CONDENSED BICYCLIC HETEROCYCLIC DERIVATIVES AS PEST CONTROL AGENTS

Abstract

The invention relates to novel compounds of formula (I), in which Aa, Ab, Ac, Ad, Ae, Q, R.sup.1 and n are defined as in the description, to the use thereof as acaricides and/or insecticides for controlling animal pests, and to processes and intermediate products for the preparation thereof.

Claims

1. A compound of the formula (I) ##STR00057## in which Aa represents nitrogen or C(R.sup.7), Ab represents nitrogen or C(R.sup.8), Ac represents nitrogen or C(R.sup.9), Ad represents nitrogen or C(R.sup.10), Ae represents nitrogen or C(R.sup.11), where Ab, Ac, Ad and Ae cannot simultaneously represent nitrogen, R.sup.1 represents (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.2-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-haloalkenyl, (C.sub.2-C.sub.6)-alkynyl, (C.sub.2-C.sub.6)-haloalkynyl, (C.sub.3-C.sub.8)-cycloalkyl, halo-(C.sub.3-C.sub.8)-cycloalkyl, (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-alkyl-(C.sub.3-C.sub.8)-cycloalkyl, (C.sub.1-C.sub.6)-haloalkyl-(C.sub.3-C.sub.8)-cycloalkyl, (C.sub.3-C.sub.8)-cycloalkyl-(C.sub.3-C.sub.8)-cycloalkyl, spiro-(C.sub.3-C.sub.8)-cycloalkyl-(C.sub.3-C.sub.8)-cycloalkyl, (C.sub.4-C.sub.12)-bicycloalkyl, (C.sub.1-C.sub.6)-cyanoalkyl, (C.sub.1-C.sub.6)-hydroxyalkyl, (C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.6)-alkyl, (C.sub.2-C.sub.6)-cyanoalkenyl, (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.2-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-cyanoalkynyl, (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.2-C.sub.6)-alkynyl, (C.sub.1-C.sub.6)-haloalkoxy-(C.sub.1-C.sub.6)-alkyl, (C.sub.2-C.sub.6)-alkenyloxy-(C.sub.1-C.sub.6)-alkyl, (C.sub.2-C.sub.6)-haloalkenyloxy-(C.sub.1-C.sub.6)-alkyl, (C.sub.2-C.sub.6)-alkynyloxy-(C.sub.1-C.sub.4)-alkyl, (C.sub.2-C.sub.6)-haloalkynyloxy-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkylthio-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkylsulfinyl-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkylsulfonyl-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkylthio-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkylsulfinyl-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkylsulfonyl-(C.sub.1-C.sub.6)-alkyl or tri-(C.sub.1-C.sub.6)-alkylsilyl, R.sup.7 represents hydrogen, cyano, halogen, acetyl, hydroxyl, amino, (C.sub.3-C.sub.8)-cycloalkyl, halo(C.sub.3-C.sub.8)-cycloalkyl, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-cyanoalkyl, (C.sub.2-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-haloalkenyl, (C.sub.2-C.sub.6)-alkynyl, (C.sub.2-C.sub.6)-haloalkynyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.1-C.sub.6)-haloalkoxy, (C.sub.1-C.sub.6)-alkylthio, (C.sub.1-C.sub.6)-haloalkylthio, (C.sub.1-C.sub.6)-alkylsulfinyl, (C.sub.1-C.sub.6)-haloalkylsulfinyl, (C.sub.1-C.sub.6)-alkylsulfonyl or (C.sub.1-C.sub.6)-haloalkylsulfonyl, R.sup.8, R.sup.9, R.sup.10, R.sup.11 independently of one another represent hydrogen, halogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.1-C.sub.6)-haloalkoxy, (C.sub.1-C.sub.6)-haloalkylthio, (C.sub.1-C.sub.6)-haloalkylsulfinyl, (C.sub.1-C.sub.6)-haloalkylsulfonyl or represent (C.sub.1-C.sub.6)-haloalkyl-(C.sub.3-C.sub.8)-cycloalkyl, optionally mono- or poly-halogen-substituted (C.sub.1-C.sub.6)-cyanoalkyl, (C.sub.1-C.sub.6)-cyanoalkyl-(C.sub.3-C.sub.8)-cycloalkyl, (C.sub.1-C.sub.6)-haloalkyl-(C.sub.3-C.sub.8)-cyanocycloalkyl, (C.sub.1-C.sub.6)-haloalkyl-(C.sub.3-C.sub.8)-halocycloalkyl, optionally mono- or poly-(C.sub.1-C.sub.6)-alkyl- or -halogen-substituted cyano-(C.sub.3-C.sub.6)-cycloalkyl, in each case optionally mono- or poly-cyano- or -halogen-substituted spiro-(C.sub.3-C.sub.8)-cycloalkyl-(C.sub.3-C.sub.8)-cycloalkyl or (C.sub.4-C.sub.12)-bicycloalkyl, where one of the radicals R.sup.8, R.sup.9, R.sup.10, R.sup.11 must be selected from (C.sub.1-C.sub.6)-haloalkyl-(C.sub.3-C.sub.8)-cycloalkyl, (C.sub.1-C.sub.6)-cyanoalkyl-(C.sub.3-C.sub.8)-cycloalkyl, (C.sub.1-C.sub.6)-haloalkyl-(C.sub.3-C.sub.8)-cyanocycloalkyl, (C.sub.1-C.sub.6)-haloalkyl-(C.sub.3-C.sub.8)-halocycloalkyl, optionally mono- or poly-(C.sub.1-C.sub.6)-alkyl- or -halogen-substituted cyano(C.sub.3-C.sub.6)-cycloalkyl, in each case optionally mono- or poly-cyano- or -halogen-substituted spiro-(C.sub.3-C.sub.8)-cycloalkyl-(C.sub.3-C.sub.8)-cycloalkyl or (C.sub.4-C.sub.12)-bicycloalkyl, where only one or two of the radicals R.sup.8, R.sup.9, R.sup.10, R.sup.11 represent a substituent other than hydrogen, Q is ##STR00058## ##STR00059## R.sup.4 represents (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl, (C.sub.1-C.sub.4)-cyanoalkyl, (C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkoxy-(C.sub.1-C.sub.4)-alkyl, (C.sub.2-C.sub.4)-alkenyl, (C.sub.2-C.sub.4)-alkenyloxy-(C.sub.1-C.sub.4)-alkyl, (C.sub.2-C.sub.4)-alkynyl, (C.sub.2-C.sub.4)-alkynyloxy-(C.sub.1-C.sub.4)-alkyl or (C.sub.3-C.sub.6)-cycloalkyl, R.sup.5, R.sup.6 are independently of one another hydrogen, cyano, halogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl, (C.sub.2-C.sub.4)-alkenyl, (C.sub.2-C.sub.4)-haloalkenyl, (C.sub.2-C.sub.4)-alkynyl, (C.sub.2-C.sub.4)-haloalkynyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.3-C.sub.6)-cycloalkyl, (C.sub.1-C.sub.4)-alkyl-(C.sub.3-C.sub.6)-cycloalkyl, (C.sub.1-C.sub.4)-alkoxy, (C.sub.1-C.sub.4)-haloalkoxy, (C.sub.1-C.sub.4)-alkoxyimino, (C.sub.1-C.sub.4)-alkylthio, (C.sub.1-C.sub.4)-haloalkylthio, (C.sub.1-C.sub.4)-alkylsulfinyl, (C.sub.1-C.sub.4)-haloalkylsulfinyl, (C.sub.1-C.sub.4)-alkylsulfonyl, (C.sub.1-C.sub.4)-haloalkylsulfonyl, (C.sub.1-C.sub.4)-alkylsulfonyloxy, (C.sub.1-C.sub.4)-alkylcarbonyl, (C.sub.1-C.sub.4)-haloalkylcarbonyl, aminocarbonyl, (C.sub.1-C.sub.4)-alkylaminocarbonyl, di-(C.sub.1-C.sub.4)-alkylaminocarbonyl, (C.sub.1-C.sub.4)-alkylsulfonylamino, (C.sub.1-C.sub.4)-alkylamino, di-(C.sub.1-C.sub.4)-alkylamino, aminosulfonyl, (C.sub.1-C.sub.4)-alkylaminosulfonyl or di-(C.sub.1-C.sub.4)-alkylaminosulfonyl, n represents 0, 1 or 2.

2. A compound of the formula (I) as claimed in claim 1, in which Aa represents nitrogen or C(R.sup.7), Ab represents nitrogen or C(R.sup.8), Ac represents nitrogen or C(R.sup.9), Ad represents nitrogen or C(R.sup.10), Ae represents nitrogen or C(R.sup.11), where Ab, Ac, Ad and Ae cannot simultaneously represent nitrogen, resulting in the following structural units: A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17, R.sup.1 represents (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.2-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-haloalkenyl, (C.sub.2-C.sub.6)-alkynyl, (C.sub.2-C.sub.6)-haloalkynyl, (C.sub.3-C.sub.8)-cycloalkyl, halo-(C.sub.3-C.sub.8)-cycloalkyl, (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-alkyl-(C.sub.3-C.sub.8)-cycloalkyl, (C.sub.1-C.sub.6)-haloalkyl-(C.sub.3-C.sub.8)-cycloalkyl, (C.sub.1-C.sub.6)-cyanoalkyl, (C.sub.1-C.sub.6)-hydroxyalkyl, (C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkoxy-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkylthio-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkylsulfinyl-(C.sub.1-C.sub.6)-alkyl or (C.sub.1-C.sub.6)-alkylsulfonyl-(C.sub.1-C.sub.6)-alkyl, R.sup.7 represents hydrogen, cyano, halogen, acetyl, hydroxyl, amino, (C.sub.3-C.sub.6)-cycloalkyl, halo(C.sub.3-C.sub.6)-cycloalkyl, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl, (C.sub.1-C.sub.4)-cyanoalkyl, (C.sub.2-C.sub.4)-alkenyl, (C.sub.2-C.sub.4)-haloalkenyl, (C.sub.2-C.sub.4)-alkynyl, (C.sub.2-C.sub.4)-haloalkynyl, (C.sub.1-C.sub.4)-alkoxy, (C.sub.1-C.sub.4)-haloalkoxy, (C.sub.1-C.sub.4)-alkylthio, (C.sub.1-C.sub.4)-haloalkylthio, (C.sub.1-C.sub.4)-alkylsulfinyl, (C.sub.1-C.sub.4)-haloalkylsulfinyl, (C.sub.1-C.sub.4)-alkylsulfonyl or (C.sub.1-C.sub.4)-haloalkylsulfonyl, R.sup.8, R.sup.9, R.sup.10, R.sup.11 independently of one another represent hydrogen, halogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.1-C.sub.6)-haloalkoxy, (C.sub.1-C.sub.6)-haloalkylthio, (C.sub.1-C.sub.6)-haloalkylsulfinyl, (C.sub.1-C.sub.6)-haloalkylsulfonyl or represent (C.sub.1-C.sub.6)-haloalkyl-(C.sub.3-C.sub.8)-cycloalkyl, represent optionally mono- or poly-halogen-substituted (C.sub.1-C.sub.6)-cyanoalkyl, (C.sub.1-C.sub.6)-cyanoalkyl-(C.sub.3-C.sub.8)-cycloalkyl, (C.sub.1-C.sub.6)-haloalkyl-(C.sub.3-C.sub.8)-cyanocycloalkyl, (C.sub.1-C.sub.6)-haloalkyl-(C.sub.3-C.sub.8)-halocycloalkyl, optionally mono- or poly-(C.sub.1-C.sub.4)-alkyl- or -halogen-substituted cyano(C.sub.3-C.sub.6)-cycloalkyl, in each case optionally mono- or poly-cyano- or -halogen-substituted spiro-(C.sub.3-C.sub.8)-cycloalkyl-(C.sub.3-C.sub.8)-cycloalkyl or (C.sub.4-C.sub.12)-bicycloalkyl, where one of the radicals R.sup.8, R.sup.9, R.sup.10 or R.sup.11 must be selected from (C.sub.1-C.sub.6)-haloalkyl-(C.sub.3-C.sub.8)-cycloalkyl, (C.sub.1-C.sub.6)-cyanoalkyl-(C.sub.3-C.sub.8)-cycloalkyl, (C.sub.1-C.sub.6)-haloalkyl-(C.sub.3-C.sub.8)-cyanocycloalkyl, (C.sub.1-C.sub.6)-haloalkyl-(C.sub.3-C.sub.8)-halocycloalkyl, optionally mono- or poly-(C.sub.1-C.sub.4)-alkyl- or -halogen-substituted cyano(C.sub.3-C.sub.6)-cycloalkyl, in each case optionally mono- or poly-cyano- or -halogen-substituted spiro-(C.sub.3-C.sub.8)-cycloalkyl-(C.sub.3-C.sub.8)-cycloalkyl or (C.sub.4-C.sub.12)-bicycloalkyl, where only one or two of the radicals R.sup.8, R.sup.9, R.sup.10, or R.sup.11 represent a substituent other than hydrogen, n represents 0, 1 or 2.

3. A compound of the formula (I) as claimed in claim 1, in which Aa represents nitrogen or C(R.sup.7), Ab represents nitrogen or C(R.sup.8), Ac represents nitrogen or C(R.sup.9), Ad represents nitrogen or C(R.sup.10), Ae represents nitrogen or C(R.sup.11), where Ab, Ac, Ad and Ae cannot simultaneously represent nitrogen, resulting in the following structural units: A1, A2, A6, A7, A9, A11, A13, A16, R.sup.1 represents (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl or (C.sub.3-C.sub.8)-cycloalkyl, R.sup.7 represents hydrogen, halogen, cyano, (C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.4)-haloalkyl, R.sup.8, R.sup.10, R.sup.11 independently of one another represent hydrogen, halogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl, (C.sub.1-C.sub.4)-alkoxy, (C.sub.1-C.sub.4)-haloalkoxy, (C.sub.1-C.sub.4)-haloalkylthio, (C.sub.1-C.sub.4)-haloalkylsulfinyl or (C.sub.1-C.sub.4)-haloalkylsulfonyl, R.sup.9 represents (C.sub.1-C.sub.4)-haloalkyl-(C.sub.3-C.sub.8)-cycloalkyl, spiro-(C.sub.3-C.sub.8)-cycloalkyl-(C.sub.3-C.sub.8)-cycloalkyl, (C.sub.4-C.sub.12)-bicycloalkyl or optionally mono- or di-(C.sub.1-C.sub.4)-alkyl- or -halogen-substituted cyano-(C.sub.3-C.sub.6)-cycloalkyl, n represents 0, 1 or 2.

4. A compound of the formula (I) as claimed in claim 1, in which Aa represents nitrogen or C(R.sup.7), Ab represents nitrogen or C(R.sup.8), Ac represents nitrogen or C(R.sup.9), Ad represents nitrogen or C(R.sup.10), Ae represents nitrogen or C(R.sup.11), where Ab, Ac, Ad and Ae cannot simultaneously represent nitrogen, resulting in the following structural units: A1, A2, A6, A11, A16 R.sup.1 represents (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl or (C.sub.3-C.sub.6)-cycloalkyl, R.sup.7 represents hydrogen, halogen, cyano, (C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.4)-haloalkyl, R.sup.8, R.sup.10, R.sup.11 independently of one another represent hydrogen, (C.sub.1-C.sub.4)-alkyl or halogen, R.sup.9 represents cyano(C.sub.3-C.sub.6)cycloalkyl, R.sup.4 represents (C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)-alkyl, R.sup.5 represents hydrogen, cyano, halogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.1-C.sub.4)-alkoxy, (C.sub.1-C.sub.4)-haloalkoxy, (C.sub.1-C.sub.4)-alkoxyimino, (C.sub.1-C.sub.4)-alkylthio, (C.sub.1-C.sub.4)-haloalkylthio, (C.sub.1-C.sub.4)-alkylsulfinyl, (C.sub.1-C.sub.4)-haloalkylsulfinyl, (C.sub.1-C.sub.4)-alkylsulfonyl, (C.sub.1-C.sub.4)-haloalkylsulfonyl, (C.sub.1-C.sub.4)-alkylcarbonyl or (C.sub.1-C.sub.4)-haloalkylcarbonyl, R.sup.6 represents hydrogen, n represents 0, 1 or 2.

5. A compound of the formula (I) as claimed in claim 1, in which Aa represents C(R.sup.7), Ab represents C(R.sup.8), Ac represents C(R.sup.9), Ad represents C(R.sup.10), Ae represents C(R.sup.11), R.sup.1 represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, R.sup.7 represents hydrogen, R.sup.8 represents hydrogen, R.sup.9 represents cyanocyclopropyl or cyanocyclobutyl, R.sup.10 represents hydrogen, R.sup.11 represents hydrogen, R.sup.4 represents methyl, ethyl, isopropyl, methoxymethyl or methoxyethyl, R.sup.5 represents fluorine, chlorine, bromine, fluoromethyl, difluoromethyl, trifluoromethyl, fluoroethyl (CH.sub.2CFH.sub.2, CHFCH.sub.3), difluoroethyl (CF.sub.2CH.sub.3, CH.sub.2CHF.sub.2, CHFCFH.sub.2), trifluoroethyl, (CH.sub.2CF.sub.3, CHFCHF.sub.2, CF.sub.2CFH.sub.2), tetrafluoroethyl (CHFCF.sub.3, CF.sub.2CHF.sub.2), pentafluoroethyl, trifluoromethoxy, pentafluoroethoxy, difluorochloromethoxy, dichlorofluoromethoxy, trifluoromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, R.sup.6 represents hydrogen, n represents 0, 1 or 2.

6. A compound of the formula (I) as claimed in claim 1, in which Aa represents C(R.sup.7), Ab represents C(R.sup.8), Ac represents C(R.sup.9), Ad represents C(R.sup.10), Ae represents C(R.sup.11), R.sup.1 represents ethyl, R.sup.7 represents hydrogen, R.sup.8 represents hydrogen, R.sup.9 represents 1-cyanocyclopropyl, R.sup.10 represents hydrogen, R.sup.11 represents hydrogen, R.sup.4 represents methyl, R.sup.5 represents trifluoromethyl, pentafluoroethyl, trifluoromethoxy, pentafluoroethoxy or trifluoromethylsulfonyl, R.sup.6 represents hydrogen, n represents 2.

7. An agrochemical formulation comprising compounds of the formula (I) as claimed in claim 1, extenders, and surfactants.

8. The agrochemical formulation as claimed in claim 7, additionally comprising a further agrochemically active compound.

9. A method of controlling animal pests, characterized in that a compound of the formula (I) as claimed in claim 1 is allowed to act on the animal pests and/or their habitat.

10. The use of compounds of the formula (I) as claimed in claim 1 for controlling animal pests.

11. The compound of claim 1, wherein Q is ##STR00060##

Description

PREPARATION EXAMPLES

1-[4-Ethylsulfonyl-3-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-7-isoquinolyl]cyclopropanecarbonitrile (I-1)

##STR00026##

[0646] 87 mg (0.18 mmol) of 1-[4-ethylsulfanyl-3-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-7-isoquinolyl]cyclopropanecarbonitrile were dissolved in 6 ml of dichloromethane, 43.5 mg (0.94 mmol) of formic acid and 128.6 mg (1.32 mmol) of hydrogen peroxide were added at room temperature, and then the mixture was stirred at room temperature for 16 h. The mixture was diluted with water, 20% sodium bisulfite solution was added, the mixture was stirred for 30 min, and then 2 ml of 20% sodium hydrogencarbonate solution was added. The organic phase was separated off, the aqueous phase was extracted twice with dichloromethane and the combined organic phases were then freed of the solvent under reduced pressure. The residue was purified by column chromatography using, as mobile phase, a cyclohexane/ethyl acetate gradient.

[0647] (log P (neutral): 3.02; MH+: 486; .sup.1H-NMR (400 MHz, D6-DMSO) ppm: 1.27 (t, 3H), 1.79-1.82 (m, 2H), 1.99-2.02 (m, 2H), 3.78-3.83 (m, 2H), 8.02 (d, 1H), 8.52 (s, 1H), 8.62 (s, 1H), 8.88 (s, 1H), 8.95 (d, 1H), 9.83 (s, 1H).

1-[4-Ethylsulfanyl-3-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-7-isoquinolyl]cyclopropanecarbonitrile

##STR00027##

[0648] To an initial charge of 140 mg (0.28 mmol) of 2-[4-ethylsulfanyl-3-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-7-isoquinolyl]acetonitrile and 108 mg (0.57 mmol) of 1,2-dibromoethane in 3 ml of dimethylformamide under argon was added 34.2 mg (0.85 mmol) of sodium hydride at 0 C., and the mixture was stirred at 0 C. for 1 h. Subsequently, the reaction mixture was added to saturated ammonium chloride solution and extracted three times with ethyl acetate. The combined organic phases were washed once each with water and a sodium chloride solution, dried over sodium sulfate and freed of the solvent under reduced pressure. The residue was purified by column chromatography using, as mobile phase, a cyclohexane/ethyl acetate gradient.

[0649] (log P (neutral): 3.67; MH.sup.+: 454; .sup.1H-NMR (400 MHz, D.sub.6-DMSO) ppm: 0.97 (t, 3H), 1.77-1.80 (m, 2H), 1.95-1.99 (m, 2H), 2.83 (q, 2H), 3.76 (s, 3H), 7.96 (d, 1H), 8.38 (s, 1H), 8.62-8.65 (m, 2H), 8.87 (s, 1H), 9.54 (s, 1H).

2-[4-Ethylsulfanyl-3-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-7-isoquinolyl]acetonitrile

##STR00028##

[0650] To an initial charge of 206 mg (0.39 mmol) of 7-bromo-4-ethylsulfanyl-3-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]isoquinoline, 390.4 mg (1.96 mmol) of 4-isoxazole boronic acid pinacol ester and 417.2 mg (2.74 mmol) of cesium fluoride under argon in a mixture of 12 ml of DMF and 2 ml of water was then added 57.4 mg (0.07 mmol) of 1,1-bis(diphenylphosphino)ferrocenedichloropalladium(II), and the mixture was stirred at 130-135 C. under argon for 16 h. Subsequently, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography with a water/acetonitrile gradient plus 0.1 ml/1 formic acid as mobile phase.

[0651] The intermediate was stirred in the presence of 37 mg of potassium fluoride in a mixture of 8 ml of water and 2 ml of methanol at 90 C. for 1 h. After the solvent have been distilled off, the residue was added to a mixture of 10 ml each of water and dichloromethane. The organic phase was separated off, the aqueous phase was extracted twice with dichloromethane, the combined organic phases were dried over sodium sulfate, and then the solvent was distilled off under reduced pressure.

[0652] (log P (neutral): 3.22; MH.sup.+: 428; .sup.1H-NMR (400 MHz, D.sub.6-DMSO) ppm: 0.98 (t, 3H), 2.84 (q, 2H), 3.77 (s, 3H), 4.42 (s, 2H), 8.02 (d, 1H), 8.35 (s, 1H), 8.65-8.67 (m, 2H), 8.87 (s, 1H), 9.57 (s, 1H).

7-Bromo-4-ethylsulfanyl-3-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]isoquinoline

##STR00029##

[0653] 500 mg (2.61 mmol) of N2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine. 1.021 g (3.27 mmol) of 7-bromo-4-ethylsulfanylisoquinoline-3-carboxylic acid and 501 mg (2.61 mmol) of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCIHCl) were dissolved in 9 ml of pyridine and stirred at 120 C. for 20 h. Subsequently, the solvent was distilled off under reduced pressure, and the residue was admixed with water and extracted with ethyl acetate. The organic phase was dried over sodium sulfate and the solvent was again distilled off under reduced pressure. The residue was admixed with 50 ml of glacial acetic acid and heated to boiling for 9 h. The reaction mixture was admixed with water, and the precipitated solids were filtered off with suction, washed with water and dried.

[0654] (log P (neutral): 4.36; MH.sup.+: 467; .sup.1H-NMR (400 MHz, D.sub.6-DMSO) ppm: 0.98 (t, 3H), 2.84 (q, 2H), 3.77 (s, 3H), 4.42 (s, 2H), 8.19 (d, 1H), 8.56 (d, 1H), 8.35 (s, 1H), 8.6 (s, 1H), 8.69 (s, 1H), 8.87 (s, 1H), 9.51 (s, 1H).

7-Bromo-4-ethylsulfanylisoquinoline-3-carboxylic acid (ex. III-C-1)

##STR00030##

[0655] To a solution of 6.60 g (20.2 mmol) of methyl 7-bromo-4-ethylsulfanylisoquinoline-3-carboxylate in 50 ml of anhydrous tetrahydrofuran (THF) were added 0.867 g (20.7 mmol) of lithium hydroxide monohydrate (LiOHH.sub.2O) and 70 ml of distilled water, and the reaction mixture was stirred at room temperature for 6 h. The tetrahydrofuran was distilled off, and the aqueous solution was adjusted to pH 4 with sodium hydrogensulfate (NaHSO.sub.4). The precipitated solids were filtered off and dissolved in 200 ml of ethyl acetate. The solution was dried over sodium sulfate and then the solvent was distilled off under reduced pressure.

[0656] .sup.1H-NMR (400 MHz, D.sub.6-DMSO) ppm: 1.08 (t, 3H), 2.89 (q, 2H), 8.10 (d, 1H), 8.44 (d, 1H), 8.56 (s, 1H), 9.32 (s, 1H), 13.57 (s, 1H).

Methyl 7-bromo-4-ethylsulfanylisoquinoline-3-carboxylate (ex. XLIII-1)

##STR00031##

[0657] To a solution of methyl 7-bromo-4-sulfanylisoquinoline-3-carboxylate that had been obtained from the preceding stage was added 20.2 g (130 mmol) of ethyl iodide, and the reaction mixture was stirred at room temperature for 16 h. Subsequently, the solvent was distilled off under reduced pressure and the residue was dissolved in 200 ml of ethyl acetate. The organic phase was washed with 100 ml of water, dried over sodium sulfate, filtered off and the solvent was distilled off again under reduced pressure. The residue was purified by column chromatography with hexane/ethyl acetate (7:3) as eluent.

[0658] .sup.1H-NMR (400 MHz, Chloroform-d) ppm: 1.17 (t, 3H), 2.88 (q, 2H), 4.02 (s, 3H), 7.90 (d, 1H), 8.18 (s, 1H) 8.49 (d, 1H), 9.11 (s, 1H).

Methyl 7-bromo-4-sulfanylisoquinoline-3-carboxylate (ex. XLII-1)

##STR00032##

[0659] To a solution of 12.0 g (32.5 mmol) of methyl 7-bromo-4-(dimethylcarbamoylsulfanyl)isoquinoline-3-carboxylate in 40 ml of methanol under argon was added a solution of sodium methoxide in methanol (prepared by addition of 2.25 g (97.8 mmol) of sodium to 100 ml of methanol). The reaction mixture was heated to 60 C. for 8 h. Subsequently, the solution was cooled to room temperature and used in the next stage without further purification.

Methyl 7-bromo-4-(dimethylcarbamoylsulfanyl)isoquinoline-3-carboxylate (ex. XLI-1)

##STR00033##

[0660] A solution of 18.0 g (48.7 mmol) of methyl 7-bromo-4-(dimethylcarbamothioyloxy)isoquinoline-3-carboxylate in 180 ml of diphenyl ether under argon was stirred at 190 C. for 6 h, then cooled to room temperature and added to 1500 ml of hexane. The product was obtained by filtering off the precipitate.

[0661] .sup.1H-NMR (400 MHz, Chloroform-d) ppm: 2.99 (s, 3H), 3.22 (s, 3H), 4.00 (s, 3H), 7.86 (d, 1H), 8.18 (s, 1H), 8.26 (d, 1H), 9.20 (s, 1H).

Methyl 7-bromo-4-(dimethylcarbamothioyloxy)isoquinoline-3-carboxylate (ex. XL-1)

##STR00034##

[0662] To a solution of 16.8 g (59.6 mmol) of methyl 7-bromo-4-hydroxyisoquinoline-3-carboxylate and 26.7 g (238 mmol) of 1,4-diazabicyclo[2.2.2]octane (DABCO) in 250 ml of DMF was added 9.60 g (77.7 mmol) of dimethylthiocarbamoyl chloride in portions. The reaction mixture was stirred at room temperature for 16 h and then added to 1 l of water. The aqueous phase was extracted three times with 400 ml each time of ethyl acetate, the combined organic phases were dried over sodium sulfate, and the solvent was finally distilled off under reduced pressure.

[0663] .sup.1H-NMR (500 MHz, Chloroform-d) ppm: 3.54 (s, 3H), 3.56 (s, 3H), 4.00 (s, 3H), 7.87 (d, 1H), 7.94 (d, 1H), 8.25 (s, 1H), 9.14 (s, 1H).

Methyl 7-bromo-4-hydroxyisoquinoline-3-carboxylate (ex. XXXIX-1)

##STR00035##

[0664] To a solution of 39.0 g (82.9 mmol) of methyl 4-bromo-2-[[(2-methoxy-2-oxoethyl)(p-tolylsulfonyl)amino]methyl]benzoate in 390 ml of DMSO was added dropwise a solution of sodium methoxide in methanol (prepared by addition of 5.90 g (257 mmol) of sodium to 80 ml of methanol), keeping the internal temperature below 25 C. The reaction mixture was stirred at room temperature for 5 h, then added to 2 l of water and extracted three times with 300 ml each time of ethyl acetate. The combined organic phases were washed with a sodium chloride solution and dried over sodium sulfate, and then the solvent was distilled off under reduced pressure. The product was obtained by washing the residue with methanol.

[0665] .sup.1H-NMR (500 MHz, Chloroform-d) ppm: 4.10 (s, 3H), 7.86 (dd, 1H), 8.14 (d, 1H), 8.28 (d, 1H), 8.74 (s, 1H), 11.76 (s, 1H).

Methyl 4-bromo-2-[[(2-methoxy-2-oxo-ethyl)(p-tolylsulfonyl)amino]methyl]benzoate (ex. XXXVII-1)

##STR00036##

[0666] A solution of 39.0 g (127 mmol) of methyl 4-bromo-2-(bromomethyl)benzoate, 33.8 g (139 mmol) of methyl (toluene-4-sulfonylamino)acetate, 28.5 g (190 mmol) of sodium iodide and 26.2 g (190 mmol) of potassium carbonate was stirred at room temperature for 16 h and then added to 3 l of water. The aqueous phase was extracted twice with 900 ml each time of ethyl acetate, the combined organic phases were concentrated to about 500 ml, washed with a sodium chloride solution and dried over sodium sulfate, and then the solvent was distilled off under reduced pressure. The product was obtained by washing the residue with methyl tert-butyl ether (MTBE).

[0667] .sup.1H-NMR (400 MHz, Chloroform-d) ppm: 2.41 (s, 3H), 3.55 (s, 3H), 3.81 (s, 3H), 3.97 (s, 2H), 4.83 (s, 2H), 7.28 (m, 2H), 7.44 (d, 1H), 7.71 (m, 4H).

[0668] In analogy to the examples and according to the above-described preparation processes, the following compounds of the formula (I) can be obtained:

TABLE-US-00001 Example Structure I-2 [00037] I-3 [00038] I-4 [00039] I-5 [00040] I-6 [00041] I-7 [00042] I-8 [00043] I-9 [00044] I-10 [00045] I-11 [00046] I-12 [00047] I-13 [00048] I-14 [00049] I-15 [00050] I-16 [00051] I-17 [00052] I-18 [00053]

TABLE-US-00002 .sup.1H NMR spectra I-2: .sup.1H-NMR(400.2 MHz, d.sub.6-DMSO): = 9.8228 (4.3); 9.2778 (3.9); 8.9542 (2.0); 8.9313 (2.2); 8.5247 (2.5); 8.5195 (2.6); 8.3162 (0.4); 8.2495 (4.0); 8.0380 (1.6); 8.0325 (1.5); 8.0150 (1.5); 8.0095 (1.5); 3.8782 (16.0); 3.7824 (1.0); 3.7650 (1.0); 3.3250 (65.8); 2.6758 (0.7); 2.6713 (1.0); 2.6667 (0.7); 2.5248 (2.8); 2.5200 (4.4); 2.5112 (62.4); 2.5069 (127.5); 2.5023 (167.2); 2.4978 (119.8); 2.4934 (57.4); 2.3337 (0.7); 2.3291 (1.0); 2.3246 (0.7); 2.0748 (0.8); 2.0271 (1.0); 2.0137 (2.9); 2.0066 (3.2); 1.9950 (1.2); 1.8210 (1.3); 1.8085 (3.0); 1.8015 (3.1); 1.7877 (1.0); 1.2692 (3.8); 1.2506 (8.5); 1.2321 (3.8); 0.1459 (0.5); 0.0080 (3.7); 0.0001 (116.8); 0.0085 (3.9); 0.1495 (0.5) I-3: .sup.1H-NMR(400.2 MHz, d.sub.6-DMSO): = 9.8283 (7.5); 8.8941 (3.4); 8.8713 (3.8); 8.5305 (4.5); 8.5253 (4.5); 8.3165 (0.5); 8.3072 (4.2); 8.3040 (4.2); 8.1733 (3.3); 8.1518 (3.9); 8.0567 (2.7); 8.0513 (2.6); 8.0338 (2.6); 8.0283 (2.6); 7.8866 (2.3); 7.8831 (2.3); 7.8650 (2.0); 7.8612 (2.0); 3.7969 (1.9); 3.7784 (6.3); 3.7599 (6.4); 3.7414 (1.9); 3.3269 (110.4); 2.6765 (0.7); 2.6719 (1.0); 2.6673 (0.7); 2.5254 (3.1); 2.5206 (4.8); 2.5119 (58.8); 2.5074 (117.8); 2.5029 (154.2); 2.4983 (112.2); 2.4938 (54.2); 2.3343 (0.7); 2.3297 (0.9); 2.3252 (0.7); 2.3210 (0.3); 2.0314 (1.9); 2.0181 (5.2); 2.0109 (5.7); 1.9992 (2.4); 1.8315 (2.4); 1.8189 (5.4); 1.8119 (5.5); 1.7979 (1.8); 1.2901 (7.2); 1.2716 (16.0); 1.2531 (7.0); 1.2341 (0.5); 0.0080 (1.8); 0.0002 (53.1); 0.0085 (1.7) I-4: .sup.1H-NMR(600.1 MHz, d.sub.6-DMSO): = 9.8246 (3.8); 8.9552 (1.8); 8.9400 (2.0); 8.8072 (2.1); 8.8040 (2.2); 8.5685 (2.1); 8.5653 (2.2); 8.5206 (2.2); 8.5169 (2.3); 8.0366 (1.4); 8.0329 (1.4); 8.0213 (1.4); 8.0176 (1.5); 4.0359 (0.8); 4.0241 (0.8); 3.8160 (0.4); 3.8049 (0.9); 3.7925 (1.0); 3.7825 (16.0); 3.3222 (82.4); 2.6150 (0.4); 2.5240 (0.9); 2.5209 (1.1); 2.5178 (1.0); 2.5090 (19.2); 2.5060 (42.6); 2.5029 (59.9); 2.4999 (43.2); 2.4969 (19.8); 2.3869 (0.4); 2.0198 (0.9); 2.0110 (2.8); 2.0065 (3.0); 1.9985 (1.0); 1.9892 (3.4); 1.8166 (1.2); 1.8080 (2.8); 1.8035 (3.0); 1.7943 (0.9); 1.3976 (0.9); 1.2771 (3.6); 1.2647 (7.9); 1.2524 (3.5); 1.1878 (1.0); 1.1759 (1.9); 1.1640 (1.0); 0.0054 (1.7); 0.0001 (55.4); 0.0057(1.6) I-5: .sup.1H-NMR(600.1 MHz, d.sub.6-DMSO): = 9.8124 (3.8); 8.9544 (1.7); 8.9391 (2.0); 8.5658 (1.9); 8.5618 (1.9); 8.5112 (2.2); 8.5076 (2.2); 8.3315 (2.0); 8.3278 (1.9); 8.0291 (1.4); 8.0254 (1.4); 8.0138 (1.4); 8.0101 (1.4); 3.8226 (0.4); 3.8105 (1.0); 3.7984 (1.0); 3.7522 (16.0); 3.3192 (99.3); 2.6174 (0.4); 2.6143 (0.5); 2.6113 (0.3); 2.5233 (1.0); 2.5202 (1.3); 2.5171 (1.2); 2.5083 (23.8); 2.5053 (53.6); 2.5022 (76.0); 2.4992 (54.6); 2.4962 (24.7); 2.3893 (0.4); 2.3861 (0.5); 2.3831 (0.3); 2.0156 (1.0); 2.0068 (2.8); 2.0023 (3.0); 1.9943 (1.1); 1.9888 (1.0); 1.8136 (1.2); 1.8050 (2.8); 1.8004 (3.0); 1.7913 (1.0); 1.3980 (0.6); 1.2768 (3.6); 1.2645 (8.1); 1.2521 (3.6); 1.1757 (0.5); 0.0054 (1.9); 0.0001 (73.0); 0.0057 (2.2) I-6: .sup.1H-NMR(600.1 MHz, d.sub.6-DMSO): = 9.7953 (3.6); 9.7947 (3.6); 8.9671 (1.8); 8.9519 (1.9); 8.4978 (2.3); 8.4942 (2.2); 8.0689 (2.0); 8.0120 (1.5); 8.0083 (1.4); 7.9967 (1.5); 7.9930 (1.5); 7.9388 (1.5); 7.9246 (1.7); 7.7139 (1.2); 7.7112 (1.2); 7.6995 (1.1); 7.6970 (1.1); 3.8263 (0.6); 3.7753 (16.0); 3.3193 (91.2); 2.6171 (0.4); 2.6141 (0.5); 2.6111 (0.4); 2.5231 (1.1); 2.5200 (1.4); 2.5169 (1.3); 2.5081 (25.4); 2.5051 (56.6); 2.5020 (79.8); 2.4989 (56.6); 2.4959 (25.2); 2.3889 (0.3); 2.3858 (0.5); 2.3827 (0.3); 2.0108 (0.9); 2.0020 (2.8); 1.9975 (3.0); 1.9887 (2.1); 1.8111 (1.2); 1.8024 (2.7); 1.7979 (3.0); 1.7887 (0.9); 1.2796 (3.6); 1.2672 (8.1); 1.2548 (3.6); 1.1874 (0.4); 1.1755 (0.7); 1.1637 (0.3); 0.0054 (2.2); 0.0001 (81.6); 0.0057 (2.4) I-7: .sup.1H-NMR(400.2 MHz, d.sub.6-DMSO): = 9.8458 (7.6); 8.8851 (3.4); 8.8622 (3.7); 8.7749 (4.3); 8.7707 (4.4); 8.5449 (4.4); 8.5397 (4.5); 8.3932 (3.3); 8.3714 (6.3); 8.3306 (3.1); 8.3262 (3.1); 8.3160 (0.7); 8.3089 (1.6); 8.3043 (1.6); 8.0687 (2.7); 8.0633 (2.7); 8.0458 (2.6); 8.0404 (2.6); 3.7952 (1.8); 3.7767 (6.1); 3.7582 (6.2); 3.7397 (1.9); 3.3284 (151.2); 2.6801 (0.5); 2.6760 (1.1); 2.6714 (1.6); 2.6669 (1.2); 2.6624 (0.6); 2.5248 (5.1); 2.5114 (91.8); 2.5070 (185.3); 2.5024 (247.1); 2.4979 (184.4); 2.4934 (92.4); 2.3384 (0.5); 2.3338 (1.1); 2.3293 (1.6); 2.3248 (1.2); 2.0865 (4.3); 2.0365 (1.9); 2.0231 (5.1); 2.0159 (5.7); 2.0043 (2.4); 1.8348 (2.4); 1.8221 (5.4); 1.8151 (5.6); 1.8012 (1.8); 1.3512 (0.6); 1.2981 (0.8); 1.2850 (7.1); 1.2666 (16.0); 1.2591 (1.9); 1.2480 (7.2); 1.2332 (1.4); 0.1458 (0.5); 0.0080 (5.1); 0.0002 (137.1); 0.0085 (5.4); 0.1497 (0.6) I-8: .sup.1H-NMR(400.2 MHz, d.sub.6-DMSO): = 9.8150 (8.7); 8.8922 (3.8); 8.8694 (4.2); 8.5207 (5.0); 8.5156 (5.2); 8.3160 (0.6); 8.0489 (2.9); 8.0435 (2.9); 8.0334 (5.8); 8.0260 (3.0); 8.0206 (3.0); 8.0111 (6.2); 7.9954 (3.8); 7.9922 (4.0); 7.5864 (2.2); 7.5823 (2.2); 7.5644 (1.9); 7.5600 (2.0); 3.7918 (2.0); 3.7734 (6.8); 3.7549 (6.9); 3.7364 (2.1); 3.3244 (197.0); 2.6754 (1.6); 2.6708 (2.2); 2.6664 (1.7); 2.5241 (6.4); 2.5064 (263.7); 2.5020 (350.2); 2.4976 (265.8); 2.3332 (1.6); 2.3289 (2.2); 2.3245 (1.6); 2.0270 (2.1); 2.0135 (5.9); 2.0063 (6.5); 1.9946 (2.7); 1.8270 (2.6); 1.8145 (6.1); 1.8075 (6.3); 1.7936 (2.0); 1.5877 (0.5); 1.2886 (7.4); 1.2701 (16.0); 1.2516 (7.4); 1.2346 (1.1); 0.1457 (0.8); 0.0078 (5.4); 0.0002 (159.7); 0.0082 (8.1); 0.1500 (0.8) I-9: .sup.1H-NMR(400.2 MHz, d.sub.6-DMSO): = 9.8632 (4.3); 8.9378 (1.9); 8.9150 (2.1); 8.7196 (6.5); 8.5558 (2.5); 8.5506 (2.5); 8.3159 (0.5); 8.0663 (1.5); 8.0609 (1.5); 8.0434 (1.5); 8.0379 (1.5); 5.7562 (0.5); 3.9438 (16.0); 3.7778 (0.6); 3.7592 (1.7); 3.7405 (1.7); 3.7228 (0.6); 3.3252 (162.8); 2.6757 (1.2); 2.6711 (1.6); 2.6666 (1.2); 2.6621 (0.6); 2.5245 (5.0); 2.5197 (7.6); 2.5111 (92.7); 2.5067 (188.4); 2.5021 (250.5); 2.4976 (184.5); 2.4931 (91.3); 2.3379 (0.5); 2.3335 (1.1); 2.3290 (1.6); 2.3245 (1.1); 2.0383 (1.0); 2.0248 (2.9); 2.0178 (3.2); 2.0061 (1.3); 1.8286 (1.3); 1.8161 (3.0); 1.8091 (3.1); 1.7953 (1.0); 1.3509 (0.6); 1.2983 (0.3); 1.2688 (4.0); 1.2584 (1.0); 1.2503 (8.9); 1.2318 (5.5); 0.8535 (0.4); 0.1460 (0.4); 0.0080 (3.0); 0.0002 (96.7); 0.0084 (3.5); 0.1497 (0.4) I-10: .sup.1H-NMR(400.2 MHz, d.sub.6-DMSO): = 9.8657 (4.8); 8.9369 (2.1); 8.9139 (2.3); 8.7628 (6.5); 8.5569 (2.8); 8.5519 (2.8); 8.0684 (1.6); 8.0631 (1.5); 8.0454 (1.5); 8.0401 (1.5); 3.9469 (16.0); 3.7783 (0.7); 3.7603 (1.9); 3.7419 (1.9); 3.7236 (0.7); 3.3261 (77.6); 2.6760 (0.6); 2.6716 (0.8); 2.6674 (0.6); 2.5246 (2.8); 2.5070 (94.6); 2.5026 (122.9); 2.4983 (92.3); 2.3337 (0.6); 2.3295 (0.7); 2.3251 (0.6); 2.0866 (2.1); 2.0400 (1.1); 2.0264 (3.2); 2.0194 (3.6); 2.0076 (1.4); 1.8296 (1.4); 1.8172 (3.3); 1.8102 (3.4); 1.7963 (1.1); 1.2686 (4.0); 1.2500 (8.6); 1.2316 (4.0); 0.0076 (1.3); 0.0002 (35.9); 0.0083 (1.6) I-11: .sup.1H-NMR(400.2 MHz, d.sub.6-DMSO): = 9.8124 (4.3); 8.9575 (2.0); 8.9346 (2.2); 8.5970 (2.1); 8.5920 (2.2); 8.5116 (2.5); 8.5065 (2.5); 8.3410 (2.0); 8.3377 (2.0); 8.0319 (1.5); 8.0264 (1.5); 8.0089 (1.5); 8.0034 (1.5); 3.8302 (0.6); 3.8120 (1.6); 3.7936 (1.7); 3.7759 (0.6); 3.7465 (16.0); 3.3214 (42.1); 2.6754 (0.6); 2.6711 (0.8); 2.6667 (0.6); 2.5246 (2.4); 2.5109 (52.4); 2.5066 (107.2); 2.5022 (141.0); 2.4977 (101.2); 2.4934 (49.0); 2.3334 (0.6); 2.3291 (0.8); 2.3244 (0.6); 2.0224 (1.0); 2.0089 (3.0); 2.0018 (3.2); 1.9892 (2.2); 1.8180 (1.3); 1.8054 (3.0); 1.7984 (3.1); 1.7846 (1.0); 1.3976 (1.6); 1.2821 (3.7); 1.2636 (8.2); 1.2450 (3.7); 1.1752 (0.6); 0.0002 (2.3) I-12: .sup.1H-NMR(400.2 MHz, d.sub.6-DMSO): = 9.7838 (4.5); 8.9686 (2.0); 8.9456 (2.2); 8.4894 (2.6); 8.4843 (2.6); 8.0103 (1.6); 8.0049 (1.5); 7.9873 (1.5); 7.9818 (1.5); 7.8272 (2.6); 7.8051 (2.9); 7.6972 (2.2); 7.3977 (1.2); 7.3756 (1.0); 7.3725 (1.0); 3.8386 (1.1); 3.8206 (1.1); 3.7430 (16.0); 3.3238 (83.0); 2.6757 (0.4); 2.6712 (0.6); 2.6668 (0.4); 2.5246 (1.8); 2.5111 (39.2); 2.5068 (79.6); 2.5023 (104.1); 2.4978 (73.9); 2.4935 (35.3); 2.3334 (0.4); 2.3290 (0.6); 2.3247 (0.4); 2.0146 (1.0); 2.0012 (3.1); 1.9940 (3.4); 1.9891 (2.0); 1.9825 (1.4); 1.8130(1.4); 1.8005 (3.2); 1.7935 (3.2); 1.7797 (1.0); 1.3976 (0.9); 1.2822 (3.8); 1.2637 (8.2); 1.2452 (3.7); 1.1930 (0.3); 1.1752 (0.7); 1.1574 (0.3); 0.0002 (1.6) I-13: .sup.1H-NMR(400.2 MHz, d.sub.6-DMSO): = 9.8225 (4.3); 9.2995 (4.0); 8.9533 (2.0); 8.9303 (2.2); 8.5238 (2.5); 8.5186 (2.6); 8.2730 (4.0); 8.2711 (4.3); 8.0400 (1.6); 8.0346 (1.5); 8.0170 (1.5); 8.0116 (1.5); 3.8778 (16.0); 3.7817 (1.0); 3.7646 (1.0); 3.3190 (50.9); 2.6752 (0.7); 2.6707 (1.1); 2.6662 (0.8); 2.5242 (2.9); 2.5195 (4.5); 2.5107 (64.5); 2.5063 (134.0); 2.5018 (177.8); 2.4972 (127.7); 2.4927 (61.7); 2.3376 (0.4); 2.3332 (0.8); 2.3286 (1.1); 2.3241 (0.8); 2.0740 (0.4); 2.0269 (1.0); 2.0134 (2.9); 2.0064 (3.2); 1.9947 (1.2); 1.8209 (1.3); 1.8083 (3.0); 1.8013 (3.1); 1.7874 (1.0); 1.2689 (3.8); 1.2503 (8.6); 1.2318 (3.8); 0.0080 (2.1); 0.0002 (67.6); 0.0085 (2.3) I-14: .sup.1H-NMR(400.2 MHz, d.sub.6-DMSO): = 9.8205 (4.5); 9.2622 (4.0); 8.9549 (1.9); 8.9318 (2.2); 8.5215 (2.6); 8.5165 (2.6); 8.3142 (0.7); 8.1618 (4.2); 8.1601 (4.2); 8.0361 (1.5); 8.0308 (1.5); 8.0132 (1.5); 8.0077 (1.4); 7.1851 (0.4); 7.0675 (0.4); 7.0544 (0.7); 7.0389 (0.4); 6.9227 (0.4); 4.0381 (0.6); 4.0202 (0.6); 3.8709 (16.0); 3.7867 (1.0); 3.7678 (1.1); 3.3260 (561.8); 2.6754 (1.7); 2.6709 (2.4); 2.6664 (1.8); 2.6618 (0.8); 2.5243 (7.5); 2.5194 (11.6); 2.5108 (156.5); 2.5065 (318.1); 2.5020 (415.9); 2.4975 (295.9); 2.4931 (141.7); 2.3377 (0.9); 2.3332 (1.8); 2.3288 (2.4); 2.3242 (1.8); 2.0258 (1.0); 2.0123 (3.1); 2.0054 (3.4); 1.9934 (1.4); 1.9886 (2.8); 1.8209 (1.4); 1.8084 (3.1); 1.8013 (3.2); 1.7876 (1.1); 1.3979 (0.8); 1.2717 (3.9); 1.2532 (8.5); 1.2346 (4.1); 1.1928 (0.7); 1.1750 (1.3); 1.1573 (0.7); 0.0002 (6.6) I-15: .sup.1H-NMR(400.2 MHz, d.sub.6-DMSO): = 9.8441 (4.2); 9.1640 (3.0); 9.1587 (3.1); 8.9756 (2.6); 8.9704 (2.5); 8.9468 (1.9); 8.9239 (2.1); 8.5403 (2.5); 8.5351 (2.5); 8.0538 (1.5); 8.0483 (1.5); 8.0308 (1.5); 8.0253 (1.5); 4.0557 (0.5); 4.0379 (1.4); 4.0201 (1.4); 4.0023 (0.5); 3.8234 (16.0); 3.7924 (1.6); 3.7740 (1.5); 3.7560 (0.6); 3.3330 (112.8); 2.6768 (0.6); 2.6722 (0.8); 2.6675 (0.6); 2.5256 (2.5); 2.5208 (3.8); 2.5122 (44.2); 2.5078 (88.5); 2.5032 (116.0); 2.4986 (85.2); 2.4941 (42.1); 2.3345 (0.5); 2.3300 (0.7); 2.3255 (0.5); 2.0339 (1.0); 2.0206 (2.8); 2.0133 (3.3); 2.0017 (1.3); 1.9896 (6.1); 1.8258 (1.3); 1.8130 (2.9); 1.8061 (3.0); 1.7923 (1.0); 1.3974 (1.2); 1.2796 (3.8); 1.2611 (8.4); 1.2426 (3.7); 1.1931 (1.7); 1.1753 (3.3); 1.1575 (1.6); 0.1459 (0.6); 0.0079 (4.5); 0.0002 (128.8); 0.0085 (5.2); 0.1496 (0.6) I-16: .sup.1H-NMR(400.2 MHz, d.sub.6-DMSO): = 9.7957 (4.5); 8.9390 (2.0); 8.9160 (2.2); 8.4967 (2.7); 8.4917 (2.6); 8.0152 (1.5); 8.0098 (1.5); 7.9922 (1.5); 7.9868 (1.4); 7.4037 (4.6); 3.9306 (16.0); 3.7577 (1.1); 3.7420 (1.1); 3.6466 (7.9); 3.3286 (144.6); 2.6759 (0.8); 2.6714 (1.0); 2.6671 (0.7); 2.5247 (3.3); 2.5070 (125.8); 2.5025 (162.7); 2.4980 (118.4); 2.3338 (0.7); 2.3293 (1.0); 2.3248 (0.7); 2.0170 (1.0); 2.0035 (3.1); 1.9965 (3.4); 1.9850(1.3); 1.8112 (1.4); 1.7987 (3.2); 1.7917 (3.2); 1.7778 (1.0); 1.2643 (3.8); 1.2457 (8.4); 1.2272 (3.8); 0.0079 (2.9); 0.0002 (75.2); 0.0085 (2.8); 0.1497 (0.3) I-17: .sup.1H-NMR(400.2 MHz, d.sub.6-DMSO): = 9.8269 (7.6); 8.8963 (3.5); 8.8734 (3.8); 8.5300 (4.5); 8.5248 (4.5); 8.3482 (4.4); 8.3165 (0.4); 8.1413 (3.1); 8.1199 (3.8); 8.0550 (2.8); 8.0495 (2.6); 8.0320 (2.6); 8.0266 (2.6); 7.9362 (2.6); 7.9326 (2.5); 7.9147 (2.1); 7.9109 (2.0); 5.7567 (6.7); 3.7965 (1.9); 3.7780 (6.3); 3.7594 (6.4); 3.7410 (2.0); 3.3302 (191.8); 3.2570 (0.7); 2.6765 (0.9); 2.6720 (1.2); 2.6674 (0.8); 2.6629 (0.4); 2.5253 (3.7); 2.5118 (73.5); 2.5075 (144.8); 2.5030 (187.4); 2.4985 (134.6); 2.4941 (64.8); 2.3343 (0.8); 2.3298 (1.1); 2.3254 (0.8); 2.3209 (0.4); 2.0306 (1.9); 2.0172 (5.4); 2.0100 (5.8); 1.9983 (2.4); 1.8312 (2.5); 1.8187 (5.5); 1.8117 (5.6); 1.7977 (1.8); 1.2908 (7.2); 1.2723 (16.0); 1.2538 (7.2); 1.2338 (0.9); 0.1460 (0.4); 0.0079 (3.0); 0.0001 (84.1); 0.0084 (3.0); 0.1495 (0.4) I-18: .sup.1H-NMR(400.2 MHz, d.sub.6-DMSO): = 9.8171 (7.7); 8.8922 (3.4); 8.8693 (3.8); 8.5225 (4.4); 8.5173 (4.5); 8.3159 (0.8); 8.0503 (3.0); 8.0432 (6.1); 8.0274 (2.9); 8.0210 (7.2); 7.9903 (3.9); 7.9845 (4.0); 7.5683 (2.3); 7.5620 (2.2); 7.5459 (2.1); 7.5400 (2.1); 3.7949 (1.8); 3.7763 (6.1); 3.7577 (6.2); 3.7392 (2.0); 3.3300 (566.1); 2.6758 (2.3); 2.6713 (3.2); 2.6669 (2.4); 2.5245 (9.3); 2.5111 (192.6); 2.5068 (385.8); 2.5023 (505.4); 2.4978 (365.7); 2.4934 (177.9); 2.3337 (2.2); 2.3291 (3.0); 2.3246 (2.2); 2.0863 (2.2); 2.0279 (1.9); 2.0145 (5.3); 2.0071 (5.7); 1.9955 (2.4); 1.8281 (2.4); 1.8156 (5.5); 1.8086 (5.6); 1.7947 (1.8); 1.2971 (0.8); 1.2895 (7.3); 1.2710(16.0); 1.2525 (7.2); 1.2345 (1.1); 0.1459 (1.0); 0.0078 (8.0); 0.0002 (223.5); 0.0084 (8.0); 0.1498 (1.0)

USE EXAMPLES

Diabrotica BalteataSpray Test

[0669] Solvent: 78 parts by weight of acetone [0670] 1.5 parts by weight of dimethylformamide

[0671] Emulsifier: alkylaryl polyglycol ether

[0672] To produce a suitable active compound formulation, 1 part by weight of active compound is dissolved using the stated parts by weight of solvent and made up with water containing an emulsifier concentration of 1000 ppm until the desired concentration is attained. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

[0673] Pre-swollen wheat grains (Triticum aestivum) are incubated in a multiwell plate filled with agar and a little water for one day (5 seed grains per cavity). The germinated wheat grains are sprayed with an active compound formulation of the desired concentration. Subsequently, each cavity is infected with 10-20 beetle larvae of Diabrotica balteata.

[0674] After 7 days, the efficacy in % is determined. 100% means that all wheat plants have grown as in the untreated, uninfected control; 0% means that no wheat plant has grown.

[0675] In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 100 g/ha (=32 g/cavity): ex. I-2, I-3, I-4, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14.

Myzus persicaeSpray Test

[0676] Solvent: 78 parts by weight of acetone [0677] 1.5 parts by weight of dimethylformamide

[0678] Emulsifier: alkylaryl polyglycol ether

[0679] To produce a suitable active compound formulation, 1 part by weight of active compound is dissolved using the stated parts by weight of solvent and made up with water containing an emulsifier concentration of 1000 ppm until the desired concentration is attained. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

[0680] Disks of Chinese cabbage leaves (Brassica pekinensis) infested by all stages of the green peach aphid (Myzus persicae) are sprayed with an active compound formulation of the desired concentration.

[0681] After 5 days, the efficacy in % is determined. 100% means that all the aphids have been killed; 0% means that no aphids have been killed.

[0682] In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 100 g/ha: I-4, I-10, I-11, I-12, I-13, I-14.

[0683] In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 100 g/ha: I-1, I-2, I-5, I-6, I-9.

Myzus PersicaeOral Test

[0684] Solvent: 100 parts by weight of acetone

[0685] To produce a suitable active compound formulation, 1 part by weight of active compound is dissolved using the specified parts by weight of solvent and made up with water until the desired concentration is attained.

[0686] 50 l of the active compound preparation are transferred into microtitre plates and made up to a final volume of 200 l with 150 l of IPL41 insect medium (33%+15% sugar). Subsequently, the plates are sealed with parafilm, which a mixed population of green peach aphids (Myzus persicae) within a second microtitre plate is able to puncture and imbibe the solution through.

[0687] After 5 days, the efficacy in % is determined. 100% means that all the aphids have been killed; 0% means that no aphids have been killed.

[0688] In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 4 ppm: ex. I-1, I-2, I-4, I-5, I-6, I-11, I-12, I-13, I-14.

[0689] In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 0.8 ppm: ex. I-4, I-11, I-13, I-14.

[0690] In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 0.8 ppm: ex. I-1, I-2, I-9, I-10, I-12.

Phaedon cochleariaeSpray Test

[0691] Solvent: 78.0 parts by weight of acetone [0692] 1.5 parts by weight of dimethylformamide

[0693] Emulsifier: alkylaryl polyglycol ether

[0694] To produce a suitable active compound formulation, 1 part by weight of active compound is dissolved using the stated parts by weight of solvent and made up with water containing an emulsifier concentration of 1000 ppm until the desired concentration is attained. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

[0695] Disks of Chinese cabbage leaves (Brassica pekinensis) are sprayed with an active compound formulation of the desired concentration and, after drying, populated with larvae of the mustard beetle (Phaedon cochleariae).

[0696] After 7 days, the efficacy in % is determined. 100% means that all the beetle larvae have been killed; 0% means that no beetle larvae have been killed.

[0697] In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 100 g/ha: ex. I-1.

Spodoptera FrugiperdaSpray Test

[0698] Solvent: 78.0 parts by weight of acetone [0699] 1.5 parts by weight of dimethylformamide

[0700] Emulsifier: alkylaryl polyglycol ether

[0701] To produce a suitable active compound formulation, 1 part by weight of active compound is dissolved using the stated parts by weight of solvent and made up with water containing an emulsifier concentration of 1000 ppm until the desired concentration is attained. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

[0702] Leaf disks of corn (Zea mays) are sprayed with an active compound formulation of the desired concentration and, after drying, populated with caterpillars of the fall armyworm (Spodopterafrugiperda).

[0703] After 7 days, the efficacy in % is determined. 100% means that all the caterpillars have been killed; 0% means that no caterpillar has been killed.

[0704] In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 100 g/ha: ex. I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14.

Tetranychus urticaeSpray Test, OP-Resistant

[0705] Solvent: 78.0 parts by weight of acetone [0706] 1.5 parts by weight of dimethylformamide

[0707] Emulsifier: alkylaryl polyglycol ether

[0708] To produce a suitable active compound formulation, 1 part by weight of active compound is dissolved using the stated parts by weight of solvent and made up with water containing an emulsifier concentration of 1000 ppm until the desired concentration is attained. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

[0709] Disks of bean leaves (Phaseolus vulgaris) infested with all stages of the greenhouse red spider mite (Tetranychus urticae) are sprayed with an active compound formulation of the desired concentration.

[0710] After 6 days, the efficacy in % is determined. 100% means that all the spider mites have been killed; 0% means that no spider mites have been killed.

[0711] In this test, for example, the following compounds from the preparation examples shows an efficacy of 90% at an application rate of 100 g/ha: ex. I-9.

Comparative Experiments

Myzus persicaeSpray Test (MYZUPE)

[0712] Solvent: 78.0 parts by weight of acetone [0713] 1.5 parts by weight of dimethylformamide

[0714] Emulsifier: alkylaryl polyglycol ether

[0715] To produce a suitable active compound formulation, 1 part by weight of active compound is dissolved using the stated parts by weight of solvent and made up with water containing an emulsifier concentration of 1000 ppm until the desired concentration is attained. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

[0716] Disks of Chinese cabbage leaves (Brassica pekinensis) infested by all stages of the green peach aphid (Myzus persicae) are sprayed with an active compound preparation of the desired concentration.

[0717] After the desired period of time, the efficacy in % is determined. 100% means that all the aphids have been killed; 0% means that no aphids have been killed.

[0718] In this test, for example, the following compounds from the preparation examples show superior efficacy to the prior art: see table.

Phaedon cochleariaeSpray Test (PHAECO)

[0719] Solvent: 78.0 parts by weight of acetone [0720] 1.5 parts by weight of dimethylformamide

[0721] Emulsifier: alkylaryl polyglycol ether

[0722] To produce a suitable active compound formulation, 1 part by weight of active compound is dissolved using the stated parts by weight of solvent and made up with water containing an emulsifier concentration of 1000 ppm until the desired concentration is attained. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

[0723] Disks of Chinese cabbage leaves (Brassica pekinensis) are sprayed with an active compound formulation of the desired concentration and, after drying, populated with larvae of the mustard beetle (Phaedon cochleariae).

[0724] After the desired period of time, the efficacy in % is determined. 100% means that all the beetle larvae have been killed; 0% means that no beetle larvae have been killed.

[0725] In this test, for example, the following compounds from the preparation examples show superior efficacy to the prior art: see table.

Spodoptera frugiperdaSpray Test (SPODFR)

[0726] Solvent: 78.0 parts by weight of acetone [0727] 1.5 parts by weight of dimethylformamide

[0728] Emulsifier: alkylaryl polyglycol ether

[0729] To produce a suitable active compound formulation, 1 part by weight of active compound is dissolved using the stated parts by weight of solvent and made up with water containing an emulsifier concentration of 1000 ppm until the desired concentration is attained. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

[0730] Leaf disks of corn (Zea mays) are sprayed with an active compound formulation of the desired concentration and, after drying, populated with caterpillars of the armyworm (Spodoptera frugiperda).

[0731] After the desired period of time, the efficacy in % is determined. 100% means that all the caterpillars have been killed; 0% means that no caterpillar has been killed.

[0732] In this test, for example, the following compounds from the preparation examples show superior efficacy to the prior art: see table.

TABLE-US-00003 Animal % efficacy Substance Structure species Concentration dat Ex. I-1 inventive [00054] PHAECO SPODFR MYZUPE 20 4 20 4 0.8 100 20 4 g of ai/ha g of ai/ha g of ai/ha g of ai/ha g of ai/ha g of ai/ha g of ai/ha g of ai/ha 100 100 100 100 83 90 90 70 7 dat 7 dat 7 dat 7 dat 7 dat 5 dat 5 dat 5 dat Ex. I-47 known from WO 2017/072039 [00055] PHAECO SPODFR 20 4 20 4 0.8 g of ai/ha g of ai/ha g of ai/ha g of ai/ha g of ai/ha 67 0 67 33 0 7 dat 7 dat 7 dat 7 dat 7 dat Ex. I-51 known from WO 2017/072039 [00056] MYZUPE 100 20 4 g of ai/ha g of ai/ha g of ai/ha 90 0 0 5 dat 5 dat 5 dat dat = days after treatment