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WO2018184984A1 - Dérivés d'oxadiazole microbiocides - Google Patents

Dérivés d'oxadiazole microbiocides Download PDF

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Publication number
WO2018184984A1
WO2018184984A1 PCT/EP2018/058102 EP2018058102W WO2018184984A1 WO 2018184984 A1 WO2018184984 A1 WO 2018184984A1 EP 2018058102 W EP2018058102 W EP 2018058102W WO 2018184984 A1 WO2018184984 A1 WO 2018184984A1
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methyl
formula
ccn
compounds
alternative name
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PCT/EP2018/058102
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English (en)
Inventor
Thomas James HOFFMAN
Daniel Stierli
Thomas Pitterna
Ramya Rajan
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Syngenta Participations Ag
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Priority to BR112019020756-2A priority Critical patent/BR112019020756B1/pt
Publication of WO2018184984A1 publication Critical patent/WO2018184984A1/fr

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    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/32—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing >N—CO—N< or >N—CS—N< groups directly attached to a cycloaliphatic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles

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 nonliving materials by phytopathogenic microorganisms, preferably fungi.
  • oxadiazole derivatives are known as insecticidal and acaricidal agents, eg, from CN 1927860.
  • WO 2013/064079, EP 0 276 432 and WO 2015/185485 describe the use of substituted oxadiazoles for combating phytopathogenic fungi.
  • A is:
  • R and R 2 are hydrogen;
  • R 3 is R 3a , wherein R 3a is hydroxyl, ethoxy, propyl, cyclopropyl or 2,2,2-trifluoroethyl;
  • R 4 is R 4a , wherein R 4a is C2-salkyl, Ci-2fluoroalkyl, C3-4alkenyl, C3-4alkynyl, cyanoCi salkyl, C2 4alkoxy, Ci-2alkoxyCi-3alkyl, C3-4cycloalkyl or C3-4cycloalkylCi-2alkyl; or
  • R 3 is R 3b , wherein R 3b is isopropyl, butyl, isobutyl, sec-butyl, propyloxy, butyloxy, prop-2-enyl, prop-2-ynyl, prop-2-enyloxy, prop-2-ynyloxy, methoxyethyl, cyclopropylmethyl, or 3-oxetanyl; and
  • R 4 is R 4b , wherein R 4b is Ci-4alkyl, Ci-2fluoroalkyl, C3-4alkenyl, C3-4alkynyl, cyanoCi-4alkyl, Ci 4alkoxy or Ci-4alkoxyC2-4alkyl; and
  • R 5 is cyano, d-salkyl, Ci sfluoroalkyl, C3-4alkenyl, C3-4alkynyl, C3-4haloalkenyl, cyanoCi salkyl, hydroxyCi salkyl, Ci-2alkoxyCi-3alkyl, Ci-2fluoroalkoxyCi-3alkyl, aminoCi-3alkyl, N-Ci-3alkylaminoCi- 3alkyl or N,N-diCi-3alkylaminoCi-3alkyl; or
  • R 5 represents C3-4cycloalkyl or C3-4cycloalkylCi-2alkyl, wherein the cycloalkyl moiety is optionally partially unsaturated, heterocyclyl or heterocyclylCi-2alkyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, wherein for R 5 , any cycloalkyl or heterocyclyl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R 6 ;
  • R 6 represents cyano, halogen, hydroxy, amino, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, difluoromethoxy; and wherein when R 5 comprises a substituted C3- 4cycloalkyl or heterocyclyl, these cycles may contain a carbonyl (C(O)) or sulfonyl (S(0)2) group; or wherein for R 3 as defined for each of (i) and (ii), R 4 and R 5 , together with the nitrogen atom to which they are bonded , form a cycle selected from 3-oxo-pyrrolidinyl, pyrrolidinyl, 2-oxo-pyrrolidinyl, azetidinyl, isooxazolidinyl, oxazolidinyl, morpholino, oxazinanyl, 1-methoxypiperazin-4-yl, 1- methylpiperazin-4-
  • 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).
  • Such an agricultural composition may further comprise at least one additional active ingredient and/or an agrochemically- acceptable diluent or carrier.
  • 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.
  • the use may exclude methods for the treatment of the human or animal body by surgery or therapy.
  • halogen refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine.
  • cyano means a -CN group.
  • hydroxyl or "hydroxy” means an -OH group.
  • amino means an -NH2 group.
  • Ci-salkyl refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to five carbon atoms, and which is attached to the rest of the molecule by a single bond .
  • C2-salkyl, d salkyl and Ci-2alkyl are to be construed accordingly.
  • Examples of d-salkyl include, but are not limited to, methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, and 1-dimethylethyl (i-butyl).
  • a "Ci-2alkylene” group refers to the corresponding definition of Ci-2alkyl, except that such radical is attached to the rest of the molecule by two single bonds. Examples of Ci-2alkylene, are -CH2- and -CH2CH2-.
  • Ci-4alkoxy refers to a radical of the formula -ORx where R x is a Ci- 4alkyl radical as generally defined above.
  • the terms C2-4alkoxy, d salkoxy and Ci-2alkoxy are to be construed accordingly.
  • Examples of Ci-4alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, and i-butoxy.
  • Ci-2fluoroalkyl refers to a Ci-2alkyl radical as generally defined above substituted by one or more fluorine atoms.
  • Examples of Ci-2fluoroalkyl include, but are not limited to fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, and 3,3,3-trifluoropropyl.
  • C3-4alkenyl 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 three or four carbon atoms, which is attached to the rest of the molecule by a single bond .
  • Examples of C3-4alkenyl include, but are not limited to, prop-1-enyl, allyl, and but-1-enyl.
  • C3-4haloalkenyl refers to a C3-46alkenyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C3-4alkynyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having three or four carbon atoms, and which is attached to the rest of the molecule by a single bond.
  • Examples of C3-4alkynyl include, but are not limited to, prop-1-ynyl, propargyl.
  • Ci-2alkoxyCi-3alkyl refers to radical of the formula R y -0-Rx- where R y is a Ci-2alkyl radical as generally defined above, and R x is a d salkylene radical as generally defined above.
  • hydroxyCi-3alkyl refers to a d salkyl radical as generally defined above substituted by one or more hydroxy groups.
  • hydroxyCi-2alkyl should be construed accordingly.
  • cyanoCi-3alkyl refers to refers to a d salkyl radical as generally defined above substituted by one or more cyano groups.
  • Ci salkylamino refers to a -HNR X radical wherein R x is a d salkyl radical as generally defined above.
  • N,N-did-3alkylamino refers to a -N(R X )2 radical wherein R x is the same or different d salkyl radical as generally defined above.
  • N-d-3alkylaminod-3alkyl refers to a d salkyl radical as generally defined above substituted by a Ci salkylamino group as defined above.
  • N ,N-diCi-3alkylaminoCi-3alkyl refers to a d salkyl radical as generally defined above substituted by an N,N-did-3alkylamino group as defined above.
  • d-4cycloalkyl refers to a stable, monocyclic ring radical which is saturated or partially unsaturated and contains 3 or 4 carbon atoms. Examples of d-4cycloalkyl includes, cyclopropyl, cyclobutyl.
  • d-4cycloalkyld-2alkyl refers to a d-4cycloalkyl ring as defined above attached to the rest of the molecule by a d-2alkylene radical as defined above.
  • d- 4cycloalkylCi-2alkyl include, but are not limited to cyclopropyl-methyl and cyclobutyl-ethyl.
  • heterocyclyl or “heterocyclic” generally refers to a stable, saturated or partially saturated , 4- to 6-membered, non-aromatic monocyclic ring, 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, pyrrolidyl, tetrahydrofuryl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidinyl, piperazinyl, tetrahydropyranyl, dioxolanyl, and morpholinyl.
  • azetidinyl oxetanyl
  • pyrrolidyl tetrahydrofuryl
  • tetrahydrothienyl tetrahydrothiopyranyl
  • piperidinyl piperazinyl
  • tetrahydropyranyl dioxolanyl
  • morpholinyl morpholinyl
  • 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 oxidized form as an N-oxide, in covalently hydrated form, 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.
  • A is: R is hydrogen.
  • R 2 is hydrogen
  • R 3 is R 3a , wherein R 3a is hydroxyl, ethoxy, propyl, cyclopropyl or 2,2,2-trifluoroethyl; and R 4 is R 4a , wherein R 4a is C2-salkyl, Ci-2fluoroalkyl, C3- 4alkenyl, C3-4alkynyl, cyanoCi salkyl, C2-4alkoxy, Ci-2alkoxyCi-3alkyl, C3-4cycloalkyl or C3-4cycloalkylCi- 2alkyl.
  • R 3a is ethoxy or cyclopropyl.
  • R 4a is C2-salkyl, Ci-2fluoroalkyl, C3-4alkenyl, C3- 4alkynyl, cyanoCi-2alkyl, C2-4alkoxy, Ci-2alkoxyCi-2alkyl, cyclopropyl or cyclopropylCi-2alkyl. More preferably, R 4a is C2-salkyl, C3-4alkenyl or C3-4alkynyl.
  • R 3 is R 3b , wherein R 3b is represents isopropyl, butyl, isobutyl, sec-butyl, propyloxy, butyloxy, prop-2-enyl, prop-2-ynyl, prop-2-enyloxy, prop- 2-ynyloxy, methoxyethyl, cyclopropyl methyl, or 3-oxetanyl; and R 4 is R 4b , wherein R 4b is Ci-4alkyl, Ci- 2fluoroalkyl, C3-4alkenyl, C3-4alkynyl, cyanoCi-4alkyl, Ci-4alkoxy or Ci-4alkoxyC2-4alkyl In accordance with embodiment (ii), preferably R 3b is n-butyloxy, cyclopropylmethyl or 3- oxetanyl.
  • R 4b is Ci-4alkyl, Ci-2fluoroalkyl, cyanoCi-4alkyl, Ci-4alkoxy or Ci-4alkoxyC2-4alkyl. More preferably, R 4b is methyl, ethyl, Ci-2fluoroalkyl, cyanoCi-2alkyl, methoxy, ethoxy or Ci-2alkoxyC2-4alkyl.
  • R 5 is cyano, d-salkyl, Ci sfluoroalkyl, C3-4alkenyl, C3-4alkynyl, C3-4haloalkenyl, cyanoCi salkyl, hydroxyCi-3alkyl, Ci-2alkoxyCi-3alkyl, Ci-2fluoroalkoxyCi-3alkyl, aminoCi-3alkyl, N-Ci-3alkylaminoCi- 3alkyl or N,N-diCi-3alkylaminoCi-3alkyl; or R 5 represents C3-4cycloalkyl, C3-4cycloalkylCi-2alkyl, wherein the cycloalkyl moiety is optionally partially unsaturated , heterocyclyl, heterocyclylCi-2alkyl, wherein the heterocyclyl moiety is a 4- to 6- membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, where
  • R 6 represents cyano, halogen, hydroxy, amino, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, difluoromethoxy; and wherein when R 5 comprises a substituted C3- 4cycloalkyl or heterocyclyl, these cycles may contain a carbonyl (C(O)) or sulfonyl (S(0)2) group; or Preferably, R 5 is cyano, d salkyl, Ci sfluoroalkyl, C3-4alkenyl, C3-4alkynyl, C3-4haloalkenyl, cyanoCi-2alkyl, hydroxyCi-2alkyl, Ci-2alkoxyCi-2alkyl, Ci-2fluoroalkoxyCi-2alkyl, aminoCi-2alkyl, N-C1- 2alkylaminoCi-2alkyl or N,N-diCi-2alkyla
  • R 5 is d salkyl, d sfluoroalkyl, d ⁇ alkenyl, d-4alkynyl, d-4haloalkenyl, cyanoCi-2alkyl, hydroxyCi-2alkyl, Ci-2alkoxyCi-2alkyl; or R 5 is cyclopropyl, cyclopropylCi-2alkyl, heterocyclyl, heterocyclylCi-2alkyl, wherein the heterocyclyl moiety is a 4- or 5-membered non-aromatic ring which comprises 1 or 2 heteroatoms individually selected from N and O, wherein for R 5 , any cyclopropyl or heterocyclyl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R 6 . Even more preferably, R 5 is Ci salkyl, Ci sfluoroalkyl, C3-4alkynyl or cyanoCi-2alkyl, or
  • R 5 is cyclopropyl, cyclopropylCi-2alkyl, wherein any cyclopropyl is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R 6 . Still even more preferably, R 5 is Ci- 3alkyl, Ci-2fluoroalkyl, C3-4alkenyl, C3-4alkynyl or cyanoCi-2alkyl, or R 5 is cyclopropyl, cyclopropyld- 2alkyl, wherein any cyclopropyl is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R 6 , wherein R 6 is halogen, methyl or ethyl.
  • R 4 and R 5 together with the nitrogen atom to which they are bonded , form a cycle selected from 3-oxo-pyrrolidinyl, pyrrolidinyl, 2-oxo-pyrrolidinyl, azetidinyl, isooxazolidinyl, oxazolidinyl, morpholino, oxazinanyl, 1-methoxypiperazin-4-yl, 1- methylpiperazin-4-yl, or 1-piperazin-4-yl ethanone.
  • R 4 and R 5 together with the nitrogen atom to which they are bonded, form a cycle selected from morpholino or oxazinanyl.
  • R 4 when R 3 is n-butyloxy, R 4 may also be hydrogen.
  • the compound according to Formula (I) is selected from a compound 1.1 to 1.28 listed in Table T1 (below). It is understood that when in aqueous media, the compounds of Formula (I) according to the invention may be present in a reversible equilibrium with the corresponding covalently hydrated forms (i.e., the compounds of Formula (l-la) and Formula (l-lla) as shown below, which may exist in tautomeric form as the compounds of formula (l-lb) and formula (l-llb)) at the CF3-oxadiazole motif. This dynamic equilibrium may be important for the biological activity of the compounds of Formula (I).
  • A, R ⁇ R 2 , R 3 (including R 3a and R 3b ), R 4 (including R 4a and R 4b ), R 5 and R 6 with reference to the compounds of Formula (I) of the present invention apply generally to the compounds of Formulae (l-l), (l-ll), (l-la) and (l-lla), as well do the specific disclosures of combinations of A, R , R 2 , R 3 (including R 3a and R 3b ), R 4 (including R 4a and R 4b ), R 5 and R 6 , as represented in the compounds described in Tables 1.1 to 1.5 or as represented in the compounds described in Tables 2.1 to 2.9, or the compounds 1.1 to 1.28 described in Table T1 (below).
  • the compounds of formula (I) can be obtained via a coupling transformation with compounds of formula (II) and compounds of formula (III), wherein X is halogen or OH, preferably halogen, in a suitable solvent (eg, dimethylformamide, dichloromethane, or tetrahydrofuran), preferably at a temperature between 25°C and 100°C, and optionally in the presence of a base (eg, NaHC03, Na2C03, K2CO3, NaOH, triethylamine or A/,A/-diisopropylethylamine), or under conditions described in the literature for an urea coupling.
  • a suitable solvent eg, dimethylformamide, dichloromethane, or tetrahydrofuran
  • a base eg, NaHC03, Na2C03, K2CO3, NaOH, triethylamine or A/,A/-diisopropylethylamine
  • compounds of formula (I) can optionally be obtained via a coupling transformation with compounds of formula (II) and compounds of formula (III), wherein X is -OH, via a process that converts the -OH into an improved halide leaving group, such as a chloride, for example by using triphosgene, phosgene, (COCI)2, or SOCI2, prior to treatment with the compounds of formula (II).
  • Compounds of formula (III) are commercially available or prepared using known methods. For related examples, see: Nelson, T. D et al Tetrahedron Lett.
  • compounds of formula (I) can be prepared from compounds of formula (II) via treatment with triphosgene, in a suitable solvent (eg, 1 ,2-dichloroethane, water, acetonitrile, ethyl acetate, chloroform, or toluene) followed by the addition of suitable amino nucleophiles of formula (IV), in the presence of a suitable base, such as pyridine, K2CO3, or triethylamine.
  • a suitable solvent eg, 1 ,2-dichloroethane, water, acetonitrile, ethyl acetate, chloroform, or toluene
  • suitable base such as pyridine, K2CO3, or triethylamine.
  • compounds of formula (I) can be prepared from compounds of formula (V) by treatment with trifluoroacetic acid, trifluoroacetic anhydride or trifluoroacetyl halide (including trifluoroacetyl fluoride, trifluoroacetyl chloride, and trifluoroacetyl bromide) in the presence of a base (eg, pyridine or 4-dimethylaminopyridine) in a suitable solvent, (eg, ethyl acetate, tetrahydrofuran, 2- methyltetrahydrofuran, or ethanol), at a temperature between 0°C and 75°C.
  • a base eg, pyridine or 4-dimethylaminopyridine
  • suitable solvent eg, ethyl acetate, tetrahydrofuran, 2- methyltetrahydrofuran, or ethanol
  • Compounds of formula (V) can be prepared from compounds of formula (VI) by treatment with a hydroxylamine hydrochloride salt or a hydroxylamine solution in water, in the presence of a base, such as triethylamine or potassium carbonate, in a suitable solvent, such as methanol or ethanol, at a temperature between 0°C and 80°C.
  • a base such as triethylamine or potassium carbonate
  • a suitable solvent such as methanol or ethanol
  • a catalyst eg, 8-hydroxyquinoline.
  • Compounds of formula (VI) can be prepared from compounds of formula (VII), wherein Y is halogen, via metal-promoted reaction with a suitable cyanide reagent, such as Pd(0)/Zn(CN)2 or CuCN, in a suitable solvent (eg, dimethylformamide or N-methylpyrrolidone) at elevated temperature between 80°C and 120°C.
  • a suitable cyanide reagent such as Pd(0)/Zn(CN)2 or CuCN
  • a suitable solvent eg, dimethylformamide or N-methylpyrrolidone
  • Compounds of formula (II), wherein R is hydrogen can be prepared from aldehyde compounds of formula (X), via treatment with compounds of formula (IX), in a suitable solvent, (eg, tetrahydrofuran or methanol) at a temperature between 25°C and 75°C and followed by the addition of a reducing reagent, such as NaBhU, NaBh CN, or LiAlhU), in a suitable solvent, (eg, tetrahydrofuran or ethanol) at temperatures between 0°C and 25°C.
  • a suitable solvent eg, tetrahydrofuran or ethanol
  • compounds of formula (II) can be prepared from compounds of formula (XI), wherein X is CI, Br, I, OH, or OS02Me, via treatment with amines of formula (IX) in a suitable solvent (eg, tetrahydrofuran) at a temperature between 25°C and 60°C.
  • a suitable solvent eg, tetrahydrofuran
  • Compounds of formula (XI), can be prepared from compounds of formula (XII), wherein X is CI or Br, by treatment with a halogen source [eg, N-bromosuccinimide (NBS) or N-chlorosuccinimide (NCS)] and a radical initiator [eg, (PhC02)2 or azobisisobutyronitrile (AIBN)] in a suitable solvent, such as tetrachloromethane, at temperatures between 55° and 100°C in the presence of ultraviolet light.
  • a halogen source eg, N-bromosuccinimide (NBS) or N-chlorosuccinimide (NCS)
  • a radical initiator eg, (PhC02)2 or azobisisobutyronitrile (AIBN)
  • suitable solvent such as tetrachloromethane
  • the compounds of formula (VII), wherein Y is halogen or CN, can be obtained via a coupling transformation with compounds of formula (XIII) and compounds of formula (III), wherein X is halogen or OH, preferably halogen, (XIII), in a suitable solvent (eg, dimethylformamide, dichloromethane, tetrahydrofuran, or 2-methyltetrahydrofuran), preferably at a temperature of between 0°C and 100°C, and optionally in the presence of a base (eg, NaHC03, Na2C03, K2CO3, NaOH, triethylamine or N,N- diisopropylethylamine), or under conditions described in the literature for an urea coupling.
  • a suitable solvent eg, dimethylformamide, dichloromethane, tetrahydrofuran, or 2-methyltetrahydrofuran
  • a base eg, NaHC03, Na2C03, K2CO3, NaOH
  • compounds of formula (VII) can optionally be obtained via a coupling transformation with compounds of formula (XIII) and compounds of formula (III), wherein X is OH, via a process that converts the -OH into an improved halide leaving group, such as a chloride, for example by using triphosgene, phosgene, (COCI)2, or SOCI2, prior to treatment with the compounds of formula (XIII).
  • Compounds of formula (III) are commercially available or prepared using known methods. For related examples, see: Nelson, T. D et al Tetrahedron Lett. (2004), 45, 8917; Senthil, K. et al Pest. Res. Journal (2009), 21 , 133; and Crich, D., Zou, Y. J. Org. Chem. (2005), 70, 3309. This reaction is shown in Scheme 10.
  • compounds of formula (VII), wherein Y is halogen or CN can be prepared from compounds of formula (XIII) via treatment with triphosgene, in a suitable solvent (eg, 1 ,2- dichloroethane, acetonitrile, ethyl acetate, chloroform, or toluene) followed by the addition of suitable nucleophiles of formula (IX), in the presence of a suitable base such as triethylamine.
  • a suitable solvent eg, 1 ,2- dichloroethane, acetonitrile, ethyl acetate, chloroform, or toluene
  • suitable base such as triethylamine
  • Compounds of formula (XIII), wherein Y is halogen or CN can be prepared from compounds of formula (XIV), wherein X is CI, Br, I, OH, or OS02Me, via treatment with amines of formula (IX), in the presence of a suitable base, such as NaHC03, Na2C03, K2CO3, or NaH, in a suitable solvent, such as dimethylformamide, N-methylpyrolidine, or acetonitrile, at a temperature between 0°C and 100°C.
  • a suitable base such as NaHC03, Na2C03, K2CO3, or NaH
  • a suitable solvent such as dimethylformamide, N-methylpyrolidine, or acetonitrile
  • a better reaction performance may be gained from the use of a catalyst (eg, BU4NHSO4, Bu4NBr, BU4NI, Nal, or 4-dimethylaminopyridine) or optionally with microwave irradiation.
  • a catalyst eg, BU4NHSO4, Bu4NBr, BU4NI, Nal, or 4-dimethylaminopyridine
  • microwave irradiation e.g., BU4NHSO4, Bu4NBr, BU4NI, Nal, or 4-dimethylaminopyridine
  • compounds of formula (XIV), wherein X is CI, Br, I, or OS02Me and Y is halogen or CN are either commercially available or can be prepared from compounds of formula (XVI), via treatment with a suitable acid source (eg, hydrochloric acid, hydrobromic acid, or hydroiodic acid) or a suitable halogen source (eg, tetrabromomethane, tetrachloromethane, or iodine), optionally in the presence of triphenylphosphine, or with methanesulfonyl chloride (CISChMe), in a suitable solvent, (eg, dichloromethane) at a temperature between 0°C and 100°C.
  • a suitable acid source eg, hydrochloric acid, hydrobromic acid, or hydroiodic acid
  • a suitable halogen source eg, tetrabromomethane, tetrachloromethane, or iodine
  • compounds of formula (VII), wherein Y is halogen or CN can be prepared from compounds of formula (XIV), wherein X is CI, Br, I, or OS02Me and Y is halogen or CN, via treatment with ureas of formula (XVII) in the presence of a base (eg, triethylamine, A/,A/-diisopropylethylamine, K2CO3, NaHC03, or Na2C03) in a suitable solvent (eg, dimethylacetamide, tetrahydrofuran, 2- methyltetrahydrofuran, acetone, or acetonitrile) at a temperature between 0°C and 90°C.
  • a base eg, triethylamine, A/,A/-diisopropylethylamine, K2CO3, NaHC03, or Na2C03
  • a suitable solvent eg, dimethylacetamide, tetrahydrofuran,
  • a better reaction performance may be gained from the use of a catalyst (eg, BU4NHSO4, Bu4NBr, BU4NI, Nal, or 4-dimethylaminopyridine) or optionally with microwaves irradiation.
  • a catalyst eg, BU4NHSO4, Bu4NBr, BU4NI, Nal, or 4-dimethylaminopyridine
  • microwaves irradiation e.g., BU4NHSO4, Bu4NBr, BU4NI, Nal, or 4-dimethylaminopyridine
  • Compounds of formula (XVII) can be prepared from amine compounds of formula (IX) via treatment with triphosgene, optionally in a suitable solvent (eg, water, acetonitrile, ethyl acetate, tetrahydrofuran, chloroform, or toluene) via the addition of suitable amino nucleophiles of formula (IV), in the presence of a suitable base (eg, pyridine, triethylamine, K2CO3, NaHC03, Na2C03), and at a temperature between 0°C and 25°C.
  • a suitable solvent eg, water, acetonitrile, ethyl acetate, tetrahydrofuran, chloroform, or toluene
  • suitable amino nucleophiles of formula (IV) in the presence of a suitable base (eg, pyridine, triethylamine, K2CO3, NaHC03, Na2C03), and at a temperature between 0°C
  • the compounds of formula (XVII) can be obtained through a coupling transformation with amine compounds of formula (IX) and compounds of formula (III), wherein X is halogen or OH, preferably halogen, in a suitable solvent (eg, dimethylformamide, acetonitrile, dichloromethane or tetrahydrofuran), preferably at a temperature of between 25°C and 100°C, and optionally in the presence of a base (eg, K2CO3, triethylamine or A/,A/-diisopropylethylamine), or under conditions described in the literature for an urea coupling. For examples, see WO 2003/028729.
  • a suitable solvent eg, dimethylformamide, acetonitrile, dichloromethane or tetrahydrofuran
  • a base eg, K2CO3, triethylamine or A/,A/-diisopropylethylamine
  • compounds of formula (XVII) can optionally be obtained via a coupling transformation with compounds of formula (IX) and compounds of formula (III), wherein X is OH, via a process that converts the -OH into an improved halide leaving group, such as a chloride, for example by using triphosgene, phosgene, (COCI)2, or SOCI2, prior to treatment with the compounds of formula (IX).
  • Compounds of formula (III) are commercially available or prepared using known methods. For related examples, see: Nelson, T. D et al Tetrahedron Lett. (2004), 45, 8917; Senthil, K. et al Pest. Res. Journal (2009), 21 , 133; and Crich, D., Zou, Y. J. Org. Chem. (2005), 70, 3309. This reaction is shown in Scheme 17.
  • X is halogen or OS02Me, via treatment with ureas of formula (XVII) in the presence of a base (eg, triethylamine, A/,A/-diisopropylethylamine, K2CO3, NaHC03, or Na2C03) in a suitable solvent (eg, dimethylacetamide, tetrahydrofuran, 2-methyltetrahydrofuran, acetone, toluene, or acetonitrile) at a temperature between 0°C and 90°C.
  • a base eg, triethylamine, A/,A/-diisopropylethylamine, K2CO3, NaHC03, or Na2C03
  • a suitable solvent eg, dimethylacetamide, tetrahydrofuran, 2-methyltetrahydrofuran, acetone, toluene, or acetonitrile
  • a better reaction performance may be gained from the use of a catalyst (eg, BU4NHSO4, Bu4NBr, BU4NI, Nal, or 4-dimethylaminopyridine) or optionally with microwaves irradiation.
  • a catalyst eg, BU4NHSO4, Bu4NBr, BU4NI, Nal, or 4-dimethylaminopyridine
  • microwaves irradiation e.g., BU4NHSO4, Bu4NBr, BU4NI, Nal, or 4-dimethylaminopyridine
  • compounds of Formula (XI), wherein X is hydrogen, OH, OSCteMe, CI, Br, or I can be prepared from compounds of Formula (XVIII) by treatment with trifluoroacetic anhydride or trifluoroacetyl halide (including trifluoroacetyl fluoride, trifluoroacetyl chloride and trifluoroacetyl bromide) in the presence of a base (e.g., pyridine or 4-dimethylaminopyridine) in a suitable solvent, (e.g., ethyl acetate, tetrahydrofuran, 2-methyltetrahydrofuran, or ethanol), at a temperature between 0°C and 75°C.
  • a base e.g., pyridine or 4-dimethylaminopyridine
  • suitable solvent e.g., ethyl acetate, tetrahydrofuran, 2-methyltetrahydrofuran, or ethanol
  • Compounds of Formula (XVIII), wherein X is hydrogen, OH, OS02Me, CI, Br, or I, can be prepared from compounds of Formula (XIX), by treatment with a hydroxylamine hydrochloride salt or a hydroxylamine solution in water, in the presence of a base, such as triethylamine or potassium carbonate, in a suitable solvent, such as methanol or ethanol, at a temperature between 0°C and 80°C. In some cases, a better reaction performance may be gained from the use of a catalyst (eg, 8- hydroxyquinoline). For related examples, see Kitamura, S. ef al Chem. Pharm. Bull. (2001 ), 49, 268, WO 2017/055473 and WO 2013/066838. This reaction is shown in Scheme 20.
  • Compounds of Formula (XIX), wherein X is hydrogen, OH, OS02Me, CI, Br, or I, can be prepared from compounds of Formula (XIV), wherein Y is halogen, via metal-promoted reaction with a suitable cyanide reagent, such as Pd(0)/Zn(CN)2 or CuCN, in a suitable solvent (e.g., dimethylformamide or N- methylpyrrolidone) at elevated temperature between 100°C and 120°C.
  • a suitable cyanide reagent such as Pd(0)/Zn(CN)2 or CuCN
  • a suitable solvent e.g., dimethylformamide or N- methylpyrrolidone
  • Compounds of Formula (XIV), wherein X is CI, Br, I or OSCteMe and Y is halogen or CN, are either commercially available or can be prepared from compounds of Formula (XX), wherein Y is halogen or CN, via treatment with a suitable acid source (e.g., hydrochloric acid, hydrobromic acid, or hydroiodic acid), or with a suitable halogen source (e.g., CC Br, CCU or ) in the presence of triphenylphosphine, or with methanesulfonyl chloride (CISC Me), in a suitable solvent, (e.g., dichloromethane) at a temperature between 0°C and 100°C.
  • a suitable acid source e.g., hydrochloric acid, hydrobromic acid, or hydroiodic acid
  • a suitable halogen source e.g., CC Br, CCU or .
  • a suitable solvent e.g., dichlor
  • the compounds of Formula (I) of the present invention 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 where used 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 dew ' ation 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.
  • compositions of Formula (I) can be used 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.
  • 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 RoundupReady®, 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
  • transgenic crops are:
  • 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.
  • the compounds of Formula (I) may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi (such as Phakopsora pachyrhizi) on soy bean plants.
  • phytopathogenic diseases especially phytopathogenic fungi (such as Phakopsora pachyrhizi) on soy bean plants.
  • transgenic soybean plants expressing toxins for example insecticidal proteins such as delta-endotoxins, e.g. Cry1 Ac (Cry1 Ac Bt protein). Accordingly, this may include transgenic soybean plants comprising event MON87701 (see U.S. Patent No.
  • transgenic soybean plants may comprise event SYHT0H2 - HPPD tolerance (U.S. Patent Application Publication No. 2014/0201860 and related applications and patents), event MON89788 - glyphosate tolerance (U.S. Pat. No. 7,632,985 and related applications and patents), event MON87708 - dicamba tolerance (U.S. Patent Application Publication No. US 201 1/0067134 and related applications and patents), event DP-356043-5 - glyphosate and ALS tolerance (U.S. Patent Application Publication No. US 2010/0184079 and related applications and patents), event A2704-12 - glufosinate tolerance (U.S. Patent Application Publication No.
  • event DAS-40278-9 - tolerance to 2,4- dichlorophenoxyacetic acid and aryloxyphenoxypropionate see WO 201 1/022469, WO 201 1/022470, WO 201 1/022471 , and related applications and patents
  • event 127 - ALS tolerance WO 2010/080829 and related applications and patents
  • event GTS 40-3-2 - glyphosate tolerance event DAS-68416-4- 2,4-dichlorophenoxyacetic acid and glufosinate tolerance
  • event FG72 - glyphosate and isoxaflutole tolerance event BPS-CV127-9 - ALS tolerance and GU262 - glufosinate tolerance or event SYHT04R - HPPD tolerance.
  • locus 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 nonvolatile 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 systemically 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 non- 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) 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 pesticidally-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 fung
  • 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 96/11945, WO 93/19053, WO 93/25543, EP 0 626 375, EP 0 382 173, WO 94/19334, EP 0 382 173, and EP 0 503 538.
  • 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, fenvalerate,
  • 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 .1 to 1.5, Tables 2.1 to 2.9 or Table T1 (compounds 1.1 to 1 .28) (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, doramectin (alternative name) [CCN] + TX, emamectin (291 ) + TX, emamectin benzoate (291 ) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,
  • an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1 122) + TX, fenthion (346) + TX, pyridin-4-amine (lUPAC name) (23) and strychnine (745) + TX, a bactericide selected from the group of substances consisting of 1-hydroxy-1 /- -pyridine-2- thione (lUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (lUPAC name) (170) + TX, copper hydroxide (lUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1 105) + TX, dodicin (1 1 12) +
  • a soil sterilant selected from the group of substances consisting of iodomethane (lUPAC name)
  • 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 insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (lUPAC name) (591 ) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (lUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (lUPAC name) (1048) + TX, diethylamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,
  • 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) +
  • the active ingredient mixture of the compounds of Formula (I) selected from a compound 1.1 to 1.28 described in Table T1 (below) or a compound of Formula (I) described in Tables 1.1 to 1.5 or Tables 2.1 to 2.9 (below), and an active ingredient as described above, are 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, or 3:5, or 4:5, or 1 :4, or 2
  • 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 1.1 to 1.28 described in Table T1 or a compound of Formula (I) described in Tables 1.1 to 1.5 or Tables 2.1 to 2.9 (below) 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 compound of Formula (I) selected from those described in Tables 1.1 to 1.5 or 2.1 to 2.9 (below), or Table T1 (below), and the active ingredient(s) 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 the 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 the 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
  • 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.
  • rates of 0.001 to 50 g of a compound of Formula (I) per kg of seed preferably from 0.01 to 10g per kg of seed are generally sufficient.
  • 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 1.1 This table discloses 22 s ecific compounds of the formula (T-1 ):
  • A is 1 ,4-phenylene
  • R and R 2 are hydrogen
  • R 3 is hydroxy
  • NR 4 (R 5 ) is as defined below in Table 1.
  • Tables 1.2 to 1.5 make available 22 individual compounds of the formula (T-1 ) in which A, R , R 2 , and R 3 are as specifically defined in Tables 1.2 to 1.5, which refer to Table 1 wherein -NR 4 (R 5 ) is specifically defined.
  • Table 1.2 This table discloses 22 specific compounds of formula (T-1 ) wherein A is 1 ,4-phenylene, R and R 2 are hydrogen, R 3 is ethoxy, and -NR 4 (R 5 ) is as defined above in Table 1.
  • Table 1.3 This table discloses 22 specific compounds of formula (T-1 ) wherein A is 1 ,4-phenylene, R and R 2 are hydrogen, R 3 is propyl, and -NR 4 (R 5 ) is as defined above in Table 1.
  • Table 1.4 This table discloses 22 specific compounds of formula (T-1 ) wherein A is 1 ,4-phenylene, R and R 2 are hydrogen, R 3 is cyclopropyl, and -NR 4 (R 5 ) is as defined above in Table 1.
  • Table 1.5 This table discloses 22 specific compounds of formula (T-1 ) wherein A is 1 ,4-phenylene, R and R 2 are hydrogen, R 3 is 2,2,2-trifluoroethyl and -NR 4 (R 5 ) is as defined above in Table 1.
  • Table 2.1 This table discloses 23 s ecific compounds of the formula (T-2):
  • A is 1 ,4-phenylene
  • R and R 2 are hydrogen
  • R 3 is isopropyl
  • NR 4 (R 5 ) is as defined below in Table 2.
  • Tables 2.2 to 2.9 make available 23 individual compounds of the formula (T-2) in which A, R , R 2 , and R 3 are as specifically defined in Tables 2.2 to 2.9, which refer to Table 2 wherein -NR 4 (R 5 ) is specifically defined.
  • Table 2.2 This table discloses 23 specific compounds of formula (T-2) wherein A is 1 ,4-phenylene, R and R 2 are hydrogen, R 3 is isobutyl, and -NR 4 (R 5 ) is as defined above in Table 2.
  • Table 2.3 This table discloses 23 specific compounds of formula (T-2) wherein A is 1 ,4-phenylene, R and R 2 are hydrogen, R 3 is prop-2-enyl, and -NR 4 (R 5 ) is as defined above in Table 2.
  • Table 2.4 This table discloses 23 specific compounds of formula (T-2) wherein A is 1 ,4-phenylene, R and R 2 are hydrogen, R 3 is prop-2-ynyl, and -NR 4 (R 5 ) is as defined above in Table 2.
  • Table 2.5 This table discloses 23 specific compounds of formula (T-2) wherein A is 1 ,4-phenylene, R and R 2 are hydrogen, R 3 is propyloxy, and -NR 4 (R 5 ) is as defined above in Table 2.
  • Table 2.6 This table discloses 23 specific compounds of formula (T-2) wherein A is 1 ,4-phenylene, R and R 2 are hydrogen, R 3 is butyloxy, and -NR 4 (R 5 ) is as defined above in Table 2.
  • Table 2.7 This table discloses 23 specific compounds of formula (T-2) wherein A is 1 ,4-phenylene, R and R 2 are hydrogen, R 3 is methoxyethyl, and -NR 4 (R 5 ) is as defined above in Table 2.
  • Table 2.8 This table discloses 23 specific compounds of formula (T-2) wherein A is 1 ,4-phenylene, R and R 2 are hydrogen, R 3 is cyclopropylmethyl, and -NR 4 (R 5 ) is as defined above in Table 2.
  • Table 2.9 This table discloses 23 specific compounds of formula (T-2) wherein A is 1 ,4-phenylene, R and R 2 are hydrogen, R 3 is oxetan-3-yl, and -NR 4 (R 5 ) is as defined above in Table 2.
  • 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, 0.8 ppm or 0.2 ppm.
  • Compounds of Formula (I) 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).
  • 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.
  • 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, e.g., by using chiral starting materials.
  • Active ingredient [compound of Formula (I)] 25 % 50 % 75 %
  • 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.
  • Active ingredient [compound of Formula (I)] 25 % 50 % 75 %
  • 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.
  • active ingredient [compound of Formula (I)] 10 % octylphenol polyethylene glycol ether 3 %
  • Emulsions of any required dilution which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • 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 %
  • 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.
  • Active ingredient [compound of Formula (I)] 40 %
  • 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.
  • 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.
  • 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.
  • 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.
  • AIBN azobisisobutyronitrile
  • BOP-CI phosphoric acid bis(2-oxooxazolidide) chloride
  • CDI carbonyl diimidazole
  • DIPEA N,N-diisopropylethylamine
  • NBS N-bromosuccinimide
  • Example 1 This example illustrates the preparation N-cyclopropyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]oxazinane-2-carboxamide (Compound 1.4 of Table T1 )
  • Step 2 Preparation of 3-(p-tolyl)-5-(trifluoromethyl)-1 ,2,4-oxadiazole
  • Step 3a Preparation of 3-[4-(bromomethyl)phenyll-5-(trifluoromethyl)-1 ,2,4-oxadiazole
  • Step 3b Preparation of 3-[4-(bromomethyl)phenyll-5-(trifluoromethvn-1 ,2,4-oxadiazole from 3-[4- (dibromomethvnphenyll-5-(trifluoromethvn-1 ,2,4-oxadiazole
  • the resultant white slurry was extracted with dichloromethane and the combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure.
  • the resultant crude was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 99: 1 to 9: 1 ) to afford 7.10 g of the title compound as a white solid, mp: 58-63°C.
  • the titled compound can be prepared using an analaqous procedure as described in WO 2013/066839.
  • Step 4 Preparation of 1 N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyllcyclopropanamine
  • Step 5 Preparation of N-cvclopropyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yllphenyllmethylloxazinane-2-carboxamide
  • triphosgene 41 mg was dissolved in 1 ,2-dichloroethane (5 mL). The colorless solution was cooled to 0°C. Then a solution of oxazinane hydrochloride (43 mg) and triethylamine (0.1 mL) in 1 ,2-dichloroethane (2.5 mL) was added at 0°C. The reaction mixture was stirred for 4 hours at ambient temperature.
  • Example 2 This example illustrates the preparation of preparation of the intermediate N-[[4-[5- (trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]methanamine.
  • Example 3 This example illustrates the preparation of preparation of the intermediate 2,2,2-trifluoro-N- [[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]ethanamine
  • Example 4 This example illustrates the preparation of intermediate N-propoxy-1-[4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phenyl]methanamine C H 3
  • Example 5 preparation of 1-ethoxy-3-methyl-3-prop-2-ynyl-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]urea (Com ound 1.1 of Table TI )
  • Step 1 Preparation of N-ethoxy-1-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethanamine
  • N-ethoxy-1-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methanamine 50 mg was dissolved in dichloromethane (0.52 mL) and N,N-dimethylformamide (0.17 mL). To this suspension was added at room temperature in one portion CDI (45 mg) The suspension slowly turned into a clear solution. The mixture was stirred for 1 hour at ambient temperature. Then N-methylprop-2-yn-1 -amine (63 mg) was added to the reaction mixture at ambient temperature. The mixture was stirred 18 hours at ambient temperature.
  • 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).
  • 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.
  • 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.
  • Compounds (from Table T1 ) 1.1 , 1.3, 1.4, 1.5, 1 .6, 1 .7, 1 .8, 1.10, 1 .1 1 , 1.13, 1.14, 1.15, 1 .16, 1.17, 1 .18, 1.19, 1 .20, 1.21 and 1.22.
  • 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.
  • nutrient broth PDB - potato dextrose broth
  • 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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  • Life Sciences & Earth Sciences (AREA)
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  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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Abstract

L'invention concerne des composés représentés par la formule (I), dans laquelle les substituants sont tels que définis dans la revendication 1. Ces composés sont utiles en tant que pesticides, en particulier en tant que fongicides.
PCT/EP2018/058102 2017-04-05 2018-03-29 Dérivés d'oxadiazole microbiocides WO2018184984A1 (fr)

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BR112019020756-2A BR112019020756B1 (pt) 2017-04-05 2018-03-29 Compostos derivados de oxadiazol microbicidas, composição agroquímica compreendendo os mesmos, método para controlar ou prevenir a infestação de plantas úteis por microrganismos fitopatogênicos e uso desses compostos

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019150219A2 (fr) 2018-01-30 2019-08-08 Pi Industries Ltd. Nouveaux oxadiazoles

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