EP1115698A1 - Pesticidal tris-oxime compounds - Google Patents
Pesticidal tris-oxime compoundsInfo
- Publication number
- EP1115698A1 EP1115698A1 EP99948797A EP99948797A EP1115698A1 EP 1115698 A1 EP1115698 A1 EP 1115698A1 EP 99948797 A EP99948797 A EP 99948797A EP 99948797 A EP99948797 A EP 99948797A EP 1115698 A1 EP1115698 A1 EP 1115698A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- plants
- formula
- compounds
- compound
- active ingredient
- 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.)
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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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
- C07C251/60—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/61—Carboxylic acid nitriles containing cyano groups and nitrogen atoms being part of imino groups bound to the same carbon skeleton
Definitions
- the invention relates to novel pesticidally, in particular fungicidally, active tris-oxime compounds of formula I
- R 2 is hydrogen, methyl or ethyl
- R 3 is hydrogen, halogen, cyano, d-C 4 alkyl, C C 4 alkoxy, C 2 -C 4 alkenyl, C 2 -C alkynyl or halomethyl; n is 1 or 2.
- the formula I embraces all stereoisomeric forms and mixtures thereof, such as racemic and diasteromeric mixtures, for example E/Z mixtures.
- the compounds according to the invention exhibit improved biological properties which render them very suitable for practical use in agriculture and horticulture by having an extraordinarily good fungicidal activity, especially in cereals.
- the invention furthermore relates to the preparation of these compounds, to agrochemical compositions which comprise, as active ingredients, at least one of these compounds, and to the use of the active ingredients or of the compositions for protecting plants against attack by harmful microorganisms, in particular fungi.
- C C alkyl on its own or as structural element of other groups such as alkoxy, is methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl or tert-butyl.
- Alkenyl is straight-chain or branched, for example vinyl, allyl, methallyl, 1-methyivinyl or but-
- Alkynyl is straight-chain or branched, for example ethynyl, propargyl, but-1 -yn-1 -yl, but-1 -yn-
- Halogen or halo is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
- Halomethyl may contain identical or different halogen atoms; examples are fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, difluorochloromethyl, dichlorofluoromethyl; trifluoromethyl being preferred.
- R 2 is methyl
- R 3 is fluoro, chloro or bromo, CrC 4 alkyl, C ⁇ -C 4 alkoxy, ethynyl or trifluoromethyl.
- U is a leaving group, for example chlorine, bromine, iodine, mesyloxy or tosyloxy
- the compounds of formula I can be used in the agricultural sector and related fields preventively and/or curatively as active ingredients in the control of plant diseases.
- the compounds of formula I according to the invention are distinguished by having good activity even at low rates of concentration, by being well tolerated by plants and by being environmentally friendly. They possess very advantageous, especially systemic, properties and can be used for the protection of a large number of cultivated plants. With the compounds of formula I it is possible to inhibit or destroy the pests that occur on plants or on parts of plants (the fruit, blossom, leaves, stems, tubers or roots) of various crops of useful plants, while parts of plants that grow later are also protected against phytopathogenic microorganisms, in particular fungi.
- the compounds I can also be used as dressings in the treatment of seed (fruit, tubers, grains) and plant cuttings to provide protection against fungus infections as well as against phytopathogenic fungi that occur in the soil
- the compounds I are effective, for example, against phytopathogenic fungi belonging to the following classes Fungi imperfecti (e.g. Botrytis, Py ⁇ cularia, Helminthospo ⁇ um, Fusa ⁇ um, Septo ⁇ a, Cercospora und Altema ⁇ a); Basidiomycetes (e.g Rhizoctonia, Hemileia, Pucc- inia), Ascomycetes (e g Ventu ⁇ a and Erysiphe, Podosphaera, Monilinia, Uncinula) and Oomycetes (e g Phytophthora, Pythium, Plasmopara).
- Fungi imperfecti e.g. Botrytis, Py ⁇ cularia, Helminthospo ⁇ um, Fusa ⁇ um, Septo ⁇ a, Cercospora und Altema ⁇ a
- Basidiomycetes e.g Rhizoctonia, Hemileia, Pucc- inia
- Ascomycetes e
- target crops for plant protection use include, for example, the following species of plants: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related crops); beet (sugar beet and fodder beet), pomes, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries), leguminous plants (beans, lentils, peas, soybeans), oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts), cucumber plants (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocados, cinnamon, camphor), and plants such as tobacco, nuts, coffee
- the compounds I are usually used in the form of compositions and can be applied to the area or plant to be treated simultaneously or in succession with further active ingredients
- further active ingredients may be, for example, fertilisers, micronut ⁇ ent donors or other preparations that influence plant growth It is also possible to use selective herbicides, and insecticides, fungicides, bacte ⁇ cides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or other application-promoting adjuvants customarily employed in formulation technology
- Suitable carriers and adjuvants may be solid or liquid and are the substances usefully employed in formulation technology, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers.
- a preferred method of applying a compound of formula I, or an agrochemical composition comprising at least one of those compounds, is application to the foliage of the plants (foliar application).
- the frequency and the rate of application depend upon the risk of infestation by the pathogen in question.
- the compounds of formula I can also penetrate the plants through the roots via the soil (systemic action) if the locus of the plants is impregnated with a liquid formulation or if the active ingredients are incorporated into the soil in solid form, e.g. in granular form (soil application). In the case of paddy rice crops, such granules may be applied in metered amounts to the flooded rice field.
- the compounds of formula I may, however, for seed treatment, also be applied to the seed grains (coating), either by impregnating the seeds or tubers with a liquid formulation of the active ingredient or by coating them with a solid formulation.
- the compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology.
- they are advantageously formulated in known manner e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts or granules, for example by encapsulation in e.g. polymer substances.
- the methods of application such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
- Advantageous rates of application are generally from 1 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha, especially from 20 g to 600 g a.i./ha.
- rates of from 10 mg to 1 g of active ingredient per kg of seed are advantageously used.
- compositions, preparations or mixtures comprising the compound (active ingredient) of formula I and, where appropriate, a solid or liquid adjuvant are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredient with extenders, such as solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
- extenders such as solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
- the agrochemical compositions normally comprise 0.1 to 99 % by weight, especially 0.1 to 95 % by weight, compound of formula I, 99.9 to 1 % by weight, especially 99.8 to 5 % by weight, of a solid or liquid adjuvant, and 0 to 25 % by weight, especially 0.1 to 25 % by weight, of a surfactant.
- the compounds of formula I can be mixed with other fungicides, producing in some cases unexpected synergistic effects.
- Especially preferred mixing partners are azoles such as azaconazole, bitertanol, propiconazole, difenoconazole, diniconazole, cyproconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, tebuconazole, tetraconazole, fenbuconazole, metconazole, myclobutanil, perfurazoate, penconazole, bromuconazole, pyrifenox, prochloraz, triadimefon, triadimenol, triflumizole or triticonazole; pyrimidinyl carbinoles such as ancymidol, fenarimol or nuarimol; 2-amino- pyrimidine such as bupirimate, dimethirimol or ethiri
- Example B-1 Action against Puccinia qraminis on wheat a) Residual-protective action
- wheat plants are sprayed to drip point with an aqueous spray mixture (0.02 % active ingredient), prepared from a wettable powder formulation of the active ingredient, and infected 24 hours later with a uredospore suspension of the fungus. After an incubation period of 48 hours (conditions: 95-100 % relative humidity at 20°), the plants are placed in a greenhouse at 22°. Fungus infestation is evaluated 12 days after infection. In this test compounds 1 , 3, 5, 7, 8 and 10 of Table 1 showed an efficacy of 80% or more.
- wheat plants are watered with an aqueous spray mixture (0.006 % active ingredient, based on the volume of the soil), prepared from a wettable powder formulation of the active ingredient. Care is taken that the spray mixture does not come into contact with parts of the plants that are above the soil.
- the plants are infected 48 hours later with a uredospore suspension of the fungus. After an incubation period of 48 hours (conditions 95-100 % relative humidity at 20°), the plants are placed in a greenhouse at 22°. Fungus infestation is evaluated 12 days after infection.
- Example B-2 Action against Phvtophthora infestans on tomatoes a) Residual-protective action
- aqueous spray mixture (0.02 % active ingredient), prepared from a wettable powder formulation of the active ingredient, and infected 24 hours later with a sporangia suspension of the fungus. Fungus infestation is evaluated 5 days after infection, a relative humidity of 90 to 100 % and a temperature of 20° having been maintained during that period. b) Systemic action
- tomato plants are watered with an aqueous spray mixture (0.006 % active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the active ingredient. Care is taken that the spray mixture does not come into contact with parts of the plants that are above the soil. After 48 hours, the plants are infected with a sporangia suspension of the fungus. Fungus infestation is evaluated 5 days after infection, a relative humidity of 90 to 100 % and a temperature of 20° having been maintained during that period.
- aqueous spray mixture 0.006 % active ingredient, based on the volume of the soil
- Care is taken that the spray mixture does not come into contact with parts of the plants that are above the soil.
- the plants are infected with a sporangia suspension of the fungus. Fungus infestation is evaluated 5 days after infection, a relative humidity of 90 to 100 % and a temperature of 20° having been maintained during that period.
- Example B-3 Action against Plasmopara viticola on vines
- Vine seedlings at the 4- to 5-leaf stage are sprayed to drip point with an aqueous spray mixture (0.02 % active ingredient), prepared from a wettable powder formulation of the active ingredient, and infected 24 hours later with a sporangia suspension of the fungus.
- an aqueous spray mixture (0.02 % active ingredient), prepared from a wettable powder formulation of the active ingredient, and infected 24 hours later with a sporangia suspension of the fungus.
- Fungus infestation is evaluated 6 days after infection, a relative humidity of 95 to100 % and a temperature of 20° having been maintained during that period.
- Example B-4 Residual-protective action against Venturia inaequalis on apples Apple cuttings with 10-20 cm long fresh shoots are sprayed to drip point with an aqueous spray mixture (0.02 % active ingredient), prepared from a wettable powder formulation of the active ingredient, and infected 24 hours later with a conidia suspension of the fungus. The plants are incubated for 5 days at 90-100 % relative humidity and placed in a greenhouse for a further 10 days at 20-24°. Fungus infestation is evaluated 12 days after infection.
- Example B-5 Action against Erysiphe graminis on barley a) Residual-protective action
- Barley plants about 8 cm in height are watered with an aqueous spray mixture (0.002 % active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the active ingredient. Care is taken that the spray mixture does not come into contact with parts of the plants that are above the soil. The plants are dusted 48 hours later with conidia of the fungus. The infected plants are placed in a greenhouse at 22°. Fungus infestation is evaluated 12 days after infection.
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
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- General Health & Medical Sciences (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to novel pesticidal tris-oxime compounds of formula (I) wherein R2 is hydrogen, methyl or ethyl; R3 is hydrogen, halogen, cyano, C1-C4alkyl, C1-C4alkoxy, C2-C4alkenyl, C2-C4alkynyl or halomethyl; and n is 1 or 2. The novel compounds have plant-protecting properties and are suitable for protecting plants against infestation by phytopathogenic microorganisms.
Description
Pesticidal Tris-oxime Compounds
The invention relates to novel pesticidally, in particular fungicidally, active tris-oxime compounds of formula I
wherein
R2 is hydrogen, methyl or ethyl;
R3 is hydrogen, halogen, cyano, d-C4alkyl, C C4alkoxy, C2-C4alkenyl, C2-C alkynyl or halomethyl; n is 1 or 2.
The formula I embraces all stereoisomeric forms and mixtures thereof, such as racemic and diasteromeric mixtures, for example E/Z mixtures.
1 ,2-Dioxime ether derivatives having fungicidal activities are known, e.g. from
WO 95/18789.
It has been found that the compounds according to the invention exhibit improved biological properties which render them very suitable for practical use in agriculture and horticulture by having an extraordinarily good fungicidal activity, especially in cereals.
The invention furthermore relates to the preparation of these compounds, to agrochemical compositions which comprise, as active ingredients, at least one of these compounds, and to the use of the active ingredients or of the compositions for protecting plants against attack by harmful microorganisms, in particular fungi.
The general terms used herein have the following meanings:
C C alkyl, on its own or as structural element of other groups such as alkoxy, is methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl or tert-butyl.
Alkenyl is straight-chain or branched, for example vinyl, allyl, methallyl, 1-methyivinyl or but-
2-en-1 -yl.
Alkynyl is straight-chain or branched, for example ethynyl, propargyl, but-1 -yn-1 -yl, but-1 -yn-
3-yl. Ethynyl and propargyl are preferred.
Halogen or halo is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
Halomethyl may contain identical or different halogen atoms; examples are fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, difluorochloromethyl, dichlorofluoromethyl; trifluoromethyl being preferred.
Preferred are compounds of formula I wherein
R2 is methyl;
R3 is fluoro, chloro or bromo, CrC4alkyl, Cι-C4alkoxy, ethynyl or trifluoromethyl.
Particularly preferred are the compounds of the Table 1 , especially 1 to 8 and 10.
The compounds of formula I can be prepared as follows:
A compound of formula II, wherein U is a leaving group, for example chlorine, bromine, iodine, mesyloxy or tosyloxy, is reacted with a compound of formula III, wherein the substituents are as defined for formula I, preferably in an organic solvent in presence of a base.
Compounds of formula II and III are known or can be prepared by known methods.
The compounds of formula I can be used in the agricultural sector and related fields preventively and/or curatively as active ingredients in the control of plant diseases. The compounds of formula I according to the invention are distinguished by having good activity even at low rates of concentration, by being well tolerated by plants and by being environmentally friendly. They possess very advantageous, especially systemic, properties and can
be used for the protection of a large number of cultivated plants. With the compounds of formula I it is possible to inhibit or destroy the pests that occur on plants or on parts of plants (the fruit, blossom, leaves, stems, tubers or roots) of various crops of useful plants, while parts of plants that grow later are also protected against phytopathogenic microorganisms, in particular fungi.
The compounds I can also be used as dressings in the treatment of seed (fruit, tubers, grains) and plant cuttings to provide protection against fungus infections as well as against phytopathogenic fungi that occur in the soil
The compounds I are effective, for example, against phytopathogenic fungi belonging to the following classes Fungi imperfecti (e.g. Botrytis, Pyπcularia, Helminthospoπum, Fusaπum, Septoπa, Cercospora und Altemaπa); Basidiomycetes (e.g Rhizoctonia, Hemileia, Pucc- inia), Ascomycetes (e g Ventuπa and Erysiphe, Podosphaera, Monilinia, Uncinula) and Oomycetes (e g Phytophthora, Pythium, Plasmopara).
Within the scope of the invention, target crops for plant protection use include, for example, the following species of plants: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related crops); beet (sugar beet and fodder beet), pomes, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries), leguminous plants (beans, lentils, peas, soybeans), oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts), cucumber plants (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocados, cinnamon, camphor), and plants such as tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.
The compounds I are usually used in the form of compositions and can be applied to the area or plant to be treated simultaneously or in succession with further active ingredients These further active ingredients may be, for example, fertilisers, micronutπent donors or other preparations that influence plant growth It is also possible to use selective herbicides, and insecticides, fungicides, bacteπcides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or other application-promoting adjuvants customarily employed in formulation technology
Suitable carriers and adjuvants may be solid or liquid and are the substances usefully employed in formulation technology, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers.
A preferred method of applying a compound of formula I, or an agrochemical composition comprising at least one of those compounds, is application to the foliage of the plants (foliar application). The frequency and the rate of application depend upon the risk of infestation by the pathogen in question. However, the compounds of formula I can also penetrate the plants through the roots via the soil (systemic action) if the locus of the plants is impregnated with a liquid formulation or if the active ingredients are incorporated into the soil in solid form, e.g. in granular form (soil application). In the case of paddy rice crops, such granules may be applied in metered amounts to the flooded rice field. The compounds of formula I may, however, for seed treatment, also be applied to the seed grains (coating), either by impregnating the seeds or tubers with a liquid formulation of the active ingredient or by coating them with a solid formulation.
The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology. For that purpose they are advantageously formulated in known manner e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts or granules, for example by encapsulation in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
Advantageous rates of application are generally from 1 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha, especially from 20 g to 600 g a.i./ha. When used as seed dressings, rates of from 10 mg to 1 g of active ingredient per kg of seed are advantageously used.
The formulations, i.e. the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredient
with extenders, such as solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
The agrochemical compositions normally comprise 0.1 to 99 % by weight, especially 0.1 to 95 % by weight, compound of formula I, 99.9 to 1 % by weight, especially 99.8 to 5 % by weight, of a solid or liquid adjuvant, and 0 to 25 % by weight, especially 0.1 to 25 % by weight, of a surfactant.
The compounds of formula I can be mixed with other fungicides, producing in some cases unexpected synergistic effects.
Especially preferred mixing partners are azoles such as azaconazole, bitertanol, propiconazole, difenoconazole, diniconazole, cyproconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, tebuconazole, tetraconazole, fenbuconazole, metconazole, myclobutanil, perfurazoate, penconazole, bromuconazole, pyrifenox, prochloraz, triadimefon, triadimenol, triflumizole or triticonazole; pyrimidinyl carbinoles such as ancymidol, fenarimol or nuarimol; 2-amino- pyrimidine such as bupirimate, dimethirimol or ethirimol; morpholines such as dodemorph, fenpropidin, fenpropimorph, spiroxamin or tridemorph; anilinopyrimidines such as cyprodinil, pyrimethanil or mepanipyrim; pyrroles such as fenpiclonil or fludioxonil; phenylamides such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace or oxadixyl; benzimidazoles such as benomyl, carbendazim, debacarb, fuberidazole or thiabendazole; dicarboximides such as chlozolinate, dichlozoline, iprodine, myclozoline, procymidone or vinclozolin; carboxamides such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin or thifluzamide; guanidines such as guazatine, dodine or iminoctadine; strobilurines such as azoxystrobin, kresoxim- methyl, metominostrobin, SSF-129, methyl 2-[(2-trifluoromethyl)-pyrid-6-yloxymethyl]-3- methoxyacrylate or 2-[α{[( -methyl-3-trifluoromethyl-benzyl)imino]-oxy}-o-tolyl]-glyoxylic acid-methylester-O-methyloxime (trifloxystrobin); dithiocarbamates such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb or ziram; N-halomethylthio- dicarboximides such as captafol, captan, dichlofluanid, fluoromide, folpet or tolyfluanid; copper compounds such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper or oxine-copper; nitrophenol derivatives such as dinocap or nitrothal-isopropyl; organo phosphorous derivatives such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos or toclofos-methyl; and other compounds of diverse structures such as acibenzolar-S-methyl, anilazine, blasticidin-S, chinomethionat, chloroneb, chlorothalonil, cymoxanil, dichlone, diclomezine, dicloran,
diethofencarb, dimethomorph, dithianon, etridiazole, famoxadone, fenamidone, fentin, ferimzone, fluazinam, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, kasuga- mycin, methasulfocarb, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine, validamycin, (S)-5-methyl-2-methylthio-5-phenyl-3-phenyl-amino-3,5-dihydroimidazol-4-one (RPA 407213), 3,5-dichloro-N-(3-chloro-1 -ethyl-1 -methyl-2-oxopropyl)-4-methylbenzamide (RH-7281 ), N-allyl-4,5-dimethyl-2-trimethylsilylthiophene-3-carboxamide (MON 65500), 4-chloro-4-cyano-N,N-dimethyl-5-p-tolylimidazole-1 -sulfon-amide (IKF-916), N-(1 -cyano-1 ,2- dimethylpropyl)-2-(2,4-dichlorophenoxy)-propionamide (AC 382042), or iprovalicarb (SZX 722).
1. Preparation Example
Example P-1 : Preparation of compound No. 1.7
0.2 g of a 60 % sodium hydride dispersion in mineral oil is washed with hexane, and 5 ml of N,N-dimethylformamide are added thereto. To that suspension there are added 1.5 g of 2-(bromomethylphenyl)glyoxylic acid ethyl ester O-methyl oxime and 1.2 g of 1-(4-bromophenyl)-propane-1 ,2-dione-1 -(0-methyloxime)-2-oxime. The reaction mixture is heated to 50°C and stirred at room temperature for one hour. Ice-water is then added and extraction is carried out twice with 50 ml of ethyl acetate each time. The combined organic extracts are washed with water and dried over sodium sulfate and the solvent is distilled off under reduced pressure. The residue is purified by chromatography on silica gel using ethyl acetate/hexane (1 :5 % by volume to 1 :4 % by volume). 1.3 g of the desired product are obtained in the form of white crystals, m.p.103-104°C.
The compounds of the following table may be obtained in analogous manner.
Table 1
No. R3 phys. data (m.p.°C) * mixture of isomers
1. 2-F-4-C4H90 oil
2. 3-CF3-4-CI 80-82
3. 2-CH3-4-C3H70 91 -93
4. 2-F-4-CH3O 98-100
5. 4-CF3 95-97
6. 4-CH3 oil*
7. 4-Br 103-104
8. 4-F 74-75
9. 4-C≡CH oil*
10. 2,4-F2 90-93
1 1 . 4-CH3O oil*
12. 4-C2H50 100-102*
13. 4-C3H7O oil*
14. 2,5-(CH3)2 oil*
15. 4-C4H90 oil*
16. 4-CI oil*
17. 4-CN oil*
18. 4-CH=CH2 oil*
2. Formulation examples for similar purposes of pesticidal use are descibed for example in WO 97/33890
3. Biological Examples:
In the following pathosystems the compounds of the table exhibit good activities.
Example B-1 : Action against Puccinia qraminis on wheat a) Residual-protective action
6 days after sowing, wheat plants are sprayed to drip point with an aqueous spray mixture (0.02 % active ingredient), prepared from a wettable powder formulation of the active ingredient, and infected 24 hours later with a uredospore suspension of the fungus. After an incubation period of 48 hours (conditions: 95-100 % relative humidity at 20°), the plants are placed in a greenhouse at 22°. Fungus infestation is evaluated 12 days after infection. In this test compounds 1 , 3, 5, 7, 8 and 10 of Table 1 showed an efficacy of 80% or more. b) Systemic action
5 days after sowing, wheat plants are watered with an aqueous spray mixture (0.006 % active ingredient, based on the volume of the soil), prepared from a wettable powder formulation of the active ingredient. Care is taken that the spray mixture does not come into contact with parts of the plants that are above the soil. The plants are infected 48 hours later with a uredospore suspension of the fungus. After an incubation period of 48 hours (conditions 95-100 % relative humidity at 20°), the plants are placed in a greenhouse at 22°. Fungus infestation is evaluated 12 days after infection.
Example B-2: Action against Phvtophthora infestans on tomatoes a) Residual-protective action
After a cultivation period of three weeks, tomato plants are sprayed to drip point with an aqueous spray mixture (0.02 % active ingredient), prepared from a wettable powder formulation of the active ingredient, and infected 24 hours later with a sporangia suspension of the fungus. Fungus infestation is evaluated 5 days after infection, a relative humidity of 90 to 100 % and a temperature of 20° having been maintained during that period. b) Systemic action
After a cultivation period of three weeks, tomato plants are watered with an aqueous spray mixture (0.006 % active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the active ingredient. Care is taken that the spray mixture does not come into contact with parts of the plants that are above the soil. After 48 hours, the plants are infected with a sporangia suspension of the fungus. Fungus infestation is
evaluated 5 days after infection, a relative humidity of 90 to 100 % and a temperature of 20° having been maintained during that period.
Example B-3: Action against Plasmopara viticola on vines
Vine seedlings at the 4- to 5-leaf stage are sprayed to drip point with an aqueous spray mixture (0.02 % active ingredient), prepared from a wettable powder formulation of the active ingredient, and infected 24 hours later with a sporangia suspension of the fungus.
Fungus infestation is evaluated 6 days after infection, a relative humidity of 95 to100 % and a temperature of 20° having been maintained during that period.
In this test compounds 3 to 8 and 10 of Table 1 showed an efficacy of 90% or more.
Example B-4: Residual-protective action against Venturia inaequalis on apples Apple cuttings with 10-20 cm long fresh shoots are sprayed to drip point with an aqueous spray mixture (0.02 % active ingredient), prepared from a wettable powder formulation of the active ingredient, and infected 24 hours later with a conidia suspension of the fungus. The plants are incubated for 5 days at 90-100 % relative humidity and placed in a greenhouse for a further 10 days at 20-24°. Fungus infestation is evaluated 12 days after infection.
Example B-5: Action against Erysiphe graminis on barley a) Residual-protective action
Barley plants about 8 cm in height are sprayed to drip point with an aqueous spray mixture (0.02 % active ingredient), prepared from a wettable powder formulation of the active ingredient, and dusted 3 to 4 hours later with conidia of the fungus. The infected plants are placed in a greenhouse at 22°. Fungus infestation is evaluated 12 days after infection. In this test compound 2,5 and 10 of Table 1 showed an efficacy of 90% or more. b) Systemic action
Barley plants about 8 cm in height are watered with an aqueous spray mixture (0.002 % active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the active ingredient. Care is taken that the spray mixture does not come into contact with parts of the plants that are above the soil. The plants are dusted 48 hours later with conidia of the fungus. The infected plants are placed in a greenhouse at 22°. Fungus infestation is evaluated 12 days after infection.
Claims
1. A compound of formula
wherein:
R2 is hydrogen, methyl or ethyl;
R3 is hydrogen, halogen, cyano, d-C alkyl, d-C4alkoxy, C2-C alkenyl, C2-C4alkynyl or halomethyl; n is 1 or 2.
2. A compound according to claim 1 wherein
R is methyl; R3 is fluoro, chloro or bromo, C C alkyl, C C alkoxy, ethynyl or trifluoromethyl.
3. A composition for controlling fungi which comprises, as active ingredient, an effective amount of a compound according to claim 1 together with a suitable carrier material.
4. A method of controlling and preventing infestation of plants by phytopathogenic fungi, which comprises applying a compound according to claim 1 to the plants, their parts or their environment.
5. A process for the preparation of a compound of formula I according to claim 1 ,
wherein a compound of formula II, wherein U is a leaving group, is reacted with a compound of formula III, wherein R2, R3 and n are as defined for formula I.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB9820582.6A GB9820582D0 (en) | 1998-09-22 | 1998-09-22 | Organic compounds |
GB9820582 | 1998-09-22 | ||
PCT/EP1999/006953 WO2000017154A1 (en) | 1998-09-22 | 1999-09-20 | Pesticidal tris-oxime compounds |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1115698A1 true EP1115698A1 (en) | 2001-07-18 |
Family
ID=10839236
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99948797A Withdrawn EP1115698A1 (en) | 1998-09-22 | 1999-09-20 | Pesticidal tris-oxime compounds |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1115698A1 (en) |
JP (1) | JP2002526469A (en) |
AU (1) | AU6193099A (en) |
GB (1) | GB9820582D0 (en) |
WO (1) | WO2000017154A1 (en) |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU690190B2 (en) * | 1994-01-05 | 1998-04-23 | Bayer Aktiengesellschaft | Pesticides |
PL185913B1 (en) * | 1995-12-07 | 2003-08-29 | Bayer Ag | Pesticides |
-
1998
- 1998-09-22 GB GBGB9820582.6A patent/GB9820582D0/en not_active Ceased
-
1999
- 1999-09-20 JP JP2000574064A patent/JP2002526469A/en active Pending
- 1999-09-20 WO PCT/EP1999/006953 patent/WO2000017154A1/en not_active Application Discontinuation
- 1999-09-20 EP EP99948797A patent/EP1115698A1/en not_active Withdrawn
- 1999-09-20 AU AU61930/99A patent/AU6193099A/en not_active Abandoned
Non-Patent Citations (1)
Title |
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See references of WO0017154A1 * |
Also Published As
Publication number | Publication date |
---|---|
JP2002526469A (en) | 2002-08-20 |
AU6193099A (en) | 2000-04-10 |
WO2000017154A1 (en) | 2000-03-30 |
GB9820582D0 (en) | 1998-11-11 |
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