Pesticidally active pyrazole derivatives
11589585 · 2023-02-28
Assignee
Inventors
- André JEANGUENAT (Stein, CH)
- Myriem El Qacemi (Stein, CH)
- André STOLLER (Stein, CH)
- Aurelien Bigot (Stein, CH)
- Denis Gribkov (Münchwilen, CH)
Cpc classification
Y02A40/146
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
A01N43/82
HUMAN NECESSITIES
A01N43/80
HUMAN NECESSITIES
C07D403/04
CHEMISTRY; METALLURGY
International classification
A01N43/80
HUMAN NECESSITIES
Abstract
A compound of formula (II) or formula (III) ##STR00001##
As defined herein.
Claims
1. A compound of formula (II) or formula (III) ##STR00219## wherein T is selected from ##STR00220## wherein ##STR00221## indicates the bond to the pyrazole group; R.sup.5 and R.sup.6 are independently selected from H, methyl and trifluoromethoxy; A is selected from C—H and N; R.sup.2 is selected from H, methyl, trifluoromethyl and halogen; 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, formyl, 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.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 is unsubstituted or substituted with 1 to 10 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.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, N—C.sub.1-C.sub.6-alkylamino, N—C.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, N—C.sub.1-C.sub.6-alkylamino, N—C.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 10 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; or an agrochemically acceptable salt or N-oxide thereof.
2. The compound or salt according to claim 1 wherein the formula is formula (II).
3. The compound or salt according to claim 2 wherein T is selected from ##STR00222## wherein ##STR00223## indicates the bond to the pyrazole group; R.sup.5 and R.sup.6 are independently selected from H, methyl and trifluoromethoxy; A is selected from C—H and N; R.sup.2 is selected from H, methyl, trifluoromethyl and halogen; with the proviso that when T is T6, A is C—H, R.sup.5 and R.sup.6 are H, Z.sup.1 is CF.sub.3 or CF.sub.2CF.sub.2CF.sub.2CF.sub.3, and Q is cyclopropyl or 1-cyanocyclopropyl, then R.sup.1 is not H.
4. The compound or salt according to claim 2 wherein R.sub.2 is Cl; A is selected from C—H and N; and T is ##STR00224##
5. The compound or salt according to claim 2 wherein R.sup.2 is Cl; A is selected from C—H and N; and T is selected from ##STR00225##
6. The compound or salt according to claim 1 wherein the formula is formula (III).
7. The compound or salt according to claim 6 wherein T is selected from ##STR00226## wherein ##STR00227## indicates the bond to the pyrazole group; R.sup.5 and R.sup.6 are independently selected from H, methyl and trifluoromethoxy; A is selected from C—H and N; R.sup.2 is selected from H, methyl, trifluoromethyl and halogen; 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, formyl, 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.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 is unsubstituted or substituted with 1 to 10 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.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, N—C.sub.1-C.sub.6-alkylamino, N—C.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, N—C.sub.1-C.sub.6-alkylamino, N—C.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 10 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; with the proviso that when T is T6, A is C—H, R.sup.5 and R.sup.6 are H, Z.sup.1 is CF.sub.3 or CF.sub.2CF.sub.2CF.sub.2CF.sub.3, and Q is cyclopropyl or 1-cyanocyclopropyl, then R.sup.1 is not H.
8. The compound or salt according to claim 6 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.1-C.sub.6-alkylcarbonyl and C.sub.1-C.sub.6-alkoxycarbonyl, wherein each of C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6 alkynyl, C.sub.1-C.sub.6-alkylcarbonyl and C.sub.1-C.sub.6-alkoxycarbonyl is unsubstituted or substituted with 1 to 10 substituents independently selected from halogen, cyano, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-alkoxycarbonyl; R.sub.2 is Cl; A is selected from C—H and N; Q is ##STR00228## R.sup.3 is selected from H and CN; and T is ##STR00229##
9. The compound or salt according to claim 5 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.1-C.sub.6-alkylcarbonyl and C.sub.1-C.sub.6-alkoxycarbonyl, wherein each of C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6 alkynyl, C.sub.1-C.sub.6-alkylcarbonyl and C.sub.1-C.sub.6-alkoxycarbonyl is unsubstituted or substituted with 1 to 10 substituents independently selected from halogen, cyano, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-alkoxycarbonyl; R.sup.2 is Cl; A is selected from C—H and N; Q is ##STR00230## R.sup.3 is selected from H and CN; and T is selected from ##STR00231##
Description
EXAMPLES
(1) The following compounds according to embodiment 1 may be prepared according to the methods described herein or according to known methods, e.g. as disclosed in WO2017/108569.
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. 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.
Preparation of 5-fluoro-3-methoxy-1-methyl-4-(trifluoromethyl)pyrazole
(4) ##STR00130##
(5) A mixture of methylhydrazine (1.32 ml, 24.6 mmol) and triethylamine (3.15 ml, 22.4 mmol) in 12 ml of ethanol was added dropwise at 25° C.-30° C. to a solution of 1-methoxy-(perfluoro-2-methyl-1-propene) (3.32 ml, 22.4 mmol) in 8 ml of ethanol. The addition was exothermic and the reaction was stirred overnight at room temperature. The ethanol was carefully evaporated, residue was diluted with tert-butyl methyl ether, and the organic layer was washed with water, brine, dried over sodium sulfate, filtrated and evaporated to give the crude product as yellow oil.
(6) .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 3.61 (d, 3H) 3.90 (s, 3H).
Preparation of 5-(4-bromopyrazol-1-yl)-3-methoxy-1-methyl-4-(trifluoromethyl)pyrazole
(7) ##STR00131##
(8) Under Argon, 5-fluoro-3-methoxy-1-methyl-4-(trifluoromethyl)pyrazole (2.9 g, 11.7 mmol), 4-bromo-1H-pyrazole (2.11 g, 14.1 mmol) and potassium carbonate (3.43 g, 24.6 mmol) were dissolved in 35 ml THF. The yellow solution was heated over 3 days at 80° C. The mixture was then diluted with tert butyl methyl ether, quenched with 15 ml of water, extracted 2 times with 20 ml of tert-butyl methyl ether, the organic phase was washed with brine, dried over sodium sulfate, filtrated and evaporated. The crude resin obtained (4.76 g) was purified over silica to give 5-(4-bromopyrazol-1-yl)-3-methoxy-1-methyl-4-(trifluoromethyl)pyrazole.
(9) .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 3.59 (s, 3H) 3.98 (s, 3H) 7.66 (s, 1H) 7.77 (s, 1H).
Synthesis of 2-chloro-5-[1-[5-methoxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]benzoic acid
(10) ##STR00132##
(11) In a 3-neck round bottom flask under argon, 5-(4-bromopyrazol-1-yl)-3-methoxy-1-methyl-4-(trifluoromethyl)pyrazole (1.81 g, 5.01 mmol), methyl 2-chloro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate (1.56 g, 5.26 mmol) and sodium hydrogen carbonate 1 M (15 ml, 15 mmol) were dissolved in 30 ml of 2-propanol. The mixture was purged with argon for 5 min. After that, tetrakis(triphenylphosphine)palladium(0) (177 mg, 0.15 mmol) was added and the mixture was heated at 100° C. overnight. The mixture was filtrated, evaporated, diluted with ethyl acetate, quenched with 10 ml of sodium hydroxide 2N, and extracted 2 times with ethyl acetate. The water phase was acidified to pH 2 using hydrochloride acid 10% and extracted 3 times with 20 ml of ethyl acetate, the organic phase was washed with brine, dried over sodium sulfate, filtrated and evaporated to give 2-chloro-5-[1-[5-methoxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]benzoic acid as a yellow resin.
(12) .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 3.62-3.68 (m, 3H) 4.00 (s, 3H) 7.52-7.56 (m, 1H) 7.60-7.64 (m, 1H) 7.91 (s, 1H) 8.11 (d, 1H) 8.14 (d, 1H).
Preparation of 2-chloro-5-[1-[5-hydroxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]benzoic acid
(13) ##STR00133##
(14) 2-Chloro-5-[1-[5-methoxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]benzoic acid (1.99 g, 4.57 mmol) in a 33% solution HBr in AcOH (12.4 ml) was stirred under argon in a thick glass microwave tube. The colorless solution was heated at 60° C. overnight. After dilution with tert-butyl methyl ether, the solution was quenched with saturated sodium hydrogen carbonate. The water phase was acidified to pH 2 with 10% HCl and extracted with 3 times with 20 ml of ethyl acetate; the organic phase was washed with brine, dried over sodium sulfate, filtrated and evaporated. The crude beige product was purified to give 2-chloro-5-[1-[5-hydroxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]benzoic acid as white crystals.
(15) .sup.1H NMR (400 MHz, CD.sub.3OD) δ ppm 3.28-3.36 (m, 3H) 3.51-3.56 (m, 3H) 7.54 (d, 1H) 7.78 (dd, 1H) 8.11 (d, 1H) 8.28 (s, 1H) 8.40 (s, 1H)
Preparation of 2-chloro-N-cyclopropyl-5-[1-[5-hydroxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]benzamide
(16) ##STR00134##
(17) To a solution of 2-chloro-5-[1-[5-hydroxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]benzoic acid (200 mg) in dimethylformamide (1.55 mL) was added Carbonyldiimidazole (102 mg). The resulting solution was stirred at room temperature for 30 min then cyclopropylamine (0.07 mL) was added. The resulting solution was stirred at room temperature for 2 hours then allowed to stand overnight.
(18) The reaction mixture was then diluted with ethyl acetate and poured on water. The aqueous phase was extracted twice with ethyl acetate. The organic phase was extracted with water and with brine then they were combined, dried over magnesium sulfate, filtered and concentrated under vacuo to give 2-chloro-N-cyclopropyl-5-[1-[5-hydroxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]benzamide (171 mg) as a crude solid.
(19) .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 0.56-0.75 (m, 2H) 0.80-1.03 (m, 2H) 2.92-3.01 (m, 1H) 3.68 (s, 3H) 6.34-6.55 (m, 1H) 7.43 (d, 1H) 7.47-7.57 (m, 1H) 7.86 (d, 1H) 7.93 (s, 1H) 8.10 (s, 1H) .sup.19F NMR (377 MHz, CDCl.sub.3) δ ppm−56.22 (s, 1F)
Preparation of 2-chloro-N-(1-cyanocyclopropyl)-5-[1-[5-hydroxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]benzamide
(20) ##STR00135##
(21) A mixture of 2-chloro-5-[1-[5-hydroxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]benzoic acid (300 mg, 0.698 mmol), 3-(ethyliminomethylideneamino)-N,N-dimethylpropan-1-amine; hydrochloride (150 mg, 0.768 mmol), 1-amino-1-cyano-cyclopropane-HCl (211 mg, 1.75 mmol) and 3-hydroxytriazolo[4,5-b]pyridine (107 mg, 0.768 mmol) in 10 ml of dichloromethane was stirred at room temperature. To this yellow solution was added 4-dimethylaminopyridine (215 mg, 1.75 mmol) and mixture was stirred overnight at room temperature until complete conversion. The mixture was diluted with dichloromethane, quenched with HCl 2N, the organic phase was washed successively with water and once with brine, dried over MgSO.sub.4, filtrated and evaporated to give after a purification on silica gel 2-chloro-N-(1-cyanocyclopropyl)-5-[1-[5-hydroxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]benzamide as a white solid.
(22) .sup.1H NMR (400 MHz, CD.sub.3OD) δ ppm 1.27-1.31 (m, 2H) 1.48-1.52 (m, 2H) 3.42 (s, 3H) 7.40 (d, 1H) 7.63-7.67 (m, 2H) 8.18 (d, 1H) 8.29 (s, 1H)
(23) Similarly to the last two examples, the following compounds were prepared:
2-chloro-N-(1-cyanocyclopropyl)-5-[1-[5-hydroxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]-N-methyl-benzamide
(24) ##STR00136##
(25) .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.32-1.85 (m, 4H) 2.93-3.03 and 3.26 (2×m, 3H) 3.69 (m, 3H) 7.38-8.40 (m, 5H).
(26) .sup.19F NMR (377 MHz, CDCl.sub.3) δ ppm−56.25-56.20 (m, 3F)
2-chloro-N-cyclopropyl-5-[1-[5-hydroxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]-N-methyl-benzamide
(27) ##STR00137##
(28) .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 0.45-1.05 (m, 4H) 2.74-2.84 and 2.94 (2×m, 2H) 3.16 and 3.50 (2×s, 3H) 3.69 (s, 3H) 7.41-7.52 (m, 3H) 7.90 (s, 1H) 8.08 (s, 1H)
(29) 19F NMR (377 MHz, CDCl.sub.3) δ ppm−56.17 (s, 3F)
2-chloro-N-cyclopropyl-N-ethyl-5-[1-[5-hydroxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]benzamide
(30) ##STR00138##
(31) .sup.1H NMR (400 MHz, CD.sub.3OD) δ ppm 0.52-1.02 (m, 4H) 1.16-1.35 (m, 3H) 2.77-2.90 and 3.12-3.29 (2×m, 1H) 3.42-3.87 (m, 5H) 7.50 (m, 1H) 7.64-7.75 (m, 2H) 8.25-8.53 (m, 2H)
(32) .sup.19F NMR (377 MHz, CD.sub.3OD) δ ppm−58.13 (s, 3F)
Example 1: Preparation of 5-[4-[4-chloro-3-[(1-cyanocyclopropyl)carbamoyl]phenyl]pyrazol-1-yl]-1-methyl-4-(trifluoromethyl)pyrazol-3-yl]1,1,2,2,2-pentafluoroethanesulfonate
(33) ##STR00139##
(34) To a solution of 2-chloro-N-(1-cyanocyclopropyl)-5-[1-[5-hydroxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]benzamide (100 mg) in acetonitrile (0.88 mL) was added potassium carbonate (61 mg) followed by a dropwise addition of pentafluoroethanesulfonyl chloride (100 mg) at room temperature. The reaction mixture was stirred at room temperature for 1 hour and was then filtered. The resulting filtrate was concentrated under vacuo and purified on silica gel (eluant: cyclohexane/ethyl acetate, 6:4) to give 5-[4-[4-chloro-3-[(1-cyanocyclopropyl)carbamoyl]phenyl]pyrazol-1-yl]-1-methyl-4-(trifluoromethyl)pyrazol-3-yl]1,1,2,2,2-pentafluoroethanesulfonate.
(35) 1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.36-1.50 (m, 2H) 1.59-1.76 (m, 2H) 3.84 (s, 3H) 6.99 (bs, 1H) 7.46 (d, 1H) 7.56 (dd, 1H) 7.93 (d, 1H) 7.99 (s, 1H) 8.15 (s, 1H)
(36) 19F NMR (377 MHz, CDCl.sub.3) δ ppm−112.42 (s, 2F) −79.06 (s, 3F) −56.13 (s, 3F),
Preparation of methyl 2-chloro-5-(1-tetrahydropyran-2-ylpyrazol-4-yl)benzoate
(37) ##STR00140##
(38) To a solution of 4-bromo-1-tetrahydropyran-2-yl-pyrazole (0.108 g) in isopropanol (7 mL) was added methyl 2-chloro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate (0.1386 g) and an aqueous solution of sodium bicarbonate (1M, 1.4 mL). The reaction mixture was degassed with argon and then tetrakis(triphenylphosphine) palladium (0) was added (16.2 mg). The reaction mixture was then heated to 100° C. for 4 hours and cooled down to room temperature. The reaction mixture was partitioned between water and AcOEt. The aqueous phase was extracted with AcOEt twice, the combined organic layers were dried on Na.sub.2SO.sub.4 and concentrated under vacuum. The crude material was purified by flash chromatography (Cyclohexane/AcOEt) to give methyl 2-chloro-5-(1-tetrahydropyran-2-ylpyrazol-4-yl)benzoate as a colourless oil.
(39) 1H NMR (400 MHz, CDCl.sub.3) □ ppm 1.58-1.79 (m, 4H) 2.09-2.18 (m, 2H) 3.68-3.79 (m, 1H) 3.95 (s, 3H) 4.05-4.15 (m, 1H) 5.38-5.44 (m, 1H) 7.43 (d, 1H) 7.52 (dd, 1H) 7.82 (s, 1H) 7.90 (s, 1H) 7.93 (d, 1H).
Preparation of methyl 2-chloro-5-(1H-pyrazol-4-yl)benzoate
(40) ##STR00141##
(41) To a solution of methyl 2-chloro-5-(1-tetrahydropyran-2-ylpyrazol-4-yl)benzoate (2.5 g) in tetrahydrofuran (31 mL) was added concentrated hydrochloric acid (36% in water, 2.3 mL). The reaction mixture was stirred at 55° C. for 30 minutes and cooled down to room temperature. The reaction mixture was diluted with AcOEt, washed with saturated aqueous NaHCO.sub.3 and with brine. The combined organic layers were dried over Na.sub.2SO.sub.4 and concentrated under vacuum. The crude material was purified by flash chromatography (Cyclohexane/AcOEt) to give methyl 2-chloro-5-(1H-pyrazol-4-yl)benzoate as a white solid.
(42) 1H NMR (400 MHz, CDCl.sub.3) □ ppm 3.97 (s, 3H) 7.45 (d, 1H) 7.55 (dd, 1H) 7.90 (s, 2H) 7.96 (d, 1H).
Preparation of 2-chloro-5-(1H-pyrazol-4-yl)benzoic acid
(43) ##STR00142##
(44) Methyl 2-chloro-5-(1H-pyrazol-4-yl)benzoate (2 g) was dissolved in dioxane (10 ml) and water (4 ml). NaOH pellets (0.372 g) were added at r.t. and the reaction mixture was stirred overnight at r.t. The reaction mixture was then concentrated under vacuum and diluted with some water. This basic solution was washed with methyl tert-butyl ether and was then acidified with HCl 1 N. Precipitation of 2-chloro-5-(1H-pyrazol-4-yl)benzoic acid occurred. The solid was rinsed with water and dried on the filter. The solid was redissolved in CH.sub.2Cl.sub.2/methanol and dried on MgSO.sub.4. The solution was then concentrated under vacuum to give 2-chloro-5-(1H-pyrazol-4-yl)benzoic acid as white crystals. Melting point: 227-229° C.
Preparation of 2-chloro-N-cyclopropyl-5-(1H-pyrazol-4-yl)benzamide
(45) ##STR00143##
(46) 2-Chloro-5-(1H-pyrazol-4-yl)benzoic acid (825 mg) was dissolved in DMA (3 mL). Then cyclopropylamine (0.280 mL), Hünig's base (1.59 mL) were added at r.t. and the reaction mixture was stirred at r.t. for 10 minutes. The mixture was cooled down with an icebath and BOP-CI (1.037 g) was added in 1 portion. The icebath was removed and the light suspension stirred for 8 h at 55° C. then at r.t. overnight. As the reaction was not completed, cyclopropylamine (0.127 mL), Huenig's base (0.318 mL) and BOP-CI (0.471 g) were added and the reaction mixture was heated again to 55° C. for 6 hours. The reaction mixture was poured into water. The precipitation of white crystals occurred.
(47) After stirring for 10 minutes, the solid was filtered off and dried on filter. It was triturated in petrol ether to provide 2-chloro-N-cyclopropyl-5-(1H-pyrazol-4-yl)benzamide as white crystals.
(48) Melting point: 102-103° C.
Preparation of 5-methoxy-2-methyl-4-(trifluoromethyl)pyrazole-3-carbonitrile
(49) ##STR00144##
(50) 5-fluoro-3-methoxy-1-methyl-4-(trifluoromethyl)pyrazole (20.0 g) and potassium cyanide (19.7 g) were dissolved in MeCN (150 ml) and the mixture was heated under reflux for 16 h. After cooling, the precipitate was filtered off and concentrated. Column chromatography afforded title compound as colorless oil (13.2 g). .sup.1H NMR (400 MHz, CDCl.sub.3) δ 3.98 (s, 3H), 3.94 (s, 3H). .sup.19F NMR (283 MHz, CDCl.sub.3) δ−55.95 (s, 3F).
Preparation of 5-methoxy-2-methyl-4-(trifluoromethyl)pyrazole-3-carbaldehyde
(51) ##STR00145##
(52) A solution of diisobutylaluminum hydride in toluene (1.5 M, 42 mL) was added into a chilled (−40° C.) solution of 5-methoxy-2-methyl-4-(trifluoromethyl)pyrazole-3-carbonitrile (13.0 g) in toluene (100 mL). After 10 min the cooling bath was removed and the reaction was stirred at room temperature for 2 h followed by careful addition of 2 N HCl (40 mL). The mixture was stirred at room temperature for 45 min then poured into water and extracted with ethyl acetate three times, the organic combined phases were dried over sodium sulfate and concentrated. Column chromatography afforded title compound as yellow oil (7.6 g).
Preparation of (3E)-5-methoxy-2-methyl-4-(trifluoromethyl)pyrazole-3-carbaldehyde oxime
(53) ##STR00146##
(54) To a solution of 5-methoxy-2-methyl-4-(trifluoromethyl)pyrazole-3-carbaldehyde (7.2 g) in ethanol (80 mL) was added sodium bicarbonate (8.72 g) and hydroxylamine hydrochloride (4.81 g). The mixture was stirred at room temperature for 4 h. The reaction mixture was poured into water. The resulting crystals were collected by filtration, washed with water and dried to obtain title compound as a white powder (6.4 g). .sup.1H NMR (400 MHz, DMSO-d.sup.6) δ 12.23-12.22 (m, 1H), 8.11-7.62 (m, 2H), 3.99-3.51 (m, 6H). .sup.19F NMR (283 MHz, DMSO-d.sup.6) δ-52.63-51.12 (m, 3F).
Preparation of (3Z)—N-hydroxy-5-methoxy-2-methyl-4-(trifluoromethyl)pyrazole-3-carboximidoyl chloride
(55) ##STR00147##
(56) (3E)-5-methoxy-2-methyl-4-(trifluoromethyl)pyrazole-3-carbaldehyde oxime (6 g) was mixed N-Chlorosuccinimide (3.77 g) in DMF (40.0 mL) and stirred at room temperature for 2 h. The reaction mixture was poured into water and extracted with ethyl acetate two times. The combined organic layers were dried over sodium sulfate, filtered and concentrated under vacuum to give title compound as yellow oil (6.2 g). .sup.1H NMR (400 MHz, DMSO-d.sup.6) δ 13.34 (s, 1H), 3.90 (s, 3H), 3.73 (s, 3H). .sup.19F NMR (283 MHz, DMSO-d.sup.6) δ-52.48 (s, 3F).
Preparation of methyl 2-chloro-5-[3-[5-methoxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]isoxazol-5-yl]benzoate
(57) ##STR00148##
(58) To a solution of (3E)-5-methoxy-2-methyl-4-(trifluoromethyl)pyrazole-3-carbaldehyde oxime (5.7 g) and methyl 2-chloro-5-ethynyl-benzoate (5.47 g) in dichloromethane (60 mL) was added triethylamine (5.17 g). The mixture was stirred at room temperature for 16 h. The reaction mixture was poured into water and extracted with dichloromethane twice, the combined organic layers were dried over sodium sulfate and concentrated. Column chromatography afforded title compound as a white solid (4.5 g). .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.28 (s, 1H), 7.88 (d, J=8.0 Hz, 1H), 7.61 (d, J=8.4 Hz, 1H), 6.78 (s, 1H), 4.00 (d, J=3.5 Hz, 6H), 3.89 (s, 3H). .sup.19F NMR (283 MHz, CDCl.sub.3) δ−34.42 (s, 3F).
Preparation of 2-chloro-5-[3-[5-methoxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]isoxazol-5-yl]benzoic acid
(59) ##STR00149##
(60) To a stirred solution of methyl 2-chloro-5-[3-[5-methoxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]isoxazol-5-yl]benzoate (2.1 g) in THE (10 mL) was added sodium hydroxide (77 mg) and water (3 mL). The reaction mixture was stirred at room temperature for 2 h. The pH value was adjusted to 2 with concentrated HCl. The reaction mixture was extracted with ethyl acetate three times. The organic layers were dried over anhydrous sodium sulfate. After filtration and concentrated under vacuum title compound was obtained as a yellow powder (2.1 g).
Preparation of 2-chloro-5-[3-[5-hydroxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]isoxazol-5-yl]benzoic acid
(61) ##STR00150##
(62) To 20 ml of a 33 wt. % hydrogen bromide acetic acid solution was added 2-chloro-5-[3-[5-methoxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]isoxazol-5-yl]benzoic acid (1.8 g). The mixture was stirred at 60° C. for 12 h. The reaction mixture was poured into water. The resulting crystals were collected by filtration, washed with water and dried to obtain title compound as a grey powder (1.6 g). .sup.1H NMR (400 MHz, DMSO-d.sup.6) δ 13.77 (s, 1H), 11.19 (s, 1H), 8.34 (s, 1H), 8.10 (d, J=8.3 Hz, 1H), 7.78 (d, J=8.3 Hz, 1H), 7.58 (s, 1H), 3.71 (s, 3H). .sup.19F NMR (283 MHz, DMSO-d.sup.6) δ−61.33 (s, 3F).
Preparation of 2-chloro-N-(1-cyanocyclopropyl)-5-[3-[5-hydroxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]isoxazol-5-yl]-N-methyl-benzamide
(63) ##STR00151##
(64) To a stirred solution of 2-chloro-5-[3-[5-hydroxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]isoxazol-5-yl]benzoic acid (0.300 g), 1-(methylamino)cyclopropanecarbonitrile hydrochloride (0.154 g) and HATU (0.441 g) in DMF (10 mL) was added N,N-Diisopropylethylamine (0.300 g). The mixture was stirred at room temperature for 16 h. The reaction mixture was poured into water and extracted with ethyl acetate twice. The combined organic layers were dried over sodium sulfate and concentrated. Column chromatography afforded title product as a white powder (0.14 g). .sup.1H NMR (400 MHz, DMSO-d.sup.6) δ 11.19 (s, 1H), 8.07 (m, 2H), 7.78 (m, 1H), 7.53 (s, 1H), 3.70 (s, 3H), 2.86 (s, 3H), 1.69 (m, 2H), 1.52 (m, 2H). .sup.19F NMR (283 MHz, DMSO-d.sup.6) δ-61.52 (d, J=15.6 Hz, 3F).
Example 37: Preparation of [5-[5-[4-chloro-3-[(1-cyanocyclopropyl)-methyl-carbamoyl]phenyl]isoxazol-3-yl]-1-methyl-4-(trifluoromethyl)pyrazol-3-yl]1,1,1,2,3,3,3-heptafluoropropane-2-sulfonate
(65) ##STR00152##
(66) To a stirred solution of 2-chloro-N-(1-cyanocyclopropyl)-5-[3-[5-hydroxy-2-methyl-4-(trifluoromethyl)pyrazol-3-yl]isoxazol-5-yl]-N-methyl-benzamide (0.100 g) and potassium carbonate (0.0890 g) in tetrahydrofuran (15 mL) was added 1,1,1,2,3,3,3-heptafluoropropane-2-sulfonyl fluoride (0.108 g). Then the reaction was stirred at 70° C. for 24 hours. The reaction mixture were poured into water and extracted with ethyl acetate twice. The combined organic phases were dried over sodium sulfate and concentrated. Column chromatography afforded title product as a yellow oil (0.08 g). .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.99-7.82 (m, 2H), 7.70-7.52 (m, 1H), 6.88 (d, J=23.6 Hz, 1H), 4.07 (s, 3H), 3.26-2.98 (m, 3H), 1.50 (m, 2H), 1.37 (m, 2H). .sup.19F NMR (283 MHz, CDCl.sub.3) δ−64.00 (d, J=32.0 Hz, 3F), −80.32 (d, J=6.4 Hz, 6F), −175.06 (s, 1F).
Preparation of 1,1,1,2,3,3,3-heptafluoropropane-2-sulfonyl fluoride
(67) ##STR00153##
(68) To a solution of KF (4.6 g) in 40 ml of sulfolane in a 250 mL steel autoclave, sulphuryl fluoride (51 g) and perfluoropropene (57.6 g) were loaded below −100° C. After the addition the reaction mixture was heated to 140° C. for about 4 h. Subsequently the reaction mixture was cooled and distilled at atmospheric pressure. Title compound (43g) was obtained within the boiling range of 0-39° C. as a colorless liquid. .sup.19F NMR (282 Mz, CDCl.sub.3): δ 46.2 (d, J=5.6 Hz, 1F), −81.1 (m, 6F), −176.1 (d, J=7.8 Hz, 1F).
(69) The following compounds in Table 1 were prepared in analogy with Example 1 and 37.
(70) TABLE-US-00004 TABLE 1 Examples of compounds of formula (I) Ex. No. Structure NMR data 2
(71) 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 34 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.
(72) 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.
(73) The following mixtures of the compounds according to any one of embodiments 1 to 34 with active ingredients are preferred (the abbreviation “TX” means “one compound selected from the compounds according to any one of embodiments 1 to 34, preferably embodiment 34):
(74) an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628)+TX,
(75) 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 50′439 (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 I (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 I (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 I (696)+TX, pyrethrin II (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,
(76) 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,
(77) 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,
(78) 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,
(79) 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,
(80) a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537)+TX,
(81) 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,
(82) 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-1l1-en-1-yl acetate (IUPAC name) (785)+TX, trimedlure (839)+TX, trimedlure A (alternative name) (839)+TX, trimedlure B.sub.1 (alternative name) (839)+TX, trimedlure B2 (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, El 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 0-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473)+TX, isoprothiolane (474)+TX, isothioate (1244)+TX, isoxathion (480)+TX, ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX, jasmolin II (696)+TX, jodfenphos (1248)+TX, juvenile hormone I (alternative name) [CCN]+TX, juvenile hormone II (alternative name) [CCN]+TX, juvenile hormone III (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,
(83) a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580)+TX,
(84) 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,
(85) 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,
(86) 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,
(87) a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN]+TX,
(88) a wound protectant selected from the group of substances consisting of mercuric oxide (512)+TX, octhilinone (590) and thiophanate-methyl (802)+TX,
(89) 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, tebuconazole [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 [1 7501 3-1 8-0]+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, dimethomorph [110488-70-5]+TX, SYP-LI90 (Flumorph) [211867-47-9]4+TX, dithianon [3347-22-6]+TX, ethaboxam [162650-77-3]+TX, etridiazole [2593-15-9]+TX, famoxadone [131807-57-3]+7X, 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-1 1-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.
(90) The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The above described mixing partners are known. Where the active ingredients are included in “The Pesticide Manual” [The Pesticide Manual—A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound “abamectin” is described under entry number (1). Where “[CCN]” is added hereinabove to the particular compound, the compound in question is included in the “Compendium of Pesticide Common Names”, which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2004]; for example, the compound “acetoprole” is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html.
(91) 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 “develoment 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.
(92) The active ingredient mixture of the compounds according to any one of embodiments 1 to 34 with active ingredients described above comprises a compound according to any one of embodiments 1 to 34 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.
(93) 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.
(94) The mixtures comprising a compound of according to any one of embodiments 1 to 34 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 34 and the active ingredients as described above is not essential for working the present invention.
(95) 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.
(96) 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.
(97) The application methods for the compositions, that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring—which are to be selected to suit the intended aims of the prevailing circumstances—and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention. Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.
(98) 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.
(99) 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.
(100) 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.
(101) The present invention also comprises seeds coated or treated with or containing a compound according to any one of embodiments 1 to 34. 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 34. 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 34.
(102) 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 34 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.
(103) The pesticidal/insecticidal properties of the compounds according to any one of embodiments 1 to 34 can be illustrated via the following tests:
(104) Spodoptera littoralis (Egyptian Cotton Leaf Worm)
(105) Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions. After drying the leaf discs were infested with five L1 larvae. The samples were assessed for mortality, anti-feedant effect, and growith inhibition in comparison to untreated samples 3 days after infestation. Control of Spodoptera littoralis by a test sample is when at least one of mortality, anti-feedant effect, and growith inhibition is higher than the untreated sample. The following compounds resulted in at least 80% control at an application rate of 200 ppm: compounds 1, 2, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 30, 31, 32, 33, 34, 35, 36, 37, 38, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 54, 56, 57, 58, 59, 60, 62, 64, 65, 67, 68, 69.
(106) Plutella xylostella (Diamond Back Moth):
(107) 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (10 to 15 per well). The samples were assessed for mortality and growith inhibition in comparison to untreated samples 5 days after infestation. The following compounds resulted in at least 80% control at an application rate of 200 ppm: compounds 1, 2, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 54, 56, 57, 58, 59, 60, 62, 64, 65, 67, 68, 69.
(108) Diabrotica Balteata, (Corn Root Worm)
(109) Maize sprouts, placed on an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality and growith inhibition in comparison to untreated samples 4 days after infestation. The following compounds resulted in at least 80% control at an application rate of 200 ppm: compounds 1, 2, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 41, 43, 45, 46, 47, 48, 49, 50, 51, 52, 54, 56, 57, 58, 59, 60 and 62.
(110) Thrips tabaci (Onion Thrips):
(111) Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions. After drying the leaf discs were infested with a thrips population of mixed ages. The samples were assessed for mortality 6 days after infestation. The following compounds resulted in at least 80% control at an application rate of 200 ppm: compounds 2, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 17, 18, 19, 20, 21, 22, 25, 26, 27, 28, 31, 32, 33, 34, 35, 36, 37, 43, 45, 46, 47, 48, 49, 50, 51, 52, 54, 56, 57, 59, 60 and 62.
(112) Tetranychus urticae (Two-Spotted Spider Mite):
(113) Bean leaf discs on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions. After drying the leaf discs were infested with a mite population of mixed ages. The samples were assessed for mortality on mixed population (mobile stages) 8 days after infestation. The following compounds resulted in at least 80% control at an application rate of 200 ppm: compounds 1, 2, 5, 8, 9, 10, 12, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 33, 34, 35, 36, 37, 38, 45, 46, 48, 49, 50, 51, 52, 54, 57, 58, 59, 60, 62, 64, 65, 67, 68, 69.
(114) Euschistus heros (Neotropical Brown Stink Bug):
(115) Soybean leaves on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions. After drying the leaves were infested with N2 nymphs. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation. The following compounds resulted in at least 80% control at an application rate of 200 ppm: compounds 1, 2, 5, 6, 9, 12, 18, 21, 25 32, 33, 34, 35, 36, 37, 38, 45, 46, 47, 48, 49, 50, 51, 52, 54, 57, 59, 60, 62, 65, 68, 69.
(116) Myzus persicae (Green Peach Aphid):
(117) Sunflower leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test solutions at an application rate of 200 ppm. After drying, the leaf discs were infested with an aphid population of mixed ages. After an incubation period of 6 DAT, samples were checked for mortality. The following compounds resulted in at least 80% control at an application rate of 200 ppm: compounds 2, 5, 8, 9, 10, 12, 14, 17, 18, 19, 21, 22, 23, 25, 26, 27, 29, 33, 34, 35, 36, 37, 38, 41, 45, 46, 47, 48, 49, 50, 51, 52, 54, 57, 59, 60, 62, 64, 69.
(118) 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, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.
(119) Furthermore, besides of the insecticidal properties, the compounds according to any one of embodiments 1 to 34 have surprisingly shown to have improved degradation properties compared with prior art compounds. Additionally, the compounds according to any one of embodiments 1 to 34 have surprisingly shown to be environmentally more tolerated than prior art compounds.