WO2017055469A1 - Microbiocidal oxadiazole derivatives - Google Patents

Microbiocidal oxadiazole derivatives Download PDF

Info

Publication number
WO2017055469A1
WO2017055469A1 PCT/EP2016/073290 EP2016073290W WO2017055469A1 WO 2017055469 A1 WO2017055469 A1 WO 2017055469A1 EP 2016073290 W EP2016073290 W EP 2016073290W WO 2017055469 A1 WO2017055469 A1 WO 2017055469A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
hydrogen
alkoxyci
methyl
formula
Prior art date
Application number
PCT/EP2016/073290
Other languages
French (fr)
Inventor
Daniel Stierli
Thomas James HOFFMAN
Renaud Beaudegnies
Martin Pouliot
Original Assignee
Syngenta Participations Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Syngenta Participations Ag filed Critical Syngenta Participations Ag
Priority to EP16787342.1A priority Critical patent/EP3356335B1/en
Priority to MX2018003845A priority patent/MX2018003845A/en
Priority to US15/765,089 priority patent/US10501425B2/en
Priority to BR112018006630A priority patent/BR112018006630B8/en
Priority to JP2018516700A priority patent/JP6864673B2/en
Priority to CN201680058084.1A priority patent/CN108137517B/en
Publication of WO2017055469A1 publication Critical patent/WO2017055469A1/en
Priority to IL258014A priority patent/IL258014B/en
Priority to ZA2018/01769A priority patent/ZA201801769B/en
Priority to CONC2018/0003681A priority patent/CO2018003681A2/en

Links

Classifications

    • 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
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • 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
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic 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<
    • 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
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/02—Local antiseptics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents
    • 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
    • C07D413/04—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 directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to microbiocidal oxadiazole derivatives, eg, as active ingredients, which have microbiocidal activity, in particular, fungicidal activity.
  • the invention also relates to agrochemical compositions which comprise at least one of the oxadiazole derivatives, to processes of preparation of these compounds and to uses of the oxadiazole derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, preferably fungi.
  • Microbiocidal oxadiazole derivatives are known as 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.
  • n 1 or 2;
  • a 1 represents N or CR , wherein R is hydrogen, halogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy;
  • a 2 represents N or CR 2 , wherein R 2 is hydrogen, halogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy;
  • a 3 represents N or CR 3 , wherein R 3 is hydrogen or halogen
  • a 4 represents N or CR 4 , wherein R 4 is hydrogen or halogen; and wherein no more than two of A 1 to A 4 are N;
  • R 5 and R 6 are independently selected from hydrogen, C 1 _ 4 alkyl, halogen, cyano, trifluoromethyl and difluoromethyl, or R 5 and R 6 together with the carbon atom they share form a cyclopropyl;
  • R 7 is hydrogen;
  • R represents -C(0)R , wherein R is hydrogen, d- 6 alkyl, d ⁇ alkenyl, d ⁇ alkynyl, cyanod- 6 alkyl, Ci_ 6 haloalkyl, C 2 - 6 haloalkenyl, hydroxyCi_ 6 alkyl, hydroxyCi_ 6 haloalkyl, Ci. 4 alkoxyCi.
  • R 8 represents -C(0)OR °, wherein R 0 is hydrogen, Ci_ 8 alkyl, C 3 . 6 alkenyl, C 3 . 6 alkynyl, cyanod- 6 alkyl, Ci_ 6 haloalkyl, C 3 . 6 haloalkenyl, hydroxyCi_ 6 alkyl, Ci. 4 alkoxyCi_ 6 alkyl, Ci. 4 haloalkoxyCi_ 6 alkyl, Ci_ 4 alkoxyCi- 4 alkoxyCi. 6 alkyl, C 2 . 6 alkynyloxyCi. 6 alkyl, aminoCi. 6 alkyl, N-Ci. 4 alkylaminoCi.
  • R 8 represents -C(0)NR R 12 , wherein R is hydrogen, cyano, Ci_ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoCi_ 8 alkyl, Ci_ 6 haloalkyl, C 2 . 6 haloalkenyl, hydroxyCi_ 6 alkyl, Ci. 4 alkoxyCi_ 6 alkyl, Ci_ 4 haloalkoxyCi_ 6 alkyl, Ci. 4 alkoxyCi. 4 alkoxyCi. 6 alkyl, C 2 . 6 alkynyloxyCi. 6 alkyl, aminoCi. 6 alkyl, N-Ci_ 4 alkylaminoCi.
  • R 2 is hydrogen, C 1 _ 4 alkyl, C-
  • R and R 2 together with the nitrogen atom they share form a 4-, 5- or 6-membered cycle optionally containing a heteroatom moiety comprising O, S or NR 3 ;
  • R 3 is hydrogen, methyl, methoxy, formyl or acyl; or a salt or an N-oxide thereof; with the proviso that the compound of Formula (I) is not: tert-butyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]carbamate.
  • an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I).
  • the 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 or may not include methods for the treatment of the human or animal body by surgery or therapy.
  • halogen or “halo” refers to fluorine (fluoro), chlorine (chloro), bromine
  • bromine iodine
  • iodo iodine
  • cyano means a -CN group.
  • amino means an -NH 2 group.
  • hydroxy means an -OH group.
  • formyl means an -C(0)H group.
  • acyl means an -C(0)CH 3 group.
  • Ci_ 8 alkyl refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to eight carbon atoms, and which is attached to the rest of the molecule by a single bond.
  • the terms "Ci_ 6 alkyl” and “Ci_ 4 alkyl” are to be construed accordingly.
  • Examples of d- 8 alkyl include, but are not limited to, methyl, ethyl, n-propyl, 1-methylethyl (iso-propyl), n-butyl, 2-methylpropyl (/so-butyl) and n-pentyl.
  • C 2 . 6 alkenyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond that can be of either the (E)- or (Z)-configu ration, having from two to six carbon atoms, which is attached to the rest of the molecule by a single bond.
  • C 2 - 4 alkenyl is to be construed accordingly. Examples of C 2 . 6 alkenyl include, but are not limited to, ethenyl, prop-1-enyl, but-1-enyl.
  • C 2 . 6 alkynyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from two to six carbon atoms, and which is attached to the rest of the molecule by a single bond.
  • C 2 . 4 alkynyl is to be construed accordingly. Examples of C 2 . 6 alkynyl include, but are not limited to, ethynyl, prop-1-ynyl, but-1-ynyl.
  • N-Ci_ 4 alkylamino refers to a radical of the formula -NH-R a where R a is a Ci- 4 alkyl radical as defined above.
  • N,N-diCi_ 4 alkylamino refers to a radical of the formula -N(R a )-R a where each R a is a C 1 _ 4 alkyl radical, which may be the same or different, as defined above.
  • d- 6 alkoxy refers to a radical of the formula -OR a where R a is a d. 6 alkyl radical as generally defined above.
  • Ci_ 4 alkoxy is to be construed accordingly. Examples of Ci_ 6 alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, iso-propoxy, butoxy.
  • Ci_ 6 alkylcarbonyl refers to a radical of the formula -C(0)R a where R a is a Ci- 6 alkyl radical as generally defined above.
  • Ci_ 4 alkylcarbonyl is to be construed accordingly.
  • Ci_ 6 alkoxycarbonyl refers to a radical of the formula -C(0)OR a where R a is a Ci- 6 alkyl radical as generally defined above.
  • Ci_ 4 alkoxycarbonyl is to be construed accordingly.
  • Ci_ 6 alkylcarbonyloxy refers to a radical of the formula -OC(0)R a where R a is a Ci_ 6 alkyl radical as generally defined above.
  • Ci_ 4 alkylcarbonyloxy is to be construed accordingly.
  • N-Ci_ 4 alkylaminocarbonyl refers to a radical of the formula - C(0)NHR a where R a is a Ci_ 4 alkyl radical as generally defined above.
  • N,N-diCi_ 4 alkylaminocarbonyl refers to a radical of the formula -
  • each R a is a Ci_ 4 alkyl radical, which may be the same or different, as generally defined above.
  • Ci. 6 alkylsulfanyl refers to a radical of the formula -SR a where R a is a Ci- 6 alkyl radical as generally defined above.
  • Ci_ 4 alkylsulfanyl is to be construed accordingly.
  • Ci. 6 alkylsulfonyl refers to a radical of the formula -S(0) 2 R a where R a is a Ci- 6 alkyl radical as generally defined above.
  • Ci_ 4 alkylsulfonyl is to be construed accordingly.
  • Ci_ 6 alkylsulfonylamino refers to a radical of the formula -NHS(0) 2 R a where R a is a Ci_ 6 alkyl radical as generally defined above.
  • Ci_ 4 alkylsulfonylamino is to be construed accordingly.
  • C 2 . 6 alkenoxy refers to a radical of the formula -OR a where R a is a C 2 . 6 alkenyl radical as generally defined above.
  • R a is a C 2 . 6 alkenyl radical as generally defined above.
  • C 2 . 4 alkenoxy is to be construed accordingly.
  • C 2 . 6 alkynoxy refers to a radical of the formula -OR a where R a is a C 2 . 6 alkynyl radical as generally defined above.
  • R a is a C 2 . 6 alkynyl radical as generally defined above.
  • C 2 . 4 alkynoxy is to be construed accordingly.
  • Ci_ 4 haloalkoxy refers to a Ci_ 4 alkoxy group as defined above substituted by one or more of the same or different halogen atoms.
  • Examples of Ci_ 4 haloalkoxy include, but are not limited to, fluoromethoxy, fluoroethoxy (including 2-fluoroethoxy), trifluoromethoxy, 2,2,2-trifluoroethoxy.
  • cyanoCi_ 6 alkyl refers to a Ci_ 6 alkyl radical as generally defined above substituted by one or more cyano groups as defined above.
  • cyanoCi_ 4 alkyl is to be construed accordingly. Examples of cyanoCi_ 6 alkyl include, but are not limited to cyanomethyl, cyanoethyl (including 2-cyanoethyl).
  • Ci_ 6 haloalkyl refers to a Ci_ 6 alkyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • the term “Ci_ 4 haloalkyl” is to be construed accordingly.
  • Examples of Ci_ 6 haloalkyl include, but are not limited to fluoromethyl, fluoroethyl (including 2-fluoroethyl), trifluoromethyl, 2,2,2-trifluoroethyl.
  • hydroxyCi_ 6 haloalkyl refers to a d- 6 haloalkyl radical as generally defined above substituted by one or more hydroxy groups as defined above.
  • C 2 - 6 haloalkenyl refers to a d ⁇ alkenyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C 2 - 4 haloalkenyl is to be construed accordingly.
  • hydroxyCi_ 6 alkyl refers to a Ci_ 6 alkyl radical as generally defined above substituted by one or more hydroxy groups as defined above.
  • hydroxyCi_ 4 alkyl is to be construed accordingly.
  • Ci. 4 alkoxyCi. 6 alkyl refers to a Ci_ 6 alkyl radical as generally defined above substituted by a Ci_ 4 alkoxy group as defined above.
  • Ci_ 4 alkoxyCi. 4 alkyl is to be construed accordingly. Examples of Ci. 4 alkoxyCi_ 6 alkyl include, but are not limited to methoxymethyl, 2-methoxyethyl.
  • Ci_ 4 haloalkoxyCi. 6 alkyl refers to a Ci_ 6 alkyl radical as generally defined above substituted by a Ci_ 4 haloalkoxy group as defined above.
  • Ci_ 4 halolkoxyCi_ 4 alkyl is to be construed accordingly.
  • Ci. 4 alkoxyCi. 4 alkoxyCi. 6 alkyl refers to a Ci_ 6 alkyl radical as generally defined above substituted by a Ci_ 4 alkoxy group as defined above, the Ci_ 4 alkoxy group itself substituted by the same or a different Ci_ 4 alkoxy group as defined above.
  • C 2 - 6 alkynyloxyCi. 6 alkyl refers to a Ci_ 6 alkyl radical as generally defined above substituted by one or more C 2 . 6 alkynyloxy group as defined above.
  • aminoCi_ 6 alkyl refers to a Ci_ 6 alkyl radical as generally defined above substituted by one or more amino groups as defined above.
  • aminoCi_ 4 alkyl is to be construed accordingly.
  • N-Ci. 4 alkylaminoCi. 6 alkyl refers to a Ci_ 6 alkyl radical as generally defined above substituted by a Ci_ 4 alkylamino group as defined above.
  • Ci_ 4 alkylaminoCi. 4 alkyl is to be construed accordingly.
  • N,N-diCi. 4 alkylaminoCi. 6 alkyl refers to a Ci_ 6 alkyl radical as generally defined above substituted by an N,N-diCi_ 4 alkylamino group as defined above.
  • the term "N,N-diCi_ 4 alkylaminoCi_ 4 alkyl” is to be construed accordingly.
  • Ci. 6 alkylcarbonylCi. 6 alkyl refers to a Ci_ 6 alkyl radical as generally defined above substituted by a Ci_ 6 alkylcarbonyl group as defined above.
  • d_ 6 alkylcarbonylCi_ 4 alkyl is to be construed accordingly.
  • Ci_ 6 alkylcarbonylC 2 . 6 alkenyl refers to a C 2 . 6 alkenyl radical as generally defined above substituted by a Ci_ 6 alkylcarbonyl group as defined above.
  • d_ 6 alkylcarbonylC 2 . 4 alkenyl is to be construed accordingly.
  • Ci. 6 alkoxycarbonylCi. 6 alkyl refers to a Ci_ 6 alkyl radical as generally defined above substituted by a Ci_ 6 alkoxycarbonyl group as defined above.
  • d_ 6 alkoxycarbonyld- 4 alkyl is to be construed accordingly.
  • Ci. 6 alkylcarbonyloxyCi. 6 alkyl refers to a d- 6 alkyl radical as generally defined above substituted by a Ci_ 6 alkylcarbonyloxy group as defined above.
  • d. 6 alkylcarbonyloxyCi_ 4 alkyl is to be construed accordingly.
  • N-Ci_ 4 alkylcarbonylamino refers to a -N(H)C(0)R a radical wherein R a refers to a C 1 _ 4 alkyl radical as generally defined above
  • N-Ci- 4 alkylcarbonylaminoCi- 6 alky ' refers to a Ci_ 6 alkyl radical as generally defined above substituted by an N-Ci_ 4 alkylcarbonylamino group as defined above.
  • N-Ci. 4 alkylaminocarbonylCi. 6 alkyl refers to a Ci_ 6 alkyl radical as generally defined above substituted by a N-Ci_ 4 alkylaminocarbonyl group as defined above.
  • N-Ci_ 4 alkylaminocarbonylCi- 4 alkyl is to be construed accordingly.
  • N,N-diCi. 4 alkylaminocarbonylCi. 6 alkyl refers to a Ci_ 6 alkyl radical as generally defined above substituted by a N,N-diCi. 4 alkylaminocarbonylCi. 6 alkyl group as defined above.
  • the term "N,N-diCi. 4 alkylaminocarbonylCi_ 4 alkyl" is to be construed accordingly.
  • Ci- 6 alkylsulfanylCi- 6 alkyr' refers to a Ci_ 6 alkyl radical as generally defined above substituted by a Ci_ 6 alkylsulfanyl group as defined above.
  • Ci_ 6 alkylsulfanylCi_ 4 alkyl is to be construed accordingly.
  • Ci- 6 alkylsulfonylCi- 6 alkyr' refers to a Ci_ 6 alkyl radical as generally defined above substituted by a Ci_ 6 alkylsulfonyl group as defined above.
  • Ci_ 6 alkylsulfonylCi_ 4 alkyl is to be construed accordingly.
  • Ci- 6 alkylsulfonylaminoCi- 6 alkyr' refers to a Ci_ 6 alkyl radical as generally defined above substituted by a Ci_ 6 alkylsulfonylamino group as defined above.
  • d. 6 alkylsulfonylaminoCi_ 4 alkyl is to be construed accordingly.
  • asymmetric carbon atoms in a compound of formula (I) means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. Also atropisomers may occur as a result of restricted rotation about a single bond.
  • Formula (I) is intended to include all those possible isomeric forms and mixtures thereof.
  • the present invention includes all those possible isomeric forms and mixtures thereof for a compound of formula (I).
  • formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism) where present.
  • the present invention includes all possible tautomeric forms for a compound of formula (I).
  • the compounds of formula (I) according to the invention are in free form, in 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.
  • the compound of Formula (I) which is not according to the present invention is:
  • the compound not according to the invention may be used in a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of the compound or a composition comprising the compound as active ingredient is applied to the plants, to parts thereof or the locus thereof.
  • the aforementioned compound not according to the invention may be useful as a fungicidal agent.
  • n represents 1 or 2. In some embodiments of the invention, n is 1 , In other embodiments of the invention, n is 2. Preferably, n is 1.
  • a 1 represents N or CR , wherein R represents hydrogen, halogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy.
  • a 2 represents N or CR 2 , wherein R 2 represents hydrogen, halogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy;
  • a 3 represents N or CR 3 , wherein R 3 represents hydrogen or halogen
  • a 4 represents N or CR 4 , wherein R 4 represents hydrogen or halogen; and wherein no more than two of A 1 to A 4 are N (ie, 0, 1 or 2 of A 1 to A 4 may be N);
  • a 1 represents N or CR 1 , wherein R is selected from hydrogen, fluoro, chloro, methoxy, or trifluoromethyl.
  • a 2 represents CR 2 and R 2 is hydrogen or fluoro.
  • a 3 represents CR 3 and R 3 is hydrogen, and
  • a 4 represents CR 4 and R 4 is hydrogen.
  • a 1 to A 4 are C-H.
  • a 1 is N or CR wherein R is hydrogen, halogen, methyl or trifluoromethyl;
  • a 2 is N or C-H;
  • a 3 is N or CR 3 wherein R 3 is hydrogen or halogen; and
  • a 4 is C-H.
  • a 1 is N or CR 1 wherein R is hydrogen or fluoro; A 2 is C-H;
  • a 3 is CR 3 wherein R 3 is hydrogen or fluoro; and
  • a 4 is C-H.
  • the 6-membered ring comprising A 1 to A 4 is a phenyl (where A 1 to A 4 are C-H), pyridinyl (where A 1 or A 3 is N and the other A positions are C-H), pyrimidinyl (where A 1 and A 3 are N and the other A positions are C-H), fluorophenyl (where A 1 or A 3 are C-F (preferably A 3 is C-F) and the other A positions are C-H) or difluorophenyl (where A 1 and A 3 are C-F and the A 2 and A 4 positions are C-H) group.
  • R and R 2 may be independently selected from hydrogen, chloro, fluoro, methyl, methoxy and trifluoromethyl.
  • R and R 2 may be independently selected from hydrogen and fluoro.
  • R 3 and R 4 may be independently selected from hydrogen and halogen.
  • R 3 and R 4 may be independently selected from hydrogen and fluoro. More preferably, R 3 and R 4 are hydrogen.
  • at least two of R , R 2 , R 3 and R 4 may be hydrogen.
  • three of R , R 2 , R 3 and R 4 are hydrogen, wherein more preferably R 2 , R 3 and R 4 are hydrogen.
  • R 5 and R 6 are independently selected from hydrogen, C 1 _ 4 alkyl, halogen, cyano, trifluoromethyl and difluoromethyl, or R 5 and R 6 together with the carbon atom they share form a cyclopropyl.
  • R 5 and R 6 are independently selected from hydrogen and C 1 _ 4 alkyl (eg, methyl), or R 5 and R 6 together with the carbon atom they share form a cyclopropyl. More preferably, R 5 and R 6 are independently selected from hydrogen and C 1 _ 4 alkyl. Even more preferably, R 5 and R 6 are hydrogen, or R 5 is hydrogen and R 6 is C 1 _ 4 alkyl, preferably methyl or ethyl. Still more preferably, R 5 and R 6 are hydrogen.
  • n is 1 , and R 5 and R 6 are independently selected from hydrogen and methyl. In other embodiments of the invention, in compounds according to Formula (I), n is 2, and R 5 and R 6 are independently selected from hydrogen and fluoro.
  • R 7 is hydrogen.
  • R 8 represents -C(0)R 9 .
  • R 9 is hydrogen, d- 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoCi_ 6 alkyl, Ci_ 6 haloalkyl, C 2 - 6 haloalkenyl, hydroxyCi- 6 alkyl, hydroxyCi_ 6 haloalkyl, Ci. 4 alkoxyCi. 6 alkyl, Ci. 4 haloalkoxyCi. 6 alkyl, Ci_ 4 alkoxyCi_ 4 alkoxyCi- 6 alkyl, C 2 - 6 alkynyloxyCi- 6 alkyl, aminoCi_ 6 alkyl, N-Ci. 4 alkylaminoCi.
  • R 9 is hydrogen, d- 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoCi_ 6 alkyl, Ci_ 6 haloalkyl, C 2 . 6 haloalkenyl, hydroxyCi_ 6 alkyl, hydroxyCi_ 6 haloalkyl, Ci. 4 alkoxyCi. 6 alkyl, Ci. 4 haloalkoxyCi. 6 alkyl, Ci_ 4 alkoxyCi. 4 alkoxyCi. 6 alkyl, C 2 - 4 alkynyloxyCi. 6 alkyl, aminoCi. 6 alkyl, N-Ci. 4 alkylanriinoCi.
  • R 9 is Ci_ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoCi_ 6 alkyl, Ci_ 6 haloalkyl, hydroxyCi_ 6 alkyl, hydroxyCi_ 6 haloalkyl, Ci. 4 alkoxyCi. 6 alkyl, Ci.
  • R 9 is Ci_ 6 alkyl, C 3 . 6 alkenyl, C 3 . 6 alkynyl, cyanoCi. 4 alkyl, Ci_ 6 haloalkyl, hydroxyCi_ 4 alkyl, hydroxyCi_ 4 haloalkyl, Ci_ 2 alkoxyCi_ 4 alkyl, Ci_ 2 haloalkoxyCi_ 4 alkyl, Ci_ 2 alkylcarbonylCi_ 4 alkyl or N-Ci. 2 alkylcarbonylaminoCi_ 2 alkyl.
  • R 9 is hydrogen, Ci_ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoC-i. 6 alkyl, Ci_ 6 fluoroalkyl, Ci_ 6 chloroalkyl, hydroxyCi_ 6 alkyl, Ci. 4 alkoxyCi_ 6 alkyl, Ci. 4 fluoroalkoxyCi_ 6 alkyl,
  • R 9 is hydrogen, d.
  • R 9 is Ci_ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoCi_ 6 alkyl, Ci_ 6 fluoroalkyl, Ci_ 6 chloroalkyl, Ci. 4 alkoxyCi_ 6 alkyl or Ci. 6 alkylcarbonylCi. 6 alkyl, or R 9 is Ci_ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl,
  • R 9 is Ci_ 6 alkyl (such as methyl, ethyl, iso-propyl, n-butyl, pentyl), Ci. 4 alkoxyCi_ 6 alkyl or C 2 . 6 alkynyl.
  • R 9 is Ci_ 6 alkyl, C 3 . 6 alkenyl, C 3 . 6 alkynyl, cyanoCi_ 4 alkyl, Ci_ 6 haloalkyl, hydroxyCi_ 4 alkyl, hydroxyCi_ 4 haloalkyl, Ci_ 2 alkoxyCi_ 4 alkyl, Ci_ 2 haloalkoxyCi_ 4 alkyl, Ci_ 2 alkylcarbonylCi_ 4 alkyl or N-Ci. 2 alkylcarbonylaminoCi_ 2 alkyl.
  • R 9 is Ci_ 6 alkyl, C 3 . 4 alkenyl, C 3 .
  • R 9 is methyl, ethyl, n-propyl, iso-propyl, sec-butyl (1-methylpropyl), iso-butyl (2-methylpropyl), tert-butyl (1 ,1-dimethylethyl), 2,2-dimethylpropyl, (1-methyl-1-ethyl)propyl, (l-methyl)ethenyl, (1 ,1-dimethyl)prop- 2-ynyl, 2,2,2-trifluoroethyl, (1 ,1-dimethyl-2-chloro)ethyl, methoxy-(1 ,1-dimethyl)methyl, 2-methoxyethyl, (difluoromethoxy)methyl or 2-(difluofluo
  • a 1 is CR and A 2 is CR 2 wherein R and R 2 are independently selected from hydrogen and fluoro;
  • a 3 is CR 3 and A 4 is CR 4 wherein R 3 and R 4 are independently selected from hydrogen and fluoro;
  • R 5 and R 6 are hydrogen, or R 5 is hydrogen and R 6 is methyl;
  • R 7 is hydrogen
  • R 8 is -C(0)R 9 _
  • R 9 is Ci_ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoCi_ 6 alkyl, Ci_ 6 haloalkyl, Ci. 4 alkoxyCi. 6 alkyl or d. 6alkylcarbonylCi. 6 alkyl; and
  • n is 1. More preferably, A 1 is CR and A 2 is CR 2 wherein R and R 2 are hydrogen;
  • a 3 is CR 3 and A 4 is CR 4 wherein R 3 and R 4 are hydrogen;
  • R 5 and R 6 are hydrogen
  • R 7 is hydrogen
  • R 8 is -C(0)R 9 ;
  • R 9 is Ci_ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, Ci_ 6 haloalkyl or Ci. 4 alkoxyCi. 6 alkyl: and
  • n 1.
  • a 1 is CR 1 and A 2 is CR 2 wherein R and R 2 are hydrogen;
  • a 3 is CR 3 and A 4 is CR 4 wherein R 3 and R 4 are hydrogen;
  • R 5 and R 6 are hydrogen
  • R 7 is hydrogen
  • R 8 is -C(0)R 9
  • R 9 is Ci- 6 alkyl, Ci. 4 alkoxyCi. 6 alkyl or C 2 . 6 alkynyl;
  • n 1.
  • n represents 1 or 2. In some embodiments of the invention, n is 1. In other embodiments of the invention, n is 2. Preferably, n is 1.
  • a 1 represents N or CR 1 , wherein R represents hydrogen, halogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy;
  • a 2 represents N or CR 2 , wherein R 2 represents hydrogen, halogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy;
  • a 3 represents N or CR 3 , wherein R 3 represents hydrogen or halogen;
  • a 4 represents N or CR 4 , wherein R 4 represents hydrogen or halogen; and wherein no more than two of A 1 to A 4 are N (ie, 0, 1 or 2 of A 1 to A 4 may be N);
  • a 1 represents N or CR 1 , wherein R is selected from hydrogen, fluoro, chloro, methoxy, or trifluoromethyl.
  • a 2 represents CR 2 and R 2 is hydrogen or fluoro.
  • a 3 represents CR 3 and R 3 is hydrogen, and A 4 represents CR 4 and R 4 is hydrogen.
  • a 1 to A 4 are C-H, or A 1 is N and A 2 to A 4 are C-H.
  • the 6-membered ring comprising A 1 to A 4 is a phenyl (where A 1 to A 4 are C-H), pyridinyl (where A 1 or A 3 is N and the other A positions are C-H), pyrimidinyl (where A 1 and A 3 are N and the other A positions are C-H), fluorophenyl (where A 1 or A 3 are C-F (preferably A 3 is C-F) and the other A positions are C-H) or difluorophenyl (where A 1 and A 3 are C-F and the A 2 and A 4 positions are C-H) group.
  • R 5 and R 6 are independently selected from hydrogen, C 1 _ 4 alkyl, halogen, cyano, trifluoromethyl and difluoromethyl, or R 5 and R 6 together with the carbon atom they share form a cyclopropyl.
  • R 5 and R 6 are independently selected from hydrogen and C 1 _ 4 alkyl.
  • R 5 and R 6 are hydrogen, or R 5 is hydrogen and R 6 is C 1 _ 4 alkyl, preferably methyl or ethyl. More preferably, R 5 and R 6 are hydrogen.
  • n is 1 , and R 5 and R 6 are independently selected from hydrogen and methyl. In other embodiments of the invention, in compounds according to Formula (I), n is 2, and R 5 and R 6 are independently selected from hydrogen and fluoro.
  • R 7 is hydrogen.
  • R 8 represents -C(0)OR °, wherein R 0 is hydrogen, d- 8 alkyl, C 3 . 6 alkenyl, C 3 . 6 alkynyl, cyanoC-i.
  • R 0 is hydrogen, Ci_ 8 alkyl, C 3 .
  • R 0 is Ci_ 8 alkyl, C 3 . 6 alkenyl, C 3 . 6 alkynyl, Ci_ 6 haloalkyl or Ci. 4 alkoxyCi_ 6 alkyl.
  • R 0 is Ci_ 8 alkyl, C 3 . 4 alkenyl, C 3 . 4 alkynyl, Ci_ 4 haloalkyl or Ci. 2 alkoxyCi. 4 alkyl. Still more preferably, R 0 is methyl, propyl, iso-propyl, n-butyl, iso- butyl, sec-butyl, pentyl, hexyl or Ci. 4 alkoxyCi_ 6 alkyl.
  • R 0 may be methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl (1-methylpropyl), tert-butyl (1 ,1-dimethylethyl), n-pentyl, 2,2-dimethylpropyl, n-octyl, allyl (2- propen-1-yl), prop-2-yn-yl, but-2-ynyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 4-chlorobutyl, methoxymethyl, methoxyethyl or ethoxyethyl.
  • R 0 When R 0 is d- 8 alkyl, it may be Ci_ 3 alkyl, n-butyl, iso-butyl, sec-butyl or C 5 . 8 alkyl, or alternatively it may be methyl, ethyl, propyl, iso-propyl, butyl (n-butyl, iso-butyl, sec-butyl), pentyl, hexyl, heptyl or octyl. Further still, when R 0 is Ci_ 8 alkyl it may be methyl, propyl, iso-propyl, butyl (n-butyl, iso-butyl, sec-butyl), pentyl or hexyl.
  • a 1 is N or CR and A 2 is CR 2 , wherein R and R 2 are independently selected from hydrogen and fluoro;
  • a 3 is CR 3 and A 4 is CR 4 , wherein R 3 and R 4 are independently selected from hydrogen and fluoro;
  • R 5 and R 6 are hydrogen, or R 5 is hydrogen and R 6 is methyl;
  • R 7 is hydrogen
  • R 8 is -C(0)OR 10 ;
  • R 0 is hydrogen, Ci_ 8 alkyl, C 3 . 6 alkenyl, C 3 . 6 alkynyl, cyanoCi_ 6 alkyl, Ci_ 6 haloalkyl, C 3 .
  • n is 1. More preferably, A 1 is N or CR 1 and A 2 is CR 2 , wherein R and R 2 are hydrogen;
  • a 3 is CR 3 and A 4 is CR 4 , wherein R 3 and R 4 are hydrogen;
  • R 5 and R 6 are hydrogen
  • R 7 is hydrogen
  • R 8 is -C(0)OR 10 ;
  • R 0 is hydrogen, Ci_ 8 alkyl, C 3 . 6 alkenyl, C 3 . 6 alkynyl, cyanoCi_ 6 alkyl, Ci_ 6 haloalkyl, C 3 .
  • n is 1. Even more preferably, A 1 is N or CR 1 and A 2 is CR 2 , wherein R and R 2 are hydrogen;
  • a 3 is CR 3 and A 4 is CR 4 , wherein R 3 and R 4 are hydrogen;
  • R 5 and R 6 are hydrogen
  • R 7 is hydrogen
  • R 8 is -C(0)OR 10 ;
  • R 0 is methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl (1-methylpropyl), n-pentyl, 2,2- dimethylpropyl, n-octyl, allyl (2-propen-1-yl), prop-2-yn-yl, but-2-ynyl, 2-fluoroethyl, 2- chloroethyl, 3-chloropropyl, 4-chlorobutyl, methoxymethyl, methoxyethyl or ethoxyethyl; and n is 1.
  • the following lists provide definitions, including preferred definitions, for substituents n, A 1 , A 2 ,
  • n represents 1 or 2. In some embodiments of the invention, n is 1. In other embodiments of the invention, n is 2. Preferably, n is 1.
  • a 1 represents N or CR , wherein R represents hydrogen, halogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy;
  • a 2 represents N or CR 2 , wherein R 2 represents hydrogen, halogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy;
  • a 3 represents N or CR 3 , wherein R 3 represents hydrogen or halogen;
  • a 4 represents N or CR 4 , wherein R 4 represents hydrogen or halogen; and wherein no more than two of A 1 to A 4 are N (ie, 0, 1 or 2 of A 1 to A 4 may be N);
  • a 1 represents N or CR 1 , wherein R is selected from hydrogen, fluoro, chloro, methoxy, or trifluoromethyl.
  • a 2 represents CR 2 and R 2 is hydrogen or fluoro.
  • a 3 represents CR 3 and R 3 is hydrogen, and A 4 represents CR 4 and R 4 is hydrogen.
  • a 1 to A 4 are C-H, or A 1 is N and A 2 to A 4 are C-H.
  • the 6-membered ring comprising A 1 to A 4 is a phenyl (where A 1 to A 4 are C-H), pyridinyl (where A 1 or A 3 is N and the other A positions are C-H), pyrimidinyl (where A 1 and A 3 are N and the other A positions are C-H), fluorophenyl (where A 1 or A 3 are C-F (preferably A 3 is C-F) and the other A positions are C-H) or difluorophenyl (where A 1 and A 3 are C-F and the A 2 and A 4 positions are C-H) group.
  • R 5 and R 6 are independently selected from hydrogen, C 1 _ 4 alkyl, halogen, cyano, trifluoromethyl and difluoromethyl, or R 5 and R 6 together with the carbon atom they share form a cyclopropyl.
  • R 5 and R 6 are independently selected from hydrogen and C 1 _ 4 alkyl, or R 5 and R 6 together with the carbon atom they share form a cyclopropyl.
  • R 5 and R 6 are hydrogen, or R 5 is hydrogen and R 6 is C 1 _ 4 alkyl, preferably methyl or ethyl. More preferably, R 5 and R 6 are hydrogen.
  • n is 1 , and R 5 and R 6 are independently selected from hydrogen and methyl. In other embodiments of the invention, in compounds according to Formula (I), n is 2, and R 5 and R 6 are independently selected from hydrogen and fluoro.
  • R 7 is hydrogen.
  • R 8 represents -C(0)NR R 12 , wherein R is hydrogen, cyano, d- 7 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoCi- 6 alkyl, Ci_ 6 haloalkyl, C 2 - 6 haloalkenyl, hydroxyCi_ 6 alkyl, Ci. 4 alkoxyCi. 6 alkyl, Ci. 4 haloalkoxyCi_ 6 alkyl, Ci- 4 alkoxyCi. 4 alkoxyCi. 6 alkyl, C 2 - 6 alkynyloxyCi- 6 alkyl, aminoCi.
  • R is hydrogen, cyano, Ci_ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoCi_ 4 alkyl, Ci_ 6 haloalkyl, C 2 . 6 haloalkenyl, hydroxyCi_ 6 alkyl, Ci. 4 alkoxyCi_ 6 alkyl, aminoCi. 6 alkyl or Ci- 4 alkylsulfanylCi- 6 alkyl. More preferably, R is hydrogen, cyano, Ci_ 6 alkyl, C 2 .
  • R is hydrogen, Ci_ 6 alkyl or Ci. 4 alkoxyCi_ 6 alkyl (including Ci_ 4 alkoxyCi_ 4 alkyl).
  • R may be hydrogen, cyano, methyl, ethyl, n-propyl, iso-propyl (1-methylethyl), n-butyl, iso-butyl (2-methylpropyl), sec-butyl (1-methylpropyl), tert-butyl (1 ,1-dimethylethyl), n-pentyl, n-heptyl, 2,2-dimethylpropyl, allyl (2-propen-1-yl), cyanomethyl, 2- chloroethyl, 3-chloropropyl, 2,2,2-trifluoroethyl, methoxymethyl, methoxyethyl, ethoxycarbonylmethyl or methylsulfanylethyl.
  • R 2 is hydrogen, C 1 _ 4 alkyl, Ci_ 4 alkoxy, Ci. 4 alkoxyCi_ 6 alkyl, C 3 . 6 alkenoxy or C 3 . 6 alkynoxy.
  • R 2 is hydrogen, Ci_ 4 alkyl or Ci_ 4 alkoxy.
  • R 2 is hydrogen, methyl, ethyl, methoxy or ethoxy.
  • R 2 is hydrogen, methyl, methoxy or ethoxy.
  • R and R 2 together with the nitrogen atom they share may form a 4-, 5- or 6-membered cycle optionally containing a heteroatom comprising O, S or NR 3 , wherein R 3 is hydrogen, methyl, methoxy, formyl or acyl.
  • a 1 is N or CR and A 2 is CR 2 , wherein R and R 2 are independently selected from hydrogen and fluoro;
  • a 3 is CR 3 and A 4 is CR 4 , wherein R 3 and R 4 are independently selected from hydrogen and fluoro;
  • R 5 and R 6 are hydrogen, or R 5 is hydrogen and R 6 is methyl;
  • R 7 is hydrogen
  • R 8 is -C(0)NR R 12
  • R is hydrogen, cyano, Ci_ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoCi_ 4 alkyl, Ci_ 6 haloalkyl, C 2 . 6haloalkenyl, hydroxyCi_ 6 alkyl, Ci. 4 alkoxyCi_ 6 alkyl, aminoCi_ 6 alkyl or Ci. 4 alkylsulfanylCi_ 6 alkyl; R 2 is hydrogen, methyl, methoxy or ethoxy; and
  • n is i . More preferably, A 1 is N or CR and A 2 is CR 2 , wherein R and R 2 are hydrogen;
  • a 3 is CR 3 and A 4 is CR 4 , wherein R 3 and R 4 are hydrogen;
  • R 5 and R 6 are hydrogen
  • R 7 is hydrogen
  • R 8 is -C(0)NR R 12
  • R is hydrogen, d- 4 alkyl or Ci. 4 alkoxyCi. 4 alkyl;
  • R 2 is hydrogen, cyano, Ci_ 6 alkyl, C 2 - 6 alkenyl, cyanoCi_ 4 alkyl, Ci_ 6 haloalkyl, Ci. 4 alkoxyCi_ 6 alkyl or Ci- 4 alkylsulfanylCi. 6 alkyl;
  • n 1.
  • a 1 is N or CR 1 and A 2 is CR 2 , wherein R and R 2 are hydrogen;
  • a 3 is CR 3 and A 4 is CR 4 , wherein R 3 and R 4 are hydrogen;
  • R 5 and R 6 are hydrogen
  • R 7 is hydrogen
  • R 8 is -C(0)NR R 12
  • R is hydrogen, cyano, methyl, ethyl, n-propyl, iso-propyl (1-methylethyl), n-butyl, iso-butyl (2- methylpropyl), sec-butyl (1-methylpropyl), tert-butyl (1 ,1-dimethylethyl), n-pentyl, n-heptyl, 2,2- dimethylpropyl, allyl (2-propen-1-yl), cyanomethyl, 2-chloroethyl, 3-chloropropyl, 2,2,2- trifluoroethyl, methoxymethyl, methoxyethyl, ethoxycarbonylmethyl or methylsulfanylethyl; R 2 is hydrogen, methyl, methoxy or ethoxy; and
  • n 1.
  • the compound according to Formula (I) is selected from: 2-methoxy-2-methyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide;
  • the compound of Formula I) may be a compound accordin to Formula (IA):
  • R and R 2 are independently selected from hydrogen, chloro, fluoro, methyl, methoxy and trifluoromethyl
  • R 3 and R 4 are independently selected from hydrogen and halogen; wherein at least two of R , R 2 , R 3 and R 4 are hydrogen;
  • R 5 and R 6 are independently selected from hydrogen and C 1 _ 4 alkyl; R 7 is hydrogen; and R 8 represents -C(0)R 9 , wherein R 9 is hydrogen, Ci_ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoCi.
  • R and R 2 are independently selected from hydrogen and fluoro.
  • R 3 and R 4 are independently selected from hydrogen and fluoro. More preferably, R 3 and R 4 are hydrogen. In the compounds of Formula (IA), three of R , R 2 , R 3 and R 4 may be hydrogen, wherein more preferably R 2 , R 3 and R 4 are hydrogen.
  • R 5 and R 6 are hydrogen, or R 5 is hydrogen and R 6 is Ci- 4 alkyl, preferably methyl or ethyl. More preferably, R 5 and R 6 are hydrogen.
  • R 9 is hydrogen, d- 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoCi_ 6 alkyl, Ci_ 6 haloalkyl, C 2 - 6 haloalkenyl, hydroxyCi_ 6 alkyl, Ci. 4 alkoxyCi. 6 alkyl, Ci. 4 haloalkoxyCi_ 6 alkyl, Ci. 4 alkoxyC 2 - 4 alkoxyCi. 6 alkyl, C 2 - 4 alkynyloxyCi. 6 alkyl, aminoCi_ 6 alkyl, N-Ci. 4 alkylaminoCi.
  • R 9 is hydrogen, Ci_ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoCi. 6 alkyl, Ci_ 6 fluoroalkyl, Ci_ 6 chloroalkyl, hydroxyCi_ 6 alkyl, Ci. 4 alkoxyCi_ 6 alkyl, Ci.
  • R 9 is hydrogen, Ci_ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoCi_ 6 alkyl, Ci_ 6 fluoroalkyl, Ci_ 6 chloroalkyl, hydroxyCi_ 6 alkyl, Ci_ 2 alkoxyCi_ 6 alkyl, Ci. 2 fluoroalkoxyCi_ 6 alkyl, Ci- 2 alkoxyC 2 - 3 alkoxyCi- 6 alky or Ci.
  • R 9 is Ci_ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoCi_ 6 alkyl, Ci_ 6 fluoroalkyl, Ci_ 6 chloroalkyl, Ci. 4 alkoxyCi_ 6 alkyl or Ci. 6 alkylcarbonylCi. 6 alkyl, or R 9 is Ci_ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, Ci- 6 fluoroalkyl, Ci_ 6 chloroalkyl or Ci. 4 alkoxyCi_ 6 alkyl.
  • R 9 is Ci_ 6 alkyl (such as methyl, ethyl, iso-propyl, n-butyl, pentyl), Ci. 4 alkoxyCi_ 6 alkyl or C 2 . 6 alkynyl.
  • R and R 2 are independently selected from hydrogen and fluoro;
  • R 3 and R 4 are independently selected from hydrogen and fluoro
  • R 5 and R 6 are hydrogen, or R 5 is hydrogen and R 6 is methyl;
  • R 7 is hydrogen
  • R 8 is -C(0)R 9 ;
  • R 9 is Ci_ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoCi_ 6 alkyl, Ci_ 6 haloalkyl, Ci. 4 alkoxyCi_ 6 alkyl or d. 6alkylcarbonylCi_ 6 alkyl.
  • R and R 2 are hydrogen
  • R 3 and R 4 are hydrogen
  • R 5 and R 6 are hydrogen
  • R 7 is hydrogen
  • R 8 is -C(0)R 9 ;
  • R 9 is Ci_ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, Ci_ 6 haloalkyl or Ci. 4 alkoxyCi_ 6 alkyl.
  • R and R 2 are hydrogen; R 3 and R 4 are hydrogen;
  • R 5 and R 6 are hydrogen
  • R 7 is hydrogen
  • R 8 is -C(0)R 9 ;
  • R 9 is Ci_ 6 alkyl, Ci. 4 alkoxyCi. 6 alkyl or C 2 - 6 alkynyl.
  • the compounds of the present invention may be enantiomers of the compound of Formula (I) as represented by a Formula (la) or a Formula (lb) when n is 1 , wherein R 5 and R 6 are different (see below), or indeed when n is 2 and at only one of the two carbon positions bound to R 5 and R 6 , R 5 and R 6 are different.
  • the compounds of the present invention may be diastereomers of the compound of Formula (I) when n is 2, and wherein at each of the two carbon positions bound to R 5 and R 6 , R 5 and R 6 are different.
  • the compounds of formula (I) according to the invention may be present in a reversible equilibrium with the corresponding covalently hydrated forms (ie, the compounds of formula (l-l) and formula (l-ll) as shown below) at the CF 3 -oxadiazole motif. This dynamic equilibrium may be important for the biological activity of the compounds of Formula (I).
  • n, A 1 , A 2 , A 3 , A 4 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 , R 11 , R 2 and R 3 with reference to the compounds of formula (I) of the present invention apply generally to the compounds of Formula (l-l) and Formula (l-ll), as well as to the specific disclosures of combinations of n, A 1 , A 2 , A 3 , A 4 , R , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 , R 11 , R 2 and R 3 as represented in the compounds of Tables 1.1 to 1.10, and 2.1 to 2.10 and Tables 3.1 to 3.13 below or the compounds 1.1 to 1.1 11 described in Table T1 (below) or the compounds 2.1 to 2.36 described in Table T2 (below), or the compounds 3.1 to
  • the compounds of formula (I) can be obtained by an amide coupling transformation with compounds of formula (II) and compounds of formula (III), wherein Z represents -R 9 , -OR 10 , or - NR R 12 , by activating the carboxylic acid function of the compounds of formula (III), a process that usually takes place by converting the -OH of the carboxylic acid into a good leaving group, such as a chloride group, for example by using (COCI) 2 or SOCI 2 , prior to treatment with the compounds of formula (II), preferably in a suitable solvent (eg, dimethylformamide, dichloromethane or tetrahydrofuran), preferably at a temperature of between 25°C and 100°C, and optionally in the presence of a base such as triethylamine or A/,A/-diisopropylethylamine, or under conditions described in the literature for an amide coupling.
  • a suitable solvent eg, dimethylformamide, dichloromethane
  • compounds of formula (I) can be prepared from compounds of formula (II) via treatment with triphosgene, in a suitable solvent (eg, ethyl acetate, CHCI 3 , or toluene) with heating between 65°C and 100°C followed by the addition of suitable nucleophiles of formula (IV), wherein Z- Nu is an organometallic (eg, an organomagnesium, organozinc, or organolithium) reagent in a suitable solvent (eg, toluene, diethyl ether or tetrahydrofuran) at a temperature between -78°C and 25°C.
  • a suitable solvent eg, ethyl acetate, CHCI 3 , or toluene
  • suitable solvent eg, toluene, diethyl ether or tetrahydrofuran
  • compounds of formula (I) can be prepared from compounds of formula (II) via treatment with triphosgene, in a suitable solvent (eg, 1 ,2- dichloroethane, CHCI 3 , or toluene) followed by the addition of suitable nucleophiles of formula (IV), wherein Z-Nu represents HOR 0 or HN(R )R 12 in the presence of a suitable base such as trieth lamine.
  • a suitable solvent eg, 1 ,2- dichloroethane, CHCI 3 , or toluene
  • suitable nucleophiles of formula (IV) wherein Z-Nu represents HOR 0 or HN(R )R 12 in the presence of a suitable base such as trieth lamine.
  • compounds of formula (I), wherein R is -C(0)R can be prepared from compounds of formula (VI), wherein X is CI, Br or I, via treatment with amides of formula (V), wherein Y is tert-butylcarboxylate, in the presence of a suitable base, such as NaH, in a suitable solvent, such as dimethylformamide, at a temperature between 0°C and 100°C.
  • a suitable base such as NaH
  • a suitable solvent such as dimethylformamide
  • compounds of formula (I) can be prepared from compounds of formula (VII) by treatment with trifluoroacetic anhydride in the presence of a base (eg, pyridine or 4- dimethylaminopyridine) in a suitable solvent, such as tetrahydrofuran or ethanol, at a temperature between 25°C and 75°C.
  • a base eg, pyridine or 4- dimethylaminopyridine
  • suitable solvent such as tetrahydrofuran or ethanol
  • Compounds of formula (VII) can be prepared from compounds of formula (VIII) by treatment with a hydroxylamine hydrochloride salt in the presence of a base, such as triethylamine, in a suitable solvent, such as methanol, at a temperature between 0°C and 100°C.
  • a base such as triethylamine
  • a suitable solvent such as methanol
  • Compounds of formula (II), wherein n is 1 or 2 can be prepared from carbonyl compounds of formula (X), wherein m is 0 or 1 , when R 6A is hydrogen, starting with treatment by compounds of formula (XI), wherein R PG is tert-butylsulfinamide, optionally in the presence of an activating reagent (eg, Ti(OEt) 4 ), in a suitable solvent, (eg, tetrahydrofuran) at a temperature between 60°C and 75°C and followed by the addition of a reagent of formula (XII), wherein R 5A is H, cyano, or C 1 _ 4 alkyl, such as an alkyl Grignard reagent (eg.
  • compounds of formula (II) can be prepared from compounds of formula (XIV), wherein X is CI or Br, by treatment with amines of formula (XIII), wherein Y is tert-butylcarboxylate, in a suitable solvent (eg, tetrahydrofuran) at a temperature between 25°C and 60°C.
  • a suitable solvent eg, tetrahydrofuran
  • HCI or trifluoroacetic acid eg, dioxane or MeOH.
  • Compounds of formula (XIV), wherein n is 1 and X is CI or Br, can be prepared from compounds of formula (XV), by treatment with a halogen source (eg, N-bromosuccimide (NBS) or N- chlorosuccimide (NCS)) and a radical initiator (eg, (PhC0 2 )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-bromosuccimide (NBS) or N- chlorosuccimide (NCS)
  • a radical initiator eg, (PhC0 2 )2 or azobisisobutyronitrile (AIBN)
  • suitable solvent such as tetrachloromethane
  • Compounds of formula (XVI), wherein W is Br, I, or CN, can be obtained by an amide coupling transformation with compounds of formula (III) (wherein Z represents -R 9 , -OR 10 , or -N(R )R 12 ) and compounds of formula (XVII) by activating the carboxylic acid function of the compounds of formula (III), a process that usually takes place by converting the -OH of the carboxylic acid into a good leaving group, such as a chloride group, for example by using (COCI) 2 or SOCI 2 , prior to treatment with the compounds of formula (XVII), preferably in a suitable solvent (eg, dimethylformamide, dichloromethane or tetrahydrofuran), preferably at a temperature of between 25°C and 100°C, and optionally in the presence of a base such as triethylamine or A/,A/-diisopropylethylamine, or under conditions described in the literature for an amide coupling.
  • compounds of formula (XVI), wherein R is -C(0)R and W is Br, I, or CN can be prepared from compounds of formula (XVIII), wherein X is CI, Br or I, via treatment with amides of formula (V), wherein Y is tert-butylcarboxylate, in the presence of a suitable base, such as NaH, in a suitable solvent, such as dimethylformamide, at a temperature between 0°C and 100°C.
  • a catalyst eg, Nal or 4- dimethylaminopyridine
  • compounds of formula (XVI), wherein W is Br, I or CN can be prepared from compounds of formula (XVIII), wherein X is CI, Br, I, or -OS0 2 Me, via treatment with amines of formula (XIII), wherein Y is tert-butylcarboxylate in a suitable solvent (eg, methanol or ethanol) at a temperature between 0°C and 100°C.
  • a suitable solvent eg, methanol or ethanol
  • a catalyst eg, Nal or 4-dimethylaminopyridine
  • compounds of formula (XVIII), wherein W is Br, I, or CN and X is CI, Br, I, or OS0 2 Me are either commercially available or can be prepared from compounds of formula (XX), by treatment with a halogen source (eg, CBr 4, CCI 4 or l 2 ) in the presence of triphenylphosphine, or with methanesulfonyl chloride (CIS0 2 Me), in a suitable solvent, (eg, dichloromethane) at a temperature between 0°C and 100°C.
  • a suitable solvent eg, dichloromethane
  • novel 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. It is also possible to use compounds of formula (I) as fungicide.
  • 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 deviation from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection.
  • compounds of formula (I) as dressing agents for the treatment of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings, for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
  • the propagation material can be treated with a composition comprising a compound of formula (I) before planting: seed, for example, can be dressed before being sown.
  • the active compounds of formula (I) can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation.
  • the composition can also be applied to the planting site when the propagation material is being planted, for example, to the seed furrow during sowing.
  • the invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.
  • the compounds of formula (I) can be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management.
  • the invention could be used to protect non-living materials from fungal attack, e.g. lumber, wall boards and paint.
  • the compounds of formula (I) are for example, effective against fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses.
  • These fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses are for example:
  • Absidia corymbifera Alternaria spp, Aphanomyces spp, Ascochyta spp, Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terms, Aureobasidium spp. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. comprising B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C.
  • capsulatum Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp, Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp, Peronosclerospora spp. Including P. maydis, P.
  • leucotricha Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp, Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila, Puccinia Spp. including P. hordei, P. recondita, P. striiformis, P. triticina, Pyrenopeziza spp, Pyrenophora spp, Pyricularia spp. including P. oryzae, Pythium spp. including P.
  • the compounds of formula (I) may be used for example on turf, ornamentals, such as flowers, shrubs, broad-leaved trees or evergreens, for example conifers, as well as for tree injection, pest management and the like.
  • target crops and/or useful plants to be protected typically comprise perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St.
  • perennial and annual crops such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries
  • cereals for example barley, maize (corn), millet, oats
  • Augustine grass and Zoysia grass herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.
  • herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme
  • legumes for example beans, lentils, peas and soya beans
  • useful plants is to be understood as also including useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol- pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering.
  • herbicides like bromoxynil or classes of herbicides
  • EPSPS (5-enol- pyrovyl-shikimate-3-phosphate-synthase) inhibitors
  • GS glutamine synthetase
  • PPO protoporphyrinogen-oxidase
  • imazamox by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola).
  • crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names Round upReady®, Herculex I® and LibertyLink®.
  • useful plants is to be understood as also including useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g. CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
  • insecticidal proteins from Bacillus cereus or Bacillus popilliae such as ⁇ -endotoxins, e.g. CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl- transferase, cholesterol oxidases, ecdy
  • ⁇ -endotoxins for example CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins.
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ).
  • Truncated toxins for example a truncated CrylAb, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • amino acid replacements preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO93/07278, W095/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
  • Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a
  • 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 CrylAb toxin. Bt1 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
  • MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. 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.
  • NK603 * MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 * MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • locus 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 system ically acquired resistance inducers ("SAR" inducer).
  • SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
  • the compounds of formula (I) are normally used in the form of agrochemical compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds.
  • further compounds can be e.g. fertilizers or micronutrient donors or other preparations, which influence the growth of plants. They can also be selective herbicides or 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 pesticidal ly-active compounds, for example an additional fungicidal active ingredient in addition to the compound of formula (I).
  • the compound of formula (I) may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate.
  • An additional active ingredient may, in some cases, result in unexpected synergistic activities.
  • Suitable additional active ingredients include the following: acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenical fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine fung
  • Suitable additional active ingredients also include the following: 3-difluoromethyl-
  • 1- methyl-1 H-pyrazole-4-carboxylic acid (9-dichloromethylene-1 ,2,3,4-tetrahydro-1 ,4-methano- naphthalen-5-yl)-amide , 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid methoxy-[1-methyl- 2-(2,4,6-trichlorophenyl)-ethyl]-amide , 1-methyl-3-difluoromethyl-1 H-pyrazole-4-carboxylic acid (2- dichloromethylene-3-ethyl-1-methyl-indan-4-yl)-amide (1072957-71-1 ), 1-methyl-3-difluoromethyl-1 H- pyrazole-4-carboxylic acid (4'-methylsulfanyl-biphenyl-2-yl)-amide, 1-methyl-3-difluoromethyl-4H- pyrazole-4-carboxylic acid [2-(2,4-dichloro
  • 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
  • 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
  • halofenozide methoxyfenozide, tebufenozide
  • juvenoids pyriproxyfen, methoprene (including S-methoprene), fenoxycarb
  • 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,
  • Biological agents Bacillus thuringiensis ssp aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, virus and fungi.
  • Another aspect of invention is related to the use of a compound of formula (I) or of a preferred individual compound as defined herein, of a composition comprising at least one compound of formula (I) or at least one preferred individual compound as above-defined, or of a fungicidal or insecticidal mixture comprising at least one compound of formula (I) or at least one preferred individual compound as above-defined, in admixture with other fungicides or insecticides as described above, for controlling or preventing infestation of plants, e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living materials by insects or by phytopathogenic microorganisms, preferably fungal organisms.
  • useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living materials by insects or by phytopathogenic microorganisms, preferably fungal organisms.
  • a further aspect of invention is related to a method of controlling or preventing an infestation of plants, e.g., useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g., harvested food crops, or of non-living materials by insects or by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of formula (I) or of a preferred individual compound as above-defined as active ingredient to the plants, to parts of the plants or to the locus thereof, to the propagation material thereof, or to any part of the non-living materials.
  • useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g., harvested food crops, or of non-living materials by insects or by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms
  • a compound of formula (I) or of a preferred individual compound as above-defined as active ingredient to the plants, to parts of
  • Controlling or preventing means reducing infestation by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, to such a level that an improvement is demonstrated.
  • a preferred method of controlling or preventing an infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, or insects which comprises the application of a compound of formula (I), or an agrochemical composition which contains at least one of said compounds, is foliar application.
  • the frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen or insect.
  • the compounds of formula (I) can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field.
  • the compounds of formula I may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
  • a formulation e.g. a composition containing the compound of formula (I), and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of formula (I), may be prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface active compounds (surfactants).
  • 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.
  • a 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 107 specific compounds of the formula T-1 ):
  • n is 1 , A 1 is C-R , A 2 is C-R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are hydrogen and R 9 is as defined below in the Table 1.
  • Tables 1.2 to 1.10 make available 107 individual compounds of the formula (T-1 ) in which n, A 1 , A 2 , A 3 , A 4 , R 5 , R 6 and R 7 are as specifically defined in Tables 1.2 to 1.10, which refer to Table 1 wherein R 9 is specifically defined.
  • Table 1
  • Table 1.2 This table discloses 107 specific compounds of formula (T-1 ) wherein A 1 is C-R 1 , A 2 is C- R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are hydrogen, R is fluorine, n is 1 , and R 9 is as defined above in the Table 1.
  • Table 1.3 This table discloses 107 specific compounds of formula (T-1 ) wherein A 1 is C-R 1 , A 2 is C- R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are hydrogen, R is chlorine, n is 1 , and R 9 is as defined above in the Table 1.
  • Table 1.4 This table discloses 107 specific compounds of formula (T-1 ) wherein A 1 is C-R 1 , A 2 is C- R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are hydrogen, R is methyl, n is 1 , and R 9 is as defined above in the Table 1.
  • Table 1.5 This table discloses 107 specific compounds of formula (T-1 ) wherein A 1 is C-R 1 , A 2 is C- R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are hydrogen, R is trifluoromethyl, n is 1 , and R 9 is as defined above in the Table 1.
  • Table 1.6 This table discloses 107 specific compounds of formula (T-1 ) wherein A 1 is N, A 2 is C-R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are hydrogen, n is 1 , and R 9 is as defined above in the Table 1.
  • Table 1.7 This table discloses 107 specific compounds of formula (T-1 ) wherein A 1 is C-R 1 , A 2 is C- R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R , R 2 , R 4 , R 5 , R 6 , and R 7 are hydrogen, R 3 is fluorine, n is 1 , and R 9 is as defined above in the Table 1.
  • Table 1.8 This table discloses 107 specific compounds of formula (T-1 ) wherein A 1 is C-R 1 , A 2 is C- R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 2 , R 4 , R 5 , R 6 , and R 7 are hydrogen, R and R 3 are fluorine, n is 1 , and R 9 is as defined above in the Table 1.
  • Table 1.9 discloses 107 specific compounds of formula (T-1 ) wherein A 1 is C-R 1 , A 2 is C- R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 3 , R 4 , R 5 , R 6 , and R 7 are hydrogen, R and R 2 are fluorine, n is 1 , and R 9 is as defined above in the Table 1.
  • Table 1.10 This table discloses 107 specific compounds of formula (T-1 ) wherein A 1 is C-R 1 , A 2 is C- R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are hydrogen, n is 2, and R 9 is as defined above in the Table 1.
  • n is 1
  • a 1 is C-R
  • a 2 is C-R 2
  • a 3 is C-R 3
  • a 4 is C-R 4 and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are hydrogen and R 0 is as defined below in the Table 2.
  • Tables 2.2 to 2.10 make available 69 individual compounds of the formula (T-2) in which n, A 1 , A 2 , A 3 , A 4 , R 5 , R 6 and R 7 are as specifically defined in Tables 2.2 to 2.10, which refer to Table 2 wherein R 0 is specifically defined.
  • Table 2.2 This table discloses 69 specific compounds of formula (T-2) wherein A 1 is C-R 1 , A 2 is C-R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are hydrogen, R is fluorine, n is 1 , and R 0 is as defined above in the Table 2.
  • Table 2.3 This table discloses 69 specific compounds of formula (T-2) wherein A 1 is C-R 1 , A 2 is C-R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are hydrogen, R is chlorine, n is 1 , and R 0 is as defined above in the Table 2.
  • Table 2.4 This table discloses 69 specific compounds of formula (T-2) wherein A 1 is C-R 1 , A 2 is C-R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are hydrogen, R is methyl, n is 1 , and R 0 is as defined above in the Table 2.
  • Table 2.5 This table discloses 69 specific compounds of formula (T-2) wherein A 1 is C-R 1 , A 2 is C-R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are hydrogen, R is trifluoromethyl, n is 1 , and R 0 is as defined above in the Table 2.
  • Table 2.6 This table discloses 69 specific compounds of formula (T-2) wherein A 1 is N, A 2 is C-R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are hydrogen, n is 1 , and R 0 is as defined above in the Table 2.
  • Table 2.7 This table discloses 69 specific compounds of formula (T-2) wherein A 1 is C-R 1 , A 2 is C-R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R , R 2 , R 4 , R 5 , R 6 , and R 7 are hydrogen, R 3 is fluorine, n is 1 , and R 0 is as defined above in the Table 2.
  • Table 2.8 This table discloses 69 specific compounds of formula (T-2) wherein A 1 is C-R 1 , A 2 is C-R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 2 , R 4 , R 5 , R 6 , and R 7 are hydrogen, R and R 3 are fluorine, n is 1 , and R 0 is as defined above in the Table 2.
  • Table 2.9 This table discloses 69 specific compounds of formula (T-2) wherein A 1 is C-R 1 , A 2 is C-R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 3 , R 4 , R 5 , R 6 , and R 7 are hydrogen, R and R 2 are fluorine, n is 1 , and R 0 is as defined above in the Table 2.
  • Table 2.10 This table discloses 69 specific compounds of formula (T-2) wherein A 1 is C-R 1 , A 2 is C- R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are hydrogen, n is 2, and R 0 is as defined above in the Table 2.
  • n 1
  • a 1 is C-R
  • a 2 is C-R 2
  • a 3 is C-R 3
  • a 4 is C-R 4 and n
  • R , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 2 are hydrogen and R is as defined below in the Table 3.
  • Tables 3.2 to 3.13 make available 64 individual compounds of the formula (T-3) in which n, A 1 , A 2 , A 3 , A 4 , R 5 , R 6 , R 7 and R 2 are as specifically defined in Tables 3.2 to 3.13, which refer to Table 3 wherein R is specifically defined.
  • Table 3.2 This table discloses 64 specific compounds of formula (T-3) wherein A 1 is C-R 1 , A 2 is C-R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 2 are hydrogen, R is fluorine, n is 1 , and R is as defined above in the Table 3.
  • Table 3.3 This table discloses 64 specific compounds of formula (T-3) wherein A 1 is C-R 1 , A 2 is C-R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 2 are hydrogen, R is chlorine, n is 1 , and R is as defined above in the Table 3.
  • Table 3.4 discloses 64 specific compounds of formula (T-3) wherein A 1 is C-R 1 , A 2 is C-R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 2 are hydrogen, R is methyl, n is 1 , and R is as defined above in the Table 3.
  • Table 3.5 This table discloses 64 specific compounds of formula (T-3) wherein A 1 is C-R 1 , A 2 is C-R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 2 are hydrogen, R is trifluoromethyl, n is 1 , and R is as defined above in the Table 3.
  • Table 3.6 This table discloses 64 specific compounds of formula (T-3) wherein A 1 is N, A 2 is C-R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 2 are hydrogen, n is 1 , and R is as defined above in the Table 3.
  • Table 3.7 discloses 64 specific compounds of formula (T-3) wherein A 1 is C-R 1 , A 2 is C-R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R , R 2 , R 4 , R 5 , R 6 , R 7 and R 2 are hydrogen, R 3 is fluorine, n is 1 , and R is as defined above in the Table 3.
  • Table 3.8 This table discloses 64 specific compounds of formula (T-3) wherein A 1 is C-R 1 , A 2 is C-R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 2 , R 4 , R 5 , R 6 , R 7 and R 2 are hydrogen, R and R 3 are fluorine, n is 1 , and R is as defined above in the Table 3.
  • Table 3.9 discloses 64 specific compounds of formula (T-3) wherein A 1 is C-R , A 2 is C-R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 3 , R 4 , R 5 , R 6 , R 7 and R 2 are hydrogen, R and R 2 are fluorine, n is 1 , and R is as defined above in the Table 3.
  • Table 3.10 This table discloses 64 specific compounds of formula (T-3) wherein A 1 is C-R 1 , A 2 is C- R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 2 are hydrogen, n is 2, and R is as defined above in the Table 3.
  • Table 3.1 1 This table discloses 64 specific compounds of formula (T-3) wherein A 1 is N, A 2 is N, A 3 is C-R 3 , A 4 is C-R 4 and R 3 , R 4 , R 5 , R 6 , R 7 and R 2 are hydrogen, n is 1 , and R is as defined above in the Table 3.
  • Table 3.12 This table discloses 64 specific compounds of formula (T-3) wherein wherein A 1 is C-R 1 , A 2 is C-R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are hydrogen, R 2 is methyl, n is 1 , and R is as defined above in the Table 3.
  • Table 3.13 This table discloses 64 specific compounds of formula (T-3) wherein wherein A 1 is C-R 1 , A 2 is C-R 2 , A 3 is C-R 3 , A 4 is C-R 4 and R , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are hydrogen, R 2 is ethyl, n is 1 , and R is as defined above in the Table 3.
  • 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).
  • LC/MS means Liquid Chromatography Mass Spectrometry and the description of the apparatus and the method (Methods A and B) is as follows:
  • Electrospray Polarity positive and negative ions
  • Type of column Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1.8 micron; Temperature: 60°C.
  • Type of column Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1 .8 micron; Temperature: 60°C.
  • enantiomerically pure final compounds may be obtained from racemic materials as appropriate via standard physical separation techniques, such as reverse phase chiral chromatography, or through stereoselective synthetic techniques, eg, by using chiral starting materials.
  • the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
  • Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water. Dusts a) b) c)
  • Active ingredient [compound of formula (I)] 5 % 6 % 4 %
  • Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
  • the active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • polyethylene glycol (mol. wt. 200) 3 %
  • Kaolin 89 % The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
  • nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
  • silicone oil (in the form of a 75 % emulsion in water) 1 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • Flowable concentrate for seed treatment active ingredient [compound of formula (I)] 40 %
  • Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • 28 parts of a combination of the compound of formula I are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8: 1 ).
  • This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved.
  • To this emulsion a mixture of 2.8 parts 1 ,6- diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • LC/MS Liquid Chromatography Mass Spectrometry and the description of the apparatus and the methods used for LC/MS analysis are given below.
  • AIBN azobisisobutyronitrile
  • BOP-CI phosphoric acid bis(2-oxooxazolidide) chloride
  • CDI carbonyl diimidazole
  • DIBAL-H diisobutylaluminium hydride
  • DIEA N-ethyl-N-isopropyl-propan-2-amine
  • DIPEA N,N-diisopropylethylamine
  • EdCI 3-(ethyliminomethyleneamino)-/V,/V-dimethylpropan-1-amine
  • HOAt 1-hydroxy-7-azabenzotriazole
  • HATU 1-[bis(dimethylamino)methylene]-1 H-1 ,2 ⁇ -triazolo[4,5-b]pyridinium 3-oxid- hexafluorophosphate
  • NBS N-bromosuccinimide
  • Step 1 Preparation of N'-hvdroxy-4-methyl-benzamidine To a stirring suspension of 4-methylbenzonitrile (35 g, 0.29 mol) in ethanol (220 mL) and water
  • 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
  • Step 4 Preparation of [4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethanamine hydrochloride
  • the titled compound can be prepared using an analaqous procedure as described in WO 2013/066839.
  • Step 5 Preparation of 2,2-dimethyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyll- propanamide
  • Step 1 Preparation of tert-butyl N-[2-(4-cyanophenyl)ethyl]carbamate
  • Step 2 Preparation of tert-butyl N-[2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]ethyl]carbamate
  • Step 3 Preparation of 2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]ethylammonium chloride
  • Step 4 Preparation of N-[2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]ethyl]propanamide
  • Protocol A Portions of triphosgene (5.94 mg) in DCE (0.3 imL) were transferred at 0°C to a 5 96 slot deep well plate (DWP96) containing the alcohol derivative [HOR 10 ] or amine derivative [HN(R )R 12 ] of formula (IV) (0.05 mmol) and triethylamine (0.12 mmol) in 200 ⁇ _ DMA. The reaction mixtures were stirred at RT for 30 minutes. [4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]aryl]methanamine derivatives of formula (II) (0.05 mmol) and triethylamine (0.12 mmol) in 200 ⁇ _ DMA were added.
  • Protocol B The alcohol derivative [HOR 10 ] or amine derivative [HNR R 12 ] of formula (IV) 5 (0.05 mmol) and DIPEA (0.25 mmol) in 300 ⁇ _ DMA were transferred at RT to a 96 slot deep well plate (DWP96). CDI (0.10 mmol) in DMA (300 ⁇ _) was added and stirred until solubilization. [4-[5- (trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]aryl]methanamine derivatives of formula (II) (0.05 mmol) and triethylamine (0.12 mmol) in 200 ⁇ _ DMA were added. The DWP was sealed and stirred at RT for 18 hours.
  • Table T1 Melting point (mp) data and/or retention times (RT) for the compounds of Formula (I).
  • Table T3 Melting point (mp) data and/or retention times (RT) for the compounds of Formula (I).
  • 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 10 concentration with 0.025% Tween20 just before spraying.
  • the inoculated leaf disks or segments are incubated under defined conditions (temperature, relative humidity, light, etc.) according to the respective test system.
  • a single evaluation of disease level is carried out 3 to 14 days after inoculation, depending on the pathosystem. Percent disease control relative to the untreated check leaf disks or segments is then calculated.
  • Mycelia fragments or conidia suspensions of a fungus prepared either freshly from liquid cultures of the fungus or from cryogenic storage, are directly mixed into nutrient broth.
  • DMSO solutions of the test compound (max. 10 mg/ml) are diluted with 0.025% Tween20 by a factor of 50 and 10 ⁇ of this solution is pipetted into a microtiter plate (96-well format). The nutrient broth containing the fungal spores/mycelia fragments is then added to give an end concentration of the tested compound.
  • the test plates are incubated in the dark at 24°C and 96% relative humidity.
  • 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.
  • Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates (24-well format). The leaf segments are then inoculated with a spore suspension of the fungus. Plates were stored in darkness at 19°C and 75% relative humidity. The formulated test compound diluted in water was applied 1 day after inoculation.
  • the leaf segments were incubated at 19°C and 75% relative humidity under a light regime of 12 hours light / 12 hours darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (6 to 8 days after application).
  • the following compounds at 200 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.
  • Soybean leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. One day after application leaf discs are inoculated by spraying a spore suspension on the lower leaf surface. After an incubation period in a climate cabinet of 24-36 hours in darkness at 20°C and 75% rh leaf disc are kept at 20°C with 12 h light/day and 75% rh. 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.
  • 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
  • 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.
  • Field bean leaf discs are placed on water agar in multiwell plates (96-well format) and 10 ⁇ of the formulated test compound diluted in acetone and a spreader pipetted onto the leaf disc. Two hours 30 after application leaf discs are inoculated by spraying a spore suspension on the lower leaf surface.
  • the leaf discs are incubated in a climate cabinet at 22°C with 18 hour light/day and 70% relative humidity.
  • 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 days after application).

Abstract

Compounds of the formula (I) wherein, the substituents are as defined in claim 1, useful as a pesticides, especially as fungicides.

Description

Microbiocidal Oxadiazole Derivatives
The present invention relates to microbiocidal oxadiazole derivatives, eg, as active ingredients, which have microbiocidal activity, in particular, fungicidal activity. The invention also relates to agrochemical compositions which comprise at least one of the oxadiazole derivatives, to processes of preparation of these compounds and to uses of the oxadiazole derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, preferably fungi.
Microbiocidal oxadiazole derivatives are known as 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.
According to the present invention, there is rovided a compound of formula (I):
Figure imgf000002_0001
n is 1 or 2; A1 represents N or CR , wherein R is hydrogen, halogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy;
A2 represents N or CR2, wherein R2 is hydrogen, halogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy;
A3 represents N or CR3, wherein R3 is hydrogen or halogen;
A4 represents N or CR4, wherein R4 is hydrogen or halogen; and wherein no more than two of A1 to A4 are N;
R5 and R6 are independently selected from hydrogen, C1_4alkyl, halogen, cyano, trifluoromethyl and difluoromethyl, or R5 and R6 together with the carbon atom they share form a cyclopropyl; R7 is hydrogen; R represents -C(0)R , wherein R is hydrogen, d-6alkyl, d ^alkenyl, d ^alkynyl, cyanod- 6alkyl, Ci_6haloalkyl, C2-6haloalkenyl, hydroxyCi_6alkyl, hydroxyCi_6haloalkyl, Ci.4alkoxyCi.6alkyl, Ci_ 4haloalkoxyCi.6alkyl, Ci-4alkoxyCi.4alkoxyCi.6alkyl, C2-6alkynyloxyCi.6alkyl, aminoCi.6alkyl, N-Ci_ 4alkylaminoCi.6alkyl, N,N-diCi.4alkylanriinoCi.6alkyl, Ci.6alkylcarbonylCi.6alkyl, Ci.6alkylcarbonylC2. 6alkenyl, Ci.6alkoxycarbonylCi.6alkyl, Ci.6alkylcarbonyloxyCi.6alkyl, N-Ci.4alkylcarbonylanriinoCi.6alkyl, N-Ci.4alkylanriinocarbonylCi.6alkyl, N,N-diCi.4alkylanriinocarbonylCi.6alkyl, Ci.6alkylsulfanylCi.6alkyl, d- 6alkylsulfonylCi_6alkyl or Ci.6alkylsulfonylanriinoCi.6alkyl; or
R8 represents -C(0)OR °, wherein R 0 is hydrogen, Ci_8alkyl, C3.6alkenyl, C3.6alkynyl, cyanod- 6alkyl, Ci_6haloalkyl, C3.6haloalkenyl, hydroxyCi_6alkyl, Ci.4alkoxyCi_6alkyl, Ci.4haloalkoxyCi_6alkyl, Ci_ 4alkoxyCi-4alkoxyCi.6alkyl, C2.6alkynyloxyCi.6alkyl, aminoCi.6alkyl, N-Ci.4alkylaminoCi.6alkyl, N,N-diCi_ 4alkylaminoCi.6alkyl, Ci.6alkylcarbonylCi.6alkyl, Ci.6alkylcarbonylC2.6alkenyl, Ci.6alkoxycarbonylCi_ 6alkyl, Ci.6alkylcarbonyloxyCi.6alkyl, N-Ci.4alkylaminocarbonylCi.6alkyl, N,N-diCi_
4alkylaminocarbonylCi.6alkyl, Ci.4alkylsulfanylCi_6alkyl, Ci.6alkylsulfonylCi.6alkyl or d- 6alkylsulfonylaminoCi.6alkyl; or
R8 represents -C(0)NR R12, wherein R is hydrogen, cyano, Ci_6alkyl, C2.6alkenyl, C2. 6alkynyl, cyanoCi_8alkyl, Ci_6haloalkyl, C2.6haloalkenyl, hydroxyCi_6alkyl, Ci.4alkoxyCi_6alkyl, Ci_ 4haloalkoxyCi_6alkyl, Ci.4alkoxyCi.4alkoxyCi.6alkyl, C2.6alkynyloxyCi.6alkyl, aminoCi.6alkyl, N-Ci_ 4alkylaminoCi.6alkyl, N,N-diCi.4alkylaminoCi.6alkyl, Ci.6alkylcarbonylCi.6alkyl, Ci.6alkylcarbonylC2. 6alkenyl, Ci.6alkoxycarbonylCi.6alkyl, Ci.6alkylcarbonyloxyCi.6alkyl, N-Ci.4alkylaminocarbonylCi.6alkyl, N,N-diCi.4alkylaminocarbonylCi.6alkyl, Ci.4alkylsulfanylCi_6alkyl, Ci.6alkylsulfonylCi.6alkyl or d- 6alkylsulfonylaminoCi.6alkyl; R 2 is hydrogen, C1_4alkyl, C-|.4alkoxy, Ci.4alkoxyd.6alkyl, d ^alkenoxy or d ealkynoxy; or
R and R 2 together with the nitrogen atom they share form a 4-, 5- or 6-membered cycle optionally containing a heteroatom moiety comprising O, S or NR 3; R 3 is hydrogen, methyl, methoxy, formyl or acyl; or a salt or an N-oxide thereof; with the proviso that the compound of Formula (I) is not: tert-butyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]carbamate.
Surprisingly, it has been found that the 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. According to a second aspect of the invention, there is provided an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I). The composition may further comprise at least one additional active ingredient and/or an agrochemically-acceptable diluent or carrier.
According to a third aspect of the invention, there is provided 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.
According to a fourth aspect of the invention, there is provided the use of a compound of formula (I) as a fungicide. According to this particular aspect of the invention, the use may or may not include methods for the treatment of the human or animal body by surgery or therapy. As used herein, the term "halogen" or "halo" refers to fluorine (fluoro), chlorine (chloro), bromine
(bromo) or iodine (iodo), preferably fluorine, chlorine or bromine.
As used herein, cyano means a -CN group.
As used herein, amino means an -NH2 group.
As used herein, hydroxy means an -OH group.
As used herein, formyl means an -C(0)H group.
As used herein, acyl means an -C(0)CH3 group.
As used herein, the term "Ci_8alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to eight carbon atoms, and which is attached to the rest of the molecule by a single bond. The terms "Ci_6alkyl" and "Ci_4alkyl" are to be construed accordingly. Examples of d-8alkyl include, but are not limited to, methyl, ethyl, n-propyl, 1-methylethyl (iso-propyl), n-butyl, 2-methylpropyl (/so-butyl) and n-pentyl.
As used herein, the term "C2.6alkenyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond that can be of either the (E)- or (Z)-configu ration, having from two to six carbon atoms, which is attached to the rest of the molecule by a single bond. The term "C2-4alkenyl" is to be construed accordingly. Examples of C2.6alkenyl include, but are not limited to, ethenyl, prop-1-enyl, but-1-enyl.
As used herein, the term "C2.6alkynyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from two to six carbon atoms, and which is attached to the rest of the molecule by a single bond. The term "C2.4alkynyl" is to be construed accordingly. Examples of C2.6alkynyl include, but are not limited to, ethynyl, prop-1-ynyl, but-1-ynyl.
As used herein, the term "N-Ci_4alkylamino" refers to a radical of the formula -NH-Ra where Ra is a Ci-4alkyl radical as defined above.
As used herein, the term "N,N-diCi_4alkylamino" refers to a radical of the formula -N(Ra)-Ra where each Ra is a C1_4alkyl radical, which may be the same or different, as defined above. As used herein, the term "d-6alkoxy" refers to a radical of the formula -ORa where Ra is a d. 6alkyl radical as generally defined above. The term "Ci_4alkoxy" is to be construed accordingly. Examples of Ci_6alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, iso-propoxy, butoxy.
As used herein, the term "Ci_6alkylcarbonyl" refers to a radical of the formula -C(0)Ra where Ra is a Ci-6alkyl radical as generally defined above. The term "Ci_4alkylcarbonyl" is to be construed accordingly.
As used herein, the term "Ci_6alkoxycarbonyl" refers to a radical of the formula -C(0)ORa where Ra is a Ci-6alkyl radical as generally defined above. The term "Ci_4alkoxycarbonyl" is to be construed accordingly.
As used herein, the term "Ci_6alkylcarbonyloxy" refers to a radical of the formula -OC(0)Ra where Ra is a Ci_6alkyl radical as generally defined above. The term "Ci_4alkylcarbonyloxy" is to be construed accordingly.
As used herein, the term "N-Ci_4alkylaminocarbonyl" refers to a radical of the formula - C(0)NHRa where Ra is a Ci_4alkyl radical as generally defined above.
As used herein, the term "N,N-diCi_4alkylaminocarbonyl" refers to a radical of the formula -
C(0)NRa(Ra) where each Ra is a Ci_4alkyl radical, which may be the same or different, as generally defined above.
As used herein, the term "Ci.6alkylsulfanyl" refers to a radical of the formula -SRa where Ra is a Ci-6alkyl radical as generally defined above. The term "Ci_4alkylsulfanyl" is to be construed accordingly.
As used herein, the term "Ci.6alkylsulfonyl" refers to a radical of the formula -S(0)2Ra where Ra is a Ci-6alkyl radical as generally defined above. The term "Ci_4alkylsulfonyl" is to be construed accordingly.
As used herein, the term "Ci_6alkylsulfonylamino" refers to a radical of the formula -NHS(0)2Ra where Ra is a Ci_6alkyl radical as generally defined above. The term "Ci_4alkylsulfonylamino" is to be construed accordingly.
As used herein, the term "C2.6alkenoxy" refers to a radical of the formula -ORa where Ra is a C2. 6alkenyl radical as generally defined above. The term "C2.4alkenoxy" is to be construed accordingly.
As used herein, the term "C2.6alkynoxy" refers to a radical of the formula -ORa where Ra is a C2. 6alkynyl radical as generally defined above. The term "C2.4alkynoxy" is to be construed accordingly.
As used herein, the term "Ci_4haloalkoxy" refers to a Ci_4alkoxy group as defined above substituted by one or more of the same or different halogen atoms. Examples of Ci_4haloalkoxy include, but are not limited to, fluoromethoxy, fluoroethoxy (including 2-fluoroethoxy), trifluoromethoxy, 2,2,2-trifluoroethoxy.
As used herein, the term "cyanoCi_6alkyl" refers to a Ci_6alkyl radical as generally defined above substituted by one or more cyano groups as defined above. The term "cyanoCi_4alkyl" is to be construed accordingly. Examples of cyanoCi_6alkyl include, but are not limited to cyanomethyl, cyanoethyl (including 2-cyanoethyl).
As used herein, the term "Ci_6haloalkyl" refers to a Ci_6alkyl radical as generally defined above substituted by one or more of the same or different halogen atoms. The term "Ci_4haloalkyl" is to be construed accordingly. Examples of Ci_6haloalkyl include, but are not limited to fluoromethyl, fluoroethyl (including 2-fluoroethyl), trifluoromethyl, 2,2,2-trifluoroethyl.
As used herein, the term "hydroxyCi_6haloalkyl" refers to a d-6haloalkyl radical as generally defined above substituted by one or more hydroxy groups as defined above.
As used herein, the term "C2-6haloalkenyl" refers to a d^alkenyl radical as generally defined above substituted by one or more of the same or different halogen atoms. The term "C2-4haloalkenyl" is to be construed accordingly.
As used herein, the term "hydroxyCi_6alkyl" refers to a Ci_6alkyl radical as generally defined above substituted by one or more hydroxy groups as defined above. The term "hydroxyCi_4alkyl" is to be construed accordingly.
As used herein, the term "Ci.4alkoxyCi.6alkyl" refers to a Ci_6alkyl radical as generally defined above substituted by a Ci_4alkoxy group as defined above. The term "Ci.4alkoxyCi.4alkyl" is to be construed accordingly. Examples of Ci.4alkoxyCi_6alkyl include, but are not limited to methoxymethyl, 2-methoxyethyl.
As used herein, the term "Ci.4haloalkoxyCi.6alkyl" refers to a Ci_6alkyl radical as generally defined above substituted by a Ci_4haloalkoxy group as defined above. The term "Ci_4halolkoxyCi_ 4alkyl" is to be construed accordingly.
As used herein, the term "Ci.4alkoxyCi.4alkoxyCi.6alkyl" refers to a Ci_6alkyl radical as generally defined above substituted by a Ci_4alkoxy group as defined above, the Ci_4alkoxy group itself substituted by the same or a different Ci_4alkoxy group as defined above.
As used herein, the term "C2-6alkynyloxyCi.6alkyl" refers to a Ci_6alkyl radical as generally defined above substituted by one or more C2.6alkynyloxy group as defined above.
As used herein, the term "aminoCi_6alkyl" refers to a Ci_6alkyl radical as generally defined above substituted by one or more amino groups as defined above. The term "aminoCi_4alkyl" is to be construed accordingly.
As used herein, the term "N-Ci.4alkylaminoCi.6alkyl" refers to a Ci_6alkyl radical as generally defined above substituted by a Ci_4alkylamino group as defined above. The term "Ci_4alkylaminoCi. 4alkyl" is to be construed accordingly.
As used herein, the term "N,N-diCi.4alkylaminoCi.6alkyl" refers to a Ci_6alkyl radical as generally defined above substituted by an N,N-diCi_4alkylamino group as defined above. The term "N,N-diCi_ 4alkylaminoCi_4alkyl" is to be construed accordingly.
As used herein, the term "Ci.6alkylcarbonylCi.6alkyl" refers to a Ci_6alkyl radical as generally defined above substituted by a Ci_6alkylcarbonyl group as defined above. The term "d_ 6alkylcarbonylCi_4alkyl" is to be construed accordingly.
As used herein, the term "Ci.6alkylcarbonylC2.6alkenyl" refers to a C2.6alkenyl radical as generally defined above substituted by a Ci_6alkylcarbonyl group as defined above. The term "d_ 6alkylcarbonylC2.4alkenyl" is to be construed accordingly.
As used herein, the term "Ci.6alkoxycarbonylCi.6alkyl" refers to a Ci_6 alkyl radical as generally defined above substituted by a Ci_6alkoxycarbonyl group as defined above. The term "d_ 6alkoxycarbonyld-4alkyl" is to be construed accordingly. As used herein, the term "Ci.6alkylcarbonyloxyCi.6alkyl" refers to a d-6alkyl radical as generally defined above substituted by a Ci_6alkylcarbonyloxy group as defined above. The term "d. 6alkylcarbonyloxyCi_4alkyl" is to be construed accordingly.
As used herein, the term "N-Ci_4alkylcarbonylamino" refers to a -N(H)C(0)Ra radical wherein Ra refers to a C1_4alkyl radical as generally defined above
As used herein, the term "N-Ci-4alkylcarbonylaminoCi-6alky ' refers to a Ci_6alkyl radical as generally defined above substituted by an N-Ci_4alkylcarbonylamino group as defined above.
As used herein, the term "N-Ci.4alkylaminocarbonylCi.6alkyl", refers to a Ci_6alkyl radical as generally defined above substituted by a N-Ci_4alkylaminocarbonyl group as defined above. The term "N-Ci_4alkylaminocarbonylCi-4alkyl" is to be construed accordingly.
As used herein, the term "N,N-diCi.4alkylaminocarbonylCi.6alkyl", refers to a Ci_6alkyl radical as generally defined above substituted by a N,N-diCi.4alkylaminocarbonylCi.6alkyl group as defined above. The term "N,N-diCi.4alkylaminocarbonylCi_4alkyl " is to be construed accordingly.
As used herein, the term "Ci-6alkylsulfanylCi-6alkyr', refers to a Ci_6alkyl radical as generally defined above substituted by a Ci_6alkylsulfanyl group as defined above. The term "Ci.6alkylsulfanylCi_ 4alkyl" is to be construed accordingly.
As used herein, the term "Ci-6alkylsulfonylCi-6alkyr', refers to a Ci_6alkyl radical as generally defined above substituted by a Ci_6alkylsulfonyl group as defined above. The term "Ci.6alkylsulfonylCi_ 4alkyl" is to be construed accordingly.
As used herein, the term "Ci-6alkylsulfonylaminoCi-6alkyr', refers to a Ci_6alkyl radical as generally defined above substituted by a Ci_6alkylsulfonylamino group as defined above. The term "d. 6alkylsulfonylaminoCi_4alkyl" is to be construed accordingly.
The presence of one or more possible asymmetric carbon atoms in a compound of formula (I) means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. Also atropisomers may occur as a result of restricted rotation about a single bond. Formula (I) is intended to include all those possible isomeric forms and mixtures thereof. The present invention includes all those possible isomeric forms and mixtures thereof for a compound of formula (I). Likewise, 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).
In each case, 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. The compound of Formula (I) which is not according to the present invention (known from WO 2013/066839) is:
Figure imgf000008_0001
tert-butyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]carbamate.
The compound not according to the invention may be used in a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of the compound or a composition comprising the compound as active ingredient is applied to the plants, to parts thereof or the locus thereof. Likewise, the aforementioned compound not according to the invention may be useful as a fungicidal agent.
The following lists provide definitions, including preferred definitions, for substituents n, A1 , A2, A3, A4, R , R2, R3, R4, R5, R6, R7 and R8 (when R8 is -C(0)R9) with reference to the compounds of formula (I). For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below or elsewhere in this document. n represents 1 or 2. In some embodiments of the invention, n is 1 , In other embodiments of the invention, n is 2. Preferably, n is 1. A1 represents N or CR , wherein R represents hydrogen, halogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy.
A2 represents N or CR2, wherein R2 represents hydrogen, halogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy;
A3 represents N or CR3, wherein R3 represents hydrogen or halogen;
A4 represents N or CR4, wherein R4 represents hydrogen or halogen; and wherein no more than two of A1 to A4 are N (ie, 0, 1 or 2 of A1 to A4 may be N);
Preferably, A1 represents N or CR1 , wherein R is selected from hydrogen, fluoro, chloro, methoxy, or trifluoromethyl. Preferably, A2 represents CR2 and R2 is hydrogen or fluoro. Preferably, A3 represents CR3 and R3 is hydrogen, and A4 represents CR4 and R4 is hydrogen. Preferably, A1 to A4 are C-H. In some embodiments of the invention, A1 is N or CR wherein R is hydrogen, halogen, methyl or trifluoromethyl; A2 is N or C-H; A3 is N or CR3 wherein R3 is hydrogen or halogen; and A4 is C-H. In other embodiments, A1 is N or CR1 wherein R is hydrogen or fluoro; A2 is C-H; A3 is CR3 wherein R3 is hydrogen or fluoro; and A4 is C-H.
In some embodiments of the invention, the 6-membered ring comprising A1 to A4 is a phenyl (where A1 to A4 are C-H), pyridinyl (where A1 or A3 is N and the other A positions are C-H), pyrimidinyl (where A1 and A3 are N and the other A positions are C-H), fluorophenyl (where A1 or A3 are C-F (preferably A3 is C-F) and the other A positions are C-H) or difluorophenyl (where A1 and A3 are C-F and the A2 and A4 positions are C-H) group.
In some embodiments of the invention, R and R2 may be independently selected from hydrogen, chloro, fluoro, methyl, methoxy and trifluoromethyl. Preferably, R and R2 may be independently selected from hydrogen and fluoro. R3 and R4 may be independently selected from hydrogen and halogen. Preferably, R3 and R4 may be independently selected from hydrogen and fluoro. More preferably, R3 and R4 are hydrogen. In the compounds according to Formula (I), at least two of R , R2, R3 and R4 may be hydrogen. Preferably, three of R , R2, R3 and R4 are hydrogen, wherein more preferably R2, R3 and R4 are hydrogen. R5 and R6 are independently selected from hydrogen, C1_4alkyl, halogen, cyano, trifluoromethyl and difluoromethyl, or R5 and R6 together with the carbon atom they share form a cyclopropyl. Preferably, R5 and R6 are independently selected from hydrogen and C1_4alkyl (eg, methyl), or R5 and R6 together with the carbon atom they share form a cyclopropyl. More preferably, R5 and R6 are independently selected from hydrogen and C1_4alkyl. Even more preferably, R5 and R6 are hydrogen, or R5 is hydrogen and R6 is C1_4alkyl, preferably methyl or ethyl. Still more preferably, R5 and R6 are hydrogen.
In some embodiments of the invention, in compounds according to Formula (I), n is 1 , and R5 and R6 are independently selected from hydrogen and methyl. In other embodiments of the invention, in compounds according to Formula (I), n is 2, and R5 and R6 are independently selected from hydrogen and fluoro.
R7 is hydrogen. In one embodiment of the compounds of Formula (I), R8 represents -C(0)R9.
R9 is hydrogen, d-6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoCi_6alkyl, Ci_6haloalkyl, C2-6haloalkenyl, hydroxyCi-6alkyl, hydroxyCi_6haloalkyl, Ci.4alkoxyCi.6alkyl, Ci.4haloalkoxyCi.6alkyl, Ci_4alkoxyCi_ 4alkoxyCi-6alkyl, C2-6alkynyloxyCi-6alkyl, aminoCi_6alkyl, N-Ci.4alkylaminoCi.6alkyl, N,N-diCi_ 4alkylaminoCi-6alkyl, Ci.6alkylcarbonylCi.6alkyl, Ci.6alkylcarbonylC2.6alkenyl, Ci.6alkoxycarbonylCi_ 6alkyl, Ci.6alkylcarbonyloxyCi.6alkyl, N-Ci.4alkylcarbonylaminoCi.6alkyl, N-Ci_4alkylaminocarbonylCi. 6alkyl, N,N-diCi-4alkylaminocarbonylCi-6alkyl, Ci.6alkylsulfanylCi.6alkyl, Ci.6alkylsulfonylCi.6alkyl or Ci_ 6alkylsulfonylaminoCi-6alkyl.
Preferably, R9 is hydrogen, d-6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoCi_6alkyl, Ci_6haloalkyl, C2. 6haloalkenyl, hydroxyCi_6alkyl, hydroxyCi_6haloalkyl, Ci.4alkoxyCi.6alkyl, Ci.4haloalkoxyCi.6alkyl, Ci_ 4alkoxyCi.4alkoxyCi.6alkyl, C2-4alkynyloxyCi.6alkyl, aminoCi.6alkyl, N-Ci.4alkylanriinoCi.6alkyl, N,N-diCi_ 4alkylaminoCi.6alkyl, Ci.6alkylcarbonylCi.6alkyl, Ci.4alkylsulfanylCi.6alkyl or Ci.6alkylsulfonylCi.6alkyl. More preferably, R9 is Ci_6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoCi_6alkyl, Ci_6haloalkyl, hydroxyCi_6alkyl, hydroxyCi_6haloalkyl, Ci.4alkoxyCi.6alkyl, Ci.4haloalkoxyCi_6alkyl, Ci.4alkylcarbonylCi_4alkyl or N-Ci_ 4alkylcarbonylaminoCi-6alkyl. Even more preferably, R9 is Ci_6alkyl, C3.6alkenyl, C3.6alkynyl, cyanoCi. 4alkyl, Ci_6haloalkyl, hydroxyCi_4alkyl, hydroxyCi_4haloalkyl, Ci_2alkoxyCi_4alkyl, Ci_2haloalkoxyCi_ 4alkyl, Ci_2alkylcarbonylCi_4alkyl or N-Ci.2alkylcarbonylaminoCi_2alkyl.
In other embodiments, preferably, R9 is hydrogen, Ci_6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoC-i. 6alkyl, Ci_6fluoroalkyl, Ci_6chloroalkyl, hydroxyCi_6alkyl, Ci.4alkoxyCi_6alkyl, Ci.4fluoroalkoxyCi_6alkyl,
Ci.4alkoxyC2.4alkoxyCi.6alkyl or Ci.6alkylcarbonylCi.6alkyl. Even more preferably, R9 is hydrogen, d.
6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoCi_6alkyl, Ci_6fluoroalkyl, Ci_6chloroalkyl, hydroxyCi_6alkyl, d.
4alkoxyCi_6alkyl, Ci.2fluoroalkoxyCi_6alkyl, Ci.2alkoxyC2.3alkoxyCi.6alkyl or Ci.6alkylcarbonylCi.6alkyl.
Still more preferably, R9 is Ci_6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoCi_6alkyl, Ci_6fluoroalkyl, Ci_ 6chloroalkyl, Ci.4alkoxyCi_6alkyl or Ci.6alkylcarbonylCi.6alkyl, or R9 is Ci_6alkyl, C2.6alkenyl, C2.6alkynyl,
Ci_6fluoroalkyl, Ci_6chloroalkyl or Ci.4alkoxyCi_6alkyl. Most preferably, R9 is Ci_6alkyl (such as methyl, ethyl, iso-propyl, n-butyl, pentyl), Ci.4alkoxyCi_6alkyl or C2.6alkynyl.
In certain embodiments of the invention, R9 is Ci_6alkyl, C3.6alkenyl, C3.6alkynyl, cyanoCi_4alkyl, Ci_6haloalkyl, hydroxyCi_4alkyl, hydroxyCi_4haloalkyl, Ci_2alkoxyCi_4alkyl, Ci_2haloalkoxyCi_4alkyl, Ci_ 2alkylcarbonylCi_4alkyl or N-Ci.2alkylcarbonylaminoCi_2alkyl. Preferably, R9 is Ci_6alkyl, C3.4alkenyl, C3. 6alkynyl, Ci_4fluoroalkyl, Ci_4chloroalkyl, Ci_2alkoxyCi_4alkyl or Ci_2fluoroalkoxyCi_4alkyl, in particular, R9 is methyl, ethyl, n-propyl, iso-propyl, sec-butyl (1-methylpropyl), iso-butyl (2-methylpropyl), tert-butyl (1 ,1-dimethylethyl), 2,2-dimethylpropyl, (1-methyl-1-ethyl)propyl, (l-methyl)ethenyl, (1 ,1-dimethyl)prop- 2-ynyl, 2,2,2-trifluoroethyl, (1 ,1-dimethyl-2-chloro)ethyl, methoxy-(1 ,1-dimethyl)methyl, 2-methoxyethyl, (difluoromethoxy)methyl or 2-(difluoromethoxy)ethyl.
Preferably, in a compound according to formula (I) of the invention,
A1 is CR and A2 is CR2 wherein R and R2 are independently selected from hydrogen and fluoro;
A3 is CR3 and A4 is CR4 wherein R3 and R4 are independently selected from hydrogen and fluoro;
R5 and R6 are hydrogen, or R5 is hydrogen and R6 is methyl;
R7 is hydrogen;
R8 is -C(0)R9 _„
10
R9 is Ci_6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoCi_6alkyl, Ci_6haloalkyl, Ci.4alkoxyCi.6alkyl or d. 6alkylcarbonylCi.6alkyl; and
n is 1. More preferably, A1 is CR and A2 is CR2 wherein R and R2 are hydrogen;
A3 is CR3 and A4 is CR4 wherein R3 and R4 are hydrogen;
R5 and R6 are hydrogen;
R7 is hydrogen; and
R8 is -C(0)R9;
R9 is Ci_6alkyl, C2.6alkenyl, C2.6alkynyl, Ci_6haloalkyl or Ci.4alkoxyCi.6alkyl: and
n is 1.
Even more preferably, A1 is CR1 and A2 is CR2 wherein R and R2 are hydrogen;
A3 is CR3 and A4 is CR4 wherein R3 and R4 are hydrogen;
R5 and R6 are hydrogen;
R7 is hydrogen;
R8 is -C(0)R9
R9 is Ci-6alkyl, Ci.4alkoxyCi.6alkyl or C2.6alkynyl; and
n is 1.
The following lists provide definitions, including preferred definitions, for substituents n, A1, A2, A3, A4, R1, R2, R3, R4, R5, R6, R7 and R8 (when R8 is -C(0)OR °) with reference to the compounds of formula (I). For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below or elsewhere in this document. n represents 1 or 2. In some embodiments of the invention, n is 1. In other embodiments of the invention, n is 2. Preferably, n is 1.
A1 represents N or CR1, wherein R represents hydrogen, halogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy;
A2 represents N or CR2, wherein R2 represents hydrogen, halogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy; A3 represents N or CR3, wherein R3 represents hydrogen or halogen;
A4 represents N or CR4, wherein R4 represents hydrogen or halogen; and wherein no more than two of A1 to A4 are N (ie, 0, 1 or 2 of A1 to A4 may be N); Preferably, A1 represents N or CR1, wherein R is selected from hydrogen, fluoro, chloro, methoxy, or trifluoromethyl. Preferably, A2 represents CR2 and R2 is hydrogen or fluoro. Preferably, A3 represents CR3 and R3 is hydrogen, and A4 represents CR4 and R4 is hydrogen. Most preferably, A1 to A4 are C-H, or A1 is N and A2 to A4 are C-H.
In some embodiments of the invention, the 6-membered ring comprising A1 to A4 is a phenyl (where A1 to A4 are C-H), pyridinyl (where A1 or A3 is N and the other A positions are C-H), pyrimidinyl (where A1 and A3 are N and the other A positions are C-H), fluorophenyl (where A1 or A3 are C-F (preferably A3 is C-F) and the other A positions are C-H) or difluorophenyl (where A1 and A3 are C-F and the A2 and A4 positions are C-H) group.
R5 and R6 are independently selected from hydrogen, C1_4alkyl, halogen, cyano, trifluoromethyl and difluoromethyl, or R5 and R6 together with the carbon atom they share form a cyclopropyl. Preferably, R5 and R6 are independently selected from hydrogen and C1_4alkyl. Preferably, R5 and R6 are hydrogen, or R5 is hydrogen and R6 is C1_4alkyl, preferably methyl or ethyl. More preferably, R5 and R6 are hydrogen.
In some embodiments of the invention, in compounds according to Formula (I), n is 1 , and R5 and R6 are independently selected from hydrogen and methyl. In other embodiments of the invention, in compounds according to Formula (I), n is 2, and R5 and R6 are independently selected from hydrogen and fluoro.
R7 is hydrogen. R8 represents -C(0)OR °, wherein R 0 is hydrogen, d-8alkyl, C3.6alkenyl, C3.6alkynyl, cyanoC-i.
6alkyl, Ci_6haloalkyl, C3.6haloalkenyl, hydroxyCi_6alkyl, Ci.4alkoxyCi.6alkyl, Ci.4haloalkoxyCi.6alkyl, d. 4alkoxyCi-4alkoxyCi-6alkyl, C2-6alkynyloxyCi.6alkyl, aminoCi_6alkyl, N-Ci.4alkylaminoCi.6alkyl, N,N-diCi_ 4alkylaminoCi-6alkyl, Ci.6alkylcarbonylCi.6alkyl, Ci.6alkylcarbonylC2-6alkenyl, Ci.6alkoxycarbonylCi_ 6alkyl, Ci.6alkylcarbonyloxyCi.6alkyl, N-Ci.4alkylaminocarbonylCi.6alkyl, N,N-diCi_ 4alkylaminocarbonylCi-6alkyl, Ci.4alkylsulfanylCi_6alkyl, Ci.6alkylsulfonylCi.6alkyl or d. 6alkylsulfonylaminoCi-6alkyl. Preferably, R 0 is hydrogen, Ci_8alkyl, C3.6alkenyl, C3.6alkynyl, cyanoC-i. 6alkyl, Ci_6haloalkyl, C3.6haloalkenyl, hydroxyCi_6alkyl, Ci.4alkoxyCi_6alkyl, Ci.4haloalkoxyCi_6alkyl, Ci_ 4alkoxyCi-4alkoxyCi.6alkyl or aminoCi_6alkyl. More preferably, R 0 is Ci_8alkyl, C3.6alkenyl, C3.6alkynyl, Ci_6haloalkyl or Ci.4alkoxyCi_6alkyl. Even more preferably, R 0 is Ci_8alkyl, C3.4alkenyl, C3.4alkynyl, Ci_ 4haloalkyl or Ci.2alkoxyCi.4alkyl. Still more preferably, R 0 is methyl, propyl, iso-propyl, n-butyl, iso- butyl, sec-butyl, pentyl, hexyl or Ci.4alkoxyCi_6alkyl.
In certain embodiments of the invention, R 0 may be methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl (1-methylpropyl), tert-butyl (1 ,1-dimethylethyl), n-pentyl, 2,2-dimethylpropyl, n-octyl, allyl (2- propen-1-yl), prop-2-yn-yl, but-2-ynyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 4-chlorobutyl, methoxymethyl, methoxyethyl or ethoxyethyl. When R 0 is d-8alkyl, it may be Ci_3alkyl, n-butyl, iso-butyl, sec-butyl or C5.8alkyl, or alternatively it may be methyl, ethyl, propyl, iso-propyl, butyl (n-butyl, iso-butyl, sec-butyl), pentyl, hexyl, heptyl or octyl. Further still, when R 0 is Ci_8alkyl it may be methyl, propyl, iso-propyl, butyl (n-butyl, iso-butyl, sec-butyl), pentyl or hexyl.
Preferably, in a compound according to formula (I) of the invention:
A1 is N or CR and A2 is CR2, wherein R and R2 are independently selected from hydrogen and fluoro;
A3 is CR3 and A4 is CR4, wherein R3 and R4 are independently selected from hydrogen and fluoro;
R5 and R6 are hydrogen, or R5 is hydrogen and R6 is methyl;
R7 is hydrogen;
R8 is -C(0)OR10;
R 0 is hydrogen, Ci_8alkyl, C3.6alkenyl, C3.6alkynyl, cyanoCi_6alkyl, Ci_6haloalkyl, C3.
6haloalkenyl, hydroxyCi_6alkyl, Ci.4alkoxyCi.6alkyl, Ci.4haloalkoxyCi.6alkyl, Ci.4alkoxyCi_ 4alkoxyCi.6alkyl or aminoCi_6alkyl; and
n is 1. More preferably, A1 is N or CR1 and A2 is CR2, wherein R and R2 are hydrogen;
A3 is CR3 and A4 is CR4, wherein R3 and R4 are hydrogen;
R5 and R6 are hydrogen;
R7 is hydrogen;
R8 is -C(0)OR10;
R 0 is hydrogen, Ci_8alkyl, C3.6alkenyl, C3.6alkynyl, cyanoCi_6alkyl, Ci_6haloalkyl, C3.
6haloalkenyl, hydroxyCi_6alkyl, Ci.4alkoxyCi_6alkyl, Ci.4haloalkoxyCi_6alkyl, Ci_4alkoxyCi_ 4alkoxyCi_6alkyl or aminoCi_6alkyl; and
n is 1. Even more preferably, A1 is N or CR1 and A2 is CR2, wherein R and R2 are hydrogen;
A3 is CR3 and A4 is CR4, wherein R3 and R4 are hydrogen;
R5 and R6 are hydrogen;
R7 is hydrogen;
R8 is -C(0)OR10;
R 0 is methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl (1-methylpropyl), n-pentyl, 2,2- dimethylpropyl, n-octyl, allyl (2-propen-1-yl), prop-2-yn-yl, but-2-ynyl, 2-fluoroethyl, 2- chloroethyl, 3-chloropropyl, 4-chlorobutyl, methoxymethyl, methoxyethyl or ethoxyethyl; and n is 1. The following lists provide definitions, including preferred definitions, for substituents n, A1, A2,
A3, A4, R1, R2, R3, R4, R5, R6, R7, R8 and R 3 (when R8 is -C(0)NR R12) with reference to the compounds of formula (I). For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below or elsewhere in this document. n represents 1 or 2. In some embodiments of the invention, n is 1. In other embodiments of the invention, n is 2. Preferably, n is 1.
A1 represents N or CR , wherein R represents hydrogen, halogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy; A2 represents N or CR2, wherein R2 represents hydrogen, halogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy;
A3 represents N or CR3, wherein R3 represents hydrogen or halogen; A4 represents N or CR4, wherein R4 represents hydrogen or halogen; and wherein no more than two of A1 to A4 are N (ie, 0, 1 or 2 of A1 to A4 may be N);
Preferably, A1 represents N or CR1 , wherein R is selected from hydrogen, fluoro, chloro, methoxy, or trifluoromethyl. Preferably, A2 represents CR2 and R2 is hydrogen or fluoro. Preferably, A3 represents CR3 and R3 is hydrogen, and A4 represents CR4 and R4 is hydrogen. Most preferably, A1 to A4 are C-H, or A1 is N and A2 to A4 are C-H.
In some embodiments of the invention, the 6-membered ring comprising A1 to A4 is a phenyl (where A1 to A4 are C-H), pyridinyl (where A1 or A3 is N and the other A positions are C-H), pyrimidinyl (where A1 and A3 are N and the other A positions are C-H), fluorophenyl (where A1 or A3 are C-F (preferably A3 is C-F) and the other A positions are C-H) or difluorophenyl (where A1 and A3 are C-F and the A2 and A4 positions are C-H) group. R5 and R6 are independently selected from hydrogen, C1_4alkyl, halogen, cyano, trifluoromethyl and difluoromethyl, or R5 and R6 together with the carbon atom they share form a cyclopropyl. Preferably, R5 and R6 are independently selected from hydrogen and C1_4alkyl, or R5 and R6 together with the carbon atom they share form a cyclopropyl. Preferably, R5 and R6 are hydrogen, or R5 is hydrogen and R6 is C1_4alkyl, preferably methyl or ethyl. More preferably, R5 and R6 are hydrogen.
In some embodiments of the invention, in compounds according to Formula (I), n is 1 , and R5 and R6 are independently selected from hydrogen and methyl. In other embodiments of the invention, in compounds according to Formula (I), n is 2, and R5 and R6 are independently selected from hydrogen and fluoro.
R7 is hydrogen. R8 represents -C(0)NR R12, wherein R is hydrogen, cyano, d-7alkyl, C2.6alkenyl, C2.6alkynyl, cyanoCi-6alkyl, Ci_6haloalkyl, C2-6haloalkenyl, hydroxyCi_6alkyl, Ci.4alkoxyCi.6alkyl, Ci.4haloalkoxyCi_ 6alkyl, Ci-4alkoxyCi.4alkoxyCi.6alkyl, C2-6alkynyloxyCi-6alkyl, aminoCi.6alkyl, N-Ci-4alkylaminoCi-6alkyl, N,N-diCi.4alkylanriinoCi.6alkyl, Ci.6alkylcarbonylCi.6alkyl, Ci.6alkylcarbonylC2.6alkenyl, d. 6alkoxycarbonylCi_6alkyl, Ci.6alkylcarbonyloxyCi.6alkyl, N-Ci.4alkylanriinocarbonylCi.6alkyl, N,N-diCi_ 4alkylanr)inocarbonylCi-6alkyl, Ci.4alkylsulfanylCi.6alkyl, Ci.6alkylsulfonylCi.6alkyl or Ci_ 6alkylsulfonylanr)inoCi-6alkyl. Preferably, R is hydrogen, cyano, Ci_6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoCi_4alkyl, Ci_6haloalkyl, C2.6haloalkenyl, hydroxyCi_6alkyl, Ci.4alkoxyCi_6alkyl, aminoCi.6alkyl or Ci-4alkylsulfanylCi-6alkyl. More preferably, R is hydrogen, cyano, Ci_6alkyl, C2.4alkenyl, C2.4alkynyl, cyanoCi_4alkyl, Ci_4haloalkyl, C2.4haloalkenyl, hydroxyCi_4alkyl, Ci_4alkoxyCi_4alkyl, aminoCi.4alkyl or Ci-4alkylsulfanylCi_4alkyl. Still more preferably, R is hydrogen, Ci_6alkyl or Ci.4alkoxyCi_6alkyl (including Ci_4alkoxyCi_4alkyl). In certain embodiments of the invention, R may be hydrogen, cyano, methyl, ethyl, n-propyl, iso-propyl (1-methylethyl), n-butyl, iso-butyl (2-methylpropyl), sec-butyl (1-methylpropyl), tert-butyl (1 ,1-dimethylethyl), n-pentyl, n-heptyl, 2,2-dimethylpropyl, allyl (2-propen-1-yl), cyanomethyl, 2- chloroethyl, 3-chloropropyl, 2,2,2-trifluoroethyl, methoxymethyl, methoxyethyl, ethoxycarbonylmethyl or methylsulfanylethyl.
R 2 is hydrogen, C1_4alkyl, Ci_4alkoxy, Ci.4alkoxyCi_6alkyl, C3.6alkenoxy or C3.6alkynoxy. Preferably, R 2 is hydrogen, Ci_4alkyl or Ci_4alkoxy. More preferably, R 2 is hydrogen, methyl, ethyl, methoxy or ethoxy. Still more preferably, R 2 is hydrogen, methyl, methoxy or ethoxy. R and R 2 together with the nitrogen atom they share may form a 4-, 5- or 6-membered cycle optionally containing a heteroatom comprising O, S or NR 3, wherein R 3 is hydrogen, methyl, methoxy, formyl or acyl.
Preferably, in a compound according to formula (I) of the invention:
A1 is N or CR and A2 is CR2, wherein R and R2 are independently selected from hydrogen and fluoro;
A3 is CR3 and A4 is CR4, wherein R3 and R4 are independently selected from hydrogen and fluoro;
R5 and R6 are hydrogen, or R5 is hydrogen and R6 is methyl;
R7 is hydrogen;
R8 is -C(0)NR R12
R is hydrogen, cyano, Ci_6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoCi_4alkyl, Ci_6haloalkyl, C2. 6haloalkenyl, hydroxyCi_6alkyl, Ci.4alkoxyCi_6alkyl, aminoCi_6alkyl or Ci.4alkylsulfanylCi_6alkyl; R 2 is hydrogen, methyl, methoxy or ethoxy; and
n is i . More preferably, A1 is N or CR and A2 is CR2, wherein R and R2 are hydrogen;
A3 is CR3 and A4 is CR4, wherein R3 and R4 are hydrogen;
R5 and R6 are hydrogen;
R7 is hydrogen;
R8 is -C(0)NR R12
R is hydrogen, d-4alkyl or Ci.4alkoxyCi.4alkyl;
R 2 is hydrogen, cyano, Ci_6alkyl, C2-6alkenyl, cyanoCi_4alkyl, Ci_6haloalkyl, Ci.4alkoxyCi_6alkyl or Ci-4alkylsulfanylCi.6alkyl; and
n is 1.
Even more preferably, A1 is N or CR1 and A2 is CR2, wherein R and R2 are hydrogen;
A3 is CR3 and A4 is CR4, wherein R3 and R4 are hydrogen;
R5 and R6 are hydrogen;
R7 is hydrogen;
R8 is -C(0)NR R12
R is hydrogen, cyano, methyl, ethyl, n-propyl, iso-propyl (1-methylethyl), n-butyl, iso-butyl (2- methylpropyl), sec-butyl (1-methylpropyl), tert-butyl (1 ,1-dimethylethyl), n-pentyl, n-heptyl, 2,2- dimethylpropyl, allyl (2-propen-1-yl), cyanomethyl, 2-chloroethyl, 3-chloropropyl, 2,2,2- trifluoroethyl, methoxymethyl, methoxyethyl, ethoxycarbonylmethyl or methylsulfanylethyl; R 2 is hydrogen, methyl, methoxy or ethoxy; and
n is 1.
Preferably, the compound according to Formula (I) is selected from: 2-methoxy-2-methyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide;
2-(difluoromethoxy)-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]acetamide;
N-[[2,3-difluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]-3,3,3-trifluoro-propanamide;
N-[[2,3-difluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]-2-methyl-butanamide;
N-[[2,3-difluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]butanamide;
3,3,3-trifluoro-N-[[2-fluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide;
3,3,3-trifluoro-N-[[3-fluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide;
2-fluoroethyl N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]carbamate;
1.1- diethyl-3-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]urea;
2-(difluoromethoxy)-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide;
1-methoxy-1-methyl-3-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]urea;
2- ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]butanamide;
3,3-dimethyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]butanamide;
3- chloro-2,2-dimethyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide;
2.2- dimethyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]but-3-ynamide;
1-ethoxy-3-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]urea;
methyl N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]carbamate; 2-methoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamid
2- methyl-N [4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]buta
3- methyl-N [4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]buta
N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]butanamide;
2,2-dimethyl-N [4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methy^
N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide;
prop-2-ynyl N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]carbamate; or
2-methyl-N-[2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]ethyl]propanamide. The compound of Formula I) may be a compound accordin to Formula (IA):
Figure imgf000017_0001
wherein
R and R2 are independently selected from hydrogen, chloro, fluoro, methyl, methoxy and trifluoromethyl; and
R3 and R4 are independently selected from hydrogen and halogen; wherein at least two of R , R2, R3 and R4 are hydrogen;
R5 and R6 are independently selected from hydrogen and C1_4alkyl; R7 is hydrogen; and R8 represents -C(0)R9, wherein R9 is hydrogen, Ci_6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoCi.
6alkyl, Ci_6haloalkyl, C2-6haloalkenyl, hydroxyd-6alkyl, Ci.4alkoxyCi.6alkyl, Ci.4haloalkoxyCi.6alkyl, Ci_ 4alkoxyCi.4alkoxyCi.6alkyl, C2-6alkynyloxyCi-6alkyl, aminoCi_6alkyl, N-Ci.4alkylaminoCi.6alkyl, N,N-diCi_ 4alkylaminoCi_6alkyl, Ci.6alkylcarbonylCi.6alkyl, Ci.6alkylcarbonylC2.6alkenyl, Ci.6alkoxycarbonylCi_ 6alkyl, Ci.6alkylcarbonyloxyCi.6alkyl, N-Ci.4alkylaminocarbonylCi.6alkyl, N,N-diCi_ 4alkylaminocarbonylCi_6alkyl, Ci.6alkylsulfanylCi.6alkyl, Ci.6alkylsulfonylCi.6alkyl or Ci_ 6alkylsulfonylaminoCi.6alkyl; or a salt or an N-oxide thereof. In the compounds of Formula (IA), preferably R and R2 are independently selected from hydrogen and fluoro. In the compounds of Formula (IA), preferably, R3 and R4 are independently selected from hydrogen and fluoro. More preferably, R3 and R4 are hydrogen. In the compounds of Formula (IA), three of R , R2, R3 and R4 may be hydrogen, wherein more preferably R2, R3 and R4 are hydrogen.
In the compounds of Formula (IA), preferably R5 and R6 are hydrogen, or R5 is hydrogen and R6 is Ci-4alkyl, preferably methyl or ethyl. More preferably, R5 and R6 are hydrogen.
In the compounds of Formula (IA), preferably R9 is hydrogen, d-6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoCi_6alkyl, Ci_6haloalkyl, C2-6haloalkenyl, hydroxyCi_6alkyl, Ci.4alkoxyCi.6alkyl, Ci.4haloalkoxyCi_ 6alkyl, Ci.4alkoxyC2-4alkoxyCi.6alkyl, C2-4alkynyloxyCi.6alkyl, aminoCi_6alkyl, N-Ci.4alkylaminoCi.6alkyl, or N,N-diCi.4alkylaminoCi.6alkyl, Ci.6alkylcarbonylCi.6alkyl, Ci.4alkylsulfanylCi_6alkyl or Ci_ 6alkylsulfonylCi_6alkyl. More preferably, R9 is hydrogen, Ci_6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoCi. 6alkyl, Ci_6fluoroalkyl, Ci_6chloroalkyl, hydroxyCi_6alkyl, Ci.4alkoxyCi_6alkyl, Ci.4fluoroalkoxyCi_6alkyl, Ci-4alkoxyC2-4alkoxyCi-6alkyl or Ci.6alkylcarbonylCi.6alkyl. Even more preferably, R9 is hydrogen, Ci_ 6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoCi_6alkyl, Ci_6fluoroalkyl, Ci_6chloroalkyl, hydroxyCi_6alkyl, Ci_ 2alkoxyCi_6alkyl, Ci.2fluoroalkoxyCi_6alkyl, Ci-2alkoxyC2-3alkoxyCi-6alky or Ci.6alkylcarbonylCi.6alkyl. Still more preferably, R9 is Ci_6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoCi_6alkyl, Ci_6fluoroalkyl, Ci_ 6chloroalkyl, Ci.4alkoxyCi_6alkyl or Ci.6alkylcarbonylCi.6alkyl, or R9 is Ci_6alkyl, C2.6alkenyl, C2.6alkynyl, Ci-6fluoroalkyl, Ci_6chloroalkyl or Ci.4alkoxyCi_6alkyl. Most preferably, R9 is Ci_6alkyl (such as methyl, ethyl, iso-propyl, n-butyl, pentyl), Ci.4alkoxyCi_6alkyl or C2.6alkynyl. In the compounds of Formula (IA), preferably R and R2 are independently selected from hydrogen and fluoro;
R3 and R4 are independently selected from hydrogen and fluoro;
R5 and R6 are hydrogen, or R5 is hydrogen and R6 is methyl;
R7 is hydrogen;
R8 is -C(0)R9; and
R9 is Ci_6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoCi_6alkyl, Ci_6haloalkyl, Ci.4alkoxyCi_6alkyl or d. 6alkylcarbonylCi_6alkyl.
In the compounds of Formula (IA), more preferably, R and R2 are hydrogen;
R3 and R4 are hydrogen;
R5 and R6 are hydrogen;
R7 is hydrogen;
R8 is -C(0)R9; and
R9 is Ci_6alkyl, C2.6alkenyl, C2.6alkynyl, Ci_6haloalkyl or Ci.4alkoxyCi_6alkyl.
In the compounds of Formula (IA), even more preferably, R and R2 are hydrogen; R3 and R4 are hydrogen;
R5 and R6 are hydrogen;
R7 is hydrogen;
R8 is -C(0)R9; and
R9 is Ci_6alkyl, Ci.4alkoxyCi.6alkyl or C2-6alkynyl.
The compounds of the present invention may be enantiomers of the compound of Formula (I) as represented by a Formula (la) or a Formula (lb) when n is 1 , wherein R5 and R6 are different (see below), or indeed when n is 2 and at only one of the two carbon positions bound to R5 and R6 , R5 and R6 are different.
Figure imgf000019_0001
(la) (lb)
Likewise, the compounds of the present invention may be diastereomers of the compound of Formula (I) when n is 2, and wherein at each of the two carbon positions bound to R5 and R6, R5 and R6 are different.
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 (ie, the compounds of formula (l-l) and formula (l-ll) as shown below) at the CF3-oxadiazole motif. This dynamic equilibrium may be important for the biological activity of the compounds of Formula (I). The designations of n, A1, A2, A3, A4, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 0, R11, R 2 and R 3 with reference to the compounds of formula (I) of the present invention apply generally to the compounds of Formula (l-l) and Formula (l-ll), as well as to the specific disclosures of combinations of n, A1, A2, A3, A4, R , R2, R3, R4, R5, R6, R7, R8, R9, R 0, R11, R 2 and R 3 as represented in the compounds of Tables 1.1 to 1.10, and 2.1 to 2.10 and Tables 3.1 to 3.13 below or the compounds 1.1 to 1.1 11 described in Table T1 (below) or the compounds 2.1 to 2.36 described in Table T2 (below), or the compounds 3.1 to 3.41 described in Table T3 (below).
Figure imgf000020_0001
(l-l) (l-ll)
Compounds of the present invention can be made as shown in the following schemes 1 to 14, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula (I).
The compounds of formula (I) can be obtained by an amide coupling transformation with compounds of formula (II) and compounds of formula (III), wherein Z represents -R9, -OR10, or - NR R12, by activating the carboxylic acid function of the compounds of formula (III), a process that usually takes place by converting the -OH of the carboxylic acid into a good leaving group, such as a chloride group, for example by using (COCI)2 or SOCI2, prior to treatment with the compounds of formula (II), preferably in a suitable solvent (eg, dimethylformamide, dichloromethane or tetrahydrofuran), preferably at a temperature of between 25°C and 100°C, and optionally in the presence of a base such as triethylamine or A/,A/-diisopropylethylamine, or under conditions described in the literature for an amide coupling. For examples, see WO 2003/028729. 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 is shown in Scheme 1.
Figure imgf000021_0001
Scheme
Alternatively, compounds of formula (I) can be prepared from compounds of formula (II) via treatment with triphosgene, in a suitable solvent (eg, ethyl acetate, CHCI3, or toluene) with heating between 65°C and 100°C followed by the addition of suitable nucleophiles of formula (IV), wherein Z- Nu is an organometallic (eg, an organomagnesium, organozinc, or organolithium) reagent in a suitable solvent (eg, toluene, diethyl ether or tetrahydrofuran) at a temperature between -78°C and 25°C. For related examples, see Charalambides, Y. C, Moratti, S. C. Synth. Commun. (2007), 37, 1037; Schaefer, G. ei al Angew. Chem., Int. Ed. (2012) 51, 9173; Lengyel, I. ei al Heterocycles (2007), 73, 349; and Benalil, A ei al Synthesis (1991 ), 9, 787. Furthermore, compounds of formula (I) can be prepared from compounds of formula (II) via treatment with triphosgene, in a suitable solvent (eg, 1 ,2- dichloroethane, CHCI3, or toluene) followed by the addition of suitable nucleophiles of formula (IV), wherein Z-Nu represents HOR 0 or HN(R )R12 in the presence of a suitable base such as trieth lamine. This reaction is shown in Scheme 2
Figure imgf000021_0002
Scheme 2
Additionally, compounds of formula (I), wherein R is -C(0)R , can be prepared from compounds of formula (VI), wherein X is CI, Br or I, via treatment with amides of formula (V), wherein Y is tert-butylcarboxylate, in the presence of a suitable base, such as NaH, in a suitable solvent, such as dimethylformamide, at a temperature between 0°C and 100°C. In some cases, a better reaction performance may be gained from use of a catalyst (eg, Nal or 4-dimethylaminopyridine) and with microwaves irradiation. Removal of the tert-butylcarboxylate group with concomitant liberation of benzylamides of formula (I) occurs upon treatment with HCI or trifluoroacetic acid in a suitable solvent (eg, dioxane or MeOH). Compounds of formula (V) are commercially available. For related examples, see Miyawaki, K. et al Heterocycles (2001 ), 54, 887. This reaction is shown in Scheme 3.
Figure imgf000022_0001
Scheme 3
Furthermore, compounds of formula (I) can be prepared from compounds of formula (VII) by treatment with trifluoroacetic anhydride in the presence of a base (eg, pyridine or 4- dimethylaminopyridine) in a suitable solvent, such as tetrahydrofuran or ethanol, at a temperature between 25°C and 75°C. For related examples, see WO 2003/028729 and WO 2010/045251. This is shown in Scheme 4.
Figure imgf000022_0002
(VII) (I)
Scheme 4
Compounds of formula (VII) can be prepared from compounds of formula (VIII) by treatment with a hydroxylamine hydrochloride salt in the presence of a base, such as triethylamine, in a suitable solvent, such as methanol, at a temperature between 0°C and 100°C. For related examples, see Kitamura, S. ei al Chem. Pharm. Bull. (2001 ), 49, 268 and WO 2013/066838. This reaction is shown in Scheme 5.
Figure imgf000022_0003
(VIII) (VII)
Scheme 5 Compounds of formula (VIII) can be prepared from compounds of formula (IX), wherein Z is Br or I, 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 100°C and 120°C. For related examples, see US 2007/0155739 and WO 2009/022746. Compounds of formula (IX) are commercially available or prepared using known methods. This reaction is shown in Scheme 6.
Figure imgf000023_0001
(IX) (VIII)
Scheme 6
Compounds of formula (II), wherein n is 1 or 2, can be prepared from carbonyl compounds of formula (X), wherein m is 0 or 1 , when R6A is hydrogen, starting with treatment by compounds of formula (XI), wherein RPG is tert-butylsulfinamide, optionally in the presence of an activating reagent (eg, Ti(OEt)4), in a suitable solvent, (eg, tetrahydrofuran) at a temperature between 60°C and 75°C and followed by the addition of a reagent of formula (XII), wherein R5A is H, cyano, or C1_4alkyl, such as an alkyl Grignard reagent (eg. alkylMgBr), Me3SiCN, or a metal hydride (eg, NaBH4, NaBH3CN, or LiAIH4), in a suitable solvent, (eg, tetrahydrofuran or ethanol) at temperatures between 0°C and 25°C. Removal of the tert-butanesulfinyl group with concomitant liberation of amine compounds of formula (II) occurs upon treatment with methanolic HCI. For related examples, see Cogan, D., Ellman J. A. J. Am. Chem. Soc. 1999), 121, 268. This reaction is shown in Scheme7.
Figure imgf000023_0002
(X)
Scheme 7
Additionally, compounds of formula (II) can be prepared from compounds of formula (XIV), wherein X is CI or Br, by treatment with amines of formula (XIII), wherein Y is tert-butylcarboxylate, in a suitable solvent (eg, tetrahydrofuran) at a temperature between 25°C and 60°C. Removal of the tert- butylcarboxylate groups with concomitant liberation of benzylamines of formula (II) occurs upon treatment with HCI or trifluoroacetic acid in a suitable solvent (eg, dioxane or MeOH). For related examples, see Miyawaki, K. ef al Heterocycles (2001 ), 54, 887, WO 2003/028729, and WO 2013/066839. This reaction is shown in Scheme 8.
Figure imgf000024_0001
Scheme 8
Compounds of formula (XIV), wherein n is 1 and X is CI or Br, can be prepared from compounds of formula (XV), by treatment with a halogen source (eg, N-bromosuccimide (NBS) or N- chlorosuccimide (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. For related examples, see Liu, S. ei al Synthesis (2001 ), 14, 2078 and Kompella, A. ei al Or . Proc. Res. Dev. (2012), 16, 1794. This reaction is shown in Scheme 9.
Figure imgf000024_0002
QV) (XIV)
Scheme 9
Compounds of formula (XVI), wherein W is Br, I, or CN, can be obtained by an amide coupling transformation with compounds of formula (III) (wherein Z represents -R9, -OR10, or -N(R )R12) and compounds of formula (XVII) by activating the carboxylic acid function of the compounds of formula (III), a process that usually takes place by converting the -OH of the carboxylic acid into a good leaving group, such as a chloride group, for example by using (COCI)2 or SOCI2, prior to treatment with the compounds of formula (XVII), preferably in a suitable solvent (eg, dimethylformamide, dichloromethane or tetrahydrofuran), preferably at a temperature of between 25°C and 100°C, and optionally in the presence of a base such as triethylamine or A/,A/-diisopropylethylamine, or under conditions described in the literature for an amide coupling. This reaction is shown in Scheme 12 below. For examples, see WO 2003/028729; Dosa, S. ei al Bioorg. Med. Chem. (2012), 20, 6489; and WO 2014/093378. 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 Pesticide Research Journal (2009), 21 , 133; and Crich, D., Zou, Y. J. Org. Chem. (2005), 70, 3309. This reaction is shown in Scheme 10.
Figure imgf000025_0001
(III) (XVII) (XVI)
Scheme 10
Alternatively, compounds of formula (XVI), wherein R is -C(0)R and W is Br, I, or CN, can be prepared from compounds of formula (XVIII), wherein X is CI, Br or I, via treatment with amides of formula (V), wherein Y is tert-butylcarboxylate, in the presence of a suitable base, such as NaH, in a suitable solvent, such as dimethylformamide, at a temperature between 0°C and 100°C. In some cases, a better reaction performance may be gained from use of a catalyst (eg, Nal or 4- dimethylaminopyridine) and with microwave irradiation. Removal of the tert-butylcarboxylate groups with concomitant liberation of benzylamides of formula (XVI) occurs upon treatment with HCI or trifluoroacetic acid in a suitable solvent (eg, dioxane or MeOH). Compounds of formula (XVIII) are commercially available. For related examples, see Miyawaki, K. ef al Heterocycles (2001 ), 54, 887. This reaction is shown in Scheme 1 1.
Figure imgf000025_0002
(V) (XVIII) (XVI)
Scheme 1 1
Additionally, compounds of formula (XVI), wherein W is Br, I or CN, can be prepared from compounds of formula (XVIII), wherein X is CI, Br, I, or -OS02Me, via treatment with amines of formula (XIII), wherein Y is tert-butylcarboxylate in a suitable solvent (eg, methanol or ethanol) at a temperature between 0°C and 100°C. In some cases, a better reaction performance may be gained from use of a catalyst (eg, Nal or 4-dimethylaminopyridine) and with microwave irradiation. Removal of the tert-butylcarboxylate groups with concomitant liberation of benzylamines of formula (XVI) occurs upon treatment with HCI or trifluoroacetic acid in a suitable solvent (eg, dioxane or MeOH). For related examples, see WO 2010/1 12461 , WO 2008/040492, and WO 2013/071232. This reaction is shown in Scheme 12.
Figure imgf000026_0001
Scheme 12
Compounds of formula (XVIII), wherein W is Br, I, or CN and X is CI or Br, are either commercially available or can be prepared from compounds of formula (XIX), by treatment with a halogen source, (eg, N-bromosuccimide (NBS) or N-chlorosuccimide (NCS)) and a radical initiator, such as (PhC02)2 or azobisisobutyronitrile (AIBN), in the presence of ultraviolet light, in a suitable solvent, such as tetrachloromethane, at temperatures between 55°C and 100°C. For related examples, see Liu, S. ef al Syntheis (2001 ), 14, 2078 and Kompella, A. ef al Org. Proc. Res. Dev. (2012), 16, 1794. This reaction is shown in Scheme 13.
Figure imgf000026_0002
(XIX) (XVIII)
Scheme 13
Alternatively, compounds of formula (XVIII), wherein W is Br, I, or CN and X is CI, Br, I, or OS02Me are either commercially available or can be prepared from compounds of formula (XX), by treatment with a halogen source (eg, CBr4, CCI4 or l2) in the presence of triphenylphosphine, or with methanesulfonyl chloride (CIS02Me), in a suitable solvent, (eg, dichloromethane) at a temperature between 0°C and 100°C. For related examples, see Liu, H. ef al Bioorg. Med. Chem. (2008), 16, 10013, WO 2014/020350 and Kompella, A. ef al Bioorg. Med. Chem. Lett. (2001 ), 7, 3161 . Compounds of formula (XXII) are commercially available. This reaction is shown in Scheme 14.
Figure imgf000026_0003
(XX) (XVIII)
Scheme 14 As already indicated, surprisingly, it has now been found that the novel 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. It is also possible to use compounds of formula (I) as fungicide. The term "fungicide" as used herein means a compound that controls, modifies, or prevents the growth of fungi. The term "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 deviation from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection.
It may also be possible to use compounds of formula (I) as dressing agents for the treatment of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings, for 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.
Furthermore, 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. In addition, the invention could be used to protect non-living materials from fungal attack, e.g. lumber, wall boards and paint.
The compounds of formula (I) are for example, effective against 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. inclusing B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp, Cercospora spp. including C. arachidicola, Cercosporidium personatum, Cladosporium spp, Claviceps purpurea, Coccidioides immitis, Cochliobolus spp, Colletotrichum spp. including C. musae, Cryptococcus neoformans, Diaporthe spp, Didymella spp, Drechslera spp, Elsinoe spp,Epidermophyton spp, Erwinia amylovora, Erysiphe spp. including E. cichoracearum, Eutypa lata, Fusarium spp. including F. culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, F. solani, Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium spp, Hemileia spp, Histoplasma spp. including H. 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. philippinensis and P. sorghi, Peronospora spp, Phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp, Phoma spp, Phomopsis viticola, Phytophthora spp. including P. infestans, Plasmopara spp. including P. halstedii, P. viticola, Pleospora spp., Podosphaera spp. including 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. ultimum, Ramularia spp, Rhizoctonia spp, Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium spp, Scedosporium spp. including S. apiospermum and S. prolificans, Schizothyrium pomi, Sclerotinia spp, Sclerotium spp, Septoria spp, including S. nodorum, S. tritici, Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix spp, Stagonospora nodorum, Stemphylium spp,. Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia spp, Trichoderma spp. including T. harzianum, T. pseudokoningii, T. viride, Trichophyton spp, Typhula spp, Uncinula necator, Urocystis spp, Ustilago spp, Venturia spp. including V. inaequalis, Verticillium spp, and Xanthomonas spp. 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.
Within the scope of present invention, 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. 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.
The term "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. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names Round upReady®, Herculex I® and LibertyLink®.
The term "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.
Examples of such plants are: 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 expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CrylllA toxin); NatureGard® Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt1 1 corn borer (CB) trait), Agrisure® RW (corn rootworm trait) and Protecta®.
The term "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 δ-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. or 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, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
Further, in the context of the present invention there are to be understood by δ-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. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such 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.
The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. 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. Such 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). „„
30
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 CrylAc toxin); Bollgard II® (cotton variety that expresses a CrylAc and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a CrylAb toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt1 1 corn borer (CB) trait) and Protecta®.
Further examples of such transgenic crops are:
1. 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 CrylAb toxin. Bt1 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
2. Bt176 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 CrylAb toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. 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.
4. 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. 6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1 160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cryl F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.
7. NK603 * 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 term "locus" as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
The term "plants" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
The term "plant propagation material" is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There 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. Preferably "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, e.g. for agricultural use, 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; and/or stickers such as dextrins, glue or synthetic resins.
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. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene- butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
Other useful formulations 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, Ν,Ν-dimethyl formamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethyl acetate, 2-ethyl hexanol, ethylene carbonate, 1 , 1 ,1-trichloroethane, 2-heptanone, alpha pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octyl amine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerine and N-methyl-2-pyrrolidinone. Water is generally the carrier of choice for the dilution of concentrates.
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. 18 ethoxylate; 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; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.
Other 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.
In addition, further, other 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.
In addition, the compositions of the invention may also be applied with one or more system ically acquired resistance inducers ("SAR" inducer). SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
The compounds of formula (I) are normally used in the form of agrochemical compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g. fertilizers or micronutrient donors or other preparations, which influence the growth of plants. They can also be selective herbicides 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. Preferably said composition may comprise at least one or more pesticidal ly-active compounds, for example an additional fungicidal active ingredient in addition to the compound of formula (I).
The compound of formula (I) may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingredient may, in some cases, result in unexpected synergistic activities.
Examples of 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 fungicides, organophosphorous fungicides, organotin fungicides, oxathiin fungicides, oxazole fungicides, phenylsulfamide fungicides, polysu If ide fungicides, pyrazole fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungicides, quinone fungicides, quinoxaline fungicides, strobilurin fungicides, sulfonanilide fungicides, thiadiazole fungicides, thiazole fungicides, thiazolidine fungicides, thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, valinamide fungicides, and zinc fungicides.
Examples of suitable additional active ingredients also include the following: 3-difluoromethyl-
1- methyl-1 H-pyrazole-4-carboxylic acid (9-dichloromethylene-1 ,2,3,4-tetrahydro-1 ,4-methano- naphthalen-5-yl)-amide , 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid methoxy-[1-methyl- 2-(2,4,6-trichlorophenyl)-ethyl]-amide , 1-methyl-3-difluoromethyl-1 H-pyrazole-4-carboxylic acid (2- dichloromethylene-3-ethyl-1-methyl-indan-4-yl)-amide (1072957-71-1 ), 1-methyl-3-difluoromethyl-1 H- pyrazole-4-carboxylic acid (4'-methylsulfanyl-biphenyl-2-yl)-amide, 1-methyl-3-difluoromethyl-4H- pyrazole-4-carboxylic acid [2-(2,4-dichloro-phenyl)-2-methoxy-1-methyl-ethyl]-amide, (5-Chloro-2,4- dimethyl-pyridin-3-yl)-(2,3,4-trimethoxy-6-methyl-phenyl)-methanone, (5-Bromo-4-chloro-2-methoxy- pyridin-3-yl)-(2,3,4-trimethoxy-6-methyl-phenyl)-methanone, 2-{2-[(E)-3-(2,6-Dichloro-phenyl)-1- methyl-prop-2-en-(E)-ylideneaminooxymethyl]-phenyl}-2-[(Z)-methoxyimino]-N-methyl-acetamide, 3-[5- (4-Chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, (E)-N-methyl-2- [2- (2, 5- dimethylphenoxymethyl) phenyl]-2-methoxy-iminoacetamide, 4-bromo-2-cyano-N, N-dimethyl-6- trifluoromethylbenzimidazole-1-sulphonamide, a- [N-(3-chloro-2, 6-xylyl)-2-methoxyacetamido]-y- butyrolactone, 4-chloro-2-cyano-N, - dimethyl-5-p-tolylimidazole-1-sulfonamide, N-allyl-4, 5,-dimethyl-
2- trimethylsilylthiophene-3-carboxamide, N- (l-cyano-1 , 2-d i m ethyl p ropy I )-2- (2, 4-dichlorophenoxy) propionamide, N- (2-methoxy-5-pyridyl)-cyclopropane carboxamide, (.+-.)-cis-1-(4-chlorophenyl)-2- (1 H-1 ,2,4-triazol-1-yl)-cycloheptanol, 2-(1-iert-butyl)-1-(2-chlorophenyl)-3-(1 ,2,4-triazol-1-yl)-propan-2- ol, 2',6'-dibromo-2-methyl-4-trifluoromethoxy-4'-trifluoromethyl-1 ,3-thiazole- 5-carboxanilide, 1- imidazolyl-1-(4'-chlorophenoxy)-3,3-dimethylbutan-2-one, methyl (E)-2-[2-[6-(2- cyanophenoxy)pyrimidin-4-yloxy]phenyl]3-methoxyacrylate, methyl (E)-2-[2-[6-(2- thioamidophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[6-(2- fluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[6-(2,6- difluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacryla te, methyl (E)-2-[2-[3-(pyrimidin-2- yloxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[3-(5-methylpyrimidin-2-yloxy)- phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[3-(phenyl-sulphonyloxy)phenoxy]phenyl-3- methoxyacrylate, methyl (E)-2-[2-[3-(4-nitrophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2- [2-phenoxyphenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3,5-dimethyl-benzoyl)pyrrol-1-yl]-3- methoxyacrylate, methyl (E)-2-[2-(3-methoxyphenoxy)phenyl]-3-methoxyacrylate, methyl (E)-2[2-(2- phenylethen-1-yl)-phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3,5-dichlorophenoxy)pyridin-3-yl]-3- methoxyacrylate, methyl (E)-2-(2-(3-(1 ,1 ,2,2-tetrafluoroethoxy)phenoxy)phenyl)-3-methoxyacrylate, methyl (E)-2-(2-[3-(alpha-hydroxybenzyl)phenoxy]phenyl)-3-methoxyacrylate, methyl (E)-2-(2-(4- phenoxypyridin-2-yloxy)phenyl)-3-methoxyacrylate, methyl (E)-2-[2-(3-n-propyloxy-phenoxy)phenyl]3- methoxyacrylate, methyl (E)-2-[2-(3-isopropyloxyphenoxy)phenyl]-3-methoxyacrylate, methyl (E)-2-[2- [3-(2-fluorophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3-ethoxyphenoxy)phenyl]-3- methoxyacrylate, methyl (E)-2-[2-(4-ieri-butyl-pyridin-2-yloxy)phenyl]-3-methoxyacrylate, methyl (E)-2- [2-[3-(3-cyanophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[(3-methyl-pyridin-2- yloxymethyl)phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[6-(2-methyl-phenoxy)pyrimidin-4- yloxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(5-bromo-pyridin-2-yloxymethyl)phenyl]-3- methoxyacrylate, methyl (E)-2-[2-(3-(3-iodopyridin-2-yloxy)phenoxy)phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[6-(2-chloropyridin-3-yloxy)pyrimidin-4-yloxy]phenyl]-3-methoxyac rylate, methyl (E),(E)-2-[2- (5,6-dimethylpyrazin-2-ylmethyloximinomethyl)phenyl]-3-methox yacrylate, methyl (E)-2-{2-[6-(6- methylpyridin-2-yloxy)pyrimidin-4-yloxy]phenyl}-3-methoxy-a crylate, methyl (E),(E)-2-{ 2-(3- methoxyphenyl)methyloximinomethyl]-phenyl}-3-methoxyacrylate, methyl (E)-2-{2-(6-(2- azidophenoxy)-pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate, methyl (E),(E)-2-{2-[6-phenylpyrimidin-4- yl)-methyloximinomethyl]phenyl}-3-methox yacrylate, methyl (E),(E)-2-{2-[(4-chlorophenyl)- methyloximinomethyl]-phenyl}-3-methoxyacryl ate, methyl (E)-2-{2-[6-(2-n-propylphenoxy)-1 ,3,5- triazin-4-yloxy]phenyl}-3-methoxyacr ylate, methyl (E),(E)-2-{2-[(3- nitrophenyl)methyloximinomethyl]phenyl}-3-methoxyacrylate, 3-chloro-7-(2-aza-2,7,7-trimethyl-oct-3- en-5-ine), 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, 3-iodo-2-propinyl alcohol, 4- chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenyl ethylcarbamate, 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propinyl n-butylcarbamate, 3-iodo-2-propinyl n-hexylcarbamate, 3-iodo-2-propinyl cyclohexyl-carbamate, 3-iodo-2-propinyl phenylcarbamate; phenol derivatives, such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl- 4-chlorophenol, phenoxyethanol, dichlorophene, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2- benzyl-4-chlorophenol, 5-hydroxy-2(5H)-furanone; 4,5-dichlorodithiazolinone, 4,5-benzodithiazolinone, 4,5-trimethylenedithiazolinone, 4,5-dichloro-(3H)-1 ,2-dithiol-3-one, 3,5-dimethyl-tetrahydro-1 ,3,5- thiadiazine-2-thione, N-(2-p-chlorobenzoylethyl)-hexaminium chloride, acibenzolar, acypetacs, alanycarb, albendazole, aldimorph, allicin, allyl alcohol, ametoctradin, amisulbrom, amobam, ampropylfos, anilazine, asomate, aureofungin, azaconazole, azafendin, azithiram, azoxystrobin, barium polysulfide, benalaxyl, benalaxyl-M, benodanil, benomyl, benquinox, bentaluron, benthiavalicarb, benthiazole, benzalkonium chloride, benzamacril, benzamorf, benzohydroxamic acid, benzovindiflupyr, berberine, bethoxazin, biloxazol, binapacryl, biphenyl, bitertanol, bithionol, bixafen, blasticidin-S, boscalid, bromothalonil, bromuconazole, bupirimate, buthiobate, butylamine calcium polysulfide, captafol, captan, carbamorph, carbendazim, carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA41396, CGA41397, chinomethionate, chitosan, chlobenthiazone, chloraniformethan, chloranil, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlorozolinate, chlozolinate, climbazole, clotrimazole, clozylacon, copper containing compounds such as copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper oxyquinolate, copper silicate, copper sulphate, copper tallate, copper zinc chromate and Bordeaux mixture, cresol, cufraneb, cuprobam, cuprous oxide, cyazofamid, cyclafuramid, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole, cyprodinil, dazomet, debacarb, decafentin, dehydroacetic acid, di-2-pyridyl disulphide 1 , 1 '-dioxide, dichlofluanid, diclomezine, dichlone, dicloran, dichlorophen, dichlozoline, diclobutrazol, diclocymet, diethofencarb, difenoconazole, difenzoquat, diflumetorim, O, O-di-iso-propyl-S-benzyl thiophosphate, dimefluazole, dimetachlone, dimetconazole, dimethomorph, dimethirimol, diniconazole, diniconazole-M, dinobuton, dinocap, dinocton, dinopenton, dinosulfon, dinoterbon, diphenylamine, dipyrithione, disulfiram, ditalimfos, dithianon, dithioether, dodecyl dimethyl ammonium chloride, dodemorph, dodicin, dodine, doguadine, drazoxolon, edifenphos, enestroburin, epoxiconazole, etaconazole, etem, ethaboxam, ethirimol, ethoxyquin, ethilicin, ethyl (Z)-N-benzyl-N ([methyl (methyl-thioethylideneamino- oxycarbonyl) amino] thio)^-alaninate, etridiazole, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, flupicolide, fluopyram, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutanil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fuberidazole, furalaxyl, furametpyr, furcarbanil, furconazole, furfural, furmecyclox, furophanate, glyodin, griseofulvin, guazatine, halacrinate, hexa chlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexylthiofos, hydrargaphen, hydroxyisoxazole, hymexazole, imazalil, imazalil sulphate, imibenconazole, iminoctadine, iminoctadine triacetate, inezin, iodocarb, ipconazole, ipfentrifluconazole, iprobenfos, iprodione, iprovalicarb, isopropanyl butyl carbamate, isoprothiolane, isopyrazam, isotianil, isovaledione, izopamfos, kasugamycin, kresoxim- methyl, LY186054, LY21 1795, LY248908, mancozeb, mandipropamid, maneb, mebenil, mecarbinzid, mefenoxam, mefentrifluconazole, mepanipyrim, mepronil, mercuric chloride, mercurous chloride, meptyldinocap, metalaxyl, metalaxyl-M, metam, metazoxolon, metconazole, methasulfocarb, methfuroxam, methyl bromide, methyl iodide, methyl isothiocyanate, metiram, metiram-zinc, metominostrobin, metrafenone, metsulfovax, milneb, moroxydine, myclobutanil, myclozolin, nabam, natamycin, neoasozin, nickel dimethyldithiocarbamate, nitrostyrene, nitrothal-iso- propyl, nuarimol, octhilinone, ofurace, organomercury compounds, orysastrobin, osthol, oxadixyl, oxasulfuron, oxine- copper, oxolinic acid, oxpoconazole, oxycarboxin, parinol, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, penthiopyrad, phenamacril, phenazin oxide, phosdiphen, phosetyl-AI, phosphorus acids, phthalide, picoxystrobin, piperalin, polycarbamate, polyoxin D, polyoxrim, polyram, probenazole, prochloraz, procymidone, propamidine, propamocarb, propiconazole, propineb, propionic acid, proquinazid, prothiocarb, prothioconazole, pydiflumetofen, pyracarbolid, pyraclostrobin, pyrametrostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyridinitril, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, pyroxychlor, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinacetol, quinazamid, quinconazole, quinomethionate, quinoxyfen, quintozene, rabenzazole, santonin, sedaxane, silthiofam, simeconazole, sipconazole, sodium pentachlorophenate, spiroxamine, streptomycin, sulphur, sultropen, tebuconazole, tebfloquin, tecloftalam, tecnazene, tecoram, tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide, 2- (thiocyanomethylthio) benzothiazole, thiophanate-methyl, thioquinox, thiram, tiadinil, timibenconazole, tioxymid, tolclofos- methyl, tolylfluanid, triadimefon, triadimenol, triamiphos, triarimol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumazole, triforine, triflumizole, triticonazole, uniconazole, urbacide, validamycin, valifenalate, vapam, vinclozolin, zarilamid, zineb, ziram, and zoxamide.
The compounds of the invention may also be used in combination with anthelmintic agents. Such 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.
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.
Other examples of such biologically active compounds that the compounds of the invention may be used in combination with include but are not restricted to the following:
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, methacriphos, methamidophos, methidathion, methyl- parathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, paraoxon, parathion, parathion-methyl, phenthoate, phosalone, phosfolan, phosphocarb, phosmet, phosphamidon, phorate, phoxim, pirimiphos, pirimiphos- methyl, profenofos, propaphos, proetamphos, prothiofos, pyraclofos, pyridapenthion, quinalphos, sulprophos, temephos, terbufos, tebupirimfos, tetrachlorvinphos, thimeton, triazophos, trichlorfon, vamidothion.
5 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-
10 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, flucythrinate, flumethrin, fluvalinate (D isomer), imiprothrin, cyhalothrin, lambda-cyhalothrin, permethrin, phenothrin,
15 prallethrin, pyrethrins (natural products), resmethrin, tetramethrin, transfluthrin, theta-cypermethrin, silafluofen, t-fluvalinate, tefluthrin, tralomethrin, Zeta-cypermethrin.
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
20 antagonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenoids: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.
Other 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,
25 diacloden, diafenthiuron, DBI-3204, dinactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, ethofenprox, fenazaquin, flumite, MTI- 800, fenpyroximate, fluacrypyrim, flubenzimine, flubrocythrinate, flufenzine, flufenprox, fluproxyfen, halofenprox, hydramethylnon, IKI-220, kanemite, NC-196, neem guard, nidinorterfuran, nitenpyram, SD-35651 , WL-108477, pirydaryl, propargite, protrifenbute, pymethrozine, pyridaben, pyrimidifen, NC-1 1 1 1 , R-
30 195,RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601 , silafluofen, silomadine, spinosad, tebufenpyrad, tetradifon, tetranactin, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad, triazamate, triethoxyspinosyn, trinactin, verbutin, vertalec, YI-5301.
Biological agents: Bacillus thuringiensis ssp aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, virus and fungi.
35 Bactericides: chlortetracycline, oxytetracycline, streptomycin.
Other biological agents: enrofloxacin, febantel, penethamate, moloxicam, cefalexin, kanamycin, pimobendan, clenbuterol, omeprazole, tiamulin, benazepril, pyriprole, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, ceftiour, carprofen, metaflumizone, praziquarantel, thiabendazole. Another aspect of invention is related to the use of a compound of formula (I) or of a preferred individual compound as defined herein, of a composition comprising at least one compound of formula (I) or at least one preferred individual compound as above-defined, or of a fungicidal or insecticidal mixture comprising at least one compound of formula (I) or at least one preferred individual compound as above-defined, in admixture with other fungicides or insecticides as described above, for controlling or preventing infestation of plants, e.g. useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living materials by insects or by phytopathogenic microorganisms, preferably fungal organisms.
A further aspect of invention is related to a method of controlling or preventing an infestation of plants, e.g., useful plants such as crop plants, propagation material thereof, e.g. seeds, harvested crops, e.g., harvested food crops, or of non-living materials by insects or by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of formula (I) or of a preferred individual compound as above-defined as active ingredient to the plants, to parts of the plants or to the locus thereof, to the propagation material thereof, or to any part of the non-living materials.
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. However, the compounds of formula (I) can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field. The compounds of formula I may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
A formulation, 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. When used as seed drenching agent, convenient dosages are from 10mg to 1g of active substance per kg of seeds.
When the combinations of the present invention are used for treating seed, 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. Suitably, a 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.
The 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), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
Such 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). Also 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. the ondensation product of formaldehyde with naphthalene sulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkyl sulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.
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. Such 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.
In general, 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.
Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations. „„
42
Table 1.1 : This table discloses 107 specific compounds of the formula T-1 ):
Figure imgf000043_0001
wherein n is 1 , A1 is C-R , A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1 , R2, R3, R4, R5, R6, and R7 are hydrogen and R9 is as defined below in the Table 1.
Each of Tables 1.2 to 1.10 (which follow Table 1.1 ) make available 107 individual compounds of the formula (T-1 ) in which n, A1 , A2, A3, A4, R5, R6 and R7 are as specifically defined in Tables 1.2 to 1.10, which refer to Table 1 wherein R9 is specifically defined. Table 1
Compound Compound
no. R9 no. R9
1.001 methyl 1.055 2,2,2-trifluoroethyl
1.002 ethyl 1.056 3,3,3-trifluoropropyl
1.003 propyl 1.057 4,4,4-trifluorobutyl
1.004 isopropyl 1.058 fluoromethyl
1.005 butyl 1.059 difluoromethyl
1.006 sec-butyl 1.060 2-fluoroethyl
1.007 tert-butyl 1.061 3-fluoropropyl
1.008 isobutyl 1.062 4-fluorobutyl
1.009 pentyl 1.063 1-fluoroethyl
1.010 1-ethylpropyl 1.064 2-fluoropropyl
1.01 1 2-ethylbutyl 1.065 chloromethyl
1.012 2,2-dimethylpropyl 1.066 2-chloroethyl
1.013 1 , 1-dimethylbutyl 1.067 methylsulfanylmethyl
1.014 2,2-dimethylbutyl 1.068 methylsulfonylmethyl
1.015 ethenyl 1.069 2-methylsulfanylethyl
1.016 propen-2-yl 1.070 2-methylsulfonylethyl
1.017 allyl 1.071 methanesulfonamidomethyl
1.018 (E)-but-2-enyl 1.072 methanesulfonamidoethyl
1.019 2-methylallyl 1.073 2-(methylamino)-2-oxo-ethyl
1.020 1 , 1-dimethylallyl 1.074 2-(ethylamino)-2-oxo-ethyl
1.021 3-methylbut-2-enyl 1.075 acetamidomethyl
1.022 (E)-1 , 1-dimethylbut-2-enyl 1.076 acetamidoethyl 1.023 but-3-enyl 1.077 1-methyl-3-oxo-butyl
1.024 prop-2-ynyl 1.078 3-m ethoxy- 1 -methyl-3-oxo-propyl
1.025 but-3-ynyl 1.079 3-methoxy-3-oxo-propyl
1.026 but-2-ynyl 1.080 1-hydroxyethyl
1.027 1-methylprop-2-ynyl 1.081 difluoromethoxymethyl
1.028 1-methylbut-2-ynyl 1.082 1-difluoromethoxyethyl
1.029 1 , 1-dimethylprop-2-ynyl 1.083 2-difluoromethoxyethyl
1.030 cyanomethyl 1.084 prop-2-enyl
1.031 2-cyanoethyl 1.085 but-2-enyl
1.032 3-cyanopropyl 1.086 5,5,5-trifluoropentyl
1.033 1-methoxymethyl 1.087 2-methylpropenyl
1.034 2-methoxyethyl 1.088 2-methylbutyl
1.035 3-methoxypropyl 1.089 2-methoxy-1 , 1-dimethylethyl
1.036 4-methoxybutyl 1.090 2-hydroxy-2-methylpropyl
1.037 2-ethoxyethyl 1.091 2-hyd roxy- 1 , 1 -d i m ethyl ethyl
1.038 1-methoxyethyl 1.092 2-chloro-1 , 1-dimethylethyl
1.039 2-methoxypropyl 1.093 2-acetoxy-1 , 1-dimethylethyl
1.040 1 -(methoxymethyl)propyl 1.094 2-(trifluoromethyl)butyl
1.041 2-m ethoxy- 1 , 1 -d imethyl-ethyl 1.095 2-(difluoromethoxy)methyl
1.042 2-methoxyethoxymethyl 1.096 2-(difluoromethoxy)ethyl
1.043 1 -acetoxymethyl 1.097 1-methyoxymethyl
1.044 2-acetoxyethyl 1.098 1-methylpropyl
1.045 2-acetoxy-1 , 1 -dimethyl-ethyl 1.099 1-methylallyl
1.046 2,2-diethoxyethyl 1.100 1 -hydroxymethyl
1.047 2,2-dimethoxyethyl 1.101 1-hydroxy-1-methylethyl
1.048 hydroxymethyl 1.102 1-ethyl-1-methylpropyl
1.049 2-hydroxyethyl 1.103 1 -cyanomethyl
1.050 2-hydroxypropyl 1.104 1-acetamidomethyl
1-(chloromethyl)-2-hydroxy-1-
1.051 3-hydroxypropyl 1.105 methylethyl
1.052 2-hydroxy-1 , 1 -dimethyl-ethyl 1.106 (E)-bu -enyl
1.053 2-hydroxy-2-methyl-propyl 1.107 (E)-1-methylprop-1-enyl
1.054 trifluoromethyl
Table 1.2: This table discloses 107 specific compounds of formula (T-1 ) wherein A1 is C-R1 , A2 is C- R2, A3 is C-R3, A4 is C-R4 and R2, R3, R4, R5, R6, and R7 are hydrogen, R is fluorine, n is 1 , and R9 is as defined above in the Table 1. Table 1.3: This table discloses 107 specific compounds of formula (T-1 ) wherein A1 is C-R1, A2 is C- R2, A3 is C-R3, A4 is C-R4 and R2, R3, R4, R5, R6, and R7 are hydrogen, R is chlorine, n is 1 , and R9 is as defined above in the Table 1. Table 1.4: This table discloses 107 specific compounds of formula (T-1 ) wherein A1 is C-R1, A2 is C- R2, A3 is C-R3, A4 is C-R4 and R2, R3, R4, R5, R6, and R7 are hydrogen, R is methyl, n is 1 , and R9 is as defined above in the Table 1.
Table 1.5: This table discloses 107 specific compounds of formula (T-1 ) wherein A1 is C-R1, A2 is C- R2, A3 is C-R3, A4 is C-R4 and R2, R3, R4, R5, R6, and R7 are hydrogen, R is trifluoromethyl, n is 1 , and R9 is as defined above in the Table 1.
Table 1.6: This table discloses 107 specific compounds of formula (T-1 ) wherein A1 is N, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R2, R3, R4, R5, R6, and R7 are hydrogen, n is 1 , and R9 is as defined above in the Table 1.
Table 1.7: This table discloses 107 specific compounds of formula (T-1 ) wherein A1 is C-R1, A2 is C- R2, A3 is C-R3, A4 is C-R4 and R , R2, R4, R5, R6, and R7 are hydrogen, R3 is fluorine, n is 1 , and R9 is as defined above in the Table 1.
Table 1.8: This table discloses 107 specific compounds of formula (T-1 ) wherein A1 is C-R1, A2 is C- R2, A3 is C-R3, A4 is C-R4 and R2, R4, R5, R6, and R7 are hydrogen, R and R3 are fluorine, n is 1 , and R9 is as defined above in the Table 1. Table 1.9: This table discloses 107 specific compounds of formula (T-1 ) wherein A1 is C-R1, A2 is C- R2, A3 is C-R3, A4 is C-R4 and R3, R4, R5, R6, and R7 are hydrogen, R and R2 are fluorine, n is 1 , and R9 is as defined above in the Table 1.
Table 1.10: This table discloses 107 specific compounds of formula (T-1 ) wherein A1 is C-R1, A2 is C- R2, A3 is C-R3, A4 is C-R4 and R , R2, R3, R4, R5, R6, and R7 are hydrogen, n is 2, and R9 is as defined above in the Table 1.
Table 2.1 : This table discloses 69 specific compounds of the formula T-2):
Figure imgf000045_0001
(T-2) _.
45
wherein n is 1 , A1 is C-R , A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1 , R2, R3, R4, R5, R6, and R7 are hydrogen and R 0 is as defined below in the Table 2.
Each of Tables 2.2 to 2.10 (which follow Table 2.1 ) make available 69 individual compounds of the formula (T-2) in which n, A1 , A2, A3, A4, R5, R6 and R7 are as specifically defined in Tables 2.2 to 2.10, which refer to Table 2 wherein R 0 is specifically defined.
Table 2
Compound Compound
no. R10 no. R10
2.001 methyl 2.036 2,2-dimethoxyethyl
2.002 ethyl 2.037 hydroxymethyl
2.003 propyl 2.038 2-hydroxyethyl
2.004 isopropyl 2.039 2-hydroxypropyl
2.005 butyl 2.040 3-hydroxypropyl
2.006 sec-butyl 2.041 2-hydroxy-1 , 1 -dimethyl-ethyl
2.007 isobutyl 2.042 2-hydroxy-2-methyl-propyl
2.008 allyl 2.043 trifluoromethyl
2.009 2-methylallyl 2.044 2,2,2-trifluoroethyl
2.010 1 , 1-dimethylallyl 2.045 3,3,3-trifluoropropyl
2.01 1 pentyl 2.046 4,4,4-trifluorobutyl
2.012 octyl 2.047 fluoromethyl
2.013 prop-2-ynyl 2.048 difluoromethyl
2.014 but-3-ynyl 2.049 2-fluoroethyl
2.015 but-2-ynyl 2.050 3-fluoropropyl
2.016 1-methylprop-2-ynyl 2.051 4-fluorobutyl
2.017 1-methylbut-2-ynyl 2.052 1-fluoroethyl
2.018 1 , 1-dimethylprop-2-ynyl 2.053 2-fluoropropyl
2.019 cyanomethyl 2.054 chloromethyl
2.020 2-cyanoethyl 2.055 2-chloroethyl
2.021 3-cyanopropyl 2.056 2-(methylamino)-2-oxo-ethyl
2.022 1-methoxymethyl 2.057 2-(ethylamino)-2-oxo-ethyl
2.023 2-methoxyethyl 2.058 acetamidomethyl
2.024 3-methoxypropyl 2.059 acetamidoethyl
2.025 4-methoxybutyl 2.060 1-methyl-3-oxo-butyl
2.026 2-ethoxyethyl 2.061 3-m ethoxy- 1 -methyl-3-oxo-propyl
2.027 1-methoxyethyl 2.062 3-methoxy-3-oxo-propyl
2.028 2-methoxypropyl 2.063 1-hydroxyethyl
2.029 1 -(methoxymethyl)propyl 2.064 difluoromethoxymethyl
2.030 2-m ethoxy- 1 , 1 -d imethyl-ethyl 2.065 1-difluoromethoxyethyl 2.031 2-methoxyethoxymethyl 2.066 2-difluoromethoxyethyl
2.032 1 -acetoxymethyl 2.067 3-chloropropyl
2.033 2-acetoxyethyl 2.068 4-chlorobutyl
2.034 2-acetoxy-1 , 1 -dimethyl-ethyl 2.069 2, 2-di methyl propyl
2.035 2,2-diethoxyethyl
Table 2.2: This table discloses 69 specific compounds of formula (T-2) wherein A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R2, R3, R4, R5, R6, and R7 are hydrogen, R is fluorine, n is 1 , and R 0 is as defined above in the Table 2.
Table 2.3: This table discloses 69 specific compounds of formula (T-2) wherein A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R2, R3, R4, R5, R6, and R7 are hydrogen, R is chlorine, n is 1 , and R 0 is as defined above in the Table 2. Table 2.4: This table discloses 69 specific compounds of formula (T-2) wherein A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R2, R3, R4, R5, R6, and R7 are hydrogen, R is methyl, n is 1 , and R 0 is as defined above in the Table 2.
Table 2.5: This table discloses 69 specific compounds of formula (T-2) wherein A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R2, R3, R4, R5, R6, and R7 are hydrogen, R is trifluoromethyl, n is 1 , and R 0 is as defined above in the Table 2.
Table 2.6: This table discloses 69 specific compounds of formula (T-2) wherein A1 is N, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R2, R3, R4, R5, R6, and R7 are hydrogen, n is 1 , and R 0 is as defined above in the Table 2.
Table 2.7: This table discloses 69 specific compounds of formula (T-2) wherein A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R , R2, R4, R5, R6, and R7 are hydrogen, R3 is fluorine, n is 1 , and R 0 is as defined above in the Table 2.
Table 2.8: This table discloses 69 specific compounds of formula (T-2) wherein A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R2, R4, R5, R6, and R7 are hydrogen, R and R3 are fluorine, n is 1 , and R 0 is as defined above in the Table 2. Table 2.9: This table discloses 69 specific compounds of formula (T-2) wherein A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R3, R4, R5, R6, and R7 are hydrogen, R and R2 are fluorine, n is 1 , and R 0 is as defined above in the Table 2.
Table 2.10: This table discloses 69 specific compounds of formula (T-2) wherein A1 is C-R1, A2 is C- R2, A3 is C-R3, A4 is C-R4 and R , R2, R3, R4, R5, R6, and R7 are hydrogen, n is 2, and R 0 is as defined above in the Table 2. „_
47
Table 3.1 : This table discloses 64 specific compounds of the formula T-3):
Figure imgf000048_0001
wherein n is 1 , A1 is C-R , A2 is C-R2, A3 is C-R3, A4 is C-R4 and n, R , R2, R3, R4, R5, R6, R7 and R 2 are hydrogen and R is as defined below in the Table 3.
Each of Tables 3.2 to 3.13 (which follow Table 3.1 ) make available 64 individual compounds of the formula (T-3) in which n, A1 , A2, A3, A4, R5, R6, R7 and R 2 are as specifically defined in Tables 3.2 to 3.13, which refer to Table 3 wherein R is specifically defined.
Table 3
Compound Compound
no. R11 no. R11
3.001 methyl 3.033 2-methoxyethoxymethyl
3.002 ethyl 3.034 1 -acetoxymethyl
3.003 propyl 3.035 2-acetoxyethyl
3.004 isopropyl 3.036 2-acetoxy-1 , 1-dimethylethyl
3.005 butyl 3.037 2,2-diethoxyethyl
3.006 sec-butyl 3.038 2,2-dimethoxyethyl
3.007 isobutyl 3.039 2-methoxyethoxymethyl
3.008 tert-butyl 3.040 hydroxymethyl
3.009 pentyl 3.041 2-hydroxyethyl
3.010 2,2-dimethylpropyl 3.042 2-hydroxypropyl
3.01 1 cyano 3.043 3-hydroxypropyl
3.012 allyl 3.044 2-hyd roxy- 1 , 1 -d i m ethyl ethyl
3.013 2-methylallyl 3.045 2-hydroxy-2-methylpropyl
3.014 1 , 1-dimethylallyl 3.046 trifluoromethyl
3.015 prop-2-ynyl 3.047 2,2,2-trifluoroethyl
3.016 but-3-ynyl 3.048 3,3,3-trifluoropropyl
3.017 but-2-ynyl 3.049 4,4,4-trifluorobutyl
3.018 1-methylprop-2-ynyl 3.050 fluoromethyl
3.019 1-methylbut-2-ynyl 3.051 difluoromethyl
3.020 1 , 1-dimethylprop-2-ynyl 3.052 2-fluoroethyl 3.021 cyanomethyl 3.053 2-chloroethyl
3.022 2-cyanoethyl 3.054 2-methylsulfanylethyl
3.023 3-cyanopropyl 3.055 3-chloropropyl
3.024 1-methoxymethyl 3.056 methoxy
3.025 2-methoxyethyl 3.057 ethoxy
3.026 3-methoxypropyl 3.058 propoxy
3.027 4-methoxybutyl 3.059 isopropoxy
3.028 2-ethoxyethyl 3.060 butoxy
3.029 1-methoxyethyl 3.061 sec-butoxy
3.030 2-methoxypropyl 3.062 isobutoxy
3.031 1 -(methoxymethyl)propyl 3.063 allyloxy
3.032 2-methoxy-1 , 1-dimethylethyl 3.064 prop-2-ynyloxy
Table 3.2: This table discloses 64 specific compounds of formula (T-3) wherein A1 is C-R1 , A2 is C-R2, A3 is C-R3, A4 is C-R4 and R2, R3, R4, R5, R6, R7 and R 2 are hydrogen, R is fluorine, n is 1 , and R is as defined above in the Table 3.
Table 3.3: This table discloses 64 specific compounds of formula (T-3) wherein A1 is C-R1 , A2 is C-R2, A3 is C-R3, A4 is C-R4 and R2, R3, R4, R5, R6, R7 and R 2 are hydrogen, R is chlorine, n is 1 , and R is as defined above in the Table 3. Table 3.4: This table discloses 64 specific compounds of formula (T-3) wherein A1 is C-R1 , A2 is C-R2, A3 is C-R3, A4 is C-R4 and R2, R3, R4, R5, R6, R7 and R 2 are hydrogen, R is methyl, n is 1 , and R is as defined above in the Table 3.
Table 3.5: This table discloses 64 specific compounds of formula (T-3) wherein A1 is C-R1 , A2 is C-R2, A3 is C-R3, A4 is C-R4 and R2, R3, R4, R5, R6, R7 and R 2 are hydrogen, R is trifluoromethyl, n is 1 , and R is as defined above in the Table 3.
Table 3.6: This table discloses 64 specific compounds of formula (T-3) wherein A1 is N, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R2, R3, R4, R5, R6, R7 and R 2 are hydrogen, n is 1 , and R is as defined above in the Table 3.
Table 3.7: This table discloses 64 specific compounds of formula (T-3) wherein A1 is C-R1 , A2 is C-R2, A3 is C-R3, A4 is C-R4 and R , R2, R4, R5, R6, R7 and R 2 are hydrogen, R3 is fluorine, n is 1 , and R is as defined above in the Table 3.
Table 3.8: This table discloses 64 specific compounds of formula (T-3) wherein A1 is C-R1 , A2 is C-R2, A3 is C-R3, A4 is C-R4 and R2, R4, R5, R6, R7 and R 2 are hydrogen, R and R3 are fluorine, n is 1 , and R is as defined above in the Table 3. „„
49
Table 3.9: This table discloses 64 specific compounds of formula (T-3) wherein A1 is C-R , A2 is C-R2, A3 is C-R3, A4 is C-R4 and R3, R4, R5, R6, R7 and R 2 are hydrogen, R and R2 are fluorine, n is 1 , and R is as defined above in the Table 3. Table 3.10: This table discloses 64 specific compounds of formula (T-3) wherein A1 is C-R1 , A2 is C- R2, A3 is C-R3, A4 is C-R4 and R1 , R2, R3, R4, R5, R6, R7 and R 2 are hydrogen, n is 2, and R is as defined above in the Table 3.
Table 3.1 1 : This table discloses 64 specific compounds of formula (T-3) wherein A1 is N, A2 is N, A3 is C-R3, A4 is C-R4 and R3, R4, R5, R6, R7 and R 2 are hydrogen, n is 1 , and R is as defined above in the Table 3.
Table 3.12: This table discloses 64 specific compounds of formula (T-3) wherein wherein A1 is C-R1 , A2 is C-R2, A3 is C-R3, A4 is C-R4 and R , R2, R3, R4, R5, R6, and R7 are hydrogen, R 2 is methyl, n is 1 , and R is as defined above in the Table 3.
Table 3.13: This table discloses 64 specific compounds of formula (T-3) wherein wherein A1 is C-R1 , A2 is C-R2, A3 is C-R3, A4 is C-R4 and R , R2, R3, R4, R5, R6, and R7 are hydrogen, R 2 is ethyl, n is 1 , and R is as defined above in the Table 3.
EXAMPLES
The Examples which follow serve to illustrate the invention. 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) (including those according to the invention) may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).
Throughout this description, temperatures are given in degrees Celsius (°C) and "m.p." means melting point.
LC/MS means Liquid Chromatography Mass Spectrometry and the description of the apparatus and the method (Methods A and B) is as follows:
The description of the LC/MS apparatus and the method A is: SQ Detector 2 from Waters
lonisation method: Electrospray Polarity: positive and negative ions
Capillary (kV) 3.0, Cone (V) 30.00, Extractor (V) 2.00, Source Temperature (°C) 150, Desolvation Temperature (°C) 350, Cone Gas Flow (L/Hr) 0, Desolvation Gas Flow (L/Hr) 650
Mass range: 100 to 900 Da
DAD Wavelength range (nm): 210 to 500
Method Waters ACQUITY UPLC with the following HPLC gradient conditions:
(Solvent A: Water/Methanol 20:1 + 0.05% formic acid and Solvent B: Acetonitrile+ 0.05% formic acid)
Time (minutes) A (%) B (%) Flow rate (ml/mm)
0 100 0 0.85
1.2 0 100 0.85
1.5 0 100 0.85
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.
The description of the LC/MS apparatus and the method B is:
SQ Detector 2 from Waters
lonisation method: Electrospray
Polarity: positive ions
Capillary (kV) 3.5, Cone (V) 30.00, Extractor (V) 3.00, Source Temperature (°C) 150, Desolvation Temperature (°C) 400, Cone Gas Flow (L/Hr) 60, Desolvation Gas Flow (L/Hr) 700
Mass range: 140 to 800 Da
DAD Wavelength range (nm): 210 to 400
Method Waters ACQUITY UPLC with the following HPLC gradient conditions
(Solvent A: Water/Methanol 9: 1 + 0.1 % formic acid and Solvent B: Acetonitrile + 0.1 % formic acid) Time (minutes) A (%) B (%) Flow rate (ml/min)
0 100 0 0.75
2.5 0 100 0.75
2.8 0 100 0.75
3.0 100 0 0.75
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.
Where necessary, 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.
Formulation Examples
Wettable powders a) b) c)
active ingredient [compound of formula (I)] 25 % 50 % 75 %
sodium lignosulfonate 5 % 5 %
sodium lauryl sulfate 3 % - 5 %
sodium diisobutylnaphthalenesulfonate - 6 % 10 %
phenol polyethylene glycol ether - 2 %
(7-8 mol of ethylene oxide)
highly dispersed silicic acid 5 % 10 % 10 %
Kaolin 62 % 27 %
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.
Powders for dry seed treatment a) b) c)
active ingredient [compound of formula (I)] 25 % 50 % 75 %
light mineral oil 5 % 5 % 5 %
highly dispersed silicic acid 5 % 5 %
Kaolin 65 % 40 %
Talcum - 20%
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.
Emulsifiable concentrate
active ingredient [compound of formula (I)] 10 %
octylphenol polyethylene glycol ether 3 %
(4-5 mol of ethylene oxide)
calcium dodecylbenzenesulfonate 3 %
castor oil polyglycol ether (35 mol of ethylene oxide) 4 %
Cyclohexanone 30 %
xylene mixture 50 %
Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water. Dusts a) b) c)
Active ingredient [compound of formula (I)] 5 % 6 % 4 %
Talcum 95 %
Kaolin 94 %
mineral filler 96 %
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.
Extruder granules
Active ingredient [compound of formula (I)] 15 %
sodium lignosulfonate 2 %
Carboxymethylcellulose 1 %
Kaolin 82 %
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.
Coated granules
Active ingredient [compound of formula (I)] 8 %
polyethylene glycol (mol. wt. 200) 3 %
Kaolin 89 % The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
Suspension concentrate
active ingredient [compound of formula (I)] 40 %
propylene glycol 10 %
nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
Sodium lignosulfonate 10 %
Carboxymethylcellulose 1 %
silicone oil (in the form of a 75 % emulsion in water) 1 %
Water 32 %
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion. Flowable concentrate for seed treatment active ingredient [compound of formula (I)] 40 %
propylene glycol 5 %
copolymer butanol PO/EO 2 %
tristyrenephenole with 10-20 moles EO 2 %
1 ,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 %
monoazo-pigment calcium salt 5 %
Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
Water 45.3 %
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
Slow-Release Capsule Suspension
28 parts of a combination of the compound of formula I are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8: 1 ). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1 ,6- diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns.
The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
Preparation Examples
Using the synthetic techniques described both above and below, compounds of formula (I) may be prepared accordingly.
Throughout this description, temperatures are given in degrees Celsius (°C) and "mp" means melting point. LC/MS means Liquid Chromatography Mass Spectrometry and the description of the apparatus and the methods used for LC/MS analysis are given below.
List of Abbreviations:
AIBN = azobisisobutyronitrile BOP-CI = phosphoric acid bis(2-oxooxazolidide) chloride
CDI = carbonyl diimidazole
DCE = 1 ,2-dichloroethane
DCM = dichloromethane
DIBAL-H = diisobutylaluminium hydride
DIEA = N-ethyl-N-isopropyl-propan-2-amine
DIPEA = N,N-diisopropylethylamine
DMA = dimethylacetamide
DMAP = 4-dimethylaminopyridine
DMF = dimethylformamide
EdCI = 3-(ethyliminomethyleneamino)-/V,/V-dimethylpropan-1-amine
EtOAc = ethyl acetate
EtOH = ethyl alcohol
HCI = hydrochloric acid
HOAt = 1-hydroxy-7-azabenzotriazole
HATU = 1-[bis(dimethylamino)methylene]-1 H-1 ,2^-triazolo[4,5-b]pyridinium 3-oxid- hexafluorophosphate
mp = melting point
MeOH = methyl alcohol
NaOH = sodium hydroxide
NBS = N-bromosuccinimide
RT = room temperature
TFAA = trifluoroacetic acid anhydride
THF = tetrahydrofuran
Example 1 : Preparation of 2,2-dimethyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]- propanamide (Compound 1.2 of Table 1 )
Figure imgf000055_0001
Step 1 : Preparation of N'-hvdroxy-4-methyl-benzamidine
Figure imgf000055_0002
To a stirring suspension of 4-methylbenzonitrile (35 g, 0.29 mol) in ethanol (220 mL) and water
(440 mL) at RT were added hydroxylamine hydrochloride (41.1 g, 0.58 mol), potassium carbonate (65.4 g, 0.47 mol) and 8-hydroxyquinoline (0.22 g, 1.5 mmol). The reaction mixture was heated at 80°C for 4 hours. The mixture was cooled to RT and diluted with 2M HCI until pH 8. Ethanol was evaporated under reduced pressure. The mixture was filtered, washed with water and dried under vacuum to afford 39.1 g of the title compound. LC/MS (Method A) retention time = 0.23 minutes, 151.0 (M+H).
Step 2: Preparation of 3-(p-tolyl)-5-(trifluoromethyl)-1 ,2,4-oxadiazole
Figure imgf000056_0001
To a stirred solution of N'-hydroxy-4-methyl-benzamidine (38.7 g, 0.25 mol) in 2- methyltetrahydrofuran (750 mL) was added TFAA at 0°C. The reaction mixture was stirred at 15°C for two hours and diluted with water. The organic layer was separated, washed successively with sodium bicarbonate solution, ammonium chloride solution and water, dried over sodium sulfate, filtered and evaporated to dryness. The crude was subject to combiflash chromatography over silica gel with heptane/EtOAc 99: 1 to 90: 10 to afford 54.1 g of the title compound as clear oil, which solidified upon storage.
LC/MS (Method A) retention time = 1.15 minutes, mass not detected.
H NMR (400 MHz, CDCI3) δ ppm: 8.00 (d, 2H), 7.32 (d, 2H), 2.45 (s, 3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.41 (s).
Step 3a: Preparation of 3-[4-(bromomethyl)phenyll-5-(trifluoromethyl)-1 ,2,4-oxadiazole
Figure imgf000056_0002
A stirring mixture of 3-(p-tolyl)-5-(trifluoromethyl)-1 ,2,4-oxadiazole (56.0 g, 0.24 mol) and NBS
(45.4 g, 0.25 mol) in tetrachloromethane (480 mL) under argon was heated to 70°C. AIBN (4.03 g, 24 mmol) was added and the reaction mixture was stirred at 65°C for 18 hours. The mixture was cooled to 25°C and diluted with dichloromethane and water. The organic layer was washed with sodium bicarbonate solution, dried over sodium sulfate, filtered and evaporated to dryness. The crude was subject to flash chromatography over silica gel (750g pre packed column) with cyclohexane/EtOAc 100:0 to 95:5 to afford 44.7 g of the title compound as a white solid mp: 58-63°C. H NMR (400 MHz, CDCI3) δ ppm: 8.1 1 (d, 2H), 7.55 (d, 2H), 4.53 (s,2H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.32 (s). 3-[4-(dibromomethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (see below) was isolated as by-product as white solid (mp 61-66°C .
Figure imgf000057_0001
H NMR (400 MHz, CDCI3) δ ppm: 8.15 (d, 2H), 7.73 (d, 2H), 6.68 (s,1 H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.34 (s).
Step 3b: Preparation of 3-[4-(bromomethyl)phenyll-5-(trifluoromethvn-1 ,2,4-oxadiazole
Figure imgf000057_0002
To a stirring 1 :9 ratio mixture of 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole and 3-[4-(dibromomethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (10.2 g) in acetonitrile (95 mL), water (1.9 mL) and DIEA (6.20 mL, 35.7 mmol) was added diethylphosphite (4.7 mL, 35.7 mmol) at 5°C. The mixture was stirred at 5-10°C for two hours, water and 1 M HCI were added, and acetonitrile was evaporated under reduced pressure. The white slurry was extracted with dichloromethane and the combined organic layers were dried over sodium sulfate, and filtered. The solvent was removed under reduced pressure and the resultant crude was subject to flash chromatography over silicagel (40g prepacked column) with cyclohexane/EtOAc 99: 1 to 9: 1 to afford 7.10 g of 3-[4- (bromomethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole. H NMR (400 MHz, CDCI3) δ ppm: 8.1 1 (d, 2H), 7.55 (d, 2H), 4.53 (s, 2H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.32 (s).
Step 4: Preparation of [4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethanamine hydrochloride
Figure imgf000057_0003
A dry flask was charged with sodium hydride (2 equiv., 3.13 mmol, 60 mass% NaH) and tetrahydrofuran (25 mL). To this white suspension was added tert-butyl N-tert- butoxycarbonylcarbamate (1.1 equiv, 1.72 mmol) and while stirring for 5 minutes gas evolution was observed. 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (0.500 g, 1.56 mmol) was then introduced and the contents were stirred for 12 hours. Upon reaction completion, the solution was poured into water and extracted with ethyl acetate (2x30ml_). The organic layers were combined and dried over sodium sulfate, filtered, and concentrated at reduced pressure to produce a pale yellow oil which partially crystalize upon sitting. The yellow material was dissolved in dioxane (5 mL) and a hydrogen chloride solution (15 equiv., 24.7 mmol, 4M in dioxane) was introduced dropwise. After stirring overnight at 25°C the reaction solution was diluted with ether and provided a white precipitate (70% yield) whose analytics matched the reported values and which was used without further purification.
mp: >200 °C, LC/MS (Method A) retention time = 0.61 minutes, 244 (M+H). H NMR (400 MHz, DMSO-c/6) δ ppm: 8.56 (s,br, 2H), 8.13 (d, 2H), 7.75 (d, 2H), 4.15 (s,2H). 9F NMR (400 MHz, DMSO-c/6) δ ppm: -64.69 (s).
Alternatively, the titled compound can be prepared using an analaqous procedure as described in WO 2013/066839.
To a stirring solution of tert-butyl N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]- carbamate, (23.1 g, 65.4 mmol) in 1 ,4-dioxane (196 mL) heated to 70°C was added dropwise a HCI solution (41 mL, 163 mmol, 4M 1 ,4-dioxane). Precipitation of a white solid and gas liberation started 5 minutes after addition. The mixture was stirred for 6 hours at 70°C. The white suspension was cooled down to 23°C, filtered, washed with 1 ,4-dioxane, and dried under reduced pressure at 40°C to yield 17.3 g of [4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methanamine hydrochloride as a yellow solid.
Step 5: Preparation of 2,2-dimethyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyll- propanamide
Figure imgf000058_0001
To a stirring suspension of [4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methanamine hydrochloride (0.20 g, 0.70 mmol) in dichloromethane (3.5 mL) under an atmosphere of nitrogen was added triethylamine (0.29 mL, 2.1 mmol) at 0°C then pivaloyl chloride (0.97 mL, 0.77 mmol). The reaction mixture was stirred for 18 hours at room temperature, poured into a satuarted ammonium chloride solution and extracted with dichloromethane. The combined organic layers were washed with water, dried over sodium sulfate, and filtered. The solvent was removed under reduced pressure and the resultant crude residue was subjected to flash chromatography over silica gel (cyclohexane: EtOAc eluent gradient 9: 1 to 1 : 1 ) to afford 0.23 g of 2,2-dimethyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]-propanamide as a white solid mp: 183-190°C, LC/MS (Method A) retention time = 0.95 minutes, mass not detected. H NMR (400 MHz, CDCI3) δ ppm: 8.09 (d, 2H), 7.40 (d, 2H), 6.05 (sbr, 1 H), 4.52 (d,2H), 1.25
(s,9H).
9F NMR (400 MHz, CDCI3) δ ppm: -64.5(s).
Example 2: Preparation of methyl N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]carbamate (Compound 2.4 of Table T2)
Figure imgf000059_0001
To a solution of [4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methanamine hydrochloride (0.10 g, 0.36 mmol) in DCM (1 .19 mL) was added methyl chloroformate (0.06 mL, 0.72 mmol) followed by triethylamine (0.15 mL, 1.07 mmol). The reaction mixture was stirred for 1 h 20min at RT LCMS showed completion. A saturated sodium bicarbonate solution was added and the solution was extracted with DCM. The combined organic layers were dried over sodium sulfate, filtered, concentrated and purified by combiflash using cyclohexane/EtOAc as eluent to give methyl N-[[4-[5- (trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]carbamate as a white solid. LC/MS (Method A) retention time = 0.97 minutes, 302 (M+H). H NMR (400 MHz, DMSO-c/6) δ ppm 8.05 (d, 2H), 7.84 (t, 1 H), 7.51 (d, 2H), 4.30 (d, 2H), 3.59 (s, 3H) 9F NMR (400 MHz, DMSO-c/6) δ ppm: -64.68 (s)
Example 3: Preparation of 1-(2-methoxyethyl)-3-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]urea: (Compound 3.3 of Table T3)
Figure imgf000059_0002
To a solution of [4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methanamine hydrochloride (0.10 g, 0.36 mmol) in DCM (1.19 mL) was added 1-isocyanato-2-methoxy-ethane (0.07 g, 0.72 mmol) followed by triethylamine (0.10 mL, 0.72 mmol). The reaction mixture was stirred for 1 h 20min at RT. LCMS showed completion. A saturated sodium bicarbonate solution was added and the solution was extracted with DCM. The combined organic layers were dried over sodium sulfate, filtered, concentrated and purified by Isco combiflash using DCM/MeOH as eluent to give 1-(2-methoxyethyl)- 3-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]urea as a white solid. LC/MS (Method A) retention time = 0.88 minutes, 345 (M+H). H NMR (400 MHz, DMSO-c/6) δ ppm 8.04 (d, 2H), 7.49 (d, 2H), 6.56 (t, 1 H), 6.1 1 (t, 1 H), 4.32 (d, 2H),
3.35 (t, 2H), 3.28 (s, 3H), 3.20 (q, 2 H).
9F NMR (400 MHz, DMSO-c/6) δ ppm: -64.70 (s). Example 4: Preparation of N-[2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]ethyl]propanamide (Compound 1.29 of Table T1
Figure imgf000060_0001
Step 1 : Preparation of tert-butyl N-[2-(4-cyanophenyl)ethyl]carbamate
Figure imgf000060_0002
To a solution of 2-(4-cyanophenyl)ethylammonium chloride (3.0 g, 16 mmol) in THF (70 mL) was added triethylamine (6.9 mL, 49 mmol) and DMAP (200mg, 1.6 mmol). The resulting beige solution was cooled using an ice bath and tert-butoxycarbonyl tert-butyl carbonate (5.4 g, 25 mmol) was introduced dropwise as a THF solution (12 mL). The ice bath was removed and stirring continued overnight. Ice and water were added and extraction was carried out with Et20 (2 x 40 mL). The combined organic layers were washed with brine, dried over Na2S04, filtered, and concentrated under reduced pressure to afford a light yellow solid. The resulting crude residue was absorbed on isolute and purified via combiflash column chromatography using a cyclohexane/ethyl acetate eluent gradient to afford 1.56 g of tert-butyl N-[2-(4-cyanophenyl)ethyl]carbamate as a white solid, mp. 70-74°C. LC/MS (Method A) retention time = 0.94 min; mass not detected H NMR (400 MHz, CDCI3) δ ppm: 7.60 (d, 2H), 7.30 (d, 2H), 4.55 (brs, 1 H), 3.37 (m, 2H), 2.85 (m, 2H), 1.40 (s, 9H).
Step 2: Preparation of tert-butyl N-[2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]ethyl]carbamate
Figure imgf000060_0003
To a solution of tert-butyl N-[2-(4-cyanophenyl)ethyl]carbamate (912 mg, 3.7 mmol) in ethanol (18.5 mL) was added triethylamine (1.04 mL, 7.4 mmol) followed by the portion-wise introduction hydroxylamine hydrochloride (520 mg, 7.4 mmol). The reaction mixture was then heated to 80°C for 3.5 hours. After the reaction mixture cooled to 25°C, the ethanol was removed under reduced pressure, and the resulting crude tert-butyl N-[2-[4-[N'-hydroxycarbamimidoyl]phenyl]ethyl]carbamate residue was suspended in THF (37 mL). Pyridine (1.2 mL, 14.8 mL) was introduced and the reaction contents were cooled using an ice bath. Trifluoroacetic anhydride (1.57 mL, 1 1.1 mmol) was then added dropwise. The ice bath was removed and stirring was continued overnight. The reaction contents were concentrated under reduced pressure and diethyl acetate and water were introduced. The layers were separated and the organic fraction was washed sequentially with an aqueous 1 M NaOH solution, water, and brine then dried over sodium sulfate, filtered, and concentrated to give a yellow crude solid that was absorbed on isolute and purified via combiflash column chromatography using a cyclohexane/ethyl acetate eluent gradient to afford 826 mg of tert-butyl N-[2-[4-[5- (trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]ethyl]carbamate as a white solid, mp: 81-83°C. LC/MS (Method A) retention time = 1.17 min; mass not detected. H NMR (400 MHz, CDCI3) δ ppm: 8.05 (d, 2H), 7.85 (d, 2H), 4.55 (brs, 1 H), 3.48 (m, 2H), 2.88 (m 2H), 1.42 (s, 9H).
Step 3: Preparation of 2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]ethylammonium chloride
Figure imgf000061_0001
To a solution of tert-butyl N-[2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]ethyl]carbamate (500 mg, 1.4 mmol) in ethyl acetate (10 mL) cooled with an ice bath was introduced dropwise a 4M HCI 1 ,4-dioxane solution (2.8 mL, 1 1.2 mmol). The ice bath was removed and stirring was continued overnight. A fine white suspension slowly formed and was collected via filtration, washed twice with ethyl acetate, and dried in a vacuum oven to afford 378 mg of 2-[4-[5- (trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]ethylammonium chloride as a white solid, mp > 225°C LC/MS (Method A) retention time = 0.67 min; 258 [M-CI]+.
H NMR (400 MHz, DMSO) δ ppm: 8.05 (d, 2H), 7.52 (d, 2H), 3.10 (m, 2H), 3.00 (m 2H).
Step 4: Preparation of N-[2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]ethyl]propanamide
Figure imgf000062_0001
To a solution of 2-[4 5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]ethylammonium chloride (0.10 g, 0.34 mmol) in dichloromethane (5 mL) was added triethylamine (0.19 mL, 1.36 mmol) followed by propanoyl chloride (0.03 mL, 0.36 mmol). The reaction mixture was stirred overnight then poured on 1 M HCI, diluted with dichloromethane. The aqueous phase was removed and the organic layer was washed with 1 M NaOH then brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resultant crude residue was purified by combiflash column chromatography using a cyclohexane/EtOAc gradient as eluent to give 100 mg of N-[2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]ethyl]propanamide (0.055 g) as a white solid, mp: 133-145°C, LC/MS (Method A) retention time = 0.97 minutes, 314 (M+H)+. H NMR (400 MHz, CDCI3) δ ppm: 8.06 (d, 2H), 7.36 (d, 2H), 5.55 (brs, 1 H), 3.56 (q, 2H), 2.92 (t 2H), 2.18 (q, 2H), 1.13 (t, 3H). The following procedure was used in a combinatorial fashion using appropriate building blocks
(compounds (II) and (III)) to provide the compounds of Formula (I) wherein R8 is -C(0)R9. The com ounds prepared via the following combinatorial protocol were analyzed using LC/MS Method B.
Figure imgf000062_0002
By way of exemplification, acid derivatives of formula (III) (0.0375 mmol in 375 μί DMA) were transferred to a 96 slot deep well plate (DWP96) containing the [4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol- 3-yl]aryl]methanamine derivative of formula (II) (0.03 mmol) and DIPEA (0.09 mmol) in 250 μί DMA, followed by the addition of BOP-CI (0.06 mmol) dissolved in DMA (250 μΙ_). The DWP was sealed and stirred at 50°C for 18 hours. The solvent was removed under a stream of nitrogen. The resultant crude residues were solubilized in a mixture of MeOH (250 μΙ_) and DMA (500 μΙ_) and directly submitted for preparative LC/MS purification which provided the compounds of formula (I) in 10-85% yields.
Alternatively, the following procedures (protocol A and protocol B) were used in a combinatorial fashion using appropriate building blocks (compounds (II) and (IV)) to provide the compounds of Formula (I) wherein R8 is -C(0)OR ° or -C(0)NR R12. The compounds prepared via the following combinatorial protocol were analyzed using LC/MS Method B.
Figure imgf000063_0001
Protocol A: Portions of triphosgene (5.94 mg) in DCE (0.3 imL) were transferred at 0°C to a 5 96 slot deep well plate (DWP96) containing the alcohol derivative [HOR10] or amine derivative [HN(R )R12] of formula (IV) (0.05 mmol) and triethylamine (0.12 mmol) in 200 μΙ_ DMA. The reaction mixtures were stirred at RT for 30 minutes. [4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]aryl]methanamine derivatives of formula (II) (0.05 mmol) and triethylamine (0.12 mmol) in 200 μΙ_ DMA were added. The DWP was sealed and stirred at RT for 18 hours. DCE was removed under the 0 Barkey station. The crude residues were solubilized in a mixture of MeOH (200 μΙ_) and DMA (600 μΙ_) and directly submitted for preparative LC/MS purification which provided the compounds of formula (I) in 3-45% yields.
Protocol B: The alcohol derivative [HOR10] or amine derivative [HNR R12] of formula (IV) 5 (0.05 mmol) and DIPEA (0.25 mmol) in 300 μΙ_ DMA were transferred at RT to a 96 slot deep well plate (DWP96). CDI (0.10 mmol) in DMA (300 μΙ_) was added and stirred until solubilization. [4-[5- (trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]aryl]methanamine derivatives of formula (II) (0.05 mmol) and triethylamine (0.12 mmol) in 200 μΙ_ DMA were added. The DWP was sealed and stirred at RT for 18 hours. The DCE was removed under the Barkey station. The crude residues were solubilized in a 0 mixture of MeOH (200 μΙ_) and DMA (600 μΙ_) and directly submitted for preparative LC/MS purification which provided the compounds of formula (I) in 5-47% yields.
Table T1 : Melting point (mp) data and/or retention times (RT) for the compounds of Formula (I).
Figure imgf000063_0002
„„
63
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Table T2: Melting point (mp) data and/or retention times (RT) for the compounds of Formula (I):
Figure imgf000087_0002
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
Table T3: Melting point (mp) data and/or retention times (RT) for the compounds of Formula (I).
Figure imgf000096_0002
Figure imgf000097_0001
Figure imgf000098_0001
Figure imgf000099_0001
Figure imgf000100_0001
Figure imgf000101_0001
Figure imgf000102_0001
Figure imgf000103_0001
Figure imgf000104_0001
Figure imgf000105_0001
BIOLOGICAL EXAMPLES:
General examples of leaf disk tests in well plates:
5
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 10 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.
General examples of liquid culture tests in well plates:
Mycelia fragments or conidia suspensions of a fungus prepared either freshly from liquid cultures of the fungus or from cryogenic storage, are directly mixed into nutrient broth. DMSO solutions of the test compound (max. 10 mg/ml) are diluted with 0.025% Tween20 by a factor of 50 and 10 μΙ of this solution is pipetted into a microtiter plate (96-well format). The nutrient broth containing the fungal spores/mycelia fragments is then added to give an end concentration of the tested compound. The test plates are incubated in the dark at 24°C and 96% relative humidity. The inhibition of fungal growth is determined photometrically after 2 to 7 days, depending on the pathosystem, and percent antifungal activity relative to the untreated check is calculated. 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.
Compounds (from Table T1 ) 1.1 , 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.10, 1.1 1 , 1.12, 1.13, 1.14, 1.15, 1 .16, 1.17, 1 .18, 1 .19, 1.20, 1 .21 , 1.22, 1.23, 1 .25, 1.26, 1 .27, 1 .28, 1.29, 1 .32, 1.33, 1.34, 1.35, 1.36, 1 .37, 1.38, 1.39, 1 .40, 1.41 , 1.42, 1 .43, 1.44, 1.45, 1 .46, 1.47, 1.48, 1 .49, 1.51 , 1.53, 1 .54, 1.56, 1.59, 1 .60, 1.61 , 1 .62, 1 .63, 1.64, 1 .65, 1.66, 1.67, 1 .69, 1.71 , 1 .72, 1 .74, 1.75, 1 .77, 1.78, 1.79, 1.80, 1 .83, 1.84, 1.85, 1.86, 1.87, 1 .89, 1.90, 1.91 , 1 .92, 1.93, 1.94, 1.95, 1.96, 1 .97, 1.98, 1.99, 1 .100, 1.101 , 1.102, 1.103, 1.104, 1.105, 1.106 and 1.107.
Compounds (from Table T2) 2.1 , 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 2.10, 2.1 1 , 2.13, 2.14, 2.15, 2.16, 2.17, 2.18, 2.19, 2.20, 2.21 , 2.22, 2.23, 2.24, 2.25, 2.26, 2.28, 2.29, 2.30, 2.31 , 2.32, 2.33, 2.35 and 2.36.
Compounds (from Table T3) 3.1 , 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 3.10, 3.1 1 , 3.12, 3.13, 3.14, 3.15, 3.16, 3.17, 3.19, 3.20, 3.25, and 3.26.
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 , 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.10, 1.12, 1.13, 1.14, 1.15, 1.17, 1.19, 1.20, 1 .21 , 1.22, 1.23, 1 .25, 1.26, 1 .27, 1.28, 1 .29, 1.33, 1.34, 1 .35, 1.36, 1 .37, 1.38, 1.39, 1.40, 1 .41 , 1.42, 1 .43, 1 .44, 1.45, 1 .46, 1.47, 1.48, 1 .49, 1.51 , 1 .53, 1 .54, 1.56, 1 .57, 1.60, 1.61 , 1.62, 1.63, 1 .65, 1.66, 1.67, 1 .69, 1.71 , 1.72, 1 .73, 1.74, 1 .75, 1 .77, 1.78, 1 .79, 1.80, 1.83, 1 .84, 1.85, 1.86, 1.87, 1.89, 1.90, 1.92, 1.93, 1.94, 1 .95, 1 .96, 1 .97, 1 .98, 1.99, 1.100, 1 .101 , 1.102, 1.103, 1.104, 1.105, 1.106 and 1.107.
Compounds (from Table T2) 2.1 , 2.3, 2.4, 2.5, 2.6, 2.8, 2.10, 2.1 1 , 2.13, 2.14, 2.15, 2.16, 2.17,
2.18, 2.19, 2.20, 2.21 , 2.22, 2.24, 2.25, 2.26, 2.28, 2.29, 2.30, 2.31 , 2.32, 2.33, 2.34, 2.35, and 2.36.
Compounds (from Table T3) 3.1 , 3.2, 3.3, 3.4, 3.5, 3.9, 3.10, 3.12, 3.13, 3.14, 3.15, 3.16, 3.17, 3.25, and 3.26.
Fungicidal activity against Phakopsora pachyrhizi I soybean / leaf disc preventative (Asian soybean rust) Soybean leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. One day after application leaf discs are inoculated by spraying a spore suspension on the lower leaf surface. After an incubation period in a climate cabinet of 24-36 hours in darkness at 20°C and 75% rh leaf disc are kept at 20°C with 12 h light/day and 75% rh. 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.
Compounds (from Table T1 ) 1.1 , 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.10, 1.1 1 , 1.12, 1.13,
1.14, 1.15, 1 .16, 1.17, 1 .18, 1 .19, 1.20, 1 .21 , 1.22, 1.23, 1 .25, 1.26, 1 .28, 1 .29, 1.32, 1 .33, 1.34, 1.35, 1.36, 1.38, 1 .39, 1.41 , 1.44, 1 .46, 1.47, 1.48, 1 .49, 1.51 , 1.54, 1 .56, 1.59, 1.63, 1 .65, 1.77, 1.78, 1 .80, 1.82, 1 .83, 1.84, 1.85, 1.86, 1.87, 1 .88, 1.89, 1.90, 1.91 , 1.92, 1 .93, 1.94, 1.95, 1.96, 1.97, 1.99, 1.100, 1.101 , 1.102, 1.103 and 1.107.
Compounds (from Table T2) 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.10, 2.1 1 , 2.13, 2.14, 2.15, 2.16, 2.17,
2.19, and 2.36. _„_
107
Compounds (from Table T3) 3.1 , 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.9, 3.10, 3.12, 3.13, 3.14, 3.16, 3.17, 3.25, and 3.26.
Fungicidal activity against Glomerella lagenarium (Colletotrichum lagenarium) liquid culture / 5 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
10 24 C and the inhibition of growth is measured photometrically 3 to 4 days after application.
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.
Compounds (from Table T1 ) 1.1 , 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.10, 1.1 1 , 1.12, 1.13,
15 1.14, 1.15, 1 .16, 1.17, 1 .19, 1.20, 1.21 , 1 .23, 1.25, 1.26, 1.27, 1.28, 1.29, 1.32, 1.33, 1.34, 1.35, 1.36, 1.37, 1.38, 1 .39, 1.40, 1 .41 , 1 .42, 1.43, 1 .44, 1.45, 1.46, 1 .47, 1.48, 1 .49, 1 .50, 1.51 , 1 .52, 1.53, 1.54, 1.55, 1.56, 1 .57, 1 .58, 1.59, 1 .60, 1 .61 , 1.62, 1.63, 1 .64, 1.65, 1.66, 1 .67, 1.69, 1.70, 1 .71 , 1.72, 1 .73, 1.74, 1.75, 1 .77, 1.78, 1 .79, 1 .80, 1.81 , 1 .83, 1.84, 1.85, 1 .86, 1.87, 1 .88, 1 .89, 1.90, 1 .91 , 1.92, 1.93, 1.94, 1 .95, 1.96, 1.97, 1 .98, 1.99, 1.100, 1.101 , 1 .102, 1.103, 1 .104, 1.105 and 1.107.
20 Compounds (from Table T2) 2.1 , 2.2, 2.3, 2.4, 2.5, 2.6, 2.8, 2.10, 2.1 1 , 2.13, 2.14, 2.15, 2.16,
2.17, 2.18, 2.19, 2.20, 2.21 , 2.22, 2.23, 2.24, 2.25, 2.26, 2.28, 2.29, 2.30, 2.31 , 2.32, 2.33, 2.34, 2.35, and 2.36.
Compounds (from Table T3) 3.1 , 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.9, 3.10, 3.1 1 , 3.12, 3.13, 3.14, 3.15, 3.16, 3.17, 3.20, 3.25, and 3.26.
25
Fungicidal activity against Uromyces viciae-fabael field bean / leaf disc preventative (Faba-bean rust)
Field bean leaf discs are placed on water agar in multiwell plates (96-well format) and 10μΙ of the formulated test compound diluted in acetone and a spreader pipetted onto the leaf disc. Two hours 30 after application leaf discs are inoculated by spraying a spore suspension on the lower leaf surface.
The leaf discs are incubated in a climate cabinet at 22°C with 18 hour light/day and 70% relative humidity. 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 days after application).
35 The following compounds at 100 ppm in the applied formulation give at least 80% disease control in this test when compared to untreated control leaf discs under the same conditions, which show extensive disease development.
Compounds (from Table T1 ) 1.1 , 1.2, 1.3, 1.5, 1.1 1 , 1.13, 1.16, 1.18, 1.19, 1.22, 1.23, and
1.24.
40

Claims

Claims:
1. A compound of formula I):
Figure imgf000109_0001
wherein n is 1 or 2;
A1 represents N or CR , wherein R is hydrogen, halogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy;
A2 represents N or CR2, wherein R2 is hydrogen, halogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy;
A3 represents N or CR3, wherein R3 is hydrogen or halogen;
A4 represents N or CR4, wherein R4 is hydrogen or halogen; and wherein no more than two of A1 to A4 are N;
R5 and R6 are independently selected from hydrogen, C1_4alkyl, halogen, cyano, trifluoromethyl and difluoromethyl, or R5 and R6 together with the carbon atom they share form a cyclopropyl;
R7 is hydrogen;
R8 represents -C(0)R9, wherein R9 is hydrogen, d-6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoC-i. 6alkyl, Ci_6haloalkyl, C2-6haloalkenyl, hydroxyCi_6alkyl, hydroxyCi_6haloalkyl, Ci.4alkoxyCi.6alkyl, d. 4haloalkoxyCi-6alkyl, Ci-4alkoxyCi-4alkoxyCi-6alkyl, C2-6alkynyloxyCi-6alkyl, aminoCi_6alkyl, N-Ci_ 4alkylaminoCi.6alkyl, N,N-diCi.4alkylaminoCi.6alkyl, Ci.6alkylcarbonylCi.6alkyl, Ci.6alkylcarbonylC2. 6alkenyl, Ci.6alkoxycarbonylCi.6alkyl, Ci.6alkylcarbonyloxyCi.6alkyl, N-Ci.4alkylcarbonylaminoCi.6alkyl, N-Ci-4alkylaminocarbonylCi.6alkyl, N,N-diCi.4alkylaminocarbonylCi.6alkyl, Ci.6alkylsulfanylCi.6alkyl, Ci_ 6alkylsulfonylCi-6alkyl or Ci.6alkylsulfonylaminoCi.6alkyl; or
R8 represents -C(0)OR °, wherein R 0 is hydrogen, Ci_8alkyl, C3.6alkenyl, C3.6alkynyl, cyanoCi. 6alkyl, Ci_6haloalkyl, C3.6haloalkenyl, hydroxyCi_6alkyl, Ci.4alkoxyCi_6alkyl, Ci.4haloalkoxyCi_6alkyl, Ci_ 4alkoxyCi-4alkoxyCi.6alkyl, C2.6alkynyloxyCi.6alkyl, aminoCi_6alkyl, N-Ci.4alkylaminoCi.6alkyl, N,N-diCi_ 4alkylaminoCi-6alkyl, Ci.6alkylcarbonylCi.6alkyl, Ci-6alkylcarbonylC2-6alkenyl, Ci.6alkoxycarbonylCi_ 6alkyl, Ci.6alkylcarbonyloxyCi.6alkyl, N-Ci-4alkylaminocarbonylCi-6alkyl, N,N-diCi_
4alkylaminocarbonylCi.6alkyl, Ci.4alkylsulfanylCi.6alkyl, Ci.6alkylsulfonylCi.6alkyl or d. 6alkylsulfonylaminoCi.6alkyl; or
R8 represents -C(0)NR R12, wherein R is hydrogen, cyano, Ci_7alkyl, C2.6alkenyl, C2. 6alkynyl, cyanoCi_8alkyl, Ci_6haloalkyl, C2-6haloalkenyl, hydroxyCi_6alkyl, Ci.4alkoxyCi_6alkyl, Ci_ 4haloalkoxyCi_6alkyl, Ci.4alkoxyCi.4alkoxyCi.6alkyl, C2.6alkynyloxyCi.6alkyl, aminoCi.6alkyl, N-Ci_ 4alkylaminoCi.6alkyl, N,N-diCi.4alkylaminoCi.6alkyl, Ci.6alkylcarbonylCi.6alkyl, Ci.6alkylcarbonylC2. 6alkenyl, Ci.6alkoxycarbonylCi.6alkyl, Ci.6alkylcarbonyloxyCi.6alkyl, N-Ci.4alkylaminocarbonylCi.6alkyl, N,N-diCi.4alkylaminocarbonylCi.6alkyl, Ci.4alkylsulfanylCi_6alkyl, Ci.6alkylsulfonylCi.6alkyl or d. 6alkylsulfonylaminoCi.6alkyl;
R 2 is hydrogen, C1_4alkyl, C-|.4alkoxy, Ci.4alkoxyCi_6alkyl, C3.6alkenoxy or C3.6alkynoxy; or
R and R 2 together with the nitrogen atom they share form a 4-, 5- or 6-membered cycle optionally containing a heteroatom moiety comprising O, S or NR 3;
R 3 is hydrogen, methyl, methoxy, formyl or acyl; or a salt or an N-oxide thereof; with the proviso that the compound of Formula (I) is not: tert-butyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]carbamate.
2. A compound according to claim 1 , wherein:
A1 is N or CR1 wherein R represents hydrogen, halogen, methyl or trifluoromethyl;
A2 is N or C-H;
A3 is N or CR3 wherein R3 represents hydrogen or halogen; and
A4 is C-H.
3. A compound according to claim 1 or claim 2, wherein n is 1 , and R5 and R6 are independently selected from hydrogen and methyl.
4. A compound according to claim 1 or claim 2, wherein n is 2, and R5 and R6 are independently selected from hydrogen and fluoro. 5. A compound according to any one of claims 1 to 4, wherein: R is -C(0)R , wherein R is hydrogen, d-6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoCi_6alkyl, Ci_ 6haloalkyl, C2-6haloalkenyl, hydroxyCi_6alkyl, hydroxyCi_6haloalkyl, Ci.4alkoxyCi.6alkyl, Ci_ 4haloalkoxyCi.6alkyl, Ci-4alkoxyCi.4alkoxyCi.6alkyl, C2-4alkynyloxyCi.6alkyl, aminoCi.6alkyl, N-Ci_ 4alkylaminoCi.6alkyl, Ci.2alkylcarbonylCi_4alkyl or N-Ci.2alkylcarbonylaminoCi.2alkyl; or
5
R8 is -C(0)OR10, wherein R 0 is hydrogen, Ci_8alkyl, C3.6alkenyl, C3.6alkynyl, cyanoCi_6alkyl, Ci-6haloalkyl, C3.6haloalkenyl, hydroxyCi_6alkyl,
Figure imgf000111_0001
Ci.4haloalkoxyCi.6alkyl, d. 4alkoxyCi.4alkoxyCi.6alkyl or aminoCi.6alkyl; or
10 R8 represents -C(0)NR R12, wherein R is hydrogen, cyano, Ci_6alkyl, C2.6alkenyl, C2.
6alkynyl, cyanoCi_8alkyl, Ci_6haloalkyl, C2.6haloalkenyl, hydroxyCi_6alkyl, Ci.4alkoxyCi.6alkyl, aminoCi. 6alkyl or Ci.4alkylsulfanylCi.6alkyl; and
R 2 is hydrogen, C1_4alkyl or Ci_4alkoxy.
15
6. A compound according to any one of claims 1 to 5, wherein R9 is Ci_6alkyl, C3.6alkenyl, C3. 6alkynyl, cyanoCi_4alkyl, Ci_6haloalkyl, hydroxyCi_4alkyl, hydroxyCi_4haloalkyl, Ci.2alkoxyCi_4alkyl, Ci_ 2haloalkoxyCi-4alkyl, Ci.2alkylcarbonylCi_4alkyl or N-Ci.2alkylcarbonylaminoCi_2alkyl.
20 7. A compound according to any one of claims 1 to 6, wherein R9 is Ci_6alkyl, C3.4alkenyl, C3.
6alkynyl, Ci_4fluoroalkyl, Ci_4chloroalkyl, Ci.2alkoxyCi_4alkyl or Ci.2fluoroalkoxyCi_4alkyl.
8. A compound according to any one of claims 1 to 5, wherein R 0 is Ci_8alkyl, C3.4alkenyl, C3. 4alkynyl, Ci_4haloalkyl or Ci.2alkoxyCi_4alkyl.
25
9. A compound according to any one of claims 1 to 5, wherein R is hydrogen, cyano, Ci_6alkyl, C2.4alkenyl, C2.4alkynyl, cyanoCi_4alkyl, Ci_4haloalkyl, C2.4haloalkenyl, hydroxyCi_4alkyl, Ci.4alkoxyCi_ 4alkyl, aminoCi_4alkyl or Ci.4alkylsulfanylCi.4alkyl.
30 10. A compound according to any one of claims 1 to 5 or 9, wherein R is hydrogen, Ci_6alkyl or Ci-4alkoxyCi-6alkyl.
11. A compound according to any one of claims 1 to 5, 9 or 10, wherein R 2 is hydrogen, methyl, ethyl, methoxy or ethoxy.
35
12. An agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) according to any one of claims 1 to 1 1.
13. The composition according to claim 12, further comprising at least one additional active 40 ingredient and/or an agrochemically-acceptable diluent or carrier.
14. A method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I) according to any one of claims 1 to 1 1 , or a composition comprising this compound as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
15. Use of a compound of formula (I) according to any one of claims 1 to 1 1 as a fungicide.
PCT/EP2016/073290 2015-10-02 2016-09-29 Microbiocidal oxadiazole derivatives WO2017055469A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP16787342.1A EP3356335B1 (en) 2015-10-02 2016-09-29 Microbiocidal oxadiazole derivatives
MX2018003845A MX2018003845A (en) 2015-10-02 2016-09-29 Microbiocidal oxadiazole derivatives.
US15/765,089 US10501425B2 (en) 2015-10-02 2016-09-29 Microbiocidal oxadiazole derivatives
BR112018006630A BR112018006630B8 (en) 2015-10-02 2016-09-29 COMPOUND DERIVED FROM OXADIAZOLE MICROBIOCIDES, AGROCHEMICAL COMPOSITION COMPRISING SUCH COMPOUND, METHOD OF CONTROL OR PREVENTION OF INFESTATION OF USEFUL PLANTS BY PHYTOPATOGENIC MICROORGANISMS AND USE OF A COMPOUND
JP2018516700A JP6864673B2 (en) 2015-10-02 2016-09-29 Microbial oxadiazole derivative
CN201680058084.1A CN108137517B (en) 2015-10-02 2016-09-29 Microbicidal oxadiazole derivatives
IL258014A IL258014B (en) 2015-10-02 2018-03-11 Microbiocidal oxadiazole derivatives
ZA2018/01769A ZA201801769B (en) 2015-10-02 2018-03-15 Microbiocidal oxadiazole derivatives
CONC2018/0003681A CO2018003681A2 (en) 2015-10-02 2018-04-05 Oxadiazole derivatives microbicides

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
EP15188234 2015-10-02
EPEP15188234.7 2015-10-02
EPEP15201433.8 2015-12-18
EP15201433 2015-12-18
EP15202189 2015-12-22
EPEP15202189.5 2015-12-22

Publications (1)

Publication Number Publication Date
WO2017055469A1 true WO2017055469A1 (en) 2017-04-06

Family

ID=57206204

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2016/073290 WO2017055469A1 (en) 2015-10-02 2016-09-29 Microbiocidal oxadiazole derivatives

Country Status (11)

Country Link
US (1) US10501425B2 (en)
JP (1) JP6864673B2 (en)
CN (1) CN108137517B (en)
BR (1) BR112018006630B8 (en)
CL (1) CL2018000832A1 (en)
CO (1) CO2018003681A2 (en)
IL (1) IL258014B (en)
MX (1) MX2018003845A (en)
UY (1) UY36924A (en)
WO (1) WO2017055469A1 (en)
ZA (1) ZA201801769B (en)

Cited By (174)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017178245A1 (en) * 2016-04-11 2017-10-19 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2017211650A1 (en) 2016-06-09 2017-12-14 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2017211652A1 (en) 2016-06-09 2017-12-14 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2018177880A1 (en) * 2017-03-31 2018-10-04 Syngenta Participations Ag Fungicidal compositions
WO2018184985A1 (en) * 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184982A1 (en) * 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184970A1 (en) 2017-04-07 2018-10-11 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2018184984A1 (en) * 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184988A1 (en) * 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018188962A1 (en) 2017-04-11 2018-10-18 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2018202487A1 (en) 2017-05-04 2018-11-08 Basf Se Substituted 5-(haloalkyl)-5-hydroxy-isoxazoles for combating phytopathogenic fungi
WO2018202491A1 (en) 2017-05-04 2018-11-08 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
WO2018219797A1 (en) 2017-06-02 2018-12-06 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2019020501A1 (en) 2017-07-28 2019-01-31 Basf Se Preparation of substituted 3-aryl-5-trifluoromethyl-1,2,4-oxadiazoles
WO2019025250A1 (en) * 2017-08-04 2019-02-07 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
WO2019150219A2 (en) 2018-01-30 2019-08-08 Pi Industries Ltd. Novel oxadiazoles
WO2019171234A1 (en) 2018-03-09 2019-09-12 Pi Industries Ltd. Heterocyclic compounds as fungicides
WO2019224160A1 (en) 2018-05-25 2019-11-28 Syngenta Participations Ag Microbiocidal picolinamide derivatives
US10499644B2 (en) 2015-11-19 2019-12-10 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2020025807A1 (en) 2018-08-03 2020-02-06 Syngenta Crop Protection Ag Microbiocidal 1,2,5-oxadiazol-3(2h)-one derivatives
US10555526B2 (en) 2015-11-05 2020-02-11 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2020032071A1 (en) 2018-08-08 2020-02-13 日本農薬株式会社 Oxadiazoline compound or salt thereof, agricultural or horticultural bactericide containing said compound, and use method therefor
WO2020053364A1 (en) 2018-09-13 2020-03-19 Syngenta Participations Ag Pesticidally active azole-amide compounds
WO2020053365A2 (en) 2018-09-13 2020-03-19 Syngenta Participations Ag Pesticidally active azole-amide compounds
WO2020070610A1 (en) 2018-10-01 2020-04-09 Pi Industries Ltd. Novel oxadiazoles
WO2020070611A1 (en) 2018-10-01 2020-04-09 Pi Industries Ltd Oxadiazoles as fungicides
WO2020079111A1 (en) 2018-10-18 2020-04-23 Syngenta Crop Protection Ag Microbiocidal compounds
WO2020079198A1 (en) 2018-10-19 2020-04-23 Syngenta Participations Ag Pesticidally active azole-amide compounds
WO2020094363A1 (en) 2018-11-05 2020-05-14 Syngenta Participations Ag Pesticidally active azole-amide compounds
WO2020109511A1 (en) 2018-11-30 2020-06-04 Syngenta Crop Protection Ag Microbiocidal 2-acylamino-thiazole-4-carboxamide derivatives
WO2020109509A1 (en) 2018-11-30 2020-06-04 Syngenta Participations Ag Microbiocidal thiazole derivatives
US10674727B2 (en) 2015-11-19 2020-06-09 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2020165403A1 (en) 2019-02-15 2020-08-20 Syngenta Crop Protection Ag Phenyl substituted thiazole derivatives as microbiocidal compounds
WO2020169445A1 (en) 2019-02-18 2020-08-27 Syngenta Crop Protection Ag Pesticidally active azole-amide compounds
WO2020169526A1 (en) 2019-02-18 2020-08-27 Syngenta Crop Protection Ag Pesticidally-active cyanamide heterocyclic compounds
WO2020182649A1 (en) 2019-03-08 2020-09-17 Syngenta Crop Protection Ag Pesticidally active azole-amide compounds
WO2020188027A1 (en) 2019-03-20 2020-09-24 Syngenta Crop Protection Ag Pesticidally active azole amide compounds
WO2020188014A1 (en) 2019-03-20 2020-09-24 Syngenta Crop Protection Ag Pesticidally active azole amide compounds
US10785980B2 (en) 2016-06-09 2020-09-29 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2020193618A1 (en) 2019-03-27 2020-10-01 Syngenta Crop Protection Ag Microbiocidal thiazole derivatives
WO2020193341A1 (en) 2019-03-22 2020-10-01 Syngenta Crop Protection Ag N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-2-cyclopropyl-6-(trifluoromethyl)pyridine-4-carboxamide derivatives and related compounds as insecticides
WO2020193387A1 (en) 2019-03-22 2020-10-01 Syngenta Crop Protection Ag Fungicidal compounds
WO2020201398A1 (en) 2019-04-05 2020-10-08 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2020201079A1 (en) 2019-03-29 2020-10-08 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2020208096A1 (en) 2019-04-10 2020-10-15 Syngenta Crop Protection Ag Fungicidal compositions
WO2020208095A1 (en) 2019-04-10 2020-10-15 Syngenta Crop Protection Ag Microbiocidal picolinamide derivatives
WO2020208036A1 (en) 2019-04-11 2020-10-15 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2020239853A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020239856A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020239854A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020239855A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020254530A1 (en) 2019-06-18 2020-12-24 Syngenta Crop Protection Ag 7-sulfonyl-n-(1,3,4-thiadiazol-2-yl)-quinoxaline-6-carboxamide derivatives and the respective -benzimidazole-5-, -imidazo[4,5-b]pyridine-5-, -3h-furo[3,2b]pyridine-5-, -quinoline-2-, and -naphthalene-2-carboxamide derivatives as pesticides
JPWO2019131867A1 (en) * 2017-12-28 2021-01-07 日本農薬株式会社 Oxadiazole compounds or salts thereof, agricultural and horticultural fungicides containing the compounds, and methods of use thereof.
WO2021004968A1 (en) 2019-07-05 2021-01-14 Syngenta Crop Protection Ag Microbiocidal picolinamide derivatives
WO2021009026A1 (en) 2019-07-12 2021-01-21 Syngenta Crop Protection Ag Methyl 2-[(4-methoxyimino-tetralin-6-yl]prop-2-enoate derivatives, chromane, isochromane, 6,7,8,9-tetrahydrobenzo[7]annulene, 1h-isobenzofurane and indane analogues thereof, and similar compounds, as agrochemical fungicides
WO2021032631A1 (en) 2019-08-21 2021-02-25 Syngenta Participations Ag Precision treatment and sowing or planting method and device
WO2021032634A1 (en) 2019-08-21 2021-02-25 Syngenta Participations Ag Apparatus and method for reducing dust development in precision drill sowing
WO2021032630A1 (en) 2019-08-21 2021-02-25 Syngenta Participations Ag Sowing device and method for treating seeds during planting
WO2021032632A1 (en) 2019-08-21 2021-02-25 Syngenta Participations Ag Apparatus and method for converting existing sowing equipment
WO2021032633A1 (en) 2019-08-21 2021-02-25 Syngenta Participations Ag High precision greenhouse seed and seedling treatment
WO2021037614A1 (en) 2019-08-23 2021-03-04 Syngenta Crop Protection Ag Pesticidally active pyrazine-amide compounds
WO2021043616A1 (en) 2019-09-02 2021-03-11 Syngenta Crop Protection Ag Strigolactone derivatives as plant growth regulator compounds
WO2021053110A1 (en) 2019-09-20 2021-03-25 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur and sulfoximine containing substituents
WO2021053161A1 (en) 2019-09-20 2021-03-25 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2021083936A1 (en) 2019-11-01 2021-05-06 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
EP3709986A4 (en) * 2017-11-14 2021-05-26 Merck Sharp & Dohme Corp. Novel substituted biaryl compounds as indoleamine 2,3-dioxygenase (ido) inhibitors
WO2021110891A1 (en) 2019-12-04 2021-06-10 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic amino compounds
WO2021122645A1 (en) 2019-12-20 2021-06-24 Syngenta Crop Protection Ag Pesticidally active azole-amide compounds
WO2021136722A1 (en) 2019-12-31 2021-07-08 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021140122A1 (en) 2020-01-06 2021-07-15 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021144354A1 (en) 2020-01-15 2021-07-22 Syngenta Crop Protection Ag Pesticidally-active bicyclic heteroaromatic compounds
WO2021148639A1 (en) 2020-01-24 2021-07-29 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2021151926A1 (en) 2020-01-30 2021-08-05 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic amino compounds
WO2021160680A1 (en) 2020-02-11 2021-08-19 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2021170881A1 (en) 2020-02-27 2021-09-02 Syngenta Crop Protection Ag Pesticidally active diazine-bisamide compounds
WO2021175822A1 (en) 2020-03-02 2021-09-10 Syngenta Crop Protection Ag Pesticidally amidine-substituted benzoic acid amide compounds
WO2021176057A1 (en) 2020-03-05 2021-09-10 Syngenta Crop Protection Ag Fungicidal compositions
WO2021176007A1 (en) 2020-03-05 2021-09-10 Syngenta Crop Protection Ag Fungicidal compositions
WO2021180592A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180975A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180598A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180596A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180974A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180976A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola, cercospora sojina and/or cercospora kikuchii
WO2021204855A1 (en) 2020-04-08 2021-10-14 Syngenta Crop Protection Ag Microbiocidal quinoline dihydropyrrolopyrazine derivatives
WO2021204822A1 (en) 2020-04-08 2021-10-14 Syngenta Crop Protection Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2021204857A1 (en) 2020-04-08 2021-10-14 Syngenta Crop Protection Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2021213929A1 (en) 2020-04-20 2021-10-28 Syngenta Crop Protection Ag Pesticidally active substituted 1,3-dihydro-2h-imidazo[4,5-c]pyridin-2-one derivatives with sulfur containing substituents
WO2021219810A1 (en) 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021219775A1 (en) 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021219778A1 (en) 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Microbiocidal compounds
JP2021529746A (en) * 2018-06-26 2021-11-04 サイトキネティックス， インコーポレイテッド Cardiac sarcomere inhibitor
WO2021219780A1 (en) 2020-05-01 2021-11-04 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021224102A1 (en) 2020-05-05 2021-11-11 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021224409A1 (en) 2020-05-06 2021-11-11 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021244950A1 (en) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2021244951A1 (en) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2021244952A1 (en) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2022013417A1 (en) 2020-07-17 2022-01-20 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022017975A1 (en) 2020-07-18 2022-01-27 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022043576A2 (en) 2020-08-31 2022-03-03 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022049144A1 (en) 2020-09-02 2022-03-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022049146A1 (en) 2020-09-02 2022-03-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022048988A1 (en) 2020-09-02 2022-03-10 Syngenta Participations Ag Plant growth regulator compounds
WO2022049141A1 (en) 2020-09-01 2022-03-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022053567A1 (en) 2020-09-09 2022-03-17 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022058580A1 (en) 2020-09-21 2022-03-24 Syngenta Crop Protection Ag Microbiocidal compounds
WO2022084346A1 (en) 2020-10-22 2022-04-28 Syngenta Crop Protection Ag Zealactone derivatives as plant growth regulators
WO2022101265A1 (en) 2020-11-13 2022-05-19 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2022117653A1 (en) 2020-12-02 2022-06-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2022117650A1 (en) 2020-12-02 2022-06-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2022157334A1 (en) 2021-01-21 2022-07-28 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022157122A1 (en) 2021-01-22 2022-07-28 Syngenta Crop Protection Ag Method for the control or suppression of phytopathogenic bacteria
WO2022157188A2 (en) 2021-01-23 2022-07-28 Syngenta Crop Protection Ag Pesticidally active heteroaromatic compounds
WO2022207462A1 (en) 2021-03-30 2022-10-06 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2022207665A1 (en) 2021-03-31 2022-10-06 Syngenta Crop Protection Ag Microbiocidal quinoline/quinoxaline benzothiazine derivatives
WO2022207479A1 (en) 2021-03-27 2022-10-06 Syngenta Crop Protection Ag Microbiocidal isonicotinic amide derivatives
WO2022219146A2 (en) 2021-04-16 2022-10-20 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2022223376A1 (en) 2021-04-20 2022-10-27 Syngenta Crop Protection Ag Microbiocidal quinoline/quinoxaline isoquinoline derivatives
WO2022233869A1 (en) 2021-05-04 2022-11-10 Syngenta Crop Protection Ag Use of clethodim for insect control
WO2022253841A1 (en) 2021-06-02 2022-12-08 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfoximine containing substituents
WO2022253645A1 (en) 2021-06-01 2022-12-08 Syngenta Crop Protection Ag Microbiocidal tetrahydroisoquinoline derivatives
WO2022258481A1 (en) 2021-06-09 2022-12-15 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2022268648A1 (en) 2021-06-24 2022-12-29 Syngenta Crop Protection Ag 2-[3-[1 [(quinazolin-4-yl)amino]ethyl]pyrazin-2-yl]thiazole-5-carbonitrile derivatives and similar compounds as pesticides
WO2023275116A1 (en) 2021-07-02 2023-01-05 Syngenta Crop Protection Ag Use of fluazifop-p-butyl for insect control
WO2023006634A1 (en) 2021-07-27 2023-02-02 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023006789A1 (en) 2021-07-29 2023-02-02 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2023012081A1 (en) 2021-08-05 2023-02-09 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023012044A1 (en) 2021-08-02 2023-02-09 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2023017094A1 (en) 2021-08-10 2023-02-16 Syngenta Crop Protection Ag 2,2-difluoro-5h-[1,3]dioxolo[4,5-f]isoindol-7-one derivatives as pesticides
WO2023017016A1 (en) 2021-08-10 2023-02-16 Syngenta Crop Protection Ag Fungicide mixture
WO2023021020A1 (en) 2021-08-19 2023-02-23 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023061838A1 (en) 2021-10-14 2023-04-20 Syngenta Crop Protection Ag Imidazo[1,2-a]pyridine derivatives
WO2023072785A1 (en) 2021-10-29 2023-05-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2023072945A1 (en) 2021-10-25 2023-05-04 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023072784A1 (en) 2021-10-29 2023-05-04 Syngenta Crop Protection Ag Fungicidal compositions comprising fludioxonil
WO2023072849A1 (en) 2021-10-27 2023-05-04 Syngenta Crop Protection Ag Pesticidally active pyridazinone compounds
WO2023089049A2 (en) 2021-11-19 2023-05-25 Syngenta Crop Protection Ag Microbiocidal isonicotinic amide derivatives
WO2023094303A1 (en) 2021-11-25 2023-06-01 Syngenta Crop Protection Ag Microbiocidal heterobiaryl amide derivatives
WO2023094304A1 (en) 2021-11-25 2023-06-01 Syngenta Crop Protection Ag Microbiocidal heterobiaryl amide derivatives
WO2023099460A1 (en) 2021-12-02 2023-06-08 Syngenta Crop Protection Ag Fungicidal compositions
WO2023104714A1 (en) 2021-12-10 2023-06-15 Syngenta Crop Protection Ag Pesticidally active pyridazinone compounds
EP4197333A1 (en) 2021-12-15 2023-06-21 Syngenta Crop Protection AG Method for controlling diamide resistant pests & compounds therefor
WO2023110869A1 (en) 2021-12-15 2023-06-22 Syngenta Crop Protection Ag Microbiocidal bicycle heterocyclic derivatives
WO2023110928A1 (en) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Fungicidal compositions
WO2023110871A1 (en) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2023111215A1 (en) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Microbiocidal pyridine-substituted benzothiazine derivatives
WO2023110710A1 (en) 2021-12-13 2023-06-22 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023118434A1 (en) 2021-12-22 2023-06-29 Globachem Nv Pesticidally active amide compounds
WO2023118011A1 (en) 2021-12-22 2023-06-29 Syngenta Crop Protection Ag Microbiocidal aza-heterobiaryl derivatives
WO2023117625A1 (en) 2021-12-22 2023-06-29 Syngenta Crop Protection Ag Fungicidal compositions
WO2023139166A1 (en) 2022-01-19 2023-07-27 Syngenta Crop Protection Ag Methods for controlling plant pathogens
WO2023148206A1 (en) 2022-02-02 2023-08-10 Syngenta Crop Protection Ag Microbiocidal n-amide derivatives
WO2023148369A1 (en) 2022-02-07 2023-08-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023148368A1 (en) 2022-02-07 2023-08-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023166067A1 (en) 2022-03-02 2023-09-07 Syngenta Crop Protection Ag Microbiocidal pyridazinone amide derivatives
WO2023187191A1 (en) 2022-04-01 2023-10-05 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023209238A1 (en) 2022-04-29 2023-11-02 Syngenta Crop Protection Ag Fungicidal compositions
WO2023217989A1 (en) 2022-05-12 2023-11-16 Syngenta Crop Protection Ag Alkoxy heteroaryl- carboxamide or thioamide compounds
WO2023247360A1 (en) 2022-06-21 2023-12-28 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2023247552A1 (en) 2022-06-21 2023-12-28 Syngenta Crop Protection Ag Microbiocidal bicyclic heterocyclic carboxamide derivatives
WO2024008567A1 (en) 2022-07-07 2024-01-11 Syngenta Crop Protection Ag Precision application devices and compositions
WO2024017788A1 (en) 2022-07-22 2024-01-25 Syngenta Crop Protection Ag Solid form of a heterocyclic amide derivative
WO2024018016A1 (en) 2022-07-21 2024-01-25 Syngenta Crop Protection Ag Crystalline forms of 1,2,4-oxadiazole fungicides
WO2024022910A1 (en) 2022-07-26 2024-02-01 Syngenta Crop Protection Ag 1-[1-[2-(pyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-3-[2,4-dichloro-5-phenyl]urea derivatives and similar compounds as pesticides
WO2024033374A1 (en) 2022-08-11 2024-02-15 Syngenta Crop Protection Ag Novel arylcarboxamide or arylthioamide compounds
WO2024038053A1 (en) 2022-08-16 2024-02-22 Syngenta Crop Protection Ag New use of pydiflumetofen
WO2024056732A1 (en) 2022-09-16 2024-03-21 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2024068950A1 (en) 2022-09-30 2024-04-04 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2024068656A1 (en) 2022-09-28 2024-04-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2024068838A1 (en) 2022-09-28 2024-04-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2024068947A1 (en) 2022-09-30 2024-04-04 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2024068655A1 (en) 2022-09-28 2024-04-04 Syngenta Crop Protection Ag Fungicidal compositions
US11964967B2 (en) 2018-06-26 2024-04-23 Cytokinetics, Inc. Cardiac sarcomere inhibitors

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10640497B2 (en) * 2015-12-02 2020-05-05 Syngenta Participations Ag Microbiocidal oxadiazole derivatives

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0276432A2 (en) * 1986-12-12 1988-08-03 Ciba-Geigy Ag Pesticides
CN1927860A (en) * 2005-09-08 2007-03-14 国家南方农药创制中心江苏基地 Pyrazolecarboxamide compounds, intermediate thereof and pest control chemicals with the same as active component
WO2008037789A1 (en) * 2006-09-29 2008-04-03 Bayer Cropscience Sa Fungicide n-cycloalkyl-carboxamide, thiocarboxamide and n-substituted-carboximidamide derivatives
WO2013064079A1 (en) * 2011-11-02 2013-05-10 中国中化股份有限公司 Use of compound of pyrazole amides as agricultural fungicide
WO2013066839A2 (en) * 2011-10-31 2013-05-10 Glaxosmithkline Llc Compounds and methods

Family Cites Families (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103221047B (en) 2010-01-13 2014-12-17 坦颇罗制药股份有限公司 Compounds and methods
WO2011088192A1 (en) 2010-01-13 2011-07-21 Tempero Pharmaceuticals, Inc. Compounds and methods
CA2815105A1 (en) 2010-10-21 2012-04-26 Bayer Intellectual Property Gmbh N-benzyl heterocyclic carboxamides
WO2013006408A1 (en) 2011-07-01 2013-01-10 Tempero Pharmaceuticals, Inc. Compounds and methods
ES2556822T3 (en) 2011-07-08 2016-01-20 Novartis Ag Novel trifluoromethyl-oxadiazole derivatives and their use in the treatment of disease
WO2013009830A1 (en) 2011-07-13 2013-01-17 Tempero Pharmaceuticals, Inc. Methods of treatment
WO2013009810A1 (en) 2011-07-13 2013-01-17 Tempero Pharmaceuticals, Inc. Methods of treatment
WO2013009827A1 (en) 2011-07-13 2013-01-17 Tempero Pharmaceuticals, Inc. Methods of treatment
WO2013066835A2 (en) 2011-10-31 2013-05-10 Glaxosmithkline Llc Compounds and methods
CA2856334A1 (en) 2011-11-28 2013-06-06 Christina Hebach Novel trifluoromethyl-oxadiazole derivatives and their use in the treatment of disease
WO2015055706A2 (en) 2013-10-16 2015-04-23 Bayer Cropscience Ag N-cycloalkyl-n-(biheterocyclymethylene)-(thio)carboxamide derivatives
FR3021902B1 (en) 2014-06-05 2016-07-22 Inria Inst Nat Rech Informatique & Automatique METHOD FOR DETERMINING THE POINTS TO BE SUPPORTED FOR AN OBJECT MADE BY MEANS OF AN ADDITIVE MANUFACTURING PROCESS; INFORMATION RECORDING MEDIUM AND RELATED SUPPORT STRUCTURE
JP6556146B2 (en) 2014-08-26 2019-08-07 武田薬品工業株式会社 Heterocyclic compounds
EP3342772A4 (en) 2015-08-25 2019-03-27 Takeda Pharmaceutical Company Limited Heterocyclic compound
WO2017055473A1 (en) 2015-10-02 2017-04-06 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
US20190135798A1 (en) 2015-11-02 2019-05-09 Basf Se Substituted Oxadiazoles for Combating Phytopathogenic Fungi
EP3165094A1 (en) 2015-11-03 2017-05-10 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
EP3371155A1 (en) 2015-11-03 2018-09-12 Basf Se Use of substituted oxadiazoles for combating phytopathogenic fungi
WO2017076935A1 (en) 2015-11-04 2017-05-11 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
BR112018008288A2 (en) 2015-11-04 2018-10-30 Basf Se use of formula compounds, formula compounds, mixture, agrochemical composition and method for combating fungi
EP3165093A1 (en) 2015-11-05 2017-05-10 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
CR20180310A (en) 2015-11-05 2018-11-30 Basf Se OXADIAZOLS REPLACED TO COMBAT HONGOD PHYTOOPATHOGENS
BR112018009566A2 (en) 2015-11-13 2018-11-06 Basf Se compounds, mixture, agrochemical composition, use of compounds and method to combat phytopathogenic harmful fungi
AR106679A1 (en) 2015-11-13 2018-02-07 Basf Se OXADIAZOLS REPLACED TO FIGHT FITOPATHOGEN FUNGI
WO2017081309A1 (en) 2015-11-13 2017-05-18 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
BR112018009579A2 (en) 2015-11-13 2018-11-06 Basf Se compound of formula i, mixture, agrochemical composition, compound use and fungal control method
WO2017085098A1 (en) * 2015-11-19 2017-05-26 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2017085100A1 (en) 2015-11-19 2017-05-26 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
US10640497B2 (en) 2015-12-02 2020-05-05 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017093019A1 (en) 2015-12-03 2017-06-08 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
JP2019507110A (en) * 2015-12-17 2019-03-14 シンジェンタ パーティシペーションズ アーゲー Microbicidal oxadiazole derivative
CN108368098B (en) * 2015-12-18 2022-01-28 先正达参股股份有限公司 Microbicidal oxadiazole derivatives
WO2017111152A1 (en) 2015-12-25 2017-06-29 住友化学株式会社 Oxadiazole compounds and use thereof
WO2017110864A1 (en) 2015-12-25 2017-06-29 住友化学株式会社 Plant disease control composition and application for same
WO2017110861A1 (en) 2015-12-25 2017-06-29 住友化学株式会社 Plant disease control agent containing oxadiazole compound
WO2017110862A1 (en) 2015-12-25 2017-06-29 住友化学株式会社 Oxadiazole compound and use thereof
JP6841234B2 (en) 2015-12-25 2021-03-10 住友化学株式会社 Oxadiazole compounds and their uses
WO2017169893A1 (en) 2016-03-31 2017-10-05 住友化学株式会社 Oxadiazole compound and use thereof
CA3020532A1 (en) 2016-04-11 2017-10-19 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
JP2017190296A (en) 2016-04-13 2017-10-19 住友化学株式会社 Pest control composition and use therefor
WO2017211649A1 (en) 2016-06-09 2017-12-14 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
BR112018074569B1 (en) 2016-06-09 2022-10-04 Basf Se COMPOUNDS, USE OF N-(2,4-DIFLUOROPHENYL)-4-[5-(TRIFLUOROMETHYL)-1,2,4-OXADIAZOLE-3-YL] BENZAMIDE, AGROCHEMICAL COMPOSITION AND METHOD TO FIGHT HARMFUL PHYTOPATOGENIC FUNGI
BR112018074559A2 (en) 2016-06-09 2019-03-12 Basf Se compounds, agrochemical composition, use of compounds and method to combat phytopathogenic harmful fungi
WO2017213252A1 (en) 2016-06-10 2017-12-14 Sumitomo Chemical Company, Limited Oxadiazole compound and use as pesticide
US11066396B2 (en) 2016-06-23 2021-07-20 Merck Sharp & Dohme Corp. 3-aryl- heteroaryl substituted 5-trifluoromethyl oxadiazoles as histonedeacetylase 6 (HDAC6) inhibitors
AR109304A1 (en) 2016-08-10 2018-11-21 Sumitomo Chemical Co OXADIAZOL COMPOUND AND ITS USE

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0276432A2 (en) * 1986-12-12 1988-08-03 Ciba-Geigy Ag Pesticides
CN1927860A (en) * 2005-09-08 2007-03-14 国家南方农药创制中心江苏基地 Pyrazolecarboxamide compounds, intermediate thereof and pest control chemicals with the same as active component
WO2008037789A1 (en) * 2006-09-29 2008-04-03 Bayer Cropscience Sa Fungicide n-cycloalkyl-carboxamide, thiocarboxamide and n-substituted-carboximidamide derivatives
WO2013066839A2 (en) * 2011-10-31 2013-05-10 Glaxosmithkline Llc Compounds and methods
WO2013064079A1 (en) * 2011-11-02 2013-05-10 中国中化股份有限公司 Use of compound of pyrazole amides as agricultural fungicide

Cited By (181)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10555526B2 (en) 2015-11-05 2020-02-11 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
US10499644B2 (en) 2015-11-19 2019-12-10 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
US10674727B2 (en) 2015-11-19 2020-06-09 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
US10986839B2 (en) 2016-04-11 2021-04-27 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2017178245A1 (en) * 2016-04-11 2017-10-19 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2017211652A1 (en) 2016-06-09 2017-12-14 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2017211650A1 (en) 2016-06-09 2017-12-14 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
US10785980B2 (en) 2016-06-09 2020-09-29 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2018177880A1 (en) * 2017-03-31 2018-10-04 Syngenta Participations Ag Fungicidal compositions
WO2018184985A1 (en) * 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184982A1 (en) * 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184984A1 (en) * 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184988A1 (en) * 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184970A1 (en) 2017-04-07 2018-10-11 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2018188962A1 (en) 2017-04-11 2018-10-18 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2018202487A1 (en) 2017-05-04 2018-11-08 Basf Se Substituted 5-(haloalkyl)-5-hydroxy-isoxazoles for combating phytopathogenic fungi
JP7160487B2 (en) 2017-05-04 2022-10-25 ビーエーエスエフ ソシエタス・ヨーロピア Substituted 5-(haloalkyl)-5-hydroxy-isoxazoles for combating plant pathogens
WO2018202491A1 (en) 2017-05-04 2018-11-08 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
JP2020518607A (en) * 2017-05-04 2020-06-25 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Substituted 5-(haloalkyl)-5-hydroxy-isoxazoles for combating phytopathogens
CN110621669A (en) * 2017-05-04 2019-12-27 巴斯夫欧洲公司 Substituted 5-haloalkyl-5-hydroxyisoxazoles for controlling phytopathogenic fungi
WO2018219797A1 (en) 2017-06-02 2018-12-06 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2019020501A1 (en) 2017-07-28 2019-01-31 Basf Se Preparation of substituted 3-aryl-5-trifluoromethyl-1,2,4-oxadiazoles
WO2019025250A1 (en) * 2017-08-04 2019-02-07 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
US11498904B2 (en) 2017-11-14 2022-11-15 Merck Sharp & Dohme Llc Substituted biaryl compounds as indoleamine 2,3-dioxygenase (IDO) inhibitors
EP3709986A4 (en) * 2017-11-14 2021-05-26 Merck Sharp & Dohme Corp. Novel substituted biaryl compounds as indoleamine 2,3-dioxygenase (ido) inhibitors
JPWO2019131867A1 (en) * 2017-12-28 2021-01-07 日本農薬株式会社 Oxadiazole compounds or salts thereof, agricultural and horticultural fungicides containing the compounds, and methods of use thereof.
US11286242B2 (en) 2018-01-30 2022-03-29 Pi Industries Ltd. Oxadiazoles for use in controlling phytopathogenic fungi
WO2019150219A2 (en) 2018-01-30 2019-08-08 Pi Industries Ltd. Novel oxadiazoles
WO2019171234A1 (en) 2018-03-09 2019-09-12 Pi Industries Ltd. Heterocyclic compounds as fungicides
WO2019224160A1 (en) 2018-05-25 2019-11-28 Syngenta Participations Ag Microbiocidal picolinamide derivatives
US11964967B2 (en) 2018-06-26 2024-04-23 Cytokinetics, Inc. Cardiac sarcomere inhibitors
JP2021529746A (en) * 2018-06-26 2021-11-04 サイトキネティックス， インコーポレイテッド Cardiac sarcomere inhibitor
WO2020025807A1 (en) 2018-08-03 2020-02-06 Syngenta Crop Protection Ag Microbiocidal 1,2,5-oxadiazol-3(2h)-one derivatives
JP7407114B2 (en) 2018-08-08 2023-12-28 日本農薬株式会社 Oxadiazoline compounds or salts thereof, agricultural and horticultural fungicides containing the compounds, and methods for using the same
WO2020032071A1 (en) 2018-08-08 2020-02-13 日本農薬株式会社 Oxadiazoline compound or salt thereof, agricultural or horticultural bactericide containing said compound, and use method therefor
WO2020053365A2 (en) 2018-09-13 2020-03-19 Syngenta Participations Ag Pesticidally active azole-amide compounds
WO2020053364A1 (en) 2018-09-13 2020-03-19 Syngenta Participations Ag Pesticidally active azole-amide compounds
WO2020070611A1 (en) 2018-10-01 2020-04-09 Pi Industries Ltd Oxadiazoles as fungicides
WO2020070610A1 (en) 2018-10-01 2020-04-09 Pi Industries Ltd. Novel oxadiazoles
WO2020079111A1 (en) 2018-10-18 2020-04-23 Syngenta Crop Protection Ag Microbiocidal compounds
WO2020079198A1 (en) 2018-10-19 2020-04-23 Syngenta Participations Ag Pesticidally active azole-amide compounds
WO2020094363A1 (en) 2018-11-05 2020-05-14 Syngenta Participations Ag Pesticidally active azole-amide compounds
WO2020109511A1 (en) 2018-11-30 2020-06-04 Syngenta Crop Protection Ag Microbiocidal 2-acylamino-thiazole-4-carboxamide derivatives
WO2020109509A1 (en) 2018-11-30 2020-06-04 Syngenta Participations Ag Microbiocidal thiazole derivatives
WO2020165403A1 (en) 2019-02-15 2020-08-20 Syngenta Crop Protection Ag Phenyl substituted thiazole derivatives as microbiocidal compounds
WO2020169445A1 (en) 2019-02-18 2020-08-27 Syngenta Crop Protection Ag Pesticidally active azole-amide compounds
WO2020169526A1 (en) 2019-02-18 2020-08-27 Syngenta Crop Protection Ag Pesticidally-active cyanamide heterocyclic compounds
WO2020182649A1 (en) 2019-03-08 2020-09-17 Syngenta Crop Protection Ag Pesticidally active azole-amide compounds
WO2020188027A1 (en) 2019-03-20 2020-09-24 Syngenta Crop Protection Ag Pesticidally active azole amide compounds
WO2020188014A1 (en) 2019-03-20 2020-09-24 Syngenta Crop Protection Ag Pesticidally active azole amide compounds
WO2020193387A1 (en) 2019-03-22 2020-10-01 Syngenta Crop Protection Ag Fungicidal compounds
WO2020193341A1 (en) 2019-03-22 2020-10-01 Syngenta Crop Protection Ag N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-2-cyclopropyl-6-(trifluoromethyl)pyridine-4-carboxamide derivatives and related compounds as insecticides
WO2020193618A1 (en) 2019-03-27 2020-10-01 Syngenta Crop Protection Ag Microbiocidal thiazole derivatives
WO2020201079A1 (en) 2019-03-29 2020-10-08 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2020201398A1 (en) 2019-04-05 2020-10-08 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2020208095A1 (en) 2019-04-10 2020-10-15 Syngenta Crop Protection Ag Microbiocidal picolinamide derivatives
WO2020208096A1 (en) 2019-04-10 2020-10-15 Syngenta Crop Protection Ag Fungicidal compositions
WO2020208036A1 (en) 2019-04-11 2020-10-15 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2020239853A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020239856A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020239854A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020239855A1 (en) 2019-05-29 2020-12-03 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2020254530A1 (en) 2019-06-18 2020-12-24 Syngenta Crop Protection Ag 7-sulfonyl-n-(1,3,4-thiadiazol-2-yl)-quinoxaline-6-carboxamide derivatives and the respective -benzimidazole-5-, -imidazo[4,5-b]pyridine-5-, -3h-furo[3,2b]pyridine-5-, -quinoline-2-, and -naphthalene-2-carboxamide derivatives as pesticides
WO2021004968A1 (en) 2019-07-05 2021-01-14 Syngenta Crop Protection Ag Microbiocidal picolinamide derivatives
WO2021009026A1 (en) 2019-07-12 2021-01-21 Syngenta Crop Protection Ag Methyl 2-[(4-methoxyimino-tetralin-6-yl]prop-2-enoate derivatives, chromane, isochromane, 6,7,8,9-tetrahydrobenzo[7]annulene, 1h-isobenzofurane and indane analogues thereof, and similar compounds, as agrochemical fungicides
WO2021032634A1 (en) 2019-08-21 2021-02-25 Syngenta Participations Ag Apparatus and method for reducing dust development in precision drill sowing
WO2021032631A1 (en) 2019-08-21 2021-02-25 Syngenta Participations Ag Precision treatment and sowing or planting method and device
WO2021032633A1 (en) 2019-08-21 2021-02-25 Syngenta Participations Ag High precision greenhouse seed and seedling treatment
WO2021032632A1 (en) 2019-08-21 2021-02-25 Syngenta Participations Ag Apparatus and method for converting existing sowing equipment
WO2021032630A1 (en) 2019-08-21 2021-02-25 Syngenta Participations Ag Sowing device and method for treating seeds during planting
WO2021037614A1 (en) 2019-08-23 2021-03-04 Syngenta Crop Protection Ag Pesticidally active pyrazine-amide compounds
WO2021043616A1 (en) 2019-09-02 2021-03-11 Syngenta Crop Protection Ag Strigolactone derivatives as plant growth regulator compounds
WO2021053110A1 (en) 2019-09-20 2021-03-25 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur and sulfoximine containing substituents
WO2021053161A1 (en) 2019-09-20 2021-03-25 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2021083936A1 (en) 2019-11-01 2021-05-06 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2021110891A1 (en) 2019-12-04 2021-06-10 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic amino compounds
WO2021122645A1 (en) 2019-12-20 2021-06-24 Syngenta Crop Protection Ag Pesticidally active azole-amide compounds
WO2021136722A1 (en) 2019-12-31 2021-07-08 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021140122A1 (en) 2020-01-06 2021-07-15 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021144354A1 (en) 2020-01-15 2021-07-22 Syngenta Crop Protection Ag Pesticidally-active bicyclic heteroaromatic compounds
WO2021148639A1 (en) 2020-01-24 2021-07-29 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2021151926A1 (en) 2020-01-30 2021-08-05 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic amino compounds
WO2021160680A1 (en) 2020-02-11 2021-08-19 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2021170881A1 (en) 2020-02-27 2021-09-02 Syngenta Crop Protection Ag Pesticidally active diazine-bisamide compounds
WO2021175822A1 (en) 2020-03-02 2021-09-10 Syngenta Crop Protection Ag Pesticidally amidine-substituted benzoic acid amide compounds
WO2021176007A1 (en) 2020-03-05 2021-09-10 Syngenta Crop Protection Ag Fungicidal compositions
WO2021176057A1 (en) 2020-03-05 2021-09-10 Syngenta Crop Protection Ag Fungicidal compositions
WO2021180976A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola, cercospora sojina and/or cercospora kikuchii
WO2021180975A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180592A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180598A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180974A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021180596A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
WO2021204822A1 (en) 2020-04-08 2021-10-14 Syngenta Crop Protection Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2021204857A1 (en) 2020-04-08 2021-10-14 Syngenta Crop Protection Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2021204855A1 (en) 2020-04-08 2021-10-14 Syngenta Crop Protection Ag Microbiocidal quinoline dihydropyrrolopyrazine derivatives
WO2021213929A1 (en) 2020-04-20 2021-10-28 Syngenta Crop Protection Ag Pesticidally active substituted 1,3-dihydro-2h-imidazo[4,5-c]pyridin-2-one derivatives with sulfur containing substituents
WO2021219778A1 (en) 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021219775A1 (en) 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021219810A1 (en) 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021219780A1 (en) 2020-05-01 2021-11-04 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021224102A1 (en) 2020-05-05 2021-11-11 Syngenta Crop Protection Ag Microbiocidal compounds
WO2021224409A1 (en) 2020-05-06 2021-11-11 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2021244950A1 (en) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2021244951A1 (en) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2021244952A1 (en) 2020-06-03 2021-12-09 Syngenta Crop Protection Ag Microbiocidal derivatives
WO2022013417A1 (en) 2020-07-17 2022-01-20 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022017975A1 (en) 2020-07-18 2022-01-27 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022043576A2 (en) 2020-08-31 2022-03-03 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022049141A1 (en) 2020-09-01 2022-03-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022048988A1 (en) 2020-09-02 2022-03-10 Syngenta Participations Ag Plant growth regulator compounds
WO2022049146A1 (en) 2020-09-02 2022-03-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022049144A1 (en) 2020-09-02 2022-03-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022053567A1 (en) 2020-09-09 2022-03-17 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022058580A1 (en) 2020-09-21 2022-03-24 Syngenta Crop Protection Ag Microbiocidal compounds
WO2022084346A1 (en) 2020-10-22 2022-04-28 Syngenta Crop Protection Ag Zealactone derivatives as plant growth regulators
WO2022101265A1 (en) 2020-11-13 2022-05-19 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2022117650A1 (en) 2020-12-02 2022-06-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2022117653A1 (en) 2020-12-02 2022-06-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2022157334A1 (en) 2021-01-21 2022-07-28 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2022157122A1 (en) 2021-01-22 2022-07-28 Syngenta Crop Protection Ag Method for the control or suppression of phytopathogenic bacteria
WO2022157188A2 (en) 2021-01-23 2022-07-28 Syngenta Crop Protection Ag Pesticidally active heteroaromatic compounds
WO2022207479A1 (en) 2021-03-27 2022-10-06 Syngenta Crop Protection Ag Microbiocidal isonicotinic amide derivatives
WO2022207462A1 (en) 2021-03-30 2022-10-06 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2022207665A1 (en) 2021-03-31 2022-10-06 Syngenta Crop Protection Ag Microbiocidal quinoline/quinoxaline benzothiazine derivatives
WO2022219146A2 (en) 2021-04-16 2022-10-20 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2022223376A1 (en) 2021-04-20 2022-10-27 Syngenta Crop Protection Ag Microbiocidal quinoline/quinoxaline isoquinoline derivatives
WO2022233869A1 (en) 2021-05-04 2022-11-10 Syngenta Crop Protection Ag Use of clethodim for insect control
WO2022253645A1 (en) 2021-06-01 2022-12-08 Syngenta Crop Protection Ag Microbiocidal tetrahydroisoquinoline derivatives
WO2022253841A1 (en) 2021-06-02 2022-12-08 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfoximine containing substituents
WO2022258481A1 (en) 2021-06-09 2022-12-15 Syngenta Crop Protection Ag Pesticidally active diazine-amide compounds
WO2022268648A1 (en) 2021-06-24 2022-12-29 Syngenta Crop Protection Ag 2-[3-[1 [(quinazolin-4-yl)amino]ethyl]pyrazin-2-yl]thiazole-5-carbonitrile derivatives and similar compounds as pesticides
WO2023275116A1 (en) 2021-07-02 2023-01-05 Syngenta Crop Protection Ag Use of fluazifop-p-butyl for insect control
WO2023006634A1 (en) 2021-07-27 2023-02-02 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023006789A1 (en) 2021-07-29 2023-02-02 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2023012044A1 (en) 2021-08-02 2023-02-09 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2023012081A1 (en) 2021-08-05 2023-02-09 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023017016A1 (en) 2021-08-10 2023-02-16 Syngenta Crop Protection Ag Fungicide mixture
WO2023017094A1 (en) 2021-08-10 2023-02-16 Syngenta Crop Protection Ag 2,2-difluoro-5h-[1,3]dioxolo[4,5-f]isoindol-7-one derivatives as pesticides
WO2023021020A1 (en) 2021-08-19 2023-02-23 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
WO2023061838A1 (en) 2021-10-14 2023-04-20 Syngenta Crop Protection Ag Imidazo[1,2-a]pyridine derivatives
WO2023072945A1 (en) 2021-10-25 2023-05-04 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023072849A1 (en) 2021-10-27 2023-05-04 Syngenta Crop Protection Ag Pesticidally active pyridazinone compounds
WO2023072784A1 (en) 2021-10-29 2023-05-04 Syngenta Crop Protection Ag Fungicidal compositions comprising fludioxonil
WO2023072785A1 (en) 2021-10-29 2023-05-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2023089049A2 (en) 2021-11-19 2023-05-25 Syngenta Crop Protection Ag Microbiocidal isonicotinic amide derivatives
WO2023094303A1 (en) 2021-11-25 2023-06-01 Syngenta Crop Protection Ag Microbiocidal heterobiaryl amide derivatives
WO2023094304A1 (en) 2021-11-25 2023-06-01 Syngenta Crop Protection Ag Microbiocidal heterobiaryl amide derivatives
WO2023099460A1 (en) 2021-12-02 2023-06-08 Syngenta Crop Protection Ag Fungicidal compositions
WO2023104714A1 (en) 2021-12-10 2023-06-15 Syngenta Crop Protection Ag Pesticidally active pyridazinone compounds
WO2023110710A1 (en) 2021-12-13 2023-06-22 Syngenta Crop Protection Ag Method for controlling diamide resistant pests & compounds therefor
EP4197333A1 (en) 2021-12-15 2023-06-21 Syngenta Crop Protection AG Method for controlling diamide resistant pests & compounds therefor
WO2023110869A1 (en) 2021-12-15 2023-06-22 Syngenta Crop Protection Ag Microbiocidal bicycle heterocyclic derivatives
WO2023110928A1 (en) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Fungicidal compositions
WO2023111215A1 (en) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Microbiocidal pyridine-substituted benzothiazine derivatives
WO2023110871A1 (en) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2023118434A1 (en) 2021-12-22 2023-06-29 Globachem Nv Pesticidally active amide compounds
WO2023118011A1 (en) 2021-12-22 2023-06-29 Syngenta Crop Protection Ag Microbiocidal aza-heterobiaryl derivatives
WO2023117625A1 (en) 2021-12-22 2023-06-29 Syngenta Crop Protection Ag Fungicidal compositions
WO2023139166A1 (en) 2022-01-19 2023-07-27 Syngenta Crop Protection Ag Methods for controlling plant pathogens
WO2023148206A1 (en) 2022-02-02 2023-08-10 Syngenta Crop Protection Ag Microbiocidal n-amide derivatives
WO2023148368A1 (en) 2022-02-07 2023-08-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023148369A1 (en) 2022-02-07 2023-08-10 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023166067A1 (en) 2022-03-02 2023-09-07 Syngenta Crop Protection Ag Microbiocidal pyridazinone amide derivatives
WO2023187191A1 (en) 2022-04-01 2023-10-05 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2023209238A1 (en) 2022-04-29 2023-11-02 Syngenta Crop Protection Ag Fungicidal compositions
WO2023217989A1 (en) 2022-05-12 2023-11-16 Syngenta Crop Protection Ag Alkoxy heteroaryl- carboxamide or thioamide compounds
WO2023247360A1 (en) 2022-06-21 2023-12-28 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
WO2023247552A1 (en) 2022-06-21 2023-12-28 Syngenta Crop Protection Ag Microbiocidal bicyclic heterocyclic carboxamide derivatives
WO2024008567A1 (en) 2022-07-07 2024-01-11 Syngenta Crop Protection Ag Precision application devices and compositions
WO2024018016A1 (en) 2022-07-21 2024-01-25 Syngenta Crop Protection Ag Crystalline forms of 1,2,4-oxadiazole fungicides
WO2024017788A1 (en) 2022-07-22 2024-01-25 Syngenta Crop Protection Ag Solid form of a heterocyclic amide derivative
WO2024022910A1 (en) 2022-07-26 2024-02-01 Syngenta Crop Protection Ag 1-[1-[2-(pyrimidin-4-yl)-1,2,4-triazol-3-yl]ethyl]-3-[2,4-dichloro-5-phenyl]urea derivatives and similar compounds as pesticides
WO2024033374A1 (en) 2022-08-11 2024-02-15 Syngenta Crop Protection Ag Novel arylcarboxamide or arylthioamide compounds
WO2024038053A1 (en) 2022-08-16 2024-02-22 Syngenta Crop Protection Ag New use of pydiflumetofen
WO2024056732A1 (en) 2022-09-16 2024-03-21 Syngenta Crop Protection Ag Pesticidally active cyclic amine compounds
WO2024068656A1 (en) 2022-09-28 2024-04-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2024068838A1 (en) 2022-09-28 2024-04-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2024068655A1 (en) 2022-09-28 2024-04-04 Syngenta Crop Protection Ag Fungicidal compositions
WO2024068950A1 (en) 2022-09-30 2024-04-04 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2024068947A1 (en) 2022-09-30 2024-04-04 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives

Also Published As

Publication number Publication date
BR112018006630A2 (en) 2018-10-23
CL2018000832A1 (en) 2018-07-06
BR112018006630B8 (en) 2022-07-12
BR112018006630B1 (en) 2022-05-17
US10501425B2 (en) 2019-12-10
CN108137517A (en) 2018-06-08
IL258014B (en) 2021-04-29
JP6864673B2 (en) 2021-04-28
MX2018003845A (en) 2018-06-18
IL258014A (en) 2018-05-31
CN108137517B (en) 2022-04-12
JP2018535935A (en) 2018-12-06
CO2018003681A2 (en) 2018-07-10
UY36924A (en) 2017-04-28
US20180265483A1 (en) 2018-09-20
ZA201801769B (en) 2019-01-30

Similar Documents

Publication Publication Date Title
US10501425B2 (en) Microbiocidal oxadiazole derivatives
US11066375B2 (en) Microbiocidal oxadiazole derivatives
US10640497B2 (en) Microbiocidal oxadiazole derivatives
US11259524B2 (en) Microbiocidal oxadiazole derivatives
AU2017275603B2 (en) Microbiocidal thiazole derivatives
WO2016087593A1 (en) Novel fungicidal quinolinylamidines
EP3356335B1 (en) Microbiocidal oxadiazole derivatives
EP3383179B1 (en) Microbiocidal oxadiazole derivatives

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16787342

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 258014

Country of ref document: IL

WWE Wipo information: entry into national phase

Ref document number: MX/A/2018/003845

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 15765089

Country of ref document: US

Ref document number: 2018516700

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112018006630

Country of ref document: BR

WWE Wipo information: entry into national phase

Ref document number: 2016787342

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 112018006630

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20180402