WO2013156431A1

WO2013156431A1 - Pesticidally active pyridyl- and pyrimidyl- substituted thiazole and thiadiazole derivatives

Info

Publication number: WO2013156431A1
Application number: PCT/EP2013/057782
Authority: WO
Inventors: Andrew Edmunds; Aurelien BIGOT; Roger Graham Hall; André Jeanguenat; Torsten LUKSCH; Sebastian RENDLER
Original assignee: Syngenta Participations Ag
Priority date: 2012-04-17
Filing date: 2013-04-15
Publication date: 2013-10-24

Abstract

Compounds of formula (I), wherein the substituents are as defined in claim 1, and the agrochemically acceptable salts and all stereoisomers and tautomeric forms of the compounds of formula (I) can be used as agrochemical active ingredients and can be prepared in a manner known per se.

Description

Pesticidally active pyridyl- and pyrimidyl- substituted thiazole and thiadiazole derivatives

The present invention relates to pesticidally active pyridyl and pyrimidyl -substituted thiazole and thiadiazole derivatives, to processes for their preparation, to compositions comprising those compounds, and to their use for controlling insects or representatives of the order Aca- rina.

2-(3-Pyridyl)-thiazole derivatives with pesticidal action are known and described, for example, in US-4,080,457, WO 2009/149858, WO 2010/129497, WO 2010/006713, WO 201 1/138285 and WO 2012/000896.

There have now been found novel, pesticidally active 2-(3-pyridyl)-thiazole derivatives with specific aromatic bicyclic substituents on the thiazole and thiadiazole ring.

The present invention accordingly relates to compounds of formula I

wherein

X-i is nitrogen or CR-i;

X₂ is nitrogen or CR₂;

m is 0 or 1 ;

Ri is hydrogen, fluoro, chloro, bromo, iodo, C₂-C₃alkynyl or C₂-C₃haloalkynyl;

R₂ is hydrogen, halogen, d-C₃alkyl, CrC₃alkylthio, CrC₃alkylsulfinyl, Ci-C₃alkylsulfonyl, CrC₃alkoxy or cyano; or R₂ is a three- to four- membered ring which can be partially saturated or fully saturated and can contain one heteroatom selected form the group consisting of nitrogen, oxygen and sulphur; said three- to four- membered ring system can be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, methyl and trifluoromethyl; or

R₂ is C₂-C₆alkenyl which can be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, methyl and trifluoromethyl; or R₂ is C₂-C₆alkynyl which can be substituted by substituents selected from the group consisting of halogen, methyl and trifluoromethyl;

Q is an aromatic bicyclic ring system selected from Q₂ and Q₃

in which the arrow shows the connectivity to the thiazole or thiadiazole ring and wherein Gi is nitrogen, N-CrC₄alkyl, sulpher, oxygen, a direct bond or C-R₃;

G₂ is nitrogen, N-CrC₄alkyl, sulpher, oxygen, a direct bond or C-R₄;

G₃ is nitrogen, N-CrC₄alkyl, sulpher, oxygen, a direct bond or C-R₅;

G₄ is nitrogen, N-CrC₄alkyl, sulpher, oxygen, a direct bond or C-R₆; with the provisos that a) not more than 1 substituent G can at the same time form a direct bond,

b) not more than 2 substituents G can be oxygen or sulpher, and

c) 2 substituents G as oxygen and/or sulpher are separated by at least one carbon atom; d) only one substituent G can be N-CrC₄alkyl;

X₃ is nitrogen, a direct bond or C-R₇;

X₄ is nitrogen or C-R₈ or when X₃ is a direct bond, X₄ is N R₉, oxygen or sulpher;

X₅ is nitrogen, a direct bond or C-Ri₀;

X₆ is nitrogen, a direct bond or C-Rn or when X₅ is a direct bond, X₆ is N R₁₂, oxygen or sulphur, and when X₆ is a direct bond, X₅ is N R₁₂, oxygen or sulpher ;

X₇ is nitrogen, a direct bond or C-Ri₄;

X₈ is nitrogen, or C-Ri₅ or when X₇ is a direct bond, X₈ is N R₁₆, oxygen or sulphur;

each of R₃, R₄, R5, R6, R7, Rs, R10, R11 , Ri₄, and Ri₅, which may be the same or different, represents hydrogen, halogen, nitro, cyano, hydroxy, CHO, CrC₆alkyl, C₂-C₆alkenyl, C₂- C₆alkynyl, C₃-C₆cycloalkyl, CrC₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃- C₆halocycloalkyl, CrC₄alkoxy, Ci-C₄alkoxy-Ci-C₄alkoxy-Ci-C₄alkyl, d-C₄haloalkoxy, C C₄alkylthio, CrC₄haloalkylthio, CrC₄haloalkylsulfinyl, CrC₄haloalkylsulfonyl, d-

C₄alkylsulfinyl, Ci-C₄alkylsulfonyl, Ci-C₄alkylsulfonyl-Ci-C₄alkyl, Ci-C₄alkylsulfoximino-Ci- C₄alkyl, Ci-C₄alkylamino, C₂-C₄dialkylamino, C₃-C₆cycloalkylamino, CrC₆alkyl-C₃- C₆cycloalkylamino, C₂-C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃- C₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy, C₃- C₆dialkylaminocarbonyloxy, Ci-C₄alkoxyimino-Ci-C₄alkyl, , -CONHS0₂-CrC₆-alkyl, - CONHS0₂N(Ci-C₆-alkyl)₂, C₃-C₆trialkylsilyl or a three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated, said three- to ten-membered, monocyclic or fused bicyclic ring system can be substituted by one to three substituents independently selected from the group consisting of CrC₄alkyl, C₂- C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, d-C₄haloalkyl, C₂-C₄haloalkenyl, C₂-C₄haloalkynyl, C₃-C₆halocycloalkyl, halogen, cyano, nitro, CrC₄alkoxy, CrC₄haloalkoxy, CrC₄alkylthio, C C₄alkylsulfinyl, Ci-C₄alkylsulfonyl, Ci-C₄alkylsulfoximino, Ci-C₄alkylamino, C₂-C₆dialkylamino, C₃-C₆cycloalkylamino, Ci-C₄alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl, C₂- C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₂-C₈ dialkylaminocarbonyl and C₂-C₆ trialkylsilyl;

or each of R₃, R₄, R5, R6, Ri₄, and Ri₅ which may be the same or different, represents a group Ji

wherein R₆i and R₆₂ independently from each other, are hydrogen, CrC₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, or are phenyl which can be mono-, di- or trisubstituted with substitutents selected from the group consisting of CrC₂alkyl, CrC₂haloalkyl, halogen, cyano, nitro, Ci-C₃alkoxy, CrC₄alkylthio, CrC₃alkylsulfinyl, CrC₃alkylsulfonyl, C₂- C₄alkylcarbonyl, C₂-C₄alkoxycarbonyl and C₂-C₄alkylaminocarbonyl;

X₉ is oxygen, NH, or N-CrC₄alkyl;

R₉, R₁₂, Ri₃ and Ri₆ are, independently from each other, hydrogen, CrC₂alkyl, C₃- C₆c cloalkyl or CrC₂haloalkyl; with the proviso that Q is different from the following groups

Z-1 Z-2 Z-3 and Z-4

in which the free radical shows the connectivity to the thiazole or thiadiazole ring;

and agrochemically acceptable salts, enantiomers, tautomers and N-oxides of those compounds. 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, sulphuric acid, nitric acid, nitrose acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as Ci-C₄alkanecarboxylic 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 CrC₄alkane- 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.

The alkyl groups occurring in the definitions of the substituents can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl, hexyl, nonyl, decyl and their branched isomers. Alkoxy, alkenyl and alkynyl radicals are derived from the alkyl radicals mentioned. The alkenyl and alkynyl groups can be mono- or polyunsaturated.

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 preferably have a chain length of from 1 to 6 carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 ,1 -difluoro- 2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

Alkoxy groups preferably have a preferred chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and also the isomeric pentyloxy and hexyloxy radicals; preferably methoxy and ethoxy.

Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert- butoxycarbonyl; preferably methoxycarbonyl or ethoxycarbonyl. Haloalkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1 ,1 ,2,2- tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2- trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.

Alkylthio groups preferably have a chain length of from 1 to 6 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio and ethylthio. Alkylsulphinyl is, for example, methylsulphinyl, ethylsulphinyl, propylsulphinyl, isopropylsulphinyl, n-butylsulphinyl, isobutylsulphinyl, sec-butylsulphinyl, tert-butylsulphinyl; preferably methylsulphinyl and ethylsulphinyl.

Alkylsulphonyl is, for example, methylsulphonyl, ethylsulphonyl, propylsulphonyl,

isopropylsulphonyl, n-butylsulphonyl, isobutylsulphonyl, sec-butylsulphonyl or tert- butylsulphonyl; preferably methylsulphonyl or ethylsulphonyl.

Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or the isomeric butylamines. Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, dibutylamino and diisopropylamino. Preference is given to alkylamino groups having a chain length of from 1 to 4 carbon atoms.

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

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

The cycloalkyl groups preferably have from 3 to 6 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Phenyl, also as part of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl, phenoxyalkyl, may be substituted. In this case, the substituents can be in ortho, meta and/or para position. The preferred substituent positions are the ortho and para positions to the ring attachment point.

In the context of the present invention "mono- to polysubstituted" in the definition of the substituents, means typically, depending on the chemical structure of the substituents, monosubstituted to seven-times substituted, preferably monosubstituted to five-times substituted, more preferably mono-, double- or triple-substituted.

In the context of the present invention "halo-substituted phenyl" in the definition of the substituents, means for example a phenyl group which is mono- to polysubstituted by substituents selected from the group consisting of fluoro, chloro, bromo and iodo. Preferably "halo-substituted phenyl" is phenyl which is mono- di or tri-substituted by chloro, in particular mono-substituted by chloro.

According to the present invention, a five- to ten-membered monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated is, depending of the number of rin members, for example, selected from the group consisting of

cyclopentyl, cyclohexyl, where said cycloalkylgroups for their part may be preferably unsubstituted or substituted by CrC₆alkyl or halogen, or is phenyl, benzyl, naphthyl or the following heterocyclic groups: pyrrolyl; pyridyl; pyrazolyl; pyrimidyl; pyrazinyl; imidazolyl; thiadiazolyl; quinazolinyl; furyl; oxadiazolyl; indolizinyl; pyranyl; isobenzofuranyl; thienyl; naphthyridinyl; (1 -methyl-1 H-pyrazol-3-yl)-; (1 -ethyl-1 H-pyrazol-3-yl)-; (1 -propyl-1 H-pyrazol-3- yl)-; (1 H-pyrazol-3-yl)-; (1 ,5-dimethyl-1 H-pyrazol-3-yl)-; (4-chloro-1 -methyl-1 H-pyrazol-3-yl)-; (1 H-pyrazol-1 -yl)-; (3-methyl-1 H-pyrazol-1 -yl)-; (3,5-dimethyl-1 H-pyrazol-1 -yl)-; (3-isoxazolyl)- ; (5-methyl-3-isoxazolyl)-; (3-methyl-5-isoxazolyl)-; (5-isoxazolyl)-; (1 H-pyrrol-2-yl)-; (1 - methyl-1 H-pyrrol-2-yl)-; (1 H-pyrrol-1 -yl)-; (1 -methyl-1 H-pyrrol-3-yl)-; (2-furanyl)-; (5-methyl-2- furanyl)-; (3-furanyl)-; (5-methyl-2-thienyl)-; (2-thienyl)-; (3-thienyl)-; (1 -methyl-1 H-imidazol-2- yl)-; (1 H-imidazol-2-yl)-; (1 -methyl-1 H- imidazol-4-yl)-; (1 - methyl-1 H-imidazol-5-yl)-; (4- methyl-2-oxazolyl)-; (5-methyl-2-oxazolyl)-; (2-oxazolyl)-; (2-methyl-5-oxazolyl)-; (2-methyl-4- oxazolyl)-; (4-methyl-2-thiazolyl)-; (5-methyl-2-thiazolyl)-; (2-thiazolyl)-; (2-methyl-5- thiazolyl)-; (2-methyl-4-thiazolyl)-; (3-methyl-4-isothiazolyl)-; (3-methyl-5-isothiazolyl)-; (5- methyl-3-isothiazolyl)-; (1 -methyl-1 H-1 ,2,3-triazol-4-yl)-; (2-methyl-2H-1 ,2,3-triazol-4-yl)-; (4- methyl-2H-1 ,2,3-triazol-2-yl)-; (1 -methyl-1 H-1 ,2,4-triazol-3-yl)-; (1 ,5-dimethyl-1 H-1 ,2,4-triazol 3-yl)-; (3-methyl-1 H-1 ,2,4-triazol-1 -yl)-; (5-methyl-1 H-1 ,2,4-triazol-1 -yl)-; (4,5-dimethyl-4H- 1 ,2,4-triazol-3-yl)-; (4-methyl-4H-1 ,2,4-triazol-3-yl)-; (4H-1 ,2,4-triazol-4-yl)-; (5-methyl-1 ,2,3- oxadiazol-4-yl)-; (1 ,2,3-oxadiazol-4-yl)-; (3-methyl-1 ,2,4-oxadiazol-5-yl)-; (5-methyl-1 ,2,4- oxadiazol-3-yl)-; (4-methyl-3-furazanyl)-; (3-furazanyl)-; (5-methyl-1 ,2,4-oxadiazol-2-yl)-; (5- methyl-1 ,2,3-thiadiazol-4-yl)-; (1 ,2,3-thiadiazol-4-yl)-; (3-methyl-1 ,2,4-thiadiazol-5-yl)-; (5- methyl-1 ,2,4-thiadiazol-3-yl)-; (4-methyl-1 ,2,5-thiadiazol-3-yl)-; (5-methyl-1 ,3,4-thiadiazol-2- yl)-; (1 -methyl-1 H-tetrazol-5-yl)-; (1 H-tetrazol-5-yl)-; (5-methyl-1 H-tetrazol-1 -yl)-; (2-methyl- 2H-tetrazol-5-yl)-; (2-ethyl-2H-tetrazol-5-yl)-; (5-methyl-2H-tetrazol-2-yl)-; (2H-tetrazol-2-yl)-; (2-pyridyl)-; (6-methyl-2-pyridyl)-; (4-pyridyl)-; (3-pyridyl)-; (6-methyl-3-pyridazinyl)-; (5- methyl-3-pyridazinyl)-; (3-pyridazinyl)-; (4,6-dimethyl-2-pyrimidinyl)-; (4-methyl-2-pyrimidinyl) ; (2-pyrimidinyl)-; (2-methyl-4-pyrimidinyl)-; (2-chloro-4-pyrimidinyl)-; (2,6-dimethyl-4- pyrimidinyl)-; (4-pyrimidinyl)-; (2-methyl-5-pyrimidinyl)-; (6-methyl-2-pyrazinyl)-; (2-pyrazinyl)- (4,6-dimethyl-1 ,3,5-triazin-2-yl)-; (4,6-dichloro-1 ,3,5-triazin-2-yl)-; (1 ,3,5-triazin-2-yl)-; (4- methyl-1 ,3,5-triazin-2-yl)-; (3-methyl-1 ,2,4-triazin-5-yl)-; (3-methyl-1 ,2,4-triazin-6-yl)-;

wherein each R₂6 is methyl, each R₂₇ and each R₂₈ are independently hydrogen, CrC₃alkyl, CrC₃alkoxy, CrC₃alkylthio or trifluoromethyl, X_4a is oxygen or sulfur and r = 1 , 2, 3 or 4.

CH

Where no free valency is indicated in those definitions, for example as in °^~ ^ , the linkage

site is located at the carbon atom labelled "CH" or in a case such as, for example,

at the bonding site indicated at the bottom left.

In a preferred embodiment of the present invention,

Gi is nitrogen, sulpher, oxygen, a direct bond or C-R₃;

G₂ is nitrogen, sulpher, oxygen, a direct bond or C-R₄;

G₃ is nitrogen, sulpher, oxygen, a direct bond or C-R₅;

G₄ is nitrogen, sulpher, oxygen, a direct bond or C-R₆; with the provisos that

a) not more than 1 substituent G can at the same time form a direct bond,

b) not more than 2 substituents G can be oxygen or sulpher, and

c) 2 substituents G as oxygen and/or sulpher are separated by at least one carbon atom; each of R₃, R₄, R5, R6, R7, Rs, Rio_> Rn , Ri₄, and Ri₅, which may be the same or different, represents hydrogen, halogen, nitro, cyano, hydroxy, CHO, CrC₆alkyl, C₂-C₆alkenyl, C₂- C₆alkynyl, C₃-C₆cycloalkyl, CrC₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃- C₆halocycloalkyl, CrC₄alkoxy, Ci-C₄alkoxy-Ci-C₄alkoxy-Ci-C₄alkyl, CrC₄haloalkoxy, C C₄alkylthio, CrC₄haloalkylthio, CrC₄haloalkylsulfinyl, CrC₄haloalkylsulfonyl, d-

C₄alkylsulfinyl, Ci-C₄alkylsulfonyl, Ci-C₄alkylsulfonyl-Ci-C₄alkyl, Ci-C₄alkylsulfoximino-Ci- C₄alkyl, Ci-C₄alkylamino, C₂-C₄dialkylamino, C₃-C₆cycloalkylamino, CrC₆alkyl-C₃- C₆cycloalkylamino, C₂-C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃- C₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy, C₃- C₆dialkylaminocarbonyloxy, Ci-C₄alkoxyimino-Ci-C₄alkyl, , -CONHS0₂-CrC₆-alkyl, -

CONHS0₂N(CrC₆-alkyl)₂, C₃-C₆trialkylsilyl or a three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated, said three- to ten-membered, monocyclic or fused bicyclic ring system can be substituted by one to three substituents independently selected from the group consisting of CrC₄alkyl, C₂- C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, CrC₄haloalkyl, C₂-C₄haloalkenyl, C₂-C₄haloalkynyl, C₃-C₆halocycloalkyl, halogen, cyano, nitro, CrC₄alkoxy, CrC₄haloalkoxy, CrC₄alkylthio, C C₄alkylsulfinyl, Ci-C₄alkylsulfonyl, Ci-C₄alkylsulfoximino, Ci-C₄alkylamino, C₂-C₆dialkylamino, C₃-C₆cycloalkylamino, Ci-C₄alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl, C₂- C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₂-C₈ dialkylaminocarbonyl and C₂-C₆ trialkylsilyl.

In further preferred compounds of formula I,

Ri is hydrogen;

R₂ is hydrogen, halogen, Ci-C₃alkyl, Ci-C₃alkylthio, CrC₃alkylsulfinyl, Ci-C₃alkylsulfonyl, CrC₃alkoxy or cyano; or R₂ is a three- to four- membered ring which can be partially saturated or fully saturated and can contain one heteroatom selected form the group consisting of nitrogen, oxygen and sulphur; said three- to four- membered ring system can be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, methyl and trifluoromethyl;

Q is a group Q₃;

wherein

Gi , G₂, G₃ and G₄ form together with the two carbon atoms to which Gi and G₄ are attached, an aromatic ring system; wherein Gi is nitrogen, N-CrC₄alkyl, sulpher, oxygen, a direct bond or C-R₃; preferably Gi is nitrogen, sulpher, oxygen, a direct bond or C-R₃;

G₂ is nitrogen, N-CrC₄alkyl, sulpher, oxygen, a direct bond or C-R₄; preferably G₂ is nitrogen, sulpher, oxygen, a direct bond or C-R₄;

G₃ is nitrogen, N-CrC₄alkyl, sulpher, oxygen, a direct bond or C-R₅; preferably G₃ is nitrogen, sulpher, oxygen, a direct bond or C-R₅;

G₄ is nitrogen, N-CrC₄alkyl, sulpher, oxygen, a direct bond or C-R₆; preferably G₄ is nitrogen, sulpher, oxygen, a direct bond or C-R₆;

with the provisos that

a) not more than 1 substituent G can at the same time form a direct bond,

b) not more than 2 substituents G can be oxygen or sulpher, and

X₇ is nitrogen, a direct bond or C-Ri₄;

X₈ is nitrogen, or C-Ri₅ or when X₇ is a direct bond, X₈ is N R₁₆ , oxygen or sulphur;

each of R₃, R₄, R5, R6, Ri₄, and Ri₅, which may be the same or different, represents hydrogen, halogen, nitro, cyano, hydroxy, CHO, CrC₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃- C₆cycloalkyl, CrC₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, d- C₄alkoxy, Ci-C₄alkoxy-Ci-C₄alkoxy-Ci-C₄alkyl, CrC₄haloalkoxy, CrC₄alkylthio, d- C₄haloalkylthio, CrC₄haloalkylsulfinyl, CrC₄haloalkylsulfonyl, CrC₄alkylsulfinyl, d- C₄alkylsulfonyl, Ci-C₄alkylsulfonyl-Ci-C₄alkyl, Ci-C₄alkylsulfoximino-Ci-C₄alkyl, d- C₄alkylamino, C₂-C₄dialkylamino, C₃-C₆cycloalkylamino, Ci-C₆alkyl-C₃-C₆cycloalkylamino, C₂- C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy, C₃-C₆dialkylaminocarbonyloxy, d- dalkoxyimino-d-dalkyl, , -CONHS0₂-d-C₆-alkyl, -CONHS0₂N(d-C₆-alkyl)₂, C3-

C₆trialkylsilyl, or a three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated, said three- to ten-membered, monocyclic or fused bicyclic ring system can be substituted by one to three substituents independently selected from the group consisting of d-dalkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, d-dhaloalkyl, C₂-C₄naloalkenyl, C₂-C₄naloalkynyl, C₃-C₆halocycloalkyl, halogen, cyano, nitro, d-dalkoxy, d-dhaloalkoxy, d-dalkylthio, d-dalkylsulfinyl, d- dalkylsulfonyl, d-dalkylsulfoximino, d-dalkylamino, d-C₆dialkylamino, C3- C₆cycloalkylamino, d-dalkyl-d-C₆cycloalkylamino, d-dalkylcarbonyl, C₂- C₆alkoxycarbonyl, C2-C₆alkylaminocarbonyl, C₂-C₈ dialkylaminocarbonyl and C₂-C₆ trialkylsilyl; and

Ri₆ is hydrogen, CrC₂alkyl, C₃-C₆cycloalkyl or CrC₂haloalkyl. In further preferred compounds of formula I,

Ri is hydrogen;

R₂ is hydrogen, halogen, d-C₃alkyl, CrC₃alkylthio, CrC₃alkylsulfinyl, Ci-C₃alkylsulfonyl, CrC₃alkoxy or cyano; or R₂ is a three- to four- membered ring which can be partially saturated or fully saturated and can contain one heteroatom selected form the group consisting of nitrogen, oxygen and sulphur; said three- to four- membered ring system can be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, methyl and trifluoromethyl;

Q is a group Q₂;

wherein

Gi, G₂, G₃ and G₄ form together with the two carbon atoms to which Gi and G₄ are attached, an aromatic ring system; wherein

Gi is nitrogen, N-Ci-C₄alkyl, sulpher, oxygen, a direct bond or C-R₃; preferably Gi is nitrogen, sulpher, oxygen, a direct bond or C-R₃;

G₂ is nitrogen, N-Ci-C₄alkyl, sulpher, oxygen, a direct bond or C-R₄; preferably G₂ is nitrogen, sulpher, oxygen, a direct bond or C-R₄;

G₃ is nitrogen, N-Ci-C₄alkyl, sulpher, oxygen, a direct bond or C-R₅; preferably G₃ is nitrogen, sulpher, oxygen, a direct bond or C-R₅;

G₄ is nitrogen, N-Ci-C₄alkyl, sulpher, oxygen, a direct bond or C-R₆; preferably G₄ is nitrogen, sulpher, oxygen, a direct bond or C-R₆;

with the provisos that

a) not more than 1 substituent G can at the same time form a direct bond,

b) not more than 2 substituents G can be oxygen or sulpher, and

c) 2 substituents G as oxygen and/or sulpher are separated by at least one carbon atom; d) only one substituent G can be N-Ci-C₄alkyl;

X₅ is nitrogen, a direct bond or C-Ri₀;

X₆ is nitrogen, a direct bond or C-Rn or when X₅ is a direct bond, X₆ is NR₁₂, oxygen or sulphur, and when X₆ is a direct bond, X₅ is NR₁₂, oxygen or sulpher ;

each of R₃, R₄, R₅, R6, Rio, and Rn, which may be the same or different, represents hydrogen, halogen, nitro, cyano, hydroxy, CHO, CrC₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃- C₆cycloalkyl, Ci-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, d- C₄alkoxy, Ci-C₄alkoxy-Ci-C₄alkoxy-Ci-C₄alkyl, CrC₄haloalkoxy, CrC₄alkylthio, d- C₄haloalkylthio, CrC₄haloalkylsulfinyl, CrC₄haloalkylsulfonyl, CrC₄alkylsulfinyl, d- C₄alkylsulfonyl, Ci-C₄alkylsulfonyl-Ci-C₄alkyl, Ci-C₄alkylsulfoximino-Ci-C₄alkyl, d- C₄alkylamino, C₂-C₄clialkylamino, C₃-C₆cycloalkylamino, Ci-C₆alkyl-C₃-C₆cycloalkylamino, C₂- C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₆clialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy, C₃-C₆dialkylaminocarbonyloxy, d- dalkoxyimino-d-dalkyl, -CONHS0₂-Ci-C₆-alkyl, -CONHS0₂N(d-C₆-alkyl)₂, C₃- C₆trialkylsilyl, or a three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated, said three- to ten-membered, monocyclic or fused bicyclic ring system can be substituted by one to three substituents independently selected from the group consisting of d-dalkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, d-dhaloalkyl, C₂-C₄naloalkenyl, C₂-C₄naloalkynyl, C₃-C₆halocycloalkyl, halogen, cyano, nitro, d-dalkoxy, d-dhaloalkoxy, d-dalkylthio, d-dalkylsulfinyl, d- dalkylsulfonyl, d-dalkylsulfoximino, d-dalkylamino, d-ddialkylamino, d- C₆cycloalkylamino, d-dalkyl-d-dcycloalkylamino, d-dalkylcarbonyl, C₂- C₆alkoxycarbonyl, d-dalkylaminocarbonyl, C₂-C₈ dialkylaminocarbonyl and d-d

trialkylsilyl; and

Ri₂ is hydrogen, d-dalkyl, C₃-C₆cycloalkyl or d-dhaloalkyl;

and agrochemically acceptable salts, enantiomers, tautomers and N-oxides of those compounds.

In especially preferred compounds of formula I,

Ri is hydrogen;

R₂ is hydrogen, halogen, d-dalkyl, d-dalkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, Crdalkoxy or cyano; or R₂ is a three- to four- membered ring which can be partially saturated or fully saturated and can contain one heteroatom selected form the group consisting of nitrogen, oxygen and sulphur; said three- to four- membered ring system can be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, methyl and trifluoromethyl;

Q is a group Qi,

wherein

Gi, G₂, G₃ and G₄ form together with the two carbon atoms to which Gi and G₄ are attached, an aromatic ring system; wherein Gi is nitrogen, N-CrC₄alkyl, sulpher, oxygen, a direct bond or C-R₃; preferably Gi is nitrogen, sulpher, oxygen, a direct bond or C-R₃;

with the provisos that

a) not more than 1 substituent G can at the same time form a direct bond,

b) not more than 2 substituents G can be oxygen or sulpher, and

X₃ is nitrogen, a direct bond or C-R₇;

X₄ is nitrogen or C-R₈ or when X₃ is a direct bond, X₄ is NR₉, oxygen or sulpher;

each of R₃, R₄, R₅, R₆, R7 and R₈, which may be the same or different, represents hydrogen, halogen, nitro, cyano, hydroxy, CHO, CrC₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, CrC₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, d-C₄alkoxy, C C₄alkoxy-Ci-C₄alkoxy-Ci-C₄alkyl, CrC₄haloalkoxy, CrC₄alkylthio, CrC₄haloalkylthio, C C₄haloalkylsulfinyl, CrC₄haloalkylsulfonyl, CrC₄alkylsulfinyl, Ci-C₄alkylsulfonyl, d- C₄alkylsulfonyl-Ci-C₄alkyl, Ci-C₄alkylsulfoximino-Ci-C₄alkyl, Ci-C₄alkylamino, C₂- C₄dialkylamino, C₃-C₆cycloalkylamino, Ci-C₆alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₆dialkylaminocarbonyl, C₂- C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy, C₃-C₆dialkylaminocarbonyloxy, C

C₄alkoxyimino-Ci-C₄alkyl, -CONHS0₂-C C₆-alkyl, -CONHS0₂N(C C₆-alkyl)₂, C₃-

C₆trialkylsilyl, or a three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated, said three- to ten-membered, monocyclic or fused bicyclic ring system can be substituted by one to three substituents independently selected from the group consisting of CrC₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, CrC₄haloalkyl, C₂-C₄haloalkenyl, C₂-C₄haloalkynyl, C₃-C₆halocycloalkyl, halogen, cyano, nitro, CrC₄alkoxy, CrC₄haloalkoxy, CrC₄alkylthio, CrC₄alkylsulfinyl, d- C₄alkylsulfonyl, Ci-C₄alkylsulfoximino, Ci-C₄alkylamino, C₂-C₆dialkylamino, C₃- C₆cycloalkylamino, Ci-C₄alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl, C₂- C₆alkoxycarbonyl, C2-C₆alkylaminocarbonyl, C₂-C₈ dialkylaminocarbonyl and C₂-C₆ trialkylsilyl; and

R₉ is hydrogen, CrC₂alkyl, C₃-C₆cycloalkyl or CrC₂haloalkyl;

In each of the preferred embodiments mentioned above, R₂ is preferably hydrogen, d- C₃alkyl, CrC₃alkylthio, CrC₃alkylsulfinyl, Ci-C₃alkylsulfonyl or Ci-C₃alkoxy; or R₂ is a three- to four- membered ring which can be partially saturated or fully saturated and can contain one heteroatom selected form the group consisting of nitrogen, oxygen and sulphur; said three- to four- membered ring system can be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, methyl and trifluoromethyl;

In each of the preferred embodiments mentioned above, R₂ is most preferably

CrC₃alkylsulfinyl or Ci-C₃alkylsulfonyl; or R₂ is a three- to four- membered ring which can be partially saturated or fully saturated and can contain one heteroatom selected form the group consisting of nitrogen, oxygen and sulphur; said three- to four- membered ring system can be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, methyl and trifluoromethyl.

A particular preferred embodiment are compounds of formula I represented by the compounds of formula 1-1

wherein

G₂, G₃ and G₄ form together with the two carbon atoms to which G₂ and G₄ are attached, an aromatic ring system; wherein

G₂ is nitrogen, N-Ci-C₄alkyl, sulpher, oxygen, or C-R₄; preferably G₂ is nitrogen, sulpher, oxygen, or C-R₄;

G₃ is nitrogen, N-Ci-C₄alkyl, sulpher, oxygen, or C-R₅; preferably G₃ is nitrogen, sulpher, oxygen, or C-R₅; G₄ is nitrogen, N-Ci-C₄alkyl, sulpher, oxygen, or C-R₆; preferably G₄ is nitrogen, sulpher, oxygen, or C-R₆; with the provisos that

a) not more than 2 substituents G can be oxygen or sulpher, and

each of R₄, R₅, and R₆ which may be the same or different, represents hydrogen, halogen, nitro, C C₃alkyl, -CONHS0₂-Ci-C₆-alkyl, -CONHS0₂N(Ci-C₆-alkyl)₂, C C₃haloalkyl, or an unsubstituted three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated.

Further particular preferred are compounds of formula I represented by the compound of formula I-2

wherein

R₂ is halogen, hydrogen or Ci-C₂alkyl;

G₃ is nitrogen, N-Ci-C₄alkyl, sulpher, oxygen, or C-R₅; preferably G₃ is nitrogen, sulpher, oxygen, or C-R₅;

G₄ is nitrogen, N-Ci-C₄alkyl, sulpher, oxygen, or C-R₆; preferably G₄ is nitrogen, sulpher, oxygen, or C-R₆; with the provisos that

a) not more than 2 substituents G can be oxygen or sulpher, and

each of R₄, R₅, and R₆ which may be the same or different, represents hydrogen, halogen, nitro, Ci-C₃alkyl, -CONHS0₂-C C₆-alkyl, -CONHS0₂N(CrC₆-alkyl)₂, C C₃haloalkyl, or an unsubstituted three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated. Further particular preferred are compounds of formula I represented by the compound of formula I-3

wherein

a) not more than 2 substituents G can be oxygen or sulpher, and

each of R₄, R₅, and R₆ which may be the same or different, represents hydrogen, halogen, nitro, CrC₃alkyl, or CrC₆haloalkyl;

R₆o represents hydrogen, halogen, CrC₆alkyl, C₃-C₆cycloalkyl, CrC₆haloalkyl, C₃- C₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy, C₃- Cedialkylaminocarbonyloxy, -CONHS0₂-C C₆-alkyl, -CONHS0₂N(C C₆-alkyl)₂ , or an unsubstituted three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated, or R₆o represents a group Ji as definded above.

Further particular preferred are compounds of formula I represented by the compounds of formula I-4

wherein

R₂ is halogen, hydrogen or CrC₂alkyl;

G₂ is nitrogen, N-CrC₄alkyl, sulpher, oxygen, or C-R₄; preferably G₂ is nitrogen, sulpher, oxygen, or C-R₄;

G₃ is nitrogen, N-CrC₄alkyl, sulpher, oxygen, or C-R₅; preferably G₃ is nitrogen, sulpher, oxygen, or C-R₅;

G₄ is nitrogen, N-CrC₄alkyl, sulpher, oxygen, or C-R₆; preferably G₄ is nitrogen, sulpher, oxygen, or C-R₆; with the provisos that

a) not more than 2 substituents G can be oxygen or sulpher, and

R₆o represents hydrogen, halogen, CrC₆alkyl, C₃-C₆cycloalkyl, CrC₆haloalkyl, C₃- C₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy, C₃- Cedialkylaminocarbonyloxy, -CONHS0₂-C C₆-alkyl, -CONHS0₂N(CrC₆-alkyl)₂, or an unsubstituted three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated.

Further preferred compounds of formula I are represented by the formula IAA

wherein

Xio is nitrogen or -C-R₂oi ; R201 is hydrogen or d-C₃alkyl; ZX is is selected from ZXi

wherein R₂₀₂ is -C(=0)-0-Ci-C₄alkyl, -C(=0)-Ci-C₄alkyl, C(CH₃)=N-0-Ci-C₄alkyl or C(=0)- N H-CrC₄halogenalkyl; and ZX₂

wherein R202 and R203 independently from each other, are hydrogen or halogen; and

wherein R₂o₄ is halogen; and ZX₅

wherein R209 is hydrogen or phenyl; and ZX₆

wherein R₂os is halogen and R₂₀6 is CrC₄alkyl; and ZX₇

wherein R₂₀7 is halogen; and ZX₈

wherein R₂os is CrC₄alkyl.

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.

For example, a compound of the formula lib, where Xa is a halogen or a triflate, can be treated with a compound of formula Ilia, where Xb is an alkyi boron (Suzuki reaction), or alkyi tin (Stille reaction) in the presence of a palladium catalyst, to give compounds of formula la where X-i , X₂ and Q are as defined in formula I (Scheme 1 ).

Scheme 1

Alternatively, a compound of the formula 1Mb, where Xc is halogen Stille reactions this type are well precedented in the literature (e.g. Branowska et al, Bioorg. Med. Chem., 3551 -3558; 2010) and are usually carried out in an inert solvent, for example dioxane or terahydrofurane, with a palladium(O) catalyst, for example tetrakis(triphenylphosphine)palladium, at a temperature between 25-150°C. When Xd or Xa is a boron alkyl ester or boronic acid, the reaction is usually carried out in the presence of a base, for example potassium carbonate, cesium carbonate, or potassium phosphate, in an inert solvent, such as dioxane, optionally in the presence of water, at temperatures between 25-150°C. Such Suzuki reactions are also well precendented in the literature, see for example J. Med. Chem., 54, 6342-6363; 2011, and US 201 1/01 12067. An alternative synthesis of compounds of formula la comprises reaction of a compound of formula lib, where Xa is H, with a compound a formula l llb, wherein Xc is chloride, bromide or iodide, most preferably bromide, using C-H activation. This methodology is well known to those skilled in the art, and has been demonstrated on similar examples using a catalytic system consisting of Pd(OAc)₂ and 1 ,10-phenanthroline, in the presence of a base, for example cesium carbonate, at temperatures between 25-150°C, preferably 140 °C (see Yu et al, J. Am. C em. Soc, 133, 19090, 2011). This is shown in scheme 2:

Scheme 2.

C-H activation

reaction

Base, e.g. CS2CO3 Compounds of formula I , where X₂ is CR₂ can be prepared as shown in scheme 3.

Scheme 3:

In scheme 3, compounds of formula IVa can be condensed with compounds of formula Va by methods to those skilled in the art or as described in Helv. Chim. Acta, 820, 1945 and DE 22221647 to give compounds of formula Via, where R₂ and Xi are defined as described for formula I. Compounds of formula Via can be coupled to compounds of formula Qia, Q₂a, and Q₃a, wherein Gi, G₂, G₃, G₄, X3, X₄, Xs, Χβ, X7 and X₈ are defined as described for formula I, and Xe, Xf and Xg are leaving groups such as halogen or triflate using C-H activation methodology. Here, a compound of formula Va is treated with a compound of formula Qia, Q₂a, or Q₃a, in an inert solvents, such as DMF, with a palladium catalyst, such as Pd(OAc)₂ , with an appropriate ligand, such as tri.tert-butyl phosphine, optionally in the presence of a base such as potassium carbonate, at temperatures between 25-150°C. Such C-H activation technology is known to those skilled in the art, and has been described in , for example, e.g. L. Ackermann et al. Angew. C em. Int Ed. ,48, 9792, 2009, J. Q. Yu, Z. Shi Eds., Topics in Current Chemistry, 2010, vol. 292, Springer, or US 201 1/212949A1 .

A further synthesis of compounds of formula I is illustrated in scheme 4. Scheme 4:

In scheme 4, a compound of formula Via is brominated, for example with Br₂ in

dichloromethane, and the obtained compound of formula VII converted to a compound of formula VII by, for example, treatment with a hexaalkyi distannane compound, for example hexa -n-butyl distannane, or diboryl ester, for example bis(pinacolato)diboron, in the presence of a palladium catalyst, for example 1 ,1 '-Bis(diphenylphosphino)ferrocene- palladium(ll)dichloride dichloromethane complex, in an inert solvent to give a compound of formula VIII. Such reactions are well precedented in the literature, see for example U.S. Pat. Appl. 20100160303 (Xh is B(OR)₂) and Kuoei al, J. Med. Chem, 1886, 2005 (Xh is Tri- n-butyl tin). Compounds of formula VIII, wherein X-i and R₂ are as described for formula I, Xh is a trialkyl stannane, for example tri-n-butyl stannane, or a boron ester, for example pinacolborane, can be converted to compounds of formula lb, lc, and Id by Suzuki or Stille couplings, i.e. by treatment with a Pd(l l) catalyst, for example Palladium(ll)acetate in the presence of a phosphine ligand, for example tri-ortho-toluene phosphine, and a base, for example potassium carbonate, in a polar diprotic solvent, for example DMF. Such examples of Suzuki and Stille thiazoles are known in the literature see for example Bioorg. Med.

Chem. , 12, 5579, 2004 (Stille coupling) and Bioorg. Med. Chem. Letts, 18, 321 1 , 2008

(Suzuki coupling). Analogously, compounds of formula I, wherein X₂ is N, can be prepared as shown in scheme 5.

Scheme 5

In scheme 5, a compound of formula IX is treated with formic acid to generate a compound of formula X analogously to methods described in Bull. Soc. Chem. Belg., 106, 109, 1997. The required thiadiazole of formula XI, is obtained by treatment, for example, Lawesssons reagent in an inert solvent, for example toluene, as described for example in J. Ind. Chem. , 509, 1970. Coupling of compounds of formula XI to compounds of formula Qi_a,

and Q_3a, wherein d , G2,G₃ ,G₄ ,Χβ, X₄, Xs, Χβ, X7 and X₈ are defined as described for formula I , and Xe, Xf and Xg are leaving groups such as halogen or triflate using C-H activation

methodology, analogously to that described in scheme 3.

A further method of preparation of compounds of formula I, wherein X₂ is N, and Q is as defined in formula I, is depicted in scheme 6.

Scheme 6:

Base, e.g.

Et3N, cat. e.g DMAP,

CH2CI2 In scheme 6, a hydrazide of formula IX is coupled to an acid of formula Xlla, wherein Q is as described in formula I, or to a compound of formula Xllb, wherein Xi is a leaving group, for example halogen, using coupling methodology known to those skilled in the art and as described in March's Advanced Organic Chemistry, 6^th edition, Wiley, New York, 2007. More detailed syntheses of compounds of formula IAA are shown in the following schemes. Scheme 7:

In scheme 7, R₀i and R₀2 are H or C1-C4 Alkyl. Compounds of formula Yi can be treated with a vinyl Grignard of formula Y₂ to give azaindoles of formula Y₃. Such Bertoli Indole syntheses are well precedented in the literatute (see J. Org. C em., 2002, 67 , pp 2345-2347). After alkylation of compounds of formula Y₃ in the presence of base, for example sodium hydride, in an aprotic solvent, such as dimethyl formamide, compounds of formula Y₄ are

obtained,wherein R₀i and R₀2 are H or CrC₄Alkyl.

Palladium can be selectively inserted into the C-CI bond at the 7 position of compounds Y₄ allowing for example as shown in scheme 8 , compounds of formula Y₈ to be obtained by reacting Y₄ under carbon monoxide between 1 -20 bar, in an alcohol, such as methanol, in the presence of a base, such as triethylamine at temperatures between 25-150°C). The catalyst used in such a reaction is for example ,dichlorobis(benzonitrile)palladium(ll), in the presence of a bidentate phosphine ligand such such as 4,5-Bis(diphenylphosphino)-9,9- dimethylxanthene (Xantphos). Such carbonylation reactions have been described for example in WO2012079583. Stille coupling of Y₈ with a compound of formula Villa leads to a compound of formula ZX1 c, wherein R₀i and R₀2 are H or CrC₄Alkyl. . The ester group of ZXIa can be hydrolysed to the acid ZXIb and converted to the amide ZXIc according to methods known to thoese skilled in the art. Alternatively, Y₄ can be selectively converted to a compound of formual ZX7a, via Stille coupling according to methods described in for Haemmerle, Johanna et al, Synlett, 2975-2978, 2007.

Scheme 8:

in Scheme 9, compounds of formula Y₆ can be obtained by treatment of a compound of formula Y₄ with a compound of formula Y₅ under Stille reaction conditions known to those skilled in the art and described in, for example,. Branowska et al, Bioorg. Med. Chem., 3551 - 3558; 2010. Acidic hydrolysis of compounds of formula Y₆ with an aquous acid, for example hydrochloric acid, in the presence of a water miscible co-solvent, for example acetone leads to compounds of formula Y₇ wherein R₀i and R₀₂ are H or Ci-C₄alkyl. Reaction of compounds of the formula Y₇ with a compound of formula Villa under Stille coupling conditions previously, leads to compounds of formula ZXId which can be condensed with either a compound of formula ZY^ or ZY₂, optionally in the presence of a base, for example potassium carbonate, or a dehydrating agent, such as 4A° Molecular sieves in an inert solvent, such as tetrahydrofuran, or hexane, or protic solvents, for example ethanol, at temperatures between 25°C and 150°C, preferably between 25°C and 150°C. Such chemistries are well known in the literature, for example for compounds of formula ZXIe, obtained upon reaction with compounds of formula ZY-i, where ZY-i is N-OR₆₂, with compounds of formula ZX1 d, a whole range of methods are known to those skilled in the art as exemplified for example in "Reaktionen der organischen Synthese", Cesare Ferri, Georg Thieme Verlag, Stuttgart, 1978, p. 540-541.

Similarly, compounds of formula ZXIf can be obatained by reaction of compounds of formula ZXId with compounds of formual ZY₃, where ZY₃ is N-NR₆2R63, wherein R₆₂ is a previously described and R₆3 is H, or N-Ci-C₄alkyl, according to methods known by those skiled in the art and more specifically as described in "Reaktionen der organischen Synthese", Cesare Ferri, Georg Thieme Verlag, Stuttgart, 1978, p. 537-538.

Compounds of formula ZX₆ can be prepared according to scheme 10:

Scheme 10:

Compounds of formula Y₈ and Y₉ can be prepared according to methods known in the literterature (see Journal of Heterocyclic Chemistry, 14, 435-8, 1977). Stille coupling of the intermediate Y-|₀ with a compound of formul Vi lla, according to methods previously described, leads to compounds of formula ZX₆-, where R₂o6 is as previously defined.

Compounds of Formula ZX5 can be prepared according to scheme 1 1 .

Scheme 1 1 :

protic solvent, e.g. MeOH

Villa

X Pd(OAc)₂ 10 mol%

Wherein X

Cs₂C0₃

Solvent e.g. PhCI 160°C.

R209susbtituted phenyl, 2-,3- or 4-pyridyl

In scheme 1 1 , 2,6-Dichloro-nicotinealdehyde (Yn) is reacted with methyl hydrazine in a protic solvent, for example methanol, at temperatures between 25-140°C in a microwave. The resultant compound Y12 is then coupled with a compound of formula Villa under standard Stille coupling conditions discussed previously. The resultant compound ZX5a can then undergo C-H activation with a compound of X-R209 , wherein X is bromine or iodine and R209 is optionally substituted phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl, in the presence of a catalytic palladium source, preferably Pd(OAc)₂, and an alkali metal base, preferably Cs₂C0₃, and a catalytic bidentate ligand, for example phenanthroline, in an inert solvent, for example, xylene or chlorobenzene, at temperatures between 50-160°C, preferably 160°C, to give compounds of formula ZX5b, wherein R209 is optionally substituted phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl.

The reactants can be reacted in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines.

Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine,

triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine,

benzyltrimethylammonium hydroxide and 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

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

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

A compound of formula I can be converted in a manner known per se into another compound of formula I by replacing one or more substituents of the starting compound of formula I in the customary manner by (an)other substituent(s) according to the invention.

Depending on the choice of the reaction conditions and starting materials which are suitable in each case, it is possible, for example, in one reaction step only to replace one substituent by another substituent according to the invention, or a plurality of substituents can be re- placed by other substituents according to the invention in the same reaction step.

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

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

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

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

The compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case. Diastereomer mixtures or racemate mixtures of compounds of formula I, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diasteromers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography. Enantiomer mixtures, such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high- performance liquid chromatography (HPLC) on acetyl celulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is com- plexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the diastereomers, from which the desired enantiomer can be set free by the action of suitable agents, for example basic agents. Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereose- lective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.

N-oxides can be prepared by reacting a compound of the formula I with a suitable oxidizing agent, for example the H₂0₂/urea adduct in the presence of an acid anhydride, e.g.

trifluoroacetic anhydride. Such oxidations are known from the literature, for example from J. Med. Chem., 32 (12), 2561 -73, 1989 or WO 00/15615.

It is advantageous to isolate or synthesize in each case the biologically more effective isomer, for example enantiomer or diastereomer, or isomer mixture, for example enantiomer mixture or diastereomer mixture, if the individual components have a different biological activity.

The compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.

The compounds of formula I according to the invention are preventively and/or curatively valuable active 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 or representatives of the order Acarina. The insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i. e. 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%.

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, Euchistus spp., Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Lep- tocorisa spp., Lygus spp, Margarodes spp, Murgantia histrionic, Neomegalotomus spp, Nesidiocoris tenuis, Nezara spp., Nysius simulans, Oebalus insularis, Piesma spp.,

Piezodorus spp, Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp. , Thyanta spp , Triatoma spp., Vatiga illudens;

Acyrthosium pisum, Adalges spp, Agalliana ensigera, Agonoscena targionii, Aleurodicus spp, Aleurocanthus spp, Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp, Brachycaudus spp,

Brevicoryne brassicae, Cacopsylla spp, Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp, Cofana spectra, Cryptomyzus spp, 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, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Pogonomyrmex spp, Slenopsis invicta, Solenopsis spp. and Vespa spp.;

from the order Isoptera, for example,

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

from the order Lepidoptera, for example,

Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp, Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp, Crocidolomia binotalis, Cryptophlebia 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, Grapholita 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 gossypiela, Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Pseudoplusia spp, Rachiplusia nu, Richia albicosta, Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Sylepta derogate, Synanthedon spp., Thaumetopoea spp., Tortrix spp., 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, especi- ally 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, latex plants and ornamentals.

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 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 δ-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 δ-endotoxins, for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , 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 Cry1 Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1 Ab 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 CrylAc 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); Nature- Gard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt1 1 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. Bt1 1 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 Tervuren, B-1 150 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-1 150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1 160 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-1 150 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 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 CrylAb 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 fur

Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).

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 storerooms 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. 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 invention therefore also relates to pesticidal compositions such as emulsifiable concentrates, suspension concentrates, microemulsions, oil dispersibles, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances, which comprise - at least - one of the active ingredients according to the invention and which are to be selected to suit the intended aims and the prevailing circumstances.

In these compositions, the active ingredient is employed in pure form, a solid active ingredi- 5 ent for example in a specific particle size, or, preferably, together with - at least - one of the auxiliaries conventionally used in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants).

Examples of suitable solvents are: unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably the fractions C₈ to Ci₂ of alkylbenzenes, such as xylene mixtures, ali o kylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols such as ethanol, propanol or butanol, glycols and their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-me- 15 thylpyrrolid-2-one, dimethyl sulfoxide or Ν,Ν-dimethylformamide, water, unepoxidized or epoxidized vegetable oils, such as unexpodized or epoxidized rapeseed, castor, coconut or soya oil, and silicone oils.

Solid carriers which are used for example for dusts and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite. To im- 20 prove the physical properties, it is also possible to add highly disperse silicas or highly disperse absorbtive polymers. Suitable particulate adsorptive carriers for granules are porous types, such as pumice, brick grit, sepiolite or bentonite, and suitable non-sorptive carrier materials are calcite or sand. In addition, a large number of granulated materials of inorganic or organic nature can be used, in particular dolomite or comminuted plant residues.

25

Suitable surface-active compounds are, depending on the type of the active ingredient to be formulated, non-ionic, cationic and/or anionic surfactants or surfactant mixtures which have good emulsifying, dispersing and wetting properties. The surfactants mentioned below are only to be considered as examples; a large number of further surfactants which are conven- 30 tionally used in the art of formulation and suitable according to the invention are described in the relevant literature.

Suitable non-ionic surfactants are, especially, polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, of saturated or unsaturated fatty acids or of alkyl phenols which may contain approximately 3 to approximately 30 glycol ether groups and approximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatic hydrocarbon radical or approximately 6 to approximately 18 carbon atoms in the alkyl moiety of the alkyl phenols. Also suitable are water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopo- lypropylene glycol or alkyl polypropylene glycol having 1 to approximately 10 carbon atoms in the alkyl chain and approximately 20 to approximately 250 ethylene glycol ether groups and approximately 10 to approximately 100 propylene glycol ether groups. Normally, the abovementioned compounds contain 1 to approximately 5 ethylene glycol units per propylene glycol unit. Examples which may be mentioned are nonylphenoxypolyethoxyethanol, castor oil polyglycol ether, polypropylene glycol/polyethylene oxide adducts, tributylpheno- xypolyethoxyethanol, polyethylene glycol or octylphenoxypolyethoxyethanol. Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate. The cationic surfactants are, especially, quarternary ammonium salts which generally have at least one alkyl radical of approximately 8 to approximately 22 C atoms as substituents and as further substituents (unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates.

Examples are stearyltrimethylammonium chloride and benzylbis(2-chloroethyl)ethyl- ammonium bromide.

Examples of suitable anionic surfactants are water-soluble soaps or water-soluble synthetic surface-active compounds. Examples of suitable soaps are the alkali, alkaline earth or (un- substituted or substituted) ammonium salts of fatty acids having approximately 10 to approximately 22 C atoms, such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which are obtainable for example from coconut or tall oil; mention must also be made of the fatty acid methyl taurates. However, synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates. As a rule, the fatty sulfonates and fatty sulfates are present as alkali, alkaline earth or (substituted or unsubstituted) ammonium salts and they generally have an alkyl radical of approximately 8 to approximately 22 C atoms, alkyl also to be understood as including the alkyl moiety of acyl radicals; examples which may be mentioned are the sodium or calcium salts of lignosulfonic acid, of the dodecylsulphuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulphuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulphonyl groups and a fatty acid radical of approximately 8 to approximately 22 C atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of decylbenzenesulfonic acid, of dibutyl- naphthalenesulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensate. Also possible are, furthermore, suitable phosphates, such as salts of the phosphoric ester of a p- nonylphenol/(4-14)ethylene oxide adduct, or phospholipids.

As a rule, the compositions comprise 0.1 to 99%, especially 0.1 to 95%, of active ingredient and 1 to 99.9%, especially 5 to 99.9%, of at least one solid or liquid adjuvant, it being possible as a rule for 0 to 25%, especially 0.1 to 20%, of the composition to be surfactants(% in each case meaning percent by weight). Whereas concentrated compositions tend to be preferred for commercial goods, the end consumer as a rule uses dilute compositions which have substantially lower concentrations of active ingredient. Preferred compositions are composed in particular as follows (% = percent by weight):

Emulsifiable concentrates:

active ingredient: 1 to 95%, preferably 5 to 20%

surfactant: 1 to 30%, preferably 10 to 20 %

solvent: 5 to 98%, preferably 70 to 85%

Dusts:

active ingredient: 0.1 to 10%, preferably 0.1 to 1 %

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%

surfactant: 1 to 40%, preferably 2 to 30%

Wettable powders:

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

surfactant: 0.5 to 20%, preferably 1 to 15%

solid carrier: 5 to 99%, preferably 15 to 98%

Granulates:

active ingredient: 0.5 to 30%, preferably 3 to 15%

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

"M.p." means melting point in °C.

Example P1 : 4-[4-methyl-2-(3-pyridyl)thiazol-5-yllthieno[3,2-clpyridine (Compound G-19, Table 7).

A mixture of 4-methyl-2-(3-pyridyl)thiazole (88mg, 0.48mmol, prepared as described in WO 2010 006713), 4-chlorothieno[3,2-c]pyridine (70mg, 0.4mmol, prepared as described in J. Med. C em, 32,1 147, 1989) potassium acetate (48mg, 0.48mmol) in 3ml of

dimethylacetamide was treated at ambient temperature with [1 ,2- bis(diphenylphosphino)ethane]palladium(ll) dichloride (12mg, 0.02mmol) and the mixture then irradiated at 170°C for 30min in a microwave. LCMS analysis showed incomplete reaction and thus the mixture was heated for a further 45min at 100°C. After this time the recation mixture was diluted with water and extracted with ethyl acetate. The organic phase was washed with brine, dried over anhydrous Mg_?S04 and concentrated in vacuo.

Purification by flash chromatography, eluting with 100:0 to 80:20 cyclohexane:ethylacetate gradient gave 4-[4-methyl-2-(3-pyridyl)thiazol-5-yl]thieno[3,2-c]pyridine (9mg) in form of white crystals. Example P2: 4-r5-(3-pyridyl)-1 ,3,4-thiadiazol-2-yllthienor3,2-clpyridine (Compound G-25, Table 7).

A mixture of 2-(3-pyridyl)-1 ,3,4-thiadiazole (177mg, 1 .04 mmol, prepared as described in WO 2010/006713), 4-chlorothieno[3,2-c]pyridine (150mg, 0.867mmol, prepared as described in J. Med. Chem, 32,1 147, 1989) and potassium acetate (104mg, 0.867mmol) in 5ml of dimethylacetamide was treated at ambient temperature with [1 ,2- bis(diphenylphosphino)ethane]palladium(ll) dichloride (25.5mg, 0.0433mmol), and the mixture then irradiated at 180°C for 60min in a microwave. LCMS analysis showed incomplete reaction and thus the mixture was heated for a further 45min at 200°C. The recation mixture was then diluted with water and extracted with ethyl acetate. The organic phase was washed with brine, dried over anhydrous Mg₂S04 and concentrated in vacuo. Purification by flash chromatography, eluting with 100:0 to 0:100 cyclohexane:ethylacetate gradient gave the title compound (6mg) as a pale yellow solid. Example P3: 5-(5-chloro-1 -methyl-pyrrolo[2,3-clpyridin-7-yl)-4-methyl-2-(3-pyridyl)thiazole (Compound N-26):

Step A: 5,7-dichloro-1 H-pyrrolo[2,3-clpyridine:

A solution of 2,6-dichloro-3-nitro-pyridine (1 1 g, 56.998 mmol) in dry tetrahydrofurane (350 ml_). was cooled to -78°C and treated dropwise with bromo(vinyl)magnesium (1 M in THF 200 ml_, 199.5 mmol). The reaction mixture was allowed to warm to -20°C and stirred for 1 hour at this temperature. The reaction mixture was quenched with 200 ml of aqueous NH₄CI and extracted with ethylacetate and the combined organic layer dried over Na₂S0₄, filtered and evaporated under vacuum at 50°C. Purification by Combi flash chromatography with a column of 24g and a gradient cyclohexane:0-70% ethyl acetate gave the title compound as a yellow foam (3.7 g, 35%).

Step B: 5,7-dichloro-1 -methyl-pyrrolo[2,3-clpyridine:

A solution of 5,7-dichloro-1 H-pyrrolo[2,3-c]pyridine (2 g, 10.693 mmol) in dry N,N- dimethylformamide (50 mL) was treated with sodium hydride (0.77 g, 16.04 mmol) at ambient temperature and reaction stirred for 15 min at this temperature. The reaction mixture was cooled to 0°C and iodomethane (1 mL, 16.04 mmol) was added, and the mixture allowed to stir 18 hours at ambient temperature. The reaction mixture was then quenched with NH₄CI saturated solution, extracted with ethyl acetate (three times), and the combined organic layer was dried over Na₂S0₄, filtered and evaporated under vacuum. Purification by Combi flash chromatography with a column of 24g and a gradient cyclohexane:0-100% ethyl acetate to give the title compound as a yellow solid (1.8 g, 84%).

Step C: tributyl-[4-methyl-2-(3-pyridyl)thiazol-5-yllstannane:

In a dry flask under argon, 5-bromo-4-methyl-2-(3-pyridyl)thiazole (15.00 g, 55.85 mmol) was dissolved in THF (140 mL), and with cooling to keep the temperature at 25°-30°C, treated dropwise with /^'-PrMgCI'LiCI (TurboGrignard, 60 mL, 78.19 mmol,). The resulting mixture was allowed to stir at ambient temperature for 1 hour. The reaction mixture was then cooled to 10°C, and tri-n-butyl tin chloride (19 mL, 67.02 mmol) was added over 5 min. The reaction was stirred for 30min at ambient temperature and then at reflux (66°C) for 18 hours. The reaction mixture was quenched with saturated NH₄CI solution and diluted with ethyl acetate. Then aqueous layer was extracted 3 times with ethyl acetate and the combined organic layers washed with brine, dried over MgS0₄, filtrated and evaporated. Purification by Combi flash chromatography with a column of 24g and a gradient cyclohexane:0-100% ethyl acetate to give the title compound as a yellow solid (9.17 g, 26%).

Step D: 5-(5-chloro-1 -methyl-pyrrolo[2,3-clpyridin-7-yl)-4-methyl-2-(3-pyridyl)thiazole

(Compound N-26): A mixture of tributyl-[4-methyl-2-(3-pyridyl)thiazol-5-yl]stannane (0.204 g, 0.438 mmol) and 5,7-dichloro-1 -methyl-pyrrolo[2,3-c]pyridine (0.08 g, 0.4 mmol) in 1 ,4-dioxane (2ml_) was flushed with argon for 10min and then tetrakis(triphenylphosphine)palladium(0) (0.046 g, 0.04 mmol) added and the orange solution was irradiated in the microwave at 160°C for 40 min. The reaction mixture was then partitioned between ethyl acetate and water. The aqueous layer was extracted 3 times with ethyl acetate and the combined organic layers dried over Na₂S0₄, filtered and evaporated under vacuum. Purification by Combi flash chromatography with a column of 12g and a gradient of dichloromethane:0-10% methanol to give the title compound as a yellow foam (65 mg, 38%). Example P4: 1 -[1 -methyl-5-[4-methyl-2-(3-pyridyl)thiazol-5-yllpyrrolo[2,3-clpyridin-7- yllethanone (Compound D-28):

Step A: 5-chloro-7-(1 -ethoxyvinyl)-1 -methyl-pyrrolo[2,3-clpyridine:

A mixture of 5,7-dichloro-1 -methyl-pyrrolo[2,3-c]pyridine (0.25 g, 1 .24 mmol, preparation described above) and tributyl(1 -ethoxyvinyl)stannane (1 .05 equiv., 0.49 g, 1 .306 mmol) in dioxane (2 ml_), was flushed with argon for a few minutes and tetrakis(triphenylphosphine)palladium(0) (0.145 g, 0.124 mmol) was added at ambient temperature. The reaction mixture was irradiated in the microwave at 160°C for 20 min. The reaction mixture was cooled down to ambient temperature and quenched with NaHC0₃ sat. aq (4 mL) and NaOH 1 N (4 ml_). This mixture was vigorously stirred for 2 hours and then extracted with ethyl acetate (3X) and the combined organic layers washed with brine, dried over MgS0₄, filtered and evaporated under vacuum. Purification by Combi flash chromatography with a column of 12g and a gradient cyclohexane:0-60% ethylacetate gave the title compound as a yellow foam (168 mg, 57%)

Step B: 1 -(5-chloro-1 -methyl-pyrrolo[2,3-clpyridin-7-yl)ethanone:

To a solution of 5-chloro-7-(1 -ethoxyvinyl)-1 -methyl-pyrrolo[2,3-c]pyridine (0.16 g, 0.676 mmol) in acetone (7 mL, 0.676 mmol) was added HCI 1 N (1 .4 mL) and the solution was stirred for 18 hours at ambient temperature. The reaction mixture was then quenched with saturated aqueous NaHC0₃ and the aqueous layer was extracted 2 times with ethyl acetate at pH 9. The combined organic layer were washed with brine, dried over anhydrous Na₂S0₄, filtered and evaporated under vacuum to give the title compound as a yellow solid (150 mg, 99%).

Step C: 1 -[1 -methyl-5-[4-methyl-2-(3-pyridyl)thiazol-5-yllpyrrolo[2,3-clpyridin-7-yllethanone (Compound D-28):

A mixture of tri-n-butyl-[4-methyl-2-(3-pyridyl)thiazol-5-yl]stannane (0.318 g, 0.685 mmol) and 1 -(5-chloro-1 -methyl-pyrrolo[2,3-c]pyridin-7-yl)ethanone (0.130 g, 0.623 mmol) in 1 ,4-dioxane (3 mL) was flushed with argon for 10 min and then tetrakis(triphenylphosphine)palladium(0) (0.072 g, 0.0623 mmol) was added and the orange solution was irradiated in the microwave at 160°C for 40 min. The reaction mixture was dissolved in ethylacetate and water. The aqueous layer was extracted 3 times with ethyl acetate and the combined organic layer dried over Na₂S0₄, filtered and evaporated under vacuum. Purification by Combi flash chromatography with a column of 12g and a gradient cyclohexane:0-100% ethyl acetate to give the title compound as a yellow foam (81 mg, 37%).

Example P5: N-ethoxy-1 -[1 -methyl-5-[4-methyl-2-(3-pyridyl)thiazol-5-yllpyrrolo[2,3-clpyridin- 7-yllethanimine (Compound D-29)

To a solution of 1 -[1 -methyl-5-[4-methyl-2-(3-pyridyl)thiazol-5-yl]pyrrolo[2,3-c]pyridin-7- yl]ethanone (0.054g, 0.15 mmol)in ethanol (3 mL) were added potassium carbonate (0.032 g, 0.23 mmol) and O-ethylhydroxylamine hydrochloride (0.016 g, 0.16 mmol). The cloudy solution was stirred for 18 hours at ambient temperature, and then concentrated in vacuo. Purification by Combi flash chromatography with a column of 4 g and a gradient dichloromethane:0-20% methanol gave the title compound as a yellow solid (0.021 g, 35%).

Example P6: methyl 1 -methyl-5-[4-methyl-2-(3-pyridyl)thiazol-5-yllpyrrolo[2,3-clpyridine-7- carboxylate (Compound D-27):

Step A: methyl 5-chloro-1 -methyl-pyrrolo[2,3-clpyridine-7-carboxylate: A mixture of 5,7-dichloro-1 -methyl-pyrrolo[2,3-c]pyridine (0.6 g, 2.99 mmol) , methanol (8 mL), triethylamine (0.395 g, 3.8795 mmol), Xantphos (0.0177764 g, 0.0298 mmol) and DibenzonitrilePdCI₂ (0.012 g, 0.03 mmol) were transferred to an autoclave and heated at 130°C under 20 bar of CO for 12hours. The crude reaction mixture was evaporated and purified by Combi flash chromatography with a column of 12g and a gradient cyclohexane: 0- 100% ethyl acetate to give the title compound as a beige solid (264 mg, 40%).

Step B: methyl 1 -methyl-5-[4-methyl-2-(3-pyridyl)thiazol-5-yllpyrrolo[2,3-clpyridine-7- carboxylate (Compound D-27):

A mixture of tri-n-butyl-[4-methyl-2-(3-pyridyl)thiazol-5-yl]stannane (0.342 g, 0.734 mmol) and methyl 5-chloro-1 -methyl-pyrrolo[2,3-c]pyridine-7-carboxylate (0.15 g, 0.67 mmol) was dissolved in 1 ,4-dioxane (3 mL, 0.67 mmol). This yellow solution was flushed with argon for 10 min, treated with tetrakis(triphenylphosphine)palladium(0) (0.077 g, 0.067 mmol) and the orange solution was irradiated at 160°C for 40min in the microwave. The reaction mixture was dissolved in ethyl acetate and water and the aqueous layer was extracted 3 times with ethyl acetate. The combined organic layers were dried over Na₂S0₄, filtered and evaporated under vacuum. Purification by Combi flash chromatography with a column of 12g and a gradient cyclohexane: 0-100% ethyl acetate to give the title compound as a beige solid (71 mg, 29%).

Example P7: 1 -methyl-5-r4-methyl-2-(3-pyridyl)thiazol-5-yll-N-(2,2,2-trifluoroethyl)pyrrolor2,3- clpyridine-7-carboxamide (Compound D-30):

Step A: 1 -methyl-5-[4-methyl-2-(3-pyridyl)thiazol-5-yllpyrrolo[2,3-clpyridine-7-carboxylic acid:

Compound D-27 (0.05 g, 0.1372 mmol) was dissolved in a mixture of THF and H₂0 3:1 (4 mL) and LiOH.H₂0 (0.009 g, 0.2058 mmol) was added at ambient temperature. The reaction mixture was stirred one night at ambient temperature, and then treated with 1 mL of HCI 1 N (pH 1 ), and the solvent was evaporated under vacuum at 55°C to give the title compound with LiCI salt (65 mg, 135%).

Step B: 1 -methyl-5-r4-methyl-2-(3-pyridyl)thiazol-5-yll-N-(2,2,2-trifluoroethyl)pyrrolor2,3- clpyridine-7-carboxamide (Compound D-30):

1 -methyl-5-[4-methyl-2-(3-pyridyl)thiazol-5-yl]pyrrolo[2,3-c]pyridine-7-carboxylic acid (0.065g, 0.178 mmol) was dissolved in dichloromethane (5 mL) and treated with 1 -Ethyl-3-(3- dimethylaminopropyl)carbodiimide (0.038g, 0.196 mmol), 2,2,2-Trifluoroethylamine hydrochloride (0.027g, 0.196 mmol), benzohydroxytriazole (0.027g, 0.196 mmol) and DMAP (0.033 g, 0.267 mmol). The reaction mixture was stirred for 18 hours at ambient temperature and then diluted with water and dichloromethane. The organic layer was washed successively with water and once with brine, dried over MgS0₄, filtered and concentrated in vacuo. Purification by Combi flash chromatography with a column of 12 g and a gradient dichloromethane:0-10% ethyl acetate gave the title compound as a beige solid (20 mg, 26%) Example P8: 5-(1 ,7-dimethylpyrrolo[3,2-blpyridin-5-yl)-4-methyl-2-(3-pyridyl)thiazole

(Compound P-4):

Step A: 5-chloro-7-methyl-1 H-pyrrolo[3,2-blpyridine:

2-chloro-4-methyl-5-nitro-pyridine (5 g, 28.97 mmol) was dissolved in dry tetrahydrofurane (200 mL) and the solution was cooled to

-78°C. Then bromo(vinyl)magnesium (1 M in THF, 100 mL, 101 .4075 mmol) was added dropwise and the reaction mixture allowed to warm to -20°C and stirred 2 hours. After this time, the reaction mixture was quenched with 200 ml of aqueous NH₄CI and the mixture obtained was diluted with ethyl acetate. The aqueous layer was extracted 3 times with ethyl acetate and the combined organic layers dried over Na₂S0₄, filtered and evaporated under vacuum at 50°C. Purification by Combi flash chromatography with a column of 80 g and a gradient cyclohexane:0-50% ethyl acetate and finally crystallization from ether gave the title compound as orange solid (0.86 g, 18%).

Step B: 5-chloro-1 ,7-dimethyl-pyrrolo[3,2-blpyridine:

A solution of 5-chloro-7-methyl-1 H-pyrrolo[3,2-b]pyridine (0.86 g, 5.16 mmol) in dry N,N- dimethylformamide (30 mL), was treated at rt with sodium hydride (0.37 g, 7.74 mmol). After stirring for 15 min, the reaction mixture was cooled to 0°C and iodomethane (0.48 mL, 7.75 mmol) was added. Upon completion, the mixture partitioned between ethyl acetate and NH₄CI, the aqueous layer was extracted 3 times with ethyl acetate and the combined organic layers dried over Na₂S0₄, filtered and concentrated in vacuo. Purification by Combi flash chromatography with a column of 12 g and a gradient cyclohexane:0-100% ethyl acetate gave the title compound as a yellow solid (0.817 g, 88%).

Step C: 5-(1 ,7-dimethylpyrrolo[3,2-blpyridin-5-yl)-4-methyl-2-(3-pyridyl)thiazole (Compound P-4):

A mixture of tri-n-butyl-[4-methyl-2-(3-pyridyl)thiazol-5-yl]stannane (0.255 g, 0.55 mmol) and 5-chloro-1 ,7-dimethyl-pyrrolo[3,2-b]pyridine (0.09 g, 0.5 mmol) in 1 ,4-dioxane (3 mL) was flushed with argon for 10 min and treated with tetrakis(triphenylphosphine)palladium(0) (0.058 g, 0.05 mmol). The orange solution was then irradiated in the microwave at 160°C for 180 min. The reaction mixture was dissolved in ethyl acetate and water. The aqueous layer was extracted 3 times with ethyl acetate and the combined organic layers dried over Na₂S0₄, filtered and concentrated in vacuo. Purification by Combi flash chromatography with a column of 12g and a gradient dichloromethane:0-10% methanol gave the title compound as a yellow foam (15 mg, 10%).

Example P9: (6-chloro-1 -methyl-pyrrolo[3,2-clpyridin-4-yl)-4-methyl-2-(3-pyridyl)thiazole (Compound I-28):

Step A: 4,6-dichloro-1 H-pyrrolor3,2-clpyridine:

2,6-dichloro-4-nitro-pyridine (1 1 g, 57 mmol) was dissolved in dry tetrahydrofurane (300 ml_), cooled to -78°C and treated dropwise with bromo(vinyl)magnesium (1 M in THF, 200 ml_, 200 mmol). The reaction was allowed to react at this temperature for 1 hour and then allowed to warm to -20°C. The reaction mixture was then quenched with 200 ml of aqueous NH₄CI and the mixture obtained was partitioned in ethyl acetate. The aqueous layer was extracted 3 times with 200 ml of ethyl acetate and the combined organic layer dried over Na₂S0₄, filtered and concentrated in vacuo. Purification by Combi flash chromatography with a column of 120g and a gradient cyclohexane:0-100% ethyl acetate, and then with a column of 40 g and a gradient dichloromethane:0-10% ethyl acetate gave the title compound as brown solid (0.150 g, 1 .4%).

Step B: 4,6-dichloro-1 -methyl-pyrrolo[3,2-clpyridine:

A solution of 5-chloro-7-methyl-1 H-pyrrolo[3,2-b]pyridine (0.15 g, 0.80 mmol) in dry N,N- dimethylformamide (4 mL) was treated with sodium hydride (0.0577 g, 1 .20 mmol) at ambient temperature and the mixture was stirred 15 min. The suspension was cooled to 0°C and iodomethane (0.07 mL, 1 .20 mmol) was added. The reaction was stirred overnight at ambient temperature. Aqueous work up, extracting with ethyl acetate gave the crude product which was purified by Combi flash chromatography with a column of 24 g and a gradient cyclohexane:0-100% ethyl acetate to yield the title compound as a yellow solid (0.100 g, 62%).

Step C: 5-(6-chloro-1 -methyl-pyrrolo[3,2-clpyridin-4-yl)-4-methyl-2-(3-pyridyl)thiazole

(Compound I-28): A mixture of tri-n-butyl-[4-methyl-2-(3-pyridyl)thiazol-5-yl]stannane (0.204 g, 0.438 mmol) and 4,6-dichloro-1 -methyl-pyrrolo[3,2-c]pyridine (0.08 g, 0.39791 mmol) in 1 ,4-dioxane (2 rmL, 0.39791 mmol) was flushed with argon for 10 min and tetrakis(triphenylphosphine)palladium(0) (0.046 g, 0.04 mmol) was added and the orange solution was irradiated in the microwave at 160°C for 40 min. The reaction mixture was dissolved in ethyl acetate and water, the aqueous layer extracted 3 times with ethyl acetate and the combined organic layers dried over Na₂S0₄, filtered and concentrated in vacuo. Purification by Combi flash chromatography with a column of 12 g and a gradient dichloromethane:0-10% methanol to give the title compound as a yellow foam (75 mg, 55%)

Example P10: 4-methyl-5-(1 -methylpyrazolo[3,4-blpyridin-6-yl)-2-(3-pyridyl)thiazole

(Compound K-1 ):

Step A: 6-chloro-1 -methyl-pyrazolo[3,4-blpyridine:

A solution of 2,6-dichloro-nicotinealdehyde (8g, 44.1 mmol) and methyl hydrazine (2.44 rmL, 46.3 mmol) in methanol (160 ml) was irradiated in the microwave for 18 hr at 135°C. The mixture was evaporated and the residue was diluted with ethyl acetate and sat. aqueous NaHC0₃. The aqueous layer was extracted 2 times with ethyl acetate and the combined organic layers washed with brine, dried over MgS0₄, filtrated and concentrated in vacuo. Purification by Combi flash chromatography with a gradient cyclohexane : 5-10% ethyl acetate gave the title compound as a yellow foam (2.61 g, 35%).

Step B: 4-methyl-5-(1 -methylpyrazolo[3,4-blpyridin-6-yl)-2-(3-pyridyl)thiazole (Compound K-

A mixture of tri-n-butyl-[4-methyl-2-(3-pyridyl)thiazol-5-yl]stannane (0.300 g, 0.619 mmol) and 6-chloro-1 -methyl-pyrazolo[3,4-b]pyridine (0.120 g, 0.681 mmol) in 1 ,4-dioxane (2.5 rmL) was flushed with argon for 10 min. To this solution was added tetrakis(triphenylphosphine)palladium(0) (0.071 g, 0.0619 mmol) and the orange solution was irradiated in the microwave at 160°C for 45 min. The reaction mixture was quenched with 2 rmL of sat. aqueous NaHC0₃, 2 mL 1 N NaOH, and stirred for 60 min, before being diluted with 10ml water. The mixture was filtered, and the filtrate extracted 3 times with 25 mL of ethyl acetate. The combined organic layers were washed with brine, dried over MgS0₄, filtrated and concentrated in vacuo. Purification by Combi flash chromatography with a column of 12 g and a gradient cyclohexane:0-100% ethyl acetate gave the title compound as a yellow foam (125 mg, 66%)

Example P11 : 4-methyl-5-(1 -methyl-3-phenyl-pyrazolo[3,4-blpyridin-6-yl)-2-(3- pyridyQthiazole (Compound K-23): Compound K-1 (0.084g, 0.27 mmol) was dissolved in Chlorobenzene (2.5 mL) and iodobenzene (0.230g, 1 .1 mmol), cesium carbonate (0.270g, 0.28 mmol) and 1 ,10- Phenanthroline hydrate (0.016g, 0.081 mmol) were added. The mixture was flushed with argon for 10 min, Pd(ll) acetate (0.006g, 0.027 mmol) was added and the mixture heated to 160°C for 40 hours. The mixture was concentrated in vacuo and purified by Combi flash chromatography with a column of 12 g and a gradient cyclohexane:50-100% ethyl acetate, and then recrystallized from di-isopropylether to give the title compound as a yellow solid (44 mg, 42%).

Example P12: 4-chloro-3-methyl-6-[4-methyl-2-(3-pyridyl)thiazol-5-yllisoxazolo[5,4-blpyridine (Compound L-8):

Step A: Ethyl-4,6-dihvdroxy-3-methyl-isoxazolo[5,4-blpyridine-5-carboxylate:

A solution of diethyl malonate (4.56g, 28.2 mmol) in ethanol ( 20 mL) and sodium ethoxide

(2.7 M in ethanol, 1 1.3 mL, 30.6 mmol) was added over 5 min at ambient temperature. The resulting mixture was stirred for 1 hour at ambient temperature. Ethyl 5-amino-3-methyl- isoxazole-4-carboxylate (2g, 1 1.8 mmol) was added at ambient temperature and the mixture was heated to reflux (78°C) overnight. The reaction mixture was filtered and the solid obtained was dissolved in water and acidified to pH 2-3 with cone. HCI. The mixture was filtered and the solid obtained was washed with water and dried in vacuo to give the title compound as a white solid (1.52g, 54%)

Step B: 3-methylisoxazolo[5,4-blpyridine-4,6-diol:

A solution of ethyl-4,6-dihydroxy-3-methyl-isoxazolo[5,4-b]pyridine-5-carboxylate (1 .5g, 6.05 mmol) was stirred in 4N NaOH (30 mL) at reflux for 4 hours. The mixture was cooled to 10°C and acidified with cone. HCI to pH 2-3. The solid obtained was filtrated, washed with water, ethanol and diisopropylether and dried in vacuo to give the title compound as a white solid (1 .02g, 100%) Step C: 4,6-dichloro-3-methyl-isoxazolo[5,4-blpyridine:

3- methylisoxazolo[5,4-b]pyridine-4,6-diol (1 g, 5.78 mmol) was dissolved in phenyl dichlorophosphate (3.55 mL, 23.1 mmol), and the solution was heated at 170°C for 4 hours. After cooling to ambient temperature the mixture was poured onto ice and stirred for 30 min. The mixture was extracted 3 times with 10ml of ethyl acetate and the combined organic layers were carefully washed with 25ml sat. NaHC03 and brine, dried over MgS0₄, filtrated and concentrated in vacuo. Purification by Combi flash chromatography with a gradient cyclohexane:80-90% ethyl acetate gave the title compound as a yellow solid (819 mg, 70%)

Step D: 4-chloro-3-methyl-6-[4-methyl-2-(3-pyridyl)thiazol-5-yllisoxazolo[5,4-blpyridine (Compound L-8):

A mixture of Pd₂(dba)₃ (0.01 Og, 0.001 1 mmol), [(t-Bu)₃PH]BF₄ (0.0086g, 0.03 mmol), and cesium fluoride (0.247g, 1 .59 mmol) were weighed in air and transferred to a microwave tube, which was evacuated and refilled with argon (five cycles). Then, Dioxane (3 mL), tri-n- butyl-[4-methyl-2-(3-pyridyl)thiazol-5-yl]stannane (0.368 g, 0.76 mmol) and 4,6-dichloro-3- methyl-isoxazolo[5,4-b]pyridine (0.150 g, 0.724 mmol) were added, the mixture was irradiated in the Microwave at 140 °C for 45 min and then concentrated in vacuo. Purification by Combi flash chromatography with a column of 12 g and a gradient cyclohexane:10-100% ethyl acetate to give as the first eluting product 6-chloro-3-methyl-4-[4-methyl-2-(3- pyridyl)thiazol-5-yl]isoxazolo[5,4-b]pyridine (37 mg, 15%), LCMS, ret time 1.00 min, MH+ 343, ¹H NMR (500 MHz, CHLOROFORM-d) d ppm: 9.20 (dd, J=2.32, 0.73 Hz, 1 H); 8.73 (dd, J=4.88, 1 .59 Hz, 1 H); 8.28 (dt, J=7.93, 1.95 Hz, 1 H); 7.45 (ddd, J=7.96, 4.85, 0.85 Hz, 1 H); 7.33 (s, 1 H); 2.44 (s, 3 H) 2.38 (s, 3 H).

The second eluted fraction was the title compound (10mg, 4%) as a white foam.

Example P13: 3-bromo-4-[4-methyl-2-(3-pyridyl)thiazol-5-yllthieno[3,2-clpyridine (Compound G-28) and 2,3-dibromo-4-[4-methyl-2-(3-pyridyl)thiazol-5-yllthieno[3,2-clpyridine (Compound G-27):

Step A: 4-[4-methyl-2-(3-pyridyl)thiazol-5-yllthieno[3,2-clpyridine:

A mixture of tri-n-butyl-[4-methyl-2-(3-pyridyl)thiazol-5-yl]stannane (0.350 g, 0.730 mmol) and

4- chlorothieno[3,2-C]-pyridine (0.133 g, 0.766 mmol) in 1 ,4-dioxane (2.5 mL) was flushed with argon for 10 min. To this solution was added tetrakis(triphenylphosphine)palladium(0) (0.084 g, 0.073 mmol) and the orange solution was irradiated in the microwave at 160°C for 45 min. The reaction mixture was quenched with 2ml sat. NaHC03, 2ml 1 N NaOH and stirred for 60 min, and then diluted with 10ml water. This mixture was filtered, and the filtrate extracted 3 times with 25ml of ethyl acetate. The combined organic layers were washed with brine, dried over MgS0₄, filtrated and concentrated in vacuo. Purification by Combi flash chromatography with a column of 12 g and a gradient cyclohexane:0-100% ethyl acetate gave the title compound as a yellow foam (1 18 mg, 52%). Step B: 3-bromo-4-r4-methyl-2-(3-pyridyl)thiazol-5-yllthienor3,2-clpyridine (Compound G-28) and 2,3-dibromo-4-[4-methyl-2-(3-pyridyl)thiazol-5-yllthieno[3,2-clpyridine (Compound G-27):

4-[4-methyl-2-(3-pyridyl)thiazol-5-yl]thieno[3,2-c]pyridine (0.1 10g, 0.356 mmol) was dissolved in TFA (1 ml_, 12.9 mmol), then 0.25ml sulfuric acid (0.25 ml_, 4.5 mmol) and NBS (0.095g, 0.533 mmol) were added. The reaction mixture was stirred 6 days at ambient temperature. The reaction mixture was poured onto ice, neutralized with saturated NaHC0₃ solution and extracted 3 times with 10 ml of dichloromethane. The organic layer was washed with brine, dried over MgS0₄, filtered and concentrated in vacuo. Purification by Combi flash chromatography with a gradient cyclohexane + 20-100% ethyl acetate gave as the first eluted product them title compound G-28 (15mg, 1 1 %). Further elution gave the compound G-27 (1 1 mg, 7%) as a yellow solid.

Example P14: 7-bromo-4-[4-methyl-2-(3-pyridyl)thiazol-5-yllthieno[3,2-clpyridine (Compound G-29):

4-[4-methyl-2-(3-pyridyl)thiazol-5-yl]thieno[3,2-c]pyridine (0.20 g, 0.582 mmol) and sodium acetate (97 mg 0.20 g, 1.16 mmol) were dissolved in acetic acid (8 ml_), and treated with bromine (0.098 g , 0.61 mmol). The reaction mixture was stirred at ambient temperature for 2hr and then heated to 60°C. After this time the reaction mixture was poured onto ice, neutralized with saturated NaHC0₃ solution and extracted ethyl acetate. The organic layer was washed with brine, dried over MgS0₄, filtered and concentrated in vacuo. Purification by Combi flash chromatography with a gradient cyclohexan:ethyl acetate 0:100 gave the title compound G-29 (1 1 mg, 7%) as a yellow solid. The compounds according to the following tables 1 to 15 can be prepared analogously. The examples which follow are intended to illustrate the invention and show preferred compounds of formula I. In the drawings, free radicals signify a methyl group.

For example, compound

A-1

Compounds of formula IL

Table 2.

Compounds of formula Im

Table 4.

Compound of formula lo

Comp. Xi X₂ R101 R102 R103 R104 R105 Structure

Table 5.

Compound of formula Ip

Compound Xi X₂ R101 R102 R103 R104 Structure

Table 6.

Compound of formula Iq

Table 7.

Compound of formula Ir

Table 9.

Compound of formula It

Table 10.

Compound of formula lu

Table 12

Table13.

Compound of formula Ix

Compound Xi X₂ R101 R102 R103 R104 Structure

Table 15

Compounds of formula l_P

LCMS methods:

Method A - Standard: (SQD-ZDQ-ZCQ)

Spectra were recorded on a Mass Spectrometer from Waters (SQD or 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: 0 L/Hr, Desolvation Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment and diode- array detector. Solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3 , 1.8 μηη, 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: gradient: 0 min 0% B, 100%A; 1 .2-1.5min 100% B; Flow (ml/min) 0.85

Method B - Standard long: (SQD-ZDQ-ZCQ)

Spectra were recorded on a Mass Spectrometer from Waters (SQD or 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: 0 L/Hr, Desolvation Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment and diode-array detector. Solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3 , 1.8 μηη, 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: gradient: 0 min 0% B, 100%A; 2.7-3.0min 100% B; Flow (ml/min) 0.85

Table 16. Physical chemical properties of selected compounds:

LCMS (method A)

Comp. Mpt. Ret. Time (min); ¹H NMR

[M+H] measured

(400 MHz, CHLOROFORM-d) δ ppm: 9.22 (s, 1 H); 8.69 (d, J=4.6, 1 H); 8.58 (d, J=5.50 Hz, 1

G-19 0.85, 310 H); 8.30 (m, 1 H); 7.87 (d, J=5.50 Hz, 1 H); 7.60

(d, J=5.50 Hz, 1 H); 7.48 (d, J=5.50 Hz, 1 H); 7.40 - 7.45 (m, 1 H); 2.55 (s, 3 H)..

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 9.28 (dd, J=2.20, 0.73 Hz, 1 H); 8.78 (m, 2 H);

G-25 0.94, 297 8.55 (d, J=5.50 Hz, 1 H) 8.42 (dt, J=7.61 , 2.2

Hz, 1 H); 7.95 (dd, J=5.32, 0.92 Hz, 1 H); 7.74 (d, J=5.50 Hz, 1 H); 7.45 - 7.53 (m, 1 H).

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 9.15 - 9.28 (m, 1 H); 8.59 - 8.72 (m, 1 H); 8.28 (d, J=7.70 Hz, 1 H); 7.82 (s, 1 H); 7.40 (br. s., 1

D-29 1 .13, 392 H); 7.22 (d, J=2.93 Hz, 1 H); 6.59 (d, J=2.93 Hz,

1 H); 4.30 (q, J=6.97 Hz, 2 H); 3.91 (s, 3 H); 2.78 - 2.82 (m, 4 H); 2.50 (s, 3 H) 1 .37 (t, J=6.97 Hz, 3 H).

¹H NMR (500 MHz, CHLOROFORM-d) δ ppm: 9.23 (d, J=1.59 Hz, 1 H); 8.70 (dd, J=4.76, 1.59

L-8 1 .06, 343 Hz, 1 H); 8.29 (dt, J=7.96, 1 .88 Hz, 1 H); 7.59 (s,

1 H); 7.43 (ddd, J=7.99, 4.82, 0.61 Hz, 1 H); 2.89 (s, 3 H); 2.75 (s, 3 H).

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm:

D-30 1 .02, 432 9.19 (d, J=1.83 Hz, 1 H); 8.65 (dd, J=4.77, 1.47

Hz, 1 H); 8.41 (br. s., 1 H); 8.26 (dt, J=8.25, 1.83 LCMS (method A)

Comp. Mpt. Ret. Time (min); ¹H NMR

[M+H] measured

Hz, 1 H); 7.97 (s, 1 H); 7.36 - 7.41 (m, 1 H); 7.32 (d, J=2.93 Hz, 1 H); 6.65 (d, J=2.93 Hz, 1 H); 4.17 - 4.24 (m, 5 H); 2.79 (s, 3 H)

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 9.24 (d, J=1.83 Hz, 1 H); 8.69 (d, J=4.77 Hz, 1 H); 8.40 (d, J=8.44 Hz, 1 H); 8.32 (d, J=8.07 Hz,

K-23 1 .20, 384

1 H); 7.98 (d, J=8.07 Hz, 2 H); 7.50 - 7.57 (m, 3 H); 7.39 - 7.48 (m, 2 H); 4.25 (s, 3 H); 2.91 (s, 3 H).

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 9.21 -9.25 (m, 1 H); 8.64 - 8.67 (m, 1 H); 8.27 -

D-28 1 .01 , 349 8.31 (m, 1 H); 8.00 (s, 1 H); 7.38 - 7.43 (m, 1 H);

7.28 (s, 1 H); 6.64 (d, J=2.93 Hz, 1 H); 3.99 (s, 3 H); 2.93 (s, 3 H); 2.85 (s, 3 H).

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 9.19 - 9.23 (m, 1 H); 8.68 (dd, J=4.95, 1 .93 Hz, 1 H); 8.29 (dt, J=8.25, 1 .93 Hz, 1 H), 7.38 - 7.43

I-28 170-171 0.98, 341

(m, 1 H), 7.29 (d, J=0.73 Hz, 1 H), 7.18 (d, J=3.30 Hz, 1 H), 6.68 (dd, J=3.30, 0.73 Hz, 1 H), 3.84 (s, 3 H); 2.70 (s, 3 H).

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 9.19 - 9.22 (m, 1 H); 8.69 (dd, J=4.95, 1 .65 Hz, 1 H); 8.27 (dt, J=8.07, 1 .65 Hz, 1 H); 7.60 (s, 1

N-26 68-70 0.93, 341

H); 7.40 - 7.44 (m, 1 H); 7.25 (d, J=3.30 Hz, 1 H); 6.56 (d, J=3.30 Hz, 1 H); 3.58 (s, 3 H); 2.36 (s, 3 H).

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 9.20 (br. s., 1 H); 8.65 (d, J=3.67 Hz, 1 H); 8.27

D-27 167-168 0.04, 365

(dt, J=7.98, 1.88 Hz, 1 H); 7.95 (s, 1 H), 7.39 (dd, J=8.07, 4.77 Hz, 1 H); 7.29 (d, J=2.93 Hz, 2 LCMS (method A)

Comp. Mpt. Ret. Time (min); ¹H NMR

[M+H] measured

H); 6.65 (d, J=2.93 Hz, 1 H); 4.10 (s, 3 H); 3.99 (s, 3 H); 2.78 (s, 3 H).

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 9.23 (dd, J=2.20, 0.73 Hz, 1 H); 8.68 (dd, J=4.77, 2.20 Hz, 1 H); 8.28 - 8.33 (m, 1 H); 8.12

K-1 155-159 1 .36, 308

(d, J=8.44 Hz, 1 H); 8.03 (s, 1 H); 7.48 - 7.50 (d, 8.44 Hz, 1 H); 7.39 - 7.44 (m, 1 H), 4.20 (s, 3 H); 2.89 (s, 3 H).

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 9.22 (d, J=1.83 Hz, 1 H); 8.68 (dd, J=4.77, 1.47

G-27 - 1 .05, 468 Hz, 1 H); 8.61 (d, J=5.50 Hz, 1 H); 8.30 (dt,

J=7.98, 1.88 Hz, 1 H); 7.79 (d, J=5.50 Hz, 1 H) 7.38 - 7.44 (m, 1 H); 2.28 (s, 3 H).

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 9.22 (d, J=1.47 Hz, 1 H); 8.67 (dd, J=4.77, 1.83 Hz, 1 H); 8.63 (d, J=5.50 Hz, 1 H), 8.30 (dt,

G-28 - 0.91 , 390

J=7.98, 1.88 Hz, 1 H), 7.92 (d, J=5.50 Hz, 1 H); 7.58 - 7.62 (m, 1 H); 7.38 - 7.44 (m, 1 H); 2.29 (s, 3 H).

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: (400 MHz, J=1.83 Hz, 1 H) 8.67 - 8.72 (m, 1 H)

G-29 8.30 (d, J=8.07 Hz, 1 H) 7.68 (d, J=5.87 Hz, 1 H)

7.59 (d, J=5.50 Hz, 1 H) 7.43 (d, J=3.67 Hz, 1 H) 2.55 (s, 3 H)

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 9.15 - 9.26 (m, 1 H); 8.64 (dd, J=4.95, 1 .65 Hz,

P-4 - 0.71 , 321 1 H); 8.21 - 8.33 (m, 1 H); 7.32 - 7.45 (m, 1 H);

7.13 - 7.25 (m, 2 H); 6.69 (d, J=3.30 Hz, 1 H); 4.08 (s, 3 H); 2.82 (s, 3 H); 2.74 (s, 3 H).

^"able 17. LCMS data for intermediates:

Formulation examples (% = percent by weight)

Example F1: Emulsion concentrates a) b) c)

Active ingredient 25% 40% 50%

Calcium dodecylbenzenesulfonate 5 % 8 % 6 %

Castor oil polyethylene

glycol ether (36 mol of EO) 5 % - Tnbutylphenoxypolyethylene glycol

ether (30 mol of EO) - 12% 4%

Cyclohexanone - 15% 20%

Xylene mixture 65% 25% 20%

Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.

Example F2: Solutions a) b) c) d)

Active ingredient 80% 10% 5% 95%

Ethylene glycol monomethyl

ether 20% -

Polyethylene glycol

MW 400 - 70 % -

N-Methylpyrrolid-2-one - 20% -

Epoxidized coconut oil - - 1 % 5 %

Petroleum ether

(boiling range: 160-190°) - - 94% - The solutions are suitable for use in the form of microdrops.

Example F3: Granules a) b) c) d)

Active ingredient 5% 10% 8% 21 %

Kaolin 94% - 79% 54%

Highly disperse silica 1 % - 13% 7%

Attapulgite - 90% - 18%

The active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier(s), and the solvent is subsequently evaporated in vacuo.

Example F4: Dusts a) b)

Active ingredient 2 % 5 %

Highly disperse silica 1 % 5 %

Talc 97% -

Kaolin - 90 %

Ready-to-use dusts are obtained by intimately mixing the carriers and the active ingredient.

Example F5: Wettable powders a) b) c)

Active ingredient 25% 50% 75%

Sodium lignosulfonate 5 % 5 %

Sodium lauryl sulfate 3 % - 5 %

Sodium diisobutyl- naphthalenesulfonate - 6% 10%

Octylphenoxypolyethylene glycol

ether (7-8 mol of EO) - 2% -

Highly disperse silica 5% 10% 10%

Kaolin 62% 27% -

The active ingredient is mixed with the additives and the mixture is ground thoroughly in a suitable mill. This gives wettable powders, which can be diluted with water to give suspensions of any desired concentration.

Example F6: Extruder granules

Active ingredient 10% Sodium lignosulfonate 2 %

Carboxymethylcellulose 1 %

Kaolin 87 %

The active ingredient is mixed with the additives, and the mixture is ground, moistened with water, extruded, granulated and dried in a stream of air.

Example F7: Coated granules

Active ingredient 3 %

Polyethylene glycol (MW 200) 3 %

Kaolin 94 %

In a mixer, the finely ground active ingredient is applied uniformLy to the kaolin, which has been moistened with the polyethylene glycol. This gives dust-free coated granules.

Example F8: Suspension concentrate

Active ingredient 40 %

Ethylene glycol 10 %

Nonylphenoxypolyethylene glycol ether (15 mol of EO) 6 %

Sodium lignosulfonate 10 %

Carboxymethylcellulose 1 %

37 % aqueous formaldehyde solution 0.2 %

Silicone oil (75 % aqueous emulsion) 0.8 %

Water 32 %

The finely ground active ingredient is mixed intimately with the additives. Suspensions of any desired concentration can be prepared from the thus resulting suspension concentrate by dilution with water.

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, pyridyl- methyleneamino 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 specifically described in Tables 1 to 15 of the present invention"): an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX,

an acaricide selected from the group of substances consisting of 1 ,1 -bis(4-chlorophenyl)-2- ethoxyethanol (lUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate

(lUPAC/Chemical Abstracts name) (1059) + TX, 2-fluoro-/V-methyl-/V-1 -naphthylacetamide (lUPAC name) (1295) + TX, 4-chlorophenyl phenyl sulfone (lUPAC name) (981 ) + TX, abamectin (1 ) + TX, acequinocyl (3) + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, alpha-cypermethrin (202) + TX, amidithion (870) + TX, amidoflumet [CCN] + TX, amidothioate (872) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, aramite (881 ) + TX, arsenous oxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azobenzene (lUPAC name) (888) + TX, azocyclotin (46) + TX, azothoate (889) + TX, benomyl (62) + TX, benoxafos (alternative name) [CCN] + TX, benzoximate (71 ) + TX, benzyl benzoate (I UPAC name) [CCN] + TX, bifenazate (74) + TX, bifenthrin (76) + TX, binapacryl (907) + TX, brofenvalerate (alternative name) + TX, bromocyclen (918) + TX, bromophos (920) + TX, bromophos-ethyl (921 ) + TX, bromopropylate (94) + TX, buprofezin (99) + TX,

butocarboxim (103) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, calcium polysulfide (lUPAC name) (1 1 1 ) + TX, camphechlor (941 ) + TX, carbanolate (943) + TX, carbaryl (1 15) + TX, carbofuran (1 18) + TX, carbophenothion (947) + TX, CGA 50'439 (development code) (125) + TX, chinomethionat (126) + TX, chlorbenside (959) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorfenapyr (130) + TX, chlorfenethol (968) + TX, chlorfenson (970) + TX, chlorfensulphide (971 ) + TX, chlorfenvinphos (131 ) + TX, chlorobenzilate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, clofentezine (158) + TX, closantel (alternative name) [CCN] + TX, coumaphos (174) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, cufraneb (1013) + TX, cyanthoate (1020) + TX, cyflumetofen (CAS Reg. No.: 400882-07-7) + TX, cyhalothrin (196) + TX, cyhexatin (199) + TX, cypermethrin (201 ) + TX, DCPM (1032) + TX, DDT (219) + TX, demephion (1037) + TX, demephion-0 (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-0 (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S-methyl (224) + TX, demeton-S-methylsulphon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diazinon (227) + TX, dichlofluanid (230) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicofol (242) + TX, dicrotophos (243) + TX, dienochlor (1071 ) + TX, dimefox (1081 ) + TX, dimethoate (262) + TX, dinactin (alternative name) (653) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX, dinobuton (269) + TX, dinocap (270) + TX, dinocap-4 [CCN] + TX, dinocap-6 [CCN] + TX, dinocton (1090) + TX, dinopenton (1092) + TX, dinosulfon (1097) + TX,

dinoterbon (1098) + TX, dioxathion (1 102) + TX, diphenyl sulfone (lUPAC name) (1 103) + TX, disulfiram (alternative name) [CCN] + TX, disulfoton (278) + TX, DNOC (282) + TX, dofenapyn (1 1 13) + TX, doramectin (alternative name) [CCN] + TX, endosulfan (294) + TX, endothion (1 121 ) + TX, EPN (297) + TX, eprinomectin (alternative name) [CCN] + TX, ethion (309) + TX, ethoate-methyl (1 134) + TX, etoxazole (320) + TX, etrimfos (1 142) + TX, fenazaflor (1 147) + TX, fenazaquin (328) + TX, fenbutatin oxide (330) + TX, fenothiocarb (337) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fen- pyroximate (345) + TX, fenson (1 157) + TX, fentrifanil (1 161 ) + TX, fenvalerate (349) + TX, fipronil (354) + TX, fluacrypyrim (360) + TX, fluazuron (1 166) + TX, flubenzimine (1 167) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1 169) + TX, flufenoxuron (370) + TX, flumethrin (372) + TX, fluorbenside (1 174) + TX, fluvalinate (1 184) + TX, FMC 1 137 (development code) (1 185) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1 192) + TX, formparanate (1 193) + TX, gamma-HCH (430) + TX, glyodin (1205) + TX, halfenprox (424) + TX, heptenophos (432) + TX, hexadecyl cyclopropanecarboxylate (lUPAC/Chemical Abstracts name) (1216) + TX, hexythiazox (441 ) + TX, iodomethane (lUPAC name) (542) + TX, isocarbophos

(alternative name) (473) + TX, isopropyl 0-(methoxyaminothiophosphoryl)salicylate (lUPAC name) (473) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, lindane (430) + TX, lufenuron (490) + TX, malathion (492) + TX, malonoben (1254) + TX, mecarbam (502) + TX, mephosfolan (1261 ) + TX, mesulfen (alternative name) [CCN] + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methidathion (529) + TX, methiocarb (530) + TX, methomyl (531 ) + TX, methyl bromide (537) + TX, metolcarb (550) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, monocrotophos (561 ) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naled (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) + TX, nifluridide (1309) + TX, nikkomycins (alternative name) [CCN] + TX, nitrilacarb (1313) + TX, nitrilacarb 1 :1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum oils

(alternative name) (628) + TX, phenkapton (1330) + TX, phenthoate (631 ) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosphamidon (639) + TX, phoxim (642) + TX, pirimiphos-methyl (652) + TX,

polychloroterpenes (traditional name) (1347) + TX, polynactins (alternative name) (653) + TX, proclonol (1350) + TX, profenofos (662) + TX, promacyl (1354) + TX, propargite (671 ) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothoate (1362) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridaphenthion (701 ) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, quinalphos (71 1 ) + TX, quintiofos (1381 ) + TX, R-1492

(development code) (1382) + TX, RA-17 (development code) (1383) + TX, rotenone (722) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, sophamide (1402) + TX,

spirodiclofen (738) + TX, spiromesifen (739) + TX, SSI-121 (development code) (1404) + TX, sulfiram (alternative name) [CCN] + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulphur (754) + TX, SZI-121 (development code) (757) + TX, tau-fluvalinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, terbam (alternative name) + TX,

tetrachlorvinphos (777) + TX, tetradifon (786) + TX, tetranactin (alternative name) (653) + TX, tetrasul (1425) + TX, thiafenox (alternative name) + TX, thiocarboxime (1431 ) + TX, thiofanox (800) + TX, thiometon (801 ) + TX, thioquinox (1436) + TX, thuringiensin (alternative name) [CCN] + TX, triamiphos (1441 ) + TX, triarathene (1443) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trifenofos (1455) + TX, trinactin (alternative name) (653) + TX, vamidothion (847) + TX, vaniliprole [CCN] and YI-5302 (compound code) + TX,

an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (lUPAC 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 (lUPAC name) (347) and triphenyltin hydroxide (lUPAC name) (347) + TX,

an anthelmintic selected from the group of substances consisting of abamectin (1 ) + TX, crufomate (101 1 ) + 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 (1 122) + TX, fenthion (346) + TX, pyridin-4-amine (lUPAC name) (23) and strychnine (745) + TX,

a bactericide selected from the group of substances consisting of 1 -hydroxy-1 /-/-pyridine-2- thione (lUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (lUPAC name) (170) + TX, copper hydroxide (lUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1 105) + TX, dodicin (1 1 12) + TX, fenaminosulf (1 144) + TX, formaldehyde (404) + TX, hydrargaphen (alternative name) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (lUPAC 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-l 1 -enal (lUPAC name) (436) + TX, (Z)-hexadec- 1 1 -en-1 -yl acetate (lUPAC name) (437) + TX, (Z)-hexadec-13-en-1 1 -yn-1 -yl 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,1 1 £)-tetradeca-9,1 1 -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 B-i (alternative name) (839) + TX, trimedlure B₂ (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 (1 137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,

an insecticide selected from the group of substances consisting of 1 -dichloro-1 -nitroethane (lUPAC/Chemical Abstracts name) (1058) + TX, 1 ,1 -dichloro-2,2-bis(4-ethylphenyl)ethane (lUPAC name) (1056), + TX, 1 ,2-dichloropropane (lUPAC/Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene (lUPAC name) (1063) + TX, 1 -bromo- 2-chloroethane (lUPAC/Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-1 -(3,4- dichlorophenyl)ethyl acetate (lUPAC name) (1451 ) + TX, 2,2-dichlorovinyl 2- ethylsulphinylethyl methyl phosphate (lUPAC name) (1066) + TX, 2-(1 ,3-dithiolan-2-yl)phenyl dimethylcarbamate (lUPAC/ Chemical Abstracts name) (1 109) + TX, 2-(2- butoxyethoxy)ethyl thiocyanate (lUPAC/Chemical Abstracts name) (935) + TX, 2-(4,5- dimethyl-1 ,3-dioxolan-2-yl)phenyl methylcarbamate (lUPAC/ Chemical Abstracts name) (1084) + TX, 2-(4-chloro-3,5-xylyloxy)ethanol (lUPAC name) (986) + TX, 2-chlorovinyl diethyl phosphate (lUPAC name) (984) + TX, 2-imidazolidone (lUPAC name) (1225) + TX, 2-isovalerylindan-1 ,3-dione (lUPAC name) (1246) + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate (lUPAC name) (1284) + TX, 2-thiocyanatoethyl laurate (lUPAC name) (1433) + TX, 3-bromo-1 -chloroprop-1 -ene (lUPAC name) (917) + TX, 3-methyl-1 - phenylpyrazol-5-yl dimethylcarbamate (lUPAC name) (1283) + TX, 4-methyl(prop-2- ynyl)amino-3,5-xylyl methylcarbamate (lUPAC name) (1285) + TX, 5,5-dimethyl-3- oxocyclohex-1 -enyl dimethylcarbamate (lUPAC name) (1085) + TX, abamectin (1 ) + TX, acephate (2) + TX, acetamiprid (4) + TX, acethion (alternative name) [CCN] + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, acrylonitrile (lUPAC name) (861 ) + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, aldrin (864) + TX, allethrin (17) + TX, allosamidin (alternative name) [CCN] + TX, allyxycarb (866) + TX, alpha-cypermethrin (202) + TX, alpha-ecdysone (alternative name) [CCN] + TX, aluminium phosphide (640) + TX, amidithion (870) + TX, amidothioate (872) + TX, aminocarb (873) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, anabasine (877) + TX, athidathion (883) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azadirachtin (alternative name) (41 ) + TX, azamethiphos (42) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azothoate (889) + TX, Bacillus thuringiensis delta endotoxins (alternative name) (52) + TX, barium

hexafluorosilicate (alternative name) [CCN] + TX, barium polysulfide (lUPAC/Chemical Abstracts name) (892) + TX, barthrin [CCN] + TX, Bayer 22/190 (development code) (893) + TX, Bayer 22408 (development code) (894) + TX, bendiocarb (58) + TX, benfuracarb (60) + TX, bensultap (66) + TX, beta-cyfluthrin (194) + TX, beta-cypermethrin (203) + TX, bifenthrin (76) + TX, bioallethrin (78) + TX, bioallethrin S-cyclopentenyl isomer (alternative name) (79) + TX, bioethanomethrin [CCN] + TX, biopermethrin (908) + TX, bioresmethrin (80) + TX, bis(2-chloroethyl) ether (lUPAC name) (909) + TX, bistrifluron (83) + TX, borax (86) + TX, brofen vale rate (alternative name) + TX, bromfenvinfos (914) + TX,

bromocyclen (918) + TX, bromo-DDT (alternative name) [CCN] + TX, bromophos (920) + TX, bromophos-ethyl (921 ) + TX, bufencarb (924) + TX, buprofezin (99) + TX, butacarb (926) + TX, butathiofos (927) + TX, butocarboxim (103) + TX, butonate (932) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, calcium arsenate [CCN] + TX, calcium cyanide (444) + TX, calcium polysulfide (lUPAC name) (1 1 1 ) + TX, camphechlor (941 ) + TX, carbanolate (943) + TX, carbaryl (1 15) + TX, carbofuran (1 18) + TX, carbon disulfide (lUPAC/Chemical Abstracts name) (945) + TX, carbon tetrachloride (lUPAC name) (946) + TX, carbophenothion (947) + TX, carbosulfan (1 19) + TX, cartap (123) + TX, cartap hydrochloride (123) + TX, cevadine (alternative name) (725) + TX, chlorbicyclen (960) + TX, chlordane (128) + TX, chlordecone (963) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorethoxyfos (129) + TX, chlorfenapyr (130) + TX, chlorfenvinphos (131 ) + TX, chlorfluazuron (132) + TX, chlormephos (136) + TX, chloroform [CCN] + TX, chloropicrin (141 ) + TX, chlorphoxim (989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, chromafenozide (150) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, cis-resmethrin (alternative name) + TX, cismethrin (80) + TX, clocythrin (alternative name) + TX, cloethocarb (999) + TX, closantel (alternative name) [CCN] + TX, clothianidin (165) + TX, copper acetoarsenite [CCN] + TX, copper arsenate [CCN] + TX, copper oleate [CCN] + TX, coumaphos (174) + TX, coumithoate (1006) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, crufomate (101 1 ) + TX, cryolite (alternative name) (177) + TX, CS 708 (development code) (1012) + TX, cyanofenphos (1019) + TX, cyanophos (184) + TX, cyanthoate (1020) + TX, cyclethrin [CCN] + TX, cycloprothrin (188) + TX, cyfluthrin (193) + TX, cyhalothrin (196) + TX, cypermethrin (201 ) + TX, cyphenothrin (206) + TX, cyromazine (209) + TX, cythioate (alternative name) [CCN] + TX, d-limonene (alternative name) [CCN] + TX, d-tetramethrin (alternative name) (788) + TX, DAEP (1031 ) + TX, dazomet (216) + TX, DDT (219) + TX, decarbofuran (1034) + TX, deltamethrin (223) + TX, demephion (1037) + TX, demephion-0 (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-0 (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S-methyl (224) + TX, demeton-S-methylsulphon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diamidafos (1044) + TX, diazinon (227) + TX, dicapthon (1050) + TX, dichlofenthion (1051 ) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicresyl

(alternative name) [CCN] + TX, dicrotophos (243) + TX, dicyclanil (244) + TX, dieldrin (1070) + TX, diethyl 5-methylpyrazol-3-yl phosphate (lUPAC name) (1076) + TX, diflubenzuron (250) + TX, dilor (alternative name) [CCN] + TX, dimefluthrin [CCN] + TX, dimefox (1081 ) + TX, dimetan (1085) + TX, dimethoate (262) + TX, dimethrin (1083) + TX, dimethylvinphos (265) + TX, dimetilan (1086) + TX, dinex (1089) + TX, dinex- diclexine (1089) + TX, dinoprop (1093) + TX, dinosam (1094) + TX, dinoseb (1095) + TX, dinotefuran (271 ) + TX, diofenolan (1099) + TX, dioxabenzofos (1 100) + TX, dioxacarb (1 101 ) + TX, dioxathion (1 102) + TX, disulfoton (278) + TX, dithicrofos (1 108) + TX, DNOC (282) + TX, doramectin (alternative name) [CCN] + TX, DSP (1 1 15) + TX, ecdysterone (alternative name) [CCN] + TX, El 1642 (development code) (1 1 18) + TX, emamectin (291 ) + TX, emamectin benzoate (291 ) + TX, EMPC (1 120) + TX, empenthrin (292) + TX, endosulfan (294) + TX, endothion (1 121 ) + TX, endrin (1 122) + TX, EPBP (1 123) + TX, EPN (297) + TX, epofenonane (1 124) + TX, eprinomectin (alternative name) [CCN] + TX, esfenvalerate (302) + TX, etaphos (alternative name) [CCN] + TX, ethiofencarb (308) + TX, ethion (309) + TX, ethiprole (310) + TX, ethoate-methyl (1 134) + TX, ethoprophos (312) + TX, ethyl formate (I UPAC name) [CCN] + TX, ethyl-DDD (alternative name) (1056) + TX, ethylene dibromide (316) + TX, ethylene dichloride (chemical name) (1 136) + TX, ethylene oxide [CCN] + TX, etofenprox (319) + TX, etrimfos (1 142) + TX, EXD (1 143) + TX, famphur (323) + TX, fenamiphos (326) + TX, fenazaflor (1 147) + TX, fenchlorphos (1 148) + TX, fenethacarb (1 149) + TX, fenfluthrin (1 150) + TX, fenitrothion (335) + TX, fenobucarb (336) + TX, fenoxacrim (1 153) + TX, fenoxycarb (340) + TX, fenpirithrin (1 155) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fensulfothion (1 158) + TX, fenthion (346) + TX, fenthion-ethyl [CCN] + TX, fenvalerate (349) + TX, fipronil (354) + TX, flonicamid (358) + TX, flubendiamide (CAS. Reg. No.: 272451 -65-7) + TX, flucofuron (1 168) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1 169) + TX, flufenerim [CCN] + TX, flufenoxuron (370) + TX, flufenprox (1 171 ) + TX, flumethrin (372) + TX, fluvalinate (1 184) + TX, FMC 1 137 (development code) (1 185) + TX, fonofos (1 191 ) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1 192) + TX, formparanate (1 193) + TX, fosmethilan (1 194) + TX, fospirate (1 195) + TX, fosthiazate (408) + TX, fosthietan (1 196) + TX, furathiocarb (412) + TX, furethrin (1200) + TX, gamma- cyhalothrin (197) + TX, gamma-HCH (430) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, GY-81 (development code) (423) + TX, halfenprox (424) + TX, halofenozide (425) + TX, HCH (430) + TX, HEOD (1070) + TX, heptachlor (121 1 ) + TX, heptenophos (432) + TX, heterophos [CCN] + TX, hexaflumuron (439) + TX, HHDN (864) + TX, hydramethylnon (443) + TX, hydrogen cyanide (444) + TX, hydroprene (445) + TX, hyquincarb (1223) + TX, imidacloprid (458) + TX, imiprothrin (460) + TX, indoxacarb (465) + TX, iodomethane (lUPAC name) (542) + TX, IPSP (1229) + TX, isazofos (1231 ) + TX, isobenzan (1232) + TX, isocarbophos (alternative name) (473) + TX, isodrin (1235) + TX, isofenphos (1236) + TX, isolane (1237) + TX, isoprocarb (472) + TX, isopropyl O- (methoxyaminothiophosphoryl)salicylate (lUPAC name) (473) + TX, isoprothiolane (474) + TX, isothioate (1244) + TX, isoxathion (480) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, juvenile hormone I (alternative name) [CCN] + TX, juvenile hormone II (alternative name) [CCN] + TX, juvenile hormone III (alternative name) [CCN] + TX, kelevan (1249) + TX, kinoprene (484) + TX, lambda-cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepimectin (CCN) + TX, leptophos (1250) + TX, lindane (430) + TX, lirimfos (1251 ) + TX, lufenuron (490) + TX, lythidathion (1253) + TX, m-cumenyl methylcarbamate (lUPAC name) (1014) + TX, magnesium phosphide (lUPAC name) (640) + TX, malathion (492) + TX, malonoben (1254) + TX, mazidox (1255) + TX, mecarbam (502) + TX, mecarphon (1258) + TX, menazon (1260) + TX, mephosfolan (1261 ) + TX, mercurous chloride (513) + TX, mesulfenfos (1263) + TX, metaflumizone (CCN) + TX, metam (519) + TX, metam- potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methanesulphonyl fluoride (lUPAC/Chemical Abstracts name) (1268) + TX, methidathion (529) + TX, methiocarb (530) + TX, methocrotophos (1273) + TX, methomyl (531 ) + TX, methoprene (532) + TX, methoquin-butyl (1276) + TX, methothrin (alternative name) (533) + TX, methoxychlor (534) + TX,

methoxyfenozide (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methylchloroform (alternative name) [CCN] + TX, methylene chloride [CCN] + TX, metofluthrin [CCN] + TX, metolcarb (550) + TX, metoxadiazone (1288) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, mirex (1294) + TX, monocrotophos (561 ) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naftalofos (alternative name) [CCN] + TX, naled (567) + TX, naphthalene

(lUPAC/Chemical Abstracts name) (1303) + TX, NC-170 (development code) (1306) + TX, NC-184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (578) + TX, nifluridide (1309) + TX, nitenpyram (579) + TX, nithiazine (131 1 ) + TX, nitrilacarb (1313) + TX, nitrilacarb 1 :1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, nornicotine (traditional name) (1319) + TX, novaluron (585) + TX, noviflumuron (586) + TX, 0-5-dichloro-4-iodophenyl O-ethyl

ethylphosphonothioate (lUPAC name) (1057) + TX, 0,0-diethyl 0-4-methyl-2-oxo-2H- chromen-7-yl phosphorothioate (lUPAC name) (1074) + TX, Ο,Ο-diethyl 0-6-methyl-2- propylpyrimidin-4-yl phosphorothioate (lUPAC name) (1075) + TX, Ο,Ο,Ο',Ο'-tetra propyl dithiopyrophosphate (lUPAC name) (1424) + TX, oleic acid (lUPAC name) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydemeton-methyl (609) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, para-dichlorobenzene

[CCN] + TX, parathion (615) + TX, parathion-methyl (616) + TX, penfluron (alternative name) [CCN] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (lUPAC name) (623) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, PH 60-38 (development code) (1328) + TX, phenkapton (1330) + TX, phenothrin (630) + TX, phenthoate (631 ) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosnichlor (1339) + TX, phosphamidon (639) + TX, phosphine (lUPAC name) (640) + TX, phoxim (642) + TX, phoxim-methyl (1340) + TX, pirimetaphos (1344) + TX, pirimicarb (651 ) + TX, pirimiphos-ethyl (1345) + TX, pirimiphos-methyl (652) + TX, polychlorodicyclopentadiene isomers (lUPAC name) (1346) + TX, polychloroterpenes (traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, prallethrin (655) + TX, precocene I (alternative name) [CCN] + TX, precocene II (alternative name) [CCN] + TX, precocene III (alternative name) [CCN] + TX, primidophos (1349) + TX, profenofos (662) + TX, profluthrin [CCN] + TX, promacyl (1354) + TX, promecarb (1355) + TX, propaphos (1356) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothiofos (686) + TX, prothoate (1362) + TX, protrifenbute [CCN] + TX, pymetrozine (688) + TX, pyraclofos (689) + TX, pyrazophos (693) + TX, pyresmethrin (1367) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridalyl (700) + TX, pyridaphenthion (701 ) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, pyriproxyfen (708) + TX, quassia (alternative name) [CCN] + TX, quinalphos (71 1 ) + TX, quinalphos- methyl (1376) + TX, quinothion (1380) + TX, quintiofos (1381 ) + TX, R-1492

(development code) (1382) + TX, rafoxanide (alternative name) [CCN] + TX, resmethrin (719) + TX, rotenone (722) + TX, RU 15525 (development code) (723) + TX, RU 25475 (development code) (1386) + TX, ryania (alternative name) (1387) + TX, ryanodine (traditional name) (1387) + TX, sabadilla (alternative name) (725) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, silafluofen (728) + TX, SN 72129 (development code) (1397) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoride (lUPAC/Chemical Abstracts name) (1399) + TX, sodium hexafluorosilicate (1400) + TX, sodium pentachlorophenoxide (623) + TX, sodium selenate (lUPAC name) (1401 ) + TX, sodium thiocyanate [CCN] + TX, sophamide (1402) + TX, spinosad (737) + TX, spiromesifen (739) + TX, spirotetrmat (CCN) + TX, sulcofuron (746) + TX, sulcofuron- sodium (746) + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulphuryl fluoride (756) + TX, sulprofos (1408) + TX, tar oils (alternative name) (758) + TX, tau-fluvalinate (398) + TX, tazimcarb (1412) + TX, TDE (1414) + TX, tebufenozide (762) + TX, tebufenpyrad (763) + TX, tebupirimfos (764) + TX, teflubenzuron (768) + TX, tefluthrin (769) + TX, temephos (770) + TX, TEPP (1417) + TX, terallethrin (1418) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachloroethane [CCN] + TX, tetrachlorvinphos (777) + TX, tetramethrin (787) + TX, theta-cypermethrin (204) + TX, thiacloprid (791 ) + TX, thiafenox (alternative name) + TX, thiamethoxam (792) + TX, thicrofos (1428) + TX, thiocarboxime (1431 ) + TX, thiocyclam (798) + TX, thiocyclam hydrogen oxalate (798) + TX, thiodicarb (799) + TX, thiofanox (800) + TX, thiometon (801 ) + TX, thionazin (1434) + TX, thiosultap (803) + TX, thiosultap-sodium (803) + TX, thuringiensin (alternative name) [CCN] + TX, tolfenpyrad (809) + TX, tralomethrin (812) + TX, transfluthrin (813) + TX, transpermethrin (1440) + TX, triamiphos (1441 ) + TX, triazamate (818) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trichlormetaphos-3 (alternative name) [CCN] + TX, trichloronat (1452) + TX, trifenofos (1455) + TX, triflumuron (835) + TX, trimethacarb (840) + TX, triprene (1459) + TX, vamidothion (847) + TX, vaniliprole [CCN] + TX, veratridine (alternative name) (725) + TX, veratrine (alternative name) (725) + TX, XMC (853) + TX, xylylcarb (854) + TX, YI-5302 (compound code) + TX, zeta-cypermethrin (205) + TX, zetamethrin (alternative name) + TX, zinc phosphide (640) + TX, zolaprofos (1469) and ZXI 8901 (development code) (858) + TX, cyantraniliprole [736994-63-19 + TX, chlorantraniliprole [500008-45-7] + TX, cyenopyrafen [560121 -52-0] + TX, cyflumetofen [400882-07-7] + TX, pyrifluquinazon

[337458-27-2] + TX, spinetoram [187166-40-1 + 187166-15-0] + TX, spirotetramat [203313- 25-1] + TX, sulfoxaflor [946578-00-3] + TX, flufiprole [704886-18-0] + TX, meperfluthrin

[915288-13-0] + TX, tetramethylfluthrin [84937-88-2] + 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 (1 18) + TX, carbon disulfide (945) + TX, carbosulfan (1 19) + TX, chloropicrin (141 ) + TX, chlorpyrifos (145) + TX, cloethocarb (999) + 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 (1 196) + 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 verrucaria 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,

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 (1 183) + TX, flupropadine hydrochloride (1 183) + 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 fluoro- acetate (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, and biologically active compounds selected from the group consisting of azaconazole (60207-31 -0] + TX, bitertanol [70585-36-3] + TX, bromuconazole [1 16255-48-2] + TX, cyproconazole [94361 -06-5] + TX, difenoconazole [1 19446-68-3] + TX, diniconazole

[83657-24-3] + TX, epoxiconazole [106325-08-0] + TX, fenbuconazole [1 14369-43-6] + TX, fluquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol [76674- 21 -0] + TX, hexaconazole [79983-71 -4] + TX, imazalil [35554-44-0] + TX, imibenconazole [86598-92-7] + TX, ipconazole [125225-28-7] + TX, metconazole [1251 16-23-6] + TX, myclobutanil [88671 -89-0] + TX, pefurazoate [101903-30-4] + TX, penconazole [66246-88- 6] + TX, prothioconazole [178928-70-6] + TX, pyrifenox [88283-41 -4] + TX, prochloraz [67747-09-5] + TX, propiconazole [60207-90-1] + TX, simeconazole [149508-90-7] + TX, tebuconazole [107534-96-3] + TX, tetraconazole [1 12281 -77-3] + TX, triadimefon [43121 - 43-3] + TX, triadimenol [55219-65-3] + TX, triflumizole [99387-89-0] + TX, triticonazole [131983-72-7] + TX, ancymidol [12771 -68-5] + TX, fenarimol [60168-88-9] + TX, nuarimol [63284-71 -9] + TX, bupirimate [41483-43-6] + TX, dimethirimol [5221 -53-4] + TX, ethirimol [23947-60-6] + TX, dodemorph [1593-77-7] + TX, fenpropidine [67306-00-7] + TX, fenpropimorph [67564-91 -4] + TX, spiroxamine [1 18134-30-8] + TX, tridemorph

[81412-43-3] + TX, cyprodinil [121552-61 -2] + TX, mepanipyrim [1 10235-47-7] + TX, pyrimethanil [531 12-28-0] + TX, fenpiclonil [74738-17-3] + TX, fludioxonil [131341 -86-1 ] + TX, benalaxyl [71626-1 1 -4] + TX, furalaxyl [57646-30-7] + TX, metalaxyl [57837-19-1 ] + TX, R-metalaxyl [70630-17-0] + TX, ofu race [58810-48-3] + TX, oxadixyl [77732-09-3] + TX, benomyl [17804-35-2] + TX, carbendazim [10605-21 -7] + TX, debacarb [62732-91 -6] + TX, fuberidazole [3878-19-1 ] + TX, thiabendazole [148-79-8] + TX, chlozolinate [84332- 86-5] + TX, dichlozoline [24201 -58-9] + TX, iprodione [36734-19-7] + TX, myclozoline [54864-61 -8] + TX, procymidone [32809-16-8] + TX, vinclozoline [50471 -44-8] + TX, boscalid [188425-85-6] + TX, carboxin [5234-68-4] + TX, fenfuram [24691 -80-3] + TX, flutolanil [66332-96-5] + TX, mepronil [55814-41 -0] + TX, oxycarboxin [5259-88-1] + TX, penthiopyrad [183675-82-3] + TX, thifluzamide [130000-40-7] + TX, guazatine [108173-90- 6] + TX, dodine [2439-10-3] [1 12-65-2] (free base) + TX, iminoctadine [13516-27-3] + TX, azoxystrobin [131860-33-8] + TX, dimoxystrobin [149961 -52-4] + TX, enestroburin {Proc. BCPC, Int. Congr., Glasgow, 2003, 1 , 93} + TX, fluoxastrobin [361377-29-9] + TX, kresoxim-methyl [143390-89-0] + TX, metominostrobin [133408-50-1 ] + TX, trifloxystrobin [141517-21 -7] + TX, orysastrobin [248593-16-0] + TX, picoxystrobin [1 17428-22-5] + TX, pyraclostrobin [175013-18-0] + TX, ferbam [14484-64-1 ] + TX, mancozeb [8018-01 -7] + TX, maneb [12427-38-2] + TX, metiram [9006-42-2] + TX, propineb [12071 -83-9] + TX, thiram [137-26-8] + TX, zineb [12122-67-7] + TX, ziram [137-30-4] + TX, captafol [2425- 06-1 ] + TX, captan [133-06-2] + TX, dichlofluanid [1085-98-9] + TX, fluoroimide [41205- 21 -4] + TX, folpet [133-07-3 ] + TX, tolylfluanid [731 -27-1 ] + TX, bordeaux mixture [801 1 - 63-0] + TX, copperhydroxid [20427-59-2] + TX, copperoxychlorid [1332-40-7] + TX, coppersulfat [7758-98-7] + TX, copperoxid [1317-39-1 ] + TX, mancopper [53988-93-5] + TX, oxine-copper [10380-28-6] + TX, dinocap [131 -72-6] + TX, nitrothal-isopropyl [10552- 74-6] + TX, edifenphos [17109-49-8] + TX, iprobenphos [26087-47-8] + TX, isoprothiolane [50512-35-1 ] + TX, phosdiphen [36519-00-3] + TX, pyrazophos [13457-18- 6] + TX, tolclofos-methyl [57018-04-9] + TX, acibenzolar-S-methyl [135158-54-2] + TX, anilazine [101 -05-3] + TX, benthiavalicarb [413615-35-7] + TX, blasticidin-S [2079-00-7] + TX, chinomethionat [2439-01 -2] + TX, chloroneb [2675-77-6] + TX, chlorothalonil [1897- 45-67 ⁺ TX, cyflufenamid [180409-60-3] + TX, cymoxanil [57966-95-7] + TX, dichlone [117-80-6] + TX, diclocymet [139920-32-4] + TX, diclomezine [62865-36-5] + TX, dicloran [99-30-9] + TX, diethofencarb [87130-20-9] + TX, dimethomorph [110488-70-5] + TX, SYP-LI90 (Flumorph) [211867-47-9] + TX, dithianon [3347-22-6] + TX, ethaboxam

[162650-77-3] + TX, etridiazole [2593-15-9] + TX, famoxadone [131807-57-3] + TX, fenamidone /^"767326-34-77 + TX, fenoxanil [115852-48-7] + TX, fentin [668-34-8] + TX, ferimzone [89269-64-7] + TX, fluazinam [79622-59-6] + TX, fluopicolide [2391 10-15-7] + TX, flusulfamide [106917-52-6] + TX, fenhexamid [126833-17-8] + TX, fosetyl-aluminium [39148-24-8] + TX, hymexazol [10004-44-1] + TX, iprovalicarb [140923-17-7] + TX, IKF-916 (Cyazofamid) [120116-88-3] + TX, kasugamycin [6980-18-3] + TX, methasulfo- carb [66952-49-6] + TX, metrafenone [220899-03-6] + TX, pencycuron [66063-05-6] + TX, phthalide [27355-22-2] + TX, polyoxins [1 1 1 13-80-7] + TX, probenazole [27605-76-1 ] + TX, propamocarb [25606-41 -1 ] + TX, proquinazid [189278-12-4] + TX, pyroquilon

[57369-32-1 ] + TX, quinoxyfen [124495-18-7] + TX, quintozene [82-68-8] + TX, sulphur [7704-34-9] + TX, tiadinil [223580-51 -6] + TX, triazoxide [72459-58-6] + TX, tricyclazole [41814-78-2] + TX, triforine [26644-46-2] + TX, validamycin [37248-47-8] + TX, zoxamide (RH7281 ) [156052-68-5] + TX, mandipropamid [374726-62-2] + TX, isopyrazam [881685- 58-1] + TX, sedaxane [874967-67-6] + TX, 3-difluoromethyl-1 -methyl-1 H-pyrazole-4- carboxylic acid (9-dichloromethylene-1 ,2,3,4-tetrahydro-1 ,4-methano-naphthalen-5-yl)-amide (dislosed in WO 2007/048556) + TX, 3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide (dislosed in WO 2006/087343) + TX,

[(3S,4R,4aR,6S,6aS, 12R, 12aS, 12bS)-3-[(cyclopropylcarbonyl)oxy]- 1 ,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-1 1 -oxo-9-(3- pyridinyl)-2/-/,1 1 /-/naphtho[2,1 -b]pyrano[3,4-e]pyran-4-yl]methyl- cyclopropanecarboxylate [915972-17-7] + TX and 1 ,3,5-trimethyl-N-(2-methyl-1 -oxopropyl)- N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1 -methoxy-1 -(trifluoromethyl)ethyl]phenyl]-1 H- pyrazole-4-carboxamide [926914-55-8] + 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 1 to 15 with active ingredients described above comprises a compound selected from Tables 1 to 15 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 understood to include, on the one hand, ratios by weight and also, on other hand, molar ratios.

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 1 to 15 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 1 to 15 and the active ingredients as described above is not essential for working the present invention.

The compositions 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 circum- stances - 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 compositions according to the invention are also 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 compositions prior to planting, for example seed can be treated prior to sowing. Alternatively, the compositions 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.

Biological Examples:

Example B1 : Activity against Myzus persicae (green peach aphid):

(mixed population, feeding/residual contact activity, preventive)

Sunflower leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test solutions. After drying, the leaf discs were infested with an aphid population of mixed ages. After an incubation period of 6 days, samples were checked for mortality. In this test, compounds D-29, I-28, D-27 and P-4 showed an activity of over 80% at a concentration of 200 ppm.

Example B2: Activity against Bemisia tabaci (cotton white fly):

(feeding/residual contact activity, preventive)

Cotton leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test solutions. After drying, the leaf discs were infested with 12 to 18 adults. After an incubation period of 6 days after infestation, samples were checked for mortality and special effects (e.g. phytotoxicity). In this test, compound D-29, K-23 and N-26 showed an activity of over 80% at a concentration of 200 ppm.

Claims

What is claimed is:

1 . A compound of formula I x2

wherein

is nitrogen or CRi;

X₂ is nitrogen or CR₂;

m is 0 or 1 ;

R₂ is C₂-C₆alkenyl which can be mono- to polysubstituted by substituents independently selected from the group consisting of halogen, methyl and trifluoromethyl; or

R₂ is C₂-C₆alkynyl which can be substituted by substituents selected from the group consisting of halogen, methyl and trifluoromethyl;

Q is an aromatic bicyclic ring system selected from Q₂ and Q₃

(Q₃); in which the arrow shows the connectivity to the thiazole or thiadiazole ring and wherein

Gi is nitrogen, N-CrC₄alkyl, sulpher, oxygen, a direct bond or C-R₃;

G₂ is nitrogen, N-CrC₄alkyl, sulpher, oxygen, a direct bond or C-R₄;

G₃ is nitrogen, N-CrC₄alkyl, sulpher, oxygen, a direct bond or C-R₅;

G₄ is nitrogen, N-CrC₄alkyl, sulpher, oxygen, a direct bond or C-R₆; with the provisos that a) not more than 1 substituent G can at the same time form a direct bond, b) not more than 2 substituents G can be oxygen or sulpher, and

X₃ is nitrogen, a direct bond or C-R₇;

X₅ is nitrogen, a direct bond or C-Ri₀;

X₆ is nitrogen, a direct bond or C-Rn or when X₅ is a direct bond, X₆ is NR₁₂, oxygen or sulphur, and when X₆ is a direct bond, X₅ is NR₁₂, oxygen or sulpher;

X₇ is nitrogen, a direct bond or C-Ri₄;

X₈ is nitrogen, or C-Ri₅ or when X₇ is a direct bond, X₈ is NR₁₆, oxygen or sulphur;

each of R₃, R₄, Rs, R6, R7, Rs, Rio, Rn, Ri₄, and Ri₅, which may be the same or different, represents hydrogen, halogen, nitro, cyano, hydroxy, CHO, CrC₆alkyl, C₂-C₆alkenyl, C₂- C₆alkynyl, C₃-C₆cycloalkyl, CrC₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃- C₆halocycloalkyl, CrC₄alkoxy, Ci-C₄alkoxy-Ci-C₄alkoxy-Ci-C₄alkyl, CrC₄haloalkoxy, d- C₄alkylthio, CrC₄haloalkylthio, CrC₄haloalkylsulfinyl, CrC₄haloalkylsulfonyl, d- C₄alkylsulfinyl, Ci-C₄alkylsulfonyl, Ci-C₄alkylsulfonyl-Ci-C₄alkyl, Ci-C₄alkylsulfoximino-Ci- C₄alkyl, Ci-C₄alkylamino, C₂-C₄dialkylamino, C₃-C₆cycloalkylamino, CrC₆alkyl-C₃- C₆cycloalkylamino, C₂-C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃- C₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy, C₃- C₆dialkylaminocarbonyloxy, Ci-C₄alkoxyimino-Ci-C₄alkyl, , -CONHS0₂-CrC₆-alkyl, - CONHS0₂N(CrC₆-alkyl)₂, C₃-C₆trialkylsilyl or a three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated, said three- to ten-membered, monocyclic or fused bicyclic ring system can be substituted by one to three substituents independently selected from the group consisting of CrC₄alkyl, C₂-

C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, CrC₄haloalkyl, C₂-C₄haloalkenyl, C₂-C₄haloalkynyl, C₃-C₆halocycloalkyl, halogen, cyano, nitro, CrC₄alkoxy, CrC₄haloalkoxy, CrC₄alkylthio, C C₄alkylsulfinyl, Ci-C₄alkylsulfonyl, Ci-C₄alkylsulfoximino, Ci-C₄alkylamino, C₂-C₆dialkylamino, C₃-C₆cycloalkylamino, Ci-C₄alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl, C₂- C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₂-C₈ dialkylaminocarbonyl and C₂-C₆ trialkylsilyl;

wherein R₆i and R₆2 independently from each other, are hydrogen, CrC₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, or are phenyl which can be mono-, di- or trisubstituted with substitutents selected from the group consisting of CrC₂alkyl, CrC₂haloalkyl, halogen, cyano, nitro, CrC₃alkoxy, Ci-C₄alkylthio, CrC₃alkylsulfinyl, d-C₃alkylsulfonyl, C₂- C₄alkylcarbonyl, C₂-C₄alkoxycarbonyl and C₂-C₄alkylaminocarbonyl;

X₉ is oxygen, NH, or N-Ci-C₄alkyl;

R₉, R₁₂, R₁₃ and Ri₆ are, independently from each other, hydrogen, Ci-C₂alkyl, C₃- C cycloalkyl or Ci-C₂haloalkyl; with the proviso that Q is different from the following groups

Z-1 Z-2 Z-3 and Z-4 in which the free radical shows the connectivity to the thiazole or thiadiazole ring; and agrochemically acceptable salts, enantiomers, tautomers and N-oxides of those compounds.

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

Gi is nitrogen, sulpher, oxygen, a direct bond or C-R₃;

G₂ is nitrogen, sulpher, oxygen, a direct bond or C-R₄;

G₃ is nitrogen, sulpher, oxygen, a direct bond or C-R₅;

a) not more than 1 substituent G can at the same time form a direct bond,

b) not more than 2 substituents G can be oxygen or sulpher, and

c) 2 substituents G as oxygen and/or sulpher are separated by at least one carbon atom; each of R₃, R₄, R₅, R6, R7, Re, R10, R11 , Ri₄, and Ri₅, which may be the same or different, represents hydrogen, halogen, nitro, cyano, hydroxy, CHO, CrC₆alkyl, C₂-C₆alkenyl, C₂-

C₆alkynyl, C₃-C₆cycloalkyl, CrC₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃- C₆halocycloalkyl, Ci-C₄alkoxy, Ci-C₄alkoxy-Ci-C₄alkoxy-CrC₄alkyl, Ci-C₄haloalkoxy, C

C₄alkylthio, Ci-C₄haloalkylthio, CrC₄haloalkylsulfinyl, CrC₄haloalkylsulfonyl, d- C₄alkylsulfinyl, Ci-C₄alkylsulfonyl, Ci-C₄alkylsulfonyl-Ci-C₄alkyl, Ci-C₄alkylsulfoximino-Ci- C₄alkyl, CrC₄alkylamino, C₂-C₄clialkylamino, C₃-C₆cycloalkylamino, CrC₆alkyl-C₃- C₆cycloalkylamino, C₂-C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃- C₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy, C₃- C₆dialkylaminocarbonyloxy, Ci-C₄alkoxyimino-Ci-C₄alkyl, , -CONHS0₂-Ci-C₆-alkyl, -

CONHS0₂N(Ci-C₆-alkyl)₂, C₃-C₆trialkylsilyl or a three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated, said three- to ten-membered, monocyclic or fused bicyclic ring system can be substituted by one to three substituents independently selected from the group consisting of CrC₄alkyl, C₂- C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, d-C₄haloalkyl, C₂-C₄haloalkenyl, C₂-C₄haloalkynyl, C₃-C₆halocycloalkyl, halogen, cyano, nitro, CrC₄alkoxy, CrC₄haloalkoxy, CrC₄alkylthio, C C₄alkylsulfinyl, Ci-C₄alkylsulfonyl, Ci-C₄alkylsulfoximino, Ci-C₄alkylamino, C₂-C₆dialkylamino, C₃-C₆cycloalkylamino, Ci-C₄alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl, C₂- C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₂-C₈ dialkylaminocarbonyl and C₂-C₆ trialkylsilyl.

3. A compound of formula I according to claim 1 ,

wherein

Ri is hydrogen;

Q is a group Q₃;

wherein

Gi is nitrogen, N-CrC₄alkyl, sulpher, oxygen, a direct bond or C-R₃;

G₂ is nitrogen, N-CrC₄alkyl, sulpher, oxygen, a direct bond or C-R₄;

G₃ is nitrogen, N-CrC₄alkyl, sulpher, oxygen, a direct bond or C-R₅;

X₇ is nitrogen, a direct bond or C-Ri₄;

X₈ is nitrogen, or C-Ri₅ or when X₇ is a direct bond, X₈ is NR₁₆ , oxygen or sulphur;

each of R₃, R₄, Rs, R6, Ri₄, and Ri₅, which may be the same or different, represents hydrogen, halogen, nitro, cyano, hydroxy, CHO, CrC₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃- C₆cycloalkyl, CrC₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, d- C₄alkoxy, Ci-C₄alkoxy-Ci-C₄alkoxy-Ci-C₄alkyl, CrC₄haloalkoxy, CrC₄alkylthio, d- C₄haloalkylthio, CrC₄haloalkylsulfinyl, CrC₄haloalkylsulfonyl, CrC₄alkylsulfinyl, d- C₄alkylsulfonyl, Ci-C₄alkylsulfonyl-Ci-C₄alkyl, Ci-C₄alkylsulfoximino-Ci-C₄alkyl, d- C₄alkylamino, C₂-C₄dialkylamino, C₃-C₆cycloalkylamino, Ci-C₆alkyl-C₃-C₆cycloalkylamino, C₂- C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy, C₃-C₆dialkylaminocarbonyloxy, d- dalkoxyimino-d-dalkyl, , -CONHS0₂-d-C₆-alkyl, -CONHS0₂N(d-C₆-alkyl)₂, C3-

C₆trialkylsilyl, or a three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated, said three- to ten-membered, monocyclic or fused bicyclic ring system can be substituted by one to three substituents independently selected from the group consisting of d-dalkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, d-dhaloalkyl, C₂-C₄naloalkenyl, C₂-C₄naloalkynyl, C₃-C₆halocycloalkyl, halogen, cyano, nitro, d-dalkoxy, d-dhaloalkoxy, d-dalkylthio, d-dalkylsulfinyl, d- dalkylsulfonyl, d-dalkylsulfoximino, d-dalkylamino, d-ddialkylamino, C₃- C₆cycloalkylamino, d-dalkyl-d-dcycloalkylamino, d-dalkylcarbonyl, C₂- C₆alkoxycarbonyl, d-dalkylaminocarbonyl, d-d dialkylaminocarbonyl and C₂-C₆ trialkylsilyl; and

Ri₆ is hydrogen, d-dalkyl, C₃-C₆cycloalkyl or d-dhaloalkyl.

4. A compound of formula I according to claim 1 ,

wherein

Ri is hydrogen;

Q is a group Q₂;

wherein

Gi is nitrogen, N-CrC₄alkyl, sulpher, oxygen, a direct bond or C-R₃;

G₂ is nitrogen, N-CrC₄alkyl, sulpher, oxygen, a direct bond or C-R₄;

G₃ is nitrogen, N-CrC₄alkyl, sulpher, oxygen, a direct bond or C-R₅;

b) not more than 2 substituents G can be oxygen or sulpher, and

X₅ is nitrogen, a direct bond or C-Ri₀;

each of R₃, R₄, Rs, R6, Rio, and Rn, which may be the same or different, represents hydrogen, halogen, nitro, cyano, hydroxy, CHO, CrC₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃- C₆cycloalkyl, CrC₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, d- C₄alkoxy, Ci-C₄alkoxy-Ci-C₄alkoxy-Ci-C₄alkyl, CrC₄haloalkoxy, CrC₄alkylthio, d- C₄haloalkylthio, CrC₄haloalkylsulfinyl, CrC₄haloalkylsulfonyl, CrC₄alkylsulfinyl, d- C₄alkylsulfonyl, Ci-C₄alkylsulfonyl-Ci-C₄alkyl, Ci-C₄alkylsulfoximino-Ci-C₄alkyl, d- C₄alkylamino, C₂-C₄dialkylamino, C₃-C₆cycloalkylamino, Ci-C₆alkyl-C₃-C₆cycloalkylamino, C₂- C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy, C₃-C₆dialkylaminocarbonyloxy, d- dalkoxyimino-d-dalkyl, -CONHS0₂-d-C₆-alkyl, -CONHS0₂N(d-C₆-alkyl)₂, C₃- C₆trialkylsilyl, or a three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated, said three- to ten-membered, monocyclic or fused bicyclic ring system can be substituted by one to three substituents independently selected from the group consisting of d-dalkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, d-dhaloalkyl, C₂-C₄naloalkenyl, C₂-C₄naloalkynyl, C₃-C₆halocycloalkyl, halogen, cyano, nitro, d-dalkoxy, d-dhaloalkoxy, d-dalkylthio, d-dalkylsulfinyl, d- dalkylsulfonyl, d-dalkylsulfoximino, d-dalkylamino, C₂-C₆dialkylamino, C₃- C₆cycloalkylamino, Ci-C₄alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl, C₂- C₆alkoxycarbonyl, C2-C₆alkylaminocarbonyl, C₂-C₈ dialkylaminocarbonyl and C₂-C₆ trialkylsilyl; and

Ri2 is hydrogen, CrC₂alkyl, C₃-C₆cycloalkyl or CrC₂haloalkyl.

5. A compound of formula I according to claim 1 ,

wherein

Ri is hydrogen;

Q is a group Qi ,

wherein

Gi is nitrogen, N-Ci-C₄alkyl, sulpher, oxygen, a direct bond or C-R₃;

G₂ is nitrogen, N-Ci-C₄alkyl, sulpher, oxygen, a direct bond or C-R₄;

G₃ is nitrogen, N-Ci-C₄alkyl, sulpher, oxygen, a direct bond or C-R₅;

G₄ is nitrogen, N-Ci-C₄alkyl, sulpher, oxygen, a direct bond or C-R₆; with the provisos that a) not more than 1 substituent G can at the same time form a direct bond,

b) not more than 2 substituents G can be oxygen or sulpher, and

X₃ is nitrogen, a direct bond or C-R₇;

each of R₃, R₄, R₅, R₆, R7 and R₈, which may be the same or different, represents hydrogen, halogen, nitro, cyano, hydroxy, CHO, CrC₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, CrC₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, Ci-C₄alkoxy, C C₄alkoxy-Ci-C₄alkoxy-CrC₄alkyl, Ci-C₄haloalkoxy, CrC₄alkylthio, Ci-C₄haloalkylthio, C C₄haloalkylsulfinyl, CrC₄haloalkylsulfonyl, Ci-C₄alkylsulfinyl, Ci-C₄alkylsulfonyl, d- C₄alkylsulfonyl-CrC₄alkyl, Ci-C₄alkylsulfoximino-Ci-C₄alkyl, Ci-C₄alkylamino, C₂- C₄dialkylamino, C₃-C₆cycloalkylamino, Ci-C₆alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C2-C₆alkylaminocarbonyl, C₃-C₆dialkylaminocarbonyl, C₂- C₆alkoxycarbonyloxy, C2-C₆alkylaminocarbonyloxy, C₃-C₆dialkylaminocarbonyloxy, d- C₄alkoxyimino-Ci-C4alkyl, -CONHS0₂-Ci-C₆-alkyl, -CONHS0₂N(Ci-C₆-alkyl)_2! C₃- C₆trialkylsilyl, or a three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated, said three- to ten-membered, monocyclic or fused bicyclic ring system can be substituted by one to three substituents independently selected from the group consisting of CrC₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, CrC₄haloalkyl, C₂-C₄haloalkenyl, C₂-C₄haloalkynyl, C₃-C₆halocycloalkyl, halogen, cyano, nitro, CrC₄alkoxy, CrC₄haloalkoxy, CrC₄alkylthio, CrC₄alkylsulfinyl, d- C₄alkylsulfonyl, Ci-C₄alkylsulfoximino, Ci-C₄alkylamino, C₂-C₆dialkylamino, C₃- C₆cycloalkylamino, Ci-C₄alkyl-C₃-C₆cycloalkylamino, C₂-C₄alkylcarbonyl, C₂- C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₂-C₈ dialkylaminocarbonyl and C₂-C₆ trialkylsilyl; and

R₉ is hydrogen, Ci-C₂alkyl, C₃-C₆cycloalkyl or Ci-C₂haloalkyl.

6. A compound of formula I according to claim 1 represented by the compound of formula 1-1

wherein

G₂ is nitrogen, N-CrC₄alkyl, sulpher, oxygen, or C-R₄;

G₃ is nitrogen, N-CrC₄alkyl, sulpher, oxygen, or C-R₅;

G₄ is nitrogen, N-CrC₄alkyl, sulpher, oxygen, or C-R₆; with the provisos that

a) not more than 2 substituents G can be oxygen or sulpher, and

each of R₄, R₅, and R₆ which may be the same or different, represents hydrogen, halogen, nitro, Ci-C₃alkyl, -CONHS0₂-C C₆-alkyl, -CONHS0₂N(CrC₆-alkyl)₂, C C₃haloalkyl, or an unsubstituted three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated.

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

wherein

R₂ is halogen, hydrogen or CrC₂alkyl;

G₂ is nitrogen, N-Ci-C₄alkyl, sulpher, oxygen, or C-R₄;

G₃ is nitrogen, N-Ci-C₄alkyl, sulpher, oxygen, or C-R₅;

G₄ is nitrogen, N-Ci-C₄alkyl, sulpher, oxygen, or C-R₆; with the provisos that

a) not more than 2 substituents G can be oxygen or sulpher, and

each of R₄, R₅, and R₆ which may be the same or different, represents hydrogen, halogen, nitro, C C₃alkyl, -CONHS0₂-C C₆-alkyl, -CONHS0₂N(CrC₆-alkyl)₂, C C₃haloalkyl, or an unsubstituted three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated.

8. A compound of formula I accordin to claim 1 represented by the compound of formula I-3

wherein

G₂, G₃ and G₄ form together with the two carbon atoms to which G₂ and G₄ are attached, aromatic ring system; wherein

G₂ is nitrogen, N-Ci-C₄alkyl, sulpher, oxygen, or C-R₄; G₃ is nitrogen, N-CrC₄alkyl, sulpher, oxygen, or C-R₅;

a) not more than 2 substituents G can be oxygen or sulpher, and

R₆o represents hydrogen, halogen, CrC₆alkyl, C₃-C₆cycloalkyl, CrC₆haloalkyl, C₃- C₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy, C₃- Cedialkylaminocarbonyloxy, -CONHS0₂-Ci-C₆-alkyl, -CONHS0₂N(Ci-C₆-alkyl)₂ , or an unsubstituted three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated.

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

wherein

R₂ is halogen, hydrogen or Ci-C₂alkyl;

G₂ is nitrogen, N-Ci-C₄alkyl, sulpher, oxygen, or C-R₄;

G₃ is nitrogen, N-Ci-C₄alkyl, sulpher, oxygen, or C-R₅;

a) not more than 2 substituents G can be oxygen or sulpher, and

each of R₄, R₅, and R₆ which may be the same or different, represents hydrogen, halogen, nitro, Ci-C₃alkyl, or CrC₆haloalkyl;

R₆o represents hydrogen, halogen, CrC₆alkyl, C₃-C₆cycloalkyl, CrC₆haloalkyl, C₃- C₆dialkylaminocarbonyl, C₂-C₆alkoxycarbonyloxy, C₂-C₆alkylaminocarbonyloxy, C₃- Cedialkylaminocarbonyloxy, -CONHS0₂-Ci-C₆-alkyl, -CONHS0₂N(Ci-C₆-alkyl)_2! or an unsubstituted three- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated.

10. A pesticidal composition, which comprises at least one compound of formula I according to claim 1 or, where appropriate, a tautomer thereof, in each case in free form or in agrochemically utilizable salt form, as active ingredient and at least one auxiliary.

1 1 . A method for controlling pests, which comprises applying a composition according to claim 10 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.

12. A method for the protection of plant propagation material from the attack by pests, which comprises treating the propagation material or the site, where the propagation material is planted, with a composition according to claim 10.

13. Plant propagation material treated in accordance with the method described in claim 12.