WO2017055473A1 - Microbiocidal oxadiazole derivatives - Google Patents

Microbiocidal oxadiazole derivatives Download PDF

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Publication number
WO2017055473A1
WO2017055473A1 PCT/EP2016/073295 EP2016073295W WO2017055473A1 WO 2017055473 A1 WO2017055473 A1 WO 2017055473A1 EP 2016073295 W EP2016073295 W EP 2016073295W WO 2017055473 A1 WO2017055473 A1 WO 2017055473A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
heterocyclyl
phenyl
cycloalkyl
hydrogen
Prior art date
Application number
PCT/EP2016/073295
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
Priority to CN201680058005.7A priority Critical patent/CN108137570B/en
Priority to JP2018516818A priority patent/JP6864675B2/en
Application filed by Syngenta Participations Ag filed Critical Syngenta Participations Ag
Priority to ES16774508T priority patent/ES2807849T3/en
Priority to SI201630854T priority patent/SI3356358T1/en
Priority to DK16774508.2T priority patent/DK3356358T3/en
Priority to US15/765,138 priority patent/US10899724B2/en
Priority to EP16774508.2A priority patent/EP3356358B1/en
Priority to MX2018004038A priority patent/MX2018004038A/en
Priority to PL16774508T priority patent/PL3356358T3/en
Priority to BR112018006623-0A priority patent/BR112018006623B1/en
Publication of WO2017055473A1 publication Critical patent/WO2017055473A1/en
Priority to IL258012A priority patent/IL258012B/en
Priority to ZA2018/01828A priority patent/ZA201801828B/en
Priority to CONC2018/0003840A priority patent/CO2018003840A2/en
Priority to US16/786,688 priority patent/US11180462B2/en
Priority to US16/786,672 priority patent/US11066375B2/en

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to microbiocidal oxadiazole derivatives, eg, as active ingredients, which have microbiocidal activity, in particular, fungicidal activity.
  • the invention also relates to agrochemical compositions which comprise at least one of the oxadiazole derivatives, to processes of preparation of these compounds and to uses of the oxadiazole derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, preferably fungi.
  • Microbiocidal oxadiazole derivatives are known as insecticidal and acaricidal agents, eg, from CN 1927860.
  • WO 2013/064079, EP 0 276 432 and WO 2015/185485 describe the use of substituted oxadiazoles for combating phytopathogenic fungi.
  • a 1 represents N or CR , wherein R is hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy;
  • a 2 represents N or CR 2 , wherein R 2 is hydrogen, halogen, methyl, ethyl, difluoromethyl, 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 0, 1 or 2 of A 1 , A 2 , A 3 and 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 hydroxy, C 1 _ 4 alkyl, C 1 _ 4 haloalkyl, C 1 _ 4 alkoxy, hydroxyC 1 _ 4 alkyl, C 1 _ 2 alkoxyC 1 _ 4 alkyl, C 1 _ 2 haloalkoxyC 1 _ 4 alkyl, C 3 _ 6 alkenyl, C 3 _ 4 alkynyl, C 3 _ 6 alkenyloxy, C 3 _ 6 alkynyloxy, C 3 _ 6 haloalkenyl, C 3 _ 6 haloalkenyloxy, C 1 _ 4 alkylcarbonyloxy, C 1 _ 4 haloalkylcarbonyloxy, C 1 _
  • R 7 is C 3 _ 6 cycloalkyl, C 3 _ 6 cycloalkylC 1 _ 2 alkyl, C 3 - 6 cycloalkylC 1 - 2 alkoxy, phenyl, phenylC 1 _ 2 alkyl, phenylC 1 _ 2 alkoxy, heteroaryl, heteroarylC 1 _ 2 alkyl, heteroarylC 1 _ 2 alkoxy, heterocyclyl, heterocyclylC 1 _ 2 alkyl, heterocyclylC 1 _ 2 alkoxy, C 3 _ 6 cycloalkylcarbonyloxy, heterocyclylcarbonyloxy phenylcarbonyloxy, C 3 _ 6 cycloalkylcarbonyloxyC 1 _ 4 alkyl, heterocyclylcarbonyloxyC 1 _ 4 alkyl or phenylcarbonyloxyC 1 _ 4 alkyl, wherein the heteroaryl moiety is a 5- or 6-membered mono
  • R 8 is hydrogen, C 1 _ 6 alkyl, C 2 _ 6 alkenyl, C 2 _ 6 alkynyl, cyanoC 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 2 _ 6 haloalkenyl, hydroxyC 1 _ 6 alkyl, C 1 _ 4 alkoxyC 1 _ 6 alkyl, C 1 _ 4 haloalkoxyC 1 _ 6 alkyl, C 1 _ 4 alkoxyC 1 _ 4 alkoxyC 1 _ 6 alkyl, C 2 _ 4 alkynyloxyC 1 _ 6 alkyl, aminoC 1 _ 6 alkyl, N-C 1 _ 4 alkylaminoC 1 _ 6 alkyl, N,N-diC 1 _ 4 alkylaminoC 1 _ 6 alkyl, C 1 - 6 alkylcarbonylC 1 - 6 alkyl, C 1 _ 6 alkylcarbonylC 2
  • R 8 is C 3 _ 8 cycloalkyl, C 3 _ 8 cycloalkylC 1 _ 6 alkyl, wherein the cycloalkyl moiety is optionally partially unsaturated, phenyl, phenylC 1 _ 6 alkyl, phenylC 2 _ 6 alkenyl, napthyl, naphthylC 1 _ 6 alkyl, heteroaryl, heteroarylC 1 - 6 alkyl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterodiaryl, heterodiarylC 1 - 6 alkyl wherein the heterodiaryl moiety is a 9- or 10-membered bicyclic aromatic system which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl, heterocyclylC 1 - 6 alkyl wherein the heterocyclyl
  • R 10 is C 3 _ 8 cycloalkyl, C 3 - 8 cycloalkylC 1 - 2 alkyl, phenyl, phenylC 1 _ 2 alkyl, heteroaryl, heteroarylC 1 _ 2 alkyl wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl or heterocyclylC 1 _ 6 alkyl wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, and wherein any of said cycloalkyl, phenyl, heteroaryl and heterocyclyl moieties are optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R 11 ; wherein
  • R 11 is hydrogen, cyano, fluoro, chloro, bromo, methyl, trifluoromethyl, methoxy and ethoxy; or R 8 represents -OR 12 , wherein R 12 is hydrogen, C 1 _ 6 alkyl, C 3 _ 6 alkenyl, C 3 _ 6 alkynyl, cyanoC 1 _
  • R 12 is d scycloalkyl, C 1 _ 8 cycloalkylC 1 _ 6 alkyl, wherein the cycloalkyl moiety is optionally partially unsaturated, phenyl, phenylC 1 _ 6 alkyl, heteroaryl, heteroarylC 1 _ 6 alkyl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl or heterocyclylC 1 _ 6 alkyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S; wherein for R 12 , any cycloalkyl, phenyl, heteroaryl or heterocyclyl moiety is optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R 13 ; where
  • R 8 represents -NR 14 R 15 , wherein R 14 is hydrogen, cyano, C 1 _ 6 alkyl, C 1 _ 6 alkoxy, C 2 _ 6 alkenyl, C 2 _ 6 alkynyl, C 3 _ 6 alkenyloxy, C 3 _ 6 alkynyloxy, cyanoC 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 1 _ 6 haloalkenyl, hydroxyC 1 _ 6 alkyl, C 1 - 4 alkoxyC 1 _ 6 alkyl, C 1 _ 4 haloalkoxyC 1 _ 6 alkyl, C 1 _ 4 alkoxyC 1 _ 4 alkoxyC 1 _ 6 alkyl, aminoC 1 _ 6 alkyl, N-C 1 _ 4 alkylaminoC 1 _ 6 alkyl, N,N-diC 1 _ 4 alkylaminoC 1 _ 6 alkyl, C 1 _
  • R 14 is C 3 _ 8 cycloalkyl, C 3 _ 8 cycloalkylC 1 _ 6 alkyl, C 3 _ 8 cycloalkylC 1 _ 6 alkoxy, C 3 _ 6 cycloalkyloxy, wherein the cycloalkyi moiety is optionally partially unsaturated, phenyl, phenylC 1 _ 6 alkyl, phenylC 1 _ 6 alkoxy, heteroaryl, heteroarylC 1 _ 6 alkyl, heteroarylC 1 _ 6 alkoxy, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl, heterocyclylC 1 _ 6 alkyl or heterocyclylC 1 _ 6 alkoxy wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 hetero
  • R 16 may also represent oxo on the C 3 _ 8 cycloalkyl or heterocyclyl moiety;
  • novel compounds of formula (I) have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.
  • an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I).
  • 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 refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine.
  • cyano means a -CN group.
  • amino means an -NH 2 group.
  • hydroxy means an -OH group.
  • carbonylamino means an -N(H)C(0)H group.
  • formyl means an -C(0)H group.
  • acyl means an -C(0)CH 3 group.
  • C 1 _ 6 alkyl refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to six carbon atoms, and which is attached to the rest of the molecule by a single bond.
  • C 1 _ 4 alkyl and “C 1 - 2 alkyl” are to be construed accordingly.
  • C 1 _ 6 alkyl examples include, but are not limited to, methyl, ethyl, n-propyl, 1 -methylethyl (iso-propyl), n-butyl, 1 , 1 -dimethylethyl (ieri-butyl) and n-pentyl.
  • a "C 1 -C 6 alkylene" group refers to the corresponding definition of C 1 -C 6 alkyl (and C 1 _ 4 alkyl and C 1 _ 2 alkyl), except that such radical is attached to the rest of the molecule by two single bonds.
  • Examples of C 1 _ C 6 alkylene include, but are not limited to, -CH 2 -, -CH 2 CH 2 - and -(CH 2 )3-.
  • 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 3 _ 6 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 3 _ 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-C 1 _ 4 alkylamino refers to a radical of the formula -NH-R a where R a is a C 1 - 4 alkyl radical as defined above.
  • N,N-diC 1 _ 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.
  • C 1 _ 6 alkoxy refers to a radical of the formula -OR a where R a is a C 1 _ 6 alkyl radical as generally defined above.
  • R a is a C 1 _ 6 alkyl radical as generally defined above.
  • C 1 _ 4 alkoxy and “C 1 _ 2 alkoxy” are to be construed accordingly.
  • Examples of C 1 _ 6 alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, iso- propoxy, butoxy.
  • C 1 _ 4 alkoxycarbonyloxy refers to a radical of the formula -OC(0)R a where R a is a C 1 _ 4 alkoxy radical as generally defined above.
  • C 1 _ 4 alkoxycarbonyloxyC 1 _ 4 alkyl refers to a C 1 _ 4 alkyl radical as generally defined above substituted by a C 1 _ 4 alkoxycarbonyloxy radical as generally defined above.
  • hydroxyC 1 _ 4 alkyl refers to a C 1 _ 4 alkyl radical as generally defined above substituted by one or more hydroxy groups as defined above.
  • C 1 _ 6 alkylcarbonyl refers to a radical of the formula -C(0)R a where R a is a C 1 - 6 alkyl radical as generally defined above.
  • C 1 _ 4 alkylcarbonyl is to be construed accordingly.
  • C 1 _ 6 alkoxycarbonyl refers to a radical of the formula -C(0)OR a where R a is a C 1 - 6 alkyl radical as generally defined above.
  • R a is a C 1 - 6 alkyl radical as generally defined above.
  • C 1 _ 4 alkoxycarbonyl is to be construed accordingly.
  • C 1 _ 6 alkylcarbonyloxy refers to a radical of the formula -OC(0)R a where R a is a C 1 _ 6 alkyl radical as generally defined above.
  • C 1 _ 4 alkylcarbonyloxy is to be construed accordingly.
  • N-C 1 _ 4 alkylaminocarbonyl refers to a radical of the formula - C(0)NHR a where R a is a C 1 _ 4 alkyl radical as generally defined above.
  • N,N-diC 1 _ 4 alkylaminocarbonyl refers to a radical of the formula -
  • C 1 _ 4 alkylcarbonylamino refers to a radical of the formula -NHC(0)R a where R a is a C 1 _ 4 alkyl radical as generally defined above.
  • C 1 - 4 alkylcarbonylaminoC 1 - 6 alkyr' refers to a C 1 _ 6 alkyl radical as generally defined above substituted by a C 1 _ 4 alkylcarbonylamino group as defined above.
  • C 1 _ 4 alkoxycarbonylamino refers to a radical of the formula -
  • R a is a C 1 _ 4 alkyl radical as generally defined above.
  • C 1 _ 4 alkoxycarbonylaminoC 1 _ 6 alkyl refers to a C 1 _ 6 alkyl radical as generally defined above substituted by a C 1 _ 4 alkoxycarbonylamino group as defined above.
  • C 1 _ 6 alkylsulfanyl refers to a radical of the formula -SR a where R a is a C 1 - 6 alkyl radical as generally defined above.
  • C 1 _ 4 alkylsulfanyl is to be construed accordingly.
  • C 1 _ 6 alkylsulfinyl refers to a radical of the formula -S(0)R a where R a is a C 1 - 6 alkyl radical as generally defined above.
  • C 1 _ 4 alkylsulfonyl is to be construed accordingly.
  • C 1 _ 6 alkylsulfonyl refers to a radical of the formula -S(0) 2 R a where R a is a C 1 - 6 alkyl radical as generally defined above.
  • R a is a C 1 - 6 alkyl radical as generally defined above.
  • C 1 _ 4 alkylsulfonyl is to be construed accordingly.
  • C 1 _ 6 alkylsulfonylamino refers to a radical of the formula -NHS(0) 2 R a where R a is a C 1 _ 6 alkyl radical as generally defined above.
  • R a is a C 1 _ 6 alkyl radical as generally defined above.
  • C 1 _ 4 alkylsulfonylamino is to be construed accordingly.
  • C 3 _ 6 alkenyloxy refers to a radical of the formula -OR a where R a is a C 3 _ 6 alkenyl radical as generally defined above.
  • C 2 _ 6 alkynloxy 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 alkynloxy and “C 3 _ 6 alkynyloxy” are to be construed accordingly.
  • C 3 _ 6 haloalkenyloxy refers to a C 3 _ 6 alkenyloxy radical as generally defined above substituted by one or more of the same or different halogen atoms_
  • C 2 _ 6 alkynyloxycarbonylamino refers to a radical of the formula - NHC(0)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 alkynyloxycarbonylamino is to be construed accordingly.
  • C 1 _ 4 haloalkoxy refers to a C 1 _ 4 alkoxy group as defined above substituted by one or more of the same or different halogen atoms.
  • Examples of C 1 _ 4 haloalkoxy include, but are not limited to, fluoromethoxy, fluoroethoxy, trifluoromethoxy, trifluoroethoxy.
  • cyanoC 1 _ 6 alkyl refers to a C 1 _ 6 alkyl radical as generally defined above substituted by one or more cyano groups as defined above.
  • cyanoC 1 _ 4 alkyl is to be construed accordingly. Examples of cyanoC 1 _ 6 alkyl include, but are not limited to cyanomethyl, cyanoethyl.
  • C 1 _ 6 haloalkyl refers to a C 1 _ 6 alkyl radical as generally defined above substituted by one or more of the same or different halogen atoms.
  • C 1 _ 4 haloalkyl is to be construed accordingly.
  • Examples of C 1 _ 6 haloalkyl include, but are not limited to fluoromethyl, fluoroethyl, trifluoromethyl, 2,2,2-trifluoroethyl.
  • 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 and “C 3 _ 6 haloalkenyl” are to be construed accordingly.
  • C 1 _ 4 haloalkylcarbonyloxy refers to a radical of the formula -OC(0)R a where R a is a C 1 _ 4 haloalkyl radical as generally defined above.
  • C 1 _ 4 haloalkylcarbonyloxyC 1 _ 4 alkyl refers to a C 1 _ 4 alkyl radical as generally defined above substituted by a C 1 _ 4 haloalkylcarbonyloxy radical as generally defined above.
  • hydroxyC 1 _ 6 alkyl refers to a C 1 _ 6 alkyl radical as generally defined above substituted by one or more hydroxy groups as defined above.
  • hydroxyC 1 _ 4 alkyl is to be construed accordingly.
  • C 1 _ 4 alkoxyC 1 _ 6 alkyl refers to a C 1 _ 6 alkyl radical as generally defined above substituted by a C 1 _ 4 alkoxy group as defined above.
  • the terms “C 1 _ 4 alkoxyC 1 _ 4 alkyl” and “C 1 _ 2 alkoxyC 1 _ 4 alkyl” are to be construed accordingly.
  • Examples of C 1 _ 4 alkoxyC 1 _ 6 alkyl include, but are not limited to methoxymethyl, 2-methoxyethyl.
  • C 1 _ 4 haloalkoxyC 1 _ 6 alkyl refers to a C 1 _ 6 alkyl radical as generally defined above substituted by a C 1 _ 4 haloalkoxy group as defined above.
  • C 1 _ 4 halolalkoxyC 1 _ 4 alkyl and “C 1 _ 2 haloalkoxyC 1 _ 4 alkyl” are to be construed accordingly.
  • C 1 _ 4 alkoxyC 1 _ 4 alkoxyC 1 _ 6 alkyl refers to a C 1 _ 6 alkyl radical as generally defined above substituted by a C 1 _ 4 alkoxy group as defined above, the C 1 _ 4 alkoxy group itself substituted by a C 1 _ 4 alkoxy group as defined above.
  • C 2 _ 6 alkynyloxyC 1 _ 6 alkyl refers to a C 1 _ 6 alkyl radical as generally defined above substituted by a C 2 _ 6 alkynyloxy group as defined above.
  • aminoC 1 _ 6 alkyl refers to a C 1 _ 6 alkyl radical as generally defined above substituted by one or more amino groups as defined above.
  • aminoC 1 _ 4 alkyl is to be construed accordingly.
  • N-C 1 _ 4 alkylaminoC 1 _ 6 alkyl refers to a C 1 _ 6 alkyl radical as generally defined above substituted by a N-C 1 _ 4 alkylamino group as defined above.
  • N-C 1 _ 4 alkylaminoC 1 _ 4 alkyl is to be construed accordingly.
  • N,N-diC 1 _ 4 alkylaminoC 1 _ 6 alkyl refers to a C 1 _ 6 alkyl radical as generally defined above substituted by a N,N-diC 1 _ 4 alkylamino group as defined above.
  • the term "N,N-diC 1 _ 4 alkylaminoC 1 _ 4 alkyl” is to be construed accordingly.
  • C 1 _ 6 alkylcarbonylC 1 _ 6 alkyl refers to a C 1 _ 6 alkyl radical as generally defined above substituted by a C 1 _ 6 alkylcarbonyl group as defined above.
  • C 1 _ 6 alkylcarbonylC 1 _ 4 alkyl is to be construed accordingly.
  • C 1 _ 6 alkylcarbonylC 2 _ 6 alkenyl refers to a C 2 _ 6 alkenyl radical as generally defined above substituted by a C 1 _ 6 alkylcarbonyl group as defined above.
  • C 1 _ 6 alkylcarbonylC 2 - 4 alkenyl is to be construed accordingly.
  • C 1 _ 6 alkoxycarbonylC 1 _ 6 alkyl refers to a C 1 _ 6 alkyl radical as generally defined above substituted by a C 1 _ 6 alkoxycarbonyl group as defined above.
  • C 1 _ 6 alkoxycarbonylC 1 _ 4 alkyl is to be construed accordingly.
  • C 1 _ 6 alkylcarbonyloxyC 1 _ 6 alkyl refers to a C 1 _ 6 alkyl radical as generally defined above substituted by a C 1 _ 6 alkylcarbonyloxy group as defined above.
  • C 1 _ 6 alkylcarbonyloxyC 1 _ 4 alkyl is to be construed accordingly.
  • N-C 1 - 4 alkylaminocarbonylC 1 - 6 alkyr' refers to a C 1 _ 6 alkyl radical as generally defined above substituted by a N-C 1 _ 4 alkylaminocarbonyl group as defined above.
  • N-C 1 _ 4 alkylaminocarbonylC 1 _ 4 alkyl is to be construed accordingly.
  • N,N-diC 1 _ 4 alkylaminocarbonylC 1 _ 6 alkyl refers to a C 1 _ 6 alkyl radical as generally defined above substituted by a N,N-diC 1 _ 4 alkylaminocarbonylC 1 _ 6 alkyl group as defined above.
  • C 1 - 6 alkylsulfanylC 1 - 6 alkyr' refers to a C 1 _ 6 alkyl radical as generally defined above substituted by a C 1 _ 6 alkylsulfanyl group as defined above.
  • C 1 _ 6 alkylsulfanylC 1 _ 4 alkyl is to be construed accordingly.
  • C 1 - 6 alkylsulfonylC 1 - 6 alkyr' refers to a C 1 _ 6 alkyl radical as generally defined above substituted by a C 1 _ 6 alkylsulfonyl group as defined above.
  • C 1 _ 6 alkylsulfonylC 1 _ 4 alkyl is to be construed accordingly.
  • C 1 - 6 alkylsulfonylaminoC 1 - 6 alkyr' refers to a C 1 _ 6 alkyl radical as generally defined above substituted by a C 1 _ 6 alkylsulfonylamino group as defined above.
  • C 1 _ 6 alkylsulfonylaminoC 1 _ 4 alkyl is to be construed accordingly.
  • C 1 _ 6 alkylsulfonylaminoC 1 _ 6 alkynyr refers to a d ⁇ alkynyl radical as generally defined above substituted by a C 1 _ 6 alkylsulfonylamino group as defined above.
  • C 1 _ 6 alkylsulfonylaminoC 1 _ 4 alkynyl is to be construed accordingly.
  • C 1 _ 6 alkynyloxycarbonylaminoC 1 _ 6 alkyl refers to a C 1 _ 6 alkyl radical as generally defined above substituted by a d ealkynyloxycarbonylamino group as defined above.
  • the term "C 2 - 4 alkynyloxycarbonylaminoC 1 _ 4 alkyl" is to be construed accordingly.
  • C 1 _ 8 cycloalkyl may be mono- or bi-cyclic and contains 3 to 8 carbon atoms.
  • C 1 _ 6 cycloalkyl is to be construed accordingly.
  • Examples of C 1 _scycloalkyl include, but are not limited to, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • aryl refers to an aromatic ring system consisting solely of carbon and hydrogen atoms which may be mono-, bi- or tricyclic. Examples of such ring systems include phenyl, naphthalenyl, anthracenyl, indenyl or phenanthrenyl.
  • heteroaryl refers to a 5- or 6-membered aromatic monocyclic ring radical which comprises 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur.
  • the heteroaryl radical may be bonded via a carbon atom or heteroatom.
  • heteroaryl include, but are not limited to, furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl or pyridyl.
  • heteroaryl refers to a stable 9- or 10-membered bicyclic aromatic ring system which comprises 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur.
  • the heteroaryl radical may be bonded via a carbon atom or heteroatom.
  • heterocyclyl refers to a stable 4-, 5- or 6-membered non-aromatic monocyclic ring radical which comprises 1 , 2, or 3, heteroatoms individually selected from nitrogen, oxygen and sulfur.
  • the heterocyclyl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom.
  • heterocyclyl examples include, but are not limited to, azetidinyl, oxetanyl, pyrrolinyl, pyrrolidyl, thietanyl, tetrahydrofuryl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidyl, piperazinyl, tetrahydropyranyl, morpholinyl or perhydroazepinyl.
  • C 3 - 8 cycloalkylCo- 6 alkyl refers to a C 3 _ 8 cycloalkyl ring as defined above attached to the rest of the molecule by a single bond or by a C 1 -C 6 alkylene radical as defined above. "C 3 - 6 cycloalkylC 1 - 2 alkyr' is to be construed accordingly.
  • Examples of C 3 _ 8 cycloalkylC 0 - 6 alkyl include, but are not limited to, cyclopropyl, cyclopropylmethyl, cyclopropylethyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • C 3 - 6 cycloalkylC 1 - 2 alkoxy refers to a C 1 _ 2 alkoxy radical as generally defined above substituted by a C 3 - 6 cycloalkyl ring as defined above.
  • C 3 _ 6 cycloalkylcarbonyl refers to a -C(0)R a radical, wherein R a is a C 3 - 6 cycloalkyl ring as defined above.
  • C 3 _ 6 cycloalkylcarbonyloxy refers to a -OC(0)R a radical wherein R a is a C 3 _ 6 cycloalkyl ring as described above.
  • C 3 _ 6 cycloalkylcarbonyloxyC 1 _ 4 alkyl refers to a C 3 _ 6 cycloalkylcarbonyloxy group as described above attached to the rest of the molecule by a C 1 _ 4 alkylene radical as defined above.
  • phenylC 0 - 6 alkyl refers to a phenyl ring attached to the rest of the molecule by a single bond or by a C 1 _ 6 alkylene radical as defined above.
  • PhenylC 1 _ 6 alkyl and “phenylC 1 _ 2 alkyl” are to be construed accordingly.
  • Examples of phenylC 0 - 6 alkyl include, but are not limited to, phenyl, benzyl or 2-phenylethyl.
  • phenylC 1 _ 2 alkoxy refers to a C 1 _ 2 alkoxy radical as generally defined above substituted by a phenyl ring.
  • phenylC 2 _ 6 alkenyl refers to a C 2 _ 6 alkenyl radical as generally defined above substituted by a phenyl ring.
  • phenylcarbonyloxy refers to a -OC(0)R a radical wherein R a is a phenyl ring.
  • phenylcarbonyloxyC 1 _ 4 alkyl refers to a phenylcarbonyloxy group as described above attached to the rest of the molecule by a C 1 _ 4 alkylene radical as defined above.
  • naphthylC 0 - 6 alkyl refers to a naphthalene ring attached to the rest of the molecule by a single bond or by a C 1 _ 6 alkylene radical as defined above.
  • heteroarylC 0 - 6 alkyl refers to a heteroaryl ring as described above attached to the rest of the molecule by a single bond or by a C 1 _ 6 alkylene radical as defined above.
  • “HeteroarylC 1 - 6 alkyr' and “heteroarylC 1 _ 2 alkyl” are to be construed accordingly.
  • heteroarylC 1 _ 6 alkoxy refers to a C 1 _ 6 alkoxy radical as generally defined above substituted by a heteroaryl group as generally defined above.
  • HeteroarylC 1 _ 2 alkoxy is to be construed accordingly.
  • heteroarylC 0 - 6 alkyl refers to a heterodiaryl ring as described above attached to the rest of the molecule by a single bond or by a C 1 _ 6 alkylene radical as defined above.
  • HeterodiarylC 1 - 6 alkyr' and “heterodiarylC 1 _ 2 alkyl” are to be construed accordingly.
  • heterocyclylC 0 - 6 alkyl refers to a heterocyclyl ring as described above attached to the rest of the molecule by a single bond or by a C 1 _ 6 alkylene radical as defined above.
  • “HeterocyclylC 1 - 6 alkyr' and “heterocyclylC 1 _ 2 alkyl” are to be construed accordingly.
  • heterocyclylC 1 _ 6 alkoxy refers to a C 1 _ 6 alkoxy radical as generally defined above substituted by a heterocyclyl group as generally defined above.
  • HeterocyclylC 1 - 2 alkoxy is to be construed accordingly.
  • heterocyclylcarbonyloxy refers to a -OC(0)R a radical wherein R a is a heteroaryl ring as described above.
  • heterocyclylcarbonyloxyC 1 - 4 alkyl refers to a heterocyclylcarbonyloxy group as described above attached to the rest of the molecule by a C 1 _ 4 alkylene radical as defined above.
  • C3- 6 cycloalkylcarbonylaminoC 1 - 6 alkyr' refers to a a radical of the formula -R a NHC(0)R b , wherein R a is a C 1 _ 6 alkyl radical as defined above and R b is a C 3 - 6 cycloalkyl ring as described above.
  • asymmetric carbon atoms in a compound of formula (I) means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. Also atropisomers may occur as a result of restricted rotation about a single bond.
  • Formula (I) is intended to include all those possible isomeric forms and mixtures thereof.
  • the present invention includes all those possible isomeric forms and mixtures thereof for a compound of formula (I).
  • formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism) where present.
  • the present invention includes all possible tautomeric forms for a compound of formula (I).
  • the compounds of formula (I) according to the invention are in free form, in covalently hydrated form, in oxidized form as an N-oxide or in salt form, e.g., an agronomically usable or agrochemically acceptable salt form.
  • N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
  • 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 1 is hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy.
  • a 2 represents N or CR 2 , wherein R 2 is hydrogen, halogen, methyl, ethyl, difluoromethyl, 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 0, 1 or 2 of A 1 , A 2 , A 3 and A 4 are N;
  • R 1 and R 2 are independently selected from hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy.
  • R 1 and R 2 are independently selected from hydrogen and halogen. More preferably, R 1 and R 2 are hydrogen.
  • R 3 and R 4 are independently selected from hydrogen and halogen.
  • R 3 and R 4 are independently selected from hydrogen and fluoro. More preferably, R 3 and R 4 are hydrogen.
  • a 3 may represent CR 3 , wherein R 3 is hydrogen or halogen.
  • a 4 may represent CR 4 , wherein R 4 is hydrogen or halogen.
  • R 1 , R 2 , R 3 and R 4 may be hydrogen.
  • three of R 1 , R 2 , R 3 and R 4 may be hydrogen, wherein more preferably R 2 , R 3 and R 4 are hydrogen.
  • 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 8 when R 8 is not -OR 12 or -NR 14 R 15 , preferably A 1 , A 2 , A 3 and A 4 are C-H; A 2 , A 3 and A 4 are C-H and A 1 is N; A 1 , A 2 and A 4 are C-H and A 3 is N; A 1 , A 2 and A 4 are C-H and A 3 is C-halogen (preferably fluoro); A 2 , A 3 and A 4 are C-H and A 1 is C-halogen (preferably fluoro) or A 2 , A 3 and A 4 are C-H and A 1 is C-halogen (preferably fluoro); A 2 and A 4 are C-H and A 1 and A 3 are C-halogen (preferably fluoro); or A 3 and A 4 are C-H and A 1 and A 2 are C-halogen (preferably fluoro). More preferably, A 1 , A 2 , A 3 and A 4 are C-H.
  • R 8 when R 8 is -OR 12 , preferably A 1 , A 2 , A 3 and A 4 are C-H.
  • R 8 when R 8 is -NR 14 R 15 , preferably A 1 , A 2 , A 3 and A 4 are C-H; A 1 , A 2 and A 4 are C-H and A 3 is C-halogen (preferably fluoro); or A 2 , A 3 and A 4 are C-H and A 1 is C-halogen (preferably fluoro). More preferably, A 1 , A 2 , A 3 and A 4 are C-H.
  • R 5 and R 6 independently represent 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 may be 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. More preferably, R 5 and R 6 are independently selected from hydrogen, C 1 _ 4 alkyl (in particular methyl) and cyano.
  • R 5 and R 6 are hydrogen; R 5 is hydrogen and R 6 is methyl; or R 5 is hydrogen and R 6 is cyano. More preferably, R 5 and R 6 are hydrogen and n is 1.
  • R 8 when R 8 is -OR 12 , preferably R 5 and R 6 are hydrogen and n is 1.
  • R 8 is -NR 14 R 15 , preferably R 5 and R 6 are hydrogen and n is 1.
  • R 7 is hydroxy, C 1 _ 4 alkyl, C 2 - 4 haloalkyl, C 1 _ 4 alkoxy, hydroxyC 1 _ 4 alkyl, C 1 . 2 alkoxyC 1 _ 4 alkyl, d. 2 haloalkoxyC 1 - 4 alkyl, C 3 _ 4 alkynyl, C 3 . 6 alkenyl, C 3 . 6 alkenyloxy, C 3 . 6 alkynyloxy, C 3 . 6 haloalkenyl, C 3 .
  • heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S
  • the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 or 2 heteroatoms individually selected from N, O and S
  • any of said cycloalkyl, phenyl, heteroaryl and heterocyclyl moieties are optionally substituted by 1 or 2 substituents selected from cyano, fluoro, chloro, bromo, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy.
  • R 7 is C 1 _ 4 alkyl, C 1 _ 4 alkoxy, C 1 - 2 haloalkoxyC 1 - 4 alkyl, C 3 . 6 alkenyl, C 3 _ 4 alkynyl, C 3 . 6 alkenyloxy, C 3 . 6 alkynyloxy, C 3 . 6 haloalkenyl, C 3 . 6 haloalkenyloxy, C 3 . 6 cycloalkyl, C 3 .
  • R 7 is C 1 _ 4 alkyl, C 1 _ 4 alkoxy, C 1 _ 2 alkoxyC 1 _ 4 alkyl, C 3 . 6 alkenyl, C 3 _ 4 alkynyl, C 3 .
  • R 7 is hydroxy, C 1 _ 4 alkyl, C 2 _ 4 haloalkyl, C 1 _ 4 alkoxy, hydroxyC 1 _ 4 alkyl, C 1 _ 2 alkoxyC 1 _ 4 alkyl, C 3 . 6 alkenyl, C 3 . 4 alkynyl, C 3 . 6 haloalkenyloxy, C 3 . 6 cycloalkyl, C 3 .
  • R 7 is hydroxy, C 1 _ 4 alkyl, C 2 _ 4 fluoroalkyl, C 1 _ 4 alkoxy, hydroxyC 1 _ 4 alkyl, C 1 _ 2 alkoxyC 1 _ 4 alkyl, C 3 . 4 alkenyl, C 3 _ 4 alkynyl, C 3 .
  • R 7 is C 1 _ 4 alkyl, C 2 _ 4 haloalkyl, C 1 _ 4 alkoxy or C 3 . 6 cycloalkyl. Further more preferably, R 7 is C 1 _ 4 alkyl, C 2 _ 4 fluoroalkyl, methoxy, ethoxy or cyclopropyl. Most preferably, R 7 is methyl, ethyl, n-propyl, iso-propyl, 2,2,2-fluoroethyl, methoxy, ethoxy or cyclopropyl. In the compounds according to Formula (I), when R 8 is -OR 12 , preferably R 7 is hydroxy, C 1 _
  • R 7 is hydroxy, C 1 _ 4 alkyl, C 2 _ 4 haloalkyl, C 1 _ 4 alkoxy, C 3 . 6 alkenyl, C 3 _ 4 alkynyl, C 1 _ 4 alkoxycarbonyloxy. More preferably, R 7 is hydroxy, C 1 _ 4 alkyl, C 2 _ 4 haloalkyl, C 1 _ 4 alkoxy, C 3 _ 4 alkenyl, C 3 _ 4 alkynyl, C 1 _ 4 alkoxycarbonyloxy. Even more preferably, R 7 is C 1 _ 4 alkoxy, in particular, methoxy. In the compounds according to Formula (I), when R 8 is -NR 14 R 15 , preferably R 7 is hydroxy, C 1 _
  • R 7 is hydroxy, C 1 _ 4 alkyl, C 2 haloalkyl, C 1 . 2 alkoxy, C 1 _ 4 alkenyl, C 1 _ 4 alkynyl, cyclopropyl. Even more preferably, R 7 is C 1 _ 4 alkyl or C 1 _ 4 alkoxy, and in particular, methyl, ethyl or methoxy.
  • R 8 is hydrogen, C 1 _ 6 alkyl, d ⁇ alkenyl, d ⁇ alkynyl, cyanoC 1 . 6 alkyl, d. 6 haloalkyl, C 2 -
  • R 8 is C 3 . 8 cycloalkyl, C3. 8 cycloalkylC 1 . 6 alkyl, wherein the cycloalkyl moiety is optionally partially unsaturated, phenyl, phenylC 1 _ 6 alkyl, phenylC 2 .
  • heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterodiaryl, heterodiarylC 1 - 6 alkyl wherein the heterodiaryl moiety is a 9- or 10-membered bicyclic aromatic system which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl, heterocyclylC 1 - 6 alkyl wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, or C 3 .
  • any cycloalkyl, phenyl, napthyl, heteroaryl, heterodiaryl, heterocyclyl moiety is optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R 9 ; or, additionally, when R 8 is cyclopropyl, the cyclopropyl moiety is substituted by 4 substituents, which may be the same or different, selected from R 9 , with the proviso that at least 2 R 9 substituents are the same;
  • R 9 is cyano, halogen, hydroxy, C 1 _ 4 alkyl, C 2 - 4 alkenyl, C 2 _ 4 alkynyl, C 1 _ 4 haloalkyl, C 2 _ 4 haloalkenyl, C 1 - 4 alkoxy, C 1 _ 4 haloalkoxy, C 3 _ 4 alkynyloxy, N-C 1 _ 4 alkylamino, N,N-diC 1 _ 4 alkylamino, C 1 _ 4 alkylcarbonyl, C 3 .
  • R 9 may also represent oxo on the C 3 .
  • any cycloalkyl, phenyl, napthyl, heteroaryl, heterodiaryl, heterocyclyl, moiety is optionally substituted by 1 substituent selected from R 10 and further optionally substituted by 1 or 2 substituents selected from R 9 ; wherein R 10 is C 3 . 8 cycloalkyl, C 3 . 8 cycloalkylC 1 _ 2 alkyl, phenyl, phenylC 1 _ 2 alkyl, heteroaryl, heteroarylC 1 _
  • heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl, heterocyclylC 1 _ 6 alkyl wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, and wherein any of said cycloalkyl, phenyl, heteroaryl and heterocyclyl moieties are optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R 11 ; wherein R 11 is hydrogen, cyano, fluoro, chloro, bromo, methyl, trifluoromethyl, methoxy and ethoxy.
  • R 8 is hydrogen, C 1 _ 6 alkyl, C 2 -6alkenyl, C 2 -6alkynyl, cyanoC 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 1 _ 6 haloalkenyl, hydroxyC 1 _ 6 alkyl, C 1 _ 4 alkoxyC 1 _ 6 alkyl, C 1 _ 4 haloalkoxyC 1 . 6 alkyl, C 1 -4alkoxyC 1 .4alkoxyC 1 . 6 alkyl, C 2 -4alkynyloxyC 1 .
  • R 8 is C 3 . 8 cycloalkyl, C 3 . 8 cycloalkylC 1 - 6 alkyl, wherein the cycloalkyl moiety is optionally partially unsaturated, phenyl, phenylC 1 _ 6 alkyl, phenylC 2 .
  • heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterodiaryl, heterodiarylC 1 _ 6 alkyl wherein the heterodiaryl moiety is a 9- or 10-membered bicyclic aromatic system which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl, heterocyclylC 1 _ 6 alkyl wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, and C3.
  • 6 cycloalkylcarbonylaminoC 1 . 6 alkyl At least one of C 3 . scycloalkyl, C 3 -8cycloalkylC 1 - 6 alkyl, phenyl, phenylC 1 _ 6 alkyl, phenylC 2 . 6 alkenyl, napthyl, naphthylC 1 _ 6 alkyl, heteroaryl, heteroarylC 1 _ 6 alkyl, heterodiaryl, heterodiarylC 1 _ 6 alkyl, heterocyclyl, heterocyclylC 1 . 6 alkyl and C3. 6 cycloalkylcarbonylaminoC 1 .
  • 6 alkyl moieties may be substituted by 1 , 2 or 3 substituents selected from cyano, halogen, hydroxy, C 1 _ 4 alkyl, C 2 _ 4 alkenyl, C 2 _ 4 alkynyl, C 1 _ 4 haloalkyl, C 2 .
  • R 8 is hydrogen, C 1 _ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoC 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 2 . 6 haloalkenyl, hydroxyC 1 _ 6 alkyl, C 1 _ 4 alkoxyC 1 _ 6 alkyl, C 1 _ 4 haloalkoxyC 1 _ 6 alkyl, C 1 _ 4 alkoxyC 1 _ 4 alkoxyC 1 . 6 alkyl, C 2 _ 4 alkynyloxyC 1 _ 6 alkyl, aminoC 1 _ 6 alkyl, C 1 .
  • R 8 is C 3 . 8 cycloalkyl, C 3 .
  • cycloalkylC 1 _ 6 alkyl wherein the cycloalkyl moiety is optionally partially unsaturated, phenyl, phenylC 1 _ 6 alkyl, phenylC 1 _ 6 alkenyl, napthyl, heteroaryl, heteroarylC 1 . 6 alkyl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl, heterocyclyld.
  • heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, or C 3 -6cycloalkylcarbonylaminoC 1 _ 6 alkyl, wherein for R 8 , any of C 1 _scycloalkyl, C 1 _scycloalkylC 1 _ 6 alkyl, phenyl, phenyld. 6 alkyl, phenylC 1 _ 6 alkenyl, napthyl, heteroaryl, heteroaryld.
  • R is cyano, halogen, hydroxy, C 1 _ 4 alkyl, C-
  • R 10 is phenyl, heteroaryl wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein any of said phenyl and heteroaryl moieties are optionally substituted by a single substituents selected from R 11 ; wherein R 11 is cyano, fluoro, chloro, bromo, methyl, trifluoromethyl, methoxy and ethoxy.
  • R 8 is C 1 _ 6 alkyl, C 2 - 4 alkenyl, C 2 - 4 alkynyl, cyanoC 1 _ 4 alkyl, C 1 _ 5 haloalkyl, C 2 . 4 haloalkenyl, hydroxyC 1 _ 4 alkyl, C 1 _ 2 alkoxyC 1 _ 4 alkyl, C 1 _ 2 haloalkoxyC 1 _ 4 alkyl, C 1 . 2 alkoxyC 1 _ 2 alkoxyC 1 .
  • R 8 is C 3 . 6 cycloalkyl, C 3 . 6 cycloalkylC 1 _ 2 alkyl, wherein the cycloalkyl moiety is optionally partially unsaturated, phenyl, phenyld.
  • heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, heterocyclyl, heterocyclylC 1 _ 2 alkyl wherein the heterocyclyl moiety is a 4- to 6- membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, or C 3 .
  • phenyl moieties are optionally substituted by 1 substituent selected from R 10 and are further optionally substituted by 1 or 2 substituents selected from R 9 ; wherein R 10 is phenyl, heteroaryl wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein any of said phenyl and heteroaryl moieties are optionally substituted by a single substituents selected from R 11 ; wherein R 11 is cyano, fluoro, chloro, bromo, methyl, trifluoromethyl, methoxy and ethoxy.
  • R 8 is C 1 _ 6 alkyl, C 2 _ 4 alkenyl, C 2 _ 4 alkynyl, cyanoC 1 _ 4 alkyl, C 1 _ 5 haloalkyl, C 2 . 4 haloalkenyl, hydroxyC 1 _ 4 alkyl, C 1 _ 2 alkoxyC 1 _ 4 alkyl, C 1 _ 2 haloalkoxyC 1 _ 4 alkyl, C 1 . 2 alkoxyC 1 _ 2 alkoxyC 1 .
  • R 8 is C 3 . 6 cycloalkyl, C 3 . 6 cycloalkylC 1 _ 2 alkyl, phenyl, phenylC 1 _ 4 alkyl, phenylC 2 _ 4 alkenyl, napthyl, a heteroaryl-containing moiety selected from furanyl (including furan-2-yl, furan-3-yl), pyrazolyl (including pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl), imidazolyl (including imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl), triazolyl (including 1 ,2,3-triazol-1-yl), 1 ,
  • R 9 is cyano, methyl, chloro, fluoro, hydroxyl, methoxy, trifluoromethyl, C 2 -haloalkenyl, methylcarbonyl, ethylcarbonyl, carbonylamino; or wherein the cycle of each heteroaryl-containing moiety or heterocyclyl-containing moiety is optionally substituted by 1 substituent selected from R 10 and further optionally substituted by 1 or 2 substituents selected from R 9 , wherein
  • R 10 is phenyl or pyridinyl (including pyridin-2-yl), wherein phenyl or pyridinyl is optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R 11 ; wherein
  • R 11 is fluoro, chloro, bromo and methoxy.
  • R 8 is C 1 _ 6 alkyl, C 1 - 2 haloalkyl, hydroxyC 1 _ 6 alkyl, C 1 - 2 alkoxyC 1 - 4 alkyl, C 3 . 6 cycloalkyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- or 5-membered non-aromatic ring which comprises 1 or 2 heteroatoms individually selected from N and O, wherein C 3 .
  • R 9 is cyano, halogen, hydroxy, C 1 _ 4 alkyl, C 2 - 4 alkenyl, C 2 _ 4 alkynyl, d ⁇ haloalkyl or C 1 _ 4 alkoxy. More preferably, R 8 is C 1 _ 4 alkyl, C 1 _ 2 haloalkyl, hydroxyC 1 _ 4 alkyl, C 1 _ 2 alkoxyC 1 _ 4 alkyl, C 3 .
  • 6 cycloalkyl or heterocyclyl wherein the heterocyclyl moiety is a 4- or 5-membered non-aromatic ring which comprises 1 or 2 heteroatoms which are oxygen, wherein C 3 . 6 cycloalkyl and heterocyclyl are optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R 9 ; wherein R 9 is cyano, fluoro, chloro, hydroxy, methyl, ethyl, trifluoromethyl and methoxy. Even more preferably, R 8 is C 1 _ 4 alkyl, C 1 _ 2 haloalkyl, hydroxyC 1 _ 4 alkyl, C 3 .
  • heterocyclyl moiety is a 4- or 5-membered non-aromatic ring which comprises 1 or 2 heteroatoms which are oxygen, wherein C 3 . 6 cycloalkyl and heterocyclyl are optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R 9 ; wherein R 9 is fluoro, chloro, methyl.
  • R 8 is C 1 _ 4 alkyl (methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso- butyl, t-butyl), 2,2,2-trifluoroethyl, hydroxyC 1 _ 4 alkyl, cyclopropyl or heterocyclyl, wherein the heterocyclyl moiety is tetrahydrofuran-2-yl, oxetan-3-yl or 1 ,3-dioxolan-2-yl, wherein cyclopropyl and heterocyclyl are each optionally substituted by 1 or 2 substituents selected from R 9 , wherein R 9 is fluoro, chloro, methyl.
  • R 8 may represent -OR 12 , wherein R 12 is hydrogen, C 1 _ 6 alkyl, C 3 . 6 alkenyl, C 3 . 6 alkynyl, cyanoC-i. 6 alkyl, C 1 _ 6 haloalkyl, C 3 . 6 haloalkenyl, hydroxyC 1 _ 6 alkyl, C 1 _ 4 alkoxyC 1 _ 6 alkyl, C 1 _ 4 haloalkoxyC 1 _ 6 alkyl, C 1 _ 4 alkoxyC 1 - 4 alkoxyC 1 . 6 alkyl, aminoC 1 _ 6 alkyl, N-C 1 _ 4 alkylaminoC 1 .
  • R 12 is C 3 . 8 cycloalkyl, C 3 . 8 cycloalkylC 1 . 6 alkyl, wherein the cycloalkyl moiety is optionally partially unsaturated, phenyl, phenylC 1 _ 6 alkyl, heteroaryl, heteroarylC 1 _ 6 alkyl, wherein the heteroaryl moiety is a
  • 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl, heterocyclylC 1 _ 6 alkyl, wherein the heterocyclyl moiety is a 4- to
  • any cycloalkyl, phenyl, heteroaryl, heterocyclyl moiety is optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R 13 ; wherein R 13 is cyano, halogen, hydroxy, C 1 _ 4 alkyl, C 2 - 4 alkenyl, C 2 - 4 alkynyl, C 1 _ 4 haloalkyl, C 2 -
  • R 13 may also represent oxo on the C 3 . 8 cycloalkyl or heterocyclyl moiety;
  • R 12 is hydrogen, C 1 _ 6 alkyl, C 3 . 6 alkenyl, C 3 . 6 alkynyl, cyanoC 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 3 . 6 haloalkenyl, hydroxyC 1 _ 6 alkyl, C 1 _ 4 alkoxyC 1 _ 6 alkyl, C 1 _ 4 haloalkoxyC 1 _ 6 alkyl, C 1 _ 4 alkoxyC 1 _ 4 alkoxyC 1 . 6 alkyl, aminoC 1 _ 6 alkyl, N-C 1 _ 4 alkylaminoC 1 .
  • R 12 is hydrogen, C 1 _ 6 alkyl, C 3 . 6 alkenyl, C 3 . 6 alkynyl, C 1 _ 6 haloalkyl, C 1 - 4 alkoxyC 1 - 6 alkyl, phenyl, phenylC 1 _ 6 alkyl.
  • R 12 is C 1 _ 6 alkyl, C 3 _ 4 alkenyl, C 3 . 4 alkynyl, C 1 _ 4 haloalkyl, C 1 . 2 alkoxyC 1 _ 4 alkyl, phenyl, phenylC 1 _ 2 alkyl. Still more preferably, R 12 is C 1 _ 6 alkyl, C 3 _ 4 alkenyl, C 3 _ 4 alkynyl, C 1 _ 4 fluoroalkyl, C 1 _ 4 chloroalkyl, phenyl, benzyl.
  • R 8 represents -NR 14 R 15 , wherein R 14 is hydrogen, cyano, C 1 _ 6 alkyl, C 1 _ 6 alkoxy, C 2 - 6 alkenyl, C 2 . 6 alkynyl, C 3 . 6 alkenyloxy, C 3 . 6 alkynyloxy, cyanoC 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 1 _ 6 haloalkenyl, hydroxyC 1 _ 6 alkyl, C 1 - 4 alkoxyC 1 - 6 alkyl, C 1 _ 4 haloalkoxyC 1 _ 6 alkyl, C 1 _ 4 alkoxyC 1 _ 4 alkoxyC 1 .
  • R 14 is C 3 . 8 cycloalkyl, C 3 . 8 cycloalkylC 1 . 6 alkyl, C 3 . 8 cycloalkylC 1 _ 6 alkoxy, C 3 . 6 cycloalkyloxy, wherein the cycloalkyl moiety is optionally partially unsaturated, phenyl, phenylC 1 _ 6 alkyl, phenyld.
  • heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl, heterocyclylC 1 _ 6 alkyl, heterocyclylC 1 _ 6 alkoxy wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S; wherein for R 14 , any cycloalkyl, phenyl, heteroaryl, heterocyclyl moiety is optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R 16 ; wherein
  • R 16 is cyano, halogen, hydroxy, C 1 _ 4 alkyl, C 2 - 4 alkenyl, C 2 _ 4 alkynyl, C 1 _ 4 haloalkyl, C 2 . 4 haloalkenyl, C 1 _ 4 alkoxy, C 1 _ 2 alkoxyC 1 _ 2 alkyl, C 1 _ 4 haloalkoxy, C 3 _ 4 alkenyloxy, C 3 _ 4 alkynyloxy, N-C 1 _ 4 alkylamino, N,N-diC 1 _ 4 alkylamino, C 1 _ 4 alkylcarbonyl, C 1 _ 4 alkoxycarbonyl, carbonylamino, N-C 1 _ 4 alkylaminocarbonyl, N,N-diC 1 _ 4 alkylaminocarbonyl or C 1 _ 4 alkoxycarbonylamino; and wherein when R 14 is substituted C 3 .
  • R 16 may also represent oxo on the C 3 . 8 cycloalkyl or heterocyclyl moiety;
  • R 15 is hydrogen, C 1 _ 4 alkyl, C 3 _ 4 alkynyl, C 1 _ 4 alkoxyC 1 _ 4 alkyl, cyanoC 1 _ 4 alkyl, C 3 . 6 cycloalkyl, C 3 . 6 cycloalkylC 1 _ 2 alkyl; or R 14 and R 15 , together with the nitrogen atom to which they are bonded, form a 4-, 5- or 6- membered cycle optionally containing an additional heteroatom selected from O, S and NR 17 ; wherein R 17 is hydrogen, methyl, methoxy, formyl or acyl.
  • R 8 represents -NR 14 R 15 , wherein R 14 is hydrogen, C 1 _ 6 alkyl, C 1 _ 6 alkoxy, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoC 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 1 _ 6 haloalkenyl, hydroxyC 1 _ 6 alkyl, C 1 _ 4 alkoxyC 1 . 6 alkyl, C 1 _ 4 haloalkoxyC 1 - 6 alkyl, C 1 - 4 alkoxyC 1 _ 4 alkoxyC 1 .
  • R 14 is hydrogen, cyano, C 1 _ 6 alkyl, C 1 _ 6 alkoxy, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoC 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 1 _ 4 alkoxyC 1 _ 6 alkyl, C 1 . 6 alkoxycarbonylC 1 . 6 alkyl, or C 3 . 8 cycloalkyl, C 3 .
  • R 14 is hydrogen, C 1 _ 6 alkyl, d.
  • R 14 is hydrogen, methyl, ethyl, propyl, iso-propyl, sec-butyl, methoxy, ethoxy, allyl, propyn-2-yl, 2,2,2-trifluoromethyl, cyclopropyl or cyclobutyl.
  • R 15 is hydrogen, methyl, ethyl, C 3 _ 4 alkynyl or methoxyethyl. More preferably, R 15 is hydrogen, methyl or ethyl, in particular, hydrogen.
  • R 15 may be hydrogen, C 1 _ 4 alkyl, C-
  • R 14 and R 15 together with the nitrogen atom to which they are bonded, may form a 5- or 6- membered cycle optionally containing an additional heteroatom which is oxygen.
  • n 1 ;
  • a 1 to A 4 are C-H, A 1 is C-F and A 2 to A 4 are C-H, A 1 and A 2 are C-F and A 3 and A 4 are C-H, A 1 and A 3 are C-F and A 2 and A 4 are C-H or A 1 is N and A 2 to A 4 are C-H;
  • R 5 and R 6 are independently selected from hydrogen, C 1 _ 4 alkyl and cyano;
  • R 7 is hydroxy, C 1 _ 4 alkyl, C 2 _ 4 fluoroalkyl, C 1 _ 4 alkoxy, hydroxyC 1 _ 4 alkyl, C 1 _ 2 alkoxyC 1 _ 4 alkyl, C 3 .
  • R 8 is C 1 - 6 alkyl, C 1 _ 2 haloalkyl, hydroxyC 1 _ 6 alkyl, C 1 - 2 alkoxyC 1 - 4 alkyl, C 3 . 6 cycloalkyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- or 5-membered non-aromatic ring which comprises 1 or 2 heteroatoms individually selected from N and O, wherein C 3 . 6 cycloalkyl and heterocyclyl are optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R 9 ; and
  • R 9 is cyano, halogen, hydroxy, C 1 _ 4 alkyl, C 2 - 4 alkenyl, C 2 - 4 alkynyl, C 1 _ 4 haloalkyl or C 1 _ 4 alkoxy.
  • n is 1 ;
  • a 1 to A 4 are C-H
  • R 5 and R 6 are independently selected from hydrogen and C 1 _ 4 alkyl
  • R 7 is C 1 - 4 alkyl, C 2 _ 4 fluoroalkyl, methoxy, ethoxy or cyclopropyl;
  • R 8 is C 1 - 6 alkyl, C 1 _ 2 haloalkyl, hydroxyC 1 _ 6 alkyl, C 1 _ 2 alkoxyC 1 _ 4 alkyl, C 3 . 6 cycloalkyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- or 5-membered non-aromatic ring which comprises 1 or 2 heteroatoms individually selected from N and O, wherein C 3 . 6 cycloalkyl and heterocyclyl are optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R 9 ; and
  • R 9 is cyano, halogen, hydroxy, C 1 _ 4 alkyl, C 2 _ 4 alkenyl, C 2 _ 4 alkynyl, C 1 _ 4 haloalkyl or C 1 _ 4 alkoxy.
  • n is 1 ;
  • a 1 to A 4 are C-H
  • R 5 and R 6 are independently selected from hydrogen and methyl, preferably hydrogen;
  • R 7 is methyl, ethyl, n-propyl, iso-propyl, 2,2,2-fluoroethyl, methoxy, ethoxy or cyclopropyl;
  • R 8 is C 1 - 4 alkyl, C 1 _ 2 haloalkyl, hydroxyC 1 _ 4 alkyl, C 1 _ 2 alkoxyC 1 _ 2 alkyl, C 3 . 6 cycloalkyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- or 5-membered non-aromatic ring which comprises 1 or 2 heteroatoms which are oxygen, wherein C 3 . 6 cycloalkyl and heterocyclyl are optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R 9 ; and
  • R 9 is fluoro, chloro, methyl.
  • n 1 ;
  • a 1 to A 4 are C-H
  • R 5 and R 6 are independently selected from hydrogen and methyl
  • R 7 is hydroxy, C 1 _ 4 alkyl, C 2 _ 4 haloalkyl, C 1 _ 4 alkoxy, C 3 . 6 alkenyl, C 3 _ 4 alkynyl or d.
  • R 8 is -OR 12 ;
  • R 12 is hydrogen, C 1 _ 6 alkyl, C 3 . 6 alkenyl, C 3 . 6 alkynyl, C 1 _ 6 haloalkyl, C 1 _ 4 alkoxyC 1 _ 6 alkyl, phenyl, phenylC 1 - 6 alkyl.
  • n is 1 ;
  • a 1 to A 4 are C-H
  • R 5 and R 6 are hydrogen
  • R 7 is methoxy
  • R 8 is -OR 12 ;
  • R 12 is hydrogen, C 1 _ 6 alkyl, C 3 . 6 alkenyl, C 3 . 6 alkynyl, C 1 _ 6 haloalkyl, C 1 _ 4 alkoxyC 1 . 6 alkyl, phenyl, phenylC 1 _ 6 alkyl.
  • n is 1 ;
  • a 1 to A 4 are C-H or A 1 , A 2 and A 4 are C-H and A 3 is C-F;
  • R 5 and R 6 are hydrogen
  • R 7 is hydroxy, C 1 _ 4 alkyl, C 2 - 4 haloalkyl, C 1 _ 4 alkoxy, C 3 . 6 alkenyl, C 3 _ 4 alkynyl, C 3 . 6 cycloalkyl;
  • R 8 is -NR 14 R 15 ;
  • R 14 is hydrogen, cyano, C 1 _ 6 alkyl, C 1 _ 6 alkoxy, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoC 1 _ 6 alkyl, C 1 _
  • R 16 is cyano, halogen, hydroxy, C 1 _ 4 alkyl, C 1 _ 4 haloalkyl, C 1 - 4 alkoxy, C 1 _ 4 haloalkoxy or C 1 _ 4 alkoxycarbonyl;
  • R 15 is hydrogen, methyl, ethyl, C 3 _ 4 alkynyl or methoxyethyl.
  • n is 1 ;
  • a 1 to A 4 are C-H
  • R 5 and R 6 are hydrogen
  • R 7 is hydroxy, C 1 _ 4 alkyl, C 2 _ 4 haloalkyl, C 1 _ 2 alkoxy, C 3 _ 4 alkenyl, C 3 _ 4 alkynyl or cyclopropyl;
  • R 8 is -NR 14 R 15 ;
  • R 14 is hydrogen, methyl, ethyl, propyl, iso-propyl, sec-butyl, methoxy, ethoxy, allyl, propyn-2-yl, 2,2,2-trifluoromethyl, cyclopropyl or cyclobutyl;
  • R 15 is hydrogen, methyl or ethyl.
  • n is 1 ;
  • a 1 to A 4 are C-H
  • R 5 and R 6 are hydrogen
  • R 7 is C 1 - 4 alkyl or C 1 _ 2 alkoxy
  • R 8 is -NR 14 R 15 ;
  • R 14 is hydrogen, methyl, ethyl, propyl, iso-propyl, sec-butyl, methoxy, ethoxy, allyl, propyn-2-yl, 2,2,2-trifluoromethyl, cyclopropyl or cyclobutyl;
  • R 15 is hydrogen
  • the compound according to Formula (I) may be selected from compound 1.1 to 1.811 listed in Table T1 below, from compound 2.1 to 2.26 listed in Table T2 below, and from compound 3.1 to 3.140 listed in Table T3 below.
  • the compound of Formula (I) may be a compound according to Formula (IA):
  • R 1 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 1 , 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 C 1 _ 4 alkyl or C 1 _ 4 alkoxy;
  • R 8 is hydrogen, C 1 _ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoC 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 2 .
  • R 8 is C 3 . 8 cycloalkylC 0 - 6 alkyl, wherein the cycloalkyl moiety is optionally partially unsaturated, phenylC 0 - 6 alkyl, phenylC 2 .
  • R 9 is cyano, halogen, hydroxy, C 1 _ 4 alkyl, C 2 - 4 alkenyl, C 2 - 4 alkynyl, C 1 _ 4 haloalkyl, C 2 - 4 haloalkenyl, C 1 _ 4 alkoxy, C 1 _ 4 haloalkoxy, C 3 _ 4 alkynyloxy, N-C 1 _ 4 alkylamino, N,N-diC 1 _ 4 alkylamino, C 1 _ 4 alkylcarbonyl, C 1 - 4 alkoxycarbonyl, carbonylamino, N-C 1 _ 4 alkylaminocarbonyl, N,N-diC 1 _ 4 alkylaminocarbonyl or d
  • R 8 is substituted C 3 . 8 cycloalkylC 0 - 6 alkyl or heterocyclylC 0 - 6 alkyl
  • R 9 may also represent oxo on the C 3 . 8 cycloalkyl or heterocyclyl moiety; or wherein for R 8 , any of C 3 .
  • R 10 is C 3 . 8 cycloalkylC 0 - 2 alkyl, phenylC 0 - 2 alkyl, heteroarylC 0 - 2 alkyl wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclylC 0 - 6 alkyl wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, and wherein any of said cycloalkyi, phenyl, heteroaryl and heterocyclyl moieties are optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R 11 ; wherein
  • R 11 is hydrogen, cyano, fluoro, chloro, bromo, methyl, trifluoromethyl, methoxy and ethoxy; or a salt or an N-oxide thereof.
  • R 8 as a C 3 . 8 cycloalkylC 0 - 6 alkyl, phenylC 0 - 6 alkyl, phenylC 2 . 6 alkenyl, naphthylC 0 - 6 alkyl, heteroarylC 0 - 6 alkyl, heterodiarylC 0 - 6 alkyl, heterocyclylC 0 - 6 alkyl or C 3 - 6 cycloalkylcarbonylaminoC 1 - 6 alkyl moiety is indicated as optionally substituted by R 9 or R 10 , the cycloalkyi, phenyl, naphthyl, heteroaryl, heterodiaryl, heterocyclyl fragment only may be substituted.
  • R 1 and R 2 are independently selected from hydrogen and fluoro. More preferably, R 1 and R 2 are hydrogen.
  • R 3 and R 4 are independently selected from hydrogen and fluoro. More preferably, R 3 and R 4 are hydrogen.
  • R 1 , 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 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.
  • R 7 is methyl, ethyl, propyl, isopropyl, butyl, sec- butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, or sec-butoxy. More preferably, R 7 is methyl, ethyl, sec-butyl, methoxy, ethoxy, or propoxy. Most preferably, R 7 is sec-butyl, methoxy or propoxy.
  • R 8 is hydrogen, C 1 _ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, cyanoC 1 - 6 alkyl, C 1 _ 6 haloalkyl, C 2 - 6 haloalkenyl, hydroxyC 1 _ 6 alkyl, C 1 _ 4 alkoxyC 1 . 6 alkyl, C 1 _ 4 haloalkoxyC 1 _ 6 alkyl, C 1 - 4 alkoxyC 1 - 4 alkoxyC 1 - 6 alkyl, C 2 - 4 alkynyloxyC 1 . 6 alkyl, C 1 . 6 alkylcarbonylC 2 .
  • C 3 - 8 cycloalkylCo- 2 alkyl wherein the cycloalkyi moiety is optionally partially unsaturated, phenylC 0 - 2 alkyl, heteroarylC 0 - 2 alkyl wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, or heterocyclylC 0 - 2 alkyl wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S; wherein any of said C 3 - 8 cycloalkylCo- 2 alkyl, phenylC 0 - 2 alkyl, heteroarylC 0 - 2 alkyl and heterocyclylC 0 - 2 alkyl moieties are optionally substituted by 1 , 2 or 3 substituents, which
  • R 8 is C 1 _ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, C 1 _ 6 fluoroalkyl, C 1 _ 6 chloroalkyl, C 1 _ 4 alkoxyC 1 - 6 alkyl, C 1 _ 4 alkoxyC 1 _ 4 alkoxyC 1 . 6 alkyl, C 1 . 6 alkylcarbonylC 2 . 6 alkenyl, C 1 . 6 alkylcarbonyloxyC 1 _ 6 alkyl, C 1 _ 6 alkylsulfonylaminoC 2 . 6 alkynyl or C 2 . 6 alkynyloxycarbonylaminoC 1 .
  • R 8 is C 1 _ 6 alkyl, C 2 _ 4 alkenyl, C 2 ⁇ alkynyl, C 1 _ 6 fluoroalkyl, C 1 _ 4 chloroalkyl, C 1 - 4 alkoxyC 1 _ 4 alkyl, C 1 _ 4 alkoxyC 1 .
  • R 8 is a group selected from C 3 . 8 cycloalkylC 0 - 6 alkyl, phenylC 0 - 6 alkyl, phenylC 2 . 6 alkenyl, naphthylC 0 - 6 alkyl, heteroarylC 0 - 6 alkyl, heterodiarylC 0 - 6 alkyl, heterocyclylC 0 - 6 alkyl, preferably R 8 is C 3 .
  • R 8 cycloalkylC 0 - 2 alkyl, phenylC 0 - 2 alkyl, phenylC 2 _ 4 alkenyl, naphthylC 0 - 2 alkyl, heteroarylC 0 - 2 alkyl, heterodiarylC 0 - 2 alkyl or heterocyclylC 0 - 2 alkyl.
  • R 8 is a group selected from C 3 - 8 cycloalkylC 0 - 6 alkyl, preferably C 3 . 8 cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • R 8 is phenyl or benzyl.
  • R 8 is a group selected from heterocyclylC 0 - 6 alkyl
  • the heterocyclyl group has 1 or 2 heteroatoms selected from N, O and S. More preferably, the heterocyclyl group has a single heteroatom selected from O and S.
  • Most preferable for R 8 as a heterocyclylC 0 - 6 alkyl are oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, thietanyl or tetrahydrothiopyranyl.
  • R 1 and R 2 are independently selected from hydrogen and fluoro;
  • R 3 and R 4 are independently selected from hydrogen and fluoro
  • R 1 , 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 methyl;
  • R 7 is C 1 - 4 alkyl or C 1 _ 4 alkoxy
  • R 8 is C 1 - 6 alkyl, C 2 - 6 alkenyl, C 2 - 6 alkynyl, C 1 _ 6 fluoroalkyl, C 1 _ 6 chloroalkyl, C 1 _ 4 alkoxyC 1 . 6 alkyl, d.
  • R 1 and R 2 are independently selected from hydrogen and fluoro;
  • R 3 and R 4 are independently selected from hydrogen and fluoro
  • R 1 , 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 methyl;
  • R 7 is methoxy, propoxy or sec-butyl
  • R 8 is C 1 - 6 alkyl, C 2 _ 4 alkenyl, C 2 _ 4 alkynyl, C 1 _ 6 fluoroalkyl, C 1 _ 4 chloroalkyl, C 1 _ 4 alkoxyC 1 _ 4 alkyl, C 1 _ 4alkoxyC 1 - 2 alkoxyC 1 - 4 alkyl, C 1 _ 4 alkylcarbonylC 2 _ 4 alkenyl, C 1 _ 2 alkylcarbonyloxyC 1 _ 4 alkyl, C 1 _ 4alkylsulfonylaminoC 2 _ 4 alkynyl or C 2 _ 4 alkynyloxycarbonylaminoC 1 _ 4 alkyl; C 3 .
  • R 9 is cyano, fluoro, chloro, hydroxy, methyl, ethyl, trifluoromethyl, 2,2-dichloroethenyl, propynyloxy, acetyl, methoxycarbonyl; or wherein any of said cycloalkyl, phenyl, and heterocyclyl moieties are optionally substituted by 1 substituent selected from R 10 which is a phenyl.
  • R 1 and R 2 are hydrogen;
  • R 3 and R 4 are hydrogen
  • R 5 and R 6 are hydrogen
  • R 7 is methoxy, propoxy or sec-butyl
  • R 8 is C 1 - 6 alkyl, C 2 - 4 alkenyl, C 2 - 4 alkynyl, C 1 _ 6 fluoroalkyl, C 1 _ 4 chloroalkyl, C 1 _ 4 alkoxyC 1 _ 4 alkyl, C 1 _ 4alkoxyC 1 . 2 alkoxyC 1 _ 4 alkyl, C 1 _ 4 alkylcarbonylC 2 - 4 alkenyl, C 1 . 2 alkylcarbonyloxyC 1 _ 4 alkyl, C 1 _
  • 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 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 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 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 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 as represented in Tables 1.1 to 1.29, 2.1 to 2.5, 3.1 to 3.14 and 4.1 to 4.4 below or the compounds 1.1 to 1.81 1 described in
  • the compounds of formula (I) can be obtained by an amide coupling transformation with compounds of formula (II) and compounds of formula (III) 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 N,N- diisopropylethylamine, or under conditions described in the literature for an amide coupling.
  • a suitable solvent eg, dimethylformamide, dichloromethane or tetrahydrofuran
  • 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 R 8 - 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 R 8 -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
  • R 8 -Nu represents HOR 0 or HN(R )R 12 in the presence of a suitable base such as trieth lamine.
  • compounds of formula (I) can be prepared from compounds of formula (V) 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 (V) can be prepared from compounds of formula (VI) 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 (VI) can be prepared from compounds of formula (VII), 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.
  • a suitable cyanide reagent such as Pd(0)/Zn(CN) 2 or CuCN
  • a suitable solvent eg, dimethylformamide or N-methylpyrrolidone
  • Compounds of formula (VII), wherein the N-R 7 bond contains a directly linked -CH 2 segement can be prepared from compounds of formula (VIII), wherein Z is Br or I, via a base-promoted reaction (eg, sodium hydride) with a suitable alkylating reagent (eg, methyl iodide or propyl iodide), in a suitable solvent (eg, dimethylformamide or N-methylpyrrolidone) at elevated temperature between 100°C and 120°C.
  • a base-promoted reaction eg, sodium hydride
  • a suitable alkylating reagent eg, methyl iodide or propyl iodide
  • a suitable solvent eg, dimethylformamide or N-methylpyrrolidone
  • Compounds of formula (II), wherein n is preferably 0 and R 6 is hydrogen, can be prepared from carbonyl compounds of formula (IX), starting with treatment by compounds of formula (X), 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 (XI), such as an alkyl Grignard reagent (eg.
  • an activating reagent eg, Ti(OEt) 4
  • a suitable solvent eg, tetrahydrofuran
  • compounds of formula (II), wherein n is preferably 1 can be prepared from compounds of formula (XIII), wherein X is CI or Br, by treatment with amines of formula (XII), 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 (XIII), wherein n is 1 can be prepared from compounds of formula (XIV), wherein X is CI or Br, by treatment with a halogen source (eg, N-bromosuccinimide (NBS) or N- chlorosuccinimide (NCS)) and a radical initiator (eg, (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-bromosuccinimide (NBS) or N- chlorosuccinimide (NCS)
  • a radical initiator eg, (PhC0 2 )2 or azobisisobutyronitrile (AIBN)
  • suitable solvent such as tetrachloromethane
  • the compounds of formula (VII) can be obtained by an amide coupling transformation with compounds of formula (XV) and compounds of formula (III) 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 (XV), 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 N,N- diisopropylethylamine, or under conditions described in the literature for an amide coupling.
  • a suitable solvent eg, dimethylformamide, dichloromethane or tetrahydrofuran
  • compounds of formula (VII), wherein Z is Br, I, or CN and R 8 may also be OR 12 or NR 4 R 15 where R 5 is not hydrogen and n is preferably 1 can be prepared from compounds of formula (XVIII), wherein X is CI, Br or I, via treatment with amides of formula (XVII), 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 (XVIII), wherein X is CI, Br, I, or OS0 2 Me and Z is Br, I and n is preferably 1 , or CN 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 halogen source eg, CBr 4, CCI 4 or l 2
  • CIS0 2 Me methanesulfonyl chloride
  • suitable solvent eg, dichloromethane
  • novel compounds of formula (I) according to the invention have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.
  • the compounds of formula (I) can be used in the agricultural sector and related fields of use, e.g., as active ingredients for controlling plant pests or on non-living materials for the control of spoilage microorganisms or organisms potentially harmful to man.
  • the novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and can be used for protecting numerous cultivated plants.
  • the compounds of formula I can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later, e.g., from phytopathogenic microorganisms.
  • the present invention further relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein an effective amount a compound of formula (I) is applied to the plants, to parts thereof or the locus thereof.
  • fungicide as used herein means a compound that controls, modifies, or prevents the growth of fungi.
  • fungicidally effective amount 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 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® (cott
  • 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.
  • 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.
  • 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. 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.
  • 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.
  • 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 non- volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
  • Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required.
  • Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound.
  • Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils
  • Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.
  • Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates.
  • Encapsulated droplets are typically 1 to 50 microns in diameter.
  • the enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound.
  • Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores.
  • Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring.
  • Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene- butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
  • compositions for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents.
  • Pressurised sprayers wherein the active ingredient is dispersed in finely-divided form as a result of vaporisation of a low boiling dispersant solvent carrier, may also be used.
  • Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to those skilled in the art.
  • Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, ⁇ , ⁇ -dimethyl formamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glyco
  • Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller's earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.
  • a broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application.
  • These agents when used, normally comprise from 0.1 % to 15% by weight of the formulation. They can be anionic, cationic, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes.
  • Typical surface active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub.
  • alcohol-alkylene oxide addition products such as tridecyl alcohol-C.sub. 16 ethoxylate
  • soaps such as sodium stearate
  • alkylnaphthalenesulfonate salts such as sodium dibutylnaphthalenesulfonate
  • dialkyi 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 dialkyi phosphate esters such as mono and dialkyi phosphate esters.
  • adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, anti-foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.
  • biocidally active ingredients or compositions may be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention. When applied simultaneously, these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank. These further biocidally active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.
  • Pesticidal agents are referred to herein using their common name are known, for example, from “The Pesticide Manual”, 15th Ed., British Crop Protection Council 2009.
  • compositions of the invention may also be applied with one or more system ically acquired resistance inducers ("SAR" inducer).
  • SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
  • the compounds of formula (I) are normally used in the form of agrochemical compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds.
  • further compounds can be e.g. fertilizers or micronutrient donors or other preparations, which influence the growth of plants. They can also be selective herbicides or nonselective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
  • the compounds of formula (I) may be used in the form of (fungicidal) compositions for controlling or protecting against phytopathogenic microorganisms, comprising as active ingredient at least one compound of formula (I) or of at least one preferred individual compound as defined herein, in free form or in agrochemically usable salt form, and at least one of the above-mentioned adjuvants.
  • the invention therefore provides a composition, preferably a fungicidal composition, comprising at least one compound formula (I) an agriculturally acceptable carrier and optionally an adjuvant.
  • An agricultural acceptable carrier is for example a carrier that is suitable for agricultural use.
  • Agricultural carriers are well known in the art.
  • said composition may comprise at least one or more pesticidally-active compounds, for example an additional fungicidal active ingredient in addition to the compound of formula (I).
  • the compound of formula (I) may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate.
  • An additional active ingredient may, in some cases, result in unexpected synergistic activities.
  • Suitable additional active ingredients include the following: acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenical fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, , dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine
  • Suitable additional active ingredients also include the following: 3-difluoromethyl-
  • 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-
  • Additional anthelmintic agents include semisynthetic and biosynthetic avermectin/milbemycin derivatives such as those described in US-5015630, WO-9415944 and WO-
  • Additional anthelmintic agents include the benzimidazoles such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of the class. Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines such as tetramisole, levamisole, pyrantel pamoate, oxantel or morantel.
  • Additional anthelmintic agents include flukicides, such as triclabendazole and clorsulon and the cestocides, such as praziquantel and epsiprantel.
  • the compounds of the invention may be used in combination with derivatives and analogues of the paraherquamide/marcfortine class of anthelmintic agents, as well as the antiparasitic oxazolines such as those disclosed in US-5478855, US- 4639771 and DE-19520936.
  • the compounds of the invention may be used in combination with derivatives and analogues of the general class of dioxomorpholine antiparasitic agents as described in WO 96/15121 and also with anthelmintic active cyclic depsipeptides such as those described in WO 96/1 1945, WO 93/19053,
  • the compounds of the invention may be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
  • ectoparasiticides for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
  • the compounds of the invention may be used in combination with terpene alkaloids, for example those described in International Patent Application Publication Numbers WO 95/19363 or WO 04/72086, particularly the compounds disclosed therein.
  • Organophosphates acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, bromophos, bromophos-ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl, demeton-S-methyl sulphone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosthiazate, hep
  • Carbamates alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801 , isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717.
  • Pyrethroids acrinathin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E) -(1 R)-cis-2,2- dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, beta -cyfluthrin, cyfluthrin, a-cypermethrin, beta -cypermethrin, bioallethrin, bioallethrin((S)-cyclopentylisomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin, cythithrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, ethofenprox, fenfluthrin, fenpropathrin, fenval
  • Arthropod growth regulators a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole, chlorfentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenoids: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.
  • antiparasitics acequinocyl, amitraz, AKD-1022, ANS-1 18, azadirachtin, Bacillus thuringiensis, bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidine, cyromazine, diacloden, diafenthiuron, DBI-3204, dinactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, ethofenprox, fenazaquin, flumite, MTI- 800, fenpyroximate, fluacrypyrim, flubenzimine, flubrocythrinate, flufenzine, flufenprox, fluproxyfen, halofenprox, hydra
  • Biological agents Bacillus thuringiensis ssp aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, virus and fungi.
  • Bactericides chlortetracycline, oxytetracycline, streptomycin.
  • 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.
  • rates of 0.001 to 50 g of a compound of formula I per kg of seed preferably from 0.01 to 10g per kg of seed are generally sufficient.
  • composition comprising a compound of formula (I) according to the present invention is applied either preventative, meaning prior to disease development or curative, meaning after disease development.
  • compositions of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK
  • compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects).
  • appropriate formulation inerts diiluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects.
  • conventional slow release formulations may be employed where long lasting efficacy is intended.
  • Particularly formulations to be applied in spraying forms such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g.
  • a seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds.
  • suitable seed dressing formulation form e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds.
  • seed dressing formulations are known in the art.
  • Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules.
  • the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least the compound of formula (I) optionally together with other active agents, particularly microbiocides or conservatives or the like.
  • Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent.
  • Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.
  • Table 1.1 This table discloses 149 s ecific compounds of the formula (T-1 ):
  • n is 1
  • a 1 is C-R 1
  • a 2 is C-R 2
  • a 3 iiss CC--RR 3
  • a 4 is C-R 4 and R 1
  • R 2 , R 3 , R 4 , R 5 and R 6 are hydrogen
  • R 7 is methoxy
  • R 8 is as defined below in the Table 1
  • Tables 1.2 to 1.29 make available 149 individual compounds of the formula (T-1 ) in which n, A 1 , A 2 , A 3 , A 4 , R , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are as specifically defined in Tables 1.2 to 1.29, which refer to Table 1 wherein R 8 is specifically defined.
  • Table 1
  • Table 1.2 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is methoxy, R is fluorine, and R 8 is as defined above in Table 1.
  • Table 1.3 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is methoxy, R is chlorine, and R 8 is as defined above in Table 1.
  • Table 1.4 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is methoxy, R is methyl, and R 8 is as defined above in Table 1.
  • Table 1.5 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is methoxy, and R 8 is as defined above in Table 1.
  • Table 1.6 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is methoxy, R 3 is fluorine, and R 8 is as defined above in Table 1.
  • Table 1.7 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is methoxy, R and R 3 are fluorine, and R 8 is as defined above in Table 1.
  • Table 1.8 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is methoxy, R 1 and R 2 are fluorine, and R 8 is as defined above in Table 1.
  • Table 1.9 discloses 149 specific compounds of formula (T-1 ) wherein n is 2, 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 , and R 6 are hydrogen, R 7 is methoxy, and R 8 is as defined above in Table 1.
  • Table 1.10 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 5 are hydrogen, R 7 is methoxy, R 6 is methyl, and R 8 is as defined above in Table 1.
  • Table 1.11 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 5 are hydrogen, R 7 is methyl, R 6 is cyano, and R 8 is as defined above in Table 1.
  • Table 1.13 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is methyl, and R 8 is as defined above in Table 1.
  • Table 1.14 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is ethyl, and R 8 is as defined above in Table 1.
  • Table 1.15 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is propyl, and R 8 is as defined above in Table 1.
  • Table 1.16 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is isopropyl, and R 8 is as defined above in Table 1.
  • Table 1.17 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is allyl, and R 8 is as defined above in Table 1.
  • Table 1.18 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is isobutyl, and R 8 is as defined above in Table 1.
  • Table 1.19 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is 2-methoxyethyl, and R 8 is as defined above in Table 1.
  • Table 1.20 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is propyloxy, and R 8 is as defined above in Table 1.
  • Table 1.21 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is 2-propynl, and R 8 is as defined above in Table 1.
  • Table 1.22 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is 2-furylmethyl, and R 8 is as defined above in Table 1.
  • Table 1.23 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is tetrahydrofuran-2- ylmethyl, and R 8 is as defined above in Table 1.
  • Table 1.24 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is cyclopropyl methyl, and R 8 is as defined above in Table 1.
  • Table 1.25 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is cyclopropyl, and R 8 is as defined above in Table 1.
  • Table 1.26 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is ethoxy, and R 8 is as defined above in Table 1.
  • Table 1.27 discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is hydroxy, and R 8 is as defined above in Table 1.
  • Table 1.28 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is 2,2,2-trifluoroethyl, and R 8 is as defined above in Table 1.
  • Table 1.29 This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is 2-hydroxyethyl, and R 8 is as defined above in Table 1.
  • Table 2.1 This table discloses 26 specific compounds of the formula (T-2):
  • n is 1
  • 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 and R 6 are hydrogen
  • R 7 is methoxy and R 12 is as defined below in Table 2.
  • Tables 2.2 to 2.5 make available 26 individual compounds of the formula (T-2) in which n, A 1 , A 2 , A 3 , A 4 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as specifically defined in Tables 2.2 to 2.5, which refer to Table 2 wherein R 12 is specifically defined.
  • Table 2.2 This table discloses 26 specific compounds of formula (T-2) wherein n is 1 , A 1 is C-R 1 , A 2 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 , and R 6 are hydrogen, R 7 is allyl, and R 12 is defined above in Table 2.
  • Table 2.3 This table discloses 26 specific compounds of formula (T-2) wherein n is 1 , A 1 is C-R 1 , A 2 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 , and R 6 are hydrogen, R 7 is ethoxy, and R 12 is defined above in Table 2.
  • Table 2.4 This table discloses 26 specific compounds of formula (T-2) wherein n is 1 , A 1 is C-R 1 , A 2 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 , and R 6 are hydrogen, R 7 is hydroxy, and R 12 is defined above in Table 2.
  • Table 2.5 This table discloses 26 specific compounds of formula (T-2) wherein n is 1 , 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 , and R 6 are hydrogen, R 7 is 2,2,2-trifluoroethyl, and R 12 is as defined above in Table 2.
  • Table 3.1 This table discloses 100 specific compounds of the formula (T-3):
  • n is 1
  • 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 , and R 15 are hydrogen
  • R 7 is methoxy
  • R 14 is as defined below in Table 3.
  • Tables 3.2 to 3.14 make available 100 individual compounds of the formula (T-3) in which n, A 1 , A 2 , A 3 , A 4 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 15 are as specifically defined in Tables 3.2 to 3.14, which refer to Table 3 wherein R 14 is specifically defined.
  • Table 3.3 This table discloses 100 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 , and R 15 are hydrogen, R 7 is methoxy, n is 1 , and R 14 is as defined above in Table 3.
  • Table 3.4 discloses 100 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 4 , R 5 , R 6 , and R 15 are hydrogen, R 7 is methoxy, R 3 is fluorine, n is 1 , and R 14 is as defined above in Table 3.
  • Table 3.5 This table discloses 100 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 3 , R 4 , R 5 , R 6 , and R 15 are hydrogen, R 7 is methoxy, R 1 and R 2 are fluorine, n is 1 , and R 14 is as defined above in Table 3.
  • Table 3.6 This table discloses 100 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 , and R 15 are hydrogen, R 7 is isopropyl, n is 2, and R 14 is as defined above in Table 3.
  • Table 3.7 discloses 100 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 , and R 6 , are hydrogen, R 7 is methoxy, R 15 is methyl, n is 1 , and R 14 is as defined above in Table 3.
  • Table 3.8 This table discloses 100 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 , and R 6 are hydrogen, R 7 is methoxy, R 1 is fluorine, R 15 is methyl, n is 1 , and R 14 is as defined above in Table 3.
  • Table 3.9 discloses 100 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 4 , R 5 , and R 6 are hydrogen, R 7 is methoxy, R 3 is fluorine, R 15 is methyl, n is 1 , and R 14 is as defined above in Table 3.
  • Table 3.10 This table discloses 100 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 and R 15 are hydrogen, R 7 is methyl, n is 1 , and R 14 is as defined above in Table 3.
  • Table 3.1 1 This table discloses 100 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 and R 15 are hydrogen, R 7 is ethyl, n is 1 , and R 14 is as defined above in Table 3.
  • Table 3.12 This table discloses 100 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 and R 15 are hydrogen, R 7 is isopropyl, n is 1 , and R 14 is as defined above in Table 3.
  • Table 3.13 This table discloses 100 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 and R 15 are hydrogen, R 7 is cyclopropyl, n is 1 , and R 14 is as defined above in Table 3.
  • Table 3.14 This table discloses 100 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 and R 15 are hydrogen, R 7 is hydroxy, n is 1 , and R 14 is as defined above in Table 3.
  • Table 4.1 This table discloses 4 specific compounds of the formula (T-4):
  • n is 1
  • 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 , and R 6 are hydrogen
  • R 7 is methoxy
  • R 14 -N-R 15 is as defined below in the Table 4.
  • Tables 4.2 to 4.4 make available 4 individual compounds of the formula (T-4) in which n, A 1 , A 2 , A 3 , A 4 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are as specifically defined in Tables 4.2 to 4.4, which refer to Table 4 wherein R 14 -N-R 15 is specifically defined.
  • Table 4.2 This table discloses 4 specific compounds of formula (T-4) wherein n is 1 , A 1 is C-R 1 , A' 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 , and R 6 are hydrogen, R 7 is methyl, and R 14 -N-R 15 as defined above in Table 4.
  • Table 4.3 This table discloses 4 specific compounds of formula (T-4) wherein n is 1 , 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 , and R 6 , are hydrogen, R 7 is ethyl and R 4 -N-R 15 is as defined above in Table 4.
  • Table 4.4 This table discloses 4 specific compounds of formula (T-4) wherein 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 , R 2 , R 3 , R 4 , R 5 , R 6 are hydrogen, R 7 is isopropyl, and R 4 -N-R 15 is as defined above in Table 4.
  • the compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm or 0.2 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 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:
  • 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.
  • 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.
  • 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.
  • Active ingredient [compound of formula (I)] 5 % 6 %
  • 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.
  • 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.
  • polyethylene glycol (mol. wt. 200) 3 %
  • the finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
  • nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
  • silicone oil (in the form of a 75 % emulsion in water) 1 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • 28 parts of a combination of the compound of formula I are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1 ).
  • This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved.
  • a mixture of 2.8 parts 1 ,6- diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • AIBN azobisisobutyronitrile
  • BOP-CI phosphoric acid bis(2-oxooxazolidide) chloride
  • CDI carbonyl diimidazole
  • DIBAL-H diisobutylaluminium hydride
  • DIPEA N,N-diisopropylethylamine
  • EdCI 3-(ethyliminomethyleneamino)-A/,A/-dimethylpropan-1-amine
  • HOAt 1-hydroxy-7-azabenzotriazole
  • HATU 1-[bis(dimethylamino)methylene]-1 H-1 ,2,3-triazolo[4,5-b]pyridinium 3-oxid- hexafluorophosphate
  • NBS N-bromosuccinimide
  • Example 1 This example illustrates the preparation of N-methoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]meth l]-acetamide (Compound 1.1 of Table T1 below).
  • Step 1 Preparation of 4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllbenzoyl chloride
  • Step 2 Preparation of N-methoxy-N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllbenzamide
  • Step 3 Preparation of 4-[5-(trifluorometh l)-1 ,2,4-oxadiazol-3-yl]benzaldehyde
  • Step 4 Preparation of N-methoxy-1-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethanimine
  • Step 6 Preparation of N-methoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyll- acetamide
  • the aqueous layer was extracted trice with dichloromethane and the combined organic layers were washed with brine, dried over sodium sulfate, filtered and evaporated to dryness.
  • the crude oil was purified by flash chromatography over silica gel (heptane: EtOAc eluent gradient 99:1 to 80:20) to give 0.08 g of the title compound as a clear oil.
  • Example 2 This example illustrates the preparation of intermediate 3-[4-(bromomethyl)phenyl]-5- trifluoromethyl)-1 ,2,4-oxadiazole
  • 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-(trifluoromethyl)-1 ,2,4-oxadiazole from 3-[4- (dibromomethyl)phenyll-5-(trifluoromethyl)-1 ,2,4-oxadiazole
  • Example 3 This example illustrates the preparation of intermediate N-propoxy-1-[4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phenyl]methanamine
  • Example 4 This example illustrates the preparation of intermediate N-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]ethanamine.
  • Example 5 This example illustrates the preparation of the intermediate N-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]ethanamine.
  • Example 6 This example illustrates the preparation of the intermediate N-methoxy-1-[4-[5- (trifluoromethyl)-1 ,2,4-oxadiazol-3- l]phenyl]ethanamine.
  • Step 1 Preparation of 4-[(E)-N-methoxy-C-methyl-carbonimidoyllbenzonitrile
  • Step 3 Preparation of N-methoxy-1-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllethanimine
  • Step 4 Preparation of N-methoxy-1-[4-[5-(trifluoromethvn-1 ,2,4-oxadiazol-3-yllphenyllethanamine
  • Example 7 This example illustrates the preparation of the 1-[cyano-[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]meth l -3-methoxy-1 ,3-dimethyl-urea (Compound 3.31 of Table T3)
  • Step 1 Preparation of 2-(methylamino)-2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllacetonitrile
  • Step 2 Preparation of 1-[cvano-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyll-3-methoxy- 1 ,3-dimethyl-urea
  • Step 2 Preparation of N-(oxetan-3-yl)-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyll propanamide
  • reaction mixture was evaporated under reduced pressure and the resultant crude residue was subjected to flash chromatography over silica gel (heptane: EtOAc eluent gradient 9: 1 to 1 :9) to afford the desired product as a white solid mp: 88.8°-93.5°C.
  • Example 9 This example illustrates the preparation N-[[3-fluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol- 3-yl]phenyl]methyl]-N,2-dimethoxy-propanamide (Compound 1.783 of Table T1 )
  • Step 2 Preparation of 3-(2-fluoro-4-methyl-phenyl)-5-(trifluoromethyl)-1 ,2,4-oxadiazole
  • Step 3b Preparation of 3-[4-(bromomethyl)-2-fluoro-phenyll-5-(trifluoromethyl)-1 ,2,4-oxadiazole from 33-[4-(dibromomethyl)-2-fluoro-phenyll-5-(trifluoromethyl)-1 ,2,4-oxadiazole
  • Step 4 Preparation of N-[[3-fluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyll-N,2- dimethoxy-propanamide
  • N- ethyl-N-isopropyl-propan-2-amine 0.2 mL, 1.03 mmol
  • 1-[3-fluoro-4-[5- (trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]-N-methoxy-methanamine 0.02 g, 0.07 mmol
  • Example 10 This example illustrates the preparation 1-[[3-fluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol- 3-yl]phenyl]methyl]-1-methoxy-3-methyl-urea (Compound 3.45 of Table T1 )
  • Example 1 1 This example illustrates the preparation 2-chloro-N-[[2,3-difluoro-4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phenyl]methyl]-N-methoxy-benzamide (Compound 1.576 of Table T1 )
  • Step 1 Preparation of 2,3-difluoro-N'-hvdroxy-4-methyl-benzamidine
  • Step 3 Preparation of 3-[4-(bromomethyl)-2,3-difluoro-phenyll-5-(trifluoromethyl)-1 ,2,4-oxadiazole
  • Step 4 Preparation of 1-[2,3-difluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyll-N-methoxy- methanamine
  • Example 12 This example illustrates the preparation N-methoxy-N-[[5-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]-2-pyridyl]methyl]cyclopropanecarboxamide (Compound 1.570 of Table T1 ).
  • Step 1 Preparation of N'-hvdroxy-6-methyl-pyridine-3-carboxamidine
  • Step 2 Preparation of 3-(6-methyl-3-pyridyl)-5-(trifluoromethyl)-1 ,2,4-oxadiazole
  • Step 3 Preparation of 3-[6-(bromomethyl)-3-pyridyll-5-(trifluoromethyl)-1 ,2,4-oxadiazole
  • Step 4 Preparation of N-methoxy-1-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yll-2-pyridyllmethanamine
  • Step 5 Preparation of N-methoxy-N-[[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yll-2-pyridyllmethyll cyclopropanecarboxamide
  • Example 13 This example illustrates the preparation methyl N-methoxy-N-[[4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phenyl]methyl]carbamate (Compound 2.3 of Table T2)
  • Step 2 Preparation of 3-[4-(2-bromoethvnphenyll-5-(trifluoromethvn-1 ,2,4-oxadiazole
  • Step 4j Preparation of N-isopropyl-N-[2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yllphenyllethyllcyclopropanecarboxamide
  • Protocol A Portions of triphosgene (6 mg) in DCE (0.3 mL) were transferred at 0°C to a 96 slot deep well plate (DWP96) containing the alcohol derivative [HOR 0 ] 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 room temperature for 30 minutes.
  • DWP96 96 slot deep well plate
  • Protocol B The alcohol derivative [HOR 0 ] or amine derivative [HNR R 12 ] of formula (IV) (0.05 mmol) and DIPEA (0.25 mmol) in 300 [it DMA were transferred at room temperature to a 96 slot deep well plate (DWP96). CDI (0.10 mmol) in DMA (300 ⁇ _) was added and stirred until solubilization.
  • 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).

Abstract

Compounds of the formula (I) wherein the substituents are as defined in claim 1, useful as a pesticides, especially 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 provided a compound of formula (I):
Figure imgf000002_0001
wherein n is 1 or 2 A1 represents N or CR , wherein R is hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy;
A2 represents N or CR2, wherein R2 is hydrogen, halogen, methyl, ethyl, difluoromethyl, 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 0, 1 or 2 of A1 , A2, A3 and 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 hydroxy, C1_4alkyl, C1_4haloalkyl, C1_4alkoxy, hydroxyC1_4alkyl, C1_2alkoxyC1_4alkyl, C1_ 2haloalkoxyC1_4alkyl, C3_6alkenyl, C3_4alkynyl, C3_6alkenyloxy, C3_6alkynyloxy, C3_6haloalkenyl, C3_ 6haloalkenyloxy, C1_4alkylcarbonyloxy, C1_4haloalkylcarbonyloxy, C1_4alkoxycarbonyloxy, C1_ 4alkylcarbonyloxyC1-4alkyl, C1_4haloalkylcarbonyloxyC1_4alkyl or C1_4alkoxycarbonyloxyC1_4alkyl; or
R7 is C3_6cycloalkyl, C3_6cycloalkylC1_2alkyl, C3-6cycloalkylC1-2alkoxy, phenyl, phenylC1_2alkyl, phenylC1_2alkoxy, heteroaryl, heteroarylC1_2alkyl, heteroarylC1_2alkoxy, heterocyclyl, heterocyclylC1_ 2alkyl, heterocyclylC1_2alkoxy, C3_6cycloalkylcarbonyloxy, heterocyclylcarbonyloxy phenylcarbonyloxy, C3_6cycloalkylcarbonyloxyC1_4alkyl, heterocyclylcarbonyloxyC1_4alkyl or phenylcarbonyloxyC1_4alkyl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 or 2 heteroatoms individually selected from N, O and S, and wherein any of said cycloalkyl, phenyl, heteroaryl and heterocyclyl moieties are optionally substituted by 1 or 2 substituents selected from cyano, fluoro, chloro, bromo, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy;
R8 is hydrogen, C1_6alkyl, C2_6alkenyl, C2_6alkynyl, cyanoC1_6alkyl, C1_6haloalkyl, C2_ 6haloalkenyl, hydroxyC1_6alkyl, C1_4alkoxyC1_6alkyl, C1_4haloalkoxyC1_6alkyl, C1_4alkoxyC1_4alkoxyC1_ 6alkyl, C2_4alkynyloxyC1_6alkyl, aminoC1_6alkyl, N-C1_4alkylaminoC1_6alkyl, N,N-diC1_4alkylaminoC1_6alkyl, C1-6alkylcarbonylC1-6alkyl, C1_6alkylcarbonylC2_6alkenyl, C1_6alkoxycarbonylC1_6alkyl, C1_ 6alkylcarbonyloxyC1_6alkyl, N-C1_4alkylaminocarbonylC1_6alkyl, N,N-diC1_4alkylaminocarbonylC1_6alkyl, C1_6alkylsulfanylC1_6alkyl, C1_6alkylsulfonylC1_6alkyl, C1_6alkylsulfonylaminoC1_6alkyl, C1_6 alkylsulfonylaminoC2_6alkynyl, C2_6alkynyloxycarbonylaminoC1_6alkyl, C1_4alkylcarbonylaminoC1_6alkyl or C1-4alkoxycarbonylaminoC1-6alkyl; or
R8 is C3_8cycloalkyl, C3_8cycloalkylC1_6alkyl, wherein the cycloalkyl moiety is optionally partially unsaturated, phenyl, phenylC1_6alkyl, phenylC2_6alkenyl, napthyl, naphthylC1_6alkyl, heteroaryl, heteroarylC1-6alkyl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterodiaryl, heterodiarylC1-6alkyl wherein the heterodiaryl moiety is a 9- or 10-membered bicyclic aromatic system which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl, heterocyclylC1-6alkyl wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, or C3_ 6cycloalkylcarbonylaminoC1-6alkyl, wherein for R8, any cycloalkyl, phenyl, napthyl, heteroaryl, heterodiaryl or heterocyclyl moiety is optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R9; or, additionally, when R8 is cyclopropyl, the cyclopropyl moiety is substituted by 4 substituents, which may be the same or different, selected from R9, with the proviso that at least 2 R9 substituents are the same; wherein R is cyano, halogen, hydroxy, C1_4alkyl, C2-4alkenyl, C2-4alkynyl, C1_4haloalkyl, C2-4haloalkenyl, C1_4alkoxy, C1_4haloalkoxy, C3_4alkynyloxy, N-C1_4alkylamino, N,N-diC1_4alkylamino, C1_4alkylcarbonyl, C3_6cycloalkylcarbonyl, C1_4alkoxycarbonyl, carbonylamino, N-C1_4alkylaminocarbonyl, N,N-diC1_ 4alkylaminocarbonyl or C1_4alkoxycarbonylamino, and wherein when R8 is substituted C3_8cycloalkyl, C3_8cycloalkylC1_6alkyl, heterocyclyl, or heterocyclylC1_6alkyl, R9 may also represent oxo on the C3_ scycloalkyl or heterocyclyl moiety; or wherein for R8, any cycloalkyl, phenyl, napthyl, heteroaryl, heterodiaryl or heterocyclyl moiety is optionally substituted by 1 substituent selected from R10 and further optionally substituted by 1 or 2 substituents selected from R9; wherein
R10 is C3_8cycloalkyl, C3-8cycloalkylC1-2alkyl, phenyl, phenylC1_2alkyl, heteroaryl, heteroarylC1_ 2alkyl wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl or heterocyclylC1_6alkyl wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, and wherein any of said cycloalkyl, phenyl, heteroaryl and heterocyclyl moieties are optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R11; wherein
R11 is hydrogen, cyano, fluoro, chloro, bromo, methyl, trifluoromethyl, methoxy and ethoxy; or R8 represents -OR12, wherein R12 is hydrogen, C1_6alkyl, C3_6alkenyl, C3_6alkynyl, cyanoC1_
6alkyl, C1_6haloalkyl, C3_6haloalkenyl, hydroxyC1_6alkyl, C1_4alkoxyC1_6alkyl, C1_4haloalkoxyC1_6alkyl, C1_ 4alkoxyC1-4alkoxyC1-6alkyl, aminoC1_6alkyl, N-C1_4alkylaminoC1_6alkyl, N,N-diC1_4alkylaminoC1_6alkyl, C1_ 6alkylcarbonylC1_6alkyl, C1_6alkylcarbonylC1_6alkenyl, C1_6alkoxycarbonylC1_6alkyl, C1_ 6alkylcarbonyloxyC1_6alkyl, N-C1_4alkylaminocarbonylC1_6alkyl, N,N-diC1_4alkylaminocarbonylC1_6alkyl, C1_4alkylsulfanylC1_6alkyl, C1_6alkylsulfonylC1_6alkyl or C1_6alkylsulfonylaminoC1_6alkyl; or
R12 is d scycloalkyl, C1_8cycloalkylC1_6alkyl, wherein the cycloalkyl moiety is optionally partially unsaturated, phenyl, phenylC1_6alkyl, heteroaryl, heteroarylC1_6alkyl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl or heterocyclylC1_6alkyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S; wherein for R12, any cycloalkyl, phenyl, heteroaryl or heterocyclyl moiety is optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R13; wherein R13 is cyano, halogen, hydroxy, C1_4alkyl, C2-4alkenyl, C2-4alkynyl, C1_4haloalkyl, C2_ 4haloalkenyl, C1_4alkoxy, C1_4haloalkoxy, C3_4alkenyloxy, C3_4alkynyloxy, N-C1_4alkylamino, N,N-diC1_ 4alkylamino, C1_4alkylcarbonyl, C1_4alkoxycarbonyl, carbonylamino, N-C1_4alkylaminocarbonyl, N,N- diC1-4alkylaminocarbonyl or C1_4alkoxycarbonylamino; and wherein when R12 is substituted C3_8cycloalkyl, C3_8cycloalkylC1_6alkyl, heterocyclyl, or heterocyclylC1-6alkyl, R13 may also represent oxo on the C3_8cycloalkyl or heterocyclyl moiety; or
R8 represents -NR14R15, wherein R14 is hydrogen, cyano, C1_6alkyl, C1_6alkoxy, C2_6alkenyl, C2_ 6alkynyl, C3_6alkenyloxy, C3_6alkynyloxy, cyanoC1_6alkyl, C1_6haloalkyl, C1_6haloalkenyl, hydroxyC1_6alkyl, C1-4alkoxyC1_6alkyl, C1_4haloalkoxyC1_6alkyl, C1_4alkoxyC1_4alkoxyC1_6alkyl, aminoC1_6alkyl, N-C1_ 4alkylaminoC1_6alkyl, N,N-diC1_4alkylaminoC1_6alkyl, C1_6alkylcarbonylC1_6alkyl, C1_6alkylcarbonylC2_ 6alkenyl, C1_6alkoxycarbonylC1_6alkyl, C1_6alkylcarbonyloxyC1_6alkyl, N-C1_4alkylaminocarbonylC1_6alkyl, N,N-diC1-4alkylaminocarbonylC1_6alkyl, C1_4alkylsulfanylC1_6alkyl, C1_6alkylsulfonylC1_6alkyl or C1_ 6alkylsulfonylaminoC1_6alkyl; or
R14 is C3_8cycloalkyl, C3_8cycloalkylC1_6alkyl, C3_8cycloalkylC1_6alkoxy, C3_6cycloalkyloxy, wherein the cycloalkyi moiety is optionally partially unsaturated, phenyl, phenylC1_6alkyl, phenylC1_ 6alkoxy, heteroaryl, heteroarylC1_6alkyl, heteroarylC1_6alkoxy, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl, heterocyclylC1_6alkyl or heterocyclylC1_6alkoxy wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S; wherein for R14, any cycloalkyi, phenyl, heteroaryl, heterocyclyl moiety is optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R16; wherein R16 is cyano, halogen, hydroxy, C1_4alkyl, C2_4alkenyl, C2_4alkynyl, C1_4haloalkyl, C2_
4haloalkenyl, C1_4alkoxy, C1_2alkoxyC1_2alkyl, C1_4haloalkoxy, C3_4alkenyloxy, C3_4alkynyloxy, N-C1_ 4alkylamino, N,N-diC1_4alkylamino, C1_4alkylcarbonyl, C1_4alkoxycarbonyl, carbonylamino, N-C1_ 4alkylaminocarbonyl, N,N-diC1_4alkylaminocarbonyl and C1_4alkoxycarbonylamino; and wherein when R14 is substituted C3_8cycloalkyl, C3_8cycloalkylC1_6alkyl, C3_8cycloalkylC1_
6alkoxy, heterocyclyl, heterocyclylC1_6alkyl or heterocyclylC1_6alkoxy, R16 may also represent oxo on the C3_8cycloalkyl or heterocyclyl moiety;
R15 is hydrogen, C1_4alkyl, C3_4alkynyl, C1_4alkoxyC1_4alkyl, cyanoC1_4alkyl, C3_6cycloalkyl, C3. 6cycloalkylC1-2alkyl; or R14 and R15, together with the nitrogen atom to which they are bonded , form a 4-, 5- or 6- membered cycle optionally containing an additional heteroatom or group selected from O, S, S(0)2, oxo (=0) and NR17; wherein R17 is hydrogen, methyl, methoxy, formyl or acyl; or a salt or an N-oxide thereof.
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, carbonylamino means an -N(H)C(0)H 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 "C1_6alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to six carbon atoms, and which is attached to the rest of the molecule by a single bond. The terms "C1_4alkyl" and "C1-2alkyl" are to be construed accordingly. Examples of C1_6alkyl include, but are not limited to, methyl, ethyl, n-propyl, 1 -methylethyl (iso-propyl), n-butyl, 1 , 1 -dimethylethyl (ieri-butyl) and n-pentyl. A "C1-C6alkylene" group refers to the corresponding definition of C1-C6alkyl (and C1_4alkyl and C1_2alkyl), except that such radical is attached to the rest of the molecule by two single bonds. Examples of C1_ C6alkylene, include, but are not limited to, -CH2-, -CH2CH2- and -(CH2)3-.
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 "C3_6alkenyl" 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 "C3_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, oxo means an =0 group, eg, a ketonyl (-C(O)-), sulfinyl (-S(O)-) or sulfonyl (- S(0)2-) oxygen.
As used herein, the term "N-C1_4alkylamino" refers to a radical of the formula -NH-Ra where Ra is a C1-4alkyl radical as defined above.
As used herein, the term "N,N-diC1_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 "C1_6alkoxy" refers to a radical of the formula -ORa where Ra is a C1_ 6alkyl radical as generally defined above. The terms "C1_4alkoxy" and "C1_2alkoxy" are to be construed accordingly. Examples of C1_6alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, iso- propoxy, butoxy.
As used herein, the term "C1_4alkoxycarbonyloxy" refers to a radical of the formula -OC(0)Ra where Ra is a C1_4alkoxy radical as generally defined above.
As used herein, the term " C1_4alkoxycarbonyloxyC1_4alkyl" refers to a C1_4alkyl radical as generally defined above substituted by a C1_4alkoxycarbonyloxy radical as generally defined above.
As used herein, the term "hydroxyC1_4alkyl" refers to a C1_4alkyl radical as generally defined above substituted by one or more hydroxy groups as defined above.
As used herein, the term "C1_6alkylcarbonyl" refers to a radical of the formula -C(0)Ra where Ra is a C1-6alkyl radical as generally defined above. The term "C1_4alkylcarbonyl" is to be construed accordingly.
As used herein, the term "C1_6alkoxycarbonyl" refers to a radical of the formula -C(0)ORa where Ra is a C1-6alkyl radical as generally defined above. The term "C1_4alkoxycarbonyl" is to be construed accordingly.
As used herein, the term "C1_6alkylcarbonyloxy" refers to a radical of the formula -OC(0)Ra where Ra is a C1_6alkyl radical as generally defined above. The term "C1_4alkylcarbonyloxy" is to be construed accordingly.
As used herein, the term "N-C1_4alkylaminocarbonyl" refers to a radical of the formula - C(0)NHRa where Ra is a C1_4alkyl radical as generally defined above.
As used herein, the term "N,N-diC1_4alkylaminocarbonyl" refers to a radical of the formula -
C(0)NRa(Ra) where each Ra is a C1_4alkyl radical as generally defined above. As used herein, the term "C1_4alkylcarbonylamino" refers to a radical of the formula -NHC(0)Ra where Ra is a C1_4alkyl radical as generally defined above.
As used herein, the term "C1-4alkylcarbonylaminoC1-6alkyr' refers to a C1_6alkyl radical as generally defined above substituted by a C1_4alkylcarbonylamino group as defined above.
As used herein, the term "C1_4alkoxycarbonylamino" refers to a radical of the formula -
NHC(0)ORa where Ra is a C1_4alkyl radical as generally defined above.
As used herein, the term "C1_4alkoxycarbonylaminoC1_6alkyl" refers to a C1_6alkyl radical as generally defined above substituted by a C1_4alkoxycarbonylamino group as defined above.
As used herein, the term "C1_6alkylsulfanyl" refers to a radical of the formula -SRa where Ra is a C1-6alkyl radical as generally defined above. The term "C1_4alkylsulfanyl" is to be construed accordingly.
As used herein, the term "C1_6alkylsulfinyl" refers to a radical of the formula -S(0)Ra where Ra is a C1-6alkyl radical as generally defined above. The term "C1_4alkylsulfonyl" is to be construed accordingly.
As used herein, the term "C1_6alkylsulfonyl" refers to a radical of the formula -S(0)2Ra where Ra is a C1-6alkyl radical as generally defined above. The term "C1_4alkylsulfonyl" is to be construed accordingly.
As used herein, the term "C1_6alkylsulfonylamino" refers to a radical of the formula -NHS(0)2Ra where Ra is a C1_6alkyl radical as generally defined above. The term "C1_4alkylsulfonylamino" is to be construed accordingly.
As used herein, the term "C3_6alkenyloxy" refers to a radical of the formula -ORa where Ra is a C3_6alkenyl radical as generally defined above.
As used herein, the term "C2_6alkynloxy" refers to a radical of the formula -ORa where Ra is a C2_ 6alkynyl radical as generally defined above. The terms "C2_4alkynloxy" and "C3_6alkynyloxy" are to be construed accordingly.
As used herein, the term "C3_6haloalkenyloxy" refers to a C3_6alkenyloxy radical as generally defined above substituted by one or more of the same or different halogen atoms_
As used herein, the term "C2_6alkynyloxycarbonylamino" refers to a radical of the formula - NHC(0)ORa where Ra is a C2_6alkynyl radical as generally defined above. The term "C2_ 4alkynyloxycarbonylamino" is to be construed accordingly.
As used herein, the term "C1_4haloalkoxy" refers to a C1_4alkoxy group as defined above substituted by one or more of the same or different halogen atoms. Examples of C1_4haloalkoxy include, but are not limited to, fluoromethoxy, fluoroethoxy, trifluoromethoxy, trifluoroethoxy.
As used herein, the term "cyanoC1_6alkyl" refers to a C1_6alkyl radical as generally defined above substituted by one or more cyano groups as defined above. The term "cyanoC1_4alkyl" is to be construed accordingly. Examples of cyanoC1_6alkyl include, but are not limited to cyanomethyl, cyanoethyl.
As used herein, the term "C1_6haloalkyl" refers to a C1_6alkyl radical as generally defined above substituted by one or more of the same or different halogen atoms. The term "C1_4haloalkyl" is to be construed accordingly. Examples of C1_6haloalkyl include, but are not limited to fluoromethyl, fluoroethyl, trifluoromethyl, 2,2,2-trifluoroethyl. 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 terms "C2-4haloalkenyl" and "C3_6haloalkenyl" are to be construed accordingly.
As used herein, the term "C1_4haloalkylcarbonyloxy" refers to a radical of the formula -OC(0)Ra where Ra is a C1_4haloalkyl radical as generally defined above.
As used herein, the term "C1_4haloalkylcarbonyloxyC1_4alkyl" refers to a C1_4alkyl radical as generally defined above substituted by a C1_4haloalkylcarbonyloxy radical as generally defined above.
As used herein, the term "hydroxyC1_6alkyl" refers to a C1_6alkyl radical as generally defined above substituted by one or more hydroxy groups as defined above. The term "hydroxyC1_4alkyl" is to be construed accordingly.
As used herein, the term "C1_4alkoxyC1_6alkyl" refers to a C1_6alkyl radical as generally defined above substituted by a C1_4alkoxy group as defined above. The terms "C1_4alkoxyC1_4alkyl" and "C1_ 2alkoxyC1_4alkyl" are to be construed accordingly. Examples of C1_4alkoxyC1_6alkyl include, but are not limited to methoxymethyl, 2-methoxyethyl.
As used herein, the term "C1_4haloalkoxyC1_6alkyl" refers to a C1_6alkyl radical as generally defined above substituted by a C1_4haloalkoxy group as defined above. The terms "C1_4halolalkoxyC1_ 4alkyl" and "C1_2haloalkoxyC1_4alkyl" are to be construed accordingly.
As used herein, the term "C1_4alkoxyC1_4alkoxyC1_6alkyl" refers to a C1_6alkyl radical as generally defined above substituted by a C1_4alkoxy group as defined above, the C1_4alkoxy group itself substituted by a C1_4alkoxy group as defined above.
As used herein, the term "C2_6alkynyloxyC1_6alkyl" refers to a C1_6alkyl radical as generally defined above substituted by a C2_6alkynyloxy group as defined above.
As used herein, the term "aminoC1_6alkyl" refers to a C1_6alkyl radical as generally defined above substituted by one or more amino groups as defined above. The term "aminoC1_4alkyl" is to be construed accordingly.
As used herein, the term "N-C1_4alkylaminoC1_6alkyl" refers to a C1_6alkyl radical as generally defined above substituted by a N-C1_4alkylamino group as defined above. The term "N-C1_ 4alkylaminoC1_4alkyl" is to be construed accordingly.
As used herein, the term "N,N-diC1_4alkylaminoC1_6alkyl" refers to a C1_6alkyl radical as generally defined above substituted by a N,N-diC1_4alkylamino group as defined above. The term "N,N-diC1_ 4alkylaminoC1_4alkyl" is to be construed accordingly.
As used herein, the term "C1_6alkylcarbonylC1_6alkyl" refers to a C1_6alkyl radical as generally defined above substituted by a C1_6alkylcarbonyl group as defined above. The term "C1_ 6alkylcarbonylC1_4alkyl" is to be construed accordingly.
As used herein, the term "C1_6alkylcarbonylC2_6alkenyl" refers to a C2_6alkenyl radical as generally defined above substituted by a C1_6alkylcarbonyl group as defined above. The term "C1_ 6alkylcarbonylC2-4alkenyl" is to be construed accordingly.
As used herein, the term "C1_6alkoxycarbonylC1_6alkyl" refers to a C1_6alkyl radical as generally defined above substituted by a C1_6alkoxycarbonyl group as defined above. The term "C1_ 6alkoxycarbonylC1_4alkyl" is to be construed accordingly. As used herein, the term "C1_6alkylcarbonyloxyC1_6alkyl" refers to a C1_6alkyl radical as generally defined above substituted by a C1_6alkylcarbonyloxy group as defined above. The term "C1_ 6alkylcarbonyloxyC1_4alkyl" is to be construed accordingly.
As used herein, the term "N-C1-4alkylaminocarbonylC1-6alkyr', refers to a C1_6alkyl radical as generally defined above substituted by a N-C1_4alkylaminocarbonyl group as defined above. The term "N-C1_4alkylaminocarbonylC1_4alkyl" is to be construed accordingly.
As used herein, the term "N,N-diC1_4alkylaminocarbonylC1_6alkyl", refers to a C1_6alkyl radical as generally defined above substituted by a N,N-diC1_4alkylaminocarbonylC1_6alkyl group as defined above. The term "N,N-diC1_4alkylaminocarbonylC1_4alkyl " is to be construed accordingly.
As used herein, the term "C1-6alkylsulfanylC1-6alkyr', refers to a C1_6alkyl radical as generally defined above substituted by a C1_6alkylsulfanyl group as defined above. The term "C1_6alkylsulfanylC1_ 4alkyl" is to be construed accordingly.
As used herein, the term "C1-6alkylsulfonylC1-6alkyr', refers to a C1_6alkyl radical as generally defined above substituted by a C1_6alkylsulfonyl group as defined above. The term "C1_6alkylsulfonylC1_ 4alkyl" is to be construed accordingly.
As used herein, the term "C1-6alkylsulfonylaminoC1-6alkyr', refers to a C1_6alkyl radical as generally defined above substituted by a C1_6alkylsulfonylamino group as defined above. The term "C1_ 6alkylsulfonylaminoC1_4alkyl" is to be construed accordingly.
As used herein, the term "C1_6alkylsulfonylaminoC1_6alkynyr, refers to a d^alkynyl radical as generally defined above substituted by a C1_6alkylsulfonylamino group as defined above. The term "C1_ 6alkylsulfonylaminoC1_4alkynyl" is to be construed accordingly.
As used herein, C1_6alkynyloxycarbonylaminoC1_6alkyl refers to a C1_6alkyl radical as generally defined above substituted by a d ealkynyloxycarbonylamino group as defined above. The term "C2- 4alkynyloxycarbonylaminoC1_4alkyl" is to be construed accordingly.
As used herein, the term "C1_8cycloalkyl" may be mono- or bi-cyclic and contains 3 to 8 carbon atoms. "C1_6cycloalkyl" is to be construed accordingly. Examples of C1_scycloalkyl include, but are not limited to, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
As used herein, the term "aryl" refers to an aromatic ring system consisting solely of carbon and hydrogen atoms which may be mono-, bi- or tricyclic. Examples of such ring systems include phenyl, naphthalenyl, anthracenyl, indenyl or phenanthrenyl.
As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic ring radical which comprises 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur. The heteroaryl radical may be bonded via a carbon atom or heteroatom. Examples of heteroaryl include, but are not limited to, furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl or pyridyl.
As used herein, the term "heterodiaryl" refers to a stable 9- or 10-membered bicyclic aromatic ring system which comprises 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur. The heteroaryl radical may be bonded via a carbon atom or heteroatom.
As used herein, the term "heterocyclyl" or "heterocyclic" refers to a stable 4-, 5- or 6-membered non-aromatic monocyclic ring radical which comprises 1 , 2, or 3, heteroatoms individually selected from nitrogen, oxygen and sulfur. The heterocyclyl radical may be bonded to the rest of the molecule via a carbon atom or heteroatom. Examples of heterocyclyl include, but are not limited to, azetidinyl, oxetanyl, pyrrolinyl, pyrrolidyl, thietanyl, tetrahydrofuryl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidyl, piperazinyl, tetrahydropyranyl, morpholinyl or perhydroazepinyl.
As used herein, the term "C3-8cycloalkylCo-6alkyl" refers to a C3_8cycloalkyl ring as defined above attached to the rest of the molecule by a single bond or by a C1-C6alkylene radical as defined above. "C3-6cycloalkylC1-2alkyr' is to be construed accordingly. Examples of C3_8cycloalkylC0-6alkyl include, but are not limited to, cyclopropyl, cyclopropylmethyl, cyclopropylethyl, cyclobutyl, cyclopentyl or cyclohexyl.
As used herein, the term "C3-6cycloalkylC1-2alkoxy" refers to a C1_2alkoxy radical as generally defined above substituted by a C3-6cycloalkyl ring as defined above.
As used herein, the term "C3_6cycloalkylcarbonyl" refers to a -C(0)Ra radical, wherein Ra is a C3-6cycloalkyl ring as defined above.
As used herein, the term "C3_6cycloalkylcarbonyloxy" refers to a -OC(0)Ra radical wherein Ra is a C3_6cycloalkyl ring as described above.
As used herein, the term "C3_6cycloalkylcarbonyloxyC1_4alkyl" refers to a C3_ 6cycloalkylcarbonyloxy group as described above attached to the rest of the molecule by a C1_ 4alkylene radical as defined above.
As used herein, the term "phenylC0-6alkyl" refers to a phenyl ring attached to the rest of the molecule by a single bond or by a C1_6alkylene radical as defined above. "PhenylC1_6alkyl" and "phenylC1_2alkyl" are to be construed accordingly. Examples of phenylC0-6alkyl include, but are not limited to, phenyl, benzyl or 2-phenylethyl.
As used herein, the term "phenylC1_2alkoxy" refers to a C1_2alkoxy radical as generally defined above substituted by a phenyl ring.
As used herein, the term "phenylC2_6alkenyl" refers to a C2_6alkenyl radical as generally defined above substituted by a phenyl ring.
As used herein, the term "phenylcarbonyloxy" refers to a -OC(0)Ra radical wherein Ra is a phenyl ring.
As used herein, the term "phenylcarbonyloxyC1_4alkyl" refers to a phenylcarbonyloxy group as described above attached to the rest of the molecule by a C1_4alkylene radical as defined above.
As used herein, the term "naphthylC0-6alkyl" refers to a naphthalene ring attached to the rest of the molecule by a single bond or by a C1_6alkylene radical as defined above.
As used herein, the term "heteroarylC0-6alkyl" refers to a heteroaryl ring as described above attached to the rest of the molecule by a single bond or by a C1_6alkylene radical as defined above. "HeteroarylC1-6alkyr' and "heteroarylC1_2alkyl" are to be construed accordingly.
As used herein, the term "heteroarylC1_6alkoxy" refers to a C1_6alkoxy radical as generally defined above substituted by a heteroaryl group as generally defined above. HeteroarylC1_2alkoxy" is to be construed accordingly. As used herein, the term "heterodiarylC0-6 alkyl" refers to a heterodiaryl ring as described above attached to the rest of the molecule by a single bond or by a C1_6alkylene radical as defined above. "HeterodiarylC1-6alkyr' and "heterodiarylC1_2alkyl" are to be construed accordingly.
As used herein, the term "heterocyclylC0-6alkyl" refers to a heterocyclyl ring as described above attached to the rest of the molecule by a single bond or by a C1_6alkylene radical as defined above. "HeterocyclylC1-6alkyr' and "heterocyclylC1_2alkyl" are to be construed accordingly.
As used herein, the term "heterocyclylC1_6alkoxy" refers to a C1_6alkoxy radical as generally defined above substituted by a heterocyclyl group as generally defined above. "HeterocyclylC1-2alkoxy" is to be construed accordingly.
As used herein, the term "heterocyclylcarbonyloxy" refers to a -OC(0)Ra radical wherein Ra is a heteroaryl ring as described above.
As used herein, the term "heterocyclylcarbonyloxyC1-4alkyl" refers to a heterocyclylcarbonyloxy group as described above attached to the rest of the molecule by a C1_4alkylene radical as defined above.
As used herein, the term "C3-6cycloalkylcarbonylaminoC1-6alkyr' refers to a a radical of the formula -RaNHC(0)Rb, wherein Ra is a C1_6alkyl radical as defined above and Rb is a C3-6cycloalkyl ring as described above.
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 covalently hydrated form, in oxidized form as an N-oxide or in salt form, e.g., an agronomically usable or agrochemically acceptable salt form.
N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
The following list provides definitions, including preferred definitions, for substituents n, A1, A2, A3, A4, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 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 R1 is hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy.
A2 represents N or CR2, wherein R2 is hydrogen, halogen, methyl, ethyl, difluoromethyl, 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 0, 1 or 2 of A1 , A2, A3 and A4 are N;
R1 and R2 are independently selected from hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy. Preferably, R1 and R2 are independently selected from hydrogen and halogen. More preferably, R1 and R2 are hydrogen. R3 and R4 are independently selected from hydrogen and halogen. Preferably, R3 and R4 are independently selected from hydrogen and fluoro. More preferably, R3 and R4 are hydrogen.
A3 may represent CR3, wherein R3 is hydrogen or halogen. A4 may represent CR4, wherein R4 is hydrogen or halogen.
In the compounds according to Formula (I), at least two of R1 , R2, R3 and R4 may be hydrogen. Preferably, three of R1 , R2, R3 and R4 may be hydrogen, wherein more preferably R2, R3 and R4 are hydrogen.
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 the compounds according to Formula (I), when R8 is not -OR12 or -NR14R15, preferably A1 , A2, A3 and A4 are C-H; A2, A3 and A4 are C-H and A1 is N; A1 , A2 and A4 are C-H and A3 is N; A1 , A2 and A4 are C-H and A3 is C-halogen (preferably fluoro); A2, A3 and A4 are C-H and A1 is C-halogen (preferably fluoro) or A2, A3 and A4 are C-H and A1 is C-halogen (preferably fluoro); A2 and A4 are C-H and A1 and A3 are C-halogen (preferably fluoro); or A3 and A4 are C-H and A1 and A2 are C-halogen (preferably fluoro). More preferably, A1, A2, A3 and A4 are C-H.
In the compounds according to Formula (I), when R8 is -OR12, preferably A1, A2, A3 and A4 are C-H.
In the compounds according to Formula (I), when R8 is -NR14R15, preferably A1, A2, A3 and A4 are C-H; A1, A2 and A4 are C-H and A3 is C-halogen (preferably fluoro); or A2, A3 and A4 are C-H and A1 is C-halogen (preferably fluoro). More preferably, A1, A2, A3 and A4 are C-H. R5 and R6 independently represent 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 may be 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. More preferably, R5 and R6 are independently selected from hydrogen, C1_4alkyl (in particular methyl) and cyano.
In the compounds according to Formula (I), when R8 is not -OR12 or -NR14R15, preferably R5 and R6 are hydrogen; R5 is hydrogen and R6 is methyl; or R5 is hydrogen and R6 is cyano. More preferably, R5 and R6 are hydrogen and n is 1.
In the compounds according to Formula (I), when R8 is -OR12, preferably R5 and R6 are hydrogen and n is 1.
In the compounds according to Formula (I), when R8 is -NR14R15, preferably R5 and R6 are hydrogen and n is 1.
R7 is hydroxy, C1_4alkyl, C2-4haloalkyl, C1_4alkoxy, hydroxyC1_4alkyl, C1.2alkoxyC1_4alkyl, d. 2haloalkoxyC1-4alkyl, C3_4alkynyl, C3.6alkenyl, C3.6alkenyloxy, C3.6alkynyloxy, C3.6haloalkenyl, C3. 6haloalkenyloxy, C1_4alkylcarbonyloxy, C1_4haloalkylcarbonyloxy, C1_4alkoxycarbonyloxy, d. 4alkylcarbonyloxyC1-4alkyl, C1_4haloalkylcarbonyloxyC1^alkyl, C1_4alkoxycarbonyloxyC1_4alkyl; or R7 is C3.6cycloalkyl, C3-6cycloalkylC1-2alkyl, C3.6cycloalkylC1_2alkoxy, phenyl, phenylC1_2alkyl, phenyld. 2alkoxy, heteroaryl, heteroarylC1_2alkyl, heteroarylC1_2alkoxy, heterocyclyl, heterocyclylC1_2alkyl, heterocyclylC1_2alkoxy, C3.6cycloalkylcarbonyloxy, heterocyclylcarbonyloxy, phenylcarbonyloxy, C3. 6cycloalkylcarbonyloxyC1_4alkyl, heterocyclylcarbonyloxyC1_4alkyl or phenylcarbonyloxyC1_4alkyl; wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 or 2 heteroatoms individually selected from N, O and S, and wherein any of said cycloalkyl, phenyl, heteroaryl and heterocyclyl moieties are optionally substituted by 1 or 2 substituents selected from cyano, fluoro, chloro, bromo, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy. Preferably, R7 is C1_4alkyl, C1_4alkoxy,
Figure imgf000015_0001
C1-2haloalkoxyC1-4alkyl, C3.6alkenyl, C3_4alkynyl, C3.6alkenyloxy, C3.6alkynyloxy, C3.6haloalkenyl, C3.6haloalkenyloxy, C3.6cycloalkyl, C3. 6cycloalkylC1_2alkyl, C3-6cycloalkylC1-2alkoxy, phenyl, phenylC1_2alkyl, phenylC1_2alkoxy, heteroaryl, heteroarylC1-2alkyl, heteroarylC1_2alkoxy, heterocyclyl, heterocyclylC1_2alkyl, or heterocyclylC1_2alkoxy.
More preferably, R7 is C1_4alkyl, C1_4alkoxy, C1_2alkoxyC1_4alkyl, C3.6alkenyl, C3_4alkynyl, C3.
6alkenyloxy, C3.6haloalkenyl, C3.6haloalkenyloxy, C3.6cycloalkyl, C3.6cycloalkylC1_2alkyl, phenylC1. 2alkoxy, heteroarylC1_2alkyl, or heterocyclylC1_2alkyl.
In the compounds according to Formula (I), when R8 is not -OR12 or -NR14R15, preferably R7 is hydroxy, C1_4alkyl, C2_4haloalkyl, C1_4alkoxy, hydroxyC1_4alkyl, C1_2alkoxyC1_4alkyl, C3.6alkenyl, C3. 4alkynyl, C3.6haloalkenyloxy, C3.6cycloalkyl, C3.6cycloalkylC1_2alkyl, phenylC1_2alkoxy, heterocyclyl, heterocyclylC1_2alkyl, heteroaryl or heteroarylC1_2alkyl, wherein the heteroaryl moiety is a 5-membered monocyclic aromatic ring which comprises 1 or 2 heteroatoms individually selected from N, O and S, the heterocyclyl moiety is a 5-membered non-aromatic ring which comprises 1 or 2 heteroatoms individually selected from N, O and S, and wherein any of said cycloalkyi, phenyl, heteroaryl and heterocyclyl moieties are optionally substituted by 1 or 2 substituents selected from cyano, fluoro, chloro, bromo, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy. More preferably, R7 is hydroxy, C1_4alkyl, C2_4fluoroalkyl, C1_4alkoxy, hydroxyC1_4alkyl, C1_2alkoxyC1_4alkyl, C3. 4alkenyl, C3_4alkynyl, C3.6haloalkenyloxy, cyclopropyl, (cyclopropyl)methyl, phenylC1_2alkoxy, (tetrahydrofuran-2-yl)methyl or (2-furyl)methyl, wherein any of said cyclopropyl, phenyl, tetrahydrofuran-2-yl and 2-furyl moieties are optionally substituted by 1 or 2 substituents selected from cyano, fluoro, chloro, bromo, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy. In the compounds according to Formula (I), when R8 is not -OR12 or -NR14R15, still more preferably R7 is C1_4alkyl, C2_4haloalkyl, C1_4alkoxy or C3.6cycloalkyl. Further more preferably, R7 is C1_ 4alkyl, C2_4fluoroalkyl, methoxy, ethoxy or cyclopropyl. Most preferably, R7 is methyl, ethyl, n-propyl, iso-propyl, 2,2,2-fluoroethyl, methoxy, ethoxy or cyclopropyl. In the compounds according to Formula (I), when R8 is -OR12, preferably R7 is hydroxy, C1_
4alkyl, C2_4haloalkyl, C1_4alkoxy, C3.6alkenyl, C3_4alkynyl, C1_4alkoxycarbonyloxy. More preferably, R7 is hydroxy, C1_4alkyl, C2_4haloalkyl, C1_4alkoxy, C3_4alkenyl, C3_4alkynyl, C1_4alkoxycarbonyloxy. Even more preferably, R7 is C1_4alkoxy, in particular, methoxy. In the compounds according to Formula (I), when R8 is -NR14R15, preferably R7 is hydroxy, C1_
4alkyl, C1_4haloalkyl, C1_4alkoxy, d^alkenyl, C1_4alkynyl, d ecycloalkyl. More preferably, R7 is hydroxy, C1_4alkyl, C2haloalkyl, C1.2alkoxy, C1_4alkenyl, C1_4alkynyl, cyclopropyl. Even more preferably, R7 is C1_ 4alkyl or C1_4alkoxy, and in particular, methyl, ethyl or methoxy. R8 is hydrogen, C1_6alkyl, d^alkenyl, d^alkynyl, cyanoC1.6alkyl, d.6haloalkyl, C2-
6haloalkenyl, hydroxyd.6alkyl, C1_4alkoxyd.6alkyl, C1_4haloalkoxyd.6alkyl, C1_4alkoxyC1_4alkoxyC1_ 6alkyl, C2-4alkynyloxyC1.6alkyl, aminoC1.6alkyl, N-C1_4alkylaminoC1.6alkyl, N,N-diC1_4alkylaminoC1.6alkyl, C1.6alkylcarbonylC1.6alkyl, C1-6alkylcarbonylC2-6alkenyl, C1.6alkoxycarbonylC1.6alkyl, C1_ 6alkylcarbonyloxyC1_6alkyl, N-C1_4alkylaminocarbonylC1.6alkyl, N,N-diC1_4alkylaminocarbonylC1.6alkyl, C1.6alkylsulfanylC1.6alkyl, C1.6alkylsulfonylC1.6alkyl, C1.6alkylsulfonylaminoC1.6alkyl, C1_6 alkylsulfonylaminoC2-6alkynyl, C2-6alkynyloxycarbonylaminoC1-6alkyl, C1_4alkylcarbonylaminoC1.6alkyl, C1 _4alkoxycarbonylam i noC1 _6al kyl ; or
R8 is C3.8cycloalkyl, C3.8cycloalkylC1.6alkyl, wherein the cycloalkyl moiety is optionally partially unsaturated, phenyl, phenylC1_6alkyl, phenylC2.6alkenyl, napthyl, naphthylC1_6alkyl, heteroaryl, heteroarylC1_6alkyl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterodiaryl, heterodiarylC1-6alkyl wherein the heterodiaryl moiety is a 9- or 10-membered bicyclic aromatic system which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl, heterocyclylC1-6alkyl wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, or C3. 6cycloal kylcarbonylam i noC1 _6alkyl , wherein for R8, any cycloalkyl, phenyl, napthyl, heteroaryl, heterodiaryl, heterocyclyl moiety is optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R9; or, additionally, when R8 is cyclopropyl, the cyclopropyl moiety is substituted by 4 substituents, which may be the same or different, selected from R9, with the proviso that at least 2 R9 substituents are the same; wherein
R9 is cyano, halogen, hydroxy, C1_4alkyl, C2-4alkenyl, C2_4alkynyl, C1_4haloalkyl, C2_4haloalkenyl, C1-4alkoxy, C1_4haloalkoxy, C3_4alkynyloxy, N-C1_4alkylamino, N,N-diC1_4alkylamino, C1_4alkylcarbonyl, C3.6cycloalkylcarbonyl, C1_4alkoxycarbonyl, carbonylamino, N-C1_4alkylaminocarbonyl, N,N-diC1_ 4alkylaminocarbonyl or C1_4alkoxycarbonylamino, and wherein when R8 is substituted C3.8cycloalkyl, C3.8cycloalkylC1-6alkyl, heterocyclyl, or heterocyclylC1_6alkyl, R9 may also represent oxo on the C3. scycloalkyl or heterocyclyl moiety; or wherein for R8, any cycloalkyl, phenyl, napthyl, heteroaryl, heterodiaryl, heterocyclyl, moiety is optionally substituted by 1 substituent selected from R10 and further optionally substituted by 1 or 2 substituents selected from R9; wherein R10 is C3.8cycloalkyl, C3.8cycloalkylC1_2alkyl, phenyl, phenylC1_2alkyl, heteroaryl, heteroarylC1_
2alkyl wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl, heterocyclylC1_6alkyl wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, and wherein any of said cycloalkyl, phenyl, heteroaryl and heterocyclyl moieties are optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R11 ; wherein R11 is hydrogen, cyano, fluoro, chloro, bromo, methyl, trifluoromethyl, methoxy and ethoxy.
In some embodiments of the compounds according to Formula (I), R8 is hydrogen, C1_6alkyl, C2-6alkenyl, C2-6alkynyl, cyanoC1_6alkyl, C1_6haloalkyl, C1_6haloalkenyl, hydroxyC1_6alkyl, C1_4alkoxyC1_ 6alkyl, C1_4haloalkoxyC1.6alkyl, C1-4alkoxyC1.4alkoxyC1.6alkyl, C2-4alkynyloxyC1.6alkyl, aminoC1_6alkyl, N- C1_4alkylaminoC1.6alkyl, N,N-diC1_4alkylaminoC1.6alkyl, C1.6alkylcarbonylC1.6alkyl, C1.6alkylcarbonylC2- 6alkenyl, C1.6alkoxycarbonylC1.6alkyl, C1.6alkylcarbonyloxyC1.6alkyl, N-C1_4alkylaminocarbonylC1.6alkyl, N,N-diC1_4alkylaminocarbonylC1.6alkyl, C1.6alkylsulfanylC1.6alkyl, C1.6alkylsulfonylC1.6alkyl, C1_ 6alkylsulfonylaminoC1-6alkyl, C1.6alkylsulfonylaminoC2.6alkynyl, or C2.6alkynyloxycarbonylaminoC1. 6alkyl.
In some embodiments of the compounds according to Formula (I), R8 is C3.8cycloalkyl, C3. 8cycloalkylC1-6alkyl, wherein the cycloalkyl moiety is optionally partially unsaturated, phenyl, phenylC1_ 6alkyl, phenylC2.6alkenyl, napthyl, naphthylC1_6alkyl, heteroaryl, heteroarylC1_6alkyl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterodiaryl, heterodiarylC1_6alkyl wherein the heterodiaryl moiety is a 9- or 10-membered bicyclic aromatic system which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl, heterocyclylC1_6alkyl wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, and C3.6cycloalkylcarbonylaminoC1.6alkyl. At least one of C3. scycloalkyl, C3-8cycloalkylC1-6alkyl, phenyl, phenylC1_6alkyl, phenylC2.6alkenyl, napthyl, naphthylC1_ 6alkyl, heteroaryl, heteroarylC1_6alkyl, heterodiaryl, heterodiarylC1_6alkyl, heterocyclyl, heterocyclylC1. 6alkyl and C3.6cycloalkylcarbonylaminoC1.6alkyl moieties may be substituted by 1 , 2 or 3 substituents selected from cyano, halogen, hydroxy, C1_4alkyl, C2_4alkenyl, C2_4alkynyl, C1_4haloalkyl, C2. 4haloalkenyl, C1_4alkoxy, C1_4haloalkoxy, C3_4alkynyloxy, N-C1_4alkylamino, N,N-diC1_4alkylamino, C1_ 4alkylcarbonyl, C1_4alkoxycarbonyl, carbonylamino, N-C1_4alkylaminocarbonyl, N,N-diC1_ 4alkylaminocarbonyl and C1_4alkoxycarbonylamino.
Preferably, R8 is hydrogen, C1_6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoC1_6alkyl, C1_6haloalkyl, C2. 6haloalkenyl, hydroxyC1_6alkyl, C1_4alkoxyC1_6alkyl, C1_4haloalkoxyC1_6alkyl, C1_4alkoxyC1_4alkoxyC1. 6alkyl, C2_4alkynyloxyC1_6alkyl, aminoC1_6alkyl, C1.6alkylcarbonylC1.6alkyl, C1.6alkylcarbonylC2.6alkenyl, C1.6alkylcarbonyloxyC1.6alkyl, C1.6alkylsulfonylaminoC2.6alkynyl, C2.6alkynyloxycarbonylaminoC1.6alkyl, C1-4alkylcarbonylaminoC1.6alkyl, C1_4alkoxycarbonylaminoC1.6alkyl; or R8 is C3.8cycloalkyl, C3. 8cycloalkylC1_6alkyl, wherein the cycloalkyl moiety is optionally partially unsaturated, phenyl, phenylC1_ 6alkyl, phenylC1_6alkenyl, napthyl, heteroaryl, heteroarylC1.6alkyl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl, heterocyclyld.6alkyl wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, or C3-6cycloalkylcarbonylaminoC1_6alkyl, wherein for R8, any of C1_scycloalkyl, C1_scycloalkylC1_ 6alkyl, phenyl, phenyld.6alkyl, phenylC1_6alkenyl, napthyl, heteroaryl, heteroaryld.6alkyl, heterocyclyl and heterocyclylC1_6alkyl moieties are optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R ; wherein R is cyano, halogen, hydroxy, C1_4alkyl, C-|_4haloalkyl, C2-4haloalkenyl, C1_4alkoxy, C1_4haloalkoxy, C3_4alkynyloxy, C1_4alkylcarbonyl, C3.6cycloalkylcarbonyl, C1_4alkoxycarbonyl, carbonylamino; or wherein for R8, any of C3.8cycloalkyl, phenyl moieties are optionally substituted by 1 substituent selected from R10 and are further optionally substituted by 1 or 2 substituents selected from R9; wherein R10 is phenyl, heteroaryl wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein any of said phenyl and heteroaryl moieties are optionally substituted by a single substituents selected from R11; wherein R11 is cyano, fluoro, chloro, bromo, methyl, trifluoromethyl, methoxy and ethoxy.
More preferably, R8 is C1_6alkyl, C2-4alkenyl, C2-4alkynyl, cyanoC1_4alkyl, C1_5haloalkyl, C2. 4haloalkenyl, hydroxyC1_4alkyl, C1_2alkoxyC1_4alkyl, C1_2haloalkoxyC1_4alkyl, C1.2alkoxyC1_2alkoxyC1. 4alkyl, C2_4alkynyloxyC1_4alkyl, aminoC1_4alkyl, C1_4alkylcarbonylC1_4alkyl, C1_4alkylcarbonylC2_4alkenyl, C1-4alkylcarbonyloxyC1_4alkyl, C1_4alkylsulfonylaminoC2_4alkynyl, C2_4alkynyloxycarbonylaminoC1_4alkyl, C1-2alkylcarbonylaminoC1-4alkyl, C1.2alkoxycarbonylaminoC1_4alkyl; or R8 is C3.6cycloalkyl, C3. 6cycloalkylC1_2alkyl, wherein the cycloalkyl moiety is optionally partially unsaturated, phenyl, phenyld. 4alkyl, phenylC2_4alkenyl, napthyl, heteroaryl, heteroarylC1_2alkyl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, heterocyclyl, heterocyclylC1_2alkyl wherein the heterocyclyl moiety is a 4- to 6- membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, or C3.6cycloalkylcarbonylaminoC1_4alkyl, wherein for R8, any of C3.6cycloalkyl, C3.6cycloalkylC1_ 2alkyl, phenyl, phenylC1_2alkyl, phenylC2_4alkenyl, napthyl, heteroaryl, heteroarylC1_2alkyl, heterocyclyl and heterocyclylC1-2alkyl moieties are optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R9; wherein R9 is cyano, halogen, hydroxy, C1_4alkyl, C1_4haloalkyl, C2_4haloalkenyl, C1_4alkoxy, C1_4haloalkoxy, C3_4alkynyloxy, C1_4alkylcarbonyl, C3.6cycloalkylcarbonyl, C1_4alkoxycarbonyl, carbonylamino; or wherein for R8, any of C3.6cycloalkyl, phenyl moieties are optionally substituted by 1 substituent selected from R10 and are further optionally substituted by 1 or 2 substituents selected from R9; wherein R10 is phenyl, heteroaryl wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein any of said phenyl and heteroaryl moieties are optionally substituted by a single substituents selected from R11; wherein R11 is cyano, fluoro, chloro, bromo, methyl, trifluoromethyl, methoxy and ethoxy.
Even more preferably, R8 is C1_6alkyl, C2_4alkenyl, C2_4alkynyl, cyanoC1_4alkyl, C1_5haloalkyl, C2. 4haloalkenyl, hydroxyC1_4alkyl, C1_2alkoxyC1_4alkyl, C1_2haloalkoxyC1_4alkyl, C1.2alkoxyC1_2alkoxyC1. 4alkyl, aminoC1_4alkyl, C1_2alkylcarbonylC1_4alkyl, C1_4alkylcarbonylC2_4alkenyl, C1_4alkylcarbonyloxyC1_ 4alkyl, C1_4alkylsulfonylaminoC2_4alkynyl, C1.2alkylcarbonylaminoC1_4alkyl, C2.
4alkynyloxycarbonylaminoC1_4alkyl, C1.2alkoxycarbonylaminoC1_4alkyl; or R8 is C3.6cycloalkyl, C3.6cycloalkylC1_2alkyl, phenyl, phenylC1_4alkyl, phenylC2_4alkenyl, napthyl, a heteroaryl-containing moiety selected from furanyl (including furan-2-yl, furan-3-yl), pyrazolyl (including pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl), imidazolyl (including imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl), triazolyl (including 1 ,2,3-triazol-1-yl), 1 ,2,3- benzothiadiazole, (pyridinyl)methyl (including pyridin-2-methyl, pyridin-3-methyl, pyridin-4-methyl), or a heterocyclyl-containing moiety selected from oxetanyl (including oxetan-2-yl, oxetan-3-yl), pyrrolidinyl (including pyrrolidin-2-yl, pyrrolidin-3-yl), azetidinyl (including azetidin-2-yl, azetidin-3-yl), tetrahydrofuranyl (including tetrahydrofuran-2-yl, tetrahydrofuran-3-yl), 1 ,3-dioxolanyl (including 1 ,3- dioxolan-2-yl), thietanyl (including thietan-2-yl, thietan-3-yl), 1-oxo-thietan-3-yl, 1 ,1-dioxo-thietan-3-yl, tetrahydropyranyl (including tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl), tetrahydrothiopyranyl (including tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl), C3.6cycloalkylcarbonylaminoC1_4alkyl, wherein the cycle of each heteroaryl-containing moiety or heterocyclyl-containing moiety is optionally substituted by 1 or 2 or 3 substituents, which may be the same of different, selected from R9; wherein
R9 is cyano, methyl, chloro, fluoro, hydroxyl, methoxy, trifluoromethyl, C2-haloalkenyl, methylcarbonyl, ethylcarbonyl, carbonylamino; or wherein the cycle of each heteroaryl-containing moiety or heterocyclyl-containing moiety is optionally substituted by 1 substituent selected from R10 and further optionally substituted by 1 or 2 substituents selected from R9, wherein
R10 is phenyl or pyridinyl (including pyridin-2-yl), wherein phenyl or pyridinyl is optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R11; wherein
R11 is fluoro, chloro, bromo and methoxy.
In some embodiments of the compounds according to Formula (I), preferably, R8 is C1_6alkyl, C1-2haloalkyl, hydroxyC1_6alkyl, C1-2alkoxyC1-4alkyl, C3.6cycloalkyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- or 5-membered non-aromatic ring which comprises 1 or 2 heteroatoms individually selected from N and O, wherein C3.6cycloalkyl and heterocyclyl are optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R9; wherein R9 is cyano, halogen, hydroxy, C1_4alkyl, C2-4alkenyl, C2_4alkynyl, d^haloalkyl or C1_4alkoxy. More preferably, R8 is C1_4alkyl, C1_2haloalkyl, hydroxyC1_4alkyl, C1_2alkoxyC1_4alkyl, C3.
6cycloalkyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- or 5-membered non-aromatic ring which comprises 1 or 2 heteroatoms which are oxygen, wherein C3.6cycloalkyl and heterocyclyl are optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R9; wherein R9 is cyano, fluoro, chloro, hydroxy, methyl, ethyl, trifluoromethyl and methoxy. Even more preferably, R8 is C1_4alkyl, C1_2haloalkyl, hydroxyC1_4alkyl,
Figure imgf000020_0001
C3. 6cycloalkyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- or 5-membered non-aromatic ring which comprises 1 or 2 heteroatoms which are oxygen, wherein C3.6cycloalkyl and heterocyclyl are optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R9; wherein R9 is fluoro, chloro, methyl.
Still more preferably, R8 is C1_4alkyl (methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso- butyl, t-butyl), 2,2,2-trifluoroethyl, hydroxyC1_4alkyl,
Figure imgf000020_0002
cyclopropyl or heterocyclyl, wherein the heterocyclyl moiety is tetrahydrofuran-2-yl, oxetan-3-yl or 1 ,3-dioxolan-2-yl, wherein cyclopropyl and heterocyclyl are each optionally substituted by 1 or 2 substituents selected from R9, wherein R9 is fluoro, chloro, methyl.
R8 may represent -OR12, wherein R12 is hydrogen, C1_6alkyl, C3.6alkenyl, C3.6alkynyl, cyanoC-i. 6alkyl, C1_6haloalkyl, C3.6haloalkenyl, hydroxyC1_6alkyl, C1_4alkoxyC1_6alkyl, C1_4haloalkoxyC1_6alkyl, C1_ 4alkoxyC1-4alkoxyC1.6alkyl, aminoC1_6alkyl, N-C1_4alkylaminoC1.6alkyl, N,N-diC1_4alkylaminoC1.6alkyl, C1_ 6alkylcarbonylC1_6alkyl, C1.6alkylcarbonylC2-6alkenyl, C1.6alkoxycarbonylC1.6alkyl, C1_ 6alkylcarbonyloxyC1_6alkyl, N-C1_4alkylaminocarbonylC1.6alkyl, N,N-diC1_4alkylaminocarbonylC1.6alkyl, C1-4alkylsulfanylC1-6alkyl, C1.6alkylsulfonylC1.6alkyl, C1.6alkylsulfonylaminoC1.6alkyl; or R12 is C3.8cycloalkyl, C3.8cycloalkylC1.6alkyl, wherein the cycloalkyl moiety is optionally partially unsaturated, phenyl, phenylC1_6alkyl, heteroaryl, heteroarylC1_6alkyl, wherein the heteroaryl moiety is a
5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl, heterocyclylC1_6alkyl, wherein the heterocyclyl moiety is a 4- to
6- membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S; wherein for R12, any cycloalkyl, phenyl, heteroaryl, heterocyclyl moiety is optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R13; wherein R13 is cyano, halogen, hydroxy, C1_4alkyl, C2-4alkenyl, C2-4alkynyl, C1_4haloalkyl, C2-
4haloalkenyl, C1_4alkoxy, C1_4haloalkoxy, C3_4alkenyloxy, C3_4alkynyloxy, N-C1_4alkylamino, N,N-diC1_ 4alkylamino, C1_4alkylcarbonyl, C1_4alkoxycarbonyl, carbonylamino, N-C1_4alkylaminocarbonyl, N,N- diC1_4alkylaminocarbonyl or C1_4alkoxycarbonylamino; and wherein when R12 is substituted C3.8cycloalkyl, C3.8cycloalkylC1.6alkyl, heterocyclyl, or heterocyclylC1-6alkyl, R13 may also represent oxo on the C3.8cycloalkyl or heterocyclyl moiety;
Preferably, R12 is hydrogen, C1_6alkyl, C3.6alkenyl, C3.6alkynyl, cyanoC1_6alkyl, C1_6haloalkyl, C3. 6haloalkenyl, hydroxyC1_6alkyl, C1_4alkoxyC1_6alkyl, C1_4haloalkoxyC1_6alkyl, C1_4alkoxyC1_4alkoxyC1. 6alkyl, aminoC1_6alkyl, N-C1_4alkylaminoC1.6alkyl, N,N-diC1_4alkylaminoC1.6alkyl, C1.6alkylcarbonylC1_ 6alkyl, C1.6alkylcarbonylC2-6alkenyl, C1.6alkoxycarbonylC1.6alkyl, C1.6alkylcarbonyloxyC1.6alkyl, N-C1_ 4alkylaminocarbonylC1-6alkyl, N,N-diC1_4alkylaminocarbonylC1.6alkyl, C1_4alkylsulfanylC1.6alkyl, C1_ 6alkylsulfonylC1_6alkyl, C1.6alkylsulfonylaminoC1.6alkyl, phenyl, phenylC1_6alkyl, C3.8cycloalkyl or C3. 8cycloalkylC1-6alkyl. More preferably, R12 is hydrogen, C1_6alkyl, C3.6alkenyl, C3.6alkynyl, C1_6haloalkyl, C1-4alkoxyC1-6alkyl, phenyl, phenylC1_6alkyl. Even more preferably, R12 is C1_6alkyl, C3_4alkenyl, C3. 4alkynyl, C1_4haloalkyl, C1.2alkoxyC1_4alkyl, phenyl, phenylC1_2alkyl. Still more preferably, R12 is C1_ 6alkyl, C3_4alkenyl, C3_4alkynyl, C1_4fluoroalkyl, C1_4chloroalkyl,
Figure imgf000021_0001
phenyl, benzyl.
R8 represents -NR14R15, wherein R14 is hydrogen, cyano, C1_6alkyl, C1_6alkoxy, C2-6alkenyl, C2. 6alkynyl, C3.6alkenyloxy, C3.6alkynyloxy, cyanoC1_6alkyl, C1_6haloalkyl, C1_6haloalkenyl, hydroxyC1_6alkyl, C1-4alkoxyC1-6alkyl, C1_4haloalkoxyC1_6alkyl, C1_4alkoxyC1_4alkoxyC1.6alkyl, aminoC1_6alkyl, N-C1_ 4alkylaminoC1_6alkyl, N,N-diC1_4alkylaminoC1.6alkyl, C1.6alkylcarbonylC1.6alkyl, C1.6alkylcarbonylC2- 6alkenyl, C1.6alkoxycarbonylC1.6alkyl, C1.6alkylcarbonyloxyC1.6alkyl, N-C1_4alkylaminocarbonylC1.6alkyl, N,N-diC1-4alkylaminocarbonylC1.6alkyl, C1_4alkylsulfanylC1_6alkyl, C1.6alkylsulfonylC1.6alkyl, C1_ 6alkylsulfonylaminoC1.6alkyl; or
R14 is C3.8cycloalkyl, C3.8cycloalkylC1.6alkyl, C3.8cycloalkylC1_6alkoxy, C3.6cycloalkyloxy, wherein the cycloalkyl moiety is optionally partially unsaturated, phenyl, phenylC1_6alkyl, phenyld. 6alkoxy, heteroaryl, heteroarylC1_6alkyl, heteroarylC1_6alkoxy, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl, heterocyclylC1_6alkyl, heterocyclylC1_6alkoxy wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S; wherein for R14, any cycloalkyl, phenyl, heteroaryl, heterocyclyl moiety is optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R16; wherein
R16 is cyano, halogen, hydroxy, C1_4alkyl, C2-4alkenyl, C2_4alkynyl, C1_4haloalkyl, C2. 4haloalkenyl, C1_4alkoxy, C1_2alkoxyC1_2alkyl, C1_4haloalkoxy, C3_4alkenyloxy, C3_4alkynyloxy, N-C1_ 4alkylamino, N,N-diC1_4alkylamino, C1_4alkylcarbonyl, C1_4alkoxycarbonyl, carbonylamino, N-C1_ 4alkylaminocarbonyl, N,N-diC1_4alkylaminocarbonyl or C1_4alkoxycarbonylamino; and wherein when R14 is substituted C3.8cycloalkyl, C3.8cycloalkylC1_6alkyl, C3.8cycloalkylC1_ 6alkoxy, heterocyclyl, or heterocyclylC1_6alkyl, heterocyclylC1_6alkoxy, R16 may also represent oxo on the C3.8cycloalkyl or heterocyclyl moiety;
R15 is hydrogen, C1_4alkyl, C3_4alkynyl, C1_4alkoxyC1_4alkyl, cyanoC1_4alkyl, C3.6cycloalkyl, C3. 6cycloalkylC1_2alkyl; or R14 and R15, together with the nitrogen atom to which they are bonded, form a 4-, 5- or 6- membered cycle optionally containing an additional heteroatom selected from O, S and NR17; wherein R17 is hydrogen, methyl, methoxy, formyl or acyl.
Preferably, R8 represents -NR14R15, wherein R14 is hydrogen, C1_6alkyl, C1_6alkoxy, C2.6alkenyl, C2.6alkynyl, cyanoC1_6alkyl, C1_6haloalkyl, C1_6haloalkenyl, hydroxyC1_6alkyl, C1_4alkoxyC1.6alkyl, C1_ 4haloalkoxyC1-6alkyl, C1-4alkoxyC1_4alkoxyC1.6alkyl, aminoC1_6alkyl, N-C1_4alkylaminoC1.6alkyl, N,N-diC1_ 4alkylaminoC1.6alkyl, C1.6alkylcarbonylC1.6alkyl, C1-6alkylcarbonylC2-6alkenyl, C1.6alkoxycarbonylC1_ 6alkyl, C1.6alkylcarbonyloxyC1.6alkyl, N-C1_4alkylaminocarbonylC1.6alkyl, N,N-diC1_
4alkylaminocarbonylC1.6alkyl, C1_4alkylsulfanylC1_6alkyl, C1.6alkylsulfonylC1.6alkyl, C1_ 6alkylsulfonylaminoC1.6alkyl or C3.8cycloalkyl and R15 is hydrogen, C1_4alkyl, C1_4alkoxyC1_4alkyl or cyanoC1_4alkyl.
More preferably, R14 is hydrogen, cyano, C1_6alkyl, C1_6alkoxy, C2.6alkenyl, C2.6alkynyl, cyanoC1_6alkyl, C1_6haloalkyl, C1_4alkoxyC1_6alkyl, C1.6alkoxycarbonylC1.6alkyl, or C3.8cycloalkyl, C3.
8cycloalkylC1_6alkyl, phenyl or heteroarylC1_6alkyl, wherein the heteroaryl moiety is a 5-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and
S, wherein any of C3.8cycloalkyl, phenyl or heteroaryl, are optionally substituted by 1 or 2 substituents selected from R16, wherein R16 is cyano, halogen, hydroxy, C1_4alkyl, C1_4haloalkyl, d.
4alkoxy, C1_4haloalkoxy or C1_4alkoxycarbonyl. Even more preferably, R14 is hydrogen, C1_6alkyl, d.
6alkoxy, C2_4alkenyl, C2_4alkynyl, C1_2haloalkyl, C3.6cycloalkyl. Still more preferably, R14 is hydrogen, methyl, ethyl, propyl, iso-propyl, sec-butyl, methoxy, ethoxy, allyl, propyn-2-yl, 2,2,2-trifluoromethyl, cyclopropyl or cyclobutyl.
Preferably, R15 is hydrogen, methyl, ethyl, C3_4alkynyl or methoxyethyl. More preferably, R15 is hydrogen, methyl or ethyl, in particular, hydrogen.
In other embodiments, R15 may be hydrogen, C1_4alkyl, C-|_4alkoxyC1_4alkyl or cyanoC1_4alkyl.
R14 and R15, together with the nitrogen atom to which they are bonded, may form a 5- or 6- membered cycle optionally containing an additional heteroatom which is oxygen.
In some embodiments, for the compounds of Formula (I), preferably n is 1 ;
A1 to A4 are C-H, A1 is C-F and A2 to A4 are C-H, A1 and A2 are C-F and A3 and A4 are C-H, A1 and A3 are C-F and A2 and A4 are C-H or A1 is N and A2 to A4 are C-H;
R5 and R6 are independently selected from hydrogen, C1_4alkyl and cyano;
R7 is hydroxy, C1_4alkyl, C2_4fluoroalkyl, C1_4alkoxy, hydroxyC1_4alkyl, C1_2alkoxyC1_4alkyl, C3.
4alkenyl, C3_4alkynyl, C3.6haloalkenyloxy, cyclopropyl, (cyclopropyl)methyl, phenylC1_2alkoxy, (tetrahydrofuran-2-yl)methyl or (2-furyl)methyl, wherein any of said cyclopropyl, phenyl, tetrahydrofuran-2-yl and 2-furyl moieties are optionally substituted by 1 or 2 substituents selected from cyano, fluoro, chloro, bromo, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy; _
22
R8 is C1-6alkyl, C1_2haloalkyl, hydroxyC1_6alkyl, C1-2alkoxyC1-4alkyl, C3.6cycloalkyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- or 5-membered non-aromatic ring which comprises 1 or 2 heteroatoms individually selected from N and O, wherein C3.6cycloalkyl and heterocyclyl are optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R9; and
R9 is cyano, halogen, hydroxy, C1_4alkyl, C2-4alkenyl, C2-4alkynyl, C1_4haloalkyl or C1_4alkoxy.
More preferably in the compounds of Formula (I), n is 1 ;
A1 to A4 are C-H;
R5 and R6 are independently selected from hydrogen and C1_4alkyl;
R7 is C1-4alkyl, C2_4fluoroalkyl, methoxy, ethoxy or cyclopropyl;
R8 is C1-6alkyl, C1_2haloalkyl, hydroxyC1_6alkyl, C1_2alkoxyC1_4alkyl, C3.6cycloalkyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- or 5-membered non-aromatic ring which comprises 1 or 2 heteroatoms individually selected from N and O, wherein C3.6cycloalkyl and heterocyclyl are optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R9; and
R9 is cyano, halogen, hydroxy, C1_4alkyl, C2_4alkenyl, C2_4alkynyl, C1_4haloalkyl or C1_4alkoxy.
Even more preferably in the compounds of Formula (I), n is 1 ;
A1 to A4 are C-H;
R5 and R6 are independently selected from hydrogen and methyl, preferably hydrogen;
R7 is methyl, ethyl, n-propyl, iso-propyl, 2,2,2-fluoroethyl, methoxy, ethoxy or cyclopropyl;
R8 is C1-4alkyl, C1_2haloalkyl, hydroxyC1_4alkyl, C1_2alkoxyC1_2alkyl, C3.6cycloalkyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- or 5-membered non-aromatic ring which comprises 1 or 2 heteroatoms which are oxygen, wherein C3.6cycloalkyl and heterocyclyl are optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R9; and
R9 is fluoro, chloro, methyl.
In other embodiments, for the compounds of Formula (I), preferably n is 1 ;
A1 to A4 are C-H;
R5 and R6 are independently selected from hydrogen and methyl;
R7 is hydroxy, C1_4alkyl, C2_4haloalkyl, C1_4alkoxy, C3.6alkenyl, C3_4alkynyl or d.
4alkoxycarbonyloxy;
R8 is -OR12; and
R12 is hydrogen, C1_6alkyl, C3.6alkenyl, C3.6alkynyl, C1_6haloalkyl, C1_4alkoxyC1_6alkyl, phenyl, phenylC1-6alkyl.
More preferably in the compounds of Formula (I), n is 1 ;
A1 to A4 are C-H;
R5 and R6 are hydrogen;
R7 is methoxy; _
23
R8 is -OR12; and
R12 is hydrogen, C1_6alkyl, C3.6alkenyl, C3.6alkynyl, C1_6haloalkyl, C1_4alkoxyC1.6alkyl, phenyl, phenylC1_6alkyl. In still other embodiments, for the compounds of Formula (I), preferably n is 1 ;
A1 to A4 are C-H or A1, A2 and A4 are C-H and A3 is C-F;
R5 and R6 are hydrogen;
R7 is hydroxy, C1_4alkyl, C2-4haloalkyl, C1_4alkoxy, C3.6alkenyl, C3_4alkynyl, C3.6cycloalkyl;
R8 is -NR14R15;
R14 is hydrogen, cyano, C1_6alkyl, C1_6alkoxy, C2.6alkenyl, C2.6alkynyl, cyanoC1_6alkyl, C1_
6haloalkyl, C1_4alkoxyC1.6alkyl, C1.6alkoxycarbonylC1.6alkyl, or C3.8cycloalkyl, C3.8cycloalkylC1_ 6alkyl, phenyl or heteroarylC1_6alkyl, wherein the heteroaryl moiety is a 5-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, wherein any of C3.8cycloalkyl, phenyl or heteroaryl, are optionally substituted by 1 or 2 substituents selected from R16, wherein R16 is cyano, halogen, hydroxy, C1_4alkyl, C1_4haloalkyl, C1-4alkoxy, C1_4haloalkoxy or C1_4alkoxycarbonyl; and
R15 is hydrogen, methyl, ethyl, C3_4alkynyl or methoxyethyl.
More preferably in the compounds of Formula (I), n is 1 ;
A1 to A4 are C-H;
R5 and R6 are hydrogen;
R7 is hydroxy, C1_4alkyl, C2_4haloalkyl, C1_2alkoxy, C3_4alkenyl, C3_4alkynyl or cyclopropyl;
R8 is -NR14R15;
R14 is hydrogen, methyl, ethyl, propyl, iso-propyl, sec-butyl, methoxy, ethoxy, allyl, propyn-2-yl, 2,2,2-trifluoromethyl, cyclopropyl or cyclobutyl; and
R15 is hydrogen, methyl or ethyl.
Even more preferably in the compounds of Formula (I), n is 1 ;
A1 to A4 are C-H;
R5 and R6 are hydrogen;
R7 is C1-4alkyl or C1_2alkoxy;
R8 is -NR14R15;
R14 is hydrogen, methyl, ethyl, propyl, iso-propyl, sec-butyl, methoxy, ethoxy, allyl, propyn-2-yl, 2,2,2-trifluoromethyl, cyclopropyl or cyclobutyl; and
R15 is hydrogen.
The compound according to Formula (I) may be selected from compound 1.1 to 1.811 listed in Table T1 below, from compound 2.1 to 2.26 listed in Table T2 below, and from compound 3.1 to 3.140 listed in Table T3 below.
The compound of Formula (I) may be a compound according to Formula (IA):
Figure imgf000025_0001
wherein
R1 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 R1, R2, R3 and R4 are hydrogen;
R5 and R6 are independently selected from hydrogen and C1_4alkyl; R7 is C1_4alkyl or C1_4alkoxy; and R8 is hydrogen, C1_6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoC1_6alkyl, C1_6haloalkyl, C2.
6haloalkenyl, hydroxyC1_6alkyl, C1_4alkoxyC1.6alkyl, C1_4haloalkoxyC1_6alkyl, C1_4alkoxyC1_4alkoxyC1.
6alkyl, C2-4alkynyloxyC1.6alkyl, aminoC1_6alkyl, N-C1_4alkylaminoC1.6alkyl, N,N-diC1_4alkylaminoC1.6alkyl, C1.6alkylcarbonylC1.6alkyl, C1.6alkylcarbonylC2.6alkenyl, C1.6alkoxycarbonylC1.6alkyl, d.
6alkylcarbonyloxyC1_6alkyl, N-C1_4alkylaminocarbonylC1.6alkyl, N,N-diC1_4alkylaminocarbonylC1.6alkyl, C1-6alkylsulfanylC1-6alkyl, C1.6alkylsulfonylC1.6alkyl, C1.6alkylsulfonylaminoC1.6alkyl, C1_6 alkylsulfonylaminoC2.6alkynyl, C2.6alkynyloxycarbonylaminoC1.6alkyl; or
R8 is C3.8cycloalkylC0-6alkyl, wherein the cycloalkyl moiety is optionally partially unsaturated, phenylC0-6alkyl, phenylC2.6alkenyl, naphthylC0-6alkyl, heteroarylC0-6alkyl wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterodiarylC0-6alkyl wherein the heterodiaryl moiety is a 9- or 10- membered bicyclic aromatic system which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclylC0-6alkyl wherein the heterocyclyl moiety is a 4- to 6-membered non- aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, or C3. 6cycloalkylcarbonylaminoC1-6alkyl, wherein for R8, any of C3-8cycloalkylCo-6alkyl, phenylC0-6alkyl, phenylC2.6alkenyl, naphthylC0- 6alkyl, heteroarylC0-6alkyl, heterodiarylC0-6alkyl, heterocyclylC0-6alkyl and C3. 6cycloalkylcarbonylaminoC1-6alkyl moieties are optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R9; wherein R9 is cyano, halogen, hydroxy, C1_4alkyl, C2-4alkenyl, C2-4alkynyl, C1_4haloalkyl, C2-4haloalkenyl, C1_4alkoxy, C1_4haloalkoxy, C3_4alkynyloxy, N-C1_4alkylamino, N,N-diC1_4alkylamino, C1_4alkylcarbonyl, C1-4alkoxycarbonyl, carbonylamino, N-C1_4alkylaminocarbonyl, N,N-diC1_4alkylaminocarbonyl or d. 4alkoxycarbonylamino, and wherein R8 is substituted C3.8cycloalkylC0-6alkyl or heterocyclylC0-6alkyl, R9 may also represent oxo on the C3.8cycloalkyl or heterocyclyl moiety; or wherein for R8, any of C3.8cycloalkylC0-6alkyl, phenylC0-6alkyl, phenylC2-6alkenyl, naphthylC0- 6alkyl, heteroarylC0-6alkyl, heterodiarylC0-6alkyl, heterocyclylC0-6alkyl and C3. 6cycloalkylcarbonylaminoC1.6alkyl moieties are optionally substituted by 1 substituent selected from R10; wherein
R10 is C3.8cycloalkylC0-2alkyl, phenylC0-2alkyl, heteroarylC0-2alkyl wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclylC0-6alkyl wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, and wherein any of said cycloalkyi, phenyl, heteroaryl and heterocyclyl moieties are optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R11; wherein
R11 is hydrogen, cyano, fluoro, chloro, bromo, methyl, trifluoromethyl, methoxy and ethoxy; or a salt or an N-oxide thereof.
For the compounds of Formula (IA), when R8 as a C3.8cycloalkylC0-6alkyl, phenylC0-6alkyl, phenylC2.6alkenyl, naphthylC0-6alkyl, heteroarylC0-6alkyl, heterodiarylC0-6alkyl, heterocyclylC0-6alkyl or C3-6cycloalkylcarbonylaminoC1-6alkyl moiety is indicated as optionally substituted by R9 or R10, the cycloalkyi, phenyl, naphthyl, heteroaryl, heterodiaryl, heterocyclyl fragment only may be substituted.
In the compounds of Formula (IA), preferably R1 and R2 are independently selected from hydrogen and fluoro. More preferably, R1 and R2 are hydrogen.
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), preferably three of R1, R2, R3 and R4 are 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 C1-4alkyl, preferably methyl or ethyl. More preferably, R5 and R6 are hydrogen. In the compounds of Formula (IA), preferably R7 is methyl, ethyl, propyl, isopropyl, butyl, sec- butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, or sec-butoxy. More preferably, R7 is methyl, ethyl, sec-butyl, methoxy, ethoxy, or propoxy. Most preferably, R7 is sec-butyl, methoxy or propoxy. In the compounds of Formula (IA), preferably R8 is hydrogen, C1_6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoC1-6alkyl, C1_6haloalkyl, C2-6haloalkenyl, hydroxyC1_6alkyl, C1_4alkoxyC1.6alkyl, C1_4haloalkoxyC1_ 6alkyl, C1-4alkoxyC1-4alkoxyC1-6alkyl, C2-4alkynyloxyC1.6alkyl, C1.6alkylcarbonylC2.6alkenyl, d. 6alkylcarbonyloxyC1_6alkyl, C1.6alkylsulfonylaminoC2.6alkynyl, C2.6alkynyloxycarbonylaminoC1.6alkyl; or C3-8cycloalkylCo-2alkyl, wherein the cycloalkyi moiety is optionally partially unsaturated, phenylC0-2alkyl, heteroarylC0-2alkyl wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, or heterocyclylC0- 2alkyl wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S; wherein any of said C3-8cycloalkylCo-2alkyl, phenylC0-2alkyl, heteroarylC0-2alkyl and heterocyclylC0-2alkyl moieties are optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R9; and R9 is cyano, halogen, hydroxy, C1_4alkyl, C1_4haloalkyl, C1_4alkoxy, C2_4haloalkenyl, C3_4alkynyloxy, C1_4alkylcarbonyl and d. 4alkoxycarbonyl.
More preferably, R8 is C1_6alkyl, C2.6alkenyl, C2.6alkynyl, C1_6fluoroalkyl, C1_6chloroalkyl, C1_ 4alkoxyC1-6alkyl, C1_4alkoxyC1_4alkoxyC1.6alkyl, C1.6alkylcarbonylC2.6alkenyl, C1.6alkylcarbonyloxyC1_ 6alkyl, C1_6 alkylsulfonylaminoC2.6alkynyl or C2.6alkynyloxycarbonylaminoC1.6alkyl; C3.8cycloalkylC0- 6alkyl, phenylC0-6alkyl, or heterocyclylC0-6alkyl, wherein any of said cycloalkyi, phenyl, and heterocyclyl moieties are optionally substituted by 1 , 2 or 3 substituents which may be the same or different, selected from R9, wherein R9 is cyano, halogen, hydroxy, C1_4alkyl, C1_4haloalkyl, C2_4haloalkenyl, C3. 4alkynyloxy, C1_4alkylcarbonyl, C1_4alkoxycarbonyl; or wherein any of said cycloalkyi, phenyl, and heterocyclyl moieties are optionally substituted by 1 substituent selected from R10 which is a phenyl.
Even more preferably, R8 is C1_6alkyl, C2_4alkenyl, C2^alkynyl, C1_6fluoroalkyl, C1_4chloroalkyl, C1-4alkoxyC1_4alkyl, C1_4alkoxyC1.2alkoxyC1_4alkyl, C1_4alkylcarbonylC2_4alkenyl, C1_2alkylcarbonyloxyC1_ 4alkyl, C1_4alkylsulfonylaminoC2_4alkynyl or C2_4alkynyloxycarbonylaminoC1_4alkyl; C3.6cycloalkylC0- -lalkyl, phenylC0-ialkyl or heterocyclylC0-ialkyl, wherein any of said cycloalkyi, phenyl, and heterocyclyl moieties are optionally substituted by 1 , 2 or 3 substituents which may be the same or different, selected from R9, wherein R9 is cyano, fluoro, chloro, hydroxy, methyl, ethyl, trifluoromethyl, 2,2- dichloroethenyl, propynyloxy, acetyl, methoxycarbonyl; or wherein any of said cycloalkyi, phenyl, and heterocyclyl moieties are optionally substituted by 1 substituent selected from R10 which is a phenyl.
In some embodiments of the invention according to Formula (IA) where R8 is a group selected from C3.8cycloalkylC0-6alkyl, phenylC0-6alkyl, phenylC2.6alkenyl, naphthylC0-6alkyl, heteroarylC0-6alkyl, heterodiarylC0-6alkyl, heterocyclylC0-6alkyl, preferably R8 is C3.8cycloalkylC0-2alkyl, phenylC0-2alkyl, phenylC2_4alkenyl, naphthylC0-2alkyl, heteroarylC0-2alkyl, heterodiarylC0-2alkyl or heterocyclylC0-2alkyl. In some embodiments of the invention according to Formula (IA) where R8 is a group selected from C3-8cycloalkylC0-6alkyl, preferably C3.8cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. In some embodiments of the invention according to Formula (IA) where R8 is a group selected from phenylC0-6alkyl, preferably, R8 is phenyl or benzyl.
In some embodiments of the invention according to Formula (IA) where R8 is a group selected from heterocyclylC0-6alkyl, preferably the heterocyclyl group has 1 or 2 heteroatoms selected from N, O and S. More preferably, the heterocyclyl group has a single heteroatom selected from O and S. Most preferable for R8 as a heterocyclylC0-6alkyl are oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, thietanyl or tetrahydrothiopyranyl.
In the compounds of Formula (IA), preferably R1 and R2 are independently selected from hydrogen and fluoro;
R3 and R4 are independently selected from hydrogen and fluoro;
wherein at least two of R1, R2, R3 and R4 are hydrogen,
R5 and R6 are hydrogen, or R5 is hydrogen and R6 is methyl;
R7 is C1-4alkyl or C1_4alkoxy; and
R8 is C1-6alkyl, C2-6alkenyl, C2-6alkynyl, C1_6fluoroalkyl, C1_6chloroalkyl, C1_4alkoxyC1.6alkyl, d.
4alkoxyC1-4alkoxyC1-6alkyl, C1.6alkylcarbonylC2-6alkenyl, C1.6alkylcarbonyloxyC1.6alkyl, C1_6 alkylsulfonylaminoC2-6alkynyl or C2.6alkynyloxycarbonylaminoC1.6alkyl; C3.8cycloalkylC0-6alkyl, phenylC0-6alkyl, or heterocyclylC0-6alkyl, wherein any of said cycloalkyl, phenyl, and heterocyclyl moieties are optionally substituted by 1 , 2 or 3 substituents which may be the same or different, selected from R9, wherein R9 is cyano, halogen, hydroxy, C1_4alkyl, d.
4haloalkyl, C2_4haloalkenyl, C3_4alkynyloxy, C1_4alkylcarbonyl, C1_4alkoxycarbonyl; or wherein any of said cycloalkyl, phenyl, and heterocyclyl moieties are optionally substituted by 1 substituent selected from R10 which is a phenyl. In the compounds of Formula (IA), more preferably R1 and R2 are independently selected from hydrogen and fluoro;
R3 and R4 are independently selected from hydrogen and fluoro;
wherein at least two of R1, R2, R3 and R4 are hydrogen
R5 and R6 are hydrogen, or R5 is hydrogen and R6 is methyl;
R7 is methoxy, propoxy or sec-butyl; and
R8 is C1-6alkyl, C2_4alkenyl, C2_4alkynyl, C1_6fluoroalkyl, C1_4chloroalkyl, C1_4alkoxyC1_4alkyl, C1_ 4alkoxyC1-2alkoxyC1-4alkyl, C1_4alkylcarbonylC2_4alkenyl, C1_2alkylcarbonyloxyC1_4alkyl, C1_ 4alkylsulfonylaminoC2_4alkynyl or C2_4alkynyloxycarbonylaminoC1_4alkyl; C3.6cycloalkylC0-ialkyl, phenylCo-ialkyl or heterocyclylC0-ialkyl, wherein any of said cycloalkyl, phenyl, and heterocyclyl moieties are optionally substituted by 1 , 2 or 3 substituents which may be the same or different, selected from R9, wherein R9 is cyano, fluoro, chloro, hydroxy, methyl, ethyl, trifluoromethyl, 2,2-dichloroethenyl, propynyloxy, acetyl, methoxycarbonyl; or wherein any of said cycloalkyl, phenyl, and heterocyclyl moieties are optionally substituted by 1 substituent selected from R10 which is a phenyl. In the compounds of Formula (IA), even more preferably, R1 and R2 are hydrogen;
R3 and R4 are hydrogen;
R5 and R6 are hydrogen;
R7 is methoxy, propoxy or sec-butyl; and
R8 is C1-6alkyl, C2-4alkenyl, C2-4alkynyl, C1_6fluoroalkyl, C1_4chloroalkyl, C1_4alkoxyC1_4alkyl, C1_ 4alkoxyC1.2alkoxyC1_4alkyl, C1_4alkylcarbonylC2-4alkenyl, C1.2alkylcarbonyloxyC1_4alkyl, C1_
4alkylsulfonylaminoC2-4alkynyl or C2_4alkynyloxycarbonylaminoC1_4alkyl; C3.6cycloalkylC0-ialkyl, phenylCo-ialkyl or heterocyclylC0-ialkyl, wherein any of said cycloalkyl, phenyl, and heterocyclyl moieties are optionally substituted by 1 , 2 or 3 substituents which may be the same or different, selected from R9, wherein R9 is cyano, fluoro, chloro, hydroxy, methyl, ethyl, trifluoromethyl, 2,2-dichloroethenyl, propynyloxy, acetyl, methoxycarbonyl; or wherein any of said cycloalkyl, phenyl, and heterocyclyl moieties are optionally substituted by 1 substituent selected from R10 which is a phenyl.
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 imgf000029_0001
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, R10, R11, R12, R13, R14, R15, R16 and R17 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, R1 , R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 , R12, R13, R14, R15, R16 and R17 as represented in Tables 1.1 to 1.29, 2.1 to 2.5, 3.1 to 3.14 and 4.1 to 4.4 below or the compounds 1.1 to 1.81 1 described in Table T1 (below), the compounds 2.1 to 2.26 described in Table T2 (below), and the compounds 3.1 to 3.140 described in Table T3 below).
Figure imgf000030_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) 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 N,N- 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 ef al Tetrahedron Lett. (2004), 45, 8917; Senthil, K. et al Pest. Res. Journal (2009), 21 , 133; and Crich, D., Zou, Y. J. Org. Chem. (2005), 70, 3309. This reaction is shown in Scheme 1.
Figure imgf000031_0001
(») (I)
Scheme 1
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 R8- 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 R8-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 imgf000031_0002
(IV) (II) (I)
Scheme 2
Additionally, compounds of formula (I) can be prepared from compounds of formula (V) 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 reaction is shown in Scheme 3.
Figure imgf000032_0001
Compounds of formula (V) can be prepared from compounds of formula (VI) 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. ef al Chem. Pharm. Bull. (2001 ), 49, 268 and WO 2013/066838. This reaction is shown in Scheme 4.
Figure imgf000032_0002
(VI) (V)
Scheme 4
Compounds of formula (VI) can be prepared from compounds of formula (VII), 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. This reaction is shown in Scheme 5.
Figure imgf000032_0003
(VII) (VI)
Scheme 5
Compounds of formula (VII), wherein the N-R7 bond contains a directly linked -CH2 segement, can be prepared from compounds of formula (VIII), wherein Z is Br or I, via a base-promoted reaction (eg, sodium hydride) with a suitable alkylating reagent (eg, methyl iodide or propyl iodide), in a suitable solvent (eg, dimethylformamide or N-methylpyrrolidone) at elevated temperature between 100°C and 120°C. This reaction is shown in Scheme 6.
Figure imgf000033_0001
Scheme 6
Compounds of formula (II), wherein n is preferably 0 and R6 is hydrogen, can be prepared from carbonyl compounds of formula (IX), starting with treatment by compounds of formula (X), 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 (XI), 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 Scheme 7.
Figure imgf000033_0002
Scheme 7
Alternatively, compounds of formula (II), wherein n is preferably 1 , can be prepared from compounds of formula (XIII), wherein X is CI or Br, by treatment with amines of formula (XII), 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. et al Heterocycles (2001 ), 54, 887, WO 2003/028729, and WO 2013/066839. This reaction is shown in Scheme 8.
Figure imgf000034_0001
Compounds of formula (XIII), wherein n is 1 , can be prepared from compounds of formula (XIV), wherein X is CI or Br, by treatment with a halogen source (eg, N-bromosuccinimide (NBS) or N- chlorosuccinimide (NCS)) and a radical initiator (eg, (PhC02)2 or azobisisobutyronitrile (AIBN)) in a suitable solvent, such as tetrachloromethane, at temperatures between 55° and 100°C in the presence of ultraviolet light. For related examples, see Liu, S. ef al Synthesis (2001 ), 14, 2078 and Kompella, A. ef al Or . Proc. Res. Dev. (2012), 16, 1794. This reaction is shown in Scheme 9.
Figure imgf000034_0002
(XIV) (Xiii)
Scheme 9
The compounds of formula (VII) can be obtained by an amide coupling transformation with compounds of formula (XV) and compounds of formula (III) 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 (XV), 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 N,N- 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 ef al Tetrahedron Lett. (2004), 45, 8917; Senthil, K. et al Pest. Res. Journal (2009), 21 , 133; and Crich, D., Zou, Y. J. Org. Chem. (2005), 70, 3309. This reaction is shown in Scheme 10.
Figure imgf000035_0001
(XV) (vii)
Scheme 10
Furthermore, compounds of formula (VII), wherein Z is Br, I, or CN and R8 may also be OR12 or NR 4R15 where R 5 is not hydrogen and n is preferably 1 , can be prepared from compounds of formula (XVIII), wherein X is CI, Br or I, via treatment with amides of formula (XVII), 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 the 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 (VIII) occurs upon treatment with HCI or trifluoroacetic acid in a suitable solvent (eg, dioxane, dichloromethane or MeOH). For related examples, see Miyawaki, K. ef al Heterocycles (2001 ), 54, 887. This reaction is shown in Scheme 1 1.
Figure imgf000035_0002
(XVII) (XVIII) (VII)
Scheme 1 1
Compounds of formula (XVIII), wherein Z is Br, I, or CN and X is CI or Br and n is preferably 1 , are either commercially available or can be prepared from compounds of formula (XIX), by treatment with a halogen source, (eg, N-bromosuccinimide (NBS) or N-chlorosuccinimide (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 12.
Figure imgf000036_0001
(XIX) (xviii)
Scheme 12
Alternatively, compounds of formula (XVIII), wherein X is CI, Br, I, or OS02Me and Z is Br, I and n is preferably 1 , or CN 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. ei al Bioorg. Med. Chem. (2008), 16, 10013, WO 2014/020350 and Kompella, A. et al Bioorg. Med. Chem. Lett. (2001 ), 1, 3161. Compounds of formula (XIX) are commercially available. This reaction is shown in Scheme 13.
Figure imgf000036_0002
Scheme 13 Compounds of formula (XV), wherein n is 0 or 1 , and R is preferably hydrogen, can be prepared from compounds of formula (XXI), starting with treatment by compounds of formula (X), wherein RPG is a tert-butylsulfinamides or hydrogen, 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 an organometallic compound of formula (XI), such as an alkyl Grignard reagent (eg. alkylMgBr) and Me3SiCN, or a metal hydride of formula (XI), wherein the metal is B or Al (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 benzylamines of formula (XV) 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 Scheme 14.
Figure imgf000037_0001
(XXI) (XJ) (XV)
Scheme 14
As already indicated, surprisingly, it has now been found that the novel compounds of formula (I) according to the 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" 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).
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 non- volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound. Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; 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; dialkyi 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 dialkyi 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 nonselective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
The compounds of formula (I) may be used in the form of (fungicidal) compositions for controlling or protecting against phytopathogenic microorganisms, comprising as active ingredient at least one compound of formula (I) or of at least one preferred individual compound as defined herein, in free form or in agrochemically usable salt form, and at least one of the above-mentioned adjuvants.
The invention therefore provides a composition, preferably a fungicidal composition, comprising at least one compound formula (I) an agriculturally acceptable carrier and optionally an adjuvant. An agricultural acceptable carrier is for example a carrier that is suitable for agricultural use. Agricultural carriers are well known in the art. Preferably said composition may comprise at least one or more pesticidally-active compounds, for example an additional fungicidal active ingredient in addition to the compound of formula (I). The compound of formula (I) may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingredient may, in some cases, result in unexpected synergistic activities.
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-triiod oal ly I 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, solatenol, 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 96/1 1945, 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.
Carbamates: alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801 , isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717.
Pyrethroids: acrinathin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E) -(1 R)-cis-2,2- dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, beta -cyfluthrin, cyfluthrin, a-cypermethrin, beta -cypermethrin, bioallethrin, bioallethrin((S)-cyclopentylisomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin, cythithrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, ethofenprox, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (D isomer), imiprothrin, cyhalothrin, lambda-cyhalothrin, permethrin, phenothrin, 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 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, 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- 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. 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.
Table 1.1 : This table discloses 149 s ecific compounds of the formula (T-1 ):
Figure imgf000053_0001
wherein n is 1 , A1 is C-R1 , A2 is C-R2, A3 iiss CC--RR3, A4 is C-R4 and R1 , R2, R3, R4, R5 and R6 are hydrogen, R7 is methoxy and R8 is as defined below in the Table 1
Each of Tables 1.2 to 1.29 (which follow Table 1.1 ) make available 149 individual compounds of the formula (T-1 ) in which n, A1 , A2, A3, A4, R , R2, R3, R4, R5, R6, and R7 are as specifically defined in Tables 1.2 to 1.29, which refer to Table 1 wherein R8 is specifically defined. Table 1
Compound Compound
no. R8 no. R8
1.001 methyl 1.076 2-fluoroethyl
1.002 ethyl 1.077 1-fluoroethyl
1.003 propyl 1.078 chloromethyl
1.004 isopropyl 1.079 2-chloroethyl
1.005 butyl 1.080 2-chloro-1 , 1-dimethylethyl
1.006 sec-butyl 1.081 2-(methylamino)-2-oxo-ethyl
1.007 2-methylbutyl 1.082 2-(ethylamino)-2-oxo-ethyl
1.008 tert-butyl 1.083 2-(tert-butylamino)-2-oxo-ethyl
1.009 isobutyl 1.084 2-(isopropylamino)-2-oxo-ethyl
1.010 pentyl 1.085 acetamidomethyl
1.01 1 1-ethylpropyl 1.086 acetamidoethyl
1.012 2-ethylbutyl 1.087 1-methyl-3-oxo-butyl
1.013 2,2-dimethylpropyl 1.088 3-m ethoxy- 1 -methyl-3-oxo-propyl
1.014 1 , 1-dimethylbutyl 1.089 3-methoxy-3-oxo-propyl
1.015 2,2-dimethylbutyl 1.090 phenyl
1.016 1-ethyl-1-methylpropyl 1.091 2-chlorophenyl
1.017 but-2-enyl 1.092 2-fluorophenyl
1.018 2-methylpropenyl 1.093 3-fluorophenyl 1.019 ethenyl 1.094 4-fluorophenyl
1.020 propen-2-yl 1.095 3,5-difluorophenyl
1.021 allyl 1.096 4-pyrimidinyl
1.022 1-methylallyl 1.097 thiazol-5-yl
1.023 2-methylallyl 1.098 oxazol-5-yl
1.024 1 , 1-dimethylallyl 1.099 isoxazol-3-yl
1.025 1-methylprop-1-enyl 1.100 2-pyridyl
1.026 but-1-enyl 1.101 benzyl
1.027 3-methylbut-2-enyl 1.102 3-chlorophenylmethyl
1.028 (E)-1 , 1-dimethylbut-2-enyl 1.103 3-fluorophenylmethyl
1.029 but-3-enyl 1.104 2-pyridylmethyl
1.030 prop-2-ynyl 1.105 cyclopentyl
1.031 but-3-ynyl 1.106 cyclohexyl
1.032 but-2-ynyl 1.107 cyclopentylmethyl
1.033 1-methylprop-2-ynyl 1.108 cyclohexylmethyl
1.034 1-methylbut-2-ynyl 1.109 cyclopropylmethyl
1.035 1 , 1-dimethylprop-2-ynyl 1.1 10 cyclopropyl
1.036 cyanomethyl 1.1 1 1 1 -chlorocycloprop-1 -yl
1.037 2-cyanoethyl 1.1 12 1 -cyanocycloprop-1 -yl
1.038 3-cyanopropyl 1.1 13 1 -f luorocycloprop-1 -yl
1.039 1 -ethoxymethyl 1.1 14 1-methylcyclopropyl
1.040 1-methoxymethyl 1.1 15 1 -trifluoromethylcycloprop-1 -yl
1.041 difluoromethoxymethyl 1.1 16 2-cyanocyclopropyl
1.042 1-difluoromethoxyethyl 1.1 17 2-fluorocyclopropyl
1.043 1-methoxyethyl 1.1 18 2-methylcyclopropyl
1.044 1-methoxyisopropyl 1.1 19 2,2-dichlorocyclopropyl
1.045 1 -ethyloxyisopropyl 1.120 2,2-difluorocyclopropyl
1.046 1-difluoromethoxyisopropyl 1.121 2,2-dimethylcyclopropyl
1.047 2-methoxyethyl 1.122 2,2,3, 3-tetramethylcyclopropyl
1.048 2-(difluoromethoxy)ethyl 1.123 2 ,2-d ich loro- 1 -methyl-cyclopropyl
1.049 3-methoxypropyl 1.124 cyclobutyl
1.050 4-methoxybutyl 1.125 1-methylcyclobutyl
1.051 2-ethoxyethyl 1.126 1 -(trif luoromethyl)cyclobutyl
1.052 1-ethoxyethyl 1.127 1 -cyanocyclobut-1 -yl
1.053 2-methoxypropyl 1.128 cyclobutylmethyl
1.054 1 -(methoxymethyl)propyl 1.129 2,2-difluorocyclopropylmethyl
1.055 2-m ethoxy- 1 , 1 -d imethyl-ethyl 1.130 tetra hyd rot h io py ran-2-yl
1.056 2-methoxyethoxymethyl 1.131 tetra hyd rot h io py ran-3-yl
1.057 1 -acetoxymethyl 1.132 tetra hyd rot h io py ran-4-yl
1.058 2-acetoxyethyl 1.133 oxetan-3-yl 1.059 2-acetoxy-1 , 1 -dimethyl-ethyl 1.134 3-cyanooxetan-3-yl
1.060 2,2-diethoxyethyl 1.135 3-m ethyloxetan-3-yl
1.061 2,2-dimethoxyethyl 1.136 3-trifluoromethyloxetan-3-yl
1.062 hydroxymethyl 1.137 oxetan-2-yl
1.063 1-hydroxyethyl 1.138 oxetan-3-ylmethyl
1.064 1-hydroxyisopropyl 1.139 oxetan-2-ylmethyl
1.065 2-hydroxyethyl 1.140 tetra hyd rof u ran-2-y I
1.066 2-hydroxypropyl 1.141 tetra hyd rof u ran-3-y I
1.067 3-hydroxypropyl 1.142 tetra hyd rof u ran-2-y I m ethy I
1.068 2-hydroxy-1 , 1 -dimethyl-ethyl 1.143 tetrahyd ropyran-2-yl
1.069 2-hydroxy-2-methyl-propyl 1.144 tetrahyd ropyran-3-yl
1.070 trifluoromethyl 1.145 tetrahyd ropyran-4-yl
1.071 2,2,2-trifluoroethyl 1.146 2-methyl-1 ,3-dioxolan-2-yl
1.072 3,3,3-trifluoropropyl 1.147 1 ,3-dioxolan-2-yl
1.073 4,4,4-trifluorobutyl 1.148 1-acetylpyrrolidin-2-yl
1.074 fluoromethyl 1.149 1-imidazoyl
1.075 difluoromethyl
Table 1.2: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1 , A2 is C-R2, A3 is C-R3, A4 is C-R4 and R2, R3, R4, R5, and R6 are hydrogen, R7 is methoxy, R is fluorine, and R8 is as defined above in Table 1.
Table 1.3: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1 , A2 is C-R2, A3 is C-R3, A4 is C-R4 and R2, R3, R4, R5, and R6 are hydrogen, R7 is methoxy, R is chlorine, and R8 is as defined above in Table 1. Table 1.4: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1 , A2 is C-R2, A3 is C-R3, A4 is C-R4 and R2, R3, R4, R5, and R6 are hydrogen, R7 is methoxy, R is methyl, and R8 is as defined above in Table 1.
Table 1.5: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is N, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R2, R3, R4, R5, and R6 are hydrogen, R7 is methoxy, and R8 is as defined above in Table 1.
Table 1.6: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1 , A2 is C-R2, A3 is C-R3, A4 is C-R4 and R , R2, R4, R5, and R6 are hydrogen, R7 is methoxy, R3 is fluorine, and R8 is as defined above in Table 1.
Table 1.7: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1 , A2 is C-R2, A3 is C-R3, A4 is C-R4 and R2, R4, R5, and R6 are hydrogen, R7 is methoxy, R and R3 are fluorine, and R8 is as defined above in Table 1. Table 1.8: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R3, R4, R5, and R6 are hydrogen, R7 is methoxy, R1 and R2 are fluorine, and R8 is as defined above in Table 1.
Table 1.9: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 2, A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is methoxy, and R8 is as defined above in Table 1. Table 1.10: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3 R4, and R5 are hydrogen, R7 is methoxy, R6 is methyl, and R8 is as defined above in Table 1.
Table 1.11 : This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3 R4, and R5 are hydrogen, R7 is methyl, R6 is cyano, and R8 is as defined above in Table 1.
Table 1.13: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is methyl, and R8 is as defined above in Table 1.
Table 1.14: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is ethyl, and R8 is as defined above in Table 1.
Table 1.15: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is propyl, and R8 is as defined above in Table 1. Table 1.16: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is isopropyl, and R8 is as defined above in Table 1.
Table 1.17: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is allyl, and R8 is as defined above in Table 1.
Table 1.18: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is isobutyl, and R8 is as defined above in Table 1. Table 1.19: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is 2-methoxyethyl, and R8 is as defined above in Table 1. Table 1.20: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is propyloxy, and R8 is as defined above in Table 1.
Table 1.21 : This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is 2-propynl, and R8 is as defined above in Table 1.
Table 1.22: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is 2-furylmethyl, and R8 is as defined above in Table 1.
Table 1.23: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is tetrahydrofuran-2- ylmethyl, and R8 is as defined above in Table 1.
Table 1.24: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is cyclopropyl methyl, and R8 is as defined above in Table 1. Table 1.25: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is cyclopropyl, and R8 is as defined above in Table 1.
Table 1.26: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is ethoxy, and R8 is as defined above in Table 1.
Table 1.27: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is hydroxy, and R8 is as defined above in Table 1.
Table 1.28: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is 2,2,2-trifluoroethyl, and R8 is as defined above in Table 1. Table 1.29: This table discloses 149 specific compounds of formula (T-1 ) wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is 2-hydroxyethyl, and R8 is as defined above in Table 1. Table 2.1 : This table discloses 26 specific compounds of the formula (T-2):
Figure imgf000058_0001
wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5 and R6 are hydrogen, R7 is methoxy and R12 is as defined below in Table 2.
Each of Tables 2.2 to 2.5 (which follow Table 2.1 ) make available 26 individual compounds of the formula (T-2) in which n, A1, A2, A3, A4, R1, R2, R3, R4, R5, R6 and R7 are as specifically defined in Tables 2.2 to 2.5, which refer to Table 2 wherein R12 is specifically defined.
Table 2
Figure imgf000058_0002
Table 2.2: This table discloses 26 specific compounds of formula (T-2) wherein n is 1 , A1 is C-R1, A2 C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is allyl, and R12 is defined above in Table 2. Table 2.3: This table discloses 26 specific compounds of formula (T-2) wherein n is 1 , A1 is C-R1 , A2 C-R2, A3 is C-R3, A4 is C-R4 and R1 , R2, R3, R4, R5, and R6 are hydrogen, R7 is ethoxy, and R12 is defined above in Table 2.
Table 2.4: This table discloses 26 specific compounds of formula (T-2) wherein n is 1 , A1 is C-R1 , A2 C-R2, A3 is C-R3, A4 is C-R4 and R1 , R2, R3, R4, R5, and R6 are hydrogen, R7 is hydroxy, and R12 is defined above in Table 2.
Table 2.5: This table discloses 26 specific compounds of formula (T-2) wherein n is 1 , A1 is C-R1 , A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1 , R2, R3, R4, R5, and R6 are hydrogen, R7 is 2,2,2-trifluoroethyl, and R12 is as defined above in Table 2.
Table 3.1 : This table discloses 100 specific compounds of the formula (T-3):
Figure imgf000059_0001
wherein n is 1 , A1 is C-R1 , A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1 , R2, R3, R4, R5, R6, and R15 are hydrogen, R7 is methoxy and R14 is as defined below in Table 3.
Each of Tables 3.2 to 3.14 (which follow Table 3.1 ) make available 100 individual compounds of the formula (T-3) in which n, A1, A2, A3, A4, R1, R2, R3, R4, R5, R6, R7 and R15 are as specifically defined in Tables 3.2 to 3.14, which refer to Table 3 wherein R14 is specifically defined.
Figure imgf000059_0002
3.01 1 2-methylallyl 3.061 cyano
3.012 1 , 1-dimethylallyl 3.062 1-methylprop-2-ynyl
3.013 prop-2-ynyl 3.063 1-methylbut-2-ynyl
3.014 2-acetoxyethyl 3.064 1 , 1-dimethylprop-2-ynyl
3.015 2-hyd roxyethyl 3.065 cyanomethyl
3.016 2-hyd roxypropyl 3.066 2-cyanoethyl
3.017 3-hydroxypropyl 3.067 3-cyanopropyl
3.018 2,2-difluoroethyl 3.068 l-methoxymethyl
3.019 2,2,2-trifluoroethyl 3.069 2-methoxyethyl
3.020 3,3,3-trifluoropropyl 3.070 3-methoxypropyl
3.021 4,4,4-trifluorobutyl 3.071 4-methoxybutyl
3.022 but-3-ynyl 3.072 1-methoxyethyl
3.023 but-2-ynyl 3.073 1 -(methoxymethyl)propyl
3.024 2-cyanoethyl 3.074 2-methoxy-1 , 1-dimethylethyl
3.025 2-methoxyethyl 3.075 2-methoxyethoxymethyl
3.026 2-ethoxyethyl 3.076 1 -acetoxymethyl
3.027 2-methoxypropyl 3.077 2-acetoxy-1 , 1-dimethylethyl
3.028 1-methoxy-4-piperidyl 3.078 2,2-diethoxyethyl
3.029 oxetan-3-yl 3.079 2,2-dimethoxyethyl
3.030 phenyl 3.08 hydroxymethyl
3.031 pyrid-2-yl 3.081 2-hyd roxypropyl
3.032 pyrid-3-yl 3.082 2-hyd roxy- 1 , 1 -d i m ethyl ethy I
3.033 pyrid-4-yl 3.083 2-hydroxy-2-methylpropyl
3.034 phenyl methyl 3.084 trifluoromethyl
3.035 pyrid-2-ylmethyl 3.085 fluoromethyl
3.036 cyclopropyl 3.086 difluoromethyl
3.037 1 -cyanocyclopropyl 3.087 2-fluoroethyl
3.038 1 -f luorocyclopropyl 3.088 2-chloroethyl
3.039 1-methylcyclopropyl 3.089 3-chloropropyl
3.040 cyclobutyl 3.090 methoxy
3.041 cyclopentyl 3.091 ethoxy
3.042 cyclohexyl 3.092 propoxy
3.043 cyclopropylmethyl 3.093 isopropoxy
3.044 cyclobutylmethyl 3.094 butoxy
3.045 cyclopentylmethyl 3.095 sec-butoxy
3.046 cyclohexylmethyl 3.096 isobutoxy
3.047 tetra hyd rof u ran-3-y I 3.097 allyloxy
3.048 tetrahyd ropyran-3-yl 3.098 prop-2-ynyloxy
3.049 tetrahyd ropyran-4-yl 3.099 ethoxycarbonylmethyl
3.050 tetra hyd rof u ran-2-y I m ethy I 3.100 methylaminocarbonylmethyl Table 3.2: This table discloses 100 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 R2, R3, R4, R5, R6, and R15 are hydrogen, R7 is methoxy, R1 is fluorine, n is 1 , and R14 is as defined above in Table 3.
Table 3.3: This table discloses 100 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, and R15 are hydrogen, R7 is methoxy, n is 1 , and R14 is as defined above in Table 3. Table 3.4: This table discloses 100 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, R4, R5, R6, and R15 are hydrogen, R7 is methoxy, R3 is fluorine, n is 1 , and R14 is as defined above in Table 3.
Table 3.5: This table discloses 100 specific compounds of formula (T-3) wherein A1 is C-R1, A2 is C- R2, A3 is C-R3, A4 is C-R4 and R3, R4, R5, R6, and R15 are hydrogen, R7 is methoxy, R1 and R2 are fluorine, n is 1 , and R14 is as defined above in Table 3.
Table 3.6: This table discloses 100 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, and R15 are hydrogen, R7 is isopropyl, n is 2, and R14 is as defined above in Table 3.
Table 3.7: This table discloses 100 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, and R6, are hydrogen, R7 is methoxy, R15 is methyl, n is 1 , and R14 is as defined above in Table 3.
Table 3.8: This table discloses 100 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, and R6 are hydrogen, R7 is methoxy, R1 is fluorine, R15 is methyl, n is 1 , and R14 is as defined above in Table 3. Table 3.9: This table discloses 100 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, R4, R5, and R6 are hydrogen, R7 is methoxy, R3 is fluorine, R15 is methyl, n is 1 , and R14 is as defined above in Table 3.
Table 3.10: This table discloses 100 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 and R15 are hydrogen, R7 is methyl, n is 1 , and R14 is as defined above in Table 3.
Table 3.1 1 : This table discloses 100 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 and R15 are hydrogen, R7 is ethyl, n is 1 , and R14 is as defined above in Table 3. Table 3.12: This table discloses 100 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 and R15 are hydrogen, R7 is isopropyl, n is 1 , and R14 is as defined above in Table 3.
Table 3.13: This table discloses 100 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 and R15 are hydrogen, R7 is cyclopropyl, n is 1 , and R14 is as defined above in Table 3. Table 3.14: This table discloses 100 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 and R15 are hydrogen, R7 is hydroxy, n is 1 , and R14 is as defined above in Table 3.
Table 4.1 : This table discloses 4 specific compounds of the formula (T-4):
Figure imgf000062_0001
wherein n is 1 , A1 is C-R1, A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is methoxy, and R14-N-R15 is as defined below in the Table 4.
Each of Tables 4.2 to 4.4 (which follow Table 4.1 ) make available 4 individual compounds of the formula (T-4) in which n, A1, A2, A3, A4, R1, R2, R3, R4, R5, R6, and R7 are as specifically defined in Tables 4.2 to 4.4, which refer to Table 4 wherein R14-N-R15 is specifically defined.
Table 4
Figure imgf000062_0002
Table 4.2: This table discloses 4 specific compounds of formula (T-4) wherein n is 1 , A1 is C-R1, A' C-R2, A3 is C-R3, A4 is C-R4 and R1, R2, R3, R4, R5, and R6 are hydrogen, R7 is methyl, and R14-N-R15 as defined above in Table 4. „„
62
Table 4.3: This table discloses 4 specific compounds of formula (T-4) wherein n is 1 , A1 is C-R1 , A2 is C-R2, A3 is C-R3, A4 is C-R4 and R1 , R2, R3, R4, R5, and R6, are hydrogen, R7 is ethyl and R 4-N-R15 is as defined above in Table 4. Table 4.4: This table discloses 4 specific compounds of formula (T-4) wherein n is 1 , A1 is C-R , A2 is C-R2, A3 is C-R3, A4 is C-R4 and R , R2, R3, R4, R5, R6 are hydrogen, R7 is isopropyl, and R 4-N-R15 is as defined above in Table 4.
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 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 "mp." 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/min)
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 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)
Active ingredient [compound of formula (I)] 5 % 6 %
Figure imgf000065_0001
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.
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
DIPEA = N,N-diisopropylethylamine
DMA = dimethylacetamide
DMF = dimethylformamide
EdCI = 3-(ethyliminomethyleneamino)-A/,A/-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 ,2,3-triazolo[4,5-b]pyridinium 3-oxid- hexafluorophosphate
min = minutes
mp = melting point
MeOH = methyl alcohol
NaOH = sodium hydroxide
NBS = N-bromosuccinimide
TFAA = trifluoroacetic acid anhydride
THF = tetrahydrofuran Preparation Examples
Using the synthetic techniques described both above and below, compounds of formula (I) may be prepared accordingly.
Example 1 : This example illustrates the preparation of N-methoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]meth l]-acetamide (Compound 1.1 of Table T1 below).
Figure imgf000068_0001
Step 1 : Preparation of 4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllbenzoyl chloride
Figure imgf000068_0002
4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzoic acid (4.00 g, 15.0 mmol) was suspended in dichloromethane (90 mL) DMF (0.01 mL, 0.150 mmol) was added followed by oxalyl chloride (1.46 mL, 16.5 mmol). The mixture was heated at reflux for 2 hours. The mixture was evaporated under reduced pressure to afford 4.15 g of 4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzoyl chloride as a yellow solid.
Step 2: Preparation of N-methoxy-N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllbenzamide
Figure imgf000068_0003
A solution of 4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzoyl chloride from Step 1 (4.15 g,
14.6 mmol) in dichloromethane (20 mL) was added drop wise at room temperature to a stirred solution of N-methoxymethanamine (1.10 g, 17.5 mmol) and triethylamine (3.10 ml, 21.8 mmol) in dichloromethane (80 mL). The mixture was stirred at room temperature for 18 hours. The reaction mixture was poured into water extracted twice with dichloromethane. The combined organic layers were washed with brine, 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 (heptane: EtOAc eluent gradient 9: 1 to 65:35) to afford 4.12 g of N-methoxy-N-methyl-4-[5- (trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide as a solid. LC/MS (Method A) retention time = 0.97 minutes, 302 (M+H). H NMR (400 MHz, CDCI3) δ ppm: 8.18 (d, 2H), 7.84 (d, 2H), 3.56 (s,3H), 3.40 (s,3H).
Step 3: Preparation of 4-[5-(trifluorometh l)-1 ,2,4-oxadiazol-3-yl]benzaldehyde
Figure imgf000069_0001
In a 75-mL multi neck flask equipped with stirrer, thermometer at -78°C under argon, DIBAL-H, 1.0M in toluene (16 mL, 16.0 mmol) was added drop-wise to a solution of N-methoxy-N-methyl-4-[5- (trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide (4.10 g, 13.3 mmol) in 2-methyltetrahydrofuran (90 mL). The mixture was stirred two hours at -78°C and for one hour temperature was let increase to 0°C. Complete conversion observed by LC-MS. The mixture was quenched by drop wise addition of sat. ammonium chloride solution. Precipitation of a white solid occurred. 4 M HCI was added until full solubilisation. The mixture was extracted thrice with ethyl acetate. Combined organics were dried over magnesium sulfate and evaporated to afford the crude as beige solid. The crude was subject to flash chromatography over silicagel (heptane: EtOAc eluent gradient 99: 1 to 90: 10) to afford 2.93 g of 4-[5- (trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzaldehyde as a white solid mp: 40-50°C.
H NMR (400 MHz, CDCI3) δ ppm: 10.12 (s, 1 H), 8.31 (d, 2H), 8.05 (d, 2H).
19,
9F NMR (400 MHz, CDCI3) δ ppm: -65.29 (s).
Step 4: Preparation of N-methoxy-1-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethanimine
Figure imgf000069_0002
A solution of 4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzaldehyde (0.30 g, 1.1 mmol) in methanol (1 1 mL) was treated at room temperature with pyridine (0.15 mL, 1.9 mmol) followed by addition of O-methylhydroxylamine hydrochloride (0.15 g, 1.8 mmol). The mixture was stirred at room temperature over the weekend, poured on water, acidified with 1 M HCI and extracted trice with ethyl acetate. Combined organics were washed with water, dried over magnesium sulfate and evaporated to afford a resin. The crude was subject to flash chromatography over silicagel (heptane: EtOAc eluent gradient 100:0 to 95:5) to afford the title compound as a white solid mp: 55-65°C. H NMR (400 MHz, CDCI3) δ ppm: 8.14 (s, 1 H), 8.1 1 (d, 2H), 7.73 (d, 2H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.40 (s). _
69
Step 5: Preparation of N-methoxy-1-[4-[5-(trifluorom
Figure imgf000070_0001
A solution of N-methoxy-1-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3^
(0.81 g, 2.89 mmol) in acetic acid (1 1 mL) was treated at 15°C with sodium cyano borohydride (0.4 g, 6.1 mmol). The mixture was stirred at 22°C for 18 hours until complete consumption of starting material was observed. The reaction mixture was carefully poured in 0.1 M NaOH solution. By addition of 1 M NaOH pH was adjusted to 12-13. The mixture was extracted four times with TBME. Combined organics were washed twice with water and once with brine then dried over magnesium sulfate and concentrated under reduced. The resultant green oil was purified by flash chromatography over silica gel (heptane: EtOAc eluent gradient 99:1 to 70:30) to give 0.60 g of the title compound as an oil. H NMR (400 MHz, CDCI3) δ ppm: 8.09 (d, 2H), 7.53 (d, 2H), 5.33 (Sbr,1 H), 4.12 (s,2H), 3.50 (s,3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.32 (s).
Step 6: Preparation of N-methoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyll- acetamide
Figure imgf000070_0002
To a stirred solution of acetic acid (0.03 g, 0.49 mmol), EDCI (0.15 g, 0.76 mmol), HOAt (0.03 g, 0.19 mmol) and triethylamine (0.16 mL, 1.14 mmol) in dry dichloromethane (2.9 mL) under an atmosphere of nitrogen at room temperature was added N-methoxy-1-[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methanamine (0.1 1 g, 0.38 mmol). The reaction mixture was stirred at room temperature for 18 hours and then 1 M HCI and dichloromethane were added. The resultant mixture was shaken and the layers were separated. The aqueous layer was extracted trice with dichloromethane and the combined organic layers were washed with brine, dried over sodium sulfate, filtered and evaporated to dryness. The crude oil was purified by flash chromatography over silica gel (heptane: EtOAc eluent gradient 99:1 to 80:20) to give 0.08 g of the title compound as a clear oil.
LC/MS (Method A) retention time = 0.98 minutes, 316.3 (M+H).
H NMR (400 MHz, CDCI3) δ ppm: 8.09 (d, 2H), 7.47 (d, 2H), 4.86 (s, 2H), 3.68 (s,3H). 7Q 9F NMR (400 MHz, CDCI3) δ ppm: -65.34 (s).
Example 2: This example illustrates the preparation of intermediate 3-[4-(bromomethyl)phenyl]-5- trifluoromethyl)-1 ,2,4-oxadiazole
Figure imgf000071_0001
To a stirred suspension of 4-methylbenzonitrile (35 g, 0.29 mol) in ethanol (220 mL) and water (440 mL) was added at room temperature 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 room temperature and diluted with 2N 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 imgf000071_0002
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 layerwas 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 flash chromatography over silica gel (750g prepacked column) with heptane/EtOAc 99: 1 to 90: 10 to afford 54.1 g of the title compound as clear oil, which solidified after 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 imgf000072_0001
A stirred 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 room temperature and diluted with dichloromethane and water. Layers were separated. 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 silicagel (750g pre packed column) with cyclohehane/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 was isolated as by-product as white solid mp: 61-66°C. 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-(trifluoromethyl)-1 ,2,4-oxadiazole from 3-[4- (dibromomethyl)phenyll-5-(trifluoromethyl)-1 ,2,4-oxadiazole
Figure imgf000072_0002
To a 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 DIPEA (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 was added and acetonitrile was evaporated under reduced pressure. The white slurry was extracted thrice with dichloromethane. 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). F NMR (400 MHz, CDCI3) δ ppm: -65.32 (s).
Example 3: This example illustrates the preparation of intermediate N-propoxy-1-[4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phenyl]methanamine
Figure imgf000073_0001
A solution of 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (1.30 g, 4.06 mmol) in dichloromethane (10 mL) was added drop wise at room temperature to a stirred solution of O-propylhydroxylamine hydrochloride (3.74 g, 32.5 mmol) and DIEA (6.40 ml, 36.6 mmol) in dichloromethane (6 mL). The mixture was stirred at room temperature for 24 hours. The reaction mixture was poured onto water and the layers were separated. The aqueous layer was extracted trice with dichloromethane. The combined organic layers were washed with brine, dried over sodium sulfate, and filtered. The solvent was removed under reduced pressure and the resultant crude was purified by flash chromatography over silica gel (cyclohexane: EtOAc eluent gradient 1 :0 to 1 :1 ) to give 0.92 g of the title compound as a clear oil. LC/MS (Method A) retention time = 1 .12 minutes, 302 (M+H). H NMR (400 MHz, CDCI3) δ ppm: 8.09 (d, 2H), 7.02 (d, 2H), 5.70 (sbr, 1 H), 4.1 1 (s,2H), 3.59
(m,2H), 1.52 (m,2H), 0.86 (s,3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.33 (s).
Example 4: This example illustrates the preparation of intermediate N-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]ethanamine.
Figure imgf000073_0002
A solution of 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (1.50 g, 4.69 mmol) in dichloromethane (9.4 mL) was added drop-wise at room temperature to a stirred solution of ethylamine 2 M in MeOH (12 mL, 24.0 mmol). The mixture was stirred at room temperature for 24 hours. The reaction mixture was poured into water and the layers were separated. The aqueous layer was extracted trice with dichloromethane. The combined organic layers were washed with brine, dried over sodium sulfate and filtered. The solvent was removed under reduced pressure and the resultant crude was purified by flash chromatography over silica gel (cyclohexane: EtOAc eluent gradient 1 :0 to 1 :1 ) to give 0.92 g of the title compound as a white solid mp: 102-1 12°C, LC/MS (Method A) retention time = 0.66 minutes, 272 (M+H). H NMR (400 MHz, DMSO) δ ppm: 8.01 (d, 2H), 7.57 (d, 2H), 3.86 (q,2H), 3.29 (sbr, 1 H), 2.53 (q,2H), 1.05 (t,3H).
9F NMR (400 MHz, CDCI3) δ ppm: -64.77 (s).
Example 5: This example illustrates the preparation of the intermediate N-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]ethanamine.
Figure imgf000074_0001
A solution of 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (1.50 g, 4.69 mmol) in dichloromethane (9.4 mL) was added drop wise at room temperature to a stirred solution of sec-butylamine (2.4 mL, 23.4 mmol) in dichloromethane (5 mL). The mixture was stirred at room temperature for 24 hours. The reaction mixture was poured into water and extracted trice with dichloromethane. The combined organic layers were washed with brine, dried over sodium sulfate, and filtered. The solvent was removed under reduced pressure and the resultant crude residue was purified by flash chromatography over silica gel (cyclohexane: EtOAc eluent gradient 1 :0 to 1 :1 ) to give 1 .18 g of the title compound as a clear oil, LC/MS (Method A) retention time = 0.71 minutes, 300 (M+H). H NMR (400 MHz, CDCI3) δ ppm: 8.06 (d, 2H), 7.49 (d, 2H), 3.86 (q,2H), 2.62 (m,1 H), 1.53 (m,1 H), 1.49 (m,1 H), 1.09 (d,3H), 0.91 (m,3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.39 (s). Example 6: This example illustrates the preparation of the intermediate N-methoxy-1-[4-[5- (trifluoromethyl)-1 ,2,4-oxadiazol-3- l]phenyl]ethanamine.
Figure imgf000074_0002
Step 1 : Preparation of 4-[(E)-N-methoxy-C-methyl-carbonimidoyllbenzonitrile
Figure imgf000075_0001
A solution of 4-acetyl benzonitrile (5.0 g, 33.8 mmol) in EtOH (270 mL) was treated at room temperature with O-methylhydroxylamine hydrochloride (4.32 g, 50.6 mmol). The mixture was stirred at room temperature for 70 hours, poured on water and extracted thrice with dichloromethane. Combined organics were washed with water, dried over magnesium sulfate and evaporated to afford 5.95 g of the title compound as clear oil. No further purification was required. LC/MS (Method A) retention time = 0.93 minutes, 175 (M+H). H NMR (400 MHz, CDCI3) δ ppm: 7.78 (d, 2H), 7.65 (d, 2H), 4.03 (s, 3H), 2.22 (s, 3H).
Step 2: Preparation of N'-hvdroxy-4-[(E)-N-methoxy-C-methyl-carbonimidoyllbenzamidine
Figure imgf000075_0002
To a stirred suspension of 4-[(E)-N-methoxy-C-methyl-carbonimidoyl]benzonitrile (5.95 g, 33.5 mmol) in ethanol (50 mL) and water (100 mL) was added at room temperature hydroxylamine hydrochloride (4.7 g, 66.9 mmol), potassium carbonate (7.48 g, 53.6 mmol) and 8-hydroxyquinoline (0.025 g, 0.17mmol). The reaction mixture was heated at 80°C for 3 hours. The mixture was cooled to room temperature and 1 M HCI was added until pH 8-9. Ethanol was removed under reduced pressure at 50°C. The mixture was stirred 30 minutes at 5°C, filtered, washed with water and dried under vacuum to afford 6.6 g of the title compound as a white solid mp: 134-139°C, LC/MS (Method A) retention time = 0.43 minutes, 208 (M+H). H NMR (400 MHz, CDCI3) δ ppm: 8.23(sbr, 1 H), 7.69 (d, 2H), 7.62 (d, 2H), 4.88 (sbr, 2H), 4.00 (s, 3H), 2.23 (s, 3H).
Step 3: Preparation of N-methoxy-1-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllethanimine
Figure imgf000075_0003
To a stirred solution of N'-hydroxy-4-[(E)-N-methoxy-C-methyl-carbonimidoyl]benzamidine (6.46 g, 31.2 mmol) in 2-methyltetrahydrofuran (93 mL) was added TFAA (6.24 mL, 43.7 mmol) at 15°C. The reaction mixture was stirred at 15°C for two hours and diluted with water. The organic layer was separated and washed successively with sodium bicarbonate solution, ammonium chloride solution and water, dried over sodium sulfate, filtered and evaporated to dryness to afford 8.9 g of the title compound as beige solid mp: 56-61 °C, LC/MS (Method A) retention time = 1.19 minutes, 286 (M+H). 1H NMR (400 MHz, CDCI3) δ ppm: 8.13 (d, 2H), 7.81 (d, 2H), 4.03 (s, 3H), 2.25 (s, 3H).
19F NMR (400 MHz, CDCI3) δ ppm: -65.34 (s).
Step 4: Preparation of N-methoxy-1-[4-[5-(trifluoromethvn-1 ,2,4-oxadiazol-3-yllphenyllethanamine
Figure imgf000076_0001
A solution of N-methoxy-1-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]ethanimine
(8.9 g, 29.6 mmol) in acetic acid (1 19 mL) was treated at 15°C portion wise with sodium cyano borohydride (4.12 g, 62.3 mmol). The mixture was stirred at 23°C for 18 hours. Partial consumption of starting material was observed. Additional cyano borohydride (4.12 g, 62.3 mmol) was added portion wise. The reaction mixture was carefully poured in 0.1 M sodium hydroxide solution. By addition of 4 M NaOH pH was adjusted to 9-12. The mixture was extracted four times with TBME. Combined organics were washed twice with water and once with brine then dried over magnesium sulfate and concentrated under reduced. The resultant green oil was purified by flash chromatography over silica gel (heptane: EtOAc eluent gradient 99: 1 to 70:30) to give 5.0 g of the title compound as an oil. LC/MS retention time = 1.05 minutes, 288 (M+H).
1H NMR (400 MHz, CDCI3) δ ppm: 8.10 (d, 2H), 7.51 (d, 2H), 5.65 (Sbr, 1 H), 4.22 (q,1 H), 3.47 (s,3H), 1.38 (d,3H).
19F NMR (400 MHz, CDCI3) δ ppm: -65.37 (s). Example 7: This example illustrates the preparation of the 1-[cyano-[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]meth l -3-methoxy-1 ,3-dimethyl-urea (Compound 3.31 of Table T3)
Figure imgf000076_0002
Step 1 : Preparation of 2-(methylamino)-2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllacetonitrile
Figure imgf000077_0001
To a stirred solution of 4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzaldehyde (2.5 g, 10.3 mmol) in THF (16 mL) was added at room temperature methylamine (0.38 g, 12.4 mmol). After 10 minutes water (51.6 ml) and acetone cyanohydrin (0. 8 g, 10.3 mmol) was added. The mixture was stirred overnight, poured on water and extracted twice with ethyl acetate. The organic layer was washed successively with brine, dried over sodium sulfate, filtered and evaporated to dryness. The crude was subject to flash chromatography over silica gel with cyclohexane/t-butylmethylether 9: 1 to afford 2.1 g of the title compound as white solid. H NMR (400 MHz, CDCI3) δ ppm: 8.17 (d, 2H), 7.72 (d, 2H), 4.87 (s,1 H), 2.61 (s,3H), 1.62
(Sbr, 1 H).
Step 2: Preparation of 1-[cvano-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyll-3-methoxy- 1 ,3-dimethyl-urea
Figure imgf000077_0002
To a stirred solution of 2-(methylamino)-2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]acetonitrile (0.17 g, 0.60 mmol) in dichloromethane (5 mL) under an atmosphere of nitrogen was added at 0°C triethylamine (0.17 mL, 1.20 mmol), N,N-dimethylpyridin-4-amine (0.07 g, 0.60 mmol) followed by Ν,Ν-dimethylcarbamoyl chloride (0.09 g, 0.72 mmol). The reaction mixture was stirred for 18 hours at room temperature, poured on HCI 1 M solution and extracted with dichloromethane. The combined organic layers were washed with 1 M NaOH, brine, 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 7: 1 to 5: 1 ) to afford 0.085 g of 1-[cyano-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]-3- methoxy-1 ,3-dimethyl-urea as a white solid mp: 106-107°C. H NMR (400 MHz, CDCI3) δ ppm: 8.20 (d, 2H), 7.67 (d, 2H), 6.57 (s,1 H), 3.67 (s,3H), 3.1 1 (s,3H), 2.86 (s,3H). Example 8: Preparation of N-(oxetan-3-yl)-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]propanamide (Compound 1.604 of Table T1 ) Step 1 : Preparation of N-[[4-[5-(trifluoromethvn-1 ,2,4-oxadiazol-3-yllphenyllmethylloxetan-3-amine
Figure imgf000078_0001
To a stirred solution of 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (2.0 g, 6.25 mmol) in dichloromethane (13 mL) was added drop wise at room temperature N-ethyl-N- isopropyl-propan-2-amine (1.1 mL) followed by the addition of oxetan-3-amine (3.5 g, 50 mmol). The mixture was stirred at room temperature for 24 hours. The reaction mixture was poured into water and extracted trice with dichloromethane. The combined organic layers were washed with brine, dried over sodium sulfate, and filtered. The solvent was removed under reduced pressure and the resultant crude residue was purified by flash chromatography over silica gel (cyclohexane: EtOAc eluent gradient 1 :0 to 0:1 ) to give the title compound as a clear oil. H NMR (400 MHz, CDCI3) δ ppm: 8.08 (d, 2H), 7.48 (d, 2H), 4.80 (t,2H), 4.44 (t,2H), 4.04 (m,1 H), 3.83 (s,2H), 2.01 (s,1 H).
Step 2: Preparation of N-(oxetan-3-yl)-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyll propanamide
Figure imgf000078_0002
To a stirred suspension of N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]oxetan- 3-amine (0.10 g, 0.33 mmol) in dichloromethane (6 mL) under an atmosphere of nitrogen was added triethylamine (0.09 mL, 0.66 mmol) at 0°C followed by propanoyl chloride (0.03 mL, 0.35 mmol). The reaction mixture was evaporated under reduced pressure and the resultant crude residue was subjected to flash chromatography over silica gel (heptane: EtOAc eluent gradient 9: 1 to 1 :9) to afford the desired product as a white solid mp: 88.8°-93.5°C.
Example 8: N-(2,2,2-trifluoroethyl)-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]tetrahydrofuran-2-carboxamide (Compound 1.587 of Table T1 )
Figure imgf000079_0001
Figure imgf000079_0002
To a stirred solution of 3-[4-(bromomethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (1.5 g,
4.69 mmol) in dichloromethane (10 mL) was added drop wise at room temperature N-ethyl-N- isopropyl-propan-2-amine (0.82 mL, 4.69 mmol) followed by the addition of 2,2,2-trifluoroethanamine (2.94 mL, 37.5 mmol). The mixture was stirred at room temperature for 24 hours. The reaction mixture was poured into water and extracted trice with dichloromethane. The combined organic layers were dried over sodium sulfate, and filtered. The solvent was removed under reduced pressure and the resultant crude residue was purified by flash chromatography over silica gel (cyclohexane: EtOAc eluent gradient 1 :0 to 0: 1 ) to give the title compound as a clear oil.
1H NMR (400 MHz, CDCI3) δ ppm: 8.09 (d, 2H), 7.51 (d, 2H), 4.00 (s,2H), 3.22 (q,2H), 1.71
Figure imgf000079_0004
(s,1 H).
Step Preparation of N-(2,2,2-trifluoroethyl)-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yll phenyl! methylltetrahyd rof u ran-2-carboxam ide
Figure imgf000079_0003
To a stirred suspension of 2,2,2-trifluoro-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]ethanamine (0.09 g, 0.27 mmol) in dichloromethane (6 mL) under an atmosphere of nitrogen was added triethylamine (0.08 mL, 0.55 mmol) at 0°C followed by tetrahydrofuran-2-carbonyl chloride (0.04 g, 0.29 mmol). The reaction mixture was evaporated under reduced pressure and the resultant crude residue was subjected to combiflash chromatography over 12g pre packed silica gel (heptane: EtOAc eluent gradient 9: 1 to 1 :9) to afford the desired product as a clear yellowish oil. LC/MS (Method A) retention time = 1.14 minutes, 424.3 (M+H).
Example 9: This example illustrates the preparation N-[[3-fluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol- 3-yl]phenyl]methyl]-N,2-dimethoxy-propanamide (Compound 1.783 of Table T1 )
Figure imgf000080_0001
Step 1 : Preparation of 2-fluoro-N'-hvdroxy-4-methyl-benzamidine
Figure imgf000080_0002
To a suspension of 2-fluoro-4-methylbenzonitrile (5 g, 37.0 mmol) in ethanol (125 mL) at 25°C was added hydroxylamine hydrochloride (7.7 g, 1 1 1 mmol). The reaction mixture was heated at 80°C for 2 h. After cooling to room temperature the volatiles were removed under reduced pressure thus affording a white solid that was used in the next step without any purification. LC/MS (Method A) retention time = 1.14 minutes, 169.2 (M+H). H NMR (400 MHz, CDCI3) δ ppm: 7.96 (t, 1 H), 7.1 1 (m, 2H), 2.45 (s, 3H).
Step 2: Preparation of 3-(2-fluoro-4-methyl-phenyl)-5-(trifluoromethyl)-1 ,2,4-oxadiazole
Figure imgf000080_0003
To a solution of 2-fluoro-N'-hydroxy-4-methyl-benzamidine (37 mmol) in tetrahydrofuran (122 mL) cooled via an ice bath was added TFAA (7.71 mL, 55.5 mmol). The reaction mixture was stirred at 25°C overnight and then diluted with water. The organic layer was separated, washed successively with sodium bicarbonate solution, ammonium chloride solution, and water then dried over sodium sulfate, filtered and evaporated to dryness. The crude product was subjected to flash chromatography over silica gel with cyclohexane/EtOAc 99:1 to 1 :1 to afford the title compound (6.6 g, 72% yield) as an amorphous white solid. LC/MS (Method A) retention time = 1.14 minutes, 247 (M+H). H NMR (400 MHz, CDCI3) δ ppm: 8.00 (d, 1 H), 7.32 (d, 2H), 2.45 (s,
9F NMR (400 MHz, CDCI3) δ ppm: -65.3 (s), 108.1 (s). Step 3a: Preparation of 3-[4-(bromomethyl)phenyll-5-(trifluoromethyl)-1 ,2,4-oxadiazole
Figure imgf000081_0001
A stirred mixture of 3-(2-fluoro-4-methyl-phenyl)-5-(trifluoromethyl)-1 ,2,4-oxadiazole (4.2 g, 17.1 mmol) and NBS (3.1 1 g, 17.1 mmol) in tetrachloromethane (34.3 mL) under argon was heated to 70°C. AIBN (0.29 g, 1.71 mmol) was added and the reaction mixture stirred at 65°C for 18 h. The mixture was cooled to 25°C then diluted with dichloromethane and water afterwhich the layers were separated. The succinimide by-product was filtrated off, and the solvent was removed under reduced pressure to afford a brown gum. This crude residue was subjected to flash chromatography over silica gel (with cyclohexane/EtOAc 100:0 to 4: 1 to afford the title compound as a white solid (1.7 g, 31 % yield. LC/MS (Method A) retention time = 1.13 minutes, (M+H) not detected.
Figure imgf000081_0003
3-[4-(dibromomethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole was isolated as by-product in the form of a beige solid (4.0 g, 58% yield) LC/MS (Method A) retention time = 1.20 minutes, (M+H) not detected.
Figure imgf000081_0004
Step 3b: Preparation of 3-[4-(bromomethyl)-2-fluoro-phenyll-5-(trifluoromethyl)-1 ,2,4-oxadiazole from 33-[4-(dibromomethyl)-2-fluoro-phenyll-5-(trifluoromethyl)-1 ,2,4-oxadiazole
Figure imgf000081_0002
To a 1 :20 ratio mixture of 3-[4-(bromomethyl)-2-fluoro-phenyl]-5-(trifluoromethyl)-1 ,2,4- oxadiazole and 3-[4-(dibromomethyl)-2-fluoro-phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (4.0 g, 9.9 mmol) in acetonitrile (37 mL), water (0.8 mL) and DIPEA (2.59 mL, 14.8 mmol) at 5°C was added diethylphosphite (2.0 mL, 14.8 mmol). The mixture was stirred at 5-10°C for 2 h, water and 1 M HCI were added, and volatiles were removed under reduced pressure. The white slurry was extracted three times with dichloromethane and the combined organic layers were dried over sodium sulfate and filtered. The solvent was removed under reduced pressure and the resultant light orange colored crude residue was subjected to flash chromatography over silica gel with cyclohexane/EtOAc 99: 1 to 1 : 1 to afford 3-[4-(bromomethyl)-2-fluoro-phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (2.2 g, 68% yield). LC/MS (Method A) retention time = 1.13 minutes, (M+H) not detected. „_
81
1H NMR (400 MHz, CDCI3) δ ppm: 8.09 (t, 1 H), 7.34 (m, 2H), 4.49 (s, 2H).
19F NMR (400 MHz, CDCI3) δ ppm: -65.18 (s), -106.2 (s). Step 4: Preparation of 1-[3-fluoro-4-[5-(trifluoromethvn-1 ,2,4-oxadiazol-3-yllphenyll-N-methoxy- methanamine
Figure imgf000082_0001
A solution of O-methylhydroxylamine hydrochloride (4.9 g, 59mmol) in dichloromethane (15ml_) was treated dropwise with DIPEA (12 mL, 66 mmol) followed by a solution of 3-[4- (bromomethyl)-2-flurorphenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (1.2 g, 3.7 mmol) in dichloromethane (5 mL). After 18h, water was introduced (10mL) and the reaction contents were extracted twice with dichloromethane and the combined organic layers were dried over sodium sulfate and filtered. The resultant residue was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 1 :0 to 1 : 1 ) to afford 1-[3-fluoro-4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]-N-methoxy-methanamine as a colorless oil (410 mg, 38% yield). LC/MS (Method A) retention time = 1.01 minutes, (M+H) not detected .
1H NMR (400 MHz, CDCI3) δ ppm: 8.05 (t, 1 H), 7.45 (m, 2H), 5.85 (brs, 1 H), 4.12 (s, 2H), 3.50 (s, 3H).
19F NMR (400 MHz, CDCI3) δ ppm: -65.21 (s), -107.33 (s).
Step 4: Preparation of N-[[3-fluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyll-N,2- dimethoxy-propanamide
Figure imgf000082_0002
To a stirring solution of 2-methoxy propanoic acid (0.01 g, 0.08 mmol) and HATU (0.03 g, 0.08 mmol in DMF (0.35 mL) under an atmosphere of nitrogen at room temperature was introduced N- ethyl-N-isopropyl-propan-2-amine (0.2 mL, 1.03 mmol). After 5 minutes, 1-[3-fluoro-4-[5- (trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]-N-methoxy-methanamine (0.02 g, 0.07 mmol) was added. After 2 hours, ethyl acetate and water were introduced and the layers were separated. The aqueous layer was extracted with EtOAc and the combined organic phase was washed with brine, dried over sodium sulfate, filtered and evaporated to dryness. A crude white gum was purified by flash chromatography over silica gel (cycloheptane: EtOAc eluent gradient 99: 1 to 1 : 1 ) to give N-[[3-fluoro- 4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]-N,2-dimethoxy-propanamide (0.08 g, 35%) as a clear oil. LC/MS (Method A) retention time = 1.02 minutes, 378 (M+H). H NMR (400 MHz, CDCI3) δ ppm: 8.06 (t, 1 H), 7.25 (m, 2H), 4.96 (m, 1 H), 4.83 (m, 1 H), 4.28
(q, 1 H), 3.71 (s, 3H), 3.38 (s, 3H), 1.26 (d, 3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.21 (s), -106.58 (s). Example 10: This example illustrates the preparation 1-[[3-fluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol- 3-yl]phenyl]methyl]-1-methoxy-3-methyl-urea (Compound 3.45 of Table T1 )
Figure imgf000083_0001
To a solution of 1-[3-fluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]-N-methoxy- methanamine (20mg, 0.07 mmol) in DCM (0.23 mL, 0.07 mmol) was added N-methylcarbamoyl chloride (0.012 g, 0.14 mmol) followed by triethylamine (0.02 mL, 0.02 mmol). After 1 hour, the reaction mixture was concentrated under reduced pressure and the residue was was purified by flash chromatography over silica gel (cyclohexane: EtOAc eluent gradient 99: 1 to 1 : 1 ) to provide 1-[[3- fluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]-1-methoxy-3-methyl-urea (12 mg, 50% yield) as a gum. LC/MS (Method A) retention time = 0.97 minutes, 349 (M+H). H NMR (400 MHz, CDCI3) δ ppm: 8.04 (t, 1 H), 7.31 (m, 2H), 5.81 (m, 1 H), 4.71 (s, 2H), 3.60 (s, 3H), 2.87 (d, 3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.17 (s), -107.10 (s). Example 1 1 : This example illustrates the preparation 2-chloro-N-[[2,3-difluoro-4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phenyl]methyl]-N-methoxy-benzamide (Compound 1.576 of Table T1 )
Figure imgf000083_0002
Step 1 : Preparation of 2,3-difluoro-N'-hvdroxy-4-methyl-benzamidine
Figure imgf000084_0001
To a suspension of 2,3-difluoro-4-methylbenzonitrile (5.0 g, 32.6 mmol) in ethanol (1 1 1 mL) at 25°C was added hydroxylamine hydrochloride (4.5 g, 65.3 mmol). The reaction mixture was heated at 80°C for 2 h. After cooling to room temperature the volatiles were removed under reduced pressure thus affording a white solid that was used in the next step without purification. H NMR (400 MHz, CDCI3) δ ppm: 7.30 (m, 1 H), 6.95 (m, 1 H), 6.50 (brs, 1 H), 5.05 (brs, 2H), 2.30 (s, 3H). Step 2: Preparation of 3-(2,3-difluoro-4-methyl-phenyl)-5-(trifluoromethyl)-1 ,2,4-oxadiazole
Figure imgf000084_0002
To a solution of 2,3-difluoro-N'-hydroxy-4-methyl-benzamidine (2.6 mmol) in tetrahydrofuran (108 mL) cooled using an ice bath was added TFAA (6.9 mL, 49 mmol). The reaction mixture was stirred at 25°C overnight and then diluted with water. The organic layer was separated, washed successively with sodium bicarbonate solution, ammonium chloride solution, and water then dried over sodium sulfate, filtered and evaporated to dryness. The crude title compound (6.6 g, 72% yield) was isolated as a light brown solid that was used in the next transformation without further purification. LC/MS (Method A) retention time = 1.16 minutes, 265 (M+H). H NMR (400 MHz, CDCI3) δ ppm: 7.76 (d, 1 H), 7.12 (d, 1 H), 2.41 (s, 3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.41 (s), -133.3 (s), -140.1 (s).
Step 3: Preparation of 3-[4-(bromomethyl)-2,3-difluoro-phenyll-5-(trifluoromethyl)-1 ,2,4-oxadiazole
Figure imgf000084_0003
A mixture of 3-(2,3-difluoro-4-methyl-phenyl)-5-(trifluoromethyl)-1 ,2,4-oxadiazole (6.0 g, 22.6 mmol) and NBS (7.17 g, 10.0 mmol) in tetrachloromethane (79 mL) under argon was heated to 70°C. AIBN (0.68 g, 3.95 mmol) was added and the reaction mixture stirred at 65°C for 36 h. The mixture was cooled to 25°C, diluted with dichloromethane and water, and the layers were separated. The succinimide by-product was filtered off, and the solvent was removed under vacuum, to afford a brown gum. This crude residue was subjected to flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 100:0 to 4: 1 ) to afford the title compound as a white solid (4.8 g, 72% yield). LC/MS (Method A) retention time = 1.16 minutes, 344 (M+H). H NMR (400 MHz, CDCI3) δ ppm: 7.80 (m, 1 H), 7.37 (m, 1 H), 4.55 (s, 2H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.1 (s), -131 .2 (s), -139.1 (s).
Step 4: Preparation of 1-[2,3-difluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyll-N-methoxy- methanamine
Figure imgf000085_0001
A solution of O-methylhydroxylamine hydrochloride (3.5g, 42 mmol) in dichloromethane (8 mL) was treated dropwise with DIPEA (8.3 mL, 47 mmol) followed by a solution of 3-[4-(bromomethyl)-2,3- difluoro-phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (2 g, 5.2 mmol) in dichloromethane (5 mL). After 18h, water was introduced (10 mL) and the reaction contents were extracted twice with dichloromethane and the combined organic layers were dried over sodium sulfate and filtered. The resultant residue was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 1 :0 to 1 : 1 ) to afford 1-[2,3-difluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]-N- methoxy-methanamine as a pale yellow oil (1.1g, 68% yield). LC/MS (Method A) retention time = 1 .03 minutes, 310 (M+H). H NMR (400 MHz, CDCI3) δ ppm: 7.84 (t, 1 H), 7.38 (t, 1 H), 5.87 (brs, 1 H), 4.20 (s, 2H), 3.52 (s, 3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.21 (s), -132.53 (s), -147.50 (s). Step 5: Preparation 2-chloro-N-[[2,3-difluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yllphenyllmethyll-
N-methoxy-benzamide
Figure imgf000085_0002
A clear solution of 1-[2,3-difluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]-N-methoxy- methanamine (0.150 g, 0.485 mmol) and DCM (3 mL) was treated with triethylamine (0.13 mL, 0.970 mmol) followed by 2-chlorobenzoyl chloride (80 mg, 0.51 mmol). After 2 hr, isolute was added to the reaction mixture and volatiles were removed under reduced pressure. The crude product was subjected to flash chromatography over silica gel with cyclohexane/EtOAc 99: 1 to 1 : 1 to afford 2- chloro-N-[[2,3-difluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]-N-methoxy-benzamide (212mg, 98% yield) as a colourless oil. LC/MS (Method A) retention time = 1.16 minutes, 448 (M+H). H NMR (400 MHz, CDCI3) δ ppm: 7.88 (m, 1 H), 7.54 (m, 1 H), 7.40 (m, 4H), 5.14 (brs, 2H), 3.52 (brs, 3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.21 (s), -131.98 (s), -141.10 (s). Example 12: This example illustrates the preparation N-methoxy-N-[[5-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]-2-pyridyl]methyl]cyclopropanecarboxamide (Compound 1.570 of Table T1 ).
Figure imgf000086_0001
Step 1 : Preparation of N'-hvdroxy-6-methyl-pyridine-3-carboxamidine
To a suspension of 5-cyano-2-picoline (3 g, 25.0 mmol) in ethanol (86 mL) at 25°C was added hydroxylamine hydrochloride (5.3 g, 76 mmol). The reaction mixture was heated at 80°C for 2 h. After cooling to room temperature the volatiles were removed under reduced pressure thus affording a white solid that was used in the next step without any purification. LC/MS (Method A) retention time = 0.17 minutes, 152 (M+H). H NMR (400 MHz, CDCI3) δ ppm: 8.75 (s, 1 H), 7.83 (d, 1 H), 7.19 (d, 1 H), 4.86 (brs, 2H), 2.63 (s, 3H).
Step 2: Preparation of 3-(6-methyl-3-pyridyl)-5-(trifluoromethyl)-1 ,2,4-oxadiazole
Figure imgf000086_0003
To a solution of N'-hydroxy-6-methyl-pyridine-3-carboxamidine (25 mmol) in tetrahydrofuran (84ml_) cooled via an ice bath was added TFAA (5.28 mL, 38.0 mmol). The reaction mixture was stirred at 25°C overnight and then diluted with water. The organic layer was separated, washed successively with sodium bicarbonate solution, ammonium chloride solution, and water then dried over sodium sulfate, filtered and evaporated to dryness to afford 3-(6-methyl-3-pyridyl)-5-(trifluoromethyl)- 1 ,2,4-oxadiazole (5.8 g, 84% yield) as an amorphous white solid. LC/MS (Method A) retention time = 1.14 minutes, 247 (M+H). H NMR (400 MHz, CDCI3) δ ppm: 9.23 (d, 1 H), 8.27 (dd, 1 H), 7.33 (d, 1 H), 2.63 (s, 3H). 9F NMR (400 MHz, CDCI3) δ ppm: -65.3 (s).
Step 3: Preparation of 3-[6-(bromomethyl)-3-pyridyll-5-(trifluoromethyl)-1 ,2,4-oxadiazole
Figure imgf000087_0001
A solution of 3-(6-methyl-3-pyridyl)-5-(trifluoromethyl)-1 ,2,4-oxadiazole (4.4 g, 19 mmol), AIBN (0.32 g, 1.9 mmol), and tetrachloromethane (38 mL) under argon was heated to 65°C. NBS (3.1 1 g, 17.1 mmol) was added portionwise and the reaction mixture stirred at 65°C for 5 h and then a second equivalent of NBS (3.1 1 g, 17.1 mmol) and stirring continued overnight. The mixture was cooled to 25°C then diluted with dichloromethane and water afterwhich the layers were separated. The succinimide by-product was filtrated off, and the solvent was removed under reduced pressure to afford a brown gum. This crude residue was subjected to flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 100:0 to 4: 1 ) to afford 3-[6-(bromomethyl)-3-pyridyl]-5- (trifluoromethyl)-1 ,2,4-oxadiazole as a white solid (5.9 g, 37% yield. LC/MS (Method A) retention time = 1.01 minutes, 308 (M+H). H NMR (400 MHz, CDCI3) δ ppm: 9.30 (d, 1 H), 8.40 (dd, 1 H), 7.63 (d, 1 H), 4.62 (s, 2H). 9F NMR (400 MHz, CDCI3) δ ppm: -65.2 (s).
Step 4: Preparation of N-methoxy-1-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yll-2-pyridyllmethanamine
Figure imgf000087_0002
A solution of O-methylhydroxylamine hydrochloride (4.4 g, 52 mmol) in dichloromethane (26 mL) was treated dropwise with DIPEA (10.3 mL, 58 mmol) followed by a solution of 33-[6- (bromomethyl)-3-pyridyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (2 g, 6.5 mmol) in dichloromethane (10 mL). After 18h, additional equivalents O-methylhydroxylamine hydrochloride (4.4 g, 52 mmol) and DIPEA (10.3 mL, 58 mmol) were introduced and the reaction was heated atr 40°C for 48 hr. of water was introduced (50 mL) and the reaction contents were extracted twice with dichloromethane and the combined organic layers were dried over sodium sulfate and filtered. The resultant residue was purified by flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 1 :0 to 1 : 1 ) to afford 1-[2,3-difluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]-N-methoxy-methananriine as a pale yellow solid (1.4 g, 79% yield). LC/MS (Method A) retention time = 0.87 minutes, 275 (M+H). H NMR (400 MHz, CDCI3) δ ppm: 9.31 (s, 1 H), 8.37 (d, 1 H), 7.52 (d, 1 H), 6.42 (brs, 1 H), 4.24 (s, 2H), 3.56 (s, 3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.25 (s).
Step 5: Preparation of N-methoxy-N-[[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yll-2-pyridyllmethyll cyclopropanecarboxamide
Figure imgf000088_0001
A clear solution of N-methoxy-1-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2- pyridyl]methanamine (0.10 g, 0.36 mmol) and DCM (2 mL) cooled to 0°C was treated with triethylamine (0.10 mL, 0.73 mmol) followed by cyclopropanecarbonyl chloride (38 mg, 0.36 mmol). After 2 hr, isolute was added to the reaction mixture and volatiles were removed under reduced pressure. The crude product was subjected to flash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 99: 1 to 1 :1 ) to afford N-methoxy-N-[[5-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]-2-pyridyl]methyl]cyclopropanecarboxamide (212 mg, 98% yield) as a colourless oil. LC/MS (Method A) retention time = 1.16 minutes, 448 (M+H). H NMR (400 MHz, CDCI3) δ ppm: 7.88 (m, 1 H), 7.54 (m, 1 H), 7.40 (m, 4H), 5.14 (brs, 2H),
3.52 (brs, 3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.21 (s), -131.98 (s), -141.10 (s).
Example 13: This example illustrates the preparation methyl N-methoxy-N-[[4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]phenyl]methyl]carbamate (Compound 2.3 of Table T2)
Figure imgf000088_0002
To a solution of N-methoxy-1-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methanamine (0.10 g, 0.37 mmol) in DCM (1.2 mL) was added methyl chloroformate (0.06 mL, 0.732 mmol) and triethylamine (0.10 mL, 0.73 mmol). The reaction mixture was stirred for 1 h 30min at room temperature afterwhich time the solvent was removed under rweduced pressure and the resultant crude residue was purified by combiflash chromatography over silica gel (cyclohexane/EtOAc eluent gradient 1 :0 to 1 :1 ) give methyl N-methoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]carbamate (0.105 g, 87% Yield) as a yellow oil. LC/MS (Method A) retention time = 1.06 minutes, 332 (M+H). H NMR (400 MHz, CDCI3) δ ppm: 8.04 (d, 2H), 7.42 (d, 2H), 4.64 (s, 2H), 3.75 (s, 3H), 3.57 (s, 3H).
9F NMR (400 MHz, CDCI3) δ ppm: -65.33 (s). Example 14: Preparation of N-isopropyl-N-[2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]ethyl]cyclopropanecarboxamide Compound 1.810 of Table T1 )
Figure imgf000089_0001
Step 1 : Preparation of 4-(2-bromoethvD-N'-hvdroxy-benzamidine
Figure imgf000089_0002
To a stirring solution of 4-(2-bromoethyl)benzonitrile (5 g, 24 mmol) in ethanol (80 mL) was added at room temperature triethylamine (15 mL, 1 10 mmol) and hydroxylamine hydrochloride (3.3 g, 48 mmol). After 6 hours the solvent was evaporated under reduced pressure to afford the title compound as crude solid that was used without further purification.
Step 2: Preparation of 3-[4-(2-bromoethvnphenyll-5-(trifluoromethvn-1 ,2,4-oxadiazole
Figure imgf000089_0003
To a stirring suspension of crude 4-(2-bromoethyl)-N'-hydroxy-benzamidine (24 mmol) in 2- methyltetrahydrofuran (150 mL) was added TFAA (10 mL, 71 mmol) at 0°C. The reaction mixture was stirred at 25°C for 15 hours and then diluted with water (100 mL), followed by extraction with EtOAc. The organic layers were separated, washed successively with saturated aqueous sodium bicarbonate solution and water, dried over sodium sulfate, filtered and evaporated to dryness under reduced pressure. The crude residue was subject to flash chromatography over silicagel(cyclohexane/EtOAc eluent gradient 95:5) to afford 3-[4-(2-bromoethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (4.93 g, 65% yield) as white solid m.p 39-40°C. LC/MS (Method A) retention time = 1.19 minutes, mass not detected. H NMR (400 MHz, CDCI3) δ ppm: 8.07 (d, 2H), 7.37 (d, 2H), 3.61 (t, 2H), 3.25 (t, 2H). Step 3: Preparation of N-[2-[4-[5-(trifluoromethvn-1 ,2,4-oxadiazol-3-yllphenyllethyllpropan-2-amine
Figure imgf000090_0001
To a stirring solution of 3-[4-(2-bromoethyl)phenyl]-5-(trifluoromethyl)-1 ,2,4-oxadiazole (1.5 g, 4.40 mmol) in dichloromethane (10 mL) was added dropwise N-ethyl-N-isopropyl-propan-2-amine (0.76 mL, 4.40 mmol) at room temperature followed by the addition of isopropylamine (9.2 mL, 1 10 mmol). The mixture was stirred at room temperature for 37 hours then poured into water and extracted three times with EtOAc. The combined organic layers were washed with brine, dried over sodium sulfate, and filtered. The solvent was removed under reduced pressure and the resultant crude residue was purified by flash chromatography over silica gel (cyclohexane: EtOAc eluent gradient 98:2 to 95:5) to give N-[2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]ethyl]propan-2-amine (530 mg, 44% yield) as a clear oil. LC/MS (Method A) retention time = 0.75 minutes, minutes, 300.5 (M+H).
Ή NMR (400 MHz, CDCI3) δ ppm: 8.05 (d, 2H), 7.37 (d, 2H), 2.91 (m, 4H), 2.85 (m, 1 H), 1.06 (d, 6H).
Step 4j Preparation of N-isopropyl-N-[2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yllphenyllethyllcyclopropanecarboxamide
Figure imgf000090_0002
To a stirring suspension of N-[2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]ethyl]propan-2-amine (0.075 g, 0.25 mmol) in dichloromethane (5 mL) under an atmosphere of nitrogen was added triethylamine (0.04 mL, 0.30 mmol) at 0°C followed by cyclopropanecarbonyl chloride (0.024 mL, 0.26 mmol). The reaction mixture was stirred at room temperature for 17 hours, poured into water, and extracted twice with EtOAc. The combined organic layers were washed with brine, dried over sodium sulfate, and filtered. The solvent was evaporated under reduced pressure and the resultant crude residue was subjected to flash chromatography over silica gel (cyclohexane: EtOAc eluent gradient 3:1 to 2:1 ) to afford N-isopropyl-N-[2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]ethyl]cyclopropanecarboxamide (89mg, 96% yield) as a white solid. LC/MS (Method A) retention time = 1 .17 minutes, minutes, 368.5 (M+H). H NMR (400 MHz, CDCI3) δ ppm: 8.06 (m, 2H), 7.38 (m, 2H), 4.79 (m, 0.5H), 4.47 (m, 0.5H), 3.58 (m, 1 H), 3.40 (m, 1 H), 3.05 (m, 1 H), 2.95( m, 1 H), 1.76 (m, 1 H), 1.29 (m, 3H), 1.13 (d, 3H), 1 .04 (m, 1 H), 0.83 (m, 2H). 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 imgf000091_0001
By way of exemplification, acid derivatives of formula (III) (0.0375 mmol in 375 μΙ_ 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 μΙ_ 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 imgf000091_0002
(IV) (ii) (I) Protocol A: Portions of triphosgene (6 mg) in DCE (0.3 mL) were transferred at 0°C to a 96 slot deep well plate (DWP96) containing the alcohol derivative [HOR 0] or amine derivative [HN(R )R12] of formula (IV) (0.05 mmol) and triethylamine (0.12 mmol) in 200 μί DMA. The reaction mixtures were stirred at room temperature 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 [it DMA were added. The DWP was sealed and stirred at room temperature for 18 hours. DCE was removed under the 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 [HOR 0] or amine derivative [HNR R12] of formula (IV) (0.05 mmol) and DIPEA (0.25 mmol) in 300 [it DMA were transferred at room temperature 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 [it DMA were added. The DWP was sealed and stirred at room temperature for 18 hours. The DCE was removed under the 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 5-47% yields.
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).
Table T1 : Melting point (mp) data and/or retention times (RT) for compounds according to Formula (I):
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
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
Figure imgf000106_0001
Figure imgf000107_0001
Figure imgf000108_0001
Figure imgf000109_0001
Figure imgf000110_0001
Figure imgf000111_0001
Figure imgf000112_0001
Figure imgf000113_0001
Figure imgf000114_0001
Figure imgf000115_0001
Figure imgf000116_0001
Figure imgf000117_0001
Figure imgf000118_0001
Figure imgf000119_0001
Figure imgf000120_0001
Figure imgf000121_0001
Figure imgf000122_0001
Figure imgf000123_0001
Figure imgf000124_0001
Figure imgf000125_0001
Figure imgf000126_0001
Figure imgf000127_0001
Figure imgf000128_0001
Figure imgf000129_0001
Figure imgf000130_0001
Figure imgf000131_0001
Figure imgf000132_0001
Figure imgf000133_0001
Figure imgf000134_0001
Figure imgf000135_0001
Figure imgf000136_0001
Figure imgf000137_0001
Figure imgf000138_0001
Figure imgf000139_0001
Figure imgf000140_0001
Figure imgf000141_0001
Figure imgf000142_0001
Figure imgf000143_0001
Figure imgf000144_0001
Figure imgf000145_0001
Figure imgf000147_0001
Figure imgf000148_0001
Figure imgf000149_0001
Figure imgf000150_0001
Figure imgf000151_0001
Figure imgf000152_0001
Figure imgf000153_0001
Figure imgf000154_0001
Figure imgf000155_0001
Figure imgf000156_0001
Figure imgf000157_0001
Figure imgf000158_0001
Figure imgf000159_0001
Figure imgf000160_0001
Figure imgf000161_0001
Figure imgf000162_0001
Figure imgf000163_0001
Figure imgf000164_0001
Figure imgf000165_0001
Figure imgf000166_0001
Figure imgf000167_0001
Figure imgf000168_0001
Figure imgf000169_0001
Figure imgf000170_0001
Figure imgf000171_0001
Figure imgf000172_0001
Figure imgf000173_0001
Figure imgf000174_0001
Figure imgf000175_0001
Figure imgf000176_0001
Figure imgf000177_0001
Figure imgf000178_0001
Figure imgf000179_0001
Figure imgf000180_0001
Figure imgf000181_0001
Figure imgf000182_0001
Figure imgf000183_0001
Figure imgf000184_0001
Figure imgf000185_0001
Figure imgf000186_0001
Figure imgf000187_0001
Figure imgf000188_0001
Figure imgf000189_0001
Figure imgf000190_0001
Figure imgf000191_0001
Figure imgf000192_0001
Figure imgf000193_0001
Figure imgf000194_0001
Figure imgf000195_0001
Figure imgf000196_0001
Figure imgf000197_0001
Figure imgf000198_0001
Figure imgf000199_0001
Figure imgf000200_0001
Figure imgf000201_0001
Figure imgf000202_0001
Figure imgf000203_0001
Figure imgf000204_0001
Figure imgf000205_0001
Figure imgf000206_0001
Figure imgf000207_0001
Figure imgf000208_0001
Figure imgf000209_0001
Figure imgf000210_0001
Figure imgf000211_0001
Figure imgf000212_0001
Figure imgf000213_0001
Figure imgf000214_0001
Figure imgf000215_0001
Figure imgf000216_0001
Figure imgf000217_0001
Figure imgf000218_0001
Figure imgf000219_0001
Figure imgf000220_0001
Figure imgf000221_0001
Figure imgf000222_0001
Figure imgf000223_0001
Figure imgf000224_0001
Figure imgf000225_0001
Figure imgf000226_0001
Figure imgf000227_0001
Figure imgf000228_0001
Figure imgf000229_0001
Figure imgf000230_0001
Figure imgf000231_0001
Figure imgf000232_0001
Figure imgf000233_0001
Figure imgf000234_0001
Figure imgf000235_0001
Figure imgf000236_0001
Figure imgf000237_0001
Figure imgf000238_0001
Figure imgf000239_0001
Figure imgf000240_0001
Figure imgf000241_0001
Figure imgf000242_0001
Figure imgf000243_0001
Figure imgf000244_0001
Figure imgf000245_0001
Figure imgf000246_0001
Figure imgf000247_0001
Figure imgf000248_0001
Figure imgf000249_0001
Figure imgf000250_0001
Figure imgf000251_0001
Figure imgf000252_0001
Figure imgf000253_0001
azole-1-carboxamide
Table T2: Melting point (mp) data and/or retention times (RT) for compounds according to Formula (I):
Figure imgf000253_0002
Figure imgf000254_0001
Figure imgf000255_0001
Figure imgf000256_0001
Figure imgf000257_0001
Figure imgf000258_0001
Figure imgf000259_0001
Figure imgf000260_0001
Table T3: Melting point (mp) data and/or retention times (RT) for compounds according to Formula (I): ; Entry · Name ' Structure ; RT i [M+H] \ Method ; MP
3.1 N-methoxy-N-[[4-[5- (trifluoromethyl)- 1 ,2,4-oxadiazol-3- yl]phenyl]methyl]mor
pholine-4- carboxamide
3.2 1-methoxy-3-(2- m ethoxyethyl)- 1 -[[4- [5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3- yl]phenyl]methyl]urea
Figure imgf000260_0002
Figure imgf000261_0001
Figure imgf000262_0001
Figure imgf000263_0001
Figure imgf000264_0001
Figure imgf000265_0001
Figure imgf000266_0001
yl]phenyl]methyl]urea
Figure imgf000267_0001
Figure imgf000268_0001
Figure imgf000269_0001
Figure imgf000270_0001
Figure imgf000271_0001
Figure imgf000272_0001
Figure imgf000273_0001
Figure imgf000274_0001
Figure imgf000275_0001
Figure imgf000276_0001
Figure imgf000277_0001
Figure imgf000278_0001
Figure imgf000279_0001
Figure imgf000280_0001
Figure imgf000281_0001
Figure imgf000282_0001
Figure imgf000283_0001
Figure imgf000284_0001
Figure imgf000285_0001
Figure imgf000286_0001
Figure imgf000287_0001
Figure imgf000288_0001
Figure imgf000289_0001
Figure imgf000290_0001
Figure imgf000291_0001
Figure imgf000292_0001
Figure imgf000293_0001
BIOLOGICAL EXAMPLES: General examples of leaf disk tests in well plates:
Leaf disks or leaf segments of various plant species are cut from plants grown in a greenhouse. The cut leaf disks or segments are placed in multiwell plates (24-well format) onto water agar. The leaf disks are sprayed with a test solution before (preventative) or after (curative) inoculation. Compounds to be tested are prepared as DMSO solutions (max. 10 mg/ml) which are diluted to the appropriate concentration with 0.025% Tween20 just before spraying. The inoculated leaf disks or segments are incubated under defined conditions (temperature, relative humidity, light, etc.) according to the respective test system. A single evaluation of disease level is carried out 3 to 14 days after inoculation, depending on the pathosystem. Percent disease control relative to the untreated check leaf disks or segments is then calculated.
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, 1.6, 1.8, 1.10, 1 .1 1 , 1.12, 1.15, 1.16, 1.17, 1.19, 1.20, 1.22, 1 .24, 1.25, 1 .26, 1 .27, 1.28, 1 .29, 1.30, 1.31 , 1 .32, 1.33, 1 .34, 1 .35, 1.36, 1 .38, 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 .57, 1.59, 1 .60, 1.62, 1.64, 1.67, 1.69, 1.77, 1.81 , 1.83, 1.86, 1.87, 1.89, 1.90, 1.91 , 1.92, 1.93, 1.95, 1.97, 1.99, 1.100, 1.101 ,
1.102, 1.103, 1.104, 1.105, 1.106, 1.107, 1.109, 1.1 10, 1.1 1 1 , 1.1 12, 1.1 13, 1.1 14, 1.1 15, 1.1 17,
1.1 18, 1.1 19, 1.120, 1.121 , 1.122, 1.123, 1.124, 1.125, 1.126, 1.127, 1.128, 1.129, 1.130, 1.132,
1.133, 1.134, 1.135, 1.136, 1.138, 1.139, 1.140, 1.141 , 1.142, 1.143, 1.144, 1.145, 1.146, 1.147,
1.149, 1.150, 1.151 , 1.152, 1.154, 1.155, 1.157, 1.158, 1.159, 1.161 , 1.162, 1.164, 1.165, 1.167, 1.168, 1.169, 1.170, 1.171 , 1.172, 1.173, 1.175, 1.176, 1.177, 1.178, 1.180, 1.181 , 1.182, 1.183,
1.184, 1.185, 1.186, 1.187, 1.188, 1.189, 1.190, 1.191 , 1.192, 1.193, 1.194, 1.196, 1.198, 1.199,
1.200, 1.201 , 1.202, 1.205, 1.206, 1.209, 1.212, 1.214, 1.215, 1.216, 1.217, 1.218, 1.219, 1.221 ,
1.222, 1.223, 1.225, 1.226, 1.227, 1.229, 1.230, 1.233, 1.234, 1.235, 1.237, 1.238, 1.242, 1.243,
1.244, 1.245, 1.247, 1.248, 1.249, 1.250, 1.251 , 1.252, 1.253, 1.258, 1.259, 1.260, 1.264, 1.266, 1.270, 1.273, 1.274, 1.275, 1.276, 1.279, 1.280, 1.283, 1.287, 1.298, 1.305, 1.306, 1.308, 1.309,
1.312, 1.313, 1.314, 1.315, 1.316, 1.320, 1.323, 1.324, 1.325, 1.326, 1.327, 1.328, 1.329, 1.330,
1.331 , 1.332, 1.333, 1.334, 1.335, 1.336, 1.337, 1.338, 1.339, 1.340, 1.341 , 1.342, 1.344, 1.345,
1.346, 1.347, 1.348, 1.350, 1.351 , 1.352, 1.353, 1.354, 1.355, 1.356, 1.357, 1.358, 1.359, 1.360,
1.361 , 1.362, 1.363, 1.364, 1.365, 1.366, 1.367, 1.368, 1.369, 1.370, 1.371 , 1.372, 1.373, 1.374, 1.375, 1.376, 1.378, 1.379, 1.383, 1.384, 1.387, 1.388, 1.389, 1.390, 1.391 , 1.392, 1.395, 1.396,
1.398, 1.399, 1.400, 1.401 , 1.402, 1.403, 1.404, 1.405, 1.406, 1.407, 1.408, 1.410, 1.41 1 , 1.412,
1.413, 1.414, 1.415, 1.416, 1.417, 1.418, 1.421 , 1.422, 1.423, 1.424, 1.426, 1.427, 1.430, 1.431 ,
1.432, 1.433, 1.434, 1.435, 1.436, 1.437, 1.438, 1.440, 1.441 , 1.442, 1.443, 1.446, 1.447, 1.448,
1.449, 1.450, 1.451 , 1.452, 1.453, 1.456, 1.457, 1.458, 1.459, 1.460, 1.461 , 1.462, 1.463, 1.464, 1.465, 1.466, 1.467, 1.468, 1.469, 1.471 , 1.472, 1.473, 1.474, 1.475, 1.476, 1.477, 1.478, 1.479,
1.480, 1.481 , 1.482, 1.483, 1.484, 1.485, 1.486, 1.487, 1.488, 1.489, 1.490, 1.491 , 1.492, 1.493, 1.494, 1.495, 1.496, 1.497, 1.498, 1.499, 1.500, 1.501 , 1.502, 1.503, 1.504, 1.505, 1.506, 1.507, 1.508, 1.509, 1.510, 1.51 1 , 1.512, 1.513, 1.514, 1.515, 1.516, 1.517, 1.518, 1.519, 1.520, 1.521 , 1.522, 1.523, 1.524, 1.525, 1.526, 1.527, 1.528, 1.529, 1.530, 1.531 , 1.532, 1.537, 1.550, 1.552, 1.562, 1.563, 1.564, 1.565, 1.566, 1.567, 1.569, 1.570, 1.572, 1.573, 1.574, 1.575, 1.576, 1.577, 1.578, 1.579, 1.580, 1.581 , 1.582, 1.583, 1.584, 1.585, 1.587, 1.589, 1.590, 1.591 , 1.592, 1.593, 1.594, 1.595, 1.596, 1.597, 1.598, 1.599, 1.600, 1.602, 1.603, 1.604, 1.605, 1.606, 1.607, 1.608, 1.609, 1.610, 1.61 1 , 1.612, 1.613, 1.614, 1.615, 1.617, 1.618, 1.619, 1.620, 1.621 , 1.622, 1.623, 1.624, 1.625, 1.626, 1.627, 1.628, 1.629, 1.631 , 1.636, 1.640, 1.647, 1.651 , 1.652, 1.654, 1.655, 1.656, 1.658, 1.659, 1.660, 1.661 , 1.662, 1.663, 1.664, 1.665, 1.666, 1.668, 1.669, 1.670, 1.671 , 1.672, 1.673, 1.674, 1.675, 1.676, 1.677, 1.678, 1.679, 1.680, 1.681 , 1.682, 1.683, 1.684, 1.685, 1.686, 1.687, 1.688, 1.689, 1.690, 1.692, 1.696, 1.698, 1.701 , 1.702, 1.703, 1.704, 1.705, 1.707, 1.708, 1.709, 1.71 1 , 1.712, 1.713, 1.714, 1.715, 1.716, 1.717, 1.718, 1.720, 1.721 , 1.722, 1.723, 1.724, 1.725, 1.726, 1.727, 1.728, 1.729, 1.731 , 1.732, 1.733, 1.734, 1.735, 1.736, 1.737, 1.738, 1.739, 1.740, 1.741 , 1.742, 1.743, 1.744, 1.745, 1.747, 1.748, 1.749, 1.751 , 1.752, 1.753, 1.754, 1.756, 1.757, 1.758, 1.759, 1.760, 1.761 , 1.762, 1.763, 1.764, 1.765, 1.766, 1.767, 1.768, 1.769, 1.770, 1.771 , 1.772, 1.773, 1.774, 1.775, 1.776, 1.777, 1.778, 1.779, 1.781 , 1.782, 1.783, 1.784, 1.785, 1 .786, 1.787, 1.788, 1.789, 1.790, 1 .791 , 1.792, 1.793, 1.794, 1.795 and 1.810.
Compounds (from Table T2) 2.1 , 2.4, 2.6, 2.7, 2.14, 2.16, 2.21 , 2.22, 2.24, and 2.25.
Compounds (from Table T3) 3.1 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, 3.18, 3.19, 3.20, 3.21 , 3.22, 3.23, 3.24, 3.25, 3.26, 3.28, 3.29, 3.30, 3.31 , 3.32, 3.33, 3.34, 3.35, 3.36, 3.37, 3.38, 3.39, 3.40, 3.41 , 3.42, 3.43, 3.44, 3.45, 3.46, 3.47, 3.48, 3.49, 3.50, 3.51 , 3.52, 3.53, 3.54, 3.55, 3.56, 3.57, 3.58, 3.59, 3.60, 3.61 , 3.62, 3.63, 3.64, 3.65, 3.66, 3.67, 3.68, 3.69, 3.70, 3.71 , 3.72, 3.73, 3.74, 3.75, 3.76, 3.77, 3.78, 3.79, 3.80, 3.81 , 3.82, 3.83, 3.84, 3.85, 3.86, 3.87, 3.88, 3.89, 3.90, 3.91 , 3.92, 3.93, 3.94, 3.95, 3.96, 3.97, 3.98, 3.99, 3.101 , 3.102, and 3.103.
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, 1.6, 1.8, 1.10, 1.1 1 , 1.12, 1 .13, 1.14, 1.15, 1.16,
1.17, 1 .19, 1.20, 1.22, 1 .23, 1.24, 1 .25, 1.26, 1.27, 1 .28, 1.29, 1 .30, 1.31 , 1.32, 1 .34, 1.35, 1 .36, 1.37, 38, 1.40, 1.41, 1.42, 1.43, 1.44, 1.45, 1.46, 1.47, 1.48, 1.49, 1.50, 1.52, 1.53, 1.54, 1.57, 1.59, 1.64
71, 1.77, 1.81, 1.83, 1.86, 1.87, 1.89, 1.91, 1.92, 1.95, 1.97, 1.99, 1.100, 1.101, 1.102, 1.103, 1 104
106, 1 109, 1.110, 1 111, 1 .112, 1 114, 1.115, 1.117, 1 118, 1.119, 1.121, 1 .122, 1 123, 1 124
125, 1 126, 1.127, 1 128, 1 .129, 1 130, 1.131, 1.132, 1 134, 1.136, 1.137, 1 .138, 1 139, 1 145
146, 1 147, 1.149, 1 150, 1 .151, 1 153, 1.154, 1.155, 1 157, 1.159, 1.160, 1 .161, 1 162, 1 164
165, 1 167, 1.168, 1 169, 1 .170, 1 171, 1.172, 1.173, 1 175, 1.176, 1.177, 1 .178, 1 180, 1 181
182, 1 183, 1.185, 1 187, 1 .188, 1 189, 1.191, 1.192, 1 194, 1.196, 1.199, 1 .200, 1 201, 1 202
204, 1 206, 1.207, 1 210, 1 .215, 1 216, 1.217, 1.223, 1 225, 1.226, 1.227, 1 .229, 1 230, 1 233
235, 1 237, 1.242, 1 243, 1 .244, 1 245, 1.248, 1.249, 1 253, 1.259, 1.260, 1 .264, 1 266, 1 270
273, 1 275, 1.276, 1 279, 1 .280, 1 308, 1.309, 1.314, 1 315, 1.316, 1.317, 1 .323, 1 324, 1 325
326, 1 327, 1.328, 1 329, 1 .330, 1 331, 1.332, 1.333, 1 334, 1.335, 1.336, 1 .337, 1 339, 1 340
341, 1 344, 1.345, 1 346, 1 .347, 1 348, 1.349, 1.350, 1 351, 1.353, 1.355, 1 .356, 1 357, 1 358
359, 1 360, 1.361, 1 362, 1 .363, 1 364, 1.365, 1.366, 1 368, 1.369, 1.370, 1 .371, 1 372, 1 373
374, 1 375, 1.377, 1 378, 1 .379, 1 383, 1.384, 1.387, 1 388, 1.389, 1.390, 1 .391, 1 392, 1 395
396, 1 398, 1.399, 1 400, 1 .401, 1 402, 1.403, 1.404, 1 406, 1.407, 1.408, 1 .411, 1 412, 1 415
417, 1 421, 1.422, 1 426, 1 .427, 1 431, 1.432, 1.433, 1 434, 1.435, 1.438, 1 .442, 1 443, 1 444
445, 1 446, 1.447, 1 448, 1 .450, 1 451, 1.452, 1.455, 1 456, 1.457, 1.458, 1 .459, 1 460, 1 463
465, 1 466, 1.467, 1 468, 1 .469, 1 472, 1.473, 1.474, 1 476, 1.477, 1.478, 1 .479, 1 480, 1 481
483, 1 484, 1.485, 1 486, 1 .487, 1 488, 1.489, 1.490, 1 491, 1.492, 1.493, 1 .494, 1 495, 1 496
497, 1 498, 1.499, 1 500, 1 .501, 1 502, 1.503, 1.504, 1 505, 1.506, 1.507, 1 .508, 1 509, 1 510
511, 1 512, 1.513, 1 514, 1 .515, 1 516, 1.517, 1.518, 1 519, 1.520, 1.521, 1 .522, 1 523, 1 524
525, 1 526, 1.527, 1 528, 1 .529, 1 530, 1.531, 1.532, 1 563, 1.564, 1.566, 1 .567, 1 568, 1 569
570, 1 571, 1.573, 1 574, 1 .575, 1 577, 1.578, 1.579, 1 580, 1.582, 1.583, 1 .584, 1 585, 1 586
587, 1 589, 1.590, 1 591, 1 .592, 1 593, 1.594, 1.595, 1 596, 1.597, 1.599, 1 .600, 1 603, 1 604
605, 1 606, 1.607, 1 608, 1 .609, 1 610, 1.611, 1.612, 1 613, 1.614, 1.615, 1 .617, 1 618, 1 620
621, 1 622, 1.623, 1 624, 1 .625, 1 626, 1.629, 1.631, 1 640, 1.651, 1.652, 1 .654, 1 655, 1 656
658, 1 659, 1.660, 1 661, 1 .662, 1 663, 1.664, 1.665, 1 666, 1.667, 1.668, 1 .669, 1 670, 1 671
673, 1 674, 1.675, 1 676, 1 .677, 1 678, 1.679, 1.680, 1 681, 1.682, 1.683, 1 .684, 1 685, 1 686
687, 1 688, 1.689, 1 690, 1 .692, 1 693, 1.696, 1.698, 1 701, 1.702, 1.703, 1 .705, 1 707, 1 711
712, 1 713, 1.714, 1 717, 1 .718, 1 721, 1.722, 1.723, 1 724, 1.725, 1.726, 1 .727, 1 731, 1 732
738, 1 739, 1.740, 1 741, 1 .742, 1 743, 1.744, 1.745, 1 747, 1.748, 1.749, 1 .750, 1 751, 1 752
753, 1 756, 1.757, 1 758, 1 .759, 1 760, 1.761, 1.762, 1 763, 1.764, 1.765, 1 .766, 1 767, 1 768
769, 1 770, 1.771, 1 772, 1 .773, 1 774, 1.775, 1.776, 1 777, 1.778, 1.779, 1 .781, 1 782, 1 783
784, 1.785, 1.786, 1.787, 1.788, 1.789, 1.790, 1.791, 1.792, 1.793, 1.794, 1.795 and 1.810.
Compounds (from Table T2) 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.11, 2.14, 2.15, 2.16, 2.17, 2.20, 2.2224, and 2.25.
Compounds (from Table T3) 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 3.10, 3.12, 3.13, 3.1415, 3.16, 3.17, 3.18, 3.19, 3.20, 3.21, 3.22, 3.23, 3.24, 3.25, 3.26, 3.28, 3.29, 3.30, 3.31, 3.32, 3.3334, 3.36, 3.37, 3.38, 3.39, 3.40, 3.41, 3.42, 3.43, 3.44, 3.45, 3.46, 3.47, 3.48, 3.49, 3.50, 3.51, 3.5253, 3.54, 3.55, 3.56, 3.57, 3.58, 3.59, 3.60, 3.61, 3.63, 3.64, 3.65, 3.67, 3.68, 3.69, 3.70, 3.71, 3.72 3.73, 3.74, 3.75, 3.76, 3.77, 3.78, 3.79, 3.80, 3.81 , 3.82, 3.83, 3.84, 3.85, 3.86, 3.87, 3.88, 3.89, 3.90, 3.91 , 3.92, 3.93, 3.94, 3.95, 3.97, 3.98, 3.99, 3.100, 3.101 , 3.102, and 3.103.
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, 1.8, 1 .1 1 , 1.12, 1.14, 1.15, 1.16, 1.17, 1.19, 1.20, 1 .22, 1.23, 1 .24, 1 .26, 1.27, 1 .28, 1.29, 1.30, 1 .31 , 1.32, 1 .33, 1 .34, 1.35, 1 .36, 1.38, 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 .53, 1.54, 1 .57, 1 .58, 1.59, 1 .60, 1.64, 1.71 , 1.77, 1.81 , 1.82, 1.83, 1.84, 1.86, 1.87, 1.89, 1.90, 1.91 , 1.92, 1.93, 1.95, 1.97, 1.99, 1.100, 1.101 , 1.102, 1.103, 1.104, 1.106, 1.109, 1.1 10, 1.1 1 1 , 1.1 12, 1.1 14, 1.1 15, 1.1 17, 1.1 18, 1.1 19, 1.121 , 1.122, 1.123, 1.124, 1.125, 1.126, 1.128, 1.130, 1.132, 1.134, 1.135, 1.136, 1.138, 1.144, 1.145, 1.146, 1.147, 1.149, 1.150, 1.151 , 1.154, 1.155, 1.157, 1.158, 1.159, 1.164, 1.165, 1.166, 1.167, 1.168, 1.169, 1.170, 1.171 , 1.172, 1.173, 1.175, 1.176, 1.177, 1.178, 1.180, 1.181 , 1.182, 1.183, 1.185, 1.187, 1.189, 1.190, 1.191 , 1.192, 1.193, 1.194, 1.195, 1.196, 1.197, 1.199, 1.200, 1.201 , 1.202, 1.206, 1.207, 1.209, 1.210, 1.212, 1.215, 1.216, 1.217, 1.218, 1.220, 1.221 , 1.222, 1.223, 1.224, 1.226, 1.227, 1.229, 1.230, 1.233, 1.235, 1.238, 1.241 , 1.242, 1.243, 1.244, 1.245, 1.246, 1.253, 1.264, 1.273, 1.274, 1.275, 1.309, 1.312, 1.314, 1.315, 1.316, 1.324, 1.325, 1.327, 1.329, 1.331 , 1.335, 1.337, 1.339, 1.341 , 1.342, 1.344, 1.345, 1.346, 1.350, 1.351 , 1.355, 1.356, 1.358, 1.359, 1.360, 1.361 , 1.363, 1.365, 1.368, 1.369, 1.372, 1.379, 1.383, 1.384, 1.387, 1.389, 1.390, 1.392, 1.395, 1.398, 1.399, 1.401 , 1.402, 1.403, 1.404, 1.407, 1.408, 1.412, 1.416, 1.418, 1.432, 1.457, 1.466, 1.471 , 1.472, 1.475, 1.476, 1.477, 1.478, 1.479, 1.480, 1.483, 1.484, 1.485, 1.486, 1.487, 1.488, 1.489, 1.491 , 1.492, 1.493, 1.494, 1.495, 1.496, 1.497, 1.498, 1.499, 1.500, 1.503, 1.504, 1.505, 1.506, 1.507, 1.508, 1.509, 1.510, 1.51 1 , 1.512, 1.513, 1.514, 1.515, 1.516, 1.517, 1.518, 1.519, 1.520, 1.521 , 1.523, 1.524, 1.525, 1.526, 1.527, 1.528, 1.529, 1.531 , 1.532, 1.562, 1.563, 1.564, 1.566, 1.567, 1.568, 1.569, 1.570, 1.571 , 1.573, 1.574, 1.575, 1.576, 1.577, 1.578, 1.579, 1.580, 1.581 , 1.582, 1.583, 1.584, 1.585, 1.586, 1.587, 1.589, 1.590, 1.591 , 1.592, 1.594, 1.595, 1.596, 1.597, 1.599, 1.600, 1.603, 1.604, 1.605, 1.606, 1.607, 1.608, 1.610, 1.61 1 , 1.612, 1.613, 1.614, 1.615, 1.616, 1.617, 1.618, 1.619, 1.620, 1.621 , 1.622, 1.623, 1.624, 1.625, 1.626, 1.627, 1.628, 1.629, 1.630, 1.631 , 1.632, 1.634, 1.636, 1.637, 1.639, 1.640, 1.641 , 1.642, 1.643, 1.644, 1.645, 1.646, 1.647, 1.648, 1.649, 1.651, 1.652, 1.653, 1.654, 1.655, 1.656, 1.657, 1.658, 1.659, 1.660, 1.661, 1.662, 1.663, 1.664, 1.665, 1.666, 1.667, 1.668, 1.669, 1.670, 1.671, 1.672, 1.673, 1.674, 1.675, 1.676, 1.677, 1.678, 1.679, 1.680, 1.681, 1.682, 1.683, 1.684, 1.685, 1.686, 1.687, 1.688, 1.689, 1.690, 1.691, 1.692, 1.693, 1.694, 1.695, 1.696, 1.697, 1.698, 1.699, 1.700, 1.701, 1.702, 1.703, 1.704, 1.705, 1.706, 1.707, 1.708, 1.709, 1.710, 1.711, 1.712, 1.714, 1.715, 1.716, 1.717, 1.718, 1.720, 1.721, 1.722, 1.723, 1.724, 1.725, 1.726, 1.727, 1.728, 1.729, 1.730, 1.731, 1.732, 1.733, 1.734, 1.735, 1.736, 1.737, 1.738, 1.739, 1.740, 1.741, 1.742, 1.743, 1.744, 1.745, 1.746, 1.747, 1.748, 1.749, 1.750, 1.751, 1.752, 1.753, 1.754, 1.755, 1.756, 1.757, 1.758, 1.759, 1.760, 1.761, 1.762, 1.763, 1.764, 1.765, 1.766, 1.767, 1.768, 1.769, 1.770, 1.771, 1.772, 1.773, 1.774, 1.775, 1.776, 1.777, 1.778, 1.779, 1.781, 1.782, 1.783, 1.784, 1.786 and 1.810.
Compounds (from Table T2) 2.2, 2.3, 2.4, 2.5, 2.21, 2.24, and 2.25.
Compounds (from Table T3) 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 3.11, 3.12, 3.13, 3.14, 3.15, 3.16, 3.17, 3.18, 3.19, 3.20, 3.21, 3.22, 3.23, 3.24, 3.25, 3.26, 3.28, 3.29, 3.30, 3.31, 3.32, 3.33, 3.34, 3.36, 3.37, 3.38, 3.39, 3.40, 3.41, 3.42, 3.43, 3.44, 3.45, 3.46, 3.47, 3.48, 3.51, 3.52, 3.53, 3.55, 3.56, 3.57, 3.58, 3.59, 3.60, 3.61 , and 3.62.
Fungicidal activity against Glomerella lagenarium (Colletotrichum lagenarium) liquid culture / cucumber / preventative (Anthracnose) Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB - potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96- well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 C and the inhibition of growth is measured photometrically 3 to 4 days after application.
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, 1.11, 1.12, 1.13, 1.15, 1.16, 1.17, 1.18, 1.19, 1.20, 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29, 1.30, 1.31, 1.32, 1.33, 1.34, 1.35, 1.36, 1.37, 1.38, 1.40, 1.41, 1.42, 1.43, 1.44, 1.45, 1.46, 1.47, 1.48, 1.49, 1.50, 1.51, 1.53, 1.54, 1.55, 1.57, 1.58, 1.59, 1.61, 1.64, 1.67, 1.68, 1.69, 1.71, 1.72, 1.74, 1.77, 1.81, 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, 1.98, 1.99, 1.100, 1.101, 1.102, 1.103, 1.104, 1.105, 1.106, 1.107, 1.108, 1.109, 1.110, 1.111, 1.112, 1.113, 1.114, 1.115, 1.116, 1.117, 1.118, 1.119, 1.120, 1.121, 1.122, 1.123, 1.124, 1.125, 1.126, 1.127, 1.128, 1.129, 1.130, 1.131, 1.132, 1.133, 1.134, 1.135, 1.136, 1.138, 1.139, 1.142, 1.144, 1.145, 1.146, 1.147, 1.148, 1.149, 1.150, 1.151, 1.152, 1.153, 1.154, 1.155, 1.157, 1.158, 1.159, 1.161, 1.162, 1.163, 1.164, 1.165, 1.166, 1.167, 1.168, 1.169, 1.170, 1.171, 1.173, 1.174, 1.175, 1.176, 1.177, 1.178, 1.179, 1.180, 1.181, 1.182, 1.183, 1.184, 1.185, 1.187, 1.189, 1.190, 1.191, 1.192, 1.193, 1.194, 1.195, 1.196, 1.199, 1.201, 1.202, 1.203, 1.205, 1.206, 1.207, 1.208, 1.209, 1.210, 1.211, 1.212, 1.213, 1.214, 1.215, 1.216, 1.217, 1.218, 1.219, 1.220, 1.221, 1.222, 1.223, 1.224, 1.225, 1.226, 1.227, 1.228, 1.229, 1.230, 1.231, 1.232, 1.233, 1.235, 1.236, 1.237, 1.238, 1.239, 1.240, 1.242, 1 243, 1 244, 1.245, 1 246, 1.247, 1 248, 1.249, 1.250, 1 251 , 1.252, 1 253, 1.254, 1 255, 1.256,
1 257, 1 258, 1.259, 1 260, 1.261 , 1 262, 1.264, 1.265, 1 266, 1.268, 1 269, 1.270, 1 271 , 1.272,
1 273, 1 274, 1.275, 1 276, 1.277, 1 278, 1.279, 1.280, 1 281 , 1.282, 1 283, 1.284, 1 285, 1.286,
1 287, 1 288, 1.289, 1 290, 1.291 , 1 292, 1.293, 1.294, 1 295, 1.297, 1 298, 1.299, 1 301 , 1.302,
5 1 303, 1 304, 1.305, 1 306, 1.307, 1 308, 1.309, 1.310, 1 31 1 , 1.312, 1 313, 1.314, 1 315, 1.316,
1 317, 1 318, 1.319, 1 320, 1.321 , 1 322, 1.323, 1.324, 1 325, 1.326, 1 327, 1.328, 1 329, 1.330,
1 331 , 1 332, 1.333, 1 334, 1.335, 1 336, 1.337, 1.338, 1 339, 1.340, 1 341 , 1.342, 1 343, 1.344,
1 345, 1 346, 1.347, 1 348, 1.349, 1 350, 1.351 , 1.352, 1 355, 1.356, 1 358, 1.359, 1 360, 1.361 ,
1 362, 1 363, 1.364, 1 365, 1.366, 1 367, 1.368, 1.369, 1 370, 1.371 , 1 372, 1.373, 1 374, 1.375,
10 1 376, 1 377, 1.378, 1 379, 1.380, 1 381 , 1.382, 1.384, 1 385, 1.387, 1 388, 1.389, 1 390, 1.391 ,
1 392, 1 393, 1.394, 1 395, 1.396, 1 397, 1.398, 1.399, 1 400, 1.401 , 1 402, 1.403, 1 404, 1.405,
1 406, 1 407, 1.408, 1 409, 1.410, 1 41 1 , 1.412, 1.413, 1 414, 1.415, 1 416, 1.417, 1 418, 1.419,
1 420, 1 421 , 1.422, 1 423, 1.424, 1 425, 1.426, 1.427, 1 428, 1.429, 1 430, 1.431 , 1 432, 1.433,
1 434, 1 435, 1.436, 1 437, 1.438, 1 439, 1.440, 1.442, 1 443, 1.445, 1 446, 1.447, 1 448, 1.449,
15 1 450, 1 451 , 1.452, 1 453, 1.455, 1 456, 1.457, 1.458, 1 459, 1.460, 1 461 , 1.462, 1 463, 1.464,
1 465, 1 466, 1.467, 1 468, 1.469, 1 470, 1.471 , 1.472, 1 473, 1.474, 1 475, 1.476, 1 477, 1.478,
1 479, 1 480, 1.481 , 1 482, 1.483, 1 484, 1.485, 1.486, 1 487, 1.488, 1 489, 1.490, 1 491 , 1.492,
1 493, 1 494, 1.495, 1 496, 1.497, 1 498, 1.499, 1.500, 1 501 , 1.502, 1 503, 1.504, 1 505, 1.506,
1 507, 1 508, 1.509, 1 510, 1.51 1 , 1 512, 1.513, 1.514, 1 515, 1.516, 1 517, 1.518, 1 519, 1.520,
20 1 521 , 1 522, 1.523, 1 524, 1.525, 1 526, 1.527, 1.528, 1 529, 1.530, 1 531 , 1.532, 1 533, 1.534,
1 535, 1 536, 1.537, 1 538, 1.539, 1 540, 1.541 , 1.542, 1 543, 1.544, 1 545, 1.546, 1 547, 1.548,
1 549, 1 550, 1.551 , 1 553, 1.554, 1 555, 1.556, 1.557, 1 558, 1.559, 1 560, 1.561 , 1 562, 1.563,
1 564, 1 565, 1.566, 1 567, 1.568, 1 569, 1.570, 1.571 , 1 572, 1.573, 1 574, 1.575, 1 576, 1.577,
1 578, 1 579, 1.580, 1 581 , 1.582, 1 583, 1.584, 1.585, 1 586, 1.587, 1 588, 1.589, 1 590, 1.591 ,
25 1 592, 1 593, 1.594, 1 595, 1.596, 1 597, 1.598, 1.599, 1 600, 1.601 , 1 602, 1.603, 1 604, 1.605,
1 606, 1 607, 1.608, 1 609, 1.610, 1 61 1 , 1.612, 1.613, 1 614, 1.615, 1 616, 1.617, 1 618, 1.619,
1 620, 1 621 , 1.622, 1 623, 1.624, 1 625, 1.626, 1.627, 1 628, 1.629, 1 630, 1.631 , 1 632, 1.633,
1 634, 1 636, 1.637, 1 638, 1.639, 1 641 , 1.642, 1.643, 1 644, 1.645, 1 646, 1.647, 1 648, 1.649,
1 650, 1 651 , 1.652, 1 653, 1.654, 1 655, 1.656, 1.657, 1 658, 1.659, 1 660, 1.661 , 1 662, 1.663,
30 1 664, 1 665, 1.666, 1 667, 1.668, 1 669, 1.670, 1.671 , 1 672, 1.673, 1 674, 1.675, 1 676, 1.677,
1 678, 1 679, 1.680, 1 681 , 1.682, 1 683, 1.684, 1.685, 1 686, 1.687, 1 688, 1.689, 1 690, 1.691 ,
1 692, 1 693, 1.694, 1 695, 1.696, 1 697, 1.698, 1.699, 1 700, 1.701 , 1 702, 1.703, 1 704, 1.705,
1 706, 1 707, 1.708, 1 709, 1.713, 1 714, 1.715, 1.716, 1 717, 1.718, 1 720, 1.723, 1 724, 1.725,
1 726, 1 727, 1.729, 1 730, 1.733, 1 734, 1.735, 1.736, 1 737, 1.738, 1 739, 1.740, 1 741 , 1.742,
35 1 743, 1 745, 1.749, 1 751 , 1.752, 1 753, 1.754, 1.755, 1 756, 1.757, 1 758, 1.759, 1 760, 1.761 ,
1 762, 1 763, 1.764, 1 765, 1.766, 1 768, 1.769, 1.770, 1 771 , 1.772, 1 773, 1.774, 1 775, 1.776,
1 777, 1 778, 1.779, 1 780, 1.781 , 1 782, 1.783, 1.784, 1 785, 1.786, 1 787, 1.790, 1 791 , 1.793,
1 .795, 1.810 and 1.81 1.
Compounds (from Table T2) 2.1 , 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 2.10, 2.1 1 , 2.12, 2.13, 2.14, 2.15, 2.16, 2.17, 2.18, 2.19, 2.20, 2.21 , 2.22, 2.24, and 2.25. 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, 3.18, 3.19, 3.20, 3.21 , 3.22, 3.23, 3.24, 3.25, 3.26, 3.28, 3.29, 3.30, 3.31 , 3.32, 3.33, 3.34, 3.35, 3.36, 3.37, 3.38, 3.39, 3.40, 3.41 , 3.42, 3.43, 3.44, 3.45, 3.46, 3.47, 3.48, 3.49, 3.51 , 3.52, 3.53, 3.54, 3.55, 3.56, 3.57, 3.58, 3.59, 3.60, 3.61 , 3.62, 3.63, 3.64, 3.65, 3.66, 3.67, 3.69, 3.70, 3.71 , 3.72, 3.73, 3.74, 3.75, 3.76, 3.77, 3.78, 3.79, 3.80, 3.81 , 3.82, 3.83, 3.84, 3.85, 3.87, 3.88, 3.89, 3.90, 3.91 , 3.92, 3.93, 3.94, 3.95, 3.96, 3.97, 3.98, 3.99, 3.100, 3.101 , 3.102, and 3.103.

Claims

Claims:
1. A compound of formula (I)
Figure imgf000301_0001
n is 1 or 2
A1 represents N or CR1, wherein R1 is hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy;
A2 represents N or CR2, wherein R2 is hydrogen, halogen, methyl, ethyl, difluoromethyl, 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 0, 1 or 2 of A1, A2, A3 and 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 hydroxy, C1_4alkyl, C1_4haloalkyl, C1_4alkoxy, hydroxyC1_4alkyl, C1.2alkoxyC1_4alkyl, d. 2haloalkoxyC1-4alkyl, C3.6alkenyl, C3_4alkynyl, C3.6alkenyloxy, C3.6alkynyloxy, C3.6haloalkenyl, C3.
6haloalkenyloxy, C1_4alkylcarbonyloxy, C1_4haloalkylcarbonyloxy, C1_4alkoxycarbonyloxy, C1_ 4alkylcarbonyloxyC1_4alkyl, C1_4haloalkylcarbonyloxyC1_4alkyl or C1_4alkoxycarbonyloxyC1_4alkyl; or
R7 is C3.6cycloalkyl, C3.6cycloalkylC1.2alkyl, C3.6cycloalkylC1.2alkoxy, phenyl, phenylC1_2alkyl, phenylC1-2alkoxy, heteroaryl, heteroarylC1_2alkyl, heteroarylC1_2alkoxy, heterocyclyl, heterocyclylC1_ 2alkyl, heterocyclylC1_2alkoxy, C3.6cycloalkylcarbonyloxy, heterocyclylcarbonyloxy, phenylcarbonyloxy, C3.6cycloalkylcarbonyloxyC1_4alkyl, heterocyclylcarbonyloxyC1_4alkyl or phenylcarbonyloxyC1_4alkyl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 or 2 heteroatoms individually selected from N, O and S, and wherein any of said cycloalkyl, phenyl, heteroaryl and heterocyclyl moieties are optionally substituted by 1 or 2 substituents selected from cyano, fluoro, chloro, bromo, methyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, or difluoromethoxy; R8 is hydrogen, C1_6alkyl, C2.6alkenyl, C2.6alkynyl, cyanoC1_6alkyl, C1_6haloalkyl, C2.
6haloalkenyl, hydroxyC1_6alkyl, C1_4alkoxyC1.6alkyl, C1_4haloalkoxyC1.6alkyl,
Figure imgf000302_0001
6alkyl, C2-4alkynyloxyC1.6alkyl, aminoC1_6alkyl, N-C1_4alkylaminoC1.6alkyl, N,N-diC1_4alkylaminoC1.6alkyl, C1.6alkylcarbonylC1.6alkyl, C1.6alkylcarbonylC2.6alkenyl, C1.6alkoxycarbonylC1.6alkyl, d. 6alkylcarbonyloxyC1_6alkyl, N-C1_4alkylaminocarbonylC1.6alkyl, N,N-diC1_4alkylaminocarbonylC1.6alkyl, C1-6alkylsulfanylC1-6alkyl, C1.6alkylsulfonylC1.6alkyl, C1.6alkylsulfonylaminoC1.6alkyl, C1_6 alkylsulfonylaminoC2.6alkynyl, C2.6alkynyloxycarbonylaminoC1.6alkyl, C1_4alkylcarbonylaminoC1.6alkyl or C1-4alkoxycarbonylaminoC1.6alkyl; or
R8 is C3.8cycloalkyl, C3.8cycloalkylC1.6alkyl, wherein the cycloalkyl moiety is optionally partially unsaturated, phenyl, phenylC1_6alkyl, phenylC2.6alkenyl, napthyl, naphthylC1_6alkyl, heteroaryl, heteroarylC1_6alkyl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterodiaryl, heterodiarylC1-6alkyl wherein the heterodiaryl moiety is a 9- or 10-membered bicyclic aromatic system which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl, heterocyclylC1-6alkyl wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, or C3. 6cycloal kylcarbonylam i noC1 _6alkyl ,
wherein for R8, any cycloalkyl, phenyl, napthyl, heteroaryl, heterodiaryl or heterocyclyl moiety is optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R9; or, additionally, when R8 is cyclopropyl, the cyclopropyl moiety is substituted by 4 substituents, which may be the same or different, selected from R9, with the proviso that at least 2 R9 substituents are the same; wherein
R9 is cyano, halogen, hydroxy, C1_4alkyl, C2_4alkenyl, C2_4alkynyl, C1_4haloalkyl, C2_4haloalkenyl, C1-4alkoxy, C1_4haloalkoxy, C3_4alkynyloxy, N-C1_4alkylamino, N,N-diC1_4alkylamino, C1_4alkylcarbonyl, C3.6cycloalkylcarbonyl, C1_4alkoxycarbonyl, carbonylamino, N-C1_4alkylaminocarbonyl, N,N-diC1_ 4alkylaminocarbonyl or C1_4alkoxycarbonylamino, and wherein when R8 is substituted C3.8cycloalkyl, C3.8cycloalkylC1-6alkyl, heterocyclyl or heterocyclylC1_6alkyl, R9 may also represent oxo on the C3. scycloalkyl or heterocyclyl moiety; or wherein for R8, any cycloalkyl, phenyl, napthyl, heteroaryl, heterodiaryl or heterocyclyl moiety is optionally substituted by 1 substituent selected from R10 and further optionally substituted by 1 or 2 substituents selected from R9; wherein R10 is C3.8cycloalkyl, C3.8cycloalkylC1_2alkyl, phenyl, phenylC1_2alkyl, heteroaryl, heteroarylC1_
2alkyl wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl or heterocyclylC1_6alkyl wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S, and wherein any of said cycloalkyl, phenyl, heteroaryl and heterocyclyl moieties are optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R11; wherein
R11 is hydrogen, cyano, fluoro, chloro, bromo, methyl, trifluoromethyl, methoxy and ethoxy; or R8 represents -OR12, wherein R12 is hydrogen, C1_6alkyl, C3.6alkenyl, C3.6alkynyl, cyanoC-i.
6alkyl, C1_6haloalkyl, C3.6haloalkenyl, hydroxyC1_6alkyl, C1_4alkoxyC1.6alkyl, C1_4haloalkoxyC1.6alkyl, d. 4alkoxyC1-4alkoxyC1-6alkyl, aminoC1_6alkyl, N-C1_4alkylaminoC1.6alkyl, N,N-diC1_4alkylaminoC1.6alkyl, C1_ 6alkylcarbonylC1-6alkyl, C1.6alkylcarbonylC2-6alkenyl, C1.6alkoxycarbonylC1.6alkyl, C1_ 6alkylcarbonyloxyC1_6alkyl, N-C1_4alkylaminocarbonylC1.6alkyl, N,N-diC1_4alkylaminocarbonylC1.6alkyl, C1-4alkylsulfanylC1.6alkyl, C1.6alkylsulfonylC1.6alkyl or C1.6alkylsulfonylaminoC1.6alkyl; or
R12 is C3.8cycloalkyl, C3.8cycloalkylC1.6alkyl, wherein the cycloalkyl moiety is optionally partially unsaturated, phenyl, phenylC1_6alkyl, heteroaryl, heteroarylC1_6alkyl, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl or heterocyclylC1_6alkyl, wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S,
wherein for R12, any cycloalkyl, phenyl, heteroaryl or heterocyclyl moiety is optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R13; wherein
R13 is cyano, halogen, hydroxy, C1_4alkyl, C2-4alkenyl, C2-4alkynyl, C1_4haloalkyl, C2. 4haloalkenyl, C1_4alkoxy, C1_4haloalkoxy, C3_4alkenyloxy, C3_4alkynyloxy, N-C1_4alkylamino, N,N-diC1_ 4alkylamino, C1_4alkylcarbonyl, C1_4alkoxycarbonyl, carbonylamino, N-C1_4alkylaminocarbonyl, N,N- diC1_4alkylaminocarbonyl or C1_4alkoxycarbonylamino;
and wherein when R12 is substituted C3.8cycloalkyl, C3.8cycloalkylC1.6alkyl, heterocyclyl or heterocyclylC1-6alkyl, R13 may also represent oxo on the C3.8cycloalkyl or heterocyclyl moiety; or R8 represents -NR14R15, wherein R14 is hydrogen, cyano, C1_6alkyl, C1_6alkoxy, C2.6alkenyl, C2.
6alkynyl, C3.6alkenyloxy, C3.6alkynyloxy, cyanoC1_6alkyl, C1_6haloalkyl, C1_6haloalkenyl, hydroxyC1_6alkyl, C1-4alkoxyC1.6alkyl, C1_4haloalkoxyC1_6alkyl, C1_4alkoxyC1_4alkoxyC1.6alkyl, aminoC1_6alkyl, N-C1_ 4alkylaminoC1_6alkyl, N,N-diC1_4alkylaminoC1.6alkyl, C1.6alkylcarbonylC1.6alkyl, C1.6alkylcarbonylC2. 6alkenyl, C1.6alkoxycarbonylC1.6alkyl, C1.6alkylcarbonyloxyC1.6alkyl, N-C1_4alkylaminocarbonylC1.6alkyl, N,N-diC1-4alkylaminocarbonylC1.6alkyl, C1_4alkylsulfanylC1_6alkyl, C1.6alkylsulfonylC1.6alkyl or C1_ 6alkylsulfonylaminoC1.6alkyl; or R14 is C3.8cycloalkyl, C3-8cycloalkylC1-6alkyl, C3.8cycloalkylC1.6alkoxy, C3.6cycloalkyloxy, wherein the cycloalkyl moiety is optionally partially unsaturated, phenyl, phenylC1_6alkyl, phenyld. 6alkoxy, heteroaryl, heteroarylC1_6alkyl, heteroarylC1_6alkoxy, wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and S, heterocyclyl, heterocyclylC1_6alkyl or heterocyclylC1_6alkoxy wherein the heterocyclyl moiety is a 4- to 6-membered non-aromatic ring which comprises 1 , 2 or 3 heteroatoms individually selected from N, O and S,
wherein for R14, any cycloalkyl, phenyl, heteroaryl, heterocyclyl moiety is optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R16; wherein
R16 is cyano, halogen, hydroxy, C1_4alkyl, C2-4alkenyl, C2-4alkynyl, C1_4haloalkyl, C2. 4haloalkenyl, C1_4alkoxy, C1-2alkoxyC1-2alkyl, C1_4haloalkoxy, C3_4alkenyloxy, C3_4alkynyloxy, N-C1_ 4alkylamino, N,N-diC1_4alkylamino, C1_4alkylcarbonyl, C1_4alkoxycarbonyl, carbonylamino, N-C1_ 4alkylaminocarbonyl, N,N-diC1_4alkylaminocarbonyl and C1_4alkoxycarbonylamino;
and wherein when R14 is substituted C3.8cycloalkyl, C3.8cycloalkylC1.6alkyl, C3.8cycloalkylC1_ 6alkoxy, heterocyclyl, heterocyclylC1_6alkyl or heterocyclylC1_6alkoxy, R16 may also represent oxo on the C3.8cycloalkyl or heterocyclyl moiety; R15 is hydrogen, C1_4alkyl, C3_4alkynyl, C1_4alkoxyC1_4alkyl, cyanoC1_4alkyl, C3.6cycloalkyl, C3.
6cycloalkylC1_2alkyl; or
R14 and R15, together with the nitrogen atom to which they are bonded , form a 4-, 5- or 6- membered cycle optionally containing an additional heteroatom or group selected from O, S, S(0)2, oxo (=0) and NR17; wherein
R17 is hydrogen, methyl, methoxy, formyl or acyl; or a salt or an N-oxide thereof.
2. A compound according to claim 1 , wherein A1, A2, A3 and A4 are C-H.
3. A compound according to claim 1 or claim 2, wherein R5 and R6 are hydrogen and n is 1.
4. A compound according to any one of claims 1 to 3, wherein: when R8 is not OR12 or NR14R15, R7 is d_4alkyl, C2-4haloalkyl, d_4alkoxy or C3_ 6cycloalkyl; or when R8 is OR12, R7 is hydroxy, C1_4alkyl, C2_4haloalkyl, C1_4alkoxy, C3_4alkenyl, C3. 4alkynyl or C1_4alkoxycarbonyloxy; or when R8 is NR14R15, R7 is hydroxy, C1_4alkyl, C2haloalkyl, C1_2alkoxy, C3_4alkenyl, C3. 4alkynyl or cyclopropyl.
5. A compound according to any one of claims 1 to 4, wherein:
R8 is C1-6alkyl, C2-4alkenyl, C2-4alkynyl, cyanoC1_4alkyl, C1_5haloalkyl, C2_4haloalkenyl, hydroxyC1_4alkyl, C1_2alkoxyC1_4alkyl, C1_2haloalkoxyC1_4alkyl, C1.2alkoxyC1.2alkoxyC1_4alkyl, aminod. 4alkyl, C1_2alkylcarbonylC1_4alkyl, C1_4alkylcarbonylC2_4alkenyl, C1_4alkylcarbonyloxyC1_4alkyl, d. 4alkylsulfonylaminoC2_4alkynyl, C1.2alkylcarbonylaminoC1_4alkyl, C2_4alkynyloxycarbonylaminoC1_4alkyl or C1-2alkoxycarbonylaminoC1-4alkyl; or
R8 is C3.6cycloalkyl, C3.6cycloalkylC1.2alkyl, phenyl, phenylC1_4alkyl, phenylC2_4alkenyl, napthyl, a heteroaryl-containing moiety selected from furanyl, pyrazolyl, imidazolyl, triazolyl, 1 ,2,3- benzothiadiazole, (pyridinyl)methyl, or a heterocyclyl-containing moiety selected from oxetanyl, pyrrolidinyl, azetidinyl, tetrahydrofuranyl, 1 ,3-dioxolanyl, thietanyl, 1-oxo-thietan-3-yl, 1 ,1-dioxo-thietan- 3-yl, tetrahydropyranyl, tetrahydrothiopyranyl or C3.6cycloalkylcarbonylaminoC1_4alkyl, wherein the cycle of each heteroaryl-containing moiety or heterocyclyl-containing moiety is optionally substituted by 1 , 2 or 3 substituents, which may be the same of different, selected from R9, or
wherein the cycle of each heteroaryl-containing moiety or heterocyclyl-containing moiety is optionally substituted by 1 substituent selected from R10 and further optionally substituted by 1 or 2 substituents selected from R9; R9 is cyano, methyl, chloro, fluoro, hydroxyl, methoxy, trifluoromethyl, C2-haloalkenyl, methylcarbonyl, ethylcarbonyl and carbonylamino;
R10 is phenyl or pyridinyl, wherein phenyl or pyridinyl is optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R11;
R11 is fluoro, chloro, bromo and methoxy; or when R8 is -OR12, R12 is hydrogen, C1_6alkyl, C3.6alkenyl, C3.6alkynyl, C1_6haloalkyl, d.
4alkoxyC1-6alkyl, phenyl or phenylC1_6alkyl; or when R8 is -NR14R15, R14 is hydrogen, cyano, C1_6alkyl, C1_6alkoxy, C2.6alkenyl, C2.6alkynyl, cyanoC1-6alkyl, C1_6haloalkyl, C1_4alkoxyC1_6alkyl, C1.6alkoxycarbonylC1.6alkyl, or C3.8cycloalkyl, C3. 8cycloalkylC1-6alkyl, phenyl or heteroarylC1_6alkyl, wherein the heteroaryl moiety is a 5-membered monocyclic aromatic ring which comprises 1 , 2, 3 or 4 heteroatoms individually selected from N, O and
5. wherein any cycloalkyl, phenyl or heteroaryl moiety is optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R16, wherein R16 is cyano, halogen, hydroxy, d.
5 4alkyl, C1_4haloalkyl, C1_4alkoxy, C1_4haloalkoxy and C1_4alkoxycarbonyl; and
R15 is hydrogen, methyl, ethyl, C3_4alkynyl or methoxyethyl.
6. A compound according to any one of claims 1 to 4, wherein R8 is C1_6alkyl, C1_2haloalkyl, 10 hydroxyC1-6alkyl, C1.2alkoxyC1_4alkyl, C3.6cycloalkyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- or 5-membered non-aromatic ring which comprises 1 or 2 heteroatoms individually selected from N and O, wherein C3.6cycloalkyl and heterocyclyl are optionally substituted by 1 , 2 or 3 substituents, which may be the same or different, selected from R9; wherein R9 is cyano, halogen, hydroxy, d. 4alkyl, C2-4alkenyl, C2-4alkynyl, C1_4haloalkyl and C1_4alkoxy.
15
7. A compound according to any one of claims 1 to 4 or 6, wherein R8 is C1_4alkyl, C1_2haloalkyl, hydroxyC1-4alkyl, C1_2alkoxyC1_4alkyl, C3.6cycloalkyl or heterocyclyl, wherein the heterocyclyl moiety is a 4- or 5-membered non-aromatic ring which comprises 1 or 2 heteroatoms which are oxygen, wherein C3.6cycloalkyl and heterocyclyl are optionally substituted by 1 or 2 substituents, which may be the
20 same or different, selected from R9; wherein R9 represents cyano, fluoro, chloro, hydroxy, methyl, ethyl, trifluoromethyl and methoxy.
8. A compound according to any one of claims 1 to 4, 6 or 7, wherein R8 is C1_4alkyl, 2,2,2- trifluoroethyl, hydroxyC1_4alkyl, C1_2alkoxyC1_2alkyl, cyclopropyl or heterocyclyl, wherein the
25 heterocyclyl moiety is tetrahydrofuran-2-yl, oxetan-3-yl or 1 ,3-dioxolan-2-yl, wherein cyclopropyl and heterocyclyl are each optionally substituted by 1 or 2 substituents, which may be the same or different, selected from R9, wherein R9 is fluoro, chloro and methyl.
9. A compound according to any one of claims 1 to 5, wherein R12 is C1_6alkyl, C3_4alkenyl, C3. 30 4alkynyl, C1_4fluoroalkyl, C1_4chloroalkyl, C1_2alkoxyC1_2alkyl, phenyl or benzyl.
10. A compound according to any one of claims 1 to 5, wherein R14 is hydrogen, C1_6alkyl, d. 6alkoxy, C2_4alkenyl, C2_4alkynyl, C1_2haloalkyl or C3.6cycloalkyl.
35 11. A compound according to any one of claims 1 to 5 or 10, wherein R15 is hydrogen, methyl or ethyl.
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.
40
13. A composition according to claim 12, further comprising at least one additional active 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.
Use of a compound of formula (I) according to any one of claims 1 to 1 1 as a fungicide.
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