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Title:
7-SULFONYL-N-(1,3,4-THIADIAZOL-2-YL)-QUINOXALINE-6-CARBOXAMIDE DERIVATIVES AND THE RESPECTIVE -BENZIMIDAZOLE-5-, -IMIDAZO[4,5-B]PYRIDINE-5-, -3H-FURO[3,2B]PYRIDINE-5-, -QUINOLINE-2-, AND -NAPHTHALENE-2-CARBOXAMIDE DERIVATIVES AS PESTICIDES
Document Type and Number:
WIPO Patent Application WO/2020/254530
Kind Code:
A1
Abstract:
Compounds of formula (I) wherein the substituents are as defined in claim 1, and the agrochemically acceptable salts; stereoisomers, enantiomers, tautomers and N-oxides of those compounds.. Furthermore, the present invention relates to agrochemical compositions which comprise compounds of formula (I), to preparation of these compositions, and to the use of the compounds or compositions in agriculture or horticulture for combating, preventing or controlling animal pests, including arthropods and in particular insects, nematodes, molluscs or representatives of the order Acarina.

Inventors:
SIKERVAR VIKAS (IN)
SEN INDIRA (IN)
MUEHLEBACH MICHEL (CH)
JUNG PIERRE (CH)
EDMUNDS ANDREW (CH)
RENDLER SEBASTIAN (CH)
EMERY DANIEL (CH)
BUCHHOLZ ANKE (CH)
Application Number:
PCT/EP2020/067025
Publication Date:
December 24, 2020
Filing Date:
June 18, 2020
Export Citation:
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Assignee:
SYNGENTA CROP PROTECTION AG (CH)
International Classes:
C07D417/12; A01N43/42; A01N43/52; A01N43/60; A01N43/82; A01N43/824; A01N43/90; C07D285/12; C07D471/04
Domestic Patent References:
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Foreign References:
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Other References:
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Claims:
Claims:

1. A compound of formula I

( l), wherein

Ri is Ci-C4haloalkyl;

f is hydrogen or Ci-C3alkyl;

J represents Ji , J2, J3, or J4

j

3 J 4

wherein the wavy line denotes the point of attachment to the thiadiazole amide moiety; and wherein

X is S, SO, or S02;

R3 is Ci-C4alkyl or C3-C4cycloalkyl-Ci-C2alkyl;

A is CH or N;

R is hydrogen, Ci-C3alkyl, Ci-C3haloalkyl or cyclopropyl;

R5 is Ci-C3alkyl, Ci-C3haloalkyl or cyclopropyl;

Ai is CH or N;

A2 is CH or N; f¾6 is hydrogen, halogen, cyano, Ci-C3alkyl or Ci-C3haloalkyl;

R is hydrogen, halogen, cyano, Ci-C3alkyl or Ci-C3haloalkyl;

Re is Ci-C3alkyl or Ci-C3haloalkyl;

Rg is Ci-C3alkyl or Ci-C3haloalkyl;

or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of the formula I.

2. A compound of formula I according to claim 1 , represented by the compounds of formula 1-1

wherein Ri, R2, R3, R4, Rs, A and X are as defined under formula I in claim 1.

3. A compound of formula 1-1 according to claim 2, wherein

A is N or CH, preferably A is CH;

X is S or SO , preferably X is SO ;

Ri is Ci-C haloalkyl, preferably Ri is Ci-C fluoroalkyl;

R IS Ci-C3alkyl; preferably R IS Ci-C alkyl;

R3 is Ci-C alkyl or cyclopropyl-Ci-C alkyl, preferably R3 is ethyl or cyclopropylmethyl;

R is Ci-C3haloalkyl, preferably R is Ci-C haloalkyl; and

Rs is Ci-C3alkyl; preferably Rs is Ci-C alkyl. 4. A compound of formula 1-1 according to claim 2, wherein

A is N or CH;

X is S or SO ;

Ri is CF2H, CFs, CH2CHF2, CH2CF3, CF2CHF2, or CF2CF3, preferably Ri is trifluoromethyl or pentafluoroethyl;

R is methyl or ethyl; preferably R is methyl;

R3 is ethyl or cyclopropylmethyl;

R is Ci-C fluoroalkyl; preferably R is trifluoromethyl; and

Rs is Ci-C alkyl; preferably Rs is methyl. 5. A compound of formula I according to claim 1 , represented by the compounds of formula I-2 wherein Ri, R2, R3, R6, R7, A, Ai, A2 and X are as defined under formula I in claim 1.

6. A compound of formula I-2 according to claim 5, wherein

A is N or CH, preferably A is CH;

X is S or SO , preferably X is SO ;

Ri is Ci-C haloalkyl, preferably Ri is Ci-C fluoroalkyl;

R IS Ci-C3alkyl; preferably R IS Ci-C alkyl;

R3 is Ci-C alkyl or cyclopropyl-Ci-C alkyl, preferably R3 is ethyl or cyclopropylmethyl;

Ai is N or CH;

A is N or CH;

Re is hydrogen or Ci-C3haloalkyl, preferably R6 is Ci-C3haloalkyl; and

R7 is hydrogen or Ci-C3alkyl, preferably R7 is hydrogen or Ci-C alkyl. 7. A compound of formula i-2 according to claim 5, wherein

A is N or CH;

X is S or SO ;

Ri is CF2H, CFs, CH2CHF2, CH2CF3, CF2CHF2, or CF2CF3, preferably Ri is trifluoromethyl or pentafluoroethyl;

R is methyl or ethyl; preferably R is methyl;

R3 is ethyl or cyclopropylmethyl;

Ai is N or CH;

A is N or CH;

R6 is hydrogen or Ci-C3haloalkyl, preferably R6 is Ci-C3haloalkyl; and

R7 is hydrogen or Ci-C3alkyl, preferably R7 is hydrogen or Ci-C alkyl.

8. A compound of formula i-2 according to any one of claims 5, 6 or 7 wherein, Ai and A are both N; or Ai and A are both CH; preferably Ai and A are both CH. 9. A compound of formula i-2 according to any one of claims 5, 6, 7 or 8 wherein, R6 and R7 are both

H.

10. A compound of formula I according to claim 1 , represented by the compounds of formula I-3 wherein Ri, R2, R3, A and X are as defined under formula I in claim 1.

11. A compound of formula I-3 according to claim 10, wherein

A is N or CH, preferably A is N;

X is S or SO , preferably X is SO ;

Ri is Ci-C haloalkyl, preferably Ri is Ci-C fluoroalkyl;

R IS Ci-C3alkyl; preferably R IS Ci-C alkyl; and

R3 is Ci-C alkyl or cyclopropyl-Ci-C alkyl, preferably R3 is ethyl or cyclopropylmethyl.

12. A compound of formula i-3 according to claim 10, wherein

A is N or CH;

X is S or SO ;

Ri is CF2H, CFs, CH2CHF2, CH2CF3, CF2CHF2, or CF2CF3, preferably Ri is trifluoromethyl or pentafluoroethyl;

R IS methyl or ethyl; preferably R IS methyl; and

R is ethyl or cyclopropylmethyl.

13. A compound of formula I according to claim 1 , represented by the compounds of formula I-4

wherein Ri, R2, R3, Re, R9, A and X are as defined under formula I in claim 1.

14. A compound of formula i-4 according to claim 13, wherein

A is N or CH, preferably A is CH;

X is S or SO , preferably X is SO ;

Ri is Ci-C haloalkyl, preferably Ri is Ci-C fluoroalkyl; R IS Ci-C3alkyl; preferably R IS Ci-C alkyl;

R3 is Ci-C alkyl or cyclopropyl-Ci-C alkyl, preferably R3 is ethyl or cyclopropylmethyl;

Re is Ci-C3alkyl, preferably Re is Ci-C alkyl; and

Rg is Ci-C3alkyl; preferably Rg is Ci-C alkyl.

15. A compound of formula I-4 according to claim 13, wherein

A is N or CH;

X is S or SO ;

Ri is CF2H, CFS, CH2CHF2, CH2CF3, CF2CHF2, or CF2CF3, preferably Ri is trifluoromethyl or pentafluoroethyl;

R IS methyl or ethyl; preferably R IS methyl;

R3 is ethyl or cyclopropylmethyl;

Re is methyl; and

Rg is methyl.

16. A compound of formula I according to any one of the preceeding claims, wherein Ri is pentafluoroethyl or trifluoromethyl; R2 IS methyl; and R3 is ethyl.

17. A compound of formula I according to claim 1 , selected from the group consisting of:

7-ethylsulfonyl-N-methyl-N-[5-(1 , 1 ,2,2,2-pentafluoroethyl)-1 , 3,4-thiad iazol-2-yl]-3- (trifluoromethyl)quinoxaline-6-carboxamide (compound P1 );

6-ethylsulfonyl-N , 1 -dimethyl-N-[5-(1 , 1 ,2,2,2-pentafluoroethyl)-1 ,3,4-thiadiazol-2-yl]-2- (trifluoromethyl)benzimidazole-5-carboxamide (compound P2);

6-ethylsulfanyl-N , 1 -dimethyl-N-[5-(1 , 1 ,2,2,2-pentafluoroethyl)-1 ,3,4-thiadiazol-2-yl]-2- (trifluoromethyl)benzimidazole-5-carboxamide (compound P3);

6-ethylsu Ifonyl-N, 1 ,3-trimethyl-2-oxo-N-[5-(1 , 1 ,2,2,2-pentafluoroethyl)-1 ,3,4-thiadiazol-2- yl]imidazo[4,5-b]pyridine-5-carboxamide (compound P4);

6-ethylsu Ifonyl-N, 1 ,3-trimethyl-2-oxo-N-[5-(1 , 1 ,2,2,2-pentafluoroethyl)-1 ,3,4-thiadiazol-2- yl]benzimidazole-5-carboxamide (compound P5);

6-ethylsu Ifanyl-N, 1 ,3-trimethyl-2-oxo-N-[5-(1 , 1 ,2,2,2-pentafluoroethyl)-1 ,3,4-thiadiazol-2- yl]benzimidazole-5-carboxamide (compound P6);

7-ethylsulfonyl-N-methyl-N-[5-(1 , 1 ,2,2,2-pentafluoroethyl)-1 , 3,4-thiad iazol-2-yl]-2- (trifluoromethyl)quinoxaline-6-carboxamide (compound P7);

6-ethylsulfonyl-N, 2, 2-trimethyl-N-[5-(1 , 1 ,2, 2, 2-pentafluoroethyl)-1 , 3, 4-thiadiazol-2-yl]-3H-furo[3, 2- b]pyridine-5-carboxamide (compound P8);

3-ethylsulfonyl-N-methyl-N-[5-(1 , 1 ,2,2,2-pentafluoroethyl)-1 , 3,4-thiad iazol-2-yl]quinoline-2- carboxamide (compound P9);

6-ethylsulfonyl-N,1-dimethyl-2-(trifluoromethyl)-N-[5-(trifluoromethyl)-1 ,3,4-thiadiazol-2- yl]benzimidazole-5-carboxamide (compound P10); 6-ethylsulfanyl-N,1-dimethyl-2-(trifluoromethyl)-N-[5-(trifluoromethyl)-1 ,3,4-thiadiazol-2- yl]benzimidazole-5-carboxamide (compound P1 1 );

3-ethylsulfonyl-N- ethyl-N-[5-(trifluoro ethyl)-1 ,3,4-thiadiazol-2-yl]naphthalene-2 -carboxamide (compound P12); and

3-ethylsulfanyl-N-methyl-N-[5-(trifluoromethyl)-1 ,3,4-thiadiazol-2-yl]naphthalene-2 -carboxamide

(compound P13).

18. A composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined in any of claims 1 - 17 and, optionally, an auxiliary or diluent.

19. A method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined in any one of claims 1 - 17 or a composition as defined claim 18.

20. A method for the protection of plant propagation material from the attack by insects, acarines, nematodes or molluscs, which comprises treating the propagation material or the site, where the propagation material is planted, with a composition according to claim 18.

Description:
7-SULFONYL-N-(1 ,3,4-THIADIAZOL-2-YL)-QUINOXALINE-6-CARBOXAMIDE DERIVATIVES AND THE RESPECTIVE -BENZIMIDAZOLE-5-, -IMIDAZO[4,5-B]PYRIDINE-5-,

-3H-FURO[3,2B]PYRIDINE-5-, -QUINOLINE-2-, AND -NAPHTHALENE-2-CARBOXAMIDE

DERIVATIVES AS PESTICIDES

The present invention relates to pesticidally active, in particular insecticidally active thiadiazole derivatives containing sulfur substituents, to processes for their preparation, to compositions comprising those compounds, and to their use for controlling animal pests including arthropods and in particular insects or representatives of the order Acarina.

5

Heterocyclic amides with pesticidal action are known and described, for example, in J. Pestic. Sci. 28, 310-312 (2003), WO 2014/086734, W02016/175017, WO 2016/087265, WO 2013/191041 , WO 2014/002754, WO 2014/021468, WO 2002/092584 and WO 2005/041665, WO 2015/072463, WO2015/068719. There have now been found novel pesticidally active thiadiazole amide derivatives 10 with sulfur containing aryl and heteroaryl substituents.

The present invention accordingly relates to compounds of formula I,

15

wherein

Ri is Ci-C 4 haloalkyl;

F¾2 is hydrogen or Ci-C3alkyl;

J represents Ji , J2, J3, or J4

wherein the wavy line denotes the point of attachment to the thiadiazole amide moiety; and wherein

X is S, SO, or S02;

f¾3 is Ci-C 4 alkyl or C3-C 4 cycloalkyl-Ci-C 2 alkyl;

A is CH or N;

f¾4 is hydrogen, Ci-C3alkyl, Ci-C3haloalkyl or cyclopropyl;

Rs is Ci-C3alkyl, Ci-C3haloalkyl or cyclopropyl;

Ai is CH or N;

A 2 is CH or N;

R6 is hydrogen, halogen, cyano, Ci-C3alkyl or Ci-C3haloalkyl;

R is hydrogen, halogen, cyano, Ci-C3alkyl or Ci-C3haloalkyl;

Re is Ci-C3alkyl or Ci-C3haloalkyl;

Rg is Ci-C3alkyl or Ci-C3haloalkyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of the formula I. Compounds of formula I which have at least one basic centre 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, nitrose acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as Ci-C 4 alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as Ci-C4alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid. Compounds of formula I which have 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 an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.

In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form as a N-oxide or in salt form, e.g. an agronomically usable salt form.

N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book“Heterocyclic N-oxides” by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.

The alkyl groups occurring in the definitions of the substituents can be straight-chain or branched hydrocarbon radical attached via any of the carbon atoms having 1 to n carbon atoms and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl. Haloalkyl radicals are derived from the alkyl radicals mentioned.

Halogen is generally fluorine, chlorine, bromine or iodine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl or halophenyl.

Haloalkyl groups occurring in the definitions of the substituents refer to a straight-chain or branched saturated alkyl radical attached via any of the carbon atoms having 1 to n carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these radicals may be replaced by fluorine, chlorine, bromine and/or iodine. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 , 1 -difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl, dichlorofluoromethyl and pentafluoroethyl.

The cycloalkyl groups preferably have from 3 to 4 ring carbon atoms, for example cyclopropyl or cyclobutyl. Cycloalkyl-alkyl refers to a straight-chain or branched saturated alkyl radical attached via any of the carbon atoms having 1 to n carbon atoms (as mentioned above), where at least one of the hydrogen atoms in these radicals may be replaced by a cycloalkyl radical having 3 to 4 carbon atoms (as mentioned above). For example, cycloalkyl-alkyl refers to cyclopropylmethyl.

Certain embodiments according to the invention are provided as set out below.

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

Embodiment 2 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to embodiment 1 wherein J is Ji and having preferred values of Ri, F? , Pa, F¾4, RS, A and X as set out below.

Embodiment 3 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to embodiment 1 wherein J is J and having preferred values of Ri, R2, R3, Re, R7, A, Ai, A2 and X as set out below.

Embodiment 4 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to embodiment 1 wherein J is J3 and having preferred values of Ri, R2, R3, A and X as set out below.

Embodiment 5 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to embodiment 1 wherein J is J and having preferred values of Ri, R2, R3, Re, R9, A and X as set out below.

With respect to embodiments 1 - 5, preferred values of are, in any combination thereof, as set out below:

A is N or CH, preferably A is CH.

X is S or SO , preferably X is SO .

Ri is Ci-C haloalkyl, preferably Ri is Ci-C fluoroalkyl.

More preferably Ri is CF2H, CF3, CH2CHF2, CH2CF3, CF2CHF2, or CF2CF3, most preferably Ri is trifluoromethyl or pentafluoroethyl.

R IS Ci-C3alkyl; preferably R IS Ci-C alkyl.

More preferably R IS methyl or ethyl; most preferably R IS methyl.

R3 is Ci-C alkyl or cyclopropyl-Ci-C alkyl, preferably R3 is ethyl or cyclopropylmethyl.

More preferably R3 is ethyl or cyclopropylmethyl.

R is Ci-C3haloalkyl, preferably R is Ci-C haloalkyl, More preferably R 4 is Ci-C 2 fluoroalkyl; most preferably R 4 IS trifluoromethyl.

R5 is Ci-C3alkyl; preferably Rs is Ci-C 2 alkyl.

More preferably Rs is Ci-C2alkyl; most preferably Rs is methyl.

Ai is N or CH.

A 2 is N or CH.

In one embodiment, Ai and A2 are both N; in another embodiment Ai and A2 are both CH. Preferably preferably Ai and A2 are both CH.

Re is hydrogen or Ci-C3haloalkyl, preferably R6 is Ci-C3haloalkyl.

More preferably R6 is hydrogen or Ci-C 2 fluoroalkyl, most preferably R6 is trifluoromethyl R7 is hydrogen or Ci-C3alkyl, preferably R7 is hydrogen or Ci-C 2 alkyl.

More preferably R7 is hydrogen or Ci-C2alkyl, most preferably R7 is hydrogen.

Rs is Ci-C3alkyl, preferably Rs is Ci-C 2 alkyl; more preferably Rs is methyl.

Rg is Ci-C3alkyl; preferably Rg is Ci-C 2 alkyl; more preferably Rg is methyl. A preferred group of compounds of formula I is represented by the compounds of formula 1-1

wherein Ri, R 2 , R3, R 4, Rs, A and X are as defined under formula I above.

In a preferred embodiment of said compounds of formula 1-1 :

A is N or CH, preferably A is CH;

X is S or SO2, preferably X is SO2;

Ri is Ci-C 2 haloalkyl, preferably Ri is Ci-C 2 fluoroalkyl;

R 2 IS Ci-C3alkyl; preferably R 2 IS Ci-C 2 alkyl;

R3 is Ci-C 2 alkyl or cyclopropyl-Ci-C 2 alkyl, preferably R3 is ethyl or cyclopropylmethyl; R 4 is Ci-C3haloalkyl, preferably R 4 is Ci-C 2 haloalkyl; and

Rs is Ci-C3alkyl; preferably Rs is Ci-C 2 alkyl.

In another preferred group of compounds of formula 1-1 :

A is N or CH;

X is S or SO2;

Ri is CF 2 H, CFS, CH 2 CHF 2 , CH 2 CF3, CF 2 CHF 2 , or CF 2 CF3, preferably Ri is trifluoromethyl or pentafluoroethyl; R 2 IS methyl or ethyl; preferably R 2 IS methyl;

R3 is ethyl or cyclopropylmethyl;

R4 is Ci-C2fluoroalkyl; preferably R4 is trifluoromethyl; and

R5 is Ci-C 2 alkyl; preferably Rs is methyl.

In the compounds of formula 1-1 and all of the preferred embodiments of compounds of formula 1-1 mentioned above, preferred definitions of Ri, R2, R3, R4, Rs, A and X are, in any combination thereof, as set out below:

A is N or CH, preferably A is CH;

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

Ri is trifluoromethyl or pentafluoroethyl; preferably Ri is pentafluoroethyl;

R 2 is methyl;

R3 is ethyl or cyclopropylmethyl; preferably R3 is ethyl;

R 4 is trifluoromethyl; and

Rs is methyl.

In another preferred group of compounds of formula 1-1 , and in all of the preferred embodiments of compounds of formula 1-1 mentioned above, Ri is trifluoromethyl or pentafluoroethyl; preferably Ri is trifluoromethyl.

Another preferred group of compounds of formula I is represented by the compounds of formula I-2

wherein Ri, R2, R3, R6, R7, A, Ai, A2 and X are as defined under formula I above. In a preferred embodiment of said compounds of formula i-2:

A is N or CH, preferably A is CH;

X is S or SO2, preferably X is SO2;

Ri is Ci-C 2 haloalkyl, preferably Ri is Ci-C 2 fluoroalkyl;

R 2 IS Ci-C3alkyl; preferably R 2 IS Ci-C 2 alkyl;

R3 is Ci-C2alkyl or cyclopropyl-Ci-C2alkyl, preferably R3 is ethyl or cyclopropylmethyl;

Ai is N or CH;

A 2 is N or CH;

Re is hydrogen or Ci-C3haloalkyl, preferably R6 is Ci-C3haloalkyl; and f¾7 is hydrogen or Ci-C3alkyl, preferably R is hydrogen or Ci-C alkyl.

In another preferred group of compounds of formula I-2:

A is N or CH;

X is S or SO ;

Ri is CF2H, CFs, CH2CHF2, CH2CF3, CF2CHF2, or CF2CF3, preferably Ri is trifluoromethyl or pentafluoroethyl;

R IS methyl or ethyl; preferably R IS methyl;

R3 is ethyl or cyclopropylmethyl;

Ai is N or CH;

A is N or CH;

Re is hydrogen or Ci-C3haloalkyl, preferably R6 is Ci-C3haloalkyl; and

R7 is hydrogen or Ci-C3alkyl, preferably R7 is hydrogen or Ci-C alkyl.

In the compounds of formula i-2 and all of the preferred embodiments of compounds of formula i-2 mentioned above, preferred definitions of Ri, R 2 , R3, R6, R7, A, Ai, A 2 and X are, in any combination thereof, as set out below:

A is N or CH, preferably A is CH;

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

Ri is trifluoromethyl or pentafluoroethyl; preferably Ri is pentafluoroethyl;

R is methyl;

R3 is ethyl or cyclopropylmethyl; preferably R3 is ethyl;

Ai is N or CH;

A is N or CH;

Re is hydrogen or Ci-C fluoroalkyl, preferably R6 is trifluoromethyl; and

R7 is hydrogen or Ci-C alkyl, preferably R7 is hydrogen.

In another preferred group of compounds of formula i-2, and in all of the preferred embodiments of compounds of formula i-2 mentioned above, Ai and A are both N; or Ai and A are both CH; preferably Ai and A are both CH.

In another preferred group of compounds of formula i-2, and in all of the preferred embodiments of compounds of formula i-2 mentioned above, R6 and R7 are both H.

In another preferred group of compounds of formula i-2, and in all of the preferred embodiments of compounds of formula i-2 mentioned above, Ri is trifluoromethyl or pentafluoroethyl; preferably Ri is trifluoromethyl.

Another preferred group of compounds of formula I is represented by the compounds of formula 1-3

wherein Ri, R2, R3, A and X are as defined under formula I above. In a preferred embodiment of said compounds of formula I-3:

A is N or CH, preferably A is N;

X is S or SO2, preferably X is SO2;

Ri is Ci-C2haloalkyl, preferably Ri is Ci-C2fluoroalkyl;

R2 IS Ci-C3alkyl; preferably R2 IS Ci-C2alkyl; and

R3 is Ci-C2alkyl or cyclopropyl-Ci-C2alkyl, preferably R3 is ethyl or cyclopropylmethyl.

In another preferred group of compounds of formula i-3:

A is N or CH;

X is S or SO2;

Ri is CF2H, CFs, CH2CHF2, CH2CF3, CF2CHF2, or CF2CF3, preferably Ri is trifluoromethyl or pentafluoroethyl;

R 2 IS methyl or ethyl; preferably R 2 IS methyl; and

R3 is ethyl or cyclopropylmethyl. In the compounds of formula I-3 and all of the preferred embodiments of compounds of formula I-3 mentioned above, preferred definitions of Ri, R 2 , R3, A and X are, in any combination thereof, as set out below:

A is N or CH, preferably A is N;

X is S, SO or SO2; preferably X is SO2;

Ri is trifluoromethyl or pentafluoroethyl; preferably Ri is pentafluoroethyl;

R2 is methyl; and

R3 is ethyl or cyclopropylmethyl; preferably R3 is ethyl.

Another preferred group of compounds of formula I is represented by the compounds of formula I-4

wherein Ri, R 2 , R3, Re, R9, A and X are as defined under formula I above.

In a preferred embodiment of said compounds of formula I-4:

A is N or CH, preferably A is CH;

X is S or SO2, preferably X is SO2;

Ri is Ci-C2haloalkyl, preferably Ri is Ci-C2fluoroalkyl;

R2 IS Ci-C3alkyl; preferably R2 IS Ci-C2alkyl;

R3 is Ci-C2alkyl or cyclopropyl-Ci-C2alkyl, preferably R3 is ethyl or cyclopropylmethyl;

Re is Ci-C3alkyl, preferably Re is Ci-C2alkyl; and

R9 is Ci-C3alkyl; preferably R9 is Ci-C2alkyl.

In another preferred group of compounds of formula i-4:

A is N or CH;

X is S or SO2;

Ri is CF 2 H, CFS, CH 2 CHF 2 , CH 2 CF3, CF 2 CHF 2 , or CF 2 CF3, preferably Ri is trifluoromethyl or pentafluoroethyl;

R 2 IS methyl or ethyl; preferably R 2 IS methyl;

R3 is ethyl or cyclopropylmethyl;

Re is methyl; and

Rg is methyl.

In the compounds of formula I-4 and all of the preferred embodiments of compounds of formula I-4 mentioned above, preferred definitions of Ri , R2, R3, Re, R9, A and X are, in any combination thereof, as set out below:

A is N or CH, preferably A is CH;

X is S, SO or SO2; preferably X is SO2;

Ri is trifluoromethyl or pentafluoroethyl; preferably Ri is pentafluoroethyl;

R2 is methyl;

R3 is ethyl or cyclopropylmethyl; preferably R3 is ethyl;

Re is methyl; and

R9 is methyl. In each case, the foregoing groups of compounds of formula I, 1-1 , I-2, I-3 and I-4 according to the invention are in free form, in oxidized form as a N-oxide or in salt form, e.g. an agronomically usable salt form.

In another aspect the present invention provides a composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula I, 1-1 , I-2, I-3 or I-4, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined in any of the foregoing embodiments (above), and, optionally, an auxiliary or diluent.

In a further aspect the present invention provides a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula I, 1-1 , I-2, I-3 or I-4, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined in any of the foregoing embodiments (above) or a composition as defined above.

In a yet further aspect the present invention provides a method for the protection of plant propagation material from the attack by insects, acarines, nematodes or molluscs, which comprises treating the propagation material or the site, where the propagation material is planted, with a composition as defined above.

The process according to the invention for preparing compounds of formula I is carried out in principle by methods known to those skilled in the art. More specifically, the subgroup of compounds of formula I, wherein X is SO (sulfoxide) and/or SO (sulfone), may be obtained by means of an oxidation reaction of the corresponding sulfide compounds of formula I, wherein X is S, involving reagents such as, for example, m-chloro-peroxybenzoic acid (mCPBA), hydrogen peroxide, oxone, sodium periodate, sodium hypochlorite or tert-butyl hypochlorite amongst other oxidants. The oxidation reaction is generally conducted in the presence of a solvent. Examples of the solvent to be used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform; alcohols such as methanol and ethanol; acetic acid; water; and mixtures thereof. The amount of the oxidant to be used in the reaction is generally 1 to 3 moles, preferably 1 to 1.2 moles, relative to 1 mole of the sulfide compounds I to produce the sulfoxide compounds I, and preferably 2 to 2.2 moles of oxidant, relative to 1 mole of of the sulfide compounds I to produce the sulfone compounds I. Such oxidation reactions are disclosed, for example, in WO 2013/018928.

Compounds of formula I, wherein X is S, SO (sulfoxide) and/or SO (sulfone), may be prepared following scheme 1. Compounds of formula I, wherein X is S, SO (sulfoxide) and/or SO (sulfone), may be obtained by the coupling reactions of carboxylic acids IV, wherein J is as defined in formula I above and thiazole amine II, wherein Ri, R are as defined in formula I above. The reaction may optionally require Scheme 1 :

lewis acids such as AlCb, POCI , ZrC , Ti(0-/Pr)4 amongst other lewis acids. Such transformations are reported in Chem. Eur. J. 2012, 18, 3822 - 3826 and Synlett 2012, 23, 2201 - 2204. The coupling reactions of carboxylic acids IV, wherein J is as defined in formula I and thiazole amine II, wherein Ri, R are as defined in formula I above may also be carried out in the presence of coupling reagents such as EDC, HOBt, DCC, DIC, HATU or PyBOP. Additionally such transformations can also be carried out in 2 steps, first by converting the carboxylic acid IV, wherein J is as defined in formula I to a carboxyl halide especially carbonyl chloride or other carboxyl substituted with a leaving group and treating further with thiazole amine II, wherein Ri, R are as defined in formula I in the presence of a suitable base. Examples of reagents that may be used for transforming carboxylic acids to carbonyl chloride include oxalyl chloride or SOCh and which are used in presence of catalytics DMF. The example of suitable bases include include EΪ3N, DIPEA, pyridine, 2,6-lutidine and amongst others. The above transformations are generally conducted in the presence of a solvent. Examples of the solvent to be used in the reactions include aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane and chloroform or cyclic hydrocarbons optionally containing 1 to 2 oxygen atom such as THF, 1 ,4-dioxane.

Compounds of formula II, wherein Ri and R are as defined above, may be prepared by coupling reactions of carboxylic acid III, wherein Ri is as defined in formula I above and carbothioamide V, wherein R is as defined in formula I above and a subsequent ring closure reaction with elimination of water molecule. The reactions proceeds in the presence of activating agent which facilitate such coupling reactions and ring cyclization reactions. Examples of such activating agent include such as POCI or PCI The reactions are conducted in the presence of inert solvent in the temperature ranging from -15 °C to 150 °C preferably from room temperature to the boiling point of solvent. Examples of inert solvent includes aliphatic halogenated hydrocarbons such as dichloromethane, chloroform, or oxygenated hydrocarbons such as THF or 1 ,4-dioxane. Such reactions are reported for example in J. Med. Chem. 2004, 47, 6760-6767, J. Het. Chem., 1980, 17, 1469 or in WO 201 1/035900, WO 2016/087265.

Alternatively such transformations may also be performed in 2 steps following scheme 2 which involves

Scheme 2:

activation of carboxylic acid III, wherein Ri is as defined in formula I above with activating agent such as oxalyl chloride, SOCI which are used in the presence of catalytic DMF. Carboxylic acid III, wherein Ri is as defined in formula I above may also be converted to the anhydride, analogous to the one known in Yamaguchi Esterification. The activated carboxylic acid derivatives may react with carbothioamide V, wherein R is as defined in formula I above optionally in the presence of acylation catalyst such as DMAP and optionally in the presence of base such as triethyl amine, DIPEA or pyridine. The reactions are conducted in the presence of suitable solvent and at temperatures between 0 and 50 °C, to form acylthiosemicarbazide compounds of formula XI, wherein Ri and R are as described above. Examples of solvent to be used include ethers such as tetrahydrofuran, ethylene glycoldimethyl ether, tert- butylmethyl ether, and 1 ,4-dioxane, aromatic hydrocarbons such as toluene andxylene, halogenated hydrocarbons such as dichloromethane and chloroform, nitriles such asacetonitrile or polar aprotic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N methyl-2-pyrrolidone or dimethyl sulfoxide. Cyclodehydration of acylthiosemicarbazide compounds of formula XI, wherein Ri and R are as described above, in presence of polyphosphoric acid PPA or concentrated sulfuric acid H SO cone for example, may give the compounds of formula II, or salts thereof. Such coupling and dehydrative cyclization are reported for example in Acta Chimica Academiae Scientiarum Hungaricae 1974, 82, 91- 97 or in DE 2231664 or in J. Med. Chem. 2004, 47, 6760-6767.

Alternatively compounds of formula II, wherein Ri and R are as defined above, may be prepared following scheme 3 which involves nucleophilic aromatic substitution reaction of halogen with the amino compound. Such reactions may be conducted optionally in the presence of a suitable base for example potassium carbonate, cesium carbonate, sodium carbonate, triethyl amine, N, N-Diisopropylethylamine

Scheme 3: or pyridine and in the presence of inert solvent and at temperature range from 0 °C to the boiling point of the solvent preferably between room temperature and boiling point of solvent. Suitable solvent may include polar aprotic solvent such as DMF, DMSO or DME.

Compounds of formula X, wherein Ri is as defined above, may be prepared by Sandmeyer Reaction of compounds of formula VII, wherein Ri is as defined above. Such reactions may require combination of reagents which can promote the sequential generation of diazonium salt and halogenation reaction. The reagents which facilitate the diazotization reaction include sodium nitrite, tert-butyl nitrite or isoamyl nitrite. These reagents may optionally be used in the presence of suitable acids such as HCI, HBr, H SO or TsOH. The halogenation reaction may require salt or metal complexes such as NaBr, NaCI, Kl, KBr, Cul, CuBr and amongst others. The reaction may be conducted in between -40 °C to 100 °C and in the presence of suitable solvent such as MeCN, MeOH, water or acetic acid.

Compounds of formula VII, wherein Ri is as defined above, may be prepared by similar procedure as defined above for the preparation of compound II from compound III in scheme 1 and 2.

Alternatively compounds of formula I, wherein X is S, SO (sulfoxide) and/or SO (sulfone), Ri and J are as defined above may be prepared following scheme 4 via alkylation reaction as shown below and described in WO 2016/087265.

Scheme 4:

In particular situation for compounds of formula IV when J is Ji, wherein X is S, SO, or SO 2 ; R3 is Ci- C 4 alkyl, C3-C 4 cycloalkyl-Ci-C 2 alkyl; A is CH or N; R is hydrogen, Ci-C3alkyl, Ci-C3haloalkyl, cyclopropyl; and Rs is Ci-C3alkyl, Ci-C3haloalkyl, cyclopropyl (CAS Registry Number: 1943762-00-2, when R3 is ethyl, X is SO , A is N, R4 is trifluoromethyl and Rs is methyl, CAS Registry Number: 1943761- 92-9 when R3 is ethyl, X is S, A is N, R 4 is trifluoromethyl and Rs is methyl) can be prepared by methods known in the literature and described in WO 2016/091731 A1 and WO 2017/133994 A1.

In particular situation for compounds of formula IV when J is J , wherein X is S, SO, or SO ; R3 is Ci-

C 4 alkyl, C3-C 4 cycloalkyl-Ci-C 2 alkyl; A is N; Ai and A are CH; R6 is hydrogen, halogen, cyano, Ci- C3alkyl, Ci-C3haloalkyl; and R7 is hydrogen, halogen, cyano, Ci-C3alkyl, Ci-C3haloalkyl; represented by compounds of formula IVa, wherein X is S, SO, or SO ; R3 is Ci-C 4 alkyl, C3-C 4 cycloalkyl-Ci-C 2 alkyl; R6 is hydrogen, halogen, cyano, Ci-C3alkyl, Ci-C3haloalkyl; and R is hydrogen, halogen, cyano, Ci- C3alkyl, Ci-C3haloalkyl can be prepared by methods known in the literature and described in WO16091731 A1.

In particular situation for compounds of formula IV when J is J 2 , wherein X is S, SO, or SO 2 ; R3 is Ci-

C4alkyl, C3-C4cycloalkyl-Ci-C2alkyl; A is N or CH; Ai and A are N; R6 is hydrogen, halogen, cyano, Ci- C3alkyl, Ci-C3haloalkyl; and R7 is hydrogen, halogen, cyano, Ci-C3alkyl, Ci-C3haloalkyl; represented by compounds of formula IVb, wherein X is S, SO, or S0 2 ; R3 is Ci-C 4 alkyl, C3-C 4 cycloalkyl-Ci-C 2 alkyl; A

Scheme 5: is N or CH; f¾6 is hydrogen, halogen, cyano, Ci-C3alkyl, Ci-C3haloalkyl; and R is hydrogen, halogen, cyano, Ci-C3alkyl, Ci-C3haloalkyl can be prepared following scheme 5 by saponification of compounds of the formula XIV, wherein X is S, SO or SO , and in which A, R , R6 and R are as defined in formula I, and wherein Roo is Ci-C 4 alkyl. Conditions for such a reaction, typically hydrolysis by water in presence of a base, are known to a person skilled in the art (using for example: aqueous sodium, potassium or lithium hydroxide in methanol, ethanol, tetrahydrofuran or dioxane at room temperature or up to refluxing conditions; or alternatively treating compounds of formula XIV with an acid, such as for example a hydrohalide acid, preferably hydrochloride or hydrobromide acid, or trifluoroacetic acid, optionally in presence of a solvent, such as tetrahydrofuran, dioxane or dichloromethane, at temperatures between 0 and 150°C).

Compounds of formula XIV, wherein X is S, SO or SO , and in which A, R , R6 and R are as defined in formula I, and wherein Roo is Ci-C 4 alkyl can be prepared by the condensation reaction of compounds of formula XII, wherein X, Ri and A are as defined in formula I above and wherein Roo is Ci-C 4 alkyl with diketo compounds of formula XIII, wherein R6 and R are as defined in formula I above optionally in the presence of acid such as trifluoroacetic acid, para-toluene sulfonic acid amongst others or in the presence of base such as potassium tert-butoxide, sodium hydroxide amongst others. The reaction can be carried out in the presence of an inert solvent, like methanol, ethanol, dioxane, THF, or toluene, usually at temperature between 50 to 150°C. Such reactions are known in the literature for example in Green Chemistry Letters and Reviews Vol. 5, No. 2, June 2012, 127-134.

Compounds of formula XII, wherein wherein X, Ri and A are as defined in formula I above and wherein Roo is Ci-C 4 alkyl, can be prepared following scheme 6 by reduction of compounds of the formula XVIII,

or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), wherein X, A and Ri are as defined in formula I, and wherein Roo is Ci-C 4 alkyl, under conditions known to a person skilled in the art, such as for example using zinc dust and acetic acid or trifluoroacetic acid, or mixtures thereof, or using molecular hydrogen (hte), optionally under pressure, usually in the presence of a catalyst such as nickel, palladium (for example palladium on charcoal, typically 5-10% Pd/C) or platinum, in alcoholic solvents (such as for example methanol or ethanol), or in inert solvents (such as for example ethyl acetate), at temperatures between 0°C and 120°C, preferably between room temperature and reflux temperature. Compounds of the formula XVIII, or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), wherein X, A, and Ri are as defined in formula I, and wherein Roo is Ci-C 4 alkyl, can be prepared by reacting compounds of the formula XV (described in WO 2019008072 A1 , CAS registry number 2260877-37-8, when X is S, Rt is ethyl, A is CH, Roo is ethyl, Hal is chloro) wherein X, A and Ri are as defined in formula I, and wherein Roo is Ci-C 4 alkyl, and wherein Hal is a halogen such as, for example, fluorine, chlorine or bromine (preferably fluorine or chlorine), with ammonia or ammonia surrogates such as ammonium hydroxide, or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), optionally in presence of metal catalyst such as copper, copper iodide, copper sulfate or combinations of them and optionally in the presence of an additional base. This transformation is preferably performed in suitable solvents (or diluents) such as alcohols, amides, esters, ethers, nitriles and water, particularly preferred are methanol, ethanol, 2,2,2- trifluoroethanol, propanol, iso-propanol, N,N-dimethylformamide, N,N-dimethylacetamide, dioxane, tetrahydrofuran, dimethoxyethane, acetonitrile, ethyl acetate, water or mixtures thereof, at temperatures between 0-150°C, preferably at temperatures ranging from room temperature to the boiling point of the reaction mixture, optionally under microwave irradiation or pressurized conditions using an autoclave. Alternatively compounds of the formula XVIII, or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), wherein X, A, and Ri are as defined in formula I, and wherein Roo is Ci-C 4 alkyl, can be prepared by reacting compounds of the formula XV (described in WO 2019008072 A1 , CAS registry number 2260877-37-8, when X is S, Ri is ethyl, A is CH, Roo is ethyl, Hal is chloro) wherein X, A and Ri are as defined in formula I, and wherein Roo is Ci-C 4 alkyl, and wherein Hal is a halogen such as, for example, chlorine or bromine (preferably chlorine), with compounds of formula XVI optionally in the presence of a base, such as potassium carbonate, cesium carbonate, sodium hydroxide, in an inert solvent, such as toluene, dimethylformamide DMF, N-methyl pyrrolidine, dimethyl sulfoxide DMSO, dioxane, tetrahydrofuran THF, and the like, optionally in the presence of a catalyst, for example palladium(ll)acetate, bis(dibenzylideneacetone)palladium(0) (Pd(dba)2) or tris(dibenzylideneacetone)dipalladium(0) (Pd 2 (dba)3, optionally in form of a chloroform adduct), or a palladium pre-catalyst such as for example ferf-BuBrettPhos Pd G3 [(2-Di-ferf-butylphosphino-3,6-dimethoxy-2',4',6'-triisoprop yl-1 ,1 '-biphenyl)-2- (2'-amino-1 , T-biphenyl)]palladium(ll) methanesulfonate or BrettPhos Pd G3 [(2-di- cyclohexylphosphino-3,6-dimethoxy-2',4',6'- triisopropyl-1 , 1 '-biphenyl)-2-(2'-amino-1 , 1 ' biphenyl)]palladium(ll) methanesulfonate, and optionally a ligand, for example SPhos, f-BuBrettPhos or Xantphos, at temperatures between 60-120°C, optionally under microwave irradiation. Such reactions are known in the literature and have been reported for example in in Green Chemistry, 16(3), 1480- 1488; 2014, Tetrahedron, 2009, 65, 6576, Org. Lett. 2013, 15, 2876.and J. Am. Chem. Soc. 2009, 131, 16720.

Alternatively compounds of formula XII, or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), wherein wherein X, Ri and A are as defined in formula I above and wherein Roo is Ci-C 4 alkyl, can be prepared from compounds of formula XXII, or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), wherein wherein X, Ri and A are as defined in formula I above and wherein Roo is Ci-C 4 alkyl, and Hal’ is a halogen such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), by analogous procedure as decribed above for the preparation of compounds of formula XVIII from compounds of formula XV. Compounds of formula XXII, or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), wherein wherein X, Ri and A are as defined in formula I above and wherein Roo is Ci-C 4 alky I, and Hal’ is a halogen such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), can be prepared by a halogenation reaction, which involves for example, reacting compounds of the formula XXI, or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), wherein wherein X, Ri and A are as defined in formula I above and wherein Roo is Ci-C 4 alkyl, with halogenating reagents such as N-chlorosuccinimide (NCS), N- bromosuccinimide (NBS) or N-iodosuccinimide (NIS), or alternatively chlorine, bromine or iodine. Such halogenation reactions are carried out in an inert solvent, such as chloroform, carbon tetrachloride, 1 ,2- dichloroethane, acetic acid, ethers, acetonitrile or N,N-dimethylformamide, at temperatures between 20- 200°C, preferably room temperature to 100°C. Compounds of formula XXI, or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or a hydrobromide salt, or a trifluoroacetic acid salt, or any other equivalent salt), wherein wherein X, Ri and A are as defined in formula I above and wherein Roo is Ci-C 4 alky I, can be prepared from compounds of formula XX, wherein wherein X, Ri and A are as defined in formula I above and wherein Roo is Ci-C 4 alkyl, and Hal” is a halogen such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), by analogous methods as described above for the preparation of compounds of formula XVIII from compounds of formula XV. Compounds of formula XX, wherein wherein X, Ri and A are as defined in formula I above and wherein Roo is Ci- C 4 alkyl, and Hal” is a halogen such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), can be prepared from the corresponding carboxylic acid compounds of formula XIX, wherein X, Ri and A are as defined in formula I above and wherein Roo is Ci-C4alkyl, and Hal” is a halogen such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), by reaction with an alcohol of formula R OH, wherein Roo is Ci-C 4 alkyl, optionally in the presence of an acid (such as sulfuric acid), under esterification methods well known to a person skilled in the art.

Compounds of formula XIX, wherein X is S, and in which A and Ri are as defined in formula I, and wherein Hal is a halogen such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), may be either known, commercially available or may be prepared by methods known to a person skilled in the art. See for example, W016/030229 (compound XIX, CAS registry number 1857366-13-2, wherein X=S, A=N, RI=CH 2 CH 3 , Hal=Br).

In particular situation for compounds of formula IV when J is J3, wherein X is S, SO, or SO ; R3 is Ci- C4alkyl, C3-C4cycloalkyl-Ci-C2alkyl; A is N or CH; Ai is CH and A is N; f¾6 is hydrogen, halogen, cyano, Ci-C3alkyl, Ci-C3haloalkyl; and R7 is hydrogen, halogen, cyano, Ci-C3alkyl, Ci-C3haloalkyl; represented by compounds of formula IVc, wherein X is S, SO, or SO ; R3 is Ci-C 4 alkyl, C3-C 4 cycloalkyl-Ci-C 2 alkyl; A is N or CH; R6 is hydrogen, halogen, cyano, Ci-C3alkyl, Ci-C3haloalkyl; and R7 is hydrogen, halogen, cyano, Ci-C3alkyl, Ci-C3haloalkyl and for compounds of formula formula IV when J is J3, wherein X is S, SO, or SO ; R3 is Ci- C 4 alkyl, C3-C 4 cycloalkyl-Ci-C 2 alkyl; A is N or CH; Ai is N and A is CH; R6 is hydrogen, halogen, cyano, Ci-C3alkyl, Ci-C3haloalkyl; and R7 is hydrogen, halogen, cyano, Ci-C3alkyl, Ci-C3haloalkyl; represented by compounds of formula IVd, wherein X is S, SO, or SO ; R3 is Ci-C 4 alkyl, C3-C4cycloalkyl-Ci-C2alkyl; A is N or CH; R6 is hydrogen, halogen, cyano, Ci-C3alkyl, Ci-C3haloalkyl; and R7 is hydrogen, halogen, cyano, Ci-C3alkyl, Ci-C3haloalkyl can be prepared by analogous methods known in the literature for example as decribed in WO2016038173. In particular situation for compounds of formula IV when J is J3, wherein X is S, SO, or S02; R3 is Ci- C4alkyl, C3-C4cycloalkyl-Ci-C2alkyl; A is CH or N (CAS Registry number: 2253772-22-2 when R3 is ethyl, X is S and A is N; CAS Registry number: 2137868-29-0 when R3 is ethyl, X is SO and A is N) can be prepared by methods known in the literature and described in WO 2018/215304 A1.

In particular situation for compounds of formula IV when J is J4, wherein X is S, SO, or S02; R3 is Ci- C 4 alkyl, C3-C 4 cycloalkyl-Ci-C 2 alkyl; A is CH or N; Re is Ci-C3alkyl, Ci-C3haloalkyl and Rg is Ci-C3alkyl, Ci-C3haloalkyl (CAS Registry number: 2260877-25-4 when R3 is ethyl, X is SO , Rs and Rg are methyl and A is N; CAS Registry number: 2260877-42-5 when R3 is ethyl, X is S, Rs and Rg are methyl and A is CH) can be prepared by methods known in the literature and described in WO 2019/008072 A1. The compounds according to the following Tables A-1 to A-6, Tables C-1 to C-6, Tables E-1 to E-4, and Tables G-1 to G-24 below can be prepared according to the methods described above. The examples which follow are intended to illustrate the invention and show preferred compounds of formula I as represented by the compounds of formulae (1-1 a), (l-2a), (l-3a), and (l-4a). In the tables which follow below, cPr represents the cyclopropyl group.

The tables below illustrate specific compounds of the invention.

Table A-1 provides 4 compounds A-1.001 to A-1.004 of formula l-4a wherein R 2 is Me, Rg is Me, Re is Me, X is S, R3 is CH 2 CH3 and Ri, A are as defined in table B.

Table B: Substituent definitions of Ri and A:

Table A-2 provides 4 compounds A-2.001 to A-2.004 of formula l-4a wherein R 2 is Me, Rg is Me, Re is Me, X is S, R3 is ChhcPr and Ri , A are as defined in table B. Table A-3 provides 4 compounds A-3.001 to A-3.004 of formula l-4a wherein R 2 is Me, Rg is Me, Re is Me, X is SO, R3 is CH 2 CH3 and Ri, A are as defined in table B.

Table A-4 provides 4 compounds A-4.001 to A-4.004 of formula l-4a wherein R 2 is Me, Rg is Me, Re is Me, X is SO, R3 is ChhcPr and Ri , A are as defined in table B.

Table A-5 provides 4 compounds A-5.001 to A-5.004 of formula l-4a wherein R 2 is Me, Rg is Me, Re is

Me, X is SO 2 , R3 is CH 2 CH3 and Ri, A are as defined in table B.

Table A-6 provides 4 compounds A-6.001 to A-6.004 of formula l-4a wherein R 2 is Me, Rg is Me, Re is

Me, X is SO 2 , R3 is ChhcPr and Ri, A are as defined in table B. The tables below illustrate specific compounds of the invention.

(l-3a)

Table D: Substituent definitions of Ri and R :

Table C-1 provides 4 compounds C-1.001 to C-1.004 of formula l-3a wherein R 2 is Me, X is S, A is N and Ri, R3 are as defined in table D.

Table C-2 provides 4 compounds C-2.001 to C-2.004 of formula l-3a wherein R 2 is Me, X is S, A is CH and Ri, R3 are as defined in table D.

Table C-3 provides 4 compounds C-3.001 to C-3.004 of formula l-3a wherein R 2 is Me, X is SO, A is N and Ri, R3 are as defined in table D. Table C-4 provides 4 compounds C-4.001 to C-4.004 of formula l-3a wherein R is Me, X is SO, A is CH and Ri, R3 are as defined in table D.

Table C-5 provides 4 compounds C-5.001 to C-5.004 of formula l-3a wherein R is Me, X is SO , A is N and Ri, R are as defined in table D.

Table C-6 provides 4 compounds C-6.001 to C-6.004 of formula l-3a wherein R 2 is Me, X is SO 2 , A is CH and Ri, R3 are as defined in table D.

The tables below illustrate specific compounds of the invention.

Table F: Substituent definitions of Ri and X:

Table E-1 provides 6 compounds E-1.001 to E-1.006 of formula 1-1 a wherein R 2 is Me, R3 is CH 2 CH3, A is N, R5 is CH2CH3, R4 is CF3 and Ri, X are as defined in table F.

Table E-2 provides 6 compounds E-2.001 to E-2.006 of formula 1-1 a wherein R 2 is Me, R3 is CH 2 CH3, A is CH, R5 is CH2CH3, R4 is CF3 and Ri, X are as defined in table F.

Table E-3 provides 6 compounds E-3.001 to E-3.006 of formula 1-1 a wherein R 2 is Me, R3 is CH cPr, A is N, R5 is CH CH , R4 is CF and Ri, X are as defined in table F. Table E-4 provides 6 compounds E-4.001 to E-4.006 of formula 1-1 a wherein R 2 is Me, R3 is Ch cPr, A is CH, R5 is CH2CH3, R4 is CF3 and Ri, X are as defined in table F.

The tables below illustrate specific compounds of the invention.

Table H: Substituent definitions of A, Ai, f¾6 and A :

Table G-1 provides 16 compounds G-1.001 to G-1.016 of formula l-2a wherein R 2 is Me, R7 is CF3, X is S, R3 is CH2CH3, Ri is CF3 and A, Ai, R6, A2 are as defined in table H.

Table G-2 provides 16 compounds G-2.001 to G-2.016 of formula l-2a wherein R2 is Me, R7 is CF3, X is S, R3 is CH2CH3, Ri is CF2CF3 and A, Ai, R6, A2 are as defined in table H.

Table G-3 provides 16 compounds G-3.001 to G-3.016 of formula l-2a wherein R 2 is Me, R7 is CF3, X is S, R3 is CFhcPr, Ri is CF3 and A, Ai, R6, A 2 are as defined in table H.

Table G-4 provides 16 compounds G-4.001 to G-4.016 of formula l-2a wherein R 2 is Me, R7 is CF3, X is S, R3 is CFhcPr, Ri is CF2CF3 and A, Ai, Re, A2 are as defined in table H.

Table G-5 provides 16 compounds G-5.001 to G-5.016 of formula l-2a wherein R 2 is Me, R7 is CF3, X is SO, R3 is CH2CH3, Ri is CF3 and A, Ai , R6, A2 are as defined in table H.

Table G-6 provides 16 compounds G-6.001 to G-6.016 of formula l-2a wherein R 2 is Me, R7 is CF3, X is SO, R3 is CH2CH3, Ri is CF2CF3 and A, Ai, R6, A2 are as defined in table H.

Table G-7 provides 16 compounds G-7.001 to G-7.016 of formula l-2a wherein R 2 is Me, R7 is CF3, X is SO, R3 is CFhcPr, Ri is CF3 and A, Ai, Re, A2 are as defined in table H.

Table G-8 provides 16 compounds G-8.001 to G-8.016 of formula l-2a wherein R2 is Me, R7 is CF , X is SO, R3 is CH cPr, Ri is CF CF and A, Ai, R6, A are as defined in table H.

Table G-9 provides 16 compounds G-9.001 to G-9.016 of formula l-2a wherein R 2 is Me, R7 is CF3, X is SO2, R3 is CH2CH3, Ri is CF3 and A, Ai, R6, A2 are as defined in table H.

Table G-10 provides 16 compounds G-10.001 to G-10.016 of formula l-2a wherein R 2 is Me, R7 is CF3, X is SO2, R3 is CH2CH3, Ri is CF2CF3 and A, Ai, R6, A2 are as defined in table H.

Table G-11 provides 16 compounds G-11.001 to G-11.016 of formula l-2a wherein R 2 is Me, R7 is CF3, X is SO2, R3 is CFhcPr, Ri is CF3 and A, Ai, Re, A2 are as defined in table H.

Table G-12 provides 16 compounds G-12.001 to G-12.016 of formula l-2a wherein R 2 is Me, R7 is CF , X is SO , R3 is CH cPr, Ri is CF CF and A, Ai, Re, A2 are as defined in table H.

Table G-13 provides 16 compounds G-13.001 to G-13.016 of formula l-2a wherein R 2 is Me, R7 is H, X is S, R3 is CH2CH3, Ri is CF3 and A, Ai, Re, A2 are as defined in table H.

Table G-14 provides 16 compounds G-14.001 to G-14.016 of formula l-2a wherein R2 is Me, R7 is H, X is S, R3 is CH2CH3, Ri is CF2CF3 and A, Ai, Re, A2 are as defined in table H.

Table G-15 provides 16 compounds G-15.001 to G-15.016 of formula l-2a wherein R 2 is Me, R7 is H, X is S, R3 is CFhcPr, Ri is CF3 and A, Ai, Re, A 2 are as defined in table H. Table G-16 provides 16 compounds G-16.001 to G-16.016 of formula l-2a wherein R 2 is Me, R7 is H, X is S, R3 is ChhcPr, Ri is CF 2 CF3 and A, Ai, R6, A 2 are as defined in table H.

Table G-17 provides 16 compounds G-17.001 to G-17.016 of formula l-2a wherein R2 is Me, R7 is H, X is SO, R3 is CH2CH3, Ri is CF3 and A, Ai, R6, A2 are as defined in table H.

Table G-18 provides 16 compounds G-18.001 to G-18.016 of formula l-2a wherein R 2 is Me, R7 is H, X is SO, R3 is CH2CH3, Ri is CF2CF3 and A, Ai, R6, A2 are as defined in table H.

Table G-19 provides 16 compounds G-19.001 to G-19.016 of formula l-2a wherein R 2 is Me, R7 is H, X is SO, R3 is ChhcPr, Ri is CF3 and A, Ai, Re, A 2 are as defined in table H.

Table G-20 provides 16 compounds G-20.001 to G-20.016 of formula l-2a wherein R 2 is Me, R7 is H, X is SO, R3 is CH cPr, Ri is CF CF and A, Ai, Re, A are as defined in table H.

Table G-21 provides 16 compounds G-21.001 to G-21.016 of formula l-2a wherein R 2 is Me, R7 is H, X is SO2, R3 is CH2CH3, Ri is CF3 and A, Ai, R6, A2 are as defined in table H.

Table G-22 provides 16 compounds G-22.001 to G-22.016 of formula l-2a wherein R 2 is Me, R7 is H, X is SO2, R3 is CH2CH3, Ri is CF2CF3 and A, Ai, Re, A2 are as defined in table H.

Table G-23 provides 16 compounds G-23.001 to G-23.016 of formula l-2a wherein R2 is Me, R7 is H, X is SO2, R3 is ChhcPr, Ri is CF3 and A, Ai, Re, A2 are as defined in table H.

Table G-24 provides 16 compounds G-24.001 to G-24.016 of formula l-2a wherein R 2 is Me, R7 is H, X is SO2, R3 is ChhcPr, Ri is CF2CF3 and A, Ai, Re, A2 are as defined in table H.

The compounds of formula I according to the invention are preventively and/or curatively valuable ac tive ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. The active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects, molluscs, nematodes or or representatives of the order Acarina. The insecticidal, molluscicidal, nematicidal or acaricidal activity of the active in gredients according to the invention can manifest itself directly, i. e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate, a good activity corresponding to a destruction rate (mortality) of at least 50 to 60%.

Compounds of formula I according to the invention may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile, improved physico-chemical properties, or increased biodegradability or environmental profile). In particular, it has been surprisingly found that certain compounds of formula I show an advantageous safety profile with respect to non-target organisms, for example, non-target arthropods, in particular pollinators such as honey bees, solitary bees, and bumble bees. Most particularly, Apis mellifera.

In this regard, certain compounds of formula I of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using experimental procedures similar to or adapted from those outlined in the biological examples, using lower application rates if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

Further it has surprisingly found that that compounds of formula I show advantageous physico chemical properties for application in crop protection, in particular reduced melting point, reduced lipophilicity and increased water solubility. Such properties have been found to be advantageous for plant uptake and systemic distribution, see for example A. Buchholz, S. Trapp, Pest Manag Sci 2016; 72: 929-939) in order to control certain pest species named below.

Examples of the abovementioned 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, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp, Tarsonemus spp. and Tetranychus spp.;

from the order Anoplura, for example,

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

from the order Coleoptera, for example,

Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis, Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala 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, Euschistus spp., Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp, Margarodes spp, Murgantia histrionic, Neomegalotomus spp, Nesidiocoris tenuis, Nezara spp., Nysius simulans, Oebalus insularis, Piesma spp., Piezodorus spp, Rhodnius spp., 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 big uttula, Amritodus atkinsoni, Aonid iella 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, Cicadulina 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 pallidus, 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., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., 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, Hoplo- campa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Pogonomyrmex spp, Slenopsis invicta, Solenopsis spp. and Vespa spp.;

from the order Isoptera, for example,

Coptotermes spp, Corniternes cumulans, Incisitermes spp, Macrotermes spp, Mastotermes spp, Microtermes spp, Reticulitermes spp.; Solenopsis geminate from the order Lepidoptera, for example,

Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp, Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp, Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima 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, Gra- pholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Herpetogramma 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 flammea, Papaipema nebris, Pectinophora gossypi- ela, 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., Trichoplusia ni, Tuta absoluta, and Yponomeuta spp.;

from the order Mallophaga, for example,

Damalinea spp. and Trichodectes spp.;

from the order Orthoptera, for example,

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

from the order Psocoptera, for example,

Liposcelis spp.;

from the order Siphonaptera, for example,

Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis; from the order Thysanoptera, for example,

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

from the order Thysanura, for example, Lepisma saccharina.

The active ingredients according to the invention can be used for controlling, i. e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests. Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines, hops, the plantain family and latex plants.

The compositions and/or methods of the present invention may be also used on any ornamental and/or vegetable crops, including flowers, shrubs, broad-leaved trees and evergreens.

For example the invention may be used on any of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antimhinum spp., Aster spp., Begonia spp. (e g. B. elatior, B. se perflorens, B. tubereux), Bougainvillea spp., Brachycome spp., Brassica spp. (ornamental), Calceolaria spp., Capsicum annuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemum spp., Cineraria spp. (C. maritime), Coreopsis spp., Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp.,

Gomphrena globosa, Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (/. Wallehana), Iresines spp., Kalanchoe spp., Lantana camara, Lavatera trimesths, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesia spp., Tagetes spp., Dianthus spp. (carnation), Canna spp., Oxalis spp., Beilis spp., Pelargonium spp. (P. peltatum, P. Zonale), Viola spp. (pansy), 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 bedding plants.

For example the invention may be used on any of the following vegetable species: Allium spp. (A. sativum, A. cepa, A. oschaninii, A. Porrum, A. ascalonicum, A. fistulosum), Anthhscus 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), Cithllus lanatus, Cucumis spp. (C. sativus, C. melo), Cucurbita spp. (C. pepo, C. maxima), Cyanara spp. (C. scolymus, C. cardunculus), Daucus carota, Foeniculum vulgare, Hypericum spp., Lactuca sativa, Lycopersicon spp. ( L . esculentum, L. lycopersicum), Mentha spp., Ocimum basilicum, Petroselinum crispum, Phaseolus spp. (P. vulgaris, P. coccineus), Pisum sativum, Raphanus sativus, Rheum rhaponticum, Rosemarinus spp., Salvia spp., Scorzonera hispanica, Solanum melongena, Spinacea oleracea, Valerianella spp. (V. locusta, V. eriocarpa) and Vida faba.

Preferred ornamental 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. Johnswort, mint, sweet pepper, tomato and cucumber.

The active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and

Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops. The active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca(preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).

The active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and

Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops. The active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca(preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).

In a further aspect, the invention may also relate to a method of controlling damage to plant and parts thereof by plant parasitic nematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasitic nematodes), especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species;

Needle nematodes, Longidorus elongatus and other Longidorus species; Pin nematodes,

Pratylenchus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans,

Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp..

The compounds of the invention may also have activity against the molluscs. Examples of which 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" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as d-endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or

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 (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood by d-endotoxins, for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip 1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ). Truncated toxins, for example a truncated CrylAb, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810). Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type

deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).

Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry1 Ac toxin); Bollgard I® (cotton variety that expresses a CrylAc toxin); Bollgard II® (cotton variety that expresses a CrylAc and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a CrylAb toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

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

2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer ( Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylAb toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de T ervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.

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

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry1 F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.

7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 c MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1 Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain

Lepidoptera, include the European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS (Zentrum far Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003,

(http://bats.ch1.

The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

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

Further areas of use of the compositions according to the invention are the protection of stored goods and store rooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.

The present invention 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, the method for controlling pests comprises applying the compositions of the invention to the target pests, to their locus or to a surface or substrate by brushing, rolling, spraying, spreading or dipping. By way of example, an IRS (indoor residual spraying) application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention. In another embodiment, it is contemplated to apply such compositions to a substrate such as non-woven or a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.

In one embodiment, the method for controlling such pests comprises applying a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate. Such application may be made by brushing, rolling, spraying, spreading or dipping the pesticidal composition of the invention. By way of example, an IRS application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention so as to provide effective residual pesticidal activity on the surface. In another embodiment, it is contemplated to apply such compositions for residual control of pests on a substrate such as a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.

Substrates including non-woven, fabrics or netting to be treated may be made of natural fibres such as cotton, raffia, jute, flax, sisal, hessian, or wool, or synthetic fibres such as polyamide, polyester, polypropylene, polyacrylonitrile or the like. The polyesters are particularly suitable. The methods of textile treatment are known, e.g. WO 2008/151984, WO 2003/034823, US 5631072, WO 2005/64072, W02006/128870, EP 1724392, W02005113886 or WO 2007/090739.

Further areas of use of the compositions according to the invention are the field of tree injection/trunk treatment for all ornamental trees as well all sort of fruit and nut trees.

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

Table A. Examples of exotic woodborers of economic importance

Table B. Examples of native woodborers of economic importance.

The present invention may be also used to control any insect pests that may be present in turfgrass, including for example beetles, caterpillars, fire ants, ground pearls, millipedes, sow bugs, mites, mole crickets, scales, mealybugs ticks, spittlebugs, southern chinch bugs and white grubs. The present invention may be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults.

In particular, the present invention may be used to control insect pests that feed on the roots of turfgrass including white grubs (such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e g. European chafer, R. majalis), Cotinus spp. (e g. Green June beetle, C. nitida), Popillia spp. (e g. Japanese beetle, P. japonica), Phyllophaga spp. (e g. May/June beetle), Ataenius spp. (e.g. Black turfgrass ataenius, A. spretulus), Maladera spp. (e.g. Asiatic garden beetle, M.

castanea) and Tomarus spp.), ground pearls ( Margarodes spp.), mole crickets (tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula spp.).

The present invention may also be used to control insect pests of turfgrass that are thatch dwelling, including armyworms (such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta), cutworms, billbugs ( Sphenophorus spp., such as S. venatus verstitus and S. parvulus), and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis).

The present invention may also be used to control insect pests of turfgrass that live above the ground and feed on the turfgrass leaves, including chinch bugs (such as southern chinch bugs, Blissus insularis), Bermudagrass mite ( Eriophyes cynodoniensis), rhodesgrass mealybug ( Antonina graminis), two-lined spittlebug ( Propsapia bicincta), leafhoppers, cutworms ( Noctuidae family), and greenbugs. The present invention may also be used to control other pests of turfgrass such as red imported fire ants ( Solenopsis invicta) that create ant mounds in turf.

In the hygiene sector, the compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.

Examples of such parasites are:

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

Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp.,

Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp..

Of the order Diptera and the suborders Nematocerina and Brachycerina, for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., 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..

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

Of the order Heteropterida, for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.. Of the order Blattarida, for example Blatta orientalis, Periplaneta americana, Blattelagermanica and Supella spp..

Of the subclass Acaria (Acarida) and the orders Meta- and Meso-stigmata, 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., Sternostoma spp. and Varroa spp..

Of 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 invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.

The compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec.,Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus augur, and termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes,

Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and Coptotermes formosanus, and bristletails such as Lepisma saccharina.

The compounds according to the invention can be used as pesticidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances. The formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water- dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil- in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water- miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can either be used directly or diluted prior to use. The dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.

The formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.

The active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.

The formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p- diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, A/,A/-dimethylformamide, dimethyl sulfoxide, 1 ,4- dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alky Ipyrrolidone, 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, glycerol, 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, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, /V-methyl-2- pyrrolidone and the like.

Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapu Igite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.

A large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surface- active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyljsulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di- alkylphosphate esters; and also further substances described e.g. in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981 ).

Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.

The compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied. For example, the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. Preferred oil additives comprise alkyl esters of C -C fatty acids, especially the methyl derivatives of C -C fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010. The inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formula tion adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations.

The rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. As a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.

Preferred formulations can have the following compositions (weight %):

Emulsifiable concentrates:

active ingredient: 1 to 95 %, preferably 60 to 90 %

surface-active agent: 1 to 30 %, preferably 5 to 20 %

liquid carrier: 1 to 80 %, preferably 1 to 35 %

Dusts:

active ingredient: 0.1 to 10 %, preferably 0.1 to 5 %

solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %

Suspension concentrates:

active ingredient: 5 to 75 %, preferably 10 to 50 %

water: 94 to 24 %, preferably 88 to 30 %

surface-active agent: 1 to 40 %, preferably 2 to 30 %

Wettable powders:

active ingredient: 0.5 to 90 %, preferably 1 to 80 %

surface-active agent: 0.5 to 20 %, preferably 1 to 15 %

solid carrier: 5 to 95 %, preferably 15 to 90 %

Granules:

active ingredient: 0.1 to 30 %, preferably 0.1 to 15 %

solid carrier: 99.5 to 70 %, preferably 97 to 85 %

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

The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.

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

Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.

Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.

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

The finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

Suspension concentrate

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

Flowable concentrate for seed treatment

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

Slow Release Capsule Suspension

28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8: 1 ). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.

Formulation types include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo- emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

Preparatory Examples:

“Mp” means melting point in °C. Free radicals represent methyl groups. 1 H NMR measurements were recorded on a Brucker 400MHz spectrometer, chemical shifts are given in ppm relevant to a TMS standard. Spectra measured in deuterated solvents as indicated. Either one of the LCMS methods below was 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 (M+H) + or (M-H)-.

LCMS Methods:

Method 1 :

Spectra were recorded on a Mass Spectrometer from Waters (ZQ Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 350°C, Cone Gas Flow: 50 L/Hr, Desolvation Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment and diode-array detector. Solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3 , 1.8 pm, 30 x 2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A = water + 5% MeOH + 0.05 % HCOOH, B= Acetonitrile + 0.05 % HCOOH:

gradient: 0 min 0% B, 100%A; 1.2-1.5min 100% B; Flow (mL/min) 0.85.

Method 2:

Spectra were recorded on a Mass Spectrometer from Agilent Technologies (6410 Triple Quadrupole mass spectrometer) equipped with an equipped with an electrospray source (Polarity: positive or negative ions, MS2 Scan, Capillary: 4.00 kV, Fragmentor: 100 V, Desolvatation Temperature: 350°C, Gas Flow: 11 L/min, Nebulizer Gas: 45 psi, Mass range: 110 to 1000 Da) and a 1200 Series HPLC from Agilent: quaternary pump, heated column compartment and diode-array detector. Column: KINETEX EVO C18, 2.6 pm, 50 x 4.6 mm, Temp: 40 °C, DAD Wavelength range (nm): 210 to 400, Solvent Gradient: A = water + 5% Acetonitrile + 0.1 % HCOOH, B= Acetonitrile + 0.1 % HCOOH: gradient: 0 min 0% B, 100%A; 0.9-1.8 min 100% B; Flow (mL/min) 1.8.

Method 3:

Spectra were recorded on a Mass Spectrometer from Waters (SQD Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Full Scan, Capillary: 3.00 kV, Cone range: 41 V, Source Temperature: 150°C, Desolvation Temperature: 500°C, Cone Gas Flow: 50 L/Hr, Desolvation Gas Flow: 1000 L/Hr, Mass range: 110 to 800 Da) and a FI- Class UPLC from Waters: Binary pump, heated column compartment and diode-array detector.

Column: Waters UPLC HSS T3 C18, 1.8 pm, 30 x 2.1 mm, Temp: 40 °C, DAD Wavelength range (nm): 210 to 400, Solvent Gradient: A = water + 5% Acetonitrile + 0.1 % HCOOH, B= Acetonitrile + 0.1

% HCOOH: gradient: 0 min 10% B; 0.-0.2 min 10-50%B; 0.2-0.7 min 50-100% B; Flow (mL/min) 0.8.

Preparation of Examples of Compounds of Formula (P:

Example P4: Preparation of 6-ethylsulfonyl-N, 1 ,3-trimethyl-2-oxo-N-i5-(1 ,1 ,2,2,2-pentafluoroethyl)-

1.3.4-thiadiazol-2-yl1imidazo[4.5-b1pyridine-5-carboxamid e (compound P4)

Step 1 : Preparation of tert-butyl 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylate (intermediate ID

4-Dimethylaminopyridine (235 mg, 0.19 mmol, 0.10 equiv.) and di-tert-butyl dicarbonate (6.31 g, 28.6 mmol, 1.5 equiv.) were added to a solution of 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylic acid (CAS 1857366-13-2, prepared as described in WO2017084879) (5.00 g, 19.1 mmol) in acetonitrile (100 mL) with trimethylamine (4.03 mL, 28.6 mmol, 1.5 equiv.). The reaction mixture was heated at 50°C overnight. After cooling down to room temperature, the reaction mixture was diluted with water (80 mL) and the aqueous phase was extracted with ethyl acetate (3x 100mL). The combined organic phases were dried over sodium sulfate, filtered and concentrated. The crude oil obtained was purified by flash chromatography over silica gel (35% ethyl acetate in cyclohexane) to afford the desired compound as a yellow oil (2.12 g). 1 H NMR (400 MHz, CDCb) d ppm 1.39-1.45 (t, J=7.34 Hz, 3H), 1.65 (s, 9H), 2.92 (q, J=7.34 Hz, 2H), 7.75 (d, J=1.96 Hz, 1 H), 8.45 (d, J=1.96 Hz, 1 H).

Step 2: Preparation of tert-butyl 5-bromo-3-ethylsulfonyl-pyridine-2-carboxylate (intermediate 12)

3-Chloroperbenzoic acid (2.20 g, 9.70 mmol, 2.0 equiv.) was added in portions to a 0°C cooled solution of tert-butyl 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylate (intermediate 11 prepared as described above) (1.50 g, 4.70 mmol) in dichloromethane (27 mL). The reaction mixture was stirred at 0°C for 40 min, then at room temperature for 2 hours. After quenching with a saturated sodium thiosulfate solution (10 mL), and 1 N sodium hydroxide (10 mL), the aqueous phase was extracted with dichloromethane (3x 30 mL). The combined organic phases were dried over sodium sulfate, filtered and concentrated. The crude material was used in the next step without purification. 1 H NMR (400 MHz, CDCb) d ppm 1.35 (t, 3H), 1.65 (s, 9H), 3.53 (q, 2H), 8.45 (d, 1 H), 8.87 (d, 1 H).

Step 3: Preparation of tert-butyl 3-ethylsulfonyl-5-(methylamino)pyridine-2-carboxylate

(intermediate I31

A mixture of te rt-buty I 5-bromo-3-ethylsulfonyl-pyridine-2-carboxylate (intermediate I2 prepared as described above) (1.30 g, 3.70 mmol), methylamine (40% in water solution) (1.0 mL, 11.6 mmol, 3.14 equiv.) and copper powder (47 mg, 0.74 mmol, 0.2 equiv.) in tetrahydrofuran (4.0 mL) was heated at 100°C in a sealed tube for 8 hours. After cooling down to room temperature, the reaction mixture was quenched with water (10 mL), and the aqueous phase was extracted with ethyl acetate (3x 30 mL). The combined organic phases were dried over sodium sulfate, filtered and concentrated. The crude material was used directly without purification. LCMS (method 3): retention time 0.92 min, 299 (M-H) . 1 H NMR (400 MHz, CDCIs) d ppm 1.26 (t, J=7.15 Hz, 3H), 1.62 (s, 1 H), 2.94 (s, 3H), 3.59 (q, J=7.46 Hz, 2H), 7.39 (s, 1 H), 8.3 (br s, 1 H).

Step 3: Preparation of tert-butyl 6-bromo-3-ethylsulfonyl-5-(methylamino)pyridine-2-carboxylat e

(intermediate 14)

N-bromopyrrolidine-2,5-dione (652 mg, 3.66 mmol, 1.1 equiv.) was added to a solution of crude tert- butyl 3-ethylsulfonyl-5-(methylamino)pyridine-2-carboxylate (intermediate I3 prepared as described above) (1.0 g, 3.33 mmol) in anhydrous N,N-dimethylformamide (10 mL). After stirring for 2 hours at room temperature, the reaction mixture was diluted with water (30 mL), and the aqueous phase was extracted with ethyl acetate (2x 20 mL). The combined organic phases were dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was used directly without purification. LCMS (method 3): retention time 1.14 min, 377 (M-H) . 1 H NMR (400 MHz, CDCIs) d ppm 1.35 (t, 3H), 1.63 (s, 9H), 3.00 (m, 3H), 3.56 (m, 3H), 7.28 (s, 1 H).

Step 4: Preparation of tert-butyl 3-ethylsulfonyl-5.6-bis(methylamino)pyridine-2-carboxylate

(intermediate I5)

A mixture of tert-butyl 6-bromo-3-ethylsulfonyl-5-(methylamino)pyridine-2-carboxylat e (intermediate I4 prepared as described above) (1.00 g, 2.64 mmol) and methylamine (2M in tetrahydrofuran) (6.6 mL, 13.2 mmol, 5.0 equiv.) in tetrahydrofuran (8.0 mL) was heated at 100°C in a sealed tube for 7 hours. After cooling down to room temperature, the reaction mixture was quenched with water (10 mL), and the aqueous phase was extracted with ethyl acetate (3x 30 mL). The combined organic phases were washed with brine, dried over sodium sulfate, filtered and concentrated. The crude material was used directly without purification. LCMS (method 2): retention time 1.31 min, 330 (M+H) + . 1 H NMR (400 MHz, CDCb) d ppm 0.56-0.57 (m, 1 H), 0.98-0.99 (m, 1 H), 1.30-1.35 (m, 5H), 1.63 (s, 10H), 1.74-1.97 (m, 1 H), 2.86 (s, 3H), 3.04 (s, 3H), 3.40 (q, J=7.46 Hz, 2H), 4.76 (br s, 1 H), 7.06 (s, 1 H).

Step 5: Preparation of tert-butyl 6-ethylsulfonyl-1.3-dimethyl-2-oxo-imidazo[4,5-blpyridine-5- carboxylate (intermediate 16)

Triphosgene (4.90 g, 16.0 mmol, 1.20 equiv.) was added to a 0°C cooled solution of crude tert-butyl 3- ethylsulfonyl-5,6-bis(methylamino)pyridine-2-carboxylate (intermediate I5 prepared as described above) (4.50 g, 14.0 mmol) in anhydrous tetrahydrofuran (20 mL) with triethylamine (5.70 mL, 41 mmol, 3.00 equiv.). After stirring for 1 hour at 0°C and 2 hours at room temperature, the reaction was quenched with water and the aqueous phase was extracted with dichloromethane. The combined organic layer was washed with water, brine solution, dried with anhydrous sodium sulfate and concentrated under reduced pressure. The crude material was purified by flash chromatography using ethyl acetate/hexane (8:2) to get the desired product (3.40 g). 1 H NMR (400 MHz, CDCb) d ppm 1.33 (t, 3H), 1.66 (s, 9H), 3.51 (m, 5H), 3.56 (s, 3H), 7.68 (s, 1 H).

Step 6: Preparation of 6-ethylsulfonyl-1.3-dimethyl-2-oxo-imidazor4.5-b1pyridine-5- carboxylic acid

(intermediate 17)

Trifluoroacetic acid (5.39 mL, 5.00 equiv.) was added to a solution of tert-butyl 6-ethylsulfonyl-1 ,3- dimethyl-2-oxo-imidazo[4,5-b]pyridine-5-carboxylate (intermediate I6 prepared as described above) (4.00 g, 13.4 mmol) in dichloromethane (130 mL). After stirring at room temperature for 3 h, the reaction mixture was concentrated and the crude material was used directly without purification. LCMS (method 2): retention time 0.31 min, 330.0 (M+H) + . 1 H NMR (400 MHz, CDCIs) d ppm 1.19 (t, 3H), 3.38 (s, 3H), 3.44 (s, 3H), 3.50 (q, 2H), 7.92 (s, 1 H).

Step 7: Preparation of 6-ethylsulfonyl-N.1.3-trimethyl-2-oxo-N-[5-(1.1.2.2.2-pentaf luoroethyl)-1 ,3.4- thiadiazol-2-yl1imidazor4.5-b1pyridine-5-carboxamide (compound P4)

1-[Bis(dimethylamino)methylene]-1 H-1 ,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU, 230 mg, 0.75 mmol, 1.10 equiv.) and N-ethyl diisopropylamine (360 mI_, 2.07 mmol, 3.09 equiv.) were added to a solution of 6-ethylsulfonyl-1 ,3-dimethyl-2-oxo-imidazo[4,5-b]pyridine-5- carboxylic acid (intermediate I7 prepared as described above) (200 mg, 0.67 mmol), N-methyl-5- (1 ,1 ,2,2,2-pentafluoroethyl)-1 ,3,4-thiadiazol-2-amine (156 mg, 0.67 mmol, 1.00 equiv.) in N,N- dimethylformamide (4.00 mL). After stirring at room temperature for 2 hours, the reaction mixture was quenched with water and the aqueous phase was extracted with ethyl acetate (3x 20 mL). The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure. The crude was purified by flash chromatography over silica gel to afford 6-ethylsulfonyl-N, 1 ,3- trimethyl-2-oxo-N-[5-(1 , 1 ,2,2,2-pentafluoroethyl)-1 ,3,4-thiadiazol-2-yl]imidazo[4,5-b]pyridine-5- carboxamide (compound P4). LCMS (method 3): retention time 1.09 min, 515.37 (M+H) + . 1 H NMR (400 MHz, CDCb) d ppm 1.20 (t, 3H), 3.37 (q, 2H), 3.47 (s, 3H), 3.47 (s, 3H), 3.60 (s, 3H), 7.67 (s,

1 H).

Example P5: Preparation of 6-ethylsulfonyl-N.1.3-trimethyl-2-oxo-N-r5-i1.1.2.2.2-pentaf luoroethvh- 1 ,3.4-thiadiazol-2-yl1benzimidazole-5-carboxamide (compound P5)

Step 1 : Preparation of ethyl 4-chloro-2-ethylsulfanyl-5-nitro-benzoate (intermediate I8) Concentrated sulfuric acid (4.6 mL, 84.8 mmol, 3.00 equiv.) was added dropwise to a solution of 4- chloro-2-ethylsulfanyl-5-nitro-benzoic acid (10.0 g, 28.3 mmol, 1.00 equiv., prepared according to WO 2016091731 ) in ethanol (150 mL). The reaction mixture was heated to reflux and stirred overnight. After cooling down to room temperature, the reaction mixture was concentrated under reduced pressure, and the resiude was diluted with water. The aqueous phase was extracted three times with ethyl acetate, the combined organic phases were washed with saturated sodium bicarbonate solution, water, dried over sodium sulfate, filtered and concentrated. The crude material was pure enough to be engaged in the next step directly. LCMS (method 2): 290/292 (M+H) + ; retention time: 1.62 min.

Step 2: Preparation of ethyl 2-ethylsulfanyl-4-imethylamino)-5-nitro-benzoate (intermediate I91

A methylamine solution (2.0 M in tetrahydrofuran, 155 mL, 310 mmol, 3.00 equiv.) was carefully added to a solution of crude ethyl 4-chloro-2-ethylsulfanyl-5-nitro-benzoate (30.0 g, 104 mmol, intermediate I8 prepared as described above) in tetrahydrofuran (80 mL) under vigorous stirring. After stirring for 2 hours at room temperature, the reaction mixture was concentrated under reduced pressure. The residue was diluted in a mixture of dichloromethane (200 mL) and chloroform (100 mL). The organic phase was washed with water (500 mL), dried over sodium sulfate, filtered and concentrated. The crude material was pure enough to be engaged in the next step directly. LCMS (method 3): retention time: 1.12 min, 285 (M+H) + .

Step 3: Preparation of ethyl 5-amino-2-ethylsulfanyl-4-imethylamino)benzoate (intermediate 110) A solution of ethyl 2-ethylsulfanyl-4-(methylamino)-5-nitro-benzoate (2.75 g, 9.67 mmol, intermediate I9 prepared as described above) in methanol (35 mL) was evacuated and backfilled with nitrogen, before adding Pd/C 10% (300 mg, 0.28 mmol, 0.03 equiv.). The mixture was evacuated and backfilled with nitrogen again, then with hydrogen, and stirred under hydrogen pressure (with a balloon) for 4.5 hours at room temperature. After evacuation and purge with nitrogen, the resulting mixture was filtered through Celite, and the obtained filtrate was concentrated under reduced pressure. The crude material was purified by flash chromatography over silica gel, eluting with ethyl acetate in cyclohexane, to afford the desired material. LCMS (method 3): 255 (M+H) + ; retention time: 0.83 min.

Step 4: Preparation of ethyl 6-ethylsulfanyl-1-methyl-2-oxo-3H-benzimidazole-5-carboxylat e

(intermediate 11 1 )

A 20% wt solution of phosgene in toluene (1.37 mL, 1. 26 g, 2.66 mmol, 1.33 equiv.) was added dropwise to a 0°C cooled solution of ethyl 5-amino-2-ethylsulfanyl-4-(methylamino)benzoate (500 mg, 2.00 mmol, 1.00 equiv, intermediate 110 prepared as described above) and triethylamine (1. 64 mL,

11.8 mmol, 5.90 equiv.) in dichloromethane (75 mL). After stirring for 1 hour at 0°C, the reaction mixture was slowly quenched with water. The aqueous phase was extracted with dichloromethane, the combined organic phases were washed with water, brine, dried over sodium sulfate, filtered and concentrated. The crude material was purified by flash chromatography over silica gel, eluting with ethyl acetate in cyclohexane, to afford the desired compound as a white solid. LCMS (method 3): retention time: 0.85 min, 281 (M+H) + . Step 5: Preparation of ethyl 6-ethylsulfanyl-1.3-dimethyl-2-oxo-benzimidazole-5-carboxyla te (intermediate 112)

Cesium carbonate (349 mg, 1.07 mmol, 3.00 equiv.) followed by methyl iodide (44 mI_, 0.71 mmol, 2.00 equiv.) were added to a solution of ethyl 6-ethylsulfanyl-1 -methyl-2-oxo-3H-benzimidazole-5- carboxylate (100 mg, 0.355 mmol, intermediate 111 prepared as described above) in N,N- dimethylformamide (5.0 mL). After stirring for 3 hours at room temperature, the reaction mixture was poured into water, and the aqueous phase was extracted with ethyl acetate. The combined organic phases were washed with water, brine, dried over sodium sulfate, filtered and concentrated.

Purification of the crude material by flash chromatography over silica gel, eluting with ethyl acetate in cyclohexane, afforded the desired compound. LCMS (method 3): retention time: 0.91 min, 295 (M+H) + .

Step 6: Preparation of 6-ethylsulfanyl-1.3-dimethyl-2-oxo-benzimidazole-5-carboxyli c acid

(intermediate 113)

Sodium hydroxide (81 mg, 2.04 mmol, 6.00 equiv.) was added to a solution of ethyl 6-ethylsulfanyl- 1 ,3-dimethyl-2-oxo-benzimidazole-5-carboxylate (100 mg, 0.34 mmol, intermediate 112 prepared as described above) in tetrahydrofuran (10 mL) and water (1.0 mL). The reaction mixture was heated to reflux and stirred for 2 hours. After cooling down to room temperature, the reaction mixture was poured into a 2N hydrochloric acid solution, and the aqueous phase was extracted three times with ethyl acetate. The combined organic phases were washed with brine, dried over sodium sulfate, filtered and concentrated. The crude material was engaged in the next step directly. LCMS (method 3): retention time: 0.69 min, 267 (M+H) + .

Step 7: Preparation of 6-ethylsulfanyl-N.1.3-trimethyl-2-oxo-N-r5-i1.1.2.2.2-pentaf luoroethvh-1.3.4- thiadiazol-2-yl1benzimidazole-5-carboxamide (compound P6)

To a 0°C cooled solution of 6-ethylsulfanyl-1 ,3-dimethyl-2-oxo-benzimidazole-5-carboxylic acid (100 mg, 0.40 mmol, 1.00 equiv., intermediate 113 prepared as described above) in dichloromethane (2.0 mL) containing also one drop of N,N-dimethylformamide, was added oxalyl chloride (60 mI_, 0.70 mmol, 1.8 equiv) dropwise. After stirring for 2 hours at room temperature, the reaction mixture was concentrated under reduced pressure and the crude material used directly. A suspension of 6- ethylsulfanyl-1 ,3-dimethyl-2-oxo-benzimidazole-5-carbonyl chloride (obtained above) in

dichloromethane (2.0mL) was added slowly to a 0°C cooled and pre stirred solution of N-methyl-5- (1 ,1 ,2,2,2-pentafluoroethyl)-1 ,3,4-thiadiazol-2-amine (100 mg, 0.44 mmol, 1.10 equiv.), N,N- dimethylaminopyridine (5.0 mg, 0.04 mmol, 0.10 equiv.) and triethylamine (80 mI_, 0.60 mmol, 1.50 equiv.) in dichloromethane (5.0 mL). After stirring for 3 hours at room temperature, the reaction mixture was poured over water, and the aqueous phase was extracted with dichloromethane. The combined organic phases were dried over sodium sulfate, filtered and concentrated. The crude material was purified by flash chromatography over silica gel (30% ethyl acetate in cyclohexane) to afford the desired compound as white solid (120 mg). LCMS (method 2): retention time 1.18 min, 482 (M+H) + . 1 H NMR (400 MHz, CDCIs) d ppm 1.20-1.25 (t, 3H), 2.87 (q, J=7.30 Hz, 2H), 3.45 (s, 3H),

3.47-3.51 (s, 3H), 3.64 (s, 3H), 6.96(s, 1 H), 7.19 (s, 1 H). 19 F NMR (377 MHz, CDCIs) d ppm -107.79 (s, 1 F), -83.23 (s, 1 F).

Step 8: Preparation of 6-ethylsulfonyl-N.1.3-trimethyl-2-oxo-N-r5-i1.1.2.2.2-oentaf luoroethvh-1.3.4- thiadiazol-2-yl1benzimidazole-5-carboxamide (compound P51 3-Chloroperbenzoic acid 70% mass( 100 mg, 0.50 mmol, 2.20 equiv.) was added portionwise to a 0°C cooled solution of 6-ethylsulfanyl-N, 1 ,3-trimethyl-2-oxo-N-[5-(1 ,1 ,2,2,2-pentafluoroethyl)-1 ,3,4- thiadiazol-2-yl]benzimidazole-5-carboxamide (100 mg, 0.20 mmol, 1.00 equiv, compound P8 as prepared above) in dichloromethane (5.0 mL). After stirring for 2 hours at room temperature, the reaction mixture was quenched with a saturated sodium hydrogenocarbonate solution. The aqueous phase was extracted with dichloromethane, the combined organic phases were washed with water, brine, dried over sodium sulfate, filtered and concentrated. Purification of the crude material by flash chromatography over silica gel, eluting with ethyl acetate in cyclohexane afforded the desired compound (87 mg). LCMC (method 2): retention time 1.06 min, 514 (M+H) + . 1 H NMR (400 MHz,

CDC ) d ppm 1.31 -1.37 (t, 3H), 3.30-3.38 (q, 2H), 3.49-3.53 (s, 3H), 3.55 (s, 3H), 3.67 (s, 3H), 7.00 (s, 1 H), 7.66 (s, 1 H).

Example P1 and P7: 7-ethylsulfonyl-N-methyl-N-r5-(1.1.2.2.2-pentafluoroethvh-1. 3.4-thiadiazol-2-yll-

3-(trifluoromethyl)quinoxaline-6-carboxamide (compound P1 ) and 7-ethylsulfonyl-N-methyl-N-[5- (1 ,1.2.2.2-pentafluoroethyl)-1.3.4-thiadiazol-2-yll-2-(trifluo romethyl)quinoxaline-6-carboxamide

(compound P71

(P1 ) (P7)

Step 1 : Preparation of ethyl 4-(tert-butoxycarbonylamino)-2-ethylsulfanyl-5-nitro-benzoat e

(intermediate 114) Ethyl 4-chloro-2-ethylsulfanyl-5-nitro-benzoate (intermediate 18 prepared as described above) (5 g, 17.26 mmol, 1.0 equiv.) was dissolved in anhydrous 1 ,4-dioxane (100 mL), to it cesium carbonate (7.88 g, 24.16 mmol, 1.4 equiv.), tert-butyl carbamate (2.42 g, 20.71 mmol, 1.2 equiv.), 2-dicyclohexyl- phosphino-2',4',6'-triisopropylbiphenyl X-PHOS (0.75 g, 1 .553 mmol, 0.09 equiv.) were added under nitrogen. Reaction mixture was degassed with nitrogen for 25-30 mins. Palladium(l l) acetate (0.1 16 g, 0.5178 mmol, 0.03 equiv. ) . The reaction mixture was heated at 1 10°C for 5-6 hours. Solution became dark brown in colour. TLC checked and LCMS taken which showed the formation of desired product. Reaction mixture was filtered through celite bed and celite bed washed with ethyl acetate (100 mL). Organic layer was concentrated under reduced pressure to get crude product. Methanol (150 mL) was added to it and stirred for 30 min. Precipitated solid was washed with methanol (50 mL) dried under reduced pressure to afford pure ethyl 4-(tert-butoxycarbonylamino)-2-ethylsulfanyl-5-nitro-benzoat e (4.2 g). LCMS (method 3): retention time 1 .22 min, 270 (M+H) + . 1 H NMR (400 MHz, CDCIs) d ppm 1.39-1.51 (m, 6H), 1 .55-1 .58 (m, 9H), 3.06 (q, 2H), 4.40 (q, 2H), 8.66 (s, 1 H), 8.90 (s, 1 H), 10.04 (s, 1 H).

Step 2: Preparation of ethyl 4-amino-2-ethylsulfanyl-5-nitro-benzoate (intermediate 1151

To a solution of ethyl 4-(tert-butoxycarbonylamino)-2-ethylsulfanyl-5-nitro-benzoat e (intermediate I25 prepared as described above) (3.9 g, 1 1 mmol, 1.0 equiv. ) in dichloromethane (30 mL) was added 2,2,2-trifluoroacetic acid (8.1 mL, 1 10 mmol, 10 equiv. ) and the reaction mass was stirred at room temperature overnight, monitered by TLC. After completion of the reaction, the mixture was evaporated under reduced pressure and neutralised using aqueous sat. potassium carbonate solution (100 mL). The product was extracted with dichloromethane (3x 100 mL), the combined organic layers dried over sodium sulfate and concentrated to afford crude ethyl 4-amino-2-ethylsulfanyl-5-nitro- benzoate (2.8 g). LCMS (method 3): retention time 1 .06 min, 269 (M-H) . Step 3: Preparation of ethyl 4,5-diamino-2-ethylsulfanyl-benzoate (intermediate 116)

To a solution of ethyl 4-amino-2-ethylsulfanyl-5-nitro-benzoate (intermediate 126 prepared as described above) (2.8 g, 10 mmol, 1.0 equiv. ) in acetic acid (28 mL) at room temperature was added iron (4.6 g, 83 mmol, 8.0 equiv. ). The reaction mixture was stirred at room temperature overnight and the volatiles removed under reduced pressure. Methanol (50 mL) and dichloromethane (50 mL) were added to the residue and the mixture was filtered through celite, washing the collected solids thoroughly with dichloromethane. The combined filtrates were concentrated under reduced pressure. Water was added to the obtained residue and the product extracted with dichloromethane. The combined organic layers were washed with a sodium bicarbonate solution (50 mL), dried over sodium sulfate, and concentrate under reduced pressure. The crude compound was purified by combiflash (silica gel, 60% ethyl acetate in cyclohexane) to afford ethyl 4,5-diamino-2-ethylsulfanyl-benzoate (1.5 g). LCMS (method 3): retention time 0.74 min, 241 (M+H) + . 1 H NMR (400 MHz, DMSO-de) d ppm 1 .23 (br t, 3H), 1.27 (t, 3H), 2.77 (q, 2H), 4.16 (q, 2H), 4.58 (br s, 2H), 5.33 (s, 2H), 6.52 (s, 1 H), 7.16 (s, 1 H).

Step 4: Preparation of ethyl 7-ethylsulfanyl-2-itrifluoromethyl)auinoxaline-6-carboxylate (intermediate

117) and ethyl 7-ethylsulfanyl-3-(trifluoromethyl)quinoxaline-6-carboxylate (intermediate 118)

To a solution of ethyl 4,5-diamino-2-ethylsulfanyl-benzoate (intermediate I27 prepared as described above) (2.9 g, 12 mmol, 1.0 equiv.) in ethanol (40 mL) was added 3,3,3-trifluoro-2-oxo-propanal (3.0 g, 24 mmol, 2 equiv.). Reaction mass was heated at 60°C for 16 hours, monitored by TLC and LCMS. After completion of the reaction, the mixture was concentrated under reduced pressure, diluted with water (100mL) and the product extracted with ethyl acetate (3x 100 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The crude compound was purified by combiflash (silica gel, 30% EA in Cyclohexane) to afford ethyl 7-ethylsulfanyl-2-

(trifluoromethyl)quinoxaline-6-carboxylate and ethyl 7-ethylsulfanyl-3-(trifluoromethyl)quinoxaline-6- carboxylate as a mixture (3.4 g). Compound 117, LCMS (method 2): retention time 1.58 min, 331 (M+H) + . Compound 118, LCMS (method 2): retention time 1.58 min, 331 (M+H) + . Step 5: Preparation of ethyl 7-ethylsulfonyl-2-(trifluoromethyl)quinoxaline-6-carboxylate (intermediate 119) and ethyl 7-ethylsulfonyl-3-(trifluoromethyl)quinoxaline-6-carboxylate (intermediate I20)

To a solution of ethyl 7-ethylsulfanyl-2-(trifluoromethyl)quinoxaline-6-carboxylate (intermediate I28 and intermediate I29 prepared as described above) (3.0 g, 9.1 mmol) in dichloromethane (30 mL) was added 3-chlorobenzenecarboperoxoic acid (3.9 g, 2.5 mmol). The reaction mixture was stirred at room temperature for 6 hours, monitored by TLC. The reaction mass was quenched with a sodium carbonate solution (100 mL), the aqueous layer extracted with dichloromethane (3x 100 mL), the combined organic layers dried over sodium sulfate, filtered and concentrated under reduced pressure to afford ethyl 7-ethylsulfonyl-2-(trifluoromethyl)quinoxaline-6-carboxylate and ethyl 7-ethylsulfonyl-3- (trifluoromethyl)quinoxaline-6-carboxylate as mixture (3.4 g). Compound 119, LCMS (method 3): retention time 1.07 min, 363 (M+H) + . Compound I20, LCMS (method 3): retention time 1.07 min, 363 (M+H) + .

Step 6: Preparation of 7-ethylsulfonyl-3-(trifluoromethyl)quinoxaline-6-carboxylic acid (intermediate 121 )and 7-ethylsulfonyl-2-(trifluoromethyl)quinoxaline-6-carboxylic acid (intermediate 122)

To a solution of ethyl 7-ethylsulfonyl-2-(trifluoromethyl)quinoxaline-6-carboxylate (intermediate 130 and intermediate 131 prepared as described above) (3.4 g, 9.4 mmol, 1.0 equiv.) in tetrahydrofuran (51 mL) was added lithium hydroxide hydrate (0.79 g, 19 mmol, 2.0 equiv.) in water (14 mL). The reaction was stirred at room temperaturefor 2-4 hours, monitored by TLC and LCMS. The mixture was acidified with an aqueous 2N HCI solution (50 mL), the product extracted with ethyl acetate (3x 50 mL). The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure to afford 7-ethylsulfonyl-3-(trifluoromethyl)quinoxaline-6-carboxylic acid and 7-ethylsulfonyl-2- (trifluoromethyl)quinoxaline-6-carboxylic acid as a mixture (2.9 g). Compound 121 , LCMS (method 3): retention time 0.84 min, 335 (M+H) + . Compound 122, LCMS (method 3): retention time 0.84 min, 335 (M+H) + .

Step 7: Preparation of 7-ethylsulfonyl-N-methyl-N-r5-(1.1.2.2.2-pentafluoroethvh-1. 3.4-thiadiazol-2-yll-

3-(trifluoromethyl)quinoxaline-6-carboxamide (compound P1 ) and 7-ethylsulfonyl-N-methyl-N-[5- (1 ,1 ,2.2.2-pentafluoroethyl)-1.3.4-thiadiazol-2-yll-2-(trifluoro methyl)quinoxaline-6-carboxamide

(compound P7)

To a solution of N-methyl-5-(1 , 1 ,2,2,2-pentafluoroethyl)-1 ,3,4-thiadiazol-2-amine (300 mg, 1.28 mmol, 1.0 equiv.), 7-ethylsulfonyl-2-(trifluoromethyl)quinoxaline-6-carboxylic acid (intermediate I32 and intermediate I33 prepared as described above) (0.516 g, 1.54 mmol, 1.2 equiv.) and 1 -[bis(d imethyl- amino)methylene]-1 H-1 ,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU, 0.57678 g, 1.44 mmol, 1.12 equiv.) in N,N-dimethylformamide (6 mL) was added Hunig's base (0.695 mL, 3.9887 mmol, 3.1 equiv.) dropwise. The reaction mass was stirred at room temperature for 2 hours, monitored by TLC and LCMS. Purification by preparative-HPLC afforded 7-ethylsulfonyl-N-methyl-N-[5- (1 ,1 ,2,2,2-pentafluoroethyl)-1 ,3,4-thiadiazol-2-yl]-3-(trifluoromethyl)quinoxaline-6-carbo xamide (0.053 g) and 7-ethylsulfonyl-N-methyl-N-[5-(1 ,1 ,2,2,2-pentafluoroethyl)-1 ,3,4-thiadiazol-2-yl]-2- (trifluoromethyl)quinoxaline-6-carboxamide (0.12 g).

Compound P1 : LCMS (method 3): retention time 1.20 min, 550 (M+H) + . 1 H NMR (400 MHz, CDCIs) d ppm 1.43 (t, 3H), 3.50 (q, 2H), 3.78 (s, 3H), 8.38 (s, 1 H), 9.07 (s, 1 H), 9.46 (s, 1 H).

Compound P7: LCMS (method 3): retention time 1.20 min, 550 (M+H) + . 1 H NMR (400 MHz, CDCIs) d ppm 1.41 (t, J=7.53 Hz, 3H) 3.48 (q, 2H), 3.76 (s, 3H), 8.36 (s, 1 H), 9.07 (s, 1 H), 9.43 (s, 1 H).

Example P2: 6-ethylsulfonyl-N.1 -dimethyl-N-r5-(1.1.2.2.2-pentafluoroethvh-1.3.4-thiadiazol- 2-yl1-2- (trifluoromethvhbenzimidazole-5-carboxamide (compound P21

Step 1 : Preparation of 6-ethylsulfanyl-N.1 -dimethyl-N-[5-(1.1.2.2.2-pentafluoroethyl)-1.3,4-thiadiazol -2- yl1-2-itrifluoromethvhbenzimidazole-5-carboxamide (compound P31

To a solution of 6-ethylsulfanyl-1-methyl-2-(trifluoromethyl)benzimidazole-5- carboxylic acid (CAS NO 1943761-92-9, prepared as described in WO2017/174449) (0.783 g, 2.57 mmol, 1.2 equiv.), N-methyl-

5-(1 ,1 ,2,2,2-pentafluoroethyl)-1 ,3,4-thiadiazol-2-amine (0.50 g, 2.14 mmol, 1.0 equiv.) and HATU (1.03 g, 2.57 mmol, 1.2 equiv.) in N,N-dimethylformamide (10 mL) was added Hunig's base (1.16 mL, 6.64 mmol, 3.1 equiv.) dropwise. The reaction mass was stirred at room temperature for 16 hours, quenched with water, and the product extracted in ethyl acetate (3x 30 ml). Thecombined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. The crude compound was purified by combiflash (silica gel, 20% ethyl acetate-cyclohexane) to afford 6-ethy Isulfanyl-N, 1 - dimethyl-N-[5-(1 , 1 ,2,2,2-pentafluoroethyl)-1 ,3,4-thiadiazol-2-yl]-(trifluoromethyl)benzimidazole-5- carboxamide (0.7 g) as white solid. LCMS (method 3): retention time 1.25 min, 520 (M+H) + . 1 H NMR (400 MHz, CDC ) d ppm 1.29 (t, 3H), 2.97 (q, 2H), 3.62 (s, 3H), 4.02 (s, 3H), 7.65 (s, 1 H), 7.85 (s, 1 H).

Step 2: Preparation of 6-ethylsulfonyl-N.1 -dimethyl-N-r5-i1.1.2.2.2-pentafluoroethvh-1.3.4-thiadiazol- 2- yl1-2-(trifluoromethyl)benzimidazole-5-carboxamide (compound P2)

To a stirred solution of 6-ethylsulfanyl-N, 1 -dimethyl-N-[5-(1 , 1 ,2,2,2-pentafluoroethy l)-1 , 3,4-thiad iazol- 2-yl]-2-(trifluoromethyl)benzimidazole-5-carboxamide (compound P3 prepared as described above)

(300 mg, 0.57 mmol, 1.0 equiv.) in dichloromethane (6 mL) was added 3-chlorobenzenecarboperoxoic acid (0.299 mg, 1.213 mmol, 2.12 equiv.) at 0°C. Reaction mass was allowed to stirred at room temperature for 2 hours. The mixture was quenched with an aqueous 2M sodium hydroxide solution (10 mL), extracted with dichloromethane (3x 20 mL). The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by combiflash (silica gel, 50% ethyl acetate in cyclohexane) to afford 6-ethylsulfonyl-N,1 -dimethyl-N-[5- (1 ,1 ,2,2,2-pentafluoroethyl)-1 ,3,4-thiadiazol-2-yl]-2-(trifluoromethyl)benzimidazole-5-car boxamide (0.23 g) as a white solid. LCMS (method 3): retention time 1.16 min, 552 (M+H) + . 1 H NMR (400 MHz, CDC ) d ppm 1.33 (t, 3H), 3.45 (q, 2H), 3.66 (s, 3H), 4.14 (s, 3H), 7.96 (s, 1 H), 8.32 (s, 1 H).

Table P: Examples of compounds of formula (I)

The activity of the compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients. The mixtures of the compounds of formula I with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use.

Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.

The following mixtures of the compounds of formula I with active ingredients are preferred (the abbreviation“TX” means“one compound selected from the group consisting of the compounds described in Tables A-1 to A-6, Tables C-1 to C-6, Tables E-1 to E-4, Tables G-1 to G-24 and Table P of the present invention”): an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX,

an insect control active substance selected from Abamectin + TX, Acequinocyl + TX, Acetamiprid +

TX, Acetoprole + TX, Acrinathrin + TX, Acynonapyr + TX, Afidopyropen + TX, Afoxalaner + TX, Alanycarb + TX, Allethrin + TX, Alpha-Cypermethrin + TX, Alphamethrin + TX, Amidoflumet + TX, Aminocarb + TX, Azocyclotin + TX, Bensultap + TX, Benzoximate + TX, Benzpyrimoxan + TX, Betacyfluthrin + TX, Beta-cypermethrin + TX, Bifenazate + TX, Bifenthrin + TX, Binapacryl + TX, Bioallethrin + TX, Bioallethrin S)-cyclopentylisomer + TX, Bioresmethrin + TX, Bistrifluron + TX, Broflanilide + TX, Brofluthrinate + TX, Bromophos-ethyl + TX, Buprofezine + TX, Butocarboxim + TX, Cadusafos + TX, Carbaryl + TX, Carbosulfan + TX, Cartap + TX, CAS number: 1472050-04-6 + TX, CAS number: 1632218-00-8 + TX, CAS number: 1808115-49-2 + TX, CAS number: 2032403-97-5 + TX, CAS number: 2044701-44-0 + TX, CAS number: 2128706-05-6 + TX, CAS number: 2249718-27-0 + TX, Chlorantraniliprole + TX, Chlordane + TX, Chlorfenapyr + TX, Chloroprallethrin + TX,

Chromafenozide + TX, Clenpirin + TX, Cloethocarb + TX, Clothianidin + TX, 2-chlorophenyl N- methylcarbamate (CPMC) + TX, Cyanofenphos + TX, Cyantraniliprole + TX, Cyclaniliprole + TX, Cyclobutrifluram + TX, Cycloprothrin + TX, Cycloxaprid + TX, Cycloxaprid + TX, Cyenopyrafen + TX, Cyetpyrafen (or Etpyrafen) + TX, Cyflumetofen + TX, Cyfluthrin + TX, Cyhalodiamide + TX,

Cyhalothrin + TX, Cypermethrin + TX, Cyphenothrin + TX, Cyromazine + TX, Deltamethrin + TX, Diafenthiuron + TX, Dialifos + TX, Dibrom + TX, Dicloromezotiaz + TX, Diflovidazine + TX,

Diflubenzuron + TX, dimpropyridaz + TX, Dinactin + TX, Dinocap + TX, Dinotefuran + TX,

Dioxabenzofos + TX, Emamectin + TX, Empenthrin + TX, Epsilon - momfluorothrin + TX, Epsilon- metofluthrin + TX, Esfenvalerate + TX, Ethion + TX, Ethiprole + TX, Etofenprox + TX, Etoxazole + TX, Famphur + TX, Fenazaquin + TX, Fenfluthrin + TX, Fenitrothion + TX, Fenobucarb + TX, Fenothiocarb + TX, Fenoxycarb + TX, Fenpropathrin + TX, Fenpyroxymate + TX, Fensulfothion + TX, Fenthion +

TX, Fentinacetate + TX, Fenvalerate + TX, Fipronil + TX, Flometoquin + TX, Flonicamid + TX, Fluacrypyrim + TX, Fluazaindolizine + TX, Fluazuron + TX, Flubendiamide + TX, Flubenzimine + TX, Flucitrinate + TX, Flucycloxuron + TX, Flucythrinate + TX, Fluensulfone + TX, Flufenerim + TX, Flufenprox + TX, Flufiprole + TX, Fluhexafon + TX, Flumethrin + TX, Fluopyram + TX, Flupentiofenox + TX, Flupyradifurone + TX, Flupyrimin + TX, Fluralaner + TX, Fluvalinate + TX, Fluxametamide + TX, Fosthiazate + TX, Gamma-Cyhalothrin + TX, Gossyplure™ + TX, Guadipyr + TX, Halofenozide + TX, Halofenozide + TX, Halofenprox + TX, Heptafluthrin + TX, Hexythiazox + TX, Hydramethylnon + TX, Imicyafos + TX, Imidacloprid + TX, Imiprothrin + TX, Indoxacarb + TX, lodomethane + TX, Iprodione + TX, Isocycloseram + TX, Isothioate + TX, Ivermectin + TX, Kappa-bifenthrin + TX, Kappa-tefluthrin + TX, Lambda-Cyhalothrin + TX, Lepimectin + TX, Lufenuron + TX, Metaflumizone + TX, Metaldehyde + TX, Metam + TX, Methomyl + TX, Methoxyfenozide + TX, Metofluthrin + TX, Metolcarb + TX, Mexacarbate + TX, Milbemectin + TX, Momfluorothrin + TX, Niclosamide + TX, Nitenpyram + TX, Nithiazine + TX, Omethoate + TX, Oxamyl + TX, Oxazosufyl + TX, Parathion-ethyl + TX, Permethrin + TX, Phenothrin + TX, Phosphocarb + TX, Piperonylbutoxide + TX, Pirimicarb + TX, Pirimiphos-ethyl + TX, Polyhedrosis virus + TX, Prallethrin + TX, Profenofos + TX, Profenofos + TX, Profluthrin + TX, Propargite + TX, Propetamphos + TX, Propoxur + TX, Prothiophos + TX, Protrifenbute + TX, Pyflubumide + TX, Pymetrozine + TX, Pyraclofos + TX, Pyrafluprole + TX, Pyridaben + TX, Pyridalyl + TX, Pyrifluquinazon + TX, Pyrimidifen + TX, Pyrimostrobin + TX, Pyriprole + TX, Pyriproxyfen + TX, Resmethrin + TX, Sarolaner + TX, Selamectin + TX, Silafluofen + TX, Spinetoram + TX, Spinosad + TX, Spirodiclofen + TX, Spiromesifen + TX, Spiropidion + TX, Spirotetramat + TX, Sulfoxaflor + TX, Tebufenozide + TX, Tebufenpyrad + TX, Tebupirimiphos + TX, Tefluthrin + TX, Temephos + TX, Tetrachloraniliprole + TX, Tetradiphon + TX, Tetramethrin + TX, Tetramethylfluthrin + TX, Tetranactin + TX, Tetraniliprole + TX, Theta-cypermethrin + TX, Thiacloprid + TX, Thiamethoxam + TX,

Thiocyclam + TX, Thiodicarb + TX, Thiofanox + TX, Thiometon + TX, Thiosultap + TX, Tioxazafen + TX, Tolfenpyrad + TX, Toxaphene + TX, Tralomethrin + TX, Transfluthrin + TX, Triazamate + TX, Triazophos + TX, Trichlorfon + TX, Trichloronate + TX, Trichlorphon + TX, Triflumezopyrim + TX, Tyclopyrazoflor + TX, Zeta-Cypermethrin + TX, Extract of seaweed and fermentation product derived from melasse + TX, Extract of seaweed and fermentation product derived from melasse comprising urea + TX, amino acids + TX, potassium and molybdenum and EDTA-chelated manganese + TX, Extract of seaweed and fermented plant products + TX, Extract of seaweed and fermented plant products comprising phytohormones + TX, vitamins + TX, EDTA-chelated copper + TX, zinc + TX, and iron + TX, Azadirachtin + TX, Bacillus aizawai + TX, Bacillus chitinosporus AQ746 (NRRL Accession No B-21 618) + TX, Bacillus firmus + TX, Bacillus kurstaki + TX, Bacillus mycoides AQ726 (NRRL Accession No. B-21664) + TX, Bacillus pumilus (NRRL Accession No B-30087) + TX, Bacillus pumilus AQ717 (NRRL Accession No. B-21662) + TX, Bacillus sp. AQ178 (ATCC Accession No. 53522) + TX, Bacillus sp. AQ175 (ATCC Accession No. 55608) + TX, Bacillus sp. AQ177 (ATCC Accession No. 55609) + TX, Bacillus subtilis unspecified + TX, Bacillus subtilis AQ153 (ATCC Accession No. 55614) + TX, Bacillus subtilis AQ30002 (NRRL Accession No. B-50421 ) + TX, Bacillus subtilis AQ30004 (NRRL Accession No. B- 50455) + TX, Bacillus subtilis AQ713 (NRRL Accession No. B-21661 ) + TX, Bacillus subtilis AQ743 (NRRL Accession No. B-21665) + TX, Bacillus thuringiensis AQ52 (NRRL Accession No. B-21619) + TX, Bacillus thuringiensis BD#32 (NRRL Accession No B-21530) + TX, Bacillus thuringiensis subspec. kurstaki BMP 123 + TX, Beauveria bassiana + TX, D-limonene + TX, Granulovirus + TX, Harpin + TX, Helicoverpa armigera Nucleopolyhedrovirus + TX, Helicoverpa zea Nucleopolyhedrovirus + TX, Heliothis virescens Nucleopolyhedrovirus + TX, Heliothis punctigera Nucleopolyhedrovirus + TX, Metarhizium spp. + TX, Muscodor albus 620 (NRRL Accession No.

30547) + TX, Muscodor roseus A3-5 (NRRL Accession No. 30548) + TX, Neem tree based products + TX, Paecilomyces fumosoroseus + TX, Paecilomyces lilacinus + TX, Pasteuria nishizawae + TX, Pasteuria penetrans + TX, Pasteuria ramosa + TX, Pasteuria thornei + TX, Pasteuria usgae + TX, P- cymene + TX, Plutella xylostella Granulosis virus + TX, Plutella xylostella Nucleopolyhedrovirus + TX, Polyhedrosis virus + TX, pyrethrum + TX, QRD 420 (a terpenoid blend) + TX, QRD 452 (a terpenoid blend) + TX, QRD 460 (a terpenoid blend) + TX, Quillaja saponaria + TX, Rhodococcus globerulus AQ719 (NRRL Accession No B-21663) + TX, Spodoptera frugiperda Nucleopolyhedrovirus + TX, Streptomyces galbus (NRRL Accession No. 30232) + TX, Streptomyces sp. (NRRL Accession No. B- 30145) + TX, Terpenoid blend + TX, and Verticillium spp.,

an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347)

+ TX,

an anthelmintic selected from the group of substances consisting of abamectin (1 ) + TX, crufomate (1011 ) + TX, Cyclobutrifluram + 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,

an 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, a bactericide selected from the group of substances consisting of 1 -hydroxy-1 /-/-pyridine-2-thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodicin (1112) + TX, fenaminosulf (1 144) + TX, formaldehyde (404) +

TX, hydrargaphen (alternative name) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (61 1 ) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX, and thiomersal (alternative name) [CCN] + TX,

a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis (alternative name) (33) + TX, Aphidius colemani (alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide (scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51 ) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51 ) + TX,

Bacillus thuringiensis subsp. tenebrionis (scientific name) (51 ) + TX, Beauveria bassiana (alternative name) (53) + TX, Beauveria brongniartii (alternative name) (54) + TX, Chrysoperla carnea (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 var.

acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. lecontei NPV (alternative name) (575) + TX, Orius spp.

(alternative name) (596) + TX, Paecilomyces fumosoroseus (alternative name) (613) + TX, Phytoseiulus persimilis (alternative name) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741 ) + TX, Steinernema bibionis (alternative name) (742) + TX, Steinernema carpocapsae (alternative name) (742) + TX, Steinernema feltiae (alternative name) (742) + TX, Steinernema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinernema riobravis (alternative name) (742) + TX, Steinernema scapterisci (alternative name) (742) + TX, Steinernema spp. (alternative name) (742) + TX, Trichogramma spp. (alternative name) (826) + TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848) + TX,

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

a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate [CCN] + TX, morzid [CCN] + TX, penfluron (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine (alternative name) [CCN] and uredepa (alternative name) [CCN] + TX, an insect pheromone selected from the group of substances consisting of (£)-dec-5-en-1-yl acetate with (£)-dec-5-en-1-ol (lUPAC name) (222) + TX, (£)-tridec-4-en-1 -yl acetate (lUPAC name) (829) + TX, (£)-6-methylhept-2-en-4-ol (lUPAC name) (541 ) + TX, (£,Z)-tetradeca-4,10-dien-1 -yl acetate (lUPAC name) (779) + TX, (Z)-dodec-7-en-1-yl acetate (lUPAC name) (285) + TX, (Z)-hexadec-11 - enal (lUPAC name) (436) + TX, (Z)-hexadec-l 1-en-1-yl acetate (lUPAC name) (437) + TX, (Z)- hexadec-13-en-11 -yn-1 -y I acetate (lUPAC name) (438) + TX, (Z)-icos-13-en-10-one (lUPAC name) (448) + TX, (Z)-tetradec-7-en-1 -al (lUPAC name) (782) + TX, (Z)-tetradec-9-en-1-ol (lUPAC name) (783) + TX, (Z)-tetradec-9-en-1 -yl acetate (lUPAC name) (784) + TX, (7£,9Z)-dodeca-7,9-dien-1-yl acetate (lUPAC name) (283) + TX, (9Z, 11 £)-tetradeca-9, 11-dien-1 -yl acetate (lUPAC name) (780) + TX, (9Z, 12£)-tetradeca-9, 12-dien-1-yl acetate (lUPAC name) (781 ) + TX, 14-methyloctadec-1-ene (lUPAC name) (545) + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one (lUPAC name) (544) + TX, alpha-multistriatin (alternative name) [CCN] + TX, brevicomin (alternative name) [CCN] + TX, codlelure (alternative name) [CCN] + TX, codlemone (alternative name) (167) + TX, cuelure (alternative name) (179) + TX, disparlure (277) + TX, dodec-8-en-1-yl acetate (lUPAC name) (286)

+ TX, dodec-9-en-1-yl acetate (lUPAC name) (287) + TX, dodeca-8 + TX, 10-dien-1 -yl acetate (lUPAC name) (284) + TX, dominicalure (alternative name) [CCN] + TX, ethyl 4-methyloctanoate (lUPAC name) (317) + TX, eugenol (alternative name) [CCN] + TX, frontalin (alternative name) [CCN] + TX, gossyplure (alternative name) (420) + TX, grandlure (421 ) + TX, grandlure I (alternative name) (421 ) + TX, grandlure II (alternative name) (421 ) + TX, grandlure III (alternative name) (421 ) + TX, grandlure IV (alternative name) (421 ) + TX, hexalure [CCN] + TX, ipsdienol (alternative name) [CCN] + TX, ipsenol (alternative name) [CCN] + TX, japonilure (alternative name) (481 ) + TX, lineatin (alternative name) [CCN] + TX, litlure (alternative name) [CCN] + TX, looplure (alternative name) [CCN] + TX, medlure [CCN] + TX, megatomoic acid (alternative name) [CCN] + TX, methyl eugenol (alternative name) (540) + TX, muscalure (563) + TX, octadeca-2, 13-dien-1-yl acetate (lUPAC name) (588) + TX, octadeca-3,13-dien-1-yl acetate (lUPAC name) (589) + TX, orfralure (alternative name) [CCN] + TX, oryctalure (alternative name) (317) + TX, ostramone (alternative name) [CCN] + TX, siglure [CCN] + TX, sordidin (alternative name) (736) + TX, sulcatol (alternative name) [CCN] + TX, tetradec-1 1 -en-1 -yl acetate (lUPAC name) (785) + TX, trimedlure (839) + TX, trimedlure A (alternative name) (839) + TX, trimedlure Bi (alternative name) (839) + TX, trimedlure B (alternative name) (839) + TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN] + TX,

an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (lUPAC name) (591 ) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (lUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (lUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX, a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (lUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (lUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, trifenmorph (1454) + TX, trimethacarb (840) + TX, triphenyltin acetate (lUPAC name) (347) and triphenyltin hydroxide (lUPAC name) (347) + TX, pyriprole [394730-71-3] + TX,

a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, 1 ,2-dibromo-3-chloropropane (lUPAC/Chemical Abstracts name) (1045) + TX, 1 ,2-dichloropropane (lUPAC/ Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene (lUPAC name) (1063) + TX, 1 ,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1 ,1 - dioxide (lUPAC/Chemical Abstracts name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (lUPAC name) (980) + TX, 5-methyl-6-thioxo-1 ,3,5-thiadiazinan-3-ylacetic acid (lUPAC name) (1286)

+ TX, 6-isopentenylaminopurine (alternative name) (210) + TX, abamectin (1 ) + TX, acetoprole [CCN] + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, AZ 60541

(compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbosulfan (1 19) + TX, chloropicrin (141 ) + TX, chlorpyrifos (145) + TX, cloethocarb (999) + TX, Cyclobutrifluram + TX, cytokinins (alternative name) (210) + TX, dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafos (1044) + TX, dichlofenthion (1051 ) + TX, dicliphos (alternative name) + TX, dimethoate (262) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291 )

+ TX, emamectin benzoate (291 ) + TX, eprinomectin (alternative name) [CCN] + TX, ethoprophos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fenpyrad (alternative name) + TX, fensulfothion (1 158) + TX, fosthiazate (408) + TX, fosthietan (1196) + TX, furfural (alternative name) [CCN] + TX, GY-81 (development code) (423) + TX, heterophos [CCN] + TX, iodomethane (lUPAC name) (542) + TX, isamidofos (1230) + TX, isazofos (1231 ) + TX, ivermectin (alternative name) [CCN] + TX, kinetin (alternative name) (210) + TX, mecarphon (1258) + TX, metam (519) + TX, metam-potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, Myrothecium verrucaha composition (alternative name) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX,

phosphamidon (639) + TX, phosphocarb [CCN] + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachlorothiophene (lUPAC/ Chemical Abstracts name) (1422) + TX, thiafenox (alternative name) + TX, thionazin (1434) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, xylenols [CCN] + TX, YI-5302 (compound code) and zeatin (alternative name) (210) + TX, fluensulfone [318290-98-1 ] + TX, fluopyram + TX, a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,

a plant 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,

a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1 ,3-dione (lUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, alpha- chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891 ) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX,

bromadiolone (91 ) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) +

TX, chlorophacinone (140) + TX, cholecalciferol (alternative name) (850) + TX, coumachlor (1004) + TX, coumafuryl (1005) + TX, coumatetralyl (175) + TX, crimidine (1009) + TX, difenacoum (246) + TX, difethialone (249) + TX, diphacinone (273) + TX, ergocalciferol (301 ) + TX, flocoumafen (357) + TX, fluoroacetamide (379) + TX, flupropadine (1183) + TX, flupropadine hydrochloride (1183) + TX, gamma-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444) + TX, iodomethane (lUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (lUPAC name) (640) + TX, methyl bromide (537) + TX, norbormide (1318) + TX, phosacetim (1336) + TX, phosphine (lUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341 ) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371 ) + TX, scilliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851 ) and zinc phosphide (640) + TX,

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

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

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

a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX, a biologically active substance selected from 1 ,1 -bis(4-chlorophenyl)-2-ethoxyethanol + TX, 2,4- dichlorophenyl benzenesulfonate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 4- chlorophenyl phenyl sulfone + TX, acetoprole + TX, aldoxycarb + TX, amidithion + TX, amidothioate + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, aramite + TX, arsenous oxide + TX, azobenzene + TX, azothoate + TX, benomyl + TX, benoxafos + TX, benzyl benzoate + TX, bixafen + TX, brofenvalerate + TX, bromocyclen + TX, bromophos + TX, bromopropylate + TX, buprofezin + TX, butocarboxim + TX, butoxycarboxim + TX, butylpyridaben + TX, calcium polysulfide + TX, camphechlor + TX, carbanolate + TX, carbophenothion + TX, cymiazole + TX, chinomethionat + TX, chlorbenside + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorfenethol + TX, chlorfenson + TX, chlorfensulfide + TX, chlorobenzilate + TX, chloromebuform + TX, chloromethiuron + TX, chloropropylate + TX, chlorthiophos + TX, cinerin I + TX, cinerin II + TX, cinerins + TX, closantel + TX, coumaphos + TX, crotamiton + TX, crotoxyphos + TX, cufraneb + TX, cyanthoate + TX, DCPM + TX, DDT + TX, demephion + TX, demephion-O + TX, demephion-S + TX, demeton-methyl + TX, demeton-O + TX, demeton-O-methyl + TX, demeton-S + TX, demeton-S-methyl + TX, demeton-S- methylsulfon + TX, dichlofluanid + TX, dichlorvos + TX, dicliphos + TX, dienochlor + TX, dimefox + TX, dinex + TX, dinex-diclexine + TX, dinocap-4 + TX, dinocap-6 + TX, dinocton + TX, dinopenton + TX, dinosulfon + TX, dinoterbon + TX, dioxathion + TX, diphenyl sulfone + TX, disulfiram + TX, DNOC + TX, dofenapyn + TX, doramectin + TX, endothion + TX, eprinomectin + TX, ethoate-methyl + TX, etrimfos + TX, fenazaflor + TX, fenbutatin oxide + TX, fenothiocarb + TX, fenpyrad + TX, fen- pyroximate + TX, fenpyrazamine + TX, fenson + TX, fentrifanil + TX, flubenzimine + TX, flucycloxuron + TX, fluenetil + TX, fluorbenside + TX, FMC 1 137 + TX, formetanate + TX, formetanate hydrochloride + TX, formparanate + TX, gamma-HCH + TX, glyodin + TX, halfenprox + TX, hexadecyl

cyclopropanecarboxylate + TX, isocarbophos + TX, jasmolin I + TX, jasmolin II + TX, jodfenphos + TX, lindane + TX, malonoben + TX, mecarbam + TX, mephosfolan + TX, mesulfen + TX, methacrifos +

TX, methyl bromide + TX, metolcarb + TX, mexacarbate + TX, milbemycin oxime + TX, mipafox + TX, monocrotophos + TX, morphothion + TX, moxidectin + TX, naled + TX, 4-chloro-2-(2-chloro-2-methyl- propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, nifluridide + TX, nikkomycins + TX, nitrilacarb + TX, nitrilacarb 1 : 1 zinc chloride complex + TX, omethoate + TX, oxydeprofos + TX, oxydisulfoton + TX, pp'-DDT + TX, parathion + TX, permethrin + TX, phenkapton + TX, phosalone + TX, phosfolan + TX, phosphamidon + TX, polychloroterpenes + TX, polynactins + TX, proclonol + TX, promacyl + TX, propoxur + TX, prothidathion + TX, prothoate + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrins + TX, pyridaphenthion + TX, pyrimitate + TX, quinalphos + TX, quintiofos + TX, R-1492 + TX, phosglycin + TX, rotenone + TX, schradan + TX, sebufos + TX, selamectin + TX, sophamide + TX, SSI-121 + TX, sulfiram + TX, sulfluramid + TX, sulfotep + TX, sulfur + TX, diflovidazin + TX, tau- fluvalinate + TX, TEPP + TX, terbam + TX, tetradifon + TX, tetrasul + TX, thiafenox + TX, thiocarboxime + TX, thiofanox + TX, thiometon + TX, thioquinox + TX, thuringiensin + TX, triamiphos + TX, triarathene + TX, triazophos + TX, triazuron + TX, trifenofos + TX, trinactin + TX, vamidothion +

TX, vaniliprole + TX, bethoxazin + TX, copper dioctanoate + TX, copper sulfate + TX, cybutryne + TX, dichlone + TX, dichlorophen + TX, endothal + TX, fentin + TX, hydrated lime + TX, nabam + TX, quinoclamine + TX, quinonamid + TX, simazine + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, crufomate + TX, piperazine + TX, thiophanate + TX, chloralose + TX, fenthion + TX, pyridine- amine + TX, strychnine + TX, 1 -hydroxy-1 H-pyridine-2-thione + TX, 4-(quinoxalin-2- ylamino)benzenesulfonamide + TX, 8-hydroxyquinoline sulfate + TX, bronopol + TX, copper hydroxide + TX, cresol + TX, dipyrithione + TX, dodicin + TX, fenaminosulf + TX, formaldehyde + TX, hydrargaphen + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel bis(dimethyldithiocarbamate) + TX, nitrapyrin + TX, octhilinone + TX, oxolinic acid + TX,

oxytetracycline + TX, potassium hydroxyquinoline sulfate + TX, probenazole + TX, streptomycin + TX, streptomycin sesquisulfate + TX, tecloftalam + TX, thiomersal + TX, Adoxophyes orana GV + TX, Agrobacterium radiobacter + TX, Amblyseius spp. + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, Autographa californica NPV + TX, Bacillus sphaericus Neide + TX, Beauveria brongn iartii + TX, Chrysoperla carnea + TX, Cryptolaemus montrouzieri + TX, Cydia pomonella GV + TX, Dacnusa sibirica + TX, Diglyphus isaea + TX, Encarsia formosa + TX, Eretmocerus eremicus + TX,

Heterorhabditis bacteriophora and H. megidis + TX, Hippodamia convergens + TX, Leptomastix dactylopii + TX, Macrolophus caliginosus + TX, Mamestra brassicae NPV + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acrihdum + TX, Metarhizium anisopliae var. anisopliae + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, Orius spp. + TX, Paecilomyces fumosoroseus +

TX, Phytoseiulus persimilis + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Trichogramma spp. + TX, Typhlodromus occidentalis + TX , Verticillium lecanii + TX, apholate + TX, bisazir + TX, busulfan + TX, dimatif + TX, hemel + TX, hempa + TX, metepa + TX, methiotepa + TX, methyl apholate + TX, morzid + TX, penfluron + TX, tepa + TX, thiohempa + TX, thiotepa + TX, tretamine + TX, uredepa + TX, (E)- dec-5-en-1-yl acetate with (E)-dec-5-en-1 -ol + TX, (E)-tridec-4-en-1-yl acetate + TX, (E)-6-methylhept- 2-en-4-ol + TX, (E,Z)-tetradeca-4, 10-dien-1 -yl acetate + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)- hexadec-11-enal + TX, (Z)-hexadec-l 1 -en-1 -yl acetate + TX, (Z)-hexadec-13-en-1 1 -yn-1 -yl acetate + TX, (Z)-icos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec- 9-en-1-yl acetate + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX, (9Z, 11 E)-tetradeca-9,1 1-dien-1-yl acetate + TX, (9Z,12E)-tetradeca-9, 12-dien-1-yl acetate + TX, 14-methyloctadec-1-ene + TX, 4- methylnonan-5-ol with 4-methylnonan-5-one + TX, alpha-multistriatin + TX, brevicomin + TX, codlelure + TX, codlemone + TX, cuelure + TX, disparlure + TX, dodec-8-en-1-yl acetate + TX, dodec-9-en-1-yl acetate + TX, dodeca-8 + TX, 10-dien-1 -yl acetate + TX, dominicalure + TX, ethyl 4-methyloctanoate + TX, eugenol + TX, frontalin + TX, grandlure + TX, grandlure I + TX, grandlure II + TX, grandlure III + TX, grandlure IV + TX, hexalure + TX, ipsdienol + TX, ipsenol + TX, japonilure + TX, lineatin + TX, litlure + TX, looplure + TX, medlure + TX, megatomoic acid + TX, methyl eugenol + TX, muscalure + TX, octadeca-2, 13-dien-1-yl acetate + TX, octadeca-3, 13-dien-1-yl acetate + TX, orfralure + TX, oryctalure + TX, ostramone + TX, siglure + TX, sordidin + TX, sulcatol + TX, tetradec-11 -en-1 -yl acetate + TX, trimedlure + TX, trimedlure A + TX, trimedlure Bi + TX, trimedlure B + TX, trimedlure C + TX, trunc-call + TX, 2-(octylthio)ethanol + TX, butopyronoxyl + TX, butoxy(polypropylene glycol) + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, diethyltoluamide + TX, dimethyl carbate + TX, dimethyl phthalate + TX, ethyl hexanediol + TX, hexamide + TX, methoquin- butyl + TX, methylneodecanamide + TX, oxamate + TX, picaridin + TX, 1-dichloro-1-nitroethane + TX, 1 ,1 -dichloro-2,2-bis(4-ethylphenyl)ethane + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene + TX, 1 - bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2-(1 ,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-(2- butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1 ,3-dioxolan-2-yl)phenyl methylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidone + TX, 2- isovalerylindan-1 ,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate + TX, 2- thiocyanatoethyl laurate + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate + TX, 5,5-dimethyl-3- oxocyclohex-1-enyl dimethylcarbamate + TX, acethion + TX, acrylonitrile + TX, aldrin + TX, allosamidin + TX, allyxycarb + TX, alpha-ecdysone + TX, aluminium phosphide + TX, aminocarb + TX, anabasine + TX, athidathion + TX, azamethiphos + TX, Bacillus thuringiensis delta endotoxins + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, barthrin + TX, Bayer 22/190 + TX, Bayer 22408 + TX, beta-cyfluthrin + TX, beta-cypermethrin + TX, bioethanomethrin + TX, biopermethrin +

TX, bis(2-chloroethyl) ether + TX, borax + TX, bromfenvinfos + TX, bromo-DDT + TX, bufencarb + TX, butacarb + TX, butathiofos + TX, butonate + TX, calcium arsenate + TX, calcium cyanide + TX, carbon disulfide + TX, carbon tetrachloride + TX, cartap hydrochloride + TX, cevadine + TX, chlorbicyclen + TX, chlordane + TX, chlordecone + TX, chloroform + TX, chloropicrin + TX, chlorphoxim + TX, chlorprazophos + TX, cis-resmethrin + TX, cismethrin + TX, clocythrin + TX, copper acetoarsenite + TX, copper arsenate + TX, copper oleate + TX, coumithoate + TX, cryolite + TX, CS 708 + TX, cyanofenphos + TX, cyanophos + TX, cyclethrin + TX, cythioate + TX, d-tetramethrin + TX, DAEP + TX, dazomet + TX, decarbofuran + TX, diamidafos + TX, dicapthon + TX, dichlofenthion + TX, dicresyl + TX, dicyclanil + TX, dieldrin + TX, diethyl 5-methylpyrazol-3-yl phosphate + TX, dilor + TX, dimefluthrin + TX, dimetan + TX, dimethrin + TX, dimethylvinphos + TX, dimetilan + TX, dinoprop +

TX, dinosam + TX, dinoseb + TX, diofenolan + TX, dioxabenzofos + TX, dithicrofos + TX, DSP + TX, ecdysterone + TX, El 1642 + TX, EMPC + TX, EPBP + TX, etaphos + TX, ethiofencarb + TX, ethyl formate + TX, ethylene dibromide + TX, ethylene dichloride + TX, ethylene oxide + TX, EXD + TX, fenchlorphos + TX, fenethacarb + TX, fenitrothion + TX, fenoxacrim + TX, fenpirithrin + TX, fensulfothion + TX, fenthion-ethyl + TX, flucofuron + TX, fosmethilan + TX, fospirate + TX, fosthietan + TX, furathiocarb + TX, furethrin + TX, guazatine + TX, guazatine acetates + TX, sodium

tetrathiocarbonate + TX, halfenprox + TX, HCH + TX, HEOD + TX, heptachlor + TX, heterophos + TX, HHDN + TX, hydrogen cyanide + TX, hyquincarb + TX, IPSP + TX, isazofos + TX, isobenzan + TX, isodrin + TX, isofenphos + TX, isolane + TX, isoprothiolane + TX, isoxathion + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, kelevan + TX, kinoprene + TX, lead arsenate + TX, leptophos + TX, lirimfos + TX, lythidathion + TX, m-cumenyl methylcarbamate + TX, magnesium phosphide + TX, mazidox + TX, mecarphon + TX, menazon + TX, mercurous chloride + TX, mesulfenfos + TX, metam + TX, metam-potassium + TX, metam-sodium + TX, methanesulfonyl fluoride + TX, methocrotophos + TX, methoprene + TX, methothrin + TX, methoxychlor + TX, methyl isothiocyanate + TX, methylchloroform + TX, methylene chloride + TX, metoxadiazone + TX, mirex + TX, naftalofos + TX, naphthalene + TX, NC-170 + TX, nicotine + TX, nicotine sulfate + TX, nithiazine + TX, nornicotine + TX, 0-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate + TX, O,O-diethyl O- 4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate + TX, O,O-diethyl 0-6-methyl-2-propylpyrimidin-4- yl phosphorothioate + TX, O,O,O',O'-tetrapropyl dithiopyrophosphate + TX, oleic acid + TX, para- dichlorobenzene + TX, parathion-methyl + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH 60-38 + TX, phenkapton + TX, phosnichlor + TX, phosphine + TX, phoxim-methyl + TX, pirimetaphos + TX, polychlorodicyclopentadiene isomers + TX, potassium arsenite + TX, potassium thiocyanate + TX, precocene I + TX, precocene II + TX, precocene III + TX, primidophos + TX, profluthrin + TX, promecarb + TX, prothiofos + TX, pyrazophos + TX, pyresmethrin + TX, quassia +

TX, quinalphos-methyl + TX, quinothion + TX, rafoxanide + TX, resmethrin + TX, rotenone + TX, kadethrin + TX, ryania + TX, ryanodine + TX, sabadilla) + TX, schradan + TX, sebufos + TX, SI-0009 + TX, thiapronil + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium hexafluorosilicate + TX, sodium pentachlorophenoxide + TX, sodium selenate + TX, sodium thiocyanate + TX, sulcofuron + TX, sulcofuron-sodium + TX, sulfuryl fluoride + TX, sulprofos + TX, tar oils + TX, tazimcarb + TX, TDE + TX, tebupirimfos + TX, temephos + TX, terallethrin + TX, tetrachloroethane + TX, thicrofos + TX, thiocyclam + TX, thiocyclam hydrogen oxalate + TX, thionazin + TX, thiosultap + TX, thiosultap-sodium + TX, tralomethrin + TX, transpermethrin + TX, triazamate + TX, trichlormetaphos-3 + TX, trichloronat + TX, trimethacarb + TX, tolprocarb + TX, triclopyricarb + TX, triprene + TX, veratridine + TX, veratrine + TX, XMC + TX, zetamethrin + TX, zinc phosphide + TX, zolaprofos + TX, and meperfluthrin + TX, tetramethylfluthrin + TX, bis(tributyltin) oxide + TX, bromoacetamide + TX, ferric phosphate + TX, niclosamide-olamine + TX, tributyltin oxide + TX, pyrimorph + TX, trifenmorph + TX, 1 ,2-dibromo-3-chloropropane + TX, 1 ,3-dichloropropene + TX, 3,4- dichlorotetrahydrothiophene 1 , 1-dioxide + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6- thioxo-1 ,3,5-thiadiazinan-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, benclothiaz + TX, cytokinins + TX, DCIP + TX, furfural + TX, isamidofos + TX, kinetin + TX, Myrothecium verrucaria composition + TX, tetrachlorothiophene + TX, xylenols + TX, zeatin + TX, potassium ethylxanthate + TX .acibenzolar + TX, acibenzolar-S-methyl + TX, Reynoutria sachalinensis extract + TX, alpha- chlorohydrin + TX, antu + TX, barium carbonate + TX, bisthiosemi + TX, brodifacoum + TX, bromadiolone + TX, bromethalin + TX, chlorophacinone + TX, cholecalciferol + TX, coumachlor + TX, coumafuryl + TX, coumatetralyl + TX, crimidine + TX, difenacoum + TX, difethialone + TX, diphacinone + TX, ergocalciferol + TX, flocoumafen + TX, fluoroacetamide + TX, flupropadine + TX, flupropadine hydrochloride + TX, norbormide + TX, phosacetim + TX, phosphorus + TX, pindone + TX, pyrinuron + TX, scilliroside + TX, sodium fluoroacetate + TX, thallium sulfate + TX, warfarin + TX, 2-(2- butoxyethoxy)ethyl piperonylate + TX, 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, farnesol with nerolidol + TX, verbutin + TX, MGK 264 + TX, piperonyl butoxide + TX, piprotal + TX, propyl isomer + TX, S421 + TX, sesamex + TX, sesasmolin + TX, sulfoxide + TX, anthraquinone + TX, copper naphthenate + TX, copper oxychloride + TX, dicyclopentadiene + TX, thiram + TX, zinc naphthenate + TX, ziram + TX, imanin + TX, ribavirin + TX, mercuric oxide + TX, thiophanate-methyl + TX, azaconazole + TX, bitertanol + TX, bromuconazole + TX, cyproconazole + TX, difenoconazole + TX, diniconazole + TX, epoxiconazole + TX, fenbuconazole + TX, fluquinconazole + TX, flusilazole + TX, flutriafol + TX, furametpyr + TX, hexaconazole + TX, imazalil + TX, imibenconazole + TX, ipconazole + TX, metconazole + TX, myclobutanil + TX, paclobutrazole + TX, pefurazoate + TX, penconazole + TX, prothioconazole + TX, pyrifenox + TX, prochloraz + TX, propiconazole + TX, pyrisoxazole + TX, simeconazole + TX, tebuconazole + TX, tetraconazole + TX, triadimefon + TX, triadimenol + TX, triflumizole + TX, triticonazole + TX, ancymidol + TX, fenarimol + TX, nuarimol + TX, bupirimate + TX, dimethirimol + TX, ethirimol + TX, dodemorph + TX, fenpropidine + TX, fenpropimorph + TX, spiroxamine + TX, tridemorph + TX, cyprodinil + TX, mepanipyrim + TX, pyrimethanil + TX, fenpiclonil + TX, fludioxonil + TX, benalaxyl + TX, furalaxyl + TX, metalaxyl + TX, R-metalaxyl + TX, ofurace + TX, oxadixyl + TX, carbendazim + TX, debacarb + TX, fuberidazole + TX, thiabendazole + TX, chlozolinate + TX, dichlozoline + TX, myclozoline + TX, procymidone + TX, vinclozoline + TX, boscalid + TX, carboxin + TX, fenfuram + TX, flutolanil + TX, mepronil + TX, oxycarboxin + TX, penthiopyrad + TX, thifluzamide + TX, dodine + TX, iminoctadine + TX, azoxystrobin + TX, dimoxystrobin + TX, enestroburin + TX, fenaminstrobin + TX, flufenoxystrobin +

TX, fluoxastrobin + TX, kresoxim-methyl + TX, metominostrobin + TX, trifloxystrobin + TX, orysastrobin + TX, picoxystrobin + TX, pyraclostrobin + TX, pyrametostrobin + TX, pyraoxystrobin +

TX, ferbam + TX, mancozeb + TX, maneb + TX, metiram + TX, propineb + TX, zineb + TX, captafol + TX, captan + TX, fluoroimide + TX, folpet + TX, tolylfluanid + TX, bordeaux mixture + TX, copper oxide + TX, mancopper + TX, oxine-copper + TX, nitrothal-isopropyl + TX, edifenphos + TX, iprobenphos + TX, phosdiphen + TX, tolclofos-methyl + TX, anilazine + TX, benthiavalicarb + TX, blasticidin-S + TX, chloroneb + TX, chlorothalonil + TX, cyflufenamid + TX, cymoxanil + TX, diclocymet + TX, diclomezine + TX, dicloran + TX, diethofencarb + TX, dimethomorph + TX, flumorph + TX, dithianon + TX, ethaboxam + TX, etridiazole + TX, famoxadone + TX, fenamidone + TX, fenoxanil + TX, ferimzone + TX, fluazinam + TX, fluopicolide + TX, flusulfamide + TX, fluxapyroxad + TX, fenhexamid + TX, fos- etyl-aluminium + TX, hymexazol + TX, iprovalicarb + TX, cyazofamid + TX, methasulfocarb + TX, metrafenone + TX, pencycuron + TX, phthalide + TX, polyoxins + TX, propamocarb + TX, pyribencarb + TX, proquinazid + TX, pyroquilon + TX, pyriofenone + TX, quinoxyfen + TX, quintozene + TX, tiadinil + TX, triazoxide + TX, tricyclazole + TX, triforine + TX, validamycin + TX, valifenalate + TX, zoxamide + TX, mandipropamid + TX, isopyrazam + TX, sedaxane + TX, benzovindiflupyr + TX, pydiflumetofen + TX, 3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, isoflucypram + TX, isotianil + TX, dipymetitrone + TX, 6-ethyl-5,7-dioxo- pyrrolo[4,5][1 ,4]dithiino[1 ,2-c]isothiazole-3-carbonitrile + TX, 2-(difluoromethy l)-N-[3-ethy 1-1 , 1 -dimethyl- indan-4-yl]pyridine-3-carboxamide + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3- carbonitrile + TX, (R)-3-(difluoromethyl)-1-methyl-N-[1 ,1 ,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5 -dimethyl-pyrazol-3-amine + TX, 4- (2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1 , 3-dimethyl-1 H-pyrazol-5-amine + TX, + TX, coumethoxystrobin (jiaxiangjunzhi) + TX, Ivbenmixianan + TX, dichlobentiazox + TX, mandestrobin + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1 -yl)quinolone + TX, 2-[2-fl uoro-6-[( 8-flu oro-2- methyl-3-quinolyl)oxy]phenyl]propan-2-ol + TX, oxathiapiprolin + TX, tert-butyl N-[6-[[[(1 - methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyr idyl]carbamate + TX, pyraziflumid + TX, inpyrfluxam + TX, trolprocarb + TX, mefentrifluconazole + TX, ipfentrifluconazole+ TX, 2- (difluoromethyl)-N-[(3R)-3-ethyl-1 , 1 -dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, N'-(2,5- dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N'-[4-(4,5-dichlorothiazol-2-yl)oxy- 2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + TX, [2-[3-[2-[1 -[2-[3,5-bis(difluoromethyl)pyrazol-

1 -yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5- yl]-3-chloro-phenyl] methanesulfonate + TX, but-3-ynyl N-[6-[[(Z)-[(1 -methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-py ridyl]carbamate + TX, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]m ethyl]carbamate + TX, 3-chloro- 6- ethyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, pyridachlometyl + TX, 3-(difluoromethyl)-1 - methyl-N-[1 , 1 ,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3- yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one + TX, 1 -methyl-4-[3-methyl-2-[[2-methyl-4- (3,4,5-trimethylpyrazol-1 -yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX, a inopyrifen + TX, ametoctradin + TX, amisulbrom + TX, penflufen + TX, (Z,2E)-5-[1 -(4-chlorophenyl)pyrazol-3-yl]oxy-2- methoxyimino-N,3-dimethyl-pent-3-enamide + TX, florylpicoxa id + TX, fenpicoxamid + TX, tebufloquin + TX, ipflufenoquin + TX, quinofumelin + TX, isofetamid + TX, N-[2-[2,4-dichloro- phenoxy]phenyl]-3-(difluoromethyl)-1 -methyl-pyrazole-4-carboxamide + TX, N-[2-[2-chloro-4- (trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1 -methyl-pyrazole-4-carboxamide + TX, benzothiostrobin + TX, phenamacril + TX, 5-amino-1 ,3,4-thiadiazole-2-thiol zinc salt (2: 1 ) + TX, fluopyram + TX, flutianil + TX, fluopimomide + TX, pyrapropoyne + TX, picarbutrazox + TX, 2- (difluoromethyl)-N-(3-ethyl-1 , 1 -dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N- ((3R)-1 , 1 ,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, 4-[[6-[2-(2,4-difluorophenyl)-1 , 1 -difluoro-

2-hydroxy-3-(1 ,2,4-triazol-1 -yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, metyltetraprole + TX, 2 (difluoromethyl)-N-((3R)-1 , 1 ,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, a-(1 , 1 -dimethylethyl)- a-[4'-(trifluoromethoxy)[1 , T-biphenyl]-4-yl]-5-pyrimidinemethanol + TX, fluoxapiprolin + TX, enoxastrobin + TX, 4-[[6-[2-(2,4-difluorophenyl)-1 , 1 -difluoro-2-hydroxy-3-(1 ,2,4-triazol-1 -yl)propyl]-3- pyridyl]oxy] benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1 , 1 -difluoro-2-hydroxy-3-(5-sulfanyl-1 ,2,4- triazol-1 -y l)propyl]-3-pyridyl]oxy] benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1 , 1 -difluoro-2-hydroxy-

3-(5-thioxo-4H-1 ,2,4-triazol-1 -yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, trinexapac + TX,

coumoxystrobin + TX, zhongshengmycin + TX, thiodiazole copper + TX, zinc thiazole + TX, amectotractin + TX, iprodione + TX, mixtures Of (N-methoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]cyclopropanecarboxamide + TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]propanamide + TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1 ,3-dimethoxy-1-[[4-[5- (trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]urea + TX, N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 4,4-dimethyl-2- [[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, ethyl 1 -[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]pyrazole-4-carboxylate + TX, and N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]- 1 ,2,4-triazoi-3-amine + TX), wherein the compound in the mixture, other than TX, may be prepared from the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689, 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1 ,2,4-triazol-1 -yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO 2017/029179), 2-[6-(4-bromophenoxy)-2- (trifluoromethyl)-3-pyridyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO 2017/029179), 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy- propyl]imidazole-4-carbonitrile + TX (this compound may be prepared from the methods described in WO 2016/156290), 3-[2-(1 -chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-p ropyl]imidazole-4- carbonitrile + TX (this compound may be prepared from the methods described in WO 2016/156290), (4- phenoxyphenyljmethyl 2-amino-6-methyl-pyridine-3-carboxylate + TX (this compound may be prepared from the methods described in WO 2014/006945), 2,6-Dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6- c']dipyrrole-1 ,3,5,7(2H,6H)-tetrone + TX (this compound may be prepared from the methods described in WO 201 1/138281 ), N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzenecarbothioamide + TX, N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide + TX,

(Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyim ino-N,3-dimethyl-pent-3-enamide + TX (this compound may be prepared from the methods described in WO 2018/153707), N'-(2-chloro-5- methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N'-[2-chloro-4-(2-fluorophenoxy)-5- methyl-phenyl]-N-ethyl-N-methyl-formamidine + TX (this compound may be prepared from the methods described in WO 2016/202742), and 2-(difluoromethyl)-N-[(3S)-3-ethyl-1 ,1 -dimethyl-indan-4- yl]pyridine-3-carboxamide + TX (this compound may be prepared from the methods described in WO 2014/095675),

microbials including: Acinetobacter Iwoffii + TX, Acremonium alternatum + TX + TX, Acremonium cephalospohum + 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 FIB-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 var. amyloliquefaciens strain FZB24 (Taegro® + TX, Rhizopro®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1 Ab + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis israelensis (BMP123® + TX, Aquabac® + TX, VectoBac®) + TX, Bacillus thuringiensis kurstaki (Javelin® + TX, Deliver® + TX, CryMax® + TX, Bonide® + TX, Scutella WP® + TX, Turilav WP ® +

TX, Astuto® + TX, Dipel WP® + TX, Biobit® + TX, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®) + TX, Bacillus thuringiensis kurstaki FID-1 (Bioprotec-CAF / 3P®) + TX, Bacillus thuringiensis strain BD#32 + TX, Bacillus thuringiensis strain AQ52 + TX, Bacillus thuringiensis var. aizawai (XenTari® + TX, DiPel®) + TX, bacteria spp. (GROWMEND® + TX, GROWSWEET® + TX, Shootup®) + TX, bacteriophage of Clavipacter michiganensis (AgriPhage®) + TX, Bakflor® + TX, Beauveria bassiana (Beaugenic® + TX, Brocaril WP®) + TX, Beauveria bassiana GFIA (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, Canadian thistle fungus (CBFI 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 PRAA4-1 T (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 humicoia + 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 nucleopolyhedrovirus (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 nucleopolyhedrosis 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 corrugate + TX, Pseudomonas fluorescens strain A506 (BlightBan A506®) + TX, Pseudomonas putida + TX, Pseudomonas reactans + TX, Pseudomonas spp. + TX, Pseudomonas syringae (Bio-Save®) + TX, Pseudomonas viridiflava + TX, Pseudomons fluorescens (Zequanox®) + TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®) + TX, Puccinia canaliculata + TX, Puccinia thlaspeos (Wood Warrior®) + TX, Pythium paroecandrum + TX, Pythium oligandrum (Polygandron® + TX, Polyversum®) + TX, Pythium periplocum + TX, Rhanella aquatilis + TX, Rhanella spp. + TX, Rhizobia (Dormal® + TX, Vault®) + TX, Rhizoctonia + TX, Rhodococcus globerulus strain AQ719 + TX, Rhodosporidium diobovatum + TX, Rhodosporidium toruloides + TX, Rhodotorula spp. + TX, Rhodotorula glutinis + TX, Rhodotorula graminis + TX, Rhodotorula mucilagnosa + TX, Rhodotorula rubra + TX, Saccharomyces cerevisiae + TX, Salinococcus roseus + TX, Sclerotinia minor + TX, Sclerotinia minor (SARRITOR®) + TX, Scytalidium spp. + TX, Scytalidium uredinicola + TX, Spodoptera exigua nuclear polyhedrosis virus (Spod-X® + TX, Spexit®) + TX, Serratia marcescens + TX, Serratia plymuthica + TX, Serratia spp. + TX, Sordaria fimicola + TX, Spodoptera littoralis nucleopolyhedrovirus (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 supplementary micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Verticillium lecanii (Mycotal® + TX, Vertalec®) + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv. Poae (Camperico®) + TX, Xenorhabdus bovienii + TX, Xenorhabdus nematophilus ;

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, extract of neem oil (Trilogy®) + TX, essentials oils of Labiatae (Botania®) + TX, extracts of clove rosemary peppermint and thyme oil (Garden insect killer®) + TX, Glycinebetaine (Greenstim®) + TX, garlic + TX, lemongrass oil (GreenMatch®) + TX, neem oil + TX, Nepeta cataria (Catnip oil) + TX, Nepeta catarina + TX, nicotine + TX, oregano oil (MossBuster®)

+ TX, Pedaliaceae oil (Nematon®) + TX, pyrethrum + 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, thymus oil + TX, AGNIQUE® MMF + TX, BugOil® + TX, mixture of rosemary sesame pepermint thyme and cinnamon extracts (EF 300®) + TX, mixture of clove rosemary and peppermint extract (EF 400®) + TX, mixture of clove pepermint garlic oil and mint (Soil Shot®) + TX, kaolin (Screen®) + TX, storage glucam of brown algae (Laminarin®);

pheromones including: blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®) + TX, Codling Moth Pheromone (Paramount dispenser-(CM)/ Isomate C-Plus®) + TX, Grape Berry Moth Pheromone (3M MEC-GBM Sprayable Pheromone®) + TX, Leafroller pheromone (3M MEC - LR Sprayable Pheromone®) + TX, Muscamone (Snip7 Fly Bait® + TX, Starbar Premium Fly Bait®) + TX, Oriental Fruit Moth Pheromone (3M oriental fruit moth sprayable pheromone®) + TX, Peachtree Borer Pheromone (Isomate-P®) + TX, Tomato Pinworm Pheromone (3M Sprayable pheromone®) + TX, Entostat powder (extract from palm tree) (Exosex CM®) + TX, (E + TX,Z + TX,Z)- 3 + TX,8 + TX,1 1 Tetradecatrienyl acetate + TX, (Z + TX,Z + TX,E)-7 + TX, 11 + TX,13- Hexadecatrienal + TX, (E + TX,Z)-7 + TX,9-Dodecadien-1-yl acetate + TX, 2-Methyl-1-butanol + TX, Calcium acetate + TX, Scenturion® + TX, Biolure® + TX, Check-Mate® + TX, Lavandulyl senecioate;

Macrobials 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-M ite®) + 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, Anthocohs 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 matricahae (Aphipar-M®) + TX, Aphidoletes aphidimyza (Aphidend®) + TX, Aphidoletes aphidimyza (Aphidoline®) + TX, Aphytis lingnanensis + TX, Aphytis melinus + TX, Aprostocetus hagenowii + TX, Atheta coriaha (Staphyline®) + TX, Bombus spp. + TX, Bombus terresths (Natupol Beehive®) + TX, Bombus terresths (Beeline® + TX, Tripol®) + TX, Cephalonomia stephanodehs +

TX, Chilocorus nigritus + TX, Chrysoperla carnea (Chrysoline®) + TX, Chrysoperla carnea

(Chrysopa®) + TX, Chrysoperla rufilabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadhsthatus + 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 sibihca + TX, Dacnusa sibihca (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 sibihca (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, Oriline i®) + TX, Orius laevigatus (Thripor-L® + TX, Oriline I®) + TX, Orius majusculus (Oriline m®) + TX, Orius strigicollis (Thripor-S®) + TX, Pauesia juniperorum + TX, Pediobius foveolatus + TX, Phasmarhabditis hermaphrodite (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 (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, BioNe 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, Ferri-phosphate (Ferramol®) + TX, Funnel traps (Trapline y®) + TX, Gallex® + TX, Grower's Secret® + TX, Homo-brassonolide + TX, Iron Phosphate (Lilly Miller Worry Free Ferramol Slug & Snail Bait®) + TX, MCP hail trap (Trapline f®) + TX, Microctonus hyperodae + TX, Mycoleptodiscus terrestris (Des-X®) + TX, BioGain® + TX, Aminomite® + TX, Zenox® + TX, Pheromone trap (Thripline ams®) + TX, potassium bicarbonate (MilStop®) + TX, potassium salts of fatty acids (Sanova®) + TX, potassium silicate solution (Sil-Matrix®) + TX, potassium iodide + potassiumthiocyanate (Enzicur®) + TX, SuffOil-X® + TX, Spider venom + TX, Nosema locustae (Semaspore Organic Grasshopper Control®) + TX, Sticky traps (Trapline YF® + TX, Rebell Amarillo®) + TX and Traps (Takitrapline y + b®) + TX.

The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The above described mixing partners are known. Where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound "abamectin" is described under entry number (1 ). Where "[CCN]" is added hereinabove to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names. Copyright © 1995-2004]; for example, the compound "acetoprole" is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html.

Most of the active ingredients described above are referred to hereinabove by a so-called "common name", the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a "common name", the nature of the designation used instead is given in round brackets for the particular compound; in that case, the lUPAC name, the lUPAC/Chemical Abstracts name, a "chemical name", a "traditional name", a "compound name" or a "develoment code" is used or, if neither one of those designations nor a "common name" is used, an "alternative name" is employed.“CAS Reg. No” means the Chemical Abstracts Registry Number.

The active ingredient mixture of the compounds of formula I selected from Tables A-1 to A-6, Tables C-1 to C-6, Tables E-1 to E-4, Tables G-1 to G-24 and Table P with active ingredients described above comprises a compound selected from Tables A-1 to A-6, Tables C-1 to C-6, Tables E-1 to E-4, Tables G-1 to G-24 and Table P and an active ingredient as described above preferably in a mixing ratio of from 100: 1 to 1 :6000, especially from 50:1 to 1 :50, more especially in a ratio of from 20: 1 to 1 :20, even more especially from 10:1 to 1 : 10, very especially from 5: 1 and 1 :5, special preference being given to a ratio of from 2:1 to 1 :2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1 : 1 , or 5: 1 , or 5:2, or 5:3, or 5:4, or 4: 1 , or 4:2, or 4:3, or 3: 1 , or 3:2, or 2:1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 :150, or 1 :35, or 2:35, or 4:35, or 1 :75, or 2:75, or 4:75, or 1 :6000, or 1 :3000, or 1 :1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750. Those mixing ratios are by weight. The mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.

The mixtures comprising a compound of formula I selected from Tables A-1 to A-6, Tables C-1 to C-6, Tables E-1 to E-4, Tables G-1 to G-24 and Table P and one or more active ingredients as described above can be applied, for example, in a single“ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a“tank- mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula I selected from Tables A-1 to A-6, Tables C-1 to C-6, Tables E-1 to E-4, Tables G-1 to G-24 and Table P and the active ingredients as described above is not essential for working the present invention.

The compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.

The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds I for the preparation of these compositions are also a subject of the invention.

The application methods for the compositions, that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention. Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.

A preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.

The compounds of the invention and compositions thereof are also be suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type. The propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing. Alternatively, the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention. Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds.

The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.

The present invention also comprises seeds coated or treated with or containing a compound of formula I. The term "coated or treated with and/or containing" generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the ingredient may penetrate into the seed material, depending on the method of application. When the said seed product is (re)planted, it may absorb the active ingredient. In an embodiment, the present invention makes available a plant propagation material adhered thereto with a compound of formula (I). Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound of formula (I).

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

Biological Examples:

The Examples which follow serve to illustrate the invention. Certain compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 25 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm, 0.2 ppm or 0.05 ppm.

Example B1 : Bemisia tabaci (Cotton white fly): Feeding/contact activity

Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'OOO ppm DMSO stock solutions. After drying the leaf discs were infested with adult white flies. The samples were checked for mortality 6 days after incubation.

The following compounds resulted in at least 80% mortality at an application rate of 200 ppm:

P2, P3, P5, P7, P10, P11.

Example B2: Diabrotica balteata (Corn root worm)

Maize sprouts placed onto an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10Ό00 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 4 days after infestation.

The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:

P1 , P2, P3, P4, P5, P6, P7, P8, P9, P10, P11 , P12, P13.

Example B3: Euschistus herns (Neotropical Brown Stink Bug)

Soybean leaves on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10Ό00 ppm DMSO stock solutions. After drying the leaves were infested with N2 nymphs. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation.

The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:

P1 , P2, P3, P4, P5, P6, P8, P9, P10, P1 1 , P13.

Example B4: Frankliniella occidentalis (Western flower thrips): Feeding/contact activity

Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'OOO DMSO stock solutions. After drying the leaf discs were infested with a Frankliniella population of mixed ages. The samples were assessed for mortality 7 days after infestation.

The following compounds resulted in at least 80% mortality at an application rate of 200 ppm:

P2, P3, P5, P11.

Example B5: Plutella xylostella (Diamond back moth)

24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10'OOO ppm DMSO stock solutions by pipetting. After drying, Plutella eggs were pipetted through a plastic stencil onto a gel blotting paper and the plate was closed with it. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 8 days after infestation.

The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:

P1 , P2, P3, P4, P5, P6, P7.

Example B6: Mvzus oersicae (Green peach aphid): Feeding/Contact activity

Sunflower leaf discs were placed onto agar in a 24-well microtiter plate and sprayed with aqueous test solutions prepared from 10Ό00 ppm DMSO stock solutions. After drying, the leaf discs were infested with an aphid population of mixed ages. The samples were assessed for mortality 6 days after infestation.

The following compounds resulted in at least 80% mortality at an application rate of 200 ppm:

P4, P5, P8, P9, P10.

Example B7: Mvzus oersicae (Green peach aphid). Systemic activity

Roots of pea seedlings infested with an aphid population of mixed ages were placed directly into aqueous test solutions prepared from 10Ό00 DMSO stock solutions. The samples were assessed for mortality 6 days after placing seedlings into test solutions.

The following compounds resulted in at least 80% mortality at a test rate of 24 ppm:

P5.

Example B8: Plutella xylostella (Diamond back moth)

24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10'OOO ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (10 to 15 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation.

The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:

P8, P9, P10, P1 1 , P12, P13.

Example B9: Soodootera littoralis (Egyptian cotton leaf worm)

Cotton leaf discs were placed onto agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'OOO ppm DMSO stock solutions. After drying the leaf discs were infested with five L1 larvae. The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 3 days after infestation. Control of Spodoptera littoralis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.

The following compounds resulted in at least 80% control at an application rate of 200 ppm: PI , P2, P3, P4, P5, P6, P7, P8, P9, P10, P11 , P13.

Example B10: Tetranvchus urticae (Two-spotted spider mite): Feeding/contact activity

Bean leaf discs on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10'OOO ppm DMSO stock solutions. After drying the leaf discs were infested with a mite population of mixed ages. The samples were assessed for mortality on mixed population (mobile stages) 8 days after infestation.

The following compounds resulted in at least 80% mortality at an application rate of 200 ppm:

P12, P13.

Example B1 1 : Soodootera littoralis (Egyptian cotton leaf worm)

Test compounds were applied by pipette from 10Ό00 ppm DMSO stock solutions into 24-well plates and mixed with agar. Lettuce seeds were placed onto the agar and the multi well plate was closed by another plate which contained also agar. After 7 days the compound was absorbed by the roots and the lettuce grew into the lid plate. The lettuce leaves were then cut off into the lid plate. Spodoptera eggs were pipetted through a plastic stencil onto a humid gel blotting paper and the lid plate was closed with it. The samples were assessed for mortality, anti-feedant effect and growth inhibition in comparison to untreated samples 6 days after infestation.

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

P9, P10, P1 1.