PESTICIDALLY ACTIVE CYCLIC AMINE COMPOUNDS
20230146180 · 2023-05-11
Assignee
Inventors
- Ottmar Franz Hueter (Stein, CH)
- Caroline CHENEL (Basel, CH)
- Pierre Joseph Marcel Jung (Stein, CH)
- Elke Maria HILLESHEIM (Stein, CH)
- Ruifang CHEN (Shanghai, CN)
- Hua Li (Shanghai, CN)
- Long Lu (Shanghai, CN)
Cpc classification
A01N25/00
HUMAN NECESSITIES
C07D241/04
CHEMISTRY; METALLURGY
C07D211/24
CHEMISTRY; METALLURGY
C07D413/04
CHEMISTRY; METALLURGY
C07D211/34
CHEMISTRY; METALLURGY
A01N25/04
HUMAN NECESSITIES
C07D205/04
CHEMISTRY; METALLURGY
A61K45/06
HUMAN NECESSITIES
A01N43/82
HUMAN NECESSITIES
C07D213/74
CHEMISTRY; METALLURGY
A01N43/80
HUMAN NECESSITIES
C07D211/20
CHEMISTRY; METALLURGY
A01N25/00
HUMAN NECESSITIES
C07D211/72
CHEMISTRY; METALLURGY
C07D417/04
CHEMISTRY; METALLURGY
International classification
A01N43/82
HUMAN NECESSITIES
A01N25/04
HUMAN NECESSITIES
A01N43/80
HUMAN NECESSITIES
C07D205/04
CHEMISTRY; METALLURGY
C07D211/20
CHEMISTRY; METALLURGY
C07D213/74
CHEMISTRY; METALLURGY
C07D413/04
CHEMISTRY; METALLURGY
Abstract
Compounds of formula (I) wherein the substituents are as defined in claim 1, and the agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds, can be used as insecticides.
##STR00001##
Claims
1. A compound of the formula (I) ##STR00073## wherein R.sup.1 is CN, C(═S)NH.sub.2 or C.sub.1-C.sub.6-haloalkyl; R.sup.2 is H, OH, halogen, C.sub.1-C.sub.6-alkoxy or C.sub.1-C.sub.6-haloalkoxy; R.sup.3 is H, halogen, cyano, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-haloalkynyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halocycloalkyl, C.sub.1-C.sub.6-alkoxy, or C.sub.1-C.sub.6-haloalkyoxy; R.sup.4 is H, halogen, cyano, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-haloalkynyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halocycloalkyl, C.sub.1-C.sub.6-alkoxy, or C.sub.1-C.sub.6-haloalkyoxy; R.sup.5 is phenyl, phenyl substituted with 1 to 3 substituents R.sup.6, heteroaryl (which is either a 5 or 6 membered monocyclic or a 9 or 10 membered bicyclic), heteroaryl (which is either a 5 or 6 membered monocyclic or a 9 or 10 membered bicyclic) substituted with 1 to 3 substituents R.sup.7; Q is a cyclic amine represented by the formula IIa or a cyclic amine represented by the formula IIb, ##STR00074## wherein the arrow indicates the connection to the carbonyl group; p.sup.1 is 0, 1 or 2 and indicates the number of methylene groups; p.sup.2 is 0, 1 or 2 and indicates the number of methylene groups; q.sup.1 is 1 or 2 and indicates the number of methylene groups; q.sup.2 is 1 or 2 and indicates the number of methylene groups; X is hydrogen, hydroxyl, C.sub.1-C.sub.6-alkoxy, cyano or halogen; Y is cyano, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkylsulfanyl-C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkylsulfinyl-C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkylsulfonyl-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenylsulfanyl-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenylsulfinyl-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenylsulfonyl-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkynylsulfanyl-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkynylsulfinyl-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkynylsulfonyl-C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxycarbonyl, C.sub.1-C.sub.6-alkoxycarbonylamino, R.sup.aR.sup.bNC(O), R.sup.cC(O)NR.sup.d, R.sup.eSO.sub.2NR.sup.f, R.sup.gO—N═CR.sup.h, 4 to 6 membered non-aromatic heterocyclic ring system in which one or two carbons are replaced independently by nitrogen, oxygen, sulfur, or sulfonyl, phenyl, phenyl substituted with 1 to 3 substituents R.sup.8, 5 or 6 membered monocyclic heteroaryl, or 5 or 6 membered monocyclic heteroaryl substituted with 1 to 3 substituents R.sup.9; or X and Y together form a double bond to a nitrogen which is substituted with a group R.sup.mO; A is cyano, C.sub.1-C.sub.6-cyanoalkyl, C.sub.2-C.sub.6-cyanoalkenyl, C.sub.3-C.sub.6-cyanocycloalkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.2-C.sub.6-haloalkenyl, C.sub.3-C.sub.6-halocycloalkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxycarbonyl, C.sub.2-C.sub.6-alkenyloxycarbonyl, C.sub.2-C.sub.6-alkynyloxycarbonyl, C.sub.1-C.sub.6-alkylsulfanyl-C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkylsulfinyl-C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkylsulfonyl-C.sub.1-C.sub.6-alkyl, R.sup.iSO.sub.2, R.sup.jR.sup.kNSO.sub.2, phenyl, phenyl substituted with 1 to 3 substituents R.sup.10, heteroaryl (which is either a 5 or 6 membered monocyclic or a 9 or 10 membered bicyclic), or heteroaryl (which is either a 5 or 6 membered monocyclic or a 9 or 10 membered bicyclic) substituted with 1 to 3 substituents R.sup.11; R.sup.a and R.sup.b are independently selected from hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-haloalkynyl, C.sub.3-C.sub.6-cycloalkyl and C.sub.3-C.sub.6-halocycloalkyl and C.sub.1-C.sub.6-alkylsulfonyl; R.sup.c and R.sup.d are independently selected from hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-haloalkynyl, C.sub.3-C.sub.6-cycloalkyl and C.sub.3-C.sub.6-halocycloalkyl; R.sup.f is hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-haloalkynyl, C.sub.3-C.sub.6-cycloalkyl or C.sub.3-C.sub.6-halocycloalkyl; R.sup.e and R.sup.i are independently selected from C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-haloalkynyl, C.sub.3-C.sub.6-cycloalkyl and C.sub.3-C.sub.6-halocycloalkyl; R.sup.g and R.sup.h are independently selected from hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-haloalkynyl, C.sub.3-C.sub.6-cycloalkyl and C.sub.3-C.sub.6-halocycloalkyl; R.sup.j and R.sup.k are independently selected from hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-haloalkynyl, C.sub.3-C.sub.6-cycloalkyl and C.sub.3-C.sub.6-halocycloalkyl; R.sup.m is hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-haloalkynyl, C.sub.3-C.sub.6-cycloalkyl or C.sub.3-C.sub.6-halocycloalkyl; and R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11 are independently selected from halogen, cyano, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-haloalkynyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halocycloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, C.sub.1-C.sub.6-alkylsulfonyl and C.sub.1-C.sub.6-haloalkylsulfanyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer and N-oxide of the compound of formula I.
2. The compound according to claim 1 wherein p.sup.1 and p.sup.2 are each 0, or p.sup.1 and p.sup.2 are each 1.
3. The compound according to either claim 1 wherein R.sup.1 is CN or C(═S)NH.sub.2.
4. The compound according to claim 1 wherein R.sup.2 is hydrogen and R.sup.4 is hydrogen or cyano.
5. The compound according to claim 1 wherein R.sup.5 is phenyl or phenyl substituted with 1 to 3 substituents R.sup.6, wherein the R.sup.6 is independently selected from halogen, cyano, C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.3-haloalkyl, C.sub.1-C.sub.3-alkoxy; C.sub.1-C.sub.3-haloalkoxy, C.sub.1-C.sub.3-alkylsulfonyl and C.sub.1-C.sub.3-haloalkylsulfanyl.
6. The compound according to claim 1 wherein Q is formula IIa, wherein X is hydrogen or, hydroxyl; Y is C.sub.1-C.sub.3-alkylsulfanyl-methyl, C.sub.1-C.sub.3-alkylsulfinyl-methyl, C.sub.1-C.sub.3-alkylsulfonyl-methyl, C.sub.3-C.sub.4-alkenylsulfanyl-methyl, C.sub.3-C.sub.4-alkenylsulfinyl-methyl, C.sub.3-C.sub.4-alkenylsulfonyl-methyl, C.sub.3-C.sub.4-alkynylsulfanyl-methyl, C.sub.3-C.sub.4-alkynylsulfinyl-methyl, C.sub.3-C.sub.4-alkynylsulfonyl-methyl, methanesulfonylamido, ethanesulfonylamido, 1,1-dioxo-1,2-thiazolidin-2-yl, 1,2,4-oxadiazole-3-yl, 2-pyridyl, substituted 2-pyridyl or, substituted 1,2,4-oxadiazole-3-yl, where the substituents for each are 1 to 3 substituents independently selected from chlorine and methyl; or X and Y together form a double bond to a nitrogen which is substituted with methoxy or ethoxy.
7. The compound according to claim 1 wherein q.sup.1 and q.sup.2 are each 1.
8. The compound according tom claim 1 wherein Q is formula IIb, wherein A is cyano, C.sub.1-C.sub.3-cyanoalkyl, C.sub.1-C.sub.3-haloalkyl, C.sub.2-C.sub.3-haloalkenyl, C.sub.1-C.sub.3-alkoxy-C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.3-alkoxycarbonyl, C.sub.1-C.sub.3-alkylsulfanyl-C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.3-alkylsulfinyl-C.sub.1-C.sub.3-alkyl, R.sup.iSO.sub.2), or 6 membered monocyclic heteroaryl substituted with 1 to 3 substituents independently selected from fluorine and chlorine.
9. A composition comprising a compound as defined in claim 1, one or more auxiliaries and diluent, and optionally one or more other active ingredient.
10. A method (i) of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound as defined as defined in claim 1; or (ii) for the protection of plant propagation material from the attack by insects, acarines, nematodes or molluscs, which comprises treating the propagation material or the site, where the propagation material is planted, with an effective amount of a compound as defined in claim 1; or (iii) of controlling parasites in or on an animal in need thereof comprising administering an effective amount of a compound as defined in claim 1.
11. A plant propagation material, such as a seed, comprising, or treated with or adhered thereto, a compound as defined in claim 1.
12. A compound of the formula III ##STR00075## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are as defined in claim 1.
13. A compound of the formula V ##STR00076## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are as defined claim 1.
14. A compound of the formula VI ##STR00077## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are as defined in claim 1; and R.sup.12 is C.sub.1-C.sub.6-alkyl.
15. A method (i) of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a a composition as defined claim 9; or (ii) for the protection of plant propagation material from the attack by insects, acarines, nematodes or molluscs, which comprises treating the propagation material or the site, where the propagation material is planted, with an effective amount of a composition as defined claim 9; or (iii) of controlling parasites in or on an animal in need thereof comprising administering an effective amount of a composition as defined claim 9.
16. A plant propagation material, such as a seed, comprising, or treated with or adhered thereto, a composition as defined claim 9.
Description
PREPARATORY EXAMPLES
Lcms Methods:
Method 1:
[0407] Spectra were recorded on a ZQ Mass Spectrometer from Waters (Single quadrupole mass spectrometer); Instrument Parameter: Ionisation method: Electrospray Polarity: positive (negative) ions; Capillary (kV) 3.00, Cone (V) 30.00, Extractor (V) 2.00, Gas Temperature (° C.) 350, Drying Gas Flow (mL/min) 9.8, Neb press 45 psig, Mass range: 90 to 1000 Da.
[0408] LC: HP 1100 HPLC from Agilent: solvent degasser, quaternary pump (ZCQ)/binary pump (ZDQ), heated column compartment and diode-array detector. Column: porpshell 120 C.sub.18, 2.7 m particle size, 120 Angström, 4.6×50 mm; Temp: 30° C. DAD Wavelength range (nm): 190 to 400 Solvent Gradient: A=water+n 0.1% HCOOH. B=Acetonitrile+0.8% HCOOH
TABLE-US-00012 Time (min) A % B % Flow (ml/min) 0.00 85.0 15.0 0.6 4.00 5.00 95.00 0.6 10.00 5.00 95.00 0.6
Method 2:
[0409] Spectra were recorded on a ACQUITY Mass Spectrometer from Waters Corporations (SQD or SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.0 kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150° C., Desolvation Temperature: 400° C., Cone Gas Flow: 60 L/hr, Desolvation Gas Flow: 700 L/hr, Mass range: 140 to 800 Da) and an ACQUITY UPLC from Waters Corporations with solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C., DAD Wavelength range (nm): 210 to 400, Solvent Gradient: A=Water/Methanol 9:1+0.1% formic acid, B=Acetonitrile+0.1% formic acid, gradient: 0-100% B in 2.5 min; Flow (ml/min) 0.75.
Method 3:
[0410] Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions, Capillary: 3.00 kV, Cone range: 30 V, Extractor: 2.00 V, Source Temperature: 150° C., Desolvation Temperature: 350° C., Cone Gas Flow: 50 I/h, Desolvation Gas Flow: 650 I/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment, diode-array detector and ELSD detector. Column: Waters UPLC HSS T3, 1.8 m, 30×2.1 mm, Temp: 60° C., DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5% MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH, gradient: 10-100% B in 1.2 min; Flow (ml/min) 0.85.
[0411] The following abbreviations are used in the experimental description below: s=singlet, d=doublet, t=triplet, q=quartet, m=multiplet, RT=retention time, min=minutes.
Example P1: 5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)Piperidine-1-carbonyl]-4-(trifluoromethyl)-2-[4-(trifluoromethyl)phenyl]benzonitrile (Compound P1.1)
[0412] ##STR00025##
Step 1: Methyl 4-hydroxy-5-iodo-2-(trifluoromethyl)benzoate
[0413] ##STR00026##
[0414] Methyl 4-hydroxy-2-(trifluoromethyl)benzoate (10.5 g, 47.7 mmol), iodine (18.0 g, 70.9 mmol) and potassium carbonate (13.2 g, 95.5 mmol) were added to THE (150 mL). The reaction mixture was heated under reflux for 16 hours. Then sodium thiosulfate solution was added. The mixture was extracted with ethyl acetate, and the organic phase was washed three times with brine. The solvent was evaporated and the residue was purified by chromatography (petroleum ether: ethyl acetate=5:1) to give a white solid (6.90 g, 41.8%). .sup.1H-NMR [ppm] in DMSO-d6: 11.75 (s, 1H), 8.23 (s, 1H), 7.23 (s, 1H), 3.81 (s, 3H). LC-MS (method 1): RT=4.34 min; [M−H].sup.−=344.9.
Step 2: Methyl 5-cyano-4-hydroxy-2-(trifluoromethyl)benzoate
[0415] ##STR00027##
[0416] Methyl 4-hydroxy-5-iodo-2-methyl-benzoate (2.50 g, 8.56 mmol) and copper (I) cyanide (1.94 g, 21.7 mmol) were stirred in 1-methylpyrrolidin-2-one (20 mL) at 110° C. for 12 hours. The mixture was poured into water and extracted with ethyl acetate (50 mL), dried over Na.sub.2SO.sub.4, filtered and concentrated under vacuum. The crude product was purified by column chromatography on silica gel (ethyl acetate/petroleum ether=1/5) to give a white solid (1.30 g, 73.4%). .sup.1H-NMR [ppm] in DMSO-d6: 12.75 (bs, 1H), 8.23 (s, 1H), 7.40 (s, 1H), 3.83 (s, 3H). LC-MS (method 1): RT=3.88 min; [M−H]−=244.
Step 3: Methyl 5-cyano-2-(trifluoromethyl)-4-(trifluoromethylsulfonyloxy)benzoate
[0417] ##STR00028##
[0418] Into the reaction vessel was added methyl 5-cyano-4-hydroxy-2-(trifluoromethyl)benzoate (1.00 g, 4.08 mmol), dichloromethane (20 mL), and pyridine (0.968 g, 12.2 mmol), The reaction mixture was cooled to 0° C. and triflic anhydride (2.88 g, 10.2 mmol). The reaction mixture was allowed to warm to room temperature, stirred at room temperature for 30 minutes, cooled to 0° C. Dichloromethane (30 mL) and water (50 mL) were added. The organic phase was collected, dried over Na.sub.2SO.sub.4, concentrated under reduced pressure, and subjected to silica gel chromatography purification (ethyl acetate/petroleum ether=1:10) to give colorless oil (1.38 g, 90.0%). .sup.1H-NMR [ppm] in DMSO-d6: 8.70 (s, 1H), 8.46 (s, 1H), 3.92 (s, 3H).
Step 4: Methyl 5-cyano-2-(trifluoromethyl)-4-[4-(trifluoromethyl)phenyl]benzoate
[0419] ##STR00029##
[0420] A mixture of methyl 5-cyano-2-(trifluoromethyl)-4-(trifluoromethylsulfonyloxy)benzoate (1.75 g, 4.64 mmol), [4-(trifluoromethyl)phenyl]boronic acid (1.76 g, 9.28 mmol), tetrakis(triphenylphosphine)-palladium(0) (0.536 g, 0.464 mmol), potassium carbonate (1.6 g, 11.6 mmol) in 1,4-dioxane (30.0 mL) was stirred at 110° C. under nitrogen atmosphere for 16 hours. The reaction mixture was poured into water and extracted with ethyl acetate three times. The combined organic layers were dried over Na2SO.sub.4, filtered and concentrated under vacuum. The crude product was purified by column chromatography on silica gel to give a white solid (1.50 g, 86.6%). .sup.1H-NMR [ppm] in DMSO-d6: 8.53 (s, 1H), 8.17 (s, 1H), 7.90-8.10 (m, 4H), 3.93 (s, 3H).
Step 5: 5-Cyano-2-(trifluoromethyl)-4-[4-(trifluoromethyl)phenyl]benzoate
[0421] ##STR00030##
[0422] Sodium hydroxide (0.643 g, 16.1 mmol) in water (5 mL) was added dropwise to a solution of methyl 5-cyano-2-(trifluoromethyl)-4-[4-(trifluoromethyl)phenyl]benzoate (2.00 g, 5.36 mmol) in methanol (10 mL) and water (5 mL). Tetrahydrofuran (10 mL) was added after 5 minutes. The mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into aqueous hydrochloric acid and extracted with ethyl acetate (50 mL), dried over Na.sub.2SO.sub.4, filtered and concentrated under vacuum to give white solid (1.40 g, 72.7%). .sup.1H-NMR [ppm] in DMSO-d6: 8.46 (s, 1H), 8.11 (s, 1H), 7.90-8.10 (m, 4H). This material was used for next step.
Step 6: 5-[4-(5-Methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]-4-(trifluoromethyl)-2-[4-(trifluoromethyl)phenyl]benzonitrile (Compound P1.1)
[0423] ##STR00031##
[0424] To a solution of 5-cyano-2-(trifluoromethyl)-4-[4-(trifluoromethyl)phenyl]benzoic acid (200 mg, 0.557 mmol) in dichloromethane (10.0 mL) was added the hydrochloride salt of 5-methyl-3-(4-piperidyl)-1,2,4-oxadiazole (126 mg, 0.618 mmol, 1.11 eq) which was synthesized as described in Nippon Soda patent application WO 2017195703. Subsequently HATU (234 mg, 0.615 mmol, 1.11eq) and diisopropyl-ethyl-amine (216 mg, 1.68 mmol, 3.01 eq) were added. The reaction mixture was stirred at room temperature for 21 hours and then poured into an aqueous NaHCO.sub.3 solution. The mixture was extracted three times with ethyl acetate. The water layer was acidified with 2N hydrochloric acid and extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure. The residue was purified via chromatography (ethyl acetate/petroleum ether=1:2) to give 205 mg (yield: 72%) of 5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperidine-1-carbonyl]-4-(trifluoromethyl)-2-[4-(trifluoromethyl)phenyl]benzonitrile as a white solid. .sup.1H-NMR [ppm] in CDCl.sub.3: 7.85 (d, 2H), 7.82-7.74 (m, 2H), 7.70 (d, 2H), 4.64 (s, 1H), 3.49 (d, 1H), 3.31-3.02 (m, 3H), 2.59 (d, 3H), 2.19 (d, 1H), 2.06-1.79 (m, 3H). 7.74-7.88 (m, 4H), 7.70 (d, 2H), 4.60 (t, 1H), 3.50 (t, 1H), 3.02-3.40 (m, 3H), 2.57 (d, 3H), 2.10-2.25 (m, 1H), 1.79-2.06 (m, 3H). LC-MS (method 1): RT=4.80 min; [M+H].sup.+=509.
Example P2: 5-[4-(3,5-Dichloro-2-pyridyl)piperazine-1-carbonyl]-4-(trifluoromethyl)-2-[4-(trifluoromethyl)phenyl]benzonitrile (Compound P2.1)
[0425] ##STR00032##
[0426] To a solution of 5-cyano-2-(trifluoromethyl)-4-[4-(trifluoromethyl)phenyl]benzoic acid (158 mg, 0.44 mmol) in DMF (5 mL) was added 4-(3,5-dichloro-2-pyridyl)piperazine (108 mg, 0.463 mmol), HATU (201 mg, 0.528 mmol) and diisopropylethylamine (227 mg, 1.76 mmol). The reaction mixture was stirred at room temperature for 16 hours. Then the mixture was poured into water and extracted with ethyl acetate three times. The combined organic layer were washed two times with water and once with brine, dried over Na.sub.2SO.sub.4 and the solvent was removed. The crude product was purified by chromatography on silica gel (ethyl acetate/petroleum ether=1:1) to give the product (187 mg, 74%) as a white solid. .sup.1H-NMR [ppm] in CDCl.sub.3: 8.16 (s, 1H), 7.88 (s, 1H), 7.76-7.85 (m, 3H), 7.71 (d, 2H), 7.70 (s, 1H), 3.85-4.10 (m, 2H), 3.25-3.53 (m, 6H). LC-MS (method 1): RT=5.51 min; [M+H].sup.+=574.
Example P3: 5-[4-(3,5-Dichloro-2-pyridyl)piperazine-1-carbonyl]-4-(trifluoromethyl)-2-[4-(trifluoromethyl)phenyl]benzenecarbothioamide (Compound P8.1)
[0427] ##STR00033##
[0428] To a solution of 5-[4-(3,5-dichloro-2-pyridyl)piperazine-1-carbonyl]-4-(trifluoromethyl)-2-[4-(trifluoromethyl)phenyl]benzonitrile (0.134 g, 0.234 mmol) in DMF (2.3 mL) was added magnesium dichloride (0.062 g, 0.304 mmol, 1.3 eq). The mixture was stirred for 1 hour at room temperature. Then sodium hydrosulfide (0.05 g, 0.888 mmol, 3.8 eq) was added and stirring was continued for 1 hour at room temperature. The reaction mixture was treated with saturated aqueous NHCl.sub.4 solution and then extracted three times with ethyl acetate. The organic phase was dried over Na2SO.sub.4 and the solvent was removes solvent under reduced pressure. The residue was purified by chromatography to give the desired product (130 mg, 91%) as a white foam. .sup.1H-NMR [ppm] in CDCl.sub.3: 8.18 (s, 1H), 7.62-7.80 (m, 7H), 7.01 (bs, 1H), 6.97 (bs, 1H), 3.85-4.10 (m, 2H), 3.25-3.60 (m, 6H). LC-MS (method 2): RT=1.25 min; [M+H].sup.+=607.
Example P4: 5-[4-(3,5-Dichloro-2-pyridyl)piperazine-1-carbonyl]-4-ethoxy-2-[4-(trifluoromethyl)-phenyl]-benzonitrile (Compound P2.5)
[0429] ##STR00034##
Step 1: Ethyl 4-amino-5-cyano-2-hydroxy-benzoate
[0430] ##STR00035##
[0431] To a solution of sodium ethoxide (1.1 eq.) in ethanol (20% w/w) was added slowly propanedinitrile (1.32 g, 20 mmol, 1 eq) at 4° C. and the mixture was stirred for 15 minutes. Then a solution ethyl (2E)-2-(ethoxymethylene)-3-oxo-butanoate (3.72 g, 20 mmol) in ethanol (50 mL) was added under ice cooling. The reaction mixture was heated to reflux for 1 hour. After cooling the reaction mixture was diluted with ethyl acetate and water. The phases were separated and the aqueous phase was extracted three times with ethyl acetate. The combined organic layer was washed two times with water and once with brine, dried over Na.sub.2SO.sub.4 and the solvent was removed. 2.45 g (59% yield) of ethyl 4-amino-5-cyano-2-hydroxy-benzoate were obtained as a white solid. .sup.1H NMR [ppm] in DMSO: 10.98 (s, 1H), 7.89 (s, 1H), 6.79 (s, 2H), 6.20 (s, 1H), 4.28 (q, 2H), 1.30 (t, 3H). LC-MS (method 1): RT=3.98 min; [M+H].sup.+=207.
Step 2: Ethyl 5-cyano-2-hydroxy-4-iodo-benzoate
[0432] ##STR00036##
[0433] To a solution of boron trifluoride diethyl etherate (568 mg, 4 mmol) in THE (5 mL) was added a solution of ethyl 4-amino-5-cyano-2-hydroxy-benzoate (412 mg, 4 mmol) in THE (5 mL) at 0° C. Then the mixture was cooled to −10° C., tert-butyl nitrite (268 mg, 2.6 mmol) was added and the reaction mixture was stirred at −10° C. for 0.5 hours. Then sodium iodide (390 mg, 2.6 mmol) in acetone (10 mL) was added and the mixture was stirred at room temperature for 1.5 hours. The reaction mixture was diluted with ethyl acetate and water. The phases were separated, and the aqueous phase was extracted three times with ethyl acetate. The combined organic layer was washed two times with water and once with brine, dried over Na.sub.2SO.sub.4 and the solvent was removed. The crude product was purified by chromatography on silica gel (ethyl acetate/petroleum ether=1:2) to afford the product (599 mg, 94.5%) as a white solid. .sup.1H NMR [ppm] in DMSO-d6: 11.36 (s, 1H), 8.07 (s, 1H), 7.63 (s, 1H), 4.32 (q, 2H), 1.32 (t, 3H). LC-MS (method 1): RT=4.76 min; [M+H].sup.+=318.
Step 3: Ethyl 5-cyano-2-ethoxy-4-iodo-benzoate
[0434] ##STR00037##
[0435] To a solution of ethyl 5-cyano-2-hydroxy-4-iodo-benzoate (1.17 g, 3.7 mmol) in acetone (50 mL) was added iodoethane (867 mg, 5.56 mmol) and potassium carbonate (767 mg, 5.56 mmol). The mixture was stirred and heated to reflux for 5 hours. After cooling, the reaction mixture was diluted with ethyl acetate and water. The phases were separated and the aqueous phase was extracted three times with ethyl acetate. The combined organic layer was washed two times with water and once with brine, dried over Na.sub.2SO.sub.4 and the solvent was removed. The crude product was purified by chromatography on silica gel (ethyl acetate/petroleum ether=1:5) to afford the product (372 mg, 29%) as a white solid. .sup.1H NMR [ppm] in CDCl.sub.3: 7.99 (s, 1H), 7.45 (s, 1H), 4.35 (q, 2H), 4.16 (q, 2H), 1.49 (t, 3H), 1.38 (t, 3H). LC-MS (method 1): RT=4.683 min; [M+H].sup.+=346.
Step 4: Ethyl 5-cyano-2-ethoxy-6-[4-(trifluoromethyl)phenyl]pyridine-3-carboxylate
[0436] ##STR00038##
[0437] A mixture of ethyl 5-cyano-2-ethoxy-6-iodo-pyridine-3-carboxylate (370 mg, 1.07 mmol), 1-[4-(trifluoromethyl)phenyl]boronic acid (408 mg, 2.14 mmol), Pd(PPh.sub.3).sub.4 (247 mg, 0.21 mmol) and potassium carbonate (443 mg, 3.21 mmol) in 1,4-dioxane (20.0 mL) was stirred under nitrogen at 90° C. for 16 hours. Then the mixture was poured into water and extracted with ethyl acetate three times. The combined organic layer was washed two times with water and once with brine, dried over Na.sub.2SO.sub.4 and the solvent was removed. The crude product was purified by chromatography on silica gel (ethyl acetate/petroleum ether=1:5) to give the product (380 mg, 97.5%) as a white solid. .sup.1H NMR [ppm] in CDCl.sub.3: 8.22 (s, 1H), 7.77 (d, 2H), 7.68 (d, 2H), 7.01 (s, 1H), 4.40 (q, 2H), 4.22 (q, 2H), 1.52 (t, 3H), 1.41 (t, 3H). LC-MS (method 1): RT=3.615 min; [M+H].sup.+=364.
Step 5: 5-Cyano-2-ethoxy-4-[4-(trifluoromethyl)phenyl]benzoic Acid
[0438] ##STR00039##
[0439] Ethyl 5-cyano-2-ethoxy-4-[4-(trifluoromethyl)phenyl]benzoate (1.3 g, 3.58 mmol) was dissolved in tetrahydrofuran (10 mL) and potassium hydroxide (429 mg, 10.7 mmol, 3.0 eq.) dissolved in water (2 mL) was added. The reaction mixture was stirred at room temperature for 16 hours. Then the reaction mixture was diluted with ethyl acetate and 2 N hydrochloric acid. The mixture was extracted three times with ethyl acetate. The combined organic layer was washed two times with water and once with brine, dried over Na.sub.2SO.sub.4 and the solvent was removed to give the crude product (1.2 g, 100%) as a white solid witch was used directly for the next step.
Step 6: 5-[4-(3,5-Dichloro-2-pyridyl)piperazine-1-carbonyl]-4-ethoxy-2-[4-(trifluoromethyl)-phenyl]-benzonitrile (Compound P2.5)
[0440] ##STR00040##
[0441] To a solution of 5-cyano-2-ethoxy-4-[4-(trifluoromethyl)phenyl]benzoic acid (121 mg, 0.36 mmol) in DMF (5 mL) was added 1-(3,5-dichloro-2-pyridyl)piperazine (99 mg, 0.43 mmol), HATU (163 mg, 0.43 mmol) and diisopropylethylamine (139 mg, 1.08 mmol). The reaction mixture was stirred at room temperature for 16 hours. Then the mixture was poured into water and extracted with ethyl acetate three times. The combined organic layer was washed two times with water and once with brine, dried over Na.sub.2SO.sub.4 and the solvent was removed. The crude product was purified by chromatography on silica gel (ethyl acetate/petroleum ether=1/1) to give the product (140 mg, 71%) as a white solid. .sup.1H NMR [ppm] in CDCl.sub.3: 8.16 (d, 1H), 7.74 (d, 2H), 7.71 (s, 1H), 7.64-7.68 (m, 3H), 6.97 (s, 1H), 4.15-4.25 (m, 2H), 3.80-4.20 (m, 2H), 1.48 (t, 3H). LC-MS (method 1): RT=5.627 min; [M+H].sup.+=550.
Example P5: 4-Ethoxy-5-[4-(ethylsulfanylmethyl)piperidine-1-carbonyl]-2-[4-(trifluoromethyl)phenyl]-benzonitrile (Compound P1.46)
[0442] ##STR00041##
[0443] To a solution of 5-cyano-2-ethoxy-4-[4-(trifluoromethyl)phenyl]benzoic acid (140 mg, 0.42 mmol) in DMF (5 mL) was added 4-(ethylsulfanylmethyl)piperidine hydrochloride (117 mg, 0.598 mmol), HATU (190 mg, 0.5 mmol) and diisopropylethylamine (163 mg, 1.62 mmol). The reaction mixture was stirred at room temperature for 16 hours. Then the mixture was poured into water and extracted with ethyl acetate three times. The combined organic layer was washed two times with water and once with brine, dried over Na.sub.2SO.sub.4 and the solvent was removed. The crude product was purified by chromatography on silica gel (ethyl acetate/petroleum ether=1:1) to give the product (127 mg, 64%) as a white solid. .sup.1H NMR [ppm] in CDCl.sub.3: 7.76 (d, 2H), 7.60-7.70 (m, 3H), 6.94 (d, 1H), 4.78 (t, 1H), 4.09-4.25 (m, 2H), 3.49 (d, 1H), 2.90-3.10 (m, 1H), 2.79 (q, 1H), 2.42-2.59 (m, 4H), 1.90-2.05 (m, 1H), 1.69-1.85 (m, 2H), 1.40-1.51 (m, 3H), 1.20-1.30 (m, 5H). LC-MS (method 1): RT=5.32 min; [M+H].sup.+=477.
Example P6: 4-Ethoxy-5-[4-(ethylsulfanylmethyl)piperidine-1-carbonyl]-2-[4-(trifluoromethyl)phenyl]-benzonitrile (Compound P3.7)
[0444] ##STR00042##
Step 1: tert-Butyl 3-(acetylsulfanylmethyl)azetidine-1-carboxylate
[0445] ##STR00043##
[0446] Acetyl sulfanyl sodium (85.0%, 0.462 g, 4.00 mmol) was added to the tert-butyl 3-(bromomethyl)-azetidine-1-carboxylate (0.500 g, 2.00 mmol) in acetone (10.0 mL) at room temperature and the mixture was stirred at room temperature for 16 hours. Then the mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate three times. The combined organic layers were dried over Na.sub.2SO.sub.4, filtered and concentrated under vacuum. The crude product was purified by column chromatography on silica gel (petroleum ether/ethyl acetate=20:1) to afford 315 mg (yield: 64%) tert-butyl 3-(acetylsulfanylmethyl)-azetidine-1-carboxylate. .sup.1H NMR [ppm] in CDCl.sub.3: 3.98 (t, 2H), 3.56 (dd, 2H), 3.09 (d, 2H), 2.62-2.78 (m, 1H), 2.34 (s, 3H), 1.42 (d, 9H). LC-MS (method 1): RT=4.25 min; [M+Na].sup.+=268.
Step 2: tert-Butyl 3-(sulfanylmethyl)azetidine-1-carboxylate
[0447] ##STR00044##
[0448] Sodium borohydride (0.308 g, 8.15 mmol) was added to tert-butyl 3-(acetylsulfanylmethyl)azetidine-1-carboxylate (1.00 g, 4.08 mmol) in methanol (10.0 mL) and stirred for 16 hours at room temperature. Then the mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate three times. The combined organic layers were dried over Na.sub.2SO.sub.4, filtered and concentrated under vacuum. The crude product was purified by column chromatography on silica gel (petroleum ether/ethyl acetate=20:1) to afford 528 mg (yield: 64%) tert-butyl 3-(sulfanylmethyl)azetidine-1-carboxylate. .sup.1H NMR [ppm] in CDCl.sub.3: 4.02 (t, 2H), 3.60 (dd, 2H), 2.73 (t, 2H), 2.61-2.65 (m, 1H), 1.43 (s, 9H), 1.30 (t, 1H). LC-MS (method 1): RT=4.11 min; [M+Na].sup.+=226.
Step 3: tert-Butyl 3-(propylsulfanylmethyl)azetidine-1-carboxylate
[0449] ##STR00045##
[0450] 1-Iodopropane (0.627 g, 3.69 mmol) was added to tert-butyl 3-(sulfanylmethyl)azetidine-1-carboxylate (500 mg, 2.46 mmol) and K.sub.2CO.sub.3 (1.02 g, 7.38 mmol) in acetone (10.0 mL) and the reaction mixture was stirred for 16 hours at room temperature. Then the mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate three times. The combined organic layers were dried over Na.sub.2SO.sub.4, filtered and concentrated under vacuum. The crude product was purified by column chromatography on silica gel (petroleum ether/ethyl acetate=20:1) to afford 331 mg (yield: 52%) of tert-butyl 3-(propylsulfanylmethyl)azetidine-1-carboxylate. .sup.1H NMR [ppm] in CDCl.sub.3: 4.02 (t, 2H), 3.60 (dd, 2H), 2.60-2.75 (m, 3H), 2.47 (t, 2H), 1.54-1.63 (m, 2H), 1.43 (s, 9H), 0.98 (t, 3H).
Step 4: Trifluoroacetic acid salt of 3-(propylsulfanylmethyl)azetidine
[0451] ##STR00046##
[0452] tert-Butyl 3-(propylsulfanylmethyl)azetidine-1-carboxylate (500 mg, 2.04 mmol) and 2,2,2-trifluoroacetic acid (0.929 g, 8.15 mmol) in dichloromethane (15.0 mL) was stirred at room temperature for 16 hours. The reaction mixture was concentrated under vacuum and used for the next step. .sup.1H NMR [ppm] in DMSO-d6: 4.17 (s, 2H), 3.90 (s, 2H), 3.13 (t, 1H), 2.78 (d, 2H), 2.48 (t, 2H), 1.64-1.52 (m, 2H), 0.98 (t, 3H).
Step 5: 5-[3-(propylsulfanylmethyl)azetidine-1-carbonyl]-4-(trifluoromethyl)-2-[4-(trifluoromethyl)-phenyl]benzonitrile
[0453] ##STR00047##
[0454] To a solution of 5-cyano-2-(trifluoromethyl)-4-[4-(trifluoromethyl)phenyl]benzoic acid (150 mg, 0.418 mmol) in DMF (5 mL) was added the trifluoroacetic acid salt of 3-(propylsulfanylmethyl)azetidine (162 mg, 0.626 mmol, 1.5eq). Subsequently HATU (238 mg, 0.626 mmol, 1.5 eq.) and diisopropylethylamine (162 mg, 1.25 mmol, 3.00 eq.) were added. The reaction mixture was stirred at room temperature for 16 hours and then poured into an aqueous NaHCO.sub.3 solution. The mixture was extracted three times with ethyl acetate. The water layer was acidified with 2N hydrochloric acid and extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure. The residue was purified via chromatography (petroleum ether/ethyl acetate=1:1) to afford 121 mg (yield: 60%) of 5-[3-(propylsulfanylmethyl)azetidine-1-carbonyl]-4-(trifluoromethyl)-2-[4-(trifluoromethyl)phenyl]-benzonitrile were obtained as a colorless gum. .sup.1H-NMR [ppm] in CDCl.sub.3): 7.85 (s, 1H), 7.77-7.83 (m, 3H), 7.69 (d, 2H), 4.33 (t, 1H), 4.05 (t, 1H), 3.92 (dd, 1H), 3.66 (dd, 1H), 2.65-2.99 (m, 3H), 2.40-2.60 (m, 2H), 1.55-1-70 (m, 2H), 0.98 (t, 3H). LC-MS (method 1): RT=5.38 min; [M+H].sup.+=487.
Step 6: 5-[3-(Propylsulfinylmethyl)azetidine-1-carbonyl]-4-(trifluoromethyl)-2-[4-(trifluoromethyl)phenyl]-benzonitrile (Compound P3.7)
[0455] ##STR00048##
[0456] 3-Chloro-perbenzoic acid (0.034 g, 0.197 mmol, 0.8 eq) was added to 5-[3-(propylsulfanylmethyl)-azetidine-1-carbonyl]-4-(trifluoromethyl)-2-[4-(trifluoromethyl)phenyl]benzonitrile (120 mg, 0.247 mmol) in dichloromethane (20 mL) and stirred for 2 hours at room temperature. Then the mixture was poured into a saturated solution of NaHCO.sub.3 and Na.sub.2SO.sub.3 in water and extracted with ethyl acetate three times. The combined organic layers were dried over Na.sub.2SO.sub.4, filtered and concentrated under vacuum. The crude product was purified by column chromatography on silica gel (ethyl acetate/petroleum ether=1:2) to give 41 mg (yield: 33%) of 5-[3-(propylsulfinylmethyl)azetidine-1-carbonyl]-4-(trifluoromethyl)-2-[4-(trifluoromethyl)phenyl]benzonitrile as a colorless gum. .sup.1H-NMR [ppm] in DMSO-d6): 8.32 (s, 1H), 8.09 (s, 1H), 7.88-7.96 (m, 4H), 4.24 (t, 1H), 4.05-4.15 (m, 1H), 3.68-3.97 (m, 1H), 3.82 (dd, 1H), 2.96-3.20 (m, 3H), 2.60-2.75 (m, 2H), 1.53-1.71 (m, 2H), 0.98 (t, 3H). LC-MS (method 1): RT=4.36 min; [M+H].sup.+=503.
Example P7: 4-Methyl-5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperazine-1-carbonyl]-2-[4-(trifluoromethyl)phenyl]benzene-1,3-dicarbonitrile (Compound P6.1)
[0457] ##STR00049##
Step 1: Ethyl 4-amino-3,5-dicyano-2-methyl-benzoate
[0458] ##STR00050##
[0459] A solution of ethyl acetoacetate (1.3 mL, 0.01 mmol) in methanol was cooled to 0° C., then treated with aqueous formaldehyde (1 mL). The reaction mixture was stirred for 3 hours and then a solution of malononitrile (1.2 g, 0.2 mmol) in methanol (30 mL) was added gradually with stirring over a period of 1 hour after which time a morpholine solution (0.8 mL, 0.1 mmol) in methanol (20 mL) was added to the mixture. This mixture was cooled with ice for 3 hours, then allowed to stand at room temperature for 48 hours. The solid was filtered off and washed with a small amount of methanol to give the target compound (1.8 g, 78%). .sup.1H-NMR [ppm] in CDCl.sub.3: 8.02 (s, 1H), 7.17 (s, 2H), 4.26 (q, 2H), 2.65 (s, 3H), 1.35 (t, 3H). MS (ESI) [M+H].sup.+=230.0.
Step 2: Ethyl 3,5-dicyano-4-iodo-2-methyl-benzoate
[0460] ##STR00051##
[0461] Ethyl 4-amino-3,5-dicyano-2-methyl-benzoate (1.90 g, 8.3 mmol) was suspended in H.sub.2SO.sub.4 (40 mL, 50%), cooled to −5° C. and stirred for 1 hour. A solution of sodium nitrite (0.86 g, 12.5 mmol) in water (5 mL) was added slowly, and the mixture stirred for 30 minutes at 0° C. The yellow slurry was then slowly added to an ice-cooled solution of potassium iodide (13.8 g, 83 mmol) in water (230 mL). The ice bath was then removed, and the foamy suspension was stirred for 2 hours at room temperature. Dichloromethane (100 mL) was added, followed by a saturated Na.sub.2S.sub.2O.sub.3 solution. The organic layer was separated, and the aqueous layer was extracted with dichloromethane. The combined dichloromethane layer was dried over Na.sub.2SO.sub.4, the solvent was evaporated to yield ethyl 3,5-dicyano-4-iodo-2-methyl-benzoate. (0.8 g, 28%). .sup.1H-NMR [ppm] in CDCl.sub.3: 8.27 (s, 1H), 4.20 (q, 2H), 2.50 (s, 3H), 1.42 (t, 3H). MS (ESI) [M+H].sup.+=341.1.
Step 3: Ethyl 3,5-dicyano-2-methyl-4-[4-(trifluoromethyl)phenyl]benzoate
[0462] ##STR00052##
[0463] The mixture of ethyl 3,5-dicyano-4-iodo-2-methyl-benzoate (0.74 g, 2.18 mmol), [4-(trifluoromethyl)phenyl]boronic acid (0.62 g, 3.26 mmol), sodium carbonate (0.46 g, 4.33 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.25 g, 0.218 mmol) in toluene (20 mL)/water (6 mL) was stirred at 80° C. overnight. The reaction mixture was cooled to room temperature and extracted with ethyl acetate. The organic layer was separated, washed with brine (20 mL), dried over magnesium sulfate and concentrated in vacuum. Purification through column chromatography (ethyl acetate/petroleum ether=2:1) gave the target compound (0.7 g, 90%). .sup.1H-NMR [ppm] in CDCl.sub.3: 8.45 (s, 1H), 7.84 (d, 2H), 7.64 (d, 2H), 4.46 (q, 2H), 2.97 (s, 3H), 1.45 (t, 3H). MS (ESI) [M+H].sup.+=359.3.
Step 4: 3,5-dicyano-2-methyl-4-[4-(trifluoromethyl)phenyl]benzoic Acid
[0464] ##STR00053##
[0465] A solution of ethyl 3,5-dicyano-2-methyl-4-[4-(trifluoromethyl)phenyl]benzoate (0.56 g, 1.56 mmol) in methanol (10 mL), sodium hydroxide (75 mg, 1.88 mmol) was added. The mixture was stirred at room temperature for 2 hours. Then the pH was adjusted to 2-3 by addition of hydrochloric acid and the mixture was extracted with ethyl acetate. The organic layer was separated, washed with brine, dried over magnesium sulfate and concentrated in vacuum to give the product (0.5 g, 97%). .sup.1H-NMR [ppm] in DMSO-d6: 8.57 (s, 1H), 8.02 (d, 2H), 7.87 (d, 2H), 2.83 (s, 3H). MS (ESI) [M+H].sup.+=331.3.
Step 5: 4-Methyl-5-[4-(5-methyl-1,2,4-oxadiazol-3-yl)piperazine-1-carbonyl]-2-[4-(trifluoromethyl)-phenyl]benzene-1,3-dicarbonitrile (Compound P6.1)
[0466] ##STR00054##
[0467] A mixture of 3,5-dicyano-2-methyl-4-[4-(trifluoromethyl)phenyl]benzoic acid (250 mg, 0.757 mmol), 5-methyl-3-(4-piperidyl)-1,2,4-oxadiazole (127 mg, 0.757 mmol) which was synthesized as described in Nippon Soda patent application WO 2017195703, diisopropylethylamine (294 mg, 2.27 mmol) and HATU (431 mg, 1.14 mol) in dichloromethane (10 mL) was stirred at room temperature for 4 hours. The mixture was poured into water (50 mL) and the mixture extracted three times with ethyl acetate (50 mL each), the combined organic phases were dried over Na.sub.2SO.sub.4 and concentrated. The material was purified by chromatography (ethyl acetate/petroleum ether=1:2) to give the title compound as solid (230 mg, 63%). .sup.1H-NMR [ppm] in CDCl.sub.3: 7.84 (d, 2H), 7.76, 7.79 (2s, 1H), 7.63 (d, 2H), 4.63 (t, 1H), 3.53 (d, 1H), 3.10-3.30 (m, 3H), 2.64, 2.59 (2s, 3H), 2.58 (s, 3H), 1.75-2.25 (m, 4H). MS (ESI) [M+H].sup.+=480.2.
[0468] The compounds in Tables P1, P2, P3, P4, P5, P6, P7 and P8 were prepared as described in the examples above or similar methodology.
Table P1: Compounds of Formula (I-c)
[0469] ##STR00055##
[0470] The compounds in Table P1 can be prepared as described in the examples above or similar methodology. The following abbreviations are used in the table below: RT=retention time, min=minutes m.p.=melting point or melting range.
TABLE-US-00013 TABLE P1 Comp. LC-MS m.p. No Y R.sup.3 [M + H].sup.+ RT (min) Method [° C.] P1.1 5-methyl-1,2,4- CF.sub.3 509 4.80 1 91-92 oxadiazole-3-yl P1.2 CH.sub.2SCH.sub.2CH.sub.3 CF.sub.3 501 5.47 1 118-120 P1.3 CH.sub.2S(═O)CH.sub.2CH.sub.3 CF.sub.3 517 4.34 1 85-88 P1.4 CH.sub.2SO.sub.2CH.sub.2CH.sub.3 CF.sub.3 533 4.63 1 87-89 P1.5 1,1-dioxo-1,2- CF.sub.3 546 4.61 1 92-94 thiazolidin-2-yl P1.6 5-methyl-1,2,4- CH.sub.3 455 4.56 1 90-92 oxadiazole-3-yl P1.7 CH.sub.2SCH.sub.2CH.sub.3 CH.sub.3 447 5.24 1 95-97 P1.8 1,1-dioxo-1,2- CH.sub.3 492 4.36 1 208-210 thiazolidin-2-yl P1.9 5-methyl-1,2,4- H 441 4.45 1 oxadiazole-3-yl P1.10 CH.sub.2SCH.sub.2CH.sub.3 H 433 5.16 1 96-98 P1.11 1,1-dioxo-1,2- H 478 4.26 1 92-94 thiazolidin-2-yl P1.12 CH.sub.2SCH.sub.3 CF.sub.3 487 5.30 1 148-150 P1.13 CH.sub.2S(═O)CH.sub.3 CF.sub.3 503 4.24 1 98-100 P1.14 CH.sub.2SO.sub.2CH.sub.3 CF.sub.3 519 4.55 1 186-188 P1.15 CH.sub.2SCH.sub.2CH═CH.sub.2 CF.sub.3 513 5.53 1 110-112 P1.16 CH.sub.2S(═O)CH.sub.2CH═CH.sub.2 CF.sub.3 529 4.47 1 P1.17 CH.sub.2SO.sub.2CH.sub.2CH═CH.sub.2 CF.sub.3 545 4.75 1 96-98 P1.18 CH.sub.2SCH.sub.2CHCH CF.sub.3 511 5.25 1 P1.19 CH.sub.2S(═O)CH.sub.2CHCH CF.sub.3 527 4.46 1 P1.20 CH.sub.2SO.sub.2CH.sub.2CHCH CF.sub.3 543 4.73 1 P1.21 CH.sub.2SCH.sub.2CH.sub.2CH.sub.3 CF.sub.3 515 5.68 1 112-114 P1.22 CH.sub.2S(═O)CH.sub.2CH.sub.2CH.sub.3 CF.sub.3 531 4.54 1 91-93 P1.23 CH.sub.2SO.sub.2CH.sub.2CH.sub.2CH.sub.3 CF.sub.3 547 4.63 1 93-95 P1.24 CH.sub.2SCH.sub.3 CH.sub.3 433 5.11 1 120-122 P1.25 CH.sub.2S(═O)CH.sub.3 CH.sub.3 449 3.99 1 167-169 P1.26 CH.sub.2SO.sub.2CH.sub.3 CH.sub.3 465 5.11 1 161-163 P1.27 CH.sub.2SCH.sub.2CH═CH.sub.2 CH.sub.3 459 5.37 1 100-102 P1.28 CH.sub.2S(═O)CH.sub.2CH═CH.sub.2 CH.sub.3 475 4.25 1 P1.29 CH.sub.2SO.sub.2CH.sub.2CH═CH.sub.2 CH.sub.3 491 4.56 1 90-92 P1.30 CH.sub.2SCH.sub.2CHCH CH.sub.3 457 5.10 1 P1.31 CH.sub.2S(═O)CH.sub.2CHCH CH.sub.3 473 4.25 1 63-65 P1.32 CH.sub.2SO.sub.2CH.sub.2CHCH CH.sub.3 489 4.53 1 P1.33 CH.sub.2SCH.sub.2CH.sub.2CH.sub.3 CH.sub.3 461 5.56 1 118-120 P1.34 CH.sub.2S(═O)CH.sub.2CH.sub.2CH.sub.3 CH.sub.3 477 4.26 1 P1.35 CH.sub.2SO.sub.2CH.sub.2CH.sub.2CH.sub.3 CH.sub.3 493 4.60 1 99-101 P1.36 (E)-N-methoxy-imino- CF.sub.3 484 5.04 1 130-132 methyl P1.37 (E)-N-ethoxy-imino- CF.sub.3 498 5.22 1 115-117 methyl P1.38 methylsulfonyl- CF.sub.3 1 188-190 carbamoyl P1.39 dimethylcarbamoyl CF.sub.3 498 4.47 1 143-145 P1.40 ethyl(methyl)carbamoyl CF.sub.3 1 P1.41 methanesulfonamido CF.sub.3 520 4.48 1 215-217 P1.42 ethanesulfonamido CF.sub.3 534 4.60 1 224-226 P1.43 5-methyl-1,2,4- OCH.sub.3 471 4.47 1 oxadiazole-3-yl P1.44 CH.sub.2SCH.sub.2CH.sub.3 OCH.sub.3 463 5.14 1 162-164 P1.45 5-methyl-1,2,4- OCH.sub.2CH.sub.3 485 4.66 1 oxadiazole-3-yl P1.46 CH.sub.2SCH.sub.2CH.sub.3 OCH.sub.2CH.sub.3 477 5.32 1 68-70 P1.47 ethoxycarbonyl CF.sub.3 499 5.09 1 P1.48 tert-butoxy- CF.sub.3 5.11 1 168-170 carbonylamino P1.49 trifluoromethyl- CF.sub.3 538 4.66 1 215-217 sulfonylamino P1.50 1-methyl-1,2,4-triazol- CF.sub.3 508 4.36 1 3-yl P1.51 phenyl CF.sub.3 503 5.51 1 154-156 P1.52 ethoxymethyl CF.sub.3 485 5.23 1 110-112 P1.53 cyano CF.sub.3 452 5.25 1 102-104
Table P2: Compounds of Formula (I-d)
[0471] ##STR00056##
[0472] The compounds in Table P2 can be prepared as described in the examples above or similar methodology. The following abbreviations are used in the table below: RT=retention time, min=minutes, m.p.=melting point.
TABLE-US-00014 TABLE P2 Comp. LC-MS m.p. No A R.sup.3 [M + H].sup.+ RT (min) Method [° C.] P2.1 3,5-dichloro-2-pyridyl CF.sub.3 573 5.69 1 79-80 P2.2 3,5-dichloro-2-pyridyl CH.sub.3 519 5.55 1 135-137 P2.3 3,5-dichloro-2-pyridyl H 505 5.43 1 160-162 P2.4 3,5-dichloro-2-pyridyl OCH.sub.3 536 5.45 1 222-224 P2.5 3,5-dichloro-2-pyridyl OCH.sub.2CH.sub.3 549 5.63 1 97-99 P2.6 cyano CF.sub.3 453 1.03 2 152-155 P2.7 CH.sub.2CN CF.sub.3 467 4.63 2 138-140 P2.8 CH.sub.2CH.sub.2CN CF.sub.3 481 4.27 1 140-142 P2.9 2,2,2-trifluoroethyl CF.sub.3 510 1.17 2 142-144 P2.10 3,3-dichloroallyl CF.sub.3 536 4.52 1 148-150 P2.11 CH.sub.2CH.sub.2SCH.sub.3 CF.sub.3 502 3.95 1 114-116 P2.12 CH.sub.2CH.sub.2S(═O)CH.sub.3 CF.sub.3 518 3.71 1 94-96 P2.13 methylsulfonyl CF.sub.3 506 4.64 1 200-202 P2.14 trifluoromethyl- CF.sub.3 560 5.21 1 217-219 sulfonyl P2.15 tert-butoxy-carbonyl CF.sub.3 n/a 1.19 2 159-161 P2.16 trifluoromethyl- CF.sub.3 524 4.97 1 193-195 carbonyl P2.17 methoxyethyl CF.sub.3 486 3.81 1
[0473] Table P: Compounds of Formula (I-e)
##STR00057##
[0474] The compounds in Table P3 can be prepared as described in the examples above or similar methodology. The following abbreviations are used in the table below: RT=retention time, min=minutes; m.p.=melting point.
TABLE-US-00015 TABLE P3 Comp. LC-MS m.p. No Y R.sup.3 [M + H].sup.+ RT (min) Method [° C.] P3.1 CH.sub.2SCH.sub.3 CF.sub.3 459 5.01 1 120-122 P3.2 CH.sub.2S(═O)CH.sub.3 CF.sub.3 475 4.07 1 142-144 P3.3 CH.sub.2SO.sub.2CH.sub.3 CF.sub.3 491 4.39 1 167-169 P3.4 CH.sub.2SCH.sub.2CH.sub.3 CF.sub.3 473 5.78 1 97-99 P3.5 CH.sub.2S(═O)CH.sub.2CH.sub.3 CF.sub.3 489 4.20 1 75-77 P3.6 CH.sub.2SO.sub.2CH.sub.2CH.sub.3 CF.sub.3 505 4.50 1 150-152 P3.7 CH.sub.2S(═O)CH.sub.2CH.sub.2CH.sub.3 CF.sub.3 503 4.36 1 P3.8 CH.sub.2SO.sub.2CH.sub.2CH.sub.2CH.sub.3 CF.sub.3 519 4.66 1 80-82 P3.9 CH.sub.2SCH.sub.2CH.sub.2CH.sub.3 CF.sub.3 487 5.38 1
Table P4: Compounds of Formula (I-e)
[0475] ##STR00058##
[0476] The compounds in Table P2 can be prepared as described in the examples above or similar methodology. The following abbreviations are used in the table below: RT=retention time, min=minutes, m.p.=melting point.
TABLE-US-00016 TABLE P4 Comp. LC-MS m.p. No R.sup.m R.sup.3 [M + H].sup.+ RT (min) Method [° C.] P4.1 methyl CF.sub.3 470 4.93 1 136-138 P4.2 ethyl CF.sub.3 484 5.11 1 118-120
Table P5: Compounds of Formula (I-q)
[0477] ##STR00059##
[0478] The compound in Table P5 can be prepared as described in the examples above or similar methodology. The following abbreviations are used in the table below: RT=retention time, min=minutes; m.p.=melting point.
TABLE-US-00017 TABLE P5 Comp. LC-MS m.p. No Y X R.sup.3 [M + H].sup.+ RT (min) Method [° C.] P5.1 phenyl OH CF.sub.3 519 4.4 1 221-223 P5.2 4-Cl-phenyl OH CF.sub.3 553 5.2 1 250-251 P5.3 4-Cl-phenyl OCH.sub.3 CF.sub.3 567 1.29 2 103-105
Table P6: Compounds of Formula (I-h)
[0479] ##STR00060##
[0480] The compound in Table P6 can be prepared as described in the examples above or similar methodology. The following abbreviations are used in the table below: RT=retention time, min=minutes; m.p.=melting point.
TABLE-US-00018 TABLE P6 Comp. LC-MS m.p. No Y R.sup.3 [M + H].sup.+ RT (min) Method [° C.] P6.1 5-methyl-1,2,4- CH.sub.3 480 4.46 1 118-120 oxadiazole-3-yl
Table P7: Compounds of Formula (I-i)
[0481] ##STR00061##
[0482] The compound in Table P7 can be prepared as described in the examples above or similar methodology. The following abbreviations are used in the table below: RT=retention time, min=minutes; m.p.=melting point.
TABLE-US-00019 TABLE P7 Comp. LC-MS m.p. No A R.sup.3 [M + H].sup.+ RT (min) Method [° C.] P7.1 3,5-dichloro- CH.sub.3 544 5.31 1 185-187 2-pyridyl
Table P8: Compounds of Formula (I-j)
[0483] ##STR00062##
[0484] The compound in Table P8 can be prepared as described in the examples above or similar methodology. The following abbreviations are used in the table below: RT=retention time, min=minutes; m.p.=melting point.
TABLE-US-00020 TABLE P8 Comp. LC-MS m.p. No A R.sup.3 [M + H].sup.+ RT (min) Method [° C.] P8.1 3,5-dichloro- CF.sub.3 607 1.25 2 2-pyridyl
[0485] The intermediates in Table U1 are new and useful for the synthesis of some compounds of the general structure I. They can be prepared as described in the examples above or similar methodology. The following abbreviations are used in the table below: s=singlet, d=doublet, t=triplet, q=quartet, m=multiplet.
TABLE-US-00021 TABLE U1 Comp. No Structure .sup.1H-NMR: δ in [ppm] U1.1
[0486] The activity of the compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients. The mixtures of the compounds of formula (I) with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use.
[0487] 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.
[0488] The following mixtures of a compound of formula (I) with an active substances are preferred (the abbreviation “TX” means “one compound selected from the compounds defined in Tables 1 to 35 and Tables P1 to P8):
[0489] an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628)+TX,
[0490] an insect control active substance selected from Abamectin+TX, Acequinocyl+TX, Acetamiprid+TX, Acetoprole+TX, Acrinathrin+TX, Acynonapyr+TX, Afidopyropen+TX, Afoxolaner+TX, Alanycarb+TX, Allethrin+TX, Alpha-Cypermethrin+TX, Alphamethrin+TX, Amidoflumet+TX, Aminocarb+TX, Azocyclotin+TX, Bensultap+TX, Benzoximate+TX, Benzpyrimoxan+TX, Betacyfluthrin+TX, Beta-cypermethrin+TX, Bifenazate+TX, Bifenthrin+TX, Binapacryl+TX, Bioallethrin+TX, Bioallethrin S)-cyclopentylisomer+TX, Bioresmethrin+TX, Bistrifluron+TX, Broflanilide+TX, Brofluthrinate+TX, Bromophos-ethyl+TX, Buprofezine+TX, Butocarboxim+TX, Cadusafos+TX, Carbaryl+TX, Carbosulfan+TX, Cartap+TX, CAS number: 1632218-00-8+TX, CAS number: 1808115-49-2+TX, CAS number: 2032403-97-5+TX, CAS number: 2044701-44-0+TX, CAS number: 2128706-05-6+TX, CAS number: 2246757-58-2 (or 2249718-27-0)+TX, CAS number: 907187-07-9+TX, Chlorantraniliprole+TX, Chlordane+TX, Chlorfenapyr+TX, Chloroprallethrin+TX, Chromafenozide+TX, Clenpirin+TX, Cloethocarb+TX, Clothianidin+TX, 2-chlorophenyl N-methylcarbamate (CPMC)+TX, Cyanofenphos+TX, Cyantraniliprole+TX, Cyclaniliprole+TX, Cyclobutrifluram+TX, Cycloprothrin+TX, Cycloxaprid+TX, Cycloxaprid+TX, Cyenopyrafen+TX, Cyetpyrafen+TX, Cyflumetofen+TX, Cyfluthrin+TX, Cyhalodiamide+TX, Cyhalothrin+TX, Cypermethrin+TX, Cyphenothrin+TX, Cyproflanilide+TX, Cyromazine+TX, Deltamethrin+TX, Diafenthiuron+TX, Dialifos+TX, Dibrom+TX, Dicloromezotiaz+TX, Diflovidazine+TX, Diflubenzuron+TX, dimpropyridaz+TX, Dinactin+TX, Dinocap+TX, Dinotefuran+TX, Dioxabenzofos+TX, Emamectin (or Emamectin Benzoate)+TX, Empenthrin+TX, Epsilon-momfluorothrin+TX, Epsilon-metofluthrin+TX, Esfenvalerate+TX, Ethion+TX, Ethiprole+TX, Etofenprox+TX, Etoxazole+TX, Famphur+TX, Fenazaquin+TX, Fenfluthrin+TX, Fenitrothion+TX, Fenobucarb+TX, Fenothiocarb+TX, Fenoxycarb+TX, Fenpropathrin+TX, Fenpyroxymate+TX, Fensulfothion+TX, Fenthion+TX, Fentinacetate+TX, Fenvalerate+TX, Fipronil+TX, Flometoquin+TX, Flonicamid+TX, Fluacrypyrim+TX, Fluazaindolizine+TX, Fluazuron+TX, Flubendiamide+TX, Flubenzimine+TX, Flucitrinate+TX, Flucycloxuron+TX, Flucythrinate+TX, Fluensulfone+TX, Flufenerim+TX, Flufenprox+TX, Flufiprole+TX, Fluhexafon+TX, Flumethrin+TX, Fluopyram+TX, Flupentiofenox+TX, Flupyradifurone+TX, Flupyrimin+TX, Fluralaner+TX, Fluvalinate+TX, Fluxametamide+TX, Fosthiazate+TX, Gamma-Cyhalothrin+TX, Gossyplure™+TX, Guadipyr+TX, Halofenozide+TX, Halofenozide+TX, Halfenprox+TX, Heptafluthrin+TX, Hexythiazox+TX, Hydramethylnon+TX, Imicyafos+TX, Imidacloprid+TX, Imiprothrin+TX, Indoxacarb+TX, Iodomethane+TX, Iprodione+TX, Isocycloseram+TX, Isothioate+TX, Ivermectin+TX, Kappa-bifenthrin+TX, Kappa-tefluthrin+TX, Lambda-Cyhalothrin+TX, Lepimectin+TX, Lufenuron+TX, Metaflumizone+TX, Metaldehyde+TX, Metam+TX, Methomyl+TX, Methoxyfenozide+TX, Metofluthrin+TX, Metolcarb+TX, Mexacarbate+TX, Milbemectin+TX, Momfluorothrin+TX, Niclosamide+TX, Nicofluprole+TX; Nitenpyram+TX, Nithiazine+TX, Omethoate+TX, Oxamyl+TX, Oxazosulfyl+TX, Parathion-ethyl+TX, Permethrin+TX, Phenothrin+TX, Phosphocarb+TX, Piperonylbutoxide+TX, Pirimicarb+TX, Pirimiphos-ethyl+TX, Pirimiphos-methyl+TX, Polyhedrosis virus+TX, Prallethrin+TX, Profenofos+TX, Profenofos+TX, Profluthrin+TX, Propargite+TX, Propetamphos+TX, Propoxur+TX, Prothiophos+TX, Protrifenbute+TX, Pyflubumide+TX, Pymetrozine+TX, Pyraclofos+TX, Pyrafluprole+TX, Pyridaben+TX, Pyridalyl+TX, Pyrifluquinazon+TX, Pyrimidifen+TX, Pyriminostrobin+TX, Pyriprole+TX, Pyriproxyfen+TX, Resmethrin+TX, Sarolaner+TX, Selamectin+TX, Silafluofen+TX, Spinetoram+TX, Spinosad+TX, Spirodiclofen+TX, Spiromesifen+TX, Spiropidion+TX, Spirotetramat+TX, Sulfoxaflor+TX, Tebufenozide+TX, Tebufenpyrad+TX, Tebupirimiphos+TX, Tefluthrin+TX, Temephos+TX, Tetrachlorantraniliprole+TX, Tetradiphon+TX, Tetramethrin+TX, Tetramethylfluthrin+TX, Tetranactin+TX, Tetraniliprole+TX, Theta-cypermethrin+TX, Thiacloprid+TX, Thiamethoxam+TX, Thiocyclam+TX, Thiodicarb+TX, Thiofanox+TX, Thiometon+TX, Thiosultap+TX, Tioxazafen+TX, Tolfenpyrad+TX, Toxaphene+TX, Tralomethrin+TX, Transfluthrin+TX, Triazamate+TX, Triazophos+TX, Trichlorfon+TX, Trichloronate+TX, Trichlorphon+TX, Triflumezopyrim+TX, Tyclopyrazoflor+TX, Zeta-Cypermethrin+TX, Extract of seaweed and fermentation product derived from melasse+TX, Extract of seaweed and fermentation product derived from melasse comprising urea+TX, amino acids+TX, potassium and molybdenum and EDTA-chelated manganese+TX, Extract of seaweed and fermented plant products+TX, Extract of seaweed and fermented plant products comprising phytohormones+TX, vitamins+TX, EDTA-chelated copper+TX, zinc+TX and iron+TX, Azadirachtin+TX, Bacillus aizawai+TX, Bacillus chitinosporus AQ746 (NRRL Accession No B-21 618)+TX, Bacillus firmus+TX, Bacillus kurstaki+TX, Bacillus mycoides AQ726 (NRRL Accession No. B-21664)+TX, Bacillus pumilus (NRRL Accession No B-30087)+TX, Bacillus pumilus AQ717 (NRRL Accession No. B-21662)+TX, Bacillus sp. AQ178 (ATCC Accession No. 53522)+TX, Bacillus sp. AQ175 (ATCC Accession No. 55608)+TX, Bacillus sp. AQ177 (ATCC Accession No. 55609)+TX, Bacillus subtilis unspecified+TX, Bacillus subtilis AQ153 (ATCC Accession No. 55614)+TX, Bacillus subtilis AQ30002 (NRRL Accession No. B-50421)+TX, Bacillus subtilis AQ30004 (NRRL Accession No. B-50455)+TX, Bacillus subtilis AQ713 (NRRL Accession No. B-21661)+TX, Bacillus subtilis AQ743 (NRRL Accession No. B-21665)+TX, Bacillus thuringiensis AQ52 (NRRL Accession No. B-21619)+TX, Bacillus thuringiensis BD #32 (NRRL Accession No B-21530)+TX, Bacillus thuringiensis subspec. kurstaki BMP 123+TX, Beauveria bassiana+TX, D-limonene+TX, Granulovirus+TX, Harpin+TX, Helicoverpa armigera Nucleopolyhedrovirus+TX, Helicoverpa zea Nucleopolyhedrovirus+TX, Heliothis virescens Nucleopolyhedrovirus+TX, Heliothis punctigera Nucleopolyhedrovirus+TX, Metarhizium spp.+TX, Muscodor albus 620 (NRRL Accession No. 30547)+TX, Muscodor roseus A3-5 (NRRL Accession No. 30548)+TX, Neem tree based products+TX, Paecilomyces fumosoroseus+TX, Paecilomyces lilacinus+TX, Pasteuria nishizawae+TX, Pasteuria penetrans+TX, Pasteuria ramosa+TX, Pasteuria thornei+TX, Pasteuria usgae+TX, P-cymene+TX, Plutella xylostella Granulosis virus+TX, Plutella xylostella Nucleopolyhedrovirus+TX, Polyhedrosis virus+TX, pyrethrum+TX, QRD 420 (a terpenoid blend)+TX, QRD 452 (a terpenoid blend)+TX, QRD 460 (a terpenoid blend)+TX, Quillaja saponaria+TX, Rhodococcus globerulus AQ719 (NRRL Accession No B-21663)+TX, Spodoptera frugiperda Nucleopolyhedrovirus+TX, Streptomyces galbus (NRRL Accession No. 30232)+TX, Streptomyces sp. (NRRL Accession No. B-30145)+TX, Terpenoid blend+TX and Verticillium spp.;
[0491] 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;
[0492] an anthelmintic selected from the group of substances consisting of abamectin (1)+TX, crufomate (1011)+TX, Cyclobutrifluram+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;
[0493] 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;
[0494] 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;
[0495] a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537)+TX;
[0496] 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;
[0497] an insect pheromone selected from the group of substances consisting of (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol (IUPAC name) (222)+TX, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829)+TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541)+TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate (IUPAC name) (779)+TX, (Z)-dodec-7-en-1-yl acetate (IUPAC name) (285)+TX, (Z)-hexadec-11-enal (IUPAC name) (436)+TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name) (437)+TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438)+TX, (Z)-icos-13-en-10-one (IUPAC name) (448)+TX, (Z)-tetradec-7-en-1-al (IUPAC name) (782)+TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783)+TX, (Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784)+TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283)+TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780)+TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate (IUPAC name) (781)+TX, 14-methyloctadec-1-ene (IUPAC name) (545)+TX, 4-methylnonan-5-ol with 4-methylnonan-5-one (IUPAC name) (544)+TX, alpha-multistriatin (alternative name) [CCN]+TX, brevicomin (alternative name) [CCN]+TX, codlelure (alternative name) [CCN]+TX, codlemone (alternative name) (167)+TX, cuelure (alternative name) (179)+TX, disparlure (277)+TX, dodec-8-en-1-yl acetate (IUPAC name) (286)+TX, dodec-9-en-1-yl acetate (IUPAC name) (287)+TX, dodeca-8+TX, 10-dien-1-yl acetate (IUPAC name) (284)+TX, dominicalure (alternative name) [CCN]+TX, ethyl 4-methyloctanoate (IUPAC name) (317)+TX, eugenol (alternative name) [CCN]+TX, frontalin (alternative name) [CCN]+TX, gossyplure (alternative name) (420)+TX, grandlure (421)+TX, grandlure I (alternative name) (421)+TX, grandlure II (alternative name) (421)+TX, grandlure III (alternative name) (421)+TX, grandlure IV (alternative name) (421)+TX, hexalure [CCN]+TX, ipsdienol (alternative name) [CCN]+TX, ipsenol (alternative name) [CCN]+TX, japonilure (alternative name) (481)+TX, lineatin (alternative name) [CCN]+TX, litlure (alternative name) [CCN]+TX, looplure (alternative name) [CCN]+TX, medlure [CCN]+TX, megatomoic acid (alternative name) [CCN]+TX, methyl eugenol (alternative name) (540)+TX, muscalure (563)+TX, octadeca-2,13-dien-1-yl acetate (IUPAC name) (588)+TX, octadeca-3,13-dien-1-yl acetate (IUPAC name) (589)+TX, orfralure (alternative name) [CCN]+TX, oryctalure (alternative name) (317)+TX, ostramone (alternative name) [CCN]+TX, siglure [CCN]+TX, sordidin (alternative name) (736)+TX, sulcatol (alternative name) [CCN]+TX, tetradec-11-en-1-yl acetate (IUPAC name) (785)+TX, trimedlure (839)+TX, trimedlure A (alternative name) (839)+TX, trimedlure B.sub.1 (alternative name) (839)+TX, trimedlure B.sub.2 (alternative name) (839)+TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN]+TX;
[0498] 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; 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].sup.+TX;
[0499] 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, Cyclobutrifluram+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].sup.+TX, fluopyram+TX;
[0500] a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580)+TX;
[0501] 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;
[0502] 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 (including alpha-bromadiolone)+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, S.sub.421 (development code) (724)+TX, sesamex (1393)+TX, sesasmolin (1394) and sulfoxide (1406)+TX;
[0503] 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;
[0504] a wound protectant selected from the group of substances consisting of mercuric oxide (512)+TX, octhilinone (590) and thiophanate-methyl (802)+TX;
[0505] a biologically active substance selected from 1,1-bis(4-chloro-phenyl)-2-ethoxyethanol+TX, 2,4-dichlorophenyl benzenesulfonate+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide+TX, 4-chlorophenyl phenyl sulfone+TX, acetoprole+TX, aldoxycarb+TX, amidithion+TX, amidothioate+TX, amiton+TX, amiton hydrogen oxalate+TX, amitraz+TX, aramite+TX, arsenous oxide+TX, azobenzene+TX, azothoate+TX, benomyl+TX, benoxa-fos+TX, benzyl benzoate+TX, bixafen+TX, brofenvalerate+TX, bromo-cyclen+TX, bromophos+TX, bromopropylate+TX, buprofezin+TX, butocarboxim+TX, butoxycarboxim+TX, butylpyridaben+TX, calcium polysulfide+TX, camphechlor+TX, carbanolate+TX, carbophenothion+TX, cymiazole+TX, chino-methionat+TX, chlorbenside+TX, chlordimeform+TX, chlordimeform hydrochloride+TX, chlorfenethol+TX, chlorfenson+TX, chlorfensulfide+TX, chlorobenzilate+TX, chloromebuform+TX, chloromethiuron+TX, chloropropylate+TX, chlorthiophos+TX, cinerin I+TX, cinerin II+TX, cinerins+TX, closantel+TX, coumaphos+TX, crotamiton+TX, crotoxyphos+TX, cufraneb+TX, cyanthoate+TX, DCPM+TX, DDT+TX, demephion+TX, demephion-O+TX, demephion-S+TX, demeton-methyl+TX, demeton-O+TX, demeton-O-methyl+TX, demeton-S+TX, demeton-S-methyl+TX, demeton-S-methylsulfon+TX, dichlofluanid+TX, dichlorvos+TX, dicliphos+TX, dienochlor+TX, dimefox+TX, dinex+TX, dinex-diclexine+TX, dinocap-4+TX, dinocap-6+TX, dinocton+TX, dino-penton+TX, dinosulfon+TX, dinoterbon+TX, dioxathion+TX, diphenyl sulfone+TX, disulfiram+TX, DNOC+TX, dofenapyn+TX, doramectin+TX, endothion+TX, eprinomectin+TX, ethoate-methyl+TX, etrimfos+TX, fenazaflor+TX, fenbutatin oxide+TX, fenothiocarb+TX, fenpyrad+TX, fen-pyroximate+TX, fenpyrazamine+TX, fenson+TX, fentrifanil+TX, flubenzimine+TX, flucycloxuron+TX, fluenetil+TX, fluorbenside+TX, FMC 1137+TX, formetanate+TX, formetanate hydrochloride+TX, formparanate+TX, gamma-HCH+TX, glyodin+TX, halfenprox+TX, hexadecyl cyclopropanecarboxylate+TX, isocarbophos+TX, jasmolin I+TX, jasmolin II+TX, jodfenphos+TX, lindane+TX, malonoben+TX, mecarbam+TX, mephosfolan+TX, mesulfen+TX, methacrifos+TX, methyl bromide+TX, metolcarb+TX, mexacarbate+TX, milbemycin oxime+TX, mipafox+TX, monocrotophos+TX, morphothion+TX, moxidectin+TX, naled+TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one+TX, nifluridide+TX, nikkomycins+TX, nitrilacarb+TX, nitrilacarb 1:1 zinc chloride complex+TX, omethoate+TX, oxydeprofos+TX, oxydisulfoton+TX, pp′-DDT+TX, parathion+TX, permethrin+TX, phenkapton+TX, phosalone+TX, phosfolan+TX, phosphamidon+TX, polychloroterpenes+TX, polynactins+TX, proclonol+TX, promacyl+TX, propoxur+TX, prothidathion+TX, prothoate+TX, pyrethrin I+TX, pyrethrin II+TX, pyrethrins+TX, pyridaphenthion+TX, pyrimitate+TX, quinalphos+TX, quintiofos+TX, R-1492+TX, phosglycin+TX, rotenone+TX, schradan+TX, sebufos+TX, selamectin+TX, sophamide+TX, SSI-121+TX, sulfiram+TX, sulfluramid+TX, sulfotep+TX, sulfur+TX, diflovidazin+TX, tau-fluvalinate+TX, TEPP+TX, terbam+TX, tetradifon+TX, tetrasul+TX, thiafenox+TX, thiocarboxime+TX, thiofanox+TX, thiometon+TX, thioquinox+TX, thuringiensin+TX, triamiphos+TX, triarathene+TX, triazophos+TX, triazuron+TX, trifenofos+TX, trinactin+TX, vamidothion+TX, vaniliprole+TX, bethoxazin+TX, copper dioctanoate+TX, copper sulfate+TX, cybutryne+TX, dichlone+TX, dichlorophen+TX, endothal+TX, fentin+TX, hydrated lime+TX, nabam+TX, quinoclamine+TX, quinonamid+TX, simazine+TX, triphenyltin acetate+TX, triphenyltin hydroxide+TX, crufomate+TX, piperazine+TX, thiophanate+TX, chloralose+TX, fenthion+TX, pyridin-4-amine+TX, strychnine+TX, 1-hydroxy-1H-pyridine-2-thione+TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide+TX, 8-hydroxyquinoline sulfate+TX, bronopol+TX, copper hydroxide+TX, cresol+TX, dipyrithione+TX, dodicin+TX, fenaminosulf+TX, formaldehyde+TX, hydrargaphen+TX, kasugamycin+TX, kasugamycin hydrochloride hydrate+TX, nickel bis(dimethyldithiocarbamate)+TX, nitrapyrin+TX, octhilinone+TX, oxolinic acid+TX, oxytetracycline+TX, potassium hydroxyquinoline sulfate+TX, probenazole+TX, streptomycin+TX, streptomycin sesquisulfate+TX, tecloftalam+TX, thiomersal+TX, Adoxophyes orana GV+TX, Agrobacterium radiobacter+TX, Amblyseius spp.+TX, Anagrapha falcifera NPV+TX, Anagrus atomus+TX, Aphelinus abdominalis+TX, Aphidius colemani+TX, Aphidoletes aphidimyza+TX, Autographa californica NPV+TX, Bacillus sphaericus Neide+TX, Beauveria brongniartii+TX, Chrysoperla carnea+TX, Cryptolaemus montrouzieri+TX, Cydia pomonella GV+TX, Dacnusa sibirica+TX, Diglyphus isaea+TX, Encarsia formosa+TX, Eretmocerus eremicus+TX, Heterorhabditis bacteriophora and H. megidis+TX, Hippodamia convergens+TX, Leptomastix dactylopii+TX, Macrolophus caliginosus+TX, Mamestra brassicae NPV+TX, Metaphycus helvolus+TX, Metarhizium anisopliae var. acridum+TX, Metarhizium anisopliae var. anisopliae+TX, Neodiprion sertifer NPV and N. lecontei NPV+TX, Orius spp.+TX, Paecilomyces fumosoroseus+TX, Phytoseiulus persimilis+TX, Steinernema bibionis+TX, Steinernema carpocapsae+TX, Steinernema feltiae+TX, Steinernema glaseri+TX, Steinernema riobrave+TX, Steinernema riobravis+TX, Steinernema scapterisci+TX, Steinernema spp.+TX, Trichogramma spp.+TX, Typhlodromus occidentalis+TX, Verticillium lecanii+TX, apholate+TX, bisazir+TX, busulfan+TX, dimatif+TX, hemel+TX, hempa+TX, metepa+TX, methiotepa+TX, methyl apholate+TX, morzid+TX, penfluron+TX, tepa+TX, thiohempa+TX, thiotepa+TX, tretamine+TX, uredepa+TX, (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol+TX, (E)-tridec-4-en-1-yl acetate+TX, (E)-6-methylhept-2-en-4-ol+TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate+TX, (Z)-dodec-7-en-1-yl acetate+TX, (Z)-hexadec-11-enal+TX, (Z)-hexadec-11-en-1-yl acetate+TX, (Z)-hexadec-13-en-11-yn-1-yl acetate+TX, (Z)-icos-13-en-10-one+TX, (Z)-tetradec-7-en-1-al+TX, (Z)-tetradec-9-en-1-ol+TX, (Z)-tetradec-9-en-1-yl acetate+TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate+TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate+TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate+TX, 14-methyloctadec-1-ene+TX, 4-methylnonan-5-ol with 4-methylnonan-5-one+TX, alpha-multistriatin+TX, brevicomin+TX, codlelure+TX, codlemone+TX, cuelure+TX, disparlure+TX, dodec-8-en-1-yl acetate+TX, dodec-9-en-1-yl acetate+TX, dodeca-8+TX, 10-dien-1-yl acetate+TX, dominicalure+TX, ethyl 4-methyloctanoate+TX, eugenol+TX, frontalin+TX, grandlure+TX, grandlure I+TX, grandlure II+TX, grandlure III+TX, grandlure IV+TX, hexalure+TX, ipsdienol+TX, ipsenol+TX, japonilure+TX, lineatin+TX, litlure+TX, looplure+TX, medlure+TX, megatomoic acid+TX, methyl eugenol+TX, muscalure+TX, octadeca-2,13-dien-1-yl acetate+TX, octadeca-3,13-dien-1-yl acetate+TX, orfralure+TX, oryctalure+TX, ostramone+TX, siglure+TX, sordidin+TX, sulcatol+TX, tetradec-11-en-1-yl acetate+TX, trimedlure+TX, trimedlure A+TX, trimedlure B.sub.1+TX, trimedlure B.sub.2+TX, trimedlure C+TX, trunc-call+TX, 2-(octylthio)-ethanol+TX, butopyronoxyl+TX, butoxy(polypropylene glycol)+TX, dibutyl adipate+TX, dibutyl phthalate+TX, dibutyl succinate+TX, diethyltoluamide+TX, dimethyl carbate+TX, dimethyl phthalate+TX, ethyl hexanediol+TX, hexamide+TX, methoquin-butyl+TX, methylneodecanamide+TX, oxamate+TX, picaridin+TX, 1-dichloro-1-nitroethane+TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)-ethane+TX, 1,2-dichloropropane with 1,3-dichloropropene+TX, 1-bromo-2-chloroethane+TX, 2,2,2-trichloro-1-(3,4-dichloro-phenyl)ethyl acetate+TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate+TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate+TX, 2-(2-butoxyethoxy)ethyl thiocyanate+TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate+TX, 2-(4-chloro-3,5-xylyloxy)ethanol+TX, 2-chlorovinyl diethyl phosphate+TX, 2-imidazolidone+TX, 2-isovalerylindan-1,3-dione+TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate+TX, 2-thiocyanatoethyl laurate+TX, 3-bromo-1-chloroprop-1-ene+TX, 3-methyl-1-phenylpyrazol-5-yl dimethyl-carbamate+TX, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate+TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate+TX, acethion+TX, acrylonitrile+TX, aldrin+TX, allosamidin+TX, allyxycarb+TX, alpha-ecdysone+TX, aluminium phosphide+TX, aminocarb+TX, anabasine+TX, athidathion+TX, azamethiphos+TX, Bacillus thuringiensis delta endotoxins+TX, barium hexafluorosilicate+TX, barium polysulfide+TX, barthrin+TX, Bayer 22/190+TX, Bayer 22408+TX, beta-cyfluthrin+TX, beta-cypermethrin+TX, bioethanomethrin+TX, biopermethrin+TX, bis(2-chloroethyl) ether+TX, borax+TX, bromfenvinfos+TX, bromo-DDT+TX, bufencarb+TX, butacarb+TX, butathiofos+TX, butonate+TX, calcium arsenate+TX, calcium cyanide+TX, carbon disulfide+TX, carbon tetrachloride+TX, cartap hydrochloride+TX, cevadine+TX, chlorbicyclen+TX, chlordane+TX, chlordecone+TX, chloroform+TX, chloropicrin+TX, chlorphoxim+TX, chlorprazophos+TX, cis-resmethrin+TX, cismethrin+TX, clocythrin+TX, copper acetoarsenite+TX, copper arsenate+TX, copper oleate+TX, coumithoate+TX, cryolite+TX, CS 708+TX, cyanofenphos+TX, cyanophos+TX, cyclethrin+TX, cythioate+TX, d-tetramethrin+TX, DAEP+TX, dazomet+TX, decarbofuran+TX, diamidafos+TX, dicapthon+TX, dichlofenthion+TX, dicresyl+TX, dicyclanil+TX, dieldrin+TX, diethyl 5-methylpyrazol-3-yl phosphate+TX, dilor+TX, dimefluthrin+TX, dimetan+TX, dimethrin+TX, dimethylvinphos+TX, dimetilan+TX, dinoprop+TX, dinosam+TX, dinoseb+TX, diofenolan+TX, dioxabenzofos+TX, dithicrofos+TX, DSP+TX, ecdysterone+TX, El 1642+TX, EMPC+TX, EPBP+TX, etaphos+TX, ethiofencarb+TX, ethyl formate+TX, ethylene dibromide+TX, ethylene dichloride+TX, ethylene oxide+TX, EXD+TX, fenchlorphos+TX, fenethacarb+TX, fenitrothion+TX, fenoxacrim+TX, fenpirithrin+TX, fensulfothion+TX, fenthion-ethyl+TX, flucofuron+TX, fosmethilan+TX, fospirate+TX, fosthietan+TX, furathiocarb+TX, furethrin+TX, guazatine+TX, guazatine acetates+TX, sodium tetrathiocarbonate+TX, halfenprox+TX, HCH+TX, HEOD+TX, heptachlor+TX, heterophos+TX, HHDN+TX, hydrogen cyanide+TX, hyquincarb+TX, IPSP+TX, isazofos+TX, isobenzan+TX, isodrin+TX, isofenphos+TX, isolane+TX, isoprothiolane+TX, isoxathion+TX, juvenile hormone I+TX, juvenile hormone II+TX, juvenile hormone III+TX, kelevan+TX, kinoprene+TX, lead arsenate+TX, leptophos+TX, lirimfos+TX, lythidathion+TX, m-cumenyl methylcarbamate+TX, magnesium phosphide+TX, mazidox+TX, mecarphon+TX, menazon+TX, mercurous chloride+TX, mesulfenfos+TX, metam+TX, metam-potassium+TX, metam-sodium+TX, methanesulfonyl fluoride+TX, methocrotophos+TX, methoprene+TX, methothrin+TX, methoxychlor+TX, methyl isothiocyanate+TX, methylchloroform+TX, methylene chloride+TX, metoxadiazone+TX, mirex+TX, naftalofos+TX, naphthalene+TX, NC-170+TX, nicotine+TX, nicotine sulfate+TX, nithiazine+TX, nornicotine+TX, 0-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate+TX, O,O-diethyl 0-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate+TX, O,O-diethyl 0-6-methyl-2-propylpyrimidin-4-yl phosphorothioate+TX, O,O,O ′,O′-tetrapropyl dithiopyrophosphate+TX, oleic acid+TX, para-dichlorobenzene+TX, parathion-methyl+TX, pentachlorophenol+TX, pentachlorophenyl laurate+TX, PH 60-38+TX, phenkapton+TX, phosnichlor+TX, phosphine+TX, phoxim-methyl+TX, pirimetaphos+TX, polychlorodicyclopentadiene isomers+TX, potassium arsenite+TX, potassium thiocyanate+TX, precocene I+TX, precocene II+TX, precocene III+TX, primidophos+TX, profluthrin+TX, promecarb+TX, prothiofos+TX, pyrazophos+TX, pyresmethrin+TX, quassia+TX, quinalphos-methyl+TX, quinothion+TX, rafoxanide+TX, resmethrin+TX, rotenone+TX, kadethrin+TX, ryania+TX, ryanodine+TX, sabadilla)+TX, schradan+TX, sebufos+TX, SI-0009+TX, thiapronil+TX, sodium arsenite+TX, sodium cyanide+TX, sodium fluoride+TX, sodium hexafluorosilicate+TX, sodium pentachlorophenoxide+TX, sodium selenate+TX, sodium thiocyanate+TX, sulcofuron+TX, sulcofuron-sodium+TX, sulfuryl fluoride+TX, sulprofos+TX, tar oils+TX, tazimcarb+TX, TDE+TX, tebupirimfos+TX, temephos+TX, terallethrin+TX, tetrachloroethane+TX, thicrofos+TX, thiocyclam+TX, thiocyclam hydrogen oxalate+TX, thionazin+TX, thiosultap+TX, thiosultap-sodium+TX, tralomethrin+TX, transpermethrin+TX, triazamate+TX, trichlormetaphos-3+TX, trichloronat+TX, trimethacarb+TX, tolprocarb+TX, triclopyricarb+TX, triprene+TX, veratridine+TX, veratrine+TX, XMC+TX, zetamethrin+TX, zinc phosphide+TX, zolaprofos+TX and meperfluthrin+TX, tetramethylfluthrin+TX, bis(tributyltin) oxide+TX, bromoacetamide+TX, ferric phosphate+TX, niclosamide-olamine+TX, tributyltin oxide+TX, pyrimorph+TX, trifenmorph+TX, 1,2-dibromo-3-chloropropane+TX, 1,3-dichloropropene+TX, 3,4-dichlorotetrahydrothio-phene 1,1-dioxide+TX, 3-(4-chlorophenyl)-5-methylrhodanine+TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid+TX, 6-isopentenylaminopurine+TX, 2-fluoro-N-(3-methoxyphenyl)-9H-purin-6-amine+TX, benclothiaz+TX, cytokinins+TX, DCIP+TX, furfural+TX, isamidofos+TX, kinetin+TX, Myrothecium verrucaria composition+TX, tetrachlorothiophene+TX, xylenols+TX, zeatin+TX, potassium ethylxanthate+TX, acibenzolar+TX, acibenzolar-S-methyl+TX, Reynoutria sachalinensis extract+TX, alpha-chlorohydrin+TX, antu+TX, barium carbonate+TX, bisthiosemi+TX, brodifacoum+TX, bromadiolone+TX, bromethalin+TX, chlorophacinone+TX, cholecalciferol+TX, coumachlor+TX, coumafuryl+TX, coumatetralyl+TX, crimidine+TX, difenacoum+TX, difethialone+TX, diphacinone+TX, ergocalciferol+TX, flocoumafen+TX, fluoroacetamide+TX, flupropadine+TX, flupropadine hydrochloride+TX, norbormide+TX, phosacetim+TX, phosphorus+TX, pindone+TX, pyrinuron+TX, scilliroside+TX, -sodium fluoroacetate+TX, thallium sulfate+TX, warfarin+TX, -2-(2-butoxyethoxy)ethyl piperonylate+TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone+TX, farnesol with nerolidol+TX, verbutin+TX, MGK 264+TX, piperonyl butoxide+TX, piprotal+TX, propyl isomer+TX, S421+TX, sesamex+TX, sesasmolin+TX, sulfoxide+TX, anthraquinone+TX, copper naphthenate+TX, copper oxychloride+TX, dicyclopentadiene+TX, thiram+TX, zinc naphthenate+TX, ziram+TX, imanin+TX, ribavirin+TX, chloroinconazide+TX, mercuric oxide+TX, thiophanate-methyl+TX, azaconazole+TX, bitertanol+TX, bromuconazole+TX, cyproconazole+TX, difenoconazole+TX, diniconazole-+TX, epoxiconazole+TX, fenbuconazole+TX, fluquinconazole+TX, flusilazole+TX, flutriafol+TX, furametpyr+TX, hexaconazole+TX, imazalil-+TX, imiben-conazole+TX, ipconazole+TX, metconazole+TX, myclobutanil+TX, paclobutrazole+TX, pefurazoate+TX, penconazole+TX, prothioconazole+TX, pyrifenox+TX, prochloraz+TX, propiconazole+TX, pyrisoxazole+TX, -simeconazole+TX, tebucon-azole+TX, tetraconazole+TX, triadimefon+TX, triadimenol+TX, triflumizole+TX, triticonazole+TX, ancymidol+TX, fenarimol+TX, nuarimol+TX, bupirimate+TX, dimethirimol+TX, ethirimol+TX, dodemorph+TX, fenpropidin+TX, fenpropimorph+TX, spiroxamine+TX, tridemorph+TX, cyprodinil+TX, mepanipyrim+TX, pyrimethanil+TX, fenpiclonil+TX, fludioxonil+TX, benalaxyl+TX, furalaxyl+TX, -metalaxyl-+TX, Rmetalaxyl+TX, ofurace+TX, oxadixyl+TX, carbendazim+TX, debacarb+TX, fuberidazole-+TX, thiabendazole+TX, chlozolinate+TX, dichlozoline+TX, myclozoline-+TX, procymidone+TX, vinclozoline+TX, boscalid+TX, carboxin+TX, fenfuram+TX, flutolanil+TX, mepronil+TX, oxycarboxin+TX, penthiopyrad+TX, thifluzamide+TX, dodine+TX, iminoctadine+TX, azoxystrobin+TX, dimoxystrobin+TX, enestroburin+TX, fenaminstrobin+TX, flufenoxystrobin+TX, fluoxastrobin+TX, kresoxim-methyl+TX, metominostrobin+TX, trifloxystrobin+TX, orysastrobin+TX, picoxystrobin+TX, pyraclostrobin+TX, pyrametostrobin+TX, pyraoxystrobin+TX, ferbam+TX, mancozeb+TX, maneb+TX, metiram+TX, propineb+TX, zineb+TX, captafol+TX, captan+TX, fluoroimide+TX, folpet+TX, tolylfluanid+TX, bordeaux mixture+TX, copper oxide+TX, mancopper+TX, oxine-copper+TX, nitrothal-isopropyl+TX, edifenphos+TX, iprobenphos+TX, phosdiphen+TX, tolclofos-methyl+TX, anilazine+TX, benthiavalicarb+TX, blasticidin-S+TX, chloroneb-+TX, chloro-tha-lonil+TX, cyflufenamid+TX, cymoxanil+TX, cyclobutrifluram+TX, diclocymet+TX, diclomezine-+TX, dicloran+TX, diethofencarb+TX, dimethomorph-+TX, flumorph+TX, dithianon+TX, ethaboxam+TX, etridiazole+TX, famoxadone+TX, fenamidone+TX, fenoxanil+TX, ferimzone+TX, fluazinam+TX, fluopicolide+TX, flusulfamide+TX, fluxapyroxad+TX,-fenhexamid+TX, fosetyl-aluminium-+TX, hymexazol+TX, iprovalicarb+TX, cyazofamid+TX, methasulfocarb+TX, metrafenone+TX, pencycuron+TX, phthalide+TX, polyoxins+TX, propamocarb+TX, pyribencarb+TX, proquinazid+TX, pyroquilon+TX, pyriofenone+TX, quinoxyfen+TX, quintozene+TX, tiadinil+TX, triazoxide+TX, tricyclazole+TX, triforine+TX, validamycin+TX, valifenalate+TX, zoxamide+TX, mandipropamid+TX, flubeneteram+TX, isopyrazam+TX, sedaxane+TX, benzovindiflupyr+TX, pydiflumetofen+TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3′,4′,5′-trifluoro-biphenyl-2-yl)-amide+TX, isoflucypram+TX, isotianil+TX, dipymetitrone+TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile+TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile+TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide+TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine+TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1, 3-dimethyl-1H-pyrazol-5-amine+TX, fluindapyr+TX, coumethoxystrobin (jiaxiangjunzhi)+TX, Ivbenmixianan+TX, dichlobentiazox+TX, mandestrobin+TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone+TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol+TX, oxathiapiprolin+TX, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate+TX, pyraziflumid+TX, inpyrfluxam+TX, trolprocarb+TX, mefentrifluconazole+TX, ipfentrifluconazole+TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX, N′-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine+TX, N′-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine+TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl] methanesulfonate+TX, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate+TX, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate+TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine+TX, pyridachlometyl+TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide+TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one+TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one+TX, aminopyrifen+TX, ametoctradin+TX, amisulbrom+TX, penflufen+TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide+TX, florylpicoxamid+TX, fenpicoxamid+TX, tebufloquin+TX, ipflufenoquin+TX, quinofumelin+TX, isofetamid+TX, N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide+TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide+TX, benzothiostrobin+TX, phenamacril+TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1)+TX, fluopyram+TX, flutianil+TX, fluopimomide+TX, pyrapropoyne+TX, picarbutrazox+TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide+TX, 2-(difluoromethyl)-N-((3R)-1, 1, 3-trimethylindan-4-yl) pyridine-3-carboxamide+TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile+TX, metyltetraprole+TX, 2-(difluoromethyl)-N-((3R)-1, 1, 3-trimethylindan-4-yl) pyridine-3-carboxamide+TX, α-(1, 1-dimethylethyl)-α-[4′-(trifluoromethoxy) [1, 1′-biphenyl]-4-yl]-5-pyrimidinemethanol+TX, fluoxapiprolin+TX, enoxastrobin+TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile+TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile+TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile+TX, trinexapac+TX, coumoxystrobin+TX, zhongshengmycin+TX, thiodiazole copper+TX, zinc thiazole+TX, amectotractin+TX, iprodione+TX, N-octyl-N′-[2-(octylamino)ethyl]ethane-1,2-diamine+TX; N′-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine+TX, N′-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine+TX, N′-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine+TX, N′-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine+TX, N′-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine+TX (these compounds may be prepared from the methods described in WO2015/155075); N′-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine+TX (this compound may be prepared from the methods described in IPCOM000249876D); N-isopropyl-N′-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine+TX, N′-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine+TX (these compounds may be prepared from the methods described in WO2018/228896); N-ethyl-N′-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine+TX, N-ethyl-N′-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine+TX (these compounds may be prepared from the methods described in WO2019/110427); N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide+TX, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide+TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide+TX, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide+TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide+TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide+TX, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide+TX, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide+TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide+TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide+TX, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide+TX, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide+TX (these compounds may be prepared from the methods described in WO2017/153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline+TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline+TX, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline+TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline+TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline+TX (these compounds may be prepared from the methods described in WO2017/025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline+TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline+TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline+TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline+TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole+TX (these compounds may be prepared from the methods described in WO2016/156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide+TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide+TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide+TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide+TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one+TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one+TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate+TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine+TX. The compounds in this paragraph may be prepared from the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol+TX (this compound may be prepared from the methods described in WO 2017/029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol+TX (this compound may be prepared from the methods described in WO 2017/029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile+TX (this compound may be prepared from the methods described in WO 2016/156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile+TX (this compound may be prepared from the methods described in WO 2016/156290); (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate+TX (this compound may be prepared from the methods described in WO 2014/006945); 2,6-Dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone+TX (this compound may be prepared from the methods described in WO 2011/138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide+TX; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide+TX (this compound may be prepared from the methods described in WO 2018/153707); N′-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine+TX; N′-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine+TX (this compound may be prepared from the methods described in WO 2016/202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX (this compound may be prepared from the methods described in WO 2014/095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone+TX, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone+TX (these compounds may be prepared from the methods described in WO 2017/220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide+TX (this compound may be prepared from the methods described in WO 2018/065414); ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate+TX (this compound may be prepared from the methods described in WO 2018/158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide+TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX, N—[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX, N—[N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX (these compounds may be prepared from the methods described in WO 2018/202428);
[0506] microbials including: Acinetobacter Iwoffii+TX, Acremonium alternatum+TX+TX, Acremonium cephalosporium+TX+TX, Acremonium diospyri+TX, Acremonium obclavatum+TX, Adoxophyes orana granulovirus (AdoxGV) (Capex®)+TX, Agrobacterium radiobacter strain K84 (Galltrol-A®)+TX, Alternaria alternate+TX, Alternaria cassia+TX, Alternaria destruens (Smolder®)+TX, Ampelomyces quisqualis (AQ10®)+TX, Aspergillus flavus AF36 (AF36®)+TX, Aspergillus flavus NRRL 21882 (Aflaguard®)+TX, Aspergillus spp.+TX, Aureobasidium pullulans+TX, Azospirillum+TX, (MicroAZ®+TX, TAZO B®)+TX, Azotobacter+TX, Azotobacter chroocuccum (Azotomeal®)+TX, Azotobacter cysts (Bionatural Blooming Blossoms®)+TX, Bacillus amyloliquefaciens+TX, Bacillus cereus+TX, Bacillus chitinosporus strain CM-1+TX, Bacillus chitinosporus strain AQ746+TX, Bacillus licheniformis strain HB-2 (Biostart™ Rhizoboost®)+TX, Bacillus licheniformis strain 3086 (EcoGuard®+TX, Green Releaf®)+TX, Bacillus circulans+TX, Bacillus firmus (BioSafe®+TX, BioNem-WP®+TX, VOTiVO®)+TX, Bacillus firmus strain 1-1582+TX, Bacillus macerans+TX, Bacillus marismortui+TX, Bacillus megaterium+TX, Bacillus mycoides strain AQ726+TX, Bacillus papillae (Milky Spore Powder®)+TX, Bacillus pumilus spp.+TX, Bacillus pumilus strain GB34 (Yield Shield®)+TX, Bacillus pumilus strain AQ717+TX, Bacillus pumilus strain QST 2808 (Sonata®+TX, Ballad Plus®)+TX, Bacillus spahericus (VectoLex®)+TX, Bacillus spp.+TX, Bacillus spp. strain AQ175+TX, Bacillus spp. strain AQ177+TX, Bacillus spp. strain AQ178+TX, Bacillus subtilis strain QST 713 (CEASE®+TX, Serenade®+TX, Rhapsody®)+TX, Bacillus subtilis strain QST 714 (JAZZ®)+TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilis strain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 (Taegro®+TX, Rhizopro®)+TX, Bacillus thuringiensis Cry 2Ae+TX, Bacillus thuringiensis Cry1 Ab+TX, Bacillus thuringiensis aizawai GC 91 (Agree®)+TX, Bacillus thuringiensis israelensis (BMP123®+TX, Aquabac®+TX, VectoBac®)+TX, Bacillus thuringiensis kurstaki (Javelin®+TX, Deliver®+TX, CryMax®+TX, Bonide®+TX, Scutella WP®+TX, Turilav WP®+TX, Astuto®+TX, Dipel WP®+TX, Biobit®+TX, Foray®)+TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®)+TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF/3P®)+TX, Bacillus thuringiensis strain BD #32+TX, Bacillus thuringiensis strain AQ52+TX, Bacillus thuringiensis var. aizawai (XenTari®+TX, DiPel®)+TX, bacteria spp. (GROWMEND@+TX, GROWSWEET®+TX, Shootup®)+TX, bacteriophage of Clavipacter michiganensis (AgriPhage®)+TX, Bakflor®+TX, Beauveria bassiana (Beaugenic®+TX, Brocaril WP®)+TX, Beauveria bassiana GHA (Mycotrol ES®+TX, Mycotrol O®+TX, BotaniGuard®)+TX, Beauveria brongniartii (Engerlingspilz®+TX, Schweizer Beauveria®+TX, Melocont®)+TX, Beauveria spp.+TX, Botrytis cineria+TX, Bradyrhizobium japonicum (TerraMax®)+TX, Brevibacillus brevis+TX, Bacillus thuringiensis tenebrionis (Novodor®)+TX, BtBooster+TX, Burkholderia cepacia (Deny®+TX, Intercept®+TX, Blue Circle®)+TX, Burkholderia gladii+TX, Burkholderia gladioli+TX, Burkholderia spp.+TX, Canadian thistle fungus (CBH Canadian Bioherbicide®)+TX, Candida butyri+TX, Candida famata+TX, Candida fructus+TX, Candida glabrata+TX, Candida guilliermondii+TX, Candida melibiosica+TX, Candida oleophila strain O+TX, Candida parapsilosis+TX, Candida pelliculosa+TX, Candida pulcherrima+TX, Candida reukaufii+TX, Candida saitoana (Bio-Coat®+TX, Biocure®)+TX, Candida sake+TX, Candida spp.+TX, Candida tenius+TX, Cedecea dravisae+TX, Cellulomonas flavigena+TX, Chaetomium cochliodes (Nova-Cide®)+TX, Chaetomium globosum (Nova-Cide®)+TX, Chromobacterium subtsugae strain PRAA4-1T (Grandevo®)+TX, Cladosporium cladosporioides+TX, Cladosporium oxysporum+TX, Cladosporium chlorocephalum+TX, Cladosporium spp.+TX, Cladosporium tenuissimum+TX, Clonostachys rosea (EndoFine®)+TX, Colletotrichum acutatum+TX, Coniothyrium minitans (Cotans WG®)+TX, Coniothyrium spp.+TX, Cryptococcus albidus (YIELDPLUS®)+TX, Cryptococcus humicola+TX, Cryptococcus infirmominiatus+TX, Cryptococcus laurentii+TX, Cryptophlebia leucotreta granulovirus (Cryptex®)+TX, Cupriavidus campinensis+TX, Cydia pomonella granulovirus (CYD-X®)+TX, Cydia pomonella granulovirus (Madex®+TX, Madex Plus®+TX, Madex Max/Carpovirusine®)+TX, Cylindrobasidium laeve (Stumpout®)+TX, Cylindrocladium+TX, Debaryomyces hansenii+TX, Drechslera hawaiinensis+TX, Enterobacter cloacae+TX, Enterobacteriaceae+TX, Entomophtora virulenta (Vektor®)+TX, Epicoccum nigrum+TX, Epicoccum purpurascens+TX, Epicoccum spp.+TX, Filobasidium floriforme+TX, Fusarium acuminatum+TX, Fusarium chlamydosporum+TX, Fusarium oxysporum (Fusaclean®/Biofox C®)+TX, Fusarium proliferatum+TX, Fusarium spp.+TX, Galactomyces geotrichum+TX, Gliocladium catenulatum (Primastop®+TX, Prestop®)+TX, Gliocladium roseum+TX, Gliocladium spp. (SoilGard®)+TX, Gliocladium virens (Soilgard®)+TX, Granulovirus (Granupom®)+TX, Halobacillus halophilus+TX, Halobacillus litoralis+TX, Halobacillus trueperi+TX, Halomonas spp.+TX, Halomonas subglaciescola+TX, Halovibrio variabilis+TX, Hanseniaspora uvarum+TX, Helicoverpa armigera nucleopolyhedrovirus (Helicovex®)+TX, Helicoverpa zea nuclear polyhedrosis virus (Gemstar®)+TX, Isoflavone-formononetin (Myconate®)+TX, Kloeckera apiculata+TX, Kloeckera spp.+TX, Lagenidium giganteum (Laginex®)+TX, Lecanicillium longisporum (Vertiblast®)+TX, Lecanicillium muscarium (Vertikil®)+TX, Lymantria dispar nucleopolyhedrosis virus (Disparvirus®)+TX, Marinococcus halophilus+TX, Meira geulakonigii+TX, Metarhizium anisopliae (Met52®)+TX, Metarhizium anisopliae (Destruxin WP®)+TX, Metschnikowia fruticola (Shemer®)+TX, Metschnikowia pulcherrima+TX, Microdochium dimerum (Antibot®)+TX, Micromonospora coerulea+TX, Microsphaeropsis ochracea+TX, Muscodor albus 620 (Muscudor®)+TX, Muscodor roseus strain A3-5+TX, Mycorrhizae spp. (AMykor®+TX, Root Maximizer®)+TX, Myrothecium verrucaria strain AARC-0255 (DiTera®)+TX, BROS PLUS®+TX, Ophiostoma piliferum strain D97 (Sylvanex®)+TX, Paecilomyces farinosus+TX, Paecilomyces fumosoroseus (PFR-97®+TX, PreFeRal®)+TX, Paecilomyces linacinus (Biostat WP®)+TX, Paecilomyces lilacinus strain 251 (MeloCon WG®)+TX, Paenibacillus polymyxa+TX, Pantoea agglomerans (BlightBan C.sub.9-1®)+TX, Pantoea spp.+TX, Pasteuria spp. (Econem®)+TX, Pasteuria nishizawae+TX, Penicillium aurantiogriseum+TX, Penicillium billai (Jumpstart®+TX, TagTeam®)+TX, Penicillium brevicompactum+TX, Penicillium frequentans+TX, Penicillium griseofulvum+TX, Penicillium purpurogenum+TX, Penicillium spp.+TX, Penicillium viridicatum+TX, Phlebiopsis gigantean (Rotstop®)+TX, phosphate solubilizing bacteria (Phosphomeal®)+TX, Phytophthora cryptogea+TX, Phytophthora palmivora (Devine®)+TX, Pichia anomala+TX, Pichia guilermondii+TX, Pichia membranaefaciens+TX, Pichia onychis+TX, Pichia stipites+TX, Pseudomonas aeruginosa+TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®)+TX, Pseudomonas cepacia+TX, Pseudomonas chlororaphis (AtEze®)+TX, Pseudomonas corrugate+TX, Pseudomonas fluorescens strain A506 (BlightBan A506®)+TX, Pseudomonas putida+TX, Pseudomonas reactans+TX, Pseudomonas spp.+TX, Pseudomonas syringae (Bio-Save®)+TX, Pseudomonas viridiflava+TX, Pseudomons fluorescens (Zequanox®)+TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®)+TX, Puccinia canaliculata+TX, Puccinia thlaspeos (Wood Warrior®)+TX, Pythium paroecandrum+TX, Pythium oligandrum (Polygandron®+TX, Polyversum®)+TX, Pythium periplocum+TX, Rhanella aquatilis+TX, Rhanella spp.+TX, Rhizobia (Dormal®+TX, Vault®)+TX, Rhizoctonia+TX, Rhodococcus globerulus strain AQ719+TX, Rhodosporidium diobovatum+TX, Rhodosporidium toruloides+TX, Rhodotorula spp.+TX, Rhodotorula glutinis+TX, Rhodotorula graminis+TX, Rhodotorula mucilagnosa+TX, Rhodotorula rubra+TX, Saccharomyces cerevisiae+TX, Salinococcus roseus+TX, Sclerotinia minor+TX, Sclerotinia minor (SARRITOR®)+TX, Scytalidium spp.+TX, Scytalidium uredinicola+TX, Spodoptera exigua nuclear polyhedrosis virus (Spod-X®+TX, Spexit®)+TX, Serratia marcescens+TX, Serratia plymuthica+TX, Serratia spp.+TX, Sordaria fimicola+TX, Spodoptera littoralis nucleopolyhedrovirus (Littovir®)+TX, Sporobolomyces roseus+TX, Stenotrophomonas maltophilia+TX, Streptomyces ahygroscopicus+TX, Streptomyces albaduncus+TX, Streptomyces exfoliates+TX, Streptomyces galbus+TX, Streptomyces griseoplanus+TX, Streptomyces griseoviridis (Mycostop®)+TX, Streptomyces lydicus (Actinovate®)+TX, Streptomyces lydicus WYEC-108 (ActinoGrow®)+TX, Streptomyces violaceus+TX, Tilletiopsis minor+TX, Tilletiopsis spp.+TX, Trichoderma asperellum (T34 Biocontrol®)+TX, Trichoderma gamsii (Tenet®)+TX, Trichoderma atroviride (Plantmate®)+TX, Trichoderma hamatum TH 382+TX, Trichoderma harzianum rifai (Mycostar®)+TX, Trichoderma harzianum T-22 (Trianum-P®+TX, PlantShield HCO+TX, RootShield®+TX, Trianum-G®)+TX, Trichoderma harzianum T-39 (Trichodex®)+TX, Trichoderma inhamatum+TX, Trichoderma koningii+TX, Trichoderma spp. LC 52 (Sentinel®)+TX, Trichoderma lignorum+TX, Trichoderma longibrachiatum+TX, Trichoderma polysporum (Binab T®)+TX, Trichoderma taxi+TX, Trichoderma virens+TX, Trichoderma virens (formerly Gliocladium virens GL-21) (SoilGuard®)+TX, Trichoderma viride+TX, Trichoderma viride strain ICC 080 (Remedier®)+TX, Trichosporon pullulans+TX, Trichosporon spp.+TX, Trichothecium spp.+TX, Trichothecium roseum+TX, Typhula phacorrhiza strain 94670+TX, Typhula phacorrhiza strain 94671+TX, Ulocladium atrum+TX, Ulocladium oudemansii (Botry-Zen®)+TX, Ustilago maydis+TX, various bacteria and supplementary micronutrients (Natural II®)+TX, various fungi (Millennium Microbes®)+TX, Verticillium chlamydosporium+TX, Verticillium lecanii (Mycotal®+TX, Vertalec®)+TX, Vip3Aa20 (VIPtera®)+TX, Virgibaclillus marismortui+TX, Xanthomonas campestris pv. Poae (Camperico®)+TX, Xenorhabdus bovienii+TX, Xenorhabdus nematophilus;
[0507] Plant extracts including: pine oil (Retenol®)+TX, azadirachtin (Plasma Neem Oil®+TX, AzaGuard®+TX, MeemAzal®+TX, Molt-X®+TX, Botanical IGR (Neemazad®+TX, Neemix®)+TX, canola oil (Lilly Miller Vegol®)+TX, Chenopodium ambrosioides near ambrosioides (Requiem®)+TX, Chrysanthemum extract (Crisant®)+TX, extract of neem oil (Trilogy®)+TX, essentials oils of Labiatae (Botania®)+TX, extracts of clove rosemary peppermint and thyme oil (Garden insect killer®)+TX, Glycinebetaine (Greenstim®)+TX, garlic+TX, lemongrass oil (GreenMatch®)+TX, neem oil+TX, Nepeta cataria (Catnip oil)+TX, Nepeta catarina+TX, nicotine+TX, oregano oil (MossBuster®)+TX, Pedaliaceae oil (Nematon®)+TX, pyrethrum+TX, Quillaja saponaria (NemaQ®)+TX, Reynoutria sachalinensis (Regalia®+TX, Sakalia®)+TX, rotenone (Eco Roten®)+TX, Rutaceae plant extract (Soleo®)+TX, soybean oil (Ortho ecosense®)+TX, tea tree oil (Timorex Gold®)+TX, thymus oil+TX, AGNIQUE® MMF+TX, BugOil®+TX, mixture of rosemary sesame pepermint thyme and cinnamon extracts (EF 300®)+TX, mixture of clove rosemary and peppermint extract (EF 400®)+TX, mixture of clove peppermint garlic oil and mint (Soil Shot®)+TX, kaolin (Screen®)+TX, storage glucam of brown algae (Laminarin®);
[0508] pheromones including: blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®)+TX, Codling Moth Pheromone (Paramount dispenser-(CM)/Isomate C-Plus®)+TX, Grape Berry Moth Pheromone (3M MEC-GBM Sprayable Pheromone®)+TX, Leafroller pheromone (3M MEC—LR Sprayable Pheromone®)+TX, Muscamone (Snip7 Fly Bait®+TX, Starbar Premium Fly Bait®)+TX, Oriental Fruit Moth Pheromone (3M oriental fruit moth sprayable Pheromone®)+TX, Peachtree Borer Pheromone (Isomate-P®)+TX, Tomato Pinworm Pheromone (3M Sprayable pheromone®)+TX, Entostat powder (extract from palm tree) (Exosex CM®)+TX, (E+TX,Z+TX,Z)-3+TX,8+TX,11 Tetradecatrienyl acetate+TX, (Z+TX,Z+TX,E)-7+TX,11+TX,13-Hexadecatrienal+TX, (E+TX,Z)-7+TX,9-Dodecadien-1-yl acetate+TX, 2-Methyl-1-butanol+TX, Calcium acetate+TX, Scenturion®+TX, Biolure®+TX, Check-Mate®+TX, Lavandulyl senecioate; Macrobials including: Aphelinus abdominalis+TX, Aphidius ervi (Aphelinus-System®)+TX, Acerophagus papaya+TX, Adalia bipunctata (Adalia-System®)+TX, Adalia bipunctata (Adaline®)+TX, Adalia bipunctata (Aphidalia®)+TX, Ageniaspis citricola+TX, Ageniaspis fuscicollis+TX, Amblyseius andersoni (Anderline®+TX andersoni-System®)+TX, Amblyseius californicus (Amblyline®+TX, Spical®)+TX, Amblyseius cucumeris (Thripex®+TX, Bugline cucumeris®)+TX, Amblyseius fallacis (Fallacis®)+TX, Amblyseius swirskii (Bugline swirskii®+TX, Swirskii-Mite®)+TX, Amblyseius womersleyi (WomerMite®)+TX, Amitus hesperidum+TX, Anagrus atomus+TX, Anagyrus fusciventris+TX, Anagyrus kamali+TX, Anagyrus loecki+TX, Anagyrus pseudococci (Citripar®)+TX, Anicetus benefices+TX, Anisopteromalus calandrae+TX, Anthocoris nemoralis (Anthocoris-System®)+TX, Aphelinus abdominalis (Apheline®+TX, Aphiline®)+TX, Aphelinus asychis+TX, Aphidius colemani (Aphipar®)+TX, Aphidius ervi (Ervipar®)+TX, Aphidius gifuensis+TX, Aphidius matricariae (Aphipar-M®)+TX, Aphidoletes aphidimyza (Aphidend®)+TX, Aphidoletes aphidimyza (Aphidoline®)+TX, Aphytis lingnanensis+TX, Aphytis melinus+TX, Aprostocetus hagenowii+TX, Atheta coriaria (Staphyline®)+TX, Bombus spp.+TX, Bombus terrestris (Natupol Beehive®)+TX, Bombus terrestris (Beeline®+TX, Tripol®)+TX, Cephalonomia stephanoderis+TX, Chilocorus nigritus+TX, Chrysoperla carnea (Chrysoline®)+TX, Chrysoperla carnea (Chrysopa®)+TX, Chrysoperla rufilabris+TX, Cirrospilus ingenuus+TX, Cirrospilus quadristriatus+TX, Citrostichus phyllocnistoides+TX, Closterocerus chamaeleon+TX, Closterocerus spp.+TX, Coccidoxenoides perminutus (Planopar®)+TX, Coccophagus cowperi+TX, Coccophagus lycimnia+TX, Cotesia flavipes+TX, Cotesia plutellae+TX, Cryptolaemus montrouzieri (Cryptobug®+TX, Cryptoline®)+TX, Cybocephalus nipponicus+TX, Dacnusa sibirica+TX, Dacnusa sibirica (Minusa®)+TX, Diglyphus isaea (Diminex®)+TX, Delphastus catalinae (Delphastus®)+TX, Delphastus pusillus+TX, Diachasmimorpha krausii+TX, Diachasmimorpha longicaudata+TX, Diaparsis jucunda+TX, Diaphorencyrtus aligarhensis+TX, Diglyphus isaea+TX, Diglyphus isaea (Miglyphus®+TX, Digline®)+TX, Dacnusa sibirica (DacDigline®+TX, Minex®)+TX, Diversinervus spp.+TX, Encarsia citrina+TX, Encarsia formosa (Encarsia max®+TX, Encarline®+TX, En-Strip®)+TX, Eretmocerus eremicus (Enermix®)+TX, Encarsia guadeloupae+TX, Encarsia haitiensis+TX, Episyrphus balteatus (Syrphidend®)+TX, Eretmoceris siphonini+TX, Eretmocerus californicus+TX, Eretmocerus eremicus (Ercal®+TX, Eretline e®)+TX, Eretmocerus eremicus (Bemimix®)+TX, Eretmocerus hayati+TX, Eretmocerus mundus (Bemipar®+TX, Eretline m®)+TX, Eretmocerus siphonini+TX, Exochomus quadripustulatus+TX, Feltiella acarisuga (Spidend®)+TX, Feltiella acarisuga (Feltiline®)+TX, Fopius arisanus+TX, Fopius ceratitivorus+TX, Formononetin (Wirless Beehome®)+TX, Franklinothrips vespiformis (Vespop®)+TX, Galendromus occidentalis+TX, Goniozus legneri+TX, Habrobracon hebetor+TX, Harmonia axyridis (HarmoBeetle®)+TX, Heterorhabditis spp. (Lawn Patrol®)+TX, Heterorhabditis bacteriophora (NemaShield HB®+TX, Nemaseek®+TX, Terranem-Nam®+TX, Terranem®+TX, Larvanem®+TX, B-Green®+TX, NemAttack®+TX, Nematop®)+TX, Heterorhabditis megidis (Nemasys H®+TX, BioNem H®+TX, Exhibitline hm®+TX, Larvanem-M®)+TX, Hippodamia convergens+TX, Hypoaspis aculeifer (Aculeifer-System®+TX, Entomite-A®)+TX, Hypoaspis miles (Hypoline m®+TX, Entomite-M®)+TX, Lbalia leucospoides+TX, Lecanoideus floccissimus+TX, Lemophagus errabundus+TX, Leptomastidea abnormis+TX, Leptomastix dactylopii (Leptopar®)+TX, Leptomastix epona+TX, Lindorus lophanthae+TX, Lipolexis oregmae+TX, Lucilia caesar (Natufly®)+TX, Lysiphlebus testaceipes+TX, Macrolophus caliginosus (Mirical-N®+TX, Macroline c®+TX, Mirical®)+TX, Mesoseiulus longipes+TX, Metaphycus flavus+TX, Metaphycus lounsburyi+TX, Micromus angulatus (Milacewing®)+TX, Microterys flavus+TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®)+TX, Neodryinus typhlocybae+TX, Neoseiulus californicus+TX, Neoseiulus cucumeris (THRYPEX®)+TX, Neoseiulus fallacis+TX, Nesideocoris tenuis (NesidioBug®+TX, Nesibug®)+TX, Ophyra aenescens (Biofly®)+TX, Orius insidiosus (Thripor-I@+TX, Oriline i®)+TX, Orius laevigatus (Thripor-L®+TX, Oriline I®)+TX, Orius majusculus (Oriline m®)+TX, Orius strigicollis (Thripor-S®)+TX, Pauesia juniperorum+TX, Pediobius foveolatus+TX, Phasmarhabditis hermaphrodita (Nemaslug®)+TX, Phymastichus coffea+TX, Phytoseiulus macropilus+TX, Phytoseiulus persimilis (Spidex®+TX, Phytoline p®)+TX, Podisus maculiventris (Podisus®)+TX, Pseudacteon curvatus+TX, Pseudacteon obtusus+TX, Pseudacteon tricuspis+TX, Pseudaphycus maculipennis+TX, Pseudleptomastix mexicana+TX, Psyllaephagus pilosus+TX, Psyttalia concolor (complex)+TX, Quadrastichus spp.+TX, Rhyzobius lophanthae+TX, Rodolia cardinalis+TX, Rumina decollate+TX, Semielacher petiolatus+TX, Sitobion avenae (Ervibank®)+TX, Steinernema carpocapsae (Nematac C®+TX, Millenium®+TX, BioNem C®+TX, NemAttack@+TX, Nemastar®+TX, Capsanem®)+TX, Steinernema feltiae (NemaShield®+TX, Nemasys F®+TX, BioNem F®+TX, Steinernema-System®+TX, NemAttack®+TX, Nemaplus®+TX, Exhibitline sf®+TX, Scia-rid®+TX, Entonem®)+TX, Steinernema kraussei (Nemasys L®+TX, BioNem L®+TX, Exhibitline srb®)+TX, Steinernema riobrave (BioVector®+TX, BioVektor®)+TX, Steinernema scapterisci (Nematac S®)+TX, Steinernema spp.+TX, Steinernematid spp. (Guardian Nematodes®)+TX, Stethorus punctillum (Stethorus®)+TX, Tamarixia radiate+TX, Tetrastichus setifer+TX, Thripobius semiluteus+TX, Torymus sinensis+TX, Trichogramma brassicae (Tricholine b®)+TX, Trichogramma brassicae (Tricho-Strip®)+TX, Trichogramma evanescens+TX, Trichogramma minutum+TX, Trichogramma ostriniae+TX, Trichogramma platneri+TX, Trichogramma pretiosum+TX, Xanthopimpla stemmator;
[0509] other biologicals including: abscisic acid+TX, bioSea®+TX, Chondrostereum purpureum (Chontrol Paste®)+TX, Colletotrichum gloeosporioides (Collego®)+TX, Copper Octanoate (Cueva®)+TX, Delta traps (Trapline d®)+TX, Erwinia amylovora (Harpin) (ProAct®+TX, Ni-HIBIT Gold CST®)+TX, Ferri-phosphate (Ferramol®)+TX, Funnel traps (Trapline y®)+TX, Gallex®+TX, Grower's Secret®+TX, Homo-brassonolide+TX, Iron Phosphate (Lilly Miller Worry Free Ferramol Slug & Snail Bait®)+TX, MCP hail trap (Trapline f®)+TX, Microctonus hyperodae+TX, Mycoleptodiscus terrestris (Des-X®)+TX, BioGain®+TX, Aminomite®+TX, Zenox®+TX, Pheromone trap (Thripline ams®)+TX, potassium bicarbonate (MilStop®)+TX, potassium salts of fatty acids (Sanova®)+TX, potassium silicate solution (Sil-Matrix®)+TX, potassium iodide+potassiumthiocyanate (Enzicur®)+TX, SuffOil-X®+TX, Spider venom+TX, Nosema locustae (Semaspore Organic Grasshopper Control®)+TX, Sticky traps (Trapline YF®+TX, Rebell Amarillo®)+TX and Traps (Takitrapline y+b®)+TX; and a safener, such as benoxacor+TX, cloquintocet (including cloquintocet-mexyl)+TX, cyprosulfamide+TX, dichlormid+TX, fenchlorazole (including fenchlorazole-ethyl)+TX, fenclorim+TX, fluxofenim+TX, furilazole+TX, isoxadifen (including isoxadifen-ethyl)+TX, mefenpyr (including mefenpyr-diethyl)+TX, metcamifen+TX and oxabetrinil+TX.
[0510] 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.
[0511] 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.
[0512] The active ingredient mixture of the compounds of formula (I) selected from the compounds defined in the Tables 1 to 35 and Table P1 to P8 with active ingredients described above comprises a compound selected from one compound defined in the Tables 1 to 35 and Table P1 to P8 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.
[0513] 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.
[0514] The mixtures comprising a compound of formula (I) selected from the compounds defined in the Tables 1 to 35 and Table P1 to P8 and one or more active ingredients as described above can be applied, for example, in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula (I) and the active ingredients as described above is not essential for working the present invention.
[0515] 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.
[0516] 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.
[0517] 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.
[0518] 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.
[0519] The compounds of formula (I) of the invention and compositions thereof are also be suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type. The propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing. Alternatively, the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention. Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds.
[0520] 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.
[0521] The present invention also comprises seeds coated or treated with or containing a compound of formula I. The term “coated or treated with and/or containing” generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the ingredient may penetrate into the seed material, depending on the method of application. When the said seed product is (re)planted, it may absorb the active ingredient. In an embodiment, the present invention makes available a plant propagation material adhered thereto with a compound of formula I. Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound of formula I.
[0522] Seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting. The seed treatment application of the compound formula (I) can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds.
[0523] The compounds of the invention can be distinguished from other similar compounds by virtue of greater efficacy at low application rates and/or different pest control, which can be verified by the person skilled in the art using the experimental procedures, using lower concentrations if necessary, for example 10 ppm, 5 ppm, 2 ppm, 1 ppm or 0.2 ppm; or lower application rates, such as 300, 200 or 100, mg of Al per m.sup.2. The greater efficacy can be observed by an increased safety profile (against non-target organisms above and below ground (such as fish, birds and bees), improved physico-chemical properties, or increased biodegradability).
[0524] In each aspect and embodiment of the invention, “consisting essentially” and inflections thereof are a preferred embodiment of “comprising” and its inflections, and “consisting of” and inflections thereof are a preferred embodiment of “consisting essentially of” and its inflections.
[0525] The disclosure in the present application makes available each and every combination of embodiments disclosed herein.
[0526] It should be noted that the disclosure herein in respect of a compound of formula I applies equally in respect of a compound of each of formulae Ia, Ib, and Tables 1 to 35.
BIOLOGICAL EXAMPLES
[0527] The Examples which follow serve to illustrate the invention. Certain compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 24 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.
Example B1: Diabrotica balteata (Corn Root Worm)
[0528] Maize sprouts placed onto an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 4 days after infestation.
[0529] The following compounds gave an effect of at least 80% control in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1.2, P2.1, P2.2, P2.5, P2-17, P3.4, P7.1, P8.1
Example B2: Euschistus heros (Neotropical Brown Stink Bug)
[0530] 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.
[0531] The following compounds gave an effect of at least 80% control in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P2.1., P8.1
Example B3: Plutella xylostella (Diamond Back Moth)
[0532] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions by pipetting. After drying, Plutella eggs were pipetted through a plastic stencil onto a gel blotting paper and the plate was closed with it. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 8 days after infestation. The following compounds gave an effect of at least 80% control in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1.2, P1.15, P1.51, P2.1, P2.2, P2.5, P2.10, P2.15, P2.16, P5.1, P5.2, P5.3, P7.1, P8.1
Example B4: Myzus persicae (Green Peach Aphid). Intrinsic Activity
[0533] Test compounds prepared from 10′000 ppm DMSO stock solutions were applied by pipette into 24-well microtiter plates and mixed with sucrose solution. The plates were closed with a stretched Parafilm. A plastic stencil with 24 holes was placed onto the plate and infested pea seedlings were placed directly on the Parafilm. The infested plate was closed with a gel blotting paper and another plastic stencil and then turned upside down. The samples were assessed for mortality 5 days after infestation.
[0534] The following compounds resulted in at least 80% mortality at a test rate of 12 ppm: P1.3, P1.4, P1.22, P1.26
Example B5: Tetranychus urticae (Two-Spotted Spider Mite): Feeding/Contact Activity
[0535] 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.
[0536] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P1.1, P1.2, P1.3, P1.4, P1.5, P1.6, P1.7, P1.8, P1.10, P1.11, P1.12, P1.13, P1.14, P1.15, P1.16, P1.17, P1.18, P1.19, P1.20, P1.21, P1.22, P1.23, P1.24, P1.25, P1.26, P1.27, P1.28, P1.29, P1.30, P1.31, P1.33, P1.34, P1.35, P1.36, P1.37, P1.39, P1.40, P1.41, P1.42, P1.43, P1.44, P1.45, P1.46, P1.49, P1.50, P1.52, P2.1, P2.2, P2.3, P2.4, P2.5, P2.6, P2.7, P2.8, P2.9, P2.10, P2.11, P2.12, P2.13, P2.17, P3.1, P3.2, P3.3, P3.4, P3.5, P3.6, P3.7, P3.8, P3.9, P4.1, P4.2, P5.2, P6.1, P7.1., P8.1