WO2011076501A1 - Nouveaux dérivés de 5-(pyridin-3-yl)-pyridazine et leur utilisation en tant que microbicides - Google Patents

Nouveaux dérivés de 5-(pyridin-3-yl)-pyridazine et leur utilisation en tant que microbicides Download PDF

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WO2011076501A1
WO2011076501A1 PCT/EP2010/067880 EP2010067880W WO2011076501A1 WO 2011076501 A1 WO2011076501 A1 WO 2011076501A1 EP 2010067880 W EP2010067880 W EP 2010067880W WO 2011076501 A1 WO2011076501 A1 WO 2011076501A1
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compound
formula
methyl
chloro
plants
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PCT/EP2010/067880
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Stephan Trah
Clemens Lamberth
Francesca Peruccio
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Syngenta Participations Ag
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    • 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
    • C07D405/04—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 directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D233/44—Nitrogen atoms not forming part of a nitro radical
    • C07D233/50—Nitrogen atoms not forming part of a nitro radical with carbocyclic radicals directly attached to said nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to novel pyridazine derivatives as active ingredients which have microbiocidal activity, in particular fungicidal activity.
  • the invention also relates to preparation of these active ingredients, to novel heterocyclic derivatives used as intermediates in the preparation of these active ingredients, to preparation of these novel intermediates, to agrochemical compositions which comprise at least one of the novel active ingredients, to preparation of these compositions and to use of the active ingredients or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, preferably fungi.
  • Pyridazine derivatives for use as fungicides are proposed in international patent applications WO 2005/121 104, WO 2006/001 175, WO 2007/066601 , WO 2007/080720, WO2008/009405 and WO2008/009406.
  • new compounds may possess improved fungicidal properties, such as improved efficacy, improved selectivity, lower tendency to generate resistance or activity against a broader spectrum of fungi.
  • Compounds may be more advantageously formulated or provide more efficient delivery and retention at sites of action, or may be more readily biodegradable.
  • fungicides having an improved curative action.
  • the pyridazine compounds of the present invention exhibit unexpected fungicidal activity, including unexpected curative activity, and are therefore suitable for use in agriculture as crop protection agents to combat or prevent fungal infestations.
  • the present invention provid ula (I)
  • R 1 is methyl or ethyl
  • R 2 is H, fluoro or chloro
  • R 3 is fluoro or chloro
  • R 4 is fluoro or methoxy
  • R 5 is chloro or methoxy
  • the present invention includes all those possible isomeric forms and mixtures thereof for a compound of formula (I). For instance, atropisomers may occur as a result of restricted rotation about a single bond.
  • R 1 is methyl
  • R 2 is H or fluoro
  • R 3 is fluoro or chloro
  • R 4 is fluoro or methoxy
  • R 5 is chloro
  • Preferred individual compounds are selected from
  • the compounds of formula (1.2) may be obtained by transformation of a compound of formula (1.1 ) with methanol and base or with sodium methoxide.
  • the compounds of formula (1.1 ) may be obtained by transformation of a compound of formula (1.3) with phosphorus oxychloride or thionyl chloride.
  • the compounds of formula (1.3) may be obtained by transformation of a compound of formula (II) with a hydrazine derivative, e.g. hydrazine hydrate.
  • the compounds of formula (II) may be obtained by transformation of a compound of formula (III) by oxidation with oxygen, air or 3-chloroperbenzoic acid.
  • the compounds of formula (III) may be obtained by transformation of a compound of formula (IV), wherein R 1 , R 2 , R 3 and R 4 are as defined for formula (I), with a base, e.g. pyridine, triethylamine, diisopropylethylamine, 1 ,5-diazabicyclo[4.3.0]non-5-e n e or 1 ,8-diazabicyclo[5.4.0]undec-7-ene.
  • a base e.g. pyridine, triethylamine, diisopropylethylamine, 1 ,5-diazabicyclo[4.3.0]non-5-e n e or 1 ,8-diazabicyclo[5.4.0]undec-7-ene.
  • the compounds of formula (IV) may be obtained by transformation of a compound of formula (V), wherein Hal is halogen, preferably chlorine or bromine, with a compound of formula (VI) and a base, e.g. pyridine, triethylamine, diisopropylethylamine, 1 ,5-diazabicyclo[4.3.0]non-5-ene or 1 ,8-diazabicyclo[5.4.0]undec-7-ene.
  • a base e.g. pyridine, triethylamine, diisopropylethylamine, 1 ,5-diazabicyclo[4.3.0]non-5-ene or 1 ,8-diazabicyclo[5.4.0]undec-7-ene.
  • the compounds of formula (I) can be used in unmodified form or, preferably, together with carriers and adjuvants conventionally employed in the art of formulation. Therefore the invention additionally provides compositions for controlling and protecting against phytopathogenic micro-organisms, comprising a compound of formula (I) and an inert carrier, and to a method of controlling or preventing infestation of useful plants by phytopathogenic micro-organisms, wherein a composition, comprising a compound of formula (I) as active ingredient and an inert carrier, is applied to the plants, to parts thereof or the locus thereof.
  • the invention could be used to protect non-living materials from fungal attack, e.g. lumber, wall boards and paint.
  • compositions are conveniently formulated in known manner to mollifiable concentrates, coat able pastes, directly spray able or dilatable solutions, dilute emulsions, wet table powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric 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.
  • the compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or pacifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
  • Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation tech nology, e.g . natu ral or regenerated mi neral su bstances , solvents , dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.
  • the compounds of formula (I) or compositions, comprising a compound of formula (I) as active ingredient and an inert carrier can be applied to the locus of the plant or plant to be treated, simultaneously or in succession with further compounds.
  • further compounds can be e.g. fertilizers or micronutrient donors or other preparations which influence the growth of plants. They can also be selective herbicides, plant growth regulators as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
  • a preferred method of applying a com pound of formula (I), or a com position , comprising a compound of formula (I) as active ingredient and an inert carrier is foliar application.
  • the frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen.
  • the compounds of formula (I) can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field.
  • the compounds of formula (I) may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
  • a formulation i.e. a composition comprising the compound of formula (I) and, if desired, a solid or liquid adjuvant, is prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface-active compounds (surfactants).
  • the agrochemical formulations will usually contai n from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula (I), 99.9 to 1 % by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant. Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.
  • Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 10g to 1 kg a.i./ha, most preferably from 20g to 600g a.i./ha.
  • convenient rates of application are from 10mg to 1 g of active substance per kg of seeds.
  • the rate of application for the desired action can be determined by experiments. It depends for example on the type of action, the developmental stage of the useful plant, and on the application (location, timing, application method) and can, owing to these parameters, vary within wide limits.
  • the invention relates to a method of controlling or preventing infestation of useful plants by phytopathogenic micro-organisms, wherein a compound of formula (I) is applied as active ingredient to the plants, to parts thereof or the locus thereof.
  • the compounds of formula (I) according to the invention are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and are used for protecting numerous useful plants.
  • the compounds of formula (I) can be used to inhibit or destroy the diseases that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later e.g. from phytopathogenic micro-organisms.
  • compounds of formula (I) as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
  • the compounds of formula (I) according to the invention may be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related techn ical products, i n food storage or in hygiene management.
  • useful plants to be protected typically comprise the following groups of plants: cereals (wheat, barley, rye, oat, rice, maize, sorghum and related species); beets (sugar beet and fodder beet); pomes, drupes 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); cucurbit plants (pumpkins, 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 (avocado, cinnamomum, camphor)
  • useful plants and / or “target crops” is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inh ibitors, GS (glutamine synthetase) in hibitors or P PO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering.
  • herbicides like bromoxynil or classes of herbicides
  • EPSPS 5-enol-pyrovyl-shikimate-3-phosphate-synthase
  • GS glutamine synthetase
  • P PO protoporphyrinogen-oxidase
  • An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola).
  • crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names Round upReady® , Herculex I® and LibertyLink®.
  • useful plants and / or target crops is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • useful plants and / or target crops is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called “pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392 225).
  • PRPs pathogenesis-related proteins
  • locus of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed into the soil.
  • An example for such a locus is a field, on which crop plants are growing.
  • plant propagation material is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably "plant propagation material” is understood to denote seeds.
  • the compounds of formula (I) are, for example, effective against the phytopathogenic fungi of the following classes:
  • the compounds of formula (I) are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Alternaria spp.), Basidiomycetes (e.g. Corticium spp., Ceratobasidium spp., Waitea spp., Thanatephorus spp., Rhizoctonia spp., Hemileia spp., Puccinia spp., Phakopsora spp., Ustilago spp., T/V/ef/ ' a spp.), Ascomycetes (e.g.
  • Venturia spp. Blumeria spp., Erysiphe spp., Podosphaera spp., Uncinula spp., Monilinia spp., Sclerotinia spp., Colletotrichum spp., Glomerella spp., Fusarium spp., Gibberella spp., Monographella spp., Phaeosphaeria spp., Mycosphaerella spp., Cercospora spp., Pyrenophora spp., Rhynchosporium spp., Magnaporthe spp., Gaeumannomyces spp., Oculimacula spp., Ramularia spp., Botryotinia spp.) and Oomycetes (e.g.
  • Phytophthora spp. Pythium spp., Plasmopara spp., Peronospora spp., Pseudoperonospora spp. Bremia spp).
  • Outstanding activity has been observed against powdery mildews (e.g. Uncinula necator), rusts (e.g. Puccinia spp.) and leaf spots (e.g. Mycosphaerella spp.).
  • the novel compounds of formula (I) are effective against phytopathogenic gram negative and gram positive bacteria (e.g. Xanthomonas spp, Pseudomonas spp, Erwinia amylovora, Ralstonia spp.) and viruses (e.g. tobacco mosaic virus).
  • the compounds and compositions of the present invention are used against the fungal organism Mycosphaerella graminicola.
  • the compounds of formula (I) are normally used in the form of fungicidal compositions for controlling or protecting against phytopathogenic microorganisms, comprising as active ingredient at least one compound of formula (I) or at least one preferred individual compound as above-defined, in free form or in agrochemically usable salt form, and at least one of the above-mentioned adjuvants.
  • Said fungicidal compositions for controlling or protecting against phytopathogenic microorganisms comprising as active ingredient at least one compound of formula (I) or at least one preferred individual compound as above-defined, in free form or in agrochemically usable salt form, and at least one of the above-mentioned adjuvants can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities.
  • Mixing components which are particularly preferred are:
  • Azoles such as azaconazole, BAY 14120, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, proth ioconazole, pyrifenox, proch loraz, propiconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole;
  • Pyrimidinyl carbinoles such as ancymidol, fenarimol, nuarimol;
  • 2-amino-pyrimidines such as bupirimate, dimethirimol, ethirimol
  • Morpholines such as dodemorph , fenpropidine, fenpropimorph , spiroxamine, tridemorph;
  • Anilinopyrimidines such as cyprodinil, mepanipyrim, pyrimethanil;
  • Pyrroles such as fenpiclonil, fludioxonil
  • Phenylamides such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl;
  • Benzimidazoles such as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole;
  • Dicarboximides such as chlozolinate, dichlozoline, iprodione, myclozoline, procymi- done, vinclozoline;
  • Carboxamides such as boscalid, carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, penthiopyrad, thifluzamide; guanidines, such as guazatine, dodine, iminoctadine;
  • Strobi lu ri nes such as azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, orysastrobin, picoxystrobin, pyraclostrobin;
  • Dithiocarbamates such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram;
  • N-halomethylthiotetrahydrophthalim ides such as captafol , captan , d ich lofl uan id , fluoromides, folpet, tolyfluanid;
  • Cu-compounds such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper, oxine-copper;
  • Nitrophenol-derivatives such as dinocap, nitrothal-isopropyl
  • Organo-phosphorus-derivatives such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-methyl;
  • Pyridazine-derivatives wh ich are known and may be prepared by methods as described in WO 05/121 104, WO 06/001 175 and WO 07/066601 , such as 3-chloro-5-(4- chloro-phenyl)-6-methyl-4-(2,4,6-trifluoro-phenyl)-pyridazine (formula P.1 ), 3-chloro-6-methyl- 5-p-tolyl-4-(2,4,6-trifluoro-phenyl)-pyri d azi n e (fo rm u l a P .2 ) a n d 3-chloro-4-(3-chloro-5- methoxy-pyridin-2-yl)-5-(4-chloro-phenyl)-6-methyl-pyridazine (formula P.3);
  • Triazolopyrimidine derivatives which are known and may be prepared by methods as described in WO98/46607, such as 5-chloro-7-(4-methyl-piperidin-1-yl)-6-(2,4,6-trifluoro- phenyl)- [1,2,4]triazolo[1,5-a]pyrimidine (formula T.1);
  • Carboxamide derivatives which are known and may be prepared by methods as described in WO04/035589, WO06/37632, WO03/074491 or WO03070705, such as 3- difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid (9-isopropyp-1,2,3,4-tetrahaydro-1,4- methano-naphthalen-5-yl)-amide (formula U.1), 3-difluoromethyl-1-methyl-1 H-pyrazole-4- carboxylic acid (2-bicyclopropyl-2-yl-phenyl)-amide (formula U.2) or N-(3',4'-dichloro-5-fluoro- 1 ,1'-biphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1 H-pyrazole-4-carboxamide;
  • Benzamide derivatives which are known and may be prepared by methods as described in WO 2004/016088, such as N- ⁇ -2-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]ethyl ⁇ - 2-trifluoromethylbenzamide, which is also known under the name fluopyram (formula V.1 );
  • Another aspect of invention is related to the use of a compound of formula (I) or of a preferred individual compound as above-defined, of a composition comprising at least one compound of formula (I) or at least one preferred individual compound as above-defined, or of a fungicidal mixture comprising at least one compound of formula (I) or at least one preferred individual compound as above-defined, in admixture with other fungicides, as described above, for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, preferably fungal organisms.
  • a further aspect of invention is related to a method of controlling or preventing an infestation of crop plants, harvested food crops or of non-living materials by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of formula (I) or of a preferred individual compound as above-defined as active ingredient to the plants, to parts of the plants or to the locus thereof, to seeds or to any part of the non-living materials.
  • Controlling or preventing means reducing the infestation of crop plants or of non-living materials by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, to such a level that an improvement is demonstrated.
  • Table 1 illustrates examples of individual compounds of formula (I) and intermediate (II) according to the invention.
  • Example 1 Prepa rati on of 3-chloro-4-(2,6-difluoro-4-methoxy-phenyl)-6-methyl-5-(6- trifluoromethyl-pyridin-3-yl)-pyridazine (Compound No. 3) a) Preparation of 2-methyl-3-oxo-3-(6-trifluoromethyl-pyridin-3-yl)-propionic acid tert-butyl ester n-Butyllithium (1 .6 M solution in hexane, 46 ml) is added dropwise to the mixture of diisopropylamine (6.8 g) and 70 ml of tetrahydrofuran at -70°C under a nitrogen atmosphere.
  • Bromine (5.0 g) is slowly added to the mixture of 2-methyl-3-oxo-3-(6-trifluoromethyl-pyridin- 3-yl)-propionic acid tert-butyl ester (10.5 g), 0.5 ml of hydrobromic acid (33 % solution in acetic acid) and 30 ml of acetic acid at room temperature under a nitrogen atmosphere. Subsequently, the mixture is slowly heated to 60 °C. The reaction mixture is stirred at 60 °C for 30 min and then cooled down. After neutralisation with saturated aqueous sodium bicarbonate solution the mixture is extracted with ethyl acetate. The organic layer is washed with brine, dried over sodium sulfate and concentrated under reduced pressure.
  • Triethylamine (1.2 g) is slowly added to a solution of 2-bromo-1-(6-trifluoromethyl-pyridin-3- yl)-propan-1-one (3.0 g), 2,4,6-trifluorophenylacetic acid (2.1 g) in 50 ml of acetonitrile and this mixture is stirred for 16h at room temperature. Subsequently 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 3.9 g) is slowly added under cooling and stirring is continued for 1 h. Then air is blown through the reaction mixture for 1 h.
  • DBU 1,8-diazabicyclo[5.4.0]undec-7-ene
  • reaction mixture is poured into an aqueous ammonium chloride solution and the mixture is extracted with ethyl acetate.
  • the combined organic layer is washed with brine, dried over sodium sulfate and evaporated under reduced pressure.
  • the remainder is purified by chromatography on silica gel, using a mixture of cyclohexane / ethyl acetate 3 : 1 as eluent to obtain 5-hydroxy-5- methyl-4-(6-trifluoromethyl-6-pyridin-yl)-3-(2,4,6-trifluoro-phenyl)-5H-furan-2-one a s a yellowish foam.
  • Hydrazine hydrate (0.5 g) is added to a solution of 5-hydroxy-5-methyl-4-(6-trifluoromethyl- pyridin-3-yl)-3-(2,4,6-trifluoro-phenyl)-5H-furan-2-one (3.4 g) in 20 ml of 1-butanol and this mixture is heated for 4 h to 120 °C. Subsequently, the mixture is poured into 20 ml of tert- butyl methyl ether. The resulting mixture is stirred for 30 min, then cooled to 0 °C and filtered.
  • Botryotinia fuckeliana (Botrytis cinerea) I tomato / preventative (Action against Botrytis on tomato)
  • test plants 5- week old grape seedlings cv. Gutedel were treated with the formulated test compound in a spray chamber.
  • the test plants are inoculated by shaking plants infected with grape powdery mildew above them 1 day after application.
  • the inoculated test plants were incubated at 24/22° C (day/night) and 70% rh under a light regime of 14/10 h (light/dark) and the percentage leaf area covered by disease was assessed when an appropriate level of disease appears on untreated check plants (7 - 9 days after application).
  • Mycosphaerella graminicola (Septoria tritici) / wheat / preventive (Action against Septoria leaf spot on wheat)
  • 2-week old wheat plants cv. Riband were treated with the formulated test compound in a spray chamber.
  • the test plants were inoculated by spraying a spore suspension on them one day after application. After an incubation period of 1 day at 22°C/21 °C (day/night) and 95% rh, the test plants were kept at 22°C/21 °C (day/night) and 70% rh in a greenhouse.
  • the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (16 - 19 days after application).
  • Compounds 2 and 3 according to the invention at 200 ppm inhibited fungal infestation in this test to at least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %.
  • Mycosphaerella graminicola (Septoria tritici) I wheat / curative (Action against Septoria leaf spot on wheat)
  • 2-week old wheat plants cv. Ri band are inocu lated by spraying them with a spore suspension. After an incubation period of 2 days at 22°C/21 °C (day/night) and 95% rh, the test plants are kept at 22°C/21 °C (day/night) and 70% rh in a climate chamber. The inoculated test plants are treated with the formulated test compound in a spray chamber 5 days after inoculation. The percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (1 1 - 14 days after application).
  • the percentage leaf area covered by disease was assessed when an appropriate level of disease appears on untreated check plants (12 - 14 days after application).
  • Compounds 2, 3 and 4 according to the invention at 200 ppm inhibited fungal infestation in this test to at least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %.

Abstract

Cette invention concerne de nouveaux dérivés de pyridazine de formule (I) en tant qu'agents actifs ayant une activité microbicide, en particulier une activité fongicide.
PCT/EP2010/067880 2009-12-22 2010-11-22 Nouveaux dérivés de 5-(pyridin-3-yl)-pyridazine et leur utilisation en tant que microbicides WO2011076501A1 (fr)

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EP0392225A2 (fr) 1989-03-24 1990-10-17 Ciba-Geigy Ag Plantes transgéniques résistantes aux maladies
WO1995033818A2 (fr) 1994-06-08 1995-12-14 Ciba-Geigy Ag Genes pour la synthese des substances antipathogenes
WO1997033890A1 (fr) 1996-03-11 1997-09-18 Novartis Ag Derives de pyrimidine-4-one utilises comme pesticide
WO1998046607A1 (fr) 1997-04-14 1998-10-22 American Cyanamid Company Trifluorophenyl-triazolopyrimidines fongicides
WO2003070705A1 (fr) 2002-02-19 2003-08-28 Bayer Cropscience Aktiengesellschaft Carboxanilides de pyrazolyle disubstitues
WO2003074491A1 (fr) 2002-03-05 2003-09-12 Syngenta Participations Ag O-cyclopropyle-carboxanilides et leur utilisation comme fongicides
WO2004016088A2 (fr) 2002-08-12 2004-02-26 Bayer Cropscience S.A. Nouveau derive de 2-pyridylethylbenzamide
WO2004035589A1 (fr) 2002-10-18 2004-04-29 Syngenta Participations Ag Derives d'heterocyclocarboxamide
WO2005121104A1 (fr) 2004-06-09 2005-12-22 Sumitomo Chemical Company, Limited Composé pyridazine et utilisation de celui-ci
WO2006001175A1 (fr) 2004-06-28 2006-01-05 Sumitomo Chemical Company, Limited Compose de pyridazine et son utilisation
WO2006037632A1 (fr) 2004-10-08 2006-04-13 Syngenta Participations Ag Compositions fongicides synergiques
WO2007066601A1 (fr) 2005-12-07 2007-06-14 Sumitomo Chemical Company, Limited Compose de pyridazine et son emploi
WO2007080720A1 (fr) 2005-12-07 2007-07-19 Sumitomo Chemical Company, Limited Compose de pyridazine et son emploi
WO2008009406A1 (fr) 2006-07-17 2008-01-24 Syngenta Participations Ag Nouveaux dérivés de pyridazine
WO2008009405A2 (fr) 2006-07-17 2008-01-24 Syngenta Participations Ag Nouveaux dérivés de pyridazine

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0353191A2 (fr) 1988-07-29 1990-01-31 Ciba-Geigy Ag Séquences d'ADN codant des polypeptides avec activité béta-1,3-glucanase
EP0392225A2 (fr) 1989-03-24 1990-10-17 Ciba-Geigy Ag Plantes transgéniques résistantes aux maladies
WO1995033818A2 (fr) 1994-06-08 1995-12-14 Ciba-Geigy Ag Genes pour la synthese des substances antipathogenes
WO1997033890A1 (fr) 1996-03-11 1997-09-18 Novartis Ag Derives de pyrimidine-4-one utilises comme pesticide
WO1998046607A1 (fr) 1997-04-14 1998-10-22 American Cyanamid Company Trifluorophenyl-triazolopyrimidines fongicides
WO2003070705A1 (fr) 2002-02-19 2003-08-28 Bayer Cropscience Aktiengesellschaft Carboxanilides de pyrazolyle disubstitues
WO2003074491A1 (fr) 2002-03-05 2003-09-12 Syngenta Participations Ag O-cyclopropyle-carboxanilides et leur utilisation comme fongicides
WO2004016088A2 (fr) 2002-08-12 2004-02-26 Bayer Cropscience S.A. Nouveau derive de 2-pyridylethylbenzamide
WO2004035589A1 (fr) 2002-10-18 2004-04-29 Syngenta Participations Ag Derives d'heterocyclocarboxamide
WO2005121104A1 (fr) 2004-06-09 2005-12-22 Sumitomo Chemical Company, Limited Composé pyridazine et utilisation de celui-ci
EP1767529A1 (fr) * 2004-06-09 2007-03-28 Sumitomo Chemical Company, Limited Composé pyridazine et utilisation de celui-ci
WO2006001175A1 (fr) 2004-06-28 2006-01-05 Sumitomo Chemical Company, Limited Compose de pyridazine et son utilisation
WO2006037632A1 (fr) 2004-10-08 2006-04-13 Syngenta Participations Ag Compositions fongicides synergiques
WO2007066601A1 (fr) 2005-12-07 2007-06-14 Sumitomo Chemical Company, Limited Compose de pyridazine et son emploi
WO2007080720A1 (fr) 2005-12-07 2007-07-19 Sumitomo Chemical Company, Limited Compose de pyridazine et son emploi
WO2008009406A1 (fr) 2006-07-17 2008-01-24 Syngenta Participations Ag Nouveaux dérivés de pyridazine
WO2008009405A2 (fr) 2006-07-17 2008-01-24 Syngenta Participations Ag Nouveaux dérivés de pyridazine

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UY33133A (es) 2011-07-29
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TW201143615A (en) 2011-12-16

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