EP0835242A1 - S-oxydes de thioamide utilises comme pesticide - Google Patents

S-oxydes de thioamide utilises comme pesticide

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Publication number
EP0835242A1
EP0835242A1 EP96922792A EP96922792A EP0835242A1 EP 0835242 A1 EP0835242 A1 EP 0835242A1 EP 96922792 A EP96922792 A EP 96922792A EP 96922792 A EP96922792 A EP 96922792A EP 0835242 A1 EP0835242 A1 EP 0835242A1
Authority
EP
European Patent Office
Prior art keywords
phenyl
substituted
alkyl
methyl
crc
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP96922792A
Other languages
German (de)
English (en)
Inventor
René Zurflüh
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis Pharma GmbH
Novartis AG
Original Assignee
Novartis Erfindungen Verwaltungs GmbH
Ciba Geigy AG
Novartis AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Novartis Erfindungen Verwaltungs GmbH, Ciba Geigy AG, Novartis AG filed Critical Novartis Erfindungen Verwaltungs GmbH
Publication of EP0835242A1 publication Critical patent/EP0835242A1/fr
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/60—Thiocarboxylic acids having sulfur atoms of thiocarboxyl groups further doubly-bound to oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/20—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings condensed with carbocyclic rings or ring systems

Definitions

  • the present invention relates to thioamide S-oxides of the formula
  • R-i is hydrogen or C-
  • R 2 is hydrogen, C ⁇ -C -alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl or C 3 -C 6 cycloalkyl,
  • R3 and R4 independently of one another are hydrogen, cyano, C-
  • R 3 and R A together with the joint carbon atom form an unsubstituted or up to trisubstituted ring which has not more than 15 ring carbon atoms, which can be polycyclic and which contains 0-3 hetero atoms N, O or S,
  • R 3 and R 4 being selected from the series consisting of C ⁇ -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C C 4 alkoxy, C ⁇ -C 4 alkylthio, C C 4 haloalkyl, C 2 -C 4 halo- alkenyl, C 2 -C haloalkynyl, C C haloalkoxy, dihalocyclopropylmethoxy, halogen, cyano, cyano-C 1 -C 2 alkyl, cyano-C Caalkoxy, OH, N0 2 , -SCN, -OCN, thiocyano- methyl, -SF 5l Si(CH 3 ) 3 , NH 2) NH(C ⁇ C 4 alkyl), N(C C 4 alkyl) 2 , CVO-alkoxymethyl, C 1 -C 4
  • the compounds of the formula I exist in optically active form.
  • the compounds exist in the [E] or [Z] form, merely on the basis of an imino double bond which is ' present. Atropisomerism can furthermore exist.
  • the formula I is intended to embrace all these isomeric forms which are possible and their mixtures, for example racemic mixtures and any [E/Z] mixtures.
  • the compounds according to the invention have fungicidal, insecticidal and acaricidal properties and are suitable for use as active ingredients in crop protection.
  • the compounds I may form acid addition salts. These are formed, for example, with strong inorganic acids such as mineral acids (for example sulfuric acid, phosphorus - containing acid or a hydrohalic acid), with strong organic carboxylic acids, such as substituted or unsubstituted (for example halogen-substituted) C C 4 alkanecarboxylic acids, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid; or they are formed with organic sulfonic acids, such as substituted or unsubstituted (for example halogen-substituted) C C 4 alkane- or arylsulfonic acids, for example methane- or
  • Alkyl groups alone or as structural element of other groups can be straight-chain or branched, depending on the number of the carbon atoms.
  • C,-C 4 alkyl is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.
  • Alkenyl as a group or as structural element of other groups and compounds such as alkenyloxy, arylalkenyl and heteroarylalkenyl is either straight-chain, for example ethenyl, propen-1-yl or but-1-en-1-yl, or branched, for example propen-2-yl or but-1- en-2-yl.
  • Alkynyl as a group or as a structural element of other groups and compounds such as alkynyloxy is either straight-chain, for example ethynyl, propyn-1-yl or but-1-yn-1- yl, or branched, for example propyn-2-yl or but-1-yn-2-yl.
  • Cycloalkyl as a group or as a structural element of other groups and compounds, such as cycloalkylmethoxy, is, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • Carbocyclic rings alone or as structural elements of other groups such as aryl- C C alkyl, aryloxy-C 1 -C alkyl, arylthio-C C ⁇ alkyl, arylcarbonyl and aryl-C 2 - C 4 alkenyl groups have, in particular, 6 to 14 C atoms and are, for example, naphthyl, tetrahydronaphthyl, indanyl, fluorenyl, phenanthryl or, in particular, phenyl. They can be aromatic, partially hydrogenated or fully saturated. One or two benzene rings may be fused onto carbocyclic rings.
  • Rings containing hetero atoms as a group by themselves and as structural elements of other groups and compounds, such as heteroaryl-C C alkyl, heteroaryloxy- C 1 -C 4 alkyl, heteroarylthio-C-
  • benzimidazolyl benzocoumarinyl, benzofuryl, benzothiadiazolyl, benzothiazolyl, benzisothiazolyl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzoxdiazolyl, quinazolinyl, quinolyl, quinoxalinyl, carbazolyl, dihydrobenzofuryl, ethylenedioxyphenyl, furyl, imidazolyl, indazolyl, indolyl, isoquinolyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl, naphthyridinyl, oxazolyl, phenanthridinyl, phthalazinyl, pteridinyl, purinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyrazolo[3,4-b]pyri
  • Preferred heteroaryl radicals R 3 and/or R 4 are benzofuryl, benzothienyl, quinolyl, quinoxalinyl, dihydrobenzofuryl, ethylenedioxy, furyl, methylenedioxy, pyridyl, pirimidinyl, pyrrolyl, thiazolyl, benzisoxazolyl, benzisothiazolyl, indazolyl and thienyl.
  • One or two benzene rings may be fused onto heterocyclic rings.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • haloalkyl and haloalkoxy groups are -CH 2 F, -CHF 2 , -CF 3 , -CH 2 CI, -CHCI 2 , -CCI 3 , -CCI 2 CCI 3> -CH 2 Br, -CH 2 CH 2 Br, -CHBrCI, -OCHF 2 , OCF 3 , OCH 2 CF 3 , OCF 2 CHF 2 , OCF 2 CHFCF 3 , OCF 2 Br, OCF 2 CI, OCF 2 CF 2 Br.
  • a preferred group of compounds of the formula I are those compounds in which Ri is hydrogen and R 2 is methyl (sub-group la).
  • Another preferred group of compounds of the formula I are those compounds in which R T is hydrogen, R 2 is methyl and R 3 is methyl, ethyl, methoxy, methylthio, cyano or cyclopropyl (sub-group Ib).
  • Another preferred group of compounds of the formula I are those compounds in which Ri is hydrogen, R 2 is methyl and R 3 is methyl, ethyl, methoxy, methylthio, cyano or cyclopropyl and in which R 4 is phenyl which is mono- or disubstituted by subsituents selected from the group consisting of halogen, methoxy, trifluoromethyl and trifluoromethoxy (sub-group Ic).
  • R 4 is 3-chlorophenyl, 3-bromophenyl, 4-chlorophenyl, 4-bromophenyl, 3-trifluoromethylphenyl, 3-trifluoromethoxyphenyl, 3,5-dichlorophenyl, 3-fluoro-4- methoxyphenyl or 3-chloro-4-methoxyphenyl (sub-group Ice).
  • R-i H, C C 2 alkyl
  • R 2 H
  • R 3 H, C C 4 alkyl, cyclopropyl, CrC 2 alkoxy, C C 2 -alkylthio, methoxymethyl, cyano, trifluoromethyl
  • R 4 halophenyl having 1 to 2 halogen atoms, mono-C C 2 alkylphenyl, mono- Cr ⁇ alkoxyphenyl, monohalomono(C ⁇ -C 2 alkoxy)phenyl, 3-halo-C C 4 alkylphenyl having 1 to 3 halogen atoms, trifluoromethylphenyl which is substituted by fluorine or chlorine, 3-halo-C ⁇ -C 4 alkoxyphenyl having 1 to 6 halogen atoms (in particular fluorine), 3-C 2 -C 4 alkenyloxyphenyl, 3-C 2 -C 4 alkynyloxyphenyl, 3-C 3 -C 6 cycloalkyl- methoxyphenyl, 3-cyano-Ci-C-jalkoxyphenyl, bis(trifluoromethyl)phenyl, tolyl which is substituted by fluorine or chlorine, monocyanophenyl, trifluoro- methylphenyl which is substituted
  • substitutents have the following meanings:
  • Ri H, C 1 -C 2 alkyl
  • R 2 H, C 1 -C 4 alkyl
  • R 3 H, C ⁇ C 2 alkyl, cyclopropyl, methoxy, methylthio, methoxymethyl, cyano, trifluoromethyl
  • R monohalophenyl, dihalophenyl, mono-C C 2 alkylphenyl, mono-C 1 -C alkoxy- phenyl, halomethoxyphenyl, 2-naphthyl, 3,4-methylenedioxyphenyl, 3,4-ethylene- dioxyphenyl, 2,2-difluoro-5-benzodioxolyl, 2-methoxy-5-benzodioxolyl, 3-fluoro- C-
  • R 3 and R 4 together are a 5,6-dihydro-2H-1 ,4-thiazin ring which is subsituted in the 3-position by mono- or dihalophenyl, methoxyphenyl, trifluoromethylphenyl, phenoxy or 3,4-methylenedioxyphenyl, or R 3 and R 4 together are a cyclopentane or tetrahydropyran ring to which an unsubstituted or fluorine-substituted benzene ring is fused.
  • R 3 methyl, cyclopropyl
  • R 4 3-chlorophenyl, 3-trifluoromethylphenyl, 3-trifluoromethoxyphenyl, 3-difluoro- chloromethoxyphenyl or 4-chlorophenyl (sub-group Id).
  • the thioamide S-oxides according to the invention can be prepared from the corresponding thioamides by oxidation.
  • Particularly suitable oxidants are peroxides or peracids, for example hydrogen peroxide, in, for example, glacial acetic acid.
  • the invention furthermore relates to a process for the preparation of the compounds of the formula I according to the invention, to pesticides which comprise such compounds as insecticidally, acaricidally, but in particular as fungicidally active ingredients, and to the use of such compounds and compositions for controlling noxious insects, pests from the order Acarina and, in particular, phytopathogenic fungi and for preventing fungus infestation.
  • the pests found on plants or parts of plants can be contianed or destroyed, and even parts of the plants which form at a later point in time remain free from phytopathogenic microorganisms.
  • the compounds of the formula I can furthermore be used as seed-dressing products for the treatment of seed (fruits, tubers, kernels) and propagation stock to protect these against fungal infection and against phytopathogenic soil-borne fungi.
  • Compounds of the formula I act for example against the phytopathogenic fungi which belong to the following classes: Fungi imperfecti (in particular Botrytis, furthermore Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora, Cercosporella and Alternaria); Basidiomycetes (for example Rhizoctonia, Hemileia, Puccinia). Moreover, they are active against the class of the Ascomycetes (for example Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula), but especially against the class of the Oomycetes (for example Phytophthora, Peronospora, Bremia, Pythium, Plasmopara).
  • Fungi imperfecti in particular Botrytis, furthermore Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora, Cercosporella and Alternaria
  • Basidiomycetes for example Rhizoctonia, He
  • a particular advantage of the compounds I in comparison with the analogous prior- art thioamide structures is a markedly Iower crop plant phytotoxicity and a favourable metastability which will have caused biodegradation of the compound at crop maturity at the lastest.
  • Target crops for the crop-protecting use disclosed herein are within the scope of the present invention for example the following plant species: cereals (wheat, barley, rye, oats, triticale, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomaceous fruit, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, gooseberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soya); oil crops (oil seed rape, mustard, poppies, olives, sunflowers, coconuts, castor, cocoa, groundnuts); cucurbits (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, tangerines); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, bell peppers); Lauraceae (a
  • Active ingredients of the formula I are usually used in the form of compositions and can be applied to the plant or area to be treated simultaneously or in succession with other active ingredients.
  • These other active ingredients can be fertilizers, trace element mediators or other preparations which affect plant growth. Selected herbicides, and insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of a plurality of these preparations, if desired together with other carriers, surfactants or other application-enhancing additives conventionally used in the art of formulation may also be used.
  • Suitable carriers and additives can be solid or liquid and are the substances expediently used in the art of formulation, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.
  • aromatic hydrocarbons preferably the fractions C 8 to C 12 , for example xylene mixtures or substituted naphthalenes, phthalic esters such as dibutyl phthalate or dioctylphthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and free or • epoxidized vegetable oils, such as epoxidized coconut oil or soya oil; or water.
  • aromatic hydrocarbons preferably the fractions C 8 to C 12
  • phthalic esters such as dibutyl phthalate or dioctylphthalate
  • aliphatic hydrocarbons such as cyclo
  • Solid carriers which are used for example for dusts and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • Particularly advantageous application-enhancing additives which may lead to a drastic reduction in application rate are furthermore natural (animal or vegetable) or synthetic phosphoiipids from the series of the cephalins and lecithins which can be obtained, for example, from soybeans.
  • Surface-active compounds are, depending on the nature of the active ingredient of the formula I to be formulated, non-ionic, cationic and/or anionic surfactants which have good emulsifying, dispersing and wetting properties. Surfactants are also to be understood as meaning surfactant mixtures.
  • Suitable anionic surfactants can be either so-called water-soluble soaps or water ⁇ soluble synthetic surface-active compounds.
  • Suitable soaps which may be mentioned are the alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts of higher fatty acids (C 10 - C 22 ), for example the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained, for example, from coconut oil or tallow oil. Fatty acid methyltaurides may furthermore be mentioned.
  • Suitable non-ionic surfactants are polyglycoi ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.
  • non-ionic surfactants examples include nonylphenol polyethoxyethanols, castor oil polyglycoi ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethyleneglycol and octylphenoxypolyethoxyethanol.
  • Fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate, are also suitable.
  • the cationic surfactants are mainly quaternary ammonium salts which have, as N-substituent, at least one alkyl radical having 8 to 22 C atoms and, as further substituents, Iower, free or halogenated alkyl, benzyl or Iower hydroxyalkyl radicals.
  • anionic, non-ionic or cationic surfactants conventionally used in the art of formulation are known to those skilled in the art or can be found in the relevant specialist literature:
  • the agrochemical preparations comprise from 0.1 to 99 %, in particular 0.1 to 95 %, of active ingredient of the formula I, 99.9 to 1 %, in particular 99.9 to 5 %, of a solid or liquid additive and 0 to 25 %, in particular 0.1 to 25 %, of a surfactant.
  • compositions are more preferred as commercially available goods, the end user uses, as a rule, dilute compositions.
  • the compositions can also comprise other additives such as stabilizers, antifoams, viscosity regulators, binders, adhesives and fertilizers, or other active ingredients for achieving specific effects.
  • compositions, preparations or combinations comprising the active ingredient of the formula I and, if desired, a solid or liquid additive are prepared in a known manner, for example by intimately mixing and/or grinding the active ingredient with an extender, for example a solvent (mixture), a solid carrier material, and, if desired, surface-active compounds (surfactants).
  • an extender for example a solvent (mixture), a solid carrier material, and, if desired, surface-active compounds (surfactants).
  • a preferred method of applying an active ingredient of the formula I, or an agrochemical composition which comprises at least one of these active ingredients, is application to the foliage (foliar application). Frequency and rate of application depend on the danger of infestation with the pathogen in question.
  • the active ingredients of the formula I can reach the plant via the soil through the root system (systemic action) by drenching the locus of the plant with a liquid preparation or by incorporating the substances into the soil in solid form, for example in the form of granules (soil application). In the case of paddy rice, such granules can be metered into the flooded paddy field.
  • the compounds of the formula I can be applied to seed kernels (coating), either by soaking the kernels in a liquid preparation of the active ingredient or by coating them with a solid preparation.
  • seed kernels coating
  • any type of plant propagation material can be protected using the compounds of the formula I, for example the seed, roots or stalk.
  • the compounds of the formula I are employed as pure active ingredients or, preferably, together with the auxiliaries conventionally used in the art of formulation. To this end, they are expediently processed in a manner known per se, for example to give emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or encapsulations for example in polymeric substances.
  • the methods of application such as spraying, atomizing, dusting, scattering, brushing on or pouring, and the type of composition are selected to suit the intended aims and the prevailing circumstances.
  • Favourable rates of application are generally 5 g to 2 kg of active ingredient (a.i.) per ha, preferably 25g to 800g of a.i./ha, particularly preferably 50g to 400g of a.i./ha.
  • dosage rates When used as a seed-dressing product, it is advantageous to use dosage rates of from 0.001 g to 1.0g of active ingredient per kg of seed.
  • the reaction mixture is carefully stirred into 4.3 litres of saturated sodium bicarbonate solution (5°C).
  • the weakly basic yellow suspension is extracted three times using 600 ml of ethyl acetate.
  • the combined organic extracts are washed twice using 100 ml of bicarbonate solution (10 %) and twice using 100 ml of water.
  • the dark oil obtained is dissolved by stirring in 80 ml of tert-butyl methyl ether, 80 ml of hexane are then added, and the product is brought to crystallization.
  • the active ingredient is mixed thoroughly with the additives and the mixture is ground thoroughly in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.
  • Soya oil (39 mol of ethylene oxide) 5 %
  • Emulsions of any desired dilution can be prepared from this concentrate by diluting it with water.
  • Kaolin - 92 % Ready-to-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill.
  • the active ingredient is mixed with the additives, and the mixture is ground and moistened with water. This mixture is extruded and subsequently dried in a stream of air.
  • the finely ground active ingredient is applied uniformly to the kaolin which has been moistened with polyethylene glycol. This gives dust-free coated granules.
  • the finely ground active ingredient is mixed intimately with the additives. This gives a suspension concentrate from which suspensions of any desired dilution can be prepared by diluting it with water.
  • Example B-1 Activity against Phytophthora infestans in tomatoes
  • Tomato plants cv. "Roter Gnom" are grown for three weeks and then sprayed with a zoospore suspension of the fungus and incubated in a cabin at 18 to 20° and saturated atmospheric humidity. The humidification is interrupted after 24 hours. After the plants have dried, they are sprayed with a mixture which comprises the active ingredient, formulated as a wettable powder, at a concentration of 200 ppm. After the spray coating has dried on, the plants are returned into the humid chamber for 4 days. Number and size of the typical foliar lesions which have formed after this time are used as an assessment scale for the efficacy of the test substances. b) Preventive-systemic action
  • the active ingredient formulated as a wettable powder, is applied at a concentration of 60 ppm (based on the soil volume) to the soil surface of three-week-old tomato plants cv. "Roter Gnom" in pots. After a waiting period of three days, the underside of the leaves is sprayed with a zoospore suspension of Phytophthora infestans. They are then kept for 5 days in a spray cabinet at 18 to 20°C and saturated atmospheric humidity. After this time, typical foliar lesions are formed, whose number and size are used to assess the efficacy of the test substances.
  • Example B-2 Activity against Plasmopara viticola (Bert, et Curt.) (Berl. et DeToni) in grapevines
  • Grapevine cuttings cv. "Chasselas” are grown in the greenhouse. Three plants in the 10- leaf stage are sprayed with a mixture (200 ppm of active ingredient). After the spray coating has dried on, the plants are infected uniformly on the underside of the leaves with the spore suspension of the fungus. The plants are subsequently kept in a humid chamber for 8 days. After this time, the control plants show marked disease symptoms. Number and size of the infection sites in the treated plants are used as an assessment scale for the efficacy of the test substances.
  • Grapevine cuttings cv. "Chasselas” are grown in the greenhouse and, in the 10-leaf stage, infected on the underside of the leaves with a spore suspension of Plasmopara viticola. After the plants have remained in a humid chamber for 24 hours, they are sprayed with a mixture of the active ingredient (200 ppm of active ingredient). The plants are subsequently kept for a further 7 days in the humid chamber. After this time, the disease symptoms emerge on the control plants. Number and size of the infection sites in the treated plants are used as an assessment scale for the efficacy of the test substances. In comparison with the control plants, the plants which have been treated with active ingredients of the formula I show an infestation level of 20 % or less. A particularly sustained activity is shown by the compounds No. 2.58, 2.151 and others.
  • Example B-3 Activity against Pythium debaryanum in sugar beet (Beta vulgaris)
  • the fungus is grown on sterile oat kernels and admixed with a soil/sand mixture. This infected soil is filled into flowe ⁇ ots, and sugar beet seeds are sown.
  • the test preparations formulated as wettable powders, are poured on the soil in the form of an aqueous suspension (20 ppm of active ingredient based on the soil volume).
  • the pots are then placed in a greenhouse at 20-24°C for 2-3 weeks.
  • the soil is always kept uniformly moist by gently spraying on water.
  • the fungus is grown on sterile oat kernels and admixed with a soil/sand mixture. This infected soil is filled into flowerpots, and sugar beet seeds are sown which had been treated with the test preparations formulated as seed-dressing powders (1000 ppm of active ingredient based on the weight of the seeds).
  • the pots together with the seeds are placed in a greenhouse at 20-24°C for 2-3 weeks. The soil is kept uniformly moist by gently spraying on water.
  • Example B-4 Residual-protecive action against Cercospora arachidicola in groundnuts
  • Groundnut plants 10 to 15 cm in height are sprayed to drip point with an aqueous spray mixture (0.02% of active ingredient) and, 48 hours later, infected with a conidia suspension of the fungus.
  • the plants are incubated for 72 hours at 21 ° and high atmospheric humidity and subsequently placed in a greenhouse until the typical foliar lesions appear.
  • the activity of the active ingredient is assessed 12 days after infection basd on the number and size of the foliar lesions.
  • Active ingredients of the formula I cause a reduction in foliar lesions to below approximately
  • Example B-5 Activity against Puccinia graminis in wheat a) Residual-protective action
  • wheat plants are sprayed to drip point with an aqueous spray mixture (0.02% of active ingredient) and, 24 hours later, infected with a uredospore suspension of the fungus. After an incubation time of 48 hours (conditions: 95 to 100 per cent relative atmospheric humidity at 20°), the plants are placed in a greenhouse at 22°. The rust pustule development is assessed 12 days after infection.
  • an aqueous spray mixture (0.006% of active ingredient based on the soil volume) is poured next to wheat plants. Care is taken that the spray mixture does not come into contact with aerial parts of the plants. 48 hours later, the plants are infected with a uredospore suspension of the fungus. After an incubation time of 48 hours (conditions: 95 to 100 per cent relative atmospheric humidity at 20°), the plants are placed in a greenhouse at 22°. The rust pustule development is assessed 12 days after infection. Compounds of the formula I cause a marked reduction in fungus infestation, in some cases down to 10-0%, for example the compounds No. 2.80, 2.82, 2.83, 2.90 and others.
  • Example B-6 Activity against Pyricularia oryzae in rice a) Residual-protective action
  • Rice plants are grown for two weeks and then sprayed to drip point with an aqueous spray mixture (0.02% of active ingredient) and, 48 hours later, infected with a conidia suspension of the fungus.
  • the fungus infestation is assessed 5 days after the infection, during which a relative atmospheric humidity of 95 to 100 percent and a temperature of 22° are maintained.
  • aqueous spray mixture (0.006% of active ingredient based on the soil volume) is poured next to rice plants which are 2 weeks old. Care is taken that the spray mixture-does not come into contact with aerial parts of the plants. The pots are then filled with water to such an extent that the bottommost parts of the rice plant stalks are submerged. After 96 hours, the plants are infected with a conidia suspension of the fungus and kept for 5 days at a relative atmospheric humidity of 95 to 100 percent and a temperature of 24°C.
  • Example B-7 Residual-protective action against Venturia inaequalis in apples
  • Apple cuttings having fresh shoots 10 to 20 cm in length are sprayed to drip point with a spray mixture (0.02% of active ingredient) and, 24 hours later, infected with a conidia suspension of the fungus.
  • the plants are incubated for 5 days at a relative atmospheric humidity of 90 to 100 percent and for a further 10 days in a greenhouse at 20 bis 24°.
  • the scab infestation is assessed 15 days after infection.
  • Example B-8 Activity against Erysiphe graminis in barley a) Residual-protective action
  • Barley plants approximately 8 cm in height are sprayed to drip point with an aqueous spray mixture (0.02% of active ingredient) and, 3 to 4 hours later, dusted with conidia of the fungus.
  • the infected plants are placed in a greenhouse at 22°. Fungus infestation is assessed 10 days after the infection.
  • aqueous spray mixture (0.002% of active ingredient, based on the soil volume) is poured next to barley plants approximately 8 cm in height. Care is taken that the spray mixture does not come into contact with aerial parts of the plants. 48 hours later, the plants are dusted with conidia of the fungus. The infected plants are placed in a greenhouse at 22°. The fungus infestation is assessed 10 days after the infection.
  • Compounds of the formula I are generally capable of reducing the disease level to less than 20%, in some cases also completely (for example compounds of sub-group Ic).
  • Example B-9 Activity against Podosphaera leucotricha in apple shoots
  • Apple cuttings which have fresh shoots of approximately 15 cm length are sprayed with a spray mixture (0.06% of active ingredient). After 24 hours, the treated plants are infected with a conidia suspension of the fungus' and placed in a controlled-environment cabinet at a relative atmospheric humidity of 70% and 20°C. The fungus infestation is assessed 12 days after the infection.
  • the disease level is less than 20%.
  • the disease level of the control plants is 100%.
  • Example B-10 Activity against Botrytis cinerea in apple fruits. Residual-protective action Artificially damaged apples are treated by dropwise application of a spray mixture (0.02% of active ingredient) to the sites of damage. The treated fruits are subsequently inoculated with a spore suspension of the fungus and incubated for one week at high atmospheric humidity and approximately 20°C. The fungicidal activity of the test substance is deduced from the number of sites of damage where rot has started.
  • Active ingredients of the formula I from Table 1 or 2 are capable of preventing the rot from spreading, in some cases completely.
  • Example B-11 Activity against Helminthosporium gramineum
  • Wheat kernels are contaiminated with a spore suspension of the fungus and left to dry.
  • the contaiminated kernels are treated with a suspension of the test substance (600 ppm of active ingredient based on the weight of the seeds). After two days, the kernels are placed on suitable agar dishes, and after a further four days the development of the fungal colonies around the kernels is assessed. Number and size of the fungal colonies are taken into consideration for assessing the test substance.
  • Example B-12 Activity against Colletotrichum la ⁇ enarium in cucumbers Cucumber plants are grown for 2 weeks and then sprayed with a spray mixture (concentration 0.002%). After 2 days, the plants are infected with a spore sus ension of the fungus (1.5 x 10 5 spores/ml) and incubated for 36 hours at 23°C and high atmospheric humidity. The incubation is then continued at normal atmospheric humidity and approximately 22-23°C. 8 days after the infection, the fungus infestation is assessed. Untreated, but infected control plants have a fungus infestation of 100 %. Some of the compounds of the formula I cause almost complete inhibition of the incidence of disease.
  • Example B-13 Activity against Fusarium nivale in rye
  • rye cv. Tetrahell which was naturally infected with Fusarium nivale was treated with the test fungicide, the following concentrations being used: 20 or 6 ppm of a.i. (based on the seed weight).
  • the infected and treated rye is sown in October in the open in plots of 3 m length and 6 seed rows. 3 replications per concentration.
  • test field is grown under normal field conditions (preferably in a region with closed snow cover during the winter months).
  • the percentage of Fusarium-infested plants is counted immediately after the snow has melted. In the present case, the number of treated plants was less than 5%. Those plants which had emerged were healthy in appearance.
  • Example B-14 Activity against Septoria nodorum in wheat
  • Wheat plants in the 3-leaf stage are sprayed with a spray mixture (60 ppm of a.i.) prepared from a wettable powder of the active ingredients (2.8:1). After 24 hours, the treated plants are infected with a conidia suspension of the fungus. The plants are then incubated for 2 days at a relative atmospheric humidity of 90-100% and placed for a further 10 days in a greenhouse at 20-24°C. 13 days after infection, the fungus infestation is assessed. Less than 1 % of the wheat plants were infested. The compounds No. 2.80 and 2.90 had a particularly sustained action.
  • Example B-15 Activity against Rhizoctonia solani in rice Protective local soil application:
  • Rice plants which are 10 days old are watered with a suspension (spray mixture) prepared from a formulated test substance without contaminating aerial parts of the plants. Infection takes place three days later by placing a stem of barley straw which is infected with Rhizoctonia solani between the rice plants of each pot. After 6 days, incubation in a controlled-environment cabinet at a daytime temperature of 29°C and a nighttime temperature of 26°C and 95 % relative atmospheric humidity, the fungus infestation is assessed. Less than 5% of the rice plants were infested. The plants were healthy in appearance.
  • Rice plants which are 12 days old are sprayed with a suspension prepared from a formulated test substance. Infection takes place one day later by placing a stem of barley straw which is infected with Rhizoctonia solani between the rice plants of each pot. After 6 days' incubation in a controlled-environment cabinet at a daytime temperature of 29°C and a nighttime temperature of 26°C and 95 % relative atmospheric humidity, the plants are scored. Untreated, but infected control plants show a fungus infestation of 100%. Compounds of the formula I cause inhibition of the incidence of disease, in some cases almost completely.

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

Abstract

La présente invention décrit des S-oxydes de thiaomide de formule (I) servant d'ingrédients actifs fongicides, insecticides et contre les acariens en matière de protection des récoltes, formule dans laquelle R1 représente hydrogène ou alkyle C1-C4, et R2 représente hydrogène, alkyle C1-C4, alkényle C2-C4, alkynyle C2-C4 ou cycloalkyle C3-C6, et dans laquelle R3 et R4 sont indépendants et représentent hydrogène, cyano, alkyle C1-C4, haloalkyle C1-C4, alkényle C2-C4, alkynyle C2-C4, cycloalkyle C3-C6, cyclopropylméthyle, alkyle C2-C5thioalkyle; un noyau non substitué jusqu'à un noyau trisubstitué ne comportant pas plus de 15 atomes de carbone cyclique, pouvant être polycyclique et contenant 0-3 hétéro atomes de N, O ou S, ledit noyau pouvant être lié par un pont aliphatique ne comportant pas plus de 4 atomes de carbone et/ou par soit CO, oxygène ou soufre; ou dans laquelle R3 et R4 ensemble avec le carbone combiné forment un noyau non substitué ou jusqu'à un noyau trisubstitué ne comportant pas plus de 15 atomes de carbone cyclique, pouvant être polycyclique et qui contient 0-3 hétéro atomes de N, O ou S. Ces composés peuvent être utilisés par eux-mêmes ou en tant que compositions formulées, de préférence pour contrôler ou pour empêcher l'infestation par des micro-organismes.
EP96922792A 1995-06-21 1996-06-10 S-oxydes de thioamide utilises comme pesticide Ceased EP0835242A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH182395 1995-06-21
CH1823/95 1995-06-21
PCT/EP1996/002520 WO1997000859A1 (fr) 1995-06-21 1996-06-10 S-oxydes de thioamide utilises comme pesticide

Publications (1)

Publication Number Publication Date
EP0835242A1 true EP0835242A1 (fr) 1998-04-15

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EP96922792A Ceased EP0835242A1 (fr) 1995-06-21 1996-06-10 S-oxydes de thioamide utilises comme pesticide

Country Status (7)

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EP (1) EP0835242A1 (fr)
JP (1) JPH11513018A (fr)
AR (1) AR002524A1 (fr)
AU (1) AU6354896A (fr)
BR (1) BR9609210A (fr)
WO (1) WO1997000859A1 (fr)
ZA (1) ZA965230B (fr)

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WO2017107939A1 (fr) 2015-12-25 2017-06-29 沈阳中化农药化工研发有限公司 Composé éther d'oxime de malononitrile et son utilisation

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JP3188286B2 (ja) * 1991-08-20 2001-07-16 塩野義製薬株式会社 フェニルメトキシイミノ化合物およびそれを用いる農業用殺菌剤
TW299310B (fr) * 1993-05-18 1997-03-01 Ciba Geigy Ag

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Title
See references of WO9700859A1 *

Also Published As

Publication number Publication date
BR9609210A (pt) 1999-05-11
AU6354896A (en) 1997-01-22
AR002524A1 (es) 1998-03-25
WO1997000859A1 (fr) 1997-01-09
JPH11513018A (ja) 1999-11-09
ZA965230B (en) 1996-12-23

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