Pesticidally active pryazole derivatives

Abstract

Compounds of formula (I), as defined herein, to processes for preparing them, to pesticidal, in particular insecticidal, acaricidal, molluscicidal and nematicidal compositions comprising them and to methods of using them to combat and control pests such as insect, acarine, mollusc and nematode pests. ##STR00001##

Claims

1. A compound of formula (I), ##STR00142## wherein R.sup.1 is selected from H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6 alkynyl, C.sub.3-C.sub.7 cycloalkyl, C.sub.3-C.sub.7 cycloalkyl-C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.6-alkylcarbonyl, C.sub.1-C.sub.6-alkoxycarbonyl, aryl(C.sub.0-C.sub.3)-alkyl and heteroaryl(C.sub.0-C.sub.3)-alkyl, wherein each of C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6 alkenyl, C.sub.3-C.sub.6 alkynyl, C.sub.3-C.sub.7 cycloalkyl, C.sub.3-C.sub.7 cycloalkyl-C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.6-alkylcarbonyl, C.sub.1-C.sub.6-alkoxycarbonyl, aryl(C.sub.0-C.sub.3)-alkyl and heteroaryl(C.sub.0-C.sub.3)-alkyl is unsubstituted or substituted with 1 to 5 substituents independently selected from halogen, cyano, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-alkoxycarbonyl; Q is selected from H, hydroxy, HC(O), C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6 alkynyl, C.sub.3-C.sub.7 cycloalkyl, C.sub.3-C.sub.7 heterocycloalkyl, C.sub.3-C.sub.7 cycloalkyl-C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.3-alkyl-C.sub.3-C.sub.7 cycloalkyl, aryl(C.sub.0-C.sub.3)-alkyl, heteroaryl(C.sub.0-C.sub.3)-alkyl, NC.sub.1-C.sub.6-alkylamino, NC.sub.1-C.sub.6-alkylcarbonylamino and N,N-di (C.sub.1-C.sub.6-alkyl)amino, wherein each of C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6 alkenyl, C.sub.3-C.sub.6 alkynyl, C.sub.3-C.sub.7 cycloalkyl, C.sub.3-C.sub.7 heterocycloalkyl, C.sub.3-C.sub.7 cycloalkyl-C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.3-alkyl-C.sub.3-C.sub.7 cycloalkyl, aryl(C.sub.0-C.sub.3)-alkyl, heteroaryl(C.sub.0-C.sub.3)-alkyl, NC.sub.1-C.sub.6-alkylamino, NC.sub.1-C.sub.6-alkylcarbonylamino and N,N-di (C.sub.1-C.sub.6-alkyl)amino is unsubstituted or substituted with 1 to 5 substituents independently selected from halogen, hydroxyl, nitro, amino, cyano, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkoxycarbonyl, hydroxycarbonyl, C.sub.1-C.sub.6-alkylcarbamoyl, C.sub.3-C.sub.6-cycloalkylcarbamoyl and phenyl; W is O or S; A.sup.1 is CR.sup.2 or N; A.sup.2 is CR.sup.3 or N; A.sup.3 is CR.sup.4 or N; A.sup.4 is CR.sup.5 or N; with the proviso that no more than 3 of A.sup.1, A.sup.2, A.sup.3 and A.sup.4 are N; R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are independently selected from H, halogen, cyano, nitro, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, NC.sub.1-C.sub.6-alkoxy-imino-C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.6-alkylsulfanyl, C.sub.1-C.sub.6-alkylsulfinyl, C.sub.1-C.sub.6-alkylsulfonyl, NC.sub.1-C.sub.6-alkylamino and N,N-di-C.sub.1-C.sub.6-alkylamino, wherein each of C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, NC.sub.1-C.sub.6-alkoxy-imino-C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.6-alkylsulfanyl, C.sub.1-C.sub.6-alkylsulfinyl, C.sub.1-C.sub.6-alkylsulfonyl, NC.sub.1-C.sub.6-alkylamino and N,N-di-C.sub.1-C.sub.6-alkylamino is unsubstituted or substituted with 1 to 5 substituents independently selected from halogen, hydroxy, nitro, amino, cyano, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkoxycarbonyl, hydroxycarbonyl, C.sub.1-C.sub.6-alkylcarbamoyl, C.sub.3-C.sub.6-cycloalkylcarbamoyl and phenyl; T is a 5-membered heteroaryl of formula ##STR00143## wherein ##STR00144## indicates the bond to the pyrazole group; D.sup.1 is selected from CR.sup.6a, N, NR.sup.6b, O and S; D.sup.2 is selected from CR.sup.7a, N, NR.sup.7b, O and S; D.sup.3 is C or N; D.sup.4 is selected from CR.sup.8a, N, NR.sup.8b and O; D.sup.5 is C or N; with the proviso that at least one of D.sup.1, D.sup.2, D.sup.3, D.sup.4 and D.sup.5 is selected from N, O and S, and that no more than one of D.sup.1, D.sup.2 and D.sup.4 is O or S, and that at least one of D.sup.3 and D.sup.5 is C; R.sup.6a, R.sup.7a and R.sup.8a are independently selected from H, halogen, cyano, nitro, amino, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylcarbonyl, C.sub.1-C.sub.6-alkylsulfanyl, C.sub.1-C.sub.6-alkylsulfinyl and C.sub.1-C.sub.6-alkylsulfonyl, wherein each of C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylcarbonyl, C.sub.1-C.sub.6-alkylsulfanyl, C.sub.1-C.sub.6-alkylsulfinyl, C.sub.1-C.sub.6-alkylsulfonyl is unsubstituted or substituted with 1 to 5 halogen; R.sup.6b, R.sup.7b and R.sup.8b are independently selected from H and C.sub.1-C.sub.6-alkyl, wherein each of C.sub.1-C.sub.6-alkyl is unsubstituted or substituted with 1 to 5 halogen; Z.sup.1 is selected from C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.7 heterocycloalkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl and C.sub.3-C.sub.6-halocycloalkyl, wherein each of C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.7 heterocycloalkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl and C.sub.3-C.sub.6-halocycloalkyl is unsubstituted or substituted with 1 to 5 substituents independently selected from halogen, hydroxy, nitro, amino, cyano, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkoxycarbonyl, hydroxycarbonyl, C.sub.1-C.sub.6-alkylcarbamoyl, C.sub.3-C.sub.6-cycloalkylcarbamoyl and phenyl; U is OCHF.sub.2; Z.sup.3 is selected from H, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-cycloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, aryl and heteroaryl, wherein each of C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-cycloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, aryl and heteroaryl is unsubstituted or substituted with 1 to 5 substituents independently selected from halogen, hydroxy, nitro, amino, cyano, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkoxycarbonyl, hydroxycarbonyl, C.sub.1-C.sub.6-alkylcarbamoyl, C.sub.3-C.sub.6-cycloalkylcarbamoyl and phenyl; or an agrochemically acceptable salt or N-oxide thereof.

2. A compound according to claim 1, wherein T is ##STR00145## wherein ##STR00146## indicates the bond to the pyrazole group.

3. A compound according to claim 1, wherein Z.sup.1 is selected from methyl, ethyl, 1,1-dimethylethyl, difluoromethyl, trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, bromodichloromethyl, 1-fluoroethyl, 1-fluoro-1-methylethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,2,2,2-tetrafluoroethyl, 1-chloro-1,2,2,2-tetrafluoroethyl, 2,2,2-trichloroethyl, 2-chloro-2,2-difluoroethyl, 1,1-difluoroethyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoro-isopropyl, nonafluoro-n-butyl, cyclopropyl, 1-chlorocyclopropyl, 1-fluorocyclopropyl, 1-bromocyclopropyl, 1-cyano-cyclopropyl, 1-trifluoromethyl-cyclopropyl, cyclobutyl and 2,2-difluoro-1-methyl-cyclopropyl.

4. A compound according to claim 1, wherein Z.sup.1 is CF.sub.2CF.sub.3.

5. A compound according to claim 1, wherein Z.sup.3 is selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, ethenyl, 1-propenyl, 1-propinyl, cyclopropyl, 1-butinyl, difluoromethyl, trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, 1-fluoroethyl, 1 fluoro-1-methylethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,5-dichlorophenyl, 3,4-dichlorophenyl, 2,6-dichlorophenyl 2,6-dichloro-4-trifluoromethylphenyl, 3-chlor-5-trifluoromethylpyridin-2-yl, 4-NO.sub.2-phenyl and 3-chloro-pyridin-2-yl.

6. A compound according to claim 1, wherein Z.sup.3 is methyl.

7. A compound according to claim 1, wherein: R.sup.1 is H or C.sub.1-C.sub.6alkyl; Q is cyclopropyl or 1-cyanocyclopropyl; T is ##STR00147## R.sup.7a and R.sup.8a are hydrogen; W is O; A.sup.1 is CH; A.sup.2 is CH or N; A.sup.3 is CR.sup.4; A.sup.4 is CH; R.sup.4 is selected from H, halogen, cyano, and C.sub.1-C.sub.6alkyl; Z.sup.1 is C.sub.1-C.sub.6-haloalkyl; and Z.sub.3 is H or C.sub.1-C.sub.6alkyl.

8. A compound according to claim 7, wherein T is T47.

9. A compound according to claim 8, wherein: R.sup.1 is C.sub.1-C.sub.6alkyl; R.sup.4 is selected from H, halogen, and cyano; and Z.sub.3 is C.sub.1-C.sub.6alkyl.

10. A compound according to claim 9, wherein: R.sup.1 is methyl or ethyl; Z.sup.1 is CF.sub.2CF.sub.3; and Z.sup.3 is methyl.

11. A compound according to claim 10, wherein A.sup.2 is CH.

12. A compound according to claim 7, wherein T is T52.

13. A compound according to claim 12, wherein: R.sup.1 is C.sub.1-C.sub.6alkyl; R.sup.4 is selected from H, halogen, and cyano; and Z.sub.3 is C.sub.1-C.sub.6alkyl.

14. A pesticidal composition, which comprises at least one compound according to claim 1, as active ingredient and at least one auxiliary.

15. The composition according to claim 14, which further comprises one or more other insecticidally, acaricidally, nematicidally and/or fungicidally active agents.

16. A method for controlling pests, which comprises applying a composition according to claim 14 to the pests or their environment.

17. A method for the protection of plant propagation material from the attack by pests, which comprises treating the propagation material or the site, where the propagation material is planted, with a composition according to claim 14.

18. A coated plant propagation material, wherein the coating of the plant propagation material comprises a compound as defined in claim 1.

Description

EXAMPLES

(1) The following compounds according to embodiment 1 may be prepared according to the methods described herein or according to known methods.

Experimental

(2) The following examples are intended to illustrate the invention and are not to be construed as being limitations thereon.

(3) Mp means melting point in C. .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.

(4) LC MS Method A: Standard:

(5) Spectra were recorded on a Mass Spectrometer from Waters (SQD or ZQ Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150 C., Desolvation Temperature: 350 C., Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment and diode-array detector. Solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 m, 302.1 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: gradient: 0 min 0% B, 100% A; 1.2-1.5 min 100% B; Flow (ml/min) 0.85.

(6) LC MS Method B: Standard Long:

(7) Spectra were recorded on a Mass Spectrometer from Waters (SQD or ZQ Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150 C., Desolvation Temperature: 350 C., Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment and diode-array detector. Solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 m, 302.1 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: gradient: 0 min 0% B, 100% A; 2.7-3.0 min 100% B; Flow (ml/min) 0.85.

(8) LC MS Method C: Unpolar:

(9) Spectra were recorded on a Mass Spectrometer from Waters (SQD or ZQ Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150 C., Desolvation Temperature: 350 C., Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment and diode-array detector. Solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 m, 302.1 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: gradient: 0 min 40% B, 60% A; 1.2-1.5 min 100% B; Flow (ml/min) 0.85.

Example 1: 2-chloro-N-(1-cyanocyclopropyl)-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]benzamide

a) Preparation of 2-Methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-ol

(10) ##STR00048##

(11) A solution of ethyl 4,4,5,5,5-pentafluoro-3-oxo-pentanoate (30 g, 128 mmol) and methyl hydrazine (6.2 g, 135 mmol) in 120 ml of ethanol was stirred at RT overnight under Argon, the reaction mixture was then heated to 60 C. for 24 h to have a complete conversion. The solvent was evaporated under vacuum and the residue purified by flash chromatography to give 2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-ol as a beige solid.

(12) .sup.1H NMR (400 MHz, DMSO-d.sub.6) ppm 3.60 (s, 3H) 5.71 (s, 1H) 11.70 (s, 1H).

(13) LC-MS (Method B): t.sub.R=1.03 min, m/z=215 [M1], 217 [M+1].

b) Preparation of 5-Chloro-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)pyrazole-4-carbaldehyde

(14) ##STR00049##

(15) Under Argon and at 0 C., POCl.sub.3 (16.3 ml, 175 mmol) was carefully added dropwise to 2.5 ml of N,N-dimethylformamide. To this reaction mixture was added 2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-ol (5 g, 23.1 mmol), the mixture was then heated at 100 C. for 18 h. The reaction mixture was then cooled to RT and poured slowly on an aqueous solution of sodium hydrogen carbonate, the solution was extracted three time with ethyl acetate, dried over magnesium sulfate and evaporated under vacuum. The residue was purified by flash chromatography to give 5-chloro-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)pyrazole-4-carbaldehyde as a yellow oil.

(16) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 4.00 (s, 3H) 10.00 (s, 1H)

(17) LC-MS (Method B): t.sub.R=1.37 min, m/z=263 [M+1].

c) Preparation of 5-(4-Bromopyrazol-1-yl)-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)pyrazole-4-carbaldehyde

(18) ##STR00050##

(19) Under Argon, 5-chloro-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)pyrazole-4-carbaldehyde (12.85 g, 48.9 mmol) was dissolved in acetonitrile (500 ml), then cesium carbonate (31.89 g, 97.8 mmol) was added. To this mixture, 4-bromo-1H-pyrazole (7.9 g, 53.8 mmol) was added and the mixture was stirred at RT for 18 h. The mixture was diluted with ethyl acetate, washed with water and brine, the organic layers were dried over magnesium sulfate and evaporated under vacuum. The residue was purified by flash chromatography to give 5-(4-bromopyrazol-1-yl)-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)pyrazole-4-carbaldehyde as a white solid.

(20) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 3.98 (s, 3H) 7.83 (s, 1H) 8.09 (s, 1H) 9.97 (s, 1H).

(21) LC-MS (Method B): t.sub.R=1.63 min, m/z=371 [M1], 373 [M+1].

d) Preparation of 5-(4-Bromopyrazol-1-yl)-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)pyrazol-4-ol

(22) ##STR00051##

(23) To a solution of 5-(4-bromopyrazol-1-yl)-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)pyrazole-4-carbaldehyde (500 mg, 1.34 mmol) in dichloromethane (5 ml) was added meta-chloroperbenzoic acid (642 mg, 2.68 mmol). The mixture was stirred at RT for 5 days. The mixture was diluted with ethyl acetate, and washed with water, and aqueous solutions of sodium hydrogen carbonate and sodium thiosulfate. The organic layers were dried over magnesium sulfate and reduced under vacuum. The residue was purified by flash chromatography to give 5-(4-bromopyrazol-1-yl)-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)pyrazol-4-ol as a white solid.

(24) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 3.79 (s, 3H) 6.35 (s, 1H) 7.66 (s, 1H) 7.75 (s, 1H) LC-MS (Method B): t.sub.R=1.39 min, m/z=361 [M1], 363 [M+1].

e) Preparation of 5-(4-Bromopyrazol-1-yl)-4-(difluoromethoxy)-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)pyrazole

(25) ##STR00052##

(26) To a solution of 5-(4-bromopyrazol-1-yl)-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)pyrazol-4-ol (466 mg, 1.29 mmol) and potassium hydroxide (1.44 g, 25.81 mmol) in a mixture of 4 ml of acetonitrile/water (1:1) was added at 78 C. 1-[[bromo(difluoro)methyl]-ethoxy-phosphoryl]oxyethane (689 mg, 2.58 mmol). The mixture was allowed to warm to RT and stirred in a closed vessel for 3 h. In order to complete the reaction, 1-[[bromo(difluoro)methyl]-ethoxy-phosphoryl]oxyethane (172 mg, 0.645 mmol) was added at 78 C. and the reaction was stirred at RT for another 1 h. The reaction mixture was diluted with ether, washed with brine and water. The organic layers were dried over magnesium sulfate and reduced under vacuum. The residue was purified by flash chromatography to give 5-(4-bromopyrazol-1-yl)-4-(difluoro-methoxy)-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)pyrazole as a colourless oil.

(27) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 3.87 (s, 3H) 6.08-6.52 (m, 1H) 7.78 (s, 1H) 7.81 (s, 1H).

(28) LC-MS (Method B): t.sub.R=1.79 min, m/z=409 [M1], 411 [M+1].

f) Preparation of Methyl 2-chloro-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]benzoate

(29) ##STR00053##

(30) In a microwave tube, 5-(4-bromopyrazol-1-yl)-4-(difluoromethoxy)-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)pyrazole (50 mg, 0.121 mmol), 5-(4-bromopyrazol-1-yl)-4-(difluoromethoxy)-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)pyrazole (56 mg, 0.182 mmol) and cesium fluoride (37 mg, 0.243 mmol) were dissolved in 4 ml dioxane/water (3/1). The mixture was purged with argon for 5 min. Pd(dppf)Cl.sub.2 (4.8 mg, 0.006 mmol) was added and the mixture was irradiated in the microwave oven at 160 C. for 30 min. The mixture was evaporated, diluted with ethyl acetate, quenched with 25 ml water, extracted three times with ethyl acetate; the combined organic phases were washed with brine, dried over sodium sulfate, filtrated and evaporated. The black-brown resin was purified over silica gel to give methyl 2-chloro-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]benzoate as a colorless oil.

(31) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 3.93 (s, 3H) 3.98 (s, 3H) 6.11-6.51 (m, 1H) 7.49-7.54 (m, 1H) 7.49-7.54 (m, 1H) 7.55-7.60 (m, 1H) 7.97-8.04 (m, 2H) 8.13 (s, 1H) LC-MS (Method B): t.sub.R=1.98 min, m/z=499 [M1], 501 [M+1].

g) Preparation of 2-Chloro-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]benzoic acid

(32) ##STR00054##

(33) Methyl 2-chloro-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]benzoate (192 mg, 0.38 mmol) was dissolved in 5 ml tetrahydrofuran/water (4:1). LiOH monohydrate (46 mg, 1.9 mmol) was added in one portion and the reaction mixture was warmed at 50 C. for 3 h. The mixture was evaporated, diluted with ethyl acetate and 25 ml water. The water phase was acidified to pH 4, extracted with 330 ml ethyl acetate; the organic phase was washed with brine, dried over sodium sulfate, filtrated and evaporated. The residue was purified by flash chromatography to give 2-chloro-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]benzoic acid as a colorless oil.

(34) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 3.94 (s, 3H) 6.13-6.51 (m, 1H) 7.54-7.58 (m, 1H) 7.61-7.66 (m, 1H) 8.04 (s, 1H) 8.13-8.18 (m, 2H).

(35) LC-MS (Method B): t.sub.R=1.73 min, m/z=485 [M1], 487 [M+1].

h) Preparation of 2-Chloro-N-(1-cyanocyclopropyl)-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]benzamide

(36) ##STR00055##

(37) A mixture of 2-chloro-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]benzoic acid (45 mg, 0.092 mmol), 1-amino-1-cyano-cyclopropane hydrochloride (33.5 mg, 0.277 mmol), EDCl (22.61 mg, 0.115 mmol), HOAT (16.39 mg, 0.115 mmol) and triethylamine (42.1 mg, 0.416 mmol) in 3 ml DMF was stirred at RT for 2 hours. The mixture was diluted with ethyl acetate, quenched with water; the organic phase was washed successively with water and once with brine. The organic phase was dried over magnesium sulfate, filtrated and evaporated. The crude product was purified by flash chromatography to give 2-chloro-N-(1-cyanocyclopropyl)-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]benzamide as a white solid.

(38) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 1.41-1.46 (m, 2H) 1.67-1.72 (m, 2H) 3.93 (s, 3H) 6.12-6.51 (m, 1H) 7.46 (d, J=8.07 Hz, 1H) 7.57 (dd, J=8.25, 2.38 Hz, 1H) 7.96 (d, J=2.20 Hz, 1H) 8.03 (s, 1H) 8.12 (s, 1H).

(39) LC-MS (Method B): t.sub.R=1.74 min, m/z=549 [M1], 551 [M+1].

(40) Mp: 138-139 C.

Example 2: 2-Chloro-N-cyclopropyl-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-pyrazol-3-yl]pyrazol-4-yl]benzamide

(41) ##STR00056##

(42) A mixture of 2-chloro-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]benzoic acid (45 mg, 0.092 mmol), cyclopropylamine (15.84 mg, 0.28 mmol), EDCl (22.61 mg, 0.115 mmol), HOAT (16.39 mg, 0.115 mmol) and triethylamine (32.75 mg, 0.323 mmol) in 3 ml DMF was stirred at RT for 2 hours. The mixture was diluted with ethyl acetate and water; the organic phase was washed successively with water and once with brine. The organic phase was dried over magnesium sulfate, filtrated and evaporated. The crude product was purified by flash chromatography to give 2-chloro-N-cyclopropyl-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]benzamide as a white solid.

(43) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 0.56-0.63 (m, 2H) 0.81-0.87 (m, 2H) 2.88 (tq, J=7.08, 3.71 Hz, 1H) 3.85 (s, 3H) 6.02-6.46 (m, 2H) 7.33-7.48 (m, 2H) 7.75-7.96 (m, 2H) 7.98-8.07 (m, 1H).

(44) LC-MS (Method B): t.sub.R=1.77 min, m/z=524 [M1], 526 [M+1].

Example 15: 2-Chloro-N-(1-cyanocyclopropyl)-5-[1-[2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-vinyl-pyrazol-3-yl]pyrazol-4-yl]benzamide

a) Preparation of 5-(4-Bromopyrazol-1-yl)-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)-4-vinyl-pyrazole

(45) ##STR00057##

(46) To a stirred mixture of methyl(triphenyl)phosphonium bromide (7.3 g, 20 mmol) in dry THF (100 ml) under argon at 78 C. was added dropwise n-BuLi (1.6 mol/L) in hexane (13 ml, 20 mmol)). The resulting mixture was stirred at 78 C. for 30 min. To this yellow mixture was added a solution of 5-(4-bromopyrazol-1-yl)-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)pyrazole-4-carbaldehyde (5.0 g, 13 mmol) in THF. The mixture was allowed to warm to RT. The reaction mixture was quenched with aqueous ammonium chloride and then diluted with ethyl acetate; organic phase was washed with water and brine, dried over magnesium and evaporated under vacuum. The crude product was purified by flash chromatography to give 5-(4-bromopyrazol-1-yl)-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)-4-vinyl-pyrazole as a white solid.

(47) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 3.73-3.76 (m, 3H) 4.91 (d, J=17.97 Hz, 1H) 5.20-5.28 (m, 1H) 6.44-6.53 (m, 1H) 7.66 (s, 1H) 7.85 (s, 1H).

(48) LC-MS (Method B): t.sub.R=1.89 min, m/z=369 [M1].

b) Preparation of Methyl 2-chloro-5-[1-[2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-vinyl-pyrazol-3-yl]pyrazol-4-yl]benzoate

(49) ##STR00058##

(50) 5-(4-Bromopyrazol-1-yl)-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)-4-vinyl-pyrazole (1.2 g, 3.2 mmol), methyl 2-chloro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate (1.2 g, 3.9 mmol) and sodium carbonate (1.7 g, 16 mmol) were dissolved in 10 ml 1,2-dimethoxyethane and 2 ml water. The mixture was purged with argon for 5 min. Then Pd(P(Ph.sub.3)).sub.4 (560 mg, 0.49 mmol) was added and the mixture was irradiated in the microwave oven at 100 C. for 40 min. The reaction was not complete and 0.05 eq. of Pd(P(Ph.sub.3)).sub.4 was added and the mixture was further irradiated in the microwave oven at 120 C. for 20 min. The mixture was filtrated over celite and evaporated to dryness; crude mixture was separated over silica gel to give 2-chloro-5-[1-[2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-vinyl-pyrazol-3-yl]pyrazol-4-yl]benzoate as a yellow oil.

(51) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 3.81 (s, 3H) 3.99 (s, 3H) 4.95 (d, J=17.97 Hz, 1H) 5.20-5.25 (m, 1H) 6.52 (dd, J=17.97, 11.74 Hz, 1H) 7.52-7.55 (m, 1H) 7.58-7.62 (m, 1H) 7.91 (d, J=0.73 Hz, 1H) 8.01 (d, J=2.20 Hz, 1H) 8.17 (d, J=0.73 Hz, 1H).

(52) LC-MS (Method B): t.sub.R=2.09 min, m/z=459 [M1], 461 [M+1].

c) Preparation of 2-Chloro-5-[1-[2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-vinyl-pyrazol-3-yl]pyrazol-4-yl]benzoic acid

(53) ##STR00059##

(54) Methyl 2-chloro-5-[1-[2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-vinyl-pyrazol-3-yl]pyrazol-4-yl]benzoate (450 mg, 0.976 mmol) was dissolved in a mixture of THF and water (5 ml, 4:1). LiOH monohydrate (233 mg, 9.76 mmol) was added in one portion and the reaction mixture was stirred at RT overnight. The mixture was evaporated, diluted with ethyl acetate, quenched with 25 ml water and acidified to pH 4. The water phase was extracted 3 times with ethyl acetate; the combined organic phases were washed with brine, dried over sodium sulfate, filtrated and evaporated. The crude product was purified over silica gel to give 2-chloro-5-[1-[2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-vinyl-pyrazol-3-yl]pyrazol-4-yl]benzoic acid as a white solid.

(55) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 3.82 (s, 3H) 4.96 (d, J=17.97 Hz, 1H) 5.23 (dd, J=11.74, 1.10 Hz, 1H) 6.52 (dd, J=17.97, 11.74 Hz, 1H) 7.56-7.59 (m, 1H) 7.64-7.68 (m, 1H) 7.93 (d, J=0.73 Hz, 1H) 8.19 (dd, J=3.30, 1.47 Hz, 2H).

(56) LC-MS (Method B): t.sub.R=1.8 min, m/z=445 [M1], 447 [M+1].

d) Preparation of 2-Chloro-N-(1-cyanocyclopropyl)-5-[1-[2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-vinyl-pyrazol-3-yl]pyrazol-4-yl]benzamide

(57) ##STR00060##

(58) A mixture of 2-chloro-5-[1-[2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-vinyl-pyrazol-3-yl]pyrazol-4-yl]benzoic acid (158 mg, 0.353 mmol), 1-amino-1-cyano-cyclopropane hydrochloride (128 mg, 1.06 mmol), EDCl (86.47 mg, 0.44 mmol), HOAT (62 mg, 0.44 mmol) and triethylamine (161 mg, 1.6 mmol) in 5 ml DMF was stirred at RT for 16 hours. The mixture was diluted with ethyl acetate and water. The organic phase was washed successively with water and once with brine and a solution of hydrochloride acid (1N). The organic phase was dried over magnesium sulfate, filtrated and evaporated. The crude product was purified by chromatography to give 2-chloro-N-(1-cyanocyclopropyl)-5-[1-[2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-vinyl-pyrazol-3-yl]pyrazol-4-yl]benzamide as a white solid.

(59) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 1.41-1.44 (m, 2H) 1.68-1.72 (m, 2H) 3.79 (s, 3H) 4.92 (d, J=17.97 Hz, 1H) 5.17-5.23 (m, 1H) 6.49 (dd, J=17.79, 11.55 Hz, 1H) 6.90 (s, 1H) 7.45 (d, J=8.07 Hz, 1H) 7.57 (dd, J=8.44, 2.20 Hz, 1H) 7.90 (s, 1H) 7.96 (d, J=2.20 Hz, 1H) 8.14 (d, J=0.73 Hz, 1H).

(60) LC-MS (Method B): t.sub.R=1.77 min, m/z=509 [M1], 511 [M+1].

Example 16: Preparation of 2-Chloro-N-cyclopropyl-5-[1-[2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-vinyl-pyrazol-3-yl]pyrazol-4-yl]benzamide

a) Preparation of 2-Chloro-5-[1-[2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-vinyl-pyrazol-3-yl]pyrazol-4-yl]benzoyl chloride

(61) ##STR00061##

(62) To a suspension of 2-chloro-5-[1-[2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-vinyl-pyrazol-3-yl]pyrazol-4-yl]benzoic acid (example 3, step c; 50 mg, 0.111 mmol) in 5 ml dry dichloromethane was added sequentially oxalyl dichloride (2 ml) and one drops of DMF in argon atmosphere. The reaction mixture was stirred until gas evolution stopped. The solvent was removed under reduced pressure to dryness and the crude product was used directly for the next step.

b) Preparation of 2-Chloro-N-cyclopropyl-5-[1-[2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-vinyl-pyrazol-3-yl]pyrazol-4-yl]benzamide

(63) ##STR00062##

(64) To a solution of cyclopropanamine (19 mg, 0.335 mmol) and 2-chloro-5-[1-[2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-vinyl-pyrazol-3-yl]pyrazol-4-yl]benzoyl chloride (52 mg, 0.111 mmol) in 3 ml THF was added pyridine (44 mg, 0.0559 mmol) at RT. The reaction mixture was heated to 60 C. for 16 hours. The mixture was diluted with water and ethyl acetate, washed with water/brine and with diluted hydrochloride acid (1N). The organic layer was dried over magnesium sulfate and evaporated under vacuum. The crude product was purified by flash chromatography to give a white solid.

(65) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 0.66-0.70 (m, 2H) 0.89-0.94 (m, 2H) 2.91-2.97 (m, 1H) 3.78 (s, 3H) 4.88-4.95 (m, 1H) 5.19 (dd, J=11.55, 0.92 Hz, 1H) 6.40 (br. s., 1H) 6.49 (dd, J=17.97, 11.37 Hz, 1H) 7.41-7.45 (m, 1H) 7.49-7.53 (m, 1H) 7.87 (d, J=0.73 Hz, 2H) 8.13 (d, J=0.73 Hz, 1H).

(66) LC-MS (Method B): t.sub.R=1.86 min, m/z=484 [M1], 486 [M+1].

Example 64: Preparation of 2-Chloro-N-(1-cyanocyclopropyl)-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]triazol-4-yl]benzamide

a) Preparation of 5-Azido-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)pyrazole-4-carbaldehyde

(67) ##STR00063##

(68) 5-Chloro-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)pyrazole-4-carbaldehyde (1.0 g, 3.8 mmol) was dissolved in dimethyl sulfoxide (5.0 ml), then sodium azide (0.28 g, 4.2 mmol) was added. The mixture was stirred at RT overnight (18 h). The mixture was diluted with diethyl ether, washed with water and brine, the organic layers were dried over magnesium sulfate and evaporated under vacuum to obtain the crude product which was taken forward to the next step.

(69) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 3.78 (s, 3H), 9.92 (s, 1H).

(70) LC-MS (Method A): t.sub.R=1.00 min.

b) Preparation of Methyl 2-chloro-5-[1-[4-formyl-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]triazol-4-yl]benzoate

(71) ##STR00064##

(72) To a solution of 5-azido-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)pyrazole-4-carbaldehyde (1.0 g, 3.7 mmol) in a mixture of tert-butanol (4 ml) and water (2 ml) were added methyl 2-chloro-5-ethynyl-benzoate (0.60 g, 3.1 mmol), L-Ascorbic acid sodium salt (0.062 g, 0.31 mmol) and copper(II) sulfate pentahydrate (0.0049 g, 0.031 mmol). The mixture was stirred at RT overnight (18 h). The mixture was diluted with ethyl acetate, washed with water and brine, the organic layer were dried over magnesium sulfate, filtered and evaporated under vacuum. The crude product was purified by flash chromatography (Silica, Cyclohexane/gradient of ethyl acetate 0 to 25%) to afford a yellow solid.

(73) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 3.99 (s, 3H), 4.08 (s, 3H), 7.61 (d, J=8.4 Hz, 1H), 8.02 (dd, J=8.4, 2.2 Hz, 1H), 8.38 (d, J=2.2 Hz, 1H), 8.50 (s, 1H), 10.03 (s, 1H).

(74) LC-MS (Method A): t.sub.R=1.12 min, m/z=464 [M+1].

c) Preparation of Methyl 2-chloro-5-[1-[4-hydroxy-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]triazol-4-yl]benzoate

(75) ##STR00065##

(76) To a stirred solution of methyl 2-chloro-5-[1-[4-formyl-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]triazol-4-yl]benzoate (1.5 g, 3.2 mmol) in trifluoroacetic acid (4.2 ml) was added urea hydrogen peroxide (0.63 g, 6.5 mmol) in 5 portions over a period of 25 minutes at RT under argon. The reaction mixture was stirred at RT for 2 h and then at 40 C. for 1 h. The mixture was diluted with ethyl acetate, and consecutively washed with water, aqueous solutions of sodium hydrogen carbonate and saturated sodium metabisulfite solutions. The organic layer were dried over magnesium sulfate, filtered and evaporated under vacuum. The residue was purified by flash chromatography to give the title compound as a yellow solid.

(77) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 3.99 (2 overlapped s, 6H), 5.35 (br. S, 1H), 7.59 (d, J=8.4 Hz, 1H), 7.97 (dd, J=8.4, 2.2 Hz, 1H), 8.22 (s, 1H), 8.31 (d, J=2.2 Hz, 1H).

(78) LC-MS (Method A): t.sub.R=1.04 min, m/z=450 [M1], 452 [M+1].

d) Preparation of 2-Chloro-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]triazol-4-yl]benzoic acid

(79) ##STR00066##

(80) To a stirred solution of 2-chloro-5-[1-[4-hydroxy-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]triazol-4-yl]benzoate (0.24 g, 0.53 mmol) and potassium hydroxide (0.6 g, 11 mmol) in a mixture of acetonitrile/water=1:1 (10.6 ml) cooled to 78 C. was added diethyl (bromodifluoromethyl)phosphonate (0.29 g, 1.1 mmol). The reaction mixture was allowed to warm to RT and then it was stirred at this temperature over a weekend. The conversion was monitored by GCMS and UPLC. The reaction mixture was diluted with ethyl acetate and then consecutively washed with 1N HCl, water and brine. The organic layer was dried over magnesium sulfate, filtered and evaporated under vacuum to afford the title compound which was used in the next step without further purification.

(81) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 3.98 (s, 3H), 6.37 (t, J=72.6 Hz, 1H), 7.64 (d, J=8.4 Hz, 1H), 8.08 (dd, J=8.4, 2.2 Hz, 1H), 8.22 (s, 1H), 8.47 (d, J=2.2 Hz, 1H).

(82) LC-MS (Method A): t.sub.R=1.04 min, m/z=486 [M1], 488 [M+1].

e) Preparation of 2-Chloro-N-(1-cyanocyclopropyl)-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]triazol-4-yl]benzamide

(83) ##STR00067##

(84) Oxalyl chloride (0.07 g, 0.53 mmol) was dissolved in dry dichloromethane (2.7 ml) followed by the addition of 1 drop of dimethylformamide and 2-chloro-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]triazol-4-yl]benzoic acid (0.13 g, 0.27 mmol). The reaction mixture was stirred at RT for 30 minutes and then at 35 C. for 10 minutes. Afterwards the mixture was evaporated to dryness. The remaining acid chloride was dissolved in dry pyridine (1.3 ml) and 1-amino-1-cyano-cyclopropane hydrochloride (0.047 g, 0.40 mmol) was added at 0 C. The reaction mixture was stirred at RT for 1 h. The product was isolated by flash chromatography.

(85) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 1.44 (m, 2H), 1.72 (m, 2H), 3.99 (s, 3H), 6.37 (t, J=72.4 Hz, 1H), 6.90 (brs, 1H), 7.56 (d, J=8.4 Hz, 1H), 8.08 (dd, J=8.4, 2.2 Hz, 1H), 8.21 (d, J=2.2 Hz, 1H), 8.22 (s, 1H), 8.47 (d, J=2.2 Hz, 1H).

(86) LC-MS (Method A): t.sub.R=1.05 min, m/z=550 [M1], 552 [M+1].

Example 54: Preparation of 2-Chloro-N-cyclopropyl-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]-N-methyl-pyridine-3-carboxamide

a) Preparation of 4-(Difluoromethoxy)-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)-5-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazol-1-yl]pyrazole

(87) ##STR00068##

(88) A microwave tube was charged with 5-(4-bromopyrazol-1-yl)-4-(difluoromethoxy)-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)pyrazole (8.0 g, 18 mmol), 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2-dioxaborolane (5.6 g, 22 mmol), potassium acetate (5.4 g, 55 mmol) and dioxane (37 ml). After purging with argon, Pd(PPh.sub.3).sub.4 (1.1 g, 0.91 mmol) was added. The tube was sealed up and heated in the microwave reacter to 140 C. for 45 min. The reaction mixture was taken up in ethyl acetate, washed with water and brine. The organic layer were dried over magnesium sulfate, filtered and evaporated under vacuum to obtain the crude product which was used directly in the next step.

(89) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 1.36 (s, 12H), 3.85 (s, 3H), 6.28 (t, J=72.8 Hz, 1H), 8.01 (s, 1H), 8.07 (s, 1H).

(90) LC-MS (Method A): t.sub.R=1.18 min, m/z=457 [M1], 459 [M+1].

b) Preparation of Methyl 2-chloro-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]pyridine-3-carboxylate

(91) ##STR00069##

(92) A microwave tube was charged with 4-(difluoromethoxy)-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)-5-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazol-1-yl]pyrazole (3.1 g, 4.4 mmol), methyl 5-bromo-2-chloro-pyridine-3-carboxylate (1.0 g, 4.0 mmol), tetrahydrofurane (53 ml), water (5.9 ml) and potassium hydrocarbonate (1.2 g, 12 mmol). After purging with argon, Pd(dppf).sub.2Cl.sub.2 (0.17 g, 0.20 mmol, 0.050) was added. The tube was sealed up and heated in the microwave reacter to 120 C. for 45 min. The reaction mixture was taken up in ethyl acetate and filtered over a celite pad. The filtrate was washed with water and brine. The organic layer was dried over magnesium sulfate, filtered and evaporated under vacuum.

(93) The crude product was purified by flash chromatography (Silica, Cyclohexane/gradient of ethyl acetate 0 to 30%).

(94) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 3.95 (s, 3H), 4.02 (s, 3H), 6.33 (t, J=73.0 Hz, 1H), 8.11 (s, 1H), 8.17 (s, 1H), 8.30 (d, J=2.6 Hz, 1H), 8.71 (d, J=2.6 Hz, 1H).

(95) LC-MS (Method A): t.sub.R=1.12 min, m/z=502 [M+1].

c) Preparation of 2-Chloro-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]pyridine-3-carboxylic acid

(96) ##STR00070##

(97) Methyl 2-chloro-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]pyridine-3-carboxylate (1.4 g, 2.8 mmol) was dissolved in tetrahydrofurane (14 mL). Water (3 mL) and lithium hydroxide monohydrate (0.29 g, 7.0 mmol, 2.5) were subsequently added and the mixture was stirred at RT for 1 h. Most of tetrahydrofurane was removed by rotary evaporation. The aqueous residue was acidified at 0 C. with 32% HCl and the product was extracted with ethyl acetate. The extract was washed with water and brine, dried over magnesium sulfate, filtered and evaporated to result in a yellow solid which was used as is in the next step.

(98) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 3.96 (s, 3H), 6.34 (t, J=73.0 Hz, 1H), 8.13 (s, 1H), 8.19 (s, 1H), 8.44 (d, J=2.6 Hz, 1H), 8.77 (d, J=2.6 Hz, 1H).

(99) LC-MS (Method A): t.sub.R=1.00 min, m/z=486 [M1], 488 [M+1].

d) Preparation of 2-Chloro-N-cyclopropyl-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]pyridine-3-carboxamide

(100) ##STR00071##

(101) Oxalyl chloride (0.30 g, 2.3 mmol) was dissolved in dry dichloromethane (11 ml) followed by the addition of 1 drop of dimethylformamide and 2-chloro-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]pyridine-3-carboxylic acid (0.55 g, 1.1 m mol). The reaction mixture was stirred at RT for 30 minutes and then at 35 C. for 10 minutes. Afterwards the mixture was evaporated to dryness. The remaining acid chloride was dissolved in dry pyridine (6 ml) and cyclopropylamine (0.13 g, 2.3 mmol) was added at 0 C. The reaction mixture was stirred at RT for 1 h.

(102) The product was isolated by flash chromatography.

(103) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 0.71 (m, 2H), 0.95 (m, 2H), 2.98 (m, 1H), 3.95 (s, 3H), 6.33 (t, J=72.8 Hz, 1H), 6.69 (br s, 1H), 8.10 (s, 1H), 8.17 (s, 1H), 8.29 (d, J=2.6 Hz, 1H), 8.64 (d, J=2.6 Hz, 1H).

(104) LC-MS (Method A): t.sub.R=1.02 min, m/z=525 [M1], 527 [M+1].

e) Preparation of 2-Chloro-N-cyclopropyl-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]-N-methyl-pyridine-3-carboxamide

(105) ##STR00072##

(106) To a solution of 2-chloro-N-cyclopropyl-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]pyridine-3-carboxamide (0.15 g, 0.28 mmol) in N,N-dimethylformamide sodium hydride (0.014 g, 0.36 mmol, 60% dispersion in mineral oil) was added at RT. The reaction mixture was stirred at RT for 30 minutes followed by the addition of iodomethane (0.081 g, 0.57 mmol). The reaction mixture was stitted overnight at RT. The product was isolated by flash chromatography.

(107) LC-MS (Method A): t.sub.R=1.08 min, m/z=541 [M+1].

Example 49: Preparation of 2-Cyano-N-cyclopropyl-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]pyridine-3-carboxamide

(108) ##STR00073##

(109) A microwave tube was charged with 2-chloro-N-cyclopropyl-5-[1-[4-(difluoromethoxy)-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazol-3-yl]pyrazol-4-yl]pyridine-3-carboxamide (0.05, 0.095 mmol), zinc cyanide (0.011 g, 0.095 mmol), zinc powder (1 mg, 0.011 mmol), 1,1-bis(diphenylphosphino)ferrocen (2.1 mg, 0.0038 mmol), tris(dibenzylideneacetone)dipalladium(0) (1.8 mg, 0.0019 mmol) and dry N,N-dimethylacetamide (2.0 mL). The mixture was purged with argon, the tube was sealed up and heated in the microwave reacter to 140 C. for 1 h. The crude reaction mixture was subjected to flash chromatography on silica. The product decomposed on silica resulting in a product with the same molecular mass.

(110) .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 1.05-1.15 (m, 4H), 2.82 (m, 1H), 3.97 (s, 3H), 6.35 (t, J=72.8 Hz, 1H), 8.21 (s, 1H), 8.25 (d, J=1.8 Hz, 1H), 8.26 (s, 1H), 9.14 (d, J=2.2 Hz, 1H).

(111) LC-MS (Method A): t.sub.R=1.02 min, m/z=516 [M1], 518 [M+1].

(112) The following compounds which have been characterized were prepared in analogy to Examples 1, 2, 15, 16, 49, 54 and 64.

(113) TABLE-US-00003 TABLE 1 Examples of compounds of formula (I): 1H-NMR (400 MHz) Mp Structure LC MS (method) [ C.] 1 (CDCl.sub.3) ppm: 1.41-1.46 (m, 2 H) 1.67-1.72 (m, 2 H) 3.93 (s, 3 H) 6.12-6.51 (m, 1 H) 7.46 (d, J = 8.07 Hz, 1 H) 7.57 (dd, J = 8.25, 2.38 Hz, 1 H) 7.96 (d, J = 2.20 Hz, 1 H) 8.03 (s, 1 H) 8.12 (s, 1 H) 138-139 2 (CDCl.sub.3) ppm 0.56-0.63 (m, 2 H) 0.81-0.87 (m, 2 H) 2.88 (tq, J = 7.08, 3.71 Hz, 1 H) 3.85 (s, 3 H) 6.02-6.46 (m, 2 H) 7.33-7.48 (m, 2 H) 7.75-7.96 (m, 2 H) 7.98-8.07 (m, 1 H). 3 LC-MS (A): t.sub.R = 1.09 min, m/z = 583/5 [M + 1].sup.+ 4 5 6 LC-MS (B): t.sub.R = 1.69 min, m/z = 490/2 [M + 1].sup.+ 7 0 8 9 LC-MS (B): t.sub.R = 1.79 min, m/z = 525/7 [M + 1].sup.+ 10 11 12 13 14 15 (CDCl.sub.3) ppm 1.41-1.44 (m, 2 H) 1.68-1.72 (m, 2 H) 3.79 (s, 3 H) 4.92 (d, J = 17.97 Hz, 1 H) 5.17-5.23 (m, 1 H) 6.49 (dd, J = 17.79, 11.55 Hz, 1 H) 6.90 (s, 1 H) 7.45 (d, J = 8.07 Hz, 1 H) 7.57 (dd, J = 8.44, 2.20 Hz, 1 H) 7.90 (s, 1 H) 7.96 (d, J = 2.20 Hz, 1 H) 8.14 (d, J = 0.73 Hz, 1 H). 16 (CDCl.sub.3) ppm 0.66-0.70 (m, 2 H) 0.89-0.94 (m, 2 H) 2.91- 2.97 (m, 1 H) 3.78 (s, 3 H) 4.88-4.95 (m, 1 H) 5.19 (dd, J = 11.55, 0.92 Hz, 1 H) 6.40 (br. s., 1 H) 6.49 (dd, J = 17.97, 11.37 Hz, 1 H) 7.41-7.45 (m, 1 H) 7.49-7.53 (m, 1 H) 7.87 (d, J = 0.73 Hz, 2 H) 8.13 (d, J = 0.73 Hz, 1 H). 17 0 LC-MS (B): t.sub.R = 1.75 min, m/z = 509/11 [M + 1].sup.+ 18 LC-MS (B): t.sub.R = 1.77 min, m/z = 484/6 [M + 1].sup.+ 19 72-4 20 69-71 21 LC-MS (B): t.sub.R = 1.64 min, m/z = 552/4 [M + 1].sup.+ 22 LC-MS (B): t.sub.R = 1.64 min, m/z = 527/9 [M + 1].sup.+ 23 24 25 26 27 00 28 01 29 02 30 03 31 04 32 05 33 06 95-7 34 07 72-4 35 08 102-4 36 09 104-6 37 0 LC-MS (B): t.sub.R = 1.80 min, m/z = 601/03 [M + 1].sup.+ 38 LC-MS (B): t.sub.R = 1.77 min, m/z = 529/31 [M + 1].sup.+ 169-70 39 LC-MS (B): t.sub.R = 1.75 min, m/z = 565/7 [M + 1].sup.+ 40 LC-MS (B): t.sub.R = 2.07 min, m/z = 669/71 [M + 1].sup.+ 41 LC-MS (B): t.sub.R = 1.86 min, m/z = 565/7 [M + 1].sup.+ 42 LC-MS (B): t.sub.R = 1.92 min, m/z = 579/81 [M + 1].sup.+ 43 LC-MS (B): t.sub.R = 1.92 min, m/z = 651/3 [M + 1].sup.+ 44 LC-MS (B): t.sub.R = 1.76 min, m/z = 540/2 [M + 1].sup.+ 45 LC-MS (B): t.sub.R = 2.11 min, m/z = 644/6 [M + 1].sup.+ 46 LC-MS (B): t.sub.R = 1.94 min, m/z = 626/8 [M + 1].sup.+ 47 0 LC-MS (A): t.sub.R = 1.13 min, m/z = 544 [M + 1]+, 542 [M 1] 48 LC-MS (A): t.sub.R = 1.11 min, m/z = 569 [M + 1]+, 567 [M 1] 49 LC-MS (A): t.sub.R = 1.01 min, m/z = 518 [M + 1]+, 516 [M 1] 50 LC-MS (A): t.sub.R = 1.17 min, m/z = 558 [M + 1]+ 51 LC-MS (A): t.sub.R = 1.17 min, m/z = 597 [M + 1]+ 52 LC-MS (A): t.sub.R = 1.07 min, m/z = 566 [M + 1]+ 53 LC-MS (A): t.sub.R = 1.09 min, m/z = 580 [M + 1]+ 54 LC-MS (A): t.sub.R = 1.08 min, m/z = 541 [M + 1]+ 55 LC-MS (A): t.sub.R = 1.12 min, m/z = 555 [M + 1]+, 553 [M 1] 56 LC-MS (A): t.sub.R = 1.03 min, m/z = 543 [M + 1]+, 541 [M 1] 57 0 LC-MS (B): t.sub.R = 2.09 min, m/z = 676/8 [M + 1].sup.+ 58 LC-MS (A): t.sub.R = 1.12 min, m/z = 545 [M + 1]+ 59 LC-MS (A): t.sub.R = 1.08 min, m/z = 531 [M + 1]+ 60 LC-MS (A): t.sub.R = 1.10 min, m/z = 570 [M + 1]+ 61 LC-MS (A): t.sub.R = 1.07 min, m/z = 556 [M + 1]+ 62 LC-MS (A): t.sub.R = 1.04 min, m/z = 517 [M + 1]+, 516 [M 1] 63 LC-MS (A): t.sub.R = 1.03 min, m/z = 542 [M + 1]+, 540 [M 1] 64 LC-MS (A): t.sub.R = 1.05 min, m/z = 552 [M + 1]+, 550 [M 1] 65 LC-MS (A): t.sub.R = 1.06 min, m/z = 527 [M + 1]

Formulation Examples (%=Percent by Weight)

(114) TABLE-US-00004 Example F1: Emulsion concentrates a) b) c) Active ingredient 25% 40% 50% Calcium dodecylbenzenesulfonate 5% 8% 6% Castor oil polyethylene 5% glycol ether (36 mol of EO) Tributylphenoxypolyethylene glycol 12% 4% ether (30 mol of EO) Cyclohexanone 15% 20% Xylene mixture 65% 25% 20%

(115) Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.

(116) TABLE-US-00005 Example F2: Solutions a) b) c) d) Active ingredient 80% 10% 5% 95% Ethylene glycol monomethyl 20% ether Polyethylene glycol 70% MW 400 N-Methylpyrrolid-2-one 20% Epoxidized coconut oil 1% 5% Petroleum ether 94% (boiling range: 160-190)

(117) The solutions are suitable for use in the form of microdrops.

(118) TABLE-US-00006 Example F3: Granules a) b) c) d) Active ingredient 5% 10% 8% 21% Kaolin 94% 79% 54% Highly disperse silica 1% 13% 7% Attapulgite 90% 18%

(119) The active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier(s), and the solvent is subsequently evaporated in vacuo.

(120) TABLE-US-00007 Example F4: Dusts a) b) Active ingredient 2% 5% Highly disperse silica 1% 5% Talc 97% Kaolin 90%

(121) Ready-to-use dusts are obtained by intimately mixing the carriers and the active ingredient.

(122) TABLE-US-00008 Example F5: Wettable powders a) b) c) Active ingredient 25% 50% 75% Sodium lignosulfonate 5% 5% Sodium lauryl sulfate 3% 5% Sodium diisobutyl- 6% 10% naphthalenesulfonate Octylphenoxypolyethylene glycol 2% ether (7-8 mol of EO) Highly disperse silica 5% 10% 10% Kaolin 62% 27%

(123) The active ingredient is mixed with the additives and the mixture is ground thoroughly in a suitable mill.

(124) This gives wettable powders, which can be diluted with water to give suspensions of any desired concentration.

(125) TABLE-US-00009 Example F6: Extruder granules Active ingredient 10% Sodium lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 87%

(126) The active ingredient is mixed with the additives, and the mixture is ground, moistened with water, extruded, granulated and dried in a stream of air.

(127) TABLE-US-00010 Example F7: Coated granules Active ingredient 3% Polyethylene glycol (MW 200) 3% Kaolin 94%

(128) In a mixer, the finely ground active ingredient is applied uniformly to the kaolin, which has been moistened with the polyethylene glycol. This gives dust-free coated granules.

(129) TABLE-US-00011 Example F8: Suspension concentrate Active ingredient 40% Ethylene glycol 10% Nonylphenoxypolyethylene glycol ether (15 mol of EO) 6% Sodium lignosulfonate 10% Carboxymethylcellulose 1% 37% aqueous formaldehyde solution 0.2% Silicone oil (75% aqueous emulsion) 0.8% Water 32%

(130) The finely ground active ingredient is mixed intimately with the additives. Suspensions of any desired concentration can be prepared from the thus resulting suspension concentrate by dilution with water.

(131) TABLE-US-00012 Example F9: Powders for dry seed treatment a) b) c) active ingredient 25% 50% 75% light mineral oil 5% 5% 5% highly dispersed silicic acid 5% 5% Kaolin 65% 40% Talcum 20%

(132) The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.

(133) TABLE-US-00013 Example F10: Emulsifiable concentrate active ingredient 10% octylphenol polyethylene glycol ether 3% (4-5 mol of ethylene oxide) calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether (35 mol of ethylene oxide) 4% Cyclohexanone 30% xylene mixture 50%

(134) Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.

(135) TABLE-US-00014 Example F11: Flowable concentrate for seed treatment active ingredients 40% propylene glycol 5% copolymer butanol PO/EO 2% Tristyrenephenole with 10-20 moles EO 2% 1,2-benzisothiazolin-3-one 0.5%.sup. (in the form of a 20% solution in water) monoazo-pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2%.sup. Water 45.3%

(136) The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

(137) 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 according to any one of embodiments 1 to 25 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.

(138) 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.

(139) The following mixtures of the compounds according to any one of embodiments 1 to 25 with active ingredients are preferred (the abbreviation TX means one compound selected from the compounds according to any one of embodiments 1 to 25, preferably one compound from Table 1):

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

(141) an acaricide selected from the group of substances consisting of 1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910)+TX, 2,4-dichlorophenyl benzenesulfonate (IUPAC/Chemical Abstracts name) (1059)+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name) (1295)+TX, 4-chlorophenyl phenyl sulfone (IUPAC name) (981)+TX, abamectin (1)+TX, acequinocyl (3)+TX, acetoprole [CCN]+TX, acrinathrin (9)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, alpha-cypermethrin (202)+TX, amidithion (870)+TX, amidoflumet [CCN]+TX, amidothioate (872)+TX, amiton (875)+TX, amiton hydrogen oxalate (875)+TX, amitraz (24)+TX, aramite (881)+TX, arsenous oxide (882)+TX, AVI 382 (compound code)+TX, AZ 60541 (compound code)+TX, azinphos-ethyl (44)+TX, azinphos-methyl (45)+TX, azobenzene (IUPAC name) (888)+TX, azocyclotin (46)+TX, azothoate (889)+TX, benomyl (62)+TX, benoxafos (alternative name) [CCN]+TX, benzoximate (71)+TX, benzyl benzoate (IUPAC name) [CCN]+TX, bifenazate (74)+TX, bifenthrin (76)+TX, binapacryl (907)+TX, brofenvalerate (alternative name)+TX, bromocyclen (918)+TX, bromophos (920)+TX, bromophos-ethyl (921)+TX, bromopropylate (94)+TX, buprofezin (99)+TX, butocarboxim (103)+TX, butoxycarboxim (104)+TX, butylpyridaben (alternative name)+TX, calcium polysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX, carbanolate (943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbophenothion (947)+TX, CGA 50439 (development code) (125)+TX, chinomethionat (126)+TX, chlorbenside (959)+TX, chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX, chlorfenapyr (130)+TX, chlorfenethol (968)+TX, chlorfenson (970)+TX, chlorfensulfide (971)+TX, chlorfenvinphos (131)+TX, chlorobenzilate (975)+TX, chloromebuform (977)+TX, chloromethiuron (978)+TX, chloropropylate (983)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl (146)+TX, chlorthiophos (994)+TX, cinerin 1 (696)+TX, cinerin II (696)+TX, cinerins (696)+TX, clofentezine (158)+TX, closantel (alternative name) [CCN]+TX, coumaphos (174)+TX, crotamiton (alternative name) [CCN]+TX, crotoxyphos (1010)+TX, cufraneb (1013)+TX, cyanthoate (1020)+TX, cyflumetofen (CAS Reg. No.: 400882-07-7)+TX, cyhalothrin (196)+TX, cyhexatin (199)+TX, cypermethrin (201)+TX, DCPM (1032)+TX, DDT (219)+TX, demephion (1037)+TX, demephion-O (1037)+TX, demephion-S(1037)+TX, demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O (1038)+TX, demeton-O-methyl (224)+TX, demeton-S(1038)+TX, demeton-S-methyl (224)+TX, demeton-S-methylsulfon (1039)+TX, diafenthiuron (226)+TX, dialifos (1042)+TX, diazinon (227)+TX, dichlofluanid (230)+TX, dichlorvos (236)+TX, dicliphos (alternative name)+TX, dicofol (242)+TX, dicrotophos (243)+TX, dienochlor (1071)+TX, dimefox (1081)+TX, dimethoate (262)+TX, dinactin (alternative name) (653)+TX, dinex (1089)+TX, dinex-diclexine (1089)+TX, dinobuton (269)+TX, dinocap (270)+TX, dinocap-4 [CCN]+TX, dinocap-6 [CCN]+TX, dinocton (1090)+TX, dinopenton (1092)+TX, dinosulfon (1097)+TX, dinoterbon (1098)+TX, dioxathion (1102)+TX, diphenyl sulfone (IUPAC name) (1103)+TX, disulfiram (alternative name) [CCN]+TX, disulfoton (278)+TX, DNOC (282)+TX, dofenapyn (1113)+TX, doramectin (alternative name) [CCN]+TX, endosulfan (294)+TX, endothion (1121)+TX, EPN (297)+TX, eprinomectin (alternative name) [CCN]+TX, ethion (309)+TX, ethoate-methyl (1134)+TX, etoxazole (320)+TX, etrimfos (1142)+TX, fenazaflor (1147)+TX, fenazaquin (328)+TX, fenbutatin oxide (330)+TX, fenothiocarb (337)+TX, fenpropathrin (342)+TX, fenpyrad (alternative name)+TX, fenpyroximate (345)+TX, fenson (1157)+TX, fentrifanil (1161)+TX, fenvalerate (349)+TX, fipronil (354)+TX, fluacrypyrim (360)+TX, fluazuron (1166)+TX, flubenzimine (1167)+TX, flucycloxuron (366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX, flufenoxuron (370)+TX, flumethrin (372)+TX, fluorbenside (1174)+TX, fluvalinate (1184)+TX, FMC 1137 (development code) (1185)+TX, formetanate (405)+TX, formetanate hydrochloride (405)+TX, formothion (1192)+TX, formparanate (1193)+TX, gamma-HCH (430)+TX, glyodin (1205)+TX, halfenprox (424)+TX, heptenophos (432)+TX, hexadecyl cyclopropanecarboxylate (IUPAC/Chemical Abstracts name) (1216)+TX, hexythiazox (441)+TX, iodomethane (IUPAC name) (542)+TX, isocarbophos (alternative name) (473)+TX, isopropyl O-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473)+TX, ivermectin (alternative name) [CCN]+TX, jasmolin 1 (696)+TX, jasmolin II (696)+TX, jodfenphos (1248)+TX, lindane (430)+TX, lufenuron (490)+TX, malathion (492)+TX, malonoben (1254)+TX, mecarbam (502)+TX, mephosfolan (1261)+TX, mesulfen (alternative name) [CCN]+TX, methacrifos (1266)+TX, methamidophos (527)+TX, methidathion (529)+TX, methiocarb (530)+TX, methomyl (531)+TX, methyl bromide (537)+TX, metolcarb (550)+TX, mevinphos (556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX, milbemycin oxime (alternative name) [CCN]+TX, mipafox (1293)+TX, monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternative name) [CCN]+TX, naled (567)+TX, NC-184 (compound code)+TX, NC-512 (compound code)+TX, nifluridide (1309)+TX, nikkomycins (alternative name) [CCN]+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1 zinc chloride complex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250 (compound code)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp-DDT (219)+TX, parathion (615)+TX, permethrin (626)+TX, petroleum oils (alternative name) (628)+TX, phenkapton (1330)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone (637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosphamidon (639)+TX, phoxim (642)+TX, pirimiphos-methyl (652)+TX, polychloroterpenes (traditional name) (1347)+TX, polynactins (alternative name) (653)+TX, proclonol (1350)+TX, profenofos (662)+TX, promacyl (1354)+TX, propargite (671)+TX, propetamphos (673)+TX, propoxur (678)+TX, prothidathion (1360)+TX, prothoate (1362)+TX, pyrethrin 1 (696)+TX, pyrethrin 11 (696)+TX, pyrethrins (696)+TX, pyridaben (699)+TX, pyridaphenthion (701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, quinalphos (711)+TX, quintiofos (1381)+TX, R-1492 (development code) (1382)+TX, RA-17 (development code) (1383)+TX, rotenone (722)+TX, schradan (1389)+TX, sebufos (alternative name)+TX, selamectin (alternative name) [CCN]+TX, SI-0009 (compound code)+TX, sophamide (1402)+TX, spirodiclofen (738)+TX, spiromesifen (739)+TX, SSI-121 (development code) (1404)+TX, sulfiram (alternative name) [CCN]+TX, sulfluramid (750)+TX, sulfotep (753)+TX, sulfur (754)+TX, SZI-121 (development code) (757)+TX, tau-fluvalinate (398)+TX, tebufenpyrad (763)+TX, TEPP (1417)+TX, terbam (alternative name)+TX, tetrachlorvinphos (777)+TX, tetradifon (786)+TX, tetranactin (alternative name) (653)+TX, tetrasul (1425)+TX, thiafenox (alternative name)+TX, thiocarboxime (1431)+TX, thiofanox (800)+TX, thiometon (801)+TX, thioquinox (1436)+TX, thuringiensin (alternative name) [CCN]+TX, triamiphos (1441)+TX, triarathene (1443)+TX, triazophos (820)+TX, triazuron (alternative name)+TX, trichlorfon (824)+TX, trifenofos (1455)+TX, trinactin (alternative name) (653)+TX, vamidothion (847)+TX, vaniliprole [CCN] and YI-5302 (compound code)+TX,
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, 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,
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, 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,
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, a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537)+TX,
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,
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 Bi (alternative name) (839)+TX, trimedlure B.sub.2 (alternative name) (839)+TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN]+TX,
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, an insecticide selected from the group of substances consisting of 1-dichloro-1-nitroethane (IUPAC/Chemical Abstracts name) (1058)+TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), +TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062)+TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063)+TX, 1-bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916)+TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451)+TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate (IUPAC name) (1066)+TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate (IUPAC/Chemical Abstracts name) (1109)+TX, 2-(2-butoxyethoxy)ethyl thiocyanate (IUPAC/Chemical Abstracts name) (935)+TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/Chemical Abstracts name) (1084)+TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986)+TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984)+TX, 2-imidazolidone (IUPAC name) (1225)+TX, 2-isovalerylindan-1,3-dione (IUPAC name) (1246)+TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate (IUPAC name) (1284)+TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433)+TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917)+TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283)+TX, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name) (1285)+TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPAC name) (1085)+TX, abamectin (1)+TX, acephate (2)+TX, acetamiprid (4)+TX, acethion (alternative name) [CCN]+TX, acetoprole [CCN]+TX, acrinathrin (9)+TX, acrylonitrile (IUPAC name) (861)+TX, alanycarb (15)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, aldrin (864)+TX, allethrin (17)+TX, allosamidin (alternative name) [CCN]+TX, allyxycarb (866)+TX, alpha-cypermethrin (202)+TX, alpha-ecdysone (alternative name) [CCN]+TX, aluminium phosphide (640)+TX, amidithion (870)+TX, amidothioate (872)+TX, aminocarb (873)+TX, amiton (875)+TX, amiton hydrogen oxalate (875)+TX, amitraz (24)+TX, anabasine (877)+TX, athidathion (883)+TX, AVI 382 (compound code)+TX, AZ 60541 (compound code)+TX, azadirachtin (alternative name) (41)+TX, azamethiphos (42)+TX, azinphos-ethyl (44)+TX, azinphos-methyl (45)+TX, azothoate (889)+TX, Bacillus thuringiensis delta endotoxins (alternative name) (52)+TX, barium hexafluorosilicate (alternative name) [CCN]+TX, barium polysulfide (IUPAC/Chemical Abstracts name) (892)+TX, barthrin [CCN]+TX, Bayer 22/190 (development code) (893)+TX, Bayer 22408 (development code) (894)+TX, bendiocarb (58)+TX, benfuracarb (60)+TX, bensultap (66)+TX, beta-cyfluthrin (194)+TX, beta-cypermethrin (203)+TX, bifenthrin (76)+TX, bioallethrin (78)+TX, bioallethrin S-cyclopentenyl isomer (alternative name) (79)+TX, bioethanomethrin [CCN]+TX, biopermethrin (908)+TX, bioresmethrin (80)+TX, bis(2-chloroethyl) ether (IUPAC name) (909)+TX, bistrifluron (83)+TX, borax (86)+TX, brofenvalerate (alternative name)+TX, bromfenvinfos (914)+TX, bromocyclen (918)+TX, bromo-DDT (alternative name) [CCN]+TX, bromophos (920)+TX, bromophos-ethyl (921)+TX, bufencarb (924)+TX, buprofezin (99)+TX, butacarb (926)+TX, butathiofos (927)+TX, butocarboxim (103)+TX, butonate (932)+TX, butoxycarboxim (104)+TX, butylpyridaben (alternative name)+TX, cadusafos (109)+TX, calcium arsenate [CCN]+TX, calcium cyanide (444)+TX, calcium polysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX, carbanolate (943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbon disulfide (IUPAC/Chemical Abstracts name) (945)+TX, carbon tetrachloride (IUPAC name) (946)+TX, carbophenothion (947)+TX, carbosulfan (119)+TX, cartap (123)+TX, cartap hydrochloride (123)+TX, cevadine (alternative name) (725)+TX, chlorbicyclen (960)+TX, chlordane (128)+TX, chlordecone (963)+TX, chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX, chlorethoxyfos (129)+TX, chlorfenapyr (130)+TX, chlorfenvinphos (131)+TX, chlorfluazuron (132)+TX, chlormephos (136)+TX, chloroform [CCN]+TX, chloropicrin (141)+TX, chlorphoxim (989)+TX, chlorprazophos (990)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl (146)+TX, chlorthiophos (994)+TX, chromafenozide (150)+TX, cinerin I (696)+TX, cinerin II (696)+TX, cinerins (696)+TX, cis-resmethrin (alternative name)+TX, cismethrin (80)+TX, clocythrin (alternative name)+TX, cloethocarb (999)+TX, closantel (alternative name) [CCN]+TX, clothianidin (165)+TX, copper acetoarsenite [CCN]+TX, copper arsenate [CCN]+TX, copper oleate [CCN]+TX, coumaphos (174)+TX, coumithoate (1006)+TX, crotamiton (alternative name) [CCN]+TX, crotoxyphos (1010)+TX, crufomate (1011)+TX, cryolite (alternative name) (177)+TX, CS 708 (development code) (1012)+TX, cyanofenphos (1019)+TX, cyanophos (184)+TX, cyanthoate (1020)+TX, cyclethrin [CCN]+TX, cycloprothrin (188)+TX, cyfluthrin (193)+TX, cyhalothrin (196)+TX, cypermethrin (201)+TX, cyphenothrin (206)+TX, cyromazine (209)+TX, cythioate (alternative name) [CCN]+TX, d-limonene (alternative name) [CCN]+TX, d-tetramethrin (alternative name) (788)+TX, DAEP (1031)+TX, dazomet (216)+TX, DDT (219)+TX, decarbofuran (1034)+TX, deltamethrin (223)+TX, demephion (1037)+TX, demephion-O (1037)+TX, demephion-S(1037)+TX, demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O (1038)+TX, demeton-O-methyl (224)+TX, demeton-S(1038)+TX, demeton-S-methyl (224)+TX, demeton-S-methylsulphon (1039)+TX, diafenthiuron (226)+TX, dialifos (1042)+TX, diamidafos (1044)+TX, diazinon (227)+TX, dicapthon (1050)+TX, dichlofenthion (1051)+TX, dichlorvos (236)+TX, dicliphos (alternative name)+TX, dicresyl (alternative name) [CCN]+TX, dicrotophos (243)+TX, dicyclanil (244)+TX, dieldrin (1070)+TX, diethyl 5-methylpyrazol-3-yl phosphate (IUPAC name) (1076)+TX, diflubenzuron (250)+TX, dilor (alternative name) [CCN]+TX, dimefluthrin [CCN]+TX, dimefox (1081)+TX, dimetan (1085)+TX, dimethoate (262)+TX, dimethrin (1083)+TX, dimethylvinphos (265)+TX, dimetilan (1086)+TX, dinex (1089)+TX, dinex-diclexine (1089)+TX, dinoprop (1093)+TX, dinosam (1094)+TX, dinoseb (1095)+TX, dinotefuran (271)+TX, diofenolan (1099)+TX, dioxabenzofos (1100)+TX, dioxacarb (1101)+TX, dioxathion (1102)+TX, disulfoton (278)+TX, dithicrofos (1108)+TX, DNOC (282)+TX, doramectin (alternative name) [CCN]+TX, DSP (1115)+TX, ecdysterone (alternative name) [CCN]+TX, EI 1642 (development code) (1118)+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, EMPC (1120)+TX, empenthrin (292)+TX, endosulfan (294)+TX, endothion (1121)+TX, endrin (1122)+TX, EPBP (1123)+TX, EPN (297)+TX, epofenonane (1124)+TX, eprinomectin (alternative name) [CCN]+TX, esfenvalerate (302)+TX, etaphos (alternative name) [CCN]+TX, ethiofencarb (308)+TX, ethion (309)+TX, ethiprole (310)+TX, ethoate-methyl (1134)+TX, ethoprophos (312)+TX, ethyl formate (IUPAC name) [CCN]+TX, ethyl-DDD (alternative name) (1056)+TX, ethylene dibromide (316)+TX, ethylene dichloride (chemical name) (1136)+TX, ethylene oxide [CCN]+TX, etofenprox (319)+TX, etrimfos (1142)+TX, EXD (1143)+TX, famphur (323)+TX, fenamiphos (326)+TX, fenazaflor (1147)+TX, fenchlorphos (1148)+TX, fenethacarb (1149)+TX, fenfluthrin (1150)+TX, fenitrothion (335)+TX, fenobucarb (336)+TX, fenoxacrim (1153)+TX, fenoxycarb (340)+TX, fenpirithrin (1155)+TX, fenpropathrin (342)+TX, fenpyrad (alternative name)+TX, fensulfothion (1158)+TX, fenthion (346)+TX, fenthion-ethyl [CCN]+TX, fenvalerate (349)+TX, fipronil (354)+TX, flonicamid (358)+TX, flubendiamide (CAS. Reg. No.: 272451-65-7)+TX, flucofuron (1168)+TX, flucycloxuron (366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX, flufenerim [CCN]+TX, flufenoxuron (370)+TX, flufenprox (1171)+TX, flumethrin (372)+TX, fluvalinate (1184)+TX, FMC 1137 (development code) (1185)+TX, fonofos (1191)+TX, formetanate (405)+TX, formetanate hydrochloride (405)+TX, formothion (1192)+TX, formparanate (1193)+TX, fosmethilan (1194)+TX, fospirate (1195)+TX, fosthiazate (408)+TX, fosthietan (1196)+TX, furathiocarb (412)+TX, furethrin (1200)+TX, gamma-cyhalothrin (197)+TX, gamma-HCH (430)+TX, guazatine (422)+TX, guazatine acetates (422)+TX, GY-81 (development code) (423)+TX, halfenprox (424)+TX, halofenozide (425)+TX, HCH (430)+TX, HEOD (1070)+TX, heptachlor (1211)+TX, heptenophos (432)+TX, heterophos [CCN]+TX, hexaflumuron (439)+TX, HHDN (864)+TX, hydramethylnon (443)+TX, hydrogen cyanide (444)+TX, hydroprene (445)+TX, hyquincarb (1223)+TX, imidacloprid (458)+TX, imiprothrin (460)+TX, indoxacarb (465)+TX, iodomethane (IUPAC name) (542)+TX, IPSP (1229)+TX, isazofos (1231)+TX, isobenzan (1232)+TX, isocarbophos (alternative name) (473)+TX, isodrin (1235)+TX, isofenphos (1236)+TX, isolane (1237)+TX, isoprocarb (472)+TX, isopropyl O-(methoxy-aminothiophosphoryl)salicylate (IUPAC name) (473)+TX, isoprothiolane (474)+TX, isothioate (1244)+TX, isoxathion (480)+TX, ivermectin (alternative name) [CCN]+TX, jasmolin 1 (696)+TX, jasmolin 11 (696)+TX, jodfenphos (1248)+TX, juvenile hormone I (alternative name) [CCN]+TX, juvenile hormone II (alternative name) [CCN]+TX, juvenile hormone Ill (alternative name) [CCN]+TX, kelevan (1249)+TX, kinoprene (484)+TX, lambda-cyhalothrin (198)+TX, lead arsenate [CCN]+TX, lepimectin (CCN)+TX, leptophos (1250)+TX, lindane (430)+TX, lirimfos (1251)+TX, lufenuron (490)+TX, lythidathion (1253)+TX, m-cumenyl methylcarbamate (IUPAC name) (1014)+TX, magnesium phosphide (IUPAC name) (640)+TX, malathion (492)+TX, malonoben (1254)+TX, mazidox (1255)+TX, mecarbam (502)+TX, mecarphon (1258)+TX, menazon (1260)+TX, mephosfolan (1261)+TX, mercurous chloride (513)+TX, mesulfenfos (1263)+TX, metaflumizone (CCN)+TX, metam (519)+TX, metam-potassium (alternative name) (519)+TX, metam-sodium (519)+TX, methacrifos (1266)+TX, methamidophos (527)+TX, methanesulfonyl fluoride (IUPAC/Chemical Abstracts name) (1268)+TX, methidathion (529)+TX, methiocarb (530)+TX, methocrotophos (1273)+TX, methomyl (531)+TX, methoprene (532)+TX, methoquin-butyl (1276)+TX, methothrin (alternative name) (533)+TX, methoxychlor (534)+TX, methoxyfenozide (535)+TX, methyl bromide (537)+TX, methyl isothiocyanate (543)+TX, methylchloroform (alternative name) [CCN]+TX, methylene chloride [CCN]+TX, metofluthrin [CCN]+TX, metolcarb (550)+TX, metoxadiazone (1288)+TX, mevinphos (556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX, milbemycin oxime (alternative name) [CCN]+TX, mipafox (1293)+TX, mirex (1294)+TX, monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternative name) [CCN]+TX, naftalofos (alternative name) [CCN]+TX, naled (567)+TX, naphthalene (IUPAC/Chemical Abstracts name) (1303)+TX, NC-170 (development code) (1306)+TX, NC-184 (compound code)+TX, nicotine (578)+TX, nicotine sulfate (578)+TX, nifluridide (1309)+TX, nitenpyram (579)+TX, nithiazine (1311)+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1 zinc chloride complex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250 (compound code)+TX, nornicotine (traditional name) (1319)+TX, novaluron (585)+TX, noviflumuron (586)+TX, O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate (IUPAC name) (1057)+TX, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate (IUPAC name) (1074)+TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate (IUPAC name) (1075)+TX, O,O,O,O-tetrapropyl dithiopyrophosphate (IUPAC name) (1424)+TX, oleic acid (IUPAC name) (593)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydemeton-methyl (609)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp-DDT (219)+TX, para-dichlorobenzene [CCN]+TX, parathion (615)+TX, parathion-methyl (616)+TX, penfluron (alternative name) [CCN]+TX, pentachlorophenol (623)+TX, pentachlorophenyl laurate (IUPAC name) (623)+TX, permethrin (626)+TX, petroleum oils (alternative name) (628)+TX, PH 60-38 (development code) (1328)+TX, phenkapton (1330)+TX, phenothrin (630)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone (637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosnichlor (1339)+TX, phosphamidon (639)+TX, phosphine (IUPAC name) (640)+TX, phoxim (642)+TX, phoxim-methyl (1340)+TX, pirimetaphos (1344)+TX, pirimicarb (651)+TX, pirimiphos-ethyl (1345)+TX, pirimiphos-methyl (652)+TX, polychlorodicyclopentadiene isomers (IUPAC name) (1346)+TX, polychloroterpenes (traditional name) (1347)+TX, potassium arsenite [CCN]+TX, potassium thiocyanate [CCN]+TX, prallethrin (655)+TX, precocene I (alternative name) [CCN]+TX, precocene II (alternative name) [CCN]+TX, precocene III (alternative name) [CCN]+TX, primidophos (1349)+TX, profenofos (662)+TX, profluthrin [CCN]+TX, promacyl (1354)+TX, promecarb (1355)+TX, propaphos (1356)+TX, propetamphos (673)+TX, propoxur (678)+TX, prothidathion (1360)+TX, prothiofos (686)+TX, prothoate (1362)+TX, protrifenbute [CCN]+TX, pymetrozine (688)+TX, pyraclofos (689)+TX, pyrazophos (693)+TX, pyresmethrin (1367)+TX, pyrethrin 1 (696)+TX, pyrethrin II (696)+TX, pyrethrins (696)+TX, pyridaben (699)+TX, pyridalyl (700)+TX, pyridaphenthion (701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, pyriproxyfen (708)+TX, quassia (alternative name) [CCN]+TX, quinalphos (711)+TX, quinalphos-methyl (1376)+TX, quinothion (1380)+TX, quintiofos (1381)+TX, R-1492 (development code) (1382)+TX, rafoxanide (alternative name) [CCN]+TX, resmethrin (719)+TX, rotenone (722)+TX, RU 15525 (development code) (723)+TX, RU 25475 (development code) (1386)+TX, ryania (alternative name) (1387)+TX, ryanodine (traditional name) (1387)+TX, sabadilla (alternative name) (725)+TX, schradan (1389)+TX, sebufos (alternative name)+TX, selamectin (alternative name) [CCN]+TX, SI-0009 (compound code)+TX, SI-0205 (compound code)+TX, SI-0404 (compound code)+TX, SI-0405 (compound code)+TX, silafluofen (728)+TX, SN 72129 (development code) (1397)+TX, sodium arsenite [CCN]+TX, sodium cyanide (444)+TX, sodium fluoride (IUPAC/Chemical Abstracts name) (1399)+TX, sodium hexafluorosilicate (1400)+TX, sodium pentachlorophenoxide (623)+TX, sodium selenate (IUPAC name) (1401)+TX, sodium thiocyanate [CCN]+TX, sophamide (1402)+TX, spinosad (737)+TX, spiromesifen (739)+TX, spirotetrmat (CCN)+TX, sulcofuron (746)+TX, sulcofuron-sodium (746)+TX, sulfluramid (750)+TX, sulfotep (753)+TX, sulfuryl fluoride (756)+TX, sulprofos (1408)+TX, tar oils (alternative name) (758)+TX, tau-fluvalinate (398)+TX, tazimcarb (1412)+TX, TDE (1414)+TX, tebufenozide (762)+TX, tebufenpyrad (763)+TX, tebupirimfos (764)+TX, teflubenzuron (768)+TX, tefluthrin (769)+TX, temephos (770)+TX, TEPP (1417)+TX, terallethrin (1418)+TX, terbam (alternative name)+TX, terbufos (773)+TX, tetrachloroethane [CCN]+TX, tetrachlorvinphos (777)+TX, tetramethrin (787)+TX, theta-cypermethrin (204)+TX, thiacloprid (791)+TX, thiafenox (alternative name)+TX, thiamethoxam (792)+TX, thicrofos (1428)+TX, thiocarboxime (1431)+TX, thiocyclam (798)+TX, thiocyclam hydrogen oxalate (798)+TX, thiodicarb (799)+TX, thiofanox (800)+TX, thiometon (801)+TX, thionazin (1434)+TX, thiosultap (803)+TX, thiosultap-sodium (803)+TX, thuringiensin (alternative name) [CCN]+TX, tolfenpyrad (809)+TX, tralomethrin (812)+TX, transfluthrin (813)+TX, transpermethrin (1440)+TX, triamiphos (1441)+TX, triazamate (818)+TX, triazophos (820)+TX, triazuron (alternative name)+TX, trichlorfon (824)+TX, trichlormetaphos-3 (alternative name) [CCN]+TX, trichloronat (1452)+TX, trifenofos (1455)+TX, triflumuron (835)+TX, trimethacarb (840)+TX, triprene (1459)+TX, vamidothion (847)+TX, vaniliprole [CCN]+TX, veratridine (alternative name) (725)+TX, veratrine (alternative name) (725)+TX, XMC (853)+TX, xylylcarb (854)+TX, YI-5302 (compound code)+TX, zeta-cypermethrin (205)+TX, zetamethrin (alternative name)+TX, zinc phosphide (640)+TX, zolaprofos (1469) and ZXI 8901 (development code) (858)+TX, cyantraniliprole [736994-63-19+TX, chlorantraniliprole [500008-45-7]+TX, cyenopyrafen [560121-52-0]+TX, cyflumetofen [400882-07-7]+TX, pyrifluquinazon [337458-27-2]+TX, spinetoram [187166-40-1+187166-15-0]+TX, spirotetramat [203313-25-1]+TX, sulfoxaflor [946578-00-3]+TX, flufiprole [704886-18-0]+TX, meperfluthrin [915288-13-0]+TX, tetramethylfluthrin [84937-88-2]+TX, triflumezopyrim (disclosed in WO 2012/092115)+TX,
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,
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,
a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580)+TX,
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,
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,
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,
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,
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,
and biologically active compounds selected from the group consisting of azaconazole (60207-31-0]+TX, bitertanol [70585-36-3]+TX, bromuconazole [116255-48-2]+TX, cyproconazole [94361-06-5]+TX, difenoconazole [119446-68-3]+TX, diniconazole [83657-24-3]+TX, epoxiconazole [106325-08-0]+TX, fenbuconazole [114369-43-6]+TX, fluquinconazole [136426-54-5]+TX, flusilazole [85509-19-9]+TX, flutriafol [76674-21-0]+TX, hexaconazole [79983-71-4]+TX, imazalil [35554-44-0]+TX, imibenconazole [86598-92-7]+TX, ipconazole [125225-28-7]+TX, metconazole [125116-23-6]+TX, myclobutanil [88671-89-0]+TX, pefurazoate [101903-30-4]+TX, penconazole [66246-88-6]+TX, prothioconazole [178928-70-6]+TX, pyrifenox [88283-41-4]+TX, prochloraz [67747-09-5]+TX, propiconazole [60207-90-1]+TX, simeconazole [149508-90-7]+TX, tebucon-azole [107534-96-3]+TX, tetraconazole [112281-77-3]+TX, triadimefon [43121-43-3]+TX, triadimenol [55219-65-3]+TX, triflumizole [99387-89-0]+TX, triticonazole [131983-72-7]+TX, ancymidol [12771-68-5]+TX, fenarimol [60168-88-9]+TX, nuarimol [63284-71-9]+TX, bupirimate [41483-43-6]+TX, dimethirimol [5221-53-4]+TX, ethirimol [23947-60-6]+TX, dodemorph [1593-77-7]+TX, fenpropidine [67306-00-7]+TX, fenpropimorph [67564-91-4]+TX, spiroxamine [118134-30-8]+TX, tridemorph [81412-43-3]+TX, cyprodinil [121552-61-2]+TX, mepanipyrim [110235-47-7]+TX, pyrimethanil [53112-28-0]+TX, fenpiclonil [74738-17-3]+TX, fludioxonil [131341-86-1]+TX, benalaxyl [71626-11-4]+TX, furalaxyl [57646-30-7]+TX, metalaxyl [57837-19-1]+TX, R-metalaxyl [70630-17-0]+TX, ofurace [58810-48-3]+TX, oxadixyl [77732-09-3]+TX, benomyl [17804-35-2]+TX, carbendazim [10605-21-7]+TX, debacarb [62732-91-6]+TX, fuberidazole [3878-19-1]+TX, thiabendazole [148-79-8]+TX, chlozolinate [84332-86-5]+TX, dichlozoline [24201-58-9]+TX, iprodione [36734-19-7]+TX, myclozoline [54864-61-8]+TX, procymidone [32809-16-8]+TX, vinclozoline [50471-44-8]+TX, boscalid [188425-85-6]+TX, carboxin [5234-68-4]+TX, fenfuram [24691-80-3]+TX, flutolanil [66332-96-5]+TX, mepronil [55814-41-0]+TX, oxycarboxin [5259-88-1]+TX, penthiopyrad [183675-82-3]+TX, thifluzamide [130000-40-7]+TX, guazatine [108173-90-6]+TX, dodine [2439-10-3] [112-65-2] (free base)+TX, iminoctadine [13516-27-3]+TX, azoxystrobin [131860-33-8]+TX, dimoxystrobin [149961-52-4]+TX, enestroburin {Proc. BCPC, Int. Congr., Glasgow, 2003, 1, 93}+TX, fluoxastrobin [361377-29-9]+TX, kresoxim-methyl [143390-89-0]+TX, metominostrobin [133408-50-1]+TX, trifloxystrobin [141517-21-7]+TX, orysastrobin [248593-16-0]+TX, picoxystrobin [117428-22-5]+TX, pyraclostrobin [175013-18-0]+TX, ferbam [14484-64-1]+TX, mancozeb [8018-01-7]+TX, maneb [12427-38-2]+TX, metiram [9006-42-2]+TX, propineb [12071-83-9]+TX, thiram [137-26-8]+TX, zineb [12122-67-7]+TX, ziram [137-30-4]+TX, captafol [2425-06-1]+TX, captan [133-06-2]+TX, dichlofluanid [1085-98-9]+TX, fluoroimide [41205-21-4]+TX, folpet [133-07-3]+TX, tolylfluanid [731-27-1]+TX, bordeaux mixture [8011-63-0]+TX, copperhydroxid [20427-59-2]+TX, copperoxychlorid [1332-40-7]+TX, coppersulfat [7758-98-7]+TX, copperoxid [1317-39-1]+TX, mancopper [53988-93-5]+TX, oxine-copper [10380-28-6]+TX, dinocap [131-72-6]+TX, nitrothal-isopropyl [10552-74-6]+TX, edifenphos [17109-49-8]+TX, iprobenphos [26087-47-8]+TX, isoprothiolane [50512-35-1]+TX, phosdiphen [36519-00-3]+TX, pyrazophos [13457-18-6]+TX, tolclofos-methyl [57018-04-9]+TX, acibenzolar-S-methyl [135158-54-2]+TX, anilazine [101-05-3]+TX, benthiavalicarb [413615-35-7]+TX, blasticidin-S [2079-00-7]+TX, chinomethionat [2439-01-2]+TX, chloroneb [2675-77-6]+TX, chlorothalonil [1897-45-6]+TX, cyflufenamid [180409-60-3]+TX, cymoxanil [57966-95-7]+TX, dichlone [117-80-6]+TX, diclocymet [139920-32-4]+TX, diclomezine [62865-36-5]+TX, dicloran [99-30-9]+TX, diethofencarb [87130-20-9]+TX, dimetho-morph [110488-70-5]+TX, SYP-LI90 (Flumorph) [211867-47-9]+TX, dithianon [3347-22-6]+TX, ethaboxam [162650-77-3]+TX, etridiazole [2593-15-9]+TX, famoxadone [131807-57-3]+TX, fenamidone [161326-34-7]+TX, fenoxanil [115852-48-7]+TX, fentin [668-34-8]+TX, ferimzone [89269-64-7]+TX, fluazinam [79622-59-6]+TX, fluopicolide [239110-15-7]+TX, flusulfamide [106917-52-6]+TX, fenhexamid [126833-17-8]+TX, fosetyl-aluminium [39148-24-8]+TX, hymexazol [10004-44-1]+TX, iprovalicarb [140923-17-7]+TX, IKF-916 (Cyazofamid) [120116-88-3]+TX, kasugamycin [6980-18-3]+TX, methasulfocarb [66952-49-6]+TX, metrafenone [220899-03-6]+TX, pencycuron [66063-05-6]+TX, phthalide [27355-22-2]+TX, polyoxins [11113-80-7]+TX, probenazole [27605-76-1]+TX, propamocarb [25606-41-1]+TX, proquinazid [189278-12-4]+TX, pyroquilon [57369-32-1]+TX, quinoxyfen [124495-18-7]+TX, quintozene [82-68-8]+TX, sulfur [7704-34-9]+TX, tiadinil [223580-51-6]+TX, triazoxide [72459-58-6]+TX, tricyclazole [41814-78-2]+TX, triforine [26644-46-2]+TX, validamycin [37248-47-8]+TX, zoxamide (RH7281) [156052-68-5]+TX, mandipropamid [374726-62-2]+TX, isopyrazam [881685-58-1]+TX, sedaxane [874967-67-6]+TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide (dislosed in WO 2007/048556)+TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3,4,5-trifluoro-biphenyl-2-yl)-amide (disclosed in WO 2006/087343)+TX, [(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11Hnaphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methyl-cyclopropanecarboxylate [915972-17-7]+TX and 1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide [926914-55-8]+TX.

(142) 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 ManualA 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.

(143) 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.

(144) The active ingredient mixture of the compounds according to any one of embodiments 1 to 25 with active ingredients described above comprises a compound according to any one of embodiments 1 to 25 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.

(145) 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.

(146) The mixtures comprising a compound of according to any one of embodiments 1 to 25 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 according to any one of embodiments 1 to 25 and the active ingredients as described above is not essential for working the present invention.

(147) 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.

(148) 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.

(149) 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 pouringwhich are to be selected to suit the intended aims of the prevailing circumstancesand 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.

(150) 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.

(151) The compounds 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.

(152) 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.

(153) The present invention also comprises seeds coated or treated with or containing a compound according to any one of embodiments 1 to 25. 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 according to any one of embodiments 1 to 25. Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound according to any one of embodiments 1 to 25.

(154) 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 according to any one of embodiments 1 to 25 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.

(155) The pesticidal/insecticidal properties of the compounds according to any one of embodiments 1 to 25 can be illustrated via the following tests:

(156) Diabrotica balteata (Corn Root Worm):

(157) Maize sprouts placed onto an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10000 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 4 days after infestation. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: 1, 2, 6, 9, 15, 16, 17, 19, 20, 21, 22, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 58, 59, 61, 62, 64, and 65.

(158) Euschistus heros (Neotropical Brown Stink Bug): Feeding/contact activity

(159) Soybean leaves on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10000 ppm DMSO stock solutions. After drying the leaves were infested with N2 nymphs. The samples were assessed for mortality 5 days after infestation. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: 1, 2, 6, 9, 15, 16, 17, 19, 20, 21, 22, 33, 34, 35, 36, 37, 38, 39, 40, 41 and 42.

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

(161) Sunflower leaf discs were placed onto agar in a 24-well microtiter plate and sprayed with aqueous test solutions prepared from 10000 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. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: 1, 2, 9, 15, 16, 19, 20, 21, 22, 34, 17, 36, 42 and 57.

(162) Plutella xylostella (Diamond Back Moth): Feeding/Contact Activity

(163) 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10000 ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (10 to 15 per well). The samples were assessed for mortality 5 days after infestation. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: 1, 2, 6, 9, 15, 16, 17, 19, 20, 21, 22, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46 and 47.

(164) Spodoptera littoralis (Egyptian Cotton Leaf Worm): Feeding/Contact Activity

(165) Cotton leaf discs were placed onto agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10000 ppm DMSO stock solutions. After drying the leaf discs were infested with five L1 larvae. The samples were assessed for mortality 3 days after infestation. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: 1, 2, 6, 9, 15, 16, 18, 18, 19, 20, 21, 22, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45 and 46.

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

(167) Bean leaf discs on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10000 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. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: 1, 2, 6, 9, 15, 16, 17, 19, 20, 21, 22, 33, 34, 35, 36, 37, 38, 39, 41, 42 and 44.

(168) Thrips tabaci (Onion Thrips): Feeding/Contact Activity

(169) Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10000 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. The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: 6, 9, 16, 19, 20, 22, 22, 33, 34, 35, 36, 37, 40, 41, 42, 43, 45 and 46.

(170) The 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, 12.5 ppm, ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

(171) Biological Comparison Data:

(172) Compound A is disclosed in WO2014/122083 as example (Ic-2) (p. 82, Table 3). The activities of compounds A is compared with the activities of compound 41 and 42, according to the present invention. The tests are carried out at different concentrations (ppm). It can be seen that compounds 41 and 42 of the present invention have surprisingly improved activity in comparison with compounds A.

(173) a) Insecticidal Activity Against Plutella xylostella (Diamond Back Moth, Larvicide L-2/3, Feeding/Contact)

(174) Chinese cabbage plants are sprayed with diluted test solutions in an application chamber. 1 day after treatment, excised leaves are placed in petri dishes and infested with 10 L2 (2 replicates). Samples are checked 5 days after infestation for mortality, feeding behavior, and growth regulation.

(175) TABLE-US-00015 Concentration Mortality Compound Compound Structure (ppm) (%) Cpd A 0.8 0.2 0.05 0.0125 100 100 85 35 Cpd 41 0 0.8 0.2 0.05 0.0125 100 100 100 90 Cpd 42 0.8 0.2 0.05 0.0125 100 100 100 95

(176) Furthermore, besides of the insecticidal properties, the compounds according to any one of embodiments 1 to 25 have surprisingly shown to have improved degradation properties compared with prior art compounds. Additionally, the compounds according to any one of embodiments 1 to 25 have surprisingly shown to be less toxic to bees compared with prior art compounds.