WO2014195232A1 - Bicyclische arylsulfid- und arylsulfoxid-derivate als schädlingsbekämpfungsmittel - Google Patents
Bicyclische arylsulfid- und arylsulfoxid-derivate als schädlingsbekämpfungsmittel Download PDFInfo
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- WO2014195232A1 WO2014195232A1 PCT/EP2014/061231 EP2014061231W WO2014195232A1 WO 2014195232 A1 WO2014195232 A1 WO 2014195232A1 EP 2014061231 W EP2014061231 W EP 2014061231W WO 2014195232 A1 WO2014195232 A1 WO 2014195232A1
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- 0 *c(c(N(C(*)=Nc1c2ccnc1)C2=O)c1)cc(*)c1S(CC(F)(F)F)=O Chemical compound *c(c(N(C(*)=Nc1c2ccnc1)C2=O)c1)cc(*)c1S(CC(F)(F)F)=O 0.000 description 3
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P33/00—Antiparasitic agents
- A61P33/14—Ectoparasiticides, e.g. scabicides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
Definitions
- the present application relates to novel heterocyclic compounds, to processes for their preparation and their use for controlling animal pests, which include arthropods and in particular insects, as well as intermediates for the preparation of the heterocyclic compounds.
- Arylquinazolinones and their insecticides and acaricidal action are already known from WO 2010/100189 AI.
- Plant protection products including pesticides, must meet many requirements, for example, in terms of the level, duration and breadth of their effect and possible use. Issues of toxicity, of the ability to be combined with other active substances or formulation auxiliaries play a role, as well as the question of the effort that has to be spent on the synthesis of an active substance. Furthermore, resistances can occur. For all these reasons, the search for new pesticides can not be considered complete and there is a constant need for new compounds with improved properties over the known compounds, at least with respect to individual aspects.
- the object of the present invention was to provide compounds which broaden the spectrum of pesticides from various aspects.
- V is an oxygen, a sulfur or a substituted nitrogen
- Q is a substituted carbon or nitrogen
- Q 1 , Q 2 , Q 3 , Q 4 each independently represent a substituted carbon or nitrogen, wherein at least one of the structural elements Q 1 , Q 2 , Q 3 , Q 4 is nitrogen and at most two of the structural elements Q 1 , Q 2 , Q 3 , Q 4 are nitrogen;
- W is hydrogen or halogen; is the number 0, 1 or 2; independently of one another are hydrogen, halogen, hydroxy, amino, cyano, nitro, OCN, SCN, SF5; or for trialkylsilyl, alkyl, haloalkyl, cyanoalkyl, hydroxyalkyl, alkoxycarbonylalkyl, alkoxyalkyl, alkenyl, haloalkenyl, cyanoalkenyl, alkynyl, haloalkynyl, cyanoalkynyl, alkoxy, haloalkoxy, cyanoalkoxy, hydroxycarbonylalkoxy, alkoxycarbonylalkoxy, alkoxyalkoxy, alkylhydroxyimino, alkoxyimino, alkylalkoxyimino, haloalkylalkoxyimino, alkylthio, haloalkylthio, alkoxyalkylthio, alkylthi
- novel compounds of the formula (I) have good activity as pesticides, for example against arthropods and, in particular, insects and acarids, moreover, in general, especially with respect to crop plants, are very well plant tolerated and / or have favorable toxicological and / or environmental relevance Features.
- Q is C-R or nitrogen
- R is hydrogen, hydroxy, halogen, cyano, alkyl, cycloalkyl, haloalkyl, alkoxy,
- Q 1 is CR 1 or nitrogen;
- Q 2 is CR 2 or nitrogen
- Q 3 is CR 3 or nitrogen
- Q 4 is CR 4 or nitrogen; wherein at least one of the structural elements Q 1 , Q 2 , Q 3 , Q 4 is nitrogen and at most two of the structural elements Q 1 , Q 2 , Q 3 , Q 4 are nitrogen;
- R 1 , R 2 , R 3 , R 4 are each independently hydrogen, hydroxy, halogen, cyano, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy, hetaryl, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, amino, Monoalkylamino or dialkylamino;
- W is hydrogen or halogen;
- n stands for the number 0 or 1;
- X, Y and z independently represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, amino, hydroxy, alkyl, haloalkyl, alkenyl, alkynyl, alkoxy, haloalkoxy or aminothiocarbonyl; or benzyl, phenoxy, phenylthio, cyclopropylmethyl, cyclopropyloxy or
- Cyclopropylthio which is optionally mono- or polysubstituted by identical or different substituents with fluorine, chlorine, bromine, cyano, nitro, hydroxy, amino, methyl, ethyl, trifluoromethyl, difluoromethyl, trifluoroethyl, difluoroethyl, methoxy, ethoxy, trifluoromethoxy, trifluoroethoxy or optionally Methyl, fluorine, chlorine or cyano substituted cyclopropyl;
- cyclopropyl or represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or phenyl which is optionally mono- or polysubstituted, identically or differently, by fluorine, chlorine, bromine, cyano, nitro, hydroxyl, amino, methyl, ethyl, trifluoromethyl, difluoromethyl, trifluoroethyl, difluoroethyl, Methoxy, ethoxy, trifluoromethoxy, trifluoroethoxy or optionally substituted by methyl, fluorine, chlorine or cyano substituted cyclopropyl.
- R is hydrogen, halogen, (CC 4 ) alkyl, (C 1 -C 4 ) haloalkyl or (C 3 -C 6 ) cycloalkyl;
- Q 1 is CR 1 or nitrogen
- Q 2 is CR 2 or nitrogen
- Q 3 is CR 3 or nitrogen
- Q 4 is CR 4 or nitrogen; wherein at least one of the structural elements Q 1 , Q 2 , Q 3 , Q 4 is nitrogen and at most two of the structural elements Q 1 , Q 2 , Q 3 , Q 4 are nitrogen;
- R 1 , R 2 , R 3 , R 4 are each independently hydrogen, halogen, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) haloalkyl or (C 3 -C 6 ) cycloalkyl;
- W is hydrogen or fluorine; n stands for the number 0 or 1;
- X and Y independently of one another represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl,
- Trifluoromethyl (2,2) -difluoromethyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyano, amino, hydroxy or nitro; z is hydrogen.
- R is hydrogen, halogen, (C r C4) alkyl, (Ci-C 4) haloalkyl, (CC 4) alkoxy, (C
- Q 1 is CR 1 or nitrogen
- Q 2 is CR 2 or nitrogen
- Q 3 is CR 3 or nitrogen
- Q 4 is CR 4 or nitrogen; wherein at least one of the structural elements Q 1 , Q 2 , Q 3 , Q 4 is nitrogen and at most two of the structural elements Q 1 , Q 2 , Q 3 , Q 4 are nitrogen;
- R 1 , R 2 , R 3 , R 4 are each independently hydrogen, halogen, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) haloalkyl, (CC 4 ) alkoxy, (CC 4 ) haloalkoxy or (C 3 -C 6 ) cycloalkyl;
- W is hydrogen or fluorine; n stands for the number 0 or 1; X and Y independently of one another represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl,
- Trifluoromethyl (2,2) -difluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyano, amino, hydroxy or nitro; z is hydrogen.
- substituents or ranges of the radicals listed in the compounds of the formula (I) are explained below.
- V is oxygen
- Q is C-R or nitrogen
- R is hydrogen, fluorine, chlorine, methyl, ethyl, tert-butyl, trifluoromethyl
- Q 1 is CR 1 or nitrogen
- Q 2 is CR 2 or nitrogen
- Q 3 is CR 3 or nitrogen
- Q 4 is CR 4 or nitrogen; wherein at least one of the structural elements Q 1 , Q 2 , Q 3 , Q 4 is nitrogen and at most two of the structural elements Q 1 , Q 2 , Q 3 , Q 4 are nitrogen;
- R 1 , R 2 , R 3 , R 4 are each independently hydrogen, fluorine, chlorine, methyl, ethyl, tert-butyl, trifluoromethyl, methoxy, trifluoromethoxy or cyclopropyl;
- W is hydrogen or fluorine; n stands for the number 0 or 1;
- X is hydrogen, chlorine, fluorine or methyl
- Y is chlorine, bromine, cyano, methyl, trifluoromethyl, fluorine or methoxy; z is hydrogen.
- X and Y represent the following combinations (Y, X): (Me, F), (Me, H), (Me, Cl), (Me, Me) , (C1, C1), (C1, F), (CN, F), (MeO, F), (MeO, H), (C1, H), (Br, H), (Br, F), CN, H), (F, F), (CF 3 , H).
- Y, X represent the following combinations (Y, X): (Me, F), (Me, H), (Me, Cl), (Me, Me) , (C1, C1), (C1, F), (CN, F), (MeO, F), (MeO, H), (C1, H), (Br, H), (Br, F), CN, H), (F, F), (CF 3 , H).
- V is oxygen
- R is hydrogen or methyl
- Q 2 stands for CR 2 ;
- Q 3 stands for CR 3 ;
- Q 4 stands for CR 4 ;
- R 2 , R 3 , R 4 are each hydrogen
- W is fluorine
- n stands for the number 0 or 1;
- X is chlorine, fluorine or methyl
- Y is chlorine or methyl
- X and Y are in particular the following combinations (Y, X): (Me, F), (Me, Me), (C1, C1);
- V is oxygen
- R is hydrogen
- Q 1 stands for CR 1 ;
- Q 3 stands for CR 3 ;
- Q 4 stands for CR 4 ;
- R 1 , R 3 , R 4 are each hydrogen
- W is fluorine; n stands for the number 0 or 1;
- X is fluorine
- Y is methyl
- Y is oxygen
- R is hydrogen
- Q 1 stands for CR 1 ;
- Q 2 stands for CR 2 ;
- Q 4 stands for CR 4 ;
- R 1 , R 2 , R 4 are each hydrogen
- W is fluorine
- n stands for the number 0 or 1;
- X is fluorine
- Y is methyl
- R is hydrogen
- Q 1 stands for CR 1 ;
- Q 2 stands for CR 2 ;
- Q 3 stands for CR 3 ;
- R 1 , R 2 , R 3 are each hydrogen
- W is fluorine; n stands for the number 0 or 1;
- X is fluorine
- Y is methyl
- Halogen selected from the group fluorine, chlorine, bromine and iodine, preferably again from the series fluorine, chlorine and bromine,
- Hetaryl (equivalent to heteroaryl, also as part of a larger unit such as hetarylalkyl) selected from the series furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1, 2,4-triazolyl, oxazolyl, isoxazolyl , Thiazolyl, isothiazolyl, 1, 2,3-oxadiazolyl, 1, 2,4-oxadiazolyl, 1, 3,4-oxadiazolyl, 1, 2,5-oxadiazolyl, 1, 2,3-thiadiazolyl, 1, 2,4 Thiadiazolyl, 1,3,4-thiadiazolyl, 1, 2,5-thiadiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1, 2,3-triazinyl, 1, 2,4-triazinyl, 1, 3,5-triazinyl , Benzof
- Halogen selected from the group fluorine, chlorine, bromine and iodine, preferably again from the series fluorine, chlorine and bromine,
- Hetaryl (also as part of a larger moiety such as hetarylalkyl) selected from the series furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1, 2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl , 1, 2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1, 3,4-oxadiazolyl, 1, 2,5-oxadiazolyl, 1, 2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1 , 3,4-thiadiazolyl, 1, 2,5-thiadiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1, 2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl.
- Optionally substituted radicals may be monosubstituted or polysubstituted, with multiple substituents the substituents may be the same or different.
- the invention relates to compounds of the formula (IB)
- the invention relates to compounds of the formula (I-C)
- X and Y represent the following combinations (Y, X): (Me, F), (Me, H), (Me, Cl), (Me, Me), (C1, C1) and (Cl, F).
- the invention relates to compounds of the formula (I-A-1)
- the invention relates to compounds of the formula (I-C-1)
- the invention relates to compounds of the formula (I-D-1)
- X and Y represent the following combinations (Y, X): (Me, F), (Me, H), (Me, Cl), (Me, Me), (C1, C1) and (Cl, F).
- the compounds of the formula (I) according to the invention and their acid addition salts and metal salt complexes have good activity, in particular for controlling animal pests, which include arthropods and in particular insects and acarids.
- the compounds of the formula (I) may also be present in different compositions as stereoisomers, ie as geometric and / or optical isomers or mixtures of isomers. Both the pure Stereoisomers as well as any mixtures of these isomers are the subject matter of this invention, although generally only compounds of the formula (I) are mentioned here.
- the compounds of the formula (I) according to the invention can be present in different polymorphic forms or as a mixture of different polymorphic forms. Both the pure polymorphs and the polymorph mixtures are the subject of the invention and can be used according to the invention.
- optically active stereoisomeric forms of the compounds of the formula (I) and salts thereof are used according to the invention.
- the invention therefore relates to both the pure enantiomers and diastereomers, as well as their mixtures for controlling animal pests, which include arthropods and in particular insects and acarids.
- Suitable salts of the compounds of general formula (I) may be conventional non-toxic salts, i. H. Salts with corresponding bases and salts with added acids.
- salts with inorganic bases such as alkali metal salts, for example sodium, potassium or cesium salts, alkaline earth metal salts, for example calcium or magnesium salts, ammonium salts, salts with organic bases and with inorganic amines, for example triethylammonium, dicyclohexylammonium, ⁇ , ⁇ '- Dibenzylethylenediammonium, pyridinium, picolinium or ethanolammonium salts, salts with inorganic acids, for example hydrochlorides, hydrobromides, dihydrosulfates, trihydrosulfates, or phosphates, salts with organic carboxylic acids or organic sulfonic acid, for example formates, acetates, trifluoroacetates, maleates, tartrates, methanesul
- the compounds of the invention are generally defined by the formula (I) and which also includes all possible rotamers, tautomers and mixtures thereof. Examples which may be mentioned are the following tautomers of the general formula (I) in which Q is C-R and R is hydroxy, thiol, amino or alkylamino:
- novel compounds of the formula (I) can be prepared by customary methods known to the person skilled in the art. Various preparation methods, which are also the subject of the invention, are described in the following Reaction Schemes Method A to Method F.
- the amidation reactions are carried out in the presence of a condensing agent, if appropriate in the presence of an acid activator, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a solvent.
- a condensing agent if appropriate in the presence of an acid activator, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a solvent.
- Suitable condensing agents are all condensing agents customarily used for such amidation reactions.
- acid halide formers are phosgene, phosphorus trichloride, oxalyl chloride or thionyl chloride; Carbodiimides, such as N, N'-dicyclohexylcarbodiimide (DCC) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide (EDCI), or other conventional condensing agents, such as phosphorus pentoxide, polyphosphoric acid, N, N'-carbonyldiimidazole, 2-chloropyridine 1-Methoiodide (Mukaiyamas reagent), 2-ethoxy-N-ethoxycarbonyl-l, 2-dihydroquinoline (EEDQ),
- Suitable acid acceptors are all customary inorganic or organic bases, for example triethylamine, diisopropylethylamine, N-methylmorpholine or N, N-dimethylaminopyridine. If appropriate, process A according to the invention is carried out in the presence of a suitable reaction auxiliary, for example N, N-dimethylformamide or N, N-dimethylaminopyridine. Furthermore, mixed anhydrides can also be used to prepare (III), as described, for example, in J. Am. Chem. Soc. 1967, 5012, published.
- various chloroformate can be used, such as isobutyl chloroformate, isopropyl chloroformate.
- diethylacetyl chloride, trimethylacetyl chloride and the like can be used therefor.
- Compounds of the general formula (IIa) or tautomers thereof can be prepared, for example, by reduction of the nitro compounds of the general formula (IIIa) by methods known from the literature getting produced. Suitable methods for such reductions are especially metal-mediated reactions such as stannous chloride, iron powder, zinc powder, Raney nickel, palladium (O) on carbon or platinum dioxide (as hydrate).
- the metal-mediated reductions, such as with tin (II) chloride can be made according to an Organic Synthesis Coli. Vol. (III), 453 described methods.
- compounds of general formula (IIa) can be prepared by an acylation reaction according to process B, in which an aniline of general formula (IVa) is reacted with a suitable carboxylic acid derivative of formula (VI), wherein R ** is preferably alkyl.
- process B in which an aniline of general formula (IVa) is reacted with a suitable carboxylic acid derivative of formula (VI), wherein R ** is preferably alkyl.
- R ** is preferably alkyl.
- Aluminum amides can be prepared from the anilines or their salts by reaction with trimethylaluminum or their air-stable adduct with 1,4-diazobicyclo [2.2.3] octane (DABCO), as described by S. Woodward in Tet. Lett. 2006, 47, 5767-5769.
- DABCO 1,4-diazobicyclo [2.2.3] octane
- R ** may also be hydrogen, so that all the synthesis methods described in Method A would be suitable for the synthesis of compounds of the formula (IIa).
- thioethers of the general formula (Ia) For the preparation of thioethers of the general formula (Ia), different methods are suitable. Examples are: starting from compounds of the formula (IIa) by ring closure; starting from anilines of the formula (IVa) by reaction with bicyclic compounds of the formula (IX) according to process C or starting from halides of the formula (VIIa) or boronic acids of the formula (Villa) or (VHIb) by metal-catalyzed reactions according to process D. or method E.
- compounds of formula (IIa) are added with a nitrite source, such as sodium nitrite or isobutyl nitrite, typically in water, alcohol or a polar, inert solvent, at 0 to 5 ° C in the presence of an organic or inorganic acid.
- a nitrite source such as sodium nitrite or isobutyl nitrite
- water, alcohol or a polar, inert solvent typically in water, alcohol or a polar, inert solvent
- the compounds of the formula (Ia) can be prepared starting from anilines of the formula (IVa) by reaction with bicyclic compounds of the formula (IX) or their tautomeric hydroxypyrimidinones according to process C.
- bicyclic compounds of the formula (IX) or their tautomeric hydroxypyrimidinones according to process C.
- the N-arylation of Hydroxypyrimidinonen under mild reaction conditions for example, by HATU-mediated coupling with primary amines with DBU as the base in acetonitrile as a solvent, usually at room temperature or up to 70 ° C.
- An alternative preparation of the compounds of the formula (Ia) is the reaction of halides of the formula (VIIa) with bicyclic compounds of the formula (IX) under metal-catalyzed reaction conditions.
- Numerous methods are known in the literature, for example in Chem. Pharm. Bull. 1997, 45, 4, 719-721; in Tet. Lett. 2006, 47, 7677-7680; or Synlett 2008, 9, 1335-1340, in which copper iodide is used as metal source in the presence of a base and optionally a ligand at higher temperatures (for example 120 to 150 ° C).
- Compounds of general formula (Ib) and (Ic) can be prepared by oxidation by literature methods from compounds of general formula (Ia), for example by a Oxidizing agent in a suitable solvent and diluent.
- Suitable oxidizing agents are, for example, dilute nitric acid, hydrogen peroxide and peroxycarboxylic acids, such as raeta-chloroperbenzoic acid.
- Suitable solvents are inert organic solvents, typically acetonitrile and halogenated solvents such as dichloromethane, chloroform or dichloroethane.
- Enantiomerically enriched sulfoxides can be prepared by a variety of methods, such as those described by AR Maguire in ARKIVOC, 201 l (i), 1-110: metal-catalyzed asymmetric oxidations of thioethers, for example with titatium and vanadium as the most commonly used catalyst sources Form of Ti (O 1 Pr 4 ) and VO (acac) 2 , together with a chiral ligand and an oxidizing agent such as tert-butyl hydrogen peroxide (TBHP), 2-phenylpropan-2-yl hydroperoxide (CHP) or hydrogen peroxide; non-metal catalyzed asymmetric oxidations by using chiral oxidants or chiral catalysts; electrochemical or biological asymmetric oxidation as well as kinetic resolution of sulfoxides and nucleophilic displacement (according to Andersen's method).
- TBHP tert-butyl hydrogen peroxide
- CHP 2-pheny
- the enantiomers can also be obtained from the racemate by, for example, separating them preparatively on a chiral HPLC.
- compounds of the general formula (Ib) can be prepared in a different order by methods similar to those mentioned here, for example by oxidation of the anilines of the formula (IV a) to sulfoxides of the formula (IVb) and their further reaction according to process A, B or C.
- Anilines of the formula (IVa) can lead with oxazinones of the formula to target compounds of the formula (Ia), for example according to Assiut Univ. J. of Chemistry 2006, 45-63.
- Oxazinones of the formula (XXII) are known or can be prepared by methods known from the literature, as for example in Journal ofthe Chemical Society 1965, 4240-4246.
- any commercially available microwave apparatus suitable for these reactions may be used (e.g., Anton Paar Monowave 300, CEM Disco ver S, Biotage Initiator 60).
- Anilines of the formula (IV), halides of the formula (VII) and boronic acids of the formula (VIII) are central building blocks for preparing the compounds of the formula (I)
- Anilines of the formula (IVa) are known in the literature, e.g. from JP 2007/284356, or can be synthesized by methods known from the literature.
- anilines of the general formula (IVa) can be prepared, for example, as shown in the following scheme;
- Anilines of formula (XIV) are either commercially available or can be prepared by known methods. They may be treated with a suitable protecting group, e.g. an acetyl group, to compounds of formula (XIII) are protected.
- a suitable protecting group e.g. an acetyl group
- the anilines (XIV) can be converted into the corresponding anilides (XIII). Chlorosulfonation of the protected anilines (XIII) with chlorosulfonic acid gives the corresponding sulfonyl chlorides (XII).
- the reduction of the sulfonyl chlorides (XII) in the disulfides (XI) is possible with methods known from the literature such as iron in hydrochloric acid or iodide.
- the sulfonyl chloride (XII) can be reduced to the alkyl thioate (XVII) with a suitable reducing agent, such as iodine / phosphorus, and then, by a suitable method, such as reaction with potassium hydroxide solution, to give thiols of the formula (XVI) are deprotected.
- a suitable reducing agent such as iodine / phosphorus
- a suitable method such as reaction with potassium hydroxide solution
- the thioethers of the formula (IVa) can alternatively be prepared according to the following scheme,
- X, Y, Z and W have the meanings given above and Hai is chlorine, bromine or iodine
- WO 2007/034755, JP 2007/081019, JP 2007/284385, JP 2008/260706 , JP 2008/308448, JP 2009/023910 or WO 2012/176856 or can be synthesized by methods known from the literature, which may optionally be slightly modified.
- Suitable starting materials for the synthesis of the iodides of the general formula (VIIa) are bromides of the same formula, for example in halogen exchange reactions by methods known from the literature, if appropriate under metal catalysis (see H. Suzuki, Chem.
- X, Y, Z and W have the meanings given above are known from the literature, e.g. WO2007 / 034755, JP2007 / 284385, JP2009 / 023910 and WO2012 / 176856 or can be synthesized by methods known from the literature.
- the active compounds according to the invention or to be used in accordance with the invention are suitable for plant tolerance, favorable warm-blooded toxicity and good environmental compatibility for protecting plants and plant organs, for increasing crop yields, improving the quality of the crop and for controlling animal pests, in particular insects, arachnids, helminths, Nematodes and molluscs found in agriculture, horticulture, livestock, forestry, gardens and recreational facilities, in the protection of materials and materials and in the hygiene sector. They can preferably be used as crop protection agents. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
- the above mentioned pests include:
- Pests of the genus Arthropoda in particular of the class Arachnida eg Acarus spp., Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Amphitetranychus viennensis, Argas spp., Boophilus spp., Brevipalpus spp., Bryobia graminum , Bryobia praetiosa, Centruroides spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermacentor spp., Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Glycyphagus domesticus, Halotydeus destructor, Hemitarsonemus spp
- Hyalomma spp. Ixodes spp., Latrodectus spp., Loxosceles spp., Metatetranychus spp., Neutrombicula autumnalis, Nuphersa spp., Oligonychus spp., Ornithodorus spp., Ornithonyssus spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes Spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Steneotarsonemus spp., Steneotarsonemus spinki, Tarsonemus spp., Tetranychus spp., Trombicula alfreddugesi, Vaejo vis spp., Vasates lycopersici.
- Curculio spp. Cryptolestes ferruginus, Cryptorhynchus lapathi, Cylindrocopturus spp., Dermestes spp., Diabrotica spp., Dichocrocis spp., Dicladispa armigera, Diloboderus spp., Epilachna spp., Epitrix spp., Faustinus spp., Gibbium psylloides, Gnathocerus cornutus , Hellula and alis, Heteronychus arator, Heteronyx spp., Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypomeces squamosus, Hypothenemus spp., Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp., Leptinotarsa decem
- Pentomidae Piesma quadrata, Piezodorus spp., Psallus spp., Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp.
- Protoparce spp. Pseudaletia spp., Pseudaletia unipuncta, Pseudoplusia includens, Pyrausta nubilalis, Rachiplusia nu, Schoenobius spp., Scirpophaga spp., Scirpophaga innotata, Ontario segetum, Sesamia spp., Sesamia inferens, Sparganothis spp.
- Pests from the strain of Mollusca in particular from the class of bivalvia, eg Dreissena spp., And from the class of Gastropoda eg Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp., Succinea spp .; Animal parasites from the strains of Plathelminthes and Nematoda, eg Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp.,
- Opisthorchis spp. Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosome spp., Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis , Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti; Plant pests from the Nematoda strain, ie plant parasitic nematodes, in particular Aphelenchoides spp., Bursaphelenchus spp., Ditylenchus spp., Globodera spp., Heterodera spp., Longidorus spp., Meloidogy
- Rotylenchus spp. Neotylenchus spp., Paraphelenchus spp., Dolichodorus spp., Hoplolaimus spp., Punctodera spp., Criconemella spp., Quinisulcius spp., Hemicycliophora spp., Anguina spp., Subanguina spp., Hemicriconemoides spp., Psilenchus spp , Pseudohalenchus spp., Criconemoides spp., Cacopaurus spp.
- the order of coccidia can be determined, e.g. Eimeria spp. fight.
- the present invention further relates to formulations and application forms prepared therefrom as crop protection agents and / or pesticides such.
- B. drench, drip and spray comprising at least one of the active compounds according to the invention.
- the use forms contain other crop protection agents and / or pesticides and / or the effect of improving adjuvants such as penetration enhancers, eg.
- vegetative oils such as rapeseed oil, sunflower oil, mineral oils such as paraffin oils, alkyl esters of vegetal fatty acids such as rapeseed oil or soybean oil methyl ester or alkanol alkoxylates and / or spreading agents such as alkyl siloxanes and / or salts, e.g.
- organic or inorganic ammonium or phosphonium salts such as ammonium sulfate or diammonium hydrogen phosphate and / or retention-promoting agents such.
- Typical formulations are, for example, water-soluble liquids (SL), emulsion concentrates (EC), emulsions in water (EW), suspension concentrates (SC, SE, FS, OD), water-dispersible granules (WG), granules (GR) and capsule concentrates (CS). ;
- SL water-soluble liquids
- EC emulsion concentrates
- EW emulsions in water
- SC suspension concentrates
- SC SE, SE, FS, OD
- WG water-dispersible granules
- GR granules
- capsule concentrates CS
- the formulations contain, in addition to one or more active compounds according to the invention, further agrochemical active substances.
- auxiliaries such as extenders, solvents, spontaneity promoters, carriers, emulsifiers, dispersants, antifreeze agents, biocides, thickeners and / or further auxiliaries, for example adjuvants.
- An adjuvant in this context is a component that enhances the biological effect of the formulation without the component itself having a biological effect.
- Examples of adjuvants are agents that promote retention, spreading behavior, adherence to the leaf surface, or penetration.
- formulations are prepared in a known manner, for example by mixing the active compounds with excipients such as extenders, solvents and / or solid carriers and / or other excipients such as surface-active substances.
- excipients such as extenders, solvents and / or solid carriers and / or other excipients such as surface-active substances.
- the preparation of the formulations is carried out either in suitable systems or before or during use.
- Excipients which can be used are those which are suitable for imparting special properties, such as certain physical, technical and / or biological properties, to the formulation of the active substance or to the forms of use prepared from these formulations (such as, for example, ready-to-use crop protection agents such as spray mixtures or seed dressing).
- Suitable extenders include, for example, water, polar and non-polar organic chemical liquids, for example from the classes of aromatic and non-aromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), alcohols and polyols (which may also be substituted, etherified and / or esterified esters (also fats and oils) and (poly) ethers, simple and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, sulfones and sulfoxides (like Thylsulfoxid).
- aromatic and non-aromatic hydrocarbons such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes
- alcohols and polyols which may also be substituted, etherified and / or esterified esters (also fats and oils) and (poly)
- Suitable liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g.
- Petroleum fractions mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide and water.
- alcohols such as butanol or glycol and their ethers and esters
- ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone
- strongly polar solvents such as dimethylformamide and dimethyl sulfoxide and water.
- Suitable solvents are, for example, aromatic hydrocarbons, e.g. Xylene, toluene or alkylnaphthalenes, chlorinated aromatic or aliphatic hydrocarbons, e.g. Chlorobenzene, chloroethylene, or methylene chloride, aliphatic hydrocarbons, e.g. Cyclohexane, paraffins, petroleum fractions, mineral and vegetable oils, alcohols such as e.g. Methanol, ethanol, iso-propanol, butanol or glycol and their ethers and esters, ketones such as e.g. Acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents such as dimethyl sulfoxide and water.
- aromatic hydrocarbons e.g. Xylene, toluene or alkylnaphthalenes
- chlorinated aromatic or aliphatic hydrocarbons e
- Suitable carriers are in particular: for example, ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock flour, such as finely divided silica, alumina and natural or synthetic silicates, resins, waxes and / or solid fertilizers , Mixtures of such carriers can also be used.
- Suitable carriers for granules are: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, paper, coconut shells, corn cobs and tobacco stems.
- liquefied gaseous diluents or solvents can be used.
- Particularly suitable are those extenders or carriers which are gaseous at normal temperature and under atmospheric pressure, for example aerosol propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
- Examples of emulsifying and / or foaming agents, dispersants or wetting agents having ionic or non-ionic properties or mixtures of these surfactants are salts of polyacrylic acid, salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthalenesulphonic acid, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, with substituted phenols (preferably alkylphenols or arylphenols), salts of sulphosuccinic acid esters, taurine derivatives (preferably alkyltaurates), phosphoric acid esters of polyethoxylated alcohols or phenols, fatty acid esters of polyols and derivatives of the compounds containing sulphates, sulphonates and phosphates, for example alkylarylpolyglycol ethers, alkylsulphonates, alkyl - sulfates, arylsulfonates, protein
- dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes, and nutrient and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
- Stabilizers such as cold stabilizers, preservatives, antioxidants, light stabilizers or other chemical and / or physical stability-improving agents may also be present. It may also contain foam-forming agents or defoamers.
- formulations and the use forms derived therefrom may also contain, as additional auxiliaries, adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-containing polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate and natural phospholipids such as cephalins and lecithins and synthetic phospholipids.
- additional auxiliaries may be mineral and vegetable oils.
- auxiliaries may be present in the formulations and in the use forms derived therefrom.
- additives are, for example, fragrances, protective colloids, binders, adhesives, thickeners, thixotropic substances, penetration promoters, retention promoters, stabilizers, sequestrants, complexing agents, humectants, spreading agents.
- the active ingredients can be combined with any solid or liquid additive commonly used for formulation purposes.
- retention promoters are all those substances considered that the dynamic Reduce surface tension such as dioctylsulfosuccinate or increase the visco-elasticity such as hydroxypropyl guar polymers.
- Suitable penetration promoters in the present context are all those substances which are usually used to improve the penetration of agrochemical active substances into plants.
- Penetration promoters are in this context defined by the fact that they can penetrate from the (usually aqueous) application broth and / or from the spray coating into the cuticle of the plant and thereby increase the material mobility (mobility) of the active ingredients in the cuticle.
- the method described in the literature can be used to determine this property.
- Examples include alcohol alkoxylates such as coconut oil ethoxylate (10) or Isotridecylethoxylat (12), fatty acid esters such as rapeseed oil or soybean oil, fatty amine alkoxylates such as Tallowamine ethoxylate (15) or ammonium and / or phosphonium salts such as ammonium sulfate or diammonium hydrogen phosphate.
- alcohol alkoxylates such as coconut oil ethoxylate (10) or Isotridecylethoxylat (12)
- fatty acid esters such as rapeseed oil or soybean oil
- fatty amine alkoxylates such as Tallowamine ethoxylate (15) or ammonium and / or phosphonium salts such as ammonium sulfate or diammonium hydrogen phosphate.
- the formulations preferably contain between 0.00000001 and 98% by weight of active ingredient or, more preferably, between 0.01 and 95% by weight of active compound, more preferably between 0.5 and 90% by weight of active ingredient, based on the weight of the formulation.
- the active substance content of the application forms (pesticides) prepared from the formulations can vary within wide ranges.
- the active ingredient concentration of the use forms can usually be between 0.00000001 and 95% by weight of active ingredient, preferably between 0.00001 and 1% by weight, based on the weight of the application form.
- the application is done in a custom forms adapted to the application.
- the active substances to be used according to the invention or according to the invention can also be used as such or in their formulations as a mixture with one or more suitable fungicides, bactericides, acaricides, molluscicides, nematicides, insecticides, microbiologicals, beneficials, fertilizers, bird repellents, phytotonics, sterilants, synergists, Safeners, semiochemicals and / or plant growth regulators can be used, for example, to broaden the spectrum of action, to extend the duration of action, to increase the rate of action, to prevent repellence or to prevent the development of resistance. Furthermore, such drug combinations plant growth and / or tolerance to abiotic factors such.
- Acetylcholinesterase (AChE) inhibitors such as
- Carbamates e.g. Alanycarb, Aldicarb, Bendiocarb, Benfuracarb, Butocarboxime, Butoxycarboxime, Carbaryl, Carbofuran, Carbosulfan, Ethiofencarb, Fenobucarb, Formetanate, Furathiocarb, Isoprocarb, Methiocarb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Propoxur, Thiodicarb, Thiofanox, Triazamate, Trimethacarb, XMC and xylylcarb; or
- Organophosphates e.g. Acephate, Azamethiphos, Azinophos-ethyl, Azinophos-methyl, Cadusafos, Chloroethoxyfos, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos-methyl, Coumaphos, Cyanophos, Demeton-S-methyl, Diazinone, Dichlorvos / DDVP, Dicrotophos, Dimethoates, Dimethylvinphos, Disulfone, EPN, Ethion, Ethoprophos, Famphur, Fenamiphos, Fenitrothion, Fenthion, Fosthiazate, Heptenophos, Imicyafos, Isofenphos, Isopropyl O- (methoxyaminothio-phosphoryl) salicylate, Isoxathione, Malathion, Mecarbam, Methamidophos, Methida
- GABA-controlled chloride channel antagonists such as cyclodiene organochlorines, e.g. Chlordane and endosulfan; or phenylpyrazoles (fiproles), e.g. Ethiprole and fipronil.
- Pyrethroids eg acrinathrin, aethrin, d-cis-trans aethrin, d-trans aethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfiuthrin, beta-cyfiuthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin [(lR) trans isomers], deltamethrin, empenthrin [(EZ) (lR) isomers], esfenvalerates,
- nicotinergic acetylcholine receptor (nAChR) agonists such as
- Neonicotinoids e.g. Acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or
- nicotinergic acetylcholine receptor (nAChR) allosteric activators such as spinosines, e.g. Spinetoram and spinosad.
- Avermectins / milbemycins e.g. Abamectin, Emamectin benzoate, Lepimectin and Milbemectin.
- Juvenile hormone mimics such as juvenile hormone analogs, e.g. Hydroprene, kinoprene and methoprene; or fenoxycarb; or pyriproxyfen.
- agents with unknown or nonspecific modes of action such as alkyl halides, e.g. Methyl bromide and other alkyl halides; or
- mite growth inhibitors e.g. Clofentezine, hexythiazox and difiovidazine; or Etoxazole.
- Microbial disruptors of the insect gut membrane eg Bacillus thuringiensis subspecies israelensis, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis and Bt plant proteins: CrylAb, CrylAc, CrylFa, CrylA.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, Cry34 From 1/35 Abi; or Bacillus sphaericus.
- inhibitors of oxidative phosphorylation, ATP disruptors such as diafenthiuron; or
- Organotin compounds e.g. Azocyclotine, cyhexatin and fenbutatin oxide; or propargite; or tetradifon.
- Nicotinergic acetylcholine receptor antagonists such as Bensultap, Cartap hydrochloride, thiocyclam and thiosultap sodium.
- Type 0 inhibitors of chitin biosynthesis such as bistrilluron, chloraluazuron, dillubenzuron, flucycloxuron, flufenoxuron, hexallumuron, lufenuron, novaluron, novillumuron, tellubenzuron and trillumuron.
- inhibitors of chitin biosynthesis type 1, such as buprofezin.
- Moulting agents dipteran, such as cyromazine.
- ecdysone receptor agonists such as chromafenozides, halofenozides, methoxyfenozides, and tebufenozides.
- Octopaminergic agonists such as amitraz.
- complex III electron transport inhibitors such as hydramethylnone; or acequinocyl; or fluacrypyrim.
- complex I electron transport inhibitors for example
- METI acaricides e.g. Fenazaquin, Fenpyroximate, Pyrimidifen, Pyridaben, Tebufenpyrad and Tolfenpyrad; or
- Tetronic and tetramic acid derivatives eg spirodiclofen, spiromesifen and spirotetramat.
- complex IV electron transport inhibitors such as
- Phosphines e.g. Aluminum phosphide, calcium phosphide, phosphine and zinc phosphide; or cyanide.
- Diamides e.g. Chlorantraniliprole, Cyantraniliprole and Flubendiamide.
- agents such as Amidofiumet, Azadirachtin, Benclothiaz, Benzoximate, Bifenazate, Bromopropylate, Chinomethionat, Cryolite, Dicofol, Difiovidazine, Fluensulfone, Flufenerim, Flufiprole, Fluopyram, Fufenozide, Imidaclothiz, Iprodione, Meperfluthrin, Pyridalyl, Pyrifiuquinazone, Tetramethylfluthrin and Iodomethane; furthermore preparations based on Bacillus firmus (in particular strain CNCM 1-1582, for example VOTiVO TM, BioNem) and the following compounds:
- inhibitors of ergosterol biosynthesis such as aldimorph, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, dodemorph, dodemorph acetate, epoxiconazole, etaconazole, fenarimol, fenbuconazole, fenhexamide, fenpropidin, fenpropimorph, Fluquinconazole, flurprimidol, flusilazole, flutriafol, furconazole, furconazole cis, hexaconazole, imazalil, imazalil sulfate, imibenconazole, ipconazole, metconazole, myclobutanil, naftifine, nuarimol, oxpoconazole, paclobutrazole, pe
- inhibitors of respiration such as bixafen, boscalid, carboxin, diflumetorim, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, furmecyclox,
- inhibitors of respiration on the complex III of the respiratory chain, such as, for example, ametoctradin, amisulbrom, azoxystrobin, cyazofamide, coumethoxystrobin,
- Coumoxystrobin Dimoxystrobin, Enestroburin, Famoxadone, Fenamidon, Fenoxystrobin, Fluoxastrobin, Kresoxim-methyl, Metominostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin, Pyrametostrobin, Pyraoxystrobin, Pyribencarb, Triclopyricarb, Trilloxystrobin, (2E) -2- (2- ⁇ [6- (2- 3-chloro-2-methylphenoxy) -5-fluoro-4-pyrridin-4-yl] oxy ⁇ phenyl) -2- (methoxyimino) -N-methylethanamide, (2E) -2- (methoxyimino) -N-methyl-2- ( 2- ⁇ [( ⁇ (1E) -1- [3- (trifluoromethyl) phenyl] ethylidene ⁇ amino) oxy] methyl ⁇ phenyl) ethanamide, (2
- Mitosis and cell division inhibitors such as benomyl, carbendazim, chlfenazole, diethofencarb, ethaboxam, fluopicolide, fuberidazole, pencycuron, thiabendazole, thiophanate-methyl, thiophanate, zoxamide, 5-chloro-7- (4-methylpiperidine-1) yl) -6- (2,4,6-trifluorophenyl) [l, 2,4] triazolo [l, 5-a] pyrimidine and 3-chloro-5- (6-chloropyridin-3-yl) -6-methyl -4- (2,4,6-trilluorphenyl) pyridazine.
- Compounds with multisite activity such as Bordeaux mixture, captafol, captan, chlorothalonil, copper preparations such as copper hydroxide, copper naphthenate, copper oxide, copper oxychloride, copper sulfate, dichlofiuanide, dithianone, dodine, dodine free base, Ferbam, Fluorofolpet, Folpet, guazatine, guazatin acetate , Iminoctadine, iminoctadinal besylate, iminoctadine triacetate, mancopper, mancozeb, maneb, metiram, zinc metiram, copper oxine, propamidine, propineb, sulfur and sulfur preparations such as calcium polysulfide, thiram, tolylfluanid, zineb and ziram.
- copper preparations such as copper hydroxide, copper naphthenate, copper oxide, copper oxychloride, copper sulfate, dichlofiu
- resistance inducers such as acibenzolar-S-methyl, isotianil, probenazole and tiadinil.
- Inhibitors of amino acid and protein biosynthesis such as andoprim, blasticidin-S, cyprodinil, kasugamycin, kasugamycin hydrochloride hydrate, mepanipyrim, pyrimethanil and 3- (5-fluoro-3,3,4,4-tetramethyl-3 , 4-dihydroisoquinoline-l-yl) quinoline.
- inhibitors of ATP production such as fentin acetate, fentin chloride, fentin hydroxide and silthiofam.
- inhibitors of cell wall synthesis such as benthiavalicarb, dimethomorph, flumorph, iprovalicarb, mandipropamide, polyoxins, polyoxorim, validamycin A, and valifenalate.
- inhibitors of lipid and membrane synthesis such as biphenyl, chloroneb, dicloran, edifenphos, etridiazole, iodocarb, Iprobenfos, isoprothiolane, propamocarb, propamocarb hydrochloride, prothiocarb, pyrazophos, quintozene, tecnazene and tolclofos-methyl.
- Inhibitors of melanin biosynthesis such as carpropamide, diclocymet, fenoxanil, fthalide, pyroquilone, tricyclazole and 2,2,2-trifluoroethyl ⁇ 3-methyl-1 - [(4-methylbenzoyl) amino] butan-2-yl carbamate ,
- inhibitors of nucleic acid synthesis such as benalaxyl, benalaxyl-M (kiralaxyl), bupirimate, clozylacon, dimethirimol, ethirimol, furalaxyl, hymexazole, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl and oxolic acid.
- signal transduction inhibitors such as chlozolinate, fenpiclonil, fludioxonil, iprodione, procymidone, quinoxyfen and vinclozolin.
- Decouplers such as binapacryl, dinocap, ferimzone, fluazinam and meptyldinocap.
- plants and parts of plants can be treated.
- plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
- Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or can not be protected by plant breeders' rights.
- Plant parts are understood to mean all aboveground and subterranean parts and organs of plants such as shoot, leaf, flower and root, examples of which include leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, and roots, tubers and rhizomes.
- the plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.
- all plants and their parts can be treated.
- wild or organic plant cultivars such as hybridization or protoplast fusion obtained Pfianzenart and Pilanzensorten and their parts are treated.
- transgenic plants and plant cultivars which have been obtained by genetic engineering, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated.
- the term “parts” or “parts of plants” or “Pfianzenmaschine” has been explained above.
- Purple cultivars according to the invention are treated with plants of the respective commercially available or in use types of plants.Purple species are understood as meaning plants with new properties (“traits”) have been bred either by conventional breeding, by mutagenesis or by recombinant DNA techniques. These may be varieties, breeds, biotypes and genotypes.
- the treatment of the plants and plant parts with the active substances or active compound combinations or agents to be used according to the invention or according to the invention is carried out directly or by acting on their environment, habitat or storage space according to the usual treatment methods, e.g. by dipping, (spraying) spraying, (spraying), sprinkling, vaporizing, atomizing, atomizing, (scattering, foaming, brushing, spreading, injecting, pouring, drip irrigation and propagating material, in particular in the case of seed) Dry pickling, wet pickling, slurry pickling, encrusting, single or multi-layer wrapping, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient itself into the soil.
- a preferred direct treatment of the plants is the foliar application, ie, the active ingredients, drug combinations or agents are applied to the foliage, the frequency of treatment and the rate of application can be tailored to the infestation pressure of the respective pathogen, pest or weed.
- the active ingredients, active ingredient combinations or agents reach the plants via the root system. The treatment of the plants is then carried out by the action of the active ingredients, drug combinations or agents on the habitat of the plant.
- the control of animal pests by the treatment of the seed of plants has long been known and is the subject of constant improvement.
- seed treatment methods should also include the intrinsic insecticidal or nematicidal properties of pest-resistant transgenic plants in order to achieve optimum protection of the seed and of the germinating plant with a minimum of pesticide use.
- the present invention therefore also relates in particular to a method for protecting seed and germinating plants from attack by pests by treating the seed with an active substance according to the invention or to be used according to the invention.
- the method according to the invention for the protection of seeds and germinating plants from infestation by pests comprises a method in which the seed is treated simultaneously in one operation with an active compound of the formula I and mixing partner. It also includes a method in which the seed is treated at different times with an active ingredient of formula I and mixing partners.
- the invention also relates to the use of the active ingredients according to the invention for the treatment of seed for the protection of the seed and the resulting plant from animal pests.
- the invention relates to seed which has been treated with an active ingredient according to the invention for protection against animal pests.
- the invention also relates to seed which has been treated at the same time with an active compound of the formula I and mixing partner.
- the invention further relates to seed which has been treated at different times with an active compound of the formula I and mixing partner.
- the individual active compounds of the agent according to the invention may be present in different layers on the seed. In this case, the layers which contain an active compound of the formula I and mixing partners may optionally be separated by an intermediate layer.
- the invention also relates to seed in which an active compound of the formula I and mixing partner are applied as a constituent of a coating or as a further layer or further layers in addition to a coating. Furthermore, the invention relates to seed, which after the treatment with the active ingredient of the formula (I) or an active ingredient combination containing it has been subjected to a film coating process in order to avoid dust abrasion on the seed.
- One of the advantages of the present invention is that because of the particular systemic properties of the agents according to the invention, treatment of the seed with these agents not only protects the seed itself but also the resulting plants after emergence from animal pests. In this way, the immediate treatment of the culture at the time of sowing or shortly afterwards can be omitted.
- Another advantage is the fact that by the treatment of the seed with active ingredient of the formula (I) or combination of active substances containing germination and emergence of the treated seed can be promoted.
- active compounds of the formula (I) and the named active substance combinations can be used in particular also in the case of transgenic seed.
- active compounds of the formula (I) can be used in combination with signal technology agents, by way of example a better colonization with symbionts, such as rhizobia, mycorrhiza and / or endophytic bacteria, taking place and / or optimizing them Nitrogen fixation is coming.
- compositions according to the invention are suitable for the protection of seeds of any plant variety used in agriculture, in the greenhouse, in forests or in horticulture.
- these are seeds of cereals (eg wheat, barley, rye, millet and oats), corn, cotton, soy, rice, potatoes, sunflower, coffee, tobacco, canola, oilseed rape, turnip (eg sugar beet and Fodder beet), peanut, vegetables (eg tomato, cucumber, bean, cabbage, onions and lettuce), fruit plants, turf and ornamental plants.
- cereals eg wheat, barley, rye and oats
- corn, soya, cotton, canola, oilseed rape and rice are examples of seeds of cereals (eg wheat, barley, rye and oats), corn, soya, cotton, canola, oilseed rape and rice.
- transgenic seed with active ingredients of the formula (I) or a combination of active substances is of particular importance.
- active ingredients of the formula (I) or a combination of active substances are of particular importance.
- the heterologous genes in transgenic seed can come from microorganisms such as Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium.
- the present invention is particularly useful for the treatment of transgenic seed containing at least one heterologous gene derived from Bacillus sp. comes.
- the active ingredient of the formula (I) is applied to the seed alone (or as active ingredient combination) or in a suitable formulation.
- the seed is treated in a state where it is so stable that no damage occurs during the treatment.
- the treatment of the seed can be done at any time between harvesting and sowing.
- seed is used which has been separated from the plant and freed from flasks, shells, stems, hull, wool or pulp.
- seeds may be used which have been harvested, cleaned and dried to a moisture content of less than 15% by weight.
- seed can also be used, which after drying, for example, treated with water and then dried again.
- care must be taken in the treatment of the seed that the amount of the agent and / or other additives applied to the seed is chosen so that germination of the seed is not impaired or the resulting plant is not damaged. This is especially important for active ingredients, which can show phytotoxic effects in certain application rates.
- the agents according to the invention can be applied directly, ie without containing further components and without being diluted. In general, it is preferable to apply the agents to the seed in the form of a suitable formulation.
- Suitable formulations and methods for seed treatment are known to those skilled in the art and are described, for example, in the following documents: US 4,272,417 A, US 4,245,432 A, US 4,808,430 A, US 5,876,739 A, US 2003/0176428 Al, WO 2002/080675 Al, WO 2002 / 028186 A2.
- the active compounds / active substance combinations that can be used according to the invention can be converted into the customary seed dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other seed coating compositions, as well as ULV formulations.
- formulations are prepared in a known manner by mixing the active ingredients / drug combinations with conventional additives, such as conventional extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and also water.
- conventional additives such as conventional extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and also water.
- Dyes which may be present in the seed dressing formulations which can be used according to the invention are all dyes customary for such purposes. Both water-insoluble pigments and water-soluble dyes are useful in this case. Examples which may be mentioned under the names rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1 known dyes.
- Suitable wetting agents which may be present in the seed dressing formulations which can be used according to the invention are all wetting agents customary for the formulation of agrochemical active compounds promoting substances in question.
- Preferably used are alkylnaphthalene sulfonates, such as diisopropyl or diisobutyl naphthalene sulfonates.
- Suitable dispersants and / or emulsifiers which may be present in the seed dressing formulations which can be used according to the invention are all nonionic, anionic and cationic dispersants customary for the formulation of agrochemical active compounds.
- Preferably usable are nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants.
- Particularly suitable nonionic dispersants are, in particular, ethylene oxide-propylene oxide block polymers, alkylphenol polyglycol ethers and tristryrylphenol polyglycol ethers and their phosphated or sulfated derivatives.
- Suitable anionic dispersants are in particular lignosulfonates, polyacrylic acid salts and arylsulfonate-formaldehyde condensates.
- Defoamers which may be present in the seed dressing formulations which can be used according to the invention are all foam-inhibiting substances customary for the formulation of agrochemical active compounds.
- Defoamers which may be present in the seed dressing formulations which can be used according to the invention are all foam-inhibiting substances customary for the formulation of agrochemical active compounds.
- Preferably usable are silicone defoamers and magnesium stearate.
- Preservatives which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for such purposes in agrochemical compositions. Examples include dichlorophen and Benzylalkoholhemiformal.
- Suitable secondary thickeners which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for such purposes in agrochemical compositions. Preference is given to cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica.
- Suitable adhesives which may be present in the seed dressing formulations which can be used according to the invention are all customary binders which can be used in pickling agents.
- Preferably mentioned are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose.
- the gibberellins are known (see R. Wegler "Chemie der convinced- und Swdlingsbekungsstoff", Vol. 2, Springer Verlag, 1970, pp. 401-412).
- the seed dressing formulations which can be used according to the invention can be used either directly or after prior dilution with water for the treatment of seed of various kinds.
- the concentrates or the preparations obtainable therefrom by dilution with water can be used for dressing the seeds of cereals such as wheat, barley, rye, oats and triticale, as well as the seeds of corn, rice, rape, peas, beans, cotton, sunflowers and beets or even vegetable seeds of various nature.
- the pickling agent usable according to the invention Formulations or their diluted preparations can also be used to pickle seeds of transgenic plants. In this case, additional synergistic effects may occur in interaction with the substances formed by expression.
- the seed dressing formulations which can be used according to the invention or the preparations prepared therefrom by the addition of water
- all mixing devices customarily usable for the dressing can be considered.
- the seed is placed in a mixer which adds either desired amount of seed dressing formulations either as such or after prior dilution with water and mixes until evenly distributed the formulation on the seed.
- a drying process follows.
- the application rate of the seed dressing formulations which can be used according to the invention can be varied within a relatively wide range. It depends on the respective content $ of the active substance (s) in the formulations and on the seed.
- the application rates for active ingredient / active ingredient combinations are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 15 g per kilogram of seed.
- the active compounds of the formula (I) according to the invention are suitable for increasing the plant's own defenses (pathogen defense in plants).
- These may be, for example, (a) low molecular weight substances, such as phytoalexins, (b) non-enzymatic proteins, such as. (C) enzymatic proteins such as chitinases, glucanases, or (d) specific inhibitors of essential proteins, such as protease inhibitors, xylanase inhibitors attack the pathogen directly or impede its proliferation (Dangl and Jones, Nature 411, 826-833, 2001; Kessler and Baldwin, Annual Review of Plant Biology, 53, 299-328, 2003).
- HR hypersensitive reaction
- SAR systemic acquired resistance
- a known synthetic product which one of the salicylic acid similar function is performed and can provide a protective effect against phytopathogenic fungi, bacteria and viruses, is benzothiadiazole (CGA 245704; Common name: acibenzolar-5-methyl; trade name: Bion ®) (Achuo et al. , Plant Pathology 53 (1), 65-72, 2004, Tamblyn et al., Pesticide Science 55 (6), 676-677, 1999, EP-OS 0 313 512).
- pathogenesis-related proteins which primarily support plants in the defense against biotic stressors, such as phytopathogens Fungi, Bacteria and Viruses (DE 10 2005 045 174 A; DE 10 2005 022 994 A and WO 2006/122662 A; Thielert Maischutz-Nachzin Bayer, 59 (1), 73-86, 2006; Francis et al., European Journal of Plant Pathology, publ. online 23.1.2009).
- plants have a number of endogenous reaction mechanisms that can effect effective defense against various harmful organisms (biotic stress) and / or abiotic stress.
- the cultivation of healthy and uniformly grown seedlings is an essential prerequisite for the large-scale cultivation and economic management of agricultural, horticultural and forestry crops.
- the seed is sown in special containers, eg Styrofoam perforated trays, in special potting soil based on peat culture substrate and then cultivated in containers with suitable nutrient solution until the desired transplant size is reached (Figure 1). It is allowed to drive the containers on the nutrient solution, from which derives the name of the culture method (Leal, 2001, supra).
- Floating processes have been using insecticides from the class of neonicotiniodes (chlornicotinyls) for the control of sucking pests for several years.
- the plants are sprayed with neonicotinoid (chloronicotinyl) insecticides in the float process shortly before transplanting or are infused with neonicotinoid (chloronicotinyl) insecticides immediately before or during transplantation, which is termed "drenching" (Leal, 2001, supra; and Rogers, 2001, supra) Both methods of application are technically relatively complex.
- Fungicides and insecticides are used to protect the crops of seed or plant material from fungal pathogens and pests until they are transplanted.
- the choice of pesticides, the place and time of application and the application rate of the funds depend here mainly on the type of fungal diseases and pests occurring, the specific mode of action and duration of action of the agents and their plant compatibility, and thus directly to the specific requirements of different Adapted to crops and regions.
- the active ingredients of the formula (I) thereby lead to a good protection of the plant from damage by fungal, bacterial or viral pathogens, independently of an insect control. Without wishing to be bound by theory, it is currently believed that defense of the pathogens by induction of PR proteins occurs as a result of treatment with at least one drug of formula (I).
- the use according to the invention in seed treatment, in soil treatment, in special cultivation and cultivation methods e.g., Floating Box, Rockwool, Hydroponic
- stem and foliar treatment has the advantages described.
- Combinations of an active compound of the formula (I), inter alia, with insecticides, fungicides and bactericides have a synergistic effect in the control of plant diseases.
- the combined use of the active ingredients of the formula (I) with genetically modified varieties with respect to increased abiotic stress tolerance also leads to a synergistic improvement in growth.
- the active compounds of the formula (I) not only increase the pathogen defense in plants, but also improve plant growth and / or increase the resistance of plants to plant diseases caused by fungi, bacteria, viruses, MLO (Mycoplasma -like organisms) and / or RLO (Rickettsia-like organisms) are caused, especially against soil-borne fungal diseases, and / or are suitable for increasing the resistance of plants to abiotic stress factors.
- Abiotic stress conditions may include, for example, drought, cold and heat conditions, osmotic stress, waterlogging, increased soil salinity, increased exposure to minerals, ozone conditions, high light conditions, limited availability of nitrogen nutrients, limited availability of phosphorous nutrients, or avoidance of shade.
- the present invention therefore relates firstly to the use of at least one active substance of the formula (I) for increasing plant-specific defense forces and / or for improving plant growth and / or for increasing the resistance of plants to plant diseases caused by fungi, bacteria, viruses, MLO (mycoplasma-like organisms) and / or RLO (Rickettsia-like organisms) are caused, in particular against soil-borne fungal diseases, and / or to increase the resistance of plants to abiotic stress factors.
- the term plant growth is understood to mean various advantages for plants which are not directly related to the known pesticidal activity, preferably to the insecticidal activity of the active compounds of the formula (I).
- Such advantageous properties include, for example, the following improved plant characteristics: accelerated germination and emergence of the seed and planting material, improved surface and depth root growth, increased lagging or stalking, stronger and more productive shoots and tillers, improvement in shoot growth, increased stability, increased shoot base diameter, increased leaf area, greener leaf color, higher yields of nutrients and ingredients, such as Carbohydrates, fats, oils, proteins, vitamins, minerals, essential oils, dyes, fibers, better fiber quality, earlier flowering, increased number of flowers, reduced content of toxic products such as mycotoxins, reduced content of residues or unfavorable ingredients of any kind or better digestibility, improved Storage stability of the crop, improved tolerance to unfavorable temperatures, improved tolerance to drought and drought, as well as oxygen depletion due to excess water, improved tolerance to increased salt levels in soils and
- Soche terms are, for example, the following: phytotonic effect, resistance to stressors, less plant stress, plant health, healthy plants, Plant Fitness, Plant Wellness, Plant Concept, Vigor Effect, Stress Shield "Crop Health Properties”, “Crop Health Products”, “Crop Health Management”, “Crop Health Therapy”, “Plant Health”, “Plant Health Properties”, “Plant Health Products”, “Plant Health Management”, “Plant Health Therapy”, “Greening Effect” or “Re-greening Effect”), "Freshness” or other terms that are well known to a person skilled in the art.
- Fertilizers which can be used according to the invention together with the above-described active agents or agents are generally organic and inorganic nitrogen-containing compounds such as ureas, urea-formaldehyde condensation products, amino acids, ammonium salts and nitrates, potassium salts (preferably chlorides, sulfates, nitrates ), Phosphoric acid salts and / or salts of phosphorous acid (preferably potassium salts and ammonium salts).
- NPK fertilizers ie fertilizers containing nitrogen, phosphorus and potassium, calcium ammonium nitrate, ie fertilizers which still contain calcium, ammonium sulphate nitrate (general formula (NH 4 ) 2 SO 4 NH 4 NO 3 ), Ammonium phosphate and ammonium sulfate.
- These fertilizers are well known to those skilled in the art, see also, for example, Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 10, pages 323 to 431, Verlagsgesellschaft, Weinheim, 1987.
- the fertilizers may also contain salts of micronutrients (preferably calcium, sulfur, boron, manganese, magnesium, iron, boron, copper, zinc, molybdenum and cobalt) and phytohormones (eg vitamin B l and indol-3-ylacetic acid (IAA) ) or mixtures thereof.
- Fertilizers used according to the invention may also contain other salts such as monoammonium phosphate (MAP), diammonium phosphate (DAP), potassium sulfate, potassium chloride or magnesium sulfate.
- Suitable amounts for the secondary nutrients or trace elements are amounts of from 0.5 to 5% by weight, based on the total fertilizer.
- Further possible ingredients are crop protection agents, insecticides or fungicides, growth regulators or mixtures thereof. Further explanations follow below.
- the fertilizers can be used, for example, in the form of powders, granules, prills or compactates. However, the fertilizers can also be used in liquid form dissolved in an aqueous medium. In this case, dilute aqueous ammonia can be used as nitrogen fertilizer.
- Other possible ingredients for fertilizers are For example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, 1987, Volume A 10, pages 363 to 401, DE-A 41 28 828, DE-A 19 05 834 and DE-A 196 31 764 described.
- the general composition of the fertilizers which in the context of the present invention may be single nutrient and / or multi-nutrient fertilizers, for example nitrogen, potassium or phosphorus, may vary within a wide range.
- a content of 1 to 30% by weight of nitrogen preferably 5 to 20% by weight
- of 1 to 20% by weight of potassium preferably 3 to 15% by weight
- Phosphorus preferably 3 to 10 parts by weight
- the content of microelements is usually in the ppm range, preferably in the range of 1 to 1000 ppm.
- the fertilizer and the active ingredient of the formula (I) at the same time, i. synchronously, administered.
- the fertilizer and then the active ingredient of the formula (I) or first the active ingredient of the formula (I) and then the fertilizer In the case of non-simultaneous application of the active ingredient of the formula (I) and of the fertilizer, however, the application takes place in a functional context, in particular within a period of generally 24 hours, preferably 18 hours, more preferably 12 hours, especially 6 hours, even more specifically 4 hours, more specifically within 2 hours.
- the active compounds of the general formula (I) and of the fertilizer according to the invention are used in a time frame of less than 1 hour, preferably less than 30 minutes, more preferably less than 15 minutes.
- dimensionally stable mixtures for example in the form of rods, granules, tablets, etc., starting from at least one active ingredient to be used according to the invention and at least one fertilizer.
- the corresponding constituents can be mixed with one another and optionally extruded or the at least one active compound of the formula (I) to be used according to the invention can be applied to the fertilizer.
- formulation aids may also be used in the dimensionally stable mixtures, such as extenders or pressure-sensitive adhesives, to achieve dimensional stability of the resulting mixture.
- corresponding mixtures are suitable, in particular for use in the "Home & Garden” sector, ie for a private user or home gardener, who can use the dimensionally stable mixture or the constituents contained therein with a predetermined, clearly defined amount and without special aids ,
- the mixtures of at least one of the active ingredients to be used according to the invention and the at least one fertilizer may also be liquid, so that For example, for a professional user in the field of agriculture - the resulting mixture can be applied as a so-called tank solution.
- the active compounds to be used according to the invention can, if appropriate in combination with fertilizers, preferably be applied to the following plants, the following listing not being restrictive.
- the forest stock includes trees for the production of wood, pulp, paper and products made from parts of the trees.
- crops refers to crops used as plants for the production of food, feed, fuel or for technical purposes.
- the crops include e.g. the following plant species: turf, vines, cereals, for example wheat, barley, rye, oats, triticale, rice, corn and millet; Beets, for example sugar beets and fodder beets; Fruits, such as pome fruit, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries and berries, eg.
- Particularly suitable target crops are the following plants: bamboo wool, eggplant, turf, pome fruit, stone fruit, berry fruit, corn, wheat, barley, cucumber, tobacco, vines, rice, cereals, pear, beans, soybeans, oilseed rape, tomatoes, peppers, melons , Cabbage, potato and apple.
- trees are: Abies sp., Eucalyptus sp., Picea sp., Pinus sp., Aesculus sp., Platanus sp., Tilia sp., Acer sp., Tsuga sp., Fraxinus sp., Sorbus sp., Betula sp., Crataegus sp., Ulmus sp., Quercus sp., Fagus sp., Salix sp., Populus sp.
- Aesculus A. hippocastanum, A. par hopea, A.
- trees may be mentioned: From the tree species Pinus: P. radiate, P. ponderosa, P. contorta, P. sylvestre, P. strobes; from the tree species Eucalyptus: E. grandis, E. globulus, E. camadentis. Particularly preferred trees can be called: horse chestnut, sycamore, linden, maple tree.
- the present invention may also be practiced on any turfgrasses, including "cool season turfgrasses” and “warm season turfgrasses.”
- cold season turf species are blue grasses (Poa spp “Kentucky bluegrass” (Poa pratensis L.), “rough bluegrass” (Poa trivialis L.), “Canada bluegrass” (Poa compressa L.), “annual bluegrass” (Poa annua L.), “upland bluegrass” (Poa glaucantha Gaudin), “wood bluegrass” (Poa nemoralis L.) and “bulbous bluegrass” (Poa bulbosa L.); ostrich grasses ("Bentgrass”, Agrostis spp.), such as “creeping bentgrass” (Agrostis palustris Huds.), “ colonial bentgrass “(Agrostis tenuis sib.),” velvet bentgrass “(Agrostis canina L.),” South German Mixed Ben
- Fescue Fescues, Festucu spp.
- red fescue Festuca rubra L. spp. Rubra
- creeping fescue Festuca rubra L.
- chewings fescue Festuca rubra commutata Gaud.
- sheep fescue (Festuca ovina L.)
- hard fescue (Festuca longifolia ThuilL)
- hair fescue (Festucu capsuleata lam.)
- tall fescue (Festuca arundinacea Schreb.) and” meadow fescue "(Festuca elanor L .)
- Lolium ryegrass, Lolium spp.
- Such as “annual ryegrass” (Lolium multiflorum Lam.)
- Perennial ryegrass (Lolium perenne L.) and "Italian ryegrass” (Lolium mult
- Examples of other "cool season turfgrasses” are “beachgrass” (Ammophila breviligulata Fern.), “Smooth bromegrass” (Bromus inermis leyss.), Reeds ("cattails") such as “Timothy” (Phleum pratense L.), “sand cattail “(Phleum subulatum L.),” orchardgrass “(Dactylis glomerata L.),” weeping alkaligrass “(Puccinellia distans (L.) Pari.) And” crested dog's-tail “(Cynosurus cristatus L.).
- Examples of “warm season turfgrasses” are “Bermudagrass” (Cynodon spp., LC Rieh), “zoysiagrass” (Zoysia spp. Willd.), “St. Augustine grass” (Stenotaphrum secundatum Walt Kuntze), “centipedegrass” (Eremochloa ophiuroides Munrohack.), “Carpetgrass” (Axonopus affinis chase), “Bahia grass” (Paspalum notatum flügge), “Kikuyugrass” (Pennisetum clandestinum detergent, ex Chiov.), “Buffalo grass” (Buchloe daetyloids (Nutt.) Engelm.) , “Blue gramma” (Bouteloua gracilis (HBK) lag.
- the active compounds of the formula (I) and their compositions are suitable for controlling animal pests in the hygiene sector.
- the invention can be used in household, hygiene and storage protection, especially for controlling insects, arachnids and mites, which occur in enclosed spaces, such as apartments, factories, offices, vehicle cabins.
- the active compounds or compositions are used alone or in combination with other active ingredients and / or adjuvants.
- they are used in household insecticide products.
- the active compounds according to the invention are active against sensitive and resistant species as well as against all stages of development.
- pests of the class Arachnida from the orders Scorpiones, Araneae and Opiliones, from the classes Chilopoda and Diplopoda, from the class Insecta the order Blattodea, from the orders Coleoptera, Dermaptera, Diptera, Heteroptera, Hymenoptera, Isoptera, Lepidoptera, Phthiraptera, Psocoptera, Saltatoria or Orthoptera, Siphonaptera and Zygentoma and from the class Malacostraca the order Isopoda.
- Application is for example in aerosols, non-pressurized sprays, e.g. Pump and atomizer sprays, fog machines, foggers, foams, gels, evaporator products with cellulose or plastic evaporator plates, liquid evaporators, gel and membrane evaporators, propeller-driven evaporators, energy-less or passive evaporation systems, moth papers, moth cushions and moth gels, as granules or dusts, in litter or bait stations.
- Pump and atomizer sprays e.g. Pump and atomizer sprays, fog machines, foggers, foams, gels, evaporator products with cellulose or plastic evaporator plates, liquid evaporators, gel and membrane evaporators, propeller-driven evaporators, energy-less or passive evaporation systems, moth papers, moth cushions and moth gels, as granules or dusts, in litter or bait stations.
- the active ingredients of formula (I) may be used to combat a variety of pests including, for example, noxious sucking insects, biting insects and other plant parasitic pests, storage pests, pests that destroy industrial materials, and use and include sanitary pests including animal health parasites combat such as their extinction and eradication.
- the present invention thus also includes a method of controlling pests.
- the active compounds according to the invention are active against animal parasites, in particular ectoparasites or endoparasites.
- the term endoparasite includes in particular helminths and protozoa such as coccidia.
- Ectoparasites are typically and preferably arthropods, especially insects and acarids.
- the compounds of the present invention having favorable toxicity to warm-blooded animals are useful in the control of parasites found in livestock and livestock in livestock, breeding animals, zoo animals, laboratory animals, experimental animals and domestic animals. They are effective against all or individual stages of parasite development.
- Farm animals include, for example, mammals such as sheep, goats, horses, donkeys, camels, buffaloes, rabbits, reindeer, fallow deer, and especially cattle and pigs; or poultry such as turkeys, ducks, geese and, in particular, chickens; or fish or crustaceans, e.g. in aquaculture; or possibly insects such as bees.
- the domestic animals include, for example, mammals such as hamsters, guinea pigs, rats, mice, chinchillas, ferrets or, in particular, dogs, cats; Caged birds; reptiles; Amphibians or aquarium fish.
- mammals such as hamsters, guinea pigs, rats, mice, chinchillas, ferrets or, in particular, dogs, cats; Caged birds; reptiles; Amphibians or aquarium fish.
- the compounds of the invention are administered to mammals.
- the compounds according to the invention are administered to birds, namely caged birds or, in particular, poultry.
- birds namely caged birds or, in particular, poultry.
- active substances for combating animal parasites according to the invention disease, deaths and reductions in performance (in the case of meat, milk, wool, hides, eggs, honey and the like) should be reduced or prevented so that a more economical and simpler animal husbandry is possible and a better Well-being of the animals is achievable.
- control means that the agents can effectively reduce the incidence of the particular parasite in an animal infected with such parasites to a harmless extent. More specifically, “combat” in the present context means that the active ingredient can kill the respective parasite, prevent its growth or prevent its replication.
- arthropods include, but are not limited to, the order Anoplurida, for example Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp .; from the order Mallophagida and the suborders Amblycerina and Ischnocerina, for example Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp .; out of order Diptera and the suborders Nematocerina and Brachycerina, for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus
- the following Akari are exemplary, but without limitation, from the subclass Akari (Acarina) and the order Metastigmata, for example, from the family Argasidae, such as Argas spp., Ornithodorus spp., Otobius spp., From the family Ixodidae, such as Ixodes spp., Amblyomma spp., Rhipicephalus (Boophilus) spp. Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp.
- Argasidae such as Argas spp., Ornithodorus spp., Otobius spp.
- Ixodidae such as Ixodes spp., Amblyomma spp., Rhipicephalus (Boophilus) spp. Dermacentor spp., Haem
- Examples of parasitic protozoa include, but are not limited to: Mastigophora (Flagellata), such as Trypanosomatidae, for example Trypanosoma b. brucei, T.b. gambiense, T.b. rhodesiense, T. congolense, T. cruzi, T. evansi, T. equinum, T. lewisi, T. percae, T. simiae, T. vivax, Leishmania brasiliensis, L. donovani, L. tropica, such as Trichomonadidae, for example Giardia lamblia, G. canis.
- Mastigophora Flagellata
- Trypanosomatidae for example Trypanosoma b. brucei, T.b. gambiense, T.b. rhodesiense, T. congolense, T. cruzi, T. evansi
- Sarcomastigophora such as Entamoebidae, for example Entamoeba histolytica, Hartmanellidae, for example Acanthamoeba sp., Harmanella sp.
- Apicomplexa such as Eimeridae, for example Eimeria acervulina, E. adenoides, E. alabamensis, E. anatis, E. anserina, E. arloingi, E. ashata, E. auburnensis, E. bovis, E. brunetti, E canis, E. chinchillae, E. clupearum, E. columbae, E. contorta, E. crandalis, E. debliecki, E. dispersa, E. ellipsoidales, E. falciformis, E. faurei, E. flavescens, E.
- Eimeridae for example Eimeria acervulina, E. adenoides, E. alabamensis, E. anatis, E. anserina, E. arloingi, E. ashata, E. auburnensis, E. bovis, E.
- gallopavonis E. hagani, E. intestinalis, E. iroquoina, E. irresidua, E. labbeana, E. leucarti, E. magna, E. maxima, E.media, E. meleagridis, E. meleagrimitis, E. mitis, E. necatrix, E. ninakohlyakimovae, E. ovis, E. parva, E. pavonis, E. perforans, E. phasani, E. piriformis, E. praecox, E. residua, E. scabra, E. spec., E. sitesdai, E. suis, E.
- S. suihominis such as Leucozoidae, for example Leucocytozoon simondi, such as Plasmodiidae, for example Plasmodium berghei, P. falciparum, P. malariae, P. ovale, P.vivax, P.spec, such as piroplasmea, for example Babesia argentina, B.bovis, B.canis, B.spec, Theileriaparva, Theileria spec, such as Adeleina, for example Hepatozoon canis, H. spec
- pathogenic endoparasites examples include flatworms (e.g., Monogenea, Cestodes, and Trematodes), roundworms, Acanthocephala, and Pentastoma.
- Other helminths include, but are not limited to: Monogenea: e.g., Gyrodactylus spp., Dactylogyrus spp., Polystoma spp.
- Cestodes from the order Pseudophyllidea for example: Diphyllobothrium spp., Spirometra spp., Schistocephalus spp., Ligula spp., Bothridium spp., Diplogonoporus spp.
- Taenia spp. Echinococcus spp., Hydatigera spp., Davainea spp., Raillietina spp., Hymenolepis spp., Echinolepis spp., Echinocotyle spp., Diorchis spp., Dipylidium spp., Joyeuxiella spp., Diplopylidium spp.
- Trematodes from the genus Digenea, for example: Diplostomum spp., Posthodiplostomum spp., Schistosoma spp., Trichobilharzia spp., Ornithobilharzia spp., Austrobilharzia spp., Gigantobilharzia spp., Leucochloridium spp., Brachylaima spp., Echinostoma spp., Echinoparyphium spp., Echinochasmus spp., Hypoderaeum spp., Fasciola spp., Fasciolides spp., Fasciolopsis spp., Cyclocoelum spp., Typhlocoelum spp., Paramphistomum spp., Calicophoron spp., Cotylophoron spp., Gigantocoty
- Roundworms Trichinellida for example: Trichuris spp., Capillaria spp., Trichomosoides spp., Trichinella spp.
- Tylenchida Micronema spp., Strongyloides spp.
- Rhabditina Strongylus spp., Triodontophorus spp., Oesophagodontus spp., Trichonema spp., Gyalocephalus spp., Cylindropharynx spp., Poteriostomum spp., Cyclococercus spp., Cylicostephanus spp., Oesophagostomum spp., Chabertia spp.
- Stephanurus spp. Ancylostoma spp., Uncinaria spp., Bunostomum spp., Globocephalus spp., Syngamus spp., Cyathostoma spp., Metastrongylus spp., Dictyocaulus spp., Muellerius spp., Protostrongylus spp., Neostrongylus spp., Cystocaulus spp., Pneumostrongylus spp., Spicocaulus spp., Elaphostrongylus spp.
- Parelaphostrongylus spp. Crenosoma spp., Paracrenosoma spp., Angiostrongylus spp., Aelurostrongylus spp., Filaroides spp., Parafilaroides spp., Trichostrongylus spp., Haemonchus spp., Ostertagia spp., Marshallagia spp., Cooperia spp., Nematodirus spp , Hyostrongylus spp., Obeliscoides spp., Amidostomum spp., Ollulanus spp.
- Acanthocephala from the order Oligacanthorhynchida, for example: Macracanthorhynchus spp., Prosthenorchis spp .; from the order Polymorphida for example: Filicollis spp .; from the order Moniliformida for example: Moniliformis spp., From the order Echinorhynchida for example Acanthocephalus spp., Echinorhynchus spp., Leptorhynchoides spp.
- Pentastoma from the order Porocephalida for example Linguatula spp.
- the administration of the active compounds according to the invention is carried out by methods well known in the art, such as enteral, parenteral, dermal or nasal in the form of suitable preparations.
- the administration can be prophylactic or therapeutic.
- one embodiment of the present invention relates to compounds of the invention for use as a medicament.
- Another aspect relates to compounds of the invention for use as antiendoparasitic agents, in particular a helminthicide or antiprotozoal agent.
- compounds of the invention for use as antiendoparasitic agents in particular a helminthicide or antiprotozoal agents, e.g. in animal husbandry, animal husbandry, stables and in the hygiene sector.
- Another aspect in turn relates to compounds of the invention for use as Antiektoparasitikum, in particular an arthropodicide such as an insecticide or an acaricide.
- compounds according to the invention for use as anti-topazarasitic, in particular an arthropodicide such as an insecticide or acaricide for example in animal husbandry, in animal husbandry, in stables, in the hygiene sector.
- the active compounds of the formula (I) and compositions containing them are suitable for protecting industrial materials against attack or destruction by insects, for example from the order Coleoptera, Hymenoptera, Isoptera, Lepidoptera, Psocoptera and Zygentoma.
- compositions or compositions according to the invention contain at least one further insecticide and / or at least one fungicide.
- this composition of the invention is a ready-to-use composition, that is, it can be applied to the corresponding material without further changes.
- insecticides or as fungicides the above-mentioned in question.
- the active compounds and compositions according to the invention can be used to protect against fouling of objects, in particular hulls, sieves, nets, structures, quays and signal systems, which come into contact with seawater or brackish water.
- the active compounds and compositions according to the invention can be used alone or in combinations with other active substances as antifouling agents.
- LogP [a] is also called logP (HCOOH).
- the NMR spectra were measured on a Bruker II Avance 400 equipped with a 1.7 mm TCI probe. In individual cases, the NMR spectra were determined with a Bruker Avance II 600.
- the NMR data of selected examples are listed in classical form ( ⁇ values, multiplet splitting, number of H atoms).
- the splitting of the signals was described as follows: s (singlet), d (doublet), t (triplet), q (quartet), m (multiplet), broad (for broad signals).
- the solvents used were CD 3 CN, CDCl 3 or D6-DMSO, tetramethylsilane (0.00 ppm) being used as reference.
- NMR data of selected examples can be listed as NMR peak lists.
- the ⁇ value in ppm and then the signal intensity are separated by a space for each signal peak.
- the ⁇ -value signal intensity number pairs of different signal peaks are listed separated by semicolons.
- the peak list of an example therefore has the form: ⁇ intensity ! ; ⁇ 2 intensity 2 ; ; 5j intensity ⁇ ; ; ⁇ ⁇ intensity ⁇ , n
- the solvent in which the NMR spectrum was recorded is shown in square brackets after the number of the example and before the NMR peak list or the classical NMR interpretation list.
- GC-MS spectra are determined on an Agilent 6890 GC, HP 5973 MSD on dimethylsilicone phase with a temperature gradient of 50 ° C to 320 ° C.
- GC-MS indices are determined as Kovats indices with solution of a homologous series of n-alkanes (with even number from 8 to 38 carbon atoms).
- Preparation Example 1 3- ⁇ 2-Fluoro-4-methyl-5 - [(2,2,2-trifluoroethyl) sulfinyl] -phenyl ⁇ -pyrido [2,3-d] pyrimidin-4 (3H) -one (Ex. No. 5)
- Step 1 2-Amino-N- ⁇ 2-fluoro-4-methyl-5 - [(2,2,2-trifluoroethyl) sulfanyl] phenyl ⁇ nicotinamide
- Step 3 3- ⁇ 2-Fluoro-4-methyl-5 - [(2,2,2-trifluoroethyl) sulfinyl] phenyl ⁇ -pyrido [2,3-d] pyrimidin-4 (3H) -one (Ex. No. 5)
- Step 2 3- ⁇ 2-Fluoro-4-methyl-5 - [(2,2,2-trifluoroethyl) sulfanyl] phenyl ⁇ -2-methylpyrido [2,3-d] pyrirnidine-4 (3H) -one ( Ex. No. 8)
- Step 3 3- ⁇ 2-Fluoro-4-methyl-5 - [(2,2,2-trifluoroethyl) sulfinyl] phenyl ⁇ -2-methyl-pyrido [2,3-d] pyrim 4 (3H) -one (Ex No. 10)
- Solvent Dimethylsulfoxide To prepare a suitable preparation of active compound, 10 mg of active compound are mixed with 0.5 ml of solvent and the concentrate is diluted with solvent to the desired concentration.
- ⁇ of the drug solution is injected into the abdomen of 5 wet, adult, female bovine ticks (Boophilus microplus).
- the animals are transferred to trays and kept in an air-conditioned room.
- the effect control takes place after 7 days on storage of fertile eggs.
- Eggs whose fertility is not visible from the outside are stored in the climatic cabinet for about 42 days until larval hatching.
- An effect of 100% means that none of the ticks have laid fertile eggs, 0% means that all eggs are fertile.
- Vessels are filled with sand, drug solution, an egg larvae suspension of the southern root gallbladder (Meloidogyne incognita) and lettuce seeds.
- the lettuce seeds germinate and the plantlets develop.
- the galls develop at the roots.
- the nematicidal activity is determined on the basis of bile formation in%. 100% means that no bile was found; 0% means that the number of bile on the treated plants corresponds to the untreated control.
- Emulsifier alkylaryl polyglycol ether
- a suitable preparation of active compound 1 part by weight of active compound is dissolved with the stated parts by weight of solvent and filled with water containing an emulsifier concentration of 1000 ppm until reaching the desired concentration.
- emulsifier concentration 1000 ppm until reaching the desired concentration.
- dilute with emulsifier-containing water Chinese cabbage leaf discs (Brassica pekinensis) are sprayed with a preparation of active compound of the desired concentration and, after drying, are populated with larvae of the horseradish leaf beetle (Phaedon cochleariae).
- Emulsifier alkylaryl polyglycol ether
- active compound 1 part by weight of active compound is dissolved with the stated parts by weight of solvent and filled with water containing an emulsifier concentration of 1000 ppm until reaching the desired concentration. To prepare further test concentrations, dilute with emulsifier-containing water.
- Bean leaf discs Phaseolus vulgaris infected by all stages of the common spider mite (Tetranychus urticae) are sprayed with an active compound preparation of the desired concentration. After 6 days, the effect is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Environmental Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Dentistry (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Tropical Medicine & Parasitology (AREA)
- Medicinal Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- General Chemical & Material Sciences (AREA)
- Pharmacology & Pharmacy (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Public Health (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Catching Or Destruction (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Description
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Priority Applications (5)
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BR112015030074A BR112015030074A2 (pt) | 2013-06-04 | 2014-05-30 | sulfeto de arila bicíclica e derivados de sulfóxido de arila como agentes de controle de pestes |
EP14727213.2A EP3004091A1 (de) | 2013-06-04 | 2014-05-30 | Bicyclische arylsulfid- und arylsulfoxid-derivate als schädlingsbekämpfungsmittel |
CN201480043535.5A CN105431434A (zh) | 2013-06-04 | 2014-05-30 | 作为害虫防治剂的二环芳基硫化物和芳基亚砜衍生物 |
US14/895,326 US20160108038A1 (en) | 2013-06-04 | 2014-05-30 | Bicyclic aryl sulfide and aryl sulfoxide derivatives as pest control agent |
JP2016517247A JP2016526047A (ja) | 2013-06-04 | 2014-05-30 | 有害生物防除剤としての二環式アリールスルフィド及びアリールスルホキシド誘導体 |
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US (1) | US20160108038A1 (de) |
EP (1) | EP3004091A1 (de) |
JP (1) | JP2016526047A (de) |
CN (1) | CN105431434A (de) |
BR (1) | BR112015030074A2 (de) |
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CN105601577A (zh) * | 2014-10-24 | 2016-05-25 | 沈阳中化农药化工研发有限公司 | 一种苯基硫醚类化合物及其用途 |
EP3168615A1 (de) * | 2015-11-13 | 2017-05-17 | Waters Technologies Corporation | Verfahren zur detektion von nichtpolaren analyten mit hoher empfindlichkeit |
Citations (2)
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WO2010100189A1 (en) * | 2009-03-04 | 2010-09-10 | Basf Se | 3-arylquinazolin-4-one compounds for combating invertebrate pests |
WO2012176856A2 (en) * | 2011-06-24 | 2012-12-27 | Ishihara Sangyo Kaisha, Ltd. | Pesticide |
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CH490801A (de) * | 1968-02-27 | 1970-05-31 | Ciba Geigy | Schädlingsbekämpfungsmittel und dessen Verwendung |
DE69934224T2 (de) * | 1998-04-27 | 2007-10-04 | Kumiai Chemical Industry Co., Ltd. | 3-arylphenylsulfid-derivate und insektizide und mitizide |
-
2014
- 2014-05-30 WO PCT/EP2014/061231 patent/WO2014195232A1/de active Application Filing
- 2014-05-30 JP JP2016517247A patent/JP2016526047A/ja active Pending
- 2014-05-30 CN CN201480043535.5A patent/CN105431434A/zh active Pending
- 2014-05-30 EP EP14727213.2A patent/EP3004091A1/de not_active Withdrawn
- 2014-05-30 US US14/895,326 patent/US20160108038A1/en not_active Abandoned
- 2014-05-30 BR BR112015030074A patent/BR112015030074A2/pt not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2010100189A1 (en) * | 2009-03-04 | 2010-09-10 | Basf Se | 3-arylquinazolin-4-one compounds for combating invertebrate pests |
WO2012176856A2 (en) * | 2011-06-24 | 2012-12-27 | Ishihara Sangyo Kaisha, Ltd. | Pesticide |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105601577A (zh) * | 2014-10-24 | 2016-05-25 | 沈阳中化农药化工研发有限公司 | 一种苯基硫醚类化合物及其用途 |
EP3168615A1 (de) * | 2015-11-13 | 2017-05-17 | Waters Technologies Corporation | Verfahren zur detektion von nichtpolaren analyten mit hoher empfindlichkeit |
US10520510B2 (en) | 2015-11-13 | 2019-12-31 | Waters Technologies Corporation | Methods for detecting and quantifying non-polar analytes with high sensitivity |
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JP2016526047A (ja) | 2016-09-01 |
CN105431434A (zh) | 2016-03-23 |
US20160108038A1 (en) | 2016-04-21 |
EP3004091A1 (de) | 2016-04-13 |
BR112015030074A2 (pt) | 2017-07-25 |
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