PESTICIDALLY ACTIVE AZOLE-AMIDE COMPOUNDS

Abstract

Compounds of formula I wherein the substituents are as defined in claim 1, and the agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds, can be used as insecticides.

##STR00001##

Claims

1. A compound of the formula I ##STR00148## wherein: R.sub.1 is hydrogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6cyanoalkyl, aminocarbonylC.sub.1-C.sub.6alkyl, hydroxycarbonylC.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6nitroalkyl, trimethylsilaneC.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6alkynyl, C.sub.2-C.sub.6haloalkynyl; C.sub.3-C.sub.4cycloalkylC.sub.1-C.sub.2alkyl- wherein the C.sub.3-C.sub.4cycloalkyl is optionally substituted with 1 or 2 halo atoms; oxetan-3-yl-CH.sub.2—; or benzyl optionally substituted with halo or C.sub.1-C.sub.6haloalkyl; R.sub.2 is phenyl, pyridine, pyrimidine, pyrazine or pyridazine, wherein the phenyl, pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to three substituents, provided the substituent(s) are not on either carbon adjacent to the carbon C═O is attached, and each substituent is independently selected from: C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3thiohaloalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3haloalkoxy, halogen, NO.sub.2, SF.sub.5, CN, CONH.sub.2, COOH and C(S)NH.sub.2; R.sub.3 is C.sub.1-C.sub.3alkyl or C.sub.1-C.sub.3haloalkyl; R.sub.4 is pyridine, pyrimidine, pyrazine or pyridazine, wherein the pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one substituent selected from C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3alkoxy, C.sub.3-C.sub.4cycloalkyl, halogen or hydroxy; Z.sub.1 is halogen, CN, NH.sub.2C(O), amino (i.e NH.sub.2), (C.sub.1-C.sub.3alkyl)amino, diC.sub.1-C.sub.3alkyl)amino, hydroxy, C.sub.3-C.sub.4halocycloalkyl, C.sub.3-C.sub.4cyanocycloalkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6alkynyl, C.sub.2-C.sub.6haloalkynyl, C.sub.1-C.sub.4haloalkylsulfanyl, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl, C.sub.1-C.sub.4alkylsulfanyl, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.3alkoxy-C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3alkoxy-C.sub.1-C.sub.3alkoxy, (C.sub.1-C.sub.3alkyl)sulfonylamino, (C.sub.1-C.sub.3alkyl)sulfonyl(C.sub.1-C.sub.3alkyl)amino, (C.sub.1-C.sub.3alkyl)NHC(O), (C.sub.1-C.sub.3alkyl).sub.2NC(O), (C.sub.1-C.sub.3cycloalkyl)NHC(O), (C.sub.1-C.sub.3cycloalkyl)(C.sub.1-C.sub.3alkyl)NC(O), (C.sub.1-C.sub.3alkyl)C(O)(C.sub.1-C.sub.3alkyl)N, (C.sub.1-C.sub.3alkyl)C(O)NH, (C.sub.1-C.sub.3alkyl)C(O), HC(O), diphenylmethanimine, C.sub.1-C.sub.3haloalkoxy, phenyl or a 5-membered heteroaromatic ring wherein the phenyl or the 5-membered heteroaromatic ring can be optionally substituted with one to three substituents selected from C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3alkoxy, C.sub.3-C.sub.4cycloalkyl, halogen, CN or hydroxy; or a stereoisomer, enantiomer, tautomer and N-oxide of the compound of formula I, or agrochemically acceptable salt thereof.

2. The compound according to claim 1, wherein R.sub.3 is methyl.

3. The compound according to claim 1, wherein R.sub.1 is hydrogen; C.sub.1-C.sub.6alkyl optionally substituted with one substituent selected from: CN, CONH.sub.2, COOH, NO.sub.2, and —Si(CH.sub.3).sub.3; C.sub.1-C.sub.6haloalkyl; C.sub.2-C.sub.6alkenyl; C.sub.2-C.sub.6alkynyl; C.sub.2-C.sub.6haloalkynyl; C.sub.3-C.sub.4cycloalkyl-C.sub.1-C.sub.2alkyl—wherein the C.sub.3-C.sub.4cycloalkyl- is optionally substituted with 1 or 2 halo atoms; oxetan-3-yl-CH.sub.2—; or benzyl optionally substituted with halo or C.sub.1-C.sub.3haloalkyl.

4. The compound according to claim 1, wherein R.sub.2 is one of Y.sub.1 to Y.sub.21 ##STR00149## ##STR00150## ##STR00151## ##STR00152##

5. The compound according to claim 1, wherein R.sub.4 is selected from J.sub.1 to J.sub.8 ##STR00153##

6. The compound according to claim 1, wherein R.sub.4 is selected from J.sub.1, J.sub.2, J.sub.3, J.sub.4, J.sub.6, and J.sub.7 and J.sub.8.

7. The compound according to claim 1, wherein R.sub.1 is cyclopropyl-CH.sub.2—, CH≡CCH.sub.2—, CH.sub.2═CHCH.sub.2—, hydrogen, or methyl; R.sub.2 is one of Y.sub.1 to Y.sub.21; and R.sub.3 is methyl.

8. The compound according to claim 1, wherein Z.sub.1 is halogen, CN, amino, (C.sub.1-C.sub.3alkyl)amino, di(C.sub.1-C.sub.3alkyl)amino, hydroxyl, C.sub.3-C.sub.4halocycloalkyl, C.sub.3-C.sub.4cyanocycloalkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6alkynyl, C.sub.2-C.sub.6haloalkynyl, C.sub.1-C.sub.4haloalkylsulfanyl, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl, C.sub.1-C.sub.4alkylsulfanyl, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.3alkoxy-C.sub.1-C.sub.3alkyl, (C.sub.1-C.sub.3alkyl)sulfonylamino, (C.sub.1-C.sub.3alkyl)sulfonyl(C.sub.1-C.sub.3alkyl)amino, (C.sub.1-C.sub.3alkyl)NHC(O), (C.sub.1-C.sub.3alkyl).sub.2NC(O), NH.sub.2C(O), (C.sub.1-C.sub.3cycloalkyl)NHC(O), (C.sub.1-C.sub.3cycloalkyl)(C.sub.1-C.sub.3alkyl)NC(O), (C.sub.1-C.sub.3alkyl)C(O)(C.sub.1-C.sub.3alkyl)N, (C.sub.1-C.sub.3alkyl)C(O)NH, C.sub.1-C.sub.3haloalkoxy, (C.sub.1-C.sub.3alkyl)C(O), C.sub.1-C.sub.3alkoxy-C.sub.1-C.sub.3alkoxy, HC(O), or diphenylmethanimine.

9. The compound according to claim 4, wherein Z.sub.1 is halogen, CN, amino, di(C.sub.1-C.sub.3alkyl)amino, hydroxyl, C.sub.3-C.sub.4halocycloalkyl, C.sub.3-C.sub.4cyanocycloalkyl, (C.sub.1-C.sub.3alkyl)NHC(O), (C.sub.1-C.sub.3alkyl).sub.2NC(O), NH.sub.2C(O), (C.sub.1-C.sub.3cycloalkyl)NHC(O), (C.sub.1-C.sub.3cycloalkyl)(C.sub.1-C.sub.3alkyl)NC(O), (C.sub.1-C.sub.3alkyl)C(O)(C.sub.1-C.sub.3alkyl)N, (C.sub.1-C.sub.3alkyl)C(O)NH, C.sub.1-C.sub.3haloalkoxy, (C.sub.1-C.sub.3alkyl)C(O), C.sub.1-C.sub.3alkoxy-C.sub.1-C.sub.3alkoxy, HC(O), or diphenylmethanimine.

10. A composition comprising a compound as defined in claim 1, one or more auxiliaries and diluent, and optionally one more other active ingredient.

11. A method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound as defined as defined in claim 1.

12. (canceled)

13. A plant propagation material, such as a seed, comprising, or treated with or adhered thereto, a compound as defined in claim 1.

14. (canceled)

15. The compound according to 5, wherein Z.sub.1 is halogen, CN, amino, di(C.sub.1-C.sub.3alkyl)amino, hydroxyl, C.sub.3-C.sub.4halocycloalkyl, C.sub.3-C.sub.4cyanocycloalkyl, (C.sub.1-C.sub.3alkyl)NHC(O), (C.sub.1-C.sub.3alkyl).sub.2NC(O), NH.sub.2C(O), (C.sub.1-C.sub.3cycloalkyl)NHC(O), (C.sub.1-C.sub.3cycloalkyl)(C.sub.1-C.sub.3alkyl)NC(O), (C.sub.1-C.sub.3alkyl)C(O)(C.sub.1-C.sub.3alkyl)N, (C.sub.1-C.sub.3alkyl)C(O)NH, C.sub.1-C.sub.3haloalkoxy, (C.sub.1-C.sub.3alkyl)C(O), C.sub.1-C.sub.3alkoxy-C.sub.1-C.sub.3alkoxy, HC(O), or diphenylmethanimine.

16. The compound according to 1, wherein R.sub.1 is cyclopropyl-CH.sub.2—, CH≡CCH.sub.2—, CH.sub.2═CHCH.sub.2—, hydrogen, or methyl; R.sub.4 is selected from J.sub.1 to J.sub.8; and Z.sub.1 is halogen, CN, amino, di(C.sub.1-C.sub.3alkyl)amino, hydroxyl, C.sub.3-C.sub.4halocycloalkyl, C.sub.3-C.sub.4cyanocycloalkyl, (C.sub.1-C.sub.3alkyl)NHC(O), (C.sub.1-C.sub.3alkyl).sub.2NC(O), NH.sub.2C(O), (C.sub.1-C.sub.3cycloalkyl)NHC(O), (C.sub.1-C.sub.3cycloalkyl)(C.sub.1-C.sub.3alkyl)NC(O), (C.sub.1-C.sub.3alkyl)C(O)(C.sub.1-C.sub.3alkyl)N, (C.sub.1-C.sub.3alkyl)C(O)NH, C.sub.1-C.sub.3haloalkoxy, (C.sub.1-C.sub.3alkyl)C(O), C.sub.1-C.sub.3alkoxy-C.sub.1-C.sub.3alkoxy, HC(O), or diphenylmethanimine.

Description

PREPARATORY EXAMPLES

[0472] “Mp” means melting point in ° C. Free radicals represent methyl groups. .sup.1H NMR measurements were recorded on a Brucker 400 MHz spectrometer, chemical shifts are given in ppm relevant to a TMS standard. Spectra measured in deuterated solvents as indicated. The method below was used to characterize the compounds. The characteristic LCMS values obtained for each compound were the retention time (“Rt”, recorded in minutes) and the measured molecular ion (M+H).sup.+.

[0473] LCMS Method:

[0474] Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions, Capillary: 3.00 kV, Cone range: 30 V, Extractor: 2.00 V, Source Temperature: 150° C., Desolvation Temperature: 350° C., Cone Gas Flow: 50 I/h, Desolvation Gas Flow: 650 I/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment, diode-array detector and ELSD detector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C., DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5% MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH, gradient: 10-100% B in 1.2 min; Flow (ml/min) 0.85

Example 1: Preparation of N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (compound P3)

[0475] ##STR00070##

Step A: Preparation of 2-(methylamino)propanamide

[0476] ##STR00071##

[0477] To a solution of 2-bromopropanamide (10 g, 65.8 mmol) in acetonitrile was added potassium carbonate (27.5 g, 197.4 mmol) and a 2 M solution of methylamine in THF (66 mL, 131.6 mmol). The resulting suspension is stirred at 80° C. for 16 hours, filtered and concentrated in vacuo. The residue was dissolved in ethyl acetate (100 mL), washed successively with water and brine, dried over sodium sulfate, filtered and concentrated in vacuo to give 2-(methylamino)propanamide as white crystals.

[0478] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=3.06 (q, J=7.0 Hz, 1H), 2.42 (s, 3H), 1.32 (d, J=7.0 Hz, 3H) ppm.

Step B: Preparation of N-(2-amino-1-methyl-2-oxo-ethyl)-N-methyl-3,5-bis(trifluoromethyl)benzamide

[0479] ##STR00072##

[0480] A solution of 2-(methylamino)propanamide (6.7 g, 65.8 mmol), N,N-diisopropylethylamine (34.5 mL, 197 mmol), 3,5-bis(trifluoromethyl)benzoic acid (17 g, 65.8 mmol) in ethyl acetate (230 mL) and N,N-dimethylformamide (164 mL) was cooled at 0° C. and treated dropwise with a 50% solution of 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphorinane-2,4,6-trioxide (T3P) in ethyl acetate (47 mL, 79 mmol). The resulting orange solution was stirred at room temperature for 45 minutes and then concentrated in vacuo. The residue was dissolved in methyl tert-butyl ether (200 mL), and washed with water (2×30 mL), 2 M NaOH (2×30 mL), brine (30 mL), and the organic phase dried over sodium sulfate, filtered and concentrated in vacuo to give N-(2-amino-1-methyl-2-oxo-ethyl)-N-methyl-3,5-bis(trifluoromethyl)benzamide as a crude orange gum, which was used without any further purification in the following step.

[0481] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=7.98 (s, 1H), 7.92 (s, 2H), 5.25-5.15 (m, 1H), 2.95 (bs, 3H), 1.50 (d, J=7.0 Hz, 3H) ppm; LCMS: R.sub.t 0.85, m/z=341 (M−H.sup.+, negative mode).

Step C: Preparation of N-[2-[dimethylaminomethyleneamino]-1-methyl-2-oxo-ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide

[0482] ##STR00073##

[0483] To a solution of N-(2-amino-1-methyl-2-oxo-ethyl)-N-methyl-3,5-bis(trifluoromethyl)benzamide (19 g, 55.52 mmol) in dichloromethane (285 mL) was added N,N-dimethylformamid dimethyl acetal (11 mL, 83 mmol). The resulting mixture was stirred at 40° C. for four hours and then concentrated in vacuo to give N-[2-[dimethylaminomethyleneamino]-1-methyl-2-oxo-ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide as a crude orange gum.

[0484] LCMS: R.sub.t 0.89, m/z=398 (M+H.sup.+).

Step D: Preparation of N-methyl-N-[1-(1H-1,2,4-triazol-5-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide

[0485] ##STR00074##

[0486] To a solution of N-[2-[dimethylaminomethyleneamino]-1-methyl-2-oxo-ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (2 g, 4.78 mmol) in a mixture of 1,4-dioxane (20 mL) and acetic acid (20 mL) was added hydrazine monohydrate (0.465 mL, 9.56 mmol). The reaction mixture was stirred at 65° C. for two hours and then concentrated in vacuo. Purification by chromatography on silica gel (eluting with ethyl acetate in cyclohexane) afforded N-methyl-N-[1-(1H-1,2,4-triazol-5-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide.

[0487] LCMS: R.sub.t 0.86, m/z=367 (M+H.sup.+).

Step E: Preparation of N-[1-(3-bromo-1H-1,2,4-triazol-5-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (16)

[0488] ##STR00075##

[0489] To a solution of N-methyl-N-[1-(1H-1,2,4-triazol-5-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (0.95 g, 2.6 mmol) in dichloromethane (30 mL) was added a 2 M aqueous solution of NaOH (3.9 mL, 7.8 mmol) and a solution of benzyltrimethylammonium tribromide (1.1 g, 2.9 mmol) in dichloromethane (10 mL). The reaction mixture was stirred for 45 minutes and then carefully quenched with a 2 M aqueous solution of HCl. The organic phase was separated, dried over sodium sulfate, filtered and concentrated in vacuo to give N-[1-(3-bromo-1H-1,2,4-triazol-5-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide as a yellow solid.

[0490] LCMS: R.sub.t 0.98, m/z=445, 447 (M+H.sup.+).

Step F: Preparation of N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide compound P3)

[0491] ##STR00076##

[0492] To a solution of N-[1-(3-bromo-1H-1,2,4-triazol-5-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (0.84 g, 1.9 mmol) in dry DMF (9.4 mL) was added NaH (0.11 g, 2.8 mmol) under argon followed by stirring at room temperature for 30 min. A solution of 2-bromopyrimidine (0.60 g, 3.8 mmol) in dry DMF (2.0 mL) was added to this mixture and the reaction was stirred at room temperature for 1 hour followed by heating to 120° C. for 15 hours. The reaction mixture was taken up in ethyl acetate and washed with water (5×5 mL), once with brine, dried over anhydrous MgSO4, filtered and concentrated in vacuo. Purification by reverse phase chromatography (eluting with acetonitrile/water) afforded N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide.

[0493] LCMS: R.sub.t 1.05, m/z=525 (M+H.sup.+).

Example 2: Preparation of N-[1-[5-(methoxymethyl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (Compound P2)

[0494] ##STR00077##

Step A: Preparation of ethyl 2-[[3,5-bis(trifluoromethyl)benzoyl]amino]propanoate

[0495] ##STR00078##

[0496] To a stirred solution of 3,5-bis(trifluoromethyl)benzoic acid (10.0 g, 38.7 mmol) in dichloromethane 10.0 mL) was added SOCl.sub.2 (9.21 g, 77.5 mmol) at 0° C. and the resulting mixture stirred at room temperature for 2 hours. The mixture was then concentrated in vacuo and the residue obtained was added to a stirred solution of ethyl alaninate (5.44 g, 46.5 mmol) in pyridine (100 mL) at 0° C. The reaction mixture was stirred for 2 hours at room temperature. After reaction completion, the mixture was diluted with water, and extracted with ethyl acetate (10 ml×2). The combined organic phases were washed successively with 2 N HCl and brine, dried over Na.sub.2SO.sub.4 and concentrated in vacuo. The crude product was purified by chromatography over silica gel (eluting with ethyl acetate in cyclohexane) to afford ethyl 2-[[3,5-bis(trifluoromethyl)benzoyl]amino]propanoate.

[0497] LCMS: R.sub.t 1.06, m/z=358 (M+H.sup.+).

Step B: Preparation of 2-[[3,5-bis(trifluoromethyl)benzoyl]amino]propanoic acid

[0498] ##STR00079##

[0499] To a stirred solution of ethyl 2-[[3,5-bis(trifluoromethyl)benzoyl]amino]propanoate (5.00 g, 14.0 mmol) in THF:H.sub.2O (1:1, 50 mL) was added LiOH.H.sub.2O (1.76 g, 42.0 mmol) at 0° C. and the resulting mixture stirred for 2 hours at room temperature. The mixture was concentrated in vacuo, and the residue obtained acidified with 1N HCl to pH 1. The solid formed was collected by filtration and dried under reduced pressure to afford 2-[[3,5-bis(trifluoromethyl)benzoyl]amino]propanoic acid.

[0500] LCMS: R.sub.t 0.91, m/z=330 (M+H.sup.+).

Step C: Preparation of N-[1-[5-(methoxymethyl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (Compound P2)

[0501] ##STR00080##

[0502] To a stirred solution of 2-[[3,5-bis(trifluoromethyl)benzoyl]amino]propanoic acid (90.0%, 200 mg, 0.547 mmol) in DMF (4.0 mL) were added 2-methoxyacetamidine (48.2 mg. 0.547 mmol), HATU (312 mg, 0.820 mmol) and DIPEA (176 mg, 1.37 mmol) at room temperature. The resulting mixture was stirred at room temperature for 3 hours and then pyrimidin-2-ylhydrazine (72.3 mg, 0.656 mmol) and AcOH (249 mg, 4.16 mmol) were added at room temperature. The reaction mixture was stirred at 80° C. for 1 hour and then cooled down at room temperature. Ethyl acetate (25 mL) was added and the organic layer was washed with bicarbonate sat sol, and then water. Drying over Na.sub.2SO.sub.4 and concentration in vacuo gave the crude product which was purified by chromatography over silica gel (eluting with ethyl acetate in cyclohexane) to afford N-[1-[5-(methoxymethyl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (Compound P2).

[0503] LCMS: R.sub.t 0.92, m/z=475 (M+H.sup.+); Mp: 155-160° C.; .sup.1H NMR (400 MHz, CDCl.sub.3): δ 8.92 (d, J=4.0 Hz 2H), 8.29 (s, 2H), 8.01 (s, 1H), 7.67 (d, J=8.0 Hz, 1H), 7.41 (t, J=4.0 Hz, 1H), 6.52 (t, J=7.4 Hz, 1H), 4.64 (s, 2H), 3.49 (s, 3H), 1.74 (d, J=8.0 Hz, 3H) ppm.

Example 3: Preparation of N-methyl-N-[1-(5-phenyl-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P6)

[0504] ##STR00081##

[0505] To a stirred solution of N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (60 mg, 0.11 mmol) in dioxane (1.1 mL) were added phenylboronic acid (29 mg. 0.23 mmol), Pd(PPh.sub.3).sub.4 (13 mg, 0.011 mmol) and an aqueous solution of potassium carbonate (2M, 0.17 mmol). The resulting mixture was stirred at reflux for 1 hour. After that time, LCMS indicated complete conversion, Isolute® was added into the reaction mixture, and the solvent removed by concentration in vacuo. The crude product was purified by chromatography over silica gel (eluting with ethyl acetate in cyclohexane) to afford N-methyl-N-[1-(5-phenyl-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P6).

[0506] LCMS: R.sub.t 1.15, m/z=521 (M+H.sup.+); .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=8.9 (d, J=4.77 Hz, 2H) 8.3 (dd, J=7.52, 2.02 Hz, 2H) 7.9 (s, 1H) 7.7 (s, 2H) 7.4-7.5 (m, 3H) 7.4 (br t, J=4.58 Hz, 1H) 6.8 (q, J=6.72 Hz, 1H) 2.9 (s, 3H) 1.9 (br d, J=6.97 Hz, 3H) ppm.

Example 4: Preparation N-[1-(5-chloro-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (Compound P15)

[0507] ##STR00082##

Step A: Preparation of N-[1-[5-(benzhydrylideneamino)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (Compound P22)

[0508] ##STR00083##

[0509] To a stirred solution of N-[1-(3-bromo-1H-1,2,4-triazol-5-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (P1) (100 mg, 0.19 mmol) in toluene (1.9 mL) were added benzophenone imine (71 mg. 0.38 mmol), xantphos (23 mg, 0.038 mmol), Pd.sub.2(dba).sub.3(PPh.sub.3).sub.4 (18 mg, 0.019 mmol) and cesium carbonate (19 mg, 0.57 mmol). The resulting mixture was stirred at reflux for 18 hours. After that time, LCMS indicated complete conversion, Isolute® was added into the reaction mixture, and the solvent removed in vacuo. The crude product was purified by chromatography over silica gel (eluting with ethyl acetate in cyclohexane) to afford N-[1-[5-(benzhydrylideneamino)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (compound P22) as a gum.

[0510] LCMS: R.sub.t 1.19, m/z=624 (M+H.sup.+).

Step B: Preparation of N-[1-(5-amino-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (Compound P7)

[0511] ##STR00084##

[0512] To a stirred solution of N-[1-[5-(benzhydrylideneamino)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide in THF (1.4 mL) was added a aqueous solution of HCl (2N, 0.20 mL, 0.41 mmol) and the resulting mixture was stirred at room temperature for 1 hour. Ethyl acetate (20 mL) was added and the organic layer was washed with bicarbonate sat sol, and then water. Drying over Na.sub.2SO.sub.4 and concentration in vacuo gave the crude product which was purified by chromatography over silica gel (eluting with ethylacetate/hexane) to afford N-[1-(5-amino-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (compound P7) as a brownish solid.

[0513] LCMS: R.sub.t 0.88, m/z=460 (M+H.sup.+); .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=8.76 (br d, J=4.8 Hz, 2H), 7.91 (br s, 1H), 7.69 (s, 2H), 7.2-7.3 (m, 1H), 6.7-6.8 (m, 1H), 4.38 (s, 2H) 2.87 (s, 3H), 1.73 (br d, J=7.0 Hz, 3H) ppm

Step C: Preparation of N-[1-(5-chloro-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (P15)

[0514] ##STR00085##

[0515] To a cooled suspension of N-[1-(5-amino-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (100 mg, 0.22 mmol) and CuCl.sub.2.2H.sub.2O (45 mg, 0.26 mmol) in concentrated HCl (1.0 mL) was added dropwise a solution of sodium nitrite (23 mg, 0.33 mmol) in 0.5 mL water. The reaction was stirred at room temperature for 12 h. Water was added, and the precipitate that formed was filtered off. It was purified by chromatography over silica gel (eluting with ethyl acetate/hexane) to afford N-[1-(5-chloro-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (Compound P15).

[0516] LCMS: R.sub.t 1.05, m/z=479 (M+H.sup.+); .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=8.86 (br d, J=4.4 Hz, 2H), 7.92 (br s, 1H), 7.69 (s, 2H), 7.40 (t, J=4.8 Hz, 1H), 6.72 (q, J=6.6 Hz, 1H), 2.93 (s, 3H), 1.79 (br d, J=7.0 Hz, 3H) ppm

Example 5: Preparation of N-[1-[5-(1,2,4-oxadiazol-5-yl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P1)

[0517] ##STR00086##

Step A: Preparation of methyl 5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxylate

[0518] ##STR00087##

[0519] In a high pressure metal reactor, triethylamine (35.6 μL, 255 μmol) and [1,3-bis(diphenylphosphino)propane]palladium(ii) dichloride (8.11 mg, 13.7 μmol) were added at room temperature to a solution of N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (100 mg, 196 μmol) in methanol (2 mL). The reaction mixture was heated up to 100° C. and stirred overnight under a 10 bar carbon monoxide atmosphere. After cooling down at room temperature, the reaction mixture was filtered over celite and concentrated under reduced pressure. The resulting residue was diluted with ethyl acetate and washed with water and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. Purification of the crude material by flash chromatography over silica gel (eluting with methanol in dichloromethane) afforded the desired product.

[0520] LCMS: R.sub.t 0.99, m/z=489 (M+H.sup.+); .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=8.98 (d, J=4.77 Hz, 2H), 8.26 (s, 2H), 7.98 (s, 1H), 7.76 (br d, J=7.34 Hz, 1H), 7.50 (t, J=4.77 Hz, 1H), 6.54 (quin, J=7.06 Hz, 1H), 4.02 (s, 3H), 1.82-1.75 (m, 3H) ppm.

Step B: Preparation of 5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide (Compound P37)

[0521] ##STR00088##

[0522] To a solution of methyl 5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxylate (35 mg, 72 μmol) in aqueous ammonia (0.350 mL) was added at room temperature lanthanum(III) trifluoromethanesulfonate (4.2 mg, 7.2 μmol). The reaction mixture was heated up to 70° C. and stirred for 2 hours. After cooling down to room temperature, the reaction mixture was concentrated under reduced pressure. Precipitation in diethyl ether afforded 5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide (Compound P37) as a white solid.

[0523] LCMS: R.sub.t 0.88, m/z=474 (M+H.sup.+); .sup.1H NMR (400 MHz, methanol-d4) δ=8.99 (d, J=5.14 Hz, 2H), 8.42 (s, 2H), 8.15 (s, 1H), 7.62 (t, J=4.77 Hz, 1H), 6.31 (s, 1H), 1.79 (d, J=6.97 Hz, 3H) ppm.

Step C: Preparation of (NE)-5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-N-(dimethylaminomethylene)-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide

[0524] ##STR00089##

[0525] To a solution of 5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide (110 mg, 0.232 mmol) in toluene (0.93 mL) was added at room temperature 1,1-dimethoxy-N,N-dimethyl-methanamine (0.062 mL, 0.465 mmol). The reaction mixture was heated up to 100° C. and stirred for 2 hours. After cooling down to room temperature, the reaction mixture was concentrated under reduced pressure to afford (NE)-5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-N-(dimethylaminomethylene)-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide as a white solid which was used without further purification.

[0526] .sup.1H NMR (400 MHz, DMSO-d6) δ=9.70-9.61 (m, 1H), 9.01 (d, J=4.77 Hz, 2H), 8.64 (s, 1H), 8.42 (s, 2H), 8.31 (s, 1H), 7.66 (s, 1H), 6.09-5.96 (m, 1H), 3.23-3.09 (m, 6H), 1.69 (d, J=6.97 Hz, 3H) ppm.

Step D: Preparation of (NE)-5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-N-[(hydroxyamino)methylene]-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide

[0527] ##STR00090##

[0528] To a solution of hydroxylamine hydrochloride (24.6 mg, 0.355 mmol) in acetic acid (1.25 mL) was added dropwise sodium hydroxide (1 N in water, 0.355 mL, 0.355 mmol). As the reaction was slightly exothermic, the reaction mixture was cooled to room temperature and stirred for 15 minutes. Then a solution of (NE)-5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-N-(dimethylaminomethylene)-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide (125 mg, 0.237 mmol) in acetic acid (1 mL) was added and the reaction mixture was stirred at room temperature for 1 hour then concentrated under reduced pressure to afford (NE)-5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-N-[(hydroxyamino)methylene]-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide which was used without further purification.

[0529] LCMS: R.sub.t 0.93, m/z=517 (M+H.sup.+).

Step E: Preparation of N-[1-[5-(1,2,4-oxadiazol-5-yl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P1)

[0530] ##STR00091##

[0531] To a solution of (NE)-5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-N-[(hydroxyamino)methylene]-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide (164 mg, 0.318 mmol) in dioxane (0.79 mL) was added dropwise at room temperature acetic acid (0.79 mL). The reaction mixture was heated up to 90° C. and stirred for 2 hours. After cooling down to room temperature, the reaction mixture was quenched with water and extracted with ethyl acetate. The combined organic layers were washed with water, dried over sodium sulfate, filtered and concentrated under reduced pressure. Purification of the crude material by reverse-phase chromatography (eluting with acetonitrile in water) afforded N-[1-[5-(1,2,4-oxadiazol-5-yl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P1) as a beige solid.

[0532] LCMS: R.sub.t 1.01, m/z=499 (M+H.sup.+).

[0533] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=9.02 (d, J=4.77 Hz, 2H), 8.64 (s, 1H), 8.27 (s, 2H), 8.02 (s, 1H), 7.59-7.50 (m, 2H), 6.64-6.57 (m, 1H), 1.84 (d, J=6.97 Hz, 3H) ppm

Example 6: Preparation of N-[1-[5-(1,3,4-oxadiazol-2-yl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P30)

[0534] ##STR00092##

Step A: Preparation of N-[1-[5-(hydrazinecarbonyl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide

[0535] ##STR00093##

[0536] To a solution of methyl 5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxylate (119 mg, 0.244 mmol) in methanol (1 mL) was added at room temperature hydrazine hydrate (35%, 52 μL, 0.37 mmol). The reaction mixture was heated up to 60° C. and stirred for 1 hour. After cooling down to room temperature, the reaction mixture was concentrated under reduced pressure to afford N-[1-[5-(hydrazinecarbonyl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide as a beige solid which was used without further purification.

[0537] LCMS: R.sub.t 0.87, m/z=489 (M+H.sup.+).

Step B: Preparation of N-[1-[5-(1,3,4-oxadiazol-2-yl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P30)

[0538] ##STR00094##

[0539] To a mixture of N-[1-[5-(hydrazinecarbonyl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (120 mg, 0.246 mmol) and trimethylorthoformate (1.38 mL) was added at room temperature p-toluenesulfonic acid (17 mg, 0.098 mmol). The reaction mixture was heated up to 140° C. and stirred for 5 hours. After cooling down to room temperature, the reaction mixture was concentrated under reduced pressure. Purification of the crude material by flash chromatography over silica gel (ethyl acetate in cyclohexane) afforded N-[1-[5-(1,3,4-oxadiazol-2-yl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P30) as a white solid.

[0540] LCMS: R.sub.t 0.95, m/z=499 (M+H.sup.+).

[0541] .sup.1H-NMR (400 MHz, DMSO-d6): δ=9.72 (br d, J=6.60 Hz, 1H), 9.48 (s, 1H), 9.06 (d, J=4.77 Hz, 2H), 8.43 (s, 2H), 8.32 (s, 1H), 7.75-7.70 (m, 1H), 6.11 (s, 1H), 1.75 (d, J=6.97 Hz, 3H) ppm.

Example 7: Preparation of N-[1-[5-(difluoromethoxy)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P28)

[0542] ##STR00095##

Step A: Preparation of 2-(5-ethyl-3-methoxy-1,2,4-triazol-1-yl)pyrimidine

[0543] ##STR00096##

[0544] To a suspension of potassium thiocyanate (7.8 g, 79 mmol) in dry acetone (56 mL) was added at room temperature propionyl chloride (7.5 g, 79 mmol). The reaction was heated up to 60° C. and stirred for 1 hour. After cooling down to room temperature, methanol (8.1 mL) was added and the reaction was heated up to 60° C. and stirred for 14 hours. After cooling down to room temperature, the suspension was filtered over celite and the filtrate was concentrated to afford O-methyl N-propanoylcarbamothioate. A mixture of O-methyl N-propanoylcarbamothioate (7.0 g, 48 mmol) and 2-hydrazinopyrimidine (CAS 7504-94-1, 8.1 g, 71 mmol) in dry ethanol (95 mL) was heated up to 90° C. and stirred for 4 hours. After cooling down to room temperature, the reaction mixture was filtered and concentrated under reduced pressure. Purification of the crude material by flash chromatography over silica gel (isopropanol in chloroform) afforded 2-(5-ethyl-3-methoxy-1,2,4-triazol-1-yl)pyrimidine.

[0545] LCMS: R.sub.t 0.62, m/z=206 (M+H.sup.+); .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=8.84-8.80 (m, 2H), 7.27-7.24 (m, 1H), 4.11 (s, 3H), 3.28 (q, J=7.58 Hz, 2H), 1.38 (t, J=7.52 Hz, 3H) ppm.

Step B: Preparation of 2-[5-(1-bromoethyl)-3-methoxy-1,2,4-triazol-1-yl]pyrimidine

[0546] ##STR00097##

[0547] A mixture of 2-(5-ethyl-3-methoxy-1,2,4-triazol-1-yl)pyrimidine (1.50 g, 7.30 mmol), N-bromosuccinimide (2.1 g, 12 mmol) and benzoyl peroxide (0.18 g, 0.73 mmol) in acetonitrile (8.5 mL) was irradiated under a 230 Watt white lamp for 30 minutes. The reaction mixture was concentrated under reduced pressure. Purification of the crude material by flash chromatography over silica gel (ethyl acetate in cyclohexane) afforded 2-[5-(1-bromoethyl)-3-methoxy-1,2,4-triazol-1-yl]pyrimidine as a yellow solid.

[0548] LCMS: R.sub.t 0.75, m/z=284, 286 (M+H.sup.+); .sup.1H-NMR (400 MHz, DMSO-d6): δ=8.98 (d, J=4.77 Hz, 2H), 7.61 (s, 1H), 6.30 (q, J=6.97 Hz, 1H), 3.97 (s, 3H), 2.05 (d, J=6.60 Hz, 3H) ppm.

Step C: Preparation of 1-(5-methoxy-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethanamine;hydrobromide

[0549] ##STR00098##

[0550] A solution of 2-[5-(1-bromoethyl)-3-methoxy-1,2,4-triazol-1-yl]pyrimidine (2.1 g, 7.4 mmol) in ammonia (7 M in methanol, 110 mL) was stirred at room temperature for 40 hours. The reaction mixture was concentrated under reduced pressure. Trituration in diethyl ether afforded 1-(5-methoxy-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethanamine;hydrobromide which was used without further purification.

[0551] LCMS: R.sub.t 0.18, m/z=221 (M+H.sup.+).

Step D: Preparation of N-[1-(5-methoxy-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide

[0552] ##STR00099##

[0553] To a solution of 1-(5-methoxy-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethanamine;hydrobromide (2.20 g, 6.56 mmol) and triethylamine (2.51 mL, 17.9 mmol) in dry dichloromethane (60 mL) was added dropwise at 0-5° C. 3-5-bis(trifluoromethyl)benzoyl chloride (CAS 785-56-8, 1.08 mL, 5.97 mmol). The reaction mixture was stirred at room temperature for 1 hour. After concentration under reduced pressure, the crude material was purified by flash chromatography over silica gel (ethyl acetate in cyclohexane) to afford N-[1-(5-methoxy-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide as a yellow solid.

[0554] LCMS: R.sub.t 0.99, m/z=461 (M+H.sup.+); .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=8.97-8.81 (m, 2H), 8.33-8.19 (m, 2H), 8.08-7.97 (m, 1H), 7.60-7.46 (m, 1H), 7.44-7.31 (m, 1H), 6.58-6.33 (m, 1H), 4.26-4.08 (m, 3H), 1.80-1.68 (m, 3H) ppm; .sup.19F NMR (377 MHz, CDCl.sub.3)=−62.86 (s, 6 F) ppm.

Step E: Preparation of N-[1-(5-oxo-2-pyrimidin-2-yl-1H-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (Compound P26)

[0555] ##STR00100##

[0556] To a solution of N-[1-(5-methoxy-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (0.20 g, 0.43 mmol) in acetic acid (2.2 mL) was added at room temperature hydrobromic acid (33% in acetic acid, 0.76 mL, 4.3 mmol). The reaction mixture was stirred first at room temperature for 18 hours, then at 40° C. for 5 hours. After concentration under reduced pressure, the crude material was purified by flash chromatography over silica gel (ethyl acetate in cyclohexane) to afford N-[1-(5-oxo-2-pyrimidin-2-yl-1H-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P26) as a yellow solid.

[0557] LCMS: R.sub.t 0.92, m/z=447 (M+H.sup.+); .sup.1H-NMR (400 MHz, DMSO-d6): δ=11.6 (s, 1H), 9.51 (d, J=6.97 Hz, 1H), 8.90 (d, J=4.77 Hz, 2H), 8.46 (s, 2H), 8.31 (s, 1H), 7.50 (t, J=4.77 Hz, 1H), 6.03 (t, J=6.97 Hz, 1H), 1.63 (d, J=6.97 Hz, 3H) ppm; .sup.19F NMR (377 MHz, DMSO-d6): δ=−61.30 (s, 6 F) ppm.

Step F: Preparation of N-[1-[5-(difluoromethoxy)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide

[0558] ##STR00101##

[0559] A solution of N-[1-(5-oxo-2-pyrimidin-2-yl-1H-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (0.20 g, 0.45 mmol), chlorodifluoroacetic acid (0.30 g, 2.2 mmol) and potassium carbonate (0.63 g, 4.5 mmol) in N,N-dimethylformamide (5 mL) was heated up to 80° C. and stirred for 16 hours. After cooling down at room temperature, the reaction mixture was diluted in ethyl acetate and washed with water and brine. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. Purification of the crude material by flash chromatography over silica gel (ethyl acetate in cyclohexane) afforded N-[1-[5-(difluoromethoxy)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide.

[0560] LCMS: R.sub.t 1.07, m/z=497 (M+H.sup.+); .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=8.94 (d, J=5.14 Hz, 2H), 8.25 (s, 2H), 8.05 (s, 1H), 7.43 (d, J=4.77 Hz, 1H), 7.07-7.25-7.45 (br t, 1H, CHF.sub.2), 6.47 (dd, J=8.25, 6.79 Hz, 1H), 1.76 (d, J=6.60 Hz, 3H) ppm; .sup.19F-NMR (377 MHz, CDCl.sub.3): δ=−61.30 (s, 6 F), −86.16 (d, 2 F) ppm.

Example 8: Preparation of N-methyl-N-[1-[2-pyrimidin-2-yl-5-(trifluoromethylsulfonyl)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P19)

[0561] ##STR00102##

Step A: Preparation of N-methyl-N-[1-[2-pyrimidin-2-yl-5-(trifluoromethylsulfanyl)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (P20)

[0562] ##STR00103##

[0563] To a solution of N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (0.20 g, 0.38 mmol) in dry 1,4-dioxane (11 mL) was added at room temperature trifluoromethylthiolato(2,2-bipyridine)copper(I) (CAS 1413732-47-4, 0.18 g, 0.57 mmol). The reaction mixture was heated up to 100° C. and stirred for 20 hours. After cooling down at room temperature, the reaction mixture was filtered over celite and concentrated under reduced pressure. Purification of the crude material first, by flash chromatography over silica gel (ethyl acetate in cyclohexane) and then, by reverse-phase chromatography (acetonitrile in water) afforded N-methyl-N-[1-[2-pyrimidin-2-yl-5-(trifluoromethylsulfanyl)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (P20) as a gum.

[0564] LCMS: R.sub.t 1.15, m/z=545 (M+H.sup.+); .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=8.90 (br d, J=4.40 Hz, 2H), 7.97-7.85 (m, 1H), 7.70 (s, 2H), 7.44 (br t, J=4.58 Hz, 1H), 6.75 (br d, J=6.97 Hz, 1H), 2.95 (s, 3H), 1.82 (d, J=7.34 Hz, 3H) ppm; .sup.19F-NMR (377 MHz, CDCl.sub.3): δ=−39.77 (s, 3 F), −63.02 (s, 6 F).

Step B: Preparation of N-methyl-N-[1-[2-pyrimidin-2-yl-5-(trifluoromethylsulfonyl)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P19)

[0565] ##STR00104##

[0566] To a solution of N-methyl-N-[1-[2-pyrimidin-2-yl-5-(trifluoromethylsulfanyl)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (55 mg, 0.10 mmol) in dichloromethane (3 mL) was added at 0° C. in three portions 3-chloroperoxybenzoic acid (29 mg, 0.12 mmol). The reaction mixture was allowed to reach room temperature and stirred for 6 days. The reaction mixture was quenched with sodium bicarbonate sat. solution. The organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure. Purification of the crude material by reverse-phase chromatography (acetonitrile in water) afforded N-methyl-N-[1-[2-pyrimidin-2-yl-5-(trifluoromethylsulfonyl)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P19) as an oil.

[0567] LCMS: R.sub.t 1.17, m/z=577 (M+H.sup.+).

Example 9: Preparation of N-[(1S)-1-[2-pyrimidin-2-yl-5-(trifluoromethoxy)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P23)

[0568] ##STR00105##

[0569] To a solution of N-[(1S)-1-(2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (0.547 g, 1.27 mmol) in acetonitrile (13 mL) were added at room temperature 1-(trifluoromethoxy)pyridine-4-carbonitrile;1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonamide (0.200 g, 0.424 mmol) and tris(2,2′-bipyridine)ruthenium(II) hexafluorophosphate (0.018 g, 0.021 mmol). The reaction mixture was stirred under irradiation of blue LED light for 2 hours at room temperature. After concentration under reduced pressure, the crude material was purified by flash chromatography over silica gel (methanol in dichloromethane) to afford N-[(1S)-1-[2-pyrimidin-2-yl-5-(trifluoromethoxy)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide as a yellow solid.

[0570] LCMS: R.sub.t 1.10, m/z=515 (M+H.sup.+); .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=8.96 (d, J=4.8 Hz, 2H), 8.27 (s, 2H), 8.05 (s, 1H), 7.50-7.44 (m, 1H), 7.41-7.34 (m, 1H), 6.56-6.43 (m, 1H), 1.77 (d, J=7.0 Hz, 3H) ppm.

TABLE-US-00013 TABLE P Examples of compounds of formula I RT [M + H] Entry IUPAC name STRUCTURE (min) (measured) MP °C. P1 N-[1-[5-(1,2,4- oxadiazol-5-yl)-2- pyrimidin-2-yl-1,2,4- triazol-3-yl]ethyl]-3,5- bis(trifluoromethyl) benzamide [00106] 1.01 499 P2 N-[1-[5- (methoxymethyl)-2- pyrimidin-2-yl-1,2,4- triazol-3-yl]ethyl]-3,5- bis(trifluoromethyl)be nzamide [00107] 155-160 P3 N-[1-(5-bromo-2- pyrimidin-2-yl-1,2,4- triazol-3-yl)ethyl]-N- methyl-3,5- bis(trifluoromethyl) benzamide [00108] 1.05 523/525 P4 N-[1-(5-bromo-2- pyrimidin-2-yl-1,2,4- triazol-3-yl)ethyl]-3,5- bis(trifluoromethyl) benzamide [00109] 1.05 509/511 P5 N- (cyclopropylmethyl)- N-[1-(5-iodo-2- pyrimidin-2-yl-1,2,4- triazol-3-yl)ethyl]-3,5- bis(trifluoromethyl) benzamide [00110] 1.14 611 P6 N-methyl-N-[1-(5- phenyl-2-pyrimidin-2- yl-1,2,4-triazol-3- yl)ethyl]-3,5- bis(trifluoromethyl) benzamide [00111] 1.15 521 P7 N-[1-(5-amino-2- pyrimidin-2-yl-1,2,4- triazol-3-yl)ethyl]-N- methyl-3,5- bis(trifluoromethyl) benzamide [00112] 0.88 460 162-164 P8 N-methyl-N-[1(5- prop-1-ynyl-2- pyrimidin-2-yl-1,2,4- triazol-3-yl)ethyl]-3,5- bis(trifluoromethyl) benzamide [00113] 1.05 483 P9 N-[1-(5-cyano-2- pyrimidin-2-yl-1,2,4- triazol-3-yl)ethyl]-N- methyl-3,5- bis(trifluoromethyl) benzamide [00114] 1.05 470 P10 N-methyl-N-[1-[2- pyrimidin-2-yl-5- (3,3,3-trifluoroprop-1- ynyl)-1,2,4-triazol-3- yl]ethyl]-3,5- bis(trifluoromethyl) benzamide [00115] 1.18 537 P11 5-[1-[[3,5- bis(trifluoromethyl) benzoyl]-methyl- amino]ethyl]-N,N- dimethyl-1-pyrimidin- 2-yl-1,2,4-triazole-3- carboxamide [00116] 55-57 P12 5-[1-[[3.5- bis(trifluoromethyl) benzoyl]-methyl- amino]ethyl]-N- methyl-1-pyrimidin-2- yl-1,2,4-triazole-3- carboxamide [00117] 78-79 P13 N-methyl-N-[1-(2- pyrimidin-2-yl-5-vinyl- 1,2,4-triazol-3- yl)ethyl]-3,5- bis(trifluoromethyl) benzamide [00118] 1.05 471 P14 N-[1-[5-(1- fluorovinyl)-2- pyrimidin-2-yl-1,2,4- triazol-3-yl]ethyl]-N- methyl-3,5- bis(trifluoromethyl) benzamide [00119] 1.08 489 P15 N-[1-(5-chloro-2- pyrimidin-2-yl-1,2,4- triazol-3-yl)ethyl]-N- methyl-3,5- bis(trifluoromethyl) benzamide [00120] 1.05 479 P16 N-[1-[5- (dimethylamino)-2- pyrimidin-2-yl-1,2,4- triazol-3-yl]ethyl]-N- methyl-3,5- bis(trifluoromethyl) benzamide [00121] 1.04 488 P17 N-[1-(5-acetamido-2- pyrimidin-2-yl-1,2,4- triazol-3-yl)ethyl]-N- methyl-3,5- bis(trifluoromethyl) benzamide [00122] 0.99 502 P18 N-methyl-N-[1-[5- (methylamino)-2- pyrimidin-2-yl-1,2,4- triazol-3-yl]ethyl]-3,5- bis(trifluoromethyl) benzamide [00123] 0.93 474 P19 N-methyl-N-[1-[2- pyrimidin-2-yl-5- (trifluoromethylsulfonyl)- 1,2,4-triazol-3- yl]ethyl]-3,5- bis(trifluoromethyl) benzamide [00124] 1.17 577 P20 N-methyl-N-[1-[2- pyrimidin-2-yl-5- (trifluoromethylsulfanyl)- 1,2,4-triazol-3- yl]ethyl]-3,5- bis(trifluoromethyl) benzamide [00125] 1.15 545 P21 N-[1-(5- methylsulfonyl-2- pyrimidin-2-yl-1,2,4- triazol-3-yl)ethyl]-3,5- bis(trifluoromethyl) benzamide [00126] 0.98 509 P22 N-[1-[5- (benzhydrylideneamino)- 2-pyrimidin-2-yl- 1,2,4-triazol-3- yl]ethyl]-N-methyl- 3,5- bis(trifluoromethyl) benzamide [00127] 1.19 624 P23 N-[(1S)-1-[2- pyrimidin-2-yl-5- (trifluoromethoxy)- 1,2,4-triazol-3- yl]ethyl]-3,5- bis(trifluoromethyl) benzamide [00128] 1.10 515 P24 N-[1-[5-bromo-2-(2- pyridyl)-1,2,4-triazol- 3-yl]ethyl]-N-methyl- 3,5- bis(trifluoromethyl) benzamide [00129] 1.15 523/525 P25 N-[1-[2-(2-pyridyl)-5- (trifluoromethoxy)- 1,2,4-triazol-3- yl]ethyl]-3,5- bis(trifluoromethyl) benzamide [00130] 1.23 514 P26 N-[1-(5-hydroxy-2- pyrimidin-2-yl-1,2)4- triazol-3-yl)ethyl]-3,5- bis(trifluoromethyl) benzamide [00131] 0.92 447 P27 N-[1-[2-pyrimidin-2- yl-5-(2,2,2- trifluoroethoxy)-1,2,4- triazol-3-yl]ethyl]-3,5- bis(trifluoromethyl) benzamide [00132] 1.09 529 P28 N-[1-[5- (difluoromethoxy)-2- pyrimidin-2-yl-1,2,4- triazol-3-yl]ethyl]-3,5- bis(trifluoromethyl) benzamide [00133] 1.07 497 P29 N-[1-[5-(2,2- difluoroethoxy)-2- pyrimidin-2-yl-1,2,4- triazol-3-yl]ethyl]-3,5- bis(trifluoromethyl) benzamide [00134] 1.05 511 P30 N-[1-[5-(1,3,4- oxadiazol-2-yl)-2- pyrimidin-2-yl-1,2,4- [triazol-3-yl]ethyl]-3,5- bis(trifluoromethyl) benzamide [00135] 245-246 P31 3-bromo-N-[1-(5- bromo-2-pyrimidin-2- yl-1,2,4-triazol-3- yl)ethyl]-5- (trifluoromethyl) benzamide [00136] 125-130 P32 N-[1-(5-bromo-2- pyrimidin-2-yl-1,2,4- triazol-3-yl)ethyl]-3- chloro-5- (trifluoromethoxy)ben zamide [00137] 75-80 P33 N-[1-(5-bromo-2- pyrimidin-2-yl-1,2,4- triazol-3-yl)ethyl]-3- chloro-5- (trifluoromethyl) benzamide [00138] 215-220 P34 N-[1-(5-chloro-2- pyrimidin-2-yl-1,2,4- triazol-3-yl)ethyl]-3,5- bis(trifluoromethyl) benzamide [00139] 225-226 P35 N-[1-(5-acetyl-2- pyrimidin-2-yl-1,2,4- triazol-3-yl)ethyl]-3,5- bis(trifluoromethyl) benzamide [00140] 210-211 P36 N-[1-[5-(2- methoxyethoxy)-2- pyrimidin-2-yl-1,2,4- triazol-3-yl]ethyl]-3,5- bis(trifluoromethyl) benzamide [00141] 1.00 505 P37 5-[1-[[3,5- bis(trifluoromethyl) benzoyl]-methyl- amino]ethyl]-1- pyrimidin-2-yl-1,2,4- triazole-3- earboxamide [00142] 225-226 P38 N-[1-(5-formyl-2- pyrimidin-2-yl-1,2,4- triazol-3-yl)ethyl]-3,5- bis(trifluoromethyl) benzamide [00143] 200-205

TABLE-US-00014 TABLE I Table of Intermediates: RT [M + H] Entry IUPAC name STRUCTURE (min) (measured) MP, °C. I1 N- 1.05 533 — (cyclopropylmethyl)- N-[1-(3-iodo- 1H-1,2,4-triazol- 5-yl)ethyl]-3,5- bis(trifluoromethyl) benzamide I2 N-[1-(3-bromo- 1.06 485/487 — 1H-1,2,4-triazol- 5-yl)ethyl]-N- (cyclopropyl- methyl)-3,5-bis (trifluoromethyl) benzamide I3 N-methyl-N-[1- (3-phenyl-1H- 1,2,4-triazol-5- yl)ethyl]-3,5- bis(trifluoromethyl) benzamide [00144] 1.14 483 — I4 N-[1-[3-(4- fluorophenyl)-1H- 1,2,4-triazol-5- yl]ethyl]-3,5- bis(trifluoromethyl) benzamide [00145] 1.04 447 — I5 N-[1-(3-bromo- 1H-1,2,4-triazol- 5-yl)ethyl]-3,5- bis(trifluoromethyl) benzamide [00146] 0.96 431/433 — I6 N-[1-(3-bromo- 1H-1,2,4-triazol- 5-yl)ethyl]-N- methyl-3,5- bis(trifluoromethyl) benzamide [00147] 0.98 445/447 —

[0571] The activity of the compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients. The mixtures of the compounds of formula I with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use.

[0572] Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.

[0573] The following mixtures of the compounds of formula I with active ingredients are preferred (where the abbreviation “TX” means “one compound selected from the compounds defined in the Tables A-1 to A-92 and Table P”):

[0574] an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628)+TX,

[0575] an insect control active substance selected from Abamectin+TX, Acequinocyl+TX, Acetamiprid+TX, Acetoprole+TX, Acrinathrin+TX, Acynonapyr+TX, Afidopyropen+TX, Afoxalaner+TX, Alanycarb+TX, Allethrin+TX, Alpha-Cypermethrin+TX, Alphamethrin+TX, Amidoflumet+TX, Aminocarb+TX, Azocyclotin+TX, Bensultap+TX, Benzoximate+TX, Benzpyrimoxan+TX, Betacyfluthrin+TX, Beta-cypermethrin+TX, Bifenazate+TX, Bifenthrin+TX, Binapacryl+TX, Bioallethrin+TX, Bioallethrin S)-cyclopentylisomer+TX, Bioresmethrin+TX, Bistrifluron+TX, Broflanilide+TX, Brofluthrinate+TX, Bromophos-ethyl+TX, Buprofezine+TX, Butocarboxim+TX, Cadusafos+TX, Carbaryl+TX, Carbosulfan+TX, Cartap+TX, CAS number: 1472050-04-6+TX, CAS number: 1632218-00-8+TX, CAS number: 1808115-49-2+TX, CAS number: 2032403-97-5+TX, CAS number: 2044701-44-0+TX, CAS number: 2128706-05-6+TX, CAS number: 2249718-27-0+TX, Chlorantraniliprole+TX, Chlordane+TX, Chlorfenapyr+TX, Chloroprallethrin+TX, Chromafenozide+TX, Clenpirin+TX, Cloethocarb+TX, Clothianidin+TX, 2-chlorophenyl N-methylcarbamate (CPMC)+TX, Cyanofenphos+TX, Cyantraniliprole+TX, Cyclaniliprole+TX, Cycloprothrin+TX, Cycloxaprid+TX, Cycloxaprid+TX, Cyenopyrafen+TX, Cyetpyrafen (or Etpyrafen)+TX, Cyflumetofen+TX, Cyfluthrin+TX, Cyhalodiamide+TX, Cyhalothrin+TX, Cypermethrin+TX, Cyphenothrin+TX, Cyromazine+TX, Deltamethrin+TX, Diafenthiuron+TX, Dialifos+TX, Dibrom+TX, Dicloromezotiaz+TX, Diflovidazine+TX, Diflubenzuron+TX, dimpropyridaz+TX, Dinactin+TX, Dinocap+TX, Dinotefuran+TX, Dioxabenzofos+TX, Emamectin+TX, Empenthrin+TX, Epsilon—momfluorothrin+TX, Epsilon-metofluthrin+TX, Esfenvalerate+TX, Ethion+TX, Ethiprole+TX, Etofenprox+TX, Etoxazole+TX, Famphur+TX, Fenazaquin+TX, Fenfluthrin+TX, Fenitrothion+TX, Fenobucarb+TX, Fenothiocarb+TX, Fenoxycarb+TX, Fenpropathrin+TX, Fenpyroxymate+TX, Fensulfothion+TX, Fenthion+TX, Fentinacetate+TX, Fenvalerate+TX, Fipronil+TX, Flometoquin+TX, Flonicamid+TX, Fluacrypyrim+TX, Fluazaindolizine+TX, Fluazuron+TX, Flubendiamide+TX, Flubenzimine+TX, Flucitrinate+TX, Flucycloxuron+TX, Flucythrinate+TX, Fluensulfone+TX, Flufenerim+TX, Flufenprox+TX, Flufiprole+TX, Fluhexafon+TX, Flumethrin+TX, Fluopyram+TX, Flupyradifurone+TX, Flupyrimin+TX, Fluralaner+TX, Fluvalinate+TX, Fluxametamide+TX, Fosthiazate+TX, Gamma-Cyhalothrin+TX, Gossyplure™+TX, Guadipyr+TX, Halofenozide+TX, Halofenozide+TX, Halofenprox+TX, Heptafluthrin+TX, Hexythiazox+TX, Hydramethylnon+TX, Imicyafos+TX, Imidacloprid+TX, Imiprothrin+TX, Indoxacarb+TX, Iodomethane+TX, Iprodione+TX, Isocycloseram+TX, Isothioate+TX, Ivermectin+TX, Kappa-bifenthrin+TX, Kappa-tefluthrin+TX, Lambda-Cyhalothrin+TX, Lepimectin+TX, Lufenuron+TX, Metaflumizone+TX, Metaldehyde+TX, Metam+TX, Methomyl+TX, Methoxyfenozide+TX, Metofluthrin+TX, Metolcarb+TX, Mexacarbate+TX, Milbemectin+TX, Momfluorothrin+TX, Niclosamide+TX, Nitenpyram+TX, Nithiazine+TX, Omethoate+TX, Oxamyl+TX, Oxazosufyl+TX, Parathion-ethyl+TX, Permethrin+TX, Phenothrin+TX, Phosphocarb+TX, Piperonylbutoxide+TX, Pirimicarb+TX, Pirimiphos-ethyl+TX, Polyhedrosis virus+TX, Prallethrin+TX, Profenofos+TX, Profenofos+TX, Profluthrin+TX, Propargite+TX, Propetamphos+TX, Propoxur+TX, Prothiophos+TX, Protrifenbute+TX, Pyflubumide+TX, Pymetrozine+TX, Pyraclofos+TX, Pyrafluprole+TX, Pyridaben+TX, Pyridalyl+TX, Pyrifluquinazon+TX, Pyrimidifen+TX, Pyrimostrobin+TX, Pyriprole+TX, Pyriproxyfen+TX, Resmethrin+TX, Sarolaner+TX, Selamectin+TX, Silafluofen+TX, Spinetoram+TX, Spinosad+TX, Spirodiclofen+TX, Spiromesifen+TX, Spiropidion+TX, Spirotetramat+TX, Sulfoxaflor+TX, Tebufenozide+TX, Tebufenpyrad+TX, Tebupirimiphos+TX, Tefluthrin+TX, Temephos+TX, Tetrachloraniliprole+TX, Tetradiphon+TX, Tetramethrin+TX, Tetramethylfluthrin+TX, Tetranactin+TX, Tetraniliprole+TX, Theta-cypermethrin+TX, Thiacloprid+TX, Thiamethoxam+TX, Thiocyclam+TX, Thiodicarb+TX, Thiofanox+TX, Thiometon+TX, Thiosultap+TX, Tioxazafen+TX, Tolfenpyrad+TX, Toxaphene+TX, Tralomethrin+TX, Transfluthrin+TX, Triazamate+TX, Triazophos+TX, Trichlorfon+TX, Trichloronate+TX, Trichlorphon+TX, Triflumezopyrim+TX, Tyclopyrazoflor+TX, Zeta-Cypermethrin+TX, Extract of seaweed and fermentation product derived from melasse+TX, Extract of seaweed and fermentation product derived from melasse comprising urea+TX, amino acids+TX, potassium and molybdenum and EDTA-chelated manganese+TX, Extract of seaweed and fermented plant products+TX, Extract of seaweed and fermented plant products comprising phytohormones+TX, vitamins+TX, EDTA-chelated copper+TX, zinc+TX, and iron+TX, Azadirachtin+TX, Bacillus aizawai+TX, Bacillus chitinosporus AQ746 (NRRL Accession No B-21 618)+TX, Bacillus firmus+TX, Bacillus kurstaki+TX, Bacillus mycoides AQ726 (NRRL Accession No. B-21664)+TX, Bacillus pumilus (NRRL Accession No B-30087)+TX, Bacillus pumilus AQ717 (NRRL Accession No. B-21662)+TX, Bacillus sp. AQ178 (ATCC Accession No. 53522)+TX, Bacillus sp. AQ175 (ATCC Accession No. 55608)+TX, Bacillus sp. AQ177 (ATCC Accession No. 55609)+TX, Bacillus subtilis unspecified+TX, Bacillus subtilis AQ153 (ATCC Accession No. 55614)+TX, Bacillus subtilis AQ30002 (NRRL Accession No. B-50421)+TX, Bacillus subtilis AQ30004 (NRRL Accession No. B-50455)+TX, Bacillus subtilis AQ713 (NRRL Accession No. B-21661)+TX, Bacillus subtilis AQ743 (NRRL Accession No. B-21665)+TX, Bacillus thuringiensis AQ52 (NRRL Accession No. B-21619)+TX, Bacillus thuringiensis BD #32 (NRRL Accession No B-21530)+TX, Bacillus thuringiensis subspec. kurstaki BMP 123+TX, Beauveria bassiana+TX, D-limonene+TX, Granulovirus+TX, Harpin+TX, Helicoverpa armigera Nucleopolyhedrovirus+TX, Helicoverpa zea Nucleopolyhedrovirus+TX, Heliothis virescens Nucleopolyhedrovirus+TX, Heliothis punctigera Nucleopolyhedrovirus+TX, Metarhizium spp.+TX, Muscodor albus 620 (NRRL Accession No. 30547)+TX, Muscodor roseus A3-5 (NRRL Accession No. 30548)+TX, Neem tree based products+TX, Paecilomyces fumosoroseus+TX, Paecilomyces lilacinus+TX, Pasteuria nishizawae+TX, Pasteuria penetrans+TX, Pasteuria ramosa+TX, Pasteuria thornei+TX, Pasteuria usgae+TX, P-cymene+TX, Plutella xylostella Granulosis virus+TX, Plutella xylostella Nucleopolyhedrovirus+TX, Polyhedrosis virus+TX, pyrethrum+TX, QRD 420 (a terpenoid blend)+TX, QRD 452 (a terpenoid blend)+TX, QRD 460 (a terpenoid blend)+TX, Quillaja saponaria+TX, Rhodococcus globerulus AQ719 (NRRL Accession No B-21663)+TX, Spodoptera frugiperda Nucleopolyhedrovirus+TX, Streptomyces galbus (NRRL Accession No. 30232)+TX, Streptomyces sp. (NRRL Accession No. B-30145)+TX, Terpenoid blend+TX, and Verticillium spp.,

[0576] an algicide selected from the group of substances consisting of bethoxazin [CCN]+TX, copper dioctanoate (IUPAC name) (170)+TX, copper sulfate (172)+TX, cybutryne [CCN]+TX, dichlone (1052)+TX, dichlorophen (232)+TX, endothal (295)+TX, fentin (347)+TX, hydrated lime [CCN]+TX, nabam (566)+TX, quinoclamine (714)+TX, quinonamid (1379)+TX, simazine (730)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347)+TX,

[0577] an anthelmintic selected from the group of substances consisting of abamectin (1)+TX, crufomate (1011)+TX, doramectin (alternative name) [CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, eprinomectin (alternative name) [CCN]+TX, ivermectin (alternative name) [CCN]+TX, milbemycin oxime (alternative name) [CCN]+TX, moxidectin (alternative name) [CCN]+TX, piperazine [CCN]+TX, selamectin (alternative name) [CCN]+TX, spinosad (737) and thiophanate (1435)+TX,

[0578] an avicide selected from the group of substances consisting of chloralose (127)+TX, endrin (1122)+TX, fenthion (346)+TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745)+TX,

[0579] a bactericide selected from the group of substances consisting of 1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222)+TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX, 8-hydroxyquinoline sulfate (446)+TX, bronopol (97)+TX, copper dioctanoate (IUPAC name) (170)+TX, copper hydroxide (IUPAC name) (169)+TX, cresol [CCN]+TX, dichlorophen (232)+TX, dipyrithione (1105)+TX, dodicin (1112)+TX, fenaminosulf (1144)+TX, formaldehyde (404)+TX, hydrargaphen (alternative name) [CCN]+TX, kasugamycin (483)+TX, kasugamycin hydrochloride hydrate (483)+TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308)+TX, nitrapyrin (580)+TX, octhilinone (590)+TX, oxolinic acid (606)+TX, oxytetracycline (611)+TX, potassium hydroxyquinoline sulfate (446)+TX, probenazole (658)+TX, streptomycin (744)+TX, streptomycin sesquisulfate (744)+TX, tecloftalam (766)+TX, and thiomersal (alternative name) [CCN]+TX,

[0580] a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12)+TX, Agrobacterium radiobacter (alternative name) (13)+TX, Amblyseius spp. (alternative name) (19)+TX, Anagrapha falcifera NPV (alternative name) (28)+TX, Anagrus atomus (alternative name) (29)+TX, Aphelinus abdominalis (alternative name) (33)+TX, Aphidius colemani (alternative name) (34)+TX, Aphidoletes aphidimyza (alternative name) (35)+TX, Autographa californica NPV (alternative name) (38)+TX, Bacillus firmus (alternative name) (48)+TX, Bacillus sphaericus Neide (scientific name) (49)+TX, Bacillus thuringiensis Berliner (scientific name) (51)+TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51)+TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51)+TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51)+TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51)+TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51)+TX, Beauveria bassiana (alternative name) (53)+TX, Beauveria brongniartii (alternative name) (54)+TX, Chrysoperla carnea (alternative name) (151)+TX, Cryptolaemus montrouzieri (alternative name) (178)+TX, Cydia pomonella GV (alternative name) (191)+TX, Dacnusa sibirica (alternative name) (212)+TX, Diglyphus isaea (alternative name) (254)+TX, Encarsia formosa (scientific name) (293)+TX, Eretmocerus eremicus (alternative name) (300)+TX, Helicoverpa zea NPV (alternative name) (431)+TX, Heterorhabditis bacteriophora and H. megidis (alternative name) (433)+TX, Hippodamia convergens (alternative name) (442)+TX, Leptomastix dactylopii (alternative name) (488)+TX, Macrolophus caliginosus (alternative name) (491)+TX, Mamestra brassicae NPV (alternative name) (494)+TX, Metaphycus helvolus (alternative name) (522)+TX, Metarhizium anisopliae var. acridum (scientific name) (523)+TX, Metarhizium anisopliae var. anisopliae (scientific name) (523)+TX, Neodiprion sertifer NPV and N. lecontei NPV (alternative name) (575)+TX, Orius spp. (alternative name) (596)+TX, Paecilomyces fumosoroseus (alternative name) (613)+TX, Phytoseiulus persimilis (alternative name) (644)+TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741)+TX, Steinernema bibionis (alternative name) (742)+TX, Steinernema carpocapsae (alternative name) (742)+TX, Steinernema feltiae (alternative name) (742)+TX, Steinernema glaseri (alternative name) (742)+TX, Steinernema riobrave (alternative name) (742)+TX, Steinernema riobravis (alternative name) (742)+TX, Steinernema scapterisci (alternative name) (742)+TX, Steinernema spp. (alternative name) (742)+TX, Trichogramma spp. (alternative name) (826)+TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848)+TX,

[0581] a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537)+TX,

[0582] a chemosterilant selected from the group of substances consisting of apholate [CCN]+TX, bisazir (alternative name) [CCN]+TX, busulfan (alternative name) [CCN]+TX, diflubenzuron (250)+TX, dimatif (alternative name) [CCN]+TX, hemel [CCN]+TX, hempa [CCN]+TX, metepa [CCN]+TX, methiotepa [CCN]+TX, methyl apholate [CCN]+TX, morzid [CCN]+TX, penfluron (alternative name) [CCN]+TX, tepa [CCN]+TX, thiohempa (alternative name) [CCN]+TX, thiotepa (alternative name) [CCN]+TX, tretamine (alternative name) [CCN] and uredepa (alternative name) [CCN]+TX,

[0583] an insect pheromone selected from the group of substances consisting of (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol (IUPAC name) (222)+TX, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829)+TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541)+TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate (IUPAC name) (779)+TX, (Z)-dodec-7-en-1-yl acetate (IUPAC name) (285)+TX, (Z)-hexadec-11-enal (IUPAC name) (436)+TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name) (437)+TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438)+TX, (Z)-icos-13-en-10-one (IUPAC name) (448)+TX, (Z)-tetradec-7-en-1-al (IUPAC name) (782)+TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783)+TX, (Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784)+TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283)+TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780)+TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate (IUPAC name) (781)+TX, 14-methyloctadec-1-ene (IUPAC name) (545)+TX, 4-methylnonan-5-ol with 4-methylnonan-5-one (IUPAC name) (544)+TX, alpha-multistriatin (alternative name) [CCN]+TX, brevicomin (alternative name) [CCN]+TX, codlelure (alternative name) [CCN]+TX, codlemone (alternative name) (167)+TX, cuelure (alternative name) (179)+TX, disparlure (277)+TX, dodec-8-en-1-yl acetate (IUPAC name) (286)+TX, dodec-9-en-1-yl acetate (IUPAC name) (287)+TX, dodeca-8+TX, 10-dien-1-yl acetate (IUPAC name) (284)+TX, dominicalure (alternative name) [CCN]+TX, ethyl 4-methyloctanoate (IUPAC name) (317)+TX, eugenol (alternative name) [CCN]+TX, frontalin (alternative name) [CCN]+TX, gossyplure (alternative name) (420)+TX, grandlure (421)+TX, grandlure I (alternative name) (421)+TX, grandlure II (alternative name) (421)+TX, grandlure III (alternative name) (421)+TX, grandlure IV (alternative name) (421)+TX, hexalure [CCN]+TX, ipsdienol (alternative name) [CCN]+TX, ipsenol (alternative name) [CCN]+TX, japonilure (alternative name) (481)+TX, lineatin (alternative name) [CCN]+TX, litlure (alternative name) [CCN]+TX, looplure (alternative name) [CCN]+TX, medlure [CCN]+TX, megatomoic acid (alternative name) [CCN]+TX, methyl eugenol (alternative name) (540)+TX, muscalure (563)+TX, octadeca-2,13-dien-1-yl acetate (IUPAC name) (588)+TX, octadeca-3,13-dien-1-yl acetate (IUPAC name) (589)+TX, orfralure (alternative name) [CCN]+TX, oryctalure (alternative name) (317)+TX, ostramone (alternative name) [CCN]+TX, siglure [CCN]+TX, sordidin (alternative name) (736)+TX, sulcatol (alternative name) [CCN]+TX, tetradec-11-en-1-yl acetate (IUPAC name) (785)+TX, trimedlure (839)+TX, trimedlure A (alternative name) (839)+TX, trimedlure B.sub.1 (alternative name) (839)+TX, trimedlure B.sub.2 (alternative name) (839)+TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN]+TX,

[0584] an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (IUPAC name) (591)+TX, butopyronoxyl (933)+TX, butoxy(polypropylene glycol) (936)+TX, dibutyl adipate (IUPAC name) (1046)+TX, dibutyl phthalate (1047)+TX, dibutyl succinate (IUPAC name) (1048)+TX, diethyltoluamide [CCN]+TX, dimethyl carbate [CCN]+TX, dimethyl phthalate [CCN]+TX, ethyl hexanediol (1137)+TX, hexamide [CCN]+TX, methoquin-butyl (1276)+TX, methylneodecanamide [CCN]+TX, oxamate [CCN] and picaridin [CCN]+TX,

[0585] a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (IUPAC name) (913)+TX, bromoacetamide [CCN]+TX, calcium arsenate [CCN]+TX, cloethocarb (999)+TX, copper acetoarsenite [CCN]+TX, copper sulfate (172)+TX, fentin (347)+TX, ferric phosphate (IUPAC name) (352)+TX, metaldehyde (518)+TX, methiocarb (530)+TX, niclosamide (576)+TX, niclosamide-olamine (576)+TX, pentachlorophenol (623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX, thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX, trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347)+TX, pyriprole [394730-71-3]+TX,

[0586] a nematicide selected from the group of substances consisting of AKD-3088 (compound code)+TX, 1,2-dibromo-3-chloropropane (IUPAC/Chemical Abstracts name) (1045)+TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062)+TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063)+TX, 1,3-dichloropropene (233)+TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstracts name) (1065)+TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980)+TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid (IUPAC name) (1286)+TX, 6-isopentenylaminopurine (alternative name) (210)+TX, abamectin (1)+TX, acetoprole [CCN]+TX, alanycarb (15)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, AZ 60541 (compound code)+TX, benclothiaz [CCN]+TX, benomyl (62)+TX, butylpyridaben (alternative name)+TX, cadusafos (109)+TX, carbofuran (118)+TX, carbon disulfide (945)+TX, carbosulfan (119)+TX, chloropicrin (141)+TX, chlorpyrifos (145)+TX, cloethocarb (999)+TX, cytokinins (alternative name) (210)+TX, dazomet (216)+TX, DBCP (1045)+TX, DCIP (218)+TX, diamidafos (1044)+TX, dichlofenthion (1051)+TX, dicliphos (alternative name)+TX, dimethoate (262)+TX, doramectin (alternative name) [CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, eprinomectin (alternative name) [CCN]+TX, ethoprophos (312)+TX, ethylene dibromide (316)+TX, fenamiphos (326)+TX, fenpyrad (alternative name)+TX, fensulfothion (1158)+TX, fosthiazate (408)+TX, fosthietan (1196)+TX, furfural (alternative name) [CCN]+TX, GY-81 (development code) (423)+TX, heterophos [CCN]+TX, iodomethane (IUPAC name) (542)+TX, isamidofos (1230)+TX, isazofos (1231)+TX, ivermectin (alternative name) [CCN]+TX, kinetin (alternative name) (210)+TX, mecarphon (1258)+TX, metam (519)+TX, metam-potassium (alternative name) (519)+TX, metam-sodium (519)+TX, methyl bromide (537)+TX, methyl isothiocyanate (543)+TX, milbemycin oxime (alternative name) [CCN]+TX, moxidectin (alternative name) [CCN]+TX, Myrothecium verrucaria composition (alternative name) (565)+TX, NC-184 (compound code)+TX, oxamyl (602)+TX, phorate (636)+TX, phosphamidon (639)+TX, phosphocarb [CCN]+TX, sebufos (alternative name)+TX, selamectin (alternative name) [CCN]+TX, spinosad (737)+TX, terbam (alternative name)+TX, terbufos (773)+TX, tetrachlorothiophene (IUPAC/Chemical Abstracts name) (1422)+TX, thiafenox (alternative name)+TX, thionazin (1434)+TX, triazophos (820)+TX, triazuron (alternative name)+TX, xylenols [CCN]+TX, YI-5302 (compound code) and zeatin (alternative name) (210)+TX, fluensulfone [318290-98-1]+TX, fluopyram+TX,

[0587] a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580)+TX,

[0588] a plant activator selected from the group of substances consisting of acibenzolar (6)+TX, acibenzolar-S-methyl (6)+TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720)+TX,

[0589] a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1,3-dione (IUPAC name) (1246)+TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX, alpha-chlorohydrin [CCN]+TX, aluminium phosphide (640)+TX, antu (880)+TX, arsenous oxide (882)+TX, barium carbonate (891)+TX, bisthiosemi (912)+TX, brodifacoum (89)+TX, bromadiolone (91)+TX, bromethalin (92)+TX, calcium cyanide (444)+TX, chloralose (127)+TX, chlorophacinone (140)+TX, cholecalciferol (alternative name) (850)+TX, coumachlor (1004)+TX, coumafuryl (1005)+TX, coumatetralyl (175)+TX, crimidine (1009)+TX, difenacoum (246)+TX, difethialone (249)+TX, diphacinone (273)+TX, ergocalciferol (301)+TX, flocoumafen (357)+TX, fluoroacetamide (379)+TX, flupropadine (1183)+TX, flupropadine hydrochloride (1183)+TX, gamma-HCH (430)+TX, HCH (430)+TX, hydrogen cyanide (444)+TX, iodomethane (IUPAC name) (542)+TX, lindane (430)+TX, magnesium phosphide (IUPAC name) (640)+TX, methyl bromide (537)+TX, norbormide (1318)+TX, phosacetim (1336)+TX, phosphine (IUPAC name) (640)+TX, phosphorus [CCN]+TX, pindone (1341)+TX, potassium arsenite [CCN]+TX, pyrinuron (1371)+TX, scilliroside (1390)+TX, sodium arsenite [CCN]+TX, sodium cyanide (444)+TX, sodium fluoroacetate (735)+TX, strychnine (745)+TX, thallium sulfate [CCN]+TX, warfarin (851) and zinc phosphide (640)+TX,

[0590] a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934)+TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903)+TX, farnesol with nerolidol (alternative name) (324)+TX, MB-599 (development code) (498)+TX, MGK 264 (development code) (296)+TX, piperonyl butoxide (649)+TX, piprotal (1343)+TX, propyl isomer (1358)+TX, S421 (development code) (724)+TX, sesamex (1393)+TX, sesasmolin (1394) and sulfoxide (1406)+TX,

[0591] an animal repellent selected from the group of substances consisting of anthraquinone (32)+TX, chloralose (127)+TX, copper naphthenate [CCN]+TX, copper oxychloride (171)+TX, diazinon (227)+TX, dicyclopentadiene (chemical name) (1069)+TX, guazatine (422)+TX, guazatine acetates (422)+TX, methiocarb (530)+TX, pyridin-4-amine (IUPAC name) (23)+TX, thiram (804)+TX, trimethacarb (840)+TX, zinc naphthenate [CCN] and ziram (856)+TX,

[0592] a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN]+TX, a wound protectant selected from the group of substances consisting of mercuric oxide (512)+TX, octhilinone (590) and thiophanate-methyl (802)+TX,

[0593] a biologically active substance selected from 1,1-bis(4-chlorophenyl)-2-ethoxyethanol+TX, 2,4-dichlorophenyl benzenesulfonate+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide+TX, 4-chlorophenyl phenyl sulfone+TX, acetoprole+TX, aldoxycarb+TX, amidithion+TX, amidothioate+TX, amiton+TX, amiton hydrogen oxalate+TX, amitraz+TX, aramite+TX, arsenous oxide+TX, azobenzene+TX, azothoate+TX, benomyl+TX, benoxafos+TX, benzyl benzoate+TX, bixafen+TX, brofenvalerate+TX, bromocyclen+TX, bromophos+TX, bromopropylate+TX, buprofezin+TX, butocarboxim+TX, butoxycarboxim+TX, butylpyridaben+TX, calcium polysulfide+TX, camphechlor+TX, carbanolate+TX, carbophenothion+TX, cymiazole+TX, chinomethionat+TX, chlorbenside+TX, chlordimeform+TX, chlordimeform hydrochloride+TX, chlorfenethol+TX, chlorfenson+TX, chlorfensulfide+TX, chlorobenzilate+TX, chloromebuform+TX, chloromethiuron+TX, chloropropylate+TX, chlorthiophos+TX, cinerin I+TX, cinerin II+TX, cinerins+TX, closantel+TX, coumaphos+TX, crotamiton+TX, crotoxyphos+TX, cufraneb+TX, cyanthoate+TX, DCPM+TX, DDT+TX, demephion+TX, demephion-O+TX, demephion-S+TX, demeton-methyl+TX, demeton-O+TX, demeton-O-methyl+TX, demeton-S+TX, demeton-S-methyl+TX, demeton-S-methylsulfon+TX, dichlofluanid+TX, dichlorvos+TX, dicliphos+TX, dienochlor+TX, dimefox+TX, dinex+TX, dinex-diclexine+TX, dinocap-4+TX, dinocap-6+TX, dinocton+TX, dinopenton+TX, dinosulfon+TX, dinoterbon+TX, dioxathion+TX, diphenyl sulfone+TX, disulfiram+TX, DNOC+TX, dofenapyn+TX, doramectin+TX, endothion+TX, eprinomectin+TX, ethoate-methyl+TX, etrimfos+TX, fenazaflor+TX, fenbutatin oxide+TX, fenothiocarb+TX, fenpyrad+TX, fen-pyroximate+TX, fenpyrazamine+TX, fenson+TX, fentrifanil+TX, flubenzimine+TX, flucycloxuron+TX, fluenetil+TX, fluorbenside+TX, FMC 1137+TX, formetanate+TX, formetanate hydrochloride+TX, formparanate+TX, gamma-HCH+TX, glyodin+TX, halfenprox+TX, hexadecyl cyclopropanecarboxylate+TX, isocarbophos+TX, jasmolin I+TX, jasmolin II+TX, jodfenphos+TX, lindane+TX, malonoben+TX, mecarbam+TX, mephosfolan+TX, mesulfen+TX, methacrifos+TX, methyl bromide+TX, metolcarb+TX, mexacarbate+TX, milbemycin oxime+TX, mipafox+TX, monocrotophos+TX, morphothion+TX, moxidectin+TX, naled+TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one+TX, nifluridide+TX, nikkomycins+TX, nitrilacarb+TX, nitrilacarb 1:1 zinc chloride complex+TX, omethoate+TX, oxydeprofos+TX, oxydisulfoton+TX, pp′-DDT+TX, parathion+TX, permethrin+TX, phenkapton+TX, phosalone+TX, phosfolan+TX, phosphamidon+TX, polychloroterpenes+TX, polynactins+TX, proclonol+TX, promacyl+TX, propoxur+TX, prothidathion+TX, prothoate+TX, pyrethrin I+TX, pyrethrin II+TX, pyrethrins+TX, pyridaphenthion+TX, pyrimitate+TX, quinalphos+TX, quintiofos+TX, R-1492+TX, phosglycin+TX, rotenone+TX, schradan+TX, sebufos+TX, selamectin+TX, sophamide+TX, SSI-121+TX, sulfiram+TX, sulfluramid+TX, sulfotep+TX, sulfur+TX, diflovidazin+TX, tau-fluvalinate+TX, TEPP+TX, terbam+TX, tetradifon+TX, tetrasul+TX, thiafenox+TX, thiocarboxime+TX, thiofanox+TX, thiometon+TX, thioquinox+TX, thuringiensin+TX, triamiphos+TX, triarathene+TX, triazophos+TX, triazuron+TX, trifenofos+TX, trinactin+TX, vamidothion+TX, vaniliprole+TX, bethoxazin+TX, copper dioctanoate+TX, copper sulfate+TX, cybutryne+TX, dichlone+TX, dichlorophen+TX, endothal+TX, fentin+TX, hydrated lime+TX, nabam+TX, quinoclamine+TX, quinonamid+TX, simazine+TX, triphenyltin acetate+TX, triphenyltin hydroxide+TX, crufomate+TX, piperazine+TX, thiophanate+TX, chloralose+TX, fenthion+TX, pyridin-4-amine+TX, strychnine+TX, 1-hydroxy-1H-pyridine-2-thione+TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide+TX, 8-hydroxyquinoline sulfate+TX, bronopol+TX, copper hydroxide+TX, cresol+TX, dipyrithione+TX, dodicin+TX, fenaminosulf+TX, formaldehyde+TX, hydrargaphen+TX, kasugamycin+TX, kasugamycin hydrochloride hydrate+TX, nickel bis(dimethyldithiocarbamate)+TX, nitrapyrin+TX, octhilinone+TX, oxolinic acid+TX, oxytetracycline+TX, potassium hydroxyquinoline sulfate+TX, probenazole+TX, streptomycin+TX, streptomycin sesquisulfate+TX, tecloftalam+TX, thiomersal+TX, Adoxophyes orana GV+TX, Agrobacterium radiobacter+TX, Amblyseius spp.+TX, Anagrapha falcifera NPV+TX, Anagrus atomus+TX, Aphelinus abdominalis+TX, Aphidius colemani+TX, Aphidoletes aphidimyza+TX, Autographa californica NPV+TX, Bacillus sphaericus Neide+TX, Beauveria brongniartii+TX, Chrysoperla carnea+TX, Cryptolaemus montrouzieri+TX, Cydia pomonella GV+TX, Dacnusa sibirica+TX, Diglyphus isaea+TX, Encarsia formosa+TX, Eretmocerus eremicus+TX, Heterorhabditis bacteriophora and H. megidis+TX, Hippodamia convergens+TX, Leptomastix dactylopii+TX, Macrolophus caliginosus+TX, Mamestra brassicae NPV+TX, Metaphycus helvolus+TX, Metarhizium anisopliae var. acridum+TX, Metarhizium anisopliae var. anisopliae+TX, Neodiprion sertifer NPV and N. lecontei NPV+TX, Orius spp.+TX, Paecilomyces fumosoroseus+TX, Phytoseiulus persimilis+TX, Steinernema bibionis+TX, Steinernema carpocapsae+TX, Steinernema feltiae+TX, Steinernema glaseri+TX, Steinernema riobrave+TX, Steinernema riobravis+TX, Steinernema scapterisci+TX, Steinernema spp.+TX, Trichogramma spp.+TX, Typhlodromus occidentalis+TX, Verticillium lecanii+TX, apholate+TX, bisazir+TX, busulfan+TX, dimatif+TX, hemel+TX, hempa+TX, metepa+TX, methiotepa+TX, methyl apholate+TX, morzid+TX, penfluron+TX, tepa+TX, thiohempa+TX, thiotepa+TX, tretamine+TX, uredepa+TX, (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol+TX, (E)-tridec-4-en-1-yl acetate+TX, (E)-6-methylhept-2-en-4-ol+TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate+TX, (Z)-dodec-7-en-1-yl acetate+TX, (Z)-hexadec-11-enal+TX, (Z)-hexadec-11-en-1-yl acetate+TX, (Z)-hexadec-13-en-11-yn-1-yl acetate+TX, (Z)-icos-13-en-10-one+TX, (Z)-tetradec-7-en-1-al+TX, (Z)-tetradec-9-en-1-ol+TX, (Z)-tetradec-9-en-1-yl acetate+TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate+TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate+TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate+TX, 14-methyloctadec-1-ene+TX, 4-methylnonan-5-ol with 4-methylnonan-5-one+TX, alpha-multistriatin+TX, brevicomin+TX, codlelure+TX, codlemone+TX, cuelure+TX, disparlure+TX, dodec-8-en-1-yl acetate+TX, dodec-9-en-1-yl acetate+TX, dodeca-8+TX, 10-dien-1-yl acetate+TX, dominicalure+TX, ethyl 4-methyloctanoate+TX, eugenol+TX, frontalin+TX, grandlure+TX, grandlure I+TX, grandlure II+TX, grandlure III+TX, grandlure IV+TX, hexalure+TX, ipsdienol+TX, ipsenol+TX, japonilure+TX, lineatin+TX, litlure+TX, looplure+TX, medlure+TX, megatomoic acid+TX, methyl eugenol+TX, muscalure+TX, octadeca-2,13-dien-1-yl acetate+TX, octadeca-3,13-dien-1-yl acetate+TX, orfralure+TX, oryctalure+TX, ostramone+TX, siglure+TX, sordidin+TX, sulcatol+TX, tetradec-11-en-1-yl acetate+TX, trimedlure+TX, trimedlure A+TX, trimedlure B.sub.1+TX, trimedlure B.sub.2+TX, trimedlure C+TX, trunc-call+TX, 2-(octylthio)ethanol+TX, butopyronoxyl+TX, butoxy(polypropylene glycol)+TX, dibutyl adipate+TX, dibutyl phthalate+TX, dibutyl succinate+TX, diethyltoluamide+TX, dimethyl carbate+TX, dimethyl phthalate+TX, ethyl hexanediol+TX, hexamide+TX, methoquin-butyl+TX, methylneodecanamide+TX, oxamate+TX, picaridin+TX, 1-dichloro-1-nitroethane+TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane+TX, 1,2-dichloropropane with 1,3-dichloropropene+TX, 1-bromo-2-chloroethane+TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate+TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate+TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate+TX, 2-(2-butoxyethoxy)ethyl thiocyanate+TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate+TX, 2-(4-chloro-3,5-xylyloxy)ethanol+TX, 2-chlorovinyl diethyl phosphate+TX, 2-imidazolidone+TX, 2-isovalerylindan-1,3-dione+TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate+TX, 2-thiocyanatoethyl laurate+TX, 3-bromo-1-chloroprop-1-ene+TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate+TX, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate+TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate+TX, acethion+TX, acrylonitrile+TX, aldrin+TX, allosamidin+TX, allyxycarb+TX, alpha-ecdysone+TX, aluminium phosphide+TX, aminocarb+TX, anabasine+TX, athidathion+TX, azamethiphos+TX, Bacillus thuringiensis delta endotoxins+TX, barium hexafluorosilicate+TX, barium polysulfide+TX, barthrin+TX, Bayer 22/190+TX, Bayer 22408+TX, beta-cyfluthrin+TX, beta-cypermethrin+TX, bioethanomethrin+TX, biopermethrin+TX, bis(2-chloroethyl) ether+TX, borax+TX, bromfenvinfos+TX, bromo-DDT+TX, bufencarb+TX, butacarb+TX, butathiofos+TX, butonate+TX, calcium arsenate+TX, calcium cyanide+TX, carbon disulfide+TX, carbon tetrachloride+TX, cartap hydrochloride+TX, cevadine+TX, chlorbicyclen+TX, chlordane+TX, chlordecone+TX, chloroform+TX, chloropicrin+TX, chlorphoxim+TX, chlorprazophos+TX, cis-resmethrin+TX, cismethrin+TX, clocythrin+TX, copper acetoarsenite+TX, copper arsenate+TX, copper oleate+TX, coumithoate+TX, cryolite+TX, CS 708+TX, cyanofenphos+TX, cyanophos+TX, cyclethrin+TX, cythioate+TX, d-tetramethrin+TX, DAEP+TX, dazomet+TX, decarbofuran+TX, diamidafos+TX, dicapthon+TX, dichlofenthion+TX, dicresyl+TX, dicyclanil+TX, dieldrin+TX, diethyl 5-methylpyrazol-3-yl phosphate+TX, dilor+TX, dimefluthrin+TX, dimetan+TX, dimethrin+TX, dimethylvinphos+TX, dimetilan+TX, dinoprop+TX, dinosam+TX, dinoseb+TX, diofenolan+TX, dioxabenzofos+TX, dithicrofos+TX, DSP+TX, ecdysterone+TX, EI 1642+TX, EMPC+TX, EPBP+TX, etaphos+TX, ethiofencarb+TX, ethyl formate+TX, ethylene dibromide+TX, ethylene dichloride+TX, ethylene oxide+TX, EXD+TX, fenchlorphos+TX, fenethacarb+TX, fenitrothion+TX, fenoxacrim+TX, fenpirithrin+TX, fensulfothion+TX, fenthion-ethyl+TX, flucofuron+TX, fosmethilan+TX, fospirate+TX, fosthietan+TX, furathiocarb+TX, furethrin+TX, guazatine+TX, guazatine acetates+TX, sodium tetrathiocarbonate+TX, halfenprox+TX, HCH+TX, HEOD+TX, heptachlor+TX, heterophos+TX, HHDN+TX, hydrogen cyanide+TX, hyquincarb+TX, IPSP+TX, isazofos+TX, isobenzan+TX, isodrin+TX, isofenphos+TX, isolane+TX, isoprothiolane+TX, isoxathion+TX, juvenile hormone I+TX, juvenile hormone II+TX, juvenile hormone III+TX, kelevan+TX, kinoprene+TX, lead arsenate+TX, leptophos+TX, lirimfos+TX, lythidathion+TX, m-cumenyl methylcarbamate+TX, magnesium phosphide+TX, mazidox+TX, mecarphon+TX, menazon+TX, mercurous chloride+TX, mesulfenfos+TX, metam+TX, metam-potassium+TX, metam-sodium+TX, methanesulfonyl fluoride+TX, methocrotophos+TX, methoprene+TX, methothrin+TX, methoxychlor+TX, methyl isothiocyanate+TX, methylchloroform+TX, methylene chloride+TX, metoxadiazone+TX, mirex+TX, naftalofos+TX, naphthalene+TX, NC-170+TX, nicotine+TX, nicotine sulfate+TX, nithiazine+TX, nornicotine+TX, O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate+TX, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate+TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate+TX, O,O,O′,O′-tetrapropyl dithiopyrophosphate+TX, oleic acid+TX, para-dichlorobenzene+TX, parathion-methyl+TX, pentachlorophenol+TX, pentachlorophenyl laurate+TX, PH 60-38+TX, phenkapton+TX, phosnichlor+TX, phosphine+TX, phoxim-methyl+TX, pirimetaphos+TX, polychlorodicyclopentadiene isomers+TX, potassium arsenite+TX, potassium thiocyanate+TX, precocene I+TX, precocene II+TX, precocene III+TX, primidophos+TX, profluthrin+TX, promecarb+TX, prothiofos+TX, pyrazophos+TX, pyresmethrin+TX, quassia+TX, quinalphos-methyl+TX, quinothion+TX, rafoxanide+TX, resmethrin+TX, rotenone+TX, kadethrin+TX, ryania+TX, ryanodine+TX, sabadilla)+TX, schradan+TX, sebufos+TX, SI-0009+TX, thiapronil+TX, sodium arsenite+TX, sodium cyanide+TX, sodium fluoride+TX, sodium hexafluorosilicate+TX, sodium pentachlorophenoxide+TX, sodium selenate+TX, sodium thiocyanate+TX, sulcofuron+TX, sulcofuron-sodium+TX, sulfuryl fluoride+TX, sulprofos+TX, tar oils+TX, tazimcarb+TX, TDE+TX, tebupirimfos+TX, temephos+TX, terallethrin+TX, tetrachloroethane+TX, thicrofos+TX, thiocyclam+TX, thiocyclam hydrogen oxalate+TX, thionazin+TX, thiosultap+TX, thiosultap-sodium+TX, tralomethrin+TX, transpermethrin+TX, triazamate+TX, trichlormetaphos-3+TX, trichloronat+TX, trimethacarb+TX, tolprocarb+TX, triclopyricarb+TX, triprene+TX, veratridine+TX, veratrine+TX, XMC+TX, zetamethrin+TX, zinc phosphide+TX, zolaprofos+TX, and meperfluthrin+TX, tetramethylfluthrin+TX, bis(tributyltin) oxide+TX, bromoacetamide+TX, ferric phosphate+TX, niclosamide-olamine+TX, tributyltin oxide+TX, pyrimorph+TX, trifenmorph+TX, 1,2-dibromo-3-chloropropane+TX, 1,3-dichloropropene+TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide+TX, 3-(4-chlorophenyl)-5-methylrhodanine+TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid+TX, 6-isopentenylaminopurine+TX, benclothiaz+TX, cytokinins+TX, DCIP+TX, furfural+TX, isamidofos+TX, kinetin+TX, Myrothecium verrucaria composition+TX, tetrachlorothiophene+TX, xylenols+TX, zeatin+TX, potassium ethylxanthate+TX, acibenzolar+TX, acibenzolar-S-methyl+TX, Reynoutria sachalinensis extract+TX, alpha-chlorohydrin+TX, antu+TX, barium carbonate+TX, bisthiosemi+TX, brodifacoum+TX, bromadiolone+TX, bromethalin+TX, chlorophacinone+TX, cholecalciferol+TX, coumachlor+TX, coumafuryl+TX, coumatetralyl+TX, crimidine+TX, difenacoum+TX, difethialone+TX, diphacinone+TX, ergocalciferol+TX, flocoumafen+TX, fluoroacetamide+TX, flupropadine+TX, flupropadine hydrochloride+TX, norbormide+TX, phosacetim+TX, phosphorus+TX, pindone+TX, pyrinuron+TX, scilliroside+TX, sodium fluoroacetate+TX, thallium sulfate+TX, warfarin+TX, 2-(2-butoxyethoxy)ethyl piperonylate+TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone+TX, farnesol with nerolidol+TX, verbutin+TX, MGK 264+TX, piperonyl butoxide+TX, piprotal+TX, propyl isomer+TX, S421+TX, sesamex+TX, sesasmolin+TX, sulfoxide+TX, anthraquinone+TX, copper naphthenate+TX, copper oxychloride+TX, dicyclopentadiene+TX, thiram+TX, zinc naphthenate+TX, ziram+TX, imanin+TX, ribavirin+TX, mercuric oxide+TX, thiophanate-methyl+TX, azaconazole+TX, bitertanol+TX, bromuconazole+TX, cyproconazole+TX, difenoconazole+TX, diniconazole+TX, epoxiconazole+TX, fenbuconazole+TX, fluquinconazole+TX, flusilazole+TX, flutriafol+TX, furametpyr+TX, hexaconazole+TX, imazalil+TX, imibenconazole+TX, ipconazole+TX, metconazole+TX, myclobutanil+TX, paclobutrazole+TX, pefurazoate+TX, penconazole+TX, prothioconazole+TX, pyrifenox+TX, prochloraz+TX, propiconazole+TX, pyrisoxazole+TX, simeconazole+TX, tebuconazole+TX, tetraconazole+TX, triadimefon+TX, triadimenol+TX, triflumizole+TX, triticonazole+TX, ancymidol+TX, fenarimol+TX, nuarimol+TX, bupirimate+TX, dimethirimol+TX, ethirimol+TX, dodemorph+TX, fenpropidine+TX, fenpropimorph+TX, spiroxamine+TX, tridemorph+TX, cyprodinil+TX, mepanipyrim+TX, pyrimethanil+TX, fenpiclonil+TX, fludioxonil+TX, benalaxyl+TX, furalaxyl+TX, metalaxyl+TX, R-metalaxyl+TX, ofurace+TX, oxadixyl+TX, carbendazim+TX, debacarb+TX, fuberidazole+TX, thiabendazole+TX, chlozolinate+TX, dichlozoline+TX, myclozoline+TX, procymidone+TX, vinclozoline+TX, boscalid+TX, carboxin+TX, fenfuram+TX, flutolanil+TX, mepronil+TX, oxycarboxin+TX, penthiopyrad+TX, thifluzamide+TX, dodine+TX, iminoctadine+TX, azoxystrobin+TX, dimoxystrobin+TX, enestroburin+TX, fenaminstrobin+TX, flufenoxystrobin+TX, fluoxastrobin+TX, kresoxim-methyl+TX, metominostrobin+TX, trifloxystrobin+TX, orysastrobin+TX, picoxystrobin+TX, pyraclostrobin+TX, pyrametostrobin+TX, pyraoxystrobin+TX, ferbam+TX, mancozeb+TX, maneb+TX, metiram+TX, propineb+TX, zineb+TX, captafol+TX, captan+TX, fluoroimide+TX, folpet+TX, tolylfluanid+TX, bordeaux mixture+TX, copper oxide+TX, mancopper+TX, oxine-copper+TX, nitrothal-isopropyl+TX, edifenphos+TX, iprobenphos+TX, phosdiphen+TX, tolclofos-methyl+TX, anilazine+TX, benthiavalicarb+TX, blasticidin-S+TX, chloroneb+TX, chlorothalonil+TX, cyflufenamid+TX, cymoxanil+TX, diclocymet+TX, diclomezine+TX, dicloran+TX, diethofencarb+TX, dimethomorph+TX, flumorph+TX, dithianon+TX, ethaboxam+TX, etridiazole+TX, famoxadone+TX, fenamidone+TX, fenoxanil+TX, ferimzone+TX, fluazinam+TX, fluopicolide+TX, flusulfamide+TX, fluxapyroxad+TX, fenhexamid+TX, fos-etyl-aluminium+TX, hymexazol+TX, iprovalicarb+TX, cyazofamid+TX, methasulfocarb+TX, metrafenone+TX, pencycuron+TX, phthalide+TX, polyoxins+TX, propamocarb+TX, pyribencarb+TX, proquinazid+TX, pyroquilon+TX, pyriofenone+TX, quinoxyfen+TX, quintozene+TX, tiadinil+TX, triazoxide+TX, tricyclazole+TX, triforine+TX, validamycin+TX, valifenalate+TX, zoxamide+TX, mandipropamid+TX, isopyrazam+TX, sedaxane+TX, benzovindiflupyr+TX, pydiflumetofen+TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3′,4′,5′-trifluoro-biphenyl-2-yl)-amide+TX, isoflucypram+TX, isotianil+TX, dipymetitrone+TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile+TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile+TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide+TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine+TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine+TX, fluindapyr+TX, coumethoxystrobin (jiaxiangjunzhi)+TX, Ivbenmixianan+TX, dichlobentiazox+TX, mandestrobin+TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone+TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol+TX, oxathiapiprolin+TX, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate+TX, pyraziflumid+TX, inpyrfluxam+TX, trolprocarb+TX, mefentrifluconazole+TX, ipfentrifluconazole+TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX, N′-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine+TX, N′-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine+TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl] methanesulfonate+TX, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate+TX, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate+TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine+TX, pyridachlometyl+TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide+TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one+TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one+TX, aminopyrifen+TX, ametoctradin+TX, amisulbrom+TX, penflufen+TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide+TX, florylpicoxamid+TX, fenpicoxamid+TX, tebufloquin+TX, ipflufenoquin+TX, quinofumelin+TX, isofetamid+TX, N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide+TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide+TX, benzothiostrobin+TX, phenamacril+TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1)+TX, fluopyram+TX, flutianil+TX, fluopimomide+TX, pyrapropoyne+TX, picarbutrazox+TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide+TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide+TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile+TX, metyltetraprole+TX, 2-(difluororethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide+TX, α-(1,1-dirmethylethyl)-α-[4′-(trifluoromethoxy)[1,1′-biphenyl]-4-yi]-5-pyrimidinemethanol+TX, fluoxapiprolin+TX, enoxastrobin+TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile+TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile+TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile+TX, trinexapac+TX, coumoxystrobin+TX, zhongshengmycin+TX, thiodiazole copper+TX, zinc thiazole+TX, amectotractin+TX, iprodione+TX, mixtures of (N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide+TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide+TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide+TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide+TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one+TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one+TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate+TX, and N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine+TX), wherein the compound in the mixture, other than TX, may be prepared from the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689, 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol+TX (this compound may be prepared from the methods described in WO 2017/029179), 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol+TX (this compound may be prepared from the methods described in WO 2017/029179), 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile+TX (this compound may be prepared from the methods described in WO 2016/156290), 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile+TX (this compound may be prepared from the methods described in WO 2016/156290), (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate+TX (this compound may be prepared from the methods described in WO 2014/006945), 2,6-Dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone+TX (this compound may be prepared from the methods described in WO 2011/138281), N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide+TX, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX, (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide+TX (this compound may be prepared from the methods described in WO 2018/153707), N′-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine+TX, N′-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine+TX (this compound may be prepared from the methods described in WO 2016/202742), and 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX (this compound may be prepared from the methods described in WO 2014/095675),

[0594] microbials including: Acinetobacter iwoffii+TX, Acremonium alternatum+TX+TX, Acremonium cephalosporium+TX+TX, Acremonium diospyri+TX, Acremonium obclavatum+TX, Adoxophyes orana granulovirus (AdoxGV) (Capex®)+TX, Agrobacterium radiobacter strain K84 (Galltrol-A®)+TX, Alternaria alternate+TX, Alternaria cassia+TX, Alternaria destruens (Smolder®)+TX, Ampelomyces quisqualis (AQ10®)+TX, Aspergillus flavus AF36 (AF36®)+TX, Aspergillus flavus NRRL 21882 (Aflaguard®)+TX, Aspergillus spp.+TX, Aureobasidium pullulans+TX, Azospirillum+TX, (MicroAZ®+TX, TAZO B®)+TX, Azotobacter+TX, Azotobacter chroocuccum (Azotomeal®)+TX, Azotobacter cysts (Bionatural Blooming Blossoms®)+TX, Bacillus amyloliquefaciens+TX, Bacillus cereus+TX, Bacillus chitinosporus strain CM-1+TX, Bacillus chitinosporus strain AQ746+TX, Bacillus licheniformis strain HB-2 (Biostart™ Rhizoboost®)+TX, Bacillus licheniformis strain 3086 (EcoGuard®+TX, Green Releaf®)+TX, Bacillus circulans+TX, Bacillus firmus (BioSafe®+TX, BioNem-WP®+TX, VOTiVO®)+TX, Bacillus firmus strain 1-1582+TX, Bacillus macerans+TX, Bacillus marismortui+TX, Bacillus megaterium+TX, Bacillus mycoides strain AQ726+TX, Bacillus papillae (Milky Spore Powder®)+TX, Bacillus pumilus spp.+TX, Bacillus pumilus strain GB34 (Yield Shield®)+TX, Bacillus pumilus strain AQ717+TX, Bacillus pumilus strain QST 2808 (Sonata®+TX, Ballad Plus®)+TX, Bacillus spahericus (VectoLex®)+TX, Bacillus spp.+TX, Bacillus spp. strain AQ175+TX, Bacillus spp. strain AQ177+TX, Bacillus spp. strain AQ178+TX, Bacillus subtilis strain QST 713 (CEASE®+TX, Serenade®+TX, Rhapsody®)+TX, Bacillus subtilis strain QST 714 (JAZZ®)+TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilis strain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 (Taegro®+TX, Rhizopro®)+TX, Bacillus thuringiensis Cry 2Ae+TX, Bacillus thuringiensis Cry1Ab+TX, Bacillus thuringiensis aizawai GC 91 (Agree®)+TX, Bacillus thuringiensis israelensis (BMP123®+TX, Aquabac®+TX, VectoBac®)+TX, Bacillus thuringiensis kurstaki (Javelin®+TX, Deliver®+TX, CryMax®+TX, Bonide®+TX, Scutella WP®+TX, Turilav WP®+TX, Astuto®+TX, Dipel WP®+TX, Biobit®+TX, Foray®)+TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®)+TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF/3P®)+TX, Bacillus thuringiensis strain BD #32+TX, Bacillus thuringiensis strain AQ52+TX, Bacillus thuringiensis var. aizawai (XenTari®+TX, DiPel®)+TX, bacteria spp. (GROWMEND®+TX, GROWSWEET®+TX, Shootup®)+TX, bacteriophage of Clavipacter michiganensis (AgriPhage®)+TX, Bakflor®+TX, Beauveria bassiana (Beaugenic®+TX, Brocaril WP®)+TX, Beauveria bassiana GHA (Mycotrol ES®+TX, Mycotrol O®+TX, BotaniGuard®)+TX, Beauveria brongniartii (Engerlingspilz®+TX, Schweizer Beauveria®+TX, Melocont®)+TX, Beauveria spp.+TX, Botrytis cineria+TX, Bradyrhizobium japonicum (TerraMax®)+TX, Brevibacillus brevis+TX, Bacillus thuringiensis tenebrionis (Novodor®)+TX, BtBooster+TX, Burkholderia cepacia (Deny®+TX, Intercept®+TX, Blue Circle®)+TX, Burkholderia gladii+TX, Burkholderia gladioli+TX, Burkholderia spp.+TX, Canadian thistle fungus (CBH Canadian Bioherbicide®)+TX, Candida butyri+TX, Candida famata+TX, Candida fructus+TX, Candida glabrata+TX, Candida guilliermondii+TX, Candida melibiosica+TX, Candida oleophila strain 0+TX, Candida parapsilosis+TX, Candida pelliculosa+TX, Candida pulcherrima+TX, Candida reukaufii+TX, Candida saitoana (Bio-Coat®+TX, Biocure®)+TX, Candida sake+TX, Candida spp.+TX, Candida tenius+TX, Cedecea dravisae+TX, Cellulomonas flavigena+TX, Chaetomium cochliodes (Nova-Cide®)+TX, Chaetomium globosum (Nova-Cide®)+TX, Chromobacterium subtsugae strain PRAA4-1T (Grandevo®)+TX, Cladosporium cladosporioides+TX, Cladosporium oxysporum+TX, Cladosporium chlorocephalum+TX, Cladosporium spp.+TX, Cladosporium tenuissimum+TX, Clonostachys rosea (EndoFine®)+TX, Colletotrichum acutatum+TX, Coniothyrium minitans (Cotans WG®)+TX, Coniothyrium spp.+TX, Cryptococcus albidus (YIELDPLUS®)+TX, Cryptococcus humicola+TX, Cryptococcus infirmo-miniatus+TX, Cryptococcus laurentii+TX, Cryptophlebia leucotreta granulovirus (Cryptex®)+TX, Cupriavidus campinensis+TX, Cydia pomonella granulovirus (CYD-X®)+TX, Cydia pomonella granulovirus (Madex®+TX, Madex Plus®+TX, Madex Max/Carpovirusine®)+TX, Cylindrobasidium laeve (Stumpout®)+TX, Cylindrocladium+TX, Debaryomyces hansenii+TX, Drechslera hawaiinensis+TX, Enterobacter cloacae+TX, Enterobacteriaceae+TX, Entomophtora virulenta (Vektor®)+TX, Epicoccum nigrum+TX, Epicoccum purpurascens+TX, Epicoccum spp.+TX, Filobasidium floriforme+TX, Fusarium acuminatum+TX, Fusarium chlamydosporum+TX, Fusarium oxysporum (Fusaclean®/Biofox C®)+TX, Fusarium proliferatum+TX, Fusarium spp.+TX, Galactomyces geotrichum+TX, Gliocladium catenulatum (Primastop®+TX, Prestop®)+TX, Gliocladium roseum+TX, Gliocladium spp. (SoilGard®)+TX, Gliocladium virens (Soilgard®)+TX, Granulovirus (Granupom®)+TX, Halobacillus halophilus+TX, Halobacillus litoralis+TX, Halobacillus trueperi+TX, Halomonas spp.+TX, Halomonas subglaciescola+TX, Halovibrio variabilis+TX, Hanseniaspora uvarum+TX, Helicoverpa armigera nucleopolyhedrovirus (Helicovex®)+TX, Helicoverpa zea nuclear polyhedrosis virus (Gemstar®)+TX, Isoflavone—formononetin (Myconate®)+TX, Kloeckera apiculata+TX, Kloeckera spp.+TX, Lagenidium giganteum (Laginex®)+TX, Lecanicillium longisporum (Vertiblast®)+TX, Lecanicillium muscarium (Vertikil®)+TX, Lymantria Dispar nucleopolyhedrosis virus (Disparvirus®)+TX, Marinococcus halophilus+TX, Meira geulakonigii+TX, Metarhizium anisopliae (Met52®)+TX, Metarhizium anisopliae (Destruxin WP®)+TX, Metschnikowia fruticola (Shemer®)+TX, Metschnikowia pulcherrima+TX, Microdochium dimerum (Antibot®)+TX, Micromonospora coerulea+TX, Microsphaeropsis ochracea+TX, Muscodor albus 620 (Muscudor®)+TX, Muscodor roseus strain A3-5+TX, Mycorrhizae spp. (AMykor®+TX, Root Maximizer®)+TX, Myrothecium verrucaria strain AARC-0255 (DiTera®)+TX, BROS PLUS®+TX, Ophiostoma piliferum strain D97 (Sylvanex®)+TX, Paecilomyces farinosus+TX, Paecilomyces fumosoroseus (PFR-97®+TX, PreFeRal®)+TX, Paecilomyces (linacinus Biostat WP®)+TX, Paecilomyces lilacinus strain 251 (MeloCon WG®)+TX, Paenibacillus polymyxa+TX, Pantoea agglomerans (BlightBan C.sub.9-1®)+TX, Pantoea spp.+TX, Pasteuria spp. (Econem®)+TX, Pasteuria nishizawae+TX, Penicillium aurantiogriseum+TX, Penicillium billai (Jumpstart®+TX, TagTeam®)+TX, Penicillium brevicompactum+TX, Penicillium frequentans+TX, Penicillium griseofulvum+TX, Penicillium purpurogenum+TX, Penicillium spp.+TX, Penicillium viridicatum+TX, Phlebiopsis gigantean (Rotstop®)+TX, phosphate solubilizing bacteria (Phosphomeal®)+TX, Phytophthora cryptogea+TX, Phytophthora palmivora (Devine®)+TX, Pichia anomala+TX, Pichia guilermondii+TX, Pichia membranaefaciens+TX, Pichia onychis+TX, Pichia stipites+TX, Pseudomonas aeruginosa+TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®)+TX, Pseudomonas cepacia+TX, Pseudomonas chlororaphis (AtEze®)+TX, Pseudomonas corrugate+TX, Pseudomonas fluorescens strain A506 (BlightBan A506®)+TX, Pseudomonas putida+TX, Pseudomonas reactans+TX, Pseudomonas spp.+TX, Pseudomonas syringae (Bio-Save®)+TX, Pseudomonas viridiflava+TX, Pseudomons fluorescens (Zequanox®)+TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®)+TX, Puccinia canaliculata+TX, Puccinia thlaspeos (Wood Warrior®)+TX, Pythium paroecandrum+TX, Pythium oligandrum (Polygandron®+TX, Polyversum®)+TX, Pythium periplocum+TX, Rhanella aquatilis+TX, Rhanella spp.+TX, Rhizobia (Dormal®+TX, Vault®)+TX, Rhizoctonia+TX, Rhodococcus globerulus strain AQ719+TX, Rhodosporidium diobovatum+TX, Rhodosporidium toruloides+TX, Rhodotorula spp.+TX, Rhodotorula glutinis+TX, Rhodotorula graminis+TX, Rhodotorula mucilagnosa+TX, Rhodotorula rubra+TX, Saccharomyces cerevisiae+TX, Salinococcus roseus+TX, Sclerotinia minor+TX, Sclerotinia minor (SARRITOR®)+TX, Scytalidium spp.+TX, Scytalidium uredinicola+TX, Spodoptera exigua nuclear polyhedrosis virus (Spod-X®+TX, Spexit®)+TX, Serratia marcescens+TX, Serratia plymuthica+TX, Serratia spp.+TX, Sordaria fimicola+TX, Spodoptera littoralis nucleopolyhedrovirus (Littovir®)+TX, Sporobolomyces roseus+TX, Stenotrophomonas maltophilia+TX, Streptomyces ahygroscopicus+TX, Streptomyces albaduncus+TX, Streptomyces exfoliates+TX, Streptomyces galbus+TX, Streptomyces griseoplanus+TX, Streptomyces griseoviridis (Mycostop®)+TX, Streptomyces lydicus (Actinovate®)+TX, Streptomyces lydicus WYEC-108 (ActinoGrow®)+TX, Streptomyces violaceus+TX, Tilletiopsis minor+TX, Tilletiopsis spp.+TX, Trichoderma asperellum (T34 Biocontrol®)+TX, Trichoderma gamsii (Tenet®)+TX, Trichoderma atroviride (Plantmate®)+TX, Trichoderma hamatum TH 382+TX, Trichoderma harzianum rifai (Mycostar®)+TX, Trichoderma harzianum T-22 (Trianum-P®+TX, PlantShield HC®+TX, RootShield®+TX, Trianum-G®)+TX, Trichoderma harzianum T-39 (Trichodex®)+TX, Trichoderma inhamatum+TX, Trichoderma koningii+TX, Trichoderma spp. LC 52 (Sentinel®)+TX, Trichoderma lignorum+TX, Trichoderma longibrachiatum+TX, Trichoderma polysporum (Binab T®)+TX, Trichoderma taxi+TX, Trichoderma virens+TX, Trichoderma virens (formerly Gliocladium virens GL-21) (SoilGuard®)+TX, Trichoderma viride+TX, Trichoderma viride strain ICC 080 (Remedier®)+TX, Trichosporon pullulans+TX, Trichosporon spp.+TX, Trichothecium spp.+TX, Trichothecium roseum+TX, Typhula phacorrhiza strain 94670+TX, Typhula phacorrhiza strain 94671+TX, Ulocladium atrum+TX, Ulocladium oudemansii (Botry-Zen®)+TX, Ustilago maydis+TX, various bacteria and supplementary micronutrients (Natural II®)+TX, various fungi (Millennium Microbes®)+TX, Verticillium chlamydosporium+TX, Verticillium lecanii (Mycotal®+TX, Vertalec®)+TX, Vip3Aa20 (VIPtera®)+TX, Virgibaclillus marismortui+TX, Xanthomonas campestris pv. Poae (Camperico®)+TX, Xenorhabdus bovienii+TX, Xenorhabdus nematophilus;

[0595] Plant extracts including: pine oil (Retenol®)+TX, azadirachtin (Plasma Neem Oil®+TX, AzaGuard®+TX, MeemAzal®+TX, Molt-X®+TX, Botanical IGR (Neemazad®+TX, Neemix®)+TX, canola oil (Lilly Miller Vegol®)+TX, Chenopodium ambrosioides near ambrosioides (Requiem®)+TX, Chrysanthemum extract (Crisant®)+TX, extract of neem oil (Trilogy®)+TX, essentials oils of Labiatae (Botania®)+TX, extracts of clove rosemary peppermint and thyme oil (Garden insect Killer®)+TX, Glycinebetaine (Greenstim®)+TX, garlic+TX, lemongrass oil (GreenMatch®)+TX, neem oil+TX, Nepeta cataria (Catnip oil)+TX, Nepeta catarina+TX, nicotine+TX, oregano oil (MossBuster®)+TX, Pedaliaceae oil (Nematon®)+TX, pyrethrum+TX, Quillaja saponaria (NemaQ®)+TX, Reynoutria sachalinensis (Regalia®+TX, Sakalia®)+TX, rotenone (Eco Roten®)+TX, Rutaceae plant extract (Soleo®)+TX, soybean oil (Ortho Ecosense®)+TX, tea tree oil (Timorex Gold®)+TX, thymus oil+TX, AGNIQUE® MMF+TX, BugOil®+TX, mixture of rosemary sesame pepermint thyme and cinnamon extracts (EF 300®)+TX, mixture of clove rosemary and peppermint extract (EF 400®)+TX, mixture of clove pepermint garlic oil and mint (Soil Shot®)+TX, kaolin (Screen®)+TX, storage glucam of brown algae (Laminarin®);

[0596] pheromones including: blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®)+TX, Codling Moth Pheromone (Paramount dispenser-(CM)/Isomate C-Plus®)+TX, Grape Berry Moth Pheromone (3M MEC-GBM Sprayable Pheromone®)+TX, Leafroller pheromone (3M MEC—LR Sprayable Pheromone®)+TX, Muscamone (Snip7 Fly Bait®+TX, Starbar Premium Fly Bait®)+TX, Oriental Fruit Moth Pheromone (3M oriental fruit moth sprayable Pheromone®)+TX, Peachtree Borer Pheromone (Isomate-P®)+TX, Tomato Pinworm Pheromone (3M Sprayable Pheromone®)+TX, Entostat powder (extract from palm tree) (Exosex CM®)+TX, (E+TX,Z+TX,Z)-3+TX,8+TX,11 Tetradecatrienyl acetate+TX, (Z+TX,Z+TX,E)-7+TX,11+TX,13-Hexadecatrienal+TX, (E+TX,Z)-7+TX,9-Dodecadien-1-yl acetate+TX, 2-Methyl-1-butanol+TX, Calcium acetate+TX, Scenturion®+TX, Biolure®+TX, Check-Mate®+TX, Lavandulyl senecioate; Macrobials including: Aphelinus abdominalis+TX, Aphidius ervi (Aphelinus-System®)+TX, Acerophagus papaya+TX, Adalia bipunctata (Adalia-System®)+TX, Adalia bipunctata (Adaline®)+TX, Adalia bipunctata (Aphidalia®)+TX, Ageniaspis citricola+TX, Ageniaspis fuscicollis+TX, Amblyseius andersoni (Anderline®+TX, Andersoni-System®)+TX, Amblyseius californicus (Amblyline®+TX, Spical®)+TX, Amblyseius cucumeris (Thripex®+TX, Bugline cucumeris®)+TX, Amblyseius fallacis (Fallacis®)+TX, Amblyseius swirskii (Bugline Swirskii®+TX, Swirskii-Mite®)+TX, Amblyseius womersleyi (WomerMite®)+TX, Amitus hesperidum+TX, Anagrus atomus+TX, Anagyrus fusciventris+TX, Anagyrus kamali+TX, Anagyrus loecki+TX, Anagyrus pseudococci (Citripar®)+TX, Anicetus benefices+TX, Anisopteromalus calandrae+TX, Anthocoris nemoralis (Anthocoris-System®)+TX, Aphelinus abdominalis (Apheline®+TX, Aphiline®)+TX, Aphelinus asychis+TX, Aphidius colemani (Aphipar®)+TX, Aphidius ervi (Ervipar®)+TX, Aphidius gifuensis+TX, Aphidius matricariae (Aphipar-M®)+TX, Aphidoletes aphidimyza (Aphidend®)+TX, Aphidoletes aphidimyza (Aphidoline®)+TX, Aphytis lingnanensis+TX, Aphytis melinus+TX, Aprostocetus hagenowii+TX, Atheta coriaria (Staphyline®)+TX, Bombus spp.+TX, Bombus terrestris (Natupol Beehive®)+TX, Bombus terrestris (Beeline®+TX, Tripol®)+TX, Cephalonomia stephanoderis+TX, Chilocorus nigritus+TX, Chrysoperla carnea (Chrysoline®)+TX, Chrysoperla carnea (Chrysopa®)+TX, Chrysoperla rufilabris+TX, Cirrospilus ingenuus+TX, Cirrospilus quadristriatus+TX, Citrostichus phyllocnistoides+TX, Closterocerus chamaeleon+TX, Closterocerus spp.+TX, Coccidoxenoides perminutus (Planopar®)+TX, Coccophagus cowperi+TX, Coccophagus lycimnia+TX, Cotesia flavipes+TX, Cotesia plutellae+TX, Cryptolaemus montrouzieri (Cryptobug®+TX, Cryptoline®)+TX, Cybocephalus nipponicus+TX, Dacnusa sibirica+TX, Dacnusa sibirica (Minusa®)+TX, Diglyphus isaea (Diminex®)+TX, Delphastus catalinae (Delphastus®)+TX, Delphastus pusillus+TX, Diachasmimorpha krausii+TX, Diachasmimorpha longicaudata+TX, Diaparsis jucunda+TX, Diaphorencyrtus aligarhensis+TX, Diglyphus isaea+TX, Diglyphus isaea (Miglyphus®+TX, Digline®)+TX, Dacnusa sibirica (DacDigline®+TX, Minex®)+TX, Diversinervus spp.+TX, Encarsia citrina+TX, Encarsia formosa (Encarsia Max®+TX, Encarline®+TX, En-Strip®)+TX, Eretmocerus eremicus (Enermix®)+TX, Encarsia guadeloupae+TX, Encarsia haitiensis+TX, Episyrphus balteatus (Syrphidend®)+TX, Eretmoceris siphonini+TX, Eretmocerus californicus+TX, Eretmocerus eremicus (Ercal®+TX, Eretline e®)+TX, Eretmocerus eremicus (Bemimix®)+TX, Eretmocerus hayati+TX, Eretmocerus mundus (Bemipar®+TX, Eretline m®)+TX, Eretmocerus siphonini+TX, Exochomus quadripustulatus+TX, Feltiella acarisuga (Spidend®)+TX, Feltiella acarisuga (Feltiline®)+TX, Fopius arisanus+TX, Fopius ceratitivorus+TX, Formononetin (Wirless Beehome®)+TX, Franklinothrips vespiformis (Vespop®)+TX, Galendromus occidentalis+TX, Goniozus legneri+TX, Habrobracon hebetor+TX, Harmonia axyridis (HarmoBeetle®)+TX, Heterorhabditis spp. (Lawn Patrol®)+TX, Heterorhabditis bacteriophora (NemaShield HB®+TX, Nemaseek®+TX, Terranem-Nam®+TX, Terranem®+TX, Larvanem®+TX, B-Green®+TX, NemAttack®+TX, Nematop®)+TX, Heterorhabditis megidis (Nemasys H®+TX, BioNem H®+TX, Exhibitline hm®+TX, Larvanem-M®)+TX, Hippodamia convergens+TX, Hypoaspis aculeifer (Aculeifer-System®+TX, Entomite-A®)+TX, Hypoaspis miles (Hypoline m®+TX, Entomite-M®)+TX, Lbalia leucospoides+TX, Lecanoideus floccissimus+TX, Lemophagus errabundus+TX, Leptomastidea abnormis+TX, Leptomastix dactylopii (Leptopar®)+TX, Leptomastix epona+TX, Lindorus lophanthae+TX, Lipolexis oregmae+TX, Lucilia caesar (Natufly®)+TX, Lysiphlebus testaceipes+TX, Macrolophus caliginosus (Mirical-N®+TX, Macroline c®+TX, Mirical®)+TX, Mesoseiulus longipes+TX, Metaphycus flavus+TX, Metaphycus lounsburyi+TX, Micromus angulatus (Milacewing®)+TX, Microterys flavus+TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®)+TX, Neodryinus typhlocybae+TX, Neoseiulus californicus+TX, Neoseiulus cucumeris (THRYPEX®)+TX, Neoseiulus fallacis+TX, Nesideocoris tenuis (NesidioBug®+TX, Nesibug®)+TX, Ophyra aenescens (Biofly®)+TX, Orius insidiosus (Thripor-I®+TX, Oriline i®)+TX, Orius laevigatus (Thripor-L®+TX, Oriline I®)+TX, Orius majusculus (Oriline m®)+TX, Orius strigicollis (Thripor-S®)+TX, Pauesia juniperorum+TX, Pediobius foveolatus+TX, Phasmarhabditis hermaphrodita (Nemaslug®)+TX, Phymastichus coffea+TX, Phytoseiulus macropilus+TX, Phytoseiulus persimilis (Spidex®+TX, Phytoline p®)+TX, Podisus maculiventris (Podisus®)+TX, Pseudacteon curvatus+TX, Pseudacteon obtusus+TX, Pseudacteon tricuspis+TX, Pseudaphycus maculipennis+TX, Pseudleptomastix mexicana+TX, Psyllaephagus pilosus+TX, Psyttalia concolor (complex)+TX, Quadrastichus spp.+TX, Rhyzobius lophanthae+TX, Rodolia cardinalis+TX, Rumina decollate+TX, Semielacher petiolatus+TX, Sitobion avenae (Ervibank®)+TX, Steinernema carpocapsae (Nematac C®+TX, Millenium®+TX, BioNem C®+TX, NemAttack®+TX, Nemastar®+TX, Capsanem®)+TX, Steinernema feltiae (NemaShield®+TX, Nemasys F®+TX, BioNem F®+TX, Steinernema-System®+TX, NemAttack®+TX, Nemaplus®+TX, Exhibitline sf®+TX, Scia-Rid®+TX, Entonem®)+TX, Steinernema kraussei (Nemasys L®+TX, BioNem L®+TX, Exhibitline srb®)+TX, Steinernema riobrave (BioVector®+TX, BioVektor®)+TX, Steinernema scapterisci (Nematac S®)+TX, Steinernema spp.+TX, Steinernematid spp. (Guardian Nematodes®)+TX, Stethorus punctillum (Stethorus®)+TX, Tamarixia radiate+TX, Tetrastichus setifer+TX, Thripobius semiluteus+TX, Torymus sinensis+TX, Trichogramma brassicae (Tricholine b®)+TX, Trichogramma brassicae (Tricho-Strip®)+TX, Trichogramma evanescens+TX, Trichogramma minutum+TX, Trichogramma ostriniae+TX, Trichogramma platneri+TX, Trichogramma pretiosum+TX, Xanthopimpla stemmator; and

[0597] other biologicals including: abscisic acid+TX, bioSea®+TX, Chondrostereum purpureum (Chontrol Paste®)+TX, Colletotrichum gloeosporioides (Collego®)+TX, Copper Octanoate (Cueva®)+TX, Delta traps (Trapline d®)+TX, Erwinia amylovora (Harpin) (ProAct®+TX, Ni-HIBIT Gold CST®)+TX, Ferri-phosphate (Ferramol®)+TX, Funnel traps (Trapline y®)+TX, Gallex®+TX, Grower's Secret®+TX, Homo-brassonolide+TX, Iron Phosphate (Lilly Miller Worry Free Ferramol Slug & Snail Bait®)+TX, MCP hail trap (Trapline f®)+TX, Microctonus hyperodae+TX, Mycoleptodiscus terrestris (Des-X®)+TX, BioGain®+TX, Aminomite®+TX, Zenox®+TX, Pheromone trap (Thripline Ams®)+TX, potassium bicarbonate (MilStop®)+TX, potassium salts of fatty acids (Sanova®)+TX, potassium silicate solution (Sil-Matrix®)+TX, potassium iodide+potassiumthiocyanate (Enzicur®)+TX, SuffOil-X®+TX, Spider venom+TX, Nosema locustae (Semaspore Organic Grasshopper Control®)+TX, Sticky traps (Trapline YF®+TX, Rebell Amarillo®)+TX and Traps (Takitrapline y+b®)+TX.

[0598] The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The above described mixing partners are known. Where the active ingredients are included in “The Pesticide Manual” [The Pesticide Manual—A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound “abamectin” is described under entry number (1). Where “[CCN]” is added hereinabove to the particular compound, the compound in question is included in the “Compendium of Pesticide Common Names”, which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2004]; for example, the compound “acetoprole” is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html.

[0599] Most of the active ingredients described above are referred to hereinabove by a so-called “common name”, the relevant “ISO common name” or another “common name” being used in individual cases. If the designation is not a “common name”, the nature of the designation used instead is given in round brackets for the particular compound; in that case, the IUPAC name, the IUPAC/Chemical Abstracts name, a “chemical name”. a “traditional name”, a “compound name” or a “development code” is used or, if neither one of those designations nor a “common name” is used, an “alternative name” is employed. “CAS Reg. No” means the Chemical Abstracts Registry Number.

[0600] The active ingredient mixture of the compounds of formula I selected from the compounds defined in the Tables A-1 to A-92, and Table P, and with active ingredients described above comprises a compound selected from Tables A-1 to A-92, and Table P, and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5:1 and 1:5, special preference being given to a ratio of from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. Those mixing ratios are by weight.

[0601] The mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.

[0602] The mixtures comprising a compound of formula I selected from the compounds defined in the Tables A-1 to A-92, and Table P, and one or more active ingredients as described above can be applied, for example, in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula I and the active ingredients as described above is not essential for working the present invention.

[0603] The compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.

[0604] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds I for the preparation of these compositions are also a subject of the invention.

[0605] The application methods for the compositions, that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring—which are to be selected to suit the intended aims of the prevailing circumstances—and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention. Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.

[0606] A preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.

[0607] The compounds of formula I of the invention and compositions thereof are also be suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type. The propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing. Alternatively, the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention. Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds.

[0608] The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.

[0609] The present invention also comprises seeds coated or treated with or containing a compound of formula I. The term “coated or treated with and/or containing” generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the ingredient may penetrate into the seed material, depending on the method of application. When the said seed product is (re)planted, it may absorb the active ingredient. In an embodiment, the present invention makes available a plant propagation material adhered thereto with a compound of formula I. Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound of formula I.

[0610] Seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting. The seed treatment application of the compound formula I can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds.

[0611] The compounds of the invention can be distinguished from other similar compounds by virtue of greater efficacy at low application rates and/or different pest control, which can be verified by the person skilled in the art using the experimental procedures, using lower concentrations if necessary, for example 10 ppm, 5 ppm, 2 ppm, 1 ppm or 0.2 ppm; or lower application rates, such as 300, 200 or 100, mg of Al per m.sup.2. The greater efficacy can be observed by an increased safety profile (against non-target organisms above and below ground (such as fish, birds and bees), improved physico-chemical properties, or increased biodegradability).

BIOLOGICAL EXAMPLES

[0612] The Examples which follow serve to illustrate the invention. Certain compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 24 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

Example B1: Diabrotica balteata (Corn Root Worm)

[0613] Maize sprouts placed onto an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 4 days after infestation.

[0614] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:

[0615] P2, P3, P4, P5, P6, P7, P8, P14, P15, P16, P17, P18, P19, P20, P21, P22, P23, P24, P25, P27, P28, P29, P30, P31, P32, P33, P34, P35

Example B2: Euschistus heros (Neotropical Brown Stink Bug)

[0616] Soybean leaves on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions. After drying the leaves were infested with N2 nymphs. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation.

[0617] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:

[0618] P1, P2, P3, P7, P11, P12, P16, P17, P18, P22, P25, P29, P32, P33, P37, P38

Example B3: Frankliniella occidentalis (Western Flower Thrips):Feeding/Contact Activity

[0619] Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10′000 DMSO stock solutions. After drying the leaf discs were infested with a Frankliniella population of mixed ages. The samples were assessed for mortality 7 days after infestation.

[0620] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm:

[0621] P1, P4, P12, P16, P28, P37

Example B4: Chilo suppressalis (Striped Rice Stemborer)

[0622] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (6-8 per well). The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 6 days after infestation. Control of Chilo suppressalis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.

[0623] The following compounds resulted in at least 80% control in at least one of the categories (mortality, anti-feedant effect, or growth inhibition) at an application rate of 200 ppm:

[0624] P1, P3, P4, P8, P11, P12, P14, P19, P21, P25, P27, P28, P29, P30, P31, P32, P33, P34, P35, P36, P37

Example B5: Plutella xylostella (Diamond Back Moth)

[0625] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions by pipetting. After drying, Plutella eggs were pipetted through a plastic stencil onto a gel blotting paper and the plate was closed with it. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 8 days after infestation.

[0626] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:

[0627] P1, P2, P3, P4, P5, P7, P8, P9, P14, P15, P16, P17, P18, P21, P22, P23, P24, P25, P27, P28, P29, P30, P31, P32, P33, P34, P35, P36

Example B6: Myzus persicae (Green Peach Aphid): Feeding/Contact Activity

[0628] Sunflower leaf discs were placed onto agar in a 24-well microtiter plate and sprayed with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions. After drying, the leaf discs were infested with an aphid population of mixed ages. The samples were assessed for mortality 6 days after infestation.

[0629] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm:

[0630] P3, P4, P7, P11, P12, P16, P17, P18, P21, P22

Example B7: Myzus persicae (Green Peach Aphid): Systemic Activity

[0631] Roots of pea seedlings infested with an aphid population of mixed ages were placed directly into aqueous test solutions prepared from 10′000 DMSO stock solutions. The samples were assessed for mortality 6 days after placing seedlings into test solutions.

[0632] The following compounds resulted in at least 80% mortality at a test rate of 24 ppm:

[0633] P2, P12, P16, P17, P21

Example B8: Myzus persicae (Green Peach Aphid): Intrinsic Activity

[0634] Test compounds prepared from 10′000 ppm DMSO stock solutions were applied by pipette into 24-well microtiter plates and mixed with sucrose solution. The plates were closed with a stretched Parafilm. A plastic stencil with 24 holes was placed onto the plate and infested pea seedlings were placed directly on the Parafilm. The infested plate was closed with a gel blotting paper and another plastic stencil and then turned upside down. The samples were assessed for mortality 5 days after infestation.

[0635] The following compounds resulted in at least 80% mortality at a test rate of 12 ppm:

[0636] P2, P3, P4, P7, P11, P12, P16, P17, P18, P21, P22, P28, P30, P31, P32, P34, P36, P37, P38

Example B9: Spodoptera littoralis (Egyptian Cotton Leaf Worm)

[0637] Cotton leaf discs were placed onto agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions. After drying the leaf discs were infested with five L1 larvae. The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 3 days after infestation. Control of Spodoptera littoralis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.

[0638] The following compounds resulted in at least 80% control in at least one of the categories (mortality, anti-feedant effect, or growth inhibition) at an application rate of 200 ppm:

[0639] P2, P3, P4, P5, P7, P15, P16, P17, P18, P20, P21, P22, P23, P24, P25, P27, P28, P29, P30, P31, P32, P33, P34, P35, P36

Example B10: Spodoptera littoralis (Egyptian Cotton Leaf Worm)

[0640] Test compounds were applied by pipette from 10′000 ppm DMSO stock solutions into 24-well plates and mixed with agar. Lettuce seeds were placed onto the agar and the multi well plate was closed by another plate which contained also agar. After 7 days the compound was absorbed by the roots and the lettuce grew into the lid plate. The lettuce leaves were then cut off into the lid plate. Spodoptera eggs were pipetted through a plastic stencil onto a humid gel blotting paper and the lid plate was closed with it. The samples were assessed for mortality, anti-feedant effect and growth inhibition in comparison to untreated samples 6 days after infestation.

[0641] The following compounds gave an effect of at least 80% in at least one of the three categories (mortality, anti-feeding, or growth inhibition) at a test rate of 12.5 ppm:

[0642] P3, P15, P32

Example B11: Tetranychus urticae (Two-Spotted Spider Mite): Feeding/Contact Activity

[0643] Bean leaf discs on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions. After drying the leaf discs were infested with a mite population of mixed ages. The samples were assessed for mortality on mixed population (mobile stages) 8 days after infestation.

[0644] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm:

[0645] P36

Example B12: Thrips tabaci (Onion thrips): Feeding/Contact Activity

[0646] Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions. After drying the leaf discs were infested with a thrips population of mixed ages. The samples were assessed for mortality 6 days after infestation.

[0647] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm:

[0648] P5, P7, P17, P18, P22

Example B13: Myzus persicae (Green Peach Aphid)

[0649] Test compounds prepared from 10′000 ppm DMSO stock solutions were applied by a liquid handling robot into 96-well microtiter plates and mixed with a sucrose solution. Parafilm was stretched over the 96-well microtiter plate and a plastic stencil with 96 holes was placed onto the plate. Aphids were sieved into the wells directly onto the Parafilm. The infested plates were closed with a gel blotting card and a second plastic stencil and then turned upside down. The samples were assessed for mortality 5 days after infestation.

[0650] The following compounds resulted in at least 80% mortality at an application rate of 50 ppm:

[0651] P2, P3, P5, P7, P11, P12, P14, P15, P16, P17, P18, P21, P22, P30, P32, P33, P37, P38

Example B14: Plutella xylostella (Diamondback Moth)

[0652] 96-well microtiter plates containing artificial diet were treated with aqueous test solutions, prepared from 10′000 ppm DMSO stock solutions, by a liquid handling robot. After drying, eggs (˜30 per well) were infested onto a netted lid which was suspended above the diet. The eggs hatch and L1 larvae move down to the diet. The samples were assessed for mortality 9 days after infestation.

[0653] The following compounds gave an effect of at least 80% average mortality at an application rate of 500 ppm:

[0654] P2, P3, P5, P6, P7, P9, P15, P16, P17, P18, P20, P22, P24, P25, P30, P31, P32, P33, P38.