RU2804355C2 - Pesticidally active heterocyclic derivatives with sulphur-containing substitutes - Google Patents

Abstract

FIELD: organic chemistry.

SUBSTANCE: compound of formulas I-Q1, I-Q4, their agrochemically acceptable salts, a pesticide composition, a method for controlling insects, mites and nematodes, a method for protecting plant propagation material. In formula I-Q1, A is CH or N; X is S or SO₂ ; R₁ represents C₁-C₄ alkyl; R₇ and R₈ are independently C₁-C₆ alkyl; R₂ is C₁-₆ haloalkyl, C₁-C₄ haloalkylsulphanyl, C₁-C₄ haloalkylsulphinyl, C₁-C₄ haloalkylsulphonyl or C₁-C₆ haloalkoxy; G₂ is N or CH. In formula I-Q4, A is CH or N; X is S, SO, or SO₂; R₁ is C₁-C₄ alkyl, C₁-C₄ haloalkyl or C₃-C₆ cycloalkyl; C₁-C₄ alkyl; R₇ and R₈ are independently C1-C6 alkyl; R2 is C1-C6 haloalkyl, C1-C4 haloalkylsulphanyl, C1-C4 haloalkylsulphinyl, C1-C4 haloalkylsulphonyl or C1-C6 haloalkoxy.

EFFECT: connection of formulas I-Q1, I-Q4 for use in agriculture as an effective agent against insects, mites and nematodes.

7 cl, 12 tbl, 16 ex

Description

The present invention relates to pesticide active, in particular insecticidal 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 particular insects or members of the order Acarina).

Heterocyclic compounds with pesticidal action are known and described, for example, in

WO 2012/086848, WO 2013/018928, WO 2016/071214, EP 2862853 and WO 2016/026848.

Currently, new pesticide-active derivatives with a heterocyclic 6/5-bicyclic ring with sulfur-containing phenyl and pyridyl substituents have been found.

The present invention accordingly relates to compounds of formula I,

Where

A represents CH or N;

X represents S, SO or SO ₂ ;

R ₁ represents C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or C ₃ -C ₆ cycloalkylC ₁ -C ₄ alkyl;

R ₇ and R ₈ independently represent 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 alkoxyC 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 alkoxycarbonyl;

Q is a radical selected from the group consisting of the formulas Q ₁ , Q ₂ , Q ₃ and Q ₄

where the arrow indicates the point of attachment to the ring containing radical A;

and where

R ₂ represents 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 ₃ represents C ₁ -C ₄ alkyl;

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

G ₁ and G ₂ independently represent N or CH;

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 can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrohalic acid, with strong organic carboxylic acids, such as C ₁ -C ₄ alkane carboxylic acids, which are unsubstituted or substituted, for example with a 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 a halogen, for example methane or p-toluenesulfonic acid. Compounds of formula I which contain at least one acidic group can form, for example, salts with bases, for example mineral salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or organic an amine such as morpholine, piperidine, pyrrolidine, a lower mono-, di- or trialkylamine such as ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a lower mono-, di- or trihydroxyalkylamine such as mono-, di - or triethanolamine.

Alkyl groups appearing in the definitions of substituents may be straight or branched and include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, nonyl, decyl and their branched isomers. Alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, alkoxy, alkenyl and alkynyl radicals are obtained from the mentioned alkyl radicals. Alkenyl and alkynyl groups may be mono- or polyunsaturated.

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

Haloalkyl groups preferably have 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.

Alkylsulfanyl is, for example, methylsulfanyl, ethylsulfanyl, propylsulfanyl, isopropylsulfanyl, butylsulfanyl, pentylsulfanyl and hexylsulfanyl.

Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, pentylsulfinyl and hexylsulfinyl.

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

Haloalkylsulfanyl groups preferably have a chain length of 1 to 4 carbon atoms. A haloalkylsulfanyl is, for example, difluoromethylsulfanyl, trifluoromethylsulfanyl or 2,2,2-trifluoroethylsulfanyl. Similar considerations apply to the C ₁ -C ₄ haloalkylsulfinyl and C ₁ -C ₄ haloalkylsulphonyl radicals, which may be, for example, trifluoromethylsulfinyl, trifluoromethylsulfonyl or 2,2,2-trifluoroethylsulfonyl.

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 the isomeric radicals pentyloxy and hexyloxy.

Alkoxycarbonyl groups preferably have a preferred chain length of 1 to 5 carbon atoms. Alkoxycarbonyl represents, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl and tert-butoxycarbonyl radicals.

Alkoxyalkyl groups preferably have a chain length of 1 to 6 carbon atoms.

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

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

Cycloalkylalkyl groups preferably contain 4-8 carbon atoms, for example, cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclopentylmethyl and cyclohexylmethyl.

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

A preferred group of compounds of formula I is represented by compounds of formula I-Q1,

where A, X, R ₁ , R ₂ , G ₂ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q1

A is preferably N;

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

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

A particularly preferred group of compounds of formula I-Q1 include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Another particularly preferred group of compounds of formula I-Q1 include those wherein R ₁ is ethyl and X is SO ₂ .

A more preferred group of compounds of formula I-Q1 is represented by compounds of formula I-Q1a,

where A, X, R ₁ , R ₂ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q1a

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

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

A particularly preferred group of compounds of formula I-Q1a include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Another particularly preferred group of compounds of formula I-Q1a include those wherein R ₁ is ethyl and X is SO ₂ .

An even more preferred group of compounds of formula I-Q1a is represented by compounds of formula I-Q1a1,

where X, R ₁ , R ₂ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q1a1

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

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

A particularly preferred group of compounds of formula I-Q1a1 include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Another particularly preferred group of compounds of formula I-Q1a1 include those wherein R ₁ is ethyl and X is SO ₂ .

Another even more preferred group of compounds of formula I-Q1a is represented by compounds of formula I-Q1a2,

where X, R ₁ , R ₂ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q1a2

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

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

A particularly preferred group of compounds of formula I-Q1a2 include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Another particularly preferred group of compounds of formula I-Q1a2 include those wherein R ₁ is ethyl and X is SO ₂ .

Another more preferred group of compounds of formula I-Q1 are represented by compounds of formula I-Q1b,

where A, X, R ₁ , R ₂ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q1b

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

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

A particularly preferred group of compounds of formula I-Q1b include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Another particularly preferred group of compounds of formula I-Q1b include those wherein R ₁ is ethyl and X is SO ₂ .

An even more preferred group of compounds of formula I-Q1b is represented by compounds of formula I-Q1b1,

where X, R ₁ , R ₂ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q1b1

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

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

A particularly preferred group of compounds of formula I-Q1b1 include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Another particularly preferred group of compounds of formula I-Q1b1 include those wherein R ₁ is ethyl and X is SO ₂ .

Another even more preferred group of compounds of formula I-Q1b are represented by compounds of formula I-Q1b2,

where X, R ₁ , R ₂ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q1b2

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

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

A particularly preferred group of compounds of formula I-Q1b2 include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Another particularly preferred group of compounds of formula I-Q1b2 include those wherein R ₁ is ethyl and X is SO ₂ .

A second preferred group of compounds of formula I is represented by compounds of formula I-Q2,

where A, X, R ₁ , R ₂ , G ₁ , G ₂ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q2

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

R ₂ preferably represents a C ₁ -C ₄ haloalkyl; and X is preferably SO ₂ .

A particularly preferred group of compounds of formula I-Q2 include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Another particularly preferred group of compounds of formula I-Q2 include those wherein R ₁ is ethyl and X is SO ₂ .

A more preferred group of compounds of formula I-Q2 is represented by compounds of formula I-Q2a,

where A, X, R ₁ , R ₂ , G ₁ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q2a

A is preferably N;

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

R ₂ preferably represents a C ₁ -C ₄ haloalkyl; G ₁ is preferably CH; and X is preferably SO ₂ .

A particularly preferred group of compounds of formula I-Q2a include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Another particularly preferred group of compounds of formula I-Q2a include those wherein R ₁ is ethyl and X is SO ₂ .

An even more preferred group of compounds of formula I-Q2a is represented by compounds of formula I-Q2a1,

where X, R ₁ , R ₂ , G ₁ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q2a1

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

R ₂ preferably represents a C ₁ -C ₄ haloalkyl; G ₁ is preferably CH; and X is preferably SO ₂ .

A particularly preferred group of compounds of formula I-Q2a1 include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Another particularly preferred group of compounds of formula I-Q2a1 include those wherein R ₁ is ethyl and X is SO ₂ .

Another even more preferred group of compounds of formula I-Q2a is represented by compounds of formula I-Q2a2,

where X, R ₁ , R ₂ , G ₁ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q2a2

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

R ₂ preferably represents a C ₁ -C ₄ haloalkyl; G ₁ is preferably CH; and X is preferably SO ₂ .

A particularly preferred group of compounds of formula I-Q2a2 include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Another particularly preferred group of compounds of formula I-Q2a1 include those wherein R ₁ is ethyl and X is SO ₂ .

Another more preferred group of compounds of formula I-Q2 is represented by compounds of formula I-Q2b,

where A, X, R ₁ , R ₂ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q2b

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

R ₂ preferably represents a C ₁ -C ₄ haloalkyl; and X is preferably SO ₂ .

A particularly preferred group of compounds of formula I-Q2b include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Another particularly preferred group of compounds of formula I-Q2b include those wherein R ₁ is ethyl and X is SO ₂ .

An even more preferred group of compounds of formula I-Q2b is represented by compounds of formula I-Q2b1,

where X, R ₁ , R ₂ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q2b1

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

R ₂ preferably represents a C ₁ -C ₄ haloalkyl; and X is preferably SO ₂ .

A particularly preferred group of compounds of formula I-Q2b1 include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Other particularly preferred compounds of formula I-Q2b1 are those wherein R ₁ is ethyl and X is SO ₂ .

Another even more preferred group of compounds of formula I-Q2b are represented by compounds of formula I-Q2b2,

where X, R ₁ , R ₂ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q2b2

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

R ₂ preferably represents C ₁ -C ₄ alogenalkyl; and X is preferably SO ₂ .

A particularly preferred group of compounds of formula I-Q2b2 include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Another particularly preferred group of compounds of formula I-Q1b2 include those wherein R ₁ is ethyl and X is SO ₂ .

A third preferred group of compounds of formula I are represented by compounds of formula I-Q3,

where A, X, R ₁ , R ₂ , R ₄ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q3

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

R ₂ preferably represents a C ₁ -C ₄ haloalkyl;

R ₃ is preferably methyl;

R ₄ is preferably methyl, ethyl, 2,2,2-trifluoroethyl or cyclopropyl, and X is preferably SO ₂ .

A particularly preferred group of compounds of formula I-Q3 include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Another particularly preferred group of compounds of formula I-Q3 include those wherein R ₁ is ethyl and X is SO ₂ .

A more preferred group of compounds of formula I-Q3 is represented by compounds of formula I-Q3a,

where X, R ₁ , R ₂ , R ₄ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q3a

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

R ₂ preferably represents a C ₁ -C ₄ haloalkyl;

R ₃ is preferably methyl;

R ₄ is preferably methyl, ethyl, 2,2,2-trifluoroethyl or cyclopropyl, and X is preferably SO ₂ .

A particularly preferred group of compounds of formula I-Q3a include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Another particularly preferred group of compounds of formula I-Q3a include those wherein R ₁ is ethyl and X is SO ₂ .

Another more preferred group of compounds of formula I-Q3 is represented by compounds of formula I-Q3b,

where X, R ₁ , R ₂ , R ₄ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q3b

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

R ₂ preferably represents a C ₁ -C ₄ haloalkyl;

R ₃ is preferably methyl;

R ₄ is preferably methyl, ethyl, 2,2,2-trifluoroethyl or cyclopropyl, and X is preferably SO ₂ .

A particularly preferred group of compounds of formula I-Q3b include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C 1 -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Another particularly preferred group of compounds of formula I-Q3b include those wherein R ₁ is ethyl and X is SO ₂ .

A particularly preferred group of compounds of formula I-Q3 is represented by compounds of formula I-Q3c,

where A, X, R ₁ , R ₂ , R ₄ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q3c

A represents CH or N; preferably A is N;

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

R ₂ preferably represents a C ₁ -C ₄ haloalkyl;

R ₄ is preferably methyl, ethyl, 2,2,2-trifluoroethyl or cyclopropyl, and X is S or SO ₂ ; preferably X is SO ₂ .

A particularly preferred group of compounds of formula I-Q3c include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Another particularly preferred group of compounds of formula I-Q3c include compounds where

A represents CH or N; in particular A is N;

R ₁ represents ethyl;

X represents S or SO ₂ ; in particular X is SO ₂ ;

R ₇ and R ₈ independently of each other represent C ₁ -C ₆ alkyl, preferably methyl;

R ₂ represents a C ₁ -C ₄ haloalkyl, preferably trifluoromethyl; And

R ₄ is ethyl, 2,2,2-trifluoroethyl or cyclopropyl.

Another particularly preferred group of compounds of formula I-Q3c include those wherein R ₁ is ethyl and X is SO ₂ .

A fourth preferred group of compounds of formula I are represented by compounds of formula I-Q4,

where A, X, R ₁ , R ₂ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q4

A is preferably N;

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

R ₂ preferably represents C ₁ -C ₄ alogenalkyl; and X is preferably SO ₂ .

A particularly preferred group of compounds of formula I-Q4 include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Another particularly preferred group of compounds of formula I-Q4 include those wherein R ₁ is ethyl and X is SO ₂ .

A more preferred group of compounds of formula I-Q4 is represented by compounds of formula I-Q4a,

where X, R ₁ , R ₂ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q4a

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

R ₂ preferably represents C ₁ -C ₄ alogenalkyl; and X is preferably SO ₂ .

A particularly preferred group of compounds of formula I-Q4a include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Another particularly preferred group of compounds of formula I-Q4a include those wherein R ₁ is ethyl and X is SO ₂ .

Another more preferred group of compounds of formula I-Q4 are represented by compounds of formula I-Q4b,

where X, R ₁ , R ₂ , R ₇ and R ₈ are defined by formula I above. In said preferred group of compounds of formula I-Q4b

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

R ₂ preferably represents a C ₁ -C ₄ haloalkyl; and X is preferably SO ₂ .

A particularly preferred group of compounds of formula I-Q4b include those wherein R ₇ and R ₈ are independently halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxycarbonyl; preferably C ₁ -C ₆ alkyl.

Another particularly preferred group of compounds of formula I-Q4b include those wherein R ₁ is ethyl and X is SO ₂ .

In all preferred embodiments mentioned above, regardless

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

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

R ₂ preferably represents a C ₁ -C ₄ haloalkyl; most preferably trifluoromethyl;

R ₇ preferably represents C ₁ -C ₆ alkyl; most preferably methyl;

R ₈ preferably represents C ₁ -C ₆ alkyl; most preferably methyl.

In all preferred embodiments mentioned above, it is preferable

X is S or SO ₂ , most preferably SO ₂ , and

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

R ₂ represents C ₁ -C ₄ haloalkyl; most preferably methyl trifluoro; And

R ₇ represents C ₁ -C ₆ alkyl; most preferably methyl; And

R ₈ represents C ₁ -C ₆ alkyl; most preferably methyl.

The remaining group of compounds of formula I is represented by compounds of formula 1-1,

Where

A represents CH or N; in particular A is N; R ₇ and R ₈ independently of each other represent C ₁ -C ₆ alkyl, preferably methyl; And

Q is a radical selected from the group consisting of the formulas Q _1a , Q _1b , Q _2a , Q _2b , C _3a and Q _3b ,

in particular selected from Q _1a , C _2a and C _3b ;

where the arrow indicates the point of attachment to the ring containing radical A;

and in which

R2 is a C ₁ -C ₄ haloalkyl, preferably trifluoromethyl.

The process for preparing the compounds of formula I according to the present invention is carried out using methods known to those skilled in the art. Compounds of formula I-a3, where X is SO ₂ , a Q, A, R ₁ , R ₇ and R ₈ are defined under formula I above, can be prepared by oxidation of compounds of formula I-a2, where X is SO, and Q , A, R ₁ , R ₇ and R ₈ are defined by Formula I above. The reaction can be carried out using 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, a Q, A, R ₁ , R ₇ and R ₈ are defined under formula I above, can be prepared by oxidation of compounds of formula I-a1, where X is S, a Q, A, R ₁ , R ₇ and R ₈ are defined under formula I above, under conditions similar to those described above. These reactions can be carried out in a variety of organic or aqueous solvents compatible with such conditions, at temperatures ranging 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 presented in Scheme 1.

Scheme 1

Compounds of formula I, where X, Q, A, R ₁ , R ₇ and R ₈ are defined by formula I above, can be prepared using the methods described in Scheme 2. By treating compounds of formula III, where Q, A and R ₁ defined by formula I above, X is S or SO ₂ , and Xb ₁ is preferably a halogen (even more preferably chlorine, bromine or iodine), a compound of formula 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 ), a ligand, for example Xantphos, in an inert solvent such as DMF, at temperatures of 100-160° C., optionally heating with microwave radiation, obtain compounds of formula II, where A, Q and R ₁ are defined under the general formula I above, and X represents S or SO ₂ . Such methods have been described in the literature, for example in Org. Lett., 16(24), 6314-6317; 2014. Compounds of formula II can be treated sequentially with alkylating reagents of the general formula VI, where Xb ₂ is preferably Br, I, OSO ₃ Me or OTf, and R ₇ and R ₈ are defined by 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 I. Alternatively, compounds of formula II can be exposed to an excess of the above base and reagent VI to give compounds of general type Ia- 4, where R ₇ = R ₈ . Alternatively, a compound 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 Krapcho. Such methods have been described, for example, in Tetradehron 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. This reaction can occur 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. Likewise, processes involving transition metal catalysis are known, see, for example, Angew. Chem. Int. Ed. 2011, 50, 4470-4474. Alternatively, compounds of formula I can be prepared 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, in J. Am. Chem. Soc. 2005, 127, 15824-15832; J. Org. Chem. 2005, 70, 10186-10189 or Org. Lett. 2011, 13, 1690-1693

Scheme 2

Compounds of general formula III, wherein A, X and R ₁ are defined under formula I above, and Xb ₁ is preferably a halogen (even more preferably chlorine, bromine or iodine), are known (Scheme 3). For example, compounds of formula III, where Q=Q ₁ , are represented by compounds of formula IIIa below, where A, G2, X, R ₁ and R ₂ are defined under formula I above, and Xb ₁ is preferably halogen (even more preferably chlorine, bromine or iodine). The synthesis of compounds of formula IIIa, where G ₂ represents N, was described in WO 2016/071214. The synthesis of compounds of formula IIIa where G ₂ represents CH has been described in WO 2015/000715. Likewise, compounds of formula III, where Q=Q ₂ , are represented by compounds of formula IIIb below, wherein A, G ₁ , G ₂ , X, R ₁ and R ₂ are defined under formula I above, and Xb ₁ is preferably halogen (even more preferably chlorine, bromine or iodine). The synthesis of compounds of formula IIIb where G ₂ represents CH and G ₁ represents N or CH has been described in WO 2013/191113. The synthesis of compounds of formula IIIa where G ₂ is N and G ₁ is CH has been described in WO 2017/134066. The synthesis of compounds of formula IIIb where G ₂ is N and G ₁ is N has been described in WO 2016/020286. In addition, WO 2016/023954 and WO 2017/089190 described the synthesis of compounds of formula IIIc, wherein A, X, R ₁ , R ₂ , R ₃ and R ₄ are defined by formula I above, and Xb ₁ is preferably halogen ( even more preferably chlorine, bromine or iodine). The synthesis of compounds of formula IIId, where Q=Q ₄ , was described in WO 2015/000715.

Scheme 3

Alternatively, compounds of formula I-Q1, wherein A, X, R ₁ , R ₂ , G ₂ , R ₇ and R ₈ are defined under formula I above, can be prepared using the methods described in Scheme 4. Compounds of formula IX, where R ₂ and G ₂ are defined by formula I, are reacted with compounds of formula X, where X, A, R ₁ , R ₇ and R ₈ are defined by formula I above, and Xb ₃ is a halogen, preferably bromine, iodine or chlorine , in an inert solvent, for example ethanol or acetonitrile, optionally in the presence of a suitable base, at temperatures of 80-150°C to obtain compounds of formula I-Q1. Such reactions can optionally be carried out in a microwave oven and have been described in the literature, for example in WO 2012/49280 or WO 2003/031587. The compounds of formula IX are either commercially available or can be prepared using methods known to those skilled in the art.

Scheme 4

Compounds of formula X, where X, A, R ₁ , R ₇ and R ₈ are defined under formula I above and Xb ₃ is a halogen, preferably bromine, iodine or chlorine, can be prepared in two steps from compounds of formula XI, where X and R ₁ are defined under formula I above (Scheme 5). The compounds of formula XI are known and their synthesis has been described, for example, in WO 2016/071214. The compounds of formula XI can be treated sequentially with alkylating agents of the general formula VIa, where Xb ₂ is preferably Br, I, OSO ₃ Me or OTf, and R ₇ is defined by 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 obtain compounds of formula XIIa, wherein A, X, R ₁ , R ₇ and R ₈ are defined by formula I above. As a result of subsequent treatment of compounds of formula XIIa with a halogenating reagent (source "Xb ₃ ⁺ "), for example, N-bromosuccinimide, N-iodosuccinimide, N-chlorosuccinimide, I2, CuBr ₂ , Br ₂ in acetic acid, PhNMe ₃ ⁺ Br ₃ ^- , Typically, compounds of formula X are prepared in a solvent such as methanol, acetonitrile, THF, chloroform or dichloromethane at temperatures ranging from 0°C to 120°C. In addition, compounds of formula X can be prepared analogously to the methods described in WO 2016/ 071214.

Scheme 5

Alternatively, compounds of formula I-Q3 can be prepared as described in Scheme 6. Treatment of compounds of formula XIII, where R ₁ , A, X, R ₇ and R ₈ are defined above for formula I, can be applied to compounds of formula XIV with using methods known to those skilled in the art and is described, for example, in Tempahedron 2005, 61 (46), 10827-10852. For example, compounds of formula XIV, where X ₀ represents chlorine, are formed by treatment, for example, with oxalyl chloride or thionyl chloride in the presence of catalytic quantities of DMF in inert solvents such as methylene chloride or THF, at temperatures ranging from 20° C. to 100° C., preferably at 25°C. By treating compound XIV with compounds of formula XV, wherein R ₂ , R ₃ and R ₄ are defined as described in formula I, optionally in the presence of a base, for example triethylamine or pyridine, compounds of formula XVI are obtained. Alternatively, compounds of formula XVI can be prepared by treating compounds of formula XIII with dicyclohexylcarbodiimide (DCC) or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) to obtain activated compounds XIV, where X ₀ represents X ₀₁ and X ₀₂ , respectively , in an inert solvent, for example pyridine or tetrahydrofuran (THF), optionally in the presence of a base, for example triethylamine, at temperatures of 50-180°C. The resulting compounds of formula XVI can then be converted to compounds of formula I-Q3 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 temperatures of 25-180°C, preferably 130-170°C. Such processes and methods for the synthesis of compounds of formula XV have been previously described in WO 2016/023951 and WO 2017/089190.

Scheme 6

Compounds of formula XIII, where R ₁ , A, X, R ₇ and R ₈ are defined above for formula I, can be prepared using the methods described in Scheme 7. Synthesis of the necessary starting materials of formula XX, where R ₁ , X, A are defined above for formula I, and where Xb ₁ may 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 XX with trimethylsilylacetonitrile (V) in the presence of zinc(II) fluoride and a palladium(O) catalyst such as the adduct of tris(dibenzylideneacetone)dipalladium(0) and chloroform (Pd ₂ (dba) ₃ ), a ligand, for example Xantphos, in an inert solvent such as DMF, at temperatures of 100-160° C., optionally by heating with microwave radiation, produces compounds of formula XVIII, where X is S or SO ₂ , R ₁ , A and R ₇ are defined in formula I above, and R _LG represents C ₁ -C ₄ alkyl. Such methods have been described in the literature, for example in Org. Lett, 16(24), 6314-6317; 2014. Compounds of formula XVIII can be treated sequentially with alkylating reagents of formula VI, where Xb ₂ is preferably Br, I, or OTf, and R ₈ is defined by 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 obtain compounds of formula XVII, where X is S or SO ₂ , R ₁ , A, R ₇ and R ₈ are defined in formula I above, and R _LG is is a C ₁ -C ₄ alkyl. Alternatively, compounds of formula XVIII can be reacted with an excess of the above base and reagent VI to give compounds of general type XVII-a, where R ₇ =R ₈ .

Alternatively, compounds of formula XVII can be prepared directly from compounds of formula XX by treatment with compounds of formula IV, wherein 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 or Org. Lett. 2011, 13, 1690-1693.

Alternatively, a compound of formula XVIII can be prepared from compounds of formula XIX, wherein A, X and R ₁ are defined under formula I above, R _LG and R ₁₁ independently of each other represent a C ₁ -C ₆ alkyl group, preferably methyl or ethyl, by decarboxylation of Krapcho. Such methods have been described, for example, in Tetradehron Lett. 1974, 15, 1091-1094. Compounds of formula XIX can be prepared by reacting compounds of formula XX with cyanoacetates of formula VIII, where R ₁₁ is a C ₁ -C ₆ alkyl group, preferably methyl or ethyl. This reaction can occur 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. Likewise, processes involving transition metal catalysis are known, see, for example, Angew. Chem. Int. Ed. 2011, 50, 4470-4474. Compounds of formula XVII or XVII-a can be converted to compounds of formula XIII by saponification under conditions known to one skilled in the art. The compounds of formulas VIII, V and VI are commercially available, or methods for preparing such compounds are known to one skilled in the art. The compounds of formula XX are known and their synthesis has been described in the literature, see for example WO 2016/005263.

Scheme 7

Alternatively, compounds of formula I-Q4, wherein A, X, R ₁ , R ₂ , R ₇ and R ₈ are defined by formula I above, can be prepared using the methods described in Scheme 8. Compounds of formula I-Q4 can be prepared similarly compounds I-Q1 by reacting compounds of formula XXI, where R ₂ is defined by formula I, with compounds of formula X, where X, A, R ₁ , R ₇ and R ₈ are defined by formula I above, and Xb ₃ is a halogen , preferably bromine, iodine or chlorine, in an inert solvent, for example ethanol or acetonitrile, optionally in the presence of a suitable base, at temperatures of 80-150°C to obtain compounds of formula I-Q4. Such reactions can optionally be carried out in a microwave oven to produce compounds of formula XXI wherein R ₂ is trifluoromethyl, known for example from WO 2016/051193, or which can be prepared using methods similar to those described herein or known to one skilled in the art. field of technology.

Scheme 8

Reactants can be reacted in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkaline earth metals or alkylsilylamides of alkali metals or alkaline earth metals, 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, 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 reagents can be reacted with each other as is, i.e. without adding solvent or thinner. 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, then bases that 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 per se known manner to another compound of formula I by replacing one or more substituents of the parent compound of formula I in a conventional manner with other substituent(s) in accordance with the present invention.

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

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

Salts of compounds of formula I can be converted in the conventional manner into free compounds 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 an inorganic acid salt, for example the hydrochloride, with a suitable metal acid salt, such as a sodium salt , barium or silver, for example silver acetate, in a suitable solvent in which the inorganic salt that is formed, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.

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

The compounds of formula I and, where appropriate, their tautomers, in each case in free or 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 number, absolute and relative configuration of asymmetric carbon atoms that are present in the molecule, and/or depending on the configuration of non-aromatic double bonds, which are in the molecule; the present invention relates to pure isomers as well as to all possible mixtures of isomers, and should be understood in each instance above and below herein in this sense, even if stereochemical details have not been specifically mentioned in each instance.

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 the physicochemical differences of the components eg by fractional crystallization, distillation and/or chromatography.

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

Pure diastereomers or enantiomers can be obtained according to the present invention not only by separating suitable mixtures of isomers, but also by generally known diastereoselective or enantioselective synthetic 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, for example an H ₂ O ₂ /urea adduct, in the presence of an acid anhydride, for example 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 have different biological activities.

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

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

Table X. This table reveals 15 definitions of substituents X.001-X.015 of formula I-Q1,

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

and N-oxides of the compounds from Table X. Me represents a methyl group, Et represents an ethyl group, C(O)OEt represents an ethoxycarbonyl group.

Table 1. This table discloses 15 compounds 1.001-1.015 of formula I-Q1, where X represents S, and R ₂ , G ₂ , A, R ₁ , R ₇ and R ₈ are defined in table X. For example, compound 1.001 is characterized with the following structure:

Table 2. This table discloses 15 compounds 2.001-2.015 of formula I-Q1, where X is SO and R ₂ , G ₂ , A, R ₁ , R ₇ and R ₈ are defined in Table X.

Table 3. This table discloses 15 compounds 3.001-3.015 of formula I-Q1, where X is SO ₂ , and R ₂ , G ₂ , A, R ₁ , R ₇ and R ₈ are defined in table X.

Table Y. This table reveals 20 definitions of substituents Y.001-Y.020 of formula I-Q2,

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

and N-oxides of the compounds from Table Y. Me represents a methyl group, Et represents an ethyl group, C(O)OEt represents an ethoxycarbonyl group.

Table 4. This table discloses 20 compounds 4.001-4.020 of formula I-Q2, where X represents S, and R ₂ , G ₂ , G ₁ , A, R ₁ , R ₇ and R ₈ are defined in table Y. For example, compound 4.001 is characterized by the following structure:

Table 5. This table discloses 20 compounds 5.001-5.020 of formula I-Q2, where X is SO and R2, _{G2 , G1} , A, _R1 , _R7 and _R8 are defined in Table Y.

_Table 6. This table discloses 20 compounds 6.001-6.020 of formula I-Q2, where X is SO ₂ , and R 2, G ₂ , G ₁ , A, R ₁ , R ₇ and R ₈ are defined in table Y.

Table Z. This table reveals 20 definitions of substituents Z.001-Z.020 of formula I-Q3,

where R ₂ , R ₃ , R ₄ , A, R ₁ , R ₇ and R ₈ are defined below:

and N-oxides of the compounds from Table Z. Me represents a methyl group, Et represents an ethyl group, C(O)OEt represents an ethoxycarbonyl group. c-Pr represents a cyclopropyl group.

Table 7. This table discloses 20 compounds 7.001-7.020 of formula I-Q3, where X is S, and _R2 , _R3 , _R4 , A, _R1 , _R7 and _R8 are defined in Table Z. For example, compound 7.001 is characterized by the following structure:

Table 8. This table discloses 20 compounds 8.001-8.020 of formula I-Q3, where X is SO and _R2 , _R3 , _R4 , A, _R1 , _R7 and _R8 are defined in Table Z.

Table 9. This table discloses 20 compounds 9.001-9.020 of formula I-Q3, where X is SO ₂ , and R ₂ , R ₃ , R ₄ , A, R ₁ , R ₇ and R ₈ are defined in table Z.

Table XA. This table reveals 10 definitions of substituents ХА.001-ХА.010 of formula I-Q4,

where R ₂ , A, R ₁ , R ₇ and R ₈ are defined below:

and N-oxides of compounds from the XA table. Me represents a methyl group, Et represents an ethyl group, C(O)OEt represents an ethoxycarbonyl group.

Table 10. This table discloses 10 compounds 10.001-10.010 of formula I-Q4, where X represents S, and R ₂ , A, R ₁ , R ₇ and R ₈ are defined in table XA. For example, compound 10.001 has the following structure:

Table 11. This table discloses 10 compounds 11.001-11.010 of formula I-Q4, where X is SO, and R ₂ , A, R ₁ , R ₇ and R ₈ are defined in table XA.

Table 12. This table reveals 10 compounds 12.001-12.010 of the formula I-Q4, where X represents SO ₂ , and R ₂ , A, R ₁ , R ₇ and are defined in table XA.

The compounds of formula I according to the present invention find use as pesticides in the control, inhibition or destruction of animal pests (including arthropods, nematodes and molluscs, and in particular insects or members of the order Acarina, nematodes and molluscs). In particular, the compounds of formula I according to 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 according to the present invention act against generally susceptible, but also resistant, animal pests, such as insects or members of the order Acarina, at all or individual stages of development. The insecticidal, nematocidal, molluscicidal or acaricidal activity of the active ingredients according to the present invention can be exerted directly, i.e. in the destruction of pests, which occurs either immediately or over time, for example during molting, or indirectly, for example, in slowing growth, reducing egg laying and/or brood yield.

Examples of the above mentioned animal pests are:

from the order Acarina, for example,

Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp., Eotetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp., Polyphagotarsonemus spp., Psorop tes 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 spp., Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemLineata, Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Maladera castanea, Megascelis spp., Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp. , Sitotroga spp., Somaticus spp., Sphenophorus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp. and Trogoderma spp.;

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., Eu rydema 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., Sahlbergella 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. ., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp., Brachycaudus spp., Brevicoryne brassicae, Cacopsylla spp., Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp., Cofana spectra, Cryptomyzus spp., Ci cadulina spp. , Coccus hesperidum, Dalbulus maidis, Dialeurodes spp., Diaphorina citri, Diuraphis noxia, Dysaphis spp., Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae, Hyalopterus spp., Hyperomyzus pal lidus, Idioscopus clypealis, Jacobiasca lybica, 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, Odonaspis ruthae, Oregma lanigera Zehnter, Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Peregrinus maidis, Perkinsiella spp., Phorodon humuli, Phylloxera spp., Planococcus spp., Pseudaulaca spis spp ., Pseudococcus spp., Pseudatomoscelis seriatus, psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Rhopalosiphum spp., Saisetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Sogatella furcifera, spissistilus festinus, Tarophagus Proserpina, Toxoptera spp., Trialeurodes spp., Tridiscus 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 geminated

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 llava, Crambus spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydal ima perspectalis, Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea, Earias spp., Eldana saccharina, Ephestia spp., Epinotia spp., Estigmene acrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp. ., Feltia jaculiferia, Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hephetogramma spp., Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostege bifidalis, Lymantria spp. , Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Mythimna spp., Noctua spp., Operophtera spp., Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis llammea, Papaipema nebris, Pectinophora gossypiela, Perileucoptera coffeella , Pseudaletia 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., Sylepta derogate, Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusiani, 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 according to the present invention can be used as a control, i.e. 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 the organs of such plants, such as fruits, flowers, leaves, stems, tubers or roots, and in some cases even on plant organs, which are formed at a later date and at the same time remain protected from these pests.

Suitable target crops include, in particular, cereal crops such as wheat, barley, rye, oats, rice, maize or sorghum; beets such as sugar beets or fodder beets; fruit crops, for example pome, stone fruit or berry crops, such as apple, pear, plum, peach, almond, cherry or berry varieties, for example strawberry, raspberry or blackberry varieties; legumes such as varieties of beans, lentils, peas or soybeans; oilseeds such as oilseed rape, mustard, poppy, olives, sunflowers, coconut, castor beans, cocoa or peanuts; 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, carrots, onions, tomatoes, potatoes or bell peppers; members of Lauraceae such as avocado, Cinnamonium or camphor; as well as tobacco, nuts, coffee, eggplant varieties, sugar cane, tea, pepper, cultivated grape varieties, hops, plantain and rubber plants.

The compositions and/or methods of the present invention can also be applied to any ornamental and/or vegetable crops, including flowers, shrubs, broadleaf 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. tubereux), Bougainvillea spp., Brachycome spp., Brassica spp. (decorative), Calceolaria spp., Capsicum annuum, Catharanthus roseus, Carina 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. (clove), Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (P. peltatum, P. Zonale), Viola spp. (pansies), Petunia spp., Phlox spp., Plecthranthus 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., Surfinia 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 vegetable crops: Allium spp. (A sativum, A. sulfur, A. oschaninii, A. Porrum, A. ascalonicum, A. fistulosum), Anthriscus cerefolium, Apium graveolus, Asparagus officinalis, Beta vulgarus, Brassica spp. (B. Oleracea, B. Pekinensis, B. rapa), Capsicum annuum, Cicer arietinum, Cichorium endivia, Cichorum spp. (C. intybus, C. endivia), Citrillus lanatus, Cucumis spp. (C. sativus, C. melo), Cucurbita spp. (S. pepo, S. 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 Viciafaba.

Preferred ornamental plant species include African violet, Begonia, Dahlia, Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hortensia, rosemary, sage, St. John's wort, mint, bell 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 in cotton, vegetable, corn, rice and soybean crops. Moreover, the active ingredients according to the present invention are particularly suitable for the control of Mamestra (preferably in vegetable crops), Cydia pomonella (preferably in apple varieties), Empoasca (preferably in vegetable crops, 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 in cotton, vegetable, corn, rice and soybean crops. Moreover, the active ingredients according to the present invention are particularly suitable for the control of Mamestra (preferably in vegetable crops), Cydia pomonella (preferably in apple varieties), Empoasca (preferably in vegetable crops, 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 its parts by plant parasitic nematodes (endoparasitic, semi-parasitic and ectoparasitic nematodes), especially plant parasitic nematodes such as root nodule nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica , Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii and other Heterodera species; seed root-knot nematodes, Anguina spp.; stem and leaf nematodes, Aphelenchoides spp.; sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; 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; Spine-nosed nematodes, Dolichodorus spp.; spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; tunicate and tunicate nematodes, Hemicycliophora spp. and Hemicriconemoides spp.; Hirshmanniella spp.; lanceolate nematodes, Hoploaimus spp.; root growth nematodes, Nacobbus spp.; needle nematodes, Longidorus elongatus and other Longidorus species; short-bodied nematodes, Pratylenchus spp.; 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; Scutellonema spp.; bristle root nematodes, Trichodorus primitivus and other Trichodorus spp., Paratricodorus spp.; dwarf nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; citrus nematodes, Tylenchulus spp.; dagger nematodes, Xiphinema spp.; 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 shellfish. Examples of these molluscs 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 that have been transformed by recombinant DNA techniques in such a way that they have acquired the ability to synthesize one or more selective toxins, such as those known, for example, from toxin-producing bacteria, in characteristics of bacteria of the genus Bacillus.

Toxins that may 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 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; or insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi such as Streptomycetes toxins, plant lectins such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome inactivating proteins (RIPs), such as ricin, corn RIP, abrin, luffin, saporin or bryodin; steroid metabolic enzymes such as 3-hydroxysteroid oxidase, ecdysteroid UDP glycosyltransferase, cholesterol oxidases, 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, δ-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 using a new 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 replaced. With such amino acid substitutions, sequences recognized by proteases that are 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 producing such transgenic plants are generally known to one 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 transgenic plants gives the plants tolerance to harmful insects. Such insects can belong to any taxonomic group of insects, but are especially common among beetles (Coleoptera), dipterans (Diptera) and moths (Lepidoptera).

Transgenic plants containing one or more genes that encode insect resistance and express one or more toxins are known, and some of them are commercially available. Examples of such plants are: YieldGard® (a maize variety expressing the Cry1Ab toxin); YieldGard Rootworm® (maize variety expressing CRy3BB1 toxin); YieldGard Plus ® (maize variety expressing Cry1Ab toxin and CRy3BB1 toxin); Starlink® (a maize variety expressing the Cry9C toxin); Herculex I® (a maize variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin-N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety expressing Cry1Ac toxin); Bollgard I® (cotton variety expressing the Cry1Ac toxin); Bollgard II® (cotton variety expressing Cry1Ac toxin and Cry2Ab toxin); VipCot® (cotton variety expressing Vip3A toxin and Cry1Ab toxin); NewLeaf® (potato variety expressing the Cry3A toxin); NatureGard® Agrisure® GT Advantage (GA21 with glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 with corn borer (CB) resistance trait) and Protecta®.

Additional examples of such transgenic crops are the following.

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

2. Maize Bt176 from Syngenta Seeds SAS, Chemin de 1'Hobit 27, F-31 790 Saint-Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays that has been rendered resistant to corn borer (Osthnia nubilalis and Sesamia nonagrioides) through transgenic expression of the Cry1Ab toxin. Bt176 maize also transgenically expresses the PAT enzyme to achieve tolerance to the herbicide glufosinate ammonium.

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 resistant to insects by transgenic expression of a modified CRy3A toxin. This toxin is CRy3A055 modified by insertion of a sequence recognized by the protease cathepsin G. The production of such transgenic maize plants is described in WO 03/018810.

4. Maize MON 863 from Monsanto Europe SA 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses the CRy3Bb1 toxin and is resistant to some insects of the order Cole opt era.

5. Cotton plant 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 Lepidoptera insects and the PAT protein to achieve tolerance to the herbicide glufosinate ammonium.

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

Transgenic insect-resistant crop crops are also described in the 2003 BATS report (Zentrum Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) (http://bats.ch).

The term "crops" should be understood to also include crop plants that have been transformed by the use of recombinant DNA technologies in such a way that they are capable of synthesizing antipathogenic substances with selective action, such as, for example, so-called "pathogenesis-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 producing such transgenic plants are generally known to one skilled in the art and are described, for example, in the publications mentioned above.

Crops can also be modified to provide increased resistance to fungal (e.g., Fusarium, Anthracnose, or Phytophthora), bacterial (e.g., Pseudomonas), or viral (e.g., Potato leafroll virus, Tomato bronzing virus, Cucumber mosaic virus) pathogens.

Crops also include those with increased resistance to nematodes, such as soybean cyst nematode.

Crops that are tolerant to abiotic stress include those that have increased tolerance to drought, high salt, heat, cold, frost, or light, such as through the expression of NF-YB or other proteins known in this field of technology.

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

Additional areas of application for the compositions according to 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 applications in the field of sanitation, in particular the protection of humans, domestic animals and productive livestock from pests of the mentioned type.

The present invention also provides a method for controlling pests (such as mosquitoes and other disease vectors; see also http://www.who.int/malaria/vector_control/irs/en/). In one embodiment, a method of controlling pests includes applying the compositions of the present invention to a target pest, to a location, or to a surface or substrate by brushing, rolling, spraying, spreading, or dipping. As an example, the method of the present invention involves IRS application (indoor residual spraying) to a surface such as a wall, ceiling or floor surface. Another embodiment contemplates the use of these compositions in relation to a substrate, such as a non-woven or woven material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.

In one embodiment, a method of controlling such pests involves applying a pesticidal effective amount of the compositions of the present invention to the target pest, to its location, or to a surface or substrate, thereby providing 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 dipping. By way of example, the method of the present invention involves application of IRS to a surface, such as a wall, ceiling or floor surface, thereby ensuring effective activity of residual pesticides on the surface. In another embodiment, such compositions are contemplated for use in controlling pests on a substrate, such as woven material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents, due to its residual effect.

The substrates, including the non-woven fabrics, woven fabrics or mesh to be treated, 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 the like. 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 areas of application of the compositions according to the present invention are the area of introduction into the tree/trunk of all ornamental trees, as well as all varieties of fruit and nut trees.

In the field of tree administration/trunk treatment, the compounds of the present invention are particularly suitable against wood-boring insects from the order Lepidoptera, as mentioned above, and from the order Coleoptera, especially against the wood-boring insects listed in the following tables A and B.

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

In particular, the present invention can be used to control insect pests that feed on the roots of turf grass, including beetleworm larvae (such as Cyclocephala spp. (e.g., masked beetle, C. lurida), Rhizotrogus spp. (e.g., European beetle, R. majalis), Cotinus spp. (e.g. brilliant green beetle, C.nitidd), Popillia spp. (e.g. Japanese beetle, P. japonicd), Phyllophaga spp. (e.g. May/June beetle), Ataenius spp. ( for example, black root beetle of the genus Ataenius, A. spretulus), Maladera spp. (for example, Asian garden beetle M. castaned) and Tomarus spp.), scale insects (Margarodes spp.), mole crickets (dark yellow, southern and short-winged; Scapteriscus spp., Gryllotalpa africana) and larvae of centipede mosquitoes (marsh centipede, Tipula spp.).

The present invention can also be used to control insect pests of turf grass that live in thatch, including worms (such as Spodoptera frugiperda and Pseudaletia unipuncta), fall armyworm caterpillars, weevils (Sphenophorus spp., etc.) such as 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 insect pests of turfgrass that live above ground and feed on turfgrass leaves, including turf bugs (such as turf bugs, Blissus insularis), Bermuda grass mite (Ehophyes cynodoniensis), Chloris guiana worm { Antonina graminis), two-striped pennies (Propsapia bicincta), leafhoppers, fall armyworm caterpillars (family Noctuidae) and grass aphids.

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

In the field of sanitation, the compositions of the present invention are active against ectoparasites such as hard mites, soft mites, scabies, red beetles, flies (stinging and licking), parasitic fly larvae, lice, head lice, lice and fleas.

Examples of such parasites are the following.

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 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 the subclass Acaria (Acarida) and the orders Meta- and Mesostigmata, for example, 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), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

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

The compositions of the present invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec, Tryptodendron spec, Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec, and Dinoderus minutus, as well as hymenoptera insects such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Uro cerus 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 pesticidal agents in unmodified form, but are typically formulated in various ways using formulation auxiliaries such as carriers, solvents and surfactants. The compositions may be present in various physical forms, for example, sprayable powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent tablets, emulsifiable concentrates, microemulsion concentrates, oil-in-water emulsions, oil-based fluids formulations, aqueous dispersions, oil dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as a 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 before use. Dilutions can be carried out, for example, with water, liquid fertilizers, micronutrients, biological organisms, oil or solvents.

The compositions can be prepared, for example, by mixing the active ingredient with formulation auxiliaries to obtain compositions in the form of fine solids, granules, solutions, dispersions or emulsions. The active ingredients may also be formulated with other excipients, for example, fine solids, mineral oils, vegetable or animal oils, modified vegetable or animal oils, organic solvents, water, surfactants, or combinations thereof.

The active ingredients may also be contained in very small microcapsules. Microcapsules contain active ingredients in a porous carrier. This allows the active ingredients to be released into the environment in controlled quantities (eg slow release). Microcapsules typically have a diameter ranging from 0.1 to 500 microns. They contain active ingredients in amounts ranging from approximately 25 to 95% by 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 one skilled in the art. Alternatively, very fine microcapsules may be formed in which the active ingredient is contained in the form of fine particles in a solid matrix of the base substance, but the microcapsules are not themselves encapsulated.

Formulation auxiliaries that are suitable for preparing the compositions according to the present invention are known per se. Liquid carriers that can be used are water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid , diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, 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, Ethylene glycol methyl ether, gamma-butyrolactone, glycerin, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy propanol, methyl isoamyl ketone, 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, pro pylene 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, isopropane ol and high molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerin, N-methyl-2-pyrrolidone, etc.

Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, ground shells walnuts, lignin and similar substances.

A large number of surfactants can be used successfully in both solid and liquid formulations, especially in those formulations that can be diluted with a vehicle before use. Surfactants may be anionic, cationic, nonionic, or polymeric, and may be used as emulsifiers, wetting agents or suspending agents, or for other purposes. Typical surfactants include, for example, alkyl sulfate salts such as diethanolammonium lauryl sulfate; alkylaryl sulfonate salts such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products such as nonylphenol ethyloxylate; alcohol/alkylene oxide addition products such as tridecyl alcohol ethoxylate; soaps such as sodium stearate; alkyl naphthalene sulfonate salts such as sodium dibutyl naphthalene sulfonate; dialkyl esters of sulfosuccinate salts such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters such as sorbitolate; 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 excipients that may be used in pesticide formulations include crystallization inhibitors, viscosity modifiers, suspending agents, colorants, antioxidants, foaming agents, light absorbers, mixing aids, antifoams, complexing agents, neutralizing or pH-modifying agents, and buffers. corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze, microbiocides, and liquid and solid fertilizers.

Compositions in accordance with the present invention may include an additive comprising a 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 according to 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 sprayer reservoir at the required concentration after the spray mixture is prepared. Preferred oil additives include mineral or vegetable oils, such as canola oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of vegetable oils, such as methyl derivatives, or an animal oil, 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.

The compositions of the present invention generally 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 the formulation excipient which preferably includes from 0 to 25% by weight of surfactant. Since commercial products may 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 being controlled, prevailing climatic conditions and other factors determined by application method, time of application and target crop. As a general guide, the compounds can be applied at rates from 1 to 2000 l/ha, in particular from 10 to 1000 l/ha.

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

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

The combination is thoroughly mixed with the excipients and the mixture is thoroughly ground in a suitable mill to obtain wettable powders which can be diluted with water to obtain suspensions of the required concentration.

The combination is thoroughly mixed with the 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 diluting with water, emulsions of any required dilution can be obtained, which can be used to protect plants.

Ready-to-use powdered preparations are prepared by mixing the combination with a carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry seed treatment.

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.

The finely ground combination in a mixing device is evenly applied to the kaolin moistened with polyethylene glycol. In this way, dust-free, coated granules are obtained.

Suspension concentrate

The finely ground combination is thoroughly mixed with the excipients to obtain a suspension concentrate, from which suspensions of any required dilution can be obtained by dilution with water. With the help of such diluted solutions, living plants, as well as plant propagation material, can be treated and protected from contamination by microorganisms by spraying, watering or immersing.

Flowable seed treatment concentrate

The finely ground combination is thoroughly mixed with the excipients to obtain a suspension concentrate, from which suspensions of any required dilution can be obtained by dilution with water. With the help of such diluted solutions, living plants, as well as plant propagation material, can be treated and protected from contamination by microorganisms by spraying, watering or immersing.

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 polyvinyl alcohol, 0.05 parts defoamer and 51.6 parts water to obtain particles of the required size. To this emulsion is added a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts water. The mixture is stirred until the polymerization reaction is complete. The resulting capsule suspension is stabilized by adding 0.25 parts thickener and 3 parts dispersant. The composition of the capsule suspension contains 28% active ingredients. The average diameter of capsules is 8-15 microns. The resulting composition 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 application suspension (SU), ultra low volume liquid (UL), technical concentrate (TC), dispersible concentrate (DC), wettable powder (WP), soluble granule (SG) or any other technically feasible formulation in combination with agriculturally acceptable excipients .

Examples of receiving

"Mp" means 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 were measured in the indicated declared solvents. Any of the following LCMS methods were used to characterize the compounds. The characteristic LCMS values obtained for each compound were the retention time ("Rt", recorded in minutes) and the measured molecular ion content (M+H) ⁺ or (M-H) ^- .

LCMS and GCMS methods

Method 1. Standard 1

Spectra were recorded on a Waters mass spectrometer (ZQ single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative ions, capillary voltage: 3.00 kV, cone voltage range: 30-60 V, extractor voltage : 2.00 V, source temperature: 150°C, desolvation temperature: 350°C, gas flow in the cone: 0 l/h, gas flow for desolvation: 650 l/h, mass range: 100-900 Da) , and Waters' Acquity UPLC: binary pump, heated column section, and diode array detector. Solvent degasser, binary pump, heated section of the column and diode array detector. Column: Waters UPLC HSS T3, 1.8 µm, 30×2.1 mm, temperature: 60°C, DAD wavelength range (nm): 210-500; solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH: gradient: 0 min. 0% B, 100% A; 1.2-1.5 min. 100% B; flow (ml/min.) 0.85.

Method 2. Standard length

Spectra were recorded on a Waters mass spectrometer (SQD or ZQ single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative ions, capillary voltage: 3.00 kV, cone voltage range: 30-60 V, voltage in extractor: 2.00 V, source temperature: 150°C, desolvation temperature: 350°C, gas flow in the cone: 0 l/h, gas flow for desolvation: 650 l/h, mass range: 100-900 Yes ), and Acquity UPLC from Waters: binary pump, heated column section and diode array detector. Solvent degasser, binary pump, heated section of the column and diode array detector. Column: Waters UPLC HSS T3, 1.8 µm, 30×2.1 mm, temperature: 60°C, DAD wavelength range (nm): 210-500; solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; gradient: 0 min. 0% B, 100% A; 2.7-3.0 min. 100% B; flow (ml/min.) 0.85.

Method 3. Standard length 2

Spectra were recorded on an Agilent Technologies mass spectrometer (6410 Triple Quadrupole Mass Spectrometer) equipped with an electrospray source (polarity: positive and negative polarity switch, capillary voltage: 4.00 kV, fragmentor voltage: 100.00 V, gas temperature: 350°C, gas flow: 11 l/min, nebulizer gas: 45 psi, mass range: 110-1000 Da, DAD wavelength range: 210-400 nm). Column: KINETEX EVO C18, length 50 mm, diameter 4.6 mm, particle size 2.6 µm. Column thermostat 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; from 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 Waters mass spectrometer (Acquity SDS mass spectrometer) equipped with an electrospray source (polarity: positive and negative polarity switch, capillary voltage: 3.00 kV, cone voltage: 41.00 V, source temperature: 150 °C, gas flow for desolvation: 1000 l/h, desolvation temperature: 500°C, gas flow in the cone: 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 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 PL Preparation of 2-[5-ethylsulfonyl-6-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]-2-methylpropanenitrile (compound P1)

Step 1. Preparation of 2-(6-acetyl-5-ethylsulfonyl-3-pyridyl)-2-methylpropanenitrile

To a solution of 2-(6-acetyl-5-ethylsulfonyl-3-pyridyl)acetonitrile (1.50 g, 5.95 mmol, 1.00 eq.) [prepared as described in WO 2016/071214] in dimethylformamide (24 ml ) sodium hydride (478 mg, 12.5 mmol, 2.10 eq) was added at 0°C under argon. The resulting mixture was stirred at 0°C for 30 minutes. and then added dropwise to a solution of methane iodine (0.777 ml, 341 mg, 12.5 mmol, 2.10 eq.) in dimethylformamide (24 ml) at 0°C. The mixture was slowly warmed to room temperature and stirred at this temperature for 4 hours. The reaction mixture was diluted with ethyl acetate and sat. ammonium chloride solution. The aqueous layer was separated and extracted twice with ethyl acetate. The organic layers were combined, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The crude product was purified by flash chromatography (silica gel, ethyl acetate/cyclohexane) to give 2-(6-acetyl-5-ethylsulfonyl-3-pyridyl)-2-methylpropanenitrile. LCMS (method 1): 281 (M+H) ⁺ ; retention time: 0.79 minutes

Step 2. Preparation of 2-[6-(2-bromoacetyl)-5-ethylsulfonyl-3-pyridyl]-2-methylpropanenitrile

To a solution of 2-(6-acetyl-5-ethylsulfonyl-3-pyridyl)-2-methylapropanenitrile (734 mg, 2.62 mmol, 1.00 eq.) in ethyl acetate (6.5 ml) and chloroform (6.5 mL) copper(II) bromide (1.17 g, 5.24 mmol, 2.00 eq.) was added at room temperature under argon. The resulting mixture was heated to 140°C for 2.5 hours under the influence of microwave radiation. The reaction mixture was filtered through a pad of celite and rinsed with ethyl acetate. The filtrate was concentrated under reduced pressure, and the resulting crude product was purified by column chromatography (silica gel, ethyl acetate/cyclohexane) to give 2-[6-(2-bromoacetyl)-5-ethylsulfonyl-3-pyridyl]-2-methylpropanenitrile. LCMS (method 1): 359 (M+H) ⁺ ; retention time: 0.88 minutes

Step 3. Preparation of 2-[5-ethylsulfonyl-6-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]-2-methylpropanenitrile (compound P1)

6-( trifluoromethyl)pyrimidin-4-amine (142 mg, 0.842 mmol, 1.10 eq.) [prepared as described in WO 2015/000715] at room temperature under argon. The resulting mixture was heated to 90°C for 2 days. The reaction mixture was cooled at room temperature and diluted with ethyl acetate and saturated ammonium chloride solution. The aqueous layer was separated and extracted twice with ethyl acetate. The organic layers were combined, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by reverse phase HPLC to give the title compound. LCMS (method 2): 424 (M+H) ⁺ ; retention time: 1.38 min.

Examples P14, P15, P16 and P20, shown in Table P below, were prepared using a sequence similar to that described in Example P1.

EXAMPLE P2. Preparation of 2-[5-ethylsulfonyl-6-[6-(trifluoromethyl)pyrazolo[4.3-c]pyridin-2-yl]-3-pyridyl]-2-methylpropanenitrile (compound P2)

Stage 1. Preparation of 2,5-dibromo-3-ethylsulfanylpyridine

A solution of diethyl disulfide (7.76 g, 63.5 mmol, 2.00 eq.) and tert-butyl nitrite (4.91 g, 47.6 mmol, 1.50 eq.) in DCE (60 mL) and DCM (40 ml) was heated to 40°C. To this mixture was added a solution of 2,5-dibromopyridin-3-amine (8.00 g, 31.7 mmol, 1.00 eq.) in DCE (200 ml) slowly over 90 minutes, and the reaction mixture was stirred for an additional 1 hour at 40°C. After completion of the reaction, the reaction mass was cooled, diluted with water (100 ml) and extracted with DCM (2 × 100 ml). The organic layer was separated, the combined organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by column chromatography (silica gel, 5-15% ethyl acetate/cyclohexane) to give 2,5-dibromo-3-ethylsulfanylpyridine. LCMS (Method 4): 296 (M+H) ⁺ , retention time 1.16 min.

¹ H NMR (400 MHz, CDCl ₃ ) δ/ppm: 1.32 (t, 3 H), 2.98 (m, 2 H), 7.52 (s, 1 H) 8.19 (s, 1 H ).

Step 2. Preparation of 2,5-dibromo-3-ethylsulfonylpyridine

Meta-chloroperbenzoic acid (1.83 g, 7.41 mmol, 2.20 eq.), and the resulting solution was stirred at room temperature for 2 hours. The reaction mixture was quenched with sodium hydroxide solution (1 M, 100 ml) and extracted with dichloromethane (3 x 100 ml). The combined organic layers were dried (Na ₂ SO ₄ ), filtered and concentrated under reduced pressure. The crude product was purified by column chromatography (silica gel, 30% ethyl acetate/cyclohexane) to give 2,5-dibromo-3-ethylsulfonylpyridine. LCMS (method 4): 328 (M+H) ⁺ , retention time 0.88 min.

¹ H NMR (400 MHz, CDCl ₃ ) δ/ppm: 1.34 (t, 3 H), 3.55 (q, 2 H), 8.54 (d, 1 H), 8.67 (d, 1H).

Step 3. Preparation of (5-bromo-3-ethylsulfonyl-2-pyridyl)hydrazine

Hydrazine monohydrate (6.20 g, 120 mmol, 6.00 eq.) was added to a solution of 2,5-dibromo-3-ethylsulfonylpyridine (6.80 g, 21.0 mmol, 1.00 eq.) in 1.4 -dioxane (21 ml) and the reaction mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction mixture was diluted with water (30 ml) and extracted with ethyl acetate (2 x 30 ml). The combined organic layers were washed with water (20 ml), dried (Na ₂ SO ₄ ), filtered and concentrated under reduced pressure. The resulting crude (5-bromo-3-ethylsulfonyl-2-pyridyl)hydrazine was used for the next step without any further purification. LCMS (method 3): 280 (M+H) ⁺ , retention time 0.60 min.

Step 4. Preparation of 4-[2-(5-bromo-3-ethylsulfonyl-2-pyridyl)hydrazino]-6-(trifluoromethyl)pyridine-3-carboxylic acid

Into a round bottom reflux flask charged with 4-chloro-6-(trifluoromethyl)pyridine-3-carboxylic acid (2.50 g, 11.0 mmol, 1.00 eq.) [CAS 1060810-66-3 , commercially available or prepared according to WO 2013/064460, page 120], a solution of (5-bromo-3-ethylsulfonyl-2-pyridyl)hydrazine (4.70 g, 17.0 mmol, 1.50 eq. ) in pentan-1-ol (120 ml), and the resulting reaction mixture was heated at 110°C overnight. The resulting reaction mixture was concentrated under reduced pressure to remove pentanol. The remaining pentanol was removed by adding toluene and co-evaporation. The resulting crude mixture was diluted with water (100 ml), brine (100 ml) and extracted with ethyl acetate (3 x 200 ml). The combined organic layers were dried (Na ₂ SO ₄ ), filtered and concentrated under reduced pressure to give the crude product as a solid. Trituration with cyclohexane gave 4-[2-(5-bromo-3-ethylsulfonyl-2-pyridyl)hydrazino]-6-(trifluoromethyl)pyridine-3-carboxylic acid as a solid. This compound was used for the next step without any further purification. LCMS (method 3): 469 (M+H) ⁺ , retention time 1.39 min.

Step 5. Preparation of 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-3-chloro-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine

4-[2-(5-bromo-3-ethylsulfonyl-2-pyridyl)hydrazino]-6-(trifluoromethyl)pyridine-3-carboxylic acid solution (3.00 g, 6.39 mmol, 1.00 eq.) in POCl ₃ (30 ml) was refluxed to 110°C for 1.5 hours. The resulting crude reaction mixture was then poured onto ice (500 g) and quenched with solid sodium bicarbonate. The resulting mixture was extracted with dichloromethane (3 x 200 ml). The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude solid was purified by trituration with cyclohexane to give 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-3-chloro-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine. LCMS (method 4): 469 (M+H) ⁺ , retention time 1.10 min. ¹ H NMR (400 MHz, CDCl ₃ ) δ/ppm: 1.33 (t, 3 H), 3.59 (q, 2 H), 7.97 (s, 1 H), 8.73 (s, 1 N), 8.99 (s, 1 N), 9.29 (s, 1 N).

Step 6. Preparation of 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine

To a solution of 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-3-chloro-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine (1.80 g, 3.80 mmol, 1.00 eq.) in acetic acid (90 ml), zinc (500 mg, 7.70 mmol, 2.00 eq.) was slowly added and the reaction mixture was heated to 60°C for 2 hours. The reaction mixture was allowed to cool to room temperature, it was poured into water (30 ml) and the resulting solution was extracted with ethyl acetate (3 x 20 ml). The combined organic layers were washed with brine (30 ml), dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography (40% ethyl acetate/cyclohexane) to give 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine. LCMS (method 3): 435 (M+H) ⁺ , retention time 1.05 min. ¹ H NMR (400 MHz, CDCl ₃ ) δ/ppm: 1.44 (t, 3 H), 3.99 (q, 2 H), 8.04 (s, 1 H), 8.77 (s, 1 N), 8.88 (s, 1 N), 8.91 (s, 1 N), 9.39 (s, 1 N).

Step 7. Preparation of 2-[5-ethylsulfonyl-6-[6-(trifluoromethyl)pyrazolo[4,3-c]pyridin-2-yl]-3-pyridyl]acetonitrile

To a solution of 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine (500 mg, 1.15 mmol, 1.00 eq.) in N, To N-dimethylformamide (7.0 mL), trimethylsilylacetonitrile (265 mg, 2.30 mmol, 2.00 eq), zinc(II) fluoride (73 mg, 0.69 mmol, 0.60 eq) and Xanthphos ( 27 mg, 0.046 mmol, 0.040 eq.) in a nitrogen atmosphere. The reaction mass was purged with nitrogen for 15 min. followed by the addition of Pd ₂ (aba) ₃ *CHCl ₃ (22 mg, 0.020 mmol, 0.020 eq.). The resulting reaction mixture was then heated at 140°C for 30 minutes. under the influence of microwave radiation. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate (30 ml) and water (15 ml) was added. The organic phase was separated, washed with water, brine, dried (Na ₂ SO ₄ ) and filtered. Concentration under reduced pressure provided crude material, which was purified by column chromatography (silica gel, ethyl acetate/cyclohexane) to give the title compound. LCMS (method 4): 396 (M+H) ⁺ , retention time 0.87 min. ¹ H NMR (400 MHz, DMSO-d ₆ ) δ/ppm: 1.21-1.29 (m, 3 H), 3.88 (q, 2 H), 4.40 (s, 2 H), 8.35 (s, 1 N), 8.63 (d, 1 N), 8.96 (d, 1 N), 9.44 (s, 1 N), 9.46-9.50 (m, 1 N).

Step 8. Preparation of 2-[5-ethylsulfonyl-6-[6-(trifluoromethyl)pyrazolo[4,3-c]pyridin-2-yl]-3-pyridyl]-2-methylpropanenitrile (compound P2)

To a solution of 2-[5-ethylsulfonyl-6-[6-(trifluoromethyl)pyrazolo[4,3-c]pyridin-2-yl]-3-pyridyl]acetonitrile (245 mg, 0.620 mmol, 1.00 eq.) in acetonitrile (15 ml), cesium carbonate (717 mg, 1.86 mmol, 3.00 eq.) was added followed by iodomethane (264 mg, 1.86 mmol, 3.00 eq.). The resulting brown solution was stirred at room temperature for 5 hours. The reaction mixture was then diluted with ethyl acetate (30 ml) and water (20 ml). The organic phase was separated, washed with water, brine and dried over sodium sulfate, filtered and evaporated. The crude material was purified by column chromatography (silica gel, ethyl acetate/cyclohexane) to give the title compound. LCMS (method 4): 424 (M+H) ⁺ , retention time 1.01 min. ¹ H NMR (400 MHz, CDCl ₃ ) δ/ppm: 1.45-1.50 (m, 3 H), 1.92 (s, 6 H), 4.01 (q, 2 H), 8. 05 (s, 1 N), 8.66 (d, 1 N), 8.96 (d, 1 N), 9.02 (d, 1 N), 9.42 (s, 1 N).

EXAMPLE P3. Preparation of_2-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfonyl-3-pyridyl]-2-methylpropanenitrile (P3 connections)

Step 1. Preparation of 2-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfonyl-3-pyridyl] acetonitrile

To a solution of 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-5-ethyl-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (800 mg, 1. 62 mmol, 1.00 eq.) [prepared as described in WO 2017/084879 A1] in dimethylformamide (3.5 ml) was added 2-trimethylsilylacetonitrile (0.336 ml, 278 mg, 2.43 mmol, 1.50 eq.) , Xantphos (38 mg, 0.065 mmol, 0.040 eq.), zinc(II) fluoride (102 mg, 0.973 mmol, 0.600 eq.) and (dba) ₃ Pd ₂ *CHCl ₃ (30 mg, 0.032 mmol, 0.020 eq. ) in an argon atmosphere. The reaction mixture was heated to 100°C and stirred for 20 hours. After cooling to room temperature, the reaction mixture was diluted in ethyl acetate (100 ml) and filtered through a celite plug. The filtrate was washed with water (3 x 25 ml) and saline (25 ml). The combined organic layers were dried (Na ₂ SO ₄ ) and concentrated under reduced pressure. The crude material was purified by column chromatography (silica gel, methanol/dichloromethane) to give the title compound. LCMS (method 1): 454 (M+H) ⁺ , retention time 0.93 min.

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

To a solution of 2-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfonyl-3-pyridyl]acetonitrile ( 300 mg, 0.662 mmol, 1.00 eq.) in dimethylformamide (6.0 mL), sodium hydride (60.8 mg, 1.59 mmol, 2.40 eq.) was added at 0° C. under argon. The resulting mixture was stirred for 30 minutes. at 0°C and then added dropwise to a solution of iodomethane (0.098 ml, 225 mg, 1.59 mmol, 2.40 eq.) in dimethylformamide (3 ml) at 0°C. The mixture was slowly warmed to room temperature and stirring was continued for 18 hours. The resulting reaction mixture was diluted with ethyl acetate and a saturated solution of saturated ammonium chloride. The aqueous layer was separated and extracted with ethyl acetate (2x). The organic layers were combined, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by column chromatography (silica gel, methanol/dichloromethane) to obtain the title compound as a white solid. LCMS (method 1): 482 (M+H) ⁺ ; retention time: 1.02 min. ¹ H NMR (400 MHz, CDCl ₃ ) δ/ppm: 1.37 (t, 3 H), 1.39 (brt, 3 H), 1.90 (s, 6 H), 3.82 (d, 2 N), 4.10 (s, 3 N), 4.25 (d, 2 N), 7.21 (s, 1 N), 8.51 (d, 1 N), 9.15 (d, 1 N).

Examples P10, P11, P12, P13, P17 and P18, shown in Table P below, were prepared using a sequence similar to that described in Example P3.

EXAMPLE P5. Preparation of 2-[6-[7-(difluoromethylsulfanyl)imidazo[1,2-a]pyridin-2-yl]-5-ethylsulfonyl-3-pyridyl]-2-methylpropanenitrile (compound P5)

Step 1. Preparation of 2-[5-ethylsulfonyl-6-(7-iodimidazo[1,2-a]pyridin-2-yl)-3-pyridyl]-2-methylpropanenitrile (compound I11)

A mixture of 4-iodopyridin-2-amine (368 mg, 1.67 mmol, 1.00 eq.) and 2-[6-(2-bromoacetyl)-5-ethylsulfonyl-3-pyridyl]-2-methylpropanenitrile (600 mg , 1.67 mmol, 1.00 eq.) [compound I2 prepared as described in step 2 of Example P1] in acetonitrile (12 ml) was irradiated under microwave conditions at 150° C. for 1 hour. After cooling to room temperature, the reaction mass was diluted with water (10 ml) and saline solution (10 ml) and the aqueous phase was extracted with ethyl acetate (3 * 30 ml). The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. Purification by flash silica gel chromatography (50% ethyl acetate in cyclohexane) gave 2-[5-ethylsulfonyl-6-(7-iodimidazo[1,2-a]pyridin-2-yl)-3-pyridyl]-2 -methylpropanenitrile (450 mg, 0.94 mmol). LCMS (method 4): 481 (M+H) ⁺ ; retention time: 0.94 min. 1H NMR (400 MHz, DMSO-d6) δ ppm 1.27 (t, 3 H) 1.82-1.85 (m, 6 H) 1.83 (s, 1 H) 4.22 (d, 2 N) 7.27 (dd, 1 N) 8.15 (s, 1 N) 8.44-8.49 (m, 3 H) 9.10-9.13 (m, 1 N).

Step 2. Preparation of methyl 3-[2-[5-(1-cyano-1-methylethyl)-3-ethylsulfonyl-2-pyridyl]imidazo[1,2-a]pyridin-7-yl]sulfanylpropanoate (compound I12 )

Palladium acetate (12 mg, 0.05 mmol, 0.05 eq.) was added to the mixture of 2-[5-ethylsulfonyl-6-(7-iodimidazo[1,2-a]pyridin-2-yl)-3-pyridyl ]-2-methylpropanenitrile (500 mg, 1.04 mmol) [compound I11 prepared as above], N,N-diisopropylethylamine (370 μl, 2.08 mmol, 2.00 eq.), methyl 3-mercaptopropionate (141 μl, 1.25 mmol, 1.20 eq.) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (62 mg, 0.10 mmol, 0.10 eq.) in 1,4- dioxane (10.4 ml), previously degassed with nitrogen for 10 min. The reaction mixture was stirred at 100°C for 2 hours. After cooling to room temperature, the reaction mass was diluted with water (20 ml) and the aqueous phase was extracted with ethyl acetate (3 * 30 ml). The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The resulting solid was triturated with cyclohexane to give methyl 3-[2-[5-(1-cyano-1-methylethyl)-3-ethylsulfonyl-2-pyridyl]imidazo[1,2-a]pyridin-7-yl] sulfanylpropanoate (350 mg, 0.74 mmol). LCMS (method 4): 473 (M+H) ⁺ ; retention time: 0.82 min.

Step 3. Preparation of 2-[5-ethylsulfonyl-6-(7-sulfanylimidazo[1,2-a]pyridin-2-yl)-3-pyridyl]-2-methylpropanenitrile (compound I13)

Sodium hydroxide (69 mg, 1.68 mmol, 1.50 eq.) was added to the methyl 3-[2-[5-(1-cyano-1-methylethyl)-3-ethylsulfonyl-2-pyridyl]imidazo[ solution 1,2-a]pyridin-7-yl]sulfanylpropanoate (530 mg, 1.12 mmol) [compound 112 prepared as above] in methanol (1.0 ml). After stirring for 3 hours at room temperature, the reaction mixture was diluted with water (10 ml), acidified with 1 N. HCl (10 ml) and the aqueous phase was extracted with ethyl acetate (3 * 30 ml). The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was used quickly without any purification. LCMS (method 3): 387 (M+H) ⁺ ; retention time: 1.11 min.

Step 4. Preparation of 2-[6-[7-(difluoromethylsulfanyl)imidazo[1,2-a]pyridin-2-yl]-5-ethylsulfonyl-3-pyridyl]-2-methylpropanenitrile (compound P5)

Sodium 2-Chloro-2,2-difluoroacetate (357 mg, 2.33 mmol, 2.00 eq.) and potassium carbonate (241 mg, 1.75 mmol, 1.50 eq.) were added to the 2-[5 -ethylsulfonyl-6-(7-sulfanylimidazo[1,2-a]pyridin-2-yl)-3-pyridyl]-2-methylpropanenitrile (450 mg, 1.16 mmol) in N,N-dimethylformamide (5.0 ml). After stirring at 90°C for 4 hours, the reaction mixture was cooled to room temperature and quenched with cold water (15 ml). The aqueous phase was extracted with ethyl acetate (3 * 30 ml). The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. Purification of the crude material by flash chromatography (silica gel, 30% ethyl acetate in cyclohexane) gave 2-[6-[7-(difluoromethylsulfanyl)imidazo[1,2-a]pyridin-2-yl]-5-ethylsulfonyl-3 -pyridyl]-2-methylpropanenitrile (95 mg, 0.22 mmol). LCMS (method 4): 437 (M+H) ⁺ ; retention time: 0.91 min. 1H NMR (400 MHz, DMSO-d6) δ ppm 1.25-1.31 (m, 3 H) 1.82-1.87 (m, 6 H) 4.24 (q, 2 H) 7.09 -7.16 (m, 1 N) 7.51-7.84 (m, 1 N) 7.92 (s, 1 N) 8.48 (d, 1 N) 8.54 (s, 1 N) 8.71 (d, 1 N) 9.13 (d, 1 N).

Examples P6, P7, P9 and P19, shown in Table P below, were prepared using a sequence similar to that described in Example P5.

EXAMPLE P8. Preparation of 2-[5-ethylsulfonyl-6-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridyl]-2-methylpropanenitrile (compound P8)

To a solution of 2-[6-(2-bromoacetyl)-5-ethylsulfonyl-3-pyridyl]-2-methylpropanenitrile (300 mg, 0.84 mmol, 1.00 eq.) [compound 12, prepared as described in step 2 Example P1] in acetonitrile (6.3 ml) was added 5-(trifluoromethyl)pyridazin-3-amine (150 mg, 0.88 mmol, 1.00 eq.) [prepared as described in WO 2016/051193) and magnesium oxide (67 mg, 1.70 mmol, 2.00 eq.) at room temperature under argon. The resulting mixture was heated to 90°C overnight. The reaction mixture was cooled at room temperature, filtered and concentrated. The crude material was diluted with ethyl acetate and saturated ammonium chloride solution. The aqueous layer was separated and extracted twice with ethyl acetate. The organic layers were combined, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by flash silica gel chromatography (ethyl acetate in cyclohexane) to give the title compound. LCMS (method 4): 424 (M+H) ⁺ ; retention time: 0.97 min.

Preferred are the following mixtures of compounds of formula I with active ingredients (the abbreviation “TX” means “one compound selected from the group consisting of compounds described in tables 1-12 and P of the present invention”):

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

acaricide selected from the group of substances consisting of 1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910) + TX, 2,4-dichlorophenylbenzenesulfonate (IUPAC/Chemical Abstract Service name) (1059 )+TX, 2-fluoro-N-methyl-N-1-naphtylacetamide (IUPAC name) (1295)+TX, 4-chlorophenylphenylsulfone (IUPAC name) (981)+TX, abamectin (1)+TX, acequinocyl (3) + TX, acetoprol [CCN] + TX, acrinatrine (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 hydroxalate (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, azocyclotine (46) + TX, nitrogen (889) + TX, benomyl (62) + TX, benoxaphos (alternative name) [CCN] + TX, benzoximate (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, butocarboxyme (103) + TX, butoxycarboxyme (104) + TX, butylpyridabene (alternative name) + TX, calcium polysulfide (IUPAC name) (111) + TX , camphechlor (941)+TX, carbanolate (943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbophenothione (947)+TX, CGA 50439 (development code) (125)+TX, quinomethionate ( 126)+TC, chlorobenzide (959)+TC, chlordimeform (964)+TC, chlordimeform hydrochloride (964)+TC, chlorfenapyr (130)+TC, chlorphenetol (968)+TC, chlorphenson (970)+TC, chlorphensulfide ( 971)+TC, chlorfenvinphos (131)+TC, chlorobenzilate (975)+TC, chloromebuform (977)+TC, chloromethiuron (978)+TC, chlorpropylate (983)+TC, chlorpyrifos (145)+TC, chlorpyrifos-methyl (146)+TC, chlorothiophos (994)+TC, cinerin I (696)+TC, cinerin II (696)+TC, cinerins (696)+TC, clofentesine (158)+TC, closantel (alternative name) [CCN ]+TX, coumaphos (174)+TX, crotamiton (alternative name) [CCN]+TX, crotoxyphos (1010)+TX, kufraneba (1013)+TX, cyanoate (1020)+TX, cyflumetofen (CAS registration number: 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-8-methyl (224) + TX, demeton-S-methylsulfone (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diazinon (227)+TX, dichlofluanid (230)+TX, dichlorvos (236)+TX, diclifos (alternative name)+TX, dicofol (242)+TX, dicrotophos (243)+TX, dienochlor (1071)+TX, dimefox (1081) + TX, dimethoate (262) + TX, dynactin (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, dinoterbon (1098) + TX , dioxathione (1102)+TX, diphenylsulfone (IUPAC name) (1103)+TX, disulfiram (alternative name) [CCN]+TX, disulfoton (278)+TX, DNOC (282)+TX, dophenapine (1113)+ TX, doramectin (alternative name) [CCN]+TX, endosulfan (294)+TX, endothion (1121)+TX, EPN (297)+TX, eprinomectin (alternative name) [CCN]+TX, ethion (309)+ TC, methyl ethoate (1134)+TC, etoxazole (320)+TC, etrimphos (1142)+TC, phenazaflor (1147)+TC, phenazaquin (328)+TC, phenbutatin oxide (330)+TC, phenothiocarb (337 )+TX, fenpropathrina (342)+TX, fenpyrad (alternative name)+TX, fenpyroximate (345)+TX, fenzone (1157)+TX, fentrifanil (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, fluorbenzide (1174)+TX, fluvalinate (1184)+TX, FMC 1137 (development code) (1185)+TX, formatenate (405)+TX, formatenate hydrochloride (405)+TX , formothione (1192)+TX, formparanate (1193)+TX, gamma-HCN (430)+TX, gliodin (1205)+TX, galfenprox (424)+TX, heptenophos (432)+TX, hexadecylcyclopropanecarboxylate (IUPAC name /Chemical Abstract Service) (1216)+TX, hexythiazox (441)+TX, iodomethane (IUPAC name) (542)+TX, isocarbophos (alternative name) (473)+TX, isopropyl-O-(methoxyaminothiophosphoryl) salicylate ( IUPAC name) (473) + TX, ivermectin (alternative name) [CCN] + TX, jasmoline I (696) + TX, jasmoline II (696) + TX, iodofenphos (1248) + TX, lindane (430) + TX , lufenuron (490) + TX, malathion (492) + TX, malonobene (1254) + TX, mecarbam (502) + TX, mephospholane (1261) + TX, mesulfene (alternative name) [CCN] + TX, metacryphos (1266 ) + TC, methamidophos (527) + TC, methidathione (529) + TC, methiocarb (530) + TC, methomyl (531) + TC, methyl bromide (537) + TC, metholcarb (550) + TC, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternate name) [CCN] + TX, mipafox (1293) + TX, monocrotophos (561) + TX, morphothione (1300) + TX , moxidectin (alternative name) [CCN] + TX, naleda (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) + TX, nifluridide (1309) + TX, nikkomycin (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, oxideprophos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, phencapton (1330) + TX, phentoate (631) + TX, phorate (636) + TX, fosalone (637) + TX, phospholane (1338) + TX, phosmet (638 ) + TX, phosphamidone (639) + TX, phoxime (642) + TX, pirimiphosmethyl (652) + TX, polychloroterpenes (traditional name) (1347) + TX, polynactins (alternative name) (653) + TX, proclonol (1350 ) + TX, profenofos (662) + TX, promacyl (1354) + TX, propargite (671) + TX, propetamphos (673) + TX, propoxur (678) + TX, protidation (1360) + TX, protoate (1362) + TC, pyrethrin I (696) + TC, pyrethrin II (696) + TC, pyrethrins (696) + TC, pyridabene (699) + TC, pyridafenthion (701) + TC, pyrimidifene (706) + TC, 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 (alternate 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, terbam (alternative name) + TX, tetrachlorvinphos (777 ) + TX, tetradifon (786) + TX, tetranactin (alternative name) (653) + TX, tetrasula (1425) + TX, thiaphenox (alternative name) + TX, thiocarboxyme (1431) + TX, thiophanox (800) + TX , thiometone (801) + TX, thioquinox (1436) + TX, thuringiensin (alternative name) [CCN] + TX, triamiphos (1441) + TX, triarathene (1443) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, triphenophos (1455) + TX, trinactin (alternative name) (653) + TX, vamidothione (847) + TX, vaniliprole [CCN] and YI-5302 (compound code) + TX,

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

anthelmintic selected from the group of substances 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,

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

bactericide selected from the group of substances consisting of 1-hydroxy-N-pyridin-2-thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TC, 8-hydroxyquinoline sulfate (446) + TC, bronopol (97) + TC, copper dioctanoate (IUPAC name) (170) + TC, copper hydroxide (IUPAC name) (169) + TC, cresol [CCN] + TC, dichlorophen (232) + TC, dipyrithione (1105) + TC, dodicine (1112) + TC, fenaminosulfate (1144) + TC, formaldehyde (404) + TC, hydrarhafen (alternative name) [CCN] + TC, kasugamycin ( 483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrine (580) + TX, octylinone (590) + TX, oxolinic acid (606) + TQ, oxytetracycline (611) + TQ, potassium hydroxyquinoline sulfate (446) + TQ, probenazole (658) + TQ, streptomycin (744) + TQ, streptomycin sesquisulfate (744) + TQ, teclophthalam (766) + TQ and thiomersal (alternative name ) [CCN] + TX,

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 ftrmus (alternative name) (48) + TX, Bacillus sphaericus Neide (scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51) + TX, Bacillus thuringiensis subspecies aizawai (scientific name) (51) + TX, Bacillus thuringiensis subspecies israelensis (scientific name) (51) + TX, Bacillus thuringiensis subspecies japonensis (scientific name) (51) + TX, Bacillus thuringiensis subspecies kurstaki (scientific name) (51) + TX, Bacillus thuringiensis subspecies 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 (alternative name) (491 ) + TX, Mamestra brassicae NPV (alternative name) (494) + TX, Metaphycus helvolus (alternative name) (522) + TX, Metarhizium anisopliae spp. acridum (scientific name) (523) + TX, Metarhizium anisopliae spp. 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,

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

chemosterilizer selected from the group of substances consisting of afolate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemela [CCN] + TX, hemp [CCN] + TX, metep [CCN] + TX, methiotepa [CCN] + TX, methylafolate [CCN] + TX, morzide [CCN] + TX, penfluron ( alternative name) [CCN] + TX, tepy [CCN] + TX, thiochempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine (alternative name) [CCN] and uredepy (alternative name) name) [CCN] + TX,

insect pheromone selected from the group of substances consisting of (E)-dec-5-en-1-yl acetate with (E)-dec-3-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,2)-tetradeca-4,10-dien-1-ylacetate (IUPAC name) (779) + TX, (2)-dodec-7-en-1-ylacetate (IUPAC name) (285) + TX , (Z)-hexadec-11-enal (IUPAC name) (436) + TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name) (437) + TX, (Z)-hexadece -13-en-11-yne-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-ylacetate (IUPAC name) (784) + TX, (7E,9Z)-dodeca-7,9-dien-1-ylacetate (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 (alternate name) [CCN] + TX, codlelura (alternative name) [CCN] + TX, codlemona (alternative name) (167) + TX, quelura (alternative name) (179 ) + TX, disparlura (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-ylacetate (IUPAC name) (284) + TX, dominicalur (alternate 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, hexalur [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 (alternative 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, orycthalura (alternative name) (317) + TX, ostramon (alternative name) [CCN] + TX, siglura [CCN] + TX, sordidina (alternative name) (736) + TX, sulcatol (alternative name) [CCN] + TX, tetradeum-11-en-1-yl acetate (IUPAC name) (785) + TX, trimedlur (839) + TX, trimedlur A (alternative name) (839) + TX, trimedlur Bi (alternative name ) (839) + TX, trimedlura Bg (alternative name) (839) + TX, trimedlura S (alternative name) (839) and Trank-Cola (alternative name) [CCN] + TX,

insect repellent selected from the group consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) IUPAC) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethylhexanediol ( 1137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,

insecticide selected from the group of substances consisting of 1-dichloro-1-nitroethane (IUPAC/Chemical Abstract Service name) (1058) + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane (name according to 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 name) (916) + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451) + TX, 2,2-dichlorovinyl-2-ethylsulfinylethyl methylphosphate (IUPAC name) (1066) + TX, 2-(1,3-dithiolan-2-yl)phenyldimethylcarbamate (IUPAC/Chemical Abstract Service name) (1109) + TX, 2-(2-butoxyethoxy)ethylthiocyanate (IUPAC name) (935) + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenylmethylcarbamate (IUPAC 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, acetoprole [CCN ] + TC, acrynathrine (9) + TC, acrylonitrile (IUPAC name) (861) + TC, alanicarb (15) + TC, aldicarb (16) + TC, aldoxycarb (863) + TC, aldrin (864) + TC , 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, amitone (875) + TX, amitone hydroxalate (875) + TX, amitraz (24) + TX, anabasine (877) + TX, atidation (883) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azadirachtin (alternative name) (41) + TX, azametifos (42) + TX, azinphos -ethyl (44) + TX, azinphos-methyl (45) + TX, azotoate (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, bartrin [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 ( IUPAC name) (909) + TX, bistrifluron (83) + TX, borax (86) + TX, brofenvalerate (alternative name) + TX, bromfenvinphos (914) + TX, bromocyclene (918) + TX, bromo-DDT ( alternative name) [CCN] + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, bufencarb (924) + TX, buprofezin (99) + TX, butacarb (926) + TX, butathiophos (927) + TC, butocarboxyme (103) + TC, butonate (932) + TC, butoxycarboxyme (104) + TC, butylpyridabene (alternative name) + TC, cadusafos (109) + TC, calcium arsenate [CCN] + TC, calcium cyanide ( 444) + TC, calcium polysulfide (IUPAC name) (111) + TC, camphechlor (941) + TC, carbonolate (943) + TC, carbaryl (115) + TC, carbofuran (118) + TC, carbon disulfide (name according to IUPAC/Chemical Abstract Service) (945) + TC, carbon tetrachloride (IUPAC name) (946) + TC, carbophenothione (947) + TC, carbosulfan (119) + TC, cartap (123) + TC, cartap hydrochloride ( 123) + TC, cevadin (alternative name) (725) + TC, chlorobicyclene (960) + TC, chlordane (128) + TC, chlordecone (963) + TC, chlordimeform (964) + TC, chlordimeform hydrochloride (964) + TC, chlorethoxyphos (129) + TC, chlorfenapyr (130) + TC, chlorfenvinphos (131) + TC, chlorfluazuron (132) + TC, chlormephos (136) + TC, chloroform [CCN] + TC, chloropicrin (141) + TC , chlorphoxime (989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorothiophos (994) + TX, chromafenozide (150) + TX, cinerine I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, cis-resmethrin (alternative name) + TX, cismethrin (80) + TX, clocitrin (alternative name) + TX, cloetocarb (999) + TX, closantel (alternative name) [CCN] + TX, clothianidin (165) + TX, copper acetoarsenite [CCN] + TX, copper arsenate [CCN] + TX, copper oleate [CCN] + TX, coumaphos (174) + TX, cumitoate (1006) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, crufomate (1011) + TX, cryolite (alternative name) (177) + TX, CS 708 (development code) (1012 ) + TC, cyanophenphos (1019) + TC, cyanophos (184) + TC, cyanoate (1020) + TC, cycletrin [CCN] + TC, cycloprothrin (188) + TC, cyfluthrin (193) + TC, cyhalothrin (196) + TC, cypermethrin (201) + TC, cyphenothrin (206) + TC, cyromazine (209) + TC, cythioate (alternative name) [CCN] + TX, d-limonene (alternative name) [CCN] + TX, d- tetramethrin (alternative 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, demetona (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, dialifos (1042) + TX, diamidaphos (1044) + TX, diazinon (227) + TX, dicaptone (1050) + TX, dichlorofenthion (1051) + TX, dichlorvos (236) + TX, diclifos (alternative name) + TX, dicresyl (alternative name) [CCN] + TC, dicrotophos (243) + TC, dicyclanil (244) + TC, dieldrin (1070) + TC, diethyl-5-methylpyrazol-3-ylphosphate (IUPAC name) (1076) + TC, diflubenzuron (250 ) + TX, dilor (alternative name) [CCN] + TX, dimefluthrin [CCN] + TX, dimefox (1081) + TX, dimethane (1085) + TX, dimethoate (262) + TX, dimethrin (1083) + TX, dimethylvinphos (265) + TX, dimethylane (1086) + TX, dinex (1089) + TX, dinex-diclexin (1089) + TX, dinoprop (1093) + TX, dinosam (1094) + TX, dinoseb (1095) + TX , dinotefuran (271) + TX, diophenolan (1099) + TX, dioxabenzophos (1100) + TX, dioxacarb (1101) + TX, dioxathione (1102) + TX, disulfoton (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, ERBP ( 1123) + TX, EPN (297) + TX, epophenonane (1124) + TX, eprinomectin (alternative name) [CCN] + TX, esfenvalerate (302) + TX, ethos (alternative name) [CCN] + TX, etiophencarb ( 308) + TX, ethion (309) + TX, ethiprole (310) + TX, methyl ethoate (1134) + TX, ethoprophos (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, etofenprox (319) + TX, etrymphos (1142) + TX, EXD (1143) + TX, famfura (323) + TX, fenamiphos (326) + TX, phenazaflor (1147) + TX, fenchlorvos (1148) + TX, fenetacarb (1149) + TX, fenfluthrin (1150) + TX, fenitrothion ( 335) + TX, fenobucarb (336) + TX, fenoxacrim (1153) + TX, fenoxycarb (340) + TX, fenpyritrin (1155) + TX, fenpropathrina (342) + TX, fenpyrad (alternative name) + TX, fensulfothione ( 1158) + TX, fenthion (346) + TX, fenthion-ethyl [CCN] + TX, fenvalerate (349) + TX, fipronil (354) + TX, flonicamide (358) + TX, flubendiamide (CAS Registration No.: 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, fonophos (1191) + TX, formatenate (405) + TX, formatenate hydrochloride (405 ) + TC, formothione (1192) + TC, formparanate (1193) + TC, fosmethylane (1194) + TC, fospirate (1195) + TC, fosthiazate (408) + TC, fostiethane (1196) + TC, furatiocarb (412) + TC, furethrin (1200) + TC, gamma-cyhalothrin (197) + TC, gamma-NSN (430) + TC, guazatin (422) + TC, guazatin acetates (422) + TC, GY-81 (development code) (423) + TX, galfenprox (424) + TX, halofenozide (425) + TX, NCH (430) + TX, HEOD (1070) + TX, heptachlor (1211) + TX, heptenophos (432) + TX, heterophos [ CCN] + TQ, hexaflumuron (439) + TQ, HHDN (864) + TQ, hydramethylnon (443) + TQ, hydrogen cyanide (444) + TQ, hydroprene (445) + TQ, hiquincarb (1223) + TQ, imidacloprid (458 ) + TX, imiprotrine (460) + TX, indoxacarb (465) + TX, iodomethane (IUPAC name) (542) + TX, IPSP (1229) + TX, isazophos (1231) + TX, isobenzan (1232) + TX , isocarbophos (alternative name) (473) + TX, isodrin (1235) + TX, isofenphos (1236) + TX, isolan (1237) + TX, isoprocarb (472) + TX, isopropyl-0-(methoxyaminothiophosphoryl) salicylate (name according to IUPAC) (473) + TX, isoprothiolane (474) + TX, isothioate (1244) + TX, isoxathione (480) + TX, ivermectin (alternative name) [CCN] + TX, jasmoline I (696) + TX, jasmoline II (696) + TX, iodofenphos (1248) + TX, juvenile hormone I (alternative name) [CCN] + TX, juvenile hormone II (alternative name) [CCN] + TX, juvenile hormone III (alternative name) [CCN] + TC, kelevan (1249) + TC, kinoprene (484) + TC, lambda-cyhalothrin (198) + TC, lead arsenate [CCN] + TC, lepimectin (CCN) + TC, leptophos (1250) + TC, lindane ( 430) + TX, lyrimphos (1251) + TX, lufenuron (490) + TX, lithidathione (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, menazone (1260) + TX, mephospholan (1261) + TC, mercuric chloride (513) + TC, mesulfenphos (1263) + TC, metaflumizone (CCN) + TC, metam (519) + TC, metam-potassium (alternative name) (519) + TC, metam-sodium (519) + TC, metacryphos (1266) + TC, methamidophos (527) + TC, methanesulfonyl fluoride (IUPAC/Chemical Abstract Service name) (1268) + TC, methidathione (529) + TC, methiocarb (530) + TC, methocrotophos (1273 ) + TC, methomyl (531) + TC, methoprene (532) + TC, methoquin-butyl (1276) + TC, methotrine (alternative name) (533) + TC, methoxychlor (534) + TC, methoxyfenozide (535) + TC, methyl bromide (537) + TC, methyl isothiocyanate (543) + TC, methyl chloroform (alternative name) [CCN] + TC, methylene chloride [CCN] + TC, metofluthrin [CCN] + TC, metolcarb (550) + TC, methoxadiazone (1288) + TX, mevinfos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternate name) [CCN] + TX, mipafox (1293) + TX, mirex (1294) ) + TX, monocrotophos (561) + TX, morphothione (1300) + TX, moxidectin (alternative name) [CCN] + TX, naphthalophos (alternative name) [CCN] + TX, naleda (567) + TX, naphthalene (name according to IUPAC/Chemical 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, nitrilecarb (1313) + TX, complex of nitrilecarb 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- ethyl ethylphosphonothioate (IUPAC name) (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 ( name according to IUPAC) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydemeton-methyl (609) + TX, oxydeprophos (1324) + TX, oxydisulfoton (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 (IUPAC name) (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, phosnichlor (1339) + TX , phosphamidone (639) + TX, phosphine (IUPAC name) (640) + TX, phoxim (642) + TX, phoxim-methyl (1340) + TX, pirimetaphos (1344) + TX, pirimicarb (651) + TX, pirimiphos-ethyl (1345) + TX, pirimiphos-methyl (652) + TX, polychlorodicyclopentadiene isomers (IUPAC name) (1346) + TX, polychloroterpenes (traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, prallethrin (655) + TX, precocene I (alternate name) [CCN] + TX, precocene II (alternate name) [CCN] + TX, precocene III (alternate name) [CCN] + TX , primidophos (1349) + TX, profenophos (662) + TX, profluthrin [CCN] + TX, promacyl (1354) + TX, promecarb (1355) + TX, propaphos (1356) + TX, propetamphos (673) + TX, propoxura (678) + TX, protidation (1360) + TX, prothiophos (686) + TX, protoate (1362) + TX, protrifenbuta [CCN] + TX, pymetrozine (688) + TX, pyraclophos (689) + TX, pyrazophos (693) + TC, pyrethrin (1367) + TC, pyrethrin I (696) + TC, pyrethrin II (696) + TC, pyrethrins (696) + TC, pyridabene (699) + TC, pyridalyl (700) + TC, pyridafenthione (701) + TX, pyrimidifene (706) + TX, pyrimitate (1370) + TX, pyriproxyfen (708) + TX, quassia (alternative name) [CCN] + TX, quinalphos (711) + TX, quinalphos-methyl ( 1376) + TX, quinothione (1380) + TX, quinthiophos (1381) + TX, R-1492 (development code) (1382) + TX, rafoxanide (alternate name) [CCN] + TX, resmethrin (719) + TX, rotenone (722) + TX, RU 15525 (development code) (723) + TX, RU 25475 (development code) (1386) + TX, ryanium (alternative name) (1387) + TX, ryanodine (traditional name) (1387) + TX, sabadilla (alternative name) (725) + TX, shradana (1389) + TX, sebuphos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (connection code) + TX, SI-0404 (connection code) + TX, SI-0405 (connection code) + TX, silafluofen (728) + TX, SN 72129 (development code) (1397) + TX, arsenite sodium [CCN] + TC, sodium cyanide (444) + TC, sodium fluoride (IUPAC/Chemical Abstract Service name) (1399) + TC, sodium hexafluorosilicate (1400) + TC, sodium pentachlorophenoxide (623) + TC, sodium selenate (IUPAC name) (1401) + TX, sodium thiocyanate [CCN] + TX, sofamide (1402) + TX, spinosad (737) + TX, spiromesifene (739) + TX, spirotetramate (CCN) + TX, sulcofuron (746 ) + TC, sulcofuron-sodium (746) + TC, sulfluramide (750) + TC, sulfotepa (753) + TC, sulfuryl fluoride (756) + TC, sulprophos (1408) + TC, tar oils (alternative name) (758) + TX, tau-fluvalinate (398) + TX, tazimcarb (1412) + TX, TDE (1414) + TX, tebufenozide (762) + TX, tebufenpyrad (763) + TX, tebupirimphos (764) + TX, teflubenzuron (768 ) + TX, tefluthrin (769) + TX, temephos (770) + TX, TERP (1417) + TX, terallethrin (1418) + TX, terbam (alternative name) + TX, terbufos (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, ticrofos (1428) + TX, thiocarboxime (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, thuringiensin (alternative name) [CCN] + TX, tolfenpyrad (809) + TX, tralomethrine (812) + TX, transfluthrin (813) ) + TX, transpermethrin (1440) + TX, triamiphos (1441) + TX, triazamate (818) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trichlorometaphos-3 (alternative name) [CCN] + TX, trichloronate (1452) + TX, triphenophos (1455) + TX, triflumuron (835) + TX, trimetacarb (840) + TX, triprene (1459) + TX, vamidothione (847) + TX, vaniliprole [CCN] + TX, veratridine (alternative name) (725) + TX, veratrine (alternative name) (725) + TX, CMS (853) + TX, xylylcarb (854) + TX, YI-5302 (code compounds) + TC, zeta-cypermethrin (205) + TC, zetamethrin (alternative name) + TC, zinc phosphide (640) + TC, zolaprophos (1469) and ZXI 8901 (development code) (858) + TC, cyantraniliprole [736994 -63-19] + TX, chlorantraniliprole [500008-45-7] + TX, cyenopyrafen [560121-52-0] + TX, cyflumetofen [400882-07-7] + TX, pyrifluquinazone [337458-27-2] + TX, spinetorama [187166-40-1 + 187166-15-0] + TX, spirotetramate [203313-25-1] + TX, sulfoxaflor [946578-00-3] + TX, flufiprole [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-metofluthrin [ 240494-71-7] + TX, epsilon-momofluorotrin [1065124-65-3] + TX, fluazaindolizine [1254304-22-7] + TX, chloroprallethrin [399572-87-3] + TX, fluxamethamide [928783-29- 3] + TX, cyhalodiamide [1262605-53-7] + TX, thioxazaphene [330459-31-9] + TX, broflanilide [1207727-04-5] + TX, flufiprole [704886-18-0] + TX, cyclaniliprol [1031756-98-5] + TX, tetraniliprole [1229654-66-3] + TX, guadipyr (described in WO 2010/060231) + TX, cycloxapride (described in WO 2005/077934) + TX, spiropidione + TX, aphidopyropene + TX, flupirimine + TX, momfluorothrin + TX, kappa-bifenthrin + TX, kappa-tefluthrin + TX, dichloromesothiase + TX, tetrachloraniliprole + TX, benzpyrimoxane + TX;

molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (IUPAC name) (913) + TC, bromoacetamide [CCN] + TC, calcium arsenate [CCN] + TC, cloetocarb (999) + TC, copper acetoarsenite [ CCN] + TC, copper sulfate (172) + TC, fentin (347) + TC, iron(III) phosphate (IUPAC name) (352) + TC, metaldehyde (518) + TC, methiocarb (530) + TC, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TC, triphenmorph (1454) + TC, trimetacarb (840) + TC, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, pyriprole [394730-71-3] + TX,

nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, 1,2-dibromo-3-chloropropane (IUPAC 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 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, acetoprole [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) + TC, cadusafos (109) + TC, carbofuran (118) + TC, carbon disulfide (945) + TC, carbosulfan (119) + TC, chloropicrin (141) + TC, chlorpyrifos (145) + TC, cloetocarb (999) + TX, cytokinins (alternative name) (210) + TX, dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidaphos (1044) + TX, dichlorofenthion (1051) + TX, diclifos (alternative name) + TX, dimethoate (262) + TX, doramectin (alternate name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX , ethoprophos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fenpyrad (alternative name) + TX, fensulfothione (1158) + TX, fosthiazate (408) + TX, fostiethane (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, mekarfon (1258) + TX, metam (519) + TX, metam-potassium (alternative name ) (519) + TC, sodium metam (519) + TC, methyl bromide (537) + TC, methyl isothiocyanate (543) + TC, milbemycin oxime (alternative name) [CCN] + TC, 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 (alternative name) + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachlorothiophene (name according to IUPAC/Chemical Abstract Service) (1422) + TX, thiaphenox (alternate name) + TX, thionazine (1434) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, xylenols [CCN] + TX, YI-5302 (compound code) and zeatin (alternate name) (210) + TX, fluensulfone [318290-98-1] + TX, fluopyram + TX,

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

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

rodenticide selected from the group of substances 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, bisthiosemium (912) + TX, brodifacoum (89 ) + TC, bromadiolone (91) + TC, bromethalin (92) + TC, calcium cyanide (444) + TC, chloralose (127) + TC, chlorophacinone (140) + TC, cholecalciferol (alternative name) (850) + TC , coumachlor (1004) + TX, coumafuryl (1005) + TX, coumatetral (175) + TX, crimidine (1009) + TX, difenacoum (246) + TX, difethialone (249) + TX, diphacinone (273) + TX, ergocalciferol (301) + TX, flocumafen (357) + TX, fluoroacetamide (379) + TX, flupropadine (1183) + TX, flupropadine hydrochloride (1183) + TX, gamma-NSN (430) + TX, NCH (430) + TC, hydrogen cyanide (444) + TC, iodomethane (IUPAC name) (542) + TC, lindane (430) + TC, magnesium phosphide (IUPAC name) (640) + TC, methyl bromide (537) + TC, norbormide ( 1318) + TC, phosacetim (1336) + TC, phosphine (IUPAC name) (640) + TC, phosphorus [CCN] + TC, pindone (1341) + TC, potassium arsenite [CCN] + TC, pyrinuron (1371) + TQ, scylliroside (1390) + TQ, sodium arsenite [CCN] + TQ, sodium cyanide (444) + TQ, sodium fluoroacetate (735) + TQ, strychnine (745) + TQ, thallium sulfate [CCN] + TQ, warfarin (851) and zinc phosphide (640) + TX,

a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934) + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone ( name according to IUPAC) (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, sesamex (1393) + TX, sesasmoline (1394) and sulfoxide (1406) + TX,

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

a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX,

wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octylinone (590) and methyl thiophanate (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, pyrifenox [88283-41-4] + TX, prochloraz [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, ancymidol [12771-68-5] + TX, fenarimol [60168-88-9] + TX, nuarimol [63284-71-9] + TX, bupirimol [41483-43-6] + TX, dimethyrimol [5221-53-4] + TX, ethirimol [23947- 60-6] + TX, dodemorph [1593-77-7] + TX, fenpropidine [67306-00-7] + TX, fenpropimorph [67564-91-4] + TX, spiroxamine [118134-30-8] + TX , tridemorpha [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, chlozolinate [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, carboxin [5234-68-4] + TX, fenfuram [24691-80-3] + TX, flutolanil [66332-96-5] + TX, mepronil [55814-41-0] + TX, hydroxycarboxin [5259-88-1] + TX, penthiopyrad [183675-82-3] + TX, tifluzamide [130000-40-7] + TX, guazatin [108173-90- 6] + TX, dodine [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. WSRS, bit. 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, metyrama [9006-42-2] + TX, propineba [12071-83-9] + TX, tirama [ 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, folpeta [133-07-3] + TX, tolylfluanide [731-27-1] + TX, Bordeaux mixture [ 8011-63-0] + TC, copper hydroxide [20427-59-2] + TC, copper oxychloride [1332-40-7] + TC, copper sulfate [7758-98-7] + TC, copper oxide [1317- 39-1] + TX, mancopper [53988-93-5] + TX, copper oxinate [10380-28-6] + TX, dinocap [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, phosdifene [36519-00-3] + TX, pyrazophos [ 13457-18-6] + TX, tolclofos-methyl [57018-04-9] + TX, acibenzolar-8-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, chloroneb [2675-77-6] + TX, chlorothalonil [1897-45- 6] + TX, cyflufenamide [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, diethofencarb [87130-20-9] + TX, dimethomorpha [110488-70-5] + TX, SYP-LI90 (flumorpha) [ 211867-47-9] + TX, dithianone [3347-22-6] + TX, ethaboxam [162650-77-3] + TX, etridiazole [2593-15-9] + TX, famoxadone [131807-57-3] + TX, fenamidone [161326-34-7] + TX, phenoxanil [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, proquinazide [189278-12-4] + TX, pyroquilone [57369-32-1] + TX, quinoxifene [124495-18-7] + TX, quintozene [82-68-8] + TX, sulfur [7704-34-9] + TX, tiadinyl [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, sedaxane [874967-67-6] + TX, (9-dichloromethylene-1,2,3,4- tetrahydro-1,4-methanonaphthalen-5-yl)-amide 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (disclosed in WO 2007/048556) + TX, (3',4',5' -trifluorobiphenyl-2-yl)-amide 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (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[2,1-6]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; lancotrione [1486617-21-3] + TX, florpyrauxifene [943832-81-3] + TX, ipfentrifluconazole [1417782-08-1] + TX, mefentrifluconazole [1417782-03-6] + TX, quinofumeline [861647-84- 9] + TX, chloroprallethrin [399572-87-3] + TX, cyhalodiamide [1262605-53-7] + TX, fluazaindolizine [1254304-22-7] + TX, fluxamethamide [928783-29-3] + TX, epsilon -metofluthrin [240494-71-7] + TX, epsilon-momofluorothrin [1065124-65-3] + TX, pidiflumetofen [1228284-64-7] + TX, kappa-bifenthrin [439680-76-9] + TX, broflanilide [1207727-04-5] + TX, dichloromesothiase [1263629-39-5] + TX, dipimethytrone [16114-35-5] + TX, pyraziflumide [942515-63-1] + TX, kappa-tefluthrin [391634-71 -2] + TX, fenpicoxamide [517875-34-2] + TX; fluindapir [1383809-87-7] + TX; alpha-bromadiolone [28772-56-7] + TX; flupirimine [1689566-03-7] + TX; benzpyrimoxane [1449021-97-9] + TX; acinonapir [1332838-17-1] + TX; inpirfluxam [1352994-67-2] + TX, isoflucipram [1255734-28-1] + TX; rescalura [64309-03-1] + TX; aminopyrifene [1531626-08-0] + TX; ticlopyrazoflor [1477919-27-9] + TX and spiropidione [1229023-00-0] + TX; And

microorganisms, including Acinetobacter Iwojfii + TX, Acremonium alternation + TX + TX, Acremonium cephalosporium + TX + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, Adoxophyes orana granulovirus (AdoxGV) (Capex®) + TX, Agrobacterium radiobacter, strain K84 (Galltrol-A®) + TX, Alternaria alternate + TX, Alternaria cassia + TX, Alternaria destruens (Smolder®) + TX, Ampelomyces quisqualis (AQ10®) + TX, Aspergillus flavus AF36 (AF36®) + TX, Aspergillus flavus NRRL 21882 (Aflaguard®) + TX, Aspergillus spp. + 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, Cry 2Ae Bacillus thuringiensis + TX, CrylAb Bacillus thuringiensis + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis israelensis (BMP 123® + 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, bacterial species (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, Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Bacillus thuringiensis tenebrionis (Novodor®) + TX, BtBooster + TX, Burkholderia cepacia (Deny® + TX, Intercept® + TX, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp. + TX, 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, Metschnikowia 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, Ophiostoma piliferum, 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 cor rugate + 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, Ustilago maydis + 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 (VTPtera®) + 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, extracts of clove oil, rosemary, peppermint and thyme (Garden insect killer®) + TX, glycine betaine (Greenstim®) + TX, garlic + TX, lemongrass oil (GreenMatch®) + TX, margosa oil + TX , Nepeta cataria (catnip oil) + TX, Nepeta catarina + TX, nicotine + TX, oil of oregano (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, a mixture of rosemary, sesame, peppermint, thyme and cinnamon extracts (EF 300®) + TX, a mixture of clove, rosemary and peppermint extracts ( EF 400®) + TX, a mixture of cloves, peppermint, garlic and mint oils (Soil Shot®) + TX, kaolin (Screen®) + TX, a glucan stored by brown algae (Laminarin®); And

pheromones, including blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®) + TX, codling moth pheromone (Paramount dispenser-(CM)/ Isomate C-Plus®) + TX, grape leafroller pheromone (3M MEC-GBM Sprayable Pheromone® ) + TX, leafroller pheromone (ZM MES - LR Sprayable Pheromone®) + TX, muscamon (Snip7 Fly Bait® + TX, Starbar Premium Fly Bait®) + TX, eastern peach leafroller pheromone (3M oriental fruit moth sprayable pheromone®) + TX, peach glassworm 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 tetradecatrienylacetate + TX, (Z + TX,Z + TX,E)-7 + TX,11 + TX,13-hexadecatrienal + TX, (E + TX,Z )-7 + TX,9-dodecadien-1-ylacetate + TX, 2-methyl-1-butanol + TX, calcium acetate + TX, Scenturion® + TX, Biolure® + TX, Check-Mate® + TX, lavandulyl senate; 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® + TX, 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 carnea (Chrysoline®) + TX, Chrysoperla carnea (Chrysopa ®) + TX, Chrysoperla rufilabris + 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 (Ercal® + 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, Online 1®) + 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, delta traps (Trapline d ®) + TX, Erwinia amylovora (harpin) (ProAct® + TX, Ni-HIBIT Gold CST®) + TX, ferrophosphate (Ferramol®) + TX, funnel traps (Trapline ®) + TX, Gallex® + TX, Grower's Secret® + TX, Homobrassinolide + TX, Ferric Phosphate (Lilly Miller Worry Free Ferramol Slug & Snail Bait®) + TX, MCPhail (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 broflutrinate + TX, difluvidazine + TX, flometoquine + TX, fluhexaphone + TX, Plutella xylostella granulosa virus + TX, Cydia pomonella granulosa virus + TX, imitsiaphos + TX, Heliothis virescens nuclear polyhedrosis virus + TX , nuclear polyhedrosis virus Heliothis punctigera + TX, nuclear polyhedrosis virus Helicoverpa zea + TX, nuclear polyhedrosis virus Spodoptera frugiperda + TX, nuclear polyhedrosis virus Plutella xylostella + TX, p-cymene + TX, piflubumide + TX, pirafluprol + TX, QRD 420 + TX, QRD 452 + TX, QRD 460 + TX, terpenoid mixtures + TX, terpenoids + TX, tetraniliprole + TX and a-terpinene + TX;

or the active substance indicated by code + TX, such as code AE 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 GSh-121 + TX, 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, quinofumeline + TX, mefentrifluconazole + TX, fenpicoxamide + TX, fluindapir + TX, inpirfluxam + TX or indiflumetpir + TX, isoflucipram + TX, pyrapropoin + TX, florylpicoxamide + TX, methyltetraprole + TX, ipflufenoquin + TX, pyrid achlomethyl + TX or chlopyridiflu + TX, tetrachlorantraniliprole + TX, tetrachloraniliprole + TX, ticlopyrazoflor + TX, flupirimine + TX or pyrifluramide + TX, benzpyrimoxane + TX, benzosufil + TX or oxazosulfil + TX, ethpirafen + TX, acinonapyr + TX or pyrinonafen + TX, oxotrione + TX, bixlozone + TX or clofenlizone + TX or dicloroxizone + TX, cyclopyranil + TX or pyrazocyclonil + TX or cyclopyrazonil + TX, alpha-bromadiolone + TX, code AKD-1193 + TX, oxathiapiproline + TX, fluopyram + TX, penflufen + TX, fluoxopyrosad + TX and flupyradifurone + TX.

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

Most of the above-described active ingredients are listed herein above by the so-called "common name", corresponding to the "ISO common name" or other "common name" which is used in individual cases. If the designation is not a "common name", the essence of the designation used instead is given in parentheses for the particular compound; in this case, the IUPAC name, the IUPAC/Chemical Abstract Service name, the "chemical name", the "traditional name", the "compound name" or the "development code" or, if none of these names, or the "common name" are used. , then use the "alternative name". "CAS Registration No" means the registration number under the Chemical Abstract Service.

A mixture of the active ingredients of the compounds of formula I selected from tables 1-12 and P with the active ingredients described above contains the compound selected from tables 1-12 and P and the active ingredient described above, preferably in a mixture ratio of 100: 1 to 1:6000, especially 50:1 to 1:50, more preferably 20:1 to 1:20, even more preferably 10:1 to 1:10, very preferably 5:1 to 1: 5, with particular preference given to a ratio of 2:1 to 1:2, 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 mixture ratios are given by weight.

In one embodiment, the above-described mixtures can be used in a pest control method that involves applying a composition containing the above-described mixture to pests or their habitat, excluding the method of treating a human or warm-blooded animal body by surgery or therapy and diagnostic methods used in relation to the human body or warm-blooded animal.

Mixtures containing a compound of Formula I selected from Tables 1-12 and P and one or more active ingredients as described above may be used, for example, in the form of a separate "ready mixture", in a combined spray mixture consisting of the individual formulations based on individual components representing the active ingredients, such as a "tank mix", and in the combined use of individual active ingredients, when applied in a sequential manner, i.e. one after the other within an acceptable short period such as a few hours or days. The order of application of the compounds of formula I selected from tables 1-12 and P, and the active ingredients described above, is not essential for the practice of the present invention.

The compositions of the present invention may also contain additional solid or liquid auxiliaries such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example, epoxidized coconut oil, rapeseed oil or soybean oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients to achieve certain effects, for example bactericides, fungicides, nematicides, plant growth promoters, molluscicides or herbicides.

The compositions according to the present invention are prepared in a manner known per se, in the absence of auxiliary agents, for example by grinding, sieving and/or pressing the solid active ingredient, and in the presence of at least one auxiliary agent, for example by thoroughly mixing and/or grinding the active ingredient with auxiliary agent(s). Such methods for preparing compositions and the use of compounds I to obtain such compositions are also the object of the present invention.

Methods of application of the compositions, that is, methods of controlling pests of the above type, such as spraying, spraying, dusting, brushing, pelleting, scattering or pouring, which are to be selected to suit the intended purposes taking into account the circumstances, and the use of compositions for controlling pests of the above type are different objects of the present invention. Typical concentration levels of the active ingredient 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 field of crop protection is foliar application (foliar application), and the frequency and rate of application 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 introducing the active ingredient in solid form into the plant site, for example in the soil, for example in the form of granules (applied to soil). In the case of the paddy crop, such granules can be supplied in a certain quantity 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 above. Propagation material can be treated with a compound before planting, for example seeds can be treated before sowing. Alternatively, the compound can be applied to the 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 planting propagation material in relation to the application site, 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 application rates will depend on the plant and the pest/fungus being controlled and will typically range from 1 to 200 grams per 100 kg of seed, preferably 5 to 150 grams per 100 kg of seed, such as 10 to 100 grams per 100 kg of seeds.

The term "seed" includes seeds and vegetative parts of plants 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 in 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 into the seed depending on the method of application. If said seed product is (re)planted, it can absorb the active ingredient. In one embodiment, the present invention provides a plant propagation material capable of attaching a compound of formula (I) thereto. Further provided herein is a plant propagation material containing the composition treated with a compound of formula (I).

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

Biological examples

Example B1. Spodoptera littoralis (Egyptian cotton bollworm)

Cotton 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, leaf discs were infested with five L1 larvae. Samples were assessed for mortality, antifeedant effect, and growth inhibition compared to untreated samples 3 days postinfection. Control of Spodoptera littoralis by test samples was present if at least one of the categories of mortality, antifeedant effect and growth inhibition was higher than for the untreated sample.

The following compounds provided at least 80% control at the 200 ppm application rate: P1, P2, P3, P5, P6, P7, P8, P9, P11, P12, P13, P14, P17, P18, and P19.

Example B2. Syodoytera littoralis (Egyptian cotton bollworm)

The test compounds were pipetted from 10,000 ppm stock solutions in DMSO into 24-well plates and mixed with agar. Lettuce seeds were placed on agar and the multiwell plate was covered with another plate that also contained agar. After 7 days, the roots absorbed the compound and the lettuce sprouted into the plate on top. The lettuce leaves were then cut into a tablet placed on top. Spodoptera eggs were pipetted through a plastic stencil onto moistened gel blotting paper and covered the plate. Samples were evaluated for mortality, antifeedant effect, and growth inhibition compared to untreated samples 6 days postinfection.

The following compounds produced an effect of at least 80% in at least one of three categories (mortality, antifeedant or growth inhibition) at the test rate of 12.5 ppm: P3.

Example of EOI. Plutella xvlostella (cabbage moth)

24-well microtiter plates with artificial nutrient medium were pipetted with test aqueous solutions prepared from 10,000 ppm stock solutions in DMSO. After drying, the plates were inoculated with L2 larvae (10-15 per well). Samples were assessed for mortality and growth inhibition compared to untreated samples 5 days postinfection.

The following compounds provided an effect of at least 80% in at least one of two categories (mortality or growth inhibition) at 200 ppm: P1, P2, P3, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, and P20.

Example B4. Diabrotica balteata (cereal rootworm)

Corn shoots plated on an agar layer in 24-well microtiter plates were treated with test aqueous solutions prepared from 10,000 ppm stock solutions in DMSO by nebulization. After drying, the plates were inoculated with L2 larvae (6-10 per well). Samples were assessed for mortality and growth inhibition compared to untreated samples 4 days postinfection.

The following compounds provided an effect of at least 80% in at least one of two categories (mortality or growth inhibition) at 200 ppm: P1, P2, P3, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P17, P18, P19, and P20.

Example B5. Mvzus persicae (green peach aphid)

Sunflower leaf disks 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 discs were infested with populations of aphids of different ages. At 6 days postinfection, samples were assessed for mortality.

The following compounds provided at least 80% mortality at 200 ppm:

P1, P2, P3, P5, P6, P7, P8, P9, P10, P11, P12, P14, P15, P16, P17, P18, and P20.

Example B6. Myzus persicae (green peach aphid)

Roots of pea seedlings infested with aphid populations of different 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 assessed for mortality.

The following compounds provided at least 80% mortality at the 24 ppm rate tested: P1, P3, P8, P15, P16, and P17.

Example B7. Bemisia tabaci (tobacco whitefly)

Cotton 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 infested with adult whiteflies. After 6 days of incubation, samples were checked for mortality.

The following compounds provided at least 80% mortality at 200 ppm: P1, P2, P3, P5, P6, P7, P8, P10, P11, P12, P13, P14, P17, P19, and P20.

Example B8. Euschistus heros (Neotropical brown stink 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 infested with N2 nymphs. Samples were assessed for mortality and growth inhibition compared to untreated samples 5 days postinfection.

The following compounds provided an effect of at least 80% in at least one of two categories (mortality or growth inhibition) at 200 ppm: P1, P2, P3, P8, and P14.

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

Bean leaf disks 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 infested with a population of mites of different ages. At 8 days postinfection in the mixed population (mobile stages), samples were assessed for mortality.

The following compounds provided at least 80% mortality at 200 ppm: P1, P3, P6, P9, P12, P17, and P18.

Example B11. Frankliniella occidentalis (western flower tripe)

Sunflower 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, leaf discs were infected with Frankliniella populations of different ages. At 7 days postinfection, samples were assessed for mortality.

The following compounds provided at least 80% mortality at 200 ppm: P3, P6, P7, P1, P12, and P17.

Example B12. Comparison of the insecticidal activity of the compound P1 according to the present invention with the closest compound in terms of structure from the prior art

The activity of compound P1 according to the preparation examples and compound P8 of WO 2016/0721414 against Myzus persicae by feeding/contact action (example B5 above), Myzus persicae by systemic action (example B6) and Euschistus heros (example B8) is summarized in table B13 .

Table B12 demonstrates that the compound P1 of the present invention surprisingly has significantly better insecticidal activity against Myzus persicae by feeding/contact action (B5) and systemic action (B6) and against Euschistus heros (B8) at the application rates tested than the compound from the prior art. This enhanced effect was unexpected given the structural similarity of these compounds.

Claims (31)

1. Compound of formula I-Q1, Where A represents CH or N; X represents S or SO ₂ ; R ₁ represents C ₁ -C ₄ alkyl; R ₇ and R ₈ independently of each other represent C ₁ -C ₆ alkyl; R ₂ represents 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; G ₂ represents N or CH; or an agrochemically acceptable salt of a compound of formula I-Q1. 2. Compound of formula I-Q4, Where A represents CH or N; X represents S, SO or SO ₂ ; R ₁ represents C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or C ₃ -C ₆ cycloalkylC ₁ -C ₄ alkyl; R ₇ and R ₈ independently of each other represent C ₁ -C ₆ alkyl; R ₂ represents 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; or an agrochemically acceptable salt of a compound of formula I-Q4. 3. A compound of formula I-Q1 according to claim 1 or a compound of formula I-Q4 according to claim 2, where X represents SO ₂ ; R ₁ represents ethyl; R ₂ represents trifluoromethyl; R ₇ represents methyl; And R ₈ represents methyl. 4. A compound of formula I-Q1 according to claim 1, where the compound is selected from the group consisting of compounds of formulas P1, P5, P6, P7, P9, P14, P15, P16, P19 and P20, or a compound of formula I-Q4 according to claim 2, which is selected from the compound represented by formula P8: 5. A pesticide composition that contains an insecticidal, acaricidal, or nematocidal effective amount of a compound of formula I-Q1 according to any one of paragraphs. 1, 3 or 4, or compounds of formula I-Q4 according to any one of paragraphs. 2, 3 or 4, in free form or in the form of an agrochemically useful salt as the active ingredient and optionally at least one auxiliary agent or diluent. 6. A method of controlling insects, mites or nematodes, which includes applying to the pest, to the location of the pest or to a plant susceptible to the pest, an insecticidal, acaricidal or nematicidally effective amount of a compound of formula I-Q1 according to any one of claims . 1,3 or 4, or compounds of formula I-Q4 according to any one of paragraphs. 2, 3 or 4, or compositions according to claim 5. 7. A method of protecting plant propagation material from the effects of insects, mites or nematodes, which includes treating the propagation material or the area where the propagation material is planted using a composition according to claim 5.