2-(Het)aryl-substituted fused heterocycle derivatives as pesticides
11505553 · 2022-11-22
Assignee
Inventors
- Marc Mosrin (Cologne, DE)
- Ruediger Fischer (Pulheim, DE)
- Dominik Hager (Monheim, DE)
- Laura Hoffmeister (Duesseldorf, DE)
- Nina Kausch-Busies (Bergisch Gladbach, DE)
- David Wilcke (Duesseldorf, DE)
- Matthieu Willot (Duesseldorf, DE)
- Kerstin Ilg (Cologne, DE)
- Daniela Portz (Vettweiss, DE)
- Ulrich Goergens (Ratingen, DE)
- Sascha Eilmus (Leichlingen, DE)
- Andreas Turberg (Haan, DE)
Cpc classification
International classification
Abstract
The invention relates to novel compounds of the formula (I) ##STR00001## in which R.sup.1, R.sup.a, R.sup.b, R.sup.c, R.sup.3, R.sup.4, A.sup.1, A.sup.2 and n have the definitions given above, to agrochemical formulations comprising the compounds of formula (I) and to their use as acaricides and/or insecticides for controlling animal pests, particularly arthropods and especially insects and arachnids.
Claims
1. Compound of formula (I) ##STR00042## in which A.sup.1 is nitrogen A.sup.2 is —N(R.sup.6)—, R.sup.1 is (C.sub.1-C.sub.6)-alkyl, R.sup.3 is (C.sub.1-C.sub.4)-haloalkyl, R.sup.4 is hydrogen, R.sup.6 is (C.sub.1-C.sub.6)alkyl, R.sup.b is methyl, R.sup.a is hydrogen or methyl R.sup.c is hydrogen or (C.sub.1-C.sub.4)alkyl and n is 0, 1 or 2.
2. Compound of formula (I) according to claim 1, wherein A.sup.1 is nitrogen, A.sup.2 is —N(R.sup.6)—, R.sup.1 is (C.sub.1-C.sub.4)alkyl, R.sup.3 is (C.sub.1-C.sub.4)-haloalkyl, R.sup.4 is hydrogen, R.sup.b is methyl, R.sup.a is hydrogen or methyl, R.sup.c is hydrogen, methyl or ethyl and n is 0, 1 or 2.
3. Compound of formula (I) according to claim 1, wherein A.sup.1 is nitrogen, A.sup.2 is —N(R.sup.6)—, R.sup.1 is (C.sub.1-C.sub.4)alkyl, R.sup.3 is fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, fluoromethyl, difluoromethyl or trifluoromethyl, R.sup.4 is hydrogen, R.sup.6 is (C.sub.1-C.sub.4), R.sup.b is methyl, R.sup.a is hydrogen or methyl, R.sup.c is hydrogen, methyl or ethyl and n is 0, 1 or 2.
4. Compound of formula (I) according to claim 1, wherein A.sup.1 is nitrogen, A.sup.2 is —N(R.sup.6)—, R.sup.1 is (C.sub.1-C.sub.4)alkyl, R.sup.3 is fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, fluoromethyl, difluoromethyl or trifluoromethyl, R.sup.4 is hydrogen, R.sup.6 is methyl, R.sup.b is methyl, R.sup.a is hydrogen or methyl, R.sup.c is hydrogen, methyl or ethyl and n is 0, 1 or 2.
5. Compound of formula (I) according to claim 1, wherein A.sup.1 is nitrogen, A.sup.2 is —NMe, R.sup.1 is methyl, ethyl, n-propyl, i-propyl or cyclopropyl, R.sup.3 is trifluoromethyl, difluoromethyl, pentafluoroethyl or tetrafluoroethyl (—CF.sub.2CF.sub.2H or CFHCF.sub.3), R.sup.4 is hydrogen, R.sup.a is hydrogen or methyl, R.sup.b is methyl, R.sup.c is hydrogen, methyl or ethyl and n is 0 or 2.
6. Compound of formula (I) according to claim 1, wherein A.sup.1 is nitrogen, A.sup.2 is —NMe, R.sup.1 is ethyl or methyl, R.sup.3 is trifluoromethyl or pentafluoroethyl, R.sup.4 is hydrogen, R.sup.a is hydrogen or methyl, R.sup.b is methyl, R.sup.c is hydrogen or methyl and n is 2.
7. Compound of formula (I) according to claim 1, wherein R.sup.3 is trifluoromethyl.
8. Compound of formula (I-1) ##STR00043## where R.sup.1 is (C.sub.1-C.sub.6)-alkyl, R.sup.3 is (C.sub.1-C.sub.4)-haloalkyl, R.sup.4 is hydrogen, R.sup.6 is (C.sub.1-C.sub.6)alkyl, R.sup.a is hydrogen or methyl, R.sup.c is hydrogen or (C.sub.1-C.sub.4)alkyl and n is 0, 1 or 2.
9. Compound of formula I-a to I-m: ##STR00044## ##STR00045## ##STR00046##
10. Agrochemical formulation comprising a compound of formula (I) according to claim 1 and one or more extenders and/or surfactants.
11. The agrochemical formulation according to claim 10, further comprising an additional agrochemically active ingredient.
12. A method for controlling one or more animal pests selected from the phyla consisting of: Arthropoda, Mollusca, and Nematoda comprising contacting the animal pests and/or habitat thereof with a compound of formula (I) according to claim 1.
13. A product comprising a compound of formula (I) according to claim 1 or an agrochemical formulation thereof for controlling one or more animal pests selected from the phyla consisting of: Arthropoda, Mollusca, and Nematoda.
Description
PREPARATION EXAMPLES
Synthesis of 7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine
(1) ##STR00010##
(2) N3-Methyl-6-(trifluoromethyl)pyridazine-3,4-diamine (192 mg, 1.0 mmol), dissolved in formic acid (0.4 ml, 106 mmol), was heated at 150° C. with microwaves for 2 hours. After customary workup by addition of saturated ammonium chloride solution, the reaction mixture was extracted with ethyl acetate, and the combined organic phases were dried over Na.sub.2SO.sub.4 and concentrated under membrane pump vacuum. After column chromatography purification (ethyl acetate/cyclohexane), 7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine (149 mg, 74%) was obtained as a white solid.
(3) MH.sup.+: 203.1; .sup.1H NMR (d.sub.6-DMSO): δ 8.97 (s, 1H), 8.62 (s, 1H), 4.08 (s, 3H).
Synthesis of 6-(6-bromo-3-fluoropyridin-2-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo-[4,5-c]pyridazine
(4) ##STR00011##
(5) To 7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine (340 mg, 1.7 mmol) dissolved in THF (2 ml) was added TMPZnCl.LiCl (1.31 M in THF, 1.41 ml, 1.85 mmol) at 25° C. under argon; this reaction solution was stirred for 10 min. Subsequently, 6-bromo-3-fluoro-2-iodopyridine (1.016 g, 3.36 mmol) in THF (4 ml) and tetrakis(triphenylphosphine)palladium(0) (195 mg, 0.16 mmol) were added at 25° C. and the solution was stirred at 65° C. for a further 3 hours. After customary workup by addition of saturated ammonium chloride solution, the reaction mixture was extracted with ethyl acetate, and the combined organic phases were dried over Na.sub.2SO.sub.4 and concentrated in a membrane pump vacuum. After column chromatography purification (ethyl acetate/cyclohexane), 6-(6-bromo-3-fluoropyridin-2-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine (408 mg, 62%) was obtained as a white solid.
(6) MH.sup.+: 375.9; .sup.1H NMR (d.sub.6-DMSO): δ 8.77 (s, 1H), 8.10 (m, 2H), 4.25 (s, 3H).
Synthesis of 6-[6-bromo-3-(ethylsulfanyl)pyridin-2-yl]-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine
(7) ##STR00012##
(8) A dry, argon-filled Schlenk flask equipped with a magnetic stirrer bar and a septum was initially charged with 6-(6-bromo-3-fluoropyridin-2-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine (386 mg, 1.01 mmol) in anhydrous THF (4 ml). Sodium hydride (25.1 mg, 1.03 mmol) was added at −20° C., and ethanethiol (70 mg, 1.11 mmol) dissolved in 4 ml THF was added dropwise thereto at −20° C. up to max. −10° C. The mixture was stirred at 20° C. for 1.5 h. Saturated aqueous ammonium chloride solution (25 ml) was added to the reaction mixture, which was extracted with ethyl acetate (3×50 ml) and dried over anhydrous sodium sulfate. After filtration, the solvent was removed under reduced pressure, which gave 6-[6-bromo-3-(ethylsulfanyl)pyridin-2-yl]-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine (442 mg, 95%) as a yellow solid.
(9) MH.sup.+: 418.9; .sup.1H NMR (400 MHz, d.sub.6-DMSO) δ ppm: 8.76 (s, 1H), 8.05 (d, 1H), 7.90 (d, 1H), 4.15 (s, 3H), 3.06 (s, 3H), 1.23 (t, 3H).
Synthesis of 6-[6-bromo-3-(ethylsulfonyl)pyridin-2-yl]-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine
(10) ##STR00013##
(11) A dry, argon-filled Schlenk flask equipped with a magnetic stirrer bar and a septum was initially charged with 6-[6-bromo-3-(ethylsulfanyl)pyridin-2-yl]-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]-pyridazine (442 mg, 1.05 mmol) in dichloromethane (2 ml). Formic acid (243 mg, 5.28 mmol) and hydrogen peroxide (35%; 718 mg, 7.39 mmol) were added successively at 20° C. The mixture was stirred at 20° C. for 4 h. The reaction mixture was admixed at 0° C. with a sodium bisulfite, sodium bicarbonate and saturated aqueous ammonium chloride solution, extracted with dichloromethane and dried over anhydrous sodium sulfate. After filtration, the solvent was removed under reduced pressure.
(12) The crude product was purified by chromatography, which gave 6-[6-bromo-3-(ethylsulfonyl)pyridin-2-yl]-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine (402 mg, 81%) as a white solid.
(13) MH.sup.+: 449.9; .sup.1H NMR (400 MHz, d.sub.6-DMSO) δ ppm: 8.79 (s, 1H), 8.47 (d, 1H), 8.32 (d, 1H), 3.98 (s, 3H), 3.72 (q, 2H), 1.21 (t, 3H).
Synthesis of 1-{5-(ethylsulfonyl)-6-[7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazin-6-yl]pyridin-2-yl}-3-methylurea
(14) ##STR00014##
(15) A dry, argon-filled Schlenk flask equipped with a magnetic stirrer bar and a septum was initially charged with 6-[6-bromo-3-(ethylsulfonyl)pyridin-2-yl]-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]-pyridazine (100 mg, 0.22 mmol) in anhydrous dioxane (2 ml). Methylurea (20 mg, 0.26 mmol), caesium carbonate (109 mg, 0.33 mmol), 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (13 mg, 0.02 mmol) and bis(dibenzylideneacetone)palladium(0) (6 mg, 0.02 mmol) were then added, and the mixture was stirred at 80° C. for 3 h. Saturated aqueous sodium chloride solution (25 ml) was added to the reaction mixture, which was extracted with ethyl acetate (3×50 ml) and dried over anhydrous sodium sulfate. After filtration, the solvent was removed under reduced pressure. The crude product was purified by chromatography, which gave 1-{5-(ethylsulfonyl)-6-[7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazin-6-yl]pyridin-2-yl}-3-methylurea (77 mg, 76%) as a white solid.
(16) MH.sup.+: 444.0; .sup.1H NMR (400 MHz, d.sub.6-DMSO) δ ppm: 10.14 (s, 1H), 8.37 (s, 1H), 8.11 (d, 1H), 7.05 (bd, 1H), 3.94 (s, 3H), 3.59 (q, 2H), 2.70 (d, 3H), 1.18 (t, 3H).
(17) The compounds were separated according to EEC Directive 79/831 Annex V.A8 by HPLC (high-performance liquid chromatography) on a reversed-phase column (C 18). Temperature: 55° C.
(18) The LC-MS determination of the M.sup.+ in the acidic range was effected at pH 2.7 with 0.1% aqueous formic acid and acetonitrile (containing 0.1% formic acid) as eluents; linear gradient from 10% acetonitrile to 95% acetonitrile, instrument: Agilent 1100 LC-System, Agilent MSD System, HTS PAL.
(19) The LC-MS determination of the M.sup.+ 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.
(20) The NMR data of selected examples are listed either in conventional form (6 values, multiplet splitting, number of hydrogen atoms) or as NMR peak lists.
(21) In each case, the solvent in which the NMR spectrum was recorded is stated.
(22) In analogy to the examples and according to the above-described preparation processes, the compounds of the formula (I) listed in Table 1 can be obtained:
(23) ##STR00015##
(24) TABLE-US-00001 TABLE 1 Example No. Structure I-1
(25) NMR Data of Selected Examples
(26) NMR Peak List Method
(27) The 1H-NMR data of selected examples are noted in the form of 1H-NMR peak lists. For each signal peak, first the δ value in ppm and then the signal intensity in round brackets are listed. The pairs of δ value-signal intensity numbers for different signal peaks are listed with separation from one another by semicolons.
(28) The peak list for one example therefore takes the form of:
(29) δ.sub.1 (intensity.sub.1); δ.sub.2 (intensity.sub.2); . . . ; δ.sub.i (intensity.sub.i); . . . ; δ.sub.n (intensity.sub.n)
(30) The intensity of sharp signals correlates with the height of the signals in a printed example of an NMR spectrum in cm and shows the true ratios of the signal intensities. In the case of broad signals, several peaks or the middle of the signal and the relative intensity thereof may be shown in comparison to the most intense signal in the spectrum.
(31) For calibration of the chemical shift of 1H NMR spectra we use tetramethylsilane and/or the chemical shift of the solvent, particularly in the case of spectra measured in DMSO. Therefore, the tetramethylsilane peak may but need not occur in NMR peak lists.
(32) The lists of the 1H NMR peaks are similar to the conventional 1H NMR printouts and thus usually contain all peaks listed in a conventional NMR interpretation.
(33) In addition, like conventional 1H NMR printouts, they may show solvent signals, signals of stereoisomers of the target compounds, which likewise form part of the subject-matter of the invention, and/or peaks of impurities.
(34) In the reporting of compound signals in the delta range of solvents and/or water, our lists of 1H NMR peaks show the usual solvent peaks, for example peaks of DMSO in d.sub.6-DMSO and the peak of water, which usually have a high intensity on average.
(35) The peaks of stereoisomers of the target compounds and/or peaks of impurities usually have a lower intensity on average than the peaks of the target compounds (for example with a purity of >90%).
(36) Such stereoisomers and/or impurities may be typical of the particular preparation process. Their peaks can thus help in identifying reproduction of our preparation process with reference to “by-product fingerprints”.
(37) An expert calculating the peaks of the target compounds by known methods (MestreC, ACD simulation, but also with empirically evaluated expected values) can, if required, isolate the peaks of the target compounds, optionally using additional intensity filters. This isolation would be similar to the relevant peak picking in conventional 1H NMR interpretation.
(38) Further details of 1H NMR peak lists can be found in the Research Disclosure Database Number 564025.
(39) TABLE-US-00002 TABLE 2 NMR data of selected compounds Ex. I-1 I-1: .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 10.1363(2.5); 8.7685(6.4); 8.3793(2.8); 8.3567(3.4); 8.1174(2.3); 8.0948(2.0); 7.0579(1.0); 7.0462(1.0); 4.0558(0.6); 4.0380(1.8); 4.0202(1.8); 4.0023(0.6); 3.9369(16.0); 3.6144(1.0); 3.5961(3.3); 3.5776(3.5); 3.5592(1.0); 3.3193(62.9); 2.7094(6.9); 2.6979(6.8); 2.6753(0.6); 2.6707(0.7); 2.6664(0.6); 2.5102(43.7); 2.5061(85.2); 2.5016(114.2); 2.4972(86.7); 2.3330(0.5); 2.3285(0.7); 2.3240(0.5); 1.9886(7.4); 1.3979(0.6); 1.1930(5.5); 1.1749(11.8); 1.1568(5.2); 0.1460(0.3); 0.0078(3.1); −0.0002(71.0); −0.0083(3.3); −0.1496(0.3) I-2 I-2: .sup.1H-NMR(601.6 MHz, d.sub.6-DMSO): δ = 9.9469(2.6); 8.7710(6.8); 8.3844(2.6); 8.3692(3.2); 8.2317(3.7); 8.2165(3.3); 5.7519(3.3); 4.0355(0.5); 4.0236(0.5); 3.9527(16.0); 3.9011(0.6); 3.8709(0.5); 3.5783(0.9); 3.5660(3.2); 3.5537(3.2); 3.5415(0.9); 3.3046(100.4); 2.9779(13.2); 2.6149(0.5); 2.6118(0.7); 2.6088(0.5); 2.5211(1.4); 2.5180(1.8); 2.5149(1.9); 2.5062(42.1); 2.5031(88.0); 2.5001(121.8); 2.4970(88.1); 2.4940(41.3); 2.3873(0.5); 2.3843(0.7); 2.3812(0.5); 1.9875(2.2); 1.1850(3.5); 1.1727(7.9); 1.1605(3.6); 1.1444(0.3); 0.0052(1.6); −0.0002(48.8); −0.0057(1.6) I-3 I-3: .sup.1H-NMR(601.6 MHz, d.sub.6-DMSO): δ = 8.7571(6.6); 8.3439(3.1); 8.3286(3.5); 8.0509(3.1); 8.0357(3.0); 7.9469(1.0); 7.9395(1.0); 5.7520(1.0); 4.0355(0.5); 4.0236(0.5); 3.9725(16.0); 3.6780(1.0); 3.6657(3.3); 3.6534(3.3); 3.6411(1.0); 3.3958(15.5); 3.3044(105.5); 2.7398(7.4); 2.7325(7.4); 2.6149(0.7); 2.6119(1.0); 2.6089(0.7); 2.5211(1.7); 2.5181(2.1); 2.5150(2.2); 2.5061(55.1); 2.5032(115.7); 2.5001(159.5); 2.4971(116.6); 2.4942(55.3); 2.3874(0.7); 2.3844(1.0); 2.3813(0.7); 1.9876(2.0); 1.2116(3.5); 1.1994(7.8); 1.1870(3.9); 1.1747(1.1); 1.1629(0.5); 0.0052(1.8); −0.0002(56.5); −0.0057(1.9) I-4 I-4: .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.9439(2.2); 8.7851(4.7); 8.7297(0.4); 8.4256(1.9); 8.4028(2.4); 8.2330(2.6); 8.2102(2.2); 4.2907(0.8); 4.0377(0.8); 4.0318(0.6); 4.0200(0.8); 4.0023(0.3); 3.9632(11.6); 3.9111(0.4); 3.4479(10.4); 3.3236(80.8); 2.9793(16.0); 2.9648(1.6); 2.9099(0.4); 2.6707(0.6); 2.6660(0.4); 2.5058(73.5); 2.5015(96.7); 2.4972(71.0); 2.3329(0.4); 2.3283(0.5); 2.3244(0.4); 1.9887(3.3); 1.1923(0.8); 1.1744(1.6); 1.1566(0.8); −0.0001(0.6) I-5 I-5: .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 10.1232(2.5); 8.7772(6.9); 8.7526(0.5); 8.7304(0.4); 8.4167(2.8); 8.3941(3.3); 8.1120(2.3); 8.0893(2.0); 7.0700(1.0); 7.0588(1.0); 5.7571 (0.4); 4.2286(0.7); 4.0226(0.7); 4.0182(0.8); 3.9455(16.0); 3.9119(0.4); 3.4637(14.4); 3.3220(63.4); 2.7197(1.3); 2.7108(7.2); 2.6994(6.8); 2.6749(0.6); 2.6710(0.7); 2.6666(0.6); 2.5062(89.2); 2.5018(1182); 2.4974(87.6); 2.3285(0.7); −0.0001(0.8) I-6 I-6: .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 8.7723(6.2); 8.7592(0.6); 8.6587(0.3); 8.3889(3.1); 8.3659(3.6); 8.0599(3.3); 8.0369(3.0); 7.9860(0.4); 7.9515(1.1); 7.9405(1.1); 4.2549(0.8); 4.0555(0.7); 4.0466(1.0); 4.0377(2.1); 4.0199(2.0); 4.0020(0.8); 3.9836(16.0); 3.5249(13.9); 3.3997(15.7); 3.3732(1.7); 3.3202(97.7); 2.7420(7.3); 2.7310(7.5); 2.7169(1.0); 2.7031(0.5); 2.6748(1.4); 2.6704(1.9); 2.6661(1.4); 2.5238(4.5); 2.5101(120.6); 2.5059(251.7); 2.5014(335.1); 2.4969(240.5); 2.4926(115.2); 2.3325(1, 4); 2.3281(2.0); 2.3237(1.4); 1.9888(8.9); 1.1923(2.3); 1.1745(4.6); 1.1568(2.3); −0.0001(2.0) I-7 I-7: .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 10.1290(2.7); 8.8120(6.9); 8.3799(2.9); 8.3572(3.4); 8.0855(2.2); 8.0628(1.9); 7.1345(1.0); 7.1228(1.0); 3.9414(16.0); 3.9078(0.5); 3.6262(1.0); 3.6081 (3.5); 3.5895(3.5); 3.5712(1.0); 3.3227(167.9); 2.7101(6.9); 2.6987(7.0); 2.6711(1.3); 2.5062(166.4); 2.5020(213.5); 2.4980(155.3); 2.3285(1.2); 1.1952(3.7); 1.1767(8.1); 1.1582(3.6); 1.1468(0.4); 0.1459(0.4); 0.0077(3.3); −0.0002(87.8); −0.1491(0.4) I-8 I-8: .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 8.8090(7.0); 8.3548(3.2); 8.3319(3.8); 8.0521(3.3); 8.0292(3.0); 7.9842(1.2); 7.9734(1.2); 3.9779(16.0); 3.7002(0.9); 3.6817(3.3); 3.6633(3.4); 3.6448(1.0); 3.3965(15.6); 3.3226(38.6); 2.7423(7.4); 2.7313(7.4); 2.6755(0.4); 2.6714(0.5); 2.6669(0.4); 2.5244(1.3); 2.5108(32.7); 2.5067(67.0); 2.5022(88.6); 2.4978(63.6); 2.4935(30.4); 2.3336(0.4); 2.3288(0.5); 2.3244(0.4); 1.6480(0.4); 1.2195(3.5); 1.2011(7.9); 1.1826(3.4); −0.0002(8.6); −0.0082(0.3) I-9 I-9: .sup.1H-NMR(601.6 MHz, d.sub.6-DMSO): δ = 9.9316(2.2); 8.8172(6.7); 8.3878(2.8); 8.3727(3.4); 8.2283(3.6); 8.2131(3.2); 5.7520(7.5); 3.9610(16.0); 3.5877(1.0); 3.5754(3.3); 3.5631(3.4); 3.5508(1.0); 3.3051(61.1); 2.9784(15.4); 2.6150(0.4); 2.6120(0.6); 2.6090(0.4); 2.5212(1.0); 2.5182(1.3); 2.5151(1.3); 2.5062(33.1); 2.5032(69.9); 2.5002(96.9); 2.4972(72.0); 2.4943(35.3); 2.3874(0.4); 2.3844(0.6); 2.3814(0.4); 1.9876(0.3); 1.1868(3.6); 1.1745(8.1); 1.1622(3.6); 0.0052(1.1); −0.0002(35.2); −0.0057(1.3) I-10 I-10: .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 10.1134(2.6); 8.8188(6.3); 8.7722(0.6); 8.4169(2.8); 8.3942(3.3); 8.0794(2.2); 8.0566(2.0); 7.1434(1.0); 7.1313(1.0); 5.7570(1.9); 4.3578(0.6); 3.9500(16.0); 3.9171(1.0); 3.8516(0.7); 3.4749(14.3); 3.3494(0.8); 3.3426(0.9); 3.3200(45.0); 3.0091(0.6); 2.7405(0.3); 2.7325(0.4); 2.7114(6.8); 2.7000(6.9); 2.6702(0.9); 2.6660(0.7); 2.5057(113.2); 2.5013(151.0); 2.4970(111.8); 2.3321(0.6); 2.3281(0.8); 0.1458(0.5); 0.0077(4.2); 0.0003(115.2); −0.0083(5.4); −0.1502(0.5) I-11 I-11: .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.9295(2.3); 8.8307(4.4); 8.4298(2.0); 8.4070(2.4); 8.2301(2.8); 8.2073(2.4); 7.6454(0.3); 7.6272(0.6); 7.6154(0.4); 7.5978(0.5); 7.5743(0.4); 7.5661(0.4); 7.5483(0.4); 3.9731(12.0); 3.4592(10.5); 3.3219(20.6); 2.9804(16.0); 2.5241(0.6); 2.5104(18.0); 2.5062(36.9); 2.5018(48.8); 2.4973(34.9); 2.4932(16.8); 2.0749(1.0); 0.0078(1.3); −0.0002(37.4); −0.0084(1.4) I-12 I-12: .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 8.7536 (3.3); 8.2571 (1.6); 8.2344 (1.8); 7.2688 (1.7); 7.2460 (1.6); 5.7560 (1.2); 3.9859 (8.3); 3.6736 (0.6); 3.6553 (1.8); 3.6368 (1.8); 3.6180 (0.6); 3.3202 (2.5); 3.2197(8.2); 2.9469 (16.0); 2.6705 (0.4); 2.5060 (46.5); 2.5016 (61.5); 2.4973 (47.8); 2.3282(0.4); 1.2140 (1.9); 1.1956 (4.2); 1.1770 (1.9); 0.0078 (2.8); −0.0002 (56.1) I-13 I-13: .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO):δ = 8.7951 (3.2); 8.2607 (1.6); 8.2379 (1.8); 8.2126 (0.4); 7.2709 (1.7); 7.2481 (1.7); 3.9907 (8.4); 3.6810 (0.5); 3.6626 (1.8); 3.6440 (1.8); 3.6256 (0.5); 3.3254 (11.0); 3.2183 (8.2); 2.9474 (16.0); 2.6713 (0.4); 2.5245 (0.9); 2.5108 (23.2); 2.5066 (47.0); 2.5022 (61.7); 2.4977 (44.5); 2.4936 (21.9); 2.3288 (0.4); 1.2156 (1.9); 1.1972 (4.2); 1.1787 (1.8); 0.0077 (2.3); −0.0002 (63.2); −0.0082 (2.6)
(40) Use Examples
(41) Ctenocephalides felis—In Vitro Contact Tests with Adult Cat Fleas
(42) 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.
(43) 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.
(44) A substance shows good efficacy against Ctenocephalides felis if at least 80% efficacy was achieved in this test at an application rate of 5 μg/cm.sup.2. 100% efficacy means that all the fleas were dead or moribund. 0% efficacy means that no fleas were harmed.
(45) 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): I-1, I-2, I-3, I-5, I-8, I-9, I-10, I-11
(46) Boophilus microplus—Injection Test
(47) Solvent: dimethyl sulfoxide
(48) To produce a suitable active ingredient formulation, 10 mg of active ingredient are mixed with 0.5 ml of solvent and the concentrate is diluted to the desired concentration with solvent.
(49) 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.
(50) 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.
(51) In this test, for example, the following compounds from the preparation examples show an efficacy of 80% at an application rate of 20 μg/animal: I-6
(52) Ctenocephalides felis—Oral Test
(53) Solvent: dimethyl sulfoxide
(54) 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.
(55) 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.
(56) After 2 days, the kill in % is determined. 100% means that all of the fleas have been killed; 0% means that none of the fleas have been killed.
(57) In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 100 ppm: I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11
(58) Lucilia cuprina Test
(59) Solvent: dimethyl sulfoxide
(60) 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.
(61) About 20 L1 larvae of the Australian sheep blowfly (Lucilia cuprina) are transferred into a test vessel containing minced horsemeat and the active ingredient formulation of the desired concentration.
(62) After 2 days, the kill in % is determined. 100% means that all the larvae have been killed; 0% means that no larvae have been killed.
(63) In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 100 ppm: I-1, I-2, I-7, I-8, I-9, I-10, I-11
(64) In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 100 ppm: I-3
(65) Meloidogyne incognita Test
(66) Solvent: 125.0 parts by weight of acetone
(67) To produce a suitable active ingredient formulation, 1 part by weight of active ingredient is mixed with the stated amount of solvent and the concentrate is diluted to the desired concentration with water.
(68) Vessels are filled with sand, active ingredient 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.
(69) 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.
(70) In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 20 ppm: I-1, I-2, I-3, I-7, I-8, I-9, I-11
(71) In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 20 ppm: I-13
(72) Myzus persicae—Oral Test
(73) Solvent: 100 parts by weight of acetone
(74) To produce a suitable active ingredient formulation, 1 part by weight of active ingredient is dissolved with the stated parts by weight of solvent and made up to the desired concentration with water.
(75) 50 μl of the active ingredient preparation are transferred into microtitre plates and made up to a final volume of 200 μl with 150 μl 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.
(76) 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.
(77) In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 4 ppm: I-1, I-2, I-3, I-4, I-5, I-6, I-8, I-9, I-10, I-11, I-12, I-13
(78) 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: I-2, I-3, I-5, I-6, I-9, I-10, I-11, I-12, I-13
(79) 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: I-1, I-7, I-8
(80) Myzus persicae—Spray Test
(81) Solvent: 78 parts by weight of acetone 1.5 parts by weight of dimethylformamide
(82) Emulsifier: alkylaryl polyglycol ether
(83) 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.
(84) Discs of Chinese cabbage leaves (Brassica pekinensis) infested by all stages of the green peach aphid (Myzus persicae) are sprayed with an active ingredient formulation of the desired concentration.
(85) 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.
(86) 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-1, I-12, I-13
(87) 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-2, I-5, I-6, I-7, I-11
(88) In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 20 g/ha: I-2, I-3, I-7, I-8, I-9
(89) 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: I-1, I-11, I-12, I-13
(90) Phaedon cochleariae—Spray Test
(91) Solvent: 78.0 parts by weight of acetone 1.5 parts by weight of dimethylformamide
(92) Emulsifier: alkylaryl polyglycol ether
(93) 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.
(94) Discs of Chinese cabbage leaves (Brassica pekinensis) are sprayed with an active ingredient formulation of the desired concentration and, after drying, populated with larvae of the mustard beetle (Phaedon cochleariae).
(95) 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.
(96) 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-1, I-2, I-3, I-7, I-8, I-9, I-10, I-11, I-13
(97) Tetranychus urticae—Spray Test, OP-resistant
(98) Solvent: 78.0 parts by weight of acetone 1.5 parts by weight of dimethylformamide
(99) Emulsifier: alkylaryl polyglycol ether
(100) 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.
(101) Discs of bean leaves (Phaseolus vulgaris) infested with all stages of the greenhouse red spider mite (Tetranychus urticae) are sprayed with an active ingredient formulation of the desired concentration.
(102) 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.
(103) In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 4 g/ha: I-7
(104) Contrastive Examples
(105) Phaedon cochleariae—Spray Test (PHAECO)
(106) Solvent: 78.0 parts by weight of acetone 1.5 parts by weight of dimethylformamide
(107) Emulsifier: alkylaryl polyglycol ether
(108) To produce an appropriate active ingredient formulation, 1 part by weight of active ingredient is dissolved with 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. For production of further test concentrations, the mixture is diluted with emulsifier-containing water.
(109) Discs of chinese cabbage leaves (Brassica pekinensis) are sprayed with an active ingredient formulation of the desired concentration and, after drying, populated with larvae of the mustard beetle (Phaedon cochleariae).
(110) After the desired time, the efficacy in % is determined. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.
(111) In this test, for example, the following compounds from the preparation examples show superior efficacy compared to the prior art: see table.
(112) Myzus persicae—Spray Test (MYZUPE)
(113) Solvent: 78.0 parts by weight of acetone 1.5 parts by weight of dimethylformamide
(114) Emulsifier: alkylaryl polyglycol ether
(115) 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.
(116) Discs of chinese cabbage leaves (Brassica pekinensis) infested by all stages of the green peach aphid (Myzus persicae) are sprayed with an active ingredient formulation of the desired concentration.
(117) After the desired time, the efficacy in % is determined. 100% means that all aphids have been killed; 0% means that no aphids have been killed.
(118) In this test, for example, the following compounds from the preparation examples show superior efficacy compared to the prior art: see table.
(119) Tetranychus urticae—Spray Test; OP-Resistant (TETRUR)
(120) Solvent: 78.0 parts by weight of acetone 1.5 parts by weight of dimethylformamide
(121) Emulsifier: alkylaryl polyglycol ether
(122) To produce an appropriate active ingredient formulation, 1 part by weight of active ingredient is dissolved with 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. For production of further test concentrations, the mixture is diluted with emulsifier-containing water.
(123) Discs of bean leaves (Phaseolus vulgaris) infested by all stages of the common spider mite (Tetranychus urticae) are sprayed with an active ingredient formulation of the desired concentration.
(124) After the desired time, the efficacy in % is determined. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.
(125) In this test, for example, the following compounds from the preparation examples show superior efficacy compared to the prior art: see table.
(126) Aphis gossypii—Spray Test (APHIGO)
(127) Solvent: 14 parts by weight of dimethylformamide
(128) Emulsifier: alkylaryl polyglycol ether
(129) To produce an appropriate active ingredient formulation, 1 part by weight of active ingredient is dissolved with 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. For production of further test concentrations, the mixture is diluted with emulsifier-containing water. If addition of ammonium salts or/and penetrants is required, these are each added to the preparation solution in a concentration of 1000 ppm.
(130) Cotton plants (Gossypium hirsutum) severely infested by the cotton aphid (Aphis gossypii) are sprayed with an active ingredient formulation of the desired concentration.
(131) After the desired time, the kill in % is determined. 100% means that all aphids have been killed; 0% means that no aphids have been killed.
(132) In this test, for example, the following compounds from the preparation examples show superior efficacy compared to the prior art: see table.
(133) Myzus persicae—Spray Test (MYZUPE S)
(134) Solvent: 14 parts by weight of dimethylformamide
(135) Emulsifier: alkylaryl polyglycol ether
(136) To produce an appropriate active ingredient formulation, 1 part by weight of active ingredient is dissolved with 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. For production of further test concentrations, the mixture is diluted with emulsifier-containing water. If addition of ammonium salts or/and penetrants is required, these are each added to the preparation solution in a concentration of 1000 ppm.
(137) Bell pepper plants (Capsicum annuum) severely infested by the green peach aphid (Myzus persicae) are treated by spraying with the active ingredient formulation in the desired concentration.
(138) After the desired time, the kill in % is determined. 100% means that all animals have been killed; 0% means that no animals have been killed.
(139) In this test, for example, the following compounds from the preparation examples show superior efficacy compared to the prior art: see table.
(140) Myzus persicae—Drench Test (MYZUPE D)
(141) Solvent: 7 parts by weight of dimethylformamide
(142) Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
(143) To produce an appropriate active ingredient formulation, 1 part by weight of active ingredient is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration, it being necessary to take into account soil volume into which drenching is effected. It should be ensured that a concentration of 40 ppm of emulsifier in the soil is not exceeded. For production of further test concentrations, the mixture is diluted with water.
(144) Savoy cabbage plants (Brassica oleracea) in earth pots, infested by all stages of the green peach aphid (Myzus persicae), are drenched with an active ingredient formulation of the desired concentration.
(145) After the desired time, the efficacy in % is determined. 100% means that all aphids have been killed; 0% means that no aphids have been killed.
(146) In this test, for example, the following compounds from the preparation examples show superior efficacy compared to the prior art: see table.
(147) Nilaparvata lugens—Spray Test (NILALU)
(148) Solvent: 52.5 parts by weight of acetone 7 parts by weight of dimethylformamide
(149) Emulsifier: alkylaryl polyglycol ether
(150) To produce an appropriate active ingredient formulation, 1 part by weight of active ingredient is dissolved with 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. For production of further test concentrations, the mixture is diluted with emulsifier-containing water. If addition of ammonium salts or/and penetrants is required, these are each added to the preparation solution in a concentration of 1000 ppm.
(151) Rice plants (Oryza sativa) are sprayed with an active ingredient formulation of the desired concentration and then populated with larvae of the rice cicada (Nilaparvata lugens).
(152) After the desired time, the efficacy in % is determined. 100% means that all rice cicadas have been killed; 0% means that no rice cicadas have been killed.
(153) In this test, for example, the following compounds from the preparation examples show superior efficacy compared to the prior art: see table.
(154) Nezara viridula—Spray Test (NEZARA)
(155) Solvent: 52.5 parts by weight of acetone 7 parts by weight of dimethylformamide
(156) Emulsifier: alkylaryl polyglycol ether
(157) To produce an appropriate active ingredient formulation, 1 part by weight of active ingredient is dissolved with 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. For production of further test concentrations, the mixture is diluted with emulsifier-containing water. If addition of ammonium salts or/and penetrants is required, these are each added to the preparation solution in a concentration of 1000 ppm.
(158) Barley plants (Hordeum vulgare) infested with larvae of the southern green shield bug (Nezara viridula) are sprayed with an active ingredient formulation of the desired concentration.
(159) After the desired time, the efficacy in % is determined. 100% means that all bugs have been killed; 0% means that no bugs have been killed.
(160) In this test, for example, the following compounds from the preparation examples show superior efficacy compared to the prior art: see table.
(161) Nilaparvata lugens—Test (NILALU S)
(162) Solvent: 14 parts by weight of dimethylformamide
(163) Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
(164) To produce an appropriate active ingredient formulation, 1 part by weight of active ingredient is dissolved with the stated parts by weight of solvent and emulsifier and made up with water until the desired concentration is attained. For production of further test concentrations, the mixture is diluted with water. If addition of ammonium salts or/and penetrants (rapeseed oil methyl ester) is required, these are each pipetted into the finished preparation solution in a concentration of 1000 ppm after the dilution.
(165) Rice plants (Oryza sativa, var. Balilla) are treated by spraying with the active ingredient formulation in the desired concentration and then populated with L3 larvae of the brown planthopper (Nilaparvata lugens).
(166) After the desired time, the kill in % is determined. 100% means that all planthoppers have been killed and 0%, means that no planthoppers have been killed.
(167) In this test, for example, the following compounds from the preparation examples show superior efficacy compared to the prior art: see table.
(168) TABLE-US-00003 Substance Structure Object Concentration % efficacy dat Prior art according to WO2017/025419