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WO2005040162A1 - Composes i 5-(2-arylacetamido)isothiazole - Google Patents

Composes i 5-(2-arylacetamido)isothiazole Download PDF

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Publication number
WO2005040162A1
WO2005040162A1 PCT/EP2004/012096 EP2004012096W WO2005040162A1 WO 2005040162 A1 WO2005040162 A1 WO 2005040162A1 EP 2004012096 W EP2004012096 W EP 2004012096W WO 2005040162 A1 WO2005040162 A1 WO 2005040162A1
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Prior art keywords
alkyl
formula
compound
compounds
hydrogen
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Inventor
Frank Schieweck
Jordi Tormo I Blasco
Carsten Blettner
Bernd Müller
Markus Gewehr
Wassilios Grammenos
Thomas Grote
Andreas Gypser
Joachim Rheinheimer
Peter Schäfer
Anja Schwögler
Oliver Wagner
Michael Rack
Ernst Baumann
Siegfried Strathmann
Ulrich Schöfl
Maria Scherer
Reinhard Stierl
Michael F. Treacy
Deborah L. Culbertson
Toni Bucci
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2

Definitions

  • the present invention relates to novel 5-(2-arylacetamido)isothiazole compounds and their agriculturally acceptable salts, and to the use of these compounds for controlling plant-damaging microorganisms and animal plant pests.
  • 5-(2-Arylacetamido)isothiazole compounds having pesticidal and fungicidai action have been described in various documents of the prior art, for example in DE-A 19846008, WO 95/31448, WO 97/18198 and WO 98/02424.
  • 5-[2-(Benzoxazolyl)acetamido]- isothiazole compounds having pesticidal action are described, for example, in WO 01/55144, WO 01/55145, WO 01/90105, WO 02/059118, WO 02/059119, WO 02/059120.
  • Novel active compounds should kill the harmful fungi and/or the animal pests at application rates which are as low as possible and reduce or, even better, prevent their reestablishment.
  • the active compounds should be well tolerated by useful plants, i.e. they should cause little, if any, damage to the useful plants.
  • this object should be achieved at low application rates, with good compatibility with useful plants.
  • the present invention relates to 5-(2-arylacetamido)isothiazole compounds of the formula I
  • X is oxygen or sulfur
  • Y is oxygen, sulfur or a group N-R 6 ;
  • R 1 is hydrogen, C 1 -C 4 -al yl, C C -haloalkyl, C C 4 -alkoxy or C C 4 -haloalkoxy;
  • R 2 is hydrogen, d-C 6 -alkyl, C C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C C 6 - alkylcarbonyl, C- ⁇ -C 4 -alkoxy-CrC 4 -alkyl or a group CO 2 -R 2a in which R 2a is d-C 6 - alkyl, d-C 6 -haloalkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -cycloalkyl, phenyl or benzyl, where the phenyl ring of the two last-mentioned groups may have 1 , 2 or 3 substituents selected from the group consisting of halogen, d-C 4 -alkyl, d-C 4 -haloalkyl, d-C -alkoxy and d-C 4 -haloalkoxy; R 3
  • R 4 is hydrogen, halogen, C ⁇ -C 4 -alkyl or d-C -haloalkyl
  • R 5 is hydrogen, d-C 6 -alkyl, d-d-haloalkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -cycloalkyl or d-C 4 -alkoxy-C-
  • R 6 is hydrogen, d-C 6 -alkyl, d-C 6 -haloalkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C C 4 - alkoxy-C C 4 -alkyl or C 3 -C 6 -cycloalkyl;
  • R 7 is hydrogen or methyl
  • the present invention also provides the use of the compounds of the formula I and their agriculturally acceptable salts as pesticides, i..e. for controlling plant-damaging animal organisms, and a method for controlling plant-damaging animal organisms which comprises treating the plant-damaging animal organisms or the materials, plants, the soil or seeds to be protected against attack by plant-damaging animal organisms with an effective amount of a compound of the formula I and/or with an agriculturally acceptable salt of I.
  • the present invention furthermore provides agricultural compositions, which comprise at least one compound of the formula I and/or an agriculturally acceptable salt of I and at least one agriculturally acceptable carrier.
  • the present invention furthermore provides a composition for controlling harmful fungi, which composition comprises at least one compound of the formula I and/or an agriculturally acceptable salt thereof and at least one liquid or solid carrier.
  • the compounds of the formula I may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers.
  • the present invention provides both the pure enantiomers or diastereomers and their mixtures.
  • the present invention also provides tautomers of compounds of the formula I.
  • Suitable agriculturally useful salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no negative effect on the fungicidai action of the compounds I.
  • suitable cations are in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry one to four d-C 4 -alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(d-C 4 -alkyl)sulfonium, and sulfoxonium
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen- sulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C ⁇ -C 4 -alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting I with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • C n -C m denotes the number of carbon atoms possible in each case in the respective substituent or substituent moiety: halogen: fluorine, chlorine, bromine and iodine; alkyl and all alkyl moieties in alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl and alkylcarbonyl: saturated straight-chain or branched hydrocarbon radicals having 1 to 4 or 1 to 6 carbon atoms, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl- propyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1
  • haloalkyl and all haloalkyl moieties in haioalkoxy straight-chain or branched alkyl groups having 1 to 4. or 1 to 6 carbon atoms (as mentioned above), where in these groups some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, for example C ⁇ -C 2 -haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloro- fluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chioro-2,2-difluoroethyl, 2,2-dich
  • alkenyl monounsaturated straight-chain or branched hydrocarbon radicals having 2 to 4 or 2 to 6 carbon atoms and a double bond in any position, for example C 2 -C 6 -alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1 -propenyl, 2-methyl-1 -propenyl, 1-methyl-2-propenyl, 2-methyl-2- propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methy!-1-butenyl, 2-methyl- 1-butenyl, 3-methyl- 1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2- butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1 ,1-
  • alkynyl straight-chain or branched hydrocarbon groups having 2 to 4 or 2 to 6 carbon atoms and a triple bond in any position, for example C 2 -C 6 -alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl , 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyI, 2-methyl-3- butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyI, 5-hexynyl, 1-methyl-2-penty
  • cycloalkyl monocyclic saturated hydrocarbon groups having 3 to 6 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
  • d-C 4 -alkoxy an alkyl group having 1 to 4 carbon atoms which is attached via an oxygen: for example methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methyl- propoxy, 2-methylpropoxy or 1 , 1 -dimethylethoxy;
  • d-C 6 -alkoxy d-C 4 -alkoxy as mentioned above, and also, for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methyIbutoxy, 1 ,1-dimethylpropoxy, 1 ,2-dimethyl- propoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methyl- pentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 ,1-dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3-dimethylbutoxy, 2,2-dimethyl butoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1 ,1 ,2-trimethylpropoxy, 1 ,2,2-trimethylpropoxy, 1-ethyl-1- methylpropoxy or 1-ethyl-2-methy I propoxy;
  • C C 4 -haloalkoxy a C C 4 -alkox ⁇ y radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, preferably by fluorine, i.e., for example OCH 2 F, OCHF 2 , OCF 3 , OCH 2 CI, OCHCI 2 , OCCI 3 , chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2- fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloro- ethoxy, OC 2 F 5 , 2-fluoropropoxy,
  • alkoxyalkyl an alkoxy group having 1 to 4 carbon atoms (as mentioned above) which is attached to the skeleton via a straight-chain or branched alkyl group having 1 to 4 carbon atoms (as mentioned above).
  • alkylcarbonyl a straight-chain or branched alkyl group having 1 to 6 carbon atoms (as mentioned above) which is attached to the skeleton via a carbonyl group (-CO-);
  • the group CR 3 R 4 is preferably attached in the 5-position of the benzazole radical, i.e. in the position para to the atom Y (compounds l.a), or via the 6-position, i.e. in the position para to the imino nitrogen (compounds l.b). Particular preference is given to the compounds l.a.
  • a preferred embodiment of the present invention relates to compounds of the formula I in which Y represents oxygen.
  • such compounds are also referred to as compounds l.aa (compounds having a benzoxazol-6-yl group) or l.ba (compounds having a benzoxazol-5-yl group).
  • a further embodiment of the present invention relates to compounds of the formula I in which Y is sulfur.
  • such compounds are also referred to as compounds l.ab (compounds having a benzothiazol-6-yl group) or l.bb (compounds having a benzothiazol-5-yl group).
  • a further embodiment of the present invention relates to compounds of the formula I in which Y represents N-R 6 .
  • such compounds are also referred to as compounds l.ac (compounds having a benzimidazol-6-yl group) or compounds l.bb (compounds having a benzimidazol-5-yl group).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and X independently of one another and in particular in combination have the following preferred meanings:
  • X is preferably oxygen.
  • R 1 in formula I, and correspondingly in the compounds l.a or l.b, is preferably d-C - alkyl and very particularly preferably methyl.
  • R 2 in formula I is preferably hydrogen, d-C 4 -alkyl, d-C 4 -alkoxy-C C 4 -alkyl or CO 2 R 2a , where R 2a is as defined above and is in particular alkyl. Particularly preferably, R 2 is hydrogen.
  • At least one of the radicals R 3 and R 4 and particularly preferably both radicals R 3 and R 4 in formula I, and correspondingly in the compounds l.a or l.b, is hydrogen.
  • R 5 is preferably d-C 6 -alkyl or d-d-haloalkyl and especially C 3 -C 6 -alkyl, preferably branched C 3 -C 6 -alkyl, such as neopentyl, or C 2 -C 4 -fluoroalkyI, such as heptafluoro- propyl.
  • R 5 can also be phenyl which may have 1 or 2 substituents selected from the group consisting of halogen, nitro, cyano, C C 4 -aIkyl, d-C -haloaIkyl, d-C -alkoxy, C C 4 -haloalkoxy, d-C 4 -alkylthio, d-d-alkylsulfinyl, d-C 4 -alkylsulfonyl.
  • Y is in particular oxygen.
  • R 6 is preferably C C 4 -aIkyl, C C 4 -alkoxy-C C 4 -alkyl or C 3 -C 6 - cycloalkyl and especially methyl or ethyl.
  • R 7 is preferably hydrogen.
  • Particularly preferred compounds I are the compounds of the formula l.aa.1 given below
  • R 2 , R 3 and R 5 have the meanings given above, in particular the meanings given as being preferred and R 7 is hydrogen.
  • Examples of compounds of formula l.aa.1 are the compounds listed in the table below in which R 2 , R 3 and R 5 each have the meaning given in one row of table A (compounds l.aa.1-1 to l.aa.1-48).
  • Table A
  • the compounds of the formula I according to the invention can be prepared analogously to the methods described in the prior art cited at the outset.
  • a 5-amino- isothiazole compound of the formula II is reacted in a process known per se with a carboxylic acid or a carboxylic acid derivative of the formula III in which L is a nucleophilically displaceable leaving group, for example OH, halogen, in particular chlorine, alkoxy and the like, as shown in Scheme 1.
  • L is a nucleophilically displaceable leaving group, for example OH, halogen, in particular chlorine, alkoxy and the like, as shown in Scheme 1.
  • Y, R 1 , R 3 , R 4 , R 5 and R 7 are as defined above.
  • This reaction is usually carried out at temperatures of from 0°C to 100°C, preferably from 0°C to 50°C, in an inert organic solvent. If L in formula III is a halogen atom, the reaction is preferably carried out in the presence of a base. If L in formula III is OH, the reaction is preferably carried out in the presence of a coupling agent which activates the OH group.
  • Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, disopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide and ethyl acetate. It is also possible to use mixtures of the solvents mentioned.
  • Suitable bases are, in general, alkali metal and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarboate, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, triisopropylamine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines. Particular preference is given to triethylamine, pyridine and 4-dimethylaminopyridine.
  • the bases are generally employed in equimolar amounts; however, they can also be used in excess or, if appropriate, as solvent.
  • Suitable coupling agents are in particular carbodiimides, for example 1 ,3-dicyclohexyl- carbodiimide, 1 ,3-diisopropylcarbodiimide and 1-(3-dimethylaminopropyl)-3-ethylcarbo- diimide.
  • the coupling agents are generally employed in equimolar amounts; however, they can also be used in excess, for example in an amount of up to 2 mol per mole of the compound III.
  • the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous to use an excess of one of the reaction partners.
  • reaction mixtures are worked up in a customary manner, for example by mixing with dilute acid, water or dilute base, separating the phases and, if appropriate, chromatographic purification of the crude products.
  • Some of the intermediates and end products are obtained in the form of colorless or slightly brownish viscous oils which are free from volatile components or purified under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, the purification may also be carried out by recrystallization or digestion.
  • suitable sulfurizing agents are organophosphorus sulfides such as Lawesson reagent, organotin sulfides or phosphorus(V) sulfides (see also J. March, Advanced Organic Synthesis, 2nd edition, Wiley Interscience 1985, p. 794 and literature cited there).
  • the reaction may be carried out in a solvent or in substance. Suitable solvents are the abovementioned inert solvents and the like.
  • the temperature required for the reaction is generally above room temperature and is in particular in the range from 50 to 200°C.
  • aminoisothiazoles of the formula II required for preparing the compounds I can be prepared by processes known per se. A preferred route to aminoisothiazoles II is shown in Scheme 2.
  • R 1 is as defined above and R a7 is hydrogen or methyl .
  • R is alkyl having 1 to 4 carbon atoms, for example methyl or ethyl.
  • [Pd] is a homogeneous catalyst with palladium as active metal.
  • an isothiazole compound III will be reacted with an iodinating agent, for example N-iodosuccinimide, if appropriate in an inert solvent, for example an alkane or a halogenated hydrocarbon or a mixture thereof.
  • an inert solvent for example an alkane or a halogenated hydrocarbon or a mixture thereof.
  • Processes to achieve this are known in principle, for example from WO 95/33418, and can be employed analogously to the preparation of the compound IV.
  • the resulting 5-amino-4-iodoisothiazole IV is then reacted with a trialkylsilylethyne, for example trimethylsilylethyne or an alkyne of the formula HC ⁇ C-R a7 (wherein R a7 is hydrogen or methyl) in the presence of a palladium catalyst.
  • a trialkylsilylethyne for example trimethylsilylethyne or an alkyne of the formula HC ⁇ C-R a7 (wherein R a7 is hydrogen or methyl
  • the use of copper(l) salts as cocatalysts may be recommended.
  • Processes for this purpose are known in principle, for example from N. Harris et al., Synlett 1990 (10) p. 577, US 4705799, J.M. Kehoe et al. Organic Lett. 2000 (2), p. 969, K.H.H.
  • the reaction of compound IV with the trialkylsilylethyne is preferably carried out in the presence of a base, preferably a tertiary organic amine, in particular a trialkylamine, such as triethylamine.
  • a base preferably a tertiary organic amine, in particular a trialkylamine, such as triethylamine.
  • the reaction is preferably carried out in a solvent or diluent, for example one of the solvents mentioned in connection with Scheme 1 , in particular an ether.
  • the subsequent removal of the trialkylsilyl group from the compound I can be carried out analogously to known processes.for removing acetylenically attached trialkylsilyl groups, as described, for example, by C.J. Yu et al., J. Org. Chem. 1999, (64) p. 2070 or by D. Holmes et al., Chem. Eur. J. 1999 (5), p. 3399.
  • the compound V is generally reacted with a fluoride source, for example a tetraalkylammonium fluoride, such as tetrabutylammonium fluoride, or an alkali metal fluoride, such as sodium fluoride or potassium fluoride, if appropriate in the presence of a complex ligand, such as a crown ether.
  • a fluoride source for example a tetraalkylammonium fluoride, such as tetrabutylammonium fluoride, or an alkali metal fluoride, such as sodium fluoride or potassium fluoride, if appropriate in the presence of a complex ligand, such as a crown ether.
  • a fluoride source for example a tetraalkylammonium fluoride, such as tetrabutylammonium fluoride, or an alkali metal fluoride, such as sodium fluoride or potassium fluoride, if appropriate in the presence of a complex
  • the starting materials of the formula III required for preparing the compounds I are known from the literature, for example from the prior art cited at the outset or they can be prepared in accordance with the literature cited therein.
  • the compounds I and their salts are suitable for controlling plant-damaging microorganisms, in particular harmful fungi (i.e. as fungicides) and for controlling animal plant pests, i.e. as pesticides.
  • the compounds I are also suitable for controlling harmful fungi, such as Paecilomyces variotii, in the protection of materials (e.g. wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products.
  • harmful fungi such as Paecilomyces variotii
  • materials e.g. wood, paper, paint dispersions, fibers or fabrics
  • the compounds of the formula I are furthermore suitable for the effective control of animal pests from the class of the insects, arachnids and nematodes. They can be used for controlling animal pests in crop protection and in the sectors of hygiene and of protection of stored products and in the veterinary sector.
  • Insects from the order of the lepidopterons (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana,
  • dipterons e.g. Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pe
  • Heteropterans Hymenoptera
  • Hymenoptera e.g. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata and Solenopsis invicta, • heteropterans (Heteroptera), e.g.
  • orthopterans e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus,
  • Orthoptera e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mex
  • Arachnoidea such as arachnids (Acarina), e.g. Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyes sheldoni, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Omithodorus moubata, Otobius megnini, Paratetranychus pilosus, Dermanyssus gallinae, Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei,
  • Meloidogyne hapla Meloidogyne incognita, Meloidogyne javanica, cyst-forming nematodes, e.g. Globodera rostochiensis, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, stem and leaf nematodes, e.g.
  • Belonolaimus longicaudatus Ditylenchus destructor, Ditylenchus dipsaci, Heliocotylenchus multicinctus, Longidorus elongatus, Radopholus similis, Rotylenchus robustus, Trichodorus primitivus, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus and Pratylenchus goodeyi.
  • the compounds I are employed by treating the plant-damaging microorganisms or the animal pests or the plants, seeds, materials or soil to be protected from attack by these harmful organisms with an effective amount of the active compounds.
  • the application can be carried out both before and after the infection /infestation of the materials, plants or seeds by the harmful organisms.
  • compositions according to the invention generally comprise between 0.1 and 95%, preferably between 0.5 and 90%, by weight of active compound.
  • the amounts applied are, depending on the kind of effect desired, between O.01 and 2.0 kg of active compound per ha.
  • active compound 0.001 to 1 g, preferably 0.01 to 0.05 g, per kilogram of seed are generally required.
  • the amount of active compound applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active compound per cubic meter of treated material.
  • the application rate of active compound for controlling animal pests are from 0.1 to 2.0, preferably from 0.2 to 1.0, kg/ha.
  • the compounds I can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the application form depends on the particular purpose; in each case, it should ensure a fine and uniform distribution of the compound according to the invention.
  • the formulations are prepared in a known way, e.g. by extending the active compound with solvents and/or carriers, if desired using emulsifiers and dispersants, it being possible, when water is the diluent, also to use other organic solvents as auxiliary solvents.
  • Suitable auxiliaries for this purpose are essentially: solvents, such as aromatics (e.g. xylene), chlorinated aromatics (e.g.
  • chlorobenzenes paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine, dimethylformamide) and water; carriers, such as ground natural minerals (e.g. kaolins, clays, talc, chalk) and ground synthetic ores (e.g. highly dispersed silicic acid, silicates); emulsifiers, such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants, such as lignosulfite waste liquors and methylcellulose.
  • paraffins e.g. petroleum fractions
  • alcohols e.g. methanol, butanol
  • ketones e.g. cyclohexanone
  • amines e.g. ethanolamine, di
  • Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid and dibutyl- naphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids, and alkali metal and alkaline earth metal salts thereof, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, octylphenol and nonylphenol, alkylphenol polyglycol
  • Petroleum fractions having medium to high boiling points such as kerosene or diesel fuel, furthermore coal tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene, toluene, xylene, paraffin, tetrahydro- naphthalene, alkylated naphthalenes or derivatives thereof, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene or isophorone, or highly polar solvents, e.g. dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or water, are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions.
  • aliphatic, cyclic and aromatic hydrocarbons e.g. benzene, toluene,
  • Powders, preparations for broadcasting and dusts can be prepared by mixing or mutually grinding the active substances with a solid carrier.
  • Granules e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers.
  • Solid carriers are, e.g., mineral earths, such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate or ureas, and plant products, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
  • mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess,
  • the formulations generally comprise between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, of the active compound.
  • the active compounds are employed therein in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • V. 80 parts by weight of a compound according to the invention are intimately mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene- ⁇ -sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of pulverulent silica gel and are ground in a hammer mill (active compound content 80% by weight).
  • a spray emulsion comprising 0.1 % by weight of the active compound is obtained by fine dispersion of the mixture in 20 000 parts by weight, of water.
  • the active compounds can be used as such, in the form of their formulations or of the application forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, preparations for broadcasting or granules, by spraying, atomizing, dusting, broadcasting or watering.
  • the application forms depend entirely on the intended uses; they should always ensure the finest possible dispersion of the active compounds according to the invention.
  • Aqueous use forms can be prepared from emulsifiable concentrates, pastes or wettable powders (spray powders, oil dispersions) by addition of water.
  • the substances can be homogenized in water, as such or dissolved in an oil or solvent, by means of wetting agents, tackifiers, dispersants or emulsifiers.
  • concentrates comprising active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil can also be prepared, which concentrates are suitable for dilution with water.
  • concentrations of active compound in the ready-for-use preparations can be varied within relatively wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
  • the active compounds can also be used with great success in the ultra low volume (ULV) process, it being possible to apply formulations with more than 95% by weight of active compound or even the active compound without additives.
  • UUV ultra low volume
  • Oils of various types, herbicides, fungicides, other pesticides and bactericides can be added to the active compounds, including if need be not until immediately before use (tank mix). These agents can be added to the preparations according to the invention in a weight ratio of 1 :10 to 10:1.
  • the preparations according to the invention can, in the application form as fungicides, also be present together with other active compounds, e.g. with herbicides, insecticides, growth regulators, fungicides or also with fertilizers. On mixing the compounds I or the preparations comprising them in the application form as fungicides with other fungicides, in many cases an expansion of the fungicidai spectrum of activity is obtained.
  • fungicides with which the compounds according to the invention can be used in conjunction, is intended to illustrate the possible combinations but does not limit them: • acylalanines, such as benalaxyl, metalaxyl, ofurace or oxadixyl, • amine derivatives, such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine ortridemorph, • anilinopyrimidines, such as pyrimethanil, mepanipyrim or cyprodinil, • antibiotics, such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin, • azoles, such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, epoxiconazole, fen
  • reaction mixture is concentrated and the residue is chromatographed on silica gel (mobile phase cyclohexane.ethyl acetate 8:2 v/v), giving the ethynyl compound in a yield of 14.0 g (47% of theory).
  • the residue (about 67 mmol) is dissolved in 120 ml of toluene, the solution is added to a mixture of 4-ethynyl-3-methylisothiazol-5 ⁇ ylamine, 250 ml of toluene and 125 ml of pyridine, and a small amount of dimethylaminopyridine is added.
  • the solution is stirred at 40°C for 2 h.
  • the solution is then concentrated, the residue is partitioned between ethyl acetate O 200 23 and water and the organic phase is washed successively with 10% strength aqueous hydrochloric acid and aqueous sodium bicarbonate solution. After drying over magnesium sulfate, the organic phase is concentrated, giving the title compound.
  • Nilaparvata lugens As a solution in acetone:water 20:80 v/v to which a surfactant (Alkamuls EL 620) had been added in an amount of 0.1 % by volume.
  • a surfactant Alkamuls EL 620
  • Cotton plants of the cultivar "Deltapine” were, in the cotyledon stage, infected with about 100 laboratory aphids by placing infected leaf sections on the surface of the test plants. Leaf sections were removed after 24 h. The cotyledons of the plants were briefly dipped into solutions of the test compounds. The mortality rate of the aphids on the treated plants, compared to the control plants, was determined after five days.
  • the compounds of Examples 1 , 2, and 3 caused, at 300 ppm, a mortality of at least 70% to 100%, compared to the untreated plants.
  • Bell-pepper plants in the two-leaf stage were infected with about 40 aphids, which had been cultivated in the laboratory, by placing infected leaf sections onto the surface of the test plants. The leaf sections were removed after 24 h. Leaves of the treated plants were dipped into a solution of the test compound. The mortality of the aphids on the treated plants in comparison to the mortality of the control plants was determined after five days. In this assessment, the compounds of Examples 2 and 3 caused, at a concentration of active compound of 300 ppm, a mortality of about 100%, compared to untreated control plants.
  • Nasturtium plants in the one-leaf stage were infected with about 25 aphids, which had been cultivated in the laboratory, by placing infected leaf pieces onto the surface of the test plants. The leaf sections were removed after 24 h. The leaves and stems of the test plants were dipped into a solution of the test compound. The mortality of the aphids was determined after three days.
  • the compounds of Example 2 caused, at a concentration of active compound of 300 ppm, a mortality of at least 70%, compared to the untreated control plants.
  • Example 2 Three- to four-week-old rice plants were sprayed with 10 ml of the solution of active compound using a hand-operated atomizer (Devilbiss atomizer) with a pressure of 1.7 bar. The test plants were allowed to dry for 1 h and covered with hoods. The plants were inoculated with ten adult animals of each species (5 male and 5 female) and kept at 25 to 27°C and 50 to 60% atmospheric humidity for three days. The mortality was determined 24, 48 and 72 h after the treatment. Each treatment was repeated once. In this assessment, the compounds of Example 2 caused, at 300 ppm, a mortality of a mortality of about 100%, compared to the untreated plants.
  • a hand-operated atomizer Devilbiss atomizer

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
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  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
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Abstract

L'invention concerne de nouveaux composés 5-(2-arylacétamido)isothiazole et leurs sels acceptables en agriculture, ainsi que l'utilisation de ces composés pour lutter contre les micro-organismes endommageant les plantes et les phytoparasites animaux.
PCT/EP2004/012096 2003-10-27 2004-10-26 Composes i 5-(2-arylacetamido)isothiazole Ceased WO2005040162A1 (fr)

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US60/513,992 2003-10-27

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009059607A2 (fr) 2007-11-05 2009-05-14 Vestergaard Frandsen Sa Pièce comportant deux objets insecticides qui permettent de lutter contre les insectes résistants
CN109867666A (zh) * 2017-12-02 2019-06-11 沈阳中化农药化工研发有限公司 一种含异噻唑环的芳乙酰胺类化合物及其用途
WO2020161209A1 (fr) 2019-02-06 2020-08-13 Syngenta Crop Protection Ag Composés pyridazine fusionnés herbicides
WO2020161208A1 (fr) 2019-02-06 2020-08-13 Syngenta Crop Protection Ag Composés pyridazine fusionnés herbicides

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19628569A1 (de) * 1996-07-16 1998-01-22 Bayer Ag Substituierte N-(5-Isothiazolyl)-thioamide
WO2001055145A1 (fr) * 2000-01-28 2001-08-02 Syngenta Limited Derives d'azine en tant que pesticides
WO2001090105A1 (fr) * 2000-05-25 2001-11-29 Syngenta Limited Isothiazoles utilises en tant que pesticides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19628569A1 (de) * 1996-07-16 1998-01-22 Bayer Ag Substituierte N-(5-Isothiazolyl)-thioamide
WO2001055145A1 (fr) * 2000-01-28 2001-08-02 Syngenta Limited Derives d'azine en tant que pesticides
WO2001090105A1 (fr) * 2000-05-25 2001-11-29 Syngenta Limited Isothiazoles utilises en tant que pesticides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J.G. SAMARITONI, L. ARNDT, T.J. BRUCE, J.E. DRIPPS, J. GIFFORD ET AL.: "N-Alkyl-N-(5-isothiazolyl)- and N-(Alkylisothiazolin-5-ylidene)-phenylacetamides. Synthesis and Biological Activity", J. AGRIC. FOOD CHEM., vol. 45, 1997, pages 1920 - 1930, XP002322514 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009059607A2 (fr) 2007-11-05 2009-05-14 Vestergaard Frandsen Sa Pièce comportant deux objets insecticides qui permettent de lutter contre les insectes résistants
CN109867666A (zh) * 2017-12-02 2019-06-11 沈阳中化农药化工研发有限公司 一种含异噻唑环的芳乙酰胺类化合物及其用途
CN109867666B (zh) * 2017-12-02 2021-09-07 沈阳中化农药化工研发有限公司 一种含异噻唑环的芳乙酰胺类化合物及其用途
WO2020161209A1 (fr) 2019-02-06 2020-08-13 Syngenta Crop Protection Ag Composés pyridazine fusionnés herbicides
WO2020161208A1 (fr) 2019-02-06 2020-08-13 Syngenta Crop Protection Ag Composés pyridazine fusionnés herbicides

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