WO2001064644A1 - Dichloropyridyl- and dichloroisothiazolyl-thiocarboxamides and their use as microbicides - Google Patents

Dichloropyridyl- and dichloroisothiazolyl-thiocarboxamides and their use as 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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French (fr)
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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/en

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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.

Abstract

Thiocarboxamides of the formula (I) in which Z represents a groupof formula (II) or (III) and R represents specified groups, 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.

Description

DICHLOROPYRIDYL- AND DICHLOROISOTHIAZOLYL-THIOCARBOXAMIDES AND THEIR USE AS MICROBICIDES
The present invention relates to novel thiocarboxamides, to a process for their preparation and to their use as microbicides.
It has already been known that certain isothiazolecarboxamides can be employed for the control of fungi (see JP-A 149 572-1990, JP-A 59 024-1993, JP-A 9313-1994 and WO 99-24 413). Further, it has also been described that various 4-pyridinecarb- oxylic acid amides are suitable for combating fungi and for causing resistance in plants against plant pathogens (see JP-A 130 583-1988, JP-A 501 325-1995, JP-A
283 284-1989, JP-A 208 615-1996, JP-A 165 374-1997 and JP-A 249 648-1997). The fungicidal activity of such known compounds, however, it is not always satisfactory.
There have now been found novel thiocarboxamides of the formula
S Z-C NH R W in which Z represents a group of the formula
Figure imgf000002_0001
R represents C g alkyl, Cj_4 haloalkyl, C^ alkoxy-Cι.3 alkyl, C1.4 alkylthio- Cι_3 alkyl, optionally substituted C3.6 cycloalkyl, optionally substituted aralkyl, optionally substituted phenoxyalkyl, optionally substituted phenylthioalkyl, optionally substituted phenyl or a group selected from
Figure imgf000003_0001
wherein
R1 represents C^alkyl,
R2 represents hydrogen, halogen, Cj_4 alkyl or C^alkoxy and
R3 represents hydrogen, halogen, C1.4 alkyl or Cj_4 alkoxy.
Further, it has been found that thiocarboxamides of the formula (I) can be prepared by
a) reacting carboxamides of the formula
O
II z— c- -NH- (II)
in which
R and Z have the above-mentioned meanings,
with phosphorous pentasulfide in the presence of an inert diluent.
Finally, it has been found that 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. Surprisingly, 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.
In the present context, Cι.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 CM alkyl part in CM haloalkyl, C alkoxy-Cι-3 alkyl, C alkylthio-Cι-3 alkyl, CM alkoxy and CM 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 Cι-3 alkyl part in CM alkoxy-Cι_ alkyl and CM alkylthio-C1-3 alkyl can be linear or branched, and to be specific, it represents methyl, ethyl, n-propyl or isopropyl.
CM alkoxy and a CM alkoxy part in C1-4 alkoxy-Cι-3 alkyl are C alkyl-O- in which C1-4 alkyl has the significance as described above, i.e., they include methoxy, ethoxy, n-propoxy, isopropoxy or n-, iso-, sec- or tert-butoxy.
CM alkylthio and a CM alkylthio part in CM alkylthio-C1-3 alkyl are C alkyl-S- in which CM 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.
To be specific, fluorine, chlorine, bromine and iodine are included in a halogen part of halogen and CM haloalkyl.
C3_6 cycloalkyl represents, to be specific, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Aralkyl is aryl-substituted alkyl and, to be specific, includes phenyl-Cι- 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.
To be specific, phenoxy-Cj^-alkyl includes, for example, 2-phenoxy ethyl, 1-methyl- 2-phenoxyethyl and l-ethyl-2-phenoxyethyl.
To be specific, phenylthio-Cj.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 Cj.g alkyl, haloalkyl having 1 to 3 carbon atoms and 1 to 5 halogen atoms, Cj_4 alkoxy-C2_3 alkyl, C1.4 alkylthio-C2_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
or
R represents 1,3-diphenylpropan-l-yl or l-(4-fluorophenyl)-3-phenylpropan-l- yl, or
R represents a group selected from
Figure imgf000006_0001
wherein
R1 represents C1.3 alkyl, R2 represents hydrogen, chlorine, methyl or methoxy and R3 represents hydrogen, chlorine, methyl or methoxy
and
Z represents a group of the formula
Figure imgf000007_0001
Particularly preferred are the compounds of the formula (I), in which
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
Figure imgf000008_0001
in which
R1 represents methyl, ethyl, n-propyl or isopropyl, R2 represents hydrogen, or chlorine , methyl or methoxy at the 5 -position or 6- position and
R3 represents hydrogen, or chlorine, methyl or methoxy at the 5-position or 6- position,
and
represents a group of the formula
Figure imgf000009_0001
Depending on the definition of R, the thiocarboxamides of the formula (I) according to the invention may comprise an asymmetrically substituted carbon atom. Thus, the compounds of the formula (I) may be present as (R)- or (S)-enantiomers having optical activity.
If N-(α-methyl-benzyl)-2,6-dichloro-isonicotinic acid amide and phosphorous penta- sulfide are used as starting materials, process (a) according to the invention can be illustrated by the following formula scheme:
Figure imgf000009_0002
Formula (II) provides a general definition of the carboxamides, which are required as starting materials for conducting process (a) according to the invention. In this formula R and Z preferably have those meanings, which have already been mentioned as preferred for these substituents.
The following compounds may be mentioned as examples of carboxamides of the formula (II).
N-(α-methylbenzyl)-2,6-dichloroisonicotinic acid amide, N-(3-fluoro-α-methylbenzyl)-2,6-dichloroisonicotinic acid amide, N-(4-bromo-α-methylbenzyl)-2,6-dichloroisonicotinic acid amide.
N-(4-difluoromethoxy-α-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-[3-(3'-methylphenyl)-l-ethylpropyl]-2,6-dichloroisonicotinic acid amide, N-(l,3-diphenylpropyl)-2,6-dichloroisonicotinic acid amide, N-[2-(4'-methylphenylthio)isopropyl]-2,6-dichloroisonicotinic acid amide, N-[2-(3'-fluorophenoxy)isopropyl]-2,6-dichloroisonicotinic acid amide, N-(α-methylbenzyl)-3,4-dichloroisothiazole-5-carboxylic 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,
N- (3,4-dimethoxyphenethyl)-3,4-dichloroisothiazole-5-carboxylic acid amide, N-[2-(3 '-ethylphenoxy)isopropyl]-3,4-dichloroisothiazole-5-carboxylic acid amide, N-[2-(4'-fluorophenoxy)isopropyl]-3,4-dichloroisothiazole-5-carboxylic acid amide, N- [2-(4 ' -methylphenylthio)isopropyl] -3 ,4-dichloroisothiazole-5 -carboxylic acid amide, and
N-[2-(3 ,-fluorophenylthio)isopropyl]-3,4-dichloroisothiazole-5-carboxylic acid amide. The carboxamides of the formula (II) are known or can be prepared by principally known processes. Thus, compounds of the formula (II) can be prepared by
b) reacting carbonyl chlorides of the formula
O
II z-c— Cl (III)
in which
Z has the above-mentioned meanings,
with amines of the formula
Figure imgf000011_0001
in which
R has the above-mentioned meanings,
in the presence of an inert diluent and, if appropriate, in the presence of an acid- binding agent.
Formula (III) provides a general definition of the carbonylchlorides, which are required as starting materials for conducting process (b). In this formula, Z represents a group of the formula
Figure imgf000012_0001
Thus, formula (III) includes 3,4-dichloro-5-isothiazolecarbonyl chloride and
2,6-dichloroisonicotinic acid chloride.
The compounds of the formula (III) are already known (see JP-A 59 024-1993 and JP-A 283 284-1989).
Formula (IV) provides a general definition of the amines, which are required as reaction components for conducting process (b). In this formula, R preferably has those meanings, which have already been mentioned as preferred for this substituent.
The following compounds may be mentioned as examples of amines of the formula (IN).
α-methy lb enzy lamine,
3 -fluoro-α-methy lbenzylamine,
4-bromo-α-methylbenzy lamine, 4-difluoromethoxy-α-methylbenzylamine,
4-trifluoromethoxy-α-methylbenzylamine,
3-(3 ' -methoxyphenyl)- 1 -methylpropylamine,
3-(3'-ethylphenyl)-l-ethylpropylamine,
1 ,3-diphenylpropylamine, -(3 '-fluorophenyl)- 1 -ethylpropylamine, -(3'-ethylphenoxy)isopropylamine, -(4'-methylphenoxy)isopropylamine, -(3'-fluorophenoxy)isopropylamine, 2-(4-methylphenylthio)isopropylamine, and 3 -(3 -fluoropheny lthio)isopropylamine .
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
146 876-1988).
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 isopropyl ketone and methyl isobutyl ketone (MEBK); nitriles such as acetonitrile, propionitrile and acrylonitrile; acid amines such as dimethylformamide (DMF), dimethylacetamide (DMA), N-methyl- pyrrolidone, l,3-dimethyl-2-imidazolidinone and hexamethylphosphoric triamide (HMPA); sulfones, sulfoxides such as dimethylsulfoxide (DMSO), and sulfolanes.
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]-undecane-7-ene (DBU).
When carrying out process (b), the 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.
When carrying out process (b), in general 1 mole of a carbonyl chloride of the formula (III) is reacted with 0.8 to 1.5 moles of an amine of the formula (IV) in the presence of a diluent, such as tetrahydrofuran, and in the presence of 1 to 4 moles of an acid-binding agent, such as triethy lamine.
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.
When carrying out process (a) according to the invention, the 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
60°C and about 170°C.
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. When carrying out 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.
Generally, 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.
These 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. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As 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.
By liquefied gaseous diluents or carriers are meant 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.
As solid carriers there may be used ground natural minerals, such as kaolings, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for granules there may be used 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.
As emulsifying and/or foam-forming agents there may be used 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.
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.
In many cases, synergistic effects are achieved, i.e. the activity of the mixture exceeds the activity of the individual components.
Examples of co-components in mixtures are the following compounds:
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, cyprofuram, carpropamide, debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, drazoxolon, edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole, famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fiumetover, fluoromide, fluquinconazole, flurprimidol, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium. fosetyl-sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole- cis, furmecyclox, fenhexamide, guazatine, hexachlorobenzene, hexaconazole, hymexazole, imazalil, imibenconazole, iminoctadine, iminoctadine albesilate, iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP), iprodione, irumamycin, isoprothiolane, isovaledione, iprovalicarb, kasugamycin, kresoxim-methyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture, mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram, metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim, oxyfenthiin, paclobutrazole, pefiirazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidone, propamocarb, propanosine-sodium, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, quinconazole, quintozene (PCNB), quinoxyfen, sulphur and sulphur preparations, spiroxamine, tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole, thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram, tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, trifloxystrobin, uniconazole, validamycin A, vinclozolin, viniconazole, zarilamide, zineb, ziram and also
Dagger G,
OK-8705,
OK-8801, α-(l,l-dimethylethyl)-β-(2-phenoxyethyl)-lH-l,2,4-triazole-l -ethanol, α-(2,4-dichlorophenyl)-β-fluoro-β-propyl-lH-l,2,4-triazole-l -ethanol, α-(2,4-dichlorophenyl)- β -methoxy-α-methyl- 1 H- 1 ,2 ,4-triazole- 1 -ethanol, α-(5-methyl-l,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-lH-l,2,4- triazole- 1 -ethanol,
(5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(lH-l,2,4-triazol-l-yl)-3-octanone, (E)-α-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,
1 -(2,4-dichlorophenyl)-2-( IH- 1 ,2,4-triazol- 1 -yl)-ethanone O-(phenylmethyl)-oxime,
1 -(2 -methyl- 1 -naphthalenyl)-lH-pyrrol-2,5-dione, l-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione, l-[(diiodomethyl)-sulphonyl]-4-methyl-benzene, l-[[2-(2,4-dichlorophenyl)-l,3-dioxolan-2-yl]-methyl]-lH-imidazole, l-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-lH-l,2,4-triazole, l-[l-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-lH-imidazole, l-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinole,
2 ' ,6 ' -dibromo-2-methyl-4 ' -trifluoromethoxy-4 ' -trifluoro-methyl- 1 ,3-thiazole-5- carboxanilide,
2,6-dichloro-5-(methylthio)-4-pyrimidinyl thiocyanate,
2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,
2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,
2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole, 2-[(l-methylethyl)-sulphonyl]-5-(trichloromethyl)-l,3,4-thiadiazole, 2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-α-D-glucopyranosyl]-amino]-4- methoxy- 1 H-pyrrolo [2,3-d]pyrimidine-5 -carbonitrile,
2-aminobutane,
2-bromo-2-(bromomethyl)-pentanedinitrile, 2-chloro-N-(2,3-dihydro-l,l,3-trimethyl-lH-inden-4-yl)-3-pyridinecarboxamide,
2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,
2-phenylphenol (OPP),
3,4-dichloro-l-[4-(difluoromethoxy)-phenyl]-lH-pyrrol-2,5-dione,
3,5-dichloro-N-[cyano[(l-methyl-2-propinyl)-oxy]-methyl]-benzamide, 3-( 1 , 1 -dimethylpropyl- 1 -oxo- 1 H-indene-2-carbonitrile,
3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,
4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-lH-imidazole-l-sulphonamide,
4-methyl-tetrazolo[ 1 ,5-a]quinazolin-5(4H)-one,
8-hydroxyquinoline sulphate, 9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide, bis-(l-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy] 2,5-thiophenedicarboxylate, cis- 1 -(4-chlorophenyl)-2-( 1 H- 1 ,2,4-triazol- 1 -yl)-cycloheptanol, cis-4-[3-[4-(l,l-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl- morpholinehydrochloride, ethyl [(4-chlorophenyl)-azo]-cyanoacetate, potassium hydrogen carbonate, methanetetrathiol sodium salt, methyl 1 -(2,3-dihydro-2,2-dimethyl- 1 H-inden-1 -yl)- 1 H-imidazole-5-carboxylate, methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate, methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,
N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,
N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,
N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide,
N-(4-cyclohexylphenyl)-l,4,5,6-tetrahydro-2-pyrimidineamine, N-(4-hexylphenyl)-l,4,5,6-tetrahydro-2-pyrimidineamine,
N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide, N-(6-methoxy)-3-pyridinyl)-cyclopropanecarboxamide, N-[2,2,2-trichloro-l-[(chloroacetyl)-amino]-ethyl]-benzamide, N-[3-chloro-4,5-bis(2-propinyloxy)-phenyl]-N'-methoxy-methanimidamide, N-formyl-N-hydroxy-DL-alanine-sodium salt, O,O-diethyl [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,
O-methyl S-phenyl phenylpropylphosphoramidothioate, S-methyl 1 ,2,3-benzothiadiazole-7-carbothioate, spiro[2H]-l-benzopyran-2, (3'H)-isobenzofuran]-3'-one,
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 popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, baculoviruses, Beauveria bassiana, Beauveria tenella, bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin, bifenazate, bifenthrin, bioethanomethrin, biopermethrin, BPMC, bromophos A, bufencarb, buprofezin, butathiofos, butocarboxim, butylpyridaben, cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, chlovaporthrin, cis-resmethrin, cispermethrin, clocythrin, cloethocarb, clofentezine, cyanophos, cycloprene, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron, diazinon, dichlorvos, diflubenzuron, dimethoat, dimethylvinphos, diofenolan, disulfoton, docusat-sodium, dofenapyn, eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthora spp., esfenvalerate, ethiofencarb, ethion, ethoprophos, etofenprox, etoxazole, etrimphos, fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fenvalerate, fipronil, fluazuron, flubrocythrinate, flucycloxuron, flucythrinate, flufenoxuron, flutenzine, fluvalinate, fonophos, fosmethilan, fosthiazate, fubfenprox, furathiocarb, granulosis viruses, halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox, hydroprene, imidacloprid, isazophos, isofenphos, isoxathion, ivermectin, lambda-cyhalothrin, lufenuron, malathion, mecarbam, metaldehyde, methamidophos, Metharhizium anisopliae, Metharhizium flavoviride, methidathion, methiocarb, methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos, milbemectin, monocrotophos, naled, nitenpyram, nithiazine, novaluron, nuclear polyhedrosis viruses, omethoat, oxamyl, oxydemethon M,
Paecilomyces fumosoroseus, parathion A, parathion M, permethrin, phenthoat, phorat, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos A, pirimiphos M, profenofos, promecarb, propoxur, prothiofos, prothoat, pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben, pyridathion, pyrimidifen, pyriproxyfen, quinalphos, ribavirin, salithion, sebufos, silafluofen, spinosad, sulfotep, sulprofos, tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, temivinphos, terbufos, tetrachlorvmphos, theta-cypermethrin, thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thuringiensin, tralocythrin, tralomethrin, triarathene, triazamate, triazophos, triazuron, trichlophenidine, trichlorfon, triflumuron, trimethacarb, thiacloprid, vamidothion, vaniliprole, Verticillium lecanii,
YI 5302, zeta-cypermethrin, zolaprofos,
(lR-cis)-[5-(phenylmethyl)-3-furanyl]-methyl-3-[(dihydro-2-oxo-3(2H)- furanylidene)-methyl] 2,2-dimethylcyclopropanecarboxylate, (3-phenoxyphenyl)-methyl 2,2,3,3-tetramethylcyclopropanecarboxylate, l-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-l,3,5-triazine-
2(lH)-imine,
2-(2-chloro-6-fluorophenyl)-4-[4-(l,l-dimethylethyl)phenyl]-4,5-dihydro-oxazole,
2-(acetyloxy)-3-dodecyl- 1 ,4-naphthalenedione, 2-chloro-N- [ [ [4-( 1 -phenyl ethoxy)-phenyl]-amino] -carbonyl] -benzamide,
2-chloro-N-[[[4-(2,2-dichloro- 1 , 1 -difluoroethoxy)-phenyl] -amino] -carbonyl] - benzamide,
3-methylphenyl propylcarbamate
4-[4-(4-ethoxyphenyl)-4-methylpentyl]-l-fluoro-2-phenoxy-benzene, 4-chloro-2-(l,l-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-
3(2H)-pyridazinone,
4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyri- dazinone,
4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyri- dazinone,
Bacillus thuringiensis strain EG-2348,
[2-benzoyl- 1 -( 1 , 1 -dimethylethyl)-hydrazinobenzoic acid,
2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-l-oxaspiro[4.5]dec-3-en-4-yl butanoate,
[3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide, dihydro-2-(nitromethylene)-2H-l,3-thiazine-3(4H)-carboxaldehyde, ethyl [2-[[l,6-dihydro-6-oxo-l-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate,
N-(3 ,4,4-trifluoro- 1 -oxo-3 -butenyl)-glycine,
N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-lH-pyra- zole- 1 -carboxamide, N-[(2-chloro-5-thiazolyl)methyl]-N'-methyl-N"-nitro-guanidine,
N-methyl-N'-( 1 -methyl-2-propenyl)- 1 ,2-hydrazinedicarbothioamide, N-m ethyl -N'-2-propenyl- 1 ,2-hydrazinedicarbothioamide,
O,O-diethyl [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate.
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.
In the treatment of parts of plants, 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%.
For the treatment of seed, amounts of active compound of 0.001 to 50 g, especially
0.01 to 10 g, are generally employed per kilogram of seed.
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.
As already mentioned above, all plants and parts of plants can be treated according to the invention. In a preferred embodiment 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. In an additional preferred embodiment 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.
According to the invention 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.
Depending on the species or varieties of plants, their location and growth conditions
(the types of soil, climate, vegetation period and feed concerned), superadditive ("synergistic") 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"). Examples of such properties 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. 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 ("traits") 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 refeπed to as "Bt plants") by the genetic material obtained from Bacillus Thuringiensis (e.g. by the genes CrylA(a), CrylA(b),
CrylA(c), CryllA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF and combinations thereof). Particularly significant properties ("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. Particulary significant properties ("traits") 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). The corresponding genes imparting the required properties ("traits") can also occur in the transgenic plants in combination with each other. Examples which may be mentioned of "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). Examples which may be mentioned of 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),
Liberty Link® (tolerance of phosphinotricine, e.g. rape), IMI® (tolerance of imidazolinones) and STS® (tolerance of sulphonylureas, e.g. corn). Herbicide- resistant plants (bred for herbicide tolerance in the conventional manner) which may be mentioned are also the varieties (e.g. com) sold under the name Clearfield®. The above statements do of course also apply to any plant varieties which may be developed in the future or launched onto the market in the future and which have the genetic properties ("traits") described above or developed in the future.
According to the invention 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.
Then the present invention will be described more specifically by the following examples. However, the present invention should not be restricted to them in any way.
Examples
Synthesis Example 1
Figure imgf000029_0001
(Compound No. 394)
A suspension of 0.8 g (2.71 mmol) of N-(α-methylbenzyl)-2,6-dichloroisonicotinic acid amide and 0.6 g (2.71 mmol) of phosphorous pentasulfide in 30 ml of toluene was refluxed for 6 hours by heating. After cooling to room temperature, the precipitate was filtered off and toluene was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.54 g of N-(α- methylbenzyl)-2,6-dichloroisonicotinic acid thioamide. Mp: 93 to 96°C, yield: 64%.
The compounds obtained in the same manner as in Synthesis Example 1 are shown in Tables 1 to 4 together with the compound synthesized in Synthesis Example 1.
In the following Tables,
A represents:
and B represents:
Figure imgf000029_0002
Me represents methyl; Et represents ethyl; Pr represents propyl; Bu represents butyl; Pen represents pentyl; cy-Pr represents cyclopropyl; cy-Hex represents cyclohexyl;
Ph represents phenyl; (R) represents an optical isomer of the R configuration; and (S) represents an optical isomer of the S configuration. Table 1
S
I I Z- C— NH — R
(I)
ComMp (°C) pound No. Z R or n
1 A Me
2 A Et 80-82
3 A n-Pr
4 A iso-Pr
5 A n-Bu
6 A sec-Bu
7 A iso-Bu
8 A t-Bu
9 A n-Pen
10 A FCH2CH2
11 A C1CH2CH2
12 A BrCH2CH2
13 A CF3CH2
14 A C1CH2CH2CH2
15 A BrCH2CH2CH2
16 A MeOCH2CH2
17 A EtOCH2CH2
18 A MeOCH2CH2CH2
19 A EtOCH2CH2CH2 0 A iso-PrOCH2CH2CH2 1 A n-BuOCH2CH2CH2 2 A MeSCH2CH2 ComMp (°C) pound No. Z R or nβ
23 A EtSCH2CH2
24 A MeSCH2CH2CH2
25 A EtSCH2CH2CH2
26 A cy-Pr
27 A cy-Pen
28 A cy-Hex
29 A 2-Me-cy-Hex
30 A PhCH2
31 A 3-F-PhCH2
32 A 4-F-PhCH2 128-129
33 A 2-Cl-PhCH2
34 A 4-Br-PhCH2 5 A 2-Me-PhCH2
36 A 4-Et-PhCH2 7 A 4-n-Pr-PhCH2 8 A 4-iso-Pr-PhCH2 9 A 4-tert-Bu-PhCH2 0 A 4-CF3-PhCH2 1 A 3-MeO-PhCH2 95-96 2 A 4-EtO-PhCH2 3 A 4-CF3O-PhCH2 4 A 4-CF2HO-PhCH2 5 A 4-MeS-PhCH2 6 A 4-EtS-PhCH2 7 A 4-CF3S-PhCH2 8 A 4-Ph-PhCH2 9 A 4-PhO-PhCH2 ComMp (°C) pound
No. Z R or n
50 A 4-NO2-PhCH2
51 A 2,4-diF-PhCH2
52 A 3,4-diCl-PhCH2
53 A 2,3-diMe-PhCH2
54 A 3,4-diMeO-PhCH2 109-111
55 A 2,4,6-tri-Me-PhCH2
56 A PhCH(Me) 1.6625
57 A 3-F-PhCH(Me)
58 A 4-F-PhCH(Me)
59 A 2-Cl-PhCH(Me)
60 A 4-Br-PhCH(Me) 1 A 2-Me-PhCH(Me) 2 A 4-Et-PhCH(Me) 3 A 4-n-Pr-PhCH(Me) 4 A 4-iso-Pr-PhCH(Me) 5 A 4-tert-Bu-PhCH(Me) 6 A 4-CF3-PhCH(Me) 7 A 3-MeO-PhCH(Me) 8 A 4-EtO-PhCH(Me) 9 A 4-CF3O-PhCH(Me) 1.5890 0 A 4-CF2HO-PhCH(Me) 1 A 4-MeS-PhCH(Me) 2 A 4-CF3S-PhCH(Me) 3 A 4-Ph-PhCH(Me) 4 A 4-PhO-PhCH(Me) 5 A 4-NO2-PhCH(Me) 6 A 2,4-diF-PhCH(Me) 7 A 3,4-diCl-PhCH(Me) ComMp (°C) pound
No. Z R or nj)
78 A 2,3-diMe-PhCH(Me)
79 A 3,4-diMeO-PhCH(Me)
80 A 2,4,6-tri-Me-PhCH(Me)
81 A PhCH(Et)
82 A 2-F-PhCH(Et)
83 A 3-Cl-PhCH(Et)
84 A 2-Me-PhCH(Et)
85 A 4-MeO-PhCH(Et)
86 A 3-CF3-PhCH(Et)
87 A PhCH(n-Pr)
88 A 2-F-PhCH(n-Pr)
89 A 3-Cl-PhCH(n-Pr)
90 A 2-Me-PhCH(n-Pr)
91 A 4-MeO-PhCH(n-Pr)
92 A 3-CF3-PhCH(n-Pr)
93 A PhCH(iso-Pr)
94 A 4-Cl-PhCH(iso-Pr)
95 A 4-Me-PhCH(iso-Pr)
96 A PhCH2CH2 89-90
97 A 4-F-PhCH2CH2
98 A 2-Cl-PhCH2CH2
99 A 4-Br-PhCH2CH2
100 A 2-Me-PhCH2CH2
101 A 4-Et-PhCH2CH2
102 A 4-n-Pr-PhCH2CH2
103 A 4-iso-Pr-PhCH2CH2
104 A 4-tert-Bu-PhCH2CH2
105 A 4-CF3-PhCH2CH2 ComMp (°C) pound
No. Z R or n
106 A 3-MeO-PhCH2CH2
107 A 4-EtO-PhCH2CH2
108 A 4-CF3O-PhCH2CH2
109 A 4-CF2HO-PhCH2CH2
110 A 4-MeS-PhCH2CH2
111 A 4-EtS-PhCH2CH2
112 A 4-CF3S-PhCH2CH2
113 A 4-Ph-PhCH2CH2
114 A 4-PhO-PhCH2CH2
115 A 4-NO2-PhCH2CH2
116 A 2,4-diF-PhCH2CH2
117 A 3,4-diCl-PhCH2CH2
118 A 2,3-diMe-PhCH2CH2
119 A 3,4-diMeO-PhCH2CH2 98-99
120 A 2,4,6-tri-Me-PhCH2CH2
121 A PhCH2CH(Me)
122 A 3-F-PhCH2CH(Me)
123 A 4-Cl-PhCH2CH(Me)
124 A 2-Me-PhCH2CH(Me)
125 A 3-MeO-PhCH2CH(Me)
126 A 3 ,4-diMeO-PhCH2CH(Me)
127 A PhCH2C(Me)2
128 A PhCH2CH(Et)
129 A 4-F-PhCH2CH(Et)
130 A 3-Cl-PhCH2CH(Et)
131 A 4-MeO-PhCH2CH(Et)
132 A PhCH2CH2CH2
133 A 3-F-PhCH2CH2CH2 ComMp (°C) pound
Figure imgf000035_0001
134 A 4-F-PhCH2CH2CH2
135 A 2-Cl-PhCH2CH2CH2
136 A 4-Br-PhCH2CH2CH2
137 A 2-Me-PhCH2CH2CH2
138 A 4-Et-PhCH2CH2CH2
139 A 4-n-Pr-PhCH2CH2CH2
140 A 4-iso-Pr-PhCH2CH2CH2
141 A 4-tert-Bu-PhCH2CH2CH2
142 A 4-CF3-PhCH2CH2CH2
143 A 3-MeO-PhCH2CH2CH2
144 A 4-EtO-PhCH2CH2CH2
145 A 4-CF3O-PhCH2CH2CH2
146 A 4-CF2HO-PhCH2CH2CH2
147 A 4-MeS-PhCH2CH2CH2
148 A 4-EtS-PhCH2CH2CH2
149 A 4-CF3S-PhCH2CH2CH2
150 A 4-Ph-PhCH2CH2CH2
151 A 4-PhO-PhCH2CH2CH2
152 A 4-NO2-PhCH2CH2CH2
153 A 2,4-diF-PhCH2CH2CH2
154 A 3,4-diCl-PhCH2CH2CH2
155 A 2,3-diMe-PhCH2CH2CH2
156 A 3 ,4-diMeO-PhCH2CH2CH2
157 A 2,4,6-tri-Me-PhCH2CH2CH2
158 A PhCH2CH2CH(Me)
159 A 3-F-PhCH2CH2CH(Me)
160 A 4-F-PhCH2CH2CH(Me)
161 A 2-Cl-PhCH2CH2CH(Me) ComMp (°C) pound
No. Z R orng.
162 A 4-Br-PhCH2CH2CH(Me)
163 A 2-Me-PhCH2CH2CH(Me)
164 A 4-Et-PhCH2CH2CH(Me)
165 A 4-CF3-PhCH2CH2CH(Me)
166 A 2-MeO-PhCH2CH2CH(Me) 1.6212
167 A 4-EtO-PhCH2CH2CH(Me)
168 A 4-CF3O-PhCH2CH2CH(Me)
169 A 4-CF2HO-PhCH2CH2CH(Me)
170 A 4-MeS-PhCH2CH2CH(Me)
171 A 4-EtS-PhCH2CH2CH(Me)
172 A 4-CF3S-PhCH2CH2CH(Me)
173 A 4-Ph-PhCH2CH2CH(Me)
174 A 4-PhO-PhCH2CH2CH(Me)
175 A 4-NO2-PhCH2CH2CH(Me)
176 A 2,4-diF-PhCH2CH2CH(Me)
177 A 3,4-diCl-PhCH2CH2CH(Me)
178 A 2,3-diMe-PhCH2CH2CH(Me)
179 A 3,4-diMeO-PhCH2CH2CH(Me)
180 A PhCH2CH2CH(Et)
181 A 3-F-PhCH2CH2CH(Et) 1.6163
182 A 4-F-PhCH2CH2CH(Et)
183 A 4-Cl-PhCH2CH2CH(Et)
184 A 2-Me-PhCH2CH2CH(Et)
185 A 3-MeO-PhCH2CH2CH(Et)
186 A 4-CF3O-PhCH2CH2CH(Et)
187 A PhCH2CH2CH(n-Pr)
188 A 4-F-PhCH2CH2CH(n-Pr)
189 A 4-MeO-PhCH2CH2CH(n-Pr) ComMp (°C) pound
Figure imgf000037_0001
190 A PhCH CH2CH(iso-Pr)
191 A 3-F-PhCH2CH2CH(iso-Pr)
192 A 3-Me-PhCH2CH2CH(iso-Pr)
193 A PhCH2CH2CH(n-Bu)
194 A 4-MeO-PhCH2CH2CH(n-Bu)
119955 AA 4-CF3O-PhCH2CH2CH(n-Bu)
196 A PhCH2CH2CH(Ph) 1.6548
197 A 4-F-PhCH2CH2CH(Ph)
198 A PhOCH2CH2
199 A 3-F-PhOCH2CH2
220000 AA 4-F-PhOCH2CH2
201 A 2-Cl-PhOCH2CH2
202 A 4-Br-PhOCH2CH2
203 A 2-Me-PhOCH2CH2
204 A 4-Et-PhOCH2CH2
220055 AA 4-n-Pr-PhOCH2CH2
206 A 4-iso-Pr-PhOCH2CH2
207 A 4-tert-Bu-PhOCH2CH2
208 A 4-CF3-PhOCH2CH2
209 A 3-MeO-PhOCH2CH2
221100 AA 4-EtO-PhOCH2CH2
211 A 4-CF3O-PhOCH2CH2
212 A 4-CF2HO-PhOCH2CH2
213 A 4-MeS-PhOCH2CH2
214 A 4-EtS-PhOCH2CH2
221155 AA 4-CF3S-PhOCH2CH2
216 A 4-Ph-PhOCH2CH2
217 A 4-PhO-PhOCH2CH2
Figure imgf000038_0001
218 A 4-NO2-PhOCH2CH2
219 A 2,4-diF-PhOCH2CH2
220 A 3,4-diCl-PhOCH2CH2
221 A 2,3-diMe-PhOCH2CH2
222 A 3,4-diMeO-PhOCH2CH2
223 A 2,4,6-tri-Me-PhOCH2CH2
224 A PhOCH2CH(Me)
225 A 3-F-PhOCH2CH(Me) 1.6265
226 A 4-F-PhOCH2CH(Me)
227 A 2-Cl-PhOCH2CH(Me)
228 A 4-Br-PhOCH2CH(Me)
229 A 2-Me-PhOCH2CH(Me)
230 A 3-Me-PhOCH2CH(Me) 1.6283
231 A 3-Et-PhOCH2CH(Me) 1.6211
232 A 4-Et-PhOCH2CH(Me)
233 A 4-CF3-PhOCH2CH(Me)
234 A 3-MeO-PhOCH2CH(Me)
235 A 4-EtO-PhOCH2CH(Me)
236 A 4-CF3O-PhOCH2CH(Me)
237 A 4-CF2HO-PhOCH2CH(Me)
238 A 4-MeS-PhOCH2CH(Me)
239 A 4-EtS-PhOCH2CH(Me)
240 A 4-CF3S-PhOCH2CH(Me)
241 A 4-Ph-PhOCH2CH(Me)
242 A 4-PhO-PhOCH2CH(Me)
243 A 4-NO2-PhOCH2CH(Me)
244 A 2,4-diF-PhOCH2CH(Me) )
Figure imgf000039_0001
245 A 3,4-diCl-PhOCH2CH(Me)
246 A 2,3-diMe-PhOCH2CH(Me)
247 A 3,4-diMeO-PhOCH2CH(Me)
248 A PhOCH2CH(Et)
249 A 3-F-PhOCH2CH(Et)
250 A 4-F-PhOCH2CH(Et)
251 A 4-Cl-PhOCH2CH(Et)
252 A 2-Me-PhOCH2CH(Et)
253 A 3-MeO-PhOCH2CH(Et)
254 A 4-CF3O-PhOCH2CH(Et)
255 A PhSCH2CH2
256 A 3-F-PhSCH2CH2
257 A 4-F-PhSCH2CH2
258 A 2-Cl-PhSCH2CH2
259 A 4-Br-PhSCH2CH2
260 A 2-Me-PhSCH2CH2
261 A 4-Et-PhSCH2CH2
262 A 4-n-Pr-PhSCH2CH2
263 A 4-iso-Pr-PhSCH2CH2
264 A 4-tert-Bu-PhSCH2CH2
265 A 4-CF3-PhSCH2CH2
266 A 3-MeO-PhSCH2CH2
267 A 4-EtO-PhSCH2CH2
268 A 4-CF3O-PhSCH2CH2
269 A 4-CF2HO-PhSCH2CH2
270 A 4-MeS-PhSCH2CH2
271 A 4-EtS-PhSCH2CH2
272 A 4-CF3S-PhSCH2CH2 ComMp (°C)
Figure imgf000040_0001
273 A 4-Ph-PhSCH2CH2
274 A 4-PhO-PhSCH2CH2
275 A 4-NO2-PhSCH2CH2
276 A 2,4-diF-PhSCH2CH2
277 A 3,4-diCl-PhSCH2CH2
278 A 2,3-diMe-PhSCH2CH2
279 A 3,4-diMeO-PhSCH2CH2
280 A 2,4,6-tri-Me-PhSCH2CH2
281 A PhSCH2CH(Me)
282 A 3-F-PhSCH2CH(Me)
283 A 4-F-PhSCH2CH(Me)
284 A 2-Cl-PhSCH2CH(Me)
285 A 4-Br-PhSCH2CH(Me)
286 A 2-Me-PhSCH2CH(Me)
287 A 3-Me-PhSCH2CH(Me)
288 A 3-Et-PhSCH2CH(Me)
289 A 4-Et-PhSCH2CH(Me)
290 A 4-CF3-PhSCH2CH(Me)
291 A 3-MeO-PhSCH2CH(Me)
292 A 4-EtO-PhSCH2CH(Me)
293 A 4-CF3O-PhSCH2CH(Me)
294 A 4-CF2HO-PhSCH2CH(Me)
295 A 4-MeS-PhSCH2CH(Me)
296 A 4-EtS-PhSCH2CH(Me)
297 A 4-CF3S-PhSCH2CH(Me)
298 A 4-Ph-PhSCH2CH(Me)
299 A 4-PhO-PhSCH2CH(Me)
300 A 4-NO2-PhSCH2CH(Me) )
Figure imgf000041_0001
301 A 2,4-diF-PhSCH2CH(Me)
302 A 3,4-diCl-PhSCH2CH(Me)
303 A 2,3-diMe-PhSCH2CH(Me)
304 A 3 ,4-diMeO-PhSCH2CH(Me)
305 A PhSCH2CH(Et)
306 A 3-F-PhSCH2CH(Et)
307 A 4-F-PhSCH2CH(Et)
308 A 4-Cl-PhSCH2CH(Et)
309 A 2-Me-PhSCH2CH(Et)
310 A 3-MeO-PhSCH2CH(Et)
311 A 4-CF3O-PhSCH2CH(Et)
312 A Ph
313 A 3-F-Ph
314 A 4-F-Ph
315 A 2-Cl-Ph
316 A 4-Br-Ph
317 A 2-Me-Ph
318 A 4-Et-Ph
319 A 4-n-Pr-Ph
320 A 4-iso-Pr-Ph
321 A 4-tert-Bu-Ph
322 A 4-CF3-Ph
323 A 3-MeO-Ph
324 A 4-EtO-Ph
325 A 4-CF3O-Ph
326 A 4-CF2HO-Ph
327 A 4-MeS-Ph )
Figure imgf000042_0001
328 A 4-EtS-Ph
329 A 4-CF3S-Ph
330 A 4-Ph-Ph
331 A 4-PhO-Ph
332 A 4-NO2-Ph
333 A 2,4-diF-Ph
334 A 3,4-diCl-Ph
335 A 2,3-diMe-Ph
336 A 3,4-diMeO-Ph
Figure imgf000042_0002
338 B Me
339 B Et
340 B n-Pr
341 B iso-Pr
342 B n-Bu
343 B sec-Bu
344 B iso-Bu
345 B t-Bu
346 B n-Pen
347 B FCH2CH2
348 B C1CH2CH2
349 B BrCH2CH2
350 B CF3CH2
351 B C1CH2CH2CH2
352 B BrCH2CH2CH2
353 B MeOCH2CH2
354 B EtOCH2CH2 )
Figure imgf000043_0001
355 B MeOCH2CH2CH2
356 B EtOCH2CH2CH2
357 B iso-PrOCH2CH2CH2
358 B n-BuOCH2CH2CH2
359 B MeSCH2CH2
360 B EtSCH2CH2
361 B MeSCH2CH2CH2
362 B EtSCH2CH2CH2
363 B cy-Pr
364 B cy-Pen
365 B cy-Hex
366 B 2-Me-cy-Hex
367 B PhCH2
368 B 3-F-PhCH2
369 B 4-F-PhCH2
370 B 2-Cl-PhCH2
371 B 4-Br-PhCH2
372 B 2-Me-PhCH2
373 B 4-Et-PhCH2
374 B 4-n-Pr-PhCH2
375 B 4-iso-Pr-PhCH2
376 B 4-tert-Bu-PhCH2
377 B 4-CF3-PhCH2
378 B 3-MeO-PhCH2 1.6426
379 B 4-MeO-PhCH2 1.6406
380 B 4-EtO-PhCH2
381 B 4-CF3O-PhCH2
382 B 4-CF2HO-PhCH2
Figure imgf000044_0001
383 B 4-MeS-PhCH2
384 B 4-EtS-PhCH2
385 B 4-CF3S-PhCH2
386 B 4-Ph-PhCH2
387 B 4-PhO-PhCH2
388 B 4-NO2-PhCH2
389 B 2,4-diF-PhCH2
390 B 3,4-diCl-PhCH2
391 B 2,3-diMe-PhCH2
392 B 3,4-diMeO-PhCH2 173-174
393 B 2,4,6-tri-Me-PhCH2
394 B PhCH(Me) 93-96
395 B (R)-PhCH(Me) 1.6400
396 B (S)-PhCH(Me) 1.6466
397 B 3-F-PhCH(Me) 145-147
398 B (R)-3-F-PhCH(Me) 124-125
399 B 4-F-PhCH(Me) 146-147
400 B 2-Cl-PhCH(Me) 137-141
401 B 3-Cl-PhCH(Me) 143-147
402 B 4-Cl-PhCH(Me) 179-182
403 B 4-Br-PhCH(Me) 197-198
404 B 2-Me-PhCH(Me)
405 B 4-Et-PhCH(Me)
406 B 4-n-Pr-PhCH(Me)
407 B 4-iso-Pr-PhCH(Me)
408 B 4-tert-Bu-PhCH(Me)
409 B 3-CF3-PhCH(Me) 126-128
410 B 4-CF3-PhCH(Me)
Figure imgf000045_0001
411 B 3-MeO-PhCH(Me)
412 B 4-EtO-PhCH(Me)
413 B 4-CF3O-PhCH(Me) 162-163
414 B 4-CF2HO-PhCH(Me) 146-147
415 B 4-MeS-PhCH(Me)
416 B 4-CF3S-PhCH(Me)
417 B 4-Ph-PhCH(Me) 56-60
418 B 4-PhO-PhCH(Me)
419 B 4-NO2-PhCH(Me)
420 B 2,4-diF-PhCH(Me)
421 B 3,4-diCl-PhCH(Me) 191-192
422 B 2-Me,4-Cl-PhCH(Me) 173-175
423 B 2,3-diMe-PhCH(Me)
424 B 3,4-diMeO-PhCH(Me)
425 B 2,4,6-tri-Me-PhCH(Me)
426 B PhCH(Et)
427 B 2-F-PhCH(Et)
428 B 3-Cl-PhCH(Et)
429 B 2-Me-PhCH(Et)
430 B 4-MeO-PhCH(Et)
431 B 3-CF3-PhCH(Et)
432 B PhCH(n-Pr)
433 B 2-F-PhCH(n-Pr)
434 B 3-Cl-PhCH(n-Pr)
435 B 2-Me-PhCH(n-Pr)
436 B 4-MeO-PhCH(n-Pr)
437 B 3-CF3-PhCH(n-Pr)
438 B PhCH(iso-Pr) 128-131 ComMp (°C) pound No. Z R or n^
439 B 4-Cl-PhCH(iso-Pr)
440 B 4-Me-PhCH(iso-Pr)
441 B PhCH2CH2 147-149
442 B 4-F-PhCH2CH2
443 B 2-Cl-PhCH2CH2
444 B 4-Br-PhCH2CH2
445 B 2-Me-PhCH2CH2
446 B 4-Et-PhCH2CH2
447 B 4-n-Pr-PhCH2CH2
448 B 4-iso-Pr-PhCH2CH2
449 B 4-tert-Bu-PhCH2CH2
450 B 4-CF3-PhCH2CH2
451 B 3-MeO-PhCH2CH2
452 B 4-EtO-PhCH2CH2
453 B 4-CF3O-PhCH2CH2
454 B 4-CF2HO-PhCH2CH2
455 B 4-MeS-PhCH2CH2
456 B 4-EtS-PhCH2CH2
457 B 4-CF3S-PhCH2CH2
458 B 4-Ph-PhCH2CH2
459 B 4-PhO-PhCH2CH2
460 B 4-NO2-PhCH2CH2
461 B 2,4-diF-PhCH2CH2
462 B 3,4-diCl-PhCH2CH2
463 B 2,3-diMe-PhCH2CH2
464 B 3,4-diMeO-PhCH2CH2
465 B 2,4,6-tri-Me-PhCH2CH2
466 B PhCH2CH(Me) ComMp (°C) pound
Figure imgf000047_0001
467 B 3-F-PhCH2CH(Me)
468 B 4-Cl-PhCH2CH(Me)
469 B 2-Me-PhCH2CH(Me)
470 B 3-MeO-PhCH2CH(Me)
471 B 3 ,4-diMeO-PhCH2CH(Me)
472 B PhCH2C(Me)2 194-198
473 B PhCH2CH(Et)
474 B 4-F-PhCH2CH(Et)
475 B 3-Cl-PhCH2CH(Et)
476 B 4-MeO-PhCH2CH(Et)
477 B PhCH2CH2CH2 118-120
478 B 3-F-PhCH2CH2CH2
479 B 4-F-PhCH2CH2CH2
480 B 2-Cl-PhCH2CH2CH2
481 B 4-Br-PhCH2CH2CH2
482 B 2-Me-PhCH2CH2CH2
483 B 4-Et-PhCH2CH2CH2
484 B 4-n-Pr-PhCH2CH2CH2
485 B 4-iso-Pr-PhCH2CH2CH2
486 B 4-tert-Bu-PhCH2CH2CH2
487 B 4-CF3-PhCH2CH2CH2
488 B 3-MeO-PhCH2CH2CH2
489 B 4-EtO-PhCH2CH2CH2
490 B 4-CF3O-PhCH2CH2CH2
491 B 4-CF2HO-PhCH2CH2CH2
492 B 4-MeS-PhCH2CH2CH2
493 B 4-EtS-PhCH2CH2CH2
Figure imgf000048_0001
494 B 4-CF3S-PhCH2CH2CH2
495 B 4-Ph-PhCH2CH2CH2
496 B 4-PhO-PhCH2CH2CH2
497 B 4-NO2-PhCH2CH2CH2
498 B 2,4-diF-PhCH2CH2CH2
499 B 3,4-diCl-PhCH2CH2CH2
500 B 2,3-diMe-PhCH2CH2CH2
501 B 3 ,4-diMeO-PhCH2CH2CH2
502 B 2,4,6-tri-Me-PhCH2CH2CH2
503 B PhCH2CH2CH(Me) 1.6035
504 B 3-F-PhCH2CH2CH(Me)
505 B 4-F-PhCH2CH2CH(Me)
506 B 2-Cl-PhCH2CH2CH(Me)
507 B 4-Br-PhCH2CH2CH(Me)
508 B 2-Me-PhCH2CH2CH(Me)
509 B 4-Et-PhCH2CH2CH(Me)
510 B 4-CF3-PhCH2CH2CH(Me)
511 B 3-MeO-PhCH2CH2CH(Me) 1.6171
512 B 4-EtO-PhCH2CH2CH(Me)
513 B 4-CF3O-PhCH2CH2CH(Me)
514 B 4-CF2HO-PhCH2CH2CH(Me)
515 B 4-MeS-PhCH2CH2CH(Me)
516 B 4-EtS-PhCH2CH2CH(Me)
517 B 3-CF3S-PhCH2CH2CH(Me) 1.5804
518 B 4-CF3S-PhCH2CH2CH(Me)
519 B 4-Ph-PhCH2CH2CH(Me)
520 B 4-PhO-PhCH2CH2CH(Me)
521 B 4-NO2-PhCH2CH2CH(Me) ComMp (°C) pound
No. Z R or njQ
522 B 2,4-diF-PhCH2CH2CH(Me)
523 B 3,4-diCl-PhCH2CH2CH(Me)
524 B 2,3-diMe-PhCH2CH2CH(Me)
525 B 3,4-diMeO-PhCH2CH2CH(Me)
526 B PhCH2CH2CH(Et) 1.6110
527 B 3-F-PhCH2CH2CH(Et) 87-88
528 B 4-F-PhCH2CH2CH(Et)
529 B 3-Cl-PhCH2CH2CH(Et) 1.6209
530 B 4-Cl-PhCH2H2CH(Et)
531 B 2-Me-PhCH2CH2CH(Et)
532 B 3-Me-PhCH2CH2CH(Et) 1.6096
533 B 3-MeO-PhCH2CH2CH(Et)
534 B 4-CF3O-PhCH2CH2CH(Et)
535 B PhCH2CH2CH(n-Pr) 1.6006
536 B 4-F-PhCH2CH2CH(n-Pr)
537 B 4-MeO-PhCH2CH2CH(n-Pr)
538 B PhCH2CH2CH(iso-Pr)
539 B 3-F-PhCH2CH2CH(iso-Pr)
540 B 3-Me-PhCH2CH2CH(iso-Pr)
541 B PhCH2CH2CH(n-Bu) 1.5877
542 B 4-MeO-PhCH2CH2CH(n-Bu)
543 B 4-CF3O-PhCH2CH2CH(n-Bu)
544 B PhCH2CH2CH(Ph) 121-123
545 B 4-F-PhCH2CH2CH(Ph)
546 B PhOCH2CH2
547 B 3-F-PhOCH2CH2
548 B 4-F-PhOCH2CH2
549 B 2-Cl-PhOCH2CH2 ComMp (°C) pound
Figure imgf000050_0001
550 B 4-Br-PhOCH2CH2
551 B 2-Me-PhOCH2CH2
552 B 4-Et-PhOCH2CH2
553 B 4-n-Pr-PhOCH2CH2
554 B 4-iso-Pr-PhOCH2CH2
555 B 4-tert-Bu-PhOCH2CH2
556 B 4-CF3-PhOCH2CH2
557 B 3-MeO-PhOCH2CH2
558 B 4-EtO-PhOCH2CH2
559 B 4-CF3O-PhOCH2CH2
560 B 4-CF2HO-PhOCH2CH2
561 B 4-MeS-PhOCH2CH2
562 B 4-EtS-PhOCH2CH2
563 B 4-CF3S-PhOCH2CH2
564 B 4-Ph-PhOCH2CH2
565 B 4-PhO-PhOCH2CH2
566 B 4-NO2-PhOCH2CH2
567 B 2,4-diF-PhOCH2CH2
568 B 3,4-diCl-PhOCH2CH2
569 B 2,3-diMe-PhOCH2CH2
570 B 3,4-diMeO-PhOCH2CH2
571 B 2,4,6-tri-Me-PhOCH2CH2
572 B PhOCH2CH(Me)
573 B 3-F-PhOCH2CH(Me) 129-130
574 B 4-F-PhOCH2CH(Me)
575 B 2-Cl-PhOCH2CH(Me)
576 B 4-Br-PhOCH2CH(Me)
577 B 2-Me-PhOCH2CH(Me) ComMp (°C) pound
No. Z R or n2C)
578 B 3-Me-PhOCH2CH(Me) 1.6120
579 B 3-Et-PhOCH2CH(Me)
580 B 4-Et-PhOCH2CH(Me)
581 B 4-CF3-PhOCH2CH(Me)
582 B 3-MeO-PhOCH2CH(Me)
583 B 4-EtO-PhOCH2CH(Me)
584 B 4-CF3O-PhOCH2CH(Me)
585 B 4-CF2HO-PhOCH2CH(Me)
586 B 4-MeS-PhOCH2CH(Me)
587 B 4-EtS-PhOCH2CH(Me)
588 B 4-CF3S-PhOCH2CH(Me)
589 B 4-Ph-PhOCH2CH(Me)
590 B 4-PhO-PhOCH2CH(Me)
591 B 4-N02-PhOCH2CH(Me)
592 B 2,4-diF-PhOCH2CH(Me)
593 B 3,4-diCl-PhOCH2CH(Me)
594 B 2,3-diMe-PhOCH2CH(Me)
595 B 3,4-diMeO-PhOCH2CH(Me)
596 B PhOCH2CH(Et)
597 B 3-F-PhOCH2CH(Et)
598 B 4-F-PhOCH2CH(Et)
599 B 4-Cl-PhOCH2CH(Et)
600 B 2-Me-PhOCH2CH(Et)
601 B 3-MeO-PhOCH2CH(Et)
602 B 4-CF3O-PhOCH2CH(Et)
603 B PhSCH2CH2
604 B 3-F-PhSCH2CH2
605 B 4-F-PhSCH2CH2 ComMp (°C) pound No. Z R or n20
606 B 2-Cl-PhSCH2CH2
607 B 4-Br-PhSCH2CH2
608 B 2-Me-PhSCH2CH2
609 B 4-Et-PhSCH2CH2
610 B 4-n-Pr-PhSCH2CH2
611 B 4-iso-Pr-PhSCH2CH2
612 B 4-tert-Bu-PhSCH2CH2
613 B 4-CF3-PhSCH2CH2
614 B 3-MeO-PhSCH2CH2
615 B 4-EtO-PhSCH2CH2
616 B 4-CF3O-PhSCH2CH2
617 B 4-CF2HO-PhSCH2CH2
618 B 4-MeS-PhSCH2CH2
619 B 4-EtS-PhSCH2CH2
620 B 4-CF3S-PhSCH2CH2
621 B 4-Ph-PhSCH2CH2
622 B 4-PhO-PhSCH2CH2
623 B 4-NO2-PhSCH2CH2
624 B 2,4-diF-PhSCH2CH2
625 B 3,4-diCl-PhSCH2CH2
626 B 2,3-diMe-PhSCH2CH2
627 B 3,4-diMeO-PhSCH2CH2
628 B 2,4,6-tri-Me-PhSCH2CH2
629 B PhSCH2CH(Me) 1.6545
630 B 3-F-PhSCH2CH(Me)
631 B 4-F-PhSCH2CH(Me)
632 B 2-Cl-PhSCH2CH(Me)
633 B 4-Br-PhSCH2CH(Me) Com- Mp (°C) pound
No. Z R or nj)
634 B 2-Me-PhSCH2CH(Me)
635 B 3-Me-PhSCH2CH(Me) 131-133
636 B 4-Me-PhSCH CH(Me) 1.6362
637 B 3-Et-PhSCH2CH(Me)
638 B 4-Et-PhSCH2CH(Me)
639 B 4-CF3-PhSCH2CH(Me)
640 B 3-MeO-PhSCH2CH(Me)
641 B 4-EtO-PhSCH2CH(Me)
642 B 4-CF3O-PhSCH2CH(Me)
643 B 4-CF2HO-PhSCH2CH(Me)
644 B 4-MeS-PhSCH2CH(Me)
645 B 4-EtS-PhSCH2CH(Me)
646 B 4-CF3S-PhSCH2CH(Me)
647 B 4-Ph-PhSCH2CH(Me)
648 B 4-PhO-PhSCH2CH(Me)
649 B 4-NO2-PhSCH2CH(Me)
650 B 2,4-diF-PhSCH2CH(Me)
651 B 3,4-diCl-PhSCH2CH(Me)
652 B 2,3-diMe-PhSCH2CH(Me)
653 B 3 ,4-diMeO-PhSCH2CH(Me)
654 B PhSCH2CH(Et)
655 B 3-F-PhSCH2CH(Et)
656 B 4-F-PhSCH2CH(Et)
657 B 4-Cl-PhSCH2CH(Et)
658 B 2-Me-PhSCH2CH(Et)
659 B 3-MeO-PhSCH2CH(Et)
660 B 4-CF3O-PhSCH2CH(Et)
Figure imgf000054_0001
661 B Ph
662 B 3-F-Ph
663 B 4-F-Ph 664 B 2-Cl-Ph
665 B 4-Br-Ph
666 B 2-Me-Ph
667 B 4-Et-Ph
668 B 4-n-Pr-Ph 669 B 4-iso-Pr-Ph
670 B 4-tert-Bu-Ph
671 B 4-CF3-Ph
672 B 3-MeO-Ph
673 B 4-EtO-Ph 674 B 4-CF3O-Ph
675 B 4-CF2HO-Ph
676 B 4-MeS-Ph
677 B 4-EtS-Ph
678 B 4-CF3S-Ph 679 B 4-Ph-Ph
680 B 4-PhO-Ph
681 B 4-NO2-Ph
682 B 2,4-diF-Ph
683 B 3,4-diCl-Ph 684 B 2,3-diMe-Ph
685 B 3,4-diMeO-Ph
Figure imgf000054_0002
Table 2
R1
S
1 1 | z- -c- -NH — CH2 — N — CH =S (la)
Compound Mp (°C)
No. z R1 orn5)
687 A Me 112-113 (dec.)
688 A Et
689 A n-Pr
690 A iso-Pr
691 B Me
692 B Et
693 B n-Pr
694 B iso-Pr
Table 3
Figure imgf000056_0001
Compound Mp (°C)
No. Z R2
695 A H
696 A 5-MeO
697 A 6-Me
698 A 5-Cl
699 A 6-C1
700 B H 128-132
701 B 5-Me
702 B 6-Me
703 B 5-Cl
704 B 6-C1
Table 4
Figure imgf000057_0001
ComMp °C) pound
No. Z R3 or
705 A H
706 A 5-Me
707 A 6-Me
708 A 5-Cl
709 A 6-C1
710 B H 149-151
711 B 5-Me
712 B 6-MeO
713 B 5-Cl
714 B 6-C1
Preparation of intermediates
Synthesis Example 2
Figure imgf000058_0001
A tetrahydrofuran solution (5 ml) of a mixture of 0.61 g (5 mmol) of α- 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-(α-methylbenzyl)-2,6-dichloroisonicotinic acid amide. Mp: 162 to 163 °C, yield: 75 %.
Synthesis Example 3
Figure imgf000058_0002
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. After cooling, water was added, and the mixture was alkalized with sodium hydroxide and then extracted with methylene chloride. The methylene chloride layer was washed with water and dried over anhydrous potassium carbonate. Then, methylene chloride was distilled off under reduced pressure, and the residue was refined by distillation to obtain 7.2 g of 4-(trifluoromethoxy)-α-methylbenzyl- amine. Yield: 72 %.
Synthesis Example 4
Figure imgf000059_0001
An excess amount of thionyl chloride was added to 22.7 g (114.65 mmol) of 3,4- dichloro-5-carboxylic acid, and refluxed for 2 hours by heating. Excess thionyl chloride was distilled off, and then the residue was refined by distillation to obtain 16.3 g of 3,4-dichloroisothiazole-5-carboxylic acid chloride. Yield: 66 %.
Biological Test Examples
Test Example A
Seed treatment efficacy test against rice blast
Preparation of formulations of the compounds tested
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.
Testing procedure
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.
This test is an average of the results of 2 replications. Infection rate Percentage of lesion area in (%
0 0
0.5 less than 2
1 2-less than 5
2 5 -less than 10
0 10-less than 20
4 20-less than 40
5 more than 40
, ,n /O \ — -1 Infection rate of treated section
Control value (%) = 1 x ιoo
Infection rate of untreated section
Test results
Compounds Nos. 69, 181, 196, 231, 378, 394, 395, 396, 441, 511, 537, 636 and 687 showed complete control (control value higher than 95%) at an active compound concentration of 500 ppm. Phytotoxicity was not observed in any case.
Formulation Examples
Formulation Example I (Granules)
25 parts by weight of water were added to a mixture of 10 parts by weight of Compound No. 441 according to the invention, 30 parts by weight of bentonite (mont- morillonite), 58 parts by weight of talc and 2 parts by weight of lignin sulphonic acid salt, and the mixture was kneaded thoroughly. The resulting product was granulated by means of an extrusion granulator to form granules having a size of from 10 to 40 meshes. The granules were dried at a temperature between 40 and 50°C. Formulation Example II (Granules)
95 parts by weight of a clay mineral having a particle size distribution within a range of from 0.2 to 2 mm were introduced into a rotary mixer. This product was uniformly wetted by spraying thereto under rotation a mixture of 5 parts by weight of Compound No. 527 according to the invention and a liquid diluent. The granules obtained in this manner were dried at a temperature between 40 and 50°C.
Formulation Example III (Emulsifiable Concentrate)
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.
Formulation Example IV (Wettable Powder)
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.
Formulation Example V (Wettable Granules)
20 parts by weight of Compound No. 69 according to the invention, 30 parts by weight of sodium lignin sulphonate, 15 parts by weight of bentonite and 35 parts by weight of calcined diatomaceous earth powder were thoroughly mixed with water. The resulting product was granulated by means of extrusion through a 0.3 mm screen. After drying the product, wettable granules were obtained.

Claims

Patent Claims
1. Thiocarboxamides of the formula
S
II z-c- -NH- -R (I)
in which
represents a group of the formula
Figure imgf000063_0001
R represents
Figure imgf000063_0002
haloalkyl, Cj_4 alkoxy-Cμ3 alkyl, Cj_4 alkylthio-Cj.3 alkyl, optionally substituted C3.6 cycloalkyl, optionally substituted aralkyl, optionally substituted phenoxyalkyl, optionally substituted phenylthioalkyl, optionally substituted phenyl or a group selected from
Figure imgf000063_0003
wherein
R1 represents C 1.4 alkyl,
R2 represents hydrogen, halogen, C1.4 alkyl or C 1.4 alkoxy and
R3 represents hydrogen, halogen, C1.4 alkyl or C 1.4 alkoxy. Thiocarboxamides of the formula (I) according to claim 1, in which
R represents Cj.g alkyl, haloalkyl having 1 to 3 carbon atoms and 1 to 5 halogen atoms, C^ alkoxy-C2.3 alkyl, C1.4 alkylthio-C2_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-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, trifluoro- methoxy, difluoromethyl, difluoromethxy, phenyl, phenoxy, trifluoromethylthio and/or nitro, or
R represents 1,3-diphenylpropan-l-yl or l-(4-fluorophenyl)-3 -phenyl - propan-1-yl, or
R represents a group selected from
Figure imgf000065_0001
wherein
Ri represents C1.3 alkyl, R2 represents hydrogen, chlorine, methyl or methoxy and R3 represents hydrogen, chlorine, methyl or methoxy
and
represents a group of the formula
Figure imgf000065_0002
3. Thiocarboxamides of the formula (I) according to claim 1, in which
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-ethoxypropyl, 3-isopropoxypropyl, 3-n-butoxy- propyl, 2-methylthioethyl, 2-ethylthioethyl, 3-methylthiopropyl, 3- ethylthiopropyl, cyclopropyl, cyclopentyl, cyclohexyl or 2-methyl- cyclohexyl, 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, trifluoro- methyl, 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, trifluoro- methoxy, difluoromethyl, difluoromethoxy, phenyl, phenoxy, trifluoromethylthio and/or nitro, or
R represents 1,3-diphenylpropan-l-yl or l-(4-fluorophenyl)-3-phenyl- propan-1-yl, or
R represents a group selected from
Figure imgf000067_0001
in which
R1 represents methyl, ethyl, n-propyl or isopropyl,
R2 represents hydrogen, or chlorine , methyl or methoxy at the 5- position or 6-position and
R3 represents hydrogen, or chlorine, methyl or methoxy at the 5- position or 6-position,
and
represents a group of the formula
Figure imgf000067_0002
4. Process for the preparation of thiocarboxamides of the formula (I) according to claim 1, characterized in that
a) carboxamides of the formula
O Z-C- -NH- — R CD) in which
R and Z have the above-mentioned meanings,
are reacted with phosphorous pentasulfide in the presence of an inert diluent.
5. Microbicidal compositions, characterized in that they contain at least one thiocarboxamide of the formula (I) according to claim 1 plus extenders and/or surface active agents.
6. Process for combating undesired microorganisms, characterized in that thiocarboxamide of the formula (I) according to claim 1 are applied to the microorganisms and/or to their habitat.
7. Use of thiocarboxamide of the formula (I) according to claim 1 for combating undesired microorganisms.
8. Process for the preparation of microbicidal compositions, characterized in that thiocarboxamide of the formula (I) according to claim 1 are mixed with extenders and/or surface-active agents.
PCT/EP2001/001824 2000-03-01 2001-02-19 Dichloropyridyl- and dichloroisothiazolyl-thiocarboxamides and their use as microbicides WO2001064644A1 (en)

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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
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