TRICYCLIC CARBOXAMIDES FOR CONTROLLING ARTHROPODS

Abstract

The invention relates, inter alia, to compounds of general formula (I). The invention also relates to methods for synthesizing the compounds of formula (I). The compounds according to the invention are in particular suitable for controlling insects, arachnids and nematodes in agricultural applications and for controlling ectoparasites in veterinary medicine.

Claims

1. A compound of formula (I) ##STR00035## in which R.sup.1 is H, optionally in each case mutually independently substituted by one or more substituents, selected from amino, hydroxyl, halogen, nitro, cyano, isocyano, mercapto, isothiocyanato, C.sub.1-C.sub.4-carboxyl, carbonamide, SF.sub.5, aminosulfonyl, C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.4-cycloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.5-C.sub.6-cycloalkenyl, C.sub.2-C.sub.4-alkynyl, N-mono-C.sub.1-C.sub.4-alkylamino, N,N-di-C.sub.1-C.sub.4-alkylamino, N—C.sub.1-C.sub.4-alkanoylamino, C.sub.1-C.sub.4-alkoxy, C.sub.2-C.sub.4-alkenyloxy, C.sub.2-C.sub.4-alkynyloxy, C.sub.3-C.sub.4-cycloalkoxy, C.sub.5-C.sub.6-cycloalkenyloxy, C.sub.1-C.sub.4-alkoxycarbonyl, C.sub.2-C.sub.4-alkenyloxycarbonyl, C.sub.2-C.sub.4-alkynyloxycarbonyl, C.sub.6-,C.sub.10-,C.sub.4-aryloxycarbonyl, C.sub.1-C.sub.4-alkanoyl, C.sub.2-C.sub.4-alkenylcarbonyl, C.sub.2-C.sub.4-alkynylcarbonyl, C.sub.6-,C.sub.10-,C.sub.14-arylcarbonyl, C.sub.1-C.sub.4-alkylsulfanyl, C.sub.3-C.sub.4-cycloalkylsulfanyl, C.sub.1-C.sub.4-alkylthio, C.sub.2-C.sub.4-alkenylthio, C.sub.5-C.sub.6-cycloalkenylthio, C.sub.2-C.sub.4-alkynylthio, C.sub.1-C.sub.4-alkylsulfenyl and C.sub.1-C.sub.4-alkylsulfinyl, wherein both enantiomers of the C.sub.1-C.sub.4-alkylsulfinyl group are included, C.sub.1-C.sub.4-alkylsulfonyl, N-mono-C.sub.1-C.sub.4-alkylaminosulfonyl, N,N-di-C.sub.1-C.sub.4-alkylaminosulfonyl, C.sub.1-C.sub.4-alkylphosphinyl, C.sub.1-C.sub.4-alkylphosphonyl, wherein for C.sub.1-C.sub.4-alkylphosphinyl or C.sub.1-C.sub.4-alkylphosphonyl both enantiomers are included, N—C.sub.1-C.sub.4-alkylaminocarbonyl, N,N-di-C.sub.1-C.sub.4-alkylaminocarbonyl, N—C.sub.1-C.sub.4-alkanoylaminocarbonyl, N—C.sub.1-C.sub.4-alkanoyl-N—C.sub.1-C.sub.4-alkylaminocarbonyl, C.sub.6-,C.sub.10-,C.sub.14-aryl, C.sub.6-,C.sub.10-,C.sub.14-aryloxy, benzyl, benzyloxy, benzylthio, C.sub.6-,C.sub.10-,C.sub.14-arylthio, C.sub.6-,C.sub.10-,C.sub.14-arylamino, benzylamino, heterocyclyl and trialkylsilyl, having substituents linked by a double bond such as C.sub.1-C.sub.4-alkylidene, an oxo group-substituted or an imino group-substituted C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.7-cycloalkyl, C.sub.1-C.sub.6-alkylcarbonyl, C.sub.1-C.sub.6-alkoxycarbonyl, C.sub.6-,C.sub.10-,C.sub.14-aryl(C.sub.1-C.sub.3)-alkyl, 3, 4, 5, 6, 7, 8, 9 or 10-membered heterocyclyl (optionally thietanyl optionally thiethanyl-3-yl, oxidothiethane such as 1-oxidothietan-3-yl, or dioxidothiethane such as 1,1-dioxidothietan-3-yl) or 3, 4, 5, 6, 7, 8, 9 or 10-membered-heterocyclyl(C.sub.1-C.sub.3)-alkyl, optionally C.sub.3-C.sub.7-cycloalkyl optionally substituted by halogen or cyano, or C.sub.6-,C.sub.10-,C.sub.14-aryl(C.sub.1-C.sub.3)-alkyl, wherein C.sub.6-,C.sub.10-,C.sub.14-Aryl may optionally be substituted mutually independently by one or more substituents selected from amino, hydroxyl, halogen, nitro, cyano, isocyano, mercapto and C.sub.1-C.sub.4-alkyl, or C.sub.1-C.sub.6-alkylcarbonyl; optionally C.sub.3-cycloalkyl optionally substituted by cyano or C.sub.6-aryl(C.sub.1-C.sub.3)-alkyl; R.sup.2 is H or optionally mutually independently substituted by one or more substituents selected from amino, hydroxyl, halogen, nitro, cyano, mercapto, C.sub.1-C.sub.4-carboxyl, carbonamide, aminosulfonyl, C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.4-cycloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.5-C.sub.6-cycloalkenyl, C.sub.2-C.sub.4-alkynyl, N-mono-C.sub.1-C.sub.4-alkylamino, N,N-di-C.sub.1-C.sub.4-alkylamino, N—C.sub.1-C.sub.4-alkanoylamino, C.sub.1-C.sub.4-alkoxy, C.sub.2-C.sub.4-alkenyloxy, C.sub.2-C.sub.4-alkynyloxy, C.sub.3-C.sub.4-cycloalkoxy, C.sub.5-C.sub.6-cycloalkenyloxy, C.sub.1-C.sub.4-alkoxycarbonyl, C.sub.2-C.sub.4-alkenyloxycarbonyl, C.sub.2-C.sub.4-alkynyloxycarbonyl, C.sub.6-,C.sub.10-,C.sub.14-aryloxycarbonyl, C.sub.1-C.sub.4-alkanoyl, C.sub.2-C.sub.4-alkenylcarbonyl, C.sub.2-C.sub.4-alkynylcarbonyl, C.sub.6-,C.sub.10-,C.sub.14-arylcarbonyl, C.sub.1-C.sub.4-alkylsulfanyl, C.sub.3-C.sub.4-cycloalkylsulfanyl, C.sub.1-C.sub.4-alkylthio, C.sub.2-C.sub.4-alkenylthio, C.sub.5-C.sub.6-cycloalkenylthio, C.sub.2-C.sub.4-alkynylthio, C.sub.1-C.sub.4-alkylsulfenyl and C.sub.1-C.sub.4-alkylsulfinyl, wherein both enantiomers of the C.sub.1-C.sub.4-alkylsulfinyl group are included, C.sub.1-C.sub.4-alkylsulfonyl, N-mono-C.sub.1-C.sub.4-alkylaminosulfonyl, N,N-di-C.sub.1-C.sub.4-alkylaminosulfonyl, C.sub.1-C.sub.4-alkylphosphinyl, C.sub.1-C.sub.4-alkylphosphonyl, wherein both enantiomers are included for C.sub.1-C.sub.4-alkylphosphinyl or C.sub.1-C.sub.4-alkylphosphonyl, N—C.sub.1-C.sub.4-alkylaminocarbonyl, N,N-di-C.sub.1-C.sub.4-alkylaminocarbonyl, N—C.sub.1-C.sub.4-alkanoylaminocarbonyl, N—C.sub.1-C.sub.4-alkanoyl-N—C.sub.1-C.sub.4-alkylaminocarbonyl, C.sub.6-,C.sub.10-,C.sub.14-aryl, C.sub.6-,C.sub.10-,C.sub.4-aryloxy, benzyloxy, benzylthio, C.sub.6-,C.sub.10-,C.sub.14-arylthio, C.sub.6-,C.sub.10-,C.sub.14-arylamino, benzylamino, heterocyclyl and trialkylsilyl, having substituents linked by a double bond such as C.sub.1-C.sub.4-alkylidene or an oxo group-substituted C.sub.1-C.sub.6-alkyl; the moieties A.sub.1, A.sub.2 and A.sub.3 are each independently N, O, CR.sup.3, S or N—R.sup.4, optionally N, CR.sup.3, S or N—R.sup.4, wherein A.sub.1, A.sub.2, A.sub.3, Z and the carbon atom of the ring form an aromatic system; R.sup.3 is each independently H, Cl, F, I, Br or optionally halogenated C.sub.1-C.sub.4-alkyl, optionally methyl; R.sup.4 is each independently H or optionally halogenated C.sub.1-C.sub.4-alkyl, optionally methyl; Q is O or S, optionally O; Z is C or N; optionally C; B.sub.1 and B.sub.5 are each independently N or C—R.sup.5 and B.sub.2, B.sub.3 and B.sub.4 are each independently C—R.sup.5, wherein R.sup.5 is each independently H, halogen, cyano, nitro, SF.sub.5, in each case optionally substituted by one or more substituents selected from amino, hydroxyl, halogen, nitro, cyano, isocyano, mercapto, isothiocyanato, C.sub.1-C.sub.4-carboxyl, carbonamide, SF.sub.5, aminosulfonyl, C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.4-cycloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.5-C.sub.6-cycloalkenyl, C.sub.2-C.sub.4-alkynyl, N-mono-C.sub.1-C.sub.4-alkylamino, N,N-di-C.sub.1-C.sub.4-alkylamino, N—C.sub.1-C.sub.4-alkanoylamino, C.sub.1-C.sub.4-alkoxy, C.sub.2-C.sub.4-alkenyloxy, C.sub.2-C.sub.4-alkynyloxy, C.sub.3-C.sub.4-cycloalkoxy, C.sub.5-C.sub.6-cycloalkenyloxy, C.sub.1-C.sub.4-alkoxycarbonyl, C.sub.2-C.sub.4-alkenyloxycarbonyl, C.sub.2-C.sub.4-alkynyloxycarbonyl, C.sub.6-,C.sub.10-,C.sub.14-aryloxycarbonyl, C.sub.1-C.sub.4-alkanoyl, C.sub.2-C.sub.4-alkenylcarbonyl, C.sub.2-C.sub.4-alkynylcarbonyl, C.sub.6-,C.sub.10-,C.sub.14-arylcarbonyl, C.sub.1-C.sub.4-alkylsulfanyl, C.sub.3-C.sub.4-cycloalkylsulfanyl, C.sub.1-C.sub.4-alkylthio, C.sub.2-C.sub.4-alkenylthio, C.sub.5-C.sub.6-cycloalkenylthio, C.sub.2-C.sub.4-alkynylthio, C.sub.1-C.sub.4-alkylsulfenyl and C.sub.1-C.sub.4-alkylsulfinyl, wherein both enantiomers of the C.sub.1-C.sub.4-alkylsulfinyl group are included, C.sub.1-C.sub.4-alkylsulfonyl, N-mono-C.sub.1-C.sub.4-alkylaminosulfonyl, NN-di-C.sub.1-C.sub.4-alkylaminosulfonyl, C.sub.1-C.sub.4-alkylphosphinyl, C.sub.1-C.sub.4-alkylphosphonyl, wherein both enantiomers are included for C.sub.1-C.sub.4-alkylphosphinyl or C.sub.1-C.sub.4-alkylphosphonyl, N—C.sub.1-C.sub.4-alkylaminocarbonyl, N,N-di-C.sub.1-C.sub.4-alkylaminocarbonyl, N—C.sub.1-C.sub.4-alkanoylaminocarbonyl, N—C.sub.1-C.sub.4-alkanoyl-N—C.sub.1-C.sub.4-alkylaminocarbonyl, C.sub.6-,C.sub.10-,C.sub.14-aryl, C.sub.6-,C.sub.10-,C.sub.14-aryloxy, benzyl, benzyloxy, benzylthio, C.sub.6-,C.sub.10-,C.sub.14-arylthio, C.sub.6-,C.sub.10-,C.sub.14-arylamino, benzylamino, heterocyclyl and trialkylsilyl, having substituents linked by a double bond such as C.sub.1-C.sub.4-alkylidene, an oxo group-substituted or an imino group-substituted C.sub.1-C.sub.6-alkyl, C.sub.3—C-cycloalkyl, C.sub.1—C-alkoxy, N—C.sub.1-C.sub.6-alkoxyimino-C.sub.1-C.sub.3-alkyl, C.sub.1—C-alkylsulfanyl, C.sub.1-C.sub.6-alkylsulfinyl, C.sub.1—C-alkylsulfonyl, N—C.sub.1-C.sub.6-alkylamino or N,N-di-C.sub.1-C.sub.6-alkylamino; T is one of the following listed 5-membered heteroaromatics T1-T4 and T6, wherein the bond to ##STR00036## is marked with a hash #, ##STR00037## And/or a salt, N-oxide and/or tautomeric form of a compound of formula (I).

2. The compound as claimed in claim 1, wherein R.sup.2 is H or methyl.

3. The compound as claimed claim 1, wherein T is T1, T2 or T4, optionally T1.

4. The compound as claimed in claim 1, wherein R.sup.1 is benzyl, cyclopropyl or 1-CN-cyclopropyl.

5. The compound as claimed in claim 1, wherein the compound is a compound according to one of formulae of formula (Ia), (Ib), (Ic), (Id) or (1f) to (1k). ##STR00038## ##STR00039##

6. The compound as claimed in claim 1, wherein the compound is a compound of formula (I′a). ##STR00040##

7. The compound as claimed in claim 1, wherein the compound is a compound of formula (I′b). ##STR00041##

8. The compound as claimed in claim 1, wherein the compound is a compound of formula (I′c). ##STR00042##

9. The compound as claimed in claim 1, wherein the compound is a compound of formula (I′d). ##STR00043##

10. The compounds as claimed in claim 1, wherein B.sub.2 and B.sub.4 are in each case C—H.

11. The compound as claimed in claim 1, wherein B.sub.3 is CR.sup.5 and R.sup.5 is perhalogenated C.sub.1-C.sub.4-alkyl.

12. The compound as claimed in claim 11, wherein R.sup.5 is perfluorinated C.sub.1-C.sub.4-alkyl, optionally perfluorinated propyl.

13. An insecticidal composition comprising at least one compound as claimed in claim 1 and an extender and/or a surface-active substance.

14. A method for protecting transgenic or conventional seed and/or a plant that arises therefrom from infestation by one or more pests, comprising treating the seed with at least one compound as claimed in claim 1.

15. A product comprising a compound as claimed in claim 1 or an insecticidal composition thereof.

16. A seed in which a compound as claimed in claim 1 has been applied to the seed as a constituent of a coating or as a further layer or further layers in addition to a coating.

17. A compound of formulae (B) and/or (C). ##STR00044##

Description

BIOLOGICAL EXAMPLES

[0351] Ctenocephalides Felis—In Vitro Contact Tests with Adult Cat Fleas

[0352] For the coating of the test tubes, 9 mg of active ingredient are first dissolved in 1 ml of acetone p.a. and then diluted to the desired concentration with acetone p.a. 250 μl of the solution are distributed homogeneously on the inner walls and the base of a 25 ml glass tube by turning and rocking on an orbital shaker (rocking rotation at 30 rpm for 2 h). With 900 ppm of active ingredient solution and internal surface area 44.7 cm.sup.2, given homogeneous distribution, an area-based dose of 5 μg/cm.sup.2 is achieved.

[0353] After the solvent has evaporated off, the tubes are populated with 5-10 adult cat fleas (Ctenocephalides felis), sealed with a perforated plastic lid and incubated in a horizontal position at room temperature and ambient humidity. After 48 h, efficacy is determined. To this end, the tubes are stood upright and the fleas are knocked to the base of the tube. Fleas which remain motionless at the base or move in an uncoordinated manner are considered to be dead or moribund.

[0354] A substance shows good efficacy against Ctenocephalides felis if at least 80% efficacy was achieved in this test at an application rate of 5 gg/cm.sup.2. 100% efficacy means that all the fleas were dead or moribund. 0% efficacy means that no fleas were harmed.

[0355] In this test, for example, the following compounds from the preparation examples shows an efficacy of 100% at an application rate of 5 μg/cm.sup.2 (=500 g/ha): 1, 11, 12

[0356] Rhipicephalus sanguineus—in vitro contact tests with adult brown dog ticks

[0357] For the coating of the test tubes, 9 mg of active ingredient are first dissolved in 1 ml of acetone p.a. and then diluted to the desired concentration with acetone p.a. 250 μl of the solution are distributed homogeneously on the inner walls and the base of a 25 ml glass tube by turning and rocking on an orbital shaker (rocking rotation at 30 rpm for 2 h). With 900 ppm of active ingredient solution and internal surface area 44.7 cm.sup.2, given homogeneous distribution, an area-based dose of 5 μg/cm.sup.2 is achieved.

[0358] After the solvent has evaporated off, the tubes are populated with 5-10 adult dog ticks (Rhipicephalus sanguineus), sealed with a perforated plastic lid and incubated in a horizontal position in the dark at room temperature and ambient humidity. After 48 h, efficacy is determined. To this end, the ticks are knocked to the base of the tube and incubated on a hotplate at 45-50° C. for not more than 5 min. Ticks which remain motionless on the base or move in such an uncoordinated manner that they are unable to deliberately avoid the heat by climbing upwards are considered to be dead or moribund.

[0359] A substance shows good activity against Rhipicephalus sanguineus if, in this test, an efficacy of at least 80% was achieved at an application rate of 5 μg/cm.sup.2. An efficacy of 100% means that all the ticks were dead or moribund. 0% efficacy means that none of the ticks were harmed.

[0360] In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 5 μg/cm.sup.2 (=500 g/ha): 1, 2, 3, 11, 12, 14

[0361] In this test, for example, the following compounds from the preparation examples show an efficacy of 80% at an application rate of 5 μg/cm.sup.2 (=500 g/ha): 15

[0362] Boophilus microplus—Dip Test

[0363] Test animals: cattle ticks (Boophilus microplus) Parkhurst strain, SP-resistant

[0364] Solvent: dimethyl sulfoxide

[0365] 10 mg of active ingredient are dissolved in 0.5 ml of dimethyl sulfoxide. To produce a suitable formulation, the active ingredient solution is diluted with water to the concentration desired in each case.

[0366] This active ingredient formulation is pipetted into tubes. 8-10 engorged adult female cattle ticks (Boophilus microplus) are transferred into a further tube with holes. The tube is immersed into the active ingredient formulation, and all the ticks are completely wetted. After the liquid has run out, the ticks are transferred on filter discs into plastic dishes and stored in a climate-controlled room.

[0367] Efficacy is assessed after 7 days by laying of fertile eggs. Eggs which are not visibly fertile are stored in a climate-controlled cabinet until the larvae hatch after about 42 days. An efficacy of 100% means that none of the ticks has laid any fertile eggs; 0% means that all the eggs are fertile.

[0368] In this test, for example, the following compounds of the preparation examples show an efficacy of 100% at an application rate of 100 ppm: 1, 2, 11, 14

[0369] Boophilus microplus—Injection Test

[0370] Solvent: dimethyl sulfoxide

[0371] To produce a suitable active compound preparation, 10 mg of active compound are mixed with 0.5 ml of solvent and the concentrate is diluted to the desired concentration with solvent.

[0372] 1 μl of the active ingredient solution is injected into the abdomen of 5 engorged adult female cattle ticks (Boophilus microplus). The animals are transferred into dishes and kept in a climate-controlled room.

[0373] Efficacy is assessed after 7 days by laying of fertile eggs. Eggs which are not visibly fertile are stored in a climate-controlled cabinet until the larvae hatch after about 42 days. An efficacy of 100% means that none of the ticks has laid any fertile eggs; 0% means that all the eggs are fertile.

[0374] In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 20 μg/animal: 1, 2, 3, 4, 6, 7, 10, 11, 13, 14, 15

[0375] Ctenocephalides felis—Oral Test

[0376] Solvent: dimethyl sulfoxide

[0377] To produce a suitable active ingredient formulation, 10 mg of active ingredient are mixed with 0.5 ml of dimethyl sulfoxide. Dilution with citrated cattle blood gives the desired concentration.

[0378] About 20 unfed adult cat fleas (Ctenocephalides felis) are placed into a chamber which is closed at the top and bottom with gauze. A metal cylinder whose bottom end is closed with parafilm is placed onto the chamber. The cylinder contains the blood/active ingredient formulation, which can be imbibed by the fleas through the parafilm membrane.

[0379] After 2 days, the rate of extermination in % is determined. 100% means that all of the fleas have been killed; 0% means that none of the fleas have been killed.

[0380] In this test, for example, the following compounds of the preparation examples show an efficacy of 100% at an application rate of 100 ppm: 1, 2, 3, 4, 5, 6, 8, 10, 11, 12, 13, 14, 15

[0381] Lucilia cuprina Test

[0382] Solvent: dimethyl sulfoxide

[0383] To produce a suitable active ingredient formulation, 10 mg of active ingredient are mixed with 0.5 ml of dimethyl sulfoxide, and the concentrate is diluted with water to the desired concentration.

[0384] About 20 L1 larvae of the Australian sheep blowfly (Lucilia cuprina) are transferred into a test vessel containing minced horsemeat and the active compound preparation of the desired concentration.

[0385] After 2 days, the rate of extermination in % is determined. 100% means that all the larvae have been killed; 0% means that no larvae have been killed.

[0386] In this test, for example, the following compounds of the preparation examples show an efficacy of 100% at an application rate of 100 ppm: 1, 2, 3, 4, 10, 11, 12, 13, 14, 15

[0387] In this test, for example, the following compounds from the preparation examples show an efficacy of 95% at an application rate of 100 ppm: 6

[0388] In this test, for example, the following compounds of the preparation examples show an efficacy of 80% at an application rate of 100 ppm: 5, 8

[0389] Musca domestica Test

[0390] Solvent: dimethyl sulfoxide

[0391] To produce a suitable active ingredient formulation, 10 mg of active ingredient are mixed with 0.5 ml of dimethyl sulfoxide, and the concentrate is diluted with water to the desired concentration.

[0392] Vessels containing a sponge treated with sugar solution and the active ingredient formulation of the desired concentration are populated with 10 adult houseflies (Musca domestica).

[0393] After 2 days, the rate of extermination in % is determined. 100% means that all of the flies have been killed; 0% means that none of the flies have been killed.

[0394] In this test, for example, the following compounds of the preparation examples show an efficacy of 100% at an application rate of 100 ppm: 1, 2, 10, 11, 12, 13, 14, 15

[0395] In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 100 ppm: 5

[0396] Myzus persicae—Oral Test

TABLE-US-00003 Solvent: 100 parts by weight of acetone

[0397] To produce a suitable active compound preparation, 1 part by weight of active compound is dissolved with the specified amounts by weight of solvent and made up to the desired concentration with water.

[0398] 50 ul of the active compound preparation are transferred to microtiter plates and made up to a final volume of 200 μl with 150 μl of IPL41 insect medium (33%+15% sugar). Then the plates are sealed with parafilm through which a mixed population of the green peach aphid (Myzus persicae), which is located in a second microtiter plate, can pierce and absorb the solution.

[0399] 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.

[0400] In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 4 ppm: 10, 12, 16

[0401] In this test, for example, the following compounds from the preparation examples show efficacy of 90% at an application rate of 4 ppm: 11

[0402] Myzus persicae—Spray Test

TABLE-US-00004 Solvent: 78 parts by weight of acetone 1.5 parts by weight of dimethylformamide Emulsifier: alkylaryl polyglycol ether

[0403] To produce a suitable active ingredient formulation, 1 part by weight of active ingredient is dissolved with the specified parts by weight of solvent and made up to the desired concentration with water containing an emulsifier concentration of 1000 ppm. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

[0404] Discs 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.

[0405] 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.

[0406] 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: 1, 2, 16

[0407] 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: 11

[0408] Phaedon cochleariae—Spray Test

TABLE-US-00005 Solvent: 78.0 parts by weight of acetone 1.5 parts by weight of dimethylformamide Emulsifier: alkylaryl polyglycol ether

[0409] To produce a suitable active ingredient formulation, 1 part by weight of active ingredient is dissolved with the specified parts by weight of solvent and made up to the desired concentration with water containing an emulsifier concentration of 1000 ppm. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

[0410] Discs of Chinese cabbage leaves (Brassica pekinensis) are sprayed with an active compound preparation of the desired concentration and, after drying, populated with larvae of the mustard beetle (Phaedon cochleariae).

[0411] 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.

[0412] 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: 1, 2, 3, 4, 5, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18

[0413] In this test, for example, the following compounds from the preparation examples show efficacy of 83% at an application rate of 100 g/ha: 7, 8

[0414] Spodoptera frugiperda—Spray Test

TABLE-US-00006 Solvent: 78.0 parts by weight of acetone 1.5 parts by weight of dimethylformamide Emulsifier: alkylaryl polyglycol ether

[0415] To produce a suitable active ingredient formulation, 1 part by weight of active ingredient is dissolved with the specified parts by weight of solvent and made up to the desired concentration with water containing an emulsifier concentration of 1000 ppm. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

[0416] Leaf discs of maize (Zea mays) are sprayed with an active ingredient formulation of the desired concentration and, after drying, populated with caterpillars of the armyworm (Spodoptera frugiperda).

[0417] 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.

[0418] 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: 1, 2, 3, 6, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18

[0419] Tetranychus urticae—Spray Test, OP-Resistant

TABLE-US-00007 Solvent: 78.0 parts by weight of acetone 1.5 parts by weight of dimethylformamide Emulsifier: alkylaryl polyglycol ether

[0420] To produce a suitable active ingredient formulation, 1 part by weight of active ingredient is dissolved with the specified parts by weight of solvent and made up to the desired concentration with water containing an emulsifier concentration of 1000 ppm. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

[0421] Discs of bean leaves (Phaseolus vulgaris) infested with all stages of the greenhouse red spider mite (Tetranychus urticae) are sprayed with an active compound preparation of the desired concentration.

[0422] 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.

[0423] 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: 10, 11, 13, 14, 15, 16, 17

[0424] In this test, for example, the following compounds from the preparation examples show efficacy of 100% at an application rate of 20 g/ha: 1, 10, 11, 17

[0425] In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 20 g/ha: 2, 13, 15, 16

[0426] Anopheles Test (ANPHGB Surface Treatment)

[0427] Solvent: acetone+2000 ppm rapeseed oil methyl ester (RME)

[0428] To produce a suitable active compound formulation, the active compound is dissolved in the solvent (2 mg/ml). The active compound formulation is pipetted onto a glazed tile and, after it has dried off, adult mosquitoes of the species Anopheles gambiae strain RSPH (homozygot kdr) are placed onto the treated tile. The exposure time is 30 minutes.

[0429] 24 hours after contact with the treated surface, mortality in % is determined. 100% means that all mosquitoes have been killed; 0% means that none of the mosquitoes have been killed.

[0430] In this test, for example, the following compounds from the preparation examples show efficacy of 80-100% at an application rate of 100 mg/m.sup.2: 1, 2, 3, 8, 6, 9, 10, 14, 15.

[0431] Anopheles Test (ANPHFU Surface Treatment)

[0432] Solvent: acetone+2000 ppm rapeseed oil methyl ester (RME)

[0433] To produce a suitable active compound formulation, the active compound is dissolved in the solvent (2 mg/ml). The active compound formulation is pipetted onto a glazed tile and, after it has dried off, adult mosquitoes of the species Anopheles funestus strain FUMOZ-R (Hunt et al., Med Vet Entomol. 2005 September; 19(3):271-5) are placed onto the treated tile. The exposure time is 30 minutes.

[0434] 24 hours after contact with the treated surface, mortality in % is determined. 100% means that all mosquitoes have been killed; 0% means that none of the mosquitoes have been killed.

[0435] In this test, for example, the following compounds from the preparation examples show efficacy of 80-100% at an application rate of 100 mg/m.sup.2: 1, 2, 9, 10, 14, 15.

[0436] Aedes Test (AEDSAE Surface Treatment)

[0437] Solvent: acetone+2000 ppm rapeseed oil methyl ester (RME)

[0438] To produce a suitable active compound formulation, the active compound is dissolved in the solvent (2 mg/ml). The active compound formulation is pipetted onto a glazed tile and, after it has dried off, adult mosquitoes of the species Aedes aegypti strain MONHEIM are placed onto the treated tile.

[0439] The exposure time is 30 minutes.

[0440] 24 hours after contact with the treated surface, mortality in % is determined. 100% means that all mosquitoes have been killed; 0% means that none of the mosquitoes have been killed.

[0441] In this test, for example, the following compounds from the preparation examples show efficacy of 80-100% at an application rate of 100 mg/m.sup.2: 1, 2, 9, 10, 13, 14, 15.

CONTRASTING EXAMPLES

[0442] Phaedon cochleariae—Spray Test (PHAECO)

TABLE-US-00008 Solvent: 78.0 parts by weight of acetone 1.5 parts by weight of dimethylformamide Emulsifier: alkylaryl polyglycol ether

[0443] To produce a suitable active compound formulation, 1 part by weight of active compound is dissolved with the specified parts by weight of solvent and made up to the desired concentration with water containing an emulsifier concentration of 1000 ppm. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

[0444] Discs 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).

[0445] After the desired 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.

[0446] In this test, for example, the following compounds from the preparation examples show a superior efficacy compared to the prior art: see Table II

[0447] Spodoptera frugiperda—Spray Test (SPODFR)

TABLE-US-00009 Solvent: 78.0 parts by weight of acetone 1.5 parts by weight of dimethylformamide Emulsifier: alkylaryl polyglycol ether

[0448] To produce a suitable active compound formulation, 1 part by weight of active compound is dissolved with the specified parts by weight of solvent and made up to the desired concentration with water containing an emulsifier concentration of 1000 ppm. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

[0449] Leaf discs of maize (Zea mays) are sprayed with an active compound formulation of the desired concentration and, after drying, populated with caterpillars of the armyworm (Spodoptera frugiperda).

[0450] After the desired time, the efficacy in % is determined. 100% means that all the caterpillars have been killed; 0% means that no caterpillar has been killed.

[0451] In this test, for example, the following compounds from the preparation examples show a superior efficacy compared to the prior art: see Table II

[0452] Myzus persicae—Spray Test (MYZUPE)

TABLE-US-00010 Solvent: 78.0 parts by weight of acetone 1.5 parts by weight of dimethylformamide Emulsifier: alkylaryl polyglycol ether

[0453] To produce a suitable active compound formulation, 1 part by weight of active compound is dissolved with the specified parts by weight of solvent and made up to the desired concentration with water containing an emulsifier concentration of 1000 ppm. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

[0454] Discs of Chinese cabbage leaves (Brassica pekinensis) infested with all stages of the green peach aphid (Myzus persicae) are sprayed with an active compound formulation of the desired concentration.

[0455] After the desired time, the efficacy in % is determined. 100% means that all the aphids have been killed; 0% means that no aphids have been killed.

[0456] In this test, for example, the following compounds from the preparation examples show a superior efficacy compared to the prior art: see Table II

[0457] Tetranychus urticae—Spray Test; OP-Resistant (TETRUR)

TABLE-US-00011 Solvent: 78.0 parts by weight of acetone 1.5 parts by weight of dimethylformamide Emulsifier: alkylaryl polyglycol ether

[0458] To produce a suitable active compound formulation, 1 part by weight of active compound is dissolved with the specified parts by weight of solvent and made up to the desired concentration with water containing an emulsifier concentration of 1000 ppm. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

[0459] Discs 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.

[0460] After the desired time, the efficacy in % is determined. 100% means that all the spider mites have been killed; 0% means that no spider mites have been killed.

[0461] In this test, for example, the following compounds from the preparation examples show a superior efficacy compared to the prior art: see Table II

TABLE-US-00012 TABLE II Substance Structure Object Concentration % efficacy dat Example No. 36 WO2012/000896 [00033] PHAECO SPODFR MYZUPE TETRUR 500 g ai/ha 500 g ai/ha 100 g ai/ha 100 g ai/ha 0  7 dat 0  7 dat 0  6 dat 0  6 dat Example No. I- T1-1 inventive [00034] PHAECO SPODFR MYZUPE TETRUR 100 g ai/ha 100 g ai/ha 100 g ai/ha 100 g ai/ha 100  7 dat 100  7 dat 100  5 dat  70  6 dat