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WO2006066872A1 - Novel triazolopyrimidine derivatives - Google Patents

Novel triazolopyrimidine derivatives Download PDF

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Publication number
WO2006066872A1
WO2006066872A1 PCT/EP2005/013708 EP2005013708W WO2006066872A1 WO 2006066872 A1 WO2006066872 A1 WO 2006066872A1 EP 2005013708 W EP2005013708 W EP 2005013708W WO 2006066872 A1 WO2006066872 A1 WO 2006066872A1
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WO
WIPO (PCT)
Prior art keywords
formula
independently
compound
hydrogen
compounds
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PCT/EP2005/013708
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French (fr)
Inventor
Sebastian Volker Wendeborn
Clemens Lamberth
Kurt Nebel
Patrick Jelf Crowley
Hannes Nussbaumer
Original Assignee
Syngenta Participations Ag
Syngenta Limited
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Publication date
Application filed by Syngenta Participations Ag, Syngenta Limited filed Critical Syngenta Participations Ag
Priority to EP05824434A priority Critical patent/EP1828211A1/en
Priority to BRPI0519179-3A priority patent/BRPI0519179A2/en
Priority to JP2007547321A priority patent/JP2008524292A/en
Publication of WO2006066872A1 publication Critical patent/WO2006066872A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom

Definitions

  • the present invention relates to novel triazolopyrimidine 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 or non-living materials by phytopathogenic microorganisms , preferably fungi.
  • the present invention provides a compound of formula I:
  • R 1 , R 2 , R 3 and R 4 are hydrogen, halogen, CrC 6 alkyl, d-C 6 haloalkyl or CrCealkyloxy, or
  • R 5 and R 6 are CrC 6 alkyl, CrC 6 haloalkyl, C 3 - C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, CrC 6 alkyloxy, hydroxyl or an optionaly substituted aryl, or R 5 and R 6 together with the silicon atom to which they are attached, form an optionally substituted, four- to seven-membered spiro-attached ring;
  • R 7 is an optionally substituted aryl, or heteroaryl
  • R 8 is Ci-C 6 alkyl, halogen or cyano
  • R 9 is hydrogen, mercapto or d-C 3 alkylthio
  • R 10 and R 11 each independently of each other are hydrogen, halogen, Ci-C 6 alkyl, C 1 -
  • the R 1 and R 2 substituents on those carbon atoms can be the same or different substituents each independently of each other.
  • the first carbon atom can be substituted by R 1 as ethyl and by R 2 as bromine
  • the second carbon atom can be substituted by R 1 as methyl and by R 2 as methoxy.
  • the same situation could happen to (R 3 R 4 C) n when n is 2, 3 or 4, for R 3 and R 4 , respectively.
  • R 1 and R 2 form an optionally substituted saturated or unsaturated three- to six-membered ring together with the carbon atom to which they are attached, this ring is necessarily linked to the same carbon atom when m is 1 , and can be linked to the same carbon atom or to another carbon atom when m is 2, 3 or 4.
  • (R 3 R 4 C) n when n is 2, 3 or 4, for R 3 and R 4 , respectively.
  • R 1 and R 2 form an optionally substituted saturated or unsaturated annulated five- to eight-membered ring together with the carbon atom to which they are attached; this annulated ring is necessarily linked to two different carbon atoms.
  • (R 3 R 4 C) n when n is 2, 3 or 4, for R 3 and R 4 , respectively.
  • aryl includes aromatic hydrocarbon rings like phenyl, naphthyl, anthracenyl, phenanthrenyl and biphenyl, with phenyl being preferred.
  • Heteroaryl stands for aromatic ring systems comprising mono-, bi- or tricyclic systems wherein at least one oxygen, nitrogen or sulfur atom is present as a ring member.
  • Examples are furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalin
  • aryl and heteroaryl groups may be optionally substituted. This means that they may carry one or more identical or different substituents. Normally not more than three substituents are present at the same time.
  • substituents of aryl or heteroaryl groups are: halogen, alkyl, haloalkyl, cycloalkyl, cycloalkylalkyl, alkenyl, haloalkenyl, cycloalkenyl, alkynyl, haloalkynyl, alkyloxy, haloalkyloxy, cycloalkoxy, alkenyloxy, haloalkenyloxy, alkynyloxy, haloalkenyloxy, alkylthio, haloalkylthio, cycloalkylthio, alkenylthio, alkynylthio, alkylcarbonyl, haloalkylcarbonyl, cycloalkylcarbonyl, alkenylcarbony
  • Typical examples include phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-trifluoromethylphenyl, 2- methylphenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6- difluorophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6- dichlorophenyl, 2-chloro-3-fluorophenyl, 2-chloro-4-fluorophenyl, 2-chloro-5- fluorophenyl, 2-chloro-6-fluorophenyl, 3-chloro-2-fluorophenyl, 4-chloro-2- fluorophenyl, 5-chloro-2-fluorophenyl, 2-fluoro-3-trifluoromethylphenyl, 2-fluoro-4- trifluoromethylphenyl, 2-
  • R 1 and R 2 or R 3 and R 4 each independently of each other can form an optionally substituted three- to six-membered spiro-attached ring together with the carbon atom to which they are attached.
  • Typical examples of three- to six-membered spiro-attached ring include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, oxiranyl, aziridinyl, oxetanyl, azetidinyl, tetrahydrofuranyl, pyrrolidinyl, 1 ,3- dioxolanyl, 1 ,3-dioxanyl and 1 ,4-dioxanyl.
  • the above-defined three- to six-membered spiro-attached rings may be optionally substituted. This means that they may carry one or more identical or different substituents. Normally not more than three substituents are present at the same time.
  • substituents of spiro-attached ring include hydrogen, halogen, Ci-C ⁇ alkyl, d-C ⁇ haloalkyl, d-C 6 cycloalkyl and cyano.
  • R 1 and R 2 or R 3 and R 4 each independently of each other, can form an optionally substituted saturated or unsaturated annulated five- to eight-membered ring together with the carbon atoms to which they are attached when m or n are 2, 3 or 4.
  • Typical examples of the annulated ring include cyclopentane, cyclohexane, cycloheptane or benzene.
  • annulated rings may be optionally substituted. This means that they may carry one or more identical or different substituents. Normally not more than three substituents are present at the same time.
  • substituents of annulated ring include hydrogen, halogen, C r C 6 alkyl, CrC 6 haloalkyl, d-C ⁇ cycloalkyl and cyano.
  • R 1 and R 2 or R 3 and R 4 each independently of each other, form an optionally substituted saturated or unsaturated annulated five- to eight-membered ring together with the carbon atom to which they are attached; the annulated ring is linked to two different carbon atoms when m or n are 2, 3 or 4.
  • R 5 and R 6 can form together with the silicon atom to which they are attached, an optionally substituted, four- to seven-membered spiro- attached ring.
  • Typical examples of three- to six-membered spiro-attached ring include siletanyl, silolanyl, silinanyl or silepanyl.
  • the above-defined three- to six-membered spiro-attached rings comprising a silicon atom may be optionally substituted. This means that they may carry one or more identical or different substituents. Normally not more than three substituents are present at the same time.
  • substituents of spiro-attached ring include hydrogen, halogen, Ci-C 6 alkyl, Ci-C 6 haloalkyl, C r C 6 cycloalkyl or cyano.
  • halogen is fluorine, chlorine, bromine or iodine.
  • alkyl, alkenyl or alkynyl radicals may be straight-chained or branched.
  • Alkyl on its own or as part of another substituent is, depending upon the number of carbon atoms mentioned, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl and the isomers thereof, for example, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl or tert-pentyl.
  • a haloalkyl group may contain one or more identical or different halogen atoms and, for example, may stand for CH 2 CI, CHCI 2 , CCI 3 , CH 2 F, CHF 2 , CF 3 , CF 3 CH 2 , CH 3 CF 2 , CF 3 CF 2 , CCI 3 CCI 2 , etc.
  • Cycloalkyl on its own or as part of another substituent is, depending upon the number of carbon atoms mentioned, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • Alkenyl on its own or as part of another substituent is, depending upon the number of carbon atoms mentioned, for example, ethenyl, allyl, 1-propenyl, buten-2- yl, buten-3-yl, penten-1-yl, penten-3-yl, hexen-1-yl or 4-methyl-3-pentenyl.
  • Alkynyl on its own or as part of another substituent is, depending upon the number of carbon atoms mentioned, for example, ethynyl, propyn-1-yl, propyn-2-yl, butyn-1-yl, butyn-2-yl, 1-methyl-2-butynyl, hexyn-1-yl or 1-ethyl-2-butynyl.
  • the presence of one or more possible asymmetric carbon atoms in the compounds of formula I means that the compounds may occur in optically isomeric, that means enantiomeric or diastereomeric forms.
  • optically isomeric that means enantiomeric or diastereomeric forms.
  • geometric isomerism that means cis-trans or (E)-(Z) isomerism may also occur.
  • atropisomers may occur as a result of restricted rotation about a single bond.
  • Formula I is intended to include all those possible isomeric forms and mixtures thereof.
  • the compounds of formula I according to the invention are in free form or in an agronomically usable salt form.
  • R 1 , R 2 , R 3 and R 4 are hydrogen, halogen or C 1 - C 6 alkyl
  • R 5 and R 6 are Ci-C 6 alkyl, CrC 6 haloalkyl or C 3 -
  • R 7 is an optionally substituted aryl
  • R 8 is CrC 6 alkyl or halogen
  • R 9 is hydrogen, mercapto or methylthio
  • R 1 , R 2 , R 3 and R 4 are hydrogen or CrC 6 alkyl;
  • R 5 and R 6 are d-C 6 alkyl or d-C ⁇ haloalkyl;
  • R 7 is phenyl substituted at least in one ort ⁇ oposition with halogen
  • R 8 is chloro or fluoro
  • R 9 is hydrogen or mercapto
  • R 1 , R 2 , R 3 and R 4 are hydrogen or methyl
  • R 5 and R 6 are methyl or ethyl
  • R 7 is 2,4,6-trifluorophenyl or 2-chloro-6-fluorophenyl; R 8 is chloro;
  • R 9 is hydrogen
  • Preferred individual compounds are: 5-chloro-7-(3,3-dimethyl-[1 ,3]azasilolidin-1 -yl)-6-(2,4,6-trif luoro-phenyl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidine (Compound No.l.c.081), 5-chloro-6-(2-chloro-6-fluoro-phenyl)-7-(3,3-dimethyl-[1 ,3]azasilolidin-1-yl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidine (Compound No.l.c.031), 5-chloro-7-(3,3-dimethyl-[1 > 3]azasilinan-1-yl)-6-(2,4,6-trifluoro-phenyl)- [i ⁇ . ⁇ triazoloti .S-alpyrimidine (Compound No.l.h.081), 5-chloro-6-
  • the compounds of formula I can be obtained by coupling of a compound of formula II, wherein R 7 , R 8 and R 9 are as defined for formula I and Hal is halogen, preferably fluorine, chlorine or bromine, with a compound of formula III, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , m and n are as defined for formula I. ) n (III)
  • the reaction (Il + III ⁇ I) can be carried out in a manner known per se for the transformation of amines with heterocyclic halides, e.g. 4-halopyrimidines or 7- halotriazolo[1 ,5-a]pyrimidines.
  • the reaction is carried out in solution.
  • organic solvents like N.N-dimethylformamide, N,N- dimethylacetamide, acetonitrile, dioxane, N-methylpyrrolidon, methanol, ethanol or dimethylsulfoxide, or organic solvents, like toluene or xylene in mixture with water and a phase transfer catalyst.
  • the reaction is advantageously carried out in the presence of a base.
  • organic or inorganic bases may be used, for instance triethylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium carbonate or potassium carbonate.
  • Reaction temperatures are between 0 0 C and +100 0 C, preferably between +10 0 C and +50 0 C.
  • the reaction of cyclic amines with compounds of formula Il is already described in WO 98/46607, US 6297251 and US 6117876.
  • [1 ,3]azasilolidines of formula (I I Ib) may be obtained from bromomethyl-chlorosilanes of formula (VIII).
  • [1 ,3]azasilolidines of formula (NIb) can also be obtained from 2,5- dihydropyrazines (bis-lactim ethers) of formula (XII), following a route to 4-sila-proline esters of formula (XIV) described in Eur. J. Org. Chem. 2000, 807 - 811 and Z. Naturforsch. 2000, 55b, 133 - 138 and a subsequent decarboxylation step as already described in Synlett 1995, 55 - 57, Synth. Commun. 1994, 24, 1381 - 1387 and Chem. Lett. 1986, 893 - 896.
  • novel compounds of formula I have, for practical purposes, a very advantageous spectrum of activities for protecting plants against diseases that are caused by fungi as well as by bacteria and viruses.
  • the compounds of formula I can be used in the agricultural sector and related fields of use as active ingredients for controlling plant pests or on non-living materials for control of spoilage microorganisms or organisms potentially harmful to man.
  • the novel compounds 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 cultivated plants.
  • the compounds of formula I can be used to inhibit or destroy the pests 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 protec- ting also those parts of the plants that grow later e.g. from phytopathogenic microorganisms.
  • compositions comprising a compound of formula I before planting: seed, for example, can be dressed before being sown.
  • the active ingredients according to the invention can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation.
  • the composition can also be applied to the planting site when the propagation material is being planted, for example, to the seed furrow during sowing. The invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.
  • the compounds according to present invention can be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management.
  • the invention could be used to protect non-living materials from fungal attack, e.g. lumber, wall boards and paint.
  • the compounds of formula I are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis spp., Alternaria spp.) and Basidiomycetes (e.g. Rhizoctonia spp., Hemileia spp., Puccinia spp., Phakopsora spp.). Additionally, they are also effective against Ascomycetes (e.g.
  • Vent ⁇ ria spp. Blumeria spp., Podosphaera leucotricha, Monilinia spp., Fusarium spp., Uncinula spp., Mycosphaerella spp., Pyrenophora spp.,
  • Rhynchosporium secalis Magnaporthe spp., Colletotrichum spp.
  • Oomycetes e.g. Phytophthora spp., Pythium spp., Plasmopara spp.
  • Outstanding activity has been observed against powdery mildews (e.g. Uncinula necato ⁇ , rusts (e.g. Puccinia spp.) and leaf spots (e.g. Septoria tritici).
  • the novel compounds of formula I are effective against phytopathogenic bacteria and viruses (e.g. against Xanthomonas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus).
  • target crops to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (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); cucumber 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) or plants such as tobacco
  • the target crops in accordance with the invention include conventional as well as genetically enhanced or engineered varieties such as, for example, insect resistant (e.g. Bt. And VIP varieties) as well as disease resistant, herbicide tolerant (e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®) and nematode tolerant varieties.
  • suitable genetically enhanced or engineered crop varieties include the Stoneville 5599BR cotton and Stoneville 4892BR cotton varieties.
  • the compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they are conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable 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 tackifiers 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 technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.
  • the compounds of formula I are normally used in the form of compositions and can be applied to the crop area 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 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.
  • the compounds of formula I are normally used in the form of fungicidal compositions for controlling and protecting against phytopathogenic microorganisms, comprising as active ingredient at least one compound of formula I, in free form or in agrochemically usable salt form, and at least one of the above-mentioned adjuvants.
  • the compounds of formula I 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, prothioconazole, pyrifenox, prochloraz, propiconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole;
  • Pyrimidinyl carbinole 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, procymidone, vinclozoline;
  • Carboxamides such as boscalid, carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, penthiopyrad, thifluzamide;
  • guanidines such as guazatine, dodine, iminoctadine;
  • Strobilurines such as azoxystrobin, dimoxystrobin (SSF 129), enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, orysastrobin, picoxystrobin, pyraclostrobin;
  • Dithiocarbamates such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram; N-halomethylthiotetrahydrophthalimides, such as captafol, captan, dichlofluanid, fluoromides, folpet, tolyfluanid;
  • Cu-compounds such as Bordeaux mixture, copper hydroxide, copper oxychlo- ride, copper sulfate, cuprous oxide, mancopper, oxine-copper; Nitrophenol-derivatives, such as dinocap, nitrothal-isopropyl;
  • Organo-p-derivatives such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-methyl; and
  • a method of controlling and preventing an infestation of crop plants 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 as active ingredient to the plants, to parts of the plants or to the locus thereof, or to any part of the non-living materials.
  • a preferred method of controlling and preventing an infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, which comprises the application of a compound of formula I, or an agrochemical composition which contains at least one of said compounds, 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 that is, a composition containing the compound of formula I] and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of formula I, 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 contain 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.
  • Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 1Og to 1 kg a.i./ha, most preferably from 2Og to 60Og a.i./ha.
  • convenient dosages are from 10mg to 1 g of active substance per kg of seeds.
  • Example 1 This example illustrates the preparation of 5-chloro-7-(4,4-dimethyl- [1 ,4]azasilinan-1 -yl)-6-(2,4,6-trifluoro-phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine (Compound No.l.p.081)
  • Example 2 This example illustrates the preparation of 5-chloro-7-(3,3-dimethyl- [1 ,3]azasilinan-1 -yl)-6-(2,4,6-trifluoro-phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine (Compound No.l.h.081) a) Preparation of allyl-bromomethyl-dimethyl-silane
  • Hydrogen bromide (2.3 g, 28 mmol) is bubbled under waterbath cooling to a solution of allyl-bromomethyl-dimethyl-silane (2.7 g, 14 mmol) and 2,2'-azobis-(2-methyl- propionitrile) (20 mg, 0.14 mmol) in 40 ml of pentane.
  • the reaction is started via short lighting with a UV-lamp. After the end of the exothermic conversion (the reaction temperature should not raise above 30 0 C), the mixture is filtered and evaporated to yield 3.5 g of bromomethyl-(3-bromo-propyl)-dimethyl-silane, which can be directly used in the next step without further purification.
  • Table 1 provides 144 compounds of formula (I. a):
  • R 7 , R 8 and R 9 are as defined in Table 1.
  • Table 1 provides 144 compounds of formula (l.b):
  • R 7 , R 8 and R 9 are as defined in Table 1.
  • Table 1 provides 144 compounds of formula (l.c):
  • R 7 , R 8 and R 9 are as defined in Table 1.
  • Table 1 provides 144 compounds of formula (l.d):
  • R 7 , R 8 and R 9 are as defined in Table 1.
  • Table 1 provides 144 compounds of formula (l.f):
  • R 7 , R 8 and R 9 are as defined in Table 1.
  • Table 1 provides 144 compounds of formula (l.g):
  • R 7 , R 8 and R 9 are as defined in Table 1.
  • Table 1 provides 144 compounds of formula (l.h):
  • R , R and R 9 are as defined in Table 1.
  • Table 1 provides 144 compounds of formula (l.k):
  • R 7 , R 8 and R 9 are as defined in Table 1.
  • Table 1 provides 144 compounds of formula (I.I):
  • R 7 , R 8 and R 9 are as defined in Table 1.
  • Table 1 provides 144 compounds of formula (l.m):
  • R J 7 , R and r Rj9 are as defined in Table 1.
  • Table 1 provides 144 compounds of formula (l.o):
  • R 7 , R 8 and R 9 are as defined in Table 1.
  • Table 1 provides 144 compounds of formula (l.p):
  • R 7 , R 8 and R 9 are as defined in Table 1.
  • R 7 , R 8 and R 9 are as defined in Table 1.
  • R , R 8 and R are as defined in Table 1.
  • R 7 , R 8 and R 9 are as defined in Table 1.
  • R 7 , R 8 and R 9 are as defined in Table 1.
  • Table 1 provides 144 compounds of formula (l.w):
  • R ⁇ R and R are as defined in Table 1.
  • Table 1 provides 144 compounds of formula (l.x):
  • R 7 , R 8 and R 9 are as defined in Table 1.
  • Table 1 provides 144 compounds of formula (l.y):
  • R , R and R are as defined in Table 1.
  • Table 2 shows selected melting point and selected NMR data, all with CDCI 3 as the solvent (unless otherwise stated, no attempt is made to list all characterising data in all cases) for compounds of Table 1.
  • Table 2 Melting point and selected NMR data for compounds of Table 1
  • Alternaria solani/ tomato / preventive (Action against Alternaria on tomato) 4 weeks old tomato plants cv. Roter Gnom are treated with the formulated test compound in a spray chamber. Two days after application tomato plants are inoculated by spraying a spore suspension on the test plants. After an incubation period of 4 days at 22/18° C and 95% r. h. in a greenhouse the disease incidence is assessed.
  • plants After an incubation period of 1 day at 20° C and 95% r. h. plants are kept for 10 days 20° C / 18° C (day/night) and 60% r.h. in a greenhouse. The disease incidence is assessed 11 days after inoculation.
  • Uncinula necator/ grape / preventive (Action against powdery mildew on grape) 5 weeks old grape seedlings cv. Gutedel are treated with the formulated test compound in a spray chamber.
  • grape plants are inoculated by shaking plants infected with grape powdery mildew above the test plants.

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Abstract

The present invention relates to novel triazolopyrimidine derivatives of formula (I) as active ingredients which have microbiocidal activity, in particular fungicidal activity: wherein the substituents are as defined in claim 1.

Description

Novel triazolopyrimidine derivatives
The present invention relates to novel triazolopyrimidine 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 or non-living materials by phytopathogenic microorganisms , preferably fungi.
The present invention provides a compound of formula I:
Figure imgf000002_0001
wherein
R1, R2, R3 and R4, each independently of each other and independently of m and n when m and/or n are 2, 3 or 4, are hydrogen, halogen, CrC6alkyl, d-C6haloalkyl or CrCealkyloxy, or
R1 and R2 or R3 and R4, each independently of each other, together with the carbon atom to which they are attached, form a group C=O, C=S or C=CR10R11, or R1 and R2 or R3 and R4, each independently of each other, together with the carbon atom to which they are attached form an optionally substituted three- to six- membered spiro-attached ring, or
R1 and R2 or R3 and R4, each independently of each other, are part of an endocyclic C=C double bond when m or n, each independently of each other, are 2, 3 or 4, or R1 and R2 or R3 and R4, each independently of each other, form an optionally substituted saturated or unsaturated annulated ring together with the carbon atoms to which they are attached when m or n are 2, 3 or 4;
R5 and R6, each independently of each other, are CrC6alkyl, CrC6haloalkyl, C3- C6cycloalkyl, C2-C6alkenyl, C2-C6alkynyl, CrC6alkyloxy, hydroxyl or an optionaly substituted aryl, or R5 and R6 together with the silicon atom to which they are attached, form an optionally substituted, four- to seven-membered spiro-attached ring;
R7 is an optionally substituted aryl, or heteroaryl;
R8 is Ci-C6alkyl, halogen or cyano; R9 is hydrogen, mercapto or d-C3alkylthio;
R10 and R11 each independently of each other are hydrogen, halogen, Ci-C6alkyl, C1-
C3haloalkyl or CrCealkyloxy; m and n, independently of each other, are 1 , 2, 3 or 4, and
(m + n) is equal to 2, 3, 4, 5 or 6.
In the instance where m is 2, 3 or 4, which means that 2, 3 or 4 contiguous carbon atoms respectively are present in the endocyclic ring, the R1 and R2 substituents on those carbon atoms can be the same or different substituents each independently of each other. For example, when m is 2, the first carbon atom can be substituted by R1 as ethyl and by R2 as bromine, and the second carbon atom can be substituted by R1 as methyl and by R2 as methoxy. The same situation could happen to (R3R4C)n when n is 2, 3 or 4, for R3 and R4, respectively.
When R1 and R2 form an optionally substituted saturated or unsaturated three- to six-membered ring together with the carbon atom to which they are attached, this ring is necessarily linked to the same carbon atom when m is 1 , and can be linked to the same carbon atom or to another carbon atom when m is 2, 3 or 4. The same situation applies to (R3R4C)n when n is 2, 3 or 4, for R3 and R4, respectively.
When R1 and R2 form an optionally substituted saturated or unsaturated annulated five- to eight-membered ring together with the carbon atom to which they are attached; this annulated ring is necessarily linked to two different carbon atoms. The same situation applies to (R3R4C)n when n is 2, 3 or 4, for R3 and R4, respectively.
In the above definition aryl includes aromatic hydrocarbon rings like phenyl, naphthyl, anthracenyl, phenanthrenyl and biphenyl, with phenyl being preferred.
Heteroaryl stands for aromatic ring systems comprising mono-, bi- or tricyclic systems wherein at least one oxygen, nitrogen or sulfur atom is present as a ring member. Examples are furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl and naphthyridinyl. Each heteroaryl can be linked by a carbon atom or by a nitrogen atom to the [1 ,2,4]triazolo[1 ,5-a]pyrimidine.
The above aryl and heteroaryl groups may be optionally substituted. This means that they may carry one or more identical or different substituents. Normally not more than three substituents are present at the same time. Examples of substituents of aryl or heteroaryl groups are: halogen, alkyl, haloalkyl, cycloalkyl, cycloalkylalkyl, alkenyl, haloalkenyl, cycloalkenyl, alkynyl, haloalkynyl, alkyloxy, haloalkyloxy, cycloalkoxy, alkenyloxy, haloalkenyloxy, alkynyloxy, haloalkenyloxy, alkylthio, haloalkylthio, cycloalkylthio, alkenylthio, alkynylthio, alkylcarbonyl, haloalkylcarbonyl, cycloalkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, alkoxyalkyl, cyano, nitro, hydroxy, mercapto, amino, alkylamino, dialkylamino. Typical examples include phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-trifluoromethylphenyl, 2- methylphenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6- difluorophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6- dichlorophenyl, 2-chloro-3-fluorophenyl, 2-chloro-4-fluorophenyl, 2-chloro-5- fluorophenyl, 2-chloro-6-fluorophenyl, 3-chloro-2-fluorophenyl, 4-chloro-2- fluorophenyl, 5-chloro-2-fluorophenyl, 2-fluoro-3-trifluoromethylphenyl, 2-fluoro-4- trifluoromethylphenyl, 2-fluoro-5-trifluoromethylphenyl, 2-fluoro-6- trifluoromethylphenyl, 2-chloro-3-trifluoromethylphenyl, 2-chloro-4- trifluoromethylphenyl, 2-chloro-5-trifluoromethylphenyl, 2-chloro-6- trifluoromethylphenyl, 4-fluoro-2-trifluoromethylphenyl, 4-chloro-2- trifluoromethylphenyl, 2-fluoro-3-methylphenyl, 2-fluoro-4-methylphenyl, 2-fluoro-5- methylphenyl, 2-fluoro-6-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4- methylphenyl, 2-chloro-5-methylphenyl, 2-chloro-6-methylphenyl, 4-fluoro-2- methylphenyl, 4-chloro-2-methylphenyl, 2,3,4-trifluorophenyl, 2,3,6-trifluorophenyl, 2,4,6-trifluorophenyl, 2,3,4-trichlorophenyl, 2,3,6-trichlorophenyl, 2,4,6- trichlorophenyl, 2,6-difluoro-4-methoxyphenyl, 2,6-difluoro-4-trifluoromethoxyphenyl, 2,6-difluoro-4-trifluoromethylphenyl, 2,6-difluoro-4-cyanophenyl, 2,6-difluoro-4- methylphenyl, 2,6-dichloro-4-methoxyphenyl, 2,6-dichloro-4-trifluoromethoxyphenyl, 2,6-dichloro-4-trifluoromethylphenyl, 2,6-dichloro-4-cyanophenyl, 2,6-dichloro-4- methylphenyl, pentafluorophenyl, 3,5-difluoropyridin-2-yl, 3,5-dichloropyridin-2-yl, 3- chloro-5-fluoropyridine-2-yl, 5-chloro-3-fluoropyridin-2-yl, 3-fluoro-5- trifluoromethylpyridin-2-yl, S-chloro-δ-trifluoromethylpyridin^-yl, 2,4-difluoropyridin-3- yl, 2,4-dichloropyridin-3-yl, 2A6-trifluoropyridin-3-yl, 2,4>6-trichloropyridin-3-yl, 3,5- difluoropyridin-4-yl, 3,5-dichloropyridin-4-yl, 2,5-difluorothiophen-3-yl and 2,5- dichlorothiophen-3-yl.
In the above definition, R1 and R2 or R3 and R4, each independently of each other can form an optionally substituted three- to six-membered spiro-attached ring together with the carbon atom to which they are attached. Typical examples of three- to six-membered spiro-attached ring include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, oxiranyl, aziridinyl, oxetanyl, azetidinyl, tetrahydrofuranyl, pyrrolidinyl, 1 ,3- dioxolanyl, 1 ,3-dioxanyl and 1 ,4-dioxanyl.
The above-defined three- to six-membered spiro-attached rings may be optionally substituted. This means that they may carry one or more identical or different substituents. Normally not more than three substituents are present at the same time. Typical examples of substituents of spiro-attached ring include hydrogen, halogen, Ci-Cβalkyl, d-Cβhaloalkyl, d-C6cycloalkyl and cyano.
In the above definition, R1 and R2 or R3 and R4, each independently of each other, can form an optionally substituted saturated or unsaturated annulated five- to eight-membered ring together with the carbon atoms to which they are attached when m or n are 2, 3 or 4. Typical examples of the annulated ring include cyclopentane, cyclohexane, cycloheptane or benzene.
The above-defined annulated rings may be optionally substituted. This means that they may carry one or more identical or different substituents. Normally not more than three substituents are present at the same time. Typical examples of substituents of annulated ring include hydrogen, halogen, CrC6alkyl, CrC6haloalkyl, d-Cβcycloalkyl and cyano.
When R1 and R2 or R3 and R4, each independently of each other, form an optionally substituted saturated or unsaturated annulated five- to eight-membered ring together with the carbon atom to which they are attached; the annulated ring is linked to two different carbon atoms when m or n are 2, 3 or 4.
In the above definition, R5 and R6 can form together with the silicon atom to which they are attached, an optionally substituted, four- to seven-membered spiro- attached ring. Typical examples of three- to six-membered spiro-attached ring include siletanyl, silolanyl, silinanyl or silepanyl.
The above-defined three- to six-membered spiro-attached rings comprising a silicon atom may be optionally substituted. This means that they may carry one or more identical or different substituents. Normally not more than three substituents are present at the same time. Typical examples of substituents of spiro-attached ring include hydrogen, halogen, Ci-C6alkyl, Ci-C6haloalkyl, CrC6cycloalkyl or cyano.
In the above definition halogen is fluorine, chlorine, bromine or iodine.
The alkyl, alkenyl or alkynyl radicals may be straight-chained or branched.
Alkyl on its own or as part of another substituent is, depending upon the number of carbon atoms mentioned, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl and the isomers thereof, for example, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl or tert-pentyl.
A haloalkyl group may contain one or more identical or different halogen atoms and, for example, may stand for CH2CI, CHCI2, CCI3, CH2F, CHF2, CF3, CF3CH2, CH3CF2, CF3CF2, CCI3CCI2, etc.
Cycloalkyl on its own or as part of another substituent is, depending upon the number of carbon atoms mentioned, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Alkenyl on its own or as part of another substituent is, depending upon the number of carbon atoms mentioned, for example, ethenyl, allyl, 1-propenyl, buten-2- yl, buten-3-yl, penten-1-yl, penten-3-yl, hexen-1-yl or 4-methyl-3-pentenyl.
Alkynyl on its own or as part of another substituent is, depending upon the number of carbon atoms mentioned, for example, ethynyl, propyn-1-yl, propyn-2-yl, butyn-1-yl, butyn-2-yl, 1-methyl-2-butynyl, hexyn-1-yl or 1-ethyl-2-butynyl.
The presence of one or more possible asymmetric carbon atoms in the compounds of formula I means that the compounds may occur in optically isomeric, that means enantiomeric or diastereomeric forms. As a result of the presence of a possible aliphatic C=C double bond, geometric isomerism, that means cis-trans or (E)-(Z) isomerism may also occur. Also atropisomers may occur as a result of restricted rotation about a single bond. Formula I is intended to include all those possible isomeric forms and mixtures thereof.
In each case, the compounds of formula I according to the invention are in free form or in an agronomically usable salt form.
Preferred subgroups of compounds of formula I are those wherein
R1, R2, R3 and R4, each independently of each other, are hydrogen, halogen or C1- C6alkyl;
R5 and R6, each independently of each other, are Ci-C6alkyl, CrC6haloalkyl or C3-
C6cycloalkyl;
R7 is an optionally substituted aryl;
R8 is CrC6alkyl or halogen; R9 is hydrogen, mercapto or methylthio;
(m + n) is equal to 2, 3, 4 or 5.
More preferred subgroups of compounds of formula I are those wherein
R1, R2, R3 and R4, each independently of each other, are hydrogen or CrC6alkyl; R5 and R6, each independently of each other, are d-C6alkyl or d-Cβhaloalkyl;
R7 is phenyl substituted at least in one ortΛoposition with halogen;
R8 is chloro or fluoro;
R9 is hydrogen or mercapto;
(m + n) is equal to 2, 3 or 4.
Most preferred subgroups of compounds of formula I are those wherein
R1, R2, R3 and R4, each independently of each other, are hydrogen or methyl;
R5 and R6, each independently of each other, are methyl or ethyl;
R7 is 2,4,6-trifluorophenyl or 2-chloro-6-fluorophenyl; R8 is chloro;
R9 is hydrogen;
(m + n) is equal to 3 or 4.
Preferred individual compounds are: 5-chloro-7-(3,3-dimethyl-[1 ,3]azasilolidin-1 -yl)-6-(2,4,6-trif luoro-phenyl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidine (Compound No.l.c.081), 5-chloro-6-(2-chloro-6-fluoro-phenyl)-7-(3,3-dimethyl-[1 ,3]azasilolidin-1-yl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidine (Compound No.l.c.031), 5-chloro-7-(3,3-dimethyl-[1 >3]azasilinan-1-yl)-6-(2,4,6-trifluoro-phenyl)- [i ^.^triazoloti .S-alpyrimidine (Compound No.l.h.081), 5-chloro-6-(2-chloro-6-fluoro-phenyl)-7-(3,3-dimethyl-[1 ,3]azasilinan-1 -yl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidine (Compound No.l.h.031), 5-chloro-7-(4,4-dimethyl-[1 ,4]azasilinan-1-yl)-6-(2,4,6-trifluoro-phenyl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidine (Compound No.l.p.081), 5-chloro-6-(2-chloro-6-fluoro-phenyl)-7-(4,4-dimethyl-[1 ,4]azasilinan-1-yl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidine (Compound No.l.p.031 ),
7-(4,4-dimethyl-[1 ,4]azasilinan-1-yl)-5-fluoro-6-(2,4,6-trifluoro-phenyl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidine (Compound No.l.p.083), 5-chloro-7-(4,4-dimethyl-[1 ,4]azasilinan-1-yl)-6-(2,4,6-trifluoro-phenyl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidine-2-thiol (Compound No.l.p.082), 5-chloro-7-(4,4-diethyl-[1 ,4]azasilinan-1 -yl)-6-(2,4,6-trifluoro-phenyl)- [1 ,2,4]triazok>[1 ,5-a]pyrimidine (Compound No.l.q.081), 5-chloro-6-(2-chloro-6-fluoro-phenyl)-7-(4,4-diethyl-[1 ,4]azasilinan-1-yl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidine (Compound No.l.q.031), 7-(8-aza-5-sila-spiro[4.5]dec-8-yl)-5-chloro-6-(2,4,6-trifluoro-phenyl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidine (Compound No.l.t.081 ),
7-(8-aza-5-sila-spiro[4.5]dec-8-yl)-5-chloro-6-(2-chloro-6-fluoro-phenyl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidine (Compound No.l.t.031).
Certain triazolo[1 ,5-a]pyrimidine derivatives with cyclic amines in position 7 have been proposed for controlling plant-destructive fungi, for example in WO
98/46607, US 6117876 and US 6297251. However, the action of those preparations is not satisfactory in all aspects of agricultural needs. Surprisingly, with the compounds of formula I, new kinds of fungicides having a high level of biological actitivity have now been found.
The compounds of formula I can be obtained by coupling of a compound of formula II, wherein R7, R8 and R9 are as defined for formula I and Hal is halogen, preferably fluorine, chlorine or bromine, with a compound of formula III, wherein R1, R2, R3, R4, R5, R6, m and n are as defined for formula I. )n (III)
Figure imgf000009_0001
The reaction (Il + III → I) can be carried out in a manner known per se for the transformation of amines with heterocyclic halides, e.g. 4-halopyrimidines or 7- halotriazolo[1 ,5-a]pyrimidines. Preferably the reaction is carried out in solution. Preferred are either organic solvents like N.N-dimethylformamide, N,N- dimethylacetamide, acetonitrile, dioxane, N-methylpyrrolidon, methanol, ethanol or dimethylsulfoxide, or organic solvents, like toluene or xylene in mixture with water and a phase transfer catalyst. The reaction is advantageously carried out in the presence of a base. In general all types of organic or inorganic bases may be used, for instance triethylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium carbonate or potassium carbonate. Reaction temperatures are between 0 0C and +1000C, preferably between +10 0C and +50 0C. The reaction of cyclic amines with compounds of formula Il is already described in WO 98/46607, US 6297251 and US 6117876.
The compounds of formula II, wherein R7, R8 and R9 are as defined for formula I and Hal is halogen, preferably fluorine, chlorine or bromine, can be obtained by halogenation of a compound of formula IV, wherein R7 and R9 are as defined for formula I and R12 is hydroxy, d-C^alky! or cyano.
(II) The preparation of compounds of formula Il is already describedjn WO 2002/038565, US 6297251 and US 6117876.
The compounds of formula III, wherein R1, R2, R3, R4, R5, R6, m and n are as defined for formula I, can be obtained by known methods for the synthesis of N, Si- heterocycles.
For instance, the synthesis of [1 ,4]azasilinanes of formula (Ilia) can be achieved from divinylsilanes of formula (V), following a route described in Z. Naturforsch. 1982, 37b, 657 - 662, JP 02160766 and JP 04041494.
Rsχ /=CH2 HBr, (BzO)2, hv Rsχ /— CH2Br BnNH2, NEt3
VSI .. (V) - ,.68'' Si (Vl)
R" V=CH, -CH2Br
H (MIa)
Figure imgf000010_0001
Analogously to the above shown reaction scheme, [1 ,3]azasilolidines of formula (I I Ib) may be obtained from bromomethyl-chlorosilanes of formula (VIII).
R 5 χ Cl H2C=CHMgBr R 5 χ /=CH2 HBr, (BzO)2, hv
6,Si (VIII) - y (IX)
R CH2Br R CH2Br
Figure imgf000010_0002
Alternatively, [1 ,3]azasilolidines of formula (NIb) can also be obtained from 2,5- dihydropyrazines (bis-lactim ethers) of formula (XII), following a route to 4-sila-proline esters of formula (XIV) described in Eur. J. Org. Chem. 2000, 807 - 811 and Z. Naturforsch. 2000, 55b, 133 - 138 and a subsequent decarboxylation step as already described in Synlett 1995, 55 - 57, Synth. Commun. 1994, 24, 1381 - 1387 and Chem. Lett. 1986, 893 - 896.
Figure imgf000011_0001
Figure imgf000011_0002
Surprisingly, it has now been found that the novel compounds of formula I have, for practical purposes, a very advantageous spectrum of activities for protecting plants against diseases that are caused by fungi as well as by bacteria and viruses.
The compounds of formula I can be used in the agricultural sector and related fields of use as active ingredients for controlling plant pests or on non-living materials for control of spoilage microorganisms or organisms potentially harmful to man. The novel compounds 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 cultivated plants. The compounds of formula I can be used to inhibit or destroy the pests 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 protec- ting also those parts of the plants that grow later e.g. from phytopathogenic microorganisms.
It is also possible to use compounds of formula I as dressing agents for the treatment of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings (for example rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil. The propagation material can be treated with a composition comprising a compound of formula I before planting: seed, for example, can be dressed before being sown. The active ingredients according to the invention can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the planting site when the propagation material is being planted, for example, to the seed furrow during sowing. The invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.
Furthermore the compounds according to present invention can be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management.
In addition, the invention could be used to protect non-living materials from fungal attack, e.g. lumber, wall boards and paint.
The compounds of formula I are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis spp., Alternaria spp.) and Basidiomycetes (e.g. Rhizoctonia spp., Hemileia spp., Puccinia spp., Phakopsora spp.). Additionally, they are also effective against Ascomycetes (e.g. Ventυria spp., Blumeria spp., Podosphaera leucotricha, Monilinia spp., Fusarium spp., Uncinula spp., Mycosphaerella spp., Pyrenophora spp.,
Rhynchosporium secalis, Magnaporthe spp., Colletotrichum spp.) and Oomycetes (e.g. Phytophthora spp., Pythium spp., Plasmopara spp.). Outstanding activity has been observed against powdery mildews (e.g. Uncinula necatoή, rusts (e.g. Puccinia spp.) and leaf spots (e.g. Septoria tritici). Furthermore, the novel compounds of formula I are effective against phytopathogenic bacteria and viruses (e.g. against Xanthomonas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus).
Within the scope of present invention, target crops to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (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); cucumber 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) or plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as turf and ornamentals.
The target crops in accordance with the invention include conventional as well as genetically enhanced or engineered varieties such as, for example, insect resistant (e.g. Bt. And VIP varieties) as well as disease resistant, herbicide tolerant (e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®) and nematode tolerant varieties. By way of example, suitable genetically enhanced or engineered crop varieties include the Stoneville 5599BR cotton and Stoneville 4892BR cotton varieties.
The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they are conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type 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. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers 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 technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.
The compounds of formula I are normally used in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These 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 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.
The compounds of formula I are normally used in the form of fungicidal compositions for controlling and protecting against phytopathogenic microorganisms, comprising as active ingredient at least one compound of formula I, in free form or in agrochemically usable salt form, and at least one of the above-mentioned adjuvants.
The compounds of formula I 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, prothioconazole, pyrifenox, prochloraz, propiconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole;
Pyrimidinyl carbinole, 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, procymidone, vinclozoline; Carboxamides, such as boscalid, carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, penthiopyrad, thifluzamide; guanidines, such as guazatine, dodine, iminoctadine;
Strobilurines, such as azoxystrobin, dimoxystrobin (SSF 129), enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, orysastrobin, picoxystrobin, pyraclostrobin;
Dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram; N-halomethylthiotetrahydrophthalimides, such as captafol, captan, dichlofluanid, fluoromides, folpet, tolyfluanid;
Cu-compounds, such as Bordeaux mixture, copper hydroxide, copper oxychlo- ride, copper sulfate, cuprous oxide, mancopper, oxine-copper; Nitrophenol-derivatives, such as dinocap, nitrothal-isopropyl;
Organo-p-derivatives, such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-methyl; and
Various others, such as acibenzolar-S-methyl, anilazine, benthiavalicarb, blasticidin-S, chinomethionate, chloroneb, chlorothalonil, cyflufenamid, cymoxanil, dichlone, diclocymet, diclomezine, dicloran, diethofencarb, dimethomorph, SYP-LI90 (proposed name: flumorph), dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, fentin, ferimzone, fluazinam, fluopicolide, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, iprovalicarb, IKF-916 (cyazofamid), kasugamycin, methasulfocarb, metrafenone, nicobifen, pencycuron, phthalide, polyoxins, probenazole, propamocarb, proquinazid, pyroquilon, quinoxyfen, quintozene, sulfur, tiadinil, triazoxide, tricyclazole, triforine, validamycin, zoxamide (RH7281 ).
A method of controlling and preventing an infestation of crop plants 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 as active ingredient to the plants, to parts of the plants or to the locus thereof, or to any part of the non-living materials.
A preferred method of controlling and preventing an infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, which comprises the application of a compound of formula I, or an agrochemical composition which contains at least one of said compounds, is foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen. However, 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 [that is, a composition containing the compound of formula I] and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of formula I, 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 contain 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.
Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 1Og to 1 kg a.i./ha, most preferably from 2Og to 60Og a.i./ha. When used as seed drenching agent, convenient dosages are from 10mg to 1 g of active substance per kg of seeds.
Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.
The following non-limiting Examples illustrate the above-described invention in more detail.
Example 1 : This example illustrates the preparation of 5-chloro-7-(4,4-dimethyl- [1 ,4]azasilinan-1 -yl)-6-(2,4,6-trifluoro-phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine (Compound No.l.p.081)
a) Preparation of bis-(2-bromo-ethyl)-dimethyl-silane Hydrogen bromide (17 g, 0.21 mol) is bubbled under waterbath cooling to a solution of dimethyl-divinyl-silane (11.5 g, 0.1 mol) and dibenzoyl peroxide (0.25 g, 1.0 mmol) in 180 ml of pentane. The reaction is started via short lighting with a U V-lamp. After the end of the exothermic conversion (the reaction temperature should not raise above 30 0C), the mixture is filtered and evaporated to yield 28 g of bis-(2-bromo- ethyl)-dimethyl-silane, which can be directly used in the next step without further purification. b) Preparation of 1 -benzyl-4,4-dimethyl-[1 ,4]azasilinane hydrochloride Benzylamine (50 g, 0.46 mol) is added to a solution of bis-(2-bromo-ethyl)-dimethyl- silane (25.5 g, 93 mmol) and triethylamine (28 g, 0.28 mol) in 200 ml of chloroform. This mixture is stirred for 16 h at 70 0C. Subsequently the reaction mixture is cooled, diluted with 2 N sodium hydroxide and extracted with dichloromethane. The combined organic layer is washed with water, dried over magnesium sulfate and evaporated, the remainder is chromatographed on silica gel, using ethyl acetate and hexane as eluents to obtain 14 g of 1-benzyl-4,4-dimethyl-[1 ,4]azasilinane as free amine. This colourless oil is dissolved in 140 ml of ethanol, and 6 N hydrochloric acid (10.5 ml, 64 mmol) is added. After removal of the solvent, the residue is coevaporated three times with ethanol. Crystallisation of the remainder from ethanol and diethyl ether delivers 14.5 g of 1 -benzyl-4,4-dimethyl-[1 ,4]azasilinane hydrochloride.
c) Preparation of 4,4-dimethyl-[1 ,4]azasilinane hydrochloride
A solution of 1-benzyl-4,4-dimethyl-[1 ,4]azasilinane hydrochloride (4.9 g, 19 mmol) in 75 ml of methanol is slowly added to a suspension of palladium (10 wt. % on activated carbon, 0.4 g) in 75 ml of methanol. This mixture is stirred for 72 h under argon. Subsequently the mixture is filtered through celite. The filtrate is evaporated, the residue is triturated with diethyl ether to yield 3 g of 4,4-dimethyl-[1 ,4]azasilinane hydrochloride as colourless cristalls.
d) 4,4-dimethyl-[1 ,4]azasilinane hydrochloride (120 mg, 0.7 mmol) is added to a suspension of 5>7-dichloro-6-(2,4,6)-trifluoro-phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine
(190 mg, 0.6 mmol), potassium carbonate anhydrous (200 mg, 1.5 mmol) and catalytic amounts of 4-(dimethylamino)pyridine in 4 ml of N.N-dimethylacetamide. This mixture is stirred 2 h at room temperature, then poured on icewater and extracted with ethyl acetate. The combined organic layer is washed with water and brine, dried over magnesium sulfate and evaporated. The residue is purified by chromatography on silica gel, using ethyl aceate and hexane as eluents, to deliver 100 mg of 5-chloro-7-(4,4-dimethyl-[1 ,4]azasilinan-1-yl)-6-(2,4,6-trifluoro-phenyl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidine (Compound No.l.p.081).
Example 2: This example illustrates the preparation of 5-chloro-7-(3,3-dimethyl- [1 ,3]azasilinan-1 -yl)-6-(2,4,6-trifluoro-phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine (Compound No.l.h.081) a) Preparation of allyl-bromomethyl-dimethyl-silane
A 2 M solution of allylmagnesium chloride in tetrahydrofuran (15 ml, 30 mmol) is added dropwise to a solution of bromomethyl-chloro-dimethyl-silane (5.6 g, 30 mmol) in 20 ml of tetrahydrofuran at 0 0C. After this mixture is stirred for 1 h at room temperature, 10 ml of water are added carefully, followed by the addition of 8 ml 1 N hydrochloric acid. This mixture is extracted with pentane. The combined organic layer is washed with brine, dried over magnesium sulfate and evaporated. The residue is purified by chromatography on silica gel, using pentane as eluent, to deliver 2.7 g of allyl-bromomethyl-dimethyl-silane.
b) Preparation of bromomethyl-(3-bromo-propyl)-dimethyl-silane
Hydrogen bromide (2.3 g, 28 mmol) is bubbled under waterbath cooling to a solution of allyl-bromomethyl-dimethyl-silane (2.7 g, 14 mmol) and 2,2'-azobis-(2-methyl- propionitrile) (20 mg, 0.14 mmol) in 40 ml of pentane. The reaction is started via short lighting with a UV-lamp. After the end of the exothermic conversion (the reaction temperature should not raise above 30 0C), the mixture is filtered and evaporated to yield 3.5 g of bromomethyl-(3-bromo-propyl)-dimethyl-silane, which can be directly used in the next step without further purification.
c) Preparation of 1 -benzyl-3,3-dimethyl-[1 ,3]azasilinane hydrochloride Benzylamine (6.9 g, 64 mmol) is added to a solution of bromomethyl-(3-bromo- propyl)-dimethyl-silane (3.5 g, 13 mmol) and triethylamine (3.9 g, 39 mmol) in 30 ml of chloroform. This mixture is stirred for 16 h at 70 0C. Subsequently the reaction mixture is cooled, diluted with 2 N sodium hydroxide and extracted with dichloromethane. The combined organic layer is washed with water, dried over magnesium sulfate and evaporated, the remainder is chromatographed on silica gel, using ethyl acetate and hexane as eluents to obtain 2.2 g of 1 -benzyl-3,3-dimethyl- [1 ,3]azasilinane as free amine. This colourless oil is dissolved in 20 ml of diethyl ether, and a 2 N solution of hydrochloric acid in diethyl ether (4.9 ml, 9.8 mmol) is added. The mixture is filtered and the solid is washed with diethyl ether and dried to deliver 2.4 g of 1-benzyl-3,3-dimethyl-[1 ,3]azasilinane hydrochloride.
d) Preparation of 3,3-dimethyl-[1 ,3]azasilinane hydrochloride A solution of 1-benzyl-3,3-dimethyl-[1 ,3]azasilinane hydrochloride (2.4 g, 9.0 mmol) in 45 ml of methanol is slowly added to a suspension of palladium (10 wt. % on activated carbon, 0.2 g) in 75 ml of methanol. This mixture is stirred for 72 h under argon. Subsequently the mixture is filtered through celite. The filtrate is evaporated, the residue is triturated with dichloromethane and diethyl ether to yield 1.3 g of 3,3- dimethyl-[1 ,3]azasilinane hydrochloride as colourless cristalls. e) N.N-diisopropyl-ethyl-amine (0.2 g, 1.5 mmol) is added dropwise to a solution of 5,7-dichloro-6-(2,4,6)-trifluoro-phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine (190 mg, 0.6 mmol) and 3,3-dimethyl-[1 ,3]azasilinane hydrochloride (100 mg, 0.6 mmol) in 4 ml of dichloromethane at 0 0C. This mixture is stirred 1 h at room temperature and then evaporated in vacuo. The residue is purified by chromatography on silica gel, using ethyl aceate and hexane as eluents, to deliver 150 mg of 5-chloro-7-(3,3- dimethyl-[1 ,3]azasilinan-1 -yl)-6-(2,4,6-trifluoro-phenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine (Compound No.l.h.081).
Table 1 below illustrates individual compounds of formula I according to the invention.
Table 1 : individual com ounds of formula I accordin to the invention
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Table 1 provides 144 compounds of formula (I. a):
Figure imgf000024_0001
wherein R7, R8 and R9 are as defined in Table 1.
Table 1 provides 144 compounds of formula (l.b):
Figure imgf000024_0002
wherein R7, R8 and R9 are as defined in Table 1.
Table 1 provides 144 compounds of formula (l.c):
Figure imgf000024_0003
wherein R7, R8 and R9 are as defined in Table 1.
Table 1 provides 144 compounds of formula (l.d):
Figure imgf000024_0004
wherein R7, R8 and R9 are as defined in Table 1. Table 1 provides 144 compounds of formula (l.e):
Figure imgf000025_0001
wherein R7, R8 and R9 are as defined in Table 1.
Table 1 provides 144 compounds of formula (l.f):
Figure imgf000025_0002
wherein R7, R8 and R9 are as defined in Table 1.
Table 1 provides 144 compounds of formula (l.g):
Figure imgf000025_0003
wherein R7, R8 and R9 are as defined in Table 1.
Table 1 provides 144 compounds of formula (l.h):
Figure imgf000025_0004
wherein R7, R8 and R9 are as defined in Table 1. Table 1 provides 144 compounds of formula (l.i):
Figure imgf000026_0001
wherein R , R and R9 are as defined in Table 1.
Table 1 provides 144 compounds of formula (l.k):
Figure imgf000026_0002
wherein R7, R8 and R9 are as defined in Table 1.
Table 1 provides 144 compounds of formula (I.I):
Figure imgf000026_0003
wherein R7, R8 and R9 are as defined in Table 1.
Table 1 provides 144 compounds of formula (l.m):
Figure imgf000026_0004
wherein R7, R8 and R9 are as defined in Table 1. Table 1 provides 144 compounds of formula (l.n):
Figure imgf000027_0001
wherein R J7 , R and r Rj9 are as defined in Table 1.
Table 1 provides 144 compounds of formula (l.o):
Figure imgf000027_0002
wherein R7, R8 and R9 are as defined in Table 1.
Table 1 provides 144 compounds of formula (l.p):
Figure imgf000027_0003
wherein R7, R8 and R9 are as defined in Table 1.
Table 1 provides 144 compounds of formula (l.q):
Figure imgf000027_0004
wherein R7, R8 and R are as defined in Table 1. Table 1 provides 144 compounds of formula (Lr):
Figure imgf000028_0001
wherein R7, R8 and R9 are as defined in Table 1.
Table 1 provides 144 compounds of formula (Ls):
Figure imgf000028_0002
wherein R , R8 and R are as defined in Table 1.
Table 1 provides 144 compounds of formula (Lt):
Figure imgf000028_0003
wherein R7, R8 and R9 are as defined in Table 1.
Table 1 provides 144 compounds of formula (Lu):
Figure imgf000028_0004
wherein R , R8 and R are as defined in Table 1. Table 1 provides 144 compounds of formula (l.v):
Figure imgf000029_0001
wherein R7, R8 and R9 are as defined in Table 1.
Table 1 provides 144 compounds of formula (l.w):
Figure imgf000029_0002
wherein R\ R and R are as defined in Table 1. -
Table 1 provides 144 compounds of formula (l.x):
Figure imgf000029_0003
wherein R7, R8 and R9 are as defined in Table 1.
Table 1 provides 144 compounds of formula (l.y):
Figure imgf000029_0004
wherein R7, R8 and R9 are as defined in Table 1. Table 1 provides 144 compounds of formula (l.z):
Figure imgf000030_0001
wherein R , R and R are as defined in Table 1.
Throughout this description, temperatures are given in degrees Celsius; "NMR" means nuclear magnetic resonance spectrum; and "%" is percent by weight, unless corresponding concentrations are indicated in other units.
The following abbreviations are used throughout this description: m.p. = melting point br = broad s = singlet dd = doublet of doublets d = doublet dt = doublet of triplets t = triplet q = quartet m = multiplet ppm = parts per million
Table 2 shows selected melting point and selected NMR data, all with CDCI3 as the solvent (unless otherwise stated, no attempt is made to list all characterising data in all cases) for compounds of Table 1.
Table 2: Melting point and selected NMR data for compounds of Table 1
Figure imgf000030_0002
Figure imgf000031_0001
The compounds according to the present invention may be prepared according to the above-mentined reaction schemes, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula I.
Biological examples
Alternaria solani/ tomato / preventive (Action against Alternaria on tomato) 4 weeks old tomato plants cv. Roter Gnom are treated with the formulated test compound in a spray chamber. Two days after application tomato plants are inoculated by spraying a spore suspension on the test plants. After an incubation period of 4 days at 22/18° C and 95% r. h. in a greenhouse the disease incidence is assessed.
Compounds of formula I, in particular compounds l.c.081 , l.f .081 , l.h.081 and l.t.081 at 200 ppm inhibit fungal infestation in this test to a least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %.
Botrytis cinerea I tomato / preventive (Action against Botrvtis on tomato)
4 weeks old tomato plants cv. Roter Gnom are treated with the formulated test compound in a spray chamber. Two days after application tomato plants are inoculated by spraying a spore suspension on the test plants. After an incubation period of 3 days at 20° C and 95% r. h. in a greenhouse the disease incidence is assessed.
Compounds of formula I, in particular compounds l.f.081 , l.h.081 and l.t.081 at 200 ppm inhibit fungal infestation in this test to a least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %. Pυccinia recondita /wheat / preventive (Action against brown rust on wheat) 1 week old wheat plants cv. Arina are treated with the formulated test compound in a spray chamber. One day after application wheat plants are inoculated by spraying a spore suspension (1 x 105 uredospores/ml) on the test plants. After an incubation period of 1 day at 20° C and 95% r. h. plants are kept for 10 days 20° C / 18° C (day/night) and 60% r.h. in a greenhouse. The disease incidence is assessed 11 days after inoculation.
Compounds of formula I, in particular compounds l.c.081 , l.f.081 , l.g.081 and l.t.081 at 200 ppm inhibit fungal infestation in this test to a least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %.
Maαnaporthe αrisea (Pyricularia oryzae) I rice / preventive (Action against rice blast) 3 weeks old rice plants cv. Koshihikari are treated with the formulated test compound in a spray chamber. Two days after application rice plants are inoculated by spraying a spore suspension (1 x 105 conidia/ml) on the test plants. After an incubation period of 6 days at 25° C and 95% r. h. the disease incidence is assessed.
Compounds of formula I, in particular compounds l.f.081 and l.h.081 at 200 ppm inhibit fungal infestation in this test to a least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %.
Pyrenophora teres (Helminthosporium teres) I barley / preventive (Action against net blotch on barley)
1 -week-old barley plants cv. Regina are treated with the formulated test compound in a spray chamber. Two days after application barley plants are inoculated by spraying a spore suspension (2.6 x 104 conidia/ml) on the test plants. After an incubation period of 4 days at 20° C and 95% r. h. the disease incidence is assessed.
Compounds of formula I, in particular compounds l.c.081 and l.t.081 at 200 ppm inhibit fungal infestation in this test to a least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %.
Seotoria tritiα f /wheat / preventive (Action against Septoria leaf spot on wheat)
2 weeks old wheat plants cv. Riband are treated with the formulated test compound in a spray chamber. One day after application wheat plants are inoculated by spraying a spore suspension (106 conidia/ml) on the test plants. After an incubation period of 1 day at 22°C/21 0C and 95% r. h. plants are kept at 22°C/21°C and 70% r.h. in a greenhouse. The disease incidence is assessed 16 - 18 days after inoculation.
Compounds of formula I, in particular compounds l.c.081 , Lf .081 , l.g.081 , l.h.081 , l.r.081 and l.t.081 at 200 ppm inhibit fungal infestation in this test to a least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %.
Uncinula necator/ grape / preventive (Action against powdery mildew on grape) 5 weeks old grape seedlings cv. Gutedel are treated with the formulated test compound in a spray chamber. One day after application grape plants are inoculated by shaking plants infected with grape powdery mildew above the test plants. After an incubation period of 7 days at 24/22° C and 70% r. h. under a light regime of 14/1O h (light/dark) the disease incidence is assessed.
Compounds of formula I, in particular compounds l.c.081 , l.f.081 , l.g.081 , l.h.081 and IΛ.081 at 200 ppm inhibit fungal infestation in this test to a least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %.

Claims

What is claimed is:
1. A compound of formula I
Figure imgf000034_0001
wherein R1, R2, R3 and R4, each independently of each other and independently of m and n when m and/or n are 2, 3 or 4, are hydrogen, halogen, Ci-C6alkyl, d-C6haloalkyl or
Ci-C6alkyloxy, or
R1 and R2 or R3 and R4, each independently of each other, together with the carbon atom to which they are attached, form a group C=O, C=S or C=CR10R11, or R1 and R2 or R3 and R4, each independently of each other, together with the carbon atom to which they are attached form an optionally substituted three- to six- membered spiro-attached ring, or
R1 and R2 or R3 and R4, each independently of each other, are part of an endocyclic
C=C double bond when m or n are each independently of each other 2, 3 or 4, or R1 and R2 or R3 and R4, each independently of each other, form an optionally substituted saturated or unsaturated annulated ring together with the carbon atoms to which they are attached when m or n are 2, 3 or 4;
R5 and R6, each independently of each other, are CrC6alkyl, CrC6haloalkyl, C3-
Cecycloalkyl, C2-C6alkenyl, C2-C6alkynyl, CrC6alkyloxy, hydroxyl or an optionaly substituted aryl, or
R5 and R6 together with the silicon atom to which they are attached, form an optionally substituted, four- to seven-membered spiro-attached ring;
R7 is an optionally substituted aryl, or heteroaryl;
R8 is CrC6alkyl, halogen or cyano; R9 is hydrogen, mercapto or CrC3alkylthio;
R10 and R11 each independently of each other are hydrogen, halogen, CrCβalkyl, Cr
C3haloalkyl or Ci-C6alkyloxy; m and n, independently of each other, are 1 , 2, 3 or 4, and
(m + n) is equal to 2, 3, 4, 5 or 6.
2. A compound of formula I according to claim 1 in free form.
3. A compound of formula I according to claim 1 in an agrochemically usable salt form.
4. A compound of formula I according to any one of claims 1 to 3 wherein
R1, R2, R3 and R4, each independently of each other, are hydrogen, halogen or d-
C6alkyl;
R5 and R6, each independently of each other, are CrC6alkyl, CrC6haloalkyl or C3- C6cycloalkyl;
R7 is an optionally substituted aryl;
R8 is Ci-C6alkyl or halogen;
R9 is hydrogen, mercapto or methylthio;
(m + n) is equal to 2, 3, 4 or 5.
5. A compound of formula I according to any one of claims 1 to 4, wherein
R1, R2, R3 and R4, each independently of each other, are hydrogen or Ci-C6alkyl; R5 and R6, each independently of each other, are CrC6alkyl or CrC6haloalkyl; R7 is phenyl substituted at least in one ortΛo-position with halogen; R8 is chloro or fluoro;
R9 is hydrogen or mercapto; (m + n) is equal to 2, 3 or 4.
6. A compound of formula I according to any one of claims 1 to 5, wherein R1, R2, R3 and R4, each independently of each other, are hydrogen or methyl;
R5 and R6, each independently of each other, are methyl or ethyl; R7 is 2,4,6-trifluorophenyl or 2-chloro-6-fluorophenyl; R8 is chloro; R9 is hydrogen; (m + n) is equal to 3 or 4.
7. A process for the preparation of a compound of formula I defined in claim 1 , which comprises reacting a compound of formula II,
Hal N — N-^γR7
R9ΛNANAR8 wherein R7, R8 and R9 are as defined for formula I and Hal is halogen, preferably fluorine, chlorine or bromine, with a compound of formula III
(R2R1C)m (CR3R4)n (Ml)
H wherein R1, R2, R3, R4, R5, R6, m and n are as defined for formula I.
8. A fungicidal composition for controlling and protecting against phytopathogenic microorganisms, comprising as active ingredient at least one compound of formula I defined in claim 1 , in free form or in agrochemically usable salt form, and at least one adjuvant.
9. A composition according to claim 8, which comprises at least one additional fungicidally active compound, preferably selected from the group consisting of azoles, pyrimidinyl carbinoles, 2-amino-pyrimidines, morpholines, anilinopyrimidines, pyrroles, phenylamides, benzimidazoles, dicarboximides, carboxamides, strobilurines, dithiocarbamates, N-halomethylthiotetrahydrophthalimides, copper-compounds, nitrophenols, organo-phosphor-derivatives.
10. The use of a compound of formula I defined in claim 1 for controlling or preventing infestation of plants or non-living materials by phytopathogenic microorganisms.
11. A method of controlling and preventing an infestation of crop plants or non-living materials by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, which comprises the application of a compound of formula I defined in claim 1 as active ingredient to the plant, to parts of the plants or to the locus thereof, or to any part of the non-living materials.
12. A method according to claim 11 , wherein the phytopathogenic microorganisms are fungal organisms.
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