WO2001064644A1 - Dichloropyridyl- et dichloroisothiazolyl-thiocarboxamides et leur utilisation comme microbicides - Google Patents

Dichloropyridyl- et dichloroisothiazolyl-thiocarboxamides et leur utilisation comme microbicides Download PDF

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Publication number
WO2001064644A1
WO2001064644A1 PCT/EP2001/001824 EP0101824W WO0164644A1 WO 2001064644 A1 WO2001064644 A1 WO 2001064644A1 EP 0101824 W EP0101824 W EP 0101824W WO 0164644 A1 WO0164644 A1 WO 0164644A1
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phch
methyl
phenyl
methoxy
alkyl
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PCT/EP2001/001824
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English (en)
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Yukiyoshi Watanabe
Yoshinori Kitagawa
Haruko Sawada
Yasuo Araki
Lutz Assmann
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Nihon Bayer Agrochem K.K.
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Priority to AU54649/01A priority Critical patent/AU5464901A/en
Publication of WO2001064644A1 publication Critical patent/WO2001064644A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/83—Thioacids; Thioesters; Thioamides; Thioimides
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/02—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
    • C07D275/03—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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

Definitions

  • the present invention relates to novel thiocarboxamides, to a process for their preparation and to their use as microbicides.
  • R represents C g alkyl, Cj_ 4 haloalkyl, C ⁇ alkoxy-C ⁇ .3 alkyl, C 1 . 4 alkylthio- C ⁇ _3 alkyl, optionally substituted C3. 6 cycloalkyl, optionally substituted aralkyl, optionally substituted phenoxyalkyl, optionally substituted phenylthioalkyl, optionally substituted phenyl or a group selected from
  • R 1 represents C ⁇ alkyl
  • R 2 represents hydrogen, halogen, C j _ 4 alkyl or C ⁇ alkoxy and
  • R 3 represents hydrogen, halogen, C 1.4 alkyl or C j _ 4 alkoxy.
  • R and Z have the above-mentioned meanings
  • the thiocarboxamides of the formula (I) are outstandingly active as microbicides in agriculture and horticulture, particularly as fungicides for the direct control of plant diseases or for causing resistance in plants against plant pathogens.
  • the thiocarboxamides of the formula (I) according to the invention have a much better microbicidal activity than the already known compounds, which are structurally most similar and have the same type of action.
  • C ⁇ . 6 alkyl can be linear or branched, and to be specific, it includes, for example, methyl, ethyl, n-propyl, isopropyl, n-(iso-, sec- or tert-)butyl, n-pentyl, isopentyl and n-hexyl.
  • C alkyl and a C M alkyl part in C M haloalkyl, C alkoxy-C ⁇ -3 alkyl, C alkylthio-C ⁇ -3 alkyl, C M alkoxy and C M alkylthio can be linear or branched, and to be specific, they represent methyl, ethyl, n-propyl, isopropyl or n-, iso, sec- or tert- butyl.
  • a C ⁇ -3 alkyl part in C M alkoxy-C ⁇ _ alkyl and C M alkylthio-C 1-3 alkyl can be linear or branched, and to be specific, it represents methyl, ethyl, n-propyl or isopropyl.
  • C M alkoxy and a C M alkoxy part in C 1-4 alkoxy-C ⁇ -3 alkyl are C alkyl-O- in which C 1-4 alkyl has the significance as described above, i.e., they include methoxy, ethoxy, n-propoxy, isopropoxy or n-, iso-, sec- or tert-butoxy.
  • C M alkylthio and a C M alkylthio part in C M alkylthio-C 1-3 alkyl are C alkyl-S- in which C M alkyl is synonymous with that described above, and to be specific, they include methylthio, ethylthio, n-propylthio, isopropylthio or n-, iso, sec- or tert- butylthio.
  • fluorine, chlorine, bromine and iodine are included in a halogen part of halogen and C M haloalkyl.
  • C 3 _ 6 cycloalkyl represents, to be specific, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • Aralkyl is aryl-substituted alkyl and, to be specific, includes phenyl-C ⁇ - alkyl and diphenyl-propyl.
  • Suitable examples thereof include benzyl, 1-methylbenzyl, 1- ethylbenzyl, 1-n-propylbenzyl, 1-isopropylbenzyl, 2-phenylethyl, 2-phenyl-l- methyl ethyl, 2-phenyl-l-ethylethyl, 2-phenyl- 1,1 -dimethyl ethyl, 3-phenylpropyl, 3- phenyl-1-methylpropyl, 3-phenyl-l-ethylpropyl, 3-phenyl-l-n-propyl-propyl, 3- phenyl-1-isopropyl-propyl, 3-phenyl-l-n-butyl-propyl, 4-phenylbutyl and 1.3- diphenylpropane- 1 -yl.
  • phenoxy-C j ⁇ -alkyl includes, for example, 2-phenoxy ethyl, 1-methyl- 2-phenoxyethyl and l-ethyl-2-phenoxyethyl.
  • phenylthio-C j . 4 -alkyl includes, for example, 2-phenylthioethyl, 1- methyl-2-phenylthioethyl and l-ethyl-2-phenylthioethyl.
  • Formula (I) provides a general definition of the thiocarboxamides according to the invention.
  • Preferred compounds of the formula (I) are those, in which
  • R represents C j .g alkyl, haloalkyl having 1 to 3 carbon atoms and 1 to 5 halogen atoms, C j _ 4 alkoxy-C2_3 alkyl, C1. 4 alkylthio-C 2 _ 3 -alkyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, which may be substituted by 1 to 3 methyl groups, or
  • R represents phenylalkyl having 1 to 7 carbon atoms in the alkyl part and being optionally substituted in the phenyl part by 1 to 3 radicals selected from fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, tert-buryl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, difluoro- methyl, difluoromethoxy, phenyl, phenoxy, trifluoromethylthio and/or nitro. or
  • R represents phenoxyalkyl having 1 to 4 carbon atoms in the alkyl part and being optionally substituted in the phenoxy part by 1 to 3 radicals selected from fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, tert- butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, phenyl, phenoxy, trifluoromethylthio and/or nitro, or
  • R represents phenylthioalkyl having 1 to 4 carbon atoms in the alkyl part and being optionally substituted in the phenylthio part by 1 to 3 radicals selected from fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, tert- butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, phenyl, phenoxy, trifluoromethylthio and/or nitro, or
  • R represents phenyl optionally substituted by 1 to 3 radicals selected from fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethxy, phenyl, phenoxy, trifluoromethylthio and/or nitro, or
  • R represents 1,3-diphenylpropan-l-yl or l-(4-fluorophenyl)-3-phenylpropan-l- yl, or
  • R represents a group selected from
  • R 1 represents C1.3 alkyl
  • R 2 represents hydrogen, chlorine, methyl or methoxy
  • R 3 represents hydrogen, chlorine, methyl or methoxy
  • Z represents a group of the formula
  • R represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, n-pentyl, fluoroethyl, chloroethyl, bromoethyl, 2,2,2-trifluoroethyl, 3- chloropropyl, 3-bromopropyl, 2-methoxyethyl, 3-methoxypropyl, 3-ethoxy- propyl, 3-isopropoxypropyl, 3-n-butoxypropyl, 2-methylthioethyl, 2-ethyl- thioethyl, 3-methylthiopropyl, 3-ethylthiopropyl, cyclopropyl, cyclopentyl, cyclohexyl or 2-methylcyclohexyl, or
  • R represents phenylalkyl having 1 to 7 carbon atoms in the alkyl part and being optionally substituted in the phenyl part by 1 to 3 radicals selected from fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, phenyl, phenoxy, trifluoromethylthio and/or nitro, or
  • R represents phenoxyalkyl having 1 to 4 carbon atoms in the alkyl part and being optionally substituted in the phenoxy part by 1 to 3 radicals selected from fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, tert- butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, phenyl, phenoxy, trifluoromethylthio and/or nitro or
  • R represents phenylthioalkyl having 1 to 4 carbon atoms in the alkyl part and being optionally substituted in the phenylthio part by 1 to 3 radicals selected from fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, tert- butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, phenyl, phenoxy, trifluoromethylthio and/or nitro, or
  • R represents phenyl optionally substituted by 1 to 3 radicals selected from fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, phenyl, phenoxy, trifluoromethylthio and/or nitro, or
  • R represents 1,3-diphenylpropan-l-yl or l-(4-fluorophenyl)-3-phenylpropan-l- yl, or
  • R represents a group selected from
  • R 1 represents methyl, ethyl, n-propyl or isopropyl
  • R2 represents hydrogen, or chlorine , methyl or methoxy at the 5 -position or 6- position
  • R 3 represents hydrogen, or chlorine, methyl or methoxy at the 5-position or 6- position
  • the thiocarboxamides of the formula (I) according to the invention may comprise an asymmetrically substituted carbon atom.
  • the compounds of the formula (I) may be present as (R)- or (S)-enantiomers having optical activity.
  • Formula (II) provides a general definition of the carboxamides, which are required as starting materials for conducting process (a) according to the invention.
  • R and Z preferably have those meanings, which have already been mentioned as preferred for these substituents.
  • N-( ⁇ -methylbenzyl)-2,6-dichloroisonicotinic acid amide N-(3-fluoro- ⁇ -methylbenzyl)-2,6-dichloroisonicotinic acid amide, N-(4-bromo- ⁇ -methylbenzyl)-2,6-dichloroisonicotinic acid amide.
  • N-(4-difluoromethoxy- ⁇ -methylbenzyl)-2,6-dichloroisonicotinic acid amide N-(3-methoxybenzyl)-2,6-dichloroisonicotmic acid amide, N-(phenethyl)-2,6-dichloroisonicotinic acid amide, N-[3-(3'-methoxyphenyl)-l-methylpropyl]-2,6-dichloroisonicotinic acid amide, N-[3-(3'-fluorophenyl)-l-ethylpropyl]-2,6-dichloroisonicotinic acid amide,
  • N-(4-trifluoromethoxybenzyl)-3,4-dichloroisothiazole-5-carboxylic acid amide N-(4-fluorobenzyl)-3,4-dichloroisothiazole-5-carboxylic acid amide, N-(l ,3-diphenylpropyl)-3,4-dichloroisothiazole-5-carboxylic acid amide, N-[3-(3'-fluorophenyl)-l-ethylpropyl]-3,4-dichloroisothiazole-5-carboxylic acid amide, N-[3-(3'-methoxyphenyl)-l-ethylpropyl]-3,4-dichloroisothiazole-5-carboxylic acid amide,
  • Formula (III) provides a general definition of the carbonylchlorides, which are required as starting materials for conducting process (b).
  • Z represents a group of the formula
  • formula (III) includes 3,4-dichloro-5-isothiazolecarbonyl chloride and
  • Formula (IV) provides a general definition of the amines, which are required as reaction components for conducting process (b).
  • R preferably has those meanings, which have already been mentioned as preferred for this substituent.
  • the amines of the formula (IV) are known or can be prepared by known methods (see Organic Reactions, Vol. 5 (1949), 301-330, JP-A 264 465-1988 and JP-A
  • Suitable diluents for conducting process (b) are all customary inert organic solvents.
  • Suitable solvents preferably include aliphatic, alicyclic and aromatic hydrocarbons (which may be chlorinated), such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1 ,2-dichloroethane, chlorobenzene and dichlorobenzene; ethers, such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and diethylene glycol dimethyl ether (DGM); ketones such as acetone, methyl ethyl ketone, (MEK), methyl iso
  • Suitable acid-binding agents for conducting process (b) are all customary inorganic and organic acid acceptors. The following can preferably be used:
  • Inorganic bases including hydrides, hydroxides, carbonates and bicarbonates of alkaline metals and alkaline earth metals, such as sodium hydride, lithium hydride, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; inorganic alkaline metal amides such as lithium amide, sodium amide and potassium amide; and organic bases including alcoholates, tertiary amines, dialkylaminoanilines and pyridines, such as triethylamine, 1,1,4,4-tetramethylethyl- enediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimeth- ylaminopyridine (DMAP), l,4-diazabicyclo[2,2,2]octane (DABCO) and 1,8-di- azabicyclo[5,4,0]-und
  • reaction temperatures can be varied within a substantially wide range.
  • the reaction is generally carried out at a temperature between about -20°C and about +100°C, preferably between about -10°C and about +60°C.
  • Process (b) is generally carried out under atmospheric pressure but, if desired, can also be carried out under elevated or reduced pressure.
  • Suitable diluents for carrying out process (a) according to the invention preferably included aliphatic, alicyclic and aromatic hydrocarbons (which may be chlorinated), such as pentane, li groin, benzene, toluene, xylene, 1 ,2-dichloroethane, chlorobenzene and dichlorobenzene; ethers such as isopropyl ether, butyl ether, dioxane, dimethoxy- ethane (DME), tetrahydrofuran (THF) and diethylene glycol dimethyl ether (DGM; and bases such as pyridine.
  • aliphatic, alicyclic and aromatic hydrocarbons which may be chlorinated
  • ethers such as isopropyl ether, butyl ether, dioxane, dimethoxy- ethane (DME), tetrahydrofuran (THF) and diethylene glycol dimethyl ether (
  • reaction temperatures can be varied within a substantially wide range.
  • the reaction is generally carried out at a temperature between about 20°C and about 200°C, preferably between about
  • Process (a) according to the invention is generally carried out under atmospheric pressure but, if desired, can also be carried out under elevated or reduced pressure.
  • process (a) according to the invention in general one mole of a carboxamide of the formula (II) is reacted with 0.8 to 1.5 moles of phosphorous pentasulfide in the presence of a diluent, such as toluene.
  • the compounds of the formula (I) prepared by the above-mentioned process can in each case be isolated from the reaction mixtures by customary procedures and can be purified by known methods, such as crystallization, chromatography etc.
  • the compounds according to the present invention exhibit a strong microbicidal activity. Thus, they can be used for combating undesired microorganisms, such as phytopathogenic fungi and bacteriae, in agriculture and horticulture.
  • the compounds are suitable for the direct control of undesired microorganisms as well as for generating resistance in plants against attack by undesired plant pathogens.
  • Resistance-inducing substances in the present context are to be understood as those substances which are capable of stimulating the defense system of plants such that the treated plants, when subsequently inoculated with undesirable microorganisms, display substantial resistance to these microorganisms.
  • Undesirable microorganisms in the present case are to be understood as phytopathogenic fungi and bacteriae.
  • the substances according to the invention can thus be employed to generate resistance in plants against attack by the harmful organisms mentioned within a certain period of time after the treatment.
  • the period of time within which resistance is brought about in general extends from 1 to 10 days, prefer- ably 1 to 7 days, after treatment of the plants with the active compounds.
  • the compounds according to the invention can be used as fungicides for combating phytopathogenic fungi, such as Plasmodiophoromycetes, Oomycetes,
  • Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deutero- mycetes and can also be used as bactericides for combating bacteriae, such as Pseudomonadaceae, R izobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
  • the compounds according to the present invention are particularly suitable for causing resistance against infection of plants by plant pathogens, such as Pyricularia oryzae, Phythophthora infestans etc.
  • the good toleration, by plants, of the active compounds, at the concentrations required for combating plants diseases permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.
  • the compounds according to the present invention have a low toxicity against warmblooded animals and therefore can be used safely.
  • the active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, foams, pastes, granules, tablets, aerosols, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances, coating compositions for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as ULV cold mist and warm mist formulations.
  • customary formulations such as solutions, emulsions, wettable powders, suspensions, powders, foams, pastes, granules, tablets, aerosols, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances, coating compositions for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as ULV cold mist and warm mist formulations.
  • formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents.
  • extenders that is to say liquid or liquefied gaseous or solid diluents or carriers
  • surface-active agents that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents.
  • organic solvents can, for example, also be used as auxiliary solvents.
  • liquid solvents diluents or carriers there are suitable in the main, aromatic hydrocarbons such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl-isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethyl-sulphoxide, as well as water.
  • aromatic hydrocarbons such as xylene, toluene or alkyl naphthalenes
  • chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene
  • liquefied gaseous diluents or carriers liquids which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
  • ground natural minerals such as kaolings, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth
  • ground synthetic minerals such as highly-dispersed silicic acid, alumina and silicates.
  • crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.
  • non-ionic and anionic emulsifiers such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products.
  • Dispersing agents include, for example, lignin sulphite waste liquors and methyl - cellulose.
  • Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and poly- vinyl acetate, can be used in the formulation. It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue
  • organic dyestuffs such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs
  • trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc
  • the formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
  • the active compounds according to the invention can be present in the formulations or in the various use forms as a mixture with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellents, growth factors, plant nutrients and agents for improving soil structure.
  • active compounds such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellents, growth factors, plant nutrients and agents for improving soil structure.
  • Fungicides aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin, benalaxyl, benodanil, benomyl, benzamacril, benzamacril-isobutyl, bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate, calcium polysulphide, capsimycin, captafol, captan, carbendazim, carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chloro- thalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyproconazole, cyprodinil, cypro
  • Bactericides bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
  • Insecticides / acaricides / nematicides abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb, aldoxycarb, alpha- cypermethrin, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azamethiphos, azinphos A, azinphos M, azocyclotin,
  • Bacillus thuringiensis strain EG-2348 Bacillus thuringiensis strain EG-2348,
  • the active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, tablets, pastes, microcapsules and granules. They are used in the customary manner, for example by watering, immersion, spraying, atomizing, misting, vaporizing, injecting, forming a slurry, brushing on, dusting, scattering, dry dressing, moist dressing, wet dressing, slurry dressing or encrusting.
  • the active compounds concentration in the use forms can be varied within a substantial range. They are, in general, from 1 to 0.0001% by weight, preferably from 0.5 and 0.001%.
  • active compound concentrations for the treatment of soil, active compound concentrations, at the point of action, of 0.00001 to 0.1% by weight, especially of 0.0001 to 0.02%, are generally employed.
  • plants and parts of plants can be treated according to the invention.
  • naturally occurring plant species and plant varieties or those obtained by conventional biological breeding methods such as crossbreeding or protoplast fusion as well as parts of such plants are treated.
  • transgenic plants and plant varieties which have been obtained by genetic engineering methods possibly in combination with conventional methods (genetically modified organisms) and parts of such plants are treated.
  • the term "parts" or “parts of plants” or “plant parts” is explained above.
  • plants of the plant varieties commercially available or used at any particular time are very preferably treated.
  • Plant varieties are understood to be plants with specific properties ("traits") which have been obtained both by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be varieties, biotypes or genotypes.
  • superadditive effects can occur as a result of the treatment according to the invention. Effects such as for example reduced application rates and/or broadening of the activity spectra and/or increased activity of the compounds and compositions usable according to the invention, improved plant growth, increased tolerance of high or low temperatures, increased tolerance of dry conditions or water or ground salt contents, increased flowering capacity, facilitated harvesting, acceleration of maturity, increased crop yields, higher quality and/or increased nutritional value of the harvested crops and increased storing quality and/or processibility of the harvested crops are possible, which are greater than those actually expected.
  • Preferred transgenic plants or plant varieties (obtained by genetic engineering) to be treated according to the invention include all plants which as a result of the genetic modification concerned have received genetic material which provides them with particularly advantageous valuable properties ("traits").
  • traits are improved plant growth, increased tolerance of high or low temperatures, increased tolerance of dry conditions or water or ground salt contents, increased flowering capacity, facilitated harvesting, acceleration of maturity, increased crop yields, higher quality and/or increased nutritional value of the harvested crops and increased storing quality and/or processibility of the harvested crops.
  • Additional and particularly noteworthy examples of such properties are increased resistance of the plants to animal and microbial pests, such as to insects, mites, phytopathogenic fungi, bacteria and/or viruses as well as increased tolerance by the plants of certain herbicidal active compounds.
  • transgenic plants examples which may be mentioned of transgenic plants are the important crop plants such as cereals (wheat and rice), com, soybeans, potatoes, cotton, rape and fruit plants (producing apples, pears, citrus fruits and grapes), the crop plants corn, soybeans, potatoes, cotton and rape being particularly noteworthy.
  • Particularly significant properties are increased resistance of the plants to insects due to the toxins forming in the plants, and in particular those which are produced in the plants (hereinafter refe ⁇ ed to as "Bt plants”) by the genetic material obtained from Bacillus Thuringiensis (e.g. by the genes CrylA(a), CrylA(b),
  • traits are the increased resistance of plants to fungi, bacteria and viruses due to systemically acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins.
  • SAR systemically acquired resistance
  • Particulary significant properties are also increased tolerance by the plants of certain herbicidal active compounds, such as for example imidazolinones, sulphonylureas, glyphosate or phosphinotricine (e.g. the "PAT" gene).
  • twins can also occur in the transgenic plants in combination with each other.
  • “Bt plants” are varieties of corn, cotton, soybeans and potatoes which are sold under the trade names YIELD GARD® (e.g. com, cotton, soybeans), KnockOut® (e.g. corn), StarLink® (e.g. corn), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potatoes).
  • herbicide-tolerant plants are varieties of corn, cotton and soybeans which are sold under the trade names Roundup Ready® (tolerance of glyphosate, e.g. com, cotton, soybeans),
  • the above-mentioned plants can be particularly advantageously treated with the compounds of the general formula I or the active compound mixtures according to the invention.
  • the preferred ranges mentioned above for the active compounds or mixtures also apply to the treatment of these plants.
  • Particularly advantageous is the treatment of plants with the compounds or mixtures specifically listed in the present text.
  • A represents:
  • Ph represents phenyl
  • R represents an optical isomer of the R configuration
  • S represents an optical isomer of the S configuration.
  • a tetrahydrofuran solution (5 ml) of a mixture of 0.61 g (5 mmol) of ⁇ - methylbenzylamine and 1.51 g (15 mmol) of triethylamine was added dropwise to a tetrahydrofuran solution (10 ml) of 2,6-dichloroisonicotinic acid chloride under cooling with ice. After stirring for 2 hours at a room temperature, water (20 ml) and ether (40 ml) were added and the mixture was stirred.
  • the ether layer was successively washed with a 10 % hydrochloric acid aqueous solution, water, a saturated sodium hydrogencarbonate aqueous solution and a saturated brine solution and then dried over anhydrous sodium sulfate. After distilling ether off under reduced pressure, the residue was subjected to silica gel column chromatography to obtain 1.1 1 g of N-( ⁇ -methylbenzyl)-2,6-dichloroisonicotinic acid amide. Mp: 162 to 163 °C, yield: 75 %.
  • a mixture of 10 g (49 mmol) of 4-(trifluoromethoxy)-acetophenone and 33 ml of formamide was heated to 140 to 150°C, and 6.77 g (147 mmol) of formic acid were slowly added dropwise while maintaining this temperature. After finishing the addition, the solution was heated for further 2 hours at 150°C. After cooling, water was added, and the mixture was extracted with methylene chloride. The methylene chloride layer was washed with water and dried over anhydrous sodium sulfate. After distilling methylene chloride off under reduced pressure, 28 ml of concentrated hydrochloric acid were added to the residue, and the solution was refluxed for 2 hours by heating.
  • Active compound 30 - 40 parts by weight
  • Carrier mixture of diatomaceous earth and kaolin (1:5), 55-65 parts by weight
  • Emulsifier polyoxyethylene alkyl phenyl ether, 5 parts by weight
  • the above-mentioned amounts of active compound, carrier and emulsifier are crushed and mixed to make a wettable powder.
  • a portion of the wettable powder comprising the prescribed amount of active compound is diluted with water and used for testing.
  • Seeds of paddy rice (cultivar: Kasabue) were soaked in a diluted solution of an active compound having the prescribed concentration. 5 ml of such solution, which had been prepared as mentioned above, were used per 150 grains of seed. Soaking was conducted at a temperature of 20°C for 5 days. After the soaking, the air-dried seeds were sown in 2 plastic pots, each having a diameter of 9 cm, and the seeds were germinated by placing the pots in a warmed nursery box (32°C) for 3 days. After cultivating the seedlings for 2 weeks, the plants reached the 2 - 2.5 leaf stage.
  • a spore suspension of artificially cultured Pyricularia oryzae was then sprayed on the test plants once, and the plants were kept at a temperature of 25°C and a relative atmospheric humidity of 100% for infection. Seven days after the inoculation, the infection rate per pot was classified and evaluated and the control value (%) was calculated. Phytotoxicity was tested at the same time.
  • Control value (%) 1 x ⁇ oo
  • An emulsifiable concentrate was prepared by mixing 30 parts by weight of Compound No. 399 according to the invention, 5 parts by weight of xylene, 8 parts by weight of polyoxyethylene alkyl phenyl ether and 7 parts by weight of calcium alkylbenzene sulphonate with stirring.
  • a wettable powder was prepared by thoroughly mixing 15 parts by weight of Compound No. 441 according to the invention, 80 parts by weight of a mixture (1:5) of White Carbon (fine powder of hydrated non-crystalline silicon oxide) and powdery clay, 2 parts by weight of sodium alkylbenzene sulphonate and 3 parts by weight of a condensate of sodium alkylnaphthalene sulphonate and formaldehyde in powdery state.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
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Abstract

L'invention concerne des thiocarboxamides représentés par la formule (I), dans laquelle Z représente un groupe de formule (II) ou (III) et R représente des groupes spécifiés. Ces composés présentent une activité microbicide efficace dans l'agriculture et l'horticulture, et peuvent notamment être utilisés comme fongicides afin de lutter contre les maladies des plantes ou d'augmenter la résistance des plantes aux agents pathogènes.
PCT/EP2001/001824 2000-03-01 2001-02-19 Dichloropyridyl- et dichloroisothiazolyl-thiocarboxamides et leur utilisation comme microbicides WO2001064644A1 (fr)

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JP2000-056101 2000-03-01

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WO2012010579A2 (fr) 2010-07-20 2012-01-26 Bayer Cropscience Ag Benzocycloalcènes à titre d'agents antifongiques
US8389021B2 (en) 2009-02-03 2013-03-05 Microbion Corporation Bismuth-thiols as antiseptics for epithelial tissues, acute and chronic wounds, bacterial biofilms and other indications
US9028878B2 (en) 2009-02-03 2015-05-12 Microbion Corporation Bismuth-thiols as antiseptics for biomedical uses, including treatment of bacterial biofilms and other uses
US9408393B2 (en) 2010-02-03 2016-08-09 Microbion Corporation Bismuth-thiols as antiseptics for agricultural, industrial and other uses
CN108912005A (zh) * 2013-08-09 2018-11-30 奥斯瓦道·克鲁兹基金会 二苯氧基烷基胺衍生物及其药物组合物
CN111741944A (zh) * 2018-02-01 2020-10-02 悉尼大学 抗癌化合物
US20210120817A1 (en) * 2017-03-17 2021-04-29 Meiji Seika Pharma Co., Ltd. Plant disease control agent
US11207288B2 (en) 2018-07-31 2021-12-28 Microbion Corporation Bismuth-thiol compositions and methods for treating wounds
US20220280476A1 (en) * 2019-05-03 2022-09-08 Praxis Precision Medicines, Inc. Kcnt1 inhibitors and methods of use
US11464749B2 (en) 2018-07-31 2022-10-11 Microbion Corporation Bismuth-thiol compositions and methods of use

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US10835510B2 (en) 2009-02-03 2020-11-17 Microbion Corporation Bismuth-thiols as antiseptics for epithelial tissues, acute and chronic wounds, bacterial biofilms and other indications
US8389021B2 (en) 2009-02-03 2013-03-05 Microbion Corporation Bismuth-thiols as antiseptics for epithelial tissues, acute and chronic wounds, bacterial biofilms and other indications
US9028878B2 (en) 2009-02-03 2015-05-12 Microbion Corporation Bismuth-thiols as antiseptics for biomedical uses, including treatment of bacterial biofilms and other uses
US10960012B2 (en) 2009-02-03 2021-03-30 Microbion Corporation Bismuth-thiols as antiseptics for biomedical uses, including treatment of bacterial biofilms and other uses
US9408393B2 (en) 2010-02-03 2016-08-09 Microbion Corporation Bismuth-thiols as antiseptics for agricultural, industrial and other uses
WO2012010579A3 (fr) * 2010-07-20 2012-08-16 Bayer Cropscience Ag Benzocycloalcènes à titre d'agents antifongiques
CN103003246A (zh) * 2010-07-20 2013-03-27 拜尔农科股份公司 作为抗真菌剂的苯并环烯烃
JP2013532648A (ja) * 2010-07-20 2013-08-19 バイエル・クロップサイエンス・アーゲー 抗菌剤としてのベンゾシクロアルケン類
US9173399B2 (en) 2010-07-20 2015-11-03 Bayer Intellectual Property Gmbh Benzocycloalkenes as antifungal agents
CN103003246B (zh) * 2010-07-20 2015-11-25 拜尔农科股份公司 作为抗真菌剂的苯并环烯烃
US10093611B2 (en) 2010-07-20 2018-10-09 Bayer Intellectual Property Gmbh Benzocycloalkenes as antifungal agents
WO2012010579A2 (fr) 2010-07-20 2012-01-26 Bayer Cropscience Ag Benzocycloalcènes à titre d'agents antifongiques
CN108912005A (zh) * 2013-08-09 2018-11-30 奥斯瓦道·克鲁兹基金会 二苯氧基烷基胺衍生物及其药物组合物
CN108912005B (zh) * 2013-08-09 2022-01-14 奥斯瓦道·克鲁兹基金会 二苯氧基烷基胺衍生物及其药物组合物
US20210120817A1 (en) * 2017-03-17 2021-04-29 Meiji Seika Pharma Co., Ltd. Plant disease control agent
CN111741944A (zh) * 2018-02-01 2020-10-02 悉尼大学 抗癌化合物
US11939296B2 (en) 2018-02-01 2024-03-26 The University Of Sydney Anti-cancer compounds
US11207288B2 (en) 2018-07-31 2021-12-28 Microbion Corporation Bismuth-thiol compositions and methods for treating wounds
US11464749B2 (en) 2018-07-31 2022-10-11 Microbion Corporation Bismuth-thiol compositions and methods of use
US11974978B2 (en) 2018-07-31 2024-05-07 Microbion Corporation Bismuth-thiol compositions and methods for treating wounds
US20220280476A1 (en) * 2019-05-03 2022-09-08 Praxis Precision Medicines, Inc. Kcnt1 inhibitors and methods of use

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