Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
  • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
  • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

• the present invention relates to microbiocidal oxadiazole derivatives, eg, as active ingredients, which have microbiocidal activity, in particular fungicidal activity.
• the invention also relates to agrochemical compositions which comprise at least one of the oxadiazole derivatives, to processes of preparation of these compounds and to uses of the oxadiazole derivatives 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.
• Microbiocidal oxadiazole derivatives are known as pharmaceutical ly-active agents from, eg, WO 2013/008162.
• WO 2015/185485 discloses the use of substituted oxadiazoles for combating phytopathogenic fungi.
• X represents O, CR 0 R 11 or NR 2 ;
• n 0 or 1 ;
• R , R 2 , R 3 and R 4 independently represent hydrogen, halogen, d-C 4 alkyl or Ci_C 4 alkoxy;
• R 5 represents hydrogen or Ci_C 4 alkyl
• R 6 represents hydrogen or Ci_C 4 alkyl
• R 7 and R 8 independently represent hydrogen, halogen, Ci_C 4 alkyl or Ci_C 4 alkyl substituted with 1 to 3 groups represented by halogen; or Ci-C 4 alkoxy when X is CR 0 R 11 , with the proviso that only one of R 7 and R 8 is Ci-C 4 alkoxy;
• R 9 represents hydrogen, Ci-C 6 alkyl, Ci-C 6 alkyl substituted with 1 to 3 groups represented by R 3 , C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, Ci-C 6 alkoxy, Ci-C 6 haloalkyl, formyl, Ci-C 6 alkylcarbonyl, Ci-C 6 alkoxycarbonyl, Ci-C 6 alkylcarboxylate, C 3 -C 7 cycloalkyl, C 3 -C 7 cycloalkyl substituted with 1 to 3 groups represented by R 3 , aryl, aryl substituted with 1 to 3 groups represented by R 3 , heteroaryl, heteroaryl substituted with 1 to 3 groups represented by R 3 , heterocyclyl, heterocyclyl substituted with 1 to 3 groups represented by R 3 , phenyl-Ci-C 6 alkyl, or phenyl-Ci-C 6 alkyl substituted with 1 to 3 groups represented by R 3 ;
• R 0 and R independently represent hydrogen, Ci.C 4 alkyl or Ci.C 4 alkyl substituted with 1 to 3 groups represented by halogen;
• R 2 represents hydrogen or d-C 4 alkyl;
• R 3 independently represents halogen, cyano, amino, nitro, hydroxy, sulfhydryl, C 1 -C4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C4 alkoxy, Ci-C 4 alkylthio, C 1 -C4 haloalkoxy, C 1 .C4 alkoxycarbonyl, N- Ci-C 4 alkylamino or N,N-di-Ci-C 4 alkylamino; or a salt or an N-oxide thereof.
• novel compounds of formula (I) have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.
• an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I).
• a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms wherein a fungicidally effective amount of a compound of formula (I), or a composition comprising this compound as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
• a compound of formula (I) as a fungicide
• substituents are themselves indicated as being substituted, this means that they may carry one or more (eg, 1 , 2 or 3) identical or different substituents.
• halogen refers to fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
• Ci_C 6 alkyl refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to six carbon atoms, and which is attached to the rest of the molecule by a single bond.
• the term "Ci_C 4 alkyl” is to be construed accordingly.
• Examples of Ci_C 6 alkyl include, but are not limited to, methyl, ethyl, n-propyl, 1-methylethyl (iso-propyl), n-butyl,1-dimethylethyl (i-butyl) and n-pentyl.
• C 3 .C 6 alkenyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond that can be of either the (E)- or (Z)-configu ration, having from three to six carbon atoms, which is attached to the rest of the molecule by a single bond.
• C 2 -C 4 alkenyl is to be construed accordingly. Examples of C 2 -C 4 alkenyl include, but are not limited to, ethenyl, prop-1-enyl, but-1-enyl.
• C 3 -C 6 alkynyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from three to six carbon atoms, and which is attached to the rest of the molecule by a single bond.
• C 2 -C 4 alkynyl is to be construed accordingly. Examples of C 2 -C 4 alkynyl include, but are not limited to, ethynyl, prop-1-ynyl, but-1-ynyl.
• Ci_C 6 alkoxy refers to a radical of the formula -OR a where R a is a d. C 6 alkyl radical as generally defined above.
• the term "Ci_C 4 alkoxy” is to be construed accordingly. Examples of Ci_C 6 alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, iso-propoxy, butoxy.
• Ci_C 6 haloalkyl refers to a Ci_C 6 alkyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
• the term “Ci_C 4 haloalkyl” is to be construed accordingly.
• Examples of Ci_C 6 haloalkyl include, but are not limited to fluoromethyl, fluoroethyl, trifluoromethyl, 2,2,2-trifluoroethyl.
• Examples of Ci_C 6 alkylcarbonyl include, but are not limited to, acetyl.
• Ci_C 4 alkoxycarbonyl is to be construed accordingly. Examples of Ci_C 6 alkoxycarbonyl include, but are not limited to, methoxycarbonyl, ethoxycarbonyl and iso-propoxycarbonyl.
• Ci_C 4 alkylcarboxylate is to be construed accordingly. Examples of Ci-C 6 alkylcarboxylate include acetate, propionate and butyrate.
• C 3 -C 7 cycloalkyl may be mono- or bi-cyclic and contains 3 to 7 carbon atoms.
• C 3 -C 6 cycloalkyl is to be construed accordingly.
• Examples of C 3 -C 7 cycloalkyl include, but are not limited to, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
• aryl refers to an aromatic ring system consisting solely of carbon and hydrogen atoms which may be mono-, bi- or tricyclic. Examples of such ring systems include phenyl, naphthalenyl, anthracenyl, indenyl or phenanthrenyl.
• heteroaryl refers to a 5- or 6-membered aromatic monocyclic ring radical which comprises 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur. The heteroaryl radical may be bonded via a carbon atom or heteroatom.
• heteroaryl examples include, but are not limited to, furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl or pyridyl.
• heterocyclyl refers to a stable 5- or 6-membered non-aromatic monocyclic ring radical which comprises 1 , 2, or 3, heteroatoms individually selected from nitrogen, oxygen and sulfur.
• the heterocyclyl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom.
• heterocyclyl examples include, but are not limited to, azetidinyl, oxetanyl, pyrrolinyl, pyrrolidyl, tetrahydrofuryl, tetrahydrothienyl, piperidyl, piperazinyl, tetrahydropyranyl, morpholinyl or perhydroazepinyl.
• phenylCi-C 6 alkyi refers to a phenyl ring attached to the rest of the molecule by a single bond or by a Ci_C 6 alkyi radical as defined above.
• phenylCi-C 6 alkyi include, but are not limited to, benzyl or 2-phenylethyl.
• cyano means a -CN group.
• amino means an -NH 2 group.
• nitro means an -N0 2 group.
• hydroxy means an -OH group.
• sulfhydryl means an -SH group.
• Ci-C 4 alkylthio means an -SR a group, where each R a is a Ci_C 4 alkyi radical as defined above.
• Ci-C 4 haloalkoxy refers to a Ci_C 4 alkoxy group as defined above substituted by one or more of the same or different halogen atoms.
• Ci-C 4 haloalkoxy include, but are not limited to, fluoromethoxy, fluoroethoxy, trifluoromethoxy, trifluoroethoxy.
• N-Ci_C 4 alkylamino refers to a radical of the formula -NH-R a where R a is a Ci-C 4 alkyi radical as defined above.
• N,N-diCi_C 4 alkylamino refers to a radical of the formula -N(R a )-R a where each R a is a Ci.C 4 alkyi radical, which may be the same or different, as defined above.
• O, N, S mean oxygen, nitrogen and sulphur, respectively.
• substituted with 1 to 3 groups represented by R 3 in relation to R 9 means substitution by 1 , 2 or 3 groups represented by R 3 .
• R 3 when n is 0, a four-membered ring structure is present bearing the -
• asymmetric carbon atoms in a compound of formula (I) means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. 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.
• the present invention includes all those possible isomeric forms and mixtures thereof for a compound of formula (I).
• formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism) where present.
• the present invention includes all possible tautomeric forms for a compound of formula (I).
• the compounds of formula (I) according to the invention are in free form, in covalently hydrated form , in oxidized form as an N-oxide or in salt form, e.g., an agronomically usable or agrochemically acceptable salt form.
• N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
• X represents O or CR 0 R 11 .
• X represents O.
• n represents 1 ;
• R , R 2 , R 3 and R 4 independently represent hydrogen, halogen, d-C 4 alkyl, and more preferably hydrogen, chloro or fluoro or methyl. Even more preferably, R is chloro, fluoro or methyl and R 2 , R 3 and R 4 are hydrogen, or R 2 is chloro, fluoro or methyl and R , R 3 and R 4 are hydrogen, and most preferably, R , R 2 , R 3 and R 4 are hydrogen.
• R 5 represents hydrogen or methyl. More preferably, R 5 represents hydrogen.
• R represents hydrogen or methyl. More preferably, R represents hydrogen.
• R 7 and R 8 independently represent hydrogen, halogen, Ci_C 4 alkyl or Ci_C 4 alkyl substituted by 1 to 3 halogen atoms. More preferably, R 7 and R 8 independently represent hydrogen, halogen or methyl. Even more preferably, R 7 and R 8 independently of one another represent hydrogen or methyl.
• R 9 is selected from hydrogen, Ci-C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 7 cycloalkyl, Ci-C 6 alkyl substituted with 1 to 3 groups represented by R 3 , Ci-C 6 alkoxy, Ci-C 6 alkylcarbonyl, Ci-C 6 alkoxycarbonyl, aryl, aryl substituted with 1 to 3 groups represented by R 3 , heteroaryl or heteroaryl substituted with 1 to 3 groups represented by R 3 .
• R 9 is selected from hydrogen, Ci-C 6 alkyl, Ci-C 6 alkyl substituted with halogen or cyano, Ci-C 6 alkoxy, Ci-C 6 alkylcarbonyl, Ci-C 6 alkoxycarbonyl, aryl, aryl substituted with halogen or cyano, heteroaryl or heteroaryl substituted with halogen or cyano, or R 9 is phenyl, phenyl substituted with 1 , 2 or 3 groups represented by R 3 , benzyl or benzyl substituted with 1 , 2 or 3 groups represented by R 3 , C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl substituted with 1 , 2 or 3 groups represented by R 3 pyrazolyl or pyrazolyl substituted with 1 , 2 or 3 groups represented by R 3 tetrahydropyranyl or tetrahydropyranyl substituted with 1 , 2 or 3 groups represented by R 3
• R 9 represents hydrogen, Ci-C 6 alkyl or Ci-C 6 alkyl substituted with 1 to 3 groups represented by halogen.
• R 9 represents hydrogen, Ci-C 4 alkyl or C 1 -C4 alkyl substituted with 1 to 3 groups represented by halogen, preferably fluorine.
• R 9 represents hydrogen, methyl, ethyl, trifluoromethyl or 2,2,2-trifluoroethyl.
• R 9 represents a group selected from hydrogen, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, sec-butyl, cyclopropyl, 2-iso-butyl, tert-butyl, 2-allyl, 1-methylallyl, 2- methylallyl, 1-methylprop-2-ynyl, prop-2-ynyl, but-2-ynyl, 1-methylbut-2-ynyl, 2-methoxyethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl, 1 , 1-difluoroethyl, fluoromethyl, difluoromethyl, trifluoromethyl, cyclobutyl, cyclopentyl, cyclohexyl, oxetan-3-yl, tetrahydrofuran-3-yl, tetrahydropyran-4-yl, (4- cyanoph
• R 0 and R independently of one another represent hydrogen, methyl, trichloromethyl or trifluoromethyl. Most preferably, R 0 and R are both hydrogen, wherein CR 0 R 11 is - CH 2 -. Preferably, R 2 represents hydrogen, methyl, ethyl or iso-propyl.
• R 3 represents halogen or cyano.
• Halogen may be individually selected from fluoro, chloro, bromo or iodo, and R 9 substituted by 1 , 2 or 3 R 3 substituents.
• X represents O or CR 0 R 11 and n represents 1. More preferably, X represents O and n represents 1. Preferably, X represents O;
• n 1 ;
• R , R 2 , R 3 and R 4 independently represent hydrogen, halogen and d-C 4 alkyl
• R 5 represents hydrogen or methyl
• R 6 represents hydrogen or methyl
• R 7 and R 8 independently represent hydrogen, halogen or methyl
• R 9 is hydrogen, Ci-C 4 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyi, Ci-C 4 alkyl substituted with 1 to 3 groups represented by R 3 , C 1 -C4 alkoxy, Ci-C 4 alkylcarbonyl, Ci-C 4 alkoxycarbonyl, aryl, aryl substituted with 1 to 3 groups represented by R 3 , heteroaryl or heteroaryl substituted with 1 to 3 groups represented by R 3 .
• X represents O
• n 1 ;
• R , R 2 , R 3 and R 4 independently represent hydrogen, halogen and Ci_C 4 alkyl
• R 5 represents hydrogen or methyl
• R 6 represents hydrogen or methyl
• R 7 and R 8 independently represent hydrogen, fluorine or methyl
• n 1 ;
• R , R 2 , R 3 and R 4 independently represent hydrogen, halogen and Ci_C 4 alkyl
• R 5 represents hydrogen or methyl
• R 6 represents hydrogen or methyl
• R 7 and R 8 independently represent hydrogen, methyl or trifluoromethyl
• X represents O
• n 1 ;
• R is chloro, fluoro or methyl and R 2 , R 3 and R 4 are hydrogen, or R 2 is chloro, fluoro or methyl and R , R 3 and R 4 are hydrogen, or R , R 2 , R 3 and R 4 are hydrogen;
• R 5 represents hydrogen or methyl
• R 6 represents hydrogen or methyl
• R 7 and R 8 independently represent hydrogen, methyl or trifluoromethyl
• R 9 represents hydrogen, methyl, ethyl, trifluoromethyl or 2,2,2-trifluoroethyl.
• the compound according to Formula (I) is selected from a compound disclosed in Table T1 below.
• the compounds of the present invention may be enantiomers of the compound of Formula (I) as represented by a Formula (la) or a Formula (lb).
• the compounds of formula (I) according to the invention may be present in a reversible equilibrium with the corresponding covalently hydrated forms (ie, the compounds of formula (l-l) and formula (l-ll) as shown below) at the CF 3 -oxadiazole motif. This dynamic equilibrium may be important for the biological activity of the compounds of Formula (I).
• the compounds of formula (I) can be obtained by an amide coupling transformation with compounds of formula (A) and compounds of formula (B) by activating the carboxylic acid function of the compounds of formula (B), a process that usually takes place by converting the -OH of the carboxylic acid into a good leaving group, such as a chloride group, for example by using (COCI) 2 or SOCI 2 , prior to treatment with the compounds of formula (A), preferably in a suitable solvent (for example, dimethylformamide, dichloromethane or tetrahydrofuran), preferably at a temperature of between 25 °C and 200 °C, and optionally in the presence of a base such as triethyl amine or N,N- diisopropylethylamine, or under conditions described in the literature for an amide coupling.
• a suitable solvent for example, dimethylformamide, dichloromethane or tetrahydrofuran
• compounds of formula (I) can be prepared from compounds of formula (C) by treatment with trifluoroacetic anhydride (TFAA) in a suitable solvent, such as tetrahydrofuran, at a temperature between 0 °C and 25 °C.
• TFAA trifluoroacetic anhydride
• suitable solvent such as tetrahydrofuran
• Compounds of formula (C) can be prepared from compounds of formula (D) by treating them with hydroxylamine hydrochloride salt in the presence of a base, such as sodium carbonate, in a suitable solvent, such as methanol, at a temperature between 0 °C and 100 °C. This is shown in Scheme 3 below. For related examples, see Kitamura, S. et al. Chem. Pharm. Bull. (2001 ), 49, 268.
• Scheme 3 The compounds of formula (D) can be obtained by an amide coupling transformation with compounds of formula (A) and compounds of formula (E) using the transformation described previously in Scheme 1. This reaction is shown in Scheme 4 below. Preferably, neither X or N-R 9 is equal to N-H.
• Compounds of formula (E) can be made by known methods from known compounds or are commercially available. For additional examples, see: Chobanian, H. R. et al Tetrahedron Lett. (2006), 47, 3303; Makovec, F. et al. J. Med. Chem. (1992), 35, 3633.
• novel compounds of formula (I) have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.
• the compounds of formula (I) can be used in the agricultural sector and related fields of use, e.g., as active ingredients for controlling plant pests or on non-living materials for the 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 can be 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 protecting also those parts of the plants that grow later, e.g., from phytopathogenic microorganisms.
• the present invention further relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein an effective amount a compound of formula (I) is applied to the plants, to parts thereof or the locus thereof.
• fungicide as used herein means a compound that controls, modifies, or prevents the growth of fungi.
• fungicidally effective amount means the quantity of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all deviation from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection.
• 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 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 compounds of formula (I) 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 of formula (I) 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 fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses.
• These fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses are for example:
• Absidia corymbifera Alternaria spp, Aphanomyces spp, Ascochyta spp, Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terms, Aureobasidium spp. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. comprising B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C.
• capsulatum Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp, Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp, Peronosclerospora spp. Including P. maydis, P.
• leucotricha Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp, Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila, Puccinia Spp. including P. hordei, P. recondita, P. striiformis, P. triticina, Pyrenopeziza spp, Pyrenophora spp, Pyricularia spp. including P. oryzae, Pythium spp. including P.
• compounds of the invention according to formula (I) and fungicidal compositions containing these compounds may be used to control plant diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and/or Deuteromycete, Blasocladiomycete, Chrytidiomycete, Glomeromycete and/or Mucoromycete classes.
• pathogens may include:
• Oomycetes including Phytophthora diseases such as those caused by Phytophthora capsici, Phytophthora infestans, Phytophthora sojae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora and Phytophthora erythroseptica; Pythium diseases such as those caused by Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare and Pythium ultimum; diseases caused by Peronosporales such as Peronospora destructor, Peronospora parasitica, Plasmopara viticola, Plasmopara halstedii, Pseudoperonospora cubensis, Albugo Candida, Sclerophthora macrospora and Br
• Ascomycetes including blotch, spot, blast or blight diseases and/or rots for example those caused by Pleosporales such as Stemphylium solani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma destructiva, Phaeosphaeria herpotrichoides, Phaeocryptocus gaeumannii, Ophiosphaerella graminicola, Ophiobolus graminis, Leptosphaeria maculans, Hendersonia creberrima, Helminthosporium triticirepentis, Setosphaeria turcica, Drechslera glycines, Didymella bryoniae, Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus, Bi
• Valsa ceratosperma and others such as Actinothyrium graminis, Ascochyta pisi, Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans, Asperisporium caricae, Blumeriella jaapii, Candida spp.
• Gerlachia nivale Gibberella fujikuroi
• Gibberella zeae Gibberella zeae
• Gliocladium spp. Myrothecium verrucaria
• Nectria ramulariae Trichoderma viride
• Trichothecium roseum Trichothecium roseum
• Verticillium theobromae Myrothecium verrucaria
• Basidiomycetes including smuts for example those caused by Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, rusts for example those caused by Pucciniales such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp.
• Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae
• rusts for example those caused by Pucciniales such as Cerotelium fici, Chr
• Puccinia striiformis f.sp. Secalis Pucciniastrum coryli, or Uredinales such as Cronartium ribicola, Gymnosporangium juniperi- viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor and Uromyces viciae-fabae; and other rots and diseases such as those caused by Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani,
• Blastocladiomycetes such as Physoderma maydis.
• Mucoromycetes such as Choanephora cucurbitarum.; Mucor spp.; Rhizopus arrhizus, As well as diseases caused by other species and genera closely related to those listed above.
• the compounds and compositions comprising them may also have activity against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Strptomyces scabies and other related species as well as certain protozoa.
• the compounds of formula (I) may be used for example on turf, ornamentals, such as flowers, shrubs, broad-leaved trees or evergreens, for example conifers, as well as for tree injection, pest management and the like.
• target crops and/or useful plants to be protected typically comprise perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St.
• perennial and annual crops such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries
• cereals for example barley, maize (corn), millet, oats
• Augustine grass and Zoysia grass herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.
• herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme
• legumes for example beans, lentils, peas and soya beans
• useful plants is to be understood as also including 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) inhibitors, GS (glutamine synthetase) inhibitors or PPO (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) inhibitors
• GS glutamine synthetase
• PPO protoporphyrinogen-oxidase
• 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 is to be understood as also including 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.
• YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that
• crops is to be understood as including also crop 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.
• Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g. CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
• insecticidal proteins from Bacillus cereus or Bacillus popilliae such as ⁇ -endotoxins, e.g. CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins
• Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
• toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
• toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
• agglutinins proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
• ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
• steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl- transferase, cholesterol oxidases, ecdy
• ⁇ -endotoxins for example CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins.
• Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ).
• Truncated toxins for example a truncated CrylAb, are known.
• modified toxins one or more amino acids of the naturally occurring toxin are replaced.
• amino acid replacements preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
• Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO93/07278, W095/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
• Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
• the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
• insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
• Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a
• Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1 Ab toxin. Bt1 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
• Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence.
• the preparation of such transgenic maize plants is described in WO 03/018810.
• MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects. 5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/ES/96/02.
• NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
• NK603 * MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
• locus as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
• plants refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
• 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.
• vegetative material such as cuttings or tubers, for example potatoes.
• seeds in the strict sense
• roots in the strict sense
• fruits in the tubers
• bulbs rhizomes
• parts of plants there can 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 can be protected before transplantation by a total or partial treatment by immersion.
• plant propagation material is understood to denote seeds.
• the compounds of formula I may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they may be 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.
• Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti-foam and a crystal growth inhibitor. In use, these concentrates are diluted in water and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
• Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers.
• the particles contain the active ingredient retained in a solid matrix.
• Typical solid matrices include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.
• Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non- volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
• Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required.
• Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound.
• Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils
• Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.
• Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates.
• Encapsulated droplets are typically 1 to 50 microns in diameter.
• the enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound.
• Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores.
• Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring.
• Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene- butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
• compositions for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents.
• Pressurised sprayers wherein the active ingredient is dispersed in finely-divided form as a result of vaporisation of a low boiling dispersant solvent carrier, may also be used.
• Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to those skilled in the art.
• Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, ⁇ , ⁇ -dimethyl formamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glyco
• Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller's earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.
• a broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application.
• These agents when used, normally comprise from 0.1 % to 15% by weight of the formulation. They can be anionic, cationic, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes.
• Typical surface active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub.
• alcohol-alkylene oxide addition products such as tridecyl alcohol-C.sub. 16 ethoxylate
• soaps such as sodium stearate
• alkylnaphthalenesulfonate salts such as sodium dibutylnaphthalenesulfonate
• dialkyl esters of sulfosuccinate salts such as sodium di(2-ethylhexyl) sulfosuccinate
• sorbitol esters such as sorbitol oleate
• quaternary amines such as lauryl trimethylammonium chloride
• polyethylene glycol esters of fatty acids such as polyethylene glycol stearate
• salts of mono and dialkyl phosphate esters such as mono and dialkyl phosphate esters.
• adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, anti-foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.
• biocidally active ingredients or compositions may be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention. When applied simultaneously, these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank.
• These further biocidally active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators. Pesticidal agents are referred to herein using their common name are known, for example, from “The Pesticide Manual", 15th Ed., British Crop Protection Council 2009.
• compositions of the invention may also be applied with one or more system ically acquired resistance inducers ("SAR" inducer).
• SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
• the compounds of formula (I) are normally used in the form of agrochemical 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 or nonselective 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) may be 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 of at least one preferred individual compound as defined herein, in free form or in agrochemically usable salt form, and at least one of the above-mentioned adjuvants.
• the invention therefore provides a composition, preferably a fungicidal composition, comprising at least one compound formula (I) an agriculturally acceptable carrier and optionally an adjuvant.
• An agricultural acceptable carrier is for example a carrier that is suitable for agricultural use.
• Agricultural carriers are well known in the art.
• said composition may comprise at least one or more pesticidal ly-active compounds, for example an additional fungicidal active ingredient in addition to the compound of formula (I).
• the compound of formula (I) may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate.
• An additional active ingredient may, in some cases, result in unexpected synergistic activities.
• Suitable additional active ingredients include the following: acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenical fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, , dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine
• Suitable additional active ingredients also include the following: 3-difluoromethyl-
• the compounds of the invention may also be used in combination with anthelmintic agents.
• anthelmintic agents include, compounds selected from the macrocyclic lactone class of compounds such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives as described in EP- 357460, EP- 444964 and EP-594291.
• Additional anthelmintic agents include semisynthetic and biosynthetic avermectin/milbemycin derivatives such as those described in US-5015630, WO-9415944 and WO- 9522552. Additional anthelmintic agents include the benzimidazoles such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of the class. Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines such as tetramisole, levamisole, pyrantel pamoate, oxantel or morantel.
• Additional anthelmintic agents include flukicides, such as triclabendazole and clorsulon and the cestocides, such as praziquantel and epsiprantel.
• the compounds of the invention may be used in combination with derivatives and analogues of the paraherquamide/marcfortine class of anthelmintic agents, as well as the antiparasitic oxazolines such as those disclosed in US-5478855, US- 4639771 and DE-19520936.
• the compounds of the invention may be used in combination with derivatives and analogues of the general class of dioxomorpholine antiparasitic agents as described in WO 96/15121 and also with anthelmintic active cyclic depsipeptides such as those described in WO 96/1 1945, WO 93/19053,
• the compounds of the invention may be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
• ectoparasiticides for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
• the compounds of the invention may be used in combination with terpene alkaloids, for example those described in International Patent Application Publication Numbers WO 95/19363 or WO 04/72086, particularly the compounds disclosed therein.
• Organophosphates acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, bromophos, bromophos-ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl, demeton-S-methyl sulphone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosthiazate, heptenophos, isazophos, isothioate, isoxathion, malathion, me
• Carbamates alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801 , isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717.
• Pyrethroids acrinathin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E) -(1 R)-cis-2,2- dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, beta -cyfluthrin, cyfluthrin, a-cypermethrin, beta -cypermethrin, bioallethrin, bioallethrin((S)-cyclopentylisomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin, cythithrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, ethofenprox, fenfluthrin, fenpropathrin, fenval
• Arthropod growth regulators a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole, chlorfentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenoids: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.
• antiparasitics acequinocyl, amitraz, AKD-1022, ANS-1 18, azadirachtin, Bacillus thuringiensis, bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidine, cyromazine, diacloden, diafenthiuron, DBI-3204, dinactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, ethofenprox, fenazaquin, flumite, MTI- 800, fenpyroximate, fluacrypyrim, flubenzimine, flubrocythrinate, flufenzine, flufenprox, fluproxyfen, halofenprox, hydra
• Biological agents Bacillus thuringiensis ssp aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, virus and fungi.
• Bactericides chlortetracycline, oxytetracycline, streptomycin.
• TX means "one compound selected from the group consisting of the compounds described in Tables 1 to 33 (below) of the present invention or the compounds 1 to 60 described in Table T1 (below)):
• an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX,
• an acaricide selected from the group of substances consisting of 1 , 1-bis(4-chlorophenyl)-2- ethoxyethanol (lUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate (lUPAC/Chemical Abstracts name) (1059) + TX, 2-fluoro-A/-methyl-A/-1-naphthylacetamide (lUPAC name) (1295) + TX, 4-chlorophenyl phenyl sulfone (lUPAC name) (981 ) + TX, abamectin (1 ) + TX, acequinocyl (3) + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, alpha- cypermethrin (202) + TX, amidithion (870) + TX, amid
• an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (lUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (lUPAC name) (347) and triphenyltin hydroxide (lUPAC name) (347) + TX, an anthelmintic selected from the group of substances consisting of abamectin (1 ) + TX, crufomate (101 1 ) + TX,
• a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis (alternative name) (33) + TX, Aphidius colemani (alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide (scientific name) (49) + TX, Bacillus thuringiensis Hopkins (scientific name) (
• a soil sterilant selected from the group of substances consisting of iodomethane (lUPAC name) (542) and methyl bromide (537) + TX,
• a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate [CCN] + TX, morzid [CCN] + TX, penfluron (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine (alternative name) [CCN] and
• an insecticide selected from the group of substances consisting of 1-dichloro-1-nitroethane (lUPAC/Chemical Abstracts name) (1058) + TX, 1 ,1-dichloro-2,2-bis(4-ethylphenyl)ethane (lUPAC name) (1056), + TX, 1 ,2-dichloropropane (lUPAC/Chemical Abstracts name) (1062) + TX, 1 ,2- dichloropropane with 1 ,3-dichloropropene (lUPAC name) (1063) + TX, 1-bromo-2-chloroethane (lUPAC/Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (lUPAC name) (1451 ) + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate (lUPAC
• a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (lUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (lUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913)
• a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, 1 ,2-dibromo-3-chloropropane (lUPAC/Chemical Abstracts name) (1045) + TX, 1 ,2- dichloropropane (lUPAC/ Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3- dichloropropene (lUPAC name) (1063) + TX, 1 ,3-dichloropropene (233) + TX, 3,4- dichlorotetrahydrothiophene 1 , 1-dioxide (lUPAC/Chemical Abstracts name) (1065) + TX, 3-(4- chlorophenyl)-5-methylrhodanine (lUPAC name) (980) + TX, 5-methyl-6-thioxo-1 ,3,5-thiadiazinan-3- ylacetic acid (lUPAC name) (1286)
• a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,
• a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX,
• a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1 ,3-dione (lUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891 ) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91 ) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol (alternative name) (850) + TX, coumachlor (1004) + TX, co
• a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (lUPAC name) (934) + TX, 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (lUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX,
• an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171 ) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, methiocarb (530) + TX, pyridin-4-amine (lUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX,
• a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX,
• a wound protectant selected from the group of substances consisting of mercuric oxide (512)
• azaconazole 60207- 31-0] + TX, bitertanol [70585-36-3] + TX, bromuconazole [1 16255-48-2] + TX, cyproconazole [94361- 06-5] + TX, difenoconazole [1 19446-68-3] + TX, diniconazole [83657-24-3] + TX, epoxiconazole [106325-08-0] + TX, fenbuconazole [1 14369-43-6] + TX, fluquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol [76674-21-0] + TX, hexaconazole [79983-71-4] + TX, imazalil [35554-44-0] + TX, imibenconazole [86598-92-7] + TX
• the active ingredient mixture of the compounds of formula I selected from Tables 1 to 33 (below) of the present invention or the compounds 1 to 60 described in Table T1 with active ingredients described above comprises a compound selected from Tables 1 to 33 (below) of the present invention or the compounds 1 to 60 described in Table T1 and an active ingredient as described above preferably in a mixing ratio of from 100: 1 to 1 :6000, especially from 50: 1 to 1 :50, more especially in a ratio of from 20: 1 to 1 :20, even more especially from 10:1 to 1 :10, very especially from 5: 1 and 1 :5, special preference being given to a ratio of from 2: 1 to 1 :2, and a ratio of from 4: 1 to 2: 1 being likewise preferred, above all in a ratio of 1 : 1 , or 5: 1 , or 5:2, or 5:3, or 5:4, or 4: 1 , or 4:2, or 4:3, or 3: 1 , or 3:2, or 2: 1 , or 1 :5, or 2:5,
• the mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.
• the mixtures comprising a compound of formula I selected from Tables 1 to 33 (below) of the present invention or the compounds 1 to 60 described in Table T1 and one or more active ingredients as described above can be applied, for example, in a single "ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
• the order of applying the compounds of formula I selected from Tables 1 to 33 (below) of the present invention or the compounds 1 to 60 described in Table T1 and the active ingredients as described above is not essential for working the present invention.
• compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
• auxiliaries such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides
• compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
• auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
• Another aspect of invention is related to the use of a compound of formula (I) or of a preferred individual compound as defined herein, 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 or insecticidal mixture comprising at least one compound of formula (I) or at least one preferred individual compound as above-defined, in admixture with other fungicides or insecticides as described above, for controlling or preventing infestation of plants, e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living materials by insects or by phytopathogenic microorganisms, preferably fungal organisms.
• useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living materials by insects or by phytopathogenic microorganisms, preferably fungal organisms.
• a further aspect of invention is related to a method of controlling or preventing an infestation of plants, e.g., useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g., harvested food crops, or of non-living materials by insects or 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 the propagation material thereof, or to any part of the non-living materials.
• useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g., harvested food crops, or of non-living materials by insects or by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms
• a compound of formula (I) or of a preferred individual compound as above-defined as active ingredient to the plants, to parts of
• Controlling or preventing means reducing infestation by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, to such a level that an improvement is demonstrated.
• a preferred method of controlling or preventing an infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, or insects 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 or insect.
• 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 e.g. 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), may be 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).
• 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 dosages are from 10mg to 1g of active substance per kg of seeds.
• composition comprising a compound of formula (I) according to the present invention is applied either preventative, meaning prior to disease development or curative, meaning after disease development.
• compositions of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK
• compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects).
• appropriate formulation inerts diiluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects.
• conventional slow release formulations may be employed where long lasting efficacy is intended.
• Particularly formulations to be applied in spraying forms such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g.
• a seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds.
• suitable seed dressing formulation form e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds.
• seed dressing formulations are known in the art.
• Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules.
• the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least the compound of formula (I) optionally together with other active agents, particularly microbiocides or conservatives or the like.
• Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent.
• Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.
• Table 1 discloses 146 combinations (1.001 to 1.146) of R 5 , R 6 and R 9 substituents in accordance with compounds as defined for Formula (T-1 ).
• Formula (T-1 ) corresponds to Formula (I) as defined for the present invention.
• Tables 2 to 33 make available 146 individual compounds of the formula (T-1 ) in which R 5 , R 6 and R 9 are the substituents defined in Table 1 and X, n, R , R 2 , R 3 , R 4 , R 7 , R 8 , R 0 , R 11 , R 2 , and R 3 are specifically defined in Tables 2 to 33 (T-1.2 to T-1.33).
• R 9 R 5 R 6 .016 prop-2-ynyl H methyl.017 but-2-ynyl H methyl.018 1-methylbut-2-ynyl H methyl.019 2-methoxyethyl H methyl.020 2,2-difluoroethyl H methyl.021 2,2,2-trifluoroethyl H methyl.022 1 , 1-difluoroethyl H methyl.023 fluoromethyl H methyl.024 difluoromethyl H methyl.025 trifluoromethyl H methyl.026 cyclobutyl H methyl.027 cyclopentyl H methyl.028 cyclohexyl H methyl.029 oxetan-3-yl H methyl.030 tetra hyd rof u ran-3-y I H methyl.031 tetrahyd ropyran-4-yl H methyl.032 (4-cyanopheny
• Table 2 This table discloses 146 specific compounds of formula (T-1 )
• R 5 , R 6 , and R 9 are as defined above in the Table 1
• Table 3 This table discloses 146 specific compounds of formula (T-1 )
• Table 4 This table discloses 146 s ecific compounds of formula (T-1 )
• R 5 , R 6 , and R M are as defined above in the Table 1
• Table 5 This table discloses 146 s ecific compounds of formula (T-1 )
• R 5 , R 6 , and R M are as defined above in the Table 1
• Table 6 This table discloses 146 specific compounds of formula (T-1 )
• R 5 , R 6 , and R M are as defined above in the Table 1
• Table 7 This table discloses 146 s ecific compounds of formula (T-1 )
• R 5 , R 6 , and R M are as defined above in the Table 1
• Table 9 This table discloses 146 s ecific compounds of formula (T-1 )
• R 5 , R 6 , and R 9 are as defined above in the Table 1
• Table 10 This table discloses 146 s ecific compounds of formula (T-1 )
• R 5 , R 6 , and R 9 are as defined above in the Table 1
• Table 1 1 This table discloses 146 s ecific compounds of formula (T-1 )
• R 5 , R 6 , and R M are as defined above in the Table 1
• Table 12 This table discloses 146 specific compounds of formula (T-1 )
• R 5 , R 6 , and R M are as defined above in the Table 1
• Table 13 This table discloses 146 s ecific compounds of formula (T-1 )
• R 5 , R 6 , and R 9 is as defined above in the Table 1
• Table 14 This table discloses 146 s ecific compounds of formula (T-1 )
• R 5 , R 6 , and R M are as defined above in the Table 1
• Table 15 This table discloses 146 s ecific compounds of formula (T-1 )
• R 5 , R 6 , and R M are as defined above in the Table 1
• Table 16 This table discloses 146 specific compounds of formula (T-1 )
• R 5 , R 6 , and R M are as defined above in the Table 1
• Table 17 This table discloses 146 s ecific compounds of formula (T-1 )
• R 5 , R 6 , and R M are as defined above in the Table 1
• Table 18 This table discloses 146 s ecific compounds of formula (T-1 )
• R 5 , R 6 , and R 9 are as defined above in the Table 1
• Table 19 This table discloses 146 s ecific compounds of formula (T-1 )
• R 5 , R 6 , and R M are as defined above in the Table 1.
• Table 20 This table discloses 146 specific compounds of formula (T-1 )
• R 5 , R 6 , and R M are as defined above in the Table 1
• Table 21 This table discloses 146 s ecific compounds of formula (T-1 )
• R 5 , R 6 , and R 9 are as defined above in the Table 1
• Table 22 This table discloses 146 s ecific compounds of formula (T-1 )
• R 5 , R 6 , and R M are as defined above in the Table 1.
• Table 23 This table discloses 146 s ecific compounds of formula (T-1 )
• R 5 , R 6 , and R M are as defined above in the Table 1.
• Table 24 This table discloses 146 specific compounds of formula (T-1 )
• R 5 , R 6 , and R 9 are as defined above in the Table 1.
• Table 25 This table discloses 146 s ecific compounds of formula (T-1 )
• R 5 , R 6 , and R 9 are as defined above in the Table 1.
• Table 26 This table discloses 146 s ecific compounds of formula (T-1 )
• R 5 , R 6 , and R 9 are as defined above in the Table 1.
• Table 27 This table discloses 146 s ecific compounds of formula (T-1 )
• R 5 , R 6 , and R 9 are as defined above in the Table 1.
• Table 28 This table discloses 146 specific compounds of formula (T-1 )
• R 5 , R 6 , and R 9 are as defined above in the Table 1.
• Table 29 This table discloses 146 specific compounds of formula (T-1 )
• R 5 , R 6 , and R 9 are as defined above in the Table 1.
• Table 30 This table discloses 146 specific compounds of formula (T-1 )
• R 5 , R 6 , and R 9 are as defined above in the Table 1.
• Table 31 This table discloses 146 s ecific compounds of formula (T-1 )
• R 5 , R 6 , and R 9 are as defined above in the Table 1.
• Table 32 This table discloses 146 specific compounds of formula (T-1 )
• Table 33 This table discloses 146 specific compounds of formula (T-1 )
• R 5 , R 6 , and R 9 are as defined above in the Table 1.
• Compounds of Formula (I) according to the invention may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).
• advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).
• the compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm or 0.8 ppm.
• LC/MS Liquid Chromatography Mass Spectrometry and the description of the apparatus and the method (Methods A and B) is as follows: The description of the LC/MS apparatus and the method A is:
• Electrospray Polarity positive and negative ions
• Type of column Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1 .8 micron; Temperature: 60°C.
• Type of column Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1 .8 micron; Temperature: 60°C.
• enantiomerically pure final compounds may be obtained from racemic materials as appropriate via standard physical separation techniques, such as reverse phase chiral chromatography, or through stereoselective synthetic techniques, eg, by using chiral starting materials.
• the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
• the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
• Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water. Dusts a) b) c)
• Active ingredient [compound of formula (I)] 5 % 6 % 4 %
• Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
• the active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water.
• the mixture is extruded and then dried in a stream of air.
• polyethylene glycol (mol. wt. 200) 3 %
• Kaolin 89 % The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
• nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
• silicone oil (in the form of a 75 % emulsion in water) 1 %
• the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
• Flowable concentrate for seed treatment active ingredient [compound of formula (I)] 40 %
• Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
• the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
• a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
• living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
• 28 parts of a combination of the compound of formula I are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8: 1 ).
• This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved.
• To this emulsion a mixture of 2.8 parts 1 ,6- diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.
• the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
• the capsule suspension formulation contains 28% of the active ingredients.
• the medium capsule diameter is 8-15 microns.
• Example 1 This example illustrates the preparation of 2-fluoro-N-(2-methyl-3-oxo-isoxazolidin-4-yl)-4- [5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide (Compound 6 of Table T1 below)
• Step 1 Preparation of 2-fluoro-4-(N-hydroxycarbamimidoyl)-benzoic acid
• Step 2 Preparation of 2-fluoro-4-(5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl)benzoic acid
• Trifluoroacetic anhydride (4.1 mL) was added dropwise at 10 to 15 °C to a stirred suspension of 2-fluoro-4-(N-hydroxycarbamimidoyl)-benzoic acid (3.80 g, 19.0 mmol) in THF (77 mL). The beige suspension was warmed to room temperature and stirred overnight. After evaporation, the crude product was stirred with heptane/ethylacetate (95:5), filtered and dried under reduced pressure at 50 °C to yield 2-fluoro-4-(5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl)benzoic acid as yellow solid. Mp: 175- 177 °C. H NMR (400 MHz, DMSO-d 6 ) ⁇ ppm: 13.55 (s, 1 H), 8.12 (t, 1 H), 8.00 (d, 1 H), 7.94(d, 1 H).
• Step 3 Preparation of 2-fluoro-4- 5-(trifluoromethyl)-[1 ,2,4]oxadiazol-3-yl)-benzoyl chloride
• Example 2 This example illustrates the preparation of N-(2-methyl-3-oxo-isoxazolidin-4-yl)-4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]benzamide (Compound 9 of Table T1 )
• amine derivatives of formula (A) (0.0375 mmol in 375 ⁇ DMA) were transferred to a 96 slot deep well plate (DWP96) containing the acid derivative of formula (B) (0.03 mmol) and DIPEA (0.09 mmol) in 250 ⁇ DMA, followed by the addition of BOP-CI (0.06 mmol) dissolved in DMA (250 ⁇ ).
• the DWP was sealed and stirred at 50°C for 18 hours. The solvent was removed under a stream of nitrogen.
• the resultant crude residues were solubilized in a mixture of MeOH (250 ⁇ ) and DMA (500 ⁇ ) and directly submitted for preparative LC/MS purification which provided the compounds of formula (I) in 10-85% yields.
• enantiomerically pure final compounds may be obtained from racemic materials as appropriate via standard physical separation techniques, such as reverse phase chiral chromatography, or through stereoselective synthetic techniques, (eg, by using chiral starting materials).
• Table T1 Melting point (m.p.) data and/or retention times for the compounds of Formula (I) j Entry j Name j Structure T [M+H] j Method j MP j
• BIOLOGICAL EXAMPLES General examples of leaf disk tests in well plates:
• Leaf disks or leaf segments of various plant species are cut from plants grown in a greenhouse.
• the cut leaf disks or segments are placed in multiwell plates (24-well format) onto water agar.
• the leaf disks are sprayed with a test solution before (preventative) or after (curative) inoculation.
• Compounds to be tested are prepared as DMSO solutions (max. 10 mg/ml) which are diluted to the appropriate concentration with 0.025% Tween20 just before spraying.
• the inoculated leaf disks or segments are incubated under defined conditions (temperature, relative humidity, light, etc.) according to the respective test system.
• a single evaluation of disease level is carried out 3 to 14 days after inoculation, depending on the pathosystem. Percent disease control relative to the untreated check leaf disks or segments is then calculated.
• Mycelia fragments or conidia suspensions of a fungus prepared either freshly from liquid cultures of the fungus or from cryogenic storage, are directly mixed into nutrient broth.
• DMSO solutions of the test compound (max. 10 mg/ml) are diluted with 0.025% Tween20 by a factor of 50 and 10 ⁇ of this solution is pipetted into a microtiter plate (96-well format). The nutrient broth containing the fungal spores/mycelia fragments is then added to give an end concentration of the tested compound.
• the test plates are incubated in the dark at 24°C and 96% relative humidity.
• Example 1 Fungicidal activity against Puccinia recondita f. sp. tritici I wheat / leaf disc preventative (Brown rust)
• Wheat leaf segments cv. Kanzler were placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
• the leaf disks were inoculated with a spore suspension of the fungus 1 day after application.
• the inoculated leaf segments were incubated at 19 C and 75% relative humidity (rh) under a light regime of 12 hours light / 12 hours darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (7 to 9 days after application).
• the following compounds at 200 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
• Example 2 Fungicidal activity against Puccinia recondita f. sp. tritici I wheat / leaf disc curative (Brown rust)
• Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates (24-well format). The leaf segments are then inoculated with a spore suspension of the fungus. Plates were stored in darkness at 19°C and 75% relative humidity. The formulated test compound diluted in water was applied 1 day after inoculation. The leaf segments were incubated at 19°C and 75% relative humidity under a light regime of 12 hours light / 12 hours darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (6 to 8 days after application).
• the following compounds at 200 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
• Soybean leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water.
• leaf discs are inoculated by spraying a spore suspension on the lower leaf surface.
• the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (12 to 14 days after application).
• the following compounds at 200 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
• Example 4 fungicidal activity against Glomerella lagenarium (Colletotrichum lagenarium) liguid culture / cucumber / preventative (Anthracnose) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB - potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96- well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 C and the inhibition of growth is measured photometrically 3 to 4 days after application.
• DMSO DMSO
• the following compounds at 20 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control under the same conditions, which show extensive disease development.

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