mixture) at a temperature between 20°C and 200°C, preferably at room temperature to 100°C.

[0453] Alternatively, a compound of formula II (wherein Q is Q1, defining a compound of formula II-Q1,

[0454] wherein R1, R9, A, X1, G1 and R2 are as defined in Formula I)

[0455] Plan 11 :

[0456]

[0457] Can be prepared by cyclizing a compound of formula (XX) (wherein R1, R9, A, X1, G1 and R2 are as defined in formula I) (Scheme 11), for example by heating in acetic acid or trifluoroacetic acid (preferably when X1 is NR3, wherein R3 is C1-C4 alkyl) at a temperature between 0°C and 180°C, preferably between 20°C and 150°C, optionally under microwave irradiation. Cyclization of the compound of formula (XX) can also be carried out in the presence of an acid catalyst (e.g., methanesulfonic acid or p-toluenesulfonic acid p-TsOH) in an inert solvent (e.g., N-methylpyrrolidone, toluene or xylene) at a temperature between 25°C and 180°C, preferably between 100°C and 170°C. Such methods have previously been described, for example, in WO 2010 / 125985. Alternatively, compounds of formula (XX) can be converted to compounds of formula II-Q1 (preferably when X1 is O) using triphenylphosphine, diisopropyl azodicarboxylate (or diethyl azodicarboxylate) in an inert solvent such as tetrahydrofuran (THF) at temperatures between 20° C. and 50° C. Such Mitsunobu reaction conditions have been previously described for these transformations (see WO 2009 / 131237).

[0458] Compounds of formula (XX) wherein R1, R9, A, X1, G1 and R2 are as defined in formula I can be prepared via acylation by the following steps:

[0459] i) activating a compound of formula (XXIII) wherein R1, R9 and A are as defined in formula I 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 (XXII) wherein R1, R9 and A are as defined in formula I, and wherein X 00 is halogen, preferably chlorine). For example, in an inert solvent (such as dichloromethane CH2Cl2 or tetrahydrofuran THF), at a temperature between 20°C and 100°C, preferably 25°C, in the presence of a catalytic amount of N,N-dimethylformamide DMF, compound (XXII) (wherein X is obtained) can be formed by treating (XXIII) with, for example, oxalyl chloride (COCl)2 or thionyl chloride SOCl2. 00is halogen, preferably chlorine). Alternatively, treatment of a compound of formula (XXIII) with, for example, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide EDC or dicyclohexylcarbodiimide DCC in an inert solvent such as pyridine or tetrahydrofuran (THF), optionally in the presence of a base such as triethylamine, at a temperature between 50°C and 180°C will yield activated species (XXII), wherein X 00 X 01 or X 02 ; then

[0460] ii) treating the activated substance (XXII) with a compound of formula (XI) (wherein X1, G1 and R2 are as defined in formula I) in an inert solvent (such as dichloromethane, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, ethyl acetate or toluene) in the presence of a base (such as triethylamine, N,N-diisopropylethylamine or pyridine) at a temperature between 0°C and 50°C to form a compound of formula (XX).

[0461] Alternatively, a compound of formula II (wherein Q is Q6, defining a compound of formula II-Q6, wherein R1, R9, A, X1 and R2 are as defined in formula I)

[0462] Option 11a :

[0463]

[0464] It can be prepared by cyclizing compounds of formula (XX-N) (wherein R1, R9, A, X1 and R2 are as defined in formula I) under similar conditions as described above (see Scheme 11 in the text) (Scheme 11a).

[0465] Compounds of formula (XX-N) (wherein R1, R9, A, X1 and R2 are as defined in formula I) can be prepared by reacting the above-mentioned activated substance (XXII) with a compound of formula (XI-N) (wherein X1 and R2 are as defined in formula I) under similar conditions to those described above (see Scheme 11 in the main text).

[0466] A compound of formula (XXIII) (wherein R1, R9 and A are as defined in formula I)

[0467] Plan 12 :

[0468]

[0469] Compounds of formula (XXIV) wherein R1, R9 and A are as defined in formula I and wherein R 00 is C1-C6 alkyl) (Scheme 12).

[0470] A compound of formula (XXIV) wherein R1, R9 and A are as defined in formula I, and wherein R 00 is C1-C6 alkyl) can be obtained by converting a compound of formula (XXV-b) (wherein R9, R1 and A are as defined in formula I, and wherein R 00 is C1-C6 alkyl) with a compound of formula IV (wherein Xb is a leaving group such as, for example, chlorine, bromine or iodine (preferably iodine or bromine), or an arylsulfonate, an alkylsulfonate or a haloalkylsulfonate (such as trifluoromethanesulfonate)).

[0471] A compound of formula (XXV-b) wherein R9, R1 and A are as defined in formula I, and wherein R 00 is C1-C6 alkyl) can be obtained by converting a compound of formula (XXV-a) (wherein R1, R9 and A are as defined in formula I, and wherein R 00 is C1-C6 alkyl) with a compound of formula VI (wherein Xa is a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an arylsulfonate, an alkylsulfonate or a haloalkylsulfonate (such as trifluoromethanesulfonate)).

[0472] Alternatively, a compound of formula (XXIV) wherein R1, R9 and A are as defined in formula I, and wherein R 00 is C1-C6 alkyl) can be prepared by making a compound having formula (XXV-c) (wherein R1, R9 and A are as defined in formula I, and wherein R 00 is C1-C6 alkyl) by subjecting it to the dehydration conditions described above (see Scheme 7 for the conversion of compound VII to II).

[0473] A compound of formula (XXV-c) wherein R1, R9 and A are as defined in formula I, and wherein R 00is C1-C6 alkyl) can be obtained by converting a compound of formula (XXV-a) (wherein R1, R9 and A are as defined in formula I, and wherein R 00 is C1-C6 alkyl) with a compound of formula VIII (wherein Xa is a leaving group such as, for example, chlorine, bromine or iodine (preferably bromine), or an arylsulfonate, an alkylsulfonate or a haloalkylsulfonate (such as trifluoromethanesulfonate)).

[0474] A compound of formula (XXV-a) wherein R1, R9 and A are as defined in formula I, and wherein R 00 is C1-C6 alkyl) can be obtained by converting a compound of formula (XXV) (wherein R1, R9 and A are as defined in formula I, and wherein R 00 is C1-C6 alkyl, and wherein Xc is a leaving group such as, for example, chlorine, bromine or iodine (preferably bromine), or an arylsulfonate, alkylsulfonate or haloalkylsulfonate (such as trifluoromethanesulfonate)) with, for example, benzaldehyde oxime PhC=NOH (preferably (E)-benzaldehyde oxime). Alternatively, the method for preparing compounds of formula (XXV-a) from compounds of formula (XXV) may also include borylation / oxidation conditions as also described in Scheme 9.

[0475] A compound of formula (XXV) wherein R1, R9 and A are as defined in formula I, and wherein R 00 Compounds wherein Xc is C1-C6 alkyl, and wherein Xc is a leaving group such as, for example, chlorine, bromine or iodine, or an arylsulfonate, alkylsulfonate or haloalkylsulfonate such as trifluoromethanesulfonate), in particular those wherein Xc is halogen (even more preferably chlorine, bromine or iodine) are known compounds, commercially available or can be prepared by known methods described in the literature such as, for example, in WO 2016 / 005263, WO 2016 / 023954, WO 2016 / 026848 and WO 2016 / 104746.

[0476] Alternatively, a compound of formula II (wherein Q is Q2, defining a compound of formula II-Q2,

[0477] wherein R1, R9, A and R2 are as defined in Formula I)

[0478] Plan 13 :

[0479]

[0480] Can be prepared by the following method (Scheme 13): in an inert solvent (such as ethanol or acetonitrile), optionally in the presence of a suitable base (such as sodium carbonate, potassium carbonate or cesium carbonate, or magnesium oxide), at a temperature between 50 ° C and 150 ° C, optionally under microwave heating conditions, a compound of formula (XXVI) (wherein R1, R9 and A are as defined in formula I, and wherein Xd is a leaving group, such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine)) and a compound of formula (XXVII) (wherein R2 is as defined in formula I) are condensed. Such methods have been previously described, for example, in WO 2012 / 49280 or WO 2003 / 031587. Compounds of formula (XXVII) (wherein R2 is as defined in formula I) are known compounds, commercially available or can be prepared by known methods known to those skilled in the art (see in particular WO 2016 / 071214).

[0481] A compound of formula (XXVI) wherein R1, R9 and A are as defined in formula I, and wherein Xd is a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine)

[0482] Plan 14 :

[0483]

[0484] It can be prepared in the following manner (Scheme 14): typically in a solvent (such as methanol, acetonitrile, tetrahydrofuran, ethyl acetate, chloroform or dichloromethane, or a mixture thereof) at a temperature between 0°C and 150°C, preferably between room temperature and 120°C, optionally under microwave heating conditions, with a halogenating agent ("Xd + " source" (e.g., N-bromosuccinimide, N-iodosuccinimide, N-chlorosuccinimide, I2, CuBr2, Br2 in acetic acid, or trimethyl(phenyl)ammonium tribromide PhNMe3 + Br3 - ) treating a compound of formula (XXVIII) wherein R1, R9 and A are as defined in formula I. Such methods have been previously described, for example, in WO 2016 / 071214.

[0485] Compounds of formula (XXVIII) (wherein R1, R9 and A are as defined in formula I) can be prepared by reacting compounds of formula (XXIX-b) (wherein R9, R1 and A are as defined in formula I) with compounds of formula IV (wherein Xb is a leaving group such as, for example, chlorine, bromine or iodine (preferably iodine or bromine), or an arylsulfonate, an alkylsulfonate or a haloalkylsulfonate such as a triflate) under the conditions described above (see Scheme 5 for the conversion of compound III to II).

[0486] Compounds of formula (XXIX-b) (wherein R9, R1 and A are as defined in formula I) can be prepared by reacting a compound of formula (XXIX-a) (wherein R1, R9 and A are as defined in formula I) with a compound of formula VI (wherein Xa is a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an arylsulfonate, an alkylsulfonate or a haloalkylsulfonate such as a trifluoromethanesulfonate) under the conditions described above (see Scheme 6 for the conversion of compound V to III).

[0487] Alternatively, compounds of formula (XXVIII) (wherein R1, R9 and A are as defined in formula I) can be prepared by subjecting compounds of formula (XXIX-c) (wherein R1, R9 and A are as defined in formula I) to the dehydration conditions described above (see Scheme 7 for the conversion of compound VII to II).

[0488] Compounds of formula (XXIX-c) (wherein R1, R9 and A are as defined in formula I) can be prepared by reacting compounds of formula (XXIX-a) (wherein R1, R9 and A are as defined in formula I) with compounds of formula VIII (wherein Xa is a leaving group such as, for example, chlorine, bromine or iodine (preferably bromine), or an arylsulfonate, an alkylsulfonate or a haloalkylsulfonate such as a triflate) under the conditions described above (see Scheme 8 for the conversion of compound V to VII).

[0489] Compounds of formula (XXIX-a) (wherein R1, R9 and A are as defined in formula I) can be prepared by reacting compounds of formula (XXIX) (wherein R1, R9 and A are as defined in formula I and wherein Xf is a leaving group such as, for example, chlorine, bromine or iodine (preferably bromine), or an arylsulfonate, alkylsulfonate or haloalkylsulfonate (such as trifluoromethanesulfonate)) with, for example, benzaldehyde oxime PhC=NOH (preferably (E)-benzaldehyde oxime) under the conditions already described above (see Scheme 9 for the conversion of compound IX to V). Alternatively, the process for preparing compounds of formula (XXIX-a) from compounds of formula (XXIX) can also include the borylation / oxidation conditions also already described in Scheme 9.

[0490] Compounds of formula (XXIX) wherein R1, R9 and A are as defined in formula I, and wherein Xf is a leaving group such as, for example, chlorine, bromine or iodine, or an arylsulfonate, alkylsulfonate or haloalkylsulfonate such as trifluoromethanesulfonate, in particular those wherein Xf is halogen (even more preferably chlorine, bromine or iodine; particularly preferred is chlorine or bromine) are known compounds, commercially available or can be prepared by known methods described in the literature, such as, for example, in WO 2016 / 071214.

[0491] Alternatively, a compound of formula II (wherein Q is Q5, defining a compound of formula II-Q5,

[0492] wherein R1, R9, A, R3, R4 and R2 are as defined in Formula I)

[0493] Plan 15 :

[0494]

[0495] It can be prepared by cyclizing a compound of formula (XXXa) (wherein R1, R9, A, R3, R4 and R2 are as defined in formula I) or a regioisomer of formula (XXXb) having the same substituent definitions, or a mixture thereof in any ratio under the conditions described above (see Scheme 11 for conversion of compound (XX) to II-Q1) (Scheme 15).

[0496] Compounds of formula (XXXa) (wherein R1, R9, A, R3, R4 and R2 are as defined in formula I), or regioisomers of formula (XXXb) having the same substituent definitions, or mixtures thereof in any ratio can be prepared by treating the above-mentioned activated material (XXII) with a compound of formula (XXXI) (wherein R3, R4 and R2 are as defined in formula I) under the conditions described above (see Scheme 11 for converting compounds (XXII) and (XI) to compound (XX)).

[0497] Compounds of formula (XXXI), wherein R3, R4 and R2 are as defined in formula I, have been previously described in, for example, WO 2016 / 023954, WO 2016 / 142326 and WO 2017 / 133994.

[0498] Alternatively, a compound of formula II (wherein Q is Q3, defining a compound of formula II-Q3,

[0499] wherein R1, R9, A and R2 are as defined in Formula I)

[0500] Plan 16 :

[0501]

[0502] Can be prepared by the following manner (Scheme 16): in an inert solvent (such as ethanol, toluene or acetonitrile), optionally in the presence of a suitable base (such as sodium carbonate, potassium carbonate or cesium carbonate (or sodium bicarbonate or potassium bicarbonate)), at a temperature between 50 ° C and 150 ° C, optionally under microwave heating conditions, the above-mentioned compound of formula (XXVI) (wherein R1, R9 and A are as defined in formula I, and wherein Xd is a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine)) and a compound of formula (XXXII) (wherein R2 is as defined in formula I) are condensed. Such methods have been previously described, for example, in WO 2011 / 074658. Compounds of formula (XXXII) (wherein R2 is as defined in formula I) are known compounds, commercially available or can be prepared by known methods known to those skilled in the art (see, for example, WO 2011 / 074658 and WO 2010 / 083145).

[0503] Alternatively, a compound of formula II (wherein Q is Q4, defining a compound of formula II-Q4,

[0504] wherein R1, R9, A, G1, G2 and R2 are as defined in Formula I)

[0505] Plan 17 :

[0506]

[0507] Can be prepared by reductive cyclization of a compound of formula (XXXIII) (wherein R1, R9, A, G1, G2 and R2 are as defined in formula I) in the presence of a reducing agent (such as a trialkyl phosphite (more specifically, for example, triethyl phosphite), a trialkylphosphine or triphenylphosphine) (Scheme 17). The principle of this reductive cyclization is similar to the known Cadogan reaction. Alternatively, the reaction can be carried out in the presence of a metal catalyst, for example a molybdenum (VI) catalyst such as MoO2Cl2(dmf)2[molybdenum oxychloride-bis(dimethylformamide)], or more generally with a combination of a transition metal complex and a reducing agent (such as triethyl phosphite, triphenylphosphine or CO). Suitable solvents may include an excess of a reducing agent (such as triethyl phosphite), or for example toluene or xylene, optionally under microwave heating conditions, at temperatures between room temperature and 200°C, preferably between 50°C and 160°C. Such reductive cyclization reaction conditions are described, for example, in WO 2017 / 134066.

[0508] Compounds of formula (XXXIII) (wherein R1, R9, A, G1, G2 and R2 are as defined in formula I) can be prepared by reaction between compounds of formula (XXXIV) (wherein R1, R9 and A are as defined in formula I) and compounds of formula (XXXV) (wherein G1, G2 and R2 are as defined in formula I) in a suitable solvent (which may include, for example, toluene or xylene) typically at a temperature between room temperature and 200°C, preferably between 40°C and 160°C. The formation of compounds of formula (XXXIII) may require removal of water by azeotropic distillation or with a drying agent such as TiCl4 or molecular sieves. Such formation of Schiff bases of formula (XXXIII) is known to those skilled in the art and is described in, for example, WO 2017 / 134066.

[0509] Compounds of formula (XXXV), wherein G1, G2 and R2 are as defined in formula I, are known compounds, commercially available or can be prepared by known methods known to those skilled in the art.

[0510] A compound of formula (XXXIV) (wherein R1, R9 and A are as defined in formula I)

[0511] Plan 18 :

[0512]

[0513] Can be prepared by subjecting the above compounds of formula (XXIII) (or their corresponding activated species (XXII) as described above) to Curtius rearrangement / degradation conditions known to those skilled in the art (Scheme 18). Such conditions have been described, for example, in WO 2009099086 and Journal of Medicinal Chemistry, 55(22), 9589-9606; 2012.

[0514] Alternatively, a compound of formula II (wherein Q is Q7 and X1 is NR3, defining a compound of formula II-Q7-a, wherein R1, R9, A and R3 are as defined in formula I)

[0515] Plan 19 :

[0516]

[0517] It can be prepared by cyclizing a compound of formula (XX-a) (wherein R1, R9, A and R3 are as defined in formula I) under the conditions described above (see Scheme 11 for converting compound (XX) to II-Q1) (Scheme 19).

[0518] Compounds of formula (XX-a) (wherein R1, R9, A and R3 are as defined in formula I) can be prepared by reacting the above-mentioned activated substance (XXII) with a compound of formula (XI-a) or a salt thereof (wherein R3 is as defined in formula I) under similar acylation conditions as described above (see Scheme 11 in the main text).

[0519] Alternatively, compounds of formula (XX-a) wherein R1, R9, A and R3 are as defined in formula I can also be prepared by reacting the alkyl group of the compound of formula (XX-a) with an acylation catalyst (such as 4-dimethylaminopropyl) in the presence of an activator such as propanephosphonic anhydride (T3P), a carbodiimide (such as dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide (DIC) and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC)), optionally in the presence of a suitable base (such as triethylamine, diisopropylethylamine or pyridine), optionally in the presence of a acylation catalyst (such as 4-dimethylaminopropyl)carbodiimide (EDC)). The above compound of formula (XXIII) is prepared by reacting a compound of formula (XI-a) or a salt thereof (wherein R3 is as defined in formula I) in the presence of 2-aminopyridine (DMAP) in a suitable solvent (such as dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, ethyl acetate, toluene, xylene or chlorobenzene and any mixture thereof) and at a temperature between 0°C and about 80°C.

[0520] Alternatively, a compound of formula II-Q7-a (wherein R1, R9, A and R3 are as defined in formula I) can be prepared by reacting a compound of formula II-Q7-a-1 (wherein R1, R9 and A are as defined in formula I) with a compound of formula R3-X in the presence of a base (such as, for example, potassium carbonate, cesium carbonate, lithium hexamethyldisilazane or lithium diisopropylamide) in a suitable solvent (such as acetonitrile, tetrahydrofuran or N,N-dimethylformamide) at a temperature between -78°C and 100°C (preferably between -10°C and 80°C). g The reagent (wherein R3 is as defined in formula I and X g In the specific case where R3 is CH3, methyl iodide, methyl bromide or dimethyl sulfate is the alkylating agent R3-X g A typical representative.

[0521] Compounds of formula II-Q7-a-1 (wherein R1, R9 and A are as defined in formula I) can be prepared by cyclizing compounds of formula (XX-a-1) (wherein R1, R9 and A are as defined in formula I) under the conditions described above (see Scheme 19 for converting compound (XX-a) to II-Q7-a).

[0522] The compound of formula (XX-a-1) (wherein R1, R9 and A are as defined in formula I) can be prepared by reacting the above-mentioned activated substance (XXII) with a compound of formula (XI-a-1) or a salt thereof under similar acylation conditions as described above (see Scheme 19, converting compound (XI-a) into (XX-a)). Alternatively, the compound of formula (XX-a-1) (wherein R1, R9 and A are as defined in formula I) can also be prepared by reacting the above-mentioned compound of formula (XXIII) with a compound of formula (XI-a-1) or a salt thereof under similar acylation conditions as described above (see Scheme 19, converting compound (XI-a) into (XX-a)).

[0523] As another alternative, compounds of formula II-Q7-a-1 (wherein R1, R9 and A are as defined in formula I) can be prepared by directly condensing a compound of formula (XI-a-1) or a salt thereof with the above-mentioned compound of formula (XXII) or (XXIII) under similar conditions as described, for example, in WO20 / 013147.

[0524] Alternatively, a compound of formula II (wherein Q is Q7 and X1 is O, defining a compound of formula II-Q7-b, wherein R1, R9 and A are as defined in formula I)

[0525] Plan 20 :

[0526]

[0527] It can be prepared by cyclizing a compound of formula (XX-b) wherein R1, R9, A and R3 are as defined in formula I, and wherein X is 1, 2 or 3, in the presence of a base such as sodium carbonate, potassium carbonate or cesium carbonate, or potassium tert-butoxide, in the presence of a metal catalyst such as a copper catalyst such as copper (I) iodide, optionally in the presence of a ligand such as a diamine ligand such as N,N′-dimethylethylenediamine or trans-cyclohexyldiamine or dibenzylideneacetone (dba) or 1,10-phenanthroline, in a solvent such as toluene, N,N-dimethylformamide DMF, N-methylpyrrolidone NMP, dimethyl sulfoxide DMSO, dioxane or tetrahydrofuran THF, at a temperature between 30° C. and 180° C., optionally under microwave irradiation (Scheme 20). f is a halogen leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine)).

[0528] A compound of formula (XX-b) wherein R1, R9, A and R3 are as defined in formula I, and wherein X f is a halogen leaving group such as chlorine, bromine or iodine (preferably chlorine or bromine)) can be obtained by reacting the above activated substance (XXII) with a compound of formula (XI-b) or a salt thereof (wherein X f It can be prepared by reacting a halogen leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine).

[0529] Alternatively, compounds of formula (XX-b) (wherein R1, R9, A and R3 are as defined in formula I) can also be prepared by reacting an activator such as propanephosphonic anhydride (T3P), a carbodiimide such as dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide (DIC) and 1-ethyl-3-(3-dimethylamino-propyl)carbodiimide (EDC)), optionally in the presence of a suitable base such as triethylamine, diisopropylethylamine or pyridine, optionally The compound of formula (XXIII) is reacted with a compound of formula (XI-b) or a salt thereof (wherein X is a hydroxyl radical) in the presence of an acylation catalyst (such as 4-dimethylaminopyridine (DMAP)) in a suitable solvent (such as dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, ethyl acetate, toluene, xylene or chlorobenzene and any mixture thereof) at a temperature between 0° C. and about 80° C. f The reaction is carried out with a halogen leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine).

[0530] 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).

[0531] Compounds having formula XXXVI

[0532]

[0533] in

[0534] R1, R9 and A are as defined above under Formula I, and R 100 is OH, chlorine or C1-C4 alkoxy,

[0535] are novel, have been specially developed for the preparation of the compounds according to the invention of formula I and therefore represent a further object of the present invention. The preferences and preferred embodiments of the substituents of the compounds of formula I are also valid for the compounds of formula XXXVI.

[0536] These reactants can react with each other as is, i.e. without adding solvents or diluents. However, in most cases, it is advantageous to add inert solvents or diluents or mixtures thereof. 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.

[0537] The reaction is advantageously carried out in a temperature range of from about -80°C to about +140°C, preferably from about -30°C to about +100°C, and in many cases in a range between ambient temperature and about +80°C.

[0538] 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 other substituent(s) according to the invention in a conventional manner.

[0539] Depending on the reaction conditions and 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 other substituents according to the invention in one and the same reaction step.

[0540] 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 exchanger reagent, and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.

[0541] Salts of compounds of the 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 salts with bases (for example by treatment with suitable acids or with suitable ion exchange reagents).

[0542] Salts of compounds of the formula I can be converted in a manner known per se into other salts, acid addition salts of compounds of the formula I, for example into other acid addition salts, for example by treating salts of inorganic acids (such as hydrochlorides) with suitable metal salts of the acid (such as sodium, barium or silver salts, 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.

[0543] Depending on the procedure or reaction conditions, those compounds of the formula I which have salt-forming properties can be obtained in free form or in the form of salts.

[0544] Depending on the number of asymmetric carbon atoms present in the molecule, the absolute and relative configuration and / or on 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 of these, 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 and also to all possible isomer mixtures, and the above and below are to be understood as such in each case, even if stereochemical details are not explicitly mentioned in each case.

[0545] 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.

[0546] 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, for example, camphoric acid, tartaric acid or malic acid, or a sulfonic acid, for example, camphorsulfonic acid) and separating the diastereomeric mixtures obtainable in this way, for example, by fractional crystallization on the basis of their different solubilities, to give the diastereomers from which the desired enantiomer can be freed by the action of suitable reagents, for example, basic reagents.

[0547] 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 methods of diastereoselective or enantioselective synthesis, for example by carrying out the method according to the invention with starting materials having the appropriate stereochemistry.

[0548] 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.

[0549] Compounds wherein R2 is C1-C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl may be prepared from the corresponding compounds wherein R2 is C1-C4 haloalkylsulfanyl using a suitable oxidation method as described, for example, in WO 19 / 008115.

[0550] If the individual components have different biological activities, it is advantageous to isolate or synthesize the biologically more effective isomers, such as enantiomers or diastereomers or isomer mixtures, such as enantiomeric mixtures or diastereomeric mixtures, in each case.

[0551] If appropriate, the compounds of formula I and, where appropriate, their tautomers (in each case in free form or in salt form) can 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.

[0552] The compounds of formula I according to the following tables X, A-1 to A-22 and B-1 to B-4 can be prepared according to the above methods. The following examples are intended to illustrate the invention and show preferred compounds of formula I.

[0553] Tables A-1 to A-22 below illustrate specific compounds of the present invention.

[0554]

[0555] Table A-1 provides four compounds A-1.001 to A-1.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q6, such as:

[0556]

[0557] Table X: Definition of Substituents of A and R9

[0558]

[0559]

[0560] For example, compound A-1.004 has the following structure:

[0561]

[0562] Table A-2 provides four compounds A-2.001 to A-2.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q6, such as:

[0563]

[0564] Table A-3 provides four compounds A-3.001 to A-3.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q1, such as:

[0565]

[0566] Table A-4 provides four compounds A-4.001 to A-4.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q1, such as:

[0567]

[0568] Table A-5 provides four compounds A-5.001 to A-5.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q2, such as:

[0569]

[0570] Table A-6 provides four compounds A-6.001 to A-6.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q3, such as:

[0571]

[0572] Table A-7 provides four compounds A-7.001 to A-7.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q1, such as:

[0573]

[0574] Table A-8 provides four compounds A-8.001 to A-8.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q1, such as:

[0575]

[0576] Table A-9 provides four compounds A-9.001 to A-9.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q4, such as:

[0577]

[0578] Table A-10 provides four compounds A-10.001 to A-10.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q4, such as:

[0579]

[0580] Table A-11 provides four compounds A-11.001 to A-11.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q5, such as:

[0581]

[0582] Table A-12 provides four compounds A-12.001 to A-12.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q5, such as:

[0583]

[0584] Table A-13 provides four compounds A-13.001 to A-13.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q5, such as:

[0585]

[0586] Table A-14 provides four compounds A-14.001 to A-14.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q5, such as:

[0587]

[0588] Table A-15 provides four compounds A-15.001 to A-15.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q1, such as:

[0589]

[0590] Table A-16 provides four compounds A-16.001 to A-16.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q1, such as:

[0591]

[0592] Table A-17 provides four compounds A-17.001 to A-17.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q1, such as:

[0593]

[0594] Table A-18 provides four compounds A-18.001 to A-18.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q1, such as:

[0595]

[0596] Table A-19 provides four compounds A-19.001 to A-19.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q1, such as:

[0597]

[0598] Table A-20 provides four compounds A-20.001 to A-20.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q2, such as:

[0599]

[0600] Table A-21 provides four compounds A-21.001 to A-21.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q7, such as:

[0601]

[0602] Table A-22 provides four compounds A-22.001 to A-22.004 of formula I, wherein R1 is ethyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q7, such as:

[0603]

[0604] Tables B-1 to B-4 below further illustrate specific compounds of the present invention.

[0605] Table B-1 provides four compounds B-1.001 to B-1.004 of formula I, wherein R1 is -CH2 cyclopropyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q6, such as:

[0606]

[0607] Table B-2 provides four compounds B-2.001 to B-2.004 of formula I, wherein R1 is -CH2 cyclopropyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q1, such as:

[0608]

[0609] Table B-3 provides four compounds B-3.001 to B-3.004 of formula I, wherein R1 is -CH2 cyclopropyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q2, such as:

[0610]

[0611] Table B-4 provides four compounds B-4.001 to B-4.004 of formula I, wherein R1 is -CH2 cyclopropyl, and A and R9 are as defined in Table X, and Q is selected from a group of formula Q1, such as:

[0612]

[0613] The compounds of formula I according to the present 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 ingredient according to the present invention acts on all or individual developmental stages of normally sensitive and resistant animal pests (such as representatives of insects or Acarina, nematodes or molluscs). The insecticide, nematode, molluscicide or acaricide activity of the active ingredient according to the present invention can be directly shown per se, i.e., immediately or only after some time has passed (e.g., during molting) the death or destruction of the pest occurs; or indirectly, such as by reducing egg laying and / or hatching rate, antifeedant effect, and / or growth inhibition.

[0614] The compounds of formula (I) according to the present invention can have many benefits, including in particular favorable levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (e.g., higher biological activity, favorable activity spectrum, increased safety profile, improved physico-chemical properties, or increased biodegradability or environmental properties). In particular, it has been unexpectedly found that certain compounds of formula (I) exhibit favorable safety profiles relative to non-target organisms, such as non-target arthropods, particularly pollinators (such as honey bees, solitary bees, and bumblebees). Most particularly, relative to Apis mellifera.

[0615] In this respect, certain compounds of formula (I) according to the invention may be distinguished from known compounds by a greater efficacy at low application rates, which can be demonstrated by a person skilled in the art using experimental procedures similar to or adapted from those outlined in the Biological Examples, using lower application rates (if necessary) such as 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

[0616] Furthermore, it has been surprisingly found that the compounds of formula (I) according to the invention exhibit advantageous physicochemical properties for use in crop protection, in particular a reduced melting point, reduced lipophilicity and increased water solubility. Such properties have been found to be advantageous for plant uptake and systemic distribution, see for example A. Buchholz, S. Trapp, Pest Management Sci [Pest Management] 2016; 72: 929-939) for controlling certain pest species listed below.

[0617] Postulated metabolites of compounds of Formula I that may be formed in the practice of the present invention in combination with one or more of the following methods, pests, crops, and / or targets include amide compounds of Formula I-M1 and acid compounds of Formula I-M2, each corresponding to the parent nitrile compound of Formula I:

[0618]

[0619] wherein Q, R1, R2, R3, R4, R9, X1, G1, G2 and A are as defined above under formula I, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof. Among specific putative metabolites, mention may be made of: (1) amide compounds of formula I-M1 corresponding to the parent nitrile selected from the group consisting of the compounds described in Tables A-1 to A-22 and B-1 to B-4 and Table P; and (2) acid compounds of formula I-M2 corresponding to the parent nitrile selected from the group consisting of the compounds described in Tables A-1 to A-22 and B-1 to B-4 and Table P.

[0620] Examples of the above-mentioned animal pests are:

[0621] From the order Acarina, e.g.

[0622] 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.;

[0623] From the order Phthirus, e.g.

[0624] Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp., and Phylloxera spp.;

[0625] From the order Coleoptera, e.g.

[0626] Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotomas spp., Conoderus spp., Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephalas spp., Dermestes spp., Diabrotica spp.), Argentine beetle (Diloboderus abderus), herbivorous ladybirds (Epilachna spp.), Eremnus species, Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemlineata, Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Maladera castanea, American leaf beetles (Megascelis spp.), rapeseed beetles (Melighetes aeneus), Melolontha spp., Myochrousarmatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp.), Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp.), Somaticus spp., Cryptorhynchus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp., and Trogoderma spp.;

[0627] From the order Diptera, e.g.

[0628] 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.;

[0629] From the order Hemiptera, e.g.

[0630] Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Amblypelta nitida, Bathycoeliathalassina, Acanthocoris spp., Acrosternum spp., Clavigralla tomentosicollis, Creontiades spp., Dichelops furcatus, Acanthocoris spp., Edessa spp., and Acanthocoris spp. Euschistus spp.), six-spotted cabbage bug (Eurydema pulchrum), flat shield bug species, brown-winged stink bug, Horcias nobilellus, rice-margined stink bug species, grass stink bug species, tropical scale species, Murgantia histrionic, new long-margined stink bug species, tobacco blind bug (Nesidiocoris tenuis), green stink bug species, Nysius simulans, island stink bug, skin stink bug species, wall stink bug species, red assassin bug species, cocoa brown stink bug, chestnut stink bug (Scaptocoris castanea), black stink bug species (Scotinophara spp.), Thyanta species, trypanosoma species, cassava web stink bug (Vatiga illudens);

[0631] Acyrthosium pisum, Adalges species, Agalliano ensigera, Targuiron vein psyllid, Aleurodicus species, Aleurocanthus species, sugarcane hole whitefly, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, lemon leafhopper, Nephrodisiac species, Aphididae, Aphid species, Aspidiotus species, eggplant groove aphid, Bactericera cockerelli, Aleurodicus species, Brachycaudus species, cabbage aphid, Cavariella species, Cavariella aegopodii Scop.), wax scale species, black-brown round shield scale, orange-brown round shield scale, leafhopper species, large white leafhopper (Cofana spectra), Cryptophyllum species, leafhopper species, brown soft scale, corn yellow-winged leafhopper, naked whitefly species, citrus psyllid, wheat aphid, western round tail aphid species, small green leafhopper species, apple aphid, grape leafhopper species, Gascardia species, red eucalyptus psyllid (Glycaspis brimblecombei), cabbage constrictor aphid (Hyadaphis pseudobrassicae), large tail aphid species (Hyalopterus spp.), Hyperomyzus pallidus, lemon green leafhopper (Idioscopus clypealis), African leafhopper, Laodelphax striatellus species, water-hard scale, oyster shield scale species, radish aphid (Lopaphis erysimi), Lyogenys maidis, Aphid species, Cicada species, Metcalfa pruinosa, Aphid, Cicada, Aphid species, Neotoxoptera sp, Blacktail leafhopper species, Nilaparvata spp.), pear green aphid, Odonaspis ruthae, sugarcane cotton aphid, bayberry whitefly, Caulis psyllid, Shield scale species, Gall aphid species, Corn waxhopper, Flat-horned planthopper species, Hob wart aphid, Phylloxera species, Mosella species, Mulberry white scale species, Mealybug species, Cotton blind bug (Pseudatomoscelis seriatus), Psyllid species, Cotton scale (Pulvinaria aethiopica), Toothed scale species, Quesada gigas, Electric leafhopper (Recilia dorsalis), Constrictor aphid species, Black helmet scale species, Banded leafhopper species, Aphid species, Sitobion spp., White-backed planthopper, Spissistilus triangularis festinus), Tarophagus Proserpina, aphid species, whitefly species, Tridiscus sporoboli, Trionymus spp., African psyllids, scaly scale, flame leafhopper, and Zyginidia scutellaris.

[0632] From the order Hymenoptera, e.g.

[0633] Acromyrmex, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprions spp., Pogonomyrmex spp., imported fire ants, Solenopsis spp., and Vespa spp.

[0634] From the order Isoptera, e.g.

[0635] Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Tropical fire ants (Solenopsis geminate)

[0636] From the order Lepidoptera, for example,

[0637] Species of the genus Long-winged Roller Moth, species of the genus Brown-banded Roller Moth, species of the genus Clearwing Moth, species of the genus Noctua, cotton leafworm, species of the genus Amylois, species of the genus Mucuna, species of the genus Yellow Roller Moth, species of the genus Argyresthia, species of the genus Banded Roller Moth, species of the genus Spodoptera, species of cotton miner, corn armyworm, powdery moth, peach fruit moth, species of the genus Graminus, species of the genus Color Roller Moth, Chrysoteuchia topiaria, grape fruit moth, species of the genus Leaf Roller, species of the genus Cloud Roller, species of the genus Striped Roller Moth, species of the genus Sheath Moth, Colias lesbia, Cosmophila flava), grass borer species, cabbage borer, apple anomaly moth, boxwood moth, moth moth species, boxwood moth, stem borer species, Sudan cotton bollworm, Spodoptera species, sweet potato stem borer, mealybug species, leaf moth species (Epinotias spp.), salt marsh moth (Etiella acrea), Etiella zinckinella, flower moth species, ring needle moth, yellow tussock moth species, root cutter species, Feltia jaculiferia, Grapholitas spp., cloud moth, Heliothis species, cabbage borer, leaf cutter species (Herpetogramma spp.), gypsy moth, tomato borer, Lasmopalpus lignosellus, spiral leaf miner, leaf miner species, grape flower moth, Loxostege bifidalis, tussock moth species, miner species, leaf moth species (Malacosoma spp.), cabbage armyworm, tobacco hornworm, smooth-bellied moth species (Mythimna spp.), noctuid species, fall moth species, Orniodes indica, European corn borer, super-small tortoise species, brown tortoise species, small-eyed moth, stem borer, red bell moth, coffee leaf miner, one-star armyworm, potato moth, cabbage butterfly, Pieris species, diamondback moth, white nest moth species, leaf moth species, mint gray moth (Rachiplusia nu), western bean incense (Richia albicosta), white grain borer species (Scirpophaga spp.), Spodoptera species, Cyprinodon species, Spodoptera species, Cotton leaf roller, Cnaphalocrocis species, Heteroptera species, Trichoplusia species, Tomato leafminer, and Lymantria species;

[0638] From the order Mallophaga, for example,

[0639] Damalina spp. and Trichodectes spp.;

[0640] From the order Orthoptera, for example,

[0641] Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscus spp., and Schistocerca spp.;

[0642] From the order Psocoptera, for example,

[0643] Liposcelis spp.;

[0644] From the order Siphonaptera, for example,

[0645] Ceratophyllus spp., Ctenocephalides spp., and Xenopsylla cheopis;

[0646] From the order Thysanoptera, for example,

[0647] Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp.

[0648] From the order of the Thysanura, for example, Lepisma saccharina.

[0649] The active ingredients according to the invention can be used for controlling (i.e. suppressing or destroying) pests of the above-mentioned type, which occur in particular on plants, especially on useful and ornamental plants in agriculture, in horticulture and in 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.

[0650] In particular, suitable target crops are 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, sunflower, coconut, castor, cocoa beans, or peanuts; cucurbits such as pumpkin, cucumber, or melon; fiber plants such as cotton, flax, hemp, or jute; citrus fruits such as oranges, lemons, grapefruits, or tangerines; vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, or bell peppers; lauraceae such as avocado, cinnamon, or camphor; and also tobacco, nuts, coffee, eggplant, sugarcane, tea, pepper, grapevines, hops, plantago, and latex plants.

[0651] 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.

[0652] For example, the present invention can be used with any of the following ornamental plant species: Ageratum species, Alonsoa species, Anemone species, Anisodontea capsenisis, Anthemis species, Antirrhinum species, Aster species, Begonia species (e.g., Rieger Begonia, Begonia sempervirens, Begonia tubéreux), Bougainvillea species, Brachycome species, Brassica species (ornamentals), Calceolaria species, Capsicum, Catharanthus roseus, Canna species, Centaurea species, Chrysanthemum species, Cineraria species (C. maritime), Coreopsis species, Crassula coccinea, Cupheaignea, Dahlia species, Delphinium species, Dicentra species, Dorotheantus species. spp.), Lisianthus, Forsythia species, Fuchsia species, Geranium gnaphalium, Gerbera species, Globe amaranth, Heliotrope species, Sunflower species, Hibiscus species, Hydrangea species, Hydrangea species, Rhododendron, Impatiens species (African balsam), Amaranth species (Iresines spp.), Kalanchoe species, Lantana, March flower, Lion's ear, Lilium species, Mesembryanthemum species, Physalis species, Monarda species, Dracaena species, Marigold species, Dianthus species (carnation), Canna species, Oxalis species, Daisy species, Pelargonium species (Shieldleaf Pelargonium, Horseshoe Pelargonium), Viola species (Viola tricolor), Petunia species, Phlox species, Plecthranthus species spp.), poinsettia species, creeper species (five-leaf creeper, Parthenocissus quinquefolia), primula species, ranunculus species, azalea species, Rosa species (roses), rudbeckia species, African violet species, salvia species, Scaevola aemola, Schizanthus wisetonensis, sedum species, Solanum species, Surfinia petunia species (Surfinia spp.), marigold species, Nicotiana species, verbena species, zinnia species, and other bedding plants.

[0653] For example, the present invention can be used with any of the following vegetable species: Allium (garlic, onion, shallot (A.oschaninii), leek, shallot, scallion), beaked parsley, celery, asparagus, beets, Brassica (cabbage, 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, rhubarb, rosemary, sage, black salsify, eggplant, spinach, Valerian (V. eriocarpa), and broad beans.

[0654] Preferred ornamental plant species include African violet, begonia, dahlia, gerbera, hydrangea, verbena, rose, kalanchoe, poinsettia, aster, cornflower, coreopsis, delphinium, monarda, phlox, rudbeckia, sedum, petunia, violet, impatiens, geranium, chrysanthemum, ranunculus, fuchsia, salvia, hydrangea, rosemary, sage, St. John's wort, mint, sweet pepper, tomato, and cucumber.

[0655] 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 beetle (preferably on potatoes) and the striped stem borer (preferably on rice).

[0656] 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 beetle (preferably on potatoes) and the striped stem borer (preferably on rice).

[0657] In another aspect, the present invention may also relate to a method for controlling damage to plants and parts thereof 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 species of root knot nematodes; cyst-forming nematodes, Globodera rostochiensis and other species of Globodera; Heterodera avenae, Heteroderaglycines, 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 Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus, and other Bursaphelenchus species; Ring nematodes, nematodes), Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stemand bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci, and other Ditylenchus species; Awl nematodes, Dolichodorus species;Spiral nematodes, Heliocotylenchus multicinctus, and other species of the genus Helicotylenchus; Sheath and sheathoid nematodes, species of the genera Hemicycliophora, and species of the genera Hemicriconemoides; Hirshmanniella species; Lancenematodes, species of the genus Hoploaimus; False rootknot nematodes, species of the genus Nacobbus; Needle nematodes, Longidoruse longatus, and other species of the genus Longidorus; Pin nematodes, species of the genus Pratylenchus; Lesion nematodes. nematodes), Pratylenchus negletus, 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.

[0658] The compounds of the present invention may also have activity against molluscs. Examples include, for example, the Pomacea family; the Arion family (A. ater, A. circumscriptus, A. hortensis, A. rufus); the Bradybaenidae family (Bradybaenidae, A. rufus); fruticum); Cepaea (Cepaea hortensis, C. nemoralis); Ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (Galba trunculata); Helicelia (H. itala, H. obvia); Helicigona (Helicidae). 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.

[0659] The term "crops" is to be understood as also including crop plants which have been transformed by the use of recombinant DNA techniques such 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.

[0660] 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, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or vegetative insecticidal proteins (Vips), such as Vip1, Vip2, Vip3, or Vip3A; or insecticidal proteins of bacterial colonizing nematodes, for example, Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophila, or Xenorhabdus spp. nematophilus); toxins produced by animals, such as scorpion toxins, spider toxins, bee toxins and other insect-specific neurotoxins; toxins produced by fungi, such as streptomycin, plant lectins, such as pea lectin, barley lectin or snowdrop lectin; agglutinin; protease inhibitors, such as trypsin inhibitor, silk proteinase inhibitor, potato glycoprotein, cystatin, papain inhibitor; ribosome inactivating protein (RIP), such as ricin, maize-RIP, abrin, luffain, saporin or bryophyllin; steroid metabolizing enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysteroid 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.

[0661] In the context of the present invention, δ-endotoxins (e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C) or vegetative insecticidal proteins (Vips) (e.g., Vip1, Vip2, Vip3, or Vip3A) are understood to include, but are not limited to, mixed toxins, truncated toxins, and modified toxins. Mixed toxins are recombinantly produced by combining different domains of those proteins (see, e.g., 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).

[0662] 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.

[0663] Methods for preparing such transgenic plants are generally 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.

[0664] The toxins contained 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).

[0665] Transgenic plants comprising 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 varieties expressing Cry9C toxin); (corn varieties expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) that confer tolerance to the herbicide glufosinate-ammonium); (cotton variety expressing Cry1Ac toxin); (cotton variety expressing Cry1Ac toxin); (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

[0666] Further examples of such genetically modified crops are:

[0667] 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 transgenicly expresses the PAT enzyme to confer tolerance to the herbicide glufosinate-ammonium.

[0668] 2. Bt176 maize, from Syngenta Seeds, 27 Rue de Hobbit, 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 toxin Cry1Ab. Bt176 maize also transgenicly expresses the enzyme PAT to confer tolerance to the herbicide glufosinate-ammonium.

[0669] 3. MIR604 maize, from Syngenta Seeds, 27 Rue de Hobbit, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. This maize plant 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 this transgenic maize plant is described in WO 03 / 018810.

[0670] 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.

[0671] 5. IPC 531 cotton, from Monsanto Europe AB, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0672] 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.

[0673] 7. NK603×MON 810 corn, from Monsanto Europe, 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 NK603 and MON 810. NK603×MON 810 corn transgenically expresses the protein CP4 EPSPS obtained from the Agrobacterium strain CP4, rendering it herbicide tolerant. (contains glyphosate) and also expresses the Cry1Ab toxin from Bacillus thuringiensis subsp. kurstakia, which confers resistance to certain lepidopteran insects, including the European corn borer.

[0674] 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.

[0675] The term "crop" should be understood to also include crop plants 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.

[0676] 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.

[0677] Crops also include those with increased resistance to nematodes, such as Heterodera glycines.

[0678] 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.

[0679] Antipathogenic substances that can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers of sodium channels and calcium channels, for example 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 (see, for example, WO 95 / 33818) or proteins or polypeptide factors which are involved in plant pathogen defense (so-called "plant disease resistance genes", as described in WO 03 / 000906).

[0680] Other areas of use of the compositions according to the invention are the protection of stored goods and storage rooms and the protection of raw materials such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, in particular the protection of humans, domestic animals and productive livestock from pests of the types mentioned.

[0681] 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 compositions to substrates such as nonwoven or fabric materials in the form of (or that can be used in the manufacture of) netting, coverings, bedding, curtains, and tents is contemplated.

[0682] In one embodiment, the method for controlling this type of harmful organism comprises applying the composition of the present invention of pest-killing effective dose to target harmful organism, their place or surface or substrate, so that on this surface or substrate, effective pest-killing activity of retention is provided.Such application can be carried out by brushing, rolling, spraying, coating or dipping pest-killing composition of the present invention.By way of example, the IRS application of surface (such as wall, ceiling or floor surface) is considered by method of the present invention, so that effective pest-killing activity of retention is provided on this surface.In another embodiment, it is considered to use this type of composition for the residual control of the harmful organism on substrate, this substrate is the fabric material as in the form (or can be used for the manufacture of these articles) of netting, covering, quilt, curtain and tent.

[0683] 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, etc.). 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.

[0684] 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.

[0685] In the field of tree injection / trunk treatment, the compounds according to the invention are particularly suitable for combating wood-boring insects from the orders Lepidoptera and from the orders Coleoptera mentioned above, in particular against the wood-boring insects listed in the following Tables A and B:

[0686] Table A. Examples of economically important exotic wood-boring insects.

[0687]

[0688] Table B. Examples of economically important native wood-boring insects.

[0689]

[0690]

[0691]

[0692] 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, ticks, 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.

[0693] In particular, the present invention can be used to control insect pests that feed on the roots of turfgrasses, including grubs (such as Cyclocephala spp. (e.g., the marked beetle, C. lurida), Rhizotrogus spp. (e.g., the European beetle, R. majalis), Cotinus spp. (e.g., the Green June beetle, C. nitida), Popillia spp. (e.g., the Japanese beetle, P. japonica), Phyllophaga spp. (e.g., the May / June beetle), Ataenius spp. (e.g., the Black turfgrass ataenius, A. spretulus), Maladera spp. (e.g., the Asiatic garden beetle, A. beetle, M. castanea, and Tomarus genera), ground pearls (Margarodes spp.), mole crickets (tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana), and leatherjackets (European crane fly, Tipula spp.).

[0694] 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).

[0695] 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.

[0696] 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.

[0697] In the hygiene sector, the compositions according to the invention are effective against epiparasites such as hard ticks, soft ticks, scabies, autumn mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.

[0698] Examples of such parasites are:

[0699] From the order of the Pediculus: Haemaphysalis spp., Linognathus spp., Pediculus hominis spp., and Phtirus spp., Phitirus spp.

[0700] From the order Trichophagus: Felicola species, Felicola species, Felicola species, Felicola species, Werneckiella spp., Lepikentron spp., Felicola species, Felicola species, and Felicola species.

[0701] Of the order Diptera and the suborders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp. spp.), Braula spp., Musca spp., Hydrotaea spp., Biting flies, Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp.) and Melophagus spp.

[0702] From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllum spp.

[0703] From the order of the Heteropterida, for example, Cimex spp., Triatominae spp., Panstrongylus spp.

[0704] From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattelagermanica and Supella spp.

[0705] Subclass Acaria (family Acarida) and orders Meta-stigmata and Meso-stigmata, for example, Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyommas spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp. spp.), Sternostoma spp., and Varroa spp.

[0706] From the orders Actinedida (Prostigmata) and Acaridida (Astigmata), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp. spp.), Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcooptes spp., Notoedress spp., Knemidocoptes spp., Cytodites spp., and Laminosioptes spp.

[0707] 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 construction materials from infestation by insects.

[0708] The compositions according to the invention can be used, for example, to combat the following pests: beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale), Minthes rugicollis, Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec., and Dinoderus minutus, as well as Hymenoptera, such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, and Urocerus augu, and termites, such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes spp. indicola), Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, and Coptotermes formosanus, as well as borers such as Silverfish (Lepisma saccharina).

[0709] The compounds according to the invention can be used as pesticides in unmodified form, but they are usually formulated into compositions in various ways using formulation adjuvants such as carriers, solvents and surfactants. 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, mobile 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 diluted before use. Dilution can be performed with, for example, water, liquid fertilizers, micronutrients, biological organisms, oils or solvents.

[0710] These formulations can be prepared, for example, by mixing the active ingredient with a formulation adjuvant in order to obtain a composition in the form of a finely divided solid, granules, solution, dispersion or emulsion. The active ingredients can also be formulated with other adjuvants such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surfactants or combinations thereof.

[0711] These active ingredients can also be contained in very fine microcapsules. Microcapsules contain active ingredients in porous carriers. This allows the active ingredient to be released (e.g., slowly released) into the environment in a controlled amount. Microcapsules typically have a diameter of from 0.1 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 skilled 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.

[0712] Formulation adjuvants suitable for preparing the compositions according to the invention are known per se. Liquid carriers which can be used include: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol rosinate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide , dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol (diproxitol), 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, acetic acid glyceryl, diacetic acid glyceryl, triethylhexane Glyceryl esters, 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 octanoate, methyl oleate, dichloromethane, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, lactic acid Propyl acetate, 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.

[0713] 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, ground walnut shells, lignin, and similar substances.

[0714] 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; salts of dialkylsulfosuccinates, 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 dialkyl phosphates; and further substances, such as are described, for example, in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Company. Corp.), Ridgewood New Jersey (1981).

[0715] Additional 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 alter the pH, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze agents, microbicides, and liquid and solid fertilizers.

[0716] 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 and an oil derivative. The amount of the oil additive in the composition according to the invention is generally from 0.01% to 10% based on the mixture to be applied. For example, the oil additive 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.

[0717] These compositions according to the invention generally comprise from 0.1% to 99% by weight, in particular from 0.1% to 95% by weight, of a compound according to the invention and from 1% to 99.9% by weight of formulation adjuvants, which preferably include from 0 to 25% by weight of surface-active substances. Whereas commercial products may preferably be formulated as concentrates, the end user will generally use dilute formulations.

[0718] The application rate varies within wide limits and depends on the nature of the soil, the application method, the crop plants, the harmful organisms to be controlled, the prevailing climatic conditions, and other factors dictated by the application method, the time of application, and the target crop. In general, the compound can be applied at a rate of from 1 to 2000 l / ha, in particular from 10 to 1000 l / ha.

[0719] A preferred formulation may have the following composition (wt %):

[0720] Emulsifiable concentrates :

[0721] Active ingredient: 1% to 95%, preferably 60% to 90%

[0722] Surfactant: 1% to 30%, preferably 5% to 20%

[0723] Liquid carrier: 1% to 80%, preferably 1% to 35%

[0724] Dust agent :

[0725] Active ingredient: 0.1% to 10%, preferably 0.1% to 5%

[0726] Solid carrier: 99.9% to 90%, preferably 99.9% to 99%

[0727] Suspension concentrate:

[0728] Active ingredient: 5% to 75%, preferably 10% to 50%

[0729] Water: 94% to 24%, preferably 88% to 30%

[0730] Surfactant: 1% to 40%, preferably 2% to 30%

[0731] wettable powder :

[0732] Active ingredient: 0.5% to 90%, preferably 1% to 80%

[0733] Surfactants: 0.5% to 20%, preferably 1% to 15%

[0734] Solid carrier: 5% to 95%, preferably 15% to 90%

[0735] Granules:

[0736] Active ingredient: 0.1% to 30%, preferably 0.1% to 15%

[0737] Solid carrier: 99.5% to 70%, preferably 97% to 85%

[0738] The following examples further illustrate (but do not limit) the present invention.

[0739] <![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 of ethylene oxide) - 2％ - Highly dispersed silicic acid 5％ 10％ 10％ Kaolin 62％ 27％ -

[0740] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a wettable powder which can be diluted with water to give a suspension of the desired concentration.

[0741]

[0742]

[0743] 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.

[0744] <![CDATA[ Emulsifiable concentrates ]]> Active ingredient 10％ Octylphenol polyglycol ether (4-5 mol of ethylene oxide) 3％ Calcium dodecylbenzenesulfonate 3％ Castor oil polyglycol ether (35 mol of ethylene oxide) 4％ Cyclohexanone 30％ Xylene mixture 50％

[0745] Emulsions of any desired dilution which can be used in plant protection can be obtained from these concentrates by dilution with water.

[0746]

[0747] 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 seed dressing of seeds.

[0748] <![CDATA[ Extruder granules ]]> Active ingredient 15％ Sodium lignin sulfonate 2％ Carboxymethyl cellulose 1％ Kaolin 82％

[0749] The combination is mixed and ground with the adjuvants, and the mixture is moistened with water.

[0750] The mixture is extruded and then dried in a stream of air.

[0751] <![CDATA[ Coated granules ]]> Active ingredient 8％ Polyethylene glycol (molecular weight 200) 3％ Kaolin 89％

[0752] 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.

[0753] Suspension concentrates

[0754] Active ingredient 40％ Propylene glycol 10％ Nonylphenol polyglycol ether (15 mol of ethylene oxide) 6％ Sodium lignin sulfonate 10％ Carboxymethyl cellulose 1％ Silicone oil (in the form of a 75% emulsion in water) 1％ water 32％

[0755] The finely ground combination is intimately mixed with adjuvants to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation materials can be treated and protected against microbial infestation by spraying, pouring or immersion.

[0756] Flowable concentrate for seed treatment

[0757]

[0758] The finely ground combination is intimately mixed with adjuvants to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation materials can be treated and protected against microbial infestation by spraying, pouring or immersion.

[0759] Extended-release capsule suspension

[0760] 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 polymerization 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 8-15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for this purpose.

[0761] 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 concentrates (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume concentrates (UL), finished products (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG), or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0762] Preparation example:

[0763] "Mp" refers to the melting point in ° C. Free radicals represent methyl groups. Recorded on a Brucker 400 MHz spectrometer 1 H NMR measurements, chemical shifts are given in ppm relative to TMS standards. Spectra were measured in deuterated solvents as specified. The compounds were characterized using any of the following LCMS methods. Characteristic LCMS values obtained for each compound are the retention time ("Rt", reported in minutes) and the measured molecular ion (M+H) + or (MH) - .

[0764] LCMS and GCMS methods:

[0765] Method 1 :

[0766] Spectra were recorded on a Waters mass spectrometer (ZQ single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative, capillary voltage: 3.00 kV, cone range: 30-60 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 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 μm, 30×2.1 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: 0 min 0% B, 100% A; 1.2-1.5 min 100% B; flow rate (ml / min) 0.85.

[0767] Method 2 :

[0768] Spectra were recorded on a Waters mass spectrometer (SQD or ZQ single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative, capillary voltage: 3.00 kV, cone range: 30-60 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 to 900 Da) and a Waters Acquity UPLC: binary pump, heated column compartment, and diode array detector. Solvent degasser, binary pump, heated column compartment, and diode array detector. Column: Waters UPLCHSS T3, 1.8 μm, 30×2.1 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: 0 min 0% B, 100% A; 2.7-3.0 min 100% B; flow rate (ml / min) 0.85.

[0769] Method 3 :

[0770] Spectra were recorded on an Agilent Technologies mass spectrometer (6410 triple quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative switching, capillary voltage: 4.00 kV, fragmentor voltage: 100.00 V, gas temperature: 350° C., gas flow: 11 L / min, nebulizer gas: 45 psi, mass range: 110-1000 Da; DAD wavelength range: 210-400 nm). Column: KINETEX EVO C18, length 50 mm, diameter 4.6 mm, particle size 2.6 μm. Column oven temperature 40° C. Solvent gradient: A = water with 0.1% formic acid: acetonitrile (95:5 v / v). B = acetonitrile with 0.1% formic acid. Gradient = 0 min 90% A, 10% B; 0.9-1.8 min 0% A, 100% B, 2.2-2.5 min 90% A, 10% B. Flow rate 1.8 mL / min.

[0771] Method 4 :

[0772] Spectra were recorded on a mass spectrometer from Waters (Acquity SDS mass spectrometer) equipped with an electrospray source (polarity: positive and negative switching, capillary voltage: 3.00 kV, cone voltage: 41.00 V, source temperature: 150° C., desolvation gas flow: 1000 L / Hr, desolvation temperature: 500° C., cone gas flow: 50 L / hr, mass range: 110-800 Da; PDA wavelength range: 210-400 nm. Column: Acquity UPLC HSS T3 C18, length 30 mm, diameter 2.1 mm, particle size 1.8 μm. Column oven temperature 40° C. Solvent gradient: A = water with 0.1% formic acid: acetonitrile (95:5 v / v). B = acetonitrile with 0.05% formic acid. Gradient = 0 min 90% A, 10% B; 0.2 min 50% A, 50% B; 0.7-1.3min 0% A, 100% B; 1.4-1.6min 90% A, 10% B. The flow rate is 0.8mL / min.

[0773] Method 5:

[0774] Spectra were recorded on a Waters mass spectrometer (SQ Detector 2 single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative, capillary voltage: 2.50 kV, cone voltage: 41 V, extractor: 3.00 V, source temperature: 150°C, desolvation temperature: 500°C, cone gas flow: 50 L / Hr, desolvation gas flow: 1000 L / Hr, mass range: 100 to 600 Da) and a Waters Acquity UPLC with a quaternary pump, heated column compartment, and diode array detector. The column used was a Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm. The column oven temperature was 40°C. DAD wavelength range (nm): 200 to 350. Solvent gradient: A = water + 5% acetonitrile + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH. Gradient = 0 min 90% A, 10% B; 0.2 min 50% A, 50% B; 0.7-1.3 min 0% A, 100% B; 1.4-1.6 min 90% A, 10% B. Flow rate 0.6 mL / min.

[0775] Preparation of examples of compounds of formula (I):

[0776] Example P1: 2-[[5-(cyclopropylmethylsulfonyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridinium Preparation of [6-oxazinyl]-3-pyridyl]oxy]-2-methyl-propionitrile (Compound P1)

[0777]

[0778] Step 1: 2-[[5-(cyclopropylmethylsulfanyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridinium Preparation of [6-oxazine]-3-pyridinyl]oxy]-2-methyl-propionamide (Compound I8)

[0779]

[0780] 5-(Cyclopropylmethylsulfanyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]pyridin-3-ol (compound I7 prepared similarly to Example P2, Step 1) was treated under the same conditions as described in Example P2, Step 2 to give the desired compound.

[0781] LCMS (Method 5): m / z 467 [M+H] + ; Retention time: 1.13min.

[0782] Step 2: 2-[[5-(cyclopropylmethylsulfanyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridinium Preparation of [6-oxazinyl]-3-pyridyl]oxy]-2-methyl-propionitrile (Compound I9)

[0783]

[0784] 2-[[5-(Cyclopropylmethylsulfanyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridinyl]oxy]-2-methyl-propionamide (Compound I8 prepared as described above) was treated under the same conditions as described in Step 3 of Example P2 to give the desired compound.

[0785] LCMS (Method 5): m / z 449 [M+H] + ; Retention time: 1.21min.

[0786] Step 3: 2-[[5-(cyclopropylmethylsulfonyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridinium Preparation of [6-oxazinyl]-3-pyridyl]oxy]-2-methyl-propionitrile (Compound P1)

[0787]

[0788] 2-[[5-(Cyclopropylmethylsulfanyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile (Compound I9 prepared as described above) was treated under the same conditions as described in Step 4 of Example P2 to give the desired compound.

[0789] LCMS (Method 5): m / z 481 [M+H] + ; Retention time: 1.17min.

[0790] Example P2: 2-[[5-ethylsulfonyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazine-6- Preparation of 3-pyridyl]-2-methyl-3-pyridyl]-oxy-2-methyl-propionitrile (Compound P2)

[0791]

[0792] Step 1: 5-Ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]pyridine- Preparation of 3-alcohol (Compound I1)

[0793]

[0794] Cesium carbonate (19.5 g, 59.8 mmol, 2.50 equiv) and (E)-benzaldehyde oxime (3.4 mL, 31.1 mmol, 1.30 equiv) were added to a solution of 6-(5-bromo-3-ethylsulfanyl-2-pyridyl)-7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazine (prepared according to WO 2016059145) (10.0 g, 23.9 mmol) in acetonitrile (240 mL). The resulting suspension was stirred at 50 ° C for 42 hours. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure, the crude residue was partitioned between ethyl acetate and water, and the pH of the aqueous phase was adjusted to 1-2 by adding 1N hydrochloric acid solution. The aqueous phase was extracted twice with ethyl acetate, and the combined organic phases were dried over sodium sulfate, filtered, and concentrated. The crude material was purified by silica gel flash chromatography (0%-10% methanol in dichloromethane) to give the desired product (6.90 g, 19.0 mmol) as a yellow solid.

[0795] 1 H NMR (400 MHz, dimethyl sulfoxide-d6) δ ppm 1.25 (t, J = 7.34 Hz, 3H) 2.99 (q, J = 7.34 Hz, 2H) 4.13 (s, 3H) 7.38 (d, J = 2.20 Hz, 1H) 8.17 (d, J = 2.20 Hz, 1H) 8.55 (s, 1H) 10.94 (s, 1H).

[0796] Step 2: 2-[[5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]- Preparation of 3-pyridyl]oxy]-2-methyl-propionamide (Compound I2)

[0797]

[0798] Cesium carbonate (303 mg, 0.93 mmol, 1.10 equiv) was added to a solution of 5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]pyridin-3-ol (Compound I1 prepared as described above) (300 mg, 0.84 mmol) in acetonitrile (8.4 mL). The resulting suspension was stirred for 5 min, after which 2-bromo-2-methyl-propionamide (294 mg, 1.77 mmol, 2.10 equiv) was added and the reaction mixture was heated at 70 ° C and stirred overnight. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure, the crude residue was partitioned between ethyl acetate and water, and the pH of the aqueous phase was adjusted to 1 by adding 1N hydrochloric acid solution. The aqueous phase was extracted three times with ethyl acetate and once with dichloromethane, and the combined organic phases were dried over sodium sulfate, filtered, and concentrated. The crude material was purified by silica gel flash chromatography (0%-10% methanol in dichloromethane) to give the desired product (156 mg, 0.56 mmol) as a yellow solid.

[0799] 1 H NMR (400 MHz, dimethyl sulfoxide-d6) δ ppm 1.26 (t, J = 7.34 Hz, 3H) 1.60 (s, 6H) 2.96 (q, J = 7.34 Hz, 2H) 4.15 (s, 3H) 7.30 (s broad, 1H) 7.41 (d, J = 2.20 Hz, 1H) 7.49 (m, 1H) 8.23 (d, J = 2.20 Hz, 1H) 8.69 (s, 1H).

[0800] Step 3: 2-[[5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]- Preparation of 3-pyridyl]oxy]-2-methyl-propionitrile (Compound I3)

[0801]

[0802] Trifluoroacetic anhydride (182 μL, 1.30 mmol, 3.00 equivalents) and triethylamine (243 μL, 1.73 mmol, 4.00 equivalents) were added together at 0 ° C. to a solution of 2-[[5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propionamide (Compound I2 prepared as described above) (317 mg, 0.43 mmol) in dichloromethane (4.30 mL). After stirring at room temperature overnight, trifluoroacetic anhydride (182 μL, 1.30 mmol, 3.00 equivalents) and triethylamine (243 μL, 1.73 mmol, 4.00 equivalents) were added, and the reaction mixture was further stirred at room temperature for 2 hours. The reaction mixture was carefully quenched by adding methanol followed by saturated sodium bicarbonate solution. The aqueous phase was extracted twice with dichloromethane and the combined organic layers were dried over sodium sulfate, filtered and concentrated.The crude material was purified by silica gel flash chromatography (0%-10% methanol in dichloromethane) to give the desired product (156 mg, 0.37 mmol) as a yellow oil.

[0803] 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.42 (t, J = 7.34 Hz, 3H) 1.88 (s, 6H) 3.03 (q, J = 7.34 Hz, 2H) 4.31 (s, 3H) 7.72 (d, J = 2.57 Hz, 1H) 8.26 (s, 1H) 8.39 (d, J = 2.57 Hz, 1H).

[0804] Step 4: 2-[[5-ethylsulfonyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]- Preparation of 3-pyridyl]oxy]-2-methyl-propionitrile (Compound P2)

[0805]

[0806] At 0 ° C, to a solution of 2- [ [5-ethylsulfanyl -6- [7- methyl -3- (trifluoromethyl) imidazo [4,5-c] pyridazine -6- base] -3-pyridyl] oxy] -2-methyl - propionitrile (compound I3 prepared as described above) (156 mg, 0.37 mmol) in dichloromethane (3.12 mL) was added 3-chlorobenzenecarbonyl peroxy acid (191.2 mg, 0.776 mmol) and the mixture was stirred at 0 ° C for 30 minutes and then at room temperature overnight. The reaction mixture was quenched with aqueous sodium hydroxide solution (1N, 5 mL) and aqueous sodium thiosulfate solution (5 mL). The aqueous layer was extracted 3 times with dichloromethane, and the combined organic layers were washed twice with 1N aqueous sodium hydroxide solution, brine, dried over sodium sulfate, filtered and evaporated in vacuo. The crude material was ground in cyclohexane, and the formed precipitate was filtered and dried to obtain the desired product. Alternatively, the crude material can be purified by flash chromatography on silica gel.

[0807] LCMS (Method 1): m / z 455 [M+H] + ; Retention time: 0.98min.

[0808] Example P3: 2-[[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine-2- Preparation of 3-pyridyl]-2-methyl-3-pyridyl]-oxy-2-methyl-propionitrile (Compound P3)

[0809]

[0810] Step 1: 5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]pyridine- Preparation of 3-alcohol (Compound I4)

[0811]

[0812] Cesium carbonate (12.9 g, 39.5 mmol, 2.20 equiv) and (E)-benzaldehyde oxime (2.55 mL, 23.4 mmol, 1.30 equiv) were added to a solution of 2-(5-bromo-3-ethylsulfanyl-2-pyridinyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine (CAS 1421955-74-9) (7.50 g, 18.0 mmol) in N,N-dimethylformamide (36 mL). The resulting suspension was stirred at 80 ° C overnight. After cooling to room temperature, the reaction mixture was diluted with dichloromethane (500 mL), the organic phase was washed with water (3×200 mL), and the pH of the aqueous phase was adjusted to 1-2 by adding 1N hydrochloric acid solution. The aqueous phase was extracted with dichloromethane (5×300 mL), and the combined organic phases were dried over sodium sulfate, filtered, and concentrated. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired product (5.80 g, 16.4 mmol).

[0813] LCMS (method 1): m / z 355 [M+H] + ; Retention time: 0.94min.

[0814] Step 2: 2-[[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]- Preparation of 3-pyridyl]oxy]acetonitrile (Compound I5)

[0815]

[0816] Under argon, potassium carbonate (1.21 g, 8.47 mmol, 1.50 equivalents) was added to a solution of 5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]pyridin-3-ol (compound I4 prepared as described above) (2.00 g, 5.64 mmol) in N, N-dimethylformamide (40 mL) at room temperature, followed by bromoacetonitrile (608 μL, 8.47 mmol, 1.50 equivalents). After stirring for 5 hours, the reaction mixture was poured into water (300 mL), and the aqueous phase was extracted twice with ethyl acetate (300 mL). The combined organic phases were washed with water (3 × 200 mL), dried over sodium sulfate, filtered and concentrated. The crude material was purified by silica gel chromatography (ethyl acetate in cyclohexane) to give the desired compound (2.08 g, 5.28 mmol) as a yellow solid.

[0817] LCMS (Method 1): m / z 394 [M+H] + ; Retention time: 1.01min.

[0818] Step 3: 2-[[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]- Preparation of 3-pyridyl]oxy]-2-methyl-propionitrile (Compound I6)

[0819]

[0820] A 1 M solution of lithium hexamethyldisilazane in tetrahydrofuran (15.8 mL, 15.8 mmol, 3.00 equiv) was added dropwise through a dropping funnel to a solution of 2-[[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridinyl]oxy]acetonitrile (Compound I5 prepared as described above) (2.07 g, 5.26 mmol) and methyl iodide (1.31 mL, 21.0 mmol, 4.00 equiv) in tetrahydrofuran (32 mL) (cooled at 0 ° C). After complete addition, the reaction mixture was stirred in an ice bath for 1 hour, then warmed to room temperature and stirred overnight. The reaction mixture was quenched by pouring into a saturated aqueous sodium bicarbonate solution (50 mL) at 0 ° C. The aqueous phase was extracted with ethyl acetate (2×50 mL). The combined organic phases were dried over sodium sulfate, filtered and evaporated. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired compound (700 mg, 1.66 mmol).

[0821] LCMS (Method 1): m / z 422 [M+H] + ; Retention time: 1.11min.

[0822] Step 4: 2-[[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]- Preparation of 3-pyridyl]oxy]-2-methyl-propionitrile (Compound P3)

[0823]

[0824] 2-[[5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile (Compound I6 prepared as described above) was treated under the same conditions as described in Step 4 of Example P2 to give the desired compound.

[0825] LCMS (Method 1): m / z 454 [M+H] + ; Retention time: 1.05min.

[0826] Example P5: 2-[[5-ethylsulfonyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo] Preparation of [4,5-c]pyridin-2-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile (Compound P5)

[0827]

[0828] 2-[[5-Ethylsulfanyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile (Compound I10) was treated under the same conditions as described in Step 4 of Example P2 to give the desired compound.

[0829] LCMS (Method 5): m / z 500 [M+H] + ; Retention time: 1.02min.

[0830] Example P4: 2-[[5-ethylsulfonyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyrrolidone] Preparation of [pyridin-2-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile (Compound P4)

[0831]

[0832] Step 1: 5-ethylsulfanyl-2-iodo-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine-2- Preparation of 1,2-dimethyl-1,3-pyridin-3-ol (Compound I13)

[0833]

[0834] Molecular iodine (8.69 g, 34.2 mmol) was added portionwise to a mixture of 5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]pyridin-3-ol (Compound I4 prepared as described in Step 1 of Example P3) (10.1 g, 28.5 mmol) and sodium carbonate (6.34 g, 59.8 mmol) in water (85.5 mL) and acetonitrile (85.5 mL) at room temperature under argon. After stirring for 3 hours, the reaction mixture was quenched with 10% w / w aqueous sodium thiosulfate solution and then extracted with ethyl acetate. The combined organic phases were washed with brine, dried over sodium sulfate, filtered, and concentrated to give the desired product. This material was used as is in the next step.

[0835] LCMS (Method 1): m / z 481 [M+H] + ; Retention time: 1.06min.

[0836] Step 2: 5-ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine-2- Preparation of 1,2-dimethyl-1,3-pyridin-3-ol (Compound I14)

[0837]

[0838] At room temperature under argon, trimethylborane (10.4mL, 73.49mmol) is added to 5-ethylsulfanyl-2-iodo-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]pyridin-3-ol (compound I13 prepared as described above) (14.12g, 29.39mmol), potassium carbonate (12.83g, 88.18mmol) and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex (6.05g, 7.42mmol) in a mixture of 1,4-dioxane (147mL). The reaction mixture is heated to 100°C and stirred for 3 hours. After cooling to room temperature, the crude mixture is filtered through a celite pad and the residue is washed with ethyl acetate. The filtrate was concentrated in vacuo to give the crude product which was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to afford the desired product.

[0839] LCMS (method 1): m / z 369 [M+H] + ; Retention time: 0.96min.

[0840] Step 3: 2-[[5-ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyrrolidone] Preparation of [pyridin-2-yl]-3-pyridinyl]oxy]acetonitrile (Compound I15)

[0841]

[0842] 5-Ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]pyridin-3-ol (Compound I14 prepared as described above) was treated under the same conditions as described in Step 2 of Example P3 to give the desired compound.

[0843] LCMS (Method 1): m / z 408 [M+H] + ; Retention time: 1.05min.

[0844] Step 4: 2-[[5-ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyrrolidone] Preparation of [pyridin-2-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile (Compound I16)

[0845]

[0846] 2-[[5-Ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridinyl]oxy]acetonitrile (Compound I15 prepared as described above) was treated under the same conditions as described in Step 3 of Example P3 to give the desired compound.

[0847] LCMS (Method 1): m / z 436 [M+H] + ; Retention time: 1.16min.

[0848] Step 5: 2-[[5-ethylsulfonyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyrrolidone] Preparation of [pyridin-2-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile (Compound P4)

[0849]

[0850] 2-[[5-Ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile (Compound I16 prepared as described above) was treated under the same conditions as described in Step 4 of Example P2 to give the desired compound.

[0851] LCMS (Method 1): m / z 468 [M+H] + ; Retention time: 1.07min.

[0852] Example P7: 2-[[6-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridine-2- Preparation of [5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propionitrile (Compound P7)

[0853]

[0854] Step 1: 5-cyclopropyl-2-(3-ethylsulfanyl-5-hydroxy-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazole Preparation of oxazolo[4,5-c]pyridin-4-one (Compound I17)

[0855]

[0856] Cesium carbonate (2.75 g, 8.43 mmol, 3.00 equiv) and (E)-benzaldehyde oxime (614 μL, 5.62 mmol, 2.00 equiv) were added to a solution of 2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-5-cyclopropyl-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (prepared as described in WO2017089190) (1.33 g, 2.81 mmol) in N,N-dimethylformamide (12 mL). The resulting suspension was stirred at 45 ° C overnight. After cooling to room temperature, the reaction mixture was diluted with water, and the pH of the aqueous phase was adjusted to 1 by adding 2N hydrochloric acid solution. The aqueous phase was extracted with ethyl acetate, and the combined organic phases were dried over sodium sulfate, filtered and concentrated. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired product (1.00 g, 2.44 mmol) as a white solid.

[0857] LCMS (method 1): m / z 355 [M+H] + ; Retention time: 0.94min.

[0858] 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.06 (br s, 2H) 1.18-1.37 (m, 5H) 2.75 (q, J = 7.38 Hz, 2H) 3.07-3.16 (m, 1H) 4.04 (s, 3H) 7.06 (d, J = 2.45 Hz, 1H) 7.28 (m, 1H) 7.98 (d, J = 2.45 Hz, 1H).

[0859] Step 2: 2-[[6-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridine-2- Preparation of 5-ethylsulfanyl-3-pyridyl]oxy]acetonitrile (Compound I18)

[0860]

[0861] Under argon at 0 ° C, potassium carbonate (404 mg, 2.92 mmol, 1.50 equivalents) was added to a solution of 5-cyclopropyl-2-(3-ethylsulfanyl-5-hydroxy-2-pyridinyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (compound I17 prepared as described above) (800 mg, 1.95 mmol) in N,N-dimethylformamide (8.0 mL), followed by the addition of bromoacetonitrile (177 μL, 2.53 mmol, 1.30 equivalents) thereto after stirring for 10 min. After stirring at room temperature for 2 hours, the reaction mixture was poured into ice water, and the aqueous phase was extracted twice with ethyl acetate. The combined organic phases were washed with water, dried over sodium sulfate, filtered and concentrated. The crude material was used directly without further purification.

[0862] LCMS (Method 3): m / z 450 [M+H] + ; Retention time: 1.48min.

[0863] Step 3: 2-[[6-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridine-2- Preparation of [3-[4 ...dimethylamino]-2-methyl-2-propionitrile]]-3-pyridyl]-5-ethylsulfanyl-3-pyridyl]oxy]-2-methyl-propionitrile (Compound I19)]]

[0864]

[0865] 2M lithium hexamethyldisilazane in tetrahydrofuran (2.50mL, 5.00mmol, 3.00 equivalents) is added dropwise to 2-[[6-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfanyl-3-pyridinyl]oxy]acetonitrile (compound I18 prepared as described above) (750mg, 1.67mmol) and methyl iodide (418 μL, 6.68mmol, 4.00 equivalents) in tetrahydrofuran (20mL) (cooled at 0°C). The reaction mixture is stirred under an ice bath for 2 hours and then quenched by pouring into a saturated aqueous sodium bicarbonate solution. The aqueous phase is extracted with ethyl acetate. The combined organic phases are washed with brine, dried over sodium sulfate, filtered and evaporated. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired compound (700 mg, 1.66 mmol).

[0866] LCMS (Method 3): m / z 478 [M+H] + ; Retention time: 1.54min.

[0867] Step 4: 2-[[6-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridine-2- Preparation of [5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propionitrile (Compound P7)

[0868]

[0869] 2-[[6-[5-Cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfanyl-3-pyridinyl]oxy]-2-methyl-propionitrile (Compound I19 prepared as described above) was treated under the same conditions as described in Step 4 of Example P2 to give the desired compound.

[0870] LCMS (Method 3): m / z 510 [M+H] + ; Retention time: 1.46min.

[0871] Example P6: 2-[[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridine-2- Preparation of [5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propionitrile (Compound P6)

[0872]

[0873] Step 1: 5-ethyl-2-(3-ethylsulfanyl-5-hydroxy-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazole Preparation of 4-[4,5-c]pyridin-4-one (Compound I20)

[0874]

[0875] 2-(5-Bromo-3-ethylsulfanyl-2-pyridinyl)-5-ethyl-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (prepared as described in WO 2017084879) was treated under the same conditions as described in Step 1 of Example P7 to give the desired compound.

[0876] LCMS (Method 3): m / z 399 [M+H] + ; Retention time: 1.38min.

[0877] 1 H NMR (400 MHz, chloroform-d) δ ppm 7.99 (m, 1H) 7.29 (m, 1H) 7.06 (m, 1H) 4.26 (q, J = 6.89 Hz,

[0878] 2H)4.08(s,3H)2.75(q,J=7.46Hz,2H)1.42-1.37(m,3H)1.18-1.23(m,3H).

[0879] Step 2: 2-[[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridine-2- Preparation of 5-ethylsulfanyl-3-pyridyl]oxy]acetonitrile (Compound I21)

[0880]

[0881] 5-Ethyl-2-(3-ethylsulfanyl-5-hydroxy-2-pyridinyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (Compound I20 prepared as described above) was treated under the same conditions as described in Step 2 of Example P7 to give the desired compound.

[0882] LCMS (Method 4): m / z 438 [M+H] + ; Retention time: 1.01min.

[0883] 1 H NMR (400 MHz, chloroform-d) δ ppm 8.25 (m, 1H) 7.33 (m, 1H) 7.31 (m, 1H) 4.93 (m,

[0884] 2H)4.28(m,2H)4.20(m,3H)2.95(m,2H)1.41-1.34(m,6H).

[0885] Step 3: 2-[[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridine-2- Preparation of [3-[4 ...dimethylamino]-2-methyl-2-nitropropionitrile]]]]]-5-ethylsulfanyl-3-pyridyl]oxy]-2-methyl-propionitrile (Compound I22)]

[0886]

[0887] 2-[[6-[5-Ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfanyl-3-pyridinyl]oxy]acetonitrile (Compound I21 prepared as described above) was treated under the same conditions as described in Step 3 of Example P7 to give the desired compound.

[0888] LCMS (Method 4): m / z 466 [M+H] + ; Retention time: 1.10min.

[0889] 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 8.31 (m, 1H) 7.65 (m, 1H) 7.32 (m, 1H) 4.25 (m, 6H) 2.96 (m, 2H) 1.81-1.84 (m, 6H).

[0890] Step 4: 2-[[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridine-2- Preparation of [5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propionitrile (Compound P6)

[0891]

[0892] 2-[[6-[5-Ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfanyl-3-pyridinyl]oxy]-2-methyl-propionitrile (Compound I22 prepared as described above) was treated under the same conditions as described in Step 4 of Example P2 to give the desired compound.

[0893] LCMS (Method 5): m / z 498 [M+H] + ; Retention time: 1.05min.

[0894] Example P8: 2-[[5-ethylsulfonyl-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridine Preparation of 2-methyl-1,2-di ...

[0895]

[0896] Step 1: Preparation of 1-(3-ethylsulfanyl-5-hydroxy-2-pyridyl)ethanone (Compound I23)

[0897]

[0898] Cesium carbonate (6.65g, 20.40mmol, 2.20 equivalents) and (E)-benzaldehyde oxime (1.32mL, 12.1mmol, 1.30 equivalents) are added to a solution of 1-(5-chloro-3-ethylsulfanyl-2-pyridyl) ethanone (prepared as described in WO 2016071214) (2.00g, 9.27mmol) in N,N-dimethylformamide (18mL). The resulting suspension is stirred at room temperature overnight. The reaction mixture is diluted with water, and the pH of the aqueous phase is adjusted to 1 by adding 1N hydrochloric acid solution. The aqueous phase is extracted with ethyl acetate, and the combined organic phases are dried over sodium sulfate, filtered and concentrated. The crude material is purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to obtain the desired product (1.47g, 2.44mmol) as a white solid.

[0899] 1 H NMR (400 MHz, dimethyl sulfoxide-d6) δ ppm 1.28 (t, J = 7.34 Hz, 3H) 2.86 (q, J = 7.34 Hz, 2H) 3.33 (s, 3H) 7.15 (d, J = 2.20 Hz, 1H) 7.98 (d, J = 2.20 Hz, 1H) 10.94 (s br, 1H).

[0900] Step 2: 2-[(6-Acetyl-5-ethylsulfanyl-3-pyridyl)oxy]-2-methyl-propionamide (Compound Preparation of I24)

[0901]

[0902] Cesium carbonate (9.2 g, 28 mmol, 1.5 equiv) was added to a solution of 1-(3-ethylsulfanyl-5-hydroxy-2-pyridyl)ethanone (Compound I23 prepared as described above) (3.7 g, 19 mmol) in acetonitrile (94 mL). The resulting suspension was stirred for 5 min, after which 2-bromo-2-methyl-propionamide (5.0 g, 30 mmol, 1.6 equiv) was added and the reaction mixture was heated and stirred at room temperature overnight. After cooling to room temperature, the reaction mixture was poured into water, and the aqueous phase was extracted three times with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered, and concentrated. The crude material was used in the next step without further purification.

[0903] 1 H NMR (400 MHz, dimethyl sulfoxide-d6) δ ppm 1.28 (t, J = 7.34 Hz, 3H) 1.56 (s, 6H) 1.85 (s, 3H) 2.83 (q, J = 7.34 Hz, 2H) 7.15 (d, J = 2.20 Hz, 1H) 7.33 (s, 1H) 7.45 (s, 1H) 8.04 (d, J = 2.20 Hz, 1H).

[0904] Step 3: 2-[(6-Acetyl-5-ethylsulfanyl-3-pyridyl)oxy]-2-methyl-propionitrile (Compound I25) Preparation

[0905]

[0906] Trifluoroacetic anhydride (6.27 mL, 44.6 mmol, 3.00 equiv) was added together with triethylamine (8.38 mL, 59.5 mmol, 4.00 equiv) at 0 ° C. to a solution of 2-[(6-acetyl-5-ethylsulfanyl-3-pyridyl)oxy]-2-methyl-propionamide (compound I24 prepared as described above) (6.0 g, 14.9 mmol) in dichloromethane (149 mL). After stirring at room temperature for 2 hours, the reaction mixture was carefully quenched by adding methanol followed by saturated sodium bicarbonate solution. The aqueous phase was extracted twice with dichloromethane and the combined organic layers were dried over sodium sulfate, filtered and concentrated. The crude material was purified by flash chromatography on silica gel (0%-100% ethyl acetate in cyclohexane) to give the desired product (3.69 g) as a yellow oil.

[0907] 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.44 (t, J = 7.34 Hz, 3H) 1.83 (s, 6H) 2.71 (s, 3H) 2.93 (q, J = 7.34 Hz, 2H) 7.57 (d, J = 2.20 Hz, 1H) 8.22 (d, J = 2.20 Hz, 1H).

[0908] Step 4: 2-[[6-(2-bromoacetyl)-5-ethylsulfanyl-3-pyridyl]oxy]-2-methyl-propionitrile (compound Preparation of compound I26

[0909]

[0910] Trimethyl(phenyl)ammonium tribromide (1.43 g, 3.78 mmol) is added to a 0 ° C cooling solution of 2-[(6-acetyl-5-ethylsulfanyl-3-pyridyl)oxy]-2-methyl-propionitrile (compound 125 prepared as described above) (1.00 g, 3.78 mmol) in tetrahydrofuran (14.4 mL, freshly opened bottle). The resulting orange suspension is stirred at room temperature for 42 hours before quenching the reaction with water. The aqueous phase is extracted three times with ethyl acetate, the combined organic phases are washed with brine, dried over sodium sulfate, filtered and concentrated. The thick yellow oil is ground in cold cyclohexane (15 mL) containing some dichloromethane (1.0 mL) to obtain a precipitate, which is filtered and washed with cyclohexane to give the desired compound (812 mg) as a yellow solid. The filtrate is purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give a second portion of the desired compound (500 mg) as a yellow oil with lower purity.

[0911] 1 H NMR (400 MHz, chloroform-d) δ ppm 1.45 (t, J = 7.34 Hz, 3H) 1.85 (s, 6H) 2.96 (q, J = 7.34 Hz, 2H) 4.82 (s, 2H) 7.59 (d, J = 2.57z, 1H) 8.21 (d, J = 2.57 Hz, 1H).

[0912] Step 5: 2-[[5-Ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridine Preparation of 2-methyl-1,2-di ...

[0913]

[0914] A suspension of 2-[[6-(2-bromoacetyl)-5-ethylsulfanyl-3-pyridyl]oxy]-2-methyl-propionitrile (compound 126 prepared as described above) (100 mg, 0.20 mmol) and 4-(trifluoromethyl)pyridine-2-amine (commercially available) (35 mg, 0.21 mmol) in acetonitrile (1.5 mL) was heated at 70 ° C and stirred overnight. Magnesium oxide (8 mg, 0.20 mmol) was added to the reaction mixture and heating was continued for 3 hours to complete the reaction. After cooling to room temperature, the mixture was poured into water, and the aqueous phase was extracted twice with ethyl acetate. The combined organic phases were washed with brine, dried over sodium sulfate, filtered and concentrated. The crude material was partially purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to obtain the desired product (60 mg) as a yellow oil.

[0915] 1 H NMR (400MHz, chloroform-d) δppm 1.44(t,J=7.34Hz,3H)1.81(s,6H)3.04(q,J=7.34Hz,2H)7.02(dd,J1=7.34; J2=1.65Hz,1H)7.65( d,J=2.57Hz,1H)8.06(s,1H)8.29(d,J=7.34Hz,1H)8.32(d,J=2.57Hz,1H)8.37(d,J=1.65Hz,1H).

[0916] Step 6: 2-[[5-ethylsulfonyl-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridine Preparation of 2-methyl-1,2-di ...

[0917]

[0918] 2-[[5-Ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile (Compound I28 prepared as described above) was treated under the same conditions as described in Step 4 of Example P2 to give the desired compound.

[0919] LCMS (Method 1): m / z 439 [M+H] + ; Retention time: 0.98min.

[0920] Example P9: 2-[[5-ethylsulfonyl-6-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridine Preparation of 2-methyl-1,2-di ...

[0921]

[0922] Step 1: 2-[[5-Ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridine Preparation of 2-methyl-1,2-di ...

[0923]

[0924] 2-[[6-(2-Bromoacetyl)-5-ethylsulfanyl-3-pyridinyl]oxy]-2-methyl-propionitrile (Compound I26 prepared as described above) and 5-(trifluoromethyl)pyridazin-3-amine (CAS 1211591-88-6) were treated under similar conditions as described in Step 5 of Example P8 to give the desired compound.

[0925] LCMS (Method 1): m / z 408 [M+H] + ; Retention time: 1.09min.

[0926] Step 2: 2-[[5-ethylsulfonyl-6-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridine Preparation of 2-methyl-1,2-di ...

[0927]

[0928] 2-[[5-Ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-b]pyridin-2-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile (Compound Ill prepared as described above) was treated under the same conditions as described in Step 4 of Example P2 to give the desired compound.

[0929] LCMS (Method 1): m / z 440 [M+H] + ; Retention time: 0.99min.

[0930] Example P14: 2-[[5-Ethylsulfonyl-6-[1-methyl-5-(trifluoromethylsulfonyl)benzimidazol-2-yl]- Preparation of 3-pyridyl]oxy]-2-methyl-propionitrile (Compound P14)

[0931]

[0932] Step 1: N-[2-amino-4-(trifluoromethylsulfanyl)phenyl]-5-(1-cyano-1-methyl-ethoxy)-3-ethyl Preparation of 2-methyl-4-thiazolylsulfanyl-N-methyl-pyridine-2-carboxamide (Compound I41)

[0933]

[0934] To a solution of N1-methyl-4-(trifluoromethylsulfanyl)benzene-1,2-diamine (WO2012 / 086848) (400 mg, 1.80 mmol, 1.05 equiv) and triethylamine (3.0 equiv) in tetrahydrofuran (15 mL) was added dropwise a solution of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carbonyl chloride (Compound I32 prepared as described below) (1.0 equiv) in tetrahydrofuran (15 mL) at 0 ° C. The reaction mixture was stirred at room temperature for 3 hours and then evaporated in vacuo. The residue was diluted with water (50 mL) and extracted with ethyl acetate (3×50 mL). The combined organic layers were washed with brine (20 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to give the crude desired product. This material was used as is in the next step.

[0935] LCMS (Method 3): m / z 471 [M+H] + ; Retention time: 1.64min.

[0936] Step 2: 2-[[5-Ethylsulfanyl-6-[1-methyl-5-(trifluoromethylsulfanyl)benzimidazol-2-yl]-3- Preparation of pyridyl]oxy]-2-methyl-propionitrile (Compound I40)

[0937]

[0938] A solution of N-[2-amino-4-(trifluoromethylsulfanyl)phenyl]-5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide (Compound I41 prepared as described above) (800 mg, 1.70 mmol) in glacial acetic acid (12 mL) was heated at 150° C. for 2 hours. The reaction mixture was concentrated under reduced pressure, and the residue was quenched with water (50 mL) and extracted with ethyl acetate (3×50 mL). The combined organic layers were washed with brine (20 mL), dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by silica gel column chromatography (combiflash) (30% ethyl acetate-cyclohexane) to give the desired product as an off-white solid.

[0939] LCMS (Method 5): m / z 453 [M+H] + ; Retention time: 1.12min.

[0940] Step 3: 2-[[5-ethylsulfonyl-6-[1-methyl-5-(trifluoromethylsulfanyl)benzimidazol-2-yl]-3- Preparation of [pyridyl]oxy]-2-methyl-propionitrile (Compound P13)

[0941]

[0942] 2-[[5-Ethylsulfanyl-6-[1-methyl-5-(trifluoromethylsulfanyl)benzimidazol-2-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile (Compound I40 prepared as described above) was treated with 2.2 equivalents of the oxidizing agent 3-chlorobenzenecarboperoxyacid under similar conditions as described in Step 4 of Example P2 to give the desired compound after stirring at room temperature for 2 hours. The crude product obtained after extractive workup was purified by combiflash chromatography on silica gel (40% ethyl acetate in cyclohexane).

[0943] LCMS (Method 5): m / z 485 [M+H] + ; Retention time: 1.12min.

[0944] Step 4: 2-[[5-ethylsulfonyl-6-[1-methyl-5-(trifluoromethylsulfonyl)benzimidazol-2-yl]-3- Preparation of [pyridyl]oxy]-2-methyl-propionitrile (Compound P14)

[0945]

[0946] 2-[[5-Ethylsulfanyl-6-[1-methyl-5-(trifluoromethylsulfanyl)benzimidazol-2-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile (Compound I40 prepared as described above) was treated with 4.5 equivalents of the oxidant 3-chlorobenzenecarboperoxyacid under similar conditions as described in Step 4 of Example P2 to give the desired compound after stirring at room temperature overnight. The crude product obtained after extractive workup was purified by combiflash chromatography on silica gel (40% ethyl acetate in cyclohexane).

[0947] LCMS (Method 5): m / z 517 [M+H] + ; Retention time: 1.02min.

[0948] Example P15: 2-[[6-(2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazole- Preparation of [6-yl]-5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propionitrile (Compound P15)

[0949]

[0950] Step 1: 5-(1-cyano-1-methyl-ethoxy)-N-[2,2-difluoro-6-(methylamino)-1,3-benzodioxy Preparation of [5-heterocyclopentenyl]-3-ethylsulfanyl-pyridine-2-carboxamide (Compound I42)

[0951]

[0952] To a solution of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid (Compound I36 prepared as described below) (350 mg, 1.31 mmol) in ethyl acetate (5.25 mL) was added dropwise 2,2-difluoro-N5-methyl-1,3-benzodioxole-5,6-diamine hydrochloride (408 mg, 1.71 mmol), N,N-diisopropyl-ethylamine (0.689 mL, 4.02 mmol) and T3P [propanephosphonic anhydride] in methyl-tetrahydrofuran (1.61 mL, 2.63 mmol) under nitrogen at 0°C. A 50% solution of the mixture was added dropwise. The mixture was stirred at 0°C for 2 hours and then diluted with aqueous sodium bicarbonate solution. The product was extracted twice with ethyl acetate, and the combined organic layers were washed with a saturated aqueous sodium bicarbonate solution, dried over magnesium sulfate, filtered and concentrated in vacuo. The residue was purified by Combiflash (gradient ethyl acetate in cyclohexane) to give the desired product.

[0953] LCMS (Method 1): m / z 451 [M+H] + ; Retention time: 1.17min.

[0954] Step 2: 2-[[6-(2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazole-6- Preparation of [3-[(1-[(2-[(2-[(2-[(2-[(2-( ...-((-(-(-(-(-(-(-(-(-(-(-(-(-(-(-(

[0955]

[0956] A solution of 5-(1-cyano-1-methyl-ethoxy)-N-[2,2-difluoro-6-(methylamino)-1,3-benzodioxol-5-yl]-3-ethylsulfanyl-pyridine-2-carboxamide (Compound I42 prepared as described above) (245 mg, 0.54 mmol) was refluxed in glacial acetic acid (2.2 mL) for one hour. The mixture was concentrated in vacuo, and the residue was diluted with ethyl acetate and aqueous sodium bicarbonate. The product was extracted twice with ethyl acetate, and the combined organic layers were washed with saturated aqueous sodium bicarbonate, dried over magnesium sulfate, filtered, and concentrated in vacuo. The residue was purified by combiflash (gradient ethyl acetate in cyclohexane) to give the desired product.

[0957] LCMS (Method 1): m / z 433 [M+H] + ; Retention time: 1.11min.

[0958] Step 3: 2-[[6-(2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazole-6- Preparation of [5-(2 ...2-(2-(2-2-1-5-

[0959]

[0960] 2-[[6-(2,2-Difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazol-6-yl)-5-ethylsulfanyl-3-pyridyl]oxy]-2-methyl-propionitrile (Compound I43 prepared as described above) in ethyl acetate was treated with 2.3 equivalents of the oxidant 3-chlorobenzenecarboperoxyacid under similar conditions as described in Step 4 of Example P2 to give the desired compound after stirring at room temperature for 4 hours. The crude product obtained after extractive workup was purified by silica gel column chromatography (combiflash) (10%-45% ethyl acetate in cyclohexane).

[0961] LCMS (Method 1): m / z 465 [M+H] + ; Retention time: 1.05min. 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.39 (t, 3H), 1.91 (s, 6H), 3.77 (s, 3H), 3.87 (q, 2H), 7.13 (s, 1H), 7.44 (s, 1H), 8.30 (d, 1H), 8.83 (d, 1H).

[0962] Example P16: 2-[[6-(2,2-difluoro-[1,3]dioxolo[4,5-f][1,3]benzoxazole-6- Preparation of [5-(2 ...2-1-5-sulfonyl-3-pyrid

[0963]

[0964] Step 1: N-(6-bromo-2,2-difluoro-1,3-benzodioxol-5-yl)-5-(1-cyano-1-methyl- Preparation of (4-(2-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxamide (Compound I44)

[0965]

[0966] To a solution of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid (Compound I36 prepared as described below) (250 mg, 0.94 mmol) in ethyl acetate (3.75 mL) was added dropwise 6-bromo-2,2-difluoro-1,3-benzodioxol-5-amine (CAS 887267-84-7) (241 mg, 0.94 mmol), triethylamine (0.196 mL, 1.41 mmol) and a 50% solution of T3P [propanephosphonic anhydride] in methyl-tetrahydrofuran (0.747 mL, 1.22 mmol) at 0 ° C under nitrogen. The mixture was stirred at room temperature for 16 hours and then diluted with aqueous sodium bicarbonate solution. The product was extracted twice with ethyl acetate, and the combined organic layers were washed with a saturated aqueous solution of sodium bicarbonate, dried over magnesium sulfate, filtered and concentrated in vacuo. The residue was purified by Combiflash (gradient tert-butyl methyl ether in cyclohexane) to give the desired product.

[0967] LCMS (Method 1): m / z 500 / 502 [M+H] + ; Retention time: 1.34min.

[0968] Step 2: 2-[[6-(2,2-difluoro-[1,3]dioxolo[4,5-f][1,3]benzoxazole-6- Preparation of [3-[(1-[(2-[(2-[(2-[(2-[(2-( ...-((-(-((-(-(-(-(-(-(-(-(-(-(-(-(-(-(

[0969]

[0970] Into a microwave vial was charged N-(6-bromo-2,2-difluoro-1,3-benzodioxol-5-yl)-5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxamide (Compound I44 prepared as described above) (131 mg, 0.26 mmol), potassium carbonate (47 mg, 0.34 mmol), copper (I) iodide (10 mg, 0.052 mmol), N,N'-dimethylethylenediamine (5.7 mL, 0.052 mmol) and toluene (1.3 mL). The mixture was flushed with argon and then heated in a microwave at 150 ° C for 4 hours. Additional copper (I) iodide (10 mg) was added and heating was continued at 150 ° C for 3 hours. The reaction mixture was filtered through Hyflo and the residue was washed with ethyl acetate and water. The layers of the filtrate were separated, the aqueous phase was extracted twice with ethyl acetate, the combined organic layers were washed with brine, dried over magnesium sulfate, filtered and concentrated in vacuo.The residue was purified by Combiflash (gradient ethyl acetate in cyclohexane) to give the desired product.

[0971] LCMS (Method 1): m / z 420 [M+H] + ; Retention time: 1.20min.

[0972] Step 3: 2-[[6-(2,2-difluoro-[1,3]dioxolo[4,5-f][1,3]benzoxazole-6- Preparation of [5-(2 ...2-1-5-sulfonyl-3-pyrid

[0973]

[0974] 2-[[6-(2,2-Difluoro-[1,3]dioxolo[4,5-f][1,3]benzoxazol-6-yl)-5-ethylsulfanyl-3-pyridyl]oxy]-2-methyl-propionitrile (Compound I45 prepared as described above) in ethyl acetate was treated with 2.2 equivalents of the oxidant 3-chlorobenzenecarboperoxyacid under similar conditions as described in Step 4 of Example P2 to give the desired compound after stirring at room temperature for 16 hours. The crude product obtained after extractive workup was purified by silica gel column chromatography (combiflash) (0%-45% ethyl acetate in cyclohexane).

[0975] LCMS (Method 1): m / z 452 [M+H]+ ; Retention time: 1.09min. 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.46 (t, 3H), 1.91 (s, 6H), 4.05 (q, 2H), 7.43 (s, 1H), 7.51 (s, 1H), 8.37 (d, 1H), 8.88 (d, 1H).

[0976] Table P: Examples of compounds of formula (I)

[0977]

[0978]

[0979]

[0980] Table I: Formula (II), (III), (V), (Va), (Vb), (Vc), (VII), (XXII), (XXIII), (XXIV), Examples of intermediate compounds of (XXV-c), (XXV-a), (XXVI), (XXVIII), (XXIX-a) and (XXIX-c)

[0981]

[0982]

[0983]

[0984]

[0985]

[0986]

[0987]

[0988]

[0989] 1)1 H NMR (400 MHz, dimethyl sulfoxide-d6) δ ppm 1.25 (t, J = 7.34 Hz, 3H) 2.99 (q, J = 7.34 Hz, 2H) 4.13 (s, 3H) 7.38 (d, J = 2.20 Hz, 1H) 8.17 (d, J = 2.20 Hz, 1H) 8.55 (s, 1H) 10.94 (s, 1H)

[0990] 2)1 H NMR (400 MHz, chloroform-d) δ ppm 1.42 (t, J = 7.34 Hz, 3H) 1.88 (s, 6H) 3.03 (q, J = 7.34 Hz, 2H) 4.31 (s, 3H) 7.72 (d, J = 2.57 Hz, 1H) 8.26 (s, 1H) 8.39 (d, J = 2.57 Hz, 1H)

[0991] 3)1 H NMR (400 MHz, chloroform-d) δ ppm 1.06 (br s, 2H) 1.18-1.37 (m, 5H) 2.75 (q, J = 7.38 Hz, 2H) 3.07-3.16 (m, 1H) 4.04 (s, 3H) 7.06 (d, J = 2.45 Hz, 1H) 7.28 (m, 1H) 7.98 (d, J = 2.45 Hz, 1H)

[0992] 4)1 H NMR (400 MHz, dimethyl sulfoxide-d6) δ ppm 1.28 (t, J = 7.34 Hz, 3H) 2.86 (q, J = 7.34 Hz, 2H) 3.33 (s, 3H) 7.15 (d, J = 2.20 Hz, 1H) 7.98 (d, J = 2.20 Hz, 1H) 10.94 (s br, 1H)

[0993] 5)1 H NMR (400 MHz, dimethyl sulfoxide-d6) δ ppm 1.28 (t, J = 7.34 Hz, 3H) 1.56 (s, 6H) 1.85 (s, 3H) 2.83 (q, J = 7.34 Hz, 2H) 7.15 (d, J = 2.20 Hz, 1H) 7.33 (s, 1H) 7.45 (s, 1H) 8.04 (d, J = 2.20 Hz, 1H)

[0994] 6)1 H NMR (400 MHz, chloroform-d) δ ppm 1.44 (t, J = 7.34 Hz, 3H) 1.83 (s, 6H) 2.71 (s, 3H) 2.93 (q, J = 7.34 Hz, 2H) 7.57 (d, J = 2.20 Hz, 1H) 8.22 (d, J = 2.20 Hz, 1H)

[0995] 7)1 H NMR (400 MHz, chloroform-d) δ ppm 1.45 (t, J = 7.34 Hz, 3H) 1.85 (s, 6H) 2.96 (q, J = 7.34 Hz, 2H) 4.82 (s, 2H) 7.59 (d, J = 2.57z, 1H) 8.21 (d, J = 2.57 Hz, 1H)

[0996] 8)1H NMR (400MHz, chloroform-d) δppm 1.44(t,J=7.34Hz,3H)1.81(s,6H)3.04(q,J=7.34Hz,2H)7.02(dd,J1=7.34; J2=1.65Hz,1H)7.65 (d,J=2.57Hz,1H)8.06(s,1H)8.29(d,J=7.34Hz,1H)8.32(d,J=2.57Hz,1H)8.37(d,J=1.65Hz,1H)

[0997] Example I32: 5-(1-Cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carbonyl chloride (Compound Preparation of I32)

[0998]

[0999] Step 1: Preparation of 3-ethylsulfanyl-5-hydroxy-pyridine-2-carboxylic acid methyl ester (Compound I33)

[1000]

[1001] To a solution of 5-bromo-3-ethylsulfanyl-pyridine-2-formic acid methyl ester (prepared as described in WO 2016 / 026848) (10.0 g, 36.21 mmol) in acetonitrile (72 ml) was added cesium carbonate (25.96 g, 79.67 mmol) and (E)-benzaldehyde oxime (5.7 g, 47.08 mmol), and the suspension was heated to 80 ° C overnight. The solvent was evaporated in a vacuum and the residue was dissolved in ethyl acetate and water. The separated aqueous layer was acidified with an aqueous solution of 1M hydrochloric acid and extracted with ethyl acetate (3x) and extracted once with dichloromethane. The combined organic phases were dried over sodium sulfate, filtered and concentrated. The residue was purified by flash chromatography on silica gel (0%-10% methanol gradient in dichloromethane) to obtain 3-ethylsulfanyl-5-hydroxy-pyridine-2-formic acid methyl ester (compound I33). LCMS (method 1): m / z 214 [M+H] + ; Retention time: 0.68min.

[1002] Step 2: 5-(2-Amino-1,1-dimethyl-2-oxo-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl Preparation of ester (Compound I34)

[1003]

[1004] To a solution of 3-ethylsulfanyl-5-hydroxy-pyridine-2-carboxylic acid methyl ester (Compound I33) (2.5 g, 11.72 mmol) in acetonitrile (59 ml) was added cesium carbonate (5.7 g, 17.49 mmol) and 2-bromo-2-methyl-propionamide (3.1 g, 18.67 mmol) was added after 5 minutes. The reaction mixture was stirred at room temperature overnight and poured into water and ethyl acetate. The separated aqueous layer was extracted with ethyl acetate (3x), and the combined organic layers were dried over sodium sulfate, filtered and evaporated to give crude 5-(2-amino-1,1-dimethyl-2-oxo-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester (Compound I34). This material was used in the next step without further purification. LCMS (Method 1): m / z 299 [M+H] + ; Retention time: 0.71min.

[1005] Step 3: 5-(1-Cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester (Compound Preparation of I35)

[1006]

[1007] To a mixture of crude 5-(2-amino-1,1-dimethyl-2-oxo-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester (compound 134 prepared above) (4.18 g, 14.0 mmol) and triethylamine (5.73 g, 7.89 ml, 56.0 mmol) in dichloromethane (140 ml) at 0 ° C. trifluoroacetic anhydride (8.92 g, 5.90 ml, 42.0 mmol) was added dropwise. The resulting suspension was stirred at room temperature for two hours. The reaction mixture was carefully quenched with methanol and then with aqueous sodium bicarbonate. The aqueous layer was extracted twice with dichloromethane, and the combined organic layers were dried over sodium sulfate, filtered and evaporated. The residue was purified by combiflash (0%-45% gradient ethyl acetate in cyclohexane) to give 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester (compound 135). LCMS (method 1): m / z 281 [M+H] + ; Retention time: 0.90min. 1 H NMR (400MHz, CDCl3) δppm 1.43 (t, J = 7.40Hz, 3H), 1.80 (s, 6H), 2.95 (q, J = 7.40Hz, 2H), 3.99 (s, 3H), 7.58 (d, J = 2.32Hz, 1H), 8.22 (d, J = 2.32Hz, 1H).

[1008] Step 4: Preparation of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid (Compound I36) preparation

[1009]

[1010] To a solution of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester (compound 135) (6.0 g, 21.41 mmol) in tetrahydrofuran (60 ml) was added lithium hydroxide hydrate (1.8 g, 42.81 mmol) and water (10 ml). The reaction mixture was stirred at room temperature until completion (TLC monitoring), then concentrated under reduced pressure. The residue was diluted with water (100 ml), acidified with an aqueous solution of 2N hydrochloric acid, and the aqueous phase was extracted with ethyl acetate (3×100 ml). The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was washed twice with n-pentane (50 ml), filtered, and evaporated to dryness to obtain 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid (compound 136) as a solid. LCMS (method 4): m / z 267[M+H] + and m / z 265[MH] - ; Retention time: 0.82min. 1 H NMR (400MHz, DMSO-d6) δppm 1.27 (t, J = 7.21Hz, 3H), 1.78 (s, 6H), 2.97 (q, J = 7.21Hz, 2H), 7.58 (d, J = 2.32Hz, 1H), 8.24 (d, J = 2.32Hz, 1H).

[1011] Step 5: 5-(1-Cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carbonyl chloride (Compound I32) Preparation

[1012]

[1013] To a solution of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid (Compound I36) (771 mg, 2.90 mmol) and N,N-dimethylformamide (one drop) in tetrahydrofuran (19 ml) at 0°C-5°C was added oxalyl chloride (0.328 ml, 3.76 mmol) and the mixture was stirred at room temperature for 2 hours. The solution was concentrated under reduced pressure, diluted twice with tetrahydrofuran and evaporated to dryness. The LCMS data of an aliquot quenched with dimethylamine were consistent with those of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-N,N-dimethyl-pyridine-2-carboxamide (C 14 H 19 N3O2S, 293.38) consistent: LCMS (method 1): m / z 294 [M+H] + ; Retention time: 0.83min.

[1014] The following mixtures of a compound of formula I with an active ingredient are preferred (the abbreviation "TX" means "a compound selected from the group consisting of the compounds of the invention described in Tables A-1 to A-22, Tables B-1 to B-4 and Table P"):

[1015] An auxiliary agent selected from the group consisting of: petroleum (alias) (628) + TX;

[1016] Insect control active substances, the insect control active substances are selected from Abamectin + TX, Acetoquin + TX, Acetamiprid + TX, Acetaminophen + TX, Acynonapyr + TX, Bifenapyr + TX, Afolan + TX, Cotton Boll + TX, Allethrin + TX, α-Cypermethrin + TX, Alpha-Cypermethrin + TX, Sulfonamido + TX, Mefenamic Acid + TX, Azofentin + TX, Cyprodinil + TX, Benzophenone + TX, Benzpyrimoxan + TX, β-Cypermethrin + TX, β-Cypermethrin + TX, Bifenazate + TX, Bifenthrin + TX, Bifenazate + TX, Bio-allethrin + TX, Bio- Allethrin S)-cyclopentyl isomer + TX, bioresmethrin + TX, bistrifluan + TX, brofenoxam (Broflanilide) + TX, bromothrin + TX, bromophos-ethyl + TX, buprofezin + TX, butacarb + TX, cadusafos + TX, carbaryl + TX, butacarb + TX, batan + TX, CAS No.: 1632218-00-8 + TX, CAS No.: 1808115-49-2 + TX, CAS No.: 2032403-97-5 + TX, CAS No.: 2044701-44-0 + TX, CAS No.: 2128706-05-6 + TX, CAS No.: 2246757-58-2 (or 22 49718-27-0)+TX, CAS No.: 907187-07-9+TX, Chlorantraniliprole+TX, Chlordane+TX, Chlorfenapyr+TX, Chlorprophmethrin+TX, Cyclofenazol+TX, Clenpyrine+TX, Cloethocarb+TX, Clothianidin+TX, 2-Chlorophenyl N-methylcarbamate (CPMC)+TX, Cyanophos+TX, Cyantraniliprole+TX, Cyclofenapyr+TX, Cyclobutrifluram+TX, Pyrethroids+TX, Cyclofenapyr+TX, Cyclopyrafen+TX, Cytoxanil+TX, Cytoxanil+TX, Cytoxanil+TX, Cytoxanil+TX, Cytoxanil+TX, Cytoxanil+TX, Cytoxanil (Cyhalodiamide) + TX, cyhalothrin + TX, cypermethrin + TX, cypermethrin + TX, Cyproflanilide + TX, cyromazine + TX, deltamethrin + TX, cypermethrin + TX, cypermethrin + TX, chlorfenapyr + TX, chlormet + TX, dibrom + TX, Diclomezotiaz + TX, fluazifop + TX, dimpropyridaz + TX, diclofenac + TX, dinotefuran + TX, vegetable phosphorus + TX, emamectin (or emamectin benzoate) + TX, dextromethorphan + TX, ε-momfluorothrin + TX, ε-metofluthrin + TX,Cypermethrin + TX, Ethion + TX, Ethioprolin + TX, Ethofenprox + TX, Etofenazole + TX, Fenamiphos + TX, Fenfluthrin + TX, Fenitrothion + TX, Fenbutar + TX, Fenthiocarb + TX, Fenoxycarb + TX, Cypermethrin + TX, Fenpyroxymate + TX, Fensulfuron + TX, Fenthion + TX, Yesalin + TX, Fenvalerate + TX, Fipronil + TX, Flometoquin + TX, Flonicamid + TX, Fifop-Azolam + TX, Fluazaindolizine + TX, Fifoxazolidinone + TX, Flubendiamide + TX , Flumethrin + TX, Flucitrinate + TX, Flufenacet + TX, Flucythrin + TX, Fluthiazolin + TX, Flumethrin + TX, Flufenacet + TX, Flupyram + TX, Flupentiofenox + TX, Flupyrimin + TX, Fluralaner + TX, Fluvalinate + TX, Fluxametamide + TX, Fosthiazol + TX, γ-Flucythrin + TX, Gossyplure, TM+TX, pyramid +TX, chlorfenapyr +TX, benzylaminofen +TX, Heptafluthrin +TX, hexythiazox +TX, hydrazone +TX, Imicyafos +TX, Imidacloprid +TX, imiprodinil +TX, indoxacarb +TX, iodomethane +TX, iprodione +TX, Isocycloseram +TX, Isosulfuron +TX, Ivermectin +TX, κ-bifenthrin +TX, κ-tefluthrin +TX, λ-cyhalothrin +TX, lepidomectin +TX, chlorfenapyr +TX, metaflumizone +TX, metaldehyde +TX, methomyl +TX, methomyl +TX, methoxyfenozide +TX, metofluthrin +TX, methomyl +TX, Zikewei + TX, cypermethrin + TX, Momfluorothrin + TX, cypermethrin + TX, Nicofluprole + TX; Nitenpyram + TX, Nithiothiazide + TX, Oxydemeton + TX, Oxamyl + TX, Oxazosulfyl + TX, Parathion-ethyl + TX, Permethrin + TX, Phenothrin + TX, Phosphamidon + TX, Piperonyl butoxide + TX, Pirimicarb + TX, Pyrimidophos-ethyl + TX, Pyrimidophos-methyl + TX, Polyhedrosis virus + TX, Promethrin + TX, Profenofos + TX, Profluthrin + TX, Propargite + TX, Afenacet + TX, Proxathiophos + TX, Profenthrin + TX, Protrifen )+TX, Pyflubumide+TX, Pymetrozine+TX, Pyraclofos+TX, Pyrafluprole+TX, Pyridaben+TX, Pyridalyl+TX, Pyrifluquinazon+TX, Pyrimidine+TX, Pyrimidine+TX, Pyrafluprid+TX, Pyriflupyrid+TX, Resmothrin+TX, Sarolaner+TX, Selamectin+TX, Silafluthrin+TX, Spinetoram+TX, Spinosad+TX, Spirodiclofen+TX, Spiromesifen+TX, Spiropyrim+TX, Spiropyrim+TX, Spiropyrim+TX, Spiropidion+TX, Spirotetramat+TX, Sulfonamide+TX, Tebufenozide +TX, tebufenpyrad+TX, butylpyrimidinphos (Tebupirimiphos) +TX, tefluthrin +TX, tebufenphos +TX, tetrachlorvinphos +TX, tetrachlorvinphos sulfone (Tetradiphon) +TX, tetramethrin +TX, tetrafluthrin +TX, acaricide +TX, flucyramid +TX, θ-cypermethrin +TX, thiacloprid +TX, thiamethoxam +TX, thiophanate +TX, thiodicarb +TX, long-lasting carboxylic acid +TX, methyl benzylphos +TX, thiophanate +TX, tioxazafen +TX, tolfenpyrad +TX, toxaphene +TX, tralomethrin +TX, transfluthrin +TX, triazophos +TX, trichlorfon +TX, chlorpyrifos +TX,Trichlorfon + TX, Triflumezopyrim + TX, Tyclopyrazoflor + TX, ζ-cypermethrin + TX, seaweed extract and fermentation products derived from sugar acyl + TX, seaweed extract and fermentation products derived from sugar acyl (containing urea + TX, amino acids + TX, potassium and molybdenum, and EDTA-chelated manganese) + TX, seaweed extract and fermented plant products + TX, seaweed extract and fermented plant products (containing plant hormones + TX, vitamins + TX, EDTA-chelated copper + TX, zinc + TX, and iron + TX), azadirachtin + TX, Bacillus aizawai + TX, Bacillus chitinosporus AQ746 (NRRL Accession No. B-21 618) + TX, Bacillus firmus + TX, Bacillus kurstak (Bacillus Kurstaki) + TX, Bacillus mycoides AQ726 (NRRL Accession No. B-21664) + TX, Bacillus pumilus (NRRL Accession No. B-30087) + TX, Bacillus pumilus AQ717 (NRRL Accession No. B-21662) + TX, Bacillus species AQ178 (ATCC Accession No. 53522) + TX, Bacillus species AQ175 (ATCC Accession No. 55608) + TX, Bacillus species AQ177 (ATCC Accession No. 55609) + TX, unspecified Bacillus subtilis + TX, Bacillus subtilis AQ153 (ATCC Accession No. 55614) +TX, Bacillus subtilis AQ30002 (NRRL Accession No. B-50421) +TX, Bacillus subtilis AQ30004 (NRRL Accession No. B-50455) +TX, Bacillus subtilis AQ713 (NRRL Accession No. B-21661) +TX, Bacillus subtilis AQ743 (NRRL Accession No. B-21665) +TX, Bacillus thuringiensis AQ52 (NRRL Accession No. B-21619) +TX, Bacillus thuringiensis BD#32 (NRRL Accession No. B-21530) +TX, Bacillus thuringiensis subsp. Kurstaki BMP 123+TX, Beauveria bassiana+TX, D-limonene+TX, Granulovirus+TX, Harpin+TX, Helicoverpa armigera nuclear polyhedrosis virus+TX, Helicoverpa tatarinowii nuclear polyhedrosis virus+TX, Helicoverpa virescens nuclear polyhedrosis virus+TX, Helicoverpa virescens nuclear polyhedrosis virus+TX, Metarhizium species+TX, Muscodor albus 620 (NRRL registration number 30547)+TX, Muscodor roseus A3-5 (NRRL registration number 30548)+TX, Neem-based products+TX,Paecilomyces fumosorum + TX, Paecilomyces lilacinus + TX, Pasteuria szabalensis + TX, Pasteuria penetranta + TX, Pasteuria mycoides + TX, Pasteuria thornei + TX, Pasteuria thunbergii + TX, p-cymene + TX, Plutella xylostella granulosis virus + TX, Plutella xylostella nuclear polyhedrosis virus + TX, polyhedrosis virus + TX, pyrethrum + TX, QRD 420 (terpenoid blend) + TX, QRD 452 (terpenoid blend) + TX, QRD 460 (terpenoid blend) + TX, Quillaja sapodilla + TX, Rhodococcus sphaeroides AQ719 (NRRL Accession No. B-21663) + TX, Spodoptera frugiperda nuclear polyhedrosis virus + TX, Streptomyces flavus (NRRL Accession No. 30232) + TX, Streptomyces sp. (NRRL Accession No. B-30145) + TX, terpenoid blend + TX, and Verticillium sp.;

[1017] an algaecide selected from the group consisting of bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, 2-tert-butylamino-4-cyclopropylamino-6-methylthio-s-triazine (cybutryne) [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endoxan (295) + TX, fentin (347) + TX, slaked lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX;

[1018] Anthelmintics selected from the group consisting of: avermectin (1) + TX, clefonate (1011) + TX, cyclohexine + TX, doramectin (alias) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alias) [CCN] + TX, ivermectin (alias) [CCN] + TX, milbemycin oxime (alias) [CCN] + TX, moxidectin (alias) [CCN] + TX, piperazine [CCN] + TX, selamectin (alias) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX;

[1019] Avicides 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;

[1020] 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, mercaptophenone ( Synonyms) [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 (synonyms) [CCN] + TX;

[1021] A biological agent selected from the group consisting of: GV of cotton brown banded moth (alias) (12) + TX, Agrobacterium radiobacterium (alias) (13) + TX, Amblyseius spp. (alias) (19) + TX, NPV of celery budworm (alias) (28) + TX, Anagrus atomus (alias) (29) + TX, Aphelinus abdominalis (alias) (33) + TX, Aphidius colemani (alias) (34) + TX, Aphidoletes aphidimyza (alias) (35) + TX, NPV of lucerne budworm (alias) (38) + TX, Bacillus firmus (alias) (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 (alias) (53) + TX, Beauveria brongniartii (alias) (54) + TX, Chrysoperla carnea (alias) (151) + TX, Cryptolaemus montrouzieri (alias) (178) + TX, Codling moth GV (alias) (191) + TX, Dacnusa sibirica (alias) (212) + TX, Diglyphus isaea (alias) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus) (alias) (300) + TX, Spodoptera exigua NPV (alias) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alias) (433) + TX, Hippodamia convergens (alias) (442) + TX, Leptomastix dactylopii (alias) (488) + TX, Macrolophus caliginosus (alias) (491) + TX, Spodoptera exigua NPV (alias) (494) + TX, Metaphycus helvolus (alias) (522) + TX, Metarhizium anisopliae var.acridum)(scientific name)(523)+TX, Metarhizium anisopliae var.anisopliae)(scientific name)(523)+TX, Neodiprionsertifer NPV and Neodiprionsertifer rubrum (N.lecontei)NPV (alias) (575) + TX, Paecilomyces spp. (alias) (596) + TX, Paecilomyces fumosoroseus (alias) (613) + TX, Phytoseiulus persimilis (alias) (644) + TX, Spodopteraexigua multicapsid nuclear polyhedrosis virus (scientific name) (741) + TX, Steinernema bibionis (alias) (742) + TX, Steinernema carpocapsae (alias) (742) + TX, Steinernema glaseri (alias) (742) + TX, Steinernema riobrave) (alias) (742) + TX, Steinernema riobravis (alias) (742) + TX, Steinernema scapterisci (alias) (742) + TX, Steinernema spp. (alias) (742) + TX, Trichogramma spp. (alias) (826) + TX, Typhlodromus occidentalis (alias) (844) and Verticillium lecanii (alias) (848) + TX;

[1022] Soil disinfectant selected from the group consisting of methyl iodide (IUPAC name) (542) and methyl bromide (537) + TX;

[1023] A chemical sterilant selected from the group consisting of: apholanate [CCN] + TX, bis(aziridine) methylaminophosphine sulfide (bisazir) (alias) [CCN] + TX, busulfan (alias) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alias) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methylsulfonate Methotepa [CCN] + TX, methylapholate [CCN] + TX, morzid [CCN] + TX, penfluron (other name) [CCN] + TX, tepa [CCN] + TX, thiohempa (other name) [CCN] + TX, thiotepa (other name) [CCN] + TX, trotamide (other name) [CCN] and urethaneimide (other name) [CCN] + TX;

[1024] An insect pheromone 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 X, (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-methyloctadec-1-ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol and 4-methylnonan-5-one (IUPAC name) (544) + TX, alpha-multistriatin (alias) [CCN] + TX, western pine beetle gathering pheromone (brevicomin) (alias) [CCN] + TX, codlelure (alias) [CCN] + TX, codlemon mone)(alias)(167)+TX、cuelure)(alias)(179)+TX、disparlure)(277)+TX、1-dodecane-8-en-1-yl acetate(IUPAC name)(286)+TX、1-dodecane-9-en-1-yl acetate(IUPAC name)(287)+TX、10-10-dien-1-yl acetate(IUPAC name)(284)+TX、dominicalure(alias)[CCN]+TX、ethyl 4-methyloctanoate(IUPAC name) C name) (317) + TX, eugenol (alias) [CCN] + TX, southern pine beetle gathering pheromone (frontalin) (alias) [CCN] + TX, gossyplure (alias) (420) + TX, grandlure (421) + TX, grandlure I (alias) (421) + TX, grandlure II (alias) (421) + TX, grandlure III (alias) (421) + TX, grandlure IV (alias) (421) + TX, hexalure )[CCN]+TX、ipsdienol(alias)[CCN]+TX、ipsenol(alias)[CCN]+TX、japonilure(alias)(481)+TX、lineatin(alias)[CCN]+TX、litlure(alias)[CCN]+TX、looplure(alias)[CCN]+TX、medlure[CCN]+TX、megatomoic acid(alias)[CCN]+TX、methyl eugenol(alias)(540)+TX、muscalure(563)+TX、octadeca-2,13-dien-1-yl acetate(IUPAC name)(588)+TX、octadeca-3,13-Dien-1-yl acetate (IUPAC name) (589) + TX, orfralure (alias) [CCN] + TX, oryctalure (alias) (317) + TX, ostramone (alias) [CCN] + TX, siglure [CCN] + TX, sordidin (alias) (736) + TX, sulcatol )(Synonym)[CCN]+TX, tetradec-11-en-1-yl acetate (IUPAC name) (785)+TX, Mediterranean fruit fly attractant (839)+TX, Mediterranean fruit fly attractant A (Synonym) (839)+TX, Mediterranean fruit fly attractant B1 (Synonym) (839)+TX, Mediterranean fruit fly attractant B2 (Synonym) (839)+TX, Mediterranean fruit fly attractant C (Synonym) (839) and trunc-call (Synonym)[CCN]+TX;

[1025] Insect repellents 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, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexylurea [CCN] + TX, methoquin-butyl (1276) + TX, methyl neodecylamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX;

[1026] Molluscicides selected from the group consisting of di(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, chloranil (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 (576) + 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;

[1027] 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) Abstract 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 (alias) (210) + TX, avermectin (1) + TX, acetofenamide [CCN] + TX, cotton bell carb (15) + TX, aldicarb (16) + TX, aldicarb (863) + TX, AZ60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alias) + TX, chlorpyrifos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbofuran (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, chlorpyrifos (999) + TX, cyclohexane + TX, cytokinin (alias) (2 10)+TX, dazomethane (216)+TX, DBCP (1045)+TX, DCIP (218)+TX, diamidafos (1044)+TX, dimethoate (1051)+TX, dicliphos (alias)+TX, dimethoate (262)+TX, doramectin (alias) [CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, eprinomectin (alias) [CCN]+TX, ethoprophos (312) + TX, dibromoethane (316) + TX, fenamiphos (326) + TX, fenpyrad (alias) + TX, fensulfonyl (1158) + TX, thiazophos (408) + TX, butythiophos (1196) + TX, furfural (alias) [CCN] + TX, GY-81 (research code) (423) + TX, thiophene [CCN] + TX, iodomethane (IUPAC name) (542) + TX, isamidophos (1230) + TX , chlorfenapyr (1231) + TX, ivermectin (alias) [CCN] + TX, kinetin (alias) (210) + TX, methyl azomethine (1258) + TX, metamectin (519) + TX, metamectin potassium salt (alias) (519) + TX, metamectin sodium salt (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alias) [CCN] + TX, moxidectin (alias) [CCN] + TX, Myrotheciumverrucaria) combination (alias) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosphamidon [CCN] + TX, clomiphene (alias) + TX, selamectin (alias) [CCN] + TX, spinosad (737) + TX, terbufos (alias) + TX, terbufos (773) + TX, tetrachlorothiophene (IUPAC / Chemical Abstract name) (1422) + TX, thiafenox (alias) + TX, cypermethrin (1434) + TX, triazophos (820) + TX, triazuron (alias) + TX, dimethylol [CCN] + TX, YI-5302 (compound code) and zeatin (alias) (210) + TX, fluensulfone [318290-98-1] + TX, fluopyram + TX;

[1028] A nitrification inhibitor selected from the group consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX;

[1029] Plant activators selected from the group consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alias) (720) + TX;

[1030] Rodenticide, the rodenticide is selected from the group consisting of: 2-isovaleryl indane-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, dithiocarbamide (912) + TX, brodifacoum (89) + TX, bromodisulfuron (89) + TX, Bromadiolone (including α-bromadiolone) + TX, bromodiolone (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlordiolone (140) + TX, cholecalciferol (alias) (850) + TX, chlordiol (1004) + TX, chlordiol (1005) + TX, chlordiol (175) + TX, chlordiol (1009) + TX, bromodiol (246) + TX, thiazolin (249) + TX, difacoum (273) + TX, calciferol (301) + T X、Fluorofuram (357) + TX、Fluoroacetamide (379) + TX、Fluorofuram (1183) + TX、Fluorofuram hydrochloride (1183) + TX、γ-HCH (430) + TX、HCH (430) + TX、Hydrogen cyanide (444) + TX、Methyl iodide (IUPAC name) (542) + TX、Lindane (430) + TX、Magnesium phosphide (IUPAC name) (640) + TX、Methyl bromide (537) + TX、Fluorofuram (1318) + TX、Fluorofuram ( 1336) + 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;

[1031] Synergists selected from the group consisting of 2-(2-butoxyethoxy)ethyl piperate (IUPAC name) (934) + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (alias) (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;

[1032] Animal repellents 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;

[1033] Virucidal agents selected from the group consisting of: imipenem (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX;

[1034] A wound protection agent selected from the group consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX;

[1035] Biologically active substances, the biologically active substances are selected from 1,1-bis(4-chlorophenyl)-2-ethoxyethanol+TX, 2,4-dichlorophenylbenzenesulfonate+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide+TX, 4-chlorophenylphenyl sulfone+TX, acetofenapyr+TX, aldisulfonyl+TX, sagofos+TX, fomanphos+TX, amitriptyline+TX, amitriptyline hydrogen oxalate+TX, amitraz+TX, cypermethrin+TX, arsenic trioxide+TX, azobenzene+TX, azophos+TX, benomyl+TX, benoxafos+TX, benzyl benzoate+TX, bixafenthion+TX, bromothiophene+TX, bromothiophene+TX, bromothiophene+TX, bromothiophene Phosphorus + TX, bromoxifen + TX, buprofezin + TX, butamethoxam + TX, butamethoxam + TX, butylpyridaben + TX, calcium polysulfide + TX, octachlorocamphene + TX, chlormethoxam + TX, trithion + TX, cypermethrin + TX, cypermethrin + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorfenapyr + TX, chlorfenapyr + TX, chlorfenapyr + TX, dimethoate + TX, ethyl chlorfenapyr + TX, chlordimeform (chloromebuform) + TX, chlorfenapyr + TX, propyl chlorfenapyr + TX, chlorfenapyr + TX, chlorfenapyr + TX, chlorfenapyr I + TX, chlorfenapyr II + TX, chlorfenapyr + TX, closantel + TX, coumaphos + TX, crotamiton + TX , Baclofos+TX, Thiamin+TX, Fruitworm+TX, DCPM+TX, DDT+TX, Tianlephos+TX, Tianlephos-O+TX, Tianlephos-S+TX, Demeton-methyl+TX, Demeton-O+TX, Demeton-O-methyl+TX, Demeton-S+TX, Demeton-S-methyl+TX, Demeton-S-methyl+TX, Demeton-S-methyl+TX, Demeton-S-methyl+TX, Dimethoate+TX, Dichlorvos+TX, Dichlorvos+TX, Dichlorvos+TX, Dimethoate+TX, Dimethoate+TX, Dimethoate+TX, Dimethoate+TX, Dimethoate+TX, Dimethoate-4+TX, Dimethoate Mup-6+TX, anthelmintic+TX, nitropentyl+TX, nitrooctyl+TX, nitrobutyl+TX, dithiophos+TX, sulfodiphenyl+TX, disulfiram+TX, DNOC+TX, dofenapyn+TX, doramectin+TX, fenoxaphos+TX, eprinomectin+TX, thiophos+TX, ethiopthion+TX, anti-mite+TX, fenbutatin+TX, fenthiocarb+TX, fenpyrad+TX, fenpyroximate+TX, anthracene+TX, fentrifanil+TX, fluazifop+TX, flufenoxuron+TX, diflubenzuron+TX, fluazifop+TX, FMC 1137+TX, fluazifop+TX, fluazifop hydrochloride+TX, formparanate+TX, γ-HCH+TX, cypermethrin+TX,Benzylfen + TX, hexadecylcyclopropanecarboxylate + TX, isocarbophos + TX, jasmonate I + TX, jasmonate II + TX, iodonium + TX, lindane + TX, propanil + TX, cypermethrin + TX, dithiophos + TX, methylthiophene + TX, cypermethrin + TX, methylbromide + TX, methicillin + TX, chlorpyrifos + TX, milbemycin + TX, propylamine + TX, monocrotophos + TX, maoguo + TX, moxidectin + TX, naled + TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, fluazifop + TX, nikkomycin + TX, penbufenac + TX, penbufenac 1:1 zinc chloride complex TX, omethoate + TX, isothiophos + TX, sulfone + TX, pp'-DDT + TX, parathion + TX, permethrin + TX, fenthion + TX, phosalone + TX, thiophanate + TX, phosphamidon + TX, polychloroterpenes + TX, polynactins + TX, prochlorperazine + TX, cypermethrin + TX, propoxur + TX, ethidium + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrin + TX, pyrimethanthiophos + TX, pyrimithiophos + TX, quinalphos + TX, quintiofos + TX, R-1 492+TX, glyphosate+TX, rotenone+TX, octamidine+TX, clomartin+TX, selamectin+TX, threon+TX, SSI-121+TX, sulfilam+TX, sulfluramid+TX, sulfotep+TX, sulfur+TX, fluazifop+TX, τ-fluvalinate+TX, TEPP+TX, terbucarb+TX, tetrachlorvinphos+TX, thiafenox+TX, thiafenox+TX, pyrimidine+TX, long-lasting cypermethrin+TX, methyl sulfophos+TX, chlorpyrifos+TX, thiamethoxam ... TX, vaniliprole + TX, bethoxazin + TX, copper dioctanoate + TX, copper sulfate + TX, cybutryne + TX, dichloronaphthoquinone + TX, dichlorophen + TX, endoxan + TX, triphenyltin + TX, slaked lime + TX, sodium mancozeb + TX, quinone + TX, quinone + TX, simazine + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, fusulin + TX, piperazine + TX, thiophanate + TX, chloralose + TX, fenthion + TX, pyridin-4-amine + TX, strychnine + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide + TX,8-Hydroxyquinoline sulfate + TX, bronopol + TX, copper hydroxide + TX, cresol + TX, dispyrithione + TX, dodesine + TX, sodium disulfide + TX, formaldehyde + TX, mercurophen + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel bis(dimethyldithiocarbamate) + TX, trichloromethylpyridine + TX, octhilone + TX, oxolinic acid + TX, oxytetracycline + TX, potassium hydroxyquinoline sulfate + TX, thiabendazole + TX, streptomycin + TX, streptomycin sesquisulfate + TX, chlorothiazol + TX, thimerosal + TX, cotton brown-banded tormenter GV + TX, Agrobacterium radiobacterium + TX, Amblyseius spp. + TX, celery budworm NPV + TX, Anagrus atomus + TX, Aphelinus abdominalis + TX, cotton aphid parasitoid (Aphidius colemani+TX, Aphidoletes aphidimyza+TX, Spodoptera alfalfa NPV+TX, Bacillus sphaericus Neide+TX, Beauveria brongniartii+TX, Chrysoperla carnea+TX, Cryptolaemus montrouzieri+TX, Codling moth GV+TX, Dacnusa sibirica+TX, Diglyphus isaea+TX, Encarsia formosa+TX, Eretmocerus eremicus+TX, Heterorhabditis bacteriophora) and H.megidis+TX, Hippodamia convergens+TX, Leptomastix dactylopii+TX, Macrolophus caliginosus+TX, Cabbage looper NPV+TX, Metaphycus helvolus+TX, Metarhizium anisopliaevar.acridum+TX, Metarhizium anisopliaevar.anisopliae+TX, Neodiprion sertifer NPV and N.lecontei NPV+TX,TX, Paecilomyces fumosoroseus+TX, Phytoseiulus persimilis+TX, Steinernema bibionis+TX, Steinernema carpocapsae+TX, Steinernema glaseri+TX, Steinernema riobrave+TX, Steinernema riobravis+TX, Steinernema scapterisci+TX, Steinernema spp.+TX, Trichogramma species+TX, Typhlodromus occidentalis)+TX, Verticillium lecanii+TX, apholonate+TX, bis(aziridine) methylaminophosphine sulfide (bisazir)+TX, busulfan+TX, dimatif+TX, hemelamine+TX, hempa+TX, metepa+TX, methiotepa+TX, methyl apholonate Apholate) + TX, Morzid + TX, Penfluron + TX, Tepa + TX, Thiohempa + TX, Thiohempa + TX, Tetramethylenetetramine + TX, Urethaneimine + TX, (E)-Deca-5-en-1-yl acetate and (E)-Deca-5-en-1-ol + TX, (E)-Tridec-4-en-1-yl acetate + TX, (E)-6-Methylhept-2-en-4-ol + TX, (E,Z)-Tetradec-4,10-dien-1-yl acetate + TX, (Z)-Dodec-7-en-1-yl acetate + TX, (Z)-Hexadecane 1-enal + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-eicos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, (7E,9Z)-dodec-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradec-9,12-dien-1-yl acetate + TX,14-Methyloctadec-1-ene+TX, 4-methylnon-5-ol and 4-methylnon-5-one+TX, α-polystyrene+TX, western pine beetle aggregation pheromone+TX, codlelure+TX, codlemone+TX, cuelure+TX, epoxynonadecane+TX, dodec-8-en-1-yl acetate+TX, dodec-9-en-1-yl acetate+TX, dodec-8+TX, 10-dien-1-yl acetate+TX, dominicalure+TX, ethyl 4-methyloctanoate+TX, eugenol+TX, southern pine beetle aggregation pheromone (f rontalin)+TX, grandlure+TX, grandlure mixture I+TX, grandlure mixture II+TX, grandlure mixture III+TX, grandlure mixture IV+TX, hexalure+TX, ipsdienol+TX, ipsenol+TX, japonilure+TX, lineatin+TX, litlure+TX, looplure+TX, medlure+TX, megatomoic acid+TX, methyl benzoate eugenol) + TX, muscalure + TX, octadec-2,13-dien-1-yl acetate + TX, octadec-3,13-dien-1-yl acetate + TX, orfralure + TX, oryctalure + TX, ostramone + TX, siglure + TX, sordidin + TX, sulcatol + TX, tetradec-11-en-1-yl acetate Ester + TX, Mediterranean fruit fly attractant (trimedlure) + TX, Mediterranean fruit fly attractant A + TX, Mediterranean fruit fly attractant B1 + TX, Mediterranean fruit fly attractant B2 + TX, Mediterranean fruit fly attractant C + TX, trunc-call + TX, 2-(octylthio)-ethanol + TX, butopyronoxyl + TX, butoxy (polypropylene glycol) + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, DEET + TX, dimethyl carbate + TX, dimethyl phthalate + TX, ethyl hexanediol + TX, hexamide + TX, methoquin-butyl + TX, methylneodecanamide + TX,Oxamate + TX, picaridin + TX, 1-dichloro-1-nitroethane + TX, 1,1-dichloro-2,2-di(4-ethylphenyl)ethane + TX, 1,2-dichloropropane and 1,3-dichloropropylene + TX, 1-bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichloro-phenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)benzene 1-Hydroxy-1-methylpyrazol-5-yldimethylcarbamate + TX, 4-methyl-1-hydroxy-2-methylpyrazol-5-yldimethylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidinone + TX, 2-isovalerylindan-1,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenylmethylcarbamate + TX, 2-thiocyanatoethyl laurate + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-methyl-1-phenylpyrazol-5-yldimethyl-carbamate + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate + TX, 5,5-dimethyl-3-oxocyclohex-1-enyldimethylcarbamate + TX, acethion + TX, acrylonitrile + TX, Agent + TX, aloamicin + TX, cypermethrin + TX, α-decandrin + TX, aluminum phosphide + TX, cypermethrin + TX, neonicotinoid + TX, ethyl athidathion + TX, methyl pyrifos + TX, Bacillus thuringiensis δ-endotoxin + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, cypermethrin + TX, Bayer 22 / 190 + TX, Bayer 22408 + TX, β-cyfluthrin + TX, β-cypermethrin + TX, bioethanomethrin + TX, biopermethrin + TX, bis(2-chloroethyl) ether + TX, borax + TX, bromophenirone + TX, bromo-DDT + TX, cypermethrin + TX, Cytoxan + TX, butathiofos + TX, butyl phosphate + TX, calcium arsenate + TX, calcium cyanide + TX, carbon disulfide + TX, carbon tetrachloride + TX, cypermethrin hydrochloride + TX, cevadine + TX, borneol + TX, chlordane + TX, chlordecone + TX, chloroform + TX, chloropicrin + TX, chloraniloxime + TX, chlorprazophos + TX, cis-resmethrin + TX, cismethrin + TX, clocythrin + TX, copper acetylarsenite + TX, copper arsenate + TX, copper oleate + TX,Coumithoate + TX, cryolite + TX, CS 708 + TX, benzonitrile + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, d-cypermethrin + TX, DAEP + TX, dazomethon + TX, decarbofuran + TX, diamidafos + TX, isochlorvos + TX, cypermethrin + TX, dicresyl + TX, cypermethrin + TX, dieldrin + TX, diethyl 5-methylpyrazol-3-yl phosphate + TX, dior + TX, tetrafluthrin + TX, demacarb + TX, pyrethrin + TX, methylchlorfenapyr + TX, difenocarb + TX, propanol + TX, pentotropol + TX, dinoseb + TX, fenpyroxene + TX, vegetable phosphorus + TX, thiopyrafos + TX, DSP + TX, ecdysterone + TX, EI 1642+TX, EMPC+TX, EPBP+TX, etaphos+TX, ethiobencarb+TX, ethyl formate+TX, dibromoethane+TX, dichloroethane+TX, ethylene oxide+TX, EXD+TX, fenoxaphos+TX, ethiobencarb+TX, fenitrothion+TX, fenoxacrim+TX, cypermethrin+TX, fenthion+TX, ethylfenthion+TX, flucofuron+TX, butane Benthion + TX, phosphonium arsenate + TX, butyl thiophos + TX, furathiocarb + TX, pyrethroid + TX, biguanide salt + TX, biguanide acetate + TX, sodium tetrathiocarbonate + TX, halfenprox + TX, HCH + TX, HEOD + TX, heptachlor + TX, cypermethrin + TX, HHDN + TX, hydrogen cyanide + TX, quinolincarb + TX, IPSP + TX, chlorfenapyr + TX, carbofuran + TX, isodrin + TX, isofenphos + TX, Transplanting spirit + TX, rice blast + TX, oxazophos + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, chlorpentyl + TX, methoprene + TX, lead arsenate + TX, bromophenylphos + TX, acetamiprid + TX, thiazophos + TX, m-isopropyl methylcarbamate + TX, magnesium phosphide + TX, phosphorus azide + TX, methyl azoxyphos + TX, thiazophos + TX, mercurous chloride + TX, methyl sulfoxide + TX, metamifene + TX, metamifene potassium salt + T X, sodium salt of Metamex + TX, methylsulfonyl fluoride + TX, butylphos + TX, methoprene + TX, methylthiothrin + TX, methoxychlor + TX, methyl isothiocyanate + TX, methyl chloroform + TX, dichloromethane + TX, anthracene + TX, mirex + TX, napeptide + TX, naphthalene + TX, NC-170 + TX, nicotine + TX, nicotine sulfate + TX, nithiazine + TX, pronicotine + TX, O-5-dichloro-4-iodophenyl O-ethylethylphosphonothioate + TX,O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-ylphosphonothioate + TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-ylphosphonothioate + TX, O,O,O',O'-tetrapropyl dithiopyrophosphate + TX, oleic acid + TX, p-dichlorobenzene + TX, methyl parathion + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH 60-38+TX, fenthion+TX, parachlorothion+TX, phosphine+TX, methyl phoxim+TX, methamidophos+TX, polychlorinated dicyclopentadiene isomers+TX, potassium arsenite+TX, potassium thiocyanate+TX, precocious I+TX, precocious II+TX, precocious III+TX, amidopyrimidin+TX, fluthrin+TX, fenvalerate+TX, prothiophos+TX, pyraclostrobin+TX, anti-pyrethroid+TX, quassia extract+TX, quinalphos-methyl+TX, fenvalerate+TX, iodophos-amide+TX, resmethrin+TX, rotenone+TX, thiamethoxam+TX TX, ryanodine + TX, ryanodine + TX, sabadilla + TX, octamethoxazole + TX, clostridium + TX, SI-0009 + TX, thiapronil + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium hexafluorosilicate + TX, sodium pentachlorophenol + TX, sodium selenate + TX, sodium thiocyanate + TX, sulcofuron + TX, sulcofuron-sodium + TX, sulfuryl fluoride + TX, thioprofen + TX, tar + TX, thiabendazim + TX, TDE + TX, butylpyrimidinphos + TX, bispyribac + TX, cyclopentyl thiophanate + TX, tetrachloroethane + TX, thiochlorvos + TX, cyclohexane + TX, cyclohexane oxalate + TX, cypermethrin + TX, cypermethrin sodium + TX, tralomethrin + TX, permethrin + TX, trichlormetaphos-3 + TX, chlorpyrifos + TX, tolprocarb + TX, chlorpyrifos-methyl + TX, methoprene + TX, veratridine + TX, veratridine + TX, XMC + TX, zetamethrin + TX , zinc phosphide + TX, tolfenphos + TX, and chlorfluanidine + TX, tetrafluanidine + TX, bis(tributyltin) oxide + TX, bromoacetamide + TX, iron phosphate + TX, niclosamide-ethanolamine + TX, tributyltin oxide + TX, pyrimorph + TX, snail killer + TX, 1,2-dibromo-3-chloropropane + TX, 1,3-dichloropropylene + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6-thioxo-1,3,5-thiadiazin-3-yl acetic acid + TX, 6-isopentenylaminopurine + TX,2-Fluoro-N-(3-methoxyphenyl)-9H-purin-6-amine+TX, benclothiaz+TX, cytokinin+TX, DCIP+TX, furfural+TX, isamidophos+TX, kinetin+TX, verrucous myroculitis combination+TX, tetrachlorothiophene+TX, xylenol+TX, zeatin+TX, potassium ethylxanthate+TX, acibenzolar+TX, acibenzolar-S-methyl+TX, Reynoutria sachalinensis) extract + TX, α-chlorohydrin + TX, Antu + TX, barium carbonate + TX, bismuth urea + TX, brodifacoum + TX, brodifacoum + TX, brodifacoum + TX, chlorofacitin + TX, cholecalciferol + TX, chlorfenapyr ... +TX, flumethrin hydrochloride +TX, warfarin +TX, fosfomycin +TX, phosphorus +TX, warfarin +TX, warfarin +TX, scilla glycoside +TX, sodium fluoroacetate +TX, thallium sulfate +TX, warfarin +TX, 2-(-2-butoxyethoxy)ethyl piperate +TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone +TX, farnesol with nerolidol +TX, synergistic acetyl ether +TX, MGK 264 +TX, synergistic butoxide +TX, synergistic aldehyde +TX, synergistic ester (propyl isomer)+TX, S421+TX, Zengxiaosan+TX, sesasmolin+TX, sulfoxide+TX, anthraquinone+TX, copper cyclohexane+TX, copper oxychloride+TX, dicyclopentadiene+TX, salam+TX, zinc cyclohexane+TX, ziram+TX, imanin+TX, ribavirin+TX, chloroindole hydrazide+TX, mercuric oxide+TX, thiophanate-methyl+TX, azaconazole+TX, bifenthiazolin+TX, fuconazole+TX, cyproconazole+TX, difenoconazole+TX, diniconazole+TX, fluoxepiconazole+TX, fenbuconazole+TX, fluquinconazole+TX, flusilazole+TX, flutriafol+TX, furopyr Bacillus thiocarb + TX, hexaconazole + TX, imazalil + TX, imidazole + TX, piclonil + TX, ipconazole + TX, metconazole + TX, myclobutrazol + TX, paclobutrazol + TX, blastifen + TX, penconazole + TX, prothioconazole + TX, pyrifenox + TX, prochloraz + TX, propiconazole + TX, pyraconazole + TX, simeconazole + TX, tebuconazole + TX, fluconazole + TX, triadimefon + TX, triadimenol + TX, triflumizole + TX, triclosan + TX, pyrimidine + TX, chlorfenapyr + TX, flufenapyr + TX, bupirimate + TX,Dimethirimol + TX, ethirimol + TX, dodecacyclic morpholine + TX, fenpropidin + TX, fenpropimorph + TX, spiroxazoline + TX, tridemorph + TX, cyprodinil + TX, pyraclostrobin + TX, pyrimethanil + TX; fenpiclonil + TX, fludioxonil + TX, benalaxyl + TX, furalaxyl + TX, metalaxyl + TX, R metalaxyl + TX, furamide + TX, oxadixyl + TX, carbendazim + TX, debacarb + TX, oxadixyl + TX, Thiabendazole + TX, chlozolinate + TX, dichlozoline + TX, myclozoline + TX, procymidone + TX, vinclozoline + TX, boscalid + TX, carboxin + TX, furamide + TX, flutolanil + TX, mefenamic acid + TX, oxycarboxin + TX, penthiopyrad + TX, thiofuran + TX, docoquin + TX, biguanide + TX, azoxystrobin + TX, etherstrobin + TX, enestrobin (ene stroburin)+TX, enoxastrobin+TX, flutoxistrobin+TX, fluoxastrobin+TX, kresoxim-methyl+TX, oxathiocarb+TX, trifloxystrobin+TX, trifloxystrobin+TX, picoxystrobin+TX, pyraclostrobin+TX, pyraclostrobin+TX, pyraclostrobin+TX, ferbam+TX, mancozeb+TX, maneb+TX, maneb+TX, metiram+TX, methyl propineb+TX, maneb+TX, captol+TX, captan+TX, pyraclostrobin+TX, pyraclostrobin+TX, tolylfluanid+TX, Bordeaux mixture+TX, copper oxide+TX, mancozeb+TX, quinoline copper+TX, phthalostrobin+TX, kefansan+TX, isoflavone+TX, chlorpyrifos+TX, methyl tolclofos+TX TX, difop-butyl + TX, benzathiapiprolin + TX, blasticidin-S + TX, chloroneb + TX, chlorothalonil + TX, cyfluanid + TX, cymoxanil + TX, triflupyramide + TX, diclocymet + TX, diclomezine + TX, dicloran + TX, diethofencarb + TX, dimethomorph + TX, flumorph + TX, dithianon + TX, ethaboxam + TX, etridiazole + TX, famoxadone + TX,Fenamidone + TX, fenoxanil + TX, ferimzone + TX, fluazinam + TX, fluopicolide + TX, flusulfamide + TX, fluopyram + TX, fenhexamid + TX, fosetyl-aluminium + TX, hymexazol + TX, propineb + TX, cyazofamid + TX, methasulfocarb + TX, mefenoxam + TX, pencycuron + TX, oxadiaz ... uron) + TX, phthalide + TX, polyoxins + TX, propamocarb + TX, pyraclostrobin + TX, proquinazid + TX, pyroquilon + TX, pyriofenone + TX, quinoxyfen + TX, pentachloronitrobenzene + TX, thiazide + TX, triazoxide + TX, tricyclazole + TX, triamcinol + TX, validamycin + TX, valosin + TX, zoxamide + TX, mandipropamid + TX, fluorophenyletheramide + TX, pyrazole Isopyrazam + TX, sedaxane + TX, benzovinflumizone + TX, fluopyram + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, isoflurane + TX, isothianid + TX, dipymetitrone + TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile + TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 4-(2,6 -difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine + TX, fluindapyr + TX, Jiaxiangjunzhi + TX, lvbenmixianan + TX, dichlobentiazox + TX,Mandestrobin + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolinyl)oxy]phenyl]propan-2-ol + TX, fluthiazolinone + TX, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamate + TX, pyraziflumid + TX, inpyrfluxam + TX, trolprocarb + TX, chlorfluanidazole + TX, ipfentrifluconazole + TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl] methanesulfonate + TX, N-[6-[[(Z)-[(1-methyl Tetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamic acid but-3-ynyl ester + TX, N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, pyridachlometyl + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one+TX, aminopyrifen+TX, pyraclostrobin+TX, indazolesulfamide+TX, fluopicolide+TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine+TX, florylpicoxamid+TX, pyrimidine+TX, isobutylethoxyquinoline+TX, ipflufenoquin+TX, quinofumelin+TX, isopropylthiopyrad+TX,N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, benzathiostrobin + TX, cyproconazole + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, fluopyram + TX, fluthiazolinone + TX, fluopyram + TX, pyrapropoyne + TX, picarbutrazox + TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan- 4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, metyltetraprole + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidinyl 1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, [(1-oxazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, trinexapac-ethyl + TX, syringostibrate + TX, zhongshengmycin + TX, thiophanate-methyl + TX, zinc thiazole + TX, amethocone + TX, iprodione + TX, N-octyl-N'-[2-(octylamino)ethyl]ethane-1,2-diamine + TX; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX,N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds can be prepared by the method described in WO2015 / 155075); N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX -methyl-6-(2-propoxypropoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared by the method described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine + TX, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds can be prepared by the method described in WO 2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine + TX (these compounds can be prepared by WO 2019 / 110427); N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide+TX, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide+TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide+TX, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide+TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide+TX, Benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX,N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide+TX, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide+TX, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide+TX (these compounds can be prepared by WO 2017 / 153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline+TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline+TX, 4,4-difluoro-3 ,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline+TX,4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline+TX,1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline+T X (these compounds can be prepared by the method described in WO2017 / 025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline + TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole + TX (these compounds can be prepared by the method described in WO2017 / 025510); 2016 / 156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide+TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide+TX, N-ethyl-2-methyl-N-[[4 -[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide+TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX,3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide+TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one+TX, 5,5-dimethyl -2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one+TX, 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylic acid ethyl ester+TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine+TX. The compounds in this paragraph can be prepared by WO 2017 / 055473, WO 2017 / 055469,Prepared by the method described in WO 2017 / 093348 and WO 2017 / 118689; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol+TX (this compound can be prepared by the method described in WO 2017 / 029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol+TX (this compound can be prepared by the method described in WO 2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile+TX (this compound can be prepared by the method described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester + TX (this compound can be prepared by the method described in WO 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']bipyrrole-1,3,5,7(2H,6H)-tetraone + TX (this compound can be prepared by the method described in WO 2011 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide+TX (this compound can be prepared by the method described in WO 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine+TX; N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine+TX (this compound can be prepared by the method described in WO 2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX (this compound can be prepared by the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX,(3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX (these compounds can be prepared by the method described in WO 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX (this compound can be prepared by the method described in WO 2018 / 065414); 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylic acid ethyl ester + TX (this compound can be prepared by the method described in WO2018 / 158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX, N-[(E) -methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX, N-[N-methoxy-C-methyl-carbonimido]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX (these compounds can be prepared by the method described in WO 2018 / 202428);

[1036] Microorganisms including: Acinetobacter lwoffii + TX, Acremonium alternatum + TX + TX, Acremonium cephalosporium + TX + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, Adoxophyes orana granulovirus (AdoxGV) +TX, Agrobacterium radiobacter strain K84 +TX, Alternaria alternate +TX, Alternaria cassia +TX, Alternaria destruens +TX, Ampelomyces quisqualis +TX, Aspergillus flavus AF36 +TX, Aspergillus flavus NRRL 21882 +TX, Aspergillus species +TX, Aureobasidium pullulans +TX, Azospirillum +TX, ( +TX, )+TX, Azotobacter+TX, Azotobacter chroocuccum +TX, Azotobacter cysts (Bionatural Blooming )+TX, Bacillus amyloliquefaciens+TX, Bacillus cereus+TX, Bacillus chitinosporus strain CM-1+TX, Bacillus 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 papillomae (Milky Spore )+TX, Bacillus pumilus spp.+TX, Bacillus pumilus strain GB34 (Yield )+TX, Bacillus pumilus strain AQ717+TX, Bacillus pumilus strain QST 2808( +TX, Ballad )+TX, Bacillus sphaericus +TX, Bacillus spp. +TX, Bacillus strain AQ175 +TX, Bacillus strain AQ177 +TX, Bacillus strain AQ178 +TX, Bacillus subtilis strain QST 713 ( +TX, +TX, )+TX, Bacillus subtilis strain QST714 +TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilis strain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis variant Bacillus amyloliquefaciens strain FZB24 ( +TX, )+TX, Bacillus thuringiensis Cry 2Ae+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 kurstaki BMP 123 +TX, Bacillus thuringiensis subsp. Kurstaki HD-1 (Bioprotec- )+TX, Bacillus thuringiensis strain BD#32+TX, Bacillus thuringiensis strain AQ52+TX, Bacillus thuringiensis var.aizawai ( +TX, )+TX, bacterial species ( +TX, +TX, )+TX, bacteriophage of Clavipacter michiganensis +TX, +TX, Beauveria bassiana ( +TX, Brocaril )+TX, Beauveria bassiana GHA (Mycotrol +TX, Mycotrol +TX, Botani )+TX, Beauveria brongniartii ( +TX, Schweizer +TX, )+TX, Beauveria spp.+TX, Botrytis cineria+TX, Bradyrhizobium japonicum +TX, Brevibacillus brevis +TX, Bacillus thuringiensis (Bacillus thuringiensis) +TX, BtBooster+TX, Burkholderia cepacia ( +TX, +TX、Blue )+TX, Burkholderia gladii+TX, Burkholderia gladioli+TX, Burkholderia spp.+TX, Canadian thistle fungus (CBHCanadian )+TX, Candida butyri+TX, Candida famata+TX, Candida fructus+TX, Candida glabrata+TX, Candida guilliermondii+TX, Candida melibiosica+TX, Candida oleophila strain O+TX, Candida parapsilosis+TX, Candida pelliculosa+TX, Candida pulcherrima+TX, Candida reukaufii+TX, Candida saitoana (Bio- +TX, )+TX, Candida sake+TX, Candida spp.+TX, Candida tenius+TX, Cedecea dravisae+TX, Cellulomonas flavigena+TX, Chaetomium cochliodes(Nova- )+TX, Chaetomium globosum (Nova- )+TX, Chromobacterium subtsugae strain PRAA4-1T +TX, Cladosporium cladosporioides +TX, Cladosporium oxysporum +TX, Cladosporium chlorocephalum +TX, Cladosporium spp. +TX, Cladosporium tenuissimum +TX, Clonostachys rosea +TX, Colletotrichum acutatum +TX, Coniothyrium minitans (Cotans )+TX, Coniothyrium spp.+TX, Cryptococcus albidus +TX, Cryptococcus humicola +TX, Cryptococcus infirmo-miniatus +TX, Cryptococcus laurentii +TX, Cryptophlebia leucotreta granulovirus +TX, Cupriavidus campinensis+TX, Cydia pomonella granulovirus (CYD- )+TX, codling moth granulosis virus ( +TX, Madex +TX, Madex Max / )+TX、Cylindrobasidium laeve +TX, Cylindrocladium +TX, Debaryomyceshansenii +TX, Drechslera hawaiinensis +TX, Enterobacter cloacae +TX, Enterobacteriaceae +TX, Entomophtora virulenta +TX, Epicoccum nigrum +TX, Epicoccum purpurascens +TX, Epicoccum species +TX, Filobasidium floriforme +TX, Fusarium acuminate +TX, Fusarium chrysosporium +TX, Fusarium oxysporum ( / Biofox )+TX, Fusarium spp.+TX, Fusarium spp.+TX, Galactomyces geotrichum+TX, Gliocladium catenulatum ( +TX, )+TX, Gliocladium roseum+TX, Gliocladium species +TX, Gliocladium virens +TX, granulovirus +TX, Halobacillus halophilus +TX, Halobacillus litoralis +TX, Halobacillus trueperi +TX, Halomonas species +TX, Halomonas subglaciescola +TX, Halovibrio variabilis +TX, Hansenula vitis +TX, Helicoverpa armigera nuclear polyhedrosis virus +TX, Spodoptera nucleus polyhedrosis virus +TX, isoflavone-formononetin +TX, Kloeckner's yeast +TX, Kloeckner's yeast species +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, Metschnikowia pulcherrima+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 lilacinus (Biostat )+TX, Paecilomyces lilacinus strain 251 (MeloCon )+TX, Paenibacillus polymyxa+TX, Pantoea agglomerans (BlightBan )+TX, Pantoea species+TX, Pasteurella species +TX, Pasteuria nishizawae+TX, Penicillium chrysogenum+TX, Penicillium billai ( +TX, )+TX, Penicillium breviscompactum+TX, Penicillium spp.+TX, Penicillium chrysogenum+TX, Penicillium purpurogenum+TX, Penicillium species+TX, Penicillium viridiflorum+TX, Phlebiopsis gigantean +TX, phosphate-solubilizing bacteria +TX, Phytophthora cryptogenomica +TX, Phytophthora palmi +TX, Pichia anomala +TX, Pichia guilermondii +TX, Pichia membranaceus +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 species+TX, Pseudomonas syringae (Bio- )+TX, Pseudomonas aeruginosa+TX, Pseudomonas fluorescens +TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex )+TX、Puccinia canaliculata+TX、Puccinia thlaspeos(Wood )+TX、Pythium paroecandrum+TX、Pythium oligandrum +TX, )+TX, Pythium+TX, Rhanella aquatilis+TX, Rhanella spp.+TX, Rhizobia ( +TX, )+TX, Rhizoctonia+TX, Rhodococcus globerulus strain AQ719+TX, Rhodosporidium diobovatum+TX, Rhodosporidium toruloides+TX, Rhodotorula spp.+TX, Rhodotorula glutinis+TX, Rhodotorula graminis+TX, Rhodotorula mucilagnosa+TX, Rhodotorula rubra+TX, Saccharomyces cerevisiae+TX, Salinococcus roseus+TX, Sclerotinia minor+TX, Sclerotinia minor +TX, Scytalidium spp.+TX, Scytalidium uredinicola+TX, Spodoptera exigua nuclear polyhedrosisvirus ( +TX, )+TX, Serratia marcescens+TX, Serratia plymuthica+TX, Serratia spp.+TX, Sordaria fimicola+TX, Spodoptera littoralis nuclear polyhedrovirus +TX, Sporobolomyces roseus +TX, Stenotrophomonas maltophilia +TX, Streptomyces ahygroscopicus +TX, Streptomyces albaduncus +TX, Streptomyces exfoliates +TX, Streptomyces galbus +TX, Streptomyces griseoplanus +TX, Streptomyces griseoviridis +TX, Streptomyces lydicus +TX, Streptomyces lydicus WYEC-108 +TX, Streptomyces violaceus +TX, Tilletiopsis minor +TX, Tilletiopsis spp. +TX, Trichoderma asperellum (T34 )+TX, Trichoderma gamsii +TX, Trichoderma atroviride +TX, Trichoderma hamatum TH 382+TX, Trichoderma harzianum rifai +TX, Trichoderma harzianum T-22 (Trianum- +TX, PlantShield +TX, +TX、Trianum- )+TX, Trichoderma harzianum T-39 +TX, Trichoderma inhamatum +TX, Trichoderma koningii +TX, Trichoderma spp. LC 52 +TX, Trichoderma lignorum +TX, Trichoderma longibrachiatum +TX, Trichoderma polysporum ( )+TX, Trichoderma taxi+TX, Trichoderma virens+TX, Trichoderma virens (formerly known as Gliocladium virens GL-21) +TX, Trichoderma viride +TX, Trichoderma viride strain ICC 080 +TX, Trichosporon pullulans +TX, Trichosporon spp. +TX, Trichothecium spp. +TX, Trichothecium roseum +TX, Typhula phacorrhiza strain 94670 +TX, Typhula phacorrhiza strain 94671 +TX, Ulocladium atrum +TX, Ulocladium oudemansii (Botry- )+TX, Ustilago maydis+TX, various bacteria and supplemented micronutrients (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;

[1037] Plant extracts including: pine oil +TX, Azadirachtin (Plasma Neem +TX, +TX, +TX、Molt- +TX, plant IGR ( +TX, )+TX, canola oil (Lilly Miller )+TX, Chenopodium ambrosioides near ambrosioides +TX, chrysanthemum extract +TX, neem oil extract +TX, Labiatae essential oil +TX, clove-rosemary-peppermint and thyme oil extracts (Garden insect )+TX, betaine +TX, garlic +TX, lemongrass oil (Green )+TX, neem oil+TX, catnip (Nepeta cataria) (catnip oil)+TX, nepeta catarina (Nepeta catarina)+TX, nicotine+TX, oregano oil (Moss )+TX, Pedaliaceae oil +TX, Pyrethrum+TX, Soapbark Tree (Quillaja saponaria) +TX, Reynoutria sachalinensis ( +TX, )+TX, rotenone (Eco )+TX, Rutaceae plant extract +TX, soybean oil (Ortho )+TX, tea tree oil (Timorex )+TX, thyme oil+TX, MMF+TX, +TX, Rosemary-Sesame-Peppermint-Thyme and Cinnamon Extract Blend (EF )+TX, clove-rosemary and peppermint extract mixture (EF )+TX, Clove-Peppermint-Garlic Oil and Mint Blend (Soil )+TX, kaolin +TX, storage glucan of brown algae

[1038] Pheromones including: 3M Sprayable Blackheaded Fireworm )+TX, codling moth pheromone (Paramount dispenser-(CM) / Isomate C- )+TX, Grape Leaf Roller Pheromone (3M MEC-GBM Sprayable )+TX, leaf roller pheromone (3MMEC–LR Sprayable )+TX, housefly pheromone (Muscamone)(Snip7Fly +TX、Starbar Premium Fly )+TX, 3M oriental fruit moth sprayable )+TX, Peachtree Borer pheromone (Isomate- )+TX, Tomato Pinworm Pheromone (3M Sprayable )+TX, Entostat powder (from palm tree extract) (Exosex )+TX、(E+TX,Z+TX,Z)-3+TX,8+TX,11-tetradecatriene 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、Check- +TX, Lavandulyl senecioate;

[1039] Macrobial agents include: Aphidius ervi + TX, Aphidius ervi (Aphelinus- )+TX、Acerophagus papaya+TX、Adalia- )+TX, Coccinella bispotata +TX, Coccinella bispotata +TX, Ageniaspiscitricola+TX, Amblyseius andersoni ( +TX、Andersoni- )+TX, Amblyseius californicus ( +TX, )+TX, Amblyseius cucumber mite ( +TX, Bugline )+TX, Pseudo-Amblyseius +TX, Bugline +TX、Swirskii- )+TX, Amblyseius osseius (Womer )+TX, Amitushesperidum+TX, Anagrus atomus+TX, Anagyrusfusciventris+TX, Anagyrus kamali+TX, Anagyrus loecki+TX, Anagyrus pseudococci +TX, Red wax scale flat-horned jumping wasp (Anicetusbenefices) +TX, Golden wasp (Anisopteromalus calandrae) +TX, Woodland flower stink bug (Anthocorisnemoralis) (Anthocoris- )+TX, short-spur aphid wasp ( +TX, )+TX, Aphelinus asychis+TX, Aphidius colemani +TX, Alphididae +TX, tobacco aphid braconid +TX, peach red aphid aphid braconid (Aphipar- )+TX, aphid midge +TX, aphid-eating gall midge +TX, Lingnan yellow aphid wasp +TX, Indian yellow aphid wasp +TX, Aprostocetus hagenowii +TX, Atheta coriaria +TX, Bombus species +TX, European bumblebee (Natupol )+TX, European Bumblebee ( +TX, )+TX, Cephalonomiastephanoderis+TX, Black-backed Ladybird (Chilocorus nigritus)+TX, Common Lacewing (Chrysoperlacarnea) +TX, Common Lacewing +TX, Chrysoperlarufilabris+TX, Cirrospilus ingenuus+TX, Cirrospilusquadristriatus+TX, Citrostichus phyllocnistoides+TX, Closterocerus chamaeleon+TX, Closterocerus species+TX, Coccidoxenoides perminutus +TX, Coccophagus cowperi+TX, Coccophagus lycimnia+TX, Coccophagus lutescens+TX, Coccophagus rapae+TX, Coccophagus moniliformis+TX, Coccophagus spp. +TX, )+TX、Japanese square-headed beetle+TX、Siberian jawed braconid wasp+TX、Siberian jawed braconid wasp +TX, Pea leafminer +TX, small black ladybug (Delphastuscatalinae) +TX, Delphastus pusillus+TX, Diachasmimorpha krausii+TX, Long-tailed fly miner+TX, Diaparsis jucunda+TX, Diaphorencyrtusaligarhensis+TX, Pea leafminer+TX, Pea leafminer +TX, )+TX, Siberian Braconid Wasp ( +TX, )+TX, Encarsia species+TX, Encarsia long-tasseled aphid wasp+TX, Encarsia +TX, +TX、En- )+TX, Eretmocerus eremicus +TX, Encarsia guadeloupae +TX, Encarsia haitiensis +TX, Slender Hoverfly +TX, Eretmoceris siphonini+TX, Eretmoceruscalifornicus+TX, Eretmocerus eremicus( +TX, Eretline )+TX, Eretmocerus eremicus +TX, Heinrich's aphid wasp+TX, Monterey's aphid wasp ( +TX, Eretline )+TX, Eretmocerus siphonini+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, Coccinella spp. +TX, Harmo )+TX, Heterorhabditis species (Lawn )+TX, Heterorhabditis elegans (NemaShield +TX, +TX、Terranem- +TX, +TX, +TX、B- +TX, +TX, )+TX, Heterorhabditis megidis (Nemasys +TX, BioNem +TX、Exhibitline +TX, Larvanem- )+TX, Hippodamiaconvergens+TX, Hypoaspis aculeifer (Aculeifer- +TX、Entomite- )+TX、Hypoaspis miles(Hypoline +TX、Entomite- )+TX, Lbalia leucospoides+TX, Lecanoideus floccissimus+TX, Lemophagus errabundus+TX, Leptomastidea abnormis+TX, Leptomastix dactylopii +TX, Leptomastix epona+TX, Lindorus lophanthae+TX, Lipolexis oregmae+TX, Lucilia caesar +TX, Lysiphlebus testaceipes +TX, Macrolophus caliginosus (Mirical- +TX、Macroline +TX, )+TX, Mesoseiulus longipes+TX, Metaphycus flavus+TX, Metaphycuslounsburyi+TX, Micromus angulatus +TX, Microterys flavus +TX, Muscidifurax raptorellus and Spalangia cameroni +TX, Neodryinus typhlocybae+TX, Neoseiulus californicus+TX, Neoseiulus cucumeris +TX, Neoseiulus fallacis+TX, Nesideocoris tenuis( +TX, )+TX, bronze black fly (Ophyra aenescens) +TX, Orius insidiosus (Thripor- +TX, Oriline )+TX、Orius laevigatus (Thripor- +TX, Oriline )+TX、Orius majusculus(Oriline )+TX、Orius strigicollis (Thripor- )+TX, Pauesia juniperorum+TX, Pediobius foveolatus+TX, Phasmarhabditis hermaphrodita +TX, Phymastichus coffea+TX, Phytoseiulus macropilus+TX, Phytoseiulus persimilis ( +TX、Phytoline )+TX, Podisus maculiventris +TX, Pseudacteon curvatus+TX, Pseudacteon obtusus+TX, Pseudacteon tricuspis+TX, Pseudaphycus maculipennis+TX, Pseudleptomastix mexicana+TX, Psyllaephagus pilosus+TX, Psyttalia concolor (complex)+TX, Quadrastichus spp.+TX, Rhyzobius lophanthae+TX, Rodolia cardinalis+TX, Rumina decollate+TX, Semielacher petiolatus+TX, Sitobion avenae +TX, Steinernema carpocapsae (Nematac +TX, +TX, BioNem +TX, +TX, +TX, )+TX, Nematode +TX, Nemasys +TX, BioNem +TX, Steinernema- +TX, +TX, +TX、Exhibitline +TX、Scia- +TX, )+TX, Steinernema kraussei (Nemasys +TX, BioNem +TX、Exhibitline )+TX, Steinernema riobrave (Bio +TX、Bio )+TX, Steinernema scapterisci ( )+TX、Steinernema spp.+TX、Steinernematid spp. )+TX, Stethorus punctillum +TX, Tamarixia radiate +TX, Tetrastichus setifer +TX, Thropobius semiluteus +TX, Torymus sinensis +TX, Tricholine )+TX, Trichogramma brassicae (Tricho- )+TX, Trichogramma evanescens+TX, Trichogramma minutum+TX, Trichogramma ostriniae+TX, Trichogramma platneri+TX, Trichogramma pretiosum+TX, Xanthopimpla stemmator;

[1040] 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, Funnel trap (Trapline )+TX、 +TX, Grower's +TX, Homo-brassonolide +TX, Ferric Phosphate (Lilly Miller Worry Free Ferramol Slug & Snail )+TX、MCP hail trap (Trapline )+TX、parasitic insects Microctonus hyperodae+TX、Mycoleptodiscus terrestris(Des- )+TX、 +TX, +TX, +TX, Pheromone Net (Thripline )+TX, potassium bicarbonate +TX, potassium salt of fatty acids +TX, potassium silicate solution +TX, potassium iodide + potassium thiocyanate +TX、SuffOil- +TX, spider venom +TX, locust microsporidia (Semaspore Organic Grasshopper )+TX, Trapline +TX, Rebell )+TX and capture (Takitrapline y+ )+TX; and

[1041] Safeners, such as oxadiazine+TX, oxadiazine-methyl (including oxadiazine-methyl)+TX, cyclopropylsulfonamide+TX, dichloropropane+TX, oxadiazine (including oxadiazine-ethyl)+TX, oxadiazine+TX, fluazifop+TX, oxadiazine+TX, isoxadiazine (including isoxadiazine-ethyl)+TX, mefenpyr (including mefenpyr-diethyl)+TX, metcamifen+TX and oxadiazonil+TX.

[1042] 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. In the case where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; 13th edition; Editor: CDSTomLin; The British Crop Protection Council], they are described therein by the entry number given above in parentheses for the specific compound; e.g. the compound "avermectin" is described by entry number (1). In the case where "[CCN]" is added above to a specific compound, the compound in question is included in the "Compendium of Pesticide Common Names", which can be found on the Internet [A.Wood; Compendium of Pesticide Common Names , 1995-2004]; for example, the compound "acetoprolin" is described on the Internet at http: / / www.alanwood.net / pesticides / acetoprole.html middle.

[1043] Most of the active ingredients mentioned above are referred to by what are referred to as "common names" above, with the relevant "ISO common name" or another "common name" being used in individual cases. If a name is not a "common name," the type of name used is replaced by the name given in parentheses for the specific compound; in this case, the IUPAC name, IUPAC / Chemical Abstracts name, "Chemical Name," "Traditional Name," "Compound Name," or "Research Code" is used, or if neither one of those names nor the "common name" is used, the "synonym" is used. "CAS Registry Number" means the Chemical Abstracts Registry Number.

[1044] Active ingredient mixtures of compounds of formula I selected from Tables A-1 to A-22, Tables B-1 to B-4 and Table P and the above-mentioned active ingredients comprise compounds selected from Tables A-1 to A-22, Tables B-1 to B-4 and Table P and the above-mentioned active ingredients, these compounds and these active ingredients are 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 in a ratio of from 5:1 and 1:5, particularly preferably in a ratio of from 2:1 to 1:2, and likewise preferably in a ratio of from 4:1 to 2:1, especially In a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 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.

[1045] The mixtures as described above may be used in a method for controlling pests which comprises applying a composition comprising a mixture as described above to the pests or their environment, excluding methods for treating the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body.

[1046] Mixtures comprising a compound of formula I selected from Tables A-1 to A-22, Tables B-1 to B-4 and Table 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 (the mixture is composed of separate formulations of the single active ingredient components, such as a "tank mix"), and when applied in a sequential manner (i.e., one after another within a reasonably short period of time, such as a few hours or days) using a combination of these single active ingredients. The order in which the compound of formula I selected from Tables A-1 to A-22, Tables B-1 to B-4 and Table P and the active ingredients as described above are applied is not critical to the practice of the present invention.

[1047] 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.

[1048] 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.

[1049] 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 - selected to suit the intended purpose in 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 rates are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The application rate per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g / ha, preferably 10 to 600 g / ha.

[1050] In the field of crop protection, the preferred method of application is application to the leaves of the plants (foliar application), it being possible to select the frequency and rate of application in accordance with 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 (e.g. 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.

[1051] Compound of the present invention and composition thereof are also suitable for the protection of plant propagation materials (such as seeds, such as fruits, tubers or grains, or nursery plants), to resist the harmful organism of above-mentioned type.Can be used before planting, this propagation material is processed, for example, can be processed before sowing, seed.Alternately, can be by being immersed in liquid composition by seed or by applying solid composition layer, this compound is applied to seed grain (coating).Also may be when this propagation material is planted in application site, use these compositions, for example, during drilling, these compositions are applied to seed furrow.These treatment methods for plant propagation materials and the plant propagation materials so 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.

[1052] 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 etc. and in preferred embodiments means true seeds.

[1053] The present invention also includes seeds coated or treated with a compound of formula I or seeds containing a compound of formula I. Although more or less of the ingredient may penetrate into the seed material depending on the method of application, the term "coated or treated with and / or containing" generally means that at the time of application, in most cases, the active ingredient is on the surface of the seed. When the seed product is (re)planted, it can absorb the active ingredient. In an embodiment, the present invention makes available plant propagation material having a compound of formula I adhered thereto, the compound including those selected from Tables A-1 to A-22, Tables B-1 to B-4 and Table P. In addition, compositions comprising plant propagation material treated with a compound of formula I are made available, the compound including those selected from Tables A-1 to A-22, Tables B-1 to B-4 and Table P.

[1054] Seed treatment includes all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting. Seed treatment application of a compound of Formula I (including those selected from Tables A-1 to A-22, Tables B-1 to B-4 and Table P) can be carried out by any known method, such as spraying or by dusting the seeds before sowing or during sowing / planting.

[1055] Biological examples:

[1056] The following examples illustrate the present invention. Certain compounds of the present invention may differ from known compounds in that they exhibit greater efficacy at low application rates, which can be demonstrated by one skilled in the art using the experimental procedures outlined in the examples, using lower application rates (if necessary) such as 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

[1057] Example B1: Activity against Bemisia tabaci (cotton whitefly)

[1058] 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.

[1059] The following compounds produced at least 80% mortality at an application rate of 200 ppm: P1 , P2, P3, P4, P5, P6, P9, P10, P1 1 , P12, P13, P14, P15.

[1060] Example B2: Activity against Diabrotica cucumeris (corn rootworm)

[1061] Corn sprouts placed on an agar layer in a 24-well microtiter plate were treated with an aqueous test solution prepared from a 10,000ppm DMSO stock solution by spraying. After drying, the plates were infested with L2 larvae (6 to 10 / well). Four days after infestation, these samples were evaluated for mortality and growth inhibition compared to untreated samples.

[1062] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1 , P2, P3, P4, P5, P6, P7, P8, P9, P10, P1 1 , P12, P13, P14, P15, P16.

[1063] Example B3: Activity against Euschistus heros (Neotropical brown stink bug)

[1064] 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 N-2 stage nymphs. Five days after infestation, these samples were evaluated for mortality and growth inhibition compared to untreated samples.

[1065] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1 , P2, P3, P4, P5, P6, P7, P8, P10, P1 1 , P12, P13, P14, P15, P16.

[1066] Example B4: Against Frankliniella occidentalis (Western Flower Thrips Activity of flower thrips

[1067] Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with an aqueous test solution prepared from a 10,000 μL DMSO stock solution. After drying, the leaf discs were infested with a population of flower thrips of mixed ages. Seven days after infestation, the samples were evaluated for mortality.

[1068] The following compounds produced at least 80% mortality at an application rate of 200 ppm: P3, P6, P7, P8, P9, P10, P12, P13, P14.

[1069] Example B5: Against Plutella xylostella (Diamond back moth))'s life sex

[1070] 24-well microtiter plates with artificial diet were treated by pipetting with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, Plutella xylostella eggs were pipetted through a plastic template onto gel blotting paper and the plates were sealed with the plastic template. Eight days after infestation, these samples were evaluated for mortality and growth inhibition compared to untreated samples.

[1071] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1 , P3, P13, P14, P15, P16.

[1072] Example B6: Activity against Myzus persicae (green peach aphid)

[1073] 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 population of aphids of mixed ages. Six days after infestation, the samples were evaluated for mortality.

[1074] The following compounds produced at least 80% mortality at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P8, P9, P10, P11, P12, P13, P14, P15, P16.

[1075] Example B7: Activity against Myzus persicae (green peach aphid)

[1076] The roots of pea seedlings infested with a population of mixed-age aphids were placed directly into an aqueous test solution prepared from a 10,000 DMSO stock solution. Six days after the seedlings were placed in the test solution, the samples were evaluated for mortality.

[1077] The following compounds produced at least 80% mortality at a test rate of 24 ppm: P2, P5, P11.

[1078] Example B8: Against Plutella xylostella (Diamond back moth))'s life sex

[1079] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from a 10,000 ppm DMSO stock solution by pipetting. After drying, the plates were infested with L2 larvae (10 to 15 per well). Five days after infestation, the samples were evaluated for mortality and growth inhibition compared to untreated samples.

[1080] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P2, P4, P5, P6, P7, P8, P9, P10, P11, P12.

[1081] Example B9: Activity against Spodoptera littoralis (Egyptian cotton leafworm)

[1082] The cotton leaf disk is placed on the agar in the 24 hole microtiter plates and sprayed with the aqueous test solution prepared from 10 '000ppm DMSO stock solution.After drying, the leaf disk is infested with five L1 stage larvae. Infested afterwards 3 days, compared to untreated sample, these samples were assessed at mortality rate, antifeedant effect and growth inhibition.When at least one in these classifications (mortality rate, antifeedant effect and growth inhibition) was higher than untreated sample, realized the control of test sample to Spodoptera littoralis.

[1083] The following compounds gave at least 80% control at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16.

[1084] Example B10: Activity against Tetranychus urticae (Two-spotted spider mite)

[1085] Soybean 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, these samples were evaluated for mortality of the mixed population (active stage).

[1086] The following compounds produced at least 80% mortality at an application rate of 200 ppm: P1, P4, P5, P8, P10.

[1087] Example B11: Activity against brown rice planthopper (Nilaparvata lugens), larvicide, feeding / contact

[1088] Rice plants were treated with the diluted test solutions in a spray chamber. After drying, the plants were infested with approximately 20 N3 nymphs. Seven days after treatment, samples were evaluated for mortality and growth regulation.

[1089] The following compounds produced at least 80% mortality at an application rate of 50 ppm: P1, P2, P9, P10, P11.

[1090] Example B12: Active against brown rice planthopper (Nilaparvata lugens), larvicide, systemic into water

[1091] Rice plants grown in nutrient solution were treated with the diluted test solution in a nutrient culture system. One day after application, the plants were infested with approximately 20 N3 nymphs. Seven days after infestation, the samples were evaluated for mortality and growth regulation.

[1092] The following compounds produced at least 80% mortality at an application rate of 12.5 ppm: P1, P2, P4, P5, P9, P10, P11.

[1093] Example B13: Combating beet cyst nematode (Heterodera schachtii) Activity (in vitro characterization of larval mobility in 96-well plates)

[1094] Test solutions were prepared using a TECAN robot from a 10,000ppm DMSO stock solution to obtain 20 μL of 500ppm, 100ppm, 50ppm, 25ppm, 12.5ppm, and 6.25ppm. Three replicates were produced for each concentration. 80 μL of a nematode solution containing 100 to 150 freshly harvested second-stage larvae of Heterodera schachtii was added to each well. The plates were covered and stored in the dark at room temperature and incubated for 48 hours. The mobility of the exposed larvae in the treated wells was measured using an imaging tool and compared to the average of 12 untreated replicates.

[1095] The following compounds achieved at least 60% control at 100 ppm after 48 h: P1 , P4, P6, P8, P9, P10.

[1096] Example B14: Activity against southern root-knot nematode (Meloidogyne incognita) (In vitro characterization of larval migration in 96-well plates)

[1097] Test solutions were prepared using a TECAN robot from a 10,000ppm DMSO stock solution to obtain 20 μL of 1000ppm, 200ppm, 100ppm, 50ppm, 25ppm, and 12.5ppm. Three replicates were produced for each concentration. 80 μL of a nematode solution containing 100 to 150 freshly harvested second-stage larvae of the southern root-knot nematode was added to each well. The plates were covered and stored in the dark at room temperature and incubated for 48 hours. The mobility of the exposed larvae in the treated wells was measured using an imaging tool and compared to the average of 12 untreated replicates.

[1098] The following compounds achieved at least 60% control at 200 ppm after 48 h: P4, P8.

[1099] Example B15: Against Carpocapsa (Cydia) pomonella (Codling moth) moth), larvicides, ingestion / contact

[1100] Paraffin-coated diet cubes were sprayed with the diluted test solution in an application chamber. After drying, the treated cubes (10 replicates) were infested with one L1 larva. The samples were incubated at 26-27°C and examined for mortality and growth inhibition 14 days after infestation.

[1101] 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 12.5 ppm: P4, P5, P11, P15, P16.

Claims

1. A compound having formula (I) in A is CH or N; R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl; R9 is hydrogen or C1-C4 alkyl; Q is a group Q6 wherein the arrow indicates the point of attachment to the ring incorporating group A; And among them X1 is NR3; R3 is a C1-C4 alkyl group; R2 is C1-C6 haloalkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C1-C6 haloalkoxy; or Agrochemically acceptable salts of compounds of formula I.

2. The compound according to claim 1, wherein R3 is methyl.

3. The compound according to claim 1, wherein R2 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl or trifluoromethylsulfonyl.

4. The compound according to claim 1, wherein R2 is trifluoromethyl, trifluoromethylsulfonyl or trifluoromethylsulfanyl.

5. The compound according to claim 1, wherein R1 is ethyl or -CH2 cyclopropyl. The compound according to claim 1 , wherein R 1 is ethyl.

7. The compound according to claim 1, wherein R9 is hydrogen, methyl or ethyl.

8. The compound of claim 1, wherein R9 is hydrogen.

9. The compound of formula I according to claim 1 , which is selected from the group consisting of: 2-[[5-(cyclopropylmethylsulfonyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile (Compound P1); 2-[[5-Ethylsulfonyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile (Compound P2); 2-[[5-ethylsulfonyl-2-methyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridinyl]oxy]-2-methyl-propionitrile (Compound P11); and 2-[3-Ethylsulfonyl-4-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]phenoxy]-2-methyl-propionitrile (Compound P12).

10. A pesticidal composition comprising as active ingredient at least one compound of formula I as defined in any one of claims 1 to 9, in free form or in the form of an agrochemically utilizable salt, and at least one adjuvant.

11. A method for non-therapeutic control of pests, the method comprising applying a pesticidally effective amount of a compound of formula I as defined in any one of claims 1 to 9 or a pesticidal composition according to claim 10 to the pests, to the locus of the pests, or to plants susceptible to attack by the pests.

12. A method for protecting plant propagation material from attack by pests, the method comprising treating the propagation material or the locus where the propagation material is planted with the pesticidal composition according to claim 10.

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