RU2796535C2 - Pesticidally active heterocyclic derivatives with sulfur-containing substitutes - Google Patents

Abstract

FIELD: pharmaceuticals.

SUBSTANCE: invention relates to a compound of formula I and its agrochemically acceptable salts, where A represents CH or N; X is S or SO₂; R₁ represents C₁-C₄ alkyl; G₁ is either N or CH; X₁ is NR₃; where R₃ represents C₁-C₄ alkyl; R₂ is either halogen or C₁-C₄ haloalkyl; R₇ represents hydrogen, fluorine, cyano or C₁-C₆ alkyl; and R₈ is fluoro, cyano, C₁-C₈ alkyl or C₁-C₄ alkyloxycarbonyl. The invention also relates to an insect control composition, a method for controlling insects, and a method for protecting plant propagation material from attack by insects.

EFFECT: obtaining new compounds and a composition based on them which can be used in agriculture as effective insecticides.

7 cl, 4 tbl, 23 ex

Description

The present invention relates to pesticidally active, in particular to insecticidally active, heterocyclic derivatives with sulfur-containing substituents, to intermediate compounds for the preparation of these compounds, to compositions containing these compounds, and to their use for the control of animal pests (including arthropods and, in in particular, insects or members of the order Acarina).

Heterocyclic compounds with pesticide action are known and are described, for example, in WO 2012/086848, WO 2013/018928 and WO 2016/026848.

It has surprisingly been found that certain new pesticidally active heterocyclic derivatives containing a 6/5-bicyclic ring with sulfur-containing phenyl and pyridyl substituents have favorable properties as pesticides.

Therefore, the present invention provides compounds of formula (I),

Where

A is CH or N;

X is S, SO or SO ₂ ;

R ₁ is C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or C ₃ -C ₆ cycloalkyl-C ₁ -C ₄ alkyl;

G ₁ is N or CH;

X ₁ is O, S or NR ₃ ; where R ₃ represents hydrogen or C ₁ -C ₄ alkyl;

R ₂ is halogen, C ₁ -C ₆ haloalkyl, C ₁ -C ₄ haloalkylsulfanyl, C ₁ -C ₄ haloalkylsulfinyl, C ₁ -C ₄ haloalkylsulfonyl or C ₁ -C ₆ haloalkoxy;

R ₇ is hydrogen, halogen, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfanyl, C ₁ -C ₄ alkylsulfanyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfinyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfonyl-C ₁ -C ₄ alkyl or C ₁ -C ₄ alkyloxycarbonyl; And

R ₈ is halogen, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfanyl, C ₁ -C ₄ alkylsulfanyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfinyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfonyl-C ₁ -C ₄ alkyl or C ₁ -C ₄ alkyloxycarbonyl; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of the compounds of formula I.

Compounds of formula I which contain at least one basic center are capable of forming, for example, acid addition salts, for example, with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrohalic acid, with strong organic carboxylic acids such as C ₁ -C ₄ alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids such as C ₁ - C ₄ alkane or arylsulfonic acids which are unsubstituted or substituted, for example with halogen, for example methane or p-toluenesulfonic acid. Compounds of formula I which contain at least one acid group are capable of forming, for example, salts with bases, for example mineral salts, such as alkali metal salts or alkaline earth metal salts, for example sodium, potassium and magnesium salts, or salts with ammonia or an organic amine such as morpholine, piperidine, pyrrolidine, a lower mono-, di- or trialkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a lower mono-, di- or trihydroxyalkylamine, for example mono-, di- or triethanolamine.

The alkyl groups that occur in the substituent definitions may be straight or branched chain and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, nonyl , decyl and their branched isomers. The alkylsulfonyl, alkylsulfinyl, alkylsulfonyl, alkoxy, alkenyl and alkynyl radicals are derived from the alkyl radicals mentioned. Alkenyl and alkynyl groups may be mono- or polyunsaturated.

The halogen is typically fluorine, chlorine, bromine, or iodine. This also applies, respectively, to halogen in combination with other meanings such as haloalkyl or halophenyl.

Haloalkyl groups are preferably characterized by a chain length of 1 to 6 carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl.

Alkoxy groups are preferably characterized by a preferred chain length of 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy, as well as isomeric pentyloxy and hexyloxy radicals.

Alkoxyalkyl groups are preferably characterized by a chain length of 1 to 6 carbon atoms.

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

Cycloalkyl groups preferably contain from 3 to 6 carbon atoms in the ring, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

Free radicals are methyl groups.

The compounds of formula I according to the present invention also include hydrates, which can be formed during salt formation.

Preferred values for R ₁ , R ₂ , X, R ₇ , R ₈ , A, G ₁ and X ₁ in any combination thereof are given below.

Preferably R ₁ is C ₁ -C ₄ alkyl or C ₃ -C ₆ cycloalkyl-C ₁ -C ₄ alkyl.

More preferably R ₁ is C ₁ -C ₄ alkyl or cyclopropylmethyl.

Even more preferably R ₁ is methyl, ethyl, n-propyl, isopropyl or cyclopropylmethyl.

Most preferably R ₁ is ethyl.

Preferably R ₂ is halogen, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkylsulfanyl, C ₁ -C ₄ haloalkylsulfinyl or C ₁ -C ₄ haloalkylsulfonyl.

More preferably R ₂ is halo or C ₁ -C ₃ haloalkyl.

Even more preferably R ₂ is C ₁ -C ₂ haloalkyl.

Most preferably R ₂ is trifluoromethyl.

Preferably X is S or SO ₂ .

Most preferably X is SO ₂ .

Preferably R ₇ is hydrogen, fluorine, cyano, C ₁ -C ₄ alkoxycarbonyl, C ₁ -C ₄ alkyl.

More preferably R ₇ is hydrogen, methyl, ethyl or fluorine.

Even more preferably R ₇ is methyl or fluoro.

Most preferably R ₇ is methyl.

Preferably R ₈ is cyano, fluoro or C ₁ -C ₄ alkyl.

More preferably is fluorine, methyl or ethyl.

Even more preferably R ₈ is fluoro or methyl.

Most preferably R ₈ is methyl.

Preferably A is N.

Preferably G ₁ is N.

Preferably X ₁ is NR ₃ where R ₃ is C ₁ -C ₄ alkyl.

Most preferably X ₁ is NCH ₃ .

The following are embodiments of the present invention.

Embodiment 1 provides compounds of formula I, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, as defined above.

Embodiment 2 provides compounds or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof according to Embodiment 1, wherein R ₁ is C ₁ -C ₄ alkyl or C ₃ -C ₆ cycloalkyl-C ₁ - C ₄ alkyl.

Embodiment 3 provides the compounds or their agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide according to Embodiment 1 or 2, wherein R ₂ is halo, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkylsulfanyl , C ₁ -C ₄ haloalkylsulfinyl or C ₁ -C ₄ haloalkylsulfonyl.

Embodiment 4 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any one of Embodiments 1, 2, or 3, wherein X is S or SO ₂ .

Embodiment 5 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any one of Embodiments 1, 2, 3, or 4, wherein R ₇ is hydrogen, fluorine, cyano, C ₁ - C ₄ alkoxycarbonyl, C ₁ -C ₄ alkyl.

Embodiment 6 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any of Embodiments 1, 2, 3, 4, or 5, wherein R ₈ is cyano, fluoro, or C ₁ - C ₄ alkyl.

Embodiment 7 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any of Embodiments 1, 2, 3, 4, 5, or 6, wherein X ₁ is NR ₃ , where R ₃ is C ₁ -C ₄ alkyl.

Embodiment 8 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any one of Embodiments 1, 2, 3, 4, 5, 6, or 7, wherein R ₁ is C ₁ - C ₄ alkyl or cyclopropylmethyl.

Embodiment 9 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any of Embodiments 1, 2, 3, 4, 5, 6, 7, or 8, wherein R ₂ is halogen or C ₁ -C ₃ haloalkyl.

Embodiment 10 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any one of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, or 9, wherein R ₇ is is hydrogen, methyl, ethyl or fluorine.

Embodiment 11 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, wherein R ₈ is fluorine, methyl or ethyl.

Embodiment 12 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any one of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, where X ₁ represents NCH ₃ .

Embodiment 13 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any one of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, where R ₁ is methyl, ethyl, n-propyl, isopropyl or cyclopropylmethyl.

Embodiment 14 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, where R ₂ is C ₁ -C ₂ haloalkyl.

Embodiment 15 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, where X is SO ₂ .

Embodiment 16 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15, where R ₇ is methyl or fluorine.

Embodiment 17 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, where R ₈ is fluorine or methyl.

Embodiment 18 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, where R ₁ is ethyl.

Embodiment 19 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18, where R ₂ is trifluoromethyl.

Embodiment 20 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19, where R ₇ is methyl.

Embodiment 21 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, where R ₈ is methyl.

Embodiment 22 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or 21, where A is CH.

Embodiment 23 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or 21, where A is N.

Embodiment 24 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 or 23, where G ₁ is N.

Embodiment 25 provides the compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, according to any of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 or 23, where G ₁ is CH.

One group of compounds of formula I is represented by compounds of formula I-1,

where A, X, R ₁ , R ₂ , R ₇ and R ₈ are defined under formula I above. In this preferred group of compounds of formula I-1

R ₁ is preferably methyl, ethyl, n-propyl, isopropyl or cyclopropylmethyl;

R ₂ is preferably C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkylsulfanyl, C ₁ -C ₄ haloalkylsulfinyl or C ₁ -C ₄ haloalkylsulfonyl; and X is preferably SO ₂ .

Particularly preferred compounds of formula I-1 are those in which R ₁ is ethyl and X is SO ₂ .

One group of compounds of formula I-1 is represented by compounds of formula I-1a,

where X, R ₁ , R ₂ , R ₇ and R ₈ are defined under formula I above. In this preferred group of compounds of formula I-1

R ₁ is preferably methyl, ethyl, n-propyl, isopropyl or cyclopropylmethyl;

R ₂ is preferably C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkylsulfanyl, C ₁ -C ₄ haloalkylsulfinyl or C ₁ -C ₄ haloalkylsulfonyl; and X is preferably SO ₂ .

Particularly preferred compounds of formula I-1a are those in which R ₁ is ethyl and X is SO ₂ .

Another group of compounds of formula I-1 is represented by compounds of formula I-1b,

where X, R ₁ , R ₂ , R ₇ and R ₈ are defined under formula I above. In this preferred group of compounds of formula I-1

R ₁ is preferably methyl, ethyl, n-propyl, isopropyl or cyclopropylmethyl;

R ₂ is preferably C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkylsulfanyl, C ₁ -C ₄ haloalkylsulfinyl or C ₁ -C ₄ haloalkylsulfonyl; and X is preferably SO ₂ .

Particularly preferred compounds of formula I-1b are those in which R ₁ is ethyl and X is SO ₂ .

Another group of compounds of formula I is represented by compounds of formula I-2,

where A, X, R ₁ , R ₂ , R ₇ and R ₈ are defined under formula I above. In this preferred group of compounds of formula I-1

R ₁ is preferably methyl, ethyl, n-propyl, isopropyl or cyclopropylmethyl;

R ₂ is preferably C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkylsulfanyl, C ₁ -C ₄ haloalkylsulfinyl or C ₁ -C ₄ haloalkylsulfonyl; and X is preferably SO ₂ .

Particularly preferred compounds of formula I-2 are those in which R ₁ is ethyl and X is SO ₂ .

One group of compounds of formula I-2 is represented by compounds of formula I-2a,

where X, R ₁ , R ₂ , R ₇ and R ₈ are defined under formula I above. In this preferred group of compounds of formula I-1

R ₁ is preferably methyl, ethyl, n-propyl, isopropyl or cyclopropylmethyl;

R ₂ is preferably C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkylsulfanyl, C ₁ -C ₄ haloalkylsulfinyl or C ₁ -C ₄ haloalkylsulfonyl; and X is preferably SO ₂ .

Particularly preferred compounds of formula I-2a are those in which R ₁ is ethyl and X is SO ₂ .

Another group of compounds of formula I-2 is represented by compounds of formula I-2b,

where X, R ₁ , R ₂ , R ₇ and R ₈ are defined under formula I above. In this preferred group of compounds of formula I-1

R ₁ is preferably methyl, ethyl, n-propyl, isopropyl or cyclopropylmethyl;

R ₂ is preferably C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkylsulfanyl, C ₁ -C ₄ haloalkylsulfinyl or C ₁ -C ₄ haloalkylsulfonyl; and X is preferably SO ₂ .

Particularly preferred compounds of formula I-2b are those in which R ₁ is ethyl and X is SO ₂ .

The compounds of the present invention may have any number of advantages including, but not limited to, advantageous levels of biological activity for plant protection against insects or superior properties for use as agrochemically active ingredients (e.g., higher biological activity, advantageous spectrum of activity, improved safety profile, improved physico-chemical properties or increased biodegradability). In particular, it has surprisingly been found that certain compounds of formula (I) may show an advantageous safety profile against non-target arthropods, in particular pollinators such as honey bees, solitary bees and bumblebees. Most specifically, Apis mellifera.

In another aspect, the present invention provides a composition comprising an insecticidal, acaricidal, nematocidal or molluscicidal effective amount of a compound of formula (I), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, as defined in any of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 (above) or in any of the embodiments under the compounds of formulas (I-1), (I-1a), (I-1b), (I-2), (I-2a) and (I-2b) (above) and optionally an auxiliary agent or diluent.

In another aspect, the present invention provides a method for controlling and controlling insects, mites, nematodes, or mollusks, which comprises applying to a pest, a pest habitat, or a plant susceptible to pest attack, an insecticidal, acaricidal, nematocidal, or molluscicidal effective an amount of a compound of formula (I) or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof as defined in any of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 (above) or in any of the embodiments under the compounds of formula (I-1), (I-1a) , (I-1b), (I-2), (I-2a) and (I-2b) (above), or a composition as defined above.

In yet another further aspect, the present invention provides a method of protecting plant propagation material from attack by insects, mites, nematodes or mollusks, which comprises treating the propagation material or the area where the propagation material is planted with a composition as defined above.

The method of obtaining compounds of formula I according to the present invention is carried out using methods known to specialists in this field of technology. Compounds of formula I-a3, where X is SO ₂ and A, X ₁ , G ₁ , R ₁ , R ₂ , R ₇ and R ₈ are defined under formula I above, can be obtained by oxidation of compounds of formula I-a2, where X is SO, and A, X ₁ , G ₁ , R ₁ , R ₂ , R ₇ and R ₈ are defined under formula I above. The reaction can be carried out with reagents such as a peracid, such as peracetic acid or meta-chloroperbenzoic acid, or a hydroperoxide, such as hydrogen peroxide or tert-butyl hydroperoxide, or an inorganic oxidizing agent, such as monoperoxodisulfate salt or potassium permanganate. Similarly, compounds of formula I-a2, where X is SO and A, X ₁ , G ₁ , R ₁ , R ₂ , R ₇ and R ₈ are defined under formula I above, can be obtained by oxidizing compounds of formula I-a1, where X represents S, and A, X ₁ , G ₁ , R ₁ , R ₂ , R ₇ and R ₈ are defined under formula I above, under similar conditions described above. 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. The conversion of compounds of formula I-a1 to compounds of formulas I-a2 and I-a3 is shown in Scheme 1.

Scheme 1

Compounds of formula I, where Q is defined as the radical shown at the bottom of scheme 2, and where X, A, X ₁ , G ₁ , R ₁ , R ₂ , R ₇ and R ₈ are defined under formula I above, can be obtained using methods, described in Scheme 2. By treating compounds of formula III wherein Q and A and R ₁ are defined under formula I above, X is S or SO ₂ and Xb ₁ is preferably halogen (even more preferably chlorine, bromine or iodine), a compound of formula V (trimethylsilylacetonitrile) in the presence of zinc(II) fluoride and a palladium(0) catalyst such as tris(dibenzylideneacetone)dipalladium(0) chloroform (Pd ₂ (dba) ₃ ), a ligand, e.g. Xantphos, in an inert solvent such as DMF, at temperatures of 100-160° C., optionally heated with microwave radiation, compounds of formula II are obtained, where A, Q, and R ₁ are defined under the general formula I above, and X is is S or SO ₂ . Such methods have been described in the literature, for example, J. Am. Chem. soc. 2005, 127, 15824-15832. Compounds of formula II can be treated sequentially with alkylating reagents of the general formulas VIa and VIb, where Xb ₂ is preferably Br, I, OSO ₃ Me or OTf and R ₇ is R ₈ and they are defined under formula I, in the presence of a base, such as sodium hydride, K ₂ CO ₃ or Cs ₂ CO ₃ in an inert solvent such as THF, DMF, 1,4-dioxane or acetonitrile to give compounds of formula I.

Alternatively, compounds of formula II can be treated with an excess of the above base and reagent VIb to give compounds of the general type Ia-4 where R ₇ =R ₈ . Alternatively, compounds of formula II can be prepared from compounds of formula VII wherein A, Q, X and R ₁ are defined under formula I above and R ₁₁ is a C ₁ -C ₆ alkyl group, preferably methyl or ethyl, by decarboxylation of Crapcio. Such methods have been described, for example, in Tetrahedron Lett. 1974, 15, 1091-1094. Compounds of formula VII can be prepared by reacting compounds of formula III with cyanoacetates of general formula VIII, where R ₁₁ is a C ₁ -C ₆ alkyl group, preferably methyl or ethyl. Such a reaction can take place in polar aprotic solvents such as dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF) or N-methylpyrrolidone (NMP) in the presence of a base such as K ₂ CO ₃ or Na ₂ CO ₃ , in the presence of or in the absence of a phase transfer catalyst ("PTC"), at temperatures of 20-180°C, preferably 80-140°C. Similarly, transition metal catalyzed processes are known, see, for example, Angew. Chem. Int. Ed. 2011, 50, 4470-4474. Alternatively, compounds of formula I can be obtained directly from compounds of formula III by treatment with compounds of formula IV, where R ₇ and R ₈ are defined above for formula I, in the presence or absence of a catalyst such as Pd ₂ (dba) ₃ and a ligand , such as BINAP, using a strong base, such as LiHMDS, in an inert solvent, such as THF, at temperatures ranging from -20 to 120°C. Such methods have been described in the literature, for example, Org. Lett. 2014, 16, 6314-6317; J. Org. Chem. 2005, 70, 10186-10189 or Org. Lett. 2011, 13, 1690-1693.

Scheme 2

Alternatively, compounds of formula I can be prepared as described in Scheme 3. Treatment of compounds of formula XII, where R ₁ , A, X, R ₇ and R ₈ are defined above for formula I, can be used in relation to compounds of formula XI with methods known to those skilled in the art and described, for example, in Tetrahedron 2005, 61 (46), 10827-10852. For example, compounds of formula XI, where X ₀ represents chlorine, are formed by treatment with, for example, oxalyl chloride or thionyl chloride in the presence of catalytic amounts of DMF in inert solvents such as dichloromethane or THF at temperatures from 20°C to 100°C, preferably 25°C. Treatment of compound XI with compounds of formula X, where R ₂ , G ₁ and X ₁ are defined as described in formula I, optionally in the presence of a base, for example triethylamine or pyridine, compounds of formula IX are obtained. Alternatively, compounds of formula XI can be prepared by treating compounds of formula XII with dicyclohexylcarbodiimide (DCC) or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) to give activated species of compounds XI, where X ₀ is X ₀₁ and X ₀₂ , respectively, in an inert solvent, such as pyridine or tetrahydrofuran (THF), optionally in the presence of a base, such as triethylamine, at temperatures of 50-180°C. The resulting compounds of formula IX can then be converted to compounds of formula I by dehydration, for example by heating under microwave radiation, in the presence of an acid catalyst, for example methanesulfonic acid or p-toluenesulfonic acid, in an inert solvent such as N-methylpyrrolidone, at values temperature 25-180°C, preferably 130-170°C. Such methods have been previously described in WO 2010/125985. Alternatively, compounds of formula IX can be converted to compounds of formula I (where X ₁ is O) using triphenylphosphine, diisopropyl azodicarboxylate in an inert solvent such as THF at temperatures of 25-50°C. Such Mitsunobu reaction conditions have previously been described for these transformations (see WO 2009/131237). Compounds of formula X have been described previously, for example in WO 2012/086848, WO 2015/000715 and WO 2016/116338.

Scheme 3

Compounds of formula XII, where R ₁ , A, X, R ₇ and R ₈ are defined above for formula I, can be obtained using the methods described in scheme 4. Synthesis of the necessary starting materials of formula XV, where R ₁ , X, A are defined above for formula I, and where Xb ₁ can be a halogen, preferably chlorine, bromine or iodine, or a sulfonate such as, for example, trifluoromethanesulfonate, most preferably bromine or iodine, and R _LG is C ₁ -C ₄ alkyl, was previously described, for example, in WO 2016/026848. By treating compounds of formula XV with trimethylsilylacetonitrile (V) in the presence of zinc(II) fluoride and a palladium(0) catalyst such as the adduct of tris(dibenzylideneacetone)dipalladium(0) and chloroform (Pd ₂ (dba) ₃ ), the ligand, for example, Xantphos, in an inert solvent such as DMF, at temperatures of 100-160°C, optionally under microwave heating, compounds of formula XIV are obtained, where X is S or SO ₂ , R ₁ and A are defined in formula I above, and R _LG is C ₁ -C ₄ alkyl. Such methods have been described in the literature, for example, in J. Am. Chem. soc. 2005, 127, 15824-15832. Compounds of formula XIV can be sequentially treated with alkylating reagents of formula VIa or VIb, where Xb ₂ is preferably Br, I or OTf and R ₇ and R ₈ are defined under formula I, in the presence of a base such as sodium hydride, K ₂ CO ₃ or Cs ₂ CO ₃ in an inert solvent such as THF, DMF or acetonitrile to give compounds of formula XIII wherein X is S or SO ₂ , R ₁ , A, R ₇ and R ₈ are defined in formula I above and R _LG is C ₁ -C ₄ alkyl. Alternatively, compounds of formula XIV can be treated with an excess of the above base and reagent VIb to give compounds of the general type XIII-a, where R ₇ =R ₈ . Alternatively, compounds of formula XIII can be obtained directly from compounds of formula XV by treatment with compounds of formula IV, where R ₇ and R ₈ are defined above for formula I, in the presence or absence of a catalyst such as Pd ₂ (dba) ₃ and a ligand , such as BINAP, using a strong base, such as LiHMDS, in an inert solvent, such as THF, at temperatures ranging from -20 to 120°C. Such methods have been described in the literature, for example, in J. Am. Chem. soc. 2005, 127, 15824-15832; J. Org. Chem. 2005, 70, 10186-10189, Org. Lett. 2014, 16, 6314-6317 or Org. Lett. 2011, 13, 1690-1693.

Alternatively, compounds of formula XIV can be obtained from compounds of formula XVI, where A, X and R ₁ are defined under formula I above, R _LG and R ₁₁ independently of each other mean a C ₁ -C ₆ alkyl group, preferably methyl or ethyl, by decarboxylation of Crapcho. Such methods have been described, for example, in Tetrahedron Lett. 1974, 15, 1091-1094. Compounds of formula XVI can be prepared by reacting compounds of formula XV with cyanoacetates of formula VIII, where R ₁₁ is a C ₁ -C ₆ alkyl group, preferably methyl or ethyl. Such a reaction can take place in polar aprotic solvents such as dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF) or N-methylpyrrolidone (NMP) in the presence of a base such as K ₂ CO ₃ or Na ₂ CO ₃ , in the presence of or in the absence of a phase transfer catalyst ("PTC"), at temperatures of 20-180°C, preferably 80-140°C. Similarly, transition metal catalyzed processes are known, see, for example, Angew. Chem. Int. Ed. 2011, 50, 4470-4474. Compounds of formula XIII or XIII-a can be converted to compounds of formula XII by saponification under conditions known to the person skilled in the art. Compounds of formula IV, V, VIa, VIb and VIII are commercially available, or methods for preparing such compounds are known to the person skilled in the art. Compounds of formula XV are known and their synthesis has been reported in the literature, see for example WO 2016/005263.

Compounds of formula XIII or XIII-a can be converted to compounds of formula XII by saponification under conditions known to the person skilled in the art. Compounds of formula IV, V and VIa, VIb and VIII are commercially available, or methods for preparing such compounds are known to the person skilled in the art.

Scheme 4

Compounds of formulas IX, XI, XII, XIII, XVI are new, specially designed for the preparation of compounds of formula I.

Thus, in another further aspect of the present invention, there are

compounds of formula IX,

Where

A is CH or N, preferably N;

X is S, SO or SO ₂ , preferably S or SO ₂ ;

R ₁ is C ₁ -C ₄ alkyl, preferably ethyl;

G ₁ is N or CH;

R ₃ is hydrogen or C ₁ -C ₄ alkyl, preferably methyl;

R ₂ is halogen, C ₁ -C ₆ haloalkyl, C ₁ -C ₄ haloalkylsulfanyl, C ₁ -C ₄ haloalkylsulfinyl, C ₁ -C ₄ haloalkylsulfonyl or C ₁ -C ₆ haloalkoxy; preferably CF ₃ ;

R ₇ is hydrogen, halogen, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfanyl, C ₁ -C ₄ alkylsulfanyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfinyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfonyl-C ₁ -C ₄ alkyl or C ₁ -C ₄ alkyloxycarbonyl, preferably R ₇ is methyl or fluorine; And

R ₈ is halogen, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfanyl, C ₁ -C ₄ alkylsulfanyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfinyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfonyl-C ₁ -C ₄ alkyl or C ₁ -C ₄ alkyloxycarbonyl, preferably R ₈ is methyl or fluorine; or their regioisomer, or a mixture of their isomers;

And

compounds of formula XI,

Where

A is CH or N, preferably N;

X is S, SO or SO ₂ , preferably S or SO ₂ ;

R ₁ is C ₁ -C ₄ alkyl, preferably ethyl;

R ₇ is hydrogen, halogen, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfanyl, C ₁ -C ₄ alkylsulfanyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfinyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfonyl-C ₁ -C ₄ alkyl or C ₁ -C ₄ alkyloxycarbonyl, preferably R ₇ is methyl or fluorine; And

R ₈ is halogen, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfanyl, C ₁ -C ₄ alkylsulfanyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfinyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfonyl-C ₁ -C ₄ alkyl or C ₁ -C ₄ alkyloxycarbonyl, preferably R ₈ is methyl or fluorine;

And

compounds of formula XII,

Where

A is CH or N, preferably N;

X is S, SO or SO ₂ , preferably S or SO ₂ ;

R ₁ is C ₁ -C ₄ alkyl, preferably ethyl;

R ₇ is hydrogen, halogen, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfanyl, C ₁ -C ₄ alkylsulfanyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfinyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfonyl-C ₁ -C ₄ alkyl or C ₁ -C ₄ alkyloxycarbonyl, preferably R ₇ is methyl or fluorine;

R ₈ is halogen, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfanyl, C ₁ -C ₄ alkylsulfanyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfinyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfonyl-C ₁ -C ₄ alkyl or C ₁ -C ₄ alkyloxycarbonyl, preferably R ₈ is methyl or fluorine;

And

compounds of formula XIII,

Where

A is CH or N, preferably N;

X is S, SO or SO ₂ , preferably S or SO ₂ ;

R ₁ is C ₁ -C ₄ alkyl, preferably ethyl;

R ₇ is hydrogen, halogen, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfanyl, C ₁ -C ₄ alkylsulfanyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfinyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfonyl-C ₁ -C ₄ alkyl or C ₁ -C ₄ alkyloxycarbonyl, preferably R ₇ is methyl or fluorine;

R ₈ is halogen, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfanyl, C ₁ -C ₄ alkylsulfanyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfinyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfonyl-C ₁ -C ₄ alkyl or C ₁ -C ₄ alkyloxycarbonyl, preferably R ₈ is methyl or fluorine; And

R _LG is C ₁ -C ₄ alkyl, preferably methyl or ethyl;

And

compounds of formula XVI,

Where

A is CH or N, preferably N;

X is S, SO or SO ₂ , preferably S or SO ₂ ;

R ₁ is C ₁ -C ₄ alkyl, preferably ethyl;

R ₁₁ is C ₁ -C ₄ alkyl, preferably methyl or ethyl; And

R _LG is C ₁ -C ₄ alkyl, preferably methyl or ethyl.

A regioisomer by-product is sometimes obtained in the preparation of compounds of formula (IX), namely compounds of formula (IX-z),

where A, X, R ₁ , G ₁ , R ₃ , R ₂ , R ₇ and R ₈ are defined above for compounds of formula (IX).

Reagents can be introduced into the reaction 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 dialkylamides or alkaline earth metals or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. 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, potassium hydride calcium, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1, 8-diazabicyclo[5.4.0]undec-7-ene (DBU).

The reactants can be reacted with each other as such, i. without the addition of a solvent or diluent. However, in most cases it is advantageous to add an inert solvent or diluent or a mixture thereof. If the reaction is carried out in the presence of a base, bases which are used in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, can also act as solvents or diluents.

The reaction is preferably carried out at a temperature in the range from about -80°C to about +140°C, preferably from about -30°C to about +100°C, in many cases in the range from ambient temperature to about +80°C.

A compound of formula I can be converted in a known manner per se to another compound of formula I by substituting one or more substituents on the parent compound of formula I in a conventional manner with another substituent(s) according to the present invention.

Depending on the choice of reaction conditions and starting materials that are suitable in each case, it is possible, for example, in one reaction step to replace only one substituent with another substituent according to the present invention, or it is possible to replace several substituents with other substituents according to the present invention in one reaction step .

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

Salts of compounds of formula I can be converted in the conventional manner to the free compounds of I, acid addition salts, for example by treatment with a suitable basic compound or a suitable ion exchange reagent, and salts with bases, for example, by treatment with a suitable acid or a suitable ion exchange reagent.

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

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

The compounds of formula I and, if appropriate, their tautomers, in each case in free form or in salt form, may be present in the form of one of the possible isomers or as a mixture thereof, for example in the form of pure isomers such as antipodes and/or diastereomers , or in the form of mixtures of isomers, such as mixtures of enantiomers, for example, racemates, mixtures of diastereomers or mixtures of racemates, depending on the numerical, absolute or relative configuration of the asymmetric carbon atoms that are in the molecule, and / or depending on the configuration of non-aromatic double bonds, that are in the molecule; the present invention relates to pure isomers as well as to all possible mixtures of isomers and is to be understood in each case above and below in this sense, even if stereochemical details are not specifically mentioned in each case.

Mixtures of diastereomers or mixtures of racemates of compounds of formula I, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen, can be separated in a known manner into pure diastereomers or racemates on the basis of physicochemical differences components, for example, using fractional crystallization, distillation and/or chromatography.

Mixtures of enantiomers, such as racemates, which can be obtained in a similar way, can be separated into optical antipodes by known methods, for example, by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example, high performance liquid chromatography (HPLC) on cellulose acetate , with the help of suitable microorganisms, by cleavage with specific immobilized enzymes, by formation of inclusion compounds, for example, using chiral crown ethers, where only one enantiomer is involved in the formation of the complex, or by conversion to diastereomeric salts, for example, by performing the reaction of the racemate of the main end product with an optically active acid, such as a carboxylic acid, such as camphoric, tartaric or malic acid, or a sulfonic acid, such as camphorsulfonic acid, and separating a mixture of diastereomers that can be obtained in this way, for example, by fractional crystallization based on their different solubility, to obtain diastereomers, from which the desired enantiomer can be released under the action of suitable means, for example, base funds.

Pure diastereomers or enantiomers can be obtained according to the present invention not only by separating suitable mixtures of isomers, but also by conventional diastereoselective or enantioselective synthesis methods, for example by carrying out the process of the present invention with starting materials of suitable stereochemical configuration.

N-oxides can be prepared by reacting a compound of formula I with a suitable oxidizing agent, eg an H ₂ O ₂ /urea adduct, in the presence of an acid anhydride, eg trifluoroacetic anhydride. Such types of oxidation are known from the literature, for example from J. Med. Chem., 32 (12), 2561-73, 1989 or WO 00/15615.

It is advantageous to isolate or synthesize in each case a biologically more effective isomer, for example an enantiomer or a diastereomer, or a mixture of isomers, for example a mixture of enantiomers or a mixture of diastereomers, if the individual components are characterized by different biological activity.

The compounds of formula I and, if appropriate, their tautomers, in each case in free form or in salt form, may, if necessary, also be obtained in the form of hydrates and/or may include other solvents, for example, which could be used to crystallize the compounds present in solid form.

Compounds from table X below can be obtained in accordance with the methods described above. The following examples are intended to illustrate the present invention and show the preferred compounds of formula I.

Table X. This table discloses 15 definitions of substituents X.001-X.015 of formula I,

where R ₂ , G ₁ , X ₁ , A, R ₁ , R ₇ and R ₈ are defined below.

and N-oxides of compounds from Table X. Me is a methyl group, Et is an ethyl group, i-Pr is an isopropyl group, C(O)OEt is an ethoxycarbonyl group, MeO is a methoxy group, and MeOCH ₂ is is a methoxymethyl group.

Table 1. This table discloses 23 compounds 1.001-1.023 of formula I-1, where X is S, and R ₂ , G ₁ , X ₁ , A, R ₁ , R ₇ and R ₈ are defined in table X. For example, connection 1.001 has the following structure:

Table 2. This table discloses 23 compounds 2.001-2.023 of formula I-1a, where X is SO and R ₂ , G ₁ , X ₁ , A, R ₁ , R ₇ and R ₈ are defined in table X.

Table 3. This table discloses 23 compounds 3.001-3.023 of formula I-1a, where X is SO ₂ and R ₂ , G ₁ , X ₁ , A, R ₁ , R ₇ and R ₈ are defined in table X.

The formula I compounds of the present invention are active ingredients of importance in the field of pest control for prevention and/or treatment even at low application rates, which have a very suitable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. The active ingredients of the present invention act on all or some of the developmental stages of normally susceptible but also resistant pests such as insects or members of the order Acarina. The insecticidal or acaricidal activity of the active ingredients according to the present invention can be manifested directly, i. in the destruction of pests, which occurs either immediately, or only after some time, for example, during molting, or indirectly, for example, in reduced oviposition and/or hatching.

Examples of the aforementioned pest animals are:

from the order Acarina, for example,

Acalitus spp. Aculus spp. chus 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.;

from the order Anoplura, for example,

Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.;

from the order Coleoptera, for example,

Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis, Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala s pp, Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemLineata, Lissorhoptrus spp., Liogenys spp, Maecolaspis spp, Maladera castanea, Megascelis spp, Mel ighetes aeneus, Melolontha spp. Myochrous armatus phorus spp, Sternechus subsignatus, Tenebrio spp., Tribolium spp. and Trogoderma spp.;

from the order Diptera, for example,

Aedes spp., Anopheles spp., Antherigona soccata, Bactrocea oleae, Bibio hortulanus, Bradysia spp, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., 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., Rivelia quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;

from the order Hemiptera, for example,

Acanthocoris scabrator, Acrosternum spp, Adelphocoris lineolatus, Amblypelta nitida, Bathycoelia thalassina, Blissus spp, Cimex spp., Clavigralla tomentosicollis, Creontiades spp, Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp, Euchistus spp ., Eurydema pulchrum, Eurygaster spp. ., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp, Margarodes spp, Murgantia histrionic, Neomegalotomus spp, Nesidiocoris tenuis, Nezara spp., Nysius simulans, Oebalus insularis, Piesma spp., Piezodorus spp, Rhodnius spp., Sahl bergella singularis , Scaptocoris castanea, Scotinophara spp., Thyanta spp., Triatoma spp., Vatiga illudens;

Acyrthosium pisum, Adalges spp, Agalliana ensigera, Agonoscena targionii, Aleurodicus spp, Aleurocanthus spp, Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., As pidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp, Brachycaudus spp, Brevicoryne brassicae, Cacopsylla spp, Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp, Cofana spectra, Cryptomyzus spp, Cicadulina spp, Coccus hesperid um, Dalbulus maidis, Dialeurodes spp. , Diaphorina citri, Diuraphis noxia, Dysaphis spp, Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp. , Laodelphax spp., Lecanium corni, Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp., Mahanarva spp, Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp., Neotoxoptera sp, Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats, Odonaspi s ruthae, Oregma lanigera Zehnter, Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Peregrinus maidis, Perkinsiella spp, Phorodon humuli, Phylloxera spp, Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp. , Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp. sporoboli, Trionymus spp. , Trioza erytreae, Unaspis citri, Zygina flammigera, Zyginidia scutellaris,;

from the order Hymenoptera, for example,

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

from the order Isoptera, for example,

Coptotermes spp, Corniternes cumulans, Incisitermes spp, Macrotermes spp, Mastotermes spp, Microtermes spp, Reticulitermes spp.; Solenopsis geminate

from the order Lepidoptera, for example,

Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp, Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp, Crocidolomia binotalis, Cryptophlebia le ucotreta, Cydalima perspectalis , Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea, Earias spp., Eldana saccharina, Ephestia spp., Epinotia spp., Estigmene acrea, Etiella zinckinella, Eucosma spp. Feltia jaculiferia, Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp., Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostege bifidalis, Ly mantria spp., Lyonetia spp. , Malacosoma spp., Mamestra brassicae, Manduca sexta, Mythimna spp, Noctua spp, Operophtera spp., Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Papaipema nebris, Pectinophora gossypiela, Perileucoptera cochella, Pse udaletia unipuncta, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Pseudoplusia spp., Rachiplusia nu, Richia albicosta, Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp. Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tuta absoluta, and Yponomeuta spp.;

from the order Mallophaga, for example,

Damalinea spp. and Trichodectes spp.;

from the order Orthoptera, for example,

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

from the order Psocoptera, for example,

Liposcelis spp.;

from the order Siphonaptera, for example,

Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis;

from the order Thysanoptera, for example,

Calliothrips phaseoli, Frankliniella spp., Heliothrips spp, Hercinothrips spp., Parthenothrips spp, Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp.;

from the order Thysanura, for example, Lepisma saccharina.

The active ingredients of the present invention can be used to control, i. control or destruction of pests of the above type which occur in particular on plants, especially useful plants and ornamental plants in agriculture, horticulture and forestry, or on organs of such plants, such as fruits, flowers, leaves, stems, tubers or roots, and in some cases even on plant organs that are formed at a later date and still remain protected from these pests.

Suitable target crops are, in particular, cereals such as wheat, barley, rye, oats, rice, maize or sorghum; beetroot, such as sugar beet or fodder beet; fruit crops, for example pome, stone fruit or berry crops such as apple, pear, plum, peach, almond, cherry or berry varieties, for example strawberries, raspberries or blackberries; legumes such as beans, lentils, peas or soybeans; oilseeds such as oilseed rape, mustard, poppy, olives, sunflower varieties, coconut palm, castor beans, cocoa or groundnut varieties; cucurbits such as pumpkins, cucumbers or melons; fibrous plants such as cotton, flax, hemp or jute; citrus fruits such as oranges, lemons, grapefruit or tangerines; vegetables such as spinach, lettuce, asparagus, cabbage varieties, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae such as avocado, Cinnamonium or camphor tree; as well as tobacco, nuts, coffee, eggplant varieties, sugar cane, tea, pepper, cultivated grape varieties, hops, plantains and rubber plants.

), Bougainvillea spp., Brachycome spp., Brassica spp. (декоративные виды), Calceolaria spp., Capsicum annuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemum spp., Cineraria spp. (C. maritime), Coreopsis spp., Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (I. Walleriana), Iresines spp., Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesia spp., Tagetes spp., Dianthus spp. (гвоздика), Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (P. peltatum, P. Zonale), Viola spp. (анютины глазки), Petunia spp., Phlox spp., Plecthranthus spp., Poinsettia spp., Parthenocissus spp. (P. quinquefolia, P. tricuspidata), Primula spp., Ranunculus spp., Rhododendron spp., Rosa spp. (роза), Rudbeckia spp., Saintpaulia spp., Salvia spp., Scaevola aemola, Schizanthus wisetonensis, Sedum spp., Solanum spp., Surflnia spp., Tagetes spp., Nicotinia spp., Verbena spp., Zinnia spp. и другие грядковые растения.The compositions and/or methods of the present invention can also be applied to any ornamental and/or vegetable crops, including flowers, shrubs, deciduous trees and evergreens. For example, the present invention can be applied to any of the following ornamental plant species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g. B. elatior, B. semperflorens, B.

), Bougainvillea spp., Brachycome spp., Brassica spp. (ornamental species), Calceolaria spp., Capsicum annuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemum spp., Cineraria spp. (C. maritime), Coreopsis spp., Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (I. Walleriana), Iresines spp., Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesia spp., Tagetes spp., Dianthus spp. (cloves), Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (P. peltatum, P. Zonale), Viola spp. (pansies), Petunia spp., Phlox spp., Plechranthus spp., Poinsettia spp., Parthenocissus spp. (P. quinquefolia, P. tricuspidata), Primula spp., Ranunculus spp., Rhododendron spp., Rosa spp. (rose), Rudbeckia spp., Saintpaulia spp., Salvia spp., Scaevola aemola, Schizanthus wisetonensis, Sedum spp., Solanum spp., Surflnia spp., Tagetes spp., Nicotinia spp., Verbena spp., Zinnia spp. and other garden plants.

For example, the present invention can be applied to any of the following types of vegetable crops: Allium spp. (A sativum, A. sulfur, A. oschaninii, A. porrum, A. ascalonicum, A. ftstulosum), Anthriscus cerefolium, Apium graveolus, Asparagus officinalis, Beta vulgarus, Brassica spp. (B. Oleracea, B. Pekinensis, B. rapa), Capsicum annuum, Cicer arietinum, Cichorium endivia, Cichorum spp. (C. intybus, C. endivia), Citrillus lanatus, Cueumis spp. (C. sativus, C. melo), Cucurbita spp. (C. pepo, C. maxima), Cyanara spp. (C. scolymus, C. cardunculus), Daucus carota, Foeniculum vulgare, Hypericum spp., Lactuca sativa, Lycopersicon spp. (L. esculentum, L. lycopersicum), Mentha spp., Ocimum basilicum, Petroselinum crispum, Phaseolus spp. (P. vulgaris, P. coccineus), Pisum sativum, Raphanus sativus, Rheum rhaponticum, Rosemarinus spp., Salvia spp., Scorzonera hispanica, Solanum melongena, Spinacea oleracea, Valerianella spp. (V. locusta, V. eriocarpa) and Vicia faba.

Preferred ornamental plants include Saintpaulia, Begonia, Dahlia, Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus , Fuchsia, Salvia, Hortensia, rosemary, sage, St. John's wort, mint, sweet pepper, tomato and cucumber.

The active ingredients of the present invention are particularly suitable for the control of Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis on cotton, vegetable, corn, rice and soybeans. The active ingredients according to the present invention are additionally particularly suitable for the control of Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potato varieties) and Chilo supressalis ( preferably in rice).

The active ingredients of the present invention are particularly suitable for the control of Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis on cotton, vegetable, corn, rice and soybeans. The active ingredients according to the present invention are additionally particularly suitable for the control of Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa (preferably in potato varieties) and Chilo supressalis ( preferably in rice).

In a further aspect, the present invention may also relate to a method for controlling damage to a plant and parts thereof by plant parasitic nematodes (endoparasitic, semi-endoparasitic and ectoparasitic nematodes), in particular plant parasitic nematodes such as nodule nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica , Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other species of Globodera; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii and other Heterodera species; seed gall nematodes, Anguina species; stem and leaf nematodes, Aphelenchoides species; stinging nematodes, Belonolaimus longicaudatus and other species of Belonolaimus; conifer nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; ring nematodes, Criconema spp., Criconemella spp., Criconemoides spp., Mesocriconema spp.; stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; awl-nosed nematodes, Dolichodorus species; spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; sheath and sheath-like nematodes, Hemicycliophora spp. and Hemicriconemoides spp.; Hirshmanniella spp.; lanceolate nematodes, Hoploaimus species; fake root growth nematodes, Nacobbus spp.; needle nematodes, Longidorus elongatus and other Longidorus species; short-bodied nematodes, Pratylenchus species; wounding nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; burrowing nematodes, Radopholus similis and other Radopholus species; kidney nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species; species of Scutellonema; bristly root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; dwarf nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; citrus nematodes, Tylenchulus species; American Xifinema, Xiphinema species; as well as other plant parasitic nematode species such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp. and Quinisulcius spp.

The compounds of the present invention may also have activity against molluscs. Examples of these mollusks include, for example, Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. nemoralis); ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H. obvia); Helicidae Helicigona arbustorum); Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.

The term "crops" should be understood to also include crop plants transformed by the use of recombinant DNA technologies in such a way that they are capable of synthesizing one or more selective toxins, such as those known, for example, in toxin-producing bacteria, especially bacteria of the genus bacillus.

Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, such as insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis such as δ-endotoxins, eg Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), eg Vip1, Vip2, Vip3 or Vip3A; or insecticidal proteins of nematode colonizing bacteria, eg Photorhabdus spp. or Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus; animal-produced toxins such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi such as Streptomycetes toxins, plant lectins such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome inactivating proteins (RIPs) such as ricin, maize RIP, abrin, luffin, saporin, or bryodin; steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysteroid UDP glycosyl transferase, cholesterol oxidase, ecdysone inhibitors, HMG-COA reductase, ion channel blockers such as sodium or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, dibenzyl synthase , chitinases and glucanases.

In the context of the present invention, 6-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A, should definitely also be understood as hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly with a novel combination of different domains of these proteins (see, for example, WO 02/15701). Truncated toxins are known, such as truncated Cry1Ab. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are substituted. With such amino acid substitutions, sequences recognized by proteases not found in the natural toxin are preferably introduced into the toxin, for example, in the case of Cry3A055, a sequence recognized by cathepsin G is introduced into the Cry3A toxin (see WO 03/018810).

Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-A-0374753, WO 93/07278, WO 95/34656, EP-A-0427529, EP-A-451878 and WO 03/052073.

Methods for obtaining such transgenic plants are generally known to the person 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-0367474, EP-A-0401979 and WO 90/13651.

The toxin contained in the transgenic plants makes the plants resistant to harmful insects. Such insects can belong to any taxonomic group of insects, but are especially common among beetles (Coleoptera), diptera (Diptera) and moths (Lepidoptera). Transgenic plants containing one or more genes that encode for insect resistance and express one or more toxins are known and some are commercially available. Examples of such plants are YieldGard® (maize variety expressing Cry1Ab toxin); YieldGard Rootworm® (maize variety expressing Cry3Bb1 toxin); YieldGard Plus® (maize variety expressing Cry1Ab toxin and Cry3Bb1 toxin); Starlink® (maize variety expressing Cry9C toxin); Herculex I® (maize cultivar expressing Cry1Fa2 toxin and phosphinothricin N-acetyltransferase (PAT) enzyme to achieve tolerance to the herbicide ammonium glufosinate); NuCOTN 33B® (cotton variety expressing Cry1Ac toxin); Bollgard I® (cotton cultivar expressing Cry1Ac toxin); Bollgard II® (cotton cultivar expressing Cry1Ac toxin and Cry2Ab toxin); VipCot® (cotton variety expressing Vip3A toxin and Cry1Ab toxin); NewLeaf® (potato variety expressing Cry3A toxin); NatureGard® Agrisure® GT Advantage (GA21 with glyphosate tolerance), Agrisure® CB Advantage (Bt11 with corn borer (CB) resistance), and Protecta®. Additional examples of such transgenic crops are as follows.

1. Maize Bt11 from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 Saint Sauveur, France, registration number C/FR/96/05/10. A genetically modified Zea mays that has been rendered resistant to corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Maize Bt11 also expresses the PAT enzyme in a transgenic manner with tolerance to the herbicide ammonium glufosinate.

2. Maize Bt176 from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 Saint Sauveur, France, registration number C/FR/96/05/10. A genetically modified Zea mays that has been rendered resistant to corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of the Cry1Ab toxin. Maize Bt176 also expresses the PAT enzyme in a transgenic manner with tolerance to the herbicide ammonium glufosinate.

3. Maize MIR604 from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 Saint Sauveur, France, registration number C/FR/96/05/10. Maize that has been rendered insect resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by inserting a sequence recognized by the cathepsin G protease. The production of such transgenic maize plants is described in WO 03/018810.

4. Maize MON 863 from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses the Cry3Bb1 toxin and is resistant to some insects from the order Coleoptera.

5. Cotton IPC 531 from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02.

6. Maize 1507 from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize to express the Cry1F protein to achieve resistance to some insects of the order Lepidoptera and the PAT protein to achieve tolerance to the herbicide ammonium glufosinate.

7. Maize NK603 × MON 810 from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of hybrid maize varieties traditionally bred by crossing genetically modified varieties NK603 and MON 810. Maize NK603 × MON 810 transgenic expresses the CP4 EPSPS protein derived from Agrobacterium sp. strain CP4, which confers tolerance to the herbicide Roundup® (contains glyphosate); and Cry1Ab toxin, derived from Bacillus thuringiensis subsp. kurstaki, which confers tolerance to certain members of the order Lepidoptera, including the corn borer.

Transgenic insect-resistant crops are also described in the 2003 BATS report (Zentrum fur Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) (http://bats.ch). The term "crops" should be understood to include also crop plants that have been transformed using recombinant DNA techniques such that they are capable of synthesizing selective anti-pathogenic substances such as, for example, the so-called "pathogen-related proteins" (PRPs, see, for example, EP-A-0392225). Examples of such antipathogenic substances and transgenic plants capable of synthesizing such antipathogenic substances are known, for example, from EP-A-0392225, WO 95/33818 and EP-A-0353191. Methods for obtaining such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

Crop crops can also be modified for increased resistance to fungal (eg Fusarium, Anthracnose or Phytophthora), bacterial (eg Pseudomonas) or viral (eg potato leafroll virus, tomato spotted bronze virus, cucumber mosaic virus) pathogens.

Crops also include those with increased resistance to nematodes such as the soybean cyst nematode. Crops that are tolerant of abiotic stress include those that are more tolerant of drought, high salt, heat, cold, frost, or light exposure, such as through the expression of NF-YB or other proteins known in the art.

Anti-pathogenic substances that can be expressed by such transgenic plants include, for example, ion channel blockers such as sodium and calcium channel blockers, eg viral toxins KP1, KP4 or KP6; stilbene synthase; dibenzyl synthase; chitinases; glucanase; the so-called pathogenesis-related proteins (PRP; see, for example, EP-A-0392225); anti-pathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see, for example, WO 95/33818) or protein or polypeptide factors that play an active role in plant defense against pathogens (so-called "plant disease resistance genes", which described in WO 03/000906).

Additional applications for the compositions of the present invention are the protection of stored goods and storage areas and the protection of raw materials such as wood, fabrics, floor coverings or building materials, as well as health care applications, in particular the protection of humans, domestic animals and productive livestock from pests of this type.

The present invention also provides a method for controlling pests (such as mosquitoes and other disease vectors; see also http://www.who.int/malaria/vector_control/irs/en/). In one embodiment, a pest control method involves applying the compositions of the present invention to target pests, to their habitat, or to a surface or substrate by brushing, rolling, spraying, spreading, or dip dressing. As an example, the method of the present invention involves the application of IRS (Indoor Residual Pesticide Spraying) to a surface such as a wall, ceiling or floor surface. In another embodiment, the use of such compositions is contemplated in relation to a substrate such as a non-woven or woven material in the form of (or which may be used in the manufacture of) netting, clothing, bedding, curtains and tents.

In one embodiment, a method for controlling such pests involves applying a pesticidally effective amount of the compositions of the present invention to the target pests, to their habitat, or to a surface or substrate to provide effective residual pesticide activity on the surface or substrate. Such application of the pesticide composition of the present invention can be carried out by brushing, rolling, spraying, spreading or dip dressing. By way of example, the method of the present invention involves applying IRS to a surface such as a wall, ceiling or floor surface so as to provide effective residual pesticide activity on the surface. In another embodiment, the application of such compositions to a substrate, such as a woven material in the form of (or which may be used in the production of) netting, clothing, bedding, curtains and tents, is contemplated for pest control through residual action.

The substrates, including the nonwovens, woven fabrics or mesh to be processed, can be made from natural fibers such as cotton, raffia, jute, linen, sisal, burlap or wool, or from synthetic fibers such as polyamide, polyester, polypropylene, polyacrylonitrile or similar. Polyesters are particularly suitable. Methods for treating fabrics are known, for example, from WO 2008/151984, WO 2003/034823, US 5631072, WO 2005/64072, WO 2006/128870, EP 1724392, WO 2005113886 or WO 2007/090739.

Other fields of application of the compositions according to the present invention are the field of introduction into the tree / treatment of the trunk of all ornamental trees, as well as all varieties of fruit and nut trees.

In the area of injection/stem treatment, the compounds of the present invention are particularly useful against carpenter insects of the order Lepidoptera as mentioned above and of the order Coleoptera, especially against the carpenters listed in the following tables A and B.

The present invention can also be used to control any insect pest that may be present in lawn grass, including, for example, beetles, caterpillars, fire ants, mealybugs, millipedes, wood lice, mites, mole crickets, scale insects, felt mites, ixodid mites, pennitsy, Blissus insularis and beetle larvae. The present invention can be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults.

In particular, the present invention can be used to control insect pests that feed on turf grass roots, including beetle larvae (such as Cyclocephala spp. R. majalis), Cotinus spp. (e.g. shiny green beetle, C. nitida), Popillia spp. (e.g. Japanese beetle, P. japonica), Phyllophaga spp. (e.g. May/June beetle), Ataenius spp. ( e.g. Black turfgrass ataenius, A. spretulus), Maladera spp. (e.g. Asian garden beetle M. Castanea) and Tomarus spp.), mealybugs (Margarodes spp.), mole crickets (dark yellow, southern and short-winged; Scapteriscus spp. , Gryllotalpa africand) and larvae of long-legged mosquitoes (marsh weevil, Tipula spp.).

The present invention can also be used to control insect pests of turf grass that live in culm, including "marching worms" (such as grass cutworm Spodoptera frugiperda and meadow cutworm Pseudaletia unipuncta), winter cutworm caterpillars, weevils (Sphenophorus spp., such like S. venatus verstitus and S. parvulus) and meadow moths (such as Crambus spp. and tropical meadow moths, Herpetogramma phaeopteralis).

The present invention can also be used to control turf grass insects that live above ground and feed on turf grass leaves, including ground bugs (such as ground bugs, Blissus insularis), Bermuda grass mite (Eriophyes cynodoniensis), Antonina graminis), two-stripe chickweed (Propsapia bicincta), leafhoppers, caterpillars of the winter cutworm (family Noctuidae) and grass aphids.

The present invention can also be used to control other turf grass pests such as imported red fire ants (Solenopsis invicta) that create anthills on the turf surface.

With respect to hygiene, the compositions of the present invention are active against ectoparasites such as hard mites, soft mites, scabies, red beetles, flies (biting and licking), parasitic fly larvae, lice, hair lice, lice and fleas.

Examples of such parasites are:

from the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculus spp. and Phtirus spp., Solenopotes spp.;

from the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp.;

from 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., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.;

from the order Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.;

from the order Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.;

from the order Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattelagermanica and Supella spp.;

from subclass Acaria (Acarida) and orders Meta- and Mesostigmata, e.g. Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp. , Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Stemostoma spp. and Varroa spp.;

from the orders Actinedida (Prostigmata) and Acaridida (Astigmata), e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophoras spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.;

The compositions according to the present invention are also suitable for protection against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, adhesives, paints, paper and cardboard, leather, floor coverings and buildings.

The compositions according to the present invention can be used against, for example, 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 ctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec, Tryptodendron spec, Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec, and Dinoderus minutus, as well as Hymenoptera insects such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus augur, and termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and Coptotermes formosanus, and bristletails such as Lepisma saccharina.

The compounds of the present invention can be used as pesticides in unmodified form, but are generally formulated in various ways using formulation aids such as carriers, solvents and surfactants. Formulations may be in various physical forms, for example, powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent dragees, emulsifiable concentrates, microemulsifying concentrates, oil-in-water emulsions. , oily flowable formulations, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films, or in other forms known, for example, from Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can either be applied directly or diluted prior to use. Dilutions can be carried out, for example, with water, liquid fertilizers, micronutrients, biological organisms, oils or solvents. Formulations can be obtained, for example, by mixing the active ingredient with formulation auxiliaries to form compositions in the form of fine solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other excipients, for example, fine solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surfactants, or combinations thereof. The active ingredients may also be contained in very small microcapsules. Microcapsules contain the active ingredients in a porous carrier. This allows the active ingredients to be released into the environment in controlled amounts (eg slow release). Microcapsules typically have a diameter of 0.1 to 500 microns. They contain the active ingredients in an amount of from about 25 to 95% by weight of the weight of the capsule.

The active ingredients may be in the form of a monolithic solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. Encapsulating membranes may contain, for example, natural and synthetic rubbers, cellulose, styrene-butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art. Alternatively, very small microcapsules can be formed in which the active ingredient is contained in fine particle form in a solid matrix of base material, however, the microcapsules are not themselves encapsulated.

Formulation aids which are suitable for preparing the compositions of the present invention are known per se. Water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, acetic acid alkyl esters can be used as liquid carriers. , diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, Methyl simple ether of ethylene glycol, gamma-butyrolactone, glycerin glycerin, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecan, hexylene glycol, isoamilacetate, isobornial acetate, iso-octane, isoporone, isopylbenzole, isopropylmiristate, milk acid, laurealine acid, laurelamin, and lauserine acid, lauserine acid, and lauserine acid, and laurelain Tiloxide, methoxypropanol, methyl-amoamillet, methyl -isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichlorethylene, perchlorethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol and polyols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, and the like.

Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soy flour, pumice, wood flour, ground shells walnuts, lignin and the like.

A large number of surfactants can be successfully used in both solid and liquid formulations, especially those formulations that can be diluted with a carrier prior to use. Surfactants may be anionic, cationic, nonionic, or polymeric and may be used as emulsifiers, wetting agents, or suspending agents, or for other purposes. Exemplary surfactants include, for example, alkyl sulfate salts such as diethanol ammonium lauryl sulfate; salts of alkylarylsulfonates such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products such as nonylphenol ethyl oxylate; alcohol/alkylene oxide addition products such as tridecyl alcohol ethoxylate; soaps such as sodium stearate; salts of alkylnaphthalenesulfonates such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts such as sodium di(2-ethylhexyl)sulfosuccinate; esters of sorbitol such as sorbitoleate; quaternary amines such as lauryltrimethylammonium chloride, polyethylene glycol fatty acid esters such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide and salts of mono- and dialkyl phosphate esters; as well as additional substances described, for example, in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981).

Additional adjuvants that can be used in pesticide formulations include crystallization inhibitors, viscosity modifiers, suspending agents, colorants, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, neutralizing or pH modifying agents and buffers, inhibitors corrosion, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreezes, microbiocides, and liquid and solid fertilizers.

The compositions of the present invention may include an additive comprising vegetable or animal oil, mineral oil, alkyl esters of such oils, or mixtures of such oils and oil derivatives. The amount of oil additive in the composition of the present invention is usually from 0.01 to 10%, based on the mixture to be used. For example, the oil additive can be added to the spray tank at the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral or vegetable oils such as rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of vegetable oils such as methyl derivatives, or animal oils such as fish oil or beef tallow. Preferred oil additives include alkyl esters of C ₈ -C ₂₂ fatty acids, especially methyl derivatives of C ₁₂ -C ₁₈ fatty acids, for example methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from Compendium of Herbicide Adjuvants, ^10th Edition, Southern Illinois University, 2010.

Compositions of the present invention typically contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight of the compounds of the present invention and from 1 to 99.9% by weight of a formulation aid which preferably includes 0 to 25% by weight of a surfactant. Because commercial products can preferably be formulated as concentrates, the end user will typically use diluted formulations. Application rates vary widely and depend on soil properties, method of application, crop plant, pest to be controlled, prevailing climatic conditions and other factors determined by method of application, time of application and target crop. As a general guide, the compounds can be used at a rate of 1 to 2000 l/ha, in particular 10 to 1000 l/ha.

Preferred compositions may be characterized by the following compositions (wt.%).

Emulsifiable concentrates

active ingredient 1-95%, preferably 60-90% surfactant 1-30%, preferably 5-20% liquid carrier 1-80%, preferably 1-35%

Powdered preparations

active ingredient 0.1-10%, preferably 0.1-5% solid carrier 99.9-90%, preferably 99.9-99%

Suspension concentrates

active ingredient 5-75%, preferably 10-50% water 94-24%, preferably 88-30% surfactant 1-40%, preferably 2-30%

Wetted Powders

active ingredient 0.5-90%, preferably 1-80% surfactant 0.5-20%, preferably 1-15% solid carrier 5-95%, preferably 15-90%

Granules

active ingredient 0.1-30%, preferably 0.1-15% solid carrier 99.5-70%, preferably 97-85%

The following examples further illustrate but do not limit the present invention.

The combination is thoroughly mixed with excipients and the mixture is thoroughly ground in a suitable mill to obtain wettable powders that can be diluted with water to obtain a suspension with the desired concentration.

The combination is thoroughly mixed with excipients and the mixture is thoroughly ground in a suitable mill to obtain powders that can be used directly for seed treatment.

From this concentrate, by dilution with water, emulsions of any desired dilution can be obtained, which can be used for plant protection.

Ready-to-use pulverulent preparations are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressing of seeds.

The combination is mixed and ground with excipients and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

Finely ground combination in a mixing device is evenly applied to the kaolin moistened with polyethylene glycol. In this way, non-pulverized coated granules are obtained.

Suspension concentrate

The finely ground combination was thoroughly mixed with the excipients to give a suspension concentrate from which suspensions of any desired dilution could be obtained by dilution with water. Using such dilutions, live plants as well as plant propagation material can be treated and protected from microbial infestation by spraying, watering or dipping.

Flowable concentrate for seed treatment

The finely ground combination was thoroughly mixed with the excipients to give a suspension concentrate from which suspensions of any desired dilution could be obtained by dilution with water. Using such dilutions, live plants as well as plant propagation material can be treated and protected from microbial infestation by spraying, watering or dipping.

Slow release capsule suspension

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

Formulation types include emulsion concentrate (EC), suspension concentrate (SC), suspoemulsion (SE), capsule suspension (CS), water-dispersible granule (WG), emulsifiable granule (EG), water-in-oil emulsion (EO) , oil-in-water emulsion (EW), microemulsion (ME), oil dispersion (OD), oil-miscible fluid (OF), oil-miscible liquid (OL), soluble concentrate (SL), ultra-low volume suspension (SU), Ultra Low Volume Liquid (UL), Technical Concentrate (TK), Dispersible Concentrate (DC), Wettable Powder (WP), Soluble Granule (SG), or any other technically feasible formulation in combination with agriculturally acceptable adjuvants .

Receipt examples

"Mp" means the melting point in °C. Free radicals are methyl groups. ¹ H NMR measurements were recorded on a Brucker 400 MHz spectrometer, chemical shifts are given in ppm according to the TMS standard. The spectra measured in deuterated solvents are indicated. Any of the LCMS methods below were used to characterize compounds. The characteristic LCMS values obtained for each compound were the retention time ("Rt", written in minutes) and the measured content of the molecular ion (M+H) ⁺ or (M-H) ^- .

LCMS methods

Method 1. Standard 1

Spectra were recorded on a mass spectrometer from Waters (single quadrupole mass spectrometer SQD, SQDII) equipped with an electrospray source (polarity: positive and negative ions, capillary voltage: 3.00 kV, cone voltage range: 30 V, extractor voltage: 2.00 V, source temperature: 150°C, desolvation temperature: 350°C, cone gas flow: 50 l/h, desolvation gas flow: 650 l/h, mass range: 100-900 Da) and Acquity UPLC from Waters: two-component mixture pump, heated column section, diode array detector and ELSD detector. Column: UPLC HSS T3, 1.8 µm, 30×2.1 mm from Waters, temperature: 60° C., DAD wavelength range (nm): 210-500; solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; gradient: 10 to 100% B in 1.2 minutes; flow rate (ml/min.): 0.85.

Method 2. Standard length

Spectra were recorded on a mass spectrometer from Waters (single quadrupole mass spectrometer SQD, SQDII) equipped with an electrospray source (polarity: positive and negative ions), capillary voltage: 3.00 kV, cone voltage range: 30 V, extractor voltage : 2.00 V, source temperature: 150°C, desolvation temperature: 350°C, cone gas flow: 50 l/h, desolvation gas flow: 650 l/h, mass range: 100-900 Da) and Acquity UPLC from Waters: two-component mixture pump, heated column section, diode array detector, and ELSD detector. Column: UPLC HSS T3, 1.8 µm, 30×2.1 mm from Waters, temperature: 60° C., DAD wavelength range (nm): 210-500; solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; gradient: 10 to 100% B in 2.7 minutes; flow rate (ml/min.): 0.85.

Method 3. Standard length 2

Spectra were recorded on a mass spectrometer from Agilent Technologies (6410 Triple Quadrupole Mass Spectrometer) equipped with an electrospray source (polarity: switch between positive and negative polarity, capillarity: 4.00 kV, fragmentator 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 to 1.8 min. 0% A, 100% B, 2.2 to 2.5 min. 90% A, 10% B. Flow rate: 1.8 ml/min.

Method 4. Standard 2

Spectra were recorded on a mass spectrometer from Waters (Acquity SDS mass spectrometer) equipped with an electrospray source (polarity: switch between positive and negative polarity, capillarity: 3.00 kV, cone voltage: 41.00 V, source temperature: 150° C, desolvation gas flow rate: 1000 l/h, desolvation temperature: 500°C, cone gas flow rate: 50 l/h, 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; from 0.7 up to 1.3 min 0% A, 100% B, 1.4 to 1.6 min 90% A, 10% B. Flow rate 0.8 ml/min.

EXAMPLE P1. Preparation of 2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-2-methylpropanedinitrile (compound P1)

Stage 1. Preparation of 2-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]propanedinitrile (compound P7)

A microwave reactor vessel was charged with 2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (prepared according to WO 16096584) (5 .00 g, 12.0 mmol), propanedinitrile (0.830 ml, 13.2 mmol, 1.10 eq.), potassium hydroxide (2.02 g, 36.0 mmol, 3.00 eq.) and bis( triphenylphosphine)palladium(II) (420 mg, 0.60 mmol, 0.05 eq.). After addition of N-methylpyrrolidone (24 ml), the reaction mixture was degassed with argon for 5 min. The vessel was sealed and heated in an oil bath at 130° C. overnight. After cooling to room temperature, the reaction mixture was poured into water, the pH was carefully lowered with 2 M HCl and the aqueous phase was extracted twice with ethyl acetate. The combined organic phases were washed twice with water and these combined aqueous phases were again extracted three times with dichloromethane. A solid precipitated from the combined dichloromethane phases, which were filtered. The ethyl acetate and dichloromethane phases were combined, dried over sodium sulfate, filtered and concentrated in vacuo. The crude dark brown oil was purified by silica gel column chromatography eluting with pure ethyl acetate. Selected fractions were evaporated to give the title compound as a brown solid. LCMS (method 1): 403 (M+H) ⁺ ; retention time: 0.86 min.

Stage 2. Obtaining 2-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-2-methylpropanedinitrile (compound P8)

To a solution of 2-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]propanedinitrile (9.58 g, 10.7 mmol) in N,N-dimethylformamide (32 ml) under argon was added potassium carbonate (1.58 g, 11.3 mmol, 1.05 eq.) followed by dropwise addition of methyl iodide (1.00 ml, 16.1 mmol, 1.50 eq.). The resulting brown mixture was stirred at 40° C. for 2 hours. Additional potassium carbonate (148 mg, 1.07 mmol, 0.10 eq.) and methyl iodide (1.00 ml, 16.1 mmol, 1.50 eq.) were added and the reaction mixture was heated for an additional 3 hours at 40 °C. After completion of the reaction, the reaction mixture was cooled to room temperature and diluted with water. The aqueous phase was slightly acidified with 2M HCl and extracted twice with ethyl acetate. The combined organic phases were washed four times with water, dried over sodium sulfate, filtered and concentrated. The residue was subjected to silica gel column chromatography eluting with ethyl acetate in dichloromethane to give the title compound as a beige solid. LCMS (method 1): 417 (M+H) ⁺ ; retention time: 1.01 min.

Stage 3. Obtaining 2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-2-methylpropanedinitrile (compound P1)

In a solution of 2-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-2-methylpropandinitrile (100 mg, 0. 24 mmol) in dichloromethane (30 ml) in an argon atmosphere at 0°C was added 3-chloroperbenzoic acid (91 mg, 0.53 mmol, 2.2 eq.). After stirring for 30 min. at 0°C and then for 1 hour at room temperature, the reaction mixture was slowly extinguished by pouring into a saturated solution of sodium thiosulfate. The aqueous phase was extracted twice with ethyl acetate, the combined organic phases were dried over sodium sulfate, filtered and concentrated. The crude material was first triturated in diisopropyl ether and the resulting white solid was further purified by silica gel column chromatography eluting with ethyl acetate in dichloromethane to give the title compound as a white solid. LCMS (method 1): 449 (M+H) ⁺ ; retention time: 0.95 min.

EXAMPLE P2. Preparation of 2-[5-ethylsulfonyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]-2-methylpropanenitrile (compound P2)

Stage 1. Obtaining methyl 5-(1-cyano-1-methylethyl)-3-ethylsulfonylpyridine-2-carboxylate

Methyl 5-(cyanomethyl)-3-ethylsulfonylpyridine-2-carboxylate (prepared according to WO 16096584) (1.40 g, 5.22 mmol) was dissolved in DMF (21 ml) under argon. The reaction mixture was cooled to 0° C. and sodium hydride (480 mg, 12.5 mmol, 2.40 eq.) was added portionwise. The dark red reaction mixture was stirred for 30 minutes. at 0°C. This reaction mixture was added to a solution of methyl iodide (0.78 ml, 12.5 mmol, 2.40 eq.) in DMF (21 ml) at 0°C using a syringe. The resulting mixture was allowed to slowly warm to room temperature and stirred overnight. After completion of the reaction, the mixture was poured into a saturated ammonium chloride aqueous solution, and the aqueous phase was extracted with ethyl acetate. The organic phase was washed four times with water and then with brine, dried over sodium sulfate, filtered and concentrated. The crude material was purified by silica gel column chromatography eluting with ethyl acetate in cyclohexane to give the title compound as a white solid. LCMS (method 1): 297 (M+H) ⁺ ; retention time: 0.77 min.

Stage 2. Obtaining 5-(1-cyano-1-methylethyl)-3-ethylsulfonylpyridine-2-carboxylic acid

Methyl 5-(1-cyano-1-methylethyl)-3-ethylsulfonylpyridine-2-carboxylate (1.40 g, 4.72 mmol) was dissolved in tetrahydrofuran (40 ml) and water (13 ml). Lithium hydroxide (170 mg, 7.09 mmol, 1.50 eq.) was added and the reaction mixture was stirred at room temperature overnight. The reaction mixture was concentrated and the pH of the aqueous residue was adjusted to pH 1 with 1 M HCl. The resulting white suspension was filtered, the solid was washed with a minimum of cold water and dried under vacuum to give the desired product. The compound was used directly in the next step without further purification. LCMS (method 1): 283 (M+H) ⁺ ; retention time: 0.42 min.

Stage 3. Obtaining 5-(1-cyano-1-methylethyl)-3-ethylsulfonylpyridine-2-carbonyl chloride

Dissolve 5-(1-cyano-1-methylethyl)-3-ethylsulfonylpyridine-2-carboxylic acid (1.02 g, 3.61 mmol) in dichloromethane (24 ml) under argon atmosphere along with a catalytic amount of N,N-dimethylformamide . Oxalyl chloride (0.47 ml, 5.42 mmol, 1.50 eq.) was added dropwise via syringe. Then the reaction mixture was heated under reflux for 3 hours. After cooling to room temperature, the reaction mixture was evaporated to dryness. The resulting brown oil was used directly in the next step.

Step 4. Preparation of 5-(1-cyano-1-methylethyl)-3-ethylsulfonyl-N-[3-(methylamino)-6-(trifluoromethyl)pyridazin-4-yl]pyridine-2-carboxamide

Dissolve N-3-methyl-6-(trifluoromethyl)pyridazine-3,4-diamine (prepared according to WO 2016/116338) (150 mg, 0.78 mmol) in tetrahydrofuran (5.0 ml) along with N, N'-diisopropylethylamine. The reaction mixture was cooled to 0° C. and a solution of 5-(1-cyano-1-methylethyl)-3-ethylsulfonylpyridine-2-carbonyl chloride (258 mg, 1.1 eq.) in tetrahydrofuran (5.0 ml) was added dropwise. The reaction mixture was slowly warmed to room temperature and stirred overnight. The reaction mixture was slowly quenched by adding a saturated aqueous ammonium chloride solution, and the aqueous phase was extracted three times with ethyl acetate. The combined organic phases were washed with water, brine, dried over sodium sulfate, filtered and concentrated. The crude material was used directly in the next step without purification. LCMS (method 1): 425 (M+H) ⁺ ; retention time: 1.03 min.

Step 5. Preparation of 2-[5-ethylsulfonyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]-2-methylpropanenitrile

Dissolved 5-(1-cyano-1-methylethyl)-3-ethylsulfonyl-N-[3-(methylamino)-6-(trifluoromethyl)pyridazin-4-yl]pyridine-2-carboxamide (250 mg, 0.55 mmol ) in acetic acid (1.64 ml) and the reaction mixture was heated to 100°C for 5 hours. The reaction mixture was concentrated and the residue was evaporated with toluene to remove excess acetic acid. The crude material was purified by silica gel column chromatography eluting with ethyl acetate in cyclohexane followed by trituration in diethyl ether to give the title compound as a white solid. LCMS (method 1): 439 (M+H) ⁺ ; retention time: 0.93 min.

EXAMPLE P3. Preparation of 2-ethyl-2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]butanenitrile (compound P3)

Stage 1. Obtaining 2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]acetonitrile

A solution of 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (prepared according to WO 16096584) ( 6.00 g, 13.4 mmol) in N,N-dimethylformamide (27 ml). To this solution under argon was added trimethylsilylacetonitrile (2.77 ml, 20.0 mmol, 1.50 eq.), zinc fluoride (837 mg, 8.01 mmol, 0.60 eq.), xantphos (315 mg, 0 .53 mmol, 0.04 eq.) and Pd ₂ (dba) ₃ (250 mg, 0.27 mmol, 0.02 eq.). The vessel was hermetically sealed and heated at 140°C for 30 min. in the microwave. The reaction mixture was diluted with ethyl acetate, washed three times with water and once with brine. The organic layer was dried over sodium sulfate, filtered and concentrated. The crude material was purified by silica gel column chromatography eluting with methanol in dichloromethane to give the title compound as a white solid. LCMS (method 1): 410 (M+H) ⁺ ; retention time: 0.86 min.

Stage 2. Preparation of 2-ethyl-2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]butanenitrile

Dissolve 2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]acetonitrile (500 mg, 1.22 mmol) in N,N-dimethylformamide (5 ml) under argon. The reaction mixture was cooled to 0°C. Sodium hydride (66 mg, 1.71 mmol, 1.40 eq.) was added carefully in portions. The dark red reaction mixture was stirred at 0° C. for 30 minutes. The resulting solution was added to a solution of ethyl iodide (0.137 ml, 1.71 mmol, 1.40 eq.) in DMF (5 ml) under argon at 0°C using a syringe. The resulting mixture was slowly warmed to room temperature and stirred overnight. The mixture was then slowly poured into a saturated aqueous ammonium chloride solution and the aqueous phase was extracted with ethyl acetate. The organic phase was washed four times with water, then with brine, dried over sodium sulfate, filtered and concentrated. The crude material was purified by silica gel column chromatography eluting with ethyl acetate in cyclohexane to give the title compound as a white solid. LCMS (method 1): 466 (M+H) ⁺ ; retention time: 1.02 min.

EXAMPLE P4. Preparation of 2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]butanenitrile (compound P4)

Dissolved 2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]acetonitrile (prepared as described in step 1 of Example P3) (500 mg, 1.22 mmol) in N,N-dimethylformamide (5 ml) under argon. The reaction mixture was cooled to 0°C. Sodium hydride (66 mg, 1.71 mmol, 1.40 eq.) was added carefully in portions. The dark red reaction mixture was stirred at 0° C. for 30 minutes. The resulting reaction mixture was added dropwise to a solution of ethyl iodide (0.137 ml, 1.71 mmol, 1.40 eq.) in DMF (5 ml) under argon at 0°C. The resulting mixture was slowly warmed to room temperature and stirred overnight. The mixture was then slowly poured into a saturated aqueous ammonium chloride solution and the aqueous phase was extracted with ethyl acetate. The organic phase was washed four times with water, then with brine, dried over sodium sulfate, filtered and concentrated. The crude material was purified by silica gel column chromatography eluting with ethyl acetate in cyclohexane to give the title compound as a white solid. LCMS (method 1): 438 (M+H) ⁺ ; retention time: 0.94 min.

EXAMPLE P5. Preparation of 2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-2-methylpropanenitrile (compound P5)

Dissolved 2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]acetonitrile (prepared as described in step 1 of Example P3) (400 mg, 0.98 mmol) in N,N-dimethylformamide (4 ml) under argon. The reaction mixture was cooled to 0°C. Sodium hydride (52 mg, 1.37 mmol, 1.40 eq.) was added carefully in portions. The dark red reaction mixture was stirred at 0° C. for 30 minutes. The resulting mixture was added to a solution of methyl iodide (0.085 ml, 1.37 mmol, 1.40 eq.) in DMF (4 ml) under argon at 0°C. The resulting mixture was slowly warmed to room temperature and stirred overnight. The mixture was then slowly poured into a saturated aqueous ammonium chloride solution and the aqueous phase was extracted with ethyl acetate. The organic phase was washed four times with water, then with brine, dried over sodium sulfate, filtered and concentrated. The crude material was purified by silica gel column chromatography eluting with ethyl acetate in cyclohexane to give the title compound as a white solid. LCMS (method 1): 438 (M+H) ⁺ ; retention time: 0.93 min.

EXAMPLE P6. Preparation of 2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]propanenitrile (compound P6)

Dissolved 22-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]acetonitrile (obtained as described in step 1 of Example P3)

(400 mg, 0.98 mmol) in N,N-dimethylformamide (4 mL) under argon. The reaction mixture was cooled to 0°C. Sodium hydride (52 mg, 1.37 mmol, 1.40 eq.) was added carefully in portions. The dark red reaction mixture was stirred at 0° C. for 30 minutes. The resulting mixture was added to a solution of methyl iodide (0.085 ml, 1.37 mmol, 1.40 eq.) in DMF (4 ml) under argon at 0°C. The resulting mixture was slowly warmed to room temperature and stirred overnight. The mixture was then slowly poured into a saturated aqueous ammonium chloride solution and the aqueous phase was extracted with ethyl acetate. The organic phase was washed four times with water, then with brine, dried over sodium sulfate, filtered and concentrated. The crude material was purified by silica gel column chromatography eluting with ethyl acetate in cyclohexane to give the title compound as a white solid. LCMS (method 1): 424 (M+H) ⁺ ; retention time: 1.32 min.

Alternative procedure for the preparation of 2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]propanenitrile (compound P6)

Into a solution of ethyl 2-cyano-2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]propanoate (compound P9 ) (250 mg, 0.505 mmol, 1.00 eq.) in DMSO (2.0 ml) was added sodium chloride (298 mg, 5.05 mmol, 10.0 eq.) in water (1.0 ml) and the resulting the reaction mixture was heated to 120°C for 2 hours After cooling to room temperature, the reaction mixture was diluted with water (10 ml) and was extracted with ethyl acetate (3×20 ml). The combined organic layers were dried (Na ₂ SO ₄ ), filtered and concentrated in vacuo to give the crude product. Purification by flash chromatography (SiO2, 30% ethyl acetate/cyclohexane) gave the desired product. LCMS (method 4): 424 (M+H) ⁺ ; retention time: 0.91 min.

EXAMPLE P9. Preparation of ethyl 2-cyano-2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]propanoate (compound P9)

Stage 1. Preparation of ethyl 2-cyano-2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]acetate ( connections P25)

To a solution of 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (prepared according to WO 16096584) (5.40 g, 11.1 mmol, 1.00 eq.) in DMSO (50 ml) was added ethyl 2-cyanoacetate (3.85 g, 33.3 mmol, 3.00 eq.) followed by the addition of potassium carbonate (3.89 g , 27.8 mmol, 2.50 eq.), L-proline (261 mg, 2.23 mmol, 0.200 eq.) and copper(I) iodide (212 mg, 1.11 mmol, 0.100 eq.). The reaction mixture was heated to 150° C. for 3.5 hours. After cooling to room temperature, the reaction mixture was acidified with 2N HCl. HCl solution (50 ml), extracted with ethyl acetate (3×100 ml) and the combined organic layers were washed with brine, dried (sodium sulfate), filtered and compacted under reduced pressure to obtain the desired product. LCMS (method 4): 482 (M+H) ⁺ ; retention time: 0.95 min.

Stage 2. Preparation of ethyl 2-cyano-2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]propanoate ( connections P9)

To a solution of ethyl 2-cyano-2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]acetate (500 mg , 1.04 mmol, 1.00 eq.) in DMF (6.0 ml) was added potassium carbonate (175 mg, 1.25 mmol, 1.20 eq.) and iodomethane (78 μl, 180 mg, 1.25 mmol, 1.20 eq.). The resulting reaction mixture was stirred at room temperature overnight. The reaction mixture was then diluted with water (30 ml), extracted with ethyl acetate (3×30 ml) and the combined organic layers were dried over sodium sulfate, filtered and compacted under reduced pressure. The crude product was purified by flash chromatography (30% ethyl acetate/cyclohexane) to give the title compound. LCMS (method 4): 496 (M+H) ⁺ ; retention time: 1.00 min.

EXAMPLE P11. Preparation of 2-[3-ethylsulfanyl-4-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]phenyl]-2-methylpropanenitrile (compound P11)

Stage 1. Obtaining 4-bromo-2-ethylsulfanyl-N-[3-(methylamino)-6-(trifluoromethyl)pyridazin-4-yl]benzamide

N,N-diisopropylethylamine (1 07 ml, 807 mg, 6.25 mmol, 1.50 eq.). The reaction mixture was cooled to 0°C and a solution of 4-bromo-2-ethylsulfanylbenzoyl chloride (prepared according to WO 2016/026848) (1.28 g, 4.58 mmol, 1.10 eq.) in tetrahydrofuran (15 ml).

The reaction mixture was allowed to warm to room temperature and stirred overnight. The reaction mixture was slowly quenched by adding a saturated aqueous ammonium chloride solution, and the aqueous phase was extracted three times with ethyl acetate. The combined organic phases were washed with water, brine, dried over sodium sulfate, filtered and concentrated. The crude product was purified by flash chromatography (SiO ₂ , ethyl acetate/cyclohexane) to give the title compound. LCMS (method 1): 435 (M+H) ⁺ ; retention time: 1.05 min.

Stage 2. Obtaining 6-(4-bromo-2-ethylsulfanylphenyl)-7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazine

A round bottom flask equipped with a reflux condenser and magnetic stirrer was charged with a solution of 4-bromo-2-ethylsulfanyl-N-[3-(methylamino)-6-(trifluoromethyl)pyridazin-4-yl]benzamide (4.40 g, 10. 1 mmol, 1.00 eq.) in glacial acetic acid (30 ml) and the reaction mixture was heated to 100°C for 5 h. After cooling to room temperature, the reaction mixture was concentrated in vacuo and the remaining acetic acid was removed by repeated azeotropic distillation with toluene. The resulting crude product was purified by flash chromatography (SiO2, ethyl acetate/cyclohexane) to give the title compound. LCMS (method 1): 417 (M+H) ⁺ ; retention time: 1.09 min.

Step 3. Preparation of 2-[3-ethylsulfanyl-4-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]phenyl]acetonitrile

In an argon atmosphere, a 3-necked flask equipped with a magnetic stirrer and a reflux condenser was charged with a solution of 6-(4-bromo-2-ethylsulfanylphenyl)-7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazine (1 .30 g, 3.12 mmol, 1.00 eq.) in N,N-dimethylacetamide (16 ml). To this solution was added trimethylsilylacetonitrile (1.32 ml, 9.35 mmol, 3.00 eq.), zinc fluoride (193 mg, 1.87 mmol, 0.60 eq.), Xantphos (73.6 mg, 0.125 mmol , 0.0400 eq.) and Pd ₂ (dba) ₃ (44.6 mg, 0.046 mmol, 0.015 eq.). The reaction mixture was heated to 100° C. for 7 hours. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate, filtered through a pad of celite and washed three times with water and once with brine. The organic layers were dried over sodium sulfate, filtered and concentrated. The crude material was purified by flash column chromatography (SiO ₂ , ethyl acetate/cyclohexane) to give the title compound. LCMS (method 1): 378 (M+H) ⁺ ; retention time: 0.96 min.

Step 4 Preparation of 2-[3-ethylsulfanyl-4-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]phenyl]-2-methylpropanenitrile (compound P11)

A solution of 2-[3-ethylsulfanyl-4-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]phenyl]acetonitrile (192 mg, 0.509 mmol, 1.00 eq.) was cooled. ) in N,N-dimethylformamide (4 ml) under argon to 0°C. At this temperature, sodium hydride (60 wt% in mineral oil, 273 mg, 0.712 mmol, 1.40 eq.) was added portionwise. The dark red reaction mixture was stirred at 0° C. for 30 minutes. The resulting mixture was added via syringe to a solution of methyl iodide (44 μl, 101 mg, 0.712 mmol, 1.40 eq.) in DMF (4 ml) under argon at 0°C. The resulting mixture was slowly warmed to room temperature and stirred overnight. The mixture was then slowly poured into a saturated aqueous ammonium chloride solution and the aqueous phase was extracted with ethyl acetate. The organic phase was washed four times with water, then with brine, dried over sodium sulfate, filtered and concentrated. The crude material was purified by silica gel column chromatography eluting with ethyl acetate in cyclohexane to give the title compound. LCMS (method 1): 406 (M+H) ⁺ ; retention time: 1.03 min.

EXAMPLE P12. Preparation of 2-[3-ethylsulfonyl-4-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]phenyl]-2-methylpropanenitrile (compound P12)

To a solution of 2-[3-ethylsulfanyl-4-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]phenyl]-2-methylpropanenitrile (compound P11) (74.0 mg , 0.183 mmol, 1.00 eq.) in dichloromethane (2.0 ml) was added 3-chloroperbenzoic acid (75 wt.%, 92.4 mg, 0.384 mmol, 2.10 eq.) at room temperature. Stirring was continued for 18 hours at room temperature, after which a saturated solution of sodium thiosulfate (10 ml) and a saturated solution of NaHCO ₃ (10 ml) were added. The reaction mixture was diluted with dichloromethane (50 ml) and the mixture was stirred for 20 minutes. After separation of the aqueous layers, extraction with dichloromethane (3×20 ml), the combined organic layers were washed with water and brine, dried (Na ₂ SO ₄ ) and concentrated under reduced pressure. The resulting crude material was purified by flash chromatography (SiO ₂ , ethyl acetate/cyclohexane) to give the title compound. LCMS (method 1): 438 (M+H) ⁺ ; retention time: 0.93 min.

EXAMPLE P15. Preparation of 2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-2,2-difluoroacetonitrile (compound P15)

To a solution of 2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]acetonitrile (see example P3, step 1) (409 mg, 1.00 mmol, 1.00 eq.) in tetrahydrofuran (6.0 ml) was added Cs ₂ CO ₃ (391 mg, 1.20 mmol, 1.00 eq.) followed by the addition of N-fluorobenzenesulfonimide ( 315 mg, 1.00 mmol, 1.00 eq) under nitrogen. The reaction mixture was stirred at room temperature for 1 hour. The resulting reaction mixture was diluted with ethyl acetate (30 ml) and water (30 ml). After extraction with ethyl acetate (3×30 ml), the combined organic layers were washed with water (2×30 ml) and dried with sodium sulfate. Concentration under reduced pressure and purification by flash chromatography (SiO ₂ , ethyl acetate/cyclohexane) gave the title compound as a white solid. LCMS (method 4): 446 (M+H) ⁺ ; retention time: 1.05 min.

EXAMPLE P16. Preparation of 2-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]-2-methylpropanenitrile (compound P16)

A microwave reactor vessel was charged with 2-(4-bromo-2-ethylsulfanylphenyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (prepared according to WO 2016/026848) (500 mg, 1.20 mmol, 1.00 eq.), rac-BINAP (77.1 mg, 0.0120 mmol, 0.10 eq.) and Pd ₂ (dba) ₃ (56.7 mg, 0.0600 mmol, 0.0500 equiv.). After purging with argon, tetrahydrofuran (THF) (1.20 ml) and cyclopentyl methyl ether (CPME) (1.20 ml) were added, followed by isobutyronitrile (119 μl, 91.7 mg, 1.32 mmol, 1.10 eq. ). The vessel was closed with a stopper in an argon atmosphere and the resulting solution was cooled to -25°C. After stirring for 25 min. LiHMDS (1 M solution in THF, 1.32 ml, 1.32 mmol, 1.10 eq.) was added dropwise over 5 minutes. The resulting solution was allowed to warm to room temperature, after which it was heated to 80°C for 4 hours. After cooling to room temperature, the reaction mixture was quenched with water, filtered through a pad of celite and rinsed with ethyl acetate. The aqueous layer was extracted with ethyl acetate (3x) and the combined organic layers were washed with water and brine. Drying over sodium sulfate, filtration and concentration in vacuo gave a crude material which was purified by flash chromatography (SiO ₂ , ethyl acetate/cyclohexane) to give the title compound. LCMS (method 1): 405 (M+H) ⁺ ; retention time: 1.02 min.

EXAMPLE P17. Preparation of 2-[3-ethylsulfonyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]-2-methylpropanenitrile (compound P17)

To a solution of 2-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]-2-methylpropanenitrile (compound P16) (88.8 mg , 0.220 mmol, 1.00 eq.) in dichloromethane (1.0 ml) was added 3-chloroperbenzoic acid (75 wt.%, 103 mg, 0.461 mmol, 2.10 eq.) at room temperature. Stirring was continued for 18 hours at room temperature, after which a saturated solution of sodium thiosulfate (5 ml) and a saturated solution of NaHCO ₃ (5 ml) were added. The reaction mixture was diluted with dichloromethane (15 ml) and the mixture was stirred for 20 minutes. After separation of the aqueous layers, extraction with dichloromethane (3×10 ml), the combined organic layers were washed with water and brine, dried (Na ₂ SO ₄ ) and concentrated under reduced pressure. The resulting crude material was purified by flash chromatography (SiO ₂ , MeOH/dichloromethane) to give the title compound. LCMS (method 1): 437 (M+H) ⁺ ; retention time: 0.90 min.

EXAMPLE P19. Preparation of 2-[6-(6-bromo-3-methylimidazo[4,5-c]pyridin-2-yl)-5-ethylsulfonyl-3-pyridyl]-2-methylpropanenitrile (compound P19)

Stage 1. Obtaining methyl 5-(1-cyano-2-ethoxy-2-oxoethyl)-3-ethylsulfanylpyridine-2-carboxylate

Ethyl-2 -cyanoacetate (18.5 ml, 19.7 g, 174 mmol, 1.50 eq.), K ₂ CO ₃ (40.4 g, 290 mmol, 2.50 eq.) and tetrabutylammonium bromide (3.81 g , 11.6 mmol, 0.100 eq.). The resulting suspension was heated to 90° C. overnight. After cooling to room temperature, the reaction mixture was diluted with water (150 ml) and ethyl acetate (300 ml) and cooled to 0°C. 2 M HCl (200 ml) was slowly added to the stirred mixture (exothermic reaction) until a pH of 4-5 was reached. The aqueous layer was separated and extracted with ethyl acetate (3×500 ml). The combined organic layers were dried over sodium sulfate and concentrated in vacuo to give crude material. Recrystallization from ethanol gave the title compound as a beige solid. LCMS (method 1): 309 (M+H) ⁺ ; retention time: 0.86 min.

Stage 2. Obtaining methyl 5-(cyanomethyl)-3-ethylsulfanylpyridine-2-carboxylate

In a 3-necked flask equipped with a magnetic stirrer and a reflux condenser and gas outlet, into a solution of methyl 5-(1-cyano-2-ethoxy-2-oxoethyl)-3-ethylsulfanylpyridine-2-carboxylate (21.1 g, 68, 4 mmol, 1.00 eq.) in DMSO (210 ml) sodium chloride (40.0 g, 684 mmol, 10.0 eq.) was added first followed by water (105 ml). The reaction mixture was heated to an internal temperature of 125° C., at which strong gas evolution began. Stirring was continued for 3 hours. After cooling to room temperature, the reaction mixture was diluted with water (50 ml) and ethyl acetate (100 ml) was added. The aqueous layer was separated, extracted with ethyl acetate (3×200 ml) and the combined organic layers were washed with water, dried (Na ₂ SO ₄ ) and concentrated in vacuo to obtain the crude material. The crude product was used directly as received. LCMS (method 1): 237 (M+H) ⁺ ; retention time: 0.72 min

Stage 3. Obtaining 5-(1-cyano-1-methylethyl)-3-ethylsulfanylpyridine-2-carboxylic acid

Benzyltrimethylammonium chloride (998 mg , 4.23 mmol, 0.0500 eq.) and the resulting solution was cooled to 0°C. To this solution was slowly added an aqueous solution of NaOH (30 wt.%, 59 ml, 590 mmol, 7.0 eq.) followed by dropwise addition of iodomethane (10.5 ml, 24.0 g, 169 mmol, 2.00 eq. .) while maintaining the temperature between 0 and 5°C. Stirring at 0°C was continued for 5 hours, after which the reaction mixture was quenched by slow addition of 2 M HCl until pH 5 was reached. After adding ethyl acetate (250 ml) and stirring for 30 minutes. the layers were separated and the aqueous layer was extracted with ethyl acetate (3×100 ml). The combined organic layers were washed with water (50 ml) and brine (50 ml), dried (Na ₂ SO ₄ ) and evaporated. The crude material was purified by flash chromatography (SiO ₂ , ethyl acetate/cyclohexane) to give the title compound. LCMS (method 1): 251 (M+H) ⁺ ; retention time: 0.71 min.

Step 4. Preparation of N-[2-bromo-5-(methylamino)-4-pyridyl]-5-(1-cyano-1-methylethyl)-3-ethylsulfanylpyridine-2-carboxamide

To a solution of 5-(1-cyano-1-methylethyl)-3-ethylsulfanylpyridine-2-carboxylic acid (10.0 g, 40.0 mmol, 1.00 eq.) and a catalytic amount of N,N-dimethylformamide in dichloromethane ( 24 ml) under argon atmosphere, oxalyl chloride (5.23 ml, 7.61 g, 59.9 mmol, 1.50 eq.) was added dropwise via syringe. The reaction mixture was then heated to reflux temperature for 3 hours. After cooling to room temperature, the reaction mixture was evaporated to dryness. The resulting brown oil was dissolved in THF (190 ml) and slowly added at 0°C with an addition funnel to a solution of 6-bromo-N3-methylpyridine-3,4-diamine (prepared according to WO 2016/107831) (8 .43 g, 41.7 mmol, 1.04 eq.) and N,N-diisopropylethylamine (16.7 ml, 12.4 g, 94.9 mmol, 2.54 eq.) in THF (300 ml). The reaction mixture was allowed to warm to room temperature and stirring was continued for 20 hours. The reaction mixture was slowly quenched by adding a saturated aqueous ammonium chloride solution and the aqueous phase was extracted with ethyl acetate. The combined organic phases were washed with water, brine, dried over sodium sulfate, filtered and concentrated to give the title compound as a crude product. LCMS (method 1): 434 (M+H) ⁺ ; retention time: 0.82 min.

Step 5. Preparation of 2-[6-(6-bromo-3-methylimidazo[4,5-c]pyridin-2-yl)-5-ethylsulfanyl-3-pyridyl]-2-methylpropanenitrile (compound P23)

A solution of N-[2-bromo-5-(methylamino)-4-pyridyl]-5-(1-cyano-1-methylethyl)-3-ethylsulfanylpyridine-2-carboxamide was loaded into a round-bottom flask equipped with a reflux condenser and a magnetic stirrer. (13.0 g, 29.9 mmol, 1.00 eq.) in glacial acetic acid (90 ml) and the reaction mixture was heated to 100°C for 5 hours. After cooling to room temperature, the reaction mixture was concentrated in vacuo and the remaining acetic acid was removed by repeated azeotropic distillation with toluene. The resulting crude product was purified by flash chromatography (SiO2, ethyl acetate/cyclohexane) to give the title compound. LCMS (method 1): 416 (M+H) ⁺ ; retention time: 0.94 min.

Step 6. Preparation of 2-[6-(6-bromo-3-methylimidazo[4,5-c]pyridin-2-yl)-5-ethylsulfonyl-3-pyridyl]-2-methylpropanenitrile (compound P19)

To a solution of 2-[6-(6-bromo-3-methylimidazo[4,5-c]pyridin-2-yl)-5-ethylsulfanyl-3-pyridyl]-2-methylpropanenitrile (compound P23) (7.10 g , 17.1 mmol, 1.00 eq.) in dichloromethane (171 ml) was added in small portions 3-chloroperbenzoic acid (75 wt.%, 8.04 g, 35.0 mmol, 2.05 eq.) (exothermic reaction ) at 0°С. The reaction mixture was allowed to warm to room temperature and stirring was continued for 18 hours at room temperature, after which a saturated solution of sodium thiosulfate (100 ml) and a saturated solution of NaHCO ₃ (100 ml) were added. The reaction mixture was diluted with dichloromethane (150 ml) and the mixture was stirred for 20 minutes. After separation of the aqueous extraction layer with dichloromethane (3×10 ml), the combined organic layers were washed with saturated sodium thiosulfate solution (50 ml), saturated NaHCO ₃ solution (50 ml), followed by washing with water (50 ml) and brine (50 ml). Drying (Na ₂ SO ₄ ) and concentration under reduced pressure gave a crude material which was purified by flash chromatography (SiO ₂ , MeOH/dichloromethane) to give the title compound. LCMS (method 1): 448 (M+H) ⁺ ; retention time: 0.88 min.

EXAMPLE P20. Preparation of 2-[5-ethylsulfonyl-6-[3-methyl-6-(1,1,2,2,2-pentafluoroethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]- 2-methylpropanenitrile (compounds P20)

Stage 1. Preparation of 2-[5-ethylsulfonyl-6-(6-iodo-3-methylimidazo[4,5-c]pyridin-2-yl)-3-pyridyl]-2-methylpropanenitrile (compound P22)

To a solution of 2-[6-(6-bromo-3-methylimidazo[4,5-c]pyridin-2-yl)-5-ethylsulfonyl-3-pyridyl]-2-methylpropanenitrile (compound P19) (1.00 g , 2.23 mmol, 1.00 eq.) in 1,4-dioxane (11 ml) were added NaI (689 mg, 4.46 mmol, 2.00 eq.), CuI (224 mg, 1.12 mmol, 0500 eq.) and N,N'-dimethylethylenediamine (DMEDA) (0.29 ml, 0.24 g, 2.7 mmol, 1.2 eq.). The reaction mixture was heated to 100° C. for 40 hours. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate (50 ml) and 1 M aqueous NH ₃ was added. The aqueous layer was separated and extracted with ethyl acetate (2×20 ml). The combined organic layers were washed with sat. NaHCO ₃ , water and brine and dried (Na ₂ SO ₄ ). Concentration under reduced pressure gave the title compound. LCMS (method 1): 496 (M+H) ⁺ ; retention time: 0.90 min.

Stage 2. Obtaining 2-[5-ethylsulfonyl-6-[3-methyl-6-(1,1,2,2,2-pentafluoroethyl)imidazo[4,5-c]pyridin-2-yl]-3- pyridyl]-2-methylpropanenitrile (compounds P20)

To a solution of 2-[5-ethylsulfonyl-6-(6-iodo-3-methylimidazo[4,5-c]pyridin-2-yl)-3-pyridyl]-2-methylpropanenitrile (compound P22) (900 mg, 1 .82 mmol, 1.00 eq.) in DMF (6.5 ml) under argon was added (phen)CuC ₂ F ₅ [1360806-59-2]. The stirred reaction mixture was heated to 90° C. for 2 hours. After cooling to room temperature, the reaction mixture was filtered through celite and rinsed with ethyl acetate. The filtrate was washed with 28% aqueous ammonia (20 ml), using sat. NaHCO ₃ (20 ml), water (20 ml) and brine (20 ml). Drying over sodium sulfate, filtration and concentration under reduced pressure gave the crude product. Purification by flash chromatography (SiO ₂ , ethyl acetate/cyclohexane) gave the title compound as a white solid. LCMS (method 1): 488 (M+H) ⁺ ; retention time: 1.00 min.

EXAMPLE P23. Preparation of 2-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-2-methylpropanenitrile (compound P23)

A three-necked flask equipped with an addition funnel and an argon inlet was charged with isobutyronitrile (4.30 mL, 3.31 g, 47.9 mmol, 2.00 eq.) and cooled to -25°C. At this temperature, LiHMDS (1.0 M solution in THF, 72 ml, 64 g, 72 mmol, 3.0 eq.) was added dropwise over 30 minutes. with stirring, while the temperature of the reaction mixture was maintained at -25°C. Stirring at this temperature was continued for another 15 minutes. The resulting solution was then added dropwise to a stirred solution of 2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (prepared according to WO 2016 /026848) (10.0 g, 24.0 mmol, 1.00 eq.) in THF (50 ml) at -25° C. for a period of 1.5 h. Stirring at this temperature was continued for an additional 30 min. ., after which it was heated to room temperature. After an additional 1 hour at this temperature, the reaction mixture was quenched by slowly adding water (50 ml) and ethyl acetate (100 ml). The aqueous layer was separated and extracted with ethyl acetate (2×50 ml) and the combined organic layers were washed with brine and dried over sodium sulfate. Concentration in vacuo and purification by flash chromatography gave the desired title compound. LCMS (method 1): 406 (M+H) ⁺ ; retention time: 0.99 min.

The following mixtures of compounds of formula I with active ingredients are preferred (the abbreviation "TX" means "one compound selected from the group consisting of compounds described in tables 1-4 in accordance with the present invention"):

excipient selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX,

acaricide selected from the group consisting of 1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910) + TX, 2,4-dichlorophenylbenzenesulfonate (IUPAC name/Chemical Abstract Service) (1059 ) + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name) (1295) + TX, 4-chlorophenylphenylsulfone (IUPAC name) (981) + TX, abamectin (1) + TX, acequinocyl (3) + TX, acetoprol [CCN] + TX, acrinathrine (9) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, alpha-cypermethrin (202) + TX, amidithione (870) + TX, amidoflumet [CCN] + TX, amidothioate (872) + TX, amitone (875) + TX, amitone hydrooxalate (875) + TX, amitraz (24) + TX, aramite (881) + TX, arsenic oxide (882) + TX , AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azobenzene (IUPAC name) (888) + TX, azocyclotin (46) + TX, nitroate (889) + TX, benomyl (62) + TX, benoxaphos (alternative name) [CCN] + TX, benzoxymate (71) + TX, benzyl benzoate (IUPAC name) [CCN] + TX, biphenazate (74) + TX, bifenthrin (76) + TX, binapacryl (907) + TX, brofenvalerate (alternative name) + TX, bromocyclene (918) + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, bromopropylate (94) + TX, buprofezin (99) + TX, butocarboxym (103) + TX, butoxycarboxym (104) + TX, butylpyridabene (alternate name) + TX, calcium polysulfide (IUPAC name) (111) + TX , camphechlor (941) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbophenotion (947) + TX, CGA 50'439 (development code) (125) + TX, quinomethionate (126) + TX, chlorobenzide (959) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorfenapyr (130) + TX, chlorphenetol (968) + TX, chlorphenson (970) + TX, chlorphenesulfide (971) + TX, chlorphenvinphos (131) + TX, chlorobenzilate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, chlorpyrifos -methyl (146) + TX, chlorothiophos (994) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, clofentezin (158) + TX, closantel (alternative name) [CCN] + TX Coumaphos (174) + TX Crotamiton (alternate name) [CCN] + TX Crotoxyphos (1010) + TX Kufraneb (1013) + TX Cyantoate (1020) + TX Cyflumethophene (CAS Registration No. : 400882-07-7) + TX, cyhalothrin (196) + TX, cyhexatin (199) + TX, cypermethrin (201) + TX, DCPM (1032) + TX, DDT (219) + TX, demefion (1037) + TX, demefion-O (1037) + TX, demefion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-O (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S-methyl (224) + TX, demeton-S-methylsulfone (1039) + TX, diafenthiuron (226) + TX, dialyphos (1042) + TX , diazinon (227) + TX, dichlofluanide (230) + TX, dichlorphos (236) + TX, diclifos (alternative name) + TX, dicofol (242) + TX, dicrotophos (243) + TX, dienochlor (1071) + TX , dimefoxa (1081) + TX, dimethoate (262) + TX, dinactin (alternative name) (653) + TX, dinex (1089) + TX, dinex-diclexin (1089) + TX, dinobuton (269) + TX, dinocap (270) + TX, dinocapa-4 [CCN] + TX, dinocapa-6 [CCN] + TX, dinoctone (1090) + TX, dinopentone (1092) + TX, dinosulfone (1097) + TX, dinoterbone (1098) + TX, dioxathione (1102) + TX, diphenylsulfone (IUPAC name) (1103) + TX, disulfiram (alternate name) [CCN] + TX, disulfotone (278) + TX, DNOC (282) + TX, dofenapine (1113) + TX, doramectin (alternative name) [CCN] + TX, endosulfan (294) + TX, endothione (1121) + TX, EPN (297) + TX, eprinomectin (alternative name) [CCN] + TX, ethione (309) + TX, ethoate-methyl (1134) + TX, ethoxazole (320) + TX, etrymphos (1142) + TX, fenazaflora (1147) + TX, phenazquine (328) + TX, fenbutatin oxide (330) + TX, fenothiocarb ( 337) + TX, fenpropatrin (342) + TX, fenpyrad (alternative name) + TX, fenpyroximate (345) + TX, phenzone (1157) + TX, fentripanyl (1161) + TX, fenvalerate (349) + TX, fipronil ( 354) + TX, fluacripyrim (360) + TX, fluazuron (1166) + TX, flubenzimine (1167) + TX, flucycloxuron (366) + TX, flucitrinate (367) + TX, fluenethyl (1169) + TX, flufenoxuron (370 ) + TX, flumethrin (372) + TX, fluorobenzide (1174) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formotion (1192) + TX, formparanate (1193) + TX, gamma-HCH (430) + TX, gliodin (1205) + TX, halfenprox (424) + TX, heptenophos (432) + TX, hexadecylcyclopropanecarboxylate (name after IUPAC/Chemical Abstract Service) (1216) + TX, hexythiazoxa (441) + TX, iodomethane (IUPAC name) (542) + TX, isocarbophos (alternate name) (473) + TX, isopropyl-O-(methoxyaminothiophosphoryl) salicylate (IUPAC name) (473) + TX, ivermectin (alternate name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, iodophenphos (1248) + TX, lindane (430) + TX, lufenuron (490) + TX, malathion (492) + TX, malonoben (1254) + TX, mecarbam (502) + TX, mephospholane (1261) + TX, mesulfene (alternative name) [CCN] + TX, methacriphos ( 1266) + TX, methamidophos (527) + TX, metidathione (529) + TX, methiocarb (530) + TX, methomyl (531) + TX, methyl bromide (537) + TX, metolcarb (550) + TX, mevinphos (556 ) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin-oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, monocrotophos (561) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naleda (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) + TX, nifluridide (1309) + TX, niccomycins (alternative name) [CCN] + TX, nitrilecarb (1313) + TX, complex of nitrilecarb and zinc chloride 1:1 (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxideprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX , petroleum oils (alternative name) (628) + TX, phenkapton (1330) + TX, fentoate (631) + TX, phorate (636) + TX, fosalone (637) + TX, phospholane (1338) + TX, phosmet ( 638) + TX, phosphamidon (639) + TX, phoxim (642) + TX, pyrimiphos-methyl (652) + TX, polychloroterpenes (traditional name) (1347) + TX, polynactins (alternative name) (653) + TX, proclonol (1350) + TX, profenophos (662) + TX, promacyl (1354) + TX, propargyte (671) + TX, propetamphos (673) + TX, propoxur (678) + TX, protidathione (1360) + TX, protoate (1362) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridafenthione (701) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, quinalphos (711) + TX, quinthiophos (1381) + TX, R-1492 (development code) (1382) + TX, RA-17 (development code) (1383) + TX, rotenone (722 ) + TX, shradana (1389) + TX, sebuphos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, sofamide (1402) + TX, spirodiclofen (738 ) + TX, spiromesifene (739) + TX, SSI-121 (development code) (1404) + TX, sulfiram (alternative name) [CCN] + TX, sulfluramide (750) + TX, sulfotepa (753) + TX, sulfur (754) + TX, SZI-121 (development code) (757) + TX, tau-fluvalinate (398) + TX, tebufenpyrad (763) + TX, TERP (1417) + TX, terbama (alternate name) + TX, tetrachlorvinphos (777) + TX, tetradiphon (786) + TX, tetranactin (alternate name) (653) + TX, tetrasula (1425) + TX, thiafenox (alternative name) + TX, thiocarboxym (1431) + TX, thiophanox (800 ) + TX, thiomethone (801) + TX, thioquinox (1436) + TX, thuringiensin (alternative name) [CCN] + TX, triamiphos (1441) + TX, triarathene (1443) + TX, triazophos (820) + TX, triazuron (alternate name) + TX, trichlorfon (824) + TX, triphenophos (1455) + TX, trinactin (alternative name) (653) + TX, vamidothione (847) + TX, vaniliprol [CCN] and YI-5302 (code compounds) + TX,

algaecide selected from the group consisting of betoxazine [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutrin [CCN] + TX, dichlon (1052) + TX , dichlorophene (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamide (1379) + TX , simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX,

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

avicid selected from the group consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridine-4-amine (IUPAC name) (23) and strychnine (745) + TX ,

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, dichlorophene (232) + TX, dipyrithione (1105) + TX, dodicine (1112) + TX, phenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrarhafen (alternative name) [CCN] + TX, kasugamycin ( 483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrine (580) + TX, octylinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, teclophthalam (766) + TX and thiomersal (alternative name) [CCN] + TX,

a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis (alternative name) (33) + TX, Aphidius colemani ( alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide ( scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51) + TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51) + TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alternative name) (53 ) + TX, Beauveria brongniartii (alternative name) (54) + TX, Chrysoperla cornea (alternative name) (151) + TX, Cryptolaemus montrouzieri (alternative name) (178) + TX, Cydia pomonella GV (alternative name) (191) + TX, Dacnusa sibirica (alternative name) (212) + TX, Diglyphus isaea (alternative name) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus (alternative name) (300) + TX , Helicoverpa zea NPV (alternative name) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alternative name) (433) + TX, Hippodamia convergens (alternative name) (442) + TX, Leptomastix dactylopii (alternative name) (488 ) + TX, Macrolophus caliginosus (alternate name) (491) + TX, Mamestra brassicae NPV (alternative name) (494) + TX, Metaphycus helvolus (alternative name) (522) + TX, Metarhizium anisopliae var. acridum (scientific name) ( 523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. lecontei NPV (alternative name) (575) + TX, Orius spp. (alternative name) (596) + TX, Paecilomyces fumosoroseus (alternative name) (613) + TX, Phytoseiulus persimilis (alternative name) (644) + TX, multicapsid nuclear polyhedrosis virus Spodoptera exigua (scientific name) (741) + TX, Steinernema bibionis (alternative name) (742) + TX, Steinernema carpocapsae (alternative name) (742) + TX, Steinernema feltiae (alternative name) (742) + TX, Steinernema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinernema riobravis (alternative name) (742) + TX, Steinernema scapterisci (alternative name) (742) + TX, Steinernema spp. (alternative name) (742) + TX, Trichogramma spp. (alternative name) (826) + TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848) + TX,

a soil sterilizer selected from the group consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX,

a chemosterilizer selected from the group consisting of afolate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hemps [CCN] + TX, meteps [CCN] + TX, methiotepa [CCN] + TX, methyl folate [CCN] + TX, morzide [CCN] + TX, penfluron ( alternative name) [CCN] + TX, tepas [CCN] + TX, thiochempas (alternative name) [CCN] + TX, thiotepas (alternative name) [CCN] + TX, tretamine (alternative name) [CCN] and uredepas (alternative name) name) [CCN] + TX,

insect pheromone selected from the group consisting of (E)-dec-5-en-1-yl acetate with (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-ylacetate (IUPAC name) (779) + TX, (Z)-dodec-7-en-1-ylacetate (IUPAC name) (285) + TX, (Z)-hexadec-11-enal (IUPAC name) (436) + TX, (Z)-hexadec-11-en-1-ylacetate (IUPAC name) (437) + TX, (Z)-hexadec- 13-en-11-yn-1-yl acetate (IUPAC name) (438) + TX, (Z)-eicos-13-en-10-one (IUPAC name) (448) + TX, (Z)- tetradec-7-en-1-ala (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)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283) + TX, (9Z,11E )-tetradeca-9,11-dien-1-ylacetate (IUPAC name) (780) + TX, (9Z,12E)-tetradeca-9,12-dien-1-ylacetate (IUPAC name) (781) + TX, 14-methyloctadec-1-ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one (IUPAC name) (544) + TX, alpha-multistriatin ( alternative name) [CCN] + TX, brevicomina (alternative name) [CCN] + TX, caudelura (alternative name) [CCN] + TX, codlemona (alternative name) (167) + TX, quelura (alternative name) (179) + TX, disparlur (277) + TX, dodec-8-en-1-ylacetate (IUPAC name) (286) + TX, dodec-9-en-1-yl acetate (IUPAC name) (287) + TX, dodeca-8 + TX, 10-dien-1-yl acetate (IUPAC name) (284) + TX, dominicalura (alternative name) [CCN] + TX, ethyl 4-methyloctanoate (IUPAC name) (317) + TX , eugenol (alternative name) [CCN] + TX, frontalina (alternative name) [CCN] + TX, gossyplura (alternative name) (420) + TX, grandlura (421) + TX, grandlura I (alternative name) (421) + TX, grandlura II (alternative name) (421) + TX, grandlura III (alternative name) (421) + TX, grandlura IV (alternative name) (421) + TX, hexalura [CCN] + TX, ipsdienol (alternative name) ) [CCN] + TX, ipsenol (alternative name) [CCN] + TX, japonilura (alternative name) (481) + TX, lineatin (alternative name) [CCN] + TX, litlura (alternative name) [CCN] + TX , luplura (alternate name) [CCN] + TX, medlura [CCN] + TX, megatomoic acid (alternative name) [CCN] + TX, methyleugenol (alternative name) (540) + TX, muscalura (563) + TX, octadeca -2,13-dien-1-ylacetate (IUPAC name) (588) + TX, octadeca-3,13-dien-1-ylacetate (IUPAC name) (589) + TX, orfralur (alternate name) [CCN ] + TX, oryctalura (alternative name) (317) + TX, ostramona (alternative name) [CCN] + TX, siglura [CCN] + TX, sordidina (alternative name) (736) + TX, sulcatol (alternative name) [ CCN] + TX, tetradeyl-11-en-1-ylacetate (IUPAC name) (785) + TX, trimedlure (839) + TX, trimedlure A (alternative name) (839) + TX, trimedlure B ₁ (alternative name ) (839) + TX, trimedlura B ₂ (alternative name) (839) + TX, trimedlura C (alternative name) (839) and trunk-cola (alternative name) [CCN] + TX,

insect repellant 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, diethyltoluamide [CCN] + TX, dimethylcarbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethylhexanediol (1137 ) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methyl neodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,

an insecticide selected from the group consisting of 1-dichloro-1-nitroethane (IUPAC/Chemical Abstract Service name) (1058) + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane (name IUPAC) (1056), + TX, 1,2-dichloropropane (IUPAC/Chemical Abstract Service name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1-bromo-2-chloroethane (IUPAC/Chemical Abstract Service name) (916) + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451) + TX, 2,2-dichlorovinyl-2-ethylsulfinylethylmethyl phosphate (IUPAC name) (1066) + TX, 2-(1,3-dithiolan-2-yl)phenyldimethylcarbamate (IUPAC/Chemical Abstract Service name) (1109) + TX, 2-(2-butoxyethoxy)ethylthiocyanate (IUPAC/Chemical Abstract Service name) (935) + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenylmethylcarbamate (IUPAC/Chemical Abstract Service name) Chemical Abstract Service) (1084) + TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986) + TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984) + TX, 2 -imidazolidone (IUPAC name) (1225) + TX, 2-isovalerylindane-1,3-dione (IUPAC name) (1246) + TX, 2-methyl(prop-2-ynyl)aminophenylmethylcarbamate (IUPAC name) ( 1284) + TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433) + TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917) + TX, 3-methyl-1-phenylpyrazole-5 -yldimethylcarbamate (IUPAC name) (1283) + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate (IUPAC name) (1285) + TX, 5,5-dimethyl-3-oxocyclohex -1-enyldimethylcarbamate (IUPAC name) (1085) + TX, abamectin (1) + TX, acephate (2) + TX, acetamiprid (4) + TX, acethione (alternative name) [CCN] + TX, acetoprol [CCN ] + TX, acrinathrine (9) + TX, acrylonitrile (IUPAC name) (861) + TX, alanicarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, aldrin (864) + TX , allethrin (17) + TX, allosamidine (alternative name) [CCN] + TX, allixicarb (866) + TX, alpha-cypermethrin (202) + TX, alpha-ecdysone (alternative name) [CCN] + TX, aluminum phosphide (640) + TX, amidithione (870) + TX, amidothioate (872) + TX, aminocarb (873) + TX, amiton (875) + TX, amitone hydrooxalate (875) + TX, amitraz (24) + TX, anabasine (877) + TX, atidathione (883) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azadirachtin (alternative name) (41) + TX, azamethiphos (42) + TX, azinphos -ethyl (44) + TX, azinphos-methyl (45) + TX, nitrogenate (889) + TX, Bacillus thuringiensis delta-endotoxins (alternative name) (52) + TX, barium hexafluorosilicate (alternative name) [CCN] + TX , barium polysulfide (IUPAC/Chemical Abstract Service name) (892) + TX, bartryne [CCN] + TX, Bayer 22/190 (development code) (893) + TX, Bayer 22408 (development code) (894) + TX , bendiocarb (58) + TX, benfuracarb (60) + TX, bensultap (66) + TX, beta-cyfluthrin (194) + TX, beta-cypermethrin (203) + TX, bifenthrin (76) + TX, bioallethrin (78 ) + TX, bioallethrin-S-cyclopentenyl isomer (alternative name) (79) + TX, bioethanomethrin [CCN] + TX, biopermethrin (908) + TX, bioresmethrin (80) + TX, bis(2-chloroethyl)ether (name according to IUPAC) (909) + TX, bistrifluron (83) + TX, borax (86) + TX, brofenvalerate (alternative name) + TX, bromfenvinphos (914) + TX, bromocyclene (918) + TX, bromine-DDT (alternative name) name) [CCN] + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, bufencarb (924) + TX, buprofezin (99) + TX, butacarb (926) + TX, butathiophos (927) + TX, butocarboxym (103) + TX, butonate (932) + TX, butoxycarboxym (104) + TX, butylpyridaben (alternative name) + TX, cadusaphos (109) + TX, calcium arsenate [CCN] + TX, calcium cyanide (444) ) + TX, calcium polysulfide (IUPAC name) (111) + TX, camphechlor (941) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbon disulfide (IUPAC name /Chemical Abstract Service) (945) + TX, carbon tetrachloride (IUPAC name) (946) + TX, carbophenothion (947) + TX, carbosulfan (119) + TX, kartap (123) + TX, kartap hydrochloride (123) + TX, cevadin (alternate name) (725) + TX, chlorbicyclene (960) + TX, chlordane (128) + TX, chlordecone (963) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorethoxyphos (129) + TX, chlorfenapyr (130) + TX, chlorfenvinphos (131) + TX, chlorfluazuron (132) + TX, chlormephos (136) + TX, chloroform [CCN] + TX, chloropicrin (141) + TX, chlorphoxime ( 989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, chromafenoside (150) + TX, cinerin I (696) + TX, cynerin II (696) + TX, cynerins (696) + TX, cis-resmethrin (alternative name) + TX, cismetrin (80) + TX, clocitrin (alternative name) + TX, cloetocarb (999) + TX, closantel (alternative name) name) [CCN] + TX, clothianidin (165) + TX, copper acetoarsenite [CCN] + TX, copper arsenate [CCN] + TX, copper oleate [CCN] + TX, coumaphos (174) + TX, kumitoate (1006) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, crufomat (1011) + TX, cryolite (alternative name) (177) + TX, CS 708 (development code) (1012) + TX , cyanofenphos (1019) + TX, cyanophos (184) + TX, cyantoate (1020) + TX, cyclethrin [CCN] + TX, cycloprothrin (188) + TX, cyfluthrin (193) + TX, cyhalothrin (196) + TX, cypermethrin (201) + TX, cyfenotrin (206) + TX, cyromazine (209) + TX, cythioate (alternative name) [CCN] + TX, d-limonene (alternative name) [CCN] + TX, d-tetramethrin (alternative name) name) (788) + TX, DAEP (1031) + TX, dazomet (216) + TX, DDT (219) + TX, decarbofuran (1034) + TX, deltamethrin (223) + TX, demefion (1037) + TX, demefion-O (1037) + TX, demefion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-O (1038) + TX, demeton-O-methyl (224 ) + TX, demeton-S (1038) + TX, demeton-S-methyl (224) + TX, demeton-S-methylsulfone (1039) + TX, diafenthiuron (226) + TX, dialyphos (1042) + TX, diamidafos (1044) + TX, diazinon (227) + TX, dicaptone (1050) + TX, dichlorfenthion (1051) + TX, dichlorphos (236) + TX, diclifos (alternative name) + TX, dicresyl (alternative name) [CCN] + TX, dicrotophos (243) + TX, dicyclanil (244) + TX, dieldrin (1070) + TX, diethyl-5-methylpyrazol-3-ylphosphate (IUPAC name) (1076) + TX, diflubenzuron (250) + TX , dilora (alternative name) [CCN] + TX, dimefluthrin [CCN] + TX, dimefox (1081) + TX, dimethane (1085) + TX, dimethoate (262) + TX, dimetrin (1083) + TX, dimethylvinphos (265 ) + TX, dimethylan (1086) + TX, dinoseb (1089) + TX, dinex-diclexin (1089) + TX, dinoprop (1093) + TX, dinosam (1094) + TX, dinoseb (1095) + TX, dinotefuran ( 271) + TX, diofenolan (1099) + TX, dioxabenzophos (1100) + TX, dioxacarb (1101) + TX, dioxathion (1102) + TX, disulfotone (278) + TX, diticrophos (1108) + TX, DNOC (282 ) + TX, doramectin (alternative name) [CCN] + TX, DSP (1115) + TX, ecdysterone (alternative name) [CCN] + TX, EI 1642 (development code) (1118) + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, EMPC (1120) + TX, empentrin (292) + TX, endosulfan (294) + TX, endothion (1121) + TX, endrin (1122) + TX, EPVR (1123) + TX, EPN (297) + TX, epophenonan (1124) + TX, eprinomectin (alternative name) [CCN] + TX, esfenvalerate (302) + TX, ethaphos (alternative name) [CCN] + TX, ethiofencarb (308) + TX, ethione (309) + TX, ethiprol (310) + TX, ethoate-methyl (1134) + TX, etoprofos (312) + TX, ethyl formate (IUPAC name) [CCN] + TX, ethyl-DDD (alternative name ) (1056) + TX, ethylene dibromide (316) + TX, ethylene dichloride (chemical name) (1136) + TX, ethylene oxide [CCN] + TX, ethophenprox (319) + TX, etrymphos (1142) + TX, EXD (1143) + TX, famfur (323) + TX, fenamiphos (326) + TX, fenazaflora (1147) + TX, fenchlorphos (1148) + TX, fenetacarb (1149) + TX, fenfluthrin (1150) + TX, fenitrothion (335) + TX, fenobucarb (336) + TX, fenoxacrim (1153) + TX, fenoxycarb (340) + TX, fenpyrythrin (1155) + TX, fenpropatrin (342) + TX, fenpyrad (alternative name) + TX, fensulfothion (1158) + TX, fenthion (346) + TX, fenthion-ethyl [CCN] + TX, fenvalerate (349) + TX, fipronil (354) + TX, flonamide (358) + TX, flubendiamide (CAS registration number: 272451-65-7 ) + TX, flucofuron (1168) + TX, flucycloxuron (366) + TX, flucitrinate (367) + TX, fluenetil (1169) + TX, flufenerim [CCN] + TX, flufenoxuron (370) + TX, flufenprox (1171) + TX, flumethrin (372) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, phonophos (1191) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX , formotion (1192) + TX, formparanate (1193) + TX, phosmethylan (1194) + TX, fospirate (1195) + TX, fostiazate (408) + TX, fostiethane (1196) + TX, furatiocarb (412) + TX, furethrin (1200) + TX, gamma-cyhalothrin (197) + TX, gamma-HCH (430) + TX, guasatin (422) + TX, guasatin acetates (422) + TX, GY-81 (development code) (423) + TX, halfenprox (424) + TX, halofenoside (425) + TX, HCH (430) + TX, HEOD (1070) + TX, heptachlor (1211) + TX, heptenophos (432) + TX, heterophos [CCN] + TX, hexaflumuron (439) + TX, HHDN (864) + TX, hydramethylnon (443) + TX, hydrogen cyanide (444) + TX, hydroprene (445) + TX, hiquincarb (1223) + TX, imidacloprid (458) + TX , imiprothrin (460) + TX, indoxacarb (465) + TX, iodomethane (IUPAC name) (542) + TX, IPSP (1229) + TX, isazophos (1231) + TX, isobenzane (1232) + TX, isocarbophos ( alternative name) (473) + TX, isodrine (1235) + TX, isofenphos (1236) + TX, isolane (1237) + TX, isoprocarb (472) + TX, isopropyl-O-(methoxyaminothiophosphoryl) salicylate (IUPAC name) (473) + TX, isoprothiolane (474) + TX, isothioate (1244) + TX, isoxathion (480) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696 ) + TX, iodophenophos (1248) + TX, juvenile hormone I (alternative name) [CCN] + TX, juvenile hormone II (alternative name) [CCN] + TX, juvenile hormone III (alternative name) [CCN] + TX, kelevana (1249) + TX, kinoprene (484) + TX, lambda-cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepimectin (CCN) + TX, leptophos (1250) + TX, lindane (430) + TX, lyrimphos (1251) + TX, lufenuron (490) + TX, lithidation (1253) + TX, m-cumenylmethylcarbamate (IUPAC name) (1014) + TX, magnesium phosphide (IUPAC name) (640) + TX, malathion (492) + TX, malonobene (1254) + TX, mazidox (1255) + TX, mecarbam (502) + TX, mecarfon (1258) + TX, menasone (1260) + TX, mephospholane (1261) + TX, chloride mercury (513) + TX, mesulfenphos (1263) + TX, metaflumizone (CCN) + TX, metham (519) + TX, metam-potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methacryphos (1266) + TX, methamidophos (527) + TX, methanesulfonyl fluoride (IUPAC/Chemical Abstract Service name) (1268) + TX, metidathione (529) + TX, methiocarb (530) + TX, methocrotophos (1273) + TX , methomyl (531) + TX, methoprene (532) + TX, methoxybutyl (1276) + TX, methothrine (alternative name) (533) + TX, methoxychlor (534) + TX, methoxyfenoside (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methyl chloroform (alternative name) [CCN] + TX, methylene chloride [CCN] + TX, metofluthrin [CCN] + TX, metolcarb (550) + TX, methoxadiazon (1288) + TX, mevinfosa (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafoxa (1293) + TX, mirex (1294) + TX, monocrotophos (561) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naphtalophos (alternative name) [CCN] + TX, naleda (567) + TX, naphthalene (IUPAC/Chemical name) abstract service) (1303) + TX, NC-170 (development code) (1306) + TX, NC-184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (578) + TX, nifluridide (1309 ) + TX, nitenpyram (579) + TX, nithiazine (1311) + TX, nitrilacarb (1313) + TX, complex of nitrilacarb and zinc chloride 1:1 (1313) + TX, NNI-0101 (compound code) + TX, NNI -0250 (compound code) + TX, nornicotine (traditional name) (1319) + TX, novaluron (585) + TX, noviflumuron (586) + TX, O-5-dichloro-4-iodophenyl-O-ethylethylphosphonothioate (name after IUPAC) (1057) + TX, O,O-diethyl-O-4-methyl-2-oxo-2H-chromen-7-ylphosphorothioate (IUPAC name) (1074) + TX, O,O-diethyl-O- 6-methyl-2-propylpyrimidin-4-ylphosphorothioate (IUPAC name) (1075) + TX, O,O,O',O'-tetrapropyldithiopyrophosphate (IUPAC name) (1424) + TX, oleic acid (IUPAC name ) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydemeton-methyl (609) + TX, oxideprofos (1324) + TX, oxydisulfotone (1325) + TX, pp'-DDT (219 ) + TX, para-dichlorobenzene [CCN] + TX, parathion (615) + TX, parathion-methyl (616) + TX, penfluron (alternative name) [CCN] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (name according to IUPAC) (623) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, PH 60-38 (development code) (1328) + TX, phencapton (1330) + TX, phenothrin (630) + TX, phentoate (631) + TX, phorate (636) + TX, fosalone (637) + TX, phospholane (1338) + TX, phosmet (638) + TX, fosnichlor (1339) + TX, phosphamidone ( 639) + TX, phosphine (IUPAC name) (640) + TX, phoxime (642) + TX, phoxim-methyl (1340) + TX, pyrimetaphos (1344) + TX, pyrimicarb (651) + TX, pyrimiphos-ethyl (1345) + TX, pyrimiphos-methyl (652) + TX, polychlorodicyclopentadiene isomers (IUPAC name) (1346) + TX, polychloroterpenes (traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [ CCN] + TX, pralletrin (655) + TX, precocene I (alternative name) [CCN] + TX, precocene II (alternative name) [CCN] + TX, precocene III (alternative name) [CCN] + TX, primidophos ( 1349) + TX, profenophos (662) + TX, profluthrin [CCN] + TX, promacyl (1354) + TX, promecarb (1355) + TX, propafos (1356) + TX, propetamphos (673) + TX, propoxura (678) ) + TX, protidathione (1360) + TX, prothiophos (686) + TX, protoate (1362) + TX, protrifenbut [CCN] + TX, pimetrosine (688) + TX, pyraclophos (689) + TX, pyrazophos (693) + TX, pyresmethrin (1367) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridalyl (700) + TX, pyridafenthion (701 ) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, pyriproxyfen (708) + TX, quassia (alternative name) [CCN] + TX, quinalphos (711) + TX, quinalphos-methyl (1376) + TX, quinothion (1380) + TX, quinthiophos (1381) + TX, R-1492 (development code) (1382) + TX, rafoxanide (alternative name) [CCN] + TX, resmethrin (719) + TX, rotenone (722) ) + ТХ, RU 15525 (development code) (723) + ТХ, RU 25475 (development code) (1386) + ТХ, ryanium (alternative name) (1387) + ТХ, ryanodine (traditional name) (1387) + ТХ, sabadilla (alternate name) (725) + TX, shradana (1389) + TX, sebuphos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, silafluofen (728) + TX, SN 72129 (development code) (1397) + TX, sodium arsenite [CCN ] + TX, sodium cyanide (444) + TX, sodium fluoride (IUPAC/Chemical Abstract Service name) (1399) + TX, sodium hexafluorosilicate (1400) + TX, sodium pentachlorophenoxide (623) + TX, sodium selenate (name according to IUPAC) (1401) + TX, sodium thiocyanate [CCN] + TX, sofamide (1402) + TX, spinosad (737) + TX, spiromesifen (739) + TX, spirotetramate (CCN) + TX, sulcofuron (746) + TX , sulcofuron-sodium (746) + TX, sulfluramide (750) + TX, sulfotepa (753) + TX, sulfuryl fluoride (756) + TX, sulprofos (1408) + TX, tar oils (alternative name) (758) + TX, tau-fluvalinate (398) + TX, tazimcarb (1412) + TX, TDE (1414) + TX, tebufenoside (762) + TX, tebufenpyrad (763) + TX, tebupyrimphos (764) + TX, teflubenzuron (768) + TX , tefluthrin (769) + TX, temephos (770) + TX, TERP (1417) + TX, teralletrin (1418) + TX, terbam (alternate name) + TX, terbuphos (773) + TX, tetrachloroethane [CCN] + TX , tetrachlorvinphos (777) + TX, tetramethrin (787) + TX, theta-cypermethrin (204) + TX, thiacloprid (791) + TX, thiafenox (alternative name) + TX, thiamethoxam (792) + TX, tycrophos (1428) + TX, thiocarboxym (1431) + TX, thiocyclam (798) + TX, thiocyclam hydrooxalate (798) + TX, thiodicarb (799) + TX, thiophanox (800) + TX, thiometone (801) + TX, thionazine (1434) + TX, thiosultap (803) + TX, thiosultap sodium (803) + TX, thuringhiensin (alternative name) [CCN] + TX, tolfenpyrad (809) + TX, tralometrine (812) + TX, transfluthrin (813) + TX , transpermethrin (1440) + TX, triamiphos (1441) + TX, triazamate (818) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trichlormetaphos-3 (alternative name ) [CCN] + TX, trichloronate (1452) + TX, triphenophos (1455) + TX, triflumuron (835) + TX, trimetacarb (840) + TX, triprene (1459) + TX, vamidothione (847) + TX, vaniliprol [CCN] + TX, veratridine (alternate name) (725) + TX, veratrine (alternative name) (725) + TX, XMC (853) + TX, xylylcarb (854) + TX, YI-5302 (compound code) + TX, zeta-cypermethrin (205) + TX, zetamethrin (alternative name) + TX, zinc phosphide (640) + TX, zolaprofos (1469) and ZXI 8901 (development code) (858) + TX, cyanthraniliprole [736994-63- 19] + TX, chloranthraniliprole [500008-45-7] + TX, cyenopyraphene [560121-52-0] + TX, cyflumethophene [400882-07-7] + TX, pyrifluquinasone [337458-27-2] + TX, spinetorama [187166-40-1 + 187166-15-0] + TX, spirotetramate [203313-25-1] + TX, sulfoxaflora [946578-00-3] + TX, flufiprol [704886-18-0] + TX, meperfluthrin [915288-13-0] + TX, tetramethylfluthrin [84937-88-2] + TX, triflumesopyrim (disclosed in WO 2012/092115) + TX, fluxamethamide (WO 2007/026965) + TX, epsilon-methofluthrin [240494-71 -7] + TX, epsilon-momfluorothrin [1065124-65-3] + TX, fluazaindolizine [1254304-22-7] + TX, chloropralletrin [399572-87-3] + TX, fluxamethamide [928783-29-3] + TX, cyhalodiamide [1262605-53-7] + TX, thioxazafen [330459-31-9] + TX, broflanilide [1207727-04-5] + TX, flufiprol [704886-18-0] + TX, cyclaniliprole [1031756- 98-5] + TX, tetraniliprol [1229654-66-3] + TX, guadipyr (described in WO 2010/060231) + TX, cycloxapride (described in WO 2005/077934) + TX, spiropidion + TX, afidopyropene + TX, flupyrimine + TX, momfluorothrin + TX, kappa-bifenthrin + TX, kappa-tefluthrin + TX, dichlormesothiase + TX, tetrachloraniprole + TX, benzpyrimoxane + TX;

molluscicide selected from the group consisting of bis(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloetocarb (999) + TX, copper acetoarsenite [ CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, iron phosphate (IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576 ) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, triphenmorph (1454) + TX, trimetacarb (840) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, pyriprol [394730-71-3] + TX, nematocide , selected from the group consisting of AKD-3088 (compound code) + TX, 1,2-dibromo-3-chloropropane (IUPAC/Chemical Abstract Service name) (1045) + TX, 1,2-dichloropropane (name according to IUPAC/Chemical Abstract Service) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene -1,1-dioxide (IUPAC/Chemical Abstract Service name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo -1,3,5-thiadiazinan-3-ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alternative name) (210) + TX, abamectin (1) + TX, acetoprol [CCN] + TX , alanicarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, AZ 60541 (compound code) + TX, benclothiase [CCN] + TX, benomyl (62) + TX, butylpyridabene (alternative name) + TX, cadusafos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbosulfan (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, cloetocarb (999) + TX, cytokinins (alternative name) (210) + TX, dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidaphos (1044) + TX, dichlorfenthion (1051) + TX, dicliphos ( alternative name) + TX, dimethoate (262) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, these are profosa (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fenpyrad (alternative name) + TX, fensulfothion (1158) + TX, fostiazate (408) + TX, fostyethane (1196) + TX , furfural (alternative name) [CCN] + TX, GY-81 (development code) (423) + TX, heterophos [CCN] + TX, iodomethane (IUPAC name) (542) + TX, isamidophos (1230) + TX , isazophos (1231) + TX, ivermectin (alternative name) [CCN] + TX, kinetin (alternative name) (210) + TX, mecarfon (1258) + TX, metham (519) + TX, metham-potassium (alternative name) ) (519) + TX, metam sodium (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN ] + TX, compositions with Myrothecium verrucaria (alternative name) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidone (639) + TX, phosphocarb [CCN] + TX, sebuphos (alternate name) + TX, selamectin (alternate name) [CCN] + TX, spinosad (737) + TX, terbama (alternate name) + TX, terbufos (773) + TX, tetrachlorothiophene (name IUPAC/Chemical Abstract Service) (1422) + TX, thiafenox (alternative name) + TX, thionazine (1434) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, xylenols [CCN] + TX, YI-5302 (compound code) and zeatin (alternative name) (210) + TX, fluensulfone [318290-98-1] + TX, fluopyram + TX,

a nitrification inhibitor selected from the group consisting of potassium ethyl xanthate [CCN] and nitrapyrine (580) + TX;

a plant growth activator selected from the group consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and extract of Reynoutria sachalinensis (alternative name) (720) + TX,

a rodenticide selected from the group consisting of 2-isovalerylindane-1,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminum phosphide (640) + TX, ANTU (880) + TX, arsenic oxide (882) + TX, barium carbonate (891) + TX, bistiosemi (912) + TX, brodifacoum (89 ) + TX, bromadiolone (91) + TX, brometalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, calciferol chole (alternative name) (850) + TX, coumachlor (1004) + TX, coumafuryl (1005) + TX, cumatetralyl (175) + TX, crimidine (1009) + TX, difenacum (246) + TX, difetialon (249) + TX, difacinone (273) + TX , ergocalciferol (301) + TX, flocumafen (357) + TX, fluoroacetamide (379) + TX, flupropadine (1183) + TX, flupropadine hydrochloride (1183) + TX, gamma-HCH (430) + TX, HSN (430) + TX, hydrogen cyanide (444) + TX, iodomethane (IUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (IUPAC name) (640) + TX, methyl bromide (537) + TX, norbormide (1318) + TX, phosacetim (1336) + TX, phosphine (IUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371 ) + TX, scilliroside (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, a synergist selected from the group consisting of 2-(2-butoxyethokea)ethyl piperonylate (IUPAC name) (934) + TX, 5-(1,3-benzodioxol- 5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (Development code) (296) + TX, piperonyl butoxide (649) + TX, Piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (Development code) (724) + TX, Sezamex (1393) + TX , sesasmolin (1394) and sulfoxide (1406) + TX,

animal repellent selected from the group consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guasatin (422) + TX, guasatin acetates (422) + TX, methiocarb (530) + TX, pyridine-4-amine (IUPAC name) (23) + TX, thiram ( 804) + TX, trimetacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX,

virucide selected from the group consisting of imanin (alternate name) [CCN] and ribavirin (alternate name) [CCN] + TX, wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octylinone (590) and thiophanate-methyl (802) + TX,

and biologically active compounds selected from the group consisting of azaconazole (60207-31-0] + TX, bitertanol [70585-36-3] + TX, bromuconazole [116255-48-2] + TX, cyproconazole [94361-06- 5] + TX, difenoconazole [119446-68-3] + TX, diniconazole [83657-24-3] + TX, epoxiconazole [106325-08-0] + TX, fenbuconazole [114369-43-6] + TX, fluquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol [76674-21-0] + TX, hexaconazole [79983-71-4] + TX, imazalil [35554-44-0 ] + TX, imibenconazole [86598-92-7] + TX, ipconazole [125225-28-7] + TX, metconazole [125116-23-6] + TX, myclobutanil [88671-89-0] + TX, pefurazoate [ 101903-30-4] + TX, penconazole [66246-88-6] + TX, prothioconazole [178928-70-6] + TX, pyrefenox [88283-41-4] + TX, prochlorase [67747-09-5] + TX, propiconazole [60207-90-1] + TX, simeconazole [149508-90-7] + TX, tebuconazole [107534-96-3] + TX, tetraconazole [112281-77-3] + TX, triadimefon [43121 -43-3] + TX, triadimenol [55219-65-3] + TX, triflumizole [99387-89-0] + TX, triticonazole [131983-72-7] + TX, ancimidol [12771-68-5] + TX, fenarimol [60168-88-9] + TX, nuarimol [63284-71-9] + TX, bupirimate [41483-43-6] + TX, dimethirimol [5221-53-4] + TX, etirimol [23947- 60-6] + TX, dodemorph [1593-77-7] + TX, fenpropidine [67306-00-7] + TX, fenpropimorph [67564-91-4] + TX, spiroxamine [118134-30-8] + TX , tridemorph [81412-43-3] + TX, cyprodinil [121552-61-2] + TX, mepanipyrim [110235-47-7] + TX, pyrimethanil [53112-28-0] + TX, fenpiclonil [74738-17 -3] + TX, fludioxonil [131341-86-1] + TX, benalaxyl [71626-11-4] + TX, furalaxyl [57646-30-7] + TX, metalaxyl [57837-19-1] + TX, R-metalaxyl [70630-17-0] + TX, ofuras [58810-48-3] + TX, oxadixyl [77732-09-3] + TX, benomyl [17804-35-2] + TX, carbendazim [10605- 21-7] + TX, debacarb [62732-91-6] + TX, fuberidazole [3878-19-1] + TX, thiabendazole [148-79-8] + TX, chlosolinate [84332-86-5] + TX , dichlozolin [24201-58-9] + TX, iprodione [36734-19-7] + TX, myclozolin [54864-61-8] + TX, procymidone [32809-16-8] + TX, vinclozolin [50471-44 -8] + TX, boscalid [188425-85-6] + TX, carboxine [5234-68-4] + TX, fenfuram [24691-80-3] + TX, flutolanil [66332-96-5] + TX, mepronil [55814-41-0] + TX, oxycarboxin [5259-88-1] + TX, penthiopyrad [183675-82-3] + TX, tifluzamide [130000-40-7] + TX, guazatine [108173-90- 6] + TX, dodina [2439-10-3] [112-65-2] (free base) + TX, iminoctadine [13516-27-3] + TX, azoxystrobin [131860-33-8] + TX, dimoxystrobin [149961-52-4] + TX, enestroburin {Proc. VSRS, Int. Congr., Glasgow, 2003.1, 93} + TX, fluoxastrobin [361377-29-9] + TX, kresoxim-methyl [143390-89-0] + TX, methominostrobin [133408-50-1] + TX, trifloxystrobin [141517-21-7] + TX, orysastrobin [248593-16-0] + TX, picoxystrobin [117428-22-5] + TX, pyraclostrobin [175013-18-0] + TX, ferbam [14484-64-1 ] + TX, mancozeba [8018-01-7] + TX, maneba [12427-38-2] + TX, metirama [9006-42-2] + TX, propineba [12071-83-9] + TX, thirama [ 137-26-8] + TX, zineba [12122-67-7] + TX, ziram [137-30-4] + TX, captafol [2425-06-1] + TX, captan [133-06-2] + TX, dichlofluanide [1085-98-9] + TX, fluorimide [41205-21-4] + TX, folpet [133-07-3] + TX, tolylfluanid [731-27-1] + TX, Bordeaux mixture [ 8011-63-0] + TX, copper hydroxide [20427-59-2] + TX, copper oxychloride [1332-40-7] + TX, copper sulfate [7758-98-7] + TX, copper oxide [1317- 39-1] + TX, mancopper [53988-93-5] + TX, oxin-copper [10380-28-6] + TX, dinocapa [131-72-6] + TX, nitrotal-isopropyl [10552-74- 6] + TX, edifenphos [17109-49-8] + TX, iprobenphos [26087-47-8] + TX, isoprothiolane [50512-35-1] + TX, fosdifen [36519-00-3] + TX, pyrazophos [13457-18-6] + TX, tolclophos-methyl [57018-04-9] + TX, acibenzolar-S-methyl [135158-54-2] + TX, anilazine [101-05-3] + TX, benthiavalicarb [413615-35-7] + TX, blasticidin-S [2079-00-7] + TX, quinomethionate [2439-01-2] + TX, chloroneba [2675-77-6] + TX, chlorothalonil [1897-45 -6] + TX, cyflufenamid [180409-60-3] + TX, cymoxanil [57966-95-7] + TX, dichlon[117-80-6] + TX, diclocimet [139920-32-4] + TX, diclomesine [62865-36-5] + TX, dicloran [99-30-9] + TX, dietofencarb [87130-20-9] + TX, dimethomorph [110488-70-5] + TX, SYP-LI90 (flumorph) [211867-47-9] + TX, dithianone [3347-22-6] + TX, ethaboxam [162650-77-3] + TX, etridiasol [2593-15-9] + TX, famoxadone [131807-57-3 ] + TX, fenamidone [161326-34-7] + TX, fenoxanil [115852-48-7] + TX, fentin [668-34-8] + TX, ferimzone[89269-64-7] + TX, fluazinam[ 79622-59-6] + TX, fluopicolide [239110-15-7] + TX, flusulfamide [106917-52-6] + TX, fenhexamide [126833-17-8] + TX, fosetyl aluminum [39148-24- 8] + TX, chemexazole [10004-44-1] + TX, iprovalicarb [140923-17-7] + TX, IKF-916 (cyazofamide) [120116-88-3] + TX, kasugamycin [6980-18-3 ] + TX, metasulfocarb [66952-49-6] + TX, metrafenone [220899-03-6] + TX, pencycuron [66063-05-6] + TX, phthalide [27355-22-2] + TX, polyoxins [ 11113-80-7] + TX, probenazole [27605-76-1] + TX, propamocarb [25606-41-1] + TX, proquinazid [189278-12-4] + TX, pyroquilone [57369-32-1] + TX, quinoxyphene [124495-18-7] + TX, quintozene [82-68-8] + TX, sulfur [7704-34-9] + TX, thiadinyl [223580-51-6] + TX, triazoxide [72459 -58-6] + TX, tricyclazole [41814-78-2] + TX, triforin [26644-46-2] + TX, validamycin [37248-47-8] + TX, zoxamide (RH7281) [156052-68- 5] + TX, mandipropamide [374726-62-2] + TX, isopyrazam [881685-58-1] + TX, sedaxan [874967-67-6] + TX, (9-dichloromethylene-1,2,3,4 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid-tetrahydro-1,4-methanonaphthalen-5-yl)-amide (disclosed in WO 2007/048556) + TX, (3',4',5 3-Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid '-trifluorobiphenyl-2-yl)-amide (disclosed in WO 2006/087343) + TX, [(3S,4R,4aR,6S,6aS,12R ,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl -11-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methylcyclopropanecarboxylate [915972-17-7] + TX and 1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl )ethyl]phenyl]-1H-pyrazole-4-carboxamide [926914-55-8] + TX, microorganisms, including Acinetobacter lwoffii + TX, Acremonium alternatum + TX + TX, Acremonium cephalosporium + TX + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, Adoxophyes orana granulovirus (AdoxGV) (Capex®) + TX, Agrobacterium radiobacter strain K84 (Galltrol-A®) + TX, Alternaria alternate + TX, Alternaria cassia + TX, Alternaria destruens (Smolder®) + TX, Ampelomyces quisqualis (AQ10®) + TX, Aspergillus flams AF36 (AF36®) + TX, Aspergillus flavus NRRL 21882 (Aflaguard®) + TX, Aspergillus spp. + TX, Aureobasidium pullulans + TX, Azospirillum + TX, (MicroAZ® + TX, TAZO B®) + TX, Azotobacter + TX, Azotobacter chroocuccum (Azotomeal®) + TX, Azotobacter cysts (Bionatural Blooming Blossoms®) + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus chitinosporus strain CM-1 + TX, Bacillus chitinosporus strain AQ746 + TX, Bacillus licheniformis strain HB-2 (Biostart™ Rhizoboost®) + TX, Bacillus licheniformis strain 3086 (EcoGuard ® + TX, Green Releaf®) + TX, Bacillus circulans + TX, Bacillus firmus (BioSafe® + TX, BioNem-WP® + TX, VOTiVO®) + TX, Bacillus firmus strain 1-1582 + TX, Bacillus macerans + TX, Bacillus marismortui + TX, Bacillus megaterium + TX, Bacillus mycoides strain AQ726 + TX, Bacillus papillae (Milky Spore Powder®) + TX, Bacillus pumilus spp. + TX, Bacillus pumilus strain GB34 (Yield Shield®) + TX, Bacillus pumilus strain AQ717 + TX, Bacillus pumilus strain QST 2808 (Sonata® + TX, Ballad Plus®) + TX, Bacillus spahericus (VectoLex®) + TX, Bacillus spp. + TX, Bacillus spp., strain AQ175 + TX, Bacillus spp., strain AQ177 + TX, Bacillus spp., strain AQ178 + TX, Bacillus subtilis, strain QST 713 (CEASE® + TX, Serenade® + TX, Rhapsody®) + TX, Bacillus subtilis, strain QST 714 (JAZZ®) + TX, Bacillus subtilis, strain AQ153 + TX, Bacillus subtilis, strain AQ743 + TX, Bacillus subtilis, strain QST3002 + TX, Bacillus subtilis, strain QST3004 + TX, Bacillus subtilis variety amyloliquefaciens, strain FZB24 (Taegro® + TX, Rhizopro®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1Ab + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis israelensis (BMP123® + TX , Aquabac® + TX, VectoBac®) + TX, Bacillus thuringiensis kurstaki (Javelin® + TX, Deliver® + TX, CryMax® + TX, Bonide® + TX, Scutella WP® + TX, Turilav WP® + TX, Astuto® + TX, Dipel WP® + TX, Biobit® + TX, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF / 3P®) + TX, Bacillus thuringiensis strain BD#32 + TX, Bacillus thuringiensis strain AQ52 + TX, Bacillus thuringiensis variety aizawai (XenTari® + TX, DiPel®) + TX, bacteria spp. (GROWMEND® + TX, GROWSWEET® + TX, Shootup®) + TX, bacteriophage Clavipacter michiganensis (AgriPhage®) + TX, Bakflor® + TX, Beauveria bassiana (Beaugenic® + TX, Brocaril WP®) + TX, Beauveria bassiana GHA (Mycotrol ES® + TX, Mycotrol O® + TX, BotaniGuard®) + TX, Beauveria brongniartii (Engerlingspilz® + TX, Schweizer Beauveria® + TX, Melocont®) + TX, Beauveria spp. + TX, Boirytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Bacillus thuringiensis tenebrionis (Novodor®) + TX, BtBooster + TX, Burkholderia cepacia (Deny® + TX, Intercept® + TX, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp. + TX, wild thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reukaufii + TX, Candida saitoana (Bio-Coat® + TX, Biocure®) + TX, Candida sake + TX, Candida spp. + TX, Candida tenius + TX, Cedecea dravisae + TX, Cellulomonas flavigena + TX, Chaetomium cochliodes (Nova-Cide®) + TX, Chaetomium globosum (Nova-Cide®) + TX, Chromobacterium subtsugae strain PRAA4-1T (Grandevo®) ) + TX, Cladosporium cladosporioides + TX, Cladosporium oxysporum + TX, Cladosporium chlorocephalum + TX, Cladosporium spp. + TX, Cladosporium tenuissimum + TX, Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp. + TX, Cryptococcus albidus (YIELDPLUS®) + TX, Cryptococcus humicola + TX, Cryptococcus infirmo-miniatus + TX, Cryptococcus laurentii + TX, Cryptophlebia leucotreta granulovirus (Cryptex®) + TX, Cupriavidus campinensis + TX, Cydia pomonella granulovirus (CYD- X®) + TX, Cydia pomonella granulovirus (Madex® + TX, Madex Plus® + TX, Madex Max/Carpovirusine®) + TX, Cylindrobasidium laeve (Stumpout®) + TX, Cylindrocladium + TX, Debaryomyces hansenii + TX, Drechslera hawaiinensis + TX, Enterobacter cloacae + TX, Enterobacteriaceae + TX, Entomophtora virulenta (Vektor®) + TX, Epicoccum nigrum + TX, Epicoccum purpurascens + TX, Epicoccum spp. + TX, Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean® / Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop® + TX, Prestop®) + TX, Gliocladium roseum + TX, Gliocladium spp. (SoilGard®) + TX, Gliocladium virens (Soilgard®) + TX, Granulovirus (Granupom®) + TX, Halobacillus halophilus + TX, Halobacillus litoralis + TX, Halobacillus trueperi + TX, Halomonas spp. + TX, Halomonas subglaciescola + TX, Halovibrio variabilis + TX, Hanseniaspora uvarum + TX, Helicoverpa armigera nuclear polyhedrosis virus (Helicovex®) + TX, Helicoverpa zea nuclear polyhedrosis virus (Gemstar®) + TX, isoflavone - formononetin (Myconate®) + TX, Kloeckera apiculata + TX, Kloeckera spp. + TX, Lagenidium giganteum (Laginex®) + TX, Lecanicillium longisporum (Vertiblast®) + TX, Lecanicillium muscarium (Vertikil®) + TX, Lymantria Dispar nuclear polyhedrosis virus (Disparvirus®) + TX, Marinococcus halophilus + TX, Meira geulakonigii + TX, Metarhizium anisopliae (Met52®) + TX, Metarhizium anisopliae (Destruxin WP®) + TX, Metschnikowia fruticola (Shemer®) + TX, Meischnikowia pulcherrima + TX, Microdochium dimerum (Antibot®) + TX, Micromonospora coerulea + TX, Microsphaeropsis ochracea + TX, Muscodor albus 620 (Muscudor®) + TX, Muscodor roseus strain A3-5 + TX, Mycorrhizae spp. (AMykor® + TX, Root Maximizer®) + TX, Myrothecium verrucaria strain AARC-0255 (DiTera®) + TX, BROS PLUS® + TX, Ophiostomapiliferum strain D97 (Sylvanex®) + TX, Paecilomyces farinosus + TX, Paecilomyces fumosoroseus (PFR-97® + TX, PreFeRal®) + TX, Paecilomyces linacinus (Biostat WP®) + TX, Paecilomyces lilacinus strain 251 (MeloCon WG®) + TX, Paenibacillus polymyxa + TX, Pantoea agglomerans (BlightBan C9-1 ®) + TX, Pantoea spp. + TX, Pasteuria spp.(Econem®) + TX, Pasteuria nishizawae + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart® + TX, TagTeam®) + TX, Penicillium brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp. + TX, Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, phosphate solubilizing bacteria (Phosphomeal®) + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guilermondii + TX , Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Pseudomonas fluorescens strain A506 (BlightBan A506®) + TX, Pseudomonas putida + TX, Pseudomonas reactans + TX, Pseudomonas spp. + TX, Pseudomonas syringae (Bio-Save®) + TX, Pseudomonas viridiflava + TX, Pseudomons fluorescens (Zequanox®) + TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®) + TX, Puccinia canaliculata + TX, Puccinia thlaspeos (Wood Warrior®) + TX, Pythium paroecandrum + TX, Pythium oligandrum (Polygandron® + TX, Polyversum®) + TX, Pythium periplocum + TX, Rhanella aquatilis + TX, Rhanella spp. + TX, Rhizobia (Dormal® + TX, Vault®) + TX, Rhizoctonia + TX, 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 (SARRITOR®) + TX, Scytalidium spp. + TX, Scytalidium uredinicola + TX, nuclear polyhedrosis virus Spodoptera exigua (Spod-X® + TX, Spexit®) + TX, Serratia marcescens + TX, Serratia plymuthica + TX, Serratia spp. + TX, Sordaria fimicola + TX, nuclear polyhedrosis virus Spodoptera littoralis (Littovir®) + TX, Sporobolomyces roseus + TX, Stenotrophomonas maltophilia + TX, Streptomyces ahygroscopicus + TX, Streptomyces albaduncus + TX, Streptomyces exfoliates + TX, Streptomyces galbus + TX, Streptomyces griseoplanus + TX, Streptomyces griseoviridis (Mycostop®) + TX, Streptomyces lydicus (Actinovate®) + TX, Streptomyces lydicus WYEC-108 (ActinoGrow®) + TX, Streptomyces violaceus + TX, Tilletiopsis minor + TX, Tilletiopsis spp. + TX, Trichoderma asperellum (T34 Biocontrol®) + TX, Trichoderma gamsii (Tenet®) + TX, Trichoderma atroviride (Plantmate®) + TX, Trichoderma hamatum TH 382 + TX, Trichoderma harzianum rifai (Mycostar®) + TX, Trichoderma harzianum T-22 (Trianum-P® + TX, PlantShield HC® + TX, RootShield® + TX, Trianum-G®) + TX, Trichoderma harzianum T-39 (Trichodex®) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma spp. LC 52 (Sentinel®) + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + TX, Trichoderma taxi + TX, Trichoderma virens + TX, Trichoderma virens (formerly Gliocladium virens GL-21) ( SoilGuard®) + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, Trichosporon spp. + TX, Trichothecium spp. + TX, Trichothecium roseum + TX, Typhula phacorrhiza strain 94670 + TX, Typhula phacorrhiza strain 94671 + TX, Ulocladium atrum + TX, Ulocladium oudemansii (Botry-Zen®) + TX, Ustilagodis may + TX, various bacteria and additional trace elements (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Verticillium lecanii (Mycotal® + TX, Vertalec®) + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv.Poae (Camperico®) + TX, Xenorhabdus bovienii + TX, Xenorhabdus nematophilus; and plant extracts including Pine Oil (Retenol®) + TX, Azadirachtin (Plasma Neem Oil® + TX, AzaGuard® + TX, MeemAzal® + TX, Molt-X® + TX, Botanical IGR (Neemazad® + TX, Neemix®) + TX, canola oil (Lilly Miller Vegol®) + TX, Chenopodium ambrosioides near ambrosioides (Requiem®) + TX, Chrysanthemum extract (Crisant®) + TX, margosa oil extract (Trilogy®) + TX, Labiatae essential oils (Botania®) + TX, clove, rosemary, peppermint and thyme oil extracts (Garden insect killer®) + TX, glycine betaine (Greenstim®) + TX, garlic + TX, lemongrass oil (GreenMatch®) + TX, margose oil + TX, Nepeta cataria (catnip oil) + TX, Nepeta catarina + TX, nicotine + TX, oregano oil (MossBuster®) + TX, Pedaliaceae oil (Nematon®) + TX, feverfew + TX, Quillaja saponaria (NemaQ®) + TX, Reynoutria sachalinensis (Regalia® + TX, Sakalia®) + TX, rotenone (Eco Roten®) + TX, Rutaceae plant extract (Soleo®) + TX, soybean oil (Ortho ecosense®) + TX, tea tree oil (Timorex Gold®) + TX, Thyme Oil + TX, AGNIQUE® MMF + TX, BugOil® + TX, Blend of Rosemary, Sesame, Peppermint, Thyme and Cinnamon Extracts (EF 300®) + TX, Blend of Clove, Rosemary and Peppermint Extracts (EF 400®) + TX, blend of cloves, peppermint, garlic oil and mint (Soil Shot®) + TX, kaolin (Screen®) + TX, kelp storage glucan (Laminarin®); And

pheromones, including 3M Sprayable Blackheaded Fireworm Pheromone® + TX, Paramount dispenser-(CM)/ Isomate C-Plus® + TX, 3M MEC-GBM Sprayable Pheromone® ) + TX, leaflet pheromone (3M MEC - LR Sprayable Pheromone®) + TX, Muscamone (Snip7 Fly Bait® + TX, Starbar Premium Fly Bait®) + TX, oriental peach leaflet pheromone (3M oriental fruit moth sprayable pheromone®) + TX, glass peach pheromone (Isomate-P®) + TX, tomato pinworm pheromone (3M Sprayable pheromone®) + TX, Entostat powder (palm tree extract) (Exosex CM®) + TX, (E + TX,Z + TX,Z)-3 + TX,8 + TX,11 tetradecatrienyl acetate + TX, (Z + TX,Z + TX,E)-7 + TX,11 + TX,13-hexadecatrienal + TX, (E + TX,Z )-7 + TX,9-dodecadien-1-yl acetate + TX, 2-methyl-1-butanol + TX, calcium acetate + TX, Scenturion® + TX, Biolure® + TX, Check-Mate® + TX, lavandulyl senecyanate; And

macroorganisms, including Aphelinus abdominalis + TX, Aphidius ervi (Aphelinus-System®) + TX, Acerophagus papaya + TX, Adalia bipunctata (Adalia-System®) + TX, Adalia bipunctata (Adaline®) + TX, Adalia bipunctata (Aphidalia ®) + TX, Ageniaspis citricola + TX, Ageniaspis fuscicollis + TX, Amblyseius andersoni (Anderline® + TX, Andersoni-System®) + TX, Amblyseius californicus (Amblyline® + TX, Spical®) + TX, Amblyseius cucumeris (Thripex® + TX, Bugline cucumeris®) + TX, Amblyseius fallacis (Fallacis®) + TX, Amblyseius swirskii (Bugline swirskii® + TX, Swirskii-Mite®) + TX, Amblyseius womersleyi (WomerMite®) + TX, Amitus hesperidum + TX, Anagrus atomus + TX, Anagyrus fusciventris + TX, Anagyrus kamali + TX, Anagyrus loecki + TX, Anagyrus pseudococci (Citripar®) + TX, Anicetus benefices + TX, Anisopteromalus calandrae + TX, Anthocoris nemoralis (Anthocoris-System®) + TX, Aphelinus abdominalis (Apheline® + T, Aphiline®) + TX, Aphelinus asychis + TX, Aphidius colemani (Aphipar®) + TX, Aphidius ervi (Ervipar®) + TX, Aphidius gifuensis + TX, Aphidius matricariae (Aphipar-M®) + TX, Aphidoletes aphidimyza (Aphidend®) + TX, Aphidoletes aphidimyza (Aphidoline®) + TX, Aphytis lingnanensis + TX, Aphytis melinus + TX, Aprostocetus hagenowii + TX, Atheta coriaria (Staphyline®) + TX, Bombus spp. + TX, Bombus terrestris (Natupol Beehive®) + TX, Bombus terrestris (Beeline® + TX, Tripol®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus + TX, Chrysoperla cornea (Chrysoline®) + TX, Chrysoperla carnea (Chrysopa ®) + TX, Chrysoperla rufllabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichus phyllocnistoides + TX, Closterocerus chamaeleon + TX, Closterocerus spp. + TX, Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug® + TX, Cryptoline®) + TX, Cybocephalus nipponicus + TX , Dacnusa sibirica + TX, Dacnusa sibirica (Minusa®) + TX, Diglyphus isaea (Diminex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea + TX, Diglyphus isaea (Miglyphus® + TX, Digline®) + TX, Dacnusa sibirica (DacDigline® + TX, Minex®) + TX Diversinervus spp. + TX, Encarsia citrina + TX, Encarsia formosa (Encarsia max® + TX, Encarline® + TX, En-Strip®) + TX, Eretmocerus eremicus (Enermix®) + TX, Encarsia guadeloupae + TX, Encarsia haitiensis + TX, Episyrphus balteatus (Syrphidend®) + TX, Eretmoceris siphonini + TX, Eretmocerus californicus + TX, Eretmocerus eremicus (Ercaltg + TX, Eretline e®) + TX, Eretmocerus eremicus (Bemimix®) + TX, Eretmocerus hayati + TX, Eretmocerus mundus (Bemipar ® + TX, Eretline m®) + TX, Eretmocerus siphonini + TX, Exochomus quadripustulatus + TX, Feltiella acarisuga (Spidend®) + TX, Feltiella acarisuga (Feltiline®) + TX, Fopius arisanus + TX, Fopius ceratitivorus + TX, formononetin (Wirless Beehome®) + TX, Franklinothrips vespiformis (Vespop®) + TX, Galendromus occidentalis + TX, Goniozus legneri + TX, Habrobracon hebetor + TX, Harmonia axyridis (HarmoBeetle®) + TX, Heterorhabditis spp. (Lawn Patrol®) + TX, Heterorhabditis bacteriophora (NemaShield HB® + TX, Nemaseek® + TX, Terranem-Nam® + TX, Terranem® + TX, Larvanem® + TX, B-Green® + TX, NemAttack® + TX, Nematop®) + TX , Heterorhabditis megidis (Nemasys H® + TX, BioNem H® + TX, Exhibitline hm® + TX, Larvanem-M®) + TX, Hippodamia convergens + TX, Hypoaspis aculeifer (Aculeifer-System® + TX, Entomite-A®) + TX, Hypoaspis miles (Hypoline m® + TX, Entomite-M®) + TX, Lbalia leucospoides + TX, Lecanoideus floccissimus + TX, Lemophagus errabundus + TX, Leptomastidea abnormis + TX, Leptomastix dactylopii (Leptopar®) + TX, Leptomastix epona + TX, Lindorus lophanthae + TX, Lipolexis oregmae + TX, Lucilia caesar (Natufly®) + TX, Lysiphlebus testaceipes + TX, Macrolophus caliginosus (Mirical-N® + TX, Macroline c® + TX, Mirical®) + TX, Mesoseiulus longipes + TX, Metaphycus flavus + TX, Metaphycus lounsburyi + TX, Micromus angulatus (Milacewing®) + TX, Microterys flavus + TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®) + TX, Neodryinus typhlocybae + TX, Neoseiulus californicus + TX , Neoseiulus cucumeris (THRYPEX®) + TX, Neoseiulus fallacis + TX, Nesideocoris tenuis (NesidioBug® + TX, Nesibug®) + TX, Ophyra aenescens (Biofly®) + TX, Orius insidiosus (Thripor-I® + TX, Online i ®) + TX, Orius laevigatus (Thripor-L® + TX, Oriline l®) + TX, Orius majusculus (Oriline m®) + TX, Orius strigicollis (Thripor-S®) + TX, Pauesia juniperorum + TX, Pediobius foveolatus + TX, Phasmarhabditis hermaphrodita (Nemaslug®) + TX, Phymastichus coffea + TX, Phytoseiulus macropilus + TX, Phytoseiulus persimilis (Spidex® + TX, Phytoline p®) + TX, Podisus maculiventris (Podisus®) + TX, Pseudacteon curvatus + TX , Pseudacteon obtusus + TX, Pseudacteon tricuspis + TX, Pseudaphycus maculipennis + TX, Pseudleptomastix mexicana + TX, Psyllaephagus pilosus + TX, Psyttalia concolor (species complex) + TX, Quadrastichus spp. + TX, Rhyzobius lophanthae + TX, Rodolia cardinalis + TX, Rumina decollate + TX, Semielacher petiolatus + TX, Sitobion avenae (Ervibank®) + TX, Steinernema carpocapsae (Nematac C® + TX, Millenium® + TX, BioNem C® + TX, NemAttack® + TX, Nemastar® + TX, Capsanem®) + TX, Steinernema feltiae (NemaShield® + TX, Nemasys F® + TX, BioNem F® + TX, Steinernema-System® + TX, NemAttack® + TX, Nemaplus® + TX, Exhibitline sf® + TX, Scia-rid® + TX, Entonem®) + TX, Steinernema kraussei (Nemasys L® + TX, BioNem L® + TX, Exhibitline srb®) + TX, Steinernema riobrave (BioVector ® + TX, BioVektor®) + TX, Steinernema scapterisci (Nematac S®) + TX, Steinernema spp. + TX, Steinernematid spp. (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX, Trichogramma brassicae ( Tricho-Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator; And

other biologicals, including abscisic acid + TX, bioSea® + TX, Chondrostereum purpureum (Chontrol Paste®) + TX, Colletotrichum gloeosporioides (Collego®) + TX, copper octanoate (Cueva®) + TX, deltoid traps (Trapline d ®) + TX, Erwinia amylovora (harpin) (ProAct® + TX, Ni-HIBIT Gold CST®) + TX, ferrophosphate (Ferramol®) + TX, funnel traps (Trapline y®) + TX, Gallex® + TX, Grower's Secret® + TX, homobrassinolide + TX, iron phosphate (Lilly Miller Worry Free Ferramol Slug & Snail Bait®) + TX, MCPhail trap (Trapline f®) + TX, Microctonus hyperodae + TX, Mycoleptodiscus terrestris (Des-X®) + TX, BioGain® + TX, Aminomite® + TX, Zenox® + TX, pheromone trap (Thripline ams®) + TX, potassium bicarbonate (MilStop®) + TX, potassium salts of fatty acids (Sanova®) + TX, potassium silicate solution (Sil-Matrix®) + TX, potassium iodide + potassium thiocyanate (Enzicur®) + TX, SuffOil-X® + TX, spider venom + TX, Nosema locustae (Semaspore Organic Grasshopper Control®) + TX, glue traps (Trapline YF ® + TX, Rebell Amarillo®) + TX and traps (TakitrapLine y + b®) + TX.

or a biologically active compound or agent selected from brofluthrinate + TX, difluvidazine + TX, flomethoquin + TX, fluhexafon + TX, Plutella xylostella granulosa virus + TX, Cydia pomonella granulosa virus + TX, imiciaphos + TX, Heliothis virescens nuclear polyhedrosis virus + TX , Heliothis punctigera nuclear polyhedrosis virus + TX, Helicoverpa zea nuclear polyhedrosis virus + TX, Spodoptera frugiperda nuclear polyhedrosis virus + TX, Plutella xylostella nuclear polyhedrosis virus + TX, p-cymole + TX, piflubumide + TX, pyrafluprol + TX, QRD 420 + TX, QRD 452 + TX, QRD 460 + TX, terpenoid mixtures + TX, terpenoids + TX, tetraniliprol + TX and α-terpinene + TX;

or active substance indicated by code + TX, such as AE code 1887196 (BSC-BX60309) + TX, code NNI-0745 GR + TX, code IKI-3106 + TX, code JT-L001 + TX, code ZNQ-08056 + TX Code IPPA152201 + TX Code HNPC-A9908 (CAS: [660411-21-2]) + TX Code HNPC-A2005 (CAS: [860028-12-2]) + TX Code JS118 + TX Code ZJ0967 + TX code ZJ2242 + TX code JS7119 (CAS: [929545-74-4]) + TX code SN-1172 + TX code HNPC-A9835 + TX code HNPC-A9955 + TX code HNPC-A3061 + TX code Chuanhua 89-1 + TX code IPP-10 + TX code ZJ3265 + TX code JS9117 + TX code ZJ3757 + TX code ZJ4042 + TX code ZJ4014 + TX code ITM-121 + TX code ITM-121 + TX code ZJ3757 code DPX-RAB55 (DKI-2301) + TX code NA-89 + TX code MIE-1209 + TX code MCI-8007 + TX code BCS-CL73507 + TX code S-1871 + TX code DPX- RDS63 + TX, and code AKD-1193 + TX.

References in square brackets after the active ingredients, for example, [3878-19-1], refer to the number according to the registration number of the Chemical Abstracts Service. The above-described mixing participants are known. If the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C.D.S. TomLin; British Crop Protection Council], they are described in it under the entry number given in this document above in parentheses for a specific compound; for example, the compound "abamectin" is described under entry number (1). If "[CCN]" is added to a particular compound in this document above, then the compound in question is included in the "Compendium of Pesticide Common Names" which is available on the Internet [A. wood; Compendium of Pesticide Common Names, Copyright © 1995-2004]; for example, the compound "acetoprole" is described on the Internet at http://www.alanwood.net/pesticides/acetoprole.html.

Most of the active ingredients described above are referred to above by the so-called "common name" corresponding to the "ISO common name" or other "common name" that is used in individual cases. If the designation is not a "common name", the substance of the designation used instead is given in parentheses for the specific compound; in this case, the IUPAC name, IUPAC/Chemical Abstract Service name, "chemical name", "conventional name", "compound name" or "development code" or, if none of these designations is used, neither the "common name" ", then use the "alternative name". "CAS Registration Number" means the Chemical Abstracts Service Registration Number.

A mixture of active ingredients of compounds of formula I selected from Tables 1-4 with active ingredients described above contains a compound selected from Tables 1-4 and an active ingredient described above, preferably in a mixture ratio of 100:1 to 1:6000 , especially from 50:1 to 1:50, more preferably in a ratio of from 20:1 to 1:20, even more preferably from 10:1 to 1:10, very preferably from 5:1 to 1:5, with particular a ratio of 2:1 to 1:2 is preferred, and a ratio of 4:1 to 2:1 is also preferred, 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. These blend ratios are by weight.

The mixtures described above can be used in a pest control method that involves the use of a composition containing the mixture described above in relation to pests or their environment, with the exception of the method of treating a human or animal body by surgical intervention or therapy and diagnostic methods used in relation to the human or animal body.

Mixtures containing a compound of formula I selected from Tables 1-4 and one or more of the active ingredients as described above can be used, for example, in the form of a separate "premix", in a combined spray mixture consisting of separate formulations of the individual components , which are active ingredients, such as "tank mix", and in the combined use of individual active ingredients, when applied in a sequential manner, i. one after the other with an acceptable short period such as a few hours or days. The order of application of the compounds of formula I, selected from tables 1-4, and the active ingredients described above, is not necessary for the implementation of the present invention.

The compositions of the present invention may also contain additional solid or liquid adjuvants such as stabilizers, e.g. non-epoxidized or epoxidized vegetable oils (e.g. epoxidized coconut oil, rapeseed oil or soybean oil), antifoam agents, e.g. silicone oil, preservatives, viscosity adjusters binders and/or tackifiers, fertilizers or other active ingredients to achieve specific effects, for example bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

The compositions according to the present invention are prepared in a manner known per se, in the absence of adjuvants, for example by grinding, sieving and/or compressing the solid active ingredient, and in the presence of at least one adjuvant, for example by thoroughly mixing and/or grinding the active ingredient with adjuvant(s). These methods of obtaining compositions, as well as the use of compounds I to obtain these compositions are also the subject of the present invention.

Methods of application of compositions which are pest control methods of the aforementioned types, such as spraying, spraying, dusting, brushing, dragging, spreading or watering, which are to be selected to meet the intended purposes in the prevailing circumstances, and the use of compositions to control pests of the aforementioned type are others. objects of the present invention. Typical active ingredient concentration rates are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm. The application rate per hectare is generally from 1 to 2000 g of active ingredient per hectare, in particular from 10 to 1000 g/ha, preferably from 10 to 600 g/ha.

The preferred method of application in the area of crop protection is application to the foliage of plants (foliar application), in which case the frequency and application rate can be selected according to the risk of infestation by the pest in question. Alternatively, the active ingredient can reach the plants through the root system (systemic action), by irrigating the plant site with a liquid composition, or by incorporating the active ingredient in solid form into the plant site, e.g. into the soil, e.g. into the soil). In the case of the paddy rice crop, such granules may be supplied in a certain amount to a flooded paddy field.

The compounds of the present invention and compositions based thereon are also suitable for protecting plant propagation material, for example seeds such as fruit, tubers or grains, or seedlings, from pests of the type mentioned herein above. Propagation material can be treated with the compound before planting, for example seeds can be treated before sowing. Alternatively, the compound can be applied to seed pits (coating), either by soaking the pits in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted at the place of application, for example in a seed furrow during row sowing. These methods for treating plant propagation material and the plant propagation material thus treated are further objects of the present invention. Typical treatment rates will depend on the plant and pest/fungus to be controlled and are typically 1 to 200 grams per 100 kg seed, preferably 5 to 150 grams per 100 kg seed, e.g. 10 to 100 grams per 100 kg of seeds.

The term "seed" embraces seeds and vegetative plant parts of all kinds, including, without limitation, true seeds, seed pieces, root shoots, cereal grains, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots, and the like, and according to a preferred embodiment means true seeds.

The present invention also provides seeds coated or treated with or containing a compound of formula I. The term "coated or treated and/or containing" generally means that the active ingredient is present on most of the surface of the seed at the time of application, although more or less of the ingredient may penetrate the seed depending on the method of application. When planting (transplanting) said seed product, it can absorb the active ingredient. In one embodiment, the present invention provides a plant propagation material capable of adhering to it a compound of formula (I). Also provided herein is a composition-containing plant propagation material treated with a compound of formula (I).

Seed treatment includes all acceptable seed treatment techniques known in the art, such as seed coating, seed coating, seed dusting, seed soaking, and seed pelleting. The use of a compound of formula (I) in the treatment of seeds may be carried out by any known means, such as spraying or dusting the seeds before sowing or during the sowing/planting of the seeds.

Biological examples

The following examples serve to illustrate the present invention. Some of the compounds of the present invention can be distinguished from known compounds due to higher efficacy at low application rates, which can be verified by a person skilled in the art using the experimental procedures set forth in the examples, using lower application rates if necessary, for example, 50 ppm, 25ppm, 12.5ppm, 6ppm, 3ppm, 1.5ppm, 0.8ppm, 0.2ppm or 0.05ppm.

Example B1. Spodoptera littoralis (Egyptian cotton bollworm)

Cotton leaf disks were placed on agar in 24-well microtiter plates and sprayed with test aqueous solutions prepared from 10,000 ppm stock solutions in DMSO. After drying, the leaf discs were infected with five L1 larvae. Samples were evaluated for mortality, anti-feeding effect and growth inhibition compared to untreated samples 3 days after infection. The control of Spodoptera littoralis by the test samples was present if at least one of the categories of mortality, anti-feeding effect and growth inhibition is higher than for the untreated sample. The following compounds resulted in at least 80% control at 200 ppm application rate: P2, P5.

Example B2. Syodoytera littoralis (Egyptian cotton bollworm)

Test compounds were pipetted from stock solutions of 10,000 ppm DMSO into 24-well plates and mixed with agar. Lettuce seeds were placed on agar and the multiwell plate was covered with another plate which also contained agar. After 7 days, the roots took up the compound, and the lettuce germinated into the plate placed on top. The lettuce leaves were then cut into a plate placed on top. Spodoptera eggs were pipetted through a plastic stencil onto moistened gel blotting paper and covered with the plate. Samples were evaluated for mortality, antifeed and growth inhibition compared to untreated samples 6 days post infection.

The following compounds produced an effect of at least 80% in at least one of the three categories (mortality, anti-feeding, or growth inhibition) at the 12.5 ppm rate tested: P2.

Example B3. Plutella xylostella (cabbage moth)

24 - Well cultured microtiter plates were pipetted with test aqueous solutions prepared from 10,000 ppm stock solutions in DMSO. After drying, the plates were infected with L2 larvae (10-15 per well). Samples were evaluated for mortality and growth inhibition compared to untreated samples 5 days post infection.

The following compounds provided an effect of at least 80% in at least one of two categories (mortality or growth inhibition) at a rate of application of 200 ppm: P2, P3, P4, P5, P9, P10, P12 and P17.

Example B4. Diabrotica balteata (grass rootworm)

Corn sprouts, plated on an agar bed in 24-well microtiter plates, were sprayed with test aqueous solutions prepared from 10,000 ppm stock solutions in DMSO. After drying, the plates were infected with L2 larvae (6-10 per well). Samples were evaluated for mortality and growth inhibition compared to untreated samples 4 days post infection.

The following compounds provided an effect of at least 80% in at least one of two categories (mortality or growth inhibition) at the application rate of 200 ppm: P2, P3, P4, P5, P6, P10, P11, P12, P15, P16 and P17 .

Example B5. Myzus yersicae (green peach aphid)

Sunflower leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test aqueous solutions prepared from 10,000 ppm stock solutions in DMSO. After drying, the leaf disks were infested with aphids of various ages. 6 days after infection, the samples were evaluated for mortality.

The following compounds provided at least 80% mortality at the rate of application of 200 ppm: P2, P4, P5, P10, P12, P15 and P17.

Example B6. Myzus persicae (green peach aphid)

Pea seedling roots infested with aphids of various ages were placed directly into test aqueous solutions prepared from 10,000 ppm stock solutions in DMSO. 6 days after placing the seedlings in the test solutions, the samples were evaluated for mortality.

The following compounds provided at least 80% mortality at the studied rate of 24 ppm: P2, P5, P6, P10, P12, P15, P17 and P19.

Example B7. Bemisia tabaci (tobacco whitefly)

Cotton leaf disks were plated on agar in 24-well microtiter plates and sprayed with test aqueous solutions prepared from 10,000 ppm stock solutions in DMSO. After drying, the leaf discs were infected with adult whiteflies. Samples were checked for mortality 6 days after incubation.

The following compounds provided at least 80% mortality at the application rate of 200 ppm: P2, P5, P11, P12 and P17.

Example B8. Euschistus heros (Neotropical brown shield bug)

Soybean leaves on agar in 24-well microtiter plates were sprayed with test aqueous solutions prepared from 10,000 ppm stock solutions in DMSO. After drying, the leaves were infected with N2 nymphs. Samples were evaluated for mortality and growth inhibition compared to untreated samples 5 days post infection.

The following compounds provided an effect of at least 80% in at least one of two categories (mortality or growth inhibition) at the application rate of 200 ppm: P2, P5, P6, P9, P11, P12, P13, P15, P16, P17 and P19 .

Example B10. Tetranychus urticae (two-spotted spider mite)

Bean leaf discs on agar in 24-well microtiter plates were sprayed with test aqueous solutions prepared from 10,000 ppm stock solutions in DMSO. After drying, the leaf discs were infected with a population of ticks of different ages. After 8 days after infection in a mixed population (mobile stages), the samples were evaluated for mortality.

Example B11. Thrips tabaci (onion tripe)

Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with test aqueous solutions prepared from 10,000 ppm stock solutions in DMSO. After drying, the leaf discs were infected with a population of thrips of different ages. 6 days after infection, the samples were evaluated for mortality.

Example B12. Frankliniella occidentalis (western flower tripe)

Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with test aqueous solutions prepared from 10,000 ppm stock solutions in DMSO. After drying, the leaf discs were infected with Frankliniella populations of different ages. 7 days after infection, the samples were evaluated for mortality.

Example B13. Comparison of the insecticidal activity of the P17 compound according to the present invention with the structurally most closely comparable prior art compound

The activity of compound P17 according to the present invention and compound P15 of WO 2016/026848 against Euschistus heros is shown in Table B13.

Test Description

Soybean plants 2 weeks old were sprayed with diluted aqueous test solutions. The plants were then infected with 10 stink bug nymphs (N2). Soybean seeds were added as an additional food source to the test system. Samples were evaluated for mortality 5 days after treatment.

Claims (26)

1. Compound of formula I

Where A is CH or N; X is S or SO ₂ ; R ₁ represents C ₁ -C ₄ alkyl; G ₁ is N or CH; X ₁ is NR ₃ ; where R ₃ represents C ₁ -C ₄ alkyl; R ₂ is halogen or C ₁ -C ₄ haloalkyl; R ₇ represents hydrogen, fluorine, cyano or C ₁ -C ₆ alkyl; And R ₈ represents fluorine, cyano, C ₁ -C ₈ alkyl or C ₁ -C ₄ alkyloxycarbonyl; and agrochemically acceptable salts of a compound of formula I. 2. A compound or an agrochemically acceptable salt thereof according to claim 1, wherein R ₇ is hydrogen, methyl, ethyl or fluoro and R ₈ is fluoro, methyl or ethyl. 3. The compound or its agrochemically acceptable salt according to claim 1, where A is CH or N; X is S or SO ₂ ; G ₁ is N or CH; X ₁ is NCH ₃ ; R ₁ is methyl, ethyl, n-propyl or isopropyl; R ₂ is C ₁ -C ₂ haloalkyl; R ₇ is methyl or fluoro; And R ₈ is fluorine, methyl or ethyl. 4. The compound or its agrochemically acceptable salt according to any one of paragraphs. 1, 2 or 3, where A is N. 5. Composition for insect control, containing an insecticidally effective amount of a compound of formula (I) or its agrochemically acceptable salt according to any one of paragraphs. 1-4 and optionally an adjuvant or diluent. 6. A method of insect control and control, which involves applying to a pest, to a pest habitat or to a plant susceptible to the pest, an insecticidally effective amount of a compound of formula (I) or an agrochemically acceptable salt according to any one of paragraphs. 1-4 or compositions according to claim 5. 7. A method of protecting plant propagation material from insect attack, which involves treating the propagation material or the area where the propagation material is planted with the composition of claim 5.