Aryl sulphide and aryl sulphoxide derivatives having C-C-attached uracils as pesticides

Abstract

The invention relates to novel compounds of the formula (I)

##STR00001##

in which R.sup.1, R.sup.2, R.sup.3, n, V.sup.1, V.sup.2, W, X and Y have the meanings given in the description, a plurality of processes and intermediates for their preparation and their use as acaricides and/or insecticides and/or nematicides for controlling animal pests, for example in crop protection or in the field of animal health.

Claims

1. Compound of the formula (I) ##STR00026## in which V.sup.1 and V.sup.2 independently of one another represent oxygen or represent sulphur; R.sup.3 represents hydrogen, alkyl, halogen, haloalkyl, amino, cyano, carbamoyl, nitro, hydroxy, hydroalkyl, alkylthiosulphanyl, alkylsulphanyl, alkylsulphinyl, alkylsulphonyl, haloalkylsulphanyl, haloalkylsulphinyl, haloalkylsulphonyl, cycloalkyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkoxyalkyl, haloalkoxy or alkoxy; R.sup.1 and R.sup.2 independently of one another represent hydrogen or alkyl; or represent alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cyanoalkyl, hydroxyalkyl, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, haloalkylcarbonyl, alkoxyalkyl, haloalkoxyalkyl, alkoxy, haloalkoxy, haloalkyl, haloalkenyl or haloalkynyl, where the radicals mentioned above may optionally be substituted by fluorine, chlorine, bromine, iodine, alkyl, cycloalkyl, cyano, nitro, alkoxy, haloalkyl or haloalkoxy; W represents hydrogen or halogen; n represents the number 0, 1 or 2; Y represents hydrogen, halogen, cyano, (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)-alkoxy or (C.sub.1-C.sub.6)-haloalkoxy; X represents hydrogen, halogen, cyano, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl or (C.sub.1-C.sub.6)-alkoxy.

2. Compound according to claim 1, in which V.sup.1 and V.sup.2 independently of one another represent oxygen or represent sulphur; R.sup.3 represents hydrogen, halogen, amino, cyano, carbamoyl, nitro, hydroxy, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)hydroxyalkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.6)alkylthiosulphanyl, (C.sub.1-C.sub.6)-alkylsulphanyl, (C.sub.1-C.sub.6)-alkylsulphinyl, (C.sub.1-C.sub.6)-alkylsulphonyl, (C.sub.1-C.sub.6)-haloalkylsulphanyl, (C.sub.1-C.sub.6)-haloalkylsulphinyl, (C.sub.1-C.sub.6)-haloalkylsulphonyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.1-C.sub.6)-alkylcarbonyl, (C.sub.1-C.sub.6)-haloalkylcarbonyl, (C.sub.1-C.sub.6)-alkoxycarbonyl, (C.sub.1-C.sub.6)alkoxyalkyl, (C.sub.1-C.sub.6)haloalkoxy or (C.sub.1-C.sub.6)-alkoxy; R.sup.1 and R.sup.2 independently of one another represent hydrogen or alkyl; or represent alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cyanoalkyl, hydroxyalkyl, alkylcarbonyl, haloalkylcarbonyl, alkoxyalkyl, haloalkoxyalkyl, alkoxy or haloalkoxy, where the radicals mentioned above may optionally be substituted by fluorine, chlorine, bromine, iodine, (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, cyano, nitro, (C.sub.1-C.sub.6)-alkoxy, (C.sub.1-C.sub.6)-haloalkyl or (C.sub.1-C.sub.6)-haloalkoxy; or represent haloalkyl, haloalkenyl or haloalkynyl; W represents hydrogen or halogen; n represents the number 0 or 1; Y represents hydrogen, halogen, (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)-alkoxy or (C.sub.1-C.sub.6)-haloalkoxy; X represents hydrogen, halogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl or (C.sub.1-C.sub.6)-alkoxy.

3. Compound according to claim 1, in which V.sup.1 and V.sup.2 independently of one another represent oxygen or represent sulphur; R.sup.3 represents hydrogen, amino, halogen, cyano, (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)-alkylcarbonyl, (C.sub.1-C.sub.4)-haloalkylcarbonyl, (C.sub.1-C.sub.4)-alkoxycarbonyl or (C.sub.1-C.sub.4)-alkoxy; R.sup.1 and R.sup.2 independently of one another represent hydrogen, (C.sub.1-C.sub.4)-alkyl, cyano-(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)-alkyl, (C.sub.1-C.sub.4)-haloalkoxy-(C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy or (C.sub.1-C.sub.4)-haloalkoxy; or represent (C.sub.3-C.sub.6)-cycloalkyl or (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.1-C.sub.2)-alkyl, where the radicals mentioned above may optionally be substituted by fluorine, chlorine, bromine, iodine, (C.sub.1-C.sub.3)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, cyano, nitro, (C.sub.1-C.sub.4)-alkoxy, (C.sub.1-C.sub.3)-haloalkyl or (C.sub.1-C.sub.3)-haloalkoxy; W represents hydrogen, chlorine or fluorine; n represents the number 0 or 1; Y represents halogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.1-C.sub.4)-haloalkyl, (C.sub.1-C.sub.4)-alkoxy or (C.sub.1-C.sub.4)-haloalkoxy; X represents hydrogen, halogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl or (C.sub.1-C.sub.4)-alkoxy.

4. Compound according to claim 1, in which V.sup.1 and V.sup.2 independently of one another represent oxygen or represent sulphur; R.sup.3 represents hydrogen, chlorine, fluorine, methyl, ethyl, methoxy, cyclopropyl, cyano or trifluoromethyl; R.sup.1 and R.sup.2 independently of one another represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, CH.sub.2CH(CH.sub.3).sub.2, CH.sub.2CN, CH.sub.2CF.sub.3, CH.sub.2CHF.sub.2, CH.sub.2CH.sub.2OCH.sub.3, cyclopropyl, cyclobutyl or cyclopropylmethyl; W represents fluorine; n represents the number 0 or 1; Y represents fluorine, chlorine, bromine, methyl, trifluoromethyl or methoxy; X represents hydrogen, chlorine, fluorine or methyl.

5. Compound according to claim 1, in which V.sup.1 and V.sup.2 independently of one another represent oxygen or represent sulphur; R.sup.3 represents hydrogen, fluorine or chlorine; R.sup.1 and R.sup.2 independently of one another represent hydrogen, methyl, ethyl, n-propyl, isopropyl or CH.sub.2CF.sub.3; W represents fluorine; n represents the number 0 or 1; Y represents methyl; X represents fluorine or methyl.

6. Compound according to claim 1 according to formula (I-A) ##STR00027## in which V.sup.1 and V.sup.2 independently of one another represent oxygen or represent sulphur; R.sup.3 represents hydrogen, alkyl, halogen, haloalkyl, amino, cyano, carbamoyl, nitro, hydroxy, hydroalkyl, alkylthiosulphanyl, alkylsulphanyl, alkylsulphinyl, alkylsulphonyl, haloalkylsulphanyl, haloalkylsulphinyl, haloalkylsulphonyl, cycloalkyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkoxyalkyl, haloalkoxy or alkoxy; R.sup.1 and R.sup.2 independently of one another represent hydrogen or alkyl; or represent alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cyanoalkyl, hydroxyalkyl, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, haloalkylcarbonyl, alkoxyalkyl, haloalkoxyalkyl, alkoxy, haloalkoxy, haloalkyl, haloalkenyl or haloalkynyl, where the radicals mentioned above may optionally be substituted by fluorine, chlorine, bromine, iodine, alkyl, cycloalkyl, cyano, nitro, alkoxy, haloalkyl or haloalkoxy; W represents hydrogen or halogen; n represents the number 0, 1 or 2; Y represents hydrogen, halogen, cyano, (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)-alkoxy or (C.sub.1-C.sub.6)-haloalkoxy; X represents hydrogen, halogen, cyano, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl or (C.sub.1-C.sub.6)-alkoxy.

7. Compound according to claim 1 according to formula (I-B) ##STR00028## in which V.sup.1 and V.sup.2 independently of one another represent oxygen or represent sulphur; R.sup.3 represents hydrogen, alkyl, halogen, haloalkyl, amino, cyano, carbamoyl, nitro, hydroxy, hydroalkyl, alkylthiosulphanyl, alkylsulphanyl, alkylsulphinyl, alkylsulphonyl, haloalkylsulphanyl, haloalkylsulphinyl, haloalkylsulphonyl, cycloalkyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkoxyalkyl, haloalkoxy or alkoxy; R.sup.1 and R.sup.2 independently of one another represent hydrogen or alkyl: or represent alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cyanoalkyl, hydroxyalkyl, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, haloalkylcarbonyl, alkoxyalkyl, haloalkoxyalkyl, alkoxy, haloalkoxy, haloalkyl, haloalkenyl or haloalkynyl, where the radicals mentioned above may optionally be substituted by fluorine, chlorine, bromine, iodine, alkyl, cycloalkyl, cyano, nitro, alkoxy, haloalkyl or haloalkoxy; W represents hydrogen or halogen; n represents the number 0, 1 or 2; Y represents hydrogen, halogen, cyano, (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)-alkoxy or (C.sub.1-C.sub.6)-haloalkoxy; X represents hydrogen, halogen, cyano, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl or (C.sub.1-C.sub.6)-alkoxy.

8. Compound according to claim 1 according to formula (I-C) ##STR00029## in which V.sup.1 and V.sup.2 independently of one another represent oxygen or represent sulphur; R.sup.3 represents hydrogen, alkyl, halogen, haloalkyl, amino, cyano, carbamoyl, nitro, hydroxy, hydroalkyl, alkylthiosulphanyl, alkylsulphanyl, alkylsulphinyl, alkylsulphonyl, haloalkylsulphanyl, haloalkylsulphinyl, haloalkylsulphonyl, cycloalkyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkoxyalkyl, haloalkoxy or alkoxy; R.sup.1 and R.sup.2 independently of one another represent hydrogen or alkyl: or represent alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cyanoalkyl, hydroxyalkyl, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, haloalkylcarbonyl, alkoxyalkyl, haloalkoxyalkyl, alkoxy, haloalkoxy, haloalkyl, haloalkenyl or haloalkynyl, where the radicals mentioned above may optionally be substituted by fluorine, chlorine, bromine, iodine, alkyl, cycloalkyl, cyano, nitro, alkoxy, haloalkyl or haloalkoxy; W represents hydrogen or halogen; n represents the number 0, 1 or 2; Y represents hydrogen, halogen, cyano, (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)-alkoxy or (C.sub.1-C.sub.6)-haloalkoxy; X represents hydrogen, halogen, cyano, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl or (C.sub.1-C.sub.6)-alkoxy.

9. Compound according to claim 1 according to formula (I-D) ##STR00030## in which V.sup.1 and V.sup.2 independently of one another represent oxygen or represent sulphur; R.sup.3 represents hydrogen, alkyl, halogen, haloalkyl, amino, cyano, carbamoyl, nitro, hydroxy, hydroalkyl, alkylthiosulphanyl, alkylsulphanyl, alkylsulphinyl, alkylsulphonyl, haloalkylsulphanyl, haloalkylsulphinyl, haloalkylsulphonyl, cycloalkyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkoxyalkyl, haloalkoxy or alkoxy; R.sup.1 and R.sup.2 independently of one another represent hydrogen or alkyl; or represent alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cyanoalkyl, hydroxyalkyl, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, haloalkylcarbonyl, alkoxyalkyl, haloalkoxyalkyl, alkoxy, haloalkoxy, haloalkyl, haloalkenyl or haloalkynyl, where the radicals mentioned above may optionally be substituted by fluorine, chlorine, bromine, iodine, alkyl, cycloalkyl, cyano, nitro, alkoxy, haloalkyl or haloalkoxy: W represents hydrogen or halogen; n represents the number 0, 1 or 2; Y represents hydrogen, halogen, cyano, (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)-alkoxy or (C.sub.1-C.sub.6)-haloalkoxy; X represents hydrogen, halogen, cyano, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-haloalkyl or (C.sub.1-C.sub.6)-alkoxy.

10. Compound according to formula (II-01) ##STR00031##

11. Compound according to formula (II-02) ##STR00032##

12. Compound according to formula (VI-01) ##STR00033##

13. Formulation, optionally an agrochemical formulation, comprising at least one compound of the formula (I) according to claim 1.

14. Formulation according to claim 13, further comprising at least one extender and/or at least one surface-active substance.

15. Formulation according to claim 13, wherein the compound of the formula (I) is in a mixture with at least one further active compound.

16. Method for controlling pests, optionally one or more animal pests, comprising allowing a compound of the formula (I) according to claim 1 to act on the pests and/or a habitat thereof.

17. Method according to claim 16, wherein the pest is an animal pest and comprises an insect, an acarid or a nematode, or the pest is an insect, an acarid or a nematode.

18. A product comprising a compound of the formula (I) according to claim 1 for controlling one or more animal pests.

19. Product according to claim 18, wherein the animal pest comprises an insect, an acarid or a nematode, or the animal pest is an insect, an acarid or a nematode.

20. Product according to claim 18 adapted for use in crop protection.

21. Product according to claim 18 adapted for use in the field of animal health.

22. Method for protecting seed and/or a germinating plant from pests, optionally animal pests, comprising contacting seed with a compound of the formula (I) according to claim 1.

23. Seed obtained by a method according to claim 22.

Description

EXAMPLES

[0438] The preparation and use examples which follow illustrate the invention without limiting it. The products were characterized by 1H-NMR or 13C-NMR spectroscopy and/or LC-MS (liquid chromatography mass spectrometry).

[0439] The logP values were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) using reversed-phase columns (C 18) by the following methods:

[0440] .sup.[a] The LC-MS determination in the acidic range was effected at pH 2.7 with 0.1% aqueous formic acid and acetonitrile (contains 0.1% formic acid) as eluents; linear gradient from 10% acetonitrile to 95% acetonitrile. Called logP (HCOOH) in the table.

[0441] .sup.[b] LC-MS determination in the neutral range was effected at pH 7.8 with 0.001 molar aqueous ammonium hydrogencarbonate solution and acetonitrile as eluents; linear gradient from 10% acetonitrile to 95% acetonitrile. Called logP (neutral) in the table.

[0442] Calibration was effected with unbranched alkan-2-ones (having 3 to 16 carbon atoms) with known logP values (logP values determined on the basis of the retention times by linear interpolation between two successive alkanones).

[0443] The lambda-max values were determined in the maxima of the chromatographic signals using the UV spectra from 200 nm to 400 nm.

[0444] The NMR data for selected examples are listed in conventional form (8 values, number of hydrogen atoms, multiplet splitting).

[0445] The solvent in which the NMR spectrum was recorded is reported in each case.

Preparation Examples

Preparation Example 1: 6-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulphinyl]phenyl}-1,3-dimethylpyrimidine-2,4(1H,3H)-dione (I-1)

[0446] ##STR00015##

[0447] At 0° C., 75 mg (0.207 mmol) of 6-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}-1,3-dimethylpyrimidine-2,4(1H,3H)-dione (1-2) were initially charged in 5 ml of acetic acid. After the addition of catalytic amounts of sodium tungstate at 0-4° C., 185 mg (0.159 mmol) of 3% aqueous hydrogen peroxide solution were added thereto in portions and the reaction mixture was stirred at room temperature for 24 h. After the addition of a 33% strength aqueous bisulphite solution, the mixture was extracted twice with dichloromethane. The combined organic phases were washed with water, dried over sodium sulphate and filtered. After removal of the solvent under reduced pressure, the residue was purified by column chromatography on a 10 g SNAP column (Biotage) using the mobile phase ethyl acetate/cyclohexane (gradient 20-76% ethyl acetate). This gave 31 mg of product as a white solid (39.6% of theory, purity 91.6% according to LC/MS).

[0448] 1H-NMR (D6-DMSO) δ ppm: 7.94-7.92 (m, 1H), 7.53-7.51 (m, 1H), 5.93 (broad, 1H), 4.19 (broad, 2H), 3.23 (s, 3H), 3.09 (s, 3H), 2.46 (s, 3H)

[0449] logP (HCOOH): 1.77 logP (neutral): 1.75

Preparation Example 2: 6-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}-1,3-dimethylpyrimidine-2,4(1H,3H)-dione (I-2)

[0450] ##STR00016##

[0451] At room temperature, 100 mg (0.573 mmol) of 6-chloro-1,3-dimethylpyrimidine-2,4(1H,3H)-dione and 55 mg (0.078 mmol) of bis(triphenylphosphine)palladium(II) dichloride were stirred in 20 ml of dioxane for 2 h. 195 mg (0.728 mmol) of {2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}boric acid and 3 ml of 2 molar sodium carbonate solution were then added and the mixture was heated under reflux for 18 h. After cooling, water was added and the reaction mixture was extracted with dichloromethane. After filtration through a layer of silica gel, the combined organic phases were dried over MgSO.sub.4 and freed of the solvent under reduced pressure. The residue was purified by column chromatography on a 10 g SNAP column (Biotage) using the mobile phase ethyl acetate/cyclohexane (gradient 5-61% ethyl acetate). This gave 46 g of product as a light-yellow viscous oil (22.2% of theory, purity according to LC/MS neutral 100%).

[0452] 1H-NMR (D.sub.6-DMSO) δ ppm: 7.68-7.66 (m, 1H), 7.42-7.39 (m, 1H), 5.77 (s, 1H), 4.06-3.99 (q, 2H), 3.23 (s, 3H), 3.06 (s, 3H), 2.44 (s, 3H)

[0453] logP (HCOOH): 2.86 logP (neutral): 2.74

Preparation Example 3: 3-Ethyl-5-fluoro-6-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)-sulphanyl]phenyl}-1-methylpyrimidine-2,4(1H,3H)-dione (1-3)

[0454] ##STR00017##

[0455] At room temperature, 340 mg (1.65 mmol) of 6-chloro-3-ethyl-5-fluoro-1-methylpyrimidine-2,4(1H,3H)-dione (II-01) and 170 mg (0.242 mmol) of bis(triphenylphosphine)palladium(II) dichloride were stirred in 20 ml of dioxane for 2 h. 530 mg (1.98 mmol) of {2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)-sulphanyl]phenyl}boric acid and 9 ml of 2-molar sodium carbonate solution were added, and the mixture was heated under reflux for 18 h. After cooling, water was added and the reaction mixture was extracted with dichloromethane. The combined organic phases were, after filtration through a layer of silica gel, dried over MgSO.sub.4 and freed from the solvent under reduced pressure. The residue was purified by column chromatography using MPLC on RP(C-18) with water/acetonitrile. This gave 26 mg of product as a white solid (4% of theory, purity according to LC/MS neutral 90.2%).

[0456] 1H-NMR (D6-DMSO) δ ppm: 7.81-7.79 (m, 1H), 7.49-7.47 (m, 1H), 4.04-3.90 (m, 4H), 3.04 (s, 3H), 2.46 (s, 3H), 1.17 (t, 3H)

[0457] logP (HCOOH): 3.32 logP (neutral): 3.42

Preparation of 6-chloro-3-ethyl-5-fluoro-1-methylpyrimidine-2,4(1H,3H)-dione (II-01)

[0458] ##STR00018##

[0459] 120 mg (0.623 mmol) of 6-chloro-3-ethyl-5-fluoropyrimidine-2,4(1H,3H)-dione (Aurora Fine Chemicals, San Diego, USA; CAS-Reg. No. 13593-35-6) were dissolved in 10 ml of dimethylformamide and, after addition of 250 mg (1.81 mmol) of potassium carbonate and 250 mg of caesium carbonate (0.767 mmol), 250 mg (1.76 mmol) of iodomethane were added and the mixture was stirred at room temperature for 18 h. The solvent was then distilled off under reduced pressure and the residue was treated with water and dichloromethane. The combined organic phases were, after filtration through a layer of silica gel, dried over MgSO.sub.4 and freed from the solvent under reduced pressure. 96 mg of product (75% of theory, purity according to LC/MC 86%) remained.

[0460] 1H-NMR (D6-DMSO) δ ppm: 3.88-3.82 (q, 2H), 3.43 (s, 3H), 1.11 (t, 3H)

[0461] logP (HCOOH): 1.31

Preparation Example 4: 6-{2,4-Dimethyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}-2,4-dimethyl-1,2,4-triazine-3,5(2H,4H)-dione (1-4)

[0462] ##STR00019##

[0463] 80 mg (0.458 mmol) of 6-chloro-1,3-dimethylpyrimidine-2,4(1H,3H)-dione and 50 mg (0.043 mmol) of tetrakis(triphenylphosphine)palladium in 20 ml of dioxane were heated under reflux with 160 mg (0.462 mmol) of 2-{2,4-dimethyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and 3 ml of 2-molar sodium carbonate solution for 18 h. After cooling, water was added and the reaction mixture was extracted with dichloromethane. The combined organic phases were, after filtration through a layer of silica gel, dried over MgSO.sub.4 and freed from the solvent under reduced pressure. The residue was purified by column chromatography on a 10 g SNAP column (Biotage) using ethyl acetate/cyclohexane (gradient 10-80% ethyl acetate) as mobile phase. This gave 7 mg of product as a white solid (4.3% of theory, purity according to NMR 85%).

[0464] 1H-NMR (D.sub.6-DMSO) δ ppm: 7.47 (s, 1H), 7.27 (s, 1H), 5.56 (s, 1H), 4.03-3.94 (m, 2H), 3.23 (s, 3H), 2.93 (s, 3H), 2.37 (s, 3H), 2.16 (s, 3H)

[0465] logP (HCOOH): 2.98

Preparation Example 5: 6-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}-3-methylpyrimidine-2,4(1H,3H)-dione (1-13)

[0466] ##STR00020##

[0467] A mixture of 600 mg (1.773 mmol) of ethyl 3-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}-3-oxopropanoate (VI-01) and 175 mg (2.362 mmol) of N-methylurea was stirred at 140° C. for 12 h. The crude product was purified directly by column chromatography on a 50 g SNAP column (Biotage) using ethyl acetate/cyclohexane (gradient 5-80% ethyl acetate) as mobile phase. This gave 103 mg of product as a white solid (16.7% of theory, purity according to LC/MS 99.3%).

[0468] 1H-NMR (D.sub.6-DMSO) δ ppm: 11.46 (s, 1H), 7.74-7.73 (m, 1H), 7.37-7.35 (m, 1H), 5.86 (s, 1H), 4.09-4.04 (q, 2H), 3.17 (s, 3H), 2.43 (s, 3H)

[0469] 13C-NMR (D.sub.6-DMSO) δ ppm: 162.7, 158.0, 151.5, 145.0, 144.3, 128.9, 126.0, 118.4, 118.1, 100.4, 35.1, 26.4, 20.0

[0470] logP (HCOOH): 2.38 logP (neutral): 2.25

Preparation of ethyl 3-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}-3-oxopropanoate (VI-01)

[0471] ##STR00021##

[0472] 33.9 g (0.20 mol) of potassium monoethyl malonate were initially charged in a 2 l flask under argon, and 300 ml of acetonitrile were added. The mixture was cooled to 0° C., after which 22.2 g (0.22 mol) of triethylamine and 23.7 g (0.25 mol) of magnesium chloride were added. The reaction mixture was stirred at 20-25° C. for 3 h. The resulting suspension was cooled to 0° C., and 28.6 g (0.10 mol) of 2-fluoro-4-methyl-5-(2,2,2-trifluoroethyl)sulphanylbenzoyl chloride were added dropwise a little at a time. After subsequent addition of 2.02 g (0.02 mol) of triethylamine, the mixture was stirred at room temperature overnight. The mixture was added to 500 ml of a 10% strength HCl solution and stirred for another 2 h. The solid formed was filtered off with suction and air-dried. This gave 31.9 g of product (94% of theory, purity >95% according to 1H-NMR).

[0473] 1H-NMR (CDCl.sub.3) δ ppm: 12.70 (s, 1H), 8.05-8.03 (m, 1H), 7.03-7.00 (m, 1H), 5.81 (s, 1H), 4.30-4.24 (q, 2H), 3.41-3.34 (q, 2H), 2.50 (s, 3H), 1.34 (t, 3H)

[0474] logP (HCOOH): 3.57 logP (neutral): 3.59

Preparation Example 6: 6-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}-2-thioxo-2,3-dihydropyrimidin-4(1H)-one (1-14)

[0475] ##STR00022##

[0476] A mixture of 600 mg (1.773 mmol) of ethyl 3-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}-3-oxopropanoate (VI-01) and 175 mg (2.299 mmol) of thiourea was stirred at 140° C. for 12 h. The crude product was purified directly by column chromatography on a 50 g SNAP column (Biotage) using ethyl acetate/cyclohexane (gradient 5-50% ethyl acetate) as mobile phase. This gave 48 mg of product as a beige solid (7.7% of theory, purity according to LC/MS 92.3%), in addition, 115 mg (18.5% of theory, purity according to LC/MS 78.9%) of a further fraction were isolated. 1H-NMR (D.sub.6-DMSO) δ ppm: 12.61 (s, 1H), 12.58 (s, 1H), 7.74-7.72 (m, 1H), 7.36-7.33 (m, 1H), 6.03 (s, 1H), 4.09-4.01 (q, 2H), 2.43 (s, 3H)

[0477] logP (HCOOH): 2.34 logP (neutral): 1.54

Preparation Example 7: 5-Chloro-6-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}-1,3-dimethylpyrimidine-2,4(1H,3H)-dione (1-16)

[0478] ##STR00023##

[0479] 65 mg (0.482 mmol) of sulphuryl chloride, dissolved in 3 ml of acetonitrile, were slowly added dropwise to a solution of 109 mg (0.301 mmol) of 6-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}-1,3-dimethylpyrimidine-2,4(1H,3H)-dione (1-2) in 5 ml of acetonitrile and 50 mg of acetic acid, and the mixture was then stirred at 80° C. for 12 h. After cooling, water was added and the reaction mixture was extracted with dichloromethane. The combined organic phases were, after filtration through a layer of silica gel, dried over MgSO.sub.4 and freed from the solvent under reduced pressure. The residue was purified by column chromatography on a 10 g SNAP column (Biotage) using ethyl acetate/cyclohexane (gradient 10-80% ethyl acetate) as mobile phase. This gave 8 mg of product as a white solid (6.7% of theory, purity according to LC/MS 100%).

[0480] 1H-NMR (D.sub.6-DMSO) δ ppm: 7.74-7.73 (m, 1H), 7.48-7.46 (m, 1H), 4.02-3.94 (m, 2H), 3.30 (s, 3H), 3.05 (s, 3H), 2.46 (s, 3H)

[0481] logP (HCOOH): 3.15

[0482] The following compounds of the formula (I) were obtained analogously to the examples and in accordance with the preparation processes described above:

##STR00024##

where V.sup.2=O and W=F

TABLE-US-00001 Ex. R.sup.1 R.sup.2 R.sup.3 X Y n V.sup.1 I-5 n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 H F CH.sub.3 0 O I-6 i-Pr i-Pr H F CH.sub.3 0 O I-7 C.sub.2H.sub.5 C.sub.2H.sub.5 H F CH.sub.3 0 O I-8 H C.sub.2H.sub.5 F F CH.sub.3 0 O I-9 i-Pr i-Pr H F CH.sub.3 1 O I-10 C.sub.2H.sub.5 C.sub.2H.sub.5 H F CH.sub.3 1 O I-11 CH.sub.3 C.sub.2H.sub.5 F F CH.sub.3 1 O I-12 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 1 O I-15 CH.sub.3 F.sub.3C—CH.sub.2 H F CH.sub.3 0 S I-17 H CH.sub.3 H F CH.sub.3 1 O NMR data and logP values: logP (HCOOH) = logP[a] logP (neutral) = logP[b]

TABLE-US-00002 Ex. No. logP [b] logP [a] NMR [δ ppm] I-5  4.16 4.26 1H-NMR (D.sub.6-DMSO): 7.79-7.77 (m, 1H), 7.42-7.39 (m, 1H), 5.71 (s, 1H), 4.06-3.63 (m, 6H), 2.44 (s, 3H) 1.58 (m, 2H), 1.37 (m, 2H), 0.89 (t, 3H), 0.61 (t, 3H) I-6  4.42 4.52 1H-NMR (D.sub.6-DMSO): 7.75-7.73 (m, 1H), 7.41-7.38 (m, 1H), 5.56 (s, 1H), 5.10-5.05 (m, 1H), 4.13-3.98 (m, 2H), 3.77-3.72 (m, 1H), 2.42 (s, 3H), 1.41-1.30 (4xd, 12H) I-7  3.47 3.54 1H-NMR (D.sub.6-DMSO): 7.77-7.75 (m, 1H), 7.42-7.40 (m, 1H), 5.70 (s, 1H), 4.11-3.87 (m, 4H), 3.72-3.65 (m, 1H), 3.48-3.41 (m, 1H), 2.43 (s, 3H), 1.14 (t, 3H), 0.96 (t, 3H) I-8  2.72 1H-NMR (D.sub.6-DMSO): 7.78-7.77 (m, 1H), 7.40-7.37 (m, 1H), 4.05- 3.98 (q, 2H), 3.86 (m, 2H), 2.45 (s, 3H), 1.15 (t, 3H). I-9  3.10 3.19 1H-NMR (D.sub.6-DMSO): 7.94-7.92 (m, 1H), 7.53-7.50 (m, 1H), 5.71 (s, 1H), 5.11-5.04 (m, 1H), 4.27-4.11 (m, 2H), 3.77-3.73 (m, 1H), 2.45 (s, 3H), 1.42-1.33 (4xd, 12H) I-10 2.28 2.37 1H-NMR (D.sub.6-DMSO): 7.97-7.95 (m, 1H), 7.55-7.52 (m, 1H), 5.76 (s, 1H), 4.22-4.14 (m, 2H), 3.92-3.87 (m, 2H), 3.65 (m, 2H), 2.46 (s, 3H), 1.15 (t, 3H), 0.98 (broad, 3H) I-11 2.19 2.20 1H-NMR (D.sub.6-DMSO): 8.07-8.05 (m, 1H), 7.61-7.58 (m, 1H), 4.35- 3.99 (m, 2H), 3.96-3.90 (q, 2H), 3.08 (s, 3H), 2.47 (s, 3H), 1.17 (t, 3H) I-12 1.82 1.89 1H-NMR (D.sub.6-DMSO): 7.74 (s, 1H), 7.38 (s, 1H), 5.60 (s, 1H), 4.17- 4.06 (m, 2H), 3.24 (s, 3H), 2.94 (s, 3H), 2.40 (s, 3H), 2.26 (s, 3H) I-15 4.34 1H-NMR (D.sub.6-DMSO): 7.78-7.77 (m, 1H), 7.45-7.43 (m, 1H), 6.27 (s, 1H), 5.45-5.31 (m, 2H), 4.08-4.02 (m, 2H), 3.49 (s, 3H), 2.44 (s, 3H) 13C-NMR (D.sub.6-DMSO) δ ppm: 178.9, 158.4, 157.1, 149.9, 144.3, 132.3, 129.7, 126.0, 124.3, 119.7, 117.9, 107.5, 47.6, 42.5, 34.8, 20.3 I-17 1.43 1.41 1H-NMR (D.sub.6-DMSO): 11.54 (s, 1H), 7.94-7.92 (m, 1H), 7.53-7.50 (m, 1H), 5.76 (broad, 1H), 4.22-4.09 (m, 2H), 3.02 (s, 3H), 2.45 (s, 3H)

Further Examples of the Preparation of Starting Materials

Preparation of Compounds of the Formula (II):

Preparation of 6-chloro-3-ethyl-1,5-dimethylpyrimidine-2,4(1H,3H)-dione (11-02)

[0483] ##STR00025##

[0484] 120 mg (0.636 mmol) of 6-chloro-3-ethyl-5-methylpyrimidine-2,4(1H,3H)-dione (CAS-Reg. No. 1565665-59-9) were dissolved in 5 ml of dimethylformamide and, after addition of 250 mg (1.81 mmol) of potassium carbonate and 250 mg of caesium carbonate (0.767 mmol), 260 mg (1.83 mmol) of iodomethane were added and the mixture was stirred at room temperature for 18 h. The solvent was then distilled off under reduced pressure and the residue was treated with water and dichloromethane. The combined organic phases were, after filtration through a layer of silica gel, dried over MgSO.sub.4 and freed from the solvent under reduced pressure. 95 mg of product (73.7% of theory, purity according to LC/MS 73%) remained.

[0485] 1H-NMR (D6-DMSO) δ ppm: 3.86-3.83 (q, 2H), 3.46 (s, 3H), 1.96 (s, 3H), 1.09 (t, 3H)

[0486] logP (HCOOH): 1.59

Use Examples

[0487] 1. Boophilus microplus—Injection Test
Solvent: dimethyl sulphoxide

[0488] To produce a suitable preparation of active compound, 10 mg of active compound are mixed with 0.5 ml of solvent and the concentrate is diluted with solvent to the desired concentration.

[0489] 1 μl of the active compound 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.

[0490] 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.

[0491] In this test, for example, the following compounds from the preparation examples showed an efficacy of 100% at an application rate of 20 Gg/animal: I-1, I-2, I-9, I-10, I-11, I-12

2. Meloidogyne incognita Test
Solvent: 125.0 parts by weight of acetone

[0492] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted with water to the desired concentration.

[0493] Vessels are filled with sand, active compound solution, an egg/larvae suspension of the southern root-knot nematode (Meloidogyne incognita) and lettuce seeds. The lettuce seeds germinate and the plants develop. The galls develop on the roots.

[0494] After 14 days, the nematicidal efficacy in % is determined by the formation of galls. 100% means that no galls were found; 0% means that the number of galls on the treated plants corresponds to the untreated control.

[0495] In this test, for example, the following compounds from the preparation examples showed an efficacy of 100% at an application rate of 20 ppm: I-1

[0496] In this test, for example, the following compounds from the preparation examples showed an efficacy of 90% at an application rate of 20 ppm: I-2

3. Phaedon cochleariae—Spray Test
Solvent: 78.0 parts by weight of acetone [0497] 1.5 parts by weight of dimethylformamide
Emulsifier: alkylaryl polyglycol ether

[0498] To produce a suitable preparation of active compound, 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 preparation is diluted with emulsifier-containing water.

[0499] 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).

[0500] 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.

[0501] In this test, for example, the following compounds from the preparation examples showed an efficacy of 100% at an application rate of 500 g/ha: I-15

[0502] In this test, for example, the following compounds from the preparation examples showed an efficacy of 83% at an application rate of 500 g/ha: I-2

4. Tetranychus urticae—Spray Test, OP-Resistant
Solvent: 78.0 parts by weight of acetone [0503] 1.5 parts by weight of dimethylformamide
Emulsifier: alkylaryl polyglycol ether

[0504] To produce a suitable preparation of active compound, 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 preparation is diluted with emulsifier-containing water.

[0505] 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.

[0506] After 6 days, the efficacy in % is determined. 100% means that all the spider mites have been killed; 0% means that none of the spider mites have been killed.

[0507] In this test, for example, the following compounds from the preparation examples showed an efficacy of 100% at an application rate of 500 g/ha: I-1, I-2, I-6, I-9, I-10, I-11, I-12

[0508] In this test, for example, the following compounds from the preparation examples showed an efficacy of 90% at an application rate of 500 g/ha: I-5, I-7, I-15, I-16

5. Tetranychus urticae-Spray Test, OP-Resistant
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: alkylaryl polyglycol ether

[0509] To produce a suitable preparation of active compound, 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 preparation is diluted with emulsifier-containing water. If the addition of ammonium salts or/and penetrants is required, these are each added in a concentration of 1000 ppm to the preparation solution.

[0510] Bean plants (Phaseolus vulgaris) heavily infested by all stages of the greenhouse red spider mite (Tetranychus urticae) are sprayed with an active compound preparation of the desired concentration.

[0511] After 7 days, the efficacy in % is determined. 100% means that all the spider mites have been killed; 0% means that none of the spider mites have been killed.

[0512] In this test, for example, the following compounds from the preparation examples showed an efficacy of 100% at an application rate of 20 ppm: I-1, I-2, I-7, I-10, I-15

6. Tetranychus urticae—Drench Test, OP-Resistant
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

[0513] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration, where the volume of soil to be drenched has to be taken into account. Here, it has to be made sure that a concentration of 40 ppm of emulsifier in the soil is not exceeded. To produce further test concentrations, the mixture is diluted with water.

[0514] Bean plants (Phaseolus vulgaris) in pots filled with soil, which plants are heavily infested by all stages of the greenhouse red spider mite (Tetranychus urticae), are watered with an active compound preparation of the desired concentration.

[0515] After 14 days, the efficacy in % is assessed. 100% means that all spider mites have been killed; 0% means that none of the spider mites have been killed.

[0516] In this test, for example, the following compounds from the preparation examples showed an efficacy of 100% at an application rate of 4 ppm: I-1, I-15

[0517] In this test, for example, the following compounds from the preparation examples showed an efficacy of 99% at an application rate of 4 ppm: I-2

[0518] In this test, for example, the following compounds from the preparation examples showed an efficacy of 95% at an application rate of 4 ppm: 1-10

7. Meloidogyne incognita—Test
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 2.5 parts by weight of alkylaryl polyglycol ether

[0519] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration, where the volume of soil to be drenched has to be taken into account. Here, it has to be made sure that a concentration of 20 ppm of emulsifier in the soil is not exceeded. To produce further test concentrations, the mixture is diluted with water.

[0520] Pots filled with soil (loamy sand) are watered with the active compound solution. An egg/larvae suspension of the southern root-knot nematode (Meloidogyne incognita) is added, lettuce seeds are scattered on the surface of the soil and covered with quartz sand. The lettuce seeds germinate and the plants develop. The galls develop on the roots.

[0521] After 21 days, the nematicidal efficacy in % is determined by the formation of galls. 100% means that no galls were found; 0% means that the number of galls on the treated plants corresponds to that of the untreated control.

[0522] In this test, for example, the following compounds of the preparation examples showed an efficacy of 90% at an application rate of 8 ppm: I-1

8. Panonychus ulmi—Spray Test
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: alkylaryl polyglycol ether

[0523] To produce a suitable preparation of active compound, 1 part by weight of active compound is dissolved in the parts by weight of solvent stated and filled with water containing an emulsifier concentration of 1000 ppm until the desired concentration is reached. To prepare further test concentrations, the mixture is diluted with emulsifier-containing water. If the addition of ammonium salts and/or penetrants (rapeseed oil methyl ester) is required, these are, after dilution of the finished preparation solution, added using a pipette, at a concentration of in each case 1000 ppm.

[0524] Plum trees (Prunus domestica), infested by a mixed population of the European red mite (Panonychus ulmi) are treated by spraying with the active compound preparation of the desired concentration.

[0525] After 14 days, the kill in % is determined. 100% means that all spider mites have been killed; 0% means that none of the spider mites have been killed.

[0526] In this test, for example, the following compounds of the preparation examples showed an efficacy of 100% at an application rate of 20 ppm: I-1